JPS6187151A - Preparation of image-forming film - Google Patents

Abstract

PURPOSE:To enhance adhesion to a base by coating the base with a solvent soln. of a specified soluble epoxy polymer obtained by hardening a functional epoxy compd. with an amine type compd., and irradiating actinic rays through an image film on the obtained coat. CONSTITUTION:The coat film is imagewise hardened by hardening the 2-functional epoxy compd., such as bisphenol type diglycidyl ether, having 2 epoxy groups in the molecule, with the amine type compd., such as piperazine or aniline, having 2 active H atoms, further introducing photopolymerizable or photobridgeable groups into the molecule to form a soluble polymer, coating the base with a solvent soln. of this polymer, and irradiating actinic rays through the image film on the formed coat film, thus permitting the obtained film to be high in adhesion to the base and colorable with a dye in high density, and superior in an image-forming characteristics by light.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for manufacturing an image forming film, and the image forming film is used for solid-state image sensors, color filters for liquid crystal displays, and the like.

[Conventional technology]

Epoxy polymers that are soluble in water and organic solvents are known (-A, Renner et al.
.

, T, Po1y, Sci, : Po1y, Oh
Em, Kdi, 22, 249 (1984)),
Nothing is known that has photopolymerizability or photocrosslinkability.

Also, acrylic polymers are known as films that have photoimage-forming ability and can be colored with dyes (63rd Society of Polymer Science and Technology, 3F 22-11a (p554) (1984).
)).

[Problem that the invention seeks to solve]

The conventional technology has the following problems, and the present invention attempts to solve these problems.

(1) Inadequate adhesion to the substrate (2) Deep dyeing is not possible (3) If too many dye sheets are introduced to dye the dye deep, the photoprintability may decrease or it may peel off from the substrate during dyeing. .

[Means to solve the problem]

The present invention is configured as follows.

A difunctional epoxy compound is cured with an amine compound, and a solvent solution of a soluble epoxy polymer in which a photopolymerizable or photocrosslinkable group is introduced into the molecule is applied to a substrate to form a coating film, and an image is formed on top of this. 1. A method for producing an image-forming film, which comprises curing a coating film in an image-like manner by irradiating actinic rays through the film.

The present invention will be explained in detail below.

The method for preparing the solvent-soluble epoxy polymer used in the present invention is not particularly limited. An example of this is shown below.

As the epoxy compound, those having two epoxy groups in the molecule, such as bisphenol Am diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and 1,6-hexanesiol diglycidyl ether, are used. Amine compounds include hiheracin, monoethanolamine, 2
- Use ethylhexylamine, benzylamine, or aniline nato having two active hydrogens in the molecule.

The method for linearly polymerizing the above epoxy compound and amine compound is as follows: 2. For example, the epoxy compound and amine compound in equivalent or slightly different ratios are dissolved in methylcellosolve to a concentration of 15 to 20% by weight, and the mixture is heated at the boiling point for 10 hours. It can be obtained by polymerizing to some extent.

Photofunctionalization of linear epoxy polymers is carried out as follows.

If the solvent used in the polymerization is suitable for photofunctionalization, it may be used directly in the reaction. but.

In most cases, the polymer is soluble in the polymerization solvent and insoluble in the liquid 1. The polymer is reprecipitated in a liquid 1, such as water, and then redissolved in a solvent suitable for the photofunctionalization reaction.

Various methods can be considered for photofunctionalization. An example is shown below. In these examples, an OH group generated from an epoxy group during polymerization is used as a reactive group on the polymer side.

(1) Addition of ethylenic double bond by ring-opening esterification of glycidyl methacrylate (2) Monoesterification of maleic acid or fumaric acid (3)
1 Phenylmaleic acid or phenylfumaric acid monoesterification (4) Acrylamide methyl etherification with N-methylol acrylamide (5) Addition of ethylenic double bond by reaction with acrylic acid chloride (6) Reaction with cinnamic acid chloride There is also a method of ring-opening polymerization of an epoxy compound having a double bond by adding a protic acid to the basic tertiary nitrogen moiety present in the polymer.

Another method is to bond an epoxy compound with a double bond to the terminal amino group.

There is also a method of reacting an OH group with a dieboxide or siloisocyanate while leaving a terminal epoxy group or incyanate group, and bonding glycidyl methacrylate, acrylic acid, etc. to that portion.

Next, the following method can be mentioned as a method that enables photoimage formation without directly attaching a photofunctional group to a linear epoxy polymer.

(1) Photocrosslinking by blending diazo resin (2) Photocrosslinking by blending tetrazonium salt (3) Photopolymerization by blending (meth)acrylic acid ester monomer In either case, the basicity of the polymer is reactive or stable. If it becomes a sexual problem, neutralize it with acetic acid, hydrochloric acid, sulfuric acid, etc. in advance.

As described above, the linear epoxy polymer with or without direct photopolymerizable or photocrosslinkable groups is dissolved in a solvent such as dioxane, and if necessary, a photoinitiator and a reinforcing agent are added. A sensitizing agent is added, along with other additives such as polymers and pigments, and then applied to the substrate.

The film on the substrate is exposed through a pattern and developed with a solvent.

Methods for coloring the photo-formed image as described above with dye include a method in which the substrate is directly immersed in a dye bath, and a method in which a dye is blended into the coating solution before coating. It is effective as a means of darkening the color. Acidic dyes and reactive dyes are particularly preferably used in the present invention.

Substrates used in the present invention include glass plates 9 synthetic resin plates 9 synthetic resin films, metals, etc., but preferably transparent glass plates 9 synthetic resin plates or films.

Example 1 12.1 g of Epicomt 828 (manufactured by Yuka Ciel Exoxy), a commercially available bisphenol A diglycidyl ether type epoxy resin, was dissolved in 80 g of methyl cellosolve, and 2.7 g of anhydrous piperazine was added.

The mixture was reacted for 10 hours at the boiling point of methylcellosolve (approximately 121°C) while stirring.

When the obtained polymer solution was applied to a slide glass, a transparent film was obtained, showing excellent adhesion.

After reprecipitating in cold water and washing, the polymer was once dried and then redissolved in dioxane to form a 5% by weight solution.

20 g of this solution was cooled to -5°C, and 04 g of cinnamic acid chloride, which had been previously dissolved in 10 g of methyl ethyl ketone at -5°C, was added and reacted at -5°C.

After the reaction was completed, the polymer was reprecipitated in water, washed, and then redissolved in dioxane to make a 5% by weight solution. In addition, 5-
Nitroacenaphthene was added in an amount of 10% by weight based on the polymer.

After coating on a glass slide to a thickness of 20 μm and drying.

When the pattern was exposed to light using Jet Light 3300 (Oak Seisakusho), the pattern was exposed by dioxane development and the adhesion of the 9 image areas was excellent.

It can still be dyed with acid dye FOod Red m 104.

Even during dyeing, it adhered strongly to the substrate and did not peel off.

Example 2 1 g of the purified polymer polymerized in Example 1 was dissolved in 19 g of dioxane. To this, phenylmaleic anhydride 0.
5 g and 20 g of anhydrous pyridine were added.

React at 80°C for 5 hours.

This was reprecipitated by pouring it into acidic cold water, thoroughly washed, and then dried.

1 g of dry polymer was redissolved in 29 g of methylcellosolve and added with 0.0 g of acid dye Food Red m 104.
Added 2g. After coating on a slide glass, it was exposed to light with Jet Light 3300 and developed with Methyl Cellosolve, and a clear image was formed, but the adhesiveness of 9 image areas was weak. What is the first dye added?

Even when the image and section were immersed in water or alcohol, it did not elute.

Example 6 Commercially available 1,6-hexanethiol diglycidyl ether (Evolai) 1600. (Kyoeisha Yushi Kagaku) 15g 8
Dissolved in 0 g of methylcellosolve, anhydrous piperazine 46
g added. While stirring, reduce the boiling point of Methyl Celsolve (approximately 1
21°C) for 10 hours.

After reprecipitating with cold water and washing, the polymer was once dried and then redissolved in dioxane to form a 5% by weight solution.

Add dye Food B'lue m 10 to 20 g of this solution.
．． 3 g and a small amount of acetic acid were dissolved. Subsequently, 1 g of p-diazodiphenylamine/paraformaldehyde condensation product (diazo resin) was added and applied onto a glass slide.

Dry. When exposed and developed in the same manner as in Example 1, a clear blue image was formed and the adhesiveness of the 9 image areas was also excellent. Furthermore, there was no elution of the dye with water or alcohol.

〔Effect of the invention〕

The present invention provides a method for producing a film that has high adhesion to a substrate, can be colored deeply with dye, and has excellent photoimageability.
This could be provided by

Patent Applicant Toshi Co., Ltd. Written Amendment to Procedures 1. Display of case 1982 Patent Application No. 190033 2 Name of invention Method for manufacturing image forming film 3 Person making amendment Relationship to case Patent applicant address 2-2 Nihonbashi Muromachi, Chuo-ku, Tokyo Name (3
15) Masatoshi Ito, Representative Director and President of Toshi Co., Ltd. 4. Date of amendment order Voluntary 5. Number of inventions increased by amendment: None 6. Column 7 of “Detailed description of the invention” of the specification to be amended, Amendment In the contents specification, (1) page 4, lines 14-15, [(1> Addition of ethylenic double bond by ring-opening esterification to glycidyl methacrylate-1]) is replaced with "(1) glycidyl methacrylate-1". "Addition of ethylenic double bond by ring-opening bond of Re-1~"
I will correct it.

(2) Change “existence” in line 6 of page 5 to “existence-1”
I will correct it.

(3) Correct "cricidyl methacrylate or acrylic acid in that part" in lines 12-13 of page 5 to [acrylic acid in that part].

(4) Correct "After application and drying" in the third line of page 8 to "After application and drying."

(5) rO, 3gJ on page 9, line 15 is “0.2
9” and correct it.

Procedural amendment Showa 6-11°-8th

Claims (1)

[Claims] A difunctional epoxy compound is cured with an amine compound, and a solvent solution of a soluble epoxy polymer in which a photopolymerizable or photocrosslinkable group is introduced into the molecule is applied to a substrate to form a coating film, and an image is formed on top of this. A method for producing an image-forming film, which comprises curing a coating film in an image-like manner by irradiating actinic rays through the film.