JPH08211607A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE: To provide a photosensitive resin compsn. high in sensitivity and excellent in solvent resistance and shelf stability by incorporating a reactional product of a polymer contg. specified segments with (3,4-epoxycyclohexyl)methyl methacrylate, a polymn. initiator acting by irradiation with active rays and a solvent as essential components. CONSTITUTION: This photosensitive resin compsn. contains a reaction product of a polymer contg. segments represented by the formula with (3,4- epoxycyclohexyl)methyl methacrylate, a polymn. initiator acting by irradiation with active rays and a solvent as essential components or further contains a thermo-crosslinking agent and/or a compd. having a polymerizable unsatd. bond. in the formula, R<1> is H or methyl, plural R<1> may be different from each other, R<2> is 1-5C alkyl having a straight chain or side chain structure, each of (m) and (n) shows the degree of polymn. and the molar ratio of (m) to (n) is 0.5-2.4. This compsn. does not require the formation of an oxygen isolating film or heating during the time from exposure to development at the time of producing a color filter.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photosensitive resin composition for forming various patterns and coating films. The present invention also relates to a photosensitive resin composition for forming a colored image, and particularly to a photosensitive resin composition which is useful for producing a color filter used for a liquid crystal display device, an image pickup device and the like.

[0002]

2. Description of the Related Art Generally, a color filter used for a liquid crystal display device, an image pickup device, or the like is one in which, for example, mosaic or striped pixels are arranged on a transparent substrate such as glass. .Uchida et al: Re
cord of International Display Res.Conf. (1982) 16
6: IEEE Trans.ED-30 (1983) 503], electrodeposition method [M.Suginoya
et al: Proc. Japan Display '83 (1983) 206], printing method [Tsuda et al: Proceedings of 13th Liquid Crystal Conference (1987) 22], etc.

Among these, the dyeing method is, for example, gelatin,
For water-soluble polymers such as casein and polyacrylamide,
Photochromic acid or water-soluble azide is added to impart photosensitivity, and after exposure, development is performed to obtain a relief pattern, and then the relief pattern is dyed to form a colored image. A color filter is obtained by repeating this process for each color of red, blue, green, and between the processes of each color, for example, a dye-proof treatment with tannic acid is performed or an intermediate layer such as an acrylic resin is provided to mix colors. To prevent. Therefore, the conventional dyeing method has complicated steps, and it is difficult to control the color tone. Further, there are drawbacks such as poor heat resistance of the water-soluble polymer as a dyeing medium and poor heat resistance and weather resistance of dyeing.

In order to solve the above drawbacks, an electrodeposition method, a printing method, a pigment dispersion method and the like have been studied. However, the electrodeposition method has a problem in that the colored film becomes considerably thick, the voltage drop due to this is large, and the pattern layout is limited. Further, the printing method has drawbacks such as poor dimensional accuracy and poor surface smoothness.

As a method for solving the conventional drawbacks, there is a pigment dispersion method. This is a method of forming a colored image by dispersing a pigment in a photosensitive resin, applying it to a substrate, drying it, and then exposing and developing it. A color filter is formed by a simple process compared to the dyeing method. It has the advantage that it can be manufactured. Examples of the photosensitive resin used in the above pigment dispersion method include photosensitive polyimide resins disclosed in JP-A-60-237403 and JP-A 1-2.
00353, JP-A-4-7373 and JP-A-4-9
1173, a photosensitive resin composed of an acrylic polymer and an azide compound described in JP-A No. 1-173
Radical polymerization type photosensitive resin composed of acrylate monomer, organic polymer binder and photopolymerization initiator described in JP-A-52449, etc.
Various products such as a chemically amplified photosensitive resin composed of a phenol resin, a cross-linking agent having an N-methylol structure, and a photo-acid generator disclosed in Japanese Patent Publication No. 163552 and the like have been proposed.

[0006]

However, among the photosensitive resins prepared by the above-mentioned pigment dispersion method, those using photosensitive polyimide etc. have high heat resistance, but have low sensitivity and development by an organic solvent. There is a drawback of. Further, conventional systems using an azide compound as a photosensitizer have problems such as low sensitivity, poor heat resistance, and easy influence of oxygen during exposure. Further, although radical polymerization of an acrylate monomer or the like has high sensitivity, there is a problem that the sensitivity is significantly lowered due to the influence of oxygen during exposure. In order to avoid these, it is necessary to provide an oxygen blocking film or expose in an inert gas, but there are problems such as the process being complicated and the apparatus being expensive. Further, a chemically amplified photosensitive resin that forms an image by a catalytic reaction due to an acid generated by exposure has high sensitivity and has the advantage that it is not affected by oxygen at the time of exposure, but a heating step between exposure and development. However, there is a problem that the process control is difficult because the sensitivity and the pattern shape are affected by the time between the steps from exposure to heating and development. Further, the conventional one has a drawback that it lacks temporal stability during storage.

Further, the photosensitive resin composition containing no pigment has the same problems as those of the colored photosensitive resin composition used in the pigment dispersion method for producing the color filter. Further, the conventional photosensitive resin composition containing no pigment is not sufficiently considered in chemical resistance, heat resistance and transparency of the cured product by exposure, and when used as a protective material for the color material layer, for example, heat resistance However, the chemical resistance is insufficient, there is a problem that the color is remarkably discolored by heating, or peeling is caused by chemicals, and further improvement is required under the present circumstances.

Therefore, the object of the present invention is to have a high sensitivity, to eliminate the need for heat treatment between the exposure and development steps, and to reduce the change in sensitivity and pattern shape due to the time change between exposure and development, It is an object of the present invention to provide a colored photosensitive resin composition having excellent properties such as excellent heat resistance, water-based development, and excellent stability over time during storage. Another object of the present invention is to provide a pigment-free photosensitive resin composition which is excellent in heat resistance, chemical resistance and stability over time during storage.

[0009]

Means for Solving the Problems As a result of intensive studies conducted by the present inventors in view of the above situation, the use of a mixture having the following composition allows easy polymerization and post-exposure heat treatment. The present invention has been accomplished by finding that an image can be formed by development without any development.

That is, according to the present invention, (a) a polymer containing a segment represented by the following general formula (I):
Reaction product with (3,4-epoxycyclohexyl) methyl methacrylate,

Embedded image {In the formula, R ¹ may be the same or different and represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having a linear or side chain structure having 1 to 5 carbon atoms. Further, m and n represent the degree of polymerization, and m / n = 0.5 to 2.4 (molar ratio). A photosensitive resin composition comprising (b) a polymerization initiator by irradiation of actinic radiation and (c) a solvent as essential components is provided, and the photosensitive resin composition further comprises (d) ) A photosensitive resin composition comprising a thermal crosslinking agent and / or a compound having a polymerizable unsaturated bond. These can be used as a pattern forming material and a coating film forming material which are particularly required to have heat resistance and chemical resistance.

Further, according to the present invention, the above (a) to
Provided is a photosensitive resin composition comprising the photosensitive resin composition containing the component (c) or the components (a) to (d) and further containing a pigment (e). These photosensitive resin compositions are suitably used in a pigment dispersion method for producing a color filter.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
In the present invention, as a binder, a polymer containing a segment represented by the following general formula (I);
The reaction product with -epoxycyclohexyl) methyl methacrylate is used.

Embedded image {In the formula, R ¹ may be the same or different and represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having a linear or side chain structure having 1 to 5 carbon atoms. Further, m and n represent the degree of polymerization, and m / n = 0.5 to 2.4 (molar ratio). ｝

Particularly, in the general formula (I), at least one of R ¹ is preferably a methyl group, and R ² is preferably an alkyl group having 1 to 4 carbon atoms, and particularly n-butyl group. Is preferred. Furthermore, it is more preferable that the above general formula (I) is a polymer containing a segment represented by the following general formula (II).

Embedded image (In the formula, m and n are the same as the above.) In addition, m / n is in the range of 0.5 to 2.4 in terms of molar ratio, and particularly preferably in the range of 0.6 to 1.7. .

A polymer represented by the general formula (I),
The molecular weight (Mw) of the reaction product with (3,4-epoxycyclohexyl) methyl methacrylate is 10,000.
To 80,000, preferably 1
More preferably, it is in the range of 5,000 to 40,000. The acid value of the above reaction product is 40 to 100 KOHm.
g / g is preferred, especially 45-70 KOHmg
/ G is more preferable.

In the present invention, as the polymerization initiator upon irradiation with actinic rays, various halomethyloxazole compounds, halomethyl-s-triazine compounds, onium salts, benzoin ethers, benzophenones, xanthones, acetophenone derivatives, azides and the like can be used. Can be used. More specifically, as the halomethyloxazole-based compound, 2-trichloromethyl-5-styryl-1,
3,4-oxadiazole, 2-trichloromethyl-5
Examples include-(p-cyanostyryl) -1,3,4-oxadiazole and 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole. Further, as the halomethyl-s-triazine compound, especially a trihalomethyl-s-triazine compound, for example, 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,4-bis (trichloromethyl). ) -6- (1-p-Dimethylaminophenyl-
1,3-Butadienyl) -s-triazine, 2,4-bis (trichloromethyl) -6- (p-phenylstyryl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s- Triazine, 2,4-bis (trichloromethyl) -6-phenyl-s-triazine, 2 [2 '(5 "-methylfuryl) ethylidene]-
4,6-bis (trichloromethyl) -s-triazine,
2 (2'-furylethylidene) -4,6- (trichloromethyl) -s-triazine, 5,7-bis (tribromomethyl) -s-triazolo [1,5-a] pyrimidine and the like can be mentioned. These may be used alone or in combination.

Examples of benzoin ethers include benzoin methyl ether and benzoin isobutyl ether. As benzophenones,
Examples thereof include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, Michler's ketone and o-benzoylmethylbenzoate. As the xanthones, for example,
Examples thereof include xanthone, thioxanthone, 2-chlorothioxanthone, 2-alkylthioxanthone, and 2,4-dialkylthioxanthone. Examples of the acetophenone derivative include acetophenone, trichloroacetophenone, 2,2-diethoxyacetophenone and 2,2-
Examples thereof include dimethoxy-2-phenylacetophenone. Examples of the azide include 4,4′-diazidostilbene, 4,4′-diazidostilbene-2,2′-disulfonic acid-N, N-diethyleneoxyethylamide, p
-Azidobenzal acetophenone, azidochalcone and the like.

Examples of the onium salt include various sulfonium salts, iodonium salts and diazonium salts. Specific examples include triphenylsulfonium trifluoromethanesulfonate, benzyl-4-hydroxyphenylmethylsulfonium, hexafluorophosphate and α.
-Naphthylmethyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate (or hexafluoroantimonate), diphenyl-t-butylphenylsulfonium trifluoromethanesulfonate, diphenylmethoxyphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, diphenyl -T-butylphenyl iodonium trifluoromethanesulfonate (or hexafluoroantimonate or tetrafluoroborate), methoxyphenylphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoromethanesulfonate, aminophenylbenzenediazonium tetrafluoroborate, pyrenediazonium tetrafluoroborate Etc. The. These may be used alone or in combination.

In the composition of the present invention, in combination with the component (a) as a binder component, a halomethyl-s-triazine compound, particularly a trihalomethyl-s-triazine compound, is used as a polymerization initiator from the viewpoint of image forming property. It is preferable to use.

In the present invention, a sensitizer may be used in combination for improving sensitivity. Examples of the sensitizer include 2-nitrofluorene, 2,4,7-trinitrofluorenone, benzanthrone, picramide, 1,2-benzanthraquinone, 11-chloro-6-hydroxybenzanthrone, and fenanthraquinone. Examples include- (4-butoxyphenyl) -2,6-diphenylthiopyrylium percrate.

In the present invention, as the pigment, for example, anthraquinone-based or perylene-based condensed polycyclic pigments, phthalocyanine pigments, organic pigments such as azo pigments, and inorganic pigments such as carbon black can be used. These may be used alone or in combination of two or more. Further, in the present invention, it is preferable to use a dispersant for dispersing the pigment in the mixture. The pigment may be surface-treated in advance and internally added to the pigment, or may be externally added to the pigment. As such a nonionic, anionic or cationic dispersant is used. Further, rosin, rosin modified with unsaturated carboxylic acid and the like are also used. The amount of the dispersant added is
It is preferably 0 to 20% by weight with respect to 1 part by weight of the pigment.

In the present invention, as the solvent, ethyl cellosolve, propylene glycol methyl ether acetate (PGMEA), ethyl lactate, polyethylene glycol, polypropylene glycol, cyclohexanone, propylene glycol methyl ether, etc. are used. Either alone or in a mixed solvent form. You may use.
In addition, a stabilizer, an antioxidant and the like may be further added to the mixture of the present invention.

Further, in order to improve crack resistance, solvent resistance, etc., various thermal crosslinking agents and / or compounds having a polymerizable unsaturated bond may be added to the mixture of the present invention. Examples of the thermal crosslinking agent include compounds having at least two residues of the same type or different types such as alkoxy and acyloxy which react with the binder to form a crosslinking matrix, for example, bis-, tris- or tetra- (hydroxymethyl). ) Substituted aromatic compounds or heterocyclic aromatic compounds, bis-, tris- or tetra- (acetoxymethyl) substituted aromatic compounds or heterocyclic aromatic compounds, N
-Hydroxymethyl group-containing melamine, N-alkoxymethyl group-containing melamine or N-acyloxymethyl group-containing melamine, novolac type epoxy resin, bisphenol A type epoxy resin, halogenated bisphenol A type epoxy resin, alicyclic Compounds containing epoxy groups such as epoxy resins, acetal resins such as polyvinyl butyral, peroxides such as benzoyl peroxide, parachlorobenzoyl peroxide, acetyl peroxide, lauroyl peroxide, blocked isocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, cyclohexylene diisocyanate, etc. Various blocking agents such as ethanol, butanol, dimethyl malonate, imidazole, ε-caprolactam, methylcello. Lube, those blocks are used in the ethylene glycol. These may be used alone or in combination of two or more.

Examples of the compound having a polymerizable unsaturated bond include various vinyl monomers and vinyl oligomers. Specific examples thereof include acrylate monomers and methacrylate monomers. Esters of polyhydric alcohols such as ethylene glycol and trimethylol propanol with acrylic acid and methacrylic acid, and polymers and oligomers having an alcoholic hydroxyl group such as polyvinyl alcohol. Also included are the above esters of and. Further, acrylate melamine, methacrylate melamine, urethane methacrylate, urethane acrylate and the like are also included in the present invention. More specifically, 2-hydroxyethyl methacrylate, n-butyl methacrylate, glycidyl methacrylate, 2-ethylhexyl acrylate, diethylene glycol dimethacrylate, polyethylene glycol methacrylate, trimethylolethane tetramethacrylate, tetramethylolmethane tetraacrylate and the like can be mentioned. These may be used alone or in combination of two or more.

The composition of the present invention preferably contains the components other than the solvent (c) and the pigment (e) in the following proportions. Polymer (a): 70 to 98% by weight, compound (b):
2 to 30% by weight. Further, when the thermal crosslinking agent and / or the compound (d) having a polymerizable unsaturated bond is used in an excessively large amount, the viscosity of the composition becomes high and the composition becomes sticky. 0.01 to 0.25 per part
Parts by weight, preferably 0.025 to 0.2 parts by weight, more preferably 0.03 to 0.15 parts by weight, the polymer (a) and a thermal crosslinking agent and / or a polymerizable unsaturated bond. The compound (b) is preferably added in an amount of 2 to 30% by weight based on the total amount of the compound (d). Also,
The amount of pigment added is 0.1 with respect to 1 part by weight of the above mixture.
~ 2 parts by weight. The weight ratio of the solvent (c) to the total of 1 part of the non-solvent components is 1 to 15 parts, preferably 2 parts.
It is desirable to use 10 parts.

Suitable substrates to which the composition of the invention is applied may be any material which makes up or produces capacitors, semiconductors, multilayer printed circuit boards or integrated circuits. In particular, thermally oxidized silicon materials and / or optionally doped; aluminium-coated silicon materials and other substrates common in semiconductor technology such as silicon nitride, gallium arsenide and indium phosphide. It can be illustrated. Further, a glass substrate, a glass substrate provided with an electrode such as indium tin oxide, a metal plate,
Metal foil (eg aluminum, copper or zinc) or metallized surface, optionally aluminum coated Si
An O ₂ material or the like is used as the base material. These substrates are
It may be subjected to heat treatment, surface polishing, etching, or treatment with a reagent to improve the properties, for example, to enhance hydrophilicity.
As a specific example, an adhesion promoter may be included in order to improve the adhesion between the composition and the substrate, and in the case of silicon or silicon dioxide, 8-aminopropyltriethoxysilane, hexamethyldisilazane, or the like. A silane coupling agent can be applied. The layer thickness depends on the field of application,
For example, it is in the range of 0.1 to 100 μm, particularly 0.5 to 10 μm.

The composition of the present invention can be applied to a substrate by spraying, flow coating, roll coating, spin coating or dip coating. The solvent is then removed by evaporation, leaving the patterning material on the substrate. Removal of the solvent can be facilitated by heating and / or reduced pressure, if desired. It is important that the heating temperature is such that the pattern forming material and the base material do not deteriorate, and the heating temperature can be up to 150 ° C., for example. Then, an actinic ray is irradiated so as to reflect the pattern on the layer. The layer is then treated with a developing solution to insolubilize the exposed areas and dissolve the unexposed areas to reveal a pattern. Further, after irradiation, heating may be performed and then development may be performed. This heating can further improve the sensitivity, for example. The heating temperature is preferably such that the shape of the pattern and the deterioration of the base material do not occur.
You can do the following: The light source used for the irradiation is, for example, 190 to 450 nm, preferably 200 to
UV irradiation in the 400 nm region can be mentioned, and electron beam or X-ray irradiation can also be used.

Further, as a method for producing a color filter using the above-mentioned mixture to which the pigment of the present invention is added, for example, a glass substrate having a thickness of, for example, 0.5 to 10 μm is selected by an appropriate method among the above-mentioned coating methods. To form a coat layer. As the glass substrate, a glass substrate having a black matrix formed on its surface can be used. Then, the actinic rays are irradiated on the layer so as to reflect the pattern required for the color filter. This irradiation does not need to exclude oxygen, that is, can be performed without using an inert gas such as nitrogen and without using a protective film for blocking oxygen. After irradiation, the coat layer is treated with a developing solution to dissolve the unirradiated part of the coat layer and to expose the required pattern on the color filter. By repeating such a process according to the required number of colors, a color filter having a desired pattern can be obtained. It is also possible to further improve the crack resistance, solvent resistance and the like by further heating the image pattern obtained by the development in the above step or curing it by irradiation with actinic rays.

In the present invention, the pattern is obtained as described above because the compound (b) generates a radical or an ion upon irradiation with actinic rays, which reacts with the unsaturated bond in the polymer (a). To form a crosslinked matrix, and the irradiated portion is insolubilized in an alkaline aqueous solution. In the above, as the developer, for example, alkali metal and / or alkaline earth metal, particularly ammonium ion silicate, metasilicate, hydroxide, hydrogen phosphate, ammonia and the like are used. As a developer containing no metal ion, for example, USP 4,729,94 may be used.
Known materials described in No. 1, EP-A62,733, etc. can be used. Further, a surfactant, a cleaning agent, an organic solvent or the like may be added to the developer for the purpose of assisting the removal of the pigment residue during development. Examples of additives added to the developer for the above purpose include nonionic activators, ionic activators, alcohols, carboxylic acids, amines and their derivatives, and specifically, polyalkylene glycols and esters thereof, Examples thereof include hydric alcohol ester alkylene oxide adducts, alcohol alkylene oxide adducts, alkylphenol alkylene oxide adducts, sulfonic acid esters, sulfonates, carboxylic acid esters, carboxylic acid salts, alkylamide alkylene oxide adducts, and alkylamines. These may be added alone or in combination of two or more. The addition amount in this case is preferably 0.1 to 30% by weight with respect to 1 part by weight of the developing solution.

By the way, the photosensitive resin composition of the present invention is
It has a polymerizable unsaturated bond as a base polymer. Therefore, it can be easily polymerized by radicals or ions generated from the photosensitizer upon exposure, and an image can be formed by development. Further, since the base polymer and the photosensitizer used in the present invention have little yellowing, they are not easily affected by the yellowing even after the manufacturing process of the color filter, and show good color tone.

[0030]

The present invention will be described in more detail with reference to the following examples. The present invention is not limited to this embodiment. The base polymers used in the examples are shown in Table 1-
(1) to 1- (2).

[0031]

[Table 1- (1)]

[0032]

[Table 1- (2)]

Example 1 A washed glass substrate was used as a transparent substrate for producing a color filter, while the following sample was prepared as a colored photosensitive resin composition. (1) Composition for red color: Polymer I 95 g 2,4-bis (trichloromethyl) -6-styryl 5 g -s-triazine Red pigment dispersion containing a dispersant 290 g (pigment content 17% by weight) In the above composition In contrast, propylene glycol methyl ether acetate was added as a solvent, and the non-solvent component was 20
A composition containing wt% was prepared. (2) Blue composition: In each component of the red composition, 175 g of a blue pigment dispersion containing a dispersant (pigment content of 17% by weight) was used instead of the red pigment dispersion. It was prepared in the same manner as the composition for red. (3) Composition for green color: In each component of the composition for red color, 290 g of a green pigment dispersion liquid (pigment content: 17% by weight) containing a dispersant was used instead of the red pigment dispersion liquid. It was prepared in the same manner as the composition for red.

Each of the above compositions was spin-coated on a glass substrate to a film thickness of about 1.5 μm. Then, it was dried on a hot plate at 100 ° C. for 1 minute. The colored photosensitive resin layer was exposed with a high pressure mercury lamp through a mask having a predetermined shape. Then, the colored photosensitive resin layer subjected to pattern exposure,
Development with a 0.15N tetramethylammonium hydroxide aqueous solution gave a colored pattern. The colored pattern thus obtained was uniform and the edges were sharp.

The thickness and transparency (transmittance) of the colored layer of the obtained color filter are as shown in Table 2, and the red,
The transmission spectrum of the colored layer containing the blue and green pigments in the visible region is shown in FIG.

[Table 2]

Example 2 In each color composition of Example 1, polymer II was used instead of polymer I and 2 instead of 2,4-bis (trichloromethyl) -6-styryl-s-triazine.
Example 1 except that (2'-furylethylidene) -4,6- (trichloromethyl) -s-triazine was used.
A colored photosensitive resin composition was prepared in the same manner as above, and exposed and developed. After development, a sharp colored pattern was uniformly obtained.

Example 3 In each color composition of Example 1, polymer III was used in place of polymer I and 2,4-bis (trichloromethyl) -6-styryl-s-triazine was replaced by 2,3.
A colored photosensitive resin composition was prepared in the same manner as in Example 1 except that 4-bis (trichloromethyl) -6- (p-phenylstyryl) -s-triazine was used, exposed to light, and exposed to 0.1N. Development was carried out with an aqueous solution of tetramethylammonium hydroxide. After development, a sharp colored pattern was obtained although residues were observed.

Example 4 A colored photosensitive resin composition was prepared, exposed and developed in the same manner as in Example 3 except that Polymer IV was used in place of Polymer III in each color composition of Example 3. Was done. After development, a sharp colored pattern was obtained although residues were observed.

Example 5 In each color composition of Example 2, 90 g of Polymer II,
2 [2 '(5 "-methylfuryl) ethylidene] -4,6
A colored photosensitive resin composition was prepared, exposed and developed in the same manner as in Example 2 except that 10 g of-(trichloromethyl) -s-triazine was used. After development, a sharp colored pattern was uniformly obtained.

Example 6 The following sample was prepared as a colored photosensitive composition. (1) Composition for red color Polymer I 87.5 g Trimethoxymethyl tri (2-hydroxyethyl 7.5 g acrylate methyl) melamine 2,4-bis (trichloromethyl) -6-styryl 5 g-s-triazine Dispersant included. Red pigment dispersion 290 g (pigment content 17% by weight) Propylene glycol methyl ether acetate was added as a solvent to the above composition to prepare a composition containing 20% by weight of a non-solvent component. (2) Composition for blue color Red except that 175 g of a blue pigment dispersion liquid (pigment content: 17% by weight) containing a dispersant was used in place of the red pigment dispersion liquid in each component of the red color composition. Was prepared in the same manner as the composition for use. (3) Composition for green color Red except that 290 g of a green pigment dispersion liquid (pigment content: 17% by weight) containing a dispersant was used instead of the red pigment dispersion liquid in each component of the red color composition. Was prepared in the same manner as the composition for use.

Each of the above compositions was exposed and developed in the same manner as in Example 1. After development, the colored pattern obtained was uniform and its edges were sharp.

Example 7 In each color composition of Example 6, polymer II was used in place of polymer I, and 2,4-bis (trichloromethyl) was used.
Instead of -6-styryl-s-triazine, 2 (2'-
Furylethylidene) -4,6- (trichloromethyl)-
Exposure and development were performed in the same manner as in Example 6 except that s-triazine was used. After development, a sharp colored pattern was uniformly obtained.

Example 8 Except that Polymer II was used in place of Polymer I and hexamethoxymethylmelamine was used in place of trimethoxymethyltri (2-hydroxyethylacrylatemethyl) melamine in each color composition of Example 6. Is
A colored photosensitive resin composition was prepared, exposed and developed in the same manner as in Example 6. After development, a sharp colored pattern was uniformly obtained.

Example 9 A washed glass substrate was used as a transparent substrate for producing a color filter, while the following sample was prepared as a colored photosensitive resin composition. (1) Red composition: Polymer V 95 g 2,4-bis (trichloromethyl) -6-5 g (p-styrylphenyl) -s-triazine Red pigment dispersion containing a dispersant 290 g (pigment content 17% by weight) ) Propylene glycol methyl ether acetate is added to the above composition as a solvent, and the above non-solvent component is 20
A composition containing wt% was prepared. (2) Blue composition: In each component of the red composition, 175 g of a blue pigment dispersion containing a dispersant (pigment content of 17% by weight) was used instead of the red pigment dispersion. It was prepared in the same manner as the composition for red. (3) Composition for green color: In each component of the composition for red color, 290 g of a green pigment dispersion liquid (pigment content: 17% by weight) containing a dispersant was used instead of the red pigment dispersion liquid. It was prepared in the same manner as the composition for red.

Each of the above compositions was spin-coated on a glass substrate to a film thickness of about 1.5 μm. Then, it was dried on a hot plate at 100 ° C. for 1 minute. The colored photosensitive resin layer was exposed with a high pressure mercury lamp through a mask having a predetermined shape. Then, the colored photosensitive resin layer subjected to pattern exposure,
It was developed with a 0.1N tetramethylammonium hydroxide aqueous solution to obtain a colored pattern. The colored pattern thus obtained was uniform and the edges were sharp. Further, even after the composition was stored at room temperature for 3 months, a uniform and sharp-edged coloring pattern was obtained by the same method.

Example 10 A colored photosensitive resin composition was prepared in the same manner as in Example 9 except that Polymer VI was used in place of Polymer V in each color composition of Example 9, and exposure and development were carried out. I did. After development, a sharp colored pattern was uniformly obtained.

Example 11 A colored photosensitive resin composition was prepared in the same manner as in Example 9 except that Polymer VII was used in place of Polymer V in each color composition of Example 9, and exposure and development were carried out. I did. After development, a sharp colored pattern was uniformly obtained.

Example 12 The following sample was prepared as a colored photosensitive composition. (1) Composition for Red Polymer V 92 g Trimethoxymethyltri (2-hydroxyethyl 3 g acrylatemethyl) melamine 2,4-bis (trichloromethyl) -6- (p-styryl 5 g phenyl) -s-triazine Dispersant Red pigment dispersion containing 290 g (pigment content 17% by weight) Propylene glycol methyl ether acetate was added to the above composition as a solvent to prepare a composition containing 20% by weight of a non-solvent component. (2) Composition for blue color Red except that 175 g of a blue pigment dispersion liquid (pigment content: 17% by weight) containing a dispersant was used in place of the red pigment dispersion liquid in each component of the red color composition. Was prepared in the same manner as the composition for use. (3) Composition for green color Red except that 290 g of a green pigment dispersion liquid (pigment content: 17% by weight) containing a dispersant was used instead of the red pigment dispersion liquid in each component of the red color composition. Was prepared in the same manner as the composition for use. (4) Black composition for black matrix The red composition, the blue composition, and the green composition were mixed in equal weight ratios to obtain a black composition. (5) Black matrix composition for black matrix In each component of the above red composition, a carbon black dispersion (pigment content) containing a dispersant instead of the red pigment dispersion is used.
It was prepared in the same manner as the composition for red color except that 120 g of (17% by weight) was used. (6) Black composition for black matrix It was prepared in the same manner as the black composition of (4) using the composition of (4) to which 5 g of carbon black was further added.

Each of the above six compositions was exposed in the same manner as in Example 1 and developed with a 0.1N tetramethylammonium hydroxide aqueous solution. After development, the colored pattern obtained was uniform and its edges were sharp. Further, even after the composition was stored at room temperature for 3 months, a uniform and sharp edged coloring pattern was obtained by the same method.

Examples 13 to 18 In each of the color compositions of (1) to (3) of Example 12, polymer VI (Example 1) was used instead of polymer V.
3), Polymer VII (Example 14), Polymer VIII (Example 15), Polymer IX (Example 16), Polymer X
A colored photosensitive resin composition was prepared, exposed and developed in the same manner as in Example 12, except that (Example 17) and Polymer XI (Example 18) were used. In each case, a sharp colored pattern was uniformly obtained after development.

Example 19 In each color composition of Example 12, 2,4-bis (trichloromethyl) -6- (p-styrylphenyl) -s-
Other than changing the amount of triazine from 5g to 7g,
A colored photosensitive resin composition was prepared in the same manner as in Example 12, exposed and developed. A sharp colored pattern was uniformly obtained after development.

Example 20 Example 1 except that 10 g of blocked hexamethylene diisocyanate was added to each color composition of Example 12.
A colored photosensitive resin composition was prepared in the same manner as in 2, and exposure,
It was developed. A sharp colored pattern was uniformly obtained after development.

Example 21 Color sensitization was performed in the same manner as in Example 12 except that 5 g of a bisphenol A type epoxy resin (average molecular weight of about 1000) was added to each color composition of (1) to (3) of Example 12. A resin composition was prepared, exposed and developed. A sharp colored pattern was uniformly obtained after development.

Example 22 Using each color composition of Example 12, exposure was carried out in the same manner as in Example 12, and development was carried out with a 0.005N potassium hydroxide aqueous solution. A sharp colored pattern was uniformly obtained after development.

Example 23 The colored patterns obtained in Examples 1 to 22 were used as 23
Heat at 0 ° C. for 15 minutes on a hot plate. After cooling down,
10 in propylene glycol methyl ether acetate
After soaking for a minute, the pattern was observed under a microscope. As a result, deterioration of the pattern shape was not observed even after immersion in propylene glycol methyl ether acetate, and the patterns of Examples 1 to 22 showed good solvent resistance. From this, it was confirmed that the colored photosensitive resin composition according to the present invention has good solvent resistance and is useful for the production of color filters.

Example 24 The following sample was prepared as a photosensitive composition. Polymer V 92g Trimethoxymethyl tri (2-3g hydroxyethyl acrylate methyl) melamine 2,4-bis (trichloromethyl) -6- (p-styryl 5g phenyl) -s-triazine Propylene glycol as solvent for the above composition Methyl ether acetate was added to prepare a composition containing 20% by weight of a non-solvent component.

The resulting composition was exposed in the same manner as in Example 1 and developed with a 0.0054N tetramethylammonium hydroxide aqueous solution. After the development, a sharp pattern was uniformly obtained. Also, after patterning, 23
The one cured by heating at 0 ° C. for 15 minutes showed no deterioration in the pattern shape even after being immersed in propylene glycol methyl ether acetate for 10 minutes, and showed good solvent resistance. The cured product showed good heat resistance with a change in transmittance within 5% at 400 to 700 nm even after heating in air at 260 ° C. for 1 hour. From this, the photosensitive resin composition according to the present invention has good heat resistance,
It showed solvent resistance and was proved to be useful as a pattern forming material and a coating film forming material.

Example 25 A composition was prepared by adding 2.5 g of blocked hexamethylene diisocyanate (Coronate 2507 manufactured by Nippon Polyurethane Co.) to the photosensitive composition of Example 24. Exposure was carried out in the same manner as in Example 1 using the obtained composition,
Development was performed with a 0.05% calcium hydroxide aqueous solution.
After the development, a sharp pattern was uniformly obtained.

Example 26 A composition was prepared by adding 1 g of a bisphenol A type epoxy resin (average molecular weight: about 1000) to the photosensitive composition of Example 24. The obtained composition was exposed in the same manner as in Example 1 and developed with a 0.0054N tetramethylammonium hydroxide aqueous solution. After the development, a sharp pattern was uniformly obtained.

Example 27 A composition was prepared by adding 0.5 g of benzoyl peroxide to the photosensitive composition of Example 24. The obtained composition was exposed in the same manner as in Example 1 to obtain 0.0054N.
Development was carried out with an aqueous solution of tetramethylammonium hydroxide. After the development, a sharp pattern was uniformly obtained.

Example 28 The patterns obtained in Examples 24 to 27 were used as 230
The one cured by heating at ℃ for 15 minutes showed no deterioration of the pattern shape even after soaking in propylene glycol methyl ether acetate for 10 minutes, and showed good solvent resistance. The cured product showed good heat resistance with a change in transmittance within 5% at 400 to 700 nm even after heating in air at 260 ° C. for 1 hour. From this, the photosensitive resin composition according to the present invention has good heat resistance,
It showed solvent resistance and was proved to be useful as a pattern forming material and a coating film forming material.

Example 29 In each color composition of Example 12, 2,4-bis (trichloromethyl) -6- (p-styrylphenyl) -s-
Exposure was carried out in the same manner as in Example 12, except that 10 g of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 was used instead of 5 g of triazine, and 0.1 N was used. Development was carried out with an aqueous solution of tetramethylammonium hydroxide. After development, a colored pattern was obtained with some peeling. The edge was sharp.

Example 30 In each color composition of Example 12, 2,4-bis (trichloromethyl) -6- (p-styrylphenyl) -s-
Instead of 5 g of triazine, 2,2-dimethoxy-1,
Exposure and development were carried out in the same manner as in Example 12 except that 8 g of 2-diphenylethane-1-one was used. After development, a colored pattern was obtained with some peeling. The edge was sharp.

Example 31 In each color composition of Example 12, 2,4-bis (trichloromethyl) -6- (p-styrylphenyl) -s-
Example 1 except that 10 g of 4,4′-diazidostilbene-2,2′-disulfonic acid-N, N-diethyleneoxyethylamide was used instead of 5 g of triazine.
Exposure and development were carried out in the same manner as in 2. After development, a colored pattern was obtained with some peeling. Also,
Its edges were sharp.

Example 32 In each color composition of Example 12, 2,4-bis (trichloromethyl) -6- (p-styrylphenyl) -s-
Example 12 except that 5 g of triphenylsulfonium trifluoromethanesulfonate was used instead of 5 g of triazine and a low pressure mercury lamp was used as the exposure light source.
Exposure and development were performed in the same manner as in. After development, a colored pattern was obtained with some peeling. The edge was sharp.

Example 33 The colored patterns obtained in Examples 29 to 32 were mixed with 2
It was heat-cured on a hot plate at 30 ° C. for 15 minutes. Even after being left to cool and immersed in propylene glycol methyl ether acetate for 10 minutes, no deterioration of the pattern shape was observed and good solvent resistance was exhibited. From this, it was confirmed that the colored photosensitive resin composition according to the present invention is useful for producing a color filter.

Next, comparative examples will be shown in order to clarify the superiority of the composition of the present invention. The base polymers used in the comparative examples are shown in Table 3.

[0068]

[Table 3]

Comparative Example 1 A colored photosensitive resin was prepared, exposed and developed in the same manner as in Example 9 except that the polymer A was used in place of the polymer V in each color composition of Example 9. . The above composition gave a uniform and sharp edge pattern immediately after preparation, but after storage at room temperature for 3 months, the pattern was peeled off and the development residue was large, resulting in insufficient stability over time during storage.

Comparative Example 2 A colored photosensitive resin was prepared, exposed and developed in the same manner as in Example 9 except that the polymer B was used in place of the polymer V in each color composition of Example 9. . The above composition gave a uniform and sharp edge pattern immediately after preparation, but after storage at room temperature for 3 months, the pattern was peeled off and the development residue was large, resulting in insufficient stability over time during storage.

Comparative Example 3 A colored photosensitive resin was prepared, exposed and developed in the same manner as in Example 12, except that the polymer A was used in place of the polymer V in each color composition of Example 12. .
The above composition gave a uniform and sharp edge pattern immediately after preparation, but after storage at room temperature for 3 months, the pattern was peeled off and the development residue was large, resulting in insufficient stability over time during storage.

From the above Examples and Comparative Examples, the following will become clear. (1) Comparing Examples 9 and 12 with Comparative Examples 1 to 3,
The one using a polymer having a methacryloyl group in the side chain is more excellent in stability over time during storage than the one using a polymer having an acryloyl group in the side chain. (2) From Examples 1 to 22 and Examples 29 to 32, in the present invention, a trihalomethyl-s-triazine compound is particularly suitable as the polymerization initiator by irradiation with actinic rays. (3) As shown in Examples 3 and 4 in which R ^{1 of the} general formula is a methyl group and Examples 10 and 11 in which R ² is a butyl group as the base polymer, the molecular weight and the acid value are the same. Comparing these, when R ² is an n-butyl group, there are particularly few residues and a good pattern can be obtained.

[0073]

The photosensitive resin composition of the present invention comprises a polymer containing the segment represented by the general formula (I) and (3,4)
-Epoxycyclohexyl) methyl methacrylate contains a binder resin, a polymerization initiator by irradiation of actinic rays, and a solvent, and therefore has excellent heat resistance, solvent resistance, and stability over time during storage. It is a thing. Furthermore, it is not necessary to provide an oxygen barrier film during the production of the color filter, and it is not necessary to heat between the exposure and the development, and the storage stability is excellent during storage. Therefore, by using this composition, the manufacturing process of the color filter can be greatly simplified, and its industrial utility value is extremely large.

[Brief description of drawings]

FIG. 1 is a spectral characteristic diagram of a color filter manufactured according to Example 1 of the present invention.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical indication location G03F 7/029 7/031 (72) Inventor Yuki Nanjo 1-3-2 Minamidai, Kawagoe City, Saitama Prefecture Inside the Advanced Materials Technology Laboratory

Claims (6)

[Claims] 1. A reaction product of (a) a polymer containing a segment represented by the following general formula (I) and (3,4-epoxycyclohexyl) methyl methacrylate: {In the formula, R ¹ may be the same or different and represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having a linear or side chain structure having 1 to 5 carbon atoms. Further, m and n represent the degree of polymerization, and m / n = 0.5 to 2.4 (molar ratio). A photosensitive resin composition comprising (b) a polymerization initiator by irradiation with actinic radiation and (c) a solvent as essential components. 2. The photosensitive resin composition containing the components (a) to (c) further contains (d) a thermal crosslinking agent and / or a compound having a polymerizable unsaturated bond. The photosensitive resin composition according to claim 1. 3. The components (a) to (c) or the component (a).
The photosensitive resin composition according to claim 1 or 2, wherein the photosensitive resin composition containing the components (d) to (e) further contains a pigment (e). 4. The photosensitive resin composition according to claim 1, wherein R ² in the general formula (I) in the component (a) is an n-butyl group. 5. The photosensitive resin composition according to claim 4, wherein the general formula (I) in the component (a) is represented by the following general formula (II). Embedded image (In the formula, m and n are the same as above.) 6. The photosensitive resin composition according to claim 1, wherein the component (b) is a halomethyl-s-triazine compound.