CN114341215A - Curable composition - Google Patents

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CN114341215A
CN114341215A CN202080060289.XA CN202080060289A CN114341215A CN 114341215 A CN114341215 A CN 114341215A CN 202080060289 A CN202080060289 A CN 202080060289A CN 114341215 A CN114341215 A CN 114341215A
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curable composition
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acrylate
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长谷川宗弘
安藤秀明
福留裕树
寺田拓真
松浦洋树
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Nippon Shokubai Co Ltd
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    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
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    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
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    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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Abstract

The purpose of the present invention is to provide a curable composition that exhibits excellent curing reactivity by both energy ray curing and thermal curing. The present invention relates to a curable composition comprising a polymer (A), a polymerizable compound (B) and/or a curing catalyst (C), wherein the polymer (A) has a structural unit represented by the following general formula (1), and has a molecular weight distribution (weight average molecular weight/number average molecular weight) of 1.0 to 4.0. In the formula, R1Represents a hydrogen atom or a methyl group. R2And R3The same or different, represent a hydrogen atom or an organic group. R4Represents a hydrogen atom or an organic group. n represents an integer of 2 or more. [ formula 1]
Figure DDA0003519141540000011

Description

Curable composition
Technical Field
The present invention relates to a curable composition. More specifically, the present invention relates to a curable composition having excellent curing reactivity.
Background
A polymer compound having a reactive functional group in a side chain undergoes a crosslinking reaction by energy rays or heat to provide a good cured product, and therefore, is industrially highly versatile and useful, and is used in a wide range of applications such as adhesives, coating agents, paints, inks, and resists.
For example, it is known that a polymer compound having a cyclic ether group such as an epoxy group or a (meth) acryloyl group is cured in the presence of a compound which generates cations or radicals by irradiation with energy rays or heating. Further, it is known that a hydroxyl group and an isocyanate group or a carboxyl group and an oxazole group undergo a crosslinking reaction by heating.
It is also mentioned that a polymer compound having a vinyl ether group in a side chain is also known to undergo a crosslinking reaction by irradiation with an energy ray or heating to provide a cured product.
For example, patent document 1 describes a curable composition containing a vinyl ether group-containing polymer having a specific structure and a specific compound that generates cations or radicals upon irradiation with an energy ray, which composition does not generate bubbles even during curing by irradiation with an energy ray, and which composition has remarkably improved curing performance upon irradiation with an energy ray, and can provide a cured product having a high quality.
Further, for example, patent document 2 describes a photocurable resin composition having sufficient photocurability by containing a cationically polymerizable compound, an acrylic resin having a cationically polymerizable functional group, and a photocationic polymerization initiator in respective amounts within predetermined ranges, and having sufficient adhesiveness to hard plastics such as polycarbonate and PET which are difficult to adhere.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 6-298884
Patent document 2: japanese patent laid-open No. 2006 and 57078
Disclosure of Invention
Problems to be solved by the invention
As described above, various curable compositions have been proposed. However, in the conventional curable composition, there is still room for improvement in curing reactivity. Further, if the curable composition can be sufficiently cured in both energy ray curing and thermal curing to provide a desired cured product, the curable composition can be applied to a wider range of uses.
The present invention has been made in view of the above-described situation, and an object thereof is to provide a curable composition which exhibits excellent curing reactivity by both energy ray curing and thermal curing.
Means for solving the problems
The present inventors have conducted various studies on a curable composition and as a result, have found that a curable composition having excellent curing reactivity can be obtained by including a polymer having a specific structural unit and a molecular weight distribution (weight average molecular weight/number average molecular weight) in a specific range, and a polymerizable compound and/or a curing catalyst, and have completed the present invention.
Specifically disclosed is a curable composition containing a polymer (A), a polymerizable compound (B) and/or a curing catalyst (C), wherein the polymer (A) has a structural unit represented by the general formula (1) below, and has a molecular weight distribution (weight average molecular weight/number average molecular weight) of 1.0-4.0.
[ solution 1]
Figure BDA0003519141520000021
(in the formula, R1Represents a hydrogen atom or a methyl group. R2And R3The same or different, represent a hydrogen atom or an organic group. R4Represents a hydrogen atom or an organic group. n represents an integer of 2 or more. )
The present invention also relates to a curable composition comprising a polymer (a), a polymerizable compound (B) and/or a curing catalyst (C), wherein the polymer (a) is a group transfer polymer comprising a vinyl ether group-containing (meth) acrylate monomer component represented by the following general formula (2).
[ solution 2]
Figure BDA0003519141520000022
(in the formula, R1Represents a hydrogen atom or a methyl group. R2And R3The same or different, represent a hydrogen atom or an organic group. R4Represents a hydrogen atom or an organic group. n represents an integer of 1 or more. )
In the curable composition, the weight average molecular weight of the polymer (a) is preferably 5000 to 1000000.
In the curable composition, the curing catalyst (C) is preferably at least one selected from the group consisting of a cationic curing catalyst and a radical curing catalyst.
In the curable composition, the polymerizable compound (B) is preferably at least one selected from the group consisting of a vinyl ether compound, a cyclic ether compound, (meth) acrylate, a carboxylic acid compound, a maleimide compound, an alcohol, and a thiol.
In the curable composition, the polymerizable compound (B) is preferably at least one selected from the group consisting of a methylenemalonic acid diester compound and an α -cyanoacrylate.
In the curable composition, the polymerizable compound (B) is preferably an acid group-containing alkali-soluble resin and/or a resin having a group that generates an acid group by heat or acid.
The curable composition is preferably at least one selected from the group consisting of a curable composition for coating agents, a curable composition for adhesives, a curable composition for resists, a curable composition for coatings, a curable composition for printing ink compositions, a curable composition for electronic components, and a curable composition for optical components.
The present invention also relates to a use of the curable composition for producing at least one selected from the group consisting of a coating agent, an adhesive, a resist, a coating material, an ink composition for printing, an electronic component, and an optical component.
ADVANTAGEOUS EFFECTS OF INVENTION
The curable composition of the present invention has the above-described structure, and therefore has excellent curing reactivity. The curable composition of the present invention is suitably used for various applications such as adhesives, printing ink compositions, resist compositions, coating agents, and molding materials.
Drawings
FIG. 1 is a schematic view of a differential molecular weight distribution curve obtained by GPC measurement.
Fig. 2 is a graph showing a DSC curve of a photocationic-cured sample in the example.
Fig. 3 is a graph showing a DSC curve of a photo radical cured sample in the example.
Detailed Description
The present invention is described in detail below.
It should be noted that an embodiment in which 2 or more preferred embodiments of the present invention described below are combined is also a preferred embodiment of the present invention.
In the present specification, "(meth) acrylic acid" means "acrylic acid and/or methacrylic acid", and "(meth) acrylate" means "acrylate and/or methacrylate".
Curable composition (1)
The first curable composition (hereinafter also referred to as "curable composition (1)") of the present invention is characterized by comprising a polymer (a) and a polymerizable compound (B) and/or a curing catalyst (C), wherein the polymer (a) has a structural unit represented by the following general formula (1) and has a molecular weight distribution (weight average molecular weight/number average molecular weight) of 1.0 to 4.0.
[ solution 3]
Figure BDA0003519141520000041
(in the formula, R1Represents a hydrogen atom or a methyl group. R2And R3The same or different, represent a hydrogen atom or an organic group. R4Represents a hydrogen atom or an organic group. n represents an integer of 2 or more. )
The curable composition (1) of the present invention is excellent in curing reactivity, presumably because it contains a polymer having a vinyl ether group with very high reactivity and, in addition, because a vinyl ether group is present in the polymer in an amount sufficient for the curing reaction to proceed efficiently. In the conventional polymer having a vinyl ether group in a side chain, a part of the vinyl ether group is reacted in the production of the polymer, and coupling between the polymers or grafting of a polymer chain from a main chain occurs using this as an origin, so that the molecular weight distribution becomes large. In this case, since the vinyl ether group is consumed in the polymer, the content of the vinyl ether group in the polymer is insufficient. That is, the polymer having the molecular weight distribution controlled in the above-mentioned predetermined range is a polymer having a sufficient vinyl ether group content in the polymer, and it is considered that by using such a polymer, the curable composition can exhibit excellent curing reactivity.
Further, since the polymer (a) contains a gel component when synthesized by radical polymerization, for example, there is a possibility that a flat coating film or the like cannot be obtained and a cured product having a desired shape cannot be obtained or the strength of the cured product is lowered, but the polymer in which the molecular weight distribution of the polymer (a) is controlled in a predetermined range suppresses the generation of the gel component, and thus a good cured product can be obtained.
Hereinafter, each component contained in the curable composition (1) of the present invention will be described.
< Polymer (A) >
The polymer (A) used in the curable composition (1) of the present invention has a structural unit represented by the general formula (1) (hereinafter also referred to as "structural unit (a 1)") and has a molecular weight distribution (weight average molecular weight/number average molecular weight) of 1.0 to 4.0.
In the above general formula (1), R1Represents a hydrogen atom or a methyl group.
In the above general formula (1), R2And R3The same or different, represent a hydrogen atom or an organic group.
As R2Or R3Examples of the organic group include a linear or cyclic monovalent hydrocarbon group having 1 to 20 carbon atoms, and a group obtained by substituting at least a part of atoms constituting the hydrocarbon group with a halogen atom, an oxygen atom, a nitrogen atom, or a sulfur atom.
Examples of the chain hydrocarbon group include a straight-chain or branched-chain aliphatic hydrocarbon group.
Examples of the aliphatic hydrocarbon group include a saturated hydrocarbon group such as an alkyl group, and an unsaturated hydrocarbon group such as an alkenyl group, and preferably include a saturated hydrocarbon group.
Specific examples of the aliphatic hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, pentyl, isopentyl, neopentyl, hexyl, 2-methylpentyl, 3-methylpentyl, 2-dimethylbutyl, 2, 3-dimethylbutyl, heptyl, 2-methylhexyl, 3-methylhexyl, 2-dimethylpentyl, 2, 3-dimethylpentyl, 2, 4-dimethylpentyl, 3-ethylpentyl, 2, 3-trimethylbutyl, octyl, methylheptyl, dimethylhexyl, 2-ethylhexyl, 3-ethylhexyl, trimethylpentyl, 3-ethyl-2-methylpentyl, 2-ethyl-3-methylpentyl, 2, alkyl groups such as 2, 3, 3-tetramethylbutyl, nonyl, methyloctyl, 3, 7-dimethyloctyl, dimethylheptyl, 3-ethylheptyl, 4-ethylheptyl, trimethylhexyl, 3, 3-diethylpentyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl; alkenyl groups such as vinyl, n-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 1-pentenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 3-methyl-1-butenyl, 1-hexenyl, 2-hexenyl, 1-heptenyl, 2-heptenyl, 1-octenyl, and 2-octenyl; and so on.
Examples of the cyclic hydrocarbon group include an alicyclic hydrocarbon group and an aromatic hydrocarbon group.
Examples of the alicyclic hydrocarbon group include cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl, adamantyl, and norbornyl groups.
Examples of the aromatic hydrocarbon group include aromatic hydrocarbon groups such as a phenyl group, a naphthyl group, a biphenyl group, a methoxyphenyl group, a trichlorophenyl group, an ethylphenyl group, a tolyl group, a xylyl group, and a benzyl group.
The halogen atom is preferably chlorine, bromine or fluorine, and more preferably fluorine.
Among them, the organic group is preferably an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or an aromatic hydrocarbon group having 6 to 11 carbon atoms, and further preferably an alkyl group having 1 to 2 carbon atoms, a halogenated alkyl group having 1 to 2 carbon atoms, or an aromatic hydrocarbon group having 6 to 8 carbon atoms.
In the above general formula (1), R4Represents a hydrogen atom or an organic group.
As R4Examples of the organic group include the groups represented by the formula R2And R3The organic groups shown are the same groups. Wherein R is4Preferably a C1-11 chain or cyclic alkyl, more preferably C1-10 alkyl, C3-10 cycloalkyl, C6-11 aromatic hydrocarbon, more preferably C1-3 alkyl.
In the general formula (1), n is an integer of 2 or more.
The polymer having the structural unit (a1) is obtained, for example, by polymerizing a monomer component containing a vinyl ether group-containing (meth) acrylate represented by the following general formula (2).
[ solution 4]
Figure BDA0003519141520000061
In the above general formula (2), R1、R2、R3And R4And in the above general formula (1)R1、R2、R3And R4Are respectively the same. n represents an integer of 2 or more.
Specific examples of the vinyl ether group-containing (meth) acrylates represented by the general formula (2) include 2- (2-ethyleneoxyethoxy) ethyl (meth) acrylate and the like.
The polymer (a) may have only 1 kind of the structural unit (a1), or may have 2 or more kinds of the structural unit (a 1).
The content ratio of the structural unit (a1) in the polymer (a) is preferably 1 mol% to 100 mol% based on 100 mol% of all the structural units. The content ratio of the structural unit (a1) is more preferably 4 mol% or more, and still more preferably 8 mol% or more, from the viewpoint of improving the crosslinking density, and imparting solvent resistance and hardness to a cured product. The content ratio of the structural unit (a1) is preferably 95 mol% or less, and more preferably 90 mol% or less.
When 2 or more species are contained as the structural unit (a1), the content ratio is a total content ratio of the 2 or more species.
The polymer (a) may further have another structural unit (a 2). Examples of the other structural unit (a2) include structural units derived from other polymerizable monomers than the vinyl ether group-containing (meth) acrylates.
Examples of the other polymerizable monomer include polymerizable monomers having an electron-deficient double bond, and these can be appropriately selected depending on the purpose and use of the polymer to be produced.
Specific examples of the polymerizable monomer having an electron-deficient double bond include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, sec-pentyl (meth) acrylate, tert-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, tridecyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, n-butyl (meth) acrylate, n-pentyl (meth) acrylate, sec-pentyl (meth) acrylate, tert-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl methyl (meth) acrylate, cyclohexyl methacrylate, and the like, (meth) acrylates such as dicyclopentyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, 2- (acetoacetoxy) ethyl (meth) acrylate, and allyl (meth) acrylate;
hydroxyl group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, caprolactone-modified hydroxy (meth) acrylate, and 4-hydroxymethylcyclohexylmethyl (meth) acrylate;
(meth) acrylates containing a cyclic ether group such as glycidyl (meth) acrylate, (3, 4-epoxycyclohexyl) methyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and (3-ethyloxetan-3-yl) methyl (meth) acrylate;
halogen-containing (meth) acrylates such as trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, and perfluorooctyl ethyl (meth) acrylate;
nitrogen atom-containing polymerizable monomers such as (meth) acrylamide, N-dimethyl (meth) acrylamide, N-dimethylaminopropyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-methylol (meth) acrylamide, N' -dimethylaminoethyl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, and 2-isopropenyl-2-oxazoline;
polyfunctional polymerizable monomers such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and pentaerythritol tri (meth) acrylate;
isocyanate group-containing polymerizable monomers such as 2- (meth) acryloyloxyethyl isocyanate and (meth) acryloyl isocyanate;
ultraviolet-stable polymerizable monomers such as 4- (meth) acryloyloxy-2, 2, 6, 6-tetramethylpiperidine and 1- (meth) acryloyl-4-cyano-4- (meth) acrylamido-2, 2, 6, 6-tetramethylpiperidine;
polymerizable cyclic lactone monomers such as methylene butyrolactone and methyl methylene butyrolactone; (meth) acrylonitrile; maleic anhydride;
1, 4-dioxaspiro [4, 5] decan-2-yl methacrylic acid, (meth) acryloylmorpholine, tetrahydrofurfuryl acrylate, 4- (meth) acryloyloxymethyl-2-methyl-2-ethyl-1, 3-dioxolane, 4- (meth) acryloyloxymethyl-2-methyl-2-isobutyl-1, 3-dioxolane, 4- (meth) acryloyloxymethyl-2-methyl-2-cyclohexyl-1, 3-dioxolane, 4- (meth) acryloyloxymethyl-2, 2-dimethyl-1, 3-dioxolane, alkoxylated phenylphenol (meth) acrylate; and the like.
The other polymerizable monomer preferably has 1 to 22 carbon atoms, more preferably 1 to 18 carbon atoms, and further preferably 3 to 15 carbon atoms.
The polymer (a) may have only 1 kind of the other structural unit (a2), or may have 2 or more kinds of the other structural unit (a 2).
The content ratio of the structural unit (a2) in the polymer (a) is preferably 0 to 99 mol% based on 100 mol% of all the structural units. The content ratio of the structural unit (a2) is more preferably 5 mol% or more, still more preferably 10 mol% or more, still more preferably 96 mol% or less, and yet more preferably 92 mol% or less, from the viewpoint of imparting various physical properties derived from the structural unit (a2), such as flexibility, adhesiveness, stability, and heat resistance, to a cured product.
When 2 or more species are contained as the structural unit (a2), the content ratio is a total content ratio of the 2 or more species.
The content ratio of the structural units (a1) and (a2) may beTo use gas chromatography or liquid chromatography,1H-HMR or the like by the ratio of the reaction rates of the vinyl ether group-containing (meth) acrylate and the other monomers,1The corresponding integral values of H-NMR were determined by a comparative method.
The polymer (a) preferably has a terminal group derived from a silane compound having a carbon-carbon double bond at the end of the main chain. As described later, in the case where the polymer (a) is produced by group transfer polymerization using a silane compound having a carbon-carbon double bond as a polymerization initiator, a group derived from the silane compound having a carbon-carbon double bond is formed at the polymerization initiation side end of the main chain of the polymer.
As described later, the group transfer polymerization is one of anionic polymerization in which a monomer is polymerized using the silane compound having a carbon-carbon double bond as a polymerization initiator, and the silane compound having a carbon-carbon double bond forms a structure derived from a silane compound having a carbon-carbon double bond described later at the terminal and forms a new silyl ketene acetal at the growth terminal side of the polymer by addition to the (meth) acryloyl group of the vinyl ether group-containing (meth) acrylate or the polymerizable monomer having an electron-deficient double bond providing the structural unit (a 2). Then, a vinyl ether group-containing (meth) acrylate or a polymerizable monomer having an electron-deficient double bond providing the above-mentioned structural unit (a2) is further polymerized on the formed silyl ketene acetal. In the polymerization of the monomer component, the silyl ketene acetal at the growth end is thought to be continuously transferred to the end of the polymer molecule, thereby obtaining a polymer.
The terminal group derived from the silane compound having a carbon-carbon double bond preferably has a structure represented by the following general formula (3), (4) or (5).
[ solution 5]
Figure BDA0003519141520000081
(in the formula, R5And R6The same or different, represent a hydrogen atom or an organic group.R7Represents an organic group. )
[ solution 6]
Figure BDA0003519141520000082
(in the formula, R5、R6And R7’The same or different, represent a hydrogen atom or an organic group. )
[ solution 7]
Figure BDA0003519141520000091
(in the formula, R5、R6And R7’The same or different, represent a hydrogen atom or an organic group. )
In the above general formulae (3), (4) and (5), R is5And R6The organic group includes the same groups as those mentioned above, and among them, a hydrocarbon group having 1 to 12 carbon atoms is preferable.
Examples of the hydrocarbon group include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, and an aromatic hydrocarbon group. In the hydrocarbon group, at least a part of the atoms constituting the hydrocarbon group may be replaced with an oxygen atom, a nitrogen atom or a sulfur atom, and one or more of the hydrogen atoms constituting the hydrocarbon group may be replaced with a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom; a hydroxyl group; alkoxy, and the like.
Wherein R is5And R6The hydrocarbon group is more preferably an alkyl group, a cycloalkyl group, a haloalkyl group, or an aromatic hydrocarbon group having 1 to 6 carbon atoms, still more preferably an alkyl group or a cycloalkyl group having 1 to 6 carbon atoms, yet more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group or an ethyl group.
As R7And R7’Examples of the organic group include the same groups as those mentioned above, and among them, a hydrocarbon group having 1 to 22 carbon atoms is preferable, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aromatic hydrocarbon group is more preferable, and a methyl group, a n-butyl group, an ethyl group, a methyl group, an ethyl group, a salt, an ethyl group, an ethyl,Ethyl, propyl, butyl, tert-butyl, adamantyl, cyclohexyl, 2-ethylhexyl, and phenyl, and particularly preferably methyl, ethyl, and tert-butyl.
R7And R7’In the above-mentioned hydrocarbon group, at least a part of the atoms constituting the hydrocarbon group may be replaced with oxygen atoms, nitrogen atoms or sulfur atoms, and one or more of the hydrogen atoms constituting the hydrocarbon group may be replaced with a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom; a hydroxyl group; alkoxy, and the like.
Plural R7’May be the same or different.
In addition, R5And R6Or R6And R7Or R7’May be bonded to form a ring structure. Examples of the ring structure include alicyclic hydrocarbon structures such as cycloalkyl groups such as cyclohexyl and cyclopentyl; oxygen-containing heterocyclic structures such as a dihydrofuran ring, a tetrahydrofuran ring, a dihydropyran ring, a tetrahydropyran ring and the like; and the like.
When the polymer (a) is produced by the group transfer polymerization, when the silyl ketene acetal represented by the general formula (7), the vinyl silane compound represented by the general formula (8), and the allyl silane compound represented by the general formula (9) which will be described later are used as the polymerization initiators, the obtained polymers have the main chain ends having the structures represented by the general formulae (3), (4), and (5), respectively.
Among them, the polymer (a) preferably has a terminal group derived from a silyl ketene acetal represented by the general formula (3) in the main chain, from the viewpoint of easy control of the molecular weight distribution in the case of obtaining it by group transfer polymerization.
The polymer (a) may further have a terminal structure represented by the following general formula (6). When the main chain has a terminal structure represented by the following general formula (6) at one terminal, a desired function can be imparted to the polymer. The polymer (a) preferably has a terminal group derived from the silane compound having a carbon-carbon double bond at one end (first end) of the main chain and a terminal structure represented by the following general formula (6) at the other end (second end).
[ solution 8]
Figure BDA0003519141520000101
(in the formula, R1Represents a hydrogen atom or a methyl group. R2And R3The same or different, represent a hydrogen atom or an organic group. R4Represents a hydrogen atom or an organic group. X represents a hydrogen atom, a halogen atom, an alkyl group, a hydroxymethyl group, an allyl group or a propargyl group.
n represents an integer of 2 or more. )
In the above general formula (6), R1、R2、R3And R4And R in the above general formula (1)1、R2、R3And R4Are respectively the same.
In the general formula (6), X represents a hydrogen atom, a halogen atom, an alkyl group, a hydroxymethyl group, an allyl group or a propargyl group. The alkyl group is preferably an alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.
Among them, the above X is preferably a hydrogen atom from the viewpoint of being able to unify the terminal groups of the polymer, is preferably a propargyl group from the viewpoint of easily imparting a function to the polymer, and is preferably an alkyl group from the viewpoint of improving the stability of the polymer.
The polymer (A) has a molecular weight distribution (weight average molecular weight/number average molecular weight) of 1.0 to 4.0. By providing the polymer (a) with the structural unit (a1) and the molecular weight distribution, the curing reactivity is excellent, and variations in various physical properties as a cured product can be suppressed.
The molecular weight distribution of the polymer (a) is preferably 3.5 or less, more preferably 3.0 or less, and still more preferably 2.0 or less. The molecular weight distribution is also referred to as "dispersity".
The weight average molecular weight of the polymer (a) is in a suitable range for various applications, and is preferably 5000 to 1000000.
The weight average molecular weight of the polymer (a) is more preferably 10000 or more, further preferably 20000 or more from the viewpoint of durability, and more preferably 800000 or less, further preferably 600000 or less from the viewpoint of handling properties of the polymer.
The weight average molecular weight and the number average molecular weight of the polymer (a) can be measured by a Gel Permeation Chromatography (GPC) method, and specifically, can be determined by the method described in the examples below. The molecular weight distribution can be calculated by dividing the weight average molecular weight by the number average molecular weight.
The amount of the insoluble component in the polymer (a) is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less, based on 100% by mass of the polymer.
If the amount of the insoluble component is increased, a flat coating film or the like cannot be obtained, and there is a possibility that the shape of a cured product of the curable composition is deteriorated or the strength of the cured product is lowered.
The insoluble component is a gel component contained in the polymer, and is preferably a component insoluble in ethyl acetate, toluene or tetrahydrofuran, and has a solubility at 25 ℃ of 0.5g or less, preferably 0.1g or less, per 100g of ethyl acetate, toluene or tetrahydrofuran.
The amount of the insoluble component can be determined as follows: ethyl acetate, toluene or tetrahydrofuran was added so that the concentration of the polymer was about 33% by mass, and the mixture was sufficiently stirred at room temperature, and then passed through a filter having a pore size of 4 μm, and the mass of the insoluble matter remaining on the filter after drying was (b) and the mass of the initial polymer was (a), and the mass was obtained from (b)/(a) × 100.
With respect to the polymer (A), in a differential molecular weight distribution curve obtained by measuring the polymer (A) by a Gel Permeation Chromatography (GPC) method, a point of a maximum value of the differential molecular weight distribution curve is represented by T, and a point of a height of 5% of T on the differential molecular weight distribution curve is represented by L from a low molecular weight side0And L1In the case of (1), from T-L0-L1The area (X) of the triangle surrounded by the first and second molecular weight distribution curves and the connection L0-L1The ratio (X/Y) of the area (Y) of the portion surrounded by the lines (A) is preferably 0.8 to 2.0. When the polymer satisfies the above range of ratio, it can be said that gelation of the polymer is suppressed. The ratio (X/Y) is more preferably 0.8 to 1.5.
FIG. 1 is a schematic view showing a differential molecular weight distribution curve obtained by GPC measurement, and T, L described above0、L1。
The measurement conditions of GPC are the same as those described in the following examples.
The content of the polymer (a) is preferably 5 to 100% by mass based on 100% by mass of the total solid content of the curable composition, and more preferably 10% by mass or more, and even more preferably 15% by mass or more, from the viewpoint of improving the crosslinking density and imparting solvent resistance, hardness, and the like to a cured product. The content of the polymer (a) is more preferably 99.9% by mass or less, and still more preferably 95% by mass or less, based on 100% by mass of the total solid content of the curable composition.
In the present specification, the "total solid content" refers to the total amount of components forming a cured product (components other than a curing catalyst such as a solvent that volatilizes when the cured product is formed).
In addition, when the curable composition of the present invention is a curable composition for a resist, the content of the polymer (a) is preferably 1 to 50% by mass, more preferably 2 to 40% by mass, and still more preferably 5 to 30% by mass, based on 100% by mass of the total solid content of the curable composition, from the viewpoint of improving solvent resistance.
(method for producing Polymer (A))
The method for producing the polymer (a) is not particularly limited as long as it is a method capable of producing the polymer (a) having the above-described structure, and a method for producing the polymer (a) by group transfer polymerization of a monomer component containing the vinyl ether group-containing (meth) acrylate is preferable from the viewpoint of enabling efficient production of the polymer (a). By performing the group transfer polymerization, a polymer obtained by polymerizing only the (meth) acryloyl group of the vinyl ether group-containing (meth) acrylate can be efficiently produced. In addition, according to this method, the amount of gel components (insoluble components) contained in the obtained polymer can be suppressed to be low.
The group transfer polymerization is one of anionic polymerization in which a monomer is polymerized using a silane compound having a carbon-carbon double bond such as silyl ketene acetal as a polymerization initiator. The silane compound having a carbon-carbon double bond is added to the (meth) acryloyl group of the vinyl ether group-containing (meth) acrylate, and the silyl ketene acetal at the growth end of the newly formed polymer is transferred to the end of the polymer molecule, thereby obtaining a polymer.
By using such a group transfer polymerization, the polymerization reaction of the vinyl ether group-containing (meth) acrylate can be carried out at a relatively easily controllable temperature range such as room temperature. Further, the polymerization reaction can be carried out without strictly controlling the water content in the reaction system. In addition, when the above polymerization is applied, the generation of impurities is small, and a vinyl ether group-containing (meth) acrylate polymer can be produced at a high conversion rate in the case where a vinyl ether group remains.
A preferred method for producing the polymer (a) is described below using the above-described group transfer polymerization.
The method for producing the polymer (a) preferably includes: and a step of subjecting a monomer component comprising the vinyl ether group-containing (meth) acrylate to a group transfer polymerization in the presence of a silane compound having a carbon-carbon double bond and a catalyst.
In the polymerization reaction, specifically, before the reaction, any two of the monomer component, the catalyst, and the silane compound having a carbon-carbon double bond are charged into a reaction vessel, and the remaining one is added to start the polymerization. The order of addition of these is not particularly limited, and the polymerization may be started after addition by any method.
The silane compound having a carbon-carbon double bond, the catalyst, and the monomer component may be added in a single portion, or may be added in small amounts, or may be added in several portions.
The molecular weight of the polymer obtained by polymerizing the monomer component can be appropriately controlled by the kind and amount of the monomer component, the kind and amount of the silane compound having a carbon-carbon double bond, the kind and amount of the catalyst, and the kind and amount of the solvent used.
The amount of the silane compound having a carbon-carbon double bond is not particularly limited as long as the desired polymer can be obtained, and is preferably 1X 10 relative to the monomer component used, from the viewpoint of more efficiently producing the polymer-4Mol% to 10 mol%, more preferably 1X 10 mol%-3Mol% to 5 mol%, and more preferably 1X 10-2And (3) mol% to 1 mol%.
The amount of the catalyst to be used is not particularly limited as long as the desired polymer can be obtained, and is preferably 1X 10 relative to the monomer components to be used, from the viewpoint of more efficiently producing the polymer-4Mol% to 10 mol%, more preferably 1X 10 mol%-3Mol% to 5 mol%, and more preferably 1X 10-2And (3) mol% to 1 mol%.
The polymerization reaction can be carried out without using a solvent, but a solvent is preferably used. The solvent to be used is not limited as long as it can dissolve the raw material, the catalyst, the polymerization initiator, and the polymer, and an aprotic solvent is preferable in terms of enabling the polymerization reaction to proceed efficiently.
Specific examples of the solvent used in the present invention include: aromatic hydrocarbon solvents such as toluene, xylene, and benzene; aliphatic hydrocarbon solvents such as hexane, pentane, heptane and cyclohexane; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; halogenated hydrocarbon solvents such as chlorobenzene, dichloromethane, chloroform, 1, 2-dichloroethane and the like; nitrile solvents such as acetonitrile, propionitrile, and valeronitrile; ester-based solvents such as methyl acetate, ethyl acetate, isopropyl acetate, and butyl acetate; amide solvents such as Dimethylformamide (DMF), dimethylacetamide and N-methylpyrrolidone; ether solvents such as diethyl ether, diisopropyl ether, 1, 2-Dimethoxyethane (DME), 1, 4-dioxane, Tetrahydrofuran (THF), Tetrahydropyran (THP), anisole, diglyme (diglyme), diethylene glycol ethyl ether (carbitol), and cyclopentyl methyl ether (CPME); fluorine-based solvents such as perfluorohexane, perfluorocyclohexane, pentafluorobenzene, and octafluorotoluene; DMSO, nitromethane, and the like.
Among them, from the viewpoint of enabling the polymerization reaction to be further efficiently performed, the solvent is preferably at least one selected from the group consisting of an aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent, a ketone solvent, a halogenated hydrocarbon solvent, an ether solvent, an ester solvent, and a nitrile solvent, and more preferably an aromatic hydrocarbon solvent, an ether solvent, and an ester solvent.
The solvent can be used alone in 1, also can be combined with more than 2.
The amount of the solvent to be used is preferably 10 to 10000% by mass, more preferably 50 to 5000% by mass, and still more preferably 100 to 1000% by mass, based on 100% by mass of the total amount of the monomer components to be used.
In the above polymerization, the oxygen concentration in the solvent at the start of the polymerization is preferably 1000ppm or less. When the oxygen concentration in the solvent at the start of polymerization is in the above range, the activity of the silane compound having a carbon-carbon double bond, the catalyst, and the like is less likely to be lowered, so that the polymerization reaction proceeds more favorably, and the desired polymer can be produced more efficiently. The oxygen concentration is more preferably 800ppm or less, and still more preferably 0 to 500 ppm.
The oxygen concentration can be measured by a polarographic oxygen dissolution instrument.
In the above polymerization, the water content in the solvent at the start of the polymerization is preferably 1000ppm or less. When the water content in the solvent at the start of polymerization is in the above range, the silane compound having a carbon-carbon double bond is less likely to be decomposed, and the activity of the catalyst or the like is less likely to be lowered, so that the polymerization reaction proceeds more favorably, and the desired polymer can be produced more efficiently. The water content is more preferably 500ppm or less, and still more preferably 300ppm or less.
The above water content can be measured by the Karl Fischer moisture method.
The reaction temperature in the polymerization is not particularly limited, but is preferably-20 to 100 ℃, more preferably-10 to 50 ℃, and still more preferably 0 to 30 ℃ in view of controlling the molecular weight and molecular weight distribution and maintaining the catalyst activity. In addition, from the viewpoint of reduction in production cost, a process including polymerization at room temperature ± 20 ℃ is also one of preferable embodiments of the production method of the present invention.
The reaction time is not particularly limited, but is preferably 10 minutes to 48 hours, more preferably 30 minutes to 36 hours, and further preferably 1 hour to 24 hours.
The reaction atmosphere in the above polymerization may be an atmosphere, but is preferably an inert gas atmosphere such as nitrogen or argon.
The oxygen concentration in the atmosphere during the polymerization is preferably 10000ppm or less, more preferably 1000ppm or less, and still more preferably 100ppm or less.
The polymer obtained by the above polymerization reaction forms a silyl ketene acetal structure or an enol anion structure containing a silyl group of a polymerization initiator at the main chain end, and the silyl ketene acetal or the enol anion at one end of the polymer can be converted into a carboxylic acid or an ester by adding water, an alcohol, or an acid to the reaction system, thereby stopping the polymerization reaction.
Examples of the alcohol include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and 2-butanol.
Examples of the acid include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, and organic acids such as acetic acid and benzoic acid.
The amount of water, alcohol or acid used is not particularly limited, but is preferably 1 to 1000mol, more preferably 1 to 100mol, and still more preferably 1 to 10mol, based on 1mol of the silane compound having a carbon-carbon double bond used.
Instead of the water, alcohol or acid, an electrophile may be added. By adding an electrophile, a target functional group can be introduced to stop the polymerization reaction. Examples of the electrophile include halogen such as iodine or bromine, a halogenated succinimide compound, an alkyl halide, an allyl halide, a propargyl halide, an aldehyde, and an acid chloride.
The amount of the electrophile to be used is not particularly limited, but is preferably 0.5 to 1.5mol, more preferably 0.6 to 1.3mol, and still more preferably 0.8 to 1.2mol, based on 1mol of the silylketene acetal to be used.
The monomer components, the silane compound having a carbon-carbon double bond, and the catalyst used in the above-mentioned production method will be described.
Examples of the monomer component include a monomer capable of introducing the structural unit (a1) and a monomer capable of introducing the structural unit (a 2). Examples of the monomer capable of introducing the structural unit (a1) include the vinyl ether group-containing (meth) acrylates. Examples of the monomer capable of introducing the structural unit (a2) include the other polymerizable monomers described above.
The content of each monomer can be appropriately set so as to obtain a polymer having a structural unit in a desired content range.
Preferred examples of the silane compound having a carbon-carbon double bond include the following general formula (7):
[ solution 9]
Figure BDA0003519141520000151
(in the formula, R5And R6The same or different, represent a hydrogen atom or an organic group. R7、R8、R9And R10Identical or different, represent an organic group. R5And R6Or R6And R7May be bonded to form a ring structure. R8、R9And R10Two or more of them may be bonded to form a ring structure. ) A silicon carbide is shownAn alkylketene acetal represented by the following general formula (8):
[ solution 10]
Figure BDA0003519141520000152
(in the formula, R5、R6And R7’The same or different, represent a hydrogen atom or an organic group. R8、R9And R10Identical or different, represent an organic group. R5And R6Or R6And R7’May be bonded to form a ring structure. R8、R9And R10Two or more of them may be bonded to form a ring structure. ) A vinyl silane compound represented by the following general formula (9):
[ solution 11]
Figure BDA0003519141520000153
(in the formula, R5、R6And R7’The same or different, represent a hydrogen atom or an organic group. R8、R9And R10Identical or different, represent an organic group. R5And R6Or R6And R7’May be bonded to form a ring structure. R8、R9And R10Two or more of them may be bonded to form a ring structure. )1 or 2 or more of the allylsilane compounds shown.
Among them, silyl ketene acetal is more preferable from the viewpoint of facilitating efficient polymerization.
In the above general formulae (7), (8) and (9), R5And R6The same or different, represent a hydrogen atom or an organic group.
As the above-mentioned R5And R6Examples thereof include the compounds represented by the general formulae (3), (4) and (5) mentioned above5And R6Respectively, identical atoms or groups.
As the above-mentioned R7And R7’Can give an example ofAnd R in the above general formulae (3), (4) and (5)7And R7’Respectively, identical atoms or groups.
In the above general formulae (7), (8) and (9), R8、R9And R10Identical or different, represent an organic group.
As R8、R9And R10The organic group includes the same groups as those mentioned above, and among them, a hydrocarbon group and an alkoxy group having 1 to 12 carbon atoms are preferable, a hydrocarbon group and an alkoxy group having 1 to 6 carbon atoms are more preferable, and a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a phenyl group, a methoxy group, and an ethoxy group are further preferable.
In addition, the above R8、R9And R10In the hydrocarbon group, at least a part of the atoms constituting the hydrocarbon group may be replaced with an oxygen atom, a nitrogen atom or a sulfur atom, and one or more of the hydrogen atoms constituting the hydrocarbon group may be replaced with a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom; a hydroxyl group; alkoxy, and the like.
as-SiR in the above general formulae (7), (8) and (9)8R9R10Specific examples of the group include trimethylsilyl group, triethylsilyl group, triisopropylsilyl group, triisobutylsilyl group, tert-butyldimethylsilyl group, triphenylsilyl group, methyldiphenylsilyl group, dimethylphenylsilyl group, trimethoxysilyl group, and triethoxysilyl group. Among them, from the viewpoint of easy availability and easy synthesis, trimethylsilyl, triethylsilyl, triisopropylsilyl, tert-butyldimethylsilyl, triethoxysilyl and triphenylsilyl are preferable.
Specific examples of the silylketene acetal represented by the above general formula (7) include methyl (trimethylsilyl) dimethylketene acetal, methyl (trimethylsilyl) diisopropylketene acetal, methyl (triethylsilyl) dimethylketene acetal, methyl (triisopropylsilyl) dimethylketene acetal, methyl (t-butyldimethylsilyl) dimethylketene acetal, methyl (trimethylsilyl) diethylketene acetal, methyl (triphenylsilyl) dimethylketene acetal, methyl (methyldiphenylsilyl) dimethylketene acetal, methyl (dimethylphenylsilyl) dimethylketene acetal, methyl (triethoxysilyl) dimethylketene acetal, ethyl (trimethylsilyl) dimethylketene acetal, methyl (triisopropylsilyl) dimethylketene acetal, and the like, 2-ethylhexyl (trimethylsilyl) dimethylketene acetal, tert-butyl (trimethylsilyl) dimethylketene acetal, 1- [ (1-methoxy-2-methyl-1-propenyl) oxy ] -1-methylsilacyclobutane, and the like.
Among these, methyl (trimethylsilyl) dimethylketene acetal, methyl (triisopropylsilyl) dimethylketene acetal, and ethyl (trimethylsilyl) dimethylketene acetal are preferable from the viewpoints of easy availability, easy synthesis, and stability.
The silyl ketene acetals may be used alone in 1 kind, or in combination with 2 or more kinds.
As the vinyl silane compound represented by the above general formula (8), specifically, examples thereof include vinyltrimethylsilane, 1-trimethylsilylhexene, 1-trimethylsilyloctene, 1-trimethylsilyl-1-phenylethene, 1-trimethylsilyl-2-phenylethene, vinylt-butyldimethylsilane, 1-t-butyldimethylsilylhexene, 1-t-butyldimethylsilyloctene, 1-t-butyldimethylsilyl-2-phenylethene, vinyltris (trimethylsilyl) silane, 1-tris (trimethylsilyl) silylhexene, 1-tris (trimethylsilyl) silyloctene, and 1-tris (trimethylsilyl) silyl-2-phenylethene.
Specific examples of the allylsilane compound represented by the above general formula (9) include 3- (trimethylsilyl) -1-propene, 3- (triethylsilyl) -1-propene, 3- (dimethylethylsilyl) -1-propene, 3- (triisopropylsilyl) -1-propene, 3- (dimethylisopropylsilyl) -1-propene, 3- (tri-n-propylsilyl) -1-propene, 3- (dimethyl-n-propylsilyl) -1-propene, 3- (tri-n-butylsilyl) -1-propene, 3- (dimethyl-n-butylsilyl) -1-propene, 3- (triphenylsilyl) -1-propene, and mixtures thereof, 3- (dimethylphenylsilyl) -1-propene, 2-methyl-3- (trimethylsilyl) -1-propene, 3- (trimethylsilyl) -2-methyl-1-propene, 3- (triphenylsilyl) -2-methyl-1-propene, and the like.
The catalyst preferably includes a substance that functions as a basic catalyst such as a bronsted base or a lewis base, and includes an inorganic base such as an alkali metal hydroxide or an alkaline earth metal hydroxide; organic bases such as trialkylamine and pyridine; and so on.
Among these, the catalyst is preferably at least one selected from the group consisting of organic phosphorus compounds, N-heterocyclic carbenes, fluorine-containing ionic compounds, cyclic amine compounds and ammonium salt compounds, from the viewpoint that the polymerization of the vinyl ether group-containing (meth) acrylates can be performed more efficiently. When these specific catalysts are used, cationic polymerization of a vinyl ether group or decomposition of a vinyl ether group is less likely to occur in the vinyl ether group-containing (meth) acrylic acid ester, and only a (meth) acryloyl group can be polymerized more efficiently.
Examples of the organophosphorus compound include 1-tert-butyl-4, 4, 4-tris (dimethylamino) -2, 2-bis [ tris (dimethylamino) phosphoranylideneamino]-2λ5，4λ5Phosphonitrile (phosphazene base P4-t-BuP)4) 1-tert-octyl-4, 4, 4-tris (dimethylamino) -2, 2-bis [ tris (dimethylamino) phosphoranylideneamino]-2λ5，4λ5Bis (phosphazene) s (phosphazene base P4-tOct), 1-tert-butyl-2, 2, 4, 4, 4-pentakis (dimethylamino) -2. lambda5，-4λ5Bis (phosphazene) s (phosphazene base P2-t-Bu), 1-ethyl-2, 2, 4, 4, 4-pentakis (dimethylamino) -2. lambda5，4λ5Bis (phosphazene) s (phosphazene base P2-t-Et), t-butyliminotris (dimethylamino) phosphorane (phosphazene base P1-t-Bu), t-butyliminotris (pyrrolidinyl) phosphorane (BTPP), 2-t-butylimino-2-diethylamino-1, 3-dimethylperhydro-1,phosphazene bases such as 3, 2-diazaphosphobenzene; tris (2, 4, 6-trimethoxyphenyl) phosphine, tributylphosphine, tris (dimethylaminophosphine), 2, 8, 9-triisobutyl-2, 5, 8, 9-tetraaza-1-phosphabicyclo [3, 3] s]Undecane, 2, 8, 9-trimethyl-2, 5, 8, 9-tetraaza-1-phosphabicyclo [3, 3]Undecane, 2, 8, 9-triisopropyl-2, 5, 8, 9-tetraaza-1-phosphabicyclo [3, 3]Undecane; and so on. Among them, the phosphazene base P4-t-BuP is preferable in that it is highly basic and can effectively activate silylketene acetal 42, 8, 9-triisobutyl-2, 5, 8, 9-tetraaza-1-phosphabicyclo [3, 3]Undecane.
Examples of the N-heterocyclic carbene include 1, 3-dimethylimidazol-2-ylidene, 1, 3-diethylimidazol-2-ylidene, 1, 3-di-t-butylimidazol-2-ylidene, 1, 3-dicyclohexylimidazol-2-ylidene, 1, 3-diisopropylimidazol-2-ylidene, 1, 3-bis (1-adamantyl) imidazol-2-ylidene, and 1, 3-ditrimethylphenylimidazol-2-ylidene. Among them, 1, 3-di-tert-butylimidazol-2-ylidene and 1, 3-diisopropylimidazol-2-ylidene are preferable from the viewpoint of enabling efficient activation of the silylketene acetal.
Examples of the fluoride ion-containing compound include tetra-n-butylammonium fluoride (TBAF) and tris (dimethylamino) sulfonium difluoride (TASHF)2) Hydrogen fluoride-pyridine, tetrabutylammonium difluoride, potassium bifluoride, and the like. Among them, tetra-n-butylammonium fluoride (TBAF), tetrabutylammonium difluoride, tris (dimethylamino) sulfonium difluoride (TASHF) are preferable from the viewpoint of easy availability and effective activation of silylketene acetal2)。
Examples of the cyclic amine compound include 1, 8-diazabicyclo [5.4.0] undec-7-ene, 1, 5-diazabicyclo [4.3.0] non-5-ene, and 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene.
Examples of the ammonium salt compound include tetrabutylammonium diacetate, tetrabutylammonium acetate, tetrabutylammonium benzoate, tetrabutylammonium diphenylate, tetrabutylm-chlorobenzoate, tetrabutylammonium cyanate, tetrabutylammonium methoxide, tetrabutylammonium mercaptide, tetrabutylammonium dibromide, and compounds obtained by changing the ammonium cation of these ammonium salt compounds to tetramethylammonium, triethylammonium, benzyltributylammonium, N-methyl-N-butylpiperidinium, N-methyl-N-butylpyrrolidinium cation, or compounds obtained by changing the ammonium cation to pyridinium cation.
In addition to the above compounds, strongly basic nitrogen-containing heterocyclic compounds such as 1, 8-diazabicyclo [5.4.0] undec-7-ene, 1, 5-diazabicyclo [4.3.0] non-5-ene, and 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene can be used.
The catalyst may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
In the above polymerization, other components may be further used in addition to the above components within a range not affecting the effect of the present invention. Examples of the other components include known additives such as a polymerization initiator, a chain transfer agent, a polymerization accelerator, and a polymerization inhibitor, which are generally used in a polymerization reaction. They may be appropriately selected as necessary.
The above-mentioned production method may include a step other than the above-mentioned polymerization reaction step. Examples of the other steps include an aging step, a neutralization step, a deactivation step of a polymerization initiator or a chain transfer agent, a dilution step, a drying step, a concentration step, a purification step, and the like. These steps can be performed by a known method.
The polymer (a) is preferably produced by the above production method. That is, the polymer (a) is preferably a group transfer polymer containing a monomer component of a vinyl ether group-containing (meth) acrylate represented by the general formula (2).
In the case of producing the polymer (a) by the above production method, the conversion rate of the monomer component used in the polymerization is extremely high, and the amount of the residual monomer can be extremely reduced.
On the other hand, in the case of producing the polymer (a) by radical polymerization, even if a polymer in which the molecular weight distribution of the polymer is controlled within the above-mentioned predetermined range can be obtained without gelation, there is a possibility that the monomer remains and the amount thereof is difficult to control, and therefore, the reproducibility of the physical property expression of the obtained cured product is lowered.
The content of the residual monomer in the polymer (a) is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 0 to 3% by mass, based on 100% by mass of the polymer.
The content of residual monomers can be determined by1H-NMR, gas chromatography, liquid chromatography, and gel permeation chromatography.
< polymerizable Compound (B) >
The polymerizable compound used in the present invention is not particularly limited as long as it is a compound capable of crosslinking the polymer (a), and among them, at least one selected from the group consisting of vinyl ether compounds, cyclic ether compounds, (meth) acrylic acid esters, carboxylic acid compounds, maleimide compounds, alcohols, and thiols is preferable from the viewpoint of being capable of efficiently reacting with a vinyl ether group. Among these, the polymerizable compound is more preferably a vinyl ether compound, a cyclic ether compound, or a thiol, and still more preferably a vinyl ether compound or a cyclic ether compound.
The polymerizable compound may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
Examples of the vinyl ether compound include: alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2, 2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, and the like; vinyl aryl ethers such as vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2, 4-dichlorophenyl ether, vinyl naphthyl ether, and vinyl anthracenyl ether; alicyclic compound-containing vinyl ethers such as cyclohexyl vinyl ether and cyclohexanedimethanol monovinyl ether; allyl-containing vinyl ethers such as allyl vinyl ether; polyfunctional divinyl ethers such as diethylene glycol divinyl ether, triethylene glycol divinyl ether, 1, 4-butanediol divinyl ether, and 1, 4-cyclohexanedimethanol divinyl ether; and the like.
The molecular weight of the vinyl ether compound is preferably 10000 or less.
Examples of the cyclic ether compound include an epoxy group-containing compound, an oxetane compound, a compound having a tetrahydrofuran ring, and a cyclic ether group-containing (meth) acrylate similar to the polymerizable monomer.
Specific examples of the cyclic ether compound include: monofunctional epoxy resins such as n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, and 1, 2-epoxycyclohexane; 2-functional epoxy resins such as hexanediol diglycidyl ether, tetraethylene glycol diglycidyl ether, bisphenol a diglycidyl ether, bisphenol F diglycidyl ether, monoallyl diglycidyl isocyanurate, and glycidyl methacrylate; polyfunctional epoxy resins such as trimethylolpropane triglycidyl ether, sorbitol polyglycidyl ether, 1, 3-bis (N, N-diglycidylaminoethyl) benzene, novolak-type epoxy resins, and tetraphenolethane-type epoxy resins; epoxy resins having an alicyclic oxirane ring such as 1, 2-epoxy-4-vinylcyclohexane, 3 ', 4' -epoxycyclohexylmethyl-3, 4-epoxycyclohexylcarboxylate, and 3, 4-epoxycyclohexylmethylmethacrylate; monofunctional oxetane resins such as 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-phenoxymethyloxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl (triethoxysilylpropyloxymethyl) oxetane and 3-cyclohexyloxymethyl-3-ethyl-oxetane; 2-functional oxetane resins such as bis (3-ethyl-3-oxetanylmethyl) ether, 1, 4-bis { [ (3-ethyl-3-oxetanyl) methoxy ] methyl } benzene and the like; polyfunctional oxetane resins such as trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol penta (3-ethyl-3-oxetanylmethyl) ether and the like.
The molecular weight of the cyclic ether compound is preferably 10000 or less.
Examples of the (meth) acrylate include: monofunctional (meth) acrylates such as methyl (meth) acrylate, butyl (meth) acrylate, isoamyl (meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, ethoxydiglycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, hexafluoropropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate; polyfunctional (meth) acrylates such as 1, 6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, glycerin di (meth) acrylate, 9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl ] fluorene, dimethylol tricyclodecane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris ((meth) acryloyloxyethyl) isocyanurate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like; and macromonomers having a (meth) acryloyl group such as epoxy (meth) acrylate, urethane (meth) acrylate, and polyester (meth) acrylate.
The molecular weight of the (meth) acrylate is preferably 10000 or less.
Examples of the carboxylic acid compound include: compounds having 2 or more functional groups in the molecule, such as succinic acid, malonic acid, maleic acid, adipic acid, malic acid, tartaric acid, azobenzene-4, 4' -dicarboxylic acid, cyclohexane-1, 4-dicarboxylic acid, citric acid, trimellitic acid, and 1, 3, 5-tricarboxylic acid benzene; and polymers containing a carboxyl group in a side chain, such as poly (meth) acrylic acid.
The molecular weight of the carboxylic acid compound is preferably 10000 or less.
Examples of the maleimide compound include: n-phenylmaleimide, N-cyclohexylmaleimide, N '-tetramethylenebismaleimide, bisphenol A bis (4-maleimidophenylether), 4' -diphenylmethane bismaleimide, m-phenylenebismaleimide, maleimide compounds such as 3, 3 '-dimethyl-5, 5' -diethyl-4, 4 '-diphenylmethane bismaleimide, 4-methyl-1, 3-phenylene bismaleimide, 1, 6' -bismaleimide- (2, 2, 4-trimethyl) hexane, 4 '-diphenyl ether bismaleimide, 4' -diphenyl sulfone bismaleimide and 1, 3-bis (3-maleimidophenoxy) benzene.
The molecular weight of the maleimide compound is preferably 10000 or less.
Examples of the alcohol include compounds having 2 or more hydroxyl groups in the molecule, such as ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, 1, 7-heptanediol, pentaerythritol, trimethylolpropane, trimethylolethane, dihydroxynaphthalene, 2, 4-diethyl-1, 5-pentanediol, 4 '- (hexafluoroisopropylidene) diphenol, 1, 3-cyclohexanediol, 1, 4-cyclohexanediol, cyclohexanedimethanol, 4' -biphenyldimethanol, 9-bis (4-hydroxyphenyl) fluorene, 2-bis (4-hydroxyphenyl) propane, dipentaerythritol, and the like.
The molecular weight of the alcohol is preferably 10000 or less.
Examples of the thiol include compounds having 2 or more mercapto groups in the molecule, such as 1, 2-ethanedithiol, 1, 3-propanedithiol, 2, 4, 6-trimercaptotriazine, 2-dibutylamino-4, 6-dimercaptotriazine, 1, 4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), and the like. Further, compounds containing at least 1 carboxyl group and at least 1 mercapto group in each molecule, such as thioglycolic acid and 3-mercaptopropionic acid, may be used.
The molecular weight of the thiol is preferably 10000 or less.
In addition, the polymerizable compound is also preferably a methylene malonate diester compound in view of being curable at a low temperature.
Examples of the methylene malonate diester compound include a diester compound represented by the following general formula (10) and a polyfunctional methylene malonate diester in which a plurality of methylene malonates are bonded.
[ solution 12]
Figure BDA0003519141520000211
(in the formula (10), R11And R12The same or different, represent a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms, or R11And R12Together form a 2-valent hydrocarbon group having 3 to 15 carbon atoms. R13And R14The same or different, and represents a 1-valent organic group having 1 to 30 carbon atoms. )
The above-mentioned polyfunctional methylene malonic acid diester includes a reaction product obtained by reacting a diester compound represented by the above general formula (10) with a polyhydric alcohol under conditions such that an ester exchange reaction occurs between the diester compound and the polyhydric alcohol, and examples thereof include compounds represented by the following general formula (11) or (12).
[ solution 13]
Figure BDA0003519141520000212
(in the formula (11), R11And R12The same or different, represent a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms, or R11And R12Together form a 2-valent hydrocarbon group having 3 to 15 carbon atoms. R13Represents a 1-valent organic group having 1 to 30 carbon atoms. R15Represents an n-valent organic group. n represents the number of constitutional units included in parentheses in formula (11) and represents an integer of 2 or more. In the formula (11), a plurality of R's are present11、R12And R13May be the same or different from each other. )
[ solution 14]
Figure BDA0003519141520000221
(in the formula (12), R11And R12The same or different, represent a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms, or R11And R12Together form a 2-valent hydrocarbon group having 3 to 15 carbon atoms. R13Represents a 1-valent organic group having 1 to 30 carbon atoms. R16Represents a 2-valent organic group. R17Represents a hydroxyl group or a 1-valent organic group. m represents the number of structural units in parentheses contained in formula (12), and represents an integer of 2 or more. Multiple existence of R11、R12And R16May be the same or different from each other. )
In the above general formulae (10), (11) and (12), R is11And R12The number of carbon atoms of the hydrocarbon group is preferably 1 to 10, more preferably 1 to 5.
As R11And R12Examples of the hydrocarbon group include a methyl group, an ethyl group, an n-butyl group, an n-pentyl group (pentyl group), an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an isopropyl group, a 2-methylbutyl group, an isopentyl group, a 3, 3-dimethylbutyl group, a 2-ethylbutyl group, a 2-ethyl-2-methylpropyl group, an isoheptyl group, an isooctyl group, a 2-ethylhexyl group, a 2-propylpentyl group, a neononyl group, a 2-ethylheptyl group, a 2-propylhexyl group, a 2-butylpentyl group, an isodecyl group, a neodecyl group, a 2-ethyloctyl group, a 2-propylheptyl group, a 2-butylhexyl group, an isoundecyl group, a neoundecyl group, a 2-ethylnonyl group, a 2-propyloctyl group, 2-butylheptyl, 2-pentylhexyl, isododecyl, neododecyl, 2-ethyldecyl, 2-propylnonyl, 2-butyloctyl, 2-pentylheptyl, isotridecyl, neotridecyl, 2-ethylundecyl, 2-propyldecyl, 2-butyloctyl, 2-pentyloctyl, 2-hexylheptyl, isotetradecyl, neotetradecyl, 2-ethyldodecyl, 2-propylundecyl, 2-butyldecyl, 2-pentylnonyl, 2-hexyloctyl, isopentadecyl, neopentadecyl, cyclohexylmethyl, benzyl, etc.
In the above general formulae (10), (11) and (12), R11And R12At least one of them may be a hydrogen atom, or both may be a hydrogen atom, preferably R11And R12Both are hydrogen atoms.
In addition, the above R11And R12May be R11And R12Together form a 2-valent hydrocarbon group having 3 to 15 carbon atoms. In this case, the number of carbon atoms of the 2-valent hydrocarbon group is preferably 4 to 12, more preferably 5 to 9.
Specific examples of the above-mentioned 2-valent hydrocarbon group include 1, 3-propylene group, 1, 4-butylene group, 1, 5-pentylene group, 1, 6-hexylene group, 1, 5-hexylene group and the like.
In the above general formulae (10), (11) and (12), R13And R14Identical or different, are 1-valent organic radicals. Examples of the organic group include a 1-valent hydrocarbon group, a 1-valent heteroatom-containing group, and the like, and these groups may have 1 or 2 or more substituents. Examples of the substituent include an alkoxy group, a hydroxyl group, a nitro group, an azido group, a cyano group, an acyl group, an acyloxy group, a carboxyl group, a heterocyclic group, and an ester group, and these substituents may be further substituted with a substituent.
R13And R14The number of the substituents is not limited, but is preferably 5 or less, more preferably 3 or less.
R13And R14The number of carbon atoms in (b) is 1 to 30, preferably 1 to 20, more preferably 1 to 15, still more preferably 1 to 10, and particularly preferably 1 to 6.
R13And R14When 1 or 2 or more substituents are present, the number of carbon atoms including the substituents is preferably within the above-described range.
The 1-valent hydrocarbon group may be any of a 1-valent aliphatic hydrocarbon group and an aromatic hydrocarbon group, and the aliphatic hydrocarbon group may be any of a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, and an alicyclic hydrocarbon group. The aliphatic hydrocarbon group may be any of a saturated aliphatic hydrocarbon group and an unsaturated aliphatic hydrocarbon group.
The alicyclic hydrocarbon group is a group having a cyclic aliphatic hydrocarbon moiety, and may have a linear or branched aliphatic hydrocarbon moiety.
The aromatic hydrocarbon group is a group having an aromatic ring and may have an aliphatic moiety.
Examples of the aliphatic hydrocarbon group include the same groups as those of the aliphatic hydrocarbon group and the alicyclic hydrocarbon group.
Examples of the aromatic hydrocarbon group include the same groups as those of the aromatic hydrocarbon group.
Among them, aliphatic hydrocarbon groups are preferable, and saturated aliphatic hydrocarbon groups are more preferable.
Examples of the 1-valent heteroatom-containing group include a polyalkylene oxide group and a polyester group.
R is as defined above13And R14Or may be R13And R14Together form a 2-valent organic group having 3 to 30 carbon atoms. In this case, the number of carbon atoms of the 2-valent organic group is preferably 3 to 10, more preferably 3 to 6.
The above-mentioned 2-valent organic group may include a 2-valent hydrocarbon group, and specific examples of the above-mentioned 2-valent hydrocarbon group include a2, 2-propylene group, a1, 3-propylene group, a1, 4-butylene group, a1, 5-pentylene group, a1, 6-hexylene group, a1, 5-hexylene group, and the like.
The above-mentioned 2-valent organic group may be a group in which one or more hydrogen atoms of a 2-valent hydrocarbon group having 3 to 15 carbon atoms are substituted with a substituent. Examples of the substituent include the above-mentioned group R13And R14The same substituents as in (1) and the like. The above-mentioned 2-valent organic group preferably has 1 to 5 substituents, more preferably 1 to 3 substituents.
The above-mentioned 2-valent organic group may be a 2-valent heteroatom-containing group, and examples of the 2-valent heteroatom-containing group include polyalkylene oxide, polyester group and the like.
R in the above general formula (11)15Is an n-valent organic group, is an organic group having a valence of 2 or more, and is preferably a residue obtained by removing 2 or more hydroxyl groups from a polyol, for example.
Examples of the polyhydric alcohol include glycerin, polyglycerin, a compound obtained by adding an alkylene glycol to glycerin, erythritol, xylitol, sorbitol, trimethylolpropane, pentaerythritol, dipentaerythritol, and the like.
The upper limit of n is not particularly limited, but is preferably 100 or less, more preferably 12 or less, and still more preferably 6 or less.
R15The number of carbon atoms of the n-valent organic group is preferably 1 to 30, more preferably 1 to 20, further preferably 1 to 15, and particularly preferably 1 to 10.
R in the above general formula (12)16Is a 2-valent organic group.
As R16Examples of the 2-valent organic group include the same groups as those of the above 2-valent organic group, and preferably a residue obtained by removing 2 hydroxyl groups from a diol, a residue obtained by removing 2 hydroxyl groups from a polyalkylene glycol, and the like.
Examples of the diol or polyalkylene glycol include ethylene glycol, butanediol, polyethylene glycol, and polypropylene glycol.
R16The number of carbon atoms of the 2-valent organic group is preferably 1 to 30, more preferably 1 to 20, further preferably 1 to 15, and particularly preferably 1 to 10.
R in the above general formula (12)17Represents a hydroxyl group or a 1-valent organic group.
As R17The 1-valent organic group is not particularly limited, and examples thereof include the group represented by the formula R13And R14The 1-valent organic groups shown are the same groups, and the like.
R17Preferably a hydroxyl group or a group represented by the following general formula (13).
[ solution 15]
Figure BDA0003519141520000241
(in the formula (13), R11And R12The same or different, represent a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms, or R11And R12Together form a 2-valent hydrocarbon group having 3 to 15 carbon atoms. R14Represents a carbon number of 1 to 30A 1-valent organic group. )
As R in the above general formula (13)11、R12And R14Each of which is as defined above for R11、R12、R14The same atom or group.
Specific examples of the diester compound represented by the above general formula (10) include methylpropyl methylenemalonate, dihexyl methylenemalonate, dicyclohexyl methylenemalonate, diisopropyl methylenemalonate, butyl methyl methylenemalonate, ethoxyethyl methylenemalonate, methoxyethyl methyl methylenemalonate, hexyl ethyl methylenemalonate, diamyl methylenemalonate, ethylpentyl methylenemalonate, methyl pentyl methylenemalonate, ethylethylmethoxy methylenemalonate, ethoxyethyl methyl methylenemalonate, butyl ethyl methylenemalonate, dibutyl methylenemalonate, diethyl methylenemalonate (DEMM), diethoxyethyl methylenemalonate, dimethyl methylenemalonate, di-n-propyl methylenemalonate, ethylhexyl methylenemalonate, Fenchylmethyl methylmethylmethylmalonate, menthyl methylmalonate, 2-phenylpropylethyl methylmalonate, 3-phenylpropylpropylmethylmalonate, dimethoxyethyl methylmalonate, and the like.
The molecular weight of the methylene malonic acid diester compound is preferably 10000 or less.
Further, as the polymerizable compound, α -cyanoacrylate may also be preferably used.
As the α -cyanoacrylate, conventionally known α -cyanoacrylate can be used, and specific examples thereof include: alkyl- α -cyanoacrylates and cycloalkyl- α -cyanoacrylates such as methyl- α -cyanoacrylate, ethyl- α -cyanoacrylate, propyl- α -cyanoacrylate, butyl- α -cyanoacrylate, and cyclohexyl- α -cyanoacrylate; alkenyl- α -cyanoacrylates and cycloalkenyl- α -cyanoacrylates such as allyl- α -cyanoacrylate, methallyl- α -cyanoacrylate, and cyclohexenyl- α -cyanoacrylate; alkynyl- α -cyanoacrylates such as propynyl- α -cyanoacrylate; aryl- α -cyanoacrylates such as phenyl- α -cyanoacrylate and tolyl- α -cyanoacrylate; methoxyethyl-alpha-cyanoacrylate, ethoxyethyl-alpha-cyanoacrylate, furfuryl-alpha-cyanoacrylate containing a hetero atom; silicon-containing trimethylsilylmethyl- α -cyanoacrylate, trimethylsilylethyl- α -cyanoacrylate, trimethylsilylpropyl- α -cyanoacrylate, dimethylvinylsilylmethyl- α -cyanoacrylate; and the like. Among them, from the viewpoint of performance and cost, alkyl- α -cyanoacrylate and cycloalkyl- α -cyanoacrylate are preferable, and ethyl- α -cyanoacrylate is more preferable.
The molecular weight of the α -cyanoacrylate is preferably 10000 or less.
In addition, as the polymerizable compound, a compound capable of forming a crosslinked structure by reacting with a vinyl ether group may be used. Examples thereof include: aliphatic alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 3-methyl-1, 5-pentanediol, propylene glycol, dipropylene glycol, polytetraethylene glycol, polycarbonate glycol, and glycerin; aromatic alcohols such as 4, 4' -biphenol and bisphenol a; anhydrides such as maleic anhydride; and the like.
When the curable composition of the present invention contains the polymerizable compound (B), the content of the polymerizable compound (B) is preferably 1 to 95% by mass, and more preferably 10 to 90% by mass, based on 100% by mass of the total solid content of the curable composition.
In addition, as the polymerizable compound (B), an acid group-containing alkali-soluble resin (B1) and/or a resin (B2) having a group that generates an acid group by heat or acid can also be preferably used. By containing these resins, the polymer (a) can react with the acid groups contained in the resins, and the curable composition of the present invention can sufficiently undergo a curing reaction even under relatively low curing conditions at a temperature of 200 ℃. Further, a cured product having excellent solvent resistance can be provided, and the cured product can be suitably used in various applications such as various optical components used in liquid crystal/organic EL/quantum dot/micro LED liquid crystal display devices, solid-state imaging elements, touch panel display devices, and the like, and structural components of electric/electronic devices, and the like.
Acid group-containing alkali soluble resin (b1)
The acid group-containing alkali-soluble resin (b1) (hereinafter also referred to as "resin (b 1)") is a polymer having an acid group. By having an acid group, it becomes alkali-soluble.
Examples of the acid group include a functional group which causes a neutralization reaction with basic water, such as a carboxyl group, a phenolic hydroxyl group, a carboxylic anhydride group, a phosphoric acid group, and a sulfonic acid group, and only 1 kind or 2 or more kinds of these groups may be present. Among them, a carboxyl group or a carboxylic anhydride group is preferable, and a carboxyl group is more preferable.
(b1-1) structural Unit having acid group
The resin (b1) preferably has the structural unit (b1-1) having an acid group.
Examples of the method for obtaining the polymer having the structural unit (b1-1) include: a method (1) of polymerizing a monomer component containing an acid group-containing monomer; a method (2) in which a monomer component containing an epoxy group-containing monomer is polymerized to obtain an epoxy group-containing polymer, and then an acid group of the acid group-containing monomer is subjected to an addition reaction with the epoxy group to thereby open the epoxy group and react a polybasic acid or a polybasic acid anhydride with a hydroxyl group generated at that time to generate a carboxyl group; or the like, or a combination of these methods.
In the above method (1), the above structural unit (b1-1) is a structural unit derived from a monomer having an acid group. In the method (2), the structural unit (b1-1) is a structural unit containing a carboxyl group formed by reacting a monomer containing an acid group with a structural unit derived from a monomer containing an epoxy group, and further reacting a polybasic acid or a polybasic acid anhydride.
Among them, the structural unit (b1-1) is preferably a structural unit derived from a monomer having an acid group.
Examples of the acid group-containing monomer include compounds having the acid group and a polymerizable double bond (carbon-carbon double bond) in the molecule. Examples of the polymerizable double bond include a (meth) acryloyl group, a vinyl group, an allyl group, and a methallyl group. Among them, (meth) acryloyl groups are preferable.
Specific examples of the acid group-containing monomer include: unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, cinnamic acid, and vinylbenzoic acid; unsaturated polycarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid; long-chain unsaturated monocarboxylic acids in which chain extension has been performed between an unsaturated group such as β -carboxyethyl (meth) acrylate, mono 2- (2-acryloyloxyethyl) succinate or mono 2- (2-methacryloyloxyethyl) succinate and a carboxyl group; unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride; LIGHT ESTER P-1M (chemical Co., Ltd.) or the like; and the like. Among these, carboxylic acid monomers (unsaturated monocarboxylic acids, unsaturated polycarboxylic acids, long-chain unsaturated monocarboxylic acids, unsaturated anhydrides) are preferable from the viewpoint of versatility, availability, and the like. From the viewpoint of reactivity, alkali solubility, and the like, the acid group-containing monomer is more preferably an unsaturated monocarboxylic acid, and still more preferably (meth) acrylic acid.
The epoxy group-containing monomer includes a compound having an epoxy group and the polymerizable double bond in the molecule, and preferably includes an epoxy group-containing (meth) acrylate.
Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate, (. beta. -methylglycidyl (meth) acrylate, (. beta. -ethylglycidyl (meth) acrylate, vinylbenzyl glycidyl ether, allyl glycidyl ether, (3, 4-epoxycyclohexyl) methyl (meth) acrylate, and vinylepoxycyclohexane. Among them, glycidyl (meth) acrylate and (3, 4-epoxycyclohexyl) methyl (meth) acrylate are preferable, and glycidyl (meth) acrylate is more preferable.
Examples of the polybasic acid or polybasic acid anhydride include polybasic acids such as succinic acid, maleic acid, phthalic acid, tetrahydrophthalic acid, and the like; succinic anhydride (also known as succinic anhydride), maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydrides such as nadic anhydride, nadic methyl anhydride, itaconic anhydride, and trimellitic anhydride. Among them, polybasic acid anhydrides are preferable.
The resin (b1) may have only 1 type of the structural unit (b1-1) or 2 or more types of the structural unit (b 1-1).
From the viewpoint of maintaining appropriate developability, the content of the structural unit (b1-1) is preferably 3% by mass or more, more preferably 5% by mass or more, and still more preferably 7% by mass or more, and further preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 20% by mass or less, based on 100% by mass of all the structural units of the resin (b 1).
(b1-2) structural Unit having Ring Structure in Main chain
The resin (b1) is preferably a polymer having a ring structure in the main chain. The heat resistance of the resin (b1) can be improved by having a ring structure in the main chain. Examples of the ring structure include an imide ring, a tetrahydrofuran ring, and a lactone ring. In order to have these ring structures, the resin (b1) preferably further has a structural unit (b1-2) having a ring structure in the main chain.
Examples of the monomer capable of introducing the structural unit (b1-2) include: a monomer having a ring structure containing a double bond in a molecule; a monomer which is cyclized to form a polymer having a ring structure in the main chain; monomers forming a ring structure after polymerization; and the like. Among them, from the viewpoint of good heat resistance, solvent resistance, hardness, dispersibility of a coloring material, and the like, at least one monomer selected from the group consisting of an N-substituted maleimide-based monomer, a dialkyl-2, 2 '- (oxydimethylene) diacrylate-based monomer, and an α - (unsaturated alkoxyalkyl) acrylate-based monomer is preferable, and from the viewpoint of more excellent heat-resistant coloring property, at least one monomer selected from the group consisting of an N-substituted maleimide-based monomer and a dialkyl-2, 2' - (oxydimethylene) diacrylate-based monomer is more preferable.
Examples of the N-substituted maleimide monomer include N-cyclohexylmaleimide, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-t-butylmaleimide, N-dodecylmaleimide, N-benzylmaleimide, and N-naphthylmaleimide, and 1 or 2 or more of them may be used. Among these, N-phenylmaleimide and N-benzylmaleimide are preferable, and N-benzylmaleimide is particularly preferable from the viewpoint of transparency.
Examples of the N-benzylmaleimide include: benzyl maleimide; alkyl-substituted benzylmaleimides such as p-methylbenzylmaleimide and p-butylbenzylmaleimide; phenolic hydroxyl-substituted benzylmaleimides such as p-hydroxybenzylmaleimide; halogen-substituted benzylmaleimides such as o-chlorobenzylmaleimide, o-dichlorobenzylmaleimide and p-dichlorobenzylmaleimide; and the like.
Examples of the dialkyl-2, 2 '- (oxydimethylene) diacrylate monomers include compounds having at least 1 ester moiety containing a tertiary carbon, such as 2, 2' - [ oxybis (methylene) ] bisacrylic acid, dialkyl-2, 2 '- [ oxybis (methylene) ] bis-2-acrylate, and dialkyl-2, 2' - [ oxybis (methylene) ] bis-2-acrylate. Among these, for example, dimethyl-2, 2' - [ oxybis (methylene) ] bis-2-acrylate is preferably used from the viewpoint of transparency, dispersibility, industrial availability and the like.
Examples of the α - (unsaturated alkoxyalkyl) acrylate monomer include α -allyloxymethylacrylic acid, α -allyloxymethylmethacrylate, ethyl α -allyloxymethylacrylate, n-propyl α -allyloxymethylmethacrylate, isopropyl α -allyloxymethylacrylate, n-butyl α -allyloxymethylacrylate, sec-butyl α -allyloxymethylacrylate, tert-butyl α -allyloxymethylacrylate, n-pentyl α -allyloxymethylacrylate, sec-pentyl α -allyloxymethylacrylate, tert-pentyl α -allyloxymethylacrylate, and neopentyl α -allyloxymethylacrylate. Among them, alkyl- (. alpha. -allyloxymethyl) acrylate monomers are preferred. As the alkyl- (. alpha. -allyloxymethyl) acrylate monomer, for example, methyl- (. alpha. -allyloxymethyl) acrylate or the like is preferably used from the viewpoints of transparency, dispersibility, industrial availability, and the like.
The α - (unsaturated alkoxyalkyl) acrylate monomer can be produced, for example, by the production method disclosed in international publication No. 2010/114077.
Further, as a monomer providing the structural unit (b1-2), an alkyl 2- (hydroxyalkyl) acrylate is also preferably mentioned. The alkyl 2- (hydroxyalkyl) acrylate is capable of reacting with (meth) acrylic acid to form a lactone ring structure in the backbone.
Examples of the alkyl 2- (hydroxyalkyl) acrylate include an alkyl 2- (1-hydroxyalkyl) acrylate and an alkyl 2- (2-hydroxyalkyl) acrylate, and specific examples thereof include methyl 2- (1-hydroxymethyl) acrylate, ethyl 2- (1-hydroxymethyl) acrylate, isopropyl 2- (1-hydroxymethyl) acrylate, n-butyl 2- (1-hydroxymethyl) acrylate, tert-butyl 2- (1-hydroxymethyl) acrylate, and 2-ethylhexyl 2- (1-hydroxymethyl) acrylate. Among them, methyl 2- (1-hydroxymethyl) acrylate and ethyl 2- (1-hydroxymethyl) acrylate are preferable.
The resin (b1) may have only 1 type of the structural unit (b1-2) or 2 or more types of the structural unit (b 1-2).
The content of the structural unit (b1-2) is preferably 5% by mass or more, more preferably 8% by mass or more, further preferably 10% by mass or more, preferably 35% by mass or less, more preferably 30% by mass or less, and further preferably 25% by mass or less, based on 100% by mass of the total structural units of the resin (b1), from the viewpoint that heat resistance and solvent resistance can be improved.
(b1-3) other structural units
The resin (b1) may have a structural unit (b1-3) other than the structural units (b1-1) and (b 1-2).
Examples of the other structural unit (b1-3) include structural units derived from the following monomers.
Hydroxyl group-containing monomers such as hydroxyalkyl (meth) acrylates including 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2, 3-hydroxypropyl (meth) acrylate;
methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, n-pentyl (meth) acrylate, sec-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, tridecyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, tricyclodecyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, n-pentyl (meth) acrylate, sec-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexyl) acrylate, cyclohexyl (meth) acrylate, cyclohexyl, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, N-dimethylaminoethyl (meth) acrylate, 1, 4-dioxaspiro [4, 5] decan-2-ylmethacrylic acid, (meth) acryloylmorpholine, 4- (meth) acryloyloxymethyl-2-methyl-2-ethyl-1, 3-dioxolane, 4- (meth) acryloyloxymethyl-2-methyl-2-isobutyl-1, 3-dioxolane, 4- (meth) acryloyloxymethyl-2-methyl-2-cyclohexyl-1, 3-dioxolane, 4- (meth) acryloyloxymethyl-2, (meth) acrylate monomers such as 2-dimethyl-1, 3-dioxolane;
aromatic vinyl monomers such as styrene, vinyltoluene, α -methylstyrene and methoxystyrene;
epoxy group-containing monomers such as glycidyl (meth) acrylate, (. beta. -methylglycidyl (meth) acrylate, (. beta. -ethylglycidyl (meth) acrylate), vinylbenzyl glycidyl ether, allyl glycidyl ether, (3, 4-epoxycyclohexyl) methyl (meth) acrylate, and vinylepoxycyclohexane;
(meth) acrylamides such as N, N-dimethyl (meth) acrylamide and N-methylol (meth) acrylamide;
macromonomers having a (meth) acryloyl group at one end of a polymer molecular chain, such as polystyrene, poly (methyl) acrylate, polyethylene oxide, polypropylene oxide, polysiloxane, polycaprolactone, and polycaprolactam;
conjugated dienes such as 1, 3-butadiene, isoprene and chloroprene;
vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate;
vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether, 2-hydroxyethyl vinyl ether, and 4-hydroxybutyl vinyl ether;
n-vinyl compounds such as N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, N-vinylmorpholine and N-vinylacetamide;
unsaturated isocyanates such as isocyanatoethyl (meth) acrylate and allylisocyanate; and the like.
Among them, the structural unit (b1-3) is preferably a structural unit derived from at least one monomer selected from the group consisting of the hydroxyl group-containing monomer, (meth) acrylate monomer, aromatic vinyl monomer, and epoxy group-containing monomer.
The resin (b1) may have only 1 type of the structural unit (b1-3) or 2 or more types of the structural unit (b 1-3).
From the viewpoint of satisfactory developability, the content of the structural unit (b1-3) is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, preferably 92% by mass or less, more preferably 90% by mass or less, and further preferably 85% by mass or less, based on 100% by mass of the total structural units of the resin (b 1).
When the resin (b1) contains 2 or more kinds of the structural units (b1-3), the content ratio of each structural unit can be appropriately set according to the use and purpose of the curable composition of the present invention.
The resin (b1) preferably further has an epoxy group. By further including an epoxy group in the resin (b1), the curability of the curable composition of the present invention can be improved, and a cured product having more excellent solvent resistance can be provided.
The resin (b1) having an epoxy group can be obtained by polymerizing the monomer component containing the epoxy group-containing monomer.
When the resin (b1) has an epoxy group, the epoxy equivalent of the resin (b1) is preferably 100 to 20000, more preferably 200 to 8000, and still more preferably 500 to 5000, from the viewpoint of satisfactory solvent resistance. The epoxy equivalent can be determined by dividing the amount of the resin by the number of moles of epoxy groups contained in the resin.
The acid value of the resin (b1) is preferably 20mgKOH/g to 230 mgKOH/g. When the acid value is within the above range, a cured film having good developability and excellent solvent resistance can be provided. More preferably 30 to 200mgKOH/g, and still more preferably 40 to 180 mgKOH/g.
The acid value is a value measured by a neutralization titration method using a KOH solution.
The weight average molecular weight of the resin (b1) is not particularly limited, and may be appropriately set according to the purpose and use of the curable composition, and is preferably 1000 to 100000, more preferably 2000 to 50000, and still more preferably 4000 to 30000.
The molecular weight distribution (weight average molecular weight/number average molecular weight) of the resin (b1) is preferably 1.0 to 4.0, more preferably 1.1 to 3.5, and still more preferably 1.5 to 3.0.
The weight average molecular weight and the molecular weight distribution are values measured by Gel Permeation Chromatography (GPC), and specifically, can be determined by the methods described in the examples below.
The resin (b1) may have a polymerizable double bond in a side chain. The curability of the resin (b1) can be improved by having a polymerizable double bond in the side chain. Examples of the polymerizable double bond include the polymerizable double bond described above. Among them, from the viewpoint of reactivity, a (meth) acryloyl group is preferable.
When the resin (b1) has a polymerizable double bond in a side chain, the double bond equivalent weight is preferably 200 g/equivalent to 8000 g/equivalent, more preferably 250 g/equivalent to 5000 g/equivalent, and further preferably 300 g/equivalent to 1500 g/equivalent.
The double bond equivalent means the mass of the solid content of the resin solution per 1mol of double bonds of the resin (b 1). The mass of the solid component in the resin solution is the total mass of the monomer component constituting the resin (b1) and the mass of the polymerization inhibitor. The double bond equivalent can be determined by dividing the mass (g) of the resin solid content of the resin solution by the amount (mol) of double bonds in the resin. The amount of the double bond of the resin can be determined from the amount of the acid group-containing monomer used in polymerization and the amount of the compound having a functional group capable of bonding to the acid group and a polymerizable double bond. Examples of the functional group capable of binding the acid group include a hydroxyl group and an epoxy group. Further, the measurement may be carried out by titration, elemental analysis, various analyses such as NMR and IR, or differential scanning calorimetry.
The method for producing the resin (b1) is not particularly limited as long as it is a method capable of obtaining a polymer having at least the structural unit (b1-1) and, if necessary, the structural units (b1-2) and (b1-3), and examples thereof include a method of polymerizing a monomer component containing a monomer capable of introducing the structural units (b1-1) to (b1-3) by a known method, and examples thereof include production methods described in paragraphs [0039] to [0062] of Japanese patent laid-open No. 2015-42697.
The content of the resin (b1) is preferably 10 to 60 mass%, more preferably 20 to 50 mass%, and still more preferably 30 to 45 mass% based on 100 mass% of the total solid content of the curable composition.
Resin having group generating acid group by heat or acid (b2)
Examples of the resin (b2) having a group which generates an acid group by heat or acid include resins having a structure or a group which generates an acid group by the action of heat or acid.
Examples of the structure or group which generates an acid group by heat or action of an acid include a group containing a tertiary carbon, a group in which an acid group is blocked with a vinyl ether compound, and a group in which a phenolic hydroxyl group is protected with a protecting group such as a tert-butyl group or an acetyl group.
As the tertiary carbon-containing group, preferred is-COO*R18(R18Represents a 1-valent organic group, with O*The bonded carbon atom is a tertiary carbon atom).
above-mentioned-COO*R18R of (A) to (B)18Represents a 1-valent organic group, with O*The bonded carbon atom is a tertiary carbon atom. A tertiary carbon atom is a carbon atom having 3 carbon atoms bonded to the other carbon atoms.
The 1-valent organic group preferably includes a 1-valent linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 91 carbon atoms. The above organic group may have a substituent.
With respect to R18The carbon number of (2) is more preferably 1 to 50, still more preferably 1 to 35, still more preferably 1 to 20, particularly preferably 1 to 12, and most preferably 1 to 9.
R18Preferably may be composed of-C (R)19)(R20)(R21) And (4) showing. In this case, R19、R20And R21The same or different, preferably a hydrocarbon group having 1 to 30 carbon atoms. The hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and may have a cyclic structure or may have a substituent. In addition, R19、R20And R21May be connected at the end portions to form a ring structure.
Here, in the tertiary carbon-containing group, the tertiary carbon atom is preferablyAt least 1 of the adjacent carbon atoms is bonded to a hydrogen atom. For example, R18is-C (R)19)(R20)(R21) In the case of the groups shown, R is preferred19、R20And R21At least 1 of which contains a carbon atom having 1 or more hydrogen atoms, and the carbon atom is bonded to a tertiary carbon atom.
R is as defined above19、R20And R31The same or different, preferably a saturated hydrocarbon group having 1 to 15 carbon atoms, more preferably a saturated hydrocarbon group having 1 to 10 carbon atoms, still more preferably a saturated hydrocarbon group having 1 to 5 carbon atoms, and particularly preferably a saturated hydrocarbon group having 1 to 3 carbon atoms.
R is as defined above18Preferably, it is tert-butyl or tert-amyl.
In order to obtain the polymer having a tertiary carbon-containing group, a tertiary carbon-containing monomer may be used as a monomer component. Preferred examples of the tertiary carbon-containing monomer include t-butyl (meth) acrylate and t-amyl (meth) acrylate.
Examples of the group in which the acid group is blocked with a vinyl ether compound include a group in which a vinyl ether compound is bonded to the acid group such as a carboxyl group.
Examples of the vinyl ether compound include aliphatic vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, 2-ethylhexyl vinyl ether, and cyclohexyl vinyl ether; cyclic ether compounds such as dihydropyrans which can form vinyl ethers through ring opening; and the like.
Among the above vinyl ether compounds, dihydropyrane is preferable in that the protective group is easily released at a lower temperature.
As the group in which the acid group is blocked with dihydropyran, preferred is a group represented by the following formula.
[ solution 16]
Figure BDA0003519141520000321
The above-mentioned group having a phenolic hydroxyl group protected with a protecting group such as a tert-butyl group or an acetyl group is preferably a group represented by the following formula.
[ solution 17]
Figure BDA0003519141520000331
(wherein n represents the number of substituents and is an integer of 1 to 5.)
The group represented by the above formula is reacted at a temperature of 50 to 150 ℃ for 1 to 30 hours in a solvent in the presence of an acid catalyst such as hydrochloric acid or sulfuric acid to remove the protecting group and form an acid group.
Among them, a group in which the acid group is blocked with dihydropyran is preferable in that the acid group can be generated at a lower temperature.
(b2-1) structural Unit represented by the general formula (14)
As the resin (b2), a resin having a structural unit (b2-1) represented by the following general formula (14) is preferably used.
[ solution 18]
Figure BDA0003519141520000332
(in the formula, R22Represents a hydrogen atom or a methyl group. Y represents a direct bond or a 2-valent organic group. A represents a group which generates an acid group by heat or acid. )
In the above general formula (14), R22Represents a hydrogen atom or a methyl group. Among them, R is a group having good heat resistance22Preferably methyl.
Y represents a direct bond or a 2-valent organic group.
Examples of the above-mentioned 2-valent organic group include a 2-valent hydrocarbon group which may or may not have a substituent.
Examples of the above-mentioned 2-valent hydrocarbon group include an alkylene group, a cycloalkylene group, an arylene group, and the like.
In the above-mentioned 2-valent hydrocarbon group, at least 1 of the atoms constituting the hydrocarbon group may be substituted with an oxygen atom, a nitrogen atom or a sulfur atom.
Examples of the substituent include a hydroxyl group, an alkoxy group, and a halogen atom.
Y is preferably a direct bond.
In the general formula (14), A represents a group which generates an acid group by heat or acid.
Examples of the group which generates an acid group by heat or acid include the same structures or groups as those which generate an acid group by heat or acid.
The resin (b2) may have only 1 type of the structural unit (b2-1) or 2 or more types of the structural unit (b 2-1).
From the viewpoint of satisfactory solvent resistance, the content of the structural unit (b2-1) is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, preferably 80% by mass or less, more preferably 70% by mass or less, and further preferably 60% by mass or less, based on 100% by mass of the total structural units of the resin (b 2).
(b2-2) structural Unit having Ring Structure in Main chain
The resin (b2) is preferably a polymer having a ring structure in the main chain. The heat resistance of the resin (b2) can be improved by having a ring structure in the main chain. Examples of the ring structure include the same ring structures as those described in the structural unit (b 1-2). The resin (b2) preferably further has a structural unit (b2-2) having a ring structure in the main chain.
Examples of the monomer capable of introducing the structural unit (b2-2) include the same monomers as those capable of introducing the structural unit (b 1-2).
The resin (b2) may have only 1 type of the structural unit (b2-2) or 2 or more types of the structural unit (b 2-2).
The content of the structural unit (b2-2) is preferably 5% by mass or more, more preferably 8% by mass or more, further preferably 10% by mass or more, preferably 35% by mass or less, more preferably 30% by mass or less, and further preferably 25% by mass or less, based on 100% by mass of the total structural units of the resin (b2), from the viewpoint of satisfactory heat resistance and solvent resistance.
(b2-3) other structural units
The resin (b2) may further have another structural unit (b2-3) in addition to the structural units (b2-1) and (b 2-2).
Examples of the other structural unit (b2-3) include the same structural units as those of the other structural unit (b 1-3).
Among them, the structural unit (b2-3) is preferably a structural unit derived from at least one monomer selected from the group consisting of a hydroxyl group-containing monomer, a (meth) acrylate monomer, an aromatic vinyl monomer, and an epoxy group-containing monomer.
The resin (b2) may have only 1 type of the structural unit (b2-3) or 2 or more types of the structural unit (b 2-3).
From the viewpoint of satisfactory developability, the content of the structural unit (b2-3) is preferably 15% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, preferably 95% by mass or less, more preferably 90% by mass or less, and further preferably 85% by mass or less, based on 100% by mass of the total structural units of the resin (b 2).
When the resin (b2) contains 2 or more kinds of the structural units (b2-3), the content ratio of each structural unit can be appropriately designed according to the use and purpose of the curable composition of the present invention.
The resin (b2) preferably further has an epoxy group. By further including an epoxy group in the resin (b2), the curability of the curable composition can be improved, and a cured product having more excellent solvent resistance can be provided.
The resin (b2) having an epoxy group can be obtained by polymerizing the monomer component containing the epoxy group-containing monomer.
The acid value of the resin (b2) is preferably 20mgKOH/g to 230 mgKOH/g. When the acid value is within the above range, a cured film having good developability and excellent solvent resistance can be provided. More preferably 30 to 200mgKOH/g, and still more preferably 40 to 180 mgKOH/g.
The acid value is a value measured by a neutralization titration method using a KOH solution.
The weight average molecular weight of the resin (b2) is not particularly limited, and may be appropriately set according to the purpose and use of the curable composition of the present invention, and is preferably 1000 to 100000, more preferably 2000 to 50000, and still more preferably 4000 to 30000.
The molecular weight distribution (weight average molecular weight/number average molecular weight) of the resin (b2) is not particularly limited, but is preferably 1.0 to 4.0, more preferably 1.1 to 3.5, and still more preferably 1.5 to 3.0.
The weight average molecular weight and the molecular weight distribution of the polymer are values measured by Gel Permeation Chromatography (GPC), and specifically, can be determined by the methods described in the examples below.
The resin (b2) may have a polymerizable double bond in a side chain. The curability of the resin (b2) can be improved by having a polymerizable double bond in the side chain.
Examples of the polymerizable double bond include the same polymerizable double bonds as those in the resin (b 1). When the resin (b2) has a polymerizable double bond in the side chain, the double bond equivalent weight is preferably in the same range as that of the resin (b 1).
The method for producing the resin (b2) is not particularly limited as long as it is a method capable of obtaining a polymer having at least the structural unit (b2-1) and, if necessary, the structural units (b2-2) and (b2-3), and examples thereof include a method of polymerizing a monomer component containing a monomer capable of introducing the structural units (b2-1) to (b2-3) by a known method. In addition, after the monomer component containing the acid group-containing monomer is polymerized, a protective group may be added to the acid group.
The amount of each monomer can be appropriately adjusted so that the content of each structural unit in the polymer is within a desired range.
The polymerization method is not particularly limited, and the same method as the method for producing the resin (b1) can be used.
The content of the resin (b2) is preferably 10 to 60 mass%, more preferably 20 to 50 mass%, and still more preferably 30 to 45 mass% based on 100 mass% of the total solid content of the curable composition.
When the resin (b1) and the resin (b2) are used together, the total content of the resin (b1) and the resin (b2) is preferably 1 to 50% by mass, more preferably 3 to 40% by mass, and still more preferably 5 to 35% by mass, based on 100% by mass of the total solid content of the curable composition.
The resin (b2) may have the acid group. The resin (b) may have the acid group and the group which generates an acid group by heat or acid.
The polymerizable compound is preferably at least one selected from the group consisting of the vinyl ether compound, the cyclic ether compound, (meth) acrylic acid ester, the carboxylic acid compound, the acid group-containing alkali-soluble resin, a resin having a group that generates an acid group by heat or acid, a maleimide compound, an alcohol, and a thiol.
< curing catalyst (C) >
The curing catalyst used in the present invention is not particularly limited, and preferably includes at least one selected from the group consisting of a cationic curing catalyst and a radical curing catalyst. Among them, a cationic curing catalyst is preferable in that the crosslinking reaction of the vinyl ether group rapidly proceeds.
In the case of either a cationic curing catalyst or a radical curing catalyst, a curing catalyst having thermal or photo-latent properties may be used according to the embodiment. In addition, Lewis acids or Bronsted acids themselves may also be used as cationic curing catalysts. These catalysts may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
(Heat latent cationic curing catalyst)
The heat latent cationic curing catalyst is not particularly limited, and a known heat latent cationic curing catalyst can be used. These are compounds which cannot generate a practical amount of cationic active species by light irradiation, and the temperature at which the cationic active species are generated is preferably 40 to 200 ℃, more preferably 60 to 180 ℃, and still more preferably 80 to 150 ℃. Examples of the heat latent cationic curing catalyst include nonionic curing catalysts and ionic curing catalysts.
Examples of the nonionic curing catalyst in the above-mentioned heat-latent cationic curing catalyst include compounds composed of a combination of a lewis acid moiety such as an organoboron compound and a lewis base moiety such as a nitrogen-containing compound such as amine or pyridine, a phosphorus-containing compound such as phosphine, or a sulfur-containing compound such as sulfide.
Examples of the ionic curing catalyst in the above-mentioned heat latent cationic curing catalyst include compounds composed of a combination of a cation such as (4-hydroxyphenyl) benzylmethylthioninium, (4-hydroxyphenyl) methyl o-tolylsulfonium, (4-acetoxyphenyl) benzylmethylthioninium, diphenylmethylthioninium and the like, and an anion such as tetrafluoroborate, hexafluorophosphate, triphenylhexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, tetrakis (pentafluorophenyl) borate, bis (trifluoromethanesulfonyl) imide, tricyanomethane and the like.
(photolatent cationic curing catalyst)
The photolatent cationic curing catalyst is not particularly limited, and known photolatent cationic curing catalysts can be used, and examples thereof include nonionic curing catalysts and ionic curing catalysts. Examples of the nonionic curing catalyst include nitrobenzyl esters, sulfonic acid derivatives, phosphoric acid esters, phenol sulfonic acid esters, diazonaphthoquinones, and N-hydroxyimide phosphonic acid esters. Examples of the ionic curing catalyst include diphenyliodonium, 4-methoxydiphenyliodonium, bis (4-methylphenyl) iodonium, 4-isopropyl-4' -methyldiphenyliodonium, bis (4-tert-butylphenyl) iodonium, bis (dodecylphenyl) iodonium, diphenyl-4-thiophenylphenylsulfonium, bis [4- (diphenylsulfonium) phenyl ] sulfide, bis [4- (bis (4- (2-hydroxyethyl) phenyl) sulfonium) phenyl ] sulfide, 4-chlorophenyldiphenylsulfonium, triphenylsulfonium,. eta.5-2, 4- (cyclopentadienyl) [1, 2, 3, 4, 5, 6-. eta. - (methylethyl) benzene ] -Fe (1+), tetrafluoroborate, and the like, And (3) a compound composed of a combination of anions such as hexafluorophosphate, triphenylhexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate and tetrakis (pentafluorophenyl) borate. Further, a photosensitizer such as thioxanthone may be added as necessary.
Further, as the above-mentioned photolatent cationic curing catalyst, a photoacid generator can be used, and examples of such compounds include onium salt compounds, sulfone compounds, sulfonic acid ester compounds, quinone diazide compounds, sulfonimide compounds, diazomethane compounds, and the like.
Among these, at least one selected from the group consisting of onium salt compounds, sulfonimide compounds, and diazomethane compounds is preferable, onium salt compounds are more preferable, and triarylsulfonium salts are even more preferable.
Examples of the onium salt compound include diaryliodonium salts, triarylsulfonium salts, triarylphosphonium salts, and the like.
Specific examples of the diaryliodonium salts include diphenyliodonium salts such as Bluesil PI2074 (manufactured by Elkem corporation), diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, and diphenyliodonium p-toluenesulfonate; 4-methoxyphenyl iodonium salts such as 4-methoxyphenyl phenyliodonium tetrafluoroborate, 4-methoxyphenyl phenyliodonium hexafluorophosphate, 4-methoxyphenyl phenyliodonium hexafluoroantimonate, 4-methoxyphenyl phenyliodonium hexafluoroarsenate, 4-methoxyphenyl phenyliodonium trifluoromethanesulfonate, 4-methoxyphenyl phenyliodonium trifluoroacetate and 4-methoxyphenyl phenyliodonium p-toluenesulfonate; bis (4-t-butylphenyl) iodonium salts such as bis (4-t-butylphenyl) iodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium hexafluorophosphate, bis (4-t-butylphenyl) iodonium hexafluoroantimonate, bis (4-t-butylphenyl) iodonium hexafluoroarsenate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium trifluoroacetate, and bis (4-t-butylphenyl) iodonium p-toluenesulfonate.
Examples of the triarylsulfonium salt include triphenylsulfonium salts such as triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, and triphenylsulfonium p-toluenesulfonate; 4-methoxyphenyl diphenyl sulfonium salts such as 4-methoxyphenyl diphenyl sulfonium tetrafluoroborate, 4-methoxyphenyl diphenyl sulfonium hexafluorophosphate, 4-methoxyphenyl diphenyl sulfonium hexafluoroantimonate, 4-methoxyphenyl diphenyl sulfonium hexafluoroarsenate, 4-methoxyphenyl diphenyl sulfonium trifluoromethanesulfonate, 4-methoxyphenyl diphenyl sulfonium trifluoroacetate, 4-methoxyphenyl diphenyl sulfonium p-toluenesulfonate and the like; 4-phenylthienyldiphenylsulfonium salts such as 4-phenylthienyldiphenylsulfonium tetrafluoroborate, 4-phenylthienyldiphenylsulfonium hexafluorophosphate, 4-phenylthienyldiphenylsulfonium hexafluoroantimonate, 4-phenylthienyldiphenylsulfonium hexafluoroarsenate, 4-phenylthienyldiphenylsulfonium trifluoromethanesulfonate, 4-phenylthienyldiphenylsulfonium trifluoroacetate and 4-phenylthienyldiphenylsulfonium p-toluenesulfonate.
Examples of the triaryl phosphonium salt include triphenyl phosphonium salts such as triphenyl phosphonium tetrafluoroborate, triphenyl phosphonium hexafluorophosphate, triphenyl phosphonium hexafluoroantimonate, triphenyl phosphonium hexafluoroarsenate, triphenyl phosphonium trifluoromethanesulfonate, triphenyl phosphonium trifluoroacetate, and triphenyl phosphonium p-toluenesulfonate; 4-methoxyphenyl diphenyl phosphonium salts such as 4-methoxyphenyl diphenyl phosphonium tetrafluoroborate, 4-methoxyphenyl diphenyl phosphonium hexafluorophosphate, 4-methoxyphenyl diphenyl phosphonium hexafluoroantimonate, 4-methoxyphenyl diphenyl phosphonium hexafluoroarsenate, 4-methoxyphenyl diphenyl phosphonium trifluoromethanesulfonate, 4-methoxyphenyl diphenyl phosphonium trifluoroacetate and 4-methoxyphenyl diphenyl phosphonium p-toluenesulfonate; tris (4-methoxyphenyl) phosphonium salts such as tris (4-methoxyphenyl) phosphonium tetrafluoroborate, tris (4-methoxyphenyl) phosphonium hexafluorophosphate, tris (4-methoxyphenyl) phosphonium hexafluoroantimonate, tris (4-methoxyphenyl) phosphonium hexafluoroarsenate, tris (4-methoxyphenyl) phosphonium trifluoromethanesulfonate, tris (4-methoxyphenyl) phosphonium trifluoroacetate and tris (4-methoxyphenyl) phosphonium p-toluenesulfonate.
Examples of the above-mentioned sulfonimide compound include: n- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyloxy) bicyclo [2, 2, 1] -hept-5-ene-2, 3-dicarboximide, n- (trifluoromethylsulfonyloxy) -having sulfonyl imide compounds such as N- (trifluoromethylsulfonyloxy) -7-oxabicyclo [2, 2, 1] -hept-5-ene-2, 3-dicarboximide, N- (trifluoromethylsulfonyloxy) bicyclo [2, 2, 1] -heptane-5, 6-oxy-2, 3-dicarboximide and N- (trifluoromethylsulfonyloxy) naphthylimide; n- (camphanylsulfonyloxy) succinimide, N- (camphanylsulfonyloxy) phthalimide, N- (camphanylsulfonyloxy) diphenylmaleimide, N- (camphanylsulfonyloxy) bicyclo [2, 2, 1] -hept-5-ene-2, 3-dicarboximide, n- (camphanylsulfonyloxy) -containing sulfonimide compounds such as N- (camphanylsulfonyloxy) -7-oxabicyclo [2, 2, 1] -hept-5-ene-2, 3-dicarboximide, N- (camphanylsulfonyloxy) bicyclo [2, 2, 1] -heptane-5, 6-oxo-2, 3-dicarboximide and N- (camphanylsulfonyloxy) naphthylimide; n- (4-methylbenzenesulfonyloxy) sulfonimide, N- (4-methylbenzenesulfonyloxy) phthalimide, N- (4-methylbenzenesulfonyloxy) diphenylmaleimide, N- (4-methylbenzenesulfonyloxy) bicyclo [2, 2, 1] -hept-5-ene-2, 3-dicarboximide, N- (4-methylbenzenesulfonyloxy) -7-oxabicyclo [2, 2, 1] -hept-5-ene-2, 3-dicarboximide, N- (4-methylbenzenesulfonyloxy) bicyclo [2, 2, 1] -heptane-5, 6-oxo-2, 3-dicarboximide, N- (4-methylbenzenesulfonyloxy) naphthylimide and the like having N- (4-methylbenzenesulfonyloxy) sulfonimide An imide compound; n- (2-trifluoromethylbenzenesulfonyloxy) succinimide, N- (2-trifluoromethylbenzenesulfonyloxy) phthalimide, N- (2-trifluoromethylbenzenesulfonyloxy) diphenylmaleimide, N- (2-trifluoromethylbenzenesulfonyloxy) bicyclo [2, 2, 1] -hept-5-ene-2, 3-dicarboximide, N- (2-trifluoromethylbenzenesulfonyloxy) -7-oxabicyclo [2, 2, 1] -hept-5-ene-2, 3-dicarboximide, N- (2-trifluoromethylbenzenesulfonyloxy) bicyclo [2, 2, 1] -heptane-5, 6-oxo-2, 3-dicarboximide, N- (2-trifluoromethylbenzenesulfonyloxy) phthalimide, N-phenylmaleimide, N-5-carbonyl-2, 3-dicarboximide, N-carbonyl-2, 3-carbonyl-imide, N- (2-carbonyl-imide, N- (2-carbonyl-2, 3-carbonyl-imide, N-carbonyl-2, N-carbonyl-2, 2, 1-imide, N-carbonyl-imide, N-carbonyl-imide, or a, And a sulfonimide compound having an N- (2-trifluoromethylbenzenesulfonyloxy) group such as N- (2-trifluoromethylbenzenesulfonyloxy) naphthylimide.
Examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyl diazomethane, 1-cyclohexylsulfonyl-1- (1, 1-dimethylethylsulfonyl) diazomethane, bis (1, 1-dimethylethylsulfonyl) diazomethane, and the like.
(Heat latent radical curing catalyst)
Examples of the heat latent radical curing catalyst include: organic peroxides such as cumene hydroperoxide, dicumyl peroxide, diisopropylbenzene peroxide, di-t-butyl peroxide, lauryl peroxide, benzoyl peroxide, t-butyl peroxyisopropylcarbonate, t-butyl peroxy (2-ethylhexanoate), t-amyl peroxy-2-ethylhexanoate, and the like; azo compounds such as 2, 2 '-azobis (isobutyronitrile), 1' -azobis (cyclohexanecarbonitrile), 2 '-azobis (2, 4-dimethylvaleronitrile), and dimethyl 2, 2' -azobis (2-methylpropionate); and the like.
(photolatent radical curing catalyst)
Examples of the photolatent radical curing catalyst include: alkylphenones such as 2, 2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone ("IRGACURE 184", manufactured by BASF), 2-hydroxy-2-methyl-1-phenyl acetone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinoacetone, and 2-benzyl-2- (dimethylamino) -4' -morpholinobutanone; acylphosphine oxides such as 2, 4, 6-trimethylbenzoyldiphenylphosphine oxide and bis (2, 4, 6-trimethylbenzoyl) diphenylphosphine oxide; methyl benzoylformate;
aminoketone compounds such as 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-1-propanone ("IRGACURE 907", manufactured by BASF), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone ("IRGACURE 369", manufactured by BASF), 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-ylphenyl) butan-1-one ("IRGACURE 379", manufactured by BASF); benzyl ketal compounds such as 2, 2-dimethoxy-1, 2-diphenylethan-1-one ("IRGACURE 651", manufactured by BASF corporation), and methyl phenylglyoxylate ("DAROCUR MBF", manufactured by BASF corporation); 1-hydroxycyclohexyl phenyl ketone ("IRGACURE 184", manufactured by BASF corporation), 2-hydroxy-2-methyl-1-phenyl-propan-1-one ("DAROCUR 1173", manufactured by BASF corporation), 1- [4- (2-hydroxyethoxy) phenyl ] -2-hydroxy-2-methyl-1-propan-1-one ("IRGACURE 2959", manufactured by BASF corporation), hydroxyketone compounds such as 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropanoyl) benzyl ] phenyl } -2-methyl-propan-1-one ("IRGACURE 127", manufactured by BASF) and [ 1-hydroxycyclohexyl phenyl ketone + benzophenone ] ("IRGACURE 500", manufactured by BASF); 1, 2-octanedione, 1- [4- (phenylthio) phenyl ] -, 2- (O-benzoyloxime) ] ("OXE 01", manufactured by BASF Corp.), ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -, 1- (0-acetyloxime) ("OXE 02", manufactured by BASF Corp.), 1, 2-octanedione, 1- [4- (phenylthio) -, 2-, (O-benzoyloxime) ], ethanone ("OXE 03", manufactured by BASF Corp.), 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -, 1- (O-acetyloxime) ("OXE 04"; and, BASF corporation)), and the like; a benzophenone-based compound; a benzoin-based compound; a thioxanthone-based compound; halomethylated triazine compounds; halomethylated oxadiazole-based compounds; a biimidazole-based compound; a cyclopentadienyl titanium-based compound; a benzoate-based compound; an acridine-based compound; and the like.
When the curable composition of the present invention contains the curing catalyst (C), the content of the curing catalyst (C) is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and still more preferably 0.5 to 3 parts by mass, based on 100 parts by mass of the polymer (a).
In particular, when the photolatent radical curing catalyst is used as the curing catalyst (C), the content of the curing catalyst (C) is preferably 0.3 to 20% by mass, more preferably 0.5 to 10% by mass, and still more preferably 1 to 8% by mass, based on 100% by mass of the total solid content of the curable composition of the present invention.
In particular, when a photolatent cationic curing catalyst of the photoacid generator is used as the curing catalyst (C), the content of the curing catalyst (C) is preferably 0.3 to 20% by mass, more preferably 0.5 to 10% by mass, and still more preferably 1 to 8% by mass, based on 100% by mass of the total solid content of the curable composition of the present invention.
In addition to the above components, the curable composition (1) of the present invention may further contain other components. Examples of the other component include 1 or 2 or more optional components selected from polymerizable compounds other than the above-mentioned polymerizable compounds, epoxides, solvents, chain transfer agents, dispersants, antioxidants, leveling agents, inorganic fine particles, coupling agents, curing aids, plasticizers, polymerization inhibitors, ultraviolet absorbers, defoaming agents, antistatic agents, anti-aging agents, wettability improvers, adhesion imparting agents, coloring materials (pigments and dyes), heat resistance improvers, development aids, fillers, thermosetting resins, matting agents, slip agents, surface modifiers, thixotropic aids, quinone diazide compounds, polyphenol compounds, cationically polymerizable compounds, and thermal acid generators. These can be appropriately selected from known ones according to the purpose and use of the curable composition. In addition, the amount thereof may be appropriately set.
(other polymerizable Compound)
The curable composition (1) of the present invention preferably contains the other polymerizable compound. By further containing the other polymerizable compound, a cured product having excellent various physical properties such as solvent resistance, mechanical strength, and heat resistance in addition to curability can be provided.
The other polymerizable compound is a low-molecular compound having a polymerizable unsaturated bond (also referred to as a polymerizable unsaturated group) which is polymerizable by irradiation with active energy rays such as radicals, electromagnetic waves (e.g., infrared rays, ultraviolet rays, X-rays, etc.), electron rays, etc., and examples thereof include monofunctional compounds having 1 polymerizable unsaturated group in the molecule and polyfunctional compounds having 2 or more polymerizable unsaturated groups.
Specific examples of the other polymerizable compounds include monofunctional polymerizable compounds and polyfunctional polymerizable compounds other than the polymerizable compound (B) described in paragraphs [0077] to [0085] of Japanese patent laid-open publication No. 2015-42697.
Among the above polyfunctional polymerizable compounds, in terms of reactivity, economy, availability, and the like, compounds having a (meth) acryloyl group such as polyfunctional (meth) acrylate compounds, polyfunctional urethane (meth) acrylate compounds, and (meth) acryloyl group-containing isocyanurate compounds are preferable, and polyfunctional (meth) acrylate compounds are more preferable. By containing the compound having a (meth) acryloyl group, the curable composition is more excellent in photosensitivity and curability, and a cured product having higher hardness and higher transparency can be obtained. As the above-mentioned polyfunctional polymerizable compound, a polyfunctional (meth) acrylate compound having 3 or more functions is more preferably used.
The content of the other polymerizable compound is not particularly limited and may be appropriately set within a range in which the effect of the present invention is exhibited, and is preferably 5 to 60 mass%, more preferably 10 to 50 mass% with respect to 100 mass% of the total solid content of the curable composition, from the viewpoint of making the viscosity of the curable composition appropriate.
(epoxide)
The curable composition (1) of the present invention preferably contains an epoxy compound. When an epoxy compound is contained, cationic polymerization proceeds, so that a crosslinking reaction proceeds more easily, and a cured product having excellent solvent resistance can be provided.
Examples of the epoxy compound include compounds having an epoxy group and a polymerizable double bond, and examples thereof include the epoxy group-containing monomers.
The content of the epoxy compound is preferably 1 to 50% by mass, more preferably 2 to 40% by mass, and still more preferably 5 to 30% by mass, based on 100% by mass of the total solid content of the curable composition.
Curable composition (2)
The second curable composition (hereinafter also referred to as "curable composition (2)") of the present invention is a curable composition comprising a polymer (a) and a polymerizable compound (B) and/or a curing catalyst (C), wherein the polymer (a) is a group transfer polymer comprising a monomer component of a vinyl ether group-containing (meth) acrylate represented by the following general formula (2).
[ solution 19]
Figure BDA0003519141520000411
(in the formula, R1Represents a hydrogen atom or a methyl group. R2And R3The same or different, represent a hydrogen atom or an organic group. R4Represents a hydrogen atom or an organic group. n represents an integer of 1 or more. )
In addition, a curable composition containing such a group transfer polymer is also excellent in curing reactivity.
Further, since the above-mentioned group transfer polymer is obtained by group transfer polymerization as described above, a cured product having a desired shape with a small amount of insoluble matter and a cured product having good strength can be obtained. In addition, since the amount of residual monomer is small, the reproducibility of the physical property expression of the obtained cured product is improved.
The group transfer polymer preferably has the same structural unit as the structural unit (a1) except that n in the structural unit (a1) represented by the general formula (1) is an integer of 1 or more.
The polymer (a) used in the curable composition (2) may further have a structural unit similar to the polymer (a) used in the curable composition (1), in addition to the structural unit. The polymer (a) used in the curable composition (2) preferably has the same physical properties such as various molecular weights, insoluble matter amounts, residual monomer amounts, and the like, and the content in the curable composition as the polymer (a) used in the curable composition (1).
The method for producing the polymer (a) used in the curable composition (2) may be the same as the method for carrying out the group transfer polymerization described in the method for producing the polymer (a) used in the curable composition (1), except that a substance in which n is an integer of 1 or more in the vinyl ether group-containing (meth) acrylate represented by the general formula (2) is used as a monomer component.
Preferable examples of the vinyl ether group-containing (meth) acrylates in which n is an integer of 1 or more in the general formula (2) include 2- (2-vinyloxyethoxy) ethyl (meth) acrylate and 2-vinyloxyethyl (meth) acrylate.
Examples of the polymerizable compound (B) and the curing catalyst (C) used in the curable composition (2) include the same curing catalysts as those used in the curable composition (1). Their contents are also the same.
The curable composition (2) may further contain other components. The other components include the same components as those used in the curable composition (1).
< method for producing curable composition >
The method for producing the curable compositions (1) and (2) of the present invention is not particularly limited, and for example, the curable composition can be produced by mixing and dispersing the above components using various known mixers or dispersers such as a bead mill, a ball mill, a kneader, and a stirrer. Further, after the polymer is produced, the solvent used in the production may be desolventized, and the obtained product may be mixed with other solvents to mix with the respective components. In addition, other steps that are usually performed may be further included. For example, when the colorant is contained, a colorant composition may be prepared in advance using a solvent, a dispersant, or the like, and then mixed with the above components.
< method of use >
Examples of the method for using the curable compositions (1) and (2) of the present invention include the following methods: the curable composition is applied to a substrate, and the coated product is dried, heated, irradiated with an active energy ray, or cured by a combination of these methods to form a cured film.
The substrate is not particularly limited, and examples thereof include known substrates made of wood, glass, various plastics, or a combination thereof.
The coating method is not particularly limited, and may be performed by a known method such as gravure printing, roll coating, bar coating, coater, and inkjet.
The drying or heating method may be appropriately selected from known methods according to the composition, purpose and use of the curable composition, and is, for example, preferably performed at 50 to 300 ℃, and more preferably at 60 to 200 ℃. The drying and heating time is preferably 1 minute to 72 hours, more preferably 20 minutes to 24 hours.
The irradiation with active energy rays can be carried out by a known method using active energy rays such as infrared rays, ultraviolet rays, X-rays, and electron rays. The irradiation amount may be appropriately set according to the composition and the use of the curable composition.
The curable compositions (1) and (2) of the present invention can also be used as molding materials. The molding method is not particularly limited, and may be appropriately selected from known methods such as injection molding, extrusion molding, and 3D printing, depending on the composition, purpose, and application of the curable composition.
When the cured product of the curable composition is a cured film, the thickness thereof may be appropriately designed according to the purpose and use thereof, and is preferably 1 μm to 5mm in general.
< use >
The curable compositions (1) and (2) of the present invention have excellent curing reactivity when cured by active energy rays or heat. The curable compositions (1) and (2) of the present invention can be suitably used for various applications such as adhesives, printing ink compositions, 3D printing compositions, resist compositions, sealants, various coating agents having functions such as releasing property, fingerprint adhesion prevention, water repellency, hydrophilicity, hard coating, stain resistance, antistatic property, and insulating property, various functional coatings for automobiles, buildings and structures, industrial applications, and packaging applications, surface protection sheets, substrates, lenses, electronic components, optical films, and various molding materials for optical components.
The curable compositions (1) and (2) of the present invention can be suitably used as a resist composition, and can be more suitably used as a color filter composition. The methods for producing and using the curable compositions (1) and (2) of the present invention which are suitable as resist compositions include the methods described in paragraphs [0120] to [0140] of Japanese patent laid-open No. 2015-42697.
Examples
The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "part" means "part by mass" and "%" means "% by mass".
Various physical properties of the polymer were measured by the following methods.
< weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw/Mn) >
The obtained polymer was dissolved/diluted with tetrahydrofuran, filtered through a filter having a pore size of 0.45 μm, and the obtained filtrate was measured by the following Gel Permeation Chromatography (GPC) apparatus and conditions.
The device comprises the following steps: HLC-8020GPC (manufactured by Tosoh corporation)
Eluting solvent: tetrahydrofuran (THF)
Standard substance: standard polystyrene (manufactured by Tosoh corporation)
Separating the column: TSKgel SuperHM-M, TSKgel SuperH-RC (manufactured by Tosoh corporation)
As the polymers B-1 and B-2, TSKgel SuperHZM-M and TSKgel SuperH-RC (manufactured by Tosoh Corp.) were used as separation columns.
<IH-NMR measurement>
The obtained polymer was subjected to the following conditions1H-NMR measurement.
The device comprises the following steps: nuclear magnetic resonance apparatus (600MHz) manufactured by Agilent Technologies
And (3) determination of a solvent: deuterated chloroform
Sample preparation: several mg to several tens mg of the obtained polymer was dissolved in the measurement solvent.
< insoluble content >
Ethyl acetate was added to about 2 to 3g of the obtained polymer so that the solid content was about 33 mass%, and after sufficiently stirring at room temperature, the obtained solution was passed through a filter having a pore size of 4 μm. The residue on the filter was further washed with about 7g to 10g of ethyl acetate, and then the residue was dried at room temperature for 5 minutes, and the mass (b) of the dried residue was measured. Assuming that the mass of the polymer is (a), the insoluble content is calculated by the following formula.
Insoluble content (% by mass) of (b)/(a). times.100
< X/Y ratio >
In a differential molecular weight distribution curve obtained by measuring the molecular weight of the polymer by the GPC method, as shown in FIG. 1, the point of the maximum value is represented by T, and the point at 5% height of T on the differential molecular weight distribution curve is represented by L from the low molecular weight side0And L1In the case of (1), the value obtained is represented by T-L0-L1The area (X) of the triangle surrounded by the above-mentioned differential molecular weight distribution curve and the connection L0-L1The ratio (X/Y) is calculated as the area (Y) of the portion surrounded by the line (A).
< solid content >
About 1g of the polymer solution was weighed in an aluminum cup, dissolved by adding about 3g of acetone, and then naturally dried at room temperature. Then, the sheet was dried at 170 ℃ for 1.5 hours under vacuum using a hot air dryer (trade name: PHH-101, manufactured by Espec Co., Ltd.), and then cooled naturally in the dryer, and the mass was measured. The solid content (% by mass) of the polymer solution was calculated from the mass reduction amount.
< acid value >
3g of the polymer solution was accurately weighed, dissolved in a mixed solvent of 90g of acetone and 10g of water, and titrated using a 0.1N KOH aqueous solution as a titration solution. The titration was carried out using an automatic titrator (trade name: COM-555, manufactured by Ponga industries, Ltd.), and the acid value (mgKOH/g) per 1g of the solid content was determined from the acid value of the solution and the solid content of the solution.
Production of polymers
Production example 1
< production of 2- (2-ethyleneoxyethoxy) ethyl methacrylate Polymer >
A50 mL Schlenk flask was charged with dehydrated tetrahydrofuran (230 parts by mass), methyl (trimethylsilyl) dimethylketene acetal (0.9 part by mass), and tetrabutylammonium benzoate (0.02 part by mass), and 2- (2-vinyloxyethoxy) ethyl methacrylate (hereinafter referred to as "VEEM") was added dropwise over 10 minutes while stirring at room temperature under a nitrogen stream (100 parts by mass). After completion of the dropwise addition, the reaction solution was stirred at room temperature for 5 hours, and then passed through a silica gel column to remove the catalyst. The resulting solution was concentrated to give VEEM polymer. By using1The obtained polymer was confirmed by H-NMR, and as a result, a peak derived from vinyl ether was confirmed in the vicinity of 6.5ppm, and it was found from the integral value that all the vinyl ether groups remained.
VEEM was not observed as a monomer, and the insoluble component contained in the polymer was 0%.
The weight average molecular weight of the resulting polymer was 42000, the number average molecular weight was 25000, and the molecular weight distribution (Mw/Mn) was 1.7. The value of X/Y of the polymer was 1.16.
To this was added 100 parts by mass of ethyl acetate to prepare a 50% by mass polymer solution.
Production example 2
< production of 2- (2-ethyleneoxyethoxy) ethyl methacrylate-methyl methacrylate copolymer >
Into a 500mL flask were charged dehydrated tetrahydrofuran (200 parts by mass), methyl (trimethylsilyl) dimethylketene acetal (1.7 parts by mass), and tetrabutylammonium benzoate (0.02 part by mass). Stirring the mixture at 20 ℃ under a nitrogen streamA monomer mixture (VEEM (20 parts by mass), methyl methacrylate (hereinafter referred to as "MMA") (90 parts by mass)) was slowly added dropwise. After stirring for 5 hours, the catalyst was removed by diluting with ethyl acetate and passing through a short column of silica gel. The polymer concentration of the resulting solution was concentrated/adjusted to give a VEEM-MMA copolymer solution with a polymer concentration of 50%. By using1The obtained copolymer was confirmed by H-NMR, and as a result, a peak derived from vinyl ether was confirmed, and it was found from the integral value that all vinyl ether groups remained. VEEM and MMA were not observed as monomers, and the insoluble content in the copolymer was 0%. The proportion of structural units of the above copolymer was VEEM/MMA 11/89 (mol%). The weight average molecular weight of the copolymer was 15000, the number average molecular weight was 12800, and the molecular weight distribution (weight average molecular weight/number average molecular weight) was 1.17. The value of X/Y of the above copolymer was 1.37.
(production example 3)
< production of 2- (2-ethyleneoxyethoxy) ethyl methacrylate-methyl methacrylate copolymer >
To a flask, VEEM (100 parts by mass), MMA (50 parts by mass), dehydrated tetrahydrofuran (350 parts by mass), and methyl (trimethylsilyl) dimethylketene acetal (2 parts by mass) were added, and a phosphazene base P4-t-Bu (0.8M toluene solution, 2.5 parts by mass) was added under a nitrogen stream at room temperature with stirring. After stirring at room temperature overnight (about 20 hours), a small amount of methanol was added, and the reaction solution was concentrated to obtain a polymer composition comprising a VEEM-MMA copolymer.
By using1The obtained polymer composition was confirmed by H-NMR, and a peak derived from vinyl ether was confirmed in the vicinity of 6.5ppm, and it was found from the integral value that all the vinyl ether groups remained. This confirmed that only the methacryloyl group of VEEM was polymerized. On the other hand, no peak of VEEM as a monomer was observed. The insoluble content of the copolymer was 0%. The proportion of structural units of the above copolymer was VEEM/MMA 50/50 (mol%).
The weight average molecular weight of the obtained copolymer was 27600, the number average molecular weight was 10600, and the molecular weight distribution (Mw/Mn) was 2.61. The value of X/Y of the above copolymer was 1.11.
Production example 4
< production of 2- (2-ethyleneoxyethoxy) ethyl acrylate Polymer >
2- (2-ethyleneoxyethoxy) ethyl acrylate (hereinafter referred to as "VEEA") (100 parts by mass), dehydrated toluene (180 parts by mass), and methyl (trimethylsilyl) dimethylketene acetal (1 part by mass) were charged into a flask, and a phosphazene base P4-t-Bu (0.8M toluene solution, 2 parts by mass) was added under a nitrogen stream at 30 ℃ with stirring. After stirring at 30 ℃ overnight (about 24 hours), a small amount of methanol was added and the reaction solution was concentrated to give a polymer composition comprising a VEEA polymer.
By using1The obtained polymer composition was confirmed by H-NMR, and a peak derived from vinyl ether was confirmed in the vicinity of 6.5ppm, and it was found from the integral value that all the vinyl ether groups remained. This confirmed that only the acryloyl group of VEEA was polymerized. On the other hand, no peaks (peaks at 6.5ppm, 6.2ppm and around 5.8 ppm) of VEEA as a monomer were observed. The insoluble content of the polymer was 0%. The VEEA polymer obtained had a weight average molecular weight of 19400, a number average molecular weight of 7600, and a molecular weight distribution (Mw/Mn) of 2.57. The value of X/Y of the VEEA polymer was 1.04.
Production example 5
< production of 2- (2-ethyleneoxyethoxy) ethyl methacrylate-cyclohexyl methacrylate copolymer >
In a flask immersed in a constant temperature bath of 20 ℃, a mixture of VEEM (100 parts by mass) and cyclohexyl methacrylate (hereinafter referred to as "CHMA") (100 parts by mass) was added dropwise to a mixture of dehydrated tetrahydrofuran (400 parts by mass), methyl (trimethylsilyl) dimethylketene acetal (6 parts by mass), and tetrabutylammonium benzoate (0.1 part by mass) over 10 minutes under a nitrogen stream. After the completion of the dropwise addition, the reaction solution was stirred under the same conditions for 5 hours. The resulting solution was diluted with ethyl acetate, passed through a short column of silica gel and then concentrated under reduced pressure, thereby obtaining a polymer composition comprising the VEEM-CHMA copolymer.
By using1The resulting polymer composition was confirmed by H-NMR, and VEEM and CHMA used in the polymerization were completely consumed. The insoluble content in the obtained copolymer was 0%.
The weight average molecular weight of the copolymer was 6900, the number average molecular weight was 6272, and the molecular weight distribution (Mw/Mn) was 1.1. The value of X/Y for the VEEM-CHMA copolymer described above was 1.20.
(production example 6)
< production of glycidyl methacrylate Polymer >
Glycidyl methacrylate (hereinafter referred to as "GMA") (30 parts by mass) and methyl ethyl ketone (hereinafter referred to as "MEK") (70 parts by mass) were charged into a four-necked flask equipped with a thermometer, an inert gas introduction tube, and a reflux condenser, to obtain a reaction solution. After degassing the reaction solution by bubbling nitrogen gas through the reaction solution for 3 hours, the reaction solution was heated to 70 ℃ while introducing nitrogen gas through an inert gas inlet tube, and a MEK solution (5 parts by mass) of a polymerization initiator (azobisisobutyronitrile: AIBN) (0.34 parts by mass) was slowly added to the reaction solution. Thereafter, the mixture was stirred at the same temperature for 20 hours, and after naturally cooling to room temperature, MEK (100 parts by mass) was added to obtain a polymer solution. The polymer solution was reprecipitated using hexane, thereby obtaining GMA polymer. The resulting polymer had a weight average molecular weight of 125800, a number average molecular weight of 23200, and a molecular weight distribution (Mw/Mn) of 5.42.
Production example 7
< production of Polymer B-1 >
Into a reaction vessel equipped with a thermometer, a stirrer, a gas inlet tube, a condenser and an inlet of a dropping vessel, 81.9 parts of propylene glycol monomethyl ether acetate and 37.7 parts of propylene glycol monomethyl ether were charged, and after nitrogen substitution, the temperature was raised to 90 ℃. On the other hand, as the dropping vessel (a), a mixture of 10.0 parts of N-benzylmaleimide, 70.0 parts of t-butyl methacrylate, 20.0 parts of methacrylic acid, 34.2 parts of propylene glycol monomethyl ether acetate, 14.7 parts of propylene glycol monomethyl ether, and 2.0 parts of t-butyl peroxy (2-ethylhexanoate) was stirred and mixed in a beaker, and a stirred mixture of 1.0 part of N-dodecylmercaptan and 6.1 parts of propylene glycol monomethyl ether acetate was prepared in the dropping vessel (B). After the temperature in the reaction tank reached 90 ℃, the polymerization was carried out by starting the dropwise addition from the dropwise addition tank over a period of 3 hours while maintaining the temperature. After the completion of the dropwise addition, the temperature was maintained at 90 ℃ for 30 minutes, and then the temperature was raised to 115 ℃ to conduct aging for 90 minutes. After cooling to room temperature, 16.5 parts of GMA, 0.4 part of dimethylbenzylamine as a catalyst, and 0.2 part of Topanol as a polymerization inhibitor were charged and reacted at 110 ℃ for 7 hours to obtain a polymer solution B-1 (solid content 39.8%). The weight average molecular weight of the obtained polymer was 15000, the molecular weight distribution (Mw/Mn) was 2.5, and the acid value was 60 mgKOH/g.
Production example 8
< production of Polymer B-2 >
201.0 parts of propylene glycol monomethyl ether acetate was charged into a reaction vessel equipped with a thermometer, a stirrer, a gas inlet tube, a condenser and a dropping vessel inlet, and after nitrogen substitution, the temperature was raised to 90 ℃. On the other hand, as the dropping vessel (a), a mixture of 10.0 parts of N-benzylmaleimide, 43.6 parts of CHMA, 30.0 parts of 2-hydroxyethyl methacrylate, 16.4 parts of GMA, 30.0 parts of propylene glycol monomethyl ether acetate and 2.0 parts of t-butyl peroxy (2-ethylhexanoate) in a beaker was stirred, and a stirred mixture of 2.0 parts of N-dodecylmercaptan and 31.3 parts of propylene glycol monomethyl ether acetate was prepared in the dropping vessel (B). After the temperature in the reaction tank reached 90 ℃, the polymerization was carried out by starting the dropwise addition from the dropwise addition tank over a period of 3 hours while maintaining the temperature. After the completion of the dropwise addition, the temperature was maintained at 90 ℃ for 30 minutes, and then the temperature was raised to 115 ℃ to conduct aging for 90 minutes. After that, the mixture was cooled to room temperature, and 11.5 parts of succinic anhydride and 0.3 part of dimethylbenzylamine as a catalyst were added thereto to carry out a reaction at 60 ℃ for 3 hours, thereby obtaining a polymer solution B-2 (solid content: 28.8%). The weight average molecular weight of the obtained polymer was 10000, the molecular weight distribution (Mw/Mn) was 2.8, and the acid value was 68 mgKOH/g.
Examples 1 to 28 and comparative examples 1 to 9
< production of curable composition >
The obtained polymer solution, polymerizable compound and curing catalyst were mixed at the ratios shown in tables 1 to 3, respectively, to obtain curable compositions. The blending amounts in the table are amounts in terms of solid content.
< evaluation of curing Property (acetone Friction test) >
The obtained curable composition was applied to a PET film (7cm × 21cm) subjected to one-side easy adhesion treatment so as to have a thickness of 25 μm by a bar coater, left to stand at room temperature for about 10 minutes to 20 minutes, and then the coated product was subjected to ultraviolet curing under the irradiation energy conditions shown in table 1 or thermal curing under the curing conditions shown in tables 2 to 3 by using an ultraviolet irradiation apparatus FUSION UV manufactured by Heraeus corporation to obtain a cured coating film. The obtained cured coating film was rubbed 20 times with a Kimwipe (NIPPON PAPER CRECIA co., ltd., product) impregnated with acetone, and the degree of curing was confirmed according to the following evaluation criteria. The results are shown in tables 1 to 3.
(evaluation criteria)
O: the cured coating film does not dissolve.
And (delta): the cured coating film has a residual rubbing mark or swelling.
X: the cured coating film whitens or dissolves.
The compounds described in tables 1 to 3 are as follows.
BMI-2300: phenylmethanemaleimides, produced by Daghuazai chemical industries, Ltd
PI2074：BluesilTMPI2074, manufactured by Elkem
Irg 184: IRUGACURE184 (1-hydroxycyclohexyl phenyl ketone, BASF corporation)
Polyacrylic acid (Mw 5000): manufactured by Aldrich
FRONZA B5200 XP: manufactured by SIRRUS Inc
San-Aid SI 150L: manufactured by Sanxin chemical industries, Ltd
San-Aid SI 110L: manufactured by Sanxin chemical industries, Ltd
San-Aid SI 100L: manufactured by Sanxin chemical industries, Ltd
Organic boron compound: FX-TP-BC-PC-AD-57103, manufactured by Nippon catalyst Kabushiki Kaisha
Figure BDA0003519141520000491
Figure BDA0003519141520000501
[ Table 3]
Figure BDA0003519141520000511
As is clear from tables 1 to 3, the curable compositions of the examples have excellent curing reactivity in both ultraviolet curing and thermal curing, and provide good cured products with a small amount of energy.
It is also found that the curable compositions of the examples are also superior in curing reactivity to the curable composition containing a polymer (GMA) having an epoxy group in a side chain, which is a common example among cationic curable compounds, as a comparative example.
< evaluation of photocuring reactivity >
The photocuring reactivity was evaluated for the VEEM polymer obtained in production example 1 and the VEEM-MMA copolymer obtained in production example 2 by the following method. Further, as a control, Celloxide 2021P (3, 4-epoxycyclohexylcarboxylic acid 3 ', 4' -epoxycyclohexylmethyl ester, made by Daiiol Co., Ltd.) and trimethylolpropane triacrylate (TMPTA) were used to evaluate the photocuring reactivity in the same manner.
The device comprises the following steps: NETZSCH DSC 204F1 Phoenix
The method comprises the following steps: weighing 1 mg-2 mg of sample in a container, placing in the device, and irradiating with 10mW/cm while keeping the sample temperature at 25 deg.C under nitrogen atmosphere2For 5 minutes, the change in the exothermic amount of reaction during the period was measured.
As the photo cation curing sample, a propylene carbonate solution of 40 mass% VEEM-MMA copolymer was used, or 1 mass with respect to the solid component was mixed in an epoxy (Celloxide 2021P)% of Bluesil as a photo-cationic curing catalystTMPI2074 (manufactured by Elkem).
As the photo radical curing sample, a propylene carbonate solution of VEEM polymer 50 mass% or a sample in which Irg184 as a photo radical initiator was mixed in TMPTA at 2 mass% with respect to the solid content was used. The measurement results are shown in fig. 2 and 3.
Figure 2 shows the DSC curve of a photo-cationically cured sample. From fig. 2, it is understood that the curing reaction proceeded as the heat release rapidly started 3.5 minutes after the light irradiation started. The comparative control epoxide showed a duration of exotherm due to the curing reaction after the exotherm peaked. On the other hand, the exothermic peak of the VEEM-MMA copolymer is steep, and the curing reaction is terminated in a short time. From these results, it is clear that the vinyl ether group-containing polymer is excellent in curing reactivity.
Fig. 3 shows DSC curves for photo radical cured samples. As can be seen from fig. 3, the VEEM polymer has photoradical curability at the same level as the multifunctional acrylate compound.
The curability of the curable composition was evaluated as described above, but the physical properties of a coating film formed from the curable composition are also important in practical use. Therefore, the cured coating film was further evaluated for adhesion and pencil hardness by the following methods using the curable compositions of examples.
The cured coating film for evaluation was formed by the same method as the cured coating film used in the < acetone friction test >.
< evaluation of adhesion (Cross cut test) >
Using the cured coating film for evaluation, the adhesion of the cured coating film to a PET film was evaluated in accordance with old JIS-K5400. That is, 11 cuts were made at 1mm intervals from above the cured coating film, and then the direction was changed by 90 ℃ to make 11 cuts in the same manner, thereby forming a checkerboard of 10 squares. The cut was such that it penetrated through the coating film but did not penetrate through the PET film. The cellophane adhesive tape is adhered in a mode of completely covering the checkerboard, and the cellophane adhesive tape is fully rubbed to be tightly sealed. Thereafter, the end of the tape was grasped and peeled off at a stroke at an angle of 45 degrees. After peeling the tape, the number of squares remaining on the PET film was counted. The greater the number of remaining squares, the higher the adhesion. The results are shown in Table 4.
< Pencil hardness test >
The cured coating film for evaluation was used to evaluate the scratch hardness of the coating film in accordance with JIS K5600-5-4. As the measuring apparatus, an electrodynamic pencil hardness tester No.553-M (manufactured by Anthemis Seisakusho K.K.) was used, and a pencil manufactured by Mitsubishi Pencil Co., Ltd. was used. The hardness of the hardest pencil that did not cause scratches (plastic deformation) is shown in table 4.
[ Table 4]
Examples 1 8 9 12 16 19 20 21 27 28
Adhesion Property 100/100 100/100 96/100 100/100 100/100 100/100 100/100 100/100 100/100 100/100
Hardness of pencil F 2H H F H 2H H 2H H F
As is clear from table 4, the cured coating films formed using the curable compositions of the examples have excellent adhesion to PET films, good pencil hardness, and excellent performance.
(examples 29 to 30, comparative example 10)
The respective components were mixed in the proportions shown in table 5 to obtain a curable composition. The blending amounts in the table are amounts in terms of solid content. In addition, the pigment dispersion 1 in the table was prepared by the following method.
Preparation example 1
Preparation of pigment Dispersion 1
Propylene glycol monomethyl ether acetate 12.9 parts, Disparlon DA-73010.4 parts as a dispersant, c.i. pigment green 582.25 parts as a coloring material, and c.i. pigment yellow 1381.5 parts were mixed and dispersed with a paint mixer for 3 hours to obtain a pigment dispersion 1 (solid content 22 mass%).
The compounds described in table 5 are as follows.
Irgacure OXE 02: ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -, 1- (0-acetyloxime) (manufactured by BASF corporation)
The solvent resistance of the obtained curable composition was evaluated by the following method. The results are shown in Table 5.
< solvent resistance >
The curable composition was spin-coated on a 5cm square glass substrate, dried at 100 ℃ for 3 minutes, exposed to light at 60mJ using a high-pressure mercury lamp, and heat-treated at 110 ℃ for 40 minutes (post-curing) to obtain a cured film having a thickness of 5 μm. Then, the cured film was immersed in 20g of 1-methyl-2-pyrrolidone (NMP) at 40 ℃ for 10 minutes and then taken out, and the absorbance of the immersion liquid (NMP) from which the cured film was taken out was measured by a spectrophotometer UV3100 (manufactured by shimadzu corporation). The larger the absorbance value, the more the coloring material eluted from the dipping solution, and the lower the solvent resistance of the curable composition was evaluated.
[ Table 5]
Figure BDA0003519141520000541
As confirmed from table 5, the curable compositions of the examples can provide cured products having excellent curing reactivity and solvent resistance.
Description of the symbols
1 differential molecular weight distribution curve.

Claims (9)

1. A curable composition comprising a polymer (A), a polymerizable compound (B) and/or a curing catalyst (C),
the polymer (A) has a structural unit represented by the following general formula (1), and has a molecular weight distribution, i.e., a weight average molecular weight/number average molecular weight of 1.0 to 4.0,
[ solution 1]
Figure FDA0003519141510000011
In the formula, R1Represents a hydrogen atom or a methyl group; r2And R3Identical or different, represent a hydrogen atom or an organic group; r4Represents a hydrogen atom or an organic group; n represents an integer of 2 or more.
2. A curable composition comprising a polymer (A), a polymerizable compound (B) and/or a curing catalyst (C),
the polymer (A) is a group transfer polymer containing a vinyl ether group-containing (meth) acrylate monomer component represented by the following general formula (2),
[ solution 2]
Figure FDA0003519141510000012
In the formula, R1Represents a hydrogen atom or a methyl group; r2And R3Identical or different, represent a hydrogen atom or an organic group; r4Represents a hydrogen atom or an organic group; n represents an integer of 1 or more.
3. The curable composition according to claim 1 or 2, wherein the weight average molecular weight of the polymer (A) is 5000 to 1000000.
4. The curable composition according to any one of claims 1 to 3, wherein the curing catalyst (C) is at least one selected from the group consisting of a cationic curing catalyst and a radical curing catalyst.
5. The curable composition according to any one of claims 1 to 4, wherein the polymerizable compound (B) is at least one selected from the group consisting of a vinyl ether compound, a cyclic ether compound, (meth) acrylate, a carboxylic acid compound, a maleimide compound, an alcohol and a thiol.
6. The curable composition according to any one of claims 1 to 4, wherein the polymerizable compound (B) is at least one selected from the group consisting of a methylene malonate diester compound and an alpha-cyanoacrylate.
7. The curable composition according to any one of claims 1 to 4, wherein the polymerizable compound (B) is at least one selected from the group consisting of an acid group-containing alkali-soluble resin and/or a resin having a group that generates an acid group by heat or acid.
8. The curable composition according to any one of claims 1 to 7, which is at least one selected from the group consisting of a curable composition for coating agents, a curable composition for adhesives, a curable composition for resists, a curable composition for coatings, a curable composition for printing ink compositions, a curable composition for electronic components, and a curable composition for optical components.
9. Use of the curable composition according to any one of claims 1 to 7 for producing at least one selected from the group consisting of coating agents, adhesives, resists, coatings, printing ink compositions, electronic components, and optical components.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116057088A (en) * 2020-08-03 2023-05-02 株式会社日本触媒 Copolymer, copolymer solution, photosensitive resin composition, cured product, method for producing copolymer, and method for producing copolymer solution

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CN113667362B (en) * 2021-08-27 2022-04-12 浙江东方齐心钢业集团有限公司 High-temperature-resistant stainless steel seamless steel tube and surface treatment process thereof
WO2023120355A1 (en) * 2021-12-21 2023-06-29 株式会社日本触媒 Alkali-soluble resin, photosensitive resin composition, and cured object therefrom

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06100628A (en) * 1992-09-21 1994-04-12 Nippon Oil & Fats Co Ltd Polymer containing vinyl ether group and its production
US20100313782A1 (en) * 2007-10-24 2010-12-16 Agfa Graphics Nv Curable liquids and inks for toys and food packaging applications
US20110009586A1 (en) * 2008-03-05 2011-01-13 Nippon Shokubai Co., Ltd. Polymer, curable resin composition, cured product, and article
CN107892729A (en) * 2016-10-04 2018-04-10 信越化学工业株式会社 The copolymer and manufacture method of (methyl) acrylic acid triisopropylsilyl ester and (methyl) acrylic acid derivative

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4943648A (en) * 1988-04-01 1990-07-24 E. I. Du Pont De Nemours And Company Initiators for group transfer polymerization
JPH06256426A (en) * 1993-03-01 1994-09-13 Nippon Oil & Fats Co Ltd Production of polymer having vinyl ether group
JPH06298884A (en) * 1993-04-09 1994-10-25 Nippon Oil & Fats Co Ltd Curable composition
JP4097489B2 (en) * 2002-09-06 2008-06-11 株式会社日本触媒 Method for producing polymer having vinyl ether group, aqueous solution or dispersion of polymer, and curable composition comprising the same
JP2004302216A (en) * 2003-03-31 2004-10-28 Nippon Shokubai Co Ltd Polymer for coating resist pattern
JP4667145B2 (en) 2004-07-22 2011-04-06 三井化学株式会社 Photocurable resin composition and resin composition for plastics comprising the same
US11643490B2 (en) 2018-06-11 2023-05-09 Nippon Shokubai Co., Ltd. Method for producing vinyl-ether-group-containing (meth)acrylic acid ester polymer, vinyl-ether-group-containing (meth)acrylic acid ester polymer, and polymer composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06100628A (en) * 1992-09-21 1994-04-12 Nippon Oil & Fats Co Ltd Polymer containing vinyl ether group and its production
US20100313782A1 (en) * 2007-10-24 2010-12-16 Agfa Graphics Nv Curable liquids and inks for toys and food packaging applications
US20110009586A1 (en) * 2008-03-05 2011-01-13 Nippon Shokubai Co., Ltd. Polymer, curable resin composition, cured product, and article
CN107892729A (en) * 2016-10-04 2018-04-10 信越化学工业株式会社 The copolymer and manufacture method of (methyl) acrylic acid triisopropylsilyl ester and (methyl) acrylic acid derivative

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
于红军: "《高分子化学及工艺学》", 华东理工大学出版社, pages: 132 - 136 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116057088A (en) * 2020-08-03 2023-05-02 株式会社日本触媒 Copolymer, copolymer solution, photosensitive resin composition, cured product, method for producing copolymer, and method for producing copolymer solution

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