JP3199463B2 - Photosensitive resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition, and more particularly, to a photosensitive resin composition containing a water-based resin emulsion in a light absorber. The photosensitive resin composition according to the present invention can effectively prevent halation and easily form a high-resolution image.

[0002]

2. Description of the Related Art Conventionally, a photosensitive resin for producing a water-developing type printing plate, particularly a screen printing plate, mainly comprises an aqueous resin emulsion, a water-soluble polymer and a photo-crosslinking agent. In order to obtain a resolution image, a colorant such as an aqueous pigment or a water-soluble dye has been added as an antihalation agent.

However, in the above-described photosensitive resin composition, the volume ratio of the aqueous resin emulsion particles in the photosensitive resin composition is generally as large as 70 to 80%.
In addition, the aqueous pigment and the water-soluble dye cannot color the inside of the aqueous resin emulsion particles. Therefore, the coloring agent will color the portion of the water-soluble polymer having a small volume ratio. Therefore, with the conventional photosensitive resin composition having no means for preventing halation inside the particles of the aqueous resin emulsion occupying a large volume ratio in the photosensitive resin composition, halation cannot be sufficiently prevented, and a good image can be obtained. There is a problem that it is difficult to obtain.

In recent years, photodimerization reactions of styrylpyridinium salt compounds, styrylquinolinium salt compounds, and the like have been performed as photocrosslinking agents having higher sensitivity than conventional photocrosslinking agents such as diazo compounds and dichromates. Substances to be performed are attracting attention, but these highly sensitive photocrosslinking agents are more strongly affected by halation than conventional photocrosslinking agents such as diazo compounds and dichromates. Therefore, there is a problem that it is more difficult to obtain a good image as compared with the case where the conventional photocrosslinking agent is used.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to solve such problems of the prior art, and by using an emulsion filled with a light absorber as a component of a photosensitive resin composition. Another object of the present invention is to provide a photosensitive resin composition having a sufficient antihalation effect and capable of easily forming a high-resolution image.

[0006]

Means for Solving the Problems The present inventors have found that the above object can be achieved by using an aqueous resin emulsion having an antihalation function as a constituent of a photosensitive resin composition. It has been completed.

That is, according to the present invention, in order to solve the above-mentioned problems, a compound having an ethylenically unsaturated group is subjected to emulsion polymerization or suspension polymerization in water in the presence of a light absorber and a water-soluble polymer. The water-soluble polymer obtained as a protective colloid, a water-soluble resin emulsion filled with a light absorber which does not itself have photoreactivity, and a diazo compound or
Water-soluble photosensitive resin composition characterized by comprising a beam salt is provided. According to the present invention, the compound having an ethylenically unsaturated group, in the presence of a light absorber and a water-soluble polymer, obtained by emulsion polymerization or suspension polymerization in water, the water-soluble polymer, As a protective colloid, a styrylpyridinium salt is used as a water-soluble polymer protective colloid of an aqueous resin emulsion filled with a light absorber that does not itself have photoreactivity.
Compound, styrylquinolinium salt compound and N-methyl
One or more selected from roll acrylamide
A water-soluble photosensitive resin composition characterized by comprising a water-absorbent resin-filled aqueous resin emulsion obtained by addition-condensation of the photosensitive compound described above. According to the present invention, further, a compound having an ethylenically unsaturated group is obtained by emulsion polymerization or suspension polymerization in water in the presence of a light absorbing agent. Water-soluble resin emulsion, water-soluble polymer and diazo compound or
There is provided a water-soluble photosensitive resin composition comprising a romate . According to the present invention, further, a compound having an ethylenically unsaturated group is obtained by emulsion polymerization or suspension polymerization in water in the presence of a light absorbing agent. Water-based resin emulsion , styrylpyridinium salt compound, styrylquinolini
From sodium salt compounds and N-methylolacrylamide
A water-soluble photosensitive resin composition comprising a water-soluble polymer obtained by addition-condensation of one or more selected photosensitive compounds is provided.

In the composition of the present invention, the light absorber is contained in a polymer comprising a compound having an ethylenically unsaturated group. The light absorber used has a wavelength of 200 nm to 60 nm.
0 nm, preferably a substance that absorbs light in the range of 300 nm to 450 nm. Examples of useful substances include organic pigments, inorganic pigments, dyes, ultraviolet absorbers, photopolymerization initiators, photosensitizers and the like. be able to.

Examples of the above-mentioned organic pigments include azo, phthalocyanine, benzimidazolone, quinacridone, isoindolinone, pyrathrone, dibromoanzanthrone, indathrone, anthrapyrimidine, flavastrone, Perylene, perinone, quinophthalone, phthalone, thioindigo, indigo,
Examples include dioxazine-based, anthraquinone-based, xanthene-based, methine-based, and azomethine-based pigments, and condensed polycyclic pigments including other metal complex-based pigments. Further, examples of inorganic pigments include Miloli Blue, iron oxide, cobalt purple, manganese purple, ultramarine, navy blue, cobalt blue,
Cerulean blue, viridian, emerald green,
Cobalt green and the like can be mentioned.

These organic pigments and inorganic pigments have a particle diameter of 0.7 μm or less, preferably 0.1 μm or less, from the viewpoint of the film surface uniformity and light transmittance of the water-absorbing resin emulsion containing the light absorber to be synthesized. The thickness is preferably 1 μm or less.

Examples of dyes include nitroso, nitro, azo, stilbene azo, ketoimine, triphenylmethane, xanthene, acridine, quinoline, methine, thiazole, indamine, and azine dyes. And oxazine, thiazine, aminoketone, anthraquinone, phthalocyanine and triallylmethane dyes.

Examples of ultraviolet absorbers include cyanoacrylate-based, benzotriazole-based and salicylic acid-based ones. Examples of the photopolymerization initiator and the photosensitizer include benzophenone-based, cinnamate-based, thioxanthone-based, benzoate-based, benzoin-based, and acetophenone-based ones.

[0013] One or more of these light absorbers are appropriately selected and used.

Next, the compound having an ethylenically unsaturated group is a compound having one or more ethylenically unsaturated groups in a molecule, for example, alkyl acrylates (for example, methyl acrylate, acrylic acrylate). Ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc.), alkyl methacrylates (eg, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate), epoxy acrylates (methacrylate) ), Urethane acrylates (including methacrylate), polyether acrylates (including methacrylate), polyester acrylates (including methacrylate), acrylic acid, methacrylic acid, glycidyl acrylate, glycidyl methacrylate, Le allyl, allyl methacrylate, itaconic acid, acrylamide, methacrylamide,
Dimethylaminoethyl acrylate, diethylaminoethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, N-methylolacrylamide, N-methylolmethacrylamide, acrylonitrile, styrene, α-methylstyrene , Vinyl acetate, vinyl toluene, vinyl pyridine, 2-hydroxy-3-phenoxypropyl acrylate, p-nonylphenoxyethyl acrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol diacrylate , Neopentyl glycol dimethacrylate, 2-hydroxy-1-acryloxy-3-methacryloxypropane, 3-butyi Glycol dimethacrylate,
2,2-bis [4- (acryloxy-polyethoxy)
Phenyl] propane, 2,2-bis [4- (methacryloxy-polyethoxy) phenyl] propane, trimethylolpropane triacrylate, tetramethylolmethane triacrylate, tetramethylolmethanetetraacrylate, dipentaerythritol hexaacrylate, butadiene, isoprene, Examples thereof include chloroprene, vinyl chloride, vinyl bromide, vinylidene chloride, and vinylidene fluoride, and these can be used alone or in combination of two or more.

The content ratio of the light absorber is 0.01 to 60 parts by weight per 100 parts by weight of the compound having an ethylenically unsaturated group.
The content is preferably in the range of 0.05 to 10 parts by weight, and the content ratio is determined in consideration of the light absorption characteristics of the light absorber.

When the content of the light absorbing agent is less than 0.01 parts by weight, the effect of preventing halation is not sufficient, and halation cannot be effectively prevented. On the other hand, when the amount is more than 60 parts by weight, disadvantages such as a decrease in solvent resistance occur, which is disadvantageous.

To prepare a mixture of a light absorber and a compound having an ethylenically unsaturated group, a light absorber is added to a compound having an ethylenically unsaturated group, and the mixture is stirred and mixed. Performed by dispersing or dissolving. Next, emulsion polymerization or suspension polymerization is carried out according to a conventional method using a compound having an ethylenically unsaturated group containing the light absorber.

Examples of useful polymerization initiators include peroxides such as benzoyl peroxide, cumene hydroperoxide, succinic peroxide, lauroyl peroxide, and hydrogen peroxide, and 2,2'-azobisisopropane. Azo compounds such as butyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), and 2,2'-azobis (2-aminodipropane) dihydrochloride, and peroxides such as ammonium persulfate and potassium persulfate. Redox catalysts such as a sulfuric acid compound, a perchloric acid compound, a combination of the persulfuric acid compound and a reducing sulfoxy compound, and a combination of a perchloric acid compound and a reducing sulfoxy compound are exemplified.

The protective colloid used here includes a saponification degree of 70 to 99 mol% and a polymerization degree of 300 to 40.
00 or partially saponified polyvinyl acetate
Examples thereof include partially saponified polyvinyl acetate derivatives having a reactive unsaturated group as disclosed in JP-A-3-81101.

Other useful protective colloid agents include, for example, gelatin, casein, collagen, starch, starch derivatives, gum arabic, methylcellulose, hydroxyethylcellulose, carboxymethylcellulose, polyacrylamide, polyacrylic acid, and water-soluble nylon. In addition, water-soluble polymers having a reactive unsaturated group or a thiol group as disclosed in JP-B-44-25794 and JP-A-59-187005 can be mentioned as protective colloids.

In some cases, the protective colloid such as the water-soluble polymer and one or more surfactants selected from anionic surfactants, cationic surfactants, amphoteric surfactants and nonionic surfactants. Polymerization may be carried out in combination with an activator.

Further, one or more surfactants selected from anionic surfactants, cationic surfactants, amphoteric surfactants and nonionic surfactants without using a protective colloid such as the water-soluble polymer. The polymerization may be carried out using an agent as an emulsion stabilizer. However, when a large amount of these surfactants is used, the water resistance of an image to be formed and the adhesion to a support are adversely affected.

Then, a photosensitive resin composition is prepared using the aqueous resin emulsion filled with the light absorbing agent obtained by emulsion polymerization or suspension polymerization. As a configuration of the photosensitive resin composition considered here, for example,
There are the following.

1. One or more selected from partially saponified polyvinyl acetate, partially saponified polyvinyl acetate derivatives, gelatin, casein, collagen, starch, starch derivatives, gum arabic, cellulose derivatives, polyacrylamide, polyacrylic acid, water-soluble nylon, etc. A mixture of the light-absorbing water-containing resin emulsion obtained by polymerizing the above water-soluble polymer as a protective colloid agent, and a diazo compound or a dichromate.

Incidentally, a coloring agent such as an organic pigment, an inorganic pigment or a water-soluble dye dispersed by a dispersant such as a surfactant may be added to the photosensitive resin composition. When added, there is an advantage that halation can be more effectively prevented by a synergistic effect with the aqueous resin emulsion filled with the light absorber.

2. One or more selected from partially saponified polyvinyl acetate, partially saponified polyvinyl acetate derivatives, gelatin, casein, collagen, starch, starch derivatives, gum arabic, cellulose derivatives, polyacrylamide, polyacrylic acid, water-soluble nylon, etc. A water-absorbing resin-encapsulated aqueous resin emulsion obtained by polymerizing the above water-soluble polymer as a protective colloid agent, partially saponified polyvinyl acetate, partially saponified polyvinyl acetate derivative, gelatin, casein, collagen, starch, starch derivative , Gum arabic,
A mixture of one or more water-soluble polymers selected from cellulose derivatives, polyacrylamide, polyacrylic acid, water-soluble nylon and the like, and a diazo compound or a dichromate.

A coloring agent such as an organic pigment, an inorganic pigment or a water-soluble dye dispersed by a dispersant such as a surfactant may be added to the photosensitive resin composition. When added, there is an advantage that halation can be more effectively prevented by a synergistic effect with the aqueous resin emulsion filled with the light absorber.

3. One or more selected from partially saponified polyvinyl acetate, partially saponified polyvinyl acetate derivatives, gelatin, casein, collagen, starch, starch derivatives, gum arabic, cellulose derivatives, polyacrylamide, polyacrylic acid, water-soluble nylon, etc. An aqueous resin emulsion filled with the light absorbing agent obtained by polymerizing the above water-soluble polymer as a protective colloid agent; and at least one ethylenic ester selected from acrylates and methacrylates in which a photopolymerization initiator is dissolved. Compounds having a saturated group, partially saponified polyvinyl acetate, partially saponified polyvinyl acetate derivative, gelatin, casein, collagen, starch,
An emulsified dispersion emulsified using one or more water-soluble polymers selected from starch derivatives, gum arabic, cellulose derivatives, polyacrylamide, polyacrylic acid, water-soluble nylon, etc., and a diazo compound or a dichromate And a mixture with.

In this case, a compound having an ethylenically unsaturated group in which a photopolymerization initiator is dissolved may contain a light absorber. When a light absorbing agent is contained, there is an advantage that halation can be more effectively prevented by a synergistic effect with the aqueous resin emulsion filled with the light absorbing agent. Further, a coloring agent such as an organic pigment, an inorganic pigment, or a water-soluble dye dispersed by a dispersant such as a surfactant may be added to the photosensitive resin composition. When added, there is an advantage that halation can be more effectively prevented due to a synergistic effect with the aqueous resin emulsion filled with the light absorber.

4. One or more selected from partially saponified polyvinyl acetate, partially saponified polyvinyl acetate derivatives, gelatin, casein, collagen, starch, starch derivatives, gum arabic, cellulose derivatives, polyacrylamide, polyacrylic acid, water-soluble nylon, etc. The water-soluble polymer acting as a protective colloid agent of the water-absorbent resin-encapsulated aqueous resin emulsion obtained by polymerizing the above water-soluble polymer as a protective colloid agent has a styrylpyridinium salt compound and a styrylquinolinium salt compound. And a one or more photosensitive compounds selected from N-methylolacrylamide and addition-condensed photosensitive emulsion.

It is also possible to mix a diazo compound or a dichromate with the photosensitive resin composition. Further, a coloring agent such as an organic pigment, an inorganic pigment, or a water-soluble dye dispersed by a dispersant such as a surfactant may be added to the photosensitive resin composition. When added, there is an advantage that halation can be more effectively prevented by a synergistic effect with the aqueous resin emulsion filled with the light absorber.

5. One or more selected from partially saponified polyvinyl acetate, partially saponified polyvinyl acetate derivatives, gelatin, casein, collagen, starch, starch derivatives, gum arabic, cellulose derivatives, polyacrylamide, polyacrylic acid, water-soluble nylon, etc. The water-soluble polymer acting as a protective colloid agent of the water-absorbent resin-encapsulated aqueous resin emulsion obtained by polymerizing the above water-soluble polymer as a protective colloid agent has a styrylpyridinium salt compound and a styrylquinolinium salt compound. And one or more photosensitive compounds selected from N-methylolacrylamide and addition-condensed, partially saponified polyvinyl acetate, partially saponified polyvinyl acetate derivative, gelatin, casein, collagen, starch, Starch derivatives, gum arabic, cellulose Body, polyacrylamide, polyacrylic acid, one or more water-soluble polymers selected from water-soluble nylon and the like, a styrylpyridinium salt compound, a styrylquinolinium salt compound and one or more selected from N-methylolacrylamide. A mixture with a photosensitive polymer obtained by addition condensation of a further photosensitive compound.

It is also possible to mix a diazo compound or a dichromate with this photosensitive resin composition. Further, a coloring agent such as an organic pigment, an inorganic pigment, or a water-soluble dye dispersed by a dispersant such as a surfactant may be added to the photosensitive resin composition. When added, there is an advantage that halation can be more effectively prevented by a synergistic effect with the aqueous resin emulsion filled with the light absorber.

6. One or more selected from partially saponified polyvinyl acetate, partially saponified polyvinyl acetate derivatives, gelatin, casein, collagen, starch, starch derivatives, gum arabic, cellulose derivatives, polyacrylamide, polyacrylic acid, water-soluble nylon, etc. The water-soluble polymer acting as a protective colloid agent of the water-absorbent resin-encapsulated aqueous resin emulsion obtained by polymerizing the above water-soluble polymer as a protective colloid agent has a styrylpyridinium salt compound and a styrylquinolinium salt compound. And a photosensitive emulsion in which one or more photosensitive compounds selected from N-methylolacrylamide are addition-condensed, and one or more selected from acrylates and methacrylates in which a photopolymerization initiator is dissolved A compound having an ethylenically unsaturated group One or more selected from partially saponified polyvinyl acetate, partially saponified polyvinyl acetate derivatives, gelatin, casein, collagen, starch, starch derivatives, gum arabic, cellulose derivatives, polyacrylamide, polyacrylic acid, water-soluble nylon, etc. Emulsification using a photosensitive polymer in which one or more photosensitive compounds selected from styrylpyridinium salt compounds, styrylquinolinium salt compounds and N-methylolacrylamide are addition-condensed with the above water-soluble polymer, Mixture with dispersion.

In this case, a compound having an ethylenically unsaturated group in which a photopolymerization initiator is dissolved may contain a light absorber. When a light absorbing agent is contained, there is an advantage that halation can be more effectively prevented by a synergistic effect with the aqueous resin emulsion filled with the light absorbing agent. Further, a coloring agent such as an organic pigment, an inorganic pigment, or a water-soluble dye dispersed by a dispersant such as a surfactant may be added to the photosensitive resin composition. When added, there is an advantage that halation can be more effectively prevented due to a synergistic effect with the aqueous resin emulsion filled with the light absorber. It is also possible to use a mixture of a diazo compound or a dichromate with this photosensitive resin composition.

7. The light absorbing agent-filled aqueous resin obtained by polymerizing one or more surfactants selected from an anionic surfactant, a cationic surfactant, an amphoteric surfactant and a nonionic surfactant as an emulsion stabilizer. 1 selected from emulsion and partially saponified polyvinyl acetate, partially saponified polyvinyl acetate derivative, gelatin, casein, collagen, starch, starch derivative, gum arabic, cellulose derivative, polyacrylamide, polyacrylic acid, water-soluble nylon, etc. Mixtures of one or more water-soluble polymers with a diazo compound or dichromate.

A coloring agent such as an organic pigment, an inorganic pigment or a water-soluble dye dispersed with a dispersant such as a surfactant may be added to the photosensitive resin composition. When added, there is an advantage that halation can be more effectively prevented by a synergistic effect with the aqueous resin emulsion filled with the light absorber.

8. The water-absorbent resin containing the light absorbing agent obtained by polymerizing, as an emulsion stabilizer, one or more surfactants selected from an anionic surfactant, a cationic surfactant, an amphoteric surfactant and a nonionic surfactant. An emulsion and a compound having one or more ethylenically unsaturated groups selected from acrylates and methacrylates in which a photopolymerization initiator is dissolved are partially saponified polyvinyl acetate, partially saponified polyvinyl acetate Derivatives,
Gelatin, casein, collagen, starch, starch derivatives,
1 selected from gum arabic, cellulose derivatives, polyacrylamide, polyacrylic acid, water-soluble nylon, etc.
A mixture of an emulsified dispersion emulsified with one or more water-soluble polymers and a diazo compound or dichromate.

In this case, a compound having an ethylenically unsaturated group in which a photopolymerization initiator is dissolved may contain a light absorber. When a light absorbing agent is contained, there is an advantage that halation can be more effectively prevented by a synergistic effect with the aqueous resin emulsion filled with the light absorbing agent. Also,
A coloring agent such as an organic pigment, an inorganic pigment, or a water-soluble dye dispersed by a dispersant such as a surfactant may be added to the photosensitive resin composition. When added, there is an advantage that halation can be further effectively prevented by a synergistic effect with the aqueous resin emulsion filled with the light absorber.

9. The water-absorbent resin containing the light absorbing agent obtained by polymerizing, as an emulsion stabilizer, one or more surfactants selected from an anionic surfactant, a cationic surfactant, an amphoteric surfactant and a nonionic surfactant. 1 selected from emulsion and partially saponified polyvinyl acetate, partially saponified polyvinyl acetate derivative, gelatin, casein, collagen, starch, starch derivative, gum arabic, cellulose derivative, polyacrylamide, polyacrylic acid, water-soluble nylon, etc. Mixing with a photosensitive polymer in which one or more photosensitive compounds selected from styrylpyridinium salt compounds, styrylquinolinium salt compounds and N-methylolacrylamide are addition-condensed with one or more water-soluble polymers body.

It is also possible to mix a diazo compound or a dichromate with the photosensitive resin composition. Further, a coloring agent such as an organic pigment, an inorganic pigment, or a water-soluble dye dispersed by a dispersant such as a surfactant may be added to the photosensitive resin composition. When added, there is an advantage that halation can be more effectively prevented by a synergistic effect with the aqueous resin emulsion filled with the light absorber.

10. The water-absorbent resin containing the light absorbing agent obtained by polymerizing, as an emulsion stabilizer, one or more surfactants selected from an anionic surfactant, a cationic surfactant, an amphoteric surfactant and a nonionic surfactant. An emulsion and a compound having one or more ethylenically unsaturated groups selected from an acrylate ester and a methacrylate ester in which a photopolymerization initiator is dissolved are partially saponified polyvinyl acetate, partially saponified polyvinyl acetate. Derivatives, gelatin, casein, collagen, starch, starch derivatives, gum arabic, cellulose derivatives, polyacrylamide, polyacrylic acid, one or more water-soluble polymers selected from water-soluble nylon and the like, a styrylpyridinium salt compound, Selected from styrylquinolinium salt compounds and N-methylolacrylamide One or a mixture of an emulsified dispersion is more photosensitive compounds were emulsified with an additional fused photopolymer that.

In this case, a light absorber may be contained in a compound having an ethylenically unsaturated group in which a photopolymerization initiator is dissolved. When a light absorbing agent is contained, there is an advantage that halation can be more effectively prevented by a synergistic effect with the aqueous resin emulsion filled with the light absorbing agent. Also,
A coloring agent such as an organic pigment, an inorganic pigment, or a water-soluble dye dispersed by a dispersant such as a surfactant may be added to the photosensitive resin composition. When added, there is an advantage that halation can be more effectively prevented by a synergistic effect with the aqueous resin emulsion filled with the light absorber.
It is also possible to use a mixture of a diazo compound or a dichromate with the photosensitive resin composition.

In the constitutions shown in the above 4,5,6,9 and 10, the protective colloid of the aqueous resin emulsion filled with the light absorber and the water-soluble polymer to be mixed are described in JP-A-59-213705. As described in the above publication, there is no problem using a partially saponified polyvinyl acetate derivative having a sulfonic acid group or a carboxyl group.

Further, in the constitutions shown in the above 1 to 10, the light-absorbing agent-containing aqueous resin emulsion and the light-absorbing agent-free aqueous resin emulsion (for example, generally available vinyl acetate emulsion, acrylic emulsion) Emulsions, etc.) can also be used in combination.

Further, as a configuration other than the above 1 to 10,
The pigment was dispersed in a compound having at least one type of ethylenically unsaturated group selected from acrylates and methacrylates in which the photopolymerization initiator was dissolved without containing the light-absorbent-filled aqueous resin emulsion. Photosensitization comprising a combination of an emulsified dispersion obtained by emulsifying a pigment-containing oligomer with a protective colloid agent such as a water-soluble polymer such as partially saponified polyvinyl acetate (a surfactant may be used in combination) and a photo-crosslinking agent. The constitution of the conductive resin composition is also easily considered from the present invention.

In addition, in the photosensitive resin compositions of 1 to 10 above, additives usually contained in this kind of photosensitive resin composition,
For example, an antifoaming agent, a repelling inhibitor, a preservative, a thermal polymerization inhibitor, a leveling agent, and the like may be optionally added.

The photosensitive resin composition comprising the water-absorbing resin-incorporated aqueous resin emulsion prepared as described above includes a screen mesh, a glass substrate, a metal plate, a synthetic resin plate,
For example, 1 to 300 μm on an arbitrary support such as a semiconductor substrate.
It is applied and dried so as to have a dry film thickness of m.

The photosensitive material is exposed to a light source such as a xenon lamp, a metal halide lamp, or an ultra-high pressure mercury lamp through a mask such as a negative film or a positive film. Then, non-exposed portions are removed by spray development or immersion development with a developing solution such as water or a water / organic solvent, whereby an image is formed and used as various printing plates, resist films and the like.

[0050]

EXAMPLES The present invention will be further described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Example 1 Operation (1) As a light absorber, 1 part by weight of Seika Fast Yellow 2200 (manufactured by Dainichi Seika Kogyo Co., Ltd., yellow pigment) was mixed with 80 parts by weight of butyl acrylate and 20 parts by weight of 2-ethylhexyl acrylate 20
After mixing with 40 parts by weight of ethylene glycol dimethacrylate, the mixture was sufficiently dispersed to obtain a yellow pigment-containing oligomer.

Next, the yellow pigment-containing oligomer 10
0.5 parts by weight of 2,2'-azobisisobutylnitrile as a thermal polymerization initiator was added to 0 parts by weight, and a partially saponified polyvinyl acetate having an average degree of polymerization of 1700 and a saponification degree of 88 mol% was used as a protective colloid agent. Using 200 parts by weight of a 10% by weight aqueous solution, suspension polymerization was carried out by a conventional method.

The water-based resin emulsion containing the yellow pigment thus synthesized has a particle size of 0.5 μm or less, the yellow pigment particles are fixed in the particles of the emulsion, and the dispersion state of the emulsion particles changes over a long period of three months or more. It was not recognized (hereinafter, this yellow pigment-filled aqueous resin emulsion is referred to as "Em-1").

Operation (2) Partial saponification having an average degree of polymerization of 1700 and a saponification degree of 88 mol% was added to 100 parts by weight of the above-mentioned yellow pigment-containing aqueous resin emulsion "Em-1" adjusted to a solid concentration of 40% by weight. 20 parts by weight of a 10% by weight aqueous solution of polyvinyl acetate are added and mixed, 1 part by weight of a diazo compound composed of a condensate of p-diazodiphenylamine and formaldehyde, and a blue pigment obtained by dispersing a blue pigment in water using a surfactant One part by weight of the dispersion was mixed to obtain a photosensitive resin composition.

Operation (3) The photosensitive resin composition was fixed to an aluminum frame 25
It was applied to a 0 mesh nylon screen using a stainless steel bucket. Coating and drying were repeated 3 to 4 times to obtain a photosensitive coating having a thickness of 70 μm (including the thickness of the screen).

A positive film is adhered to the photosensitive coating,
Exposure was performed for 3 minutes from a distance of 1 m using a kW ultra-high pressure mercury lamp.
Thereafter, the image was immersed in water for 1 minute and spray-developed with water to obtain an image. The obtained image was a good image with a resolution of 50 μm, in which no "fog" of image lines caused by halation (development caused by exposure of unexposed portions due to halation) was observed.

Comparative Example 1 The operation (1) of Example 1 was repeated, except that the yellow pigment was not included as a light absorbing agent, to thereby prepare an aqueous resin emulsion (hereinafter referred to as "N- 1 ").

Except that this "N-1" was used, the same operation as in the operations (2) and (3) of Example 1 was carried out to prepare a photosensitive resin composition, and an image was formed. "Fog" due to halation was observed in the obtained image, and 1
Only an image with a resolution of 00 μm was obtained.

Example 2 3 parts by weight of a photopolymerization initiator Irugacure 651 (manufactured by Ciba-Geigy) and an oil-soluble dye Ye as a light absorber
0.2 parts by weight of low N4G (manufactured by Nippon Kayaku Co., Ltd.)
After dissolving in 25 parts by weight of 2,2'-bis (4-acryloxydiethoxyphenyl) propane and 30 parts by weight of tripropylene glycol diacrylate, a partially saponified polyacetic acid having an average degree of polymerization of 1700 and a saponification degree of 88 mol%. 120 parts by weight of an emulsified dispersion (hereinafter referred to as "H-1") emulsified using 70 parts by weight of a 10% by weight aqueous solution of vinyl, and a yellow pigment-containing aqueous resin emulsion "Em-1" synthesized in Example 1. (Solid content concentration 40% by weight) 100 parts by weight,
A photosensitive resin composition was obtained by mixing 1.5 parts by weight of a blue pigment dispersion obtained by dispersing a blue pigment in water using a surfactant.

Using this photosensitive resin composition, Example 1
The operation (3) was repeated to obtain an image. No "fogging" of image lines caused by halation was observed in the obtained image, and a good image with a resolution of 50 µm was obtained.

Example 3 The procedure (1) of Example 1 was repeated, except that 3 parts by weight of a photopolymerization initiator 3,3-dimethyl-4-methoxy-benzophenone was used as a light absorber. An aqueous resin emulsion containing the composition (hereinafter referred to as "Em-2") was obtained.

The particle size of the water-absorbent resin-containing emulsion "Em-2" thus synthesized was 0.5 .mu.m or less, and the dispersion state of the emulsion particles did not change over a long period of 3 months or more.

100 parts by weight of the above-mentioned light-absorbing agent-containing aqueous resin emulsion “Em-2” adjusted to a solid concentration of 40% by weight and 120 parts by weight of the emulsified dispersion “H-1” used in Example 2, A blue pigment dispersion liquid in which 2 parts by weight of a diazo compound composed of a condensate of diazodiphenylamine and formaldehyde and a blue pigment are dispersed in water using a surfactant,
The parts by weight were mixed to obtain a photosensitive resin composition.

Using the photosensitive resin composition, the same operation as in Example 1 was repeated to obtain an image. No "fog" of the image caused by halation was observed in the obtained image, and the image was a good image with a resolution of 50 µm.

Comparative Example 2 3 parts by weight of a photopolymerization initiator Irugacure 651 (manufactured by Ciba-Geigy), 25 parts by weight of 2,2'-bis (4-acryloxydiethoxyphenyl) propane and 30 parts by weight of tripropylene glycol diacrylate After dissolving in water, 120 parts by weight of an emulsified dispersion emulsified using 70 parts by weight of a 10% by weight aqueous solution of partially saponified polyvinyl acetate having an average degree of polymerization of 1700 and a saponification degree of 88 mol%, and synthesized in Comparative Example 1, 100 parts by weight of an aqueous resin emulsion "N-1" (solid content concentration: 40% by weight) containing no light absorber, and 1.5 parts by weight of a blue pigment dispersion obtained by dispersing a blue pigment in water using a surfactant. By mixing, a photosensitive resin composition was obtained.

Using this photosensitive resin composition, Example 1
The operation (3) was repeated to obtain an image. "Fogging" of the image caused by halation was observed in the obtained image, and only an image with a resolution of 100 μm was obtained.

Example 4 100 parts by weight of the yellow pigment-containing aqueous resin emulsion “E-1” (solid content concentration: 40% by weight) synthesized in Example 1
0.7 part by weight of N-methyl-4- (P-formylstyryl) pyridinium methosulfate is subjected to addition condensation by a conventional method,
A photosensitive yellow pigment-containing aqueous resin emulsion (hereinafter referred to as "Em-1S") adjusted to a solid concentration of 40% by weight was obtained.

Further, the average degree of polymerization was 1400 and the degree of saponification was 88.
Molar% partially saponified polyvinyl acetate 14% by weight aqueous solution 1
To 1000 parts by weight, 1.4 parts by weight of N-methyl-4- (P-formylstyryl) pyridinium methosulfate was added and condensed by a conventional method to adjust the solid content to 12% by weight. An aqueous vinyl acetate solution (hereinafter referred to as “P-1S”) was obtained.

110 parts by weight of the aqueous resin emulsion "Em-1S" containing the photosensitive yellow pigment, 20 parts by weight of a photosensitive partially saponified polyvinyl acetate aqueous solution "P-1S" and 0.2 parts by weight of a water-soluble dye methylene blue. Was mixed to obtain a photosensitive resin composition.

Using this photosensitive resin composition, the operation (3) of Example 1 was repeated to obtain an image. No "fogging" of image lines caused by halation was observed in the obtained image, and a good image with a resolution of 50 µm was obtained.

Comparative Example 3 Aqueous resin emulsion "N-1" (solid content: 40% by weight) containing no light absorbing agent and synthesized in Comparative Example 1
In parts by weight, N-methyl-4- (P-formylstyryl)
In Example 4, 110 parts by weight of a photosensitive aqueous resin emulsion (hereinafter referred to as "N-1S") prepared by subjecting 0.7 parts by weight of pyridinium methosulfate to addition condensation by a conventional method to adjust the solid content concentration to 35% by weight. Prepared photosensitive partially saponified polyvinyl acetate aqueous solution "P-1S" (solid content concentration 40% by weight) 20
The photosensitive resin composition was obtained by mixing 0.2 parts by weight of the water-soluble dye methylene blue with 0.2 parts by weight.

Using this photosensitive resin composition, the operation (3) of Example 1 was repeated to obtain an image. "Fogging" of the image caused by halation was observed in the obtained image, and only an image with a resolution of 100 μm was obtained.

Example 5 3 parts by weight of a photopolymerization initiator Irugacure 651 (manufactured by Ciba Geigy) and an oil-soluble dye Ye as a light absorber
0.2 parts by weight of low N4G (manufactured by Nippon Kayaku Co., Ltd.)
After dissolving in 25 parts by weight of 2,2'-bis (4-acryloxydiethoxyphenyl) propane and 30 parts by weight of tripropylene glycol diacrylate, the aqueous solution of the photosensitive partially saponified polyvinyl acetate prepared in Example 4 (solid 120% by weight of an emulsified dispersion emulsified with 70 parts by weight of "P-1S" and a water-based resin emulsion containing emulsified photosensitive yellow pigment synthesized in Example 4 "Em-
By mixing 110 parts by weight of "1S" (solid content concentration: 35% by weight) and 0.5 part by weight of the water-soluble dye methylene blue, a photosensitive resin composition was obtained.

Using this photosensitive resin composition, the operation (3) of Example 1 was repeated to obtain an image. No "fogging" of image lines caused by halation was observed in the obtained image, and a good image with a resolution of 50 µm was obtained.

Comparative Example 4 3 parts by weight of a photopolymerization initiator Irugacure 651 (manufactured by Ciba-Geigy), 25 parts by weight of 2,2'-bis (4-acryloxydiethoxyphenyl) propane and 30 parts by weight of tripropylene glycol diacrylate After dissolving in water, the photosensitive partially saponified polyvinyl acetate aqueous solution prepared in Example 4 (solid content concentration: 12% by weight) "P-1S" 7
120 parts by weight of an emulsified dispersion emulsified using 0 parts by weight,
100 parts by weight of a photosensitive aqueous resin emulsion "N-1S" (solid content concentration: 35% by weight), which does not include a light absorbing agent, synthesized in Comparative Example 3, and a water-soluble dye, methylene blue 0.1.
By mixing 5 parts by weight, a photosensitive resin composition was obtained.

Using this photosensitive resin composition, the operation (3) of Example 1 was repeated to obtain an image. "Fogging" of the image caused by halation was observed in the obtained image, and only an image with a resolution of 100 μm was obtained.

[0077]

According to the present invention, the use of a photosensitive resin composition containing a water-based resin emulsion filled with a light absorber effectively prevents the effects of halation and provides an image having excellent resolution. Can be easily formed.
Therefore, it can be applied to a wide variety of printing plates and resist materials that require images with excellent resolution.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI G03F 7/028 G03F 7/028 (72) Inventor Kyoichi Sato 27-2 Hiraide Industrial Park, Utsunomiya City, Tochigi Prefecture Oji Chemical Co., Ltd. In the laboratory (56) References JP-A-52-121085 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03F 7/00 501 G03F 7/004 506

Claims (4)

(57) [Claims] 1. A compound having an ethylenically unsaturated group,
In the presence of a light absorber and a water-soluble polymer, the water-soluble polymer obtained by emulsion polymerization or suspension polymerization in water is used as a protective colloid. Water-filled resin emulsion, diazo compound or
A water-soluble photosensitive resin composition comprising a dichromate . 2. A compound having an ethylenically unsaturated group,
In the presence of a light absorber and a water-soluble polymer, the water-soluble polymer obtained by emulsion polymerization or suspension polymerization in water is used as a protective colloid. Styrylpyridinium salt compound and styrylquinolate are added to water-soluble polymer protective colloid of water-filled resin emulsion.
N-methylol acrylamide and N-methylol acrylamide
A water-soluble photosensitive resin composition comprising an aqueous resin emulsion filled with a light absorber obtained by addition-condensing one or more photosensitive compounds selected from the group consisting of: 3. A compound having an ethylenically unsaturated group,
A water-absorbing resin-encapsulated water-based resin emulsion obtained by emulsion polymerization or suspension polymerization in water in the presence of a light absorber, and a water-soluble polymer and diazo
A water-soluble photosensitive resin composition comprising a compound or a dichromate . 4. A compound having an ethylenically unsaturated group,
An aqueous resin emulsion filled with a light absorber, which itself does not have photoreactivity, obtained by emulsion polymerization or suspension polymerization in water in the presence of a light absorber, and styrylpyridinium chloride
Compound, styrylquinolinium salt compound and N-methylo
A water-soluble photosensitive resin composition comprising a water-soluble polymer obtained by addition condensation of one or more photosensitive compounds selected from polyacrylamide .