JP2003233179A - Photosensitive composition and color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive composition excellent in developability and solubility and a color filter formed from the photosensitive composition. <P>SOLUTION: In the photosensitive composition including (A) a photopolymerization initiator and (B) a binder resin having a structure obtained by adding the epoxy moieties of a compound having an ethylenically unsaturated group and epoxy groups to the carboxylic acid moieties of a resin having a carboxylic acid, the compound having an ethylenically unsaturated group and epoxy groups is represented by formula I wherein R<SB>1</SB>is a divalent linking group and R<SB>2</SB>is H or methyl. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photopolymerizable composition, and in particular, in a color filter used in combination with a liquid crystal display device or a solid-state image sensor, colored images (pixels such as red, green, blue and resin black matrix). ) A photopolymerizable composition useful for formation, and a color filter using the same.

[0002]

2. Description of the Related Art Conventionally, as a method for producing a color filter using a pigment, a dyeing method, an electrodeposition method, an ink jet method,
A pigment dispersion method and the like are known. In the case of the pigment dispersion method, a photosensitive coloring composition obtained by adding a photopolymerization initiator and a photopolymerizable monomer to a coloring composition prepared by dispersing a pigment in a binder resin with a dispersant is usually used as a glass substrate. After being coated and dried, a mask is used for exposure and development is performed to form a colored pattern, which is then heated to fix the pattern and form pixels. These steps are repeated for each color to form a color filter.
Thus, in the image formation of the color filter using the photosensitive coloring composition, sufficient resolution, adhesion to the substrate, low development residue, etc. are required. Further, in recent years, a pixel having a high color density and a resin black matrix having a high optical density have been required, and the content of a coloring material such as a pigment or carbon black in the photosensitive coloring composition tends to increase.

On the other hand, in general, a photosensitive composition containing a component capable of being polymerized by light, a photopolymerization initiator and a binder resin, including the above-mentioned photosensitive coloring composition, is subjected to coating, drying, exposure and development. It is subjected to a photolithography process that goes through a process. In such a process, there is no residue or scumming in the removed part in the developing process, the removed part has sufficient solubility, and the formed pixel It is always required to increase the sensitivity of.

In particular, when a pixel is formed by using the photosensitive coloring composition having a high content of the coloring material as described above, a residue or a background stain is generated on the substrate of the unexposed portion during the developing process, Phenomena such as the phenomenon that sufficient solubility is not obtained, and the sensitivity of the pixels formed in the exposed area are not sufficient, and the phenomenon that the coating film physical properties are inferior such as poor surface smoothness is likely to occur remarkably. It was a big problem.

[0005]

It is an object of the present invention to have excellent developability and solubility, and particularly in color filter applications, developability and substrate even when a coloring material such as pigment or carbon black is contained at a high concentration. Another object of the present invention is to provide a photosensitive composition having excellent adhesion to a light-shielding layer and surface smoothness, and a color filter formed from the photosensitive composition.

[0006]

As a result of intensive studies by the present inventors, (1) that the binder resin contained in the photosensitive composition greatly affects the sensitivity and solubility of the photosensitive composition,
(2) Specifically, it is generally used as a component having the properties of both the binder resin and the photo-polymer compound.
A compound having an ethylenically unsaturated group and an epoxy group in a binder resin having a structure formed by an addition reaction between a carboxylic acid moiety of a resin having a carboxylic acid and an epoxy moiety of a compound having an ethylenically unsaturated group and an epoxy group; The present invention was found by finding that the structure is important, and (3) the compound having a specific structure as the compound having an ethylenically unsaturated group and an epoxy group gives particularly excellent results in sensitivity and solubility. It came to completion.

That is, the gist of the present invention is to add an epoxy moiety of a compound having an ethylenically unsaturated group and an epoxy group to a carboxylic acid moiety of a resin having (A) a photopolymerization initiator and (B) a carboxylic acid. In a photosensitive composition containing a binder resin having a structure consisting of, the compound having an ethylenically unsaturated group and an epoxy group,
A photosensitive composition represented by the following structural formula I, and a color filter using the same are provided.

[0008]

[Chemical 2] (In the structural formula I, R ₁ represents a divalent linking group, and R ₂ represents hydrogen or a methyl group.) JP-A-2000-2276
In Japanese Patent Publication No. 55, as a compound having an ethylenically unsaturated group and an epoxy group, (3,4-epoxycyclohexyl) methyl acrylate as shown in Comparative Example 1 described later is described. The structure is different from the compounds shown, and the difference in effect is also remarkable.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The binder resin used in the present invention has a structure in which an epoxy portion of a compound having an ethylenically unsaturated group and an epoxy group is added to a carboxylic acid portion of a resin having a carboxylic acid. Such a structure does not necessarily have to be produced by actually reacting a resin having a carboxylic acid with a compound having an ethylenically unsaturated group and an epoxy group, and as a result, the carboxylic acid moiety of the resin having a carboxylic acid, It may have a structure obtained by adding an epoxy moiety of a compound having an ethylenically unsaturated group and an epoxy group.

The compound having an ethylenically unsaturated group and an epoxy group can be specifically represented by the following structural formula I.

[0011]

[Chemical 3] Here, in the above structural formula I, R ₁ represents a divalent linking group, and R ₂ represents hydrogen or a methyl group.

In the above structural formula I, R ₁ is not particularly limited as long as it is a divalent linking group, and various organic groups having about 1 to 30 carbon atoms can be used, but preferably 1 or more carbon atoms, Particularly, it is an alkyl group having a linear structure, a branched structure or a cyclic structure of 3 or more, and preferably has 20 carbon atoms.
Hereinafter, it is an alkyl group having a linear structure, a branched structure, or a cyclic structure, particularly 10 or less. If the number of carbon atoms is too small, in other words, the distance between the epoxy group and the ethylenically unsaturated group is too short, the developability and the solubility may be insufficient.
However, if the carbon number is too large, the amount of ethylenically unsaturated double bond in the binder resin tends to decrease, and it is difficult to obtain in reality. In a preferred embodiment, in the above structural formula I, R ₁ is an alkyl chain having 1 to 20 carbon atoms, which includes a linear structure, a branched structure or a cyclic structure, particularly an alkyl group having 3 to 10 carbon atoms, Carbon number 3-10
Represents a linear alkyl group.

Specific examples of the compound represented by the structural formula I include various 4-hydroxyalkyl acrylate glycidyl ethers and 4-hydroxyalkyl methacrylate glycidyl ethers. More specifically, 4-hydroxyalkyl glycidyl ethers are mentioned. Butyl acrylate glycidyl ether can be mentioned. The compound having an ethylenically unsaturated group and an epoxy group represented by the structural formula I is
They can be used alone or in combination of two or more, or in combination with a compound having an ethylenically unsaturated group other than I and an epoxy group.

By using the above compound, a photosensitive composition excellent in developability and solubility can be obtained. Although the reason for this is not clear, the number of atoms from the ethylenically unsaturated group to the epoxy group in the above-mentioned compound having a linear structure (atoms adjacent to the ethylenically unsaturated group and carbon atoms constituting the epoxy group It is presumed that this is because the number of atoms in a continuous single atom string in which is connected is relatively long (for example, 8 or more).

The point of the present invention is a structure in which the above-mentioned "compound having an ethylenically unsaturated group and epoxy group" is added to a polymer having a specific structure, specifically a resin having a carboxylic acid, as a binder resin. The use of the polymer having the above means that a photosensitive composition having both high sensitivity and excellent solubility in a developing solution can be obtained.

Here, the structure obtained by adding a "compound having an ethylenically unsaturated group and an epoxy group" to a resin having a carboxylic acid is, for example, 4-hydroxy as a compound having an ethylenically unsaturated group and an epoxy group. When butyl acrylate glycidyl ether is used, a resin having either or both of the following structures in the molecule can be mentioned.

[0017]

[Chemical 4]

[0018]

[Chemical 5] The "resin having a carboxylic acid" in the binder resin of the present invention is not particularly limited, but more specifically,
Examples thereof include a copolymer of a polymerizable unsaturated monomer having a carboxyl group and another copolymerizable unsaturated monomer.

In the present specification, "(meth) acrylic", "(meth) acrylate" and the like mean "acrylic or methacrylic", "acrylate or methacrylate" and the like, for example "( “Meth) acrylic acid” shall mean “acrylic acid or methacrylic acid”. Examples of the polymerizable unsaturated monomer having a carboxyl group include (meth) acrylic acid, (anhydrous) maleic acid, crotonic acid, itaconic acid, fumaric acid, 2-
(Meth) acryloyloxyethyl succinic acid, 2-acryloyloxyethyl adipic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) Acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl succinic acid, 2- (meth) acryloyloxypropyl adipic acid, 2- (meth) acryloyloxypropyl hydrophthalic acid, 2- (meth) acry Royloxypropylphthalic acid, 2- (meth) acryloyloxypropyl maleic acid, 2- (meth) acryloyloxybutyl succinic acid, 2- (meth) acryloyloxybutyl adipic acid, 2- (meth) acryloyloxy Butylhydrophthalic acid, 2- (meth) acryloyloxybutylphthalic acid, 2
-(Meth) acryloyloxybutyl maleic acid (meth), a monomer obtained by adding lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone and δ-valerolactone to acrylic acid, Alternatively, a monomer obtained by adding an acid (anhydride) such as (anhydrous) succinic acid, (anhydrous) phthalic acid or (anhydrous) maleic acid to hydroxyalkyl (meth) acrylate may be used.

Particularly preferred is (meth) acrylic acid. Plural kinds of these may be used. Other copolymerizable monomers are not particularly limited, but include methyl (meth) acrylate, ethyl (meth) acrylate,
Propyl (meth) acrylate, isopropyl (meth)
Acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
Isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, glycerol mono (meth)
N-substituted maleimides such as acrylate, tetrahydrofurfuryl (meth) acrylate, N-vinylpyrrolidone, styrene and its derivatives, α-methylstyrene, N-cyclohexylmaleimide, N-phenylmaleimide, N-benzylmaleimide and polymethyl (meth).
Examples thereof include acrylate macromonomers, polystyrene macromonomers, poly-2-hydroxyethyl (meth) acrylate macromonomers, polyethylene glycol macromonomers, polypropylene glycol macromonomers, polycaprolactone macromonomers, and the like. Particularly preferred are styrene, methyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, butyl methacrylate, isobutyl methacrylate, N-cyclohexylmaleimide, N-benzylmaleimide and N-phenylmaleimide. These may be used in combination.

Examples of the "resin having a carboxylic acid" other than the above include unsaturated group-containing resins obtained by reacting a polybasic acid anhydride of epoxy acrylate, norbornene / maleic anhydride copolymers and half-esterified products thereof. Can be mentioned. Specific examples of the resin having a preferable carboxylic acid include (meth) acrylic acid esters such as benzyl (meth) acrylate, methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and 2-hydroxyethyl methacrylate. / (Meth) acrylic acid copolymer, styrene / (meth) acrylic acid copolymer, styrene / α-methylstyrene / (meth) acrylic acid copolymer, o-cresol novolac type epoxy acrylate and polybasic acid anhydride And an unsaturated group-containing resin reacted with.

The acid value of the binder resin in the present invention is usually 10 to 200 KOHmg / g, preferably 20.
~ 150 KOHmg / g. The acid value of the "resin having a carboxylic acid" in the present invention is usually 80 to 50.
0 KOHmg / g, preferably 100-350 KOHm
g / g, more preferably 150 to 300 KOHmg /
It is g. In addition, when adding a compound having an ethylenically unsaturated group and an epoxy group, the introduction rate of the "resin having a carboxylic acid" into the carboxylic acid is usually 10 to 90 mol.
%, And preferably 30 to 80 mol%. If the introduction rate is too small, the side chain having an ethylenically unsaturated double bond cannot be introduced sufficiently, so that the sensitivity tends to decrease. On the contrary, if the introduction rate is too large, the developability of the photosensitive composition tends to be low. Tends to get worse.

Further, GP of the binder resin in the present invention
The weight average molecular weight of C is usually 1000 to 1000.
00, preferably 2000-80,000, more preferably 3000-50000. If the weight average molecular weight is too small, the film-forming property may be poor and the surface properties of the obtained pixels may be deteriorated. If it is too large, the solubility may be deteriorated.

For the synthesis of the binder resin in the present invention, a method of reacting a carboxylic acid of a resin having a carboxylic acid with a compound having an ethylenically unsaturated group and an epoxy group is preferably used. As a method for reacting a compound having an ethylenically unsaturated group and an epoxy group with a carboxyl group of a resin having a carboxylic acid, a known method can be used.

For example, a resin body having the above-mentioned carboxylic acid and a compound having an unsaturated group and an epoxy group are treated with a tertiary amine such as triethylamine or benzylmethylamine, dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, Reaction temperature 50-150 ° C in organic solvent using quaternary ammonium salt such as benzyltriethylammonium chloride, pyridine, triphenylphosphine, etc.
The epoxy compound can be introduced into the carboxyl group of the polymer by reacting for several to several tens of hours.

The photopolymerization initiator used in the present invention is not particularly limited as long as it is a compound capable of polymerizing an ethylenically unsaturated group by actinic rays, but the photosensitive composition of the present invention is a compound having a polymerizable group. When it contains an ethylenic compound, it is preferable to use a photopolymerization initiator having a function of directly absorbing light or being photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization active radical. .

Specific examples of the polymerization initiator that can be used in the present invention are listed below. 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4 -Ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-
Halomethylated triazine derivatives such as bis (trichloromethyl) -s-triazine; 2-trichloromethyl-5-
(2'-benzofuryl) -1,3,4-oxadiazole,
2-trichloromethyl-5- [β- (2'-benzofuryl) vinyl] -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2 '-(6 "-benzofuryl)
Vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole and other halomethylated oxadiazole derivatives; 2- (2'-chlorophenyl)- 4,5-diphenyl imidazole dimer, 2
-(2'-chlorophenyl) -4,5-bis (3'-methoxyphenyl) imidazole dimer, 2- (2'-fluorophenyl) -4,5-diphenylimidazole dimer, 2-
Imidazole derivatives such as (2'-methoxyphenyl) -4,5-diphenylimidazole dimer and (4'-methoxyphenyl) -4,5-diphenylimidazole dimer; benzoin methyl ether, benzoin phenyl ether, Benzoin alkyl ethers such as benzoin isobutyl ether and benzoin isopropyl ether; 2
-Methylanthraquinone, 2-Ethylanthraquinone, 2
Anthraquinone derivatives such as -t-butylanthraquinone and 1-chloroanthraquinone; benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, etc. Benzophenone derivative; 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl -(P-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4 '-(methylthio) phenyl) -2-morpholino-1-propanone,
Acetophenone derivatives such as 1,1,1-trichloromethyl- (p-butylphenyl) ketone; thioxanthone, 2-
Thioxanthone derivatives such as ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone;
Benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl P-diethylaminobenzoate; acridine derivatives such as 9-phenylacridine and 9- (p-methoxyphenyl) acridine; phenazines such as 9,10-dimethylbenzphenazine Derivatives; anthrone derivatives such as benzanthrone; di-cyclopentadienyl-Ti-di-chloride, di-cyclopentagenyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,3, Four,
5,6-pentafluorophenyl-11-yl, di-cyclopentagenyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, di-cyclopentagenyl-Ti
-Bis-2,4,6-trifluorophen-1-yl, di-
Cyclopentagenyl-Ti-2,6-dipleuropheni-1-yl, di-cyclopentagenyl-Ti-2,4-di-fluorophenyl-1-yl, di-methylcyclopentagenyl-Ti -Bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentenyl-T
i-Bis-2,6-di-fluorophen-1-yl, di-cyclopentagenyl-Ti-2,6-di-fluoro-3-
Titanocene derivatives such as (pyr-1-yl) -phen-1-yl.

In addition to these, the photopolymerization initiator which can be used in the present invention is described in Fine Chemical, March 1, 1991, Vol. 20, No. 4, P. 16-P26, JP-A-59-152396, JP-A-61-1511.
97, JP-B-45-37737, JP-A-5
It is also described in JP-A-8-40302 and JP-A-10-39503.

The blending ratio of the photopolymerization initiator is usually 0.1% by weight or more, preferably 0.5% by weight or more, more preferably 0.7% by weight, based on the total solid content of the composition of the present invention. It is above 30% by weight, preferably 20% by weight or less, more preferably 10% by weight or less. If the blending ratio is extremely low, the sensitivity may be lowered. On the contrary, if the blending ratio is extremely high, the solubility of the unexposed portion in the developing solution is lowered and the development failure is likely to be induced.

If necessary, a sensitizing dye corresponding to the wavelength of the image forming exposure light source can be incorporated into the photosensitive composition for the purpose of enhancing the sensitivity. Examples of these sensitizing dyes include JP-A-4-221958 and 4-
Xanthene dyes described in JP-A-219756, JP-A-3
-239703 and 5-289335, a coumarin dye having a heterocycle, JP-A-3-239
No. 703 and No. 5-289335.
-Ketocoumarin compounds, pyrromethene dyes described in JP-A-6-19240, other JP-A-47-2528, JP-A-54-155292, and JP-B-45-37.
377, JP-A-48-84183, 52.
No. 112681, No. 58-15503, No. 60-88005, No. 59-56403,
JP-A-2-69, JP-A-57-168088, JP-A-5-107761, and JP-A-5-210
Examples thereof include dyes having a dialkylaminobenzene skeleton described in JP-A-240240 and JP-A-4-288818.

Preferred sensitizing dyes that can be used in the present invention are compounds containing an amino group, and more preferred are compounds having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4,4′-dimethylaminobenzophenone, 4,4′-dimethylaminobenzophenone,
4'-diethylaminobenzophenone, 4,4'-methylethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone,
Benzophenone compounds such as 3,4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl)
Benzo [4,5] benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl)-
1,3,4-Oxazole, 2- (p-dimethylaminophenyl) benzothiazole, 2- (p-diethylaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) ) Benzimidazole, 2,5-bis (p-diethylaminophenyl) -1,3,4-thiadiazole, (p-dimethylaminophenyl) pyridine,
(P-Diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl)
Examples thereof include p-dialkylaminophenyl group-containing compounds such as pyrimidine and (p-diethylaminophenyl) pyrimidine. Of these, the most preferred is 4,4'-dialkylaminobenzophenone.

The compounding ratio of the sensitizing dye is usually 0.05% by weight or more, preferably 0.2% by weight or more, more preferably 0.5% by weight or more, based on the total solid content of the composition of the present invention. It is usually 20% by weight or less, preferably 15% by weight or less, and more preferably 10% by weight or less. If the blending amount is too large, the pattern accuracy may decrease, while if it is too small, the pattern itself is difficult to form.

In the photosensitive composition, if necessary, further,
An accelerator can be added for the purpose of increasing the sensitivity. As the accelerator, for example, N, N-dialkylaminobenzoic acid alkyl ester such as N, N-dimethylaminobenzoic acid ethyl ester; a complex such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 2-mercaptobenzimidazole A mercapto compound having a ring, an aliphatic polyfunctional mercapto compound, or the like is used. The photopolymerization initiator and the accelerator may be combined in plural kinds.

The compounding ratio of the accelerator is usually 0.05% by weight or more, preferably 0.1% by weight based on the total solid content of the composition of the present invention.
2% by weight or more, more preferably 0.5% by weight or more, and usually 20% by weight or less, preferably 15% by weight
Hereafter, it is more preferably 10% by weight or less. If the blending amount is too large, the pattern accuracy may decrease, while if it is too small, the pattern itself is difficult to form.

In the present invention, it is preferable to use a photopolymerizable monomer (photopolymerizable compound) in addition to the photopolymerization initiator and the binder resin from the viewpoint of sensitivity and the like. Examples of the photopolymerizable monomer used in the present invention include compounds having at least one ethylenically unsaturated group. Specific examples of the compound having an ethylenically unsaturated group in the molecule include (meth) acrylic acid, an alkyl ester of (meth) acrylic acid, acrylonitrile, styrene, a carboxylic acid having one ethylenically unsaturated bond, and a poly ( single)
Examples thereof include monoesters of polyhydric alcohols.

In the present invention, it is desirable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups in one molecule. Examples of such polyfunctional ethylenic monomers include, for example, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds, aromatic Examples thereof include esters obtained by an esterification reaction of a polyhydroxy compound such as a polyhydroxy compound with an unsaturated carboxylic acid and a polycarboxylic acid.

The ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid is not limited, but includes ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, Acrylic esters of aliphatic polyhydroxy compounds such as pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, etc. Replaced methacrylic acid ester, similarly itacone replaced with itaconate Esters, maleic acid esters, and the like was replaced with crotonic acid ester or maleate was replaced Kuroneto.

Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include acrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate and pyrogallol triacrylate. Examples thereof include methacrylic acid ester.

The ester obtained by the esterification reaction of the unsaturated carboxylic acid or polyvalent carboxylic acid and the polyvalent hydroxy compound is not necessarily a single substance, but representative specific examples include acrylic acid, phthalic acid, And ethylene glycol condensates, acrylic acid, maleic acid, and diethylene glycol condensates, methacrylic acid, terephthalic acid and pentaerythritol condensates, acrylic acid, adipic acid, butanediol and glycerin.

Other examples of the polyfunctional ethylenic monomer used in the present invention include a polyisocyanate compound and a hydroxyl group-containing (meth) acrylic acid ester or a polyisocyanate compound and a polyol and a hydroxyl group-containing (meth) acrylic acid ester. Urethane (meth) acrylates obtained by reaction; epoxy acrylates such as addition reaction products of polyvalent epoxy compounds with hydroxy (meth) acrylate or (meth) acrylic acid; acrylamides such as ethylenebisacrylamide; Allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate are useful.

In the above, the term "photopolymerizable monomer" does not necessarily mean a monomer as a repeating unit for a polymer, but various compounds that become a polymer by polymerization.

The photopolymerizable composition of the present invention contains a coloring material in addition to the binder resin, the photopolymerization initiator and the photopolymerizable monomer used as the case requires, so that the pixel of the color filter ( It is possible to provide a photosensitive coloring composition effective for forming red, blue and green pixels and a resin black matrix.

As the coloring material, various dyes and pigments can be used, but pigments are preferable from the viewpoint of heat resistance and light resistance. As the pigment, various color pigments such as blue pigment, green pigment, red pigment, yellow pigment, purple pigment, orange pigment, brown pigment, and black pigment can be used. Also, as its structure, azo type, phthalocyanine type, quinacridone type,
In addition to benzimidazolone-based, isoindolinone-based, dioxazine-based, indanthrene-based, perinone-based organic pigments, various inorganic pigments and the like can be used.

Specific examples of pigments that can be used are shown below by pigment numbers. The terms such as “C.I. Pigment Red 2” mentioned below are referred to as color index (C.I.
I. ) Means. Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 1
2, 14, 15, 16, 17, 21, 22, 23, 3
1, 32, 37, 38, 41, 47, 48, 48: 1,
48: 2, 48: 3, 48: 4, 49, 49: 1, 4
9: 2, 50: 1, 52: 1, 52: 2, 53, 53:
1, 53: 2, 53: 3, 57, 57: 1, 57: 2,
58: 4, 60, 63, 63: 1, 63: 2, 64, 6
4: 1, 68, 69, 81, 81: 1, 81: 2, 8
1: 3, 81: 4, 83, 88, 90: 1, 101, 1
01: 1, 104, 108, 108: 1, 109, 11
2, 113, 114, 122, 123, 144, 14
6, 147, 149, 151, 166, 168, 16
9, 170, 172, 173, 174, 175, 17
6, 177, 178, 179, 181, 184, 18
5, 187, 188, 190, 193, 194, 20
0, 202, 206, 207, 208, 209, 21
0, 214, 216, 220, 221, 224, 23
0, 231, 232, 233, 235, 236, 23
7, 238, 239, 242, 243, 245, 24
7, 249, 250, 251, 253, 254, 25
5, 256, 257, 258, 259, 260, 26
2, 263, 264, 265, 266, 267, 26
8, 269, 270, 271, 272, 273, 27
4, 275 and 276 can be mentioned. Among these, C.I. I. Pigment Red 48: 1, 1
22, 168, 177, 202, 206, 207, 20
9, 224, 242, 254, more preferably C.I.
I. Pigment Red 177, 209, 224, 254
Can be mentioned.

As the blue pigment, C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15:
2, 15: 3, 15: 4, 15: 6, 16, 17, 1
9, 25, 27, 28, 29, 33, 35, 36, 5
6, 56: 1, 60, 61, 61: 1, 62, 63, 6
6, 67, 68, 71, 72, 73, 74, 75, 7
6, 78, 79 can be mentioned. Among these, C.I. I. Pigment Blue 15, 15: 1, 1
5: 2, 15: 3, 15: 4, 15: 6, more preferably C.I. I. Pigment Blue 15: 6 can be mentioned.

As the green pigment, C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15,
17, 18, 19, 26, 36, 45, 48, 50, 5
1, 54, 55 can be mentioned. Among these, C.I. I. Pigment Green 7, 36 can be mentioned. Examples of the yellow pigment include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10,
12, 13, 14, 16, 17, 24, 31, 32, 3
4, 35, 35: 1, 36, 36: 1, 37, 37:
1, 40, 41, 42, 43, 48, 53, 55, 6
1, 62, 62: 1, 63, 65, 73, 74, 75,
81, 83, 87, 93, 94, 95, 97, 100,
101, 104, 105, 108, 109, 110, 1
11, 116, 117, 119, 120, 126, 12
7, 127: 1, 128, 129, 133, 134, 1
36, 138, 139, 142, 147, 148, 15
0, 151, 153, 154, 155, 157, 15
8, 159, 160, 161, 162, 163, 16
4,165,166,167,168,169,17
0, 172, 173, 174, 175, 176, 18
0, 181, 182, 183, 184, 185, 18
8, 189, 190, 191, 191: 1, 192, 1
93, 194, 195, 196, 197, 198, 19
9, 200, 202, 203, 204, 205, 20
6,207,208 can be mentioned. Among these, C.I. I. Pigment Yellow 83, 11
7,129,138,139,150,154,15
5,180,185, more preferably C.I. I. Pigment Yellow 83, 138, 139, 150, 180.

Examples of orange pigments include C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 2
0, 21, 22, 23, 24, 34, 36, 38, 3
9, 43, 46, 48, 49, 61, 62, 64, 6
5, 67, 68, 69, 70, 71, 72, 73, 7
4, 75, 77, 78, 79 can be mentioned. Among these, C.I. I. Pigment Orange 3
8, 71 can be mentioned.

Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3:
3,5,5: 1,14,15,16,19,23,2
5, 27, 29, 31, 32, 37, 39, 42, 4
4, 47, 49, 50 can be mentioned. Among these, C.I. I. Pigment Violet 19,
23, more preferably C.I. I. Pigment Violet 23 can be mentioned.

Further, when the resin black matrix of the color filter is formed by using the photosensitive coloring composition, a black coloring material can be used. Black color material is a single color and uses single or multiple black color materials, or red,
It is possible to use a black color material by mixing green, blue and the like. Further, these coloring materials can be appropriately selected from inorganic or organic pigments and dyes. In the case of an inorganic or organic pigment, it is preferable to use it by dispersing it to have an average particle size of 1 μm or less, preferably 0.5 μm or less.

Specific examples of color materials that can be mixed and used include Victoria Pure Blue (42595) and Auramine O (4
1000), Catillon brilliant flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170), Safranin OK 70: 100.
(50240), Erioglaucine X (42080),
No. 120 / Rionol Yellow (21090), Rionol Yellow GRO (21090), Shimla First Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Shimla First Red 4015 (12355), Rionol Red 7
B4401 (15850), Fast Gen Blue TG
RL (74160), Lionol Blue SM (261
50), Lionol Blue ES (Pigment Blue 1
5: 6), Rionogen Red GD (Pigment Red 168), Rionol Green 2YS (Pigment Green 36) and the like (the numbers in the above parentheses () are color indexes (CI)). To).

Further, regarding other pigments which can be mixed and used, C.I. I. When it is indicated by a number, for example, C.I. I. Yellow pigment 20, 24, 86, 93, 109, 110, 11
7, 125, 137, 138, 147, 148, 15
3, 154, 166, C.I. I. Orange pigment 36, 4
3, 51, 55, 59, 61, C.I. I. Red pigment 9,9
7, 122, 123, 149, 168, 177, 18
0, 192, 215, 216, 217, 220, 22
3, 224, 226, 227, 228, 240, C.I.
I. Violet pigments 19, 23, 29, 30, 37,
40, 50, C.I. I. Blue pigment 15, 15: 1, 15:
4, 22, 60, 64, C.I. I. Green pigment 7, C.I. I.
Brown pigments 23, 25, 26 and the like can be mentioned.

As a black color material which can be used alone,
Carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black,
Examples include cyanine black and titanium black. Of these, carbon black is preferable from the viewpoint of light-shielding rate and image characteristics. Examples of carbon black include the following carbon blacks. Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA100, MA10
0R, MA220, MA230, MA600, # 5, #
10, # 20, # 25, # 30, # 32, # 33, # 4
0, # 44, # 45, # 47, # 50, # 52, # 5
5, # 650, # 750, # 850, # 950, # 96
0, # 970, # 980, # 990, # 1000, # 2
200, # 2300, # 2350, # 2400, # 26
00, # 3050, # 3150, # 3250, # 360
0, # 3750, # 3950, # 4000, # 401
0, OIL7B, OIL9B, OIL11B, OIL3
0B, OIL31B Degussa: Printex3, P
printex3OP, Printex30, Print
ex30OP, Printex40, Printex4
5, Printex55, Printex60, Pri
ntex75, Printex80, Printex8
5, Printex90, Printex A, Pri
ntex L, Printex G, Printex
P, Printex U, Printex V, Pri
ntexG, SpecialBlack550, Spe
cialBlack350, SpecialBlack
250, SpecialBlack100, Speci
alBlack6, SpecialBlack5, Sp
ecoalBlack4, Color Black F
W1, ColorBlack FW2, Color B
rack FW2V, Color Black FW1
8, Color Black FW18, Color
Black FW200, Color Black S
160, Color Black S170 manufactured by Cabot: Monarch 120, Monarch 280, M
onarch460, Monarch800, Mona
rch880, Monarch900, Monarch
1000, Monarch1100, Monarch1
300, Monarch1400, Monarch46
30, REGAL99, REGAL99R, REGAL
415, REGAL 415R, REGAL250, RE
GAL250R, REGAL330, REGAL400
R, REGAL55R0, REGAL660R, BLA
CK PEARLS 480, PEARLS 130, VU
LCAN XC72R, ELFTEX-8 Colombian Carbon Co., Ltd .: RAVEN11, RAVEN14, R
AVE15, RAVEN16, RAVEN22RAV
EN30, RAVEN35, RAVEN40, RAVE
N410, RAVEN420, RAVEN450, RA
VEN500, RAVEN780, RAVEN850,
RAVEN890H, RAVEN1000, RAVEN
1020, RAVEN1040, RAVEN1060
U, RAVEN1080U, RAVEN1170, RA
VEN1190U, RAVEN1250, RAVEN1
500, RAVEN2000, RAVEN2500U,
Raven3500, raven5000, raven
Examples of black pigments such as 5250, RAVEN 5750, and RAVEN 7000 can be used as black pigments by mixing titanium black, aniline black, iron oxide-based black pigments, and organic pigments of three colors of red, green, and blue. .

As the pigment, barium sulfate, lead sulfate, titanium oxide, yellow lead, red iron oxide, chromium oxide and the like can be used. Plural kinds of these various pigments can be used in combination. For example, in order to adjust the chromaticity, it is possible to use a green pigment and a yellow pigment together or a blue pigment and a purple pigment together as the pigment.

These pigments have an average particle size of 1 μm, preferably 0.5 μm or less, more preferably 0.25 μm.
The following is preferable. It is particularly preferable to use resin-coated carbon black for producing a resin black matrix having high optical density and high surface resistivity. The photosensitive composition of the present invention contains the photopolymerizable monomer 10 to 200 relative to 100 parts by weight of the binder resin.
From the viewpoints of developability and sensitivity, it is preferable that the content of the photopolymerization initiator is in the range of 0.05 to 70 parts by weight. Further, when the photosensitive coloring composition is used, the coloring material is preferably 15 to 15% based on the total solid content.
It is contained in the range of 70% by weight.

In the present invention, in addition to these essential components, an organic solvent, a pigment dispersant, an adhesion improver, a coatability improver, a development improver, an ultraviolet absorber, an antioxidant and the like can be added as appropriate. In addition, a silane coupling agent can be added to improve the adhesion to the substrate.

As the silane coupling agent, various types such as epoxy type, methacrylic type and amino type can be used, and epoxy type silane coupling agent is particularly preferable. The photosensitive coloring composition of the present invention is produced according to a conventional method. For example, an ink is prepared by dispersing a coloring material, an organic solvent, a binder resin having a dispersing function, a pigment dispersant, etc., and further blending and mixing the binder resin, the photopolymerizable monomer, the photopolymerization initiator, etc. It can be obtained by preparing a different solution.

The organic solvent is not particularly limited, but for example, diisopropyl ether, mineral spirit, n
-Pentane, amyl ether, ethyl caprylate, n
-Hexane, diethyl ether, isoprene, ethyl isobutyl ether, butyl stearate, n-octane, balsol # 2, Apco # 18 solvent, diisobutylene, amyl acetate, butyl butyrate, apco thinner, butyl ether, diisobutyl ketone, methylcyclohexene, Methyl nonyl ketone, propyl ether, dodecane, Socal solvent No.
1 and No. 2, amyl formate, dihexyl ether, diisopropyl ketone, Solvesso # 150, butyl acetate (n, sec, t), hexene, shell TS
28 Solvent, butyl chloride, ethyl amyl ketone, ethyl benzonate, amyl chloride, ethylene glycol diethyl ether, ethyl orthoformate, methoxymethylpentanone, methyl butyl ketone,
Methyl hexyl ketone, methyl isobutyrate, benzonitrile, ethyl propionate, methyl cellosolve acetate, methyl isoamyl ketone, methyl isobutyl ketone, propyl acetate, amyl acetate, amyl formate, bicyclohexyl, diethylene glycol monoethyl ether acetate, dipentene, Methoxymethyl pentanol, methyl amyl ketone, methyl isopropyl ketone, propyl propionate, propylene glycol-t-butyl ether, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, carbitol, cyclohexanone,
Ethyl acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, propylene glycol monoethyl ether acetate, Dipropylene glycol monomethyl ether acetate,
3-methoxypropionic acid, 3-ethoxypropionic acid, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate,
Propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, dipropylene glycol monomethyl ether, ethylene glycol acetate,
Ethyl carbitol, butyl carbitol, ethylene glycol monobutyl ether, propylene glycol-
t-butyl ether, 3-methyl-3-methoxybutanol, tripropylene glycol methyl ether, 3-
Specific examples thereof include organic solvents such as methyl-3-methoxybutyl acetate.

The solvent is capable of dissolving or dispersing each component, and it is preferable to select a solvent having a boiling point in the range of 100 to 200 ° C. More preferably 120 to 17
It has a boiling point of 0 ° C. These solvents can be used alone or as a mixture. In the dispersion treatment, it is particularly preferable to use a polymer dispersant as a pigment dispersant because the dispersion stability over time is excellent.

Usually, it is preferable that the coloring material is previously subjected to a dispersion treatment using a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer or the like. Since the coloring material is made into fine particles by the dispersion treatment, the coating characteristics of the resist can be improved. When dispersing with a sand grinder,
Glass beads or zirconia beads having a diameter of 0.1 to several millimeters are preferably used. The dispersion is usually carried out at a temperature of 0 ° C. to 100 ° C., preferably room temperature to 8 ° C.
It is in the range of 0 ° C. The dispersion time varies depending on the composition of the ink (black color material, solvent, dispersant), the size of the sand grinder, and the like, and is appropriately adjusted.

Next, a binder resin, a photopolymerizable monomer, a photopolymerization initiator, and an organic solvent are added to the ink obtained by the above dispersion treatment and mixed to form a uniform solution. Since fine dust is often mixed with the photosensitive liquid in the manufacturing process, it is desirable to filter the obtained photosensitive colored composition with a filter or the like. Next, a method of manufacturing a pixel using the photosensitive coloring composition of the present invention, a resin black matrix, and a color filter having the same will be described.

First, a photosensitive coloring composition containing a coloring material is applied on a transparent substrate by a spinner, a wire bar, a flow coater,
After coating with a coating device such as a die coater, roll coater, or spray and drying, a photomask is placed on the sample, and image exposure, development through the photomask, heat curing or photocuring as necessary. It is formed. Pixels can be formed by using a red-green-blue color material as a color material, and a resin black matrix can be formed by using a black color material. A color filter is formed by repeating this process.

The transparent substrate used here is a transparent substrate for a color filter, and its material is not particularly limited. For example, polyester such as polyethylene terephthalate, polypropylene, polyolefin such as polyethylene, polycarbonate, poly Methyl methacrylate, polysulfone thermoplastic sheet,
Examples thereof include thermosetting plastic sheets such as epoxy resin, polyester resin, poly (meth) acrylic resin, and various glass plates. In particular, a glass plate and a heat resistant plastic are preferably used from the viewpoint of heat resistance.

Such a transparent substrate is previously subjected to corona discharge treatment, ozone treatment, thin film treatment of various polymers such as silane coupling agent and urethane polymer, etc. in order to improve physical properties such as surface adhesiveness. You can also A hot plate, an IR oven, a convection oven, or the like can be used for the drying, and the preferable drying conditions are 40 to 150 ° C. and the drying time is 10 seconds to 60 minutes.

The light source used for the exposure is, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, a super high pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp or the like, an argon ion laser, a YAG laser, Examples thereof include laser light sources such as excimer lasers and nitrogen lasers. An optical filter can also be used when only the wavelength of a specific irradiation light is used.

The developing treatment is not particularly limited as long as it is a solvent capable of dissolving the resist (photosensitive coloring composition) film in the unexposed area, but for example, environmental pollution, harmfulness to human body, fire risk, etc. From the viewpoint of, it is a preferable method to use an alkali developing solution rather than an organic solvent. Examples of such an alkaline developer include inorganic alkali agents such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate, sodium silicate, potassium silicate, sodium hydroxide and potassium hydroxide, or diethanolamine, triethylamine, triethanolamine, water. An aqueous solution containing an organic alkali agent such as a tetraalkylammonium oxide salt or tetramethylammonium hydroxide can be used.

If necessary, the alkaline developer may contain a surfactant, a water-soluble organic solvent, a wetting agent, a low molecular compound having a hydroxyl group or a carboxylic acid group, and the like. In particular, it is preferable to add a surfactant because many of them have an improving effect on developability, resolution and background stain. For example, as the surfactant for the developing solution, a sodium naphthalenesulfonate group, an anionic surfactant having a sodium benzenesulfonate group, a nonionic surfactant having a polyalkyleneoxy group, a cation having a tetraalkylammonium group Examples thereof include a surface active agent.

The developing treatment method is not particularly limited, but it is usually carried out at a developing temperature of 10 to 50 ° C., preferably 15 to 45 ° C. by a method such as immersion development, spray development, brush development and ultrasonic development. . The resin black matrix and pixels formed are preferably subjected to a heat curing treatment in order to improve film strength, solvent resistance, alkali resistance, etc. after image formation.

This heat curing treatment is preferably performed at 150 ° C. or higher and lower than 300 ° C. If the temperature is 150 ° C. or lower, the thermal curing is insufficient, so that problems such as film strength, solvent resistance and alkali resistance are likely to occur. At a temperature of 300 ° C. or higher, excessive volume shrinkage occurs, and problems are likely to occur in adhesion to the substrate and accuracy.

[0069]

The present invention will be described in more detail with reference to the following examples and test examples, but the present invention is not limited to the following examples unless it exceeds the gist.

<Synthesis Example 1> Acid value 240, molecular weight 1380
0 styrene / α-methylstyrene / acrylic acid resin 1
0 g, p-methoxyphenol 0.02 g, tetraethylammonium chloride 0.05 g, propylene glycol monomethyl ether acetate 24.4 g was charged into a reaction vessel, and after heating and dissolving, 6.3 g of 4-hydroxybutyl acrylate glycidyl ether was added dropwise, 90
The reaction was conducted at 24 ° C. for 24 hours to obtain a binder resin solution having an ethylenically unsaturated group in its side chain. The thus-obtained binder resin had a polymerization average molecular weight of 34,000 in terms of polystyrene, and a neutralization titration with KOH showed an acid value of 58. The rate of introduction of 4-hydroxybutyl acrylate glycidyl ether into the carboxylic acid was 61% based on the acid value before and after the reaction. <Synthesis Example 2> 35.0 g of propylene glycol monomethyl ether acetate, 8.8 g of 1-methoxy-2-propanol, V-59 (a polymerization initiator manufactured by Wako Pure Chemical Industries, Ltd.)
1.5 g was charged into a reaction vessel, the temperature was raised to 80 ° C. under a nitrogen atmosphere, and benzyl methacrylate 9.5 g, methyl methacrylate 6.5 g, 2-hydroxyethyl methacrylate 3.5 g, and methacrylic acid 10.7 g were taken for 2 hours. The mixture was added dropwise and stirred for 4 hours to obtain a polymerization reaction liquid. Furthermore, 27.7 g of propylene glycol monomethyl ether acetate was added to this polymerization reaction liquid, and p-methoxyphenol 0.05 g and triphenylphosphine 0.3
After adding and dissolving 4 g, 18.7 g of 4-hydroxybutyl acrylate glycidyl ether was added dropwise to 85
The reaction was conducted at 24 ° C. for 24 hours to obtain a binder resin solution having an ethylenically unsaturated group in its side chain. The thus-obtained binder resin had a polymerization average molecular weight of 26000 in terms of polystyrene, and a neutralization titration with KOH showed an acid value of 47. The rate of introduction of 4-hydroxybutyl acrylate glycidyl ether into the carboxylic acid was 67% based on the acid value before and after the reaction. <Synthesis Example 3> 25 g of a tetrahydrophthalic anhydride adduct of o-cresol type novolak epoxy acrylate having an acid value of 84 and a molecular weight of 5000 (65% solution), 0.01 g of p-methoxyphenol, and 0.13 g of triphenylphosphine were added. Propylene glycol monomethyl ether acetate 9.91 g was charged into a reaction vessel, and after heating and mixing, 2.69 g of 4-hydroxybutyl acrylate glycidyl ether was added dropwise, and the mixture was reacted at 90 ° C. for 24 hours,
A binder resin solution having an ethylenically unsaturated group in its side chain was obtained. GP of the binder resin thus obtained
The weight average molecular weight by C is 540 in terms of polystyrene.
When the neutralization titration was carried out with 0 and KOH, the acid value was 37. The rate of introduction of 4-hydroxybutyl acrylate glycidyl ether into the carboxylic acid was 48% based on the acid value before and after the reaction. <Synthesis Example 4> 10 g of a styrene / α-methylstyrene / acrylic acid resin having an acid value of 240 and a molecular weight of 13800, 0.2 g of p-methoxyphenol, 0.5 g of tetraethylammonium chloride, and 23.2 g of propylene glycol monomethyl ether acetate. Charge to
5.70 g of (3,4-epoxycyclohexyl) methyl acrylate was added dropwise and reacted at a temperature of 90 ° C. for 32 hours. The thus-obtained binder resin having an ethylenically unsaturated group in its side chain had a polymerization average molecular weight by GPC of 20,100 in terms of polystyrene. KOH
The acid value was 56 when the neutralization titration by.
The rate of introduction of (3,4-epoxycyclohexyl) methyl acrylate into the carboxylic acid was 64% based on the acid value before and after the reaction. <Synthesis example 5> 35.0 g of propylene glycol monomethyl ether acetate, 8.8 g of 1-methoxy-2-propanol, and 1.5 g of V-59 (azo polymerization initiator manufactured by Wako Pure Chemical Industries, Ltd.) were charged into a reaction vessel. , Under nitrogen atmosphere,
The temperature was raised to 80 ° C., benzyl methacrylate 9.5 g, methyl methacrylate 6.5 g, 2-hydroxyethyl methacrylate 3.5 g, and methacrylic acid 10.7 g were added dropwise over 2 hours, and the mixture was further stirred for 4 hours to obtain a polymerization reaction liquid. Got Further, 25.5 g of propylene glycol monomethyl ether acetate was added to this polymerization reaction liquid, and p-
After adding and dissolving 0.05 g of methoxyphenol and 0.33 g of triphenylphosphine, 17.5 g of (3,4-epoxycyclohexyl) methyl acrylate was added dropwise and reacted at 85 ° C. for 32 hours to give ethylenic side chains. A binder resin solution having an unsaturated group was obtained. The polymerization average molecular weight of the binder resin thus obtained by GPC was 18,000 in terms of polystyrene, and the acid value was 50 when subjected to neutralization titration with KOH.
The introduction rate of carboxylic acid by (3,4-epoxycyclohexyl) methyl acrylate was 66% based on the acid value before and after the reaction. <Example 1> Phthalocyanine blue 22.4 as a pigment
g, a polymer dispersant 8.97 g, a dispersion aid 1.12 g, and propylene glycol monomethyl ether acetate 74 g as a solvent were dispersed with a paint conditioner containing zirconia beads to obtain a blue ink. Here, the polymer dispersant is Big Chemie (manufactured by Disperbyk1
61, Solsperse 5000 (manufactured by Zeneca Corp.) was used as a dispersion aid. 10.9 g of the blue ink thus obtained, 11.0 g of the alkali-soluble resin solution obtained in Synthesis Example 1, and 1.45 g of a 50% propylene glycol monomethyl ether acetate solution of dipentaerythritol hexaacrylate as a photopolymerizable monomer. ,
Biimidazole 0.26 g as a photopolymerization initiator, 4,4′-bis (diethylamino) benzophenone (EABF) 0.18 g as a sensitizer, 2-mercaptobenzothiazole (2MBT) 0.05 g as a chain transfer agent, fluorine The system surfactant (FC-430 manufactured by Sumitomo 3M Ltd.) was added to 0.
001 g, maleic anhydride 0.2 g, propylene glycol monomethyl ether acetate 28.1 as solvent
g was stirred and mixed to obtain a photosensitive blue composition.

On a glass substrate (AN635 manufactured by Asahi Glass Co., Ltd.)
The photosensitive blue composition is spin-coated and hot-played.
Heat dried at 70 ° C for 2 minutes and 30 seconds, thickness 1.5 μm
To obtain a photosensitive blue layer. Use an ultra high pressure mercury lamp for this coating
100-200 mJ / cm ²Of the ultraviolet rays. This
After alkaline developer (0.14 wt% potassium carbonate, charcoal
0.34% by weight potassium hydrogen hydrate, surfactant: made by Kao
"Emulgen A-60" 0.4% by weight aqueous solution)
-Develop and wash with ultrapure water for 10 seconds to form a blue pattern
It was When the pattern after development was observed, it was 50 mJ / c.
m²Exposure, the unexposed area can be dissolved and removed by developing for 20 seconds.
And a pattern with good line shape and good adhesion was obtained. <Comparative Example 1> Using the binder resin obtained in Synthesis Example 4
Other than that, a blue pattern is formed in the same process as in Example 1.
did. 200 mJ / cm²Exposure was required. Unexposed
It took 50 seconds of development to dissolve and remove the light portion. line
A pattern having a good shape and adhesion was obtained. <Example 2> Using the binder resin obtained in Synthesis Example 2
Other than that, a blue pattern is formed in the same process as in Example 1.
did. 50 mJ / cm²Exposure, no development after 23 seconds of development
A pattern that can dissolve and remove the light part and has a good line shape and good adhesion.
You got <Comparative Example 2> Using the binder resin obtained in Synthesis Example 5
Other than that, a blue pattern is formed in the same process as in Example 1.
did. 200 mJ / cm²Exposure was required. Unexposed
It took 80 seconds of development to dissolve and remove the light portion. line
A pattern having a good shape and adhesion was obtained. <Example 3> 22.5 g of carbon black as a pigment,
Polymer dispersant 11.0g, propylene glycol as solvent
Zirco with 83.0 g of monomethyl ether acetate
Disperse with a paint conditioner containing near beads
Then, a black ink was obtained. Here, carbon black is M
A220 (manufactured by Mitsubishi Chemical Corporation), the polymeric dispersant is
Using Disperbyk 182 manufactured by Kukemi Co., Ltd.
It was Combined with 7.16 g of the black ink thus obtained
2.71 g of the alkali-soluble resin solution obtained in Example 3,
Dipentaerythritol hexa as a photopolymerizable monomer
0.27 g of acrylate, CGI7 as a photopolymerization initiator
0.12 g of 84 (manufactured by Ciba-Geigy Co., Ltd.), sensitizer
, 0.07 g of EABF, and N-F as chain transfer agent
0.32 g of phenylglycine, fluorochemical surfactant (Sumitomo
0.05 g of 3M FC-430), a professional solvent
Pyrene glycol monomethyl ether acetate 9.1
6 g was stirred and mixed to obtain a photosensitive black composition.

A glass substrate (AN635 manufactured by Asahi Glass Co., Ltd.) was spin-coated with the above-mentioned photosensitive black composition, and dried by heating on a hot plate at 90 ° C. for 2 minutes and 30 seconds to give a thickness of 1.0 μm.
To obtain a photosensitive black layer. This coating film was irradiated with ultraviolet rays of 100 to 400 mJ / cm2 using an ultrahigh pressure mercury lamp. After this, shower development with an alkaline developer (0.06 wt% potassium carbonate, 0.24 wt% potassium hydrogen carbonate, surfactant: 0.05 wt% aqueous solution of "Emulgen A-60" manufactured by Kao) was performed with ultrapure water. It was washed with water for 10 seconds to form a black pattern. When the pattern after development was observed, it was 200 mJ
/ In exposure cm ^2, the unexposed portions can be removed by dissolving the 110 seconds development, line shape, a good pattern of adhesion are obtained.

As described above, since the photosensitive composition of the present invention has higher sensitivity than the conventional compositions shown in Comparative Examples, it can be sufficiently cured with a small amount of light and the dissolution time in an alkali developing solution can be shortened. Therefore, it can be seen that the productivity is also excellent.
Therefore, by forming a pixel and a black matrix using the photosensitive composition of the present invention, a high quality color filter can be stably manufactured.

[0074]

EFFECTS OF THE INVENTION According to the present invention, the developability and the solubility are excellent, and particularly in the case of color filter applications, even when the coloring material such as pigment or carbon black is contained in a high concentration, the developability, the substrate and the light shielding layer can be improved. It is possible to provide a photosensitive composition having excellent adhesion and surface smoothness, and a color filter formed from the photosensitive composition.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2H025 AA04 AA14 AA18 AB13 AC01                       AD01 BC14 BC74 BC85 BD53                       CA00 CC11 FA17                 2H048 BA02 BA45 BA48 BB02 BB34                       BB42 BB46                 4J027 AA01 AA02 BA04 BA05 BA06                       BA07 BA13 CA34 CB10

Claims (6)

[Claims] 1. A structure having a photopolymerization initiator (A) and a carboxylic acid moiety of a resin (B) having a carboxylic acid, and an epoxy moiety of a compound having an ethylenically unsaturated group and an epoxy group added thereto. A photosensitive composition containing a binder resin, wherein the compound having an ethylenically unsaturated group and an epoxy group is represented by the following structural formula I. [Chemical 1] (In the structural formula I, R ₁ represents a divalent linking group, and R ₂ represents hydrogen or a methyl group.) 2. R ₁ in the structural formula I has ₁ to 2 carbon atoms.
The photosensitive composition according to claim 1, which is an alkyl chain having a linear structure, a branched structure, or a cyclic structure of 0. 3. The photosensitive composition according to claim 1, wherein the compound having an ethylenically unsaturated group and an epoxy group is 4-hydroxybutyl acrylate glycidyl ether. 4. The photosensitive composition according to claim 1, further comprising (C) a photopolymerizable compound. 5. The photosensitive composition according to claim 1, further comprising a coloring material. 6. A color filter having pixels formed on the transparent substrate using the photosensitive composition according to claim 5.