JPH10301295A - Adhesion preventing layer composition for photosensitive resin plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable development in a water-based treating liquid and to suppress small wrinkles due to moisture absorption during the plate making process by forming an adhesion preventing layer containing a polyvinylbutyral. SOLUTION: This compsn. for an adhesion preventing layer of a photosensitive resin plate which can be developed with a water-based treating liquid contains a polyvinylbutyral. The polyvinylbutyral is a butyral resin obtd. by the reaction of polyvinylalcohol and butyraldehyde. The resin is widely used in various fields such as coating materials, adhesives, processing of fiber products and binders and is available for various grades of polymn. degrees and viscosities. Since polyvinylbutyral is hardly soluble with water, it is dissolved in an alcohol or org. solvent to be used. A thin film can be easily obtd. by applying the soln. and drying. Surfactants and plasticizers can be mixed to the soln. to change the physical properties of the thin film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an anti-adhesion layer composition for a photosensitive resin plate, and a water-developable photosensitive resin plate using the anti-adhesion layer composition having excellent plate making performance and handling.

[0002]

2. Description of the Related Art A photosensitive resin plate referred to in the present invention is a photosensitive resin composition molded to a certain thickness and sandwiched between two layers of films. Is a letterpress printing plate. As a method for obtaining a relief (hereinafter, plate making), a negative film is closely adhered to the photosensitive resin composition, activated light is applied to selectively expose the negative film, and then the unexposed portion is removed to remove the relief. The method of forming is common.

[0003] The surface of a photosensitive resin composition is usually tacky in many cases. Due to this tackiness, air bubbles enter when a negative film is brought into close contact, and uniform contact cannot be achieved.
Image reproduction is poor. Also, when peeling, poor adhesion occurs due to adhesion, and both the plate and the negative film are damaged.

In order to solve this problem, the most commonly used method is to coat the surface of a photosensitive resin composition with a thin anti-adhesion layer. For example, JP-A-51-49803 discloses the method. (Polyvinyl alcohol having a saponification degree of 90% or more), JP-A-54-68224 (water-soluble polymer), JP-A-56-110914 (soluble polyamide) and the like are known. In the case of a photosensitive resin composition that can be developed with an aqueous processing solution, the anti-adhesion layer generally contains a water-soluble polymer such as polyvinyl alcohol and water-soluble cellulose in order to make the anti-adhesion layer also developable with an aqueous processing solution. Is used.

However, when these polymers are used, when the cover film (usually a PET film) for protecting the anti-adhesion layer is peeled off during the plate making operation, moisture absorption of the anti-adhesion layer occurs, and fine wrinkles (hereinafter referred to as hygroscopic wrinkles) are generated on the surface. Would. If the plate material having the fine wrinkles is exposed as it is, there is a problem that the fine wrinkles are reproduced as they are on the relief. The moisture-absorbing wrinkles generated at this time vary in size depending on the composition of the anti-adhesion layer, but are wrinkles having a height difference of about 3 to 20 μm.

In order to suppress such moisture wrinkles, it has been proposed to apply a mat treatment to the cover film to make the surface of the anti-adhesion layer in contact with the negative film into a mat. However, in this method, the process becomes longer due to the matte treatment of the film, and it is very difficult to control the surface roughness by the matte treatment. In addition, since the light is scattered in the matte treatment, the resolution of the image reproduction is reduced. Problems arise.

[0007]

DISCLOSURE OF THE INVENTION The present invention provides an anti-adhesion layer composition for a photosensitive resin plate and an anti-adhesion layer which can be developed with an aqueous processing solution and can suppress fine wrinkles due to moisture absorption during plate making. It is an object of the present invention to provide a water-developable photosensitive resin plate using the composition.

[0008]

The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, an anti-adhesion layer composition containing polyvinyl butyral (hereinafter referred to as PVB) as an essential component has been obtained. They have found that they can be adapted to the purpose, and have completed the present invention based on this finding. That is, the present invention provides an anti-adhesion layer composition for a photosensitive resin plate that can be developed with an aqueous processing solution, wherein the composition contains polyvinyl butyral (PVB). The present invention relates to an anti-adhesion layer composition for use.

Hereinafter, the present invention will be described in detail. Polyvinyl butyral used in the present invention is a butyral resin obtained by reacting polyvinyl alcohol and butyraldehyde, and is used in various fields such as various paints, adhesives, textile processing, and various binders. A wide range of grades such as viscosity is available. Further, they have found that polyvinyl butyral is hardly soluble in water but can be developed with water.

Since polyvinyl butyral hardly dissolves in water, it is used by dissolving it in alcohol or an organic solvent. A thin film can be easily obtained by coating this solution in the form of a coating and drying it. In order to change the physical properties of the thin film, a surfactant, a plasticizer, or the like can be mixed and used. The content of polyvinyl butyral is 10% or more, preferably 50% or more,
More preferably, it is desirable to contain 70% or more. If the content is less than 10%, it becomes difficult to form a film as an anti-adhesion layer. The thickness of the anti-adhesion layer is selected in the range of 0.1 to 20 μm, preferably 1 to 10 μm. If the thickness is less than 0.1 μm, it becomes difficult to prevent the tackiness of the photosensitive resin, and
When the value exceeds, the resolution of the relief is lowered without further improving the anti-adhesion effect.

The anti-adhesion layer composition of the present invention is used by incorporating it into a photosensitive resin plate. The photosensitive resin plate is generally a PET film (hereinafter referred to as a base film) as a support for maintaining dimensional stability. It has a structure in which an adhesive layer, a photosensitive resin composition layer, an anti-adhesion layer, and a PET film (hereinafter, cover film) are laminated. The anti-adhesion layer is usually formed on the back surface of the cover film, and is laminated by bringing this surface into close contact with the photosensitive resin layer. As the cover film, polyethylene, polypropylene, polystyrene and other materials can be used according to the purpose,
A polyethylene terephthalate film (PET film) is optimal in view of dimensional stability, heat resistance, and mechanical performance.

This cover film (usually 50 to 250 μm)
m thickness), and a solution of the anti-adhesion layer composition of the present invention is applied so that the thickness after drying is usually 1 to 10 μm, and dried. At this time, in order to improve the coatability with the cover film, various surfactants, an antifoaming agent, a leveling agent,
A penetrant or the like may be blended. The surface of the thin film thus formed on the cover film is brought into close contact with the surface of the photosensitive resin composition to obtain a photosensitive resin plate. As a method for obtaining a photosensitive resin plate, an adhesive layer, a photosensitive resin composition layer, an anti-adhesion layer, and a cover film can be laminated on a base film, and the anti-adhesion layer of the present invention is used for the photosensitive resin plate. can do.

A water-developable photosensitive resin plate is generally a photosensitive resin comprising a polymer, a plasticizer, a crosslinkable monomer photoinitiator, a stabilizer, and other additives such as a sensitizer, a surfactant, and a gelling agent. A photosensitive resin plate that contains a resin composition and can be developed with an aqueous processing solution. Specifically, as seen in Japanese Patent Application No. 8-333202, as a polymer, sulfonic acid group-containing polyurethane, styrene / isoprene block copolymer, monomer plasticizer, and other components such as polybutadiene diacrylate, aliphatic diacrylate, dioctyl fumarate, Photosensitivity including a photosensitive resin composition comprising maleated modified polybutadiene, N-ethyltoluenesulfonamide, 2,2-dimethoxyphenylacetophenone, 2,2-di-t-butyl-p-cresol, sodium laurylbenzenesulfonate Refers to resin plate and the like.

The aqueous treatment liquid referred to here is a solution containing water or, if necessary, a surfactant, an antifoaming agent, a dispersant, an emulsifier, a corrosion inhibitor, a decay inhibitor, a pH adjuster, and a water-soluble solvent. And a solution containing 50% or more of water.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The embodiments of the present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The evaluation of the photosensitive resin plate in the examples was performed as follows.

1) Hygroscopic wrinkle resistance A photosensitive resin plate cut into a size of 10 cm × 20 cm was placed at 50 ° C. × 1% or less of humidity for 24 hours. Then 20
After cooling at 2 ° C x 2 hours, the cover film was peeled off in a room at 20 ° C x 70% RH, and the occurrence of streaky wrinkles with a height difference of 5 µm or more due to moisture absorption on the surface of the anti-adhesion layer was checked for up to 1 minute. did. 200cm of streak-like wrinkles
^If less than 3 wires per ² were found, then ○ was given if 3 or more wires were found.

2) Developability As an aqueous processing solution, 2 parts of sodium borate, 2 parts of octylphenoxypolyoxyethylene ether, 100 parts of water
Were mixed and the developability was uniform at 40 ° C., and those that could be uniformly developed were rated as ○, and those with unevenness were rated as x. 3) Resolution When 150 Line / 3% highlight dots were formed on the negative film for the resolution test, those having a depth of a 500 μm wide white line of 100 μm or more were evaluated as ○, and those less than that were evaluated as ×. 4) Adhesion Adhesion between the negative film and the photosensitive resin plate was actually evaluated by plate making, and those which were uniformly adhered and which could be easily peeled off after the completion of exposure were evaluated as ○, and those which did not were evaluated as ×.

Reference Example 1 A photosensitive resin composition was prepared with reference to Example 1 of Japanese Patent Application No. 8-333202. (1) Synthesis of polyester diol containing sulfonic acid group 1,0 equipped with a stirrer, a nitrogen inlet and an outlet pipe.
In a 00 ml separable flask, 296 g of sodium sulfoisophthalate dimethyl ester, 310 g of ethylene glycol, N, N'-hexamethylenebis (3,5-
Di-t-butyl-4-hydrocinnamamide) [IRGA
NOX1098: Ciba-Geigy], 0.43 g and zinc acetate 0.43 g, and 200
After reacting at 5 ° C. for 5 hours, unreacted ethylene glycol was distilled off under reduced pressure to obtain a pale yellow sulfonic acid group-containing polyester diol having a hydroxyl group at a terminal. Its number average molecular weight was 492 as measured by hydroxyl value.

(2) Synthesis of Sulfonic Acid Group-Containing Polyurethane 3,0 equipped with a stirrer, a nitrogen inlet and an outlet pipe.
In a 00 ml separable flask, 39.9 g of the sulfonic acid group-containing polyester diol obtained in (1), polyisoprene diol having a hydroxyl group at both terminals having a number average molecular weight of 2,439 [manufactured by Idemitsu Petrochemical] 377.7 g, octylated diphenylamine [NOCRAC AD: Ouchi Shinko Chemical] After charging 1.4 g, dimethylacetamide 10
100 g and 1000 g of 2-chlorotoluene, and
A homogeneous solution was obtained at ℃. Next, 0.11 g of dibutyltin dilaurate and 0.34 g of stannaus octoate were added, and the mixture was further reacted at 110 ° C. for 3 hours while 43.1 g of xylylene diisocyanate was added dropwise. Then, dimethylacetamide and 2-chlorotoluene were added. Evaporation under reduced pressure gave a uniform and transparent sulfonic acid group-containing polyurethane.

(3) Preparation of Photosensitive Resin Composition Under a nitrogen atmosphere, 49.5 g of a sulfonic acid group-containing polyurethane was subjected to styrene / isoprene block copolymer [Califlix TR110] at 150 ° C. using a pressure kneader.
7: Shell Chemical Co.] 20 g {styrene / isoprene block copolymer / sulfonic acid group-containing polyurethane weight ratio (hereinafter abbreviated as (A) weight ratio) = 40.4 / 100}, sodium laurylbenzenesulfonate 2 g {(A) +
(B) Weight ratio = 2.9 / 100 °, polybutadiene diacrylate [BAC-45: manufactured by Osaka Organic Chemicals] 5 g, aliphatic diacrylate [C-2000: manufactured by Sartomer] 1
g, dioctyl fumarate 2 g} or more (A) + (B) weight ratio = 11.5 with respect to the total of ethylenically unsaturated compounds.
/ 100%, 2,2-dimethoxyphenylacetophenone 2 g {(A) + (B) weight ratio = 2.9 / 100}, maleated modified polybutadiene [ME-1000-80:
10 g of Nippon Petrochemical], 7.5 g of N-ethyltoluenesulfonamide, and 0.1 g of 2,2-di-t-butyl-p-cresol to obtain a homogeneous and transparent photosensitive resin composition.

[0021] The photosensitive resin composition is treated with P having an adhesive layer.
An ET film and a PET film coated with a silicon-based release agent were sandwiched and pressed to obtain a photosensitive resin plate having a constant thickness. In order to laminate the anti-adhesion layer, PET with a silicon-based release agent was peeled off.

[0022]

【Example】

Example 1 As a coating solution of the anti-adhesion layer composition, polyvinyl butyral (Esrec B BL- manufactured by Sekisui Chemical Co., Ltd.)
1) A solution composed of 8 parts, 2.4 parts of a silicon-based surfactant (FZ-2222 manufactured by Nippon Unicar Co., Ltd.) and 100 parts of isopropyl alcohol was prepared, and 100 μm in volume was prepared.
The solution was applied to a PET film of No. 2 such that the dried coating film had a thickness of 2 μm, and dried at 80 ° C. for 3 minutes to obtain an anti-adhesion layer. The film was placed on the surface of the photosensitive resin composition obtained in Reference Example 1 so that the anti-adhesion layer was in contact with the photosensitive resin layer.
It was adhered at 30 ° C. Table 1 shows the evaluation results of the photosensitive resin plate thus obtained. As can be seen from Table 1, it was confirmed that the anti-adhesion layer had no wrinkles due to moisture absorption, was developable with an aqueous processing solution, and had excellent resolution.

Example 2 Polyvinyl butyral (Esrec B BL-, manufactured by Sekisui Chemical Co., Ltd.) was used as a coating solution for the anti-adhesion layer composition.
1) 8 parts, 0.08 part of sodium laurylbenzenesulfonate (LS-250, manufactured by Lion Corporation),
Prepare a solution consisting of 100 parts of ethyl alcohol,
The solution was applied to a 00 μm PET film so that the dried coating film became 2 μm, and dried at 80 ° C. for 3 minutes to obtain an anti-adhesion layer. The film was adhered to the surface of the photosensitive resin composition obtained in Reference Example 1 at 130 ° C. so that the anti-adhesion layer was in contact with the photosensitive resin layer. Table 1 shows the evaluation results of the photosensitive resin plate thus obtained. As can be seen from Table 1, it was confirmed that the anti-adhesion layer had no wrinkles due to moisture absorption, was developable with an aqueous processing solution, and had excellent resolution.

Example 3 Polyvinyl butyral (Eslec B BL- manufactured by Sekisui Chemical Co., Ltd.) was used as a coating solution for the anti-adhesion layer composition.
3) A solution consisting of 8 parts of a silicone surfactant (3.2 parts of FZ-2222 manufactured by Nippon Unicar Co., Ltd. and 100 parts of isopropyl alcohol) was prepared, and the dried coating film was formed on a 100 μm PET film so that the dry coating film became 2 μm. The solution was applied and dried at 80 ° C. for 3 minutes to obtain an anti-adhesion layer.
The film was placed on the surface of the photosensitive resin composition obtained in Reference Example 1 so that the anti-adhesion layer was in contact with the photosensitive resin layer.
It adhered at ° C. Table 1 shows the evaluation results of the photosensitive resin plate thus obtained. As can be seen from Table 1, it was confirmed that the anti-adhesion layer had no wrinkles due to moisture absorption, was developable with an aqueous processing solution, and had excellent resolution.

Comparative Example 1 Polyvinyl alcohol (AH-17 manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) was used as a coating solution for the anti-adhesion layer composition.
A solution composed of 6.4 parts, a silicon-based surfactant (KF-351 manufactured by Shin-Etsu Chemical Co., Ltd.), 1.6 parts, water 70 parts, isopropyl alcohol 30 parts was prepared, and 100 parts were prepared.
The solution was applied to a μm PET film so that the dry coating film became 2 μm, and dried at 80 ° C. for 3 minutes to obtain an anti-adhesion layer. The film was adhered to the surface of the photosensitive resin composition obtained in Reference Example 1 at 130 ° C. so that the anti-adhesion layer was in contact with the photosensitive resin layer. Table 1 shows the evaluation results of the photosensitive resin plate thus obtained. As can be seen from Table 1, generation of fine wrinkles due to moisture absorption was observed.

Comparative Example 2 Hydroxypropyl methylcellulose acetate succinate (AS-LG manufactured by Shin-Etsu Chemical Co., Ltd.) 8 parts as a coating solution of the anti-adhesion layer composition, PEG / PPG
Surfactant (Epan 41 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
0) 3.2 parts, water 20 parts ethyl alcohol 80
Of a 100 μm PET film, and apply the solution so that the dry coating film becomes 2 μm.
It dried at 3 degreeC for 3 minutes, and obtained the anti-adhesion layer. The film was adhered to the surface of the photosensitive resin composition obtained in Reference Example 1 at 130 ° C. so that the anti-adhesion layer was in contact with the photosensitive resin layer. Table 1 shows the evaluation results of the photosensitive resin plate thus obtained. As can be seen from Table 1, generation of fine wrinkles due to moisture absorption was observed.

Comparative Example 3 Polyvinyl alcohol (KH-17 manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) was used as a coating solution for the anti-adhesion layer composition.
A solution consisting of 4.8 parts, a silicone-based surfactant (KF-351 manufactured by Shin-Etsu Chemical Co., Ltd.), 3.2 parts, water 70 parts, isopropyl alcohol 30 parts was prepared, and 100 parts were prepared.
The solution was applied on a PET film (manufactured by Somar Co., Ltd.) having a matting treatment of μm so that the dried coating film became 2 μm, and dried at 80 ° C. for 3 minutes to obtain an anti-adhesion layer. The film was adhered to the surface of the photosensitive resin composition obtained in Reference Example 1 at 130 ° C. so that the anti-adhesion layer was in contact with the photosensitive resin layer. Table 1 shows the evaluation results of the photosensitive resin plate thus obtained. As can be seen from Table 1,
The generation of fine wrinkles due to moisture absorption was suppressed, but the resolution was reduced.

Comparative Example 4 As a coating solution of the anti-adhesion layer composition, 12.6 parts of polyamide (macromelt 6900, manufactured by Henkel Co.), hydrogenated styrene butadiene styrene copolymer (Tuftec 1913, manufactured by Asahi Kasei Corporation) 1 .4 parts, silicon surfactant (KF-35 manufactured by Shin-Etsu Chemical Co., Ltd.)
1) Prepare a solution consisting of 0.3 part, 43 parts of toluene and 43 parts of isopropyl alcohol, and prepare a 100 μm P
The solution was applied to an ET film so that the dry coating film became 4 μm, and dried at 80 ° C. for 5 minutes to obtain an anti-adhesion layer. The film was placed on the surface of the photosensitive resin composition obtained in Reference Example 1 at 130 ° C. so that the anti-adhesion layer was in contact with the photosensitive resin layer.
At close contact. When the photosensitive resin plate thus obtained was developed with an aqueous processing solution, the film remained uneven and as shown in Table 1, it was confirmed that the developability with the aqueous processing solution was poor.

Comparative Example 5 Polyvinyl butyral (Esrec B BL- manufactured by Sekisui Chemical Co., Ltd.) was used as a coating solution for the anti-adhesion layer composition.
1) A solution composed of 8 parts, 2.4 parts of a silicon-based surfactant (FZ-2222 manufactured by Nippon Unicar Co., Ltd.) and 100 parts of isopropyl alcohol was prepared, and 100 μm in volume was prepared.
The solution was applied to a PET film of No. 2 such that the dry coating film thickness was 0.08 μm, and dried at 80 ° C. for 3 minutes to obtain an anti-adhesion layer. The film was adhered to the surface of the photosensitive resin composition obtained in Reference Example 1 at 130 ° C. so that the anti-adhesion layer was in contact with the photosensitive resin layer. Table 1 shows the evaluation results of the photosensitive resin plate thus obtained. As can be seen from Table 1, it was confirmed that the adhesion of the negative film was poor.

[0030]

[Table 1]

[0031]

The anti-adhesion layer composition of the present invention can be developed with an aqueous processing solution and can suppress fine wrinkles due to moisture absorption during plate-making, and have a high resolution. Can be provided.

Claims (2)

[Claims] 1. A water-developable photosensitive resin plate, wherein the anti-adhesion layer of the photosensitive resin plate contains polyvinyl butyral. 2. An anti-adhesion layer composition for a photosensitive resin plate capable of being water-developed, wherein the composition contains polyvinyl butyral.