JPS5917730B2 - Photosensitive resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a water-soluble photosensitive resin composition,
More specifically, the present invention relates to a photosensitive polyvinyl acetal resin composition that has excellent adhesion to metal plates such as aluminum, aluminum, iron, etc., and glass, and can be developed with an aqueous developer.

Conventionally, resin compositions containing diazo compounds, azide compounds, etc. have been used as photosensitive resins, but since these compounds are developed with organic solvents5, they have problems such as toxicity to the human body, flammability, price, and This cannot be said to be preferable in terms of workability and the like.

In addition, as a photosensitive resin composition that can be developed with an aqueous solution, a composition of water-soluble gelatin, polyvinyl alcohol resin, egg white, starch, etc., and ammonium dichromate, potassium dichromate r
However, hexavalent chromium in the composition is highly toxic to the human body and is therefore undesirable. In view of the above-mentioned drawbacks, there has recently been much research into photosensitive resins that can be developed with aqueous solutions, but the development process still requires zinc, aluminum, iron,
Adhesion to copper, glass, etc. is insufficient and line drawings may peel off, and in the etching process, chemical resistance to etching solution is weak, causing line drawings to collapse or peel off. There is. The object of the present invention is to have a composition that does not have the above-mentioned drawbacks, has strong adhesion to the substrate, has strong chemical resistance to etching solutions, does not contain toxic compounds in the composition, and can be developed with an aqueous developer. The object of the present invention is to provide a photosensitive resin composition that is possible.

That is, the gist of the present invention is that when A is a monovalent aldehyde containing one or more unsaturated groups in the molecule and B is a monovalent aldehyde containing no unsaturated groups in the molecule, the degree of polymerization is 30.
0 to 3000 and saponification of 70 to 100 mol%, and the aldehyde A and aldehyde B and j0, relative to the hydroxyl group of the resin,
Polyvinyl acetal resin obtained by acetalization reaction within a range in which acetalization by aldehyde A is greater than 20 equivalent% and 40 equivalent% or less, and acetalization by aldehyde B is 2 to 30 equivalent%.・5
It consists mainly of photosensitive resin compositions.

Monovalent aldehydes containing one or more unsaturated groups in the molecule (hereinafter referred to as A and n) used in the present invention refer to monovalent aldehydes containing one or more unsaturated groups and one aldehyde group in the molecule. For example, crotonaldehyde,
Examples include furfural, cinnamaldehyde, and acrolein, with crotonaldehyde and acrolein being preferred.

The monovalent aldehyde that does not contain an unsaturated group in the molecule used in the present invention (hereinafter referred to as B) is a saturated compound that has a monovalent aldehyde group and has 1 carbon number.
Preferred examples include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, octylaldehyde, and benzaldehyde, with acetaldehyde, formaldehyde, and butyraldehyde being particularly preferred.

The polyvinyl alcohol resin used in the present invention has a polymerization degree of 300 to 3000 and a saponification degree of 70 to 100 mol%. Examples of the polyvinyl alcohol resin include polyvinyl alcohol resin, vinyl acetate and maleic acid, A copolymer resin obtained by saponifying the acetyl group of a copolymer with fumaric acid, acrylic acid, methacrylic acid, sulfostireno, acid phosphooxyethyl methacrylate, etc., or a copolymer resin in which succinic anhydride, maleic anhydride, phthalic anhydride is added to the copolymer resin. Examples include acid anhydride-modified resins reacted with acids and the like. Further, the polymerization degree of the resin is 300 to 300.
The reason why it is limited to 0 is because if the degree of polymerization is less than 300, the sensitivity to light when made into a photosensitive resin composition will decrease and the resistance to etching liquid will deteriorate.
This is because if it is larger than 00, development with an aqueous developer becomes difficult, and 500 to 2000 is preferable. The reason why the degree of saponification is limited to 70 to 100 mol% is because if the degree of saponification is lower than 70 mol%, water solubility decreases and development with an aqueous developer becomes difficult. In the present invention,
The resin is reacted with the above-mentioned aldehydes A and B to form a polyvinyl acetal resin. Aldehyde A is greater than 20 equivalent % and less than 40 equivalent % based on the hydroxyl groups of the resin, and aldehyde B is The reaction is carried out in an amount of 2 to 30 equivalents based on the hydroxyl groups of the resin. Also, the total reaction amount of aldehyde A and aldehyde B is 22 to 7
Although there is no limitation within the range of 0 equivalent%,
If the reaction amount is too large, the solubility in water will deteriorate, so
It is more preferably within the range of 2 to 50 equivalent %. In the present invention, the method for producing the polyvinyl acetal resin is not limited in any way, and any known method may be used; for example, the polyvinyl acetal resin is produced by the following method.

First, polyvinyl alcohol resin is dissolved in water, and hydrochloric acid, sulfuric acid, phosphoric acid, etc. are added as a catalyst while stirring.

Next, predetermined amounts of aldehyde A and aldehyde B were added while stirring, and the mixture was heated at a predetermined temperature (0 to 70°C) for a predetermined time (1
~12 hours) A polyvinyl acetal resin is obtained. In the present invention, the photosensitive resin composition is made mainly from the above-mentioned polyvinyl acetal resin, but the method for imparting photosensitivity to the resin is not limited in any way, and any known method may be used. For example, a method of adding a commonly used photocrosslinking agent to the resin, a method of adding or reacting a photocrosslinkable compound or monomer to the resin to form a photocrosslinkable polyvinyl acetal resin, etc. The following method is used. Examples of photocrosslinking agents that impart photosensitivity to the resin include 3,3'-dimethoxydiphenyl-4,4'-
Tetrazonium chloride, 4,4'-diazidostilbene-2-goodisulfonic acid, and alkali metal salts of these compounds, 2,6-di(4'-azidobenzal)
Cyclohexane, 2,6-di(4'-azidobenzal)
Examples include 4-methylcyclohexanone, which is used in an amount of 1 to 40 parts by weight, preferably 2 to 10 parts by weight, based on 100 parts by weight of the polyvinyl acetal resin.

Examples of compounds having photocrosslinking properties include m- or p-azizobenzaldehyde, azidocinnamaldehyde, formyl-α-naphthylamide, etc. It is preferably used within the range.

Examples of monomers having photocrosslinking properties include 2-hydroxyethyl (meth)acrylate, acrylamide,
dimethyl acrylamide, methylol acrylamide,
Examples include methylenebisacrynoleamide, acroylmorpholine, dimethylaminoethyl acrylate, tetrahydrofurfuryl acrylate, polyethylene glycol di(meth)acrylate, etc., in a range of 20 to 200 parts by weight per 100 parts by weight of polyvinyl acetal resin. It is preferably used in a range of 30 to 100 parts by weight.

The above compounds and monomers are added to or reacted with a polyvinyl acetal resin to produce a photosensitive polyvinyl acetal resin, but the method of producing the resin is not limited in any way by the present invention, and can be any known method. For example, by adding aldehyde A and aldehyde B at the same time during the production of the polyvinyl acetal resin described above, the resulting polyvinyl acetal resin may be reacted with aldehyde A and aldehyde B. It may also be simply added to the resin.

It is also generally used as a sensitizer to improve photosensitivity.

For example, 1,2 benzanthraquinone, 5-nitroacenaphthene, 2-nitrofluorene, sodium atraquinone-2-2-sulfonate, sodium anthraquinone-2,6-disulfonate, sodium benzophenonesulfonate, benzophenone-2,4-dicarboxylic acid, A photosensitizer such as p-hydroquine benzophenone or p-hydroxyacetophenone may be added. The amount of the photosensitizer used is not limited in any way, but it is preferably used in an amount of 25 parts by weight or less, more preferably 0.5 parts by weight or less, per 100 parts by weight of the polyvinyl acetal resin. ~10 parts by weight. The composition of the photosensitive resin composition of the present invention is as described above, and the composition may be used in the form of a powder or a solution. When made into a solution, since the polyvinyl acetal resin in the present invention is water-soluble, water, ethylene glycol monoethyl ether, etc. are preferably used as a solvent. Since the present invention is a water-soluble photosensitive resin composition having the above-mentioned structure, it is not only non-toxic and developable with an aqueous developer, but also suitable for substrates such as zinc, aluminum, iron, copper, glass, etc. It has excellent adhesion to other materials, has excellent photoreactivity, and is easily crosslinked by exposure to light. Therefore, when developed with an aqueous developer after exposure, a clear image can be obtained without the crosslinked portion peeling off.

Also, clear images can be obtained when etching with an etching solution such as a ferric chloride aqueous solution, and no separation or fading of the image occurs. Furthermore, as mentioned above, the resin composition of the present invention applied to a substrate can be easily crosslinked by exposure to light.
Since it forms a film with excellent adhesive properties, the resin composition of the present invention can exhibit excellent performance even when used as a photosensitive paint.

Next, examples of the photosensitive resin composition of the present invention will be described.

Example 1 A stirrer, thermometer, nitrogen inlet tube,
Install a drip load and add 4507 water and 50 tons of polyvinyl alcohol resin (degree of polymerization: 11001, degree of saponification: 99 mol%)
After completely dissolving, 27 butyraldehyde was added and stirred at room temperature for 2 hours, followed by 1 crotonaldehyde.
0y was added thereto, and the mixture was stirred at room temperature for 5 hours to react.

After the reaction was completed, an aqueous sodium hydroxide solution was added to neutralize the mixture at room temperature to obtain an aqueous polyvinyl acetal resin solution.

The resin reacts with 22 equivalents of crotonaldehyde and 4.8 equivalents of butyraldehyde with respect to the hydroxyl groups of the polyvinyl alcohol resin, and the solid content concentration of the aqueous solution is 1.
1.5% and the viscosity was 530 centipoise.

4- to the obtained polyvinyl acetal resin solution 1007
Diazodiphenylamine formaldehyde condensate 0.
5 t was added and thoroughly stirred to obtain a photosensitive resin composition.

The composition was applied to a surface-polished steel plate with a thickness of 0.8 mm using a wire coater so that the film thickness after drying was 3 μm, and dried at 60° C. for 10 minutes to obtain a photosensitive steel plate.

A negative film was adhered to the surface of the photosensitive steel plate, exposed for 1 minute from a distance of 5CTn using a 20W chemical lamp, and then developed by immersing it in an ethyl alcohol aqueous solution (1/1) for 2 minutes to obtain a positive image. It was done.

Next, the steel plate was dried at 120° C. for 5 minutes, and then immersed in an aqueous ferric chloride solution (porter at 45 degrees) for 15 minutes. After immersion, the plate was washed with water and further immersed in a 10% aqueous sodium hydroxide solution, and a clean relief plate was obtained without peeling of the photosensitive resin. Example 2 A polyvinyl acetal resin aqueous solution was obtained in the same manner as in Example 1 except that acrolein 147 was used instead of crotonaldehyde.

In this resin, 4.8 equivalents of butyraldehyde and 39.5 equivalents of acrolein reacted with the hydroxyl groups of the polyvinyl alcohol resin used, and the solid content of the aqueous solution was 1.
2% and the viscosity was 780 centipoise. 57 y of 2-hydroxyethyl methacrylate was added to 100 y of the aqueous solution.
and 0.1 t of benzophenone (1% by weight ethyl alcohol solution 107 g) were added and sufficiently stirred to obtain a photosensitive resin composition.

The composition was coated, dried and exposed in the same manner as in Example 1.

The obtained photosensitive steel plate was fed into an oven at 120°C.
After being heat-treated for 5 minutes, the film was boiled in boiling water for 5 minutes, but the film did not peel off at all.

Claims (1)

[Claims] 1. When A is a monovalent aldehyde containing one or more unsaturated groups in the molecule, and B is a monovalent aldehyde containing no unsaturated groups in the molecule, the degree of polymerization is 300 to 3000 and a saponification degree of 70 to 100 mol%, and the aldehyde A and aldehyde B.
and is acetalized within a range in which the acetalization by aldehyde A is greater than 20 equivalent % and 40 equivalent % or less, and the acetalization by aldehyde B is 2 to 30 equivalent %, based on the hydroxyl group of the resin. A photosensitive resin composition whose main component is a polyvinyl acetal resin obtained by reaction. 2. The photosensitive resin composition according to claim 1, wherein the total degree of acetalization by aldehyde A and aldehyde B is 22 to 50 equivalent %.