JP2654693B2 - Image forming method - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a photosensitive material having a photosensitive layer containing a silver halide, a reducing agent and a polymerizable compound on a support, and an image receiving material having an image receiving layer on a support. And an image forming method using the same. Further, the present invention relates to a photosensitive material having a photosensitive layer containing a photopolymerizable composition on a support and an image forming method using an image receiving material having an image receiving layer on the support.

BACKGROUND OF THE INVENTION An image forming method using a photosensitive material having a photosensitive layer containing a silver halide, a reducing agent and a polymerizable compound on a support is disclosed in JP-B-45-11149, JP-B-47-20741 and JP-B-47-20741. -10697,
It is described in JP-A-57-138632 and JP-A-58-169143. In these methods, when a silver halide in an imagewise exposed photosensitive layer is developed using a developer, a coexisting reducing agent is oxidized, and at the same time, a coexisting polymerizable compound (eg, a vinyl compound) is formed. Polymerizes to form a polymer (polymer compound) imagewise. Therefore, the above method requires a developing process using a liquid, and the process requires a relatively long time.

As an improvement of the above method, JP-A-61-69062 discloses a method capable of forming a polymer compound by dry treatment. In this method, a recording material (photosensitive material) having a photosensitive layer composed of a photosensitive silver salt (silver halide), a reducing agent, a crosslinkable compound (polymerizable compound) and a binder supported on a support is exposed by image exposure. And forming a latent image of the photosensitive silver salt, and then heating the latent image to form a polymer (polymer compound) in the portion where the latent image is formed. The dry image forming method is also described in JP-A Nos. 61-73145, 61-183640, and 61-188535.

A method of forming an image by polymerizing a polymerizable compound in a portion where a silver halide latent image is not formed is also known (JP-A-61-260241). This method is a method in which polymerization of a portion where a latent image of silver halide is formed is suppressed and polymerization is promoted in another portion (a region where a latent image is not formed).

An image forming method using a photosensitive material having a photosensitive layer containing a photopolymerizable composition on a support is a method of forming a polymer (polymer compound) on a portion exposed by imagewise exposure. Regarding the image forming method and the photosensitive material used therein, JP-A-52-89915 and JP-A-57-179836
Nos. 58-88739, 58-88740, and 60-259490
No. and other publications.

In the image forming method using the photosensitive material having the above structure, after forming a polymer compound imagewise on the photosensitive material as described above, the photosensitive material is further overlaid on an image receiving material having an image receiving layer. In general, a method of applying pressure in a state, transferring an unpolymerized polymerizable compound (or a photopolymerizable composition, the same applies hereinafter) to an image receiving material, and obtaining a transferred image on the image receiving material is generally used. In the above-described image forming method, a photosensitive material containing silver halide and a polymerizable compound in microcapsules, or a photosensitive material containing a photopolymerizable composition in microcapsules is particularly preferably used.

By the way, in the field of recording sheets of various recording materials, a method of supplying more image forming components (a dye, a dye precursor, and the like) to the recording sheet in order to enhance the image quality is known. For example, in the field of ink jet recording or the field of an image receiving sheet for thermal transfer (image receiving material), a method has been disclosed in which a gap is provided in the image receiving sheet, and the supply of image forming components is increased by increasing the space for the gap. JP-A-59-68292, JP-A-59-68293, JP-A-59-68294
Nos. 61-217289, 61-164892 and 61-164893
No.). These methods are very effective means in that more image forming components are supplied to the image receiving sheet, and include an image forming process including a pressure transfer step using the photosensitive material and the image receiving material as described above. It can also be used advantageously in systems. However, according to the study of the present inventor, in the image forming process using the photosensitive material having the above-described structure, a pressurizing step (100 to 500 kg / cm ² ) is required. When it is provided, the voids are easily broken, and especially when it is used under high temperature and high humidity (30 ° C, 80% RH), cohesive failure such that part of the image receiving layer adheres to the photosensitive layer side when peeling Sometimes occurred.

[Summary of the Invention] The present invention can easily perform a peeling operation at the time of pressure transfer,
Moreover, an object of the present invention is to provide an image forming method capable of obtaining an excellent transfer image.

The present invention has a photosensitive layer containing a silver halide, a reducing agent and a polymerizable compound on a support, and at least the silver halide and the polymerizable compound are contained in the photosensitive layer in a state encapsulated in microcapsules. The photosensitive material thus obtained is subjected to imagewise exposure, subjected to heat development at the same time as or after imagewise exposure, and then, on the support,
There is provided an image forming method comprising transferring an unpolymerized polymerizable compound to the image receiving material by pressing the image receiving materials having a porous image receiving layer containing a fluorine-based compound in a state of being superposed.

Further, the present invention provides a method for forming a photosensitive material comprising a photosensitive layer containing a photopolymerizable composition on a support, and the photopolymerizable composition being contained in a microcapsule and contained in the photosensitive layer. Exposure to light, and, on the photosensitive material that has been subjected to imagewise exposure, by pressing the image receiving material having a porous image receiving layer containing a fluorine-based compound on a support in a state of being superimposed, the unpolymerized There is provided an image forming method comprising transferring a photopolymerizable composition to the image receiving material.

In the present specification, “a porous image-receiving layer containing a fluorine-based compound” means that the fluorine-based compound may be present at any position on the porous image-receiving layer.
For example, when the fluorine compound is uniformly present in the layer, when the fluorine compound is present on the surface side of the layer, or when the fluorine compound is abundantly present in the layer and on the surface side There is.

 The present invention preferably has the following aspects.

1) The porous image receiving layer is formed by including pigment particles, and the pigment particles are added to the image receiving layer in an amount of 0.1 to 6%.
It exists in the range of 0 g / m ² .

2) The fluorine-based compound is a fluorine-based surfactant.

3) The fluorine-based compound is a fluorine-based surfactant,
In addition, the fluorine-based surfactant has a surface tension of 25 dynes / cm or more.

4) The fluorine compound is present on the surface side of the image receiving layer.

5) The fluorine-containing compound is contained in the image receiving layer in a range of 0.01 to 1 g / m ² .

6) The image receiving layer contains a color developer, and the color developer is a zinc salt of a derivative of salicylic acid.

7) The photosensitive layer further contains a color image forming substance, and the color image forming substance is contained in a microcapsule.

[Effect of the Invention] The image forming method of the present invention is a method of transferring an unpolymerized polymerizable compound under pressure to an image receiving material.

According to the study of the present inventors, when a porous image-receiving material containing a fluorine-based compound is used, the adhesive force of the entire transfer surface is reduced (dispersion of the adhesive force) mainly due to the high oil repellency of the fluorine-based compound. ) Was achieved. Therefore,
The peeling operation after the pressure transfer can be easily performed, and the cohesive failure does not occur.

On the other hand, it was found that the image density did not decrease. Although the cause is not clear, the porous image receiving layer allows the polymerizable compound to move efficiently irrespective of the presence of the fluorine-based compound. It is considered that the main reason is that the affinity between the color former and the developer contained in the polymerizable compound is increased.

As described above, by using the image receiving material containing the fluorine compound according to the present invention, a smooth image can be formed and a transferred image with good contrast can be obtained.

[Detailed Description of the Invention] The image receiving material used in the image forming method of the present invention has a porous image receiving layer containing a fluorine compound on a support.

The fluorine-based compound that can be used in the present invention preferably has high hydrophobicity and low water absorption. In particular, a fluorine-based surfactant (anionic, cationic, nonionic, or amphoteric) may be used. These may be low molecular compounds or high molecular compounds (which may be in a latex state).

Examples of the low molecular weight compound include U.S. Pat.
No. 6, No. 3,589,906, No. 3798,265, No. 3,779,768, No.
4,407,937 No., West German Patent No. 1,293,189,
UK Patent No. 1,259,398, UK Patent Application No. 58,431
No., JP-A-48-87826, JP-A-49-10722, JP-A-49-467
No. 33, No. 50-16525, No. 50-113221, No. 50-161236,
No. 51-7917, No. 51-32322, No. 51-106419, No. 51-151
No. 124, No. 51-151125, No. 51-151126, No. 51-151127
No. 51-129229, No. 52-127974, No. 53-84712, No.
53-146622, 54-14224, 54-48520, 55-7762
Nos. 56-114944, 58-16233, 59-23344, 6
0-244945, 61-20944, 61-51144, 62-17346
Nos. 3, 62-283334, 48-43130, 52-16073, Research Disclosure Magazine No. 16630,
No. 17341, No. 17611 and the like can be mentioned.

Examples of the polymer compound include, for example, U.S. Pat.
969, 4,087,394, 4,016,125, 3,676,123
Nos. 3,679,411 and 4,304,852, JP 52
-129520, 54-158222, 55-57842, 57-11342
Nos. 57-19735 and 57-179837, `` Chemical Review N
o, 27, New Fluorochemistry ”(edited by The Chemical Society of Japan, 1980),
Satokawa, “Functional Fluoropolymers” (Nikkan Kogyo Shimbun, 19
1982).

Preferred specific examples of the fluorine compound that can be used in the image receiving material according to the invention are described below.

_{(1) CF 3 CF 2 6} COONH 4 (2) CF 3 CF 2 6 SO 3 Na (3) CF 3 CF 2 6 CH 2 10 COONH 4 _{(7) CF 3 CF 2 7} SO 3 K (8) CF 3 CF 2 7 SO 3 Li (9) CF 3 CF 2 7 SO 3 Na (10) CF 3 CF 2 7 SO 3 NH 4 (11) CF 3 CF _{2 11} CH ₂ -OSO ₃ Na _{(14) CF 3 CF 2 6} CH = CHCH 2 3 COONa (22) HCF _{2 10} CH ₂ OH _{(24) CF 3 CF 2 7} SO 2 NHCH 2 3 + N- (CH 3) 3 · I - (32) CF ₃ CF _{2 12} COOCH ₂ CH ₂ O ₂₀ H _{(39) HCF 2 6 CH 2} OCH 2 CH 2 O 10 H _{(42) C 8 F 17 ·} SO 2 -NHCH 2 3 + N (CH 2 CH 2 OCH 3) 3 · I - _{(51) C 12 F 25 OCH} 2 CH 2 5 CH 2 CH 2 + N (CH 3) 3 · I - _{(55) C 9 F 19 CONHCH} 2 3 + N (CH 3) 3 · I - _{(60) HCF 2 8 COOCH 2} CH 2 - + N (CH 2 CH 2 OH) 3 · Br - (66) C ₄ F ₉ CH ₂ CH ₂ OCH _{2 3} ⁺ N (CH ₃ ) ₃ Further, a fluorine-based silane coupling agent can also be used as the fluorine-based compound.

The following are commercially available as fluorine-based surfactants and can be preferably used.

Examples of such commercially available products (trade names) include Surflon S111 (Perfluoroalkylcarboxylate, manufactured by Asahi Glass Co., Ltd.), Surflon S112 (Perfluoroalkylphosphate ester, manufactured by Asahi Glass Co., Ltd.), Surflon S145 (Perfluoroalkyl ethylene oxide adduct, manufactured by Asahi Glass Co., Ltd.), Megafac F-110 (Perfluoroalkyl sulfonate, manufactured by Dainippon Ink and Chemicals, Inc.), Daifree ME413 (fluoropolymer latex, Daikin) Industrial Co., Ltd.).

These fluorine compounds may be used alone or in combination of two or more.

In the present invention, it is particularly preferable that the above-mentioned fluorine-based surfactant has a surface tension of 25 dynes / cm or more.

Examples of such compounds include the following.

_{(2) n-C 7 F} 15 SO 3 Na (37.3 dynes / cm) (8) n- C 8 F 17 SO 3 Li (29.8 dynes / cm) (9) n- C 8 F 17 SO 3 Na (34.5 dynes / cm) (10) n- C 7 F 15 SO 3 NH 4 (27.8 dynes / cm) Surflon S112 (perfluoroalkyl phosphoric acid ester, manufactured by Asahi Glass Co., Ltd.) (37.1 dynes / cm) in particular among these And Surflon S112 are preferred.

In the present invention, anionic or nonionic fluorine-based surfactants can be advantageously used. In particular, as described later, when a color former (leuco dye) is used as a color image forming substance to be contained in a photosensitive material, a developer (acid) is generally used in the image receiving layer of the image receiving material. Therefore, in this case, an anionic or nonionic fluorine-based surfactant is effective so as not to impair the function of the color developer.

As a method of including the fluorine-based compound in the image receiving layer, a method of adding a fluorine-based compound to a coating solution for forming an image receiving layer can be used. Further, a method of preparing a solution containing a fluorine-based compound prepared using water or a suitable solvent in advance and applying the solution on the image receiving layer can be used. In this case, the solution permeates not only on the surface of the image receiving layer but also inside the image receiving layer. In the present invention, it is preferable to use the latter method to incorporate the compound into the image receiving layer.

In the present invention, the above-mentioned fluorine-based compound is added to the image receiving layer in an amount of 0.
It is preferably contained in the range of 01 to 1 g / m ² . When the solution containing a fluorine-based compound is contained in the image receiving layer by using a method of coating the solution on the image receiving layer, the content is more preferably in the range of 0.1 to 0.5 g / m ² . When used in a mixture in the coating solution for the image receiving layer, the content is more preferably in the range of 0.5 to 1 g / m ² .

In the present specification, the term "image receiving layer" means a layer provided on a support and having one or more functions relating to the image formation. For example, a function of improving the surface smoothness so that the image forming process such as transfer proceeds smoothly, a function of improving the image quality such as gloss, and a function directly related to image formation and fixing can be given.

The fluorine-based compound is contained in a porous image receiving layer. There are various methods for making the image receiving layer porous.
In the invention, the image receiving layer is preferably formed by including pigment particles.

The pigment is not particularly limited, and a known pigment can be used. Specific examples include titanium oxide, zinc oxide, barium sulfate, calcium carbonate, aluminum silicate, calcium silicate, and zirconium oxide. These pigments preferably have a surface treatment so as to be bulky or have various crystal systems. Among them, calcium carbonate is preferred.

The particle size of the pigment is preferably in the range of 0.1 to 50 μm, more preferably in the range of 0.5 to 10 μm.

The pigment is preferably contained in the image receiving layer at a coating amount of 0.1 to 60 g / m ² . More preferably 0.5 to 30 g
/ m ² .

The porous image-receiving layer as described above usually contains a binder and a substance which causes a color-forming reaction with a color image forming substance to produce a dye. Further, in order to impart a desired function, for example, a thermoplastic compound, a photopolymerization initiator, a thermal polymerization initiator, or the like can be used.

 Hereinafter, these components will be described.

As the binder, it is preferable to use mainly a hydrophilic binder. A typical example of the hydrophilic binder is a transparent or translucent hydrophilic binder.

Further, as a binder, the oxygen permeability coefficient is 1.0 × 10
A polymer having a size of ^-11 cm ³ / cm ² · second · cmHg or less may be used (Japanese Patent Application Laid-Open No. 62-209454). When a polymer having low oxygen permeability is used as described above, the color image forming substance transferred to the image receiving layer is hardly deteriorated, and the image obtained on the image receiving material is stored for a long time or under severe conditions. Hardly fades after storage.

The binder is preferably used in the image receiving layer in an amount of 0.01 to 100 g / m ² (more preferably 0.1 to 10 g / m ² ).

There is no limitation on the substance that produces a dye by causing a color development reaction with the color image forming substance. For example, acid-base reaction, oxidation-reduction reaction, coupling reaction between two or more components,
Various systems that develop color by a chelate forming reaction or the like are included. For example, Hiroyuki Moriga, Introduction to Chemistry of Special Papers
Pressure-sensitive copying paper (29-58)
Page), azography (pages 87 to 95), known color systems such as thermosensitive coloring (pages 118 to 120), or seminars sponsored by the Kinki Chemical Industry Association, “The latest dye chemistry-attractive as functional dyes” Utilization and New Development-26
A color developing system described on page 32 (June 19, 1980) can be used. Specifically, a color forming system comprising a color former having a partial structure such as lactone, lactam, and spiropyran and an acidic substance (color developer) such as acidic clay and phenols used in pressure-sensitive paper; an aromatic diazonium salt; System using azo coupling reaction of diazotate, diazosulfonates with naphthols, anilines, active methylenes, etc .; reaction of hexamethylenetetramine with ferric ion and gallic acid, and phenolphthalein-complexones Chelate formation reactions such as reactions with alkaline earth metal ions; reactions between ferric stearate and pyrogallol, and silver behenate and 4-methoxy-
An oxidation-reduction reaction such as a 1-naphthol reaction can be used.

Among the above-described color forming systems, it is preferable to use a so-called color forming / developing agent system. As a general mode of use of this system, a mode is adopted in which a color former is contained in a photosensitive layer and a developer is contained in an image receiving layer. Representative examples of the color developer include the above-mentioned phenols, organic acids or salts or esters thereof, and when a leuco dye is used as a color image-forming substance, a zinc derivative of salicylic acid is used. Salts are preferred, and among them, zinc 3,5-di-α-methylbenzylsalicylate is preferred.

The color developer is preferably contained in the image receiving layer in an amount of 0.1 to 50 g / m ² . More preferably, 0.
It is in the range of 5 to 20 g / m ² .

When a thermoplastic compound is contained in the image receiving layer, it is preferable that the image receiving layer itself be constituted as an aggregate of thermoplastic compound fine particles. The image receiving layer having the above configuration has an advantage that a transfer image can be easily formed and a glossy image can be obtained by heating after image formation. The thermoplastic compound is not particularly limited and can be arbitrarily selected from known thermoplastic resins (plastics). However, the glass transition point of the thermoplastic resin and the melting point of the wax are preferably 200 ° C. or less.

The thermoplastic compound preferably has an average particle size in the range of 0.05 to 100 μm, and more preferably 0.5 to 100 μm.
It is preferably in the range of 20 μm. Further, the content of the thermoplastic compound in the image receiving layer is preferably in the range of 0.1 to 20 g / m ² , and more preferably in the range of 0.1 to 5 g / m ² . The content is preferably in the range of 2 to 100% by weight based on the solid content of the image receiving layer.

Incidentally, for an image receiving material having an image receiving layer containing the thermoplastic compound fine particles as described above, JP-A-62-280071,
Alternatively, it is described in JP-A-62-280739.

The image receiving layer may contain a photopolymerization initiator or a thermal polymerization initiator.

By adopting this configuration, a fixing process of a transferred image (an image composed of an unpolymerized polymerizable compound) can be easily and efficiently performed.

The image receiving material having an image receiving layer containing a thermal polymerization initiator is described in JP-A-62-210444, and the image receiving material having an image receiving layer containing a photopolymerization initiator is described in JP-A-63-19964.
No. 346 discloses each of them. In the present invention, it is preferable to perform the fixing treatment by heating using a thermal polymerization initiator.

The image-receiving material according to the present invention is prepared by preparing a solution containing the above-mentioned fluorine-based compound, and then coating the image-receiving layer forming coating solution, which is a mixture of the solution and the above-mentioned components (including optional components), with an emulsion or dispersion. Alternatively, it can be obtained by preparing in the form of a dissolved substance, applying it to a support using a usual coating means, and drying. Further, after an image receiving layer is formed on a support in the same manner as described above using a coating solution for forming an image receiving layer comprising the above-mentioned components (including optional components), the above-mentioned fluorine-containing compound is contained on the image receiving layer. It can be produced by applying a solution.

The thickness of the image receiving layer is generally preferably in the range of 5 to 500 μm, and particularly preferably in the range of 10 to 200 μm.

On the image receiving layer, a protective layer or, if desired, an optional layer can be further provided.

The optional layer includes, for example, a layer made of an aggregate of a thermoplastic compound. When a layer made of an aggregate of a thermoplastic compound is provided on the image receiving layer, it is easy to form a transferred image as in the case where the thermoplastic compound is contained in the image receiving layer, and heating is performed after image formation. This has the advantage that a glossy image can be obtained. The thermoplastic compound that can be used in the layer made of the aggregate of the thermoplastic compound is also the same as the thermoplastic compound that can be included in the above-described image receiving layer. Japanese Patent Application Laid-Open No. Sho 62-210460 describes an image receiving material in which a layer made of an aggregate of a thermoplastic compound is further provided on the image receiving layer.

Materials that can be used for the support of the image receiving material include glass, paper, woodfree paper, coated paper, cast-coated paper, baryta paper, synthetic paper, metal and its analogs, polyester, acetylcellulose, cellulose ester,
Examples include films such as polyvinyl acetal, polystyrene, polycarbonate, and polyethylene terephthalate; and papers laminated with resin materials and polymers such as polyethylene. Other, JP 63
Paper supports such as those described in U.S. Pat. No. -186239 can be used.

When a porous material such as paper is used as the support of the image receiving material, the support preferably has a certain degree of smoothness. Specifically, for the smoothness, the surface of the support on which the image receiving layer is provided is a filtered undulation curve derived from a cross-sectional curve measured according to JIS-B-0610 under a cutoff value of 0.8 mm. , When the maximum swell of the filter is measured at a reference length of 0.2 mm at 100 arbitrary measurement points,
It is preferable to have a surface characteristic having a maximum swell of 4 μm or more. The image receiving material using the above-defined smooth support is described in JP-A-62-209530.
Further, in order to obtain a transparent image, the support of the image receiving material may be made of a material having light transmittance. When a transparent image is obtained, the light transmittance of the support of the image receiving material is preferably 30% or more, more preferably 50% or more. The image receiving material using a transparent support is described in JP-A-62-209513. Further, as a paper support, a fiber length distribution defined by JIS-P-8207
It is also possible to use a paper support using a base paper having a fiber length distribution such that the sum of the weight percent of the mesh residue and the weight percent of the 42 mesh residue is 30 to 60% (Japanese Patent Application Laid-Open No. 63-63). 18623
No. 9).

Next, the image forming method of the present invention will be described in detail.

In the image forming method, in the case where the photosensitive material has a photosensitive layer containing a silver halide, a reducing agent and a polymerizable compound on a support (first embodiment), the photosensitive material is exposed imagewise. It consists of a heat developing process and a transfer operation of the unpolymerized polymerizable compound to the image receiving material. In the case where the photosensitive material has a photopolymerizable composition or a photosensitive layer containing a photopolymerizable compound on a support (second embodiment), the photosensitive material is exposed imagewise, Transferring the polymerizable compound (photopolymerizable composition or compound) to the image receiving material.

Hereinafter, an image forming method using the photosensitive material of the first embodiment having a photosensitive layer containing a silver halide, a reducing agent and a polymerizable compound on a support will be mainly described.

The image formation on the photosensitive material is performed by imagewise exposure and heat development.

Various exposure means can be used as an exposure method for imagewise exposure of the photosensitive material. Generally, a latent image of silver halide is obtained by imagewise exposure to radiation containing visible light. The type of light source and the exposure amount can be selected according to the photosensitive wavelength of silver halide (in the case of dye sensitization, the sensitized wavelength) and the sensitivity. The original image may be a black and white image or a color image.

Next, simultaneously with or after the imagewise exposure,
Develop the photosensitive material. The development processing is a heat development processing (dry processing). As a heating method in the heat development treatment, various conventionally known methods can be used. Further, as in the case of a photosensitive material described in JP-A-61-294434, a heating element layer may be provided on the photosensitive material and used as a heating means. The heating temperature is generally 80 ° C to 200 ° C, preferably 100 ° C to 16 ° C.
0 ° C. The heating time is generally 1 second to 5 minutes, preferably 5 seconds to 1 minute.

In the present invention, the liquid in the photosensitive layer of the polymerizable compound 10
A method of subjecting the photosensitive material to heat development at 50 ° C. or more in a state where the photosensitive material is contained in the range of from 400 to 400% by weight (preferably from 20 to 200% by weight) can also be used.

Any liquid can be used without particular limitation as long as it does not inhibit the development reaction (reduction of silver halide and polymerization of the polymerizable compound) of the photosensitive material.

When the polymerizable compound is in a liquid state, the liquid used in the present invention preferably has an incompatibility with the polymerizable compound. When the polymerizable compound is a solid, it is preferable to use a liquid in which the polymerizable compound is not dissolved.

For example, when the polymerizable compound is hydrophobic, it is preferable to use water or a hydrophilic liquid as the liquid.

The “liquid” is defined as a substance which is in a liquid phase at the minimum heating temperature (generally 50 ° C.) required in the heat development process. Specifically, the melting point is 50 ° C. or less, and the boiling point is 50 ° C. or more (preferably 50 to 200 ° C.).

When water is used as the liquid, the amount of water contained in the photosensitive layer is preferably maintained at 1% to 100% of the weight of water corresponding to the maximum swelling volume of all coating layers on the photosensitive layer side.
The amount of water is 0.1 g to 30 g per 1 m ^{2 of} photosensitive material area.
And more preferably 1 g to 20 g.

In the image forming method using a liquid, the heating temperature is preferably 50 ° C. to 100 ° C., and 60 ° C. to 100 ° C.
It is more preferable that the temperature is ° C. The heating time is generally from 1 second to 5 minutes, preferably from 5 seconds to 30 seconds.

The photosensitive material can be subjected to the heat development treatment as described above to polymerize the polymerizable compound in either the portion where the silver halide latent image is formed or the portion where the latent image is not formed. Incidentally, in the photosensitive material, the polymerizable compound in the portion where the silver halide latent image is formed is generally polymerized in the above-mentioned thermal development process. However, as in the photosensitive material described in JP-A-62-260241, By adjusting the type and amount of the reducing agent used for the material, it is possible to polymerize the polymerizable compound in the portion where the latent image of silver halide is not formed.
As described above, the polymerizable compound in the portion where the latent image is formed (or the portion where the latent image is not formed) can be polymerized and cured.

The above-mentioned image-receiving material is then superimposed on the photosensitive material that has been subjected to the heat development processing (in a state in which substantially no liquid is present) as described above, whereby an unpolymerized polymerizable compound (color (Including an image forming substance) to an image receiving material. Various known methods can be used for the pressurizing means. The pressure is preferably in the range of 100 to 1300 kg / m ² (more preferably in the range of 500 to 800 kg / m ² ). In the light-sensitive material of the second embodiment, an unpolymerized polymerizable compound can be transferred to the image-receiving material by performing the same operation as described above after imagewise exposure.

After the pressure transfer, the image receiving material is separated (separated) from the photosensitive material. Since the image-receiving layer contains the fluorine-based compound as described above, the peeling is performed favorably, and a high-density image is obtained.

The image forming method of the present invention can be applied to various types of imaging such as black-and-white or color imaging and printing, printing, printing plates, X-ray imaging, medical diagnostic imaging (for example, ultrasonic diagnostic CRT imaging), computer graphic hard copy, and copier. It can be applied to various fields.

Next, components of the photosensitive material will be described. However,
As described above, the photosensitive material includes the photosensitive material of the first embodiment and the photosensitive material of the second embodiment. Hereinafter, the photosensitive material of the first embodiment will be mainly described.

In the light-sensitive material, any of silver chloride, silver bromide, silver iodide or silver chlorobromide, silver chloroiodide, silver iodobromide and silver chloroiodobromide can be used as silver halide. .

The halogen composition of the silver halide grains may be uniform or non-uniform on the surface and inside. Regarding silver halide grains having multiple structures having different compositions on the surface and inside, JP-A-57-154232, JP-A-58-108533, and JP-A-59-48755
Nos. 59-52237, U.S. Pat. No. 4,433,048 and European Patent No. 100984. Further, silver halide grains having a high ratio of silver iodide in the shell portion may be used as in the light-sensitive material described in JP-A-62-183453.

There is no particular limitation on the crystal habit of the silver halide grains.
For example, tabular grains having an aspect ratio of 3 or more, such as a photosensitive material described in JP-A-62-210455, may be used.

The silver halide grains described in JP-A-63-688
It is preferable to use silver halide grains having a relatively low fog value, as in the light-sensitive material described in JP-A-30.

The silver halide used for the photosensitive material includes a halogen composition,
Two or more kinds of silver halide grains having different crystal habits, grain sizes and the like can be used in combination.

There is no particular limitation on the grain size distribution of the silver halide grains. For example, monodisperse silver halide grains having a substantially uniform grain size distribution, such as the photosensitive material described in JP-A-62-210448, may be used.

In the light-sensitive material, the average grain size of the silver halide grains is preferably from 0.001 to 5 μm, and more preferably from 0.001 to 2 μm.

The amount of silver halide contained in the photosensitive layer is 0.1 mg to 10 g / m 2 in terms of silver containing an organic silver salt which is an optional component described later.
It is preferred to be in the range of ² . Further, in terms of silver equivalent of only silver halide, it is preferably 1 g / m ² or less, and 1 mg / m ² or less.
It is particularly preferred that the concentration be in the range of from 500 to 500 mg / m ² .

The reducing agent that can be used in the light-sensitive material has a function of reducing silver halide and / 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, and 4-amino-5.
-Pyrazolones, 5-aminouracils, 4,5-dihydroxy-6-aminopyrimidines, reductones, aminoreductones, o- or p-sulfonamidophenols, o- or p-sulfonamidonaphthols,
2-sulfonamidoindanones, 4-sulfonamido-5-pyrazolones, 3-sulfonamidoindoles, sulfonamidopyrazolobenzimidazoles, sulfonamidopyrazolotriazoles, α-sulfonamidoketones, hydrazines and the like There is. By adjusting the type and amount of the reducing agent, the polymerizable compound in a portion where a latent image of silver halide is formed or a portion where a latent image is not formed can be polymerized. In a system in which a polymerizable compound in a portion where a latent image of silver halide is not formed is polymerized, it is particularly preferable to use 1-phenyl-3-pyrazolidones as a reducing agent.

For various reducing agents having the above functions, JP-A-61-183640, JP-A-61-188535, JP-A-61-228441, and JP-A-62-228441
No. 70836, No. 62-86354, No. 62-86355, No. 62-264041, No. 62-198849, etc. (including those described as developing agents or hydrazine derivatives). The reducing agent is described in “The Theory of the
Photographic Process "4th edition, pp. 291-334 (1977
Year), Research Disclosure Magazine Vol. 170, No. 17029, June 1978 (pages 9-15), and the same magazine, Vol. 176, 197
No. 17643 (December 8, pp. 22-31) is also described. Further, as in the photosensitive material described in JP-A-62-210446,
Instead of the reducing agent, a reducing agent precursor that can release the reducing agent under heating conditions or in contact with a base may be used. The reducing agent and the reducing agent precursor described in each of the above publications, the specification and the literature can be effectively used also in 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. These reducing agents are
Although they may be used alone, as described in the above-mentioned respective specifications, two or more reducing agents may be mixed and used. When two or more types of reducing agents are used in combination, the reducing agents interact firstly by promoting reduction of silver halide (and / or organic silver salt) by so-called superadditivity. Causing the polymerization of the polymerizable compound via an oxidation-reduction reaction with another reducing agent coexisting with an oxidized form of the first reducing agent generated by the reduction of silver halide (and / or organic silver salt) (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.

Specific examples of the reducing agent include pentadecylhydroquinone, 5-t-butylcatechol, p- (N, N-diethylamino) phenol, 1-phenyl-3-pyrazolidone, 5-phenyl-3-pyrazolidone, 1,5 -Diphenyl-3-pyrazolidone, 1-phenyl-4-methyl-
4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-heptadecylcarbonyloxymethyl-3-pyrazolidone, 2-phenylsulfonylamino-4-hexadecyloxy-5-t-octylphenol, 2-phenyl Sulfonylamino-4-t-butyl-5-hexadecyloxyphenol, 2- (N-butylcarbamoyl) -4-phenylsulfonylaminonaphthol, 2- (N-methyl-N-octadecylcarbamoyl) -4-sulfonylaminonaphthol , 1-acetyl-2-phenylhydrazine, 1-formyl-2- (2
-Methoxyphenyl) hydrazine, 1-formyl-2-
(2-chlorophenyl) hydrazine, 1-formyl-2
-(2-butoxyphenyl) hydrazine, 1- (3,5-
Dichlorobenzoyl) -2-phenylhydrazine, 1-
(3,5-dichlorobenzoyl) -2- (2-chlorophenyl) hydrazine, 1-acetyl-2-{(p or o) -aminophenyl} hydrazine, 1-formyl-2
-{(P or o) -aminophenyl} hydrazine, 1
-Acetyl-2-{(p or o) -methoxyphenyl} hydrazine, 1-lauroyl-2-{(p or o) -aminophenyl} hydrazine, 1-trityl-2
-(2,6-dichloro-4-cyanophenyl) hydrazine, 1-trityl-2-phenylhydrazine, 1-phenyl-2- (2,4,6-trichlorophenyl) hydrazine, 1- {2- (2, 5-di-t-pentylphenoxy)
Butyroyl {-2-} (p or o) -aminophenyl} hydrazine, 1- {2- (2,5-di-t-pentylphenoxy) butyroyl} -2-{(p or o) -aminophenyl} hydrazine -Pentadecylfluorocaprylate, 3-indazolinone, 1- (3,5-dichlorobenzoyl) -2-phenylhydrazine, 1-trityl-2-[｛(2-N-butyl-N-octylsulfamoyl) -4-methanesulfonyl {phenyl] hydrazine, 1- {4- (2,5-di-t-pentylphenoxy)
Butyroyl {-2-} (p or o) -methoxyphenyl} hydrazine, 1- (methoxycarbonylbenzohydryl) -2-phenylhydrazine, 1-formyl-2-
[4- {2- (2,4-di-t-pentylphenoxy) butyramide} phenyl] hydrazine, 1-acetyl-2
-[4- {2- (2,4-di-t-pentylphenoxy)
Butylamido [phenyl] hydrazine, 1-trityl-
2-[{2,6-dichloro-4- (N, N-di-2-ethylhexyl) carbamoyl} phenyl] hydrazine, 1-
(Methoxycarbonylbenzohydryl) -2- (2,4-
Dichlorophenyl) hydrazine, 1-trityl-2-
[｛2- (N-ethyl-N-octylsulfamoyl)
-4-methanesulfonyl {phenyl] hydrazine, 1-
Benzoyl-2-tritylhydrazine, 1- (4-butoxybenzoyl) -2-tritylhydrazine, 1- (2,
4-dimethoxybenzoyl) -2-tritylhydrazine, 1- (4-dibutylcarbamoylbenzoyl) -2
-Tritylhydrazine, and 1- (1-naphthoyl)
-2-tritylhydrazine and the like.

In the light-sensitive material, the above-mentioned reducing agent is 1 mol of silver (including the above-described silver halide and an organic silver salt as an optional component).
It is preferably used in the range of 0.1 to 1500 mol% based on the total amount.

The polymerizable compound that can be used in the photosensitive material is not particularly limited, and a known polymerizable compound can be used. In addition,
As a method of using the photosensitive material, when a heat development process is scheduled, a high boiling point (for example, having a boiling point of 80
(° C. or more). Further, since the mode in which the photosensitive layer contains a color image-forming substance as an optional component described later aims to immobilize the color image-forming substance by polymerization and curing of the polymerizable compound, the polymerizable compound has a plurality of molecules in the molecule. It is preferably a crosslinkable compound having a polymerizable functional group.

The polymerizable compound that can be used for the photosensitive material is described in the above-mentioned and later-described series of photosensitive material application specifications.

The polymerizable compound used in the light-sensitive material is generally a compound having addition polymerization or ring-opening polymerization. The compound having addition polymerizability includes a compound having an ethylenically unsaturated group, and the compound having ring-opening polymerizability includes a compound having an epoxy group. A compound having an ethylenically unsaturated group is particularly preferable.

Compounds having an ethylenically unsaturated group that can be used in the photosensitive material include acrylic acid and salts thereof, acrylic esters, acrylamides, methacrylic acid and salts thereof, methacrylic esters, methacrylamides, and maleic anhydride. Acids, maleic esters, itaconic esters, styrenes, vinyl ethers, vinyl esters, N-vinyl heterocycles, allyl ethers,
There are allyl esters and their derivatives.

Specific examples of the polymerizable compound that can be used in the photosensitive material include acrylates, such as n-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, furfuryl acrylate, ethoxyethoxyethyl acrylate, and dicyclohexyloxy. Ethyl acrylate, nonylphenyloxyethyl acrylate, hexanediol diacrylate, butanediol diacrylate,
Neopentyl glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, 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-1,3-dioxane triacrylate, triacrylate of propylene oxide adduct of trimethylolpropane, polyacrylate of hydroxypolyether, polyester acrylate tricyclodecane dimethylol diacrylate and polyurethane acrylate And the like.

As other specific examples, methacrylates, methyl methacrylate, butyl methacrylate,
Ethylene glycol dimethacrylate, butanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate,
Examples thereof include pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, and dimethacrylate of polyoxyalkylenated bisphenol A.

The above polymerizable compounds may be used alone or in combination of two or more. Photosensitive materials using two or more polymerizable compounds in combination are described in JP-A-62-210445. In addition, 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 above-mentioned reducing agent or a color image forming substance which is an optional component described later can also be used as the polymerizable compound. As described above, the use of a substance which also serves as a reducing agent and a polymerizable compound or a substance which also serves as a color image forming substance and a polymerizable compound is included in the embodiment of the photosensitive material.

In the light-sensitive material, the polymerizable compound is silver halide 1
It is preferable to use 50,000 to 120,000 parts by weight based on parts by weight. A more preferred use range is from 12 to 12,000 parts by weight.

Instead of the components contained in the photosensitive layer of the photosensitive material of the first embodiment described above, a photosensitive material having a configuration (second embodiment) containing a photopolymerizable composition may be used.

As the photopolymerizable composition, a mixture of a photopolymerization initiator and a polymerizable compound can be used. The polymerizable compound that can be used for the photopolymerizable composition is the same as the polymerizable compound described above.

Examples of preferred photopolymerization initiators include α-alkoxyphenyl ketones, polycyclic quinones, benzophenones and substituted benzophenones, xanthones, thioxanthones, halogenated compounds (eg, chlorosulfonyl and chloromethyl, and others). Aromatic compounds, chlorosulfonyl and chloromethyl heterocyclic compounds, chlorosulfonyl and chloromethylbenzophenones, and fluorenones), haloalkanes, α-halo-α-phenylacetophenones, photoreducible dyes-reducing redox Couples, halogenated paraffins (eg, brominated or chlorinated paraffins), benzoyl alkyl ethers,
And a rofin dimer-mercapto compound couple.

Specific examples of preferred photopolymerization initiators include benzoylbutyl, 2,2-dimethoxy-2-phenylacetophenone, 9,10-anthraquinone, benzophenone, Michler's ketone, 4,4'-diethylaminobenzophenone, xanthone, chloroxanthone, thioxanthone, Chlorothioxanthone, 2,4-diethylthioxanthone, chlorosulfonylthioxanthone, chlorosulfonylanthraquinone, chloromethylanthracene, chloromethylbenzothiazole, chlorosulfonylbenzoxazole, chloromethylquinoline, chloromethylbenzophenone, chlorosulfonylbenzophenone, fluorenone, tetrabromide Carbon, benzoin butyl ether, benzoin isopropyl ether, 2,2'-bis (θ-chlorophenyl)-
Examples include a combination of 4,4 ', 5,5'-tetraphenylbiimidazole and 2-mercapto-5-methylthio-1,3,4-thiadiazole.

As the photopolymerization initiator, the compounds described above may be used alone or in combination of several kinds.

In the light-sensitive material of the present invention, the photopolymerization initiator is preferably used in an amount of 0.5 to 30% by weight based on the polymerizable compound used. A more preferred use range is 2
-20% by weight.

Further, a compound obtained by introducing a photosensitive group into a polymerizable compound as described above can also be used as the photopolymerizable compound.

Among the above components, the silver halide and the polymerizable compound (in the case of the second embodiment, a photopolymerizable composition) are contained in the form of microcapsules. Further, a reducing agent, a color image forming substance as an optional component (for example, the above-described color former /
In the case where a two-component color developing system such as a color developer is used, it is preferable that a color former and the like are also contained in the microcapsules.

There is no particular limitation on the wall material constituting the outer shell of the microcapsule. For a photosensitive material using a microcapsule having an outer shell made of a polyamide resin and / or a polyester resin, JP-A-62-209437 discloses a microcapsule having an outer shell made of a polyurea resin and / or a polyurethane resin. Japanese Patent Application Laid-Open No. 62-209438 discloses a photosensitive material used, and Japanese Patent Application Laid-Open No. 62-209439 discloses a photosensitive material using a microcapsule having an outer shell made of an amino-aldehyde resin. JP-A-62-209440 discloses a photosensitive material using microcapsules having a polyamide resin, and JP-A-62-209441 discloses a photosensitive material using a microcapsule having an outer shell made of an epoxy resin. For photosensitive materials using microcapsules having a composite resin shell containing polyurea resin
Japanese Patent Application Laid-Open No. 62-209442 discloses a photosensitive material using a microcapsule having a composite resin shell containing a polyurethane resin and a polyester resin.

When containing silver halide in microcapsules,
It is preferable that silver halide is present in the wall material constituting the outer shell of the microcapsule. For photosensitive materials containing silver halide in the wall material of microcapsules, see
-169147.

Further, silver halide, a reducing agent, a polymerizable compound, two or more microcapsules different in at least one component among components contained in microcapsules such as a color image forming substance which is an optional component described below may be used in combination. Good. In particular, when a full-color image is formed, it is preferable to use three or more types of microcapsules having different color hues of the contained color image forming substances. Japanese Patent Application Laid-Open No. 62-19885 describes a photosensitive material using two or more types of microcapsules in combination.
It is described in Japanese Patent Publication No. 0.

The average particle size of the microcapsules is preferably 3 to 20 μm. It is preferable that the distribution of the particle diameter of the microcapsules is uniformly distributed to a certain value or more as in the photosensitive material described in JP-A-63-5334. Also,
The thickness of the microcapsules is preferably within a certain range with respect to the particle diameter, as in the photosensitive material described in JP-A-63-81336.

When silver halide is contained in the microcapsules, the average grain size of the silver halide grains described above is preferably set to 1/5 or less of the average size of the microcapsules, and is set to 1/10 or less. Is more preferred. By setting the average grain size of the silver halide grains to 1/5 or less of the average size of the microcapsules,
A uniform and smooth image can be obtained.

The photosensitive material is obtained by providing a photosensitive layer containing the components described above on a support. There is no particular limitation on the support, but it is preferable to use a material that can withstand the processing temperature of the thermal development processing. For these specific examples, materials that can be used for the above-described image receiving material can be used.

Hereinafter, various aspects of the photosensitive material, optional components that can be included in the photosensitive layer, auxiliary layers that can be optionally provided in the photosensitive material, and the like will be sequentially described.

Optional components that can be included in the photosensitive layer of the photosensitive material include a color image forming substance, a sensitizing dye, an organic silver salt, a radical generator, various image formation accelerators, a thermal polymerization inhibitor, a thermal polymerization initiator, Development stop agents, fluorescent brighteners, anti-fading agents, dyes or pigments for preventing halation or irradiation, dyes having the property of decoloring by heating or light irradiation, matting agents, anti-smudge agents, plasticizers, water releasing agents, Examples include a binder, a photopolymerization initiator, a solvent for a polymerizable compound, and a water-soluble vinyl polymer.

The color image forming substance contained in the photosensitive layer is not particularly limited,
Various types can be used. In other words, substances that are themselves colored (dyes and pigments), or that are themselves colorless or light-colored but have external energy (heating, pressure, light irradiation, etc.) and other components (a color developer) A substance that develops color upon contact (color former) is also included in the color image forming substance. In the present invention, a color former is preferably used as described above. As the pigment, commercially available pigments and known pigments described in various documents can be used. Looking at the types of pigments by color, white pigments, black pigments,
Yellow pigment, lantern pigment, brown pigment, red pigment, purple pigment,
Blue pigment, green pigment, fluorescent pigment, metal powder pigment, etc.
Polymer-bound dyes. 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 and the like can be used. The above pigments may be surface-treated. Examples of the surface treatment method include a method of surface-coating a resin or wax, a method of attaching a surfactant, and a method of binding a reactive substance (eg, a silane coupling agent, an epoxy compound, a polyisocyanate, etc.) to the pigment surface. Can be considered. The particle size of the pigment that can be used in the present invention is preferably in the range of 0.01 μm to 10 μm after dispersion in the polymerizable compound, and more preferably in the range of 0.05 to 1 μm. The pigment is 5-1 to 100 parts by weight of the polymerizable compound.
It is preferably used in a proportion of 20 parts by weight, more preferably 10 to 60 parts by weight. As a method of dispersing the pigment in the polymerizable compound, a known dispersion technique used at the time of ink production, toner production, or the like can be used. Sand mills, attritors, pearl mills,
Examples include 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. The above pigment types,
For details on pigment surface treatment methods and pigment dispersion methods, see the Color Index (CI) Handbook, “Latest Pigment Handbook”, edited by the Japan Pigment Technical Association (1977), “Latest Pigment Application Technology”.
(CMC Publishing, 1986), and "Printing Ink Technology" (CMC Publishing, 1984).

The general photosensitive material using a color image forming substance is described in the above-mentioned JP-A-61-73145. Further, a photosensitive material using a dye or a pigment as a color image forming substance is disclosed in JP-A-62-187346, and a photosensitive material using a leuco dye is disclosed in JP-A-62-209436. Japanese Patent Application Laid-Open No. 62-251741 discloses a photosensitive material, and JP-A-62-288827 and JP-A-62-288827 describe photosensitive materials using a yellow color developing leuco dye.
Japanese Patent Application Laid-Open No. 288828/1988 describes a photosensitive material using a cyan-coloring leuco dye in Japanese Patent Application Laid-Open No. 63-53542.

The color image forming substance is based on 100 parts by weight of the polymerizable compound.
It is preferably used in a proportion of 0.5 to 50 parts by weight, more preferably in a proportion of 2 to 30 parts by weight. When a color developer is used, it is preferably used in a ratio of about 0.3 to 80 parts by weight with respect to 1 part by weight of the color former.

The sensitizing dye that can be used in the light-sensitive material is not particularly limited, and a silver halide sensitizing dye known in photographic technology or the like can be used. The sensitizing dyes include methine dyes, cyanine dyes, merocyanine dyes, complex cyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. These sensitizing dyes may be used alone or in combination. Particularly for the purpose of supersensitization, a method of using a sensitizing dye in combination is generally used. Further, together with the sensitizing dye, a dye having no spectral sensitizing effect by itself or a substance which does not substantially absorb visible light but exhibits supersensitization may be used in combination. The addition amount of the sensitizing dye is generally about 10 ^{-8 to} 10 ^-2 mol per mol of silver halide.

The sensitizing dye is preferably added at the stage of preparing a silver halide emulsion described below. A photosensitive material obtained by adding a sensitizing dye at the stage of forming silver halide grains is described in JP-A-62-947, in which a sensitizing dye is added to the silver halide emulsion after forming the silver halide grains. The photosensitive material obtained by adding in the preparation stage is disclosed in
There is a description in each of JP-A-210449. Further, specific examples of sensitizing dyes that can be used in photosensitive materials are described in JP-A-62-947 and JP-A-62-210449. Further, as in the light-sensitive material described in JP-A-63-184738, an infrared light-sensitive sensitizing dye may be used in combination.

The addition of an organic silver salt to a light-sensitive material is particularly effective in a heat development process. That is, when heated to a temperature of 80 ° C. or higher, it is considered that the organic silver salt participates in an oxidation-reduction reaction using a latent image of silver halide as a catalyst. In this case, the silver halide and the organic silver salt are preferably in a contact state or a close state. Examples of the organic compound constituting the organic silver salt include an aliphatic or aromatic carboxylic acid, a thiocarbonyl group-containing compound having a mercapto group or α-hydrogen, and an imino group-containing compound. Among them, benzotriazole is particularly preferred. The organic silver salt is generally used in an amount of 0.01 to 10 mol, preferably 0.01 to 1 mol, per 1 mol of silver halide. The same effect can be obtained by adding an organic compound (for example, benzotriazole) constituting the organic silver salt to the photosensitive layer instead of the organic silver salt. A photosensitive material using an organic silver salt is described in JP-A-62-3246. The organic silver salt as described above is preferably used in the range of 0.1 to 10 mol per mol of silver halide,
More preferably, it is used in the range of 1 to 1 mol.

To the photosensitive layer, a radical generator that participates in the above-described polymerization promotion (or polymerization inhibition) reaction of the reducing agent may be added. JP-A-62-195639 discloses a photosensitive material using triazene silver as the radical generator, and JP-A-62-195640 describes a photosensitive material using diazotate silver.
Japanese Patent Application Laid-Open No. Sho 62-195641 discloses a photosensitive material using an azo compound.

Various image formation accelerators can be used for the photosensitive material. Examples of the image formation accelerator include the promotion of an oxidation-reduction reaction between a silver halide (and / or an organic silver salt) and a redox agent with a reducing agent, and the conversion of a photosensitive material to an image receiving material or an image receiving layer (these will be described later). It has a function of promoting the transfer of the image forming substance. From the viewpoint of physicochemical functions, the image formation accelerator is a base, a base precursor, an oil, a surfactant, a compound having an antifogging function and / or a development accelerating function, a thermal solvent, a compound having an oxygen removing function, and the like. It is further classified into However, these substance groups generally have a composite function and usually have some of the above-mentioned promoting effects. Therefore, the above classification is a matter of convenience, and in practice, one compound often has a plurality of functions.

 Examples of various image formation accelerators are shown below.

Examples of preferred bases include hydroxides of alkali metals or alkaline earth metals as inorganic bases; tertiary phosphates, borates, carbonates, metaborates of alkali metals or alkaline earth metals; Zinc oxide or a combination of zinc oxide and a chelating agent such as sodium picolinate; ammonium hydroxide; quaternary alkylammonium hydroxide; hydroxides of other metals, and the like. Aromatic amines (trialkylamines, hydroxylamines, aliphatic polyamines); aromatic amines (N-alkyl-substituted aromatic amines, N-
(Hydroxylalkyl-substituted aromatic amines and bis [p- (dialkylamino) phenyl] methanes), heterocyclic amines, amidines, cyclic amidines, guanidines, cyclic guanidines, and the like.
The above are preferred.

As base precursors, salts of organic acids and bases that are decarboxylated by heating, intramolecular nucleophilic substitution, Rossen rearrangement,
Compounds which release a base by causing some reaction by heating, such as compounds which release amines by a reaction such as Beckmann rearrangement, and compounds which generate a base by electrolysis or the like are preferably used. Specific examples of the base precursor include guanidine trichloroacetic acid, piperidine trichloroacetic acid, morpholine trichloroacetic acid, p-toluidine trichloroacetic acid, 2-picoline trichloroacetic acid, guanidine phenylsulfonyl acetate, guanidine 4-chlorophenylsulfonyl acetate, and 4-methyl- Guanidine sulfonylphenylsulfonyl acetate and guanidine 4-acetylaminomethylpropiolate can be exemplified.

Bases or base precursors can be used in the photosensitive material in a wide range. The base or base precursor is suitably used in an amount of 100% by weight or less in terms of the weight of the coating film of the photosensitive layer, and more preferably in the range of 0.1% by weight to 40% by weight. In the present invention, the base and / or the base precursor may be used alone or as a mixture of two or more.

The photosensitive material using a base or a base precursor is described in JP-A-62-264041. Further, photosensitive materials using a tertiary amine as a base are described in JP-A-62-170954, and photosensitive materials using a fine particle dispersion of a hydrophobic organic base compound having a melting point of 80 to 180 ° C. JP-A-62-209523 discloses a photosensitive material using a guanidine derivative having a solubility of 0.1% or less.
Japanese Patent Application Laid-Open No. 62-209448 discloses a photosensitive material using a hydroxide or a salt of an alkali metal or an alkaline earth metal.

Further, 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, and that silver, copper, a silver compound or a copper compound is used as a catalyst for a base generation reaction. JP-A-63-46446 discloses a photosensitive material including the above-mentioned propiolate and silver, copper, a silver compound or a copper compound in a state of being isolated from each other. A photosensitive material containing a free ligand in addition to the propiolate and the silver, copper, silver compound or copper compound is disclosed in JP-A-63-963.
No. 7942, the use of propiolate as a base precursor, further for a photosensitive material containing a heat-meltable compound as a reaction accelerator of the base generation reaction, JP-A-63-46447, a sulfonyl acetate as a base precursor. JP-A-63-48543 discloses a photosensitive material containing a heat-meltable compound as a reaction accelerator for a base generation reaction, and further discloses a photosensitive material using a compound obtained by bonding an isocyanate or isothiocyanate to an organic base as a base precursor. The materials are described in JP-A-63-24242.

When a base or a base precursor is used in the photosensitive material, the above-described embodiment is to accommodate silver halide, a reducing agent and a polymerizable compound in the microcapsules, and the base or the base precursor may be present in the photosensitive layer outside the microcapsules. Good. In this case, a base or a base precursor may be contained in another microcapsule as in the light-sensitive material described in JP-A-62-209521. The light-sensitive material using a microcapsule containing a base or a base precursor is described in Japanese Patent Laid-Open No. Sho 62 (1993), as well as the above specification. -209
No. 522, a photosensitive material containing a base or solid fine particles carrying a base precursor in a microcapsule is disclosed in JP-A-62-209526, and a microcapsule containing a base compound having a melting point of 70 ° C. to 210 ° C. is used. The light-sensitive materials used are described in JP-A-63-65437, respectively. Further, instead of the microcapsules containing the base or the base precursor, particles containing a base or a base precursor and a hydrophobic substance in a compatible state, such as a photosensitive material described in JP-A-63-97943, may be used. .

Further, a base or a base precursor may be contained in the photosensitive microcapsule. As a method of incorporating the base precursor into the capsule, JP-A-64-32251, as described in Japanese Patent Application No. 63-92686, directly introduced into the polymerizable compound in the form of solid dispersion. Well, Japanese Patent Application
As described in JP-A-63-218964 and the specification filed on June 22, 1989, the base precursor may be introduced in a form dispersed in water and emulsified in the polymerizable compound.

The base or base precursor is described in JP-A-62-253.
As described in JP-A-140, it may be added to an auxiliary layer other than the photosensitive layer (a layer containing a base or a base precursor described later). Further, as described in JP-A-63-32546, the above-mentioned support may be made porous and a base or a base precursor may be contained in the porous support.

As the oil, a high-boiling organic solvent used as a solvent for emulsifying and dispersing a hydrophobic compound can be used.

Examples of the surfactant include pyridinium salts, ammonium salts, phosphonium salts described in JP-A-59-74547, and polyalkylene oxides described in JP-A-59-57231.

The compound having an antifogging function and / or a development accelerating function can be used for the purpose of obtaining a clear image having a high maximum density and a low minimum density (an image having a high S / N ratio). Japanese Patent Application Laid-Open No. 62-151838 discloses a photosensitive material using an antifoggant as a compound having an antifogging function and / or a development accelerating function. JP-A-61-151841, JP-A-62-151842 discloses a photosensitive material using a thioether compound, and JP-A-62-151843 discloses a photosensitive material using a polyethylene glycol derivative. Japanese Patent Application Laid-Open No. 62-151844 discloses a photosensitive material using acetylene compound, and Japanese Patent Application Laid-Open No. 62-17823
No. 2, JP-A-62-183450 describes a photosensitive material using a sulfonamide derivative, and JP-A-63-91653 describes a photosensitive material using a quaternary ammonium salt. .

As the thermal solvent, a compound which can be used as a solvent for a reducing agent, a compound which is a substance having a high dielectric constant and which is known to promote physical development of a silver salt, and the like are useful. Useful thermal solvents, polyethylene glycols U.S. Patent No. 3347675 Pat described derivatives such as oleic acid esters of polyethylene oxide, beeswax, glycerol monostearate, -SO ₂ -
And / or a high dielectric constant compound having a -CO- group, a polar substance described in U.S. Pat.
1,10 on pages 26-28 of the December 1976 Disclosure Magazine
-Decanediol, methyl anisate, biphenyl suberate and the like are preferably used. The photosensitive material using a thermal solvent is described in JP-A-62-86355.

The compound having an oxygen removing function can be used for the purpose of eliminating the influence of oxygen during development (oxygen has a polymerization inhibiting effect). Examples of the compound having an oxygen removing function include a compound having two or more mercapto groups. The photosensitive material using a compound having two or more mercapto groups is described in JP-A-62-209443.

The thermal polymerization initiator is generally a compound that is thermally decomposed under heating to generate a polymerization initiation species (particularly a radical), and is generally used as an initiator for radical polymerization. The thermal polymerization initiator is described in “Addition Polymerization and Ring-Opening Polymerization” edited by the Editing Committee of Polymer Experiments of the Society of Polymer Science, 1983, Kyoritsu Shuppan, No. 6.
Page 18 to page 18. The thermal polymerization initiator is used preferably in the range of 0.1 to 120% by weight, more preferably 1 to 10% by weight, based on the polymerizable compound. In a system for polymerizing a polymerizable compound in a portion where a silver halide latent image is not formed, it is preferable to add a thermal polymerization initiator to the photosensitive layer. Also,
Japanese Patent Application Laid-Open No. Sho 62-708 discloses a photosensitive material using a thermal polymerization initiator.
It is described in JP-A-36.

A development terminator that can be used in photosensitive materials is a compound that neutralizes a base or reacts with a base immediately after proper development to reduce the base concentration in the film and to interact with a compound that stops development and silver and silver salts. Is a compound that suppresses development. Specifically, an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction with a coexisting base when heated,
Alternatively, a nitrogen-containing heterocyclic compound, a mercapto compound and the like can be mentioned. Examples of the acid precursor include JP-A-60-108
Examples thereof include oxime esters described in JP-A-837 and JP-A-60-192939, and compounds which release an acid by Rossen rearrangement described in JP-A-60-230133. Also,
Examples of electrophilic compounds that undergo a substitution reaction with a base upon heating include compounds described in JP-A-60-230134.

A dye or pigment may be added to the photosensitive layer of the photosensitive material for the purpose of preventing halation or irradiation. JP-A-63-29748 describes a photosensitive material in which a white pigment is added to a photosensitive layer for the purpose of preventing halation or irradiation.

As the anti-smudge agent used in the light-sensitive material, solid particles at room temperature are preferable. A specific example is the UK patent no.
No. 1232347 Starch particles described in U.S. Pat.
No. 36, etc. described polymer fine powder, UK Patent No. 1235991
Microcapsule particles not containing a coloring agent described in the specification, cellulose fine powder described in U.S. Pat.No. 2,711,375, talc, kaolin, bentonite, rock, zinc oxide, titanium oxide, inorganic particles such as alumina, etc. Can be mentioned. The average particle size of the particles is preferably in the range of 3 to 50 μm in volume average diameter, and 5 to 40 μm.
The range of m is more preferred. As described above, when the oil droplets of the polymerizable compound are in the form of microcapsules, it is more effective that the particles are larger than the microcapsules.

The binder that can be used in the photosensitive material can be contained alone or in combination in the photosensitive layer. It is preferable to use a hydrophilic binder mainly. As the hydrophilic binder, a transparent or translucent hydrophilic binder is representative, for example, gelatin, gelatin derivatives, cellulose derivatives, starch, natural substances such as gum arabic, and polyvinyl alcohol, polyvinyl pyrrolidone, acrylamide polymer and the like Includes synthetic polymeric materials such as water-soluble polyvinyl compounds. Other synthetic polymeric substances include dispersed vinyl compounds in the form of latex, in particular for increasing the dimensional stability of the photographic material. In addition,
For photosensitive materials using a binder, see JP-A-61-690.
No. 62 describes this. For a photosensitive material using a binder together with a microcapsule, see JP-A-62-2
This is described in JP 09525.

A photopolymerization initiator may be added to the photosensitive layer of the photosensitive material for the purpose of polymerizing an unpolymerized polymerizable compound after image transfer. For photosensitive materials using photopolymerization initiators,
It is described in JP-A-62-161149. Further, the photopolymerization initiator can be used in a system for polymerizing a polymerizable compound in a portion where a silver halide latent image is not formed, similarly to the thermal polymerization initiator described above (Japanese Patent Application No. 1-27175). Specification).

When a solvent for a polymerizable compound is used for the photosensitive material, it is preferable that the solvent is used by being encapsulated in a microcapsule different from the microcapsule containing the polymerizable compound. The photosensitive material using an organic solvent miscible with the polymerizable compound encapsulated in the microcapsule is described in JP-A-62-209524.

A water-soluble vinyl polymer may be adsorbed on the silver halide grains described above before use. The photosensitive material using the water-soluble vinyl polymer as described above is described in JP-A-63-91652.

In addition to the examples described above, examples of optional components that can be included in the photosensitive layer and usage modes thereof are also described in the above-described application specification relating to the series of photosensitive materials,
Disclosure Magazine, Vol. 170, June, 1978, No. 17029 (pages 9 to 15).

The photosensitive layer of the photosensitive material comprising the above-described components preferably has a pH value of 7 or less as in the photosensitive material described in JP-A-62-275235.

Layers that can be optionally provided on the photosensitive material include a heating element layer, an antistatic layer, an anti-curl layer, a peeling layer, a cover sheet or a protective layer, a layer containing a base or a base precursor, a base barrier layer, and an antihalation layer. (Colored layer)
And the like.

 Next, examples and comparative examples of the present invention will be described.

[Example 1] [Preparation of image receiving material] 40% sodium hexametaphosphate aqueous solution in 125 g of water 11
g, and a mixed solution of 34 g of zinc 3,5-di-α-methylbenzylsalicylate and 82 g of a 55% calcium carbonate slurry was further added thereto, followed by coarse dispersion with a mixer. This liquid was further dispersed with a Dynomill disperser (dispersion A).

To 200 g of the obtained solution, 142 g of an aqueous solution of 8% polyvinyl alcohol (trade name: PVA-117, manufactured by Kuraray Co., Ltd.) and 90 ml of water were added and mixed uniformly to prepare a coating solution for forming an image receiving layer. The coating amount of the coating solution to paper having a basis weight of 55 g / m ² is 60 g / m ²
And then dried at 100 ° C. to form an image receiving layer.

Next, 1 ml of perfluoroalkyl phosphate [fluorinated compound] (Surflon S112, manufactured by Asahi Glass Co., Ltd.) was made 100 ml with water and uniformly dissolved, and the solution was coated on the above-mentioned image receiving layer in an amount of 24.6 g. / m ² (solid content: 0.03 g / m ² ), then uniformly coated and dried at 100 ° C to receive the image receiving material (A)
It was created.

[Examples 2 to 7] In Example 1, except that the compounds shown in Table 1 were used as the fluorine-based compounds so as to have the same coating amount (solid content 0.03 g / m ² ), respectively. By operating in the same manner as in Example 1, the corresponding image receiving materials (B) to (G) were prepared.

Example 8 In Example 1, instead of applying a solution containing a fluorine compound on the image receiving layer, 1.8 mg of a fluorine compound was added to the coating solution for forming the image receiving layer (0.1 g / m ² containing), except that the coated it on a support to prepare a receiving material (H) by the same operation as in example 1.

Example 9 An aqueous 8% polyvinyl alcohol (PVA-117, manufactured by Kuraray Co., Ltd.) aqueous solution 6 was added to 1000 g of the dispersion A obtained in Example 1.
11 g were mixed.

Calcium carbonate (trade name: PC700, manufactured by Shiraishi Industry Co., Ltd.)
348 g, 40% aqueous solution of acrylic acid / maleic acid copolymer 7.
18g and 1000ml of water are mixed, and a polytron disperser (PT10 / 35
(Kinematica Co., Ltd.) at 2000 revolutions per minute for 20 minutes. The above mixture and a dispersion containing calcium carbonate were mixed, and 14 g of zinc chloride and 125 g of an 8% aqueous solution of polyvinyl alcohol (PVA-117, manufactured by Kuraray Co., Ltd.) were rotated at 10,000 rpm using a homogenizer. And then add 325 g of 10% aqueous gelatin solution and 325 g of water.
And added. The coating amount 10 The coating liquid on paper having a basis weight of 55 g / m ²
Coating was carried out at ² cc / m ² and dried at 100 ° C. to form an image receiving layer.

Next, a perfluoroalkyl phosphate [fluorine compound] (trade name: Surflon S112, manufactured by Asahi Glass Co., Ltd.)
1 ml was dissolved in water to make 100 ml, and the solution was uniformly coated on the image receiving layer so that the coating amount was 24.6 g / m ² (solid content 0.03 g / m ² ). To obtain an image receiving material (I).

Comparative Example 1 An image receiving material (X-1) was prepared in the same manner as in Example 1, except that the solution containing the fluorine-based compound was not applied on the image receiving layer. .

Comparative Example 2 An image receiving material (X-2) was prepared in the same manner as in Example 9, except that the solution containing the fluorine-based compound was not applied on the image receiving layer. .

[Preparation of photosensitive material (I)] Preparation of silver halide emulsion (A) (blue sensitivity) Gelatin aqueous solution (24 g of gelatin and 1.2 g of sodium chloride were added to 1200 ml of water, and the pH was adjusted to 3.2 with 1N sulfuric acid. Then, 600 ml of an aqueous solution containing 117 g of potassium bromide and an aqueous solution of silver nitrate (0.74 ml of silver nitrate in 600 ml of water) were added thereto.
Mol dissolved) at the same time over 45 minutes at an equal flow rate. Five minutes after the addition was completed, 200 ml of an aqueous solution containing 4.3 g of potassium iodide was further added in a constant amount over 5 minutes. Further, 1.2 g of poly (isobutylene-mono-sodium maleate) was added to this emulsion, sedimented, washed with water and desalted, dissolved with 24 g of gelatin, further dissolved in 5 mg of sodium thiosulfate and sensitized as described below. 0.5 g of the dye (a) was added, and chemically sensitized at 60 ° C. for 15 minutes to prepare a silver halide emulsion (A) with a yield of 1000 g.

Preparation of silver halide emulsion (B) (green sensitivity) Gelatin aqueous solution (24 g of gelatin and 1.2 g of sodium chloride are added to 1200 ml of water, adjusted to pH 3.2 with 1N sulfuric acid,
), And 600 ml of an aqueous solution containing 117 g of potassium bromide and an aqueous solution of silver nitrate (a solution obtained by dissolving 0.74 mol of silver nitrate in 600 ml of water) were simultaneously added at an equal flow rate over 45 minutes. Five minutes after the addition was completed, 200 ml of an aqueous solution containing 4.3 g of potassium iodide was further added in a constant amount over 5 minutes. This emulsion was mixed with poly (isobutylene-co-
1.2 g of monosodium maleate) was added and allowed to settle,
After washing with water and desalting, 24 g of gelatin was added to dissolve, 5 mg of sodium thiosulfate and 0.47 g of the following sensitizing dye (b) were added, and the mixture was chemically sensitized at 60 ° C. for 15 minutes, yielding 1000 g of silver halide. Emulsion (B) was prepared.

Preparation of silver halide emulsion (C) (red sensitivity) Gelatin aqueous solution (24 g of gelatin and 1.2 g of sodium chloride are added to 1200 ml of water, and the pH is adjusted to 3.2 with 1N sulfuric acid.
), And 600 ml of an aqueous solution containing 117 g of potassium bromide and an aqueous solution of silver nitrate (a solution obtained by dissolving 0.74 mol of silver nitrate in 600 ml of water) were simultaneously added at an equal flow rate over 45 minutes. Five minutes after the completion of the addition, 200 ml of an aqueous solution containing 4.3 g of potassium iodide was further added in a constant amount over 5 minutes. To this emulsion, 1.2 g of poly (isobutylene-mono-sodium maleate) was added, sedimented, washed with water and desalted, and dissolved by adding 24 g of gelatin.
Further, 5 mg of sodium thiosulfate and 0.47 g of the following sensitizing dye (c) were added, and the mixture was chemically sensitized at 60 ° C. for 15 minutes to prepare a silver halide emulsion (C) with a yield of 1000 g.

Preparation of Photosensitive Composition (A) (Blue Sensitivity) In 83 g of the following polymerizable compound, 0.77 g of the following copolymer and 12.5 g of the following color image forming substance (a) were dissolved. 6.4 g of the following hydrazine compound in the above solution, 6.1 g of the following reducing agent,
An oily solution was prepared by dissolving 0.09 g of the following development inhibitor releasing precursor, 0.01 g of the following antifoggant, 1.8 g of the following surfactant and 20 g of methylene chloride. Further, 15 g of the above-mentioned silver halide emulsion (A) and 1.5 ml of a 10% aqueous solution of potassium bromide were added to the above solution, followed by stirring for 5 minutes. Further, 1.5 ml of a 1% aqueous solution of polyvinylpyrrolidone (K-15) was added thereto, followed by stirring for 5 minutes. Using a homogenizer, the mixed solution containing the silver halide emulsion was subjected to 15,000 / min at 40 ° C.
The mixture was stirred for 5 minutes by rotation to obtain a photosensitive composition (A) in which a silver halide emulsion was emulsified in an oily solution.

Preparation of photosensitive composition (B) (green sensitivity) The silver halide emulsion (B) was used instead of the silver halide emulsion (A) used in the preparation of the photosensitive composition (A), and A photosensitive composition (B) was prepared in the same manner as the photosensitive composition (A), except that the following color image-forming substance (b) was used instead of the image-forming substance (a).

Preparation of photosensitive composition (C) (red sensitivity) The silver halide emulsion (C) was used in place of the silver halide emulsion (A) used in the preparation of the photosensitive composition (A), and A photosensitive composition (C) was prepared in the same manner as the photosensitive composition (A), except that the following color image-forming substance (c) was used instead of the image-forming substance (a).

Preparation of Photosensitive Microcapsule Dispersion (A) (Blue Sensitivity) An isocyanate compound (trade name: Takenate D110N, manufactured by Takeda Pharmaceutical Co., Ltd.) was added to the above photosensitive composition (A).
4.5 g was dissolved and added to 125 g of a 10% aqueous solution of a polymer (trade name: Versa TL-502, manufactured by National Starch Co.) adjusted to pH 6.0, and the homogenizer was used at 9000 rpm per minute at 40 ° C. After stirring for 30 minutes, the photosensitive composition (A) was emulsified in an aqueous solvent.

Melamine-formalin prepolymer (34.5 g of melamine and 57 g of formalin were added to 186 g of water while stirring the aqueous emulsion at 1200 rpm at 25 ° C., and the mixture was stirred at 600 rpm at 60 ° C. for 30 minutes). 77 g), and the pH was adjusted to 6.0. The solution was further stirred at 60 ° C. at 1200 rpm for 90 minutes, and then 27 g of a 40% aqueous urea solution was added to adjust the pH to 3.5. The dispersion thus obtained is further subjected to 1000 rpm at 60 ° C.
Stir for 40 minutes and finally adjust the pH to 6.5. Thus, a photosensitive microcapsule dispersion liquid (A) was prepared.

Preparation of photosensitive microcapsule dispersion liquid (B) (green sensitivity) In the preparation of the photosensitive microcapsule dispersion liquid (A), the photosensitive composition (B) is used in place of the photosensitive composition (A). A photosensitive microcapsule dispersion liquid (B) was prepared in the same manner as above except for the above.

Preparation of photosensitive microcapsule dispersion liquid (C) (red sensitivity) In the preparation of the photosensitive microcapsule dispersion liquid (A), the photosensitive composition (C) is used in place of the photosensitive composition (A). A photosensitive microcapsule dispersion liquid (C) was prepared in the same manner as above except for the above.

Preparation of Base Precursor Dispersion 20 g of the following base precursor was added to 80 g of a 4% aqueous solution of polyvinyl alcohol (PVA205, manufactured by Kuraray Co., Ltd.)
The mixture was dispersed at 20 ° C. using a dyno mill until the average particle diameter became 2 μm or less to prepare a base precursor dispersion.

Preparation of paper support 20 parts of LBSP and LBKP80 are beaten to 290 cc of Canadian Freeness (CSF) using refinery, and alkyl ketene dimer (trade name: ACCOPEL 12,
0.3 parts of Dick Hercules), 0.5 parts of polyamide polyamine epichlorohydrin (trade name: Caimen 557, manufactured by Dick Hercules) as a fixing agent, and cation-modified polyacrylamide (trade names: Polystron 705, Arakawa Chemical (trade name) as a paper strength enhancer 0.5 part of the pulp was added at a pulp absolute dry weight ratio. Next, using a fourdrinier paper machine, the paper material was formed into base paper having a basis weight of 60 g / m ² and a thickness of 66 μm.

On the surface (felt surface) of the base paper prepared as described above, a coating solution for forming a moisture-proof layer composed of polyvinylidene chloride resin, and 100 parts of SBR latex (trade name: SN-304, manufactured by Sumitomo Nogatack Co., Ltd.), 1 part of sodium polyacrylate (trade name: Alon T40, manufactured by Toa Gosei Chemical Industry Co., Ltd.), 200 parts of clay (trade name: UW-90, manufactured by Engelhardt), and petroleum resin (trade name: Carbomule R) , manufactured by Dick Hercules Inc.) a composition consisting of 100 parts of moisture-proof layer-forming coating solution was prepared respectively, applying the coating liquid in order at a coverage of Tsuboryo is ^{16g / m 2, 5g / m} 2 , respectively by an air knife coater Thus, a paper support was prepared.

Preparation of photosensitive material (I) Each of the photosensitive microcapsule dispersions (A) described above,
16 g of (A) for each of (B) and (C),
18.5 g of (B), 14.8 g of (C), 6.8 g of the above base precursor dispersion, 9 ml of a 20% aqueous solution of sorbitol and 10 ml of a 10% aqueous solution of starch (KF-5, Shinshin Food Industry Co., Ltd.)
Was mixed. To this mixture, 5% of the above-mentioned surfactant was further added.
A 4% aqueous solution was added to prepare a coating solution having a total amount of 174 g.

This coating solution was applied on the above-mentioned paper support at a coating amount of 50 g / m ² and dried at about 60 ° C. to prepare a photosensitive material (I).

[Image formation and evaluation thereof] Next, each of the image receiving materials (A) to (A) obtained as described above.
An image was formed using (I), (X-1) and (X-2), and the above-mentioned photosensitive material (I), and evaluated.

(1) Evaluation of Peelability The above-mentioned image receiving material and photosensitive material were superposed under high temperature and high humidity (30 ° C., 80% RH), and passed through a pressure roller of 700 kg / cm ^{2 in} this state. Then, the image receiving material is separated from the photosensitive material,
The force required for the peeling at this time (peeling force: g / width 26 cm) was measured using a spring.

(2) Evaluation of transferred image The photosensitive material (I) was exposed to 2,000 lux illuminance for 1 second through a filter having a continuous density change pattern using a tungsten bulb, and then the photosensitive material was heated to 155 ° C. And heat-developed for 10 seconds with the photosensitive layer surface in close contact. Next, the photosensitive material was overlaid on each of the above image receiving materials under the same atmosphere as in the above (1), and passed through a pressure roller of 700 kg / cm ^{2 in} that state. Then, the image receiving material was peeled off from the photosensitive material to obtain a full-color positive image on the image receiving material. The density (maximum density) of the obtained image was measured using a Macbeth reflection densitometer.

 Table 1 summarizes the above results.

In the table, the numbers in the column of “Compound name” correspond to the numbers of the fluorine-based compounds ((1) to (81)) exemplified above.

As is clear from the results shown in Table 1, when the image forming method according to the present invention was performed using the image receiving materials (A to I) containing the fluorine-based compound, the pressure-sensitive transfer after the pressure transfer was performed. Peeling was easy and the reduction of the maximum concentration did not occur much. On the other hand, when the image forming method is performed using the image receiving materials (X-1 and X-2) containing no fluorine-based compound, peeling becomes difficult, and the image receiving materials (X-
In the case of 2), cohesive failure occurred.

[Example 10] [Preparation of photosensitive material (II)] Preparation of photosensitive composition 37.5 g of the following polymerizable compound (trade name: Kayarad R604, manufactured by Nippon Kayaku Co., Ltd.) was added to a photopolymerization initiator (trade name) : Irgacure 651, Ciba-Geigy) (3.0 g) and the following magenta image forming substance (7.5 g) were dissolved to obtain a photosensitive composition.

Preparation of photosensitive microcapsule dispersion liquid A mixture of 5.6 g of a 15% aqueous solution of potassium polyvinylbenzenesulfinate and 134.5 g of a 5.1% aqueous solution of polyvinylpyrrolidone (trade name: K-90, manufactured by Wako Pure Chemical Industries, Ltd.) This was adjusted to pH 5.0. Then, the photosensitive composition obtained above is added to the mixture, and the mixture is dissolved at 50 ° C./minute using a dissolver.
The mixture was stirred at 3000 rpm for 30 minutes to obtain an emulsion in the form of an O / W emulsion.

Separately, 14.8 g of melamine in 37% formaldehyde aqueous solution 2
0.0 g and 76.3 g of distilled water were added, and the mixture was heated at 60 ° C. and stirred for 40 minutes to obtain a transparent aqueous solution of a melamine-formaldehyde precondensate.

40.0 g of an aqueous solution of this initial condensate and 8.0 g of water were mixed with the O / W
In addition to the emulsion, adjust the pH to 5. using a 10% aqueous solution of sulfuric acid.
Adjusted to 0. Then it was heated to 60 ° C. and stirred for 60 minutes. Further, 11 g of a 40% aqueous solution of urea was added, and the mixture was stirred for 40 minutes while heating at 60 ° C. Then, the pH was adjusted to 6.5 using a 10% aqueous sodium hydroxide solution to
A photosensitive microcapsule dispersion having a formaldehyde resin as a capsule wall was prepared.

Preparation of photosensitive material (II) 35.5 g of the above-mentioned photosensitive microcapsule dispersion, 4 ml of a 5% aqueous solution of the following surfactant, and a 10% aqueous solution of polyvinyl alcohol (trade name: PVA-205, manufactured by Kuraray Co., Ltd.)
10 ml were mixed, and water was further added to prepare a coating solution having a total amount of 74 g.

This coating solution was applied onto polyethylene terephthalate (support) having a thickness of 100 μm at a coating amount of 57 g / m ² , and dried at about 60 ° C. to prepare a photosensitive material (II).

[Image formation and evaluation thereof] Next, each of the image receiving materials (A) to (I) and (X
The following image formation was carried out using -1) and (X-2) and the photosensitive material (II) obtained as described above, and evaluated.

(1) Evaluation of Peelability The above-mentioned image receiving material and photosensitive material were superposed under high temperature and high humidity (30 ° C., 80% RH), and passed through a pressure roller of 700 kg / cm ^{2 in} this state. Then, the image receiving material is separated from the photosensitive material,
The force required for the peeling at this time (peeling force: g / width 26 cm) was measured using a spring.

(2) Evaluation of transferred image The photosensitive material (II) was exposed imagewise for 2 seconds from a distance of 30 cm using a 200 W high-pressure mercury lamp.

Next, the photosensitive material was overlaid on each of the above image receiving materials under the same atmosphere as in the above (1), and passed through a pressure roller of 700 kg / cm ^{2 in} that state. Then, the image receiving material was peeled off from the photosensitive material to obtain a positive magenta image on the image receiving material. The density (maximum density) of the obtained image was measured using a Macbeth reflection densitometer.

 Table 2 summarizes the above results.

In the table, the numbers in the column of “Compound name” correspond to the numbers of the fluorine-based compounds ((1) to (81)) exemplified above.

As is clear from the results shown in Table 2, when the image forming method according to the present invention was performed using the image receiving materials (A to I) containing the fluorine-based compound, the pressure-sensitive transfer after the pressure transfer was performed. Peeling was easy and the reduction of the maximum concentration did not occur much. On the other hand, when the image forming method is performed using the image receiving materials (X-1 and X-2) containing no fluorine-based compound, peeling becomes difficult, and the image receiving materials (X-
In the case of 2), cohesive failure occurred.

 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-61-281242 (JP, A) JP-A-64-73343 (JP, A) JP-A-61-193155 (JP, A) JP-A 63-281155 132236 (JP, A) JP-A-61-278849 (JP, A) JP-A-62-187346 (JP, A) JP-A-62-110459 (JP, A)

Claims (2)

(57) [Claims] 1. A photosensitive layer containing a silver halide, a reducing agent and a polymerizable compound on a support, wherein at least the silver halide and the polymerizable compound are contained in a microcapsule in the photosensitive layer. The photosensitive material is exposed imagewise, simultaneously with or after imagewise exposure,
The heat-development process is performed, and the above-described heat-development-processed photosensitive material is pressed with an image-receiving material having a porous image-receiving layer containing a fluorine-based compound on a support. An image forming method comprising transferring a polymerizable compound of polymerization to the image receiving material. 2. A photosensitive material comprising a photosensitive layer containing a photopolymerizable composition on a support, and the photopolymerizable composition contained in the photosensitive layer in a state of being contained in a microcapsule is used for image-forming. Exposure to light, and pressurizing the photosensitive material that has been subjected to imagewise exposure in a state where an image-receiving material having a porous image-receiving layer containing a fluorine-based compound is superimposed on a support, whereby unpolymerized light is irradiated. An image forming method comprising transferring the polymerizable composition to the image receiving material.