JP3503460B2 - Photosensitive composition, photosensitive colored composition and color filter using the photosensitive colored composition - Google Patents

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 pattern formation, color filter formation, etc. used for manufacturing a display. For a photosensitive composition for, a photosensitive coloring composition, and a color filter using the photosensitive coloring composition, more specifically, excellent in heat resistance, high sensitivity, the latitude during alkali development is Wide, high process stability, good shape, high dimensional accuracy and high-definition pattern,
The present invention relates to a photosensitive composition capable of efficiently producing a color filter and the like with an excellent yield, a photosensitive coloring composition, and a color filter using the photosensitive coloring composition.

[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 Coloring compositions and the like are mainly used (JP-A-1-152449). Although the system using the radical polymerization has high sensitivity, it is difficult to form a pattern in an oxygen atmosphere because it is easily affected by oxygen during exposure, and a large amount of exposure is required. Therefore, it is necessary to form an oxygen blocking film and perform exposure in a state in which it is hardly affected by oxygen, which complicates the process.

As a photosensitive coloring composition for solving such a problem, for example, an acid-curable resin containing a phenol and a crosslinking agent having an N-methylol structure, which are disclosed in JP-A-4-163552, are used. 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 by this photosensitive composition is vertically vertical. It was a feature. The method for forming a pattern using this photosensitive composition is to apply the composition on a substrate, generate an acid by pattern exposure, heat the exposed substrate, and cure the resin by an acid-catalyzed crosslinking reaction, A pattern can be formed by performing alkali development.

However, when a pattern is formed by a photosensitive coloring composition using a novolac resin or a homopolymer of p-hydroxystyrene as a resin containing phenol, the heat resistance is poor and the resin yellows due to heating, resulting in a colored resin layer. In some cases, the phenomenon that the transmittance of P.

When a p-hydroxystyrene copolymer is used as the phenol-containing resin, it is 230 ° C. 1
With heating for a time, there is almost no decrease in transmittance,
When heated at a temperature higher than that, a phenomenon in which the transmittance was lowered sometimes occurred.

Acrylic resins having a carboxylic acid and a hydroxyl group have been studied as a resin that is cured by an acid for further improving heat resistance, and a heat resistance that does not cause a decrease in transmittance even when heated at 250 ° C. for 1 hour was obtained. , The difference in alkali dissolution rate between exposed and unexposed areas is not sufficiently obtained, the range of development conditions is narrow, and the shape of the formed pattern causes fringe changes due to changes in development conditions, and the pattern dimensions change. Something happened.

[0007]

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 high heat resistance and high sensitivity with little decrease in transmittance due to heating. A photosensitive composition capable of forming a high-definition pattern having a good shape and good dimensional accuracy, having high alkali solubility in the unexposed area, wide latitude in alkali development, high process stability, and photosensitivity. It is intended to provide a coloring composition and a color filter using the photosensitive coloring composition.

[0008]

SUMMARY OF THE INVENTION The present invention is a photosensitive composition containing an acid-curable resin, a cross-linking agent, and a photo-acid generator as main components, wherein the acid-curable resin has the following main components:
It is a photosensitive composition characterized by being a copolymer comprising an unsaturated carboxylic acid alkyl ester monomer having two adjacent hydroxyl groups in the molecule and an unsaturated carboxylic acid monomer having a carboxyl group.

The present invention also provides a resin which is cured by an acid,
Crosslinking agent, photoacid generator, a photosensitive coloring composition containing a pigment as a main component, wherein the main component of the resin curable by the acid is
A photosensitive coloring composition characterized in that it is a copolymer consisting of an unsaturated carboxylic acid alkyl ester monomer having two hydroxyl groups adjacent to each other in the molecule and an unsaturated carboxylic acid monomer having a carboxyl group. .

The present invention also provides a resin which is cured by an acid,
Crosslinking agent, photoacid generator, a photosensitive coloring composition containing a pigment as a main component, wherein the main component of the resin curable by the acid is
The above-mentioned photosensitive coloring composition, which is a copolymer composed of an unsaturated carboxylic acid alkyl ester monomer having two hydroxyl groups adjacent to each other in the molecule, and an unsaturated carboxylic acid monomer having a carboxyl group. It is a color filter characterized by being used.

The present invention also provides a resin which is cured by an acid,
A low-molecular weight compound whose polarity is changed by an acid, a cross-linking agent, and a photosensitive composition containing a photo-acid generator as a main component, wherein the low-molecular weight compound whose polarity is changed by an acid is represented by the chemical formula (2). A photosensitive composition characterized by being a low molecular weight compound.

[Chemical 3]

The present invention also provides a resin which is cured by an acid,
A low-molecular weight compound whose polarity is changed by an acid, a cross-linking agent, a photo-acid generator, a photosensitive coloring composition containing a pigment as a main component,
The low-molecular weight compound whose polarity is changed by the acid is a low-molecular weight compound represented by the chemical formula (2), which is a photosensitive coloring composition.

[Chemical 4]

The present invention also provides a resin which is cured by an acid,
A low-molecular weight compound whose polarity is changed by an acid, a cross-linking agent, a photo-acid generator, a photosensitive coloring composition containing a pigment as a main component,
A color filter using the photosensitive composition, wherein the low molecular weight compound whose polarity is changed by the acid is a low molecular weight compound represented by the chemical formula (2).

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below based on one embodiment. The copolymer in which the main component of the acid-curable resin in the present invention is a monomer of an unsaturated carboxylic acid alkyl ester having two hydroxyl groups adjacent to each other in the molecule and a monomer of an unsaturated carboxylic acid having a carboxyl group. As the monomer of the unsaturated carboxylic acid alkyl ester having two adjacent hydroxyl groups in the molecule used for the resin (hereinafter referred to as the copolymer resin), the one represented by the chemical formula (1) can be used. .

[0015]

[Chemical 5]

Further, as the unsaturated carboxylic acid monomer having a carboxyl group used for the above-mentioned copolymer resin,
Acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, etc. can be used. Further, as the other monomer used for the copolymer resin, acrylic acid-based monomer, methacrylic acid-based monomer, styrene, phenylmaleimide and the like can be used. Particularly, from the viewpoint of improving heat resistance, a copolymer with an acrylic acid-based monomer or a methacrylic acid-based monomer is preferable. Methyl acrylate, ethyl acrylate, butyl acrylate, 2-hydroxyethyl acrylate, cyclohexyl acrylate, benzyl acrylate, etc. can be used as the acrylic acid-based monomer, and methyl methacrylate is used as the methacrylic acid-based monomer. , Ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate and the like can be used.

By using an unsaturated carboxylic acid alkyl ester monomer having two adjacent hydroxyl groups in the molecule as the copolymer resin, two adjacent hydroxyl groups are dehydrated by heating in the presence of an acid generated after exposure. The reaction causes a ketone structure, the polarity of the resin is reduced, and the alkali solubility is significantly reduced. As a result, the difference between the alkali dissolution rate of the crosslinked exposed area and the alkali dissolution rate of the uncrosslinked unexposed area is expanded, the range of development conditions is widened, and the shape of the formed pattern is stable against changes in development conditions. It is possible to obtain a highly precise pattern.

As the copolymer composition of the copolymer resin, the content of the unsaturated carboxylic acid alkyl ester monomer having two adjacent hydroxyl groups in the molecule is 5 to 50% by weight.
Is preferred. If it is less than 5% by weight, the effect of lowering the alkali solubility due to the polarity change cannot be obtained, and if it is more than 50% by weight, the storage stability of the photosensitive coloring composition is deteriorated. The content of the unsaturated carboxylic acid monomer having a carboxyl group is preferably 5 to 40% by weight. If it is less than 5% by weight, the alkali solubility of the resin in the unexposed state is too low to develop, and if it is more than 40% by weight, the alkali solubility becomes too high and the effect of decreasing the alkali solubility due to polarity change is offset.

Further, in the present invention, a resin which is cured by an acid, a low molecular weight compound whose polarity is changed by an acid, a crosslinking agent
A photosensitive composition mainly comprising a photo-acid generator, wherein the low molecular weight compound whose polarity is changed by the acid is represented by the chemical formula (2)
Examples of the resin in the photosensitive composition characterized by being a low molecular weight compound represented by: are phenol and novolak, phenols typified by p-hydroxystyrene, a monomer having a carboxyl group and a hydroxyl group. A resin that is a copolymer of the monomers that it has (hereinafter referred to as the copolymer resin 2) can be used. From the viewpoint of heat resistance of the resin itself, the content of the phenolic monomer is preferably 50% by weight or less of the copolymer resin 2.

As the above-mentioned monomer having a carboxyl group, acrylic acid which is a monomer of unsaturated carboxylic acid,
Methacrylic acid, maleic acid, fumaric acid, crotonic acid, etc. can be used. Further, as the monomer having a hydroxyl group, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxymethacrylate. Monomers of hydroxy compounds of unsaturated carboxylic acid alkyl esters such as propyl, 2-hydroxybutyl methacrylate, and 4-hydroxybutyl methacrylate can be used.

Further, other monomers which can be used for the copolymerization include styrene, phenylmaleimide, methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, benzyl acrylate, methyl methacrylate, ethyl methacrylate and methacrylic acid. Butyl acid,
Examples thereof include cyclohexyl methacrylate and benzyl methacrylate.

The low molecular weight compound whose polarity changes with acid is represented by the chemical formula (2).

[0023]

[Chemical 6]

The above-mentioned low molecular weight compound has two hydroxyl groups and is in a state of high polarity before exposure and heating, but by heating in the presence of an acid generated after exposure, two adjacent hydroxyl groups cause a dehydration reaction and a ketone structure. And the polarity is significantly reduced.
Therefore, in the cross-linked exposed area, the polarity of the low molecular weight compound is lowered, so that the permeation of the alkali developing solution is suppressed and almost no dissolution occurs. On the other hand, the unexposed portion of the coating film formed from this photosensitive composition has a high polarity and a small molecular weight of the low molecular weight compound, so that the alkali developer penetrates quickly and the alkali solubility is significantly increased. There is.
As a result, the difference between the alkali dissolution rate of the crosslinked exposed area and the alkali dissolution rate of the uncrosslinked unexposed area is expanded, the range of development conditions is widened, and the shape of the formed pattern is stable against changes in development conditions. It is possible to obtain a highly precise pattern. The amount of the low molecular weight compound added is preferably 5 to 80% by weight based on 100 parts by weight of the copolymer resin 2.

As the cross-linking agent in the present invention, for example, methylolated urea, urea resin, methylolated melamine,
Butyrolylated melamine, methylol guanamine, or alkyl ethers of these compounds can be used, and the alkyl ether compound is more preferable from the viewpoint of high thermal stability. The alkyl group of this alkyl ether is preferably an alkyl group having 1 to 5 carbon atoms. In particular,
As the alkyl ether compound, an alkyl ether compound of hexamethylolmelamine is more preferable from the viewpoint of sensitivity.

The cross-linking agent causes a cross-linking reaction with the copolymer resin or the copolymer resin 2 by heating in the presence of an acid generated after exposure to form a pattern. The amount of the crosslinking agent added is about 5 to 100 parts by weight with respect to 100 parts by weight of the copolymer resin or the copolymer resin 2.

As the photo-acid generator in the present invention, a trihalomethyl group-containing triazine derivative or onium salt which can generate an acid by absorbing light can be used. Examples of the trihalomethyl group-containing triazine derivative include 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- (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 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- Toluene sulfonate, 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
Diaryl iodonium salts such as rt-butylphenyl) iodonium trifluoroacetate and 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, 4 -Methoxyphenyldiphenylsulfonium hexafluoroal Sulfonate, 4-methoxyphenyl diphenyl sulfonium trifluoromethanesulfonate,
4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium-p-trienesulfonate, 4-phenylthiophenyldiphenyltetrafluoroborate, 4-phenylthiophenyldiphenylhexafluorophosphonate, 4-phenylthiophenyldiphenylhexa Examples thereof include triarylsulfonium salts such as fluoroarsenate, 4-phenylthiophenyldiphenyltrifluoromethanesulfonate, 4-phenylthiophenyldiphenyltrifluoroacetate and 4-phenylthiophenyldiphenyl-p-toluenesulfonate.

As the photoacid generator, use of these trihalomethyl group-containing triazine derivatives is preferable, and the trihalomethyl group-containing triazine derivative has an absorption edge near a wavelength of 300 nm to 400 nm and has a longer wavelength than that of onium salts. Since an acid is generated by the light in the region of 1, there is an advantage that the pattern can be formed with sufficient sensitivity even when a glass mask is used as a mask during pattern exposure.

These photoacid generators may be used alone or in combination. For example, a combination of a light absorber and an acid generator can be used. The addition amount is preferably 0.5 to 40% by weight with respect to the resin material. This is because when added in excess of 40% by weight, the amount of acid generated is too large and the acid diffuses into the unexposed area due to heating after pattern exposure to cause a crosslinking reaction, resulting in a decrease in resolution. Become. If the amount added is less than 0.5% by weight, the amount of acid generated is insufficient, the crosslinking reaction does not proceed sufficiently, and a pattern cannot be formed.

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

These pigments may be used alone or as a mixture, and the addition amount thereof 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. Used at 10-60% by weight.

The photosensitive composition and the photosensitive coloring composition of the present invention may further contain additives if necessary. Specific examples of such additives include pigment dispersants, dissolution promoters, adhesion promoters, antioxidants, ultraviolet absorbers, and sensitizers.

As the dispersant, a wide range of dispersants such as surfactants, pigment derivatives, and "Solspers" manufactured by Zeneca Corporation are used. The addition amount of these dispersants is 1
It is used in an amount of about 1 to 30% by weight with respect to 00% by weight.

Other solvents include toluene, xylene, ethyl cellosolve, ethyl cellosolve acetate,
Diethylene glycol dimethyl ether, cyclohexanone, etc. are used, and these solvents may be used alone or in combination. The amount of these solvents to be added is preferably such that the concentration of the total solid content in the photosensitive composition and the 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 has a transparent substrate on which the photosensitive coloring composition of the present invention is applied over the entire surface, dried, and subjected to pattern exposure from the substrate to generate an acid in the composition. Then, the composition is heated to cure, and the colored resin layer is formed by developing the composition with an alkali developing solution and leaving the cured composition in a pattern, and a series of steps including these is repeated to form a plurality of layers on the same substrate. It can be manufactured by a process of forming a colored resin layer of color.

As the heating method, a heating device such as an oven or a hot plate can be used, and the temperature is 7
A temperature of 0 to 150 ° C is suitable.

Examples of the alkaline developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate, alkylamines such as triethylamine, alcohol amines such as triethanolamine, and tetramethylammonium hydroxide. Quaternary ammonium salts such as and the like can be used.

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

As described above, in the photosensitive composition and the photosensitive coloring composition of the present invention, as a resin that is cured by an acid, a monomer of an unsaturated carboxylic acid alkyl ester having two adjacent hydroxyl groups in the molecule is used. , And by using a copolymer containing an unsaturated carboxylic acid monomer having a carboxyl group, two adjacent hydroxyl groups undergo a dehydration reaction due to heating in the presence of an acid generated after exposure to form a ketone structure. , The polarity of the resin is lowered and the alkali solubility is lowered. At the same time, the unreacted hydroxyl group and carboxyl group cause a crosslinking reaction with the crosslinking agent by heating in the presence of an acid, resulting in a decrease in alkali solubility. Due to this decrease in the double alkali solubility, the alkali dissolution rate of the cross-linked exposed area is significantly reduced and the difference from the alkali dissolution rate of the unexposed area is expanded. By this action, the range of development conditions is widened, and a high-definition pattern in which the shape of the pattern formed is stable against variations in development conditions can be obtained.

In the photosensitive composition and the photosensitive coloring composition of the present invention, by using the low molecular weight compound represented by the chemical formula (2), they are adjacent to each other by heating in the presence of an acid generated after exposure. The two hydroxyl groups undergo a dehydration reaction to form a ketone structure, the polarity is significantly reduced, and the alkali solubility is reduced. At the same time, the OH group of the resin causes a cross-linking reaction with the cross-linking agent by heating in the presence of an acid, and the alkali solubility is lowered. This double decrease in alkali solubility and, on the other hand, the unexposed portion of the coating film formed from this photosensitive composition, because of the high polarity and low molecular weight of the low molecular weight compound, Rapidly penetrates and the alkali solubility is significantly higher. As a result, the alkali dissolution rate of the cross-linked exposed area is significantly reduced, and the difference from the alkali dissolution rate of the unexposed area is enlarged. By this action, the range of development conditions is widened, and a high-definition pattern in which the shape of the pattern formed is stable against variations in development conditions can be obtained.

Further, by using the photosensitive coloring composition of the present invention, the latitude during alkali development is wide,
It is possible to form a color filter having high process stability, good shape, high-definition pattern with high dimensional accuracy, high sensitivity, and heat resistance that does not cause a decrease in transmittance even when heated at 250 ° C. for 1 hour. .

[0043]

EXAMPLES Examples of the present invention will be specifically described below. <Example 1> (Preparation of photosensitive coloring composition) As a resin that is cured with an acid, 2,3-dihydroxypropyl methacrylate / methacrylic acid / methyl methacrylate copolymer (weight composition ratio 2
5/20/55), hexamethoxymethylmelamine (manufactured by Sanwa Chemical Co., Ltd .: “Nikalac MW-30M”) as a cross-linking agent, and 2- (p-
Methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine (Midori Kagaku Co., Ltd .: “TAZ
-110 "), cyclohexanone (manufactured by Kanto Chemical Co., Inc.) as a solvent, and" Solsperse "as a dispersant.
(Manufactured by Zeneca Corporation) "S24000GR" and "S50"
"00" at a ratio of 1: 1 with "Chromophthal Sun Red" as a red pigment (manufactured by Ciba Geigy) and "Rionol Green" as a green pigment (Toyo Ink Mfg. Co., Ltd.).
Manufactured by K.K.) and "Heliogen Blue" as a blue pigment (B.A.
S. F. (Manufactured by Co., Ltd.), a resin, a pigment, a dispersant and a solvent are first dispersed by a disperser, and then a crosslinking agent and a photo-acid generator are added to obtain red, green and blue photosensitive coloring compositions, respectively. Prepared. The composition ratio of this photosensitive coloring composition is Resin 1
Pigment 9g, dispersant 0.9g, crosslinking agent 4 to 0g
and 1 g of the photo-acid generator, and the 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 was spin-coated on a transparent glass substrate, and the temperature was 70 ° C.
Oven dried. 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. After that, it was immersed in a 0.3% sodium carbonate aqueous solution for 45 seconds for development, and then thoroughly washed with water. This was rubbed with a soft sponge to remove the pigment attached to the substrate, washed with water and dried, and then baked at 230 ° C. for 1 hour 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 colored pattern obtained in this manner was a fine pattern of 10 μm square, the shape was forward taper, and no fringe was generated, and the dimensional accuracy was within ± 0.5 μm. Moreover, even if the developing time is extended to 60 seconds,
The pattern dimensions did not change. Regarding the heat resistance, it had high heat resistance such that the decrease in the transmittance at 460 nm was 2% or less even after heating at 250 ° C. for 1 hour.

<Example 2> (Preparation of photosensitive composition) As a resin which is cured by an acid,
2,3-dihydroxypropyl methacrylate / methacrylic acid / methyl methacrylate copolymer (weight composition ratio 25 /
20/55), and hexamethoxymethyl melamine (manufactured by Sanwa Chemical Co., Ltd.) as a cross-linking agent: “Nikalac MW
-30M ") and 2- (p-methoxystyryl) -4,6-bis (trichloromethyl)-as a photoacid generator.
s-triazine (Midori Kagaku Co., Ltd .: "TAZ-11"
0 ”), cyclohexanone as a solvent (Kanto Chemical Co., Inc.)
Resin), a crosslinking agent, and a photo-acid generator were dissolved in a solvent to prepare a photosensitive composition. The composition ratio of this photosensitive composition was as follows: resin 10 g, crosslinking agent 4 g, photo-acid generator 1
The solvent was added so that the total solid content of the photosensitive composition was 18% by weight.

(Preparation of Pattern) A photosensitive composition was spin-coated on a substrate and dried in an oven at 70 ° C. Next, using a predetermined glass mask, exposure (30 mJ / c
m ² ). This was heated on a hot plate at 110 ° C. for 1 minute to crosslink and cure the photosensitive composition. Then, it was immersed in a 0.1% sodium carbonate aqueous solution for 30 seconds for development, washed with water and dried, and then 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 has a high definition of 3 μm square and the shape is forward tapered and no fringes occur.
The dimensional accuracy was within 0.15 μm. Further, even if the developing time was extended to 60 seconds, the pattern dimensions did not change. Regarding the heat resistance, it had high heat resistance such that the decrease in the transmittance at 460 nm was 2% or less even after heating at 250 ° C. for 1 hour.

<Example 3> (Preparation of photosensitive coloring composition) As a resin which is cured by an acid, a methacrylic acid / 2-hydroxyethyl methacrylate / methyl methacrylate copolymer (weight composition ratio 20/15) is used.
/ 65), and hexamethoxymethylmelamine (manufactured by Sanwa Chemical Co., Ltd.) as a cross-linking agent: “Nikalac MW-3
2M (p-methoxystyryl) -4,6-bis (trichloromethyl) -s- as a photoacid generator.
Triazine (Midori Kagaku Co., Ltd .: "TAZ-11"
0 "), Pinacol in which R1 to R4 of the chemical formula (2) are all methyl groups as a low molecular weight compound whose polarity is changed by an acid, cyclohexanone as a solvent, and" Solvers "(Zeneca Corporation) as a dispersant. Made) "S
"24000GR" and "S5000" are used in a ratio of 1: 1, "chromophthalsan red" (manufactured by Ciba Geigy Co., Ltd.) as a red pigment, "Rionol Green" (manufactured by Toyo Ink Mfg. Co., Ltd.) as a green pigment, "Heliogen Blue" (manufactured by BASF Co., Ltd.) is used as a blue pigment,
First, a resin, a pigment, a dispersant and a solvent were dispersed by a disperser, and then a crosslinking agent, a photo-acid generator and a low molecular weight compound were added to prepare red, green and blue photosensitive coloring compositions, respectively.
The composition ratio of this photosensitive coloring composition was 9 g of pigment, 0.9 g of dispersant, 6 g of cross-linking agent, 4 g of low molecular weight compound and 1 g of photo-acid generator with respect to 10 g of resin. The solvent was added so that the concentration of the total solid content was 20% by weight.

(Preparation of Color Filter) A blue photosensitive coloring composition was spin-coated on a substrate such as glass to form 70
Dried in oven at 0 ° C. Next, exposure (50 mJ / cm2) was performed using a predetermined glass mask. This is 110 ℃
By heating on a hot plate for 1 minute, the photosensitive coloring composition was crosslinked and cured. After that, it was immersed in a 0.3% sodium carbonate aqueous solution for 40 seconds to develop it, and it was thoroughly washed with water.
This was rubbed with a soft sponge to remove the pigment attached to the substrate, washed with water and dried, and then baked at 230 ° C. for 1 hour to form a blue pattern. The above-described 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 colored pattern obtained in this manner was a fine pattern of 10 μm square, the shape was forward taper, and no fringe was generated, and the dimensional accuracy was within ± 0.5 μm. Further, even if the developing time was extended to 60 seconds, the pattern dimensions did not change. Regarding the heat resistance, it had high heat resistance such that the decrease in the transmittance at 460 nm was 2% or less even after heating at 250 ° C. for 1 hour.

Example 4 (Preparation of Photosensitive Coloring Composition) As a resin which is cured by an acid, a 2,3-dihydroxypropyl methacrylate / methacrylic acid / ethyl methacrylate copolymer (weight composition ratio 3
0/15/55), hexamethoxymethylmelamine (manufactured by Sanwa Chemical Co., Ltd .: “Nikalac MW-30M”) as a cross-linking agent, and 2- (p-
Methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine (Midori Kagaku Co., Ltd .: “TAZ
-110 "), cyclohexanone (manufactured by Kanto Chemical Co., Inc.) as a solvent, and" Solsperse "as a dispersant.
(Manufactured by Zeneca Corporation) "S24000GR" and "S50"
"00" at a ratio of 1: 1 with "Chromophthal Sun Red" as a red pigment (manufactured by Ciba Geigy) and "Rionol Green" as a green pigment (Toyo Ink Mfg. Co., Ltd.).
Manufactured by K.K.) and "Heliogen Blue" as a blue pigment (B.A.
S. F. (Manufactured by Co., Ltd.), a resin, a pigment, a dispersant and a solvent are first dispersed by a disperser, and then a crosslinking agent and a photo-acid generator are added to obtain red, green and blue photosensitive coloring compositions, respectively. Prepared. The composition ratio of this photosensitive coloring composition is Resin 1
Pigment 9g, dispersant 0.9g, crosslinking agent 4 to 0g
and 1 g of the photo-acid generator, and the 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 was spin-coated on a transparent glass substrate, and the temperature was 70 ° C.
Oven dried. 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. After that, it was immersed in a 0.5% aqueous sodium carbonate solution for 40 seconds to develop it, and it was thoroughly washed with water. This was rubbed with a soft sponge to remove the pigment attached to the substrate, washed with water and dried, and then baked at 230 ° C. for 1 hour 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 colored pattern obtained in this manner was a fine pattern of 10 μm square, the shape was forward taper, and no fringe was generated, and the dimensional accuracy was within ± 0.5 μm. Also, even if the development time is extended to 55 seconds,
The pattern dimensions did not change. Regarding the heat resistance, it had high heat resistance such that the decrease in the transmittance at 460 nm was 2% or less even after heating at 250 ° C. for 1 hour.

<Example 5> (Preparation of photosensitive composition) As a resin which is cured by an acid,
Methacrylic acid / 2-hydroxyethyl methacrylate //
Methyl methacrylate copolymer (weight composition ratio 20/15 /
60), and hexamethoxymethylmelamine (manufactured by Sanwa Chemical Co., Ltd .: “Nikalac MW-30” as a crosslinking agent.
M ”) as a photo-acid generator, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine (Midori Kagaku Co., Ltd .:“ TAZ-11 ”).
0 ”), as a low molecular weight compound whose polarity changes with acid,
All of R _{1 to} R _{4 in} the chemical formula (2) are methyl groups, Pinacol is used, cyclohexanone (Kanto Chemical Co., Inc.) is used as a solvent, and a resin, a low molecular compound, a cross-linking agent, and a photo-acid generator are used as a solvent. It melt | dissolved and prepared the photosensitive composition. The composition ratio of this photosensitive composition is 10 g of resin, 3 g of low molecular weight compound, 4 g of cross-linking agent, and 1 g of photo-acid generator, and the concentration of total solid content in the photosensitive composition is 18% by weight. So the solvent was added.

(Preparation of Pattern) A photosensitive composition was spin-coated on a substrate and dried in an oven at 70 ° C. Next, using a predetermined glass mask, exposure (30 mJ / c
m ² ). This was heated on a hot plate at 110 ° C. for 1 minute to crosslink and cure the photosensitive composition. Then, it was immersed in a 0.05% sodium carbonate aqueous solution for 40 seconds for development, washed with water, 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 has a high definition of 3 μm square and the shape is forward tapered and no fringes occur.
The dimensional accuracy was within 0.15 μm. Further, even if the developing time was extended to 60 seconds, the pattern dimensions did not change. Regarding the heat resistance, it had high heat resistance such that the decrease in the transmittance at 460 nm was 2% or less even after heating at 250 ° C. for 1 hour.

<Example 6> (Preparation of photosensitive coloring composition) As a resin which is cured by an acid, 2,3-dihydroxypropyl methacrylate / methacrylic acid / butyl methacrylate copolymer (weight composition ratio 3
0/25/45), hexamethoxymethylmelamine (manufactured by Sanwa Chemical Co., Ltd .: “Nikalac MW-30M”) as a cross-linking agent, and 2- (p-
Methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine (Midori Kagaku Co., Ltd .: “TAZ
-110 "), cyclohexanone (manufactured by Kanto Chemical Co., Inc.) as a solvent, and" Solsperse "as a dispersant.
(Manufactured by Zeneca Corporation) "S24000GR" and "S50"
"00" at a ratio of 1: 1 with "Chromophthal Sun Red" as a red pigment (manufactured by Ciba Geigy) and "Rionol Green" as a green pigment (Toyo Ink Mfg. Co., Ltd.).
Manufactured by K.K.) and "Heliogen Blue" as a blue pigment (B.A.
S. F. (Manufactured by Co., Ltd.), a resin, a pigment, a dispersant and a solvent are first dispersed by a disperser, and then a crosslinking agent and a photo-acid generator are added to obtain red, green and blue photosensitive coloring compositions, respectively. Prepared. The composition ratio of this photosensitive coloring composition is Resin 1
Pigment 9g, dispersant 0.9g, crosslinking agent 4 to 0g
and 1 g of the photo-acid generator, and the 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 was spin-coated on a transparent glass substrate, and the temperature was 70 ° C.
Oven dried. 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. After that, it was immersed in a 0.1% sodium hydroxide aqueous solution for 30 seconds to develop it, and it was thoroughly washed with water.
This was rubbed with a soft sponge to remove the pigment attached to the substrate, washed with water and dried, and then baked at 230 ° C. for 1 hour 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 colored pattern obtained in this manner was a fine pattern of 10 μm square, the shape was forward taper, and no fringe was generated, and the dimensional accuracy was within ± 0.5 μm. Further, even when the developing time was extended to 45 seconds, the pattern dimensions did not change. Regarding the heat resistance, it had high heat resistance such that the decrease in the transmittance at 460 nm was 2% or less even after heating at 250 ° C. for 1 hour.

<Example 7> (Preparation of photosensitive coloring composition) In the photosensitive coloring composition of Example 3, R1 to R4 in the chemical formula (2) are all phenyl as a low molecular weight compound whose polarity is changed by an acid. A photosensitive coloring composition was prepared by using tetraphenyl-1,2-ethanediol as a group and making the other composition the same.

(Preparation of Color Filter) A blue photosensitive coloring composition was spin-coated on a substrate such as glass to form 70
Dried in oven at 0 ° C. Next, exposure (50 mJ / cm2) was performed using a predetermined glass mask. This is 110 ℃
By heating on a hot plate for 1 minute, the photosensitive coloring composition was crosslinked and cured. After that, it was immersed in a 0.4% sodium carbonate aqueous solution for 45 seconds to develop it, and it was thoroughly washed with water.
This was rubbed with a soft sponge to remove the pigment attached to the substrate, washed with water and dried, and then baked at 230 ° C. for 1 hour to form a blue pattern. The above-described 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 colored pattern obtained in this manner was a fine pattern of 10 μm square, the shape was forward taper, and no fringe was generated, and the dimensional accuracy was within ± 0.5 μm. Further, even if the developing time was extended to 60 seconds, the pattern dimensions did not change. Regarding the heat resistance, it had high heat resistance such that the decrease in the transmittance at 460 nm was 2% or less even after heating at 250 ° C. for 1 hour.

<Example 8> (Preparation of photosensitive coloring composition) In the photosensitive coloring composition of Example 3, as a resin curable by acid, p-hydroxystyrene / methacrylic acid / 2-hydroxymethacrylic acid was used. Ethyl / butyl methacrylate copolymer (weight composition ratio 3
(0/20/20/30) and other compositions were the same to prepare a photosensitive coloring composition.

(Preparation of Color Filter) A blue photosensitive coloring composition was spin-coated on a transparent substrate such as glass,
It was dried in an oven at 70 ° C. Next, exposure (50 mJ / cm2) was performed using a predetermined glass mask. This 11
The photosensitive coloring composition was crosslinked and cured by heating on a hot plate at 0 ° C. for 1 minute. After that, it was immersed in a 0.1% sodium hydroxide aqueous solution for 30 seconds to develop it, and it was thoroughly washed with water. This was rubbed with a soft sponge to remove the pigment attached to the substrate, washed with water and dried, and then baked at 230 ° C. for 1 hour to form a blue pattern. The above-described 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 colored pattern obtained in this manner was a fine pattern of 10 μm square, the shape was forward taper, and no fringe was generated, and the dimensional accuracy was within ± 0.5 μm. Further, even when the developing time was extended to 45 seconds, the pattern dimensions did not change. Regarding the heat resistance, it had high heat resistance such that the decrease in the transmittance at 460 nm was 2% or less even after heating at 250 ° C. for 1 hour.

Comparative Example 1 (Preparation of Photosensitive Coloring Composition) As a resin which is cured by an acid, 2-hydroxyethyl methacrylate / methacrylic acid / butyl methacrylate copolymer (weight composition ratio 30/25
/ 45), and hexamethoxymethyl melamine (manufactured by Sanwa Chemical Co., Ltd .: “Nikalac MW-3” as a cross-linking agent.
2M (p-methoxystyryl) -4,6-bis (trichloromethyl) -s- as a photoacid generator.
Triazine (Midori Kagaku Co., Ltd .: "TAZ-11"
0 ”), cyclohexanone as a solvent (Kanto Chemical Co., Inc.)
"S24000GR" and "S5000" of "Solsperse" (manufactured by Zeneca Co., Ltd.) at a ratio of 1: 1 as a dispersant, and "Chlomophthalsan Red" (Ciba Geigy Co., Ltd.) as a red pigment. Manufactured by Toyo Ink Mfg. Co., Ltd. as a green pigment, and "Heliogen Blue" as a blue pigment (BASFF Co., Ltd.)
First, a resin, a pigment, a dispersant, and a solvent were dispersed by a disperser, and then a crosslinking agent and a photoacid generator were added to prepare red, green, and blue photosensitive coloring compositions, respectively. The composition ratio of this photosensitive coloring composition was 10 g of resin.
Pigment 9g, dispersant 0.9g, crosslinking agent 4g, photo-acid generator 1
and the total solid content of the photosensitive coloring composition is 20.
Solvent was added so that it would be wt%.

(Preparation of color filter) A blue photosensitive coloring composition was spin-coated on a transparent glass substrate, and 70 ° C.
Oven dried. 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. After that, it was immersed in a 0.3% sodium carbonate aqueous solution for 30 seconds for development, and washed well with water. This was rubbed with a soft sponge to remove the pigment attached to the substrate, washed with water and dried, and then baked at 230 ° C. for 1 hour 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. In the colored pattern thus obtained, fringes occurred, and the dimensional variation of the pattern was ± 2 μm or more. Also, the development time is 4
When extended to 5 seconds, peeling of the pattern occurred.

Comparative Example 2 (Preparation of Photosensitive Coloring Composition) The same photosensitive coloring composition as in the photosensitive coloring composition of Example 3 except that the low molecular weight compound whose polarity is changed by acid is removed. The thing was prepared.

(Preparation of Color Filter) A blue photosensitive coloring composition was spin-coated on a transparent substrate such as glass,
It was dried in an oven at 70 ° C. Next, exposure (50 mJ / cm2) was performed using a predetermined glass mask. This 11
The photosensitive coloring composition was crosslinked and cured by heating on a hot plate at 0 ° C. for 1 minute. After that, it was immersed in a 0.3% sodium carbonate aqueous solution for 40 seconds to develop it, and it was thoroughly washed with water. This was rubbed with a soft sponge to remove the pigment attached to the substrate, washed with water and dried, and then baked at 230 ° C. for 1 hour to form a blue pattern. The above-described 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. In the colored pattern thus obtained, fringes occurred, and the dimensional variation of the pattern was ± 2 μm or more. When the development time was extended to 50 seconds, pattern peeling occurred.

[0063]

EFFECT OF THE INVENTION The photosensitive composition and the photosensitive coloring composition according to the present invention contain an unsaturated carboxylic acid alkyl ester monomer having two adjacent hydroxyl groups in the molecule as a resin curable by an acid, and Since a copolymer containing an unsaturated carboxylic acid monomer having a carboxyl group is used, polarity conversion and crosslinking of the resin occur, the difference in alkali solubility between the exposed and unexposed areas greatly expands, and during alkali development Has the effect of widening the latitude and improving process stability. Further, the pattern shape has no fringes, and it is possible to form a high-definition pattern having a good shape and high dimensional accuracy.

The photosensitive composition and the photosensitive coloring composition according to the present invention have the chemical formula (2) in which the polarity is changed by the acid.
Since a low molecular weight compound represented by is used, polarity conversion of the low molecular weight compound and crosslinking of the resin occur, the difference in alkali solubility between the exposed and unexposed areas is greatly expanded, and the latitude during alkali development becomes wider. It has the effect of increasing the process stability. Further, the pattern shape has no fringes, and it is possible to form a high-definition pattern having a good shape and high dimensional accuracy.

By using the photosensitive composition and the photosensitive coloring composition according to the present invention, in addition to the above effects, 2
2% decrease in transmittance at 460 nm even after heating at 50 ° C for 1 hour
It has an effect that a pattern having the following high heat resistance can be formed. Thereby, the transmittance of the colored pattern does not change even after the step of forming the ITO film on the substrate of the color filter.

By manufacturing a color filter using the photosensitive coloring composition according to the present invention, a color filter having excellent heat resistance, high dimensional accuracy, good shape, and high-definition pixels can be manufactured. .

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ identification code FI G02B 5/20 101 G02B 5/20 101 G03F 7/038 601 G03F 7/038 601 (56) Reference JP-A-8-92526 ( JP, A) JP 4-163552 (JP, A) JP 58-40351 (JP, A) JP 2-39048 (JP, A) JP 59-12971 (JP, A) JP 58-113256 (JP, A) JP-A-57-30770 (JP, A) JP-A-4-165359 (JP, A) International Publication 95/018399 (WO, A1) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03F ^7/ 00-7/42

Claims (6)

(57) [Claims] 1. A photosensitive composition comprising an acid-curable resin, a cross-linking agent, and a photoacid generator as main components, wherein the acid-curable resin has two main hydroxyl groups adjacent to each other in the molecule. A photosensitive composition comprising a monomer of an unsaturated carboxylic acid alkyl ester having a monomer and an unsaturated carboxylic acid monomer having a carboxyl group. 2. A photosensitive coloring composition comprising an acid-curable resin, a cross-linking agent, a photo-acid generator, and a pigment as main components, wherein the acid-curable resin main components are adjacent to each other in the molecule. A photosensitive coloring composition, which is a copolymer composed of an unsaturated carboxylic acid alkyl ester monomer having two hydroxyl groups and an unsaturated carboxylic acid monomer having a carboxyl group. 3. A color filter comprising the photosensitive coloring composition according to claim 2. 4. A photosensitive composition mainly comprising a resin which is cured by an acid, a low molecular weight compound whose polarity is changed by an acid, a cross-linking agent and a photo-acid generator, wherein the low molecular weight compound whose polarity is changed by said acid. A photosensitive composition, wherein the compound is a low molecular weight compound represented by the chemical formula (2). [Chemical 1] 5. A photosensitive coloring composition mainly comprising a resin which is cured by an acid, a low molecular weight compound whose polarity is changed by an acid, a cross-linking agent, a photo-acid generator and a pigment, wherein the polarity is changed by the acid. The photosensitive coloring composition, wherein the low-molecular compound is a low-molecular compound represented by the chemical formula (2). [Chemical 2] 6. A color filter comprising the photosensitive coloring composition according to claim 5.