JPH0654380B2 - Photosensitive resin plate - Google Patents

Description

TECHNICAL FIELD The present invention relates to a photosensitive resin plate used for forming a plate surface for letterpress printing. More specifically, the present invention relates to a method for suppressing the tackiness of the surface of the photosensitive layer of a photosensitive resin plate. Therefore, according to the present invention, various troubles caused by the tackiness of the surface of the photosensitive layer can be prevented.

Conventional technology Conventional photosensitive resin plates often cause tackiness on the surface of the photosensitive layer, which hinders uniform adhesion between the original film and the photosensitive resin plate, or the original film is exposed after exposure to the photosensitive layer. It was unavoidable that the surface of the photosensitive layer was transferred to the original film when the film was peeled off from the film and the film was damaged.

As a method for solving such a problem, for example, a method of directly matting the surface of the photosensitive layer (Japanese Patent Laid-Open No. 48-45304), a method of providing a polyvinyl alcohol coating on the surface of the photosensitive layer to prevent sticking (Japanese Patent Laid-Open No. No. 58-18633), a resin film for adhesion prevention is provided on the surface of a photosensitive layer provided on a support, and an adhesive layer having an adhesive force smaller than the adhesive force between the resin film and the photosensitive layer is provided thereon. A method of providing and further coating a film on the adhesive layer (JP-A-61-1)
No. 7148) is proposed.

Problems to be Solved by the Invention However, in the method of directly matting the surface of the photosensitive layer, when the photosensitive layer itself has strong adhesiveness, the adhesiveness to the original film cannot be sufficiently enhanced. Further, in the method of providing the polyvinyl alcohol film, even if the adhesion with the original film is improved, the film and the polyvinyl alcohol film are directly coated and press-bonded to the photosensitive layer. It has the drawback of low adhesion to the coating and peeling of the film during handling.

On the other hand, according to the method of providing an adhesive layer between the anti-adhesion layer such as a polyvinyl alcohol coating film and the cover film, the above-mentioned drawbacks can be solved, but when the cover film is peeled off, the adhesive layer forms with the cover film. There is a drawback that it is not peeled off and remains partially on the surface of the anti-adhesion layer.

The inventors of the present invention have solved such a problem that the surface of the photosensitive layer is not tacky, and the cover film does not peel off during handling, or the adhesive layer does not partially remain on the tackiness preventive layer. As a result of intensive studies to provide a photosensitive resin plate, the present invention has been achieved.

Means for Solving the Problems To outline the present invention, the present inventors provide an anti-adhesion layer on the surface of a photosensitive layer provided on a support, and sequentially coat an adhesive layer and a matte layer on the anti-adhesion layer. In the photosensitive resin plate comprising, by providing a difference in the adhesive force between the photosensitive layer and the anti-adhesive layer and the adhesive force between the anti-adhesive layer and the adhesive layer,
The inventors have found that the above objects can be achieved and completed the present invention.

That is, the present invention provides a photosensitive resin plate in which the surface of a photosensitive layer provided on a support is sequentially coated with an anti-adhesion layer, an adhesive layer and a matte layer, and the adhesion between the photosensitive layer and the anti-adhesion layer is obtained. The force is greater than the adhesive force between the anti-adhesion layer and the adhesive layer, the base material of the mat layer is made of a synthetic resin film, and a matting agent is dispersed on the adhesive layer side of the mat layer. Is provided, and a curing agent is contained in the coating agent, which provides a photosensitive resin plate.

The components of the present invention will be described in detail below.

(Support) The support used in the photosensitive resin plate of the present invention includes, for example, polyester, polyamide, polystyrene and other resin films used in conventional photosensitive resin plates, steel,
For example, there is a plate made of aluminum or the like provided with an antihalation layer.

(Photosensitive Layer) The photosensitive layer in the photosensitive resin plate of the present invention contains a main resin, a monomer having at least one photopolymerizable alkenyl group, and a photopolymerization initiator as main components, and if necessary, A composition to which a thermal polymerization inhibitor, a coloring agent such as a dye or a pigment, and a plasticizer is added is used.

Examples of the main resin include partially saponified vinyl acetate resin and its derivatives, cellulosic resin, polyvinylpyrrolidone, acrylic resin, polyester resin, alkyd resin, polyethylene oxide, water-soluble polyamide having a sulfonate group or a basic group. , Maleic acid copolymers, alcohol-soluble polyamides, copolymers of styrene and butadiene, copolymers of styrene and isoprene, and the like. These may be used alone or in combination of two or more. It may be used.

(Adhesion prevention resin) As the resin used for forming the adhesion prevention resin film,
For example, polyamide, polyacrylamide, cellulose,
Examples thereof include those mainly containing polyvinyl alcohol, and those in which two or more kinds of these resins are mixed.

These anti-adhesion resins need to be selected so that the coating and the photosensitive layer are soluble in the same developer. However, when the resin used for forming the anti-adhesion resin coating is the same as the main resin in the photosensitive layer, the components of the photosensitive layer may be mixed with the resin of the anti-adhesion resin coating over a long period of time. However, the effect of the resin film for adhesion prevention is reduced. Therefore, in order to solve such a problem, it is desirable to use a resin that is slightly more soluble than the photosensitive layer in forming the tackiness preventive resin film. For example, when both the anti-adhesion resin coating and the photosensitive layer are mainly made of polyvinyl alcohol, it is preferable to use polyvinyl alcohol having a larger average molecular weight than the photosensitive layer for the anti-adhesion resin coating. Such solubility adjustment can also be performed by utilizing the difference in saponification degree of polyvinyl alcohol. For example, when the saponification degree of polyvinyl alcohol is 80%, the solubility in water becomes the highest. Therefore, when polyvinyl alcohol having a saponification degree of 80% is used for the photosensitive layer, the saponification degree of polyvinyl alcohol forming the anti-adhesion resin film is Should be 90%.

The dry film thickness of the resin film for adhesion prevention is 0.1 μm to 20
It is used in the range of μm, preferably 0.5 μm to 4 μm. The dry film thickness of the resin film for anti-adhesion is 0.
If it is less than 1 μm, the anti-adhesion effect is lost. On the other hand, if it exceeds 20 μm, light scattering occurs in the tackiness-preventing resin film during exposure through a negative film, resulting in poor image reproducibility.

(Adhesive Layer) The adhesive layer in the present invention is a resin having a reactive group that chemically causes a bond at the interface with the mat film described later, or contains a reactive compound capable of chemically bonding. Must be what you are doing.

As a material satisfying the above requirements, for example, at least one polymer substance selected from polyester resin, polyurethane resin, epoxy resin, synthetic rubber, acrylic resin, ethylene-vinyl acetate resin, etc. is mainly used. What is used as an ingredient is used.

It is also necessary that the adhesive force between the adhesive layer and the tack-preventing resin coating is smaller than the adhesive force between the tack-preventing resin coating and the photosensitive layer.

The thickness of the adhesive layer is preferably in the range of 0.01 μm to 20 μm. More preferably, it is in the range of 0.5 μm to 2 μm. If the film thickness of the adhesive layer is less than 0.01 μm, sufficient adhesion strength between the anti-adhesion resin coating and the surface of the matte film cannot be obtained, and the matte film may not be formed during storage or handling of the photosensitive resin plate. It peels off. On the other hand, when the thickness of the adhesive layer exceeds 20 μm, the matte surface of the matte film is covered, and the shape of the matte surface is not transferred to the resin film for tackiness prevention. It takes an unreasonably long time to bring the resin film into close contact with the resin film, and it is not preferable because baking occurs.

(Mat film) Examples of the material of the mat film used in the present invention include polyester, polyamide, polystyrene, polypropylene, polycarbonate, polysulfone, polyvinyl chloride, polyvinylidene chloride, polyacrylate and polymethacrylate, but are not limited thereto. However, the polymer may contain additives such as a plasticizer.

Examples of the matting method for the film surface include a chemical polishing method in which the surface of the film is treated with an alkali or an acid to corrode the surface, a sandblast method in which fine particles are sprayed on the surface of the film to form pores in the surface, and fine particles are included. There are a liquid honing method in which deionized water is sprayed on the film surface to form pores in the film surface, and a coating method in which a resin containing fine particles is coated on the film surface. Among these methods, the coating method is preferably used from the viewpoint that it is relatively easy to make the surface roughness constant.

The coating method is usually performed as follows. That is, a polyester, an acrylic resin, a resin such as urethane resin and a curing agent such as an isocyanate compound are dissolved in an organic solvent to prepare a coating agent by dispersing a matting agent, and the coating agent is then applied to the film. A matte film is obtained by coating, drying, and heat treatment called aging treatment to cure.

As the matting agent, inorganic powders such as silicon dioxide, graphite and alumina, and solid powders of organic materials such as polyimide, polyamide, epoxy resin and cellulose can be used.

However, in the present invention, an isocyanate compound or the like as a curing agent is also used as a reactive species for producing a chemical bond by an adhesive layer and a urethane bond, so that the aging treatment must be performed after the adhesive layer is applied. I won't.

In the present invention, the surface roughness of the matte film is Ra = 0.01 μ according to Japanese Industrial Standard (JIS) B0601.
m to 5 μm, and R _max = 0.04 μm
It is preferably in the range of 20 to 20 μm. Particularly preferred is Ra = 0.2 μm to 0.8 μm and R _max = 1.0 μm to 3 μm. Since the adhesive layer is chemically bonded at the interface between the mat film and the mat film thus obtained, the adhesive layer can be peeled integrally with the mat film. If they are not chemically bonded, the adhesive layer partially remains on the surface of the anti-adhesion resin coating layer when the matte film is peeled off, which causes blurring of printing and poor development.

The matte film is peeled off from the photosensitive resin plate prior to the exposure process, but at this time, since the tack-preventing resin film is more firmly adhered to the photosensitive layer than the adhesive layer, the matte film is easily adhered together with the adhesive layer. It is peeled off from the surface of the prevention layer. At this time, Ra is less than 0.01 μm and R
_{If the max} is less than 0.04 μm, the effect of transferring the surface shape of the matte film to the tackiness preventive resin coating is poor, and the vacuum adhesion to the negative film becomes poor. Also Ra
Of more than 5 μm and R _max of more than 20 μm, the incident light is diffusely reflected at the time of exposure due to the depth of the surface shape of the matte film on the matt surface transferred to the anti-adhesion resin film, resulting in image reproducibility. Becomes worse.

(Production Method) Next, a preferred example of the method for producing the photosensitive resin plate of the present invention will be described.

First, a coating agent is uniformly applied on a material film that will be a matte film, and dried. The coating agent comprises a resin such as the above polyester, a powder such as silicon dioxide, a curing agent such as an isocyanate compound having a reactive species for chemically bonding with the adhesive layer, and a solvent.

Next, what melt | dissolved the said resin for adhesive layer formation in the volatile solvent is apply | coated to the matt side of the said mat film, and it dries, and an adhesive layer is formed. Then, it is left at room temperature or in a heated state. At this time, a reaction proceeds between the curing agent such as the isocyanate compound and the adhesive layer-forming resin, and a strong chemical bond is generated at the contact surface between the coating layer and the adhesive layer of the matte film, resulting in the matte film and the adhesive layer. And will adhere firmly. Next, a resin for forming an anti-adhesion resin film, for example, a composition comprising polyvinyl alcohol having an appropriate degree of saponification and polymerization and methanol-water is applied onto the adhesive layer to prevent the adhesion. A resin coating is formed to form a three-layer film.

On the other hand, a photosensitive layer is formed on the surface of the support by using the above-mentioned photosensitive layer forming composition, and a film composed of the three layers obtained as described above is formed on the photosensitive layer together with an anti-adhesive resin film and a photosensitive layer. The layers are pressed so that they face each other to obtain a photosensitive resin plate.

The method for producing the photosensitive resin plate of the present invention is not limited to the above method, and a method of sequentially laminating a photosensitive layer, an anti-adhesive resin coating, an adhesive layer and a matte film on a support can also be used.

EXAMPLES Next, the present invention will be described in more detail by way of examples.

Example 1 100 parts by weight of a saturated polyester resin having a degree of polymerization of about 20,000 was dissolved in 3,800 parts by weight of cyclohexanone, and 10 g of silicon dioxide powder having an average particle diameter of 5 μm was dispersed therein to obtain Coronate L (Nippon Polyurethane Company). 2 parts by weight of isocyanate compound) was added to obtain a coating agent for forming a matting layer.

Further, 100 parts by weight of a saturated polyester resin having a degree of polymerization of about 20,000 was dissolved in 3,800 parts by weight of cyclohexanone to obtain a composition for forming an adhesive layer.

On the other hand, partially saponified polyvinyl acetate having a degree of saponification of 90 mol% and a degree of polymerization of 1,000 is dissolved in a mixed solvent of water / methanol = 90/10 (weight / weight) to prepare a 3% by weight solution, and adhesiveness is obtained. It was used as a composition for forming a resin coating for prevention.

The coating agent for forming a matting layer was applied to a polyester film (125 μm thick) so that the dry film thickness was 4 μm, and 100% for volatilizing cyclohexanone.
Dry at 5 ° C for 5 minutes. The surface roughness thus obtained is Ra
= 0.5 μm and R _max = 2 μm. Immediately after the above coating agent is dried, the above composition for forming an adhesive layer is applied so that the dry film thickness becomes 1 μm, and the composition is dried at 100 ° C.
Dry for 0 minutes. The film thus obtained was heat-treated at 60 ° C. for 4 days to sufficiently cure the matting layer and the chemical reaction at the interface between the matting layer and the adhesive layer.
Next, a composition for forming a resin film for preventing tackiness was applied onto the adhesive layer so that the dry film thickness was 2 μm, and the composition was dried at 120 ° C. for 3 minutes.
After drying for 0 seconds, a laminate composed of a matte film, an adhesive layer and an anti-tack resin coating was prepared.

On the other hand, as a photosensitive resin composition, partially saponified polyvinyl acetate having a degree of saponification of 80 mol% and a degree of polymerization of 500 100 parts by weight Photosensitive reaction product 100 parts by weight Ethylene glycol 10 parts by weight Benzoin isopropyl ether 4 parts by weight Methylhydroquinone 0 0.05 part by weight 200 parts by weight of water was kept in a flask at 90 ° C. and stirred, and the dissolved solution was cast on a steel plate provided with an antihalation layer.
It was dried at ℃ for 15 hours to form a photosensitive layer having a thickness of 0.7 mm.

The photosensitive reaction product is described in JP-B-54-3790.
It was manufactured according to the method disclosed in Example 2 of the publication.

That is, 0.02 parts of methylhydroquinone in 10 parts by weight of water
Dissolve 5 parts by weight, and add 74 parts by weight of dimethylol urea dimethyl ether and 20 parts of N-methylol acrylamide to the solution.
2 parts by weight and 2 parts by weight of ammonium chloride were added, and the mixture was heated to 80 ° C. and stirred for 2 hours. The reaction mixture was then poured into 1,000 parts by weight of acetone and the precipitate was filtered off.

Next, the filtrate was distilled to remove acetone to obtain a viscous photosensitive reaction product. This product is soluble in water, alcohol and acetone and its infrared absorption spectrum is 800 cm.
^It showed strong absorption at ^-1 .

The surface of the photosensitive layer thus formed has strong adhesiveness, and has poor vacuum adhesion to a negative film. Onto the surface of the photosensitive layer, the laminate composed of the three layers prepared above was thermocompression bonded at 80 ° C. so that the resin film for preventing adhesion was in contact with the surface of the photosensitive layer.

The photosensitive resin plate thus obtained was allowed to stand for 1 week and then cut into A-3 size, but no peeling of the mat film around it was observed. When this film was peeled off, an adhesive layer was attached to the entire surface on the film side.
On the other hand, the tack-preventing resin coating was adhered to the surface of the photosensitive layer, and the mat-shape on the mat film transferred during thermocompression bonding was formed on the tack-preventing resin coating surface.

Further, when the matte film was peeled off, the film was peeled off while being stopped at intervals of several cm. However, the adhesive layer adhered to the entire surface of the film, and the adhesive layer did not remain on the surface of the tack-preventing resin film.

A negative film was placed on this sample, and the sample was exposed to a chemical lamp after vacuum adhesion. Then, using a spray-type washing machine, development was carried out for 2 minutes with tap water having a spray pressure of 2.7 kg / cm ² and a liquid temperature of 45 ° C., followed by drying and observing the post-exposed plate, there was no burning blur at all. , Showed that the vacuum adhesion was good. In addition, the resin film for anti-adhesion did not remain on the plate surface, the white void depth was sufficient, and the reproducibility was good. Furthermore, good printed matter was obtained from the start of printing even after a printing test.

Comparative Example 1 In the same manner as in Example 1, a matting layer forming coating agent, an adhesive layer forming composition, and a tack preventive resin film forming composition were prepared. Polyester film (125 μm
The coating material for forming a matting layer was applied onto the above layer and dried, and then the matting layer was sufficiently cured by aging treatment at 60 ° C. for 4 days. At this time, the isocyanate compound contained in the matting layer was almost consumed for curing the matting layer. Next, in the same manner as in Example 1, the composition for forming an adhesive layer and the composition for forming a resin film for preventing tackiness were sequentially applied and dried to prepare a laminate comprising a mat film, an adhesive layer and a resin film for preventing tackiness. .

The above laminate was thermocompression bonded at 80 ° C. to the surface of the photosensitive layer obtained in the same manner as in Example 1. After left for one week, it was cut into A-3 size, but there was no peeling around. Next, when the film was peeled off, the film was peeled off while being held at intervals of several cm, and the adhesive layer portion where the film was stopped remained linearly on the surface of the anti-adhesion layer. The film was exposed and developed as it was, but the portion where the adhesive layer portion remained on the surface of the tackiness preventive layer was not eluted with the developing solution.

Example 2 100 parts by weight of an acrylic resin having 60 parts by weight of methyl methacrylate and 40 parts by weight of hydroxyethyl methacrylate and having a molecular weight of about 40,000 was dissolved in 100 parts by weight of methyl ethyl ketone and 5 parts by weight of aluminum isopropylate, and an average particle size was obtained. 10 parts by weight of silicon dioxide having a diameter of 5 μm was uniformly dispersed to obtain a coating agent for forming a matting layer.

Further, 100 parts by weight of ethylene vinyl acetate resin was dissolved in 1,000 parts by weight of ethyl acetate to obtain a composition for forming an adhesive layer.

On the other hand, 3 parts by weight of partially saponified polyvinyl alcohol having a degree of saponification of 99 mol% and a degree of polymerization of 500 is dissolved in a mixed solvent of water / methanol = 60/37 (parts by weight / weight part) to form a resin film for adhesion prevention. A composition for use.

A polyester film (100 μm) was prepared in the same manner as in Example 1.
m thickness) was coated with the coating agent for forming a matting layer so that the dry film thickness was 5 μm, and dried at 100 ° C. for 2 minutes. Next, the composition for forming an adhesive layer was applied thereon to give a dry film thickness of 0.7 μm, dried at 100 ° C. for 2 minutes, and left at 60 ° C. for 10 days. Then, the composition for forming an anti-adhesion resin film was applied so as to have a dry film thickness of 2 μm, and dried at 120 ° C. for 30 seconds to prepare a laminate composed of a mat film, an adhesive layer and an anti-adhesion resin film.

A small amount of water was applied to the surface of the photosensitive layer formed in the same manner as in Example 1, and then the above-prepared laminate was pressure-bonded so that the resin film for adhesion prevention was in contact with the surface of the photosensitive layer.

The photosensitive resin plate thus obtained was allowed to stand for 1 week and then cut into A-3 size, but no peeling of the mat film around it was observed. When this film was peeled off, an adhesive layer was attached to the entire surface on the film side.
On the other hand, the anti-adhesion resin coating adhered to the entire surface of the photosensitive layer and had a matte film-like surface.

A negative film was overlaid on this sample, exposed after vacuum adhesion, developed, dried, and post-exposed, showing good vacuum adhesion during vacuum adhesion, and the obtained image shows reproducibility,
The depth was good.

Example 3 Using the coating agent for forming a matting layer and the composition for forming an adhesive layer used in Example 1, as a composition for forming a resin film for preventing tackiness, a methyl cellulose resin containing about 30% methoxy groups, Metroze SM15. (Shin-Etsu Chemical Co., Ltd.) 5 parts by weight dissolved in 95 parts by weight of water,
A laminated body was prepared in the same manner as in Example 1.

On the other hand, a partially saponified polyvinyl acetate having a degree of saponification of 80 mol% and a degree of polymerization of 580 as a photosensitive resin composition.
100 parts by weight Polyglycerin # 500 (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., having a hydroxyl group of 960 and a viscosity of 175,000 cP (30 ° C.)) is mixed with 36 g of acrylic acid, 1 g of phosphoric anhydride and 20 mg of methylhydroquinone. After stirring at 60 ° C. for 4 hours while heating, unreacted acrylic acid was distilled off under reduced pressure, the resulting reaction mixture was dissolved in 45 g of water, neutralized with ammonia, and filtered to obtain a photosensitive material. 100 parts by weight Benzoin isopropyl ester 4 parts by weight Methylhydroquinone 0.05 parts by weight Water 200 parts by weight is cast on a steel plate provided with an antihalation layer and dried at 40 ° C. for 15 hours to form a film. A photosensitive layer having a thickness of 0.4 mm was formed.

This surface has strong tackiness and poor vacuum adhesion to a negative film.

On this photosensitive layer surface, the laminate prepared above is pressure-bonded so that the adhesive-preventing resin coating is in contact with the photosensitive layer surface,
When left for one week, the same results as in Example 1 were obtained.

Example 4 As a photosensitive resin composition, 100 parts by weight of copolyamide 100 parts by weight of methylenebisacrylamide 10 parts by weight of benzophenone 2 parts by weight of hydroquinone 0.01 parts by weight of methanol 100 parts by weight of water A solution of 20 parts by weight of water was prepared to prevent halation. Cast on a layered steel plate to a film thickness of 0.6 mm,
It dried at 15 degreeC for 15 hours, and formed the photosensitive layer.

The copolymerized polyamide was produced according to the method disclosed in the example of JP-B-54-41203.

That is, 60% by weight of ε-caprolactam, 18% by weight of hexamethylene diammonium adipate and 22% by weight of a salt of 5- (sodium sulfo) isophthalic acid and hexamethylenediamine were charged in an autoclave and charged with nitrogen gas. After substituting, polymerization was carried out at a temperature of 240 to 250 ° C. under a pressure condition of heating for 1 hour, pressure (30 kg / cm ² ) for 4 hours, depressurization for 30 minutes, and atmospheric pressure for 5 hours to obtain a copolyamide.

When a polyester film having an adhesive layer and a resin film for preventing tackiness was pressure-bonded to the photosensitive layer in the same manner as in Example 1 and left for 1 week, the same result as in Example 1 was obtained.

EFFECT OF THE INVENTION The photosensitive resin plate of the present invention is a photosensitive resin plate in which the surface of a photosensitive layer provided on a support is sequentially coated with an anti-adhesion layer, an adhesive layer and a matte layer. The adhesive strength with the anti-adhesion layer is larger than the adhesive strength between the anti-adhesion layer and the adhesive layer, the base material of the mat layer is made of a synthetic resin film, and the mat layer is matted on the adhesive layer side. Since the photosensitive resin plate is characterized in that a coating agent in which the agent is dispersed is applied and a curing agent is contained in the coating agent, it is possible to prevent peeling of the surroundings and the entire surface during handling or cutting, and a mat Even when the film is peeled off, the adhesive layer does not remain on the tack-preventing resin film, so that an excellent printed matter can be obtained.

 ─────────────────────────────────────────────────── ─── Continuation of front page (56) Reference JP 61-17148 (JP, A) JP 60-39635 (JP, A) JP 57-208556 (JP, A)

Claims (1)

[Claims] 1. A photosensitive resin plate comprising a surface of a photosensitive layer provided on a support, which is successively coated with an anti-adhesion layer, an adhesive layer and a matte layer, and the adhesion between the photosensitive layer and the anti-adhesion layer. The force is greater than the adhesive force between the anti-adhesion layer and the adhesive layer,
The base material of the mat layer is made of a synthetic resin film, and a coating agent in which a matting agent is dispersed is applied to the adhesive layer side of the mat layer, and a curing agent is contained in the coating agent. And a photosensitive resin plate.