JPWO2018150764A1 - Thiol-modified polymer, composition containing the polymer and use thereof - Google Patents

Abstract

An object of the present invention is to provide a composition having excellent adhesion to a substrate (for example, plastic) and having good compatibility with a reactive resin composition. The present invention relates to a composition comprising a thiol-modified polymer obtained by polymerizing a compound represented by the general formula [I] and modifying the polymer with a thiol compound. (Wherein, R1 represents a [-CH2-CR3 = CHR2] group, a glycidyl group, an alkyl group having 1 to 5 carbon atoms, or a hydrogen atom, and each R1 may be different or the same, and at least one of them may be the same.) Is a [-CH2-CR3 = CHR2] group, and R2 and R3 in the [-CH2-CR3 = CHR2] group each represent H or CH3.)

Description

（式中、Ｒ^１は［−ＣＨ_２−ＣＲ^３＝ＣＨＲ^２］基、グリシジル基、炭素数１〜５のアルキル基又は水素原子を表し、それぞれのＲ^１は異なっていても同一でもよく、そのうちの少なくとも１個は［−ＣＨ_２−ＣＲ^３＝ＣＨＲ^２］基であり、［−ＣＨ_２−ＣＲ^３＝ＣＨＲ^２］基中のＲ^２及びＲ^３は、それぞれ、Ｈ又はＣＨ_３を表す。）The present invention provides a thiol-modified polymer obtained by modifying a polymer obtained by polymerizing a compound represented by the general formula [I] with a thiol compound, a composition containing the thiol-modified polymer, and a composition thereof. The present invention relates to an adhesive, an ink, and a paint using an object. More specifically, the present invention relates to a composition having excellent adhesion to a substrate (for example, polypropylene (PP) or polyethylene terephthalate (PET)).

(Wherein, R ¹ represents a [—CH ₂ —CR ³ ＣＨCHR ² ] group, a glycidyl group, an alkyl group having 1 to 5 carbon atoms, or a hydrogen atom, and each R ¹ may be different or the same, at least one of which is _{^{[-CH 2 -CR 3 = CHR 2}} ] ^{_{group, [- CH 2 -CR 3 =}} CHR 2] R 2 and ^{R 3} in group each represent H or CH ₃ .)

  Conventionally, various resin compositions that are cured by active energy (light (eg, ultraviolet light) or heat) have been used in inks, paints, adhesives, photoresists, and the like. For example, UV-curable printing inks are highly evaluated for their high curing speed, which can be cured in a short time, that they are compatible with the environment because they do not use solvents, and that they are resource and energy saving. It has spread.

  Among such resin compositions, a resin composition containing a diallyl phthalate resin derived from diallyl phthalate (diallyl orthophthalate, diallyl isophthalate, diallyl terephthalate, etc.) has been adopted as a UV ink for paper. .

  However, it is known that when a diallyl phthalate resin is blended when used as an ink, the adhesion to a plastic substrate is not sufficient (for example, Patent Document 1). In recent years, various types of plastic products such as polyethylene terephthalate (PET) and polypropylene (PP) have been marketed, and there has been a demand for improved adhesion to a plastic substrate, which is a disadvantage of diallyl phthalate resin.

JP-A-52-4310

  An object of the present invention is to provide a composition having excellent adhesion to a substrate (for example, polypropylene (PP) or polyethylene terephthalate (PET)).

  The present inventors have conducted intensive studies to solve the above problems, and as a result, in a composition containing a reactive resin composition, a thiol obtained by modifying a polymer obtained by polymerizing a compound having a specific structure with a thiol compound. The present inventors have found that a composition having excellent adhesion to a substrate (particularly, plastic) can be obtained by adding a modified polymer, thereby completing the present invention.

（式中、Ｒ^１は［−ＣＨ_２−ＣＲ^３＝ＣＨＲ^２］基、グリシジル基、炭素数１〜５のアルキル基又は水素原子を表し、それぞれのＲ^１は異なっていても同一でもよく、そのうちの少なくとも１個は［−ＣＨ_２−ＣＲ^３＝ＣＨＲ^２］基であり、［−ＣＨ_２−ＣＲ^３＝ＣＨＲ^２］基中のＲ^２及びＲ^３は、それぞれ、Ｈ又はＣＨ_３を表す。）That is, the present invention
The present invention relates to a thiol-modified polymer (A) obtained by modifying a polymer obtained by polymerizing a compound represented by the following general formula [I] with a thiol compound.

(Wherein, R ¹ represents a [—CH ₂ —CR ³ ＣＨCHR ² ] group, a glycidyl group, an alkyl group having 1 to 5 carbon atoms, or a hydrogen atom, and each R ¹ may be different or the same, at least one of which is _{^{[-CH 2 -CR 3 = CHR 2}} ] ^{_{group, [- CH 2 -CR 3 =}} CHR 2] R 2 and ^{R 3} in group each represent H or CH ₃ .)

The composition containing the thiol-modified polymer (A) is excellent in adhesiveness to a substrate (particularly, plastic) and excellent in dryness and curability, and thus is excellent as an adhesive.
In addition, since this composition is particularly excellent in adhesion to PP (polypropylene) resin, it has been difficult to increase the adhesion in a composition using a conventional diallyl phthalate resin. Suitable as an ingredient.

  It is preferable that the composition of the present invention further contains a reactive resin composition. By using the reactive resin composition, the drying property and the curability of the composition are improved, the viscosity can be adjusted to be suitable for use in printing, and a composition excellent in coating workability can be obtained.

  The reactive resin composition of the present invention can contain either the thermosetting resin composition (B) or the photocurable resin composition (C), and can be appropriately selected depending on the application. .

  The composition of the present invention can be used as an ink. The ink of the present invention is characterized by containing the composition of the present invention. This ink is suitable as an ink for printing on a plastic base material, and is particularly suitable as an ink for printing on a base material such as a PP resin sheet or film.

Further, the composition of the present invention can be used as a paint. The paint of the present invention is characterized by containing the composition of the present invention. This paint is suitable as a paint for drawing on a plastic base material, and particularly suitable as a paint for drawing on a base material such as a PP resin sheet or film.
Further, the paint of the present invention is preferably an overprint varnish.

  The composition of the present invention can be used as an adhesive. Since this adhesive has excellent curability, it can be used for various adhesive applications.

  ADVANTAGE OF THE INVENTION According to this invention, the composition in which an ink, a coating material, an adhesive agent, and a photoresist are excellent in the base material of a metal or a synthetic polymer, especially a plastic base material is obtained. Further, the composition of the present invention can be suitably used for inks, paints, and adhesives.

3 shows an NMR spectrum. (A) is an NMR spectrum of the polymer used in Production Example 1, (B) is an NMR spectrum of 2-ethylhexyl 3-mercaptopropionate used in Production Example 1, and (C) is a polymer used in Production Example 1. The NMR spectrum of Irgacure 184 and (D) the NMR spectrum of the thiol-modified polymer obtained in Production Example 1 are shown.

  Hereinafter, the present invention will be described in detail.

Thiol-modified polymer (A)

（式中、Ｒ^１は［−ＣＨ_２−ＣＲ^３＝ＣＨＲ^２］基、グリシジル基、炭素数１〜５（好ましくは炭素数１〜３）のアルキル基又は水素原子を表し、それぞれのＲ^１は異なっていても同一でもよく、そのうちの少なくとも１個（特には２個が好ましく、３個がより好ましい）は［−ＣＨ_２−ＣＲ^３＝ＣＨＲ^２］基であり、［−ＣＨ_２−ＣＲ^３＝ＣＨＲ^２］基中のＲ^２及びＲ^３は、それぞれ、Ｈ又はＣＨ_３を表す。）The thiol-modified polymer (A) of the present invention is a polymer modified by subjecting an allyl group of a polymer obtained by polymerizing a compound represented by the general formula [I] to a thiol compound to undergo an thiol reaction, It can be used without particular limitation.
In the present invention, it is not clear why the thiol-modified polymer (A) contains the thiol-modified polymer (A) so as to have excellent adhesion to a metal or synthetic polymer substrate, particularly to a plastic substrate. You.
In a polymer obtained by polymerizing a compound represented by the general formula [I], a structure based on an isocyanurate ring (a ring structure (a trimer of isocyanate) in the general formula [I]) is continuously present. It is presumed that due to the structure based on the continuous isocyanurate ring, the adhesiveness to a metal or synthetic polymer substrate, particularly a plastic substrate, is excellent.
The thiol-modified polymer (A) is a polymer obtained by polymerizing a compound represented by the general formula [I] having such properties, and further modified with a thiol compound, and therefore, a metal or a metal. It is presumed that they have better adhesion to synthetic polymer substrates, especially plastic substrates.

(Wherein, ^{R 1} represents _{^{[-CH 2 -CR 3 = CHR 2}} ] group, a glycidyl group, an alkyl group or a hydrogen atom of 1 to 5 carbon atoms (preferably 1 to 3 carbon atoms), each of ^{R 1} may be the same or different, at least one of which (particularly preferably 2, 3 and more preferably) is _{^{[-CH 2 -CR 3 = CHR 2}} ] group, _[- CH 2 -CR ³ = CHR ² ], wherein R ² and R ³ each represent H or CH _3. )

（式中、Ｒ^１は［−ＣＨ_２−ＣＲ^３＝ＣＨＲ^２］基、グリシジル基、炭素数１〜５のアルキル基又は水素原子を表し、それぞれのＲ^１は異なっていても同一でもよく、そのうちの少なくとも１個（特には２個が好ましく、３個がより好ましい）は［−ＣＨ_２−ＣＲ^３＝ＣＨＲ^２］基であり、［−ＣＨ_２−ＣＲ^３＝ＣＨＲ^２］基中のＲ^２及びＲ^３は、それぞれ、Ｈ又はＣＨ_３を表す。）Polymer In the thiol reaction for obtaining the thiol-modified polymer (A) of the present invention, a polymer obtained by polymerizing the compound represented by the general formula [I] can be used.

(Wherein, R ¹ represents a [—CH ₂ —CR ³ ＣＨCHR ² ] group, a glycidyl group, an alkyl group having 1 to 5 carbon atoms, or a hydrogen atom, and each R ¹ may be different or the same, at least one of which (particularly preferably 2, more preferably three) is _{^{[-CH 2 -CR 3 = CHR 2}} ] ^{_{group, [- CH 2 -CR 3 =}} CHR 2] R in the radical ² and R ³ each represent H or CH _3. )

As described above, at least one R ¹ is preferably a [—CH ₂ —CR ³ ＣＨCHR ² ] group, and ^two R ¹ groups are preferably a [—CH ₂ —CR ³ ＣＨCHR ² ] group. Is more preferably a [—CH ₂ —CR ³ ＣＨCHR ² ] group. As the number of [—CH ₂ —CR ³ ＣＨCHR ² ] groups increases, the reactivity increases, and a polymer having a higher molecular weight is easily obtained.

R ² and R ³ are preferably H (hydrogen atom), and more preferably both are H (hydrogen atom).

In the general formula [I], when R ¹ is an alkyl group, examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and a pentyl group. Among them, a methyl group, an ethyl group, a propyl group, and an isopropyl group are preferable, and a methyl group and an ethyl group are more preferable.

  Specific examples of the compound represented by the general formula [I] include triallyl isocyanurate, diallyl monoglycidyl isocyanurate, diallyl monomethyl isocyanurate, diallyl monoethyl isocyanurate, diallyl monopropyl isocyanurate, trimaryl allyl isocyanurate, diallyl Isocyanurate, monoallyl dimethyl isocyanurate, monoallyl diethyl isocyanurate, monoallyl dipropyl isocyanurate, monoallyl diglycidyl isocyanurate, monoallyl monoethyl monomethyl isocyanurate, monoallyl isocyanurate, monoallyl dimethallyl isocyanurate, mono Allyl monomethallyl monomethyl isocyanurate and the like can be mentioned. Among these, triallyl isocyanurate, diallyl monoglycidyl isocyanurate, diallyl monomethyl isocyanurate, diallyl isocyanurate are preferred, triallyl isocyanurate, diallyl monomethyl isocyanurate, diallyl isocyanurate are more preferred, and triallyl isocyanurate is particularly preferred. preferable.

  Further, a polymer obtained by copolymerizing the compound represented by the general formula [I] and another polymerizable compound can be used for the thiol reaction. As copolymerizable compounds, acrylates such as methyl acrylate and butyl acrylate, various aliphatic and aromatic carboxylates such as vinyl acetate, vinyl laurate and vinyl benzoate, vinyl chloride, bromide Vinyls such as vinyl; vinylidenes such as vinylidene chloride and vinylidene bromide; vinyl alkyl ethers such as methyl vinyl ether and butyl vinyl ether; allyl ethers such as trimethylolpropane diallyl ether and pentaerythritol triallyl ether; allyl acetate; benzoic acid Examples include various aliphatic and aromatic carboxylic acid allyl esters such as allyl acid, and polybasic acid allyl esters such as diallyl terephthalate and triallyl citrate. The compounding ratio of the copolymer component in the polymer may be 2 to 50% by weight, and preferably 2 to 20% by weight.

  As an example of a method for obtaining the compound mentioned as a specific example of the compound represented by the general formula [I], a compound may be synthesized by a generally known polymerization method, or a commercially available product may be used.

  The polymerization method of the compound represented by the general formula [I] is not particularly limited, and a usual polymerization reaction can be used. A polymerization initiator may be appropriately added to the polymerization reaction as needed. By using the polymerization initiator, a polymer having a higher molecular weight can be obtained in a short time.

  Examples of the polymerization initiator used in the polymerization reaction of the compound represented by the general formula [I] include azo initiators such as azobisisobutyronitrile and dimethyl 2,2′-azobisisobutyrate, ketone peroxide, peroxyketal, Peroxide initiators such as hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxydicarbonate, peroxyester, benzoyl peroxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino Propan-1-one, acetophenones such as 1-hydroxycyclohexylphenyl ketone, benzoin, benzoin such as benzoin ethyl ether, benzophenone such as benzophenone, phosphorus such as acylphosphine oxide, sulfur such as thioxanthone, benzyl, 9,10 Benzyl-based photopolymerization initiators such as phenanthrenequinone are mentioned.

  The amount of the polymerization initiator is preferably not more than 5.0 parts by weight, and more preferably not more than 3.0 parts by weight based on 100 parts by weight of the monomer of the compound represented by the general formula [I]. More preferred. It is particularly preferred that the amount is 0.001 to 3.0 parts by weight. The lower limit is more preferably 0.1 part by weight, and particularly preferably 1.0 part by weight.

  The reaction temperature during the polymerization is preferably from 60 to 240C, for example, from 80 to 220C. The reaction time is preferably 0.1 to 100 hours, for example, 1 to 30 hours.

  By polymerizing the compound represented by the general formula [I] by the above-mentioned method or the like, a polymer having a monomer unit based on the compound represented by the general formula [I] can be prepared.

  The content of the monomer unit based on the compound represented by the general formula [I] is preferably 20% by weight or more, more preferably 50% by weight or more, based on 100% by weight of the polymer. It is more preferably at least 98% by weight, particularly preferably at least 98% by weight, and may be at least 100% by weight.

  The weight average molecular weight of the polymer is preferably 250,000 or less, more preferably 200,000 or less. Further, it is more preferably from 2,000 to 150,000, particularly preferably from 5,000 to 140,000. Further, the lower limit is most preferably 10,000, and most preferably 15,000. The upper limit is most preferably 100,000, and most preferably 80,000.

  The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the polymer is preferably 1.5 to 10.0, and more preferably 1.7 to 7.5. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are measured at 40 ° C. using gel permeation chromatography (manufactured by Shimadzu Corporation, GPC system), and a standard polystyrene calibration curve is used. You can ask. Specifically, the weight average molecular weight and the number average molecular weight are values measured by the methods described in Examples. The weight average molecular weight and the number average molecular weight of the thiol-modified polymer (polymer modified with a thiol compound) can be measured by the same method.

The thiol compound used for the thiol compound enethiol reaction can be used without any particular problem as long as it can react with the allyl group of the polymer described above. For example, at least one selected from the group consisting of an aliphatic thiol compound, an aromatic thiol compound, an aliphatic polythiol compound, a mercaptocarboxylic acid ester compound, a mercaptocarboxylic acid, and a mercaptoether can be exemplified.

  Examples of the aliphatic thiol compound include methyl thiol, ethyl thiol, 1-propyl thiol (n-propyl mercaptan), isopropyl thiol, 1-butyl thiol (n-butyl mercaptan), isobutyl thiol, tert-butyl thiol, Pentylthiol, isopentylthiol, 2-pentylthiol, 3-pentylthiol, 1-hexylthiol, cyclohexylthiol, 4-methyl-2-pentylthiol, 1-heptylthiol (n-heptylmercaptan), 2-heptylthiol , 1-octylthiol (n-octylmercaptan), isooctylthiol, 2-ethylhexylthiol, 2,4,4-trimethyl-2-pentylthiol (tert-octylmercaptan), 1-nonylthio (N-nonylmercaptan), tert-nonylthiol (tert-nonylmercaptan), isononylthiol, 1-decylthiol, 1-undecylthiol, 1-dodecylthiol, tert-dodecylthiol (tert-dodecylmercaptan) , Tridecylthiol, tetradecylthiol, 1-pentyldecylthiol, 1-hexyldecylthiol, 1-heptyldecylthiol, 1-octyldecylthiol, nonadecylthiol, eicosanthiol, triacontanthiol, tetracontanthiol, pentacon Tanthiol, hexacontanthiol, heptacontanthiol, octacontanthiol, nonacontanthiol, heptanthiol, 1-myristylthiol, cetylthiol, 1-ster Riruchioru, isostearyl thiol, 2-octyl-decyl thiol, 2-octyldodecyl thiol, can be exemplified 2-hexyl decyl thiol, behenyl thiols like.

  As aromatic thiol compounds, benzenethiol, phenylmethanethiol, xylenetol, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis (mercaptomethyl) benzene 1,3-bis (mercaptomethyl) benzene, 1,4-bis (mercaptomethyl) benzene, 1,2-bis (2-mercaptoethyl) benzene, 1,3-bis (2-mercaptoethyl) benzene, 1 1,4-bis (2-mercaptoethyloxy) benzene, 1,2-bis (2-mercaptoethyleneoxy) benzene, 1,3-bis (2-mercaptoethyleneoxy) benzene, 1,4-bis (2-mercaptoethylene) Oxy) benzene, 1,2,3-trimercaptobenzene, 1,2,4-trimercapto Benzene, 1,3,5-trimercaptobenzene, 1,2,3-tris (mercaptomethyl) benzene, 1,2,4-tris (mercaptomethyl) benzene, 1,3,5-tris (mercaptomethyl) benzene 1,2,3-tris (2-mercaptoethyl) benzene, 1,2,4-tris (2-mercaptoethyl) benzene, 1,3,5-tris (2-mercaptoethyl) benzene, 3-tris (2-mercaptoethyleneoxy) benzene, 1,2,4-tris (2-mercaptoethyleneoxy) benzene, 1,3,5-tris (2-mercaptoethyleneoxy) benzene, 1,2,3 4-tetramercaptobenzene, 1,2,3,5-tetramercaptobenzene, 1,2,4,5-tetramercaptobenzene, 1,2,3,4 Tetrakis (mercaptomethyl) benzene, 1,2,3,5-tetrakis (mercaptomethyl) benzene, 1,2,4,5-tetrakis (mercaptomethyl) benzene, 1,2,3,4-tetrakis (2-mercapto Ethyl) benzene, 1,2,3,5-tetrakis (2-mercaptoethyl) benzene, 1,2,4,5-tetrakis (2-mercaptoethyl) benzene, 1,2,3,4-tetrakis (2- Mercaptoethyleneoxy) benzene, 1,2,3,5-tetrakis (2-mercaptoethyleneoxy) benzene, 1,2,4,5-tetrakis (2-mercaptoethyleneoxy) benzene, 2,2′-dimercaptobiphenyl , 4,4'-thiobis-benzenethiol, 4,4'-dimercaptobiphenyl, 4,4'-dimercaptobiben 2,5-toluenedithiol, 3,4-toluenedithiol, 1,4-naphthalenedithiol, 1,5-naphthalenedithiol, 2,6-naphthalenedithiol, 2,7-naphthalenedithiol, 2,4-dimethylbenzene -1,3-dithiol, 4,5-dimethylbenzene-1,3-dithiol, 9,10-anthracenedimethanethiol, 1,3-bis (2-mercaptoethylthio) benzene, 1,4-bis (2 -Mercaptoethylthio) benzene, 1,2-bis (2-mercaptoethylthiomethyl) benzene, 1,3-bis (2-mercaptoethylthiomethyl) benzene, 1,4-bis (2-mercaptoethylthiomethyl) Benzene, 1,2,3-tris (2-mercaptoethylthio) benzene, 1,2,4-tris (2-merca 1,3-, 5-tris (2-mercaptoethylthio) benzene, 1,2,3,4-tetrakis (2-mercaptoethylthio) benzene, 1,2,3,5-tetrakis (2- (Mercaptoethylthio) benzene, 1,2,4,5-tetrakis (2-mercaptoethylthio) benzene, benzylthiol, m-toluenethiol, p-toluenethiol, 2-naphthalenethiol, 2-pyridylthiol, 2-mercapto Benzimidazole, 2-mercaptobenzothiazole and the like can be exemplified.

  Examples of the aliphatic polythiol compound include methanedithiol, 1,2-ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, and 1,7-heptane Dithiol, 1,8-octanedithiol, 1,9-nonanedithiol, 1,10-decanedithiol, 1,12-dodecanedithiol, 2,2-dimethyl-1,3-propanedithiol, 3-methyl-1,5 -Pentanedithiol, 2-methyl-1,8-octanedithiol, 1,4-cyclohexanedithiol, 1,4-bis (mercaptomethyl) cyclohexane, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, bicyclo [2 , 2,1] Hepta-exo-cis-2,3-dithio- Dithiol compounds such as 1,1-bis (mercaptomethyl) cyclohexane, bis (2-mercaptoethyl) ether, ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate); , 1-Tris (mercaptomethyl) ethane, 2-ethyl-2-mercaptomethyl-1,3-propanedithiol, 1,2,3-propanetrithiol, trimethylolpropanetris (2-mercaptoacetate), trimethylolpropane Trithiol compounds such as tris (3-mercaptopropionate) and tris ((mercaptopropionyloxy) -ethyl) isocyanurate; pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3- Le mercaptopropionate), pentaerythritol tetrakis (3-mercapto pig sulfonate), it can be exemplified thiol compounds having a dipentaerythritol hexa-3-mercaptopropionate SH group such as 4 or more.

  As mercaptocarboxylic acid ester compounds, methyl mercaptoacetate, methyl 3-mercaptopropionate, 4-methoxybutyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, n-octyl 3-mercaptopropionate, 3-mercaptopropione Acid stearyl, 1,4-bis (3-mercaptopropionyloxy) butane, 1,4-bis (3-mercaptobutyryloxy) butane, trimethylolethanetris (3-mercaptopropionate), trimethylolethanetris ( 3-mercaptobutyrate), trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptopropionate) Pentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol hexakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptobutyrate), tris [2- (3-mercaptobutyrate) Propionyloxy) ethyl] isocyanurate, tris [2- (3-mercaptobutyryloxy) ethyl] isocyanurate and the like can be exemplified. Among them, 2-ethylhexyl 3-mercaptopropionate is preferred.

  Other thiol compounds include mercaptocarboxylic acids such as mercaptoacetic acid, 3-mercaptopropionic acid, 2-mercaptopropionic acid, 3-mercaptobutyric acid, mercaptohexanoic acid, mercaptooctanoic acid, mercaptostearic acid, and thioglycolic acid; Mercaptoethers such as mercaptoethyl) ether; mercaptoalcohol compounds such as 2-mercaptoethanol and 4-mercapto-1-butanol; and silane-containing compounds such as (γ-mercaptopropyl) trimethoxysilane and (γ-mercaptopropyl) triethoxysilane Thiol compounds and the like.

  In terms of reactivity with the allyl group of the polymer, an aliphatic thiol compound, an aromatic thiol compound, a mercaptocarboxylic acid ester compound, a mercaptocarboxylic acid, and a mercaptoether are preferable, and an aliphatic thiol compound and a mercaptocarboxylic acid ester compound are more preferable. Preferably, a mercaptocarboxylic acid ester compound is more preferable. With the above thiol compound, the thiol reaction with the allyl group of the polymer can be performed without any problem.

Enthiol Reaction The enethiol reaction proceeds by bringing an unsaturated compound (such as an allyl compound or a polymer obtained by polymerizing an allyl compound) into contact with a thiol compound. (Or an active energy ray) to react (enthiol reaction). The application of the activation energy allows the thiol reaction to easily proceed.

  As the active energy, heat energy and / or light energy (in particular, at least light energy) can be used depending on the type of the polymerization initiator and the like.

  When applying (or heating) thermal energy, the heating temperature may be, for example, about 50 to 250 ° C, preferably about 60 to 200 ° C, and more preferably about 80 to 180 ° C. The application of heat energy (heating) may be performed not only when a thermal polymerization initiator is used as an initiator but also when a photopolymerization initiator is used.

  Further, when applying (or irradiating) light energy (for example, when using a photopolymerization initiator), as the light, radiation (gamma ray, X ray, etc.), ultraviolet ray, visible light, etc. can be used. Usually, it is often ultraviolet light. When a thermal polymerization initiator is used as the initiator, irradiation with light energy is not always necessary.

  As a light source, for example, in the case of ultraviolet light, a deep UV lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a mercury-xenon lamp, a halogen lamp, a UV-LED lamp, a laser light source (helium-cadmium laser) And a light source such as an excimer laser). The wavelength of the light may be, for example, about 150 to 800 nm, preferably about 150 to 600 nm, and more preferably about 200 to 400 nm (particularly about 300 to 400 nm). The irradiation light amount (irradiation energy) is not particularly limited, and can be selected from a range of about 1 mW to 10000 W (for example, 0.05 to 7000 W), for example, 0.1 to 5000 W, preferably 1 to 3000 W, and more preferably 10 to 1000 W. It may be about 2,000 W (for example, 30-1000 W). The irradiation time is not particularly limited, and may be, for example, about 5 seconds to 5 hours, preferably about 10 seconds to 2 hours, more preferably about 30 seconds to 1 hour, and usually about 1 to 30 minutes. You may. Note that heat energy (heating) and light energy (light irradiation) may be combined.

  The polymerization initiator used for the enethiol reaction may be selected from thermal polymerization initiators and photopolymerization initiators according to the type of the active energy ray. As the thermal polymerization initiator, dialkyl peroxides [di-tert-butyl peroxide] are used. Oxide, dicumyl peroxide, di (2-tert-butylperoxyisopropyl) benzene, etc.], diacyl peroxides [dialkanoyl peroxide (lauroyl peroxide, etc.), dialoyl peroxide (benzoyl peroxide, benzoyl toluyl par) Oxides, toluyl peroxides, etc.), peracid esters (tert-butyl peracetate, tert-butyl peroxyoctoate, tert-butylperoxybenzoate, tert-butylperoxyacetate, tert-butylperoxide) Organic peroxides such as peroxycarboxylic acid alkyl esters such as oxy-2-ethylhexanoate), ketone peroxides, peroxycarbonates and peroxyketals; azonitrile compounds [2,2′-azobis (2 , 4-dimethylvaleronitrile), 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (4-methoxy-2,4 -Dimethylvaleronitrile)], an azoamide compound {2,2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, etc., an azoamidine compound} 2 , 2'-Azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane Dihydrochloride etc., azoalkane compounds [2,2'-azobis (2,4,4-trimethylpentane), 4,4'-azobis (4-cyanopentanoic acid) etc.], azo compounds having an oxime skeleton [2 , 2'-azobis (2-methylpropionamide oxime) etc.].

  Benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and alkyl ethers thereof; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloro Acetophenone, 4- (1-tert-butyldioxy-1-methylethyl) acetophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2-benzyl-2-dimethyl Amino-1- (4-morpholinophenyl) -butanone-1, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 4- (2-hydroxyethoxy) phenyl- 2-hydroxy-2-propyl) ketone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 1-hydroxycyclohexylphenylketone, 2- Acetophenones such as hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomer; 2-methylanthraquinone, 2-amylanthraquinone, 2-tert-butylanthraquinone and 1-chloroanthraquinone; Anthraquinones; 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro- Thioxanthones such as -propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy) -3,4-dimethyl-9H-thioxanthone-9-one mesochloride; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone 4- (1-tert-butyldioxy-1-methylethyl) benzophenone, 3,3 ′, 4,4′-tetrakis (tert-butyldioxycarbonyl) benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3 ', 4,4'-tetra (tert-butylperoxylcarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N, N- Dimethyl-N Benzophenones such as-[2- (1-oxo-2-propenyloxy) ethyl] benzenemethanaminium bromide and (4-benzoylbenzyl) trimethylammonium chloride; acylphosphine oxides and xanthones, 1,2-octane Oxime esters such as dione, 1- [4- (phenylthio)-, 2, (0-benzoyloxime)], iodonium, (4-methylphenyl) [4- (2-methylpropyl) phenyl] -hexafluorophospho Onium salt systems such as fate and triarylsulfonium hexafluorophosphate can be exemplified. Among them, acetophenones are preferred.

  The amount of the thiol compound used in the enethiol reaction is not particularly limited, but can be calculated by the following calculation method. The number of functional groups in the polymer is determined from the iodine value of the polymer used for the enethiol reaction, and the number of functional groups in 1 g of the polymer (the number of functional groups in the polymer) is calculated from the molecular weight of the polymer and Avogadro's constant. The number of molecules in 1 g of the thiol compound (the number of molecules of the thiol compound) is calculated from the molecular weight and the Avogadro constant of the thiol compound used for the thiol reaction. From the calculated value, (the number of functional groups of the polymer / the number of molecules of the thiol compound) × the weight of the polymer to be used = the amount of the thiol compound used for the enethiol reaction can be obtained. The iodine value of the polymer can be measured according to the method specified in JIS K6235.

The thiol modification rate of the allyl group of the polymer in the enethiol reaction is determined by the FT-IR peak intensity of about 2550 cm ⁻¹ indicating the thiol group (FT-IR peak intensity of thiol group before reaction−FT-IR of thiol group after reaction) Peak intensity) ÷ It can be calculated from the FT-IR peak intensity of the thiol group before the reaction. The thiol modification rate of the allyl group of the thiol-modified polymer may be 30% or more, preferably 50% or more, and more preferably 80% or more.

  The weight average molecular weight (Mw) of the polymer modified with a thiol compound (thiol-modified polymer (A)) is preferably 600,000 or less, more preferably 500,000 or less, and 400,000 or less. More preferably, it is particularly preferably 200,000 or less, and most preferably 100,000 or less. Further, the Mw is preferably at least 2,000, more preferably at least 5,000, further preferably at least 10,000, particularly preferably at least 20,000, and preferably at least 20,000. Most preferably, it is not less than 2,000.

  The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the thiol-modified polymer (A) is preferably from 1.0 to 10.0, more preferably from 1.5 to 5.0.

（式中、Ｒ^１は［−ＣＨ_２−ＣＲ^３＝ＣＨＲ^２］基、グリシジル基、炭素数１〜５のアルキル基又は水素原子を表し、それぞれのＲ^１は異なっていても同一でもよく、そのうちの少なくとも１個（特には２個が好ましく、３個がより好ましい）は［−ＣＨ_２−ＣＲ^３＝ＣＨＲ^２］基であり、［−ＣＨ_２−ＣＲ^３＝ＣＨＲ^２］基中のＲ^２及びＲ^３は、それぞれ、Ｈ又はＣＨ_３を表す。）Composition The composition of the present invention comprises a thiol-modified polymer (A) obtained by modifying a polymer obtained by polymerizing a compound represented by the following general formula [I] with a thiol compound. Features.

(Wherein, R ¹ represents a [—CH ₂ —CR ³ ＣＨCHR ² ] group, a glycidyl group, an alkyl group having 1 to 5 carbon atoms, or a hydrogen atom, and each R ¹ may be different or the same, at least one of which (particularly preferably 2, more preferably three) is _{^{[-CH 2 -CR 3 = CHR 2}} ] ^{_{group, [- CH 2 -CR 3 =}} CHR 2] R in the radical ² and R ³ each represent H or CH _3. )

  The content of the thiol-modified polymer (A) in the composition may be in the range of 1 to 70% by weight, preferably 2.5 to 65% by weight, and preferably 5 to 70% by weight based on the total amount of the composition. More preferably, it is in the range of ６０60% by weight. The upper limit is more preferably 40% by weight, particularly preferably 30% by weight, and most preferably 20% by weight.

Reactive resin composition The composition of the present invention may further contain a reactive resin composition. The reactive resin composition can be used without any particular limitation as long as it can provide adhesion to the substrate and curability. For example, the thermosetting resin composition (B) or the photocurable resin It is possible to use any of the compositions (C). In addition, the thermosetting resin composition (B) in the present invention refers to a composition in which a curing (polymerization) reaction proceeds by being subjected to a heat treatment. Further, the photocurable resin composition (C) in the present invention refers to a composition in which a curing (crosslinking / polymerization) reaction proceeds by light irradiation. In the present invention, the reactive resin composition in which the curing reaction proceeds in both heat treatment and light irradiation is included in both the thermosetting resin composition (B) and the photocurable resin composition (C). It may belong.

Thermosetting resin composition (B)
The thermosetting resin composition (B) used in the present invention contains a thermosetting compound (b-1) and a curing agent (b-2). Examples of the thermosetting compound (b-1) include resins having thermosetting properties, such as epoxy resins, phenolic resins, polyimide resins, polyurethane resins, alkyd resins, melamine resins, silicone resins, and urea resins. be able to. Among them, epoxy resin is preferred in terms of ease of handling and adhesion to a substrate.

  The content of the thermosetting resin composition (B) in the composition may be appropriately selected according to the properties of the thermosetting resin used. If the content of the thermosetting resin composition (B) in the composition is too small, sufficient adhesion to the substrate cannot be obtained, and the content of the thermosetting resin composition (B) is too large. And it takes time to cure.

Compound (b-1) having thermosetting properties
As the thermosetting compound (b-1) in the thermosetting resin composition (B) used in the present invention, a compound having an epoxy group capable of obtaining high adhesion in terms of adhesion to a substrate Is preferred. Specifically, bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A, hydrogenated bisphenol F and other hydrogenated Novolak type epoxy resins such as bisphenol type epoxy resin, phenol novolak type epoxy resin and cresol novolak type epoxy resin, alkyl diphenol type epoxy resins such as tert-butyl diphenyl glycidyl ether and methyl diphenyl glycidyl ether, triglycidyl-p-aminophenol Glycidylamine resins such as triglycidyl isocyanurate and trifunctional glycidyl ether resins such as triphenylglycidyl ether methane, alicyclic epoxy resins Resins, epoxy acrylates, oxetanes, urethane-modified, siloxane-modified, imide-modified, naphthalene-modified, can be exemplified acrylic-modified compounds having an epoxy group of various modified products of such vinyl-modified.

  The content of the thermosetting compound (b-1) in the thermosetting resin composition (B) is preferably 50 to 1500 parts by weight based on 100 parts by weight of the thiol-modified polymer (A). , 100 to 1200 parts by weight, more preferably 100 to 900 parts by weight.

Curing agent (b-2)
The curing agent (b-2) in the thermosetting resin composition (B) used in the present invention is usually a thermosetting resin as long as it has compatibility with the thermosetting compound (b-1) used. A known curing agent can be appropriately used as a resin curing agent. Specific examples include phenol curing agents, acid anhydride curing agents, curing agents such as dicyandiamide, diamine curing agents, imidazole curing agents, tertiary amine curing agents, phosphine curing agents, and the like. can do. One of the above curing agents may be used alone, or two or more of them may be used in combination.

  The curing agent (b-2) is generally an addition polymerization type curing agent (i) which is a curing agent that reacts in an equivalent amount with the compound (b-1) having thermosetting properties, for example, phenols, acid anhydrides Polymerization type (ii), which is a curing agent that reacts with a curing agent such as an amine, dicyandiamide or diamine, and a small amount of the compound (b-1) having thermosetting properties, for example, imidazoles and tertiary amines Alternatively, it can be classified as a curing agent such as phosphines. Further, a curing accelerator such as imidazole, organic phosphonium, DBU (azabicycloundecene) or the like may be further used as a curing speed regulator.

  Examples of the addition polymerization type curing agent (i) include chain aliphatic polyamines such as diethylenetriamine and diethylaminopropylamine, cyclic aliphatic polyamines such as N-aminoethylpiverazine and isophoronediamine, and aromatic polyamines such as xylene diamine. , Polyamides, acid anhydrides such as methyltetrahydrophthalic anhydride and hexahydrophthalic anhydride, phenols such as dicyclopentadiene and triphenylalkyl, thiols such as liquid polymercaptan and polysulfide resins, and boron trifluoride-amine complex And a curing agent such as dicyandiamide and the like.

  Examples of the ionic polymerization type curing agent (ii) include a cationic polymerization type and an anion polymerization type. Specifically, benzyl dimethylamine and 2,4,6-tris (dimethyl Examples thereof include secondary or tertiary amines such as (aminomethyl) phenol and imidazoles such as 2-methylimidazole and 1-cyanoethyl-2-methylimidazole. Examples of the cationic polymerization type include onium salts such as sulfonium and iodonium.

  In the present invention, when a curing system of addition polymerization is used, the curing agent (b-2) usually does not undergo a curing reaction at room temperature (near the storage temperature), and has relatively fast curing properties. ) Acid anhydrides are preferred. By using the addition polymerization type (i) curing agent, the curing start temperature of the thermosetting resin composition (B) can be controlled. In addition, when the addition polymerization type (i) curing agent is used, the amount of the curing agent (b-2) in the thermosetting resin composition (B) is different from the amount of the thermosetting compound (b-1). In contrast, a range of about 0.9 to 1.1 equivalents is preferable, and a range of about 0.95 to 1.05 equivalents is more preferable. If the amount of the curing agent (b-2) is too small, many unreacted compounds of the thermosetting compound (b-1) remain, and the adhesion to the film substrate is impaired. On the other hand, if the addition amount is too large, a large amount of the unreacted curing agent of the curing agent (b-2) remains and the adhesion to the substrate is impaired. Furthermore, the curing start temperature can be easily controlled by adding a small amount of a curing accelerator to a composition containing the compound (b-1) having thermosetting properties and the ionic polymerization type curing agent (ii). it can.

  In the present invention, when a homopolymerization curing system is used, as the curing agent (b-2), imidazoles of an ion polymerization type curing agent (ii) are preferable. When a ionic polymerization type (ii) curing agent is used, the weight ratio of the thermosetting compound (b-1) / the curing agent (b-2) in the thermosetting resin composition (B) is 100 / It is preferably in the range of 0.1 to 100/10, and more preferably in the range of 100/1 to 100/5.

Photocurable resin composition (C)
The photocurable resin composition (C) used in the present invention comprises a so-called vinyl compound having at least one group having an ethylenically unsaturated double bond curable by light irradiation, or a group having at least one group having a cyclic ether bond. It contains one or more cyclic ether compounds. These may be used alone or in combination of two or more.

Vinyl compound
Examples of the vinyl compound include an aliphatic, alicyclic or aromatic (meth) acrylate monomer, an allyl monomer, a vinyl monomer, a urethane (meth) acrylate oligomer, an epoxy (meth) acrylate oligomer, and a polyester (meth) acrylate oligomer. can do. Further, as the vinyl compound, a mixture of two or more compounds can be used. The vinyl compound (ethylenically unsaturated compound) preferably has 1 to 20 carbon-carbon double bonds, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 6 carbon-carbon double bonds.

  As the aliphatic (meth) acrylate monomer, butyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, hydroxyethyl (meth) acrylate Such as alkyl (meth) acrylates, neopentyl glycol di (meth) acrylate, alkylene glycol di (meth) acrylates such as polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, and tripropylene glycol di ( (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, alkylenediol di (meth) acrylates of 1,9-nonanediol di (meth) acrylate, Tyrolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate ethylene oxide, propylene oxide-modified trimethylolpropane triacrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol, ethoxylated Polyfunctional (meth) acrylates such as pentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate, and alkoxyalkylene glycol (meth) acrylates such as methoxypropylene glycol (meth) acrylate and ethoxydiethylene glycol (meth) acrylate , (Meth) acrylamide, N-substitution such as N-butoxymethyl (meth) acrylamide It can be exemplified acrylamide, and the like, among them, dipropylene glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate.

  Examples of the alicyclic (meth) acrylate monomer include cyclohexyl (meth) acrylate, dicyclopentadienyl di (meth) acrylate, and isobornyl (meth) acrylate, with isobornyl (meth) acrylate being preferred.

  As the aromatic (meth) acrylate monomer, phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, ethoxylated bisphenol F Examples thereof include di (meth) acrylate, and ethoxylated bisphenol A di (meth) acrylate is preferable.

  As the vinyl monomer, styrene, α-methylstyrene, divinylbenzene, N-vinylpyrrolidone, N-vinylformamide, N-vinylcaprolactam, vinyl acetate, methylvinylether, ethylvinylether, n-propylvinylether, isopropylvinylether, n-butyl Vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, isopentyl vinyl ether, tert-pentyl vinyl ether, n-hexyl vinyl ether, isohexyl vinyl ether, 2-ethylhexyl vinyl ether, allyl vinyl ether, acrylic acid 2- (2-vinyloxy) (Ethoxy) ethyl, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, acetoxymethyl vinyl Ether, hydroxypropyl vinyl ether, diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, tetraethylene glycol monovinyl ether, propylene glycol monovinyl ether, dipropylene glycol monovinyl ether, tripropylene glycol monovinyl ether, trimethylolpropane monovinyl ether, trimethylol with ethylene oxide Propane monovinyl ether, pentaerythritol monovinyl ether, propylene oxide-added pentaerythritol monovinyl ether, glycidyl vinyl ether, cyclohexyl vinyl ether, phenyl vinyl ether, diethylene glycol ethyl vinyl ether, triethylene glycol methyl vinyl ether Ter, divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, tripropylene glycol divinyl ether, neopentyl glycol divinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, ditrimethylolpropane tetravinyl ether, dipentaerythritol hexavinyl ether, etc. 2- (2-vinyloxyethoxy) ethyl acrylate is preferred.

  Examples of the allyl monomer include tri (meth) allyl isocyanurate and tri (meth) allyl cyanurate, and triallyl isocyanurate is preferable.

  As a urethane (meth) acrylate oligomer, polyester glycol is used in place of polyether urethane (meth) acrylate or ether glycol, in which ether glycol such as ethylene glycol is chain-extended with diisocyanate and both ends are (meth) acrylated. Polyester urethane (meth) acrylate, and those using caprolactone diol, polycarbonate diol, and the like, and polyether urethane (meth) acrylate is preferable.

  Examples of the epoxy (meth) acrylate oligomer include those obtained by reacting (meth) acrylic acid with an epoxy group such as a bisphenol A type epoxy resin, a novolak type epoxy resin, or an epoxidized oil type, and bisphenol A glycidyl ether. Acrylic acid adducts, hexahydrophthalic acid diglycidyl ether acrylate, and trimethylolpropane polyglycidyl ether acrylate are preferred.

  The polyester (meth) acrylate oligomer is obtained by polycondensing a polybasic acid and a polyhydric alcohol to obtain a polyester having a hydroxyl group or a carboxyl group, and then esterifying the hydroxyl group and the (meth) acrylic acid in the polyester or forming a carboxyl group. Examples thereof include those obtained by esterification of a compound with a (meth) acrylate containing a hydroxyl group, and an aliphatic polyester tetraacrylate is preferable.

Cyclic ether compound
Examples of the cyclic ether compound include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 4- (glycidyloxy) butyl (meth) acrylate, 3-methyl-3,4-epoxybutyl (meth) acrylate, and 3-ethyl- 3,4-epoxybutyl (meth) acrylate, 4-methyl-4,5-epoxypentyl (meth) acrylate, 5-methyl-5,6-epoxyhexyl (meth) acrylate, glycidyl α-ethyl acrylate, allyl glycidyl Ether, crotonyl glycidyl ale, glycidyl ether of (iso) crotonic acid, (3,4-epoxycyclohexyl) methyl (meth) acrylate, N- (3,5-dimethyl-4-glycidyl) benzyl acrylamide, o-vinylbenzyl glycidyl ether, -Vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3- Diglycidyloxymethylstyrene, 2,4-diglycidyloxymethylstyrene, 2,5-diglycidyloxymethylstyrene, 2,6-diglycidyloxymethylstyrene, 2,3,4-triglycidyloxymethylstyrene, 2, 3,5-triglycidyloxymethylstyrene, 2,3,6-triglycidyloxymethylstyrene, 3,4,5-triglycidyloxymethylstyrene, 2,4,6-triglycidyloxymethylstyrene, 3 ′, 4 '-Epoxycyclohexylmethyl -3,4-epoxycyclohexanecarboxylate, 3-methoxyoxetane, 3-ethoxyoxetane, 3-propoxyoxetane, 3-isopropoxyoxetane 3-ethyl-3-hydroxymethyloxetane, 1,4-bis [(3-ethyl -3-oxetanyl) methoxymethyl] benzene, 3-ethyl-3- (phenoxymethyl) oxetane, di (1-ethyl-3-oxetanyl) methyl ether, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane And di (1-methyl-3-oxetanyl) methyl ether and the like, and 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate is preferred.

  Among them, aliphatic, alicyclic or aromatic (meth) acrylate monomers, allyl monomers, and vinyl monomers are preferable from the viewpoint of compatibility with the thiol-modified polymer (A) and curability upon photocuring. An alicyclic or aromatic (meth) acrylate monomer is more preferred, and an aliphatic (meth) acrylate monomer is even more preferred.

  Content of the so-called vinyl compound having at least one group having an ethylenically unsaturated double bond or the cyclic ether compound having at least one group having a cyclic ether bond in the photocurable resin composition (C) of the present invention. Is preferably 50 to 1500 parts by weight, more preferably 100 to 1200 parts by weight, based on 100 parts by weight of the thiol-modified polymer (A) in the photocurable resin composition (C). More preferably, it is 950 parts by weight.

  The content of the so-called vinyl compound having one or more groups having an ethylenically unsaturated double bond or the cyclic ether compound having one or more groups having a cyclic ether bond in the photocurable resin composition (C) is as follows. It is preferable to add the photocurable resin composition (C) such that the viscosity of the photocurable resin composition (C) falls within a range of 1 to 3000 mPa · s (particularly, 1 to 2000) (25 ° C.). Specifically, the ratio of the thiol-modified polymer (A) to a so-called vinyl compound having one or more groups having an ethylenically unsaturated double bond or a cyclic ether compound having one or more groups having a cyclic ether bond is as follows: Thiol-modified polymer: a so-called vinyl compound having at least one group having an ethylenically unsaturated double bond, or a cyclic ether compound having at least one group having a cyclic ether bond = 5: 95 to 70:30. Preferably, it is more preferably in the range of 5:95 to 60:40.

  The photocurable resin composition (C) of the present invention may further contain a photopolymerization initiator in order to promote a curing reaction. Thereby, the polymerization by light irradiation proceeds smoothly, so that a cured product can be obtained in a short time. Examples of the photopolymerization initiator contained in the photocurable resin composition (C) include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one and 1-hydroxy-cyclohexylphenyl. Ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] Alkylphenones such as -1-butanone, acylphosphine oxides such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide benzoin and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; Benzoin type such as benzoin ethyl ether, benzophenone type such as benzophenone, benzyl, 9,10-phenanthrenequinone An oxime ester such as 1,2-octanedione, 1- [4- (phenylthio)-, 2, (0-benzoyloxime)], iodonium, (4-methylphenyl) [4- (2- Examples thereof include onium salt systems such as methylpropyl) phenyl] -hexafluorophosphate and triarylsulfonium hexafluorophosphate, and sulfur systems such as thioxanthone.

  The amount of the photopolymerization initiator contained in the photocurable resin composition (C) is preferably in the range of 0.1 to 20% by weight with respect to the photocurable resin composition (C). The range is more preferably from 0.5 to 15% by weight, and even more preferably from 1 to 12% by weight.

The photocurable resin composition (C) may be used in combination with a photoinitiator (for example, an amine photoinitiator such as triethanolamine).
The amount of the photoinitiating aid is preferably in the range of 0.1 to 5% by weight, more preferably 0.5 to 3% by weight, based on the photocurable resin composition (C).

Other Additives The composition of the present invention comprises various additives, for example, a thickener, a plasticizer, a filler, a flame retardant, a solvent, a viscosity modifier, and a stabilizer (for example, polymerization of hydroquinone, methoquinone, etc.). Inhibitor), pigments (eg, cyanine blue, disazo yellow, carmine 6B, lake C, carbon black, titanium white), and various additives such as fillers and viscosity modifiers according to the purpose. it can. The amount of the stabilizer contained in the composition is preferably in the range of 0.01 to 2% by weight, more preferably 0.1 to 1% by weight, based on the whole composition. The amount of the colorant is preferably in the range of 1 to 50% by weight, more preferably 1 to 45% by weight, based on the whole composition.

  The composition of the present invention comprises, as necessary, a reactive resin composition (a thermosetting resin composition (B) or a photocurable resin composition (C)), and a thiol-modified polymer (A). It can be produced by mixing other additives (for example, stabilizers, pigments, etc.).

  When the thermosetting resin composition (B) is contained as the reactive resin composition in the composition of the present invention, the curing reaction proceeds by heat treatment. As a method of heat treatment, any method may be used as long as the curing reaction proceeds efficiently, and a method of heating in a drying furnace in which a heated gas is circulated or convected under air or a desired atmosphere, an infrared heater, or the like A heating method using an electromagnetic wave, a method in which a heated metal or ceramic is brought into contact with a film and heated, and the like can be exemplified. The curing temperature at the time of the heat treatment may be appropriately selected according to the thermosetting resin composition (B) to be used and the heat-resistant temperature of the base material, and may be, for example, about 30 ° C. or higher. It can be 200 ° C. or less. The curing time is 1 to 300 minutes. By performing the curing reaction in the above range, sufficient adhesion to the substrate can be obtained.

When the photocurable resin composition (C) is contained as the reactive resin composition in the composition of the present invention, the composition is cured by irradiation with light. The light used for curing is generally ultraviolet light.
The curing device used for the curing reaction of the photocurable resin composition (C) and the curing conditions are not particularly limited, and any method may be used as long as it is a method used for a normal photocuring reaction.

  A cured product is obtained by curing the composition of the present invention. Since the composition of the present invention exhibits excellent curability, a good cured product having a thickness of about 10 μm to about 1 mm can be obtained as well as a general thickness of about several μm. The cured product can be obtained by heat treating or irradiating the composition with light.

  The use of the composition of the present invention is not particularly limited. Inks (for example, photocurable lithographic printing inks, silk screen inks, gravure inks, printing inks such as inkjets), paints (for example, paints for paper, plastics, metals, woodworking, etc. Print varnish), adhesives, photoresists and the like.

  The ink containing the composition of the present invention is the ink of the present invention, and the paint containing the composition of the present invention is the paint of the present invention. Further, the paint of the present invention is preferably an overprint varnish.

For example, a general method for producing an ink is as follows. A varnish is prepared by dissolving a thiol-modified polymer, a stabilizer and the like in the reactive resin composition while stirring at a temperature of 60C to 100C. The varnish is mixed with a pigment, a photopolymerization initiator, and other additives by stirring with a butterfly mixer and then kneaded with three rolls or the like to obtain an ink.
The overprint varnish can be prepared by the same procedure as for the ink except that no pigment is used.

(Example)
Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

(Analysis method)
The analysis of the polymer and the thiol-modified polymer described below was performed using the method described below.

Weight average molecular weight (Mw), molecular weight distribution (Mw / Mn) of polymer and thiol-modified polymer
The weight average molecular weight (Mw) and the molecular weight distribution (Mw / Mn) were measured using GPC. Mw and Mn are values of weight average molecular weight and number average molecular weight in terms of standard polystyrene.
Column: Two Shodex LF-804 connected in series Flow rate: 1.0 mL / min
Temperature: 40 ° C
Detector: RID-20A
Sample: A sample for measurement was prepared by dissolving 50 mg of a sample in 5 mL of tetrahydrofuran.

NMR Measurement The NMR measurement of the polymer, the photopolymerization initiator, the thiol compound, and the obtained thiol-modified polymer used in the production was measured by 1 H NMR (500 MHz, in CDCl 3). FIG. 1 shows the measured NMR spectra.

Iodine value measurement The iodine value of the polymer used for production was measured according to the method specified in JIS K6235.

Method for calculating thiol modification rate The modification rate of the allyl group of the polymer was calculated by the above-described method using FT-IR.

Synthesis Example 1 Synthesis of triallyl isocyanurate polymer 1 600 g of triallyl isocyanurate was added to a 3 L separable flask, 15 g of benzoyl peroxide was added, and the mixture was heated and stirred at 80 ° C. After reacting for 1 hour, it was cooled to room temperature (25 ° C.). After cooling, methanol was added to the flask to precipitate a polymer. The obtained polymer was dried under reduced pressure at 40 ° C. for 16 hours (yield: 30.4 g, yield: 5%, Mw = 21,000, Mw / Mn = 1.8, iodine value = 156). The obtained polymer was used as Production Example 1 in Production Example 1.

Production Example 1 Production of thiol-modified polymer (Polymer 1) 20 g of methyl ethyl ketone was added to a 200 mL separable flask containing a stirrer, and 14 g of the polymer obtained in Synthesis Example 1 was added with stirring, and the mixture was heated at 25 ° C. for 60 minutes. Stir and dissolve. 5.54 g of 2-ethylhexyl 3-mercaptopropionate (manufactured by Wako Pure Chemical Industries, Ltd.) and 191 mg of a photopolymerization initiator (Irgacure 184) were added thereto, followed by stirring for 10 minutes to dissolve. While stirring at 25 ° C., the light was irradiated for 60 seconds using a light irradiation device (LIGHTNINGCURE LC6 model L8858-01, manufactured by Hamamatsu Photonics, lamp type: mercury xenon lamp, center wavelength 365 nm, emission wavelength: 300 nm to 450 nm) to carry out the enethiol reaction. went. The integrated light quantity measurement was performed using an eye ultraviolet integrated illuminometer: UVPF-A1 light receiver: PD-365 (manufactured by Eye Graphics Co., Ltd.). The measured value was (6100) mJ / cm ² at 60 seconds. The solution after the reaction was concentrated by a factor of 2 using a rotary evaporator. The obtained reaction solution was added to 400 mL of methanol with stirring to precipitate the resin. The precipitated solid was vacuum-dried at 40 ° C. for 6 hours to obtain a thiol-modified polymer (Polymer 1). The obtained thiol-modified polymer was subjected to NMR measurement and GPC measurement. (Yield: 7.0 g, Mw = 34,000, Mw / Mn = 1.7). The thiol modification rate of the allyl group of the thiol-modified polymer is determined by the FT-IR peak intensity of about 2550 cm ^{−1 (} the FT-IR peak intensity of the thiol group before the reaction (0. [00203)-FT-IR peak intensity of thiol group after reaction (0.00010)] Calculated from FT-IR peak intensity of thiol group before reaction (0.00203), 95.1% of allyl groups are modified It had been. Further, a decrease in the NMR peak indicating the allyl group of the polymer before and after the reaction was also confirmed by NMR spectrum. The NMR spectrum is shown in FIG.

Example 1, Comparative Example 1
Each composition described in Table 1 below was prepared, and the characteristics of the composition were evaluated.

表１に示したポリマー１以外の成分は下記のとおりである。
また、表１に示す組成量は重量部での表記である。
ＤＡＰ樹脂：（株）大阪ソーダ製 ダイソーダップ（ジアリルフタレート樹脂；Ｍｗ＝１．８万、Ｍｗ/Ｍｎ＝１．９、ヨウ素価＝５０）
ＤＰＧＤＡ；ジプロピレングリコールジアクリレート（新中村化学工業（株）製）
Ｉｒｇａｃｕｒｅ１８４；１−ヒドロキシ−シクロヘキシル−フェニル−ケトン（ＢＡＳＦジャパン（株）製）

Components other than the polymer 1 shown in Table 1 are as follows.
The composition amounts shown in Table 1 are expressed in parts by weight.
DAP resin: Daisodap, manufactured by Osaka Soda Co., Ltd. (diallyl phthalate resin; Mw = 18,000, Mw / Mn = 1.9, iodine value = 50)
DPGDA: dipropylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
Irgacure 184; 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF Japan Ltd.)

Evaluation of quick-drying property To each prepared composition, 10 parts by weight of Irgacure 184 (manufactured by BASF Japan Co., Ltd.) was added as a photopolymerization initiator, and the mixture was heated and mixed to prepare a sample to be used for evaluation of quick-drying property.
The above sample prepared for use in the adhesion test was coated on a plastic substrate (polypropylene substrate: biaxially stretched film manufactured by Toyobo Co., Ltd., product name: Pyrene film-OTP2161 with a thickness of 50 μm) using a wire bar (coating rod). Then, the coating was cured by a metal halide lamp having an output of 160 W / cm (light irradiation at a lamp distance of 14 cm and a light amount of about 200 mW / cm ² for a period of time until the coating film became tack-free). The UV curing device used was a box-type ultraviolet curing device manufactured by Ushio Inc. The quick-drying property was confirmed by touching the obtained coating film. The sample cured with an integrated light quantity of 4456 mJ / cm ² or less was rated as “○”, and the one cured with an integrated light quantity of 4456 mJ / cm ² or more was rated “x”. Table 2 shows the evaluation results.

Adhesion Test The prepared composition was coated on a plastic (polypropylene) film and cured in the same manner as in the quick-drying test. A Nichiban 24-mm cellotape (registered trademark) (product number: CT-24, adhesive strength: 4.01 N / 10 mm) was attached to the obtained coating film, and was strongly rubbed five times with a thumb. ). The evaluation criteria were as follows. Table 2 shows the evaluation results.
5: When the tape is quickly peeled, the cured film does not peel.
4: When the tape is quickly peeled, the cured film is peeled by 50%.
3: When the tape is peeled off slowly, the cured film does not peel off.
2: When the tape is peeled slowly, the cured film peels 50%.
1: When the tape is peeled off slowly, the cured film is completely peeled off.

Using the composition whose viscosity was adjusted, a sample was prepared in the same manner as in the quick drying test. The viscosity at 30 ° C. was measured using Thermo Fisher SCIENTIFC HAAKE MARS3. Table 2 shows the evaluation results.

As shown in Example 1, the composition prepared using the polymer modified with a thiol compound (Polymer 1) has the same quick drying property as the diallyl phthalate resin shown in Comparative Example 1. And, it has better adhesion to the polypropylene sheet than Comparative Example 1 prepared using the diallyl phthalate resin.
Further, a composition prepared using a polymer modified with a thiol compound (Polymer 1) has a low viscosity, so that it can be suitably used as an ink, particularly an inkjet printing ink.

  The composition of the present invention can be used for inks (eg, offset inks) for plastic substrates, paints, adhesives, photoresists, and the like.

Claims (8)

A thiol-modified polymer (A), wherein a polymer obtained by polymerizing a compound represented by the general formula [I] is modified with a thiol compound.

(Wherein, R ¹ represents a [—CH ₂ —CR ³ ＣＨCHR ² ] group, a glycidyl group, an alkyl group having 1 to 5 carbon atoms, or a hydrogen atom, and each R ¹ may be different or the same, at least one of which is _{^{[-CH 2 -CR 3 = CHR 2}} ] ^{_{group, [- CH 2 -CR 3 =}} CHR 2] R 2 and ^{R 3} in group each represent H or CH ₃ .)   The thiol compound is at least one selected from the group consisting of an aliphatic thiol compound, an aromatic thiol compound, an aliphatic polythiol compound, a mercaptocarboxylic acid ester compound, a mercaptocarboxylic acid, and a mercaptoether. Thiol-modified polymer.   A composition containing the thiol-modified polymer (A) according to claim 1.   The composition according to claim 3, further comprising a reactive resin composition.   The composition according to claim 4, wherein the reactive resin composition is a photocurable resin composition (C). An ink comprising the composition according to claim 3. A paint containing the composition according to claim 3. The paint according to claim 7, which is an overprint varnish.

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