JPH08234419A - Colored picture forming material and its production - Google Patents

Abstract

PURPOSE: To suppress a bubble failure, to eliminate greasing and to prevent blocking by drying a colored picture forming material under a specified condition after a colored photosensitive layer is provided by coating. CONSTITUTION: A picture forming material having at least a releasable layer and a colored photosensitive layer on a substrate is produced. In this case, the colored picture forming material is dried at 70-120 deg.C for 30-120sec after the colored photosensitive layer is provided. Meanwhile, the colored picture forming material can have a protective layer on the (colored) photosensitive layer or another layer (or sheet). The drying time is the sum of the drying time and heat-treating time and the colored photosensitive layer processing time plus protective layer drying time when the protective layer is provided. The drying temp. is preferably controlled to 80-120 deg.C. Under such drying conditions, the adhesion at the interface between the releasable layer and colored photosensitive layer is secured, and greasing is never caused since the interfacial adhesion is not increased more than necessary.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored image forming material suitable for producing a color proof or the like for color proofing in color printing and a method for producing the same, and particularly to a color proof or the like having a printing similarity. The present invention relates to a colored image-forming material capable of obtaining the above-mentioned properties, improving blocking resistance and reducing bubble defects, and a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION It is well known in the art that color sheets (also called color proofs) for color proofing are used to save the labor and time required for proof printing as a pre-step of main printing in multi-color printing. . As a method for producing a multicolor transfer image using a color sheet for color proofing, for example, a direct transfer method described in JP-A-47-41830, in which a colored image is directly transferred and laminated on a final image receiving paper,
The indirect transfer method described in JP-A-59-97140 and JP-A-61-189535, in which a colored image is temporarily transferred onto a temporary (image-receiving) sheet, and JP-A-56-50127.
The method of repeating the step of forming an image after transferring the colored photosensitive layer to the image receiving paper described in JP-A No. 2003-242242 can be mentioned.

[0003]

In all of these methods, since the surface of the material to be transferred on which an image is formed is covered with an organic polymer layer, the gloss of the obtained image surface is too high, and the glossiness during actual printing is high. It has a problem that it gives an impression different from the image quality. Particularly, in the technique of JP-A-61-189535, there is a problem that the original gloss and texture cannot be obtained because the non-image area is covered with the organic polymer layer (polymer layer).

On the other hand, in order to solve this problem, there has been considered an image-only transfer system in which only a colored image is transferred and laminated on a material to be transferred to form a multicolor image (Japanese Patent Laid-Open No. 3-48248).
issue). In this method, since the material to be transferred is not covered with the organic polymer layer, it is possible in principle to obtain an image that is extremely close to the image quality at the time of actual printing. The colored image-forming material used in the transfer method for transferring only this image portion has a problem that gas such as N ₂ gas generated from the photoconductor at the time of exposure causes bubble failure in which the gas is accumulated at the interface between the release layer and the colored photosensitive layer. It turned out to be.

On the other hand, the simplest method for producing an image forming material for color proof is generally a support → a mold release treatment →
The process consists of winding, coating of the colored photosensitive layer, drying, and winding.

After the final winding step, a blocking failure in which the back surface of the support and the colored photosensitive layer adhere to each other is likely to occur. As a countermeasure, it may be considered that the back surface of the support is subjected to a release treatment, or the colored photosensitive layer contains release particles.

However, the former has the drawback that the release treatment agent migrates to the colored photosensitive layer and the transferability is lowered, and the latter causes the sensitivity and the transferability to be lowered.

According to the present invention, the blocking resistance is improved, and bubble failure (for example, N ₂ gas generated at the time of exposure when o-quinonediazide is used as a photoreceptor is generated at the interface between the release layer and the colored photosensitive layer). The purpose is to reduce the accumulated phenomenon).

[0009]

In order to achieve the above object, the present invention 1 provides a method for producing an image-forming material having at least a release layer and a colored photosensitive layer on a support, after the colored photosensitive layer is applied. A method for producing a colored image-forming material, which comprises drying at a temperature of 70 to 130 ° C. for 30 to 120 seconds. The present invention 2 is a method for producing an image-forming material having at least a release layer and a colored photosensitive layer on a support. , 35 to 45 ° C. for an image forming material having a release layer and a colored photosensitive layer
The method for producing an image-forming material, which comprises subjecting the material to aging for 8 to 48 hours, and the present invention 3 relates to a method for producing an image-forming material having at least a release layer, a colored photosensitive layer and a protective layer on a support. The method for producing a colored image-forming material, wherein the protective layer is coated with a mixed solvent of water and a water-miscible low-boiling solvent, the present invention 4 is at least a release layer and a colored photosensitive layer on a support. An image forming material having a protective layer, wherein the protective layer contains a matting agent having a different average particle size. The present invention 5 is at least a release layer and a colored photosensitive layer on a support. In the image forming material having the above, the component composition is changed in the film thickness direction of the colored photosensitive layer.

[0010]

According to the present invention, the adhesiveness at the interface between the release layer and the colored photosensitive layer is ensured during the drying treatment under the drying conditions of the present invention, so that the above object can be achieved, and the interfacial adhesiveness is increased more than necessary. Since it does not rise, there is no soiling.

According to the second aspect of the present invention, the adhesiveness at the interface between the release layer and the colored photosensitive layer is secured under the aging treatment conditions of the present invention, so that the above object can be achieved, and the interfacial adhesiveness is not increased more than necessary. Therefore, the soiling does not occur.

According to the present invention 3, by coating the protective layer using the solvent of the present invention, the drying speed is faster than the case of coating with water under the same drying conditions, and the release layer and the coloring are colored. Since the adhesiveness between the photosensitive layers can be increased, the above object can be achieved.

According to the fourth aspect of the present invention, by blending the matting agents having different average particle sizes, sufficient blocking resistance can be obtained with the same addition amount as in the case of using them alone. The same effect can be obtained by increasing the addition amount of a single substance, but there is a drawback that the sensitivity (developing property) is deteriorated, and the present invention can suppress the sensitivity decrease.

According to the present invention 5, bubble failure can be prevented and the above object can be achieved by adjusting the composition distribution of the colored photosensitive layer of the present invention.

The colored image-forming material of the present invention may have a protective layer on the (colored) photosensitive layer, or may have other layers (or sheets).

[0016]

DETAILED DESCRIPTION OF THE INVENTION The present invention is described in detail below. The water-miscible low boiling point solvent used in the present invention has a boiling point of 100.
Any solvent may be used as long as it is not more than 0 ° C and is miscible with water at 25 ° C in an arbitrary or specific weight ratio, and lower alcohols, esters, and ketones are preferable.

The matting agent used in the present invention preferably has an average particle size of 0.1 to 10 μm.

The binder for the protective layer is preferably one that swells or dissolves in water or an alkaline solution, and particularly when o-quinonediazide is used as a photoreceptor, celluloses / polyacrylic acid polymers / modified vinyl acetate having good gas permeability. Classes are particularly preferred.

The drying time is the total time of the heat treatment for drying (when a protective layer is applied, the processing time for the colored photosensitive layer + the drying time for the protective layer). The drying temperature is preferably 80-12.
0 ° C.

The present invention 2 is a method for producing an image-forming material having at least a release layer and a colored photosensitive layer on a support,
For an image forming material having a release layer and a colored photosensitive layer, 35
The method for producing an image-forming material is characterized in that the aging treatment is performed at ˜45 ° C. for 8 to 48 hours. The aging treatment of the present invention may be heating for improving the interfacial adhesion between the colored photosensitive layer and the release layer, and it is sufficient to leave it in a constant temperature atmosphere such as a constant temperature bath. Preferably, after cutting the colored image-forming material to a desired size, in order to prevent blocking of the colored photosensitive layer and the support due to heating, for example, paper laminated with polyethylene may be inserted so that the colored photosensitive layer and the polyethylene surface are in contact with each other. .

The present invention 3 is a method for producing an image-forming material having at least a releasing layer, a colored photosensitive layer and a protective layer on a support, wherein the protective layer is coated with a mixed solvent of water and a water-miscible low boiling point solvent. And a colored image forming material manufacturing method. The mixing ratio of water and solvent is mainly determined by the solubility of the protective layer binder and the solubility of the colored photosensitive layer. The mixing ratio is, for example, when hydroxypropylmethyl cellulose is used as the protective layer binder and ethanol / isopropanol or the like is used as the solvent, the content ratio of the solvent is 10 to 10.
90% is desirable. If it is more than 90%, the dissolution of the binder becomes insufficient and causes a coating failure. If it is less than 10%, the effect of the present invention is not sufficient.

The present invention 4 is an image forming material having at least a release layer, a colored photosensitive layer and a protective layer on a support,
A colored image forming material, wherein the protective layer contains matting agents having different average particle sizes. The average particle size of the matting agent used is preferably 0.1 to 10 μm. The particle size ratio is defined by the average particle size (small particle size) / the average particle size (large particle size), and the particle size ratio ≦ 0.9, preferably the particle size ratio ≦ 0.6. The mixing ratio is weight (large particle size) / weight (small particle size) = 1/9 to 9
/ 1 It is preferably in the range of 3/7 to 7/3.

The present invention 5 is an image-forming material having at least a release layer and a colored photosensitive layer on a support, wherein the component composition is changed in the thickness direction of the colored photosensitive layer. Is.

For the purpose of preventing bubble failure of the present invention, it is preferable to change the content of the o-quinonediazide compound in the film thickness direction. As a specific means therefor, there is a method in which a mixed solution is used as a solvent for the coating solution for the colored photosensitive layer and the mixing ratio is changed to control. More specifically, solvents having different solubility and boiling point of the o-quinonediazide compound are combined. Examples of the good solvent for the o-quinonediazide compound include acetone and methyl ethyl ketone (ME
K), 4-hydroxy-2-butanone, methyl lactate, and cellosolves, and examples of the poor solvent include propylene glycol alkyl ethers, dipropylene glycol alkyl ethers, diethylene glycols,
Examples thereof include 3-methoxy-1-butanol, alcohols, methyl propyl ketone, methyl butyl ketone, diacetone alcohol, cyclopentanone and cyclohexanone. For example, in order to reduce the amount of the o-quinonediazide compound in the photosensitive layer in the film thickness direction from the surface side not in contact with the support, a good solvent for the o-quinonediazide compound and a poor solvent having a boiling point higher than that are used. A mixture of the above may be used as the solvent of the coating liquid.

As another means, an o-quinonediazide-containing colored photosensitive layer is coated on a release-treated temporary support, laminated on the support of the present invention, and then the temporary support is peeled off to give a colored photosensitive material. Transfer the layers. It can be obtained by changing the amount of o-quinonediazide and repeating the above-mentioned processing a plurality of times.

As the photosensitive composition used in the colored photosensitive layer of the present invention, known positive type photosensitive compositions and negative type photosensitive compositions can be used, but positive type photosensitive compositions are preferred. As the positive photosensitive composition, it is preferable to use a photosensitive composition containing an o-quinonediazide compound. Any o-quinonediazide compound can be used as long as it can function as a photosensitizer. Specifically, for example, 1,2-benzoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-4-
A compound obtained by condensing sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, or 1,2-naphthoquinonediazide-6-sulfonyl chloride with a hydroxyl group- and / or amino group-containing compound is preferably used. Preferred is a compound having a sulfonyl chloride group at the 4-position, which is 1,2-naphthoquinonediazide-4.
A condensation compound with a sulfonyl chloride.

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

With respect to the quinonediazide compounds, including those mentioned herein, further reference is made to J. Koza (J. Kosa
r) "Light Sensitive System" (Light
Sensitive System (New York City, John Wiley and Sons, 1965), and Nagamatsu and Inui, "Photosensitive Polymer" (Kodansha, 1
1977).

Next, the photosensitive composition used in the present invention may contain known polymer compounds and synthetic resins. For example, a carboxylic acid vinyl ester polymer unit represented by the following general formula is incorporated into the molecular structure. It is preferable to contain the polymer compound.

[0030]

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However, R represents an alkyl group, and also includes an alkyl group having a substituent. Any polymer compound having the above structure can be arbitrarily used, but the following examples are preferable as the carboxylic acid vinyl ester monomer for forming the polymerized unit represented by the above general formula. The name and chemical formula are shown together.

1 vinyl acetate CH ₃ COOCH = CH ₂ 2 vinyl propionate CH ₃ CH ₃ COOCH = CH ₂ 3 vinyl butyrate CH ₃ (CH ₂ ) ₂ COOCH = CH ₂ 4 vinyl pivalate (CH ₃ ) ₃ COOCH = CH ₂ 5 Vinyl caproate CH ₃ (CH ₂ ) ₄ COOCH = CH ₂ 6 Vinyl caprylate CH ₃ (CH ₂ ) ₆ COOCH = CH ₂ 7 Vinyl caprate 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

[0033]

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(R ¹ and R ² are alkyl groups, and the sum of the carbon atoms thereof is 7. That is, R ¹ + R ² = C ₇ H ₁₆ is obtained.) The polymer compound is 1 of carboxylic acid vinyl ester. The polymer may be a polymer obtained by polymerizing a seed, or a polymer obtained by copolymerizing two or more kinds of carboxylic acid vinyl ester, and may be any component ratio of the carboxylic acid vinyl ester and another monomer copolymerizable therewith. May be a copolymer of

Examples of the monomer unit which can be used in combination with the polymer unit represented by the above general formula include ethylenically unsaturated olefins such as ethylene, propylene, isobutylene, butadiene and isoprene, such as styrene and α-methyl. Styrene, p-methylstyrene, p-
Styrenes such as chlorostyrene, acrylic acids such as acrylic acid and methacrylic acid, for example itaconic acid, maleic acid, unsaturated aliphatic dicarboxylic acids such as maleic anhydride, such as diethyl maleate, dibutyl maleate,
Diesters of unsaturated dicarboxylic acids such as di-2-ethylhexyl maleate, dibutyl fumarate, di-2-ethylhexyl fumarate, such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic acid Α such as phenyl, α-methyl chloroacrylate, methyl methacrylate, ethyl ethacrylic acid
-Methylene aliphatic monocarboxylic acid esters, for example, nitriles such as acrylonitrile and methacrylonitrile, amides such as acrylamide, such as acrylanilide, p-chloroacrylanilide, m-nitroacrylanilide, m-methoxyacrylanilide, etc. Anilides such as vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, β-chloroethyl vinyl ether, vinyl chloride, vinylidene chloride, vinylidene cyanide such as 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 There are vinyl monomers such as compounds. These monomer units have a structure in which the unsaturated double bond is cleaved and are present in the polymer compound.

Particularly preferred as the polymer compound used in the present invention is one having a vinyl acetate polymer unit in the molecular structure. Among them, those having 40 to 95% by weight of vinyl acetate polymer units, number average molecular weight (MN)
Of 1,000 to 60,000 and a weight average molecular weight (MW) of 500 to 150,000 are preferred.

More preferably, a polymer compound having a vinyl acetate polymer unit (particularly one having 40 to 95% by weight) and a carboxylic acid vinyl ester polymer unit having a longer chain than vinyl acetate is preferable, and particularly a number average molecular weight (MN). Is 2,000
0-60,000, weight average molecular weight (MW) is 10.0
It is preferably from 0 to 150,000.

In this case, the monomer constituting the polymer compound having vinyl acetate polymerized units by copolymerization with vinyl acetate may be any monomer as long as it can form a copolymer. You can choose it from your body.

The copolymers that can be used as the polymer compound in the present invention are listed below by showing the 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 8 Vinyl Acetate-Vinyl Chloride 9 Vinyl Acetate-N-Vinyl Pyrrolidone 10 Vinyl Acetate-Vinyl Propionate 11 Vinyl Acetate-Vinyl Pivalate 12 Vinyl Acetate-Varsatic Acid Vinyl 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 tic acid - crotonic acid 19 vinyl propionate - vinyl versatate 20 vinyl propionate - vinyl versatate - crotonic acid 21 pivalate - vinyl stearate - maleic acid

The above photosensitive composition can be used as an image forming material. For example, it can be used as a colored image forming material when used as a color proof. In this case, the colored photosensitive layer of the colored image forming material is image-wise removed by imagewise exposure and subsequent development to form a colored image.

Dyes and / or pigments are added as colorants in the colored photosensitive layer of the present invention. In particular, when used for color proofing, the normal color required there, that is, yellow,
Pigments and dyes that match the colors of magenta, cyan, and black are required, but other metal powders, white pigments, and fluorescent pigments are also used. When applying the present invention to a color proof, many pigments and dyes known in the art can be used, as described below.

(C.I means color index). Victoria Pure Blue (CI 42595) Auramine (CI 41000) Catillon Brilliant Flavin (CI Basic 13) Rhodamine 6GCP (CI 45160) Rhodamine B (CI 45170) Safranine OK70: 100 (CI. I 50240) Erioglaucine X (CI 42080) Fast Black HB (CI 26150) No. 1201 Lionol Yellow (CI 21090) Lionol Yellow GRO (CI 21090) Shimla Fast Yellow 8GF (CI 21105) Benzidine Yellow 4T-564D (CI 21095) Shimla Fast Red 4015 (CI 12355) ) Lionol Red 7B4401 (CI 15830) Fastgen Blue TGR-L (CI 74160) Lionol Blue SM (CI 26150) Mitsubishi Carbon Black MA-100 Mitsubishi Carbon Black # 30, # 40, # 50.

When a colorant is used in the present invention, the ratio of the colorant / a component other than the colorant in the colored photosensitive layer may be determined by those skilled in the art in consideration of the target optical density and the removability of the colored photosensitive layer from a developer. It can be determined by a known method. For example, in the case of a dye, its content is preferably 5% by weight.
.About.75%, and in the case of a pigment, the content is preferably 5% to 90% by weight.

The thickness of the colored photosensitive layer is determined by a method known to those skilled in the art according to the target optical density, the kind of the coloring agent used in the colored photosensitive layer (dye, pigment, carbon black) and its content. However, if the thickness of the colored photosensitive layer is as thin as possible within the allowable range, the resolution is higher and the image quality is better. Thus, the membrane thickness is preferably usually being used in the range of ^{0.1g / m 2 ~5g / m 2} .

In carrying out the present invention, a plasticizer, a coating property improving agent and the like may be further added to the photosensitive composition, if necessary. 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.

When the photosensitive composition is used to form the image-forming material, the support used is arbitrary, but a transparent support is preferably used. As the transparent support, a polyester film, particularly a biaxially stretched polyethylene terephthalate film is preferable from the viewpoint of dimensional stability against water and heat. In addition, an acetate film, a polyvinyl chloride film, a polyethylene film, a polypropylene film, a polyethylene film and the like can be used.

Any known protective layer may be used, but its gas permeability is preferably selected appropriately according to the type of photosensitive composition used. That is, it is preferable to provide a protective layer having high gas permeability in the case of a photosensitive composition that generates a gas during exposure such as o-quinonediazide, and to use a gas when a photopolymerizable photosensitive composition is used. It is preferable to provide a protective layer having low permeability. Further, those which are soluble in a developing solution at the time of development, particularly water-soluble polymers such as polyvinyl alcohol and celluloses, have a thickness of about 0.01 to 5 μm, particularly 0.0
It is preferably about 3 to 1 μm.

The image-forming material according to the present invention can be used in the form of transferring an image to a transfer-receiving material. In order to perform the transfer onto the material to be transferred at this time efficiently, that is, in order to improve the image transfer property, it is preferable to provide a release layer having a cushion on the upper surface of the support, which will be described later. .

In the image forming method using the image forming material of the present invention, the image forming material of the present invention is exposed and developed to form an image portion, and at least the formed image portion is a transfer material (eg, main paper). To obtain a transferred image.

When the image forming method using the image forming material of the present invention is embodied as a multicolor image forming method,
One of the basic methods is as follows.

A colored image of the first color is formed on the colored image forming material of the first color, at least the colored image is transferred to the material to be transferred, and the support is peeled off. Further, after forming the second-color coloring image on the second-color coloring image forming material, the second-color registration mark image formed in association with the second-color coloring image is registered with the first-color registration mark image on the transfer material. , The second colored image is transferred onto the first colored image, and the support is peeled off to obtain a two-color aligned image. Similarly, the colored images of the third color and the fourth color are also transferred onto the material to be transferred to obtain a multicolor image. Also,
In some cases, this multicolor image may be indirectly transferred onto another transfer material to obtain a multicolor image. In the above, the release layer is peeled off together with the support. Incidentally, this kind of method is disclosed in JP-A-47-41830, JP-A-59-97140 and JP-A-6-41830.
No. 0-28649 and U.S. Pat. No. 3,775,113.

The image-forming material of the present invention is usually imagewise exposed through a color separation mask or the like and then developed to form an image. At this time, only the image portion of the image obtained on the support is directly transferred and laminated on the material to be transferred. That is, only the colored image layer that substantially forms an image is transferred and laminated. In this case, the release layer according to the present invention is provided on the support in order to efficiently perform the transfer onto the transfer surface and to facilitate the peeling of the support after the image transfer. The thickness of the release layer is preferably 15 to 100 μm, more preferably 20 μm to 50 μm. Typical cushion materials used for the release layer include natural rubber and the following materials.

Thermoplastic rubber, Kraton G (G16
52, G1650, etc.) [made by Shell Chemical Co.] thermoplastic rubber, Cariflex TR (TR118)
4, TR1150, TR4122, etc.) (Shell Chemical Co.) ethylene-ethyl acrylate copolymer resin (EVAFL)
EX-EEA) [Mitsui DuPont Polychemical Co., Ltd.] Polybutadiene rubber styrene-butadiene copolymer Acrylonitrile-butadiene copolymer Polyisoprene rubber resin Styrene-isoprene copolymer Acrylic ester copolymer Polyurethane copolymer condensation rubber or It is also possible to put a foaming agent on the surface of the support and provide a release layer on the surface (upper part) of the support by foaming it by heating, light irradiation or the like to provide cushioning properties.

The method for producing the release layer is not limited, and is generally produced by coating. It is also effective to provide an anchor layer to increase the adhesive strength. As the anchor agent, vinyl acetate-based polymer, polyvinyl-based polymer, polyester-based polymer, polyurethane-based polymer, polyvinyl alkyl ether polymer, etc., and if necessary, it is also effective to add an isocyanate compound or an epoxy compound as a crosslinking agent. is there.

In addition to the above, other resins may be blended in the release layer within a range not impairing the effects of the present invention. The blend resin preferably has a softening point of -30 ° C to 150 ° C. The softening point temperature mentioned here is a value shown by the VICAT softening point or the ring and ball method. In the present invention, specifically, the following may be mentioned as preferable resins.

Polyolefins such as polyethylene and polypropylene. Ethylene copolymers such as ethylene and vinyl acetate, ethylene and acrylic ester, ethylene and acrylic acid. PVC. Vinyl chloride copolymers such as vinyl chloride and vinyl acetate. Polyvinylidene chloride. Vinylidene chloride copolymer. polystyrene. Styrene and styrene copolymers such as maleic anhydride. Polyacrylic ester. Polyester resin. Polyurethane resin. Acrylic ester and acrylic ester copolymers such as vinyl acetate. Polymethacrylic acid ester. Methacrylic acid ester copolymers such as methyl methacrylate and vinyl acetate, and methyl methacrylate and acrylic acid. Polyvinyl acetate. Vinyl acetate copolymer. Vinyl butyral resin. Polyamide resins such as nylon, copolymerized nylon and N-alkoxymethylated nylon. Petroleum resin. Chlorinated rubber. Polyethylene glycol. Polyvinyl alcohol hydro phthalate cellulose derivative, cellulose acetate phthalate, cellulose acetate succinate. Shellac. wax.

In the second aspect of the present invention, an image forming material having a release layer on a support and at least one colored photosensitive layer containing a photosensitive composition and a colorant thereon is subjected to image exposure and development treatment. Then, after forming the colored image on the photosensitive layer, in the method for producing an image-forming material, in which only the colored image is exposed on the surface of the non-transfer material and transferred to the non-transfer material to obtain a transferred image, aging treatment is performed. Is characterized by.

The aging treatment in the present invention may be carried out by heating for improving the interfacial adhesion between the colored photosensitive layer and the release layer, and may be carried out at 35 ° C. to 45 ° C. for about 8 to 48 hours. It is sufficient that the heating means is allowed to stand in a constant temperature chamber such as a constant temperature bath.

As a method for providing the release layer and the cover sheet on the support, particularly the transparent support, (1) a solution prepared by dissolving the natural rubber, synthetic rubber or the like in an organic solvent is provided on the support. Method, and after drying with hot air or heating, the cover sheets are overlapped and laminated by pressure bonding under heating;

(2) After the adhesive such as the natural rubber or synthetic rubber is heated as it is and kept in a molten state, it is applied on the support by a doctor blade method, a roll coating method, a gravure method, a reverse roll method or the like. , A so-called hot melt laminating method in which a cover sheet is immediately laminated, and if necessary, heated at a high temperature and then cooled to be laminated.

(3) A so-called extrusion laminating method in which synthetic rubber or the like is kept in a molten state and extruded onto a support by an extruder, and while the molten state is in a molten state, a cover sheet is pressure-bonded and laminated.

(4) When a film to be a support is formed by the melt extrusion method, a plurality of extruders are used, molten synthetic rubber or the like is used, and the synthetic rubber or the like is formed on the support by one-time molding. A layer is formed, and similarly, a cover sheet is pressure-bonded and laminated while it is in a molten state, a so-called coextrusion method or the like;

In any of the above methods (1) to (4), the cover sheet is provided on the surface of the support after the release layer is provided on the support (or at the same time). The material of the cover sheet is not limited, and polyethylene terephthalate and other materials similar to the above may be used. The cover sheet preferably contains an antistatic agent or has an antistatic layer coated on at least one surface. Above (1)
~ Cover sheet obtained by the method (4) or any other method
The support with a release layer is once wound and used in the next step.

When the cover sheet is not provided, interleaving paper is inserted if necessary, and the paper is once wound and used in the next step. The interleaving paper may be publicly known or publicly used.

The release layer of the support is obtained by applying the coating solution for the colored photosensitive layer containing the photosensitive composition and the colorant to the release surface after or while releasing the cover sheet or the interleaving paper. A colored photosensitive layer is provided on the top.

In the present invention, the developing solution used for developing the image forming material can be arbitrarily used as long as it has a developing action for developing the material to be processed.
It is preferable to use a developer containing an alkali agent and an anionic surfactant.

Alkali agents which can be used include (1) sodium silicate, potassium silicate, potassium hydroxide, sodium hydroxide, lithium hydroxide, secondary or tertiary acid sodium phosphate or ammonium salt, sodium metasilicate, Inorganic alkaline agents such as sodium carbonate and ammonia, (2) mono, di, or trimethylamine, mono,
Organic amine compounds such as di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-, di-, or triethanolamine, mono-, di-, or triisopropanolamine, ethyleneimine, ethylenediimine, and the like can be mentioned.

The 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). (Sulfate, etc.), (2) Fatty alcohol phosphate ester salts (eg,
(Sodium salt of cetyl alcohol phosphate, etc.) (3) Alkylaryl sulfonates (for example, sodium dodecylbenzenesulfonate, sodium isopropylnaphthalenesulfonate, sodium dinaphthalenesulfonate, sodium metanitrobenzenesulfonate, etc.) (4) Alkyl amide sulfonates

[0070]

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(5) Sulfonates of dibasic aliphatic esters (for example, dioctyl sodium sulfosuccinate, dihexyl sodium succinate, etc.) (6) Formaldehyde condensates of alkylnaphthalene sulfonates (for example, cibutylnaphthalene sulfonic acid) Formaldehyde condensate of sodium). The alkaline agent and the anionic surfactant can be used in any combination.

[0072]

EXAMPLES Examples of the present invention will be illustrated below together with comparative examples. However, the present invention is not limited to the examples described below. Example 1 (Invention 1) (1) Colored Photosensitive Layer Dispersion Solution The following photoreceptor, binder and pigment were combined and applied as shown in Table 1.

Photoreceptor: 1,2-naphthoquinone diad-4
-Sulfonic acid-p-cresol formalinester polymer Binder: vinyl acetate-vinyl versatate (80: 2
0 parts by weight) copolymer (50% methanol solution)

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[Table 1]

Pigment: Yellow Seica First Yellow H-7055 (manufactured by Dainichiseika) Cyan Cyanine Blue 4920 (manufactured by Dainichiseika) Magenta Seikafast Carmine 1483 (manufactured by Dainichiseika) Black Carbon Black MA-100 (manufactured by Mitsubishi Chemical) (2) Release treatment support An ethylene-vinyl acetate copolymer (trade name: Evaflex, manufactured by Mitsui DuPont Chemical) was heat-melted on PET and applied by extrusion lamination to a thickness of 30 μm. (3) Coating / Drying of Colored Photosensitive Layer The dispersion of (1) was coated on the release-treated support prepared in (2) so that the dry film thickness was 1 μm, and dried under the drying conditions shown in the table below.

On the surface of the ethylene-vinyl acetate copolymer film of the four colored image-forming materials obtained above, the color-dispersion net positive film of each color was superposed, and the image was exposed for 20 seconds from a distance of 50 cm with a 4 kW metal halide lamp. And developed by immersing in the following developing solution for 30 seconds to form a four-color colored image.

<Developer> Na ₂ CO ₃ 15 g Surfactant (Perox NBL manufactured by Kao Atlas Co., Ltd.) 50 g Distilled water 1000 g Next, the image surface of the yellow image and the art paper were brought into close contact with each other, and 8
5 kg / cm between a pair of nip rolls heated to 0 ℃
Under the pressure condition of ^2, the substrate was passed at a speed of 50 cm / min, and then the support was peeled off. The peeling was easily performed, and only the yellow image portion was transferred onto the art paper.

Subsequently, the colored images were transferred in the order of magenta, cyan and black, whereby a color proofing image consisting of four colors was obtained on the art paper.

The results are shown in Table 2.

[0080]

[Table 2] Note) Bubble failure; ○ (visually, no bubbles) by visual judgment →
A five-level evaluation with a mark X (there are many bubbles) was made.

Example 2 (Invention 2) Polyethylene terephthalate (PET) having a thickness of 75 μm
EVA resin (Vinyl acetate
Molybdenum ratio of ethylene copolymer = 10/90) was extruded to apply 40 μm by laminating method, and at the same time, thickness 2
A 5 μm PET film was laminated. Next, while peeling off the PET film laminated on the release-treated support, the following photosensitive solution and overcoat solution were sequentially applied and dried, and coiled while inserting the interleaf paper shown below. I went.

(Photosensitive solution) o-naphthoquinone diazide-4-sulfonic acid ester of p-cresol formalin novolac resin (weight average molecular weight: 2000) ... 600 g 50% of vinyl acetate / vinyl versatic acid copolymer Methanol solution (charged weight ratio = 70: 30, weight average molecular weight = 45000) ... 8784 g-Pigment (shown below) -Glutaric acid ... 20 g-Fluorosurfactant (FC-430 <manufactured by 3M Company> ) ・ ・ ・ 10 g ・ Methyl ethyl ketone ・ ・ ・ 25000 g

<Pigment> Yellow: Seica First Yellow 680 g Magenta; Seica First Carmine 1483 680 g Cyan; Cyanine Blue 4920 550 g Black; Carbon Black MA-100 990 g (Overcoat liquid) -Cellulose derivative (carboxymethyl cellulose) 100g-Water 3000g

(Coating / drying conditions) -Coating conditions; wire bar coater-Drying conditions; 80 ° C, 90 seconds-Coating speed: 10 m / min (same as the speed at which the laminate film is peeled) The transmission density of each color is yellow; 50, magenta;
It was 0.62, cyan; 0.61, and black; 0.64.

Subsequently, it was cut and subjected to the following aging treatment to obtain a colored image forming material (sensitizing material for proof) according to the present invention. Next, the color-separated positive film of each color is overlaid on the PET film surface of the four-colored colored image-forming material obtained above, and the color separation positive film of 4 KW is used to generate 50
Image exposure was performed for 30 seconds from a distance of cm, and then development processing was performed with the following developer at 30 ° C. for 45 seconds while rubbing with a sponge with a bat.

(Developer) -Potassium silicate ... 40 g-Perex NBL (manufactured by Kao Atlas) ... 80 g-Water ... 2000 g Next, a transfer machine described in JP-A-3-120552, that is, on a drum. Art paper (made by Mitsubishi Paper Mills, Tokubishi Art)
Alternatively, a high-quality paper (made by Oji Paper Co., Ltd., high-quality paper) was wrapped, and then the image on the film prepared above was thermally transferred to art paper or high-quality paper under the following temperature and pressure conditions.

(Transfer Condition) (Transfer Condition 1) • Diameter of pressure roller 12 cm • Diameter of drum 30 cm • Nip pressure between pressure roller and drum 5 kg / cm ² • Surface temperature of drum 75 ° C. • Surface of pressure roller Temperature 100 ℃ ・ Transfer speed 45 seconds

(Transfer material) Art paper; Tokubishi art (manufactured by Mitsubishi Paper Mills Co., Ltd.) Fine paper; Fine paper (Oji Paper) Transferred in the order of yellow, magenta, cyan and black A high-quality color image with less stickiness was obtained. Bubble failure during exposure was evaluated, and the results are shown in Table 3. Next, the image-forming material (light-sensitive material film) was allowed to stand naturally at room temperature in an air-conditioned room for 3 months to evaluate the blocking of the light-sensitive material (○ mark is good and no blocking → many X marks show blocking. It was evaluated as 5 levels. The results are shown in Table 3.

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[Table 3] The blocking evaluation was visually evaluated after the aging treatment.

Example 3 (Invention 3) In the photosensitive material used in Example 1, a protective layer having the following constitution was coated on the colored photosensitive layer with a wire bar. The coating thickness was 0.02 g / m ^{2 as the} coating amount. Protective layer formulation Cellulose derivative (carboxymethyl cellulose) 100 g Water 2400 g Ethanol 600 g Coating drying conditions Coating method: Wire bar Drying conditions: 80 ° C. for 30 seconds Coating speed: 10 m / min

Example 4 (Invention 4) In the photosensitive material used in Example 1, a protective layer having the following constitution was coated on the colored photosensitive layer with a wire bar. The coating thickness was 0.02 g / m ^{2 as the} coating amount. Protective layer formulation Matting agent silica (average particle size 5 μm) 5 g Matting agent silica (average particle size 1 μm) 5 g Cellulose derivative (carboxymethyl cellulose) 100 g Water 3000 g Application Drying conditions Coating method: Wire bar Drying conditions: 80 ° C. for 90 seconds Coating speed: 10 m / min Blocking evaluation After inserting into polyethylene laminated paper, 50 sheets of cut colored image forming materials are stacked, put into a 40 ° C. constant temperature bath, and taken out. After that, the peeling of the colored photosensitive layer was visually evaluated.

Example 5 (Invention 5) A colored image-forming material was prepared in the same manner as in Example 1 except that 30% of methyl ethyl ketone shown in Table 1 was replaced with methyl butyl ketone.

Comparative Example 1 The photosensitive material used in Example 2 was prepared by coating and drying under the following conditions. Coating and drying conditions Coating method: Wire bar Drying conditions: 60 ° C, 90 seconds Coating speed: 10 m / min

Comparative Example 2 A light-sensitive material was prepared in the same manner as in Comparative Example 1 except that the following protective layer was provided. Coating thickness is 0.02g / m ²
And Protective layer formulation Matting agent Silica (average particle size 5 μm) 10 g Cellulose derivative (carboxymethyl cellulose) 100 g Water 3000 g

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[Table 4]

Comparative Example 3 A color proof was prepared using a light-sensitive material different from that of the system of the present invention (a method of transferring only an image) (Japanese Patent Laid-Open No. 61-189535, a photosensitive material film of Example 1), and the same operation was performed. And evaluated. The odor during the work was not so strong although the content of the volatile component was high, but it did not have the printing approximation.

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According to the present invention, it is possible to suppress the occurrence of bubble failure in a system for obtaining an image with high print approximation.
An image forming material that does not cause scumming and can prevent blocking from occurring, and a method for producing the same can be provided.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Miyuki Hosoi 1st Sakura Town, Hino City, Tokyo Konica Stock Company (72) Inventor Tetsuya Taniguchi 1st Sakura Town, Hino City, Tokyo Konica Stock Company (72) Inventor Tetsuya Masuda 1000 Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa Sanryo Chemical Co., Ltd. (72) Inventor Hideaki Mochizuki 1000, Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa Sanryo Chemical Co., Ltd.

Claims (5)

[Claims] 1. A method for producing an image-forming material having at least a release layer and a colored photosensitive layer on a support, characterized in that after the colored photosensitive layer is applied, it is dried at a temperature of 70 to 130 ° C. for 30 to 120 seconds. A method for producing a colored image forming material. 2. A method for producing an image forming material having at least a releasing layer and a colored photosensitive layer on a support, wherein the image forming material having the releasing layer and the colored photosensitive layer has a temperature of 35 to 45 ° C.
A method for producing an image-forming material, which comprises performing aging treatment for 48 hours. 3. A method for producing an image-forming material having at least a release layer, a colored photosensitive layer and a protective layer on a support, wherein the protective layer is coated with a mixed solvent of water and a water-miscible low boiling point solvent. A method for producing a colored image-forming material, comprising: 4. An image forming material having at least a releasing layer, a colored photosensitive layer and a protective layer on a support, wherein the protective layer contains a matting agent having different average particle diameters. . 5. An image forming material having at least a release layer and a colored photosensitive layer on a support, wherein the component composition is changed in the thickness direction of the colored photosensitive layer.