JPH11258790A - Colored photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a colored photosensitive resin compsn. less liable to polymn. inhibition due to oxygen even in the air and less liable to generate halogen- contg. impurities such as gaseous hydrogen chloride owing to a photopolymn. initiator while having satisfactory sensitivity. SOLUTION: The colored photosensitive resin compsn. contains (A) a pigment, (B) a carboxyl-contg. copolymer, (C) a photo-cationic-polymerizable compd. having at least three alicyclic epoxy groups in which oxygen atoms bond directly to the alicyclic rings in one molecule, (D) a photo-radical-polymerizable monomer, in particular a compd. having a polymerizable carbon-carbon unsatd. bond, (E) a photopolymn. initiator capable of initiating both photo radical polymn. and photo cationic polymn., in particular a photopolymn. initiator having an s-triazine skeleton and (F) a solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improvement in a photosensitive resin composition which is widely used in ultraviolet curable inks and photoresists, and more particularly to an improvement in a color liquid crystal display device and an image pickup device. The present invention relates to a colored photosensitive resin composition suitable for a resist composition for forming a colored image (also referred to as a pixel).

[0002]

2. Description of the Related Art A color filter in a color liquid crystal display or an image pickup device is usually manufactured by forming three primary color pixels of red, green and blue on a substrate such as glass or a silicon wafer. In addition, a black matrix is usually provided to shield light between these pixels. Then, in order to form pixels of these colors, a resist solution containing a pigment corresponding to each color is uniformly applied on a substrate on which a light-shielding layer is formed by a spin coater, and then heated and dried (prebaked). A method of exposing and developing the coating film is adopted, and an image of each color is obtained by repeating these operations for each color required for the color filter. As such a resist, a composition containing a photopolymerizable monomer and a photopolymerization initiator together with a pigment and a binder resin is often used. In addition, a resist containing a black pigment may be used for forming a black matrix.

[0003] Most of these resists have a system for imparting a developing solution resistance (a property of hardly dissolving in a developing solution and a portion thereof remaining as an image) of a resist coating film by a curing reaction of a photo-radical polymerizable monomer. ing. A resist composition using such a photo-radical polymerization for a curing reaction is difficult to pattern under an air atmosphere because the polymerization reaction is inhibited by the presence of oxygen. Need. Therefore, a method of avoiding polymerization inhibition by applying a transparent oxygen-blocking film such as polyvinyl alcohol to the surface of the coating film before exposure has been adopted.

However, if the amount of exposure is increased to avoid polymerization inhibition due to oxygen, or if an oxygen barrier film is used, the tact time (production time per sheet) during the production of a color filter increases, For example, the number of processes increases, and productivity is greatly impaired. Therefore, in order to avoid polymerization inhibition by oxygen without impairing the productivity, Japanese Patent Application Laid-Open No. 1-152449 discloses that a highly sensitive s-triazine compound, particularly an s-triazine compound having a chloromethyl group, is photopolymerized. It was proposed to be an agent. However, when such an s-triazine compound is used as a photopolymerization initiator, hydrogen chloride gas or the like is generated due to chlorine radicals generated by photocleavage, often causing contamination of a photomask. Further, there is a high possibility that chlorine ions migrate to the liquid crystal layer and cause malfunction of the liquid crystal.

[0005] In order to capture such chlorine-based gas and the like due to chlorine radicals, it is necessary to add an epoxy compound to the resist resin as disclosed in Japanese Patent Application Laid-Open Nos. 1-254918 and 8-9.
It is proposed in 4824. However, the epoxy compound proposed in the former publication does not participate in the photocuring reaction, and there has been a problem that as the content of the epoxy compound in the resist resin increases, the sensitivity of the resist rapidly decreases. On the other hand, in the latter publication, an alicyclic bifunctional epoxy compound is recommended, but in the bifunctional epoxy compound specifically described therein, a photocuring reaction of an epoxy group which occurs competitively and a photocuring reaction of an epoxy group occur. There is a problem that it is difficult to achieve compatibility with a reaction for trapping chlorine-based gas and the like.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to prevent the polymerization from being inhibited by oxygen even in an air atmosphere.
It is an object of the present invention to provide a colored photosensitive resin composition having sufficient sensitivity and less generation of halogen-based impurities such as hydrogen chloride gas due to a photopolymerization initiator.

The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems of the prior art, and as a result, have identified a cationic photopolymerizable compound having a specific structure together with a pigment, a binder resin, and a photoradical polymerizable monomer. It has been found that excellent results can be obtained by using a composition containing the photopolymerization initiator of the present invention, and the present invention has been completed.

[0008]

That is, the present invention provides a colored photosensitive resin composition containing the following components.

(A) a pigment, (B) a carboxyl group-containing copolymer, and (C) a photocationically polymerizable compound having at least three alicyclic epoxy groups in the molecule in which an oxygen atom is directly bonded to an alicyclic ring. , (D) a photo-radical polymerizable monomer,
(E) a photopolymerization initiator capable of initiating both photoradical polymerization and photocation polymerization, and (F) a solvent.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The colored photosensitive resin composition of the present invention is mainly used as a pigment-dispersed resist, in which a pigment (A) is dispersed in a solvent, and a carboxyl group-containing copolymer (B) called a binder resin, Cationic polymerizable compound (C),
The photoradical polymerizable monomer (D) and the photopolymerization initiator (E), and optionally other additives, are dissolved or dispersed.

The pigment (A) can be an organic pigment or an inorganic pigment usually used for a pigment-dispersed resist. Examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts.Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony Oxides or composite metal oxides are mentioned. As the organic pigment, specifically, a color index (Color Index) (The Societ
y of Dyers and Colorists published)
gment). These pigments can be used alone or in combination of two or more. More specifically, compounds having the following color index (C.I.) numbers are included, but are not limited thereto.

CI Pigment Yellow 20, 24, 31, 5
3, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 13
9, 147, 148, 153, 154, 166 and 173; CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 5
9, 61, 64, 65 and 71; CI Pigment Red 9, 9
7, 105, 122, 123, 144, 149, 166, 168, 176,177, 18
0, 192, 215, 216, 224, 242 and 254; CI Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37 and 38; CI Pigment Blue 15 (15: 3, 15: 4, 15: 6
CI Pigment Green 7, 10, 15, 25, 36 and 47; CI Pigment Brown 28; CI Pigment Black 1 and 7), 21, 22, 28, 60 and 64;
Such.

The pigment (A) is used in an amount of preferably 5 to 60% by weight, more preferably 10 to 50% by weight, based on the total solid content in the colored photosensitive resin composition.

The binder resin imparts alkali developability to the unexposed coating film and acts as a dispersion medium for the pigment. In the present invention, the carboxyl group-containing copolymer (B) is used as the binder resin. Used. The carboxyl group-containing copolymer can be obtained, for example, by copolymerizing a carboxyl group-containing monomer with another monomer copolymerizable therewith.

The carboxyl group-containing monomer is, for example,
It can be an unsaturated carboxylic acid having at least one carboxyl group in the molecule, such as an unsaturated monocarboxylic acid or unsaturated dicarboxylic acid, and specifically, acrylic acid,
Methacrylic acid, crotonic acid, itaconic acid, maleic acid,
Fumaric acid and the like. These can be used alone or in combination of two or more. Further, a monomer copolymerizable with these carboxyl group-containing monomers is a compound having a polymerizable unsaturated bond. Specifically, styrene, α-methylstyrene, aromatic vinyl compounds such as vinyltoluene, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl Unsaturated carboxylic acid esters such as (meth) acrylate, unsaturated carboxylic acid aminoalkyl esters such as aminoethyl acrylate, unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate, vinyl acetate and vinyl propionate Carboxylic acid vinyl ester, (meth)
And vinyl cyanide compounds such as acrylonitrile and α-chloroacrylonitrile. These monomers can also be used alone or in combination of two or more.

Further, a copolymer obtained by copolymerizing an unsaturated carboxylic acid and an unsaturated carboxylic acid glycidyl ester, in which an unsaturated carboxylic acid is added to a glycidyl group, is obtained by copolymerizing styrene with maleic anhydride. Polymers having a photopolymerizable unsaturated group on the side chain of the polymer, such as a copolymer obtained by adding 2-hydroxyethyl acrylate to a portion derived from maleic anhydride of a copolymer obtained by the above method, can also be used as a carboxyl group-containing copolymer (B ) Can be used.

In the carboxyl group-containing copolymer (B), the carboxyl group-containing monomer unit is
It is preferably present in the range of 10 to 50% by weight, more preferably 15 to 40% by weight, based on the whole monomer. The amount of the carboxyl group-containing monomer unit referred to herein means, when the carboxyl group-containing copolymer is a copolymer of a carboxyl group-containing monomer and another monomer, the amount of the carboxyl group-containing monomer among them. When the copolymer has a photopolymerizable unsaturated group in the side chain of the polymer, it means a monomer unit that finally remains as a carboxyl group. To explain the latter more specifically, for example, a copolymer obtained by copolymerizing an unsaturated carboxylic acid and an unsaturated carboxylic acid glycidyl ester with an unsaturated carboxylic acid added to a glycidyl group of a copolymer obtained,
Finally, the unsaturated carboxylic acid to be reacted with the glycidyl group is
Only units of unsaturated carboxylic acids which are first copolymerized with unsaturated carboxylic acid glycidyl esters correspond to carboxyl group-containing monomer units because they are bonded to the polymer backbone in the form of esters. Further, in a copolymer obtained by copolymerizing styrene and maleic anhydride with 2-hydroxyethyl acrylate added to a maleic anhydride-derived portion, the maleic anhydride-derived portion opens a ring to form a carboxyl group. Therefore, the unit derived from maleic anhydride corresponds to the carboxyl group-containing monomer unit.

Preferred examples of the carboxyl group-containing copolymer (B) include benzyl methacrylate / methacrylic acid copolymer, benzyl methacrylate / methacrylic acid /
Styrene copolymers, methyl methacrylate / methacrylic acid copolymers, methyl methacrylate / methacrylic acid / styrene copolymers and the like can be mentioned. These carboxyl group-containing copolymers preferably have a polystyrene equivalent weight average molecular weight in the range of 10,000 to 400,000, and more preferably have a weight average molecular weight in the range of 20,000 to 300,000. The carboxyl group-containing copolymer (B) is generally 5 to 9 based on the total solid content in the colored photosensitive resin composition.
0% by weight, preferably in the range of 20 to 70% by weight.

In the present invention, as the cationic photopolymerizable compound (C), a compound having at least three alicyclic epoxy groups having an oxygen atom directly bonded to an alicyclic ring in a molecule is used. Since the alicyclic epoxy group undergoes cationic polymerization using an oxonium salt as a growth active species, this compound (C)
Contributes to the photocuring reaction in combination with the presence of a specific photopolymerization initiator (E) described later, and also contributes to capture of halogen-based gas and the like generated from the photopolymerization initiator (E). Such compounds having at least three alicyclic epoxy groups in the molecule and commercially available include 3
Formula (I) of functional type

[0020]

[Eporide GT301] [a + b in the formula (I) is about 1, epoxy equivalent: 185
205, manufactured by Daicel Chemical Co., Ltd.) and "Eporide GT302"
[Formula (I) wherein a + b is about 2, epoxy equivalent 22
5-250, manufactured by Daicel Chemical Co., Ltd.]

[0022]

"Eporide GT401" [formula (I
C) wherein c + d + e + f in I) is about 1, epoxy equivalent 2
10-225, manufactured by Daicel Chemical Industries, Ltd.], and "Epolead
GT403 "[c + d + e + f in the formula (II) is about 3,
Epoxy equivalent 270-300, manufactured by Daicel Chemical Co., Ltd.]. The cationic photopolymerizable compound (C) is more advantageous as the epoxy equivalent is smaller, but has at least three alicyclic epoxy groups in the molecule and has an epoxy equivalent of 350.
All can be used if it is less than or equal to.

The photo-radical polymerizable monomer (D) is a compound that undergoes radical polymerization by the action of light and a photopolymerization initiator, and generally corresponds to a compound having a polymerizable carbon-carbon unsaturated bond. This monomer (D)
Can be a bifunctional or other polyfunctional monomer in addition to a monofunctional monomer. Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-
Hydroxy-3-phenoxypropyl acrylate, 2
-Ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone and the like. As specific examples of the bifunctional monomer,
1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate and the like, and as other polyfunctional monomers, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipenta Erythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like can be mentioned. Among them, a bifunctional or higher polyfunctional monomer is preferably used.

The amounts of the cationic photopolymerizable compound (C) and the radical photopolymerizable monomer (D) will be described. The carboxyl group-containing copolymer (B), the cationic photopolymerizable compound (C) and the radical photopolymerizable monomer Photocationically polymerizable compound (C) based on 100 parts by weight of (D) in total
Is generally in the range of 0.1 to 60 parts by weight, preferably 1 to
It is contained in the range of 30 parts by weight, and the photo-radical polymerizable monomer (D) is also generally contained in the range of 0.1 to 60 parts by weight, preferably in the range of 1 to 30 parts by weight.

Next, in the present invention, a compound capable of initiating both photoradical polymerization and photocation polymerization is used as the photopolymerization initiator (E). Many of the known photopolymerization initiators initiate only photoradical polymerization, but initiators having an s-triazine skeleton, particularly s-triazine-based initiators having a trichloromethyl group, are acted upon by light as shown in the following formula. Decomposes to generate chlorine radicals, which extract hydrogen atoms from the donor RH to produce hydrogen chloride,
It is said to leave a donor radical R.

[0027]

Here, X is a group for making the initiator photoactive and adjusting the absorption wavelength, and is an aryl group, a benzene ring which may be substituted at the 2-position or a furan ring which may be substituted. Such a vinyl group and a piperonyl group to which the lowest hydrogenated ring is bonded correspond to this. The role of the donor represented by RH is present in the composition and is fulfilled by various compounds having a hydrogen atom. In the composition of the present invention, typically, the radical photopolymerization is carried out. Monomer (D)
Plays this role.

Then, the generated hydrogen chloride is dissociated into hydrogen ions and chloride ions to initiate cationic polymerization, and the radical R. of the donor initiates radical polymerization.

As described above, any compound which can initiate both photoradical polymerization and photocation polymerization with one molecule can be used as the photopolymerization initiator (E) in the present invention. A radical that is active against light and can generate an acid by abstracting a hydrogen atom from another component, such as a halogen radical, particularly a compound that generates a chlorine radical by the action of light, but typically A photopolymerization initiator having an s-triazine skeleton as described above is used.

The s-triazine-based photopolymerization initiator is
It is usually advantageous to have halomethyl groups, for example chloromethyl groups, especially trichloromethyl groups. Specifically, the following compounds can be mentioned.

2,4-bis (trichloromethyl) -6
(4-methoxyphenyl) -1,3,5-triazine,
2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-
Triazine, 2,4-bis (trichloromethyl) -6
(4-methoxystyryl) -1,3,5-triazine,
2,4-bis (trichloromethyl) -6- [2- (5-
Methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6
[2- (furan-2-yl) ethenyl] -1,3,5-
Triazine, 2,4-bis (trichloromethyl) -6
[2- (4-Diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl]- 1,3,5-triazine and the like.

In the present invention, it is essential to use a compound capable of initiating both radical photopolymerization and cationic photopolymerization as the photopolymerization initiator (E). Can also be used. The photopolymerization initiator to be used in combination can be one commonly used in this field, and examples thereof include acetophenone-based, benzoin-based, benzophenone-based, thioxanthone-based, and other initiators. More specifically,
The following compounds can be mentioned, and one or more of these compounds can be used in combination with the compound capable of initiating both the photoradical polymerization and the photocation polymerization described above.

(A) acetophenone initiator diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) Phenyl] -2-methylpropane-1-
On, 1-hydroxycyclohexyl phenyl ketone,
2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-
1-one, 2-hydroxy-2-methyl-1- [4-
(1-methylvinyl) phenyl] oligomers of propan-1-one and the like.

(B) Benzoin initiators Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and the like.

(C) Benzophenone initiator benzophenone, methyl o-benzoylbenzoate,
Phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone and the like.

(D) Thioxanthone initiator 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone,
4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like.

(E) Other initiators 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2'-bis (o-chlorophenyl)
-4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone,
2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compounds and the like.

Further, a photopolymerization initiator can be used in combination with a photoinitiator. Specific examples of the photoinitiating aid include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate,
Isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine,
4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene,
9,10-diethoxyanthracene, 2-ethyl-9,
10-diethoxyanthracene and the like. These photoinitiating aids can be used alone or in combination of two or more.

The photopolymerization initiator (E) capable of initiating both photoradical polymerization and photocationic polymerization includes a carboxyl group-containing copolymer (B) in a photosensitive resin composition, and a photocationic polymerizable compound (E). In general, 0.1 to 100 parts by weight of the total of C) and the photo-radical polymerizable monomer (D) are used.
It is contained in the range of 50 parts by weight, preferably in the range of 1 to 30 parts by weight. Further, when other photopolymerization initiators are used in combination, and when a photoinitiation auxiliary is optionally used, a photopolymerization initiator (E) capable of initiating both photoradical polymerization and photocationic polymerization is included. The total amount thereof is generally based on 100 parts by weight of the total of the carboxyl group-containing copolymer (B), the cationic photopolymerizable compound (C) and the photoradical polymerizable monomer (D) in the photosensitive resin composition. Is contained in the range of 0.1 to 50 parts by weight, preferably 1 to 30 parts by weight.

The solvent (F) can be any of those used in this field. Specific examples include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dipropyl ether. Diethylene glycol dialkyl ethers such as butyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether Propylene glycol alkyl ether acetates such as luacetate; aromatic hydrocarbons such as benzene, toluene and xylene; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone; ethanol, propanol and butanol , Hexanol, cyclohexanol,
Alcohols such as ethylene glycol and glycerin; esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; and cyclic esters such as γ-butyrolactone. These solvents can be used alone or in combination of two or more. The amount of the solvent used is preferably 60 to 9 based on the total amount of the colored photosensitive resin composition containing the solvent.
0% by weight, more preferably 70 to 85% by weight.

The colored photosensitive resin composition of the present invention may also contain, if necessary, a filler, another polymer compound, a surfactant (pigment dispersant), an adhesion promoter, an antioxidant, an ultraviolet absorber, An additive such as an anti-agglomeration material may be contained.
Specific examples of the filler include glass, silica, and alumina, and specific examples of other polymer compounds include polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate. As the (pigment dispersant), various types such as nonionic, cationic, and anionic are used. Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltris (2-methoxyethoxy) silane. , N- (2-aminoethyl)-
3-aminopropylmethyldimethoxysilane, N- (2
-Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-
Epoxycyclohexyl) ethyltrimethoxysilane,
3-Chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like, specifically, 2,2'- Thiobis (4-methyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol and the like are specifically exemplified as 2- (3-tert-butyl-2-butyl) as an ultraviolet absorber. (Hydroxy-5-methylphenyl) -5-chlorobenzotriazole, alkoxybenzophenone, and the like, and specific examples of the aggregation inhibitor include sodium polyacrylate.

The colored photosensitive resin composition of the present invention can be prepared, for example, as follows. That is, the pigment (A) is previously mixed with the solvent (F), and the average particle diameter of the pigment is 0.2 μm.
Disperse the mixture using a bead mill or the like until the dispersion becomes about the following. At this time, a dispersant is used as needed, and a part or all of the carboxyl group-containing copolymer (B) may be blended. Pigment dispersion obtained (mill base)
The remaining carboxyl group-containing copolymer (B), photocationically polymerizable compound (C), photoradical polymerizable monomer (D) and photopolymerization initiator (E), and other components used as required Further, if necessary, an additional solvent is added so as to have a predetermined concentration to obtain a desired colored photosensitive resin composition.

The photosensitive resin composition thus prepared is
For example, a colored image can be formed by applying the composition on a substrate, photocuring and developing as described below. First, the composition is spin-coated on a substrate (usually glass), and the solvent is heated and dried (prebaked) to obtain a smooth coating film. The thickness of the coating film at this time is about 1 to 2 μm. The obtained coating film is irradiated with ultraviolet rays through a negative mask for forming a target image. At this time, it is preferable to use a device such as a mask aligner so that the entire exposed portion is uniformly irradiated with parallel rays and the mask and the substrate are accurately aligned. Thereafter, the cured coating film is brought into contact with a dilute aqueous alkaline solution to dissolve the unexposed portion and develop it, thereby obtaining an intended image. After development, if necessary,
Post-curing (post-baking) for about 60 minutes can also be performed.

The developer used for the development after the patterning exposure is usually an aqueous solution containing an alkaline compound and a surfactant. The alkaline compound may be any of inorganic and organic alkaline compounds. Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide,
Disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate , Potassium borate, ammonia and the like. Further, specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine,
Triethylamine, monoisopropylamine, diisopropylamine, ethanolamine and the like. These inorganic and organic alkaline compounds can be used alone or in combination of two or more. The preferred concentration of the alkaline compound in the alkaline developer is
0.01 to 10% by weight, more preferably 0.0 to 10% by weight.
It is 3 to 5% by weight.

The surfactant may be any of a nonionic surfactant, a cationic surfactant and an anionic surfactant. Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymer, sorbitan fatty acid ester, and polyoxyethylene alkyl ether. Oxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine and the like can be mentioned. Specific examples of anionic surfactants include higher alcohol sulfates such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate; alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate; sodium dodecylbenzene sulfonate; Alkyl aryl sulfonates such as sodium dodecylnaphthalene sulfonate, and the like. Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts. These surfactants can be used alone or in combination of two or more. The concentration of the surfactant in the alkali developer is usually 0.0
1 to 10% by weight, preferably 0.05 to 8% by weight,
More preferably, the content is 0.1 to 5% by weight.

The application and drying of the photosensitive resin liquid as described above
Through each operation of patterning exposure to the obtained dried coating film and development, a pixel corresponding to the color of the pigment in the photosensitive resin composition is obtained, and these operations are further performed by the color required for the color filter. By repeating the same number of times, a color filter is obtained. That is, the color filter is usually one in which red, green and blue pixels are arranged on a substrate, and the above operation is performed using the colored photosensitive resin composition of the present invention containing a pigment corresponding to a certain color. By doing so, a pixel of that color is obtained, and the same operation is performed using the colored photosensitive resin composition of the present invention containing a pigment corresponding to a desired color also for the other colors, and the three-color pixels are formed on the substrate. Can be arranged. Of course, the colored photosensitive resin composition of the present invention can be applied to only one or two of the three colors. Further, the colored photosensitive resin composition of the present invention containing a black pigment can be used for forming a black matrix which is a light shielding layer.

[0048]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the examples, percentages and parts representing the content or the used amount are based on weight unless otherwise specified. Also,
Epoxy compounds and photopolymerization initiators used in Examples and Comparative Examples are commercially available products shown by trade names below,
Display with each product name.

(C) Epoxy compound Epolide GT401: 4-functional alicyclic epoxy compound (manufactured by Daicel Chemical Industries, Ltd., the structure is as described above), epoxy equivalent 219, cationic photopolymerization. Denacol EX-321: 2-3 functional aliphatic epoxy compound (Nagase Kasei Co., Ltd., mixture of di- and tri-glycidyl ethers of trimethylolpropane), epoxy equivalent 1
45, non-photopolymerized type.

(E) Photopolymerization initiator Triazine PP: 2,4-bis (trichloromethyl)-
6-piperonyl-1,3,5-triazine (manufactured by Nippon Siebel-Hegner, both radical polymerization and cationic polymerization can be initiated). Irgacure 907: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (manufactured by Ciba-Geigy, only radical polymerization can be started).

Example 1 and Comparative Examples 1 to 4 As representative examples, Examples and Comparative Examples in which a blue photosensitive resin composition was prepared and evaluated are shown. The composition of the photosensitive resin composition used here is as follows.

Pigment: CI Pigment Blue 15: 6 3.9 parts CI Pigment Violet 23 0.1 parts Carboxyl group-containing copolymer 8.4 parts Copolymer (polystyrene having a weight ratio of benzyl methacrylate / methacrylic acid of 80/20 (polystyrene) Equivalent weight average molecular weight 35,000) Epoxy compound described in Table 1 Photo-radical polymerizable monomer described in Table 1 Dipentaerythritol hexaacrylate ("Kayarad DPHA" manufactured by Nippon Kayaku Co., Ltd.) Photopolymerization initiator described in Table 1 Nonionic pigment dispersant 1.0 Part solvent: propylene glycol monomethyl ether acetate 79.2 parts

Of the above components, the total amount of each of the pigment and the pigment dispersant is mixed in advance with a partial amount of propylene glycol monomethyl ether acetate, and the pigment is sufficiently dispersed using a bead mill to perform a fine treatment. The remaining components including the remaining amount of propylene glycol monomethyl ether acetate were added and mixed to obtain a photosensitive resin liquid of each composition.

A 2-inch square quartz glass substrate was washed successively with a neutral detergent, water and alcohol, and then dried.
Each of the photosensitive resin solutions prepared above was spin-coated on the glass substrate so as to have a predetermined thickness, and then prebaked in a clean oven at 100 ° C. for 3 minutes.
A part of the resist film was covered with an aluminum light-shielding plate having a thickness of 1.0 mm and a width of 2.0 cm.
Light irradiation was performed at an exposure amount of mJ / cm ² . Thereafter, the coating film was immersed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at room temperature for 2 minutes. After washing with water, it was observed whether the unexposed portions protected from light were dissolved in the developer and disappeared. Subsequently, after post-baking at 220 ° C. for 30 minutes, the surface state of the coating film was changed to “200 mJ
/ Cm ² Residual film sensitivity ”, where the surface roughness of the coating film due to film loss was not recognized as“ good ”, and the surface roughness was recognized as“ poor ”.

Further, for those having a good surface condition, the amount of chloride ion eluted from the coating film was measured.
The measurement substrate was prepared as follows. That is, a resist film is formed on a 2 inch square quartz glass substrate in the same manner as above, and thereafter, without covering with a light shielding plate,
Using a super high pressure mercury lamp manufactured by Ushio Inc., the entire surface of the coating film was irradiated with light at an exposure amount of 200 mJ / cm ^{2 in} an air atmosphere. Subsequently, post-baking was performed at 220 ° C. for 30 minutes without immersion in a developer, and the obtained substrate with a coating film was used as a measurement sample.

The amount of chloride ion eluted from the coating film was measured as follows. A glass frame having an opening of 2 cm × 3 cm was placed on the coating film, and 0.5 cc of N-methyl-2-pyrrolidone was dropped into the opening, and N-methyl-2-pyrrolidone was brought into contact with the entire coating film at the opening. I spread it. These were left on a hot plate at 40 ° C. for 30 minutes. Thereafter, 2.0 cc of N-methyl-2-pyrrolidone was further added, and the amount of chloride ion eluted was measured. The measurement of the amount of eluted chloride ions was performed using an IC-7000 type ion chromatograph manufactured by Yokogawa Analytical Systems. The above results are shown together in Table 1 together with the compositional variables.

[0057]

[Table 1] 例 Example Comparative example Comparative example Comparative example Comparative example 1 1 2 3 4 Epoxy compound: Eporide GT401 3.0 parts-- 3.0 parts 6.0 parts Denacol EX-321 − − 3.0 parts − − ──────────────────────────────────── Photoradical polymerizable monomer 3.0 parts 6.0 parts 3.0 parts 3.0 parts − ──────────────────────────────────── Photopolymerization initiator: Triazine PP 1.4 parts 1.4 parts 1.4 parts-1.4 parts Irgacure 907---1.4 parts-━━━━━━━━━━━━━━━━━━━━━━━━━━現 像 Developer solubility of coating film after pre-baking Elution chlorine 3 9 from soluble soluble soluble soluble 200 mJ / cm ² residual sensitivity Good Good bad bad bad post-baking after coating - - - ion amount (ng / cm ²⁾ ──────── ──────────────────────────── Overall judgment ○ × × × × ━━━━━━━━━━━━━━━ ━━━━━━━━━━━━━━━━━━━━━

As can be seen from Table 1, according to the present invention, 3
"Eporide GT4", a functional alicyclic epoxy compound
01 "and a coating film obtained from the composition of Example 1 containing" Triazine PP "which initiates both photoradical polymerization and photocationic polymerization have high sensitivity even in an air atmosphere, and have a high amount of eluted chloride ions. On the other hand, the coating films obtained from the compositions of Comparative Examples 1 to 4 were inadequate because sensitivity and suppression of the amount of eluted chloride ions were not balanced.

[0059]

As described above, the colored photosensitive resin composition of the present invention has a good residual film sensitivity under an air atmosphere, and can form a cured film with a small amount of exposure. Therefore, when this composition is used as a pigment-dispersed resist to produce a color filter, high productivity can be ensured. Further, even when a compound having an s-triazine skeleton is used as a photopolymerization initiator capable of initiating both photoradical polymerization and photocation polymerization, the amount of halogen-based impurities such as hydrogen chloride generated therefrom is reduced. Can be suppressed.
Therefore, when a color filter is produced from this composition and used for a liquid crystal display material, malfunction of the liquid crystal caused by these impurities can be significantly reduced.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // C09D 4/06 C09D 4/06

Claims (7)

[Claims] (1) a pigment, (B) a carboxyl group-containing copolymer, and (C) a cationic photopolymerization having at least three alicyclic epoxy groups having an oxygen atom directly bonded to an alicyclic ring in a molecule. Compound, (D) photo-radical polymerizable monomer,
A colored photosensitive resin composition comprising (E) a photopolymerization initiator capable of initiating both photoradical polymerization and photocationic polymerization, and (F) a solvent. 2. The composition according to claim 1, wherein the photopolymerization initiator (E) has an s-triazine skeleton. 3. The composition according to claim 2, wherein the photopolymerization initiator (E) is a compound having a halomethyl group bonded to an s-triazine skeleton. 4. The composition according to claim 3, wherein the halomethyl group is a trichloromethyl group. 5. The photocationically polymerizable compound (C) has a content of 350
The composition according to any one of claims 1 to 4, having the following epoxy equivalent. 6. The cationic photopolymerizable compound (C) is added to the total of 100 parts by weight of the carboxyl group-containing copolymer (B), the cationic photopolymerizable compound (C) and the photoradical polymerizable monomer (D). A composition according to any of the preceding claims, being present in the range from 0.1 to 60 parts by weight. 7. The photopolymerization initiator (E) is used in an amount of 100 parts by weight of the total of the carboxyl group-containing copolymer (B), the cationic photopolymerizable compound (C) and the photoradical polymerizable monomer (D). 1 to 50 parts by weight.
7. The composition according to any one of 6.