JP2002014468A - Photopolymerizable composition, photopolymerizable colored composition and color filter - Google Patents

Abstract

(57) Abstract: Provided is a photopolymerizable composition having high sensitivity and excellent solubility in a developer, a photopolymerizable colored composition for a color filter containing the same, and a color filter using the same. . A photopolymerizable composition containing a binder resin, a photopolymerizable monomer and a photopolymerization initiator,
The binder resin is subjected to an addition reaction of an epoxy compound having an ethylenically unsaturated double bond to a polymer having a carboxyl group, and an isocyanate having an ethylenically unsaturated double bond is added to a hydroxyl group generated by the addition reaction. A photopolymerizable composition characterized by being a polymer obtained by causing the photopolymerizable composition, a colorant and a photopolymerizable colored composition characterized by containing a dispersant,
And a color filter having an image formed on a transparent substrate using the photopolymerizable coloring composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photopolymerizable composition, and more particularly to a color filter used in combination with a liquid crystal display device or a solid-state imaging device.
The present invention relates to a photopolymerizable composition suitable for forming a colored image such as a red, green, blue and resin black matrix (BM). The present invention also relates to a photopolymerizable coloring composition for a color filter, which comprises the photopolymerizable composition as a component, and a color filter using the same.

[0002]

2. Description of the Related Art Conventionally, as a method for forming an image of 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 photopolymerization initiator, a photopolymerizable coloring composition sensitized by adding a photopolymerizable monomer to a coloring composition obtained by dispersing a pigment with a dispersant or the like in a binder resin, such as glass. Is coated on a transparent substrate, dried, exposed using a mask, developed to form a colored pattern, and heated to fix the pattern. These steps are repeated for each color to form a color filter. As described above, in forming an image of a color filter using the photopolymerizable coloring composition, sufficient resolution, good adhesion to a substrate, low development residue, and the like are required. In recent years, a color filter 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 a photopolymerizable coloring composition tends to be high. In order to form a pixel using a photopolymerizable coloring composition having a high content of such a pigment or a coloring material, as the proportion of the photopolymerizable composition contained in the photopolymerizable coloring composition decreases, the composition itself increases. It is required that both the photosensitivity (curability) and the solubility in a developer are compatible at a high level.

[0003]

In general, the curability of a photopolymerizable composition can be improved by increasing the amount of photopolymerizable ethylenically unsaturated groups introduced into a binder resin in the composition. On the other hand, increasing the amount of the ethylenically unsaturated group introduced causes a decrease in the solubility of the photopolymerizable composition in an aqueous alkaline solution (developer). As described above, the curability of the photopolymerizable composition and the solubility in the developer are in a trade-off relationship, and as the proportion of the photopolymerizable composition in the photopolymerizable coloring composition decreases, the compatibility thereof becomes more difficult. To go. The present invention provides a photopolymerizable composition having high sensitivity to light and at the same time having excellent solubility in an alkali developer, a photopolymerizable colored composition for a color filter containing the photopolymerizable composition, and It is an object to provide a color filter used.

[0004]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the types of monomers constituting the binder resin contained in the photopolymerizable coloring composition, the content of each monomer, the photopolymerization It has been found that the presence or absence of the properties is complicatedly related to the developability, sensitivity, and the like of the photopolymerizable coloring composition, and that it is necessary to appropriately combine these requirements. The binder resin is dissolved by using a copolymer having a carboxyl group and an ethylenically unsaturated double bond obtained by a predetermined method from a copolymer formed using a monomer having a specific structure. It has been concluded that a photopolymerizable composition having an excellent balance of properties such as properties and photosensitivity can be obtained, and the present invention has been completed.

[0005] The gist of the present invention is to provide a photopolymerizable composition containing a binder resin, a photopolymerizable monomer and a photopolymerization initiator, wherein the binder resin is a polymer having a carboxyl group and an ethylenically unsaturated dicarboxylic acid. A photopolymerizable polymer obtained by subjecting an epoxy compound having a heavy bond to an addition reaction and subjecting a hydroxyl group generated by the addition reaction to an addition reaction of an isocyanate having an ethylenically unsaturated double bond. A composition, a photopolymerizable coloring composition comprising the photopolymerizable composition, a coloring material and a dispersant, and an image formed on a transparent substrate using the photopolymerizable coloring composition. A color filter having

In a preferred embodiment of the present invention, the polymer having a carboxyl group is a copolymer of an ethylenically unsaturated monomer having a carboxyl group represented by the following general formula (I) and another polymerizable monomer. And a general formula (I):

Embedded image (Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent; D ¹ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a carboxyl group; ² represents a hydrogen atom or a group having a carboxyl group.) In the above general formula (I), D ² represents H, -Y ² -C
^{OOH, -Y 2 -OCO-Y 3} -COOH, -Y 2 -C (C
OOH) -Y ⁴ -COOH, or the like that represented by -Y ² -R ⁶ (where, -Y ² - is an alkylene group, -
Y ³ — is an alkylene group, alkenylene group or phenylene group having 2 to 4 carbon atoms, —Y ⁴ — is an alkylene group or alkenylene group having 2 to 4 carbon atoms, R ⁶ is a phthalic acid group or hexahydrophthalic acid. Represents an acid group. ).

Further, other polymerizable monomers copolymerized with the carboxyl group-containing ethylenically unsaturated monomer represented by the above general formula (I) include vinyl compounds represented by the following general formula (II) and macro compounds thereof. A monomer represented by the general formula (II):

Embedded image CH ₂ ＣC (R ¹ ) -D ³ wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and D ³ has —COOR ² and a substituent. Represents an optionally substituted phenyl group or an alicyclic ketoamino group (however, R ² represents an alkyl group having 1 to 6 carbon atoms which may have a substituent, an aromatic group, or an alicyclic group) . And the binder resin has a weight average molecular weight in terms of polystyrene of 1500 to 150,000 in GPC, and an acid value of 5 to 200 mgKOH / g.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The photopolymerizable composition of the present invention has both high photocurability and excellent solubility in a developer, and is suitable for a photopolymerizable coloring composition for a color filter. The properties are as a binder resin of the composition,
It is synthesized by adding an epoxy compound having an ethylenically unsaturated double bond to a polymer having a carboxyl group, and further adding an isocyanate having an ethylenically unsaturated double bond to a hydroxyl group generated by the addition reaction. In addition, it can be exhibited by using a polymer having a photopolymerizable function. Then, the polymer having a carboxyl group which is the base resin polymer of the binder resin of the present invention is represented by, for example, an ethylenically unsaturated monomer having a carboxyl group represented by the above general formula (I) and the above general formula (II) It can be obtained by copolymerizing with another polymerizable monomer.

Hereinafter, in the present specification, “(meth) acrylic”, “(meth) acrylate” and the like
"Acrylic or methacrylic", "acrylate or methacrylate", and the like, for example, "(meth) acrylic acid" means "acrylic acid or methacrylic acid".

The binder resin of the present invention is a polymer having a carboxyl group obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group and any other polymerizable monomer by any method such as a radical reaction. An epoxy compound having an ethylenically unsaturated double bond is added to at least a part of the carboxyl group of the base polymer (hereinafter sometimes referred to as a base polymer), and further, at least a part of a hydroxyl group generated by the addition reaction. To an isocyanate having an ethylenically unsaturated double bond.

The ethylenically unsaturated monomer having a carboxyl group which forms the base polymer of the binder resin of the present invention is represented by, for example, the following general formula (I).

Embedded imageWhere R¹ Is a hydrogen atom or a carbon number which may have a substituent
Represents an alkyl group of 1 to 6;¹Is hydrogen atom, carbon number 1
Represents an alkyl group or a carboxyl group of^TwoIs water
Represents a group having an elemental atom or a carboxyl group. Where D
^TwoExamples of the group having a carboxyl group include -Y^Two-COO
H, -Y^Two-OCO-Y^Three-COOH, -Y^Two-C (COO
H) -Y^Four-COOH or -Y^Two-R ⁶Select from groups indicated by
(But -Y^Two-Is an alkylene group, -Y^Three−
An alkylene group having 2 to 4 carbon atoms, alkenylene group or
Nylene group, -Y^Four-Represents an alkylene group having 2 to 4 carbon atoms or
Is an alkenylene group, R⁶Is a phthalic acid group or
Represents a drophthalic acid group. ).

Specific examples of the ethylenically unsaturated monomer having a carboxyl group include unsaturated aliphatic carboxylic acids such as (meth) acrylic acid, (anhydride) maleic acid, crotonic acid, itaconic acid and fumaric acid, and 2- ( (Meth) acryloyloxyethyl succinic acid, 2-acryloyloxyethyl adipic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acrylic acid Loyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl succinic acid, 2- (meth) acryloyloxypropyl adipic acid, 2- (meth) acryloyloxypropyl hexahydrophthalic acid, 2- (meth) acrylic acid Loyloxypropyl phthalic acid, 2- (meth) acryloyloxypropyl maleic acid, 2- (meth) acyl Acryloyloxyethyl butyl succinic acid,
2- (meth) acryloyloxybutyl adipic acid, 2-
(Meth) acryloyloxybutylhexahydrophthalic acid, 2- (meth) acryloyloxybutylphthalic acid, 2
An aliphatic or aromatic dicarboxylic acid having a (meth) acryloyloxy lower alkyl group such as (meth) acryloyloxybutyl maleic acid, or (meth) acrylic acid;
And monomers to which lactones such as caprolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone are added. Of these,
Particularly preferred is (meth) acrylic acid. These monomers may be used alone or in combination.

The other polymerizable monomer copolymerizable with the above-mentioned ethylenically unsaturated monomer having a carboxyl group is selected from, for example, monomers represented by the following general formula (II) and macromonomers thereof.

Formula (II): CH ₂ ＣC (R ¹ ) -D ³ wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and D ³ represents —COOR ² , Represents a phenyl group which may have a substituent or an alicyclic ketoamino group (provided that R ² represents an alkyl group having 1 to 6 carbon atoms which may have a substituent, an aromatic group, Represents a cyclic group). ]

The other copolymerizable optional monomer is not particularly limited, but specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl ( (Meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth)
Acrylate, cyclohexyl (meth) acrylate,
(Meth) acrylates such as phenoxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate; N-vinyl Pyrrolidone; styrene and its derivatives, styrenes such as α-methylstyrene, acrylamides such as (meth) acrylamide, methylol (meth) acrylamide, alkoxymethylol (meth) acrylamide and diacetone (meth) acrylamide; (meth) acrylonitrile;
Other vinyl compounds such as ethylene, propylene, butylene, vinyl chloride, and vinyl acetate, and macromonomers such as polymethyl methacrylate macromonomer, polystyrene macromonomer, and poly 2-hydroxyethyl methacrylate macromonomer are included. Particularly preferred are styrene, methyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, butyl methacrylate, isobutyl methacrylate and tetrahydrofurfuryl (meth) acrylate.
These may be used alone or in combination of two or more.

The proportion of the monomer unit having a carboxyl group in the base polymer in the binder resin of the present invention is preferably from 10 to 90 mol%, more preferably from 20 to 80 mol%.
If the amount is less than 10 mol%, introduction of a side chain having an ethylenically unsaturated double bond by an addition reaction with an epoxy group cannot be sufficiently performed, so that the sensitivity is reduced. If the amount is more than 90 mol%, patterning of the photopolymerizable composition is performed. Tends to deteriorate. Further, the acid value of the base polymer of the present invention is 100
Preferably it is 600 mg KOH / g. 100m
If it is lower than gKOH / g, the sensitivity is lowered because the side chain having an ethylenically unsaturated double bond is not sufficiently introduced by the subsequent addition reaction of the epoxy compound.
If it is higher than 00 mgKOH / g, the patterning property of the photopolymerizable composition tends to deteriorate.

The backbone polymer having a carboxyl group of the present invention can be obtained by polymerizing the above-mentioned ethylenically unsaturated monomer having a carboxyl group and a polymerizable monomer copolymerizable with the monomer by any method. The conditions are not particularly limited. For example, the reaction is carried out by heating to 50 to 150 ° C in a suitable solvent in the presence of a polymerization initiator.
As the polymerization initiator, an azo-based radical reaction catalyst such as 2,2'-azobisisobutyronitrile, or a peroxide-based radical reaction catalyst such as lauroyl peroxide, benzoyl peroxide can be used. Any substance that dissolves the above monomer may be used, and acetone, ketones such as methyl ethyl ketone, ethers such as tetrahydrofuran,
Esters such as ethyl acetate and butyl acetate; alcohols such as ethanol; and propylene glycol monoalkyl ether acetates.

In the production of the binder resin of the present invention, a compound having an ethylenically unsaturated group and an epoxy group is added to at least a part of the carboxyl groups contained in the base polymer, and a hydroxyl group is formed by the addition reaction. It is necessary to. Hereinafter, this addition reaction method will be described.

Compounds having an ethylenically unsaturated group and an epoxy group include glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl α-ethyl acrylate, crotonyl glycidyl ether, glycidyl (iso) crotonate, N- ( 3,5-dimethyl-4
-Glycidyl) benzylacrylamide, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and the following compounds (1) to (13).

[0019]

Embedded image (Wherein, R ₁ represents a hydrogen atom or a methyl group)

[0020]

Embedded image (Wherein, R ₁ is a hydrogen atom or a methyl group, and R ₂ is
Represents 10 alkylene groups)

[0021]

Embedded image (Wherein, R ₁ is a hydrogen atom or a methyl group, and R ₂ is
Represents 10 alkylene groups)

[0022]

Embedded image (Wherein, R ₁ is a hydrogen atom or a methyl group, and R ₂ is
An alkylene group of 10, R ₃ is a hydrocarbon group having 1 to 10 carbon atoms, and k represents 0 or an integer of 1 to 10)

[0023]

Embedded image (Wherein, R ₁ is a hydrogen atom or a methyl group, and R ₂ is
Represents 10 alkylene groups)

[0024]

Embedded image (Wherein, R ₁ independently represents a hydrogen atom or a methyl group, and R ₂ represents an alkylene group having 1 to 10 carbon atoms)

[0025]

Embedded image (Wherein, R ₁ independently represents a hydrogen atom or a methyl group, and R ₂ represents an alkylene group having 1 to 10 carbon atoms)

[0026]

Embedded image (Wherein, R ₁ is a hydrogen atom or a methyl group, and R ₂ is
Represents 10 alkylene groups)

[0027]

Embedded image (Wherein, R ₁ is a hydrogen atom or a methyl group, and R ₂ is
Represents 10 alkylene groups)

[0028]

Embedded image (Wherein, R ₁ is a hydrogen atom or a methyl group, and R ₂ is
Represents 10 alkylene groups)

[0029]

Embedded image (Wherein, R ₁ is a hydrogen atom or a methyl group, and R ₂ is
Represents 10 alkylene groups)

[0030]

Embedded image (Wherein, R ₁ represents a hydrogen atom or a methyl group)

[0031]

Embedded image (Wherein, R ₁ represents a hydrogen atom or a methyl group)

Of the above compounds, those in which the epoxy group is an alicyclic epoxy group are preferred. Particularly preferably,
(3,4-epoxycyclohexyl) methyl (meth) acrylate. As a method for reacting a compound having an ethylenically unsaturated group and an epoxy group with the carboxyl group of the base polymer having a carboxyl group, a known method can be used. For example, the above-mentioned basic polymer (polymer) having a carboxyl group and a compound having an ethylenically unsaturated group and an epoxy group can be used as a catalyst with a tertiary amine such as triethylamine or benzylmethylamine, dodecyltrimethylammonium chloride, or tetramethylammonium chloride. , Quaternary ammonium salts such as tetraethylammonium chloride, pyridine, triphenylphosphine, etc., and p-methoxyphenol, hydroquinone, naphthylamine, etc. as polymerization inhibitors. By reacting for 10 hours, an epoxy group is added to the carboxyl group of the polymer, thereby forming a hydroxyl group and simultaneously introducing a group having an ethylenically unsaturated bond.

In the present invention, the addition amount of the epoxy compound having an ethylenically unsaturated double bond to the carboxyl group of the base polymer of the binder resin may be 10 to 95 mol% of the carboxyl group contained in the base polymer. Necessary, preferably 30 to 90 mol%. If it is less than 10 mol%, the crosslinking density becomes insufficient,
The sensitivity decreases. If it is more than 95 mol%, the alkali developability will be insufficient and the patterning property will be deteriorated.

The binder resin of the present invention further comprises a polymer having a hydroxyl group obtained by adding a compound having an ethylenically unsaturated group and an epoxy group to at least a part of the carboxyl group of the above-mentioned base polymer, It is produced by an addition reaction of an isocyanate having an unsaturated double bond. The isocyanate having an ethylenically unsaturated double bond in the present invention is not particularly limited, but specific examples include (meth) acryloyloxyalkyl isocyanate. As the (meth) acryloyloxyalkyl isocyanate, the (meth) acryloyloxy group has 1 carbon atom.
An isocyanate group (—NC
O), specifically, 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate and the like.

The amount of the isocyanate having an ethylenically unsaturated double bond added to the hydroxyl group formed by the addition reaction of the epoxy compound having a carboxyl group and an ethylenically unsaturated double bond in the base polymer in the present invention is as follows:
5 to 100 mol%, preferably based on the hydroxyl group,
30 to 100 mol%. If the amount is less than 5 mol%, the effect of increasing the sensitivity by increasing the amount of the crosslinking group is weak.

The reaction between the hydroxyl group formed by the epoxy compound addition reaction and the isocyanate having an ethylenically unsaturated double bond is carried out by converting the isocyanate into a polymer obtained by the epoxy compound addition reaction in the presence of a small amount of a catalyst. It is carried out by dropping into a solution and reacting at 50 to 110 ° C. for several hours to several tens of hours. Examples of the catalyst include dibutyltin dilaurate, dioctyltin dilaurate and the like, and p-methoxyphenol, hydroquinone,
A polymerization inhibitor such as naphthylamine is added as needed. In addition, a part of the isocyanate having an ethylenically unsaturated double bond may react with a carboxyl group of the base polymer. The double bond equivalent [resin weight per mole of ethylenically unsaturated double bond group (C = C)] of the binder resin of the present invention is usually 1,000 or less, preferably 7 or less.
00 or less, more preferably 500 or less.

The polymerization average molecular weight in terms of polystyrene (hereinafter abbreviated as molecular weight) in GPC of the binder resin of the present invention can be appropriately selected according to the desired properties of the composition. 15,000
0, more preferably 3,000 to 100,000. If it is less than 1500, sufficient cured film strength cannot be obtained, and if it exceeds 150,000, the applicability tends to deteriorate. Also, in order to impart a suitable alkali developability,
The acid value is preferably from 5 to 200 mgKOH / g, more preferably from 10 to 160 mgKOH / g.

The photopolymerizable monomer used in the photopolymerizable composition of the present invention includes at least one ethylenically unsaturated group.
Compound. Specific examples of the compound having one ethylenically unsaturated group in the molecule include (meth) acrylic acid, an alkyl ester of (meth) acrylic acid, acrylonitrile, styrene, and a carboxylic acid having one ethylenically unsaturated bond. Monoesters of poly (mono) hydric alcohols and the like can be mentioned.

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

The ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid is not particularly limited.
Ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate,
Acrylic esters of aliphatic polyhydroxy compounds such as pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, and these exemplified compounds And methacrylic acid esters in which acrylate is replaced by methacrylate, itaconic acid esters in which itaconate is replaced, crotonate esters in which clonate is replaced, and maleic acid esters in which maleate is replaced by maleate.

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. And methacrylic acid esters.

The ester obtained by the esterification reaction of the unsaturated carboxylic acid or the polyvalent carboxylic acid and the polyvalent hydroxy compound is not necessarily a single ester, but typical examples include (meth) acrylic acid, Phthalic acid,
Condensates of ethylene glycol and ethylene glycol; condensates of (meth) acrylic acid, maleic acid, and diethylene glycol;
Condensates of (meth) acrylic acid, terephthalic acid and pentaerythritol; condensates of (meth) 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) acrylate or a polyisocyanate compound and a polyol and a hydroxyl group-containing (meth) acrylate. Urethane (meth) acrylates obtained by the reaction; epoxy acrylates such as an addition reaction product of a polyvalent epoxy compound and hydroxy (meth) acrylate or (meth) acrylic acid; acrylamides such as ethylenebisacrylamide; Allyl esters such as diallyl phthalate; vinyl-containing compounds such as divinyl phthalate are useful.

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. For example, 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-bis (trichloromethyl) -s-
Halomethylated triazine derivatives such as 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
Halomethylated oxadiazole derivatives such as furyl-1,3,4-oxadiazole, 2- (2'-chlorophenyl) -4,5-diphenylimidazole dimer, 2-
(2'-chlorophenyl) -4,5-bis (3'-methoxyphenyl) imidazole dimer, 2- (2'-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2'- (Methoxyphenyl) -4,5-diphenylimidazole dimer, (4′-methoxyphenyl)
And imidazole derivatives such as -4,5-diphenylimidazole dimer.

Other photopolymerization initiators include benzoin ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether and benzoin isopropyl ether, 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, -Anthraquinone derivatives such as chloroanthraquinone, benzanthrone derivatives, benzophenone,
Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-
Benzophenone derivatives such as carboxybenzophenone,
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-
Acetophenone derivatives such as methyl- (4 '-(methylthio) phenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl- (p-butylphenyl) ketone, thioxanthone, 2-ethylthioxanthone,
And thioxanthone derivatives such as 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;
Phenazine derivatives such as 9,10-dimethylbenzphenazine, di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2 , 3,
4,5,6-pentafluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, di-cyclopentadienyl-Ti- Bis-2,4,6-trifluorophenyl
1-yl, di-cyclopentadienyl-Ti-2,6-
Di-fluorophenyl-1-yl, di-cyclopentadienyl-Ti-2,4-di-fluorophenyl-1-yl,
Di-methylcyclopentadienyl-Ti-bis-2,
3,4,5,6-pentafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,6-
Di-fluorophenyl-1-yl, di-cyclopentadienyl-Ti-2,6-di-fluoro-3- (pyr-1-
And titanocene derivatives such as yl) -phenyl-1-yl. Among these photopolymerization initiators, a biimidazole derivative or a titanocene derivative is preferable because of particularly high polymerization efficiency.

Preferred sensitizing dyes used in combination with these photopolymerization initiators include, for example, JP-A-3-2397.
No. 03, JP-A-5-289335, and coumarin compounds having a heterocyclic ring described in JP-A-63-22111.
0, 3-ketocoumarin compounds, JP-A-4-221958 and JP-A-4-219756.
Xanthene dye described in JP-A-6-19240
Pyrromethene dye described in JP-A-47-2528
JP, JP-A-54-155292, JP-A-56-155292
(P-dialkylaminobenzylidene) ketones and styryl dyes described in JP-A-166154 and JP-A-59-56403, sensitizing dyes having a julolidyl group described in JP-A-6-295061, WO96 / 2
And diaminobenzene compounds described in JP-A-3237.

Among these sensitizing dyes, particularly preferred are amino group-containing sensitizing dyes, and more specifically, compounds having an amino group and a phenyl group in the same molecule. Specific examples include, for example, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 2-aminobenzophenone, 4-aminobenzophenone, and 4,4'-diaminobenzophenone. , Benzophenone-based compounds such as 3,3'-diaminobenzophenone and 3,4-diaminobenzophenone, 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethyl Aminophenyl) benzo [4,5] benzoxazole, 2-
(P-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) 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, 2- (p-dimethylaminophenyl) quinoline, 2- (p-diethylaminophenyl) quinoline, 2- (p-dimethylaminophenyl) pyrimidine, 2- (p And p-dialkylaminophenyl group-containing compounds such as-(diethylaminophenyl) pyrimidine.

In addition to the above sensitizing dyes, aromatic mercapto compounds such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole and 2-mercaptobenzoxazole; dialkylbenzophenone compounds such as Michler's ketone; hexanedithiol, trimethylol A chain transfer agent such as a polyfunctional thiol compound such as propane tris thioglyconate and pentaerythritol tetrakis thiopropionate may be used together with the photopolymerization initiator.

The photopolymerizable composition of the present invention comprises, in addition to the binder resin, photopolymerizable monomer and photopolymerization initiator,
By containing a coloring material, a photopolymerizable coloring composition that is effective for forming pixels (red, blue, and green pixels and a resin black matrix) of a color filter can be obtained.
Various dyes and pigments can be used as the color material for forming the pixels of the color filter, but pigments are preferable in terms of heat resistance, light resistance and the like.

The color pigments used for forming the pixels of the color filter of the photopolymerizable coloring composition of the present invention include azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone and dioxazine. Various inorganic pigments can be used in addition to organic pigments such as indanthrene and perinone. For example, pigments having a CI (color index) number shown below can be preferably used. C. I. Red; 9, 97, 122, 123, 149, 16
8, 177, 180, 192, 215, 216, 21
7, 220, 223, 224, 226, 227, 22
8, 240 C.I. I. Blue; 15, 15; 6, 22, 60, 64 C.I. I. Green; 7, 36 C.I. I. Black; 7 C.I. I. Yellow; 20, 24, 86, 93, 109, 11
0, 117, 125, 137, 138, 139, 14
7, 148, 153, 154, 166, 168 C.I. I. Orange; 36, 43, 51, 55, 59, 6
1 C. I. Violet; 19, 23, 29, 30, 3
7, 40, 50 C.I. I. Tea; 23, 25, 26

When a resin black matrix of a color filter is formed using the photopolymerizable coloring composition of the present invention, a black coloring material is used. As the black color material, a single color black material or a plurality of black color materials may be used, or a black color material obtained by mixing red, green, and blue color materials may be used. Further, these coloring materials can be appropriately selected from inorganic or organic pigments and dyes. When the coloring material used is an inorganic or organic pigment, the average particle size is 1 μm or less,
It is preferable to use a dispersion treatment of 0.5 μm or less.

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

Further, regarding other pigments which can be used in combination, C.I. I. The number is, for example, C.I. I. Yellow pigments 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.

Further, as a black color material that can be used alone,
Carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black,
Cyanine black, titanium black and the like. Among these, carbon black is preferred from the viewpoint of light blocking ratio and image characteristics. Examples of the carbon black include the following carbon blacks. Manufactured by Mitsubishi Chemical Corporation (trade name): MA7, MA8, MA11,
MA100, MA220, MA230, # 52, # 5
0, # 47, # 45, # 2700, # 2650, # 22
00, # 1000, # 990, # 900. Degussa (product name): Printex95, Prin
tex90, Printex85, Printex7
5, Printex55, Printex45, Pri
ntex40, Printex30, Printex
3. PrintexA, PrintexG, Speci
alBlack550, SpecialBlack35
0, SpecialBlack250, Special
Black100

Made by Cabot (trade name): Monarc
h460, Monarch430, Monarch28
0, Monarch120, Monarch800, M
onarch4630, REGAL99, REGAL9
9R, REGAL415, REGAL415R, REG
AL250, REGAL250R, REGAL330,
BLACK PEARLS480, PEARLS130 manufactured by Colombian Carbon Co .: RAVE11, RAV
EN15, RAVE30, RAVE35, RAVE
N40, RAVEN410, RAVEN420, RAV
EN450, RAVEN500, RAVE780, R
AVEN850, RAVE890H, RAVE10
00, RAVEN1020, RAVEN1040 The above carbon black may be used in combination with other black or colored inorganic or organic pigments. For the production of a resin black matrix having a high optical density and a high surface resistivity, it is particularly preferable to use resin-coated carbon black.

The photopolymerizable composition of the present invention is prepared by adding the photopolymerizable monomer 10 to 100 parts by weight of the binder resin.
The amount is preferably in the range of from 200 to 200 parts by weight from the viewpoint of developability and sensitivity, and the photopolymerization initiator is preferably used in the range of from 0.05 to 70 parts by weight. In the photopolymerizable coloring composition of the present invention, the coloring material is preferably added in a range of 15 to 70% by weight based on the total solid content. In the present invention, in addition to these essential components, an organic solvent, a pigment dispersant, an adhesion improver,
A coating improver, a development improver, an ultraviolet absorber, an antioxidant and the like can be appropriately added. In order to improve the adhesion to the substrate, it is preferable to add a silane coupling agent.

As the type of the silane coupling agent, various types such as an epoxy type, a methacryl type and an amino type can be used, but an epoxy type silane coupling agent is particularly preferable. The photopolymerizable 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, and the like, and further, a binder resin, a photopolymerizable monomer, a photopolymerization initiator, and the like are mixed, mixed, and mixed. It can be obtained by preparing a suitable solution.

The organic solvent is not particularly restricted but includes, for example, diisopropyl ether, mineral spirit, n
-Pentane, amyl ether, ethyl caprylate, n
Hexane, diethyl ether, isoprene, ethyl isobutyl ether, butyl stearate, n-octane, Valsol # 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 benzoate, amyl chloride, ethylene glycol diethyl ether, ethyl orthoformate, methoxymethyl pentanone, methyl butyl ketone,
Methylhexyl 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, Methoxymethylpentanol, 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-
Organic solvents such as methyl-3-methoxybutyl acetate can be specifically mentioned.

The solvent is capable of dissolving or dispersing each component, and preferably has 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 the pigment dispersant because the dispersion stability over time is excellent. Usually, it is preferable that the coloring material is previously subjected to 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 color material is finely divided by the dispersion treatment, the coating characteristics of the resist can be improved.

In the case of dispersing with a sand grinder, glass beads or zirconia beads having a diameter of 0.1 to several millimeters are preferably used. The dispersing conditions are usually such that the temperature is from 0 ° C. to 100 ° C., preferably from room temperature to 80 ° C. The dispersion time is appropriately adjusted because the appropriate time varies depending on the composition of the ink (black color material, solvent, dispersant), the size of the sand grinder, and the like.

Next, a binder resin, a photopolymerizable monomer, a photopolymerization initiator, and an organic solvent are blended and mixed with the ink obtained by the dispersion treatment to form a uniform solution. In the production process, foreign matter such as fine dust often mixes with the photosensitive liquid, and thus the obtained photopolymerizable coloring composition is desirably filtered through a filter or the like. Next, formation of each of red, green, and blue pixels and a resin black matrix using the photopolymerizable coloring composition of the present invention and a method of manufacturing a color filter having the same will be described.

First, a photopolymerizable coloring composition containing a coloring material is applied on a transparent substrate by using a coating device such as a spinner, a wire bar, a flow coater, a die coater, a roll coater, a spray, etc., and dried to form a coating film. After the formation, a photomask is placed on the coating film, and a predetermined color pattern is formed by image exposure, development, and heat curing or light curing as necessary through the photomask. Pixels can be formed by using red, green, and blue color materials as color materials, and a resin black matrix can be formed by using black color materials.
By repeating this step, a color filter is formed.

The transparent substrate used here is a transparent substrate for a color filter, and its material is not particularly limited. Examples thereof include polyester such as polyethylene terephthalate, polypropylene, polyolefin such as polyethylene, polycarbonate, and polyolefin. Methyl methacrylate, polysulfone thermoplastic sheet,
Examples include thermosetting plastic sheets such as epoxy resin, polyester resin, and poly (meth) acrylic resin, and various glass plates. Particularly, 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 a silane coupling agent and a urethane polymer in order to improve physical properties such as surface adhesiveness. You can also. For drying, a hot plate, an IR oven, a convection oven, or the like can be used. Preferred 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 lamp light source such as a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, an argon ion laser, a YAG laser, A laser light source such as an excimer laser and a nitrogen laser is exemplified. When only the wavelength of the specific irradiation light is used, an optical filter can be used.

The development treatment is not particularly limited as long as it is a solvent capable of dissolving the resist (photopolymerizable coloring composition) film in the unexposed area, but it is preferable to use an alkali developing solution. . Examples of such an alkali developer include inorganic alkali agents such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, and the like, or diethanolamine, triethylamine, triethylamine, and the like. An aqueous solution containing an organic alkali agent such as ethanolamine, a tetraalkylammonium hydroxide salt, and tetramethylammonium hydroxide is exemplified. Incidentally, an organic solvent capable of dissolving, for example, acetone,
Methylene chloride, trichlene, and cyclohexanone are not preferred because they have environmental pollution, harm to the human body, and danger of fire.

If necessary, the alkali 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, or the like. In particular, a surfactant is preferably added because many of them have an effect of improving the developing property, the resolution and the background stain. For example, as a surfactant for a developer, an anionic surfactant having a sodium naphthalenesulfonate group, a sodium benzenesulfonate group, a nonionic surfactant having a polyalkyleneoxy group, a cation having a tetraalkylammonium group Surfactants and the like.

The development processing method is not particularly limited, but is usually carried out at a development temperature of 10 to 50 ° C., preferably 15 to 45 ° C., by a method such as immersion development, spray development, brush development, or ultrasonic development. . The formed resin black matrix and pixels are preferably subjected to a thermosetting treatment after image formation in order to improve film strength, solvent resistance, alkali resistance and the like. This heat curing treatment is preferably performed at 150 ° C. or more and less than 300 ° C. If the temperature is lower than 150 ° C., the thermosetting is insufficient, so that problems such as film strength, solvent resistance and alkali resistance tend to occur. If the temperature is higher than 300 ° C., excessive volume shrinkage occurs, and problems are likely to occur in the adhesion to the substrate and the accuracy.

[0070]

The present invention will be described in more detail with reference to the following Examples and Synthesis Examples, but the present invention is not limited to the following Examples as long as the gist of the present invention is not exceeded.

<Synthesis Example 1> Acid value 240, molecular weight 1380
0 g of styrene / α-methylstyrene / acrylic acid resin (monomer ratio (mol) 49: 9: 42) 10 g, p-
A flask was charged with 0.5 g of methoxyphenol, 0.2 g of tetraethylammonium chloride, and 21.9 g of propylene glycol monomethyl ether acetate,
4.50 g of (3,4-epoxy-cyclohexyl) methyl acrylate was added dropwise and reacted at 90 ° C. for 32 hours. G of the photopolymerizable copolymer thus obtained
The polymerization average molecular weight by PC is 17 in terms of polystyrene.
800. Upon neutralization titration with KOH, the acid value was 85 mgKOH / g.

<Synthesis Example 2> 18.1 g of the copolymer obtained in Synthesis Example 1 and 0.002 of dioctyltin dilaurate
g and propylene glycol monomethyl ether acetate (4.6 g) were charged into a flask, and methacryloyloxyethyl isocyanate (3.1 g) was added dropwise thereto. The mixture was reacted at a temperature of 70 ° C. for 7 hours. The polymerization average molecular weight by GPC of the photopolymerizable binder resin thus obtained was 28500 in terms of polystyrene. Further, when a neutralization titration with KOH was performed, the acid value was 63 mgKOH / g. The reaction solution was reprecipitated in hexane, purified, and 1H-N
When measured by MR, the composition ratio (molar ratio) of each unit
Is styrene / α-methylstyrene / acrylic acid /
(3,4-epoxy-cyclohexyl) methyl acrylate / methacryloyloxyethyl isocyanate = 3
8/7/32/16/7. The double bond equivalent was 482.

<Synthesis Example 3> Acid value 240, molecular weight 1380
0 g of styrene / α-methylstyrene / acrylic acid resin (monomer ratio (mol) 49: 9: 42), 0.5 g of p-methoxyphenol, 0.2 g of tetraethylammonium chloride, and 23.2 g of propylene glycol monomethyl ether acetate. Charge the flask,
5.70 g of (3,4-epoxy-cyclohexyl) methyl acrylate was added dropwise and reacted at a temperature of 90 ° C. for 32 hours. The polymerization average molecular weight by GPC of the photopolymerizable binder resin thus obtained was 20,100 in terms of polystyrene. Neutralization titration with KOH revealed that the acid value was 56 mg KOH / g, and (3,4-epoxy-cyclohexyl) methyl acrylate was 64 m of the -COOH group of the styrene / acrylic acid resin as the raw material.
ol%.

<Example 1> 22.4 g of phthalocyanine blue as a pigment, 8.97 g of a polymer dispersant, 1.12 g of a dispersing aid, and 74 g of propylene glycol monomethyl ether acetate as a solvent were dispersed in a paint conditioner containing zirconia beads. To obtain a blue ink. Here, phthalocyanine blue is available from Toyo Ink Co., Ltd.
Lionol Blue ES manufactured by Co., Ltd., Disperbyk161 manufactured by Big Chemie Co., Ltd. was used as a polymer dispersant, and Solsperse 5000 (manufactured by Zeneca Corporation) was used as a dispersing aid.

5.6 of the blue ink thus obtained
4. 7 g of the alkali-soluble resin solution obtained in Synthesis Example 2.
63 g, 0.75 g of dipentaerythritol hexaacrylate as a photopolymerizable monomer, and 2,2′-bis (O-chlorophenyl) -4,4′5 as a photopolymerization initiator.
0.10 g of 5'-tetraphenylbiimidazole, 0.07 g of 4,4'-bis (diethylamino) benzophenone as a sensitizing dye, 0.02 g of 2-mercaptobenzothiazole as a chain transfer agent, a fluorine-based surfactant (Sumitomo) 0.001 g of 3M FC-430) and propylene glycol monomethyl ether acetate 1 as a solvent
2.65 g was stirred and mixed to obtain a photopolymerizable blue composition.

Glass substrate (“AN635” manufactured by Asahi Glass Co., Ltd.)
Spin-coat the photopolymerizable blue composition on top, hot
The plate was dried by heating at 70 ° C. for 2 minutes and 30 seconds.
A 5 μm photopolymerizable blue layer was obtained. Ultra-high pressure mercury
100mJ / cm using a lamp ^Two UV light, photo mass
Irradiated through This is followed by an alkaline developer (potassium carbonate).
2.1 wt%, 0.15 wt% potassium bicarbonate,
Surfactant: "Emulgen A-60" manufactured by Kao 4.0 wt
% Aqueous solution), washed with ultrapure water for 10 seconds, blue
A color pattern was formed. When observing the pattern after development
Roller, 100mJ / cm^Two Exposure, 40 seconds development not yet
The exposed part can be dissolved and removed, and the line with good line shape and adhesion
A turn has been obtained.

Comparative Example A blue pattern was formed in the same manner as in Example 1 except that the photopolymerizable binder resin obtained in Synthesis Example 3 was used. An exposure of 200 mJ / cm ² was required. It took 90 seconds of development to dissolve and remove the unexposed areas. A pattern having a good line shape and good adhesion was obtained.

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

[0079]

As described above, as a binder resin of a photopolymerizable composition, an epoxy compound having an ethylenically unsaturated double bond in a part of the carboxyl group is added to a polymer having a carboxyl group. By using a copolymer obtained by the addition reaction of an isocyanate having an ethylenically unsaturated double bond to the generated hydroxyl group, the sensitivity is improved, and the solubility in an alkali developing solution is improved. Therefore, the photopolymerizable colored composition using the photopolymerizable composition has made it possible to greatly increase the working efficiency in the production of a color filter.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/004 501 G03F 7/004 501 505 505 7/027 7/027 7/028 7/028 (72) Inventor Hidefumi Fujiwara 1000 Kamoshita-cho, Aoba-ku, Yokohama-shi, Kanagawa F-term in Yokohama Research Laboratory, Mitsubishi Chemical Corporation 2H025 AA01 AA04 AB13 AC01 AD01 BC14 BC31 BC52 BC81 BC92 CA01 CA14 CA22 CA28 CA39 CC11 CC20 FA03 FA17 2H048 BA02 BA11 BA16 BA17 BA25 BA28 BA29 BA60 BB02 BB14 BB15 BB42 4J011 QA13 QA14 QA15 QA18 QA20 QA23 QA24 QB02 QB03 QB20 QC03 SA14 SA16 SA19 SA20 SA22 SA23 SA25 SA26 SA27 SA29 SA34 SA63 SA64 SA78 SA01 A07 TA01 A04 TA01 TA04 A07 TA01 TA04 AJ05 BA13 BA19 BA20 BA23 BA25 BA26 BA27 BA28 CA34 CB10 CC03 CC05 CC07 CD10 4J100 AA02Q AA03Q AA04Q AB02Q AB03Q AC03Q AG0 4Q AJ01P AJ02P AJ08P AJ09P AK32P AL03Q AL04Q AL08P AL08Q AL09Q AL11Q AL91P AM02Q AM15Q AM21Q AQ08Q BA03H BA03Q BA04Q BA14Q BA15H BA15P BA16P BA28H BA38H BC03H BC04H BC04BC31 BC03 BC08 BC08 BC08 BC08 BC08 BC08

Claims (8)

[Claims] 1. A photopolymerizable composition comprising a binder resin, a photopolymerizable monomer and a photopolymerization initiator, wherein the binder resin has an ethylenically unsaturated double bond in a polymer having a carboxyl group. The addition reaction of the epoxy compound, the hydroxyl group generated by the addition reaction,
A photopolymerizable composition, which is a polymer obtained by subjecting an isocyanate having an ethylenically unsaturated double bond to an addition reaction. 2. The polymer having a carboxyl group is a copolymer of an ethylenically unsaturated monomer having a carboxyl group represented by the following general formula (I) and another polymerizable monomer. Item 4. The photopolymerizable composition according to Item 1. General formula (I); (Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent; D ¹ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a carboxyl group; ² represents a hydrogen atom or a group having a carboxyl group.) 3. In the above general formula (I),^TwoIs H,-
Y^Two-COOH, -Y^Two-OCO-Y ^Three-COOH, -Y^Two
-C (COOH) -Y^Four-COOH or -Y^Two-R⁶Indicated by
The photopolymerizable composition according to claim 1 or 2, wherein
Composition (however, -Y^Two-Is an alkylene group, -Y^Three−
An alkylene group having 2 to 4 carbon atoms, alkenylene group or
Nylene group, -Y^Four-Represents an alkylene group having 2 to 4 carbon atoms or
Is an alkenylene group, R⁶Is a phthalic acid group or
Represents a drophthalic acid group. ). 4. Other polymerizable monomers copolymerized with the carboxyl group-containing ethylenically unsaturated monomer represented by the above general formula (I) include vinyl compounds represented by the following general formula (II) and macromonomers thereof. The photopolymerizable composition according to claim 1, wherein the composition is selected from the group consisting of: Formula (II): CH ₂ ＣC (R ¹ ) -D ³ wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and D ³ represents —COOR ² , Represents a phenyl group which may have a substituent or an alicyclic ketoamino group (provided that R ² represents an alkyl group having 1 to 6 carbon atoms which may have a substituent, an aromatic group, Represents a cyclic group). ] 5. The binder resin has a weight average molecular weight in terms of polystyrene by GPC of 1500 to 15,000.
The photopolymerizable composition according to any one of claims 1 to 4, wherein the composition is 0. 6. The binder resin having an acid value of 5 to 200 m.
The photopolymerizable composition according to any one of claims 1 to 5, wherein the photopolymerizable composition is gKOH / g. 7. A photopolymerizable coloring composition comprising the photopolymerizable composition according to claim 1, a coloring material and a dispersing agent. 8. A color filter having pixels formed on a transparent substrate using the photopolymerizable coloring composition according to claim 7.