JP2016108503A - Photocurable resin composition and method for producing light-shielding resin layer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photocurable resin which is cured in a short time by irradiating light and can impart light shielding properties to a resin layer after curing and to provide a method for producing a light-shielding resin layer by photocuring a photocurable resin.SOLUTION: There are provided: [1] a photocurable resin composition comprising a curable compound, a photopolymerization initiator and a leuco dye; and [2] a method for producing a light-shielding resin layer which comprises a step of forming a light-shielding resin layer by the photocuring reaction of a liquid film-like photocurable resin composition, wherein in the step, the liquid film-like photocurable resin composition has light-shielding properties at a predetermined temperature or less and when exceeding the predetermined temperature, the light-shielding properties are lowered.SELECTED DRAWING: None

Description

  The present invention relates to a photocurable resin composition and a method for producing a light-shielding resin layer.

  When an uncured photocurable resin (hereinafter simply referred to as a photocurable resin) composition is used as an adhesive, curing can be shortened in several seconds since the curing is completed in units of several seconds. Therefore, it greatly contributes to mass production of products in the electronics field.

  On the other hand, for example, a light-shielding resin film that requires light-shielding properties, such as a black matrix incorporated as a color filter substrate in a liquid crystal panel, is produced by curing a photocurable resin containing a colored pigment such as a black pigment. Attempts have been made (for example, Patent Document 1).

JP 2014-157179 A

  In recent years, in the production of products requiring light-shielding properties such as liquid crystal display elements, the light-shielding adhesive in which the cured adhesive layer itself has light-shielding properties even for a photocurable resin composition used as an adhesive. It may be required to form a layer.

However, when a light-curable resin composition containing a colored pigment is used to form a light-shielding resin film or a light-shielding adhesive layer (hereinafter collectively referred to as a light-shielding resin layer), the photo-curing property containing the colored pigment is used. The liquid film of the resin composition itself has a high light shielding property, it is difficult to transmit light such as ultraviolet rays, and it is difficult to form a light shielding resin layer that is cured in a short time.
For this reason, a thermosetting resin composition must be used for the production of the light-shielding resin layer, and curing of the photocurable resin composition containing the colored pigment in a short time improves the productivity of the light-shielding resin layer. It is an important issue for us.

  The present invention provides a light-shielding property by photocuring a photocurable resin composition capable of curing in a short time by light irradiation and imparting light-shielding properties to the cured resin layer, and a liquid film-like photocurable resin composition. It is an object to provide a method for producing a resin layer.

The present invention
[1] Curable compound (component A), photopolymerization initiator (component B) and the following formula (1):

(Wherein R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom, which may be the same or different from each other; ₁ , X ₂ , Y ₁ , Y _{2 each} represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alicyclic ring or an aromatic ring, which may be the same or different from each other) A photocurable resin composition comprising component C), and
[2] A method for producing a light-shielding resin layer comprising a step of photocuring a liquid film-like photocurable resin composition to obtain a light-shielding resin layer,
In the step, the liquid film-like photocurable resin composition has a light shielding property at a predetermined temperature or less, and the light shielding property is lowered when the predetermined temperature is exceeded. is there.

  According to the present invention, a photocurable resin composition capable of curing in a short time by light irradiation and imparting light-shielding properties to the cured resin layer, and a liquid film photocurable resin composition are photocured. A method for producing a light-shielding resin layer can be provided.

(1) Component A
The photocurable resin composition of the present invention (hereinafter also referred to as a photocurable resin composition) contains a curable compound (component A).

Component A is a compound that can be radically polymerized or cationically polymerized by light such as visible light or ultraviolet light, and may be a monomer, oligomer, or polymer (hereinafter, the resin includes a monomer, oligomer, or polymer). ).
From the viewpoint of rapid hardening and / or curing shrinkage reduction,
Preferred is at least one resin selected from the group consisting of epoxy resins, partially (meth) acrylated epoxy resins, (meth) acrylic acid, (meth) acrylate resins, urethane acrylate resins, polyester acrylate resins, oxetane resins and styrene derivatives. ,
More preferably, at least one resin selected from the group consisting of epoxy resins, partially (meth) acrylated epoxy resins, (meth) acrylic acid and (meth) acrylate resins,
Urethane acrylate resins and / or (meth) acrylate resins are more preferred,
In the (meth) acrylate resin, isobornyl (meth) acrylate is preferable.
In addition, (meth) acrylate means an acrylate or a methacrylate.

  When the photocurable resin composition is used as a liquid crystal sealant, the elution of component A into the liquid crystal and the unreacted compound remaining after the polymerization or crosslinking reaction are reduced, and from the viewpoint of suppressing liquid crystal contamination, as component A The preferred curable resins are preferably used alone or in combination.

An epoxy resin is a compound having one or more epoxy groups,
Diglycidyl ethers of bisphenols such as biphenol, bisphenol A, hydrogenated bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetrachlorobisphenol A, tetrabromobisphenol A;
Polyglycidyl ethers of novolak resins such as phenol novolak, cresol novolak, brominated phenol novolak, ortho cresol novolak;
Ethylene glycol, polyethylene glycol, polypropylene glycol, butanediol, 1,6-hexanediol, neopentyl glycol, trimethylolpropane, 1,4-cyclohexanedimethanol, ethyleneoside adduct of bisphenol A, propylene oxide addition of bisphenol A Diglycidyl ethers of alkylene glycols such as
Glycidyl esters such as glycidyl ester of hexahydrophthalic acid and diglycidyl ester of dimer acid;
3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexylethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexyl-3 ', 4'-Epoxy-6'-methylcyclohexanecarboxylate, vinylcyclohexene dioxide, 3,4-epoxy-4-methylcyclohexyl-2-propylene oxide, 2- (3,4-epoxycyclohexyl-5,5- Spiro-3,4-epoxy) cyclohexane-m-dioxane, bis (3,4-epoxycyclohexyl) adipate, bis (3,4-epoxycyclohexylmethyl) adipate, lactone-modified 3,4-epoxycyclohexylmethyl-3 ′, 4'-epoxy Hexanecarboxylate, methylenebis (3,4-epoxycyclohexane), ethylenebis (3,4-epoxycyclohexanecarboxylate), dicyclopentadiene diepoxide, bis (3,4-epoxycyclohexyl) ether, bis (3,4 Epoxycyclohexylmethyl) ether, tetra (3,4-epoxycyclohexylmethyl) butanetetracarboxylate, bis (3,4-epoxycyclohexylmethyl) -4,5-epoxytetrahydrophthalate, bis (3,4-epoxycyclohexyl) diethyl Examples thereof include alicyclic epoxy compounds such as siloxane and oligomers having these photoreactive functional groups.

  The (meth) acrylate resin may be a compound having one or more (meth) acryloyl groups, and (meth) acrylic acid or its ester, diol mono (meth) acrylate, diol monoether mono (meth) Examples include acrylate, monoester mono (meth) acrylate of diol, di (meth) acrylate of diol, poly (meth) acrylate of polyol, epoxy (meth) acrylate, urethane (meth) acrylate, and the like.

As (meth) acrylic acid ester,
Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, C1-C18 alkyl esters such as isostearyl (meth) acrylate;
Aralkyl esters such as benzyl (meth) acrylate; alicyclic esters such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate;
Examples include heterocyclyl esters such as tetrahydrofurfuryl (meth) acrylate.

  Diol mono (meth) acrylates include ethylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, Examples include polypropylene glycol mono (meth) acrylate and neopentyl glycol mono (meth) acrylate.

  As monoether mono (meth) acrylate of diol, mono C1-C18 alkyl ether mono (meth) acrylate, monophenyl ether of ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol or neopentyl glycol More specifically, mono (meth) acrylate and the like, ethylene glycol monomethyl ether mono (meth) acrylate, ethylene glycol monoethyl ether mono (meth) acrylate, ethylene glycol monophenyl ether mono (meth) acrylate and the like can be mentioned.

  As monoester mono (meth) acrylate of diol, monoacetate mono (meth) acrylate, monosuccinate mono (meth) of ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol or neopentyl glycol Examples include acrylate, monophthalate mono (meth) acrylate, monohexahydrophthalate mono (meth) acrylate, and monobenzoate mono (meth) acrylate.

  Di (meth) acrylate of diol includes ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, Polypropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, bisphenol A EO adduct di ( And (meth) acrylate, PO adduct di (meth) acrylate of bisphenol A, and the like.

  Poly (meth) acrylates of polyols include glycerol, trimethylolpropane, pentaerythritol or dipentaerythritol (meth) acrylate, such as glycerol tri (meth) acrylate, EO-modified glycerol tri (meth) acrylate, PO-modified glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol Examples include tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

  The partially (meth) acrylated epoxy resin is an ester of (meth) acrylic acid and an epoxy resin.

  Specific examples of the partially (meth) acrylated epoxy resin include an ester of (meth) acrylic acid and a bisphenol A type epoxy compound, an ester of (meth) acrylic acid and a bisphenol F type epoxy compound, and the like.

  The urethane (meth) acrylate resin is a reaction product of a hydroxyl group-containing (meth) acrylate compound and an isocyanate compound.

  The hydroxyl group-containing (meth) acrylate compound is not particularly limited as long as it is a (meth) acrylate compound having one or more hydroxyl groups in the molecule. For example, 2-hydroxyethyl (meth) acrylate, 2- Hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acryloyl phosphate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate Glycerin di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, caprolactone modified - hydroxyethyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate.

  The isocyanate compound is not particularly limited as long as it is a compound having two or more isocyanato groups, and is an aromatic, aliphatic, or alicyclic polyisocyanate such as tolylene diisocyanate, diphenylmethane diisocyanate, hydrogenated. Diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3- Bis (isocyanatomethyl) cyclohexane, phenylene diisocyanate, lysine diisocyanate , Lysine triisocyanate, polyisocyanate, or terminal isocyanate group-containing urethane prepolymers obtained by reacting these polyisocyanates with polyols such as naphthalene diisocyanate.

  Examples of styrene derivatives include styrene, p-methylstyrene, p-methoxystyrene, β-methylstyrene, p-methyl-β-methylstyrene, α-methylstyrene, p-methoxy-β-methylstyrene, p-hydroxystyrene, and the like. Is mentioned.

(2) Component B
The photocurable resin composition contains a photopolymerization initiator (component B).

Examples of component B include an ultraviolet polymerization initiator and a visible light polymerization initiator.
Examples of ultraviolet polymerization initiators include benzoin, benzophenone, and acetophenone,
Examples of visible light polymerization initiators include acylphosphine oxides, thioxanthones, metallocenes, and quinones.

Specifically, as an ultraviolet polymerization initiator,
Benzophenone polymerization initiators such as benzophenone, 4-phenylbenzophenone, benzoylbenzoic acid, and bisdiethylaminobenzophenone;
Acetophenone polymerization initiators such as 2,2-diethoxyacetophenone;
Benzoin polymerization initiators such as benzyl, benzoin, and benzoin isopropyl ether;
Alkylphenone polymerization initiators such as benzyldimethyl ketal; thioxanthone polymerization initiators such as thioxanthone;
1-hydroxycyclohexyl phenyl ketone, 1- (4-isopropylphenyl) 2-hydroxy-2-methylpropan-1-one, 1- (4- (2-hydroxyethoxy) -phenyl) -2-hydroxy-2-methyl Examples thereof include hydroxyalkylphenone polymerization initiators such as 1-propan-1-one and 2-hydroxy-2-methyl-1-phenylpropan-1-one.

Examples of visible light polymerization initiators include 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and bis (2,6-dimethoxybenzoyl) -2,4. Acylphosphine oxide photopolymerization initiators such as 1,4-trimethyl-pentylphosphine oxide;
Camphorquinone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1- Examples thereof include ketone-based polymerization initiators such as butanone-1.

As the component B, among the above examples, from the viewpoint of curability in addition to normal strength and durability strength, a hydroxyalkylphenone polymerization initiator and / or an acylphosphine oxide photopolymerization initiator is more preferable.
1-hydroxycyclohexyl phenyl ketone (IRGACURE184, manufactured by BASF) and / or bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (IRGACURE819, manufactured by BASF) are more preferable.

  When component A is cationically polymerizable, component B acts as a photoacid generator, and preferably generates Lewis acid or Bronsted acid by irradiation with energy rays from the viewpoint of curability in addition to normal strength and durability strength. And sulfonium salts and / or iodonium salts are preferred.

As a sulfonium salt, in addition to normal strength and durability strength, from the viewpoint of curability,
Triphenylsulfonium hexafluorophosphate,
Triphenylsulfonium hexafluoroantimonate,
Triphenylsulfonium tetrakis (pentafluorophenyl) borate,
4,4′-bis [diphenylsulfonio] diphenyl sulfide bishexafluorophosphate,
4,4′-bis [di (β-hydroxyethoxy) phenylsulfonio] diphenyl sulfide bishexafluoroantimonate,
4,4′-bis [di (β-hydroxyethoxy) phenylsulfonio] diphenyl sulfide bishexafluorophosphate,
7- [di (p-toluyl) sulfonio] -2-isopropylthioxanthone hexafluoroantimonate,
7- [di (p-toluyl) sulfonio] -2-isopropylthioxanthone tetrakis (pentafluorophenyl) borate,
4-phenylcarbonyl-4′-diphenylsulfonio-diphenyl sulfide hexafluorophosphate,
4- (p-tert-butylphenylcarbonyl) -4′-diphenylsulfonio-diphenyl sulfide hexafluoroantimonate,
4- (p-tert-butylphenylcarbonyl) -4′-di (p-toluyl) sulfonio-diphenyl sulfide tetrakis (pentafluorophenyl) borate and the like are preferable.

As the commercially available sulfonium salt cationic polymerization initiator, Adeka SP-170, SP-172, SP-150, SP-152, San Apro CPI-210S, etc. are preferable, Adeka SP-170, SP-172 or CPI-210S manufactured by San Apro is more preferable.
These salts may be used alone or in combination of two or more.

As an iodonium salt, in addition to normal strength and durability strength, from the viewpoint of curability,
Diphenyliodonium tetrakis (pentafluorophenyl) borate,
Diphenyliodonium hexafluorophosphate,
Diphenyliodonium hexafluoroantimonate,
Di (4-nonylphenyl) iodonium hexafluorophosphate and the like are preferable.
As a commercially available iodonium salt-based cationic polymerization initiator, PI2074 manufactured by Rhodia is preferable.
These salts may be used alone or in combination of two or more.

(3) Component C
The photocurable resin composition has the following formula (1):

(Wherein R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom, which may be the same or different from each other; ₁ , X ₂ , Y ₁ , Y _{2 each} represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alicyclic ring or an aromatic ring, which may be the same or different from each other) Contains component C)

  Component C is a blue leuco dye, preferably a blue leuco dye, which has excellent color density and light resistance and has a clear color tone, and is preferably dispersed in the photocurable resin composition. Thus, the light-shielding resin layer formed of the photocurable resin composition can be provided with a light-shielding property that can be used as a black matrix incorporated as a color filter substrate in the liquid crystal panel.

Component C, even if contained in the photocurable resin composition, in the process of photocuring reaction of the liquid film-like photocurable resin composition, the color disappears as the temperature rises due to reaction heat, By improving the light transmittance of ultraviolet rays or the like, the deep curability of the photocurable resin composition is improved, and the entire resin layer can be cured in a short time.
Component C develops color again when the cured resin layer falls below a certain temperature, and imparts light blocking properties to the resin layer to form a light blocking resin layer.

  In formula (1), R1, R2, R3 and R4 are each a hydrogen atom; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group and tert-butyl. An alkyl group having 1 to 4 carbon atoms composed of a group or the like; or a halogen atom such as a fluorine atom (-F), a chlorine atom (-Cl), a bromine atom (-Br) or an iodine atom (-I). May be the same as or different from each other.

In formula (1), X ₁ , X ₂ , Y ₁ , Y ₂ are each a hydrogen atom; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group , A tert-butyl group, an n-pentyl group, an isopentyl group, a tert-pentyl group, a neopentyl group, and the like; an alicyclic ring composed of a cyclopentyl group, a cyclohexyl group, etc .; or a phenyl group, a benzyl group An aromatic ring composed of a group or the like is represented, and these may be the same or different.

As a specific leuco dye represented by the formula (1), for example,
Methyl-3 ′, 6′-bisdiphenylaminofluorane,
Ethyl-3 ′, 6′-bisdiphenylaminofluorane,
Chloro-3 ′, 6′-bisdiphenylaminofluorane,
Fluoro-3 ′, 6′-bisdiphenylaminofluorane,
Bromo-3 ', 6'-bisdiphenylaminofluorane,
Iodo-3 ′, 6′-bisdiphenylaminofluorane,
3,4-Dichloro-3 ′, 6′-bisdiphenylaminofluorane and the like can be mentioned, and these can be used alone or in combination of two or more, but from the viewpoint of light shielding properties and light resistance. , at least one of X and Y is preferably a methyl group (-CH _3), more preferably X and Y are both methyl groups (-CH _3).

Specifically, as component C,
The following chemical formula (2) (2′-anilino-6 ′-[ethyl (p-tolyl) amino] -3′-methylspiro [isobenzofuran-1 (3H), 9 ′-[9H] xanthen] -3-one) ;
The following chemical formula (3) (6- (diethylamino) -2- [3- (trifluoromethyl) anilino] spiro [9H-xanthene-9,3 ′ (1′H) -isobenzofuran] -1′-one);
The following chemical formula (4) (2′-anilino-6 ′-(N-ethyl-N-isopentylamino) -3′-methylspiro [phthalide-3,9 ′-[9H] xanthene]);
The following chemical formula (5) (2′-anilino-3′-methyl-6 ′-(dipentylamino) spiro [isobenzofuran-1 (3H), 9 ′-[9H] xanthen] -3-one):

The compound shown by these is preferable.

As the component C, for example, a triarylamine derivative obtained by a commercially available or general-purpose synthesis means and a phthalic anhydride derivative are heated and reacted in the presence of an acid catalyst, thereby easily represented by the formula (1). A leuco dye excellent in light-shielding properties and light resistance can be obtained.
Component C is No. manufactured by Mitsubishi Pencil Co. It can also be obtained as TO62.

(4) Microcapsule Component C is contained in the microcapsule from the viewpoint of dispersing in the photocurable resin composition and adjusting the color developability of component C. The microcapsule containing component C is photocurable. It is preferably contained in the resin composition, and more preferably dispersed.

  The microcapsule is excellent in light-shielding property and light resistance, and is excellent in easy decolorization and stability, and can be suitably used as a carrier of component C of a photocurable resin composition for producing a light-shielding resin layer. .

  In addition to Component C, the microcapsule also contains a developer (component D) and / or a color change temperature adjusting agent (component E), and the composition in the microcapsule is a thermochromic composition. preferable.

  Component D is a component having the ability to color component C. For example, inorganic acids, aromatic carboxylic acids and anhydrides or metal salts thereof, organic sulfonic acids, other organic acids and phenolic compounds, and the like Bisphenol derivatives and / or sulfonylurea compounds are preferred, and the following formula (6):

(Wherein R1 represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and R2 represents a linear or branched alkyl group having 4 to 10 carbon atoms) (compound d) is more preferable.

Specifically, as the compound d,
4,4 '-(2-ethylhexylidene) bisphenol,
4,4 '-(2-ethylpentylidene) bisphenol,
4,4'-octylidenebisphenol,
4,4′-hexylidene bisphenol,
4,4 '-(4-methyloctylidene) bisphenol,
4,4′-decylidenebisphenol,
4,4 '-(1,3-dimethylbutylidene) bisphenol,
4,4 '-(3-methylbutylidene) bisphenol,
4,4 '-(1-methylhexylidene) bisphenol,
4,4 '-(1,2-dimethylbutylidene) bisphenol,
4,4 '-(1,5-dimethylhexylidene) bisphenol,
4,4 '-(1-ethyl-3-methylpentylidene) bisphenol,
4,4 ′-(1-methyl-4-methylheptylidene) bisphenol,
4,4 '-(1-ethyl-hexylidene) bisphenol,
4,4 '-(1-ethyl-pentylidene) bisphenol,
Mention may be made of at least one kind or a mixture of two or more kinds such as 4,4 ′-(1-ethyl-octylidene) bisphenol.

  Component E is a substance that controls the color change temperature in the coloration of Component C and Component D, and includes alcohols, esters, ketones, ethers, acid amides, azomethines, fatty acids, hydrocarbons, and the like. An ester compound composed of a compound having a hydroxyl group in the chemical structure and a saturated fatty acid having 8 to 22 carbon atoms is preferred, and is an ester compound composed of a bisphenol derivative and a saturated fatty acid having 8 to 22 carbon atoms. Yes, the following formula (7):

(Wherein R3 and R4 represent a linear or branched alkyl group having 7 to 21 carbon atoms, and R5 and R6 represent a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, or CF ₃ ). Compound e is more preferred.

Specifically, as compound e,
4,4 ′-(hexafluoroisopropylidene) bisphenol dicaprate,
4,4 ′-(hexafluoroisopropylidene) bisphenol dilaurate,
4,4 ′-(hexafluoroisopropylidene) bisphenol dimyristate,
4,4 '-(hexafluoroisopropylidene) bisphenol dipalmiate,
4,4 ′-(hexafluoroisopropylidene) bisphenol diundecanoate,
4,4 ′-(hexafluoroisopropylidene) bisphenol ditridecate,
4,4 '-(isopropylidene) bisphenol dicaplate,
4,4 '-(isopropylidene) bisphenol dilaurate,
4,4 ′-(isopropylidene) bisphenol dimyristate,
4,4 '-(isopropylidene) bisphenol dipalmiate,
4,4 ′-(isopropylidene) bisphenol diundecanoate,
4,4 '-(isopropylidene) bisphenol ditridecate,
4,4'-methylenebisphenol dicaplate,
4,4′-methylenebisphenol dilaurate,
4,4'-methylenebisphenol dimyristate,
4,4'-methylenebisphenol dipalmiate,
4,4′-methylenebisphenol diundecanoate,
Examples thereof include at least one kind or a mixture of two or more kinds such as 4,4′-methylenebisphenol ditridecaate.

When a photocurable resin composition containing microcapsules is made into a liquid film-like resin layer and irradiated with light, the temperature of the resin layer is increased by a photocuring reaction. The light shielding property of the layer is lowered, preferably the light shielding property is lost, and the resin layer is cured in a short time as the photo-curing proceeds.
When the temperature of the cured resin layer is lowered, the microcapsules are colored to provide light shielding property to the resin layer, and a light shielding resin layer can be obtained.
From the viewpoint of the light curability of the light curable resin and the light shielding property of the light shielding resin layer,
The fading temperature (predetermined temperature) of the microcapsules is preferably 40 to 70 ° C, more preferably 50 to 60 ° C,
The color development temperature of the microcapsule is preferably 20 to 40 ° C, more preferably 25 to 35 ° C.

  The microcapsules have an average particle size of preferably 0.1 by measuring a thermochromic composition comprising Component C and Component E or Component D and Component E with a particle size distribution measuring device (particle size measuring device N4Plus manufactured by COULTER). It can manufacture by microencapsulating so that it may become 3-1.0 micrometer.

  Examples of the microencapsulation method include interfacial polymerization method, interfacial polycondensation method, in situ polymerization method, liquid curing coating method, phase separation method from aqueous solution, phase separation method from organic solvent, melt dispersion cooling method, air A suspension coating method, a spray drying method, etc. can be mentioned, and can be appropriately selected according to the application.

  For example, in the phase separation method from an aqueous solution, after component C and component D and / or component E are heated and melted, they are put into an emulsifier solution, heated and stirred to disperse into oil droplets, and then used as a capsule membrane agent as a resin. By using raw materials, for example, amino resin solution, specifically, methylol melamine aqueous solution, urea solution, benzoguanamine solution, etc., are gradually added, followed by reaction, and after preparation, the dispersion is filtered. The desired thermochromic microcapsules can be produced.

The wall film of the microcapsule is preferably formed of a urethane resin, an epoxy resin, or an amino resin from the viewpoint of storage stability.
Examples of the urethane resin include a compound of an isocyanate and a polyol. Examples of the epoxy resin include an epoxy resin and an amine compound. Examples of the amino resin include a melamine resin, a urea resin, and a benzoguanamine resin. However, it is more preferable that it is a melamine resin.

The thickness of the wall film of the microcapsule is appropriately determined according to the required wall film strength and drawn line density.
In order to form the wall film with an amino resin, when using each microencapsulation method, a suitable amino resin raw material (melamine resin, urea resin, benzoguanamine resin, etc.), a dispersant, a protective colloid, etc. select.

When component C is used in a microcapsule together with component D and / or component E,
From the viewpoint of the color developability of component C and the stability of color change temperature adjustment, with respect to component C (1 part by mass),
Component D is preferably 0.1 to 100 parts by mass,
Component E is preferably 1 to 1000 parts by mass, and more preferably 1 to 100 parts by mass.

  The total amount of components C, D, and E in the contents of the microcapsule is blended with other components for adjusting the viewpoint of color development and stability of color change temperature adjustment and light-shielding property after curing and practical performance. From the viewpoint of securing room, it is preferably 65 to 97% by mass, more preferably 70 to 95% by mass, and still more preferably 70 to 90% by mass.

  It is preferable that the film agent of a microcapsule is 0.1-1 mass part with respect to the content (1 mass part) of a microcapsule.

By suitably combining the types, amounts, and the like of components C, D, and E, the color development temperature and the color erasing temperature can be set to suitable temperatures.
In addition, if it is in the range which does not impair the various characteristics of the composition of this invention, it can also be used in combination with another well-known color developer and / or color-change temperature regulator.

(5) Other additives The photocurable resin composition can be used in accordance with the purpose, for example, a solvent, an antioxidant, an ultraviolet absorber, a light stabilizer, a silane coupling agent, a polymerization inhibitor, a leveling agent, and a surface activity. An agent, a colorant, a storage stabilizer, a plasticizer, a lubricant, a filler, an anti-aging agent, a wettability improver, a release agent, and the like can be added.

  The photocurable composition can be in the form of a solution, slurry, or paste containing a solvent from the viewpoint of being applied to the surface of a substrate to be bonded such as a liquid crystal display element.

  Examples of the organic solvent include alcohols, glycol ethers, esters, and ketones.

Examples of alcohols include pentanol, hexanol, cyclohexanol, ethylene glycol, and propylene glycol.
Examples of glycol ethers include ethyl ethoxy acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxypropionic acid. Ethyl, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate , 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol Monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and the like diethylene glycol monoethyl ether acetate.
Esters include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, aceto Examples include methyl acetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.
Examples of ketones include 4-hydroxy-4-methyl-2-pentanone, 2-heptanone, 3-heptanone, 4-heptanone, cyclopentanone, cyclohexanone, and isophorone.

(6) Photocurable resin composition The suitable composition of a photocurable resin composition is demonstrated.

  The photocurable resin composition contains the component C together with the components A and B. For example, when the photocurable resin composition is formed into a liquid film and irradiated with light such as ultraviolet rays, the component C is decolored as the temperature rises due to reaction heat. In addition to improving the light transmittance of the resin layer, not only the entire resin layer can be cured in a short time, but also the colored resin is recolored when the cured resin layer falls below a certain temperature. A light shielding resin layer can be formed by imparting light shielding properties to the layer.

  In addition, when the component A or the components A and B are liquid, the photocurable resin composition constitutes a liquid material having fluidity such as a solution, a slurry, or a paste without using a solvent, and screen printing. The liquid film can be formed with a dispenser or the like.

From the viewpoint of curability in a short time and light-shielding properties after curing,
Component B is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 7 parts by mass, still more preferably 1 to 5 parts by mass,
The microcapsule containing Component C is preferably 1 to 50 parts by mass, more preferably 5 to 30 parts by mass, and still more preferably 10 to 20 parts by mass.

From the viewpoint of curability in a short time and light-shielding property after curing, and from the viewpoint of securing room for blending other components for adjusting the practical performance of the photocurable composition, the solid content of the photocurable resin composition During,
The total content of Component A, Component B and microcapsules is preferably 65 to 97% by mass, more preferably 70 to 95% by mass, and still more preferably 70 to 90% by mass.

The photocurable resin composition can be obtained by uniformly kneading and mixing the compounding components with a mixing stirrer, roll mill, bead mill or the like.
The photocurable resin composition can also be produced by adding other components to a solution in which microcapsules containing Component A, Component B and Component C or Component C are appropriately dissolved in a solvent, and stirring and mixing until uniform. it can.

(7) Manufacturing method of light-shielding resin layer A photocurable resin composition is, for example, a solution, slurry, or paste-like material on a substrate surface such as glass, silicon wafer, copper, copper-based alloy, iron, iron-based alloy, etc. The photocurable resin composition can be used by being applied in a liquid film form by screen printing, a dispenser or the like.
In addition, in this specification, a liquid film form means the state of the photocurable resin composition which has fluidity | liquidity, such as a solution, slurry, or paste form.

  The liquid film-like photocurable resin composition is preferably 200 to 450 nm, more preferably 300 to 400 nm by a metal halide lamp, high-pressure water lamp, xenon lamp, halogen lamp, LED irradiator, LD irradiator, etc. By irradiating light of a wavelength, a cured light-shielding resin layer can be obtained.

The thickness of the light-shielding resin layer varies depending on the application,
When constituting the light-shielding adhesive layer, the thickness after drying is preferably 0.1 to 10 mm, more preferably 0.3 to 5 mm, and further preferably 0.5 to 3 mm. Preferably
In the case of constituting a light-shielding resin film, the thickness after drying is preferably 0.5 to 300 μm, and preferably 1 to 100 μm, considering that it is also used for color filters in liquid crystal panels. More preferably, it is 1-20 micrometers.

〔Compound〕
(1) Component A
(Compound a1) Urethane acrylate oligomer (UN-7700, manufactured by Negami Kogyo Co., Ltd.)
(Compound a2) Isobornyl acrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD RM-1002)
(2) Component B
(Compound b1) 1-hydroxycyclohexyl-phenyl ketone (Irgacure I-184 manufactured by BASF),
(Compound b2) Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Irgacure I-819 manufactured by BASF)
(3) Microcapsules: Microcapsules containing components C, D and E (Mitsubishi Pencil leuco dye TO62)
(4) Component D: Carbon black (NBD-0730 manufactured by Nihongo Bix)

[Photocurable resin composition]
(1) Example 1
After component B is added to component A, the mixture is heated and stirred at 60 ° C. for 30 minutes to dissolve component B, and then the microcapsules are added and stirred and mixed until uniform to obtain the viscosity of Example 1 A liquid photocurable resin composition was obtained.

(2) Example 2
After adding Component B to Component A, the mixture was heated and stirred at 60 ° C. for 30 minutes to dissolve Component B, and then the microcapsules were added and stirred and mixed until uniform to obtain the viscous liquid of Example 2. A photocurable resin composition was obtained.

(3) Comparative Example 1
After component B is added to component A, the mixture is heated and stirred at 60 ° C. for 30 minutes to dissolve component B, then carbon black is added and stirred and mixed until uniform, and the viscosity of Comparative Example 1 is obtained. A liquid photocurable resin composition was obtained.

(4) Comparative Example 2
After component B is added to component A, the mixture is heated and stirred at 60 ° C. for 30 minutes to dissolve component B, then carbon black is added and stirred and mixed until uniform, and the viscosity of Comparative Example 2 is obtained. A liquid photocurable resin composition was obtained.

〔Test method〕
(1) Deep-curing property The liquid photocurable resin composition is filled into the black tube from the inlet (6 mmφ) of the black tube (Denka Electron TB-6.0B), and high-pressure mercury from above the inlet. A lamp (LC5 manufactured by Hamamatsu Photonics) was irradiated with light having a wavelength of 365 nm and 300 mW / cm ² for 10 seconds. A cylindrical cured body was taken out from the black tube, and the length was measured with a micrometer.
It can be evaluated that the deep part curability is larger as the length of the cured body is larger.

(2) Transmittance The photocurable resin composition is sandwiched between transparent slide glasses (S1127 manufactured by Matsunami Glass Co., Ltd.) so as to form a liquid film having a thickness of 0.5 mm, and a metal halide lamp (ECS-301 manufactured by Eye Graphics Co., Ltd.). ) Was cured by irradiating light with a wavelength of 365 nm at 3000 mJ / cm ² to prepare a light-shielding resin layer.
The transmittance of the light-shielding resin layer was measured with an ultraviolet-visible spectrophotometer (V-570 manufactured by JASCO Corporation).

〔result〕

  From Table 1, the photocurable resin composition of the present invention containing components C (Examples 1 and 2) is a photocurable resin composition obtained by replacing the microcapsules containing component C with carbon black (Comparative Examples 1 and 2). ), The deep part curability is excellent, and it can be seen that the light-shielding resin layer produced has a very low transmittance and excellent light-shielding properties.

Claims (5)

Curable compound (component A), photopolymerization initiator (component B) and the following formula (1):
(Wherein R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom, which may be the same or different from each other; ₁ , X ₂ , Y ₁ , Y _{2 each} represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alicyclic ring or an aromatic ring, which may be the same or different from each other) A photocurable resin composition comprising component C).   The photocurable resin composition according to claim 1, wherein the photocurable resin composition comprises a microcapsule containing the component C. A method for producing a light-shielding resin layer comprising a step of forming a light-shielding resin layer by photocuring a liquid film-like photocurable resin composition,
The method for producing a light-shielding resin layer, wherein in the step, the liquid film-like photocurable resin composition has a light-shielding property at a predetermined temperature or less, and the light-shielding property is lowered when the predetermined temperature is exceeded.   The method for producing a light-shielding resin layer according to claim 3, wherein the predetermined temperature is in the range of 40 to 70 ° C.   The method for producing a light-shielding resin layer according to claim 3 or 4, wherein the photocurable resin composition is the photocurable resin composition according to claim 1 or 2.