JP6294689B2 - Photocurable composition - Google Patents

Description

  The present invention relates to a photocurable composition containing a photopolymerizable unsaturated compound having a specific structure.

The photocurable composition usually contains a colorant, a photopolymerizable unsaturated compound, and a photopolymerization initiator. Since this photocurable composition can be polymerized and cured by irradiating with ultraviolet rays or electron beams, particularly when a black pigment is used as a colorant, the R of the color filter is used in order to enhance display contrast and coloring effect. , G and B are useful as a black matrix provided at the boundary between colored layers.
Recently, in the black matrix manufacturing process, the adhesion of the black pattern obtained through exposure, development, and post-cure is not sufficient, and by repeating the peeling process to form the black pattern, There is a problem that a part of the formed colored pattern is peeled off at the same time, the pattern is lost, or the exposed and cured part remains on the transparent substrate.

Patent Document 1 below discloses a photocurable ink composition containing a monomer having an isocyanurate skeleton modified with ε-caprolactone, and Patent Document 2 below contains a monomer having a triazine structure as a binder resin. A color composition for a color filter is disclosed. Patent Document 3 below discloses a color composition for a color filter containing an isocyanurate skeleton-containing monomer. Patent Document 4 below discloses a polymerizable reactive group in the molecule. And a curable composition comprising an isocyanuric acid derivative having an alkylene oxide chain.
However, the photocurable compositions described in these documents are insufficient in sensitivity and adhesion.

JP 2010-143974 A Special table 2012-103587 gazette JP2013-164586A WO2009 / 090803

  Accordingly, an object of the present invention is to provide a photocurable composition which is excellent in sensitivity and adhesion and suitable as a color filter.

As a result of extensive studies, the present inventors have a specific structure as a photopolymerizable unsaturated compound in a photocurable composition containing a photopolymerizable unsaturated compound, a photopolymerization initiator, and a colorant. It has been found that the above object can be achieved by using two kinds of compounds.
That is, the present invention provides a reaction obtained by an esterification reaction of an epoxy addition compound having a structure in which an unsaturated monobasic acid is added to an epoxy compound represented by the following general formula (1) and a polybasic acid anhydride. Photopolymerizable unsaturated compound (A) having a structure as a product, photopolymerizable unsaturated compound (B) represented by the following general formula (2), photopolymerization initiator (C), and colorant (D) The photocurable composition containing is provided.

(In the formula, X ¹ is an alkylidene group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a substitution represented by the following formula (A), (B) or (C) R ¹ , R ² , R ³ and R ⁴ each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or 2 to 5 carbon atoms. The alkenyl group or halogen atom of m, and m represents an integer of 0 to 10.)

(In the formula, Y ¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a complex having 2 to 20 carbon atoms. A cyclic group or a halogen atom is represented, and the alkylene part in the alkyl group and arylalkyl group may be interrupted by an unsaturated bond, -O- or -S-, and Y ¹ is adjacent to Y ^1. And may form a ring, and n represents an integer of 0 to 4.)

Wherein Y ² and Z ² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, Represents a heterocyclic group having 2 to 20 carbon atoms, or a halogen atom, and the alkylene moiety in the alkyl group and arylalkyl group may be interrupted by an unsaturated bond, -O- or -S-, ² may form a ring with adjacent Z ² , p represents an integer of 0 to 4, q represents an integer of 0 to 8, r represents an integer of 0 to 4, and s represents The integer of 0-4 is represented, and the sum total of the number of r and s is an integer of 2-4.)

Wherein R ⁵ , R ⁶ and R ⁷ are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, carbon A heterocyclic group having 2 to 20 atoms or a substituent represented by the following general formula (3) or (4), and at least one of R ⁵ , R ⁶ and R ⁷ is represented by the following general formula (3) or (It is a substituent represented by (4).)

(Wherein R ⁸ is a hydrogen atom or a methyl group, R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are each independently a hydrogen atom, a methyl group or an ethyl group, and p and q are Independently, it is a number from 1 to 14, and s is a number from 0 to 5.)

(In the formula, R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , p, q and s are the same as those in the general formula (3).)

  Moreover, this invention provides the color filter using the said photocurable composition.

  The photocurable composition of the present invention is excellent in sensitivity and adhesion by containing two kinds of photopolymerizable unsaturated compounds having a specific structure. The cured product is suitable for a color filter for display devices, a liquid crystal display panel, and an organic EL display panel.

  Hereinafter, the photocurable composition of the present invention will be described based on preferred embodiments.

  The photocurable composition of the present invention is obtained by an esterification reaction between an epoxy addition compound having a structure in which an unsaturated monobasic acid is added to the epoxy compound represented by the general formula (1) and a polybasic acid anhydride. Photopolymerizable unsaturated compound (A) having a structure which is a reaction product obtained, photopolymerizable unsaturated compound (B) represented by the above general formula (5), photopolymerization initiator (C) and colorant (D) is contained. Hereinafter, each component will be described in order.

<Photopolymerizable unsaturated compounds (A) and (B)>
The photopolymerizable unsaturated compound used in the photocurable composition of the present invention has characteristics that allow polymerization in a state where the photopolymerization initiator is activated by light irradiation.
The photopolymerizable unsaturated compound (A) is an esterification reaction between an epoxy addition compound having a structure in which an unsaturated monobasic acid is added to the epoxy compound represented by the general formula (1) and a polybasic acid anhydride. The structure is a reaction product obtained by

In the general formula (1), examples of the alkylidene group having 1 to 4 carbon atoms represented by X ¹ include methylidene, ethylidene, propylidene, isopropylidene, butylidene, isobutylidene, trifluoromethylidene, and ditrifluoroisopropylidene. Named,
Examples of the alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by X ¹ include cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, 3-methylcyclopentylidene, cyclopentenylidene, Cyclohexenylidene, 3-methylcyclohexylidene, 3,3-dimethylcyclohexylidene, 3,5-dimethylcyclohexylidene, etc.
Examples of the alkyl group having 1 to 5 carbon atoms represented by R ¹ , R ² , R ³ and R ⁴ include methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso-butyl. , Amyl, iso-amyl, tert-amyl, etc.,
The R ^1, R ^2, R ³ and alkoxy group having 1 to 8 carbon atoms represented by R ^4, methyloxy, ethyloxy, iso- propyloxy, propyloxy, butyloxy, pentyloxy, iso- pentyloxy, Hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, etc.
Examples of the alkenyl group having 2 to 5 carbon atoms represented by R ¹ , R ² , R ³ and R ⁴ include vinyl, allyl, butenyl, propenyl,
Examples of the halogen atom represented by R ¹ , R ² , R ³ and R ⁴ include fluorine, chlorine, bromine and iodine.

In (i) which is X ¹ in the general formula (1), examples of the alkyl group having 1 to 20 carbon atoms represented by Y ¹ include the description of R ¹ , R ² , R ³ and R ⁴ . In addition to those exemplified, hexyl, heptyl, isoheptyl, t-heptyl, n-octyl, isooctyl, t-octyl, 2-ethylhexyl, n-nonyl, n-decyl, trifluoromethyl, difluoromethyl, monofluoromethyl, pentafluoro Ethyl, tetrafluoroethyl, trifluoroethyl, difluoroethyl, heptafluoropropyl, hexafluoropropyl, pentafluoropropyl, tetrafluoropropyl, trifluoropropyl, perfluorobutyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclo Octyl, cyclono Le, cyclodecyl and the like,
Examples of the aryl group having 6 to 30 carbon atoms represented by Y ¹ include phenyl, naphthyl, anthracen-1-yl, phenanthren-1-yl, o-tolyl, m-tolyl, p-tolyl, and 4-vinylphenyl. 3-isopropylphenyl, 4-isopropylphenyl, 4-butylphenyl, 4-isobutylphenyl, 4-t-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4- (2-ethylhexyl) Phenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4-di- t-butylphenyl, 2,5-di-t-butylphenyl, 2,6-di-t-butylphenyl, 2,4 Di-t-pentylphenyl, 2,5-di-t-amylphenyl, cyclohexylphenyl, biphenyl, 2,4,5-trimethylphenyl, 4-chlorophenyl, 3,4-dichlorophenyl, 4-trichlorophenyl, 4-triphenyl Fluorophenyl, perfluorophenyl and the like,
Examples of the arylalkyl group having 7 to 30 carbon atoms represented by Y ¹ include benzyl, phenethyl, 2-phenylpropyl, diphenylmethyl, triphenylmethyl, styryl, cinnamyl, 4-chlorophenylmethyl, and the like.
Examples of the heterocyclic group having 2 to 20 carbon atoms represented by Y ¹ include pyrrolyl, pyridyl, pyrimidyl, pyridazyl, piperazyl, piperidyl, pyranyl, pyrazolyl, triazyl, pyrrolidyl, quinolyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furyl , Furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, yurolidyl, morpholinyl, thiomorpholinyl, 2-pyrrolidinon-1-yl, 2 -Piperidone-1-yl, 2,4-dioxyimidazolidin-3-yl, 2,4-dioxyoxazolidine-3-yl and the like.
Examples of the halogen atom represented by Y ¹ include those exemplified in the description of R ¹ , R ² , R ³ and R ⁴ above.
Rings that may be formed by adjacent Y ¹ include cyclopentane ring, cyclohexane ring, cyclopentene ring, benzene ring, piperidine ring, morpholine ring, lactone ring, lactam ring and the like, and naphthalene ring , Condensed rings such as anthracene ring, fluorene ring, acenaphthene ring, indane ring and tetralin ring.

In (c) which is X ¹ in the general formula (1), the alkyl group having 1 to 20 carbon atoms represented by Y ² and Z ² , and having 6 to 30 carbon atoms Examples of the aryl group, the arylalkyl group having 7 to 30 carbon atoms and the heterocyclic group having 2 to 20 carbon atoms include those exemplified in the description of (i) which is X ¹ in the general formula (1). It is done.
Examples of the ring that may be formed by adjacent Z ² include the same ring as the ring that may be formed by adjacent Y ¹ in (i) which is X ¹ in the general formula (1). .

Among the epoxy compounds represented by the above general formula (I), those in which X ¹ is a substituent represented by the above formula (A), (B) or (C) are preferable.

Examples of the unsaturated monobasic acid that acts on the epoxy group of the epoxy compound include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate / malate, and the like. Examples thereof include hydroxyethyl acrylate / malate, hydroxypropyl methacrylate / malate, hydroxypropyl acrylate / malate and dicyclopentadiene / malate, among which acrylic acid and methacrylic acid are preferable.
In addition, the polybasic acid anhydride to be esterified after adding the unsaturated monobasic acid includes biphenyltetracarboxylic dianhydride, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, trimellitic acid Anhydride, pyromellitic anhydride, 2,2'-3,3'-benzophenone tetracarboxylic anhydride, ethylene glycol bisanhydro trimellitate, glycerol tris anhydro trimellitate, hexahydrophthalic anhydride, methyl tetrahydro Phthalic anhydride, nadic anhydride, methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride, trialkyltetrahydro Phthalic acid-maleic anhydride adduct, dodecenyl succinic anhydride, methyl hymic anhydride and the like, among them, succinic anhydride, biphenyltetracarboxylic dianhydride, diacid anhydrides such as pyromellitic anhydride, Alternatively, a combination of the diacid anhydride and a monoacid anhydride such as succinic anhydride is preferable.

The reaction molar ratio of the epoxy compound, the unsaturated monobasic acid and the polybasic acid anhydride is preferably as follows.
That is, an epoxy having a structure in which 0.1 to 1.0, preferably 0.3 to 1.0, carboxyl groups of the unsaturated monobasic acid are added to one epoxy group of the epoxy compound. In the adduct, the ratio of the acid anhydride structure of the polybasic acid anhydride is 0.1 to 1.0, preferably 0.3 to 1.0, with respect to one hydroxyl group of the epoxy adduct. It is preferable to do so.
Reaction of the said epoxy compound, the said unsaturated monobasic acid, and the said polybasic acid anhydride can be performed in accordance with a conventional method.

  The photopolymerizable unsaturated compound (B) used in the photocurable composition of the present invention is a compound represented by the above general formula (2).

In the general formula (2), an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms represented by R ⁵ , R ⁶ and R ⁷ and the heterocyclic group having 2 to 20 carbon atoms, those exemplified in the description of which is X ¹ in the general formula (1) (b) and the like.
Among the compounds represented by the general formula (2), those in which R ⁵ , R ⁶ and R ⁷ are represented by the general formula (3) or (4) are preferable because of high adhesion.

  As the compound represented by the general formula (2), commercially available compounds may be used. For example, A-9300-1CL, A-9300-2CL, A-9300-3CL, A-9300-6CL (new Nakamura Chemical Co., Ltd.), CIC acid acrylate (Shikoku Kasei Co., Ltd.), Aronix M-327, Aronix M-325 (Toagosei Co., Ltd.) and the like.

In the photocurable composition of the present invention, the content of the photopolymerizable unsaturated compound is the sum of the photopolymerizable unsaturated compounds (A) and (B) in the composition (excluding the solvent). , Preferably, it is 10-80 mass%, More preferably, it is 15-70 mass%.
Moreover, the ratio of the said photopolymerizable unsaturated compound (A) and (B) is a mass ratio, The said photopolymerizable unsaturated compound (A): The said photopolymerizable unsaturated compound (B) = 35-95: It is preferable that it is 5-65, and it is more preferable that it is 40-90: 10-60.

<Photopolymerization initiator (C)>
As the photopolymerization initiator (C) used in the photocurable composition of the present invention, conventionally known compounds can be used. For example, benzophenone, phenylbiphenyl ketone, 1-hydroxy-1-benzoylcyclohexane, 4-benzoyl-4′-methyldiphenyl sulfide, benzoin butyl ether, 2-hydroxy-2-benzoylpropane, 2-hydroxy-2- (4′-isopropyl) benzoylpropane, 4-butylbenzoyltrichloromethane, 4-phenoxybenzoyldichloromethane , Methyl benzoylformate, benzoin, 2-morpholyl-2- (4′-methylmercapto) benzoylpropane, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-benzyl-1-dimethylamino-1 -(4'-morpholinoben Zoyl) propane and other alkylphenone compounds; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2 Oxime ester compounds such as -methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime); thioxanthone compounds such as thioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diethylthioxanthone; Anthraquinone compounds such as ethyl anthraquinone; biimidazole compounds such as 2,2-bis (2-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1-2′-biimidazole; 2-methyl-4, 6-bis (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (to Triazine compounds such as (lichloromethyl) -s-triazine and 2-naphthyl-4,6-bis (trichloromethyl) -s-triazine; azo compounds such as 4,4-azobisisobutyronitrile; Oxides; 1,7-bis (9′-acridinyl) heptane, 9-n-butyl-3,6-bis (2′-morpholinoisobutyroyl) carbazole, triphenylphosphine, camphorquinone, etc. As products, N-1414, N-1717, N-1919, PZ-808, NCI-831, NCI-930 (manufactured by ADEKA), IRGACURE 184, IRGACURE 369, IRGACURE 651, IRGACURE 907, IRGACURE OXE 01, IRGACURE OX 01 02 (BASF Corporation) Ltd.) and the like.

  Especially as a photoinitiator used for the photocurable composition of this invention, the compound represented by following General formula (5) is preferable from a sensitivity and heat resistant point.

Wherein R ¹³ and R ¹⁴ are each independently a hydrogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl having 7 to 30 carbon atoms. Represents a group or a heterocyclic group having 2 to 20 carbon atoms,
R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, halogen atom, nitro group, cyano group, hydroxyl group, carboxyl group, R ¹⁷ , OR ¹⁸ , SR ¹⁹ , NR ²⁰ R ²¹ , COR ²² , SOR ²³ , SO _2. R ²⁴ or CONR ²⁵ R ²⁶ , R ¹⁵ and R ¹⁶ may be bonded to each other to form a ring;
R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ and R ²⁶ are each independently an alkyl group having 1 to 20 carbon atoms, 6 to 6 carbon atoms A 30 aryl group, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms;
X ² represents an oxygen atom, a sulfur atom, a selenium atom, CR ²⁷ R ²⁸ , CO, NR ²⁹ or PR ³⁰ ;
X ³ represents a single bond or CO,
R ²⁷ , R ²⁸ , R ²⁹ and R ³⁰ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms or an arylalkyl group having 7 to 30 carbon atoms. The alkyl group or arylalkyl group may be substituted with a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group or a heterocyclic group, and the methylene group in the alkyl group or arylalkyl group is —O. -May be interrupted by-
R ²⁷ , R ²⁸ , R ²⁹ and R ³⁰ may each independently form a ring together with one of the adjacent benzene rings,
a represents an integer of 0 to 4,
b represents an integer of 0 to 5. )

In the above general formula (5), R ¹³ , R ¹⁴ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ and R ³⁰ , an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an arylalkyl group having 7 to 30 carbon atoms R ¹³ , R ¹⁴ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ and R ²⁶ , the heterocyclic group having 2 to 20 carbon atoms is represented by X ¹ in the general formula (1). What is illustrated in the description of (A).
Examples of the heterocyclic group that may be substituted for the alkyl group or arylalkyl group represented by R ²⁷ , R ²⁸ , R ^29, and R ³⁰ are X ¹ in the above general formula (1). Examples thereof are the same as the heterocyclic groups exemplified in the above.
The ring which R ¹⁵ and R ¹⁶ may be bonded to each other is the same as the ring which may be formed by adjacent Y ¹ in (a) which is X ¹ in the general formula (1). A ring is mentioned.

Among the compounds represented by the general formula (5), compounds represented by the following general formula (5 ′) are preferable, and those in which R ¹⁶ is a nitro group or COR ²² are particularly preferable.
(In formula, R <^13> , R <^14> , R <^15> , R <^16> , R <^29> , X < ³ >, a and b are the same as the said General formula (5).

  In the photocurable composition of the present invention, the content of the photopolymerization initiator (C) is 0.1 to 30% by mass, particularly 0.5 to 10%, in the solid content of the photocurable composition of the present invention. Mass% is preferred. When the content of the photopolymerization initiator is less than 0.1% by mass, curing by exposure may be insufficient, and when it is greater than 30% by mass, the initiator may be precipitated in the resin composition. .

<Colorant (D)>
As the colorant (D) used in the photocurable composition of the present invention, an inorganic color material or an organic color material can be used, and these can be used alone or in admixture of two or more.
Examples of the inorganic color material or organic color material include nitroso compounds, nitro compounds, azo compounds, diazo compounds, xanthene compounds, quinoline compounds, anthraquinone compounds, coumarin compounds, phthalocyanine compounds, isoindolinone compounds, isoindoline compounds, and quinacridones. Compound, anthanthrone compound, perinone compound, perylene compound, diketopyrrolopyrrole compound, thioindigo compound, dioxazine compound, triphenylmethane compound, quinophthalone compound, naphthalenetetracarboxylic acid; azo dye, metal complex compound of cyanine dye; lake pigment; hydrophobic Resin, chromium oxide green, miloli blue, cobalt green, cobalt blue, manganese, ferrocyanide, phosphate ultramarine, bitumen, ultramarine, cerulean blue, pyridian, Main lardo green, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron oxide (III)), cadmium red, can be used inorganic or organic pigments amber like.

  As the inorganic color material or organic color material, commercially available pigments can also be used. For example, Pigment Red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 3, 95, 97, 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175, 180, 185; Pigment Green 7, 10, 36; Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 22, 24, 56, 60, 61, 62, 64; pigment violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 50, and the like.

  As the inorganic color material or organic color material, known dyes can be used. Known dyes include, for example, azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, Examples thereof include phthalocyanine dyes and cyanine dyes.

  In the photocurable composition of the present invention, the content of the colorant (D) is preferably 10 to 350 masses with respect to a total of 100 mass parts of the photopolymerizable unsaturated compounds (A) and (B). Part, more preferably 20 to 250 parts by weight. When it exceeds 350 parts by mass, the colorant tends to aggregate and storage stability is deteriorated.

  A dispersant can be further used in the photocurable composition of the present invention. As the dispersant, any dispersant can be used as long as it can disperse and stabilize the colorant (D). Commercially available dispersants such as BYK series manufactured by Big Chemie can be used, and polyester having a basic functional group. , A polymer dispersant made of polyether or polyurethane, having a nitrogen atom as a basic functional group, the functional group having a nitrogen atom is an amine and / or a quaternary salt thereof, and an amine value of 1 to 100 mgKOH / g Are preferably used.

  In the photocurable composition of the present invention, a polymerizable compound having an ethylenically unsaturated bond other than that represented by the general formula (2) can be further used. The polymerizable compound having an ethylenically unsaturated bond is not particularly limited, and those conventionally used in photosensitive compositions can be used. For example, ethylene, propylene, butylene, isobutylene, vinyl chloride can be used. , Unsaturated aliphatic hydrocarbons such as vinylidene chloride, vinylidene fluoride, tetrafluoroethylene; (meth) acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, hymic acid, crotonic acid, Isocrotonic acid, vinyl acetate, allyl acetate, cinnamic acid, sorbic acid, mesaconic acid, succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω- A carboxypolycaprolactone mono (meth) acrylate, etc. having a carboxy group and a hydroxyl group at both ends Mer mono (meth) acrylates; having hydroxyethyl (meth) acrylate malate, hydroxypropyl (meth) acrylate malate, dicyclopentadiene malate or one carboxyl group and two or more (meth) acryloyl groups Unsaturated monobasic acids such as polyfunctional (meth) acrylates; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, the following compound No. A1-No. A4, methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, (t-butyl) (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, ( Isooctyl (meth) acrylate, isononyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, dimethyl (meth) acrylate Aminoethyl, aminopropyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, ethoxyethyl (meth) acrylate, poly (ethoxy) ethyl (meth) acrylate, butoxyethoxyethyl (meth) acrylate, (meta ) Ethylhexyl acrylate, (meth) acrylic acid Phenoxyethyl, tetrahydrofuryl (meth) acrylate, vinyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol Di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolethanetri (Meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol Unsaturated monobasic acids such as tra (meth) acrylate, pentaerythritol tri (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, tri [(meth) acryloylethyl] isocyanurate, polyester (meth) acrylate oligomers and the like Esters of polyhydric alcohols or polyphenols; metal salts of unsaturated polybasic acids such as zinc (meth) acrylate and magnesium (meth) acrylate; maleic anhydride, itaconic anhydride, citraconic anhydride, methyl Tetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydro Phthalic anhydride-anhydrous Acid anhydrides of unsaturated polybasic acids such as rain acid adducts, dodecenyl succinic anhydride, methyl hymic anhydride; (meth) acrylamide, methylene bis- (meth) acrylamide, diethylenetriamine tris (meth) acrylamide, xylylene bis (meth) Unsaturated monobasic acids such as acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide and amides of polyvalent amines; unsaturated aldehydes such as acrolein; (meth) acrylonitrile, α-chloroacrylonitrile, cyanide Unsaturated nitriles such as vinylidene and allyl cyanide; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinyl Unsaturated aromatic compounds such as ruphenol, vinyl sulfonic acid, 4-vinylbenzene sulfonic acid, vinyl benzyl methyl ether, vinyl benzyl glycidyl ether; unsaturated ketones such as methyl vinyl ketone; vinyl amine, allyl amine, N-vinyl pyrrolidone, vinyl Unsaturated amine compounds such as piperidine; vinyl alcohols such as allyl alcohol and crotyl alcohol; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether, allyl glycidyl ether; maleimide, N-phenylmaleimide, N -Unsaturated imides such as cyclohexylmaleimide; Indenes such as indene and 1-methylindene; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene Macromolecules having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, polysiloxane, etc .; vinyl chloride, vinylidene chloride, divinyls Cuccinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, hydroxyl group-containing vinyl monomers and vinyl isocyanate compounds of polyisocyanate compounds, hydroxyl groups Examples thereof include vinyl monomers containing vinyl monomers and polyepoxy compounds.

  In addition, as the polymerizable compound having an ethylenically unsaturated bond, an acrylic ester copolymer, a phenol and / or cresol novolac epoxy resin, or a polyphenylmethane type epoxy resin having a polyfunctional epoxy group may be used. it can.

Among the polymerizable compounds having an ethylenically unsaturated bond, when a compound having an acid value is used, alkali developability can be imparted to the photocurable composition of the present invention. When using the compound which has the said acid value, it is preferable to make the usage-amount become 50-99 mass% of the whole polymeric compound which has the said ethylenically unsaturated bond.
The compound having the acid value can be used after adjusting the acid value by further reacting with a monofunctional or polyfunctional epoxy compound. By adjusting the acid value of the compound having an acid value, the alkali developability of the photocurable composition can be improved. The compound having an acid value (that is, a polymerizable compound having an ethylenically unsaturated bond imparting alkali developability) preferably has a solid content acid value in the range of 5 to 120 mgKOH / g, and is monofunctional or polyfunctional. The amount of the functional epoxy compound used is preferably selected so as to satisfy the acid value.

  Examples of the monofunctional epoxy compound include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, t-butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl. Glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-ethylhexyl glycidyl ether, Allyl glycidylate , Propargyl glycidyl ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxy glycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl ether, 2-methyl cresyl glycidyl ether, 4-nonylphenyl glycidyl ether, benzyl glycidyl Ether, p-cumylphenyl glycidyl ether, trityl glycidyl ether, 2,3-epoxypropyl methacrylate, epoxidized soybean oil, epoxidized linseed oil, glycidyl butyrate, vinylcyclohexane monooxide, 1,2-epoxy-4-vinyl Cyclohexane, styrene oxide, pinene oxide, methyl styrene oxide, cyclohexene oxide, propylene oxide, the above-mentioned compound no. A2, No. A3 etc. are mentioned.

As the polyfunctional epoxy compound, it is preferable to use one or more compounds selected from the group consisting of bisphenol-type epoxy compounds and glycidyl ethers because a photocurable composition with better characteristics can be obtained.
As said bisphenol-type epoxy compound, the epoxy compound represented by the said General formula (1) can be used, For example, bisphenol-type epoxy compounds, such as a hydrogenated bisphenol-type epoxy compound, can also be used.
Examples of the glycidyl ethers include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl Ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri (glycidyloxymethyl) propane, 1,1,1-to (Glycidyloxymethyl) ethane, 1,1,1-tri (glycidyloxymethyl) methane, 1,1,1,1- tetra (glycidyloxymethyl) can be used such as methane.
Other novolac epoxy compounds such as phenol novolac epoxy compounds, biphenyl novolac epoxy compounds, cresol novolac epoxy compounds, bisphenol A novolac epoxy compounds, dicyclopentadiene novolac epoxy compounds; 3,4-epoxy-6-methyl Cycloaliphatic epoxies such as cyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane Compound: Glycidyl esters such as diglycidyl phthalate, diglycidyl tetrahydrophthalate, glycidyl dimer, tetraglycidyl diamino Glycidylamines such as phenylmethane, triglycidyl P-aminophenol and N, N-diglycidylaniline; heterocyclic epoxy compounds such as 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate; Dioxide compounds such as pentadiene dioxide; naphthalene type epoxy compounds; triphenylmethane type epoxy compounds; dicyclopentadiene type epoxy compounds can also be used.

  In addition, the photocurable composition of the present invention may contain a compound that does not have an ethylenically unsaturated bond and imparts alkali developability. The compound is not particularly limited as long as it is a compound that is soluble in an aqueous solution, but a typical example is an alkali-soluble novolak resin (hereinafter simply referred to as “novolak resin”). The novolak resin is obtained by polycondensation of phenols and aldehydes in the presence of an acid catalyst.

  Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2, 3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, p-phenylphenol, hydroquinone, catechol, resorcinol, 2- Methyl resorcinol, pyrogallol, α-naphthol, bisphenol A, dihydroxybenzoic acid ester, gallic acid ester and the like are used. Among these phenols, phenol, o-cresol, m-cresol, p-cresol, 2,5-xy Nord, 3,5-xylenol, 2,3,5-trimethylphenol, resorcinol, 2-methyl resorcinol and bisphenol A are preferred. These phenols are used alone or in combination of two or more.

  Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o -Chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, p N-butylbenzaldehyde and the like are used, and among these compounds, formal Dehydr, acetaldehyde and benzaldehyde are preferred. These aldehydes may be used alone or in combination of two or more. Aldehydes are preferably used in a proportion of 0.7 to 3 mol, particularly preferably 0.7 to 2 mol, per mol of phenol.

Examples of the acid catalyst include inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid, or organic acids such as formic acid, oxalic acid, and acetic acid. The amount of these acid catalysts used is preferably 1 × 10 ^{−4 to} 5 × 10 ⁻¹ mol per mol of phenols. In the condensation reaction, water is usually used as a reaction medium. However, if the phenols used in the condensation reaction do not dissolve in an aqueous solution of aldehydes and become heterogeneous from the beginning of the reaction, the reaction medium is hydrophilic. A solvent can also be used. Examples of these hydrophilic solvents include alcohols such as methanol, ethanol, propanol and butanol, and cyclic ethers such as tetrahydrofuran and dioxane. The amount of these reaction media used is usually 20 to 1000 parts by mass per 100 parts by mass of the reaction raw material. Although the reaction temperature of a condensation reaction can be suitably adjusted according to the reactivity of a reaction raw material, it is 10-200 degreeC normally, Preferably it is 70-150 degreeC. After completion of the condensation reaction, in order to remove unreacted raw materials, acid catalyst and reaction medium present in the system, the internal temperature is generally raised to 130 to 230 ° C., and the volatile component is distilled off under reduced pressure. Next, the melted novolac resin is collected on a steel belt or the like.
After completion of the condensation reaction, the reaction mixture is dissolved in the hydrophilic solvent and added to a precipitating agent such as water, n-hexane or n-heptane to precipitate a novolak resin, and the precipitate is separated and dried by heating. It can also be recovered by doing so.

  Examples other than the novolak resin include polyhydroxystyrene or a derivative thereof, styrene-maleic anhydride copolymer, polyvinylhydroxybenzoate, and the like.

  A silane coupling agent can be further used in the photocurable composition of the present invention. Examples of the silane coupling agent include dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltrimethoxysilane. Alkyl-functional alkoxysilanes, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane and other alkenyl-functional alkoxysilanes, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane , 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 2-methacryloxypropyltrimethoxysilane, etc. (Meth) acrylic acid ester functional alkoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ- ( Epoxy-functional alkoxysilanes such as 3,4-epoxycyclohexyl) propyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-amino Amino-functional alkoxysilanes such as propyltrimethoxysilane, mercaptofunctional alkoxysilanes such as γ-mercaptopropyltrimethoxysilane, titanium alkoxides such as titanium tetraisopropoxide, titanium tetranormal butoxide, titanium dioctyro Titanium chelates such as cibis (octylene glycolate) and titanium diisopropoxybis (ethyl acetoacetate), zirconium chelates such as zirconium tetraacetylacetonate and zirconium tributoxymonoacetylacetonate, zirconium tributoxy monostearate, etc. Zirconium acylates, isocyanate silanes such as methyl triisocyanate silane, etc. can be used, and in particular, alkyl functional alkoxy silane, epoxy functional alkoxy silane, and isocyanate silane are preferable because of high adhesion in a heat and humidity test. .

  Although the usage-amount of the said silane coupling agent is not specifically limited, Preferably, it is the range of 1-20 mass parts with respect to 100 mass parts of whole quantity of the solid substance in a photocurable composition.

  A solvent can be further added to the photocurable composition of the present invention. As the solvent, the above components (photopolymerizable unsaturated compounds (A) and (B) of the present invention, photopolymerization initiator (C), colorant (D), etc.) are usually dissolved as necessary. Or dispersible solvents such as ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane Ether solvents such as 1,2-diethoxyethane and dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, texanol Ester solvents such as ethylene glycol mono Cellosolve solvents such as tilether, ethylene glycol monoethyl ether; alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol; ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, Ether ester solvents such as propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate and ethoxyethyl propionate; BTX solvents such as benzene, toluene and xylene Aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; terpene hydrocarbon oils such as turpentine oil, D-limonene and pinene; minerals Paraffin solvents such as Pyrit, Swazol # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.); Halogenation of carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1,2-dichloroethane, etc. Aliphatic hydrocarbon solvents; halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N-dimethylformamide, N, N-dimethyl Examples include acetamide, N-methylpyrrolidone, dimethyl sulfoxide, water, and the like, and these solvents can be used as one or a mixture of two or more. Among these, ketones, ether ester solvents and the like, particularly propylene glycol-1-monomethyl ether-2-acetate (PGMEA), cyclohexanone, and the like are preferable because the compatibility of the resist and the photopolymerization initiator in the colored composition is good.

  In the photocurable composition of the present invention, the amount of the solvent used is preferably such that the concentration of the composition other than the solvent is 5 to 30% by mass, and if it is less than 5% by mass, the film thickness may be increased. It is difficult and is not preferable because it cannot sufficiently absorb light of a desired wavelength. When it exceeds 30% by mass, the storage stability of the composition due to the precipitation of the composition is reduced, and the handling is reduced because the viscosity is improved. It is not preferable.

  The photocurable composition of the present invention can further contain an inorganic compound. Examples of the inorganic compound include metal oxides such as nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silica, and alumina; lamellar clay mineral, miloli blue, calcium carbonate, Magnesium carbonate, cobalt, manganese, glass powder, mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, aluminum silicate, calcium silicate, aluminum hydroxide, platinum, gold, silver, copper Among these, titanium oxide, silica, layered clay mineral, silver and the like are preferable. In the photocurable composition of the present invention, the content of the inorganic compound is preferably 0.1 to 50 parts by mass with respect to a total of 100 parts by mass of the photopolymerizable unsaturated compounds (A) and (B). More preferably, it is 0.5-20 mass parts, and these inorganic compounds can use 1 type (s) or 2 or more types.

By containing an inorganic compound in the photocurable composition of the present invention, it can be used as a photosensitive paste composition. The photosensitive paste composition is used to form a fired product pattern such as a partition pattern, a dielectric pattern, an electrode pattern, and a black matrix pattern of a plasma display panel.
These inorganic compounds are also suitably used as, for example, fillers, antireflection agents, conductive agents, stabilizers, flame retardants, mechanical strength improvers, special wavelength absorbers, ink repellents, and the like.

  In addition, the photocurable composition of the present invention includes, if necessary, a thermal polymerization inhibitor such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, phenothiazine; a plasticizer; an adhesion promoter; a filler; Conventional additives such as an antifoaming agent, a leveling agent, a surface conditioner, an antioxidant, an ultraviolet absorber, a dispersion aid, a coagulation inhibitor, a catalyst, an effect promoter, a crosslinking agent, and a thickener can be added. .

  In the photocurable composition of the present invention, the inclusion of optional components other than the photopolymerizable unsaturated compounds (A) and (B), the photopolymerization initiator (C), and the colorant (D) (excluding the solvent) The amount is appropriately selected according to the purpose of use and is not particularly limited, but is preferably 50 parts by mass or less in total with respect to 100 parts by mass in total of the photopolymerizable unsaturated compounds (A) and (B). .

  Further, a chain transfer agent, a sensitizer, a surfactant, a melamine compound and the like can be used in combination with the photocurable composition of the present invention.

  As the chain transfer agent and sensitizer, a sulfur atom-containing compound is generally used. For example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- ( 2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol , 2-me Captoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3- Mercapto compounds such as mercaptopropionate), disulfide compounds obtained by oxidizing the mercapto compounds, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc. Alkyl compound, trimethylolpropane tris (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4- Methyl mercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate , Trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tristhiopropionate, the following compound no. C1, Karenz PE1, NR1 manufactured by Showa Denko KK and the like.

  Examples of the surfactant include fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates, anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates, and higher amines. Cationic surfactants such as halogenates and quaternary ammonium salts, nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters and fatty acid monoglycerides, amphoteric surfactants, silicone surfactants Surfactants such as agents can be used, and these may be used in combination.

Examples of the melamine compound include all or part of active methylol groups (CH ₂ OH groups) in nitrogen compounds such as (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, and (poly) methylol urea. Mention may be made of compounds in which (at least two) are alkyl etherified. Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, and a butyl group, which may be the same as or different from each other. Moreover, the methylol group which is not alkyletherified may be self-condensed within one molecule, or may be condensed between two molecules, and as a result, an oligomer component may be formed. Specifically, hexamethoxymethyl melamine, hexabutoxymethyl melamine, tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril and the like can be used. Among these, alkyl etherified melamines such as hexamethoxymethyl melamine and hexabutoxymethyl melamine are preferable.

In the photocurable composition of the present invention, the volume resistivity is 1 × 10 ¹¹ Ω · cm or more, and preferably 1 × 10 ¹³ Ω · cm or more from the viewpoint of non-conductivity. The surface resistivity is 1 × 10 ¹³ Ω · cm or more, and preferably 1 × 10 ¹⁴ Ω · cm or more from the viewpoint of non-conductivity.

  The photocurable composition of the present invention is a known method such as spin coater, roll coater, bar coater, die coater, curtain coater, various printing, dipping, soda glass, quartz glass, semiconductor substrate, metal, paper, It can be applied on a supporting substrate such as plastic. Moreover, after once applying on support bases, such as a film, it can also transfer on another support base | substrate, There is no restriction | limiting in the application method.

  Moreover, as the light source of the active light used when curing the photocurable composition of the present invention, one that emits light having a wavelength of 300 to 450 nm can be used, for example, ultrahigh pressure mercury, mercury vapor arc, Carbon arc, xenon arc, etc. can be used.

  Furthermore, by using laser light as the exposure light source, the laser direct drawing method that directly forms an image from digital information such as a computer without using a mask improves not only productivity but also resolution and positional accuracy. As the laser light, light having a wavelength of 340 to 430 nm is preferably used, but an argon ion laser, a helium neon laser, a YAG laser, a semiconductor laser, etc. are visible to infrared region. Those that emit light are also used. When these lasers are used, a sensitizing dye that absorbs the region from visible to infrared is added.

  The photocurable composition of the present invention (or a cured product thereof) is a photocurable paint or varnish, a photocurable adhesive, a printed circuit board, a color television, a PC monitor, a portable information terminal, a digital camera or the like. Color filters for LCD panels, color filters for CCD image sensors, touch panels, electrode materials for plasma display panels, powder coatings, printing inks, printing plates, adhesives, gel coats, photoresists for electronics, electroplating resists, etching For manufacturing resists, liquid and dry films, solder resists, insulating films, color filters for various display applications, or for forming structures in the manufacturing process of plasma display panels, electroluminescent display devices, and LCDs Composition, solder for encapsulating resist, electrical and electronic components Resist, magnetic recording materials, micromechanical components, waveguides, optical switches, plating masks, etching masks, color test systems, glass fiber cable coatings, stencils for screen printing, materials for manufacturing 3D objects by stereolithography Holographic recording material, image recording material, fine electronic circuit, decoloring material, decoloring material for image recording material, decoloring material for image recording material using microcapsules, photoresist material for printed wiring board, UV and visible It can be used for various applications such as a photoresist material for a laser direct image system, a photoresist material used for forming a dielectric layer in the sequential lamination of printed circuit boards, or a protective film, and the application is not particularly limited.

  The photocurable composition of the present invention is used for the purpose of forming a black matrix when a black pigment is used, and the black matrix is particularly useful for a color filter for a display device for an image display device such as a liquid crystal display panel. It is.

The black matrix comprises (1) a step of forming a coating film of the photocurable composition of the present invention on a substrate, and (2) a step of irradiating the coating film with active light through a mask having a predetermined pattern shape. (3) The step of developing the exposed film with a developer (particularly an alkali developer) and (4) the step of heating the film after development are preferably formed. The photocurable composition of the present invention is also useful as an ink jet system composition without a development step.
Manufacture of color filters for use in liquid crystal display panels, etc. is made by repeating the above steps (1) to (4) using the photocurable composition of the present invention or other combinations, and combining patterns of two or more colors. can do.

  Hereinafter, although an example etc. are given and the present invention is explained still in detail, the present invention is not limited to these examples.

[Production Example 1] Photopolymerizable unsaturated compound No. 1 Production of 1 1,1-bis [4- (2,3-epoxypropyloxy) phenyl] indane 30.0 g, acrylic acid 7.52 g, 2,6-di-t-butyl-p-cresol 0.080 g Then, 0.183 g of tetrabutylammonium chloride and 11.0 g of PGMEA were charged and stirred at 90 ° C. for 1 hour, 105 ° C. for 1 hour and 120 ° C. for 17 hours. After cooling to room temperature, 8.11 g of succinic anhydride, 0.427 g of tetrabutylammonium chloride and 11.1 g of PGMEA were added, and the mixture was stirred at 100 ° C. for 5 hours. Further, 12.0 g of 1,1-bis [4- (2,3-epoxypropyloxy) phenyl] indane, 0.080 g of 2,6-di-t-butyl-p-cresol and 0.600 g of PGMEA were added. After stirring at 90 ° C. for 90 minutes and at 120 ° C. for 5 hours, 24.0 g of PGMEA was added to prepare PGMEA solution as a photopolymerizable unsaturated compound no. 1 was obtained.

[Production Example 2] Photopolymerizable unsaturated compound No. 1 Production of 2 9,9-bis (4-glycidyloxyphenyl) fluorene 75.0 g, acrylic acid 23.8 g, 2,6-di-t-butyl-p-cresol 0.273 g, tetrabutylammonium chloride 0.585 g And PGMEA 65.9 g, and stirred at 90 ° C. for 1 hour, 100 ° C. for 1 hour, 110 ° C. for 1 hour and 120 ° C. for 14 hours. After cooling to room temperature, 25.9 g of succinic anhydride, 0.427 g of tetrabutylammonium chloride, and 1.37 g of PGMEA were added, and the mixture was stirred at 100 ° C. for 5 hours. Further, 90.0 g of 9,9-bis (4-glycidyloxyphenyl) fluorene, 0.269 g of 2,6-di-t-butyl-p-cresol and 1.50 g of PGMEA were added, and 90 minutes at 90 ° C. After stirring at 120 ° C. for 4 hours, 93.4 g of PGMEA was added, and the photopolymerizable unsaturated compound No. 1 as the target product as a PGMEA solution was added. 2 was obtained.

[Production Example 3] Photopolymerizable unsaturated compound No. 1 3 Preparation of bis [4- (2,3-epoxypropoxy) phenyl] -4-biphenylyl (cyclohexyl) methane 89.9 g, acrylic acid 23.5 g, 2,6-di-tert-butyl-p-cresol 457 g, benzyltriethylammonium chloride 0.534 g and PGMEA 75.6 g were charged and stirred at 120 ° C. for 16 hours. The mixture was cooled to room temperature, charged with 12.0 g of 2,4-pentanedione and 1.0 g of triethylamine, and stirred at 92 ° C. for 17 hours. After cooling to room temperature, 25.6 g of succinic anhydride, 1.39 g of tetra-n-butylammonium bromide and 40.42 g of PGMEA were added and stirred at 100 ° C. for 5 hours. After cooling to room temperature, 46.7 g of PGMEA was added, and the photopolymerizable unsaturated compound No. 1 as the target product as a PGMEA solution was added. 3 was obtained.

[Comparative Production Example 1] Comparative photopolymerizable unsaturated compound No. 1 1 Preparation of 35.0 g of bisphenol A diglycidyl ether, 7.52 g of acrylic acid, 0.080 g of 2,6-di-t-butyl-p-cresol, 0.183 g of tetrabutylammonium chloride and 11.0 g of PGMEA The mixture was stirred at 90 ° C. for 1 hour, 105 ° C. for 1 hour, and 120 ° C. for 17 hours. After cooling to room temperature, 8.11 g of succinic anhydride, 0.427 g of tetrabutylammonium chloride and 11.1 g of PGMEA were added, and the mixture was stirred at 100 ° C. for 5 hours. Further, 12.0 g of 1,1-bis [4- (2,3-epoxypropyloxy) phenyl] indane, 0.080 g of 2,6-di-t-butyl-p-cresol and 0.600 g of PGMEA were added. After stirring at 90 ° C. for 90 minutes and at 120 ° C. for 5 hours, 24.0 g of PGMEA was added to prepare a PGMEA solution as a comparative photopolymerizable unsaturated compound no. 1 was obtained.

[Examples 1 to 5 and Comparative Examples 1 to 4] Photocurable composition No. 1-No. 5 and comparative photocurable composition No. 1-No. Preparation of 4
Each component was mixed in accordance with the formulation of [Table 1], and finely pulverized with a ball mill. 1-No. No. 5 and Comparative Photocurable Composition Nos. 1-No. 4 was obtained. In addition, a number represents a mass part.

A-1 Photopolymerizable unsaturated compound No. 1 1
A-2 Photopolymerizable unsaturated compound No. 2
A-3 Photopolymerizable unsaturated compound No. 3
A′-1 Comparative photopolymerizable unsaturated compound No. 1 1
B-1 Aronix M-327 (compound represented by general formula (2); manufactured by Toagosei Co., Ltd.)
B'-1 Kayalad DPHA (dipentaerythritol hexaacrylate; manufactured by Nippon Kayaku Co., Ltd.)
B'-2 Aronix M-315 (isocyanurate-containing triacrylate; manufactured by Toagosei Co., Ltd.)
B'-3 Kayarad DPCA-120 (dipentaerythritol caprolactone-modified hexaacrylate; manufactured by Nippon Kayaku Co., Ltd.)
C-1 NCI-831 (Compound represented by the general formula (5 ′); manufactured by ADEKA)
C-2 OXE-02 (manufactured by BASF)
D-1 MA100 (carbon black; manufactured by Mitsubishi Chemical Corporation)
E-1 KBM403 (alkoxysilane coupling agent; Shin-Etsu Chemical)
E-2 PGMEA

[Evaluation Examples 1 to 5 and Comparative Evaluation Examples 1 to 4]
After spin coating γ-glycidoxypropylmethylethoxysilane on the substrate and spin drying well, the photocurable compositions No. 1 obtained in Examples 1 to 5 were used. 1-No. 5 and Comparative Photocurable Composition Nos. Obtained in Comparative Examples 1-4. 1-No. 4 was spin coated (1300 rpm, 50 seconds) and dried. After pre-baking at 70 ° C. for 20 minutes, a 5% polyvinyl alcohol solution was coated to form an oxygen barrier film. After drying at 70 ° C. for 20 minutes, using a predetermined mask, using an ultra-high pressure mercury lamp as a light source, exposure was performed, soaked in a 2.5% sodium carbonate solution at 25 ° C. for 30 seconds, developed, and washed thoroughly with water. . After washing with water and drying, the pattern was fixed by baking at 230 ° C. for 1 hour. About the obtained pattern, the following sensitivity and adhesion evaluation (seal strength and adhesion test) were measured. The results are shown in [Table 1].
(sensitivity)
During exposure, what exposure was sufficient 70 mJ / cm ² a, inadequate in 70 mJ / cm ^2, those exposed at 100 mJ / cm ² b, insufficient in 100mJ / cm ^2, 150mJ / cm ^The one exposed in ² was designated as c.
(Seal strength)
A thermosetting adhesive (sealing agent: XN-21S manufactured by Mitsui Chemicals, Inc.) was applied to a glass substrate with an area of 6 mm × 3.5 mm, and bonded to a glass substrate having a resin black matrix layer to cure the adhesive. . The bonded substrates were left in a high temperature and high humidity apparatus under conditions of 120 ° C., 2 atm, and relative humidity 100% for 5 hours. This sample was subjected to a three-point support bending test using Shimadzu EZ-Graph, and the adhesion strength was measured to obtain the seal strength.
(Adhesion test)
According to the test method of JIS D 0202, a cross-cut is put in a base form in a coating film that has been allowed to stand in a high-temperature and high-humidity device under conditions of 120 ° C., 2 atm, and relative humidity of 100%. Then, the peeled state of the substrate eyes was visually evaluated. A sample in which no peeling was observed was marked with ○, and a sample in which peeling was observed was marked with ×.

  From the above results, the photocurable composition of the present invention containing a photopolymerizable unsaturated compound having a specific structure is excellent in sensitivity and adhesion. Therefore, the photocurable composition of the present invention is useful for a color filter.

Claims (6)

A structure which is a reaction product obtained by an esterification reaction between an epoxy addition compound having a structure obtained by adding an unsaturated monobasic acid to an epoxy compound represented by the following general formula (1) and a polybasic acid anhydride A photocurable unsaturated compound (A) having, a photopolymerizable unsaturated compound (B) represented by the following general formula (2), a photopolymerization initiator (C) and a colorant (D) Composition.
(Wherein, X ¹ is a substituent represented by an alkylidene group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or the following formula (a), young properly is (c) R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkyl group having 2 to 5 carbon atoms. Represents an alkenyl group or a halogen atom, and m represents an integer of 0 to 10.)
(In the formula, Y ¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a complex having 2 to 20 carbon atoms. A cyclic group or a halogen atom is represented, and the alkylene part in the alkyl group and arylalkyl group may be interrupted by an unsaturated bond, -O- or -S-, and Y ¹ is adjacent to Y ^1. And may form a ring, and n represents an integer of 0 to 4.)
Wherein Y ² and Z ² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, Represents a heterocyclic group having 2 to 20 carbon atoms, or a halogen atom, and the alkylene moiety in the alkyl group and arylalkyl group may be interrupted by an unsaturated bond, -O- or -S-, ² may form a ring with adjacent Z ² , p represents an integer of 0 to 4, q represents an integer of 0 to 8, r represents an integer of 0 to 4, and s represents The integer of 0-4 is represented, and the sum total of the number of r and s is an integer of 2-4.)
(Wherein, R ^5, R ⁶ and R ⁷ are each independently a substituent group represented by the following following general formula (3) or (4), R ^5, R ⁶ and R ⁷ each formula (The sum of s in (3) or (4) is 1, 2, 3 or 6. )
(Wherein R ⁸ is a hydrogen atom or a methyl group, R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are each independently a hydrogen atom, a methyl group or an ethyl group, and p and q are Independently, it is a number from 1 to 14, and s is a number from 0 to 5.)
(In the formula, R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , p, q and s are the same as those in the general formula (3).) In general formula (2), R ^Five , R ⁶ And R ⁷ Are each independently a substituent represented by the following general formula (3 '); ^Five , R ⁶ And R ⁷ The photocurable composition according to claim 1, wherein the sum of s in each general formula (3 ′) is 1, 2, 3 or 6.
(In the formula, s is a number from 0 to 5.) The photocurable composition according to claim 1 or 2, wherein the photopolymerization initiator ( C ) is represented by the following general formula (5).
Wherein R ¹³ and R ¹⁴ are each independently a hydrogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl having 7 to 30 carbon atoms. Represents a group or a heterocyclic group having 2 to 20 carbon atoms,
R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, halogen atom, nitro group, cyano group, hydroxyl group, carboxyl group, R ¹⁷ , OR ¹⁸ , SR ¹⁹ , NR ²⁰ R ²¹ , COR ²² , SOR ²³ , SO _2. R ²⁴ or CONR ²⁵ R ²⁶ , R ¹⁵ and R ¹⁶ may be bonded to each other to form a ring;
R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ and R ²⁶ are each independently an alkyl group having 1 to 20 carbon atoms, 6 to 6 carbon atoms A 30 aryl group, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms;
X ² represents an oxygen atom, a sulfur atom, a selenium atom, CR ²⁷ R ²⁸ , CO, NR ²⁹ or PR ³⁰ ;
X ³ represents a single bond or CO,
R ²⁷ , R ²⁸ , R ²⁹ and R ³⁰ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms or an arylalkyl group having 7 to 30 carbon atoms. The alkyl group or arylalkyl group may be substituted with a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group or a heterocyclic group, and the methylene group in the alkyl group or arylalkyl group is —O. -May be interrupted by-
R ²⁷ , R ²⁸ , R ²⁹ and R ³⁰ may each independently form a ring together with one of the adjacent benzene rings,
a represents an integer of 0 to 4,
b represents an integer of 0 to 5. ) The photocurable composition according to any one of claims 1 to 3, wherein the colorant (D) is a black pigment. A black matrix using the photocurable composition according to claim 4 . A color filter having a black matrix according to claim 5 .