JPH0627649A - Color photographic photosensitive resin composition - Google Patents

Abstract

PURPOSE:To prevent halation and to obtain an image high in resolution by using an emulsion containing a light absorbing agent as a constituent of the photosensitive resin composition. CONSTITUTION:This photosensitive resin composition contains the aqueous resin emulsion filled with the light absorbent obtained by emulsion- or suspension-polymerizing a compound having an ethylenic unsaturated group in water in the presence of the light absorbent, and this light absorbent is mixed into the polymer c>f the compound having the ethylenic unsaturated group in a adsorbent to compound weight ratio of 0.01-60, preferably, 0.05-10, controlled in accordance with the absoption characteristics by adding the absorbent to the compound with stirring and, then, dispersing or dissolving it.

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 light absorbing agent-filled water-soluble resin emulsion. 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 A conventional water-developable printing plate, particularly a photosensitive resin for producing a screen printing plate, mainly comprises an aqueous resin emulsion, a water-soluble polymer and a photo-crosslinking agent, which is effective for preventing halation. To obtain a high-resolution image, a colorant such as an aqueous pigment or a water-soluble dye has been added as an antihalation agent.

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

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

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art by using a light absorber-containing emulsion as a constituent of the 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]

The present inventors have found that the above object can be achieved by using an aqueous resin emulsion having a halation-preventing 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 problems, a light-absorbing compound obtained by emulsion-polymerizing or suspension-polymerizing a compound having an ethylenically unsaturated group in water in the presence of a light-absorbing agent. Provided is a photosensitive resin composition comprising a water-in-resin resin emulsion.

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

Examples of the above-mentioned organic pigments include azo-based, phthalocyanine-based, benzimidazolone-based, quinacridone-based, isoindolinone-based, pyrathuron-based, dibrom zanzanthrone-based, indathuron-based, anthrapyrimidine-based, flavasuron-based, Perylene-based, Perinone-based, Quinophthalone-based, Phthalone-based, Thioindigo-based, Indigo-based,
Examples thereof include condensed polycyclic pigments including dioxazine pigments, anthraquinone pigments, xanthene pigments, methine pigments and azomethine pigments and other metal complex pigments. Examples of inorganic pigments include milori blue, iron oxide, cobalt violet, manganese violet, ultramarine blue, navy blue, cobalt blue,
Cerulean blue, viridian, emerald green,
Cobalt green etc. can be mentioned.

These organic pigments and inorganic pigments have a particle size of 0.7 μm or less, preferably 0. It is preferably 1 μm or less.

Examples of dyes include nitroso type, nitro type, azo type, stilbenazo type, ketoimine type, triphenylmethane type, xanthene type, acridine type, quinoline type, methine type, thiazole type, indamine type and azine type. , Oxazine-based, thiazine-based, aminoketone-based, anthraquinone-based, phthalocyanine-based and triallylmethane-based dyes.

Examples of the ultraviolet absorber include cyanoacrylate type, benzotriazole type and salicylic acid type. Examples of photopolymerization initiators and photosensitizers include benzophenone-based, cinnamate-based, thioxanthone-based, benzoate-based, benzoin-based and acetophenone-based compounds.

These light absorbers may be used alone or in combination of two or more.

Next, the compound having an ethylenically unsaturated group is a compound having one or more ethylenically unsaturated groups in the molecule, and examples thereof include alkyl acrylates (eg, methyl acrylate, acryl acrylate). Ethyl acid, butyl acrylate, 2-ethylhexyl acrylate, etc.), alkyl methacrylates (eg, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, etc.), epoxy acrylates (methacrylate) ), Urethane acrylates (including methacrylate), polyether acrylates (including methacrylate), polyester acrylates (including methacrylate), acrylic acid, methacrylic acid, glycidyl acrylate, glycidyl methacrylate, ac Le allyl, allyl methacrylate, itaconic acid, acrylamide, methacrylamide,
Dimethylaminoethyl acrylate, diethylaminoethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, N-methylol acrylamide, N-methylol methacrylamide, acrylonitrile, styrene, α-methyl styrene , Vinyl acetate, vinyltoluene, vinylpyridine, 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-butyl Glycol dimethacrylate,
2,2-bis [4- (acryloxy-polyethoxy)
Phenyl] propane, 2,2-bis [4- (methacryloxy-polyethoxy) phenyl] propane, trimethylolpropane triacrylate, tetramethylolmethane triacrylate, tetramethylolmethane tetraacrylate, 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 kinds.

The content ratio of the light absorber is 0.01 to 60 relative to 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 part by weight, the effect of preventing halation is insufficient and halation cannot be effectively prevented. On the other hand, if the amount is more than 60 parts by weight, disadvantages such as deterioration of solvent resistance occur, which is inconvenient.

The mixture of the light absorbing agent and the compound having an ethylenically unsaturated group is prepared by adding the light absorbing agent to the compound having an ethylenically unsaturated group, stirring and mixing, and then thoroughly using a usual method. It is carried out by dispersing or dissolving. Next, emulsion polymerization or suspension polymerization is carried out by a conventional method using the compound having an ethylenically unsaturated group containing the light absorber.

Examples of the polymerization initiator useful here include benzoyl peroxide, cumene hydroperoxide, succinic acid peroxide, lauroyl peroxide, peroxides such as hydrogen peroxide, and 2,2'-azobisisoe. Butyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-aminodipropane) dihydrochloride, and other azo compounds, ammonium persulfate, potassium persulfate, and other perazo compounds. Redox catalysts such as a sulfuric acid compound, a perchloric acid compound and the like, a combination of the persulfate compound and a reducing sulfoxy compound, a combination of a perchloric acid compound and a reducing sulfoxy compound, and the like can be mentioned.

The protective colloid used herein has a saponification degree of 70 to 99 mol% and a polymerization degree of 300 to 40.
Partially saponified poly (vinyl acetate) which is 00,
Partially saponified polyvinyl acetate derivatives having a reactive unsaturated group as disclosed in 3-81101 can be mentioned.

Other useful protective colloid agents include, for example, gelatin, casein, collagen, starch, starch derivatives, gum arabic, methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, polyacrylamide, polyacrylic acid, water-soluble nylon and the like. Further, 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.

Depending on the case, the above-mentioned protective colloid such as water-soluble polymer and one or more kinds of interfaces selected from anionic surfactants, cationic surfactants, amphoteric surfactants or nonionic surfactants. You may polymerize using an activator together.

Furthermore, one or more kinds of surface active agents selected from anionic surface active agents, cationic surface active agents, amphoteric surface active agents, or nonionic surface active agents are used without using the protective colloid such as the water-soluble polymer. You may polymerize using an agent as an emulsion stabilizer. However, if a large amount of these surfactants is used, the water resistance of the image formed and the adhesiveness to the support are adversely affected, so it is desirable to use a relatively small amount even if used.

Then, a photosensitive resin composition is prepared using the water-absorbent resin-filled resin emulsion obtained by emulsion polymerization or suspension polymerization. Examples of the constitution of the photosensitive resin composition considered here include:
There are the following.

1. One or more selected from 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. A mixture of the water-absorbent resin-containing water-absorbent resin emulsion obtained by polymerizing the above water-soluble polymer as a protective colloid agent, and a diazo compound or a dichromate.

A colorant 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 water-absorbing resin emulsion in the light absorber.

2. One or more selected from 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. Water-absorbing resin-filled resin emulsion prepared 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 dichromate.

A colorant 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 water-absorbing resin emulsion in the light absorber.

3. One or more selected from 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. The above water-absorbing resin-filled resin emulsion obtained by polymerizing the above water-soluble polymer as a protective colloid agent, and one or more ethylenic compounds selected from acrylic acid ester and methacrylic acid ester in which a photopolymerization initiator is dissolved. The compound having a saturated group is partially saponified polyvinyl acetate, partially saponified polyvinyl acetate derivative, gelatin, casein, collagen, starch,
Emulsified dispersion obtained by emulsifying one or more water-soluble polymers selected from starch derivatives, gum arabic, cellulose derivatives, polyacrylamide, polyacrylic acid, water-soluble nylon, etc., and diazo compound or dichromate. A mixture with.

In this case, the light absorber may be contained in the compound having an ethylenically unsaturated group in which the photopolymerization initiator is dissolved. When a light absorber is contained, there is an advantage that halation can be more effectively prevented by a synergistic effect with the water-absorbent resin-filled resin emulsion. In addition, a colorant 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 the synergistic effect with the water-absorbing resin emulsion in the light absorber.

4. One or more selected from 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. The water-soluble polymer that acts as a protective colloid agent in the water-absorbent resin-filled water-absorbent resin emulsion obtained by polymerizing the above water-soluble polymer as a protective colloid agent is added to the styrylpyridinium salt compound and the styrylquinolinium salt compound. And a photosensitive emulsion in which one or more photosensitive compounds selected from N-methylolacrylamide are addition-condensed.

It is also possible to mix and use a diazo compound or a dichromate with this photosensitive resin composition. In addition, a colorant 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 effectively prevented due to a synergistic effect with the water-absorbing resin emulsion in the light absorber.

5. One or more selected from 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. The water-soluble polymer that acts as a protective colloid agent in the water-absorbent resin-filled water-absorbent resin emulsion obtained by polymerizing the above water-soluble polymer as a protective colloid agent is added to the styrylpyridinium salt compound and the styrylquinolinium salt compound. And a photosensitive emulsion to which one or more photosensitive compounds selected from N-methylol acrylamide are added and condensed, and partially saponified polyvinyl acetate, partially saponified polyvinyl acetate derivative, gelatin, casein, collagen, starch, Starch derivative, gum arabic, cellulose Body, polyacrylamide, polyacrylic acid, water-soluble nylon or the like, and one or more water-soluble polymers, and one or more selected from styrylpyridinium salt compounds, styrylquinolinium salt compounds and N-methylolacrylamide or A mixture with a photosensitive polymer obtained by addition-condensing a further photosensitive compound.

It is also possible to mix and use a diazo compound or a dichromate with this photosensitive resin composition. In addition, a colorant 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 water-absorbing resin emulsion in the light absorber.

6. One or more selected from 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. The water-soluble polymer that acts as a protective colloid agent in the water-absorbent resin-filled water-absorbent resin emulsion obtained by polymerizing the above water-soluble polymer as a protective colloid agent is added to the styrylpyridinium salt compound and the styrylquinolinium salt compound. And one or more selected from N-methylolacrylamide, a photosensitive emulsion in which one or more photosensitive compounds are added and condensed, and an acrylic acid ester and a methacrylic acid ester in which a photopolymerization initiator is dissolved. A compound having an ethylenically unsaturated group of One or more selected from 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. Emulsification using a photosensitive polymer obtained by addition-condensing one or more photosensitive compounds selected from styrylpyridinium salt compounds, styrylquinolinium salt compounds and N-methylolacrylamide to the above water-soluble polymers. Mixture with dispersion.

In this case, the light absorber may be contained in the compound having an ethylenically unsaturated group in which the photopolymerization initiator is dissolved. When a light absorber is contained, there is an advantage that halation can be more effectively prevented by a synergistic effect with the water-absorbent resin-filled resin emulsion. In addition, a colorant 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 the synergistic effect with the water-absorbing resin emulsion in the light absorber. It is also possible to use a mixture of this photosensitive resin composition with a diazo compound or a dichromate.

7. The water-absorbing resin filled in the light absorber obtained by polymerizing, as an emulsion stabilizer, one or more surfactants selected from anionic surfactants, cationic surfactants, amphoteric surfactants and nonionic surfactants. Emulsion, selected from 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. 1 Mixtures of one or more water-soluble polymers with diazo compounds or dichromates.

A colorant 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 water-absorbing resin emulsion in the light absorber.

8. The water-absorbing resin filled in the light absorber obtained by polymerizing, as an emulsion stabilizer, one or more surfactants selected from anionic surfactants, cationic surfactants, amphoteric surfactants and nonionic surfactants. The emulsion and a compound having one or more ethylenically unsaturated groups selected from acrylic acid ester and methacrylic acid ester in which a photopolymerization initiator is dissolved are partially saponified polyvinyl acetate and partially saponified polyvinyl acetate. Derivative,
Gelatin, casein, collagen, starch, starch derivative,
1 selected from gum arabic, cellulose derivative, 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 a dichromate.

In this case, the light absorber may be contained in the compound having an ethylenically unsaturated group in which the photopolymerization initiator is dissolved. When a light absorber is contained, there is an advantage that halation can be more effectively prevented by a synergistic effect with the water-absorbent resin-filled resin emulsion. Also,
A colorant 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 the synergistic effect with the water-absorbing resin emulsion in the light absorber.

9. The water-absorbing resin filled in the light absorber obtained by polymerizing, as an emulsion stabilizer, one or more surfactants selected from anionic surfactants, cationic surfactants, amphoteric surfactants and nonionic surfactants. Emulsion, selected from 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. 1 Mixing with one or more water-soluble polymer, a styrylpyridinium salt compound, a styrylquinolinium salt compound, and one or more photosensitive compounds selected from N-methylolacrylamide are added and condensed with a photosensitive polymer. body.

It is also possible to mix and use a diazo compound or a dichromate with this photosensitive resin composition. In addition, a colorant 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 water-absorbing resin emulsion in the light absorber.

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

In this case, the light absorber may be contained in the compound having an ethylenically unsaturated group in which the photopolymerization initiator is dissolved. When a light absorber is contained, there is an advantage that halation can be more effectively prevented by a synergistic effect with the water-absorbent resin-filled resin emulsion. Also,
A colorant 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 the synergistic effect with the water-absorbing resin emulsion in the light absorber.
It is also possible to use a mixture of this photosensitive resin composition with a diazo compound or a dichromate.

Further, in the constitutions shown in the above 4, 5, 6, 9 and 10, the protective colloid agent for the water-absorbent resin emulsion in the light absorber and the water-soluble polymer to be mixed are disclosed in JP-A-59-213705. As disclosed in US Pat. No. 4,096,861, a partially saponified polyvinyl acetate derivative having a sulfonic acid group or a carboxyl group may be used.

In addition, in the constitutions 1 to 10 described above, the water-absorbent resin emulsion containing the light absorber and the water-soluble resin emulsion containing no light absorber (for example, commercially available vinyl acetate emulsions and acrylic emulsions) are used. It is also possible to use together (emulsion etc.).

Further, as a configuration other than the above 1 to 10,
The pigment was dispersed in a compound having at least one ethylenically unsaturated group selected from acrylic acid ester and methacrylic acid ester in which a photopolymerization initiator was dissolved, not containing the water-absorbent resin emulsion in the light absorber. Photosensitization consisting of a combination of a pigment-containing oligomer emulsified with a protective colloid agent such as a water-soluble polymer such as partially saponified polyvinyl acetate (which may be used in combination with a surfactant) and a photo-crosslinking agent. The constitution of the resin composition is also easily conceivable from the present invention.

In addition, in the photosensitive resin composition of the above 1 to 10, additives usually contained in this type of photosensitive resin composition,
For example, a defoaming agent, an anti-repellent agent, an antiseptic agent, a thermal polymerization inhibitor, a leveling agent, etc. may be optionally added.

The photosensitive resin composition containing the water-absorbent resin-filled resin emulsion prepared as described above is used as 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 used by coating and drying so that the dry film thickness is m.

The photosensitive material is brought into close contact with a mask such as a negative film or a positive film, and exposed through a light source such as a xenon lamp, a metal halide lamp or an ultra-high pressure mercury lamp through the mask. Next, the non-exposed area is removed by spray development or immersion development with a developing solution such as water or 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 (yellow pigment manufactured by Dainichi Seika Kogyo Co., Ltd.), 80 parts by weight of butyl acrylate and 20 parts of 2-ethylhexyl acrylate were used.
The mixture was mixed with 40 parts by weight of ethylene glycol dimethacrylate and then sufficiently dispersed to obtain a yellow pigment-containing oligomer.

Then, 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 of the partially saponified polyvinyl acetate having an average polymerization degree of 1700 and a saponification degree of 88 mol% as a protective colloid agent. Suspension polymerization was carried out by a conventional method using 200 parts by weight of a 10% by weight aqueous solution.

The particle size of the synthesized water-soluble resin emulsion containing yellow pigment is 0.5 μm or less, the yellow pigment particles are fixed in the emulsion particles, and the dispersion state of the emulsion particles changes over a long period of 3 months or more. It was not observed (hereinafter, this yellow pigment-containing water-filled resin emulsion is referred to as "Em-1").

Operation (2) 100 parts by weight of the yellow pigment-containing water-soluble resin emulsion "Em-1" adjusted to a solid content concentration of 40% by weight is partially saponified with an average degree of polymerization of 1700 and a degree of saponification of 88 mol%. A blue pigment in which 20 parts by weight of a 10% by weight aqueous solution of polyvinyl acetate was added and mixed, 1 part by weight of a diazo compound consisting of a condensate of p-diazodiphenylamine and formaldehyde, and a blue pigment were dispersed in water using a surfactant. 1 part by weight of the dispersion liquid was mixed to obtain a photosensitive resin composition.

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

A positive film was adhered to this photosensitive coating film, and 3
It was exposed for 3 minutes from a distance of 1 m with a kW ultra-high pressure mercury lamp.
Then, it 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 without "fogging" of image lines caused by halation (development caused by exposure of the non-exposed portion due to halation).

Comparative Example 1 The procedure (1) of Example 1 was repeated except that a yellow pigment was not incorporated as a light absorber to prepare an aqueous resin emulsion (hereinafter referred to as “N- 1 ”).

A photosensitive resin composition was prepared in the same manner as in the operations (2) and (3) of Example 1 except that this "N-1" was used to form an image. "Fog" due to halation was recognized in the obtained image. 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 being dissolved in 25 parts by weight of 2,2'-bis (4-acryloxydiethoxyphenyl) propane and 30 parts by weight of tripropylene glycol diacrylate, partially saponified polyacetic acid having an average degree of polymerization of 1700 and a degree of saponification of 88 mol%. 120 parts by weight of an emulsified dispersion (hereinafter referred to as "H-1") emulsified with 70 parts by weight of a 10% by weight aqueous solution of vinyl, and a yellow pigment-containing water-filled resin emulsion "Em-1" synthesized in Example 1 (Solid 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 liquid in which a blue pigment was dispersed 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 an excellent image having a resolution of 50 μm was obtained.

Example 3 The operation (1) of Example 1 was repeated except that 3 parts by weight of the photopolymerization initiator 3,3-dimethyl-4-methoxy-benzophenone was used as the light absorber. A water-in-resin resin emulsion (hereinafter referred to as "Em-2") was obtained.

The particle size of the water-absorbent resin emulsion in the light absorber "Em-2" thus synthesized was 0.5 µm or less, and the dispersion state of emulsion particles was not changed over a long period of 3 months or more.

100 parts by weight of the water-absorbent resin-filled resin emulsion "Em-2" adjusted to a solid content concentration of 40% by weight and 120 parts by weight of the emulsified dispersion "H-1" used in Example 2, p 2 parts by weight of a diazo compound consisting of a condensate of diazodiphenylamine and formaldehyde, a blue pigment dispersion liquid in which a blue pigment is dispersed in water using a surfactant 1.5
By mixing parts by weight, a photosensitive resin composition was obtained.

Using this photosensitive resin composition, the same operation as in Example 1 was repeated to obtain an image. No "fogging" of image lines caused by halation was observed in the obtained image, and the image was good 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 were used. Was synthesized in Comparative Example 1 with 120 parts by weight of an emulsion dispersion obtained by emulsifying with 70 parts by weight of an aqueous solution of 10% by weight of partially saponified polyvinyl acetate having an average degree of polymerization of 1700 and a degree of saponification of 88 mol%. 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 liquid in which a blue pigment was dispersed 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. In the obtained image, "fog" of the image line caused by halation was recognized, and only an image having a resolution of 100 μm was obtained.

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

The average degree of polymerization is 1400 and the degree of saponification is 88.
14% by weight aqueous solution of partially saponified polyvinyl acetate of 1 mol% 1
1.4 parts by weight of N-methyl-4- (P-formylstyryl) pyridinium methosulfate was added and condensed to 00 parts by weight by a conventional method to adjust the solid content concentration to 12% by weight. An aqueous vinyl acetate solution (hereinafter referred to as "P-1S") was obtained.

110 parts by weight of the water-soluble 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 part by weight of the water-soluble dye methylene blue. A photosensitive resin composition was obtained by mixing.

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 an excellent image having a resolution of 50 μm was obtained.

COMPARATIVE EXAMPLE 3 Aqueous resin emulsion "N-1" (solid content concentration 40% by weight) synthesized in Comparative Example 1 and containing no light absorber 100
In parts by weight, N-methyl-4- (P-formylstyryl)
0.7 parts by weight of pyridinium methosulfate was added and condensed by a conventional method to prepare a photosensitive aqueous resin emulsion (hereinafter referred to as "N-1S") having a solid content concentration of 35% by weight. Prepared photosensitive partially saponified polyvinyl acetate aqueous solution "P-1S" (solid content concentration 40% by weight) 20
A photosensitive resin composition was obtained by mixing 1 part by weight and 0.2 part by weight of the water-soluble dye methylene blue.

Using this photosensitive resin composition, the operation (3) of Example 1 was repeated to obtain an image. In the obtained image, "fog" of the image line caused by halation was recognized, and only an image having 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 photosensitive partially saponified polyvinyl acetate aqueous solution prepared in Example 4 (solid (Concentration: 12% by weight) 120 parts by weight of an emulsified dispersion emulsified with 70 parts by weight of "P-1S" and a water-soluble resin emulsion "Em-" embedded in a photosensitive yellow pigment synthesized in Example 4.
A photosensitive resin composition was obtained by mixing 110 parts by weight of 1S "(solid content concentration 35% by weight) and 0.5 parts by weight of the water-soluble dye methylene blue.

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 an excellent image having 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 were used. Dissolved in water, and then the photosensitive partially saponified polyvinyl acetate aqueous solution prepared in Example 4 (solid content 12% by weight) "P-1S" 7
120 parts by weight of an emulsified dispersion liquid emulsified with 0 parts by weight,
100 parts by weight of a photosensitive aqueous resin emulsion "N-1S" (solid content concentration: 35% by weight) synthesized in Comparative Example 3 and containing no light absorber, and a water-soluble dye methylene blue 0.1.
A photosensitive resin composition was obtained by mixing 5 parts by weight.

Using this photosensitive resin composition, the operation (3) of Example 1 was repeated to obtain an image. In the obtained image, "fog" of the image line caused by halation was recognized, and only an image having a resolution of 100 μm was obtained.

[0077]

According to the present invention, by using a photosensitive resin composition containing a water-absorbing resin-filled water-in-oil resin emulsion, the effect of halation can be effectively prevented and an image having excellent resolution can be obtained. 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.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical indication H01L 21/027 // C08F 2/44 MCR 7442-4J C08L 101/00 LTB 7242-4J (72) Inventor Kyoichi Sato 27-2 Hiraide Industrial Park, Utsunomiya City, Tochigi Prefecture Oji Kako Co., Ltd. Product Research Center

Claims (1)

[Claims] 1. A compound having an ethylenically unsaturated group,
A photosensitive resin composition comprising a light absorbing agent-filled water-soluble resin emulsion obtained by emulsion polymerization or suspension polymerization in water in the presence of a light absorbing agent.