JPS63158542A - Photosensitive material - Google Patents

Abstract

PURPOSE:To reduce the generation of transfer unevenness, even in case of using a low transfer pressure by using an original paper which is specified the total range of the wt.% of 24 mesh residue and the wt.% of 42 mesh residue according to the distribution of fibre lengths defined by JIS-P-8207, as the paper base material. CONSTITUTION:The paper base material is made of the original paper having such the distribution of the fibre lengths that the total of the wt.% of 24 mesh residue and the wt.% of 42 mesh residue is 30-60%, according to the distribution of the fibre lengths defined by JIS-P-8207. A photosensitive layer contg. a halogenide type reducing agent and a polymerizable compd. is provided on the paper base material. Thus, the clear transfer image having less tendency for generating the transfer unevenness, even in case of using a relatively low transfer pressure can be obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of the Invention] The present invention relates to a photosensitive material having a photosensitive layer containing silver halide, a reducing agent, and a polymerizable compound on a support. Furthermore, the present invention also relates to a photosensitive material having a photosensitive layer containing a photopolymerizable composition or a photopolymerizable compound on a support.

[Background of the Invention] A photosensitive material having a photosensitive layer containing silver halide, a reducing agent, and a polymerizable compound on a support forms a latent image of silver halide and polymerizes the polymerizable compound by the action of the reducing agent. It can be used in image forming methods.

Examples of image forming methods are described in Japanese Patent Publications Nos. 45-11149, 47-20741, 49-10697, and 57-138632 and 58-169143. In these methods, when exposed silver halide is developed using a developer, coexisting polymerizable compounds (e.g.

(vinyl compound) starts polymerization to form an image-like polymer compound. Therefore, the above method.

Development processing using a liquid was required, and the processing required a relatively long time.

As an improvement on the above method, Japanese Patent Application Laid-Open No. 61-69062 describes a method in which a polymer compound can be formed by dry treatment. This method uses a photosensitive silver salt (silver halide), a reducing agent, a crosslinking compound (polymerizable compound)
A latent image of a photosensitive silver salt is formed by imagewise exposing a recording material (photosensitive material) in which a photosensitive layer consisting of a binder and a binder is carried on a support to form a latent image, and then thermally developing it. A polymer compound is formed on the exposed portion.

Regarding the above dry image forming method, please refer to Japanese Patent Application Laid-Open No. 61-73
No. 145, No. 61-183640, No. 61-1885
There are also descriptions in each publication No. 35.

These image forming methods are methods of polymerizing a polymerizable compound in a portion where a silver halide latent image is formed.

In addition, the present inventors have also invented a method for polymerizing the polymerizable compound in areas where no latent image of silver halide is formed, and this invention has also already been patented (Japanese Patent Application No. 60-210657). In this method, by heating, a reducing agent acts on the area where the latent image of silver halide is formed, suppressing the polymerization of the polymerizable compound, and at the same time promoting the polymerization of other areas. be.

A photosensitive material having a photosensitive layer containing a photopolymerizable composition or a photopolymerizable compound on a support is used in an image forming method in which a polymer compound is formed in an exposed area by imagewise exposure. Regarding the above-mentioned image forming method and photosensitive materials used therein, Japanese Patent Application Laid-open Nos. 52-89915 and 57-
No. 179836, No. 58-88739, No. 58-88
No. 740 and No. 60-259490 have descriptions thereof.

As one aspect of the image forming orientation described above, after a polymer compound is imagewise formed on a photosensitive material, unpolymerized polymerizable compounds (or photopolymerizable composition or photopolymerizable compound, hereinafter the same)
There is a method of transferring the image to an image-receiving material and forming an image on the image-receiving material. In the above transfer-type image forming method, a photosensitive material containing silver halide and a polymerizable compound in microcapsules, or a photosensitive material containing a photopolymerizable composition or a photopolymerizable compound in microcapsules is particularly preferably used. . Regarding the above-mentioned transfer type image forming method, JP-A-61-73145, JP-A-58-88739,
There are descriptions in Publications No. 58-88740 and No. 60-259490.

On the other hand, paper is sometimes used as a support for photosensitive materials because it is inexpensive, easily disposable, lightweight, and easy to handle. However, when an image is obtained on an image-receiving material by the above-mentioned transfer-type image forming method using a paper support, if the transfer pressure is low, the concentration of the polymerizable compound is low in the area where the polymerizable compound is to be transferred by several millimeters. There were cases where some degree of uneven transfer occurred.

[Summary of the Invention] An object of the present invention is to provide a photosensitive material in which the above-mentioned transfer unevenness hardly occurs even with a relatively low transfer pressure, even though a single paper support is used. be.

The present invention relates to a photosensitive material comprising a photosensitive layer containing silver halide, a reducing agent, and a polymerizable compound on a paper support, wherein the paper support is made of fibers defined by JIS-P-8207. A photosensitive paper support using a base paper having a fiber length distribution such that the sum of the weight percent of the 24 mesh residue and the weight percent of the 42 mesh residue is 30 to 60%. It provides materials.

Furthermore, the present invention is a photosensitive material comprising a paper support and a photosensitive layer containing a photopolymerizable composition or a photopolymerizable compound.

The paper support has a fiber length distribution defined by JIS-P-8207 such that the sum of the weight percent of the 24 mesh residue and the weight percent of the 42 mesh residue is 30 to 60%. The present invention also provides a photosensitive material characterized in that it is a paper support using a base paper having the following properties.

The present invention is particularly effective in embodiments in which silver halide and a polymerizable compound are contained in microcapsules, or in embodiments in which a photopolymerizable composition or a photopolymerizable compound is contained in microcapsules.

[Effects of the Invention] The photosensitive material of the present invention is characterized by using a paper support using a base paper having the fiber distribution defined above.

Through research conducted by the present inventors, it has been found that the occurrence of transfer unevenness as described above when using a photosensitive material having a paper support is
This problem can be solved by using a paper support using a base paper having the fiber length distribution specified above. That is,
Weight% of 24 mesh residue and weight% of 42 mesh residue
If a base paper with a large long fiber content in which the sum of the long fiber content exceeds 60% is used, so-called uneven formation will occur on the paper support.

For this reason, it has been found that when the pressure during transfer is low, unevenness occurs in the transfer pressure distribution due to formation unevenness, and as a result, the above-mentioned transfer unevenness occurs on the image-receiving material.

The light-sensitive material of the present invention uses a paper support using a base paper with a low long fiber content in which the sum of the weight (d[%) of the 24 mesh residue and the weight % of the 42 mesh residue is 60% or less. ,
A clear transferred image with less occurrence of transfer unevenness can be obtained even with a relatively low transfer pressure.

Note that base paper with an extremely low long fiber content in which the sum of the weight percent of the 24-mesh residue and the fffffi% of the 42-mesh residue is less than 30% is difficult to use in the image forming method described above. It becomes difficult to maintain the paper strength required as a paper support in the case of paper.The present invention is based on the premise that the image forming process can be carried out easily, and it is possible to obtain a clear transferred image with less occurrence of transfer unevenness. It provides photosensitive materials.

In addition, in an embodiment in which silver halide and a polymerizable compound are accommodated in microcapsules, or in an embodiment in which a photopolymerizable composition or a photopolymerizable compound is accommodated in microcapsules, uncured microcapsules ( It destroys the polymerizable compound (or the photopolymerizable composition or the photopolymerizable compound is in an unpolymerized state). Therefore, the embodiment using microcapsules as described above.

When the pressure distribution of the transfer is uneven, the state of destruction of the microcapsules is also uneven, so the transfer unevenness is further amplified. When the paper support according to the present invention is used, the unevenness of the state of destruction of the microcapsules is increased. Occurrence can also be reduced.

Results 1 The present invention can achieve particularly remarkable effects in embodiments using microcapsules as described above.

[Detailed Description of the Invention] The photosensitive material of the present invention has a paper support.
In this specification, it means ``base paper J'' or a sheet-like product in which an arbitrary coating layer is provided on a base paper.

The base paper used for the paper support of the photosensitive material of the present invention is JIS-
The fiber length distribution defined by P-8207 is such that the sum of the weight percent of the 24 mesh residue and the weight percent of the 42 mesh residue is 30 to 60%. In addition, it is more preferable that the weight percent of the 24 mesh residue is 10% or less.

The fiber length distribution specified by the above JIS-P-8207 (test method for determining the sieve content of pulp for papermaking) is determined by thoroughly disintegrating a sample of 10g as an absolute dry weight using a standard refractory machine, and then determining the pulp sieve content using a testing machine. (commercially available from Toyo Seiki Seisakusho, etc.) for 15 minutes.

24 mesh (nominal size, 710 l), 42 mesh (
350 JL), 80 Metsuyu (177 pots), 150
Each residue in the four layers of the mesh (105 ml) was determined as a percentage (wt%) relative to the weight of the original sample. Therefore, a small amount of 24 mesh residue and 42 mesh residue means that the long fiber content is small in the base paper.

Below, the structure of the paper support used in the present invention and t'im
A specific means for keeping the i-distribution within the specified range described above will be explained.

The base paper used for the paper support uses wood pulp as its main raw material, and is manufactured by making paper from this. As wood pulp, LBKP
, NBKP, LBSP, NBSP, LDP, NDP, L
Both UKP and NUKP can be used, but LBKP, LBSP, NBSP, LDP, and ND with high short fiber content can be used.
It is preferable to use a large amount of P, especially LBSP which has a high short fiber content before beating and is easily converted into short fibers by beating.
It is preferable to use LBSP and/or LDP in an amount of 5% by weight or more. However, in order to maintain paper strength as a paper support, the amount of LBSP and/or LDP used is preferably 60% by weight or less.

If necessary, a part of the wood pulp may be replaced with other vegetable fiber pulps such as straw, esparto, bagasse, and kenaf, synthetic pulps made of polyethylene, polypropylene, etc., or synthetic pulps made of vinylon, polyester, acrylic fibers M, etc. May be replaced with fiber.

When beating pulp, the freeness is 20 according to the CSF standard.
It is preferable to beat it so that it becomes 0 to 4 oocc, and more preferably to beat it so that it becomes 250 to 350 cc. As the beating machine, it is preferable to use a beater, a conical refiner, or a disc refiner, especially A di-Jordan type conical refiner is preferred. When using a commonly used disc refiner, it is necessary to adjust the refining plate, the number of revolutions of the disc, the refining load, the pulp concentration during refining, the pulp flow rate, etc. preferable.

Various internal chemicals can be added to the base paper. Examples of internally added chemicals include fillers such as calcium carbonate, talc, clay, kaolin, titanium dioxide, and urea resin particles;
Internal sizing agents such as rosin, paraffin wax, higher fatty acid salts, alkenyl succinates, fatty acid anhydrides, and alkyl ketene dimers; Paper strength agents such as polyacrylamide, starch, polyvinyl alcohol, and melamine formaldehyde condensates: maleic anhydride Examples include a reaction product of a copolymer and a polyalkylene polyamine, a softening agent such as a quaternary ammonium salt of a higher fatty acid; a fixing agent such as sulfuric acid; a colored dye; a fluorescent dye.

The base paper used for the paper support can be made using a fourdrinier paper machine or a cylinder paper machine using the base paper as described above. The weight of IX paper is 20 to 200 g/rrf
The thickness of the base paper is preferably 25 to 250 g/rn', particularly preferably 30 to 100 g/rn'.
JLrn is preferred, and 40 to 150 gm is particularly preferred.

Also, for the base paper, for the purpose of improving smoothness.

It is preferable to carry out a calendering process such as on-machine calendering in a paper machine or super calendering after papermaking.From the above calendering process, the density of the base paper is 0.7 according to JIS-P-8118. 〜1、
2g/lr? It is preferable that the value is 0.85 to 1.
．． It is particularly preferable that it be lOg/rn'.

The fiber length distribution of the produced base paper can be adjusted by the method of producing base paper as described above, especially by selecting the type of raw material pulp, adjusting the pulp beating method, etc.
The distribution can be such that the sum of the weight percentage of the two mesh residues is 30 to 60%.

In the photosensitive material of the present invention, the above-mentioned base paper can be used as a paper support as it is, but it is also possible to use a base paper with a coating layer of a hydrophobic polymer on one or both sides as a paper support. is even more preferable. The coating layer of the hydrophobic polymer may be provided on one side or both sides of the base paper as a structure in which multiple layers are stacked one on top of the other.

Note that a known surface sizing agent may be applied to the surface of the base paper, and a coating layer of hydrophobic polyester may be provided thereon. Examples of surface sizing agents include polyvinyl alcohol, starch, polyacrylamide, gelatin, and casein. , styrene maleic anhydride copolymer, alkyl ketene dimer, polyurethane, epoxidized fatty acid amide, and the like.

The hydrophobic polymer used for the coating layer has a glass transition point of 12
Polymers between 0°C and 50°C are preferred.

The polymer may be a homopolymer or a copolymer, and in the case of a copolymer, it is sufficient that it is hydrophobic as a whole even if it has hydrophilic repeating units in part. Examples of the hydrophobic polymer include vinylidene chloride, Styrene-butadiene copolymer, methyl methacrylate-butadiene copolymer, acrylonitrile-butadiene copolymer, styrene-acrylic ester fist copolymer, methyl methacrylate-acrylic ester copolymer, and styrene-methacrylate-acrylic ester copolymer, etc. I can do it.

It is more preferable to form a crosslinked structure in the hydrophobic polymer.To form a crosslinked structure in the hydrophobic polymer, 1) Add a known curing agent (crosslinking agent) together with the hydrophobic polymer to the paper support manufacturing process. Examples of the above curing agents that may be used include 1,3-bis(vinylsulfonyl)-2
-Active vinyl compounds such as propatool and methylene bismaleimide: 2,4-dichloro-6-hydroxy-S-
) riazine sodium salt, 2,4-dichloro-6-hydroxy-5-)riazine, N,N'-bis(2-chloroethylcarbamyl)piperazine, and other active halogen compounds: bis(2,3-epoxy Epoxy compounds such as (propyl) methylpropylammonium p-toluenesulfonate; and methanesulfonic acid ester compounds such as 1,2-di(methanesulfonoxy)ethane.

The hydrophobic polymer coating layer has the following properties: improving the smoothness of the coating layer,
Pigments may be added for the purpose of facilitating layer formation during production, etc. The above pigments include known coated papers (coated papers,
Pigments used for art paper, baryta paper, etc.) can be used. Examples of pigments include titanium dioxide, barium sulfate, talc, clay, kaolin, calcined kaolin,
Examples include inorganic pigments such as aluminum hydroxide, amorphous silica, crystalline silica, and synthetic alumina silica; and organic pigments such as polystyrene resin, acrylic resin, and urea-formalin resin.

A waterproofing agent may be further added to the coating layer of the hydrophobic polymer. Examples of the waterproofing agent include polyamide polyamine epichlorohydrin resin, polyamide polyurea resin, glyoxal resin, and the like. Among these, formalin-free polyamide polyamine epichlorohydrin resins and polyamide polyurea resins are particularly preferred.

The coating layer of the hydrophobic polymer as described above can be easily formed by coating the base paper with a latex-like coating liquid prepared by dissolving, dispersing, or emulsifying components such as the hydrophobic polymer, curing agent, pigment, and waterproofing agent. It can be provided in As a method for applying the coating liquid onto the base paper, a known dip coating method, air knife coating method, curtain coating method, roller coating method, doctor coating method, gravure coating method, etc. can be used.

The coating layer of hydrophobic polymer is 3g/m? Application amount (
If multiple layers are provided, it is preferable to provide the total amount) on the base paper, and the more preferable coating amount is 5 to 30 g/rrf.
It is.

In addition, 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 performed during or after coating the above-mentioned coating layer.

The following margins describe the photosensitive layer provided on the above-mentioned support, that is, the photosensitive layer containing silver halide, a reducing agent, and a polymerizable compound, and each component of the photosensitive layer containing a photopolymerizable composition or a photopolymerizable compound. will be explained in order.

Light-sensitive materials contain silver chloride, silver bromide, silver halide,
Any grains of silver iodide, silver chlorobromide, silver chloroiodide, silver chloroiodide, or 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 multiple structures with different compositions on the surface and inside, Japanese Patent Application Laid-open Nos. 57-154232 and 58-10853 disclose
No. 3, No. 59-48755, No. 59-52237, U.S. Patent No. 4433048 and European Patent No. 1
There are descriptions in each specification of No. 00984. In addition, the special request for
Silver halide grains having a high proportion of silver iodide in the shell portion may be used, as in the photosensitive material described in Japanese Patent No. 25576.

There is no particular restriction on the crystal habit of the silver halide grains; for example, tabular grains having an aspect ratio of 3 or more may be used, as in the light-sensitive material described in Japanese Patent Application No. 55509/1982.

The above-mentioned silver halide grains are disclosed in Japanese Patent Application No. 61-2
It is preferable to use silver halide grains having a relatively low fog value, such as the photosensitive material described in No. 14580.

For the silver halide used in the photosensitive material, two or more types of silver halide grains having different halogen compositions, crystal habits, grain sizes, etc. can be used in combination.

There is no particular restriction on the grain size distribution of silver halide grains. For example, as in the photosensitive material described in Japanese Patent Application No. 61-55508, monodisperse silver halide grains with a substantially uniform grain size distribution are used. May be used.

In the light-sensitive material, the average grain size of the silver halide grains is preferably from o, ooi to 5 pm, and from 0.
More preferably, it is 0.001 to 2 pm.

The amount of silver halide contained in the photosensitive layer is calculated in terms of silver including organic tJ1 salt, which is an optional component described below.

It is preferable to set it in the range of 0.1 mg to 10 g/rrf, and in terms of silver of only silver halide, 0.1 g
/go or less, preferably from 1mg to 90mg/
It is particularly preferable to set it to rrr'.

A reducing agent that can be used in a light-sensitive material has a function of leaving behind silver halide and/or a function of promoting (or suppressing) polymerization of a polymerizable compound. As the reducing agent having the above-mentioned 4!1 moat, there are various kinds of substances. The reducing agents include hydroquinones, catechols, p-aminophenols, p-phenylenediamines, 3-pyrazolidones, 3-aminopyrazoles, 4-amino-
5-pyrazolones, 5-aminouracils, 4゜5-dihydroxy-6-aminopyrimidines, reductones,
Amyl reductones, 0- or p-sulfonamidophenols, 0- or p-sulfonamidonaphthols, 2-sulfonamidoindanones, 4-sulfonamido-5-pyrazolones, 3-sulfonamidoindoles, sulfonamides Pyrazolobenzimidazoles,
Examples include sulfonamide pyrazolotriazoles, α-sulfonamide ketones, and hydrazines. By adjusting the type, amount, etc. of the reducing agent, it is possible to polymerize the polymerizable compound in either the area where the silver halide latent image is formed or the area where no latent image is formed.

In addition, in a system in which a polymerizable compound is polymerized in a portion where a silver halide latent image is not formed, it is particularly preferable to use l-phenyl-3-pyrazolidones as the reducing agent.

Regarding various reducing agents having the above functions, please refer to JP-A-61-183640, JP-A No. 61-188535, and JP-A-61-188535.
Publications No. 1-228441 and Japanese Patent Application No. 1986-2
No. 10657, No. 60-226084, No. 460-22
No. 7527, No. 60-227528, No. 61-427
There are descriptions in each specification of No. 46 (including those described as a developer or a hydrazine derivative). Regarding the above-mentioned reducing agent, please refer to 'The Theo' by T. James.
ry or thePhotographic Pro
cess'' 4th edition, pp. 291-334 (1977),
Research Disclosure Magazine Vol.1.170.19
No. 17029 (pages 9-15) of June 1978, and Vol. 1.176 of the same magazine, No. 17643 of December 1978
No. (pages 22-31). In addition, the special request for
In place of the reducing agent, a reducing agent precursor capable of releasing the reducing agent under heating conditions or in contact with a base may be used, as in the photosensitive material described in the specification of No. 55505. The reducing agents and reducing agent precursors described in the respective specifications and literature described in ``2'' can also be effectively used in the photosensitive materials. Therefore, the term "rH source agent" in this specification includes the reducing agents and reducing agent precursors described in each of the above-mentioned publications, specifications, and literatures.

These reducing agents may be used alone, but as described in the specifications in -1-, two or more reducing agents may be used in combination. When using the above reducing agents together, the interaction of the reducing agents is, firstly,
secondly, promoting the reduction of silver halide (and/or organic silver salts) by so-called superadditivity; It is conceivable that the oxidant causes polymerization of the polymerizable compound (or suppresses the polymerization) via an oxidation-reduction reaction with another reducing agent in which the oxidant coexists. However, during actual use, the above reactions can occur simultaneously.

It is difficult to specify which effect is responsible.

Specific examples of the reducing agent include pentadecylhydroquinone, 5-t-butylcatechol, p-(N, N-
diethylamino)phenol, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, l-phenyl-4-methyl-4-heptaderelponyloxymethyl-3-pyrazolidone, 2-phenylsulfonylamine-4- Hexadecyloxy-5-t-octylphenol, 2-phenylsulfonylamine-4-t-butyl-5-hexadecyloxyphenol, 2-(N
-butylcarbamoyl)-4-phenylsulfonylaminenaphthol, 2-(N-methyl-N-octadecylcarbamoyl)-4-sulfonylaminonaphthol, l-
7cetyl-2-phenylhydrazine, l-acetyl-2
-((p or O)-aminophenyl)hydrazine, 1
-formyl-2-((p or 0)-7minophenyl)
Hydrazine, 1-acetyl-2-((p or 0)-methoxyphenyl)hydrazine, 1-lauroyl-2-(
(p or 0)-aminophenyl) hydrazine, 1-
Trityl-2-(2,6-dichloro-4-cyanophenyl)hydrazine, 1-)lythyl-2-phenylhydrazine, l-7enyl-2-(2,4,6-drichlorophenyl)hydrazine, 1-(2 -(2,5-di-t-pentylphenoxy)butyroyl) -2-((p or 0)-aminophenyl)hydrazine, 1-(2-(2,
5-di-t-pentylphenoxy)butyroyl)-2-
((p or 0)-aminophenyl)hydrazine pentadecylfluorocaprylate, 3-indazolinone,
1-(3,5-dichlorobenzoyl)-2-phenylhydrazine, l-trityl-2-[((2-N-butyl-
N-octylsulfamoyl)-4-methanesulfonyl)phenyl]hydrazine, 1-(4-(2,5-di-t)
-pentylphenoxy)butyroyl)-2-((p or 0)-methoxyphenyl)hydrazine, i-(methoxycarbonylbenzohydryl)-2-phenylhydrazine.

1-Formyl-2-[4-(2-(2,4-di-t-pentylphenoxy)butyramido)phenyl]hydrazine, l-acetyl-2-[4-(2-(2,4-di-t
-pentylphenoxy)butyramido)phenyl]hydrazine, l-trityl-2-[(2,6-dichloro-4
-(N.

N-cy2-ethylhexyl)carbamoyl)phenyl] hydrazine, l-(methoxycarbonylbenzohydryl)-2-(2,4-dichlorophenyl)hydrazine, i-trityl-2-[(2-(N-ethyl-N -octylsulfamoyl)-4-methanesulfonyl)phenyl]hydrazine, l-benzoyl-2-tritylhydrazine, 1-(4-butoxybenzoyl)-2-1lythylhydrazine, 1-(2,4-dimethoxybenzoyl) −
2-1 lytylhydrazine, 1-(4-dibutylcarbamoylbenzoyl)-2-tritylhydrazine, and 1
-(l-naphthoyl)-2-tritylhydrazine and the like can be mentioned.

In the photosensitive material, the reducing agent contains 1 mol of silver (including the aforementioned silver halide and an organic silver salt which is a component of a).
It is preferable to use it in a range of 0.1 to 1500 mol%.

The polymerizable compound that can be used in the photosensitive material is not particularly limited, and any known polymerizable compound can be used. In addition, when using a photosensitive material, if heat development processing is planned, it is necessary to use a material with a high boiling point (e.g., 8
℃ or above), and the embodiment in which the photosensitive layer contains a color image-forming substance as an optional component described below is intended to immobilize the color image-forming substance by polymerizing and curing the polymerizable compound. Therefore, it is preferable that the polymerizable compound is a crosslinkable compound having a plurality of polymerizable compounds in the molecule.Also, as will be described later, when forming a transferred image using an image-receiving material, 61-15007
It is preferable to use a highly viscous substance as the polymerizable compound, as in the photosensitive material described in No. 9.

Note that polymerizable compounds that can be used in photosensitive materials are described in the application specifications for the series of photosensitive materials described above and below.

Polymerizable compounds used in photosensitive materials generally have addition polymerizability or ring-opening polymerizability. Examples of the compound having addition polymerizability include compounds having an ethylenically unsaturated group, and compounds having ring-opening polymerizability include compounds having an epoxy group, and compounds having an ethylenically unsaturated group are particularly preferred.

Compounds with ethylenically unsaturated groups that can be used in photosensitive materials include acrylic acid and its salts, acrylic esters, acrylamides, methacrylic acid and its salts, methacrylic esters, methacrylamides, and maleic anhydride. Examples include acids, maleic esters, itaconic esters, styrenes, vinyl ethers, vinyl esters, N-vinyl compound Xis, allyl ethers, allyl esters, and derivatives thereof.

Specific examples of polymerizable compounds that can be used in photosensitive materials include n-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, furfuryl acrylate, ethoxyethoxyethyl acrylate, Dicyclohexyloxyethyl acrylate, nonylphenyl diethyl acrylate, hexanediol diacrylate, butanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate,
Examples include diacrylate of polyethylene diethylene bisphenol A, polyacrylate of hydroxy polyether, polyester acrylate, and polyurethane acrylate.

Other specific examples of methacrylic acid esters include methyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, butanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, Methacrylate and dimethacrylate of polyoxyalkylenated bisphenol A can be mentioned.

- The synthetic compounds described in - may be used alone or in combination of two or more. A light-sensitive material using a combination of two or more types of polymerizable compounds is described in Japanese Patent Application No. 55504/1983. Note that a substance in which a polymerizable functional group such as a vinyl group or a vinylidene group is introduced into the chemical structure of the 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 mentioned above, the use of a reducing agent and a polymerizable compound, or a substance that functions as a color image forming substance and a polymerizable compound, is of course included in the yE type of photosensitive material.

In the photosensitive material, the polymerizable compound is halogenated IM1
It is preferable to use it in the range of 50,000 to 120,000 parts by weight, and the more preferable range is 10 to 100,000 parts by weight.
000 parts by weight.

Instead of the structure of the photosensitive layer containing silver halide, a reducing agent, and a polymerizable compound as described above, a photosensitive layer containing a photopolymerizable composition may be used.

The above photopolymerizable composition can use a mixture of a photopolymerization initiator and a polymerizable compound. The polymerizable compounds that can be used in the photopolymerizable composition are the same as those described above.

Examples of preferred photoinitiators include α-alkoxyphenyl ketones, polycyclic quinones, benzyphenones and substituted benzophenones, xanthones, thioxanthones, halogenated compounds (e.g., chlorosulfonyl and chloromethyl aromatic compounds, chlorosulfonyl and chloromethyl heterocyclic compounds, chlorosulfonyl and chloromethylbenzophenones, and fluorescein 77), haloalkanes, α-halo α-phenylacetophenones, photoreducible dye-reducible redox couple Examples include halogenated paraffins (eg, brominated or chlorinated paraffins), benzoyl alkyl ethers, and lophine dimer-mercapto compound couples.

Specific examples of preferred photoinitiators include benzoylbutyl, 2,2-dimethoxy-2-phenylacetophenone, 9,10-anthraquinone, benzphenone, Michler's ketone, 4.4''-diethylaminobenzophenone, xanthone, chloroxanthone, thioxanthone. , chlorothioxanthone, 2,4-diethylthioxanthone, chlorosulfonylthioxanthone, chlorosulfonylanthraquinone, chloromethylanthracene, chloromethylbenzothiazole, chlorosulfonylbenzoxazole, chloromethylquinoline, chloromethylbenzophenone, chlorosulfonylbenzophenone, fluorenone, tetraodor carbon, benzoin butyl ether, benzoin isopropyl ether, 2,2'-bis(0-chlorophenyl)-4,4', 5,5'-tetraphenylbiimidazole and 2-mercapto-5-methylthio-1,3
, 4-thiadiazole, and the like.

As the photopolymerization initiator, the above-mentioned compounds may be used alone, or several types may be used in combination.

In the photosensitive material of the present invention, the photopolymerization initiator is preferably used in an amount of 0.5 to 30% by weight based on the polymerizable compound used, and more preferably used in the following range:
It is 2 to 20% by weight.

Further, instead of the photopolymerizable composition, a photopolymerizable compound that exhibits photopolymerizability by itself may be used.

Examples of photopolymerizable compounds include acrylamide, barium acrylate, glycerin triacrylate, N, N'
-Methylene bisacrylamide, polyethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, vinyl carbazole, silicate ester of polyvinyl alcohol, and the like. Moreover, a compound obtained by introducing a photosensitive group into a polymerizable compound as described above can also be used as a photopolymerizable compound.

The following optional components that can be included in the photosensitive layer of the margin photosensitive material include color image forming substances, sensitizing dyes, organic silver salts, various image formation accelerators (e.g., oils, surfactants, capri-prevention agents, etc.). and/or compounds with development accelerating properties, thermal solvents, compounds with oxygen removal mechanisms, etc.), thermal polymerization inhibitors, thermal polymerization initiators, development stoppers, fluorescent whitening agents, anti-fading agents, white These include pigments, antihalation or antiirradiation dyes, matting agents, antismudge agents, plasticizers, water release agents, binders, solvents for polymerizable compounds, and the like.

Although a polymer image can be obtained from the photosensitive material by the above-described structure of the photosensitive layer, a color image can also be formed by including a color image forming substance as an optional component in the photosensitive layer.

There are no particular restrictions on the color image-forming substance that can be used in the photosensitive material, and various types can be used. In other words, substances that themselves are colored (dyes and pigments), or substances that are colorless or light colored themselves, but come into contact with external energy (heating, pressure, light irradiation, etc.) or other component C11 colorants). Substances that develop color (color formers) are also included in color image forming substances.

Dyes and pigments, which are substances that color themselves, can be found in reprints as well as in various literature (for example, "Dye Handbook" edited by the Organic Synthetic Chemistry Association, published in 1972; "Latest Pigment Handbook" edited by the Japan Pigment Technology Association; The publicly known one described in ``Published in 1972'' can be used. These dyes or pigments are used after being dissolved or dispersed.

On the other hand, examples of substances that develop color due to some kind of energy such as heating, pressure, or light irradiation include thermochromic compounds,
Piezochromic compounds, photochromic compounds, and leuco compounds such as triarylmethane dyes, quinone dyes, indigoid dyes, and azine dyes are known. All of these develop color upon heating, pressurization, light irradiation, or air oxidation.

Examples of substances that develop color upon contact with another component include various systems that develop color due to acid-base reactions, redox reactions, coupling reactions, chelate formation reactions, etc. between two or more components. For example, pressure-sensitive copying paper (pages 29-58), Azography (pages 87-
95 pages), known coloring systems such as heat-sensitive coloring by chemical changes (pages 118-120), or the latest dye chemistry - Attractive uses and new developments as functional dyes - preliminary draft of the seminar sponsored by the Kinki Chemical Industry Association. Collection, pp. 26-32, (198
It is possible to use the coloring system described in June 19, 2013).

Incidentally, general photosensitive materials using color image-forming substances are described in the above-mentioned Japanese Patent Laid-Open No. 73145/1983. Further, regarding photosensitive materials using dyes or pigments as color image forming substances, see Japanese Patent Application No. 61-29987, and regarding photosensitive materials using leuco dyes, see Japanese Patent Application No. 61-29987.
53876, Japanese Patent Application No. 61-96339 for photosensitive materials using triazene compounds, and Japanese Patent Application No. 133091 and 1983 for photosensitive materials using yellow coloring leuco dyes. -133092
In each of the specifications, there is a description in the specification of Japanese Patent Application No. 197963/1983 regarding a light-sensitive material using a cyan color-forming leuco dye.

In addition, when using two types of substances that cause a color reaction when in contact as the solid color image forming substance described above, one of the substances that cause a color reaction and a polymerizable compound are contained in microcapsules. However, a color image can be formed on the photosensitive layer by allowing other substances among the substances that cause the color-forming reaction to exist outside the microcapsules containing the polymerizable compound. Regarding photosensitive materials that can obtain color images without using an image-receiving material as mentioned above,
It is described in the specification of Japanese Patent Application No. 61-53881.

Sensitizing dyes that can be used in photosensitive materials are particularly v1
There is no limitation, and silver halide sensitizing dyes known in the photographic technology can be used. The sensitizing dyes include methine dyes, cyanine dyes, merocyanine dyes, complex cyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, hemioxonol dyes, and the like. These sensitizing dyes may be used alone or in combination. Especially when the objective is supersensitization, it is common to use a combination of sensitizing dyes. It is true. In addition, along with the sensitizing dye, a dye that itself does not have a spectral sensitizing effect, or a substance that does not substantially absorb visible light but exhibits supersensitization may be used in combination.The amount of the sensitizing dye added is as follows: Generally, the amount is about 10-8 to 10-2 mol per 1 mol of 1M of halogenation. The sensitizing dye is preferably added at the stage of preparing the silver halide emulsion.For light-sensitive materials obtained by adding the sensitizing dye at the stage of forming the silver halide grains, Japanese Patent Application No. 139746/1983 Japanese Patent Application Nos. 61 to 55510 describe light-sensitive materials obtained by adding a sensitizing dye at the stage of preparing a silver halide emulsion after the formation of silver halide grains. Further, regarding specific examples of sensitizing dyes that can be used in light-sensitive materials,
The use of organic silver salts in the photosensitive materials described in No. 39746 and No. 61-55510 is particularly effective in thermal development processing. That is, when heated to a temperature of 80° C. or higher, the organic silver salt is considered to participate in an oxidation-reduction reaction catalyzed by a latent image of silver halide. In this case, it is preferable that the silver halide and the organic silver salt are in contact with each other or in close proximity to each other.The organic compounds constituting the organic silver salt include aliphatic or aromatic carboxylic acids, mercapto groups, or α-hydrogen. Examples include thiocarbonyl group-containing compounds and imino group-containing compounds. Among them, benzotriazole is particularly preferred.The organic silver salt is generally 0.01 to 10 mol, preferably 0.01 mol per mol of silver halide.
Use 1 to 1 mole. Note that the same effect can be obtained by adding an organic compound constituting the organic silver salt (for example, benzotriazole) to the photosensitive layer instead of the organic silver salt. A photosensitive material using a taS salt is described in Japanese Patent Application No. 141799/1983.

Various image formation accelerators can be used in the photosensitive layer of the photosensitive material.Image formation accelerators include oxidation-reduction between halogenated #i (and/or organic silver salt) and a reducing agent. From a physicochemical point of view, image forming accelerators that have functions such as accelerating reactions and promoting transfer of dyes or pigments from light-sensitive materials to image-receiving materials include bases or base precursors, oils, and surfactants. , compounds having an anti-fogging function and/or development accelerating function, thermal solvents, compounds having an oxygen removing function, and the like.

However, these substance groups generally have multiple functions and usually have some of the above-mentioned promoting effects. Therefore, the above classification is for convenience, and in reality, one compound often has multiple functions.

A photographic material using a base or a base precursor is described in Japanese Patent Application No. 227528/1982.

Regarding photosensitive materials using tertiary amines as bases, Japanese Patent Application No. 13181/1983 describes materials with melting points of 80 to 18
Regarding a photosensitive material using a fine particle dispersion of a hydrophobic organic base compound at 0°C, see Japanese Patent Application No. 61-52992, and about a photosensitive material using an alkali metal or alkaline earth metal hydroxide or salt. Patent application No. 61-9634
In the specification of No. 1, for a photosensitive material using a guanidine derivative with a solubility of 0.1% or less, Japanese Patent Application No. 61-21563 is disclosed.
Specification No. 7 contains the respective descriptions.

A photosensitive material using acetylene silver as a base precursor is described in Japanese Patent Application No. 167558/1982. Further, regarding photosensitive materials that use acetylene carboxylate as a base precursor and further contain metallic silver, metallic copper, a silver compound, or a copper compound as a decomposition accelerator for the base precursor, see Japanese Patent Application No. 1981-191000. For a photosensitive material that uses acetylene carboxylate as a base precursor and further contains a heat-melting compound as a decomposition accelerator for the base precursor, a patent application filed in 1983 is disclosed.
Specification 3 of Japanese Patent Application No. 191001 discloses a photographic material using a sulfonylacetate as a base precursor and further containing a heat-melting compound as a decomposition accelerator for the base precursor in Japanese Patent Application No. 193375/1983.

When using a base or base precursor in a photosensitive material,
It is preferable to adopt an embodiment in which silver halide, a reducing agent, and a polymerizable compound are contained in the above-mentioned microcapsules, and a base or a base precursor is present in the photosensitive layer outside the microcapsules.
In addition to the above-mentioned specification, photosensitive materials using microcapsules containing a base or base precursor, such as the photosensitive material described in No. 8, in which the base or base precursor may be accommodated in another microcapsule, include: A photosensitive material in which a base or a base precursor is dissolved or dispersed in an aqueous solution of a water retention agent and housed in a microcapsule is disclosed in Japanese Patent Application No. 61-52989. A photographic material containing a basic compound having a melting point of 70 to 210° C. is disclosed in Japanese Patent Application No. 61-21214.
They are described in Specification No. 8, respectively. Note that the base or base precursor is added to an auxiliary layer other than the photosensitive layer (a layer containing a base or a base precursor such as L, which will be described later), as described in Japanese Patent Application No. 61-96340. ) may be used.

As a compound having an antifogging function and/or a development accelerating function, an anticapri agent is used, and for a photosensitive material, a compound having a cyclic amide structure is used as described in Japanese Patent Application No. 60-294337. For photosensitive materials using X-type compounds, see Japanese Patent Application No. 60-294338, and for photosensitive materials using thioether compounds, see Japanese Patent Application No. 60-294339.
For photosensitive materials using polyethylene glycol derivatives, see Japanese Patent Application No. 60-294340, and for photosensitive materials using thiol derivatives, see Japanese Patent Application No. 60-294341 for photosensitive materials using thiol derivatives. A photosensitive material using an acetylene compound is described in Japanese Patent Application No. 20438/1983, and a photosensitive material using a sulfonamide derivative is described in Japanese Patent Application No. 25578/1988. In addition, as a compound with an oxygen removal mechanism, 2
A photosensitive material using the above compound having a mercapto group is described in Japanese Patent Application No. 53880/1983.

A thermal polymerization initiator that can be used in the photosensitive layer of a photosensitive material is generally a compound that thermally decomposes under heating to generate polymerization initiating species (particularly radicals), and is usually used as an initiator for radical polymerization. be. Regarding thermal polymerization initiators, please refer to "Addition Polymerization-
"Ring-Opening Polymerization" (1983, Kyoritsu Shuppan), pages 6 to 18, etc. The thermal polymerization initiator is preferably used in an amount of 0.1 to 120% by weight, more preferably 1 to 10% by weight, based on the polymerizable compound. In a system in which a polymerizable compound is polymerized in areas where no image is formed, it is preferable to add a thermal polymerization initiator to the photosensitive layer.
It is described in the specification of No. 10657.

Development stoppers that can be used in photosensitive materials are compounds that neutralize the base or react with the base to reduce the base concentration in the film and stop development immediately after proper development, or compounds that interact with silver and silver salts to stop development. A compound that inhibits development.

The anti-smudge agent used in the photosensitive material is preferably a particulate material that is solid at room temperature.The average particle size of the particles is preferably in the range of 3 to 50 pm in terms of volume average diameter, and more preferably in the range of 5 to 40 μm. As mentioned above, when the oil droplets of the polymerizable compound are in the form of microcapsules, it is more effective if the particles are larger than the microcapsules.

Binders that can be used in photosensitive materials and image-receiving materials described below can be contained in the photosensitive layer or image-receiving layer, either singly or in combination. It is preferable to use a mainly hydrophilic binder.For photosensitive materials using binders, Japanese Patent Laid-Open No. 61-6906
There is a description in Publication No. 2. In addition, regarding photosensitive materials using binders together with microcapsules, a patent application filed in 1983
It is described in the specification of No.-52994. The binder is similar to the binder that can be used in the image-receiving material described above. Incidentally, a photosensitive material using a binder is described in JP-A-61-69062. Further, a photosensitive material using a binder together with microcapsules is described in Japanese Patent Application No. 1983-52994.

When using a solvent for a polymerizable compound in a photosensitive material, it is preferable to encapsulate the solvent in a microcapsule separate from the microcapsule containing the polymerizable compound. For photosensitive materials using organic solvents, please refer to Japanese Patent Application No. 5299/1986.
It is stated in the specification of No. 3.

In addition to those mentioned above, materials that can be included in the photosensitive layer,
Examples of the component a and its usage are also found in the application specifications for the above-mentioned series of photosensitive materials, as well as research and
It is described in Disclosure Magazine v01゜170.No. 17029, June 1978 (pages 9-15). In addition,
The pH value of the photosensitive layer is preferably 7 or less as in the photosensitive material described in Japanese Patent Application No. 61-104226.

Layers that can be optionally provided on the photosensitive material include an image receiving layer 1 heating layer, an antistatic layer, an anti-curl layer, a release layer,
Mention may be made of cover sheets or protective layers, layers containing bases or base precursors, base barrier layers, and the like.

Instead of using the image-receiving material described below as a method of using the photosensitive material, an image-receiving layer may be provided on the photo-sensitive material and an image may be formed on this layer. It can be configured similarly to. Details of the image receiving layer will be described later.

For photosensitive materials using a heating layer, a patent application filed in 1986
For photosensitive materials provided with a cover sheet or a protective layer, see Japanese Patent Application No. 61-55507, and for photosensitive materials provided with a layer containing a base or base precursor, see Japanese Patent Application No. 61-96340. They are described in the respective specifications. Further, the base barrier layer is also described in the above-mentioned Japanese Patent Application No. 61-96340. Furthermore, examples of other auxiliary layers and their usage are also described in the applications relating to the above-mentioned series of light-sensitive materials.

Margin below The method for manufacturing the photosensitive material will be described below.

Various methods can be used to manufacture photosensitive materials, but the general manufacturing method is to prepare a coating solution by dissolving, emulsifying, or dispersing the components of the photosensitive layer in an appropriate solvent, and then coating. This process consists of applying a liquid onto a support and drying it to obtain a photosensitive material.

Generally, the above-mentioned coating liquid is prepared by preparing a liquid composition containing each component and then mixing the respective liquid compositions. The above-mentioned liquid composition may be prepared individually for each component or may be prepared to contain a plurality of components. It can also be used by adding at a stage or after preparation. Furthermore, 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 can also be used. .

Regarding the main components contained in the photosensitive layer, methods for preparing a liquid composition and a coating solution are shown below.

In the production of a photosensitive material in which the photosensitive layer contains silver halide, it is preferable to prepare the silver halide as a silver halide emulsion, and there are various methods known in photography for preparing the silver halide emulsion. However, there are no particular limitations regarding the production of the light-sensitive material of the present invention, and the silver halide emulsion may be
It can be prepared using any of the acid method, neutral method, and ammonia method. The reaction method between the soluble silver salt and the soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof.

Back mixing method in which particles are mixed under silver ion excess conditions and p
The Chondral double jet method, which keeps Ag constant, can also be used. In addition, silver halide emulsions can be either surface latent image type emulsions in which latent images are mainly formed on the grain surfaces or internal latent image type emulsions in which latent images are formed inside the grains. Direct inversion emulsions in combination with nucleating agents can also be used.

In the preparation of silver halide emulsions used in the production of light-sensitive materials, it is preferable to use woody colloids (e.g., gelatin) as protective colloids. Preparing silver halide emulsions using woody colloids. As a result, the sensitivity of light-sensitive materials produced using this emulsion is improved. /
In the silver halide emulsion, a silver halide solvent can be used in the stage of forming silver halide grains. In addition, in the process of particle formation or physical ripening, cadmium salt,
Zinc salts, lead salts, thallium salts, etc. may be present together. Furthermore, water-soluble iridium salts or water-soluble rhodium salts can be used for the purpose of improving high illuminance failure and low illuminance failure.

Soluble salts may be removed from the silver halide emulsion after precipitation or physical ripening. In this case, this can be carried out according to the Tardel water washing method or the precipitation method. Although the silver halide emulsion may be used without post-ripening, it is usually used after being chemically sensitized.

In emulsions for conventional sensitive materials, known sulfur sensitization methods, reduction sensitization methods, noble metal sensitization methods, etc. can be used alone or in combination.

In addition, when adding a sensitizing dye to a silver halide emulsion,
Patent Application No. 139746/1986 and 61-5 mentioned above
It is preferable to add the nitrogen-containing heterocyclic compound in the preparation stage of the silver halide emulsion as in the light-sensitive material described in the specification of No. In the case of silver halide emulsion preparation, the nitrogen-containing heterocyclic compound is preferably added at the stage of forming or ripening silver halide grains. The manufacturing method is described in Japanese Patent Application No. 3024/1983.

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

In the production of photosensitive materials, polymerizable compounds (including photopolymerizable compounds) can be used as a medium in preparing the composition of other components in the photosensitive layer.For example, silver halide (silver halide (including emulsions), reducing agents, photopolymerization initiators, color image forming substances, etc. can be dissolved, emulsified or dispersed in a polymerizable compound and used in the production of photosensitive materials. In particular, it is preferable that the color image-forming substance is contained in a polymerizable compound, and when microcapsulating oil droplets of a monopolymerizable compound as described later, a wall material necessary for microencapsulation is required. Components such as the following may be included in the polymerizable compound.

A photosensitive composition containing silver halide in a polymerizable compound can be prepared using a silver halide emulsion. In addition to the /X silver halide emulsion, silver halide powder prepared by freeze-drying or the like can also be used to prepare the photosensitive composition.

Photosensitive compositions containing these silver halides can be obtained by stirring with a homogenizer, blender, mixer, or other commonly used stirrers.

In addition, it is preferable that a copolymer consisting of a hydrophilic repeating unit and a hydrophobic repeating unit is dissolved in the polymerizable compound used to make 2g of the photosensitive composition. Regarding the photosensitive composition containing the above copolymer, The special request was made in 1973.
It is described in the specification of No. 0-261887.

Alternatively, instead of using the above copolymer, a photosensitive composition may be prepared by dispersing microcapsules having a silver halide emulsion as a core material in a polymerizable compound. A photosensitive composition containing microcapsules is described in Japanese Patent Application No. 5750/1983.

Polymerizable compounds (like the above photosensitive compositions, etc.)
(including those containing ingredients) is preferably used as an emulsion in an aqueous solvent.
When oil droplets of a polymerizable compound are microencapsulated as in the photosensitive material described in No. 0-117089,
It is also possible to add a wall material necessary for microcapsulation to this emulsion and further perform a treatment to form the outer shell of the microcapsules at the stage of this emulsion. Further, a reducing agent or other optional components may be added at the stage of the emulsion.

Regarding photosensitive microcapsules that can be used in the production of photosensitive materials, Japanese Patent Application No. 61-11556,
No. 61-11557, No. 61-53871, No. 61
-53872, 61-53873, 61-53
No. 874, No. 61-53875, No. 61-53877
No. 61-53878.

Among the above-mentioned emulsions of polymerizable compounds (including microcapsule liquids subjected to microencapsulation treatment), when the polymerizable compound is a photosensitive composition containing silver halide or a photopolymerizable compound, can be used as is as a coating solution for photosensitive materials. Emulsions other than those mentioned above can be mixed with a composition of other components such as a silver halide emulsion or a photopolymerization initiator, and optionally an organic silver salt emulsion to prepare a coating solution. It is also possible to add other components at the stage of this coating solution in the same manner as in the case of the emulsion described above.

The photosensitive material of the present invention can be produced by applying the coating solution prepared as described above onto the above-mentioned support and drying it. The coating liquid can be easily applied to the support according to known techniques.

An image forming method using a photosensitive material will be described below.

The photosensitive material can be used simultaneously with imagewise exposure or after imagewise exposure.
Perform development processing and use.

Although various exposure means can be used as the above-mentioned exposure method, a latent image of silver halide is generally obtained by imagewise exposure to radiation including visible light. The type of light source and amount of exposure
Sensitive wavelength of silver halide (if dye sensitization is performed,
It can be selected depending on the sensitized wavelength) and sensitivity. Further, the original image may be a black and white image or a color image. In addition, in a photosensitive material using a photopolymerizable composition or a photopolymerizable compound, the polymerizable compound in the exposed portions is polymerized by the imagewise exposure.

A photosensitive material whose photosensitive layer contains silver halide is developed at the same time as the above-mentioned imagewise exposure or after the imagewise exposure. In addition, as mentioned above, as described above, heat development processing may be performed using JP-A No. 61-69062.
Since the method described in the publication is a dry treatment, it is easy to operate and has the advantage of being able to perform the treatment in a short time.

Therefore, the latter method is particularly excellent for developing photosensitive materials.

As the heating method in the above heat development treatment, various conventionally known methods can be used. Furthermore, as in the photosensitive material described in Japanese Patent Application No. 60-135568, a heat generating layer may be provided on the photosensitive material and used as a heating means. As in the image forming method described above, heat development may be carried out while suppressing the amount of oxygen present in the photosensitive layer, and the heating temperature is generally 80°C to 200°C, preferably 100°C to 100°C.
The temperature is 60°C. The heating time is generally 1 second to 5 minutes.
Preferably it is 5 seconds to 1 minute.

A photosensitive material whose photosensitive layer contains silver halide is subjected to a heat development process as described above, and the polymerizability of the areas where a latent image of silver halide is formed or the area where a latent image of silver halide is not formed is determined. The compound can be polymerized. In addition, in the above-mentioned heat development process, generally for photosensitive materials,
The polymerizable compound in the area where the silver halide latent image is formed is polymerized, but as in the photosensitive material described in the above-mentioned Japanese Patent Application No. 60-210657, the type and quality of the transition agent are adjusted. By doing so, it is also possible to polymerize the polymerizable compound in the area where the silver halide latent image is not formed.

In the manner described above, a polymer image can be obtained on the photosensitive layer. A dye image can also be obtained by fixing dyes or pigments to the polymer.

When the photosensitive material is constructed like the photosensitive material described in the above-mentioned Japanese Patent Application No. 61-53881, the developed photosensitive material is pressurized to destroy the microcapsules containing the color image forming substance. A color image can be formed on a light-sensitive material by bringing a color image-forming substance into contact with an acidic color developer and a coupler.

However, in an image forming method using a photosensitive material, it is preferable to use an image-receiving material in combination to form an image on the image-receiving material.

The image-receiving material will be explained below. The general image forming method using an image-receiving material or an image-receiving layer is described in Japanese Patent Application No. 121284/1984.

Materials that can be used for the support of the image-receiving material include:
Glass, paper, high quality paper, coated paper, cast coated paper, baryta paper 1 synthetic paper, metals and their analogs, polyester, acetyl cellulose, cellulose ester, polyvinyl acetal, polystyrene, polycarbonate, polyethylene terephthalate, etc. films, and resin materials Paper laminated with a polymer such as polyethylene or the like can be mentioned. Note that when a porous material such as paper is used as the support for the image-receiving material, it is preferable that it has a certain level of smoothness as in the image-receiving material described in Japanese Patent Application No. 61-52990. , and regarding an image receiving material using a transparent support, Japanese Patent Application No. 61-529
It is described in the specification of No. 91.

Image-receiving materials generally have an image-receiving layer provided on a support.

The image-receiving layer can be constructed in any desired form using various compounds according to the coloring system of the color image-forming substance described above. In addition, when forming a polymer image on an image-receiving material, when a dye or a pigment is used as a color image-forming substance, the image-receiving material may be composed only of the above-mentioned support.

For example, when using a coloring system consisting of a color former and a color developer, the image receiving layer can contain the color developer. Further, the image-receiving layer can also be configured as a layer containing at least one mordant. The mordant can be selected from compounds known in the photographic technology, taking into consideration conditions such as the type of color image forming substance, and used. Note that, if necessary, two or more image-receiving layers may be constructed using a plurality of mordants having different mordant powers.

The image-receiving layer preferably contains a polymer as a binder. As the binder, binders 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 Japanese Patent Application No. 61-53879, a polymer with low oxygen permeability may be used as the binder.

For the image receiving layer, Japanese Patent Application No. 61-124952 and No. 61
As in the image-receiving materials described in the specifications of No. 124953, fine particles of a thermoplastic compound may be included, or 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. You can do it like this. Furthermore, for the purpose of polymerizing an unpolymerized polymerizable compound, a photopolymerization initiator or a thermal polymerization initiator may be added to the image receiving layer. Showa 6
Japanese Patent Application No. 1-3025 describes an image-receiving material having an image-receiving layer containing a thermal polymerization initiator.

In addition, when the image receiving layer is located on the surface of the image receiving material, it is preferable to further provide a protective layer.
As in the image-receiving material described in No. 55503, a layer made of aggregates of fine particles of a thermoplastic compound may be provided on the image-receiving layer.

The photosensitive material is imagewise exposed and/or developed as described above, and the image-receiving materials are stacked and pressed to transfer the unpolymerized polymerizable compound to the image-receiving material. Polymer images can be obtained. Regarding the above-mentioned pressurizing means, various conventionally known methods can be used.

Further, in an embodiment in which the photosensitive layer contains a color image forming substance,
Similarly, the polymerizable compound is polymerized and cured by imagewise exposure and/or development treatment, thereby immobilizing the color image-forming substance in the cured portion. By pressing the photosensitive material and the image-receiving material in a superimposed state, the uncured portion of the color image-forming substance 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 Japanese Patent Application No. 61-55501. There is an advantage that the unpolymerized polymerizable compound transferred to the image is polymerized and the storage stability of the obtained image is improved.

The applicant has already filed patent applications for various image recording apparatuses suitable for carrying out the above-described series of image forming methods using photosensitive materials. Typical of these devices are an exposure device that forms a latent image by imagewise exposure, a heat development device that hardens and immobilizes the portion corresponding to the formed latent image, and a developed photosensitive device that A transfer device that superimposes an image-receiving material on a material and presses them (Japanese Patent Application No. 60-289703 Specification B);
and a structure in which a fixing device is further added to the above structure to irradiate, pressurize, or heat the image-receiving material onto which the image has been transferred (Japanese Patent Application No. 60-2897
No. 03 Specification).

Photosensitive materials include photosensitive materials for black and white or color photography and printing, printing photosensitive materials, printing plates, X-ray photosensitive materials, medical photosensitive materials (for example, ultrasonic diagnostic ficRT photosensitive materials), computer graphics hard copy photosensitive materials, and copying materials. It has many uses such as mechanical sensitive materials.

The present invention will be explained in more detail with reference to the following examples, but the present invention is not limited thereto.

Margin below [Example 1] Preparation of paper support (a) Part of LBSPIO and 90 parts of LBKP were beaten to 280 cc of Canadian freeness using a Dijordan type conical refinery, rosin size of 1.0 part, band of sulfuric acid 2.0 parts , and 0.5 part of polyamide polyamine epichlorohydrin, both in mM relative to bone dry pulp.
Added in percent. Next, the above paper stock was made into a base paper having a weight of 50 g/g and a thickness of 55 gm using a Fourdrinier paper machine.

The fiber length distribution of the bulb used was 24 with a mesh residue of 5
, 4% by weight, and the 42 mesh residue was 47.5% by weight.

Then 300 parts of clay and 100 parts of SDR latex
The composition was applied onto the base paper at a coating amount of lOg/m'.

Preparation of silver halide emulsion Add 21 g of sodium chloride and 56 g of potassium bromide to an aqueous gelatin solution (containing 20 g of gelatin and 3 g of sodium chloride in 1000 ml of water and keeping it at 75°C) while stirring.
600 m fL of an aqueous solution containing g and an aqueous silver nitrate solution (
0.59 mol of silver nitrate dissolved in 600 ml of water was simultaneously added at a low flow rate over a period of 40 minutes. In this way, a monodisperse cubic silver chlorobromide emulsion (80 mol % bromine) with an average grain size of 0.35 pm was prepared.

After washing the emulsion with water to desalt it, 5 mg of sodium thiosulfate and 4-hydroxy-6-methyl-1,3,3
a. Add 20 mg of 7-chitrazaindene at 60°C.
Chemical sensitization was performed. The yield of emulsion was 600 g.

Preparation of benzotriazole silver emulsion 28 g of gelatin and 13.2 g of benzotriazole are mixed with 3 ml of water.
000+niL. This solution was stirred while being maintained at 40° C., and a solution of 17 g of silver nitrate dissolved in 100 mu of water was added over 2 minutes.

Excess salt was precipitated and removed by adjusting the pH of the resulting emulsion. Thereafter, the pH was adjusted to 6.30 to obtain a benzotriazole silver emulsion. The yield of emulsion was 400 g.

Preparation of photosensitive composition Add 0.40 g of the following copolymer, 6.00 g of Vargas Script Red l-6-B (manufactured by Ciba Geigy), and 2 g of Emmalex NP-8 (manufactured by Nippon Emulsion ■) to a long trimethylolpropane triacrylate. Dissolved.

Above solution 18. 0.00 of the following thiol derivative to oog
2g was dissolved. To this solution was further added 0.16 g of the following hydrazine derivative (reducing agent).

Add 1.22 g of the following developer (reducing agent) to 1.2 g of methylene chloride.
A solution of 80 g was added. Further, 3.50 g of the silver halogenide emulsion prepared as above and 3.35 g of the silver benzotriazole emulsion were added and stirred for 5 minutes at 15,000 revolutions per minute using a homogenizer to prepare the photosensitive composition. Obtained.

(Copolymer) もH2-C←20 →H2-C←60GO
2CH2CH2NCCH3) 2 COOCH
3H3 zuH2-CH20 C02C4Hq (thiol derivative) (hydrazine derivative) (developer) Preparation of microcapsule liquid 18.6% aqueous solution of isopane (manufactured by Kuraray ■) 10,5
48.56 g of a 2.89% aqueous solution of 1 gt pectin was added, and the photosensitive composition was adjusted to p) 14.0 using 10% sulfuric acid, and the photosensitive composition was added to the aqueous solution, and the mixture was heated at 7000 rpm for 2 minutes using a homogenizer. The photosensitive composition was stirred and emulsified in the aqueous solvent.

To 72.5 g of this aqueous emulsion, 8.32 g of urea 40% aqueous solution was added.
g, resorcinol 11.3% aqueous solution 2°82g, formalin 37% aqueous solution 8.56g, ammonium sulfate a, OO
% aqueous solution was added one after another, and heating was continued at 60° C. for 2 hours while stirring. Thereafter, the pH was adjusted to 7.3 using a 10% aqueous sodium hydroxide solution, and 3.62 g of a 30.9% aqueous sodium bisulfite solution was added to prepare a microcapsule liquid.

Preparation of photosensitive material (A) 10.0 g of microcapsule liquid prepared as above
Add 1.0 g of 1% wood solution of the following 7-ion surfactant, 10% guanidine trichloroacetate (water/ethanol =
50150 (volume ratio) solution was added to #4 on the surface of the coated layer side of the paper support (a) prepared as described above.
The photosensitive material (A) according to the present invention was prepared by applying the coating using a No. 0 coating rod and dry-cooking at about 40°C.

(Anionic surfactant) CH;fll:00GH2-OH(C2Hs)CaHq
NaO+S-0H-COOCH2-OH(C2Hs)G
Jq [Example 2] Creation of paper supports (b) and (C) Composition ratio of wood pulp used in creating paper support (a) in Example 1 and freeness after beating (Canadian freeness) Paper supports (b) and (C) were prepared in the same manner as in Example 1, except that 0 was changed as shown in Table 1.Fibers of the base paper of paper supports (b) and (C) The length distribution is shown in Table 1 below.

1st cover support Wood pulp Filtered water 24 mesh 42 mesh s 2
4+42 carrier (composition ratio) Degree (cc) Remaining amount Remaining amount Total (a) LBSP+LBKP 280c
c 5.4$ 47.0 52.9$(10%)(
90%) (b) LOP+LBKP 310cc 1.
2$ 38.2$ 39.4X (3o$) (7o
t) (c) LBKP+LBSP+L[]P 250cc
Og 34.2$ 34. :Q (50%)
(20%) (30%) Photosensitive materials (B) and (C) according to the present invention were prepared in the same manner as in Example 1, except that the paper supports (b) and (C) prepared as described above were used. It was created.

[Comparative Example 1] Creation of paper supports (X) to (z) The composition ratio of the wood pulp used in the creation of paper support (a) in Example 1 and the freeness (Canadian freeness) after beating were determined. Fiber length distribution of the base paper of 0 paper supports (x) to (Z) prepared in the same manner as in Example 1 except for the changes shown in Table 2 below. are shown in Table 2 below.

2nd cover support Wood pulp Filtered water 24 meters, Shu 4? mesh 2
4+42 carrier (composition ratio) degree (cc) remainder remainder total (x) LBKP 400cc 1
4.2$ 50.8$ 65.0$(tool) D) LBKP+NBKP 340cc 21.
3$ 52.9$ 74.22 (70ri (30$)
) (z) LBKP+NBKP 280cc 28
．． 4$ 55.3$ 83.7$ (50%) (5
0%) Comparative photosensitive material (X
) to (Z) were created.

[Example 3] Preparation of photosensitive material (D) A photosensitive material according to the present invention was prepared in the same manner as in Example 1, except that the benzotriazole silver emulsion was not added in the preparation of photosensitive material (A) of Example 1. (D) was created.

[Example 4] Preparation of photosensitive material (E) 2 g of trimethylolpropane triacrylate and 7 g of methyl methacrylate were added to the monomer mixture, and 0.2 g of 2-mercapto-5-methylthi-1,3°4-thiadiane was added.
7 g was added and dissolved using an ultrasonic disperser. 6 g of methylene chloride, 0.7 g of 4-4'-bis(diethylamino)benz'phenone, 2,2'-bis(0-chlorophenyl)-4,4', 5,5'-tetraphenylimidanol 2, 1 g and 2.1 g of 3-diethylamino-6-chloro-7-anilinofluorane were dissolved and added to the above solution to form an oil phase.

On the other hand, lO% gum arabic aqueous solution L7. Og.

12% inbutylene/woodless maleic acid aqueous solution 18.8g
A mixture of 26.8 g of distilled water and 26.8 g of distilled water was adjusted to pH using sulfuric acid.
3.5, and further added 4.6 g of urea and 0.6 g of resorcin, and emulsified and dispersed the oil phase in this solution. The average particle size of the oil phase droplets was 3 uLm.
Next, 36% formalin 12.9 was added and the temperature was raised to 60° C. with stirring. After 1 hour, 9.0 g of a 5% ammonium sulfate aqueous solution was added, and after stirring for 1 hour while maintaining the temperature at 60° C., the mixture was cooled. At that time, the pH was adjusted to 7.0 using an aqueous sodium hydroxide solution.

Add 15% to 5g of the microcapsule liquid obtained in this way.
Polyvinyl alcohol aqueous solution 1.53g, distilled water 3.4g
7 g and 0.57 g of starch were added to prepare a coating solution. Apply this coating liquid using a #10 coating rod.
The coating layer was coated on the surface of the paper support (a) used in the preparation of the photosensitive material (A) and dried at 40° C. to prepare the photosensitive material (E) according to the present invention.

Preparation of image-receiving material 11 g of 40% sodium hexametaphosphate aqueous solution was added to 125 g of wood, and 34 g of zinc 3,5-di-α-methylbenzylsalicylate and 82 g of 55% calcium carbonate slurry were mixed and coarsely dispersed with a mixer. . The liquid was dispersed with a Dynamyl dispersion machine, and 55 g of 50% SBR0% SBR latex 8% polyvinyl alcohol was added to 200 g of the obtained liquid and mixed uniformly.Then, this mixed liquid was applied to the surface of cast coated paper in a wet area of 30 ALm. After coating the film uniformly to obtain a film thickness, it was dried to prepare an image-receiving material.

Evaluation of Photosensitive Materials Each photosensitive material obtained in Example 1.2.3 and Comparative Example 1 was evaluated at 5000 lux using a tungsten light bulb.
Each light-sensitive material was exposed to light for 1 second through a filter whose density was continuously changed, and then heated for 30 seconds on a hot plate heated to 125°C.Then, each light-sensitive material was layered on the above image-receiving material and exposed at a rate of 500 kg/crn. The density of the magenta positive color image obtained from each light-sensitive material onto the image-receiving material by passing it through a pressure roller was measured using a Macbeth reflection densitometer.

In addition, the photosensitive material (E) obtained in Example 4 was
3 from a distance of 25 cm using a 00 watt high pressure mercury lamp.
An image was formed on the image-receiving material in the same manner as above, except that exposure was performed for one minute, and its density was measured using a Macbeth reflection densitometer.

The above measurement results are shown in Table 3 below.

However, the numerical values shown in Table 3 indicate the number of transfer irregularities with a diameter of 1 mm or more that exist in a circular color image with a diameter of 4 cm.

Margin below Table 3 Materials Special holidays Total balance 250kg/crn' 70
0kg/crn'(A) (a) 52.9$
100-300 Less than 10 (B) (b)
39.4$ 10~too less than 10 (
C) (c) 34.2$ Less than 10
Less than 10 (X) (x) 65.01 30
0 or more and 300 or more L (Y) (4) 74.2$
300 or more 300 or more (Z) (Z)
83.0 300 or more 300 or more (D)
(a) 52.9$ 100-300 1
Less than 0 (E) (a) 52.9$ 100
~300 Less than 10 As is clear from the results shown in Table 3, when the photosensitive material according to the present invention is used, the occurrence of transfer unevenness can be significantly reduced.

procedural amendment

Claims (1)

[Claims] 1. A photosensitive material comprising a photosensitive layer containing silver halide, a reducing agent, and a polymerizable compound on a paper support, wherein the paper support is compliant with JIS-P-8207. The paper support uses a base paper having a defined fiber length distribution such that the sum of the weight percent of the 24 mesh residue and the weight percent of the 42 mesh residue is 30 to 60%. Characteristic photosensitive materials. 2. In the fiber length distribution of the base paper used for the paper support,
2. The photosensitive material according to claim 1, wherein the weight percent of the 24 mesh residue is 10% or less. 3. The photosensitive material according to claim 1, wherein 5 to 60% by weight of the pulp constituting the base paper used for the paper support is LBSP and/or LDP. 4. The pulp constituting the base paper used for the paper support is C
The photosensitive material according to claim 1, which is a pulp having a freeness defined by SF of 200 to 400 cc. 5. The photosensitive material according to claim 1, wherein the paper support is formed by providing a coating layer containing a hydrophobic polymer on one or both sides of a base paper. 6. The photosensitive material according to claim 1, wherein the photosensitive layer contains the silver halide and the polymerizable compound in microcapsules. 7. The photosensitive material according to claim 1, wherein the photosensitive layer further contains a color image forming substance. 8. The photosensitive material according to claim 1, wherein the photosensitive layer further contains an organic silver salt. 9. The photosensitive material according to claim 1, which is used for thermal development. 10. A photosensitive material comprising a photosensitive layer containing a photopolymerizable composition or a photopolymerizable compound on a paper support, wherein the paper support has a fiber length distribution defined by JIS-P-8207. 1. A paper support using a base paper having a fiber length distribution such that the sum of the weight percent of the 24 mesh residue and the weight percent of the 42 mesh residue is from 30 to 60%. 11. The photosensitive material according to claim 10, wherein in the fiber length distribution of the base paper used for the paper support, the weight percent of the 24 mesh residue is 10% or less. 12. 5 to 60% by weight of the pulp constituting the base paper used for the paper support is LBSP and/or LDP
The photosensitive material according to claim 10, characterized in that: 13. The pulp constituting the base paper used for the paper support is
Freeness defined by CSF is 200 to 400cc
Claim 10, characterized in that the pulp is
Photosensitive materials described in Section 1. 14. The photosensitive material according to claim 10, wherein the paper support is formed by providing a coating layer containing a hydrophobic polymer on one or both sides of a base paper. 15. The photosensitive material according to claim 10, wherein the photopolymerizable composition or the photopolymerizable compound is contained in the photosensitive layer in a state of being accommodated in microcapsules. 16. The photosensitive material according to claim 10, wherein the photosensitive layer further contains a color image forming substance.