JPH10301267A - Photosensitive composition, colored photosensitive composition and color filter using its colored photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the photosensitive composition, the colored one, and the color filter small in drop of transmittance due to heating and high in heat resistance and sensitivity and good in the form and high in dimensional precision by using an acid hardenable resin composed essentially of repeating units derived from alkyl-unsaturated-carboxylate monomer having hydroxyl groups and those derived from an unsaturated carboxylic acid monomer. SOLUTION: The photosensitive composition is composed essentially composed of the acid-hardenable resin, a cross-linking agent, and an acid photogenerator, and a low-molecular weight compound changeable in polarity by an acid, and this acid-hardenable resin is composed essentially of repeating units each derived from an alkyl-unsaturated-carboxylate monomer having 2 hydroxyl groups adjacent to each other in the molecule and those each derived from the unsaturated carboxylic acid monomer, and the low-molecular weight compound changeable in polarity by an acid is represented by the formula in which each of R1 -R4 is, independently, a 1-8C alkyl or aryl group.

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, high sensitivity, and a latitude during alkali development. Wide, high process stability, good shape, high dimensional accuracy, high definition pattern,
The present invention relates to a photosensitive composition, a photosensitive coloring composition, and a color filter using the photosensitive coloring composition, which can efficiently produce a color filter or the like with an excellent yield.

[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. A 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 alkali development.

However, when a pattern is formed with a photosensitive coloring composition using a novolak resin or a homopolymer of p-hydroxystyrene as a resin containing phenol, heat resistance is poor, and the resin is yellowed by heating to cause a coloring resin layer. In some cases, a phenomenon that the transmittance of the film decreases.

When a copolymer of p-hydroxystyrene is used as the phenol-containing resin,
When heating for a long time, transmittance hardly decreases,
Heating at a higher temperature may cause a phenomenon in which the transmittance is reduced.

An acrylic resin having a carboxylic acid and a hydroxyl group has been studied as a resin which is cured by an acid in order to further improve heat resistance. As for heat resistance, a resin which does not cause a decrease in transmittance even when heated at 250 ° C. for 1 hour was obtained. The difference in the alkali dissolution rate between the exposed and unexposed areas cannot be obtained sufficiently, the width of the developing conditions is narrow, and the fluctuations in the developing conditions cause the shape of the formed pattern to draw fringes and change the pattern dimensions. Things happened.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in order to solve the above-mentioned problems, and it is an object of the present invention to provide a high-sensitivity, high-heat-resistance, low transmittance decrease by heating. Highly soluble alkali in the unexposed area, wide latitude during alkaline development, high process stability, good shape, high dimensional accuracy It is to provide a coloring composition and a color filter using the photosensitive coloring composition.

[0008]

The present invention relates to a photosensitive composition comprising a resin curable by an acid, a crosslinking agent and a photoacid generator as main components, wherein the main component of the resin curable by the acid is:
A photosensitive composition comprising a copolymer of a monomer of an unsaturated carboxylic acid alkyl ester having two hydroxyl groups adjacent to each other in a molecule and a monomer of an unsaturated carboxylic acid having a carboxyl group.

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

[0010] The present invention also provides a resin curable by an acid,
Crosslinking agent, photoacid generator, a photosensitive coloring composition containing a pigment as a main component, the main component of the resin that is cured by the acid,
The photosensitive coloring composition, wherein the monomer is a monomer of an unsaturated carboxylic acid alkyl ester having two hydroxyl groups adjacent to each other in a molecule and a monomer of an unsaturated carboxylic acid having a carboxyl group. A color filter characterized in that it is used.

Further, the present invention provides a resin curable by an acid,
A photosensitive composition mainly composed of a low molecular compound whose polarity is changed by an acid, a crosslinking agent, and a photoacid generator, wherein the low molecular compound whose polarity is changed by the acid is represented by the chemical formula (2). A photosensitive composition characterized by being a low molecular compound.

Embedded image

Further, the present invention provides a resin curable by an acid,
A low-molecular weight compound whose polarity is changed by an acid, a crosslinking agent, a photoacid generator, a photosensitive coloring composition containing a pigment as a main component,
The low-molecular compound whose polarity is changed by the acid is a low-molecular compound represented by a chemical formula (2).

Embedded image

Further, the present invention provides a resin curable by an acid,
A low-molecular weight compound whose polarity is changed by an acid, a crosslinking agent, a photoacid generator, a photosensitive coloring composition containing a pigment as a main component,
A color filter using the photosensitive composition, wherein the low molecular compound whose polarity is changed by the acid is a low molecular compound represented by a chemical formula (2).

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail below based on one embodiment. In the present invention, a main component of an acid-curable resin is a copolymer comprising a monomer of an unsaturated carboxylic acid alkyl ester having two hydroxyl groups adjacent to each other in a 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 hydroxyl groups adjacent to each other in the molecule used for the resin (hereinafter referred to as the copolymer resin), those represented by the chemical formula (1) can be used. .

[0015]

Embedded image

The unsaturated carboxylic acid monomer having a carboxyl group used in the copolymer resin includes:
Acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid and the like can be used. Further, as other monomers used for the copolymer resin, acrylic acid monomers, methacrylic acid monomers, 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. As the acrylate monomer, methyl acrylate, ethyl acrylate, butyl acrylate, 2-hydroxyethyl acrylate, cyclohexyl acrylate, benzyl acrylate, and the like can be used. As the methacrylate monomer, methyl methacrylate is used. , Ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate and the like can be used.

By using a monomer of an unsaturated carboxylic acid alkyl ester 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. A reaction takes place to form a ketone structure, the polarity of the resin is reduced, and the alkali solubility is greatly reduced. As a result, the difference between the alkali dissolution rate of the cross-linked exposed part and the alkali dissolution rate of the uncross-linked unexposed part is enlarged, the range of developing conditions is widened, and the shape of the formed pattern is stable against the fluctuation of the developing conditions. A high-definition pattern can be obtained.

As the copolymer composition of the copolymer resin, the content of the monomer of the unsaturated carboxylic acid alkyl ester having two hydroxyl groups adjacent to each other in the molecule is 5 to 50% by weight.
Is preferred. When the amount is less than 5% by weight, the effect of decreasing the alkali solubility due to the polarity change cannot be obtained, and when the amount is more than 50% by weight, the storage stability of the photosensitive coloring composition deteriorates. The content of the unsaturated carboxylic acid monomer having a carboxyl group is preferably 5 to 40% by weight. If the amount is less than 5% by weight, the alkali solubility of the resin before exposure is too low, so that development cannot be performed.

Further, in the present invention, a resin which is cured by an acid, a low molecular compound whose polarity is changed by an acid, a crosslinking agent,
A low-molecular-weight compound whose polarity is changed by the acid, which is a photosensitive composition containing a photoacid generator as a main component, is represented by a chemical formula (2):
As the resin in the photosensitive composition, which is a low-molecular compound represented by, for example, phenol novolak, phenols represented by p-hydroxystyrene, a monomer having a carboxyl group, and a hydroxyl group. A resin that is a copolymer of the monomer having the above (hereinafter referred to as the copolymer resin 2) can be used. From the viewpoint of the heat resistance of the resin itself, the content of the phenolic monomer is preferably 50% by weight or less of the copolymer resin 2.

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.

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

The above low molecular weight compound whose polarity is changed by an acid is represented by the chemical formula (2).

[0023]

Embedded image

The above low molecular weight compound has two hydroxyl groups and is in a high polarity state before the exposure heating, but by heating in the presence of the acid generated after the exposure, the adjacent two hydroxyl groups cause a dehydration reaction to cause a ketone structure. And the polarity is greatly reduced.
Therefore, since the polarity of the low molecular compound is reduced in the cross-linked exposed portion, the penetration of the alkali developing solution is suppressed and the alkali developing solution is hardly dissolved. On the other hand, the unexposed portion of the coating film formed with this photosensitive composition has a high polarity and a small molecular weight of the low-molecular compound, so that the alkali developer quickly permeates and the alkali solubility is greatly increased. I have.
As a result, the difference between the alkali dissolution rate of the cross-linked exposed part and the alkali dissolution rate of the uncross-linked unexposed part is enlarged, the range of developing conditions is widened, and the shape of the formed pattern is stable against the fluctuation of the developing conditions. A high-definition pattern can be obtained. The low-molecular compound is preferably used in an amount of 5 to 80% by weight based on 100 parts by weight of the copolymer resin 2.

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 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 based on 100 parts by weight of the copolymer resin or the copolymer resin 2.

As the photoacid generator in the present invention, a trihalomethyl group-containing triazine derivative or an onium salt which generates an acid by light absorption can be used. Examples of trihalomethyl group-containing triazine derivatives 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.

Examples of the onium salts include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, and 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 And 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. 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 onium salts. Since acid is generated by the light in the region, there is an advantage that a pattern can be formed with sufficient sensitivity even when a glass mask is used as a mask at the time of pattern exposure.

These photoacid generators may be used alone or as a mixture. 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 based on 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 unexposed areas due to heating after pattern exposure, causing a cross-linking reaction and reducing the resolution. Become. On the other hand, when the addition amount 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.

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 generally 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 additives, 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, and “Solsperse” manufactured by Zeneca Corporation 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.

Other solvents include 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 obtained by applying the photosensitive coloring composition of the present invention on a transparent substrate over the entire surface, drying the resultant, and performing pattern exposure from the substrate to generate an acid in the composition. The composition is cured by heating, and a colored resin layer is formed by developing the composition with an alkali developing solution and leaving the cured composition in a pattern, and repeating a series of steps including these steps on the same substrate. It can be manufactured by a process of forming a colored resin layer.

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.

Further, other additives such as a surfactant, a wetting agent, and an organic solvent may be added to the alkali developer as needed.

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

Further, in the photosensitive composition and the photosensitive coloring composition of the present invention, the low molecular weight compound represented by the chemical formula (2) is used, whereby the photosensitive composition and the photosensitive coloring composition 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, which significantly reduces the polarity and reduces the alkali solubility. At the same time, the OH group of the resin undergoes a cross-linking reaction with the cross-linking agent by heating in the presence of an acid, and the alkali solubility decreases. This double reduction in alkali solubility and, on the other hand, the unexposed portion of the coating film formed from the photosensitive composition has a high polarity and a small molecular weight of the low-molecular compound, and thus the alkali developing solution Rapidly permeate and the alkali solubility is greatly increased. As a result, the alkali dissolution rate of the cross-linked exposed portion is significantly reduced, and the effect of increasing the difference from the alkali dissolution rate of the unexposed portion is exhibited. By this action, the range of developing conditions is widened, and a high-definition pattern in which the shape of the formed pattern is stable with respect to the fluctuation of the developing conditions can be obtained.

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

[0043]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be specifically described below. <Example 1> (Preparation of photosensitive coloring composition) As a resin cured by acid, a copolymer of 2,3-dihydroxypropyl methacrylate / methacrylic acid / methyl methacrylate (weight composition ratio: 2)
5/20/55), hexamethoxymethyl melamine (manufactured by Sanwa Chemical Co., Ltd .: “Niclac MW-30M”) as a crosslinking agent, and 2- (p-) as a photoacid generator.
(Methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine (manufactured by Midori Kagaku Co., Ltd .: "TAZ
-110 "), cyclohexanone (manufactured by Kanto Chemical Co., Ltd.) as a solvent, and" Solsperse "as a dispersant.
“S24000GR” and “S50” (manufactured by Zeneca Corporation)
"00" in a ratio of 1: 1. "Chromophthal Sun Red" (manufactured by Ciba Geigy) as a red pigment and "Lionol Green" (Toyo Ink Manufacturing Co., Ltd.) as a green pigment.
"Heliogen Blue" as a blue pigment (B.A.
S. F. First, a resin, a pigment, a dispersant, and a solvent are dispersed with a disperser, and then a crosslinking agent and a photoacid generator are added, and red, green, and blue photosensitive coloring compositions are respectively obtained. Prepared. The composition ratio of this photosensitive coloring composition is as follows.
0 g, pigment 9 g, dispersant 0.9 g, crosslinking agent 4
g of the photoacid generator, 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 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 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 attached to the substrate, washed with water and dried, and 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 high-definition 10 μm square pattern having a forward tapered shape, no fringe, and a dimensional accuracy within ± 0.5 μm. Even if the development time is extended to 60 seconds,
The dimensions of the pattern did not change. Further, as for the heat resistance, even when heated at 250 ° C. for 1 hour, the transmittance of 460 nm decreased by 2% or less.

<Example 2> (Preparation of photosensitive composition)
2,3-dihydroxypropyl methacrylate / methacrylic acid / methyl methacrylate copolymer (weight composition ratio 25 /
20/55), and hexamethoxymethyl melamine (manufactured by Sanwa Chemical Co., Ltd .: “Nikarac MW”) as a crosslinking agent.
-30M ") and using 2- (p-methoxystyryl) -4,6-bis (trichloromethyl)-as a photoacid generator.
s-Triazine (manufactured by Midori Kagaku Co., Ltd .: “TAZ-11”
0 ") and cyclohexanone as a solvent (Kanto Chemical Co., Ltd.)
), A resin, a crosslinking agent, and a photoacid generator were dissolved in a solvent to prepare a photosensitive composition. The composition ratio of this photosensitive composition is such that 4 g of the crosslinking agent, 1 g of the photoacid generator,
g, and a solvent was added so that the total solid content in the photosensitive composition became 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 (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. Thereafter, the film was immersed in a 0.1% aqueous solution of sodium carbonate for 30 seconds, developed, 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 obtained in this manner was a 3 μm square high-definition pattern having a forward tapered shape and no fringe.
The dimensional accuracy was within 0.15 μm. Further, even if the developing time was extended to 60 seconds, the dimensions of the pattern did not change. Further, as for the heat resistance, even when heated at 250 ° C. for 1 hour, the transmittance of 460 nm decreased by 2% or less.

<Example 3> (Preparation of photosensitive coloring composition) As a resin cured by acid, a copolymer of methacrylic acid / 2-hydroxyethyl methacrylate / methyl methacrylate (weight composition ratio: 20/15)
/ 65) and hexamethoxymethyl melamine (manufactured by Sanwa Chemical Co., Ltd .: "Nikarac MW-3") as a crosslinking agent.
0M ”) and using 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s- as a photoacid generator.
Triazine (manufactured by Midori Kagaku Co., Ltd .: “TAZ-11
0 "), pinacol in which all of R1 to R4 in the chemical formula (2) are methyl groups as a low molecular weight compound whose polarity is changed by an acid, cyclohexanone as a solvent, and" Solspers "as a dispersant (Zeneca Corporation) Made by "S
"24,000GR" and "S5000" are used at a ratio of 1: 1. "Chromophthal Sun Red" (manufactured by Ciba Geigy) as a red pigment, "Lionol Green" (manufactured by Toyo Ink Manufacturing Co., Ltd.) as a green pigment, Using "Heliogen Blue" (manufactured by BASF) as a blue pigment,
First, a resin, a pigment, a dispersant, and a solvent were dispersed by a disperser, and thereafter, a crosslinking agent, a photoacid generator, and a low-molecular compound were added to prepare red, green, and blue photosensitive coloring compositions, respectively.
The composition ratio of this photosensitive coloring composition is such that 9 g of pigment, 0.9 g of dispersant, 6 g of crosslinking agent, 4 g of low molecular compound, and 1 g of photoacid generator are added 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 is spin-coated on a substrate such as glass.
Dried in oven at ℃. Next, exposure (50 mJ / cm2) 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 immersing it in a 0.3% aqueous solution of sodium carbonate for 40 seconds 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 baked at 230 ° C. for 1 hour 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 colored pattern obtained in this manner was a high-definition 10 μm square pattern having a forward tapered shape, no fringe, and a dimensional accuracy within ± 0.5 μm. Further, even if the developing time was extended to 60 seconds, the dimensions of the pattern did not change. Further, as for the heat resistance, even when heated at 250 ° C. for 1 hour, the transmittance of 460 nm decreased by 2% or less.

<Example 4> (Preparation of photosensitive coloring composition) As a resin cured by acid, a copolymer of 2,3-dihydroxypropyl methacrylate / methacrylic acid / ethyl methacrylate (weight composition ratio: 3)
0/15/55), hexamethoxymethyl melamine (manufactured by Sanwa Chemical Co., Ltd .: “Nikalac MW-30M”) as a crosslinking agent, and 2- (p-) as a photoacid generator.
(Methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine (manufactured by Midori Kagaku Co., Ltd .: "TAZ
-110 "), cyclohexanone (manufactured by Kanto Chemical Co., Ltd.) as a solvent, and" Solsperse "as a dispersant.
“S24000GR” and “S50” (manufactured by Zeneca Corporation)
"00" at a ratio of 1: 1. "Chromophthal Sun Red" (manufactured by Ciba Geigy) as a red pigment, and "Lionol Green" (manufactured by Toyo Ink Manufacturing Co., Ltd.) as a green pigment.
"Heliogen Blue" as a blue pigment (B.A.
S. F. First, a resin, a pigment, a dispersant, and a solvent are dispersed with a disperser, and then a crosslinking agent and a photoacid generator are added, and red, green, and blue photosensitive coloring compositions are respectively obtained. Prepared. The composition ratio of this photosensitive coloring composition is as follows.
0 g, pigment 9 g, dispersant 0.9 g, crosslinking agent 4
g of the photoacid generator, 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 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 developed by immersion in a 0.5% aqueous solution of sodium carbonate for 40 seconds 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 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 high-definition 10 μm square pattern having a forward tapered shape, no fringe, and a dimensional accuracy within ± 0.5 μm. Also, even if the development time is extended to 55 seconds,
The dimensions of the pattern did not change. Further, as for the heat resistance, even when heated at 250 ° C. for 1 hour, the transmittance of 460 nm decreased by 2% or less.

<Example 5> (Preparation of photosensitive composition)
Methacrylic acid / 2-hydroxyethyl methacrylate //
Methyl methacrylate copolymer (weight composition ratio 20/15 /
60), and hexamethoxymethyl melamine (manufactured by Sanwa Chemical Co., Ltd .: “Nikarac MW-30”) as a crosslinking agent.
M ") and 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine (manufactured by Midori Kagaku Co., Ltd .:" TAZ-11 ") as a photoacid generator.
0 "), as a low molecular weight compound whose polarity is changed by an acid,
Using pinacol, in which all of R _{1 to} R _{4 in} the chemical formula (2) are methyl groups, and using cyclohexanone (manufactured by Kanto Chemical Co., Ltd.) as a solvent, using a resin, a low-molecular compound, a crosslinking agent, and a photoacid generator as a solvent After dissolution, a photosensitive composition was prepared. The composition ratio of this photosensitive composition is such that 3 g of a low-molecular compound, 4 g of a crosslinking agent, and 1 g of a photoacid generator are added to 10 g of a resin, and the concentration of all solids in the photosensitive composition becomes 18% by weight. Solvents were added as described.

(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 (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. Thereafter, the film was developed by immersion in a 0.05% aqueous solution of sodium carbonate for 40 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 obtained in this manner was a 3 μm square high-definition pattern having a forward tapered shape and no fringe.
The dimensional accuracy was within 0.15 μm. Further, even if the developing time was extended to 60 seconds, the dimensions of the pattern did not change. Further, as for the heat resistance, even when heated at 250 ° C. for 1 hour, the transmittance of 460 nm decreased by 2% or less.

<Example 6> (Preparation of photosensitive coloring composition) As a resin curable by acid, a copolymer of 2,3-dihydroxypropyl methacrylate / methacrylic acid / butyl methacrylate (weight composition ratio: 3)
0/25/45), hexamethoxymethylmelamine (manufactured by Sanwa Chemical Co., Ltd .: “Niclac MW-30M”) as a crosslinking agent, and 2- (p-) as a photoacid generator.
(Methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine (manufactured by Midori Kagaku Co., Ltd .: "TAZ
-110 "), cyclohexanone (manufactured by Kanto Chemical Co., Ltd.) as a solvent, and" Solsperse "as a dispersant.
“S24000GR” and “S50” (manufactured by Zeneca Corporation)
"00" in a ratio of 1: 1. "Chromophthal Sun Red" (manufactured by Ciba Geigy) as a red pigment and "Lionol Green" (Toyo Ink Manufacturing Co., Ltd.) as a green pigment.
"Heliogen Blue" as a blue pigment (B.A.
S. F. First, a resin, a pigment, a dispersant, and a solvent are dispersed with a disperser, and then a crosslinking agent and a photoacid generator are added, and red, green, and blue photosensitive coloring compositions are respectively obtained. Prepared. The composition ratio of this photosensitive coloring composition is as follows.
0 g, pigment 9 g, dispersant 0.9 g, crosslinking agent 4
g of the photoacid generator, 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 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 developed by immersing it in a 0.1% aqueous sodium hydroxide solution for 30 seconds 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 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 high-definition 10 μm square pattern having a forward tapered shape, no fringe, and a dimensional accuracy within ± 0.5 μm. Further, even if the developing time was extended to 45 seconds, the dimensions of the pattern did not change. Further, as for the heat resistance, even when heated at 250 ° C. for 1 hour, the transmittance of 460 nm decreased by 2% or less.

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

(Preparation of Color Filter) A blue photosensitive coloring composition was spin-coated on a substrate such as glass.
Dried in oven at ℃. Next, exposure (50 mJ / cm2) 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 immersing it in a 0.4% aqueous sodium carbonate solution for 45 seconds 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 baked at 230 ° C. for 1 hour 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 colored pattern obtained in this manner was a high-definition 10 μm square pattern having a forward tapered shape, no fringe, and a dimensional accuracy within ± 0.5 μm. Further, even if the developing time was extended to 60 seconds, the dimensions of the pattern did not change. Further, as for the heat resistance, even when heated at 250 ° C. for 1 hour, the transmittance of 460 nm decreased by 2% or less.

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

(Preparation of Color Filter) A blue photosensitive coloring composition is 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 is 11
The photosensitive coloring composition was crosslinked and cured by heating at 0 ° C. for 1 minute on a hot plate. Thereafter, the film was developed by immersing it in a 0.1% aqueous sodium hydroxide solution for 30 seconds 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 baked at 230 ° C. for 1 hour 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 colored pattern obtained in this manner was a high-definition 10 μm square pattern having a forward tapered shape, no fringe, and a dimensional accuracy within ± 0.5 μm. Further, even if the developing time was extended to 45 seconds, the dimensions of the pattern did not change. Further, as for the heat resistance, even when heated at 250 ° C. for 1 hour, the transmittance of 460 nm decreased by 2% or less.

<Comparative Example 1> (Preparation of photosensitive coloring composition) As a resin which is cured by an acid, a 2-hydroxyethyl methacrylate / methacrylic acid / butyl methacrylate copolymer (weight composition ratio: 30/25)
/ 45) and hexamethoxymethyl melamine (manufactured by Sanwa Chemical Co., Ltd .: "Nikarac MW-3") as a crosslinking agent.
0M ”) and using 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s- as a photoacid generator.
Triazine (manufactured by Midori Kagaku Co., Ltd .: “TAZ-11
0 ") and cyclohexanone as a solvent (Kanto Chemical Co., Ltd.)
"Solsperse" (manufactured by Zeneca Corp.) "S24000GR" and "S5000" in a ratio of 1: 1 as dispersants, and "Chromophtal Sun Red" (Ciba Geigy Co., Ltd.) as a red pigment. Pigment), "Lionol Green" (manufactured by Toyo Ink Mfg. Co., Ltd.) as a green pigment, and "Heliogen Blue" (BASF, Inc.) as a blue pigment.
First, a resin, a pigment, a dispersant, and a solvent were dispersed with 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 is:
9 g of pigment, 0.9 g of dispersant, 4 g of crosslinking agent, 1 photoacid generator
g, and the concentration of the total solids in the photosensitive coloring composition is 20.
The solvent was added to make up the weight%.

(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 developed by immersing it in a 0.3% aqueous solution of sodium carbonate for 30 seconds 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 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. Fringes were generated in the thus obtained colored pattern, and the variation in the dimension of the pattern became ± 2 μm or more. In addition, the development time is 4
When extended to 5 seconds, the pattern peeled off.

<Comparative Example 2> (Preparation of photosensitive coloring composition) The same photosensitive coloring composition as in Example 3 except that a low molecular compound whose polarity is changed by an acid was removed from the photosensitive coloring composition of Example 3. Was prepared.

(Preparation of Color Filter) A blue photosensitive coloring composition is 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 is 11
The photosensitive coloring composition was crosslinked and cured by heating at 0 ° C. for 1 minute on a hot plate. Thereafter, the film was developed by immersing it in a 0.3% aqueous solution of sodium carbonate for 40 seconds 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 baked at 230 ° C. for 1 hour 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. Fringes were generated in the thus obtained colored pattern, and the variation in the dimension of the pattern became ± 2 μm or more. Further, when the development time was extended to 50 seconds, pattern peeling occurred.

[0063]

The photosensitive composition and the photosensitive coloring composition according to the present invention contain, as a resin curable by an acid, a monomer of an unsaturated carboxylic acid alkyl ester having two adjacent hydroxyl groups in a molecule, and Since a copolymer containing a monomer of an unsaturated carboxylic acid having a carboxyl group is used, the polarity conversion and cross-linking of the resin occur, and the difference in alkali solubility between exposed and unexposed areas greatly increases. Has an effect that the latitude is widened and the process stability is increased. Further, the pattern shape has no fringe, and has an effect that a high-definition pattern having a good shape and high dimensional accuracy can be formed.

Further, the photosensitive composition and the photosensitive coloring composition according to the present invention have a chemical formula (2) in which the polarity is changed by an acid.
Since the low molecular compound represented by is used, polarity conversion of the low molecular compound and cross-linking of the resin occur, the difference in alkali solubility between the exposed part and the unexposed part greatly increases, and the latitude during alkali development increases. This has the effect of increasing the process stability. Further, the pattern shape has no fringe, and has an effect that a high-definition pattern having a good shape and high dimensional accuracy can be formed.

Further, by using the photosensitive composition and the photosensitive coloring composition according to the present invention, in addition to the above effects, 2
2% reduction in transmittance at 460 nm even when heated at 50 ° C for 1 hour
There is an effect that a pattern having high heat resistance as follows can be formed. Thus, 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.

Further, by producing a color filter using the photosensitive coloring composition according to the present invention, it is possible to produce a color filter comprising pixels having excellent heat resistance, high dimensional accuracy, good shape and high definition. .

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁶ Identification code FI G02B 5/20 101 G02B 5/20 101 G03F 7/038 601 G03F 7/038 601 (72) Inventor Akira Tamura Taito, Taito-ku, Tokyo 1-5-1, Toppan Printing Co., Ltd.

Claims (6)

[Claims] 1. A photosensitive composition comprising a resin curable by an acid, a crosslinking agent, and a photoacid generator as main components, wherein the main component of the resin curable by the acid is two hydroxyl groups adjacent to each other in a molecule. A photosensitive composition, which is a copolymer comprising a monomer of an unsaturated carboxylic acid alkyl ester having the formula: and a monomer of an unsaturated carboxylic acid having a carboxyl group. 2. A photosensitive coloring composition comprising a resin curable by an acid, a crosslinking agent, a photoacid generator, and a pigment as main components, wherein the main component of the resin curable by the acid is adjacent to the molecule. A photosensitive coloring composition, which is a copolymer comprising a monomer of an unsaturated carboxylic acid alkyl ester having two hydroxyl groups and a monomer of an unsaturated carboxylic acid having a carboxyl group. 3. A color filter using the photosensitive coloring composition according to claim 2. 4. A photosensitive composition mainly comprising a resin which cures with an acid, a low molecular compound whose polarity is changed by an acid, a crosslinking agent and a photoacid generator, wherein the low molecular compound whose polarity is changed by the acid is used. The photosensitive composition, wherein the compound is a low molecular compound represented by the chemical formula (2). Embedded image 5. A photosensitive coloring composition comprising a resin which is cured by an acid, a low molecular weight compound whose polarity is changed by an acid, a crosslinking agent, a photoacid generator, and a pigment, wherein the polarity is changed by the acid. Wherein the low molecular weight compound is a low molecular weight compound represented by the chemical formula (2). Embedded image 6. A color filter using the photosensitive coloring composition according to claim 5.