JPS603623A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To develop an exposed photosensitive layer with only water without requiring an org. solvent by using a latex polymer having cationic groups, a water-soluble ethylenic unsated. compound having anionic groups, and a photopolymn. initiator. CONSTITUTION:This photosensitive resin composition consists essentially of a latex polymer having cationic groups, a water-soluble ethylenic unsatd. compound having anionic groups, and a photopolymn. initiator. Since the latex polymer and the ethylenic unsatd. compound are dissolved or dispersed well in water because of the ionized state, the photosensitive resin composition requires only water as a solvent. When the composition is exposed, the uncured parts are dissolved in water and removed, and the cured parts are made hydrophobic by the physical and chemical bond of a polymer of the unsatd. compound to the latex polymer to form a film of high strength. At this time, environmental pollution and safety and hygienic problems are not caused. When the photosensitive resin composition is used in the manufacture of a printing plate, the cured parts are not swollen, so the parts have satisfactory resolving power and high ink retentivity.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to photosensitive resin compositions, and particularly to photosensitive image forming materials having a photosensitive layer such as various plate-making materials and resists for printed wiring boards. The present invention relates to a photosensitive photopolymerizable composition which can use only water as a coating solvent, can be developed with only water, and can improve the hydrophobicity of the photosensitive layer after exposure.

PRIOR ART Printing plates such as lithographic printing plates and resin letterpress plates or plate-making films are produced by forming a photosensitive layer on a support, and converting this photosensitive layer into a hardened layer and a non-hardened layer by exposing it to light according to the brightness of the original. There is also one in which an image area and a non-image area are formed on the support by dissolving and removing the uncured layer with a developer. In addition, in printed wiring plates, a photosensitive layer is formed on the metal layer on the upper surface of the support, and a hardened layer of the circuit pattern is formed on this photosensitive layer by exposure, as in the case of the above-mentioned printing plates, and the non-exposed areas are The uncured layer is removed by melting in a developing layer, and then the metal layer on the support is etched with an acid or alkaline solution.

By the way, in order to form the above-mentioned photosensitive layer with a composition,
This composition contains a photopolymerization initiator, a photopolymerizable unsaturated compound, and a binder that adheres the cured film to the substrate when the unsaturated compound polymerizes to form a cured film. The coating is dried.Then, when the original is exposed to light, the unsaturated compound polymerizes and hardens in the areas exposed to light, while the areas not exposed to light remain uncured.When this is developed, the uncured areas is dissolved and removed in a developer. In this case, since unsaturated compounds that do not polymerize are easily removed, the binder needs to be dissolved or dispersed and removed by the developer.

In the above, most of the post-exposure development treatments have so far used organic solvents or alkaline aqueous solutions. However, when an organic solvent is used, it is not only bad for the environmental health and safety of the workplace, but also poses a problem of pollution due to the discharged solvent, and also poses a cost problem due to recovery or disposal of the solvent. Further, when using an alkaline water-soluble solution, it is troublesome to adjust the pH around 8 times, and there is also the problem that it is dangerous if it comes into contact with the eyes.

Therefore, some products have been devised that can be developed with neutral water without these problems, but these products still have strong hydrophilic properties in the image area of the photosensitive layer in the case of planographic printing plates, for example. If this ink is used as is for printing, it will impair the adhesion of the ink to the printed area, or so-called ink receptivity, since the ink is usually lipophilic. Furthermore, in the case of a printed wiring board, if the hardened layer is highly hydrophilic, the etching solution may penetrate into the hardened layer and cause pinholes, for example. Things that can be developed with this neutral water include:
For example, as described in JP-A No. 49-76602, a photosensitive resin composition is prepared by converting a polyamide resin having a sulfonate salt group into Mayingoo and containing a photopolymerizable polymerizable unsaturated compound therein. Things can be mentioned. This composition is applied and dried to form a photosensitive layer, and when this is exposed to light, the polymerizable unsaturated compound polymerizes and becomes water-insoluble.
Since the polyamide resin is water-soluble, the non-exposed areas are dissolved and removed by water. However, since the polyamide resin contained in the cured part is still hydrophilic,
It contains water and easily swells during development. This not only impairs the ink receptivity as described above, but also makes it difficult to reproduce minute images.

As a method to prevent this swelling, JP-A-50-7
No. 605 discloses a photosensitive resin composition in which a polyamide resin having a basic nitrogen atom in a portion of the main chain or side chain is used as a binder and a polymerizable unsaturated compound is contained in the binder. In this method, basic nitrogen contained in a polyamide resin is ionized with quaternary ammonium using an organic acid having a polymerizable unsaturated bond, and the unsaturated compound crosslinks the polyamide resin by light irradiation. This has a high film strength and the above-mentioned swelling property is improved to some extent. However, polyamide resin has repeated amide bonds in its main chain, and these amide groups are relatively hydrophilic, so the above-mentioned improvement in swelling properties is not sufficient.

If the binder is hydrophilic, the above-mentioned swelling problem cannot be solved, so in Japanese Patent Application Laid-Open No. 54-91585, a latex in which a water-insoluble resin is dispersed is used, and a polymerizable unsaturated compound is added to the latex. The included composition is shown. This material has a so-called filler effect as a result of latex particles being filled into a polymer of unsaturated compounds by light irradiation, and once it forms a film, it is no longer hydrophilic.
The chemical and physical bonding strength between the latex particles and the polymer of unsaturated compounds after exposure is weak, so for example, the latex particles must be resistant to being scratched by a brush during development and must have durability as a printing plate. There is a problem in that the film must be firmly held on the support.

In addition, if the polymerizable unsaturated compound is not hydrophilic, it is difficult for the water developer to penetrate into the uncured areas of the coated material when the water developer is used to remove the uncured areas, and the latex particles are difficult to remove. In addition, when using water-based latex, water-soluble polymerizable unsaturated compounds are used, so the cured product of this composition after exposure must be prevented from becoming hydrophilic. This will cause the same problem as above.

Although the above was an attempt to use neutral water as a developer, when forming a photosensitive layer for the printing plate or printed wiring board by coating a photosensitive resin composition,
When an organic solvent is used in this photosensitive resin composition, there are problems in terms of pollution and health and safety as described above. However, in conventionally known photosensitive resin compositions, it is difficult to dissolve the binder or polymerizable unsaturated compound in water only, or even if it can be dissolved in water. Most of them have extremely high viscosity and cannot be coated, so organic solvents have had to be used as the main solvent to impart coating properties.

As mentioned above, conventionally, when organic solvents are used in developing solutions, there are problems with pollution and health and safety, and when using aqueous developers, using a hydrophilic binder causes problems with the swelling of the cured part in the water developing solution. However, when latex is used, there are problems with film strength, especially when water-based latex is used, and in addition to this, it becomes hydrophilic.Furthermore, organic solvents are mainly used as coating solvents for photosensitive resin compositions. There were problems similar to those mentioned above, and improvements were desired.

OBJECTS OF THE INVENTION The first object of the present invention is to provide a photosensitive resin composition for a photosensitive layer, which allows development of the photosensitive layer after exposure using only water without using an organic solvent. There is a particular thing.

The second object of the present invention is to achieve a photosensitive layer in which the cured portion of the photosensitive layer loses its hydrophilicity and becomes hydrophobic even if it is developed using only water as described above, and the film strength becomes poor. An object of the present invention is to provide a resin composition.

A third object of the present invention is to provide a photosensitive resin composition that allows the use of an aqueous solvent containing mainly water or a solvent consisting only of water when forming a photosensitive layer on a support by coating a photosensitive resin composition. An object of the present invention is to provide a resin composition.

Structure of the Invention In order to achieve the above object, the present invention is characterized by comprising a latex polymer having a cationic group, a water-soluble ethylenically unsaturated compound having an anionic group, and a photopolymerization initiator. It is something to do.

In the present invention, in the above structure, both the latex polymer and the ethylenically unsaturated compound are ionized, so they are well dispersed or dissolved in water, and thus, it is possible to use only water as the solvent for the photosensitive resin composition. It is possible to develop the uncured part after the exposure operation only with water demon, and on the other hand, the hardened part after the exposure operation is developed by the physical and chemical reaction between the unsaturated compound polymer and the latenox polymer. The bonding makes it possible to make the film hydrophobic and increase the strength of the film.

In the present invention, the latenox polymer having a cationic group serves as a binder for adhering the ethylenically unsaturated compound photopolymer described later to the support well, and also acts as a binder (for the photopolymer layer). It is a constituent component, and its main one has a quaternary nitrogen atom in its molecule, which improves its dispersibility in water and also improves its physical interaction with the ethylenically unsaturated compound polymer. It is something that causes a bond.

This quaternary nitrogen atom is preferably contained in a side chain of the polymer molecule.

Representative examples of the heptadmer q1-position constituting such a polymer include those represented by the following general formulas [■] to [■].

General formula (1) General formula (IV) p ■ General formula (V) In general formulas (1) to [■], X- represents an anion. That is, BF containing halogen ions, sulfate ions, phosphate ions, sulfonate ions, acetate ions, and fluorine thereof:, PF6-, S1F6SbF6-1BeF
Anions such as 4- are included.

The R's bonded to N+ may be the same or different, each R being a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (e.g. methyl, ethyl, propyl, isobutyl, pentyl, hexyl, heptyl, decyl). each group)
, alkenyl groups (e.g. propenyl, butynyl groups)
, or an aralkyl group (e.g., phenyl, naphthyl group), aralkyl group (e.g., -, phenyl, phenethyl, naphthyl, methyl group) having 6 to 20 carbon atoms.
, or represents an alkaryl group (for example, tolyl or xylyl group). Moreover, those having a polymerizable unsaturated ethylene group are also preferable. This is because if the molecule has a polymerizable group, it will polymerize and form a chemical bond with the ethylenically unsaturated compound during photopolymerization, which will be described later. Z represents a nonmetallic atom group necessary to form an unsaturated heterocycle, and is preferably imidazole, pyridine, piperidine, pyrrole or morpholine 4-ring. n represents an integer.

The latex polymer having a cationic group according to the present invention, which is not represented by the general formula above, has a c-c bond in its main chain and is therefore hydrophobic and has a polar group, so when a photosensitive layer is formed. Contributes to its hydrophobicity. For example, in the case of a water-based latex polymer, the latex polymer only needs to have enough water-soluble groups to be dispersed in water, so a relatively large number of hydrophobic groups can be introduced into the polymer molecule, reducing its hydrophilicity. This is advantageous in that the dispersion containing it has a low viscosity relative to the resin concentration, so it has good coating properties when forming a photosensitive layer, and the dried film can be formed into a thick film. In order to introduce hydrophobic groups into this latex polymer and adjust its water solubility, it is sufficient to copolymerize the above-mentioned cationic monomer with a non-cationic monomer. Examples of the non-cationic monomer include acrylic acid ester, methacrylic acid Examples include ester, styrene, alkylene, vinyl acetate, acrylonitrile, and the like. This latex 11 is preferably crosslinked with a monomer having two or more unsaturated groups, such as divinylbenzene or dimecacrylate, and is preferably produced by emulsion polymerization. This is because it reduces the hydrophilicity of the monomer and enables effective emulsion polymerization, thereby contributing to the improvement of film strength.

In order to produce a copolymer of the above cationic monomer and non-cationic monomer, in the latex polymer having the above cation 4gJJH;
The content is preferably 5% by weight, more preferably 25% by weight.
~65% by weight. In addition, the non-cationic monomer is 5 to
The content is preferably 95%, and preferably 0.1 to 8% by weight of the crosslinking monomer such as divinylbenzene.

As a synthesis example of the latex polymer having the above-mentioned cationic group in the present invention, vinylbenzyl chloride is emulsion polymerized with other monomers as described in the example of JP-A-51-73440, and then A method of quaternizing with a tertiary amine can be adopted. Another preferred synthesis method is the method described in JP-A-55-22766. Another preferred synthesis method is disclosed in JP-A-56-1735.
This is the method described in Publication No. 2.

The latex polymer having a cationic group used in the present invention has a quaternary nitrogen atom in the cationic group substantially in the composition, and the latex polymer having an amine, especially a tertiary amine in its molecule is a water-based solvent. This also includes the case where the group becomes a cationic group having a quaternary nitrogen atom as a result of being dispersed in the group.

The particle size of the latex polymer is preferably 10 to 200 mμ, and if it is smaller than 10 mμ, it is difficult to manufacture and is not practical. On the other hand, if it is larger than 20Qmμ, the resolution of the image will be poor when forming the image area after exposure of the photosensitive layer.

Specific examples of the polymer having a cationic group of the present invention include the compounds shown below. Note that the value in parentheses is the molar ratio.

(The following is the margin of this page) [Exemplary compounds] (1) (4:4B74B) (3) (4:68:28) (4) (4:Silver;28) (5) (4:48:48) (6 ) Partner: 46: 46) (7) (4:38:58) (8) (2:69:29) (11) (4:68:28) CH:] (12) (6:37:57) CH3 CH3 (13) (6:47:47) CH3 I 1CH2-N-C21-15 1m (14) (4:68:28) CH3 ■ CH3 (15) (2:49:49) (16) (2:29:69) (17) (4:86=10) CH9 I - (18) ■:80) □ C6H+2 (19) (4:48:48) H=CI-12 (20) (47Fi3 :3i3) CH3 (21) (4:48:20:28) CH3 In the present invention, the ethylenically unsaturated compound having an anionic group constitutes a component that polymerizes when the photosensitive layer is exposed to light. It is a monomer that can be dissolved in As the anionic group of such ethylenically unsaturated compounds, those having a carboxyl group or a sulfonic acid group are particularly useful. Specific compounds include acrylic acid 1. Examples include aliphatic ethylenic carboxylic acids such as meccrylic acid and itaconic acid, and aromatic ethylenic carboxylic acids such as vinylbenzenecarboxylic acid. Also useful are ethylene monomers having sulfonic acid groups such as vinylhensensulfonic acid and 2-acrylamido-2methylpropanesulfonic acid. In addition, the anionic ethylenic monomer having a tyrenic unsaturated group of 2(flit or more) can also act as a crosslinking agent, so it can form a three-dimensional polymer and greatly increase the strength of the photosensitive layer cured by exposure. It is especially self-effective because it can be done.

As the photopolymerization initiator used in the present invention, various previously unknown photoradical generators can be used. Specifically, benzophenone and its derivatives, benzoin and its derivatives, anthrachytone and its derivatives, halogen compounds, sulfur compounds,
Examples include thioxanthone and its derivatives, and lophine dimers. These photoradical generators may be used in combination, and if necessary, a sensitizer such as a hydrogen donor may be added.

The preferred composition ratio range of the photosensitive resin composition of the present invention is 25 to 7% of the latex polymer having a cationic group.
4% by weight, 25 to 74% by weight of the ethylenically unsaturated compound having an anionic group, and 1 to 30% by weight of the photopolymerization initiator.

If the latex polymer is too small, it cannot function as a binder, and if it is too large, the proportion of the ethylenically unsaturated compound polymer in the photosensitive layer decreases, so the cationic polymer does not form salts with anionic groups. Since a group is formed and becomes free, it becomes more hydrophilic, which is not preferable.

The same applies when the polymer having an anionic group becomes excessive.

Therefore, in the cured layer of the photosensitive layer, it is desirable from the viewpoint of hydrophobicity that the anionic group and the cationic group exist in equimolar amounts or in the vicinity thereof.

The dispersion medium or solvent of the photosensitive resin composition in the present invention may be only water, since the latex polymer having a cationic group is dispersible and the ethylenically unsaturated compound is water-soluble. As mentioned above, there may be no problems such as pollution, but a water-miscible organic solvent may be used as an auxiliary to improve the wetting of the photosensitive resin composition to the support during application and the drying properties during drying. I can do it. Examples of such substances include methanol, ethanol, methyl cellosolve, ethyl cellosolve, acetone, halogenated hydrocarbons, ethyl acetate, and the like.

Various additives can be added to the photosensitive resin composition of the present invention as necessary. For example, an appropriate amount of hydroxyl and its analogous compounds can be added to prevent thermal polymerization during storage.

Other additives such as an adhesion improver, another jj1 combination as a binder, and a matte agent to roughen the surface of the photosensitive layer can be added.

In order to produce the photosensitive composition of the present invention, the above-mentioned ingredients may be stirred and mixed by an appropriate means.

In order to prepare a photosensitive image forming material such as a lithographic printing plate, a resin letterpress plate, a plate-making film, or a photoresist for metal etching of a printed wiring board using the photosensitive resin composition of the present invention, it is necessary to This photosensitive resin composition is applied to and dried to form a photosensitive layer. This photosensitive layer may be provided as a single layer, but, for example, when creating an ultraviolet blocking photomask for a plate-making film,
An undercoat layer may be provided on a transparent support, and then a photosensitive layer made of the photosensitive resin composition of the present invention may be formed on this undercoat layer. In this case, the undercoat layer is a polymer compound with a colored material (for example, 300 nm to 7 nm) to block ultraviolet rays.
There are some to which dyes having absorption in the 00 nm wavelength range or pigments such as copper phthalocyanine, carbon blank, and titanium dioxide are added.

The thickness of the photosensitive layer thus provided is 0.1 to 20 g/dry coating film of the photosensitive resin composition.
- range is appropriate.

Supports for producing the above-mentioned photosensitive image forming materials include metal plates such as aluminum, iron, copper, or alloys thereof, paper supports, especially synthetic paper (polypropylene, polyethylene laminated paper, etc.), and plastics. Examples include cellulose acetate, polyethylene terephthalate, polypropylene, polystyrene, vinylidene chloride, and the like.

Such a support is desirably surface-treated electrically, chemically, or mechanically for the purpose of improving adhesion with the photosensitive layer. Further, a subbing layer may be provided to improve this adhesiveness. Furthermore, in order to make the surface of the photosensitive layer formed as described above less slippery, a layer made of the above-mentioned capping agent may be provided, and in the case of a photosensitive image forming material using a flexible support, Alternatively, an anti-curl layer for preventing curling may be provided on the surface opposite to the photosensitive layer.

In order to produce a photosensitive image forming material using the photosensitive resin composition according to the present invention, a spin coating method, a bra, 1. □
Typical coating methods such as -7, 1, -Fi, 8, and 71 bar coating methods are used, and after the coating is applied by these methods, it is dried by an appropriate method.

The photosensitive image forming material prepared as described above is first imagewise exposed to actinic light. As the actinic light, any light can be used as long as it sensitizes the photopolymerization initiator contained in the photosensitive resin composition.

Examples include mercury lamps, xenon lamps, lasers, and the like.

The exposed photosensitive imaging material is developed with ordinary tap water. In this case, warm water or alkali or acid may be added as necessary. At this time, development can be carried out effectively by rubbing the surface with a suitable material such as a sponge.

In this way, a photosensitive layer made of the above photosensitive resin composition is formed on the support, and this photosensitive layer is exposed and developed to create an image-formed material. The photopolymerization initiator in the photosensitive layer is activated by actinic light to generate radicals, which are added to ethylenically unsaturated compounds to induce polymerization of these unsaturated compounds. Can be combined. In this case, the hydrophilic substance becomes hydrophobic. In addition, when a latex polymer having cationic nests has an ethylenically unsaturated group, it also polymerizes with the ethylenically unsaturated compound having the anionic group, and as a result, a chemical bond is formed between the two, resulting in three-dimensional i1 ↓Can be combined to further improve film strength.

Effects of the Invention According to the present invention, the latex polymer has a cationic group and the ethylenically unsaturated compound has an anionic group. It is possible to prepare a photosensitive resin composition by dispersing or melting it in a solvent containing Apply the photosensitive resin composition used for
(・There is no problem of pollution such as when forming a luminescent layer, and since development can be done with a developer consisting only of water, there is no problem of pollution as with conventional development using organic solvents or alkaline aqueous solution. It is possible to provide a photosensitive resin composition that does not have problems such as pH adjustment and can reduce costs.

In addition, the photosensitive resin composition of the present invention is expected to form a thick coating film, improve coating properties, and improve the water resistance of a dried coating film due to the presence of a latex polymer, and is also expected to have a filler effect. The polymer having a cationic group is in the form of latex, and the dispersion medium of this latex contains a water-soluble unsaturated compound having an ethylenic group. It can be seen that the aqueous developer easily penetrates into the uncured portion of the non-exposed area, and this uncured portion can be removed very easily when developing with the aqueous developer.

In addition, the photosensitive layer made of the photosensitive resin composition of the present invention is cured by exposure to light, and the ionic layer becomes non-ionic, losing its hydrophilicity and becoming hydrophobic. We can provide materials.

For example, when used in a printing plate, the area hardened by exposure during development will not swell with water, and when this hardened area is used as an image area, the h'+i image power can be improved, and the hydrophobic The ink adhesion to the printed image area is improved. As a result of the hardened portion becoming hydrophobic, it exhibits strong resistance to water solubility of strong acids or strong bases during metal etching, especially when used in photoresists for printed wiring patterns, eliminating the need for etching. It is possible to prevent pinholes from forming at certain locations and obtain a good mask image. In this way, it is possible to provide a photosensitive resin composition with improved performance, ease of handling, and cost, which can be used, for example, in lithographic printing plates, resin letterpress plates, plate-making films, photoresists for printing substrates, and the like.

Examples Next, the present invention will be described in detail, but the present invention is not limited to these examples. In addition, in the following examples, "parts" indicate "parts by weight" unless otherwise specified.

Example 1 7a. , 3 mm17) A716. A)jii@2
0%') y @ y -1 After immersion in an aqueous solution to milk fat and electropolishing, it was anodized in sulfuric acid, further treated with an aqueous sodium metasilicate solution, washed with water, and then dried.

This substrate (support) was coated with a photosensitive liquid having the following composition so that the film thickness after coating and drying was 3.0 μm to obtain a printing original plate having a photosensitive layer according to this example.

45.0 parts of latex polymer having a cationic group of the above exemplary compound (1) (solid content 1
0% aqueous dispersion) 2-acrylamido-2-methylpropanesulfonic acid 4.5 parts Diisopropylthioxanthone 0.5 parts Isoamyl dimethylaminobenzoate 0.5 parts Methyl cellosolve 4
．． 0 parts water 50.0 parts Above, adhere Kodasoku Temptabble Soto No. 2 as a negative film to the above printing plate and add 20 parts with Idol Fin 200 [manufactured by Iwasaki Electric Co., Ltd., 2 parts w metal halide lamp].
After exposure for seconds, the unexposed portions were removed by rubbing with a sponge in water at 20° C. for 1 minute to obtain a printing plate. The number of curing stages of the step tablet was five. Next, when this printing plate was printed on high-quality paper using a sheet-fed offset printing machine, more than 20,000 good-quality prints were obtained.

Example 2 An aluminum plate treated in the same manner as in Example 1 was coated with a photosensitive liquid having the following composition so that the film after coating and drying was 3.0 μm to obtain a printing original plate.

65.0 parts of latex polymer having a cationic group of the above exemplary compound (4) (solid content 1
0% aqueous dispersion) Divinylbenzenesulfone (yl 2 , 5 parts Isoamyl dimethylaminobenzoate 0.5 parts Diisoprobylthioxanthone 0.5 parts Polyvinyl alcohol 1.
5 children (1; water 30.0 copies) This original printing plate was exposed and developed in the same manner as in Example 1 to obtain a printing plate. When this printing plate was printed on high-quality paper using a sheet-fed offset printing machine, high-quality printed matter was obtained. More than 30,000 copies were obtained.

Example 3 An aluminum plate treated in the same manner as in Example 1 was coated with a photosensitive liquid having the following composition so that the film after coating and drying was 3.0 μm to obtain a printing original plate.

55.0 parts of latex polymer having a cananic group of the above exemplary compound (19) (solid content 1
0% aqueous dispersion) 2-acrylamido-2-methylpropanesulfonic acid 3.5 parts Diisopropylthioxanthone 0.5 parts Isoamyl dimethylaminobenzoate 0.5 parts Methyl cellosolve 4
．． 0 parts Water 36.5 parts This printing original plate was exposed and developed in the same manner as in Example 1 to obtain a printing plate. When this printing plate was printed on high-quality paper using a sheet-fed offset printing machine, more than 40,000 good-quality prints were obtained.

Example 4 Aluminum was deposited on one side of a polyethylene terephthalate film with a thickness of 100 μm to a thickness of 700 μm to form a metal thin film layer. Then, a photosensitive layer was provided on one of the metal thin film layers by coating the photosensitive liquid used in Example 2 so that the film thickness after coating and drying was 2 μm. After exposing this photosensitive layer with a negative film in close contact with it,
After immersing in water at 0° C. for 1 minute, the unexposed portion of the photosensitive layer was removed by rubbing lightly with a sponge. Then add 4g to 100m6 of water.
After being immersed in an aqueous solution of sodium hydroxide for 3 minutes, washed with water, and dried, a high-contrast positive image with few pinholes was obtained.

Comparative Example 1 An aluminum plate treated in the same manner as in Example 1 was coated with a photosensitive solution having the composition shown below so that the film after coating and drying had a thickness of 3.0 μm to provide a photosensitive layer.

Polyethyl acrylate latex polymer (solid content 10% water, 45.0 parts dispersion) 2-acrylamido-2-methylpropanesulfonic acid 4.5 parts Diisopropylthioxanthone 0.5 parts Isoamyl dimethylaminobenzoate 0.5 Methyl cellosolve 4
．． 0 parts Water 50.0 parts A negative film (Kodasoku Tesobutabure) No. 2 was adhered to this photosensitive layer, and exposed in the same manner as in Example 1.
When development was carried out, the exposed areas swelled with water and were removed when rubbed with a sponge, resulting in no image area being obtained. Even when the exposure time was increased to 60 seconds, no image area was obtained.

Comparative Example 2 On one side of a polyethylene terephthalate film having a thickness of 100 μm, aluminum was vapor-deposited to a thickness of 700 μm to form a metal thin film layer. Next, a photosensitive liquid having the following composition was applied onto this metal thin film layer, and after drying, the film was 2.
A photosensitive layer was provided so as to have a thickness of 0 μm.

Latex polymer having a cationic group of the above exemplary compound (1) (solid content 10% aqueous dispersion) 45.0 parts Trimethylolpropane triacrylate 4.5 parts Diisopropylthioxanthone 065 parts Dimethylaminobenzoic acid iso7 0.5 Part Mil Methyl Cellosolve 54.0 parts A negative film was brought into close contact with the above photosensitive layer, exposed in the same manner as in Example 1, immersed in water at 30°C for 1 minute, and then rubbed lightly with a sponge to remove the unexposed parts of the photosensitive layer. was removed. Next, it was immersed for 3 minutes in an aqueous solution of 4 g of sodium hydroxide dissolved in 100 ml of water, washed with water, and dried. The obtained image had many pinholes and lacked practicality.

June 21, 1982

Claims (1)

[Claims] (1) A latex polymer having a cationic group, a water-soluble ethylenically unsaturated compound having an anionic group,
A photosensitive resin composition comprising a photopolymerization initiator.