JP2002206014A - Photopolymerizing composition and method of producing color filter using the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photopolymerizing composition that has excellent transparency, resistance to heat, resistance to chemicals and adhesion with extremely reduced elution of impurities (acid liberation and the like) and excellent storage stability and provide a method of producing color filters by using the composition. SOLUTION: An organic acid bearing an unsaturated double bond is reacted with an epoxy group-bearing compound and the resultant reaction product is reacted with a 6membered acid anhydride having a specific structure (glutaric anhydride, 3,3-dimethylglutaric anhydride, 3,3-tetramethyleneglutaric anhydride and the like) to prepare a photopolymerizing unsaturated compound. A photopolymerization initiator or a combination thereof with a pigment of dye is formulated to the photopolymerizing compound to prepare the objective photopolymerizing composition. The resultant photopolymerizing composition is used to produced color filters.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a photopolymerizable composition and a method for producing a color filter using the composition. The present invention also relates to a photopolymerizable unsaturated compound used for producing a photopolymerizable composition.

The photopolymerizable composition of the present invention is excellent in transparency, heat resistance, chemical resistance and adhesion, has very little elution of impurities (for example, liberation of acid) with time, and is stable in storage. Excellent in nature. It is also excellent in dispersibility of pigments and dyes. Therefore, using the photopolymerizable composition of the present invention, a color filter having excellent transparency, heat resistance, chemical resistance and adhesion, excellent storage stability with very little acid release, and a uniform hue. Can be manufactured. In addition, the photopolymerizable unsaturated compound according to the present invention can be used in combination with any known photopolymerization initiator to easily produce a photopolymerizable composition having the above-mentioned excellent properties.

[0003]

2. Description of the Related Art Conventionally, various photopolymerizable compositions have been used as a photoresist for forming a protective film of a color filter of a liquid crystal device or the like, or as a solder photoresist at the time of manufacturing a printed wiring board. These photopolymerizable compositions are
Characteristics such as excellent transparency, heat resistance, chemical resistance, adhesion, and durability are required.

When the photopolymerizable composition is used as a photoresist for forming a color filter for forming a color relief resin layer, a pigment or dye such as green, blue, red, or black is added and dispersed in the composition, and this is dispersed. After coating and drying on a substrate, it is selectively exposed and developed to form a relief resin layer of a predetermined color (which forms a light-shielding layer when a black pigment or dye is used) to produce a color filter. Therefore, the photopolymerizable composition used as a photoresist for forming a color filter, in addition to the above-mentioned required characteristics,
It is further required that the dye has excellent dispersibility of the dye and that there is no display unevenness of the color filter.

As a photopolymerizable composition, for example, a resin having an epoxy group is used in JP-A-5-339356, JP-A-11-231523, and the like. A photopolymerizable composition has been proposed in which an organic acid having a saturated double bond is reacted with an acid anhydride to introduce an efficient photopolymerizable active group and an alkali developable acid value. These photopolymerizable compositions are said to exhibit properties excellent in transparency, heat resistance, adhesion to a substrate, and chemical resistance.

[0006] However, in each of the above publications, the acid anhydride reaction to epoxy acrylate is carried out by using an acid anhydride other than a 6-membered ring structure, for example, maleic anhydride, succinic anhydride,
The reaction is performed using an acid anhydride having a five-membered ring structure such as itaconic anhydride and phthalic anhydride. When an acid anhydride having a 5-membered ring structure is used, one end forms an ester with an organic substance and the other end forms a carboxyl group (half ester ), The carboxyl group reacts with the ester at one end to recyclize, causing the elimination of the esterified acid anhydride, which oozes out. There is. This problem causes a decrease in display quality (contrast), a problem such as display unevenness, and a decrease in durability of the liquid crystal, particularly in the production of liquid crystal and the like.

[0007]

Therefore, there is a need for a photopolymerizable composition which is free of impurities as described above and has excellent properties of transparency, heat resistance, adhesion and chemical resistance. .

The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a product obtained by reacting an ester compound of an epoxy group-containing compound with an organic acid with a specific acid anhydride having a 6-membered ring structure. Composition (photopolymerizable unsaturated compound) has excellent transparency, heat resistance, chemical resistance, and adhesion, and has very little elution of impurities (acid release, etc.). It has been found that the present invention has a remarkably excellent effect, and that the pigment / dye is also excellent in dispersibility, thereby completing the present invention. The present invention contributes to an improvement in reliability of a color liquid crystal display device, for example.

That is, the present invention is excellent in transparency, heat resistance, chemical resistance and adhesion, has very little impurity elution (acid release, etc.), is excellent in storage stability, and further has pigments and dyes. It is an object of the present invention to provide a photopolymerizable composition excellent in dispersibility of a color filter, and a method for producing a color filter using the composition.

[0010]

In order to achieve the above-mentioned object, the present invention provides a method comprising reacting (A) an epoxy group-containing compound with an organic acid having an unsaturated double bond. Formula (I)

[0011]

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(In the formula (I), X is -CH _2- , -CH =,
-O -, - NH -, - N =, - NR 5 -, - CHR 5 -,
Or —CR ₅ R ₆ —; R ₁ , R ₂ , R ₃ , R ₄ ,
R ₅ and R ₆ are each independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms (provided that
(Which may have an unsaturated bond or may contain a Si group), a phenyl group, an amino group, a halogen atom, or a non-existent acid anhydride. Provided is a photopolymerizable composition containing a polymerizable unsaturated compound and (B) a photopolymerization initiator.

The present invention further provides (C) a pigment and / or
Alternatively, the present invention provides the above photopolymerizable composition containing a dye.

The present invention also provides a color relief resin layer comprising the steps of: applying a photopolymerizable composition containing the above-mentioned components (A) to (C) on a substrate, selectively exposing the composition to light, and then developing the composition; (Including a light-shielding layer).

In the present invention, the photopolymerizable composition containing the above components (A) and (B) is applied on a color filter comprising a color relief resin layer (including a light-shielding layer) formed on a substrate. Thereafter, a method for manufacturing a color filter is provided, in which the entire surface is exposed to form a transparent protective film.

Further, the present invention relates to a photopolymerizable unsaturated compound used for producing a photopolymerizable composition, wherein the compound is reacted with an organic acid having an unsaturated double bond to obtain a reaction product. The product has the formula (I) (wherein, X, R ₁ , R ₂ ,
R ₃ , R ₄ , R ₅ , and R ₆ are as defined above).

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The photopolymerizable unsaturated compound (A) used in the photopolymerizable composition of the present invention is obtained by reacting an epoxy group-containing compound with an organic acid having an unsaturated double bond. The reaction product is represented by the above formula (I) (wherein X,
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ are as defined above), and is obtained by reacting an acid anhydride having a specific 6-membered ring structure.

The epoxy group-containing compound is not particularly limited as long as it has at least one epoxy group. Examples thereof include bisphenol A epoxy resin, bisphenol F epoxy resin, and bisphenol S type epoxy resin. Bisphenol type epoxy resin such as epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, alicyclic epoxy resin, glycidyl group-containing phenol resin such as phenyl glycidyl ether, p-butylphenol glycidyl ether, tri Examples include glycidyl group-containing (meth) acrylic resins such as glycidyl isocyanurate, diglycidyl isocyanurate, and allyl glycidyl ether. The glycidyl group-containing (meth) acrylic resin is a homopolymer of glycidyl (meth) acrylate alone, or methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isobutyl acrylate, isobutyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl acrylate,
Hydroxyethyl methacrylate, ethylene glycol monomethyl ether acrylate, ethylene glycol monomethyl ether methacrylate, ethylene glycol monoethyl ether acrylate, ethylene glycol monoethyl ether methacrylate, glycerol acrylate, glycerol methacrylate, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, 2-ethylhexyl acrylate, 2
-It is obtained by copolymerizing with ethylhexyl methacrylate, benzyl acrylate, benzyl methacrylate and the like.

In the present invention, one or more selected from an epoxy resin having a bisphenolfluorene structure, an epoxy resin having a bisphenolpropane structure, a phenol resin containing a glycidyl group, and a (meth) acryl resin containing a glycidyl group are used. It is preferably used.

Examples of the organic acid having an unsaturated double bond include:
Examples include acrylic acid, methacrylic acid, fumaric acid, maleic acid, crotonic acid, cinnamic acid, and sorbic acid. Also, esters and salts of these organic acids can be used, and examples thereof include monomethyl fumarate, monoethyl fumarate, monopropyl fumarate, monomethyl maleate, monoethyl maleate, monopropyl maleate and the like. Above all, acrylic acid and methacrylic acid are preferably used in terms of ease of reaction and optical sensitivity.

The reaction (esterification reaction) between the epoxy group-containing compound and the organic acid having an unsaturated double bond can be carried out by a conventional method. By this esterification reaction,
The epoxy group-containing compound is made photopolymerizable. In the above reaction, the epoxy group is opened to form a hydroxyl group.

Next, an acid anhydride is added to the hydroxyl group of the reaction product thus obtained by ring opening of the epoxy group to add an acid value, and the polymerizable unsaturated polymerizable with an aqueous alkali solution can be developed. Although a compound is obtained, the present invention is characterized in that an acid anhydride represented by the following formula (I) is used as the acid anhydride.

[0024]

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In the above formula (I), X represents —CH ₂ —, —CH
=, - O -, - NH -, - N =, - NR 5 -, - CHR 5
— Or —CR ₅ R ₆ —. Preferably, X is -C
H ₂ — or —CR ₅ R ₆ — is shown.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms (however, May have an unsaturated bond and may contain a Si group),
Indicates a phenyl group, amino group, halogen atom, or absence. Preferably, R _{1 to} R ₆ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, particularly a hydrogen atom or a methyl group.

That is, in the present invention, the acid anhydride having a six-membered ring is used. By using an acid anhydride having a six-membered ring, the three-dimensional distance between each molecule is wider than in the case of using an acid anhydride having a conventional five-membered ring structure. It becomes difficult, and no elimination of the organic acid and no liberation of the acid anhydride occur, so that a bleeding of these components and a composition having a strong structure can be obtained. When a compound having a four-membered ring or less is used, a stable anhydride cannot be produced.
When a compound having a 7-membered ring or more is used, the anhydride becomes unstable.

As the acid anhydride represented by the above formula (I), glutaric acid anhydride is preferable because of little steric hindrance. Specifically, glutaric anhydride, 3-ethyl-3
-Methyl glutaric anhydride, 3,3-dimethyl glutaric anhydride, 3,3-tetramethylene glutaric anhydride,
3- (tert-butyldimethylsilyloxy) glutaric anhydride, homophthalic anhydride, 2-phenylglutaric anhydride and the like. Also, diglycolic anhydride and the like can be used.

When the acid anhydride represented by the above formula (I) is used, pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, biphenylethertetracarboxylic dianhydride are used. A mixture with an acid dianhydride such as an anhydride may be used. The use of the mixture with the acid dihydrate is preferable because two or more esterified epoxy group-containing compounds can be connected and a high molecular weight can be obtained.

On the other hand, for the purpose of adjusting the molecular weight, the amount of maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride,
It is also effective to add tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, pyromellitic anhydride and the like. These acid anhydride compounds can be used alone or in combination of two or more.

An ester of the epoxy group-containing compound,
The reaction with the acid anhydride is performed by heating in an organic solvent.

Examples of the organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether,
Examples thereof include diethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and 3-methoxybutyl acetate. Among them, ethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate and the like are preferably used.

The reaction temperature is preferably about 100 to 130 ° C., particularly about 110 to 125 ° C.

The above reaction is carried out using the epoxy group-containing compound 100
The acid anhydride represented by the formula (I) is preferably used in an amount of 10 to 80 parts by weight, more preferably 20 to 70 parts by weight, based on parts by weight. In particular, when a mixture of the acid anhydride represented by the above formula (I) and the acid dianhydride is used as the acid anhydride, the acid anhydride represented by the above formula (I) is added to 100 parts by weight of the epoxy group-containing compound. It is preferable to use 1 to 80 parts by weight, particularly 10 to 60 parts by weight, and 1 to 60 parts by weight, particularly 10 to 50 parts by weight of the acid dianhydride. If the amount of the component used is outside the above preferred range, the transparency, heat resistance, and adhesion tend to decrease, which is not preferable.

The photopolymerizable unsaturated compound as the component (A) obtained as described above is novel and has not only excellent transparency, heat resistance and adhesion, but also an acid by a half ester as in the prior art. Is not released and exuded, and has excellent chemical resistance.

The formation of the photopolymerizable unsaturated compound is as follows:
It can be confirmed by the IR spectrum.

The component (A) has an average molecular weight of preferably from 1,000 to 100,000, particularly preferably from 2,000 to 1,
0,000 oligomers or polymers. If the average molecular weight is too large, it is not suitable for development, while if the average molecular weight is too small, peeling is likely to occur during development.

The acid value is from 20 to 200, preferably from 40 to 100. If the acid value is too low, the alkali developability deteriorates, while if the acid value is too high, peeling occurs.

The component (A) is specifically represented by the following formula (II):
(VII) are exemplified.

The compounds of formulas (II) and (V) show an example in which an epoxy resin having a bisphenolpropane structure is used, and the compounds of formulas (III) and (VI) use an epoxy resin having a bisphenolfluorene structure. The compound of the formula (VII) shows an example when a glycidyl group-containing (meth) acrylic resin is used, and the compound of the formula (IV) shows an example when a glycidyl group-containing phenol resin is used. Show.

[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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In the formulas (II) to (VII), Y, Z,
V, W, A, R ₇ , R ₈ , m, and n have the following meanings.

[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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R ₇ : hydrogen atom or 1 to 6 carbon atoms
Represents an alkyl group. It preferably represents a hydrogen atom or a methyl group. R _{8 represents a} hydrogen atom or an alkyl group having 1 to 6 carbon atoms. It preferably represents a hydrogen atom or a methyl group. m: represents an integer of 0 to 19; n: represents an integer of 1 to 20.

The photopolymerizable unsaturated compound as the component (A) can be combined with an optional photopolymerization initiator to
A photopolymerizable composition having excellent transparency, heat resistance, adhesion, and chemical resistance and free from elution of impurities (such as acid separation) can be obtained.

The photopolymerization initiator as the component (B) is not particularly limited, and any known photopolymerization initiator can be used. For example, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one,
2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-hydroxy-
2-methyl-1-phenylpropan-1-one, 2,
4,6-trimethylbenzoyldiphenylphosphine oxide, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane-1
-One, 2,4-diethylthioxanthone, 2-chlorothioquintone, 2,4-dimethylthioxanthone, 3,
3-dimethyl-4-methoxybenzophenone, benzophenone, 1-chloro-4-propoxythioxanthone,
1- (4-isopropylphenyl) -2-hydroxy-
2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-
On, 4-benzoyl-4′-methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate,
Butyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-isoamyl 4-dimethylaminobenzoate, 2,2-diethoxyacetophenone, benzyldimethylketal, benzyl-β-
Methoxyethyl acetal, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, bis (4-dimethylaminophenyl) ketone, 4,4′-bisdiethylaminobenzophenone [= Michler's ketone], 4,4 '
-Dichlorobenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether,
Benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone,
p-tert-butyldichloroacetophenone, 2-
(O-chlorophenyl) -4,5-diphenylimidazolyl dimer, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, α, α-dichloro-4-phenoxyacetophenone, pentyl-4-dimethylaminobenzoate , 9-
Phenylacridine, 1,7-bis- (9-acridinyl) heptane, 1,5-bis- (9-acridinyl) pentane, 1,3-bis- (9-acridinyl) propane, 2,4-bis-trichloromethyl -6- (3-bromo-4-methoxy) phenyl-s-triazine, 2,4
-Bis-trichloromethyl-6- (2-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s-triazine and the like.

In addition to the above, the photopolymerizable composition of the present invention may contain an organic solvent or an ethylenic compound. By blending an organic solvent or an ethylenic compound, the applicability of the photopolymerizable composition coating solution and the properties of the coating film can be further improved.

Specific examples of the organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, and propylene. Glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethyl Glycol diethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate , 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 2-methyl-3-
Methoxy butyl acetate, 3-methyl-3-methoxy butyl acetate, 3-ethyl-3-methoxy butyl acetate, 2-ethoxy butyl acetate, 4-ethoxy butyl acetate, 4-propoxy butyl acetate, 2-methoxy pentyl acetate, 3-methoxy butyl acetate Methoxypentyl acetate, 4-methoxypentyl acetate,
2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-
4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone, methyl lactate, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, methyl carbonate,
Ethyl carbonate, propyl carbonate, butyl carbonate, benzene, toluene, xylene, cyclohexanone, methanol, ethanol, propanol, butanol, hexanol,
Examples include cyclohexanol, ethylene glycol, diethylene glycol, glycerin and the like.

The above organic solvent is used in a total amount of the photopolymerizable composition of 1%.
1000 parts by weight or less, preferably 5 parts by weight
It can be contained in the range of not more than 00 parts by weight.

As the ethylenic compound, specifically, a compound having at least one ethylenically unsaturated double bond capable of addition polymerization is used, and a monomer having an ethylenically unsaturated double bond or A polymer having an ethylenically unsaturated double bond in a side chain or a main chain is exemplified.

Examples of the monomer having an ethylenically unsaturated double bond include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isobutyl acrylate, isobutyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, Ethylene glycol monomethyl ether acrylate, ethylene glycol monomethyl ether methacrylate, ethylene glycol monoethyl ether acrylate, ethylene glycol monoethyl ether methacrylate, glycerol acrylate, glycerol methacrylate, acrylamide,
Methacrylamide, acrylonitrile, methacrylonitrile, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, benzyl acrylate, benzyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene Glycol diacrylate, tetraethylene glycol dimethacrylate,
Butylene glycol diacrylate, butylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, trimethylolethane triacrylate, trimethylolethane trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolpropane tetraacrylate, Tetramethylolpropane tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hex Acrylate, dipentaerythritol hexa dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, cardo epoxy diacrylate, it includes cardo epoxy dimethacrylate.

The acrylates and methacrylates of these exemplified compounds are converted to fumarate, maleate, crotonate,
Fumaric acid ester, maleic acid ester, crotonic acid ester, itaconic acid ester, acrylic acid, methacrylic acid, fumaric acid, maleic acid, crotonic acid, itaconic acid, hydroquinone monoacrylate, hydroquinone monomethacrylate, hydroquinone di Acrylate, hydroquinone dimethacrylate, resorcin dimethacrylate, resorcin dimethacrylate, pyrogallol diacrylate, pyrogallol triacrylate, condensates of acrylic acid with phthalic acid and diethylene glycol, condensates of acrylic acid with maleic acid and diethylene glycol, methacrylic acid and terephthalic acid Condensates with acid and pentaerythritol, condensates of acrylic acid and adipic acid and of butanediol and glycerin, ethylenebis Acrylamide, ethylene bis-methacrylamide, allyl ester of diallyl phthalate, divinyl phthalate.

Examples of the polymer having an ethylenically unsaturated double bond in the side chain or main chain include polyester obtained by a polycondensation reaction between an unsaturated divalent carboxylic acid and a dihydroxy compound, and an unsaturated divalent carboxylic acid. Polyamide obtained by polycondensation reaction with diamine, itaconic acid, propylidene succinic acid, polyester obtained by polycondensation reaction of ethylidene malonic acid and dihydroxy compound,
Examples thereof include polyamides obtained by a polycondensation reaction of itaconic acid, propylidene succinic acid, ethylidene malonic acid and diamine.

In addition, a polymer having a functional group having a reactive activity such as a hydroxy group or a halogenated alkyl group in a side chain, for example, polyvinyl alcohol, poly (2-hydroxyethyl methacrylate), polyepichlorohydrin, etc., and acrylic acid And polymers obtained by a polymer reaction with unsaturated carboxylic acids such as methacrylic acid, fumaric acid, maleic acid, crotonic acid and itaconic acid.

The above-mentioned ethylenic compound is preferably blended in an amount of 10 to 70 parts by weight based on 100 parts by weight of the total solid content of the photopolymerizable composition. When the amount is less than 10 parts by weight, poor exposure curing tends to occur. On the other hand, when the amount exceeds 70 parts by weight, coating properties and heat resistance and chemical resistance of the film after exposure and curing are unpreferably reduced.

The photopolymerizable composition of the present invention may further comprise, if necessary, a sensitizer, a thermal polymerization inhibitor, a plasticizer,
Optional components such as a surfactant and an antifoaming agent can be added.

As a sensitizer, specifically, eosin B
(CI No. (= color index number)
45400), Eosin J (CI No. 4538)
0), alcohol-soluble eosin (CI No. 45)
386), cyanosine (CI No. 45410),
Bengal Rose, Erythrosin (CI No. 454)
30), xanthene dyes such as 2,3,7-trihydroxy-9-phenylxanthen-6-one and rhodamine 6G; thionin (CI No. 52000), Azure A (CI. No. 52005) ), And Azure C
Thiazine dyes such as (CI No. 52002); pyronin dyes such as pyronin B (CI No. 45005) and pyronin GY (CI No. 45005);
Coumarin compounds such as 3-acetylcoumarin and 3-acetyl-7-diethylaminocoumarin are exemplified.

Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monoethyl ether, p-methoxyphenol, pyrogallol, catechol, 2,6-di-tert.
-Butyl-p-cresol, β-naphthol and the like.

As the plasticizer, dioctyl phthalate,
Didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin and the like can be mentioned.

Examples of the surfactant include various anionic, cationic and nonionic surfactants, and examples of the antifoaming agent include various silicone and fluorine antifoaming agents.

The photopolymerizable composition of the present invention is used as a photoresist for forming a protective film of a color filter of a liquid crystal display device or the like and a color relief resin layer (including a light shielding film).
Alternatively, it can be used as a solder photoresist or the like at the time of manufacturing a printed wiring board. In particular, when it is used as a photoresist for forming a color relief resin layer (including a light shielding film) of a color filter, a pigment and / or a component (C) is further added. It must contain a dye. The photopolymerizable composition of the present invention is also excellent in dispersibility of these pigments and dyes, so that the hue of the obtained color filter can be kept uniform.

The pigment and / or dye of the component (C)
It is not particularly limited. For example, when a light-shielding film is formed as a color relief resin layer, more specifically, for example, when used as a resin black such as a black stripe for liquid crystal or a black matrix, carbon black, titanium black, chromium oxide, iron oxide, Aniline black, perylene pigment, C.I. I. Acid Black 51, C.I. I. Acid Black 52, C.I. I. Basic Black 2, C.I. I. Solvent Black 123 and the like can be preferably used.

Further, inorganic black pigments such as carbon black coated with an epoxy resin or the like, titanium black, and a composite oxide such as manganese, iron, copper, and cobalt;
The following combinations of organic pigments and combinations of organic pigments with the above-mentioned black pigments can also be used.

In the case of chromatic colors such as red, green, blue, cyan and magenta / yellow, the pigments and / or dyes are not particularly limited. For example, JP-A-60-237403 and Kaiping 4
And pigments or dyes described in JP-A-310901. That is, the color index number (C.
I. No. ), Yellow pigment: C.I. I. 20, 24, 83, 86, 93,
109, 110, 117, 125, 129, 137, 1
38, 139, 147, 148, 150, 153, 15
4, 166, 168, 180, 185, 195 Orange pigment: C.I. I. 36, 43, 51, 55, 59,
61 red pigment: C.I. I. 9, 97, 122, 123, 14
9, 168, 177, 180, 192, 215, 21
6, 217, 220, 223, 224, 226, 22
7, 228, 240, 254 Purple pigment: C.I. I. 19, 23, 29, 30, 37,
40, 50 Blue pigment: C.I. I. 15, 15: 3, 15: 6, 2
2, 60, 64 Green pigment: C.I. I. 7, 36 Brown pigment: C.I. I. Those represented by 23, 25, and 26 can be suitably used because they have high transparency and excellent heat resistance, weather resistance, and chemical resistance.

As the dye, specifically, C.I. I. N
o. And C. I. Direct Yellow 1, C.I. I. Direct Yellow 11, C.I. I. Direct Yellow 1
2, C.I. I. Direct Yellow 28, C.I. I. Acid Yellow 1, C.I. I. Acid Yellow 3, C.I. I.
Acid Yellow 11, C.I. I. Acid Yellow 1
7, C.I. I. Acid Yellow 23, C.I. I. Acid Yellow 38, C.I. I. Acid Yellow 40, C.I.
I. Acid Yellow 42, C.I. I. Acid Yellow 76, C.I. I. Acid Yellow 98, C.I. I. Basic Yellow 1, C.I. I. Disperse Yellow 3,
C. I. Disperse Yellow 4, C.I. I. Disperse Yellow 7, C.I. I. Disperse Yellow 31,
C. I. Disperse Yellow 61, C.I. I. Solvent Yellow 2, C.I. I. Solvent Yellow 14, C.I.
I. Solvent Yellow 15, C.I. I. Solvent Yellow 16, C.I. I. C. I. Solvent Yellow 21,
C. I. Solvent Yellow 33, C.I. I. Solvent Yellow 56, C.I. I. Acid Orange 1, C.I. I.
Acid orange 7, C.I. I. Acid orange 8,
C. I. Acid orange 10, C.I. I. Acid orange 20, C.I. I. Acid Orange 24, C.I. I. Acid Orange 28, C.I. I. Acid Orange 33,
C. I. Acid orange 56, C.I. I. Acid orange 74, C.I. I. Direct Orange 1, C.I. I. Disperse Orange 5, C.I. I. Solvent Orange 1, C.I. I. Solvent Orange 2, C.I. I. Solvent Orange 5, C.I. I. Solvent Orange 6, C.I.
I. Solvent Orange 45, C.I. I. Direct Red 20, C.I. I. Direct Red 37, C.I. I. Direct Red 39, C.I. I. Direct Red 44,
C. I. Acid Red 6, C.I. I. Acid Red 8, C.I. I. Acid Red 9, C.I. I. Acid Red 13, C.I. I. Acid Red 14, C.I. I. Acid Red 18, C.I. I. Acid Red 26, C.I. I.
Acid Red 27, C.I. I. Acid Red 51,
C. I. Acid Red 52, C.I. I. Acid Red 87, C.I. I. Acid Red 88, C.I. I. Acid Red 89, C.I. I. Acid Red 92, C.I. I. Acid Red 94, C.I. I. Acid Red 97, C.I.
I. Acid Red 111, C.I. I. Acid Red 1
14, C.I. I. Acid red 115, C.I. I. Acid red 134, C.I. I. Acid Red 145, C.I.
I. Acid Red 154, C.I. I. Acid Red 1
80, C.I. I. Acid Red 183, C.I. I. Acid Red 184, C.I. I. Acid Red 186, C.I.
I. Acid Red 198, C.I. I. Basic Red 12, C.I. I. Basic Red 13, C.I. I. Disperse Red 5, C.I. I. Disperse Red 7, C.I.
I. Disperse thread 13, C.I. I. Disperse thread 17, C.I. I. Disperse thread 58, C.I. I.
Solvent Red 1, C.I. I. Solvent Red 3,
C. I. Solvent Red 8, C.I. I. Solvent Red 23, C.I. I. Solvent Red 24, C.I. I. Solvent Red 25, C.I. I. Solvent Red 27,
C. I. Solvent Red 30, C.I. I. Solvent Red 49, C.I. I. Solvent Red 100, C.I. I.
Direct Violet 22, C.I. I. Acid violet 49, C.I. I. Basic Violet 2, C.I.
I. Basic Violet 7, C.I. I. Basic Violet 10, C.I. I. Disper Violet 2
4, C.I. I. Direct Blue 25, C.I. I. Direct Blue 86, C.I. I. Direct Blue 90, C.I.
I. Direct Blue 108, C.I. I. Acid Blue 1, C.I. I. Acid Blue 7, C.I. I. Acid Blue 9, C.I. I. Acid Blue 15, C.I. I. Acid blue 103, C.I. I. Acid blue 104, C.I.
I. Acid Blue 158, C.I. I. Acid Blue 1
61, C.I. I. Basic Blue 1, C.I. I. Basic Blue 3, C.I. I. Basic Blue 9, C.I. I. Basic Blue 25, C.I. I. Acid Green 3,
C. I. Acid Green 9, C.I. I. Acid Green 16, C.I. I. Basic Green 1, C.I. I. Basic Green 4, C.I. I. Direct Brown 6,
C. I. Direct Brown 58, C.I. I. Direct Brown 95, C.I. I. Direct Brown 101,
C. I. Direct Brown 173, C.I. I. Acid Brown 14 or the like is preferably used.

The pigment and / or dye is used in an amount of 5 to 200 parts by weight based on 100 parts by weight of the total solid content of the photopolymerizable composition.
It is preferable to mix in the range of parts by weight, especially 30 to 1
00 parts by weight. When the amount is less than 10 parts by weight, it is difficult to function as a color filter. On the other hand, when the amount is more than 150 parts by weight, sensitivity tends to decrease, and heat resistance and chemical resistance of the cured film tend to decrease.

The following is an example of a method for producing a color filter using the photopolymerizable composition of the present invention.

(1) Preparation of Photopolymerizable Composition To the photopolymerizable unsaturated compound of the present invention obtained as described above, a photopolymerization initiator, a pigment and / or a dye are added.
If desired, here, an organic solvent, a sensitizer, a thermal polymerization inhibitor, a plasticizer, a surfactant, a thing added with an antifoaming agent,
A three-roll mill, a ball mill, a sand mill, a jet mill, a microfluidizer, a nanomizer and the like are well dispersed and kneaded to prepare a photopolymerizable composition for a color filter.

(2) Application of Photopolymerizable Composition The above prepared photopolymerizable composition is applied onto a substrate whose surface has been cleaned in advance. Glass as substrate,
Materials such as polyethylene terephthalate, acrylic resin, and polycarbonate are exemplified. For the coating, a contact transfer type coating device such as a roll coater, a reverse coater or a bar coater, or a non-contact type coating device such as a spinner or a curtain flow coater is used. In particular, in the case of a thick film, it is preferable to apply a plurality of times or to use several kinds of the above-mentioned coating apparatuses in combination.

After application of the photopolymerizable composition, the solvent is removed by drying on a direct hot plate for several minutes or by placing it in a warm air heater or infrared heater for several tens of minutes to several hours to remove the solvent. Adjust to about 10 μm.

(3) Exposure treatment After the formation of the coating film, active rays are selectively irradiated through a negative mask. The actinic rays include ultraviolet light, excimer laser light,
X-rays, gamma rays, electron beams and the like are preferred. The amount of exposure varies depending on the component composition of the photopolymerizable composition to be used.
It is preferably about 0 to 2000 mJ / cm ² .

(4) Developing treatment After irradiating with active rays, development is carried out by using a developing solution by an immersion method, a spraying method or the like, and the unirradiated portions of the active rays are removed with an alkali developing solution. (Color relief resin layer) is formed.

Examples of the alkaline developer include hydroxides and carbonates of alkali metals such as lithium, sodium and potassium.
Bicarbonate, phosphate or pyrophosphate; primary amines such as benzylamine and butylamine; secondary amines such as dimethylamine, dibenzylamine and diethanolamine; tertiary amines such as trimethylamine, triethylamine and triethanolamine Cyclic amines such as morpholine, piperazine and pyridine; polyamines such as ethylenediamine and hexamethylenediamine; ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylbenzylammonium hydroxide and trimethylphenylbenzylammonium hydroxide And sulfonium such as trimethylsulfonium hydroxide, diethylmethylsulfonium hydroxide, and dimethylbenzylsulfonium hydroxide Hydroxides; Other aqueous choline or the like is used.

The photopolymerizable unsaturated compound of the present invention is
It can also be applied to a protective film of a color filter. In this case, the composition is used as a two-component photopolymerizable composition containing a photopolymerizable unsaturated compound and a photopolymerization initiator. After applying the photopolymerizable composition to the upper surface of the color filter, the entire surface can be exposed and cured to form a protective film. Excellent protection, transparency, adhesion, heat resistance, chemical resistance, and storage stability.

[0084]

Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

Synthesis Example 1 100 g of bisphenol A epoxy resin, 33 g of acrylic acid, 300 mg of tetraethylammonium chloride and methylhydroquinone 5
0 mg, heated to 100 ° C. and stirred for 2 hours,
The acrylate reaction of the epoxy resin was performed.

Next, the thus obtained 2,2-
After dissolving 100 g of bis [4-{(2-hydroxy-3-acryloxy) propoxy} phenyl] propane in 113 g of propylene glycol monoethyl ether acetate, 3,3-tetramethylene glutaric anhydride 70 was dissolved.
g and 0.5 g of tetraethylammonium bromide are added and mixed, and the mixture is heated to 120 ° C. and reacted for 4 hours to obtain an alkali-developable photopolymerizable unsaturated compound having two acid-added unsaturated double bonds. A compound (monomer) was obtained. The photopolymerizable unsaturated compound is represented by the formula (II) (wherein, in Y, A
Represents a group represented by the following formula 27, and R ₈ represents a hydrogen atom.
It is a compound shown by these.

[0087]

Embedded image

The formation of the photopolymerizable unsaturated compound was confirmed by an IR spectrum. The molecular weight of the photopolymerizable unsaturated compound was 2,800 and the acid value was 60.

(Synthesis Example 2) Fluorene type epoxy resin 1
00g and acrylic acid 16g, tetraethylammonium chloride 300mg and methylhydroquinone 50mg
Was heated to 100 ° C. and stirred for 2 hours to carry out an acrylate reaction of the epoxy resin.

Next, the thus obtained 9,9-
After dissolving 100 g of bis [4-{(2-hydroxy-3-acryloxy) propoxy} phenyl] fluorene in 109 g of 3-methoxybutyl acetate, 17 g of glutaric anhydride, 47 g of benzophenonetetracarboxylic dianhydride and tetraethyl bromide 0.5g ammonium
Was added, mixed, heated to 120 ° C. and reacted for 4 hours to obtain a photopolymerizable unsaturated compound. The photopolymerizable unsaturated compound is represented by the formula (VI) [wherein R ₈ in Z represents a hydrogen atom, V is as defined in the above formulas 10 or 24, and W is in the above formulas 11 or 25] in is as defined, a is -CH ₂ CH ₂ CH ₂ - is a compound represented by showing a].

The production of the photopolymerizable unsaturated compound was confirmed by an IR spectrum (shown in FIG. 1).

The molecular weight of the photopolymerizable unsaturated compound was 3,300 and the acid value was 60.

(Synthesis Example 3) Glycidyl methacrylate and benzyl methacrylate having an average molecular weight of 10,000
20 g of acrylic acid was added to 100 g of a / 50 copolymer resin, 300 mg of tetraethylammonium chloride, 50 mg of methylhydroquinone and 120 g of 3-methoxybutyl acetate were charged, the temperature was raised to 100 ° C., and the mixture was stirred for 2 hours. The reaction was carried out.

Next, 17 g of 3-3 dimethylglutaric anhydride and 0.5 g of tetraethylammonium chloride were further added to a solution of 100 g of the ester of glycidyl group-containing resin and acrylic acid thus obtained, and mixed. The temperature was raised to 120 ° C. and the reaction was carried out for 6 hours to obtain a photopolymerizable unsaturated compound. Photopolymerizable unsaturated compound is the formula (VII) (although Shikichu, A is _{-CH 2 C (CH 3) 2} CH 2
And R ₈ represents a methyl group).

The production of the photopolymerizable unsaturated compound was confirmed by IR spectrum. The molecular weight of the photopolymerizable unsaturated compound was 12,000, and the acid value was 85.

(Synthesis Example 4) In Synthesis Example 1, 3,3-
Instead of 70 g of tetramethylene glutaric anhydride,
The reaction was carried out in the same manner as in Synthesis Example 1 except for using 80 g of 1,2,3,6-tetrahydrophthalic anhydride to obtain a photopolymerizable unsaturated compound.

The production of the photopolymerizable unsaturated compound was confirmed by IR spectrum. The molecular weight of the photopolymerizable unsaturated compound was 3,000, and the acid value was 65.

(Synthesis Example 5) A photopolymerizable unsaturated compound was obtained in the same manner as in Synthesis Example 2 except that 27 g of phthalic anhydride was used instead of 17 g of glutaric anhydride. Was.

The formation of the photopolymerizable unsaturated compound was confirmed by an IR spectrum. The molecular weight of the photopolymerizable unsaturated compound was 3,800 and the acid value was 55.

(Synthesis Example 6) In Synthesis Example 3, 3,3-
The reaction was carried out in the same manner as in Synthesis Example 3 except that 17 g of succinic anhydride was used instead of 17 g of dimethylglutaric anhydride to obtain a photopolymerizable unsaturated compound.

The formation of the photopolymerizable unsaturated compound was confirmed by an IR spectrum. The molecular weight of the photopolymerizable unsaturated compound was 11,000, and the acid value was 85.

Example 1 20 g of the photopolymerizable unsaturated compound obtained in Synthesis Example 2, 4 g of pentaerythritol tetraacrylate, 2-benzyl-2-dimethylamino-1-
1 g of (4-morpholinophenyl) butan-1-one ("Irgacure 369"; manufactured by Ciba Geigy) and 0.1 g of Michler's ketone were mixed and dissolved with 80 g of 3-methoxybutyl acetate to prepare a photopolymerizable composition.

The photopolymerizable composition was coated on a glass substrate having a clean surface of 1 mm in thickness using a river coater (round coater; manufactured by Dainippon Screen Co., Ltd.) so that the dry film thickness became 2 μm. And dried at 90 ° C. for 2 minutes to form a photosensitive layer.

Next, an exposure amount of 100 mJ / c was applied to the photosensitive layer.
The whole surface was exposed to ultraviolet light at m ² and spray-developed with 0.5 parts by weight of an aqueous solution of sodium carbonate at 25 ° C. for 60 seconds.
Bake in oven at ℃.

The obtained coating film was excellent in transparency, and no peeling from the substrate was confirmed. Also, no change in the color of the coating was observed.

Example 2 20 g of the photopolymerizable unsaturated compound obtained in Synthesis Example 2, 2-benzyl-2-dimethylamino-
2 g of 1- (4-morpholinophenyl) butan-1-one (“Irgacure 369”; manufactured by Ciba-Geigy)
1 g of Michler's ketone, carbon dispersion "CF Black PC" (contains 24 parts by weight of carbon; manufactured by Okuni Pigment Co., Ltd.) 40
g, blue dispersion (containing 20% of phthalocyanine blue;
After mixing and dissolving 10 g of Okunikoseigaku Co., Ltd. and 30 g of 3-methoxybutyl acetate, the mixture was dispersed under high pressure at 1000 kg / cm ² using a microfluidizer to prepare a black photopolymerizable composition.

The above black photopolymerizable composition solution was applied to a thickness of 1 mm.
Is applied on a glass substrate having a clean surface with a spin coater (“TR-25000”; manufactured by Tokyo Ohka Kogyo Co., Ltd.) so that the dry film thickness becomes 1.5 μm, and 90 ° C.
For 2 minutes to form a photosensitive layer.

Next, an exposure amount of 100 mJ / c was applied to the photosensitive layer.
The ultraviolet flood exposure in m ^2, 25 ° C. with 0.5 part by weight of sodium carbonate aqueous solution, after 60s spray development, 200
Bake in oven at ℃.

The obtained coating film was excellent in transparency, and no peeling from the substrate was confirmed. Also, no change in the color of the coating was observed.

Example 3 5 g of the photopolymerizable unsaturated compound obtained in Synthesis Example 1 and an acrylic resin (benzyl methacrylate / methacrylic acid = 75/25, molecular weight 20,000) 2
0 g, mercaptobenzimidazole 2 g, Michler's ketone 1 g, pigment dispersion "CF Red EX-109"
(CI PR-177, anthraquinone red pigment 20)
After mixing and dissolving 40 g of a part by weight (manufactured by Mikuni Dye Co., Ltd.) and 30 g of propylene glycol monoethyl ether acetate, the mixture was dispersed under high pressure at 1500 kg / cm ² using a nanomizer to prepare a red photopolymerizable composition.

The above red photopolymerizable composition solution was 1 mm thick.
Is applied on a glass substrate having a clean surface with a spin coater (“TR-25000”; manufactured by Tokyo Ohka Kogyo Co., Ltd.) so that the dry film thickness becomes 1.5 μm, and 90 ° C.
For 2 minutes to form a photosensitive layer.

Next, an exposure amount of 100 mJ / c was applied to the photosensitive layer.
The whole surface was exposed to ultraviolet light at m ² and spray-developed with 0.5 parts by weight of an aqueous solution of sodium carbonate at 25 ° C. for 60 seconds.
Bake in oven at ℃.

The obtained coating film was excellent in transparency, and no peeling from the substrate was confirmed. Also, no change in the color of the coating was observed.

Example 4 20 g of the photopolymerizable unsaturated compound obtained in Synthesis Example 3, 5 g of dipentaerythritol hexaacrylate, 2 g of mercaptobenzimidazole, 1 g of Michler's ketone, and a pigment dispersion "CF Green EX-2"
61 "(CI PG-36, containing 16 parts by weight of halogenated phthalocyanine-based green pigment; manufactured by Mikuni Dyestuffs Co., Ltd.), 40 g of propylene glycol monoethyl ether acetate 30
g after mixing and dissolving, using a Nanomizer to 1500
The mixture was dispersed under high pressure at kg / cm ² to prepare a green photopolymerizable composition.

The above green photopolymerizable composition solution was applied to a thickness of 1 mm.
Is applied on a glass substrate having a clean surface with a spin coater (“TR-25000”; manufactured by Tokyo Ohka Kogyo Co., Ltd.) so that the dry film thickness becomes 1.5 μm, and 90 ° C.
For 2 minutes to form a photosensitive layer.

Then, the photosensitive layer was exposed to an exposure of 100 mJ / c.
The whole surface was exposed to ultraviolet light at m ² and spray-developed with 0.5 parts by weight of an aqueous solution of sodium carbonate at 25 ° C. for 60 seconds.
Bake in oven at ℃.

The obtained coating film was excellent in transparency, and no peeling from the substrate was confirmed. Also, no change in the color of the coating was observed.

(Example 5) In Example 2, "CF Yellow HM" (CI PY-139, containing 20 parts by weight of a monoazo yellow pigment, instead of 10 g of a blue dispersion as a pigment dispersion; A yellow photopolymerizable composition was prepared in the same manner as in Example 2 except that 35 g of a dye was used.

The above yellow photopolymerizable composition solution was 1 mm thick.
Is applied on a glass substrate having a clean surface with a spin coater ("TR-25000", manufactured by Tokyo Ohka Kogyo Co., Ltd.) so that the dry film thickness becomes 1.5 μm, and 90 ° C.
For 2 minutes to form a photosensitive layer.

Next, the entire surface of the photosensitive layer was exposed to ultraviolet rays of 100 mJ / cm ² , spray-developed with 0.5 parts by weight of an aqueous solution of sodium carbonate at 25 ° C. for 60 seconds, and then exposed to 200 ° C.
Bake in oven.

The obtained film was excellent in transparency and, at the same time, no peeling from the substrate was confirmed. Also, no change in the color of the coating was observed.

Example 6 In Example 3, "CF Blue UM" (CI PB-15: 6, phthalocyanine blue pigment) was used in place of 40 g of "CF Red EX-109" as the pigment dispersion. A blue light-polymerizable composition was prepared in the same manner as in Example 3, except that 35 g of a 19-part by weight component (manufactured by Mikuni Pigment Co., Ltd.) was used.

The above blue light-polymerizable composition solution was applied to a thickness of 1 mm.
Is applied on a glass substrate having a clean surface with a spin coater ("TR-25000", manufactured by Tokyo Ohka Kogyo Co., Ltd.) so that the dry film thickness becomes 1.5 μm, and 90 ° C.
For 2 minutes to form a photosensitive layer.

Next, the photosensitive layer was entirely exposed to ultraviolet rays of 100 mJ / cm ² , spray-developed with a 0.5 part by weight aqueous sodium carbonate solution at 25 ° C. for 60 seconds, and then exposed to 200 ° C.
Bake in oven.

The obtained film was excellent in transparency, and no peeling from the substrate was confirmed. Also, no change in the color of the coating was observed.

(Comparative Example 1) Synthesis Example 2 in Example 1
A photopolymerizable composition was prepared in the same manner as in Example 1 except that the photopolymerizable unsaturated compound obtained in Synthesis Example 5 was used instead of the photopolymerizable unsaturated compound obtained in A photosensitive layer was formed by using this, followed by exposure and development, and then baked.

(Comparative Example 2) In Example 2, Synthesis Example 2
A photopolymerizable composition was prepared in the same manner as in Example 2 except that the photopolymerizable unsaturated compound obtained in Synthesis Example 5 was used instead of the photopolymerizable unsaturated compound obtained in A photosensitive layer was formed by using this, followed by exposure and development, and then baked.

(Comparative Example 3) Synthesis Example 1 in Example 3
A photopolymerizable composition was prepared in the same manner as in Example 3 except that the photopolymerizable unsaturated compound obtained in Synthesis Example 4 was used instead of the photopolymerizable unsaturated compound obtained in A photosensitive layer was formed by using this, followed by exposure and development, and then baked.

(Comparative Example 4) In Example 4, Synthesis Example 3
A photopolymerizable composition was prepared in the same manner as in Example 4 except that the photopolymerizable unsaturated compound obtained in Synthesis Example 6 was used instead of the photopolymerizable unsaturated compound obtained in A photosensitive layer was formed by using this, followed by exposure and development, and then baked.

(Comparative Example 5) In Comparative Example 2, "CF Yellow HM" (CI PY-139, containing 20 parts by weight of a monoazo type yellow pigment, instead of 10 g of a blue dispersion as a pigment dispersion: A photopolymerizable composition was prepared in the same manner as in Comparative Example 2 except that 35 g of a dye was used.
Using this, a photosensitive layer was formed, subsequently exposed and developed, and baked.

(Comparative Example 6) In Comparative Example 3, "CF Blue UM" (CI PB-15: 6, phthalocyanine blue pigment) was used instead of 40 g of "CF Red EX-109" as a pigment dispersion. A photopolymerizable composition was prepared in the same manner as in Comparative Example 3, except that 35 g of a 19-part by weight component (manufactured by Mikuni Dyestuffs Co., Ltd.) was used, and a photosensitive layer was formed using the composition.
Subsequently, after exposure and development processing, baking was performed.

Examples 1 to 6 and Comparative Examples 1 to 6 were evaluated for acid release and chemical resistance according to the following evaluation criteria. Table 1 shows the results.

[Acid releasing property] The photosensitive layer (photoresist layer) obtained in each of Examples and Comparative Examples was directly subjected to GC-MS analysis, and the peak of free acid was observed at a decomposition temperature of 200 ° C. evaluated. (Evaluation) ：: no free acid peak was confirmed x: free acid peak was confirmed

[Chemical resistance] The photopolymerizable composition prepared in each of Examples and Comparative Examples was applied to a substrate so as to have a film thickness of 2.0 μm, and 200 mJ / cm was measured with a proximity exposure machine.
^The entire surface was exposed at an exposure amount of ² . Then, the substrate was spray-developed with 0.2 parts by weight of sodium carbonate developer for 45 seconds,
The substrate was washed with pure water, placed in an oven at 200 ° C., and baked. Then, the substrate was N-methyl-2-
The photosensitive layer was immersed in pyrrolidone at room temperature for 10 minutes to observe the surface state of the photosensitive layer, and evaluated according to the following evaluation criteria. (Evaluation) ：: The state of the surface of the photosensitive layer (photoresist layer) did not change. X: The state of the surface of the photosensitive layer (photoresist layer) changed.

[0135]

[Table 1]

As is evident from Table 1, the photopolymerizable compositions of Examples 1 to 6 did not release acid and thus did not cause display unevenness in the liquid crystal display device, and were similar to the compositions of Comparative Examples. Was confirmed to have chemical resistance.

[Production of Color Filter] The black photopolymerizable composition prepared in Example 2 was applied to a clean and washed glass substrate using a spin coater so that the dry film thickness became 1.2 μm. After drying for 3 minutes at
200 mJ / cm using a proximity exposure machine using a pattern of a black matrix for liquid crystal of μm line.
Selective exposure was performed at an exposure of ² .

Next, the substrate was spray-developed with 0.2 parts by weight of a sodium carbonate developer for 45 seconds, and then washed with pure water.
Post-baking was performed in an oven at 0 ° C. to form a black matrix pattern.

On the black matrix pattern,
The photopolymerizable composition obtained by mixing the red photopolymerizable composition prepared in Example 3 and the yellow photopolymerizable composition prepared in Example 5 at a ratio of 70:30 has a dry film thickness of 1.5 μm. And dried, and exposed to actinic light through a mask having a black pattern gap (80 μm) (exposure amount: 100 mJ / c).
m ² ), followed by development and post-baking to form a red pattern.

The photopolymerizable composition obtained by mixing the green photopolymerizable composition prepared in Example 4 and the yellow photopolymerizable composition prepared in Example 5 at a ratio of 80:20 was placed close to the red pattern. Coating, exposure, development, post-baking,
A green pattern was formed.

Further, the blue photopolymerizable composition prepared in Example 6 was applied close to the green pattern and exposed to light.
Develop, post-bake to form a blue pattern,
A color filter in which red, green, and blue patterns are regularly arranged has been completed.

On the color filter, the transparent photoresist obtained in Example 1 was applied, the whole surface was exposed at an exposure amount of 200 mJ / cm ² , and further post-baked to form a protective film.

The resulting color filter has excellent transparency,
There was no peeling and a uniform hue. 200 ° C
No change in surface color was observed even after heating in an oven for 1 hour, and no surface roughness was observed, confirming that the composition had excellent heat resistance. Further, when each of the photoresists was analyzed for free acid by GC-MS analysis, no free acid was detected.

[0144]

As described in detail above, the photopolymerizable composition containing the photopolymerizable unsaturated compound of the present invention forms a film having excellent transparency, heat resistance, chemical resistance and adhesion. In addition, the amount of free impurities after forming the color filter is extremely small. By further mixing a pigment and / or a dye with the photopolymerizable composition, a polymerizable composition for a color filter having the same performance can be obtained. By using these, a liquid crystal display device with high display quality can be manufactured with high accuracy.

[Brief description of the drawings]

FIG. 1 shows I of a photopolymerizable unsaturated compound obtained in Synthesis Example 2.
It is a graph which shows an R spectrum.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Junichi Onodera 150 Nakamurako Nakahara-ku, Kawasaki-shi, Kanagawa F-term in Tokyo Keika Kogyo Co., Ltd. 2H025 AA00 AA06 AA07 AA08 AA10 AA14 AB13 AB15 AC01 AD01 BC74 CA01 CA28 CC12 CC13 FA03 FA17 4J011 PB25 PC02 QB19 QB20 QB22 SA01 SA21 SA31 SA64 SA78 UA06 VA01 WA01 4J027 AE02 AE03 AE04 AE07 CB10 CC04 CD10 4J036 AA01 AD08 AD11 AF06 AK11 CA21 CA28 HA02 JA09

Claims (11)

[Claims] 1. An epoxy group-containing compound (A) is reacted with an organic acid having an unsaturated double bond, and the reaction product obtained is represented by the following formula (I): (In the formula (I), X is _{-CH 2 -, - CH =,} - O -, - N
H -, - N =, - NR 5 -, - CHR 5 -, or -CR
_{5 represents} R _6- ; R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms ( However, it may have an unsaturated bond, and may contain a Si group), a phenyl group, an amino group, a halogen atom, or an absence thereof). A photopolymerizable composition containing the photopolymerizable unsaturated compound obtained and (B) a photopolymerization initiator. 2. The component (A) wherein the epoxy group-containing compound is an epoxy resin having a bisphenolfluorene structure, an epoxy resin having a bisphenolpropane structure, a glycidyl group-containing phenol resin, and a glycidyl group-containing (meth) acrylic resin. The photopolymerizable composition according to claim 1, wherein the composition is at least one member selected from the group consisting of: 3. The component (A) wherein the acid anhydride is
3. The photopolymerizable unsaturated compound according to claim 1, wherein an acid anhydride represented by the formula (I) and an acid dianhydride are used. 4. The component (A) having an average molecular weight of 1,000 to 1,000.
The photopolymerizable composition according to any one of claims 1 to 3, which is 100,000 oligomers or polymers. 5. The photopolymerizable composition according to claim 1, wherein the acid value of the component (A) is from 20 to 200. 6. The photopolymerization according to claim 1, wherein the component (A) is a photopolymerizable unsaturated compound represented by any of the following formulas (II) to (VII). Composition. Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image However, in the formulas (II) to (VII), Y, Z, V, W, A,
R ₇ , R ₈ , m and n have the following meanings. Embedded image Embedded image Embedded image Embedded image Embedded image R _7: a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R ₈ : a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. m: an integer from 0 to 19; n: an integer from 1 to 20. 7. The photopolymerizable composition according to claim 1, further comprising (C) a pigment and / or a dye. 8. A color relief resin layer (including a light-shielding layer) is formed by applying the photopolymerizable composition according to claim 7 on a substrate, selectively exposing the composition, and then developing the composition. , Color filter manufacturing method. 9. A color filter comprising a color relief resin layer (including a light-shielding layer) formed on a substrate.
7. A method for producing a color filter, comprising forming a transparent protective film by applying the photopolymerizable composition according to any one of Items 1 to 6, and then exposing the entire surface to the photopolymerizable composition. 10. A photopolymerizable unsaturated compound used for producing a photopolymerizable composition, the compound being obtained by reacting an epoxy group-containing compound with an organic acid having an unsaturated double bond. The reaction product is represented by the following formula (I): (In the formula (I), X is _{-CH 2 -, - CH =,} - O -, - N
H -, - N =, - NR 5 -, - CHR 5 -, or -CR
_{5 represents} R _6- ; R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms ( However, it may have an unsaturated bond and may contain a Si group), a phenyl group, an amino group, a halogen atom, or an absence thereof). A photopolymerizable unsaturated compound. 11. The photopolymerizable unsaturated compound according to claim 10, wherein an acid anhydride represented by the formula (I) and an acid dianhydride are used as the acid anhydride.