JPH04223471A - Image forming material - Google Patents

Abstract

PURPOSE:To prevent the adhesion of the outermost layer of an image forming material to the surface of a substrate or a back layer, to ensure satisfactory thermal transferability and to easily identify the front and rear sides by incorporating hollow particles into the outermost layer of the image forming material. CONSTITUTION:A back layer, a substrate, an undercoat layer and a photosensitive resin compsn. layer contg. a dye or pigment or a coloring material layer contg. a dye or pigment and the photosensitive resin compsn. layer are laminated or a protective layer is further formed. The substrate is made of a flexible material having chemical and thermal stability and hollow particles are incorporated into the protective layer or into the photosensitive resin compsn. layer which is the outermost layer in the case where the protective layer is not formed. The adhesion of the outermost layer of the resulting image forming material to the surface of a substrate or a back layer is prevented.

Description

[0001] The present invention relates to a negative or positive image forming material used for printing plates, return films, color test prints, color proofs, dry film resists, etc. It is something. [0002] Image-forming materials conventionally used in various fields such as printing, photography, and microfabrication of metals, etc. are basically supported (temporary supports in transfer-type image-forming materials). It consists essentially of a photosensitive resin layer made of a photopolymer provided thereon. For example, a transfer type image forming material (photosensitive transfer sheet) having such a configuration is used for color proofing. Color proofing sheets for color proofing are produced by exposing the image forming material through a resolving mesh film for each color plate, developing it to form a decomposed image on a photosensitive resin layer, and observing this sheet as it is, or by using this decomposed image. The image can be obtained by transferring the image onto any support (image receiving surface). Moreover, a multicolor image can also be obtained by repeating the process of transferring a separated image of another color onto the above-mentioned support. Furthermore, in order to simplify the transfer process, there are also known image forming materials in which a release layer is provided between the support and the photosensitive resin layer (Japanese Patent Publication No. 49-441, Japanese Patent Application Laid-open No. 47-1988). (See Publication No. 41830, etc.). In any case, the image-forming material essentially consists of a support and a photosensitive resin layer, and if necessary, a protective layer is provided on the photosensitive resin layer, but its production is usually difficult. It is done by law. That is, after coating a coating liquid for a photosensitive resin layer (hereinafter abbreviated as photosensitive liquid) on a long sheet-shaped support made of polyethylene terephthalate or the like, it is heated and dried at a constant temperature (drying step), It is manufactured by continuous winding (winding process). If a protective layer is provided, once the film is rolled up, a coating solution for the protective layer is applied onto the photosensitive resin layer and dried, or
It is manufactured by applying a photosensitive liquid and drying it, then further applying a protective layer without winding it up. Further, the wound image forming material is subjected to post-processing such as cutting into a desired standard size (processing step), and is manufactured into a product. [0004] However, the surface of the support of such image forming materials, printing plates, return films, dry film resists, etc., or the surface of the back layer and photosensitive resin layer provided on the surface, or the surface of the protective layer. The disadvantage was that adhesion with other materials was likely to occur. In particular, the photopolymerizable photosensitive resin layer basically consists of a photopolymerizable monomer, a photopolymerization initiator, and an organic polymer binder, and the monomer acts as a kind of plasticizer for the organic polymer binder. In order to function, the photopolymerizable photosensitive resin layer is formed in a slightly soft state. Although this is necessary in order to improve image formation, on the other hand, it makes it easier for the above-mentioned adhesion phenomenon to occur. Furthermore, an adhesion phenomenon may also occur in an image forming material whose uppermost layer is a photosensitive resin layer containing a phenol resin and a quinonediazide compound. As a method to overcome these drawbacks, a method is known in which a coarse matting agent is added to the photosensitive resin layer and/or the protective layer. However, in this method, if enough matting agent is added to completely prevent adhesion, the image cannot be sufficiently pressed and thermal transfer may be inhibited. [0005] An object of the present invention is to prevent adhesion between the surface of a support or a back layer and the surface of a photosensitive resin layer or a protective layer, or to improve image quality due to good thermal transferability. It is an object of the present invention to provide an image forming material which can form an excellent image and is also easy to handle since it has good front and back discrimination. [Means for Solving the Problems] An object of the present invention is to provide an image forming material having at least a photosensitive resin layer on a support, which contains hollow particles in the uppermost layer on the side of the photosensitive resin layer. An image forming material characterized in that, or an image forming material having at least a photosensitive resin layer on a support, at least one of the layers that becomes the outermost layer after the image forming material is developed contains hollow particles. This was achieved by an image forming material characterized by: A typical image forming material of the present invention includes a back layer, a support, an undercoat layer, a photosensitive resin composition layer containing a dye or pigment, or a color material layer containing a dye or pigment and a photosensitive resin. Although the structure is such that a composition layer is laminated and a protective layer is further provided, the structure is not limited to this. For example, there may be no back layer and/or protective layer, and various intermediate layers other than the undercoat layer may be provided between the support and the photosensitive resin composition layer. The image forming material of the present invention having the above structure can be produced, for example, by the method described below. As the material for the support, a substance that is chemically and thermally stable and has flexibility is used. It may be transparent to actinic light if necessary. Specifically, polyolefins such as polyethylene and polypropylene, polyvinyl chloride,
Examples include polyvinyl halides such as polyvinylidene chloride, cellulose derivatives such as cellulose acetate, nitrocellulose, and cellophane, polyamides, polystyrene, polycarbonates, and polyimides. Among these, particularly preferred is a biaxially oriented polyethylene terephthalate film, which is excellent in dimensional stability and transparency. [0008] A back layer can be provided on the surface of the support opposite to the side on which the photopolymerizable photosensitive resin layer is provided. An example of the back layer is a layer in which a matting agent is contained and supported in acetyl cellulose in a dispersed state. Examples of acetylcellulose include monoacetylcellulose, diacetylcellulose, triacetylcellulose, and acetylbutylcellulose. The degree of acetylation (degree of acetylation) of acetylcellulose is preferably in the range of 40 to 60%, and the average degree of polymerization is preferably in the range of 50 to 400. Examples of matting agents include fine particulate inorganic compounds such as silicon dioxide (including colloidal silica), aluminum oxide, aluminum silicate, aluminum hydroxide, titanium dioxide, calcium carbonate, and zinc oxide, and solvent-insoluble compounds such as crosslinked polystyrene. Examples include organic polymers in the form of fine particles. The average particle size of these matting agents varies depending on the thickness of the back layer, but is between 0.005 and 10μ.
It is preferably in the range of m. The above matting agents may be used alone or in combination of two or more. The ratio of acetylcellulose and matting agent is such that the content ratio of matting agent to acetylcellulose is 1 to 60% by weight.
It is preferable to prepare it so that it falls within the range of . If the content ratio of the matting agent exceeds this range, the adhesiveness between the back layer and the support may become insufficient. In forming the back layer, first, the acetyl cellulose and a matting agent are mixed using a suitable solvent to prepare a coating solution. Examples of the solvent in this case include ketones such as acetone, methyl ethyl ketone, and cyclohexane; acetate esters such as methyl acetate and ethyl acetate; ethers such as methyl cellosolve, dioxane, and tetrahydrofuran; and methylene chloride and diacetone alcohol. I can do it. These may be used alone or in combination.
It may be used as a mixed solvent of more than one species. The back layer can be formed by applying the above-mentioned coating solution onto a support using a conventional method and drying it. Incidentally, an etching agent such as resorcinol or an antihalation agent may be added to the coating liquid, if necessary, for the purpose of increasing the adhesion to polyethylene terephthalate (support). The thickness of the back layer is generally preferably in the range from 0.01 to 5 .mu.m, particularly preferably from 0.1 to 0.5 .mu.m. Next, it is preferable to provide an undercoat layer on the other side of the support. The composition and forming material of the undercoat layer provided on the support are also already known. When the undercoat layer has a release function, it is called a release layer, but the material forming the release layer is generally non-adhesive at room temperature.
It is selected from organic polymers that exhibit adhesiveness and fusion properties when heated and can be peeled off from the temporary support. The materials for forming the release layer are also mentioned in the various publications mentioned above, but specifically, polyacrylic esters, acrylic ester copolymers, polymethacrylic esters, methacrylic ester copolymers, and polyacrylic esters are used. Acrylamide, acrylamide copolymer, polyvinyl acetate, vinyl acetate copolymer, polyvinyl chloride, vinyl chloride copolymer, polyvinylidene chloride,
Vinylidene chloride copolymer, polystyrene, styrene copolymer, ethylene copolymer (e.g., ethylene/vinyl acetate copolymer, ethylene/acrylic acid ester copolymer,
(ethylene/vinyl chloride copolymer, ethylene/acrylic acid copolymer), polyvinyl acetal (e.g., polyvinyl butyral, polyvinyl formal), polyester resin, polyamide resin (e.g., nylon, copolymerized nylon), various rubbers (e.g., synthetic rubber, chlorinated rubber),
and polyolefins (eg, polyethylene, polypropylene). The material forming the release layer may be one of the resins (polymer substances) mentioned above, or may be any mixture thereof. Furthermore, the release layer may be composed of two or more layers. Furthermore, various additives such as tackifying substances and plasticizers may be included if desired. To form a release layer on the support, a solution of the above-mentioned polymeric substance is prepared, and this solution is applied as a coating solution onto the temporary support by a conventional method and dried, or the polymeric substance is hot-melted. Alternatively, a method may be used in which a film made of the polymeric material is laminated onto a temporary support. The thickness of the release layer is preferably in the range of 0.2 to 10 μm. [0010] If necessary, a barrier layer is provided on the release layer. There are no particular limitations on the material for forming the barrier layer, but examples include polyacrylic ester, acrylic ester copolymer, polymethacrylic ester, methacrylic ester copolymer, polyacrylamide, acrylamide copolymer, and polyvinyl chloride. , vinyl chloride copolymer,
Polyvinylidene chloride, vinylidene chloride copolymer, polystyrene, styrene copolymer, ethylene copolymer (ethylene/vinyl acetate copolymer, ethylene/acrylic acid ester copolymer, ethylene/vinyl chloride copolymer, ethylene/acrylic) Select from organic polymers such as acid copolymers, etc.), polyvinyl acetals (polyvinyl formals, etc.), polyester resins, cellulose resins, various rubbers (synthetic rubbers, chlorinated rubbers, etc.), and polyolefins (polyethylene, polypropylene, etc.) However, these can be used alone or in any combination. Further, the barrier layer may be composed of two or more layers, and may contain various additives such as tackifying substances and plasticizers, if desired. To form a barrier layer on the release layer, these organic polymers are treated with a hydrocarbon solvent (toluene,
xylene, cyclohexane, etc.), halogenated hydrocarbon solvents (methyl chloride, dichloromethane, 1,2-dichloroethane, etc.), ketone solvents (acetone, methyl ethyl ketone, etc.), ester solvents (methyl acetate, ethyl acetate, etc.)
Prepare a coating solution by dissolving it in a solvent such as propyl acetate, etc.
The method is to apply it on the release layer and dry it using the usual method. The barrier layer has a function of preventing coloring agents such as dyes from being absorbed from the upper layer, and it is preferable to use a solvent having a polarity different from that of the coating solvent for the upper and lower layers. The thickness of the barrier layer is preferably in the range of 0.2 to 10 μm. [0011] A photosensitive resin layer is provided on the release layer or on the barrier layer overlaid on the release layer. When the photosensitive resin layer is a photopolymerizable photosensitive resin layer, usually,
A monomer compound such as a vinyl monomer or vinylidene compound that has a boiling point of 150°C or higher at normal pressure and can form a photopolymer by addition polymerization, an organic polymer binder, and a photopolymerization initiator that is activated by actinic rays. A thermal polymerization inhibitor is added as necessary. The vinyl monomer or vinylidene compound that can be used to form the photopolymerizable photosensitive resin layer is preferably, for example, an unsaturated ester of polyol, particularly an ester of acrylic acid or methacrylic acid. Specific examples include ethylene glycol diacrylate,
Glycerin triacrylate, polyacrylate, ethylene glycol dimethacrylate, 1,3-propanediol dimethacrylate, polyethylene glycol dimethacrylate, 1,2,4-butanetriol trimethacrylate, trimethylolethane triacrylate,
Pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol polyacrylate, 1,3-propanediol diol acrylate,
1,5-pentanediol dimethacrylate, 200~
Mention may be made of bisacrylates, bismethacrylates and similar compounds of polyethylene glycol with a molecular weight in the range of 400. As the monomer compound, unsaturated amides can also be used, examples of which include unsaturated amides of acrylic acid and methacrylic acid having α,ω-diamines and ethylene bismethacrylamide. The alkylene chain of the unsaturated amide may be open by carbon atoms. However, the photopolymerizable monomer is not limited to these compounds. Examples of the photopolymerization initiator include benzophenone, Michler's ketone [4,4'-bis(dimethylamino)benzophenone], 4,4'-bis(diethylamino)benzophenone, and 4-methoxy-4'-dimethylaminobenzophenone. Phenone, 2-ethylanthraquinone,
Aromatic ketones such as 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 dimer, 2-(o-chlorophenyl)
-4,5-(m-methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)
-4,5-diphenylimidazole dimer, 2-(p-
methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4-di(p-methoxyphenyl)-5-phenylimidazole dimer, 2-(2,4-dimethoxyphenyl)- 4,5-diphenylimidazole dimer,
2-(p-methylmercaptophenyl)-4,5-diphenylimidazole dimer, and U.S. Pat. No. 3,479
, No. 185, No. 3,784,557, British Patent No. 1,0
2, as described in each specification of No. 47,569,
Mention may be made of 4,5-triary-limidazole dimers. [0013] As the organic polymer binder, vinyl polymer substances are particularly preferred from the viewpoint of compatibility with the above-mentioned monomer compounds and photopolymerization initiators. Examples of vinyl polymer substances include polyvinyl chloride, polyacrylic acid, polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, polymethacrylic acid, polymethyl methacrylate, polyvinyl ether, polyvinyl acetal, and these. Various materials such as copolymers may be mentioned, but the material is not limited thereto. Here, the monomer compound and
The proper mixing ratio of the organic polymer binder varies depending on the combination of the monomer compound and the organic polymer binder used, but it is generally preferably in the range of 1:10 to 2:1 (weight ratio). Further, at this time, the amount of the photopolymerization initiator added is preferably in the range of 0.01 to 20% by weight based on the weight of the monomer compound used. Examples of the thermal polymerization inhibitor include p-methoxyphenol, hydroquinone, alkyl- or aryl-substituted hydroquinone, tert-butylcatechol, pyrogallol, naphthylamine, β-naphthol,
Mention may be made, without limitation, of phenathiazine, pyridine, nitrobenzene, o-torquinone, aryl phosphite. In addition, when the photosensitive resin layer is a photo-dissociable resin layer, US Pat. No. 2,766,
Orthoquinonediazide compounds described in No. 118, No. 3,647,443, etc., JP-A-56-1734
Examples include compounds having an orthoester group in the main chain described in No. 5, and compounds having a silyl ether group in the main chain described in JP-A-60-37549. In addition, methods and materials described in Japanese Patent Application No. 62-97091 can also be used. In this case, an organic polymer binder is not necessarily required, but a novolac type phenolic resin or the like can be used. The binder is about 40% of the photo-labile resin layer.
It can be used in a range of 90% by weight. The thickness of the photosensitive resin layer is generally in the range of 0.2 to 150 μm, preferably in the range of 0.3 to 100 μm. For details on the materials of these photosensitive resin layers and their formation methods, see, for example, Japanese Patent Publications Nos. 46-15326 and 46-35.
No. 682, JP-A-47-41830, JP-A No. 48-933
No. 37, No. 49-441, No. 51-5101, No. 5
It is described in various publications such as No. 9-97140. The effects of the present invention are particularly remarkable when the photosensitive resin layer has a hardness and a softening point determined by the Vicat method of 80° C. or lower, particularly 60° C. or lower. When a colored substance is used, the colored substance may be contained in the photosensitive resin layer, or may be contained in a separate coloring material layer. The coloring material layer can be provided either above or below the photosensitive resin layer, but from the viewpoint of the sensitivity of the photosensitive resin layer in the image exposure process, it is preferable to provide the photosensitive resin layer on top of the coloring material layer. preferable. Furthermore, known pigments and dyes can be used as the coloring substances. Details of the coloring substance and the coloring material layer are disclosed in, for example, Japanese Unexamined Patent Publication No. 59-97140. Furthermore, the image forming material of the present invention may be provided with a protective layer having low oxygen permeability in order to prevent a decrease in sensitivity due to oxygen. The protective layer is made of, for example, polyvinyl alcohol, polyvinyl acetate, methyl vinyl ether/maleic anhydride copolymer, polyvinylpyrrolidone,
It can be formed by applying and drying a solution of a polymeric substance such as gelatin or gum arabic. The thickness of the protective layer is 0.1 to 5 μm, preferably 0.2 to 3 μm.
m, more preferably 0.2 to 2 μm. The hollow particles used in the present invention are added to this protective layer, or to the photosensitive resin layer which becomes the uppermost layer when no protective layer is provided. This prevents adhesion to the back side of the support or the back layer. It can also be added to the release layer or barrier layer described above. When the image forming material is developed, the protective layer is removed and an image is formed using the photosensitive resin layer. During this development, if the non-image area of the release layer is removed at the same time, the hollow particles must be contained in the photosensitive resin layer, but if the non-image area of the release layer remains, When a barrier layer is provided on the layer, the hollow particles may be contained in at least one of the photosensitive resin layer and the release layer. This improves slipperiness, making it easy to align the image forming material and having excellent thermal adhesion. The average particle size of the preferred hollow particles is about 0.
．． 01 to 20 μm, particularly preferably about 0.01 to 20 μm
It is 1 μm. Such hollow particles are manufactured by Japan Synthetic Rubber (
JSR Hollow Particle SX 863 (A), SX from Co., Ltd.
864 (B), SX 865 (B), VONCOAT EXP PP-2 from Dainippon Ink Co., Ltd.
It is commercially available under the names such as 07S, and the synthesis method is described in the Abstracts of the 6th Polymer Microsphere Symposium (November 8 to November 10, 1990, Fukui City), pp. 39-42, 51 - pages 54, 55-56, 119-122, Proceedings of the Society of Polymer Science Vol. 38 No. 11 395
9-3961 (1989), Color Materials Association Journal Vol. 61
No. 9, pp. 494-508 (1988), etc. can be applied. These hollow particles can be used by being dispersed in an organic solvent-based coating solution for the photosensitive resin layer or protective layer, or in the case of an aqueous coating solution, they can be emulsified and dispersed. can. The amount added is 1% by weight or more based on the binder in the top layer (however, if the top layer is a photosensitive resin layer, based on the total amount including the monomer compound or photodissociation compound in addition to the binder). 60
It is added in an amount of about 5% to 40% by weight, more preferably about 10% to 30% by weight. The present invention will be explained in more detail below based on Examples, but the present invention is not limited thereto. Examples Example 1 A solution having the following composition was prepared as a coating solution for forming a back layer. Coating liquid for back layer Resorcin (etching agent)
2.8
Kg diacetylcellulose (degree of acetylation: 55+0.5
%, average degree of polymerization: 160 Acetate Flex V-AC, manufactured by Daicel Corporation) 0.
3Kg silicon dioxide (average particle size: 40nm, T
T-600, manufactured by Nippon Aerosil Co., Ltd.)


0.1Kg methanol

8Kg
Methyl ethyl ketone

30Kg Apply this coating solution to a polyethylene terephthalate film (support, thickness: 100μm, length:
2000m) and dry it (drying temperature: 12cm).
0° C.) to provide a back layer consisting essentially of diacetyl cellulose and silicon dioxide with a dry thickness of 0.3 μm, and then the film was wound up. Next, a solution having the following composition was prepared as a coating solution for forming a release layer. Alcohol-soluble polyamide (CM-8000, manufactured by Toray Industries, Inc.) “η” = 23 cps (20°C, 10% by weight
Methanol solution) 7.2g Polyhydroxystyrene (Resin M, manufactured by Maruzen Sekiyu Co., Ltd., average molecular weight: 55
00)

1.8g methanol

400g methyl cellosolve

100g UV absorber

2.0g of this coating solution was uniformly applied onto a 100 μm thick polyethylene terephthalate film and dried to a dry film thickness of 0.5 μm.
A release layer of μm was provided. Next, a solution having the following composition was prepared as a coating solution for forming a photosensitive resin layer. In this case, a coloring material dispersion having the following composition was separately prepared and mixed. Colorant dispersion Colorant

9.8Kg Benzyl methacrylate/methacrylic acid copolymer (molar ratio: 72/27,
Intrinsic viscosity of methyl ethyl ketone solution at 25°C: 0.12 cps)

16.4Kg
Methyl ethyl ketone

36.9Kg Methyl cellosolve acetate

36.9Kg Here, the coloring materials are yellow: Seika First Yellow H-0755 (Dainichiseika Co., Ltd.) Magenta: Seika First Carmine
1483 (Dainichiseika Co., Ltd.) Cyanine: Cyanine Blue 4920 (Dainichiseika Co., Ltd.)
Black: Carbon black (MA-100, manufactured by Mitsubishi Chemical Industries, Ltd.) was used. The dispersion liquid was prepared for 6 hours using a test dispersion machine (Paint Sheaker, manufactured by Toyo Seiki Co., Ltd.). The coating solution for the photosensitive resin layer was stirred for 10 minutes and then subjected to ultrasonic dispersion for 10 minutes. Coating liquid for photosensitive resin layer Coloring material dispersion liquid

24Kg methyl ethyl ketone

15Kg Methyl cellosolve acetate
7.4Kg
Benzyl methacrylate/methacrylic acid copolymer (
Molar ratio: 72/27, intrinsic viscosity of methyl ethyl ketone solution at 25°C: 0.12 cps)


4.5Kg Pentaerythritol Tetraacrylate
5.5Kg Michler Ketone

0.15Kg 2,
2'-bis(o-chlorophenyl)-4,4',5,5
'-tetra phenylbiimidazole
0.15Kg silicon dioxide (66
, manufactured by Fuji Davison Co., Ltd.) 0.
4 kg [0024] The thus prepared coating solution for forming a photosensitive resin layer is applied to the surface of the support opposite to the above-mentioned back layer, and dried (drying temperature: 100°C) to obtain a dry film thickness. 2
．． A 4 μm photosensitive resin layer was provided and wound up. The wound roll was left in an atmosphere of 25° C. and 65% RH for one week. Separately, a coating solution for forming a protective layer having the following composition is prepared, and this coating solution is applied onto the photosensitive resin layer.
Dry (drying temperature: 100℃) to a dry film thickness of 1.5μ
A protective layer of m was provided. Coating liquid for protective layer Polyvinyl alcohol (GL-05H, manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd.) 6Kg Water

97Kg
methanol

3Kg Hollow particles (manufactured by Japan Synthetic Rubber Co., Ltd., SX 864 (B)) 0
．． 9 kg In this way, an image forming material consisting of a back layer, a support, a release layer, a photosensitive resin layer and a protective layer was prepared in this order and designated as Sample I. Comparative Example 1 Thyroid 15 was added instead of the hollow particles added to the protective layer.
An image forming material was prepared as Sample II in the same manner as in Example 1, except that the same amount of 0 (silica particles, 2.0 μm, manufactured by Fuji Davison) was used. Comparative Example 2 An image forming material was prepared in the same manner as in Example 1, except that the hollow particles in the protective layer were removed, and was designated as Sample III. Evaluation of image-forming materials (1) Adhesiveness For each of the image-forming materials obtained, the back layer and the protective layer were stacked so that they overlapped, and the layers were heated at 40° C. and 70% RH for 30 minutes.
After leaving it for a day, the situation of adhesion was examined. 5x5cm
Five samples were cut into pieces, and a 2 kg weight was used as the load. (2) Thermal transferability Four color image forming materials were subjected to image exposure for 60 seconds using a 1 Kw ultra-high pressure mercury lamp P-607FW (manufactured by Dainippon Screen Mfg. Co., Ltd.) using corresponding color separation masks. After that, automatic development was performed at 31°C for 34 seconds using a 5-fold dilution of color art developer CA-1 (product name: Fuji Photo Film Co., Ltd.) (color art processor CA-600P).
: manufactured by Fuji Photo Film Co., Ltd.). In this way, a four-color proofing sheet that faithfully reproduced the color separation mask was obtained. Apart from that, the thickness is 100
The following formulation (i) (for forming the first layer) and formulation (ii) are applied on a μm biaxially stretched polyethylene terephthalate film.
Coating liquids (for forming the second layer) were prepared, and the layers were sequentially coated to dry film thicknesses of 1.0 μm and 20 μm, respectively, to prepare an image-receiving sheet. Prescription (i) Polyvinyl chloride (Zeon 25, manufactured by Nippon Zeon Co., Ltd.) 10.0 g Methyl ethyl ketone
24
0g cyclohexanone

60g prescription (ii) Methyl methacrylate polymer (average molecular weight: 100
000, manufactured by Wako Pure Chemical Industries, Ltd.)


90g Pentaerythritol Tetraacrylate
90g Michler's Ketone

0.51g benzophenone

3.18g paramethoxyphenol
0.09g methyl ethyl ketone

220g [0031] Next, first stack the black color proofing sheets so that the image side is in contact with the film surface of the image-receiving sheet, and laminate them using a color art transfer machine CA-600T (manufactured by Fuji Photo Film Co., Ltd.). conduct,
Thereafter, the support of the color proofing sheet was peeled off, and a black image was transferred onto the image-receiving sheet. Next, transfer was performed on the remaining three color proofing sheets while aligning the positions to obtain an image receiving sheet on which halftone dot images of four colors were transferred. Next, the image-receiving sheet onto which the four-color image was transferred was placed on the art paper and laminated using the transfer machine described above, and then the support of the image-receiving sheet was peeled off to form a color image on the art paper. Finally, P-
Full exposure for 120 seconds with 607FW printer (post exposure)
to obtain the final image. These steps were performed at varying lamination temperatures and the quality of the final images was evaluated. It can be used practically if the lamination temperature is 125℃ or less, but
The temperature is preferably 120°C or lower, more preferably 110°C or lower. (3) Distinguishability of front and back sides The completed image forming materials were placed next to each other with the front and back sides reversed, and the discriminability of front and back sides was visually determined under a fluorescent lamp. Class A Level B: Sufficient distinguishability Level C: Not sufficient, but practically usable
Table 1 shows the evaluation results obtained for items (1) to (3) of insufficient level or higher. [0033] As is clear from the results, the image forming material of the present invention containing hollow particles in the uppermost layer had no adhesion and was excellent in distinguishing front and back sides. Further, this material had no cloudiness or surface stains, and had a clean surface as an image forming material. Example 2 An image forming material (sample IV) and an image receiving sheet were created. Example 3 An image forming material (sample V ) and an image receiving sheet was created. Comparative Example 3 The image forming material (III) prepared in Comparative Example 1 was used. Comparative Example 4 An image forming material (Sample VI) was prepared in the same manner as in Example 2 except that Thyroid 150 (silica particles) was used instead of the hollow particles. Comparative Example 5 An image forming material (Sample VII) and an image receiving sheet were prepared in the same manner as in Example 3, except that silica particles (66, manufactured by Fuji Davison Co., Ltd.) were used instead of hollow particles. Evaluation of image-forming materials (4) Smoothness during image alignment Transfer the first color image to the image-receiving sheet, and transfer the second color image (here, the image refers to an original having a 50% mesh area). The ease of positioning when transferring images (images on a developed film created by the above process) and the ease with which the films slip on each other was investigated using the following method. The image receiving sheet with the first color image transferred and the image forming material with the image formed are each 5 cm x 1
Cut the image receiving sheet to 0 cm, overlap the image receiving sheet with the film surface and image surface aligned, and pull the upper sheet with a strain gauge.
The tension was measured. If this value is 100 g or less, it is practical, but it is preferably 50 g or less. The results are shown in Table 2. [Table 2] [0042] As is clear from this result, when hollow particles are added to the release layer or photosensitive layer that becomes the outermost layer after development of the image forming material, alignment becomes difficult due to good slipperiness. On the other hand, it can be seen that the thermal adhesion is excellent when compared with the case where a normal silica matting agent is added. Example 4 The release layer coating solution prepared in Example 1 was uniformly applied onto a polyethylene terephthalate film having a thickness of 100 μm and dried to provide a release layer having a dry thickness of 0.5 μm. Next, a solution having the following composition was prepared as a coating solution for forming a barrier layer. Polymethyl methacrylate (average molecular weight: 1000
00) 3g methyl ethyl ketone
80g
Methyl cellosolve acetate

20 g of this coating solution was uniformly applied to the above coating layer and dried to provide a barrier layer having a dry thickness of 0.5 μm. In order to form the coloring material layer, a mother liquor A for pigment dispersion having the following formulation was prepared. Mother liquor A Styrene/maleic acid copolymer resin (Oxilac S
H-101, manufactured by Nippon Shokubai Kogyo Co., Ltd.)

20g
Methyl ethyl ketone

80g Next, using mother liquor A, 4 of the following composition
Color pigment dispersions were prepared. Pigment dispersion for forming yellow coloring material layer Mother liquor A

110g methyl ethyl ketone

40g methyl cellosolve acetate
25g Seika First Yellow H-0755 (manufactured by Dainichiseika Co., Ltd.) 24.4g Pigment dispersion liquid for forming magenta color material layer Mother liquor A

110g methyl ethyl ketone

40g methyl cellosolve acetate
25g
Seika First Carmine 1483 (manufactured by Dainichiseika Co., Ltd.) 12.2g [0047] Pigment dispersion liquid for forming a cyan coloring material layer Mother liquor A

110g methyl ethyl ketone

40g methyl cellosolve acetate

25g Cyanine Blue 4920 (
(manufactured by Dainichiseika Co., Ltd.) 12
．． 2g [0048] Pigment dispersion for forming black color material layer
Mother liquor A

110g methyl ethyl ketone

40g methyl cellosolve acetate
25g
Mitsubishi Carbon Black MA-100 (Mitsubishi Chemical Industries (
(manufactured by Toyo Seiki Co., Ltd.) A 12.2 g dispersion was prepared by stirring for 3 hours using a test dispersion machine (Paint Sheaker, manufactured by Toyo Seiki Co., Ltd.). Separately, a diluted pigment dispersion liquid having the following formulation was prepared. Methyl ethyl ketone

550g methyl cellosolve acetate

130g Fluorine surfactant (Florad FC-430 manufactured by Sumitomo 3M) 2g
After diluting the pigment dispersion liquids of four colors with the above-mentioned diluting solution at the weight ratio shown in Table 4, stirring operation was performed for 10 minutes and ultrasonic dispersion operation was performed for 10 minutes to obtain a coloring material layer coating liquid. This coloring material layer coating liquid was applied to Toyo Roshi No. 63
After filtration, it was applied using a wheeler onto four supports provided with a release layer and a barrier layer, and dried at 100°C for 2 minutes to form coloring material layers for each of the four colors shown in Table 3. . [0051] [Table 3] [0052] Further, on the color material layer of each of the four colors, a positive type photosensitive station having the composition shown below was applied to the above No. 3 color material layer. After filtering through a 63 filter, the mixture was applied using a wheeler and dried at 100° C. for 2 minutes to form a photosensitive layer. 1,2-naphthoquinone diazide (2
)-Diazido-4-sulfonic acid-pt-
Octyl phenyl ester
1.36g Novolac type phenol formaldehyde resin (PR-
50716, manufactured by Sumitomo de Ures Co., Ltd.)

2.86g Abietic acid

0.32g
Fluorine-based surfactant (Megafac F-104, manufactured by Dainippon Ink and Chemicals Co., Ltd.)

0.05g
n-propyl acetate

28g toluene

67g hollow particle SX864(B)
0.2
gThe coating amount of the above photosensitive layer coating liquid (in terms of solid content)
was 0.8 g/m2, and the layer thickness of the photosensitive layer was 0.8 μm. In this way, four color imaging materials (sample V
III) was created. Comparative Example 6 Sample IX was prepared in the same manner as in Example 4 except that hollow particles were not added to the photosensitive layer. Comparative Example 7 Sample X was prepared in the same manner as in Example 4 except that the same amount of Thyroid 150 was added to the photosensitive layer instead of the hollow particles. These samples were evaluated using the method described above. The results are shown in Table 4. [Table 4] [0056] As is clear from these results, according to the present invention,
The image forming material containing hollow particles in the top layer has no adhesion, has excellent front and back discrimination, and has better thermal adhesion than when a normal silica matting agent is used. I understand. Example 5 Image-forming material XI was prepared in the same manner as in Example 4, except that 0.2 g of hollow particles was added to the barrier layer and the hollow particles were removed from the photosensitive layer, and transferred to an image-receiving sheet. Comparative Example 8 Sample IX prepared in Comparative Example 6 was used. Comparative Example 9 Sample XII was prepared in the same manner as in Example 5 except that the same amount of Thyroid 150 was added to the barrier layer instead of the hollow particles. Table 5 shows the results of evaluating these samples. [0060] [Table 5] [0061] As is clear from these results, adding hollow particles to the release layer has good slipperiness and makes positioning easier; on the other hand, compared to using a regular silica matting agent, It can be seen that the thermal adhesion is excellent.

Claims (2)

[Claims] 1. An image forming material comprising at least a photosensitive resin layer provided on a support, wherein the uppermost layer on the side of the photosensitive resin layer contains hollow particles. 2. An image forming material comprising at least a photosensitive resin layer on a support, characterized in that at least one of the layers that becomes the outermost layer after the image forming material is developed contains hollow particles. image-forming materials.