JP2023055437A - Curable resin composition and cured product thereof - Google Patents

Abstract

To provide a curable resin composition whose cured product has excellent ultraviolet permeability and achieves high light resistance to ultraviolet rays and high heat resistance, and to provide a cured product thereof.SOLUTION: The curable resin composition contains the following compound (A), the following compound (B), the following compound (C), a photoradical generator (D), and a photoacid generator (E). Compound (A): an acrylate compound having two or more acryloyl groups in one molecule. Compound (B): a methacrylate compound having one or more oxirane rings and one methacryloyl group in one molecule. Compound (C): a thiol group-containing compound having two or more thiol groups in one molecule.SELECTED DRAWING: None

Description

The present disclosure relates to a curable resin composition and a cured product thereof.

A micro LED display, which is drawing attention as a next-generation display, is a display in which fine red, green, and blue light-emitting LED elements are laid out on a substrate. , an ultraviolet curable resin composition is used (for example, Patent Document 1).

Recently, for micro LED displays, instead of light sources emitting light such as blue light, use of ultraviolet LED elements as light sources to achieve higher luminance is being studied.

Therefore, the encapsulant and the adhesive layer are required to have excellent ultraviolet transmittance and high resistance to ultraviolet rays. In addition, high heat resistance is required because an ultraviolet LED element is used as a light source. Curing containing a combination of a bifunctional acrylic compound having two (meth)acryloyl groups in one molecule and a polyfunctional acrylic compound having three or four (meth)acryloyl groups in one molecule of Patent Document 1 It is described that the cured product of the flexible resin composition is excellent in total light transmittance.

JP 2019-210481 A

However, the cured product described in Patent Document 1 did not exhibit sufficient performance in terms of light resistance to ultraviolet light and heat resistance.

In addition, when the display member and the cover member are attached together, it is required that there is enough time before the curing is completed in order to allow adjustment of the misalignment.

Therefore, the object of the present disclosure is a curable resin composition that provides a cured product with sufficient time to complete curing, excellent operability, excellent UV transparency, and high UV light resistance and heat resistance. It is to provide a product and its cured product.

The inventors of the present disclosure have made intensive studies to achieve the above object, and found that a specific curable resin composition containing an acrylate compound, a methacrylate compound having an oxirane ring, and a thiol group-containing compound has high ultraviolet transmittance, It was found that a cured product that achieves high ultraviolet light resistance and heat resistance can be obtained.

That is, the present disclosure includes a curable resin containing the following compound (A), the following compound (B), the following compound (C), a photoradical generator (D), and a photoacid generator (E) A composition is provided.
Compound (A): Acrylate compound having two or more acryloyl groups in one molecule Compound (B): Methacrylate compound having one or more oxirane rings and one methacryloyl group in one molecule Compound (C): 1 Thiol group-containing compound having two or more thiol groups in the molecule

［式（１）中、Ｒ¹はｍ価の炭化水素基、複素環基又はこれらが単結合若しくは連結基を介して結合した基を表し、ｍは２～５の整数を示す。］ Compound (A) is preferably a compound represented by the following formula (1).

[In formula (1), R ¹ represents an m-valent hydrocarbon group, a heterocyclic group, or a group in which these are bonded via a single bond or a linking group, and m represents an integer of 2-5. ]

［式（２）中、Ｘはオキシラニル基又はエポキシシクロヘキシル基を表し、Ｒ²は２価の炭化水素基を表す。］ Compound (B) is preferably a compound represented by the following formula (2).

[In formula (2), X represents an oxiranyl group or an epoxycyclohexyl group, and R ² represents a divalent hydrocarbon group. ]

［式（３）中、Ｒ³はｎ価の炭化水素基、複素環基又はこれらが単結合若しくは連結基を介して結合した基を表し、Ｙは単結合又は連結基を表し、ｎは２～５の整数を示す。］ Compound (C) is preferably a compound represented by the following formula (3).

[In formula (3), R ³ represents an n-valent hydrocarbon group, a heterocyclic group, or a group in which these are bonded via a single bond or a linking group, Y represents a single bond or a linking group, and n is 2 Indicates an integer from ~5. ]

The present disclosure also provides a sealant comprising the curable resin composition.

The present disclosure also provides an adhesive comprising the curable resin composition.

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

The present disclosure also provides a display member comprising the cured product.

The curable resin composition of the present disclosure has a sufficient time to complete curing, is excellent in operability, and can form a cured product that achieves high ultraviolet transmittance and high ultraviolet light resistance and heat resistance. It can be suitably used as a material for display members.

Although the reason why the curable resin composition of the present disclosure is likely to have sufficient time to complete curing is not clear, it is presumed as follows. That is, the compound (A) having an acryloyl group has higher radical polymerizability of the double bond portion than the compound (B) having a methacryloyl group, and the compounds (A) are preferentially added to each other. A block composed of a structural unit derived from compound (A) is interposed between the derived structural units, and the oxirane ring derived from compound (B) tends to be at a distant position. In the present disclosure, since the photoacid generator is used instead of the photobase generator, the reaction between the oxirane ring and the thiol group derived from the compound (C) due to the photobase generator is unlikely to occur, and the oxirane Since the rings are separated from each other, gelling due to promotion of the reaction between the oxirane rings by the photoacid generator is less likely to occur, and it becomes easier to obtain sufficient time until curing is completed.

[Curable resin composition]
The curable resin composition of the present disclosure includes the following compound (A), the following compound (B), the following compound (C), a photoradical generator (D), and a photoacid generator (E). .
Compound (A): Acrylate compound having two or more acryloyl groups in one molecule Compound (B): Methacrylate compound having one or more oxirane rings and one methacryloyl group in one molecule Compound (C): 1 Thiol group-containing compound having two or more thiol groups in the molecule

<Compound (A)>
Compound (A) is an acrylate compound having two or more acryloyl groups in one molecule.

Compound (A) is preferably a compound represented by the following formula (1). In formula (1) below, R ¹ represents an m-valent hydrocarbon group, a heterocyclic group, or a group in which these are bonded via a single bond or a linking group, and m is an integer of 2-5.

m is preferably 2-3.

Examples of the m-valent hydrocarbon group for R ¹ include groups obtained by removing m hydrogen atoms from the structural formula of hydrocarbons (aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, etc.). .

Examples of the aliphatic hydrocarbon include linear or branched alkanes having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms) (methane, ethane, propane, Butane, 2-methylpropane, pentane, 2-methylbutane, 2,2-dimethylpropane, hexane, decane, dodecane, etc.), 2 to 20 carbon atoms (preferably 2 to 10 carbon atoms, more preferably 2 to 3 carbon atoms) ) linear or branched alkenes (ethylene, propene, 2-methylpropene, 1-butene, 2-butene, 1-pentene, 2-pentene, 1-hexene, etc.), carbon atoms 2 to 20 (preferably is a linear or branched alkyne (ethyne, propyne, etc.) having 2 to 10 carbon atoms, more preferably 2 to 3 carbon atoms.

The above alicyclic hydrocarbons include cycloalkanes having 3 to 20 carbon atoms (preferably 3 to 15 carbon atoms, more preferably 5 to 8 carbon atoms) (cyclopropane, cyclobutane, cyclopentane, cyclohexane, cyclooctane, etc.) , cycloalkenes (cyclopentene, cyclohexene, etc.) having 3 to 20 carbon atoms (preferably 3 to 15 carbon atoms, more preferably 5 to 8 carbon atoms), bridged cyclic hydrocarbons (bicycloheptane, bicycloheptene, perhydro naphthalene, norbornene, adamantane, tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodecane, etc.).

Examples of the monovalent aromatic hydrocarbons include aromatic hydrocarbons having 6 to 14 carbon atoms (preferably 6 to 10 carbon atoms) (benzene, naphthalene, etc.).

The above hydrocarbons have various substituents [e.g., halogen atoms, oxo groups, hydroxyl groups, substituted oxy groups (e.g., alkoxy groups, aryloxy groups, aralkyloxy groups, acyloxy groups, etc.), carboxyl groups, substituted oxycarbonyl groups, (alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, etc.), substituted or unsubstituted carbamoyl group, cyano group, nitro group, substituted or unsubstituted amino group, sulfo group, heterocyclic group, etc.] may The hydroxyl group and carboxyl group may be protected with a protective group commonly used in the field of organic synthesis. Also, an aromatic or non-aromatic heterocyclic ring may be condensed with the ring of the alicyclic hydrocarbon or aromatic hydrocarbon.

Examples of the m-valent heterocyclic group include groups obtained by removing m hydrogen atoms from the heterocyclic structural formula. Examples of the heterocyclic ring include heterocyclic rings containing an oxygen atom as a heteroatom (e.g., 4-membered ring (oxetane, etc.), 5-membered ring (furan, tetrahydrofuran, oxazole, isoxazole, γ-butyrolactone, etc.), 6-membered ring (4-oxo-4H-pyran, tetrahydropyran, morpholine, etc.), condensed rings (benzofuran, isobenzofuran, 4-oxo-4H-chromene, chroman, isochroman, etc.), bridged rings (3-oxatricyclo[4. 3.1.1 ^4,8 ]undecane-2-one), 3-oxatricyclo[4.2.1.0 ^4,8 ]nonan-2-one, etc.), heterocycles containing a sulfur atom as a heteroatom (e.g., 5-membered ring (thiophene, thiazole, isothiazole, thiadiazole ring, etc.), 6-membered ring (4-oxo-4H-thiopyran, etc.), condensed ring (benzothiophene, etc.), heterocyclic ring containing nitrogen atom as heteroatom (e.g., 5-membered rings (pyrrole, pyrrolidine, pyrazole, imidazole, triazole, etc.), 6-membered rings (pyridine, pyridazine, pyrimidine, pyrazine, piperidine, piperazine, etc.), condensed rings (indole, indoline, quinoline, acridine, naphthyridine, quinazoline, purine, etc.), a heterocyclic ring containing an oxygen atom and a nitrogen atom as a heteroatom (e.g., a nurate ring, etc.), etc. The heterocyclic ring is a substituent that the hydrocarbon may have. In addition, it may have a C 1-4 alkyl group (methyl group, ethyl group, etc.), a cycloalkyl group, an aryl group (phenyl group, naphthyl group, etc.) and the like.

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

The m-valent hydrocarbon group or heterocyclic group for R ¹ may be a residue obtained by removing the hydroxyl group from the corresponding polyol compound. Examples of the polyol compound include alkanediols (ethylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, etc.), glycerin, trialkylolalkanes (trimethylolpropane, triethylolpropane, die tyrol methylolbutane, etc.), pentaerythritol, bisphenols (bisphenol A, etc.) alkylene oxide adducts, isocyanuric acid alkylene oxide adducts, and the like.

The hydrocarbon related to R ¹ above is preferably an aliphatic hydrocarbon, and is linear or branched having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms). alkanes (saturated hydrocarbons) are more preferred. That is, R ¹ is preferably an m-valent hydrocarbon group, more preferably an m-valent carbon atom having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms). A hydrogen group, more preferably an m-valent saturated aliphatic hydrocarbon group having 1 to 5 carbon atoms, particularly preferably an m-valent straight-chain saturated aliphatic hydrocarbon group having 1 to 5 carbon atoms. Among them, a nurate ring is preferable as the heterocyclic ring for R ¹ .

R ¹ is preferably a residue obtained by removing a hydroxyl group from an alkanediol (1,4-butanediol, 1,6-hexanediol, etc.). Among the m-valent heterocyclic groups represented by R ¹ , residues of alkylene oxide isocyanuric acid adducts are preferred, and residues of tris-(2-hydroxyethyl)isocyanurate are more preferred.

Compound (A) is, for example, a reaction product in which some or all of the hydroxyl groups of the polyol compound and carboxyl groups of acrylic acid are ester-bonded, and two or more (preferably 2 to 5, more preferably 2 to 3, more preferably 2) acryloyl groups.

Examples of the compound (A) having two acryloyl groups include polyalkylene glycol diacrylate, bisphenol A alkylene oxide-modified diacrylate, alkanediol diacrylate, tricyclodecanedimethanol diacrylate, pentaerythrol diacrylate, glycerin diacrylate, acrylates and the like. These can be used individually by 1 type or in combination of 2 or more types.

Examples of the polyalkylene glycol diacrylate include polyethylene glycol diacrylate, polypropylene glycol diacrylate, polytetramethylene glycol diacrylate, and the like.

Examples of the bisphenol A alkylene oxide-modified diacrylate include bisphenol A ethylene oxide-modified diacrylate and bisphenol A propylene oxide-modified diacrylate.

The alkanediol diacrylate is preferably an alkanediol diacrylate having an alkylene group having 2 to 10 carbon atoms (more preferably 3 to 6 carbon atoms), and specific examples include ethylene glycol diacrylate, 1,4- butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate and the like.

Among these, alkanediol diacrylate is preferable from the viewpoint of suppressing gelation of the curable resin composition and improving the transparency of the cured product, and 1,4-butanediol from the viewpoint of ultraviolet light resistance of the cured product. A diacrylate, 1,6-hexanediol diacrylate, is more preferred.

Examples of the compound (A) having three acryloyl groups include pentaerythrol triacrylate, trimethylolpropane triacrylate, isocyanuric acid alkylene oxide-modified triacrylate (tris-(2-acryloxyethyl) isocyanurate, tris-( 3-acryloxypropyl)isocyanurate, etc.), ε-caprolactone-modified tris(acryloxyalkyl)isocyanurate, and the like. Among them, tris-(2-acryloxyethyl)isocyanurate is preferable from the standpoint of ultraviolet light resistance of the cured product. These can be used individually by 1 type or in combination of 2 or more types.

Examples of the compound (A) having four acryloyl groups include ditrimethylolpropane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, and pentaerythritol tetraacrylate. These can be used individually by 1 type or in combination of 2 or more types.

Examples of the compound (A) having 5 acryloyl groups include dipentaerythritol pentaacrylate. These can be used individually by 1 type or in combination of 2 or more types.

The content of compound (A) in the curable resin composition of the present disclosure is preferably 10 to 75 parts by weight with respect to a total of 100 parts by weight of compound (A), compound (B) and compound (C), More preferably 15 to 70 parts by weight, still more preferably 15 to 65 parts by weight, particularly preferably 20 to 65 parts by weight.

<Compound (B)>
Compound (B) is a methacrylate compound having one or more oxirane rings and one methacryloyl group in one molecule.

Compound (B) is preferably a compound represented by the following formula (2). In formula (2), X represents an oxiranyl group or an epoxycyclohexyl group, and R ² represents a divalent hydrocarbon group.

The epoxycyclohexyl group may be any of a 3,4-epoxycyclohexyl group, a 1,2-epoxycyclohexyl group and a 2,3-epoxycyclohexyl group, but is preferably a 3,4-epoxycyclohexyl group. . The oxiranyl group and epoxycyclohexyl group may have a substituent (alkyl group, etc.) for at least part of the carbon atoms constituting them. X is preferably an oxiranyl group because it reacts with a thiol group at a relatively low temperature and the curing conditions can be easily adjusted.

Examples of the divalent hydrocarbon group for R ² include a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group.

As the divalent aliphatic hydrocarbon group, for example, a linear or branched alkylene group (methylene group, ethylene group, methylmethylene group, propylene group, isopropylene group, butylene group, isobutylene group, s-butylene group, t-butylene group, pentylene group, neopentylene group, isopentylene group, hexylene group, decylene group, dodecylene group, etc. ), a linear or branched alkenylene group having 2 to 20 carbon atoms (preferably 2 to 10 carbon atoms, more preferably 2 to 3 carbon atoms) (vinylene group, propenylene group, isopropenylene group, butenylene group , a pentenylene group, a hexenylene group, etc.), a linear or branched alkynylene group having 2 to 20 carbon atoms (preferably 2 to 10 carbon atoms, more preferably 2 to 3 carbon atoms) (ethynylene group, propynylene group, etc. ) and the like.

As the divalent alicyclic hydrocarbon group, for example, a cycloalkylene group having 3 to 20 carbon atoms (preferably 3 to 15 carbon atoms, more preferably 5 to 8 carbon atoms) (1,2-cyclopentylene group, 1,3-cyclopentylene group, 1,2-cyclohexylene group, 1,3-cyclohexylene group, 1,4-cyclohexylene group, etc.), carbon number 3-20 (preferably carbon number 3-15 , more preferably 5 to 8 carbon atoms) cycloalkylidene group (cyclopentylidene group, cyclohexylidene group, etc.), 3 to 20 carbon atoms (preferably 3 to 15 carbon atoms, more preferably 5 to 8 carbon atoms) Cycloalkenylene group (1,2-cyclopentenylene group, 1,2-cyclohexenylene group, etc.), bridged cyclic hydrocarbon group (bicycloheptanyl group, bicycloheptenyl group, perhydronaphthalen-1-yl group, norbornyl group, adamantyl group, tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodecan-3-yl group, etc.), and the like. be done.

Examples of the divalent aromatic hydrocarbon group include aromatic hydrocarbon groups having 6 to 14 carbon atoms (preferably 6 to 10 carbon atoms) (1,4-phenylene group, 1,3-phenylene group, 4 ,4'-biphenylene group, 3,3'-biphenylene group, 2,6-naphthalenediyl group, 2,7-naphthalenediyl group, 1,8-naphthalenediyl group, anthracenediyl group, etc.).

Among them, the hydrocarbon group for R ² is preferably a divalent aliphatic hydrocarbon group, more preferably a linear or branched alkylene group having 1 to 3 carbon atoms, and methylene more preferably a group.

Specific examples of the compound (B) include glycidyl methacrylate, 2-methylglycidyl methacrylate, 2-oxiranylethyl methacrylate, 2-glycidyloxyethyl methacrylate, 3-glycidyloxypropyl methacrylate, glycidyloxyphenyl methacrylate, 1, 2-epoxycyclohexylmethyl methacrylate, 2,3-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate and the like. Among them, glycidyl methacrylate and 3,4-epoxycyclohexylmethyl methacrylate are preferable, and glycidyl methacrylate is more preferable, from the viewpoint of excellent effect of suppressing gelation of the curable resin composition. Compound (B) can be used individually by 1 type or in combination of 2 or more types.

The curable resin composition of the present disclosure contains a curable compound having a reactive cyclic ether structure (for example, an oxetanyl group, etc.) corresponding to the compound (B) within a range that does not impair the effects of the present disclosure. However, the content thereof is preferably 10 parts by weight or less, more preferably 5 parts by weight or less with respect to 100 parts by weight in total with the compound (B).

The compound (B) preferably contains at least the compound (b-1) in which X is an oxiranyl group. The content of the compound (b-1) is preferably 90% by weight or more, more preferably 95% by weight, relative to the total amount of the compound (B) of 100% by weight, in terms of improving the light resistance and transparency of the cured product. Above, more preferably 100% by weight.

The content of the compound (B) in the curable resin composition of the present disclosure is preferably 10 to 65 parts by weight with respect to a total of 100 parts by weight of the compound (A), the compound (B) and the compound (C), More preferably 15 to 60 parts by weight, still more preferably 20 to 55 parts by weight, particularly preferably 20 to 45 parts by weight.

The weight ratio (A/B) of compound (A) to compound (B) is preferably 0.1 to 7.5, more preferably 0.2 to 5.0, still more preferably 0.3 to 2.0. is.

<Compound (C)>
Compound (C) is a thiol group-containing compound having two or more thiol groups in one molecule. The compound (C) is not particularly limited as long as it contains a thiol group, but is preferably a compound represented by the following formula (3), for example. In formula (3), R ³ represents an n-valent hydrocarbon group, a heterocyclic group, or a group in which these are bonded via a single bond or a linking group, Y represents a single bond or a linking group, and n is 2 to Indicates an integer of 5.

n is preferably 2-4.

Examples of the hydrocarbon group, heterocyclic group, or group in which these groups are bonded via a single bond or a linking group for R ³ include the same groups as those described for R ¹ of compound (A). R ³ is preferably a group obtained by removing n hydrogen atoms from a hydrocarbon structural formula. The n-valent hydrocarbon group, heterocyclic group, or group in which these are bonded via a single bond or a linking group for R ³ is the same as in the case of compound (A), with the hydroxyl group removed from the corresponding polyol compound. may be a residue.

The hydrocarbon for R ³ is preferably an aliphatic hydrocarbon, and has a straight or branched chain having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms). is more preferably an alkane (saturated hydrocarbon) of That is, R ³ is preferably an n-valent hydrocarbon group, more preferably an n-valent carbon atom having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms). A hydrogen group, more preferably an n-valent saturated aliphatic hydrocarbon group having 1 to 5 carbon atoms, particularly preferably an n-valent branched chain saturated aliphatic hydrocarbon group having 1 to 5 carbon atoms. R ³ is preferably a residue obtained by removing a hydroxyl group from 1,4-butanediol, 1,6-hexanediol, or pentaerythritol, more preferably a residue of pentaerythritol.

The linking group for Y is a linking group similar to the linking group for R ¹ of compound (A), a divalent hydrocarbon group for R ² of compound (B), or a group in which these are linked. mentioned.

As the linking group for Y, among others, a group in which an ester bond (--COO--) and a linear or branched alkylene group having 1 to 3 carbon atoms (more preferably a methylene group) are linked is preferable. n Y's may be the same or different.

Compound (C) is, for example, a reaction product in which some or all of the hydroxyl groups of the polyol compound and the carboxyl groups of mercaptocarboxylic acid are ester-bonded, and two or more (2 to 5, preferably 2 to 4 ) of thiol groups.

Examples of the compound (C) having two thiol groups include alkanedithiol (1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2- propanedithiol, 2,2-dimethylpropane-1,3-dithiol, 1,6-hexanedithiol, etc.), cycloalkanedithiol (1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, etc.), polyalkylene glycol dimercapto carboxylate, 1,2-dimercaptobenzene, 1,2-bis(mercaptomethyl)benzene, 1,2-bis(mercaptoethyl)benzene, 1,2-bis(mercaptomethoxy)benzene, 1,2-bis( mercaptoethoxy)benzene, bis(2-mercaptoethyl)ether, 1,2-bis(mercaptomethylthio)benzene, 2,6-naphthalenedithiol, 1,3-diphenylpropane-2,2-dithiol, bisphenol A alkylene oxide modified dimercaptocarboxylate, alkanediol mercaptocarboxylate, tricyclodecane dimercaptocarboxylate, pentaerythritol dimercaptocarboxylate, glycerin dimercaptocarboxylate and the like.

The alkanediol dimercaptocarboxylate is preferably an alkanediol dimercaptocarboxylate having an alkylene group having 2 to 10 carbon atoms (more preferably 3 to 6 carbon atoms), and specific examples include bis(3-mercapto butyryloxy)ethane, 1,4-bis(3-mercaptobutyryloxy)butane and the like. These can be used individually by 1 type or in combination of 2 or more types.

Examples of the compound (C) having three thiol groups include 2,3-dimercapto-1-propanol (2-mercaptoacetate), 2,3-dimercapto-1-propanol (3-mercaptoacetate), and pentaerythrol. trimercaptocarboxylate, trimethylolpropane trimercaptocarboxylate, 1,2,3-trimercaptobenzene, 1,2,4-tris(mercaptomethyl)benzene, 1,2,3-tris(mercaptomethoxy)benzene, 1 , 2,3-tris(mercaptomethylthio)benzene, 2,3-bis(2-mercaptoethylthio)propane-1-thiol, 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3 ,5-triazine-2,4,6(1H,3H,5H)-trione and the like. These can be used individually by 1 type or in combination of 2 or more types.

Examples of the compound (C) having four thiol groups include 2,2-bis(mercaptomethyl)-1,3-propanedithiol, ditrimethylolpropane tetramercaptocarboxylate, pentaerythritol tetramercaptocarboxylate (pentaerythritol tetrakis (mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate)), 1,2,3,4-tetramercaptobenzene, 1,2,3,4- tetrakis(mercaptoethyl)benzene, 1,2,3,5-tetrakis(mercaptomethoxy)benzene, 1,2,3,4-tetrakis(mercaptoethylthio)benzene and the like. These can be used individually by 1 type or in combination of 2 or more types.

Among these, alkanediol mercaptocarboxylate and pentaerythritol tetramercaptocarboxylate are preferred, and 1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritol tetrakis (mercaptoacetate), and pentaerythritol tetrakis (mercaptobutyrate). is more preferred, and pentaerythritol tetrakis (mercaptobutyrate) is even more preferred. Compounds (C) having different numbers of thiol groups can be used in combination of two or more.

The content of pentaerythritol tetramercaptocarboxylate is preferably 90% by weight or more, more preferably 95% by weight or more, based on 100% by weight of the total amount of thiol group-containing compounds, in terms of facilitating adjustment of curing conditions.

The content of the compound (C) in the curable resin composition of the present disclosure is preferably 5 to 40 parts by weight with respect to a total of 100 parts by weight of the compound (A), the compound (B) and the compound (C), More preferably 10 to 35 parts by weight, particularly preferably 15 to 30 parts by weight.

The weight ratio (C/B) of compound (C) to compound (B) is preferably 0.25 to 4.0, more preferably 0.45 to 2.5, still more preferably 0.65 to 1.0. is.

<Photoradical generator (D)>
The curable resin composition of the present disclosure contains a photoradical generator (D) as a curing catalyst. The photo-radical generator (D) initiates or accelerates the radical polymerization reaction of compounds (A) and (B).

Examples of the photoradical generator (D) include alkylphenone photoradical generators, acylphosphine oxide photoradical generators, oxime ester photoradical generators, α-hydroxyketone photoradical generators, and the like. . Among them, alkylphenone-based photoradical generators are preferred.

Examples of the alkylphenone photoradical generator include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1- butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-[4-(4-morpholinyl)phenyl]-1-butanone, 2-methyl-1-[4-(methylthio)phenyl] -2-morpholinopropan-1-one, benzophenone, methylbenzophenone, o-benzoylbenzoic acid, benzoylethyl ether, 2,2-diethoxyacetophenone, 2,4-diethylthioxanthone, diphenyl-(2,4,6-trimethyl benzoyl)phosphine oxide, ethyl-(2,4,6-trimethylbenzoyl)phenylphosphinate, 4,4′-bis(diethylamino)benzophenone, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-1,2-diphenyl Ethan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-(4-isopropenylphenyl)- Oligomers of 2-methylpropan-1-one and the like can be mentioned. Among them, 1-hydroxycyclohexylphenyl ketone is preferred from the viewpoint of storage stability.

Examples of the acylphosphine oxide photoradical generator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide.

Examples of the oxime ester photoradical generator include 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyloxime), 1-[6-(2-methylbenzoyl) -9-ethyl-9H-carbazol-3-yl]ethanone O-acetyloxime and the like.

Examples of the α-hydroxyketone photoradical generator include benzoin, benzoin methyl ether, benzoin butyl ether, 1-hydroxycyclohexylphenyl ketone, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1- (4-i-propylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenylketone, etc. is mentioned.

A photoradical generator (D) can be used individually by 1 type or in combination of 2 or more types.

The content of the photoradical generator (D) in the curable resin composition of the present disclosure is 0.1 to 5 parts per 100 parts by weight in total of the compound (A), the compound (B) and the compound (C). 0.0 part by weight, more preferably 0.2 to 1.0 part by weight, and still more preferably 0.3 to 2.0 part by weight. When the content is 0.1 parts by weight or more, the curing reaction proceeds easily, and when the content is 1.0 parts by weight or less, sufficient ultraviolet light resistance is easily obtained.

<Photoacid generator (E)>
The curable resin composition of the present disclosure contains a photoacid generator (E) as a curing catalyst. The photoacid generator (E) initiates or accelerates the reaction between the epoxy group and the thiol group.

Examples of the photoacid generator (E) include sulfonium salts (salts of sulfonium ions and anions), iodonium salts (salts of iodonium ions and anions), selenium salts (salts of selenium ions and anions), and ammonium salts. (salt of ammonium ion and anion), phosphonium salt (salt of phosphonium ion and anion), salt of transition metal complex ion and anion, and the like.

Examples of the sulfonium salts include [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium tris(pentafluoroethyl)trifluorophosphate, triphenylsulfonium salts, tri-p-tolylsulfonium salts, tri-o-tolylsulfonium salt, tris(4-methoxyphenyl)sulfonium salt, 1-naphthyldiphenylsulfonium salt, 2-naphthyldiphenylsulfonium salt, tris(4-fluorophenyl)sulfonium salt, tri-1-naphthylsulfonium salt, Triaryls such as tri-2-naphthylsulfonium salts, tris(4-hydroxyphenyl)sulfonium salts, diphenyl[4-(phenylthio)phenyl]sulfonium salts, 4-(p-tolylthio)phenyldi-(p-phenyl)sulfonium salts Sulfonium salts; diarylsulfonium salts such as diphenylphenacylsulfonium salts, diphenyl-4-nitrophenacylsulfonium salts, diphenylbenzylsulfonium salts, diphenylmethylsulfonium salts; phenylmethylbenzylsulfonium salts, 4-hydroxyphenylmethylbenzylsulfonium salts, 4- monoarylsulfonium salts such as methoxyphenylmethylbenzylsulfonium salts; trialkylsulfonium salts such as dimethylphenacylsulfonium salts, phenacyltetrahydrothiophenium salts and dimethylbenzylsulfonium salts;

Examples of the diphenyl[4-(phenylthio)phenyl]sulfonium salt include diphenyl[4-(phenylthio)phenyl]sulfonium hexafluoroantimonate, diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate, and the like. .

Examples of the iodonium salt include, for example, the trade name "UV9380C" (manufactured by Momentive Performance Materials Japan LLC, bis(4-dodecylphenyl) iodonium = hexafluoroantimonate 45% alkyl glycidyl ether solution), the trade name " RHODORSIL PHOTOINITIATOR 2074" (manufactured by Rhodia Japan Co., Ltd., tetrakis (pentafluorophenyl) borate = [(1-methylethyl) phenyl] (methylphenyl) iodonium), trade name "WPI-124" (Wako Pure Chemical Industries ( Co., Ltd.), diphenyliodonium salts, di-p-tolyliodonium salts, bis(4-dodecylphenyl)iodonium salts, bis(4-methoxyphenyl)iodonium salts and the like.

Examples of the selenium salts include triarylselenium salts such as triphenylselenium salts, tri-p-tolylselenium salts, tri-o-tolylselenium salts, tris(4-methoxyphenyl)selenium salts, and 1-naphthyldiphenylselenium salts. Salts; diarylselenium salts such as diphenylphenacylselenium salts, diphenylbenzylselenium salts and diphenylmethylselenium salts; monoarylselenium salts such as phenylmethylbenzylselenium salts; trialkylselenium salts such as dimethylphenacylselenium salts; .

Examples of the ammonium salt include tetramethylammonium salts, ethyltrimethylammonium salts, diethyldimethylammonium salts, triethylmethylammonium salts, tetraethylammonium salts, trimethyl-n-propylammonium salts, trimethyl-n-butylammonium salts and the like. alkylammonium salts; pyrrolidium salts such as N,N-dimethylpyrrolidium salts and N-ethyl-N-methylpyrrolidium salts; N,N'-dimethylimidazolinium salts, N,N'-diethylimidazolinium salts, etc. imidazolinium salts of; N,N'-dimethyltetrahydropyrimidium salts, N,N'-tetrahydropyrimidium salts such as diethyltetrahydropyrimidium salts; N,N-dimethylmorpholinium salts, N,N - morpholinium salts such as diethylmorpholinium salts; piperidinium salts such as N,N-dimethylpiperidinium salts and N,N-diethylpiperidinium salts; pyridinium salts such as N-methylpyridinium salts and N-ethylpyridinium salts imidazolium salts such as N,N'-dimethylimidazolium salts; quinolium salts such as N-methylquinolium salts; isoquinolium salts such as N-methylisoquinolium salts; thiazonium salts such as benzylbenzothiazonium salts; Acridium salts such as benzyl acridium salt and the like are included.

Examples of the phosphonium salts include tetraphenylphosphonium salts, tetra-p-tolylphosphonium salts, tetraarylphosphonium salts such as tetrakis(2-methoxyphenyl)phosphonium salts; triarylphosphonium salts such as triphenylbenzylphosphonium salts; triethyl Examples include tetraalkylphosphonium salts such as benzylphosphonium salts, tributylbenzylphosphonium salts, tetraethylphosphonium salts, tetrabutylphosphonium salts, triethylphenacylphosphonium salts and the like.

Salts of the transition metal complex ions include, for example, chromium salts such as (η ⁵ -cyclopentadienyl)(η ⁶ -toluene)Cr+ and (η ⁵ -cyclopentadienyl)(η ⁶ -xylene)Cr+. Salts of complex cations: Salts of iron complex cations such as (η ⁵ -cyclopentadienyl)(η ⁶ -toluene)Fe+, (η ⁵ -cyclopentadienyl)(η ⁶ -xylene)Fe+ and the like. be done.

Examples of anions constituting the above salts include SbF ^6- , PF ^6- , BF ^4- , (CF ₃ CF ₂ ) ₃ PF ^3- , (CF ₃ CF ₂ CF ₂ ) ₃ PF ^3- , (C _{6F 5} ) ₄ B ⁻ , (C ₆ F ₅ ) ₄ Ga ⁻ , sulfonate anion (trifluoromethanesulfonate anion, pentafluoroethanesulfonate anion, nonafluorobutanesulfonate anion, methanesulfonate anion, benzenesulfonate anion, p-toluenesulfonate anion, etc.), (CF ₃ SO ₂ ) ₃ C ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , perhalate ion, halogen sulfonate ion, sulfate ion, carbonate ion, aluminate ions, hexafluorobismuthate ions, carboxylate ions, arylborate ions, thiocyanate ions, nitrate ions, and the like.

The photoacid generator (E) can be used singly or in combination of two or more.

The content of the photoacid generator (E) in the curable resin composition of the present disclosure is 0.5- It is preferably 10.0 parts by weight, more preferably 1.0 to 5.0 parts by weight, still more preferably 1.5 to 3.0 parts by weight.

The curable resin composition of the present disclosure includes a thermal radical generator, a volatile organic solvent, a monofunctional (meth)acrylate that is a reactive diluent, a compound (A), and a compound A curable compound other than (B) and other components may be blended.

The amount of the volatile organic solvent to be blended is, for example, preferably 100 parts by weight or less, more preferably 50 parts by weight or less with respect to a total of 100 parts by weight of compound (A) and compound (B).

The amount of the monofunctional (meth)acrylate compounded is, for example, preferably 0 to 100 parts by weight, more preferably 0 to 100 parts by weight, based on a total of 100 parts by weight of compound (A), compound (B) and compound (C). 20 parts by weight.

The content of the curable compound other than the compound (A) and the compound (B) is preferably 100 parts by weight or less, and 50 parts by weight or less with respect to a total of 100 parts by weight of the compound (A) and the compound (B). More preferably, it is 10 parts by weight or less.

Examples of the other components include sensitizers, light stabilizers, inorganic or organic fillers, reinforcing materials such as carbon fibers and glass fibers, lubricants, antistatic agents, silane coupling agents, antifoaming agents, and leveling agents. , surfactants, flame retardants, colorants, antioxidants, ultraviolet absorbers, ion adsorbents, phosphors, release agents, and the like. The blending amount of these compounds is preferably 5 parts by weight or less with respect to a total of 100 parts by weight of compound (A) and compound (B).

The curable resin composition of the present disclosure, while removing air bubbles under vacuum as necessary, compound (A), compound (B), compound (C), photo-radical generator (D) and photo-acid generator It can be prepared by stirring and mixing (E). The temperature during stirring and mixing is, for example, about 20 to 50°C. For stirring and mixing, known devices (for example, a rotation-revolution mixer, a single- or multi-screw extruder, a planetary mixer, a kneader, a dissolver, etc.) can be used.

The curable resin composition of the present disclosure contains the compound (A), the compound (B), the compound (C), the photoradical generator (D) and the photoacid generator (E), and thus has excellent curability.

The curable resin composition of the present disclosure can form a cured product by light irradiation treatment.

Ultraviolet rays are preferably used for light irradiation for obtaining a cured product. The wavelength of ultraviolet rays used is preferably 200 to 400 nm. Preferred irradiation conditions are an illuminance of 5 to 300 mW/cm ² and a dose of 50 to 18000 mJ/cm ² .

The method of applying and printing the curable resin composition of the present disclosure varies depending on the application, and is not particularly limited. Examples include screen printing, mask printing, offset printing, inkjet printing, flexographic printing, and gravure printing. , squeegee printing, silk screen printing, stamping, dispensing, spraying, brushing, comma coating, gravure coating, die coating and the like.

The curable resin composition of the present disclosure includes, for example, sealants, adhesives, coating agents, electrical insulating materials, laminates, sealants, resists, composite materials, transparent substrates, transparent sheets, transparent films, optical elements, optical It can be used for various applications such as lenses, stereolithography, electronic paper, touch panels, solar cell substrates, optical waveguides, light guide plates, holographic memories, and optical pickup sensors.

<Sealant>
The curable resin composition of the present disclosure has excellent ultraviolet transmittance, and forms a cured product with high light resistance and heat resistance to ultraviolet rays, so that light emitting elements (ultraviolet light emitting elements, etc.) in display members etc. are sealed. It can be preferably used as a sealant or the like to be used. If the curable resin composition of the present disclosure is used as the sealing agent, the light emitting element (ultraviolet light emitting elements, etc.) can be sealed.

When using the curable resin composition of the present disclosure as a sealant, at least the curable resin composition of the present disclosure is included. The sealing agent of the present disclosure contains components other than the curable resin composition (penetration accelerator, humectant (humectant), fixing agent, antifungal agent, preservative, antioxidant, ultraviolet absorber, chelating agent, and thickener). A sticky agent, etc.) may be included, but the content thereof is preferably 10% by weight (preferably 5% by weight) or less with respect to 100% by weight of the entire sealing material.

<Adhesive>
The curable resin composition of the present disclosure has excellent ultraviolet transmittance and forms a cured product with high light resistance and heat resistance to ultraviolet rays, so for example, in display members, optical films (polarizer, polarizer protection films, retardation films, etc.) to image members, optical film adhesives for bonding optical films to each other or optical films to other films, optical semiconductor elements in optical semiconductor devices made of metal. Die attach paste for adhering and fixing to electrodes, lens adhesives for fixing camera lenses to adherends and bonding lenses together, etc. Transparency, light resistance and heat resistance to light rays It can be preferably used as an adhesive for adhering and fixing members and the like to adherends for various applications that require

In particular, the curable resin composition of the present disclosure can be preferably used as an adhesive for optical films. By using the adhesive of the present disclosure as an adhesive for an optical film, a display member in which an image member and an optical film are adhered by a cured product having excellent ultraviolet transmittance, excellent light resistance to ultraviolet rays, and excellent heat resistance. can be obtained.

When the curable resin composition of the present disclosure is used as an adhesive for optical films, at least the curable resin composition of the present disclosure is included. The adhesive of the present disclosure contains components other than the curable resin composition (penetration accelerator, humectant (humectant), fixing agent, antifungal agent, preservative, antioxidant, ultraviolet absorber, chelating agent, and thickening agent. agent, etc.), the content thereof is preferably 10% by weight (preferably 5% by weight) or less with respect to 100% by weight of the entire optical film adhesive.

[Cured product]
The cured product of the present disclosure is obtained by curing the curable resin composition of the present disclosure.

The cured product of the present disclosure has excellent ultraviolet transmittance. The UV transmittance (wavelength: 385 nm) of the cured product (thickness: 500 μm) of the present disclosure is preferably 90.0% or higher, more preferably 90.5% or higher, and still more preferably 91.0% or higher. Therefore, the upper limit is preferably 100%.

Further, the transmittance of light (wavelength 450 nm) of the cured product (thickness 500 μm) of the present disclosure is preferably 90.0% or more, more preferably 90.5% or more, and still more preferably 91.0% or more. and the upper limit is preferably 100%.

The transmittance of ultraviolet light (385 nm wavelength) and light (450 nm wavelength) can be measured according to JIS K7361-1.

In addition, the cured product of the present disclosure has excellent light resistance against light rays (ultraviolet rays, etc.). After exposing the cured product (thickness of 500 μm) of the present disclosure to ultraviolet rays having an intensity of 10 mW/cm ² for 500 hours while heating at 80° C., the transmittance retention rate of ultraviolet rays (wavelength: 385 nm) is preferably 90. It is 0% or more, more preferably 95.0% or more, still more preferably 97.0% or more, and the upper limit is preferably 100%.

The cured product of the present disclosure has excellent heat resistance. After heating at 80° C. for 500 hours, the cured product (thickness of 500 μm) of the present disclosure has a transmittance retention rate of ultraviolet rays (wavelength of 385 nm) of preferably 88.0% or more, more preferably 89.0%. It is 0% or more, more preferably 90.0% or more, and the upper limit is preferably 100%.

[Display material]
The display member of the present disclosure includes a light-emitting element sealed with a cured product of the curable resin composition of the present disclosure, and an image member adhered to an optical film by the cured product of the curable resin composition of the present disclosure. Therefore, it is excellent in light extraction efficiency, light resistance and heat resistance.

As described above, each configuration and combination thereof of the present disclosure are examples, and addition, omission, replacement, and modification of the configuration are possible as appropriate without departing from the gist of the present disclosure. Moreover, the present disclosure is not limited by the embodiments, but only by the claims.

EXAMPLES The present disclosure will be described in more detail below based on examples, but the present disclosure is not limited by these examples.

The compound (A), compound (B), compound (C), photoradical generator (D), photoacid generator (E) and photobase generator used in Examples and Comparative Examples are as follows. .

(Compound (A))
・Viscoat #230: 1,6-hexanediol diacrylate, trade name “Viscoat #230”, manufactured by Osaka Organic Chemical Industry Co., Ltd. ・Viscoat #195: 1,4-butanediol diacrylate, trade name “Viscoat #195” ”, Osaka Organic Chemical Industry Co., Ltd. A-9300: Tris-(2-acryloxyethyl) isocyanurate, trade name “NK Ester A-9300”, Shin-Nakamura Chemical Industry Co., Ltd.

(Compound (B))
・GMA: glycidyl methacrylate, trade name “glycidyl methacrylate”, manufactured by Mitsubishi Gas Chemical Co., Ltd. ・M100: 3,4-epoxycyclohexylmethyl methacrylate, trade name “Cycromer M100”, manufactured by Daicel Corporation

(Compound (C))
・ Karenz MTPE1: pentaerythritol tetrakis (3-mercaptobutyrate), trade name “Karenz MTPE1”, manufactured by Showa Denko Co., Ltd. ・ Karenz MTBD1: 1,4-bis(3-mercaptobutyryloxy)butane, trade name “ Karenz MTBD1", manufactured by Showa Denko K.K.

(Photoradical generator (D))
- Omnirad 184: 1-hydroxycyclohexyl phenyl ketone, trade name "Omnirad 184", IGM Resins B.V. V. manufactured by the company

(Photoacid generator (E))
- CPI210S: a salt of diphenyl[4-(phenylthio)phenyl]sulfonium cation and fluorophosphonate anion

(Photobase generator)
・ WPBG266: 1,2-diisopropyl-3-[bis(dimethylamino)methylene]guanidinium = 2-(3-benzoylphenyl)propianate, trade name “WPBG-266”, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

<Examples 1 to 7, Comparative Example 1>
A uniform curable resin composition was obtained by charging each component into a flask according to the formulation shown in Table 1 and stirring and mixing at room temperature.

The curable resin compositions obtained in Examples and Comparative Examples were coated on a PEN (polyethylene naphthalate) film (trade name “Teonex”, manufactured by Teijin DuPont Films Ltd., thickness 50 μm), and the thickness after curing was After cast coating using a bar coater so that the thickness is 500 μm, it is irradiated with ultraviolet rays for 10 seconds (ultraviolet wavelength: 365 nm, ultraviolet irradiation amount: 3000 mJ/cm ² ), and finally left at 23° C. for 24 hours. The PEN film was peeled off to obtain a cured product with a thickness of 500 μm.

The obtained cured product (thickness: 500 µm) was evaluated for transparency, light resistance and heat resistance as follows.

(Curability)
The curability was evaluated by applying the curable resin composition to the transparent stage of a UV irradiation rheometer (MCR302, manufactured by Anton Paar), setting the gap to 100 μm, and irradiating ultraviolet rays (ultraviolet wavelength: 365 nm, ultraviolet irradiation amount: 3000 mJ/cm ² ) When the film was held at 23° C. after UV irradiation, it was judged by the time until the storage modulus and the loss modulus intersect. When cured after 10 minutes, it was evaluated as ◯, and when it was cured within 10 minutes, it was evaluated as x.

(permeability)
Using a spectrophotometer (product name “UV-2450”, manufactured by Shimadzu Corporation), the light transmittance (%) was measured for ultraviolet light (wavelength: 385 nm) or light (wavelength: 450 nm). The higher the light transmittance value, the more excellent the transparency of the cured product.

(light resistance)
The resulting cured product (thickness: 500 μm) was exposed to ultraviolet light with an intensity of 10 mW/cm ² for 500 hours while heating at 80° C., and then measured with a spectrophotometer (product name: “UV-2450” manufactured by Shimadzu Corporation). ) was used to measure the light transmittance (%) of ultraviolet rays (wavelength: 385 nm). The value of the light transmittance after exposure to the light transmittance before exposure (light transmittance maintenance rate of the cured product) was evaluated as the transmittance maintenance rate (light resistance) (%). The higher the transparency retention rate, the better the UV light resistance of the cured product.

(Heat-resistant)
The resulting cured product (thickness 500 μm) was heated at 80° C. for 500 hours, and then subjected to ultraviolet light (wavelength 385 nm) using a spectrophotometer (product name “UV-2450” manufactured by Shimadzu Corporation). was measured for light transmittance (%). The value of the light transmittance after exposure to the light transmittance before exposure (light transmittance maintenance rate of the cured product) was evaluated as the transmittance maintenance rate (heat resistance) (%). The higher the permeability retention rate, the better the heat resistance of the cured product.

Claims (8)

A curable resin composition comprising the following compound (A), the following compound (B), the following compound (C), a photoradical generator (D), and a photoacid generator (E).
Compound (A): Acrylate compound having two or more acryloyl groups in one molecule Compound (B): Methacrylate compound having one or more oxirane rings and one methacryloyl group in one molecule Compound (C): 1 Thiol group-containing compound having two or more thiol groups in the molecule The curable resin composition according to claim 1, wherein the compound (A) is a compound represented by the following formula (1).

[In formula (1), R ¹ represents an m-valent hydrocarbon group, a heterocyclic group, or a group in which these are bonded via a single bond or a linking group, and m is an integer of 2 to 5] The curable resin composition according to claim 1 or 2, wherein the compound (B) is a compound represented by the following formula (2).

[In formula (2), X represents an oxiranyl group or an epoxycyclohexyl group, and R ² represents a divalent hydrocarbon group] The curable resin composition according to any one of claims 1 to 3, wherein the compound (C) is a compound represented by the following formula (3).

[In formula (3), R ³ represents an n-valent hydrocarbon group, a heterocyclic group, or a group in which these are bonded via a single bond or a linking group, Y represents a single bond or a linking group, and n is 2 indicates an integer of ~5] A sealant comprising the curable resin composition according to any one of claims 1 to 4. An adhesive comprising the curable resin composition according to any one of claims 1 to 4. A cured product of the curable resin composition according to any one of claims 1 to 4. A display member comprising the cured product according to claim 7.