WO2018150764A1

WO2018150764A1 - Thiol-modified polymer, and composition containing said polymer and use thereof

Info

Publication number: WO2018150764A1
Application number: PCT/JP2018/000306
Authority: WO
Inventors: 明穂上西; 英明馬越; 岩佐　成人
Original assignee: 株式会社大阪ソーダ
Priority date: 2017-02-17
Filing date: 2018-01-10
Publication date: 2018-08-23
Also published as: JPWO2018150764A1

Abstract

The present invention addresses the problem of providing a composition having excellent adhesion to a base material (e.g., a plastic) and good compatibility with a reactive resin composition. The present invention relates to a composition characterized by containing a thiol-modified polymer that is produced by modifying a polymer with a thiol compound, wherein the polymer is a polymer produced by polymerizing a compound represented by general formula [I]. (In the formula, R1s independently represent a [-CH2-CR3=CHR2] group, a glycidyl group, an alkyl group having 1 to 5 carbon atoms or a hydrogen atom, wherein the R1s may be different from or the same as one another, and at least one of the R1s represents a [-CH2-CR3=CHR2] group; and R2 and R3 in the [-CH2-CR3=CHR2] group independently represent H or CH3.)

Description

Thiol-modified polymer, composition containing the polymer, and use thereof

The present invention relates to a thiol-modified 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 made from 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 ═CHR 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 (for example, ultraviolet rays) or heat) are used in inks, paints, adhesives, photoresists, and the like. For example, UV-curing type printing inks are highly evaluated and have been put to practical use because of their fast curing speed, which can be cured in a short time, compatibility with the environment because they do not use solvents, and resource and energy savings. 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.) is employed as a UV ink for paper. .

However, it is known that when diallyl phthalate resin is blended when used as an ink, 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 improvement in adhesion to a plastic substrate, which is a drawback of diallyl phthalate resin, has been demanded.

Japanese Patent Laid-Open No. 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)).

As a result of diligent research to solve the above problems, the present inventor has found that a thiol compound obtained by polymerizing a compound having a specific structure in a composition containing a reactive resin composition is modified with a thiol compound. The inventors have found that a composition having excellent adhesion to a substrate (particularly plastic) can be obtained by adding a modified polymer, and the present invention has been completed.

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.

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

The composition of the present invention preferably further contains a reactive resin composition. By using the reactive resin composition, the drying property and curability of the composition are improved, the viscosity can be adjusted to be appropriate for use in printing, and the composition has excellent coating workability.

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 substrate, and particularly suitable as an ink for printing on a substrate such as a PP resin sheet or film.

Moreover, the composition of this invention can be used as a coating material. The paint of the present invention is characterized by including the composition of the present invention. This paint is suitable as a paint for drawing on a plastic substrate, and particularly suitable as a paint for drawing on a substrate such as a PP resin sheet or film.
Moreover, it is preferable that the coating material of this invention is an overprint varnish.

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

According to the present invention, it is possible to obtain a composition in which ink, paint, adhesive and photoresist are excellent in adhesion to a metal or synthetic polymer substrate, particularly a plastic substrate. Moreover, the composition of this invention can be used suitably for ink, a coating material, and an adhesive agent.

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

Hereinafter, the present invention will be described in detail.

Thiol-modified polymer (A)

As long as the thiol-modified polymer (A) of the present invention is modified by subjecting the allyl group of the polymer obtained by polymerizing the compound represented by the general formula [I] and the thiol compound to enethiol reaction, It can be used without particular limitation.
In the present invention, it is not clear why the inclusion of the thiol-modified polymer (A) has excellent adhesion to a metal or synthetic polymer substrate, particularly a plastic substrate, but it is presumed as follows. The
In the polymer obtained by polymerizing the compound represented by the general formula [I], the structure based on the isocyanurate ring (the ring structure (trimer of isocyanate) in the general formula [I]) continuously exists. The structure based on the continuously present isocyanurate ring is presumed to have excellent adhesion to metal and synthetic polymer substrates, particularly plastic substrates.
The thiol-modified polymer (A) is a polymer obtained by polymerizing the compound represented by the general formula [I] having such characteristics and further modified with a thiol compound. It is presumed that it has better adhesion to synthetic polymer substrates, particularly plastic substrates.

Wherein R ¹ represents a [—CH ₂ —CR ³ ═CHR ² ] group, a glycidyl group, an alkyl group having 1 to 5 carbon atoms (preferably 1 to 3 carbon atoms) or a hydrogen atom, and each R ¹ May be different or the same, and at least one of them (in particular, 2 is preferred and 3 is more preferred) is a [—CH ₂ —CR ³ ═CHR ² ] group, and [—CH ₂ —CR ³ = CHR ² ] R ² and R ³ in the group each represent H or CH _3. )

Polymer For 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 ═CHR 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 ═CHR ² ] group, and two are preferably [—CH ₂ —CR ³ ═CHR ² ] groups. Is more preferably a [—CH ₂ —CR ³ ═CHR ² ] group. The greater the number of [—CH ₂ —CR ³ ═CHR ² ] groups, the better the reactivity and the easier to obtain a higher molecular weight polymer.

R ² and R ³ are preferably H (hydrogen atom), and more preferably 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 these, 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, trimethallyl 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 And allyl monomethallyl monomethyl isocyanurate. Among these, triallyl isocyanurate, diallyl monoglycidyl isocyanurate, diallyl monomethyl isocyanurate and diallyl isocyanurate are preferred, triallyl isocyanurate, diallyl monomethyl isocyanurate and diallyl isocyanurate are more preferred, and triallyl isocyanurate is particularly preferred preferable.

Furthermore, a polymer obtained by copolymerizing a compound represented by the general formula [I] and another polymerizable compound can be used for the enethiol reaction. As copolymerizable compounds, acrylic acid esters such as methyl acrylate and butyl acrylate, various aliphatic and aromatic carboxylic acid vinyl esters such as vinyl acetate, vinyl laurate, 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 thereof include various aliphatic and aromatic carboxylic acid allyl esters such as allyl acid, polybasic acid allyl esters such as diallyl terephthalate and triallyl citrate. The blending ratio of the copolymer component in the polymer may be 2 to 50% by weight, and preferably 2 to 20% by weight.

Examples of methods for obtaining the compounds listed as specific examples of the compound represented by the general formula [I] may be synthesized by a generally known polymerization method, or commercially available products may be used.

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

Examples of the polymerization initiator used for 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 Acetophenones such as propan-1-one and 1-hydroxycyclohexyl phenyl ketone, benzoins such as benzoin and benzoin ethyl ether, benzophenones such as benzophenone, phosphoruss such as acylphosphine oxide, sulfurs such as thioxanthone, benzyl, 9,1 - benzyl-based photopolymerization initiators such as phenanthrenequinone are mentioned.

The amount of the polymerization initiator is preferably 5.0 parts by weight or less and preferably 3.0 parts by weight or less with respect to 100 parts by weight of the monomer of the compound represented by the general formula [I]. More preferred. Further, it is particularly preferably 0.001 to 3.0 parts by weight. The lower limit is more preferably 0.1 parts by weight, and particularly preferably 1.0 parts by weight.

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

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

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 in 100% by weight of the polymer, 80 More preferably, it is more than 98 weight%, and it is especially preferable that it is 100 weight%.

The weight average molecular weight of the polymer is preferably 250,000 or less, and more preferably 200,000 or less. Further, it is more preferably 2,000 to 150,000, and particularly preferably 5,000 to 140,000. Furthermore, the lower limit is most preferably 10,000, and more preferably 15,000. Further, 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, more preferably 1.7 to 7.5. In the present 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. Can be obtained. Specifically, the weight average molecular weight and the number average molecular weight are values measured by the methods described in the examples. In addition, the weight average molecular weight and number average molecular weight of a thiol-modified polymer (polymer modified with a thiol compound) can also be measured by the same method.

The thiol compound used in the thiol compound enthiol reaction can be used without any particular problem as long as it can react with the allyl group of the above-described polymer. 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 mercapto ether 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, 1- Pentylthiol, isopentylthiol, 2-pentylthiol, 3-pentylthiol, 1-hexylthiol, cyclohexylthiol, 4-methyl-2-pentylthiol, 1-heptylthiol (n-heptylmercaptan), 2-heptylthiol 1-octylthiol (n-octyl mercaptan), isooctylthiol, 2-ethylhexylthiol, 2,4,4-trimethyl-2-pentylthiol (tert-octyl mercaptan), 1-nonyl All (n-nonyl mercaptan), tert-nonyl thiol (tert-nonyl mercaptan), isononyl thiol, 1-decyl thiol, 1-undecyl thiol, 1-dodecyl thiol, tert-dodecyl thiol (tert-dodecyl mercaptan), Tridecylthiol, tetradecylthiol, 1-pentyldecylthiol, 1-hexyldecylthiol, 1-heptyldecylthiol, 1-octyldecylthiol, nonadecylthiol, eicosanethiol, triacontanethiol, tetracontanethiol, pentacontane Thiol, Hexacontanethiol, Heptacontanethiol, Octacontanethiol, Nonacontanethiol, Hectanethiol, 1-Myristylthiol, Cetylthiol, 1-Su Allyl thiol, 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, xylenethiol, 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, , 4-bis (2-mercaptoethyl) 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-trimercap 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, 1,2, 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 Tetrakis (mercaptomethyl) benzene, 1,2,3,5-tetrakis (mercaptomethyl) benzene, 1,2,4,5-tetrakis (mercaptomethyl) benzene, 1,2,3,4-tetrakis (2- Mercaptoethyl) 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'-dimercapto Biphenyl, 4,4'-thiobis-benzenethiol, 4,4'-dimercaptobiphenyl, 4,4'-dimercaptobibe Zyl, 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-mer Captoethylthio) benzene, 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 -Examples include mercaptobenzoimidazole and 2-mercaptobenzothiazole.

Aliphatic polythiol compounds include methanedithiol, 1,2-ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, 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 1, di-thiol compounds such as 1,1-bis (mercaptomethyl) cyclohexane, bis (2-mercaptoethyl) ether, ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate); 1,1-tris (mercaptomethyl) ethane, 2-ethyl-2-mercaptomethyl-1,3-propanedithiol, 1,2,3-propanetrithiol, trimethylolpropane tris (2-mercaptoacetate), trimethylol Trithiol compounds such as propanetris (3-mercaptopropionate) and tris ((mercaptopropionyloxy) -ethyl) isocyanurate; pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3 Mercaptopropionate), pentaerythritol tetrakis (3-mercapto pig sulfonate), can be exemplified thiol compounds having a dipentaerythritol hexa-3-mercaptopropionate SH group such as 4 or more.

Mercaptocarboxylic acid ester compounds include methyl mercaptoacetate, methyl 3-mercaptopropionate, 4-methoxybutyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, n-octyl 3-mercaptopropionate, 3-mercaptopropion Stearyl acid, 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-mercaptopropiate) Nate), pentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol hexakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptobutyrate), tris [2- (3-mercaptopropionyl) Examples thereof include oxy) ethyl] isocyanurate and tris [2- (3-mercaptobutyryloxy) ethyl] isocyanurate. Of these, 2-ethylhexyl 3-mercaptopropionate is preferable.

Examples of other thiol compounds include mercaptoacetic acid, 3-mercaptopropionic acid, 2-mercaptopropionic acid, 3-mercaptobutyric acid, mercaptohexanoic acid, mercaptooctanoic acid, mercaptostearic acid, thioglycolic acid and the like; Mercapto ethers such as mercaptoethyl) ether; mercaptoalcohol compounds such as 2-mercaptoethanol and 4-mercapto-1-butanol; silanes such as (γ-mercaptopropyl) trimethoxysilane and (γ-mercaptopropyl) triethoxysilane Examples include thiol compounds.

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 mercapto ether are preferable, and an aliphatic thiol compound and a mercaptocarboxylic acid ester compound are more preferable. A mercaptocarboxylic acid ester compound is more preferable. If it is the said thiol compound, an allyl group of a polymer can carry out enethiol reaction without a problem.

Enthiol reaction The enthiol reaction proceeds by bringing an unsaturated compound (such as an allyl compound or a polymer obtained by polymerizing an allyl compound) and a thiol compound into contact with each other. You may make it react (enthiol reaction) by providing (or active energy ray). By applying active energy, the enethiol reaction can be easily advanced.

As the active energy, thermal energy and / or light energy (particularly, at least light energy) can be used depending on the type of the polymerization initiator.

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

In addition, when applying (or irradiating) light energy (for example, when using a photopolymerization initiator), as light, radiation (gamma rays, X-rays, etc.), ultraviolet rays, visible rays, etc. can be used. Usually, it is often ultraviolet rays. In addition, when using a thermal polymerization initiator as an initiator, irradiation of light energy is not necessarily required.

As the light source, for example, in the case of ultraviolet rays, a deep UV lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a mercury xenon lamp, a halogen lamp, a UV-LED lamp, a laser light source (helium-cadmium laser) A light source such as an excimer laser). The wavelength of light may be, for example, about 150 to 800 nm, preferably 150 to 600 nm, more preferably about 200 to 400 nm (particularly 300 to 400 nm). The amount of irradiation light (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 It may be about 2000 W (for example, 30 to 1000 W). The irradiation time is not particularly limited, and may be, for example, 5 seconds to 5 hours, preferably 10 seconds to 2 hours, more preferably about 30 seconds to 1 hour, and usually about 1 to 30 minutes. May be. 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 a thermal polymerization initiator and a photopolymerization initiator according to the type of active energy ray. As the thermal polymerization initiator, dialkyl peroxides [di-tert-butylperoxide are used. Oxide, dicumyl peroxide, di (2-tert-butylperoxyisopropyl) benzene, etc.], diacyl peroxides [diaalkanoyl peroxide (such as lauroyl peroxide), dialoyl peroxide (benzoyl peroxide, benzoyl toluyl peroxide) Oxide, toluyl peroxide, etc.), peracid esters (tert-butyl peracetate, tert-butyl peroxyoctoate, tert-butyl peroxybenzoate, tert-butyl peroxyacetate, tert-butyl -Peroxycarboxylic acid alkyl esters such as oxy-2-ethylhexanoate), organic peroxides such as ketone peroxides, peroxycarbonates, 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), etc.], azoamide compounds {2,2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide} etc}}, azoamidine compounds {2 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propa ] Dihydrochloride, etc.}, azoalkane compounds [2,2′-azobis (2,4,4-trimethylpentane), 4,4′-azobis (4-cyanopentanoic acid), etc.], azo compounds having an oxime skeleton [ Azo compounds such as 2,2′-azobis (2-methylpropionamidooxime) and the like.

As photopolymerization initiators, 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, benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2 Acetophenones such as -hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomer; 2-methylanthraquinone, 2-amylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, etc. 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro Thioxanthones such as 4-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- Benzophenones such as N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethananium bromide, (4-benzoylbenzyl) trimethylammonium chloride; acylphosphine oxides and xanthones, 1,2- Oxane esters such as octanedione, 1- [4- (phenylthio)-, 2, (0-benzoyloxime)], iodonium, (4-methylphenyl) [4- (2-methylpropyl) phenyl] -hexafluoro Examples of the onium salt system include phosphate and triarylsulfonium-hexafluorophosphate. Of these, acetophenones are preferable.

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 of the polymer is determined from the iodine value of the polymer used for the enthiol reaction, and the number of functional groups in 1 g of polymer (the number of functional groups of the polymer) is calculated from the molecular weight of the polymer and the Avogadro constant. From the molecular weight of the thiol compound used for the enthiol reaction and the Avogadro constant, the number of molecules in 1 g of the thiol compound (the number of molecules of the thiol compound) is calculated. 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 in the enethiol reaction can be determined. The iodine value of the polymer can be measured according to the method defined in JIS K6235.

The thiol modification rate of the allyl group of the polymer in the enethiol reaction is the FT-IR peak intensity of about 2550 cm ⁻¹ indicating the thiol group (FT-IR peak intensity of the thiol group before the reaction−FT-IR of the thiol group after the reaction) (Peak intensity) / 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. The Mw is preferably 2,000 or more, more preferably 5,000 or more, still more preferably 10,000 or more, particularly preferably 20,000 or more, and 30 Most preferably, it is 1,000 or more.

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

Composition The composition of the present invention contains a thiol-modified polymer (A) characterized in that a polymer obtained by polymerizing a compound represented by the following general formula [I] is modified with a thiol compound. Features.

The content of the thiol-modified polymer (A) in the composition may be in the range of 1 to 70% by weight, preferably in the range of 2.5 to 65% by weight, based on the total amount of the composition. A range of ˜60% by weight is more preferred. 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. As the reactive resin composition, any resin can be used without particular limitation as long as adhesion to the substrate and curability can be obtained. For example, the thermosetting resin composition (B) or the photocurable resin can be used. Any of the compositions (C) can be used. In addition, the thermosetting resin composition (B) in this invention means what a hardening (polymerization) reaction advances by attaching | subjecting heat processing. Moreover, 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 the thermosetting resin composition (B) and the photocurable resin composition (C). 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 thermosetting resins such as epoxy resins, phenol resins, polyimide resins, polyurethane resins, alkyd resins, melamine resins, silicone resins, urea resins and the like. be able to. Among these, an epoxy resin is preferable from the viewpoint of ease of handling and adhesion to the substrate.

Further, the content of the thermosetting resin composition (B) in the composition may be appropriately selected according to the properties of the thermosetting resin to be used. In addition, when there is too little content of the thermosetting resin composition (B) in a composition, sufficient adhesiveness with a base material will not be obtained and there is too much content of a thermosetting resin composition (B). And it takes time to cure.

Thermosetting compound (b-1)
As the thermosetting compound (b-1) in the thermosetting resin composition (B) used in the present invention, a compound having an epoxy group that provides high adhesion in terms of adhesion to a substrate. Is preferred. Specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol type epoxy resin such as bisphenol S type epoxy resin, hydrogenated bisphenol A, hydrogenated bisphenol F and other hydrogenated Bisphenol type epoxy resin, phenol novolak type epoxy resin, novolac type epoxy resin such as cresol novolak type epoxy resin, alkyl diphenol type epoxy resin such as tert-butyldiphenylglycidyl ether and methyldiphenylglycidyl ether, triglycidyl-p-aminophenol And polyfunctional glycidylamine resins such as triglycidyl isocyanurate, polyfunctional glycidyl ether resins such as triphenylglycidyl ether methane, and alicyclic epoxies 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 with respect to 100 parts by weight of the thiol-modified polymer (A). 100 to 1200 parts by weight is more preferable, and 100 to 900 parts by weight is even more preferable.

Curing agent (b-2)
The curing agent (b-2) in the thermosetting resin composition (B) used in the present invention is usually thermosetting as long as it is compatible with the thermosetting compound (b-1) used. A known curing agent can be appropriately used as the resin curing agent. Specific examples include phenolic curing agents, acid anhydride curing agents, curing agents such as dicyandiamide, diamine curing agents, imidazole curing agents, tertiary amine curing agents, and phosphine curing agents. can do. Only 1 type may be used for the said hardening | curing agent, and it is also possible to use 2 or more types in combination.

The curing agent (b-2) is generally an addition polymerization type curing agent (i) that is a curing agent that reacts in an equivalent amount with the thermosetting compound (b-1), such as phenols, acid anhydrides. , An ionic polymerization type (ii) which is a curing agent that reacts with a thermosetting compound (b-1) in a small amount with a curing agent of an amine such as dicyandiamide or diamine, for example, imidazoles, tertiary amines Or it can classify | categorize into hardening | curing agents, such as phosphines. Moreover, you may use together hardening accelerators, such as imidazole, organic phosphonium, DBU (azabicycloundecene), as a regulator of hardening rate.

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 xylenediamine. Polyamide, acid anhydrides such as methyltetrahydrophthalic anhydride and hexahydrophthalic anhydride, phenols such as dicyclopentadiene and triphenylalkyl, thiols such as liquid polymercaptan and polysulfide resin, boron trifluoride-amine complex And a curing agent such as dicyandiamide.

Examples of the ionic polymerization type curing agent (ii) include a cation polymerization type and an anion polymerization type. Specifically, examples of the anion polymerization type include benzyldimethylamine 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 an addition polymerization curing system is used, the curing agent (b-2) is usually an addition polymerization type (i) that does not undergo a curing reaction at room temperature (near storage temperature) and exhibits 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. The addition amount of the curing agent (b-2) in the thermosetting resin composition (B) when the addition polymerization type (i) curing agent is used depends on the thermosetting compound (b-1). On the other hand, 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 addition amount of the curing agent (b-2) is too small, a large amount of unreacted compound (b-1) having thermosetting properties remains, and the adhesion to the film substrate is impaired. If the addition amount is too large, a large amount of unreacted curing agent (b-2) remains and 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 the composition containing the thermosetting compound (b-1) and the ionic polymerization type curing agent (ii). it can.

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

Photocurable resin composition (C)
The photocurable resin composition (C) used in the present invention has 1 so-called vinyl compound having one or more groups having an ethylenically unsaturated double bond that can be cured by light irradiation, or 1 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 compounds
Examples of vinyl compounds include aliphatic, alicyclic or aromatic (meth) acrylate monomers, allyl monomers, vinyl monomers, urethane (meth) acrylate oligomers, epoxy (meth) acrylate oligomers, polyester (meth) acrylate oligomers, etc. can do. Moreover, what mixed 2 or more types of compounds can also be used for a vinyl compound. The vinyl compound (ethylenically unsaturated compound) preferably has 1 to 20 carbon-carbon double bonds, more preferably 1 to 10, more preferably 1 to 6.

Aliphatic (meth) acrylate monomers include butyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, hydroxyethyl (meth) acrylate Alkyl (meth) acrylates such as neopentyl glycol di (meth) acrylate, alkylene glycol di (meth) acrylates such as polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di ( (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate alkylene diol di (meth) acrylates, Methylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate ethylene oxide, propylene oxide modified trimethylolpropane triacrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol, ethoxylation Polyfunctional (meth) acrylates such as pentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate, alkoxyalkylene glycol (meth) acrylates such as methoxypropylene glycol (meth) acrylate and ethoxydiethylene glycol (meth) acrylate , (Meth) acrylamide, N-butoxymethyl (meth) acrylamide, etc. 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, isobornyl (meth) acrylate and the like, and isobornyl (meth) acrylate is preferable.

As aromatic (meth) acrylate monomers, 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 vinyl monomers, styrene, α-methylstyrene, divinylbenzene, N-vinylpyrrolidone, N-vinylformamide, N-vinylcaprolactam, vinyl acetate, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl Vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, isopentyl vinyl ether, tert-pentyl vinyl ether, n-hexyl vinyl ether, isohexyl vinyl ether, 2-ethylhexyl vinyl ether, allyl vinyl ether, 2- (2-vinyloxy) acrylic acid Ethoxy) ethyl, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, acetoxymethyl vinyl Nyl 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, ethylene oxide-added trimethylol 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 Examples include ether, 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 urethane (meth) acrylate oligomers, polyether urethane (meth) acrylates in which ether glycol such as ethylene glycol is chain-extended with diisocyanate and both ends are (meth) acrylated, and polyester glycol is used instead of ether glycol. Polyester urethane (meth) acrylate, and others using caprolactone diol, polycarbonate diol, etc. can be exemplified, and polyether urethane (meth) acrylate is preferred.

Examples of the epoxy (meth) acrylate oligomer include bisphenol A glycidyl ethers such as bisphenol A type epoxy resin, novolac type epoxy resin, epoxidized oil type, etc., which are reacted with (meth) acrylic acid. 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 or carboxylating the hydroxyl group and (meth) acrylic acid in the polyester. What was obtained by esterifying a hydroxyl group-containing (meth) acrylate and an aliphatic polyester tetraacrylate can be illustrated.

Cyclic ether compound
Examples of cyclic ether compounds include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 4- (glycidyloxy) butyl (meth) acrylate, 3-methyl-3,4-epoxybutyl (meth) acrylate, 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, (iso) crotonic acid glycidyl ether, (3,4-epoxycyclohexyl) methyl (meth) acrylate, N- (3,5-dimethyl-4-glycidyl) benzylacrylamide, o-vinylbenzylglycidyl 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 in terms of compatibility with the thiol-modified polymer (A) and curability when photocured. An alicyclic or aromatic (meth) acrylate monomer is more preferable, and an aliphatic (meth) acrylate monomer is more preferable.

Content of so-called vinyl compound having one or more groups having ethylenically unsaturated double bond or cyclic ether compound having one or more groups having 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 in the photocurable resin composition (C) or the cyclic ether compound having one or more groups having a cyclic ether bond is The photocurable resin composition (C) is preferably added so that the viscosity is in the range of 1 to 3000 mPa · s (particularly 1 to 2000) (25 ° C.). Specifically, the ratio between the thiol-modified polymer (A) and 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, Thiol-modified polymer: 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 = 5: 95 to 70:30. Preferably, it is in the range of 5:95 to 60:40.

In order to accelerate the curing reaction, the photocurable resin composition (C) of the present invention may further contain a photopolymerization initiator. Thereby, since superposition | polymerization by light irradiation advances smoothly, a hardened | cured material 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] Alkylphenone series such as -1-butanone, acyl phosphine oxide series such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide benzoin, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, Benzoins such as benzoin ethyl ether, benzophenones such as benzophenone, benzyl, 9,10-phenanthrenequinone Oximes such as benzyl, 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, 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 of 5 to 15% by weight is more preferable, and the range of 1 to 12% by weight is more preferable.

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

Other Additives The composition of the present invention comprises various additives, for example, thickeners, plasticizers, fillers, flame retardants, solvents, viscosity modifiers, stabilizers (for example, polymerization of hydroquinone, methoquinone, etc. Inhibitors), pigments (for example, cyanine blue, disazo yellow, carmine 6B, lake C, carbon black, titanium white) and the like, and various additives such as fillers and viscosity modifiers may be contained depending on 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 in the range of 0.1 to 1% by weight, based on the entire composition. The amount of the colorant is preferably in the range of 1 to 50% by weight, more preferably in the range of 1 to 45% by weight, based on the entire composition.

The composition of the present invention includes a thiol-modified polymer (A), if necessary, a reactive resin composition (thermosetting resin composition (B) or photocurable resin composition (C)), Other additives (for example, stabilizers, pigments, etc.) can be mixed.

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 being subjected to heat treatment. The heat treatment method may be any method that allows the curing reaction to proceed efficiently, such as a method of heating in a drying furnace in which the gas heated in the air or in a desired atmosphere is circulated or convected, an infrared heater, etc. Examples thereof include a heating method using electromagnetic waves, a method of heating a heated metal or ceramic in contact with a film, and the like. The curing temperature during the heat treatment may be appropriately selected according to the thermosetting resin composition (B) to be used and the heat resistance temperature of the base material, and can be, for example, about 30 ° C. or more, It can be 200 degrees C or less. The curing time is 1 to 300 minutes. Sufficient adhesion with the substrate can be obtained by performing the curing reaction within the above range.

When the photocurable resin composition (C) is contained as the reactive resin composition in the composition of the present invention, it 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 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, an excellent cured product having a thickness of about 10 μm to 1 mm as well as a general thickness of about several μm can be obtained. The cured product can be obtained by heat-treating the composition or irradiating it with light.

The use of the composition of the present invention is not particularly limited. Ink (for example, printing ink for photo-curable lithographic printing plate, silk screen ink, gravure ink, inkjet, etc.), paint (for example, paint for paper, plastic, metal, woodwork, etc. Printing 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. Moreover, it is preferable that the coating material of this invention is an overprint varnish.

For example, a general method for producing ink is as follows. A thiol-modified polymer, a stabilizer and the like are dissolved in the reactive resin composition while stirring at a temperature of 60 ° C. to 100 ° C. to prepare a varnish. The ink is obtained by mixing the varnish with a pigment, a photopolymerization initiator, and other additives with a butterfly mixer and then kneading with a three-roll roll.
The overprint varnish can be prepared by the same procedure as that for ink except that no pigment is used.

(Example)
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not limited to these Examples.

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

Polymer, thiol-modified polymer weight average molecular weight (Mw), molecular weight distribution (Mw / Mn)
The weight average molecular weight (Mw) and 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-804s 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.

Each NMR measurement of the polymer used for NMR measurement production, the photopolymerization initiator, the thiol compound, and the obtained thiol-modified polymer was performed by 1H NMR (500 MHz, in CDCl 3). Each measured NMR spectrum is shown in FIG.

Iodine value measurement The iodine value of the polymer used for production was measured according to the method defined 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 the 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 in Production Example 1 as Polymer 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 stirring bar, and 14 g of the polymer obtained in Synthesis Example 1 was added with stirring, at 25 ° C. for 60 minutes. Stir to dissolve. To this, 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 and dissolved by stirring for 10 minutes. While stirring at 25 ° C., using an optical irradiation device (LIGHTNINGCURE LC6 model L8858-01, manufactured by Hamamatsu Photonics, lamp type: mercury xenon lamp, central wavelength 365 nm, emission wavelength: 300 nm to 450 nm), the enthiol reaction was performed for 60 seconds. went. The integrated light quantity measurement was performed using an eye ultraviolet ray integrated illuminometer: UVPF-A1 light receiver: PD-365 (manufactured by Eye Graphics). The measured value was (6100) mJ / cm ² in 60 seconds. The solution after the reaction was concentrated twice using a rotary evaporator. The resulting reaction solution was added to 400 mL of stirred methanol 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 based on the FT-IR peak intensity of about 2550 cm ⁻¹ indicating the thiol group of 2-ethylhexyl 3-mercaptopropionate (FT-IR peak intensity of the thiol group before the reaction (0. 00203) -FT-IR peak intensity of thiol group after reaction (0.00010)) ÷ FT-IR peak intensity of thiol group before reaction (0.00203) It had been. In addition, the 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 and Comparative Example 1
Each composition described in Table 1 below was prepared, and the characteristics of the composition were evaluated.

Components other than polymer 1 shown in Table 1 are as follows.
The composition amounts shown in Table 1 are expressed in parts by weight.
DAP resin: Daisoda dup 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 10 parts by weight of Irgacure 184 (manufactured by BASF Japan Ltd.) was added as a photopolymerization initiator to each prepared composition, and a sample used for evaluation of quick-drying property was prepared by heating and mixing.
A plastic base material (polypropylene base material: biaxially stretched film manufactured by Toyobo Co., Ltd., product name: pyrene film-OT P2161 thickness 50 μm) is coated with a wire bar (coating rod) on the sample prepared for use in the adhesion test. Then, it was cured with a metal halide lamp having an output of 160 W / cm (light irradiation for a time until the coating became tack-free at a lamp distance of 14 cm and a light amount of about 200 mW / cm ² ). As the UV curing device, a box type ultraviolet curing device manufactured by USHIO was used. Quick-drying property was confirmed by touching the obtained coating film. Those cured with integrated light quantity 4456mJ / cm ² or less ○, and as × those cured by the integrated quantity of light 4456mJ / cm ² or more. The evaluation results are shown in Table 2.

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

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

As shown in Example 1, the composition prepared using a polymer modified with a thiol compound (Polymer 1) has a quick drying property equivalent to that of the diallyl phthalate resin shown in Comparative Example 1. And it has the adhesiveness to the polypropylene sheet superior to the comparative example 1 prepared using diallyl phthalate resin.
Moreover, since the composition prepared using the polymer (polymer 1) modified with a thiol compound has a low viscosity, it can be suitably used as an ink, particularly an inkjet printing ink.

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

Claims

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 ═CHR 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 mercapto ether. Thiol modified polymer.
A composition containing the thiol-modified polymer (A) according to claim 1 or 2.
Furthermore, the composition of Claim 3 containing 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 any one of claims 3 to 5.
A paint comprising the composition according to any one of claims 3 to 5.
The paint according to claim 7, which is an overprint varnish.