JP3046163B2 - Photosensitive material for image transfer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light-sensitive material for forming a transferred image by utilizing a polymerization and curing reaction that occurs when silver halide is developed. In particular, the present invention relates to a high-sensitivity image transfer photosensitive material that can be drawn by scanning exposure with a laser or the like.

[0002]

2. Description of the Related Art A method of forming a polymer image by exposing a light-sensitive material containing a silver halide, a reducing agent and a polymerizable compound to an image and developing the silver halide, thereby polymerizing the polymerizable compound on the image. Are disclosed in JP-A-61-69062 and JP-A-61-73145 (U.S. Pat.
676 and European Patent Publication No. 0174634A)
It is described in. In a typical embodiment of this image forming method, an uncured portion of a polymerizable compound containing a colorant is transferred from a photosensitive material to an image receiving material to form an image on the image receiving material. When a color image is formed, a photosensitive material containing two or more types of microcapsules (or packet emulsions) containing different colorants is used.

[0003] Although the above-mentioned photosensitive material has high sensitivity, it forms an image by destroying microcapsules.
The resolution depends on the size of the microcapsules (usually about 10 μm or more). In addition, since the coloring agent flows out and diffuses together with the uncured polymerizable compound due to the pressure destruction of the microcapsules, the image becomes thick and the resolving power is further reduced.

On the other hand, as a means for transferring an image with a high resolution, a photosensitive material in which a release layer is formed on a support and a photopolymerizable layer is formed thereon is known (Japanese Patent Application Laid-Open No. 59-1984).
Nos. -97140 and 61-188537). In this method, an image is formed once on a release layer on a support, and then the image is transferred onto another support together with the release layer. Since the transfer is performed with the release layer, the image can be transferred while maintaining high resolution.

However, since this photosensitive material is of a system in which a cured image is formed by a photopolymerization initiator, the photosensitive material has low photosensitivity (1/1000 or less of the above-mentioned photosensitive material using silver halide) and is generally ultraviolet-sensitive. And does not have sufficient sensitivity to laser light sources (generally visible light to infrared light).

[0006]

As described above, both types are not image transfer photosensitive materials satisfying both high light sensitivity and high resolution, but realize image transfer photosensitive materials satisfying such requirements. Is said to be very difficult.

An object of the present invention is to improve a photosensitive material utilizing a polymerization reaction by silver halide, and to provide a photosensitive material having high sensitivity and easy image transfer.

It is another object of the present invention to provide an image transfer photosensitive material which can directly produce a color proof from digital image data without using a lith film.

It is a further object of the present invention to provide a photosensitive material for image transfer which can use as a light source scanning exposure of a laser, especially a laser having a long wavelength.

[0010]

The object of the present invention has been attained by the following photosensitive material for image transfer.

(1) A silver halide, a reducing agent,
A photosensitive material provided with a photosensitive polymerizable layer containing a polymerizable compound without using microcapsules, wherein the photosensitive material is required for a reduction reaction of the reducing agent between the support and the photosensitive polymerizable layer.
Binder having a flow softening point above the heating temperature
A photosensitive material for image transfer, comprising a release layer containing the same . (2) The photosensitive material for image transfer according to (1), wherein the release layer has a thickness of 1.0 μm or more. ( 3 ) The photosensitive polymerizable layer comprises a photosensitive layer containing silver halide and a polymerizable layer containing a polymerizable compound, and a release layer, a polymerizable layer, and a photosensitive layer are sequentially provided on a support. The photosensitive material for image transfer according to 1). ( 4 ) The photosensitive material for image transfer according to (1), wherein an overcoat layer is further provided on the photosensitive polymerizable layer. ( 5 ) The photosensitive polymerizable layer further contains a colorant (1).
3. The photosensitive material for image transfer according to item 1. (6) the polymerizable layer further photosensitive material for image transfer according to containing colorant (3).

[0012]

According to the photosensitive material for image transfer of the present invention, since silver halide is used as an optical sensor, a high-sensitivity color proof can be directly produced from digital image data without using a lith film. Silver halide is
There is the advantage that scanning exposure of a laser, especially a long wavelength laser, can be used as the light source. Further, the photosensitive material for image transfer of the present invention is characterized in that a release layer is provided between the support and the photosensitive polymerizable layer. By providing the release layer, an image formed on a photosensitive material with high sensitivity using silver halide can be directly transferred to another material such as an image receiving material. Therefore, a clear transfer image having extremely high resolution can be formed as compared with a conventional image transfer photosensitive material using microcapsules.

[0013]

DETAILED DESCRIPTION OF THE INVENTION First, the layer constitution of the photosensitive material for image transfer of the present invention will be described with reference to the drawings.

FIG. 1 is a schematic sectional view of the photosensitive material for image transfer of the present invention. A release layer (12) is provided on the support (11), and a photosensitive polymerizable layer (13) is provided thereon. The photosensitive polymerizable layer is made of silver halide (1
4) containing a reducing agent (15), a polymerizable compound (16) and a coloring agent (17). The coloring agent (17) is an optional component,
It may not be contained in the photosensitive polymerizable layer. Hereinafter, a photosensitive material for image transfer having an embodiment having a single photosensitive polymerizable layer as shown in FIG. 1 is referred to as a single-layer photosensitive material.

FIG. 2 is a schematic sectional view of another embodiment of the photosensitive material for image transfer of the present invention. A release layer (22) is provided on a support (21), and a polymerizable layer (2) is formed thereon.
3) A photosensitive layer (24) is further provided thereon. The polymerizable layer (23) contains a polymerizable compound (25), a coloring agent (26), and a reducing agent (28). The coloring agent (26) is an optional component, and need not be contained in the polymerizable layer. The photosensitive layer (24) contains a silver halide (27). Hereinafter, a photosensitive material for image transfer in which the photosensitive polymerizable layer is separated into two or more layers such as a polymerizable layer and a photosensitive layer as shown in FIG. 2 is referred to as a laminated photosensitive material. In the photosensitive material shown in FIG. 2, the reducing agent (28) is contained in the polymerizable layer (23), but may be contained in the photosensitive layer (24). Further, the reducing agent may be dividedly added to the polymerizable layer and the photosensitive layer at an arbitrary ratio. Further, a reducing agent can be added to a layer other than the polymerizable layer and the photosensitive layer (image formation accelerating layer).

The above is an example of the layer structure for explaining the image transfer photosensitive material of the present invention, and the image transfer photosensitive material of the present invention is not limited to the above examples. For example, in addition to the layers described in each drawing, if necessary, additional layers such as an undercoat layer, an overcoat layer (protective layer, cover film), an intermediate layer, a back layer, or a special layer such as an adhesive layer. Functional layers can be provided. The undercoat layer is provided on the support, the overcoat layer is provided on the layer farthest from the support, the intermediate layer is provided between each layer, and the back layer is provided on the support on the side opposite to the photosensitive polymerizable layer. Can be

Next, the components and components of the photosensitive material for image transfer of the present invention will be described in more detail.

[Release Layer] The release layer is easily peeled off from the support and is non-adhesive at room temperature, but exhibits adhesiveness or fusing property when heated. The release layer usually contains an organic polymer as a binder. Examples of organic polymers include polyacrylates, acrylate copolymers, polymethacrylates, methacrylate copolymers, polyacrylamides, acrylamide copolymers,
Polyvinyl acetate, acetic acid copolymer, polyvinyl chloride, vinyl chloride copolymer, polyvinylidene chloride, vinylidene chloride copolymer, polystyrene, styrene copolymer,
Ethylene copolymer (eg, ethylene-vinyl acetate copolymer, ethylene-vinyl chloride copolymer, ethylene-acrylate copolymer, ethylene-acrylic acid copolymer), polyvinyl acetal (eg, polyvinyl butyral, polyvinyl formal), polyester, polyamide (eg, nylon) , Nylon copolymers), various rubbers (synthetic rubbers such as natural rubber and chlorinated rubber) and polyolefins. Polyvinyl acetal and polyamide are particularly preferred. Two or more kinds of polymers may be mixed and used.

The flow softening point of the binder, Ru der than the heating temperature required for the reduction reaction of the reducing agent. In the present specification, the flow softening point is defined as a flow conditioner with a pressure of 100 kg / cm ² and a heating rate of 6 ° C.
Min means the measured softening point when measured with a nozzle diameter of 1 mmφ × 10 m. The heating temperature required for the reduction reaction of the reducing agent is usually 70 to 200 ° C. It is preferable that the type of the binder is appropriately selected according to the heating temperature.

The release layer may contain, if necessary, additives such as a surfactant, a release agent, a plasticizer or a tackifier in addition to the binder. The release layer may be configured as two or more layers. The thickness of the release layer (when the release layer is configured as two or more layers, the entire thickness) is 1.0 μm
It is preferably at least 1.4 μm.

According to the study of the present inventors, when the conventional release layer of the image transfer photosensitive material using a photopolymer is applied as it is to the image transfer photosensitive material using silver halide of the present invention, a non-image Although the releasability of the part (uncured part) is good, the releasability of the image part (cured part) deteriorates (the force required for peeling increases), making image formation difficult and sometimes It was found that transfer could not be performed. Although the cause is not clear, it is not known in the image transfer photosensitive material using the photopolymer, and is a phenomenon peculiar to the image transfer photosensitive material using the silver halide of the present invention. To solve this problem, as described above, Ru with a binder having a place flow softening point equal to or higher than a heating temperature required for the reduction reaction of Motozai.

[Support] There is no particular limitation on the support of the photosensitive material for image transfer. Examples of support materials include polyethylene terephthalate, polypropylene, polyethylene, polyvinyl chloride, polystyrene, polycarbonate and cellulose triacetate. A film obtained by depositing a metal such as aluminum on these films is also used as a support. The surface of the support may be subjected to a surface treatment such as matting. The thickness of the support is preferably 50 to 300 μm, and 70 to 150 μm.
μm is more preferred.

[Silver Halide] In the present invention, any of silver chloride, silver bromide, silver iodide or silver chlorobromide, silver chloroiodide, silver iodobromide and silver chloroiodobromide is used as the silver halide. Particles can also be used. Silver halide grains have crystal defects such as those having regular crystals such as cubic, octahedral and tetradecahedral, those having irregular crystal forms such as spheres and plates, and twin planes. Or a composite form thereof. The grain size of the silver halide may be as fine as about 0.01 micron or less, or as large as up to about 10 microns in projected area diameter. Further, a polydisperse emulsion or a monodisperse emulsion may be used. Monodisperse emulsions are described in U.S. Pat. Nos. 3,574,628 and 3,655,394 and British Patent No. 1413748. Further, tabular grains having an aspect ratio of about 5 or more can be used. Tabular grains are described in Photographic Science and Engineering by Gatoff (Gutoff, Photog
raphic Science and Engineering), Vol. 14, 248
257 (1970); and U.S. Patent No. 4434.
No. 226, No. 4414310, No. 4433048,
It can be easily prepared by the methods described in US Pat. No. 4,439,520 and British Patent No. 2,121,157.

The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, or may have a layered structure. Further, silver halides having different compositions may be bonded by epitaxial bonding, or may be bonded to a compound other than silver halide, such as, for example, silver rhodan or lead oxide. For silver halide grains,
Copper, thallium, lead, bismuth, cadmium, zinc, chalcogens (eg, sulfur, selenium, tellurium), gold or Group VIII noble metals (eg, rhodium, iridium, iron, platinum, palladium) are prepared according to standard methods. It may be added in the form of a salt at the time of particle formation or after the particle formation. A specific method is described in US Pat.
No. 2, No. 1951933, No. 2448060,
No. 2628167, No. 2950972, No. 3
No. 488709, No. 3737313, No. 3772
No. 031, No. 4,269,927, and Research Disclosure (RD), Vol. 134, N.
o. 13452 (June 1975). In the present invention, when an image is formed by high-illuminance short-time exposure, iridium ions are added in an amount of 1 to 1 mol of silver halide.
It is preferable to use 0 ^-8 to 10 ^-3 mol, more preferably 10 ^-7 to 10 ^-5 mol. Further, two or more kinds of silver halide grains having different halogen compositions, crystal habits, grain sizes and the like can be used in combination.

The silver halide is preferably used in the form of an emulsion. The silver halide emulsion for use in the present invention is described in Research Disclosure (RD), No. 5, pp. 163-64. 17643
(December, 1978), pp. 22-23, "I. Emulsion preparation and types", and No. 2, p.
18716 (November 1979), p. 648. As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. Additives used in such a process are described in Research Disclosure Magazine, No. 17643
And No. 18716. Regarding chemical sensitizers, 17643 (p. 23) and No. 18
716 (right column on page 648) shows that the spectral sensitizer is N
o. No. 17643 (pages 23 to 24) and no. 18716
(From page 648, right column), the supersensitizers are described in 1
8716 (from page 649, right column). In addition, other known additives that can be used in the present invention are described in the above-mentioned two Research Disclosures. For example, as for the sensitivity enhancer, 18
No. 716 (page 648, right column), No. 1 17643 (pages 24-25) and N
o. 18716 (from page 649, right column). It is preferable to use silver halide grains having a relatively low fog value as the silver halide grains. A photosensitive material using such silver halide grains is described in JP-A-63-68830. As the silver halide emulsion, usually, a negative silver halide is used. However, reversible silver halide from which a direct positive image can be obtained may be used.

[Reducing Agent] The reducing agent used in the present invention has a function of reducing silver halide or a function of accelerating (or suppressing) polymerization of a polymerizable compound. There are various kinds of substances as the reducing agent having the above function. Examples of the reducing agent include hydroquinones, catechols, p-aminophenols, p-phenylenediamines, 3-pyrazolidones, 3-aminopyrazoles, 4-amino-5-pyrazolones, 5-aminouracils, 4,5-dihydroxy-6-aminopyrimidines, reductones, aminoreductones, o- or p-sulfonamidophenols, o- or p-sulfonamidonaphthols,
2,4-disulfonamidophenols, 2,4-disulfonamidonaphthols, o- or p-acylaminophenols, 2-sulfonamidoindanones,
-Sulfonamido-5-pyrazolones, 3-sulfonamidoindoles, sulfonamidopyrazolobenzimidazoles, sulfonamidopyrazolotriazoles,
α-Sulfonamide ketones, hydrazines and the like.
By adjusting the type, amount, etc. of the reducing agent, the polymerizable compound in either the portion where the latent image of the silver halide is formed or the portion where the latent image is not formed can be selectively polymerized. . For example, the following system (A), (B) or (C) can be adopted.

(A) The reducing agent develops the silver halide, and is itself oxidized to an oxidized form. When the oxidant is decomposed in the layer to generate a radical, polymerization occurs in a portion where the silver halide latent image is formed. As the reducing agent having such a function, hydrazines can be used alone, or hydrazines and another reducing agent can be used in combination. (B) When the oxidized form of the reducing agent has a polymerization suppressing function, polymerization is suppressed in the portion where the latent image of silver halide is formed by coexisting a polymerization initiator in the system. Then, polymerization occurs in a portion where the latent image of silver halide is not formed. Examples of the reducing agent having such a function include 1-phenyl-3-pyrazolidones. (C) In the case where the reducing agent itself has a polymerization suppressing function, but its oxidized product does not have a polymerization suppressing function (or has a weak polymerization suppressing function), a polymerization initiator is allowed to coexist in the system. By doing so, polymerization is suppressed in the portion where the latent image of silver halide is not formed, and polymerization occurs in the portion where the latent image of silver halide is formed. Examples of the reducing agent having such a function include hydroquinones.

In the above system (B) or (C),
It is necessary to add a polymerization initiator which decomposes by heating or light irradiation to generate radicals to any layer of the photosensitive material. These systems are described in JP-A-61-75342, JP-A-61-243449 and JP-A-62-44949.
-70836 and 62-81635, and U.S. Patent No. 4,649,098 and EP Patent 0202.
No. 490, each specification. Various reducing agents having the above functions are described in JP-A-61-183640,
Nos. 61-188535 and 61-228441, JP-A Nos. 62-70836, 62-86354, and 6
2-86355, 62-206540, 62-
No. 264041, No. 62-109437, No. 63-2
No. 54442, JP-A-1-267536 and 2-14
No. 1756, No. 2-141775, No. 2-20725
No. 4, No. 2-262662, and No. 2-269352 (including those described as developing agents or hydrazine derivatives). Regarding the reducing agent, T.
“The Theory of the Photographic Process” by James
4th edition, pages 291 to 334 (1977), Research
Disclosure Magazine, Vol. 170, No. 17029,
9-15, (June 1978), and the same magazine, Vol.
76, 17643, pp. 22-31, (1980
February). Japanese Patent Application Laid-Open No. 62-210446
A reducing agent precursor capable of releasing the reducing agent under heating conditions or in contact with a base or the like may be used in place of the reducing agent as in the photosensitive material described in Japanese Patent Application Laid-Open Publication No. H11-139,036. The reducing agent and the reducing agent precursor described in each of the above publications and documents can also be effectively used for the photosensitive material in the present specification. Therefore, the “reducing agent” in the present specification includes the reducing agent and the reducing agent precursor described in each of the above publications, the specification, and the literature.

Among these reducing agents, those having a basic property of forming a salt with an acid can be used in the form of a salt with an appropriate acid. These reducing agents may be used alone or, as described in the above publications, may be used by mixing two or more kinds of reducing agents. When two or more reducing agents are used in combination, the reducing agents interact as follows: first, promotion of reduction of silver halide (and / or organic silver salt) by so-called super-additivity; Causing polymerization of a polymerizable compound via an oxidation-reduction reaction with another reducing agent in which an oxidized form of a first reducing agent formed by reduction of silver halide (and / or an organic silver salt) coexists. (Or to suppress polymerization). However, at the time of actual use, since the above-mentioned reactions can occur at the same time, it is difficult to specify which action it is. The reducing agent is used in the range of 0.1 to 10 mol per mol of silver halide, and more preferably in the range of 0.5 to 5 mol. Specific examples of the reducing agent are shown below.

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[Polymerizable Compound] As the polymerizable compound in the present invention, a polymerizable monomer or a crosslinkable polymer can be used. A polymerizable monomer and a crosslinkable polymer may be used in combination. Examples of the polymerizable monomer include a compound having addition polymerizability or ring-opening polymerizability. Compounds having addition polymerizability include compounds having an ethylenically unsaturated group, and compounds having ring-opening polymerizability include compounds having an epoxy group. Compounds having an ethylenically unsaturated group are particularly preferred. Examples of the compound having an ethylenically unsaturated group include acrylic acid and salts thereof, acrylates, acrylamides,
Methacrylic acid and its salts, methacrylic esters,
Methacrylamides, maleic anhydride, maleic esters, itaconic esters, styrenes, vinyl ethers, vinyl esters, N-vinyl heterocycles, allyl ethers, allyl esters and derivatives thereof. it can. Acrylic esters or methacrylic esters are preferred.

Specific examples of acrylic esters include:
n-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, furfuryl acrylate, ethoxyethoxyethyl acrylate, tricyclodecanyloxy acrylate, nonylphenyloxyethyl acrylate, 1,
3-dioxolane acrylate, hexanediol diacrylate, butanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, tricyclodecane dimethylol diacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexa Acrylate, diacrylate of polyoxyethylenated bisphenol A, 2- (2
-Hydroxy-1,1-dimethylethyl) -5-hydroxymethyl-5-ethyl-1,3-dioxanediacrylate, 2- (2-hydroxy-1,1-dimethylethyl) -5,5-dihydroxymethyl- Examples include 1,3-dioxane triacrylate, triacrylate of propylene oxide adduct of trimethylolpropane, polyacrylate of hydroxy polyether, polyester acrylate and polyurethane acrylate.

Specific examples of the methacrylates include methyl methacrylate, butyl methacrylate,
Ethylene glycol dimethacrylate, butanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate,
Examples include pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, and dimethacrylate of polyoxyalkylenated bisphenol A. The polymerizable monomer can also be selected from commercial products and used. Examples of commercially available polymerizable monomers include, for example, Aronix M-309, M-310, M-315, M-400, manufactured by Toa Gosei Chemical Industry Co., Ltd.
M-6100, M-8030 and M-8100, Nippon Kayaku Co., Ltd., Kayarad HX-220, HX-62
0, R-551, TMPTA, D-330, DPHA,
DPCA-60, R604 and R684.

As the crosslinkable polymer, any known polymer having a group reactive with a radical species can be used. These polymers may be homopolymers or copolymers with monomers having no groups reactive to radical species. Examples of such a polymer include a polymer having an ethylenically unsaturated double bond in a molecule, a polymer having a non-ethylenically unsaturated double bond in a molecule, a polymer having a polyoxyalkylene unit in a molecule, and a polymer having a polyoxyalkylene unit in a molecule. Examples thereof include a polymer having a halogen atom. The crosslinkable polymer has a polymerizable functional group in the polymer molecule, and generates a radical in the polymer by a deelementation reaction such as dehalogenation or dehydrogenation, and the radical is converted into a polymerizable compound. In addition, those which initiate the polymerization reaction of ## STR3 ## or which form a crosslink between polymers by coupling of two generated polymer radicals are also included. The above functional group may be contained in the main chain of the polymer, or may be contained in the side chain of the polymer. When these groups are contained in the side chain of the polymer, these groups may be introduced into the polymer by a polymer reaction, or these groups may be introduced into a monomer in advance, and then the monomer may be polymerized or copolymerized. The polymer may be synthesized by polymerization. With respect to the polymer having these crosslinkable functional groups in the side chain of the polymer, examples of the repeating unit having these functional groups are shown below.

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In addition, polymers having an ethylenically unsaturated double bond in the side chain as exemplified in JP-A-64-17047 can also be used. Examples of the polymer having a functional group in a main chain or a side chain include synthetic rubber (eg, polybutadiene, polyisoprene, styrene-butadiene copolymer, styrene-butadiene-acrylonitrile.
Copolymer), natural rubber, polyethylene oxide, polypropylene oxide, polyvinyl chloride (including copolymer), polyvinylidene chloride (including copolymer),
Mention may be made of polyvinyl acetate (including copolymers), chlorinated polyethylene, polyvinyl butyral, methyl cellulose, ethyl cellulose and butyl cellulose. These crosslinkable polymers are described in "Polymer Reaction" (Polymer Society of Japan / Kyoritsu Shuppan, 1978), pp. 147-1.
Also described on page 92. When an alkaline solvent is used as an eluent described later, the crosslinkable polymer preferably has an acidic functional group in the molecule. Examples of acidic functional groups include carboxyl groups, acid anhydride groups,
Examples include phenolic hydroxyl, sulfonic, sulfonamide and sulfonimide groups. When the binder is an addition polymer, a copolymer containing a monomer having a crosslinkable functional group and a monomer having an acidic functional group can be used. Specific examples of such a monomer include acrylic acid, methacrylic acid, crotonic acid, maleic acid, phthalic acid, maleic anhydride, p-carboxystyrene, p-hydroxystyrene, p-hydroxyphenylacrylamide, hydroxyethyl methacrylate, and hydroxyethyl methacrylate. Ethyl methacrylamide and p
-Vinylbenzene sulfonic acid.

The polymerizable compounds described above may be used alone or in combination of two or more. Photosensitive materials using two or more polymerizable compounds in combination are described in
It is described in Japanese Patent Publication No. 210445. Note that a substance in which a polymerizable functional group such as a vinyl group or a vinylidene group is introduced into the chemical structure of the reducing agent or the coloring agent can also be used as the polymerizable compound.
As described above, it is a matter of course that the use of a substance which also serves as a reducing agent and a polymerizable compound or a coloring agent and a polymerizable compound is included in the embodiment of the photosensitive material. The polymerizable compound is contained in the polymerized layer in an amount of preferably 3 to 90% by weight, more preferably 15 to 60% by weight, based on the total amount of the layer.

[Base or Base Precursor] The light-sensitive material for image transfer of the present invention can contain a base or base precursor. In particular, when performing a dry development process by heating, the photosensitive material preferably contains a base or a base precursor. As the base and the base precursor,
Inorganic bases and organic bases, or base precursors thereof (decarboxylation type, pyrolysis type, reaction type and complex salt forming type, etc.) can be used. Examples of inorganic bases are described in JP-A-62-2.
No. 09448. Examples of the organic base include tertiary amine compounds (described in JP-A-62-170954), bis-, tris-, or tetraamidine compounds (described in JP-A-63-316760), and bis-, tris-, or tetraguanidine compounds. (Described in JP-A-64-68746). In the present invention, a base having a pKa of 7 or more is preferable.

In the present invention, a base precursor is preferable to a base from the viewpoint of storage stability of the light-sensitive material. Examples of preferred base precursors include salts of organic acids and bases which are decarboxylated by heating (described in JP-A-63-316760, JP-A-64-68746, JP-A-59-180537 and JP-A-61-313431) and Urea compounds which release a base upon heating (described in JP-A-63-96159) can be exemplified. In addition, as a method of releasing a base using the reaction, transition metal acetylide,
Reaction with a salt containing an anion having an affinity higher than that of the acetylide anion with respect to the transition metal ion (JP-A-63-25)
No. 208) and a compound which is capable of forming a complex reaction with a water-soluble basic metal compound and a metal ion constituting the basic metal compound using water as a medium. A method of releasing a base by a reaction between two compounds (described in Japanese Patent Application Laid-Open No. 1-3282) is mentioned. As a base precursor, 50 ° C. to 20
Preferably, it releases a base at 0 ° C.
It is further preferred that the base is released at a temperature of from 1 to 160 ° C.

The photosensitive material using a base or a base precursor is described in JP-A-62-264041. JP-A-62-1170954 discloses a photosensitive material using a tertiary amine as a base, and discloses a photosensitive material using a fine particle dispersion of a hydrophobic organic basic compound having a melting point of 80 to 180 ° C. JP 6
Japanese Patent Application Laid-Open No. 2-209523 discloses a photosensitive material using a guanidine derivative having a solubility of 0.1% or less.
JP-A-70-845 discloses a photosensitive material using a hydroxide or a salt of an alkali metal or an alkaline earth metal.
Further, as for a photosensitive material using an acetylide compound as a base precursor, JP-A-63-24242 discloses that a propiolate is used as a base precursor.
Further, a photosensitive material containing silver, copper, a silver compound or a copper compound as a catalyst for a base formation reaction is disclosed in JP-A-63-4663.
No. 446, the propiolate and the silver, copper,
Japanese Patent Application Laid-Open No. 63-81338 discloses a light-sensitive material containing a silver compound or a copper compound in a state of being isolated from each other. Japanese Patent Application Laid-Open No. 63-97942 discloses a photosensitive material containing a polymer, while Japanese Patent Application Laid-Open Publication No. Japanese Patent No. 464747 discloses a photosensitive material containing a sulfonyl acetate salt as a base precursor and further containing a heat-meltable compound as a reaction accelerator for a base generation reaction. For light-sensitive materials using a compound to which isocyanate or isothiocyanate is bonded, The 63-96652 discloses further the light-sensitive material comprising a nucleophilic agent as a decomposition accelerator for this compound is described respectively in JP-A-63-173039.

A photosensitive material using a bis- or trisamidine salt of a carboxylic acid capable of being decarboxylated as a base precursor is described in JP-A-64-9441. Each is described in Japanese Unexamined Patent Publication No. 64-68749. The base or base precursor is preferably used in a range of 0.5 to 50 mol, more preferably 1 to 20 mol, per mol of silver halide.

[Colorant] The photosensitive material for image transfer of the present invention comprises:
A colorant can be included depending on the mode of image formation. In an embodiment in which an image is formed using a colorant, the colorant is a component having a function of making a human perceive a color image in a formed image (for example, a color proof). As the coloring agent for this purpose, any known coloring agent is used regardless of pigment or dye as long as it does not significantly hinder the curing reaction of the polymerizable compound or significantly hinder the photosensitivity and development reaction of silver halide. It is possible to As pigments that can be used as coloring agents, commercially available pigments and known pigments described in various documents and the like can be used. For literature, see the Color Index (CI) Handbook,
"Latest Pigment Handbook" (edited by Japan Pigment Technology Association, 1977), "Latest Pigment Application Technology" (CMC Publishing, 1986), "Printing Ink Technology" (CMC Publishing, 1984) and the like. Examples of the type of the pigment include a black pigment, a yellow pigment, an orange pigment, a brown pigment, a red pigment, a purple pigment, a blue pigment, a green pigment, a fluorescent pigment, a metal powder pigment, and a polymer-bound pigment. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelated azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments , Quinophthalone pigments, dyed lake pigments,
Azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments and the like can be used.

The pigment that can be used in the present invention may be used without being subjected to a surface treatment, or may be used after being subjected to a surface treatment.
Examples of the surface treatment include a method of surface-coating a resin or wax, a method of attaching a surfactant, and a method of bonding a reactive substance (for example, a silane coupling agent, an epoxy compound, or a polyisocyanate) to the pigment surface. Conceivable. The above surface treatment methods are described in “Properties and Applications of Metallic Soap” (Koshobo), “Printing Ink Technology” (CMC Publishing, 1
984) and "Latest Pigment Application Technology" (CMC Publishing, 1986). The particle size of the pigment is preferably in the range of 0.01 μm to 10 μm,
More preferably, it is in the range of 0.05 μm to 1 μm. The introduction of the pigment into the photosensitive polymerizable layer or the polymerizable layer,
A method in which these layers are added to and dispersed in a coating solution can be used. As a method for dispersing the pigment, a known dispersion technique used in the production of ink or toner can be used.
Examples of the disperser include an ultrasonic disperser, a sand mill, an attritor, a pearl mill, a super mill, a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a dynatron, a three-roll mill, and a pressure kneader. For details, refer to “Latest Pigment Application Technology” (CMC Publishing, 19
1986).

Dyes can also be used as coloring agents.
As the dye itself, which is a colored substance, commercially available dyes and known dyes described in various documents (for example, "Dye Handbook" edited by The Society of Synthetic Organic Chemistry, Japan, 1970) can be used. Specifically, azo dyes, metal complex salt azo dyes,
Dyes such as a pyrazolone azo dye, an anthraquinone dye, a phthalocyanine dye, a carbonium dye, a quinone imine dye, and a methine dye are exemplified. The content of the coloring agent may significantly prevent the polymerization reaction in the photosensitive polymerizable layer (or the polymerizable layer) or may affect the photosensitivity and development reaction of the silver halide contained in the photosensitive polymerizable layer (or the photosensitive layer). Set an upper limit so as not to interfere significantly. The specific content should be an amount necessary to give an optical density necessary to give an image density similar to that of a printed matter. This depends on the light absorption characteristics and absorbance of each pigment or dye. Generally content is preferably 0.01 to 2 g / m ^2, more preferably from 0.02 to 1 g / m ^2. These colorants may be used in combination of two or more.
The colorant preferably has a hue similar to the printing ink used for printing the printed matter. Therefore, it is most preferable to use a colorant having an absorption spectrum similar to that of the colorant used in the printing ink. Since a printing ink usually uses a pigment in many cases, it is more preferable to use a pigment than a dye as a coloring agent used in the present invention.

[Binder of Polymerizable Layer] In the case of a laminated photosensitive material, a binder can be added in order to improve the film strength of the polymerizable layer. It is preferred that the binder does not impair the solubility of the uncured portion of the polymerizable layer in the eluate. It is also preferable that the binder does not significantly increase the solubility of the cured portion of the polymerizable layer in the eluate. As the binder, natural and synthetic polymer compounds can be used. As the synthetic polymer, homopolymers and copolymers of various vinyl monomers among addition polymerization type synthetic polymers such as polystyrene, acrylic resin and methacrylic resin can be used. Polycondensation type synthetic polymers and copolymers such as polyester, polyamide, polyurethane and polyester-polyamide can also be used. When an alkaline solvent is used as an eluent described later, the binder preferably has an acidic functional group in its molecule. Examples of acidic functional groups include carboxyl groups, acid anhydride groups, hydroxyl groups,
Examples include phenolic hydroxyl, sulfonic, sulfonamide and sulfonimide groups. When the binder is an addition polymer, a homopolymer or copolymer containing a vinyl polymerizable monomer having an acidic functional group can be used. Specific examples of such a monomer include acrylic acid, methacrylic acid, crotonic acid, maleic acid, phthalic acid, maleic anhydride, p-carboxystyrene, p-hydroxystyrene, p-hydroxyphenylacrylamide, hydroxyethyl methacrylate, and hydroxyethyl methacrylate. Ethyl methacrylamide and p
-Vinylbenzene sulfonic acid. The amount of the binder to be added to the polymerizable layer is not particularly limited as long as the curing reaction of the polymerizable layer is not hindered, but is 0 to 80%, preferably 0 to 70% by weight based on the entire polymerizable layer.

[Polymerization Inhibitor] In the case of a laminated type light-sensitive material, a polymerization inhibitor can be added to the polymerizable layer in order to prevent a dark polymerization reaction. As the polymerization inhibitor for this purpose, any conventionally known polymerization inhibitors can be used. Examples of the polymerization inhibitor include nitrosamine compounds, thiourea compounds, thioamide compounds, urea compounds, phenol derivatives, nitrobenzene derivatives, and amine compounds. More specifically, Cuperon Al salt, N
-Nitrosodiphenylamine, allylthiourea, aryl phosphite, p-toluidine, φ-tolutinone,
Nitrobenzene, pyridine, phenathiazine, β-naphthol, naphthylamine, t-butylcatechol, phenothiazine, chloranil, p-methoxyphenol,
Pyrogallol, hydroquinone, and alkyl or aryl substituted hydroquinone can be mentioned.

[Organic Metal Salt] An organic metal salt can be added to the photosensitive layer of the layered photosensitive material together with silver halide. The organic silver salt is considered to participate in an oxidation-reduction reaction using a latent image of silver halide as a catalyst during heating, and as a result, an effect such as accelerating image formation is recognized. Examples of organic silver salts include organic acid silver and triazole-based silver salts such as “Basics of photographic optics, non-silver salts” (p. 247) and
Organic silver salts described in JP-A-55429 and JP-A-62-2246 can be used. Specific examples include silver salts of aliphatic carboxylic acids, aromatic carboxylic acids, thiocarbonyl group compounds having a mercapto group or α-hydrogen, acetylene compounds, and imino group-containing compounds. Aliphatic carboxylic acids include acetic, butyric, succinic, sebacic, adipic, oleic, linoleic, linolenic, tartaric, palmitic, stearic, behenic, and camphoric acids. In general, the smaller the number of carbon atoms, the more unstable the silver salt, and therefore, those having an appropriate number of carbon atoms are preferred. Examples of aromatic carboxylic acids include benzoic acid derivatives, quinolinic acid derivatives, naphthalene carboxylic acid derivatives, salicylic acid derivatives, gallic acid, tannic acid, phthalic acid, phenylacetic acid derivatives and pyromellitic acid.

Examples of the mercapto group or a thiocarbonyl group compound having α-hydrogen include 3-mercapto-4-phenyl-1,2,4-triazole, 2-mercaptobenzimidazole, 2-mercapto-5-aminothiadiazole, -Mercaptobenzothiazole, s-alkylthioglycolic acid (the alkyl group having 12 to 2 carbon atoms)
2), dithiocarboxylic acids (eg, dithioacetic acid), thioamides (eg, thiostearoamide), 5-carboxy-
1-methyl-2-phenyl-4-thiopyridine, mercaptotriazine, 2-mercaptobenzoxazole,
Mention may be made of mercaptooxadiazole and 3-amino-5-benzylthio-1,2,4-triazole. Mercapto compounds described in U.S. Pat. No. 4,123,274 can also be used. Compounds containing an imino group include benzotriazole and its derivatives,
Examples thereof include 1,2,4-triazole, 1H-tetrazole, carbazole, saccharin, imidazole and derivatives thereof. Benzotriazole and its derivatives are described in JP-B-44-30270 and JP-B-45-18416. Examples of benzotriazole and its derivatives include benzotriazole, alkyl-substituted benzotriazoles (eg, methylbenzotriazole), halogen-substituted benzotriazoles (eg, 5-chlorobenzotriazole), and carboimidobenzotriazoles (eg, butyl Carbimidobenzotriazole), nitrobenzotriazoles (described in JP-A-58-11839), sulfobenzotriazole (described in JP-A-58-15638), carboxybenzotriazole and salts thereof, and hydroxybenzotriazole. be able to. 1,
2,4-Triazole and 1H-tetrazole are described in U.S. Pat. No. 4,220,709.

In some cases, the same effect can be obtained by adding an organic compound constituting the organic silver salt to the photosensitive layer instead of the organic silver salt. Two or more organic silver salts may be used in combination. The above organic silver salt is used in an amount of 0 to 10 per mole of silver halide.
Mole, preferably 0 to 1 mole. The total coating amount of silver halide and organic silver salt is 1 mg in terms of silver in the photosensitive layer.
To 5 g / m ² , preferably 10 mg to 0.5 g / m ² .

[Binder for Photosensitive Layer] In the case of a laminated photosensitive material, any binder can be used as the binder for the photosensitive layer as long as the properties of the photosensitive layer are not significantly impaired. However, since the photosensitive layer contains silver halide, it is preferable to use a hydrophilic binder. The hydrophilic binder is a binder having a hydrophilic group or / and a bond in a molecular structure. Examples of the hydrophilic group include a carboxyl group, an alcoholic hydroxyl group, a phenolic hydroxyl group, a sulfonic acid group, a sulfonamide group, a sulfonimide group, and an amide group. Examples of hydrophilic bonds include urethane bonds,
Examples include an ether bond and an amide bond.
It is preferable to use a water-soluble polymer and / or a water-swellable polymer as the hydrophilic binder polymer.
A water-swellable polymer has an affinity for water,
Since the binder itself has a crosslinked structure or the like, it does not completely dissolve in water. As the water-soluble or water-swellable binder, a natural or synthetic polymer compound can be used. Examples of natural polymers include water-soluble polysaccharides (eg, starch derivatives, cellulose derivatives, alginic acid, pectic acid, gum arabic, pullulan, dextran) and proteins (eg, casein, gelatin). These may be artificially modified as necessary. Further, it can be used after being modified or cross-linked at the time of coating and drying. As the synthetic polymer, a polymer of a water-soluble monomer or a copolymer of this with another monomer can be used. Examples of the water-soluble monomer in this case include monomers having a chemical structure such as a carboxyl group, an acid anhydride group, a hydroxyl group, a sulfonic acid (salt) group, an amide group, an amino group, and an ether group. Such monomers are described in “Applications and Markets of Water-Soluble Polymers” (CMC pages 16-18). Copolymers obtained by polymerizing these monomers or cross-linking a polymer obtained by copolymerizing with other monomers can also be used (for example, a copolymer described in US Pat. No. 4,913,998).

As other synthetic polymers, polyvinyl alcohol, polyvinyl ether, polyvinyl pyrrolidone, polyethylene oxide and derivatives or modified products thereof can be used. For example, in the case of polyvinyl alcohol, those having various degrees of saponification can be used. Also, copolymerized modified polyvinyl alcohol can be used. Copolymerization modification is a method in which a copolymer of vinyl acetate and another monomer is saponified to form a modified polyvinyl alcohol. Any monomer can be used as long as it copolymerizes with vinyl acetate. Examples of the comonomer include ethylene, higher vinyl carboxylate, higher alkyl vinyl ether, methyl methacrylate and acrylamide. Also, post-modified polyvinyl alcohol can be used. Post-modification is a method in which a polyvinyl alcohol is modified by a polymer reaction with a compound having reactivity to a hydroxyl group. Specifically, the hydroxyl group is modified by etherification, esterification, acetalization, or the like. Furthermore, crosslinked polyvinyl alcohol can also be used. In this case, an aldehyde as a crosslinking agent,
The polyvinyl alcohol is crosslinked using a methylol compound, an epoxy compound, a diisocyanate, a divinyl compound, a dicarboxylic acid, or an inorganic crosslinking agent (eg, boric acid, titanium, copper). These modified polyvinyl alcohols and cross-linked polyvinyl alcohols are described in “Poval”, 3rd edition, Polymer Publishing Association (pp. 281-285 and 256-26).
Page 0). The molecular weight of these hydrophilic polymers is preferably in the range of 3000 to 500,000. The coating amount is 0.05 to 20 g / m ² , more preferably 0.1 to ²⁰ g / m ² .
The range is from 10 to 10 g / m ² .

Oxygen that has permeated the polymerizable layer during thermal development inhibits polymerization or crosslinking by radicals. Therefore, the photosensitive layer preferably has a function of preventing the influence of oxygen in the air on the polymerizable layer. For this function, the hydrophilic binder needs to be a substance having a low oxygen permeability, and its oxygen permeability coefficient is 1.0 ×
It is preferably 10 ^-11 cc · cm / cm ² · sec · cm · Hg or less. As the polymer having a low oxygen permeability, a polyvinyl alcohol polymer, a copolymer of gelatin and vinylidene chloride is preferable. Here, the polyvinyl alcohol-based polymer means polyvinyl alcohol and modified polyvinyl alcohol (for example, a saponified block copolymer of polyvinyl acetate and another monomer). The molecular weight is not particularly limited, but is preferably in the range of about 3000 to 500,000. As a polymer with low oxygen permeability, a saponification degree of 5
0% or more, more preferably 80% or more, further preferably 85% or more of polyvinyl alcohol is particularly preferable.

[Heat Development Accelerator] The light-sensitive material used in the present invention may contain a heat development accelerator in any of the layers in order to accelerate the heat development and perform the heat development in a shorter time. .
It is not clear why the thermal development accelerator has the above-mentioned action, but by giving a plasticizing effect to the binder of the light-sensitive material or adding a plasticizing effect to the binder at the time of heating, In the light-sensitive material, the movement or diffusion of a substance contributing to the reaction in each layer is promoted, and as a result, various reactions (decomposition of a base precursor, reduction of silver halide, , Polymerization or curing reaction). As the above thermal development accelerator, a compound having a plasticizing action at room temperature or when heated to a binder used in any layer of the photosensitive material, or a compound having no plasticizing action but capable of being melted in the layer by heating Any of them can be used. As the compound having a plasticizing action at room temperature or under heating with respect to a binder used in any layer of the photosensitive material, all known compounds known as a plasticizer of a high molecular compound can be used. Examples of such plasticizers include “Plastic Compounding Agents” Taiseisha, P21-63;
Additives, 2nd Ed "(Plastics Additives, 2nd Ed
ition) Hanser Publishers, Chap.5 P251-296; "Thermoplastics Additives" (Thermoplastics A
dditives) Marcel Dekker Inc. Chap. 9 P345-379; “Plastics Additives An Industrial Guid”
e) Noyes Publications, Section-14 P333-485; "The Technology of Solvents and Plasticizers"
sticizers) John Wiley & Sons Inc. Chap.15 P903-10
27); “Industrial Plasticizers”
(Industrial Plasticizers, Pergamon Press); "Plasticizer Technology Volume 1" (Plasticize
r Technology Vol.1, Reinhold Publishing Corp.);
“Plasticization and Plasticizer Process”
rocess, American Chemistry).

Compounds which can be melted in the layer by heating include polar substances described in US Pat. No. 3,347,675; Research Disclosure, 1976.
1,10-decanediol, methyl anisate, biphenyl suberate, described in the December issue, pages 26-28;
Sulfonamide derivatives, polyethylene glycol derivatives, and cyclic amide compounds described in JP-A Nos. 62-151841, 62-151843 and 62-183450; JP-A-63-243835 and 63
Compounds having an aromatic ring described in JP-B-59-25567, JP-A-59-101392, JP-A-60-82382 and JP-A-62-25085; 61-28359
No. 2, No. 63-15784, No. 64-1583, No. 57-146688, No. 58-104793, No. 5
Nos. 8-205795, 62-142686, 62
Compounds having an ester or amide group described in JP-A-144990 and JP-A-62-132675; JP-A-58-57989, JP-A-58-72499 and JP-A-58-72499.
Nos. -87094, 60-29587, 60-56
No. 588, No. 60-12581, No. 60-1688
No. 8, No. 61-242888, No. 61-31287
Compounds having an ether or thioether structure described in JP-A Nos. 61-27285 and 61-31287; JP-A-60-34892 and JP-A-61-112.
No. 689, No. 61-116584, No. 61-1514
Nos. 78 and 62-267186; ketones, carbonates, sulfoxides and phosphate compounds; and JP-A Nos. 59-159393 and 63-15.
Compounds having a phenolic hydroxyl group described in JP-A-783 and JP-A-63-249686 can also be used.

Preferred thermal development accelerators include glycols (eg, diethylene glycol, dipolypropylene glycol), polyhydric alcohols (eg, glycerin, butanediol, hexanediol), sugars, formate, ureas (eg, urea). , Diethyl urea, ethylene urea,
Propylene urea), urea resins, phenolic resins, amide compounds (eg, acetamide, propionamide), sulfamides and sulfonamides. Further, two or more of the above thermal development accelerators can be used in combination. Further, it can be added separately in two or more layers. The addition amount of the thermal development accelerator is optional as long as the properties of the light-sensitive material are not significantly impaired, but is preferably 0 to ² g / m ^2, more preferably 0 to 1 g.
/ M ² .

[Other Additives] Other additives include an antifoggant for preventing fogging, a silver development accelerator for accelerating silver development, a development stopping agent for stopping development at an appropriate timing, and good coating. Surfactants for obtaining a surface, and dispersibility stabilizers for improving the dispersion stability of the dispersion. An antifogging agent for preventing fogging, a silver development accelerator for promoting silver development, and a stabilizer may be contained in at least one of the layers. These examples will be described below. However, these additives may simultaneously exhibit two or more functions due to the action of one compound, and it is difficult to make a clear distinction. Examples thereof include compounds having a cyclic amide structure described in JP-A-61-151841 and JP-A-62-1518.
No. 42, a thioether compound disclosed in JP-A-62-1
No. 51843, a polyethylene glycol derivative, JP-A-62-151844, a thiol derivative, JP-A-62-178232, an acetylene compound, JP-A-62-183450, a sulfonamide derivative, and Research Disclosure Magazine No. 17643, pp. 24-25 (1978)
Year), JP-A-59-168442 and JP-A-59-1116.
Nos. 36, 62-87957 and 62-1518
Compounds described in JP-B No. 38 can be exemplified. The amount of these compounds used is in the range of 10 ^-7 mol to 1 mol per mol of silver halide. In the present invention, various development terminators can be used for the purpose of always obtaining a constant image with respect to the processing temperature and the processing time during thermal development. The term "development terminator" as used herein means that after appropriate development, the base is quickly neutralized or reacts with the base to reduce the base concentration in the layer and to inhibit development by interacting with a compound or silver and silver salt. Compound. Specific examples include an acid precursor that releases an acid when heated, an electrophilic compound that undergoes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound, and a precursor thereof. Thermal development terminators are described in JP-A-62-25315.
No. 9, pages 31 to 32 and JP-A-2-42447.
And JP-A-2-262661.

[Colorant] In the present invention, a colorant can be added to the light-sensitive material for the purpose of preventing halation. As a coloring agent for this purpose, a pigment or a pigment may be used as long as it does not significantly hinder the polymerization curing reaction of the polymerizable layer or significantly hinders the photosensitivity and developability of silver halide.
Any known coloring agent can be used regardless of the dye. When a colorant is added to prevent halation, the colorant must be capable of absorbing light at the exposure wavelength. As the coloring agent for this, any substance that can be used as a coloring agent in the present invention can be used. When the colorant is a dye, which is contained in the photosensitive layer or a layer adjacent to the photosensitive layer, an anti-irradiation dye referred to in a silver salt photosensitive material can be used. For these anti-irradiation dyes,
JP-B-41-20389, JP-B-43-3504,
JP-B-43-13168 and JP-A-2-39042.
Gazettes, and U.S. Pat.
Nos. 423207 and 2865752, British Patent No. 1
No. 030392 and No. 1100546. The content of the colorant can be used as long as it does not significantly hinder the polymerization reaction of the polymerizable layer or significantly hinders the photosensitivity and developability of the silver halide, and is not particularly limited. The appropriate amount of addition varies depending on which layer is used, and whether a pigment or a dye is used. Also, since the appropriate amount of addition changes depending on the absorbance of the colorant,
Although it is difficult to unconditionally define the optimum amount to be added, it is difficult to define the optimum amount.
01 to ² g / m ² , more preferably 0.02 to 1 g / m ^2
2 Incidentally, in the mode of forming an image using a colorant,
When a colorant is used in the polymerizable layer for the photosensitive material, the color tone of the image is changed by mixing the color with the colorant. Addition should be avoided. This is not a limitation in a mode in which an image is formed using toner. These coloring agents can be contained in any layer of the light-sensitive material. Further, a new layer such as a back layer and an intermediate layer may be provided on the light-sensitive material and introduced into these layers. Further, it can be added to each of a plurality of layers of the photosensitive material. Further, two or more colorants can be used in combination.

[Polymerization Initiator] The reducing agent used in the light-sensitive material used in the present invention or an oxidized form of the reducing agent generated when the reducing agent reduces silver halide suppresses the polymerization of the polymerizable compound. If the compound works,
It is necessary to add a polymerization initiator which generates a radical by heating or light irradiation to at least one layer of the photosensitive material. As these thermal polymerization initiators or photopolymerization initiators, conventionally known ones can be used.
When a photopolymerization initiator is used, it is necessary to irradiate the entire surface with light after thermal development. The thermal polymerization initiator is, for example, “Addition polymerization / Ring-opening polymerization”
(1983, Kyoritsu Shuppan) on pages 6-18. Specific examples of the thermal polymerization initiator include azobisisobutyronitrile, 1,1′-azobis (1-cyclohexanecarbonitrile), dimethyl-2,2′-azobisisobutyrate, and 2,2′-azobis Organic compounds such as azo compounds such as (2-methylbutyronitrile) and azobisdimethylvaleronitrile, benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, t-butyl hydroperoxide and cumene hydroperoxide. Inorganic peroxides such as peroxide, hydrogen peroxide, potassium persulfate and ammonium persulfate, and sodium p-toluenesulfinate can be mentioned.

The photopolymerization initiator is described, for example, in Oster et al.
emical Review, Vol. 68 (1968), 125-1
Page 51 and "Light-Sensitive System" by Kosar (Jo
carbonyl compounds (eg, α-alkoxyphenyl ketones, polycyclic quinones, benzophenone derivatives, xanthones, thioxanthones, benzoins) as described on pages 158-193 of hn Wiley & Sons, 1965). ), Halogen-containing compounds (eg, chlorosulfonyl and chloromethyl polynuclear aromatic compounds, chlorosulfonyl and chloromethyl heterocyclic compounds, chlorosulfonyl and chloromethylbenzophenones, fluorenones), haloalkanes, α-halo-α-phenylacetophenone , Redox couples of photoreducing dyes and reducing agents, organic sulfur compounds, peroxides, optical semiconductors (eg, titanium dioxide, zinc oxide), metal compounds (eg, iron (I)
Salt, metal carbonyl, metal complex, uranyl salt), silver halide, azo and diazo compounds, and the like.
Specific examples of the photopolymerization initiator include 2-dimethoxy-2-
Phenylacetophenone, 2-methyl- {4- (methylthio) phenyl} -2-morpholino-1-propanone,
Benzoin butyl ether, benzoin isopropyl ether, benzophenone, Michler's ketone, 4,4 '
-Diethylaminobenzophenone, chloromethylbenzophenone, chlorosulfonylbenzophenone, 9,10
-Anthraquinone, 2-methyl-9,10-anthraquinone, chlorosulfonylanthraquinone, chloromethylanthraquinone, 9,10-phenanthrenequinone, xanthone, chloroxanthone, thioxanthone, chlorothioxanthone, 2,4-diethylthioxanthone Chlorosulfonylthioxanthone, chloromethylbenzothiazole, chlorosulfonylbenzoxazole, chloromethylquinoline, fluorene and carbon tetrabromide.

Examples of the photoreducing dye include methylene blue, thionine, rose bengal, erythrosine-
β, eosin, rhodamine, phloxin-β, safranin, acriflavine, riboflavin, fluorescein, uranine, benzoflavin, acridine orange,
Acridine yellow and Benzanthrone can be mentioned. Examples of reducing agents (hydrogen-donating compounds) used with the photoreducing dye include β-diketones such as dimedone and acetylacetone, amines such as triethanolamine, diethanolamine, monoethanolamine, diethylamine and triethylamine, and p-toluene. Examples thereof include sulfinic acids such as sulfinic acid and benzenesulfinic acid and salts thereof, N-phenylglycine, L-ascorbic acid and salts thereof, thiourea and allylthiourea. The molar ratio between the photoreducing dye and the reducing agent is
A range of 1: 0.1 to 1:10 is preferred. As the photopolymerization initiator, commercially available ones, for example, "Irgacure 651 and -907" manufactured by Ciba-Geigy are preferably used. The polymerization initiator is contained in an amount of 0.001 g of the polymerizable compound.
It is preferably used in the range of 1 to 0.5 g, and more preferably in the range of 0.01 to 0.2 g.

[Adhesive Layer] Depending on the mode of image formation,
An adhesive layer may be provided on the photosensitive material. The adhesive layer needs to be a layer that does not completely dissolve in the eluate during the elution operation. Further, it is necessary to have an ability to attach a colored toner to the surface. As long as the above two points are satisfied, the adhesive layer can be constructed with any known substance. Examples of such a layer include a conventionally known arbitrary polymer and a mixed layer of a compound exemplified as a substance having a plasticizing effect among thermal development accelerators, or
A mixed layer of a conventionally known arbitrary polymer and an oligomer of a conventionally known arbitrary polymer, or a secondary transition temperature of -1
A layer containing an elastomeric polymer at 0 ° C. or lower can be mentioned. The last example is advantageous because the polymer alone can provide the necessary properties, but may be used as a mixed layer further added with a plasticizer, an oligomer and the like. Specific examples of the polymer used for the adhesive layer include natural rubber and synthetic rubber. Examples of synthetic rubber include:
Isobutylene, nitrile rubber, butyl rubber, chlorinated rubber, polyvinyl isobutyl ether, silicone elastomer, neoprene and copolymer rubber (eg, styrene-butadiene copolymer, styrene-isobutylene copolymer)
Can be mentioned. When the polymer is a copolymer, it may be any of random, block and graft copolymers.
The thickness of the adhesive layer is preferably 0.01 to 10 μm,
More preferably, the thickness is 0.05 to 5 μm.

[Arbitrarily Provided Layers] Regardless of the single-layer type photosensitive material and the laminated type photosensitive material, additional layers can be provided at any part of the photosensitive material. For example, a protective layer (or a cover film layer) for protecting the surface or preventing polymerization due to oxygen in the air, a back layer for preventing halation or preventing adhesion when the photosensitive material is stored in a stacked state, An intermediate layer or the like for improving adhesion between layers and releasability or preventing halation can be provided as necessary. In addition, when performing transfer to the image receiving material or lamination with the image receiving material, in order to prevent bubbles from being mixed and preventing uniform adhesion, a matting agent is introduced into a layer in contact with these image receiving materials, A new layer containing a matting agent may be provided. As the matting agent in this case, a conventionally known matting agent can be used. The matting agent may be introduced into the image receiving material. When the photosensitive material has an overcoat layer, the overcoat layer can be formed as a layer containing an arbitrary polymer by coating in advance. There is no particular limitation on the material of the polymer used for these overcoat layers. For example, a hydrophilic binder polymer that can be added to the photosensitive layer can be used. Among these, various polyvinyl alcohols are particularly preferably used. When it is desired to provide the overcoat layer with a function of reducing oxygen permeation, the polyvinyl alcohol has a saponification degree of 85%.
When it is desired to impart even higher oxygen impermeability to the above polyvinyl alcohol, it is preferable to use a polyvinyl alcohol having a saponification degree of 95% or more. Also,
The overcoat layer is not limited to only one layer,
Layers or more can be stacked and installed.

Next, each embodiment of the image forming method using the image transfer photosensitive material of the present invention will be described. The light-sensitive material of the present invention is preferably used for a method for transferring an image from a light-sensitive material to an image-receiving material, particularly for producing a color proof.
An image forming method for forming a color proof using a silver halide, a reducing agent and a polymerizable compound has already been proposed by the present inventors (Japanese Patent Application No. 3-1737).
Nos. 88, 3-173789 and 3-173790
And No. 3-1737991). The image transfer photosensitive material provided with the peeling layer of the present invention can be applied to most of these various image forming methods (excluding the embodiments described in Japanese Patent Application No. 3-131790). Hereinafter, each embodiment will be sequentially described.

In the first embodiment, the following steps are carried out in the following order using the photosensitive material for image transfer and the image receiving material of the present invention. (1) a step of exposing the photosensitive polymerizable layer to an image (exposure step); (2) a step of developing the photosensitive polymerizable layer and thereby selectively curing the polymerizable compound in an exposed portion or an unexposed portion ( (3) a step of forming a toner image by adhering the colored toner to the surface of the uncured portion (toner developing step); and (4) bringing the photosensitive material into close contact with the image receiving material. Step of transferring the toner image to the image receiving material (transfer step).

In the second embodiment, the following steps (A) and (B) are carried out using the photosensitive material for image transfer and the image receiving material of the present invention.
(1) (2) (3), (A) (1) (B) (2)
(3), (A) (1) (2) (B) (3), (1)
(A) (B) (2) (3), (1) (A) (2) (B)
(3) and (1), (2), (A), (B), and (3). (A) a step of laminating the photosensitive material on the image receiving material (lamination step); (B) a step of laminating the image receiving material and the photosensitive material;
(1) a step of exposing the photosensitive polymerizable layer to an image (exposure step); and (2) a step of developing the photosensitive polymerizable layer, thereby exposing the exposed portion or the unexposed portion. A step of selectively curing the polymerizable compound in the exposed area (development step); and (3) a step of adhering the colored toner to the surface of the uncured area to thereby form a toner image (toner development step).

In the third embodiment, the following steps are carried out in the following order using the photosensitive material for image transfer (including a colorant) and the image receiving material of the present invention. (1) a step of exposing the photosensitive polymerizable layer to an image (exposure step); (2) a step of developing the photosensitive polymerizable layer and thereby selectively curing the polymerizable compound in an exposed portion or an unexposed portion ( (Development step); (3) a step of dissolving the uncured portion using an eluent to obtain a cured image, thereby forming a colored image (elution step); and (4) bringing the photosensitive material into close contact with the image receiving material; Thus, a step of transferring the colored image to the image receiving material (transfer step).

In a fourth embodiment, the following steps (A), (B), (1), (2) and (3) are carried out by using the image-transferring photosensitive material (including a colorant) and the image-receiving material of the present invention. (A) (1)
(B) (2) (3), (A) (1) (2) (B)
(3), (1) (A) (B) (2) (3), (1)
(A) (2) (B) (3) and (1) (2) (A)
(B) Perform in any order of (3). (A) a step of laminating the photosensitive material on the image receiving material (lamination step); (B) a step of laminating the image receiving material and the photosensitive material;
(1) a step of exposing the photosensitive polymerizable layer to an image (exposure step); and (2) a step of developing the photosensitive polymerizable layer, thereby exposing the exposed portion or the unexposed portion. A step of selectively curing the polymerizable compound in the exposed area (development step); and (3) a step of eluting the uncured area using an eluent to obtain a cured image, thereby forming a colored image (elution step) ).

A fifth embodiment is a photosensitive material for image transfer of the present invention (having an adhesive layer between a photosensitive polymerizable layer and a release layer).
The following steps are performed in the following order using the image receiving material. (1) a step of exposing the photosensitive polymerizable layer to an image (exposure step); (2) a step of developing the photosensitive polymerizable layer and thereby selectively curing the polymerizable compound in an exposed portion or an unexposed portion ( (Development step); (3) eluting the uncured portion using an eluent, thereby exposing the adhesive layer imagewise (elution step); (4) applying a colored toner to the surface of the adhesive layer And (5) bringing the photosensitive material into close contact with the image receiving material, thereby transferring the toner image to the image receiving material (transfer step).

In the sixth embodiment, the following steps (A), (B) and (B) are carried out by using the photosensitive material for image transfer (having an adhesive layer on the photosensitive polymerizable layer) and the image receiving material of the present invention. 1)
(2) (3) (4), (A) (1) (B) (2) (3)
(4), (A) (1) (2) (B) (3) (4),
(1) (A) (B) (2) (3) (4), (1) (A)
(2) (B) (3) (4) and (1) (2) (A)
(B) Perform in any order of (3) and (4). (A) a step of laminating the photosensitive material on the image receiving material (lamination step); (B) a step of laminating the image receiving material and the photosensitive material;
(1) a step of exposing the photosensitive polymerizable layer to an image (exposure step); and (2) a step of developing the photosensitive polymerizable layer, thereby exposing the exposed portion or the unexposed portion. A step of selectively curing the polymerizable compound in the exposed area (development step); (3) a step of eluting the uncured area using an eluent, thereby exposing the adhesive layer imagewise (elution step); And (4) a step of applying a colored toner to the surface of the adhesive layer to thereby form a toner image (toner developing step).

In the seventh embodiment, the following steps are carried out in the following order using the photosensitive material for image transfer and the image receiving material of the present invention. (1) a step of exposing the photosensitive polymerizable layer to an image (exposure step); (2) a step of developing the photosensitive polymerizable layer and thereby selectively curing the polymerizable compound in an exposed portion or an unexposed portion ( (Development step); (3) a step of eluting the uncured part using an eluent, thereby forming a cured adhesive part having an image (elution step); A step of applying a toner image to the surface of the adhesive cured portion and thereby forming a toner image (toner developing step); and (5) a step of bringing the photosensitive material into close contact with the image receiving material and thereby transferring the toner image to the image receiving material (transfer step) ).

In an eighth embodiment, the following steps (A) and (B) are carried out using the photosensitive material for image transfer and the image receiving material of the present invention.
(1) (2) (3) (4), (A) (1) (B) (2)
(3) (4), (A) (1) (2) (B) (3)
(4), (1) (A) (B) (2) (3) (4),
(1) (A) (2) (B) (3) (4) and (1)
(2) Perform in any order of (A), (B), (3) and (4). (A) a step of laminating the photosensitive material on the image receiving material (lamination step); (B) a step of laminating the image receiving material and the photosensitive material;
(1) a step of exposing the photosensitive polymerizable layer to an image (exposure step); and (2) a step of developing the photosensitive polymerizable layer, thereby exposing the exposed portion or the unexposed portion. A step of selectively curing the polymerizable compound in the exposed area (development step); (3) the uncured area is eluted using an eluent, thereby forming an adhesively cured area imagewise. Step (elution step); and (4) a step of applying a colored toner to the surface of the adhesive cured portion, thereby forming a toner image (toner developing step).

In the ninth embodiment, the following steps are carried out in the following order by using the photosensitive material for image transfer (including the colorant), the removal sheet and the image receiving material of the present invention. (1) a step of exposing the photosensitive polymerizable layer to an image (exposure step); (2) a step of developing the photosensitive polymerizable layer and thereby selectively curing the polymerizable compound in an exposed portion or an unexposed portion ( (Developing step); (3) After the removal sheet is brought into close contact with the surface of the photosensitive polymerizable layer, the sheet is peeled off so that an uncured portion or a cured portion is selectively adhered to the removal sheet to remove the photosensitive polymerizable layer. Removing, thereby forming a colored image (removing step); and (4) transferring the colored image to the image receiving material by bringing the photosensitive material into close contact with the image receiving material (transfer step).

In a tenth aspect, the following steps (A), (B), (1), (2) and (A) are performed using the photosensitive material for image transfer (including a coloring material), the removal sheet and the image receiving material of the present invention. 3),
(A) (1) (B) (2) (3), (A) (1) (2)
(B) (3), (1) (A) (B) (2) (3),
(1) (A) (2) (B) (3) and (1) (2)
(A), (B), and (3) are performed in any order. (A) a step of laminating the photosensitive material on the image receiving material (lamination step); (B) a step of laminating the image receiving material and the photosensitive material;
(1) a step of exposing the photosensitive polymerizable layer to an image (exposure step); and (2) a step of developing the photosensitive polymerizable layer, thereby exposing the exposed portion or the unexposed portion. (3) a step of selectively curing the polymerizable compound in the exposed portion (development step); and (3) an uncured portion or a cured portion by peeling the sheet after closely attaching the removal sheet to the surface of the photosensitive polymerizable layer. A step of selectively adhering to the removal sheet and removing it from the photosensitive polymerizable layer, thereby forming a colored image (removal step).

In the eleventh embodiment, the following steps are carried out using the photosensitive material for image transfer of the present invention (having an adhesive layer between the photosensitive polymerizable layer and the release layer), the removal sheet and the image receiving material. In the order given. (1) a step of exposing the photosensitive polymerizable layer to an image (exposure step); (2) a step of developing the photosensitive polymerizable layer and thereby selectively curing the polymerizable compound in an exposed portion or an unexposed portion ( (Development step); (3) After the removal sheet is brought into close contact with the surface of the photosensitive polymerizable layer, the sheet is peeled off, and the uncured portion is selectively adhered to the removal sheet and removed from the photosensitive polymerizable layer. (4) applying a colored toner to the surface of the adhesive layer, thereby forming a toner image (toner developing step); and (5) forming a photosensitive material. Close contact with the image receiving material,
Thus, a step of transferring the toner image to the image receiving material (transfer step).

In a twelfth embodiment, the following steps are carried out using the photosensitive material for image transfer of the present invention (having an adhesive layer on the photosensitive polymerizable layer), a removal sheet and an image receiving material.
(B) (1) (2) (3) (4), (A) (1) (B)
(2) (3) (4), (A) (1) (2) (B) (3)
(4), (1) (A) (B) (2) (3) (4),
(1) (A) (2) (B) (3) (4) and (1)
(2) Perform in any order of (A), (B), (3) and (4). (A) a step of laminating the photosensitive material on the image receiving material (lamination step); (B) a step of laminating the image receiving material and the photosensitive material;
(1) a step of exposing the photosensitive polymerizable layer to an image (exposure step); and (2) a step of developing the photosensitive polymerizable layer, thereby exposing the exposed portion or the unexposed portion. Step of selectively curing the polymerizable compound in the exposed portion (development step); (3) After the removal sheet is adhered to the surface of the photosensitive polymerizable layer, the sheet is peeled off to selectively remove the uncured portion. Removing the photosensitive polymerizable layer by adhering to a sheet, thereby forming a colored image (removing step); and (4) applying the colored toner to the surface of the adhesive layer, thereby forming a toner image. (Toner development step).

In the thirteenth embodiment, the following steps are carried out in the following order using the photosensitive material for image transfer, the removal sheet and the image receiving material of the present invention. (1) a step of exposing the photosensitive polymerizable layer to an image (exposure step); (2) a step of developing the photosensitive polymerizable layer and thereby selectively curing the polymerizable compound in an exposed portion or an unexposed portion ( (Developing step); (3) After the removal sheet is brought into close contact with the surface of the photosensitive polymerizable layer, the sheet is peeled off, and the cured portion is selectively adhered to the removal sheet and removed from the photosensitive polymerizable layer. (4) applying a colored toner to the surface of the adhesive cured portion, thereby forming a toner image (toner developing step); and (5) forming a photosensitive material. A step of bringing the toner image into close contact with the image receiving material and thereby transferring the toner image to the image receiving material (transfer step).

In a fourteenth aspect, the following steps (A), (B), (1), (2), (3), and (4) are performed using the photosensitive material for image transfer, the removal sheet, and the image receiving material of the present invention. (A)
(1) (B) (2) (3) (4), (A) (1) (2)
(B) (3) (4), (1) (A) (B) (2) (3)
(4), (1) (A) (2) (B) (3) (4) and (1) (2) (A) (B) (3) (4) in any order. (A) a step of laminating the photosensitive material on the image receiving material (lamination step); (B) a step of laminating the image receiving material and the photosensitive material;
(1) a step of exposing the photosensitive polymerizable layer to an image (exposure step); and (2) a step of developing the photosensitive polymerizable layer, thereby exposing the exposed portion or the unexposed portion. (3) a step of selectively curing the polymerizable compound in the exposed portion (development step); (3) a sheet in which the cured portion is selectively removed by adhering the removal sheet to the photosensitive polymerizable layer surface and peeling the sheet; And removing the photosensitive polymerizable layer from the photosensitive polymerizable layer to thereby form a colored image (removal step); and (4) applying the colored toner to the surface of the adhesive cured portion, thereby forming a toner image. (Toner development step).

In the transfer step or the peeling step in each of the above embodiments, the peeling layer of the present invention functions to transfer an image formed on the photosensitive material with high sensitivity to the image receiving material while maintaining high resolution. it can. After a transfer image is formed on an image receiving material for a certain color as described above, a similar process is performed on another color to form a two-color image on the image receiving material. By repeating this operation for another color, a color image can be formed on the image receiving material. Among the above aspects, the release layer of the present invention is particularly effective in the first aspect and the third aspect. Hereinafter, the first embodiment and the third embodiment will be described in more detail with reference to the drawings.

FIG. 3 is a schematic sectional view showing an exposure step in the first embodiment of the image forming method. A latent image (35) of silver halide is formed in the exposed portion (33) of the photosensitive layer irradiated with the light (31). On the other hand, the unexposed portion (3
In 2), there is no substantial change in the silver halide (34).
In FIG. 3, the image exposure process is described using the laminated photosensitive material shown in FIG. 2 as an example. However, the same process can be performed with a single-layer photosensitive material as described in FIG.

FIG. 4 is a schematic sectional view showing a developing step in the first embodiment of the image forming method. When the photosensitive material is heated (41), the reducing agent is converted into the polymerizable layers (42 and 43).
To the photosensitive layers (44 and 45), and develops the silver halide latent image in the exposed portions (45) of the photosensitive layer. The silver halide is developed into a silver image (49),
At the same time, the reducing agent is oxidized to form an oxidant radical (47). The oxidant radical (47) of the reducing agent moves from the exposed portion (45) of the photosensitive layer to the exposed portion (43) of the polymerizable layer. The polymerizable compound is cured by the action of the radical, and a cured portion (43) is formed. On the other hand, the reducing agent (46) contained in the unexposed portion of the polymerizable layer and the silver halide (48) contained in the unexposed portion of the photosensitive layer did not substantially change. The unexposed portion (42) is an uncured portion. In FIG. 4, a heat development process is described as an example, but a wet phenomenon process using a developing solution may be performed. In FIG. 4, a system in which the polymerizable compound in the exposed portion is selectively cured has been described as an example. However, as described above, by changing the conditions such as the type of the reducing agent, the polymerizable compound in the unexposed portion is It is also possible to employ a system that selectively cures. Similarly, in each of the drawings describing the following development processing, a system in which the polymerizable compound in the heat development processing and the exposed area is selectively cured will be described as an example. A system of selective curing is of course feasible.

FIG. 5 is a schematic sectional view showing a toner developing step in the first embodiment of the image forming method. When the colored toner (51) is applied to the surface of the polymerizable layer after removing the photosensitive layer, an uncured portion (52) of the polymerizable layer having tackiness is applied.
And the toner adheres selectively to the cured portion (53). As a result, a toner image is formed on the photosensitive material.

FIG. 6 is a schematic sectional view showing the transfer step in the first embodiment of the image forming method. FIG. 6 shows a state after the transfer. The photosensitive material (62) is brought into close contact with the image receiving material (61), whereby the toner image (63) formed on the uncured portion of the polymerizable layer is transferred from the photosensitive material to the image receiving material together with the release layer (64). As described above, a transfer image is formed on the image receiving material.

FIG. 7 is a schematic sectional view showing an exposure step in the third embodiment of the image forming method. A latent image (75) of silver halide is formed in the exposed portion (73) of the photosensitive layer irradiated with the light (71). On the other hand, the unexposed portion (7
In 2), there is no substantial change in the silver halide (74).

FIG. 8 is a schematic sectional view showing a developing step in the third embodiment of the image forming method. When the photosensitive material is heated (81), the reducing agent is converted into the polymerizable layers (82 and 83).
To the photosensitive layers (84 and 85), and develops the silver halide latent image in the exposed portions (85) of the photosensitive layer. The silver halide is developed into a silver image (89),
At the same time, the reducing agent is oxidized to form an oxidant radical (87). The oxidant radical (87) of the reducing agent moves from the exposed portion (85) of the photosensitive layer to the exposed portion (83) of the polymerizable layer. The polymerizable compound is cured by the action of the radical, and a cured portion (83) is formed. On the other hand, the reducing agent (86) contained in the unexposed portion of the polymerizable layer and the silver halide (88) contained in the unexposed portion of the photosensitive layer did not substantially change. The unexposed portion (82) is an uncured portion.

FIG. 9 is a schematic sectional view showing an elution step in the third embodiment of the image forming method. The uncured portion of the polymerizable layer is removed using the eluate (91), thereby forming a colored image on the cured portion (92). The photosensitive layer is peeled off and removed before the elution step, or is removed using an eluate together with the uncured portion of the polymerizable layer in the elution step.

FIG. 10 is a schematic sectional view showing a transfer step in the third embodiment of the image forming method. FIG. 10 shows a state after the transfer. The photosensitive material (102) is transferred to the image receiving material (10
The colored image (103) formed on the cured portion of the polymerizable layer is transferred from the photosensitive material to the image receiving material together with the release layer (104).

The above is a typical embodiment of the image forming method using the light-sensitive material of the present invention. In image formation, an additional step can be added as necessary in addition to the above steps. In the case of a laminated photosensitive material, a step of removing a layer provided above a polymerizable layer such as a photosensitive layer is required before (or after) the elution step or simultaneously with the elution step. The removal of this layer may be performed by peeling. Alternatively, the layer above the polymerizable layer may be removed by elution or swelling with a liquid that does not dissolve the polymerizable layer. Further, in the elution step, the polymer may be removed together with the uncured portion of the polymerizable layer using an eluate. Further, a step of transferring the monochromatic image formed on the image receiving material to another image receiving material may be further performed. A step of transferring a color (multicolor) image formed on the image receiving material to another image receiving material can also be performed. When transferring an image, the image is turned over (reverse image). When forming a final color image on a transparent support, the image may be turned upside down.However, when forming a color image on an opaque support, it is necessary that the final image be formed with the desired normal image. It is. For this purpose, it is necessary to perform an operation such as performing the exposure upside down or transferring the image again to return the reverse image to the normal image. When adding the above-mentioned improper transfer step, it is necessary to consider such a relationship between the normal image and the reverse image. In addition, optional steps such as a step of removing additional layers such as an intermediate layer and a back layer, a step of matting the surface of the image receiving material on which an image is formed, and a step of applying a matting agent to the image receiving material are added. be able to.

Each step of the image forming method will be described in more detail. [Exposure Step] The image exposure in the exposure step may be performed from the front side of the photosensitive material (the side opposite to the support) or from the support side. Examples of the exposure method for performing image exposure include reflection image exposure using a xenon lamp, a tungsten lamp, a fluorescent lamp, or the like as a light source, close contact exposure through a transparent positive film, and scanning exposure using a laser beam, a light emitting diode, or the like. The photosensitive material of the present invention is
It is characterized in that an image can be formed by drawing by scanning exposure. Therefore, the present invention is particularly advantageous when using a scanning exposure. For scanning exposure, helium-neon laser, helium-cadmium laser, argon ion laser, krypton ion laser, YAG laser, ruby laser, nitrogen laser, dye laser, excimer laser, semiconductor (eg, GaAs / GaAlAs, InGaAsP) laser , Alexandrite laser, copper vapor laser,
Laser light such as erbium laser can be used as a light source. Scanning exposure using a light emitting diode or a liquid crystal shutter as a light source (including a line printer type light source using a light emitting diode array, a liquid crystal shutter array, or the like) is also possible. The light source or exposure wavelength that can be used for image exposure depends on the photosensitive region of the silver halide emulsion used in the photosensitive material, and wavelength regions of near ultraviolet light, visible light, and near infrared light can be used. The exposure amount is determined mainly by the sensitivity of the silver halide emulsion and is 0.01 to 100.
It can be exposed with light energy of 00 erg / cm ² . By performing the above-mentioned image exposure, a latent image of silver halide is formed in the exposed portion.

[Developing Step] In the image forming method, it is preferable to use a dry developing treatment in which the photosensitive material is heated. The developing step can be performed simultaneously with the above-mentioned exposure step. The image-exposed photosensitive material is heated by a conventionally known heating means. Heating involves contacting the photosensitive material with a heated object (eg, roller, flat plate, etc.), or heating the photosensitive material by infrared irradiation, leaving the photosensitive material in a heated zone or passing through a zone Contact and non-contact heating means such as heating can be used. Further, at the time of heating, the surface of the light-sensitive material may be heated by covering the surface thereof without exposing the surface of the light-sensitive material to the air and exposing it to an arbitrary object. The temperature and time required for heating depend on the characteristics of the photosensitive material used. Generally, the heating temperature is preferably in the range of 70 ° C to 200 ° C. The heating time is preferably in the range of 1 to 180 seconds. In the image formation, it is also possible to carry out a wet developing process using a developing solution. In the developing step, the silver halide on which the latent image has been formed by exposure is developed, and at the same time, an oxidized form of the reducing agent is formed at that portion. When the oxidized form of the reducing agent has a polymerization promoting action, the polymerizable compound in the exposed area is selectively cured, and when the oxidized form of the reducing agent has a polymerization inhibiting action, the polymerizable compound in the unexposed area is selectively cured. In the case of using a photosensitive material containing a photopolymerization initiator as a polymerization initiator in a system for curing a portion where a latent image is not formed (unexposed portion), the photosensitive material is entirely exposed after the development step.

[Elution Step] (Third to Eighth Aspects) In the developing step, the photosensitive polymerizable layer (the polymerizable layer in the case of a laminated photosensitive material)
The exposed part or the unexposed part is selectively cured. As a result,
The solubility of the hardened part and the unhardened part in the eluate changes, and the hardened part is not eluted by the eluate, but the unhardened part is eluted by the eluate to form an image on the photosensitive material. The eluent (or etchant) for removing the uncured part is
Any solvent can be used as long as the uncured portion of the (photosensitive) polymerizable layer can be removed. Preferably, an alkaline solvent is used. The alkaline solvent is an aqueous solution containing an alkaline compound, an organic solvent containing an alkaline compound, or a mixture of an aqueous solution containing an alkaline compound and an organic solvent. Various organic and inorganic compounds can be used as the alkaline compound. Examples of the alkaline compound include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, potassium silicate, sodium metasilicate, potassium metasilicate, sodium phosphate, potassium phosphate,
Ammonia and amino alcohols (eg, monoethanolamine, diethanolamine, triethanolamine) can be mentioned. As the solvent for the eluate, water or various organic solvents can be used as described above. The solvent of the eluate is preferably mainly composed of water. An organic solvent can be added to the eluate mainly composed of water, if necessary. Alcohols or ethers are preferred as the organic solvent. Examples of alcohols include lower alcohols (eg, methanol, ethanol, propanol, butanol), alcohols having an aromatic group (eg, benzyl alcohol, phenethyl alcohol), polyhydric alcohols (eg, ethylene glycol, diethylene glycol, triethylene) Glycol, polyethylene glycol) and amino alcohols (eg, monoethanolamine, diethanolamine, triethanolamine). Examples of ethers include cellosolves. The eluate is
It may contain a surfactant, an antifoaming agent, and other various additives as necessary.

[Removing Step] (Ninth to Fourteenth Aspects) In the developing step, the photosensitive polymerizable layer (polymerizable layer in the case of a laminated photosensitive material, the same applies hereinafter) is selectively exposed or unexposed. Hardens to As a result, the adhesion between the photosensitive polymerizable layer and the interface of the photosensitive material on the support side changes between the uncured portion and the cured portion. When the release sheet is brought into close contact with the surface of the photosensitive polymerizable layer of the photosensitive material, the adhesive force between the photosensitive polymerizable layer and the interface of the release sheet also differs between the uncured portion and the cured portion. When the photosensitive material and the release sheet are peeled off, the adhesive force at the interface between the uncured portion and the support side of the photosensitive material is greater than the adhesive force between the release sheet side and the adhesiveness at the interface between the cured portion and the support side of the photosensitive material. When the force is smaller than the adhesion to the release sheet, only the cured portion is transferred to the release sheet. vice versa,
The adhesive force at the interface between the uncured portion and the support of the photosensitive material is smaller than the adhesive force at the release sheet side, and the adhesive force at the interface between the cured portion and the support of the photosensitive material is less than the adhesive force between the release sheet and the release sheet. When large, only the uncured portions are transferred to the release sheet. Whether the cured portion is transferred or the uncured portion is transferred, the properties of the polymerizable compound in the photosensitive polymerizable layer, the amount of the polymerizable compound added, the properties of the binder in the photosensitive polymerizable layer,
The above-mentioned adhesion varies depending on the nature of the other components in the photosensitive polymerizable layer and the amount thereof added, as well as various conditions (heating temperature, time, pressurization temperature, etc.) in the removal step, and the above-mentioned adhesive strength varies. sell. As a result, a cured portion or an uncured portion selectively remains in an image state. In the ninth and tenth aspects, a color image is formed on a photosensitive material. In the eleventh and twelfth aspects, the adhesive layer is exposed in the form of an image, and a colored toner is attached thereto to form a toner image.
In the thirteenth and fourteenth aspects, an uncured portion having adhesiveness is formed in an image shape, and a colored toner is adhered to the uncured portion. Art paper, coated paper, printing paper, and plastic sheets can be used as the release sheet used in the removing step. These surfaces may be coated with a resin binder, a plasticizer, a surface treatment agent, a matting agent, or the like in one layer or in multiple layers. The release sheet can be formed using the same material as an image receiving material described later.

[Transfer Step] (First, third, fifth, seventh, ninth, eleventh, and thirteenth)
Aspect) In the transfer step in the third and ninth aspects,
The image receiving material and the image-form cured surface of the photosensitive material come into contact with each other, and transfer is performed by applying pressure or heat or both pressure and heat thereto. In the transfer step, the release layer is transferred to the image receiving material together with the photosensitive polymerizable layer (polymerizable layer in the case of a laminated photosensitive material, the same applies hereinafter). Another adjacent layer (such as an undercoat layer) may be simultaneously transferred to the image receiving material. The transfer conditions such as the transfer temperature and transfer pressure in this transfer step can be changed by various factors such as the properties of the photosensitive polymerizable layer and the material of the image receiving material. Generally, the transfer temperature is 1
The temperature is preferably 0 ° C. to 200 ° C., and the transfer pressure is 0 ° C.
It is preferably from 2000 to 2000 kg / cm ² . In the transfer steps in the first, fifth, seventh, eleventh, and thirteenth aspects, the image receiving material comes into contact with the surface of the photosensitive material to which the colored toner has adhered, and comes into contact with the pressure or heat or the pressure and heat. Transfer is performed by applying both. In the transfer step, what is transferred to the image receiving material is a colored toner, a photosensitive polymerizable layer, and a release layer. Further, another layer (such as an undercoat layer) adjacent to the photosensitive polymerizable layer may be simultaneously transferred thereto. The transfer temperature and transfer pressure vary greatly depending on the material of the image receiving material, the material of the colored toner, and the properties of the photosensitive material. Generally, the transfer temperature is preferably from 10 ° C. to 200 ° C., and the transfer pressure is from 0 to 2000 kg /
cm ² is preferred. As an image receiving material used in the transfer step, art paper, coated paper, printing paper, and a plastic sheet can be used. These surfaces may be coated with a resin binder, a plasticizer, a surface treatment agent, a matting agent, or the like in one layer or in multiple layers. The image receiving material and the transfer step are described in JP-B-49-441, JP-A-47-41830, JP-A-48-93337,
JP-A-51-5101, JP-A-59-97140,
JP-A-61-189533, JP-A-2-244146
JP-A-2-244147 and JP-A-2-244
No. 148, each publication.

[Toner developing step] (first, second, fifth to eighth and eleventh to eleventh)
Aspect 4) Toner development is carried out by sprinkling a colored toner on the surface of the photosensitive polymerizable layer or the adhesive layer and physically contacting the surface with a cloth, sponge or the like. The toner developing step can be performed using an automatic toner developing device such as an automatic toning machine 2900 of DuPont. The method of forming a colored image by bringing a colored toner into contact with the adhesive surface as described above is described in JP-B-48-31323, JP-A-59-104665 and JP-B1-36611. There is. In the toner developing step, the colored toner selectively adheres to the adhesive surface to form an image. As a colored toner having such properties, a particle size of 0.1 μm
A colored powder of from .mu.m to 50 .mu.m is used. The colored powder consists of a colorant (pigment or dye) alone, a mixture of a colorant and a resin binder, or a mixture of a colorant, a resin binder and other components. As the colorant, any conventionally known organic and inorganic pigments or dyes can be used. These pigments or dyes are described in "Dye Handbook", "Color Index" and the like. Further, any of the coloring agents exemplified in the photosensitive material described later can be used. As the resin binder used for the colored toner, conventionally known natural and synthetic polymers can be arbitrarily used. Examples of the resin binder include polyvinyl chloride, cellulose acetate, cellulose acetate butyrate, polystyrene, polymethyl methacrylate, methyl cellulose and carboxymethyl cellulose.
If necessary, a plasticizer, a monomer, a surfactant, an antistatic agent, a dispersion stabilizer, a surface treatment agent, and the like can be added to the colored toner. Regarding colored toners, see US Pat. Nos. 3,620,726 and 430.
No. 4843, No. 4397942, No. 4461822
Nos. 4,454,072 and 4,215,193, JP-B1-36611, JP-B-49-7750.
And JP-A-59-104665.

[Laminating Step] (Embodiments 2, 4, 6, 8, 10, 12, and 14) A photosensitive material is closely adhered to an image receiving material, and lamination is performed by heating or pressurizing, or both.
For example, lamination can be performed by an operation such that the image receiving material and the photosensitive material are brought into close contact with each other and passed between rubber rollers. Other conventionally known laminating methods can also be used in the laminating step. The image receiving material used in the laminating step is not particularly limited as long as it can stably hold a film having a thickness of about 5 to 50 μm. The image receiving materials used in the laminating process include art paper,
Coated paper, printing paper, and plastic sheets can be used. Also, a resin binder on these surfaces,
A plasticizer, a surface treatment agent, a matting agent and the like may be coated in one layer or in multiple layers. The photosensitive material may be laminated on the image receiving material at the time of manufacturing the photosensitive material.

[0115]

EXAMPLES Reference Example 1 A photosensitive material for image transfer was prepared as follows. "Peeling layer" A coating liquid for forming a release layer having the following composition was prepared, applied on a biaxially stretched 100 μm-thick polyethylene terephthalate film to a thickness of 2.0 μm, dried and dried. Was formed.塗布 Release layer coating solution ───────── ─────────────────────────── Polyvinyl butyral (Denka butyral 5000-A, flow softening point: 78 ° C, Denki Kagaku Kogyo Co., Ltd.) 3.75 g Surfactant (MegaFac F177P, manufactured by Dainippon Ink Co., Ltd.) 0.07 g Methanol 37.50 g n-propanol 37.50 g ────────────────────

[Preparation of Yellow Pigment Dispersion] A liquid having the following composition was dispersed with a Dynomill at 2000 rpm for 2 hours to obtain a yellow pigment dispersion having an average particle size of 0.25 μm.

<< Yellow Pigment Dispersion >> ───────────────────────────── Yellow Pigment (CI Pigment Yellow 14) 30.0 g Allyl methacrylate / methacrylic acid copolymer ( (Copolymerization ratio = 80/20) 50.0 g propylene glycol monomethyl ether 320.0 g ────

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[Formation of Polymerizable Layer] The following coating solution was applied on the release layer and dried to form a polymerizable layer having a thickness of 1.3 μm.

<< Coating Liquid for Polymerizable Layer >> ─────────────────────────────── Dipentaerythritol hexaacrylate 5.0 g Allyl methacrylate / methacrylic acid copolymer (copolymer Ratio = 80/20) 10.0 g The above yellow pigment dispersion 40.0 g Reducing agent (J) 1.0 g Methyl ethyl ketone 30.0 g ────────────────

[Preparation of Silver Halide Emulsion] An appropriate amount of ammonium was added to a vessel containing gelatin, potassium bromide and water and heated at 55 ° C., and the pAg value in the reaction vessel was increased to 7.60. While maintaining, an aqueous solution of silver nitrate and an aqueous solution of potassium bromide to which hexachloroiridate (III) is added so as to have a molar ratio of iridium to silver of 10 ^-7 mol are added by a double jet method, and then potassium iodide is added. A monodispersed silver iodobromide emulsion having an average grain size of 0.25 μm was prepared to have a silver iodide content of 0.2 mol%. These emulsion grains had 98% of the total number of grains within ± 40% of the average grain size. After desalting this emulsion, p
After adjusting the H to 6.2 and the pAg to 8.6, gold / sulfur sensitization was performed with sodium thiosulfate and chloroauric acid, and then a methanol solution of the following spectral sensitizing dye (concentration: 2.
(0 M / liter) was added to 1 kg of the emulsion in an amount of 200 cc and stirred at 60 ° C. for 15 minutes to obtain a silver halide emulsion.

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"Formation of Photosensitive Layer" The following coating solution was applied on the above-mentioned polymerizable layer and dried to a dry film thickness of about 1.4.
A μm photosensitive layer was provided.

<< Coating Solution for Photosensitive Layer >> １０ 10% by weight aqueous solution of polyvinyl alcohol (PVA-420, manufactured by Kuraray Co., Ltd.) 13 0.5 g of a 0.12 wt% methanol solution of the following additive (1) 0.54 g of a 0.22 wt% methanol solution of the following additive (2) 0.37 g of the above silver halide emulsion 0.3 g of the following interface 5% by weight aqueous solution of activator 1.8g Water 1.9g

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[0126]

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[0127]

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"Preparation of Base Precursor Dispersion" A 250 wt.
Dispersed in 0 g. The particle size of the base precursor was about 0.5 μm or less.

[0129]

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[Formation of Overcoat Layer] 100 g of a 10% by weight aqueous solution of polyvinyl alcohol (PVA-205, saponification degree: 88.0%, manufactured by Kuraray Co., Ltd.), 6.25 g of the base precursor dispersion, and A coating solution was prepared by mixing 4 g of a 5% by weight aqueous solution of a surfactant. This coating solution was applied on the photosensitive layer and dried to form an overcoat layer having a dry film thickness of about 3.0 μm.

Reference Example 2 An image transfer photosensitive material was prepared in the same manner as in Reference Example 1, except that the thickness of the release layer was changed to 1.5 μm.

Reference Example 3 A photosensitive material for image transfer was prepared in the same manner as in Reference Example 1, except that the thickness of the release layer was changed to 1.0 μm.

Reference Example 4 A photosensitive material for image transfer was prepared in the same manner as in Reference Example 1, except that the thickness of the release layer was changed to 0.5 μm.

Reference Example 5 A photosensitive material for image transfer was prepared in the same manner as in Reference Example 1, except that the thickness of the release layer was changed to 0.3 μm.

Comparative Example 1 For comparison, a photosensitive material for image transfer using a photopolymerization initiator was prepared as follows. "Formation of Photopolymer Layer" The following coating solution was applied onto the release layer (film thickness: 0.5 μm) used in Example 4 and dried to form a photopolymer layer having a thickness of 1.30 μm.

塗布 Coating solution for photopolymerization layer───── ─────────────────────────────── Dipentaerythritol hexaacrylate 5.0 g Allyl methacrylate / methacrylic acid copolymer (copolymer Ratio = 80/20) 10.0 g Yellow pigment dispersion used in Example 1 40.0 g Michler's ketone 0.4 g 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer 0.4 g Methyl ethyl ketone 30.0 g ────────────────────────────────────

[Formation of Overcoat Layer] 100 g of a 10% by weight aqueous solution of polyvinyl alcohol (PVA-205, saponification degree: 88.0%, manufactured by Kuraray Co., Ltd.) was prepared.
4 g of the 5% by weight aqueous solution of the surfactant used in the above was mixed to prepare a coating solution. This coating solution was applied on the photopolymerization layer and dried to form an overcoat layer having a dry film thickness of about 3.0 μm.

Comparative Example 2 A photosensitive material for image transfer was prepared in the same manner as in Comparative Example 1, except that the thickness of the release layer was changed to 0.3 μm.

[Evaluation of Peeling Property] After determining the optimum exposure amount of the image transfer photosensitive materials of Reference Examples 1 to 5 and Comparative Examples 1 and 2, quantitative evaluation of the peeling property was performed as follows. The optimum exposure amount for the photosensitive material for image transfer of Reference Examples 1 to 5 is 3 μm on the photosensitive surface with light passed through a 500 nm band-pass filter (half-width 50 nm).
J / cm ² . The optimum exposure amount of the photopolymerizable photosensitive material for image transfer of Comparative Examples 1 and 2 was 80 counts with an ultraviolet exposure apparatus (manufactured by Dainippon Screen Co., Ltd.). 4.5 cm of the photosensitive material for image transfer of Reference Examples 1 to 5
After cutting to a size of width and 12 cm length, exposure was performed at the above-mentioned optimum exposure amount. Next, on the overcoat layer side,
While applying a polyethylene terephthalate film of 5 μm, an iron plate heated to 140 ° C. was pressed against the back surface of the support and heated. Thereby, the silver halide is reduced and the polymerizable layer is cured at the same time. After washing the photosensitive layer and the overcoat layer with water, the polymerizable layer was immersed in an aqueous alkaline solution (DN-3C manufactured by Fuji Photo Film Co., Ltd. diluted with water to 1/3) for 30 seconds and dried at room temperature. . Since the polymerizable layer was cured, it did not dissolve in the aqueous alkali solution (exposed sample). The sample which was not exposed was similarly heated, washed with water, immersed in the above alkaline aqueous solution for 30 seconds, and dried at room temperature. Since the polymerizable layer was not cured, it was dissolved in an aqueous alkali solution, leaving only a release layer on the support (unexposed sample). As described above, an exposed sample and an unexposed sample were prepared for each photosensitive material for image transfer. For the photopolymerizable image transfer photosensitive materials of Comparative Examples 1 and 2, the sample subjected to ultraviolet exposure and the sample not subjected to exposure were
After removing the overcoat layer by washing with water, it was similarly immersed in the above-mentioned alkaline aqueous solution. In this way, for each photosensitive material for image transfer, a sample in which the cured photopolymerized layer remained (exposed sample) and a sample in which only the release layer remained (unexposed sample) were prepared.

An adhesive Mylar tape was attached to the front side of the obtained sample. This was used as a peel strength measuring tester (Tensilon UTM-II- manufactured by Orientec Co., Ltd.).
(Type 20), a 180-degree peel test was performed, and the force required to peel the peel layer from the support was measured. FIG.
FIG. 2 is a schematic cross-sectional view illustrating the above-described measurement method. FIG.
As shown in FIG. 1, a mylar tape (114) was stuck on the surface of the polymerizable layer (113) of the photosensitive material for image transfer.
The release layer (112) is peeled from the support ((111)) by applying a force (F) in the direction of 80 degrees, and the above results are shown in Table 1. Next, each of the photosensitive materials for image transfer is listed. An image was exposed through a film, each exposure was performed under the above-mentioned optimum exposure conditions, and then a development process was performed under each of the above-described conditions to prepare a sample having a cured image formed on the release layer. (Image receiving sheet CR-
T3, the image surface was brought into close contact with the image receiving surface of Fuji Photo Film Co., Ltd., and a laminator (Laminator CA-600) was used.
T, manufactured by Fuji Photo Film Co., Ltd.). Next, the support of the photosensitive material was peeled off, and the image was transferred to the image receiving material. The results are also shown in Table 1.

[0141]

[Table 1] Table 1 感光 Photosensitive material Release layer thickness release Unexposed sample Image transfer of exposed sample to image receiving material required for Reference Example 1 2.0 μm 11 g 10 g Good Reference Example 2 1.5 μm 12 g 11 g Good Reference Example 3 1.0 μm 13 g 120 g Good Reference Example 4 0.5 μm 12 g> 1000 g Bad Reference Example 5 0.3 μm 14 g> 1000 g Bad Comparative Example 1 0.5 μm 13 g 13 g good Comparative Example 2 0.3 μm 13 g 12 g good ─────────────────────────────────── ─

As shown in Table 1, in the case of the photopolymerizable image transfer material (Comparative Examples 1 and 2), the force required for peeling was small, and the value was the same in both the unexposed sample and the exposed sample. On the other hand, in the photosensitive material for image transfer using silver halide ( Reference Examples 1 to 5), the unexposed sample has a small force required for peeling regardless of the peeling layer thickness, but the exposed sample has a film thickness of less than 1.0 μm. In ( Reference Examples 4 and 5), the force required for peeling was very large and the peeling was not successful. When the thickness of the peeling layer was 1.0 μm or more ( Reference Examples 1 to 3), the force required for peeling was small and the peeling was easy. Further, with the photopolymerizable image transfer material (Comparative Examples 1 and 2), an image was successfully transferred. On the other hand, in the image transfer photosensitive material using silver halide, when the film thickness is less than 1.0 μm ( Reference Examples 4 and 5), the non-image portion (unexposed portion) is well transferred to the image receiving material. However, in the image portion (exposed portion), the release layer did not sufficiently peel from the support of the photosensitive material, and the image transfer was poor. However, when the thickness of the release layer is 1.0 μm or more ( Reference Examples 1 to 3),
Both the exposed part and the unexposed part were easily peeled off, and a good transferred image could be formed on the image receiving material.

[Examples 1 to 5 ] In Reference Examples 1 to 5, the binder of the release layer was changed from Denka butyral 5000A (flow softening point: 78 ° C) to Eslek BH-3 (polyvinyl butyral, flow softening).
(Point: 205 ° C., manufactured by Sekisui Chemical Co., Ltd.) to prepare a photosensitive material for image transfer in the same manner.

[Comparative Examples 3 and 4] In Comparative Examples 1 and 2, the binder of the release layer was changed to Denkabutyral 500.
0A to Eslek BH-3 (polyvinyl butyral,
A photosensitive material for image transfer was prepared in the same manner, except that Sekisui Chemical Co., Ltd.) was used.

[Evaluation of Releasability] Exposed samples and unexposed samples were prepared in the same manner as in Reference Examples 1 to 5 and Comparative Examples 1 and 2, and the releasability was evaluated. The results are shown in Table 2.

[0146]

[Table 2] Table 2 ──────────────────────────────────── Photosensitive material Release layer thickness release Unexposed sample Image transfer of exposed sample to image receiving material required for Example 1 2.0 μm 11 g 11 g Good Example 2 1.5 μm 12 g 12 g Good Example 3 1.0 μm 12 g 240 g Good Example 4 0.5 μm 12 g> 1000 g Bad Example 5 0.3 μm 11 g> 1000 g Bad Comparative Example 3 0.5 μm 11 g 12 g good Comparative Example 4 0.3 μm 12 g 11 g good ─────────────────────────────────── ─

As shown in Table 2, in the case of the photopolymerizable image transfer material (Comparative Examples 3 and 4), the force required for peeling was small, and the value was the same in both the unexposed sample and the exposed sample. On the other hand, in the photosensitive material for image transfer using silver halide (Examples 1 to 5 ), the unexposed sample requires a small force for peeling regardless of the peeling layer thickness, but the exposed sample has a film thickness of less than 1.0 μm. In Examples 4 and 5 , the force required for peeling was very large and the peeling was not successful. When the thickness of the peeling layer was 1.0 μm or more (Examples 1 to 3 ), the force required for peeling was small and the peeling was easy. In addition, with the photopolymerizable image transfer material (Comparative Examples 3 and 4), an image was successfully transferred. On the other hand, in the case of a photosensitive material for image transfer using silver halide, when the film thickness is less than 1.0 μm (Examples 4 and 5 ), the non-image portion (unexposed portion) is well transferred to the image receiving material. However, in the image portion (exposed portion), the release layer did not sufficiently peel from the support of the photosensitive material, and the image transfer was poor. However, when the thickness of the release layer is 1.0 μm or more (Examples 1 to 3 ),
Both the exposed part and the unexposed part were easily peeled off, and a good transferred image could be formed on the image receiving material.

Example 6 A black pigment (carbon black, CI Pigment) was used in Example 2 in place of the yellow pigment as the pigment for the polymerizable layer.
ment Black 7) and a photosensitive material for transferring a black image, a photosensitive material for transferring a cyan image, and a photosensitive material for transferring a magenta image were prepared in the same manner except that the following pigments were used.

[0149]

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[0150]

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(Preparation of Color Proof) A color proof was prepared as follows using the above-described photosensitive material for transferring a black image in accordance with the third mode of image formation. Using an air-cooled argon ion laser as a light source, exposure for black image formation was performed by scanning exposure (exposure amount on the film surface: 3 μJ / cm ² ) at an exposure wavelength of 488 nm. Next, while a polyethylene terephthalate film having a thickness of 75 μm was applied to the overcoat leather, a hot plate heated to 140 ° C. was pressed against the back surface of the support and heated. Thereby, the silver halide is reduced and the polymerizable layer is cured at the same time. After removing the photosensitive layer and the overcoat layer by washing with water, the polymerizable layer was immersed in an aqueous alkaline solution (DN-3C manufactured by Fuji Photo Film Co., Ltd. diluted with water to 1/3) for 30 seconds and washed with water. After that, it was dried at room temperature. Thus, a sample having a black cured image formed on the release layer was prepared. This was brought into close contact with the image receiving surface of an image receiving material (image receiving sheet CR-T3, manufactured by Fuji Photo Film Co., Ltd.), and a laminator (Laminator CA-6) was used.
00T, manufactured by Fuji Photo Film Co., Ltd.). Next, the support of the photosensitive material was peeled off, and the black image was transferred to the image receiving material. Similarly, the photosensitive material for forming a cyan image was exposed to light for forming a cyan image, developed by heat, washed with water and eluted to form a cyan image on the photosensitive material. This was brought into close contact with the image receiving material on which the black image was transferred, and the cyan image was transferred onto the black image. Further, in the same manner, the above magenta image forming photosensitive material was exposed to magenta image forming exposure, developed by heat, washed with water and eluted to form a magenta image on the photosensitive material. This was brought into close contact with the image receiving material to which the above-described black image and cyan image had been transferred, and the magenta image was further transferred. Furthermore, in the same manner, the photosensitive material for yellow image formation prepared in Example 2 was exposed for yellow image formation, heat-developed, washed with water and eluted to form a yellow image on the photosensitive material. did. This was brought into close contact with the image receiving material to which the above-mentioned black image, cyan image and magenta image had been transferred, and the yellow image was further transferred. Thus, a four-color image was formed on the image receiving material. Next, the art paper is brought into close contact with the image receiving surface of the image receiving material on which the four-color image is formed,
Thermal adhesion was performed using a laminator (Laminator CA-600T, manufactured by Fuji Photo Film Co., Ltd.). Next, the support of the image receiving material was peeled off, and the image was transferred from the image receiving material to art paper to produce a color proof similar to a printed matter. The image quality of the obtained prule was good for faithfully reproducing the original digital image data.

Example 7 (Preparation of photosensitive material) A photosensitive material for image transfer was prepared as follows. "Release layer" A coating solution for forming a release layer having the following composition was prepared, applied on a biaxially stretched 100 μm-thick polyethylene terephthalate film to a thickness of 2.4 μm, dried, and dried. Was formed.

塗布 Coating liquid for release layer────── ────────────────────────────── Polyamide resin (Diamid 452, manufactured by Daicel Corporation) 3.75 g Surfactant (Megafax F177P, manufactured by Dainippon Ink Co., Ltd.) 0.07 g methanol 37.50 g n-propanol 37.50 g ─────────

[Formation of Polymerizable Layer] The following coating solution was applied on the release layer and dried to form a polymerizable layer having a thickness of 1.3 μm.

<< Coating Liquid for Polymerizable Layer >> ─────────────────────────────── Dipentaerythritol hexaacrylate 5.0 g diacrylate monomer (A-600, Shin-Nakamura 5.0 g Allyl methacrylate / methacrylic acid copolymer (copolymerization ratio = 80/20) 10.0 g Reducing agent (J) 1.0 g Methyl ethyl ketone 70.0 g ─────────────────────────

[Formation of Photosensitive Layer] In the same manner as in Reference Example 1, a photosensitive layer was formed on the polymerizable layer so as to have a dry film thickness of 1.3 μm.

[Formation of Overcoat Layer] As in Reference Example 1, an overcoat layer was formed on the photosensitive layer so that the dry film thickness was 3.5 μm.

(Preparation of Yellow Toner) A yellow toner was prepared using the following components.

{Amount of Yellow Toner Component (g)} ──────────────────────────────── Pigment Yellow 74 (CI # 11741) 4380.0 Cellulose acetate 6548.0 Acetone 27669 2.6 water 22680.0 dimethylpolysiloxane (1253.0 g per 11 kg of toner) ───

Water and acetone were thoroughly mixed and charged into a ball mill. The mill includes a 0.049 cm diameter stainless steel ball stirred at 150 rpm. In the mixing operation, a nitrogen atmosphere was set in the mill. Then, about 2/3 of the indicated weight of cellulose acetate was added to 3
加 え 5 min and stirred in the liquid for about 2 min more.
The pigment was added over 2 minutes, and the remaining cellulose acetate was added. The mixture is then placed in a mill for 4 hours.
Stirred at 150 rpm for hours. The contents were washed with water and filtered to collect the wet toner. Wash the toner with water, and
Dried in an oven at ℃ 125 ° C. and powdered in a hammer mill. Next, the toner was surface-treated by mixing dimethylsiloxane in a blender. Further, the toner was mixed with an equivalent weight of ionic hydrocarbon copolymer beads having an average particle size of 23 μm in a tabletop blender.

(Preparation of Magenta Toner) Except that the following components were used and the stirring time was changed from 4 hours to 6 hours,
A magenta toner was prepared in the same manner as the preparation of the yellow toner.

{Magenta Toner Component Amount (g)} ──────────────────────────────── Pigment Red 122 (Quid Magenta) 3315.0 Pigment Red 123 (CI # 71145) 1560 0.0 Cellulose acetate 6299.0 Acetone 2769.6 Water 22680.0 Dimethyl polysiloxane (1679.0 g per 11.8 kg of toner) ──────────────

(Preparation of Cyan Toner) A cyan toner was prepared in the same manner as the preparation of the yellow toner, except that the following components were used and the stirring time was changed from 4 hours to 6 hours.

{Cyan Toner Component Amount (g)} ──────────────────────────────── Copper phthalocyanine (Pigment Blue 15, CI # 74160) 1064.0 Pigment Green 7 ( CI # 74260) 943.0 Cellulose acetate 7981.0 Acetone 27669.6 Water 22680.0 Dimethylpolysiloxane (574.9 g per 10 kg of toner) ─────────────────

(Preparation of Black Toner) The following components were used, and the stirring time was changed from 4 hours to 6 hours.
A black toner was prepared in the same manner as the preparation of the yellow toner.

{Amount of Black Toner Component (g)} ──────────────────────────────── Carbon black (Pigment Black 7, CI # 77266) 6300.0 Cellulose acetate 6300. 0 Acetone 27669.6 Water 22680.0 Dimethylpolysiloxane (970.0 g per 12.6 kg of toner) ────────

(Preparation of Color Proof) A color proof was prepared as described below using the above-described photosensitive material for image transfer according to the first mode of image formation. Using an air-cooled argon ion laser as a light source, exposure for yellow image formation was performed by scanning exposure (exposure amount on the film surface: 10 μJ / cm ² ) at an exposure wavelength of 488 nm. Next, this is 1
Heat development was carried out by heating the plate while in close contact with a hot plate heated to 30 ° C. for 40 seconds. Next, the layer above the photosensitive layer was peeled off from the interface between the polymerizable layer and the photosensitive layer to expose the polymerizable layer. When the yellow toner was adhered to the surface of the polymerizable layer while rubbing lightly, the toner adhered only to the unexposed portion, that is, the uncured portion, and a yellow image was formed on the photosensitive material. Similarly, on another photosensitive material, exposure for magenta image formation, thermal development, after peeling, the above magenta toner adhered while rubbing lightly,
A magenta image was formed on the photosensitive material. In the same manner, another photosensitive material is exposed for cyan image formation,
After heat development and peeling, the cyan toner was adhered while rubbing lightly to form a cyan image on the photosensitive material. Further, in the same manner, another photosensitive material is exposed for black image formation, heat-developed, peeled, and eluted, and the black toner is adhered while rubbing lightly to form a black image on the photosensitive material. did. Next, the photosensitive material on which the yellow image is formed is brought into close contact with the image receiving material made of art paper, and heated to about 100 ° C., so that the yellow toner image is formed on the image receiving material together with the polymerizable layer and the release layer of the photosensitive material. Transcribed. Similarly, the photosensitive material on which the magenta image has been formed is brought into close contact with the image receiving material on which the yellow image has been transferred, and heated to about 10 ° C., so that the magenta toner image together with the polymerizable layer and the release layer of the photosensitive material is formed. Transferred to Similarly, a cyan toner image and a black toner image were sequentially transferred to an image receiving material, and a color proof was created. The image quality of the obtained proof was good for faithfully reproducing digital image data.

[Example 8 ] In Example 2 , the binder of the release layer was changed to Esrec B
A photosensitive material for image transfer was prepared in the same manner except that H-3 was changed to Esrec BX-1 (polyvinyl butyral, manufactured by Sekisui Chemical Co., Ltd.).

[Example 9 ] In Example 2 , the binder of the release layer was changed to Esrec B
H-3 was changed to styrene-α-methylstyrene-acrylonitrile copolymer, Megafac F177P was used as a surfactant in the release layer at 2% by weight, and the thickness of the release layer was changed to 1.8 μm. To prepare a photosensitive material for image transfer.

[Example 10 ] In Example 2 , the binder of the release layer was changed to Esrec B
H-3 was changed to an ethylene-ethyl acrylate copolymer, and Megafac F17 was used as a surfactant in the release layer.
7P is used at 2% by weight, and the thickness of the release layer is set to 2.0 μm.
A photosensitive material for image transfer was prepared in the same manner, except that the above conditions were changed.

[ Comparative Example 5 ] In Example 2 , the binder of the release layer was changed to Esrec B
A photosensitive material for image transfer was prepared in the same manner except that H-3 was changed to Esrec BL-1 (polyvinyl butyral, manufactured by Sekisui Chemical Co., Ltd.).

[ Comparative Example 6 ] In Example 2 , the binder of the release layer was changed to Esrec B
A photosensitive material for image transfer was prepared in the same manner except that H-3 was changed to S-lek BM-1 (polyvinyl butyral, manufactured by Sekisui Chemical Co., Ltd.).

[Comparative Example 7 ] In Comparative Example 3, the binder of the release layer was changed to Esrec B
A photosensitive material for image transfer was prepared in the same manner except that H-3 was changed to Esrec BL-1 (polyvinyl butyral, manufactured by Sekisui Chemical Co., Ltd.) and the thickness of the release layer was changed to 1.5 μm.

[Comparative Example 8 ] In Comparative Example 7 , the binder of the release layer was changed to Esrec B
A photosensitive material for image transfer was prepared in the same manner except that L-1 was changed to S-lek BM-1 (polyvinyl butyral, manufactured by Sekisui Chemical Co., Ltd.).

[Measurement of Flow Softening Point] The flow softening point of the binder of the release layer used in Examples 2, 8 to 10 and Comparative Examples 5 to 8 was measured by a high-pressure flow tester at a pressure of 100 kg / cm ² , Heating rate 6 ° C / mi
n, measured under a flow condition of a nozzle diameter of 1 mmφ × 10 mm. The results are shown in Table 3.

[Evaluation of Peelability] Examples 1 to 5, Comparative Example 1
Exposed samples and unexposed samples were prepared in the same manner as in Examples 2 and 3, and the releasability was evaluated. The results are shown in Table 3.

[0177]

[Table 3] Table 3 ──────────────────────────────────── Photosensitive material Required for peeling binder To the image receiving material Flow softening point Unexposed sample Image transfer of exposed sample ───────────────────────────────────例 Example 2 205 ° C. 12 g 12 g Good Example 8 225 ° C. 11 g 20 g Good Example 9 160 ° C. 14 g 11 g Good Example 10 165 ° C. 17 g 30 g Poor Comparative Example 5 105 ° C. 15 g> 1000 g Poor Comparative Example 6 130 ° C. 15 g> 1000 g Poor Comparative Example 7 105 ° C 14g 12g Good Comparative Example 8 130 ° C 13g 13g Good ───────────────────────────────── ───

As shown in Table 2, in the case of the photopolymerizable image transfer material (Comparative Examples 7 and 8 ), the force required for peeling was small, and the value was the same in both the unexposed sample and the exposed sample. On the other hand, in the photosensitive material for image transfer using silver halide (Examples 2, 8 to 10, and Comparative Examples 5 and 6 ), the unexposed sample requires a small force for peeling regardless of the thickness of the peeling layer. In the case of using a release layer binder having a flow softening point lower than the heat development temperature ( Comparative Example 5 and
In the case of 6 ), the force required for peeling was very large and the peeling was not successful. When a release layer binder having a flow softening point higher than the heat development temperature was used (Examples 2 and 8 to 10 ), the force required for the release was small and the release was easy.
Also, with the photopolymerizable image transfer material (Comparative Examples 7 and 8 ), an image was successfully transferred. On the other hand, in the case of an image transfer photosensitive material using silver halide, a release layer binder having a flow softening point lower than the heat development temperature was used ( Comparative Example 5).
And 6 ), the non-image area (unexposed area) was well transferred to the image receiving material, but the image area (exposed area) did not sufficiently release the release layer from the support of the photosensitive material.
Image transfer was poor. However, when a release layer binder having a flow softening point higher than the heat development temperature was used (Examples 2 and 8 to 10 ), both the exposed and unexposed portions easily peeled off, and a good transfer image was obtained on the image receiving material. Could be formed.

Example 11 A black image was transferred in the same manner as in Example 8 , except that the black pigment, cyan pigment and magenta used in Example 6 were used instead of the yellow pigment as the pigment for the polymerizable layer. A photosensitive material for cyan, a photosensitive material for cyan image transfer, and a photosensitive material for magenta image transfer were prepared. A color proof similar to a printed matter was prepared in the same manner as in Example 6 using each of the image transfer photosensitive materials described above and the yellow image transfer photosensitive material prepared in Example 8 . The resulting quality of the proofing <br/> were those favorable to faithfully reproduce the original digital image data.

Example 12 (Preparation of photosensitive material) A photosensitive material for image transfer was prepared as follows. "Release layer" A coating solution for forming a release layer having the following composition was prepared, applied on a biaxially stretched polyethylene terephthalate film having a thickness of 100 μm to a thickness of 1.7 μm, dried, and dried. Was formed.

<< Coating Liquid for Release Layer >>ポ リ ビ ニ ル Polyvinyl butyral (ESREC BX-5, manufactured by Sekisui Chemical Co., Ltd., flow softening point: (230 ° C.) 3.75 g Surfactant (MegaFac F177P, manufactured by Dainippon Ink Co., Ltd.) 0.07 g Methanol 37.50 g n-propanol 37.50 g ─────────────────────

[Formation of Polymerizable Layer] In the same manner as in Example 7 , a polymerizable layer was formed on the release layer so as to have a dry film thickness of 1.3 μm.

[Formation of Photosensitive Layer] In the same manner as in Reference Example 1, a photosensitive layer was formed on the polymerizable layer so as to have a dry film thickness of 1.3 μm.

[Formation of Overcoat Layer] In the same manner as in Reference Example 1, an overcoat layer was formed on the photosensitive layer so that the dry film thickness was 3.5 μm.

When a color proof was prepared in the same manner as in Example 7 using the photosensitive material for image transfer prepared as described above, the image quality of the obtained proof was good for faithfully reproducing digital image data. Was.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view of a photosensitive material for image transfer according to the present invention.

FIG. 2 is a schematic cross-sectional view of another embodiment of the photosensitive material for image transfer of the present invention.

FIG. 3 is a schematic sectional view showing an exposure step in a first mode of image formation.

FIG. 4 is a schematic sectional view showing a developing step in a first mode of image formation.

FIG. 5 is a schematic sectional view showing a toner developing step in a first mode of image formation.

FIG. 6 is a schematic sectional view showing a transfer step in a first mode of image formation.

FIG. 7 is a schematic sectional view showing an exposure step in a third mode of image formation.

FIG. 8 is a schematic sectional view showing a developing step in a third mode of image formation.

FIG. 9 is a schematic sectional view showing an elution step in a third mode of image formation.

FIG. 10 is a schematic sectional view showing a transfer step in a third mode of image formation.

FIG. 11 is a schematic sectional view illustrating a method for evaluating and measuring peelability.

[Explanation of symbols]

 11, 21, 111 Support 12, 22, 64, 104, 112 Release layer 13 Photopolymerizable layer 14, 27, 34, 48, 74, 88 Silver halide 15, 28, 46, 86 Reducing agent 16, 25 Polymerizable compound 17, 26 Colorant 23, 113 Polymerizable layer 24 Photosensitive layer 31, 71 Light 32, 44, 72, 84 Unexposed portion of photosensitive layer 33, 45, 73, 85 Exposed portion of photosensitive layer 35 , 75 Latent image of silver halide 41, 81 Heat 42, 52, 82 Unexposed portion (uncured portion) of polymerizable layer 43, 53, 83, 92 Exposed portion (cured portion) of polymerizable layer 47, 87 Oxidation Body radical 49, 89 Silver image 51, 63 Colored toner (toner image) 61, 101 Image receiving material 62, 102 Photosensitive material 91 Eluate 103 Colored image 114 Mylar tape F Force required for peeling

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-1-120550 (JP, A) JP-A-2-287548 (JP, A) JP-A-3-160455 (JP, A) JP-A-4- 175755 (JP, A) JP-A-1-155350 (JP, A) JP-A-3-21953 (JP, A) JP-A-4-37856 (JP, A) JP-A-2-304444 (JP, A) JP-A-2-54270 (JP, A) JP-B-46-15326 (JP, B1) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03F 7/06 G03F 7/004 G03F 7/11

Claims (5)

(57) [Claims] 1. A photosensitive material comprising a support and a photosensitive polymerizable layer containing a silver halide, a reducing agent, and a polymerizable compound without using microcapsules, wherein the support and the photosensitive polymer Required for the reduction reaction of the reducing agent with the conductive layer
A photosensitive material for image transfer , comprising a release layer containing a binder having a flow softening point not lower than the heating temperature . 2. The photosensitive material for image transfer according to claim 1, wherein the release layer has a thickness of 1.0 μm or more. 3. The photosensitive polymerizable layer comprises a photosensitive layer containing silver halide and a polymerizable layer containing a polymerizable compound, and a release layer, a polymerizable layer and a photosensitive layer are sequentially provided on a support. The photosensitive material for image transfer according to claim 1. 4. The photosensitive material for image transfer according to claim 1, further comprising an overcoat layer provided on the photosensitive polymerizable layer. 5. The photosensitive material for image transfer according to claim 1, wherein the photosensitive polymerizable layer further contains a coloring agent.