JPH0612453B2 - Photocurable resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photocurable resin composition from which a photocured product that can be dyed with an acid dye is obtained.

When a photosensitive resin is used as a method for obtaining a colored image from a transparent film such as a photographic filter, a printing filter and a video camera pickup tube filter, a photosensitive resin solution in which a dye is dissolved is applied on a support such as glass. The easiest way is to expose it to actinic radiation through a negative image to cure it, and dissolve and remove the unexposed area with a developer. However, in this case, the curing reaction of the resin due to the exposure may be hindered by the dye, and even if it is not hindered, it is difficult to color the concentrate in a concentrated manner.

On the other hand, when a colorless image is first formed on a support using a photosensitive solution containing no dye and then the image is dyed by dipping in a dyeing bath at about 90 ° C., for example,
The curing reaction of the photosensitive solution is carried out without being affected by the dye, and a colored image having a relatively high density can be obtained. In this case, however, an acid dye is preferably used among various dyes from the viewpoint of excellent weather resistance, and conventionally, as a photosensitive resin composition that can be colored with an acid dye, casein or glue and dichromate are used. A composition containing and is known.

Since these compositions are mainly composed of natural polymers, it is difficult to obtain a product having a constant concentration of functional groups such as amino groups and a molecular weight distribution, which are involved in dyeing, and the photosensitive solution is easily decomposed. The resulting cured film has poor adhesion to a support such as glass, and has the drawback that a chromium compound harmful to the human body must be used.

An object of the present invention is to provide a resin composition which eliminates the above-mentioned drawbacks of the conventional photocurable composition used for forming the above-mentioned colored image.

As a result of various investigations on nitrogen-containing monomers, the present inventors have found that a polymer having aniline, pyridine, oxazolidine, pyridine, and the like as a constituent unit has a strong tendency to change color from yellowish brown to black when contacted with oxygen in the air. As a result of further research based on the findings, a unique nitrogen-containing monomer that is dyed well with an acid dye when used as a polymer component and good adhesion and cross-linking reactivity to a support The present invention has been completed, focusing on the hydroxyl group-containing monomer.

Therefore, the gist of the present invention is to provide a hydroxyl group-containing monomer 20-70 represented by the formula (A) (1).
A water-soluble copolymer containing 5% to 80% by weight of a nitrogen-containing monomer represented by the formula (2) or (3) as a constituent unit; (R ₁ and R ₂ represent H, CH ₃ or C ₂ H ₅ , and n represents an integer of 1 to 3) (2) (R ₃ represents H, CH ₃ , X represents NH, R ₄
Represents an alkylene group having 2 or 3 carbon atoms, and R ₅ and R ₆ represent H or an alkyl group having 1 to 4 carbon atoms. ) (3) (R ₃ represents H, CH ₃ , X represents NH, R ₄
Is an alkylene group having 2 or 3 carbon atoms, R ₅ , R ₆ , R ₇
Represents H or an alkyl group having 1 to 4 carbon atoms, and Y represents an acid group. (B) Water-soluble diazo compound is contained, and the photocurable resin composition is characterized in that the photocurable product can be dyed with an acid dye.

Suitable examples of the hydroxyl group-containing monomer represented by the formula (1) used as a constituent unit of the water-soluble copolymer (A) include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl. Examples thereof include acrylate and 2-hydroxypropyl methacrylate, and 2-hydroxyethyl methacrylate is particularly preferably used because of its excellent cross-linking reactivity and adhesion to a support such as glass. If the amount of these hydroxyl group-containing monomers used is too small, the crosslinking reactivity of the water-soluble copolymer, that is, the photocurability, will be insufficient, and if it is too large, the solubility in water will be poor and the developer will be limited to organic solvents. , 20 to 70% by weight with respect to the water-soluble polymer, preferably 30 to 6
The range is 0%.

Preferable examples of the nitrogen-containing monomer represented by the above formula (2) include N, N-dimethylaminopropylacrylamide, N, N-diethylaminopropylacrylamide,
N, N-dimethylaminopropylmethacrylamide,
N, N-diethylaminopropyl methacrylamide and the like are mentioned, and the water-soluble copolymer (A) is hardly discolored by oxygen, the polymerization reactivity is large, and the photocured product is an acid dye. In particular, N, N-dimethylaminopropylmethacrylamide is preferably used because it is easily dyed and has good developability.

Y in the formula (3) is an acid group, specifically Cl, Br, I, CH.
₃ COO, SO _{4 and the} like, and preferable examples of the monomer represented by the formula (3) include the above-mentioned monomers enumerated as the preferable examples of the formula (2) and an acid containing the above acid group. The quaternary ammonium salt formed in the reaction may be mentioned.

When the amount of the nitrogen-containing monomer represented by the formula (2) or (3) is too small, the dyeability of the photocured product is insufficient, and when it is too large, the photocurable product of the water-soluble copolymer is insufficient. Therefore, it is 5 to 80% by weight, preferably 30 to 60% by weight, based on the water-soluble copolymer.

In the above copolymer (A) in the present invention, a monomer represented by the formula (1) and (2) or (3), together with another monomer, is usually contained in a proportion of 20% or less. It may be contained as. Specific examples thereof include acrylic acid, methacrylic acid, acrylic acid esters (for example, methyl acrylate, ethyl acrylate, butyl acrylate),
Methacrylic acid esters (eg, methyl methacrylate, ethyl methacrylate), maleic acid fumaric acid, itaconic acid, the former three esters, vinylbenzenesulfonic acid, acrylamide, N-methylolacrylamide, diacetoneacrylamide, N, N-dimethylacrylamide. , Methacrylamide, N-vinylpyrrolidone, N-
Morpholyl acrylamide, acrylonitrile, P-dimethylaminostyrene, 5-ethyl-2-vinylpyridine, 2-pyridylmethacrylate, N-vinyloxazolidine, 2-vinylpyridine, 4-vinylpyridine,
4-vinyl pyridine, 2-vinyl quinoline etc. are mentioned.

The water-soluble copolymer (A) can be obtained from the above-mentioned monomer by a conventionally known solution polymerization method, suspension polymerization method or the like, but the solution polymerization method is usually employed.

The water-soluble diazo compound used as the photosensitizer in the composition of the present invention means one having one, preferably two or more diazo groups in one molecule, and an aromatic water-soluble diazo compound is usually used.

Specific examples thereof include P-diazodiphenylamine,
Examples thereof include condensates of 2.5-dimethoxy-4-P tolylmercaptonbenzenediazonium or 2.5-dimethoxy-4-morpholinobenzenediazonium and formaldehyde, and particularly, condensates of P-diazodiphenylamine and formaldehyde. Is often used.

Specific examples thereof include formaldehyde condensate of P-diazodiphenylamine and hexafluorophosphate, tetrafluoroborate, perchlorate, paratoluenesulfonic acid or 2-hydroxy-4-methoxybenzophenone. Included are diazonium salts produced by reaction with -5-sulfonic acid.

The content of the water-soluble diazo compound in the composition of the present invention is not particularly limited, but the water-soluble copolymer (A) 100
It is usually 2 to 30 parts by weight, more preferably 5 parts by weight.
~ 20 parts by weight.

Since the water-soluble diazo compound is unstable in a neutral medium, it is necessary to make the aqueous solution of the water-soluble copolymer that dissolves the water-soluble diazo compound acidic.

Specific examples of the acidic substance added for pH adjustment include inorganic acids such as sulfuric acid, hydrochloric acid and phosphoric acid, and organic salts such as acetic acid, oxalic acid, citric acid and paratoluenesulfonic acid.

To obtain a colored image from a colorless film using the composition of the present invention, for example, the composition of the present invention is first dissolved in an aqueous medium to form a photosensitive solution, and a glass substrate on which the photosensitive solution is applied is usually treated with an aqueous surfactant solution. After soaking it for 24 hours, wash it with water, and then wash with acetone. The solid content concentration of the photosensitive liquid is determined in consideration of the molecular weight of the copolymer, the coating film thickness, and the rotation speed of the spin coater.

The glass plate coated with the photosensitive liquid is usually dried in a dryer at 50 to 90 ° C. for several minutes, a mask film is brought into close contact with the obtained photosensitive film, and ultraviolet rays are irradiated with a mercury lamp to cure the photosensitive film.

Although the mechanism of curing is not clear, the acid in the hydroxyl group of the hydroxyl group-containing monomer represented by the above formula (1) contributes to the crosslinking reaction due to the action of the radical generated from the water-soluble diazo compound by irradiation with light. It is estimated that the curing reaction proceeds.

After that, the unexposed portion is dissolved and removed with a developing solution made into an acidic aqueous solution, and the sample plate is immersed in a dye bath to color the colorless image area.

The dyeing conditions are determined according to the conditions required for the colored thin film, but generally, the acid dye is 0.5 to 1%, and the acetic acid is 1 to 1.
Immerse the sample plate subjected to the above phenomenon in an aqueous solution containing 0% 6
It may be kept at 0 to 100 ° C for 1 to 10 minutes. Then, the sample plate is taken out from the dyeing bath, washed with water and dried.

Since the photocurable resin composition of the present invention is configured as described above, it exhibits the following excellent operational effects.

(1) Since the resin composition is water-soluble, both the photosensitive solution and the developing solution can be handled as a water-soluble material. Therefore, it is excellent in safety and hygiene without using an organic solvent.

(2) Compared to the conventional composition containing a natural polymer as a main component such as casein-chromium, the composition and molecular weight can be easily adjusted, and it does not decompose or deteriorate. It is safe because it is not lost and no toxic heavy metals such as chromium compounds are required.

(3) Since a water-soluble diazo compound is used as a photosensitizer,
Even when exposed in air, the reaction is not hindered by oxygen, and discoloration hardly occurs.

(4) Since a basic monomer that is stable against oxidation is used,
It is deeply and vividly dyed with an acid dye.

(5) It is possible to obtain a photosensitive film having good adhesion to a support such as glass.

Examples of the present invention will be shown below. Example 1 The mixture having the above composition was placed in a 500 ml round-bottom separable flask, nitrogen gas was introduced, and the mixture was stirred at 40 ° C. to form a uniform solution, then heated to 70 ° C. and stirred for 5 hours.

The reaction mixture was put into cyclohexane, and after suctioning, the solid was vacuum dried at 30 ° C. for 5 hours to obtain a water-soluble copolymer.

A photosensitive solution having the following composition was prepared using this water-soluble copolymer.

Next, a glass plate which was washed with an aqueous solution of a surfactant, water, and acetone in this order and dried was placed in a spin coater together with the above-mentioned photosensitive solution,
50 ° C., 100 r. p. m was applied to the photosensitive solution.

A mask film for resolution test was brought into close contact with the photosensitive film obtained by drying at 60 ° C. for 3 minutes with a hot air drier, and irradiation with a 1 KW ultra-high pressure mercury lamp was performed for 20 seconds from a distance of 1 m.

After development with a 5% acetic acid aqueous solution at 40 ° C. for 1 minute and drying, the thickness of the image area became 0121 microns.

This sample plate was immersed in a 90 ° C. dyeing bath having the following composition for 10 minutes, washed with water and dried.

The obtained blue image was clear, and the absorbance at 590 mμ was 2.94.

Comparative Example 1 The mixture having the above composition was placed in a 500 ml flask and stirred at 70 ° C. for 5 hours while introducing nitrogen gas.

The reaction mixture was precipitated in cyclohexane and dried to give 99.2g of white powder.

A photosensitive solution was prepared from this polymer with the same formulation as in Example 1,
It was applied on a glass plate and irradiated with ultraviolet rays. This photosensitive material was developed with water and then immersed in a dyeing bath containing a red dye having the following composition at 90 ° C. for 10 minutes, but it was dyed in an extremely light red color.

Dye composition

Claims (4)

[Claims] (A) 20-70% by weight of a hydroxyl group-containing monomer represented by formula (1) and 5-80% by weight of a nitrogen-containing monomer represented by formula (2) or (3). A water-soluble copolymer containing as a constituent unit (1) (R ₁ and R ₂ represent H, CH ₃ or C ₂ H ₅ , and n represents an integer of 1 to 3.) (2) (R ₃ represents H, CH ₃ , X represents NH, R ₄
Represents an alkylene group having 2 or 3 carbon atoms, and R ₅ and R ₆ represent H or an alkyl group having 1 to 4 carbon atoms. ) (3) (R ₃ represents H, CH ₃ , X represents NH, R
₄ is an alkylene group having 2 or 3 carbon atoms, and R ₅ , R ₆ , R
₇ represents H or an alkyl group having 1 to 4 carbon atoms, and Y represents an acid group. (B) A water-soluble diazo compound is contained, and the photo-cured product has an acid dye dyeing property. 2. The composition according to claim 1, wherein the hydroxyl group-containing monomer is 2-hydroxyethyl methacrylate. 3. The composition according to claim 1, wherein the nitrogen-containing monomer is N, N-dimethylaminopropylmethacrylamide. 4. The composition according to any one of claims 1 to 3, wherein the water-soluble diazo compound is a condensate of P-diazophenylamine and formaldehyde.