Dental composition

文档序号：1173419 发布日期：2020-09-18 浏览：16次中文

阅读说明：本技术 牙科组合物 (Dental composition ) 是由 C·雷恩 F·西拉特 J·E·克里 C·舍夫勒 O·埃尔斯纳 T·蒂格斯 M·沃姆 H 于 2019-01-02 设计创作，主要内容包括：一种牙科组合物,其包含下式(I)的可聚合的酸性化合物：<Image he="325" wi="700" file="DDA0002619205550000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>其中R1可以是相同或不同的,当存在多余1个R1时,其表示氢原子或甲基；R2可以是相同或不同的,当存在多余1个R2时,其表示氢原子、直链或支化的C1-6烷基、C3-8环烷基或直链或支化的C2-6烯基；R3可以是相同或不同的,当存在多余1个R3时,其表示被选自-COOM、-PO3M、-O-PO3M2和-SO3M的基团取代的单价有机结构部分,其中M独立地表示氢原子或金属原子；或R2和R3一起形成被选自-COOM、-PO3M、-O-PO3M2和-SO3M的基团取代的二价有机结构部分,其中M独立地表示氢原子或金属原子；L表示(m+n+1)价有机连接体基团；X表示氢原子或选自-COOM、-PO3M、-O-PO3M2或-SO3M的基团,其中M独立地是氢原子或金属原子；m是整数0-6；n是整数0-6；其中(m+n)至少是2；条件为当n是0时,则X不能是氢原子。(A dental composition comprising a polymerizable acidic compound of the following formula (I): wherein R is 1 May be the same or different, when more than 1R is present 1 When it represents a hydrogen atom or a methyl group; r2 may be the same or different, when more than 1R is present 2 When it represents a hydrogen atom, a linear or branched C 1‑6 Alkyl radical, C 3‑8 Cycloalkyl or straight-chain or branched C 2‑6 An alkenyl group; r3 may be the same or different, when more than 1R is present 3 When it represents a group selected from-COOM and-PO 3 M、‑O‑PO 3 M 2 and-SO 3 A monovalent organic moiety substituted with a group of M, wherein M independently represents a hydrogen atom or a metal atom; or R 2 And R 3 Together form a group selected from-COOM, -PO 3 M、‑O‑PO 3 M 2 and-SO 3 A divalent organic moiety substituted by a group of M, wherein M independently represents a hydrogen atom or a metal atom; l represents an (m + n +1) valent organic linker group; x represents a hydrogen atom or is selected from-COOM, -PO 3 M、‑O‑PO 3 M 2 or-SO 3 A group of M, wherein M is independently a hydrogen atom or a metal atom; m is an integer of 0 to 6; n is an integer from 0 to 6; wherein (m + n) is at least 2; provided that when n is 0, then X cannot be a hydrogen atom.)

1. a dental composition comprising a polymerizable acidic compound of the following formula (I):

wherein

R¹Which may be the same or different, when more than 1R is present¹When it represents a hydrogen atom or a methyl group;

R²which may be the same or different, when more than 1R is present²When it represents a hydrogen atom, a linear or branched C_1-6Alkyl radical, C_3-8Cycloalkyl or straight-chain or branched C_2-6An alkenyl group;

R³which may be the same or different, when more than 1R is present³When it represents a group selected from-COOM and-PO₃M、-O-PO₃M₂and-SO₃A monovalent organic moiety substituted with a group of M, wherein M independently represents a hydrogen atom or a metal atom; or

R²And R³Together form a group selected from-COOM, -PO₃M、-O-PO₃M₂and-SO₃A divalent organic moiety substituted by a group of M, wherein M independently represents a hydrogen atom or a metal atom;

l represents an (m + n +1) valent organic linker group;

x represents a hydrogen atom or is selected from-COOM, -PO₃M、-O-PO₃M₂or-SO₃A group of M, wherein M is independently a hydrogen atom or a metal atom;

m is an integer of 0 to 6;

n is an integer of 0 to 6;

wherein (m + n) is at least 2;

provided that when n is 0, then X cannot be a hydrogen atom.

2. A dental composition according to claim 1, wherein m is 1.

3. A dental composition according to claim 1 or 2, wherein n is 1.

4. A dental composition according to claim 1,2 or 3 wherein R³Is a group of formula (II):

wherein

R⁴Which may be the same or different, when more than 1R is present⁴When it represents a hydrogen atom or C_1-4An alkyl group;

R⁵which may be the same or different, when more than 1R is present⁵When it represents a hydrogen atom or C_1-4An alkyl group;

R⁶which may be the same or different, when more than 1R is present⁶When it represents a hydrogen atom or C_1-4An alkyl group;

R⁷which may be the same or different, when more than 1R is present⁷When it represents a hydrogen atom or C_1-4An alkyl group;

y represents an oxygen atom or a sulfur atom;

z is selected from-COOM, -PO₃M、-O-PO₃M₂or-SO₃A group of M, wherein M is independently a hydrogen atom or a metal atom;

a is an integer from 1 to 6;

b is an integer of 0 or 1; and

c is an integer of 1 to 6.

5. Dental composition according to any of the preceding claims, wherein R¹Represents a hydrogen atom.

6. Dental composition according to any of the preceding claims, wherein R²Is represented by C_1-6Alkyl or C_2-6An alkenyl group.

7. A dental composition according to any of the preceding claims wherein L represents an (m + n +1) valent aliphatic or cycloaliphatic linker group.

8. Dental composition according to any of the preceding claims wherein X represents a group selected from-COOM, -PO₃M or-O-PO₃M₂Wherein M is a hydrogen atom.

9. Dental composition according to any of claims 4 to 8, wherein R⁴、R⁵、R⁶And R⁷Represents a hydrogen atom.

10. Dental composition according to any of claims 4 to 9, wherein X is a hydrogen atom.

11. Dental composition according to any of the preceding claims, further comprising a solvent and/or a particulate filler.

12. The dental composition according to any of the preceding claims, wherein the dental composition is a dental restorative composition or a dental prosthetic composition.

13. Dental composition according to any of the preceding claims, wherein the dental composition is a dental adhesive composition, a dental composite composition, a resin modified dental cement, a pit and fissure sealant, a desensitizing agent or a varnish.

14. Use of a polymerizable acidic compound of the following formula (I) for the preparation of a dental composition,

wherein

R¹Which may be the same or different, when more than 1R is present¹When it represents a hydrogen atom or a methyl group;

l represents an (m + n +1) valent organic linker group;

x represents a hydrogen atom or is selected from-COOM, -PO₃M、-O-PO₃M₂or-SO₃A group of M, wherein M is a hydrogen atom or a metal atom;

m is an integer of 0 to 6;

n is an integer of 0 to 6;

wherein m + n is at least 2;

provided that when n is 0, then X cannot be a hydrogen atom.

15. Use according to claim 14, wherein the dental composition is selected from the group consisting of dental adhesive compositions, dental composite compositions, resin modified dental cement, pit and fissure sealants, desensitizing agents and varnishes.

Technical Field

The present invention relates to a dental composition comprising a specific polymerizable acidic compound. The invention also relates to the use of specific polymerizable acidic compounds for the preparation of dental compositions.

Background

Polymerizable dental compositions containing polymerizable compounds are known. Conventionally, polymerizable dental compositions are provided for a wide range of applications and therefore have to meet a number of different requirements. For example, the polymerizable dental composition can be a dental adhesive composition, an adhesive, a pit and fissure sealant, a dental desensitizing composition, a pulp capping composition, a dental composite, a dental glass ionomer cement, a dental root canal sealer composition, or a dental infiltrant.

Typically, (meth) acrylates are used as polymerizable components in polymerizable dental compositions due to their excellent reactivity in free radical polymerization. In order to provide crosslinking capability, polyfunctional (meth) acrylates such as bis-GMA are widely used. EP2895138a1 discloses polymerizable dental compositions comprising N-substituted acrylic acid amide compounds. EP15178515 and EP15188969 disclose N, N' -diallyl-1, 4-bisacrylamide- (2E) -but-2-ene (BAABE).

Dental restorative materials are dental compositions known for restoring the function, morphology and integrity of dental structures damaged by physical damage or caries-related decay of enamel and/or dentin. Dental restorative materials are required to have high biocompatibility, good mechanical properties and mechanical and chemical resistance over a long period of time.

Dental restorative materials include glass ionomer cement with good biocompatibility and good adhesion to dental hard tissue. In addition, the glass ionomer cement can provide anticaries properties by releasing fluoride ions. The glass ionomer cement is cured by an acid-base reaction between reactive glass powder and a polyalkenoic acid. However, conventional glass ionomer cement has relatively low flexural strength and is brittle due to the salt-like structure between the polyacid and the alkali glass.

The mechanical properties of the glass ionomer cement can be improved by the choice of polymerizable compounds in the aqueous dental glass ionomer composition.

WO03/011232a1 discloses a water-based dental glass ionomer cement, which may contain α, β -unsaturated monomers selected from: water-soluble, water-miscible or water-dispersible acrylates and methacrylates, such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, tetrahydrofurfuryl methacrylate, glycerol monomethacrylate or dimethacrylate, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, urethane methacrylate, acrylamide, methacrylamide, diacetoneacrylamide, methacrylamide, glycerol phosphate monomethacrylate, glycerol phosphate dimethacrylate, hydroxyethyl methacrylate phosphate and citric acid dimethacrylate or trimethacrylate.

Disclosure of Invention

It is a problem of the present invention to provide a dental composition comprising specific polymerizable compounds which can be copolymerized with conventional (meth) acrylates, (meth) acrylamides and allyl ethers and which have a favourable enthalpy of polymerization, good solubility in water and/or in acidic environments and biocompatibility.

Furthermore, it is a problem of the present invention to provide a specific polymerizable compound which can be used in dental compositions.

The problem of the invention is solved according to the claims. Accordingly, the present invention provides a dental composition comprising a polymerizable acidic compound of the following formula (I):

wherein

R¹Which may be the same or different, when more than 1R is present¹When it represents a hydrogen atom or a methyl group;

R²And R³

Together form a group selected from-COOM, -PO₃M、-O-PO₃M₂and-SO₃A divalent organic moiety substituted by a group of M, wherein M independently represents a hydrogen atom or a metal atom;

l represents an (m + n +1) valent organic linker group;

x represents a hydrogen atom or is selected from-COOM, -PO₃M、-O-PO₃M₂or-SO₃A group of M, wherein M is independently a hydrogen atom or a metal atom;

m is an integer of 0 to 6;

n is an integer of 0 to 6;

wherein (m + n) is at least 2;

provided that when n is 0, then X cannot be a hydrogen atom.

Furthermore, the present invention provides the use of a polymerizable acidic compound of formula (I) for the preparation of a dental composition.

The invention is based on the recognition that: the polymerizable acidic compounds of formula (I) have excellent enthalpy of polymerization. Furthermore, the invention is based on the recognition that: the viscosity of the compounds of formula (I) is in the range of (meth) acrylates typically used in the field of dental compositions. In addition, the polymerizable compounds of formula (I) provide advantageous maximum polymerization rates and desirable mechanical properties such as flexural strength. Furthermore, the polymerizable acid is soluble in water or soluble in the aqueous acidic formulation. When used in dental glass ionomer cement compositions, one or more of the acidic groups of the compound of formula (I) may participate in the cement reaction and thereby provide an additional curing mechanism.

Detailed description of the preferred embodiments

The terms "polymerization" and "polymerizable" refer to the ability to combine or combine by covalently bonding a large number of small molecules, such as monomers, to form a larger molecule (i.e., a macromolecule or polymer). The monomers may combine to form only linear macromolecules or they may combine to form three-dimensional macromolecules (often referred to as crosslinked polymers). For example, monofunctional monomers form linear polymers, while monomers having at least two functional groups form crosslinked polymers, also referred to as polymer networks. In the case of higher conversion of polymerizable monomers, the amount of polyfunctional monomers may be reduced or leaching problems may be alleviated.

The terms "cure" and "photocure" refer to the polymerization of functionalized oligomers and monomers, or even polymers, into a crosslinked polymer network and/or the hardening of the composition in the cement reaction (cement reaction). For example, curing may be the polymerization of unsaturated monomers or oligomers in the presence of a crosslinking agent.

"actinic radiation" is any electromagnetic radiation capable of producing actinic action and may have a wavelength of at least 150nm and up to and including 1250nm, and typically at least 300nm and up to and including 750 nm.

The term "photoinitiator" is any chemical compound that forms free radicals when activated, such as by interacting with a co-initiator in a photochemical process or by exposure to actinic light.

The term "co-initiator" refers to a molecule that undergoes a chemical change in another molecule, such as a photoinitiator, during a photochemical process. The co-initiator may be a photoinitiator or an electron donor.

As used herein, the term "electron donor" refers to a compound capable of donating an electron in a photochemical process. Suitable examples include organic compounds having heteroatoms and lone pairs of electrons, such as amine compounds.

The term "polyacid polymer" means that the polymer has a plurality of acidic groups, preferably carboxylic acid groups, which can participate in the reaction with the cement of the reactive glass. The carboxylic acid groups are preferably present in the backbone and are derived from acrylic acid, methacrylic acid and/or itaconic acid.

"straight-chain or branched C_1-6Alkyl "and" straight or branched C_2-6The alkenyl group "is not particularly limited. Preferably "straight-chain or branched C_1-6Alkyl "and" straight or branched C_2-6Alkenyl "denotes straight-chain C_1-4Alkyl or straight-chain C_2-4An alkenyl group. "C_3-8Cycloalkyl "is not particularly limited. Preferably, "C_3-8Cycloalkyl radicals "being C_3-6A cycloalkyl group.

Illustrative examples of straight-chain or branched alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, pentyl or hexyl, and illustrative examples of straight-chain or branched alkenyl groups are ethenyl, n-propenyl, isopropenyl, n-butenyl, isobutenyl, tert-butenyl, sec-butenyl, pentenyl or hexenyl.

The term "alkenyl" denotes a monovalent group derived from a hydrocarbon having a carbon number as defined above. The alkenyl group preferably contains at least 1 carbon-carbon double bond, more preferably 1-3 carbon-carbon double bonds, even more preferably 1 or 2 carbon-carbon double bonds, most preferably 1 carbon-carbon double bond. Furthermore, it is preferred that at least 1 carbon-carbon double bond of the alkenyl group is located between the second and third carbon atoms adjacent to the first carbon linking the alkenyl group to the compound of formula (I).

The present invention provides a dental composition. The dental composition may be a dental restorative composition or a dental prosthetic composition. Preferably, the dental composition is selected from the group consisting of dental adhesive compositions, dental composite compositions, resin modified dental cement, pit and fissure sealants, desensitizing agents, and varnishes.

The dental composition of the present invention comprises a specific polymerizable acidic compound of the following formula (I):

in the formula (I), R¹May be the same or different, when more than 1R is present¹When it is used, it represents a hydrogen atom or a methyl group. Preferably, R¹Represents a hydrogen atom.

In the formula (I), R²May be the same or different, when more than 1R is present²When it represents a hydrogen atom, a linear or branched C_1-6Alkyl radical, C_3-8Cycloalkyl or straight-chain or branched C_2-6An alkenyl group. According to a preferred embodiment, R²Represents a hydrogen atom, C_1-6Alkyl or C_2-6An alkenyl group. According to a more preferred embodiment, R²Selected from hydrogen atom, methyl, ethylMesityl, isopropyl, n-propyl and allyl.

In the formula (I), R³May be the same or different, when more than 1R is present³When it represents a group selected from-COOM and-PO₃M、-O-PO₃M₂and-SO₃A monovalent organic moiety substituted with a group of M, wherein M independently represents a hydrogen atom or a metal atom. The monovalent organic moiety is preferably an organic moiety having from 1 to 20 carbon atoms, more preferably from 2 to 10 carbon atoms. The organic moiety may contain a hetero atom selected from an oxygen atom, a sulfur atom and a nitrogen atom in its main chain. In particular, the organic moiety may contain a linkage such as an ether, ester, thioether, amide, urea or carbamate linkage. The monovalent organic moiety is attached to the nitrogen atom by a covalent single bond. The organic moiety may further be substituted with non-COOM, -PO₃M、-O-PO₃M₂and-SO₃And (ii) a group of M, wherein M is as defined above. For example, the organic moiety may be substituted with 1 to 5 groups selected from hydroxyl groups, thiol groups, keto groups and halogen atoms such as fluorine.

According to a particular embodiment of the compounds of formula (I), R²And R³May be taken together to form a group selected from-COOM, -PO₃M、-O-PO₃M₂and-SO₃A divalent organic moiety substituted by a group of M, wherein M independently represents a hydrogen atom or a metal atom.

The divalent organic moiety is preferably an organic moiety having from 1 to 20 carbon atoms, more preferably from 2 to 10 carbon atoms. The organic moiety may contain a hetero atom selected from an oxygen atom, a sulfur atom and a nitrogen atom in its main chain. In particular, the divalent organic moiety may contain a linkage such as an ether, ester, thioether, amide, urea or carbamate linkage. The divalent organic moiety is linked to the nitrogen atom by a covalent single bond. The divalent organic moiety may further be substituted by non-COOM, -PO₃M、-O-PO₃M₂and-SO₃And (ii) a group of M, wherein M is as defined above. For example, the organic moiety may be substituted with 1 to 5 groups selected from hydroxyl groups, thiol groups, keto groups and halogen atoms such as fluorine.

Preferably, R³Is a group of formula (II):

wherein

R⁴Which may be the same or different, when more than 1R is present⁴When it represents a hydrogen atom or C_1-4An alkyl group;

R⁵which may be the same or different, when more than 1R is present⁵When it represents a hydrogen atom or C_1-4An alkyl group;

R⁶which may be the same or different, when more than 1R is present⁶When it represents a hydrogen atom or C_1-4An alkyl group;

R⁷which may be the same or different, when more than 1R is present⁷When it represents a hydrogen atom or C_1-4An alkyl group;

y represents an oxygen atom or a sulfur atom;

z is selected from-COOM, -PO₃M、-O-PO₃M₂or-SO₃A group of M, wherein M is independently a hydrogen atom or a metal atom;

a is an integer from 1 to 6;

b is an integer of 0 or 1; and

c is an integer of 1 to 6.

According to a preferred embodiment, R⁴、R⁵、R⁶And R⁷Represents a hydrogen atom.

In formula (I), L represents an (m + n +1) -valent organic linker group.

The organic linker group is preferably an organic moiety having from 1 to 20 carbon atoms, more preferably from 2 to 10 carbon atoms. The organic linker group may contain a hetero atom selected from an oxygen atom, a sulfur atom and a nitrogen atom in its main chain. In particular, the organic moiety may contain a linkage such as an ether, ester, thioether, amide, urea or carbamate linkage. The monovalent organic moiety is attached to the nitrogen atom by a covalent single bond. TheThe organic moiety may further be substituted by non-COOM, -PO₃M、-O-PO₃M₂and-SO₃And (ii) a group of M, wherein M is as defined above. For example, the organic moiety may be substituted with 1 to 5 groups selected from hydroxyl groups, thiol groups, keto groups and halogen atoms such as fluorine. According to a preferred embodiment, L represents an (m + n +1) -valent aliphatic or cycloaliphatic linker group.

In formula (I), X represents a hydrogen atom or is selected from-COOM, -PO₃M、-O-PO₃M₂or-SO₃A group of M, wherein M is independently a hydrogen atom or a metal atom. According to a preferred embodiment, X represents a group chosen from-COOM, -PO₃M or-O-PO₃M₂Wherein M is a hydrogen atom. According to a preferred embodiment, X is a hydrogen atom.

In the formula (I), m is an integer of 0 to 6. According to a particular embodiment, m is 0. According to another particular embodiment, m is 1. According to another particular embodiment, m is 2. Preferably m is 0 to 2.

In the formula (I), n is an integer of 0 to 6. According to a particular embodiment, n is 0. According to another particular embodiment, n is 1. According to another particular embodiment, n is 2. Preferably n is 0 to 2.

In formula (I), (m + n) is at least 2. According to a particular embodiment, m is 0 and n is 2. According to another specific embodiment, m is 1 and n is 1. According to another specific embodiment, m is 2 and n is 0.

In the formula (I), provided that when n is 0, X cannot be a hydrogen atom. The compounds of formula (I) are therefore always present in a mixture containing a compound selected from the group consisting of-COOM, -PO₃M、-O-PO₃M₂or-SO₃M, wherein M is independently a hydrogen atom or a metal atom.

The compound of formula (I) is preferably comprised in the dental composition according to the present invention in an amount of 1 to 70 wt. -%, based on the total weight of the dental composition. More preferably, the dental composition contains 5 to 50 wt% of the compound of formula (I) based on the total weight of the dental composition.

The dental composition according to the present invention may further comprise a solvent and/or a particulate filler.

Use of a polymerizable acidic compound of formula (I) below for the preparation of a dental composition:

wherein

R¹Which may be the same or different, when more than 1R is present¹When it represents a hydrogen atom or a methyl group;

R²And R³

Together form a group selected from-COOM, -PO₃M、-O-PO₃M₂and-SO₃A divalent organic moiety substituted by a group of M, wherein M independently represents a hydrogen atom or a metal atom;

l represents an (m + n +1) valent organic linker group;

x represents a hydrogen atom or is selected from-COOM, -PO₃M、-O-PO₃M₂or-SO₃A group of M, wherein M is a hydrogen atom or a metal atom;

m is an integer of 0 to 6;

n is an integer of 0 to 6;

wherein m + n is at least 2;

provided that when n is 0, then X cannot be a hydrogen atom.

The dental composition may be selected from the group consisting of dental adhesive compositions, dental composite compositions, resin modified dental cement, pit and fissure sealants, desensitizing agents, and varnishes.

According to a preferred embodiment, the dental composition is a water-based resin-modified dental glass ionomer composition, preferably comprising

(A) The reactive particulate glass is a glass that is,

(B) a water-soluble material comprising acidic groups reactive with the particulate glass in the reaction of the cement and preferably having polymerizable groups;

(D) a polymerization initiator system.

The term "reactive particulate glass" refers to a solid mixture of primarily metal oxides that are converted to glass by a hot melt process and crushed by various processes, the glass being capable of reacting with polymers containing acidic groups in a cement reaction. The glass is in the form of particles. Furthermore, the reactive particulate glass may be surface-modified, for example by silanization or acid treatment. Any conventional reactive dental glass may be used for the purposes of the present invention. Specific examples of particulate reactive glasses are selected from calcium alumino silicate glasses, calcium aluminofluorosilicate glasses, calcium aluminofluoroborosilicate glasses, strontium alumino silicate glasses, strontium aluminofluorosilicate glasses, strontium aluminofluoroborosilicate glasses. Suitable particulate reactive glasses may be in the form of metal oxides, such as zinc oxide and/or magnesium oxide, and/or in the form of ionically leachable glasses, as described in US-A3655605, US-A3814717, US-A4143018, US-A4209434, US-A4360605 and US-A4376835.

Preferably, the reactive particulate glass according to (a) is a reactive particulate glass comprising:

1) 20-45% by weight of silica,

2) 20-40% by weight of alumina,

3) 20-40% by weight of strontium oxide,

4) 1-10% by weight of P₂O₅And are and

5) 3-25% by weight of fluoride.

The aqueous dental glass ionomer composition of the present invention preferably comprises 20 to 90 wt% of reactive particulate glass, more preferably 30 to 80 wt%, based on the total weight of the composition.

The reactive particulate glass generally has an average particle size of 0.005 to 100 μm, preferably 0.01 to 40 μm, as measured, for example, by electron microscopy or by using a conventional laser diffraction particle sizing method embodied by a MALVERN Mastersizer S or MALVERN Mastersizer 2000 apparatus.

The reactive particulate glass may have a monomodal or multimodal (e.g., bimodal) particle size distribution, wherein multimodal reactive particulate glass represents a mixture of two or more particle fractions having different average particle sizes.

The reactive particulate glass may be an agglomerated reactive particulate glass, which may be obtained by agglomerating the reactive particulate glass in the presence of a modified polyacid and/or a polymerizable (meth) acrylate resin. The particle size of the agglomerated reactive particulate glass may be adjusted by a suitable size reduction process such as milling.

The reactive particulate glass can be surface-modified by components according to (B), (C) and/or (D). In particular, the reactive particulate glass may be surface modified by one or more components of the polymerization initiator system (D) to avoid contacting the one or more components of the polymerization initiator system (D) with an acid under aqueous conditions.

The reactive particulate glass may alternatively or additionally be surface modified by a surface modifying agent. Preferably, the surface modifier is a silane. The silane provides the reactive particulate glass with a suitable hydrophobicity, which allows for an advantageous homogeneous mixing with the organic components according to (B), (C) and (D) of the aqueous dental glass ionomer composition.

The water-soluble polymer containing acidic groups and preferably having polymerizable groups is an organic polymer compound that contains pendant ionizable groups such as carboxylic acid groups. The carboxylic acid groups of the polymer are capable of reacting with the reactive particulate glass in the cement reaction to form the glass ionomer cement.

The water-soluble polymer comprising acidic groups according to (B) may be obtained by a process comprising a copolymerization step a), a coupling step B) and optionally a deprotection step.

The term "water-soluble" as used in this context together with the term "polymerizable polymer" means that at least 0.1g, preferably 0.5g, of the polymerizable polymer is dissolved in 100g of water at 20 ℃.

The term "polymer having polymerizable groups" as used in this context with component (B) refers to a polymer containing one or more polymerizable moieties capable of polymerizing and crosslinking the polymer to improve the mechanical properties and long term mechanical and chemical resistance of the cured aqueous dental glass ionomer composition.

The water-soluble polymer according to (B) is preferably hydrolytically stable, which means that the polymer is stable to hydrolysis in acidic media, such as in dental compositions. Specifically, the polymer does not contain groups such as ester groups that hydrolyze within one month at room temperature in an aqueous medium at pH 3.

A preferred water-soluble polymer comprising acidic groups and preferably having polymerizable groups according to (B) can be obtained by a process comprising a step a) of copolymerizing a mixture comprising (i) a first copolymerizable monomer comprising at least one optionally protected carboxylic acid group and a first polymerizable organic moiety, and (ii) a second copolymerizable monomer comprising one or more optionally protected primary and/or secondary amino groups and a second polymerizable organic moiety, to obtain an amino group-containing copolymer. The mixture may also contain additional monomers.

The first copolymerizable monomer to be used in step a) comprises at least 1, preferably 1 to 3, more preferably 1 or 2, most preferably 1, optionally protected carboxylic acid group.

The protecting group of the optionally protected carboxylic acid group is not particularly limited as long as it is a carboxyl protecting group known to those skilled in the art of Organic chemistry (see p.g.m.wuts and t.w.greene, Greene's protective groups in Organic Synthesis, 4 th edition, John Wiley and Sons inc., 2007). Preferably, the carboxyl protecting group is selected from trialkylsilyl, alkyl and arylalkyl groups. More preferably, the carboxy protecting group is selected from alkyl or arylalkyl. Most preferably, the carboxyl protecting group is selected from t-butyl and benzyl. In a preferred embodiment, the carboxyl protecting group is t-butyl.

As used herein, the term "polymerizable organic moiety" refers to an organic moiety of a molecule that can be used to covalently link the molecule to other molecules reactive with the moiety in a chemical reaction (polymerization) to form a macromolecule of repeating or alternating structural units. Preferably, the polymerizable organic moiety is a carbon-carbon double bond, as is the case with ethylenically unsaturated moieties.

In a preferred embodiment, the first copolymerizable monomer is represented by the general formula (1):

in the formula (1), R¹⁰Is a hydrogen atom, a-COOZ group or a linear or branched C_1-6Alkyl, which may be substituted with-COOZ groups. Preferably, R¹⁰Is a hydrogen atom, a-COOZ group or a methyl group. More preferably, R¹⁰Is a hydrogen atom or a methyl group.

In the formula (1), R²⁰Is a hydrogen atom, a-COOZ' group or a linear or branched C_1-6Alkyl, which may be substituted with-COOZ' groups. Preferably, R²⁰Is a hydrogen atom or a-COOZ' group. More preferably, R²⁰Is a hydrogen atom. In formula (1), the dotted line represents R²⁰May be in either cis or trans orientation.

In formula (1), A is a single bond or a straight or branched C_1-6An alkylene group which may contain 1 to 3 heteroatoms selected from oxygen, nitrogen and sulphur atoms between two carbon atoms of the alkylene carbon chain and/or which may contain 1 to 3 groups selected from amide or urethane linkages between two carbon atoms of the alkylene carbon chain. Preferably, A is a single bond or a linear or branched C_1-6An alkylene group, which group may beSo as to contain a heteroatom between two carbon atoms of the alkylene carbon chain, the heteroatom being selected from oxygen or nitrogen atoms, and/or the alkylene group may contain a group selected from amide or carbamate linkages between two carbon atoms of the alkylene carbon chain. More preferably, A is a single bond or a straight chain C_1-6An alkylene group. Most preferably, a is a single bond.

In formula (1), Z ', which may be the same or different, independently represents a hydrogen atom, a metal ion, a protecting group for a carboxylic acid group, or Z ' forms an intramolecular anhydride group with another-COOZ ' group present in the molecule. The metal ion may be a monovalent metal ion such as an alkali metal ion. In one embodiment, Z' is a protecting group for a carboxylic acid group. In another embodiment, Z' is a hydrogen atom. When Z ' forms an intramolecular anhydride group (-C (O) OC (O) -) with an additional-COOZ ' group present in the molecule, this additional-COOZ ' group may preferably be present in R¹As in the case of itaconic anhydride.

In a preferred embodiment, Z' is a hydrogen atom and the polymerization is carried out in an alkaline environment. In an alternative preferred embodiment, Z' is a hydrogen atom and the amino groups of the first and second copolymerizable monomers carry a protecting group.

Preferably, the first copolymerizable monomer is a protected (meth) acrylic monomer. More preferably, the first polymerizable monomer is selected from the group consisting of t-butyl acrylate and benzyl acrylate. Most preferably, the first polymerizable monomer is t-butyl acrylate.

In a preferred embodiment of the aqueous dental glass ionomer composition of the present invention, the second copolymerizable monomer is represented by the general formula (2):

in the formula (2), R³⁰Is a hydrogen atom or a straight-chain or branched C_1-6Alkyl, which may be substituted with-COOZ' groups. Preferably, R³⁰Is a hydrogen atom. In the formula (2), the dotted lineRepresents R³⁰May be in either cis or trans orientation.

In formula (2), X 'is a protected amino group or a hydrocarbon group having 1 to 20 carbon atoms, which may be substituted with an amino group having a protecting group, wherein the hydrocarbon group may contain 1 to 6 hetero atoms selected from an oxygen atom, a nitrogen atom and a sulfur atom, and/or the hydrocarbon group may contain a group selected from an amide bond or a urethane bond, and the hydrocarbon group may be further substituted with up to 6 groups selected from-COOZ', an amino group, a hydroxyl group and a thiol group. Preferably, X 'is a hydrocarbon group having 1 to 20 carbon atoms, which is substituted with an amino group which may carry a protecting group, wherein the hydrocarbon group may contain a hetero atom selected from an oxygen atom and a nitrogen atom, and/or the hydrocarbon group may contain a group selected from an amide bond or a carbamate bond, and the hydrocarbon group may be further substituted with a-COOZ' group. More preferably, X 'is a hydrocarbon group having 1 to 20 carbon atoms, even more preferably 1 to 6 carbon atoms, which is substituted with an amino group which may carry a protecting group, wherein the hydrocarbon group may contain an oxygen atom and/or the hydrocarbon group may contain an amide bond and the hydrocarbon group may be further substituted with a-COOZ' group. In one embodiment, where X is a protected amino group, the compound of formula (2) is allylamine, where the amino group bears a protecting group.

The protecting group of the protected amino group or the optionally protected amino group is not particularly limited and may be any conventional protecting group for amino Groups, as described in p.g.m.wuts and t.w.greene, Greene's Protective Groups in organic Synthesis, 4 th edition, John Wiley and Sons inc, 2007. Preferably, the amino protecting group is selected from acyl, arylalkyl, alkoxycarbonyl and aryloxycarbonyl groups. More preferably, the amino protecting group is an acyl group. Most preferably, the amino protecting group is formyl.

In formula (2), Y' is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, wherein the hydrocarbon group may contain 1 to 6 hetero atoms selected from an oxygen atom, a nitrogen atom and a sulfur atom, and/or the hydrocarbon group may contain a group selected from an amide bond or a carbamate, and the hydrocarbon group may be further substituted with up to 6 groups selected from-COOZ ", an amino group, a hydroxyl group and a thiol group. Preferably, Y is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, wherein the hydrocarbon group may contain a hetero atom selected from an oxygen atom and a nitrogen atom, and/or the hydrocarbon group may contain a group selected from an amide bond or a carbamate, and the hydrocarbon group may be further substituted with a-COOZ "group. More preferably, Y' is a hydrogen atom or a hydrocarbyl group having 1 to 20 carbon atoms, even more preferably 1 to 6 carbon atoms, wherein the hydrocarbyl group may contain an oxygen atom and/or the hydrocarbyl group may contain an amide linkage and the hydrocarbyl group may be further substituted with a-COOZ "group. In a preferred embodiment, Y is a hydrogen atom.

In formula (2), Z ", which may be the same or different, independently represents a hydrogen atom, a metal ion, a protecting group for a carboxylic acid group, or Z" forms an intramolecular anhydride group with another-COOZ "group present in the molecule. In one embodiment, Z "is a protecting group for a carboxylic acid group. In another embodiment, Z "is a hydrogen atom. The metal ion may be a monovalent metal ion such as an alkali metal ion. In another embodiment, Z "is a hydrogen atom. When Z' forms an intramolecular anhydride group (-C (O) OC (O) -) with an additional-COOZ "group present in the molecule.

In a preferred embodiment, Z "is a hydrogen atom and the polymerization is carried out in an alkaline environment. In an alternative preferred embodiment, Z "is a hydrogen atom and the amino group of the second copolymerizable monomer carries a protecting group.

In one embodiment, the second copolymerizable monomer comprises a second copolymerizable organic moiety selected from the group consisting of (meth) acrylamide moieties, which may be substituted, and (meth) acrylic acids, which may be protected, substituted. In another embodiment, the second copolymerizable monomer is selected from the group consisting of allylamine, aminopropyl vinyl ether, aminoethyl vinyl ether, N-vinylformamide, and 2-aminomethacrylic acid. In a preferred embodiment, the second copolymerizable monomer is aminopropyl vinyl ether. The amino group may be in the form of an ammonium salt such as ammonium chloride. A preferred structure in which the amino group may also carry a protecting group is depicted in scheme 1 below.

Scheme 1

In the mixture copolymerized in step a), the molar ratio of the first copolymerizable monomer to the second copolymerizable monomer (mol of first copolymerizable monomer/mol of second copolymerizable monomer) is preferably from 100:1 to 100:50, more preferably from 100:2 to 100:20, still more preferably from 100:3 to 100: 10.

The additional copolymerizable monomer optionally used in step a) contains at least 1, preferably 1 to 3, more preferably 1 or 2, most preferably 1, optionally protected acidic group which is not a carboxylic acid group. A specific example of an acidic group is a sulfonic acid group (-SO)₃M'), phosphonic acid groups (-PO), and mixtures thereof₃M’₂) Or a phosphate group (-OPO)₃M’₂) Or a salt thereof, wherein M' may independently be a hydrogen atom or a monovalent ion such as an alkali metal or ammonium ion.

Specific examples of optional additional monomers are selected from 2-acrylamido-2-methylpropanesulfonic acid, vinyl phosphonate, and vinylsulfonic acid.

In a preferred embodiment, the solutions containing the first copolymerizable monomer and the second copolymerizable monomer are separately saturated with nitrogen before combining them for copolymerization to minimize possible by-products of the competitive aza-michael addition.

Step a) of the aqueous dental glass ionomer composition is performed as chain growth polymerization. In one embodiment, step a) comprises free radical copolymerization.

The type of copolymer formed by step a) of the present invention may be a statistical copolymer, a random copolymer, an alternating copolymer, a block copolymer, or a combination thereof.

The copolymers obtained by step a) of the present invention are amino-containing copolymers, for example copolymers obtainable by copolymerization of acrylates and aminopropyl vinyl ether.

The reaction conditions of the polymerization reaction according to step a) of the present invention are not particularly limited. Thus, the reaction may be carried out in the presence or absence of a solvent. Suitable solvents may be selected from water, Dimethylformamide (DMF), Tetrahydrofuran (THF) and dioxane.

The reaction temperature is not particularly limited. Preferably, the reaction is carried out at a temperature between-10 ℃ and the boiling point of the solvent. Preferably, the reaction temperature is from 0 ℃ to 80 ℃.

The reaction time is not particularly limited. Preferably, the reaction time is from 10 minutes to 48 hours, more preferably from 1 hour to 36 hours.

The reaction is preferably carried out in the presence of a polymerization initiator. In a preferred embodiment of the aqueous dental glass ionomer composition, the polymerization initiator is selected from the group consisting of Azobisisobutyronitrile (AIBN), 2-azobis (2-amidinopropane) dihydrochloride, 2 '-azobis (2-methylbutyronitrile), 2' -azobis (N, N '-dimethyleneisobutylamidine) dihydrochloride and 4, 4' -azobis (4-cyanovaleric acid). The amount of the polymerization initiator is not particularly limited. Suitably, the amount is from 0.001 to 5 mol%, based on the total amount of monomers.

The reaction product obtained in step a) may be isolated by precipitation and filtration, or lyophilization. The product can be purified according to conventional methods.

Step b) of the aqueous dental glass ionomer composition is a step of coupling a compound having a polymerizable moiety and a functional group reactive with an amino group of a repeating unit derived from a second copolymerizable monomer in the amino group-containing copolymer obtained in the first step, wherein the optionally protected amino group is deprotected.

Preferably, the coupling reaction in step b) is an addition reaction or a condensation reaction forming a chemical bond selected from an amide bond, a urea bond or a thiourea bond.

As used herein, the term "functional group reactive with an amino group" means any group that can form a covalent bond with an amino group of an amino group-containing copolymer. Preferably, the functional group reactive with an amino group is a carboxylic acid group or a derivative thereof such as an ester group or an anhydride thereof, an isocyanate group or an isothiocyanate group. More preferably, the functional group reactive with an amino group is a carboxylic acid group or a derivative thereof.

If the amino group of the repeating unit derived from the second copolymerizable monomer in the amino group-containing copolymer obtained in the first step is protected, the amino group may be deprotected before or concomitantly with step b).

The conditions for deprotection of the optionally protected amino group are selected in accordance with the protecting group used. Preferably, the protected amino group is deprotected by hydrogenolysis or treatment with an acid or base.

If deprotection of the protected amino group is carried out concomitantly with step b), the skilled person will understand that the deprotection conditions and the conditions of step b) have to be chosen such that both reactions can be carried out efficiently.

In a preferred embodiment of the aqueous dental glass ionomer composition, the compound having a polymerizable moiety and a functional group reactive with an amino group of a repeating unit derived from a second copolymerizable monomer is a compound represented by the general formula (3):

in the formula (3), R⁴⁰Is a hydrogen atom or a straight-chain or branched C_1-6Alkyl which may be substituted by a-COOZ "group, and R⁵⁰Is a hydrogen atom or a straight-chain or branched C_1-6Alkyl, which may be substituted with a-COOZ' "group. Preferably, R⁴⁰Is a hydrogen atom, and R⁵⁰Is a hydrogen atom or a methyl group. More preferably, R⁴⁰Is a hydrogen atom, and R⁵⁰Is methyl. In formula (3), the dotted line represents R⁴⁰May be in either cis or trans orientation.

In formula (3), Z ' ", which may be the same or different, independently represents a hydrogen atom, a metal ion, a protecting group for a carboxylic acid group, or Z '" forms an intramolecular anhydride group with an additional-COOZ ' "group present in the molecule.

In one embodiment, Z' "is a protecting group for a carboxylic acid group. In another embodiment, Z' "is a hydrogen atom. In a preferred embodiment, Z' "is a hydrogen atom and the polymerization is carried out in an alkaline environment. In an alternative preferred embodiment, Z' "is a hydrogen atom and the amino group of the second copolymerizable monomer carries a protecting group.

In one embodiment, in formula (3), LG is a leaving group. Preferably, LG is a chlorine atom or a bromine atom, or forms a carboxylic anhydride moiety with an adjacent carbonyl group. More preferably, LG is a group suitable for reacting with a compound of formula (3) in a Schotten-Baumann type reaction.

In another embodiment, LG can replace Z' "and react with R⁴⁰Or R⁵⁰Forming intramolecular carboxylic anhydride groups.

In yet another embodiment, two molecules of formula (3) form an intermolecular carboxylic anhydride group by sharing a common LG, wherein LG is an oxygen atom.

Particularly preferred compounds of formula (3) are acrylic acid, (meth) acrylic acid, crotonic acid, isocrotonic acid, tiglic acid, angelic acid, or anhydrides of the foregoing acids formed from two acids which may be the same or different; more preferably anhydrides of the aforementioned acids formed from two identical acids. Most preferably, the compound of formula (3) is (meth) acrylic anhydride.

The coupling according to step b) of the present invention serves to introduce one or more polymerizable moieties into the amino group-containing copolymer, which moieties can be polymerized afterwards to provide further covalences and also advantageously form ionic crosslinks, which impart further strength to the dental material.

In one embodiment of the aqueous dental glass ionomer composition, the carboxylic acid groups of the copolymer obtained in step b) are unprotected and the copolymer can be used as a polymer according to the invention without further treatment. In an alternative embodiment, the carboxylic acid groups of the copolymer obtained in step b) are protected and the carboxylic acid groups have to be deprotected before the copolymer exhibits the characteristics of the polymer according to the invention.

The reaction conditions of the reaction of step b) according to the present invention are not particularly limited. Thus, the reaction may be carried out in the presence or absence of a solvent. Suitable solvents may be selected from Dimethylformamide (DMF), Tetrahydrofuran (THF) and dioxane.

The reaction time is not particularly limited. Preferably, the reaction time is from 10 minutes to 48 hours, more preferably from 1 hour to 36 hours.

The reaction product obtained in step b) may be isolated by precipitation and filtration. The product can be purified.

The aqueous dental glass ionomer composition optionally comprises a step after step a) or step b) of deprotecting the protected carboxylic acid groups to obtain a polymerizable polymer. In a preferred embodiment, the aqueous dental glass ionomer composition comprises the step of deprotecting the protected carboxylic acid groups to obtain a polymerizable polymer. In another preferred embodiment, the aqueous dental glass ionomer composition comprises a step of deprotecting the protected carboxylic acid groups after step b).

The conditions for deprotection of the optionally protected carboxyl group are selected in accordance with the protecting group used. Preferably, the protected carboxyl group is deprotected by hydrogenolysis or treatment with an acid or base.

The polymerizable polymer according to (B) may be the same as disclosed in EP3106146A1 or EP3231412A 2.

The polymerizable polymers according to (B) preferably have a value ranging from 10³In particular 10⁴To 10⁶Average molecular weight M of Da_w. More preferably, the average molecular weight M_wIs 10⁵-7·10⁵Da. Or 3.10⁴-2.5·10⁵Da。

The polymerizable polymer according to (B) must be sufficient in terms of number or weight percentage of carboxylic acid groups to carry out the setting or curing reaction in the presence of the reactive particulate glass according to (a) or any further unmodified or modified particulate reactive and/or non-reactive filler. Preferably, the polymerizable polymer according to (B) is present in the aqueous dental glass ionomer composition in an amount of 5 to 80 wt. -%, more preferably 10 to 50 wt. -%, still more preferably 15 to 40 wt. -%, based on the total weight of the composition.

As the polymerization initiator system according to (D), any compound or system capable of initiating the copolymerization reaction according to the present invention can be suitably used. The polymerization initiator according to (D) may be a photoinitiator or a redox initiator or a mixture thereof.

Suitable redox initiators comprise a reducing agent and an oxidizing agent, which typically react or cooperate with each other to generate free radicals capable of initiating polymerization of the polymerizable double bonds in components (B) and (C) in a dark reaction (independent of the presence of light). The reducing agent and oxidizing agent are selected such that the polymerization initiator system is sufficiently storage stable and free of undesirable discoloration to allow storage and use under typical dental conditions. In addition, the reducing agent and oxidizing agent are selected such that the polymerization initiator system is sufficiently miscible with the resin system to allow the polymerization initiator system to dissolve in the composition.

Useful reducing agents include ascorbic acid, ascorbic acid derivatives, and metal-complexed ascorbic acid compounds, as described in US 5501727; amines, i.e., tertiary amines, such as 4-tert-butyldimethylaniline; aromatic sulfinates such as p-toluenesulfinic acid salt and benzenesulfinic acid salt; thioureas such as 1-ethyl-2-thiourea, tetraethylthiourea, tetramethylthiourea, 1-dibutylthiourea and 1, 3-dibutylthiourea; and mixtures thereof. Other secondary reducing agents may include cobalt (II) chloride, ferrous sulfate, hydrazine, hydroxylamine, salts of dithionite or sulfite anions, and mixtures thereof.

Suitable oxidizing agents include persulfuric acid and its salts, such as ammonium, sodium, potassium, cesium, and alkylammonium salts. Additional oxidizing agents include peroxides such as benzoyl peroxide, hydroperoxides such as cumyl hydroperoxide, t-butyl hydroperoxide, and amyl hydroperoxide, as well as salts of transition metals such as cobalt (III) chloride and iron chloride, cerium (IV) sulfate, perboric acid and its salts, permanganic acid and its salts, perphosphoric acid and its salts, and mixtures thereof. One or more different oxidizing agents or one or more different reducing agents may be used in the polymerization initiator system. Small amounts of transition metal compounds may also be added to accelerate the rate of redox cure. The reducing agent and the oxidizing agent are present in amounts sufficient to allow for a sufficient radical reaction rate.

The reducing or oxidising agent may be microencapsulated to improve the storage stability of the composition and allow the reducing and oxidising agents to be packaged together if necessary (US 5154762). Proper selection of the encapsulant may allow for the combination of oxidizing and reducing agents and even acid-functionalized components and optional fillers in a storage-stable state. Furthermore, proper selection of the water-insoluble encapsulant allows for the combination of reducing and oxidizing agents with the particulate reactive glass and water in a storage stable state.

Suitable photoinitiators for polymerizing free radical photopolymerizable compositions may include binary and ternary systems. The ternary photoinitiator may include iodineSalts, photosensitizers, and electron donor compounds, as described in US 5545676. Suitable iodine

The salt comprises diaryl iodide

Salts, e.g. diphenyliodide chlorideDiphenyl iodideHexafluorophosphate, diphenyl-iodineTetrafluoroborate, and tolylcumyl iodideTetrakis (pentafluorophenyl) borate. Suitable photosensitizers are monoketones and diketones, which absorb some light in the range of about 400nm to about 520nm (preferably about 450nm to about 500 nm). Is especially suitable forSuitable compounds include α diketones, which have some light absorption in the range of about 400nm to about 520nm (even more preferably about 450 to about 500 nm.) examples include camphorquinone, benzil, furylcyclohexanedione, 3,6, 6-tetramethylcyclohexanedione, phenanthrenequinone, 1-phenyl-1, 2-propanedione, and other 1-aryl-2-alkyl-1, 2-ethanediones, and ring α diketones suitable electron donor compounds include substituted amines such as ethyldimethylaminobenzoate.

Suitable photoinitiators may also include phosphine oxides, which typically have a functionalized wavelength of about 380nm to about 1200 nm. Examples of phosphine oxide free radical initiators having a functionalized wavelength of about 380nm to about 450nm include acyl and bisacylphosphine oxides such as those described in US4298738, US4324744 and US4385109 and EP 0173567. Specific examples of acylphosphine oxides include 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, dibenzoylphenylphosphine oxide, bis (2, 6-dimethoxybenzoyl) phenylphosphine oxide, tris (2, 4-dimethylbenzoyl) phosphine oxide, tris (2-methoxybenzoyl) phosphine oxide, 2, 6-dimethoxybenzoyldiphenylphosphine oxide, 2, 6-dichlorobenzoyldiphenylphosphine oxide, 2,3,5, 6-tetramethylbenzoyldiphenylphosphine oxide, benzoyl-bis (2, 6-dimethylphenyl) phosphonate, and 2,4, 6-trimethylbenzoylethoxyphenylphosphine oxide. Commercially available phosphine oxide photoinitiators capable of free radical initiation when irradiated in the wavelength range of greater than about 380nm to about 450nm include bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide (IRGACURE 819), bis (2, 6-dimethoxybenzoyl) - (2,4, 4-trimethylpentyl) phosphine oxide (CGI 403), a 25:75 mixture by weight of bis (2, 6-dimethoxybenzoyl) -2,4, 4-trimethylpentylphosphine oxide and 2-hydroxy-2-methyl-1-phenylpropan-1-one (IRGACURE 1700), bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide and a 1:1 mixture by weight of 2-hydroxy-2-methyl-1-phenylpropan-1-one (DAROCUR4265), and ethyl 2,4, 6-trimethylbenzylphenylphosphinate (LUCIRIN LR 8893X). Typically, the phosphine oxide initiator is present in the composition in a catalytically effective amount, such as from 0.1 wt% to 5.0 wt%, based on the total weight of the composition.

The tertiary amine reducing agent may be used in combination with the acylphosphine oxide. Examples of suitable tertiary aromatic amines include N, N-dimethylaniline, 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-tert-butylaniline, N-dimethyl-3, 5-di-tert-butylaniline, N-bis (2-hydroxyethyl) -3, 5-dimethylaniline, N-bis (2-hydroxyethyl) -p-toluidine, N-dimethyl-3, 5-di-tert-butylaniline, N, 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, ethyl 4-N, N-dimethylaminobenzoate, methyl 4-N, N-dimethylaminobenzoate, N-butoxyethyl 4-N, N-dimethylaminobenzoate, 2- (methacryloyloxy) ethyl N, N-dimethylammonobenzoate, 4-N, N-dimethylaminobenzophenoneethyl 4- (N, N-dimethylamino) benzoate and N, N-dimethylaminoethyl methacrylate. Examples of the aliphatic tertiary amines include trimethylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-N-butyldiethanolamine, N-lauryldiethanolamine, triethanolamine, 2- (dimethylamino) ethylmethacrylate, N-methyldiethanolamine dimethacrylate, N-ethyldiethanolamine dimethacrylate, triethanolamine monomethacrylate, triethanolamine dimethacrylate, and triethanolamine trimethacrylate.

The amine reducing agent may be present in the composition in an amount of 0.1 wt% to 5.0 wt% based on the total weight of the composition.

The amount of the active species of the polymerization initiator is not particularly limited. Suitably, the amount of the polymerization initiator in the polymerization system according to (D) is 0.001 to 5 mol% based on the total amount of the monomers.

The aqueous dental glass ionomer composition is a curable dental composition, i.e. a cured dental glass ionomer composition/cement may be obtained therefrom by polymerizing the polymerizable polymer according to (B) and the monomer according to (C) in the presence of the reactive particulate glass (a) and the polymerization initiator system according to (D).

Preferably, the dental glass ionomer composition of the present invention has an adhesive bond strength to dentin of at least 5MPa measured according to ISO29022: 2013; and/or a flexural strength of at least 80MPa measured according to ISO 4049.

Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to the following examples.

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