JP2000221682A - Photosensitive composition, photosensitive colored composition and color filter using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive composition capable of forming a high definition pattern having a small film thickness, no protrusions on the surface and good flatness in the surface by using a copolymer with a side chain having an OH group and a side chain having a specified protective group which is disconnected by the action of an acid as an acid-curable resin. SOLUTION: The photosensitive resin composition contains an acid-curable resin, a crosslinking agent and a photo-acid generating agent as essential components. The resin is a copolymer with a side chain having an OH group and a side chain having a protective group of the formula which is disconnected by the action of an acid. In the formula, each of R1-R3 is a 1-8C linear, branched or cyclic aliphatic residue or aromatic residue and may be a basket-shaped alicyclic residue which combines at the terminal part. When a film formed using the composition is patterned, the bulky protective group is disconnected by heating in the presence of the acid generated after exposure and the protective group is isolated in the film, diffuses in the film and transpires from the surface of the film. The volume occupied by the resin in the film is therefore reduced and the film thickness is reduced.

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 colored composition, and a color filter using the photosensitive colored composition, and more specifically, has good in-plane flatness without protrusions on a formed pattern. Composition capable of efficiently producing a high-definition pattern and a color filter having a small film thickness with an excellent yield, a photosensitive coloring composition, and a color filter using the photosensitive coloring composition It is.

[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.

[0004] However, the above-mentioned chemically amplified photosensitive composition is not affected by oxygen and is strongly crosslinked from the surface layer of the pattern, so that the film thickness does not change much throughout the process. Therefore, for example, when a pattern is formed and a second pattern is formed while the pattern is left, or when a color filter is manufactured, a pattern already formed at the time of forming the second and subsequent colors is applied to the next color and subsequent coatings. When the film thicknesses are approximately the same, the film thickness near the already formed pattern rises thickly, and the patterns of the second and subsequent colors have protrusions on the outer peripheral portion, and the in-plane flatness is deteriorated. The projections of the patterns of the second and subsequent colors become larger as the distance between the patterns becomes narrower. For example, in a color filter used for an imaging device such as a color video camera, the projections are generated in the patterns because they are minute patterns of 10 μm or less. The projections cause color unevenness and the like.

In order to increase the color density of the color filter used in the above application, it is necessary to increase the content of the pigment in the photosensitive coloring composition or to increase the film thickness of the pattern. However, when the content of the pigment is increased, the sensitivity is reduced and pattern formation becomes difficult, and when the film thickness is increased, the projections of the second and subsequent patterns are further increased. There was a problem that peeling of the pattern easily occurred.

[0006]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a pattern having a thin film thickness, no protrusions on the pattern, It is an object of the present invention to provide a photosensitive composition capable of forming a high-definition pattern having good in-plane flatness. Further, the present invention provides a photosensitive coloring composition which has a small pattern thickness, has no protrusions on the pattern, has good flatness in the pattern plane, and can form a high-definition pattern having a high color density even with a small film thickness. To provide things. In addition, the present invention provides a photosensitive colored composition according to the present invention, in which the thickness of the pattern is thin, there are no protrusions on the pattern, the flatness in the pattern surface is good, and the color density is small even when the thickness is small. To provide a color filter in which a high-definition pattern with high density is formed.

[0007]

The present invention relates to a photosensitive composition containing a resin curable by an acid, a crosslinking agent and a photoacid generator as main components, wherein the resin curable by the acid has an OH group. A photosensitive composition comprising a copolymer having a side chain having a side chain and a side chain having a protective group represented by the chemical formula (1) which is removed by an acid.

Embedded image

Further, the present invention provides a resin curable by an acid,
A photosensitive coloring composition containing a crosslinking agent, a photoacid generator, and a pigment as main components, wherein the resin that is cured by the acid is represented by a chemical formula (1) that is released by the side chain having an OH group and the acid. A photosensitive coloring composition, which is a copolymer having a side chain having a protecting group.

Embedded image

The present invention also provides a color filter using the photosensitive coloring composition according to the present invention.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail below based on one embodiment. The resin that is cured by an acid in the present invention is a copolymer having a side chain having an OH group and a side chain having a protective group represented by the chemical formula (1), which is removed by the acid. In the patterning using the photosensitive composition according to the present invention, the side chain having a protective group detached by the acid has a bulky protective group before exposure and heating, and increases the volume occupancy in the resin film. However, the bulky protective group comes off due to heating in the presence of acid generated after exposure, and the protective group is isolated in the film, diffuses in the film and evaporates from the surface, causing a decrease in the volume occupancy of the resin in the film. The film thickness decreases. And
After removal of the protecting group, the side chain is crosslinked with the crosslinking agent. The removed protective groups remaining in the film further evaporate from the surface when the pattern formed after development is heated, and do not remain in the film, so that the film thickness is further reduced. Therefore,
The formed pattern is a high-definition pattern having a thin film thickness, no protrusions on the pattern, and good flatness in the pattern surface.

In the patterning using the photosensitive coloring composition according to the present invention, the pigment does not evaporate, so that the color density of the formed pattern does not change and the volume content of the pigment is relatively increased. Even if the film thickness is small, a pattern having a high color density is obtained. Therefore, the formed pattern has a thin pattern thickness, no protrusions on the pattern,
A high-definition pattern having good color flatness and good color density even if the film thickness is small is obtained.

In the present invention, the resin cured by an acid is
A monomer having a side chain having an OH group and a monomer having a side chain having a protecting group which is removed by an acid are copolymerized, or OH
The side chain may be added later to the resin having a side chain having a group. As the resin having the OH group, a copolymer of a phenolic monomer represented by phenol novolak and p-hydroxystyrene, a monomer having a carboxyl group, and a monomer having a hydroxyl group can be used.

The monomer having a carboxyl group includes 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 the 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.

In the present invention, the proportion of the monomer having a side chain having a protecting group which is removed by an acid as a copolymer composition of the resin which is cured by an acid is preferably 20 to 70% by weight in the resin. If the amount is less than 20% by weight, the effect of reducing the film thickness cannot be obtained, and projections occur. If the amount is more than 70% by weight, the polarity of the resin itself becomes too low, so that a pattern cannot be formed.
The proportion of the monomer having a side chain having an OH group is 5%.
% By weight is preferred. In particular, the content of the monomer having a carboxyl group is preferably more than 5% by weight when developing with an alkaline solution.

As the cross-linking agent in the present invention, one having an N-methylol structure is used. For example, a methylolated urea, a urea resin, a methylolated melamine, a butyrolated melamine, a methylolated guanamine, or an alkyl ether of these compounds is used. Alkyl etherated compounds are more preferred because they can be used and have high thermal stability. The alkyl group of the 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 in terms of sensitivity.

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

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.

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- 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, these trihalomethyl group-containing triazine derivatives are preferably used. 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 addition amount is 10 to 10% by weight of the total solid content of the photosensitive coloring composition for a color filter according to the present invention.
Used at 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.

In the present invention, a wide range of surfactants, pigment derivatives, and "Solsperse" manufactured by Zeneca Corporation are used as pigment dispersants. The addition amount of these dispersants is about 1 to 30% by weight based on 100% by weight of the pigment.

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.

Hereinafter, an example of a method for producing a color filter using the photosensitive coloring composition of the present invention will be described. The color filter using the photosensitive coloring composition of the present invention is applied to the entire surface of the photosensitive coloring composition of the present invention on a transparent substrate, dried, and exposed to a pattern from the substrate to generate radicals in the composition. Generating an acid by conversion to an acid, curing the composition by heating, developing the cured composition into a pattern by developing with a developer, forming a colored resin layer by heating,
It can be manufactured by a process of forming a plurality of colored resin layers on the same substrate by repeating a series of processes including these processes.

As the heating method, a heating device such as an oven and a hot plate can be used.
0-150 ° C is suitable. Further, the heating of the formed pattern after development is suitably at 150 to 230 ° C.

Examples of the 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 as required in the developer, for example,
A surfactant, wetting agent, organic solvent and the like may be added.

As described above, in the photosensitive composition and the photosensitive coloring composition of the present invention, the resin that is cured by an acid is represented by the side chain having an OH group and the above-mentioned chemical formula (1) that is released by the acid. By using a copolymer having a side chain having a protecting group, the side chain having a protecting group that is removed by an acid has a bulky protecting group before exposure heating, and reduces the volume occupancy in the resin film. However, the bulky protective group is removed by heating in the presence of acid generated after exposure, and the protective group is isolated in the film, diffuses in the film, evaporates from the surface, and increases the volume occupancy of the resin in the film. This causes a decrease in the film thickness. Further, the side chain after the removal of the protecting group is crosslinked with the crosslinking agent. The removed protective groups remaining in the film further evaporate from the surface by heating the pattern formed after the development, and do not remain in the film, so that the film thickness is further reduced. Therefore, the formed pattern is a high-definition pattern having a small pattern thickness, no protrusions on the pattern, and good flatness in the pattern surface.

In the patterning using the photosensitive coloring composition according to the present invention, the pigment does not evaporate, so that the color density of the formed pattern does not change, and the volume content of the pigment is relatively increased. Even if the film thickness is small, a pattern having a high color density is obtained. Therefore, the formed pattern has a thin pattern thickness, no protrusions on the pattern,
A high-definition pattern having good color flatness and good color density even if the film thickness is small is obtained.

[0031]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be specifically described below. <Example 1> (Preparation of photosensitive composition) Tert-butyl methacrylate is used as a monomer having a side chain having a protective group represented by the above chemical formula (1) which is removed by an acid, and a side chain having an OH group is used. As a resin having methacrylic acid / 2-hydroxyethyl methacrylate / methyl methacrylate / tert-butyl methacrylate copolymer (weight composition ratio 25 /
Oct. Oct. 5), 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 "), and cyclohexanone was used as a solvent.
The composition ratio of this photosensitive composition is such that 4 g of a crosslinking agent and 1 g of a photoacid generator are added to 10 g of the above-mentioned copolymer, and the concentration of all solids in the photosensitive composition is 20% by weight. Solvent was added.

(Patterning of Photosensitive Composition) The above photosensitive composition was spin-coated on a transparent glass substrate to a thickness of 1.5 μm, and dried in an oven at 70 ° C. Next, through a predetermined glass mask, 30 m using an ultra-high pressure mercury lamp
Exposure of J / cm ² was performed. After the exposure, the substrate was heated at 110 ° C. for 1 minute on a hot plate to promote the elimination, evaporation and crosslinking of the protecting group. 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 baked at 230 ° C. for 1 hour to form a pattern. The film thickness could be reduced to 0.1 μm. The above series of steps was similarly repeated on the same substrate to form green and red patterns. The thickness of each color of the colored pattern obtained in this manner is within ± 0.1 μm, and there is no protrusion on the pattern, and the in-plane flatness is excellent. The concentration was high, the cross-sectional shape of the colored pattern was vertical, and the dimensional accuracy was within ± 0.5 μm for a 10 μm square.

<Example 2> (Preparation of photosensitive coloring composition) Tert-butyl methacrylate was used as a monomer having a side chain having a protective group represented by the above chemical formula (1) which was removed by an acid, and an OH group was used. As a resin having a side chain having a methacrylic acid / 2-hydroxyethyl methacrylate / methyl methacrylate / tert-butyl methacrylate copolymer (weight composition ratio 25 /
Oct. Oct. 5), 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 as a solvent," S24000GR "and" S5000 "of" Solsperse "(manufactured by Zeneca Corporation) as dispersants in a ratio of 1: 1, and" Chromophthal Sun Red "as a red pigment. (Manufactured by Ciba Geigy), "Lionol Green" (manufactured by Toyo Ink Mfg. Co., Ltd.) as a green pigment, and "Heliogen Blue" (manufactured by BASF Co., Ltd.) as a blue pigment. Use
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 as follows: 9 g of a pigment, 0.9 g of a dispersing agent, 4 g of a crosslinking agent, and 1 g of a photoacid generator with respect to 10 g of a resin, and the concentration of all solids in the photosensitive coloring composition. Was adjusted to 20% by weight.

(Preparation of Color Filter) A blue photosensitive coloring composition was spin-coated on a transparent glass substrate to a thickness of 1.5 μm and dried in an oven at 70 ° C. 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 promote the elimination, evaporation and crosslinking of the protecting group. 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 film thickness was reduced to 1.1 μm. The above series of steps was similarly repeated on the same substrate to form green and red patterns. The thickness of each color of the colored pattern obtained in this manner is within ± 0.1 μm, and there is no protrusion on the pattern, and the in-plane flatness is excellent. The concentration was high, the cross-sectional shape of the colored pattern was vertical, and the dimensional accuracy was within ± 0.5 μm for a 10 μm square.

<Example 3> (Preparation of photosensitive coloring composition) In the photosensitive coloring composition of Example 1, tricyclohexylmethyl methacrylate was used as a monomer having a side chain having a protecting group which was removed by an acid. As the resin having a side chain having an OH group, methacrylic acid / 2-hydroxyethyl methacrylate / methyl methacrylate / tricyclohexylmethyl methacrylate copolymer (weight composition ratio 25/15/10/50) was used.
Other compositions were the same to prepare a photosensitive coloring composition.

(Preparation of Color Filter) A blue photosensitive coloring composition was spin-coated to a thickness of 1.5 μm on a transparent glass substrate and dried in an oven at 70 ° C. Next, exposure was performed (70 mJ / cm ² ) using a predetermined glass mask. This was heated on a hot plate at 110 ° C. for 1 minute to promote the elimination, evaporation and crosslinking of the protecting group. Thereafter, the film was developed by immersion in a 0.3% aqueous solution of sodium carbonate for 60 seconds and washed well with water. This was rubbed with a soft sponge to remove the pigment attached to the substrate, washed with water and dried, and baked at 230 ° C. for 1 hour to form a blue pattern. The film thickness was reduced to 1.0 μm. The above series of steps was similarly repeated on the same substrate to form green and red patterns. The thickness of each color of the colored pattern obtained in this manner is within ± 0.1 μm, and there is no protrusion on the pattern, and the in-plane flatness is excellent. The concentration was high, the cross-sectional shape of the colored pattern was vertical, and the dimensional accuracy was within ± 0.5 μm for a 10 μm square.

<Example 4> (Preparation of photosensitive coloring composition) In the photosensitive coloring composition of Example 1, atamantyl methacrylate was used as a monomer having a side chain having a protective group which was removed by an acid. OH
Examples of the resin having a side chain having a group include methacrylic acid / 2-hydroxyethyl methacrylate / methyl methacrylate /
Adamantyl methacrylate copolymer (weight composition ratio 30 /
10/20/40), and the other composition was the same to prepare a photosensitive coloring composition.

(Preparation of Color Filter) A blue photosensitive coloring composition was spin-coated on a transparent glass substrate to a thickness of 1.5 μm and dried in an oven at 70 ° C. Next, exposure was performed (70 mJ / cm ² ) using a predetermined glass mask. This was heated on a hot plate at 110 ° C. for 1 minute to promote the elimination, evaporation and crosslinking of the protecting group. Thereafter, the film was immersed in a 0.59% aqueous sodium hydroxide solution for 60 seconds, developed, and washed well with water. This was rubbed with a soft sponge to remove the pigment adhering to the substrate, washed with water and dried.
Baking at ℃ for 1 hour to form a blue pattern. The film thickness was reduced to 1.0 μm. The above series of steps was similarly repeated on the same substrate to form green and red patterns.
The thickness of each color of the thus obtained colored pattern is
In any case, there is no protrusion on the pattern within ± 0.1 μm and the in-plane flatness is excellent, and even a high-resolution 10 μm square thin film has a high color density with a thin film, and the cross-sectional shape of the colored pattern is vertical and 10 μm square On the other hand, the dimensional accuracy was within ± 0.5 μm.

<Comparative Example 1> (Preparation of photosensitive coloring composition) The photosensitive coloring composition of Example 1 does not contain a monomer having a side chain having a protecting group which is removed by an acid and has an OH group. As the resin having a side chain, methacrylic acid / 2-hydroxyethyl methacrylate / methyl methacrylate / ethyl methacrylate copolymer (weight composition ratio: 25/10/20/55) is used, and the other composition is the same and the photosensitivity is changed. A coloring composition was prepared.

(Preparation of Color Filter) A blue photosensitive coloring composition was spin-coated on a transparent glass substrate to a thickness of 1.5 μm and dried in an oven at 70 ° C. 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 promote the elimination, evaporation and crosslinking of the protecting group. Thereafter, the film was immersed in a 0.1% aqueous solution of sodium carbonate for 40 seconds, developed, 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 film thickness was reduced to 1.35 μm. The above series of steps was similarly repeated on the same substrate to form green and red patterns.
A protrusion is formed on the outer peripheral portion of the second and subsequent patterns obtained in this manner, and the protrusion has a thickness of 1.35 μm after baking.
m, the thickness was 0.3 μm or more, and the in-plane flatness was poor, resulting in color unevenness.

[0041]

The photosensitive composition according to the present invention is a photosensitive composition containing a resin curable by an acid, a crosslinking agent and a photoacid generator as main components, wherein the resin curable by an acid has an OH group. Since it is a copolymer having a side chain having a protective group and a side chain having a protective group represented by the above chemical formula (1) which is removed by an acid, the side chain having a protective group which is removed by an acid has a bulky protection before exposure heating. The resin has a high volume occupancy ratio in the resin film, but the bulky protective group is released by heating in the presence of acid generated after exposure, and the protective group is isolated in the film and diffuses in the film to spread the surface. From the resin, causing a decrease in the volume occupancy of the resin in the film and a decrease in the film thickness. Further, the side chain after the removal of the protecting group is crosslinked with the crosslinking agent. The removed protective groups remaining in the film further evaporate from the surface by heating the pattern formed after the development, and do not remain in the film, so that the film thickness is further reduced. Therefore, the formed pattern is a high-definition pattern having a small pattern thickness, no protrusions on the pattern, and good flatness in the pattern surface.

Further, the photosensitive coloring composition according to the present invention comprises:
Resin curable by acid, a cross-linking agent, a photosensitive composition containing a photoacid generator as a main component, the resin curable by acid,
Since it is a copolymer having a side chain having an OH group and a side chain having a protective group represented by the above chemical formula (1) which is removed by an acid, the side chain having a protective group removed by an acid is exposed before exposure heating. Although it has a bulky protecting group and increases the volume occupancy of the resin in the film, the bulky protecting group comes off by heating in the presence of an acid generated after exposure, and the protecting group is isolated in the film and passes through the film. It diffuses and evaporates from the surface, causing a reduction in the volume occupancy of the resin in the film and a reduction in the film thickness. Further, the side chain after the removal of the protecting group is crosslinked with the crosslinking agent. The removed protective groups remaining in the film further evaporate from the surface by heating the pattern formed after the development, and do not remain in the film, so that the film thickness is further reduced. Then, the color density of the formed pattern does not change because the pigment does not evaporate, and the volume content of the pigment is relatively increased,
Even if the film thickness is small, a pattern having a high color density is obtained. Therefore,
The formed pattern has a small pattern thickness, has no protrusions on the pattern, has good flatness in the pattern surface, and is a high-definition pattern with a high color density even when the film thickness is small.

Further, by producing a color filter using the photosensitive coloring composition according to the present invention, the thickness of the pattern is small, there are no protrusions on the pattern, and the flatness in the pattern plane is good. It is possible to manufacture a color filter in which a high-definition pattern having a high color density is formed even if the color filter is thin.

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Claims (3)

[Claims] 1. A photosensitive composition comprising a resin curable by an acid, a cross-linking agent and a photoacid generator as main components, wherein the resin curable by the acid is removed by a side chain having an OH group and an acid. A photosensitive composition which is a copolymer having a side chain having a protective group represented by the chemical formula (1). Embedded image 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 resin curable by the acid has a side chain having an OH group, and A photosensitive coloring composition, which is a copolymer having a side chain having a protective group represented by the chemical formula (1) which is removed by an acid. Embedded image 3. A color filter using the photosensitive coloring composition according to claim 2.