JP2014133875A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a curable composition which is curable in a short time at room temperature or by heating at a relatively low temperature after exposure to an active energy ray, and excellent in storage stability at 25°C; and a curing method.SOLUTION: The curable composition contains (A)-(C) components, where the (A) component is a compound having two or more thiirane rings in each molecule; the (B) component is a photobase generator containing a salt having an anion represented by the specified general formula (1); and the (C) component is a sensitizer.

Description

The present invention relates to a curable composition and a curing method that can be cured for a short time by heating or room temperature after irradiation with active energy rays.

A compound having a thiirane ring in which an oxygen atom of an oxirane ring of an epoxy resin is replaced with a sulfur atom is known as an episulfide resin. It is known that episulfide resins have characteristics such as excellent low-temperature curability with amine compounds, good water resistance, high refractive index, and flame retardancy compared to epoxy resins.

However, most of the conventional episulfide-based compositions are two-component curable, requiring complicated steps such as weighing, mixing, and defoaming the resin component and the curing agent component immediately before actual use. Since the later usable period is limited and there is a possibility of mixing errors, there is a disadvantage that workability and reliability are inferior. For example, Patent Documents 1 to 3 show an episulfide resin composition that is faster curing at a lower temperature than an epoxy resin composition, but it is two-component curable and has the above-mentioned problems in workability and reliability. Have

As a technique for solving this problem, as described above, by using a so-called latent curing agent or latent catalyst that does not react with episulfide resin at room temperature and shows reactivity by stimulation such as heating or irradiation with active energy rays. It is known that a one-component curable composition that solves the problem of such a two-component curable composition can be obtained. For example, Patent Document 4 describes a specific example in which an episulfide resin is liquefied using a carboxylic acid-containing compound and a thermal latent catalyst as a curing agent. However, since this composition requires 30 minutes at 140 ° C. for the curing time (baking time), an episulfide-based heat-curable one-component composition that can be cured under lower temperature and shorter heating conditions is desired. Patent Document 5 describes a specific example in which phenol or dicyandiamide is added as a curing agent to an episulfide resin, but there is no description about storage stability, and the curing temperature also requires 170 ° C. It is not shown. In Patent Documents 6 to 8, it is said that a thermosetting one-component resin composition using an episulfide resin is possible by using a latent curing agent. No specific examples are described as to whether good low-temperature fast curability and storage stability can be obtained.

As a technique capable of curing the episulfide resin at a relatively low temperature, a curable composition using a photobase generator, which is a latent catalyst that generates a basic compound by irradiation with active energy rays, can be mentioned. Patent Documents 9 and 10 disclose a curable composition characterized by containing an episulfide compound and a photobase generator such as N- (2-methyl-2-phenylpropionyloxy) -N-cyclohexylamine. Yes.

JP-A-50-124952 JP-A-11-140161 JP 2002-173533 A JP-A-4-202523 JP 2004-142133 A JP-A-11-279519 JP-A-11-209576 JP 2001-342253 A JP 2002-47346 A JP 2002-105110 A

However, the curable compositions disclosed in Patent Documents 9 and 10 have a problem that the curability is inferior as shown in Comparative Example 7 of the present specification.

An object of the present invention is to solve the above-mentioned problems, and to provide a curable composition that can be cured for a short time by heating or room temperature after irradiation with active energy rays, and a method for curing the same.

That is, as a result of intensive studies to achieve the object, the present invention has found that the object can be achieved by a specific curable composition, and has completed the present invention.
A curable composition comprising the following components (A) to (C):
(A) component: a compound having two or more thiirane rings in the molecule (B) component: a photobase generator containing a salt having an anion represented by the following general formula (1) (C) component: sensitizer

The curable composition of the present invention can be cured for a short time by heating or room temperature after irradiation with active energy rays, and is excellent in storage stability. Furthermore, it is excellent in curability and adhesive force by LED irradiation. The curable composition of the present invention is further improved in curability by using the component (D) in combination. In addition, by arbitrarily selecting the type and addition amount of the components (B) to (D), and arbitrarily selecting the irradiation amount of the active energy ray and the atmospheric temperature at the time of irradiation, the polymerization curing rate is kept as desired. Can be controlled. Due to this characteristic, for example, it is not cured immediately after energy irradiation, and can be cured by standing for a short time at room temperature or under heating. The curable composition of the present invention enables the adhesion of the material and the curing of the portion shaded by ultraviolet rays. Moreover, the fluidity | liquidity of the curable composition after light irradiation can be adjusted to the curable composition of this invention by adding (E) and (F) component further. Due to these characteristics, it can be used for various applications such as adhesion, sealing, casting, painting, coating, photoetching, nanoimprinting, and photoprinting materials.

The present invention will be described in detail below.
<(A) component>
(A) component in the curable composition of this invention should just be a compound which has a 2 or more thiirane ring in a molecule | numerator. In addition, the compound (A) having the thiirane ring may have a functional group other than the thiirane ring. Specific examples thereof include an epoxy group, a hydroxyl group, a vinyl group, an acryloyl group, a methacryloyl group, an acetal group, an ester group, a carbonyl group, an amide group, and an alkoxysilyl group. Furthermore, the compound (A) having a thiirane ring can be used alone or in admixture of two or more.

Examples of the method for producing the component (A) of the present invention include thermal hydrolysis of hydroxymercaptan, treatment with 1,2-chlorothiol with a weak alkaline solution, sulfur of ethylenically unsaturated ether or polysulfide dialkyl, etc. Treatment with a compound is mentioned. Further, a method for obtaining a thiirane ring-containing compound by replacing all or part of oxygen atoms in an epoxy ring with a sulfur atom using an epoxy compound as a raw material is already known. Such compounds are also called episulfides or episulfide resins. Illustratively, J.M. Polym. Sci. Polym. Phys. 17, 329 (1979), a method using an epoxy compound and thiocyanate, Org. Chem. 26, 3467 (1961), a method using an epoxy compound and thiourea, JP 2000-351829 A, JP 2001-342253 A, JP 09-255781 A, JP 09-110979 A. Examples thereof include, but are not limited to, methods disclosed in Japanese Patent Application Laid-Open No. 09-071580.

Examples of the component (A) of the present invention include 2,2-bis (4- (2,3-epithiopropoxy) phenyl) propane, bis (4- (2,3-epithiopropoxy) phenyl) methane, 1,6-di (2,3-epithiopropoxy) naphthalene, 1,1,1-tris- (4- (2,3-epithiopropoxy) phenyl) ethane, 2,2-bis (4- (2 , 3-epithiopropoxy) cyclohexyl) propane, bis (4- (2,3-epithiopropoxy) cyclohexyl) methane, 1,1,1-tris- (4- (2,3-epithiopropoxy) cyclohexyl) Ethane, 1,5-pentanediol 2,3-epithiocyclohexyl) ether, 1,6-hexanediol di (3,4-epithiooctyl) ether, and the like. Not intended to be.

The component (A) of the present invention is preferably all or one of the oxygen atoms of the oxirane ring of the epoxy compound having a bisphenol skeleton from the viewpoint that a curable composition having excellent curability, adhesive strength and storage stability can be obtained. A compound having a thiirane ring substituted with a sulfur atom, and more preferably, the carbon-carbon unsaturated bond of an aromatic ring of an epoxy compound having a bisphenol skeleton as disclosed in JP-A-2000-351829 is hydrogenated. A compound having a thiirane ring in which all or part of oxygen atoms of the oxirane ring of the hydrogenated bisphenol epoxy resin is substituted with a sulfur atom, particularly preferably a thiirane ring-containing compound having a hydrogenated bisphenol A skeleton. is there.

<(B) component>
A photobase generator comprising a salt composed of an anion represented by the general formula (1) which is the component (B) in the curable composition of the present invention and an arbitrary cation, and a basic compound obtained by irradiation with active energy rays. It is a generated compound. Moreover, the curable composition which has the outstanding sclerosis | hardenability and storage stability by (B) component is obtained.

(Wherein R ^{1 to} R ⁴ each represent a hydrogen atom, a halogen atom, a substituted or unsubstituted aromatic group, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and are the same as each other) Examples of the substituent include a hydrogen atom, a halogen atom, a hydroxy group, a linear or branched alkyl group having 1 to 20 carbon atoms, and a cycloalkyl group having 3 to 20 carbon atoms. , Aryl groups having 6 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, ester groups, carboxyl groups, aldehyde groups, amino groups, imino groups, amide groups, imide groups, cyano groups, sulfonic acid groups, sulfonyl groups, And a nitro group, a sulfide group, a thiol group, a group in which an isocyanate group is used alone, or a combination of a plurality of them.)

As the component (B), a compound represented by the general formula (2) or the general formula (3) is preferably used from the viewpoint of more excellent curability.

Wherein R ^{5 to} R ⁸ are each a hydrogen atom, a halogen atom, a hydroxy group, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, carbon Aryl group having 6 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, ester group, carboxyl group, aldehyde group, amino group, imino group, amide group, imide group, cyano group, sulfonic acid group, sulfonyl group, nitro group , A sulfide group, a thiol group, a group in which an isocyanate group is used singly or in any combination, and the like may be the same as or different from each other, Z ⁺ is a quaternary ammonium cation, an alkali metal cation, phosphonium Among them, a quaternary ammonium cation and a phosphonium cation are preferable because they represent cations and are particularly excellent in curability. Each independently represents an integer of 0-4.)

(Wherein R ^{9 to} R ¹¹ each represent a hydrogen atom, a halogen atom, a substituted or unsubstituted aromatic group, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and R ¹² represents a carbon number. Represents a 1 to 20 alkyl group, and the substituent includes a hydrogen atom, a halogen atom, a hydroxy group, a linear or branched alkyl group having 1 to 20 carbon atoms, and a cycloalkyl group having 3 to 20 carbon atoms. , Aryl group having 6 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, ester group, carboxyl group, aldehyde group, amino group, imino group, imide group, nitrile group, amide group, imide group, cyano group, sulfonyl group acid, a sulfonyl group, a nitro group, a sulfide group, a thiol group, and groups in which a combination of isocyanate groups alone or in any the like .Z ⁺ quaternary ammonium cation Emissions, alkali metal cation, represents the phosphonium cations, quaternary ammonium cations from the particularly excellent curability Among these, phosphonium cations are preferred.)

Further, the quaternary ammonium cation of Z ⁺ includes 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] non-5-ene, and triaza. The alkali metal cation of Z ⁺ is selected from the group consisting of a cation having one or more structures of bicyclodecene, hexahydromethylpyrimidopyrimidine, tetra-n-butylammonium in the molecule, and the alkali metal cation of Z ⁺ is sodium cation, potassium cation, lithium The phosphonium cation of Z ⁺ selected from the group consisting of cations is a compound represented by the following general formula (4).

(Wherein R ^{13 to} R ¹⁶ each represent a hydrogen atom, a halogen atom, a substituted or unsubstituted aromatic group, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and are the same as each other) May be different.)

Specific compounds of the component (B) in the curable composition of the present invention include tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, benzyltriphenylphosphonium tetraphenylborate, and p-tolyltriphenylphosphonium tetra. -P-tolylborate, tri-tert-butylphosphonium tetraphenylborate, di-tert-butylmethylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, tetraphenylborate sodium salt, tetraphenylborate potassium salt, 2-ethyl-4-methylimidazolium tetraphenylborate, 1-8-diazabicyclo [5.4.0] undec-7-ene-tetraphenylborate, , 5-diazabicyclo [4.3.0] non-5-ene-tetraphenylborate, tetrabutylammonium tetraphenylborate, tetrabutylammonium-butyltriphenylborate, tetrabutylammonium-butyltri-1-naphthalenylborate , Tetrabutylphosphonium tetraphenylborate and the like, but are not limited thereto.

Examples of commercially available components (B) include PBG-SA1, PBG-SA1BU, PBG-SA2, U-CAT5002 (manufactured by San Apro Co., Ltd.), DBN-K, EMZ-K, TPP-K, TPPZ-K, and TPTP. -MK, TPP-MK, TTBuP-K, DTBMP-K (made by Hokuko Chemical Co., Ltd.), P3B, BP3B, N3B, MN3B (made by Showa Denko Co., Ltd.) and the like. Moreover, it can also synthesize | combine using well-known methods, such as the compound disclosed in the patent document 10 which satisfy | filled the requirements of (B) component of this invention, and the method of a nonpatent literature 1. Among these, N3B is preferable because of its extremely high solubility and curability. Moreover, in this invention, (B) component can also use 1 type or multiple types together.

The blending amount of the component (B) in the curable composition of the present invention is not particularly limited, but is preferably in the range of 0.001 to 30 parts by mass with respect to 100 parts by mass in total of the component (A). More preferably, it is 0.1-10 mass parts. When (B) component is added within said range, the curable composition excellent in the balance of a cure rate and the intensity | strength of hardened | cured material, storage stability, etc. can be obtained. If it is less than 0.001 part by mass, the curable composition of the present invention cannot be provided with effective curability, and if it exceeds 30 parts by mass, it becomes difficult to dissolve in the component (A), storage stability and various other properties. There is a risk of adversely affecting physical properties.

In addition, (B) component in the curable composition of this invention can improve compatibility with (A) component by diluting with a solvent. The solvent is not particularly limited as long as it can dissolve the component (B). Specifically, water, alcohols, ketones, esters, ethers, hydrocarbons, and halogenated hydrocarbons may be used. Can be mentioned. Examples of alcohols include methanol, ethanol, propanol and the like. Examples of ketones include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples of the esters include ethyl acetate, propyl acetate, butyl acetate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and the like. Examples of ethers include diethyl ether, dibutyl ether, diethylene glycol monomethyl ether, and the like. Examples of the hydrocarbons include pentane, cyclopentane, hexane, cyclohexane, heptane, toluene and the like. Examples of halogens include Freon-113, trichloroethylene, 1,1,1-trichloroethane, 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether, 3,3-dichloro-1 1,1,2,2-pentafluoropropane and the like. Of these, ketones, esters, and hydrocarbon solvents are preferred because of their good solubility with the component (B). A solvent can also be used 1 type or in mixture of 2 or more types.

<(C) component>
The photosensitizer that is the component (C) of the present invention may be any compound that increases the activity of the composition with respect to light by combining with the component (B), such as energy transfer, electron transfer, and proton transfer. The type of various sensitizing mechanisms is not limited. Generally, it is roughly divided into compounds represented by the general formulas (5) to (8), photo radical polymerization initiators, aromatic hydrocarbons, nitro compounds, and dyes. The compounds represented by general formulas (5) to (8), which have good compatibility and excellent curability, radical polymerization initiators, aromatic hydrocarbons and dyes are preferred. Specifically, in the curable composition of the present invention, the component (C) is selected from the group consisting of compounds represented by the general formulas (5) to (8); benzyl ketal photoradical polymerization initiation Agent, α-hydroxyacetophenone photoradical polymerization initiator, benzoin photoradical polymerization initiator, aminoacetophenone photoinitiator, oxime ketone photoradical polymerization initiator, acylphosphine oxide photoradical polymerization initiator, benzophenone compound A radical polymerization initiator selected from the group consisting of thioxanthone compounds, anthraquinone compounds, and general formula (9); aromatic hydrocarbons selected from the group consisting of naphthalene derivatives and anthracene derivatives; nitrobenzoic acid and nitro A nitro compound selected from the group consisting of aniline; or riboflavy , Rose Bengal, eosin, Erishisuroshin, methylene blue, and from the group consisting of New Methylene Blue Rose be selected from dye selected preferably.

Examples of the compound represented by the general formula (5) include 9-fluorenone, 2-hydroxy-9-fluorenone, 2-amino-9-fluorenone and the like.

Wherein R ¹⁷ and R ¹⁸ are each a hydrogen atom, a halogen atom, a hydroxy group, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, carbon Formula 6-20 aryl group, alkoxy group, ester group, carboxyl group, aldehyde group, amino group, imino group, imide group, nitrile group, amide group, imide group, cyano group, sulfonyl group, sulfonyl group, nitro group , A sulfide group, a thiol group, a group in which an isocyanate group is used alone or in combination, and may be the same as or different from each other, and a and b each independently represent an integer of 0 to 4. .)

Examples of the compound represented by the general formula (6) include anthrone and dibenzosuberone.
(In the formula, n represents an integer of 1 to 12, and R ¹⁹ and R ²⁰ are a hydrogen atom, a halogen atom, a hydroxy group, a linear or branched alkyl group having 1 to 20 carbon atoms, carbon, respectively. C3-C20 cycloalkyl group, C6-C20 aryl group, alkoxy group, ester group, carboxyl group, aldehyde group, amino group, imino group, imide group, nitrile group, amide group, imide group, cyano group , A sulfonyl group, a sulfonyl group, a nitro group, a sulfide group, a thiol group, a group in which an isocyanate group is used alone or in any combination, and the like may be the same or different. Each independently represents an integer of 0-4.)

Examples of the compound represented by the general formula (7) include fluorene, 2-bromofluorene, 9-bromofluorene, 9,9-dimethylfluorene, 2-fluorofluorene, 2-iodofluorene, 2-fluorenamine, 9-fluorenol, 2,7-dibromofluorene, 9-aminofluorene hydrochloride, 2,7-diaminofluorene, 9,9′-spirobi [9H-fluorene], 2-fluorenecarboxaldehyde, 9-fluorenylmethanol, 2-acetylfluorene Etc.

(In the formula, R ²¹ and R ²² are each a hydrogen atom, a halogen atom or a hydroxy group, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and carbon. Formula 6-20 aryl group, alkoxy group, ester group, carboxyl group, aldehyde group, amino group, imino group, imide group, nitrile group, amide group, imide group, cyano group, sulfonyl group, sulfonyl group, nitro group , A sulfide group, a thiol group, an isocyanate group, etc., or a group in which a plurality of them are arbitrarily combined, but not limited to this, a and b each independently represent an integer of 0 to 4.)

Fluoranthene etc. are mentioned as a compound represented by General formula (8).
Wherein R ^{23 to} R ²⁵ are each a hydrogen atom, a halogen atom or a hydroxy group, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, carbon Formula 6-20 aryl group, alkoxy group, ester group, carboxyl group, aldehyde group, amino group, imino group, imide group, nitrile group, amide group, imide group, cyano group, sulfonyl group, sulfonyl group, nitro group , A sulfide group, a thiol group, an isocyanate group, etc., or a group in which a plurality of them are arbitrarily combined, but not limited thereto, a to c each independently represents an integer of 0 to 4.)

The photoradical polymerization initiator used for the component (C) of the present invention is roughly classified into an intramolecular cleavage type photoradical polymerization initiator and a hydrogen abstraction type photoradical polymerization initiator.

The intramolecular cleavage type photoradical polymerization initiator used as the component (C) is a type of radical initiator in which the compound is cleaved by irradiation with active energy rays to generate radicals. Ketal photoradical polymerization initiator, α-hydroxyacetophenone photoradical polymerization initiator, benzoin photoradical polymerization initiator, aminoacetophenone photoinitiator, oxime ketone photoradical polymerization initiator, acylphosphine oxide photoradical polymerization Examples thereof include initiators, titanocene-based photoradical polymerization initiators, thiobenzoic acid S-phenyl polymerization initiators, and derivatives obtained by increasing their molecular weight. Among these intramolecular open-radical radical initiators, benzyl ketal photoradical polymerization initiators and α-hydroxyacetophenone photoradical polymerizations are among them because of their excellent compatibility with the component (B) and excellent curability. Preferred are initiators, benzoin-based photoradical polymerization initiators, aminoacetophenone-based photoinitiators, oxime ketone-based photoradical polymerization initiators, and acylphosphine oxide-based photoradical polymerization initiators, and more preferably α-hydroxyacetophenone-based photoradicals. Examples thereof include a polymerization initiator, a benzoin photoradical polymerization initiator, an aminoacetophenone photoinitiator, and an oxime ketone photoradical polymerization initiator. Further, from the viewpoint of good storage stability, an acylphosphine oxide photoradical polymerization initiator is preferably used.

Examples of the hydrogen abstraction type photo radical polymerization initiator include a benzophenone photo radical initiator, a thioxanthone photo radical polymerization initiator, an anthraquinone photo initiator, and a compound represented by the general formula (9). Among these, a benzophenone-based photoradical initiator and a thioxanthone-based photoradical polymerization initiator are preferably used because of excellent curing acceleration by LED irradiation.

Examples of the benzyl ketal photo radical polymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one.

Examples of the α-hydroxyacetophenone photoradical polymerization initiator include 2-hydroxy-2-methyl-1-phenyl-propan-1-one and 1- [4- (2-hydroxyethoxy) -phenyl] -2. -Hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propane- 1-one, 1- (4-dodecylbenzoyl) -1-hydroxy-1-methylethane, 1- (4-isopropylbenzoyl) -1-hydroxy-1-methylethane, 1-benzoyl-1-hydroxy-1-methylethane, 1- [4- (2-hydroxyethoxy) -benzoyl] -1-hydroxy-1-methylethane, 1- [4- (acryloylio) Ciethoxy) -benzoyl] -1-hydroxy-1-methylethane, phenyl-1-hydroxy-cyclohexyl ketone, and the like. From the viewpoint of photoactivity, 1- [4- (2-hydroxyethoxy) -phenyl]- 2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propane -1-one, 1- (4-dodecylbenzoyl) -1-hydroxy-1-methylethane, 1- (4-isopropylbenzoyl) -1-hydroxy-1-methylethane, 1-benzoyl-1-hydroxy-1-methylethane 1- [4- (2-hydroxyethoxy) -benzoyl] -1-hydroxy-1-methylethane, 1- [4- (Acryloyloxyethoxy) -benzoyl] -1-hydroxy-1-methylethane, phenyl-1-hydroxy-cyclohexyl ketone and the like.

Examples of the benzoin-based photoradical polymerization initiator include benzoin, benzoin isobutyl ether, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.

Examples of the aminoacetophenone photoradical polymerization initiator include 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- ( 4-morpholinophenyl) -butanone-1 and the like.

Examples of the oxime ketone photo radical polymerization initiator include 1.2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6]. -(2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime) and the like.

Examples of the acylphosphine oxide photo radical polymerization initiator include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and the like.

Examples of the benzophenone photoradical initiator include benzophenone, 4-methylbenzophenone, 3-benzoylbiphenyl, 4- (4-methylphenylthio) benzophenone, methyl 2-benzoylbenzoate, 4-phenylbenzophenone, 4,4 ′. -Bis (dimethoxy) benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 2-benzoylbenzoic acid methyl ester, 2-methylbenzophenone, 3-methylbenzophenone, 3, Examples include benzophenone derivatives such as 3′-dimethyl-4-methoxybenzophenone and 2,4,6-trimethylbenzophenone, and preferably a tertiary amine is present on the aromatic ring of benzophenone from the viewpoint of both curability and storage stability. Place Have not compounds can be mentioned that with, especially 4- (4-methylphenyl thio) benzophenone, 4-phenyl benzophenone is preferably used.

Examples of the thioxanthone photoradical polymerization initiator include thioxanthone, xanthone, 2-chlorothioxanthone, 4-chlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, Examples thereof include thioxanthone derivatives such as 1-chloro-4-propoxythioxanthone and 2,4-diethylthioxanthen-9-one.

Examples of the fluorene-based photoradical initiator include 2-hydroxy-9-fluorenone. Examples of the anthrone photoradical initiator include anthrone, dibenzosuberone, 2-amino-9-fluorenone and the like.

Examples of the anthraquinone photoinitiator include anthraquinone, 2-ethylanthraquinone, 2-hydroxyanthraquinone, and 2-aminoanthraquinone.

Examples of the compound represented by the general formula (9) include 1-phenyl-1,2-propanedione, 1,3-diphenylpropanetrione, benzyl, 1,4-bisbenzyl, 4,4′-dimethylbenzyl, 4,4′-dibromobenzyl, 4,4′-difluorobenzyl, benzoylformic acid, methyl benzoylformate, ethyl benzoylformate, methyl 4-nitrobenzoylformate, methyl 4-methoxybenzoylformate, ethyl 4-methoxybenzoylformate, 4- ethyl n-butylbenzoylformate, ethyl 4-t-butylbenzoylformate, ethyl 3,4-dimethoxybenzoylformate, ethyl 4-isopropylbenzoylformate, ethyl 4-dimethylaminobenzoylformate, ethyl 3,4-dimethylbenzoylformate, 3 -Ethyl methylbenzoylformate, 4-methyl Ethyl rubenzoylformate, ethyl 4-phenoxybenzoylformate, ethyl 4-thiomethylbenzoylformate, ethyl 4-cyanobenzoylformate, methyl pyruvate, ethyl pyruvate, methyl 2-oxovalerate, ethyl 2-oxovalerate, 2 Examples include, but are not limited to, dimethyl oxoglutarate and ethyl 2-oxo-4-phenylbutyrate.

Wherein R ²⁶ and R ²⁷ are each a hydrogen atom, a halogen atom or a hydroxy group, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, carbon Formula 6-20 aryl group, alkoxy group, ester group, carboxyl group, aldehyde group, amino group, imino group, imide group, nitrile group, amide group, imide group, cyano group, sulfonyl group, sulfonyl group, nitro group , Sulfide group, thiol group, isocyanate group, etc., or a group in which a plurality of them are arbitrarily combined, but is not limited to this, a represents each independently an integer of 0 to 4.)

Examples of the aromatic hydrocarbon used in the component (C) of the present invention include naphthalene derivatives and anthracene derivatives.

Examples of the naphthalene derivative include 1-methylnaphthalene, 2-methylnaphthalene, 1-fluoronaphthalene, 1-chloronaphthalene, 2-chloronaphthalene, 1-bromonaphthalene, 2-bromonaphthalene, 1-iodonaphthalene, and 2-iodo. Naphthalene, 1-naphthol, 2-naphthol, 1-methoxynaphthalene, 2-methoxynaphthalene, 1,4-dicyanonaphthalene, methyl 3-hydroxy-2-naphthoate and the like can be mentioned.

Examples of the anthracene derivative include anthracene, 1,2-benzanthracene, 9,10-dichloroanthracene, 9,10-dibromoanthracene, 9,10-diphenylanthracene, 9-cyanoanthracene, 9,10-dicyanoanthracene, 2 , 6,9,10-tetracyanoanthracene and the like.

Examples of the nitro compound include nitrobenzoic acid and nitroaniline. Examples of nitroaniline include 2-nitroaniline, 3-nitroaniline, 4-nitroaniline and the like. Examples of nitrobenzoic acid include 2-nitrobenzoic acid, methyl 2-nitrobenzoate, 3-nitrobenzoic acid, 3 -Methyl nitrobenzoate, 4-nitrobenzoic acid, methyl 4-nitrobenzoate and the like.

Examples of the dye include riboflavin, rose bengal, eosin, erythrosin, methylene blue, and new methylene blue rose. Among them, rose bengal is used because of its high photoactivity.

The addition amount of the component (C) in the curable composition of the present invention needs to refer to the absorption wavelength and molar extinction coefficient, but with respect to 1 part by mass of the component (B) in the curable composition of the present invention. In addition, the component (C) is preferably 0.001 to 10 parts by mass, and more preferably 0.005 to 5 parts by mass. If the amount of the component (C) is less than 0.001 part by mass relative to 1 part by mass of the component (B), there is a possibility that heating or room temperature curing for a short time may not be obtained after irradiation with active energy rays. When it exceeds the part, there is a possibility that the cured product is likely to generate outgas.

<(D) component>
(D) component in the curable composition of this invention should just be a thiol compound which has one or more thiol groups in a molecule | numerator. Specific examples include 3-methoxybutyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, tridecyl 3-mercaptopropionate, methylthioglycolate, 2-ethylhexylthioglycolate, 1-butanethiol 1-hexanethiol, 1-dodecanethiol, cyclohexyl mercaptan, 3-mercapto-2-butanol, γ-mercaptopropyltrimethoxysilane, benzenethiol, benzyl mercaptan, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopro Pionate, ethylene glycol bisthioglycolate, 1,4-butanediol bisthioglycolate, trimethylolpropane tristhioglycolate, pentaerythritol Laxthioglycolate, di (2-mercaptoethyl) ether, 1,4-butanedithiol, 1,5-dimercapto-3-topentane, 1,8-dimercapto-3,6-dioxaoctane, 1,4-benzene Dimethanethiol, 1,3-benzenedimethanethiol, 1,5-naphthalenedithiol, 1,3,5-trimercaptomethylbenzene, 4,4'-thiodibenzenethiol, 1,3,5-trimercaptomethyl -2,4,6-trimethylbenzene, 2,4,6-trimercapto-s-triazine, 2-dibutylamino-4,6-dimercapto-s-triazine, pentaerythritol tetrakis (3-mercaptopropionate), Dipentaerythritol hexa-3-mercaptopropionate, terminal thiol group-containing polyether Terminal thiol group-containing polythioether, thiol compound obtained by reaction of epoxy compound with hydrogen sulfide, thiol compound having terminal thiol group obtained by reaction of polythiol compound and epoxy compound, etc. It is not something.

By adding the component (D), the opening of the thiirane ring in the initial stage of polymerization can be promoted, so that curing can be promoted. In addition, the rate of curing can be suppressed because the rate of chain polymerization of the thiirane group alone is reduced by the addition reaction of the thiirane group and the thiol group. By combining these actions, the curing rate can be adjusted by adding any kind and blending amount of thiol compounds according to the purpose. Moreover, the storage stability can be improved by using a thiol compound having as little basic impurities as possible. Further, when a compound having three or more thiol groups in the molecule or a thiol compound having an aromatic ring in the molecule is used, the heat resistance of the cured product can be improved. Further, when a secondary thiol compound is used, the storage stability can be further improved. Addition of these thiol compounds can adjust properties such as viscosity, transmittance, and refractive index of the curable composition and properties such as transmittance, refractive index, toughness, and flexibility of the cured product.

Examples of the product of component (D) of the present invention include JER mate QX11, QX12, JER Cure QX30, QX40, QX60, QX900, Capcure CP3-800 (manufactured by Mitsubishi Chemical Corporation), OTG, EGTG, TMTG, PETG, 3 -MPA, TMTP, PETP (manufactured by Sakai Chemical Co., Ltd.), MPM, EHMP, NOMP, NBMP, STMP, EGMP-4, TEMPIC, TMMP, Lecad 804, PEMP, PEMP-II-20P, DPMP (manufactured by SC Organic Chemical Co., Ltd.) ), Thiocol LP-2, LP-3, Polythiol QE-340M (manufactured by Toray Fine Chemical Co., Ltd.), TSIC, TSIC-2, TS-G (manufactured by Shikoku Kasei Kogyo Co., Ltd.), Karenz MTPE1, MTBD1, MTNR1, TPMB, TEMB (Showa Denko shares Although Company, Ltd.) are not limited thereto. These compounds may be used alone or in combination of two or more.

About the compounding quantity of (D) component in the curable composition of this invention, although a range is not specifically limited, In the range of 0.01-200 mass parts with respect to a total of 100 mass parts of said (A) component. It is preferable that it is 0.1-100 mass parts. When (D) component is added within said range, the curable composition excellent in the balance of a cure rate and the intensity | strength of hardened | cured material, storage stability, etc. can be obtained.

<(E) component>
The component (E) in the curable composition of the present invention is a compound having one or more epoxy groups in the molecule. Such a compound is generally called an epoxy resin. Specific examples thereof include diglycidyl ether derived from bisphenol A and epichlorohydrin, and derivatives thereof, diglycidyl ether derived from bisphenol F and epichlorohydrin, and derivatives thereof. So-called epi-bis type liquid epoxy resin, glycidyl ether derived from aliphatic / aromatic alcohol and epichlorohydrin, glycidyl ester derived from polybasic acid and epichlorohydrin, and derivatives thereof, derived from hydrogenated bisphenol A and epichlorohydrin Glycidyl ether, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexyl) (Rumethyl) adipate and other aliphatic cyclic epoxies and derivatives thereof, 5,5′-dimethylhydantoin type epoxy resins, triglycidyl isocyanate, substituted epoxy derived from isobutylene, triazine skeleton-containing epoxy compounds, and the like. It is not limited.

The commercially available (E) component is, for example, Epicoat 828, 1001, 801, 806, 807, 152, 604, 630, 871, YX8000, YX8034, YX4000 (manufactured by Mitsubishi Chemical Corporation), Epicron 830, EXA-830LVP, EXA-850CRP, 835LV, HP4032D, 703, 720, 726, HP820 (manufactured by DIC Corporation), EP4100, EP4000, EP4080, EP4085, EP4088, EPU6, EPR4023, EPR1309, EP49-20 (manufactured by Asahi Denka Kogyo Co., Ltd.), Denacol EX614B, EX252, EX111, EX146, EX721, EX411, EX314, EX201, EX212 (manufactured by Nagase ChemteX Corporation), Bremer CP-15, CP-30, P-50M, Marproof G-1005S (manufactured by NOF Corporation), TEPIC, TEPIC-S, TEPIC-VL (manufactured by Nissan Chemical Industries, Ltd.), EG-200, PG-100 (manufactured by Osaka Gas Chemical Co., Ltd.) However, it is not limited to these. These may be used alone or in admixture of two or more.

These components (E) are used for adjusting the viscosity of the whole composition, improving workability, reducing the price, adjusting the refractive index, adjusting the reactivity, and the like. The compounding amount of the compound having an epoxy group in the molecule is not particularly limited. However, when the component (D) is added, it is desirable to adjust the compounding ratio in consideration of the epoxy equivalent to the thiol equivalent. .

<(F) component>
Furthermore, you may add the compound which has one or more radically polymerizable groups in a molecule | numerator as (F) component in this invention. The radical polymerizable group is a vinyl group, an allyl group, an acryloyl group, a methacryloyl group or the like, but a compound having one or more (meth) acryloyl groups in the molecule in the sense of being excellent in radical photopolymerizability by itself. desirable.

For example, 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, isooctyl (Meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, 2-ethoxyethyl (Meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) Chlorate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, 2,2,2, -trifluoroethyl (meth) acrylate, 2,2,3,3, -tetra Fluoropropyl (meth) acrylate, 1H, 1H, 5H, -octafluoropentyl (meth) acrylate, imide (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, propyl ( (Meth) acrylate, n-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isononyl (meth) acrylate , Isomyristyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, bicyclopentenyl (meth) acrylate, isodecyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (Meth) acrylate, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl 2-hydroxypropyl phthalate, glycidyl (meth) Acrylate, 2- (meth) acryloyloxyethyl phosphate, 1,4-butanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, dipropylene glycol di (Meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) ) Acrylate, propylene oxide-added bisphenol A di (meth) acrylate, bisphenol A di (meth) acrylate, ethylene oxide-added bisphenol A di (meth) acrylate, ethyleneoxy Addition bisphenol F di (meth) acrylate, dimethylol dicyclopentadiene di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide modified isocyanuric acid di (meth) acrylate 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, carbonate diol di (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, propylene oxide-added trimethylolpropane Tri (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, caprolactone-modified trimethylolpropane tri (meth) acrylate , Ethylene oxide-added isocyanuric acid tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, glycerin tri (Meth) acrylate, propylene oxide-added glycerin tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, urethane (meth) acrylate, and the like. Among these, from the viewpoint of compatibility with the component (A), propylene oxide-added bisphenol A di (meth) acrylate, bisphenol A di (meth) acrylate, bisphenol F di (meth) acrylate ethylene oxide-added bisphenol A di (meth) acrylate Ethylene oxide-added bisphenol F di (meth) acrylate and urethane (meth) acrylate are preferably used. Although the compounding quantity of (F) component is not restrict | limited in particular, it is preferable that it is 1-500 mass parts with respect to 100 mass parts of total amounts of (A) component of this invention.

By adding this component (F), this component is quickly polymerized by light irradiation to adjust the fluidity of the composition, to develop tackiness and temporary fixability, or to attach the adhesive to the member in advance. And can be used by a process such as later curing.

In the case of photocuring a thiirane resin and a compound having a radically polymerizable group in combination, a cation initiator is generally used to polymerize a thiirane group. In this case, a urethane is added to the composition. When a compound having a binding site is present, since the urethane site works as a cationic polymerization inhibitor, there has been a problem that an acrylate having a urethane binding site in the molecule, so-called urethane (meth) acrylate, cannot be used. This problem does not occur because the polymerization of thiirane proceeds with a base catalyst. Even if the compound has a urethane (meth) acrylate or isocyanuric ring that could not be used in the past, it should be used without any problem of inhibiting the polymerization of thiirane group. Can do.

To the curable composition of the present invention, a compound having both a thiirane group and an epoxy group in one molecule may be added as long as the characteristics of the present invention are not impaired. Such a compound can be obtained, for example, by adjusting the amount of episulfide reagent used or reaction conditions when an epoxy compound is used as a raw material to synthesize an episulfide resin by exchanging oxygen atoms in the epoxy ring with sulfur atoms. Can do. Alternatively, partial episulfides obtained by separation by various purification methods can be obtained by mixing with all episulfides.

Furthermore, you may add to this invention the compound which has the effect which suppresses arbitrary anionic polymerization in the range which does not impair the characteristic of this invention. This is added to increase the stability during storage of the composition. For example, liquid or solid organic acids and inorganic acids at room temperature, oligomers, polymers, boric acid esters, phosphoric acid esters having acidic groups in the molecule, and having functional groups other than acidic groups good. Examples include, but are not limited to, sulfuric acid, acetic acid, adipic acid, tartaric acid, fumaric acid, barbituric acid, boric acid, pyrogallol, phenolic resin, carboxylic acid anhydride and the like.

Boric acid esters are boric acid esters that are liquid or solid at room temperature. For example, trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, tri-n-butyl borate, tripentyl borate, triallyl borate, trihexyl borate, tricyclohexyl borate, trioctyl borate, trinonyl borate, trinonyl borate Decyl borate, tridodecyl borate, trihexadecyl borate, trioctadecyl borate, tris (2-ethylhexyloxy) borane, bis (1,4,7,10-tetraoxaundecyl) (1,4,7,10, 13-pentaoxatetradecyl) (1,4,7-trioxaundecyl) borane, tribenzyl borate, triphenyl borate, tri-o-tolyl borate, tri-m-tolyl borate, triethanolamine borate, etc. But it is under but is not limited to this.

Examples of phosphoric acid esters include ethyl phosphate, butyl phosphate, propyl phosphate, 2-ethylhexyl phosphate, dibutyl phosphate, di- (2-ethylhexyl) phosphate, oleyl phosphate, and ethyl diethyl phosphate. However, it is not limited to this.

These acidic substances (acidic group-containing compound, boric acid ester, phosphoric acid ester) have an effect of improving the storage stability of the resin composition of the present invention before irradiation with energy rays. These compounds may be used alone or in combination of two or more. Moreover, you may add what mixed these compounds, an epoxy resin, etc. and made it a masterbatch. Examples of such products that are commercially available as storage stability improvers include Cure Duct L-07N manufactured by Shikoku Kasei Kogyo Co., Ltd., but are not limited thereto. The amount of these compounds is not particularly limited.

Furthermore, the curable composition of the present invention includes colorants such as pigments and dyes, inorganic fillers such as calcium carbonate, talc, silica, alumina and aluminum hydroxide, and conductive materials such as silver as long as the characteristics of the present invention are not impaired. Particles, flame retardants, organic fillers such as acrylic rubber and silicone rubber, polyimide resin, polyamide resin, bisphenol A type phenoxy resin, bisphenol F type phenoxy resin, bisphenol A / bisphenol F copolymer type phenoxy resin, etc. , Isocyanates, cyanate esters, polymethacrylate resins, polyacrylate resins, maleimide resins, polyimide resins, polyurethane resins, polyester resins, polyvinyl butyral resins, SBS resins and their modified epoxy resins, SEBS resins And Polymers and thermoplastic elastomers such as modified products, plasticizers, organic solvents, antioxidants, antifoaming agents, coupling agents, leveling agents, may be appropriate amount of additives such as rheology control agents. By these additions, a curable composition having excellent resin strength, adhesive strength, flame retardancy, thermal conductivity, workability, and the like and a cured product thereof can be obtained.

As a method for curing the resin composition of the present invention, a cured product can be obtained in a shorter amount of energy irradiation and in a shorter time by performing energy beam irradiation and heating simultaneously. Further, a cured product can be obtained in a short time by heating after irradiation with energy rays. Examples of active energy rays in this case include electron beams and visible rays, but are not particularly limited. The irradiation amount of the active energy ray is preferably 0.1 J / cm ² or more, and the wavelength of the active energy ray is preferably 150 to 830 nm. As heating conditions, 50-200 degreeC is preferable, More preferably, it is 70-150 degreeC.

Although it does not specifically limit as a light source for irradiating the active energy ray in this invention, For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, an excimer laser, a black light lamp, a metal halide lamp, a sodium lamp, a xenon lamp , Sunlight, LED light source, electron beam irradiation device and the like. These light sources may be used independently and 2 or more types may be used together.
The LED light source emits only long-wavelength active energy rays that do not include short-wavelength active energy rays, and is preferably used as an irradiation device from the viewpoint of being small and consuming little power. Moreover, since the curable composition of this invention can be hardened | cured only with a long wavelength active energy ray, it is optimal for hardening by LED irradiation.

Further, in the curable composition in the present invention, it can be cured immediately after irradiation with active energy rays, or it can be cured immediately after irradiation with active energy rays, and then can be cured by standing at room temperature or heating for a short time. The latter property is possible even when the adhesive member does not transmit active energy rays such as light, and can be adhered by applying and pasting the curable composition after irradiating the active energy rays.

As a method of bonding using the curable composition of the present invention, since the curable composition of the present invention exhibits delayed curing, for example, after applying the curable composition of the present invention to one substrate. A method having a step of irradiating active energy rays and a step of curing at normal temperature or after heating the other base material can be used. Such an adhesion method can be suitably used even for a member that does not transmit active energy, for example. Furthermore, after bonding, the position can be adjusted before being cured, or it can be cured while being pressed, so that the dimensional accuracy can be improved.

In the present invention, the expression “curability” is frequently used, but it means that it is cured for a short time mainly by heating or room temperature after irradiation with active energy rays.

The cured product of the curable composition of the present invention has excellent properties such as toughness and high adhesive strength, and can be used for various applications such as bonding, sealing, casting, coating, coating materials, and molding of optical components. It is. Specifically, in the field of automobiles and transportation equipment, bonding, sealing, casting, molding, coating materials for automotive switch parts, headlamps, engine internal parts, electrical components, drive engines, brake oil tanks, etc. Etc. can be used. Further, the flat panel display can be used for adhesion, sealing, casting, molding, coating material, etc. of liquid crystal displays, organic electroluminescence, light emitting diode display devices, and field emission displays. In the recording field, for video discs, CDs, DVDs, MDs, pickup lenses, hard disk peripherals (spindle motor members, magnetic head actuator members, etc.), Blu-ray discs, etc., sealing, casting, molding, coating materials, etc. Can be used. In the field of electronic materials, sealing materials for electronic components, electrical circuits, electrical contacts or semiconductor elements, die bonding agents, conductive adhesives, anisotropic conductive adhesives, interlayer adhesives for multilayer substrates including build-up substrates, A solder resist etc. can be mentioned. In the battery field, Li batteries, manganese batteries, alkaline batteries, nickel batteries, fuel cells, silicon solar cells, dye-sensitized solar cells, organic solar cells, etc., sealing, casting, molding, coating materials, etc. Can be used. In the field of optical components, for optical switch peripherals, optical connector peripherals, optical passive components, optical circuit components, optoelectronic integrated circuit peripherals, etc. in optical communication systems, adhesives, sealing, casting, molding, coating materials, etc. Can be used. In the optical equipment field, it is used for bonding, sealing, casting, molding, coating materials, etc. for lens materials for steel cameras, finder prisms, target prisms, finder covers, light-receiving sensor parts, photographic lenses, projection lenses for projection televisions, etc. Is possible. In addition, a motor, a relay, etc. are mentioned.

Further, the curable composition of the present invention has a gap provided between the protective part such as glass and the image display part in an image display device such as a liquid crystal or a touch panel. Also good.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited by the following examples. Moreover, the mixture ratio in the following table | surface is a mass reference | standard.

<Examples 1 to 40 and Comparative Examples 1 to 7>
The following components were prepared to prepare a curable composition.

The materials used in the examples and comparative examples of the present invention are the following commercially available products or reagents.
<(A) component>
YL7007: (Mitsubishi Chemical Corporation) 100% episulfide product of hydrogenated bisphenol A epoxy resin YL7000: (Mitsubishi Chemical Corporation) 100% episulfide product of bisphenol A type epoxy resin Episulfide compound A: ( (Mitsubishi Chemical Corporation) Hydrogenated bisphenol A type epoxy resin 80% episulfide product / Episulfide compound B: (Mitsubishi Chemical Corporation) Hydrogenated bisphenol A type epoxy resin 50% episulfide product <(B) component>
・ TPP-MK: Tetraphenylphosphonium ・ Tetra-p-tolylborate (manufactured by Hokuko Chemical Co., Ltd.)
TPTP-MK: p-tolyltriphenylphosphonium tetra-p-tolylborate (made by Hokuko Chemical Co., Ltd.)
TPPZ-K: benzyltriphenylphosphonium tetraphenylborate (made by Hokuko Chemical Co., Ltd.)
N3B: tetrabutylammonium-butyltri-1-naphthalenylborate (manufactured by Showa Denko)
PBG-SA1: 1,8-diazabicyclo [5.4.0] undec-7-ene structure-containing compound and phenyl borate compound UCAT-5002: 1,8-diazabicyclo [5.4.0] undeca 7-ene structure-containing compound and tetraphenylborate salt (manufactured by San Apro Co., Ltd.)
NaBPh ₄ : tetraphenylborate sodium salt (manufactured by Dojindo Laboratories, Inc., Reagents)
NBu ₄ BPh ₄ : tetrabutylammonium tetraphenylborate (reagent manufactured by Aldrich)
DBN-K: 1,5-diazabicyclo [4.3.0] non-5-ene-tetraphenylborate (made by Hokuko Chemical Co., Ltd.)
EMZ-K: 2-ethyl-4-methylimidazolium tetraphenylborate (made by Hokuko Chemical Co., Ltd.)
・ P3B: Tetrabutylammonium-butyltriphenylborate (Showa Denko)
<Comparison component of component (B)>
DBU: 1,8-diazabicyclo [5.4.0] undec-7-ene (manufactured by San Apro Co., Ltd.)
・ PK: pyridine triphenyl borate (made by Hokuko Chemical Co., Ltd.)
NBC-101: N- (2-methyl-2-phenylpropionyloxy) -N-cyclohexylamine (Midori Chemical Co., Ltd. photobase generator)
<(C) component>
・ 9-Fluorenone (Reagent manufactured by Tokyo Chemical Industry Co., Ltd.)
・ KAYACURE DETX-S: 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd.)
・ KAYACURE ITX: 2-isopropylthioxanthone (manufactured by Nippon Kayaku Co., Ltd.)
・ Benzophenone (Reagent manufactured by Tokyo Chemical Industry Co., Ltd.)
・ 4-Methylbenzophenone (Reagent manufactured by Tokyo Chemical Industry Co., Ltd.)
SPEEDCURE PBZ: 4-Phenylbenzophenone (LAMBSON)
SPEEDCURE BMS: 4- (4-methylphenylthio) benzophenone (manufactured by LAMBSON)
・ Fluoranthene (Reagent manufactured by Tokyo Chemical Industry Co., Ltd.)
DAROCUR MBF: methyl benzoylformate (BASF)
IRGACURE 184: 1-hydroxycyclohexyl phenyl ketone (manufactured by BASF)
IRGACURE 651: 2,2-dimethoxy-1,2-diphenylethane-1-one (manufactured by BASF)
IRGACURE907: 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (manufactured by BASF)
IRGACURE 819: bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (manufactured by BASF)
・ 2-Ethyl anthraquinone (Reagent manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Benzyl (Reagent manufactured by Tokyo Chemical Industry Co., Ltd.)
<(D) component>
・ 1-Dodecanethiol (Reagent manufactured by Tokyo Chemical Industry Co., Ltd.)
PEMP: pentaerythritol tetrakis (3-mercaptopropionate) (Aldrich reagent)
・ 1,4-benzenedimethanethiol (Reagent manufactured by Tokyo Chemical Industry Co., Ltd.)
<(E) component>
・ EXA-835LV: Bisphenol type epoxy resin (manufactured by DIC Corporation)
YX8000: Hydrogenated bisphenol A type epoxy resin (Mitsubishi Chemical Corporation)
<(F) component>
FA-321A: Ethylene oxide modified bisphenol A diacrylate (manufactured by Hitachi Chemical Co., Ltd.)
<Other ingredients>
・ Γ-Butyrolactone (Reagent manufactured by Wako Pure Chemical Industries, Ltd.)
KBM403: Glycidyl group-containing silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd.)
・ L07N: Boric acid ester compound (manufactured by Shikoku Chemicals Co., Ltd.)
R805: fumed silica having an average particle size of 14 nm and surface-treated with alkylsilane (manufactured by Degussa)

[Preparation of compositions of Examples 19 to 23, 33]
(B) component of the mass proportion shown in Tables 3 and 4 is mixed with 5 parts by mass of methyl ethyl ketone of component (B), stirred and dissolved at room temperature, and then the component (A) of mass proportion shown in Table 1 Are mixed at room temperature until uniform, and then stirred at room temperature under reduced pressure to remove methylethylton to prepare a uniform composition in which component (B) is dissolved in component (A). Were added and stirred and mixed at room temperature to prepare a curable composition.

[Preparation of Examples 1-18, Examples 24-32, Examples 34-40 and Comparative Examples 1-4, 6, 7]
After the components (B) and (C) are added to γ-butyrolactone and dissolved by stirring at room temperature in the mass ratios shown in Tables 1 to 4, other components are added and stirred and mixed at room temperature to cure. A sex composition was prepared.

<Characteristic evaluation>
Various characteristics were measured as follows.

<Curing test only by UV irradiation>
A test piece is prepared by dropping 0.01 g of the curable composition onto a slide glass and covering the glass with a cover glass so that the curable composition is sandwiched between the glass as a thin film. The test piece was placed on a hot plate set at 120 ° C. and left in a dark place where light was shielded, and the time until the resin hardened and the glass adhered to each other and could not be moved by hand was measured every 30 minutes. When the resin was uncured even after 3 hours, it was listed in the table as “uncured”. The results are shown in Tables 1-4.

<Curability test by UV irradiation and heating>
A test piece is prepared by dropping 0.01 g of the curable composition onto a slide glass and covering the glass with a cover glass so that the curable composition is sandwiched between the glass as a thin film. Immediately after irradiating an active energy ray with a 365 nm illuminance of 100 mW / cm ² for 30 seconds (3 J / cm ² when converted to integrated light amount) using a spot ultraviolet irradiation device (use lamp: L8252) manufactured by Hamamatsu Photonics Co., Ltd. A test piece was placed on a hot plate set at 120 ° C., and the time during which the glasses were bonded to each other and could not be moved by hand was measured as the curing time. The measurement interval is 1 second for 1 to 30 seconds, 10 seconds for 30 to 300 seconds, 1 minute for 5 to 20 minutes, and every 10 minutes for 20 minutes and thereafter, up to 3 hours. Measurements were made. The results are shown in Tables 1-4. In Examples 1 to 40 which are curable compositions of the present invention, curing was not confirmed only by heating at 120 ° C. for 3 hours, but curing was accelerated by ultraviolet irradiation, and curing at 120 ° C. was confirmed. .

<Room temperature storage stability confirmation test>
After each curable composition was stored in a light-shielding container for 30 days in a 25 ° C. room, the curable composition was a liquid that did not gel, and “◎”, and the curable composition was a gel Was evaluated as “×”. The results are shown in Tables 1-4.

The curable composition containing the components (A) to (C) of the present invention from Examples 1 to 3 in Table 1 is cured more rapidly than Comparative Examples 1 to 3 which are (C) component-free compositions. It can be seen that it has good storage stability at room temperature.

From Comparative Examples 4 to 6 in Table 1, in the case of only component (A) and in place of component (B), it has a structure similar to component (B), but does not have the characteristic borate salt structure of the present invention. It can be seen that when the compound is used, the storage stability is remarkably poor, or the curing is not accelerated by irradiation with light and does not show good curability. From Comparative Example 7, it can be seen that when a photobase generator not corresponding to the component (B) of the present invention is used, the curability is poor even when the component (C) is used in combination.

Moreover, from Examples 4 to 13, the curing time of the curable composition can be adjusted by adjusting the type and addition amount of the component (B) while keeping the curing conditions (UV irradiation amount, curing temperature) constant. I understand.

It turns out that the curing time of a curable composition can be adjusted by adjusting the kind and addition amount of (B) component and (C) component from Examples 14-23 of Table 3.

From Examples 29 to 36 in Table 4, it can be seen that any component (A) can be used. From Examples 30-38, it turns out that hardening time can be adjusted by addition of (D) component. Examples 37 and 38 show that component (E) can be added. Example 39 shows that component (F) can be added. From Example 40, even when other compounding components such as an anionic polymerization inhibitor, a coupling agent, and a filler are added to the curable composition of the present invention, irradiation with active energy rays results in room temperature or a low heating temperature. It can be seen that it can be cured quickly and has good storage stability at room temperature.

-Preparation of Comparative Example 8 100 parts by mass of YL7007 corresponding to component (A) of the present invention and PBG-SA1BU (1,8-diazabicyclo [5.4.0] undeca-corresponding to component (B) of the present invention Comparative Example 8 was obtained by adding 0.7 parts by mass of a 7-ene structure-containing compound and a salt of a phenylborate compound) and stirring and mixing at room temperature.

<Curability confirmation test under UV irradiation conditions and curing temperature conditions>
Using the curable compositions of Example 5 and Comparative Example 8, the curing time when the UV integrated light amount and the curing temperature were changed was measured. The measurement was performed in the same manner as described above [120 ° C. curing time after UV 3 J / cm ² irradiation], and the amount of accumulated light was changed as shown in Table 5 by changing the UV irradiation time, and the curing time was confirmed. . Further, the temperature of the hot plate was changed to the temperature shown in Table 5. In Table 5, when the curing time is 0 second, the resin is cured simultaneously with the end of the ultraviolet irradiation.

In Example 5, which is the curable composition of the present invention of Table 5, it can be seen that the curing time can be freely adjusted by changing the irradiation conditions or the curing temperature of the ultraviolet rays while being the same curable composition. It can be seen that, depending on the irradiation conditions, the subsequent curing time is not required, and the curable composition can be cured simultaneously with the end of the ultraviolet irradiation. Moreover, it turns out that it can harden | cure also by leaving to stand at room temperature (23 degreeC), without heating especially after ultraviolet irradiation. Moreover, Example 5 which is a curable composition of this invention shows that sclerosis | hardenability is high on any conditions rather than the curable composition of the comparative example 8. FIG.

<Curability confirmation test using LED light source>
The curable composition 0.01g of Examples 20-22 and 33 is dripped on a slide glass, a cover glass is covered, and the test piece by which the curable composition was pinched | interposed into glass as a thin film is created. This is irradiated with an active energy ray of 365 nm illuminance of 200 mW / cm ² for 30 seconds using a UV-LED irradiator ZUV-C30H (head unit: ZUV-H20MB) manufactured by OMRON Corporation (when converted to an integrated light amount, 6 J / cm ² ), The test piece was immediately placed on a hot plate set at 120 ° C., and the time during which the glass adhered to each other and could not be moved by hand was measured every second, and was set as the curing time.

From Table 6, the curable composition of the present invention emits a long-wavelength active energy ray that does not include a short-wavelength active energy ray, such as an active energy ray irradiated from a general high-pressure mercury lamp, and is small in size and consumes power. It can be seen that even when an LED light source with a small amount of light is used as an irradiation device, it can be cured quickly after irradiation conditions of ultraviolet rays.

The present invention relates to a curable composition that can be cured for a short time after irradiation with active energy rays by heating or room temperature, and a curing method and a cured product thereof, particularly potting, molding, coating, adhesive, sealing agent, and It can be widely applied to photolithography, photoprinting, various resist materials, and the like.

Claims (9)

A curable composition comprising the following components (A) to (C):
(A) Component: Compound having two or more thiirane rings in the molecule (B) Component: Photobase generator containing a salt having an anion represented by the following general formula (1)
(Wherein R ^{1 to} R ⁴ each represent a hydrogen atom, a halogen atom, a substituted or unsubstituted aromatic group, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and are the same as each other) May be different.)
(C) component: sensitizer The curability according to claim 1, wherein the component (A) is a compound having a thiirane ring in which all or part of oxygen atoms of the oxirane ring of the epoxy compound having a bisphenol skeleton is substituted with a sulfur atom. Composition. Furthermore, the compound which has a 1 or more thiol group in a molecule | numerator as (D) component is contained, The curable composition of any one of Claim 1 or 2 characterized by the above-mentioned. The curable composition according to any one of claims 1 to 3, wherein the component (B) is a salt represented by the following general formula (2) or general formula (3).
Wherein R ^{5 to} R ⁸ are each a hydrogen atom, a halogen atom or a hydroxy group, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, carbon Aryl group having 6 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, ester group, carboxyl group, aldehyde group, amino group, imino group, imide group, nitrile group, amide group, imide group, cyano group, sulfonyl acid group , A sulfonyl group, a nitro group, a sulfide group, a thiol group, and an isocyanate group, each independently or a combination of plural groups, a and b each independently represent an integer of 0 to 4. Z ⁺ is a quaternary ammonium. Represents a cation, an alkali metal cation, or a phosphonium cation.)
(Wherein R ^{9 to} R ¹¹ represent a substituted or unsubstituted aromatic group, R ¹² represents an alkyl group of 1 to 20, and Z ⁺ represents a quaternary ammonium cation, an alkali metal cation, and a phosphonium cation. Represents.) The quaternary ammonium cation of Z ⁺ is 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] non-5-ene, triazabicyclodecene. , Hexahydromethylpyrimidopyrimidine, or tetra-n-butylammonium, which is selected from the group consisting of one or more cations in the molecule, and the alkali metal cation of Z ⁺ is sodium cation, potassium cation or lithium cation. The curable composition according to claim 4, wherein the phosphonium cation of Z ⁺ is a compound represented by the following general formula (4).
(Wherein R ^{13 to} R ¹⁶ each represent a hydrogen atom, a halogen atom, a substituted or unsubstituted aromatic group, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and are the same as each other) May be different.) Compound (C) selected from the group consisting of compounds represented by general formulas (5) to (8); or benzyl ketal photoradical polymerization initiator, α-hydroxyacetophenone photoradical polymerization initiation Agent, benzoin photo radical polymerization initiator, aminoacetophenone photo initiator, oxime ketone photo radical polymerization initiator, acylphosphine oxide photo radical polymerization initiator, benzophenone compound, thioxanthone compound, anthraquinone compound, general formula A radical polymerization initiator selected from the group consisting of (9); or a nitro compound selected from the group consisting of nitrobenzoic acid and nitroaniline; or an aromatic hydrocarbon selected from the group consisting of naphthalene derivatives and anthracene derivatives Or riboflavin, rose bengal, eosin Erishisuroshin, methylene blue or curable composition according to any one of claims 1 to 5, characterized in that it is selected from a dye selected from the group consisting of New Methylene Blue Rose.
Wherein R ¹⁷ and R ¹⁸ are each a hydrogen atom, a halogen atom or a hydroxy group, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, carbon Formula 6-20 aryl group, alkoxy group, ester group, carboxyl group, aldehyde group, amino group, imino group, imide group, nitrile group, amide group, imide group, cyano group, sulfonyl group, sulfonyl group, nitro group , A sulfide group, a thiol group, an isocyanate group, or a group obtained by arbitrarily combining a plurality of groups, a and b each independently represent an integer of 0 to 4.)
(Wherein n represents an integer of 1 to 12, R ¹⁹ and R ²⁰ are each a hydrogen atom, a halogen atom or a hydroxy group, a linear or branched alkyl group having 1 to 20 carbon atoms, carbon C3-C20 cycloalkyl group, C6-C20 aryl group, alkoxy group, ester group, carboxyl group, aldehyde group, amino group, imino group, imide group, nitrile group, amide group, imide group, cyano group A sulfonyl group, a sulfonyl group, a nitro group, a sulfide group, a thiol group, and an isocyanate group, each independently or a combination of a plurality of groups, and a and b each independently represent an integer of 0 to 4.)
(In the formula, R ²¹ and R ²² are each a hydrogen atom, a halogen atom or a hydroxy group, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and carbon. Formula 6-20 aryl group, alkoxy group, ester group, carboxyl group, aldehyde group, amino group, imino group, imide group, nitrile group, amide group, imide group, cyano group, sulfonyl group, sulfonyl group, nitro group , A sulfide group, a thiol group, an isocyanate group, or a group obtained by arbitrarily combining a plurality of groups, a and b each independently represent an integer of 0 to 4.)
Wherein R ^{23 to} R ²⁵ are each a hydrogen atom, a halogen atom or a hydroxy group, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, carbon Formula 6-20 aryl group, alkoxy group, ester group, carboxyl group, aldehyde group, amino group, imino group, imide group, nitrile group, amide group, imide group, cyano group, sulfonyl group, sulfonyl group, nitro group , A sulfide group, a thiol group, an isocyanate group, or a group obtained by arbitrarily combining a plurality of groups, a to c each independently represent an integer of 0 to 4.)
Wherein R ²⁶ and R ²⁷ are each a hydrogen atom, a halogen atom or a hydroxy group, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, carbon Formula 6-20 aryl group, alkoxy group, ester group, carboxyl group, aldehyde group, amino group, imino group, imide group, nitrile group, amide group, imide group, cyano group, sulfonyl group, sulfonyl group, nitro group , A sulfide group, a thiol group, an isocyanate group, or a group obtained by arbitrarily combining a plurality thereof, and a independently represents an integer of 0 to 4.) Furthermore, the (E) component contains the compound which has one or more epoxy groups in a molecule | numerator, The curable composition of any one of Claims 1-6 characterized by the above-mentioned. Furthermore, the compound which has one or more radically polymerizable groups in a molecule | numerator as (F) component is contained, The curable composition of any one of Claims 1-7 characterized by the above-mentioned. After irradiating the curable composition according to any one of claims 1 to 8 with an active energy ray having a wavelength of 150 to 830 nm, the curable composition is cured at room temperature or in a heating environment. Curing method.