JPH05119473A - Thermodeveloping photosensitive material - Google Patents

Abstract

PURPOSE:To reduce dependence on thermodevelopment temp. for short time development by constituting the silver halide of silver chloride or of silver chloride/bromide containing specified % or higher % silver chloride. CONSTITUTION:This photosensitive material has at least a silver halide, reducing agent and polymerizable compd. on a supporting body, and is subjected to thermal development within <=5 sec. In this photosensitive material, the silver halide consists of silver chloride or silver chloride/bromide containing >=95mol% silver chloride. In this case, the silver halide, reducing agent and polymerizable compd. are contained in microcapsules, and further, this capsule contains a color picture image forming material and base precursor. Further, the silver chloride/bromide particle has the phase of high silver bromide content which is present on the surface of the silver halide particle. The volume fraction of the phase of high silver bromide content to whole particles is <=20%, and the proportion of silver bromide in the phase of high silver bromide content is >=20mol%.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-developable color light-sensitive material capable of obtaining an excellent color image in an extremely short time. More specifically, it relates to a heat-developable color light-sensitive material which is capable of stably providing an excellent color image and has little dependence on the heat-development temperature.

[0002]

2. Description of the Related Art A light-sensitive material having a light-sensitive layer comprising a light-sensitive silver halide, a reducing agent, a polymerizable compound and a binder on a support is imagewise exposed to form a latent image, and then a halogen image is developed by heat development. An image forming method for forming a polymer compound on a portion where a latent image of silver halide is formed is disclosed in JP-A-61-69.
062 and the like. Further, a light-sensitive material in which a silver halide, a reducing agent, a color image-forming substance and a polymerizable compound are contained in microcapsules (photosensitive microcapsules) is disclosed in JP-A-61-275742 and JP-A-61-275742.
It is described in Japanese Patent No. 278849. An image forming method using the light-sensitive material having the above-described structure is as follows. First, the light-sensitive material is exposed imagewise to form a latent image, and then this is heat-developed, so that the polymerizable compound in the portion where the latent image is formed is formed. And further superimpose the light-sensitive material with an image-receiving material having an image-receiving layer, pressurize in this state, transfer the color image-forming substance together with the unpolymerized polymerizable compound to the image-receiving material, and form a transferred image on the image-receiving material. The method of obtaining is generally used.

On the contrary, a method for polymerizing the polymerizable compound in the portion where the latent image is not formed is disclosed in JP-A-62-62.
-70836, 62-81635, JP-A 2-1
No. 41756, No. 2-141757, and the like. On the other hand, the development or polymerization reaction in the development process of the above image forming method proceeds smoothly under alkaline conditions. Therefore, it is preferable to include a base or a base precursor as an image formation accelerator in the photosensitive layer of the photosensitive material. For a light-sensitive material containing a base or a base precursor in the light-sensitive layer, see Japanese Patent Application Laid-Open No.
It is described in JP-A-2-26441. In this case, it is more preferable that the base or the base precursor is contained in the photosensitive microcapsule from the viewpoint of the image formation promoting function.

A light-sensitive material characterized by containing a base precursor in microcapsules is disclosed in JP-A-64 / 1988.
-32251, JP-A-1-263641, JP-A-2
No. 146041, JP-A No. 1-263641, and other publications and specifications, the solid base precursor is contained in microcapsules. Thus, by accommodating the base or the base precursor in the microcapsules, image formation is promoted, and a photosensitive material that gives a clear image in a short time can be obtained. In this case, when the base is contained in the microcapsules. However, it is preferable to store the base precursor instead of the base in the microcapsules because the deterioration of the light-sensitive material over storage becomes remarkable. Further, the photosensitive silver halide used in such a photothermographic material is disclosed in JP-A-62-183453 and 63-63.
218956, it is disclosed that an image with good discrimination can be obtained by using silver iodobromide having a high silver iodide content in the surface phase. In addition, the fact that a wider range of silver halide types can be used is disclosed in "Public Technology No. 5" (Aztec Co., Ltd., 1991).
Issued March 22, 2012) 2 to 4 pages.

[0005]

However, when an image is formed using such a light-sensitive material by heat development for an extremely short time of 5 seconds or less, the development speed is largely time-dependent and temperature-dependent. It has been found that the fluctuation of the image density becomes large, and the temperature accuracy is increased to prevent this, which causes a great burden to the processing equipment. Further, in such short-time heat development, silver halide is apt to cause development fog, and as a result, a sufficient difference does not occur in the degree of subsequent polymerization reaction of the polymerizable compound between the exposed area and the unexposed area. Therefore, it was found that the discrimination of the image was likely to deteriorate. Therefore, an object of the present invention is to provide a photothermographic material capable of obtaining a stable and good image. Still another object of the present invention is to provide a heat-developable color light-sensitive material capable of obtaining an excellent color image in a short time.

[0006]

The objects of the present invention can be achieved by the following photothermographic material. (1) In a light-sensitive material which has at least silver halide, a reducing agent and a polymerizable compound on a support and which is heat-developed in 5 seconds or less, a salt in which the silver halide is 95 mol% or more of silver chloride. A photothermographic material comprising silver bromide or silver chloride. The heat-developable photosensitive material of the present invention preferably has the following embodiments. (2) The silver halide, the reducing agent and the polymerizable compound are contained in microcapsules, and the capsule further contains a color image forming substance and a base precursor. Photothermographic material. (3) The silver chlorobromide grains have a high silver bromide phase, the high silver bromide phase is located on the surface of the silver halide grains, and the volume fraction of the high silver bromide phase in the whole grains is 20% or less, and The photothermographic material according to (1) above, wherein the content of silver bromide in the high silver bromide phase is 20 mol% or more. (4) The photothermographic material according to (1) above, wherein the surface of the silver halide grains has a high silver bromide phase, and the formation of the high silver bromide phase is carried out in the presence of a sensitizing dye. (5) The silver halide grains have a water-soluble iridium compound molar ratio with respect to the total silver halide grains of 10 ^-8 or more and 10 ^-4 or less, or iron ions have a molar ratio with respect to silver of the entire silver halide grains. The photothermographic material of (1) above, wherein the content is 10 ^-6 or more and 10 ^-3 or less.

A number of patents using high silver chloride grains as a light-sensitive material for so-called conventional silver salt photography have been published (for example, JP-A-58-95354 59-232342).
No. 60, No. 60-19140, No. 62-215272.
No.), both of them are characterized in that the development processing time can be greatly shortened by introducing high silver chloride grains in the wet development processing. Similarly, the above patent specification discloses a technique for forming a high silver bromide phase on the surface of high silver chloride grains mainly for the purpose of increasing the sensitivity. However, it has the drawback of impairing the rapid developability of. However, in the photothermographic material of the present invention, surprisingly, the presence of the high silver bromide phase as described above does not have the drawback of lowering the development rate, but rather it is rapid and stable when used in combination with high silver chloride grains. I found that development can be realized. This is completely unpredictable from the above-mentioned known technique based on wet development. Further, it has been found that iridium ions and iron ions are effective for more preferably realizing the effects of the present invention.

The silver halide grains of the present invention have regular crystals such as cubes, octahedra, dodecahedrons and tetradecahedrons, and irregular crystal systems such as spheres and plates. It may be a thing, or those compound forms. Further, tabular grains having an aspect ratio of about 5 or more can be used in the present invention. Tabular grains are described by Gatov, Photographic Science and Engineering (Gutoff, Ph
otographic Scienceand Engineering), Vol. 14, 2
48-257 (1970); U.S. Pat. No. 4,43.
4,226, 4,414,310, 4,43
It can be easily prepared by the method described in 3,048, 4,439,520 and British Patent 2,112,157. The grain size of the silver halide of the present invention is preferably 0.05 μm or more and 2 μm or less, more preferably 0.1 μm or more and 1 μm or less.

The silver halide grains of the present invention have a non-uniform crystal structure with respect to the halogen composition and the content of impurity ions, but the manner of contacting the phases having different compositions is gradually different even in the form having a clear interface. The shape may change.
They may have a layered structure, and particularly for formation of a high silver bromide phase, silver halides having different compositions may be joined by epitaxial joining.

The water-soluble iridium salt preferably used in the present invention can be appropriately selected and used from already known iridium compounds, and the water-soluble iridium salt particularly preferably used is represented by the following general formula (1) or ( It is a compound represented by 2). General formula (1): (R) _m IrX ₆ (wherein R is a monovalent anion and is a hydrogen ion,
Represents a sodium ion, potassium ion, or ammonium ion, X represents a halogen ion, and m
Represents 2 or 3. General formula (2): Ir (X) _n (wherein X represents a halogen ion and n represents 3 or 4) Of the water-soluble iridium salts represented by the above general formula, a particularly preferable compound is shown. As an example, (NH ₄ ) ₃ IrC
Mention may be made of l ₆ , Na ₃ IrCl ₆ or IrCl ₃ .

Silver halide grains containing iridium ions
Is water-soluble in the step of preparing silver halide grains.
It can be obtained by adding an iridium salt.
The iridium ion of the present invention contains 1 mol of silver halide grains.
Per 10^-8More than 10 ^-FourUsed in the range of molar or less
Preferably. More preferably 5 × 10^-8Less than a mole
Top 5 × 10^-FiveIt is in the range of mol or less. Furthermore, the present invention
Of iridium ions on the surface of high silver chloride grains
Is preferably present in Specifically, high silver bromide phase
Added to aqueous bromide solution for formation, or high
As a water-soluble iridium salt solution during the formation of the silver bromide phase
There is a method of addition, but it is not limited to this.
Yes.

In order to incorporate iron ions into the silver halide emulsion grains in the present invention, it is easy to carry out a method in which a water-soluble iron compound is allowed to coexist in the emulsion grain forming step. These iron compounds are divalent or trivalent iron ion-containing compounds and preferably have water solubility in the concentration range used in the present invention. It is more preferable to use an iron complex salt that is easily incorporated inside the silver halide grains. Specific examples of these compounds are shown below, but the iron compounds usable in the present invention are not limited to these.

Ferrous arsenate, ferrous bromide, ferrous carbonate, ferrous chloride, ferrous citrate, ferrous fluoride, formic acid first
Iron, ferrous gluconate, ferrous hydroxide, ferrous iodide, ferrous lactate, ferrous oxalate, ferrous phosphate, ferrous succinate, ferrous sulfate, thiocyanate Ferrous iron, ferrous nitrate,
Ferrous ammonium nitrate, basic ferric acetate, ferric albuminate, ferric ammonium acetate, ferric bromide, ferric chloride, ferric chromate, ferric citrate, fluorinated Ferric iron, ferric formate, ferric glycerophosphate, ferric hydroxide, ferric acid phosphate, ferric nitrate, ferric phosphate, ferric pyrophosphate, ferric pyrophosphate Sodium iron, ferric thiocyanate, ferric sulfate, ferric ammonium sulfate, ferric guanidinium sulfate, ferric ammonium citrate, potassium hexacyanoferrate (II), potassium pentacyanoammine iron (II), Sodium iron (III) diethylenetrilotetraacetate, potassium hexacyanoferrate (III), tris (bipyridyl) iron (III) chloride, potassium pentacyanonitrosyl iron (III).

Among these compounds, hexacyanoiron (II) salt, hexacyanoiron (III) salt, iron (II) thiocyanate salt, and iron (III) thiocyanate salt show remarkable effects. The above iron compound is used in a dispersion medium (gelatin or other polymer having a protective colloid property) solution, a halide aqueous solution at the time of forming silver halide grains,
It can be contained in the silver halide grains by being present in the silver salt aqueous solution or in another aqueous solution. Further, the iron ion of the present invention is preferably present at a higher concentration on the surface of the high silver chloride phase of the high silver chloride grain. More preferably, in the high silver chloride phase of the silver halide grain, the surface phase containing iron ions is 30% by volume or less of the whole grain, and the concentration of iron ions in the surface phase is 10 per mol of silver. ^-5 mol or more and 10 ^-2 mol or less.

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) No.
17643 (December 1978), pp. 22-23,
"I. Emulsion preparation
ion and types) ”, and No. 187
16 (November 1979), p.648, and the like.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such a process are described in Research Disclosure No. 17643 and No. 18716, and the corresponding portions are summarized in the table below. Known photographic additives that can be used in the present invention are also the above-mentioned two research products.
It is described in the disclosure, and the relevant parts are shown in the table below. Additive type RD17643 RD18716 Chemical sensitizer, page 23, page 648, right column, sensitivity enhancer, same as above, spectral sensitizer, page 23-24, page 648, right column, supersensitizer, page 649, right column, antifoggant, page 24-25, 649 The right column on page-and stabilizers The details of the above silver halide emulsion and photographic additives are described on pages 2 to 17 of "Public Technology No. 5". The amount of silver halide used is 0.001 to 3 g, preferably 0.005 to 1 g, in terms of silver per 1 m ² of the light-sensitive material. Further, in the present invention, an organic silver salt can be used together with silver halide. The organic silver salt is described on pages 17 to 18 of "Public Technology No. 5" mentioned above.

The polymerizable compound, the reducing agent, the color image-forming substance, the base precursor, the microcapsule, and the support used in the photothermographic material of the present invention (hereinafter simply referred to as "photosensitive material") will be described below. The polymerizable compound that can be used in the present invention is not particularly limited, and known polymerizable compounds can be used. Since the photosensitive material is subjected to heat development processing, it is preferable to use a polymerizable compound having a high boiling point (for example, a boiling point of 80 ° C. or higher) that hardly volatilizes during heating. Further, since the present invention is intended to immobilize the color image forming substance by polymerizing and curing the polymerizable compound, the polymerizable compound is preferably a crosslinkable compound having a plurality of polymerizable functional groups in the molecule. Further, as specific examples of compounds, the compounds described in "Public Technology No. 5", pages 51 to 55, can be used.

The reducing agent that can be used in the light-sensitive material of the present invention has a function of reducing silver halide and / or a function of accelerating (or suppressing) the polymerization of the polymerizable compound. Examples of the reducing agent having the above function include hydroquinones, catechols, p-aminophenols, p-phenylenediamines, 3-pyrazolidones, 3-aminopyrazoles, 4-amino-5-pyrazolones and 5-amino. Uracils, 4,5-dihydroxy-6-aminopyrimidines, reductones, aminoreductones, o-
Or p-sulfonamidophenols, o- or p
-Sulfonamidonaphthols, 2,4-disulfonamidophenols, 2,4-disulfonamidonaphthols, o- or p-acylaminophenols, 2-
Sulfonamide indanones, 4-sulfonamido-5
-Pyrazolones, 3-sulfonamidoindoles, sulfonamidepyrazolobenzimidazoles, sulfonamidepyrazolotriazoles, α-sulfonamidoketones, hydrazines and the like. The above-mentioned various reducing agents are described in detail on pages 18 to 35 of the above-mentioned known technology No. 5. The addition amount of the reducing agent can be widely varied, but it is generally 0.1 to 1500 mol%, preferably 10 to 300 mol% with respect to the silver salt.

There are no particular restrictions on the color image forming substance that can be used in the light-sensitive material of the present invention, and various types can be used. That is, the substance itself is colored (dye or pigment), or the substance itself is colorless or light-colored but external energy (heating, pressure, light irradiation, etc.) or another component (developing agent) A substance (color former) that develops a color upon contact with is also included in the color image forming substance. As the color image-forming substance of the present invention, as described in JP-A-62-187346, dyes and pigments which are excellent in image stability and colored themselves are preferable.

The dyes and pigments used in the present invention include
In addition to commercially available products, known products described in various documents can be used. Regarding literature, Color Index (CI) handbook, "Latest Pigment Handbook" edited by Japan Pigment Technology Association (1977), "Latest Pigment Application Technology" CMC Publishing (1986), "Printing Ink Technology" (CMC Publishing) ,
1984) etc. Details of the color image-forming substance that can be used in the present invention and the technique for using the same are described in the above-mentioned "Known Technology No. 5", pp. In particular, the pigment is preferable because it has excellent light fastness and causes less blurring of an image during transfer. The pigment is preferably used in a proportion of 5 to 60 parts by weight with respect to 100 parts by weight of the polymerizable compound.

As the base precursor which can be used in the light-sensitive material of the present invention, base precursors of inorganic base and organic base (decarboxylation type, thermal decomposition type, reaction type and complex salt forming type) can be used. For details of these base precursors and their use techniques, refer to the above-mentioned "Public Art No. 5".
No. ”pp. 55-86. Preferred base precursors are JP-A-59-180549, JP-A-59-180537, JP-A-59-195237, and JP-A-59-180537.
1-328844, 61-36743, 61-5
No. 1140, No. 61-52638, No. 61-5263
No. 9, No. 61-53631, No. 61-53634,
61-53635, 61-53636, 61
-53637, 61-53638, 61-53
No. 639, No. 61-53640, No. 61-55644.
No. 61, No. 61-55645, No. 61-55646, No. 61-84640, No. 61-107240, No. 61.
-219950, 61-251840, 61-
No. 252544, No. 61-313431, No. 63-3
16740, 64-68746 and Japanese Patent Application No. 1-
Salts of organic acids and bases which are decarboxylated by heating as described in JP-A-54452, and JP-A-59-15763.
No. 7, No. 59-166943, and No. 63-96159, the compounds capable of eliminating a base by heating are mentioned.

The base precursor of the present invention is 50
It is preferable to release the base at ℃ to 200 ℃, 80
More preferably, the release is carried out at a temperature of 180 to 180 ° C. The base precursor used in the light-sensitive material of the present invention is housed in microcapsules.
As described in No. 59, a base precursor composed of a salt of a carboxylic acid and an organic base having the solubility of 1% or less in water and a polymerizable compound at 25 ° C. is particularly preferable.
In the present invention, when the base precursor is accommodated in the microcapsules, a photosensitive composition in which the base precursor is directly solid-dispersed in a polymerizable compound may be used (JP-A-64-325251, JP-A-1-3521). 263641
It is particularly preferable to use a photosensitive composition in which a base precursor is dispersed in water and emulsified in a polymerizable compound. (JP-A-63-218964
No. 2-146041 and No. 3-25444.
No.

When dispersing the base precursor in water, it is preferable to use a nonionic or amphoteric water-soluble polymer. Examples of nonionic water-soluble polymers are polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polymethyl vinyl ether, polyacryloylmorpholine, polyhydroxyethyl acrylate, polyhydroxyethyl methacrylate-co-acrylamide, hydroxyethyl cellulose, hydroxypropyl cellulose and Methyl cellulose etc. can be mentioned. Moreover, gelatin can be mentioned as an amphoteric water-soluble polymer. The above-mentioned water-soluble polymer is 0.1 to the base precursor.
It is preferably contained in a proportion of 100% by weight, 1
More preferably, it is contained in a proportion of about 50% by weight. Further, the base precursor is 5 to 60 relative to the dispersion liquid.
It is preferable that the content is 10% to 50% by weight.
More preferably, it is contained. Further, the base precursor is preferably contained in a proportion of 2 to 50% by weight, more preferably 5 to 30% by weight, based on the polymerizable compound.

Various known techniques can be applied to the microcapsules that can be used in the present invention without any particular limitation, and they are described in detail on pages 88 to 98 of the above-mentioned "Known Technique No. 5". In the present invention, it is particularly preferable to use a melamine-formaldehyde resin, since a highly dense capsule can be obtained. In addition, Japanese Patent Laid-Open No. 2-2
In order to obtain capsules having particularly excellent wall compactness, Japanese Patent No. 16151 discloses that a melamine film is formed around a film composed of a reaction product of a water-soluble polymer having a sulfinic acid group and a polymerizable compound having an ethylenically unsaturated group. A microcapsule provided with a polymer wall of a high molecular compound such as formaldehyde resin is disclosed, which is preferable for the present invention. When aminoaldehyde-based microcapsules are used, as in the light-sensitive material described in JP-A-63-32535,
It is preferable that the amount of residual aldehyde is not more than a certain value.
The method is described in JP-A-63-142343. The average particle size of the microcapsules is 1 to 50 μ.
m, preferably 3 to 20 μm. The particle size distribution of the microcapsules is preferably uniform over a certain value, as in the light-sensitive material described in JP-A-63-5334. The film thickness of the microcapsules is preferably within a certain range with respect to the particle diameter, as in the light-sensitive material described in JP-A-63-81336.

When the silver halide is contained in the microcapsules, the average grain size of the silver halide grains described above is preferably ⅕ or less, and preferably ⅕ or less of the average size of the microcapsules. More preferably, By setting the average grain size of the silver halide grains to be one fifth or less of the average size of the microcapsules, a uniform and smooth image can be obtained.
When the silver halide is contained in the microcapsules, it is preferable that the silver halide be present in the wall material that constitutes the outer shell of the microcapsules. Regarding a light-sensitive material containing a silver halide in the wall material of the microcapsule, JP-A-62-62
No. 169147.

In the production of the photosensitive microcapsules of the present invention, an oily liquid composed of a polymerizable compound containing silver halide, a reducing agent, a color image-forming substance and a base precursor is dispersed in an aqueous medium to form a capsule shell. When forming, it is preferable that the aqueous medium contains a nonionic water-soluble polymer and an anionic water-soluble polymer. In this case, the oily liquid containing the polymerizable compound is preferably 10 to 120% by weight with respect to the aqueous medium,
˜90% by weight is more preferred. Examples of nonionic water-soluble polymers are polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polymethyl vinyl ether, polyacryloylmorpholine, polyhydroxyethyl acrylate, polyhydroxyethyl methacrylate-co-acrylamide, hydroxyethyl cellulose, hydroxypropyl cellulose and Methyl cellulose etc. can be mentioned. Examples of the anionic water-soluble polymer include polystyrene sulfinic acid, copolymer of styrene sulfinate, polystyrene sulfonate, copolymer of styrene sulfonate, polyvinyl sulfate ester salt, polyvinyl sulfonate, maleic anhydride. -Styrene copolymers, maleic anhydride / inbutylene copolymers and the like can be mentioned. In this case, the concentration of the anionic water-soluble polymer in the aqueous medium is 0.01 to
The range of 5% by weight is preferable, and 0.1 is more preferable.
Is in the range of up to 2% by weight. In the above case, it is particularly preferable to use the nonionic water-soluble polymer in combination with the water-soluble polymer having a small amount of sulfinic acid groups.

In order to reduce the solubility of the base precursor in the polymerizable compound, polyethylene glycol, polypropylene glycol, benzoic acid amide, cyclohexylurea, octyl alcohol, dodecyl alcohol, stearyl alcohol, stearamide and the like can be used in the polymerizable compound. OH, -SO ₂ NH _2, -CONH
_{It is} also possible to add a compound having a hydrophilic group such as ₂ , ₂ , -NHCONH ₂ .

In the present invention, in addition to the reducing agent, known antioxidants for preventing oxidative deterioration of the polymerizable compound and for preventing oxygen oxidation during thermal development can be used together with the polymerizable compound. As such an antioxidant, 2,2 '
-Methylene-bis- (4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, 2,
2'-butylidene-bis- (4-methyl-6-t-butylphenol), 2-t-butyl-6- (3'-t-butyl-5'-methyl-2'-hydroxybenzyl) -4
-Methylphenyl acrylate, 4,4'-thio-bis- (3-methyl-6-t-butylphenol) and other phenolic antioxidants; diphenyldecyl phosphite,
Triphenyl phosphite, tris- (2,4-di-t
-Butylphenyl) phosphite, tris- (2-ethylhexyl) phosphite and other phosphite antioxidants; dilauryl-3,3'-thio-dipropionic acid ester, pentaerythritol-tetrakis- (β-lauryl-thio -Propionate), thio-dipropionic acid and other sulfur-based antioxidants; phenyl-1-naphthylamine, 6-ethoxy-2,2,4-trimethyl-
Examples include amine antioxidants such as 1,2-dihydroquinoline and dioctyliminodibenzyl.

Materials that can be used for the support include glass, paper, woodfree paper, baryta paper, coated paper, cast coated paper, synthetic paper, metal and its analogs, polyester, polyethylene, polypropylene, acetyl cellulose, cellulose. Ester, polyvinyl acetal,
Examples thereof include films such as polystyrene, polycarbonate, polyethylene terephthalate, and polyimide, and paper laminated with a resin material or a polymer such as polyethylene. For details, refer to “Public Technology No. 5”
No. "pp. 144-149. Among them, the preferred support of the present invention is a polymer film, and it is particularly preferred that it is a polymer film of 50 μm or less in view of the above-mentioned thermal conductivity. Further, in order to coat the photosensitive layer on the support, it is preferable to provide an undercoat layer described in JP-A-61-113058 on a polymer film or a metal vapor deposition film of aluminum or the like on the polymer film. Therefore, the support of the light-sensitive material of the present invention is particularly preferably a polymer film having a thickness of 50 μm or less and having an aluminum vapor deposition film.

Other components that can be used in the light-sensitive material of the present invention will be described below. Details of these components are described in the above-mentioned "Known Technology No. 5", pp. 98-144 and 86-.
It is described on page 88. The binder that can be used in the light-sensitive material can be contained in the light-sensitive layer alone or in combination. It is preferable to mainly use a hydrophilic binder. As the hydrophilic binder, a transparent or translucent hydrophilic binder is typical. For example, natural substances such as gelatin, gelatin derivatives, cellulose derivatives, starch, gum arabic, etc., and polyvinyl alcohol, polyvinylpyrrolidone, acrylamide polymers, etc. Synthetic polymers such as water-soluble polyvinyl compounds. Other synthetic polymeric materials include dispersed polyvinyl compounds in the form of latices, which in particular increase the dimensional stability of photographic materials. The light-sensitive material using a binder is described in JP-A-61-69062. Further, regarding a light-sensitive material using a binder together with microcapsules, see JP-A-62-209525.
It is described in the official gazette.

As the anti-smudge agent used in the light-sensitive material, solid particles at room temperature are preferable. Specific examples thereof include starch particles described in British Patent No. 1232347, polymer fine powder described in U.S. Pat. No. 3,625,736, and microcapsule particles containing no color former described in British Patent No. 12359991. US Patent No. 2
Examples include cellulose fine powder described in No. 711375, talc, kaolin, bentonite, wax, inorganic particles such as zinc oxide, titanium oxide and alumina. The average particle size of the particles is preferably in the range of 3 to 50 μm in volume average diameter, and more preferably in the range of 5 to 40 μm. As described above, when the oil droplets of the polymerizable compound are in the microcapsule state, it is more effective that the particles are larger than the microcapsules.

Various image forming accelerators can be used in the light-sensitive material. The image forming accelerator has a function of accelerating the transfer of a base or a base precursor, accelerating the reaction between a reducing agent and a silver salt, and accelerating the immobilization of a dye-donor substance by polymerization. It is classified into a base or a base precursor, a nucleophilic compound, an oil, a thermal solvent, a surfactant, a compound having an interaction with silver or a silver salt, a compound having an oxygen removing function, and the like. However, these substance groups generally have a composite function and usually have some of the above-mentioned accelerating effects together. For details of these, U.S. Pat. No. 4,678,739, columns 38 to 40,
It is described in the specifications and publications such as JP-A-62-209443. Also, the high-valent metal compounds described in Japanese Patent Application No. 2-272878 are effective.

In the photosensitive material, a system in which a polymerizable compound in a portion where a latent image of silver halide is not formed is polymerized,
A heat or photopolymerization initiator can be used for the purpose of initiating polymerization or for polymerizing an unpolymerized polymerizable compound after image transfer. Examples of thermal polymerization initiators include azo compounds, organic peroxides, inorganic peroxides, sulfinic acids and the like. Details thereof are described in pages 6 to 18 of “Addition Polymerization / Ring-Opening Polymerization” (1983, Kyoritsu Shuppan) edited by the Society for Polymer Science, Editorial Committee for Polymer Experiments. Examples of the photopolymerization initiator include benzophenones, acetophenones, benzoins, thioxanthones and the like.
For details of these, refer to "UV Curing System" (198).
9th year, General Technology Center) pp. 63-147.

Various surface-active agents can be used in the light-sensitive material for the purposes of coating aid, improvement of peeling property, improvement of sliding property, antistatic property, acceleration of development and the like. Specific examples of the surfactant are
It is described in JP-A-62-173463 and JP-A-62-183457. An antistatic agent can be used in the light-sensitive material for the purpose of antistatic. The antistatic agent is Research Disclosure, November 1978, No. 1764.
No. 3 (page 27) and the like. Dyes or pigments may be added to the photosensitive layer of the photosensitive material for the purpose of preventing halation or irradiation. A light-sensitive material in which a white pigment is added to the light-sensitive layer
It is described in Japanese Patent No. 48.

A dye having a property of being decolorized by heating or irradiation with light may be contained in the microcapsules of the light-sensitive material. The dye having the property of being decolorized by heating or light irradiation can function as a yellow filter in a conventional silver salt photographic system. A light-sensitive material using a dye having the property of being decolorized by heating or irradiation with light as described above is described in JP-A-63-974940. When a solvent for a polymerizable compound is used in the light-sensitive material, it is preferably used by enclosing it in a microcapsule different from the microcapsule containing the polymerizable compound. The photosensitive material using an organic solvent miscible with the polymerizable compound encapsulated in microcapsules is described in JP-A-62-209524.

Various antifoggants or photographic stabilizers can be used in the present invention. For example,
Azoles and azaindenes described in RD17643 (1978), pages 24 to 25, JP-A-59-168442.
Nitrogen-containing carboxylic acids and phosphoric acids described in JP-A-59-111636, mercapto compounds and metal salts thereof described in JP-A-59-111636, and acetylene compounds described in JP-A-62-87957 are used. .

Various development stoppers can be used in the light-sensitive material for the purpose of always obtaining a constant image with respect to the processing temperature and processing time during development. The term "development terminating agent" as used herein refers to a compound that immediately neutralizes or reacts with a base to reduce the concentration of the base in the film to stop the development after proper development, or to inhibit development by interacting with silver and a silver salt. Compound. Specific examples thereof include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction of a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound and a precursor thereof. More specifically, JP-A-62-253159, pages (31) to (32), JP-A-1-724
No. 79, No. 1-3471, etc. are described.

In addition to the above, examples of optional components that can be contained in the photosensitive layer and the usage thereof are also described in the application specification regarding the series of photosensitive materials described above, and Research Disclosure Vol. 170, 197.
No. 17029 (pages 9 to 15), June 1996. As the layer that can be optionally provided in the photosensitive material,
Examples thereof 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, and an antihalation layer (colored layer). A photosensitive material using a heating element layer is disclosed in JP-A-61-294434, and a photosensitive material provided with a cover sheet or a protective layer is disclosed in JP-A-62-210447. A coloring layer as an antihalation layer is disclosed. The light-sensitive materials provided with are described in JP-A-63-101842. Further, examples of other auxiliary layers and usage modes thereof are also described in the specification of the series of photosensitive materials described above.

In the image forming method using the light-sensitive material of the present invention, it is general to use the image-receiving material together with the light-sensitive material. The image receiving material will be described below. The details are described in "Public Technology No. 5", pages 149 to 178. The image receiving material may be only the support, but it is preferable to provide an image receiving layer on the support. The support of the image receiving material is not particularly limited, but like the support of the photosensitive material, glass, paper, high-quality paper, baryta paper, coated paper, cast coated paper, synthetic paper, cloth, metal and its analogs, Examples thereof include films such as polyester, polyethylene, polypropylene, acetyl cellulose, cellulose ester, polyvinyl acetal, polystyrene, polycarbonate, polyethylene terephthalate, and paper laminated with a resin material or a polymer such as polyethylene. When a porous material such as paper is used as the support for the image receiving material, it is preferable that the image receiving material has a certain smoothness as in the image receiving material described in JP-A-62-209530. Further, an image receiving material using a transparent support is described in JP-A-62-209531.

The image-receiving layer of the image-receiving material is composed of a white pigment, a binder, and other additives, and the white pigment itself or voids between the particles of the white pigment enhance the receptivity of the polymerizable compound. Examples of the white pigment used in the image receiving layer include inorganic white pigments such as oxides of silicon oxide, titanium oxide, zinc oxide, magnesium oxide, aluminum oxide, magnesium sulfate, barium sulfate, calcium sulfate, magnesium carbonate, carbonic acid. Alkaline earth metal salts such as barium, calcium carbonate, calcium silicate, magnesium hydroxide, magnesium phosphate, magnesium hydrogen phosphate, etc., as well as aluminum silicate, aluminum hydroxide, zinc sulfide, each sugar clay, talc, kaolin, Zeolite, acid clay, activated clay, glass, etc. may be mentioned. Organic white pigments include polyethylene, polystyrene, benzoguanamine resins, urea-formalin resins,
Examples thereof include melamine-formalin resin and polyamide resin. These white pigments may be used alone or in combination, but those having a high oil absorption amount with respect to the polymerizable compound are preferable.

As the binder used in the image-receiving layer of the present invention, a water-soluble polymer, a polymer latex, a polymer soluble in an organic solvent or the like can be used. As the water-soluble polymer, for example, carboxymethyl cellulose, hydroxyethyl cellulose, cellulose derivatives such as methyl cellulose, gelatin, phthalated gelatin, casein, proteins such as ovalbumin, starches such as dextrin, etherified starch, polyvinyl alcohol,
Polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, synthetic polymers such as polyvinyl imidazole, polyvinyl pyrazole, polystyrene sulfonic acid, etc., locust bean gum, pullulan, gum arabic, alginic acid Examples include soda. Examples of the polymer latex include styrene-butadiene copolymer latex, methyl methacrylate / butadiene copolymer latex, polymer of acrylic acid ester and / or methacrylic acid ester, copolymer latex, ethylene / vinyl acetate copolymer latex. Etc. Examples of the polymer soluble in an organic solvent include polyester resin, polyurethane resin, polyvinyl chloride resin, polyacrylonitrile resin and the like.

As a method of using the above binder, two or more kinds can be used in combination, and further, two kinds of binders can also be used in a ratio such that phase separation occurs. As an example of such usage, JP-A-1-154789
There is a description in the official gazette. The average particle size of the white pigment is 0.
1 to 20 μ, preferably 0.1 to 10 μ, and the coating amount is 0.1 g to 60 g, preferably 0.5 g to 30 g
The range is. The weight ratio of the white pigment to the binder is preferably 0.01 to 0.4, more preferably 0.03 to 0.3, relative to 1 pigment.

The image-receiving layer may contain various additives as described below, in addition to the binder and the white pigment. For example, when a color-developing system including a color-developing agent and a color-developing agent is used, the image-receiving layer may contain the color-developing agent. Typical developers include phenols, organic acids or salts thereof, or esters, but when a leuco dye is used as a color image forming substance, a zinc salt of a salicylic acid derivative is preferable, Above all,
Zinc 3,5-di-α-methylbenzyl salicylate is preferred. The above color developer is preferably contained in the image receiving layer in a coating amount of 0.1 to 50 g / m ² . More preferably, it is in the range of 0.5 to 20 g / m ² .

The image receiving layer may contain a thermoplastic compound. When the image receiving layer contains a thermoplastic compound, it is preferable that the image receiving layer itself is formed as an aggregate of thermoplastic compound fine particles. The image-receiving layer having the above-described structure has an advantage that a transfer image can be easily formed and a glossy image can be obtained by heating after the image formation.
The thermoplastic compound is not particularly limited and can be arbitrarily selected and used from known plastic resins (plastics) and waxes. However, the glass transition point of the thermoplastic resin and the melting point of the wax are preferably 200 ° C. or lower. Regarding the image-receiving material having the image-receiving layer containing the above-mentioned fine particles of a thermoplastic compound, Japanese Patent Application Laid-Open Publication No. 6-58242
2-280071 and 62-280739.

The image-receiving layer may contain a photopolymerization initiator or a thermal polymerization initiator. In image formation using an image receiving material, a color image forming substance is transferred together with an unpolymerized polymerizable compound. Therefore, a photopolymerization initiator or a thermal polymerization initiator can be added to the image-receiving layer for the purpose of curing (fixing) the unpolymerized polymerizable compound. An image receiving material having an image receiving layer containing a photopolymerization initiator is disclosed in JP-A-62-161149, and an image receiving material having an image receiving layer containing a thermal polymerization initiator is disclosed in JP-A-62-161149.
Each of them is described in Japanese Patent Publication No. 210444.

In the following, the step of imagewise exposure in the image forming method of the present invention, the imagewise exposure, or after the imagewise exposure, the photosensitive material is heated from the surface of the support having no photosensitive layer coated thereon. And a series of steps such as a step of superposing the surface of the photosensitive material coated with the photosensitive layer and the image receiving material and pressurizing the same. As the exposure method in the imagewise exposure step, various exposure means can be used, but in general, a latent image of silver halide is obtained by imagewise exposure to radiation including visible light. The type of light source and the amount of exposure can be selected according to the photosensitive wavelength of silver halide (wavelength sensitized when dye sensitization is performed) and sensitivity. Typical light sources include low-energy radiation sources such as natural light, ultraviolet rays, visible light, infrared rays, fluorescent lamps, tungsten lamps, mercury lamps, halogen lamps, xenon flash lamps, laser light sources (gas laser, solid state laser, chemical laser, Semiconductor laser, etc.), light emitting diode,
A plasma arc tube, FOT, etc. can be mentioned. In special cases, it is possible to use X-rays, γ-rays, electron beams, etc., which are high-energy ray sources.

The light-sensitive material of the present invention, particularly in the case of a full-color light-sensitive material, is composed of microcapsules having photosensitivity in a plurality of spectral regions, and therefore it is necessary to perform image exposure with a plurality of corresponding spectral lines. Is. Therefore, the light sources may be used alone or in combination of two or more. When selecting the light source,
It goes without saying that a light source suitable for the photosensitive wavelength of the photosensitive material is selected, but it can be selected in consideration of whether image information passes through an electric signal, the processing speed of the entire system, compactness, power consumption, and the like.

When the image information does not pass through an electric signal, for example, direct photographing of landscapes and people, direct copying of original images,
In the case of exposing through a positive such as a reversal film, an exposure device for printing such as a camera, a printer or an enlarger, an exposure device for a copying machine or the like can be used. In this case, a two-dimensional image can be simultaneously exposed by so-called one shot, or scanning exposure can be performed through a slit or the like. You can also stretch or reduce the original image. In this case, the light source is not a monochromatic light source such as a laser but a light source such as a tungsten lamp or a fluorescent lamp, or a combination of a plurality of monochromatic light sources.

When image information is recorded via an electric signal, as an image exposure device, a light emitting diode and various lasers may be used in combination according to the color sensitivity of the heat-developable color photosensitive material. Various devices known as an image display device (CRT, liquid crystal display, electroluminescence display, electrochromic display, plasma display, etc.) can also be used. In this case, the image information is an image signal obtained from a video camera or an electronic still camera, a television signal represented by Nippon Television Signal Standard (NTSC),
An image signal obtained by dividing an original image into a large number of pixels with a scanner or the like, or an image signal stored in a recording material such as a magnetic tape or a disk can be used.

Upon exposure of a color image, LEDs, lasers, fluorescent tubes and the like are used in combination according to the color sensitivity of the light-sensitive material. However, a plurality of the same materials may be used in combination, or different kinds of materials may be used in combination. May be. The color sensitivity of the light-sensitive material is R (red), G (green), B (blue) in the photographic field.
Photosensitivity is normal, but in recent years, it is often used in combination with UV, IR, etc., and the range of use of the light source is expanding. For example, the color sensitivity of the photosensitive material is (G, R, IR)
Or (R, IR (short wave), IR (long wave)),
(UV (short wave), UV (medium wave), UV (long wave)), (U
Spectral regions such as V, B, G) are utilized. The light source may also be a combination of different types such as a combination of two LED colors and a laser. The light emitting tube or element may be scanned and exposed by using a single tube or element for each color, or an array tube may be used to increase the exposure speed. Examples of usable arrays include an LED array, a liquid crystal shutter array, and a magneto-optical element shutter array.

The image display device described above is a CRT.
As described above, there are color display and monochrome display, but a method of performing exposure several times by combining filters of monochrome display may be adopted. The existing two-dimensional image display device may be used by making it one-dimensional like FOT, or by dividing one screen into several pieces and using them in combination with scanning. By the above imagewise exposure, a latent image is obtained on the silver halide contained in the microcapsules.

The image forming method of the present invention includes a step of heating the photosensitive material at the same time as the imagewise exposure or after the imagewise exposure to thermally develop the photosensitive material. Thermal development is preferably performed by heating from the surface of the support on which the photosensitive layer of the photosensitive material is not coated. As the heating means, as in the light-sensitive material described in JP-A-61-294434,
A heating element layer may be provided on the surface of the support on which the photosensitive layer of the photosensitive material is not coated to heat it. Further, JP-A-61-1
As described in JP-A-47244, a hot plate, an iron, and a heat roller are used, or as described in JP-A-62-144166, a method of heating a photosensitive material by sandwiching it between a heat roller and a belt is used. Good. That is, the photosensitive material may be brought into contact with a heating element having a surface area larger than that of the photosensitive material to heat the entire surface at the same time, or a heating element having a smaller surface area (a heating plate, a heating roller, a heating drum, etc.) You may make it contact and make it scan and heat the whole surface over time. In addition to the heating method in which the heating element and the photosensitive material are brought into direct contact with each other as described above, electromagnetic waves, infrared rays, hot air or the like may be applied to the photosensitive material to heat it in a non-contact state.

In the image forming method of the present invention, thermal development is carried out by heating the surface of the photosensitive material on the support on which the photosensitive layer is not coated. At this time, the photosensitive layer is coated. The surface method may be in direct contact with air,
It may be covered with a heat insulating material or the like in order to keep it warm so as not to release heat. In this case, it is preferable not to apply a strong pressure (10 kg / cm ² or more) to the photosensitive layer so as not to destroy the microcapsules contained in the photosensitive layer. Further, the heat development by heating is carried out simultaneously with or after the imagewise exposure, but it is preferable to perform the heating after 0.1 seconds or more has passed after the imagewise exposure. Heating temperature is generally 60 ℃
To 250 ° C, preferably 80 ° C to 180 ° C,
The heating time is between 0.1 and 20 seconds, preferably between 0.5 and 5 seconds.

The photosensitive material can be subjected to heat development as described above to polymerize the polymerizable compound in the portion where the latent image of silver halide is formed or the portion where the latent image of silver halide is not formed. When a polymerization inhibitor is formed in the latent image-formed portion of silver halide by the reaction with a reducing agent, heat or photopolymerization initiation which has been added in advance in the photosensitive layer, preferably in the microcapsules. It is also possible to decompose the agent by heating or irradiating it with light to uniformly generate radicals and polymerize the polymerizable compound in the portion where the latent image of silver halide is not formed. In this case, in addition to the above-mentioned imagewise exposure step and heat development step, if necessary, a whole surface heating or whole surface exposure step is required, and the method is the same as the imagewise exposure step or the heat development step.

In the image forming method of the present invention, the unpolymerized polymerizable compound is transferred to the image receiving material by the step of applying pressure in the state where the photosensitive material having a polymer image and the image receiving material are superposed on the photosensitive layer, A color image can be obtained on the image receiving material. A conventionally known method can be used as the pressurizing method. For example, the photosensitive material and the image receiving material may be sandwiched between press plates such as a presser, or pressure may be applied while being conveyed using a pressure roller such as a nip roll.
The pressure may be intermittently applied by a dot impact device or the like. Further, high pressure air can be wiped with an air gun or the like, or can be pressurized with an ultrasonic wave generator, a piezoelectric element or the like. The pressure required for pressurization is 500 kg / cm ² or more, preferably 800 kg / cm ² or more. However, when heating is also used at 40 ° to 120 ° C during pressurization, 500 kg
It may be less than / cm ² .

The light-sensitive material of the present invention has many uses such as a color photographing and printing light-sensitive material, a printing light-sensitive material, a computer graphic hard copy light-sensitive material, a copying machine light-sensitive material, and the like. It is possible to create compact and inexpensive image forming systems such as copiers, printers, and simple printers.

[0057]

【Example】

Example 1 Preparation of Blue-Sensitive Silver Halide Emulsion (EB-11) 24 g of lime-treated inert gelatin was added to 900 ml of distilled water, dissolved at 40 ° C. for 1 hour and 1.5 g of KBr was added, and 1N sulfuric acid was added thereto. The pH was adjusted to 3.2.
After adding 5 mg of (AGS-1) to this solution, solution I and solution II were added at 75 ° C. by the control double jet method while keeping pAg = 8.5 at the same time for 45 minutes until solution I disappeared. After the addition is complete, adjust the pH to 1N Na
Adjusted to 6.0 with OH, (AZ-1) 2 mg, (AZ-
2) 2.5 mg, (AZ-3) 20 mg and KBr3
g and ripened at 60 ° C. for 40 minutes. After aging (SB-
1) 320 mg and (SB-2) 160 mg were added, and after 20 minutes, an aqueous solution 100 containing KI 3.5 g
ml was added over 5 minutes. To this emulsion, 1.1 g of poly (isobutylene-co-maleate monosodium) was added, precipitated, washed with water and desalted, then 6 g of lime-treated inert gelatin was added and dissolved, and 72% of (ATR-1) was added.
3 ml of an aqueous solution was added to adjust the pH to 6.2. As described above, the average particle size is 0.24 μm and the coefficient of variation is 20%.
550 g of a blue-sensitive monodisperse silver iodobromide emulsion (EB-11) was prepared.

Liquid I AgNO ₃ 120 g Distilled water 600 ml Liquid II KBr 85 g Distilled water 600 ml

Preparation of Green-Sensitive Silver Halide Emulsion (EG-11) Similar to silver halide emulsion (EB-11), except that the addition time of Solution I and Solution II was 10 minutes, and the temperature at the time of addition was 70 ° C., and further (SB-1) and (SB-2)
Instead of (SG-1) 230 mg, (SG-2) 10
0 mg and (SG-3) 200 mg were added to prepare 550 g of a green-sensitive monodisperse silver iodobromide emulsion (EG-11) having an average grain size of 0.18 μm and a coefficient of variation of 20%.

Preparation of Red-Sensitive Silver Halide Emulsion (ER-11) As in the case of silver halide emulsion (EB-11), the addition time of Solution I and Solution II was 15 minutes, and the temperature at the time of this addition was 70 ° C., and (SB-1) and (SB-
Instead of 2), (SR-1) 300 mg, (SR-
2) 150 mg and (SR-3) 30 mg were added to prepare 550 g of a red-sensitive monodisperse silver iodobromide emulsion (ER-11) having an average grain size of 0.18 μm and a coefficient of variation of 22%.

[0061]

[Chemical 1]

[0062]

[Chemical 2]

[0063]

[Chemical 3]

[0064]

[Chemical 4]

Preparation of solid dispersion (KB-1) 5. Lime-processed gelatin in a 300 ml dispersion container.
110 g of a 4% aqueous solution, 20 g of a 5% aqueous solution of polyethylene glycol (average molecular weight 2000), 70 g of a base precursor (BG-1) and 200 ml of glass beads having a diameter of 0.5 to 0.75 mm are added, and a dyno mill is used to rotate at 3000 rpm. For 30 minutes, and the pH was adjusted to 6.5 with 2N sulfuric acid to obtain a solid dispersion (KB-1) of a base precursor (BG-1) having a particle size of 1.0 μm or less.

[0066]

[Chemical 5]

Preparation of Yellow Pigment Dispersion (GY-1) To 240 g of the polymerizable compound (MN-1), 60 g of Seika Fast Yellow 2300 (trade name, manufactured by Dainichiseika Co., Ltd.)
Were mixed and stirred at 5,000 rpm for 1 hour using an Eiger motor mill (manufactured by Eiger Engineering Co.) to obtain a yellow pigment dispersion (GY-1). Polymerizable compound (MN-1) Compound described in Synthesis Example 1 of JP-A-64-68339 (manufactured by Nippon Kayaku Co., Ltd.)

Preparation of Magenta Pigment Dispersion (GM-1) After mixing 255 g of the polymerizable compound (MN-1) with 45 g of Microlith Magenta 2BA (trade name, manufactured by Ciba Geigy) and 23 g of the compound (SV-1). 20 with a 40φ dissolver at 70 ° C and 5000 rpm
After stirring for a minute, a magenta pigment dispersion (GM-1) was obtained.

Preparation of Cyan Pigment Dispersion (GC-1) To 240 g of the polymerizable compound (MN-1), 60 g of copper phthalocyanine D-1709 (trade name, manufactured by Dainichiseika Co., Ltd.), compound (SV-2) 1. 2g and Disperbic 161
(Product name, made by Big Chemie) 20g is mixed, and Eiger Motor Mill (made by Eiger Engineering)
Was stirred at 5000 rpm for 1 hour to obtain a cyan pigment dispersion (GC-1).

[0070]

[Chemical 6]

Preparation of Blue Photosensitive Composition (PB-1) To 34 g of the yellow pigment dispersion (GY-1), 11 g of the polymerizable compound (MN-1) and (SV-1) 10 of (1P-1).
9% by weight solution, (RD-1) 1.2 g, (RD-2)
4.6 g, 1 g of a 0.5% by weight solution of (SV-1) in (FF-1) and 0.5 g of (ST-1) were added and dissolved to prepare an oily solution. To this solution, 9 g of a blue-sensitive silver halide emulsion (EB-11) and 24 g of a solid dispersion (KB-1) were added.
g, and while maintaining the temperature at 60 ° C., using a 40φ dissolver, stirring at 10000 rpm for 5 minutes, and W / O
An emulsion blue-sensitive composition (PB-1) was obtained.

Preparation of Green Photosensitive Composition (PG-1) To 48 g of pigment dispersion (GM-1), (SV of (1P-1)
-1) 8 g of 10 wt% solution, (RD-1) 1 g, (RD
-2) 3.1 g, 0.8 g of (SV-1) 0.5 wt% solution of (FF-1) and (ST-2) 0.5 g were added and dissolved to prepare an oily solution. To this solution, 6 g of a green-sensitive silver halide emulsion (EG-11) and 20 g of a solid dispersion (KB-1) were added, and while keeping the temperature at 60 ° C., 4
The mixture was stirred at 0,000 rpm for 5 minutes using a 0φ dissolver, and a green photosensitive composition (PG-
1) was obtained.

Preparation of Red Photosensitive Composition (PR-1) To 36 g of the cyan pigment dispersion (GC-1), 11 g of the polymerizable compound (MN-1) and (SV-1) 10 of (1P-1).
Weight% solution 8 g, (RD-1) 1.2 g, (RD-2)
An oily solution was prepared by adding 2.6 g, 0.8 g of a (SV-1) 0.5% by weight solution of (FF-1) and 0.4 g of (ST-1) and dissolving them. 6.4 g of a red-sensitive silver halide emulsion (ER-11) and a solid dispersion (KB-
1) Add 24 g, and while maintaining the temperature at 50 ° C., stir at 10000 rpm for 5 minutes using a 40φ dissolver,
A red photosensitive composition (PR-1) of W / O emulsion was obtained.

[0074]

[Chemical 7]

[0075]

[Chemical 8]

Preparation of Blue-sensitive Microcapsule Dispersion Liquid (CB-1) 4.5 g of a 12% aqueous solution of polymer (2P-1) was added with 4 parts of water.
6 g was added and the mixed solution was adjusted to pH 5.0 with 2N sulfuric acid. A 50% 10% aqueous solution of polymer (2P-2) was added to this liquid.
g and mixed at 60 ° C. for 30 minutes. The above blue photosensitive composition (PB-1) was added to this polymer aqueous solution to obtain 40φ.
20 at 7,000 rpm with a dissolver at 60 ° C
After stirring for a minute, an emulsion in the state of W / O / W emulsion was obtained. Separately, 31.5 g of melamine and 3 parts of formaldehyde
52.2 g of a 7% aqueous solution and 170.3 g of water were added,
The mixture was heated to 60 ° C. and stirred for 30 minutes to obtain a transparent aqueous solution of melamine-formaldehyde initial condensation product. 33 g of this initial condensate was added to the emulsified product in the state of W / O / W emulsion cooled to 40 ° C., and 12 minutes per minute with a propeller blade.
The pH was adjusted to 4.0 with 2N sulfuric acid while stirring at 00 revolutions. Next, the temperature of this liquid was raised to 70 ° C. in 30 minutes, and further stirred for 30 minutes. 40% of this is urea
13.5 g of an aqueous solution was added, the pH was adjusted to 3 with 2N sulfuric acid, and stirring at 70 ° C. was continued for another 40 minutes. This solution was cooled to 40 ° C., 9 g of a 3% aqueous solution of κ-carrageenan was added, and the mixture was stirred for 10 minutes and adjusted to pH 5 with a 2N aqueous sodium hydroxide solution to prepare a blue-sensitive microcapsule dispersion (CB-1). ) Was prepared.

Preparation of Green Photosensitive Microcapsule Dispersion Liquid (CG-1) 3% of water was added to 6.8 g of a 12% aqueous solution of polymer (2P-1).
3 g was added and the mixed solution was adjusted to pH 5 with 2N sulfuric acid.
To this solution, 60 g of a 10% aqueous solution of polymer (2P-2) was added, and mixed at 60 ° C for 30 minutes. The photosensitive composition (PG-1) was added to this mixed solution, and the mixture was stirred at 60 ° C. for 20 minutes at 8000 rpm using a 40φ dissolver, and was then mixed with W.
An emulsion in the form of a / O / W emulsion was obtained. Then, a green photosensitive microcapsule dispersion liquid (CG-1) was prepared in the same manner as the preparation of (CB-1).

Preparation of Red-sensitive Microcapsule Dispersion Liquid (CR-1) 45 g of water was added to 5 g of 12% aqueous solution of polymer (2P-1).
In addition, the mixed solution was adjusted to pH 5 with 2N sulfuric acid. To this solution, 50 g of a 10% aqueous solution of polymer (2P-2) was added, and mixed at 60 ° C for 30 minutes. The above-mentioned photosensitive composition (PR-1) was added to this mixed solution, and the mixture was stirred at 60 ° C. for 20 minutes at 8000 rpm using a 40φ dissolver, and W /
An emulsion in the form of an O / W emulsion was obtained. Then (C
A red-sensitive microcapsule dispersion liquid (CR-1) was prepared in the same manner as in the preparation of B-1). Polymer (2P-1) Copolymer composition of potassium polyvinylbenzenesulfinate and acrylamide Polymer (2P-2) Polyvinylpyrrolidone K-9
0

Preparation of Emulsion (VA-1) 100 g of a 10% aqueous solution of PVA, KL-318 (trade name, carboxy-modified PVA manufactured by Kuraray Co., Ltd.) was added with the compound (WW
After adding and mixing 30 g of a 5% aqueous solution of -2), 100 g of the polymerizable compound (MN-1) was added, and then emulsified with a 40φ dissolver at 40 ° C., 10,000 rpm for 5 minutes to obtain an emulsion (VA- 1) was prepared.

Preparation of Photosensitive Material (101) The blue-sensitive microcapsule liquid (CB-1) of the present invention was used in 16
g, 14 g of green-sensitive microcapsule liquid (CG-1),
15 g of the red-sensitive microcapsule liquid (CR-1) was taken out, and each was heated to 40 ° C. to be melted and mixed, and then 13 g of the emulsion (VA-1) and the surfactant (WW
6.5 g of a 5% aqueous solution of -1) was added, and the mixture was stirred at 40 ° C. for 10 minutes and mixed. This solution was filtered with a filter cloth of 44 μm mesh to prepare a coating solution. This coating liquid has a thickness of 16 μm
Of polyethylene terephthalate film on which aluminum was vapor-deposited, was coated on the aluminum vapor-deposited surface of the support by an extrusion method so that the coating amount was 76 ml / m ² , dried at 55 ° C., and then coated at 25 ° C. and 60%. And the photosensitive material for comparison (10
1) was created.

[0081]

[Chemical 9]

Preparation of Image Receiving Material (RS-1) An aqueous solution prepared by mixing 110 g of a surfactant (Poise 520, manufactured by Kao Corporation) and 7090 g of water was mixed with a stirrer (trade name: TK homomixer O type, special type). While stirring at 4500 rpm with Kika Kogyo Co., Ltd., calcium carbonate (Callite SA, manufactured by Shiraishi Central Research Institute) 4800
g was gradually added over about 10 minutes, and dispersion was carried out for 30 minutes after starting the addition of calcium carbonate to obtain a 40 wt% slurry of calcium carbonate. This slurry 1200
0 g and 950 g of a 1% aqueous solution of a surfactant (WW-3),
Polyvinyl alcohol (PVA, KL-318, Kuraray Co., Ltd.) 10% aqueous solution 18000 g and water 11205 g
Was mixed and stirred for 1 hour while maintaining the temperature at 25 ° C., and then 3465 g of a 3% aqueous solution of polyamide epichlorohydrin resin (FL-71, manufactured by Toho Chiba Chemical Industry Co., Ltd.) was further added and stirred to form an image receiving layer. A coating solution was prepared.

[0083]

[Chemical 10]

This coating solution was weighed 80 g / m ^{2 on} a paper support (as a fiber length distribution defined by JIS-P-8207, the sum of the weight% of the 24 mesh residue and the weight% of the 42 mesh residue was 30). A paper support having a fiber length distribution such that the fiber length distribution is from 60 to 60% [JP-A-63-18623]
No. 9)]) was uniformly coated on the surface of the plate at a rate of 84 g / m ² and then dried at 110 ° C. to prepare an image receiving material (RS-1). Image forming procedure and evaluation of light-sensitive material Using a halogen lamp in which the light-sensitive material (101) was adjusted to a color temperature of 3100K, a wedge having a transmission density of 0 to 2.0 which was changed stepwise was used, and a condition of 200 lux and an exposure condition of 1 second was used. Exposed. Immediately after the exposure, the opposite side of the coated surface of the light-sensitive material was brought into close contact with a drum heated to 152 ° C. and heated for 1 second, and then the image-receiving material (RS-1) and the coated surface were overlapped with each other at 50 mm / sec. 30m diameter at speed
m, pressure 280 kg / cm ² pressure roller (surface temperature 7
0 ° C.). Immediately after passing, the image-receiving material was peeled off from the light-sensitive material, and the density of the positive image obtained on the image-receiving material was changed to X-Rite.
It was measured at 310. Next, in the image forming procedure, when the heating time is changed and each optimum temperature is recalculated, and when only the temperature is lowered by 2 ° C. with respect to the recalculated optimum temperature,
The difference in reflection density when the temperature was raised by ℃ was obtained (hereinafter this value is
2 ° C concentration fluctuation range "). This density fluctuation range was obtained as a density fluctuation value at an exposure amount that shows a reflection density of 0.6 at the optimum temperature. The experimental results are shown in Table 1 for each of the B filter density, the G filter density, and the R filter density.

(Table 1) Heating time (seconds) Optimal heating temperature “± 2 ° C. concentration fluctuation range” B concentration G concentration R concentration 0.5 159 ° C. 0.40 0.38 0.39 1.0 152 ° C. 35 0.32 0.33 2.0 147 ° C 0.28 0.26 0.27 4.0 143 ° C 0.24 0.21 0.22 8.0 140 ° C 0.15 0.14 0.14 or more From the results of the above, as compared with the development processing in which the heating time is relatively long, the development processing in which the heating time is short, particularly in the case of 5 seconds or less, the above-mentioned “± 2 ° C. concentration fluctuation range” sharply increases, and the processing is performed rapidly. It can be seen that it becomes difficult to obtain an image of stable quality.

Example 2 Blue-sensitive silver halide emulsions (EB-21, 22, 23, 2)
Preparation of 4) 24 g of lime-treated inert gelatin was added to 800 g of distilled water, dissolved at 40 ° C. over 1 hour, and then NaCl 1.7 was added.
g was added, and 1N sulfuric acid was added thereto to adjust the pH to 3.2. After adding 1 mg of (AGS-1) to this solution, (I-
Solution 1) and solution (II-1) were added at 45 ° C over 45 minutes. 10 minutes after the completion of this addition, the liquids (I-2) and (II-2) were added at 45 ° C. for 10 minutes. After this addition was completed (SB-1) 320 mg and (S
B-2) 160 mg was added, the temperature was immediately raised to 70, and stirring was continued for 40 minutes. Next, after lowering the temperature to 45 ° C., the liquids (I-3) and (II-3) were added over 45 minutes, and 1.1 g of poly (isobutylene-co-maleate monosodium) was added at 40 ° C. In addition, after sedimentation, washing with water and desalting, 6 g of lime-treated inert gelatin was added and dissolved, and further 3 ml of a 72% aqueous solution of (ATR-1).
Was added to adjust the pH to 6.2.

18 mg of (AZ-2) was added to this emulsion,
(AZ-4) 0.3 mg, (AZ-5) 0.05 mg and (AZ-6) 10 mg were added and stirred at 60 ° C. for 50 minutes, and further (AZ-7) 100 mg was added and the mixture was heated to 60 ° C. for 15 minutes. After keeping the temperature, it was cooled to 40 ° C. As described above, 600 g of a red-sensitive monodisperse silver chlorobromide emulsion (EB-21) having an average grain size of 0.31 μm and a coefficient of variation of 18% was prepared.

[0088]

[Chemical 11]

Solution I (I-1) Solution (I-2) Solution (I-3) Solution AgNO ₃ 100 g 20 g 0.6 g Distilled water 400 ml 70 ml 40 ml Solution II (II-1) Solution (II-2) ( II-3) Liquid NaCl 34.4 g 6.9 g --- KBr --- 0.42 g Distilled water 400 ml 70 ml 40 ml

Similarly, the amounts of AgNO _{3 in the} liquids (I-1), (I-2) and (I-3) and (II-1).
Emulsion (Table 2) in the same manner as the blue-sensitive monodisperse silver chloride emulsion (EB-21), except that the amounts of NaCl and KBr in Solution (II-2) and Solution (II-3) were changed. EB
-22) and (EB-23) were prepared. (Table 2) Emulsion name Silver chloride content High silver bromide phase Position within high silver bromide phase Volume fraction Silver bromide content (EB-21) 99.5 mol% Surface 2% 25 mol% Inventive Example (EB-22) 96.0 mol% Surface 10% 35 mol% Inventive Example (EB-23) 90.0 mol% Surface 25% 40 mol% Comparative Example (EB-24) 96.0 mol% Internal 20% 30 mol% Present invention An example

Green-sensitive silver halide emulsions (EG-21, 2
2, 23, 24) In the method for preparing a silver halide emulsion (EB-21, 22, 23, 24), the addition time of Solution (I-1) and Solution (II-1) is 25 minutes, and (SB-1) and (SB-
Instead of adding 2), 230 mg of (SG-1), (S
G-2) 100 mg and (SG-3) 200 mg except that silver halide emulsions (EB-2, 3, 4)
And the green-sensitive silver halide emulsion (EG-21, 2 having an average grain size of 0.26 μm and a coefficient of variation of 18%).
2, 23, 24) were prepared.

Red-sensitive silver halide emulsions (ER-21, 2
Preparation of 2, 23, 24) In the method for preparing a silver halide emulsion (EB-21, 22, 23, 24), 300 mg of (SR-1) is used instead of adding (SB-1) and (SB-2). , (SR-
2) Silver halide emulsions (EB-21, 22, 23, except that 150 mg and (SR-3) 30 mg were added.
24) average particle size 0.27μ
m, variation coefficient of 18%, red-sensitive silver halide emulsion (ER-
21, 22, 23, 24) were prepared.

Preparation of light-sensitive material (201, 202, 203, 204) In the preparation of light-sensitive material (101), except that the silver halide emulsion used for preparation of the light-sensitive composition was changed as shown in (Table 3). Photosensitive materials (201, 202, 203, 204) were prepared in the same manner as the photosensitive material (101). (Table 3) Photosensitive material No. Blue-sensitive emulsion Blue-sensitive emulsion Blue-sensitive emulsion (101) (EB-11) (EB-11) (EB-11) (201) (EB-21) (EB-21) (EB-21) (202) (EB) -22) (EB-22) (EB-22) (203) (EB-23) (EB-23) (EB-23) (204) (EB-24) (EB-24) (EB-24)

Image forming procedure and evaluation of photosensitive material The photosensitive material (201, 202, 203, 204)
The results of evaluation conducted in the same manner as the photosensitive material (101) are shown below (Table 4). Here (Table 4) is the "± 2 concentration fluctuation range" when the heating time is 1 second and the heating temperature is 152 ° C. (Table 4) Photosensitive material Silver halide grain “± 2 ° C. concentration fluctuation range” Remark Halogen composition ratio (mol%) B concentration G concentration R concentration Cl Br I (101) 97 3 0.35 0.32 0.33 Comparison Example (201) 99.5 0.5 (Surface) 0 0.14 0.13 0.13 Inventive Example (202) 96 4 (Surface) 0 0.19 0.18 0.18 Inventive Example (203) 90 10 (Surface) ) 0 0.27 0.24 0.26 Comparative Example (204) 964 (Internal) 0 0.21 0.20 0.20 Inventive Example

As is clear from the above results, by using the high silver chloride emulsion of the present invention, stable color image formation can be carried out with little dependence on the heat development temperature. Furthermore, when using silver chlorobromide grains, it is preferable that the high silver bromide phase is located on the surface. In this embodiment, the blue-sensitive silver halide, the green-sensitive silver halide and the red-sensitive silver halide of each light-sensitive material have the same halogen composition, but the present invention is not limited to this. Rather, in carrying out the method, it is necessary to determine the halogen composition of the silver halide to an optimum value if necessary.

Example 3 In the preparation of the light-sensitive material (201) of Example 2, silver halide emulsions (EB-21), (EG-21) and (E) were used.
During preparation of R-21), the solution (II-2) was added to (Table 5).
(EB-21), (E) except that the indicated amount of yellow blood salt was added.
G-21) and (ER-21) in the same manner as silver halide emulsions (EB-31, 32, 33) and (EG-3).
1, 32, 33) and (ER-31, 32, 33) were prepared.

Preparation of light-sensitive material (301, 302, 303) Light-sensitive material except that the silver halide emulsion used in the preparation of the light-sensitive composition was changed as shown in (Table 5) in the preparation of light-sensitive material (101). Photosensitive materials (301, 302, 303) were prepared in the same manner as (101).

(Table 5) Photosensitive material No. Blue-sensitive emulsion Green-sensitive emulsion Red-sensitive emulsion Yellow blood salt content (molar ratio to silver) (201) (EB-21) (EG-21) (ER-21) 0 (301) (EB-31) (EG- 31) (ER-31) ^5x10-7 (302) (EB-32) (EG-32) (ER-32) ^1x10-5 (303) (EB-33) (EG-33) (ER -33) 5 x 10 ^-4

Image Forming Procedure and Evaluation of Photosensitive Material The photosensitive materials (301, 302, 303) were evaluated in the same manner as the photosensitive material (201), and the results are shown below (Table 6). Here (Table 6) shows a heating time of 1 second and a heating temperature of 152.
“± 2 concentration fluctuation range” at ° C. (Table 6) Light-sensitive material Yellow blood salt content “± 2 ° C. concentration fluctuation range” Remark Halogen composition ratio B concentration G concentration R concentration (mol%) (101) 0 0.35 0.32 0.33 Comparative example (201 ) 0 0.16 0.14 0.15 Inventive Example (301) 5 × 10 ⁻⁷ 0.16 0.14 0.15 Inventive Example (302) 1 × 10 ⁻⁵ 0.13 0.12 0.1. 12 Inventive Example (303) 1 × 10 ⁻⁴ 0.12 0.11 0.11 Inventive Example As is clear from the above results, the high silver chloride phase of the high silver chloride grains of the present invention contains iron ions. When used in combination, a color image having less dependency on heat development temperature can be stably obtained.

Example 4 The silver halide emulsion used in the light-sensitive materials (301, 302, 303) of Example 3 was allowed to contain iridium hexachloride dipotassium salt in a molar ratio of 3 × 10 ⁻⁷ to silver halide. Other than the above, the photosensitive materials (401, 402, 403) were prepared and evaluated in the same manner as the photosensitive materials (301, 302, 303), and the photosensitive materials (301, 302, 303) were obtained.
It was found that the “± 2 ° C. density fluctuation range” is a little better than the above, but the sensitivity is high and the exposure time is short, so that high-speed image formation is possible.

Example 5 Using the light-sensitive material (402) of Example 4 of the present invention and the image-receiving material of Example 1 to form an image with the apparatus shown in FIG. 1, a full-color image of good quality was obtained. Was able to be obtained stably.

[Brief description of drawings]

FIG. 1 is a configuration diagram of an image forming apparatus used in a fifth embodiment.

[Explanation of symbols]

 1: Original plate 2: Original 3: Lamp 4: Lens 5: Exposure table 6: Photosensitive member 7: Cartridge 8: Conveying roller 9: Heat developing device 10: Pressure transfer device 11: Take-up shaft 12: Separation roller 13: Feeding Paper toilet 14: Transfer member 15: Paper feeding device 16: Paper ejection roller 17: Paper ejection toilet 18: Gas removal device

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[Procedure amendment]

[Submission date] January 10, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0055

[Correction method] Change

[Correction content]

In the image forming method of the present invention, the unpolymerized polymerizable compound is transferred to the image receiving material by the step of applying pressure in a state where the photosensitive material having a polymer image and the image receiving material are superposed on the photosensitive layer, A color image can be obtained on the image receiving material. A conventionally known method can be used as the pressurizing method. For example, the photosensitive material and the image receiving material may be sandwiched between press plates such as a presser, or pressure may be applied while being conveyed using a pressure roller such as a nip roll.
The pressure may be intermittently applied by a dot impact device or the like. Further, high pressure air can be wiped with an air gun or the like, or can be pressurized with an ultrasonic wave generator, a piezoelectric element or the like. The pressure required for pressure transfer is 200 kg /
cm ² or more, preferably 400 kg / cm ² or more. However, when heating is also used at 40 ° to 120 ° C during pressurization, the pressure may be 200 kg / cm ² or less.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0064

[Correction method] Change

[Correction content]

[0064]

[Chemical 4]

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0080

[Correction method] Change

[Correction content]

Preparation of Photosensitive Material (101) The blue-sensitive microcapsule liquid (CB-1) of the present invention was used as 16
g, 14 g of the green-sensitive microcapsule liquid (CG-1),
15 g of the red-sensitive microcapsule liquid (CR-1) was taken out, and each was heated to 40 ° C. to be melted and mixed, and then 13 g of the emulsion (VA-1) and the surfactant (WW
6.5 g of a 5% aqueous solution of -1) was added, and the mixture was stirred at 40 ° C. for 10 minutes and mixed. This solution was filtered through a 44 μm mesh to prepare a coating solution. This coating liquid was applied by an extrusion method to an aluminum vapor-deposited surface of a support obtained by vapor-depositing aluminum on a polyethylene terephthalate film having a thickness of 16 μm by an extrusion method so that the coating amount was 76 ml / m ² .
Photosensitive material for comparison (101), which was dried at 55 ° C and then wound up at 25 ° C and 60% with the coated surface facing inward.
It was created.

Claims (5)

[Claims] 1. A light-sensitive material having at least silver halide, a reducing agent and a polymerizable compound on a support, and heat development in 5 seconds or less, wherein the silver halide is 95 mol%.
A photothermographic material comprising the above silver chloride or silver chlorobromide. 2. The silver halide, the reducing agent, and the polymerizable compound are contained in microcapsules, and the capsule further contains a color image-forming substance and a base precursor. Photothermographic material. 3. The silver chlorobromide grains have a high silver bromide phase, the high silver bromide phase is located on the surface of the silver halide grains, and the volume fraction of the high silver bromide phase with respect to the entire grains is 20% or less, 2. The photothermographic material according to claim 1, wherein the silver bromide content in the high silver bromide phase is 20 mol% or more. 4. The photothermographic material according to claim 1, wherein the surface of the silver halide grain has a high silver bromide phase, and the formation of the high silver bromide phase is carried out in the presence of a sensitizing dye. 5. The silver halide grain comprises a water-soluble iridium compound in a molar ratio of 1 to 1 based on the total silver halide grain.
The thermal development according to claim 1, which contains 0 ^-8 or more and 10 ^-4 or less, or 10 to ⁶ or 10 ^-3 or less in a molar ratio of iron ions to silver in the entire silver halide grain. Photosensitive material.