JPS5946379B2 - Photosensitive resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photosensitive resin composition, and more particularly to a photosensitive polyvinyl acetal resin composition that has excellent adhesion to aluminum, zinc, etc. and can be developed with an aqueous developer. It is about things.

Conventionally, resin compositions containing diazo compounds, azudo compounds, etc. have been used as photosensitive resins, but since these compounds are developed with organic solvents, they have problems with toxicity to the human body, flammability, cost, and workability. It cannot be said that it is preferable from the viewpoint of etc.

Furthermore, 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, etc. has been used. Valent chromium 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 they still do not adhere well to zinc, aluminum, iron, copper, glass, etc. during the development process, resulting in line drawings peeling off. In addition, in the etching process, the chemical resistance to the etching solution is weak, and the line drawings may be distorted or peeled off. The object of the present invention is to provide a photosensitive material that does not have the above-mentioned drawbacks, has strong adhesion to a substrate, has low chemical resistance to etching solutions, does not contain toxic compounds in its composition, and can be developed with an aqueous developer. An object of the present invention is to provide a synthetic resin composition.

That is, the gist of the present invention is to convert monovalent aldehydes containing one or more unsaturated groups in the molecule into B monovalent aldehydes containing 1 to 9 carbon atoms in the molecule and no unsaturated groups.
When, the degree of polymerization is 300 to 2000 and the degree of saponification is 70 to 100 mol? and the aldehyde A and aldehyde B, the acetalization by aldehyde A is 1 to 20 equivalents, e1 the acetalization by aldehyde B is 1 to 30 equivalent%, based on the hydroxyl group of the resin, The total of acetalization by aldehyde A and acetalization by aldehyde B is 2 to 40
It consists in a photosensitive resin composition mainly composed of a polyvinyl acetal resin obtained by acetalization reaction within a certain range of equivalent %.

The monovalent aldehyde containing one or more unsaturated groups in the molecule used in the present invention (hereinafter referred to as A) is a compound having one or more unsaturated groups and one aldehyde group in the molecule. Among these, examples include crotonaldehyde, furfural, cinnamaldehyde, acrolein, etc., and crotonaldehyde and furfural are particularly preferably used. 1 to 9 in the molecule used in the present invention
A monovalent aldehyde containing 1 to 9 carbon atoms and no unsaturation (hereinafter referred to as B) is a saturated compound having 1 to 9 carbon atoms and having one aldehyde group, such as formaldehyde, acetaldehyde, etc. , propionaldehyde, butyraldehyde, isobutyraldehyde, octylaldehyde, benzaldehyde, etc., and acetaldehyde, propionaldehyde, and butyraldehyde are particularly preferably used.

The polyvinyl alcohol resin used in the present invention has a polymerization degree of 300 to 2000 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 in which the acetyl group of a copolymer with fumaric acid, acrylic acid, methacrylic acid, sulfostyrene, acid phosphooxyethyl methacrylate, etc. is saponified, or succinic anhydride, Examples include acid anhydride-modified resins made by reacting maleic anhydride, phthalic anhydride, and the like.

The degree of polymerization of the resin is limited to 300 to 2,000 because if the degree of polymerization is less than 300, the photosensitive resin composition will have lower sensitivity to light and poor etching resistance. Also, if the degree of polymerization is greater than 2000, development with an aqueous developer becomes difficult. Also, the degree of saponification is 70 to 100 moles? The reason for this is that 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, and the amount of aldehyde A is 1 to 20 equivalents based on the hydroxyl group of the resin. , aldehyde B is 1 to 30 equivalent% based on the hydroxyl group of the resin,
The total amount of aldehyde A and aldehyde B is reacted within a range of 2 to 40 equivalent %.

Acetalization by aldehyde A is 1 equivalent? When it is lower, the photocrosslinking property decreases, and 20 equivalents? If it becomes higher, it becomes impossible to develop with an aqueous developer. And more preferably 3~
15 equivalents? It is best to react within this range. Also, is the acetalization by aldehyde B 1 equivalent? If it is lower than 30 equivalent%, there will be no adhesion to the substrate, and if it is higher than 30 equivalent%, the adhesiveness to the substrate will be very good, but it will not be possible to develop with an aqueous developer, and more preferably 1 to 15%.
It is preferable that the reaction be carried out within the range of equivalent %. Furthermore, regarding the total reaction amount of aldehyde A and aldehyde B, if it is lower than 2 equivalents, the photocrosslinking property and adhesion will be poor, and 40 equivalents? If the content is higher, development with an aqueous developer becomes difficult, so the content is set at 2 to 40 equivalent%, preferably 4 to 3.
It is 0 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, a polyvinyl alcohol resin is dissolved in water, and an acid such as hydrochloric acid or sulfuric acid is 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. Examples of methods that can be used include adding a commonly used photocrosslinking agent to the resin, or reacting a photocrosslinkable compound with the resin to form a photocrosslinkable polyvinyl acetal resin. . Examples of photocrosslinking agents that impart photosensitivity to the resin include 3,3-dimethoxydiphenyl-4,4-tetrazonium chloride, 4,4'-diazidostilbene-2,2-disulfonic acid, and Alkali metal salts of these compounds, 2,6-
Di(47-azizobenzal)cyclohexane, 2,6-
Examples include di(4-azidobenzal)4-methylcyclohexanone, which is used in an amount of 1 to 30 parts by weight, particularly 5 to 20 parts by weight, per 100 parts by weight of polyvinyl acetal resin.
It is preferably used within the range of

Further, examples of compounds having photocrosslinking properties include m- or p-azidobenzaldehyde, azidocinnamaldehyde, formyl-α-naphthylamide, etc., in an amount of 1 to 20 equivalents to the hydroxyl group of the polyvinyl alcohol resin.
It is preferably used within the range of .

The compound reacts with a polyvinyl acetal resin to form a photosensitive polyvinyl acetal resin, but the method for producing the resin is not limited in any way in the present invention, and any known method may be used. For example, a photosensitive polyvinyl acetal resin can be obtained by adding it simultaneously with aldehyde A and aldehyde B during the production of the aforementioned polyvinyl acetal resin. In order to improve photosensitivity, photosensitizers commonly used as sensitizers, such as 1,2-benzanthraquinone, 5-nitroacenaphthene, and 2-nitrofluorene, may also 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 per 100 parts by weight of the polyvinyl acetal resin. 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 photosensitive resin composition having the above-mentioned structure, it is not only non-toxic and developable with an aqueous developer, but also has excellent properties on substrates such as zinc, aluminum, iron, copper, etc. It has adhesive properties, and 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. Next, examples of the photosensitive resin composition of the present invention will be described.

Example 1 A stirrer, a thermometer, a nitrogen introduction tube,
Install a drip load and add water 4009 and polyvinyl alcohol resin (polymerization degree 650, saponification degree 88 mol%) 1009
After completely dissolving, add concentrated hydrochloric acid (3
5%) 5.159, crotonaldehyde 6.299 and butyraldehyde 3.249 were added and reacted at 45°C for 6 hours.

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 reacted with 10 equivalents of crotonaldehyde and 5 equivalents of butyraldehyde with respect to the hydroxyl groups of the polyvinyl alcohol resin, and the solid content concentration of the aqueous solution was 20%.

Water was added to the obtained polyvinyl acetal resin solution to obtain an aqueous solution with a solid content of 12.5%.

In 100 g of the aqueous solution, 2 4,4 diazide still pens were added.
, -1.259% of sodium disulfonate was added thereto and thoroughly stirred to obtain a photosensitive resin composition.

The composition was applied to a surface-polished zinc plate with a thickness of 0.8 mm,
It was coated with a wire coater so that the film thickness after drying was 2 μm, and dried at 60° C. for 10 minutes to obtain a photosensitive zinc plate.
A negative film was closely attached to the surface of the photosensitive zinc plate, and
After irradiating it with a W chemical lamp for 3 minutes from a distance of 5CTII, it was immersed in water for 2 minutes and developed, and a positive image was obtained.

Next, the zinc plate was dried at 120° C. for 5 minutes and then etched with a commercially available etching solution, resulting in a clean zinc relief plate without peeling of the photosensitive resin. Example 2 Using cinnamaldehyde instead of crotonaldehyde
．． A polyacetal resin aqueous solution was obtained in the same manner as in Example 1 except that acetaldehyde was used instead of 939 and butyraldehyde.

Does this resin contain 5 equivalents of cinnamaldehyde relative to the hydroxyl groups of the polyvinyl alcohol resin used? , 5 equivalents of acetaldehyde? has reacted, and the solid content of the aqueous solution is 20%.
It was hot.

The aqueous solution was diluted with water to adjust the solids content to 12.5%.

To the prepared aqueous solution 1009 was added 1,259 mol of sodium 4,4 diazidostilbene-2,2'-disulfonate, and the mixture was sufficiently stirred to obtain a photosensitive resin composition. The composition was applied to a printed wiring board in the same manner as in Example 1,
After coating, drying, exposure and development, a beautiful positive image was obtained.

After drying the substrate at 120° C. for 5 minutes, the copper foil of the substrate was corroded with a ferric chloride solution, and the resist film was peeled off with methylene chloride containing 20% methanol to obtain a good printed wiring board. Example 3 Water 4009 and polyvinyl alcohol resin (polymerization degree 1650, saponification degree 88 mol%) 1009 were supplied to the same apparatus as used in Example 1, and after completely dissolving them, concentrated hydrochloric acid (35%) was added while stirring. 5.13f! and furfural 4.35
9 and butyraldehyde 3249 were added and reacted at 45° C. for 6 hours, followed by neutralization with an aqueous sodium hydroxide solution at room temperature to obtain an aqueous polyvinyl acetal resin solution.

The resin contains 5 equivalents of furfural to the hydroxyl group of the polyvinyl alcohol resin? , butyraldehyde was reacted in an amount of 5 equivalents, and the solid content concentration of the aqueous solution was 20%.

After adding water to the aqueous solution to adjust the solid content concentration to 12.5%, 3,3'-dimethoxydiphenyl-4,47-bisdiazonium talolide zinc chloride double salt 59 was added to the aqueous solution 1009. The mixture was thoroughly stirred and mixed to obtain a photosensitive resin composition. Using this composition, a photosensitive plate was obtained in the same manner as in Example 1, and a beautiful letterpress plate was made.

Example 4 Water 4009 and polyvinyl alcohol resin (degree of polymerization 600, degree of saponification 88 mol%) were added to the same apparatus as used in Example 1.
) 1009 and completely dissolved it, concentrated hydrochloric acid (35%
) 5.129, crotonaldehyde 6.609, butyraldehyde 3.249 and p-azidobenzaldehyde 6
．． 609 was added and reacted at 20° C. for 12 hours, and then neutralized with an aqueous sodium hydroxide solution at room temperature to obtain an aqueous photosensitive polyvinyl acetal resin solution.

The resin contains 5 equivalents of crotonaldehyde relative to the hydroxyl group of the polyvinyl alcohol resin. , 5 equivalents of butyraldehyde, 5 equivalents of p-azidobenzaldehyde? A reaction occurred, and the solid content concentration of the aqueous solution was 20%.

After adding water to the aqueous solution to adjust the solid content concentration to 12.5%, 0.259 of sodium 4,47-diazidostilbene-2,2-disulfonate was added to 1009 of the aqueous solution to make a sufficient amount. were stirred and mixed to obtain a photosensitive resin composition.

Using this composition, a photosensitive plate could be obtained in the same manner as in Example 1, and a clearer letterpress plate could be made.

Example 5 In a device similar to that used in Example 1, water 4009 and polyvinyl alcohol modified resin (polymerization degree 1700, saponification degree 94) were added.
Mol? , carboxylic acid amount 2.2 mol%) 1009, and after completely dissolving, concentrated hydrochloric acid (35%) 5
．． 449, 10.539 of crotonaldehyde, and 3.619 of butyraldehyde were added and reacted at 45° C. for 6 hours, and then neutralized with an aqueous sodium hydroxide solution at room temperature to obtain an aqueous polyvinyl acetal resin solution.

The resin contains 15 equivalents of crotonaldehyde relative to the hydroxyl group of the polyvinyl alcohol-modified resin. , 5 equivalents of butyraldehyde? A reaction occurred, and the solid content concentration of the aqueous solution was 20%.

Using this aqueous solution, add 1% sodium metasilicate as a developer.
A clear relief plate was made in the same manner as in Example 1 except that an aqueous solution was used.

Comparative Example 1 Water 4009 and polyvinyl alcohol resin (polymerization degree 650, saponification degree 88 mol%) were placed in the same equipment as used in Example 1.
After supplying 1009 and completely dissolving it, add concentrated hydrochloric acid (35%
) 5.129 and crotonaldehyde 6.299 were added and reacted at 45°C for 6 hours, followed by neutralization with an aqueous sodium hydroxide solution at room temperature to obtain an aqueous polyvinyl acetal resin solution.

The resin contains 10 equivalents of crotonaldehyde relative to the hydroxyl group of the polyvinyl alcohol resin. A reaction occurred, and the solid content concentration of the aqueous solution was 20%.

When a zinc relief plate was prepared using the aqueous solution in the same manner as in Example 1, part of the photosensitive resin layer was peeled off during etching.

Comparative Example 2 In a device similar to that used in Example 1, water 4009 and polyvinyl alcohol resin (polymerization degree 6501 saponification degree 88 mol%) were added.
) and after complete dissolution, add concentrated hydrochloric acid (35%)5.
44 g of crotonaldehyde, 15.729 g of crotonaldehyde, and 22.649 g of butyraldehyde were added, and the mixture was reacted at 20° C. for 12 hours, resulting in the formation of a precipitate.

After neutralizing the reaction solution with an aqueous sodium hydroxide solution, the precipitate was filtered, washed with water, and dried to obtain a polyvinyl acetal resin.
The resin contains 25% by weight of crotonaldehyde and 3% by weight of butyraldehyde based on the hydroxyl group of the polyvinyl alcohol resin.
5 equivalent% of the reaction occurred.

Note that the resin was insoluble in water. 12.5 g of this resin and 1.259 g of sodium 4,4'-diazidostilbene-2,27-disulfonate in 87.59 g of ethyl cellosolve.
was added and sufficiently stirred and mixed to obtain a photosensitive resin composition. A zinc relief plate was prepared using the composition in the same manner as in Example 1, but it could not be developed with water. When developed with a 3% octylphenol ethylene oxide aqueous solution, development was possible, but a clear image could not be obtained.

Claims (1)

[Scope of Claims] 1 A monovalent aldehyde containing one or more unsaturated groups in the molecule, A monovalent aldehyde containing 1 to 9 carbon atoms in the molecule and no unsaturated groups When B is a polymerization degree of 300 to 2000 and a saponification degree of 70 to 100
The polyvinyl alcohol resin and the aldehyde A and aldehyde B are mol%, and the acetalization by aldehyde A is 1 to 20 equivalent%, and the acetalization by aldehyde B is 1 to 30 equivalent%, based on the hydroxyl group of the resin.
A photosensitive resin composition mainly comprising a polyvinyl acetal resin obtained by carrying out an acetalization reaction in a range in which the total of acetalization with aldehyde A and acetalization with aldehyde B is 2 to 40 equivalent %. 2 Claim 1 in which A is crotonaldehyde
The photosensitive resin composition described in . 3. The photosensitive resin composition according to claim 1, wherein A is furfural. 4. The photosensitive resin composition according to claim 2 or 3, wherein B is acetaldehyde. 5. The photosensitive resin composition according to claim 2 or 3, wherein B is butyraldehyde. 6. The photosensitive resin composition according to claim 2 or 3, wherein B is propionaldehyde.