阅读说明：本技术 以硅烷偶联剂配合量指标为特征的牙科用组合物 (Dental composition characterized by index of amount of silane coupling agent blended ) 是由 山本健蔵 �原大辅 西野靖弘 北田直也 于 2021-04-01 设计创作，主要内容包括：本发明提供对各种牙科切削加工修复材料和牙质的耐久粘接强度和保存稳定性优异的牙科用粘接性组合物。本发明的牙科用粘接性组合物包含基体,基体含有(A1)式(a)表示的硅烷偶联剂、(B)具有酸性基团的聚合性单体、(C)不具有酸性基团的聚合性单体,该(C)不具有酸性基团的聚合性单体包含(C1)不具有酸性基团但具有一个以上羟基的聚合性单体,(A1)与(C1)在至少一个基体中共存,满足式(1)和式(2)中的至少一个。式(1)：0.005≤基体中硅烷偶联剂配合量指标((S1×W1)/M1)的合计≤0.070；式(2)：0.001≤组合物中硅烷偶联剂配合量指标((S2×W2)/M2)的合计≤0.015。(The invention provides an adhesive composition for dental use, which has excellent durable adhesive strength and storage stability to various dental cutting restorative materials and dentine. The dental adhesive composition comprises a base containing (A1) a silane coupling agent represented by the formula (a), (B) a polymerizable monomer having an acid group, and (C) a polymerizable monomer having no acid group, wherein the polymerizable monomer (C) has no acidThe polymerizable monomer having a polymerizable group includes (C1) a polymerizable monomer having no acidic group and having one or more hydroxyl groups, (a1) and (C1) coexist in at least one matrix, and at least one of the formulae (1) and (2) is satisfied. Formula (1): 0.005-0.070 in total of the silane coupling agent content indicators ((S1 XW 1)/M1) in the matrix; formula (2): the sum of the silane coupling agent content indices ((S2 XW 2)/M2) in the composition is 0.001-0.015.)

1. An adhesive composition for dental use, comprising a base containing:

(A) a silane coupling agent;

(B) a polymerizable monomer having an acid group;

(C) a polymerizable monomer having no acidic group; and

(D) at least one of (E) a polymerization initiator and (E) a polymerization accelerator,

the (A) silane coupling agent comprises (A1) a silane coupling agent represented by structural formula (a),

in the formula (a), R³Is represented by having C₂～C₁₅Of an alkyl group of (meth) acryloyl group, C₂～C₁₅With or without-O, -S, -NH, -c (O) -O, -O-c (O) -NH-and/or-NH-c (O) -O-groups; r¹And R²Is represented by C₁～C₄The alkyl groups of (a) are the same or different from each other; n is 1 to 3, and,

the (C) polymerizable monomer having no acid group includes (C1) polymerizable monomer having no acid group and having one or more hydroxyl groups,

the (A1) silane coupling agent represented by structural formula (a) coexists with the (C1) polymerizable monomer having no acidic group but one or more hydroxyl groups in at least one matrix,

the dental adhesive composition satisfies at least one of the following formulas (1) and (2),

formula (1): 0.005-0.070 in total of the indexes of the amount of silane coupling agent blended in the matrix ((S1 XW 1)/M1)

In the formula (1), M1 is the molecular weight of each silane coupling agent contained in the matrix, S1 is the number of alkoxysilyl groups in the molecule of each silane coupling agent contained in the matrix, and W1 is the compounding amount of each silane coupling agent in 100 parts by mass of the matrix; the index of the amount of the silane coupling agent incorporated in the matrix is calculated from the formula (1) for each silane coupling agent,

formula (2): the total of the silane coupling agent content indices ((S2 XW 2)/M2) in the composition is not less than 0.001 and not more than 0.015

In formula (2), M2 is the molecular weight of each silane coupling agent contained in the composition, S2 is the number of alkoxysilyl groups in the molecule of each silane coupling agent contained in the composition, and W2 is the compounding amount of each silane coupling agent in 100 parts by mass of the composition; the index of the amount of the silane coupling agent incorporated in the composition was calculated from the formula (2) for each silane coupling agent.

2. The dental adhesive composition according to claim 1, wherein,

the total index of the amount of silane coupling agent incorporated in the matrix is 0.010 to 0.055.

3. The dental adhesive composition according to claim 1 or 2, wherein,

the dental adhesive composition is composed of a first paste and a second paste,

the first paste comprising a first matrix and (F) a filler,

the first substrate contains (A) a silane coupling agent containing (A1) a silane coupling agent represented by the structural formula (a) and (C) a polymerizable monomer having no acidic group,

the second paste comprising a second matrix and (F) a filler,

the second substrate contains (B) a polymerizable monomer having an acid group and (C) a polymerizable monomer having no acid group,

the first matrix comprises at least one of (D1) a chemical polymerization initiator and (E) a polymerization accelerator,

the second matrix comprises at least one of (D1) a chemical polymerization initiator and (E) a polymerization accelerator,

in the case where one or more (D1) chemical polymerization initiators are contained in the first matrix, one or more (E) polymerization accelerators are contained in the second matrix,

in the case where one or more (E) polymerization accelerators are contained in the first matrix, one or more (D1) chemical polymerization initiators are contained in the second matrix.

4. The dental adhesive composition according to claim 3, wherein,

which contains substantially no (G) water.

5. The dental adhesive composition according to any one of claims 1 to 4,

the ratio of a compound having a methacryloyl group and/or a methacrylamido group is 50 to 99.9 parts by mass based on 100 parts by mass of the total of (A) a silane coupling agent, (B) a polymerizable monomer having an acid group and (C) a polymerizable monomer having no acid group, and the silane coupling agent (A) contains (A1) a silane coupling agent represented by the structural formula (a).

6. The dental adhesive composition according to claim 1 or 2, wherein,

which comprises the following steps:

a base containing (a) a silane coupling agent, (B) a polymerizable monomer having an acid group, (C) a polymerizable monomer having no acid group, and (D) a polymerization initiator, and the (a) silane coupling agent containing (a1) a silane coupling agent represented by the structural formula (a); and

(F) and (4) filling.

7. The dental adhesive composition according to claim 6, wherein,

the filler (F) is surface-treated with at least one surface-treating agent selected from silane coupling agents, surfactants, organopolysiloxanes, inorganic oxides, and polymeric compounds.

8. The dental adhesive composition according to claim 1 or 2, wherein,

the dental adhesive composition comprises a base and (F) a filler,

the dental adhesive composition comprises 25 to 75 parts by mass of a base per 100 parts by mass of the dental adhesive composition,

the dental adhesive composition contains 25 to 75 parts by mass of (F) a filler per 100 parts by mass of the dental adhesive composition,

regarding each of the silane coupling agents (A1) represented by the structural formula (a), the total index of the amount of the silane coupling agent incorporated in the base body calculated from the formula (3) satisfies the formula (3),

formula (3): 0.005-0.005 in total of (A1) the index of the amount of the silane coupling agent blended in the matrix ((S3 XW 3)/M3) -0.070

In the formula (3), M3 is the molecular weight of each (A1) silane coupling agent represented by the structural formula (a) contained in the matrix, S3 is the number of alkoxysilyl groups in the molecule of each (A1) silane coupling agent represented by the structural formula (a) contained in the matrix, W3 is the compounding amount of each (A1) silane coupling agent represented by the structural formula (a) in 100 parts by mass of the matrix,

the dental adhesive composition contains 1 to 20 parts by mass of (B) a polymerizable monomer having an acid group per 100 parts by mass of the substrate,

the dental adhesive composition contains 65 to 95 parts by mass of (C) a polymerizable monomer having no acidic group per 100 parts by mass of the base,

the dental adhesive composition contains 0.3 to 6 parts by mass of (D) a polymerization initiator per 100 parts by mass of the substrate,

the dental adhesive composition contains 0.1 to 70 parts by mass of a polymerizable monomer (C1) having no acidic group but having one or more hydroxyl groups per 100 parts by mass of the substrate,

the polymerizable monomer contained in the matrix contains a polymerizable monomer having a methacryloyl group and/or a methacrylamido group, and the amount of the compound having a methacryloyl group and/or a methacrylamido group is 50 to 99 parts by mass per 100 parts by mass of the matrix.

9. The dental adhesive composition according to any one of claims 1 to 8,

the (a1) silane coupling agent represented by the structural formula (a) is a silane coupling agent having an acryloyl group, and the dental adhesive composition satisfies at least formula (1).

10. The dental adhesive composition according to claim 3, wherein,

the dental adhesive composition is used for a dental cutting repair material,

the dental adhesive composition contains 15-80 parts by mass of (C1) a polymerizable monomer having no acidic group and at least one hydroxyl group, based on 100 parts by mass of the total of the first substrate and the second substrate.

11. The dental adhesive composition according to claim 10, wherein,

the dental adhesive composition is used for a dental cutting repair material,

15 to 80 parts by mass of a polymerizable monomer (C1) having no acidic group and having one or more hydroxyl groups, the polymerizable monomer being contained in the first matrix, based on 100 parts by mass of the first matrix,

15 to 80 parts by mass of a polymerizable monomer having one or more hydroxyl groups and not having an acid group (C1) contained in the second matrix per 100 parts by mass of the second matrix, and

the dental adhesive composition satisfies at least formula (1).

12. The dental adhesive composition according to claim 10 or 11, wherein,

the first matrix contains (C11) a polymerizable monomer having no acidic group but one or more hydroxyl groups and having a viscosity of 200 mPas or less at 25 ℃,

the amount of the polymerizable monomer (C11) having no acidic group but one or more hydroxyl groups and having a viscosity of 200 mPas or less at 25 ℃ is 0.1 to 40 parts by mass per 100 parts by mass of the first substrate.

13. The dental adhesive composition according to any one of claims 10 to 12, wherein,

the filler (F) to be blended in the first paste is surface-treated with at least one surface-treating agent selected from an organopolysiloxane, a silane coupling agent, an inorganic oxide, a surfactant, and a polymer compound.

14. The dental adhesive composition according to claim 12, wherein,

the volume ratio of the first paste to the second paste is 1: 0.8 to 1.2 parts by weight,

the first base of the first paste is 25 to 75 parts by mass per 100 parts by mass of the first paste,

the filler (F) of the first paste is 25 to 75 parts by mass per 100 parts by mass of the first paste,

regarding each of the silane coupling agents (A1) represented by the structural formula (a), the total index of the amount of the silane coupling agent incorporated in the base body calculated from the formula (3) satisfies the formula (3),

formula (3): 0.005-0.005 in total of (A1) the index of the amount of the silane coupling agent blended in the matrix ((S3 XW 3)/M3) -0.070

In the formula (3), M3 is the molecular weight of each (A1) silane coupling agent represented by the structural formula (a) contained in the matrix, S3 is the number of alkoxysilyl groups in the molecule of each (A1) silane coupling agent represented by the structural formula (a) contained in the matrix, W3 is the compounding amount of each (A1) silane coupling agent represented by the structural formula (a) in 100 parts by mass of the matrix,

the amount of the polymerizable monomer (C) having no acidic group in the first substrate is 65 to 98 parts by mass per 100 parts by mass of the first substrate,

the second base of the second paste is 25 to 75 parts by mass per 100 parts by mass of the second paste,

the filler (F) of the second paste is 25 to 75 parts by mass per 100 parts by mass of the second paste,

the amount of the polymerizable monomer (B) having an acid group in the second substrate is 1 to 30 parts by mass per 100 parts by mass of the second substrate,

the second substrate contains 65 to 95 parts by mass of (C) a polymerizable monomer having no acid group per 100 parts by mass of the second substrate,

the amount of the polymerization initiator (D) is 0.1 to 5 parts by mass based on 100 parts by mass of the total of the first substrate and the second substrate,

the amount of the polymerization accelerator (E) is 0.01 to 5 parts by mass based on 100 parts by mass of the total of the first substrate and the second substrate,

15 to 80 parts by mass of a polymerizable monomer (C1) having no acidic group and having at least one hydroxyl group per 100 parts by mass of the total of the first substrate and the second substrate,

the amount of the polymerizable monomer (C11) having no acidic group but one or more hydroxyl groups and having a viscosity of 200 mPas or less at 25 ℃ is 0.1 to 50 parts by mass per 100 parts by mass of the first substrate.

15. The dental adhesive composition according to claim 1, wherein,

the dental adhesive composition further contains (G) water and (H) a volatile organic solvent, and the dental adhesive composition satisfies at least formula (2).

16. The dental adhesive composition according to claim 15, wherein,

the amount of the polymerizable monomer having no acidic group (C1) is 20 to 70 parts by mass per 100 parts by mass of the total of the silane coupling agent (A), the polymerizable monomer having an acidic group (B), and the polymerizable monomer having no acidic group (C), and the silane coupling agent (A) contains a silane coupling agent represented by the structural formula (a) (A1).

17. The dental adhesive composition according to claim 15 or 16,

(A1) the silane coupling agent represented by structural formula (a) is a silane coupling agent having an acryloyl group.

18. The dental adhesive composition according to any one of claims 15 to 17,

the total of the indexes of the amount of silane coupling agents blended in the composition is 0.002 to 0.008.

19. The dental adhesive composition according to any one of claims 15 to 18,

further comprising (I) a polymerizable monomer having one or more sulfur atoms.

20. The dental adhesive composition according to any one of claims 15 to 19,

the total index of the amount of silane coupling agent blended in the composition calculated from the formula (4) satisfies the formula (4) for each of the silane coupling agents (A1) represented by the structural formula (a),

formula (4): 0.001. ltoreq. the total amount of (A1) the index of the amount of silane coupling agent blended in the composition ((S4 XW 4)/M4) is 0.015. ltoreq.

In formula (4), M4 is the molecular weight of each (A1) silane coupling agent represented by structural formula (a) contained in the composition, S4 is the number of alkoxysilyl groups in the molecule of each (A1) silane coupling agent represented by structural formula (a) contained in the composition, W4 is the compounding amount of each (A1) silane coupling agent represented by structural formula (a) in 100 parts by mass of the composition,

the adhesive composition for dental use contains 1 to 40 parts by mass of (B) a polymerizable monomer having an acid group per 100 parts by mass of the adhesive composition,

5 to 60 parts by mass of (C) a polymerizable monomer having no acidic group contained in 100 parts by mass of the dental adhesive composition,

the dental adhesive composition contains 0.01-5 parts by mass of (D) a polymerization initiator per 100 parts by mass of the dental adhesive composition and/or 0.01-5 parts by mass of (E) a polymerization accelerator per 100 parts by mass of the dental adhesive composition,

5 to 90 parts by mass of (H) a volatile organic solvent contained in 100 parts by mass of the dental adhesive composition,

the dental adhesive composition contains 1 to 50 parts by mass of (G) water per 100 parts by mass of the dental adhesive composition,

40 to 100 parts by mass of a polymerizable monomer having two or more polymerizable groups and having no acid group per 100 parts by mass of the polymerizable monomer having no acid group (C) contained in the dental adhesive composition,

the adhesive composition for dental use contains (A1) a silane coupling agent represented by the structural formula (a) and 20-70 parts by mass of (C1) a polymerizable monomer having no acidic group but having one or more hydroxyl groups, the polymerizable monomer having no acidic group being contained in the polymerizable monomer having no acidic group, based on 100 parts by mass of the total of (A) the silane coupling agent, (B) the polymerizable monomer having an acidic group, and (C) the polymerizable monomer having no acidic group,

the adhesive composition for dental use contains (A1) a silane coupling agent represented by the structural formula (a) and (B) a polymerizable monomer having an acidic group and (C) a polymerizable monomer having no acidic group, wherein the amount of a compound having a methacryloyl group and/or a methacrylamido group is 60 to 100 parts by mass based on 100 parts by mass of the total of the silane coupling agent (A), the polymerizable monomer (B) and the polymerizable monomer (C).

21. A self-adhesive composite resin for dental use, wherein,

comprising the dental adhesive composition according to any one of claims 1 to 20.

22. Use of the dental adhesive composition according to any one of claims 15 to 20 for adhesion to a dental cutting resin.

23. Use of the dental adhesive composition according to any one of claims 15 to 20 for bonding to a dental cutting resin comprising a glass fiber-reinforced material containing glass fibers and an epoxy resin.

24. Use of the dental adhesive composition according to any one of claims 10 to 15 for adhesion to a dental cutting repair material,

the dental cutting repair material is either a glass fiber-reinforced material containing glass fibers and epoxy resin, in which the glass fibers are randomly mixed in a non-uniform orientation direction, or a laminate material containing glass fibers and epoxy resin, in which the glass fibers are cross-woven, the laminate material having a cross-woven surface and a glass fiber laminated surface on a surface in which the woven surface is rotated to a 90 ° perpendicular direction.

25. Use of the dental adhesive composition according to any one of claims 10 to 15 for adhesion to a dental cutting repair material,

the dental cutting repair material is adhered to the surfaces to be adhered having two or more different structures.

Technical Field

The present invention relates to an adhesive composition for dental use.

Background

In the dental field, the dental adhesive composition is widely used as a dental adhesive material, a dental resin cement, a dental base building material, a dental adhesive, a dental primer, a metal primer, a ceramic primer, a composite resin, a dental pretreatment material, and the like.

In dental treatment, adherends to be bonded include dentine, precious metal alloys, non-precious metal alloys, oxide ceramics, glass ceramics, composite resins containing inorganic fillers, and the like, and therefore, a special dental adhesive composition suitable for various adherends is generally used. For example, when the adherend is dentin (dentin, enamel), a dental adhesive composition containing a polymerizable monomer having an acidic group is used. In the case of a noble metal alloy whose treated surface is mainly composed of gold, platinum, palladium, silver, or the like, a dental adhesive composition containing a polymerizable monomer containing a sulfur atom is used. In the case where the adherend is a non-noble metal alloy such as iron, nickel, chromium, cobalt, tin, aluminum, copper, titanium, or the like, or in the case of an oxide-based ceramic such as zirconia, alumina, or the like, a dental adhesive composition containing a polymerizable monomer having an acidic group is used. When the adherend is a glass ceramic or a composite resin containing an inorganic filler, a dental adhesive composition containing a silane coupling agent is used. The silane coupling agent has an alkoxysilyl group (-Si-OR group) in the molecular structure, and it is considered that the alkoxysilyl group reacts with/bonds to the glass ceramic surface OR the inorganic filler by mixing with an acidic OR alkaline aqueous solution OR heating to express adhesiveness.

In addition, in recent years, due to remarkable progress of a CAD/CAM system controlled by a computer, various dental cutting restorative materials produced by cutting using the system have been also clinically used in the dental field. In the cutting process using this system, a dental cutting restorative material for producing a block such as an inlay and a crown or for producing a disk such as a bridge is used as the dental cutting restorative material. Dental adhesive compositions are also used for bonding these dental cutting restorative materials.

As an adhesive composition for dental use, patent document 1 proposes a two-paste type adhesive composition for dental use containing an acidic group-containing polymerizable monomer and a silane coupling agent. In the invention described in patent document 1, both adhesiveness to various adherends and storage stability are successfully achieved by mixing a polymerizable monomer having an acidic group and a silane coupling agent having an alkoxysilyl group with a carbon chain length of 2 to 5 in different pastes and mixing the silane coupling agent and an alkaline filler in the same paste. Patent document 2 describes a dental adhesive composition that can exhibit adhesiveness to dentin in addition to precious metal alloys, non-precious metal alloys, oxide ceramics, glass ceramics, and composite resins. However, the durable adhesive strength and the coloring resistance to glass ceramics and dentin containing lithium disilicate are not sufficient.

Further, as a method for achieving durable adhesion to lithium disilicate glass, there has been proposed a composition using a silane coupling agent having a carbon chain length of 6 or more between a silicon atom and a polymerizable group (patent document 3), or a composition using a crosslinking agent and a silanol condensation catalyst in combination in addition to the silane coupling agent (patent document 4). However, the durable adhesive strength to glass ceramics or dentin containing lithium disilicate is insufficient. Further, there is a problem in terms of coloring resistance and stability of properties after long-term storage.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2016 and 124811.

Patent document 2: japanese patent laid-open publication No. 2018-177677.

Patent document 3: international publication No. WO 2019/00439.

Patent document 4: japanese patent laid-open publication No. 2019-94276.

Disclosure of Invention

The present invention aims to provide an adhesive composition for dental use which has excellent storage stability while achieving excellent durable adhesive strength to various dental cutting restorative materials such as a glass ceramic containing lithium disilicate and a dental cutting resin, particularly a dental cutting resin composed of a glass fiber-reinforced resin, and to dentin.

The present invention provides an adhesive composition for dental use, comprising a base containing: (A) a silane coupling agent, (B) a polymerizable monomer having an acidic group, (C) a polymerizable monomer having no acidic group, and at least one of (D) a polymerization initiator and (E) a polymerization accelerator.

The (A) silane coupling agent includes (A1) a silane coupling agent represented by structural formula (a).

(in the formula, R³Is represented by having C₂～C₁₅Of an alkyl group of (meth) acryloyl group, C₂～C₁₅With or without-O, -S, -NH, -C (O) -O, -O-C (O), O-C (O) -NH-and/or-NH-C (O) -O-groups, R¹And R²Is represented by C₁～C₄Are the same or different from each other. N is 1 to 3. )

The (C) polymerizable monomer having no acid group includes (C1) polymerizable monomer having no acid group and having one or more hydroxyl groups.

The silane coupling agent (A) and the polymerizable monomer (C1) having no acidic group but having one or more hydroxyl groups coexist in at least one matrix.

The dental adhesive composition satisfies at least one of the following formulas (1) and (2).

Formula (1): 0.005-0.070 in total of the indexes of the amount of silane coupling agent blended in the matrix ((S1 XW 1)/M1)

(in the formula (1), M1 represents the molecular weight of each silane coupling agent contained in the matrix, S1 represents the number of alkoxysilyl groups in the molecule of each silane coupling agent contained in the matrix, W1 represents the amount of each silane coupling agent mixed in 100 parts by mass of the matrix; index of the amount of each silane coupling agent mixed in the matrix is calculated from the formula (1) for each silane coupling agent.)

Formula (2): the total of the silane coupling agent content indices ((S2 XW 2)/M2) in the composition is not less than 0.001 and not more than 0.015

(in the formula (2), M2 represents the molecular weight of each silane coupling agent contained in the composition, S2 represents the number of alkoxysilyl groups in the molecule of each silane coupling agent contained in the composition, and W2 represents the amount of each silane coupling agent to be added in 100 parts by mass of the composition.) the index of the amount of each silane coupling agent to be added in the composition is calculated from the formula (2) for each silane coupling agent.)

In the present invention, the total of the indexes of the amount of the silane coupling agent blended in the matrix may be 0.010 to 0.055.

In the present invention, the dental adhesive composition may be composed of a first paste and a second paste, the first paste including a first base and (F) a filler, the first base including (a) a silane coupling agent containing (a1) a silane coupling agent represented by the structural formula (a) and (C) a polymerizable monomer having no acidic group, the second paste including a second base and (F) a filler, the second base including (B) a polymerizable monomer having an acidic group and (C) a polymerizable monomer having no acidic group, the first base including at least one of (D1) a chemical polymerization initiator and (E) a polymerization accelerator, the second base including at least one of (D1) a chemical polymerization initiator and (E) a polymerization accelerator, the second base including one or more of (E) polymerization accelerators in the case where one or more of (D1) chemical polymerization initiators are included in the first base, in the case where one or more (E) polymerization accelerators are contained in the first matrix, one or more (D1) chemical polymerization initiators are contained in the second matrix.

In the present invention, (G) water may be substantially excluded.

In the present invention, the proportion of the compound having a methacryloyl group and/or a methacrylamido group can be 50 to 100 parts by mass in 100 parts by mass of the total of (a) the silane coupling agent containing (a1) the silane coupling agent represented by the structural formula (a), (B) the polymerizable monomer having an acidic group, and (C) the polymerizable monomer having no acidic group.

In the present invention, the filler may include a matrix containing (a) a silane coupling agent containing (a1) a silane coupling agent represented by the structural formula (a), (B) a polymerizable monomer having an acid group, (C) a polymerizable monomer having no acid group, and (D) a polymerization initiator, and (F) a filler.

In the present invention, the filler (F) can be surface-treated with at least one surface-treating agent selected from silane coupling agents, surfactants, organopolysiloxanes, inorganic oxides, and polymeric compounds.

In the present invention, the dental adhesive composition may contain a base and (F) a filler, the base contained in the dental adhesive composition is 25 to 75 parts by mass per 100 parts by mass of the dental adhesive composition, the filler (F) contained in the dental adhesive composition is 25 to 75 parts by mass per 100 parts by mass of the dental adhesive composition, and the total of the indices of the amounts of silane coupling agents blended in the base calculated from formula (3) satisfies formula (3) for each of the silane coupling agents (a1) represented by structural formula (a).

Formula (3): 0.005-0.005 in total of (A1) the index of the amount of the silane coupling agent blended in the matrix ((S3 XW 3)/M3) -0.070

(in the formula (3), M3 represents the molecular weight of each (A1) of the silane coupling agent represented by the formula (a) contained in the matrix, S3 represents the number of alkoxysilyl groups in each (A1) of the silane coupling agent represented by the formula (a) contained in the matrix, and W3 represents the amount of each (A1) of the silane coupling agent represented by the formula (a) contained in 100 parts by mass of the matrix.)

The polymerizable monomer (B) having an acid group contained in the dental adhesive composition is 1 to 20 parts by mass per 100 parts by mass of the substrate.

The dental adhesive composition contains 65 to 95 parts by mass of the polymerizable monomer (C) having no acidic group per 100 parts by mass of the substrate.

The dental adhesive composition contains 0.3 to 6 parts by mass of (D) a polymerization initiator per 100 parts by mass of the substrate.

The polymerizable monomer (C1) having no acidic group but having one or more hydroxyl groups contained in the dental adhesive composition is 0.1 to 70 parts by mass per 100 parts by mass of the substrate.

The polymerizable monomer contained in the matrix contains a polymerizable monomer having a methacryloyl group and/or a methacrylamido group, and the amount of the compound having a methacryloyl group and/or a methacrylamido group is 50 to 99 parts by mass per 100 parts by mass of the matrix.

In the present invention, (a1) the silane coupling agent represented by the structural formula (a) may be a silane coupling agent having an acryloyl group, and the dental adhesive composition may satisfy at least formula (1).

In the present invention, the dental adhesive composition can be used for a dental cutting repair material, and the dental adhesive composition contains 15 to 80 parts by mass of (C1) a polymerizable monomer having no acidic group but having one or more hydroxyl groups, based on 100 parts by mass of the total of the first substrate and the second substrate.

In the present invention, an adhesive composition for dental use which can be used for a dental cutting/repairing material, wherein the amount of (C1) the polymerizable monomer having no acidic group but one or more hydroxyl groups contained in the first substrate is 15 to 80 parts by mass per 100 parts by mass of the first substrate, and the amount of (C1) the polymerizable monomer having no acidic group but one or more hydroxyl groups contained in the second substrate is 15 to 80 parts by mass per 100 parts by mass of the second substrate, and the adhesive composition for dental use satisfies at least formula (1).

In the present invention, the first substrate may contain (C11) a polymerizable monomer having no acidic group but one or more hydroxyl groups and having a viscosity at 25 ℃ of 200mPa · s or less, and the amount of the polymerizable monomer having no acidic group but one or more hydroxyl groups and having a viscosity at 25 ℃ of 200mPa · s or less is 0.1 to 40 parts by mass based on 100 parts by mass of the first substrate (C11).

In the present invention, the filler (F) to be blended in the first paste may be surface-treated with at least one surface-treating agent selected from an organopolysiloxane, a silane coupling agent, an inorganic oxide, a surfactant, and a polymer compound.

In the present invention, the first paste and the second paste may be mixed in a volume ratio of 1: 0.8 to 1.2; 25 to 75 parts by mass of the first base of the first paste per 100 parts by mass of the first paste; the filler (F) in the first paste is 25 to 75 parts by mass per 100 parts by mass of the first paste, and the total index of the amount of the silane coupling agent in the matrix calculated from the formula (3) for each of the silane coupling agents (A1) represented by the structural formula (a) satisfies the formula (3).

Formula (3): 0.005-0.005 in total of (A1) the index of the amount of the silane coupling agent blended in the matrix ((S3 XW 3)/M3) -0.070

(in the formula (3), M3 represents the molecular weight of each (A1) of the silane coupling agent represented by the formula (a) contained in the matrix, S3 represents the number of alkoxysilyl groups in each (A1) of the silane coupling agent represented by the formula (a) contained in the matrix, and W3 represents the amount of each (A1) of the silane coupling agent represented by the formula (a) contained in 100 parts by mass of the matrix.)

The amount of the polymerizable monomer (C) having no acidic group in the first substrate is 65 to 98 parts by mass per 100 parts by mass of the first substrate.

The second base of the second paste is 25 to 75 parts by mass per 100 parts by mass of the second paste.

The filler (F) in the second paste is 25 to 75 parts by mass per 100 parts by mass of the second paste.

The amount of the polymerizable monomer (B) having an acid group in the second substrate is 1 to 30 parts by mass per 100 parts by mass of the second substrate.

The amount of the polymerizable monomer (C) having no acidic group in the second substrate is 65 to 95 parts by mass per 100 parts by mass of the second substrate.

The amount of the polymerization initiator (D) is 0.1 to 5 parts by mass per 100 parts by mass of the total of the first substrate and the second substrate.

The amount of the polymerization accelerator (E) is 0.01 to 5 parts by mass per 100 parts by mass of the total of the first substrate and the second substrate.

15 to 80 parts by mass of a polymerizable monomer (C1) having no acidic group and having one or more hydroxyl groups, based on 100 parts by mass of the total of the first substrate and the second substrate.

0.1 to 50 parts by mass of a polymerizable monomer (C11) having no acidic group but one or more hydroxyl groups and having a viscosity of 200 mPas or less at 25 ℃ contained in 100 parts by mass of the first substrate.

In the present invention, (G) water and (H) a volatile organic solvent are further contained, and the dental adhesive composition can satisfy at least formula (2).

In the present invention, the amount of the (C1) polymerizable monomer having no acidic group and having one or more hydroxyl groups can be 20 to 70 parts by mass relative to 100 parts by mass of the total of the (a) silane coupling agent containing the (a1) silane coupling agent represented by the structural formula (a), (B) polymerizable monomer having an acidic group, and (C) polymerizable monomer having no acidic group.

In the present invention, (a1) the silane coupling agent represented by structural formula (a) can be a silane coupling agent having an acryloyl group.

In the present invention, the total of the indexes of the amount of the silane coupling agent blended in the composition may be 0.002 to 0.008.

In the present invention, the polymerizable monomer (I) having one or more sulfur atoms can be further contained.

In the present invention, the total index of the amount of silane coupling agent blended in the composition calculated from formula (4) for each of the silane coupling agents represented by structural formula (a1) can satisfy formula (4).

Formula (4): 0.001. ltoreq. the total amount of (A1) the index of the amount of silane coupling agent blended in the composition ((S4 XW 4)/M4) is 0.015. ltoreq.

(in the formula (4), M4 is the molecular weight of each (A1) of the silane coupling agent represented by the structural formula (a) contained in the composition, S4 is the number of alkoxysilyl groups in each (A1) of the silane coupling agent represented by the structural formula (a) contained in the composition, and W4 is the blending amount of each (A1) of the silane coupling agent represented by the structural formula (a) in 100 parts by mass of the composition.)

The adhesive composition for dental use contains 1 to 40 parts by mass of (B) a polymerizable monomer having an acid group per 100 parts by mass of the adhesive composition.

The dental adhesive composition contains 5-60 parts by mass of (C) polymerizable monomer having no acidic group per 100 parts by mass of the dental adhesive composition.

The dental adhesive composition contains 0.01-5 parts by mass of (D) a polymerization initiator per 100 parts by mass of the dental adhesive composition and/or contains 0.01-5 parts by mass of (E) a polymerization accelerator per 100 parts by mass of the dental adhesive composition.

The dental adhesive composition contains 5-90 parts by mass of (H) a volatile organic solvent per 100 parts by mass of the dental adhesive composition.

The dental adhesive composition contains 1 to 50 parts by mass of (G) water per 100 parts by mass of the dental adhesive composition.

The dental adhesive composition contains 40 to 100 parts by mass of a polymerizable monomer having two or more polymerizable groups and no acidic group per 100 parts by mass of a polymerizable monomer having no acidic group (C).

20 to 70 parts by mass of a polymerizable monomer (C1) having no acidic group but having one or more hydroxyl groups, which is contained in the polymerizable monomer (C) having no acidic group, based on 100 parts by mass of the total of the silane coupling agent (A) containing (A1) a silane coupling agent represented by the structural formula (a), the polymerizable monomer (B) having an acidic group, and the polymerizable monomer (C) having no acidic group, which are contained in the dental adhesive composition.

The adhesive composition for dental use contains a silane coupling agent (A1) represented by the structural formula (a) and a compound having a methacryloyl group and/or a methacrylamide group in an amount of 60 to 100 parts by mass in total 100 parts by mass of a polymerizable monomer (B) having an acidic group and a polymerizable monomer (C) having no acidic group.

The present invention provides a dental self-adhesive composite resin, which comprises the dental adhesive composition of the present invention.

The present invention provides the use of the dental adhesive composition of the present invention for adhesion to a dental cutting resin composed of a glass fiber-reinforced material containing glass fibers and an epoxy resin.

The present invention provides the use of the dental adhesive composition of the present invention for adhesion to a dental cutting resin.

The present invention provides the use of the dental adhesive composition of the present invention for bonding to a dental cutting restorative material, wherein the dental cutting restorative material is any of a glass fiber reinforced material containing glass fibers and epoxy resin and randomly blended with the glass fibers in such a way that the orientation directions of the glass fibers are not uniform, and a laminate material containing glass fibers and epoxy resin and cross-woven with glass fibers, the laminate material having a cross-woven surface and a surface having a glass fiber laminated surface on a surface in which the woven surface is rotated to a direction perpendicular to 90 °.

The present invention provides the use of the dental adhesive composition of the present invention for bonding to a dental cutting repair material, wherein the dental cutting repair material has two or more different structures on the surfaces to be bonded.

The present invention can provide an adhesive composition for dental use which has excellent storage stability while achieving excellent durable adhesive strength to various dental cutting restorative materials such as a glass ceramic containing lithium disilicate and a dental cutting resin, particularly a dental cutting resin composed of a glass fiber-reinforced resin, and to dentin.

Detailed Description

The dental adhesive composition of the present invention is a material that can be used for restoring the anatomical morphology of a carious portion or a missing tooth. The dental adhesive composition is cured by polymerization reaction, and properties suitable for the intended use, that is, mechanical strength against occlusion pressure, adhesive strength, color tone similar to dentin, and the like can be obtained. Polymerization reactions of dental adhesive compositions are roughly classified into photopolymerization in which polymerization is initiated by irradiation with light and chemical polymerization in which polymerization is initiated by using a chemical polymerization initiator and a chemical polymerization accelerator. Photopolymerization can be carried out at any time by the surgeon by irradiation with light, but the portion that cannot be reached by light cannot be polymerized at all. On the other hand, in chemical polymerization, the curing time depends on the kind, the amount and the like of a chemical polymerization initiator and a chemical polymerization accelerator, but since it is also possible to polymerize a portion which cannot be reached by light, it is used in many dental materials. In addition, regardless of the use, the dental material is required to have high storage stability in which no decrease in curability or change in properties is observed, high color tone stability in which color tone does not change after application in the oral cavity, and resistance to staining.

In dental treatment, adherends to be bonded include dentine, precious metal alloys, non-precious metal alloys, oxide ceramics, glass ceramics, composite resins (containing inorganic fillers), and the like, and therefore, usually, after coating a special primer or an adhesive material suitable for various adherends, filling and bonding are performed using a dental adhesive composition. In recent years, among ceramics, glass ceramics containing lithium disilicate have excellent long-term stability and mechanical strength, but materials that are difficult to bond have become widespread, and therefore materials that exhibit high durable bonding strength have been demanded.

In addition, in clinical practice, primers and adhesives are used separately according to the type of adherend, and the operation is complicated, and therefore there is a risk of causing technical errors. In addition, filling or bonding using the dental adhesive composition after applying a primer or an adhesive is not clinically preferable because the number of steps is large. Thus, there is a need for an adhesive composition for dental use which can be filled and bonded without applying a primer or an adhesive material regardless of the type of an adherend by blending an acidic group-containing polymerizable monomer and a silane coupling agent into the adhesive composition for dental use.

The dental adhesive composition of the present invention can be used as a dental adhesive composition for bonding various dental cutting restorative materials produced by cutting using a computer-controlled CAD/CAM system. Examples of the dental cutting repair material include a dental cutting resin produced using a resin material such as an acrylic resin or an epoxy resin, and a composite resin material containing inorganic particles or inorganic fibers for reinforcing the resin material. These resin materials are materials that are firmly cured using a polymerizable catalyst or a polymerization initiator and are difficult to bond.

In particular, in recent years, composite resin materials in which inorganic particles are mixed with resin materials for cutting have been attracting attention. This is a material which is difficult to bond because it is filled with a filler such as an inorganic filler or an organic composite filler at a high density and is polymerized and cured by heating under pressure, and a material which exhibits stable bonding strength is required.

In addition, since high bending strength and toughness are required in the case of providing a dental bridge, particularly a bone anchored bridge, as an implant superstructure, a glass fiber reinforced material composed of epoxy glass is used. Epoxy glass is obtained by impregnating glass fibers with an epoxy resin and then curing the resin, and has been widely used as a frame material because it can achieve higher physical properties and toughness than a composite resin material composed of a matrix containing an inorganic filler and a polymerizable monomer having a (meth) acryloyl group or a (meth) acrylamide group.

In addition to the difficulty in stable adhesion due to the stable solidification of the glass fiber reinforcement, the orientation direction of the glass fibers on the surface to be adhered is not uniform, and therefore, the state of the surface to be adhered is less likely to be uniform than in the case of blending the inorganic powder. On the other hand, in the case of weaving glass fibers, since the woven surface and the surface on which the glass fibers are laminated are present in a mixed manner, a uniform surface to be adhered is not obtained, and a material which exhibits stable adhesion strength even when either of the epoxy resin and the glass fibers is present on the surface to be adhered is required.

The dental adhesive composition of the present invention may be, for example, a composition comprising a matrix containing (a) a silane coupling agent represented by the structural formula (a) (a1), (B) a polymerizable monomer having an acid group, (C) a polymerizable monomer having no acid group, and (D) a polymerization initiator, wherein (a1) the silane coupling agent represented by the structural formula (a) has an acryloyl group.

The dental adhesive composition of the present invention is composed of, for example, a first paste containing at least a first base containing at least (a) a silane coupling agent containing (a1) a silane coupling agent represented by the structural formula (a) and (C) a polymerizable monomer having no acidic group and (F) a filler and a second paste containing at least a second base containing at least (B) a polymerizable monomer having an acidic group and (C) a polymerizable monomer having no acidic group and (F) a filler and (D1) at least one of a chemical polymerization initiator and (E) a polymerization accelerator, and a second base containing at least one of (D1) a chemical polymerization initiator and (E) a polymerization accelerator, and in the case where one or more (D1) chemical polymerization initiators are contained in the first base, one or more (E) polymerization accelerators are contained in the second base, when the first matrix contains one or more polymerization accelerators (E), the second matrix contains one or more chemical polymerization initiators (D1), and 15 to 80 parts by mass (C1) of a polymerizable monomer having no acidic group but one or more hydroxyl groups can be contained per 100 parts by mass of the first matrix and the second matrix.

The dental adhesive composition of the present invention can contain, for example, (a) a silane coupling agent containing (a1) a silane coupling agent represented by the structural formula (a), (B) a polymerizable monomer having an acid group, (C) a polymerizable monomer having no acid group, (H) a volatile organic solvent, and (G) water, and further contain either or both of (D) a polymerization initiator and (E) a polymerization accelerator.

The components of the dental adhesive composition of the present invention will be described in detail below.

The silane coupling agent and the polymerizable monomer contained in the composition described in the present invention preferably contain a polymerizable group that exhibits radical polymerizability, and specifically, from the viewpoint of easy radical polymerization, the polymerizable group preferably contains a (meth) acrylic group and/or a (meth) acrylamide group. In the present specification, "(meth) acrylic acid" means acrylic acid and/or methacrylic acid, "(meth) acryloyl group" means acryloyl group and/or methacryloyl group, and "(meth) acrylate" means acrylate and/or methacrylate.

The base included in the dental adhesive composition of the present invention contains (a1) a silane coupling agent represented by the structural formula (a).

In the present invention, (a1) the silane coupling agent represented by the structural formula (a) and (C1) the polymerizable monomer having no acidic group but having one or more hydroxyl groups coexist in at least one substrate.

In the present invention, (a) a silane coupling agent containing (a1) a silane coupling agent represented by the structural formula (a) is blended so as to satisfy at least one of the following formulae (1) and (2). That is, the silane coupling agent (a) containing the silane coupling agent (a) represented by the structural formula (a) of (a1) is blended so that the total index of the amount of the silane coupling agent blended in the matrix calculated from the following formula (1) satisfies the following formula (1) and/or the total index of the amount of the silane coupling agent blended in the composition calculated from the following formula (2) satisfies the following formula (2).

Formula (1): 0.005-0.070 in total of the indexes of the amount of silane coupling agent blended in the matrix ((S1 XW 1)/M1)

(in the formula (1), M1 represents the molecular weight of each silane coupling agent contained in the matrix, S1 represents the number of alkoxysilyl groups in the molecule of each silane coupling agent contained in the matrix, W1 represents the amount of each silane coupling agent mixed in 100 parts by mass of the matrix; index of the amount of each silane coupling agent mixed in the matrix is calculated from the formula (1) for each silane coupling agent.)

Formula (2): the total of the silane coupling agent content indices ((S2 XW 2)/M2) in the composition is not less than 0.001 and not more than 0.015

(in the formula (2), M2 represents the molecular weight of each silane coupling agent contained in the composition, S2 represents the number of alkoxysilyl groups in the molecule of each silane coupling agent contained in the composition, and W2 represents the amount of each silane coupling agent to be added in 100 parts by mass of the composition.) the index of the amount of each silane coupling agent to be added in the composition is calculated from the formula (2) for each silane coupling agent.)

The silane coupling agent to be added to the substrate and/or the composition is added for imparting a function of contributing to adhesion to an adherend, and particularly, it is preferable to contain a certain amount of the silane coupling agent in order to impart excellent adhesion strength to a dental cutting repair material such as a lithium disilicate-containing glass ceramic or a dental cutting resin, and on the other hand, when the amount of the silane coupling agent to be added is large, storage stability may be lowered, and the durable adhesion strength to dentin and the discoloration resistance may be lowered. The inventors have made extensive studies and found that the amount of alkoxysilyl group in the silane coupling agent to be incorporated in the matrix and/or the composition affects the adhesive strength, storage stability and coloring resistance. Thus, since the silane coupling agent contained in the matrix and/or the composition is preferably blended in consideration of the amount of the alkoxysilyl group, an index of the blending amount of the silane coupling agent has been found. In the index of the amount of silane coupling agent incorporated, the molecular weight can be calculated from the structural formula of the silane coupling agent, and the molecular weight cannot be judged from the structural formula, and the average molecular weight measured by Gel Permeation Chromatography (GPC) can be used. Next, the number of alkoxysilyl groups in the molecule of the silane coupling agent can be counted according to the structural formula of the silane coupling agent. For example, in the structural formula of the silane coupling agent represented by the structural formula (a1), (a) the number of alkoxysilyl groups is 3 in the case where n ═ 3, and 1 in the case where n ═ 1. The alkoxysilyl group represents (-Si-O-R). R represents a carbon chain, and at least oxygen atoms are bonded to Si and C. The number of alkoxysilyl groups in the silane coupling agent is counted separately from the number of-O-R groups even in the case where a plurality of-O-R groups are bonded to the same Si atom. The number of alkoxysilyl groups can not be determined from the structural formula, and the number of alkoxysilyl groups can be identified by adding an excess of an alcohol having a different carbon chain length from the alkoxysilyl groups of the silane coupling agent to the silane coupling agent and then quantitatively analyzing the mixture by gas chromatography. The molecular weight of the silane coupling agent relative to the number of alkoxysilyl groups can be derived from the molecular weight of the silane coupling agent and the number of alkoxysilyl groups, which can also be referred to as the molar mass of the silane coupling agent relative to the alkoxysilyl groups. By dividing 100 parts by mass of the base and/or the composition by this value, the amount of substance (mol) of the alkoxysilyl group contained in 100 parts by mass of the base and/or the composition can be expressed.

The dental adhesive composition of the present invention preferably satisfies both of the above formulae (1) and (2).

The dental adhesive composition of the present invention can determine the index of the amount of the silane coupling agent to be mixed based on the above formula (1) only when the dental adhesive composition does not contain an organic solvent such as (G) water or (H) a volatile organic solvent, and can determine the index of the amount of the silane coupling agent to be mixed based on the above formula (2) only when the dental adhesive composition contains an organic solvent such as (G) water or (H) a volatile organic solvent.

Specific examples thereof include 2- (meth) acryloyloxyethyltrimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltripropoxysilane, 3- (meth) acryloyloxypropylmethyldipropoxysilane, 3- (meth) acryloyloxypropyltributoxysilane, 3- (meth) acryloyloxypropylmethyldibutoxysilane, 4- (meth) acryloyloxybutyltrimethoxysilane, 5- (meth) acryloyloxypentyltrimethoxysilane, 6- (meth) acryloyloxyhexyltrimethoxysilane, 7- (meth) acryloyloxyheptyltrimethoxysilane, 8- (meth) acryloyloxyoctyltrimethoxysilane, 9- (meth) acryloyloxynonyltrimethoxysilane, 10- (meth) acryloyloxydecyltrimethoxysilane, 11- (meth) acryloyloxyundecyltrimethoxysilane.

Further, examples of the compound having a urethane group or an ether group include 3, 3-dimethoxy-8, 37-dioxo-2, 9, 36-trioxa-7, 38-diaza-3-silatetradelan-40-yl (meth) acrylate, 2- ((3, 3-dimethoxy-8-oxo-2, 9, 18-trioxa-7-aza-3-silanonacan-19-oleyl) amino) -2-methylpropane-1, 3-diylbis (meth) acrylate, 3-dimethoxy-8, 19-dioxo-2, 9, 18-trioxa-7, 20-diaza-3-siladocosan-22-yl (meth) acrylate, and the like, 3, 3-dimethoxy-8, 22-dioxo-2, 9,12,15,18, 21-hexaoxa-7, 23-diaza-3-silapentacan-25-yl (meth) acrylate, 3-dimethoxy-8, 22-dioxo-2, 9,12,15,18,21, 26-heptaoxa-7, 23-diaza-3-silaoctacosan-28-yl (meth) acrylate, 3-dimethoxy-8, 19-dioxo-2, 9,12,15, 18-pentaoxa-7, 20-diaza-3-siladocosan-22-yl (meth) acrylate, 3-dimethoxy-8, 19-dioxo-2, 9,12,15,18, 23-hexaoxa-7, 20-diaza-3-silapentacan-25-yl (meth) acrylate, 2- ((3, 3-dimethoxy-8-oxo-2, 9,12,15, 18-pentaoxa-7-aza-3-silanonacan-19-oleyl) amino) -2-methylpropan-1, 3-diylbis (meth) acrylate, 4-diethoxy-17-oxo-3, 16, 21-trioxa-18-aza-4-silatricosan-23-yl (meth) acrylate, 4-diethoxy-17-oxo-3, 16,21, 24-tetraoxa-18-aza-4-silahexacan-26-yl (meth) acrylate, 4-diethoxy-13-oxo-3, 12, 17-trioxa-14-aza-4-silanonacan-19-yl (meth) acrylate, 4-diethoxy-17-oxo-3, 16-dioxa-18-aza-4-silaeicosan-20-yl (meth) acrylate, 2-methyl-2- ((11- (triethoxysilyl) undecoxy) carbonylamino) propane-1, 3-diylbis (meth) acrylate, and the like. These compounds may be used alone or in combination of two or more as appropriate, and may be those obtained by condensation of alkoxysilyl groups having a condensation degree of 2 to 6. Among them, 3- (meth) acryloyloxypropyltrimethoxysilane, 8- (meth) acryloyloxyoctyltrimethoxysilane, 11- (meth) acryloyloxyundecyltrimethoxysilane, 4-diethoxy-17-oxo-3, 16-dioxa-18-aza-4-silaeicosan-20-yl (meth) acrylate, 4-diethoxy-17-oxo-3, 16, 21-trioxa-18-aza-4-silaeicosan-23-yl (meth) acrylate are preferable from the viewpoint of high affinity between the dental adhesive composition and the adherend, and high mechanical strength and adhesive strength. Since 3- (meth) acryloyloxypropyltrimethoxysilane has a small molecular weight, it is preferable because it exhibits excellent adhesive strength to a dental cutting repair material even when the amount of the compound added to the matrix is small. Since 8- (meth) acryloyloxyoctyltrimethoxysilane, 11- (meth) acryloyloxyundecyltrimethoxysilane, 4-diethoxy-17-oxo-3, 16-dioxa-18-aza-4-silaeicosan-20-yl (meth) acrylate, 4-diethoxy-17-oxo-3, 16, 21-trioxa-18-aza-4-silaeicosan-23-yl (meth) acrylate have a large molecular weight, the amount to be incorporated in the matrix increases, but since the compound has high hydrophobicity, it is preferable because it has excellent durable adhesion to a dental cutting repair material. Further, silane coupling agents having an alkoxysilyl group longer than the conventional methoxysilyl group and ethoxysilyl group, such as 3- (meth) acryloyloxypropyltripropoxysilane, 3- (meth) acryloyloxypropylmethyldipropoxysilane, 3- (meth) acryloyloxypropyltributoxysilane, and 3- (meth) acryloyloxypropylmethyldibutoxysilane, are preferable because of their excellent storage stability. In the structural formula, a compound having three alkoxysilyl groups when n ═ 3 is preferred from the viewpoint of versatility and adhesiveness.

The base in the present invention is an adhesive resin containing (a) a silane coupling agent containing (a1) a silane coupling agent represented by the structural formula (a), (B) a polymerizable monomer having an acid group, (C) a polymerizable monomer having no acid group, and (D) a polymerization initiator and/or (E) a polymerization accelerator, and is different from a paste containing a base and a filler. The matrix of the present invention does not contain a filler to which a pigment or a polymerization initiator component is adsorbed. In the present specification, unless otherwise specified, the matrix in the dental adhesive composition of the two-paste type means the sum of the matrix of the first paste and the matrix of the second paste.

When the dental adhesive composition of the present invention is a two-paste type, the above formula (1) is the following formula (5).

Formula (5): 0.005-0.070 in total of the indexes of the amount of silane coupling agent blended in the matrix ((S5 XW 5)/M5)

(in the formula (5), M5 represents the molecular weight of each silane coupling agent contained in the first substrate and/or the second substrate, S5 represents the number of alkoxysilyl groups in the molecule of each silane coupling agent contained in the first substrate and/or the second substrate, and W5 represents the amount of each silane coupling agent incorporated per 100 parts by mass of the total of the first substrate and the second substrate.)

When the total of the indices of the amount of silane coupling agent compounded in the matrix calculated from formula (1) exceeds 0.070 and the total of the indices of the amount of silane coupling agent compounded in the composition calculated from formula (2) exceeds 0.015 for each of the silane coupling agents, the dental adhesive composition of the present invention may suffer from a decrease in storage stability, a decrease in durable adhesive strength to dentin, and a decrease in storage stability and discoloration resistance. On the other hand, when the total of the indexes of the amount of the silane coupling agent blended in the matrix is less than 0.005 and the total of the indexes of the amount of the silane coupling agent blended in the composition is less than 0.001, the adhesiveness to the glass ceramic containing lithium disilicate and the adhesiveness to the resin for dental cutting may be deteriorated. The index of the amount of silane coupling agent incorporated into the matrix calculated from formula (1) and the index of the amount of silane coupling agent incorporated into the composition calculated from formula (2) are based on only the components contributing to adhesion. The silane coupling agent is bonded to the adherend via an alkoxysilyl group or the like as a hydrolyzable group. For example, a silane coupling agent used as a surface treatment agent for a filler is generally hydrolyzed and dehydration-condensed by mixing with an aqueous solution having a low pH of 5 or less or a high pH of 9 or more and performing a heating process, and since the alkoxysilane group of the silane coupling agent used as a surface treatment agent for a filler is condensed and bonded to the surface of the filler or between the silane coupling agents, it does not contribute to chemical adhesion of an adherend. Therefore, the calculation of the index of the amount of the silane coupling agent incorporated into the substrate and the index of the amount of the silane coupling agent incorporated into the composition are not included.

The total index of the amount of silane coupling agent incorporated in the matrix and the total index of the amount of silane coupling agent incorporated in the composition, and when a plurality of silane coupling agents are incorporated in the dental adhesive composition, the total index of the amount of silane coupling agent incorporated in the matrix calculated from the formula for each silane coupling agent and the total index of the amount of silane coupling agent incorporated in the composition calculated from the formula for each silane coupling agent are used. When a silane coupling agent is added to the dental adhesive composition, the index of the amount of the silane coupling agent added to the base or the index of the amount of the silane coupling agent added to the composition is calculated from the formula for the silane coupling agent.

The total of the silane coupling agent content indices in the matrix is preferably 0.010 to 0.055. The total of the indices of the amount of silane coupling agent incorporated in the composition is preferably 0.002 to 0.008.

(A1) The silane coupling agent represented by the structural formula (a) may be used singly or in combination of two or more. (A1) The amount of the silane coupling agent represented by the structural formula (a) is preferably 0.005 or more, more preferably 0.070 or less, and particularly preferably satisfies the structural formula (3), in total, as an index of the amount of the silane coupling agent (a1) incorporated in the base body calculated from the structural formula (3), with respect to each of the various silane coupling agents (a1) represented by the structural formula (a).

Formula (3): 0.005-0.005 in total of (A1) the index of the amount of the silane coupling agent blended in the matrix ((S3 XW 3)/M3) -0.070

(in the formula (3), M3 represents the molecular weight of each (A1) of the silane coupling agent represented by the formula (a) contained in the matrix, S3 represents the number of alkoxysilyl groups in each (A1) of the silane coupling agent represented by the formula (a) contained in the matrix, and W3 represents the amount of each (A1) of the silane coupling agent represented by the formula (a) contained in 100 parts by mass of the matrix.)

More preferably, the total index of the amount of the (a1) silane coupling agent incorporated in the matrix is 0.010 or more, and still more preferably 0.055 or less.

The amount of the silane coupling agent represented by the structural formula (a) in (a1) is preferably 0.001 or more, more preferably 0.015 or less, and particularly preferably satisfies the formula (4) in total of the indices of the amount of the silane coupling agent (a1) in the composition calculated from the formula (4) for each of the silane coupling agents represented by the structural formula (a 1).

Formula (4): 0.001. ltoreq. the total amount of (A1) the index of the amount of silane coupling agent blended in the composition ((S4 XW 4)/M4) is 0.015. ltoreq.

(in the formula (4), M4 is the molecular weight of each (A1) of the silane coupling agent represented by the structural formula (a) contained in the composition, S4 is the number of alkoxysilyl groups in each (A1) of the silane coupling agent represented by the structural formula (a) contained in the composition, and W4 is the blending amount of each (A1) of the silane coupling agent represented by the structural formula (a) in 100 parts by mass of the composition.)

More preferably, the total of the indices of the amount of the silane coupling agent (a1) incorporated in the composition is 0.002 or more, and still more preferably 0.008 or less.

The silane coupling agent (a1) represented by the structural formula (a) added to the dental adhesive composition of the present invention preferably has an acryloyl group. In the present invention, the silane coupling agent represented by the structural formula (a) can be contained as the silane coupling agent only in the (a1) having an acryloyl group. The silane coupling agent represented by the structural formula (a) and containing (a1) an acryloyl group improves the adhesive strength to a lithium disilicate-containing glass ceramic. When (a1) the silane coupling agent represented by the structural formula (a) having an acryloyl group is blended, (B) the polymerizable monomer having an acid group and (C) the polymerizable monomer having no acid group preferably have a methacryloyl group and/or a methacrylamido group, in this case, it can be expected that the adhesive strength to the lithium disilicate-containing glass ceramic is further improved. Specifically, when the total amount of (a) the silane coupling agent containing (a1) the silane coupling agent represented by the structural formula (a), (B) the polymerizable monomer having an acidic group, and (C) the polymerizable monomer having no acidic group (including (H) the polymerizable monomer having one or more sulfur atoms optionally contained) is 100 parts by mass, the amount of the compound having a methacryloyl group and/or an acrylamide group is preferably 99.9 parts by mass, and more preferably 80 to 99.9 parts by mass.

In this case, the total index of the amount of the silane coupling agent (a1) blended in the matrix calculated from formula (3) is preferably 0.005 or more, more preferably 0.070 or less, particularly preferably satisfies formula (3), even more preferably 0.010 or more, and even more preferably 0.055 or less, for each of the silane coupling agents (a1) represented by formula (a) and (a1) having an acryloyl group, with respect to the amount of the silane coupling agent (a1) represented by formula (a) blended in the dental adhesive composition.

The silane coupling agent represented by the structural formula (a) (a1) having an acryloyl group in the present invention can be used as long as it is a compound having an acryloyl group and an alkoxysilyl group.

Examples of the silane coupling agent represented by the structural formula (a) (A1) having an acryloyl group include 2-acryloyloxyethyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropylmethyldimethoxysilane, 4-acryloyloxybutyltrimethoxysilane, 6-acryloyloxypentyltrimethoxysilane, 6-acryloyloxyhexyltrimethoxysilane, 7-acryloyloxyheptyltrimethoxysilane, 8-acryloyloxyoctyltrimethoxysilane, 9-acryloyloxynonyltrimethoxysilane, 10-acryloyloxydecyltrimethoxysilane and 11-acryloyloxyundecyltrimethoxysilane. Further, examples of the substance having a urethane group or an ether group include 3, 3-dimethoxy-8, 37-dioxo-2, 9, 36-trioxa-7, 38-diaza-3-silatetradelan-40-yl acrylate, 2- ((3, 3-dimethoxy-8-oxo-2, 9, 18-trioxa-7-aza-3-silanonacan-19-oleyl) amino) -2-methylpropane-1, 3-diyl diacrylate, 3-dimethoxy-8, 19-dioxo-2, 9, 18-trioxa-7, 20-diaza-3-siladocosan-22-yl acrylate, and the like, 3, 3-dimethoxy-8, 22-dioxo-2, 9,12,15,18, 21-hexaoxa-7, 23-diaza-3-silapentacan-25-yl acrylate, 3-dimethoxy-8, 22-dioxo-2, 9,12,15,18,21, 26-heptaoxa-7, 23-diaza-3-silaoctacosan-28-yl acrylate, 3-dimethoxy-8, 19-dioxo-2, 9,12,15, 18-pentaoxa-7, 20-diaza-3-siladocosan-22-yl acrylate, 3-dimethoxy-8, 19-dioxo-2, 9,12,15,18, 23-hexaoxa-7, 20-diaza-3-silapentan-25-yl acrylate, 2- ((3, 3-dimethoxy-8-oxo-2, 9,12,15, 18-pentaoxa-7-aza-3-silanonacan-19-oleyl) amino) -2-methylpropan-1, 3-diyl diacrylate, 4-diethoxy-17-oxo-3, 16, 21-trioxa-18-aza-4-silacosan-12-yl acrylate, 4-diethoxy-17-oxo-3, 16,21, 24-tetraoxa-18-aza-4-silahexaen-26-yl acrylate, 4, 4-diethoxy-13-oxo-3, 12, 17-trioxa-14-aza-4-silanonacan-19-yl acrylate, 4-diethoxy-17-oxo-3, 16-dioxa-18-aza-4-silaeicosan-20-yl acrylate, 2-methyl-2- ((11- (triethoxysilyl) undecaoxy) carbonylamino) propane-1, 3-diyl diacrylate, and the like. These can be used alone or in appropriate combination of two or more. Among them, 3-acryloyloxypropyltrimethoxysilane, 8-acryloyloxyoctyltrimethoxysilane, 11-acryloyloxyundecyltrimethoxysilane, 4-diethoxy-17-oxo-3, 16-dioxa-18-aza-4-silaeicosan-20-yl acrylate, 4-diethoxy-17-oxo-3, 16, 21-trioxa-18-aza-4-silatricosyl-23-yl acrylate are preferable from the viewpoint of high affinity between the dental adhesive composition and the adherend and high mechanical strength and adhesive strength. A silane coupling agent having a relatively small molecular weight, such as 3-acryloxypropyltrimethoxysilane, is more preferable in a high viscosity composition, and it can be expected that a glass ceramic containing lithium disilicate has a high adhesive strength with a small amount of incorporation. Silane coupling agents having a relatively large molecular weight, such as 8-acryloyloxyoctyltrimethoxysilane, 4-diethoxy-17-oxy-3, 16-dioxa-18-aza-4-silaeicosan-20-ylacrylate, 4-diethoxy-17-oxy-3, 16, 21-trioxa-18-aza-4-silatricosane-23-ylacrylate, can be expected to have a high durable adhesion to a glass ceramic containing lithium disilicate. From the viewpoint of versatility and adhesiveness, the silane coupling agent used is preferably a silane coupling agent having three alkoxysilyl groups in the case where n is 3 in the structural formula.

The silane coupling agent (a1) having an acryloyl group represented by the structural formula (a) may be a condensate having an alkoxysilyl group remaining therein. The condensation product is, for example, a condensation product of the above-mentioned compound or a condensation product with trimethoxymethylsilane, trimethoxyethylsilane, trimethoxypropylsilane, trimethoxybutylsilane, trimethoxyallylsilane, triethoxymethylsilane, triethoxyethylsilane, tripropoxymethylsilane, tripropoxypropylsilane, tributoxymethylsilane, tributoxybutylsilane, dimethoxydimethylsilane or diethoxydiethylsilane, and the degree of condensation is 2 to 30, preferably 2 to 6. These silane coupling agents having an acryloyl group may be used singly or in combination of two or more. Other silane coupling agents such as a silane coupling agent having a methacryloyl group may be used in combination as long as they contain a silane coupling agent having an acryloyl group.

The dental adhesive composition of the present invention may contain (a) a silane coupling agent other than (a1) the silane coupling agent represented by the structural formula (a). As the silane coupling agent (a) other than the silane coupling agent (a1) represented by the structural formula (a), conventionally known silane coupling agents can be used. The dental adhesive composition of the present invention may not contain (a) a silane coupling agent other than (a1) the silane coupling agent represented by the structural formula (a). The dental adhesive composition of the present invention may not contain (a) a silane coupling agent other than (a1) a silane coupling agent represented by structural formula (a) having an acryloyl group.

The dental adhesive composition of the present invention comprises (B) a polymerizable monomer having an acidic group for the purpose of imparting adhesiveness to a prosthetic device to be attached to dentin or to the oral cavity. The polymerizable monomer having an acidic group can be used without limitation as long as it has one or more polymerizable groups and at least one acidic group such as a phosphoric acid group, a pyrophosphoric acid group, a thiophosphoric acid group, a phosphonic acid group, a sulfonic acid group, or a carboxylic acid group.

Examples of the polymerizable monomer having an acidic group having a phosphoric acid group include 2- (meth) acryloyloxyethyl dihydrogen phosphate, 3- (meth) acryloyloxypropyl dihydrogen phosphate, 4- (meth) acryloyloxybutyl dihydrogen phosphate, 5- (meth) acryloyloxypentyl dihydrogen phosphate, 6- (meth) acryloyloxyhexyl dihydrogen phosphate, 7- (meth) acryloyloxyheptyl dihydrogen phosphate, 8- (meth) acryloyloxyoctyl dihydrogen phosphate, 9- (meth) acryloyloxynonyl dihydrogen phosphate, 10- (meth) acryloyloxydecyl dihydrogen phosphate, 11- (meth) acryloyloxyundecyl dihydrogen phosphate, 12- (meth) acryloyloxydodecyl phosphate, 2- (meth) acryloyloxy-decyl phosphate, 3- (meth) acryloyloxypropyl) dihydrogen phosphate, and the like, 16- (meth) acryloyloxycetaxadecyl dihydrogen phosphate, 20- (meth) acryloyloxyeicosyl dihydrogen phosphate, bis [2- (meth) acryloyloxyethyl ] hydrogen phosphate, bis [4- (meth) acryloyloxybutyl ] hydrogen phosphate, bis [ 6- (meth) acryloyloxyhexyl ] hydrogen phosphate, bis [ 8- (meth) acryloyloxyoctyl ] hydrogen phosphate, bis [ 9- (meth) acryloyloxynonyl ] hydrogen phosphate, bis [ 10- (meth) acryloyloxydecyl ] hydrogen phosphate, 1, 3-bis (meth) acryloyloxypropyl hydrogen phosphate, 2- (meth) acryloyloxyethylphenyl hydrogen phosphate, 2- (meth) acryloyloxyethyl-2-bromoethyl hydrogen phosphate, hydrogen-2- (meth) acryloyloxyethyl-2-n-2-n-, Bis [2- (meth) acryloyloxy- (1-hydroxymethyl) ethyl ] hydrogen phosphate; acid chlorides, alkali metal salts, and ammonium salts of these; and (meth) acrylamide compounds in which ester bonds of these compounds are substituted with amide bonds.

Examples of the polymerizable monomer having an acidic group having a pyrophosphate group include bis [2- (meth) acryloyloxyethyl pyrophosphate ], bis [4- (meth) acryloyloxybutyl pyrophosphate ], bis [ 6- (meth) acryloyloxyhexyl pyrophosphate ], bis [ 8- (meth) acryloyloxyoctyl pyrophosphate ], bis [ 10- (meth) acryloyldecyl pyrophosphate ]; acid chlorides, alkali metal salts, and ammonium salts of these; and (meth) acrylamide compounds in which ester bonds of these compounds are substituted with amide bonds.

Examples of the polymerizable monomer having an acidic group having a thiophosphoric acid group include 2- (meth) acryloyloxyethyl dihydrogen thiophosphate, 3- (meth) acryloyloxypropyl dihydrogen thiophosphate, 4- (meth) acryloyloxybutyl dihydrogen thiophosphate, 5- (meth) acryloyloxypentyl dihydrogen thiophosphate, 6- (meth) acryloyloxyhexyl dihydrogen thiophosphate, 7- (meth) acryloyloxyheptyl dihydrogen thiophosphate, 8- (meth) acryloyloxyoctyl dihydrogen thiophosphate, 9- (meth) acryloyloxynonyl dihydrogen thiophosphate, 10- (meth) acryloyloxydecyl dihydrogen thiophosphate, 11- (meth) acryloyloxyundecyl dihydrogen thiophosphate, 1- (meth) acryloyloxy-decyl-thiophosphate, 2- (meth) acryloyloxy-undecyl-thiophosphate, and mixtures thereof, 12- (meth) acryloyloxydodecyl thiophosphate, 16- (meth) acryloyloxydodecyl thiophosphate, 20- (meth) acryloyloxydicosyl thiophosphate; acid chlorides, alkali metal salts, and ammonium salts of these; and (meth) acrylamide compounds in which ester bonds of these compounds are substituted with amide bonds.

Examples of the polymerizable monomer having an acidic group having a phosphonic acid group include 2- (meth) acryloyloxyethylphenylphosphonate, 5- (meth) acryloyloxypentyl-3-phosphonopropionate, 6- (meth) acryloyloxyhexyl-3-phosphonopropionate, 10- (meth) acryloyloxydecyl-3-phosphonopropionate, 6- (meth) acryloyloxyhexyl-3-phosphonoacetate, and 10- (meth) acryloyloxydecyl-3-phosphonoacetate; acid chlorides, alkali metal salts, and ammonium salts of these; and (meth) acrylamide compounds in which ester bonds of these compounds are substituted with amide bonds.

Examples of the polymerizable monomer having an acidic group having a sulfonic acid group include 2- (meth) acrylamide-2-methylpropanesulfonic acid and 2-sulfoethyl (meth) acrylate.

Examples of the polymerizable monomer having an acidic group having a carboxylic acid group include a (meth) acrylic compound having one carboxyl group in the molecule and a (meth) acrylic compound having a plurality of carboxyl groups in the molecule. Examples of the (meth) acrylic compound having one carboxyl group in the molecule include (meth) acrylic acid, N- (meth) acryloylglycine, N- (meth) acryloylaspartic acid, O- (meth) acryloyltyrosine, N- (meth) acryloylphenylalanine, N- (meth) acryloylp-aminobenzoic acid, N- (meth) acryloylanthranilic acid, p-vinylbenzoic acid, 2- (meth) acryloyloxybenzoic acid, 3- (meth) acryloyloxybenzoic acid, 4- (meth) acryloyloxybenzoic acid, N- (meth) acryloyl-5-aminosalicylic acid, N- (meth) acryloyl-4-aminosalicylic acid, N- (meth) acryloylglycine, N- (meth) acryloylaspartic acid, N- (meth) acryloyltyrosine, N- (meth) acryloylphenylalanine, N- (meth) acryloylp-aminobenzoic acid, N- (meth) acryloylanthranilic acid, N- (meth) acryloylo-4-aminosalicylic acid, N- (meth) acryloylamino-5-amino-benzoic acid, N- (meth) acryloyl-4-aminosalicylic acid, N- (meth) acrylic acid, N- (meth) acryloylamino-4-amino-benzoic acid, N- (meth) acrylic acid, and (meth) acrylic acid, 2- (meth) acryloyloxyethyl hydrogen succinate, 2- (meth) acryloyloxyethyl hydrogen phthalate, 2- (meth) acryloyloxyethyl hydrogen malate; acid halides of these; and (meth) acrylamide compounds in which ester bonds of these compounds are substituted with amide bonds. Examples of the (meth) acrylic compound having a plurality of carboxyl groups in the molecule include 6- (meth) acryloyloxyhexane-1, 1-dicarboxylic acid, 9- (meth) acryloyloxynonane-1, 1-dicarboxylic acid, 10- (meth) acryloyloxydecane-1, 1-dicarboxylic acid, 11- (meth) acryloyloxyundecane-1, 1-dicarboxylic acid, 12- (meth) acryloyloxydodecane-1, 1-dicarboxylic acid, 13- (meth) acryloyloxytridecyl-1, 1-dicarboxylic acid, 4- (meth) acryloyloxyethyl trimellitate, 4- (meth) acryloyloxybutyl trimellitate, 4- (meth) acryloyloxyhexyl trimellitate, 4- (meth) acryloyloxydecyl trimellitate, 2- (meth) acryloyloxyethyl-3 '- (meth) acryloyloxy-2' - (3, 4-dicarboxybenzoyloxy) propyl succinate; acid anhydrides and acid halides of these; and (meth) acrylamide compounds in which ester bonds of these compounds are substituted with amide bonds.

Among the polymerizable monomers having an acidic group (B), those having a phosphoric acid group or phosphonic acid group are preferable from the viewpoint of adhesiveness of the dental adhesive composition. Among these, an alkyl group or an alkylene group having 4 or more carbon atoms and having a main chain in the molecule is preferable, and 10- (meth) acryloyloxydecyl dihydrogen phosphate or (6-methacryloyloxy) hexylphosphonoacetate, 4-methacryloyloxyethyl trimellitic acid, and 4-methacryloyloxyethoxycarbonylphthalic anhydride are more preferable. These polymerizable monomers (B) having an acid group may be used in combination of plural kinds as required.

In the case where the dental adhesive composition of the present invention is a composition comprising a base containing (a1) a silane coupling agent represented by the structural formula (a), (B) a polymerizable monomer having an acid group, (C) a polymerizable monomer having no acid group, and (D) a polymerization initiator, the amount of the (B) polymerizable monomer having an acid group is preferably 1 to 20 parts by mass per 100 parts by mass of the base from the viewpoints of adhesiveness and storage stability.

The dental adhesive composition of the present invention is a two-paste type comprising (D1) a chemical polymerization initiator and (E) a polymerization accelerator, and when 15 to 80 parts by mass of (C1) a polymerizable monomer having no acidic group but having one or more hydroxyl groups is contained per 100 parts by mass of the first substrate and the second substrate, 1 to 30 parts by mass of the polymerizable monomer having an acidic group (B) is preferably contained per 100 parts by mass of the second substrate. When the amount is less than 1 part by mass, the reduction in the adhesion strength to dentin is particularly significant, and the adhesion strength to a dental cutting/repairing material may be reduced. When the amount is 30 parts by mass or more, the storage stability may be lowered. (B) The polymerizable monomer having an acidic group may be contained in the first base, and particularly, when the polymerizable monomer is added to a base containing a silane coupling agent in a blending amount exceeding the index of the blending amount of the silane coupling agent in the base of formula (1), it is preferable to contain only the second base because the storage stability may be lowered.

In the dental adhesive composition of the present invention, when the composition contains (a) a silane coupling agent containing (a1) a silane coupling agent represented by the structural formula (a), (B) a polymerizable monomer having an acid group, (C) a polymerizable monomer having no acid group, (H) a volatile organic solvent, and (G) water, and further contains one or both of (D) a polymerization initiator and (E) a polymerization accelerator, the amount of the (B) polymerizable monomer having an acid group is preferably 1 to 40 parts by mass per 100 parts by mass of the dental adhesive composition. When the amount is less than 1 part by mass, the expected adhesive strength may not be expressed easily, and when the amount exceeds 40 parts by mass, the storage stability may be lowered.

In this case, the amount of the polymerizable monomer having a functional group with high acidity, such as phosphate or phosphonate, for example, 10- (meth) acryloyloxydecyl dihydrogen phosphate or (6-methacryloyloxy) hexylphosphonoacetate, is preferably 0.1 to 20 parts by mass, among the polymerizable monomers having an acidic group (B). When the amount is less than 0.1 part by mass, the expected adhesive strength may not be expressed, and when the amount exceeds 20 parts by mass, the storage stability may be lowered.

The polymerizable monomer (C) having no acidic group of the present invention can be used without limitation as long as it is a known monomer having one or more polymerizable groups and no acidic group. (C) Among the polymerizable monomers having no acidic group, there are polymerizable monomers having one radical polymerizable group, polymerizable monomers having two radical polymerizable groups, and polymerizable monomers having three radical polymerizable groups.

Examples of the polymerizable monomer having one radical polymerizable group and no acidic group include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, propylene glycol mono (meth) acrylate, glycerol mono (meth) acrylate, erythritol mono (meth) acrylate, N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N- (dihydroxyethyl) (meth) acrylamide, methyl (meth) acrylate, ethyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, and (meth) acrylate, Propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, benzyl (meth) acrylate, lauryl (meth) acrylate, 2, 3-dibromopropyl (meth) acrylate, 3- (meth) acryloyloxypropyltrimethoxysilane, 11- (meth) acryloyloxyundecyltrimethoxysilane, (meth) acrylamide, and the like. Among them, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, glycerol mono (meth) acrylate, or erythritol mono (meth) acrylate is preferable in terms of high affinity with dentin of the obtainable dental adhesive composition.

Examples of the polymerizable monomer having two radically polymerizable groups and no acidic group include 2, 2-Bis ((meth) acryloyloxyphenyl) propane, 2-Bis [4- (3- (meth) acryloyloxy) -2-hydroxypropoxyphenyl ] propane (commonly referred to as "Bis-GMA"), 2-Bis (4- (meth) acryloyloxyphenyl) propane, 2-Bis (4- (meth) acryloyloxypolyethoxyphenyl) propane, 2-Bis (4- (meth) acryloyloxydiethoxyphenyl) propane), 2-Bis (4- (meth) acryloyloxytetraethoxyphenyl) propane, 2-Bis (4- (meth) acryloyloxypentaethoxyphenyl) propane, and, 2, 2-bis (4- (meth) acryloyloxydipropylphenyl) propane, 2- (4- (meth) acryloyloxydiethoxyphenyl) -2- (4- (meth) acryloyloxydiethoxyphenyl) propane, 2- (4- (meth) acryloyloxydipropylphenyl) -2- (4- (meth) acryloyloxytriethoxyphenyl) propane, 2-bis (4- (meth) acryloyloxypropylphenyl) propane, 2-bis (4- (meth) acryloyloxyisopropoxyphenyl) propane, a salt thereof, a hydrate thereof, a crystalline solid thereof, and a crystalline solid thereof, 1, 4-bis (2- (meth) acryloyloxyethyl) pyromellitate, glycerol di (meth) acrylate, 1- (acryloyloxy) -3- (methacryloyloxy) -2-propanol, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, 1, 5-pentanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, 1, 2-bis (3-methacryloyloxy-2-hydroxypropoxy) ethane, ethylene glycol di (meth) acrylate, propylene glycol (meth) acrylate, ethylene glycol (2-acrylate, propylene glycol (2-acrylate, ethylene glycol (meth) acrylate, ethylene glycol (2-acrylate, ethylene glycol (2-acrylate, propylene glycol (2-acrylate, and propylene glycol (2-acrylate, ethylene glycol (2-acrylate, and propylene glycol (2-acrylate, and propylene glycol (2-acrylate, and propylene glycol (2-acrylate), and propylene glycol (2-2, 2,2, 4-trimethylhexamethylenebis (2-carbamoyloxyethyl) dimethacrylate (commonly known as "UDMA"), 1, 2-bis (3-methacryloyloxy-2-hydroxypropoxy) ethane, and the like. Among these, from the viewpoint of mechanical strength, 2-bis ((meth) acryloyloxyphenyl) propane, 2-bis [4- (3- (meth) acryloyloxy) -2-hydroxypropoxyphenyl ] propane, 2, 4-trimethylhexamethylene bis (2-carbamoyloxyethyl) dimethacrylate and 2, 2-bis (4- (meth) acryloyloxypolyethoxyphenyl) propane are preferable, and from the viewpoint of handling properties, triethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate and glycerol di (meth) acrylate are preferable. In 2, 2-bis (4- (meth) acryloyloxypolyethoxyphenyl) propane, a compound having an average molar number of addition of ethoxy groups of 2.6 (generally referred to as "d2.6 e") is preferable.

Examples of the polymerizable monomer having three or more radically polymerizable groups and no acidic group include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolmethane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, N- (2,2, 4-trimethylhexamethylene) bis [2- (aminocarboxy) propane-1, 3-diol ] tetramethylacrylate, 1, 7-diacryloyloxy-2, 2,6, 6-tetraacryloxymethyl-4-oxyheptane, and the like. Among them, trimethylolpropane tri (meth) acrylate is preferable in terms of high mechanical strength of the obtainable dental adhesive composition.

These polymerizable monomers (C) having no acid group may be used in combination of plural kinds as required.

In the case where the dental adhesive composition of the present invention is a composition comprising a matrix containing (a) a silane coupling agent represented by the structural formula (a) (a1), (B) a polymerizable monomer having an acid group, (C) a polymerizable monomer having no acid group, and (D) a polymerization initiator, from the viewpoint of improving mechanical properties, it is preferable that 65 to 95 parts by mass of the polymerizable monomer having no acid group (C) be contained in the matrix. In addition, from the viewpoint of improving mechanical properties, the amount of the polymerizable monomer having two or more radical polymerizable groups and no acid group is preferably 40 to 100 parts by mass, and more preferably 60 to 100 parts by mass, of 100 parts by mass of the polymerizable monomer (C) having no acid group contained in the matrix. When the amount of the polymerizable monomer having two or more radically polymerizable groups and no acid group is less than 40 parts by mass, mechanical properties may be deteriorated.

The dental adhesive composition of the present invention is a two-paste type comprising (D1) a chemical polymerization initiator and (E) a polymerization accelerator, and when 15 to 80 parts by mass of (C1) a polymerizable monomer having no acidic group and one or more hydroxyl groups is contained per 100 parts by mass of the first substrate and the second substrate, from the viewpoint of improving mechanical properties, (C) the polymerizable monomer having no acidic group is preferably 65 to 98 parts by mass per 100 parts by mass of the first substrate, and is preferably 65 to 95 parts by mass per 100 parts by mass of the second substrate. In addition, from the viewpoint of improving mechanical properties, the amount of the polymerizable monomer having two or more radical polymerizable groups and no acid group is preferably 40 to 100 parts by mass, and more preferably 60 to 100 parts by mass, of 100 parts by mass of the polymerizable monomer having no acid group (C) contained in the first substrate and the second substrate. When the amount of the polymerizable monomer having two or more radically polymerizable groups and no acid group is less than 40 parts by mass, mechanical properties may be deteriorated.

In the case where the dental adhesive composition of the present invention contains (a) a silane coupling agent containing (a1) a silane coupling agent represented by the structural formula (a), (B) a polymerizable monomer having an acid group, (C) a polymerizable monomer having no acid group, (H) a volatile organic solvent, and (G) water, and further contains either or both of (D) a polymerization initiator and (E) a polymerization accelerator, it is preferable that the dental adhesive composition contains 5 to 60 parts by mass of (C) the polymerizable monomer having no acid group per 100 parts by mass of the dental adhesive composition. When the amount is less than 5 parts by mass, mechanical properties may be low when the adhesive is used as a dental adhesive, and when the amount exceeds 60 parts by mass, the thickness of the coating film at the time of coating on the surface to be adhered may be increased, and a satisfactory feeling of handling may not be obtained. In addition, in the polymerizable monomer (C) having no acidic group, the amount of the polymerizable monomer having two or more radical polymerizable groups and no acidic group is preferably set to 40 to 100 parts by mass in 100 parts by mass of the polymerizable monomer (C) having no acidic group. When the amount of the polymerizable monomer having two radically polymerizable groups and no acid group is less than 40 parts by mass, mechanical properties may be deteriorated.

In the present invention, (C) the polymerizable monomer having no acid group includes (C1) a polymerizable monomer having no acid group and having one or more hydroxyl groups. In the present invention, (C1) the polymerizable monomer having no acidic group but having one or more hydroxyl groups and (a1) the silane coupling agent represented by the structural formula (a) coexist in at least one substrate.

(C1) The polymerizable monomer having not an acid group but one or more hydroxyl groups may be used in combination of plural kinds as required.

In the case where the dental adhesive composition of the present invention is a composition comprising a base containing (a1) a silane coupling agent represented by the structural formula (a), (B) a polymerizable monomer having an acid group, (C) a polymerizable monomer having no acid group, and (D) a polymerization initiator, the amount of the (C1) polymerizable monomer having no acid group and one or more hydroxyl groups is preferably 0.1 to 70 parts by mass per 100 parts by mass of the base containing (a1) the silane coupling agent represented by the structural formula (a). More preferably 5 to 60 parts by mass. By blending (a1) the silane coupling agent represented by the structural formula (a) into a matrix, in addition to being able to expect high adhesive strength to a lithium disilicate-containing glass ceramic, by blending (a1) the silane coupling agent represented by the structural formula (a) and (C1) a polymerizable monomer having no acidic group but having one or more hydroxyl groups into the same matrix, it is possible to expect higher adhesive strength to a lithium disilicate-containing glass ceramic and improvement in storage stability. When the amount is less than 0.1 part by mass, a higher adhesive strength to a glass ceramic containing lithium disilicate cannot be expected. If the amount exceeds 70 parts by mass, the storage stability may be lowered.

The dental adhesive composition of the present invention is a two-paste type comprising (D1) a chemical polymerization initiator and (E) a polymerization accelerator, and when 15 to 80 parts by mass of (C1) a polymerizable monomer having no acidic group and one or more hydroxyl groups is contained per 100 parts by mass of a first substrate and a second substrate, the adhesive strength to a dental cutting restorative material is improved by containing 15 to 80 parts by mass of (C1) a polymerizable monomer having no acidic group and one or more hydroxyl groups per 100 parts by mass of the total of the first substrate and the second substrate contained in the dental curable adhesive composition. Preferably 20 to 70 parts by mass. When the amount is less than 15 parts by mass, good adhesion strength to the dental cutting repair material is not exhibited. On the other hand, if it exceeds 80 parts by mass, the storage stability is lowered.

In the dental adhesive composition of the present invention, when the composition contains (A) a silane coupling agent containing (A1) a silane coupling agent represented by the structural formula (a), (B) a polymerizable monomer having an acid group, (C) a polymerizable monomer having no acid group, (H) a volatile organic solvent, and (G) water, and further contains either or both of (D) a polymerization initiator and (E) a polymerization accelerator, the adhesive strength to a dental cutting resin is improved by setting the amount of (C1) a polymerizable monomer having no acid group but one or more hydroxyl groups to 20 to 70 parts by mass relative to 100 parts by mass in total of (A) the silane coupling agent containing (A1) the silane coupling agent represented by the structural formula (a), (B) a polymerizable monomer having an acid group, and (C) a polymerizable monomer having no acid group, further, the storage stability of the silane coupling agent contained in the composition can be expected to be improved. (C1) The amount of the polymerizable monomer having no acidic group and having one or more hydroxyl groups is more preferably 30 to 60 parts by mass. If the amount is more than 70 parts by mass, the storage stability may be lowered, and if the amount is less than 20 parts by mass, the expected adhesive strength to the dental cutting resin may not be exhibited.

(C1) The polymerizable monomer having one or more hydroxyl groups and no acidic group can be used without limitation as long as it is a known monomer having one or more hydroxyl groups and no acidic group. The polymerizable group is preferably a polymerizable monomer having radical polymerizability, and specifically, from the viewpoint of easy radical polymerization, the polymerizable group is preferably a (meth) acrylic group and/or a (meth) acrylamide group. Examples thereof include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, propylene glycol mono (meth) acrylate, glycerol mono (meth) acrylate, erythritol mono (meth) acrylate, N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N- (dihydroxyethyl) (meth) acrylamide, 2-bis [4- (3- (meth) acryloyloxy) -2-hydroxypropoxyphenyl ] propane, glycerol di (meth) acrylate, and mixtures thereof, 1- (acryloyloxy) -3- (methacryloyloxy) -2-propanol, pentaerythritol triacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 1, 4-cyclohexanedimethanol monoacrylate, from the viewpoints of mechanical strength of the obtainable dental adhesive composition and affinity of the curable composition for an adherend, are preferably 2-hydroxyethyl (meth) acrylate, 2-bis [4- (3- (meth) acryloyloxy) -2-hydroxypropoxyphenyl ] propane, glycerol di (meth) acrylate, 1- (acryloyloxy) -3- (methacryloyloxy) -2-propanol, and more preferably 2-bis [4- (3- (meth) acryloyloxy) -2-propanol having two polymerizable groups Hydroxypropoxyphenyl ] propane, glycerol di (meth) acrylate, 1- (acryloyloxy) -3- (methacryloyloxy) -2-propanol.

In addition, among the polymerizable monomers (C1) having no acidic group and having one or more hydroxyl groups, (C11) having no acidic group and having one or more hydroxyl groups and having a viscosity of 200mPa · s or less at 25 ℃, which is high in fluidity at room temperature, is preferably contained in the first matrix containing (a) the silane coupling agent containing (a1) the silane coupling agent represented by the structural formula (a). The low-viscosity polymerizable monomer has a viscosity of 200 mPas or less as measured at 25 ℃ with a B-type viscometer. When a polymerizable monomer having not acid group but one or more hydroxyl group (C1) having a viscosity of less than 1000 mPas was measured, a spindle No. 1 was connected to a B-type viscometer BM type, and the rotation speed was gradually increased to full scale to perform the measurement. When the measurement cannot be performed with the rotor No. 1, the measurement pressure exceeds 200mPa · s. When the viscosity of the polymerizable monomer having a viscosity of 15mPa · s or less is measured with high accuracy, it is preferable to use a B-type viscometer BL. The low-viscosity polymerizable monomer (C11) having no acidic group but having one or more hydroxyl groups and having a viscosity of 200mPa · s or less at 25 ℃ can be used without limitation as long as it is a known monomer, and examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, propylene glycol mono (meth) acrylate, glycerol di (meth) acrylate, and 1- (acryloyloxy) -3- (methacryloyloxy) -2-propanol. The low-viscosity polymerizable monomer (C11) having no acidic group but having one or more hydroxyl groups and having a viscosity of 200mPa · s or less at 25 ℃ is preferably 0.1 to 50 parts by mass, more preferably 0.1 to 40 parts by mass, and still more preferably 5 to 30 parts by mass, based on 100 parts by mass of the first substrate. When the amount is less than 0.1 part by mass, a significant adhesion improving effect may not be exhibited on the dental cutting repair material, and when the amount exceeds 50 parts by mass, storage stability may be deteriorated.

The dental adhesive composition of the present invention may contain (I) a polymerizable monomer having one or more sulfur atoms in order to impart adhesiveness to the noble metal. The polymerizable monomer having one or more sulfur atoms (I) in the present invention is not limited to any known compound as long as it has at least one functional group of a sulfur group in a molecule and has one or more polymerizable groups. Among the functional groups having a thio group, a functional group which does not form a coordinate bond with a noble metal, such as a sulfo group, is not included therein. The functional group having a thio group is formed, for example, from a partial structure of > P ═ S, > C-S-C < and the like. Examples of the sulfur atom-containing polymerizable monomer include a compound capable of generating a mercapto group by tautomerism, a disulfide compound, a thiophosphoric acid, a linear or cyclic thioether compound, and the like. Specific examples thereof include 10-methacryloyloxydecyl-6, 8-dithiooctyl, 6-methacryloyloxyhexyl-2-thiouracil-5-carboxylate, 2- (11-methacryloyloxyundecylthio) -5-mercapto-1, 3, 4-thiadiazole, 8- (meth) acryloyloxyoctyl dihydrogen thiophosphate, and 10- (meth) acryloyloxydecyl dihydrogen thiophosphate. The adhesive composition for dental use preferably contains 0.01 to 10 parts by mass of (H) a polymerizable monomer having one or more sulfur atoms per 100 parts by mass of the adhesive composition for dental use. When the amount is less than 0.01 part by mass, good adhesion to the noble metal may not be expressed, and when the amount exceeds 10 parts by mass, improvement in adhesion in proportion to the amount to be blended may not be expressed.

In order to increase the relative polymerization rate of the silane coupling agent (a) in the composition, it is preferable that the compound having a methacryloyl group and/or a methacrylamido group is contained in an amount of 50 to 99 parts by mass based on 100 parts by mass of the matrix. The compound having a methacryloyl group and/or a methacrylamido group as referred to herein is not limited to the presence or absence of an acidic group. More preferably 70 to 100 parts by mass. In the case of less than 50 parts by mass, the durable adhesive strength to the lithium disilicate-containing glass ceramic may be lowered. On the other hand, higher adhesive strength can be expected as compared with the case of using a conventional silane coupling agent having a methacryloyl group. The ratio of the compound having a methacryloyl group and/or a methacrylamido group to 100 parts by mass of the total of (a) the silane coupling agent (a) containing (a1) the silane coupling agent represented by the structural formula (a), (B) the polymerizable monomer having an acidic group, and (C) the polymerizable monomer having no acidic group can be 50 to 99 parts by mass.

When the dental adhesive composition of the present invention is composed of a base containing (a) a silane coupling agent represented by the structural formula (a) (a1), (B) a polymerizable monomer having an acid group, (C) a polymerizable monomer having no acid group, and (D) a polymerization initiator, the amount of the (E) polymerization initiator can be 0.3 to 6 parts by mass per 100 parts by mass of the base.

In the dental adhesive composition of the present invention, which is a two-paste type comprising (D1) a chemical polymerization initiator and (E) a polymerization accelerator, in the case where 15 to 80 parts by mass of (C1) a polymerizable monomer having no acidic group and one or more hydroxyl groups is contained per 100 parts by mass of the first substrate and the second substrate, the chemical polymerization initiator (F) is preferably 0.1 to 5.0 parts by mass, and more preferably 0.5 to 2.5 parts by mass per 100 parts by mass of the total of the first substrate and the second substrate, from the viewpoint of improving curability. When the amount of the chemical polymerization initiator (F) is more than 5.0 parts by mass, it may be difficult to sufficiently secure the working time, while when the amount of the chemical polymerization initiator (F) is less than 0.1 parts by mass, the mechanical strength may be insufficient.

In the case where the dental adhesive composition of the present invention is a composition containing (a) a silane coupling agent containing (a1) a silane coupling agent represented by the structural formula (a), (B) a polymerizable monomer having an acid group, (C) a polymerizable monomer having no acid group, (H) a volatile organic solvent, and (G) water, and further containing either or both of (D) a polymerization initiator and (E) a polymerization accelerator, the dental adhesive composition contains either or both of (D) a polymerization initiator and (E) a polymerization accelerator. The dental adhesive composition preferably contains 0.01 to 5 parts by mass of (D) a polymerization initiator per 100 parts by mass of the dental adhesive composition, and can contain 0.01 to 5 parts by mass of (E) a polymerization accelerator per 100 parts by mass of the dental adhesive composition.

In the dental adhesive composition of the present invention, (D2) a photopolymerization initiator may be added as the (D) polymerization initiator for the purpose of imparting photopolymerization. Examples of the photopolymerization initiator (D2) include α -diketones, mono-, di-or triacylphosphine oxide compounds, and mono-, di-acylgermanium compounds.

(D2) The amount of the photopolymerization initiator to be blended is not particularly limited, but when the dental adhesive composition of the present invention is a composition comprising a base containing (a) a silane coupling agent represented by the formula (a) of (a1), (B) a polymerizable monomer having an acidic group, (C) a polymerizable monomer having no acidic group, and (D) a polymerization initiator, and (a1) the silane coupling agent represented by the formula (a) has an acryloyl group, the amount is preferably 0.01 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, based on 100 parts by mass of the base, from the viewpoint of photocurability.

The dental adhesive composition of the present invention is a two-paste type comprising (D1) a chemical polymerization initiator and (E) a polymerization accelerator, and when 15 to 80 parts by mass of (C1) a polymerizable monomer having no acidic group and one or more hydroxyl groups is contained per 100 parts by mass of the first substrate and the second substrate, from the viewpoint of photocurability, the amount is preferably 0.01 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass per 100 parts by mass of the total amount of the polymerizable monomers.

In the case where the dental adhesive composition of the present invention is a composition containing (a) a silane coupling agent containing (a1) a silane coupling agent represented by the structural formula (a), (B) a polymerizable monomer having an acid group, (C) a polymerizable monomer having no acid group, (H) a volatile organic solvent, and (G) water, and further containing either or both of (D) a polymerization initiator and (E) a polymerization accelerator, from the viewpoint of photocurability, it is preferably 0.01 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, based on 100 parts by mass of the dental adhesive composition.

Examples of the α -diketones include butanedione, dibenzyl, camphorquinone, 2, 3-pentanedione, 2, 3-octanedione, 9, 10-phenanthrenequinone, 4' -oxybenzyl, and acenaphthenequinone. Among them, camphorquinone is preferable because it has excellent photocurability in the visible light and near ultraviolet region, and shows sufficient photocurability using any light source of a halogen lamp, a Light Emitting Diode (LED), and a xenon lamp.

Examples of the mono-, bis-or triacylphosphine oxide compound include bis (2, 6-dimethoxybenzoyl) phenylphosphine oxide, bis (2, 6-dimethoxybenzoyl) (2,4, 4-trimethylpentyl) phosphine oxide, bis (2, 6-dimethoxybenzoyl) n-butylphosphine oxide, bis (2, 6-dimethoxybenzoyl) - (2-methylpropan-1-yl) phosphine oxide, bis (2, 6-dimethoxybenzoyl) - (1-methylpropan-1-yl) phosphine oxide, bis (2, 6-dimethoxybenzoyl) tert-butylphosphine oxide, bis (2, 6-dimethoxybenzoyl) cyclohexylphosphine oxide, bis (2, 6-dimethoxybenzoyl) octylphosphine oxide, tris (2, 6-dimethoxybenzoyl) phosphine oxide, tris (2, 6-dimethoxybenzoyl) n-butylphosphine oxide, bis (2, 6-dimethoxybenzoyl) phosphine oxide, 2, 4-trimethylpentyl) phosphine oxide, bis (2, 6-dimethoxybenzoyl) phosphine oxide, 2, 4-n-butylphosphine oxide, bis (2, 6-dimethoxybenzoyl) phosphine oxide, 2, 6-dimethylphosphine oxide, 2, 6-methyloxa, Bis (2-methoxybenzoyl) (2-methylpropan-1-yl) phosphine oxide, bis (2-methoxybenzoyl) (1-methylpropan-1-yl) phosphine oxide, bis (2, 6-diethoxybenzoyl) (2-methylpropan-1-yl) phosphine oxide, bis (2, 6-diethoxybenzoyl) (1-methylpropan-1-yl) phosphine oxide, bis (2, 6-dibutoxybenzoyl) (2-methylpropan-1-yl) phosphine oxide, bis (2, 4-dimethoxybenzoyl) (2-methylpropan-1-yl) phosphine oxide, bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, bis (2, 6-methylpropan-1-yl) phosphine oxide, bis (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide, bis (2, 6-dimethoxybenzoyl) phosphine oxide, bis (2-methylpropan-1-yl) phosphine oxide, bis (2, 6-dimethoxybenzoyl diphenylphosphine oxide, bis (2-methyl-1-yl) phosphine oxide, bis (2, 6-methyl-propa-tert-butyl) phosphine oxide, bis (2-methyl-benzoyl diphenyl phosphine oxide, bis (2-methyl-phenyl) phosphine oxide, bis (2, 6-methyl-phenyl) phosphine oxide, bis (2, 6-methyl-phenyl) phosphine oxide, bis (2, 6-methyl-phenyl) phosphine oxide, bis (2, 6-methyl-phenyl) phosphine, bis (2, 6-phenyl) phosphine, bis (2, 6-phenyl) phosphine, bis (2, or a-methyl-phenyl) phosphine, or a, Bis (2,4, 6-trimethylbenzoyl) (2, 4-dipentyloxyphenyl) phosphine oxide, bis (2, 6-dimethoxybenzoyl) benzylphosphine oxide, bis (2, 6-dimethoxybenzoyl) -2-phenylpropylphosphine oxide, bis (2, 6-dimethoxybenzoyl) -2-phenylethylphosphine oxide, 2, 6-dimethoxybenzoylbenzylbutylphosphine oxide, 2, 6-dimethoxybenzoylbenzyloctylphosphine oxide, bis (2,4, 6-trimethylbenzoyl) isobutylphosphine oxide, 2, 6-dimethoxybenzoyl-2, 4, 6-trimethylbenzoyl n-butylphosphine oxide and the like. Among these, bis (2, 6-dimethoxybenzoyl) (2,4, 4-trimethylpentyl) phosphine oxide or 2,4, 6-trimethylbenzoyldiphenylphosphine oxide is preferable from the viewpoint of photocurability.

Examples of the mono-or di-acylgermanium compound include bis-benzoyldiethylgermanium, bis-benzoyldimethylgermanium, bis-benzoyldibutylgermanium, bis (4-methoxybenzoyl) dimethylgermanium, bis (4-methoxybenzoyl) diethylgermanium and the like.

Examples of the organic peroxide as the chemical polymerization initiator (D1) include diacyl peroxides, peroxyesters, dialkyl peroxides, peroxyketals, ketone peroxides, peroxyesters, peroxydicarbonates, and hydroperoxides. Specific examples of diacyl peroxides include acetyl peroxide, isobutyryl peroxide, benzoyl peroxide, decanoyl peroxide, 3,5, 5-trimethylhexanoyl peroxide, 2, 4-dichlorobenzoyl peroxide, and lauroyl peroxide. Specific examples of the peroxyesters include α -cumyl peroxyneodecanoate, t-butyl peroxypivalate, 2, 4-trimethylpentylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, di-t-butylperoxy isophthalate, di-t-butylperoxy hexahydroterephthalate, t-butylperoxy-3, 3, 5-trimethylhexanoate, t-butylperoxy acetate, t-butylperoxy benzoate, t-butylperoxy maleate and the like. Specific examples of the dialkyl peroxides include di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, 1, 3-bis (t-butylperoxyisopropyl) benzene, and 2, 5-dimethyl-2, 5-di (t-butylperoxy) -3-hexyne. Specific examples of the ketone peroxides include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, methylcyclohexanone peroxide, cyclohexanone peroxide, and the like. Specific examples of the peroxyesters include α -cumyl peroxyneodecanoate, t-butyl peroxypivalate, 2, 4-trimethylpentylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, di-t-butylperoxy isophthalate, di-t-butylperoxy hexahydroterephthalate, t-butylperoxy-3, 3, 5-trimethylhexanoate, t-butylperoxy acetate, t-butylperoxy benzoate, t-butylperoxy maleate and the like. Specific examples of the peroxydicarbonates include di-3-methoxyperoxydicarbonate, di-2-ethylhexyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, diisopropylperoxydicarbonate, di-n-propylperoxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, and diallylperoxydicarbonate. Specific examples of the hydroperoxides include 2, 5-dimethylhexane-2, 5-dihydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, tert-butyl hydroperoxide, and 1,1,3, 3-tetramethylbutyl hydroperoxide.

The organic peroxide may be used alone, or two or more organic peroxides may be used in combination. Among these organic peroxides, benzoyl peroxide and cumene hydroperoxide are preferable from the viewpoint of curability. It is considered that the photopolymerization initiator alone is insufficient for bonding the dental cutting repair material having high masking property. The dental cutting and repairing material with high shielding performance is used for repairing the front tooth part which needs aesthetic property. In addition, since the glass fiber-reinforced resin made of an epoxy resin is also high in shielding property, it is effective to cure by chemical polymerization.

In the dental adhesive composition of the present invention, when the composition comprises a base containing (a) a silane coupling agent represented by the structural formula (a) of (a1), (B) a polymerizable monomer having an acidic group, (C) a polymerizable monomer having no acidic group, and (D) a polymerization initiator, and (a1) the silane coupling agent represented by the structural formula (a) has an acryloyl group, the amount of the organic peroxide as a chemical polymerization initiator is preferably 0.1 to 5 parts by mass, and more preferably 0.5 to 3 parts by mass, per 100 parts by mass of the base, from the viewpoint of improving curability. When the amount of the organic peroxide is more than 5 parts by mass, it may be difficult to sufficiently secure the working time, while when the amount of the organic peroxide is less than 0.1 part by mass, the mechanical strength may be insufficient.

In the case where the dental adhesive composition of the present invention contains (a) a silane coupling agent containing (a1) a silane coupling agent represented by the structural formula (a), (B) a polymerizable monomer having an acid group, (C) a polymerizable monomer having no acid group, (H) a volatile organic solvent, and (G) water, and further contains either or both of (D) a polymerization initiator and (E) a polymerization accelerator, the amount of the organic peroxide is preferably 0.1 to 5 parts by mass, and more preferably 0.3 to 3 parts by mass, per 100 parts by mass of the dental adhesive composition, from the viewpoint of improving curability. When the amount of the organic peroxide is more than 5 parts by mass, it may be difficult to sufficiently secure the working time, while when the amount of the organic peroxide is less than 0.1 part by mass, the mechanical strength may be insufficient.

In the dental adhesive composition of the present invention, which is a two-paste type comprising (D1) a chemical polymerization initiator and (E) a polymerization accelerator, in the case of containing 15 to 80 parts by mass of (C1) a polymerizable monomer having no acidic group and one or more hydroxyl groups per 100 parts by mass of the first substrate and the second substrate, the chemical polymerization initiator (D1) is preferably set to 0.1 to 5.0 parts by mass, more preferably 0.5 to 2.5 parts by mass per 100 parts by mass of the total of the first substrate and the second substrate, from the viewpoint of improving curability. When the amount of the (D1) chemical polymerization initiator is more than 5.0 parts by mass, it may be difficult to sufficiently secure the working time, while when the amount of the (D1) chemical polymerization initiator is less than 0.1 parts by mass, the mechanical strength may be insufficient.

In order to further improve curability, the dental adhesive composition of the present invention may further contain (E) a polymerization accelerator. Examples of the polymerization accelerator (E) include transition metal compounds of the 4 th cycle, thiourea derivatives, aliphatic amines, aromatic amines, sulfinic acids and salts thereof, borate compounds, sulfur-containing reducing inorganic compounds, nitrogen-containing reducing inorganic compounds, barbituric acid derivatives, triazine compounds, halogen compounds, and the like.

The dental adhesive composition of the present invention is a composition comprising a base containing (a1) a silane coupling agent represented by the structural formula (a), (B) a polymerizable monomer having an acid group, (C) a polymerizable monomer having no acid group, and (D) a polymerization initiator, and when (a1) the silane coupling agent represented by the structural formula (a) has an acryloyl group, the amount of (E) the polymerization accelerator is preferably 0.01 to 3 parts by mass, more preferably 0.1 to 3.0 parts by mass, relative to 100 parts by mass of the base.

The dental adhesive composition of the present invention is a two-paste type comprising (D1) a chemical polymerization initiator and (E) a polymerization accelerator, and when 15 to 80 parts by mass of (C1) a polymerizable monomer having no acidic group and one or more hydroxyl groups is contained per 100 parts by mass of the first substrate and the second substrate, the amount of the polymerization accelerator (E) is preferably 0.01 to 5.0 parts by mass, more preferably 0.2 to 2.5 parts by mass, per 100 parts by mass of the total of the first substrate and the second substrate. When the amount of the polymerization accelerator (E) to be blended exceeds 5.0 parts by mass, it may be difficult to sufficiently secure the working time, while when the amount of the polymerization accelerator (E) to be blended is less than 0.01 parts by mass, the mechanical strength may be insufficient.

In this case, the first substrate and the second substrate contain any one or more of (D1) a chemical polymerization initiator and (E) a polymerization accelerator. In the case where one or more (D1) chemical polymerization initiators are contained in the first matrix, one or more (E) polymerization accelerators are contained in the second matrix, and in the case where one or more (E) polymerization accelerators are contained in the first matrix, one or more (D1) chemical polymerization initiators are contained in the second matrix.

For example, it is preferable that (D1) the chemical polymerization initiator is contained in the first matrix and (E) the polymerization accelerator is contained in the second matrix, or (E) the polymerization accelerator is contained in the first matrix and (D1) the chemical polymerization initiator is contained in the second matrix. In the case where the chemical polymerization initiator (D1) and the polymerization accelerator (E) are combined so as not to affect the storage stability, they can be incorporated in the same matrix. For example, even when an organic peroxide as the (D1) chemical polymerization initiator and ethyl 4-N, N-dimethylaminobenzoate as the aromatic amine compound as the (E) polymerization accelerator are present in the same matrix, the redox reaction does not occur instantaneously even at a low concentration, and the storage stability is high. Therefore, the chemical polymerization initiator (D1) and the polymerization accelerator (E) can be compounded in the same matrix. In this case, in the other matrix, (D1) a chemical polymerization initiator and/or (E) a polymerization accelerator are contained in order to initiate chemical polymerization when the first paste and the second paste are kneaded.

In the dental adhesive composition of the present invention, when the composition contains (a) a silane coupling agent containing (a1) a silane coupling agent represented by the structural formula (a), (B) a polymerizable monomer having an acid group, (C) a polymerizable monomer having no acid group, (H) a volatile organic solvent, and (G) water, and further contains either or both of (D) a polymerization initiator and (E) a polymerization accelerator, the amount of the polymerization accelerator (E) is preferably 0.01 to 5 parts by mass, and more preferably 0.1 to 3.0 parts by mass, relative to 100 parts by mass of the total amount of the dental adhesive composition.

The transition metal compound of period 4 is a metal compound of groups 3 to 12 of period 4 of the periodic table, and specifically, any metal compound of scandium (Sc), titanium (Ti), vanadium (V), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), and zinc (Zn) can be used without limitation. The above-mentioned transition metal elements may have a plurality of valences, but may be added to the dental adhesive composition of the present invention as long as the valences are stably present. For example, Sc (3-valent), Ti (4-valent), V (3-, 4-or 5-valent), Cr (2-, 3-or 6-valent), Mn (2-to 7-valent), Fe (2-or 3-valent), Co (2-or 3-valent), Ni (2-valent), Cu (1-or 2-valent), and Zn (2-valent). Specific examples of the transition metal compound include scandium iodide (3 valent), titanium chloride (4 valent), titanium tetraisopropoxide (4 valent), etc., as the titanium compound, vanadium acetylacetonate (3 valent), vanadium tetraoxide (4 valent), vanadyl acetylacetonate (4 valent), vanadyl stearate (4 valent), vanadyl oxalate (4 valent), vanadyl sulfate (4 valent), oxybis (1-phenyl-1, 3-butanedione) vanadium (4 valent), bis (maltol) oxovanadium (4 valent), vanadyl pentoxide (5 valent), sodium metavanadate (5 valent), etc., as the manganese compound, manganese acetate (2 valent), manganese naphthenate (2 valent), etc., as the iron compound, iron acetate (2 valent), iron chloride (2 valent), iron acetate (3 valent), iron chloride (3 valent), etc., examples of the cobalt compound include cobalt acetate (2-valent) and cobalt naphthenate (2-valent), examples of the nickel compound include nickel chloride (2-valent) and the like, examples of the copper compound include copper chloride (1-valent), copper bromide (1-valent), copper chloride (2-valent) and copper acetate (2-valent) and examples of the zinc compound include zinc chloride (2-valent) and zinc acetate (2-valent).

Among them, a vanadium compound having a valence of 3 or 4, a copper compound having a valence of 2 are preferable, among them, a vanadium compound having a valence of 3 or 4 with higher polymerization promoting energy is more preferable, and a vanadium compound having a valence of 4 is most preferable. These transition metal compounds of the 4 th cycle may be used in combination in plural numbers as required.

The dental adhesive composition of the present invention is a composition comprising a base containing (a) a silane coupling agent represented by the structural formula (a) of (a1), (B) a polymerizable monomer having an acid group, (C) a polymerizable monomer having no acid group, and (D) a polymerization initiator, and when (a1) the silane coupling agent represented by the structural formula (a) has an acryloyl group, the amount of the transition metal compound is preferably 0.001 to 1 part by mass relative to 100 parts by mass of the total amount of the base, and when less than 0.001 part by mass, the polymerization accelerating effect is insufficient, and when more than 1 part by mass, the composition may become a factor of discoloration or gelling of the dental adhesive composition, and the storage stability may decrease.

In the dental adhesive composition of the present invention, which is a two-paste type comprising (D1) a chemical polymerization initiator and (E) a polymerization accelerator, in the case of a composition comprising 15 to 80 parts by mass of (C1) a polymerizable monomer having no acidic group and one or more hydroxyl groups per 100 parts by mass of the first and second substrates, the amount of the transition metal compound is preferably 0.001 to 1 part by mass per 100 parts by mass of the total amount of all the polymerizable monomers, and if it is less than 0.001 part by mass, the polymerization accelerating effect is insufficient, and if it exceeds 1 part by mass, discoloration or gelation of the dental cured adhesive composition may be caused, and the storage stability may be lowered.

In the dental adhesive composition of the present invention, in the case of a composition comprising (a) a silane coupling agent comprising (a1) a silane coupling agent represented by the structural formula (a), (B) a polymerizable monomer having an acid group, (C) a polymerizable monomer having no acid group, (H) a volatile organic solvent, and (G) water, and further comprising either or both of (D) a polymerization initiator and (E) a polymerization accelerator, the amount of the transition metal compound blended is preferably 0.001 to 1 part by mass per 100 parts by mass of the dental adhesive composition, and when it is less than 0.001 part by mass, the polymerization accelerating effect is insufficient, and when it exceeds 1 part by mass, it becomes a factor of discoloration or gelation of the dental adhesive composition, and the storage stability is lowered.

The thiourea derivative can be used without limitation as long as it is a known thiourea derivative. Specific examples thereof include dimethylthiourea, diethylthiourea, tetramethylthiourea, (2-pyridyl) thiourea, N-methylthiourea, ethylenethiourea, N-allylthiourea, N-allyl-N '- (2-hydroxyethyl) thiourea, N-benzylthiourea, 1, 3-dicyclohexylthiourea, N' -diphenylthiourea, 1, 3-di (p-tolyl) thiourea, 1-methyl-3-phenylthiourea, N-acetylthiourea, N-benzoylthiourea, diphenylthiourea and dicyclohexylthiourea. Among them, (2-pyridyl) thiourea, N-acetylthiourea and N-benzoylthiourea are preferable. These thiourea derivatives may be used in combination in plural numbers as required.

The dental adhesive composition of the present invention is a composition comprising a base containing (a) a silane coupling agent represented by the structural formula (a) of (a1), (B) a polymerizable monomer having an acid group, (C) a polymerizable monomer having no acid group, and (D) a polymerization initiator, and when (a1) the silane coupling agent represented by the structural formula (a) has an acryloyl group, the amount of the thiourea derivative is preferably 0.1 to 4 parts by mass per 100 parts by mass of the total amount of the base, when less than 0.1 part by mass, the polymerization acceleration energy is insufficient, and when more than 4 parts by mass, the storage stability may be reduced.

The dental adhesive composition of the present invention is a two-paste type comprising (D1) a chemical polymerization initiator and (E) a polymerization accelerator, and when the composition contains 15 to 80 parts by mass of (C1) a polymerizable monomer having no acidic group and one or more hydroxyl groups per 100 parts by mass of the first substrate and the second substrate, the amount of the thiourea derivative is preferably 0.1 to 4 parts by mass per 100 parts by mass of the total amount of all the polymerizable monomers, and when the amount is less than 0.1 part by mass, the polymerization acceleration ability is insufficient, and when the amount exceeds 4 parts by mass, the storage stability may be lowered.

In the case of the dental adhesive composition of the present invention, which comprises (a) a silane coupling agent comprising (a1) a silane coupling agent represented by the structural formula (a), (B) a polymerizable monomer having an acid group, (C) a polymerizable monomer having no acid group, (H) a volatile organic solvent, and (G) water, and further comprises either or both of (D) a polymerization initiator and (E) a polymerization accelerator, the amount of the thiourea derivative is preferably 0.1 to 4 parts by mass per 100 parts by mass of the dental adhesive composition, and when it is less than 0.1 part by mass, the polymerization acceleration energy is insufficient, and when it exceeds 4 parts by mass, the storage stability may be lowered.

Examples of the aliphatic amine include aliphatic primary amines such as n-butylamine, n-hexylamine, and n-octylamine; aliphatic secondary amines such as diisopropylamine and dibutylamine; aliphatic tertiary amines such as N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, N-lauryldiethanolamine, 2- (dimethylamino) ethyl (meth) acrylate, N-methyldiethanolamine di (meth) acrylate, N-ethyldiethanolamine di (meth) acrylate, triethanolamine mono (meth) acrylate, triethanolamine di (meth) acrylate, triethanolamine tri (meth) acrylate, triethanolamine, trimethylamine, triethylamine, and tributylamine. Among these, aliphatic tertiary amines are preferable from the viewpoint of curability and storage stability of the composition, and among these, 2- (dimethylamino) ethyl (meth) acrylate, N-methyldiethanolamine di (meth) acrylate, and triethanolamine are preferable.

Examples of the aromatic amine compound include N, N-bis (2-hydroxyethyl) -3, 5-dimethylaniline, N-bis (2-hydroxyethyl) p-toluidine, N-bis (2-hydroxyethyl) -3, 4-dimethylaniline, N-bis (2-hydroxyethyl) -4-ethylaniline, N-bis (2-hydroxyethyl) -4-isopropylaniline, N-bis (2-hydroxyethyl) -4-tert-butylaniline, N-bis (2-hydroxyethyl) -3, 5-diisopropylaniline, N-bis (2-hydroxyethyl) -3, 5-di-tert-butylaniline, N-dimethylaniline, N-methyl aniline, N-bis (2-hydroxyethyl) -4-ethyl aniline, N-bis (2-hydroxyethyl) -4-isopropylaniline, N-bis (2-hydroxyethyl) -3, 5-di-tert-butyl aniline, N-methyl aniline, N-bis (2-hydroxyethyl) -4-butyl aniline, N-bis (2-butyl aniline, N-methyl aniline, N-bis (2-ethyl) -3, N-bis (2-butyl aniline, N-bis (2-butyl) 4-butyl aniline, N-bis (2-butyl) aniline, N-bis (2-butyl aniline, N-bis (2-butyl) p-butyl aniline, N-butyl aniline, N-bis (2-butyl) p-butyl) aniline, N-bis (2-butyl aniline, N-bis (2-butyl) p-butyl) aniline, N-butyl) p-bis (2-butyl aniline, N-butyl aniline, N-bis (2-butyl) p-butyl) aniline, N-butyl aniline, N-bis (2-butyl) p-butyl aniline, N-bis (2-butyl) p-butyl aniline, N-butyl, N-bis (2-butyl aniline, N-butyl) p-butyl aniline, N-bis (2-butyl) p-butyl aniline, N, N, N-dimethyl-p-toluidine, N-dimethyl-m-toluidine, N-diethyl-p-toluidine, N-dimethyl-3, 5-dimethylaniline, N-dimethyl-3, 4-dimethylaniline, N-dimethyl-4-ethylaniline, N-dimethyl-4-isopropylaniline, N-dimethyl-4-t-butylaniline, N-dimethyl-3, 5-di-t-butylaniline, ethyl 4-N, N-dimethylaminobenzoate, methyl 4-N, N-dimethylaminobenzoate, N-butoxyethyl N, N-dimethylaminobenzoate, 2- (methacryloyloxy) ethyl 4-N, N-dimethylaminobenzoate, ethyl 2- (methacryloyloxy) ethyl, N-diethylamino-toluate, N-diethyl-p-toluidine, N-dimethyl-3, 5-dimethyl-3, 4-dimethylanilinium, N-dimethyl-4-aminobenzoate, N-dimethyl-4-amino-benzoic acid, N-dimethyl-4- (methacryloyloxy) ethyl, N-dimethylaminobenzoate, 4-N, N-dimethylaminobenzophenone, butyl 4-dimethylaminobenzoate, and the like. Among them, N-bis (2-hydroxyethyl) p-toluidine, ethyl 4-N, N-dimethylaminobenzoate, and N, N-dimethylaminobenzoate N-butoxyethyl are preferable from the viewpoints of excellent solubility in polymerizable monomers, storage stability, and ability to impart excellent curability to the composition.

Examples of sulfinic acids and salts thereof include p-toluenesulfinic acid, sodium p-toluenesulfinate, potassium p-toluenesulfinate, lithium p-toluenesulfinate, calcium p-toluenesulfinate, benzenesulfinic acid, sodium benzenesulfinate, potassium benzenesulfinate, lithium benzenesulfinate, calcium benzenesulfinate, 2,4, 6-trimethylbenzenesulfinic acid, sodium 2,4, 6-trimethylbenzenesulfinate, potassium 2,4, 6-trimethylbenzenesulfinate, lithium 2,4, 6-trimethylbenzenesulfinate, calcium 2,4, 6-trimethylbenzenesulfinate, 2,4, 6-triethylbenzenesulfinic acid, sodium 2,4, 6-triethylbenzenesulfinate, potassium 2,4, 6-triethylbenzenesulfinate, lithium 2,4, 6-triethylbenzenesulfinate, calcium 2,4, 6-triethylbenzenesulfinate, 2,4, 6-triisopropylbenzenesulfinic acid, Sodium 2,4, 6-triisopropylsulfinate, potassium 2,4, 6-triisopropylsulfinate, lithium 2,4, 6-triisopropylsulfinate, calcium 2,4, 6-triisopropylsulfinate, and the like, and sodium benzene sulfinate, sodium p-toluene sulfinate, and sodium 2,4, 6-triisopropylsulfinate are particularly preferable.

Specific examples of the borate compound having one aryl group in one molecule include trialkylphenylboron, trialkyl (p-chlorophenyl) boron, trialkyl (p-fluorophenyl) boron, trialkyl (3, 5-bistrifluoromethyl) phenylboron, trialkyl [3, 5-bis (1,1,1,3,3, 3-hexafluoro-2-methoxy-2-propyl) phenyl ] boron, trialkyl (p-nitrophenyl) boron, trialkyl (m-nitrophenyl) boron, trialkyl (p-butylphenyl) boron, trialkyl (m-butylphenyl) boron, trialkyl (p-butoxyphenyl) boron, trialkyl (m-butoxyphenyl) boron, trialkyl (p-octyloxyphenyl) boron and trialkyl (m-octyloxyphenyl) boron (alkyl is at least one member selected from the group consisting of n-butyl, n-octyl and n-dodecyl groups), sodium salts of these compounds, Lithium salts, potassium salts, magnesium salts, tetrabutylammonium salts, tetramethylammonium salts, tetraethylammonium salts, picolinium salts, ethylpyridinium salts, butylpyridinium salts, methylquinolinium salts, ethylquinolinium salts, butylquinolinium salts, and the like. Specific examples of the borate compound having two aryl groups in one molecule include sodium salts of dialkyldiphenylboron, dialkylbis (p-chlorophenyl) boron, dialkylbis (p-fluorophenyl) boron, dialkylbis (3, 5-bistrifluoromethyl) phenylboron, dialkylbis [3, 5-bis (1,1,1,3,3, 3-hexafluoro-2-methoxy-2-propyl) phenyl ] boron, dialkylbis (p-nitrophenyl) boron, dialkylbis (m-nitrophenyl) boron, dialkylbis (p-butylphenyl) boron, dialkylbis (m-butylphenyl) boron, dialkylbis (p-butoxyphenyl) boron, dialkylbis (m-butoxyphenyl) boron, dialkylbis (p-octyloxyphenyl) boron and dialkylbis (m-octyloxyphenyl) boron (alkyl group is at least one selected from the group consisting of n-butyl, n-octyl and n-dodecyl), sodium salts thereof, and the like, Lithium salts, potassium salts, magnesium salts, tetrabutylammonium salts, tetramethylammonium salts, tetraethylammonium salts, picolinium salts, ethylpyridinium salts, butylpyridinium salts, methylquinolinium salts, ethylquinolinium salts, butylquinolinium salts, and the like. Specific examples of the borate compound having three aryl groups in one molecule include sodium salts of monoalkyltriphenylboron, monoalkyltri (p-chlorophenyl) boron, monoalkyltri (p-fluorophenyl) boron, monoalkyltri (3, 5-bistrifluoromethyl) phenylboron, monoalkyltri [3, 5-bis (1,1,1,3,3, 3-hexafluoro-2-methoxy-2-propyl) phenyl ] boron, monoalkyltri (p-nitrophenyl) boron, monoalkyltri (m-nitrophenyl) boron, monoalkyltri (p-butylphenyl) boron, monoalkyltri (m-butylphenyl) boron, monoalkyltri (p-butoxyphenyl) boron, monoalkyltri (m-butoxyphenyl) boron, monoalkyltri (p-octyloxyphenyl) boron and monoalkyltri (m-octyloxyphenyl) boron (the alkyl group is one selected from n-butyl, n-octyl or n-dodecyl), sodium salts of monoalkyltri (p-butylphenyl) boron, monoalkyltri (p-chlorophenyl) boron, monoalkyltri (p-fluorophenyl) boron, monoalkyltri (p-nitrophenyl) boron and monoalkyltri (m-octyloxyphenyl) boron, sodium salts of monoalkyltri (n-butyl, n-octyl or n-dodecyl) boron, Lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, picolinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, butylquinolinium salt, and the like. Specific examples of the borate compound having four aryl groups in one molecule include tetraphenylboron, tetrakis (p-chlorophenyl) boron, tetrakis (p-fluorophenyl) boron, tetrakis (3, 5-bistrifluoromethyl) phenylboron, tetrakis [3, 5-bis (1,1,1,3,3, 3-hexafluoro-2-methoxy-2-propyl) phenyl ] boron, tetrakis (p-nitrophenyl) boron, tetrakis (m-nitrophenyl) boron, tetrakis (p-butylphenyl) boron, tetrakis (m-butylphenyl) boron, tetrakis (p-butoxyphenyl) boron, tetrakis (m-butoxyphenyl) boron, tetrakis (p-octyloxyphenyl) boron, tetrakis (m-octyloxyphenyl) boron, (p-fluorophenyl) triphenylboron, (3, 5-bistrifluoromethyl) phenyltriphenylboron, (p-nitrophenyl), (m-butoxyphenyl) triphenylboron, tetrakis (p-octyloxyphenyl) boron, tetrakis (p-octyloxyphenyl) triphenylboron, Sodium salts, lithium salts, potassium salts, magnesium salts, tetrabutylammonium salts, tetramethylammonium salts, tetraethylammonium salts, picolinium salts, ethylpyridinium salts, butylpyridinium salts, methylquinolinium salts, ethylquinolinium salts, butylquinolinium salts, and the like of (p-butoxyphenyl) triphenylboron, (m-octyloxyphenyl) triphenylboron, and (p-octyloxyphenyl) triphenylboron.

Among these aryl borate compounds, borate compounds having three or four aryl groups in one molecule are more preferably used from the viewpoint of storage stability. These aryl borate compounds may be used singly or in combination of two or more.

Examples of the sulfur-containing reducing inorganic compound include sulfite, bisulfite, pyrosulfite, thiosulfate, dithionite (thionite), dithionite (dithionite), and the like, and specific examples thereof include sodium sulfite, potassium sulfite, calcium sulfite, ammonium sulfite, sodium bisulfite, potassium bisulfite, 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzoxazole, decylthiol, thiobenzoic acid, and the like.

Examples of the nitrogen-containing reducing inorganic compound include nitrites, and specific examples thereof include sodium nitrite, potassium nitrite, calcium nitrite, and ammonium nitrite.

Examples of the barbituric acid derivatives include barbituric acid, 1, 3-dimethylbarbituric acid, 1, 3-diphenylbarbituric acid, 1, 5-dimethylbarbituric acid, 5-butylbarbituric acid, 5-ethylbarbituric acid, 5-isopropylbarbituric acid, 5-cyclohexylbarbituric acid, 1,3, 5-trimethylbarbituric acid, 1, 3-dimethyl-5-ethylbarbituric acid, 1, 3-dimethyl-n-butylbarbituric acid, 1, 3-dimethyl-5-isobutylbarbituric acid, 1, 3-dimethylbarbituric acid, 1, 3-dimethyl-5-cyclopentylbarbituric acid, 1, 3-dimethyl-5-cyclohexylbarbituric acid, 1, 3-dimethyl-5-phenylbarbituric acid, Salts of 1-cyclohexyl-1-ethylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, 5-methylbarbituric acid, 5-propylbarbituric acid, 1, 5-diethylbarbituric acid, 1-ethyl-5-methylbarbituric acid, 1-ethyl-5-isobutylbarbituric acid, 1, 3-diethyl-5-butylbarbituric acid, 1-cyclohexyl-5-methylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, 1-cyclohexyl-5-octylbarbituric acid, 1-cyclohexyl-5-hexylbarbituric acid, 5-butyl-1-cyclohexylbarbituric acid, 1-benzyl-5-phenylbarbituric acid and thiobarbituric acid (preferably alkali metal or alkaline earth metal based salts thereof ) Specific examples of the salts of these barbituric acids include sodium 5-butylbarbiturate, sodium 1,3, 5-trimethylbarbiturate, and sodium 1-cyclohexyl-5-ethylbarbiturate.

Examples of the triazine compound include 2,4, 6-tris (trichloromethyl) -s-triazine, 2,4, 6-tris (tribromomethyl) -s-triazine, 2-methyl-4, 6-bis (trichloromethyl) -s-triazine, 2-methyl-4, 6-bis (tribromomethyl) -s-triazine, 2-phenyl-4, 6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (p-methylthiophenyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (p-trichloromethyl) -s-triazine, and mixtures thereof, 2- (2, 4-dichlorophenyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (p-bromophenyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4, 6-bis (trichloromethyl) -s-triazine, 2-n-propyl-4, 6-bis (trichloromethyl) -s-triazine, 2- (. alpha.,. beta. -trichloroethyl) -4, 6-bis (trichloromethyl) -s-triazine, 2-styryl-4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (p-methoxyphenyl) vinyl ] -4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (o-methoxyphenyl) vinyl ] -4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (p-butoxyphenyl) vinyl ] -4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (3, 4-dimethoxyphenyl) vinyl ] -4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4, 5-trimethoxyphenyl) vinyl ] -4, 6-bis (trichloromethyl) -s-triazine, 2- (1-naphthyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (4-biphenyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- [2- { N, N-bis (2-hydroxyethyl) amino } ethoxy ] -4, 6-bis (trichloromethyl) -s-triazine, 2- [2- { N-hydroxyethyl-N-ethylamino } ethoxy ] -4, 6-bis (trichloromethyl) -s-triazine, 2- [2- { N-hydroxyethyl-N-methylamino } ethoxy ] -4, 6-bis (trichloromethyl) -s-triazine, 2- [2- { N, N-diallylamino } ethoxy ] -4, 6-bis (trichloromethyl) -s-triazine, and the like.

Examples of the halogen compound include dilauryl dimethyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride, benzyl trimethyl ammonium chloride, tetramethyl ammonium chloride, benzyl dimethyl cetyl ammonium chloride, and dilauryl dimethyl ammonium bromide.

In the dental adhesive composition of the present invention, there is no limitation as long as the filler is known, and the filler (F) can be blended according to the application, and preferably, a filler such as an inorganic filler, an organic filler, or an organic-inorganic composite filler is blended. When the dental adhesive composition is composed of the first paste and the second paste, the filler (F) to be blended in the first paste and the second paste may be the same or different.

The inorganic filler (F) is not particularly limited in chemical composition, and examples thereof include silica, alumina, silica-titania-barium oxide, silica-zirconia, silica-alumina, lanthanum glass, borosilicate glass, soda glass, barium glass, strontium glass, glass ceramics, aluminosilicate glass, barium boroaluminosilicate glass, strontium boroaluminosilicate glass, fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass, strontium calcium fluoroaluminosilicate glass, and strontium calcium fluoroaluminosilicate glass. In particular, barium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, and fluoroaluminosilicate glass used for dental glass ionomer cement, resin-reinforced glass ionomer cement, resin cement, and the like can also be preferably used. The fluoroaluminosilicate glass described herein has silicon oxide and aluminum oxide as basic skeletons, and contains an alkali metal for introducing non-crosslinkable oxygen. Further, there are alkali earth metals containing strontium as a modifying/coordinating ion and fluorine. In addition, in order to further impart X-ray opacity, it is a composition in which a lanthanoid element is incorporated into a skeleton. The lanthanide is incorporated into the composition according to the composition domain as a modifying/coordinating ion as well.

Examples of the organic filler of the filler (F) include polymers such as polymethyl methacrylate, polyethyl methacrylate, a methyl methacrylate-ethyl methacrylate copolymer, an ethyl methacrylate-butyl methacrylate copolymer, a methyl methacrylate-trimethylolpropane methacrylate copolymer, polyvinyl chloride, polystyrene, chlorinated polyethylene, nylon, polysulfone, polyether sulfone, and polycarbonate.

Examples of the organic-inorganic composite filler (F) include fillers obtained by pulverizing a composite of the inorganic oxide (inorganic filler) and the polymer (organic filler).

These can be used alone or in combination of two or more. The particle shape of the filler is not particularly limited, and may be a pulverized particle or a spherical particle obtained by ordinary pulverization.

The composition ratio of the filler (F) in the dental composition of the present invention is not particularly limited, and when the dental adhesive composition of the present invention is a composition comprising a base containing (a) a silane coupling agent represented by the structural formula (a) (a1), (B) a polymerizable monomer having an acid group, (C) a polymerizable monomer having no acid group, and (D) a polymerization initiator, the amount of the filler (F) is preferably 25 to 75 parts by mass, and more preferably 40 to 70 parts by mass, based on 100 parts by mass of the total amount of the dental adhesive composition. In the case where the filler is not contained, there is a risk of reduction in storage stability or reduction in adhesive strength. When the amount of the filler is less than 25 parts by mass, the durable adhesive strength may be reduced, and when the amount exceeds 75 parts by mass, the workability may be deteriorated. In this case, the matrix is preferably 25 to 75 parts by mass with respect to 100 parts by mass of the total amount of the dental adhesive composition. The average particle diameter of the filler (F) is preferably 0.001 to 100. mu.m, more preferably 0.001 to 10 μm. When the filler in the composition is composed of fine particles having a particle size of 10 μm or less, the elongation of the paste at the time of bonding is good, and when the composition is bonded to a resin for dental cutting which is composed of a glass fiber-reinforced resin, the composition easily enters between glass fibers, and therefore, good adhesive strength can be expected.

In addition, in the dental adhesive composition of the present invention, which is a two-paste type including (D1) a chemical polymerization initiator and (E) a polymerization accelerator, when 15 to 80 parts by mass of (C1) a polymerizable monomer having no acidic group and having one or more hydroxyl groups is contained per 100 parts by mass of the first and second substrates, the amount of (F) the filler is preferably 25 to 75 parts by mass, and more preferably 40 to 70 parts by mass per 100 parts by mass of the total amount of the dental composition. In the case where the (F) filler is not contained, there is a risk of reduction in storage stability or reduction in adhesive strength. If the amount of the (F) filler is less than 25 parts by mass, the durable bond strength may be reduced, and if it exceeds 75 parts by mass, the workability may be deteriorated. The average particle diameter of the filler (F) is preferably 0.001 to 100. mu.m, more preferably 0.001 to 10 μm. When the filler (F) in the composition is composed of fine particles having a particle size of 10 μm or less, the elongation of the paste at the time of bonding is good, and when the filler (F) is bonded to a resin for dental cutting which is composed of a glass fiber-reinforced resin, the composition is likely to enter between glass fibers, and therefore, a good adhesive strength can be expected.

In the case where the filler contains silica, in particular, it is preferable to use (a) a silane coupling agent containing (a1) a silane coupling agent represented by the structural formula (a) for the purpose of bonding with lithium disilicate blended in the dental composition by surface treatment so as not to react with the following substances. The dental adhesive composition of the present invention is a two-paste type comprising (D1) a chemical polymerization initiator and (E) a polymerization accelerator, and when 15 to 80 parts by mass of (C1) a polymerizable monomer having no acidic group but having one or more hydroxyl groups is contained per 100 parts by mass of the first substrate and the second substrate, it is preferable to perform a surface treatment of (C) the filler blended in the first paste using a surface treatment agent. Can inhibit long-term storage property such as reaction with silane coupling agent. The surface treatment method includes the use of a surfactant, an inorganic oxide, a silane coupling agent, an organopolysiloxane, a polymer compound such as PMMA or polyacrylic acid, or the likeA method of surface treating a molecule. From the viewpoint of affinity with the polymerizable monomer, the surface treatment is preferably performed using a silane coupling agent. Specific examples thereof include 3- (meth) acryloyloxypropyltrimethoxysilane and 8- (meth) acryloyloxyoctyltrimethoxysilane. Further, after surface treatment with these silane coupling agents, silanol groups on the filler surface may be blocked. Examples of the silane coupling agent used for the end capping include chlorotrimethylsilane, methoxytrimethylsilane and the like. The silane coupling agent described above contributes to an improvement in affinity with the polymerizable monomer, a high filling of the filler, and an improvement in mechanical strength of the polymerizable monomer. The latter silane coupling agent for capping reacts with silanol groups on the surface of the filler which have not completely reacted with the former silane coupling agent, and prevents the silane coupling agent which is added to the dental adhesive composition for the purpose of bonding with lithium silicate from reacting with the filler during long-term storage, and long-term storage stability can be expected. SiO is preferred because the filler has few points of reaction with the silane coupling agent (A) during long-term storage₂The content of (B) is small, specifically 90 w/w% or less, preferably 50 w/w% or less. In the use of SiO₂In the case of a filler having a large content, it is preferable to improve storage stability by a method of performing surface treatment with a silane coupling agent and then capping with a low-molecular silane coupling agent such as chlorotrimethylsilane or methoxytrimethylsilane or by coating with polyorganosiloxane. When the silane coupling agent and the filler are compounded without such surface treatment, the adhesive strength to the dental cutting resin is reduced after long-term storage, and the affinity between the filler and the polymerizable monomer is significantly changed, and the workability is changed due to the change in the fluidity of the paste, which is not preferable in some cases.

The surface-treated filler is 90 parts by mass or more, preferably 95 parts by mass or more, per 100 parts by mass of the filler.

Specific examples of the water (G) to be blended in the present invention include deionized water and distilled water. The amount of (G) water is preferably 1 to 50 parts by mass, more preferably 10 to 50 parts by mass, and still more preferably 25 to 35 parts by mass, based on 100 parts by mass of the total amount of the dental adhesive composition.

The volatile organic solvent (H) in the present invention has a boiling point of usually 150 ℃ or lower at normal pressure and a solubility in water at 25 ℃ of 5 mass% or higher, more preferably 30 mass% or higher, and most preferably an organic solvent soluble in water at an arbitrary ratio is used. Among them, water-soluble volatile organic solvents having a boiling point at normal pressure of 100 ℃ or lower are preferable, and specific examples thereof include ethanol, methanol, 1-propanol, isopropanol, acetone, methyl ethyl ketone, 1, 2-dimethoxyethane, 1, 2-diethoxyethane, and tetrahydrofuran. Among the volatile organic solvents, ethanol, isopropanol, acetone, and methyl ethyl ketone are more preferable.

(H) The volatile organic solvent may be used singly or in combination of two or more. The amount of the (H) volatile organic solvent is preferably 5 to 90 parts by mass, more preferably 10 to 90 parts by mass, and still more preferably 30 to 60 parts by mass, based on 100 parts by mass of the total amount of the dental adhesive composition.

In addition, in the dental adhesive composition of the present invention, known additives can be blended within a range in which the performance is not degraded. Examples of the additives include a polymerization inhibitor, an antioxidant, a pigment, a dye, an ultraviolet absorber, an organic solvent, and a thickener.

The dental adhesive composition of the present invention is a composition comprising a base containing (a) a silane coupling agent represented by the structural formula (a) (a1), (B) a polymerizable monomer having an acidic group, (C) a polymerizable monomer having no acidic group, and (D) a polymerization initiator, and when (a1) the silane coupling agent represented by the structural formula (a) has an acryloyl group, preferable embodiments include the following one-paste type dental adhesive composition and two-paste type dental adhesive composition.

Adhesive composition for dental use of the one-pack type

When the present invention is used as a one-pack type dental adhesive composition, the composition can be used as a dental filling composite resin or a dental cement. The one-pack type dental adhesive composition of the present invention is preferably used as a dental self-adhesive composite resin, particularly preferably a dental composite resin, because of less technical errors and less risk of air bubbles being mixed in. In the case of a one-pack type dental adhesive composition, the composition contains (a1) a silane coupling agent containing a silane coupling agent represented by the structural formula (a), (B) a polymerizable monomer having an acid group, (C) a polymerizable monomer having no acid group, and (D) a polymerization initiator. Further preferably contains (F) a filler, (D2) a photopolymerization initiator, and (E) a polymerization accelerator. When the silane coupling agent represented by the structural formula (a) (a1) having an acryloyl group is used, particularly, a smaller amount of the silane coupling agent can be blended as compared with the case of using a conventional silane coupling agent having a methacryloyl group, whereby a good adhesive strength with a lithium disilicate-containing glass ceramic can be expected.

Adhesive composition for dental use of the double-paste type

When the present invention is used for a two-paste type dental adhesive composition, the composition can be used as a dental filling composite resin or a dental cement. It is used by kneading two materials classified into a first paste and a second paste immediately before use. The mixing ratio of the first paste to the second paste is preferably 1: 0.8 to 1.2, and more preferably 1: 1. the mass ratio of the components is preferably 1: 0.8 to 1.2, and more preferably 1: 1. the double-paste type dental adhesive composition of the present invention is preferably used as a dental cement, preferably a dental self-adhesive resin cement. In the case of a two-paste type dental adhesive composition, the composition contains (a1) a silane coupling agent containing a silane coupling agent represented by the structural formula (a), (B) a polymerizable monomer having an acid group, (C) a polymerizable monomer having no acid group, and (D) a polymerization initiator. Further preferably contains (F) a filler, (D1) a chemical polymerization initiator, and (E) a polymerization accelerator. When the silane coupling agent represented by the structural formula (a) (a1) having an acryloyl group is used, particularly, a smaller amount of the silane coupling agent can be blended as compared with the case of using a conventional silane coupling agent having a methacryloyl group, whereby a good adhesive strength with a lithium disilicate-containing glass ceramic can be expected.

In this case, the dental adhesive composition of the present invention may be composed of a first paste and a second paste. In this case, for example, the first paste may include (F) a filler and (a) a first base, and the first base may include (a) a silane coupling agent containing (a1) a silane coupling agent represented by structural formula (a), and (C) a polymerizable monomer having no acidic group. The second paste may include (F) a filler and a second matrix, and the second matrix may include (B) a polymerizable monomer having an acid group and (C) a polymerizable monomer having no acid group. The first matrix and the second matrix contain at least one of (D1) a chemical polymerization initiator and (E) a polymerization accelerator, and in the case where the first matrix contains one or more (D1) chemical polymerization initiators, the second matrix contains one or more (E) polymerization accelerators, and in the case where the first matrix contains one or more (E) polymerization accelerators, the second matrix contains one or more (D1) chemical polymerization initiators. In this case, the dental adhesive composition can contain substantially no water.

The dental adhesive composition of the present invention can comprise a matrix containing (a) a silane coupling agent containing (a1) a silane coupling agent represented by the structural formula (a), (B) a polymerizable monomer having an acid group, (C) a polymerizable monomer having no acid group, and (D) a polymerization initiator, and (F) a filler.

Specifically, the matrix included in the dental adhesive composition may be 25 to 75 parts by mass with respect to 100 parts by mass of the dental adhesive composition, and the filler (F) included in the dental adhesive composition may be 25 to 75 parts by mass with respect to 100 parts by mass of the dental adhesive composition.

The dental adhesive composition of the present invention is a two-paste type comprising (D1) a chemical polymerization initiator and (E) a polymerization accelerator, and when 15 to 80 parts by mass of a (C1) polymerizable monomer having no acidic group and having one or more hydroxyl groups is contained per 100 parts by mass of the first substrate and the second substrate, the mixing ratio of the first paste to the second paste is preferably 1: 0.8 to 1.2, and more preferably 1: 1. the mass ratio of the components is preferably 1: 0.8 to 1.2, and more preferably 1: 1.

in this case, the first base of the first paste may be 25 to 75 parts by mass with respect to 100 parts by mass of the first paste, the filler (F) of the first paste may be 25 to 75 parts by mass with respect to 100 parts by mass of the first paste, and the polymerizable monomer (B) having no acidic group of the first base may be 65 to 98 parts by mass with respect to 100 parts by mass of the first base.

In this case, the second matrix of the second paste may be 25 to 75 parts by mass with respect to 100 parts by mass of the second paste, and the filler (F) of the second paste may be 25 to 75 parts by mass with respect to 100 parts by mass of the second paste.

The dental adhesive composition of the present invention is preferably used in an amount of 25 to 75 parts by mass of the base per 100 parts by mass of the dental adhesive composition, and the dental adhesive composition contains 25 to 75 parts by mass of the (F) filler per 100 parts by mass of the dental adhesive composition, regardless of whether the dental adhesive composition is of a one-paste type or a two-paste type. With such a blending amount, the dental adhesive composition can be expected to have good durability due to appropriate fluidity and sufficient mechanical strength. When the matrix contained in the dental adhesive composition is less than 25 parts by mass per 100 parts by mass of the dental adhesive composition, the proportion of the filler is large, and thus the dental adhesive composition does not have appropriate fluidity, and when the proportion exceeds 75 parts by mass, the strength may not be sufficiently improved. Depending on the type of filler, high fluidity may occur even when the amount of filler filled in the composition is large, or high strength may be expressed even when the amount of filler filled is small.

The double-paste dental adhesive composition of the present invention can be used for adhesion to a dental cutting repair material. The dental cutting repair material can be, for example, a glass fiber reinforced material containing glass fibers and epoxy resin. In this case, the glass fibers may be randomly aligned in different directions. Alternatively, the glass fiber laminated body may be a laminated body in which glass fibers are cross-woven, that is, a material having a cross-woven surface and a surface in which the woven surface is rotated by 90 ° in the vertical direction.

The dental cutting repair material can have two or more different structures of the adhered surface.

The dental adhesive composition of the present invention is a preferred embodiment in the case of a composition containing (a) a silane coupling agent containing (a1) a silane coupling agent represented by the structural formula (a), (B) a polymerizable monomer having an acid group, (C) a polymerizable monomer having no acid group, (H) a volatile organic solvent, and (G) water, and further containing either or both of (D) a polymerization initiator and (E) a polymerization accelerator, and examples thereof include dental adhesives, dental primers, metallic primers, and ceramic primers. In addition, in each application, the dental adhesive composition of the present invention may be used as a two-part composition by dividing the components into two parts. The following shows a specific embodiment of applying the dental adhesive composition.

< dental adhesive Material >

When the present invention is used as a dental adhesive, there may be mentioned a two-liquid mixing one-step type in which two reagents, i.e., a first liquid and a second liquid, are mixed immediately before use and used, and a two-liquid two-step type in which the second liquid is applied after the first liquid is applied, and a one-liquid one-step type in which one reagent can be used as it is. Among these, the one-liquid one-step type is more preferable because the operation is simple and easy and a technical error is not easily generated at the time of use. In the case of the one-liquid one-step type, the composition contains (a) a silane coupling agent containing (a1) a silane coupling agent represented by the structural formula (a), (B) a polymerizable monomer having an acid group, (C) a polymerizable monomer having no acid group, (D) a polymerization initiator and/or (E) a polymerization accelerator, (H) a volatile organic solvent, and (G) water. When a dental adhesive composition of a one-liquid one-step type is prepared according to the index of the amount of silane coupling agent blended in the composition of the present invention, good storage stability can be expected. In addition, when a silane coupling agent having an acryloyl group is used as the silane coupling agent represented by the structural formula (a1), it can be expected that the adhesive strength to a glass ceramic such as a lithium disilicate-containing glass ceramic and an inorganic component-containing composite resin is more excellent than the case of using a conventional silane coupling agent having a methacryloyl group.

Primer for dentine

The primer for dentin is used to improve the bonding strength of the cement when the cement is bonded to the dentin by modifying the surface of the dentin. When the present invention is used as a primer for dentin, there may be mentioned a two-liquid mixing one-step type in which two reagents divided into a first liquid and a second liquid are mixed immediately before use and used, a two-liquid two-step type in which the second liquid is applied after the first liquid is applied, and a one-liquid one-step type in which one reagent can be used as it is. Among these, the one-liquid one-step type is more preferable because the operation is simple and easy and a technical error is not easily generated at the time of use. In the case of the one-liquid one-step type, the composition contains (a) a silane coupling agent, (B) a polymerizable monomer having an acid group, (C) a polymerizable monomer having no acid group, (D) a polymerization initiator and/or (E) a polymerization accelerator, (H) a volatile organic solvent, and (G) water. More preferably, the primer for dentin to be coated contains (D) a polymerization initiator and/or (E) a polymerization accelerator for accelerating interfacial polymerization of a material (for example, resin cement or the like) to be coated on the primer for dentin to be coated.

< primer for metal >

The primer for metal is used for modifying the surface of noble metals and non-noble metals when bonding noble metals and non-noble metals, so as to improve the bonding strength when bonding an abutment with a patch device composed of metal and non-noble metals by using a cement.

When the present invention is used as a primer for dentin, there may be mentioned a two-liquid mixing one-step type in which two reagents divided into a first liquid and a second liquid are mixed immediately before use and used, a two-liquid two-step type in which the second liquid is applied after the first liquid is applied, and a one-liquid one-step type in which one reagent can be used as it is. Among these, the one-liquid one-step type is more preferable because the operation is simple and easy and a technical error is not easily generated at the time of use. In the case of the one-liquid one-step type, the composition contains (a) a silane coupling agent containing (a1) a silane coupling agent represented by the structural formula (a), (B) a polymerizable monomer having an acid group, (C) a polymerizable monomer having no acid group, (D) a polymerization initiator and/or (E) a polymerization accelerator, (H) a volatile organic solvent, and (G) water.

< primer for ceramics >

The primer for ceramics is used for modifying the surface of ceramics such as zirconia and alumina and glass ceramics made of feldspar or lithium disilicate to improve the bonding strength when the abutment is bonded to a prosthetic device made of ceramics and glass ceramics using cement. When the present invention is used for a primer for ceramics, there is a two-liquid mixing one-step type in which two reagents, i.e., a first liquid and a second liquid, are mixed and used immediately before use, and a one-liquid one-step type in which one reagent can be used as it is. Among these, the one-liquid one-step type is more preferable because the operation is simple and easy and a technical error is not easily generated at the time of use. In the case of the one-liquid one-step type, the composition contains (a) a silane coupling agent containing (a1) a silane coupling agent represented by the structural formula (a), (B) a polymerizable monomer having an acid group, (C) a polymerizable monomer having no acid group, (D) a polymerization initiator and/or (E) a polymerization accelerator, (H) a volatile organic solvent, and (G) water. When a dental adhesive composition of a one-liquid one-step type is prepared according to the index of the amount of silane coupling agent blended in the composition of the present invention, good storage stability can be expected. In addition, when a silane coupling agent having an acryloyl group is used as the silane coupling agent represented by the structural formula (a1), it can be expected that the adhesive strength to a glass ceramic such as a lithium disilicate-containing glass ceramic and an inorganic component-containing composite resin is more excellent than the case of using a conventional silane coupling agent having a methacryloyl group.

The method for producing the dental adhesive composition of the present invention is not particularly limited, and the dental adhesive composition can be produced by mixing the respective components. Preferably, the composition can be produced by mixing (B) the polymerizable monomer having an acid group, (C) the polymerizable monomer having no acid group, (H) a volatile organic solvent to obtain a uniform solution, and then adding (a) the silane coupling agent containing (a1) the silane coupling agent represented by the structural formula (a), (D) the polymerization initiator and/or (E) the polymerization accelerator, and (G) water. When the polymerizable monomer (B) having an acidic group is brought into contact with the silane coupling agent (a) containing the silane coupling agent (a) represented by the structural formula (a) (a1) and the polymerization initiator (D) at the time of metering, the silane coupling agent (a) containing the silane coupling agent (a) represented by the structural formula (a) (a1) and the polymerization initiator (D) may be decomposed, and the production time may be shortened by mixing water (G) at the rear end.

[ examples ]

The present invention will be described in detail below by way of examples and comparative examples, but the present invention is not limited to these examples. Abbreviations used below are as follows. The proportions of the components in the examples and comparative examples are shown in parts by mass in the table.

[ (A) silane coupling agent ]

OTES: n-octyl triethoxysilane.

MTTSP: 3- [ tris (trimethylsiloxy) silyl ] propyl methacrylate.

AAPTMS: 3-acrylamidopropyl trimethoxysilane.

MAPTMS: 3-methacrylamide propyl triethoxysilane.

< (A1) the silane coupling agent represented by the formula (a)

(silane coupling agent having acryloyl group)

APTMS: acryloylpropyltrimethoxysilane.

APMES: acrylopropylmethyldiethoxysilane.

APMMS: acryloylpropylmethyldimethoxysilane.

APDMS: acryloylpropyldimethylmethoxysilane.

C11A: 4, 4-diethoxy-17-oxo-3, 16-dioxa-18-aza-4-silaeicosan-20-yl acrylate.

C11 DA: 2-methyl-2- ((((11- (triethoxysilyl) undecyl) oxy) carbonyl) amino) propane-1, 3-diyl diacrylate.

(silane coupling agent having a methacrylic group (having no acryloyl group))

MPTMS: methacryloxypropyltrimethoxysilane.

MOTMS: methacryloyl octyl trimethoxysilane.

MPTBS: methacryloxypropyltributoxysilane.

C11 EG: 4, 4-diethoxy-17-oxo-3, 16, 21-trioxa-18-aza-4-silaeicosatrien-23-yl methacrylate.

[ (B) polymerizable monomer having acidic group ]

MDP: 10-methacryloyloxydecyl dihydrogen phosphate.

MHPA: (6-methacryloyloxy) hexyl phosphonoacetate.

META: 4- [ (2-methacryloyloxyethoxy) carbonyl ] phthalic anhydride.

MET: 4-methacryloyloxyethyl trimellitic acid.

[ (C) polymerizable monomer having no acidic group ]

< (C11) Low-viscosity polymerizable monomer having no acidic group but one or more hydroxyl groups

GDMA: glycerol dimethacrylate (35 mPas) (having a methacrylic group and/or a methacrylamide group) (number of polymerizable groups: 2).

HEMA: 2-hydroxyethyl methacrylate (8 mPas) (having a methacrylic group and/or a methacrylamide group) (number of polymerizable groups: 1).

HPPA: 2-hydroxy-3-phenoxypropyl acrylate (200 mPas) (having no methacrylic group and/or methacrylamide group) (number of polymerizable groups: 1).

< (C1) polymerizable monomer having no acidic group but one or more hydroxyl groups

BisGMA: 2, 2-bis [4- (3- (meth) acryloyloxy) -2-hydroxypropoxyphenyl ] propane: the viscosity (number of polymerizable groups: 2) could not be measured at 25 ℃.

PENTA: pentaerythritol triacrylate: 800 mPas (number of polymerizable groups: 3).

< polymerizable monomer having no acidic group and no hydroxyl group >

UDMA: 2,2, 4-trimethylhexamethylenebis (2-carbamoyloxyethyl) dimethacrylate (number of polymerizable groups: 2).

3G: triethylene glycol dimethacrylate (number of polymerizable groups: 2).

NPG: neopentyl glycol dimethacrylate (number of polymerizable groups: 2).

D2.6E: 2, 2-bis (4-methacryloxypolyethoxyphenyl) propane (number of polymerizable groups: 2) having an average molar number of addition of ethoxy groups of 2.6.

A3.0E: diacrylate (having no methacryloyl group and no methacrylamido group) as an EO addition product of bisphenol A having an average addition mole number of ethoxy groups of 3 (number of polymerizable groups: 2).

DMCDA: dimethylol-tricyclodecane diacrylate (having no methacryloyl group and no methacrylamido group) (number of polymerizable groups: 2).

TMPTA: trimethylolpropane triacrylate (having no methacryloyl group and methacrylamido group) (number of polymerizable groups: 3).

EBAA: n, N' -ethylene bisacrylamide (having no methacryl group and no methacrylamido group) (number of polymerizable groups: 2).

MBMA: n, N' -methylenebismethacrylamide (having a methacrylamide group) (number of polymerizable groups: 2).

(method of measuring viscosity)

250g of a polymerizable monomer was taken out into 260mL of a wide-mouth glass bottle, and the bottle was left to stand at 25. + -. 3 ℃ for 24 hours while being shielded from light with an aluminum foil. Thereafter, the polymerizable monomer collected in the jar was measured for viscosity at 25 ℃. + -. 3 ℃ using a B-type viscometer.

[ (D) polymerization initiator ]

< (D1) chemical polymerization initiator

CHP: cumene hydroperoxide.

TMBH: 1,1,3,3, -tetramethylbutyl hydroperoxide.

BPO: benzoyl peroxide.

< (D2) photopolymerization initiator

CQ: camphorquinone.

[ (E) polymerization Accelerator ]

DMBE: 4- (dimethylamino) benzoic acid ethyl ester.

DEPT: n, N-bis (2-hydroxyethyl) p-toluidine.

PTSA: sodium p-toluenesulfinate.

BTU (BTU): n-benzoylthiourea.

PTU: n-pyridylthiourea.

COA: copper acetylacetonate.

VOA: vanadyl acetylacetonate.

GLC: copper gluconate.

[ (F) Filler ]

The following raw material glasses were used for fillers a to C.

And (3) filler A: silica Filler (SiO)₂: about 99.5 mass%, and the balance other inorganic components, average particle diameter: 0.8 μm).

And (3) filling material B: silica zirconia filler (SiO)₂: about 80 mass% of ZrO₂: about 20 mass%, and the balance of other inorganic components, average particle diameter: 1.0 μm).

And (3) filler C: fluoroaluminosilicate (SiO)₂: about 45 mass% of Al₂O₃: about 22 mass%, SrO: about 20% by massF: about 8 mass%, P₂O₅: about 5 mass%, average particle diameter: 1.2 μm).

Fillers D to I were produced as follows.

And (3) filling material D: 100.0g of filler A was added with a silane coupling treatment solution obtained by stirring 100.0g of water, 80.0g of ethanol, 0.003g of phosphoric acid, and 3.0g of 3-methacryloxypropyltrimethoxysilane as a silane coupling agent at room temperature for 2 hours, and the mixture was stirred and mixed for 30 minutes. Thereafter, heat treatment was carried out at 100 ℃ for 15 hours, and screening was carried out to obtain filler D.

And (3) filler E: 100.0g of filler B was added with a silane coupling treatment solution obtained by stirring 100.0g of water, 80.0g of ethanol, 0.003g of phosphoric acid, and 3.0g of 3-methacryloxypropyltrimethoxysilane as a silane coupling agent at room temperature for 2 hours, and the mixture was stirred and mixed for 30 minutes. Thereafter, heat treatment was carried out at 100 ℃ for 15 hours, and screening was carried out to obtain filler E.

And (3) filling material F: 100.0g of filler C was added with a silane coupling treatment solution obtained by stirring 100.0g of water, 80.0g of ethanol, 0.003g of phosphoric acid, and 3.0g of 3-methacryloxypropyltrimethoxysilane as a silane coupling agent at room temperature for 2 hours, and the mixture was stirred and mixed for 30 minutes. Thereafter, heat treatment was carried out at 100 ℃ for 15 hours, and a filler F was obtained after sieving.

And (3) filler G: 10.8g of polyorganosiloxane "MKC Silicate MS 51" (MKC Silicate MS51, Mitsubishi chemical corporation) was added to 100.0g of the raw material glass A, and the mixture was stirred and mixed for about 90 minutes. Thereafter, the obtained treated slurry was left in a hot air dryer at 50 ℃ for 40 hours, and then heated to 150 ℃ and left for 6 hours. The obtained heat-treated product was placed in a Henschel mixer and crushed at 1800rpm for 5 minutes. Filler G was obtained by sieving after crushing.

And (3) packing H: 10.8g of polyorganosiloxane "MKC Silicate MS 51" (MKC Silicate MS51, Mitsubishi chemical corporation) was added to 100.0g of the raw material glass B, and the mixture was stirred and mixed for about 90 minutes. Thereafter, the obtained treated slurry was left in a hot air dryer at 50 ℃ for 40 hours, and then heated to 150 ℃ and left for 6 hours. The obtained heat-treated product was placed in a Henschel mixer and crushed at 1800rpm for 5 minutes. Filler H was obtained by sieving after crushing.

And (3) filler I: 100.0g of glass A was added with a silane coupling treatment solution obtained by stirring 100.0g of water, 80.0g of ethanol, 0.003g of phosphoric acid, and 3.0g of 3-methacryloxypropyltrimethoxysilane as a silane coupling agent at room temperature for 2 hours, and the mixture was stirred and mixed for 30 minutes. Thereafter, heat treatment was performed at 100 ℃ for 15 hours, and after sieving, a silane coupling treatment liquid obtained by stirring 100.0g of water, 80.0g of ethanol, 0.003g of phosphoric acid, and 3.0g of methoxytrimethylsilane as a silane coupling agent at room temperature for 2 hours was added, and mixed with stirring for 5 hours. Thereafter, heat treatment was carried out at 100 ℃ for 15 hours, and filler I was obtained after sieving.

[ (G) Water ]

D.W.: and (4) distilled water.

[ (H) volatile organic solvent ]

Acetone: acetone.

EtOH: and (3) ethanol.

[ (I) polymerizable monomer having one or more sulfur atoms ]

MDDT: 10-methacryloyloxydecyl-6, 8-dithiooctyl ester (polymerizable monomer having one or more sulfur atoms).

[ others ]

BHT: 2, 6-di-tert-butyl-4-methylphenol.

[ dental adhesive composition comprising a base comprising (A) a silane coupling agent, (B) a polymerizable monomer having an acid group, (C) a polymerizable monomer having no acid group, and (D) a polymerization initiator ]

(method for producing paste)

The polymerizable monomers shown in examples and comparative examples were charged into a light-shielding plastic container, mixed for 48 hours at 100rpm using a mixing rotor VMRC-5, then a polymerization initiator was added, and further mixed for 48 hours at 100rpm using the mixing rotor VMRC-5 to obtain a resin liquid. The resin liquid and the filler were put into a kneading vessel and kneaded for 20 minutes at 1000rpm using a revolution-and-rotation mixer ARV-300 to obtain a dental adhesive composition or a first paste and a second paste.

The test methods for each characteristic evaluated in examples and comparative examples are as follows. The two-paste type dental adhesive composition is prepared by weighing the first paste and the second paste in a dark room at 23 ± 2 ℃ using an electronic balance and mixing them under conditions of equal mass. In a volume ratio of 1.0: 0.8 to 1.2, preferably 1.0: in the case of 0.9 to 1.1, the same results were obtained even when the test was carried out using a stirring tip (Mixing tip) manufactured by Mixpack, ミックスパック.

(preparation of preliminary product and accelerated test product)

The prepared paste is filled into each container, and the storage time is less than 3 months under the condition of the storage temperature of 1-30 ℃, so that the paste is called as a preparation initial product. The prepared paste was filled in each container, and stored at a set temperature of 40 ℃ for 3 months using a constant temperature thermostat (manufactured by Otsuka corporation, ヤマト science corporation), which is referred to as an accelerated test sample. The dental adhesive composition of one-paste type was filled in a 3mL syringe made of polypropylene, and the first paste and the second paste of the dental adhesive composition of two-paste type were filled in one syringe of a two-syringe made by mixing packaging company.

(adhesive Strength of Single-paste type dental adhesive composition)

The adhesive strength of the single-paste type dental adhesive composition was measured by the following method.

< adhesion strength to dentine >

Test pieces of bovine anterior teeth embedded with epoxy resin were ground using water-resistant grinding paper #600, and the dentin plane was shaved. A perforated double-sided tape having a diameter of 4mm was attached to the surface of the dentin to define an adhesive area, a plastic mold having an inner diameter of 4mm and a height of 1mm was fixed to the perforated double-sided tape, and the dental adhesive composition of examples or comparative examples was filled therein, followed by irradiation with light for 10 seconds using a dental polymerization LED illuminator (Pen Bright (ペンブライト), manufactured by Song Corp.). After the prepared adhesion test piece was immersed in water at 37 ℃ for 24 hours, the cold water phase at 4 ℃ and the high temperature phase at 60 ℃ were immersed for 60 seconds 1 time and repeated 5000 times using a thermal shock tester (manufactured by Tomasco instruments, トーマス scientific instruments). After the test piece was taken out, the shear adhesion strength was measured at a crosshead speed of 1mm/min using a universal tester (available from Instron corporation, インストロン). When the adhesive strength was 10MPa or more, it was judged that the adhesive strength was excellent. On the other hand, when the pressure is less than 5MPa, the adhesive strength is judged to be low.

< adhesion Strength to glass-ceramics containing lithium disilicate >

An adherend (15 mm in diameter and 3mm in thickness) was produced by firing a lithium disilicate-containing glass ceramic (VINTAGE PRIME PRESS (ヴィンテージ PRIME プレス), color tone E-1, pine wind) under conditions specified by the manufacturer, and the surface of the adherend was polished with water-resistant polishing paper # 600. Thereafter, the surface to be adhered of the sheet to be adhered was subjected to blast treatment (0.2MPa, 1 second) with alumina (50 μm) → water washing and drying. A perforated double-sided tape having a diameter of 4mm was attached to the surface to be adhered, a plastic mold having an inner diameter of 4mm and a height of 1mm was fixed to the perforated double-sided tape so as to have a predetermined adhesion area, the dental adhesive composition of examples or comparative examples was filled in the adhesive tape, and then light irradiation was performed for 10 seconds using a dental polymerization LED light irradiation device (Pen Bright, open air). After the prepared adhesion test piece was immersed in water at 37 ℃ for 24 hours, the immersion was repeated 5000 times for 1 time in each of a cold water phase at 4 ℃ and a high temperature phase at 60 ℃ for 60 seconds using a thermal shock tester (manufactured by Tomasco instruments Co., Ltd.). After the test piece was taken out, the shear adhesion strength was measured at a crosshead speed of 1mm/min using a universal tester (available from Instron). When the adhesive strength was 15MPa or more, it was judged that the adhesive strength was excellent. On the other hand, when the pressure is less than 10MPa, the adhesive strength is judged to be low.

(adhesive Strength of double-paste type dental adhesive composition)

The adhesive strength of the two-paste type dental adhesive composition was measured by the following method.

< adhesion strength to dentine >

Test pieces of bovine anterior teeth embedded with epoxy were ground using water-resistant paper #600 and the enamel or dentin planes were shaved. Thereafter, a perforated tape having a diameter of 4mm was attached to the surface to be adhered so as to define an adhesion area. On the other hand, the surface of the stainless steel rod (4.5 mm) to be adhered was subjected to sand blasting (0.2MPa, 1 second) with alumina (50 μm) to water washing and drying, and a metallic adhesive primer (Metal Link (メタルリンク), pine wind system) was applied. After the first paste and the second paste corresponding to the dental adhesive composition of the examples or comparative examples were sufficiently kneaded in equal mass, an appropriate amount of the paste was applied to the surface to be adhered of the stainless steel rod, and the lithium disilicate-containing glass ceramic was joined to the stainless steel rod so as to be accommodated in the frame of the holed double-sided tape. A 200N load was applied from the vertical direction of the stainless steel bar and the remaining water clock was wiped off with a cloth. Thereafter, the adhesive test piece prepared by removing the load was exposed to light for 10 seconds using an LED light irradiator for dental polymerization (Pen Bright, manufactured by Songfeng), immersed in water at 37 ℃ for 24 hours, and then immersed in a cold water phase at 4 ℃ and a high temperature phase at 60 ℃ for 60 seconds each for 1 time using a thermal shock tester (manufactured by Tomasco instruments) and repeated 5000 times. After the test piece was taken out, the tensile bond strength was measured at a crosshead speed of 1mm/min using a universal tester (available from Instron). When the adhesive strength was 10MPa or more, it was judged that the adhesive strength was excellent. On the other hand, when the pressure is less than 5MPa, the adhesive strength is judged to be low.

< adhesion Strength to glass-ceramics containing lithium disilicate >

An adherend (diameter 15mm, thickness 3mm) was produced by firing a lithium disilicate-containing glass ceramic (VINTAGE PRIME PRESS, color tone E-1, pine wind) under conditions specified by the manufacturer, and the surface of the adherend was polished with water-resistant polishing paper # 600. Thereafter, the surface to be adhered of the sheet to be adhered was subjected to blast treatment (0.2MPa, 1 second) with alumina (50 μm) → water washing and drying. A perforated tape having a diameter of 4mm was attached to the adherend surface to define the adhesion area. On the other hand, the surface of the stainless steel rod (4.5 mm) to be adhered was subjected to sand blasting (0.2MPa, 1 second) with alumina (50 μm) to water washing and drying, and a Metal Link (open air) was applied. After the first paste and the second paste corresponding to the dental adhesive composition of the examples or comparative examples were sufficiently kneaded in equal mass, an appropriate amount of the paste was applied to the surface to be adhered of the stainless steel rod, and the lithium disilicate-containing glass ceramic was joined to the stainless steel rod so as to be accommodated in the frame of the holed double-sided tape. A 200N load was applied from the vertical direction of the stainless steel bar and the remaining water clock was wiped off with a cloth. Thereafter, the adhesive test piece prepared by removing the load was immersed in water at 37 ℃ for 24 hours by irradiating with an LED light irradiator for dental polymerization (Pen Bright, pine wind) for 10 seconds, and then immersed in a cold aqueous phase at 4 ℃ and a high temperature phase at 60 ℃ for 60 seconds by a thermal shock tester (Tomasco instruments) for 1 time, and the process was repeated 5000 times. After the test piece was taken out, the tensile bond strength was measured at a crosshead speed of 1mm/min using a universal tester (available from Instron). When the adhesive strength was 15MPa or more, it was judged that the adhesive strength was excellent. On the other hand, when the pressure is less than 10MPa, the adhesive strength is judged to be low.

(resistance to staining)

In the case of the one-paste type dental adhesive composition, a needle tip was attached, and in the case of the two-paste type dental adhesive composition, after the first paste and the second paste were sufficiently kneaded in equal mass, the pastes were collected into a mold having a thickness of 1.0mm and an inner diameter of 15mm while paying attention to prevention of entry of air bubbles, both sides were pressed with a cover glass, and both sides were irradiated with light for 60 seconds using a dental polymerization LED light irradiator (Pen Bright) to produce a disc-shaped cured body having a thickness of 1.0 mm. The cured body was polished with water-resistant polishing paper #600, followed by polishing with water-resistant polishing paper #1200, and then polishing with water-resistant polishing paper #2000 to adjust the surface to be smooth. Next, the cured product was immersed in a10 mL plastic container containing 5mL of distilled water at 37 ℃ for 1 day. The cured product was taken out, sufficiently wiped off, and then subjected to color measurement under SCE and white background using a spectrophotometer (CM-26d, manufactured by Konika Meinenda Co., Ltd. (コニカミノルタ)). Thereafter, the resulting cured product was immersed in a10 mL plastic container containing 5mL of a 0.1% aqueous solution of rhodamine at 37 ℃ for 1 day, washed twice with distilled water, and after sufficiently wiping off water from the cured product, color measurement was performed under SCE and white background conditions using a spectrophotometer (CM-26 d: manufactured by Konikamebendazole). The color difference Δ E was calculated from the results of measurement before and after immersion in a 0.1% aqueous solution of rhodamine, and it was judged that A was the case where Δ E was less than 30, B was the case where Δ E was 30 to 45, and C was the case where Δ E was 45 or more. In the case of C, it is judged that the coloring resistance is poor.

(Properties)

In the case of the one-paste type dental adhesive composition, the needle tip was attached, and in the case of the two-paste type dental adhesive composition, 0.1g of the first paste and the second paste were sufficiently kneaded in equal mass, and then left on a glass slide, and the left position was marked with a sticker. Thereafter, the slide was tilted by 90 °, and after 20 seconds, the slide was restored, and the distance traveled by the paste was measured. Between the paste immediately after preparation and the paste after 3 months of storage at 40 ℃, the moving distance of the paste increases or decreases by less than 10% and is denoted as A, 10-40% as B, and more than 40% as C. In the case of C, the stability of the properties was judged to be poor.

Since examples a1 to a18 and examples B1 to B22 contain (a1) the silane coupling agent represented by the structural formula (a) in the matrix and the total index of the amount of the silane coupling agent incorporated in the matrix satisfies formula (1), the glass ceramic containing lithium disilicate has excellent durable adhesion and excellent discoloration resistance.

Although examples a5, a10, B14, B15, B16, B17, and B19 satisfied formula (1), since the sum of the indices of the amount of silane coupling agent blended in the matrix was in the vicinity of the upper limit of formula (1), it was confirmed that the adhesion strength of the accelerated test product to the glass ceramic containing lithium disilicate was lower than that of the initial product, the adhesion strength of the subject dentin was reduced, and the discoloration resistance was reduced.

Although examples a16, a17, B11, B12 and B13 satisfy formula (1), since the total of the indexes of the amount of the silane coupling agent blended in the matrix is the blending amount in the vicinity of the lower limit of formula (1), it was confirmed that the adhesive strength to the lithium disilicate-containing glass ceramic was slightly decreased although the adhesive strength to the lithium disilicate-containing glass ceramic was 10MPa or more.

Since the blending amount of the polymerizable monomer having not only an acidic group but also one or more hydroxyl groups contained in the matrix blended with the silane coupling agent in examples B1, B2, B5, B15, B16, B19, a12, a13, and a15 exceeded 60%, it was confirmed that the adhesion strength of the accelerated test product to the glass ceramic containing lithium disilicate was lower than that of the initial product. In particular, it is significant in more than 70% of examples 12A and B5.

Since the amount of the polymerizable monomer having one or more hydroxyl groups and not having an acidic group contained in the matrix in which the silane coupling agent was blended was less than 5% in examples A8, a14 and B20, it was confirmed that the adhesive strength was slightly decreased although the adhesive strength to the lithium disilicate-containing glass ceramic was 10MPa or more.

Since the amount of the polymerizable monomer having a methacryloyl group contained in the matrix was less than 70% in examples a7, a11, a14, B8, B9, B12, B17, and B18, it was confirmed that the adhesive strength was slightly decreased although the adhesive strength to the lithium disilicate-containing glass ceramic was 10MPa or more. In particular, it is significant in less than 50% of examples a11, a14, B17, B18.

Containing SiO₂Filler D in which the silica filler having a content of 99% or more was treated with a silane coupling agent, and examples a13, B8, and B15 in which a silane coupling agent having an acryloyl group was contained in the matrix, were confirmed to be within acceptable ranges although the paste fluidity tended to be slightly improved after the accelerated test.

Examples a9, a10, B21 and B22 containing the filler a and the filler B which were not treated with a silane coupling agent and containing a silane coupling agent in the matrix, although the adhesion strength to the lithium disilicate-containing glass ceramic was 10MPa or more after the accelerated test, it was confirmed that the adhesion strength was slightly decreased, the fluidity of the paste was improved and the handling feeling was deteriorated.

Since the total of the index of the amount of the silane coupling agent blended in the matrix exceeds the upper limit of the formula (1) in the amounts blended in comparative examples A1, A2, CB3 and CB4, the adhesion strength of the test article to the glass ceramic containing lithium disilicate is accelerated to 10MPa or less, and the adhesion strength of the target dentin is also decreased. In addition, a decrease in the coloring resistance is also caused.

Since the total of the amounts of the silane coupling agents blended in the matrix in comparative examples CA3, CA4, CB1 and CB2 is less than the lower limit of formula (1), the adhesion strength to a glass ceramic containing lithium disilicate is as low as 10MPa or less.

Comparative examples CA5, CA6, CA8, and CA10 are compositions in which the total of the indices of the amount of silane coupling agent incorporated in the matrix exceeds the upper limit of formula (1), and a conventional silane coupling agent having a methacryloyl group is incorporated in the matrix. Although the adhesion strength of the initial product to the lithium disilicate-containing glass ceramic is 10MPa or more, the adhesion strength of the test product to the lithium disilicate-containing glass ceramic tends to be accelerated to be 10MPa or less, and the adhesion strength of the target dentin tends to be low. Further, the coloring resistance tends to be low.

Comparative examples CA10, CA11, CB5 and CB6 do not contain a polymerizable monomer having an acid group, and thus tend to have low adhesive strength to the dentin of a subject.

Comparative examples CA1, CA5 and CB3 contain SiO₂A composition comprising filler D treated with a silane coupling agent and a silica filler having a content of 99% or more, wherein the silane coupling agent is contained in an amount such that the sum of the indices of the amount of the silane coupling agent incorporated in the matrix exceeds the upper limit of formula (1). It was confirmed that the paste fluidity was significantly improved after the accelerated test, and the stability of the properties was poor.

[ two-paste type adhesive composition for dental use comprising (D1) a chemical polymerization initiator and (E) a polymerization accelerator, wherein the adhesive composition for dental use comprises (C1) 15 to 80 parts by mass of a polymerizable monomer having no acidic group but having one or more hydroxyl groups per 100 parts by mass of a first substrate and a second substrate ]

(method for producing paste)

The polymerizable monomers shown in examples and comparative examples were charged into a light-shielding plastic container, mixed for 48 hours at 100rpm using a mixing rotor VMRC-5, then a polymerization initiator was added, and further mixed for 48 hours at 100rpm using the mixing rotor VMRC-5 to obtain a resin liquid. The resin liquid and the filler were put into a mixing vessel and mixed for 20 minutes at 1000rpm using a revolution-rotation mixer ARV-300 to obtain a first paste and a second paste.

The test methods for each characteristic evaluated in examples and comparative examples are as follows. The first paste and the second paste were weighed in a dark room at 23 ± 2 ℃ using an electronic balance, and mixed under conditions of equal mass. In a volume ratio of 1.0: 0.8 to 1.2, preferably 1.0: in the case of 0.9 to 1.1, the same results were obtained even when the test was carried out using a mixing tip (mixing tip) manufactured by mix packaging company (Mixpack).

(preparation of preliminary product and accelerated test product)

The compositions described in examples and comparative examples were filled into a 5mL double syringe manufactured by MIXED PACKAGE, and stored at 40 ℃ for 4 months using a constant temperature thermostat (manufactured by Daihu scientific Co., Ltd.), and they were referred to as accelerated test samples. In contrast, the initial product of the preparation means that the product is used within 3 months at 1 to 30 ℃ after the preparation.

(adhesion strength to dentine)

Test pieces of bovine anterior teeth embedded with epoxy resin were ground using water-resistant grinding paper #600, and the dentin plane was shaved. Thereafter, a perforated tape having a diameter of 4mm was attached to the surface to be adhered so as to define an adhesion area. On the other hand, the surface of the stainless steel rod (4.5 mm) to be adhered was subjected to sand blasting (0.2MPa, 1 second) with alumina (50 μm) to water washing and drying, and a Metal adhesive primer (Metal Link, loosely blown) was applied. After the first paste and the second paste corresponding to the dental adhesive composition of the examples or comparative examples were sufficiently kneaded in equal mass, an appropriate amount of the paste was applied to the surface to be adhered of the stainless steel rod, and the lithium disilicate-containing glass ceramic was joined to the stainless steel rod so as to be accommodated in the frame of the holed double-sided tape. A 200N load was applied from the vertical direction of the stainless steel bar and the remaining water clock was wiped off with a cloth. Thereafter, the adhesive test piece prepared by removing the load was exposed to light for 10 seconds using an LED light irradiator for dental polymerization (Pen Bright, manufactured by Songfeng), immersed in water at 37 ℃ for 24 hours, and then immersed in a cold water phase at 4 ℃ and a high temperature phase at 60 ℃ for 60 seconds each for 1 time using a thermal shock tester (manufactured by Tomasco instruments) and repeated 5000 times. After the test piece was taken out, the tensile bond strength was measured at a crosshead speed of 1mm/min using a universal tester (available from Instron). When the adhesive strength was 10MPa or more, the adhesive strength was judged to be excellent, and when the adhesive strength was less than 5MPa, the adhesive strength was judged to be low.

(adhesive Strength to dental cutting resin (resin Block))

The resin BLOCK (SHOFU BLOCK HC SUPER HARD, SHOFU ブロック HC スーパーハード), prepared by pine blowing) was processed into a plate shape having a thickness of 3mm using a linear precision cutter (Isomet (アイソメット), manufactured by JEOL Ltd.) and ground using water-resistant abrasive paper # 600. Thereafter, a perforated tape (thickness: 200 μm) having a diameter of 4mm was attached to the surface to be adhered so as to define an adhesion area. The surface of the stainless steel rod (4.5 mm) to be adhered was subjected to sand blasting (0.2MPa, 1 second) with alumina (50 μm) → water washing and drying, and coated with a metallic adhesive primer (Metal Link, loose wind). After the first paste and the second paste corresponding to the dental adhesive composition of the examples or comparative examples were sufficiently kneaded in equal mass, an appropriate amount of the paste was applied to the surface to be adhered of the stainless steel rod, and the resin block was joined to the stainless steel rod so as to be accommodated in the frame of the holed tape. A 200N load was applied from the vertical direction of the stainless steel bar and the remaining water clock was wiped off with a cloth. Thereafter, the adhesive test piece prepared by removing the load was exposed to light for 10 seconds using an LED light irradiator for dental polymerization (Pen Bright, manufactured by Songfeng), immersed in water at 37 ℃ for 24 hours, and then immersed in a cold water phase at 4 ℃ and a high temperature phase at 60 ℃ for 60 seconds each for 1 time using a thermal shock tester (manufactured by Tomasco instruments) and repeated 5000 times. After the test piece was taken out, the tensile bond strength was measured at a crosshead speed of 1mm/min using a universal tester (available from Instron). The adhesive strength to the resin block was 15MPa or more, and it was judged that the adhesive strength was good, and when the adhesive strength was less than 10MPa, it was judged that the adhesive strength was not sufficient.

[ adhesive strength to a resin for dental cutting made of a glass fiber-reinforced resin (hereinafter referred to as "GF-reinforced resin") ]

The GF-reinforced resin (TRINIA (トリニア), available from Bicon, バイコン) was processed into a sheet having a thickness of 3mm using a linear precision cutter (Isomet (アイソメット), manufactured by JEOL Ltd.), and ground with water-resistant grinding paper # 600. In this case, the processing is performed in a direction in which the web of the glass fibers is visible on the surface to be bonded (web-shaped surface to be bonded) and in a direction in which the laminated surface of the glass fibers is visible (laminated surface to be bonded). Next, a perforated tape (thickness: 200 μm) having a diameter of 4mm was attached to the surface to be adhered so as to define an adhesion area. The surface of the stainless steel rod (4.5 mm) to be adhered was subjected to sand blasting (0.2MPa, 1 second) with alumina (50 μm) → water washing and drying, and coated with a metallic adhesive primer (Metal Link, loose wind). After the first paste and the second paste corresponding to the dental adhesive composition of the examples or comparative examples were sufficiently kneaded in equal mass, an appropriate amount of the paste was applied to the surface to be adhered of the stainless steel rod, and the GF-reinforced resin was bonded to the stainless steel rod so as to be contained in the frame of the holed tape. A 200N load was applied from the vertical direction of the stainless steel bar and the remaining water clock was wiped off with a cloth. Thereafter, the adhesive test piece prepared by removing the load was exposed to light for 10 seconds using an LED light irradiator for dental polymerization (Pen Bright, manufactured by Songfeng), immersed in water at 37 ℃ for 24 hours, and then immersed in a cold water phase at 4 ℃ and a high temperature phase at 60 ℃ for 60 seconds each for 1 time using a thermal shock tester (manufactured by Tomasco instruments) and repeated 5000 times. After the test piece was taken out, the tensile bond strength was measured at a crosshead speed of 1mm/min using a universal tester (available from Instron). The adhesive strength to the GF-reinforced resin was 15MPa or more, and it was judged that the adhesive strength was good, and when the adhesive strength was less than 10MPa, it was judged that the adhesive strength was not sufficient.

(resistance to staining)

After the first paste and the second paste were sufficiently kneaded in equal mass, the pastes were collected into a mold having a thickness of 1.0mm and an inner diameter of 15mm while paying attention to prevention of entry of air bubbles, both sides were pressed with a cover glass, and both sides were irradiated with light for 60 seconds using a dental polymerization LED irradiator (Pen Bright, manufactured by pine air) to produce a disc-shaped cured body having a thickness of 1.0 mm. The cured body was polished with water-resistant polishing paper #600, followed by polishing with water-resistant polishing paper #1200, and then polishing with water-resistant polishing paper #2000 to adjust the surface to be smooth. Next, the cured product was immersed in a10 mL plastic container containing 5mL of distilled water at 37 ℃ for 1 day. The cured product was taken out, sufficiently wiped off, and then subjected to color measurement under SCE and white background using a spectrophotometer (CM-26d, manufactured by Konika Minidao). Thereafter, the resulting cured product was immersed in a10 mL plastic container containing 5mL of a 0.1% aqueous solution of rhodamine at 37 ℃ for 1 day, washed twice with distilled water, and after sufficiently wiping off water from the cured product, color measurement was performed under SCE and white background conditions using a spectrophotometer (CM-26 d: manufactured by Konikamebendazole). The color difference Δ E was calculated from the results of measurement before and after immersion in a 0.1% aqueous solution of rhodamine, and it was judged that A was the case where Δ E was less than 30, B was the case where Δ E was 30 to 45, and C was the case where Δ E was 45 or more. In the case of C, it is judged that the coloring resistance is poor.

(Properties)

After the first paste and the second paste were sufficiently kneaded in equal mass, 0.1g of the paste was left on the slide glass, and the left position was marked with a sticker. Thereafter, the slide was tilted by 90 °, and after 20 seconds, the slide was restored, and the distance traveled by the paste was measured. Between the paste immediately after preparation and the paste after 3 months of storage at 40 ℃, the moving distance of the paste increases or decreases by less than 10% and is denoted as A, 10-40% as B, and more than 40% as C.

In the case of C, the stability of the properties was judged to be poor.

Examples 101 to 126 confirmed that the adhesive strength was good for dentin, a resin block, and a GF-reinforced resin, and that the adhesive strength was good even after an accelerated test at 40 ℃ for 3 months, and the storage stability was good.

In example 107, since the amount of the polymerizable monomer having one or more hydroxyl groups incorporated in the entire matrix was less than 20 mass%, the adhesive strength to the resin masses and the GF-reinforced resin was 15MPa or less, and the adhesive strength was somewhat low in some cases.

In examples 114 and 115, since the blending amount of the polymerizable monomer having one or more hydroxyl groups contained in the entire matrix exceeded 70 mass%, the adhesive strength to the resin block and the GF reinforcing resin after the accelerated test was 15MPa or less, and the adhesive strength was somewhat low in some cases.

In example 111 in which the index of the amount of silane coupling agent incorporated in the matrix was around the lower limit of formula (1), the adhesive strength to the resin mass and the GF reinforcing resin was slightly low because the adhesive strength was sometimes 15MPa or less.

In examples 112 and 116 in which the index of the amount of silane coupling agent incorporated in the matrix was in the vicinity of the upper limit of formula (1), the adhesion strength of the accelerated test article to the resin mass and the GF-reinforced resin was 15MPa or less, and the adhesion strength was slightly low.

Examples 101, 103, 109 and 120, in which the polymerizable monomer contained in the first matrix to which the silane coupling agent was added had not only one or more hydroxyl groups but also an acidic group, and the content of the polymerizable monomer having a viscosity of 200mPa · s or less at 25 ℃ was less than 5 mass%, exhibited low adhesive strength to the GF-reinforced resin. Examples 101 and 103, in which the amount of the polymerizable monomer having no acidic group but one or more hydroxyl groups and having a viscosity of 200mPa · s or less at 25 ℃ contained in the first matrix was 0.1 mass% or less, showed an adhesive strength of 10mPa or more although the adhesive strength was low in particular.

In examples 102, 113, 118 and 119 in which the amount of the polymerizable monomer having no acidic group but one or more hydroxyl groups and having a viscosity of 200mPa · s or less at 25 ℃ contained in the first matrix to which the silane coupling agent was added was more than 30%, the adhesion strength of the accelerated test article to the resin mass and the GF-reinforced resin was 15mPa or less, and there was a problem in that the adhesion strength was slightly low and the storage stability was problematic. In particular, in example 113 in which the polymerizable monomer having not only one or more hydroxyl groups but not an acidic group and having a viscosity of 200mPa · s or less at 25 ℃ contained in the first matrix exceeded 50 mass%, the adhesion strength of the accelerated test article to the resin mass and the GF-reinforced resin was low.

Examples 122, 123 and 124, which were composed of the first paste comprising the first base to which the silane coupling agent was added and the filler a or the filler B which had not been surface-treated, had a problem in storage stability, since the adhesion strength of the accelerated test article to the resin mass and the GF-reinforced resin was 15MPa or less, and the adhesion strength was slightly low.

Example 120, in which the amount of the polymerizable monomer having an acid group blended was small, tended to reduce the adhesive strength to dentin, and example 121, in which the amount of the polymerizable monomer having an acid group blended was large, tended to accelerate the reduction in the adhesive strength to dentin of the test piece.

Since comparative examples C101 and C102 do not contain a silane coupling agent, the adhesive strength to the resin mass and the GF reinforcing resin is very low.

Comparative example C105, in which the total index of the amount of silane coupling agent blended in the matrix exceeds the upper limit of formula (1), is poor in discoloration resistance and also poor in stability of properties because it contains filler A which has not been surface-treated.

Comparative examples C103 and C104, which did not contain a polymerizable monomer having an acid group, exhibited very low adhesive strength to dentin.

Comparative examples C106 and C107, which did not contain (a1) the silane coupling agent represented by structural formula (a), exhibited very low adhesive strength to the resin masses and the GF-reinforced resin.

[ dental adhesive composition comprising (A) a silane coupling agent, (B) a polymerizable monomer having an acid group, (C) a polymerizable monomer having no acid group, (H) a volatile organic solvent, and (G) water, and further comprising either or both of (D) a polymerization initiator and (E) a polymerization accelerator ]

(method for producing paste)

The polymerizable monomers, polymerization inhibitor and volatile organic solvent shown in examples and comparative examples were charged into a light-shielding plastic container and mixed for 48 hours at 100rpm using a mixing rotor VMRC-5. Thereafter, all the ingredients described in the table except the ingredients mixed in advance were added, and further mixed for 48 hours at 100rpm using a mixing rotor VMRC-5 to obtain a composition.

The test methods for each characteristic evaluated in examples and comparative examples are as follows.

(methods for producing compositions described in examples and comparative examples)

The polymerizable monomers, polymerization inhibitor and volatile organic solvent shown in examples and comparative examples were charged into a light-shielding plastic container and mixed for 48 hours at 100rpm using a mixing rotor VMRC-5. Thereafter, all the ingredients described in the table except the ingredients mixed in advance were added, and further mixed for 48 hours at 100rpm using a mixing rotor VMRC-5 to obtain a composition.

(storage stability of dental adhesive composition)

In 23 + -2 ℃ in the dark room using plastic straw collection examples or comparative examples in the composition of 5mL, after filling in polypropylene bottle, the nozzle, cap, confirmation even reverse composition does not leak. The bottle filled with the composition was stored in a thermostat at 50 ℃ for 3 months, and it was confirmed that no significant viscosity increase or gelation occurred.

(bonding strength to a lithium disilicate-containing glass ceramic (hereinafter, referred to as lithium disilicate))

An adherend (diameter 15mm, thickness 3mm) was produced by firing a lithium disilicate-containing glass ceramic (VINTAGE PRIME PRESS, color tone E-1, pine wind) under conditions specified by the manufacturer, and the surface of the adherend was polished with water-resistant polishing paper # 600. Thereafter, the surface to be adhered of the sheet to be adhered was subjected to blast treatment (0.2MPa, 1 second) with alumina (50 μm) → water washing and drying. Thereafter, a perforated double-sided tape having a diameter of 4mm was attached to the adherend surface to define the adhesion area. The one-pack compositions described in examples and comparative examples were applied to a tape with a hole, immediately air-dried, and irradiated with light for 5 seconds using an LED irradiator for dental polymerization (Pen Bright, pine). On the other hand, the surface of the stainless steel rod (4.5 mm) to be adhered was subjected to sand blasting (0.2MPa, 1 second) with alumina (50 μm) to water washing and drying, and a Metal adhesive primer (Metal Link, loosely blown) was applied. An appropriate amount of kneaded matter of resin cement (ResiCem (レジセム), prepared by air blowing) was applied to the surface of the stainless steel rod to be adhered, and the resin block was joined to the stainless steel rod so as to be accommodated in the frame of the perforated double-sided tape. A suitable amount of kneaded material of resin cement (ResiCem, manufactured by air release) was applied to the surface of the stainless steel rod to be adhered, and the resin block was joined to the stainless steel rod so as to be accommodated in the frame of the perforated double-sided tape. A 200N load was applied from the vertical direction of the stainless steel bar and the remaining water clock was wiped off with a cloth. Thereafter, the adhesive test piece prepared by removing the load was exposed to light for 10 seconds using an LED light irradiator for dental polymerization (Pen Bright, manufactured by Songfeng), immersed in water at 37 ℃ for 24 hours, and then immersed in a cold water phase at 4 ℃ and a high temperature phase at 60 ℃ for 60 seconds each for 1 time using a thermal shock tester (manufactured by Tomasco instruments) and repeated 5000 times. After the test piece was taken out, the tensile bond strength was measured at a crosshead speed of 1mm/min using a universal tester (available from Instron). When the adhesive strength was 15MPa or more, it was judged that the adhesive strength was excellent. On the other hand, when the pressure is less than 10MPa, the adhesive strength is judged to be low.

(adhesive strength to resin for dental cutting (hereinafter, referred to as resin block))

The resin BLOCK (SHOFU BLOCK HC SUPER HARD, manufactured by JEOL) was processed into a plate shape having a thickness of 3mm using a linear precision cutter (Isomet (アイソメット), manufactured by JEOL.) and ground using a water-resistant grinding paper # 600. The surface to be adhered of the sheet to be adhered was subjected to sand blasting (0.2MPa, 1 second) with alumina (50 μm) to → water washing and drying. Thereafter, a perforated tape (thickness: 200 μm) having a diameter of 4mm was attached to the surface to be adhered so as to define an adhesion area. The one-pack compositions described in examples and comparative examples were applied to a tape with a hole, immediately air-dried, and irradiated with light for 5 seconds using an LED irradiator for dental polymerization (Pen Bright, pine). On the other hand, the surface of the stainless steel rod (4.5 mm) to be adhered was subjected to sand blasting (0.2MPa, 1 second) with alumina (50 μm) to water washing and drying, and a Metal adhesive primer (Metal Link, loosely blown) was applied. A suitable amount of kneaded material of resin cement (ResiCem, manufactured by air release) was applied to the surface of the stainless steel rod to be adhered, and the resin block was joined to the stainless steel rod so as to be accommodated in the frame of the perforated double-sided tape. A 200N load was applied from the vertical direction of the stainless steel bar and the remaining water clock was wiped off with a cloth. Thereafter, the adhesive test piece prepared by removing the load was exposed to light for 10 seconds using an LED light irradiator for dental polymerization (Pen Bright, manufactured by Songfeng), immersed in water at 37 ℃ for 24 hours, and then immersed in a cold water phase at 4 ℃ and a high temperature phase at 60 ℃ for 60 seconds each for 1 time using a thermal shock tester (manufactured by Tomasco instruments) and repeated 5000 times. After the test piece was taken out, the tensile bond strength was measured at a crosshead speed of 1mm/min using a universal tester (available from Instron). When the adhesive strength was 15MPa or more, it was judged that the adhesive strength was excellent. On the other hand, when the pressure is less than 10MPa, the adhesive strength is judged to be low.

(adhesive strength to resin for dental cutting comprising glass fiber-reinforced resin (hereinafter referred to as GF-reinforced resin))

The GF-reinforced resin (TRINIA (トリニア), available from Bicon, バイコン) was processed into a sheet having a thickness of 3mm using a linear precision cutter (Isomet (アイソメット), manufactured by JEOL Ltd.), and ground with water-resistant grinding paper # 600. In this case, the processing is performed in a direction in which the web of the glass fibers is visible on the surface to be bonded (web-shaped surface to be bonded) and in a direction in which the laminated surface of the glass fibers is visible (laminated surface to be bonded). Next, a perforated tape (thickness: 200 μm) having a diameter of 4mm was attached to the surface to be adhered so as to define an adhesion area. The one-pack compositions described in examples and comparative examples were applied to a tape with a hole, immediately air-dried, and irradiated with light for 5 seconds using an LED irradiator for dental polymerization (Pen Bright, pine). On the other hand, the surface of the stainless steel rod (4.5 mm) to be adhered was subjected to sand blasting (0.2MPa, 1 second) with alumina (50 μm) to water washing and drying, and a Metal adhesive primer (Metal Link, loosely blown) was applied. A suitable amount of kneaded material of resin cement (ResiCem, wind-loosening) was applied to the surface of the stainless steel rod to be adhered, and the GF-reinforced resin was joined to the stainless steel rod so as to be accommodated in the frame of the perforated double-sided tape. A 200N load was applied from the vertical direction of the stainless steel bar and the remaining water clock was wiped off with a cloth. Thereafter, the adhesive test piece prepared by removing the load was exposed to light for 10 seconds using an LED light irradiator for dental polymerization (Pen Bright, manufactured by Songfeng), immersed in water at 37 ℃ for 24 hours, and then immersed in a cold water phase at 4 ℃ and a high temperature phase at 60 ℃ for 60 seconds each for 1 time using a thermal shock tester (manufactured by Tomasco instruments) and repeated 5000 times. After the test piece was taken out, the tensile bond strength was measured at a crosshead speed of 1mm/min using a universal tester (available from Instron). When the adhesive strength was 15MPa or more, it was judged that the adhesive strength was excellent. On the other hand, when the pressure is less than 10MPa, the adhesive strength is judged to be low.

(adhesion strength to dentine)

Test pieces of bovine central incisors embedded with epoxy resin were ground using water-resistant grinding paper #600 and the dentin plane was shaved. Thereafter, a perforated tape (thickness: 200 μm) having a diameter of 4mm was attached to the surface to be adhered so as to define an adhesion area. The one-pack compositions described in examples and comparative examples were applied to a tape with a hole, immediately air-dried, and irradiated with light for 5 seconds using an LED irradiator for dental polymerization (Pen Bright, pine). On the other hand, the surface of the stainless steel rod (4.5 mm) to be adhered was subjected to sand blasting (0.2MPa, 1 second) with alumina (50 μm) to water washing and drying, and a Metal adhesive primer (Metal Link, loosely blown) was applied. A suitable amount of kneaded material of resin cement (ResiCem, manufactured by air release) was applied to the surface of the stainless steel rod to be adhered, and the resin block was joined to the stainless steel rod so as to be accommodated in the frame of the perforated double-sided tape. A 200N load was applied from the vertical direction of the stainless steel bar and the remaining water clock was wiped off with a cloth. Thereafter, the adhesive test piece prepared by removing the load was exposed to light for 10 seconds using an LED light irradiator for dental polymerization (Pen Bright, manufactured by Songfeng), immersed in water at 37 ℃ for 24 hours, and then immersed in a cold water phase at 4 ℃ and a high temperature phase at 60 ℃ for 60 seconds each for 1 time using a thermal shock tester (manufactured by Tomasco instruments) and repeated 5000 times. After the test piece was taken out, the tensile bond strength was measured at a crosshead speed of 1mm/min using a universal tester (available from Instron). When the adhesive strength was 10MPa or more, it was judged that the adhesive strength was excellent. On the other hand, when the pressure is less than 5MPa, the adhesive strength is determined to be low.

The adhesive compositions described in examples 201 to 231 exhibited good adhesive strength of 10MPa or more to lithium disilicate, resin masses, GF reinforcing resin, and dentin.

Examples 204, 206, 207, 208, 209, 210, 215, and 227 each contained a silane coupling agent having an acryloyl group, and thus tended to exhibit a good adhesive strength of 20MPa or more to lithium disilicate.

The compositions of examples 205, 211, 212 and 213 having an index of the amount of the silane coupling agent blended therein of about 0.001 lower limit tend to have a slightly lower adhesive strength to lithium disilicate, while examples 210, 214, 215, 216, 218, 219, 220, 225 and 227 having an index of the amount of the silane coupling agent blended therein of about 0.015 upper limit tend to have a lower permanent adhesive strength after an accelerated test as compared with the initial product.

The compositions of examples 222, 225, 226 and 228, in which the amount of the polymerizable monomer having not only one or more hydroxyl groups but also no acidic group is less than 30 parts by mass per 100 parts by mass of the polymerizable monomer contained in the composition, tend to have low adhesive strength to the resin masses and the GF-reinforced resin, and particularly tend to have low adhesive strength to the GF-reinforced resin. In particular, in examples 225, 226 and 228 in which the amount was less than 20 parts by mass, the decrease in the adhesive strength was large. On the other hand, in examples 210, 211, 220, and 227 in which the amount of the polymerizable monomer having one or more hydroxyl groups added to the polymerizable monomer was more than 60 parts by mass per 100 parts by mass of the polymerizable monomer, the adhesive strength of the test article tended to be reduced more rapidly than that of the initial article. In particular, in examples 210, 211 and 220 in which the amount of the adhesive agent was more than 70 parts by mass, the adhesive strength tended to be significantly reduced.

In examples 218, 219, 220, and 221 in which the content of the compound having a methacryloyl group and/or a methacrylamide group contained in the composition was less than 80 parts by mass, the adhesive strength of 20MPa or more to lithium disilicate was not exhibited even when the silane coupling agent having an acryloyl group was contained.

Since the blending amount of comparative examples C201 to C204 is less than the lower limit of the index of the blending amount of the silane coupling agent in the composition represented by formula 2, the adhesive strength to lithium disilicate, resin masses, and GF reinforcing resin tends to be as low as 10MPa or less.

In comparative examples C205 to C208, the amount of the silane coupling agent blended exceeds the upper limit of the index of the amount of the silane coupling agent blended in the composition represented by formula 2, and therefore, the adhesion strength to lithium disilicate, a resin block, and a GF-reinforced resin after the accelerated test tends to be 10MPa or less, and the storage stability tends to be poor.

Since comparative example C209 does not contain a polymerizable monomer having an acid group, the adhesive strength to dentin is as low as 5MPa or less.

Comparative examples C210, C211, and C212, which did not contain the silane coupling agent represented by structural formula (a), had very low adhesive strength to lithium disilicate, resin masses, and GF-reinforced resins.

In the present specification, when a constituent element of the invention is described as either a singular or a plural, or when it is not described as being limited to a singular or a plural, the constituent element may be either a singular or a plural, unless otherwise clear from the context.

Although the present invention has been described with reference to the detailed embodiments, it should be understood that various changes and modifications can be made by those skilled in the art based on the matters disclosed in the present specification. Therefore, the scope of the embodiments of the present invention is intended to include any alterations or modifications.

In the dental field of the present invention, the dental adhesive composition is widely used as a dental adhesive material, a dental resin cement, a dental abutment building material, a dental adhesive material, a dentin primer, a metal primer, a ceramic primer, a composite resin, a dental pretreatment material, and the like, and therefore, the present invention is industrially applicable.