JPS63100443A - Pattern forming method for dyeable resin film - Google Patents

Abstract

PURPOSE:To reduce a processing period of the titled film by processing the dyeable photosensitive resin film with the aqueous solution containing A a non-ionic surfactant. CONSTITUTION:The film of the dyeable photosensitive resin composition composed of a copolymer comprising a dyeable photosensitive resin composition composed of a copolymer comprising a dyeable monomer, a hydrophilic monomer except said dyeable monomer, and a hydrophobic monomer as a constituting component, is mounted on the surface of a substrate such as a glass plate, and the obtd. film is exposed through a mask. At the time of processing the obtd. film with the developer, the aqueous solution of the nonionic surfactant is used for the developer. By incorporating the aqueous solution of the non-ionic surfactant to the developer, the processing period is reduced, and the resticking of the resin which exists in an unexposed part and is removed in the processing, is reduced, comparing with no addition of the surfactant to the developer. Thus, the rationalization of the processing step, and the improvements in quality and yield are attained. In this case, the non-ionic surfactant has the effects of promoting the wetting with water at the unexposed part, and an infiltration accelator,and the restocking of the removed resin is prevented, thereby enabling to processing for a short period.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a method for forming a pattern 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 something.

In recent years, the demand for transparent substrates such as glass colored in stripes or mosaic shapes has been increasing as color separation filters for colorizing liquid crystal color TVs or cameras for color TVs.

The present invention relates to a method for forming a pattern of a dyeable resin film for dyeing a transparent substrate such as glass in stripes, mosaics, or other shapes, which has been developed to meet such demands.

(Prior Art) Conventionally, dyeable photosensitive resin compositions have been used in this field, but the method for using these dyeable photosensitive resins is to first dilute a solution to a suitable concentration and apply it to a glass plate. etc.,
Next, a color separation filter is created by repeating operations such as exposing to light through a mask, developing it to form a striped or mosaic dyeable resin film, and dyeing this with a dye having predetermined spectral characteristics. When developing this resin film, a neutral to acidic aqueous solution at 20 to 70° C. is used.

(Problems to be Solved by the Invention) As mentioned above, if a dyeable photosensitive resin composition is applied to a glass plate, etc., exposed to light through a mask, and then developed using water at 20 to 70°C. The development time is long, the sticky material of the dyeable photosensitive resin composition that once falls off during development re-adheres to the glass plate, etc., resulting in defective products, and if the development is performed with an acidic solution, Although the development time can be shortened, there are problems such as roughening of the film in the exposed area, so it is necessary to streamline the process.
Further improvement in yield was desired.

(Means for Solving the Problems) As a result of studies to solve these problems, the present inventors applied a dyeable photosensitive resin liquid to a glass plate, etc., exposed it to light through a mask, and then Contains non-ionic surfactants”
It was found that the object could be achieved by performing development using an aqueous solution, leading to the completion of the present invention.

That is, the present invention comprises a) a dyeable monomer fAl b) a hydrophilic monomer other than the dyeable monomer fB)
C) Providing a film on the surface of a substrate such as a glass plate using a dyeable photosensitive resin composition containing a copolymer (D) consisting of a hydrophobic monomer (q),
The present invention relates to a pattern forming method for a dyeable resin film, which is characterized by using an aqueous solution containing a nonionic surfactant as the developing solution when exposing using a mask and developing with a developing solution.

By using the nonionic surfactant-containing aqueous solution of the present invention, the development time can be shortened compared to when no additive is used, and the redeposition of resin in unexposed areas that has fallen off during development is also reduced, streamlining the process and improving quality. Useful for improving production and yield. In this case, the nonionic surfactant is a water wetting and penetration enhancer in the unexposed area.
It is presumed that it acts as a re-deposition preventive agent for the fallen resin and enables development in a short time.

Among surfactants, anionic surfactants are ionically bonded to the dyeable photosensitive resin, so adding anionic surfactants to the developer deteriorates the developability. In addition, using a cationic surfactant shortens the development time and eliminates the redeposition of unexposed resin compositions, but when this is dyed with dyes, the dyed exposed areas lose transparency and have no commercial value. It was inappropriate because it would be stored away.

Nonionic surfactants used in the present invention include polyoxyethylene alkyl ether and hypopolyoxyethylene alkylphenol ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester thread, polyoxyethylene alkyl ester, oxyethylene Examples include oxypropylene block polymers, fatty acid monoglycerides, and the like. These may be used alone or in a mixed system of two or more. The amount of these nonionic surfactants used is preferably 0.1 to 50 parts, particularly preferably 0.5 to 10 parts, per 1000 parts of water. Also, 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) consisting of a dyeable monomer (A), a hydrophilic monomer (C), a hydrophobic monomer (C), or a photosensitive agent such as 4,4'-diazide chalcone, 2°6-bis (4-azidopenzalnocyclohexanone, 2.6-
Bis(4-azidobenzalnocyclohexanone, 2.6
- A dyeable photosensitive resin composition made by combining bis(4-azidobenzal)4-methylcyclohexanone, 1,3-bis(4-azidobenzal)-2-propanone, etc., or a copolymer of this There are dyeable photosensitive resin compositions prepared by reacting compounds having a photosensitive group such as a cinnamoyl group, an azide group, an acrylic group, a styrylpyridinium salt structure, or a styrylquinolium salt structure.

When copolymer a itself consisting of a dyeable monomer (A), a hydrophilic monomer (B, and a hydrophobic monomer (C)) is used as a dyeable photosensitive resin composition, the monomers may include a cinnamoyl group, an azide group, and an acrylic group. A dyeable photosensitive resin composition obtained by copolymerizing a monomer having a styrylpyridinium salt structure, a styrylquinolium salt structure, or the like is preferred.

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

(N,N-dimethylaminoethyl acrylate, (N
, N-dimethylamino)ethyl methacrylate, (N,
N-diethylamino)ethyl acrylate, (N,N-
Diethylamitunoethyl methacrylate, (N,N-dimethylaminopropylacrylamide, (N,N-dimethylaminopropyl methacrylamide), (N,N-dimethylamitunoethyl vinyl ether, (N,N-dimethylamino)propyl acrylate) , (N,N-dimethylaminonepropyl methacrylate, 4-vinylpyridine, diallylamine, 2-hydroxy-3-methacryloyloxypropyl, trimethylammonium chloride, methacryloyloxyethyltrimethylammonium chloride.

Further, examples of the hydrophilic monomer (B) used in the present invention 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.

These dyeable monomers (A), hydrophilic monomer fBl,
Hydrophobic monomer (the blending ratio of Q is the dyeable monomer (A)
10 to 80% by weight of hydrophilic monomers (T32 to 60% by weight) and hydrophobic monomers fQs to 50% by weight. These monomers can be polymerized by conventional techniques.

Further, the dyeable photosensitive resin composition used in the present invention is diluted with an organic solvent to make it easier to apply to glass plates and the like. Examples of organic solvents include methyl cellosolve, ethyl cellosolve, ethylene glycol monoethyl ether acetate, diglyme, methyl isobutyl ketone,
Examples include toluene and xylene.

A base material such as glass coated with this dyeable photosensitive resin composition is exposed to ultraviolet light or the like through a mask. The unexposed areas are developed with an aqueous solution containing a nonionic surfactant.

The film thickness of the resin developed in this way is, for example, 0.2 to 10
A film can be created with any thickness of μ.

A substrate such as glass or plastic having a developed predetermined pattern is dyed with an anionic dye.

Color index (5oci) is an anionic dye.
ety of Dyers and Colors
Examples include acid dyes listed as C, lAc1d in the same C0I Direct, reactive dyes listed as C-I Reactive, etc., but especially acidic dyes. preferable.

(Example) Example 1゜Dimethylaminopropylacrylamide 30 parts 2
-Hydroxyethyl methacrylate 15 parts Vinylpyrrolidone 34' Methyl methacrylate 30# Dimethylaminoacrylamide 16 parts of a copolymer consisting of 91 and 0.6 parts of 4,4-diazide chalcone
A dyeable photosensitive resin liquid was prepared by mixing and dissolving 5 parts of ethyl cellosolve and 84 parts of ethyl cellosolve.

Next, silane coupling agent KBM503 (
A 10% ethanol solution of Shin-Etsu Chemical Co., Ltd. was applied, air-dried, and then heated at 110° C. for 5 minutes to prepare a coating substrate.

The dyeable photosensitive resin liquid was applied to the surface of the coating base material by a roll coater method, and after drying at 100°C for 30 minutes, the surface illuminance was 8.
UV irradiation was carried out at mW/cm2 for 15 seconds, and a developer solution at 60°C containing 2 parts of Emulgen 913 (polyoxyethylene nonylphenol ether type nonionic surfactant manufactured by Kao Soap ■) per 1000 parts of water was used. under stirring, 5
When development was carried out for a minute, a glass substrate having a dyeable film only in the irradiated area was obtained. This dyeable film had a thickness of 0.7μ.

After drying this glass substrate at 350°C for 30 minutes, Red 2
] P (Nippon Kayaku, color filter dye) was 0.
When it was dissolved in water to a concentration of 2% and dyed at 60°C for 0 minutes, a glass plate dyed in a deep red pattern was obtained. In this glass plate, there was very little re-adhesion of the resin that had fallen off during development to the unexposed areas, and the image was extremely clear.

In Reference Example 1゜Example, when the same operation was carried out using a 60°C developing solution that did not contain Emulgen 913, the re-adhesion of the fallen resin to the unexposed glass plate was different from that in Example 1. The development time required to obtain a clear image similar to that in Example 1 was 13
It took several minutes. Even in this case, prevention of re-adhesion of the fallen resin to the unexposed glass plate was insufficient.

Example 2 In Example 2, a developer containing 1.8 parts of Emulgen 930 (manufactured by Kao Soap, polyoxyethylene nonylphenol ether type nonionic surfactant) per 1000 parts of water was used instead of Emulgen 9J3. When the same operation as in Example 1 was carried out using , the same results as in Example were obtained.

Example 3゜Dimethylaminopropylacrylamide 32 parts 2
-Hydroxyethyl methacrylate 21 Vinyl pyrrolidone 161 Dimethyl minoacrylamide 131 Butyl acrylate 1] #Methyl methacrylate 17 parts of a copolymer consisting of J4I, 0.78 part of 2,6-bis(4-azidohenzal)4-methylcyclohexanone, A dyeable photosensitive resin liquid was prepared by mixing and dissolving 183 parts of ethylcelonol.

This dyeable photosensitive resin liquid was applied to a glass plate in the same manner as in Example 1, dried, and irradiated with UV through a patterned mask.

Next, add 2.5 parts of Emulgen 430 (manufactured by Kao Soap ■, polyoxyethylene oleyl ether) to 1000 parts of water.
When development was carried out for 8 minutes using a developer at 58.degree. The thickness of this dyeable film was 0.8μ. 15 pieces of this glass substrate
After drying at 0℃ for 30 minutes, Green IF (manufactured by Nippon Kayaku ■,
Color filter dye) was dissolved in water to a concentration of 0.1% and dyed at 62° C. for 12 minutes to obtain a glass plate dyed in a deep green pattern. In this glass plate, there was no redeposition of the resin that had fallen off during development to the unexposed areas, and the image was extremely clear.

Reference Example 2゜When the same operation as in Example 3 was performed using a developer at 58°C that did not contain Emulgen 430, the redeposition of the fallen resin to the unexposed glass plate was compared to that in Example 3. In addition, the developing time required to obtain a clear image similar to that in Example 3 is 1
I enriched my 5 minutes. Even in this case, prevention of re-adhesion of the fallen resin to the unexposed glass plate was insufficient.

Example 4 The same operation as in Example 3 was carried out using a developer containing 2.3 parts of Emulgen 9]3 per 1000 parts of water instead of Emulgen 430. Similar results to Example 3 were obtained.

(Effects of the Invention) Since the present invention uses an aqueous solution containing a nonionic surfactant for developing the dyeable photosensitive resin film, the developing time can be shortened, which is useful for streamlining the process. Furthermore, since redeposition of the fallen resin to unexposed areas can be prevented, higher quality products can be obtained and the yield can be improved. Therefore, this property can not only improve the quality of color separation filters, but also help reduce costs by streamlining the process.

Claims (1)

[Claims] a) Dyeable monomer (A) b) Hydrophilic monomer (B) other than the dyeable monomer (A)
c) A film is formed on the surface of the substrate using a dyeable photosensitive resin composition containing a copolymer (D) consisting of a hydrophobic monomer (C), and exposed using a mask, and then processed with a developer. A pattern forming method for a dyeable resin film, characterized in that during development, an aqueous solution containing a nonionic surfactant is used as a developer.