JP2622569B2 - Photosensitive material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a photosensitive material having a photosensitive layer containing a silver halide, a reducing agent and a polymerizable compound on a support.

BACKGROUND OF THE INVENTION A photosensitive material having a photosensitive layer containing a silver halide, a reducing agent and a polymerizable compound on a support is used for an image forming method in which a latent image of silver halide is formed and the polymerizable compound is polymerized. Can be used.

Examples of the image forming method include JP-B-45-11149,
Nos. 7-20741, 49-10697, JP-A-57-138632, 5
No. 8-169143. In these methods, when the exposed silver halide is developed using a developer, a coexisting polymerizable compound (eg, a vinyl compound) starts to polymerize to form an image-like polymer compound.
Therefore, the above method requires a developing process using a liquid, and the process requires a relatively long time.

As an improvement of the above method, Japanese Patent Application Laid-Open No. 61-69062 describes a method in which a high molecular weight compound can be obtained by dry treatment. This method uses a photosensitive silver salt (silver halide), a reducing agent, a crosslinkable compound (polymerizable compound).
A latent image is formed by exposing a recording material (photosensitive material) having a photosensitive layer formed of a binder and a binder on a support to form a latent image and then thermally developing the latent image to form a latent image of a photosensitive silver salt. This is a method of forming a polymer compound in the portion where the above is applied. The image forming method using the above-mentioned dry processing and the photosensitive material used therefor are described in JP-A-61-73145 and JP-A-61-164.
Nos. 83640 and 61-188535 are also described.

The above image forming method is a method of polymerizing a polymerizable compound in a portion where a silver halide latent image is formed.

In addition, a method capable of polymerizing a polymerizable compound in a portion where a silver halide latent image is not formed is already known (Japanese Patent Application Laid-Open No. 62-70836). In this method, a thermal development is performed to reduce the polymerization of the polymerizable compound by causing a reducing agent to act on a portion where the silver halide latent image is formed,
This is a method of accelerating the polymerization of other parts.

The photosensitive material used in the image forming method as described above may be constituted by using paper as a support because it is inexpensive and easily disposable, lightweight and easy to handle.

In addition, various types of photosensitive materials have been proposed depending on the purpose of use and application. For example, the surface of the support in contact with the photosensitive layer has a high white height (JIS-JIS) of a certain value or more.
There is a light-sensitive material configured to have a whiteness defined by p-8123) (Japanese Patent Application No. 62-136361). According to the photosensitive material having this configuration, the resolution of the obtained image can be further increased.

On the other hand, the photosensitive material is advantageously used for an image forming method in which an image is formed on the photosensitive material by imagewise exposure and heat development, and then the image is pressure-transferred to the image receiving material to obtain a transfer image on the image receiving material. Available.

However, when the above-described image forming method is performed using a photosensitive material composed of a paper support having a high whiteness as described in the above publication, transfer unevenness may occur in an image.

[Summary of the Invention] It is an object of the present invention to provide a photosensitive material that can obtain a high-resolution image and suppresses the occurrence of transfer unevenness.

The object is to provide a photosensitive material having a photosensitive layer containing a silver halide, a reducing agent, and a polymerizable compound on a paper support, wherein the paper support contains hollow spherical thermoplastic resin particles and a binder on a base paper. This can be achieved by the photosensitive material of the invention, which is a paper support having a coating layer on the photosensitive layer side.

In the present invention, the following preferred modes can be adopted.

(1) The binder is a hydrophobic polymer.

(2) The inner diameter of the hollow portion of the hollow sphere-shaped thermoplastic resin fine particles is in the range of 0.1 to 0.8 with respect to the outer diameter.

(3) The particle size of the hollow spherical thermoplastic resin particles is in the range of 0.05 to 5 μm.

(4) The hollow sphere-shaped thermoplastic resin fine particles contain at least one resin selected from the group consisting of a polystyrene resin, an acrylic resin, and a styrene-acrylic resin.

(5) The binder contains at least one resin selected from the group consisting of styrene-butadiene copolymer, methyl methacrylate-butadiene copolymer and polyvinylidene chloride.

(6) The coating layer is formed at a coating amount of 1 to 30 g / m ² .

(7) The photosensitive layer further contains a color image forming substance.

(8) The photosensitive layer further contains a color image forming substance, and at least the polymerizable compound and the color image forming substance are contained in the microcapsule in the photosensitive layer.

(9) For heat development.

[Effects of the Invention] The present inventors have studied the causes of the above-mentioned uneven transfer. As a result, the layer containing a hydrophilic white pigment such as titanium oxide as described above does not have sufficient hydrophobicity as a whole layer, and therefore, when a photosensitive layer is formed on such a paper support. Was found to easily cause unevenness of seepage due to the photosensitive solution. In addition, it was found that the layer composed of the above white pigment was hard to impart sufficient smoothness to the layer because the pigment was hard and hardly deformed.

Since the hollow sphere-shaped thermoplastic fine particles used for the paper support according to the present invention are made of a hydrophobic polymer resin, the formed coating layer has high waterproofness, and is impregnated with the photosensitive liquid. The occurrence of unevenness is suppressed. Further, since the fine particles are thermoplastic as well as the hollow sphere,
By performing the super calendering process in the process of manufacturing the paper support, the paper support can be easily provided with high smoothness (also having cushioning properties). For these reasons, according to the photosensitive material having the paper support of the present invention, transfer unevenness can be reduced.

In addition, the hollow spherical thermoplastic particles, light scattering occurs between the resin layer and the air inside because the center is hollow,
Has high whiteness. Therefore, the coating layer composed of these fine particles has a function as a light reflection layer, the interface between the photosensitive layer and the support at the time of exposure, or the image scattering caused by light scattering generated on the back surface of the support. The resolution can be prevented from lowering. Therefore, the obtained image has a high resolution.

[Detailed Description of the Invention] The paper support according to the present invention has a coating layer containing hollow spherical thermoplastic resin fine particles and a binder on a base paper.

 Hereinafter, the base paper and the coating layer will be described in this order.

The base paper used for the paper support is mainly wood pulp,
This is manufactured by papermaking. As the wood pulp, either softwood pulp or hardwood pulp can be used, but in the present invention, it is preferable to use a large amount of short-fiber hardwood pulp. Specifically, it is preferable that 60% by weight or more of the pulp constituting the base paper is hardwood pulp.

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

In addition, the freeness of the entire pulp used is 2 in the CSF regulations.
It is preferably 50 to 500 cc, more preferably 200 to 400 cc. Furthermore, it is preferable that the fiber length after beating is such that the 24 + 42 mesh residue specified by JIS-P-8207 is 40% by weight or less.

An internal sizing agent such as rosin, paraffin wax, higher fatty acid salt, alkenyl succinate, fatty acid anhydride, and alkyl ketene dimer may be added to the base paper.

Fillers such as calcium carbonate, talc, clay, kaolin, titanium dioxide, and urea resin fine particles as internal additives other than the internal sizing agent; paper strength agents such as polyacrylamide, starch, polyvinyl alcohol, and melamine formaldehyde condensate; anhydrous A reaction product of a maleic acid copolymer and a polyalkylene polyamine, a softened product such as a quaternary ammonium salt of a higher fatty acid; a fixing agent such as a sulfate band or a polyamide polyamine epichlorohydrin; a colored dye; May be added.

The base paper used for the paper support can be formed by using a raw material as described above and using a fourdrinier paper machine or a round paper machine.

Preferably the basis weight of the base paper is 20 to 200g / m ^2, 3
It is particularly preferred that it is 0 to 100 g / m ² . The thickness of the base paper
25 to 250 μm, preferably 40 to 1650 μm
Is particularly preferred.

Further, it is preferable that the base paper is subjected to a calender treatment such as an on-machine calender in a paper machine or a super calender after the paper making for the purpose of improving smoothness. From the calendering process, the density of the base paper is
It is preferable to be 0.7 to 1.2 g / m ² at a specified JIS-P-8118, it is particularly preferable to be 0.85 to 1.10 g / m ^2.

Further, it is preferable that the stiffness of the base paper specified by JIS-P-8143 is 20 to 150 g with respect to the scheduled transfer direction. This is because, when an image is formed using a photosensitive material, an image recording device or the like provided with a transport mechanism is often used.According to research conducted by the present inventors, the rigidity in the transport direction is 20 g. If the base paper is smaller than the above, the paper is likely to be creased during transportation, causing jamming of the photosensitive material in the apparatus. On the other hand, if the stiffness in the transport direction exceeds 150 g, the photosensitive material with a certain roller length will not enter the cassette, and the motor load on the transfer roller will increase. Will happen.

Note that a surface sizing agent may be applied to the base paper surface. Examples of the surface sizing agent include polyvinyl alcohol, starch, polyacrylamide, gelatin, casein, styrene-maleic anhydride copolymer, alkyl ketene dimer, polyurethane, and epoxidized fatty acid amide.

The coating layer is provided on one surface (the felt surface, the surface on which the photosensitive layer is provided) of the base paper as described above.

The hollow sphere-shaped thermoplastic resin fine particles (hereinafter, referred to as fine particles according to the present invention), which is a characteristic requirement of the present invention, may have an inner diameter of the hollow portion in the range of 0.1 to 0.8 with respect to the outer diameter. preferable.

Further, the particle size is preferably in the range of 0.05 to 5 μm.

Examples of the fine particles according to the present invention include those composed of thermoplastic resins such as polystyrene resin, styrene-acryl resin, acrylic resin, polyethylene resin, polypropylene resin, polyacetal resin, chlorinated polyether resin, and polyvinyl chloride resin. be able to. Among the above, a polystyrene resin, an acrylic resin or a styrene-acryl resin is preferred. Representative products are OPAQUE polymer OP-42M (acrylic-styrene.
Copolymer, Rohm and Haas Japan Co., Ltd.)
Can be mentioned.

There is no particular limitation on the binder. In the present invention, it is preferable to use a hydrophobic polymer as a latex. Thereby, a higher waterproof property can be imparted to the coating layer.

The hydrophobic polymer may be a homopolymer or a copolymer. Further, in the case of a copolymer, even if it has a hydrophilic repeating unit in a part, it may be hydrophobic as a whole. Specifically, vinylidene chloride, styrene-butadiene copolymer, methyl methacrylate-butadiene.
Copolymers, acrylonitrile-butadiene copolymers, styrene-acrylate copolymers, methyl methacrylate-acrylate copolymers,
And styrene-methacrylate-acrylate copolymers. Of these, styrene-butadiene copolymer, methyl methacrylate-butadiene copolymer or polyvinylidene chloride resin is preferred.

Other examples of the hydrophobic polymer include wax and petroleum resin.

Specific examples of the wax include paraffin wax and microcrystalline wax.

The petroleum resin is a hydrocarbon-based resin obtained by copolymerizing an unsaturated aromatic hydrocarbon or an unsaturated aliphatic hydrocarbon having 5 or more carbon atoms by-produced in naphtha cracking. Examples of the unsaturated aromatic hydrocarbons and unsaturated aliphatic hydrocarbons include cyclopentadiene, methylstyrene, ethylstyrene, dimethylstyrene, methylindene, methylpropenylbenzene, and the like. In addition, a resin to which maleic anhydride is partially added or a hydrogenated resin in the copolymerization may be used. In the present invention, a petroleum resin to which maleic anhydride is partially added is preferable.

The above binders may be used alone or in an appropriate combination.

The coating layer according to the present invention is prepared by adding a component such as a hollow sphere-shaped fine particle and a curing agent and a water-proofing agent described below to the binder, and dissolving, dispersing, or emulsifying a latex-like coating solution. However, it can be easily provided by applying it on the base paper. As a method of applying the coating solution on the base paper, a known dip coating method, air knife coating method, curtain coating method, roller coating method, doctor oad method, gravure coating method, or the like can be used.

The coating layer formed as described above is 1 to 30 g / m ²
It is preferable that it is formed with the application amount. A more preferred coating amount is 5 to 20 g / m ² .

After forming the coating layer, it is preferable to perform a calendering treatment such as a gloss calender or a super calender. High smoothness can be obtained by these calendering processes. The linear pressure in the calendar process is
It is preferably in the range of 100 to 300 kgf / cm. Also,
The temperature at this time is preferably in the range of 50 to 80 ° C.

In the present invention, it is preferable to further provide an undercoat layer on the coating layer in order to prevent blocking (adhesion) of the coating layer during the calendering treatment. This undercoat layer can be composed of a layer containing the aforementioned hydrophobic polymer. Alternatively, it can be composed of a layer containing an organic pigment and / or an inorganic pigment. In the case of a layer containing a hydrophobic polymer, a higher waterproof property is provided together with the above-described blocking prevention.

As the pigment, pigments used for known coated papers (coated paper, art paper, baryta paper, and the like) can be used. Examples of the inorganic pigment include titanium dioxide, barium sulfate, talc, clay, kaolin, calcined kaolin, aluminum hydroxide, amorphous silica, crystalline silica, and synthetic alumina silica. Examples of the organic pigment include benzoguanidine resin, polystyrene resin, acrylic resin, and urea formalin resin. These organic pigments and inorganic pigments may be used alone or in combination.

In addition, the binder (hydrophobic polymer) constituting the coating layer and the undercoat layer may have a crosslinked structure. In order 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 above curing agents include 1,3
Active vinyl compounds such as -bis (vinylsulfonyl) -2-propanol and methylenebismaleimide; 2,4-dichloro-6-hydroxy-S-triazine sodium salt, 2,4-dichloro-6-hydroxy-S- Active halogen compounds such as triazine, N, N'-bis (2-chloroethylcarbamyl) piperazine; epoxy compounds such as bis (2,3-epoxypropyl) methylpropylammonium / p-toluenesulfonate; and Examples thereof include methanesulfonic acid ester compounds such as 1,2-di (methanesulfonoxy) ethane. Further, a water-proofing agent may be added. Examples of the water-resistant agent include polyamide polyamine epichlorohydrin resin, polyamide polyurea resin, glyoxal resin, and the like. Among these, a polyamide polyamine epichlorohydrin resin and a polyamide polyurea resin containing no formalin are particularly preferred.

The undercoat layer can be provided on the coating layer by the same method as in the case where the coating layer is provided.

The undercoat layer formed as described above is 1 to 5 g / m
Preferably, it is formed with a coating amount of ² .

Hereinafter, the silver halide, the reducing agent, and the polymerizable compound constituting the photosensitivity provided on the support described above will be described.

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

The halogen composition of the silver halide grains may be uniform or non-uniform on the surface and inside. Regarding silver halide grains having multiple structures having different compositions on the surface and in the interior, JP-A-57-154232, JP-A-58-108533, and JP-A-59-48
Nos. 755, 59-52237, U.S. Pat. No. 4,433,048 and European Patent No. 100984. Also,
As in the light-sensitive material described in JP-A-62-183453, silver halide grains having a high silver iodide ratio in the shell portion may be used.

There is no particular limitation on the crystal habit of the silver halide grains.
For example, tabular grains having an aspect ratio of 3 or more, such as a photosensitive material described in JP-A-61-55509, may be used.

The silver halide grains described in JP-A-61-21
It is preferable to use silver halide grains having a relatively low fog value as in the light-sensitive material described in JP-A-4580.

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

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

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

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

The reducing agent that can be used in the light-sensitive material has a function of reducing silver halide and / or a function of accelerating (or suppressing) polymerization of a polymerizable compound. There are various kinds of substances as the reducing agent having the above function. Examples of the reducing agent include hydroquinones, catechols, p-aminophenols, p-phenylenediamines, 3-pyrazolidones, 3-aminopyrazoles, 4-amino-pyrazolones, 5-aminouracils, 5-dihydroxy-6-aminopyrimidines, reductones, aminoreductones, o- or p-sulfonamidophenols, o- or p-sulfonamidonaphthols, 2-
Sulfonamide indanones, 4-sulfonamide-5
-Pyrazolones, 3-sulfonamidoindoles, sulfonamidopyrazolobenzimidazoles, sulfonamidopyrazolotriazoles, α-sulfonamidoketones, hydrazines and the like. By adjusting the type and amount of the reducing agent, the polymerizable compound in a portion where a latent image of silver halide is formed or a portion where a latent image is not formed can be polymerized. In a system in which a polymerizable compound in a portion where a latent image of silver halide is not formed is polymerized, 1-phenyl-
It is particularly preferred to use 3-pyrazolidones.

The various reducing agents having the above functions are described in JP-A-61-183640, JP-A-61-188535, JP-A-61-228441, and JP-A-62-70836 and JP-A-62-86354. ,same
No. 62-86355, Japanese Patent Application No. 60-227528, JP-A-62-198849
(Including those described as developing agents or hydrazine derivatives). The reducing agent is described in “The Theory of the Photogr” by T. James.
aphic Process "4th edition, pp. 291-334 (1977), Research Disclosure Magazine, Vol. 170, 1702, June 1978
No. 9 (pages 9 to 15) and Vol. 176, the first of December 1978
No. 7643 (pp. 22-31). Also, Japanese Patent Application Laid-Open
As in the light-sensitive material described in JP 210446, a reducing agent precursor capable of releasing the reducing agent under heating conditions or in contact with a base or the like may be used instead of the reducing agent.
The reducing agent and the reducing agent precursor described in each of the above publications, the specification and the literature can be effectively used also in the photosensitive material in the present specification. Therefore, the “reducing agent” in the present specification includes the reducing agent and the reducing agent precursor described in each of the above publications, the specification and the literature. These reducing agents may be used alone, or as described in the above-mentioned respective specifications, two or more reducing agents may be mixed and used. When two or more types of reducing agents are used in combination, the reducing agents interact firstly by promoting reduction of silver halide (and / or organic silver salt) by so-called superadditivity. Causing the polymerization of the polymerizable compound via an oxidation-reduction reaction with another reducing agent coexisting with an oxidized form of the first reducing agent generated by the reduction of silver halide (and / or organic silver salt) (Or to suppress polymerization). However, at the time of actual use, since the above-mentioned reactions can occur at the same time, it is difficult to specify which action it is.

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

The polymerizable compound that can be used in the photosensitive material is not particularly limited, and a known polymerizable compound can be used. In addition,
As a method of using the photosensitive material, when a heat development process is scheduled, a high boiling point (for example, having a boiling point of 80
(° C. or more). Further, since the mode in which the photosensitive layer contains a color image-forming substance as an optional component described later aims to immobilize the color image-forming substance by polymerization and curing of the polymerizable compound, the polymerizable compound has a plurality of molecules in the molecule. It is preferably a crosslinkable compound having a polymerizable functional group. Further, as described later, when a transfer image is formed using an image receiving material, a high-viscosity substance may be used as a polymerizable compound as in a photosensitive material described in Japanese Patent Application No. 61-150079. preferable.

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

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

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

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

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

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

In the photosensitive material, the polymerizable compound is preferably dispersed in the photosensitive layer in the form of oil droplets. An example of a photosensitive material in which a polymerizable compound is dispersed in the photosensitive layer in the form of oil droplets is disclosed in
It is described in JP-A-62-78552. The oil droplets may contain other components in the photosensitive layer, such as silver halide, a reducing agent, and a color image forming substance. Japanese Patent Application Laid-Open Nos. Sho 62-209450 and 62-14040 each describe a light-sensitive material containing silver halide in an oil droplet, and a light-sensitive material further containing a reducing agent in an oil droplet. Each is described in JP-A-62-183453. When silver halide is contained in an oil droplet, the number of silver halide grains contained in the oil droplet is set to 5 or more as described in Japanese Patent Application No. 61-160592. Is preferred.

More preferably, the oil droplets of the polymerizable compound are in a state of microcapsules. Various known techniques can be applied to the microcapsules without any particular limitation. For an example of a photosensitive material in which oil droplets of a polymerizable compound are in the form of microcapsules, see JP-A-61-2784.
It is described in JP-A-41.

There is no particular limitation on the wall material constituting the outer shell of the microcapsule. For a photosensitive material using a microcapsule having an outer shell made of a polyamide resin and / or a polyester resin, Japanese Patent Application Laid-Open No. 62-209437 discloses a microcapsule having an outer shell made of a polyurea resin and / or a polyurethane resin. Japanese Patent Application Laid-Open No. 62-209438 discloses a photosensitive material used, and Japanese Patent Application Laid-Open No. 62-209439 discloses a photosensitive material using a microcapsule having an outer shell made of an amino-aldehyde resin. Japanese Patent Application Laid-Open No. 62-209440 discloses a photosensitive material using microcapsules having epoxy resin, and Japanese Patent Application Laid-Open No. 62-209441 discloses a photosensitive material using microcapsules having an outer shell made of epoxy resin. For photosensitive materials using microcapsules having a composite resin shell containing urea resin and polyurea resin 094
Japanese Patent Application Laid-Open No. 62-209442 discloses a photosensitive material using a microcapsule having a composite resin shell containing a polyurethane resin and a polyester resin.

When 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 containing silver halide in microcapsules,
It is preferable that silver halide is present in the wall material constituting the outer shell of the microcapsule. For photosensitive materials containing silver halide in the wall material of microcapsules, see
No. 169147.

Further, silver halide, a reducing agent, a polymerizable compound, two or more microcapsules different in at least one component among components contained in microcapsules such as a color image forming substance which is an optional component described below may be used in combination. Good. In particular, when a full-color image is formed, it is preferable to use three or more types of microcapsules having different color hues of the contained color image forming substances. A photosensitive material using two or more types of microcapsules in combination is described in JP-A-62-1988.
It is described in Japanese Patent Publication No. 50.

The average particle size of the microcapsules is preferably 3 to 20 μm. The particle size distribution of the microcapsules is preferably uniformly distributed to a certain value or more, as in the photosensitive material described in Japanese Patent Application No. 61-150080.
The thickness of the microcapsules is preferably within a certain range with respect to the particle diameter, as in the case of the photosensitive material described in Japanese Patent Application No. 61-227767.

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

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

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

There is no particular limitation on the color image forming substance that can be used for the photosensitive material, and various types can be used. That is, a substance that is itself colored (dye or pigment), or itself is colorless or light-colored, but external energy (heating, pressing, light irradiation, etc.) or another component (a color developer) A substance that develops color upon contact (color former) is also included in the color image forming substance. The general photosensitive material using a color image forming substance is described in the above-mentioned JP-A-61-73145. Further, a photosensitive material using a dye or a pigment as a color image forming substance is disclosed in JP-A-62-187346, and a photosensitive material using a leuco dye is disclosed in JP-A-62-209436. Japanese Patent Application Nos. 61-96339 and 61-133091 and 61-133302 disclose cyan-sensitive leuco dyes. Are described in Japanese Patent Application No. 61-197963.

Dyes and pigments, which are substances that themselves are colored, are commercially available, as well as various references (for example, "Dye Handbook" edited by the Society of Synthetic Organic Chemistry, published in 1970, "Latest Pigment Handbook" edited by the Japan Pigment Technical 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 a substance that develops a color by some energy such as heating, pressurizing, and light irradiation include thermochromic compounds, piezochromic compounds, photochromic compounds, and leuco such as triarylmethane dyes, quinone dyes, indigoid dyes, and azine dyes. The body is known. All of these develop color by heating, pressing, light irradiation or air oxidation.

Examples of substances that form a color when contacted with another component include an acid-base reaction between two or more components, a redox reaction,
Various systems that develop color by a coupling reaction, a chelate forming reaction, and the like are included. For example, pressure-sensitive copying paper (pages 29 to 58) and azography (87 to 95) described in "Introduction to Special Paper Chemistry" written by Hiroyuki Moriga (published in 1975).
Page), known color development systems such as thermosensitive coloring (pages 118-120), etc., or a seminar organized by Kinki Chemical Industry Association "Latest Dye Chemistry-Attractive Use and New Development as Functional Dyes" The coloring system described on pages 26 to 32 (June 19, 1980) can be used. Specifically, lactone, lactam,
Coloring system consisting of a coloring agent having a partial structure such as spiropyran and an acidic substance (coloring agent) such as acidic clay and phenols; aromatic diazonium salts, diazotates, diazosulfonates and naphthols, anilines, active methylenes A chelation-forming reaction such as a reaction between hexamethylenetetramine and ferric ion or gallic acid, or a reaction between phenolphthalein-complexones and an alkaline earth metal ion; stearic acid A redox reaction such as a reaction between ferric iron and pyrogallol and a reaction between silver behenate and 4-methoxy-1-naphthol can be used.

The color image forming substance is based on 100 parts by weight of the polymerizable compound.
It is preferably used in a proportion of 0.5 to 20 parts by weight, more preferably in a proportion of 2 to 7 parts by weight. When a color developer is used, it is preferably used in a ratio of about 0.3 to 80 parts by weight with respect to 1 part by weight of the color former.

When two types of substances that cause a color reaction in a contact state are used as the solid color image forming substances, one of the substances that cause the color reaction and a polymerizable compound are contained in a microcapsule. However, a color image can be formed on the photosensitive layer by allowing another substance among the substances that cause the color-forming reaction to exist outside the microcapsules containing the polymerizable compound. The photosensitive material from which a color image can be obtained without using an image receiving material as described above is described in JP-A-62-209444.

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

The sensitizing dye is preferably added at the stage of preparing a silver halide emulsion described below. A photosensitive material obtained by adding a sensitizing dye in the stage of forming silver halide grains is described in JP-A-62-947, in which a sensitizing dye is added to a silver halide emulsion after forming silver halide grains. Regarding the photosensitive material obtained by adding at the preparation stage,
These are described in the specification of JP 61-55510 A, respectively. Further, specific examples of sensitizing dyes that can be used in photosensitive materials are described in JP-A-62-947 and JP-A-61-55510. Further, as in the light-sensitive material described in JP-A-61-208786, an infrared light-sensitive sensitizing dye may be used in combination.

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

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

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

 Examples of various image formation accelerators are shown below.

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

As base precursors, salts of organic acids and bases that are decarboxylated by heating, intramolecular nucleophilic substitution, Rossen rearrangement,
Compounds which release a base by causing some reaction by heating, such as compounds which release amines by a reaction such as Beckmann rearrangement, and compounds which generate a base by electrolysis or the like are preferably used.

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

The light-sensitive material using a base or a base precursor is described in Japanese Patent Application No. 60-227528. Further, photosensitive materials using a tertiary amine as a base are described in JP-A-62-170954, and photosensitive materials using a particulate dispersion of a hydrophobic organic basic compound having a melting point of 80 to 180 ° C. JP-A-62-209523 discloses that the solubility is 0.1%.
The following photosensitive material using a guanidine derivative is described in JP-A-62-215637, and the photosensitive material using a hydroxide or salt of an alkali metal or alkaline earth metal is described in Japanese Patent Application No. 61-96341. There is a description in each book.

Further, as for a photosensitive material using an acetylide compound as a base precursor, Japanese Patent Application No. 61-167558 discloses that a propiolate is used as a base precursor.
Japanese Patent Application No. 61-191000 discloses a light-sensitive material containing silver, copper, a silver compound or a copper compound as a catalyst for a base formation reaction.
Japanese Patent Application No. 61-227769 discloses a light-sensitive material containing the propiolate and the silver, copper, silver compound or copper compound in a state isolated from each other. For a light-sensitive material containing a ligand in a free state in addition to copper, a silver compound or a copper compound, Japanese Patent Application No. 61-243555 discloses a propiolate as a base precursor, and further uses a heat-meltable compound as a base. Japanese Patent Application No. 61-191001 discloses a light-sensitive material containing a sulfonyl acetate as a base precursor and further contains a heat-meltable compound as a reaction accelerator for a base-forming reaction. Is disclosed in Japanese Patent Application No. 61-193375, using a compound obtained by bonding an isocyanate or isothiocyanate to an organic base as a base precursor. Japanese Patent Application No. Sho for fee 61-
No. 167558 describes each.

When a base or a base precursor is used for the photosensitive material, silver halide, a reducing agent and a polymerizable compound are contained in the microcapsules described above, and the base or the base precursor may be present in the photosensitive layer outside the microcapsules. preferable. Alternatively, JP-A-62-209521
A base or a base precursor may be contained in another microcapsule, as in the light-sensitive material described in Japanese Patent Application Laid-Open Publication No. H11-163,036. The light-sensitive material using a microcapsule containing a base or a base precursor is described in Japanese Patent Laid-Open No. Sho 62 (1993), as well as the above specification. Japanese Patent Application Laid-Open No. Sho 62-209526 discloses a photosensitive material containing solid fine particles carrying a base or a base precursor in a microcapsule.
Photosensitive materials using microcapsules containing a basic compound at 0 ° C. are described in Japanese Patent Application No. 61-212149. Further, instead of the microcapsules containing the base or the base precursor, particles containing a base or a base precursor and a hydrophobic substance in a compatible state, such as a photosensitive material described in Japanese Patent Application No. 61-243556, may be used. Good.

The base or base precursor is described in Japanese Patent Application No. 61-96.
As described in the specification of JP 3640, it may be added to an auxiliary layer other than the photosensitive layer (a layer containing a base or a base precursor described later). Further, as described in Japanese Patent Application No. 61-176417, the above-mentioned support may be made porous and a base or a base precursor may be contained in the porous support.

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

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

The compound having an antifogging function and / or a development accelerating function can be used for the purpose of obtaining a clear image having a high maximum density and a low minimum density (an image having a high S / N ratio). JP-A-62-151838 discloses a photosensitive material using an antifoggant as a compound having an antifogging function and / or a development accelerating function, and discloses a light-sensitive material using a compound having a cyclic amide structure. JP-A-61-151841 discloses a photosensitive material using a thioether compound in JP-A-62-15184, and a photosensitive material using a polyethylene glycol derivative is described in JP-A-62-151843. Japanese Patent Application Laid-Open No. Sho 62-151844 discloses a photosensitive material using a derivative, and Japanese Patent Application Laid-Open No. 62-17 / 1987 describes a photosensitive material using an acetylene compound.
No. 8232, a photosensitive material using a sulfonamide derivative is described in JP-A-62-183450, and a photosensitive material using a quaternary ammonium salt is described in JP-A-61-238871. is there.

As the thermal solvent, a compound that can be a solvent for a reducing agent, a compound that is known to promote a physical phenomenon with a substance having a high dielectric constant, and the like are useful. The photosensitive material using a thermal solvent is described in Japanese Patent Application No. 60-227527.

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

The thermal polymerization initiator that can be used for the photosensitive material is a compound that generally undergoes thermal decomposition under heating to generate a polymerization initiating species (particularly a radical), and is generally used as an initiator for radical polymerization. The thermal polymerization initiator is described in, for example, pages 6 to 18 of “Addition Polymerization and Ring-Opening Polymerization”, ed. The thermal polymerization initiator is preferably used in a range of 0.1 to 120% by weight based on the polymerizable compound, and 1 to 1%.
More preferably, it is used in the range of 0% by weight. In addition,
In a system for polymerizing a polymerizable compound in a portion where a silver halide latent image is not formed, it is preferable to add a thermal polymerization initiator to the photosensitive layer. Further, a photosensitive material using a thermal polymerization initiator is described in JP-A-62-70836.

A development terminator that can be used in a photosensitive material is a compound that neutralizes a base or reacts with a base immediately after proper development to reduce the base concentration in the film and to interact with a compound or silver and a silver salt that stops development. Is a compound that controls development.

A dye or pigment may be added to the photosensitive layer of the photosensitive material for the purpose of preventing halation or irradiation. 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.

In the case where the photosensitive layer of the photosensitive material uses the above-described microcapsules, a dye having a property of decoloring by heating or light irradiation may be contained in the microcapsules. The dye having the property of decoloring by heating or light irradiation can function as a dye corresponding to a yellow filter in a conventional silver salt photographic system. Regarding photosensitive materials using dyes that have the property of decoloring by heating or light irradiation as described above,
It is described in the specification of 61-243551.

As the anti-smudge agent used in the light-sensitive material, solid particles at room temperature are preferable. The average particle size of the above particles is preferably in the range of 3 to 50 μm by volume average diameter, more preferably in the range of 5 to 40 μm. As described above, when the oil droplets of the polymerizable compound are in the form of microcapsules, it is more effective that the particles are larger than the microcapsules.

The binder that can be used in the photosensitive material can be contained alone or in combination in the photosensitive layer. It is preferable to use a hydrophilic binder mainly. A photosensitive material using a binder together with microcapsules is described in JP-A-62-209525.

A photopolymerization initiator may be added to the photosensitive layer of the photosensitive material for the purpose of polymerizing an unpolymerized polymerizable compound after image transfer. For photosensitive materials using photopolymerization initiators,
This is described in JP-A-62-161149.

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

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

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

Incidentally, the photosensitive layer of the photosensitive material comprising the above-mentioned components 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 on the photosensitive material include an image receiving layer, a heating element layer, an antistatic layer, an anti-curl layer, a peeling layer, a cover sheet or a protective layer, a layer containing a base or a base precursor, a base barrier layer, An antihalation layer (colored layer) can be used.

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 to form an image on this layer. The image receiving layer provided on the photosensitive material can have the same configuration as the image receiving layer provided on the image receiving material. Details of the image receiving layer will be described later.

The photosensitive material using the heating element layer is disclosed in
JP-A-294434, JP-A-62-210447 for a photosensitive material provided with a cover sheet or a protective layer, and JP-A-61-96340 for a photosensitive material provided with a layer containing a base or a base precursor. Japanese Patent Application No. 61-24 / 1986 describes a photosensitive material having a colored layer as an antihalation layer.
No. 6901, respectively. In addition, the photosensitive material provided with a base barrier layer is also described in
It is described in -96340. Further, examples of other auxiliary layers and modes of use thereof are described in the above-mentioned series of photosensitive materials.

 Hereinafter, a method for producing a photosensitive material will be described.

Various methods can be used as a method for producing a photosensitive material, but a general production method uses constituents of a photosensitive layer,
A coating solution dissolved, emulsified or dispersed in an appropriate solvent is prepared, and the coating solution is coated on a support as described above.
It comprises a step of obtaining a photosensitive material by drying.

Generally, the coating liquid 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 to include a plurality of components. Some of the components of the photosensitive layer can be added to the liquid composition or the coating solution during or after the preparation. Further, as described below, a method of preparing a secondary composition by further emulsifying an oily (or aqueous) composition containing one or more components in an aqueous (or oily) solvent may be used. .

With respect to the main components contained in the photosensitive layer, methods for preparing a liquid composition and a coating solution are described below.

The preparation of the halogenated emulsion can be carried out by any of known methods such as an acidic method, a neutral method and an ammonia method.

The reaction between the soluble silver salt and the soluble halogen salt may be any of a one-side mixing method, a simultaneous mixing method, and a combination thereof. An inverse mixing method in which grains are formed under silver ion excess conditions and a controlled double jet method in which pAg is kept constant can also be employed. Further, in order to accelerate the grain growth, the concentration, amount or rate of silver salt and halogen salt to be added may be increased (JP-A-55-158124).
Nos. 55-158124 and U.S. Pat. No. 3,650,57).

Silver halide emulsions used in the production of photosensitive materials are surface latent image types in which a latent image is mainly formed on the grain surface,
An internal latent image type formed inside the grains may be used. 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 emulsions suitable for this purpose are:
It is described in U.S. Pat. Nos. 2,592,250 and 3,761,276, Japanese Patent Publication No. 58-3534, and Japanese Patent Application Laid-Open No. 58-136641. Preferred nucleating agents for combining with the above emulsions are
U.S. Pat.Nos. 3,227,552, 4,425,037, 4,255,511
No. 4,260,613, No. 4,276,364 and West German Patent Publication (OLS) No. 2,635,316.

In the preparation of a silver halide emulsion used for producing a light-sensitive material, it is preferable to use a hydrophilic colloid (eg, gelatin) as a protective colloid.

In the silver halide emulsion, at the stage of forming silver halide grains, 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. Etc. can be used. In the process of particle formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, and the like may coexist. Further, for the purpose of improving high illuminance failure and low illuminance failure, a water-soluble iridium salt such as iridium chloride (III or IV) and ammonium hexachloroiridium salt, or a water-soluble rhodium salt such as rhodium chloride can be used.

The soluble salts may be removed from the silver halide emulsion after precipitation or physical ripening. In this case, it can be carried out according to the Nudel washing method or the sedimentation method. Although the silver halide emulsion may be used as it is after unripe, it is usually used after chemical sensitization. A known sulfur sensitization method, reduction sensitization method, noble metal sensitization method and the like can be used alone or in combination in the emulsion for a normal type light-sensitive material. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (Japanese Patent Application Laid-Open No. 58-1983).
-126526 and 58-215644).

When a sensitizing dye is added to a silver halide emulsion, the method described in JP-A-62-947 and Japanese Patent Application No. 61-555 described above may be used.
It is preferably added during the preparation of a silver halide emulsion as in the light-sensitive material described in JP-A No. 10 (1994). When a nitrogen-containing heterocyclic compound is added as a compound having an antifogging function and / or a development accelerating function described above, it may be added at the stage of forming or ripening silver halide grains in the preparation of a silver halide emulsion. Is preferred. A method for producing a light-sensitive material in which a nitrogen-containing heterocyclic compound is added at the stage of forming or ripening silver halide grains is described in JP-A-62-161144.

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

In the production of a photosensitive material, the polymerizable compound can be used as a medium for preparing a composition of other components in the photosensitive 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 in the production of a photosensitive material. In particular, when a color image forming substance is added, it is preferable to include the compound in a polymerizable compound.
Further, as described below, when microdrops of oil droplets of the polymerizable compound are microencapsulated, components such as a wall material necessary for microencapsulation may be included in the polymerizable compound.

A photosensitive composition containing a polymerizable compound containing silver halide can be prepared using a silver halide emulsion.
In addition, in addition to the silver halide emulsion, a silver halide powder prepared by continuous drying or the like can be used for the preparation of the photosensitive composition. These photosensitive compositions containing silver halide can be obtained by stirring with a homogenizer, a blender, a mixer, or another commonly used stirrer.

The polymerizable compound used for preparing the photosensitive composition preferably has a copolymer of a hydrophilic repeating unit and a hydrophobic repeating unit dissolved therein. The photosensitive composition containing the above copolymer is disclosed in
No. 209449 describes this.

Further, instead of using the above copolymer, a photosensitive composition may be prepared by dispersing microcapsules having a silver halide emulsion as a core substance in a polymerizable compound. The photosensitive composition containing microcapsules containing the above silver halide emulsion as a core substance is described in JP-A-62-164041.

The polymerizable compound (including the one containing other components like the above-mentioned photosensitive composition) is preferably used as an emulsion emulsified in an aqueous solvent. In addition, JP
In the case where oil droplets of a polymerizable compound are microencapsulated as in the light-sensitive material described in -275742, a wall material necessary for microencapsulation is added to the emulsion, and the outer shell of the microcapsule is further added. Can be carried out at the stage of this emulsion. Further, a reducing agent or other optional components may be added at the stage of the emulsion.

Incidentally, photosensitive microcapsules that can be used for the production of photosensitive materials are described in JP-A-62-169147 and JP-A-62-169147.
-169148, 62-209437, 62-209438, 62-
209439, 62-209440, 62-209441, 62-20
Nos. 9447 and 62-209442.

When the polymerizable compound is a photosensitive composition containing silver halide in the emulsion of the polymerizable compound described above (including the microcapsule solution subjected to the microencapsulation treatment), the coating solution of the photosensitive material is used as it is. Can be used as Emulsions other than those described above can be mixed with a composition of other components such as a silver halide emulsion and optionally an organic silver salt emulsion to prepare a coating solution. The addition of other components at the stage of this coating solution can be carried out in the same manner as in the above-mentioned emulsion.

The coating material for the photosensitive layer prepared as described above is applied to a support and dried to produce a photosensitive material. The application of the coating solution to the support can be easily carried out according to a known technique.

 Hereinafter, a method of using the photosensitive material will be described.

The photosensitive material is used after being subjected to a development treatment simultaneously with or after the imagewise exposure.

As the above-mentioned exposure method, various exposure means can be used. In general, a line image of silver halide is obtained by imagewise exposure to radiation containing visible light. The type of light source and the exposure amount can be selected according to the photosensitive wavelength of silver halide (in the case of dye sensitization, the sensitized wavelength) and the sensitivity. The original image may be a black and white image or a color image.

The photosensitive material is subjected to a development treatment simultaneously with or after the imagewise exposure. Photosensitive material: Japanese Patent Publication No. 45-11149
Development processing using a developing solution described in Japanese Patent Application Laid-Open Publication No. HEI 7-163, etc. may be performed. Incidentally, as described above, Japanese Patent Application Laid-Open No.
The method described in Japanese Patent No. 69062 has an advantage that the operation is simple and the processing can be performed in a short time because it is a dry processing. Therefore, the latter is particularly excellent as a developing process for the photosensitive material.

As the heating method in the thermal development treatment, various conventionally known methods can be used. Further, as in the case of the photosensitive material described in JP-A-61-294434, a heating element layer may be provided on the photosensitive material and used as a heating means.
Further, as in the image forming method described in Japanese Patent Application Laid-Open No. Sho 62-210461, the heat development may be performed while suppressing the amount of oxygen present in the photosensitive layer. Heating temperature is generally 80 ℃ ~ 20
0 ° C., preferably 100 ° C. to 160 ° C. The heating time is generally 1 second or more, preferably 1 to 5 minutes, and further,
Preferably, it is 1 second to 1 minute.

Instead of including the above-mentioned base or base precursor in the light-sensitive material, development processing may be carried out while adding or immediately after adding the base or base precursor to the photosensitive layer. As a method for adding a base or a base precursor, a method using a sheet containing a base or a base precursor (base sheet) is the easiest and preferable. The image forming method using the base sheet is described in Japanese Patent Application No. 61-176417.

The photosensitive material is subjected to the heat development treatment as described above to polymerize the polymerizable compound in the portion where the silver halide latent image is formed or in the portion where the silver halide latent image is not formed. In the case of a light-sensitive material, the polymerizable compound in the portion where the latent image of silver halide is formed generally polymerizes in the above-mentioned heat development process.
As in the light-sensitive material described in JP-A-70836, 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 not formed.

As described above, the photosensitive material can obtain a polymer image on the photosensitive layer. Alternatively, a dye or pigment can be fixed to the polymer to obtain a dye image.

When the photosensitive material is configured as described in JP-A-62-209444 described above, two types of photosensitive materials that have been subjected to development processing are pressed to break microcapsules and cause a color-forming reaction. A color image can be formed on a photosensitive material by bringing the above substances into contact.

Further, an image can be formed on the image receiving material by using the image receiving material.

Next, the image receiving material will be described. A general image forming method using an image receiving material or an image receiving layer is described in JP-A-61-278849.

Materials that can be used for the support of the image receiving material include glass, paper, woodfree paper, coated paper, cast-coated paper, baryta paper, synthetic paper, metal and its analogs, polyester, acetyl cellulose, cellulose ester,
Examples include films such as polyvinyl acetal, polystyrene, polycarbonate, and polyethylene terephthalate, films laminated with resin materials and polymers such as polyethylene, and papers laminated with resin materials and polymers such as polyethylene. When a porous material such as paper is used as the support of the image receiving material, it is preferable that the image receiving material has a certain degree of smoothness like the image receiving material described in JP-A-62-209530. An image receiving material using a transparent support is described in JP-A-62-209531.

The image receiving material generally has an image receiving layer provided on a support. The image receiving layer is in accordance with the above-described color image-based raw material coloring system and the like.
It can be configured in any form using various compounds. When a polymer image is formed on an image receiving material, 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 above-mentioned support.

For example, when a color developing system including a color former and a developer is used, the image receiving layer can contain a developer.
Further, the image receiving layer may be configured as a layer containing at least one mordant. The mordant may be selected from compounds known in photographic technology and the like in consideration of conditions such as the type of a color image forming substance and used. If necessary, two or more image receiving layers may be constituted by using a plurality of mordants having different mordant powers.

The image receiving layer preferably has a structure containing a polymer as a binder. As the binder, the binder that can be used in the photosensitive layer of the photosensitive material described above can be used. Further, as in the image receiving material described in JP-A-62-209454, a polymer having low oxygen permeability may be used as a binder.

The image receiving layer may contain fine particles of a thermoplastic compound as in the image receiving materials described in Japanese Patent Application Nos. 61-12552 and 61-12553. 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, for the purpose of polymerizing the unpolymerized polymerizable compound, the image receiving layer may contain a photopolymerization initiator or a thermal polymerization initiator. The image receiving material having an image receiving layer containing a photopolymerization initiator is described in JP-A-62-161149, and the image-receiving material having an image receiving layer containing a thermal polymerization initiator is described in JP-A-62-210444. There is a description.

The image receiving layer may be configured as two or more layers according to the functions described above. The thickness of the image receiving layer is 1 to
It is preferably 100 μm, more preferably 1 to 20 μm.

Note that a protective layer may be further provided on the image receiving layer. Further, a layer composed of an aggregate of fine particles of a thermoplastic compound may be provided on the image receiving layer. Japanese Patent Application Laid-Open No. Sho 62-210460 discloses an image receiving material in which a layer comprising an aggregate of fine particles of a thermoplastic compound is further provided on the image receiving layer.

Further, a layer containing an adhesive or an adhesive and a release paper may be sequentially laminated on the surface of the support opposite to the surface on which the image receiving layer is provided. The sticker-shaped image-receiving material having the above constitution is described in JP-A-61-169264 by the present applicant.

The photosensitive material is subjected to development processing as described above, and by applying pressure while the image receiving material is superimposed, an unpolymerized polymerizable compound is transferred to the image receiving material, thereby obtaining a polymer image on the image receiving material. it can. Various known methods can be used for the pressurizing means.

In the embodiment in which the photosensitive layer contains a color image forming substance, the polymerizable compound is polymerized and cured by performing the developing treatment in the same manner, thereby immobilizing the color image forming substance in the cured portion. Then, by applying pressure while the photosensitive material and the image receiving material are overlapped, the color image forming substance in the uncured portion is transferred to the image receiving material, and a color image can be obtained on the image receiving material.

After forming an image on the image receiving material as described above,
The image receiving material may be heated as in the image forming method described in JP-A-62-210459. The above method has the advantage that the unpolymerized polymerizable compound transferred onto the image receiving material is polymerized and the preservability of the obtained image is improved.The present applicant has also described the above using a photosensitive material. Patent applications have already been filed for various image recording devices suitable for carrying out a series of image forming methods. Typical examples of these devices include an exposure device that forms a latent image by imagewise exposure, a heat development device that cures and immobilizes a portion corresponding to the formed latent image, and a developed photosensitive device. A transfer device for superimposing an image receiving material on a material and pressing the same (Japanese Patent Application No. 60-287492); and at least irradiating the image receiving material on which an image is further transferred to the above-described structure with light, With a fixing device that performs either pressurization or heating (Japanese Patent Application No. 60-289703)
and so on.

Sensitive materials include black-and-white or color effects and printing materials, printing materials, printing plates, X-ray materials, medical materials (for example, ultrasonic diagnostic CRT imaging materials), computer graphic hard copy materials, There are many uses such as photosensitive materials for copying machines.

The present invention will be described more specifically with reference to the following examples, but the present invention is not limited thereto. In addition,
In the examples, "parts" means "parts by weight" unless otherwise specified.

[Example 1] [Preparation of photosensitive material] Preparation of paper support (a) 10 parts of LPSP and 75 parts of LBKP were disc-finalized.
Beat to Canadian Freeness 270cc, 0.5 parts of sodium stearate, 0.5 parts of anionic polyacrylamide,
1.5 parts of aluminum sulfate were added to the pulp at an absolute dry weight ratio. Next, a base paper having a basis weight of 70 g / m ² and a thickness of 72 μm was formed from the above stock using a fourdrinier paper machine.

On the surface (felt surface) of the base paper created as described above,
100 parts of hollow sphere-shaped thermoplastic resin fine particles (trade name: Opaque Polymer OP-84J, particle size: 0.55 μm, manufactured by Rohm and Barth Japan KK), SBR latex (trade name: SN-304, Nogatack Co., Ltd.) Co., Ltd.) and 50 parts of petroleum resin (trade name: Carbomule R, manufactured by Dick Hercules Co.) was applied by a knife coater to form a coating solution for forming a coating layer, and the paper support (a) according to the present invention was coated. Created.

Preparation of silver halide emulsion Aqueous gelatin solution (25g gelatin in 1200ml water)
And 3 g of potassium bromide and kept at 70 ° C), 600 ml of an aqueous solution containing 117 g of potassium bromide and an aqueous solution of silver nitrate (0.74 mol of silver nitrate dissolved in 600 ml of water) are added at the same flow rate over 45 minutes did. After 5 minutes from the completion of this, 200 m of an aqueous solution further containing 4.3 g of potassium iodide
was added at an equal flow rate over 5 minutes. After the emulsion was washed with water and desalted, 24 g of gelatin was added and the mixture was stirred at 50 ° C. for 15 minutes to obtain a silver halide emulsion with a yield of 1000 g.

Preparation of W / O Emulsion In 100 g of trimethylolpropane triacrylate, 0.4 g of the following copolymer, bergascript red I-6-B
15 g (manufactured by Ciba-Geigy) was dissolved. In 18 g of this solution, 0.36 g of a surfactant (Nissan Nonion NS 208.5, manufactured by NOF Corporation) was dissolved, and 1.29 g of the following hydrazine derivative (reducing agent), 1.22 g of the following developing agent (reducing agent) and A solution prepared by dissolving 0.015 g of the above antifoggant in 4 g of methylene chloride was added to obtain an oil phase (O).

On the other hand, to 2.0 g of the silver halide emulsion obtained above, 0.45 g of a 10% aqueous solution of potassium bromide was added to obtain an aqueous phase (W).

Next, the aqueous phase (W) was added to the oil phase (O), and the mixture was stirred at 15,000 rpm for 5 minutes using a homogenizer to obtain a W / O emulsion.

Preparation of Polyurea Resin-Melamine / Formaldehyde Resin Wall Capsule Dispersion Solution A 5% aqueous solution of a partial sodium salt of polyvinylbenzenesulfonic acid (VERSA, AGS1953, manufactured by National Starch) was adjusted to pH 3.5 with a 20% aqueous solution of phosphoric acid. This aqueous solution 4
In 0 g, 0.9 g of Takenate D110N (a polyisocyanate compound, manufactured by Takeda Pharmaceutical Co., Ltd.) was added to the above W / O emulsion and mixed well, and the mixture was added at 40 ° C. using a homogenizer at 7000 rpm. For 30 minutes. A thin outer shell of polyurea resin was formed around the oil phase of the W / O / W emulsion formed here.

Separately, 13.2 g of melamine, 37% formaldehyde aqueous solution 2
1.6 g and 70.8 g of water were heated and stirred at 60 ° C., and after 30 minutes, a transparent melamine-formaldehyde initial condensate was obtained.

12.9 g of the above-mentioned initial condensate is added to the above-mentioned W / O / W emulsion (covered with a thin polyurea film), mixed and adjusted to pH 6.0 with a 20% aqueous phosphoric acid solution with stirring, and the liquid temperature is adjusted to 65 ° C. And stirring was continued for 90 minutes to prepare a microcapsule solution in which a melamine / formaldehyde resin was deposited on the outer shell of the polyurea membrane. Further, in order to remove formaldehyde remaining in the capsule solution, 5.4 g of a 40% aqueous urea solution was added, the pH was adjusted to 3.5 with a 20% aqueous phosphoric acid solution, and stirring was continued for 40 minutes. After the completion of the reaction, the capsule solution was adjusted to pH 7.0 with a 10% aqueous sodium hydroxide solution and cooled.

Preparation of photosensitive material (A) A surfactant (Nissan Nonion NS 208.5, manufactured by NOF Corporation) was added to 10 g of the microcapsule solution prepared above.
0.7g, 20% aqueous solution of solid dispersion of the following base precursor
2.7 g, sorbitol 20% aqueous solution 3 cc, 20 of the following thermal solvents
1.3% of an aqueous solution (methanol / water = 50: 50 volume ratio) was added to prepare a coating solution for forming a photosensitive layer.

Next, the above coating solution is applied to the surface of the paper support (a) prepared as described above using a # 20 coating rod, dried at about 40 ° C., and dried according to the present invention.
It was created.

[Preparation of image-receiving material] 40% sodium hexametaphosphate aqueous solution in 125 g of water 11
g, and then 34 g of zinc 3,5-di-α-methylbenzylsalicylate and 82 g of a 55% calcium carbonate slurry were mixed and coarsely dispersed by a mixer. The liquid was dispersed with a Dynomill disperser, and 50% SBR latex 6 was added to 200 g of the obtained liquid.
g and 55 g of 8% polyvinyl alcohol were added and mixed uniformly. Next, this mixed solution is applied to the surface of the same paper support (a) as the paper support (a) for the photosensitive material obtained as described above.
After evenly applying so as to have a wet film thickness of 30 μm,
After drying, an image receiving material was prepared.

Example 2 Preparation of Paper Supports (b) and (c) In the preparation of the paper support (a) of Example 1, the following first
Except for forming a coating layer having the composition shown in the table, and further forming an undercoat layer having the composition shown in the following Table 1 on the coating layer, the paper support corresponding to each was carried out in the same manner as in Example 1. The bodies (b) and (c) were made.

In Table 1, as hollow sphere-shaped thermoplastic resin fine particles, trade name: Boncoat PP-2000 (particle size: 0.40 μm, manufactured by Dainippon Ink and Chemicals, Inc.), and vinylidene chloride latex And trade name: Saran Latex L-511 (manufactured by Asahi Kasei Kogyo Co., Ltd.).

Preparation of photosensitive materials (B) and (C) Except for using the paper supports (b) and (c) prepared as described above, in the same manner as in Example 1, the photosensitive materials (B) and (C) was prepared.

Comparative Example 1 Preparation of Paper Support (d) In the preparation of the paper support (a) of Example 1, the same procedure as in Example 1 was carried out except that no coating layer was provided and no undercoat layer was provided. Thus, a paper support (d) was prepared.

Photosensitive material (D) A photosensitive material for comparison (D) was prepared in the same manner as in Example 1 except that the paper support (d) prepared as described above was used.
It was created.

[Comparative Examples 2 and 3] Preparation of Paper Supports (e) and (f) In the preparation of the paper support (a) of Example 1, the following first
Example 1 was repeated except that a coating layer having the composition shown in the table was formed.
Paper supports (e) and (f) corresponding to each were prepared in the same manner as described above.

In Table 1, as clay, trade name: UV
-90 (particle size: 2.7 µm, manufactured by Engelhardt) was used.

Photosensitive Materials (E) and (F) Photosensitive materials for comparison (E) and (F) in the same manner as in Example 1 except that the paper supports (e) and (f) prepared as described above were used. It was created.

Comparative Example 4 Preparation of Paper Support (g) In the preparation of the paper support (a) of Example 1, the following first
A paper support (g) was prepared in the same manner as in Example 1 except that a coating layer having the composition shown in Table 1 was formed and an undercoat layer having the composition shown in Table 1 below was further formed on the coating layer. It was created.

In Table 1, as the calcined kaolin, Ansilex 90 (particle size: 3.1 μm, manufactured by Engelhardt Co., Ltd.) was used.

Photosensitive material (G) A comparative photosensitive material (G) was prepared in the same manner as in Example 1 except that the paper support (g) prepared as described above was used.
It was created.

In the process of producing the photosensitive material, the flatness and the water resistance of the surface of the paper support (a) to (g) (the surface of the coating layer or the undercoat layer) used for each photosensitive material were evaluated.

The flatness of the surfaces of the paper supports (a) to (g) was visually evaluated on a six-point scale of A to F. The six steps A to F indicate that A has the best flatness, and A, B, C, D,
It shows that the flatness is inferior in the order of E and F.

Further, the water resistance of the surfaces of the paper supports (a) to (g) was evaluated by measuring the water absorption of the cups (defined by JIS-P-8140). The lower the water absorption, the higher the water resistance.

 Table 1 summarizes the above results.

[Image formation and evaluation thereof] Each of the photosensitive materials obtained in Examples 1 to 3 and Comparative examples 1 to 4 was subjected to the following image forming method to obtain (1) uneven transfer, and (2) image density of a white background portion. (Lowest density) and (3) resolution were evaluated respectively.

(1) Transfer unevenness The photosensitive material is 1 lux at 60 lux using a tungsten bulb.
After uniform exposure for 2 seconds, the film was heated on a hot plate heated to 150 ° C. for 10 seconds. Next, the photosensitive material and the image receiving material were overlapped and passed through a pressure roller of 250 kg / cm ^{2 and} a pressure roller of 700 kg / cm ² to obtain a positive magenta color image on the image receiving material.

With respect to the image on the image receiving material obtained as described above, the state of transfer unevenness was visually observed, and the results are shown in Table 2 below.

However, the numerical value in the column of “Pressure” shown in Table 2 indicates the number of transfer unevenness having a diameter of 1 mm or more existing in a color image within a circle having a diameter of 4 cm at each transfer pressure.

(2) Image density (minimum density) on white background Using a tungsten bulb as the photosensitive material, at 500 lux,
After exposure for 1 second through a filter having a continuously changing density, it was heated for 10 seconds with a heat roller type heating and developing machine heated to 150 ° C. Next, the photosensitive material was superimposed on the image receiving material and passed through a pressure roller of 500 kg / cm ² , and the density of the image receiving material surface was measured by a Macbez reflection densitometer. The results are shown in Table 2 below.

However, in Table 2, the development of the photosensitive material D for comparison did not proceed (indicated by *).

(3) Resolution The photosensitive material was exposed through a black and white transparent positive image at various exposure amounts using a tungsten light bulb, and then heated on a hot plate heated to 150 ° C. for 10 seconds. Next, the photosensitive material was superimposed on the image receiving material and passed through a pressure roller of 500 kg / cm ² to obtain a magenta image on the image receiving material. The resolution of the obtained image was measured. The results are shown in Table 2 below.

As is clear from the results in Table 2, when the above-described image forming method was performed using the photosensitive material according to the present invention having a coating layer containing a hollow spherical thermoplastic fine powder, the obtained image was transferred to the obtained image. There was little unevenness and high resolution was shown.

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Claims (2)

(57) [Claims] 1. A photosensitive material having a photosensitive layer containing a silver halide, a reducing agent and a polymerizable compound on a paper support, wherein the paper support comprises hollow sphere-shaped thermoplastic resin fine particles and a binder on base paper. A light-sensitive material, which is a paper support having a coating layer on the side of the light-sensitive layer. 2. The light-sensitive material according to claim 1, wherein said binder is a hydrophobic polymer.