JPH01247461A - Colored resin composition - Google Patents

Abstract

PURPOSE:To provide the title composition which is excellent in colorability, heat resistance, solvent resistance, etc. and can give a coating film which can be formed at low temperature, by adding a colorant compound to a specified polymer obtained by reacting a tetracarboxylic acid with a diamine. CONSTITUTION:A polymer having repeating units of formula I (wherein R is a tetravalent aliphatic or alicyclic group, R<1> is a bivalent organic group, and R<2> and R<3> are each H or a 1-5C alkyl group) and/or formula II is mixed with a colorant compound (e.g., C.I. Pigment Red 149) to produce a colored resin composition. The polymer of formula 1 can be obtained by reacting an aliphatic or alicyclic tetracarboxylic acid (e.g., 1,2,3,4-cyclobutanetetracarboxylic acid) with a diamine (e.g., p-phenylenediamine), and the polymer of formula II can be obtained by cyclizing a polymer of formula I through dehydration by heating.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a colored resin composition that can be suitably used for producing color filters, paints, and the like.

[Conventional technology]

Conventionally, heat-resistant colored resin compositions include, for example, resin compositions in which dyes and pigments are added to aromatic polyamic acid, which is a precursor of aromatic polyimide;
No. 325, JP-A No. 60-184203, J-Kokai No. 60-237441, JP-A No. 61-2549
No. 06, etc.) are known.

In order to form a heat-resistant colored resin coating film from such a resin composition, a spin coater or a roll coater is used.
After forming a coating film by applying a composition solution using a coating method such as the above, it is usually necessary to thermally imidize the composition at a temperature exceeding 300°C.

However, aromatic polyamic acid, which is a precursor of aromatic polyimide, is thermally unstable, and when its solution is left at room temperature, its viscosity changes, imidization gradually progresses, and its solubility in the solvent changes. This has the disadvantage that it becomes difficult to form a uniform coating film.

Furthermore, aromatic polyimide has a problem of coloring due to its own structure, and cannot be used as a color element of a color separation filter that requires a specific hue and color density.

Furthermore, in order to obtain aromatic polyimide, the temperature for efficiently imidizing the aromatic polyamic acid, which is the precursor thereof, usually requires a high temperature exceeding 300°C, as described above, so colored resin There is also the problem that the dyes and pigments in the composition undergo thermal decomposition, thermal deterioration, and sublimation, making it impossible to develop the desired hue and color density.

[Problem that the invention seeks to solve]

The present invention was made against the background of the above-mentioned conventional technical problems, and it is possible to form a uniform coating film with excellent coloring properties, and it is possible to form a coating film at a low temperature, and it has good heat resistance and solvent resistance. The purpose of the present invention is to provide a colored resin composition with excellent properties.

[Means for solving problems]

The present invention provides (i) a repeating structural unit represented by the following general formula (1) (hereinafter referred to as "(■) unit") and/or a repeating structural unit represented by the following general formula (II) (hereinafter referred to as "(■) unit"). (i) units") (hereinafter collectively referred to as "(i) polymers"), and (
b) A colored resin composition containing a dye compound is provided.

(In the formula, R is a tetravalent aliphatic group or alicyclic group, R1 is 2
A valent organic group, R2 and R3 may be the same or different and represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
) The polymer having the (1) unit used in the present invention (hereinafter simply referred to as "(I) polymer") can be obtained, for example, by reacting an aliphatic or alicyclic tetracarboxylic acid with a diamine in an organic solvent. .

In the present invention, tetracarboxylic acids include tetracarboxylic acid, tetracarboxylic acid anhydride, tetracarboxylic dianhydride, tetracarboxylic acid monoalkyl ester, tetracarboxylic acid dialkyl ester, tetracarboxylic acid trialkyl ester, and tetracarboxylic acid tetraalkyl ester.

Such tetracarboxylic acids include 1,2゜3.4-
Butanetetracarboxylic acid i, i, 2,3゜4-cyclobutanetetracarboxylic acids, l, 2゜3.4-cyclopentanetetracarboxylic acids, 2゜3.4-tricarboxycyclopentyl acetic acids, 2.3.5 -tricarboxycyclopentyl acetic acids, 3,5.6-dolicarboxynorbornane-2-acetic acids, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-cyclohexenedicarboxylic acids, bicyclo(2,2,2 )-octo-7-nin-tetracarboxylic acids, 1.2.3.4-furantetracarboxylic acids, 3.3', 4.4'-perfluoroisopropylidenetetracarboxylic acids, and other aliphatic or alicyclic acids Mention may be made of tetracarboxylic acids. Among these tetracarboxylic acids, particularly preferred are:
2.3゜4-tricarboxycyclopentyl acetic acids, 2
゜3.5-1-lycarboxycyclopentyl acetic acids, 1
．． 2.3.4-butanetetracarboxylic acids, 1°2.3
．． 4-cyclobutanetetracarboxylic acids, 3.5.6-
Examples include dolicalpoxynorbornane-2-acetic acids and the like.

Furthermore, in the present invention, in addition to the tetracarboxylic acid, 4,4'-bis(3,4-dicarboxyphenoxy) diphenyl sulfides, 4°4'-bis(3,4-
dicarboxyphenoxy) diphenyl sulfone [,4,
4'-bis(3,4-dicarboxyphenoxy)diphenylpropanes, 3.3', 4.4'-perfluoroisopropylidene tetracarboxylic acids, 3.3', 4.4
'-Biphenyl ether tetracarboxylic acids, bis(phthalic acid) phenylphosphine oxides, p-phenylene-bis-(triphenylphthalic acid), m-phenylene-bis-(triphenylphthalic acid), bis(triphenyl Phthalic acid)-4゜4'-diphenyl ethers, bis(triphenyl phthalic acid)-4,4'-diphenylmethanes, pyromellitic acids, 3.3', 4.4'-
Benzophenone tetracarboxylic acids, 3.3', 4.4
'-biphenylsulfonetetracarvone Ml, ■.

4.5.8-Naphthalenetetracarboxylic acids, 2°3.
6.7-Naphthalenetetracarboxylic acids, 3°3',4
．． 4'-biphenyl ether tetracarboxylic acids, 3.
Aromatic tetracarboxylic acids such as 3', 4,4'-dimethyldiphenylsilane tetracarboxylic acids and 3,3', 4°4'-tetraphenylsilane tetracarboxylic acids can be used in combination. The mixing ratio of these aromatic tetracarboxylic acids is preferably 95 mol% or less, particularly preferably 50 mol% or less, based on the aliphatic or alicyclic tetracarboxylic acids.

Further, as the diamine to be reacted with the tetracarboxylic acids, para-phenylene diamine, meta-phenylene diamine, 4,4'-diaminodiphenylmethane, 4,4'
-Diaminodiphenylethane, benzidine, 4.4'-
Diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl ether, ■,5-diaminonaphthalene, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,4'-diaminobenz Anilide, 3.4'-diaminodiphenyl ether, 3.3'-diaminobenzophenone, 3,4'-
Diaminobenzophenone, 4゜4'-diaminobenzophenone, 2.2-bis(4-(4-aminophenoxy)
phenyl]propane, bis(4-(4-aminophenoxy)phenyl)sulfone, 1.4-bis(4-aminophenoxy)benzene, 1.3-bis(4-aminophenoxy)benzene, 1.3-bis( 3-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)-1
O-hydro-anthracene, 9゜9-bis(4-aminophenyl)fluorene, 4゜4'-methylene-bis(2
-chloroaniline), 2.2',5.5'-tetrachloro-4,4'-diaminobiphenyl, 2.2'-dichloro-4°4-diamino-5,5'-dimethoxybiphenyl, 3.3 Aromatic diamines such as '-dimethoxy-4,4'-diaminobiphenyl;1,1'-methaxylylene diamine, 1,3-propanediamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, Octamethylene diamine, nonamethylene diamine, 4,4'-dimethylhebutamethylene diamine, 1,4-diaminocyclohexane, isophorone diamine, tetrahydrodicyclobentadienylene diamine, hexahydro-4,7-methanoindanilene shimethylene diamine , tricyclo(6,2,1
,0''°1]-undecylenedimethyldiamine, and diaminoorganosiloxanes represented by the following general formula.

(In the formula, p is an integer of 1 to 3, m is an integer of 2 to 20, n is an integer of 1 to 3, R4-R7 are the same or different,
It represents an alkyl group having 1 to 12 carbon atoms such as a methyl group and an ethyl group, and an aryl group having 6 to 12 carbon atoms such as a phenyl group. ) These tetracarboxylic acids and diamines can be used alone or in combination of two or more.

(1) The proportion of tetracarboxylic acids used in the production of polymers is usually 0.6 per mole of diamine.
-1.3 mol, preferably 0.9-1.1 mol.

Examples of organic solvents that can be used to synthesize this (1) polymer include N-methyl-2-pyrrolidone, N,
N-dimethylacetamide, N.

N-dimethylformamide, dimethyl sulfoxide, γ
-Aprotic polar solvents such as butyrolactone, tetramethylurea and hexamethylphosphortriamide; phenolic solvents such as m-cresol, xylenol, phenol and halogenated phenol.

(1) The reaction temperature when synthesizing the polymer is, for example, when the tetracarboxylic acids are made from monoalkyl esters, dialkyl esters, trialkyl esters, tetraalkyl esters, and monoanhydrides of tetracarboxylic acids and nucleic acids. Usually, the temperature is 50 to 250°C.

Further, when the tetracarboxylic acids are made from tetracarboxylic dianhydride, the reaction is usually carried out at 0 to 100°C.

Next, a polymer having (U) units (hereinafter simply “(■
) can be synthesized by heating the polymer (1), for example, to 80 to 160° C. to dehydrate and ring-close the polymer.

The reaction for synthesizing the (II) polymer from the (1) polymer is carried out using organic amine compounds such as triethylamine, pyridine, lutidine, and collidine, and acids such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride in an organic solvent. Perform in the presence of anhydride.

Examples of the organic solvent used in this case include the organic solvents used in the production of the polymer (T).

The (n) polymer used in the present invention may be a polymer in which the (1) unit and (II) unit, in which a part of the polyamic acid is dehydrated and ring-closed, coexist.

Further, the polymer (II) may be a polyimide synthesized from the above-mentioned polymer (1), or a polyimide synthesized from a diisocyanate and the above-mentioned tetracarboxylic acids.

Here, examples of the diisocyanate include 2゜4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, 4゜4'-diphenylmethane diisocyanate, 4゜4'-diphenyl ether diisocyanate, 4゜4'-diphenylsulfone diisocyanate, 4゜4'-diphenylsulfide diisocyanate, 1.5-naphthalene diisocyanate, 2.6-
Aromatic diisocyanates such as naphthalene diisocyanate, toridine isocyanate, 4,4'-biphenyl diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate; isophorone diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexane, l.

4-bis(isocyanatomethyl)cyclohexane, 4
．． 4'-dicyclohexylmethane diisocyanate, 4
．． Examples include alicyclic diisocyanates such as 4'-dicyclohexyl ether diisocyanate; aliphatic diisocyanates such as butane diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, lysine diisocyanate, and trimethylhexamethylene diisocyanate.

These can be used alone or in combination.

(II) The proportion of the diisocyanate used in the production of the polymer is usually 0.6 to 1.3 mol, preferably 0.9 to 1.1 mol, per 1 mol of the tetracarboxylic acid.

The conditions for the reaction between the tetracarboxylic acids and the diisocyanate are the same as those for the reaction between the tetracarboxylic anhydride and the diamine.

Furthermore, in order to obtain a polymer (a) in which (I) units and (II) units coexist, a part of the diisocyanates to be reacted with the tetracarboxylic acids can be replaced with the diamines and used in combination. In this case, the total amount of diisocyanates and diamines used is usually 0.6 to 1.3 mol, preferably 0.9 to 1.1 mol, per 1 mol of tetracarboxylic acids.

(a) Intrinsic viscosity of polymer [η1,=fn ('
7r*t/c), c=0. 5 g/d! -30℃
, in N-methyl-2-pyrrolidone] is usually 0.05
~10d! /g, preferably 0.05 to 5 dl/g.

Next, (b) examples of the dye compound include organic pigments and inorganic pigments.

Here, the organic pigment is a dye or pigment that is insoluble in water or an organic solvent. Specifically, the color index (The 5ociety of Dyers a
Pigment (P.
Compounds classified as igmen t) can be mentioned.

Inorganic pigments are metal-containing compounds such as metal oxides and metal complexes, and specifically include iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, etc. Examples include metal oxides and composite oxides.

Specific examples of these (b) dye compounds include C, 1,
Pigment Yellow 24, C, 1, P
igment Yellow 31, C, 1, Pi
gment, Yellow 53, C, I, Pi
gment Yellow 83, C, 1, Pig
ment Orange 43. .

C, 1, Pigment Red 105, C, [
, Pigment Red 149, C,1,
Pigment Red 176, C, 1, P
igment Red 17? ,C,1,P
i gment Violet 14, C,
I, Pigment Violet 29, C
11, Pigment Blue 15, C,
1, Pigment Blue 15:3, C
,1,Pigment Blue 22,
C, 1, Pigment Blue 28, C
,1,Pigment Green 15,C
,1,Pigment Green 25,C
,T, Pigment Green 36
, C, r, Pigment Brown
28, C, 1, Pigment Black
Examples include LC, 1, Pigment Black 7, and the like.

The amount of the pigment compound used in the present invention (i) is usually 0.1 to 30 parts by weight per 100 parts by weight of the polymer.
0 parts by weight, preferably 10 to 150 parts by weight, and 0.
If it is less than 1 part by weight, the color density will not be sufficient when used as a color element, while if it exceeds 300 parts by weight, the transmittance of visible light will decrease or the mechanical strength of the coating will decrease.

In addition, the (mouth) pigment compound used in the present invention is usually
Particles with an average particle size of 1 to 10 II m exceed 10 weight,
It has a particle size distribution of 50% by weight or less.

The composition of the present invention contains (a) a polymer and (b) a dye compound, and if necessary, by adding (c) a radiation-sensitive crosslinking agent, the window radiation property can be improved. It can also be made into a colored resin composition having.

This (c) radiation-sensitive crosslinking agent is a component for crosslinking the composition of the present invention by radiation such as ultraviolet rays, and includes compounds that generate carbenes, radicals, nitrene, etc., and compounds that have unsaturated double bonds. and dichromates.

Among these, examples of carbene-generating compounds include p-quinone azide compounds such as p-benzoquinonediazide and p-naphthoquinonediazide; radical-generating compounds include carbonium compounds such as diacetyl and benzoin, and azobisisobutyronitrile. , azo compounds such as diazonium compounds, organic sulfur compounds such as mercaptan disulfide; examples of compounds that generate nitrene include bisazide compounds such as water-soluble bisazide and oil-soluble bisazide.

Compounds with unsaturated double bonds include 3-acrylamidopropyltrimethylammonium chloride, triethylene glycol diacrylate, pentaerythritol triacrylate, and dichromates include ammonium dichromate and ammonium chromate. etc. can be mentioned.

As these (c) radiation-sensitive crosslinking agents, bisazide compounds are particularly preferred from the viewpoint of photosensitive characteristics and developability.

Examples of the bisazide compound include 4,4'-diazidostilhene-2,2'-disulfonic acid, 4,4'-
diazidobenzalacetophenone-2-sulfonic acid, 4
．． 4'-Diazidostilbene-α-carboxylic acid, 1.5
-Diazidonaphthalene-3,7-disulfonic acid, and water-soluble bisazide compounds such as their sodium salts, potassium salts, and ammonium salts; and p-phenylene bisazide, 4,4'-diazidobenzophenone, 4゜4
'-Diazidostilbene, 1,5-diazidonaphthalene, 4,4'-diazidodiphenylmethane, 3.3'-diazidodiphenylmethane, 4.4'-diazidodiphenylethane, 3.3'-diazidodiphenyl ethane, 4,
4'-Diazidiphenyl ether, 3.3'-Diazidiphenyl ether, 4.4'-Diazidiphenyl sulfide, 3.3'-Diazidiphenyl sulfide, 4.4'-Diazidiphenyl sulfone, 3.3' −
Diazido diphenyl sulfone, 4.4'-cyaazidobiphenyl, 3.3'-cyaazidobiphenyl, 4.4'
-Diazidobenzalacetophenone, 4.4'-Diazidochalcone, 4.4'-Diazidobenzalacetone, 2
．． 6-bis(4'-azidobenzal)cyclohexanone, 2,6-bis-(4'-azidobenzal)-4-methylcyclopentanone, 2,6-bis-(4'-azidobenzal)-4-methylcyclohexanone, 6 -Azide-
Oil-soluble bisazide compounds such as 2-(4'-azidostyryl)benzimidazole can be mentioned.

(c) The radiation-sensitive crosslinking agent can be used in any amount within the range that the composition of the present invention forms a coating film having solvent resistance and adhesive properties, but it is usually used per 100 parts by weight of the polymer (a). The amount is 0.1 to 30 parts by weight, preferably 1 to 15 parts by weight, and if it is less than 0.1 part by weight, radiation crosslinking may occur.
On the other hand, if more than 30 parts by weight is used, the products decomposed by radiation may react with each other, and furthermore, when formed into a coating film, the stability may become insufficient.

In addition, the composition of the present invention includes adjustment of the viscosity of the composition, dispersion stability of the pigment compound in the composition, coatability of the composition,
Other additives may be blended for the purpose of improving the adhesion of the coating film to the substrate, the flatness of the coating film, and the like.

Here, other additives include fillers, other polymer compounds, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, aggregation inhibitors, sensitizers, and the like.

Specific examples of these additives include fillers such as glass and alumina; polyvinyl alcohol, polyacrylic acid,
Polymer compounds such as polyethylene glycol monoalkyl ether and polyfluoroalkyl acrylate; Nonionic, cationic, and anionic surfactants: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N −(2
-aminoethyl)3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycid xyprobylmethyldimethoxysilane,
2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-
Adhesion promoters such as methacryloxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane;
Antioxidants such as 2,2-thiobis(4-methyl-6-t-butylphenol), 2,6-di-butylphenol, 12-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5 - UV absorbers such as chlorobenzotriazole and alkoxybenzophenone; anti-aggregation agents such as sodium polyacrylate and sodium polymethacrylate; 2-dibenzoylmethylene-3-methyl-
β-naphthothiazoline, N-phenylthioacridone,
4-(4-amyloxypheni)L,)-2,5-bis(
Mention may be made of sensitizers such as 4-methoxyphenyl) thiapyrylium perchlorate.

To produce the composition of the present invention, for example, (a) a polymer solution, (b) a dye compound, and, if necessary, (c) a radiation-sensitive crosslinking agent, are added to a ball mill, a pebble mill, a shaker, a homogenizer, a Miki roll, etc. , and may be mixed using a sand mill or the like.

(a) Examples of the organic solvent in which the polymer solution is AM'A include the same organic solvents as those used in the production of polyamic acid (1) above.

In addition, the organic solvent in this case includes other organic solvents such as alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons such as methyl alcohol, ethyl alcohol, isopropyl alcohol, Cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol methyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate,
Butyl acetate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether,
Ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-1-
Propyl ether, ethylene glycol-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, ■, 2-dichloroethane, I, 4-dichlorobutane, trichloroethane, chlorobenzene, 0-dichlorobenzene , hexane, heptane, octane, benzene, toluene, xylene, etc. can be mixed to an extent that the polymer (a) will not be precipitated.

The colored resin composition of the present invention usually has the polymer (a) dissolved in a solvent, and the solid content concentration is usually 0. A solution of 1 to 30% by weight, preferably 0.5 to 15% by weight is prepared.

At this time, the solution viscosity of the 5% by weight solution of the polymer (a) is usually 10 to 100 cps.

The composition of the present invention has superior storage stability compared to conventional compositions containing aromatic polyamic acids, has excellent pigment dispersion stability, and has (c) radiation sensitivity as required. In addition to these effects, products containing a crosslinking agent have high sensitivity to radiation, high resolution, and have a large film-forming ability, making it easy to form thin films. It is possible to obtain a coating film with high adhesion to, etc., and is particularly suitable for forming a colored resin layer of a color filter.

Substrates on which color filters are formed using the composition of the present invention obtained in this manner include, for example, soda glass, Pyrex glass, and quartz glass used in liquid crystal display elements, and transparent conductive films adhered to these glasses. Examples include photoelectric conversion element substrates used in solid-state imaging devices, such as silicon substrates.

When manufacturing a color filter using the composition of the present invention, the composition? The pattern of the coating film can be formed by a photolithography method using a photoresist or a printing method.

In the former photolithography method, the composition of the present invention is applied onto the above-mentioned substrate by a spin coater method, a roll coater method, a spray method, etc. to form a coating film.
Dry at 0 to 150°C for about 10 to 30 minutes, and then apply a positive or negative resist on the coating film thus formed. After drying, expose and develop as necessary. A resist layer is formed to protect the color elements of the colored resin layer, and unnecessary parts of the color elements of the colored resin layer are etched and removed using this resist layer as an etching mask. For the second and subsequent colors, the same operation as for the first color is performed, and finally the resist is removed to form the color elements of the color filter.

On the other hand, in the latter printing method, a color filter is produced by using the composition of the present invention as a printing ink and printing each color element on the above-mentioned substrate by offset printing, letterpress printing, gravure printing, or even screen printing. .

Next, in order to produce a color filter using the composition formed by adding the (c) radiation-sensitive crosslinking agent of the present invention, first, it is coated on the above-mentioned substrate using a spin coater in the same manner as the photolithography method described above. The composition is applied by a method such as a method, a roll coater method, a screen printing method, or a spray method to form a coating film, and then dried at, for example, 70 to 150° C. for about 10 to 30 minutes.

Next, the coating film is irradiated with ultraviolet rays of 10 to 1,000 mJ/CrA to the color element portions, and then developed with a developer and rinsed as necessary.

Here, as the developer, for example, a single or mixed solvent such as N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N,N-dimethylformamide, tetramethylurea, hexamethylphosphoramide, dimethylsulfoxide, etc. is used. However, it is also possible to use a developer in which the developing time is adjusted by further mixing a poor solvent such as methanol, ethanol, propatool, or acetone with these solvents. .

Further, ammonia water or an alkaline aqueous solution using a primary amine, a secondary amine, or a tertiary amine can also be used as the developer. Even in this case, the development time can be adjusted to an appropriate value by changing the alkali concentration.

These developing solutions can be used alone or in combination of two or more.

Moreover, water, acetone, etc. can be mentioned as a rinsing liquid.

The development and rinsing are carried out by dipping, spraying, or the like, and then the coating film is sufficiently dried.

Furthermore, when producing a color filter having a plurality of color elements, the above steps may be repeated as many times as necessary using a composition in which the dye compound is changed and (iii) a radiation-sensitive crosslinking agent is added.

〔Example〕

Examples of the present invention will be described below, but the present invention is not limited thereto.

Synthesis Example 1 2.3.5-) After dissolving 22.4 g (0.1 mol) of lycarboxycyclopentyl acetic dianhydride in 379.8 g of N-methyl-2-pyrrolidone (NMP), 4.
4'-diaminodiphenylmethane 19.8g (0,1
mol) and reacted at 60°C for 4 hours until the solid content concentration was 1.
A 0% by weight polyamic acid solution was obtained. The intrinsic viscosity of this polyamic acid (77anh = ln ('7r*t /c
), C=0. 5g/〃, 30℃, in NMP] is 0.
The viscosity of the NMP solution having a solid content of 65 dl/g and a solid content concentration of 5% by weight was 35 cps (25° C.).

Synthesis Example 2 In the same manner as in Synthesis Example 1, 422.0 g of an NMP solution of polyamic acid with a solid content concentration of 10% by weight was prepared from 2,3.5-tricarboxycyclopentyl acetic dianhydride and 4,4'-diaminodiphenylmethane. Obtained. Add NMP4 to this solution.
22. The mixture was diluted with Og, 30.6 g of acetic anhydride and 28.7 g of pyridine were added, and the mixture was reacted at 130° C. for 6 hours.

The obtained solution was distilled under reduced pressure to remove by-produced acetic acid, catalyst pyridine, and unreacted acetic anhydride together with NMP.
An NMP solution of polyimide having a solid content concentration of 10% by weight was obtained.

The imidization rate of the polyimide at this time was confirmed to be 98% from infrared absorption spectrum (IR) and nuclear magnetic resonance spectrum (NMR).

In addition, the intrinsic viscosity of this polyimide [ηink = 1n
('7rat/c), c=0. 5g/d1.30
℃, NMP) is 0.71d! /g, solid content concentration 5% by weight
The viscosity of the NMP solution was 48 cps (25°C).

Synthesis Example 3 2.3.5-) 11.2 g (0.05 mol) of lycarboxycyclopentyl acetic dianhydride and 16.1 g (0.05 mol) of benzophenonetetracarboxylic dianhydride were added to 425.7 g of NMP? After 8 answers, 4.4'
20.0 g (0.1 mol) of -diaminodiphenyl ether was added and reacted at 60° C. for 4 hours to obtain a polyamic acid solution with a solid content concentration of 10% by weight.

The intrinsic viscosity of this polyamic acid [η1nh=I! n('7
rt/C), c=0. 5 g/d113
0°C, in NMP] is 0.58 a/g, and the viscosity of the NMP/@ liquid with a solid concentration of 5% by weight is 32 cps (25
°C).

Example 1 NMP of the polyamic acid obtained in Synthesis Example 1 with a solid content concentration of 10% by weight? 100 g of liquid, C, I.

Pigment Red 149] Og, n-butyl cellosolve 10g, and nonionic surfactant 7f
11 (manufactured by BM Hemy, BM-1000) 0.
1 g was dispersed for 24 hours using a ball mill containing stainless steel balls.

This dispersion was filtered using a filter having a pore size of 10 μm to obtain a composition dispersion of the present invention.

The obtained composition dispersion was a uniform dispersion without precipitation of the pigment compound, precipitation of the polymer, or change in viscosity even after being left at room temperature for one week.

When this dispersion was applied onto a glass substrate using a spin coater to a dry film thickness of 3 μm and dried at 150°C for 60 minutes, a uniform red coating film was obtained, with no voids or
No membrane defects such as membrane roughness were observed.

Furthermore, negative resist 1- (Japanese Synthetic Rubber ■
Co., Ltd., ClR702) was applied using a spin coater to a dry film thickness of 1 μm, dried, exposed, and developed to form an 11×11 mosaic pattern.

Using this resist pattern as an etching mask, NMP
The colored resin layer was etched using this as an etching solution.

Next, after peeling off the resist layer, it was dried at 180° C. for 60 minutes, and a mosaic-like color element having a red uniform and good film surface was obtained.

When observed under a microscope, the edges of the color elements were sharp and there were no defects due to aggregation of the dye compounds.

Example 2 100 g of NMP solution of polyimide with a solid content concentration of 10% by weight obtained in Synthesis Example 2, C, I, Pigment B
5 g of lue 15 and 0.5 g of aminopropyltrimethoxysilane were dispersed for 24 hours using a ball mill containing a stainless steel ball with a diameter of 3 dragons.

This dispersion was filtered using a filter having a pore size of 10 μm to obtain a composition dispersion of the present invention.

The obtained composition dispersion was a uniform dispersion without precipitation of the pigment compound, precipitation of the polymer, or change in viscosity even after being left at room temperature for one week.

This dispersion was applied onto a glass substrate in the same manner as in Example 1 to form a coating film, and an etching mask was further formed on the colored resin layer using a negative resist. Using this resist pattern as an etching mask, etching was carried out in the same manner as in Example 1, the resist was peeled off and dried, and a blue patterned color element similar to that in Example 1 was obtained.

Example 3 A green composition dispersion was obtained in the same manner as in Example I except that C,1, Pigment Green 36 was used instead of C,1, Pigment Red 149. This dispersion also has excellent storage stability, with no aggregation of pigment compounds or precipitation of polymers, and the colored resin layer obtained from this composition dispersion is uniform, and can be used as a color element suitable as a color filter by buttering. was formed.

Example 4 100 g of the NMP solution of polyamic acid obtained in Synthesis Example 3 and having a solid content concentration of 10% by weight, C, I.

Pigment Black 1 (10 g), n-butyl cellosolve (5 g), ethylene glycol (2 g), and aminopropyltrimethoxysilane (1.5 g) were mixed using a ball mill containing stainless steel balls with a diameter of 3 mm.
Dispersed for 0 hours.

This dispersion was filtered using a filter having a pore size of 10 μm to obtain a composition dispersion of the present invention.

The obtained composition dispersion was a uniform dispersion without precipitation of the pigment compound, precipitation of the polymer, or change in viscosity even after being left at room temperature for one week.

When a mosaic color element was formed using this dispersion in the same manner as in Example 1, the result was a black pattern with a light transmittance of 2% or less and a sufficient light shielding effect, and could be used as a blank drive for color filters. It was satisfying. Furthermore, when observed under a microscope, the edges of the pattern were sharp, and no aggregation of the dye compound was observed.

Comparative Example 1 32.2 g (0.1 mol) of 3.3',4.4'-benzophenonetetracarboxylic dianhydride was mixed with NMP469.
After dissolving in 8 g of polyamic acid, 20.0 g (0.1 mol) of 4,4'-diaminodiphenyl ether was added and reacted at 10°C for 8 hours to obtain an NMP solution of polyamic acid with a solid concentration of 10% by weight. It was done.

The intrinsic viscosity of this polyamic acid [ηir+h = l n
(ηrat/c), c = 0. 5g/d
i, 30°C, in NMP] is 0.79 dl/g, and the viscosity of an NMP solution with a solid content concentration of 5% by weight is 32 c p s
(25°C).

When a composition dispersion was prepared in the same manner as in Example 1 using this NMP solution of polyamic acid with a solid content concentration of 10% by weight, the dispersion state of the pigment compound was poor and the pore size was l.
Filtration using a 0 μm filter was difficult. Furthermore, when filtering through a filter with a pore size of 20 μm took a long time, the color density of the obtained dispersion was insufficient because the pigment compound was removed by filtration, but the color density was sufficient for a color filter. A coating film could not be formed.

Furthermore, the storage stability of the solution was poor, and when it was left at room temperature for one week, aggregation of the dye compound and precipitation of the polymer were observed.

Use Example 1 Using the compositions of the present invention obtained in Examples 1 to 3, a color filter having a mosaic pattern of red, green, and blue was manufactured as follows.

First, the composition dispersion obtained in Example 1 was applied onto a glass substrate using a spin coater so that the dry film thickness was 3 μm, and dried at 140° C. for 15 minutes.

Next, negative resist (manufactured by Japan Synthetic Rubber ■, ClR702)
) was applied to a dry film thickness of 1 μm, dried at 100° C., exposed to light through a photomask giving a mosaic pattern of l tar X l n+, and developed to form an etching mask.

Next, the colored resin layer was etched using NMP as an etching solution to form color elements.

Similarly, the same operation as above was repeated using each of the composition dispersions obtained in Example 2 and Example 3 to form a mosaic color filter having red, green, and blue color elements of 1 mm square. I got it.

Finally, the negative resist layer of each color element was peeled off using a stripping solution (manufactured by Japan Synthetic Rubber Company, x-n).

The obtained color filter had a clear pattern of each color element, and also had sufficient color density and hue.

Example 5 100 g of the NMP solution of the polyamic acid obtained in Synthesis Example 1 and having a solid content concentration of 10% by weight.C,I.

Pigment Red 149 (10 g) and 2,6-bis(4'-azidobenzal)-4-methylcyclohexanone (1 g) were dispersed for 18 hours at 3° C. using a ball mill containing a 1 mφ stainless steel ball.

This dispersion was filtered using a filter having a pore size of 10 μm to obtain a composition dispersion of the present invention.

The obtained composition dispersion was a uniform dispersion without precipitation of the pigment compound, precipitation of the polymer, or change in viscosity even after being left at room temperature in a dark place for one week.

When this dispersion was applied onto a glass substrate using a spin coater to a dry film thickness of 2 μm and dried at 130°C for 15 minutes, a red uniform coating film was obtained, with no voids or
No membrane defects such as membrane roughness were observed.

Furthermore, 500 m was measured using a high-pressure mercury lamp through a photomask with a mask hole width of 0.1 to 1 wm for resolution measurement.
Irradiate with light energy of J/c+a, develop with NMP,
After rinsing with water, it was dried at 180°C for 60 minutes.

The obtained color element has a pattern of fine lines of 0.1 to 11 m, has no film defects such as pinholes or film roughness, and when observed under a microscope, there is no meandering in the pattern and sharp edges. Therefore, it could be suitably used as a color filter.

Example 6 100 g of the NMpi solution of the polyimide obtained in Synthesis Example 2 with a solid content concentration of 10% by weight, C, I.

5g of Pigment Blue 15, 4.4
'-Diazidostilbene-2,2'-disulfonic acid Ig
Example 5 except that , and 0.1 g of nonionic surfactant (BM-1000, manufactured by BM Hemi) were used.
A dispersion composition of the present invention was obtained in the same manner as described above.

The obtained composition dispersion was a uniform dispersion without precipitation of the pigment compound, precipitation of the polymer, or change in viscosity even after being left at room temperature in a dark place for one week.

Using this dispersion liquid, it was applied in the same manner as in Example 5 onto the glass substrate on which the red color element prepared in Example 5 was formed, and dried, and the parts other than the red resin layer were coated with Example 5. Similarly, light energy is irradiated through a photomask, and N, N
- After developing with dimethylacetamide and rinsing with acetone, drying was performed at 180° C. for 60 minutes.

The obtained color element is an excellent color element similar to that of Example 5, and there are no changes such as wrinkles, cracks, or peeling in the coating film having a red pattern, and it has good heat resistance and solvent resistance. It was of excellent quality.

Example 7 A composition dispersion of the present invention was obtained in the same manner as in Example 5, except that C,1, Pigment Green 36 was used instead of C,1, Pigment Red 149.

Even when this composition dispersion was left at room temperature in a dark place for one week, there was no precipitation of the pigment compound, no precipitation of the polymer, no change in viscosity, and the dispersion remained uniform.

When a color filter was formed using this dispersion in the same manner as in Example 5, it had sufficient hue and color density as a color filter, and the surface was smooth and the edges were clear.
A clear pattern was obtained.

Example 8 100 g of the NMP solution of the polyamic acid obtained in Synthesis Example 3 and having a solid content concentration of 10% by weight, C, I.

10 g of Pigment Black 1, 5 g of n-butyl cellosolve, 4.4'-diamidostilbene-
A composition dispersion of the present invention was obtained in the same manner as in Example 5, except that 1 g of 2,2'-disulfonic acid and 1.5 g of aminopropyltrimethoxysilane were used.

Even when this composition dispersion was left at room temperature in a dark place for one week, there was no precipitation of the pigment compound, no precipitation of the polymer, no change in viscosity, and the dispersion remained uniform.

When a color filter was formed using this dispersion in the same manner as in Example 5, a black color element with a light transmittance of 2% or less and a sufficient light shielding effect was obtained, which is satisfactory as a color filter. Met.

Use Example 2 Using the compositions of the present invention obtained in Examples 5 to 7, a color filter having red, green, and blue mosaic color elements was manufactured as follows.

First, the composition dispersion of the present invention obtained in Example 5 was coated onto a glass substrate using a spin coater so that the dry film thickness was 3 μm, and dried at 140° C. for 15 minutes.

Next, it was exposed to 500 mJ/cd of light through a photomask giving a mosaic pattern of l w Dry for 60 minutes.

Similarly, the compositions of the present invention obtained in Example 6 and Example 7 were used in this order and the same operations as above were repeated to create a mosaic of 11 m square having red, green, and blue color elements. A colored filter was obtained.

The obtained color filter had a clear pattern of each color element, and also had sufficient color density and hue.

〔Effect of the invention〕

The colored resin composition of the present invention does not cause polymer precipitation, agglomeration, sedimentation, or separation of pigment compounds, provides a uniform coating film with excellent coloring properties, can be processed at low temperatures, and has excellent heat resistance and resistance. It has excellent solvent properties.

Further, a radiation-sensitive colored resin composition obtained by blending a radiation-sensitive crosslinking agent into this colored resin composition has excellent photosensitive properties and development properties in addition to the above-mentioned effects.

Therefore, the colored resin composition of the present invention can be used as heat-resistant paints and ultraviolet curable paints in the paint industry, various plate-making materials in the printing industry, precision parts processing materials in the electronics industry, color separation filters for optical elements, and color separation filters in the photographic industry. It can be widely used in photographic materials constituting photosensitive colored resin layers, color filters for colorizing liquid crystal display elements, color filters for color separation of solid-state image sensors, and the like.

Patent applicant: Japan Synthetic Rubber Co., Ltd. Agent: Patent Attorney Takashi Shirai

Claims (1)

[Claims] (1) (i) A polymer having a repeating structural unit represented by the following general formula (I) and/or a repeating structural unit represented by the following general formula (II), and (b) a colored resin containing a pigment compound. Composition. ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(II) (In the formula, R is a tetravalent aliphatic group or alicyclic The group group R^1 is a divalent organic group, and R^2 and R^3 may be the same or different and represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.)