JP3408338B2 - Method for producing colored image forming material - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a colored image-forming material suitable for producing a color proof for color proofing in color printing, and more particularly to a color proof which more closely resembles a printed matter. The present invention relates to a method for producing a colored image-forming material that can be obtained.

[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 transfer material 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 the image portion transfers the image only from the heat-softening layer (cushion layer) to the material to be transferred during the heat laminating process. Due to the convex portion generated by, the uniformity at the time of coating, by extension, the uniformity of the density of the image area is impaired,
The present inventors have revealed that there is a problem that printed matter approximation may be impaired.

The present invention solves the above problems of the prior art,
It is an object of the present invention to provide a method for producing a colored image-forming material capable of obtaining a color proof more similar to a printed matter. In particular, (1) the surface properties of the image area and the non-image area are equal to or similar to those of the printed matter, and (2) the unevenness of the image area due to the cushion layer surface area is suppressed to approximate the printed matter. An object of the present invention is to provide a method for producing a colored image forming material capable of obtaining a color proof.

[0006]

The present invention which achieves the above object has the following constitution. 1. A cushion layer is provided on a support, a colored photosensitive layer containing a photosensitive composition and a colorant is provided on the cushion layer, and a colored image portion is formed by imagewise exposure and development, and then the colored image is obtained. A colored image-forming material which directly transfers only a part to a material to be transferred which becomes a final image-receiving paper without interposing a temporary image-receiving sheet, and which is an average of the surface of the cushion layer on the side of the colored photosensitive layer. Glossiness [GS (60
°)] is 30 or more, a cover sheet is laminated on the cushion layer, and then the cover sheet is peeled off in the production method for producing a colored image-forming material having a configuration in which a colored photosensitive layer is provided on the cushion layer. In the step of coating the colored photosensitive layer on the release surface, the cushion layer side surface of the cover sheet has an average gloss [GS (60 °)] of 30 or more and a center line average roughness (Ra) of 0.3 μm or less. A method for producing a colored image-forming material, which comprises using the cover sheet of

2. 2. The method for producing a colored image-forming material as described in 1 above, wherein the surface of the cushion layer is mirror-finished after the cover sheet is peeled off and before the colored photosensitive layer is applied.

[0008]

The methods described in JP-A-3-48248 and JP-A-61-189535 are known as methods used for color proofing for color proofing in color printing. In the method of No. 3-48248, the surface of the cushion layer is matted and the gloss of the image area of the final image is impaired, and the unevenness caused by gelation of the cushion layer resin or the like causes unevenness during application and thus the density of the image area. The present inventors have revealed that there is a problem in that the uniformity of printed matter may be impaired and the printed matter approximation may be hindered. Also, JP-A-61-1895
In the method of No. 35, since the non-image area is covered with the polymer layer, there is a problem that the original gloss and texture are not obtained. These problems can be solved at once by the present invention.
The configuration for solving the specific problem of (2) above is as follows for reference. Reference 1 A colored image-forming material having a cushion layer on a support and a colored photosensitive layer containing a photosensitive composition and a colorant on the cushion layer, wherein the colored image portion is formed by imagewise exposure and development treatment. In the colored image-forming material for forming a transferred image by transferring only the colored image portion to the material to be transferred after formation of the above, the cushion layer contains a polymer containing vinyl carboxylate as a polymerized unit, and the polymer is A colored image-forming material in which the proportion of the polymerized portion derived from the carboxylic acid vinyl ester is 11% by weight or less based on the total weight of the polymer. Reference 2 An image forming material having a cushion layer on a support, and a colored photosensitive layer containing a photosensitive composition and a colorant on the cushion layer, wherein a colored image portion is formed by imagewise exposure and development treatment. After forming, a colored image forming material is obtained by transferring only the colored image portion to the transferred material to obtain a transferred image. A transfer image forming method in which the surface is treated so that the average glossiness [GS (75 °)] of the surface is 60 or more. Reference 3 An image forming material having a cushion layer on a support and a colored photosensitive layer containing a photosensitive composition and a colorant on the cushion layer, wherein a colored image portion is formed by imagewise exposure and development treatment. In a colored image-forming material for obtaining a transferred image by transferring only the colored image portion to a material to be transferred after being formed, it is 100 μm or more thicker than the average film thickness of the cushion layer, which is present on the surface of the cushion layer facing the colored photosensitive layer. The number of protrusions is 1
A colored image forming material having 0 / m ² or less.

[0009]

DETAILED DESCRIPTION OF THE INVENTION In the present invention, the average glossiness of the surface of the cushion layer on the side of the colored photosensitive layer is 30 or more, preferably 70 or more, more preferably 100 or more.
A means for obtaining the surface glossiness of the cushion layer is a laminating method, and various laminating methods described later can be adopted.
The glossiness in the present invention refers to a value obtained by the measuring method of JIS-Z8741. The average gloss is 1 m ²
Per 10 means the arithmetic mean of the measured values obtained by measuring.

When the cover sheet is peeled off, the peeling angle with the surface of the cushion layer is preferably 90 ° or less, more preferably 80 ° or less. The cover sheet used has the structure of the present invention.

[0011]

[0012]

[0013]

[0014]

The colored image forming material used in the present invention is
A protective layer may be provided on the colored photosensitive layer, or another layer (or sheet) may be provided.

The present invention will be described in more detail below, but the references 1 to 3 will also be described. The colored photosensitive layer of the invention means a structure containing a photosensitive composition and a colorant in one layer, and a layer structure having a layer containing the photosensitive composition and a layer containing a colorant.

As the photosensitive composition used in the colored photosensitive layer of the present invention, a known positive type photosensitive composition / negative type photosensitive composition can be used. It is preferable to use a photosensitive composition containing a quinonediazide compound. The o-quinonediazide compound is
Any substance 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-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, 1,
A compound obtained by condensing 2-naphthoquinonediazide-6-sulfonyl chloride and 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 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).

As the negative photosensitive composition, a photopolymerizable photosensitive composition is preferable. Specifically, for example, as the photopolymerizable compound, any of those generally used can be arbitrarily used. For example, at least one compound arbitrarily selected from the compound group consisting of acrylic acid, methacrylic acid, acrylic acid ester and methacrylic acid ester can be used. For example, ethylene glycol diacrylate, glycerin triacrylate, polyacrylate, ethylene glycol dimethacrylate, 1,3
-Propanediol dimethacrylate, 1,2,4-butanetriol trimethacrylate, polyethylene glycol dimethacrylate, trimethylolethane triacrylate, pentaerythritol dimethacrylate,
Pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol polyacrylate, 1,3-propanediol diacrylate, 1,5-pentanediol dimethacrylate, polyethylene Examples thereof include, but are not limited to, glycol bisacrylate and bismethacrylate.

The negative type photosensitive layer may contain a photopolymerization initiator. In this case, the photopolymerization initiator is optional, but a photopolymerization initiator having less absorption in the visible region is more preferable, and examples of such a photopolymerization initiator include the following compounds. However, it is not limited to these. That is,
Benzophenone, Michler's ketone [4 ', 4'-bis (dimethylamino) benzophenone], 4,4'-bis (diethylamino) benzophenone, 4-methoxy-
Aromatic ketones such as 4'-dimethylaminobenzophenone, 2-ethylanthraquinone, phenanthraquinone, and other aromatic ketones, benzoin ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether. , Methylbenzoin, ethylbenzoin and other benzoins, and 2- (o-chlorophenyl)-
4,5-Diphenylimidazole double body, 2- (o-chlorophenyl) -4,5- (m-methoxyphenyl) imidazole double body, 2- (o-fluorophenyl)-
4,5-diphenylimidazole double body, 2- (o-methoxyphenyl) -4,5-diphenylimidazole double body, 2- (p-methoxyphenyl) -4,5-diphenylimidazole double body, 2,4-di (P-Methoxyphenyl) -5-phenylimidazole double body, 2-
(2,4-Dimethoxyphenyl) -4,5-diphenylimidazole duplex, 2- (p-methylmercaptophenyl) -4,5-diphenylimidazole duplex, and U.S. Pat. No. 3,479,185, British Patent 1 , 047,
Mention may be made of 2,4,5-triacryluimidizole duplexes such as the similar duplexes described in US Pat. No. 569 and US Pat. No. 3,784,557.

Other photopolymerizable compounds include 2,4-
Thioxanthones such as diethylthioxanthone can also be used. In this case, known compounds such as p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid ethyl ester, N-methyldiethanolamine, and bisdiethylaminobenzophenone can be used as the photopolymerization accelerator.

Next, the photosensitive composition of the present invention may contain a known polymer compound or synthetic resin, and particularly in the present invention, the carboxylic acid vinyl ester polymerization unit represented by the following general formula has a molecular structure. It is preferable to contain the polymer compound contained therein.

[0024]

[Chemical 1]

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 = C
H 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 = C
H 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 COOC
H = CH ₂ 10 vinyl palmitate CH ₃ (CH ₂ ) ₁₄ COO
CH = CH ₂ 11 vinyl stearate CH ₃ (CH ₂ ) ₁₆ COO
CH = CH ₂ 12 vinyl versatate

[0027]

[Chemical 2]

The polymer compound (where 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 a 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 Phenyl, α-methylene aliphatic monocarboxylic acid esters such as α-methyl chloroacrylate, methyl methacrylate, and ethyl methacrylate, nitriles such as acrylonitrile and methacrylonitrile, amides such as acrylamide, and acrylanilide, for example. , P-chloroacrylanilide, m-nitroacrylanilide, m-methoxyacrylanilide, etc., such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, β-chloroethyl vinyl ether. Vinyl ethers, vinyl chloride, vinylidene chloride, vinylidene cyanide, such as 1-methyl-1-methoxyethylene, 1,1-dimethoxyethylene, 1,2-ethylene, 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 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 examples.

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-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-versatiate vinyl Le - crotonic acid 19 vinyl propionate - vinyl versatate 20 vinyl propionate - vinyl versatate - crotonic acid 21 pivalate - vinyl stearate - maleic acid

The photosensitive composition of the present invention 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 portion.

Dyes and / or pigments are added as colorants in the colored photosensitive layer. In particular, when used for color proofing, pigments and dyes that have a color tone matching those of the ordinary colors required, that is, yellow, magenta, cyan, and black are required, but other metal powders, white pigments, and fluorescent pigments are also required. Are also used. When applying the present invention to color proofing, many pigments and dyes known in the art can be used, such as:

(C.I means color index). Victoria Pure Blue (CI 42595) Auramine (CI 41000) Catillon Brilliant Flavin (CI Basic 1
3) Rhodamine 6GCP (CI 45160) Rhodamine B (CI 45170) Safranine OK 70: 100 (CI 50240) Erioglaucin X (CI 42080) Fast Black HB (CI 26150) No. 1201 Lionol Yellow (C.I. 2109
0) Lionol Yellow GRO (CI 21090) Shimla First Yellow 8GF (CI 2110)
5) Benzidine Yellow 4T-564D (C.I 2109
5) Shimla Fast Red 4015 (C.I 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

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 can 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 coatability improving agent and the like may be further added to the photosensitive composition, if necessary. As plasticizers, various low molecular weight compounds, for example, phthalic acid esters, triphenyl phosphates, maleic acid esters, and as coatability improvers, surfactants such as fluorine-based surfactants and ethyl cellulose polyalkylene ethers are typical. Examples thereof include nonionic activators.

When the photosensitive composition of the present invention is used to form an image-forming material, particularly a colored image-forming material, the colored photosensitive layer is a colored layer containing a colorant and a binder, and a photosensitive layer containing a photosensitive composition. It can also be divided into two layers. In this case, either layer may be disposed on the support side.

When the photosensitive composition of the present invention is used to form an 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. Besides, 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 depending on the type of the 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 can be used in the form of transferring an image to a material to be transferred. In this case, in order to efficiently perform transfer onto the material to be transferred and to facilitate peeling of the support after image transfer, that is, to improve image transferability and to form a cushion layer and an image forming layer (coloring) with the support. In order to improve releasability between the photosensitive layer and the photosensitive layer, the upper surface of the support may be processed or molded to form a cushion, or a cushion layer may be provided on the surface of the support, which will be described later.

The image forming method using the image forming material obtained by the production method of the present invention is such that 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 transferred. A transfer image is obtained by transferring to a material (for example, real paper).

When the image forming method using the image forming material obtained by the manufacturing method of the present invention is embodied as a multicolor image forming method, one of the basic methods is
It 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 transfer material, 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. A method of this kind is disclosed in JP-A-47-41830 and 59-97140.
No. 60-28649 and US Pat. No. 377511.
No. 3 etc.

In the image forming method using the image forming material obtained by the manufacturing method of the present invention, the image forming material 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 upper surface of the support is used as a cushion or a cushion layer is provided on the support in order to efficiently perform the transfer onto the transfer surface and facilitate the peeling of the support after the image transfer. . In the present invention, these are referred to as cushion layers. The thickness of the cushion layer is preferably in the range of 5 μm to 50 μm. The resin used for the cushion layer has a softening point of -30 ° C.
It is preferably about 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. Particularly preferred are polyolefins such as polyethylene and polypropylene, ethylene and vinyl acetate, ethylene and acrylate, ethylene copolymers such as ethylene and acrylic acid, polyvinyl acetate and vinyl acetate copolymer.

The polymer containing vinyl carboxylic acid ester as a polymerized unit contained in the cushion layer used in Reference 1 is a polymer having a vinyl carboxylic acid polymerized unit used in the above-mentioned photosensitive composition in the molecular structure. Among the molecular compounds, those in which the proportion of the polymerized portion derived from the carboxylic acid vinyl ester is 11% by weight or less of the whole polymer are used. The following copolymers can be used as the copolymer. An especially preferred polymer is an ethylene-vinyl acetate copolymer having a weight ratio of 90:10 to 92: 8.
Are particularly preferred.

Carboxylic acid vinyl ester polymerized units are 11
Specific Example of Polymer Containing Less Than% by Weight As a specific example of the organic polymer compound used in Reference 1, a copolymer of ethylene and vinyl acetate (11% by weight or less of vinyl acetate, for example, ethylene and vinyl acetate Weight ratio 90:10 copolymer, 92: 8 copolymer, 94:
6 copolymer), a copolymer of ethylene and vinyl propionate (a vinyl propionate content of 11% by weight or less, for example, a copolymer of ethylene and vinyl propionate having a weight ratio of 90:10, a copolymer weight of 92: 8). Coalesce, 94: 6 copolymer),
Copolymer of ethylene and vinyl versatate (11% by weight or less of vinyl versatate, for example, a copolymer of ethylene and vinyl versatate in a weight ratio of 90:10, 9
2: 8 copolymer, 94: 6 copolymer), ethylene / vinyl acetate / vinyl versatate copolymer (vinyl acetate and vinyl versatate total 11% by weight or less,
For example, a copolymer of ethylene, vinyl acetate and vinyl versatate having a weight ratio of 90: 5: 5, a copolymer of 90: 7: 3, a copolymer of 94: 3: 3), a copolymer of propylene and vinyl acetate. Polymers (vinyl acetate is 11% by weight or less, for example, a copolymer of propylene and vinyl acetate having a weight ratio of 90:10, a copolymer of 92: 8, a copolymer of 94: 6), styrene and vinyl acetate. Copolymer (11% vinyl acetate by weight
Below, for example, the weight ratio of styrene to vinyl acetate is 90: 1.
0 copolymer, 92: 8 copolymer, 94: 6 copolymer), vinyl chloride / vinyl acetate copolymer (vinyl acetate is 11% by weight or less, for example, vinyl chloride / vinyl acetate weight ratio) Is a 90:10 copolymer, a 92: 8 copolymer, 9
4: 6 copolymer), butyl acrylate / vinyl acetate copolymer (vinyl acetate is 11% by weight or less, for example, butyl acrylate / vinyl acetate weight ratio 90:10, 92: 8). And the copolymer of 94: 6), and the like.

As a method for providing a cushion layer on a support, especially the transparent support, (1) dissolving polyvinyl acetate, polyvinyl chloride, epoxy resin, polyurethane resin, natural rubber, synthetic rubber, etc. in an organic solvent. Using the prepared solution as an adhesive, these adhesives are applied on a support, dried by hot air or heating, and then a cover sheet is superposed and pressure-bonded under heating, so-called dry laminating method;

(2) a copolymer of ethylene and vinyl acetate,
A doctor blade on the support while using ethylene / acrylic acid ester copolymer, polyamide resin, petroleum resin, rosins, waxes or a mixture thereof as an adhesive and heating these adhesives as they are to keep them in a molten state. Method, roll coating method, gravure method, reverse roll method, etc., and then immediately laminating a cover sheet, heating at high temperature if necessary, and then laminating by cooling, so-called hot melt laminating method;

(3) A so-called extrusion laminating method in which polypropylene, polyethylene and the like are kept in a molten state and extruded onto a support by an extruder, and while the molten state is maintained, 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 and polypropylene, polyethylene or the like in a molten state is used, and two or more kinds of the support are formed on the support by one-time molding. A layer made of resin is formed, and while it is in a molten state, a cover sheet is pressure-bonded and laminated, a so-called coextrusion method or the like;

(5) In any of the above methods (1) to (4), the cover sheet is necessarily applied to the surface of the support after the cushion layer is provided on the support.

In Reference 3, a transfer image forming method comprising transferring an image layer formed on a transferable photosensitive material to an image receiving sheet material and then retransferring the image onto a permanent support (transferred material). In the above, the image receiving sheet material is a support and a first layer made of a first organic polymer substance provided thereon, and a second layer made of a second organic polymer substance further provided thereon. And an adhesive force P1 between the support and the first layer when the transferable image layer is transferred to the image receiving sheet material and then the image receiving sheet material and the transferable photosensitive material are peeled off, and the first layer And the adhesion P2 between the second layer and the second layer, and the adhesion P3 between the second layer and the image layer are larger than the adhesion P4 between the transferable image layer and the support of the image, and further the permanent support. Retransfer the image layer on top and peel off the image receiving sheet material and permanent support The adhesive force between the permanent support and the transferable image layer P5 and the P1 and the P2 are the P3 greater than or the P5, and the P1 and the P3 is the P2
In the colored image-forming material used in the transfer image-forming method, which has a larger thickness, the second layer made of the second organic polymer material preferably has a thickness of less than 0.08 μm. Such image forming materials and transfer image forming methods are described in JP-A-61-18953.
See No. 5.

In the image forming method of the present invention, the developer 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 that can be used include (1) sodium silicate, potassium silicate, potassium hydroxide, sodium hydroxide, lithium hydroxide, sodium di- or triphosphate or ammonium salt, sodium metasilicate, carbonic acid. Inorganic alkaline agents such as sodium 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

[0060]

[Chemical 3]

(5) Sulfonates of dibasic aliphatic ester (eg sodium sulfosuccinate dioctyl ester, sodium sulfosuccinate dihexyl ester etc.) (6) Formaldehyde condensate of alkylnaphthalene sulfonate (eg sodium dibutylnaphthalene sulfonate) Formaldehyde condensate and the like).

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

[0063]

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.

Comparative Example 1 A polyethylene terephthalate film having a thickness of 75 μm (Lumirror T-60, manufactured by Toray Industries, Inc.) was used, and a thickness of 25 μm.
Ethylene-vinyl acetate copolymer (EVAF
LEX P-1407, vinyl acetate content 14% by weight,
MFR = 15: manufactured by Mitsui DuPont Polychemical Co., Ltd.) was formed by an extrusion laminating method to prepare a support having a cushion layer. At this time, as a cover sheet for the cushion layer, a 50 μm single-sided matt polyethylene terephthalate film (Lumimat # 200S (manufactured by Panac Co.) was used as a matte surface (Ra = 0.40 μm [Pert]).
homer S5P: made by Perthen], GS
(60 °) = 8 [JIS-Z8741 digital variable angle gloss meter VG 1D type: manufactured by Nippon Denshoku Industries Co., Ltd.] was laminated at the same time so as to be in contact with the cushion layer.

The angle of the formed cover sheet of the support having the cushion layer with the cushion layer surface after peeling is 1
It was peeled off at an angle of 60 °. Table 1 shows the surface glossiness and the number of convex portions at this time.

Next, a colored photosensitive layer dispersion liquid having the following composition was prepared. [Colored Photosensitive Layer Dispersion] Esterification product of p-cresol novolac resin and naphthoquinone-1,2-diazido-4-sulfonic acid chloride 0.616 g Vinyl acetate-vinyl versatate copolymer (weight ratio 80:20, weight Average molecular weight 50,000, 50% methanol solution) 8.768 g Pigment below <Amount below> Methyl lactate 35.2 g <Pigment> Black: Carbon black MA-100 (manufactured by Mitsubishi Kasei Co.) 0.99 g Cyan: Lionol blue FG-7330 (manufactured by Toyo Ink Co., Ltd.) 0.55 g Magenta: Lyonol Red 6BFG-4219X (manufactured by Toyo Ink Co., Ltd.) 0.68 g Yellow: Rionol Yellow No. 1206 (manufactured by Toyo Ink Co., Ltd.) 0.68 g The above coating liquid was applied and dried so that the dry film thickness was 1.8 μm, and four color (four types) of photosensitive colored image forming materials were obtained.

A color-separating net positive film of each color was adhered to the polyethylene terephthalate film surface of the obtained four-color photosensitive colored image forming material, and image exposure was performed with a 4 kw metal halide lamp from a distance of 50 cm for about 60 seconds. Development was performed by immersing in a developing solution at 32 ° C. for 30 seconds and rubbing with a sponge to obtain four colored images. [Developer] Konica PS plate developer SDR 1 (manufactured by Konica) 40 ml Perex NB-L (surfactant: manufactured by Kao Atlas) 100 ml Distilled water 400 ml Next, image surface of black image and art paper (Tokubishi) Art: made by Mitsubishi Paper Mills Co., Ltd., and passed between a pair of nip rolls heated to 80 ° C. at a speed of 0.5 m / min under a pressure condition of 5 kgf / cm ² , The support was immediately peeled off. The peeling was easily performed at the interface between the cushion layer and the colored image, and the black image was transferred onto the art paper. Subsequently, the colored images were transferred in the order of cyan, magenta, and yellow to form a color proofing image of four colors on the art paper.

Only the colored image portion was transferred onto the art paper. That is, the paper surface of the non-image area was exposed, and no background stain was observed in the non-image area.

Regarding this color proofing image,
Printing expert 15 who is different from printed matter using the same manuscript / paper
Table 3 shows the results of human observation and evaluation, and the measurement results of the glossiness of the image area and the non-image area.

Example 1 A polyethylene terephthalate film (Lumirror T-60 # 5) having a thickness of 50 μm was used as a cover sheet for the cushion layer.
0: Ra = 0.15 μm [Perthometer S
5P: made by Perthen]), GS (60 °) = 170
[JIS-Z8741, Digital variable angle gloss meter VG
1D type: manufactured by Nippon Denshoku Industries Co., Ltd.] A color proofing image was prepared in the same manner as in Comparative Example 1, and the same evaluation was performed. The results are also shown in Table 3.

Example 2 Example 1 except that the peeling angle of the cover sheet was 80 degrees.
A color proofing image was prepared in the same manner as above, and the same evaluation was performed. The results are also shown in Table 3.

Example 3 After peeling the cover sheet and before applying the colored photosensitive layer, 10
A color proofing image was prepared and evaluated in the same manner as in Example 1 except that it was heated in an oven at 0 ° C for 1 minute. The results are also shown in Table 3.

Example 4 After peeling the cover sheet and before applying the colored photosensitive layer, 10
A color proofing image was prepared and evaluated in the same manner as in Example 1 except that it was heated in an oven at 0 ° C. for 2 minutes. The results are also shown in Table 3.

Example 5 After peeling the cover sheet and before applying the colored photosensitive layer, 10
3 k between a pair of nip rolls heated to 0 ° C. (surface roughness Ra of the roll in contact with the cushion layer Ra = 0.05 μm)
A color proofing image was formed and evaluated in the same manner as in Comparative Example 1 except that the film was passed at a speed of 0.5 m / min under a pressure of gf / cm ² . The results are also shown in Table 3.

Example 6 A color proofing image was prepared in the same manner as in Comparative Example 1, and then the image was heated to 100 ° C. with a pair of nip rolls (the surface roughness Ra of the roll in contact with the image surface was Ra = 0.1).
5) is 2 m / mi under a pressure of 3 kgf / cm ^2.
The same evaluation was carried out after passing at a speed of n. The results are also shown in Table 3.

Reference Example 1 An ethylene-vinyl acetate copolymer resin (EVAFLEX P-1407, vinyl acetate content 14% by weight, MFR = 15: manufactured by DuPont Mitsui Polychemicals) used for the cushion layer in Comparative Example 1 was used. At a temperature about 50 ° C lower than the synthesis temperature of P-1407, the reaction time was doubled or more, and the other conditions were the same as those of the ethylene-vinyl acetate copolymer resin (prototype resin-A, vinyl acetate content rate). A color proofing image was prepared in the same manner as in Comparative Example 1 except that the content was changed to 14% by weight and MFR = 15), and the same evaluation was performed. The results are also shown in Table 3.

Reference Example 2 The ethylene-vinyl acetate copolymer resin (EVAFLEX P-1407, vinyl acetate content 14% by weight, MFR = 15: manufactured by DuPont Mitsui Polychemicals) used for the cushion layer in Comparative Example 1 was replaced with ethylene-acetic acid. Vinyl copolymer resin (EV
A-25K, vinyl acetate content 11% by weight, MFR =
3.5: manufactured by Mitsubishi Petrochemical Co., Ltd.) A color proofing image was prepared in the same manner as in Comparative Example 1 and the same evaluation was performed. The results are also shown in Table 3.

Reference Example 3 The ethylene-vinyl acetate copolymer resin (EVAFLEX P-1407, vinyl acetate content 14% by weight, MFR = 15: manufactured by DuPont Mitsui Polychemicals) used for the cushion layer in Comparative Example 1 was replaced with ethylene-acetic acid. Vinyl copolymer resin (EM
-5822, vinyl acetate content 8% by weight, MFR = 2
2: made by Asahi Kasei Co., Ltd.) A color proofing image was prepared in the same manner as in Comparative Example 1, and the same evaluation was performed. The results are also shown in Table 3.

Comparative Example 2 A color proofing image was prepared in the case where the thickness of the second layer in Example 2 of JP-A-61-189535 was 0.20 μm, and the same evaluation was performed. The results are also shown in Table 3.

Comparative Example 3 A color proofing image was prepared and evaluated in the same manner as in Comparative Example 2 except that the thickness of the second layer in Comparative Example 2 was 0.10 μm. The results are also shown in Table 3.

Comparative Example 4 A color proofing image was prepared and evaluated in the same manner as in Comparative Example 2 except that the photosensitive colored image forming material of Comparative Example 2 was changed to that of Comparative Example 1. The results are also shown in Table 3
Shown in.

Reference Example 4 A color proofing image was prepared and evaluated in the same manner as in Comparative Example 2 except that the thickness of the second layer in Comparative Example 2 was changed to 0.07 μm. The results are also shown in Table 3.

Reference Example 5 A color proofing image was prepared and evaluated in the same manner as in Comparative Example 2 except that the thickness of the second layer in Comparative Example 2 was changed to 0.05 μm. The results are also shown in Table 3.

Reference Example 6 A color proofing image was prepared in the same manner as in Comparative Example 2 except that the thickness of the second layer in Comparative Example 2 was 0.03 μm, and the same evaluation was performed. The results are also shown in Table 3.

Reference Example 7 A color proofing image was prepared and evaluated in the same manner as in Comparative Example 2 except that the thickness of the second layer in Comparative Example 4 was changed to 0.03 μm. The results are also shown in Table 3. Example 7 The ethylene-vinyl acetate copolymer resin (EVAFLEX P = 1407, vinyl acetate content 14% by weight, MFR = 15: manufactured by DuPont Mitsui Polychemicals) used for the cushion layer in Comparative Example 1 was mixed with ethylene-vinyl acetate. Polymer resin (EVA-25K, vinyl acetate content 11% by weight, MF
R = 3.5: manufactured by Mitsubishi Petrochemical Co., Ltd., the cover sheet of the cushion layer is a polyethylene terephthalate film of 50 μm (Lumirror T-60, # 50: Ra = 0.15 μ)
m <Perthometer S5P: Perthen
Made>, GS (60 °) = 170 <JIS-Z8741,
Digital gonio gloss meter VG-1D type: manufactured by Nippon Denshoku Industries Co., Ltd.>), and the angle between the cover sheet of the support having the cushion layer formed and the cushion layer surface after peeling is 8
It was peeled off at 0 °. Surface gloss at this time,
Table 1 shows the number of convex portions.

A colored image-forming material was obtained using the obtained support having a cushion layer, a color proofing image was formed in the same manner as in Comparative Example 1, and the same evaluation was performed.
The results are also shown in Table 3. Example 8 The ethylene-vinyl acetate copolymer resin (EVAFLEX P = 1407, vinyl acetate content 14% by weight, MFR = 15: manufactured by DuPont Mitsui Polychemicals) used for the cushion layer in Comparative Example 1 was mixed with ethylene-vinyl acetate copolymer. Polymer resin (EVA-25K, vinyl acetate content 11% by weight, MF
R = 3.5: manufactured by Mitsubishi Petrochemical Co., Ltd., the cover sheet of the cushion layer is a polyethylene terephthalate film of 50 μm (Lumirror T-60, # 50: Ra = 0.15 μ)
m <Perthometer S5P: Perthen
Made>, GS (60 °) = 170 <JIS-Z8741,
Digital variable angle gloss meter VG-1D type: manufactured by Nippon Denshoku Industries Co., Ltd.>).

The formed cover sheet of the support having the cushion layer has an angle of 80 with the surface of the cushion layer after peeling.
It was peeled off at a temperature of °. Table 1 shows the surface glossiness and the number of convex portions at this time.

Next, a colored layer dispersion liquid and a photosensitive layer coating liquid having the following compositions were prepared. [Colored layer dispersion] -Vinyl acetate-vinyl versatic acid copolymer (weight ratio 80:20, weight average molecular weight = 50,000, 50% methanol solution) 10.0 g-Pigment below <Amount below> -Methyl lactate 35.2 g <Pigment> Black: Carbon black MA-100 (manufactured by Mitsubishi Kasei Co., Ltd.) 1.98 g Cyan: Rionol Blue FG-7330 (manufactured by Toyo Ink Co., Ltd.) 1.10 g Magenta: Rionol Red 6BFG- 4219X (manufactured by Toyo Ink Co., Ltd.) 1.36 g Yellow: Rionol Yellow No. 1206 (manufactured by Toyo Ink Co., Ltd.) 1.36 g [Photosensitive layer coating liquid] -Ester compound of p-cresol novolac resin and naphthoquinone-1,2-diazide-4-sulfonic acid chloride 0.616 g-Vinyl acetate-versatitic Vinyl acetate copolymer (weight ratio 80:20, weight average molecular weight = 50,000, 50% methanol solution) 8.768 g-methyl lactate 15.2 g The above-mentioned colored layer dispersion has a film thickness of 0.9 μm after drying. And then dried, and the photosensitive layer coating liquid was applied and dried thereon so that the film thickness after drying was 0.9 μm to obtain a 4-color photosensitive colored image forming material.

Using the photosensitive colored image forming material thus obtained, a color proofing image was prepared in the same manner as in Comparative Example 1 and the same evaluation was carried out. The results are also shown in Table 3.

[0090]

[Table 1]

[0091]

[Table 2]

* Measuring method and measuring instrument glossiness-Method: GS (60 °) according to JIS-Z8741 = Method 3 of JIS-Z8741 3 GS (75 °) = Method 2 of JIS-Z8741 Equipment: Digital variable angle glossiness Total VG-1D type (manufactured by Nippon Denshoku Industries Co., Ltd.) Surface roughness-Device: Perthometer S5P
(Made by Perthen)

* Printed matter printing machine-Mitsubishi DAIYA (manufactured by Mitsubishi Heavy Industries) Ink-Mark Five New (manufactured by Toyo Ink) Paper-Tokuryo Art (manufactured by Mitsubishi Paper Mills)

[0094]

[Table 3]

* Observation Evaluation Method and Rating Scale The difference between each of the four-color images obtained and the printed matter obtained from the same original document was shown to 15 skilled printing professionals for each item shown in the table on the following scale. The average value was shown in the table as the average opinion score.

[0096]   [Rating scale]       5-I don't know the difference from printed matter         ・ ・ ・ ・ ・ ・ ・ ・ ・ (Detection limit)       4-You can see the difference with printed matter, but do not worry         ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ (Allowable limit)       3-I am worried about the difference with the printed matter, but it does not get in the way         ・ ・ ・ ・ ・ ・ ・ ・ ・ (Patience limit)       2-Difference with printed matter       1-The difference with printed matter is very disturbing

[0097]

According to the present invention, it is possible to obtain a color proof that more closely resembles a printed matter, and in particular (1) the surface property of the image is closer to that of the printed matter, and (2) it is caused by the surface portion of the cushion layer. It is possible to provide a method for producing a colored image-forming material capable of obtaining a color proof similar to a printed matter while suppressing nonuniformity of an image area.

─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Takeo Akiyama 1 Sakura-cho, Hino-shi, Tokyo Konica Co., Ltd. (72) Inventor Tetsuya Masuda 1000 Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa Mitsubishi Kasei Co., Ltd. In-house (72) Inventor Hideaki Mochizuki 1000 Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa Mitsubishi Kasei Co., Ltd. (56) References JP-A-4-358151 (JP, A) JP-A-61-286858 (JP) , A) JP-A-4-37855 (JP, A) JP-A-3-48248 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03F 7/004 G03F 3/10 G03F 7/11 G03F 7/40

Claims (2)

(57) [Claims] 1. A cushion layer is provided on a support, a colored photosensitive layer containing a photosensitive composition and a colorant is provided on the cushion layer, and a colored image portion is formed by imagewise exposure and development treatment. A colored image-forming material for obtaining a transferred image by directly transferring only the colored image portion to a material to be transferred, which is a final image-receiving paper, without interposing a temporary image-receiving sheet. Average gloss of layer surface [GS
(60 °)] is 30 or more, in the production method for producing a colored image-forming material having a structure in which a colored photosensitive layer is provided on the cushion layer, a cover sheet is laminated on the cushion layer, and then the cover sheet is formed. In the step of peeling and coating the colored photosensitive layer on the peeled surface, the surface of the cover sheet on the cushion layer side has an average gloss [G
S (60 °)] 30 or more and a centerline average roughness (Ra) of 0.3 μm or less is used, and a method for producing a colored image-forming material is characterized. 2. The method for producing a colored image-forming material according to claim 1, wherein the surface of the cushion layer is mirror-finished after the cover sheet is peeled off and before the colored photosensitive layer is applied.