JPH10177251A - Image forming material and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the color reproducibility of an image forming material having a photosensitive resin layer and a protective layer on a base, to prevent the deterioration of image reproducibility by gaseous N2 bubbles at the time of exposure and to improve the preservability of this material. SOLUTION: The gas permeability (JIS (Japanese Industrial Standards) K 7126) of the protective layer to the coating solvent vapor of the photosensitive layer of the image forming material formed by coating the surface of the base with a coloring agentcontg. photosensitive layer and the protective layer in this order is >=500cc/m<2> 24hratm. The protective layer of the image forming material formed by providing the surface of the base having a cushion property with the photosensitive layer contg. the coloring agents and an o-quinonediazide compd. and the protective layer in this order contains inorg. amorphous particles and org. spherical particles having the gaseous N2 permeability (JIS K 7126) of >=500cc/m<2> 24hratm and an average grain size larger than the film thickness at a weight ratio of 4:6 to 6:4.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image-forming material comprising a support, on which a photosensitive resin layer such as photo-modified, photo-polymerizable, photo-crosslinkable, etc., and a protective layer are coated. Relates to an improvement of the protective layer.

[0002]

2. Description of the Related Art Conventionally, an image forming material used in the fields of printing, photography and the like basically comprises a support and a photosensitive resin layer provided thereon.

For example, a transfer-type image forming material for color proofing having such a configuration is exposed through a separation netting film for each color plate and developed to form a separation image. A multicolor transfer image is formed by repeating transfer to an image receiving material.

In the image forming material for such uses, a cushion layer may be provided between the support and the photosensitive resin layer in order to transfer the image onto the rough paper satisfactorily (Japanese Patent Laid-Open No. 4-19905).
No. 6, etc.), and if necessary, a protective layer is provided on the photosensitive resin layer.

[0005] The production of this type of image forming material is as follows.
After coating and drying the coating solution for the photosensitive resin layer on a long support, if a protective layer is provided, the coating solution for the protective layer is once wound up and then coated with the photosensitive resin layer. Coated on top, dried and wound up.

In such an image forming material, in order to prevent adhesion between the front surface and the back surface of the image forming material and to prevent reticulation of the front surface which occurs with the elapse of time after production,
A technique is known in which hydrophobic silica particles are contained in the uppermost layer on the photosensitive resin layer side (JP-A-62-63930). Japanese Patent Application Laid-Open No. 7-89254 discloses that, in a transfer type image forming material having a cushion layer, a colored photosensitive layer and a protective layer on a support, solid particles contained in the protective layer to prevent blocking (adhesion). There is disclosed a technique for improving image defects caused by reducing the size of the solid particles to an average particle size of 10 μm or less.

However, although the image forming material according to the above technique was effective in preventing reticulation and blocking, it was found that there were the following problems. In other words, the residual solvent in the photosensitive resin layer makes its performance unstable, and for example, in applications such as color proofing, when the plasticizer in the photosensitive resin layer changes, the permeability of the developer changes, resulting in color reproduction. Tend to be unstable,
Further, when the photosensitive resin layer contains a component that generates N ₂ gas upon exposure to an o-quinonediazide compound or the like, there is a problem that the reproducibility of a halftone image is degraded due to bubbles of the N ₂ gas generated during image exposure.

[0008]

SUMMARY OF THE INVENTION The object of the present invention is as follows.
In order to improve the instability of performance caused by the coating solvent of the layer remaining in the photosensitive layer after the production of the image forming material, thereby improving color reproducibility when used for color proofing,
Second, it is necessary to reduce deterioration of dot image reproducibility due to bubbles of N ₂ gas during imagewise exposure of the image forming material.
Another object of the present invention is to provide an image forming material having improved dot image reproducibility and image forming material storage stability, and an image forming method using the same.

[0009]

The present invention that achieves the above object is the following (1) to (3).

(1) An image forming material comprising a support, on which a photosensitive layer containing a colorant and a protective layer are sequentially coated,
The gas permeability (JIS K7126) of the protective layer with respect to the coating solvent vapor used for coating the photosensitive layer is 500 cc /.
image forming material characterized by m is ² · ^24hratm more.

(2) An image-forming material comprising a support having a cushioning property and a photosensitive layer containing a colorant and an o-quinonediazide compound and a protective layer sequentially provided on the support.
An image forming material, wherein the protective layer satisfies the following conditions (a) and (b).

(A) Nitrogen gas gas permeability (JIS K7)
126) is 500 cc / m ² · 24 hrm or more.

(B) It contains inorganic amorphous particles having an average particle size larger than the thickness of the protective layer and organic spherical particles having an average particle size larger than the thickness of the protective layer.
The weight ratio is from 0:60 to 60:40.

(3) An image forming material obtained by sequentially coating a photosensitive layer containing a colorant and a protective layer on a support is imagewise exposed at least imagewise and developed using a developer to form an image. An image forming method, wherein the image forming material is the image forming material according to (1) or (2).

Hereinafter, the present invention will be described in detail.

In the invention according to claims 1 to 3, various photosensitive compounds or compositions can be used for the photosensitive layer containing a colorant (hereinafter referred to as "colored photosensitive layer"). When exposed to actinic rays, the molecular structure changes chemically within a short time, the solubility in the solvent changes, and when a certain solvent is applied, the exposed or unexposed portion may All compounds such as monomers, prepolymers or polymers that can be dissolved and removed are included. Examples of usable photosensitive compounds or compositions include those having a reduced solubility in the exposed area, a so-called negative type, and a photo-crosslinking type photosensitive represented by esterified polyvinyl alcohol with cinnamic acid. Aqueous resin systems; systems in which a diazonium salt or a condensate thereof is condensed with polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, or the like; systems in which an aromatic azide compound is used as a photocrosslinking agent and bonded to a binder such as solidified rubber;
Further, a photosensitive resin utilizing photoradical polymerization or photoion polymerization can also be used. In addition, as a so-called positive type in which the solubility of the exposed portion is increased, for example, a photosensitive resin composition using an o-quinonediazide compound as a photosensitive substance is exemplified.

In the invention according to claims 1 to 3, as the photosensitive composition used in the colored photosensitive layer, a known positive photosensitive composition and a known negative photosensitive composition can be used. It is preferable to use a photosensitive composition containing an o-quinonediazide compound as the photosensitive composition. Any o-quinonediazide compound can be used as long as it can function as a photosensitive agent.

Specifically, for example, 1,2-benzoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-
Naphthoquinonediazide-5-sulfonyl chloride,
A compound obtained by condensing 1,2-naphthoquinonediazide-6-sulfonyl chloride with a compound containing a hydroxyl group and / or an amino group is preferably used.

Examples of the hydroxyl group-containing compound include trihydroxybenzophenone, dihydroxyanthraquinone, bisphenol A, phenol novolak resin, resorcinbenzaldehyde condensation resin, pyrogallol acetone condensation resin and the like. Examples of the amino group-containing compound include aniline, p-aminodiphenylamine, p-aminobenzophenone, 4,4'-diaminodiphenylamine, and 4,4'-diaminobenzophenone.

With respect to o-quinonediazide compounds, including those described herein, see also J. Org. Koser (J. Kos)
ar), "Light Sensitive System" (Light
tSensitive System) (John Wiley and Sons, New York City, 1965), and Nagamatsu, Inui co-authored "Photosensitive Polymers" (Kodansha, 1
977) can be used.

In the invention according to claims 1 to 3, the colored photosensitive layer can contain a known polymer compound and a synthetic resin, and particularly contains a carboxylic acid vinyl ester monomer unit represented by the following general formula. It is preferable to contain a high molecular compound contained in the structure.

[0022]

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However, R represents an alkyl group and includes an alkyl group having a substituent.

Any polymer compound having the structure described above can be used arbitrarily. Examples of the carboxylic acid vinyl ester monomer for constituting the monomer unit represented by the above general formula include the following. Are preferred. The name and chemical formula are shown together.

1 Vinyl acetate CH ₃ COOCH ＝ CH ₂ 2 Vinyl propionate CH ₃ CH ₂ COOCH ＝ CH ₂ 3 Vinyl butyrate CH ₃ (CH ₂ ) ₂ COOCH ＝ CH ₂ 4 Vinyl pivalate (CH ₃ ) ₃ CCOOCH ＝ CH ₂ 5 vinyl caproate _{CH 3 (CH 2) 4 COOCH} = CH 2 6 caprylic vinyl _{CH 3 (CH 2) 6 COOCH} = CH 2 7 capric acid vinyl _{CH 3 (CH 2) 8 COOCH} = CH 2 8 vinyl laurate CH ₃ (CH ₂ ) ₁₀ COOCH = CH ₂ 9 Vinyl myristate CH ₃ (CH ₂ ) ₁₂ COOCH = CH ₂ 10 Vinyl palmitate CH ₃ (CH ₂ ) ₁₄ COOCH = CH ₂ 11 Vinyl stearate CH ₃ (CH ₂ ) ₁₆ COOCH = CH ₂ 12 vinyl versatate

[0026]

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[0027] (in R ^1, R ² is an alkyl group, the sum of the number of carbon atoms is 7. That is, the form of the _{^{R 1 + R 2 = C 7}} H 16) the polymer compound, the carboxylic acid vinyl ester It may be a polymer obtained by polymerizing one kind, a polymer obtained by copolymerizing two or more kinds of vinyl carboxylate, or an arbitrary component ratio of the vinyl carboxylate and another monomer copolymerizable therewith. May be a copolymer.

The monomer units which can be used in combination with the monomer units represented by the above general formula include, for example, ethylenically unsaturated olefins such as ethylene, propylene, isobutylene, butadiene and isoprene, for example, styrene, α -Methylstyrene, p-methylstyrene, p
Styrenes such as chlorostyrene, for example acrylic acid,
Acrylic acids such as methacrylic acid, for example, unsaturated aliphatic dicarboxylic acids such as itaconic acid, maleic acid and maleic anhydride, for example, diethyl maleate, dibutyl maleate, di-2-ethylhexyl maleate, dibutyl fumarate, dibutyl fumarate Diesters of unsaturated dicarboxylic acids such as -2-ethylhexyl, for example, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethacrylic acid Α-methylene aliphatic monocarboxylic acid esters such as ethyl, for example, acrylonitrile, nitriles such as methacrylonitrile, for example, amides such as acrylamide, for example, acrylanilide, p-chloroacrylanilide, m-nitroacrylanilide, Anilides such as m-methoxyacrylanilide, for example, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, vinyl ethers such as β-chloroethyl vinyl ether, vinyl chloride, vinylidene chloride, vinylidene cyanide, for example, 1-methyl-1-methoxyethylene, 1,1-dimethoxyethylene, 1,2-dimethoxyethylene, 1,1
Ethylene derivatives such as -dimethoxycarbonylethylene and 1-methyl-1-nitroethylene, for example, N-vinyl such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidene and N-vinylpyrrolidone And monomer units generated from vinyl monomers such as compounds.

Particularly preferred as the above-mentioned polymer compound is a compound having a vinyl acetate monomer unit in the molecular structure. Among them, the vinyl acetate monomer unit is 40-95.
% By weight, having a number average molecular weight (Mn) of 1,000 to
80,000, weight average molecular weight (Mw) 500-
200,000 is preferred. More preferably, a polymer compound having a vinyl acetate monomer unit (especially 40 to 95% by weight) and a carboxylic acid vinyl ester monomer unit having a longer chain than vinyl acetate is preferable, and a number average molecular weight (Mn ) Are preferred, and those having a weight average molecular weight (Mw) of 10,000 to 150,000 are preferred.

In this case, the monomer constituting the polymer compound having a vinyl acetate monomer unit by copolymerizing with vinyl acetate is arbitrary as long as it can form a copolymer. It can be arbitrarily selected from monomers.

The copolymers that can be used as the above-mentioned polymer compound are listed below by showing their monomer components. However, as a matter of course, the present invention is not limited to the following example.

1 vinyl acetate-ethylene 2 vinyl acetate-styrene 3 vinyl acetate-crotonic acid 4 vinyl acetate-maleic acid 5 vinyl acetate-2-ethylhexyl acrylate 6 vinyl acetate-di-2-ethylhexyl maleate 7 vinyl acetate-methyl vinyl ether Reference Signs List 8 vinyl acetate-vinyl chloride 9 vinyl acetate-N-vinylpyrrolidone 10 vinyl acetate-vinyl propionate 11 vinyl acetate-vinyl pivalate 12 vinyl acetate-vinyl versatate 13 vinyl acetate-vinyl laurate 14 vinyl acetate-vinyl stearate 15 Vinyl acetate-vinyl versatate-ethylene 16 Vinyl acetate-vinyl versatate-2-ethylhexyl acrylate 17 Vinyl acetate-vinyl versatate-vinyl laurate 18 Vinyl acetate-bar Vinyl tickate-crotonic acid 19 Vinyl propionate-vinyl versatate 20 Vinyl propionate-vinyl versatate-crotonic acid 21 Pivalic acid-vinyl stearate-maleic acid Dyes and / or pigments as coloring agents contained in the colored photosensitive layer Is mentioned. In particular, when the image forming material according to the first or second aspect of the present invention is used for color proofing, a pigment and / or dye having a color tone consistent with the required ordinary colors, ie, yellow, magenta, cyan and black, is used. It is necessary,
In addition, metal powders, white pigments, fluorescent pigments and the like can be used. When the image forming material according to the first or second aspect of the present invention is applied to a color proof, many pigments and dyes known in this technical field as described below can be used.

(CI stands for color index).

Victoria Pure Blue (CI 425)
95) Auramine (CI 41000) Katilon Brilliant Flavin (CI Basic 1)
3) Rhodamine 6GCP (CI 45160) Rhodamine B (CI 45170) Safranin OK70: 100 (CI 50240) Erioglaucine X (CI 42080) Fast Black HB (CI 26150) No. 1201 Lionol Yellow (CI 2109
0) Lionol Yellow GRO (CI 21090) Shimla First Yellow 8GF (CI 2110
5) Benzidine Yellow 4T-564D (CI 2109)
5) Shimla Fast Red 4015 (CI 1235)
5) Lionol Red 7B4401 (CI 15830) Fastgen Blue TGR-L (CI 7416)
0) Lionol Blue SM (CI 26150) Mitsubishi Carbon Black MA-100 Mitsubishi Carbon Black # 30, # 40, # 50 In the invention according to claim 1 or 2, except for the colorant / colorant in the colored photosensitive layer. The ratio of the components can be determined by a method known to those skilled in the art in consideration of the target optical density and the removability of the colored photosensitive layer from the developer. The amount of the coloring agent is not particularly limited. For example, in the case of a dye, the content is preferably 5 to 75% by weight, and in the case of a pigment, the content is preferably 5 to 90% by weight.

The thickness of the colored photosensitive layer is not particularly limited, and may be a method known to those skilled in the art depending on the target optical density, the type of coloring agent (dye, pigment, carbon black) used in the colored photosensitive layer and its content. The thickness is preferably 0.1 to 5 g / m ² .

In the colored photosensitive layer, if necessary, a plasticizer, a coating improver and the like can be further added. Examples of the plasticizer include various low molecular compounds such as phthalates, triphenyl phosphates and maleates, and examples of the coating improver include surfactants such as a fluorine-based surfactant and ethyl cellulose polyalkylene ether. Nonionic activators and the like.

In the first or second aspect of the present invention, the colored photosensitive layer may be divided into two layers, a colored layer composed of a coloring agent and a binder, and a photosensitive layer composed of a photosensitive composition. In this case, either layer may be arranged on the support side.

In the invention according to claim 1 or 2, the support is optional, but a transparent support is preferably used in an image forming material exposed through the support. As the transparent support, a polyester film, particularly a biaxially stretched polyethylene terephthalate film, is preferable in terms of dimensional stability against water and heat. In addition, acetate film, polyvinyl chloride film, polyethylene film,
A polypropylene film, a polyethylene film or the like can be used.

In the invention according to claim 1 or 2, the support of the image forming material may have a cushioning property if necessary. When the image-forming material is applied to a transfer-type image-forming material, for example, after imagewise exposure and development, an image is formed, and only the image portion is transferred from the image obtained on the support to the transfer material. Transferred and laminated on top, that is,
In the case where only the colored image layer that substantially forms an image is transferred and laminated, the surface of the support is used in order to efficiently transfer the image onto the surface to be transferred and to easily peel off the support after the image transfer. The upper portion may have a cushioning property, or a layer having a cushioning property may be provided on the support. In this specification,
These layers having cushioning properties are called cushion layers,
A support having a cushion layer is referred to as a support having cushioning properties.

The thickness of the cushion layer is preferably 5 to 50.
It is in the range of μm. The resin used for the cushion layer preferably has a softening point of -30C to 150C.
The softening point temperature mentioned here is a VICAT softening point or a value indicated by a ring and ball method. Specific examples of the resin used for the cushion layer include the following as preferable resins.

Polyolefins such as polyethylene and polypropylene, ethylene and vinyl acetate, ethylene and acrylate, ethylene and acrylic copolymers such as acrylic acid, polyvinyl chloride, vinyl chloride copolymers such as vinyl chloride and vinyl acetate, Vinylidene chloride, vinylidene chloride copolymer, polystyrene, styrene copolymer such as styrene and maleic anhydride, polyacrylate, polyester resin, polyurethane resin, acrylate copolymer such as acrylate and vinyl acetate, poly Methacrylate, methacrylate and vinyl acetate, methacrylate copolymer such as methyl methacrylate and acrylic acid, polyvinyl acetate, vinyl acetate copolymer, vinyl butyral resin, nylon, copolymerized nylon N- alkoxymethyl nylon such as polyamide resin, synthetic rubber, petroleum resin, chlorinated rubber, polyethylene glycol, polyvinyl alcohol hydrogel Gin phthalate, cellulose derivatives, cellulose acetate phthalate, cellulose acetate succinate, shellac, waxes, ionomer resins.

Of these, an ethylene-vinyl acetate copolymer is particularly preferred. As the ethylene-vinyl acetate copolymer, the ratio of vinyl acetate in the copolymer is 5 to 5.
It is preferably in the range of 33% by weight, and the copolymer preferably has a VICAT softening point of 80 ° C or lower. Also, in the layer of ethylene-vinyl acetate copolymer,
As long as the softening point does not substantially exceed 80 ° C., various polymers, supercooled substances, surfactants, release agents and the like can be added.

The method of providing a layer of an ethylene-vinyl acetate copolymer on a support is as follows: 1) A solution obtained by dissolving an ethylene-vinyl acetate copolymer in an organic solvent such as toluene is coated on the support. And drying to provide a layer of an ethylene-vinyl acetate copolymer.

2) A solution obtained by dissolving polyvinyl acetate, polyvinyl chloride, epoxy resin, polyurethane resin, natural rubber, synthetic rubber or the like in an organic solvent was used as an adhesive, and these adhesives were applied on a support. Thereafter, after drying by hot air or heating, the ethylene-vinyl acetate copolymer film is laminated and pressed under heat and laminated,
So-called dry lamination method.

3) A mixture of ethylene and vinyl acetate, a copolymer of ethylene and acrylate, a polyamide resin, a petroleum resin, a rosin, and a wax is used as an adhesive, and the adhesive is heated as it is to keep it in a molten state. While applying on the support by a doctor blade method, a roll coating method, a gravure method, a reverse roll method, etc., immediately adhere an ethylene-vinyl acetate copolymer film and heat to a high temperature if necessary. So-called hot-melt lamination method in which lamination is performed by cooling from

4) A so-called extrusion lamination method in which the ethylene-vinyl acetate copolymer is kept in a molten state, extruded into a film by an extruder, and while the molten state is in a molten state, the support is pressed and laminated.

5) When a film to be a support is formed by a melt extrusion method, a plurality of extruders are used together with a molten ethylene-vinyl acetate copolymer by a single molding using a plurality of extruders.
A so-called co-extrusion method in which an ethylene-vinyl acetate copolymer resin layer is formed on a support film. And the like.

The protective layer according to the first aspect of the present invention has a gas permeability (JIS K7126) to the coating solvent vapor used for coating the colored photosensitive layer of 500 cc / m ² · 24 hr.
atm or more. The protective layer having gas permeability described above is preferably a layer containing a cellulose derivative as a binder and containing a plasticizer and solid particles, that is, a uniform or non-uniform layer in a continuous phase of a cellulose derivative containing a plasticizer. It can be obtained by a layer having a discontinuous phase of mixed solid particles.

Examples of the cellulose derivative include ethyl cellulose, butyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, hydroxypropylmethyl cellulose, methyl cellulose, hydroxypropyl cellulose and the like.

As the plasticizer, a plasticizer which is easily compatible with the binder used for the protective layer is used.
Examples include polyethylene glycols, polyhydric alcohols such as glycerin, and derivatives thereof.

The solid particles include polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-propylene
Vinyl acetate copolymer, polyethylene terephthalate, cross-linked vinyl polymer, silicon dioxide (eg, colloidal silica), diatomaceous earth, zinc oxide, titanium oxide, zirconium oxide, glass, alumina, dextrin, starch (eg, rice starch), stear Calcium phosphate, zinc stearate, polysaccharide fatty acid ester, polyvinyl acetate, polyvinylidene chloride, polyethylene oxide, polyethylene glycol, polyacrylic acid, polymethyl methacrylate, polyacrylamide, polyacrylic acid alkyl ester, polystyrene and polystyrene derivatives, and polystyrene derivatives thereof Particles formed of copolymers using unified monomers, polyvinyl methyl ether, epoxy resin, fusible phenol resin, polyamide, polyvinyl butyral, etc. And the like. These particles may be used alone or in combination of two or more.

The shape of the solid particles is arbitrary, but preferably has an average particle size larger than the thickness of the protective layer. In the present specification, the film thickness of the protective layer is a dry film thickness of a portion where no solid particles affecting the shape of the protective layer are present, and the average particle size of the solid particles is a weight average particle size measured by a light scattering method. It is.

In the invention according to claim 1, when the cellulose derivative is used as a continuous phase, the thickness of the protective layer is preferably 0.001 to 5 μm, particularly preferably 0.01 to 3 μm.
m, and the weight of the solid particles is preferably 0.001 to
2 g / m ^2, particularly preferably 0.01~1.5g / m ^2, the amount of plasticizer is preferably less than 0.5 wt% with respect to the resin binder of the protective layer. The amount of plasticizer is 0.
When the content is 5 wt% or more, gas permeability is improved, but blocking is likely to occur.

In the protective layer according to the first aspect of the present invention, the binder used in the continuous phase is not limited to a cellulose derivative. As such a binder, for example, a polymer having good scratch resistance can be used. As the high-molecular polymer, those which substantially provide a light-transmitting coating layer to actinic rays are preferable, and for example, resins used for various film bases such as polyethylene terephthalate and polypropylene are also used. Alternatively, those which dissolve in the developer used are preferred. Further, it is desirable to use a high molecular weight polymer which does not cause cracks or the like during the drying process or handling after the formation of the coating layer, has excellent adhesion, and has appropriate softness and toughness.

Specific examples of such a high-molecular polymer include homopolymers of polyvinyl alcohol, vinyl ether, acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester and the like, copolymers containing these, and soluble polyamides. be able to.
Other examples include polyvinyl acetate, methyl vinyl ether, maleic anhydride copolymer, polyvinylpyrrolidone, gelatin, gum arabic, polyethylene oxide, and water-soluble polyester. , The thickness is preferably 0.1 mm.
001 to 5 μm, particularly preferably 0.01 to 3 μm.

In the protective layer according to the first aspect of the present invention, the thickness of the protective layer, the amount of the solid particles, the plasticizer, and the like are adjusted so that the gas permeability satisfies the above-mentioned conditions according to the type of the solvent for coating the photosensitive layer. It can be easily obtained by adjusting the conditions such as the type and the amount of addition. When the photosensitive layer contains a component that generates N ₂ gas at the time of exposure, such as an o-quinonediazide compound, it is preferable to provide a protective layer having high gas permeability to N ₂ gas.

Next, the invention according to claim 2 will be described.

The protective layer of the image forming material according to the second aspect of the present invention has a nitrogen gas permeability (JIS K7126) of not less than 500 cc / m ² · 24 hrm and an average particle size larger than the thickness of the protective layer. Containing inorganic amorphous particles and organic spherical particles having an average particle diameter larger than the thickness of the protective layer, wherein the ratio of the inorganic amorphous particles to the organic spherical particles is 40:60 to 60 to 40 by weight. It is assumed that.

Here, the inorganic amorphous particles are particles formed of an inorganic substance, and the shape thereof is observed with an electron microscope of 500 times, and the ratio of the longest axis length / shortest axis length is 1.2 or more. The particles occupy 90% or more of the total particles. Organic spherical particles are particles formed of an organic compound. The shape of the particles is observed with an electron microscope of 500 times. Those having a ratio of 1.1 to 10 account for 90% or more of all the particles.

With the above configuration, the reproducibility of a halftone dot image when the support is a support having cushioning properties and the photosensitive layer is a photosensitive layer that generates nitrogen gas by image exposure (nitrogen during image exposure) The storage stability of the image forming material (deterioration of dot image reproducibility due to the storage of the image forming material) is improved.

The gas permeability of the above nitrogen gas (JIS K7
The protective layer having (126) can be easily obtained by adjusting the same conditions as in the case of the protective layer according to the first aspect of the present invention.

The image forming material according to the first aspect of the present invention is imagewise exposed to light and causes an imagewise difference in adhesiveness, and the imagewise transfer of the colored photosensitive layer to the material to be transferred imagewise due to the difference in adhesiveness. The image forming material may be formed as an image forming material for forming an image portion by performing image forming exposure and developing the image portion, and transferring at least the formed image portion to a material to be transferred (for example, real paper) to obtain a transferred image. . For example, in the case of forming a multicolor image using the former image forming material, one example of the basic method is as follows.

A first color image is formed on the first color image forming material, and at least the color image is transferred to a material to be transferred, and the support is peeled off. Further, after forming the second color image on the second color image forming material, the second color register image formed along with the second color image is formed on the material to be transferred. While registering with the image, the second color image is transferred onto the first color image, and the support is peeled off to obtain a two-color aligned image. Hereinafter, similarly, the colored images of the third color and the fourth color are transferred onto the transfer-receiving material to obtain a multicolor image. In some cases, the multicolor image is indirectly transferred onto another transfer-receiving material to obtain a multicolor image.

This type of method is disclosed in Japanese Patent Application Laid-Open No. 47-41.
No. 830, No. 59-97140, No. 60-28649
And U.S. Pat. No. 3,775,113. (Invention of Claim 3) In the image forming method using the image forming material of the invention according to Claim 1 or 2, the developing solution used for developing the image forming material has a developing action of developing the image forming material. Any material can be used. Preferably, a developer containing an alkali agent and an anionic surfactant is used.

Examples of usable alkaline agents include (1) sodium silicate, potassium silicate, potassium hydroxide, sodium hydroxide, lithium hydroxide, sodium or ammonium phosphate dibasic or tertiary, sodium metasilicate, Inorganic alkali agents such as sodium carbonate and ammonia,
(2) mono, di or trimethylamine, mono, di or triethylamine, mono or diisopropylamine,
Organic amine compounds such as n-butylamine, mono, di, or triethanolamine, mono, di, or triisopropanolamine, ethyleneimine, and ethylenediimine are included.

Examples of anionic surfactants that can be used include: (1) higher alcohol sulfates (for example, sodium salt of lauryl alcohol sulfate, ammonium salt of octyl alcohol sulfate, ammonium salt of lauryl alcohol sulfate, secondary sodium alkyl (2) fatty acid phosphoric acid ester salts (for example,
(3) Alkyl aryl sulfonates (eg, sodium dodecylbenzenesulfonate, sodium isopropylnaphthalenesulfonate, sodium dinaphthalenesulfonate, sodium metanitrobenzenesulfonate, etc.) (4) Alkyl amide sulfonates

[0067]

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(5) Sulfonates of dibasic aliphatic esters (eg, dioctyl sodium sulfosuccinate, dihexyl sodium sulfosuccinate, etc.) (6) Formaldehyde condensates of alkyl naphthalene sulfonates (eg, sibutyl naphthalene sulfonic acid) Sodium formaldehyde condensate, etc.).

The alkali agent and the anionic surfactant can be used in any combination.

[0070]

EXAMPLES Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

Examples 1 to 3 and Comparative Example 1 (Claim 1 or 3)
Examples of the invention according to the invention and comparative examples) Production of a support having cushioning properties A 5% xylene solvent dispersion of a low-density polyethylene resin (Mirason C-2499, manufactured by Mitsui Petrochemical) was applied to a thickness of 38 µm.
m on a non-processed surface of an antistatic processed polyethylene terephthalate film (T-100G, manufactured by Diafoil Hoechst Co., Ltd.) so that the film thickness after drying becomes 2 μm.
The resultant was dried with a dryer at 20 ° C. to obtain a temporary support having a uniform coating film of a low-density polyethylene resin on polyethylene terephthalate. Next, an ethylene-vinyl acetate copolymer resin (E) was placed on a 75 μm-thick polyethylene terephthalate film (Lumilar T-60, manufactured by Toray Industries, Inc.).
VAFLEX P-1407 (manufactured by Mitsui Dupont Chemical Co., Ltd.) is extruded into a layer having a thickness of 30 μm by extrusion lamination, and at the same time, the low-density polyethylene resin coating surface of the temporary support is laminated, and after cooling, the temporary support is cooled. Only the polyethylene terephthalate film was peeled off and removed to produce a roll-shaped support having cushioning properties.

Coating of Colored Photosensitive Layer On a low-density polyethylene resin layer on the above-mentioned roll-shaped support, a coating solution for a photosensitive layer having the following composition was applied using a wire bar so that the dry film thickness was 1.8 μm. It was applied and dried in a drying zone to provide a photosensitive layer containing each of the yellow, magenta, cyan and black colorants.

Composition of Coating Solution for Photosensitive Layer Ester of p-cresol novolak resin with naphthoquino-1,2-diazido-4-sulfonyl chloride 0.616 parts by weight Vinyl acetate (80 wt%)-vinyl versatate (20 wt%) %) Copolymer resin (average molecular weight: about 50,000, 50% methanol solution) 8.768 parts by weight The following pigment The following amount Methyl ethyl ketone 35.200 parts by weight Pigment Yellow: Lionol Yellow No. 1206 (manufactured by Toyo Ink Manufacturing Co., Ltd.) 0.680 parts by weight Magenta: Lionol Red 6B FG-4219 (manufactured by Toyo Ink Manufacturing Co., Ltd.) 0.680 parts by weight Cyan: Lionol Blue FG-7330 (manufactured by Toyo Ink Manufacturing) 0.550 parts by weight Black: carbon black MA-100 (manufactured by Mitsubishi Chemical Corporation) 0.990 parts by weight Coating of protective layer 30 minutes after application of the coating solution for the photosensitive layer, on the photosensitive layer Table 1 below
The coating liquid for a protective layer having the composition described in the above is applied using a wire bar so as to have a dry film thickness described in the same table, and dried in a drying zone, and four types of image forming materials obtained are wound into a roll. And stored at 25 ° C. for one day.

[0074]

[Table 1]

The gas permeability of the protective layer to methyl ethyl ketone as a coating solvent for the colored photosensitive layer was measured by the following method.

A coating solution for the protective layer shown in Table 1 was applied on a low-density polyethylene film having a thickness of 25 μm so as to have a dry film thickness shown in the same table to obtain a sample for measurement. JIS K7 using a gas permeability meter (manufactured by Toyo Seiki Seisaku-sho, Ltd.)
According to the method of No. 126, gas permeability for 24 hours was measured using methyl ethyl ketone as a coating solvent for the photosensitive layer as a permeated vapor. Next, the protective layer of the measurement sample was peeled off and the gas permeability of the methyl ethyl ketone vapor of only the polyethylene film was measured, and the difference was defined as the gas permeability of the protective layer.

Preparation of Four-Color Image A four-color color separation halftone positive image film was used as an original, and the originals of the respective color image forming materials were brought into close contact with each other so as to be an inverted image when viewed from the photosensitive layer side.
An image is exposed for about 60 seconds from a distance of 0 cm, and a developing solution having the following composition is used.
D, manufactured by Konica Corporation) to form an image on the cushioning support.

Composition of developer Konica PS plate developer SDP-1 (manufactured by Konica) 40 ml Perex NB-L (surfactant, manufactured by Kao Atlas Co., Ltd.) 100 ml distilled water 100 ml Matt coated paper (New Age, manufactured by Shin-Oji Paper Co., Ltd.) on the heated transfer drum
And firstly, nip the developed yellow image forming material with a pressure roller heated to 110 ° C.
/ Min, and the support was peeled off, and only the image was transferred to mat coated paper. The resolution and the clear sensitivity of the transferred image were evaluated. Then, transfer was performed in the order of yellow, magenta, cyan, and black, and a four-color image was formed on matt coated paper.

Measurement of Transmission Density With respect to the magenta image forming material, the transmission densities of the unexposed portions before and after development were measured using a transmission densitometer (TD910, manufactured by Macbeth).

The above results are shown in Table 2 below.

[0081]

[Table 2]

Examples 4 to 7 and Comparative Examples 2 to 6 (Examples and Comparative Examples according to Claims 2 and 3) The composition and the dry film thickness of the coating solution for the protective layer were as shown in Table 3 below. Except for the above, an image forming material was prepared in the same manner as in Example 1.

[0083]

[Table 3]

The shape of the solid particles contained in the protective layer is 5
Observation with a 00 × electron microscope shows that the particles having a ratio of the longest axis length / shortest axis length of 1.2 or more occupy 90% or more of all the particles are irregular, and the ratio of the longest axis length / shortest axis length is 1. Particles in which 1 to 10 accounted for 90% or more of all particles were spherical particles.

The gas permeability of the protective layer for N ₂ gas was measured by the following method.

The coating solution for each protective layer was applied to a 25-μm-thick low-density polyethylene film so as to have a dry film thickness as shown in Table 2 to obtain a sample for measurement. Using a gas permeability measuring device (manufactured by Toyo Seiki Seisaku-sho, Ltd.), gas permeability for 24 hours was measured using N ₂ gas as a permeated vapor according to the method of JIS K7126. Next, the protective layer of the measurement sample was peeled off and the gas permeability of N gas of only the polyethylene film was measured, and the difference was defined as the gas permeability of the protective layer.

Evaluation of Image Reproducibility After storing the above image forming materials for 3 days, the image reproducibility and the closeness of the printed matter were evaluated.

A UGRA Plate was formed on the polyethylene terephthalate film of the magenta image forming material.
Control Wedge and Konica Step Tablet were closely adhered so that the image after development was an inverted image when viewed from the photosensitive layer side, and image exposure was performed for about 60 seconds from a distance of 50 cm with a 4 kW metal halide lamp. Using a developer of the same composition, an automatic development processor (EX900,
(Manufactured by Konica Corporation) to form an image on the cushioning support.

A mat-coated paper (New Age, manufactured by Shin-Oji Paper Co., Ltd.) was placed on a transfer drum heated to 70 ° C. in an automatic development processor, and the developed image forming material was heated to 110 ° C. Nip with heated pressure roller, 90cm
The laminate and the support were peeled at a rate of / min, and only the image was transferred to mat coated paper. The resolution and clear sensitivity of the transferred image were evaluated.

For each color image forming material, development and transfer were performed in the same manner as described above using yellow, magenta, cyan, and black in the same manner as described above, using a four-color color separation positive image forming film for the original. A four color image was created on paper.

The results are shown in Table 4 below.

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[Table 4]

(Note) In the column of the inorganic particles and the organic particles, the upper row shows the particle shape, and the lower row shows the ratio (weight ratio). It can be seen that an image forming material having high similarity of printed matter to an image can be obtained.

[0094]

According to the first to third aspects of the present invention,
In an image forming material in which a photosensitive layer containing a colorant and a protective layer are coated in this order on a support, after the image forming material is manufactured, the performance caused by the coating solvent of the photosensitive layer remaining in the photosensitive layer is not affected. The stability is improved, whereby the color reproducibility when used for color proofing and the like is improved. According to the invention according to claim 2 and the invention according to claim 3 using the image forming material of the invention, when the photosensitive layer is one that results in a bubble of the N ₂ gas during imagewise exposure, is improved image reproducibility degradation due to air bubbles is further improved storability reproducibility and image forming material of the halftone image.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/40 521 G03F 7/40 521

Claims (3)

[Claims] 1. An image forming material comprising a support and a photosensitive layer containing a colorant and a protective layer sequentially coated thereon, wherein the protective layer is exposed to a vapor of a coating solvent vapor used for coating the photosensitive layer. Permeability (JIS K7126) is 500cc / m ²
An image forming material having a thickness of 24 hours or more; 2. An image forming material comprising a support and a photosensitive layer containing a colorant and an o-quinonediazide compound and a protective layer sequentially coated on the support, wherein the protective layer has the following conditions (a) and (b): An image forming material characterized by satisfying the following. (B) Nitrogen gas permeability (JIS K7126) is 5
00 cc / m ² · 24 hrm or more. (Ii) inorganic amorphous particles having an average particle size larger than the thickness of the protective layer and organic spherical particles having an average particle size larger than the thickness of the protective layer, the ratio of which is 40:60 to 6;
0:40 weight ratio. 3. An image is formed by at least imagewise exposing an image-forming material comprising a support and a photosensitive layer containing a colorant and a protective layer, which are successively coated, on a support and developing using a developer. 3. An image forming method according to claim 1, wherein said image forming material is the image forming material according to claim 1.