JPH11305433A - Photosensitive composition, photosensitive colored composition and color filter using the colored composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive compsn. and a photosensitve colored compsn. capable of forming a high definition pattern less liable to reduce its transmittance by heating, having high heat resistance and excellent in chemical resistance and to provide a color filter using the photosensitive colored compsn. SOLUTION: The photosensitive compsn. contains a resin which is cured with an acid, a crosslinking agent and a photoinitiator as essential components and the photoinitiator is a combination of a photo-radical generating agent and an onium salt. The photosensitive colored compsn. contains a resin which is cured with an acid, a crosslinking agent, a photoinitiator and a pigment as essential components and the photoinitiator is a combination of a photo- radical generating agent and an onium salt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive composition and a photosensitive coloring composition used for forming a pattern by a photolithography method, and more particularly to a pattern forming method and a color filter forming method for manufacturing a display. The present invention relates to a photosensitive composition, a photosensitive coloring composition, and a color filter using the photosensitive coloring composition, and more specifically, has excellent heat resistance, chemical resistance, high sensitivity, and process stability. A photosensitive composition, a photosensitive coloring composition, and a photosensitive coloring composition capable of efficiently producing a high-definition pattern having a good shape, a high dimensional accuracy, a high dimensional accuracy, a color filter, and the like at an excellent yield. It relates to a color filter.

[0002]

2. Description of the Related Art Conventionally, as a photosensitive composition and a photosensitive coloring composition for producing a display, a radical polymerization type photosensitive composition containing a polyfunctional acrylate and a photopolymerization initiator in an acrylic resin, a photosensitive composition, Colored compositions and the like are mainly used (JP-A-1-152449). Although the system using the above radical polymerization has high sensitivity, it is easily affected by oxygen at the time of exposure, so that it is difficult to form a pattern in an oxygen atmosphere and a large amount of exposure is required. Therefore, it is necessary to form an oxygen barrier film and perform exposure in a state where it is hardly affected by oxygen, and the process is complicated.

As a photosensitive coloring composition which solves such a problem, for example, a resin containing phenol which is cured by an acid and a crosslinking agent having an N-methylol structure disclosed in JP-A-4-163552 are disclosed. There is a photosensitive coloring composition comprising a photoacid generator and a pigment. It is well known that a chemically amplified photosensitive composition utilizing this acid-catalyzed reaction has high sensitivity and high resolution, and the pattern shape obtained with this photosensitive composition is vertically steep. That was the feature. The method for forming a pattern using this photosensitive composition involves applying the photosensitive composition on a substrate, pattern exposure to generate an acid, heating the exposed substrate, and curing the resin by an acid-catalyzed crosslinking reaction. Then, a pattern can be formed by alkali development.

Onium salts and trihalomethyl group-containing triazine derivatives have been used as photoacid generators for use in the chemically amplified photosensitive compositions utilizing the above-described acid catalysis. However, onium salts have a light absorption of 300 n.
m or more, when an onium salt is used as a photoacid generator in a photosensitive coloring composition in which a pigment is dispersed, the absorption of light by a pigment or the absorption of light by a glass substrate used as a mask for pattern exposure is reduced. Therefore, sufficient sensitivity could not be obtained.

On the other hand, when a triazine derivative containing a trihalomethyl group is used as a photoacid generator, the light absorption of the triazine derivative is around 300 nm to 400 nm, and a halogen radical is generated from the triazine derivative by the light having the wavelength. I do. Then, the halogen radicals extract hydrogen and turn into hydrogen halide, which acts as an acid. Therefore, sufficient sensitivity can be obtained. However, the radicals formed on the remaining triazine derivative and halogen radicals not converted to acid cause an addition reaction to the resin and cause the resin to be colored, or cleave the main chain of the resin, resulting in heat resistance and chemical resistance. May cause a decline.

[0006]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a high heat-resistant, chemical-resistant material which causes little decrease in transmittance due to heating. Uses a photosensitive composition, a photosensitive coloring composition, and a photosensitive coloring composition capable of forming a high-definition pattern having excellent properties, high sensitivity, high process stability, good shape, high dimensional accuracy, and high dimensional accuracy. The purpose of the present invention is to provide a suitable color filter.

[0007]

The present invention provides a photosensitive composition comprising a resin curable by an acid, a crosslinking agent, and a photoinitiator, wherein the photoinitiator comprises a photoradical generator and an onium. A photosensitive composition comprising a combination of salts.

Further, the present invention provides a resin curable by an acid,
A photosensitive coloring composition containing a crosslinking agent, a photoinitiator, and a pigment as main components, wherein the photoinitiator is a combination of a photoradical generator and an onium salt. Things.

Further, the present invention provides a resin curable by an acid,
A photosensitive coloring composition containing a crosslinking agent, a photoinitiator, and a pigment as main components, wherein the photoinitiator is a combination of a photoradical generator and an onium salt. It is a color filter characterized by using an object.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail below based on one embodiment. The photoinitiator in the present invention is a combination of a photoradical generator and an onium salt. With this combination, first, radicals are generated from the photoradical generating agent by pattern exposure through a mask. Next, the onium salt oxidizes the generated radical to convert the radical into an acid. And
This converted acid acts as a catalyst.

That is, the heating after the pattern exposure causes a crosslinking reaction between the resin hardened by the acid and the crosslinking agent to proceed, and the cross-linked portion exposed to the pattern by the development treatment after the heating forms a pattern. This pattern formation can form a high-definition and high-definition pattern as compared with a case where the onium salt is used alone.

Further, when a triazine derivative containing a trihalomethyl group is used in combination with an onium salt as a photoradical generator, the conversion efficiency of radicals to acid is higher than when a triazine derivative is used alone, and the remaining Coloring of the resin due to addition reaction to the resin and cleavage of the main chain of the resin due to the radical formed on the triazine derivative side of the triazine derivative side and the halogen radical not converted to the acid are suppressed, and a high-sensitivity, high-definition pattern is formed. It can be formed, and the obtained pattern has excellent heat resistance and chemical resistance.

Examples of the photo-radical generator include benzoin, benzoin ethyl ether, benzoin isopropyl ether, diphenyl sulfide, benzophenone, 2-ethyl anthraquinone, isobutyl thioxanthone, Michler's ketone, dibenzosuberone, diphenyl disulfide, diacetyl, Hexachlorobutadiene, pentachlorobutadiene, 1-chloromethylnaphthalene, benzoinbutyl ether, 1-benzyl-2-
Dimethylamino-1- (4-morpholino-phenyl) butanone-1, benzyldimethylketal, diethoxyacetophenone, acyloxime ester, hydroxyacetophenone, benzoyloxime, triazine derivative containing trihalomethyl group and the like can be used. From the viewpoint of sensitivity, trihalomethyl group-containing triazine derivatives are preferred.

Further, the trihalomethyl group-containing triazine derivatives include 2,4,6-tris (trichloromethyl) -s-triazine and 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- (4'-methoxy-1'-naphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methylthiophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl ) -S-triazine and the like can be used.

The amount of the photo-radical generating agent added is as follows:
1 to 20% by weight is preferable to 00% by weight. This is because when added in excess of 20% by weight, the amount of radical generation and conversion to acid is too large, and the acid diffuses into unexposed areas due to heating after pattern exposure, causing a cross-linking reaction, resulting in poor resolution. It may cause a decrease. On the other hand, when the addition amount is less than 1.0% by weight, the amount of acid generated is insufficient, the crosslinking reaction does not proceed sufficiently, and a pattern cannot be formed.

Onium salts include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate. , 4-methoxyphenylphenyliodonium tetrafluoroborate,
4-methoxyphenylphenyliodonium hexafluorophosphonate, 4-methoxyphenylphenyliodonium hexafluoroarsenate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, 4-methoxyphenyliodonium-p- Toluenesulfonate, bis (4-tert
-Butylphenyl) iodonium tetrafluoroborate, bis (4-tert-butylphenyl) iodonium hexafluorophosphonate, bis (4-tert-
Butylphenyl) iodonium hexafluoroarsenate, bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-te
rt-butylphenyl) iodonium trifluoroacetate, diaryliodonium salts such as bis (4-tert-butylphenyl) iodonium-p-toluenesulfonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexa Fluoroarsenate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfonate, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, -Methoxyphenyldiphenylsulfonium hexafluoroal Sulfonate, 4-methoxyphenyl diphenyl sulfonium trifluoromethanesulfonate,
4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium-p-trienesulfonate, 4-phenylthiophenyldiphenyltetrafluoroborate, 4-phenylthiophenyldiphenylhexafluorophosphonate, 4-phenylthiophenyldiphenylhexa Triarylsulfonium salts such as fluoroarsenate, 4-phenylthiophenyldiphenyltrifluoromethanesulfonate, 4-phenylthiophenyldiphenyltrifluoroacetate, and 4-phenylthiophenyldiphenyl-p-toluenesulfonate can be used. The honium salt is preferably added in an amount of 50 to 200% by weight based on 100% by weight of the photoradical generator.

The resin which is cured by an acid in the present invention is a resin which is a copolymer of a phenol represented by phenol novolak, p-hydroxystyrene, a monomer having a carboxyl group and a monomer having a hydroxyl group. be able to. In view of the heat resistance of the resin itself, the content of the phenolic monomer is 50% of the resin.
% By weight or less is preferred.

Examples of the monomer having a carboxyl group include acrylic acid, which is a monomer of unsaturated carboxylic acid,
Methacrylic acid, maleic acid, fumaric acid, crotonic acid and the like can be used. Examples of the monomer having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxyethyl methacrylate. Hydroxy compound monomers of unsaturated carboxylic acid alkyl esters such as propyl, 2-hydroxybutyl methacrylate, and 4-hydroxybutyl methacrylate can be used.

Other monomers usable for copolymerization include styrene, phenylmaleimide, methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, benzyl acrylate, methyl methacrylate, ethyl methacrylate, methacrylic Butyl acid,
Examples include cyclohexyl methacrylate and benzyl methacrylate.

Examples of the crosslinking agent in the present invention include methylolated urea, urea resin, methylolated melamine,
Butylolated melamine, methylolated guanamine, or an alkyl ether of these compounds can be used, and an alkyl etherified compound is more preferable from the viewpoint of high thermal stability. The alkyl group of the alkyl ether is preferably an alkyl group having 1 to 5 carbon atoms. Especially,
As the alkyl ether compound, an alkyl ether compound of hexamethylolmelamine is more preferable in terms of sensitivity.

The crosslinking agent causes a crosslinking reaction with the resin by heating in the presence of an acid generated after exposure to form a pattern. The amount of the crosslinking agent is about 5 to 100% by weight based on 100% by weight of the resin.

As the pigment in the present invention, red (Re
d) as C.I. I. Pig. 9, 97, 122, 12
3, 149, 168, 177, 180, 192, 215
For example, C.I. I. Pig.
7, 36, and blue (Blue) include C.I. I. Pig.
15, 16, 22, 60, 64, Yellow
As C.I. I. Pig. 12, 20, 83, 86, 1
38, 139, 154, and purple (Violet) as C.I. I. Pig. 23 is used.

These pigments may be used alone or as a mixture. The amount of these pigments is based on 100% by weight of the total solid content of the photosensitive coloring composition for a color filter according to the present invention. It is used at 10 to 60% by weight.

The photosensitive composition and the photosensitive coloring composition of the present invention may further contain an additive, if necessary. Specific examples of such additives include a pigment dispersant, a dissolution promoter, an adhesion promoter, an antioxidant, an ultraviolet absorber, and a sensitizer.

As the dispersing agent, a wide range of dispersing agents such as surfactants, pigment derivatives, "Solsperse" manufactured by Zeneca Corporation and the like are used. The amount of these dispersants added is
It is used at about 1 to 30% by weight with respect to 00% by weight.

As the solvent in the present invention, toluene,
Xylene, ethyl cellosolve, ethyl cellosolve acetate, diethylene glycol dimethyl ether, cyclohexanone and the like are used, and these solvents may be used alone or as a mixture. It is preferable to add these solvents so that the total solid content in the photosensitive composition and photosensitive coloring composition of the present invention is about 5 to 50% by weight.

An example of a method for producing a color filter using the photosensitive coloring composition of the present invention will be described below. A color filter using the photosensitive coloring composition of the present invention is applied to the entire surface of the photosensitive coloring composition of the present invention on a substrate and dried, and is subjected to pattern exposure from the substrate to generate radicals in the composition. A series of steps including generating an acid by conversion to an acid, heating to cure the composition, developing the composition with an alkaline developer and leaving the cured composition in a pattern to form a colored resin layer, and Is repeated to form colored resin layers of a plurality of colors on the same substrate.

As the heating method, a heating device such as an oven or a hot plate can be used.
0-150 ° C is suitable.

Examples of the alkali developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate, alkylamines such as triethylamine, alcoholamines such as triethanolamine, and tetramethylammonium hydroxide. And the like can be used.

If necessary, other additives such as a surfactant, a wetting agent, and an organic solvent may be added to the alkaline developer.

As described above, in the photosensitive composition and the photosensitive coloring composition of the present invention, by using a combination of a photo-radical generator and an onium salt as a photo-initiator, a mask is firstly used. Radicals are generated from the photo-radical generating agent by the pattern exposure through. Next, the onium salt oxidizes the generated radical to convert the radical into an acid. Then, the converted acid acts as a catalyst.

That is, the heating after the pattern exposure causes the crosslinking reaction between the resin hardened by the acid and the crosslinking agent to proceed, and the cross-linked portion subjected to the pattern exposure by the developing treatment after the heating forms a pattern. This pattern formation can form a high-definition and high-definition pattern as compared with a case where the onium salt is used alone.

Further, when a trihalomethyl group-containing triazine derivative is used in combination with an onium salt as a photoradical generator, the conversion efficiency of radicals into acid is higher than when a triazine derivative is used alone, and the remaining Coloring of the resin due to addition reaction to the resin and cleavage of the main chain of the resin due to the radical formed on the triazine derivative side of the triazine derivative side and the halogen radical not converted to the acid are suppressed, and a high-sensitivity, high-definition pattern is formed. It can be formed, and the obtained pattern has excellent heat resistance and chemical resistance.

Examples of the photosensitive coloring composition and the color filter according to the present invention will be described below.

EXAMPLES <Example 1> (Preparation of photosensitive coloring composition) p-hydroxystyrene / methacrylic acid / 2-hydroxyethyl methacrylate / butyl methacrylate copolymer (weight composition ratio) 15/25/20/40), using hexamethoxymethyl melamine (manufactured by Sanwa Chemical Co., Ltd .: “Niclac MW-30M”) as a crosslinking agent, and 2-benzyl-2-dimethylamino as a photoradical generator. Using -1- (4-morpholino-phenyl) butanone-1 (manufactured by Ciba Geigy KK: [Irgacure 369]), triphenylsulfonium trifluoromethanesulfonate (manufactured by Midori Kagaku KK: "T
PS-105 "), cyclohexanone (manufactured by Kanto Chemical Co., Ltd.) as a solvent, and" S24000GR "and" S5000 "of" Solsperse "(manufactured by Zeneca) in a 1: 1 ratio as dispersants. "Chromophthal Sun Red" (manufactured by Ciba Geigy) as a red pigment, "Lionol Green" (manufactured by Toyo Ink Mfg. Co., Ltd.) as a green pigment, and "Heliogen Blue" (B.I.
A. S. F. (Manufactured by K.K.). First, a resin, a pigment, a dispersant, and a solvent were dispersed by a disperser, and thereafter, a crosslinking agent, a photoradical generator, and an onium salt were added to prepare red, green, and blue photosensitive coloring compositions, respectively. The composition ratio of this photosensitive coloring composition is such that 10 g of resin, 9 g of pigment,
0.9 g of dispersant, 6 g of crosslinking agent, 1 g of photoradical generator,
Onium salt was 1 g, and a solvent was added so that the concentration of the total solid content in the photosensitive coloring composition was 20% by weight.

(Preparation of Color Filter) A blue photosensitive coloring composition is spin-coated on a transparent glass substrate,
Dried in the oven. Next, exposure (45 mJ / cm ² ) was performed using a predetermined glass mask. This was heated on a hot plate at 110 ° C. for 1 minute to crosslink and cure the photosensitive coloring composition. Thereafter, the film was developed by immersion in a 0.3% aqueous solution of sodium carbonate for 45 seconds and washed well with water. This was rubbed with a soft sponge to remove the pigment adhering to the substrate, washed with water and dried, and baked at 230 ° C. for 30 minutes to form a blue pattern. The above series of steps was similarly repeated on the same substrate to form green and red patterns. The film thickness of each color was 1.4 μm. The thus obtained colored pattern was a high-definition 10 μm square, and the shape was vertically steep. Further, the heat resistance was excellent, with a decrease in transmittance at 460 nm of 0.5% or less when heated at 250 ° C. for 1 hour. Chemical resistance is NMP and 5
Excellent performance was shown by immersion in% NaOH.

<Example 2> (Preparation of photosensitive composition)
Using p-hydroxystyrene / methacrylic acid / 2-hydroxyethyl methacrylate / butyl methacrylate copolymer (weight composition ratio: 15/25/20/40), hexamethoxymethylmelamine (Sanwa Chemical Co., Ltd.) as a crosslinking agent Manufactured by Nikalac MW-30M) and 2-benzyl-2-dimethylamino-1- (4-morpholino-phenyl) butanone-1 (Circa Geigy KK: [Irgacure 369]) as a photoradical generator And triphenylsulfonium trifluoromethanesulfonate (manufactured by Midori Kagaku Co., Ltd .: "T
PS-105 "), cyclohexanone was used as a solvent, and a resin, a crosslinking agent, a photoradical generator, and an onium salt were added to the solvent to prepare a photosensitive composition. The composition ratio of the photosensitive composition is as follows: 10 g of the resin, 6 g of a crosslinking agent,
1 g of a photo radical generator and 1 g of an onium salt were prepared so that the total solid content in the photosensitive composition was 18% by weight.

(Preparation of Pattern) The photosensitive composition was spin-coated on a substrate and dried in an oven at 70 ° C. Next, exposure using a predetermined glass mask (20 mJ / c
m ² ). This was heated on a hot plate at 110 ° C. for 1 minute to crosslink and cure the photosensitive composition. Thereafter, the film was developed by immersion in a 0.1% aqueous sodium carbonate solution for 30 seconds, washed and dried, and baked at 150 ° C. for 1 hour to form a pattern. The film thickness of the pattern was 1.0 μm. The pattern thus obtained was a 3 μm square high-definition pattern, and the shape of the pattern stood vertically.
Regarding heat resistance, heating at 250 ° C. for 1 hour
It had high heat resistance with a decrease in transmittance at 60 nm of 0.5% or less. Also, regarding chemical resistance, NMP, 5
There was no problem when immersed in each of NaOH for 20 minutes.

<Example 3> (Preparation of photosensitive coloring composition) 2-Benzyl-2-dimethylamino-1- as the photoradical generator used in the preparation of the photosensitive coloring composition in Example 1 above. Instead of (4-morpholino-phenyl) butanone-1 (manufactured by Ciba Geigy KK: [Irgacure 369]), 2-
(P-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine (manufactured by Midori Kagaku Co., Ltd .: "T
AZ-110 "). With respect to other compositions, the same photosensitive coloring composition as the composition in Example 1 was prepared.

(Preparation of Color Filter) A blue photosensitive coloring composition was spin-coated on a transparent glass substrate,
Dried in the oven. Next, exposure (15 mJ / cm ² ) was performed using a predetermined glass mask. This was heated on a hot plate at 110 ° C. for 1 minute to crosslink and cure the photosensitive coloring composition. Thereafter, the film was immersed in a 0.3% aqueous solution of sodium carbonate for 55 seconds, developed, and washed well with water. This was rubbed with a soft sponge to remove the pigment adhering to the substrate, washed with water and dried, and baked at 200 ° C. for 30 minutes to form a blue pattern. The above series of steps was similarly repeated on the same substrate to form green and red patterns. The film thickness of each color was 1.4 μm. The thus obtained colored pattern was a high-definition 10 μm square, and the shape was vertically steep. Further, the heat resistance was excellent, with a decrease in transmittance at 460 nm of 0.5% or less when heated at 250 ° C. for 1 hour. Chemical resistance is NMP and 5
Excellent performance was shown by immersion in% NaOH.

Example 4 (Preparation of photosensitive coloring composition) Triphenylsulfonium trifluoromethanesulfonate (Midori Chemical Co., Ltd.) as the onium salt used in the preparation of the photosensitive coloring composition in Example 3 above Manufactured by "TPS-105") instead of 4-phenylthiophenyldiphenylsulfonium hexafluorophosphonate (manufactured by Midori Kagaku Co., Ltd.):
"DTS-102") was used. With respect to other compositions, the same photosensitive coloring composition as in Example 3 was prepared.

(Preparation of Color Filter) A blue photosensitive coloring composition was spin-coated on a transparent glass substrate,
Dried in the oven. Next, exposure (15 mJ / cm ² ) was performed using a predetermined glass mask. This was heated on a hot plate at 110 ° C. for 1 minute to crosslink and cure the photosensitive coloring composition. Thereafter, the film was developed by immersion in a 0.3% aqueous solution of sodium carbonate for 60 seconds and washed well with water. This was rubbed with a soft sponge to remove the pigment adhering to the substrate, washed with water and dried, and baked at 200 ° C. for 30 minutes to form a blue pattern. The above series of steps was similarly repeated on the same substrate to form green and red patterns. The film thickness of each color was 1.4 μm. The thus obtained colored pattern was a high-definition 10 μm square, and the shape was vertically steep. Further, the heat resistance was excellent, with a decrease in transmittance at 460 nm of 0.5% or less when heated at 250 ° C. for 1 hour. Chemical resistance is NMP and 5
Excellent performance was shown by immersion in% NaOH.

<Comparative Example 1> (Preparation of photosensitive coloring composition) The photo-radical generator used in the preparation of the photosensitive coloring composition in Example 1 was not used. A photosensitive coloring composition identical in composition was prepared.

(Preparation of Color Filter) A blue photosensitive coloring composition was spin-coated on a transparent glass substrate and heated at 70 ° C.
Dried in the oven. Next, exposure (150 mJ / cm ² ) was performed using a predetermined glass mask. This is 110 ° C
For 1 minute on a hot plate to crosslink and cure the photosensitive coloring composition. Thereafter, the film was developed by immersion in a 0.3% aqueous solution of sodium carbonate for 45 seconds and washed well with water.
This was rubbed with a soft sponge to remove the pigment adhering to the substrate, washed with water and dried, and baked at 200 ° C. for 30 minutes to form a blue pattern. The above series of steps was similarly repeated on the same substrate to form green and red patterns.
The film thickness of each color was 1.4 μm. The shape of the colored pattern thus obtained was reverse tapered due to low sensitivity.

<Comparative Example 2> (Preparation of photosensitive coloring composition) The onium salt used in the preparation of the photosensitive coloring composition in Example 3 was not used. The same photosensitive coloring composition was prepared.

(Preparation of Color Filter) A blue photosensitive coloring composition was spin-coated on a transparent glass substrate,
Dried in the oven. Next, exposure (50 mJ / cm ² ) was performed using a predetermined glass mask. This was heated on a hot plate at 110 ° C. for 1 minute to crosslink and cure the photosensitive coloring composition. Thereafter, the film was immersed in a 0.1% aqueous sodium hydroxide solution for 50 seconds, developed, and washed well with water.
This was rubbed with a soft sponge to remove the pigment adhering to the substrate, washed with water and dried, and baked at 200 ° C. for 30 minutes to form a blue pattern. The above-mentioned series of steps was similarly repeated on the same substrate to form green and red patterns.
The film thickness of each color was 1.4 μm. The thus obtained colored pattern was a high-definition 10 μm square, and the shape was vertically steep. However, heat resistance is 250 ° C1
Upon heating for a time, the transmittance decrease at 460 nm was 3%. As for chemical resistance, the pattern was swelled and peeled by immersion in 5% NaOH for 20 minutes.

[0046]

According to the photosensitive composition and the photosensitive coloring composition of the present invention, since the photoinitiator is a combination of a photoradical generator and an onium salt, the decrease in transmittance due to heating is small. A photosensitive composition and a photosensitive coloring composition capable of forming a high-definition pattern having excellent properties, excellent chemical resistance, high sensitivity, high process stability, good shape, high dimensional accuracy, and the like can be obtained. . Further, by producing a color filter using the photosensitive coloring composition according to the present invention,
A color filter with high heat resistance, excellent chemical resistance, high sensitivity, high process stability, good shape, high dimensional accuracy, and high definition pattern with little decrease in transmittance due to heating. be able to.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/028 G03F 7/028 7/029 7/029

Claims (3)

[Claims] 1. A photosensitive composition comprising a resin curable by an acid, a crosslinking agent, and a photoinitiator as main components, wherein the photoinitiator is a combination of a photoradical generator and an onium salt. A photosensitive composition comprising: 2. A photosensitive coloring composition comprising a resin curable by an acid, a crosslinking agent, a photoinitiator, and a pigment as a main component, wherein the photoinitiator is a combination of a photoradical generator and an onium salt. A photosensitive colored composition, characterized in that: 3. A color filter using the photosensitive coloring composition according to claim 2.