JPH07120013B2 - Image forming method - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to an image forming method using a photothermographic material. More specifically, the present invention relates to an image forming method using a photothermographic material having a photosensitive layer containing a photosensitive component provided on a paper support.

BACKGROUND OF THE INVENTION In recent years, a photothermographic material can be easily and quickly subjected to dry processing (heat treatment) without using a so-called wet development processing method using a developing solution as an image forming processing method. The development of the material is actively carried out as a new recording material field from the viewpoint of practical advantage that an image can be obtained by the method.

Regarding the photothermographic material and its process, see, for example, "Basics of Photographic Engineering (Published in 1978, Corona Publishing Co., Ltd.), 553-555.
Page, 40 pages of video information issued in April 1978, Nebletts Handbook
of Phtography and Reprography 7th Ed. (Van Nostran
d Reinhold Company), pages 32-33, U.S. Pat.
No. 4, No. 3,301,678, No. 3,392,020, No. 3, 45
7,075, British Patents 1,131,108 and 1,167,777
Each statement such as the issue, and Research Disclosure magazine
June 1978, pages 9 to 15 (RD-17029).

Many methods have already been proposed for obtaining color images (color images). Regarding the method of forming a color image by combining an oxidant of a developing solution with a coupler, US Pat. No. 3,531,281 discloses a p-phenylenediamine reducing agent and a phenolic or active methylene coupler in US Pat. No. 3,761,270. P-aminophenol-based reducing agents are described in Belgian Patent No. 802,519 and Research Disclosure, September 1975, 31-32.
In the page, the sulfonamidephenol-based reducing agent,
U.S. Pat. No. 4,021,240 proposes a combination of a sulfonamidephenol-based reducing agent and a 4-equivalent coupler, respectively.

Further, for the method of forming a positive image by the photosensitive silver dye bleaching method, see, for example, Research Disclosure Magazine.
April 1976, pages 30-32 (RD-14433), December 1976, pages 14-15 (RD-15227), U.S. Pat. No. 4,235,957, etc., describe useful dyes and bleaching methods. ing.

Further, for the method of forming a color image using a leuco dye, for example, U.S. Patent Nos. 3,985,565 and 4,022,6.
It is described in each specification such as No. 17.

Furthermore, an image forming method by thermal development using a compound having a dye portion in advance and capable of releasing a movable dye in response to the reduction reaction of silver halide to silver at a high temperature condition is described in Europe. Patent Publication Nos. 76,492, 79,056, and JP-A-58-28928, 59-26008, 58-58.
543, 58-79247, 58-149046, 58-149047
No. It is disclosed in each publicity.

The photothermographic material as described above is generally composed of a support and a photosensitive layer provided thereon and containing a photosensitive component. If necessary, a protective layer or the like may be provided on the photosensitive layer.

In image formation using a photothermographic material, usually, the photosensitive material is imagewise exposed using an exposing means that emits light according to a photosensitive component, and then the material is placed on a hot plate such as a hot plate, It is carried out by a method in which the surface side of is directly contacted with a hot plate and heat development is performed.

In the photothermographic material having the above-described structure, paper is often used as a support for the reason that the material itself is lightweight, is easy to handle, or can be provided at a low cost, but is generally composed of a paper support. When the above-mentioned image formation is carried out using the light-sensitive material described above, wrinkles tend to be generated on the support, and wrinkles are also generated on the finally obtained image with the formation of wrinkles. In some cases, the image quality may be deteriorated as a whole due to uneven density.

As one method to prevent the deterioration of image quality as described above,
For example, a method disclosed in JP-A-54-30032, in which moisture contained in the photosensitive material is removed and then the photosensitive material is heat-developed, can be used. However, even if this method is used, it is not possible to sufficiently suppress the occurrence of image unevenness (wrinkles, density unevenness, etc.), and thus it has been difficult to stably obtain a good image.

By the way, the applicant of the present invention has invented a method capable of forming an image-like polymer compound by a dry process (Japanese Patent Laid-Open No. S60-242242).
61-69062). In this method, a photosensitive material comprising a support and a photosensitive layer comprising a photosensitive silver salt (silver halide), a reducing agent, a crosslinkable compound (polymerizable compound) and a binder is imagewise exposed to form a latent image. Is formed and then heat-developed to form a polymer compound in the portion where the latent image of the photosensitive silver salt is formed. That is, this image forming method is a method of polymerizing the polymerizable compound in the portion where the latent image of silver halide is formed. Further, the present applicant has already filed a patent application for a method capable of polymerizing a polymerizable compound in a portion where a latent image of silver halide is not formed (JP-A-62-70836). According to this method, a reducing agent is caused to act on a portion where a latent image of silver halide is formed by heat development to suppress the polymerization of a polymerizable compound, and at the same time, promote the polymerization of other portions.

The light-sensitive material used in the above image forming method is generally
It is manufactured by preparing a coating solution in which the constituents of the photosensitive layer are dissolved and emulsified in an aqueous solvent, and coating the coating solution on a support. For this reason, when paper is used as the support of the photosensitive material of this structure, the above-mentioned image unevenness (wrinkles,
The density unevenness) tended to be remarkable.

SUMMARY OF THE INVENTION It is an object of the present invention to provide an image forming method in which generation of image unevenness (wrinkles, density unevenness) is suppressed and an excellent image is stably obtained.

The present invention provides a method for forming an image by performing a heat development treatment on a photothermographic material having a photosensitive layer containing a photosensitive component on a paper support, simultaneously with or after the imagewise exposure. A paper support provided with a coating layer made of a hydrophobic polymer on the photosensitive layer side so that the Cobb water absorption defined by JIS-P-8140 is 10 g / m ² or less is used. An image forming method characterized in that after the moisture content in the support is removed so that the moisture content is 4% or less while the migration of moisture to the photosensitive layer is suppressed by the coating layer, is there.

In the present invention, a heat-developable photosensitive material having a photosensitive layer containing a silver halide, a reducing agent and a polymerizable compound on a paper support is subjected to a heat development treatment simultaneously with or after imagewise exposure. In the method for forming a line image, a coating layer made of a hydrophobic polymer is provided on the photosensitive layer side as the paper support so that the Cobb water absorption defined by JIS-P-8140 is 10 g / m ² or less. Used to remove the water content in the support so that the water content is 4% or less while suppressing the migration of water to the photosensitive layer by means of a coating layer made of a hydrophobic polymer, followed by heat development treatment. There is also an image forming method characterized by carrying out.

[Advantages of the Invention] The present inventor uses a photothermographic material having a paper support having a specific function when forming an image using the photothermographic material, and uses moisture in the paper support. It has been found that image unevenness (wrinkles and density unevenness) can be effectively prevented by removing the particles before the heat development treatment.

The image unevenness is presumed to be caused by the water content contained in the paper support as described above, but wrinkles in the image are particularly caused by the uneven heating temperature of the photosensitive layer due to the evaporation of the water, It is considered that the density unevenness is mainly caused by nonuniformity of the development active components (base, thermal solvent, etc.) contained in the photosensitive layer due to the evaporation of water.

According to the image forming method of the present invention, water (water vapor), which is considered to be involved in the heat development, is removed by the coating layer made of the hydrophobic polymer while the transfer (permeation) to the photosensitive layer is directly suppressed. Therefore, the influence of water vapor on the photosensitive layer is suppressed. Further, in a photosensitive material having a structure in which the photosensitive layer is formed by using a liquid and highly penetrative coating solution, image unevenness that seems to be caused by this uneven penetration tends to occur at the same time. , These will also be suppressed. Therefore, when an image is formed by using a light-sensitive material constituted by using the above-mentioned ordinary paper support (the Cobb water absorption of ordinary paper is about 20 g / m ² ) (Japanese Patent Laid-Open No. 54-30032). Image unevenness is further suppressed as compared with (See Reference), and an excellent image can be stably obtained.

DETAILED DESCRIPTION OF THE INVENTION The photothermographic material used in the image forming method of the present invention is
It comprises a photosensitive layer containing a photosensitive component and a paper support provided with a coating layer made of a specific hydrophobic polymer on the surface on which the photosensitive layer is provided. Everything from which an image is obtained is included. That is, the image forming method of the present invention can be applied to all of the photothermographic materials having the above-mentioned constitution, which have the above-mentioned specific paper support. In particular, it is advantageous for a photothermographic material having a photosensitive layer whose photosensitive component contains a silver halide, a reducing agent, and a polymerizable compound.

The paper support of the light-sensitive material used in the image forming method of the present invention has a low water absorption such that the surface on the light-sensitive layer side has a Cobb water absorption of 10 g / m ² or less defined by JIS-P-8140. It is of sex. It is further preferable that the Cobb water absorption is 3 g / m ² or less. There is no particular lower limit to the Cobb water absorption,
The value can be as low as possible, but in the case of producing a paper support, about 0.1 g / m ² is the technical limit at present.

The above Cobb water absorption is measured at the center of the test piece of 130 × 130 mm.
The weight increase of the test paper piece was measured by contacting the 0 cm ² circular part with distilled water for 120 seconds. The weight increase (g) × 100 is taken as the Cobb water absorption. The details of the above test method and the equipment used for measurement shall comply with the Japanese Industrial Standards of 1964.

The constitution of the paper support and specific means for reducing the water absorption will be described below.

The paper support is a base paper whose main component is wood pulp,
Alternatively, it means a sheet-like material in which a coating layer is optionally provided on the base paper.

The base paper used for the paper support is produced by making wood pulp as a main raw material and making paper. As the wood pulp, either a softwood pulp or a hardwood pulp can be used, but a hardwood pulp having short fibers and easily exhibiting smoothness is more preferable.

If necessary, part of the wood pulp may be replaced with synthetic pulp made of polyethylene, polypropylene or the like, or synthetic fiber made of polyester, polyvinyl alcohol, nylon or the like.

Internal sizing agents such as rosin, paraffin wax, higher fatty acid salts, alkenyl succinates, fatty acid anhydrides and alkyl ketene dimers may be added to the base paper.

Although it is possible to reduce the Cobb water absorption of the base paper itself to 10 g / m ² or less by adding the above internally added sizing agent, it is generally preferable to provide a coating layer of a hydrophobic polymer described below. Even when the coating layer is provided, it is preferable to adjust the Cobb water absorption of the base paper itself to 25 g / m ² or less by adding the internally added sizing agent. The Cobb water absorption of the base paper itself is more preferably 20 g / m ² or less.

As internal additives other than the internally added sizing agent, paper strength enhancers such as polyacrylamide, starch, polyvinyl alcohol, and melamine formaldehyde condensate; reaction products of maleic anhydride copolymer and polyalkylene polyamine; quaternary higher fatty acid Softeners such as ammonium salts; fillers such as calcium carbonate, talc, clay, kaolin, titanium dioxide, urea resin particles; fixing agents such as sulfuric acid bands, polyamide polyamine epichlorohydrin; dyes; fluorescent dyes, etc. May be added to.

In the paper support, a coating layer made of a hydrophobic polymer is provided on the base paper as described above.

A known surface sizing agent may be applied to the surface of the raw paper and a coating layer of a hydrophobic polymer may be provided thereon. Examples of the surface sizing agent include polyvinyl alcohol, starch, polyacrylamide, gelatin, casein, styrene maleic anhydride copolymer, alkyl ketene dimer, polyurethane, epoxidized fatty acid amide and the like. Even when using a surface sizing agent, similarly to the addition of the internally added sizing agent, the Cobb water absorption before providing the coating layer of the hydrophobic polymer is preferably 25 g / m ² or less, 20 g / m ^2.
It is more preferable to set it to m ² or less. In order to reduce the Cobb water absorption to 25 g / m ² or less, it is preferable to use 1.0 to 3.0% by weight of the internally added sizing agent and / or the surface sizing agent based on the wood pulp.

The hydrophobic polymer is preferably a polymer having a glass transition point of 120 ° C to 50 ° C. The polymer may be a homopolymer or a copolymer. Further, in the case of the copolymer, it may have a hydrophilic repeating unit in a part thereof as long as it is hydrophobic as a whole. Examples of the hydrophobic polymer include
Styrene-butadiene copolymer, methylmethacrylate-butadiene copolymer, acrylonitrile-butadiene copolymer, styrene-acrylic acid ester copolymer, methylmethacrylate, acrylic acid ester copolymer, and styrene-methacrylate-
An acrylic acid ester copolymer etc. can be mentioned.

It is further preferable that the hydrophobic polymer has a crosslinked structure in order to lower the Cobb water absorption of the paper support. To introduce a crosslinked structure into the hydrophobic polymer, a known curing agent (crosslinking agent) may be used together with the hydrophobic polymer during the production of the paper support. Examples of the curing agent include active vinyl compounds such as 1,3-bis (vinylsulfonyl) -2-propanol and methylene bismaleimide; 2,4-dichloro-6-hydroxy-S-triazine.
Sodium salt, 2,4-dichloro-6-hydroxy-S-
Active halogen compounds such as triazine and N, N′-bis (2-chloroethylcarbamyl) piperazine; bis (2,3
-Epoxypropyl) methylpropylammonium.p
Epoxy compounds such as toluene sulfonate; and 1,
Examples thereof include methanesulfonic acid ester compounds such as 2-di (methanesulfonoxy) ethane. The curing agent is preferably used in an amount of 0.1 to 10% by weight, more preferably 0.5 to 5% by weight, based on the hydrophobic polymer.

A pigment may be added to the coating layer made of a hydrophobic polymer for the purpose of improving the smoothness of the coating layer and facilitating layer formation during production. As the pigment, a pigment used for a known coated paper (coated paper, art paper, baryta paper, etc.) can be used. Examples of pigments include inorganic pigments such as titanium dioxide, barium sulfate, talc, clay, kaolin, calcined kaolin, aluminum hydroxide, amorphous silica, and crystalline silica; and organic resins such as polystyrene resin, acrylic resin, urea formalin resin. Mention may be made of pigments. Since the use of inorganic pigments may increase the Cobb water absorption of the paper support, it is preferably used at 300% by weight or less, more preferably 200% by weight or less with respect to the hydrophobic polymer. preferable.

A water resistant agent may be added to the coated layer of the hydrophobic polymer in order to lower the Cobb water absorption of the paper support. Examples of the waterproofing agent include polyamide polyamine epichlorohydrin resin, melamine formaldehyde resin, urea formalin resin, polyamide polyurea resin, and glyoxal resin. Of these, formalin-free polyamide polyamine epichlorohydrin resin and polyamide polyurea resin are particularly preferable. The waterproofing agent is 0.1 per hydrophobic polymer.
It is preferably used in an amount in the range of from 10 to 10% by weight, and
More preferably, it is used in an amount ranging from 5 to 5% by weight.

The coating layer made of the hydrophobic polymer as described above can be easily obtained by coating the latex of the hydrophobic polymer on the base paper. Ingredients such as a curing agent, a pigment, and a waterproofing agent can be dissolved or dispersed in the latex. As a method for coating the latex on the base paper, a known dip coating method, air knife coating method, curtain coating method, roller coating method, doctor coating method, gravure coating method or the like can be used.

The coating layer made of a hydrophobic polymer is preferably provided on the base paper at a coating amount of 1 to 30 g / m ² . A more preferable coating amount is 5 to 20 g / m ² .

For the purpose of improving the smoothness of the paper support, a calender treatment such as a gloss calender or a super calender may be carried out during or after the coating of the coating layer.

The photothermographic material has a photosensitive layer provided on the coating layer of the paper support having the above-described specific functions.

Next, the image forming method of the present invention will be described with reference to a photothermographic material (hereinafter simply referred to as a light-sensitive material) having a light-sensitive layer whose representative component is a silver halide, a reducing agent, and a polymerizable compound. An example using will be described in order.

In the present invention, image formation requires that the water content of the paper support be removed before the heat development treatment. Here, the removal of moisture means that the moisture content of the paper support is suppressed within a range where the image obtained during heat development is not affected, and the moisture is not always completely removed from the support. There is no. Therefore, the lower the water content of the paper support, the better. In the present invention, the water content of the paper support is 4% or less, preferably 3% or less, and more preferably 1% or less. The water content of the paper support of the photosensitive material used varies depending on the composition of the paper support and the like, but is 8% under normal conditions, and image formation is generally performed at this water content. Is. Further, even in the paper support having a low water absorbency such as the Cobb water absorbency of 10 g / m ² or less, the water content is usually the same as the above.

In the present invention, image formation is preferably carried out by imagewise exposing the light-sensitive material (exposure step), removing water from the paper support (water removal step), and then performing heat development treatment (heat development step). .

The process will be described in detail below.

Although various exposing means can be used as the exposing method of the light-sensitive material, a latent image of silver halide is generally obtained by imagewise exposure to radiation including visible light. The type of light source and the amount of exposure can be selected according to the photosensitive wavelength of silver halide (wavelength sensitized when dye sensitization is performed) and sensitivity. The original image may be a monochrome image or a color image.

A feature of the present invention is a step of removing moisture in the paper support of the photosensitive material after the exposure step as described above.

There are various methods for removing water in the paper support, but the method is not particularly limited in the image forming method of the present invention. However, in consideration of advantages in image formation and operation, a method of removing the moisture of the paper support (evaporating and removing) by performing heat treatment is preferable.

As a specific heat treatment method, the following known methods can be used.

Method of blowing hot air (air heated to high temperature); Method of passing through heated atmosphere; Method of directly contacting hot plate such as hot plate or drum; Method of carrying using heat roller; High frequency heating or laser There are a method of heating with a beam; a method of heating with an infrared heater; a method of heating with an overcurrent generated by electromagnetic induction; and a method of combining these.

The conditions for removing water are set according to the means used so that the water content of the paper support finally (before the heat development step) becomes the above-mentioned water content. That is, taking into consideration the method to be used, the material of the paper, the shape, etc., the heat treatment temperature,
Set the time.

However, in the present invention, the heat treatment is preferably carried out in a state in which the temperature of the surface of the photosensitive material (surface of the photosensitive layer) is 10 ° C. or more lower than the temperature of the heat development processing. By setting the heating temperature in this range, it does not participate in the polymerization reaction during the heat development, and does not have any adverse effect on the subsequent image formation. Further, since the temperature is lower than the developing temperature, rapid evaporation and development of water can be avoided, and the generation of wrinkles is further suppressed.

In the present invention, as the above means, a method of passing through a heated atmosphere, a method of directly contacting a hot plate or a drum such as a hot plate, or a method of carrying using a heat roller or the like is a preferable method in terms of simplicity. .

Moisture in the paper support is released as water vapor by the above method, but the water vapor is removed without directly affecting the photosensitive layer because of the low water absorption surface described above, and therefore image unevenness is caused. Is suppressed.

The present invention gives particularly preferable results when image formation is carried out while suppressing the amount of oxygen present in the photosensitive layer during heat development (see Japanese Patent Application No. 61-55506).

The photosensitive material from which the water content of the paper support has been removed as described above is heat-treated in the next heat development step.

As a heating method in the heat development step, various conventionally known methods can be used. In addition, JP-A-61-29
As in the light-sensitive material described in Japanese Patent No. 4434, the light-sensitive material may be provided with a heating element layer and used as a heating means. The heating temperature is generally 80 ° C to 200 ° C, preferably 100 ° C to 160 ° C.
Is. The heating time is generally 1 second to 5 minutes, preferably 5 seconds to 1 minute.

The photosensitive material can be subjected to the heat development treatment as described above to polymerize the polymerizable compound on the portion where the latent image of silver halide is formed or the portion where the latent image of silver halide is not formed. Incidentally, in the image forming method of the present invention, in general, in the heat development treatment, the polymerizable compound in the portion where the latent image of silver halide is formed is polymerized, but the photosensitive material described in JP-A-62-70836 described above. It is also possible to polymerize the polymerizable compound in the portion where the latent image of silver halide is not formed, by adjusting the type and amount of the reducing agent, like the material.

As described above, the image forming method of the present invention can obtain a polymer image on a photosensitive material. Further, a dye or a pigment may be fixed to the polymer to obtain a dye image.

When the light-sensitive material used in the image forming method of the present invention is constituted as the light-sensitive material described in Japanese Patent Application No. 61-53881 described later, the light-sensitive material subjected to the heat development treatment is pressurized,
A color image can be formed on the light-sensitive material by breaking the microcapsules and bringing two kinds of substances that cause a color-forming reaction into contact with each other.

Further, the image receiving material can be used to form an image on the image receiving material.

The image receiving material will be described below. For general image forming methods using an image receiving material or image receiving layer, see
It is described in JP 61-278849.

As a material that can be used for the support of the image receiving material,
Glass, paper, high-quality paper, coated paper, cast coated paper, synthetic paper, metal and its analogs, polyester, acetyl cellulose, cellulose ester, polyvinyl acetal, polystyrene, polycarbonate, polyethylene terephthalate and other films, and resin materials and polyethylene, etc. Examples include paper laminated with the above polymer. In addition to the above-mentioned support, baryta paper can be used. When a porous material such as paper is used as the support of the image receiving material, Japanese Patent Application No.
It is preferable that the image receiving material described in the specification of No. 52990 has a certain smoothness. The image receiving material using a transparent support is described in Japanese Patent Application No. 61-52991.

The image receiving material generally has an image receiving layer provided on a support. The image-receiving layer can be formed in any form using various compounds according to the color-forming system of the color image-forming substance described below. When a polymer image is formed on an image receiving material without using a color image forming substance, or when a dye or a pigment is used as a color image forming substance, the image receiving material may be composed of only the support. .

For example, when a color-developing system comprising a color-developing agent and a color-developing agent is used, the image-receiving layer may contain the color-developing agent. Further, the image receiving layer may be configured as a layer containing at least one mordant. The mordant can be selected from compounds known in the photographic art and the like in consideration of conditions such as the type of color image forming substance and used. If necessary, a plurality of mordants having different mordant strengths may be used to form two or more image receiving layers.

The image receiving layer preferably contains a polymer as a binder. As the binder, a binder that can be used in the photosensitive layer of the photosensitive material described below can be used. Further, a polymer having low oxygen permeability may be used as a binder as in the image receiving material described in Japanese Patent Application No. 61-53879.

The image receiving layer may be formed as an agglomerate of fine particles of a thermoplastic substance like the image receiving materials described in Japanese Patent Application Nos. 61-124952 and 61-124953. Further, a white pigment such as titanium dioxide may be added to the image receiving layer so that the image receiving layer functions as a white reflective layer. Further, a photopolymerization initiator or a thermal polymerization initiator may be added to the image receiving layer for the purpose of polymerizing the unpolymerized polymerizable compound. An image receiving material having an image receiving layer containing a photopolymerization initiator is described in Japanese Patent Application No. 61-3025, and an image receiving material having an image receiving layer containing a thermal polymerization initiator is described in Japanese Patent Application No. 61-55502. Are described in each. Further, like the image receiving material described in Japanese Patent Application No. 61-110115, the image receiving layer may contain a dye or pigment having a property of decolorizing by heating or light irradiation.

When the image receiving layer is located on the surface of the image receiving material, it is preferable to further provide a protective layer. In addition, Japanese Patent Application No. 61-
Like the image receiving material described in the specification of No. 55503, a layer made of an aggregate of fine particles of a thermoplastic substance may be provided on the image receiving layer.

In the image forming method of the present invention, by pressing the photosensitive material subjected to heat development and the image receiving material in a state of being superposed, the unpolymerized polymerizable compound is transferred to the image receiving material,
An image forming method for obtaining a polymer image on an image receiving material is preferable. The pressurizing method can be performed according to a conventional method.

Further, in the embodiment in which the photosensitive layer contains a color image-forming substance,
Similarly, a heat development treatment is carried out to polymerize and cure the polymerizable compound, thereby immobilizing the color image forming substance in the cured portion. Then, by pressing the photosensitive material and the image receiving material in a superposed state, the color image forming substance in the uncured portion is transferred onto the image receiving material, and a color image can be formed on the image receiving material.

After forming an image on the image receiving material as described above, as in the image forming method described in Japanese Patent Application No. 61-55501,
The image receiving material may be heated. The above method also has an advantage that the unpolymerized polymerizable compound transferred onto the image receiving material is polymerized and the storability of the obtained image is improved.

The image forming method of the present invention can be applied to a large number of black and white or color photographing and printing, printing, printing plate, X-ray photographing, medical diagnostic photographing (for example, ultrasonic diagnostic machine CRT photographing), computer graphic hard copy, copying machine and the like. It can be applied to the field.

The photothermographic material that can be used in the image forming method of the present invention will be described.

As described above, the photothermographic material has a photosensitive layer provided on a specific paper support. The paper support is as described above. Below is a typical configuration,
A photosensitive material having a photosensitive layer containing a photosensitive component composed of silver halide, a reducing agent and a polymerizable compound will be described as an example.

Photosensitive materials include silver chloride, silver bromide,
Any grain of silver iodide or silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide can be used.

The halogen composition of the silver halide grains may be uniform or non-uniform on the surface and inside. Regarding silver halide grains having a multiple structure having different compositions on the surface and in the inside, JP-A-57-154232, JP-A-58-108533, and JP-A-59-4875.
5, JP-A-59-52237, US Pat. No. 4433048, 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 Japanese Patent Application No. 61-25576.

There is also no particular limitation on the crystal habit of the silver halide grains. For example, tabular grains having an aspect ratio of 3 or more as in the light-sensitive material described in Japanese Patent Application No. 61-55509 may be used.

The silver halide grains described above are those disclosed in Japanese Patent Application No. 61-2145.
It is preferable to use silver halide grains having a relatively low fog value as in the light-sensitive material described in JP-A-80.

Two or more kinds of silver halide grains having different halogen compositions, crystal habits, grain sizes and the like can be used in combination with the silver halide used in the light-sensitive material.

The grain size distribution of silver halide grains is not particularly limited. For example, monodisperse silver halide grains having a substantially uniform grain size distribution may be used as in the light-sensitive material described in Japanese Patent Application No. 61-55508.

In the light-sensitive material, the average grain size of silver halide grains is preferably 0.001 to 5 μm, and more preferably 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 including an organic silver salt which is an optional component described later.
It is preferable to set it as the range. Further, in terms of silver equivalent of silver halide alone, it is preferably 1 g / m ² or less, and particularly preferably 1 mg 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) the polymerization of the polymerizable compound. There are various kinds of substances as the reducing agent having the above function. Examples of the reducing agent include hydroquinones, catechols, p-aminophenols, p-phenylenediamines, 3-pyrazolidones, 3-aminopyrazoles, 4-amino-5-
Pyrazolones, 5-aminouracils, 4,5-dihydroxy-6-aminopyrimidines, reductones, aminoreductones, o- or p-sulfonamidophenols, o- or p-sulfonamidonaphthols, 2
-Sulfonamidoindanones, 4-sulfonamido-
5-pyrazolones, 3-sulfonamidoindoles,
Examples include sulfonamide pyrazolobenzimidazoles, sulfonamide pyrazolotriazoles, α-sulfonamide ketones, and hydrazines. By adjusting the type and amount of the reducing agent, it is possible to polymerize the polymerizable compound in the portion where the latent image of silver halide is formed or the portion where the latent image is not formed. In addition,
In the system in which the polymerizable compound in the portion where the latent image of silver halide is not formed is polymerized, it is particularly preferable to use 1-phenyl-3-pyrazolidones as the reducing agent.

Regarding various reducing agents having the above functions, see
61-183640, 61-188535, 61-228441, and Japanese Patent Application Nos. 60-210657, 60-226084, and
No. 60-227527, No. 60-227528, and No. 61-42746 are described (including those described as a developer or a hydrazine derivative). Regarding the above reducing agent, see T.
James, "The Theory of the Photographic Process," 4th Edition, pages 291-334 (1977), Research Disclosure Vol. 170, June 1978, No. 17029 (9-15).
), And Vol. 176, December 1978, No. 17643 (22
~ Page 31). Further, as in the light-sensitive material described in Japanese Patent Application No. 61-55505, a reducing agent precursor capable of releasing the reducing agent under heating conditions or in contact with a base is used instead of the reducing agent. Good. The reducing agent and the reducing agent precursor described in the above-mentioned respective specifications and references can be effectively used for the light-sensitive material in the present specification. Therefore, the “reducing agent” in the present specification includes the reducing agents and reducing agent precursors described in the above-mentioned publications, specifications and literatures. These reducing agents may be used alone, or as described in each of the above specifications, two or more reducing agents may be mixed and used. When two or more reducing agents are used in combination, the reducing agents may interact with each other by first promoting the reduction of silver halide (and / or organic silver salt) by so-called superadditivity. To cause polymerization of the polymerizable compound via an oxidation-reduction reaction with another reducing agent in which the oxidant of the first reducing agent generated by reduction of silver halide (and / or organic silver salt) coexists (Or suppressing the polymerization) is considered. However, in actual use, it is difficult to specify which of the above actions because the above reactions can occur simultaneously.

Specific examples of the reducing agent include pentadecylhydroquinone, 5-t-butylcatechol, p- (N, N-diethylamino) phenol, 1-phenyl-4-methyl-4.
-Hydroxymethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-heptadecylcarbonyloxymethyl-3-pyrazolidone, 2-phenylsulfonylamino-4-hexadecoxy-5-t-octylphenol, 2-phenylsulfonyl Amino-4-t-butyl-
5-hexadecyloxyphenol, 2- (N-butylcarbamoyl) -4-phenylsulfonylaminonaphthol, 2- (N-methyl-N-octadecylcarbamoyl) -4-sulfonylaminonaphthol, 1-acetyl-2-phenylhydrazine , 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 -Pentadecyl fluorocaprylate, 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) butylamido} 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-dimethobenzoyl) -2-tritylhydrazine,
1- (4-dibutylcarbamoylbenzoyl) -2-tritylhydrazine, and 1- (1-naphthoyl) -2
-Trityl hydrazine etc. can be mentioned.

In the light-sensitive material, the reducing agent is preferably used in the range of 0.1 to 1500 mol% with respect to 1 mol of silver (including the above-described silver halide and an organic silver salt which is an optional component).

The polymerizable compound that can be used in the photosensitive material is not particularly limited, and known polymerizable compounds can be used. As a method of using the light-sensitive material, when a heat development process is planned, a high boiling point (for example, a boiling point of 80 ° C.) that is hard to volatilize during heating is used.
It is preferable to use the above compounds). Further, in the embodiment in which the photosensitive layer contains a color image forming substance as an optional component described later, the color image forming substance is immobilized by polymerizing and curing the polymerizable compound. A crosslinkable compound having a polymerizable functional group is preferable. When a transfer image is formed using an image receiving material, it is preferable to use a highly viscous substance as the polymerizable compound, as in the light-sensitive material described in Japanese Patent Application No. 61-150079.

The polymerizable compounds that can be used in the light-sensitive material are described in the application specifications for a series of light-sensitive materials described above and below.

The polymerizable compound used in the light-sensitive material is generally a compound having addition polymerization or ring-opening polymerization. The compound having an addition-polymerizable group includes a compound having an ethylenically unsaturated group, and the compound having a ring-opening polymerizable group 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 light-sensitive material include acrylic acid and salts thereof, acrylic acid esters, acrylamides, methacrylic acid and salts thereof, methacrylic acid esters, methacrylamides, maleic anhydride. Acids, maleic acid esters, itaconic acid 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 light-sensitive material include acrylic acid esters such as n-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, furfuryl acrylate, ethoxyethoxyethyl acrylate, dicyclohexyloxy. Ethyl acrylate, nonylphenyloxyethyl acrylate, hexanediol diacrylate, butanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate,
Examples thereof include polyoxyethylenated bisphenol A diacrylate, hydroxypolyether polyacrylate, polyester acrylate, and polyurethane acrylate.

Other specific examples of methacrylic acid esters include methyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, butanediol methacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate. And dimethacrylate of polyoxyalkylenated bisphenol A and the like.

The polymerizable compounds may be used alone or in combination of two or more. A light-sensitive material containing two or more polymerizable compounds in combination is described in Japanese Patent Application No. 61-55504. A substance obtained by introducing a polymerizable functional group such as a vinyl group or a vinylidene group into the chemical structure of the above-mentioned reducing agent or an optional component described later, which is a color image forming substance, can also be used as the polymerizable compound. Needless to say, use of a substance that serves as both a reducing agent and a polymerizable compound or a color image forming substance and a polymerizable compound as described above is also included in the embodiment of the light-sensitive material.

In the light-sensitive material, the polymerizable compound is preferably used in the range of 50 to 120,000 parts by weight with respect to 1 part by weight of silver halide. A more preferred range of use is 12 to 12000 parts by weight.

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

In the photosensitive material, the polymerizable compound is preferably dispersed in the photosensitive layer in the form of oil droplets. For an example of a photosensitive material in which a polymerizable compound is dispersed in the photosensitive layer in the form of oil droplets, see Japanese Patent Application No.
-218603 has a description. Other components in the photosensitive layer such as silver halide, a reducing agent, and a color image forming substance may be contained in the oil droplets. For the light-sensitive material containing silver halide in the oil droplet, Japanese Patent Application Nos. 60-261888 and 61-5751 each, for the light-sensitive material further containing a reducing agent in the oil droplet, Each of them is described in Japanese Patent Application No. 61-25577. When silver halide is contained in oil droplets, the number of silver halide grains contained in oil droplets should be 5 or more, as described in Japanese Patent Application No. 61-160592. Preferably.

The oil droplets of the polymerizable compound are more preferably in the form of microcapsules. Various known techniques can be applied to the microcapsules without particular limitation. An example of a light-sensitive material in which oil droplets of a polymerizable compound are in a microcapsule state is disclosed in JP-A-61-278441.
It is described in the official gazette.

There is no particular limitation on the wall material that constitutes the outer shell of the microcapsule. Regarding a photosensitive material using a microcapsule having an outer shell made of a polyamide resin and / or a polyester resin, Japanese Patent Application No. 61-53871 discloses a microcapsule having an outer shell made of a polyurea resin and / or a polyurethane resin. Japanese Patent Application No. 61-53872 for a photosensitive material using, and Japanese Patent Application No. 61-53873 for a photosensitive material using a microcapsule having an outer shell made of an amino-aldehyde resin.
Japanese Patent Application No. 61-53874 discloses a photosensitive material using microcapsules having an outer shell made of gelatin, and Japanese Patent Application No. 61-53875 discloses a photosensitive material using microcapsules having an outer shell made of an epoxy resin. Japanese Patent Application Laid-Open No. 2004-242242 discloses a photosensitive material using microcapsules having a composite resin shell containing a polyamide resin and a polyurea resin.
Japanese Patent Application No. 61-53878 describes photosensitive materials using microcapsules having a composite resin outer shell containing a polyurethane resin and a polyester resin.

When aldehyde-based microcapsules are used, it is preferable that the amount of residual aldehyde is not more than a certain value as in the light-sensitive material described in Japanese Patent Application No. 61-176415.

When the silver halide is contained in the microcapsules, it is preferable that the silver halide be present in the wall material that constitutes the outer shell of the microcapsules. Regarding the light-sensitive material containing silver halide in the wall material of the microcapsule, Japanese Patent Application No. 61-
It is described in the specification of 11556.

Further, two or more microcapsules in which at least one of the components contained in the microcapsules such as silver halide, a reducing agent, a polymerizable compound, and a color image forming substance which is an optional component described later are different may be used in combination. Good. In particular, in the case of forming a full-color image, it is preferable to use together three or more types of microcapsules in which the color hue of the color image forming substance contained is different. Regarding the light-sensitive material in which two or more kinds of microcapsules are used in combination, Japanese Patent Application No. 61-42747 is available.
It is described in the specification.

The average particle size of the microcapsules is preferably 3 to 20 μm. The particle size distribution of the microcapsules is
As in the light-sensitive material described in Japanese Patent Application No. 61-150080, it is preferable that the light-sensitive material is uniformly distributed over a certain value. Also,
The film thickness of the microcapsules is preferably within a certain range with respect to the particle diameter, as in the light-sensitive material described in Japanese Patent Application No. 61-227767.

When accommodating silver halide in microcapsules, it is preferable that the average grain size of the silver halide grains described above is one-fifth or less, preferably one-tenth or less of the average size of microcapsules. Is more preferable.
By setting the average grain size of the silver halide grains to be one fifth or less of the average size of the microcapsules, a uniform and smooth image can be obtained.

As an optional component that can be contained in the photosensitive layer of the photosensitive material, a color image forming substance, a sensitizing dye, an organic silver salt, a radical generator, various image forming accelerators, a thermal polymerization inhibitor, a thermal polymerization initiator, Development stopper, fluorescent whitening agent, anti-fading agent, dye or pigment for preventing halation or irradiation, dye having a property of decolorizing by heating or light irradiation, matting agent, anti-smudge agent, plasticizer, water releasing agent, Examples include binders, photopolymerization initiators, solvents for polymerizable compounds, water-soluble vinyl polymers and the like.

The photosensitive material can obtain a polymer image by the constitution of the photosensitive layer described above, but a color image can also be formed by including a color image forming substance as an optional component in the photosensitive layer.

The color image-forming substance that can be used in the light-sensitive material is not particularly limited, and various types can be used. That is, a substance that is itself colored (dye or pigment), or energy that is colorless or pale but is external (heat, pressure, light irradiation, etc.) or another component (developing agent) A substance (color former) that develops a color upon contact is also included in the color image forming substance. Incidentally, the general light-sensitive material using a color image forming substance is described in the above-mentioned JP-A-61-73145. Also, Japanese Patent Application No. 61-29987 describes a light-sensitive material using a dye or pigment as a color image forming substance, and Japanese Patent Application No. 61-53876 describes a light-sensitive material using a leuco dye.
JP-A No. 61-96339 for a photosensitive material using a triazene compound, and Japanese Patent Application Nos. 61-133091 and 61-133092 for a photosensitive material using a yellow color-forming leuco dye. The description of the light-sensitive material using a cyan color-forming leuco dye is described in Japanese Patent Application No. 61-197963.

Dyes and pigments, which are themselves colored substances, are commercially available, as well as various documents (for example, "Dye Handbook" edited by the Society of Synthetic Organic Chemistry, published in 1970, "Latest Pigment Handbook" edited by the Japan Pigment Technology Association, Known ones described in 1977 can be used. These dyes or pigments are used after being dissolved or dispersed.

On the other hand, examples of the substance that develops color by some energy such as heating, pressurization, and light irradiation are thermochromic compounds,
Known are piezochromic compounds, photochromic compounds, and leuco bodies such as triarylmethane dyes, quinone dyes, indigoid dyes, and azine dyes. All of them develop color by heating, pressurizing, light irradiation or air oxidation.

Examples of substances that develop color when contacted with another component include acid-base reaction between two or more components, redox reaction,
Various systems that develop a color by a coupling reaction, a chelate forming reaction and the like are included. For example, pressure-sensitive copying paper (pages 29-58) and azography (87-95) described in "Introduction to Special Paper Chemistry" by Hiroyuki Moriga (published in 1975).
Page), known color development systems such as thermosensitive color development due to chemical changes (p. 118-120), or a seminar by Kinki Chemical Industry Association "Latest dye chemistry-Attractive utilization as a functional dye and parent development-" The coloring system and the like described on pages 26 to 32, (June 19, 1980) can be used. Specifically, lactones, lactams, which are used for pressure-sensitive paper,
A coloring system consisting of a color-forming agent having a partial structure such as spiropyran and an acidic substance (developing agent) such as acid clay or phenols; aromatic diazonium salts and diazotates, diazosulfonates and naphthols, anilines, active methylenes System utilizing azo coupling reaction such as; Chelate forming reaction such as reaction of hexamethylenetetramine with ferric ion and gallic acid or reaction of phenolphthalein-complexons with alkaline earth metal ion; stearic acid A redox reaction such as a reaction between ferric iron and pyrogallol or a reaction between silver behenate and 4-methoxy-1-naphthol can be used.

Color image-forming substance was 0.5 per 100 parts of the polymerizable compound.
It is preferable to use it in a ratio of from 20 to 20 polymer parts, and from 2 to 7
It is more preferable to use it in the proportion of the polymerized portion. When a color developer is used, it is about 0.
It is preferably used in a ratio of 3 to 80 polymerized parts.

When two types of substances that cause a color reaction in a contact state are used as the above-mentioned color image forming substances, one of the substances that cause the color reaction and the polymerizable compound are contained in microcapsules. Then, a color image can be formed on the photosensitive layer by allowing another substance among the substances that cause the above-mentioned color forming reaction to exist outside the microcapsules containing the polymerizable compound. A light-sensitive material capable of obtaining a color image without using an image receiving material as described above is described in Japanese Patent Application No. 61-53881.

The sensitizing dye that can be used in the light-sensitive material is not particularly limited, and a silver halide sensitizing dye known in the photographic art can be used. The sensitizing dye, methine dye, cyanine dye, merocyanine dye, complex cyanine dye, holopolar cyanine dye, hemicyanine dye,
Examples include styryl dyes and hemioxonol dyes. These sensitizing dyes may be used alone or in combination. In particular, for the purpose of supersensitization, it is common to use a combination of sensitizing dyes. Further, together with the sensitizing dye, a dye which does not have a spectral sensitizing effect itself, or a substance which does not substantially absorb visible light but exhibits supersensitization may be used together. 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. Regarding a light-sensitive material obtained by adding a sensitizing dye in the step of forming silver halide grains, JP-A-62-947 discloses a silver halide emulsion after the formation of silver halide grains. Regarding the light-sensitive material obtained by adding it at the preparation stage, Japanese Patent Application No.
Each is described in the specification of -55510. Further, regarding specific examples of sensitizing dyes that can be used in the light-sensitive material,
It is described in the above-mentioned JP-A Nos. 62-947 and 61-55510. Further, as in the light-sensitive material described in Japanese Patent Application No. 61-208786, an infrared-sensitive sensitizing dye may be used in combination.

Addition of an organic silver salt to a light-sensitive material is particularly effective in heat development processing. That is, when heated to a temperature of 80 ° C. or higher, the organic silver salt is considered to participate in the redox reaction using the latent image of silver halide as a catalyst. in this case,
It is preferable that the silver halide and the organic silver salt are in contact with or in close proximity to each other. As the organic compound that constitutes the organic silver salt, an aliphatic or aromatic carboxylic acid,
Examples thereof include thiocarbonyl group-containing compounds having a mercapto group or α-hydrogen, and imino group-containing compounds. Among them, benzotriazole is particularly preferable. The organic silver salt is generally a silver halide 1
It is used in an amount of 0.01 to 10 mol, preferably 0.01 to 1 mol, per mol. 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 light-sensitive material using an organic silver salt is described in JP-A-62-3246. The organic silver salt as described above is 0.
It is preferably used in the range of 1 to 10 mol, more preferably 0.01 to 1 mol.

The above-mentioned radical generator which participates in the polymerization acceleration (or polymerization suppression) reaction of the reducing agent may be added to the photosensitive layer.
As the radical generator, Japanese Patent Application No. 61-38510 describes a light-sensitive material using triazene silver, and Japanese Patent Application No. 61-38511 describes a light-sensitive material using silver diazotate. The light-sensitive materials mentioned above are described in Japanese Patent Application No. 61-38512.

Various image formation accelerators can be used in the light-sensitive material. The image forming accelerator includes a silver halide (and / or an organic silver salt) and a reducing agent for promoting the redox reaction between the redox agent and the photosensitive material to the image receiving material or image receiving layer (these will be described later). It has the function of promoting the movement of image forming substances. The image formation accelerator is a base, a base precursor, an oil, a surfactant, a
It is further classified into a compound having an antifoggant function and / or a development promoting function, a hot solvent, a compound having an oxygen removing function, and the like. However, these substance groups generally have a composite function, and usually have some of the above-mentioned accelerating effects together. Therefore, the above classification is convenient, and in fact, one compound often has a plurality of functions.

Examples of various image formation accelerators are shown below.

Examples of preferable bases include hydroxides of alkali metals or alkaline earth metals as inorganic bases; tertiary phosphates and borates of alcal metals or alkaline earth metals,
Carbonates, metaborates; combinations of zinc hydroxide or zinc oxide with chelating agents such as sodium picolinate;
Ammonium hydroxides; quaternary alkyl ammonium hydroxides; hydroxides of other metals, and the like, and organic bases include aliphatic 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, with a pKa of 7 or more being particularly preferable.

Examples of the base precursor include salts of organic acids and bases that are decarboxylated by heating, compounds that release amines by reactions such as intramolecular nucleophilic substitution reaction, Rossen rearrangement, Beckmann rearrangement, etc. Compounds that release and generate a base by electrolysis 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, phenylsulfonylacetic acid guanidine, 4-chlorophenylsulfonylacetic acid guanidine, and 4-methyl-. Examples thereof include guanidine sulfonylphenylsulfonylacetate and guanidine 4-acetylaminomethylpropiolate.

The base or base precursor can be used in a wide range of amount in the light-sensitive material. The base or base precursor is suitably used in an amount of 100% by weight or less, more preferably 0.1% by weight to 4% by weight of the coating film of the photosensitive layer.
A range of 0% by weight is useful. In the present invention, the base and /
Alternatively, the base precursor may be used alone or as a mixture of two or more kinds.

A light-sensitive material using a base or a base precursor is described in Japanese Patent Application No. 60-227528. Further, regarding a light-sensitive material using a tertiary amine as a base, Japanese Patent Application No. 61-13181 discloses a light-sensitive material using a fine particle dispersion of a hydrophobic organic base compound having a melting point of 80 to 180 ° C. Is Japanese Patent Application No. 61-52992, the solubility is 0.1%.
Japanese Patent Application No. 61-215637 discloses a photosensitive material using the following guanidine derivative, and Japanese Patent Application No. 96-341341 discloses a photosensitive material using a hydroxide or salt of an alkali metal or an alkaline earth metal. There is description in each book.

Further, Japanese Patent Application No. 61-167558 discloses a photosensitive material using an acetylide compound as a base precursor.
Using a propiolic acid salt as a base precursor, further silver, copper, silver compounds or a photosensitive material containing a copper compound as a catalyst for the base formation reaction is described in Japanese Patent Application No. 61-191000, the propiolic acid salt and the silver, Regarding a light-sensitive material containing copper, a silver compound or a copper compound in a state of being isolated from each other, Japanese Patent Application No. 61-227769 discloses that in addition to the propiolic acid salt and the silver, copper, the silver compound or the copper compound, it is in a free state. Japanese Patent Application No. 61-243555 discloses a light-sensitive material containing a certain ligand, and a light-sensitive material containing a heat-fusible compound as a reaction accelerator for a base-forming reaction is disclosed in Japanese Patent Application No. 61-243555. Japanese Patent Application No. 61-191001 uses a sulfonylacetate salt as a base precursor and further contains a heat-meltable compound as a reaction accelerator for a base formation reaction. For light materials Japanese Patent Application No. Sho
In Japanese Patent Application No. 61-193375, a photosensitive material using a compound in which an isocyanate or isothiocyanate is bound to an organic base is used as a base precursor.
No. 58 has a description in each.

When using a base or a base precursor for the light-sensitive material,
It is preferable that a silver halide, a reducing agent and a polymerizable compound are contained in the microcapsules described above, and a base or a base precursor is present in the photosensitive layer outside the microcapsules. Alternatively, a base or a base precursor may be contained in another microcapsule, as in the light-sensitive material described in Japanese Patent Application No. 61-52988. In addition to the above specification, a light-sensitive material containing microcapsules containing a base or a base precursor is a light-sensitive material containing a base or a base precursor dissolved or dispersed in an aqueous solution of a water retention agent in microcapsules.
No. 61-52989 discloses a light-sensitive material containing solid fine particles carrying a base or a base precursor in microcapsules, which has a melting point of 70 ° C. to 2 ° C.
Photosensitive materials using microcapsules containing a base compound at 10 ° C. are described in Japanese Patent Application No. 61-212149. Further, in place of the microcapsules containing the base or base precursor, particles containing a base or base precursor and a hydrophobic substance in a compatible state may be used as in the light-sensitive material described in Japanese Patent Application No. 61-243556. Good.

The base or base precursor is described in Japanese Patent Application No. 61-9634.
As described in No. 0 specification, it may be added to an auxiliary layer (a layer containing a base or a base precursor described later) other than the photosensitive layer. Further, as described in Japanese Patent Application No. 61-176417, the support described above may be made porous, and a base or a base precursor may be contained in this porous support.

As the oil, a high boiling point 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 Japanese Patent Application No. 59-74547 and polyalkylene oxides described in JP-A No. 59-57231.

The compound having an antifoggant function and / or a development promoting function can be used for the purpose of obtaining a clear image (image having a high S / N ratio) having a high maximum density and a low minimum density. Incidentally, regarding a photosensitive material using an antifoggant as a compound having an antifoggant function and / or a development promoting function, Japanese Patent Application No. 60-294337 discloses a photosensitive material using a compound having a cyclic amide structure. Japanese Patent Application No. 60-294338, Japanese Patent Application No. 60-294339 for a photosensitive material using a thioether compound, Japanese Patent Application No. 60-294340 for a photosensitive material using a polyethylene glycol derivative. In Japanese Patent Application No. 60-294341 for a photosensitive material using a thiol derivative and in Japanese Patent Application No. 20438/1986 for a photosensitive material using an acetylene compound, a photosensitive material using a sulfonamide derivative. Japanese Patent Application No. 61-25578, and Japanese Patent Application No. 61-25578 for a photosensitive material using a quaternary ammonium salt.
-238871 describes each.

As the hot solvent, a compound which can be a solvent for the reducing agent, a compound which is a substance having a high dielectric constant and is known to accelerate the physical development of the silver salt, and the like are useful. As a useful thermal solvent,
Polyethylene glycols of U.S. Patent No. 3347675, derivatives of acids such as oleic acid esters of polyethylene oxide, beeswax, glycerol monostearate, -SO ₂ - and /
Or a compound having a high dielectric constant having a --CO-- group, U.S. Pat.
Preferable examples include polar substances described in Japanese Patent No. 3667959, 1,10-decanediol, methyl anisate, and biphenyl suberate described in Research Disclosure, December 1976, pages 26 to 28. The photosensitive material using a hot solvent is described in Japanese Patent Application No. 60-227527.

The compound having a function of removing oxygen can be used for the purpose of eliminating the influence of oxygen during development (oxygen has a polymerization inhibiting action). Examples of the compound having an oxygen removing function include compounds having two or more mercapto groups. Regarding the photosensitive material using a compound having two or more mercapto groups, Japanese Patent Application No.
It is described in the specification of 61-53880.

The thermal polymerization initiator that can be used in the light-sensitive material is generally a compound that thermally decomposes under heating to generate a polymerization initiation species (particularly a radical), and is usually used as an initiator of radical polymerization. The thermal polymerization initiator is described on pages 6 to 18 of “Addition Polymerization / Ring-Opening Polymerization,” 1983, Kyoritsu Shuppan, edited by the Society of Polymer Science, Japan, Editorial Committee for Polymer Experiments. Specific examples of the thermal polymerization initiator include azobisisobutyronitrile, 1,1′-azobis (1-cyclohexanecarbonitrile), dimethyl-2,2′-azobisisobutyrate, 2,2-azobis ( 2-methylbutyronitrile), azo compounds such as azobisdimethylvaleronitrile, benzoyl peroxide, di-t-butylperoxide,
Organic peroxides such as dicumyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide,
Inorganic peroxides such as hydrogen peroxide, potassium persulfate and ammonium persulfate, sodium p-toluenesulfinate and the like can be mentioned. The thermal polymerization initiator is preferably used in the range of 0.1 to 120% by weight, more preferably 1 to 10% by weight, based on the polymerizable compound. In the system in which the polymerizable compound in the portion where the latent image of silver halide is not formed is polymerized, it is preferable to add a thermal polymerization initiator to the photosensitive layer. Further, regarding a light-sensitive material using a thermal polymerization initiator, the above-mentioned JP-A-61-
It is described in Japanese Patent No. 260241 and Japanese Patent Application No. 60-210657.

A development terminator that can be used in a light-sensitive material is a compound that interacts with a compound or silver and a silver salt that immediately neutralizes or reacts with a base to reduce the concentration of the base in the film to stop development after proper development. Is a compound that suppresses development. Specific examples thereof include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction with a coexisting base when heated, a nitrogen-containing heterocyclic compound, and a mercapto compound. Examples of acid precursors include JP-A-60-1088.
Examples thereof include oxime esters described in JP-A Nos. 37 and 60-192939, and compounds releasing 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 the compounds described in JP-A-60-230134.

Dyes or pigments may be added to the photosensitive layer of the photosensitive material for the purpose of preventing halation or irradiation. Incidentally, Japanese Patent Application No. 61-174402 describes a photosensitive material in which a white pigment is added to a photosensitive layer for the purpose of preventing halation or irradiation.

When the light-sensitive layer of the light-sensitive material is a mode in which the above-mentioned microcapsules are used, the microcapsules may contain a dye having a property of being decolorized by heating or light irradiation. The dye having the property of being decolorized by heating or light irradiation can function as a yellow filter in a conventional silver salt photographic system. Regarding the light-sensitive material using the dye having the property of being decolorized by heating or light irradiation as described above, Japanese Patent Application No.
It is described in the specification of -243551.

As the anti-smudge agent used in the light-sensitive material, solid particles at room temperature are preferable. As a specific example, British Patent No. 12
32347 starch particles, U.S. Pat.
Polymer powder as described in the specification, microcapsule particles containing no color former as described in British Patent No. 1235991, cellulose powder as described in U.S. Pat.No. 2711375, talc, kaolin, bentonite, wax Inorganic particles such as stone, zinc oxide, titanium oxide and alumina can be used. The average particle size of the above 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 preferable. As described above, when the oil droplets of the polymerizable compound are in the microcapsule state, it is more effective that the particles are larger than the microcapsules.

The binder that can be used in the light-sensitive material can be contained in the light-sensitive layer alone or in combination. It is preferable to mainly use a hydrophilic binder. As the hydrophilic binder, a transparent or translucent hydrophilic binder is typical, and examples thereof include natural substances such as gelatin, gelatin derivatives, cellulose derivatives, starch, and arabic gum, and polyvinyl alcohol, polyvinylpyrrolidone, acrylamide polymers and the like. Includes synthetic polymeric materials such as water soluble polyvinyl compounds. Other synthetic polymeric materials include dispersed vinyl compounds in the form of latices, which increase the dimensional stability of photographic materials in particular. For the photosensitive material using a binder, see Japanese Patent Application Laid-Open No. 61-6906.
It is described in Publication No. 2. Regarding the photosensitive material using a binder together with microcapsules, Japanese Patent Application No. 61-
It is described in the specification of No. 52994.

A photopolymerization initiator may be added to the photosensitive layer of the photosensitive material for the purpose of polymerizing the unpolymerized polymerizable compound after image transfer. A light-sensitive material using a photopolymerization initiator is described in Japanese Patent Application No. 61-3025.

When a solvent for a polymerizable compound is used in the light-sensitive material, it is preferably used by enclosing it in a microcapsule different from the microcapsule containing the polymerizable compound. A photosensitive material using an organic solvent miscible with a polymerizable compound encapsulated in microcapsules is described in Japanese Patent Application No. 61-52993.

A water-soluble vinyl polymer may be adsorbed on the above-described silver halide grains for use. The light-sensitive material using the water-soluble vinyl polymer as described above is described in Japanese Patent Application No. 61-238870.

In addition to the above, examples of optional components that can be contained in the photosensitive layer and usage thereof are also described in the application specification regarding the series of photosensitive materials described above, and Research Disclosure Magazine Vol. 170, June 1978. 17029 (pages 9 to 15).

The photosensitive layer of the photosensitive material containing the components described above preferably has a pH value of 7 or less as in the photosensitive material described in Japanese Patent Application No. 61-104226.

Examples of layers that can be optionally provided in the light-sensitive material include an image receiving layer, a heating element layer, an antistatic layer, an anti-curl layer, a peeling layer,
Examples thereof include 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).

Instead of using an image receiving material described later as a method of using the photosensitive material, the image receiving layer may be provided on the photosensitive material and an image may be formed on this layer. The image receiving layer provided on the photosensitive material may have the same structure as the image receiving layer provided on the image receiving material. Details of the image receiving layer will be described later.

For the light-sensitive material using the heating element layer, see Japanese Patent Laid-Open No. 61-
Japanese Patent Application No. 61-55507 for a photosensitive material provided with a cover sheet or a protective layer, and Japanese Patent Application No. 61-96340 for a photosensitive material provided with a layer containing a base or a base precursor. Japanese Patent Application No. 61-24 for a light-sensitive material provided with a coloring layer as an antihalation layer.
6901 specification, respectively. The above-mentioned Japanese Patent Application No. 61-
It is described in the specification of 96340. Further, examples of other auxiliary layers and usage modes thereof are also described in the specification of the series of photosensitive materials described above.

The method for producing the photosensitive material will be described below.

Although various methods can be used as a method for producing a light-sensitive material, a general production method is to prepare a coating solution by dissolving, emulsifying or dispersing the components of the photosensitive layer in an appropriate solvent, and applying the solution. It comprises a step of obtaining a light-sensitive material by applying the liquid to the support as described above and drying.

Generally, each coating solution is prepared by preparing a liquid composition containing each component for each component, and then mixing each liquid composition. The liquid composition may be prepared so as to contain a plurality of components. A part of the components of the photosensitive layer may be added and used at the stage of preparing the liquid composition or the coating solution or after the preparation. Furthermore, as described below, a method of preparing a secondary composition by emulsifying an oily (or aqueous) composition containing one or more components in an aqueous (or oily) solvent can also be used. .

With respect to the main components contained in the photosensitive layer, a method for preparing a liquid composition and a coating liquid is shown below.

The halogenated emulsion can be prepared by any known method such as an acidic method, a neutral method or an ammonia method.

The reaction type of the soluble silver salt and the soluble halogen salt,
Either a one-sided mixing method, a double-sided mixing method or a combination thereof may be used. The back-mixing method in which grains are formed under conditions of excess silver ions and the controlled double-jet method in which pAg is kept constant can also be adopted. Further, in order to accelerate the grain growth, the addition concentration, the addition amount or the addition rate of the silver salt and the halogen salt to be added may be increased (JP-A-55-158124;
55-158124 and U.S. Pat. No. 3,650,757).

The silver halide emulsion used for producing the light-sensitive material may be either a surface latent image type in which a latent image is mainly formed on the surface of the grain or an internal latent image type in which a latent image is formed inside the grain. A direct reversal emulsion in which an internal latent image type emulsion and a nucleating agent are combined can also be used. Internal latent image type emulsions suitable for this purpose are described in U.S. Pat. Nos. 2,952,250 and 3,761,276, and Japanese Patent Publication No. 58-3534 and Japanese Patent Laid-Open No. 58-136641. Preferred nucleating agents to be combined with the above emulsions are U.S. Pat.Nos. 3227552, 4245037, 4255511,
No. 42266013, No. 4276364, and West German Published Patent (OLS) No. 2635316.

In the preparation of a silver halide emulsion used for producing a light-sensitive material, it is preferable to use a hydrophilic colloid as a protective colloid. Examples of hydrophilic colloids are gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; hydroxyethyl cellulose, carboxymethyl cellulose,
Cellulose derivatives such as cellulose sulfates, etc., sodium alginate, sugar derivatives such as starch derivatives, and polyvinyl alcohol, polyvinyl alcohol partial acetals, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole. Examples thereof include various kinds of synthetic hydrophilic polymer substances such as a single or copolymer such as polyvinylpyrazole. Of these, gelatin is preferred. As the gelatin, in addition to lime-processed gelatin, acid-processed gelatin or enzyme-processed gelatin may be used, and a hydrolyzed product or an oxygen-decomposed product of gelatin may also be used.

The silver halide emulsion contains ammonia, an organic thioether derivative (see JP-B-47-386) and a sulfur-containing compound (see JP-A-53-144319) as a silver halide solvent in the step of forming silver halide grains. Etc. can be used. Further, in the process of grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt or the like may be allowed to coexist. Further, water-soluble iridium salts such as iridium chloride (III or IV) and hexachloroiridium ammonium for the purpose of improving high illumination failure and low illumination failure,
Alternatively, a water-soluble rhodium salt such as rhodium chloride can be used.

Soluble salts may be removed from the silver halide emulsion after formation of a precipitate or after physical ripening. In this case, it can be carried out according to the Nudel washing method or the sedimentation method. The silver halide emulsion may be used as it is without being post-ripened, but it is usually chemically sensitized before use. In the emulsion for a conventional type photosensitive material, known sulfur sensitizing method, reduction sensitizing method, noble metal sensitizing method and the like can be used alone or in combination. These chemical sensitizations can be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-58-58).
126526 and 58-215644).

When a sensitizing dye is added to the silver halide emulsion,
It is preferably added at the stage of preparing a silver halide emulsion as in the light-sensitive materials described in JP-A-62-947 and Japanese Patent Application No. 61-55510. When a nitrogen-containing heterocyclic compound is added as the compound having the fog-preventing function and / or the development-accelerating function, it should be added in the step of forming silver halide grains or the step of ripening in the preparation of a silver halide emulsion. Is preferred.
The method for producing a light-sensitive material in which a nitrogen-containing heterocyclic compound is added at the stage of forming silver halide grains or at the stage of ripening is described in Japanese Patent Application No. 61-3024.

When the above-mentioned organic silver salt is contained in the photosensitive layer, the organic silver salt emulsion can be prepared by a method similar to the method for preparing the silver halide emulsion.

In the production of a light-sensitive material, the polymerizable compound can be used as a medium for preparing the composition of other components in the light-sensitive layer. For example, a silver halide (including a silver halide emulsion), a reducing agent, a color image-forming substance and the like can be dissolved, emulsified or dispersed in a polymerizable compound and used for producing a light-sensitive material. In particular, when a color image forming substance is added, it is preferable to include it in the polymerizable compound. Further, as described later, when oil droplets of the polymerizable compound are microencapsulated, components such as wall material necessary for microencapsulation may be included in the polymerizable compound.

The photosensitive composition containing a polymerizable compound containing silver halide can be prepared using a silver halide emulsion.
In addition to the silver halide emulsion, a silver halide powder prepared by freeze-drying or the like can be used for the preparation of the photosensitive composition. The photosensitive composition containing these silver halides can be obtained by stirring with a homogenizer, blender, mixer, or other commonly used stirrer.

In addition, in the polymerizable compound used for preparing the photosensitive composition, it is preferable to dissolve a copolymer composed of a hydrophilic repeating unit and a hydrophobic repeating unit. Japanese Patent Application No. 60-
It is described in the specification of 261887.

Further, instead of using the above copolymer, microcapsules containing a silver halide emulsion as a core substance may be dispersed in a polymerizable compound to prepare a photosensitive composition. The photosensitive composition containing the microcapsules containing the silver halide emulsion as a core substance is described in Japanese Patent Application No. 61-5750.

The polymerizable compound (including those containing other constituents such as the above-mentioned photosensitive composition) is preferably used as an emulsion emulsified in an aqueous solvent. In addition, JP-A-61-
As in the light-sensitive material described in Japanese Patent No. 275742, when oil droplets of a polymerizable compound are microencapsulated, a wall material necessary for microencapsulation is added to this emulsion, and further,
The treatment for forming the outer shell of the microcapsules can also be carried out at this emulsion stage. Further, a reducing agent or any other component may be added at the stage of the above emulsion.

As an example of the above microencapsulation method, US Pat.
No. 2800457 and No. 2800458 A method utilizing coacervation of a hydrophilic wall forming material described in U.S. Pat. No. 3,287,154 and British Patent 990443, and Japanese Patent Publication No. 19574/1983. 42-446 and 42-771
U.S. Pat. No. 3,418,250 and U.S. Pat. No. 3,660,304. Method by precipitation of polymer; U.S. Pat. No. 3,796,669; Method using isocyanate-polyol wall material; U.S. Pat. No. 391451
A method using the isocyanate wall material described in No. 1 specification;
U.S. Patent Nos. 4001140, 4087376 and 408980
No. 2 Method using a urea-formaldehyde-based or urea-formaldehyde-resilicinol-based wall forming material; Method using a wall forming material such as melamine-formaldehyde resin and hydroxypropyl cellulose described in US Pat. No. 4025455 In situ method by polymerization of monomers described in JP-B-36-9168 and JP-A-51-9079; Polymerization dispersion cooling method described in British Patent Nos. 927807 and 965074; US Patent No. The spray drying method and the like described in the respective specifications of 3111407 and British Patent No. 930422 can be mentioned. The method of microencapsulating the oil droplets of the polymerizable compound is not limited to the above, but a method of forming a polymer film as a microcapsule wall after emulsifying the core substance is particularly preferable.

The photosensitive microcapsules that can be used in the production of the light-sensitive material are described in Japanese Patent Application Nos. 61-11556 and 61-1.
1557, 61-53871, 61-53872, 61-53873
No. 61-53874, No. 61-53875, No. 61-53877,
No. 61-53878 is described in each specification.

When the polymerizable compound is a photosensitive composition containing silver halide in the emulsion of the polymerizable compound (including the microcapsule liquid subjected to the microencapsulation treatment) described above, the coating liquid for the photosensitive material is used as it is. Can be used as Emulsions other than the above can be mixed with the composition of other components such as a silver halide emulsion and optionally an organic silver salt emulsion to prepare a coating solution. Other components may be added at the stage of this coating solution as in the case of the above emulsion.

A photosensitive material is manufactured by applying the coating solution for the photosensitive layer prepared as described above onto a paper support which has been prepared in advance and drying. The coating of the coating liquid on the paper support can be easily carried out according to known techniques.

Below, the Example and comparative example of this invention are described. In addition,
In the examples, "parts" means "parts by weight" unless otherwise specified.

[Example 1] [Preparation of light-sensitive material] Preparation of silver halide emulsion Aqueous gelatin aqueous solution (containing 1000 g of water and 0.5 g of potassium bromide in 1000 ml of water, adjusted to pH 3.8 with 1N sulfuric acid, Further kept at 70 ℃), potassium bromide 70
An aqueous solution of silver sulfate (water (600 ml of water
0.59 mol of silver nitrate) was simultaneously added at an equal flow rate for 50 minutes. Five minutes after this was completed, 100 ml of an aqueous solution containing 3.9 g of potassium iodide and an aqueous silver nitrate solution (0.024 mol of silver nitrate dissolved in 100 ml of water) were simultaneously added at the same flow rate for 5 minutes. Thus, a monodisperse tetradecahedral silver iodobromide emulsion having an average grain size of 0.25 μm was prepared.

After washing the above emulsion with water and desalting, 1 of the following sensitizing dyes was used.
A silver halide emulsion having a yield of 600 g was prepared by adding 82 ml of a% methanol solution.

(Sensitizing dye) Preparation of Photosensitive Composition 0.1 g of the following copolymer, 13 g of the following color image-forming substance and 0.5 g of Emarex NP-8 (manufactured by Nippon Emulsion Co., Ltd.) were dissolved in 100 g of trimethylolpropane triacrylate. 1.3 g of the following reducing agent (I) and 1.3 g of the reducing agent (II) were dissolved in 18 g of the above solution. Further, 2.0 g of the silver halide emulsion prepared above was added, and the mixture was stirred using a homogenizer at 15,000 rpm for 10 minutes to obtain a photosensitive composition.

(Copolymer) (Color image forming substance) (Reducing agent I) (Reducing agent II) Preparation of microcapsule solution 9.0g of 20% aqueous solution of Isoban (manufactured by Kuraray Co., Ltd.) and 50g of 2.5% aqueous solution of pectin were added, and pH was adjusted to 4.0 with 10% sulfuric acid.
The above photosensitive composition was added to the aqueous solution prepared as above, and the mixture was stirred for 5 minutes at 12000 rpm using a homogenizer to emulsify the above photosensitive composition in an aqueous solvent.

To this aqueous emulsion, 8.0g of 40% aqueous solution of urea, 10% of resorcin
Aqueous solution 3.0 g, formalin 37% aqueous solution 8.0 g, and ammonium sulfate 8% aqueous solution 3.0 g were sequentially added, and stirred at 60 ° C. for 2 hours.
Heating was continued for an hour. Then adjust the pH to 6.5 with a 10% aqueous sodium hydroxide solution and add 30% sodium bisulfite.
A microcapsule solution was prepared by adding 4.0 g of the aqueous solution.

Preparation of photosensitive material To 10.0 g of microcapsule solution prepared as above,
The following anionic surfactant 1% aqueous solution 1.g, and guanidine trichloroacetate 10% (water / ethanol = 80/20
5.0 g of solution was added to prepare a coating solution.

(Anionic surfactant) 40μ of the above coating solution on the paper support (coated paper) shown below
After applying evenly to obtain a wet film thickness of m, about 40
A photosensitive material was prepared by drying at ℃.

Preparation of paper support LBKP 70 parts and NBKP 30 parts were beaten to a Canadian freeness of 350 cc using a disc refinery, talc 5.0 parts,
Rosin (1.5 parts), sulfuric acid band (2.0 parts), and polyamide polyamine epichlorohydrin (0.5 parts) were all added at an absolute dry weight ratio of pulp. Then, using a rope rope paper machine, the above stock material was made into a base paper having a basis weight of 40 g / m ² and a thickness of 50 μm.

Then 100 parts of SBR latex, 500 parts of clay, and 2,4
A composition comprising 2 parts of dichloro-6-hydroxy-S-triazine sodium salt was coated on the above base paper in an amount of 15
A coating layer was formed by coating so that the coating layer would be g / m ² .

The Cobb water absorption of the paper support prepared as described above is 10
It was g / m ² .

[Image formation] The light-sensitive material prepared as described above was cut into a size of A4 size, and this was cut using Fuji Dichroic Color Enlarger C-450 (manufactured by Fuji Photo Film Co., Ltd.)
The surface of the photosensitive material was uniformly exposed so that the amount of light was 20 CMS. After that, this photosensitive material was placed in a constant temperature and humidity chamber (temperature: 25
℃, relative humidity 14%), the water content of the paper support is 1%
To remove the water.

Next, in the constant temperature and constant humidity chamber, the photosensitive material from which the water content of the paper support was removed was introduced into the heat developing apparatus shown in FIG. 1 attached thereto, and heat development processing was carried out at 140 ° C. for 20 seconds. In addition, the water content of the paper support is measured by an infrared moisture meter (FD-220, Ket Co., Ltd.).
Manufactured).

The heat developing apparatus shown in FIG. 1 will be briefly described below.

FIG. 1 is a diagram schematically showing a heat developing device.

The heat developing device 10 has a structure in which a heating roller 12 and a conveyor belt 13 are housed in a housing 11 as shown in the figure. The heating roller 12 has a hollow inside, and a heat source including a halogen lamp 14 is provided in the center thereof. As a result, the surface (outer periphery) of the roller is maintained at a constant heating temperature. The conveyor belt 13 is an endless belt made of fluororubber and is provided on the outer periphery of the heating roller 12 in a close contact state. It also has a mechanism that rotates at substantially the same speed as the heating roller. The photosensitive material S is sandwiched between a roller and a belt and moved, and thermal development is performed during this period. Therefore, the conditions of the heat development process are easily adjusted by the temperature of the lamp and the rotation speed of the roller.

The photosensitive material S is introduced from the insertion port 15 of the heat developing device 10 having the above-described structure and heat-developed under the above-mentioned set conditions.

[Evaluation of Image Formation] Photosensitive material on which image formation was performed as described above (Example 1)
500kg / cm by overlaying with the image receiving material created as follows
^A positive color image was obtained on the image receiving material by passing through the pressure roller of ^No.2 .

Preparation of image receiving material 40g sodium hexametaphosphate aqueous solution 11g in 125g water
Was further added, and 51 g of zinc 3,5-di-α-methylbenzylsalicylate and 82 g of 55% calcium carbonate slurry were mixed and coarsely dispersed with a mixer. Disperse the solution with Dynamill disperser, and 50% SBR latex 1 to 200 g of the obtained solution.
2 g and 77 g of 8% polyvinyl alcohol were added and mixed uniformly. This mixed solution was uniformly applied onto the above-mentioned coated paper (paper support) so as to have a wet film thickness of 36 μm, and then dried to prepare an image receiving material.

The obtained positive color image was evaluated by the following method.

(1) The occurrence of wrinkles was visually evaluated according to the following criteria.

A: Almost no wrinkles occurred.

B; There were few wrinkles.

C; There were some wrinkles.

D; Wrinkles occurred frequently.

(2) The density unevenness was evaluated by measuring the density of the obtained positive color image using a Macbeth reflection densitometer. The evaluation was performed by comparing the density difference between the maximum density (Dmax) and the minimum density (Dmin) in the image plane.

[Examples 2 to 3] In Example 1, the image formation was changed so that the relative humidity in the constant temperature and humidity chamber was changed to 23% and 42% so that the water content of the paper support became 3% and 4%, respectively. The image was evaluated by operating in the same manner as in Example 1 except that the above procedure was performed.

[Comparative Example 1] The same operation as in Example 1 was carried out except that image formation was carried out in Example 1 without removing water (constant temperature and humidity chamber; temperature: 25 ° C, relative humidity: 80%). The images were evaluated by.

The above results are summarized in Table 1.

From the results shown in Table 1, it is clear that by carrying out the image forming method of the present invention, the generation of wrinkles is suppressed and the unevenness of the image density is remarkably improved.

[Examples 4 to 5] In Example 1, the amount of clay used was changed to 300 parts and 200 parts when the paper support was prepared.
Example 1 except that a paper support having a Cobb water absorption of about 5 and about 3 was prepared and used, and image formation was carried out by removing water so that the water content of the support was 3%. The image was evaluated by operating in the same manner.

[Comparative Example 2] In Examples 4 to 5, images were evaluated by performing the same operations as in Examples 4 to 5 except that a paper support provided with no coating layer was used. I did.

The above results are shown in Table 2.

From the results in Table 2, as an image forming method of the present invention, a photosensitive material composed of a paper support having a Cobb water absorption of 10 g / m ² or less was used, and the water content of the paper support of this photosensitive material was 3%. It can be seen that the unevenness in density is remarkably improved by adopting the method of removing water as described below.

[Example 6] "Method for forming image by releasing dye in a negative image form" [Preparation of photosensitive material] Preparation of photosensitive silver iodobromide emulsion 40 g of gelatin and 26 g of potassium bromide were dissolved in 3000 ml of water. .
Stir this solution while maintaining it at 50 ° C, then add 34 g of silver nitrate.
Was added to 200 ml of water and added. Further, a solution prepared by dissolving 3.3 g of potassium iodide in 100 ml of water was added over 2 minutes. The pH of the silver iodobromide emulsion thus prepared was adjusted, allowed to settle, and excess salts were removed. Then, the pH was adjusted to 6.0, and a yield of 400 g of silver iodobromide was obtained.

Preparation of Gelatin Dispersion Material of Dye-Conjugating Substance: 10 g of the dye-contributing substance shown below, 0.5 g of sodium 2-ethylhexyl ester succinate [surfactant], and tricresyl phosphate (TPC )
Was weighed, 30 ml of ethyl acetate was added, and the mixture was heated to about 60 ° C.
This solution and 100 g of a 10% gelatin solution were stirred, and then dispersed by a homogenizer at 1000 rpm for 10 minutes to prepare a gelatin dispersion of a dye-donor substance.

Dye-sponsored substance Preparation of light-sensitive material 25 g of the silver iodobromide emulsion obtained above, 25 g of a gelatin dispersion of a dye-donor substance, 10 m of a 5% aqueous solution of the compound (a) shown below.
l, and guanidine trichloroacetic acid 1.5 g ethanol 1
A solution dissolved in 5 ml was mixed and dissolved by heating to prepare a coating solution.

Compound (a) Next, 30 μ of the above coating solution was applied onto the paper support used in Example 1.
It was applied so as to have a wet film thickness of m and dried to form a photosensitive layer.

Next, 70 ml of water was added to 25 g of a 10% aqueous gelatin solution to prepare a coating solution, which was coated on the photosensitive layer so as to have a wet film thickness of 25 μm, and dried to form a protective layer. A light-sensitive material was prepared as described above.

Preparation of dye fixing material (image receiving material) 0.75 g of gelatin hardener (H-1), 0.25 g of gelatin hardener (H-2), 160 ml of water and 100 g of 10% lime-treated gelatin were uniformly mixed. . Then, this mixed solution is
On a paper support laminated with polyethylene in which titanium oxide was dispersed, a uniform coating was applied so as to have a wet film thickness of 60 μm, followed by drying to form an intermediate layer.

Gelatin hardener _{(H-1) CH 2 =} CHSO 2 -CH 2 -CONH-CH 2 --CH 2 = NHCOCH 2 -SO 2 -C
H = CH ₂ Gelatin hardener _{(H-2) CH 2 =} CHSO 2 -CH 2 -CONH-CH 2 -CH 2 - Next, the polymer 15g below was dissolved in water 200 ml, 10% lime-processed gelatin 100g And mixed evenly. This mixed solution was uniformly applied onto the intermediate layer so as to have a wet film thickness of 85 μm, and dried to prepare a dye fixing material (image receiving material) having an image receiving layer.

polymer (Intrinsic viscosity: 0.3473, measured in a 1/20 mol disodium hydrogen phosphate aqueous solution at 30 ° C.) [Image formation] Using the light-sensitive material obtained as described above, an image was formed in the same manner as in Example 1 above. Was carried out.

[Evaluation of Image Formation] After the above dye fixing material (image receiving material) is dipped in water, the image receiving layer and the photosensitive layer of the above described light-sensitive material on which the image is formed are superposed, and the mixture is placed on a heat block at 80 ° C. for 6 minutes. Heated for seconds.
Then, the dye fixing material was peeled off from the light-sensitive material to obtain a negative magenta color image on the dye fixing material.

The obtained color image was evaluated in the same manner as in Example 1 above.

[Examples 7 to 8] Images were evaluated by operating in the same manner as in Example 1 except that the photosensitive material obtained in Example 6 was used.

Comparative Example 3 Images were evaluated in the same manner as in Example 1 except that the photosensitive material obtained in Example 6 was used.

The above results are shown in Table 3.

From the results in Table 3, by carrying out the image forming method of the present invention, even in the method of forming an image by releasing the dye in a negative image-like manner, the generation of wrinkles is suppressed and the density unevenness of the image is reduced. It turns out that it can be improved significantly.

[Example 9] "Method of forming negative image-like image by coupling reaction in heat development" [Preparation of photosensitive material] Preparation of gelatin dispersion of coupler 2-dodecylcarbamoyl-1-naphthol 5g, succinic acid 0.5 g of sodium 2-ethyl-hexyl ester sulfonate [surfactant] and tricresyl phosphate (TPC) were weighed, and 30 ml of ethyl acetate was added and dissolved. This solution and 100 g of a 10% gelatin solution were stirred and mixed, and dispersed with a homogenizer at 10,000 rpm for 10 minutes to prepare a gelatin dispersion of coupler.

Next, 3.5 g of the above dispersion, 10 g of the silver iodobromide emulsion obtained in Example 6, 0.26 g of guanidine trichloroacetic acid were added to 3 m of ethanol.
l, a solution of 10% gelatin in water, 5 g, and 2-
A coating solution was prepared by mixing a solution prepared by dissolving 0.2 g of 6-dichloro-p-aminophenol in 17 ml of water.
A photosensitive material was prepared by coating the paper support used in Example 1 so that the wet film thickness was 60 μm, and drying.

[Image formation and evaluation thereof] Image formation was carried out in the same manner as in Example 1 using the photosensitive material obtained as described above. As a result, a negative cyan image was obtained on the light-sensitive material.

The obtained color image was evaluated in the same manner as in Example 1 above.

[Examples 10 to 11] Images were evaluated in the same manner as in Example 1 except that the photosensitive material obtained in Example 9 was used.

Comparative Example 4 Images were evaluated in the same manner as in Example 1 except that the photosensitive material obtained in Example 9 was used.

The above results are shown in Table 4.

From the results shown in Table 4, by carrying out the image forming method of the present invention, even in the method of forming an image by a coupling reaction in a negative image-like manner, the generation of wrinkles is suppressed, and the density unevenness of the image is remarkable. I found that it could be improved.

[Brief description of drawings]

 FIG. 1 is a diagram schematically showing a heat developing device. 11: Housing, 12: Heating roller 13: Conveyor belt, 14: Halogen lamp S: Photosensitive material

Continuation of the front page (56) Reference JP 63-38934 (JP, A) JP 62-78552 (JP, A) JP 62-201433 (JP, A) JP 61-156045 (JP , A) JP 60-239745 (JP, A) JP-B 3-36414 (JP, B2) JP-B 5-55070 (JP, B2) JP-B 57-2585 (JP, B2) JP-B 56-32189 (JP, B2)

Claims (15)

[Claims] 1. A method for forming an image by performing a heat development treatment on a photothermographic material having a photosensitive layer containing a photosensitive component on a paper support simultaneously with imagewise exposure or after the imagewise exposure, As the paper support, one having a coating layer made of a hydrophobic polymer provided on the photosensitive layer side so that the Cobb water absorption defined by JIS-P-8140 is 10 g / m ² or less is used. An image forming method comprising the steps of: removing the water in the support so that the water content is 4% or less while suppressing the transfer of the water to the photosensitive layer by the coating layer consisting of . 2. The image forming method according to claim 1, wherein the Cobb water absorption is 3 g / m ² or less. 3. The image forming method according to claim 1, wherein the hydrophobic polymer has a crosslinked structure. 4. The image forming method according to claim 1, wherein the water content in the support is removed so that the water content is 3% or less. 5. The image forming method according to claim 1, wherein water in the paper support is removed after imagewise exposure. 6. The heating temperature in the heat development treatment is 80.degree.
The image forming method according to claim 1, wherein the temperature is from 200 ° C to 200 ° C. 7. A component of the photosensitive material is transferred to the image receiving material by pressing the image receiving material in a state of being superposed on the photosensitive material which has been subjected to the heat development treatment, and an image is obtained on the image receiving material. The image forming method according to item 1 above. 8. A photothermographic material having a photosensitive layer containing a silver halide, a reducing agent and a polymerizable compound on a paper support is subjected to a heat development treatment simultaneously with or after the imagewise exposure. In the method of forming an image with a coating layer, a coating layer made of a hydrophobic polymer is provided on the photosensitive layer side as the paper support so that the Cobb water absorption defined by JIS-P-8140 is 10 g / m ² or less. The water content in the support is removed so that the water content is 4% or less with the use of a coating layer made of a hydrophobic polymer and suppressing the transfer of water to the photosensitive layer. An image forming method characterized by the above. 9. The image forming method according to claim 8, wherein the Cobb water absorption is 3 g / m ² or less. 10. The image forming method according to claim 8, wherein the hydrophobic polymer has a crosslinked structure. 11. The image forming method according to claim 8, wherein the water content in the support is removed so that the water content is 3% or less. 12. The image forming method according to claim 8, wherein water in the paper support is removed after imagewise exposure. 13. The heating temperature in the heat development treatment is 80.
The image forming method according to claim 8, wherein the image forming temperature is from 200 to 200 ° C. 14. An unpolymerized polymerizable compound is transferred to the image receiving material by applying pressure to the photosensitive material which has been subjected to the heat development treatment while the image receiving material is superposed on the image receiving material, and an image is obtained on the image receiving material. The image forming method according to claim 8. 15. The image forming method according to claim 8, wherein the photosensitive layer further contains a color image forming substance.