JPS6215083B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a water-developable photocurable resin liquid composition.

Photocurable resins that become insolubilized by light irradiation are
Useful in printing plates, photoresists, photosensitive coatings, displays, image forming materials, etc. Among these, water-soluble photocurable resins have the great advantage that development after exposure requires only washing with water.

However, as a water-soluble photocurable resin, a mixture of polyvinyl alcohol, methyl cellulose, an acrylic acid monomer, and a photopolymerization initiator is known; The presence of water is indispensable in order to compensate for the compatibility of , and this causes problems such as drying time and cracks in the film.

The present inventors have conducted intensive studies to solve this problem, and have found that (a) polyvinylpyrrolidone, (b) phenyl glycidyl ether/acrylic acid adduct, and (c) active hydrogen-containing acrylic acid monomer. A composition containing a specific proportion of and further containing a photoinitiator can easily form a uniform resin solution without using water, can be developed after exposure by simply washing with water, and has excellent image clarity. In addition, they discovered that it has excellent adhesion to glass and completed the present invention.

(a) Polyvinylpyrrolidone in the present invention suitably has a K value of 30 to 90 (average molecular weight 40,000 to 400,000), and its proportion in the composition is 1 to 20% by weight, preferably 3 to 15% by weight. It is. If polyvinylpyrrolidone is less than 1% by weight, the coating becomes brittle and cracks are likely to occur, and if it exceeds 20% by weight, the viscosity of the resin liquid itself becomes too high, making it difficult to apply and the defoaming properties are also significantly poor. .

(b) What is the formula of phenyl glycidyl ether/acrylic acid adduct? It is a compound represented by , and the proportion in the composition is 20 to
70% by weight, preferably 30-50% by weight. If it is less than 20% by weight, the durability, adhesion and heat shockability of the film tend to be weak, and if it exceeds 70% by weight, the film tends to become brittle and the heatshockability tends to be poor.

(c) The proportion of the active hydrogen acrylic acid monomer in the composition is naturally determined by the proportions of the components (a) and (b), that is, in the range of 10 to 79% by weight. .

The active hydrogen acrylic acid monomer is 2-
Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, N-vinylpyrrolidone, 2-hydroxyethyl acryloyl phosphate, acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylate Amide, N
-Methoxymethylacrylamide, N-ethoxymethylacrylamide, ethylene glycol monoacrylate, dipropylene glycol monoacrylate, N,N-dimethylaminoethyl acrylate, etc., and these may be used alone or in combination of two or more.

Examples of the photoinitiator in the present invention include benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin phenyl ether, anthraquinone, naphthoquinone, benzophenone, pivaloin ethyl ether, benzoyl peroxide, benzyl ketal, 1, 1-dichloroacetophenone, para-t-butyldichloroacetophenone,
2-chlorothioxanthone, 2,2-diethoxyacetophenone, Michler's ketone, 2,2-dichloro-4-phenoxyacetophenone, phenylglyoxylate, α-hydroxyisobutylphenone, dibenzosparone, benzophenone/
Examples include amines (N-methyldiethanolamine, triethylamine, etc.).

The resin liquid composition of the present invention is obtained by uniformly mixing and stirring the components (a), (b), and (c) in the ratios described above. At this time, an appropriate amount of the photoinitiator is added.

An example of forming an image using this is to uniformly cast the resin liquid onto a base material (but not covered with resin liquid), and then spread the resin liquid onto it so that only the part that will become the image passes through. The prepared sheet is placed on top and illuminated with light using a UV fluorescent lamp, high-power mercury lamp, etc. The irradiation time varies depending on the amount of resin liquid, the output of the light source, etc., but it is approximately 10 to 30 minutes with a UV fluorescent lamp.
0.5 to 3 seconds with a high-power mercury lamp is sufficient. Thereafter, the sheet is removed, washed with water using a brush, the uncured portions removed, and then dried at room temperature to form a clear image.

In the present invention, dyes, extender pigments, additives (antifoaming agents, curing accelerators, etc.), antioxidants, etc. may be added and blended to the extent that they do not extremely hinder the curing of the resin liquid by light irradiation. can. It is also possible to add hardness and flexibility to the image forming resin by adding a small amount of epoxy acrylic oligomer, urethane acrylic oligomer, etc.

The photocurable resin liquid composition of the present invention is useful for printing plates, photoresists, photosensitive paints, display displays, image forming materials, etc., and has particularly excellent adhesion to glass. It is suitable for stained glass.

Next, the present invention will be specifically explained with reference to Examples. In the examples, "parts" are based on weight unless otherwise specified.

Example 1 2 parts of polyvinylpyrrolidone with a K value of 30 manufactured by Guff and 3 parts of polyvinylpyrrolidone with a K value of 90,
50 parts of 2-hydroxyethyl methacrylate and 45 parts of phenyl glycidyl ether acrylic acid adduct
Add it little by little while heating to 40℃ and stirring. After stirring for about 30 minutes to obtain a completely dissolved and transparent resin liquid, 1 part of the photoinitiator α-hydroxyisobutylphenone was added and dissolved with stirring. This resin liquid
UV-a.

Next, a frame with a height of 2 mm is placed on the glass plate, and UV-a is poured onto this glass plate. On the other hand, another glass plate is prepared in which an aluminum vapor-deposited film with only the pattern lines not vapor-deposited is tightly adhered to one surface of the glass plate, and a Tetron film is closely adhered to the other surface. This glass plate
Place the Tetron film so that it is in contact with the UV-a, and heat it under a high-power mercury lamp (80W/cm) at 2m/min.
It passed at a conveyor speed of . Next, the shielding glass plate was removed, and the uncured resin was washed off with a brush and dried at room temperature. The resin in the pattern part was hard (pencil hardness 3H), the pattern was sharp, and an image with strong adhesion to the glass was obtained.

Control example 1 2 parts of polyvinylpyrrolidone with a K value of 30 and 3 parts of polyvinylpyrrolidone with a K value of 90 manufactured by Guff,
Add little by little to 5 parts of 2-hydroxyethyl methacrylate and 90 parts of phenyl glycidyl ether acrylate while heating to 40°C and stirring. After the resin was completely dissolved to form a transparent resin liquid, 1 part of the photoinitiator benzoin isobutyl ether was added and dissolved with stirring. This resin liquid is designated as UV-b.

Next, the film was irradiated with UV-b in the same manner as in Example 1, and then the uncured resin liquid was washed off with a brush and dried at room temperature. Although the resin in the pattern is hard, it is extremely brittle, and many cracks appeared after just 24 hours of exposure to the Sunshine Weather-Ometer, and it was also exposed to -20°C (16 hours) and 80°C (2 hours).
Even in the heat shock cycle test, a crack occurred after one cycle.

Claims (1)

[Claims] 1 (a) Polyvinylpyrrolidone 1 to 20% by weight (b) Phenyl glycidyl ether/acrylic acid adduct 20 to 70% by weight (c) Active hydrogen-containing acrylic acid monomer
A photocurable resin liquid composition comprising 10 to 79% by weight and a photoinitiator.