JP2559711B2 - Non-silver image forming material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a non-silver salt image-forming material, and more specifically to a non-silver used for a photoengraving process, which has improved scratch resistance and scratch resistance. The present invention relates to a salt reversal material contact reversal lith film.

[Conventional technology and problems] Conventionally, a contact reversal lith film made of a silver halide photosensitive material has been used in the photomechanical process, but demands for avoiding restrictions on silver resources, simple development processing, cost reduction, etc. Various non-silver salt photosensitive material adhesion reversal lith films have been proposed in accordance with the above.

For example, JP-A-52-62427 discloses an image forming material comprising a transparent support and a photopolymerizable layer having an optical density of at least 3.0 and a protective layer, which is transparent by contact exposure and development treatment. It has been proposed to obtain a relief type reversal image having an optical density of at least 3.0 on a film support.

Further, an image forming material in which the above-mentioned photopolymerizable layer having an optical density of at least 3.0 is separately layered in two layers of a mask layer and a photopolymer layer is also proposed. For example,
JP-A-52-89916 discloses a mask layer in which carbon black is dispersed in a film-forming and solvent-soluble polymer substance on a transparent film support, and an image-forming material provided with a photopolymer layer on the mask layer. Is disclosed, after contact exposure,
A method has been proposed for obtaining a relief-type reverse image composed of a photopolymer layer and a mask layer on a transparent film support by leaving exposed areas in a development or development / etching process and eluting unexposed areas. There is.

As described above, it is said that the image forming material and the image forming method of the above two examples can be used as the contact reversal lith film in the photomechanical process. However, when the relief image-forming non-silver salt adhesion reversal film as described above is treated in the same manner as the conventionally used silver salt adhesion reversal lith film in the process of photolithography, the relief image-forming non-silver salt adhesion reversal film is treated. The contact reversal lith film has the drawbacks that it is inferior in scratch resistance and scratch resistance to the silver salt contact reversal film and is likely to cause partial loss of images such as line breaks and dot skips.

[Object of the Invention] The present invention has been made in order to eliminate the drawbacks of the conventional non-silver salt adhesion reversal lith film, and has scratch resistance,
An object of the present invention is to provide a non-silver salt image forming material having excellent scratch resistance.

[Summary of the Invention] In order to achieve such an object, the non-silver salt image-forming material of the present invention has a mask layer on a support, and a photopolymerizable photopolymer layer and an overcoat layer on the mask layer. In the image-forming material having, the photopolymerizable photopolymer layer comprises at least a developer-soluble or swellable polymer binder, a photopolymerizable monomer, a photopolymerization initiator and polyethylene fine particles, and the polyethylene fine particles have an average molecular weight of 1000 to 6000. Is a low molecular weight polyethylene having an average particle diameter of 0.1μ to 10μ, and the content of polyethylene fine particles is 0.3% by weight or more and less than 30% by weight based on the total amount of the polymer binder and the photopolymerizable monomer. It is a thing.

Further, in the non-silver salt image forming material of the present invention, the mask layer is
The photopolymerizable photopolymer layer comprises a black pigment layer dispersed in a polymer binder that is soluble or swellable in a developing solution or a mask layer etching solution.

 Hereinafter, the present invention will be specifically described.

The support used in the image-forming material of the present invention is a transparent film support having excellent dimensional stability, examples of which include polyethylene terephthalate film, triacetate film, polycarbonate film, polyvinyl chloride film, polystyrene film, polypropylene film. , Plastic film such as polysulfone film can be mentioned, especially thickness 50μ to 200
A polyethylene terephthalate film of μ is particularly preferred. These plastic films may be provided with an undercoat layer or may be subjected to a discharge treatment, if necessary, in order to improve adhesion with a mask layer described later.

Further, the present inventors disclosed in JP-A-61-141438, the total light transmittance is 60% or more in the wavelength range of at least 330 nm to 600 nm, and the central average line roughness is 0.10.
A chemical matte film having a thickness of μ or more and less than 0.60 μ may be used as the support.

(1) Mask Layer The mask layer has a coating film thickness of usually 0.5 to 20 μ, preferably 1 to 10 μ, and more preferably to prevent side etching of the mask layer which causes thinning of image lines in the reversing operation. It is required to be as thin as possible, and it is 1 to 5 μ if the image density for printing required for the reversing operation, for example, the near ultraviolet ray density and the ortho density is at least 2.5 or more. The mask layer is a dispersion of a black pigment in a solution of a film-forming binder soluble in water or an organic solvent, using a suitable dispersing means, for example, a ball mill, a sand grinder, an attritor, a roll mill, or a high-speed impeller disperser. It is provided by coating and drying on the transparent film.

Examples of black pigments that can be used for this mask layer include carbon black, carbon graphite, phthalocyanine pigments, graphite powder, blackened silver powder, nickel powder, iron oxide powder, titanium black, etc. Carbon black having a high covering power is particularly preferable.

The content of the black pigment in the mask layer is 10 to 500% by weight, preferably 60 to 3% by weight based on the film-forming polymer described below.
It is 00% by weight, and as described above, a sufficient amount of black pigment is contained in the film-forming polymer as far as the film performance is not deteriorated so as to obtain a sufficient print image density and form a mask layer as thin as possible. desirable.

Examples of the film-forming polymer that can be used for this mask layer include the following which can be dissolved or swelled by the photopolymer layer developing solution or the mask layer etching solution depending on the composition of the photopolymer layer developing solution and the mask layer etching solution. Polymer compounds selected from the polymer compounds of each group may be mentioned, and these may be used alone or in admixture of two or more.

(A) Water-soluble resin Gelatin, sodium alginate, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, vinyl methyl ether-maleic anhydride copolymer,
Polyethylene oxide, sodium polyacrylate, partially saponified polyacrylic acid ester, polyacrylamide,
Acrylamide-diacetone acrylamide copolymer and the like.

(B) ... Alkali-soluble resin Acrylic acid-methacrylic acid ester copolymer, 2-hydroxyethyl methacrylate-acrylonitrile-methyl methacrylate-methacrylic acid copolymer, styrene-maleic anhydride copolymer partial esterified product, polyvinyl −
P-hydroxybenzal, novolac type phenolic resin, etc.

(C) ... Acid-soluble resin such as dimethylaminoethyl methacrylate-methyl methacrylate copolymer.

(2) Photopolymerization-type photopolymer layer The photopolymerization-type photopolymer layer comprises at least a developer-soluble or swellable polymer binder, a photopolymerizable monomer, a photopolymerization initiator and polyethylene fine particles.
Dissolve the mask layer, or a coating solution using water or an organic solvent that does not significantly swell, is provided by coating and drying on the mask layer, by exposure to ultraviolet light, visible light, etc.,
The solubility, swelling property, etc. of a basic substance, an acidic substance, a neutral salt, a developing solution consisting of an aqueous solution of a mixture of two or more selected from lower alcohols compatible with water are changed, If only a portion can remain on the mask layer, and the remaining portion has a property of being insoluble in an etching solution composed of an aqueous solution of a single material selected from the same material group as described above or a mixture of two or more layers. Good.

The preferred thickness of the photopolymerizable photopolymer layer is 0.5 to 10
μ, and more preferably, the sensitivity (50%) that enables reversal printing efficiently with reversal printers that are widely used in photoengraving processes.
0 mJ / cm ² or less, 1～5Myu preferably so as to obtain a resist performance in development, etching treatment with 100 mJ / cm ² or less)
Is.

The composition of the photopolymerizable photopolymer layer is 10 to 80% by weight of a developer-soluble or swellable polymer binder, 10 to 40% by weight of a photopolymerizable monomer, 1 to 20% by weight of a photopolymerization initiator, and polyethylene fine particles. 0 to the total amount of the developer soluble or swellable binder and photopolymerizable monomer.
3 to 30% by weight and 10% by weight or less of other additives such as a sensitizer and a thermal polymerization inhibitor. The developer-soluble or swellable polymer binder may be polyvinyl alcohol, polyacrylic acid, acrylamide-diacetone acrylamide copolymer, etc. when the developer is water alone, and when the developer is an alkaline aqueous solution, Acrylic acid-methacrylic acid ester copolymer, styrene-
A maleic anhydride copolymer partially esterified product, a novolac type phenol resin, etc. can be used. In addition, the developer
In the case of using an acidic aqueous solution, a dimethylaminoethyl methacrylate-methyl methacrylate copolymer or the like can be used.

Further, the photopolymerizable monomer is an addition-polymerizable unsaturated monomer having an acryloyl group, and specifically, it is a polyfunctional acrylate, for example, 1,6-hexanediol diacrylate, polyethylene glycol 200 diacrylate, diethylene glycol diacrylate. Acrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, hydroxypivalate neopentyl glycol diacrylate, bis (acryloxyethoxy) bisphenol A, bis (acryloxypolyethoxy) bisphenol A, trimethylolpropane triacrylate, penta Erythritol triacrylate, dipentaerythritol hexaacrylate, etc. are desirable, and phenoxyethyl acrylate, stearyl acryl Over door, lauryl acrylate,
Methoxyethyl acrylate, N, N-dimethylaminoethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-methoxyethoxyethyl acrylate, 2-ethoxyethoxyethyl acrylate, 2-hydroxyethyl acryloyl phosphate, tetrahydrofurfree It is also possible to use a monofunctional acrylate such as acrylate in combination with the polyfunctional acrylate.

Photopolymerization initiators include acetophenone, P-dimethylacetophenone, benzophenone, P, P-dichlorobenzophenone, Michler's ketone (4-4'-bisdimethylaminobenzophenone), benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether. , Benzoin n-propyl ether, benzoin isobutyl ether, benzoin n-butyl ether, 2-chlorothioxanthone, 2-
Methylthioxanthone, azobisisobutylnitrile,
Benzoin peroxide, 2,4,5-triphenylimidazole dimer and the like can be used.

Polyethylene fine particles are low molecular weight polyethylene having an average molecular weight of 1000 to 6000, a softening point of 90 to 130 ° C, and a density of 0.92 to 0.99 g / ml, and are oxidized and acid modified for easy dispersion in the photopolymerizable photopolymer layer. May be done.

The low molecular weight polyethylene is dispersed in an organic solvent such as toluene to have an average particle size of 0.1 to 10 μm and added to the photopolymerization type photopolymer layer coating solution. The addition amount is preferably 0.3% by weight or more and less than 30% by weight with respect to the total amount of the polymer binder and the photopolymerizable monomer in the photopolymerization type photopolymer layer, and if less than 0.3% by weight, scratch resistance and scratch resistance. No substantial effect is obtained with respect to the property, and if it is 30% by weight or more, the scratch resistance and the scratch resistance are good, but the image performance of the photopolymerizable photopolymer layer is remarkably deteriorated.

(3) Overcoat layer An overcoat layer is provided on the photopolymerizable photopolymer layer. The overcoat layer is a layer that imparts functions such as blocking prevention, blocking of the sensitivity of the photopolymerizable photopolymer layer from the air during exposure while suppressing exposure, surface slipperiness of the exposed surface, and vacuum suction adhesion baking property, A film-forming polymer soluble in water alone or in a photopolymerizable photopolymer layer developer and fine particles imparting a matte property in a range in which active light transmittance is not excessively lowered.

Examples of the film-forming polymer that can be used in the overcoat layer include the various film-forming polymers described in the mask layer, and polyvinyl alcohol soluble in tap water at room temperature is most suitable. Further, as the fine particles, inorganic extender pigments such as calcium carbonate, barium sulfate and silicon dioxide, or polymer fine particles such as acrylic resin, epoxy resin, nylon resin, polyethylene resin and fluororesin can be used.

A desirable film thickness is 0.1 to 10 μm so as to impart the above-mentioned function and not reduce the image forming property of the photopolymerization type photopolymer layer.
And more preferably 0.3 to 3 μ.

[Examples] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Example 1 Mask Layer Coating Liquid Composition Methacrylic acid-methacrylic acid ester copolymer (comprising 30 mol% methyl metal acrylate, 40 mol% 2-hydroxyethyl methacrylate, 27 mol% methacrylonitrile, 3 mol% methacrylic acid) Copolymer) 5 g Carbon black (MA-100 manufactured by Mitsubishi Kasei) 5 g Methyl cellosolve 90 g Silicone-based surfactant (FS-XB manufactured by Dow Corning)
-2725) 0.2 g To the above composition, 100 g of glass beads was added, and the mixture was shaken and dispersed for 6 hours with a paint shaker to obtain a mask layer coating solution.
This coating solution is applied on a corona discharge treated 100 μm thick polyethylene terephthalate film support using a wire bar and dried with warm air at 90 ° C. for 1 minute and 30 seconds to form a mask with a coating film thickness of about 1.5 μm. The layer was formed on a transparent film.

On the other hand, polyethylene fine particle dispersion liquid composition Polyethylene fine particles (Dainichi Seika Color and Chemical's Daiethylene PE-11) 10 g Toluene 90 g To the above composition, 100 g of glass beads were added, and the mixture was shaken and dispersed for 2 hours with a paint shaker and then cooled to room temperature. A polyethylene fine particle dispersion was obtained.

The following composition added to the photopolymerization type photopolymer layer coating solution was coated on the above mask layer using a wire bar and dried with warm air at 90 ° C. for 1 minute to give a coating film thickness of about 1.5 μm. A photopolymerizable photopolymer layer was formed on the mask layer.

Photopolymerization system Photopolymer layer coating solution composition Acrylic acid / methacrylic acid ester copolymer solution (NK-3, manufactured by Kyodo Chemical Co., Ltd.) 20 g Trimethylolpropane triacrylate 6 g Benzophenone 0.8 g Michler's ketone 0.4 g P-methoxyphenol 0.02 g Polyethylene fine particle dispersion liquid 8 g Toluene 70 g Butyl acetate 50 g Then, an overcoat coating liquid comprising the following composition is coated on the photopolymerization type photopolymer layer, and heated at 90 ° C. for 1 hour.
It was dried for a minute to form an overcoat layer having a coating film thickness of about 0.5μ.

Overcoat layer coating liquid composition Polyvinyl alcohol (Nippon Gosei Kagaku Kogyo, Gohsenol NK-20) 3 g Silicon dioxide fine particles (Fuji Davison Kagaku, Cyloid 978) 0.1 g Distilled water 90 g Isopropyl alcohol 6 g A forming material was obtained.

Example 2 Mitsui Petrochemical Industrial Mitsui High Wax 4052E was used as the polyethylene fine particles in the composition of the photopolymerizable photopolymer layer coating solution of Example 1. An image forming material of Example 2 was obtained in the same manner as in Example 1 except for the above.

Comparative Example 1 An image forming material of Comparative Example was obtained in exactly the same manner as in Example 1 except that the polyethylene fine particle dispersion was omitted from the composition of the photopolymerizable photopolymer layer coating solution of Example 1.

150 lines / inch halftone dot area ratio is 3% of 80%, 50% and 20%
The image forming materials obtained in Examples 1 and 2 of the present invention and Comparative Example 1 were subjected to reversal exposure with an exposure amount of 100 mJ / cm ² using a high pressure mercury lamp contact printer using an original made of a kind of flat mesh. next,
Anhydrous sodium carbonate 0.01% aqueous solution was heated to 30 ℃ to make a developing solution, soaked in this developing solution for 30 seconds, and then developed by rubbing with absorbent cotton while washing with running tap water, and wiping off water droplets. It was dried with warm air at ℃ for 10 minutes.

Using the surface texture measuring machine (Shinto Scientific HEIDON-14 type), the reverse mesh images obtained in Examples 1 and 2 and Comparative Example were obtained as described above.
Strength measurement A vertical load is applied, and a scratch resistance is obtained by performing a scratch test at a scratch speed of 200 mm / min with a scratch needle made of sapphire and having a diameter of 0.1 mm.
The scratch resistance was measured.

As shown in the table below, the measurement results (strength) show that the strength is significantly improved in Examples 1 and 2 in which the polyethylene particles are contained in the photopolymerizable photopolymer layer, as compared with Comparative Example 1.

[Effects of the Invention] As is clear from the above examples, according to the non-silver salt image-forming material of the present invention, the scratch resistance and the scratch resistance are remarkably improved, and line-forming is performed in various steps of photoengraving. It was possible to provide a relief image-forming non-silver salt adhesion reversal film that does not cause partial loss of images such as breaks and skips.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshimichi Katsuoka 1115-2, Suzutani, Yono City, Kimoto Saitama Factory (72) Inventor Yasunori Sugiyama 1115-2, Suzuya, Yono City, Kimoto, Saitama Factory (56) References JP-A-61-141438 (JP, A) JP-A-57-115548 (JP, A) JP-A-58-174939 (JP, A)

Claims (2)

(57) [Claims] 1. An image forming material having a mask layer on a support, and a photopolymerizable photopolymer layer and an overcoat layer on the mask layer, wherein the photopolymerizable photopolymer layer is at least a developing solution. It consists of a soluble or swellable polymer binder, a photopolymerizable monomer, a photopolymerization initiator and polyethylene fine particles, wherein the polyethylene fine particles are low molecular weight polyethylene having an average molecular weight of 1000 to 6000 and an average particle diameter of 0.1 μ to 10 μ. The content of the polyethylene fine particles is 0.3% by weight or more and less than 30% by weight with respect to the total amount of the polymer binder and the photopolymerizable monomer. 2. The mask layer comprises a black pigment layer dispersed in a polymer binder that is soluble or swellable in a photopolymerizable photopolymer layer developing solution or a mask layer etching solution. The non-silver salt image-forming material according to item 1 above.