JPH0364754A - Photosensitive resin composition and hardened material - Google Patents

Abstract

PURPOSE:To enhance resolution, to rationalize processes and to save energy by incorporating a polymer having groups affinitive to an anionic dye, and unsaturated groups reactive with an azido compound in the same molecule, a photosensitive azido compound, and a compound having >=2 acryloyl and/or methacryloyl groups in the same molecule. CONSTITUTION:The photosensitive resin composition contains the polymer A having groups affinitive to an anionic dye, and unsaturated groups reactive with an azido compound in the same molecule, the photosensitive azido compound B, and the compound C having >=2 acryloyl and/or methacryloyl groups in the same molecule. In general, the compound C alone requires a light quantity of several times that of the compound B, but the use of the compounds C and B at the same time makes it possible to attain the purpose by a small quantity of light, because mutual actions promote cross-linking actions between the unsaturated roups of the polymer A and the azido groups, and between the azido groups of the compound B and the acryloyl and/or methacryloyl groups of the compound C, thus permitting resolution to be enhanced, the process to be rationalized, and energy to be saved.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a photosensitive resin composition and a cured product thereof for easily dyeing substrates such as glass and solid-state imaging devices into arbitrary colors with anionic dyes. It is related to.

In recent years, base materials such as glass have been colored and used in famous displays, and in particular, base materials such as glass have been colored and used as color separation filters for LCD color TV sets.
Demand for dyeing solid-state image sensors is increasing as colorization of color television cameras increases. The present invention relates to a photosensitive resin composition for dyeing substrates such as glass, and a cured product thereof, which has been made to meet such demands.

(Prior art) Conventionally, in this field, protein-based natural polymer substances such as casein and gelatin have been mainly used. Add potassium dichromate or ammonium as
Next, actinic light is irradiated through a mask to form a latent image of the dyeable layer on the glass plate, and then the dyeable layer is exposed by development. Next, a natural polymeric substance is used, such as dyeing this with a dye. Recently, products using synthetic polymers have also been put into practical use.

(Problems to be Solved by the Invention) When using casein, gelatin, etc., it is easy to spoil because they are natural products, and the quality is not consistent and varies depending on the raw material source, resulting in extremely poor color reproducibility. , easy to peel off in hot water, and physical properties deteriorate significantly due to heat.
There are drawbacks such as limited processing conditions. Furthermore, there are dyeing problems such as difficulty in obtaining deep colors because the temperature of the dye bath during dyeing is restricted.

Furthermore, when using casein, gelatin, etc., ammonium dichromate or potassium dichromate is used as a photocuring agent, so problems of pollution must be solved during the working process and during disposal. Furthermore, there is a problem that chromium incorporated into gelatin cannot be completely removed, and the remaining chromium may have an adverse effect.

The present inventors investigated synthetic polymers in order to solve these problems. As a result, patent application No. 114681/1983 was filed.

The method of patent application No. 63-88993 was invented and is now being put into practical use.

However, in recent years, there has been a demand for a further reduction in the amount of light used for curing photosensitive resin compositions due to demands for high-resolution quality, speeding up of processes, energy saving, etc. Generally, when the amount of light applied to a photosensitive resin composition is insufficient, the film becomes weak and roughness occurs during dyeing, and the dyed film becomes opaque. In addition, the dyeing properties are poor and the dispersion properties are also poor. Furthermore, there are other problems such as poor dimensional stability of the image. In order to meet this demand, various conventionally known methods have been investigated to accelerate the photoreaction rate of the azide compound in the photosensitive resin M acid, but none of them has been satisfactory.

(Means for Solving the Problems) The present inventors have completed the present invention as a result of further studies to solve these problems.

That is, the present invention provides the following features: 1. (a) a polymer (A) having both a group (a) having an affinity for anionic dyes and an unsaturated group (b) capable of reacting with an azide compound in the same molecule; A photosensitive resin composition (D) comprising an azide photosensitive compound (B) and (c) a compound (C) having two or more acryloyl groups and/or methacryloyl groups in the same molecule; 2. The above photosensitive resin composition It relates to the cured product of (D).

The photosensitive resin composition (D) of the present invention accomplishes the curing reaction with a fraction of the amount of light compared to the case where the compound (C) is not used.

In general, compound (C) alone requires several times as much light as the azide photosensitive compound (B). However, by simultaneously using the azide photosensitive compound (B) and the compound (C), the objective can be achieved with a small amount of light. This is a polymer (
The unsaturated group (b) in A), the azide group in the azide-sensitive compound (B) and the acryloyl group in the compound (c) and/or
Alternatively, it is presumed that because a favorable interaction between the compound and the methacryloyl group that causes the crosslinking reaction to occur efficiently occurs, the objective can be achieved with a smaller amount of light than in the case where compound (C) is not added.

The polymer (A) used in the present invention is a dyeable monomer (
c), a monomer having an unsaturated group that can react with an azide compound (d), a hydrophilic monomer (e), a hydrophobic monomer (
It is preferable that the polymer (A) contains as a constituent component, and the polymer (A) can be produced by using a conventionally known polymerization method.

Here, the dyeable monomer (c) includes the following.

(N, N-dimethylamino)) ethyl acrylate, (N, N-dimethylami)) ethyl methacrylate, (N, N-diethylamino)) ethyl acrylate, (N, N-diethylamino) ethyl methacrylate, (N, N- dimethylamino)) propyl acrylamide, (N, N-dimethylamino) propyl methacrylamide, (Ill, N-dimethylamino)) ethyl vinyl ether, (N, N-dimethylamino)) propyl acrylate, (N, N- dimethylamino)) progyl methacrylate, 4-vinylpyridine, diaryl ane, 2-hydroxy-3-methacryloyloxypropyltrimethylammonium chloride, methacryloyloxyethyltrimethylammonium chloride, and unsaturated groups capable of reacting with azide compounds. The monomers (2) include: allyl acrylate, allyl methacrylate, allyl acrylamide, allyl methacrylamide, diallyl, P-allylstyrene, P-vinyl blackinnamate, 1-acryloxy 1-hydroxy 2- Examples include cinnamoyloxyethane and 4-acryloyloxystilbene.

Examples of hydrophilic monomers (e) include the following.

Hydroxyethyl acrylate, hydroxyethyl methacrylate-1, hydroxyethyl acrylamide, hydroxyethyl methacrylamide, acrylamide, methacrylamide, vinylpyrrolidone, dimethylamino acrylamide, methylaminoacrylamide, dimethylaminomethacrylate Examples of hydrophobic monomers include the following.

Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, styrene, P-methylstyrene, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, these dyeable monomers (c) , the monomer having an anti-windowable unsaturated group (d), the wood-philic monomer (e), and the hydrophobic monomer (b) are mixed in the proportions of the dyeable monomer (d).
c) 10 to 80% by weight, monomers having unsaturated groups (d) 1 to 20% by weight, hydrophilic monomers (e) 2 to 60% by weight, hydrophobic monomers (f) 5 to 50% by weight It is preferable that

In addition, in some cases, a polymer containing no monomer (d) having an unsaturated group capable of reacting with an azide compound is synthesized in advance, and the unsaturated group is removed by a known method such as esterification, amidation, quaternization reaction, etc. There is also a way to introduce . Examples of the compounds used in this case include the following.

Allyl chloride, allyl bromide, 3-chloro-2
-Methylpropene, 3-chloro-1-methylpropene, 4-bromo-1-butene, chloroacetic acid allyl ester, chloroacetic acid vinyl ester, T-chloro-isobutyne, m-chloromethylstyrene, 3-chloro -2-Hydroxybrobyl methacrylate
Shi-to, β-chloroethyl cinnamic acid ester, β-bromoethyl cinnamic acid ester, β-bromoethyl cinnamylidene acetate, β-bromoethyl furyl acrylate, P-β-bromoethyloxycarbonylbenzalacetophenone, β -chloroacetoxystilbene, crotonic acid chloride, cinnamic acid chloride, β-furylacrylic acid chloride, N-(chlorocarbonylmethyl)phenylmaleimide, and the molecular weight of the polymer (A) thus prepared is 2,000 to 200.000 is preferred, especially s, o
It is preferable that it is oo~100,000.

Moreover, the following can be mentioned as the azide photosensitive compound (B) used in the present invention.

414′-Diazidochalcone, 2.6-bis(4″-azidobenzal)cyclohexanone, 2.6-bis(4′-azidobenzal)4-methylcyclohexanone, 1.3-bis(4°-azidobenzal)- 2-propanone, P-azidobenzalacetophenone, P-azidobenzalacetone, 1,3-bis(4'-azidobenzal)-2-propanone-2°-sulfonic acid, 4.4°-diazidostilbene-2 ,2'-disulfonic acid, 4.4°-diazidostilbene-2,2'-disulfonic acid sodium, 1.3-bis(4°-azido-2'-sulfonic acid-benzal)-2-propanone, 1 .3-bis(4′-azido-2″-sulfonic acid benzal)-2-propanone, 2.6-bis(4′-
Azido-2°-sulfonic acid-benzal)cyclohexanone, 2,6-bis(4'-azido-2'-sulfonic acid-benzal)methylcyclohexanone, 2,6-bis(4'-
Azido-2°-sulfonic acid benzal) methylcyclohexanone, How much of these azide photosensitive compounds (B) should be used in poly? −(
A) Preferably 70.1 to 20 parts per 100 parts, particularly preferably 0.5 to 10 parts.

Examples of the compound (C) used in the present invention include the following.

Spiroglycol diacrylate [3,9-bis(2-
acryloyloxy-1,1-dimethyl) -2,4,
8,10-tetraoxaspiro(5,5)undecane]
, cyclohexane dimethylol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, butylene glycol diacrylate, neopentyl glycol diacrylate, 1,4-butane diol diacrylate Acrylate, 1.6-hexanediol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, novolak epoxy acrylate, bisphenol A epoxy acrylate, alkylene glycol jepoxy acrylate, glycidyl ester acrylate, polyester Diacrylate, bisphenol A diacrylate, urethane diacrylate, methylene bisacrylamide, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, propylene glycol dimethacrylate, butylene glycol dimethacrylate, neopentyl Glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, trimethylolbroban trimethacrylate, the usage type of these compounds (C) is 0.1- to 100 parts of polymer (A). 20 parts is preferred, particularly 0.5 to 10 parts.

The photosensitive resin composition (j, usually has
It is used after being diluted with a solvent, etc.

Examples of organic solvents include methyl cellosolve, ethyl cellosolve, toluene, xylene, N-methylpyrrolidone, ethylene glycol monoethyl ether acetate-1.
, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, methyl isobutyl ketone,
Examples include methyl ethyl ketone, but these may be used alone or as a mixture of two or more. The proportion of the Il-containing solvent in this photosensitive resin liquid varies depending on the composition of these resin liquids, so it cannot be unconditionally defined, but it is important to ensure that the viscosity is such that it can be applied to the resin liquid and the surface of the substrate. preferable.

A base material such as glass coated with this resin liquid is usually exposed to ultraviolet rays or the like through a mask.

The unexposed area tj is developed with an aqueous solution.

The development is preferably carried out at room temperature - 60°C. The film thickness of the resin developed in this manner can be set to any desired thickness, for example, from 0.2 to 10 μm. A substrate such as glass or plastic having a developed predetermined pattern is dyed with an anionic dye.

Color Index Kyu (Soel) is an anionic dye.
eiy of Dyer! 1andColouris
Acidic dyes listed as C,K Ac1d (published by Ts), direct dyes listed as C,Ilirect and same < C,X Reactive
Among them, acidic dyes are particularly preferred. As acidic dyes, C, 1^ai
d Y@llow17, 49, 67, 72, 127 110, 135°, 161, C, I
Ac1d Red 37, 50, 111, 114
, 257, 266, 317, C, I Ac1d
B1ue41, 83, 90, 113, 12
9, 182, 125, C, I Acid Oran
ge7, same 56, C, I ^cid Green25
, 41, C,I Ac1d Violet 97, 27, 28, 48, etc.

In the dyeing method using these, 0.01 to 200 parts by weight of the dye is dissolved in 1000 parts by weight of water.

The +lH of this liquid removal may be in the weak alkaline-acid range.This dye solution is used for dyeing at a temperature range of room temperature to 100°C, but it is not recommended to dye at a high temperature because the dyeing can be done in a short time. preferable. After dyeing in this manner, the dyed product is fixed with a dye fixing agent such as tannic acid, and color filters of red, green, blue, etc. can be produced by the conventionally known method C.

(Example) Example 1 Dimethylaminopropylacrylic acid 31 parts 2-hydroxyethyl methacrylate 14 parts Vinyl bi-Olidone 15s methyl methacrylate 12 I methyl acrylate
13# dimethylaminoacrylic acid
10-allyl methacrylate-1-2,5 # diallyl methacrylate 5 Isopropyl alcohol 200 parts 2.2°-Azobis(2,4-dimethylvaleronitrile)
After carrying out the main polymerization reaction of 2 parts of the above-mentioned liquid in an atmosphere of 40" C for 18 hours, the polymerization solution was poured into a large amount of isopropyl ether to precipitate the polymer, and then the polymer was taken out and dried.

To 17 parts of this dry polymer, 0.68 part of 4.4'-diazide chalcone, 0.70 part of cyclohexane dimethylol diacrylate, 100 parts of ethyl cellosolve, 34 parts of diethylene glycol dimethyl ether, silane cuff pulling agent KBM603 ( Kei Kagaku Kogyo ■) 0.60
A solution obtained by mixing and dissolving the following parts was used as a photosensitive resin liquid. Next, this was coated on a glass plate using the spin code method, and
After drying for Cl2O, IIV irradiation with a surface illuminance of 13*W/cd was performed for 5 seconds through a mask with a resolution test pattern, and Emaluan 913 (manufactured by Kao Soap ■, a polyoxyethylene nonylphenol ether type nonionic surfactant) was applied. When development was carried out for 5 minutes with stirring in a developer solution at 40° C. containing 2 parts per 1000 parts of water, a glass plate having a dyeable film only in the irradiated area was obtained.

After this glass plate was further post-baked at 150° C. for 30 minutes, the film thickness was 0.6 μm. This glass plate is blue 43
p (manufactured by Nippon Kayaku, color filter dye) 0
．． When it was dissolved in water to a concentration of 2% and dyed at 60°C for 10 minutes, a glass plate dyed in a deep blue pattern was obtained. The resolution of the pattern on this glass plate is 3.5μ
Both the transparency of the dyed film and the dimensional stability of the image were satisfactory.

Example 2 The same procedure as in Example 1 was repeated except that 10 parts of diallyl was used instead of 7,175 parts of diallyl. In this case, the optimum irradiation time was 20 seconds, the film thickness after post-baking was 0.6 μm, and the pattern resolution was 3.1 μm.

Both the transparency of the dyed film and the dimensional stability of the image were satisfactory.

Example 3 In Example 2, 1,3-bis(4°-azidobenzal)-2-propanone was used instead of 4,4°-diazidechalcone, and 2 parts of toluene was added to 100 parts of the photoreactive resin liquid.
The same operation was performed by adding 0 copies. In this case, the optimum irradiation time was 5 seconds, the film thickness after post-baking was 0.5μ, and the resolution of the resulting pattern was 3.5μ. Both the transparency of the dyed film and the dimensional stability of the image were satisfactory.

Example 4 In the formulation of Example 1, instead of 5 parts of diallylamine, 1
The same operation was performed using 5 copies.

In this case, the optimum irradiation time was 20 seconds, the film thickness after post-baking was 0.6μ, and the pattern resolution was 2.5μ.

Both the transparency of the dyed film and the dimensional stability of the Wi pattern were satisfactory.

Example 5 In Example 1, 5 parts of diallylamine was replaced with 2 parts, and cyclohexane dimethylol diacrylate was replaced with Kayahard D-320 (dipentaerythritol tetraacrylate, alkylol modified product, manufactured by Nippon Kayaku ■).
The same operation was performed except that the drying temperature was changed to 60°C instead of 80°C.

In this case, the optimum irradiation time was 10 seconds, the film thickness after post-baking was 0.5μ, and the pattern resolution was 2.0μ. Both the transparency of the dyed film and the dimensional stability of the image were satisfactory.

Example 6 The same operation as in Example 5 was carried out using dipentaerythritol hexaacrylate instead of Kayahard D-320. In this case, the optimal irradiation time is 10 seconds, the film thickness after post-bake is 0.5μ, and the pattern resolution is 2.0μ.
Met. Both the transparency of the dyed film and the dimensional stability of the image were satisfactory.

Example 7 The same operation as in Example 4 was carried out using 5.0 parts of allyl methacrylate instead of 2.5 parts.

In this case, the optimum irradiation time was 5 seconds, the film thickness after Bonest baking was 0.6 μm, and the pattern resolution was 1.8 μm. Both the transparency of the dyed film and the dimensional stability of the image were satisfactory.

Example 8 Methyl methacrylate 5 parts N, N'-
Dimethylaminoprobyl acrylamide 30 parts 2-Hydroxyethyl methacrylate IO # Vinyl pyrrolidone 15〃Dimethylaminoacrylamide ξde 10〃Butyl acrylate
301α,α°-azobis(isobutyronitrile) 2 parts dioxane 250# After polymerizing the liquid of the above formulation in a nitrogen atmosphere at 70"C for 18 hours, the polymerization solution was poured into isopropyl ether to precipitate the polymer. I let it happen.

The polymer was taken out and dried, and 32 parts of allyl chloride was added to a solution prepared by adding and dissolving 100 parts of ethyl cellosolve to 30 parts of the polymer. After reacting at room temperature for 48 hours, the polymer was poured into isopropyl ether to precipitate the polymer.

After drying this polymer, 15 parts of this polymer, 4.4"-
A photoreactive #M sacrificial solution containing 17,006 parts of diadocal, 0.68 parts of cyclohexane dimethylol diacrylate, 0.5 parts of KRM, and 85 parts of ethyl cellosolve was prepared.

Next, the photoreactive resin liquid was applied to a glass plate by a spin code method, and after drying at 80°C for 20 minutes, UV irradiation was performed for 5 seconds at a surface illuminance of 8 mW/cffl through a mask with a predetermined pattern. A glass plate having a dyeable film only in the C irradiated area was obtained by performing development for 5 minutes at room temperature using water as a developer. After drying this glass plate at 150°C for 30 minutes, dissolve Green IP (a dye for color filters manufactured by Nippon Kayaku ■) in water to a concentration of OOL% and dye it at 60°C for 10 minutes! :WA A glass plate dyed in a thick green pattern was obtained.

The film thickness of the pattern was O08μ. The pH of the dye bath is 7
．． It was 5. Red 137p instead of green IP,
When the same operation was carried out using Blue 43p) (both dyes for color filters manufactured by Nippon Kayaku ■), glass plates having patterns dyed deep red and blue electric were obtained, respectively. The resolution of this pattern was 5μ.

Example 9 The same operation as in Example 7 was carried out using 0.3 parts of ethylene glycol dimethacrylate and 0.4 parts of cyclohexane dimethylol diacrylate instead of 0.70 parts of Schiff 0 hexane dimethylol diacrylate. Ta. In this case, the optimum irradiation time is 10 seconds, and the film thickness after boost baking is 0.
6μ, and the pattern resolution was 2.0μ. Both the transparency of the dyed film and the dimensional stability of the image were satisfactory.

Example 10 Using the photosensitive resin liquid used in Example 1, a glass plate was dried for 20 minutes using a spin code method, and then coated through a mask having a 200μ stripe pattern for making a color filter. Then, irradiation was performed for 20 seconds using the UV irradiation device W of Example 1, followed by drying, development, and drying in the same manner as in Example 1.
After post-baking, dyeing was carried out for 70'' in a bath containing 0.1% of Left 137P (Nippon Kayaku Color Filter Dye T?4) for 70'' Cl2O to obtain a glass plate with a red stripe pattern. Ta.

Next, this was treated in a bath containing 3 g/l of tannic acid and 2 g/l of acetic acid at 70°C for 5 minutes, and further treated with 21-Pavalon (
Manufactured by Dainippon Pharmaceutical ■, antimony sodium tartrate solution) 5
g/j! After treatment in a bath containing 70° C. for 5 minutes, the glass plate was treated at 150° C. for 20 minutes to fix the dye. Next, this glass plate was similarly coated with the photosensitive resin solution, dried, UV irradiated on the parts that were not dyed first, developed, and post-baked, followed by CFG.
-5113 (Color filter dye made by Nippon Kayaku 11!) After dyeing in a bath containing 0.1% at 60℃ for 10 minutes, fixation treatment with tannin and New Poweron according to the above recipe results in red and green stripes. A glass plate with a pattern was obtained.

Next, this glass plate was coated in the same manner using the photosensitive resin solution, dried, UV irradiated on the parts that were not dyed first, developed, and post-baked. Dyeing for Filters $14) Dyeing was carried out at 60° C. for 10 minutes in a bath containing 0.1%, and a glass plate for color filters having a stripe pattern of three colors of red, green, and blue was obtained.

Reference Example 1 The same operation as in Example 1 was carried out without adding 0.70 part of cyclohexane dimethylol diacrylate.

As a result, the resolution of the image was 6.2μ, and the dimensional stability of the image was also inferior to that of Example 1.

Reference f! 42 The same operation as in Example 2 was carried out without adding 0.70 part of cyclohexane dimethylol diacrylate.

As a result, the film peeled off and no image could be created.

Reference Example 3 The same operation as in Example 3 was carried out without adding 0.70 part of cyclohexane dimethylol diacrylate.

As a result, the film peeled off and it was not possible to create an image.

Reference Example 4 The same operation as in Example 4 was carried out without adding 0.70 part of cyclohexane dimethylol diacrylate.

As a result, the resolution of the image was 6.2μ, and the dimensional stability of the image was also inferior to that of Example 4.

Reference Example 5 The same operation as in Example 5 was carried out without adding 0.70 parts of Kayahard D-320. As a result, the resolution of the image was lOμ, and the dimensional stability of the image was also inferior to that of Example 5.

Reference Example 6 The same operation as in Example 7 was performed without adding 0.70 part of cyclohexane dimethylol diacrylate.

The optimal irradiation time in this case was 40 seconds, and the image resolution was 3.1μ.

Reference Example 7 The same operation as in Example 8 was performed without using 0.68 part of cyclohexane dimethylol diacrylate. As a result, the resolution of the image was 15μ, and the dimensional stability of the image was also inferior to that of Example 8.

(Effects of the Invention) Compared to conventional gelatin, which is a natural product, or casein dichromate-based photosensitive compositions, the present invention does not have the problems of spoilage and large variations in composition and raw materials. There is no problem of hexavalent chromium pollution.

Furthermore, the photosensitive resin M acid compound (D) of the present invention is a compound (C)
Since the resin is cured with a small amount of light compared to when it is not used, it is useful for creating fine patterns, saving energy, streamlining processes, and reducing costs.

Claims (1)

[Claims] 1. (a) A polymer (A) having both a group (a) having an affinity for anionic dyes and an unsaturated group (b) capable of reacting with an azide compound in the same molecule (b) ) A photosensitive resin composition comprising an azide photosensitive compound (B) and (c) a compound (c) having two or more acryloyl groups and/or methacryloyl groups in the same molecule. 2. A cured product of the photosensitive resin composition according to item 1.