JPH09311211A - Color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a color filter which can be produced without requiring a polishing treatment or UV cleaning without causing contamination on the base even when a heating process is included in the production process. SOLUTION: This color filter consists of a color resin layer in a pattern on a substrate. The color resin layer is produced by hardening a photosensitive color compsn. with light, and the color compsn. containing a binder resin essentially comprising copolymers of monomers having N-substd. maleimide and acid groups, dyes, dispersant, photopolymerizable monomers, photopolymn. initiator and solvent. In this production process of the color filter, contamination on the base due to thermally sublimated material is hardly caused, and adhesion defects between the filter and the substrate can be prevented without polishing or UV cleaning. Thus, workability and productivity can be improved.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color filter used for imaging a video camera such as a color liquid crystal display device, a color scanner, a solid-state image sensor, and a color facsimile.

[0002]

2. Description of the Related Art Heretofore, the following method has been known as a method for producing a color filter using a pigment. To a colored composition obtained by dispersing a pigment with a dispersant or the like in an acrylic binder resin, a photopolymerization initiator, a photopolymerizable monomer is added to sensitize the colored composition, and this is coated on a glass substrate. After drying, exposure and development are performed using a mask to form a colored pattern, and the pattern is fixed by heating. These steps are repeated for each color to produce a color filter (see JP-A-1-152449).

[0003]

However, according to this method, a heating step (200 to
At 230 ° C.), a thermally decomposed product of the binder resin adheres to the substrate and causes soiling. The background stain causes poor adhesion to the substrate to which the color filter is attached, and therefore must be removed by polishing treatment, UV cleaning or the like. However, there are problems such as pattern peeling and scratches on the film surface due to the polishing process, and film surface roughness due to UV cleaning. The present invention has been made to solve the above problems, and provides a color filter that is manufactured without causing scumming even if there is a heating step in the manufacturing process and without requiring polishing treatment, UV cleaning, or the like. Especially.

[0004]

The color filter of the present invention comprises a binder resin, a dye, a dispersant, a photopolymerizable monomer, and a photopolymerization containing a copolymer of N-substituted maleimide and a monomer having an acid group as a main component. A colored resin layer formed by photocuring a photosensitive colored composition comprising an initiator and a solvent is provided on a substrate. Here, the N-substituted maleimide in the binder resin is preferably 10 to 90% by weight, and the monomer having an acid group is preferably 10 to 60% by weight. The molecular weight of the binder resin is 300
It is desirable that it is 0-150,000.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Examples of the N-substituted maleimide in the present invention include cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, n-butylmaleimide, laurylmaleimide and the like. Examples of the monomer having an acid group in the present invention include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, vinylbenzoic acid or (meth) acrylic acid caprolactone adduct having at least one carboxylic acid in the molecule, and hydroxyalkyl. Examples thereof include those obtained by adding an acid anhydride such as phthalic anhydride to (meth) acrylate, and acrylic acid and methacrylic acid are particularly preferable in terms of sensitivity. Further, when synthesizing the binder resin in the present invention, it is desirable to add a monomer that improves characteristics such as adhesion to a substrate, developability, and film hardness. Such monomers include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate,
Benzyl methacrylate, cyclohexyl methacrylate, lauryl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, ethoxyethyl methacrylate, glycidyl methacrylate,
Examples include dimethylaminoethyl methacrylate, benzyl acrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, cyclohexyl acrylate, hydroxymethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, vinyl acetate, tetrahydrofurfuryl acrylate, and N-vinylpyrrolidone. To be

In this binder resin, it is desirable that the amount of the monomer having an acid group is 10 to 60% by weight, and the amount of the N-substituted maleimide as the balance is 10 to 90% by weight. When the amount of the monomer having an acid group is less than 10% by weight, the development becomes difficult, and when it is more than 60% by weight, the sensitivity to the development is too high and the control thereof becomes difficult. In addition, the molecular weight (number average molecular weight Mn) of the binder resin is preferably 3000 to 150,000. When the molecular weight is less than 3,000, it does not function as a binder resin, and when the molecular weight is more than 150,000, dispersibility deteriorates. The acid value of the binder resin is preferably 30 to 150. If the acid value is less than 30, the developability decreases, and if it is more than 150, the pattern shape cannot be maintained.

The dye in the present invention includes dyes and pigments, but pigments are desirable in terms of heat resistance and light resistance. As the pigment, CI No. 9, 97, 12 as red (Red)
2, 123, 149, 168, 177, 180, 192, 215, etc.
en) as CIPig. 7, 36, CI No. 1 as blue (Blue)
CI No. 20, 2 as yellow (Yellow), such as 5, 22, 60, 64
4, 83, 86, 93, 109, 110, 117, 139, 153, etc.
CI No. 19, 23, 29, 30, 40, 50 and the like are generally used as the iolet), and CI No. 7 and the like are used as the black.

As the dispersing agent in the present invention, a wide range of dispersing agents such as surfactants, intermediates for pigments, intermediates for dyes, and high molecular dispersing agents (for example, "Solsperse" manufactured by Zeneca Corporation) are used. . Preferably, it is a derivative of an organic dye, and the organic dye serving as a base is an azo type, a phthalocyanine type, a quinacridone type, an anthraquinone type, a berylene type, a thioindico type, a dioxazine type, or a metal complex salt type. A derivative having a substituent in these organic dyes and effective in dispersing the dye is used. As the substituent, a hydroxyl group, a carboxyl group, a sulfone group, a carbonamide group, a sulfonamide group, or any of the substituents represented by the following general formulas are preferable. A derivative having at least one kind of substituent selected from these substituents is used.

Embedded image The dye used in the present invention and the parent organic dye of the dispersant are usually combined in the same phase due to the relationship of the phases, but they do not necessarily have to match. The proportion of the composition at the time of dispersion is not particularly limited, but the amount of the pigment added to the binder resin is about 50 to 150% by weight, and the dispersant is preferably about 1 to 10% by weight of the pigment.
Further, for the spectral adjustment of the color filter, an arbitrary pigment is mixed and adjusted at two or three points.

As photopolymerizable monomers, there are difunctional, trifunctional and polyfunctional monomers.
1,6-hexanediol diacrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, etc., and trifunctional monomers such as trimethylolpropane triacrylate, pentaerythritol triacrylate, etc. The monomers include ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, and the like. These monomers are available from Osaka Organic Chemical Industry Co., Ltd., Showa High Polymer Co., Ltd., Toa Gosei Chemical Industry Co., Ltd. Co., Ltd.). The addition amount of the photopolymerizable monomer is not particularly limited, but is preferably about 20 to 150% by weight of the binder resin.

In the present invention, the photopolymerization initiator is 2,2.
4,6-Tris (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2-phenyl-
4,6-bis (trichloromethyl) -s-triazine,
2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p- Chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-
Methoxy-1′-naphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (9-n-butyl-3)
-Carbazolyl) -4,6-bis-trichloromethyl-
s-Triazine, 2- (1-ethoxycarbonylmethyl-4-carbazolyl) -4,6-bis-trichloromethyl-s-triazine, 2- (9-n-octyl-3-carbazolyl) -4,6-bis -Trichloromethyl-s-
Triazine, 2- [9- (2-phenoxyethyl) -3
-Carbazolyl] -4,6-bis-trichloromethyl-
s-triazine, 2- (N-isoamyloxycarbonylmethyl-3'-carbazolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (N-2 "-methoxy-1" -methylethoxy Carbonylmethyl-3 "-carbazolyl) -4,6-bis (trichloromethyl) -s
-Triazine, 2- (N-cyclohexylcarbonylmethyl-3'-carbazolyl) -4,6-bis (trichloromethyl) -s-triazine.

The photopolymerization initiator of the present invention may be a mixture of one or more of the following compounds as the photopolymerization initiator. Examples of acetophenone-based compounds include 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenyl (4-dodecyl) propan-1-one, and the like. . Benzophenone-based compounds include benzophenone, 3,3-dimethyl-4-methoxybenzophenone, methyl o-benzoylbenzoate and the like. As an imidazole compound, 2- (2,
3-dichlorophenyl) -4,5-diphenyl-imidazole dimer, 2- (2,3-dichlorophenyl) -4,
5-bis (3-methoxyphenyl) -imidazole dimer, 2- (2,3-dichlorophenyl) -4,5-bis (4-methoxyphenyl) -imidazole dimer, 2-
(2,3-dichlorophenyl) -4,5-bis (4-chlorophenyl) -imidazole dimer, 2- (2,3-dichlorophenyl) -4,5-di (2-furyl) -imidazole, 2,2 '-Bis (2-chlorophenyl) -4,5,
4 ', 5'-tetraphenyl-1-2'-biimidazole and the like. Thioxanthone compounds such as 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2,4-dimethylthioxanthone. Benzoin-based compounds include benzyl methyl ketal, benzoin isopropyl ether, benzoin isobutyl ether and the like. 4,4'-bis (diethyl) as an amine compound
Aminobenzophenone, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 4,4′-bis (dimethyl) aminobenzophenone and the like. The addition amount of the photopolymerization initiator is not particularly limited, but is 1 to 50% by weight, preferably 5 to 30% by weight of the photopolymerizable monomer, acetophenone compound, benzophenone compound, imidazole compound, thioxanthone. Compounds,
The benzoin-based compound and the amine-based compound are added at a ratio of 1 to 40% by weight, preferably 5 to 20% by weight of the photopolymerizable monomer.

As the solvent, methanol, ethanol,
Ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve, methyl cellosolve acetate, diglyme, cyclohexanone, ethylbenzene, xylene, isoamyl acetate, n-amyl acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monoethyl Ether acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether,
Diethylene glycol monobutyl ether acetate,
Triethylene glycol, triethylin glycol monomethyl ether, triethylin glycol monomethyl ether acetate, triethylene glycol monoethyl ether, triethylene glycol monoethyl ether acetate, liquid polyethylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether acetate, diethylene glycol Propylene glycol monoethyl ether, dipropylene glycol monoethyl ether acetate, lactate ester, ethyl ethoxy propionate, etc. are used, but since they differ depending on the monomer composition of the copolymer, photopolymerization initiator, etc., single or multiple solvents Is appropriately selected.

In the color filter of the present invention, by using the photosensitive coloring composition using a binder resin which is not easily decomposed by heat without impairing transparency or dispersibility, scumming does not occur in the production process, A color filter that adheres well to a substrate without polishing or UV cleaning.

[0014]

Example A photosensitive coloring composition was prepared as described below, and a color filter was manufactured using the photosensitive coloring composition. 20 parts by weight of methacrylic acid as a monomer having an acid group, 20 parts by weight of hydroxyethyl methacrylate,
Cyclohexylmaleimide 6 as N-substituted maleimide
0 parts by weight and dissolved in 300 parts by weight of ethyl cellosolve,
Add 0.75 parts by weight of azobisisobutyronitrile under a nitrogen atmosphere and react at 70 ° C. for 5 hours to obtain a binder resin (molecular weight Mn / Mw: 14000/40000, acid value:
130) was obtained. Then, the binder resin was diluted with ethyl cellosolve to a resin concentration of 10%. To 90.1 g of this diluted resin, red pigment (CI No. 9) 9.0
g, dispersant (trade name of Sols Perth Zeneca Co., Ltd.)
9 g was added, and the mixture was sufficiently kneaded with a triple roll to produce a red varnish. Similarly, a green varnish and a blue varnish were produced using a green pigment (CINo.Pig.36) and a blue pigment (CINo.15). Trimethylolpropane triacrylate: 0.4 g 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine: 0.02 g 2, with respect to 100 g of each colored resin. 2-bis (2-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1-2'-biimidazole ... 0.02 g was added and well stirred to obtain a photosensitive coloring composition.

Then, the above-prepared red light-sensitive coloring composition was spin-coated (1000 rpm, 40 rpm) on a glass substrate on which r-glycidoxypropylmethylethoxysilane was spin-coated and well spin-dried. For 2 seconds) and dried. After prebaking at 70 ° C. for 20 minutes, exposure was performed at an exposure amount of 150 mJ / cm ² using a mask having a pixel size of 30 μm × 100 μm. After development with a 2.5% sodium carbonate solution, the film was thoroughly washed with water. It was baked at 230 ° C. for 1 hour and fixed in a pattern. The same procedure was repeated for the green and blue photosensitive coloring compositions (exposure amount: 150 mJ / cm ^{2 for} each of green and blue) to prepare a color filter.
When the glass portion of the color filter other than the pattern formed was observed with a microscope, no background contamination was observed. [Comparative Example] A photosensitive coloring composition was prepared in the same manner as in the binder resin of the photosensitive coloring composition in the above Example, except that butyl methacrylate was used instead of cyclohexylmaleimide to manufacture a color filter. When the glass portion of the color filter other than the pattern formed was observed with a microscope, background contamination was confirmed.

[0016]

The color filter of the present invention has, as the main component of the binder resin in the photosensitive coloring composition,
By using a copolymer of N-substituted maleimide and a monomer having an acid group, thermal decomposition is less likely to occur, and there is little background stain due to the deposition of thermal sublimates on the substrate during the manufacturing process of the color filter. Since workability and productivity are improved even when there is no defective adhesion to the substrate to which the color filter is attached, the workability and productivity are improved.

Claims (3)

[Claims] 1. A binder resin, a dye, comprising a copolymer of N-substituted maleimide and a monomer having an acid group as a main component,
A color filter comprising a substrate and a colored resin layer formed by photocuring a photosensitive coloring composition containing a dispersant, a photopolymerizable monomer, a photopolymerization initiator, and a solvent. 2. The N-substituted maleimide in the binder resin is 10 to 90% by weight, and the monomer having an acid group is 10% by weight.
The color filter according to claim 1, wherein the color filter is about 60% by weight. 3. The molecular weight of the binder resin is 3000.
The color filter according to claim 1, wherein