阅读说明：本技术 单体混合物、及含有该单体混合物的固化性组合物 (Monomer mixture and curable composition containing same ) 是由 水田智也 井上庆三 于 2018-07-19 设计创作，主要内容包括：本发明提供一种具有快速固化性、可形成高硬度、耐碱性及基材密合性优异的固化物的单体混合物。本发明的单体混合物含有：式(a-1)和/或(a-2)表示的化合物、1分子中具有2个阳离子聚合性基团且上述阳离子聚合性基团的至少1个为环氧基的化合物(2B)、以及1分子中具有3个以上阳离子聚合性基团且上述阳离子聚合性基团的至少1个为环氧基的化合物(3B),其中,上述式(a-1)表示的化合物与上述式(a-2)表示的化合物的总含量为单体混合物总量的1～20重量％,上述化合物(2B)含有式(2b-1)表示的化合物,上述式(2b-1)表示的化合物的含量为单体混合物的5重量％以上,且上述化合物(2B)/化合物(3B)的含量之比为5～20。<Image he="476" wi="700" file="DDA0002331017090000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The present invention provides a monomer mixture which has rapid curing property, can form a cured product with high hardness, alkali resistance and excellent substrate adhesion. The monomer mixture of the present invention contains: a compound represented by the formula (a-1) and/or (a-2), a compound (2B) having 2 cationically polymerizable groups in1 molecule and at least 1 of the cationically polymerizable groups being an epoxy group, and a compound (3B) having 3 or more cationically polymerizable groups in1 molecule and at least 1 of the cationically polymerizable groups being an epoxy group, wherein the total content of the compound represented by the formula (a-1) and the compound represented by the formula (a-2) is 1 to 20% by weight of the total amount of the monomer mixture, and the compound(s) is/areThe substance (2B) contains a compound represented by the formula (2B-1), the content of the compound represented by the formula (2B-1) is 5% by weight or more of the monomer mixture, and the content ratio of the compound (2B)/the compound (3B) is 5 to 20.)

1. A monomer mixture comprising at least:

a compound represented by the following formula (a-1) and/or (a-2);

1a compound (2B) having 2 cationically polymerizable groups in a molecule, at least 1 of the cationically polymerizable groups being an epoxy group; and

1 compound (3B) having 3 or more cationically polymerizable groups in a molecule, at least 1 of the cationically polymerizable groups being an epoxy group,

wherein the content of the first and second substances,

the total content of the compound represented by the formula (a-1) and the compound represented by the formula (a-2) is 1 to 20% by weight of the total amount of the monomer mixture,

the compound (2B) contains at least a compound represented by the following formula (2B-1), the content of the compound represented by the formula (2B-1) is 5 wt% or more of the total amount of the monomer mixture, and the content ratio of the compound (2B)/the compound (3B) is 5 to 20,

in the formula (2b-1), X represents a single bond, an alkylene group, an alkenylene group in which part or all of the carbon-carbon double bonds have been epoxidized, or a group in which 2 or more alkylene groups are linked via an ether bond.

2. The monomer mixture according to claim 1,

the total content of the compound (2B) and the compound (3B) is 45 wt% or more of the total amount of the monomer mixture.

3. The monomer mixture according to claim 1 or 2, wherein,

the compound (2B) is the following compound (2B), the compound (3B) is the following compound (3B'),

compound (2 b): 1a compound having 2 groups of an oxygen atom and adjacent 2 carbon atoms constituting an alicyclic ring in a molecule,

compound (3 b'): 1 molecule of a compound having 3 or more glycidyl ether groups.

4. The monomer mixture according to any one of claims 1 to 3, further comprising a compound (C) having at least 1 oxetanyl group as a cationically polymerizable group in1 molecule and excluding a compound having an epoxy group in an amount of 15 to 50% by weight based on the total amount of the monomer mixture.

5. The monomer mixture according to any one of claims 1 to 4,

the content of the compound having only 1 cationically polymerizable group selected from the group consisting of a vinyl ether group, an epoxy group and an oxetanyl group in1 molecule is 30% by weight or less of the total amount of the monomer mixture.

6. A curable composition comprising:

the monomer mixture of any one of claims 1 to 5, and

a curing catalyst.

7. The curable composition according to claim 6, which contains a sensitizer, or contains a sensitizer and a sensitization auxiliary.

8. The curable composition according to claim 6 or 7, which contains a color material.

9. The curable composition according to any one of claims 6 to 8, which contains a dispersant.

10. The curable composition according to any one of claims 6 to 9, which is an ultraviolet-curable inkjet ink.

11. A cured product of the curable composition according to any one of claims 6 to 10.

12. A molded article formed from the cured product according to claim 11.

13. A method for producing a molded article, comprising:

a molded article comprising a cured product of the curable composition according to claim 10 is obtained through a step of discharging the curable composition by an ink jet method and then curing the discharged curable composition.

14. A structure comprising the cured product according to claim 11 on a surface of a substrate.

Technical Field

The present invention relates to a monomer mixture and a curable composition containing the monomer mixture. The curable composition can be suitably used for an ultraviolet-curable ink for inkjet. The present application claims priority from japanese patent application No. 2017-147078 filed in japan on 28.7.2017, the contents of which are incorporated herein by reference.

Background

The ink jet method of printing by forming recording dots by causing ink droplets to fly to a recording medium does not require a master, and therefore, can be suitably used for applications in which a small amount of each of a plurality of types is printed. As inks for printing by the inkjet system, that is, inkjet inks, cationic curable inks and radical curable inks are known.

The radical curable ink is used in an increasing number of cases because of its quick curability and the abundance of monomers. However, there is a problem that the curing reaction is hindered by oxygen. In particular, in the ink jet system, since printing is performed by discharging ink in the form of small droplets, the ink is easily exposed to oxygen, and oxygen easily diffuses from the atmosphere and enters the ink. Therefore, the curing inhibition by oxygen is significant, and a large amount of unreacted monomer that causes leakage or odor remains. In addition, there is also a problem that the adhesiveness to the substrate is low, and the surface of the substrate needs to be processed in order to improve the adhesiveness of the ink.

On the other hand, the cationic curable ink is not inhibited from curing by oxygen. Further, the adhesive property to the substrate is more excellent than that of the radical curable ink. Patent documents 1 to 3 describe the following: a cationic curable ink containing a curable compound and a curing catalyst can form an ink film having excellent curability and substrate adhesion when 30 wt% or more of the total curable compounds contain a vinyl ether compound having a cyclic ether skeleton as the curable compound.

However, since the vinyl ether compound having a cyclic ether skeleton readily absorbs moisture, the cationic curable ink containing the compound in the above-mentioned range is easily inhibited from curing by moisture, and curing failure occurs when the ink is used at a high humidity or when moisture in the air is absorbed during storage, and therefore, the ink is not suitable for practical use.

As a method for solving the above problem, patent document 4 describes the following: by limiting the content of the vinyl ether compound having a cyclic ether skeleton and blending a cationically polymerizable compound in place of the compound in combination, a monomer mixture which can be rapidly cured even in the presence of oxygen or moisture can be obtained.

Disclosure of Invention

Problems to be solved by the invention

However, it is known that the cured product of the monomer mixture described in patent document 4 is still insufficient in terms of hardness. Further, it is known that the alkali resistance is insufficient, and it is easy to eliminate printing of the ultraviolet-curable ink containing the monomer mixture described in patent document 4 by wiping with an alkali chemical or the like.

Accordingly, an object of the present invention is to provide a monomer mixture which can be rapidly cured even in the presence of oxygen or moisture and which can form a cured product having high hardness, excellent alkali resistance, and excellent adhesion to a wide range of substrates.

Another object of the present invention is to provide a curable composition containing the monomer mixture and a curing catalyst.

Another object of the present invention is to provide a curable composition which can be used as an ultraviolet-curable ink for inkjet.

Another object of the present invention is to provide a cured product or a molded product of the curable composition.

Another object of the present invention is to provide a structure comprising a cured product of the curable composition on a substrate.

Means for solving the problems

The present inventors have intensively studied to solve the above-mentioned problems, and as a result, they have found that a cured product having excellent curing sensitivity and being rapidly cured even in the presence of oxygen and moisture by irradiation with ultraviolet rays and having high hardness, excellent alkali resistance and excellent adhesion to a wide range of substrates (i.e., having wide substrate selectivity) can be formed by adding a curing catalyst to a monomer mixture containing, as a cationically polymerizable compound, a specific divinyl ether compound having a cyclic ether skeleton and a specific alicyclic epoxy compound in a specific ratio, and containing, in a specific ratio, a compound (2B) having 2 cationically polymerizable groups in1 molecule and at least 1 of the cationically polymerizable groups being an epoxy group in1 molecule, a compound (2B) having 3 or more cationically polymerizable groups in1 molecule, And at least 1 of the cationically polymerizable groups is an epoxy group (3B). The present invention has been completed based on these findings.

That is, the present invention provides a monomer mixture containing at least:

a compound represented by the following formula (a-1) and/or (a-2);

[ chemical formula 1]

1a compound (2B) having 2 cationically polymerizable groups in a molecule, at least 1 of the cationically polymerizable groups being an epoxy group; and

1 compound (3B) having 3 or more cationically polymerizable groups in a molecule, at least 1 of the cationically polymerizable groups being an epoxy group,

wherein the total content of the compound represented by the formula (a-1) and the compound represented by the formula (a-2) is 1 to 20% by weight based on the total amount of the monomer mixture,

the compound (2B) contains at least a compound represented by the following formula (2B-1),

[ chemical formula 2]

(wherein X represents a single bond, an alkylene group, an alkenylene group in which a part or all of the carbon-carbon double bonds have been epoxidized, or a group in which 2 or more alkylene groups are linked via an ether bond.)

The content of the compound represented by the formula (2B-1) is 5 wt% or more based on the total amount of the monomer mixture, and the content ratio of the compound (2B)/the compound (3B) is 5 to 20.

The present invention also provides the monomer mixture, wherein the total content of the compound (2B) and the compound (3B) is 45% by weight or more based on the total amount of the monomer mixture.

The present invention also provides the monomer mixture, wherein the compound (2B) is the following compound (2B), the compound (3B) is the following compound (3B'),

compound (2 b): 1 molecule of a compound having 2 groups of adjacent 2 carbon atoms constituting an alicyclic ring and an oxygen atom,

compound (3 b'): 1 molecule of a compound having 3 or more glycidyl ether groups.

The present invention also provides the monomer mixture described above, further comprising a compound (excluding a compound having an epoxy group) having at least 1 oxetanyl group as a cationically polymerizable group in1 molecule in an amount of 15 to 50% by weight based on the total amount of the monomer mixture (C).

The present invention also provides the monomer mixture, wherein the content of the compound having only 1 cationically polymerizable group selected from the group consisting of a vinyl ether group, an epoxy group and an oxetanyl group in1 molecule is 30% by weight or less of the total amount of the monomer mixture.

The present invention also provides a cured product composition containing the monomer mixture and a curing catalyst.

The present invention also provides the above curable composition, which contains a sensitizer or a sensitizer and a sensitization auxiliary.

The present invention also provides the above curable composition, which contains a coloring material.

The present invention also provides the above curable composition, which contains a dispersant.

The present invention also provides the above curable composition, which is an ultraviolet curable inkjet ink.

The present invention also provides a cured product of the curable composition.

The present invention also provides a molded article comprising the cured product.

Further, the present invention provides a method for producing a molded article, comprising: the curable composition is discharged by an ink jet method, and the discharged curable composition is cured to obtain a molded article formed from a cured product of the curable composition.

The present invention also provides a structure comprising the cured product on a surface of a substrate.

ADVANTAGEOUS EFFECTS OF INVENTION

The monomer mixture of the present invention having the above-described structure can be cured quickly by irradiation with ultraviolet light, and a cured product having high hardness, excellent alkali resistance, and excellent adhesion to a wide range of substrates can be obtained, if a curing catalyst is added thereto, even in the presence of oxygen or moisture. In addition, the above curable composition does not suffer from deterioration in curability even when moisture in the air is absorbed during storage. Namely, the storage stability is excellent. Further, the curable composition has excellent curability, and can suppress the residual of unreacted monomers, and therefore, the generation of odor caused by the unreacted monomers can be significantly reduced. Therefore, the curable composition can be suitably used as an ultraviolet-curable inkjet ink.

Further, when the curable composition is used as an ultraviolet-curable ink for inkjet, an ink film which is extremely fine, has high hardness, is excellent in alkali resistance, and is not easily eliminated even when wiped with an alkaline chemical or the like in an air atmosphere can be formed without particularly limiting humidity conditions and a printed material, and no odor is generated. Therefore, the curable composition can be suitably used as an ultraviolet-curable ink for inkjet in a wide range of industrial fields.

Detailed Description

[ monomer mixture ]

The monomer mixture of the present invention contains, as a cationically polymerizable compound (i.e., a compound having a cationically polymerizable group), at least: a compound represented by the above formula (a-1) and/or (a-2); 1a compound (2B) having 2 cationically polymerizable groups in a molecule, at least 1 of the cationically polymerizable groups being an epoxy group; and 1 molecule has more than 3 cationic polymerization groups, and the cationic polymerization group of at least 1 is epoxy compound (3B).

The monomer mixture of the present invention contains, in addition to the above-mentioned compounds, other cationically polymerizable compounds (compounds containing 1 or 2 or more species of groups selected from vinyl ether groups, epoxy groups and oxetane groups as cationically polymerizable groups).

(vinyl ether Compound (A))

The compound (a) in the present invention is a compound having at least 1 vinyl ether group as a cationically polymerizable group in1 molecule (excluding compounds having an epoxy group and an oxetanyl group).

The compound (A) contains at least a compound represented by the following formula (a-1) and/or (a-2).

[ chemical formula 3]

The compounds represented by the above formulae (a-1) and (a-2) can be produced by a known method. For example, the compound represented by the above formula (a-1) can be produced by reacting 2-hydroxy-6-hydroxymethyl-7-oxabicyclo [2.2.1] heptane with a vinyl ester compound (e.g., vinyl propionate) in the presence of a transition metal compound. The compound represented by formula (a-2) (i.e., isosorbide divinyl ether) can be produced by the same method as described above, except that isosorbide is used instead of 2-hydroxy-6-hydroxymethyl-7-oxabicyclo [2.2.1] heptane.

The monomer mixture of the present invention may contain, as the compound (A), a compound other than the compound represented by the above formula (a-1) and the compound represented by the above formula (a-2) (hereinafter, may be referred to as "other compound (A)"). Examples of the other compound (A) include compounds represented by the following formula (a-3).

R-(O-CH＝CH₂)_t(a-3)

(wherein R represents a t-valent hydrocarbon group, a heterocyclic group, or a group in which these groups are bonded via a single bond or a linking group, and t represents an integer of 1 or more.)

The hydrocarbon group includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.

Examples of the 1-valent aliphatic hydrocarbon group include: an alkyl group having about 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms, particularly preferably 1 to 3 carbon atoms) such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a decyl group, a dodecyl group, etc.; an alkenyl group having about 2 to 20 (preferably 2 to 10, particularly preferably 2 to 3) carbon atoms such as a vinyl group, an allyl group, a methallyl group, a 1-propenyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-pentenyl group, a 2-pentenyl group, a 3-pentenyl group, a 4-pentenyl group, a 5-hexenyl group, or the like; and an alkynyl group having about 2 to 20 carbon atoms (preferably 2 to 10 carbon atoms, particularly preferably 2 to 3 carbon atoms) such as an ethynyl group and a propynyl group. Examples of the t-valent aliphatic hydrocarbon group include groups obtained by further removing (t-1) hydrogen atoms from the structural formula of the 1-valent aliphatic hydrocarbon group.

The alicyclic ring constituting the alicyclic hydrocarbon group includes monocyclic hydrocarbon rings and polycyclic hydrocarbon rings, and the polycyclic hydrocarbon rings include spiro hydrocarbon rings, ring-assembled hydrocarbon rings, bridged hydrocarbon rings, fused hydrocarbon rings, and bridged fused hydrocarbon rings. Examples of the t-valent alicyclic hydrocarbon group include groups obtained by removing t hydrogen atoms from the alicyclic structure.

Examples of the monocyclic hydrocarbon ring include: c such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane and cyclooctane_3-12A cycloalkane ring; c of cyclopentene, cyclohexene, etc_3-12A cycloolefin ring, and the like.

Examples of the aforementioned spiro hydrocarbon ring include: spiro [4.4 ]]Nonane, spiro [4.5 ]]Decane, spirobicyclohexane, etc. C_5-16Spiro hydrocarbon rings, and the like.

Examples of the ring-assembled hydrocarbon ring include: dicyclohexyl etc. containing more than 2C_5-12A ring of a cycloalkane ring aggregates hydrocarbon rings, and the like.

Examples of the bridged hydrocarbon ring include: pinane, camphane, norpinane, norbornane, norbornene, bicycloheptane, bicycloheptene, bicyclooctane (bicyclo [ 2.2.2)]Octane, bicyclo [3.2.1]Octane, etc.) and the like; homobredan, adamantane, tricyclo [5.2.1.0^2,6]Decane, tricyclo [4.3.1.1^2,5]A tricyclic hydrocarbon ring such as undecane; tetracyclic [4.4.0.1^2,5.1^7,10]And 4-cyclic hydrocarbon rings such as dodecane and perhydro-1, 4-methano-5, 8-methanonaphthalene.

Examples of the fused ring hydrocarbon ring include: and condensed rings in which a plurality of 5-to 8-membered cycloalkane rings are condensed, such as perhydronaphthalene (decahydronaphthalene), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthylene, perhydrofluorene, perhydroindene, perhydrophenalene, and the like.

Among the bridged fused ring hydrocarbon rings, there are exemplified dimers of dienes (for example, dimers of cycloalkanedienes such as cyclopentadiene, cyclohexadiene, cycloheptadiene), hydrogenated products thereof, and the like.

The 1-valent aromatic hydrocarbon group includes aromatic hydrocarbon groups having about 6 to 14 (preferably about 6 to 10) carbon atoms such as a phenyl group and a naphthyl group. The t-valent aromatic hydrocarbon group may be a group obtained by further removing (t-1) hydrogen atoms from the structural formula of the 1-valent aromatic hydrocarbon group.

The hydrocarbon group may have various substituents [ for example, a halogen atom, an oxo group, a hydroxyl group, a substituted oxy group (for example, an alkoxy group, an aryloxy group, an aralkyloxy group, an acyloxy group, etc.), a carboxyl group, a substituted oxycarbonyl group (for example, an alkoxycarbonyl group, an aryloxycarbonyl group, an aralkoxycarbonyl group, etc.), a substituted or unsubstituted carbamoyl group, a cyano group, a nitro group, a substituted or unsubstituted amino group, a sulfo group, a heterocyclic group, etc. ]. The hydroxyl group and the carboxyl group may be protected with a protecting group which is conventionally used in the field of organic synthesis. Aromatic or non-aromatic heterocyclic rings may be fused to the alicyclic hydrocarbon groups or aromatic hydrocarbon groups.

Examples of the heterocyclic ring constituting the heterocyclic group include: heterocyclic rings containing oxygen as a heteroatom (e.g. furan, tetrahydrofuran, or the like),

Azolyl ring, iso

5-membered rings such as an azole ring and a γ -butyrolactone ring; 6-membered rings such as 4-oxo-4H-pyran ring, tetrahydropyran ring, morpholine ring and the like; fused rings such as a benzofuran ring, an isobenzofuran ring, a 4-oxo-4H-benzopyran ring, a chroman ring, and an isochroman ring; 3-oxatricyclo [4.3.1.1^4,8]Undecane-2-one ring, 3-oxatricyclo [4.2.1.0^{4 ,8}]Bridged rings such as nonane-2-one ring), heterocycles containing a sulfur atom as a heteroatom (e.g., 5-membered rings such as thiophene ring, thiazole ring, isothiazole ring, and thiadiazole ring; 6-membered rings such as 4-oxo-4H-thiopyran ring; fused rings such as a benzothiophene ring), heterocyclic rings containing a nitrogen atom as a hetero atom (for example, 5-membered rings such as a pyrrole ring, a pyrrolidine ring, a pyrazole ring, an imidazole ring, and a triazole ring; a 6-membered ring such as a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a piperidine ring, or a piperazine ring; a fused ring such as an indole ring, indoline ring, quinoline ring, acridine ring, naphthyridine ring, quinazoline ring, purine ring, etc.), and the like. The heterocyclic group may have an alkyl group (e.g., C such as methyl or ethyl) in addition to the substituent optionally contained in the hydrocarbon group_1-4Alkyl, etc.), cycloalkyl, aryl (e.g. phenyl, naphthalene)Etc.) and the like. Examples of the t-valent heterocyclic group include groups obtained by removing t hydrogen atoms from the structural formula of the above-mentioned heterocyclic ring.

Examples of the linking group include: carbonyl (-CO-), ether linkage (-O-), thioether linkage (-S-), ester linkage (-COO-), amide linkage (-CONH-), carbonate linkage (-OCOO-), silyl linkage (-Si-), and a plurality of these linked groups.

T is an integer of 1 or more, for example, 1 to 20, preferably 1 to 10.

Specific examples of the other compound (a) include: methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, allyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, isopentyl vinyl ether, tert-pentyl vinyl ether, n-hexyl vinyl ether, isohexyl vinyl ether, 2-ethylhexyl vinyl ether, n-heptyl vinyl ether, n-octyl vinyl ether, nonyl vinyl ether, decyl vinyl ether, dodecyl vinyl ether, hexadecyl vinyl ether, octadecyl vinyl ether, ethoxymethyl vinyl ether, 2-methoxyethyl vinyl ether, 2-ethoxyethyl vinyl ether, 2-butoxyethyl vinyl ether, acetoxymethyl vinyl ether, 2-acetoxyethyl vinyl ether, 3-acetoxypropyl vinyl ether, methyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, isopentyl vinyl ether, tert-pentyl vinyl ether, n-hexyl vinyl ether, 4-acetoxybutyl vinyl ether, 4-ethoxybutyl vinyl ether, 2- (2-methoxyethoxy) ethyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, ethylene glycol monovinyl ether, diethylene glycol methyl vinyl ether, diethylene glycol ethyl vinyl ether, triethylene glycol monovinyl ether, tetraethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, propylene glycol monovinyl ether, dipropylene glycol monovinyl ether, tripropylene glycol monovinyl ether, polypropylene glycol monovinyl ether, butylene glycol monovinyl ether, 4-hydroxycyclohexyl vinyl ether, cyclohexanedimethanol monovinyl ether, trimethylolpropane monovinyl ether, ethylene oxide addition trimethylolpropane monovinyl ether, pentaerythritol monovinyl ether, ethylene oxide addition trimethylolpropane monovinyl ether, ethylene oxide addition monovinyl ether, ethylene oxide, ethylene, Ethylene oxide-added pentaerythritol monovinyl ether, cyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, cyclohexyl ethyl vinyl ether, menthyl vinyl ether, tetrahydrofurfuryl vinyl ether, norbornenyl vinyl ether, 1-adamantyl vinyl ether, 2-adamantyl vinyl ether, phenyl vinyl ether, benzyl vinyl ether, 1-naphthyl vinyl ether, 2-naphthyl vinyl ether, glycidyl vinyl ether, diethylene glycol ethyl vinyl ether, triethylene glycol methyl vinyl ether, divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, tripropylene glycol divinyl ether, polypropylene glycol divinyl ether, propylene glycol divinyl ether, and mixtures thereof, Butanediol divinyl ether, neopentyl glycol divinyl ether, hexanediol divinyl ether, nonanediol divinyl ether, hydroquinone divinyl ether, 1, 4-cyclohexanediol divinyl ether, 1, 4-cyclohexanedimethanol divinyl ether, trimethylolpropane divinyl ether, ethylene oxide-added trimethylolpropane divinyl ether, pentaerythritol divinyl ether, ethylene oxide-added pentaerythritol divinyl ether, trimethylolpropane trivinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, pentaerythritol trivinyl ether, ethylene oxide-added pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, di (trimethylolpropane) tetravinyl ether, dipentaerythritol hexavinyl ether, and the like.

Among the other compounds (a), a vinyl ether compound having an aliphatic skeleton [ for example, a vinyl ether compound in which R in the formula (a-3) is an aliphatic hydrocarbon group or a group in which 2 or more aliphatic hydrocarbon groups are bonded via a linking group ] is preferable in that it has rapid curability and can form a cured product having excellent toughness.

The sum of the contents of the compound represented by the formula (a-1), the compound represented by the formula (a-2) and the vinyl ether compound having an aliphatic skeleton is, for example, 70% by weight or more, preferably 80% by weight or more, particularly preferably 90% by weight or more, and most preferably 95% by weight or more of the total amount of the compound (a) contained in the monomer mixture of the present invention. The upper limit is 100% by weight.

(epoxy Compound (B))

The compound (B) in the present invention is a compound having at least 1 epoxy group as a cationically polymerizable group in1 molecule. The epoxy group means a group having a 3-membered cyclic ether structure (oxirane ring structure).

The monomer mixture of the present invention contains, as the compound (B), a compound (2B) having 2 cationically polymerizable groups in1 molecule and at least 1 of the cationically polymerizable groups being an epoxy group, and a compound (3B) having 3 or more cationically polymerizable groups in1 molecule and at least 1 of the cationically polymerizable groups being an epoxy group. The compound (2B) and the compound (3B) may have other cationically polymerizable groups (e.g., a vinyl ether group, an oxetanyl group, etc.) as cationically polymerizable groups in addition to the epoxy group.

The monomer mixture of the present invention may contain, as the compound (B), a compound having 1 epoxy group as a cationically polymerizable group in1 molecule and having no cationically polymerizable group other than the epoxy group, in addition to the compound (2B) and the compound (3B).

The epoxy group includes a group formed of 2 adjacent carbon atoms and an oxygen atom constituting an alicyclic ring (for example, a 3-to 8-membered alicyclic ring) (hereinafter, may be referred to as "alicyclic epoxy group") such as an epoxycyclohexyl group represented by the following formula (e-1), and an oxirane group represented by the following formula (e-2). In the following formula, R¹Represents a hydrogen atom or C_1-3An alkyl group.

[ chemical formula 4]

The compound (2B) is a compound having 2 cationically polymerizable groups in1 molecule and at least 1 of the cationically polymerizable groups is an epoxy group, and among them, a compound (2B ') having 2 epoxy groups in1 molecule is preferable, a compound (2B ') having 2 alicyclic epoxy groups in1 molecule is particularly preferable, and a compound (2B ') having 2 epoxycyclohexyl groups in1 molecule is most preferable.

The compound (2B) (preferably the compound (2B '), particularly preferably the compound (2B), and most preferably the compound (2B')) includes a compound represented by the following formula (2B-1).

[ chemical formula 5]

(wherein X represents a single bond, an alkylene group, a partially or fully epoxidized carbon-carbon double bond of an alkenylene group, or a group in which 2 or more alkylene groups are connected via an ether bond.)

In the formula (2b-1), X represents a single bond, an alkylene group, an alkenylene group in which a part or all of the carbon-carbon double bonds have been epoxidized, or a group in which 2 or more alkylene groups are linked via an ether bond.

Examples of the alkylene group include: a linear or branched alkylene group having 1 to 18 carbon atoms such as a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, or a trimethylene group.

Examples of the alkenylene group in the above-mentioned alkenylene group in which a part or all of the carbon-carbon double bonds have been epoxidized (may be referred to as "epoxidized alkenylene group") include: and linear or branched alkenylene groups having 2 to 8 carbon atoms such as vinylene, propenylene, 1-butenylene, 2-butenylene, butadienylene, pentenylene, hexenylene, heptenylene, octenylene, and the like. In particular, the epoxidized alkenylene group is preferably an alkenylene group in which all of the carbon-carbon double bonds have been epoxidized, and more preferably an alkenylene group having 2 to 4 carbon atoms in which all of the carbon-carbon double bonds have been epoxidized.

The epoxycyclohexyl group in the formula (2b-1) may have a substituent bonded thereto, and examples of the substituent include: halogen atom, hydroxy group, C_1-10Alkyl radical, C_1-10Alkoxy radical, C_2-10Alkenyloxy radical, C_6-14Aryloxy radical, C_7-18Aralkyloxy radical、C_1-10Acyloxy, C_1-10Alkoxycarbonyl group, C_6-14Aryloxycarbonyl group, C_7-18Aralkoxycarbonyl radical, C_1-10Acyl, isocyanate, sulfo, carbamoyl, oxo, and the like.

As typical examples of the compound represented by the above formula (2b-1), there may be mentioned: (3,4,3 ', 4' -diepoxy) bicyclohexane, bis (3, 4-epoxycyclohexylmethyl) ether, 1, 2-epoxy-1, 2-bis (3, 4-epoxycyclohexan-1-yl) ethane, 2-bis (3, 4-epoxycyclohexan-1-yl) propane, 1, 2-bis (3, 4-epoxycyclohexan-1-yl) ethane, and the like.

The compound (2B) may contain 1 or 2 or more of the following compounds in addition to the compound represented by the formula (2B-1): for example, a compound having 1 ethylene oxide group or alicyclic epoxy group in1 molecule and 1 vinyl ether group or oxetane group in1 molecule; a compound having 2 epoxy groups in the alicyclic 1 molecule, such as a compound in which X in the formula (2b-1) is an ester bond or a 2-valent group containing an ester bond (for example, 3, 4-epoxycyclohexylmethyl (3, 4-epoxy) cyclohexanecarboxylate); compounds having 2 oxirane groups (particularly glycidyl ether groups) in1 molecule, such as bisphenol a diglycidyl ether, hydrogenated bisphenol a diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1, 6-hexanediol diglycidyl ether; and compounds having 1 ethylene oxide group and 1 alicyclic epoxy group in each molecule, such as 1,2:8, 9-diepoxy limonene.

Among the compounds (2B), the compound (2B) is preferably contained in an amount of, for example, 70% by weight or more, more preferably 80% by weight or more, particularly preferably 90% by weight or more, and most preferably 95% by weight or more of the total amount of the compounds (2B), from the viewpoint of forming a cured product having high hardness, excellent substrate adhesion, and excellent alkali resistance. The upper limit is 100% by weight.

In addition, from the viewpoint of further improving the alkali resistance of the resulting cured product, the compound (2B) preferably contains the compound represented by the formula (2B-1) in an amount of, for example, 30% by weight or more, more preferably 45% by weight or more, particularly preferably 50% by weight or more, most preferably 55% by weight or more, and particularly preferably 65% by weight or more, based on the total amount of the compound (2B). The upper limit is 100% by weight.

The compound (3B) is a compound having 3 or more cationically polymerizable groups in1 molecule and at least 1 of the cationically polymerizable groups is an epoxy group, and among them, a compound (3B ') having 3 or more epoxy groups in1 molecule is preferable, a compound (3B ') having 3 or more oxirane groups in1 molecule is particularly preferable, and a compound (3B ') having 3 or more glycidyl ether groups in1 molecule is particularly preferable.

The compound (3 b') is represented by the following formula (3b-1), for example.

[ chemical formula 6]

(wherein R' represents an s-valent hydrocarbon group or an s-valent group in which 2 or more hydrocarbon groups are bonded via an ether bond, and s represents an integer of 3 or more.)

Examples of the hydrocarbon group in R' include the same ones as those for R in the above formula (a-3). s represents an integer of 3 or more, and is preferably an integer of 3 to 6, for example. The hydrocarbon group in R' may have various substituents, and examples of the substituent include a substituent optionally contained in R in the formula (a-3), an epoxy group-containing group, and an oxetanyl group.

Examples of the compound (3 b') include: trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, glycerol triglycidyl ether, dipentaerythritol hexaglycidyl ether and the like.

The compound (3B) may contain, for example, a compound having 3 or more alicyclic epoxy groups in1 molecule, a compound having an oxirane group such as a glycidyl ether group and an alicyclic epoxy group in a total of 3 or more glycidyl ether groups in1 molecule, or the like in addition to the compound (3B) (particularly, the compound (3B '), and the content of the compound (3B) (particularly, the compound (3B')) is preferably 70% by weight or more, more preferably 80% by weight or more, particularly preferably 90% by weight or more, and most preferably 95% by weight or more of the total amount of the compound (3B). The upper limit is 100% by weight.

Examples of the compound having 3 or more of the above-mentioned alicyclic epoxy groups in1 molecule include: alicyclic epoxy-modified silicone compounds such as compounds represented by the following formula (3b-2), alicyclic epoxy compounds having a polyester skeleton or a polycaprolactone skeleton such as compounds represented by the following formula (3b-3), and alicyclic epoxy-modified silicone compounds such as compounds represented by the following formula (3 b-4). N in the following formulae (3b-2) and (3b-3)¹～n⁶The same or different, represent an integer of 1 to 30.

[ chemical formula 7]

(Oxetane Compound (C))

The compound (C) in the present invention is a compound having at least 1 oxetanyl group as a cationically polymerizable group in1 molecule (excluding a compound having an epoxy group). The compound (C) may have, as a cationically polymerizable group, other cationically polymerizable group (e.g., a vinyl ether group) in addition to the oxetanyl group. The oxetanyl group means a group having a 4-membered cyclic ether structure (oxytrimethylene ring structure).

The compound (C) can be represented by, for example, the following formula (C).

[ chemical formula 8]

(in the formula, R^aRepresents a 1-valent organic group, R^bRepresents a hydrogen atom or an ethyl group. m represents an integer of 0 or more. )

R is as defined above^aWherein the 1-valent organic group comprises a 1-valent hydrocarbon group, a 1-valent heterocyclic group, a substituted oxycarbonyl groupA group (alkoxycarbonyl group, aryloxycarbonyl group, aralkoxycarbonyl group, cycloalkoxycarbonyl group, etc.), a substituted carbamoyl group (N-alkylcarbamoyl group, N-arylcarbamoyl group, etc.), an acyl group (an aliphatic acyl group such as acetyl group, etc.; an aromatic acyl group such as benzoyl group, etc.), and a 1-valent group in which 2 or more of these groups are bonded via a single bond or a linking group.

The above-mentioned 1-valent hydrocarbon group includes a 1-valent aliphatic hydrocarbon group, a 1-valent alicyclic hydrocarbon group, and a 1-valent aromatic hydrocarbon group. Examples of these groups include those similar to the 1-valent group in R in the above formula (a-3). These groups may have a substituent, and the substituent may be the same as the substituent optionally contained in R in the formula (a-3).

Examples of the heterocyclic ring constituting the above-mentioned 1-valent heterocyclic group include an oxetane ring, in addition to the same examples as those of the heterocyclic ring in R in the above-mentioned formula (a-3). Examples of the linking group include those similar to the linking group in R in the formula (a-3).

M represents an integer of 0 or more, for example, 0to 20, preferably 0to 1.

Among the compounds (C), preferred is a compound (2C) having 2 or more oxetanyl groups in1 molecule. Examples of the compound (2c) include: a compound represented by the following formula (2c-1), a compound represented by the following formula (2c-2), and the like. In the present invention, for example: commercially available products such as "ARON OXETANE OXT-121" and "ARON OXETANE OXT-221" (manufactured by TOYOBO SYNTHETIC CO., LTD.).

[ chemical formula 9]

In addition to the above-mentioned compound (2C), the compound (C) is preferably one which contains 1 or 2 or more compounds which do not impair curing sensitivity, do not impair alkali resistance of the resulting cured product, can reduce the viscosity of the monomer mixture, and impart good coatability. The compound preferably has a viscosity of 10 mPas or less at 25 ℃. Further, the boiling point of the above compound at normal pressure is, for example, 80 ℃ or more [ particularly preferably 100 ℃ or more, and most preferably 120 ℃ or more, from the viewpoint that volatilization in the temperature environment from room temperature to the time of application can be suppressed to keep the viscosity of the monomer mixture constant, and generation of voids can be suppressed thereby. The upper limit of the boiling point is, for example, 200 ℃, preferably 180 ℃, and particularly preferably 150 ℃.

Examples of the above-mentioned compounds include: a compound having 1 oxetanyl group in1 molecule, such as a compound represented by the following formulae (c-1), (c-2) and (c-3),

[ chemical formula 10]

[ monomer mixture ]

The monomer mixture of the present invention contains at least the compound represented by the above formula (a-1) and/or (a-2), the compound (2B), and the compound (3B), and contains at least the compound (2B-1) as the compound (2B). The monomer mixture of the present invention may contain 1 or 2 or more species of other cationically polymerizable compounds in addition to the above compounds.

The total content of the compound represented by the above formula (a-1) and the compound represented by the formula (a-2) in the monomer mixture of the present invention is 1 to 20% by weight of the total amount of the monomer mixture (all monomers contained in the monomer mixture), and the lower limit thereof is preferably 3% by weight, particularly preferably 5% by weight, and most preferably 10% by weight. The upper limit is preferably 18% by weight, particularly preferably 15% by weight. When the content of the compound represented by the above formula (a-1) and/or (a-2) is higher than the above range, the curing rate is remarkably lowered in the presence of moisture, and curing becomes difficult, which is not preferable. On the other hand, when the content of the compound represented by the formula (a-1) and/or (a-2) is less than the above range, rapid curability cannot be obtained, which is not preferable.

The content of the compound (2B-1) in the monomer mixture of the present invention is preferably 20% by weight or more, more preferably 30% by weight or more, particularly preferably 40% by weight or more, and most preferably 50% by weight or more, of the total amount of the compound (B). The upper limit is, for example, 95% by weight, preferably 93% by weight. The content of the compound (2b-1) is 5% by weight or more, preferably 10% by weight or more, more preferably 15% by weight or more, still more preferably more than 20% by weight, particularly preferably 25% by weight or more, and most preferably more than 30% by weight of the total amount of the monomer mixture. The upper limit is, for example, 90% by weight, preferably 80% by weight, more preferably 70% by weight, particularly preferably 60% by weight, and most preferably 55% by weight.

The monomer mixture of the present invention contains 1 compound (2B) having 2 cationically polymerizable groups in the molecule and at least 1 of the cationically polymerizable groups being an epoxy group, and 1 compound (3B) having 3 or more cationically polymerizable groups in the molecule and at least 1 of the cationically polymerizable groups being an epoxy group, and the contents thereof are such that the weight ratio of the compound (2B)/the compound (3B) is in the range of 5 to 20. The lower limit of the above weight ratio is preferably 6, particularly preferably 8, and most preferably 9. The upper limit of the weight ratio is preferably 18, particularly preferably 16, most preferably 15, and particularly preferably 13. When the weight ratio is higher than the above range, the content of the compound (3B) is decreased, and thus the crosslinking density of the obtained cured product tends to be decreased and the hardness tends to be decreased.

The monomer mixture of the present invention preferably contains a compound (2B ') having 2 epoxy groups in1 molecule and a compound (3B') having 3 or more epoxy groups in1 molecule in such amounts that the weight ratio of the compound (2B ')/the compound (3B') is in the range of 5 to 20. The lower limit of the above weight ratio is more preferably 6, particularly preferably 8, and most preferably 9. The upper limit of the weight ratio is more preferably 18, particularly preferably 16, most preferably 15, and particularly preferably 13. When the weight ratio is higher than the above range, the content of the compound (3B') is decreased, and thus the crosslinking density of the obtained cured product tends to be decreased and the hardness tends to be decreased.

In particular, the monomer mixture of the present invention preferably contains a compound (2b) having 2 alicyclic epoxy groups in1 molecule and a compound (3b) having 3 or more oxirane groups in1 molecule, and the content thereof is such that the weight ratio of the compound (2 b)/the compound (3b) is in the range of 5 to 20. The lower limit of the above weight ratio is more preferably 6, particularly preferably 8, and most preferably 9. The upper limit of the weight ratio is more preferably 18, particularly preferably 16, most preferably 15, and particularly preferably 13. When the weight ratio is higher than the above range, the content of the compound (3b) is decreased, and thus the crosslinking density of the obtained cured product tends to be decreased and the hardness tends to be decreased.

The monomer mixture of the present invention preferably contains 1 molecule of a compound (2b) having 2 alicyclic epoxy groups and 1 molecule of a compound (3b ') having 3 or more glycidyl ether groups, and the content thereof is such that the weight ratio of the compound (2 b)/the compound (3 b') is in the range of 5 to 20. The lower limit of the above weight ratio is more preferably 6, particularly preferably 8, and most preferably 9. The upper limit of the weight ratio is more preferably 18, particularly preferably 16, most preferably 15, and particularly preferably 13. When the weight ratio is higher than the above range, the content of the compound (3 b') is decreased, and thus the crosslinking density of the obtained cured product tends to be decreased and the hardness tends to be decreased.

In particular, the monomer mixture of the present invention preferably contains the compound (2b ') having 2 epoxycyclohexyl groups in1 molecule and the compound (3 b') having 3 or more glycidyl ether groups in1 molecule in such amounts that the weight ratio of the compound (2b ')/the compound (3 b') is in the range of 5 to 20. The lower limit of the above weight ratio is more preferably 6, particularly preferably 8, and most preferably 9. The upper limit of the weight ratio is more preferably 18, particularly preferably 16, most preferably 15, and particularly preferably 13. When the weight ratio is higher than the above range, the content of the compound (3 b') is decreased, and thus the crosslinking density of the obtained cured product tends to be decreased and the hardness tends to be decreased.

In particular, the monomer mixture of the present invention preferably contains the compound (2b-1) and the compound (3b ') having 3 or more glycidyl ether groups in1 molecule in such an amount that the weight ratio of the compound (2 b-1)/the compound (3 b') is in the range of 5 to 20. The lower limit of the above weight ratio is more preferably 6, particularly preferably 8, and most preferably 9. The upper limit of the weight ratio is more preferably 18, particularly preferably 16, most preferably 15, and particularly preferably 13. When the weight ratio is higher than the above range, the content of the compound (3 b') is decreased, and thus the crosslinking density of the obtained cured product tends to be decreased and the hardness tends to be decreased.

The total content of the compound (2B) and the compound (3B) in the monomer mixture of the present invention is preferably 45% by weight or more, more preferably 50% by weight or more, and particularly preferably 55% by weight or more, of the total amount of the monomer mixture. The upper limit is, for example, 70% by weight, preferably 65% by weight, and particularly preferably 60% by weight.

The total content of the compound (2B ') and the compound (3B') in the monomer mixture of the present invention is preferably 45% by weight or more, more preferably 50% by weight or more, and particularly preferably 55% by weight or more, of the total amount of the monomer mixture. The upper limit is, for example, 70% by weight, preferably 65% by weight, and particularly preferably 60% by weight.

The total content of the compound (2b) and the compound (3b) in the monomer mixture of the present invention is preferably 45% by weight or more, more preferably 50% by weight or more, and particularly preferably 55% by weight or more, of the total amount of the monomer mixture. The upper limit is, for example, 70% by weight, preferably 65% by weight, and particularly preferably 60% by weight.

The total content of the compound (2b) and the compound (3 b') in the monomer mixture of the present invention is preferably 45% by weight or more, more preferably 50% by weight or more, and particularly preferably 55% by weight or more, of the total amount of the monomer mixture. The upper limit is, for example, 70% by weight, preferably 65% by weight, and particularly preferably 60% by weight.

The total content of the compound (2b ') and the compound (3 b') in the monomer mixture of the present invention is preferably 45% by weight or more, more preferably 50% by weight or more, and particularly preferably 55% by weight or more, of the total amount of the monomer mixture. The upper limit is, for example, 70% by weight, preferably 65% by weight, and particularly preferably 60% by weight.

The total content of the compound (2b-1) and the compound (3 b') in the monomer mixture of the present invention is preferably, for example, 45% by weight or more, more preferably 50% by weight or more, and particularly preferably 55% by weight or more, of the total amount of the monomer mixture. The upper limit is, for example, 70% by weight, preferably 65% by weight, and particularly preferably 60% by weight.

The content of the compound (C) in the monomer mixture of the present invention is, for example, 15 to 50% by weight of the total amount of the monomer mixture, and the upper limit is preferably 45% by weight, particularly preferably 40% by weight, and most preferably 35% by weight. The lower limit is preferably 20% by weight, particularly preferably 25% by weight. If the content of the compound (C) is too large, generation of odor due to volatilization, increase in viscosity (when the viscosity increases, printing by an ink jet method may be difficult), reduction in curing sensitivity, and reduction in adhesion of the obtained cured product to a substrate may be caused.

The total content of the compound (2c) and the compound having at least 1 oxetanyl group in1 molecule and having a viscosity of 10 mPas or less at 25 ℃ in the monomer mixture of the present invention is, for example, 15 to 50% by weight, and the upper limit is preferably 45% by weight, particularly preferably 40% by weight, and most preferably 35% by weight, based on the total amount of the monomer mixture. The lower limit is preferably 20% by weight, particularly preferably 25% by weight. When the total content of the above-mentioned compounds is too large, generation of odor due to volatilization, increase in viscosity (when the viscosity increases, it may be difficult to perform printing by an ink jet method), reduction in curing sensitivity, and reduction in adhesion of the obtained cured product to a substrate may be caused.

The total content of the compound (2c) and the compound having at least 1 oxetanyl group in1 molecule, a viscosity of 10mPa · s or less at 25 ℃ and a boiling point of 80 ℃ or more at normal pressure in the monomer mixture of the present invention is, for example, 15 to 50% by weight based on the total amount of the monomer mixture, and the upper limit is preferably 45% by weight, particularly preferably 40% by weight, and most preferably 35% by weight. The lower limit is preferably 20% by weight, particularly preferably 25% by weight. When the total content of the above-mentioned compounds is too large, generation of odor due to volatilization, increase in viscosity (when the viscosity increases, it may be difficult to perform printing by an ink jet method), reduction in curing sensitivity, and reduction in adhesion of the obtained cured product to a substrate may be caused.

In the monomer mixture of the present invention, the total content of the compound having only 1 cationically polymerizable group selected from the group consisting of a vinyl ether group, an epoxy group and an oxetanyl group (i.e., monofunctional monomer) in1 molecule is, for example, 30% by weight or less, preferably 25% by weight or less, and particularly preferably 20% by weight or less of the total amount of the monomer mixture. When the content of the monofunctional monomer is higher than the above range, it tends to be difficult to obtain a cured product having high hardness.

The total content of the compound represented by the formula (a-1), the compound represented by the formula (a-2), the compound (2B) and the compound (3B) in the total amount of the monomer mixture of the present invention is preferably 46% by weight or more, more preferably 50% by weight or more, particularly preferably 55% by weight or more, and most preferably 60% by weight or more of the total amount of the monomer mixture. The upper limit is, for example, 80 wt%, preferably 75 wt%, and particularly preferably 70 wt%.

The total content of the compound represented by the formula (a-1), the compound represented by the formula (a-2), the compound (2B ') and the compound (3B') in the total amount of the monomer mixture of the present invention is preferably 46% by weight or more, more preferably 50% by weight or more, particularly preferably 55% by weight or more, and most preferably 60% by weight or more of the total amount of the monomer mixture. The upper limit is, for example, 80 wt%, preferably 75 wt%, and particularly preferably 70 wt%.

The total content of the compound represented by the formula (a-1), the compound represented by the formula (a-2), the compound (2b) and the compound (3b) in the total amount of the monomer mixture of the present invention is preferably 46% by weight or more, more preferably 50% by weight or more, particularly preferably 55% by weight or more, and most preferably 60% by weight or more of the total amount of the monomer mixture. The upper limit is, for example, 80 wt%, preferably 75 wt%, and particularly preferably 70 wt%.

The total content of the compound represented by the formula (a-1), the compound represented by the formula (a-2), the compound (2b) and the compound (3 b') in the total amount of the monomer mixture of the present invention is preferably 46% by weight or more, more preferably 50% by weight or more, particularly preferably 55% by weight or more, and most preferably 60% by weight or more of the total amount of the monomer mixture. The upper limit is, for example, 80 wt%, preferably 75 wt%, and particularly preferably 70 wt%.

The total content of the compound represented by the formula (a-1), the compound represented by the formula (a-2), the compound (2b ') and the compound (3 b') in the total amount of the monomer mixture of the present invention is preferably 46% by weight or more, more preferably 50% by weight or more, particularly preferably 55% by weight or more, and most preferably 60% by weight or more of the total amount of the monomer mixture. The upper limit is, for example, 80 wt%, preferably 75 wt%, and particularly preferably 70 wt%.

The total content of the compound represented by the formula (a-1), the compound represented by the formula (a-2), the compound (2b-1) and the compound (3 b') in the total amount of the monomer mixture of the present invention is preferably 46% by weight or more, more preferably 50% by weight or more, particularly preferably 55% by weight or more, and most preferably 60% by weight or more of the total amount of the monomer mixture. The upper limit is, for example, 80 wt%, preferably 75 wt%, and particularly preferably 70 wt%.

The total content of the compound having 2 cationically polymerizable groups selected from the group consisting of a vinyl ether group, an epoxy group and an oxetanyl group in1 molecule in the total amount of the monomer mixture of the present invention is, for example, 30% by weight or more, preferably 40% by weight or more, particularly preferably 50% by weight or more, and most preferably 60% by weight or more of the total amount of the monomer mixture. The upper limit is, for example, 90% by weight, preferably 80% by weight.

The total content of the compound having 3 or more cationically polymerizable groups selected from the group consisting of a vinyl ether group, an epoxy group and an oxetanyl group in1 molecule in the total amount of the monomer mixture of the present invention is, for example, 1% by weight or more, preferably 3% by weight or more, and particularly preferably 5% by weight or more of the total amount of the monomer mixture. The upper limit is, for example, 10% by weight. When the content of the compound is less than the above range, the crosslinking density of the obtained cured product tends to decrease and the hardness tends to decrease.

In addition to the above compounds, the monomer mixture of the present invention may contain other monomers, but the content of the other monomers is, for example, 30% by weight or less, preferably 20% by weight or less, particularly preferably 10% by weight or less, most preferably 5% by weight or less, and particularly preferably 1% by weight or less of the total amount of the monomer mixture.

The monomer mixture of the present invention may contain a compound in which X in the above formula (2b-1) is an ester bond or a 2-valent group containing an ester bond, but the content of the above compound is, for example, 20% by weight or less, preferably 18% by weight or less, particularly preferably 15% by weight or less, most preferably 10% by weight or less, and particularly preferably 5% by weight or less of the total amount of the monomer mixture. When the content of the compound is in the above range, the effect of dramatically improving the alkali resistance is preferably obtained.

The monomer mixture of the present invention can be produced by uniformly mixing the compound represented by the above formula (a-1) and/or (a-2), the compound (2B) containing at least the compound (2B-1), the compound (3B), and other monomers used as needed, using a generally known mixing machine such as a rotation revolution type stirring and defoaming device, a homogenizer, a planetary mixer, a three-roll mill, or a bead mill. The components may be mixed simultaneously or may be mixed in a stepwise manner.

The monomer mixture having the above-described structure is mixed with a curing catalyst to form a curable composition which can be rapidly cured by irradiation with ultraviolet light even in the presence of oxygen or moisture to form a cured product having high hardness, excellent alkali resistance, and excellent adhesion to a wide range of substrates.

[ curable composition ]

The curable composition of the present invention contains the monomer mixture and a curing catalyst.

The content of the monomer mixture is, for example, about 50 to 99.9 wt%, preferably 70 to 98 wt% of the total amount (100 wt%) of the curable composition of the present invention.

The curing catalyst includes a known or conventional photo cation polymerization initiator and a photo radical polymerization initiator. The curable composition of the present invention preferably contains at least a photo cation polymerization initiator as a curing catalyst, and particularly preferably contains both a photo cation polymerization initiator and a photo radical polymerization initiator, because the curing reaction of the curable composition can be more efficiently performed, and particularly a cured product having high hardness can be obtained.

Examples of the photo cation polymerization initiator include: diazonium salt compound and iodine

Salt compounds, sulfonium salt compounds,Salt compound, selenium salt compound, oxygen

Salt compounds, ammonium salt compounds, bromine salt compounds, and the like. In the present invention, for example: trade names "CPI-101A", "CPI-100P", "CPI-110P" (manufactured by SAN-APRO Co., Ltd., above), trade names "CYRACURE UVI-6990", "CYRACURE UVI-6992" (manufactured by DOWCHEMAL Co., Ltd., above), trade names "UVACURE 1590" (manufactured by DAICEL-ALLNEX Co., Ltd.), trade names "CD-1010", "CD-1011", "CD-1012" (manufactured by SARTOMER, USA); commercially available products such as "IRGACURE-264" (manufactured by BASF), "CIT-1682" (manufactured by Nippon Kabushiki Kaisha) and "PHOTOINITIATOR 2074" (manufactured by Rhodia JAPAN). These may be used alone in1 kind, or may be used in combination of 2 or more kinds.

Examples of the photo radical polymerization initiator include: 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, diethoxy acetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, methyl ether, benzoin n-butyl ether, benzoin phenyl ether, benzoin dimethyl ether, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone-4-methoxybenzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2, 4-dimethylthioxanthone, isopropylthioxanthone, 2, 4-dichlorothioxanthone, 2, 4-diethylthioxanthone, 2, 4-diisopropylthioxanthone, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, methylphenylglyoxylate (methyl phenylglyyoylate), benzoyl, camphorquinone, and the like. In the present invention, for example: commercially available products such as "IRGACURE-184", "IRGACURE-127", "IRGACURE-149", "IRGACURE-261", "IRGACURE-369", "IRGACURE-500", "IRGACURE-651", "IRGACURE-754", "IRGACURE-784", "IRGACURE-819", "IRGACURE-907", "IRGACURE-1116", "IRGACURE-1173", "IRGACURE-1664", "IRGACURE-1700", "IRGACURE-1800", "IRGACURE-1850", "IRGACURE-2959", "IRGACURE-4043", "DAROCURE-1173", "DAROCURE-MBF" (manufactured by BASF). These may be used alone in1 kind, or may be used in combination of 2 or more kinds.

The amount of the photo cation polymerization initiator is, for example, preferably about 0.1 to 10 parts by weight, more preferably 0.5 to 10 parts by weight, particularly preferably 1 to 8 parts by weight, and most preferably 3 to 8 parts by weight, based on 100 parts by weight of the monomer mixture.

When a photo radical polymerization initiator and a photo cation polymerization initiator are used together as a curing catalyst, the amount of the photo radical polymerization initiator is preferably 0.1 to 5 parts by weight, particularly preferably 0.5 to 3 parts by weight, and most preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the monomer mixture.

The curable composition of the present invention may contain other components in addition to the monomer mixture and the curing catalyst, as required. Examples of the other components include: conventional sensitizers (e.g., acridine compounds, benzoflavins, perylenes, anthracenes, thioxanthone compounds, laser pigments, etc.), sensitizing aids, antioxidants, stabilizers for amines, etc. are known. Particularly, when the curable composition of the present invention is used for curing by irradiation with UV-LED, it is preferable to contain a sensitizer and a sensitizing aid used as needed in order to improve the light absorptivity of the curing catalyst and improve the curability, and the content thereof (the total amount of 2 or more types of sensitizers in the case of containing the sensitizer) is, for example, about 0.05 to 10 parts by weight, and preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the monomer mixture. The curable composition of the present invention may or may not contain a solvent. Whether or not the solvent is contained may be appropriately adjusted depending on the coating conditions and the like.

When the curable composition of the present invention is used as a color ink for an ultraviolet-curable inkjet ink, it preferably further contains a coloring material. The color material comprises pigment and dye. When the ink contains no color material, the ink can be suitably used as a transparent ink.

(pigment)

The pigment is not particularly limited as long as it is a color material which is generally known as a pigment and can be dispersed in the curable composition. The average particle diameter of the pigment is preferably 300nm or less, for example, from the viewpoint of excellent discharge properties, ink flying properties, and printing reproducibility. The pigment may be used alone in1 kind, or may be used in combination in 2 or more kinds.

The pigment may have, in addition to color developing/coloring properties, magnetic properties, fluorescent properties, conductive properties, dielectric properties, or the like.

Examples of pigments that can be used include: inorganic pigments such as earth pigments (e.g., ochre, ocher, etc.), bronze, chalks, whide, vermilion, ultramarine, chrome green, cadmium red, carbon pigments (e.g., carbon black, refined carbon, carbon nanotubes, etc.), metal oxide pigments (e.g., iron black, cobalt blue, zinc oxide, titanium oxide, chromium oxide, iron oxide, etc.), metal sulfide pigments (e.g., zinc sulfide, etc.), metal sulfates, metal carbonates (e.g., calcium carbonate, magnesium carbonate, etc.), metal silicates, metal phosphates, metal powders (e.g., aluminum powder, bronze powder, zinc powder, etc.); insoluble azo pigments (e.g. monoazo)Yellow, monoazo red, monoazo violet, disazo yellow, disazo orange, pyrazolone pigments, etc.), soluble azo pigments (e.g., azo yellow lake, azo lake red, etc.), benzimidazolone pigments, β -naphthol pigments, naphthol AS pigments, condensed azo pigments, quinacridone pigments (e.g., quinacridone red, quinacridone magenta, etc.), perylene pigments (e.g., perylene red, perylene scarlet, etc.), perinone pigments (e.g., perinone orange, etc.), isoindolinone pigments (e.g., isoindolinone yellow, isoindolinone orange, etc.), isoindoline pigments (e.g., isoindoline yellow, etc.), diindoline pigments, and the like

Oxazine pigments (e.g. diOxazine violet, etc.), thioindigo pigments, anthraquinone pigments, quinophthalone pigments (e.g., quinophthalone yellow, etc.), metal complex pigments, diketopyrrolopyrrole pigments, phthalocyanine pigments (e.g., phthalocyanine blue, phthalocyanine green, etc.), dye lake pigments, and other organic pigments; fluorescent pigments such as inorganic phosphors and organic phosphors.

(dyes)

Examples of the dye include: nitroanilines, phenylmonoazos, pyridone azides, quinophthalones, styryls, anthraquinones, naphthalimidazoles, benzothiazolylazo, phenylbisazo, thiazolylazos, and the like.

The content of the coloring material (the total amount thereof in the case of containing 2 or more species) is, for example, about 0.5 to 20 parts by weight, preferably 1 to 15 parts by weight, based on 100 parts by weight of the monomer mixture.

When the curable composition of the present invention is used as an ultraviolet-curable inkjet ink, a dispersant is preferably contained to improve the dispersibility of the coloring material. Examples of the dispersant include: nonionic surfactants, ionic surfactants, charging agents (charging agents), polymeric dispersants (for example, trade names "Solsperse 24000", "Solsperse 32000", manufactured by AVECIA Inc., ADISPER PB821 "," ADISPERPB822 "," ADISPER PB824 "," ADISPER PB881 "," ADISPER PN411 "," ADISPER PN411 ", manufactured by AJINOMOTO FINE TECHNO Co., Ltd.), and the like. These may be used alone in1 kind, or may be used in combination of 2 or more kinds.

The content of the dispersant is, for example, about 1 to 50 parts by weight, preferably 3 to 30 parts by weight, and particularly preferably 5 to 10 parts by weight, based on 100 parts by weight of the color material.

The surface tension (25 ℃ C., 1 atm) of the curable composition of the present invention is, for example, about 10to 50mN/m, preferably 15 to 40mN/m, and particularly preferably 15 to 30 mN/m. The surface tension of the composition can be measured by the Wilhelmy method (plate method) using, for example, a high-precision surface tensiometer "DY-700" (manufactured by Kyowa Kagaku Co., Ltd.).

The viscosity [25 ℃ C., shear rate 100(1/s) ] of the curable composition of the present invention is, for example, about 1 to 1000 mPas, and the upper limit is preferably 400 mPas, more preferably 100 mPas, particularly preferably 50 mPas, most preferably 30 mPas, and particularly preferably 20 mPas. The lower limit is preferably 3 mPas, particularly preferably 5 mPas, most preferably 10 mPas. Therefore, the curable composition of the present invention has excellent fluidity, and, for example, when discharged (or ejected) by an ink jet printer, the composition has excellent discharge properties.

The curable composition of the present invention can be rapidly cured by irradiation with ultraviolet light even in the presence of oxygen or moisture to form a cured product. Therefore, when used as an ultraviolet-curable ink for inkjet, bleeding and odor can be prevented, and an ink film having excellent printing quality can be formed.

As the light source of the ultraviolet rays, for example: UV-LEDs, mercury lamps such as low-, medium-, and high-pressure mercury lamps, mercury xenon lamps, metal halide lamps, tungsten lamps, arc lamps, excimer lasers, semiconductor lasers, YAG lasers, laser systems in which a laser beam is combined with a nonlinear optical crystal, high-frequency induction ultraviolet ray generators, and the like. The ultraviolet irradiation amount (cumulative light amount) is, for example, 10to 5000mJ/cm²Left and right.

After the curable composition of the present invention is irradiated with ultraviolet rays, a heat treatment may be further performed. By performing the heat treatment, the degree of curing can be further improved. When the heating treatment is performed, the heating temperature is about 40 to 200 ℃, and the heating time is about 1 minute to 15 hours. After the irradiation with ultraviolet rays, the cured degree can be improved by allowing the mixture to stand at room temperature (20 ℃) for about 1 to 48 hours.

The curable composition of the present invention can form a cured product having excellent adhesion to a wide range of substrates [ e.g., glass, metal (e.g., aluminum foil, copper foil, etc.), plastic (e.g., polyethylene, polypropylene, polyethylene terephthalate (PET), vinyl chloride resin, polycarbonate, ABS resin, etc.), natural rubber, butyl rubber, foam (e.g., polyurethane, chloroprene rubber, etc.), wood, woven fabric, nonwoven fabric, cloth, paper (e.g., fine paper, cellophane, kraft paper, japanese paper, etc.), silicon wafer, ceramics, etc., and composites thereof ], etc. ]. The base material may be a material whose surface is subjected to a known surface treatment (ozone treatment, plasma treatment, corona treatment, or the like).

The curable composition of the present invention can form a cured product having not only excellent acid resistance and neutral resistance but also excellent alkali resistance, a molded product thereof, and a structure comprising the cured product.

In the present specification, alkali resistance means alkali resistance; exhibits resistance (e.g., solubility resistance) in the presence of a basic substance (e.g., at least 1 member selected from Lewis bases such as sodium hydroxide, sodium carbonate, sodium bicarbonate, sodium hypochlorite, 2-aminoethanol, and pyridine); the acid resistance refers to: the composition exhibits resistance (e.g., solubility) under conditions (e.g., pH of 1 to 6) in which an acidic substance (e.g., at least 1 selected from hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, citric acid, and a Lewis acid such as aluminum chloride) is present.

The curable composition of the present invention can form a cured product having a high hardness (pencil hardness (based on JIS K5600-5-4), for example, B or more).

Therefore, the curable composition of the present invention can be suitably used for ultraviolet-curable ink materials for inkjet, adhesives, sealing materials, electrical and electronic components such as civil engineering and construction materials and laminates, photoresists, solder resists, interlayer constituting materials for multilayer wiring boards, insulating materials, repairing materials for concrete buildings, casting materials, sealants, photocurable stereoforming materials, optical materials such as lenses and optical waveguides, and the like.

When the curable composition of the present invention is used as an ultraviolet-curable ink for inkjet, an ink film can be formed with very high accuracy in an air atmosphere without particularly limiting the humidity conditions and the objects to be printed, and odor is not generated without particularly limiting the humidity conditions and the objects to be printed. The ink film can be cured quickly by irradiation with ultraviolet light, and can form a cured product which has high hardness, excellent adhesion to a wide range of substrates, and does not dissolve or become cloudy even when wiped with an alkaline chemical. That is, when the curable composition of the present invention is used as an ultraviolet-curable ink for inkjet, highly accurate and hard prints can be formed, and even if the prints are wiped with an alkaline chemical, the prints are not erased or white turbidity does not occur.

[ Molding and Process for producing the same ]

The molded article of the present invention is formed from a cured product of the curable composition. The molded article of the present invention can be produced by subjecting the curable composition to a step of discharging the curable composition by an ink jet method and then curing the discharged curable composition.

The three-dimensional molded article may be produced by cutting or the like of a cured product of the curable composition, may be produced by molding the curable composition, or may be produced by using a three-dimensional printer based on an ink jet system or the like.

The shape and thickness of the molded product can be appropriately adjusted according to the application.

The curable composition has rapid curability, and therefore, if used for the formation of a molded article (e.g., a three-dimensional molded article), a molded article of a desired shape can be easily and efficiently produced.

The molded article of the present invention is formed from a cured product of the curable composition, and therefore has excellent acid resistance, excellent neutral resistance, and excellent alkali resistance. Further, the resin composition has a high hardness (pencil hardness (based on JIS K5600-5-4), for example, B or more), and is less likely to be damaged (i.e., excellent in scratch resistance).

[ Structure and Process for producing the same ]

The structure of the present invention has a structure in which a cured product of the curable composition is provided on a surface of a substrate. The structure can be produced, for example, through a step of discharging the curable composition to the surface of a substrate by an ink jet method and then curing the discharged curable composition.

As the substrate, the above-mentioned substrate can be used without particular limitation. The structure of the present invention is formed using the curable composition, and therefore, the substrate and the cured product have excellent adhesion.

The shape and thickness of the cured product can be appropriately adjusted according to the application.

Since the curable composition has rapid curability, a structure (for example, a structure having a printed matter or a coating film formed from a cured product of the curable composition on a substrate surface) can be efficiently produced. Further, since the cured product of the curable composition has a high hardness (pencil hardness (according to JIS K5600-5-4), for example, B or more), the surface of the cured product of the structure of the present invention is less likely to be damaged (i.e., excellent in scratch resistance). Further, since the cured product of the curable composition has excellent alkali resistance, for example, in the case where the structure of the present invention has printed matter formed of the cured product of the curable composition on the surface of a substrate, the printed matter has a characteristic of being hardly erased even by wiping with an alkaline chemical or the like.