JPH1115147A - Production of color image forming material photosensitive element and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a stable color image forming material having a uniformly dispersed pigment without coloring process and prolonged in service life by incorporating a polymer having a lameimide group in the skeleton in a photosensitive composition. SOLUTION: The color image forming material contains the polymer having the maleimide group in the skeleton, a photoinitiator, a compound having at least one ethylenic unsaturated bond and a coloring agent. The color image forming material can be used as a negative color image formed material. And a photosensitive element is obtained by forming a layer of the color image forming material on a supporting body. A strippable cover film can be laminated on the layer of the color image forming material. The color image forming material has high sensitivity, high resolution and alkali development, and is further improved in heat resistance and small in the change of the chromaticity and the film thickness of a color filter even in the case of being stored at >=200 deg.C to <=300 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a colored image forming material, a photosensitive liquid containing the same, a liquid crystal display such as a television, a computer or a video monitor, a CCD using a photosensitive element and a color filter using the same.
And a color forming layer that can be used for an image scanner or the like.

[0002]

2. Description of the Related Art Conventionally, when a colored image is formed, a photosensitive image is formed as an aqueous solution of dichromic acid such as gelatin, PVA, casein or other water-soluble synthetic resin to form a transparent image pattern. Methods of forming a colored image by dyeing with a dye or the like are described in, for example, JP-B-52-17375 and JP-B-52-173765. This dyeing method has a drawback that a dyeing step is required, and since the dye is a dye, heat resistance is low, and there is discoloration due to light peculiar to dyeing or discoloration due to aging, so-called discoloration, and it is difficult to form a stable colored image. Was. Further, in a method of forming a three-color dot (dot) by adhering a toner on a transparent resin pattern by a photopolymerization method or a photo-crosslinking method using a photosensitive resin to form a halftone dot (dot), a color proof is used. Since dispersion is not possible, the pigment is formed on the pattern formed on the halftone dots. This step still requires an independent dyeing step.

As a method of compensating for the drawbacks of these methods, recently, photosensitive materials in which a pigment is dispersed have been studied by various companies. In the case of a heavy chromium oxygen-based light-sensitive material, secondary aggregation of the pigment occurred, and the pigment dispersion could not be obtained as a stable liquid. In this regard, the photopolymerization method using a photosensitive resin has come to be produced as a photosensitive liquid having a stable pigment dispersion.

[0004] The pigment-dispersed photosensitive liquid has a shorter process, and is excellent in hue, heat resistance and fading as compared with a dyeing method or the like. For example, JP-A-1-152449, JP-A-1-254
No. 918 has proposed a method of forming a colored pattern in which a pigment is dispersed. The main composition of the pigment-dispersed photosensitive liquid is as follows. Polymers (containing reactive double bonds),
2. Monomer, 3. Pigments, 4. It consists of a photoinitiator and the like. Until now, this photopolymerization method has been used for forming and forming a colored formation layer, but it is 240 ° C or more even if it is superior in hue, heat resistance, and fading compared to a dyeing method or the like.
At a temperature of not more than ° C., after a predetermined step, there was a decrease in film thickness and a change in chromaticity of the coloring material [[color difference (ΔEab *) was 5 or less]], which was not sufficient for required performance. It is 240 ℃ ~ 300
It is thought that this occurs because the heat resistance of the color forming layer is still insufficient at ℃. Among the above-listed materials, components that function to improve heat resistance and prevent film loss include: (Including a reactive double bond); 2. the monomer of
And the like.

[0005] However, 3. There are limits to the choice of pigments. The heat resistance of the pigment is phthalocyanines such as C.I. I. Pigment Green 36 has a temperature of 200 ° C. Hardening the acrylic polymer having the double bond of 2. In the selection of the acrylic monomer described above, the film loss or heat resistance at 240 ° C. to 300 ° C. cannot sufficiently meet the required performance.

[0006]

SUMMARY OF THE INVENTION The present invention relates to a stable colored image forming material having a long service life in which a pigment which does not require a dyeing step as described in the prior art is uniformly dispersed, and a photosensitive material containing the same. It is intended to provide a liquid, a photosensitive element using the same, and a method for producing a color filter. When the overcoat film, the ITO electrode, and the alignment film are formed, they are exposed to a temperature of 240 ° C. or more and 300 ° C. or less for a predetermined time, so that the resin contracts or decomposes due to heat, or changes in the chromaticity of the colorant [[color difference (ΔEab * ) Is 5 or more]. For this reason, the color filter has been formed to have a thickness larger than the thickness at the time of completion at the time of film formation, or a pigment having high heat resistance has been used as a colorant, but there are limitations. The present invention
An object of the present invention is to provide a photosensitive composition having excellent heat resistance, a photosensitive element, and a method for producing a color filter using the same.

[0007]

Means for Solving the Problems The present inventors incorporated a polymer having a maleimide group in the skeleton into a photosensitive composition as a colored image-forming material, so that when the film was formed as a film on a substrate, 240 It has been found that the film thickness and the chromaticity stability are improved even when stored for a certain period of time at a temperature of not lower than 300 ° C. and not higher than 300 ° C.

The colored image forming material of the present invention comprises (A) a polymer having a maleimide group in the skeleton, (B) a photoinitiator,
(C) a compound having at least one ethylenically unsaturated bond, and (D) a colorant. The colored image forming material of the present invention can be used as a negative type colored image forming material. The photosensitive element of the present invention is obtained by forming a layer of the above-mentioned colored image forming material on a support. A peelable cover film can also be laminated on the layer of the colored image forming material. The method for producing the color filter of the present invention comprises:
Using the above-mentioned colored image forming material or photosensitive element, a colored image forming material is formed as a film on a substrate, irradiated with actinic rays in an image form, the exposed portion is light-cured, and the unexposed portion is removed by development. This step is repeated for the colored image forming materials of a plurality of different colors to form pixels.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION A polymer having a maleimide group in the skeleton is

Embedded image Is a copolymer of a monomer having a maleimide group represented by the general formula (1) and R1, wherein R2 is H or OH, a halogen element, or a hydrocarbon group having 1 to 12 carbon atoms (alkyl,
Aliphatic hydrocarbons such as alkenyl, alkene, ethers and esters thereof, and saturated and unsaturated cyclic hydrocarbons such as cycloalkane, phenyl and carboxyl-substituted phenyl). For m and n, m + n = 100 mol% and m / n = 99/1 to 1/99 (mol%).
R1 is selected, for example, from the group of monomers listed below;
A copolymer is obtained from a monomer having a maleimide group and at least one or two or more monomers. The monomer forming R1 is (a) styrene such as styrene, α-methylstyrene, m or p-methoxystyrene, p-methylstyrene, p-hydroxystyrene, 3-hydroxymethyl-4hydroxy-styrene, or a derivative thereof (styrene). Monomer), (b) acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, n-propyl acrylate,
N-propyl acrylate, lauryl acrylate, octyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-methacrylate
Acrylic acid such as propyl, lauryl methacrylate, octyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, methacrylic acid, their esters or their derivatives (acrylic monomers), (c) N-hydroxymethyl Acrylamide, N
Acrylamides such as -hydroxyethylacrylamide, N-methoxymethylacrylamide, N-butoxymethylacrylamide, N, N'-methylenebisacrylamide, N-methylolacrylamide, (d) allylphenol, acrylonitrile, vinylacetic acid (e) maleic anhydride , Maleic acid, monomethyl maleate, monoethyl maleate, mono-n-propyl maleate, mono-iso-propyl maleate-n-butyl maleate, mono-iso-butyl maleate, mono-tert-butyl maleate and the like (F) at least one of fumaric acid, itaconic acid, crotonic acid or a derivative thereof is used. (B) to (f)
Can preferably be used with styrene. The present invention is not limited to these. The weight average molecular weight of the polymer is preferably in the range of 1,500 to 500,000, more preferably in the range of 1,500 to 80,000.

Further, by adding and introducing an active double bond to the carboxyl group of the above-mentioned copolymer having a maleimide group, the sensitivity of the photosensitive composition of the present invention in photopolymerizability is compared with the case where there is no double bond. Get higher. Its height depends on the rate of introduction of double bonds. A method of adding and introducing an active double bond to a carboxyl group includes an oxirane ring-containing ethylenically unsaturated compound such as glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, α-
Unsaturated alcohols such as ethyl glycidyl acrylate, crotonyl glycidyl ether, monoalkyl monoglycidyl itaconate, and allyl alcohol;
2-bran-1--2-free furyl alcohol,
Using oleyl alcohol, cinnamyl alcohol, 2-hydroxyethyl acrylate, hydroxyethyl methacrylate, N-methylol acrylamide, etc., JP-B-47-25470, JP-B-48-85679, and JP-B-51-21572. And the like. The amount of the polymer represented by the general formula (1) is 0.1 to 70% by weight, preferably 0.3 to 40% by weight of the solid content in the photosensitive composition and the color filter material of the present invention. is there.

In the present invention, a copolymer having a carboxyl group, which is a polymer component as an alkali-soluble dispersing resin having a carboxyl group, is optionally used. There is no particular limitation as long as it can be used as a polymer material of a photosensitive resin capable of alkali development, but a copolymer of a styrene monomer and maleic acid or a derivative thereof (hereinafter, referred to as an SM polymer) ), A styrene monomer (a '), an unsaturated monomer having a carboxyl group such as acrylic acid or methacrylic acid (b'), and an alkyl methacrylate such as methyl methacrylate, t-butyl methacrylate, or hydroxyethyl methacrylate. A ternary or quaternary copolymer with another monomer (c ′) such as an alkyl acrylate having an alkyl group is preferred. These polymers have a carboxyl group content of 30 to 20 in terms of acid value.
It is preferable to include them so as to be 0, particularly 50 to 170.

The photoinitiator which is the component (B) in the present invention includes, for example, benzophenone, Michler's ketone, [4,4'-bis (dimethylamino) benzophenone], benzyl, 2,2-deoxyacetophenone,
Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin butyl ether, benzyl dimethyl ketal, α-hydroxyisobutylphenone,
Thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1
-[4- (methylthio) phenyl] -2-morpholino-
1-propanone, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone,
p-chloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, octamethylanthraquinone, 1,4-naphthoquinone, 9,10-
Phenanthraquinone, 1,2-benzanthraquinone,
Alkyl-substituted or halogen-substituted anthraquinones such as 2,3-benzoanthraquinone, 1,4-dimethylanthraquinone and 2-phenylanthraquinone, or bis (cyclopentagenenyl) -bis- [2,6-difluoro-3- ( Pyyl-1-) phenyl] -titanium nititanocene, 2,2-bis (o-chlorophenyl) -4,5,
4 ', 5'-tetraphenyl-1,2'-biimidazole, 1-6-n-cumene (n-cyclopentagenenyl) iron-6-fluorophosphoric acid, dibenzosperon, 10-
Butyl-2-chloroacridone, 2,4-trichloromethyl (4'-trixistyl) -6-triazine, 2-
Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, and other sensitizers,
For example, carbon tetrachloride, ω, ω, ω-tribromomethylphenylsulfone 7,8,9,10-tetraphenylsulfone, 1,2,3,4-tetrahydroanthracene and the like are also used. The amount of the compound to be used is preferably 0.01 to 25% by weight, more preferably 1 to 20% by weight, based on the total solid content in the colored image forming material of the present invention.

The addition of an amine as an amine sensitizer for improving the sensitivity is effective because the curing speed is increased and the effect of inhibiting polymerization of oxygen and the like is reduced. Examples of such amines include primary amines such as butylamine, hexamethylenediamine, diethylenetriamine, triethylenetriamine, and monoethanolamine, diethylamine, dimethylaniline, diethanolamine, triethanolamine, triethanolamine, and triacrylate dimethyl-p. Secondary amines such as -toluidine, pyridine, methyldiethanolamine, N, N'-dimethylcyclohexylamine.
The amount of the amine sensitizer to be used is preferably 0.01 to 17% by weight, more preferably 2 to 10% by weight of the total solid content in the colored image forming material of the present invention. If the amount is too small, the photosensitivity tends to decrease. If the amount is too large, the adhesiveness tends to decrease, and the tackiness of the dried coating film tends to occur.

In the present invention, the compound having at least one reactive double bond as the component (C) includes, for example, trimethylolpropane triacrylate, trimethylolpropane diacrylate, triethylene glycol diacrylate, diethylene glycol diacrylate. Acrylate, tetraethylene glycol diacrylate, hexamethylene glycol diacrylate, neopentyl glycol diacrylate, furfuryl acrylate,
Tetramethylol methane tetraacrylate, resorcinol diacrylate, p, p'-dihydroxydiphenyl diacrylate, spiro glycol diacrylate, cyclohexane dimethylol diacrylate, bisphenol A diacrylate, polypropylene glycol diacrylate, dipentaerythritol hexaacrylate, and the above A compound having the same structure as methacrylate,
Examples include polyfunctional monomers such as methylenebisacrylamide and urethane diacrylate.

Further, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, alkyl methacrylate, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, benzyl methacrylate, mono (2-methacryloyloxyethyl) acid phosphate, dimethyl methacrylate Monofunctional monomers such as quaternary aminoethyl methacrylate are exemplified.
Further, "Light Sensitive Material List Book" (edited by Photopolymer Society, published by Bunshin Publishing, published on March 31, 1996)
It is preferably selected from those described. These (C)
The components can be used as a mixture of two or more kinds. The amount of the compound to be used is preferably 1 to 30% by weight of the total solid content in the colored image forming material of the present invention, and is 5 to 25%.
It is more preferable to set the weight%. If the amount is too small, the effect of improving the photosensitivity tends to be low. If the amount is too large, the adhesiveness is poor and the tackiness of the dried coating film tends to increase.

The coloring agent (D) effective for the colored image forming material includes inorganic pigments and organic pigments. Examples of the organic pigment include azo pigments such as azo pigments and condensation pigments insoluble in solvents (including water), phthalocyanine pigments, other indigo pigments, anthraquinone pigments, perylene pigments, quinacridone pigments, methine azomethine pigments, and isoindolinone pigments. Is mentioned.

The three primary colors Blue, Green, Re
As the organic pigment constituting d, Blue is a phthalocyanine pigment. For example, C.I. I. Pigmen
tBlue: 6 (CI No. 74160), C.I.
I. Pigment Blue 60 (CI No. 6)
9800), and C.I. I. Pig
A mixture with Ment Violet 23 is used. G
green is a halogenated phthalocyanine pigment such as C.I. I. Pigment Green 7
(CI No. 74260), C.I. I. Pigmen
t Green 36 (CI No. 74265),
C. I. Pigment Green 37 (C.I.N.
o. 74255) Also, in order to improve color reproducibility, for example, a yellow pigment C.I. I. Pigment Yellow 13
9 (no CI No.), C.I. I. Pigment
Mixing with Yellow 83 (CI No. 21108) is used. Red is a quinacridone pigment or an anthraquinone red pigment. For example, C.I. I.
Pigment Red 209 (CI No. 73)
905), C.I. I. Pigment Red 177
(CI No. 65300), in order to improve color reproducibility, similar to the case of Green, for example, a yellow pigment C.I.
I. Pigment Yellow 139, C.I. I.
Pigment Yellow 83 is used. Examples of the inorganic pigment include chromium oxide, ultramarine blue, cadmium yellow, cadmium red, cobalt green, cobalt blue, and yellow lead.

As an organic pigment constituting cyan, magenta and yellow, which are complementary colors of the three primary colors, cyan is C.I. I. P
i.g. Blue 15: 3 (CI No. 74)
160), and magenta is C.I. I. Pigment
Red 57: 3 (CI No. 1585 0:
1), for example, C.I. I. Pigment Yel
low12 (CI No. 21090) or the like is used.

The coloring agent forming the black matrix includes carbon black, titanium carbon, iron black and the like.

When these pigments are dispersed, they are dispersed with an ultrasonic disperser, a three-roll mill, a bead mill homogenizer, or the like. In a bead mill, beads such as zirconia are added to a container, and a pigment or the like is pulverized by high-speed rotation by a rotating rotor.

A polymerization inhibitor can be added to the colored image forming material of the present invention in order to prevent a dark reaction. Examples of the polymerization inhibitor include hydroquinone, P-methoxyphenol, 2,6-di-t-butyl-p-cresol, and 2,2′-methylenebis (4-methyl-6-t-
Butylphenol), cuperon and the like. The amount of the compound to be used is preferably 0.001 to 1% by weight, more preferably 0.1 to 0.5% by weight of the total solid content in the colored image forming material of the present invention. If the amount is too small, the polymerization inhibitor is ineffective, and if it is too large, the sensitivity tends to decrease.

The colored image-forming material of the present invention can be coated on a support and dried without solvent or dissolved in an appropriate solvent. In the case of no solvent, it is possible by using a monomer as a diluent and adding as much as other substances dissolve. However, since the dark reaction is accelerated as compared with the case where the solvent is present, it is necessary to add a large amount of a polymerization inhibitor.

Further, for the purpose of dissolving in a solvent to form a photosensitive solution, the solvent optionally used includes:
Ketone solvents, cellosolve solvents, alcohol solvents,
Examples include ether solvents and non-polar solvents. Specifically, methyl ethyl ketone, acetone, cyclohexane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, ethylene glycol monopropyl ether, ethylene glycol mono n-hexyl ether, ethylene glycol dimethyl ether, diethylene glycol ethyl ether , Triethylene glycol dimethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methyl-3-meth Xybutanol, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether propionate, N-methyl-2-pyrrolidone, N-hydroxymethyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, methyl alcohol, ethyl alcohol Isopropyl alcohol, tetrahydrofuran, dioxane, benzene, toluene, xylene, ethyl acetate and the like. These solvents may be used as a mixture of two or more kinds.

Such a solvent is preferably used in such an amount that the solid content of the colored image forming material is 10 to 60% by weight. If the amount of the solvent is too large, the stability of the dispersion tends to decrease. If the amount is too small, the effect of lowering the viscosity or the like may be low, or gelation may easily occur.

As a support for applying a photosensitive solution dissolved in a diluent or a solvent for forming a colored image, for example, for a color filter, a transparent glass plate,
Blue plate glass, mainly non-alkali, aluminosilicate, quartz glass and the like are used. For other uses, an acrylic resin plate, a vinyl chloride resin plate, a copper plate, an aluminum plate, a nickel plate, a metal plate of stainless steel or the like is used.

Examples of the coating method include roll coater coating, spin coater coating, spray coating, white coater coating, dipping coater coating, curtain flow coater coating, wire bar coater coating, gravure coater coating, and air knife coater coating. After the photosensitive solution is applied on these supports by the above-described method, the applied solution is naturally dried or forcibly dried by heating to form a dried coating film having a thickness of several μm.

Alternatively, the film can be formed as a film on the present support by directly coating it on a support and forming a photosensitive element instead of coating directly on the substrate, followed by lamination. This method is effective when the coating cannot be applied directly to the support. The method of coating the temporary support can be performed by the method described in the above-mentioned coating method.

As the temporary support used at this time,
For example, polyester film, polyamide film,
A polyimide film, a polypropylene film, a polystyrene film, or the like can be used. It is applied to these films and dried by a usual method such as natural drying or forced drying. It is desirable to laminate a peelable cover film on the surface of the coating film in order to prevent dust and dirt from adhering to the coating film applied to the temporary support.

As the peelable cover film, for example, a polyethylene film, a Teflon film or a polypropylene film can be used. It is only necessary that the adhesive strength of the cover film is smaller than the adhesive strength of the temporary support.

As a method of laminating the photosensitive element obtained on the temporary support to the present support, it is preferable to peel off the cover film and heat-press on the substrate as the present support to improve the adhesion. preferable.

The thickness of the colored image forming material in the method formed on the substrate surface in this way is determined depending on the application, but is usually used in the range of 0.1 to 500 μm.
When used for a color filter, it is used in the range of 0.1 to 5 μm.

The photosensitive layer, which is a dried coating film, is exposed with an exposure machine to cure the photosensitive portion. The exposing machine applicable to the composition of the present invention includes a carbon arc lamp, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp and the like.

[0033]

【Example】

Example 1 First, a dispersion was prepared. Dispersion [1] is obtained by dispersing a resin (polymer A-1), which is an N-phenyl group-containing copolymer (polymer A-1), and a pigment with a solvent in a bead mill for 3 hours, and forming a pixel blue.
It was created. Polymer A is an N-phenylmaleimide-styrene-methacrylic acid resin (N-phenylmaleimide:
The molar ratio of styrene: methacrylic acid is 3: 4: 2), the weight average molecular weight is 41,000, the acid value is 75, and the pigment at this time is C.I. I. Pigment Blue 15: 6 and C.I. I. Pigment violet-23,
The weight ratio was 91: 9, and γ-butyrolactone was used as the solvent. The composition of the dispersion [I] was 37.5% of resin, 15% of pigment, and 50% of solvent γ-butyrolactone. The dispersant was A-600 (trade name, manufactured by Dai-ichi Koyaku Co., Ltd.) at a ratio of 2.5%. The average particle size of the pigment is Horiba-CAP.
It was 0.08 μm as measured with an A-700 Particle-Analyzer. Using this dispersion [1], a photosensitive solution for a color filter was mixed with a stirrer to prepare a dispersion. As a result of measurement using an E-type viscometer manufactured by Tokimec, 44 m
・ It was Pa · S. The formulation of the color filter photosensitive liquid is as follows. The viscosity of the photosensitive solution was 24 m · Pa · S.

The composition of the photosensitive solution is as follows. Parts are parts by weight (the same applies hereinafter). [Resin] Polymer A-1 78 parts [Crosslinking agent] Trimethylolpropane triacrylate 30 parts [Photoinitiator] Benzophenone 8 parts Benzoin ethyl ether 8 parts [Solvent] N-methylpyrrolidone 5 parts γ-butyrolactone 500 parts [Polymerization prohibited 0.1 part of p-methoxyphenol [Surfactant] 0.01 part of perfluoroalkyl alkoxylate [Colorant] 48 parts of dispersion [1] 48 parts of the obtained photosensitive solution was used as a glass substrate manufactured by Corning Incorporated, trade name 7
059 was applied with a spinner at 1200 rpm and dried. The dry film thickness obtained by this coating is 2.0
μm. The dispersion stability as a pigment dispersion photosensitive liquid was very good. It was found that the film after coating and drying was also transparent, and the dispersion was stable. Next, the coating film was brought into close contact with a glass mask having a triangular mosaic pattern, and was exposed with an ultra-high pressure mercury lamp manufactured by Oak. The exposure amount was 130 mJ / cm ² , and a step tablet (21 steps) manufactured by Kodak Co. was also exposed simultaneously for sensitivity measurement. Next, development was performed by immersion development.
There was no rough edge of the pattern (pixel).

The composition of the developer is as follows. Triethanolamine 6% (weight) Isopropanol 0.5% Water 93.5% Total 100% The developing temperature was 25 ° C., and the developing time was 70 seconds. The obtained pattern was sufficiently usable as a color filter. The sensitivity at this time was 5 steps with the Kodak Step Tablet. Clean oven CSO-40
2 (manufactured by Kusumoto Kasei) at 260 ° C. for 1 hour for curing. The color difference (ΔEab *) was 1.18. The film reduction rate after heating at 260 ° C. for 1 hour was 2.8% as compared with the film after development with a film thickness meter (surface shape measuring instrument model Dektak 3030, manufactured by Nippon Vacuum Engineering Co., Ltd.).

Example 2 A test was conducted in the same manner as in Example 1 except that the dispersion [2] was used and the following formulation was used. Dispersion [2] is a resin (Polymer A)
-2) and a pigment (CI Pigment Blue 1)
5: 6 and C.I. I. Pigment violet 23
And the ratio is 91: 9, which is the same as in Example 1.)
Were dispersed with a solvent in a bead mill for 3 hours. Hereinafter, the manufacturing method is in accordance with the first embodiment. The viscosity of the dispersion is 50m · Pa · S
was. However, the polymer A-2 is an N-phenylmaleimide-styrene resin (the molar ratio of N-phenylmaleimide: styrene is 1: 1 manufactured by Nippon Shokubai) and has a molecular weight of 3200.
0, the acid value was 0. Since the resin polymer A-2 has an acid value of 0, a mixture with the resin polymer B-1 having an acid value of 77 was used. Polymer B-1 is a half ester of isopropyl alcohol with styrene-maleic acid. The formulation of the color filter photosensitive liquid is as follows. Photosensitive liquid viscosity is 26
m · Pa · S.

The composition of the photosensitive solution is as follows. [Resin] Polymer A-2 53 parts [Resin] Polymer B-1 35 parts [Crosslinking agent] Trimethylolpropane triacrylate 30 parts [Photoinitiator] Benzophenone 8 parts 2,2-bis (o-chlorophenyl) -4, 5,4 ′, 5′-Tetraphenyl-1,2′-biimidazole 8 parts [solvent] N-methylpyrrolidone 5 parts γ-butyrolactone 500 parts [polymerization inhibitor] p-methoxyphenol 0.1 part [surfactant activity] Agent] Perfluoroalkyl alkoxylate 0.01 part [Colorant] Dispersion [2] 48 parts Coating step (rotation speed 1200 rpm) in the same manner as in Example 1.
m), drying step (80 ° C./10 minutes), exposure step (130
mJ / cm2) and a development step (development time 70 seconds).
A color filter pattern was formed. The number of steps was eight. The developer was the same as in Example 1. In the same manner as in Example 1, the coating was heated and cured in a clean oven CSO-402 (manufactured by Kusumoto Kasei) at 260 ° C. for 1 hour. The color difference (ΔEab *) was 2.02. 2 compared to the film after development
The film reduction rate after heating at 60 ° C. for 1 hour was 3%.

Comparative Example A blue pixel pattern was formed in the same manner as in Example 1 except that the colored photosensitive resin layer dispersion was used. First, a dispersion was prepared. In the dispersion [3], a resin as an alkali-soluble dispersing resin having a carboxyl group (polymer B-2) and a pigment were dispersed with a solvent in a bead mill for 3 hours. Polymer B-2 is a styrene-maleic acid resin and is a half ester of isopropyl alcohol. , Molecular weight 11000, acid value 70, (one carboxylic acid is reacted with glycidyl methacrylate,
This ratio is 3/7. That is, 30% of the carboxylic acid remains in this portion. ). This color filter was heated at 260 ° C for 1 hour under air.
The film reduction rate is 20.7%, and the color difference (ΔEab *) is 7.9.
Met.

[0039]

The colored image forming material of the present invention has high sensitivity,
It has high resolution, is soluble in alkali development, has improved heat resistance, and has little change in chromaticity and thickness of the color filter even when stored at a temperature of 200 ° C. or more and 300 ° C. or less.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/028 G03F 7/028 7/033 7/033 7/038 7/038

Claims (5)

[Claims] 1. A colored image formation comprising (A) a polymer having a maleimide group in the skeleton, (B) a photoinitiator, (C) a compound having at least one ethylenically unsaturated bond, and (D) a colorant. material. 2. A negative-working colored image-forming material comprising the composition according to claim 1. 3. A photosensitive element in which a layer of the colored image forming material according to claim 1 is formed on a support. 4. The photosensitive element according to claim 3, wherein a peelable cover film is laminated on the layer of the colored image forming material. 5. A colored image forming material is formed as a film on a substrate using the colored image forming material according to claim 1 or 2 or the photosensitive element according to claim 3 or 4.
The step of irradiating actinic rays in the form of an image, photo-curing the exposed portion, and removing the unexposed portion by development is repeated for colored image forming materials of different colors to form pixels. A method for manufacturing a color filter.