JPH09178932A - Colored photosensitive resin composition and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive resin compsn. contg. a pigment, acrylic resin, a multifunctional monomer, a photopolymn. initiator and a solvent as essential components and contg. the components except the solvent in the solvent having very high safety in a uniformly dissolved or dispersed state. SOLUTION: In this photosensitive resin compsn. contg. a pigment, acrylic resin, a multifunctional monomer, a photopolymn. initiator and a solvent as essential components, the solvent is ethyl lactate and the monomer is at least one selected from among pentaerythritol acrylate, ethylene oxide modified trimethylolpropane and dipentaerythritol hexaacrylate.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored photosensitive resin composition and a color filter, and more specifically, a colored photosensitive resin used for producing a color filter used in a color liquid crystal display, a color video camera or the like. The present invention relates to a composition and a color filter in which a colored pattern is formed using the colored photosensitive resin composition.

[0002]

2. Description of the Related Art In a color liquid crystal display, a three-dimensional image is formed on a transparent substrate.
A color filter in which color pixels are formed is used.
As the three colors, the three primary colors of red, blue and green are usually used. Further, in order to prevent unnecessary light from leaking and improve the contrast, the gap between the pixels is generally filled with a light shielding layer (black matrix). As a method for forming such colored pixels and a black matrix, a method using a colored photosensitive resin composition containing a pigment is known. That is, by forming a coating film of a photosensitive resin composition in which a pigment of the first hue is dispersed on a transparent substrate, and then exposing through a mask pattern and developing, the first patterned transparent The second and third pixels are formed by forming a colored image (pixel) and repeating the same process. The black matrix is formed using a photosensitive resin composition containing a black pigment.

Regarding the production of such a colored photosensitive resin composition and a color filter, for example, Japanese Patent Publication No. 6-9521.
No. 1 discloses, as a photosensitive resin, a polyfunctional (meth) acrylate monomer, an organic binder, and photopolymerization initiation comprising at least one selected from a halomethyloxadiazole compound and a halomethyl-S-triazine compound. A color filter using a composition containing an agent is disclosed.

In Japanese Patent Laid-Open No. 6-201913, photopolymerization initiation is carried out when a photosensitive coloring composition is produced from an acrylic resin, a pigment, a dispersant, a photopolymerizable monomer, a photopolymerization initiator and a solvent. It is disclosed that a triazine-based compound or an imidazole-based compound is used as the agent. Then, the publication discloses a method for producing a color filter using the photosensitive coloring composition.

JP-A-6-3521 discloses that a pigment, a binder polymer, and a radiation-sensitive compound are dissolved or dispersed in an organic solvent, and the organic solvent has a boiling point of 100 to 200 ° C. under normal pressure. A feeling for a color filter, which is a solvent containing at least one kind of ester, ether or ketone having a vapor pressure at 20 ° C. of 0.05 to 10 mmHg in an amount of 50% by weight or more. Radioactive compositions are disclosed.

In these known colored photosensitive resin compositions,
Each component is dissolved or dispersed in an organic solvent such as ethyl cellosolve acetate. For example, Japanese Unexamined Patent Application Publication No.
In the example of JP-A-11-1999, ethyl cellosolve acetate is used as a solvent, and in the example of JP-A-6-201913, ethyl cellosolve is used as a solvent. In the examples of JP-A-6-3521, ethyl 3-ethoxypropionate, propion glycol monomethyl acetate, diethylene glycol dimethyl ether / carbitol acetate, diethylene glycol dimethyl ether / n-butyl carbitol acetate, diethylene glycol dimethyl ether /
Methyl ethyl ketone is used as a solvent.

However, recently, new research results have been reported on the toxicity of these organic solvents or their effects on the human body. For example, the problem that ethyl cellosolve acetate, which has been widely used as a solvent for semiconductor photoresists in the past, may inhibit male reproductive function or cause female infertility or teratogenicity to offspring. Is presented. As described above, even in the colored photosensitive resin composition, ethyl cellosolve acetate is used as a solvent, and there is a strong demand for switching the solvent from the viewpoint of safety.

The reason why ethyl cellosolve acetate causes the above problems has not been clarified yet. Although it has been pointed out that ethoxyacetic acid, which is generated in the process of substance substitution of ethyl cellosolve acetate in the body, may be the causative substance, it cannot be said that it has been sufficiently investigated. Therefore, in the future, not only ethyl cellosolve acetate but also other organic solvents may have a new adverse effect on the human body and heredity.

Therefore, as for the solvent of the colored photosensitive resin composition, not only the use of a solvent such as ethyl cellosolve acetate, which has been pointed out to have a bad effect on the human body, is stopped, but also the safety is already sufficient. It is desirable to switch to a confirmed solvent. However, when the conventional solvent is changed to a new solvent, the dissolving power for each component naturally changes, and it is not always possible to obtain a colored photosensitive resin composition in which each component is uniformly dissolved or dispersed.
In the patent document, as a solvent for the colored photosensitive resin composition, conventionally, many organic solvents have been exemplified, but in practice, a specific solvent such as ethyl cellosolve acetate has been widely used for each component. This is because it has an excellent dissolving power for.

For example, as a solvent whose safety has been sufficiently confirmed, ethyl lactate can be mentioned. Ethyl lactate has high safety and is used not only as a solvent but also as a food additive. It is said that it decomposes rapidly in the body and in the natural world. However, even though the polyfunctional monomer that can be used with ethyl cellosolve acetate, etc. up to now can be dissolved in ethyl lactate itself, the polymer is precipitated by mixing with the polymer solution, or is mixed with the polymer during coating / drying. Problems such as minute separation occur. In the examples of the above publications, pentaerythritol tetraacrylate and trimethylolpropane triacrylate are used as the polyfunctional monomer, but even if these monomers are actually added to the binder resin solution using ethyl lactate, a uniform solution is obtained. And a coating film cannot be obtained.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to provide a pigment, an acrylic resin, a polyfunctional monomer, a photopolymerization initiator,
And a colored photosensitive resin composition containing a solvent as an essential component, a highly safe solvent is used, and a colored photosensitive resin in which each component such as an acrylic resin or a polyfunctional monomer is uniformly dissolved or dispersed It is to provide a resin composition. The present inventors, as a solvent, also used as a food additive, in the body, focusing on ethyl lactate, which is said to be rapidly decomposed in the natural world, as a result of earnest research, a polyfunctional monomer compatible with ethyl lactate was found. I found it. That is, by combining ethyl lactate and a selected specific polyfunctional monomer, not only the polyfunctional monomer is dissolved but also other components such as an acrylic resin are mixed and uniformly dissolved or dispersed. It was found that a solution was obtained. It was also found that by using this solution, a uniform coating film can be formed without separating each component. Further, it was found that a highly sensitive colored photosensitive resin composition can be obtained by adding a specific triazine compound as a photopolymerization initiator to this system. The present invention has been completed based on these findings.

[0012]

According to the present invention, a pigment,
In a colored photosensitive resin composition containing an acrylic resin, a polyfunctional monomer, a photopolymerization initiator, and a solvent as essential components, the solvent is ethyl lactate, and the polyfunctional monomer is pentaerythritol acrylate or ethylene oxide modified trioxide. Methylolpropane triacrylate,
And a colored photosensitive resin composition, which is at least one selected from the group consisting of dipentaerythritol hexaacrylate.

As the photopolymerization initiator, 2- (o-methoxystyryl) -4,6-bis (trichloromethyl) -S is used.
-Triazine, 2- (2,4-dimethoxystyryl)-
4,6-bis (trichloromethyl) -S-triazine,
And 2- (3,4,5-trimethoxystyryl) -4,
It is preferable to use at least one selected from the group consisting of 6-bis (trichloromethyl) -S-triazine. Further, according to the present invention, there is provided a color filter characterized in that a colored layer made of a photocured product of the colored photosensitive resin composition is formed in a pattern on a transparent substrate.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The first feature of the present invention is to use ethyl lactate as a solvent in a colored photosensitive resin composition containing a pigment, an acrylic resin, a polyfunctional monomer, a photopolymerization initiator, and a solvent as essential components. . The second feature of the present invention is to use, as the polyfunctional monomer, at least one selected from the group consisting of pentaerythritol acrylate, ethylene oxide-modified (EO-modified) trimethylolpropane triacrylate, and dipentaerythritol hexaacrylate. .

In order to obtain sufficient exposure sensitivity, it is desirable to use a trifunctional or higher-functional polyfunctional monomer from the viewpoint of the degree of crosslinking. However, for polyfunctional monomers other than the above,
Even though it can be dissolved in ethyl lactate itself, problems such as precipitation of the polymer due to mixing with the polymer (acrylic resin) solution, and minute separation from the polymer during coating and drying occur. For example, when pentaerythritol tetraacrylate or trimethylolpropane triacrylate, which is widely used as a polyfunctional monomer, is combined with ethyl lactate, it becomes cloudy or a polymer is deposited, and a satisfactory colored photosensitive resin composition and coating film can be obtained. Can't get

In the present invention, as the acrylic resin, those conventionally used in the technical field can be used, but specifically, copolymers of the following monomers are preferable. That is, as acrylic monomers, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, cyclohexyl acrylate, benzyl acrylate, benzyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl. Acrylate,
2-hydroxypropyl methacrylate, glycidyl methacrylate, acrylamide, methacrylamide, etc. can be mentioned. These monomers can be copolymerized using a polymerization initiator such as azobisisobutyronitrile. Molecular weight of acrylic resin (light scattering method)
Is preferably in the range of 10,000 to 50,000.
If this molecular weight is too small, the exposure sensitivity will decrease, and conversely, if it is too large, alkali development will become difficult. Since the acrylic resin enables alkali development, it is preferable to copolymerize acrylic acid or methacrylic acid at a ratio of 10 to 30% by weight.

Examples of the photopolymerization initiator include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one and 2-methyl-1- (4-
Methylthiophenyl) -2-morpholinopropane-1
-One, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone,
2-hydroxy-2-methyl-1-phenylpropane-
1-one, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propoxythioxanthone, 2,
4-diethylthioxanthone, 2- (o-methoxystyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (2,4-dimethoxystyryl) -4,6
-Bis (trichloromethyl) -S-triazine, and 2
Examples thereof include-(3,4,5-trimethoxystyryl) -4,6-bis (trichloromethyl) -S-triazine. These photopolymerization initiators may be used alone or in combination of two or more. Among these photopolymerization initiators, in that a highly sensitive composition can be obtained,

[0018]

Embedded image 2- (o-methoxystyryl) -4,6-bis (trichloromethyl) -S-triazine represented by

[0019]

Embedded image 2- (2,4-dimethoxystyryl) -4 represented by
6-bis (trichloromethyl) -S-triazine, and

[0020]

Embedded image

2- (3,4,5-trimethoxystyryl) -4,6-bis (trichloromethyl) -S represented by
-It is particularly preferable to use at least one selected from the group consisting of triazine. These specific triazine-based compounds can give a highly sensitive colored photosensitive resin composition in the system of ethyl lactate and the selected polyfunctional monomer, even if the use ratio is small. Even if the triazine compound has a similar structure, if the position of the methoxy group is different from those of the three compounds, the compound is not substantially dissolved in ethyl lactate.

In the present invention, as the photoinitiator aid, for example,
4-Dimethylaminobenzoic acid isoamyl ester, 4-
Dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid-2-ethylhexyl, triethanolamine, methyldiethanolamine, triisopropanolamine and the like may be used. These photoinitiating aids can be used alone or in combination of two or more.

The contents (weight ratio) of the acrylic resin, the polyfunctional monomer and the photopolymerization initiator in the colored photosensitive resin composition are as follows: acrylic resin: polyfunctional monomer: photopolymerization initiator = 1: 0. The range of 3: 0.03 to 1: 1: 0.8 is preferable. If the amount of polyfunctional monomer is too small, the degree of crosslinking will be small, and the formed pattern will flow. Conversely, if it is too large, tack will appear in the coating film and stick to the mask etc.
Problems such as easy scratching occur. If the amount of the photopolymerization initiator is too small, the sensitivity cannot be obtained. On the contrary, if the amount of the photopolymerization initiator is too large, problems occur such as precipitation as crystals in the dry coating film and a decrease in adhesion. When the above-mentioned three types of triazine-based compounds are used as the photopolymerization initiator, acrylic resin: polyfunctional monomer: photopolymerization initiator = 1: 0.3: 0.03 to 1:
The range of 1: 0.2 is preferable.

The pigment used in the colored photosensitive resin composition includes azo lake type, insoluble azo type, condensed azo type, phthalocyanine type, quinacridone type, dioxazine type, isoindolinone type, anthraquinone type, perinone type, thioindico type, Organic pigments such as perylene pigments can be mentioned. These pigments may be used alone or in combination with
Combinations of more than one species can be used. further,
You may use pigments, such as carbon, titanium carbon, and iron oxide.

The colored photosensitive resin composition can be prepared by dispersing a pigment in an acrylic resin. When the pigment is dispersed in the acrylic resin, the pigment may be directly dispersed in the acrylic resin, or a coloring paste in which the pigment is completely dispersed in a dispersant such as a polymer dispersant may be prepared and then mixed. The polymer dispersant is a polymer such as an acrylic type, a polyester type, a maleic acid type, or an ethyl cellulose type,
_{-COOH, -SO 3 H, -P (} O) (OH) 2, -OH
Etc. or a salt thereof, or a proton accepting group such as —NH ₂ , —NHR, and —NR ₁ R ₂ , and one or more such as a quaternary ammonium group having an ion pair bond. The composition as it is included. For the dispersion, the colored photosensitive resin composition can be prepared by kneading with a pigment disperser such as a two-roll, three-roll, ball mill, and sand mill, and centrifuging and filtering with a filter.

The colored photosensitive resin composition thus obtained is useful for producing a color filter. The color filter of the present invention is obtained by curing the colored photosensitive resin composition of the present invention into a predetermined pattern on a substrate to form a colored layer. The substrate used is not particularly limited, and transparent glass, synthetic resin, or the like can be used. The color filter is produced by uniformly applying the colored photosensitive resin composition on a transparent substrate using a spinner or a roll coater and drying it using an oven or a hot plate, and a stripe pattern that is a normal color filter pattern, mosaic. UV exposure is performed through a mask of a pattern or a triangle pattern, and then the unexposed portion is dissolved using an alkaline aqueous solution or the like.
By repeating these operations, it is possible to obtain a color filter in which a desired number of hue coloring patterns are formed. At the time of exposure to ultraviolet light, an oxygen barrier film such as polyvinyl alcohol may be provided to prevent polymerization inhibition by oxygen. Further, the black matrix may be formed by the same operation.

The colored photosensitive resin composition of the present invention uses ethyl lactate, which is a safe compound that is used as a solvent as a food additive and is rapidly decomposed in the body and in the natural world.
It is obtained by combining polyfunctional monomers suitable for it. Thereby, a highly sensitive colored photosensitive resin composition can be produced. Furthermore, the colored photosensitive resin composition enables the production of a color filter with a safe solvent.

[0028]

The present invention will be described more specifically below with reference to examples and comparative examples.

Example 1 Binder Resin First, in order to clarify the properties, the adaptability of the polyfunctional monomer was confirmed in a system in which the pigment was not dispersed. Acrylic acid 15 parts by weight, 2-hydroxyethyl methacrylate 35
Parts by weight, 35 parts by weight of butyl methacrylate, 15 parts by weight of methyl methacrylate are dissolved in 500 g of ethanol,
Azobisisobutyronitrile 0.5 under argon atmosphere
The weight part was added and it was made to react at 70 degreeC for 5 hours. The polymerized acrylic resin was precipitated in hexane and then dried to obtain a solid acrylic resin. The acrylic resin thus obtained was dissolved in ethyl lactate at a resin concentration of 10% by weight to prepare a binder resin solution. When the molecular weight of the binder resin was measured by the light scattering method, it was 2
It was 5,000.

With respect to 100 parts by weight of the binder resin solution, 7 parts by weight of pentaerythritol triacrylate (PE-3A, Kyoeisha Chemical Co., Ltd.) and 2-benzyl-2-
Dimethylamino-1- (4-morpholinophenyl)-
Butan-1-on (Ciba Geigy Il Ga Cure-36
9) 4 parts by weight, 1-chloro-4-propoxythioxanthone (Nippon Kayaku Kayakyu-CPTX) 1 part by weight, and 4-dimethylaminobenzoic acid isoamyl ester (Nippon Kayaku Kayakyu-DMBI) 0.5 part by weight. When a part was added and dissolved, a transparent photosensitive resin composition solution was obtained. The transparent photosensitive resin composition solution was applied onto a glass substrate with a spinner to a thickness of 1.20 μm, and prebaked at 100 ° C. for 5 minutes on a hot plate. A coating film of the photosensitive resin composition could be formed.

The coating film thus obtained was coated with an ultra-high pressure ultraviolet lamp (1
UV light is radiated through a mask using a kw) and then PEB (Post Exposu) at 100 ° C. for 5 minutes.
reBake) treatment, and a developer (pH of Na ₂ CO ₃ (0.25% by weight) + NaHCO ₃ (0.25% by weight))
= 10.0). Then, it was sufficiently washed with pure water and post-baked at 200 ° C. for 30 minutes.
As a result, a transparent pattern could be formed at 5 mJ / cm ² in terms of 365 nm.

Example 2 In place of the pentaerythritol triacrylate of Example 1, EO-modified trimethylolpropane triacrylate (Kyoeisha Chemical Co., Ltd. TMP) was used.
-6EO-3A), the same operation was performed,
A transparent pattern could be formed at 6 mJ / cm ² in terms of 365 nm.

[Example 3] Dipentaerythritol hexaacrylate (Kyoeisha Chemical Co., Ltd. DPE-6) was used in place of the pentaerythritol triacrylate of Example 1.
When the same operation was performed using A), a transparent pattern could be formed at 3 mJ / cm ² in terms of 365 nm.

Comparative Example 1 Instead of the pentaerythritol triacrylate of Example 1, trimethylolpropane triacrylate (TMP-A, Kyoeisha Chemical Co., Ltd.) was used. However, it became cloudy when added to the binder resin solution. A coating film was formed in the same manner as in Example 1, but it was cloudy and a transparent coating film could not be obtained. Exposure and development were performed using a cloudy coating film, but pattern formation could not be performed.

Comparative Example 2 Pentaerythritol tetraacrylate (PE-4A, Kyoeisha Chemical Co., Ltd.) was used in place of the pentaerythritol triacrylate of Example 1. However, the polymer was precipitated when it was added to the binder resin solution, and it was unusable.

Example 4 Colored Photosensitive Resin Composition A colored photosensitive resin composition was prepared using the polyfunctional monomer which was confirmed to be applicable in Examples 1 to 3. Example 4-1 Using the acrylic resin produced in Example 1, the following red photosensitive resin composition was prepared. Acrylic resin AA / HEMA / BMA / MMA = 15/35/35 /
15 (8.4% by weight) Polyfunctional monomer pentaerythritol triacrylate (PE-3A, Kyoeisha Chemical Co., Ltd.) (5.9% by weight) Photopolymerization initiator 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) -butan-1-one (Ciba-Geigy-Irgacure-369) (3.4% by weight): 1-chloro-
4-propoxythioxanthone (Nippon Kayaku Kayakyu-
CPTX) (0.9% by weight) Photoinitiator aid 4-Dimethylaminobenzoic acid isoamyl ester (Nippon Kayaku Kayakyu DMBI) (0.4% by weight) Solvent Ethyl lactate (74.8% by weight) Pigment Chromophtal Red: Disazo Yellow = 85:15
(6.2% by weight)

The above red photosensitive resin composition solution was applied onto a glass substrate using a spinner so as to have a thickness of 1.1 μm, and prebaked at 100 ° C. for 5 minutes to give a red color on the glass substrate. A coating film of the photosensitive resin composition was formed. The obtained coating film was irradiated with ultraviolet rays through a mask using an ultra-high pressure ultraviolet lamp (1 kw), and then PEB treatment was carried out at 100 ° C. for 5 minutes to obtain Na ₂ CO ₃
(0.25% by weight) + NaHCO ₃ (0.25% by weight)
Development was performed using the developing solution (pH = 10.0). Then, it was sufficiently washed with pure water and post-baked at 230 ° C. for 30 minutes. As a result, 100 at 365 nm conversion
The pattern could be formed at mJ / cm ² .

Example 4-2 A green photosensitive resin composition in which the pigment was phthalocyanine green: disazo yellow = 60: 40 was prepared in the same manner as in Example 4-1, and a 1.2 μm thick coating film pattern was similarly formed. Was performed, 170 mJ / in terms of 365 nm
The pattern could be formed in cm ² .

Example 4-3 In Example 4-1, the pigment is phthalocyanine blue:
A blue photosensitive resin composition with dioxazine violet = 80: 20 was prepared, and a 1.0 μm thick coating film was formed in the same manner.
The pattern could be formed at J / cm ² .

Example 4-4 A black photosensitive resin composition in which the pigment was carbon black was prepared in Example 4-1, and a coating film having a thickness of 1.2 μm was formed in the same manner. It was possible to form a pattern at 400 mJ / cm ² .

[Example 5] In Example 4, instead of pentaerythritol triacrylate (PE-3A, Kyoeisha Chemical Co., Ltd.) as the polyfunctional monomer, EO-modified trimethylolpropane triacrylate (TMP, Kyoeisha Chemical Co., Ltd.) was used. The same operation was performed using -6EO-3A), and it was possible to perform pattern formation in the same manner for red, green, blue and black.

[Example 6] In Example 4, dipentaerythritol hexaacrylate (Kyoeisha Chemical Co., Ltd. DPE) was used in place of pentaerythritol acrylate (Kyoeisha Chemical Co., Ltd. PE-3A) as the polyfunctional monomer.
When the same operation was performed using -6A), red, green,
Pattern formation could be performed similarly for blue and black.

[Example 7] The pattern formation was repeated by the method of Example 4 to prepare a color filter having a stripe pattern with openings of 100 µm x 300 µm and a black matrix line width of 30 µm. 5 color filters
% NaOH, 5% H ₂ SO ₄ , N-methylpyrrolidone, γ
-As a result of immersing each in butyl lactone and isopropyl alcohol at 25 ° C for 30 minutes and evaluating the appearance thereafter, no change was observed and the chemical resistance was good.

Example 8 Binder Resin Acrylic resin (molecular weight 25,000) obtained in Example 1
0) was dissolved in ethyl lactate to a resin concentration of 10% by weight to prepare a binder resin solution. To 100 parts by weight of this binder resin solution, 7 parts by weight of pentaerythritol triacrylate (PE-3A, Kyoeisha Chemical Co., Ltd.) and 2- (o-methoxystyryl) -4,6-bis (trichloromethyl) -S- Triazine (Midori Chemical Co., Ltd.)
When 0.85 part by weight of TAZ-118) was added and stirred, the triazine-based compound was completely dissolved, and a transparent photosensitive resin composition solution was obtained.

The above transparent photosensitive resin composition solution was applied onto a glass substrate with a spinner so as to have a thickness of 1.20 μm, and prebaked at 100 ° C. for 5 minutes on a hot plate to be transparent on the glass substrate. A coating film of a different photosensitive resin composition was formed. The obtained coating film was irradiated with ultraviolet rays through a mask using an ultra-high pressure ultraviolet lamp (1 kw), and then PEB treatment was performed at 100 ° C. for 5 minutes,
Na ₂ CO ₃ (0.25% by weight) + NaHCO ₃ (0.2
Development was performed using a developing solution (pH = 10.0) of 5% by weight). Then, it was sufficiently washed with pure water and post-baked at 200 ° C. for 30 minutes. As a result, pattern formation could be performed at 4 mJ / cm ² in terms of 365 nm.

Example 9 2- (o-methoxystyryl) -4,6-bis (trichloromethyl) -S of Example 8
The same operation was performed using 2- (2,4, -dimethoxystyryl) -4,6-bis (trichloromethyl) -S-triazine (Midori Kagaku Co., Ltd. TAZ-114) instead of -triazine. However, it was completely dissolved and was 365 nm
The pattern could be formed at a conversion of 3 mJ / cm ² .

Example 10 2- (o-methoxystyryl) -4,6-bis (trichloromethyl) -of Example 8
Instead of S-triazine, 2- (3,4,5-trimethoxystyryl) -4,6-bis (trichloromethyl)-
The same operation was performed using S-triazine (Midori Kagaku Co., Ltd. TAZ-111).
The pattern could be formed at 5 mJ / cm ² in terms of 5 nm.

Comparative Example 3 2- (o-methoxystyryl) -4,6-bis (trichloromethyl) -S of Example 8
-2- (p-methoxystyryl) instead of triazine
When -4,6-bis (trichloromethyl) -S-triazine (Midori Kagaku Co., Ltd. TAZ-110) was used,
It was insoluble in ethyl lactate, precipitated, and was unusable.

Comparative Example 4 2- (o-methoxystyryl) -4,6-bis (trichloromethyl) -S of Example 8
When 2- (3,4-dimethoxystyryl) -4,6-bis (trichloromethyl) -S-triazine (Midori Kagaku Co., Ltd. TAZ-113) was used instead of triazine, it was insoluble in ethyl lactate. , Precipitated and was unusable.

[Example 11] Colored photosensitive resin composition A colored photosensitive resin composition was prepared using the triazine-based photopolymerization initiator which was confirmed to be applicable in Examples 8 to 10. Example 11-1 Using the acrylic resin produced in Example 1, the following red photosensitive resin compositions were prepared. Acrylic resin AA / HEMA / BMA / MMA = 15/35/35 /
15 (8.7% by weight) Polyfunctional monomer pentaerythritol triacrylate (PE-3A, Kyoeisha Chemical Co., Ltd. PE-3A) (6.1% by weight) Photoinitiator 2- (o-methoxystyryl) -4,6-bis (Trichloromethyl) -S-triazine (Midori Kagaku Co., Ltd. TA
Z-118) (0.7% by weight) Solvent Ethyl lactate (78.0% by weight) Pigment Chromophtal red: Disazo yellow = 85:15
(6.5% by weight)

The above red photosensitive resin composition solution was applied onto a glass substrate with a spinner so as to have a thickness of 1.1 μm, and prebaked at 100 ° C. for 5 minutes on a hot plate to give a red color on the glass substrate. A coating film of the photosensitive resin composition was formed. The obtained coating film is irradiated with ultraviolet rays through a mask using an ultra-high pressure ultraviolet lamp (1 kw),
After that, PEB treatment is performed at 100 ° C. for 5 minutes, and Na ₂ C is added.
Development was performed using a developer (pH = 10.0) of O ₃ (0.25% by weight) + NaHCO ₃ (0.25% by weight). Then, it was sufficiently washed with pure water and post-baked at 230 ° C. for 30 minutes. As a result, 80m when converted to 365nm
The pattern could be formed at J / cm ² .

Example 11-2 A green photosensitive resin composition in which the pigment was phthalocyanine green: disazo yellow = 60: 40 was prepared in the same manner as in Example 11-1, and a 1.2 μm thick coating film pattern was similarly formed. Was carried out, 140 mJ / in terms of 365 nm
The pattern could be formed in cm ² .

Example 11-3 In Example 11-1, a blue photosensitive resin composition was prepared in which the pigment was phthalocyanine blue: dioxazine violet = 80: 20, and a 1.0 μm thick coating film pattern was prepared in the same manner. When formed, it is 7 in terms of 365 nm.
The pattern could be formed at 0 mJ / cm ² .

Example 11-4 In Example 11-1, a black photosensitive resin composition in which the pigment was carbon black was prepared, and a coating film having a thickness of 1.2 μm was formed in the same manner. It was possible to form a pattern at 350 mJ / cm ² .

[Embodiment 12] In Embodiment 11-1,
As a photopolymerization initiator, 2- (o-methoxystyryl)-
2- (2,4-dimethoxystyryl) -4, in place of 4,6-bis (trichloromethyl) -S-triazine
When a similar operation was performed using 6-bis (trichloromethyl) -S-triazine (Midori Kagaku Co., Ltd. TAZ-114), pattern formation could be similarly performed.

[Embodiment 13] In Embodiment 11-1,
As a photopolymerization initiator, 2- (o-methoxystyryl)-
Instead of 4,6-bis (trichloromethyl) -S-triazine, 2- (3,4,5-trimethoxystyryl)-
When the same operation was performed using 4,6-bis (trichloromethyl) -S-triazine (Midori Kagaku Co., Ltd. TAZ-111), pattern formation could be similarly performed.

[Embodiment 14] The pattern formation was repeated by the method of Embodiment 11, and the openings were 100 μm × 300 μm.
m, and a black matrix line width 30 μm stripe pattern color filter was produced. The obtained color filter was immersed in 5% NaOH, 5% H ₂ SO ₄ , N-methylpyrrolidone, γ-butyl lactone and isopropyl alcohol at 25 ° C. for 30 minutes, and the appearance was evaluated. It was not seen, and the chemical resistance was good.

[0058]

Industrial Applicability According to the present invention, ethyl lactate, which is a safe solvent which is said to be rapidly decomposed in the body and in the natural world, is used as a solvent, and a polyfunctional monomer adapted to it was found, thereby obtaining a highly sensitive transparent polymer. It is possible to provide a different colored photosensitive resin composition. Further, according to the present invention, the colored photosensitive resin composition enables the production of a color filter using a safe solvent. Furthermore, according to the present invention, a highly sensitive triazine-based photopolymerization initiator corresponding to ethyl lactate was found, whereby a highly sensitive colored photosensitive resin composition can be prepared.

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Claims (4)

[Claims] 1. A colored photosensitive resin composition comprising a pigment, an acrylic resin, a polyfunctional monomer, a photopolymerization initiator, and a solvent as essential components, wherein the solvent is ethyl lactate and the polyfunctional monomer is penta A colored photosensitive resin composition, which is at least one selected from the group consisting of erythritol acrylate, ethylene oxide-modified trimethylolpropane triacrylate, and dipentaerythritol hexaacrylate. 2. The photopolymerization initiator is 2- (o-methoxystyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (2,4-dimethoxystyryl) -4,
6-bis (trichloromethyl) -S-triazine, and 2- (3,4,5-trimethoxystyryl) -4,6-
The colored photosensitive resin composition according to claim 1, which is at least one selected from the group consisting of bis (trichloromethyl) -S-triazine. 3. The acrylic resin, polyfunctional monomer, and photopolymerization initiator content (weight ratio) are as follows:
Polyfunctional monomer: Photopolymerization initiator = 1: 0.3: 0.03
The colored photosensitive resin composition according to claim 1, wherein the colored photosensitive resin composition is in the range of 1: 1 to 0.8. 4. A colored layer comprising a photocured product of the colored photosensitive resin composition according to any one of claims 1 to 3 formed in a pattern on a transparent substrate. Color filter.