JPH0644151B2 - Pattern forming method for dyeable resin film - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a patterning method of a dyeable resin film for dyeing a transparent substrate such as glass into a stripe, mosaic or other shape with a dye. It is a thing.

In recent years, a transparent base material such as glass colored in a stripe or mosaic shape has been increasingly used as a color separation filter for colorizing a liquid crystal color TV or a camera for a color TV. The present invention relates to a method for forming a pattern of a dyeable resin film for dyeing a transparent base material such as glass in a stripe shape, a mosaic shape or the like, or in another shape, in order to meet such demands.

(Prior Art) Conventionally, dyeable photosensitive resin compositions have been used in this field, but those who use these dyeable photosensitive resins should first dilute a solution to an appropriate concentration. Repeat operations such as applying to a plate, etc., then exposing through a mask and then developing to form a stripe or mosaic dyeable resin film, which is dyed with a dye having a predetermined spectral characteristic. I have created a filter for color separation by
In developing the resin film, a neutral to acidic aqueous solution at 20 to 70 ° C. is used.

(Problems to be Solved by the Invention) As described above, when the dyeable photosensitive resin composition is applied to a glass plate or the like, exposed through a mask, and then developed using water at 20 to 70 ° C. If the development time is long, or because the cake-like material of the dyeable photosensitive resin composition once dropped by development is reattached to a glass plate or the like, defective products are likely to occur, or if development is performed with an acidic solution, The development time can be shortened, but there is a problem that the exposed part of the film will be rough, so the process is rationalized,
Further improvements have been desired in terms of yield.

(Means for Solving Problems) As a result of investigations by the present inventors to solve these problems, the dyeable photosensitive resin liquid was applied to a glass plate or the like and exposed through a mask. It has been found that the object can be achieved by developing using an aqueous solution containing a nonionic surfactant, and the present invention has been completed.

That is, the present invention comprises: a) a dyeable monomer (A) 10 to 80% by weight b) a hydrophilic monomer (B) other than the dyeable monomer (A) 2 to 60% by weight c) a hydrophobic monomer (C) A dyeable photosensitive resin composition comprising a copolymer (D) obtained by copolymerizing a mixture of 5 to 50% by weight is used to form a film on the surface of a substrate such as a glass plate, The present invention relates to a method for forming a pattern of a dyeable resin film, which is characterized in that an aqueous solution containing a nonionic surfactant is used as a developing solution when exposed using a mask and developing with a developing solution.

When the nonionic surfactant-containing aqueous solution of the present invention is used, the development time can be shortened as compared with the case where no addition is made, and the re-adhesion of the resin in the unexposed portion which has fallen off due to the development is also reduced, and the process is rationalized and the quality is improved. It helps to improve the yield and yield. In this case, the nonionic surfactant is a wetting and penetration promoter for water in the unexposed area,
It is presumed that it acts as an anti-redeposition agent for the dropped resin and enables development in a short time.

Among the surfactants, the anionic surfactant is ionically bound to the dyeable photosensitive resin, so that the addition of the anionic surfactant to the developer deteriorates the developability. Further, when a cationic surfactant is used, the development time is shortened and the redeposition of the unexposed resin composition is eliminated, but when this is dyed with a dye, the transparency of the dyed exposed part is lost and the commercial value is lost. It was unsuitable because it would end up.

Examples of the nonionic surfactant used in the present invention include polyoxyethylene alkyl ether and polyoxyethylene alkylphenol ether-based, sorbitan fatty acid ester-based, polyoxyethylene sorbitan fatty acid ester-based, polyoxyethylene acyl ester-based, oxyethyleneoxypropylene. Block polymers, fatty acid monoglycerides, etc. may be mentioned. These may be one type or a mixed system of two or more types. The amount of these nonionic surfactants used is preferably 0.1 to 50 parts, and particularly preferably 0.5 to 10 parts, per 1000 parts of water. The developing temperature is 15-80 ° C.
Is preferred.

Examples of the dyeable photosensitive resin composition used in the present invention include the following.

That is, a copolymer (D) comprising a dyeable monomer (A), a hydrophilic monomer (B) and a hydrophobic monomer (C) or a sensitizer such as 4,4'-diazidochalcone, 2,6 -Bis (4 '
-Azidobenzal) cyclohexanone, 2,6-bis (4'-azidobenzal) cyclohexanone, 2,6-
A dyeable photosensitive resin composition obtained by combining bis (4'-azidobenzal) 4-methylcyclohexanone, 1,3-bis (4'-azidobenzal) -2-propanone, or a copolymer thereof (D ) Is reacted with a compound having a photosensitive group such as a cinnamoyl group, an azido group, an acrylic group, a styrylpyridinium salt structure or a styrylquinolium salt structure to give a dyeable photosensitive resin composition. When the dyeable monomer (A), the hydrophilic monomer (B), and the copolymer (D) itself composed of the hydrophobic monomer (C) are used as the dyeable photosensitive resin composition, a cinnamoyl group and an azide are used as the monomer. A dyeable photosensitive resin composition obtained by copolymerizing a monomer having a group, an acrylic group, a styrylpieridinium salt structure, a styrylquinolium salt structure, or the like is preferable.

Examples of the dyeable monomer (A) used in the present invention include the following.

(N, N-dimethylamino) ethyl acrylate (N,
N-dimethylamino) ethyl methacrylate, (N, N
-Diethylamino) ethyl acrylate, (N, N-diethylamino) ethyl methacrylate, (N, N-dimethylamino) propylacrylamide, (N, N-dimethylamino) propylmethacrylamide, (N, N-dimethylamino) ethyl vinyl ether, (N, N-dimethylamino) propyl acrylate, (N, N-dimethylamino) propyl methacrylate, 4-vinylpyridine, diallylamine, 2-hydroxy-3-methacryloyloxypropyl, trimethylammonium chloride, methacryloyloxyethyltrimethylammonium chloride. The hydrophilic monomer used in the present invention
Examples of (B) include the following.

Hydroxyethyl acrylate, hydroxyethyl methacrylate, acrylamide, methacrylamide, vinylpyrrolidone, N, N-dimethylacrylamide.

Examples of the hydrophobic monomer (C) used in the present invention include methyl acrylate, methyl methacrylate, ethyl acrylate, styrene, p-methylstyrene, butyl acrylate and butyl methacrylate.

The copolymer (D) used in the present invention is a dyeable monomer (A) 10 to 80.
It can be obtained by polymerizing a mixture consisting of 2% to 60% by weight of hydrophilic monomer (B) and 5 to 50% by weight of hydrophobic monomer (C) by conventional techniques.

The dyeable photosensitive resin composition used in the present invention is used by diluting it with an organic solvent so that it can be easily applied to a glass plate or the like. Examples of the organic solvent include methyl cellosolve, ethyl cellosolve, ethylene glycol monoethyl ether acetate, diglyme, methyl isobutyl ketone, toluene and xylene.

The substrate such as glass coated with the dyeable photosensitive resin composition is exposed to ultraviolet rays or the like through a mask. The unexposed area is developed with an aqueous solution containing a nonionic surfactant.

The film thickness of the resin thus developed is, for example, 0.2 to 10 μm.
It is possible to create a film of any thickness. The developed base material such as glass or plastic having a predetermined pattern is dyed with an anionic dye.

Color Index (Society
Acid dyes described as CI Acid in Dyers and Colorlsts), direct dyes also described as CI Direct and reactive dyes also described as CI Reactive, etc., but particularly acid dyes are preferable. .

(Example) Example 1. Dimethylaminopropyl acrylamide 30 parts 2-Hydroxyethyl methacrylate 15 parts Vinylpyrrolidone 14 〃 Methyl ethacrylate 30 〃 Dimethylaminoacrylamide 9 〃 Copolymer 16 parts to 4,4'-diazide chalcone
A solution in which 0.65 parts and 84 parts of ethyl cellosolve were mixed and dissolved was used as a dyeable photosensitive resin liquid.

Next, the silane coupling agent KBM503 is applied to the glass substrate.
(Shin-Etsu Chemical Co., Ltd.) A 10% ethanol solution was applied, air-dried, and then dried by heating at 110 ° C. for 5 minutes to obtain a coating substrate.

The dyeable photosensitive resin liquid is applied to the surface of the coating substrate by the roll coater method, dried at 100 ° C. for 30 minutes, and then the surface illuminance is 8 mW through a mask having a predetermined pattern.
UV irradiation of / cm ² for 15 seconds, and then Emulgen 913
(Polyoxyethylene nonylphenol ether type nonionic surfactant manufactured by Kao Soap Co., Ltd.) 2 parts with respect to 1000 parts of water is developed with stirring at a developing solution of 60 ° C. for 5 minutes to develop an irradiated part. A glass substrate having a dyeable film was obtained. This dyeable film had a film thickness of 0.7μ.

After drying this glass substrate at 150 ° C for 30 minutes, red 2
1P (Nippon Kayaku Co., Ltd., color filter dye)
When it was dissolved in water to a concentration of 0.2% and dyed at 60 ° C. for 10 minutes, a glass plate dyed in a deep red pattern was obtained. The glass plate had very little reattachment of the resin dropped to the unexposed area due to development, and the image was extremely clear.

Reference Example 1 The same operation as in Example 1 was carried out using a developing solution at 60 ° C. containing no emulgen 913. In many cases, the development time required to obtain a clear image similar to that in Example 1 was 13
It took a minute. Even in this case, prevention of reattachment of the dropped resin to the unexposed glass plate was insufficient.

Example 2. In Example 1, instead of Emulgen 913, Emulgen 930 (manufactured by Kao Soap Co., Ltd., polyoxyethylene nonylphenol ether type nonionic surfactant) was added to water 100.
When the same operation as in Example 1 was carried out using a developing solution containing 1.8 parts per 0 part, the same results as in Example 1 were obtained.

Example 3 Dimethylaminopropylacrylamide 32 parts 2-Hydroxyethylmethacrylate 12〃 Vinylpyrrolidone 16〃 Dimethylaminoacrylamide 11〃 Butylacrylate 11〃 Methylmethacrylate 14〃 Copolymer containing 17 parts and 2,6-bis (4'azidobenzal) ) A solution in which 0.78 parts of 4-methylcyclohexanone and 83 parts of ethyl cellosolve were mixed and dissolved was used as a dyeable photosensitive resin liquid.

This dyeable photosensitive resin liquid was applied to a glass plate by the same operation as in Example 1, dried, and UV-irradiated through a mask having a pattern.

Next, Emulgen 430 (polyoxyethylene oleyl ether, manufactured by Kao Soap Co., Ltd.) was added to 1000 parts of water for 2.
When development was carried out for 8 minutes with a developer containing 5 parts of 58 ° C., a glass substrate having a dyeable film only on the irradiated part was obtained. The film thickness of this dyeable film was 0.8 μm. This glass substrate 15
After drying at 0 ° C for 30 minutes, Green 1P (Nippon Kayaku Co., Ltd.)
(Manufactured by Color Filter Co., Ltd.) was dissolved in water to 0.1%, and dyeing was carried out at 62 ° C. for 12 minutes to obtain a glass plate dyed in a dark green pattern. This glass plate has no redeposition of resin that has fallen off due to development on the unexposed area,
The image was extremely sharp.

Reference example 2. When the same operation was carried out in Example 3 using a developer at 58 ° C. containing no Emulgen 430, the re-adhesion of the dropped resin to the unexposed glass plate was higher than that in Example 3, and The developing time required to obtain a clear image similar to that in Example 3 is 1
It took 5 minutes. Even in this case, prevention of reattachment of the dropped resin to the unexposed glass plate was insufficient.

Example 4. The same operation as in Example 3 was carried out by using the developing solution containing 2.3 parts of Emulgen 913 in place of Emulgen 430 in 1000 parts of water, and the same result as in Example 3 was obtained. Was given.

(Effects of the Invention) The present invention uses a nonionic surfactant-containing aqueous solution for the development of a dyeable photosensitive resin film, so that the development time can be shortened, which is useful for streamlining the process. Furthermore, since redeposited resin can be prevented from adhering to the unexposed area, higher quality can be obtained and the yield can be improved. Therefore, this method can improve the quality of the color separation filter and also contribute to cost reduction by streamlining the process.

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Claims (1)

[Claims] 1. A) dyeable monomer (A) 10 to 80% by weight b) hydrophilic monomer (B) other than dyeable monomer (A) 2 to 60% by weight c) hydrophobic monomer (C) 5 ~ 50% by weight of a mixture, a dyeable photosensitive resin composition containing the copolymer (D) obtained as a constituent component is coated to form a film on the surface of the substrate and exposed using a mask. A method for forming a pattern of a dyeable resin film, wherein an aqueous solution containing a nonionic surfactant is used as a developing solution when developing with a developing solution.