JPH05289324A - Photosensitive material using microcapsule - Google Patents

Abstract

PURPOSE:To obtain a photosensitive material using microcapsules and giving an image having high image density and excellent in graininess. CONSTITUTION:A substrate is coated with a lower layer consisting of nonphotosensitive microcapsules involving an oily liq. and using polyurea resin as the wall material and the coated substrate is further coated with an upper layer contg. photosensitive microcapsules involving at least silver halide, a reducing agent, a color image forming material and a polymerizable compd. and having 3-10mum volume-average particle diameter and nonphotosensitive microcapsules involving an oily liq. and using polyurea resin as the wall material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light-sensitive material having a high image density and an image excellent in graininess.

[0002]

2. Description of the Related Art A light-sensitive material having a light-sensitive layer containing a silver halide, a reducing agent, and a polymerizable compound on a support causes a latent image to be formed on the silver halide, and the polymerizable compound is polymerized correspondingly. The image forming method can be used. An example of this image forming method is Japanese Patent Publication No. 45-111149.
No. 47-20741, No. 49-10697, JP-A No. 57-138632, No. 57-142638,
57-176033, 57-21146, 58-107529, 58-121031, 5;
No. 8-169143. These methods form an image-like polymer compound by polymerizing a coexisting polymerizable compound (eg, vinyl compound) when developing exposed silver halide using a developing solution. . Therefore, the above method requires a development process using a liquid, and the process requires a relatively long time.

As an improvement of the above method, Japanese Patent Laid-Open No. 61-69 has been proposed.
062, 61-73145, 61-18364.
No. 0, No. 61-188535, No. 61-228441
Each of the publications describes a method capable of forming a polymer compound by a dry treatment. The above method uses a recording material (photosensitive material) in which a photosensitive layer comprising a photosensitive silver salt (silver halide), a reducing agent, a crosslinkable compound (polymerizable compound) and a binder is carried on a support. is there.
The above image forming method is a method of polymerizing the polymerizable compound in the portion where the latent image of silver halide is formed.

Further, a method of polymerizing a polymerizable compound in a portion where a latent image of silver halide is not formed is disclosed in JP-A-61 / 1986.
-183641, 61-260241, 62-
70836, 62-81635, JP-A 2-14
No. 1756, No. 2-141757, No. 2-20725
No. 4 and No. 2-262662.

As one mode of the light-sensitive material that can be used in the above-mentioned image forming method, there is disclosed a light-sensitive material in which the constituent components of the light-sensitive layer such as silver halide and polymerizable compound are contained in microcapsules. It is described in JP-A-61-275572. The light-sensitive material of the embodiment using the above-mentioned microcapsules (hereinafter referred to as photosensitive microcapsules) has an advantage that a clear image, particularly excellent in sharpness can be obtained. On the other hand, the development and the polymerization reaction in the above image forming method proceed 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. A light-sensitive material characterized in that the light-sensitive layer contains a base or a base precursor is described in JP-A-62-264041.

When the base or the base precursor is added to the light-sensitive material using the above-mentioned photosensitive microcapsules, it is necessary to store the base or the base precursor in the photosensitive microcapsules because of the function of promoting the image formation of the base or the base precursor. It is preferable in terms. Japanese Patent Laid-Open No. 64-322
51, JP-A-1-263641, JP-A2-1
JP-A No. 46041 and JP-A-3-25444 describe a photosensitive material using a photosensitive microcapsule characterized by containing a base or a base precursor therein.

In each of the light-sensitive materials described above, a leuco dye is usually used as a color image forming substance. However, an image obtained from a leuco dye has a drawback that the fading property is poor, and as a means for improving this point, it has been proposed to use a pigment as a color image-forming substance, which are disclosed in JP-A-62-187346. JP-A-3-6994
No. 9, No. 3-69953, No. 3-69954, and the like.

However, since an image obtained by pressure-transferring the above-mentioned light-sensitive material with an image-receiving material described below is poor in discrimination, a high-boiling organic compound is contained outside the photosensitive microcapsules to discriminate. To obtain an excellent image of Japanese Patent Application No. 3-198245
No. Furthermore, since the density of the yellow, magenta, and cyan monochromatic areas was insufficient, the density of the transferred image was improved by incorporating an oily liquid and coexisting with another microcapsule having a heat-permeable wall in the photosensitive layer. Japanese Patent Application No. 3-272650 discloses that the color of the monochromatic part is improved. On the other hand, in order to improve the graininess of the transferred image, the present inventor proposes to reduce the microcapsule size in Japanese Patent Application No. 3-268575.
At this time, there is a problem that the image density of the transferred image is still low, and the effect is insufficient even when the method according to the above-mentioned prior application is used.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide an image having high image density and excellent graininess.

[0010]

The main object of the present invention is to enclose an oily liquid on a support and to form a non-photosensitive microcapsule having a polyurea resin as a wall material in the lower layer, and at least a silver halide, a reducing agent, A photosensitive material comprising a photosensitive microcapsule containing a color image-forming substance and a polymerizable compound and an oily liquid, and a photosensitive layer including a non-photosensitive microcapsule having a polyurea resin as a wall material as an upper layer. Achieved

When the light-sensitive material of the present invention is imagewise exposed and heated and developed, microcapsules containing a silver halide, a reducing agent, a polymerizable compound and a color image-forming substance are imagewise cured.
Next, the light-sensitive material is superposed on the image receiving material and transferred under pressure to destroy the uncured microcapsules, and the contents thereof are transferred onto the image receiving material. At this time, in the non-photosensitive microcapsules containing the oily liquid contained in the photosensitive layer and the lower layer, the inner phase thereof penetrates the wall, and the released oily liquid acts as a transfer aid to increase the transfer amount.

At this time, the non-photosensitive microcapsules need to be coated below the photosensitive layer, and the density of the transferred image is improved as compared with the case where it is contained only in the photosensitive layer. When the particle size of the capsule is small, the transfer image density is most significantly improved. Incidentally, even if the oily liquid contained in the non-photosensitive microcapsules of the upper layer and the lower layer is the same,
May be different. The cause of this is unclear at present, but when the non-photosensitive microcapsules are contained in the photosensitive layer and the lower layer, the internal phase in the non-photosensitive microcapsules is released through the wall when the photosensitive material is heat-developed. ,
In particular, it is presumed that the transfer amount of the inclusions of the photosensitive microcapsules released from the lower part of the photosensitive layer at the time of pressure transfer is increased.

For the non-photosensitive microcapsules containing the oily liquid, it is preferable to use a heat permeable wall material as described in Japanese Patent Application No. 3-272650. In the present invention, a polyurea resin is used.

The oily liquid contained in the non-photosensitive microcapsules is preferably compatible with the polymerizable compound contained in the photosensitive microcapsules, and more preferably has a high affinity with the color image forming substance. is there. If the compatibility with the polymerizable compound is poor, it is easy to separate from the polymerizable compound released from the photosensitive microcapsules during pressure transfer,
Satisfactory image quality cannot be obtained. When the affinity for the color image forming substance is poor, the density of the transferred image is insufficient.

The following may be mentioned as the oily liquid that can be used. First, as an ethylenically unsaturated compound, acrylic acid and its salts, acrylic acid esters, acrylamides, methacrylic acid and its salts, methacrylic acid esters, methacrylamides,
Maleic anhydride, maleic acid esters, itaconic acid esters, styrenes, vinyl ethers, vinyl esters, N-vinyl heterocycles, allyl ethers, allyl esters and their derivatives, etc. There are similar polymerizable compounds included.

Next, esters such as phosphoric acid ester, phthalic acid ester, benzoic acid ester, ethers,
Alcohols, tung oil, flaxseed oil, deer oil,
Dry oil such as safflower oil, semi-dry oil such as soybean oil, vegetable oil such as non-drying oil such as castor oil, and further dehydrated castor oil, polymerized oil, maleated oil, styrenated oil, vinyltoluene oil, urethane oil, etc. Mineral oils such as processing oil, spindle oil, machine oil and the like can be mentioned.

The oily liquid does not have to be liquid at room temperature, and may be solid at room temperature as long as it is a liquid at the time of pressure transfer, since the object of the present invention is achieved. These oily liquids such as esters, ethers, alcohols and fats and oils may be used alone or in combination of two or more.

Among these oily liquids, esters such as acrylic acid esters, phthalic acid esters and benzoic acid esters are preferable. Further, since the compatibility with the polymerizable compound is good, the same compound as the polymerizable compound in the photosensitive microcapsule is particularly preferable.

The separate capsule containing the oily liquid is preferably used in a proportion of 100% or more and 300% or less, particularly 150% to 250%, based on the weight of the oily liquid in the photosensitive microcapsule. It is preferably used in proportion.

The silver halide, reducing agent, color image-forming substance, polymerizable compound, microcapsule, and support used in the light-sensitive material of the present invention will be described below.

The silver halide used in the light-sensitive material of the present invention is any of silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide. Particles can also be used. The silver halide grains in the photographic emulsion are cubic,
Those having regular crystals such as octahedron, dodecahedron and tetradecahedron, those having an irregular crystal system such as spheres and plates, those having crystal defects such as twin planes, or A composite form of them may be used.

The grain size of the silver halide may be fine grains of about 0.01 micron or less, or large size grains having a projected area diameter of up to about 10 microns, and a polydisperse emulsion or US Pat. No. 3,574,628 may be used. No., 3,655,394
And monodisperse emulsions described in British Patent No. 1,413,748 and the like may be used.

Further, tabular grains having an aspect ratio of about 5 or more can be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineering.
Engineering), Vol. 14, pp. 248-257 (1970)
); U.S. Pat. Nos. 4,434,226 and 4,41
4,310, 4,433,048, 4,43
It can be easily prepared by the method described in 9,520 and British Patent 2,112,157.

The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. Further, silver halides having different compositions may be joined by epitaxial joining,
Further, it may be bonded with a compound other than silver halide such as silver rhodanide and lead oxide. Also, the halogen composition,
Two or more kinds of silver halide grains having different crystal habits, grain sizes and the like can be used in combination.

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) No1.
7643 (Dec. 1978), pp. 22-23, "I.
"Emulsion preparation and types", and No. 18716 (November 1979), page 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 to page 24, page 648, right column ~ Supersensitizer, page 649, right column, antifoggant 24- Page 25 Page 649 Right column ~ and Stabilizer

Details of the above silver halide emulsion and photographic additives are described in "Public Technology No. 5" (Aztec Co., Ltd., issued March 22, 1991), pages 2 to 17. The amount of silver halide used is 1
0.001 to 10 g, preferably 0.0 per m ^{2 in} terms of silver
It is 5 to 2 g. 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 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 various reducing agents are described in detail in "Public Technology No. 5", pages 18 to 35. 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. The color image-forming substance that can be used in the light-sensitive material of the present invention is not particularly limited, 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.

The polymerizable compound used in the light-sensitive material is generally a compound having addition polymerization or ring-opening polymerization. The compound having an addition-polymerizable compound has a compound having an ethylenically unsaturated group, and the compound having a ring-opening polymerizable compound has a compound having an epoxy group, but the compound having an ethylenically unsaturated group is polymerizable. Particularly preferred.

Examples of the compound having an ethylenically unsaturated group which can be used in the light-sensitive material include acrylic acid and its salts, acrylic acid esters, acrylamides, methacrylic acid and its salts, methacrylic acid esters and methacrylamides. , Maleic anhydride, maleic acid esters, itaconic acid esters, styrenes, vinyl ethers, vinyl esters, N-vinyl heterocycles, allyl ethers, allyl esters and their derivatives.

Specific examples of preferable polymerizable compounds that can be used in the light-sensitive material include acrylic acid esters, such as n-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, furfuryl acrylate, and ethoxyethoxyethyl. Acrylate, tricyclodecanyloxy acrylate, nonylphenyloxyethyl acrylate, 1,3-dioxolane acrylate, hexanediol diacrylate, butanediol diacrylate,
Neopentyl glycol diacrylate, tricyclodecane dimethylol diacrylate, trimethylol propane triacrylate, pentaerythritol tetraacrylate,

Dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, diacrylate of polyoxyethylenated bisphenol A,
2- (2-hydroxy-1,1-dimethylethyl) -5
-Hydroxymethyl-5-ethyl-1,3-dioxane diacrylate, 2- (2-hydroxy-1,1-dimethylethyl) -5,5-dihydroxymethyl-1,3-
Dioxane triacrylate, triacrylate of propylene oxide adduct of trimethylolpropane, tetraacrylate of propylene oxide adduct of ditrimethylolpropane, hexaacrylate of caprolactone adduct of dipentaerythritol, hydroxypolyether polyacrylate, polyester acrylate and polyurethane An acrylate etc. can be mentioned.

As another specific example, regarding methacrylic acid esters, methyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, butanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate,
Examples thereof include pentaerythritol tetramethacrylate and dioxymethacrylate of polyoxyalkylenated bisphenol A.

The above polymerizable compounds may be used alone or in combination of two or more kinds. Regarding a light-sensitive material in which two or more kinds of polymerizable compounds are used in combination, see JP-A-62-210445.
It is described in the official gazette. A substance obtained by introducing a polymerizable functional group such as a vinyl group or a vinylidene group into the chemical structure of the reducing agent described above can also be used as the polymerizable compound. Further, the compounds described on pages 51 to 55 of the above-mentioned "Known technology No. 5" are also applicable to the present invention.

Various known techniques can be applied to the microcapsules that can be used in the present invention without particular limitation, and they are described in detail in the above-mentioned "Known Technique No. 5", pp. 88-98. 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, it is preferable that the amount of residual aldehyde is not more than a certain value, as in the light-sensitive material described in JP-A-63-32535. The method is disclosed in JP-A-63-14.
No. 2343, etc. The average particle size of the microcapsules is 1 to 50 μm, preferably 3 to 20 μm. The particle size distribution of microcapsules is described in JP-A-63 / 1988.
As in the light-sensitive material described in JP-A-5334, it is preferable that the light-sensitive material is uniformly distributed over a certain value. 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 accommodating silver halide in the microcapsules, the average grain size of the silver halide grains described above is preferably not more than 1/5 of the average size of the microcapsules, and preferably not more than 1/10. More preferably, By setting the average grain size of silver halide grains to be one fifth or less of the average size of 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 comprising a polymerizable compound containing a silver halide, a reducing agent and a color image-forming substance is dispersed in an aqueous medium,
When forming the outer shell of the capsule, 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 10 to 1 with respect to the aqueous medium.
20% by weight is preferable, and 20 to 90% by weight is more preferable.

Examples of nonionic water-soluble polymers are polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polymethyl vinyl ether, polyacryloylmorpholine, polyhydroxyethyl acrylate, polyhydroxyethyl methacrylate-co-acrylamide, hydroxyethyl cellulose, hydroxy. Examples thereof include propyl cellulose and methyl cellulose. 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 preferably 0.01 to 5% by weight, more preferably 0.1 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.

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 the undercoat layer described in JP-A-61-113058 on the polymer film, or to provide a metal vapor deposition film of aluminum or the like on the polymer film.
Therefore, as the support of the light-sensitive material of the present invention, 50 μm
A polymer film having the following thickness and having an aluminum vapor deposition film is particularly preferable.

Other components that can be used in the light-sensitive material of the present invention will be described below. In the light-sensitive material of the present invention, since development is promoted under basic conditions, it is preferable to use a base or a base precursor. As the base precursor, base precursors of inorganic bases and organic bases (decarboxylation type, thermal decomposition type, reaction type, complex salt forming type, etc.) can be used. Details of these base precursors and the techniques for using them are described in "Public Technology No. 5," pages 55-86.

Preferred base precursors are JP-A Nos. 59-180549, 59-180537, 59-195237, 61-32844 and 61.
-36743, 61-51140, 61-52.
No. 638, No. 61-52639, No. 61-53631.
No. 61-53634, No. 61-53635, No. 61-53636, No. 61-53637, No. 61-
53638, 61-53639, 61-536.
40, 61-55644, 61-55645.
No. 61, No. 61-55646, No. 61-84640, No. 61-107240, No. 61-2119950, No. 6
1-251840, 61-252544, 61
-313431, 63-316740, 64-
68746 and 64-54452, salts of organic acids and bases which are decarboxylated by heating, and JP-A-59-157637 and 59-16694.
Examples thereof include compounds capable of eliminating a base by heating as described in JP-A Nos. 3 and 63-96159.

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 as described below, which has a 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 contained in the microcapsules, a photosensitive composition in which the base precursor is directly solid-dispersed in a polymerizable compound may be used (Japanese Patent Application Laid-Open No. 64-32521, Japanese Patent Application Laid-Open No. 32-3251). Kaihei 1-2
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-63-21
8964, JP-A Nos. 2-146041, and 3-2.
(See Japanese Patent No. 5444) Here, 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, hydroxy. Examples thereof include propyl cellulose and methyl cellulose. Further, as the amphoteric water-soluble polymer,
Mention may be made of gelatin.

The above water-soluble polymer is preferably contained in the base precursor in a proportion of 0.1 to 100% by weight, more preferably 1 to 50% by weight. The base precursor is preferably contained in the dispersion in an amount of 5 to 60% by weight, more preferably 10 to 50% by weight. The base precursor is preferably contained in a proportion of 2 to 50% by weight with respect to the polymerizable compound,
It is more preferable that the content is 5 to 30% by weight.

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, 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, a known antioxidant can be used together with the polymerizable compound for preventing oxidative deterioration of the polymerizable compound and for preventing oxygen oxidation during heat development. 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.

Further, other components that can be used in the light-sensitive material of the present invention will be described. 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 formation 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 of a reducing agent with a silver salt, and accelerating the immobilization of a dye-donor substance by polymerization. Are classified into the above-mentioned bases or base precursors, nucleophilic compounds, oils, thermal solvents, surfactants, compounds that interact with silver or silver salts, compounds having an oxygen scavenging function, and the like. However, these substance groups generally have a composite function and usually have some of the above-mentioned accelerating effects together. Details thereof are described in the specifications and publications of U.S. Pat. No. 4,678,739, columns 38 to 40, JP-A-62-209443 and the like. Further, the polyvalent metal compounds described in Japanese Patent Application No. 2-272878 are also effective.

In the system for polymerizing the polymerizable compound in the portion where the latent image of silver halide is not formed,
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. Details thereof are described in "UV Curing System" (1989, Comprehensive Technical Center), pages 63 to 147, and the like. Various surfactants may be used in the light-sensitive material for the purpose 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 disclosed in JP-A-62-17.
No. 3463, No. 62-183457 and the like.

An antistatic agent can be used in the light-sensitive material for the purpose of antistatic. As an antistatic agent, it is described in Research Disclosure Magazine, November 1978, No. 17643 (page 27). In the photosensitive layer of the photosensitive material,
Dyes or pigments may be added for the purpose of preventing halation or irradiation. A light-sensitive material having a white pigment added to the light-sensitive layer is disclosed in JP-A-63-29748.
It is described in the official gazette.

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 of a polymerizable compound is used for the light-sensitive material, it is preferable to use it by enclosing it in a microcapsule different from the microcapsule containing the polymerizable compound.
A photosensitive material using an organic solvent miscible with a polymerizable compound encapsulated in microcapsules is disclosed in Japanese Patent Laid-Open No.
It is described in JP-A-2-209524.

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 modes of use 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-62-2.
Japanese Patent Application Laid-Open No. 63-101842 discloses a light-sensitive material provided with a coloring layer as an antihalation layer.
Each of them is described in Japanese Patent Publication No. 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 light-sensitive material, glass, paper, high-quality paper, baryta paper, coated paper, cast coated paper, synthetic paper, cloth, metal and its analogs. , Polyester, polyethylene, polypropylene, acetyl cellulose, cellulose ester, polyvinyl acetal,
Examples thereof include films such as polystyrene, polycarbonate and 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 of the image receiving material, it is disclosed in JP-A-62-20953.
It is preferable that the image-receiving material described in JP-A-No. 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.

The white pigment used in the image-receiving layer is an inorganic white pigment, for example, oxides of silicon oxide, titanium oxide, zinc oxide, magnesium oxide, aluminum oxide, magnesium sulfate, barium sulfate, calcium sulfate, carbonic acid. Alkaline earth metal salts such as magnesium, barium carbonate, calcium carbonate, calcium silicate, magnesium hydroxide, magnesium phosphate, and magnesium hydrogen phosphate, as well as aluminum silicate, aluminum hydroxide, zinc sulfide, sugar clay, talc , Kaolin, zeolite, acid clay, activated clay, glass and the like. 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 or a polymer soluble in an organic solvent 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, polymers of acrylic acid ester and / or methacrylic acid ester, copolymer latex, ethylene / vinyl acetate copolymer. Polymer latex etc. are mentioned. Examples of the polymer soluble in an organic solvent include polyester resin, polyurethane resin, polyvinyl chloride resin, polyacrylonitrile resin and the like.

The binder may be used in a combination of two or more kinds, and may also be used in a ratio such that the two kinds of binders cause phase separation. 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 generally, 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 depend on the photosensitive wavelength of silver halide (the wavelength sensitized when dye-sensitized)
Alternatively, it can be selected according to the 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 laser, Chemical lasers, semiconductor lasers, etc.), light emitting diodes, plasma arc tubes, FOTs and the like. 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 the 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 this heating means, there is disclosed in JP-A-61-29.
As in the light-sensitive material described in Japanese Patent No. 4434, a heating element layer may be provided on the surface of the support on which the light-sensitive layer of the light-sensitive material is not coated to heat it. Further, as described in JP-A-61-147244, a hot plate, an iron, and a heat roller are used, or as described in JP-A-62-144166, a photosensitive material is sandwiched between a heat roller and a belt. You may use the method of heating.

That is, the photosensitive material may be brought into contact with a heating element having a surface area larger than the area of the photosensitive material to heat the entire surface at the same time, or a heating element having a smaller surface area (heating plate,
The entire surface may be heated over time by bringing it into contact with a heat roller, a heat drum, etc. and scanning it.
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 from the surface of the support on which the photosensitive layer is not coated. At this time, the photosensitive layer is coated. The surface that is marked may be in direct contact with the 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.

The heat development by heating is carried out at the same time as or after the imagewise exposure, but it is preferable that the heating is carried out at least 0.1 seconds after the imagewise exposure. The heating temperature is generally 60 ° C to 250 ° C, preferably 80 ° C to 180 ° C.
And the heating time is between 0.1 and 20 seconds, preferably between 0.1 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 the 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 by 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. However, when pressure is applied, it is possible to transfer by pressure at a pressure of 20 kg / cm ² or more and 500 kg / cm ² or less while heating at a temperature of 30 ° C. or more and 130 ° C. or less in a state where the light-sensitive material and the image receiving material are superposed. preferable.

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

[0092]

【Example】

Example 1 Preparation of silver halide emulsion (EB-1) 24 g of lime-treated inert gelatin was added to distilled water, and 4
After dissolution at 0 ° C. for 1 hour, 3 g of NaCl was added, and 1N sulfuric acid was added to adjust the pH to 3.2.

After 10 mg of (AGS-1) was added to this solution, the solution I and the solution II were kept at 60 ° C. by the control double jet method while keeping pAg = 8.5 at the same time, it took 45 minutes until the solution I disappeared. Added. PH after addition
Was adjusted to 6.0 with 1N NaOH and (AZ-1) 6.
4 mg and (AZ-2) 4.8 mg were added to 60 at 60 ° C.
Aged. After aging, 480 mg of (SB-1) was added, and 100 g of an aqueous solution containing 4.1 g of KI was added at an equal flow rate from 20 minutes to 3 minutes after the addition.

1.1 g of (CK-1) was added to this emulsion, precipitated, washed with water to desalinize, and 6 g of lime-processed gelatin was added to dissolve it, and a 3.5% aqueous solution of (ATR-3) 1. The pH was adjusted to 6.2 by adding 5 cc. 550 g of a monodisperse silver iodobromide emulsion (EB-1) having an average grain size of 0.24 μm and a coefficient of variation of 20% was prepared.

Liquid I AgNO ₃ 120 g Distilled water 550 cc Liquid II KBr 85 g Distilled water 550 cc

Preparation of silver halide emulsion (EG-1) Same as silver halide emulsion (EB-1) except that solution I
Solution II was added for 15 minutes, and 450 mg of (SG-1) was added instead of (SB-1). 550 g of a monodisperse silver iodobromide emulsion (EG-1) having an average grain size of 0.18 μm and a coefficient of variation of 20% was prepared.

Preparation of Silver Halide Emulsion (ER-1) Same as Silver Halide Emulsion (EB-1) except for Solution I and II.
The addition time of the liquid was set to 15 minutes, and instead of (SB-1), 450 mg of (SR-1) and 100 mg of (SR-2)
Was added. Average particle size 0.18 μm, coefficient of variation 2
550 g of a 2% monodisperse silver iodobromide emulsion (ER-1) was prepared.

[0098]

[Chemical 1]

[0099]

[Chemical 2]

(CK-1): poly (isobutylene-co-
Monosodium maleate)

Preparation of solid dispersion (KB-1) 5.4 of lime-processed gelatin in a 300 ml dispersion container.
% Aqueous solution 110 g, polyethylene glycol (average molecular weight 2000) 5% aqueous solution 20 g, base precursor (BG-1) 70 g, and glass beads 200 ml having a diameter of 0.5 to 0.75 mm are added, and 300 using a Dynomill.
Disperse at 0 rpm for 30 minutes, adjust the pH to 6.5 with 2N sulfuric acid and adjust the base precursor (BG
A solid dispersion (KB-1) of -1) was obtained.

[0102]

[Chemical 3]

Preparation of Pigment Dispersion (GY-1) To 255 g of the polymerizable compound (MN-1), 45 g of Chromofine Yellow 5900 (trade name, manufactured by Dainichiseika Co., Ltd.) was mixed, and an Eiger Motor Mill (Eiger. (Manufactured by Engineering Co., Ltd.) was stirred at 5000 rpm for 1 hour to obtain a 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 Pigment Dispersion (GM-1) To 270 g of the polymerizable compound (MN-1), Rubin F6B was added.
(Product name, manufactured by Hoechst Co., Ltd.) 30 g was mixed and stirred for 1 hour at 5000 rpm using an Eiger Motor Mill (manufactured by Eiger Engineering Co.) to obtain a dispersion (GM-
1) was obtained.

Preparation of Pigment Dispersion (GC-1) Polymerizable compound (MN-1) (255 g), copper phthalocyanine (CI Pigment 15) (45 g) and Solsperse 500 were prepared.
0 (manufactured by ICI) 1.13 g, Sols Perth 24000
3.37 g (manufactured by ICI) was mixed and stirred for 1 hour at 5000 rpm using an Eiger motor mill (manufactured by Eiger Engineering) to obtain a dispersion (GC-1).

Preparation of Photosensitive Composition (PB-1) 45 g of pigment dispersion (GY-1) was added with (SV of (1P-1)).
-1) 9 g of 10% (wt%) solution, (RD-1) 2.
3 g, (RD-3) 3.1 g, (FF-3) (SV-
1) 2 g of 0.5% (wt%) solution and (ST-1)
0.5 g was added and dissolved to prepare an oily solution. To this solution, 7.6 g of silver halide emulsion (EB-1) and 24 g of solid dispersion (KB-1) were added, and the mixture was stirred at 10,000 rpm for 5 minutes using a 40φ dissolver while maintaining the temperature at 60 ° C. Then, a W / O emulsion photosensitive composition (PB-1) was obtained.

Preparation of Photosensitive Composition (PG-1) 45 g of pigment dispersion (GM-1) was added to (1P-1) of (SV
-1) 9 g of 10% (wt%) solution, (RD-1) 2.
3 g, (RD-3) 3.1 g, (FF-3) (SV-
1) 2 g of 0.5% (wt%) solution and (ST-1)
0.5 g was added and dissolved to prepare an oily solution. To this solution, 7.6 g of silver halide emulsion (EG-1) and 24 g of solid dispersion (KB-1) were added, and the mixture was stirred at 10,000 rpm for 5 minutes using a 40φ dissolver while maintaining the temperature at 60 ° C. , W / O emulsion photosensitive composition (P
G-1) was obtained.

Preparation of Photosensitive Composition (PR-1) 45 g of pigment dispersion (GC-1) was added with (S) of (1P-1).
V-1) 9 g of 10% (wt%) solution, (RD-1)
2.3 g, (RD-2) 3.1 g, (FF-3) (S
V-1) 2 g of 0.5% (wt%) solution and (ST-
1) 0.5 g was added and dissolved to prepare an oily solution.

A silver halide emulsion (ER-1) was added to this solution.
7.6 g and 24 g of solid dispersion (KB-1) were added, and 5
While maintaining the temperature at 0 ° C., a 40φ dissolver was used to stir at 10000 rpm for 5 minutes to obtain a W / O emulsion photosensitive composition (PR-1).

[0110]

[Chemical 4]

[0111]

[Chemical 5]

[0112]

[Chemical 6]

Photosensitive microcapsule dispersion (CB-
Preparation of 1) 26 g of water was added to 4 g of 15% aqueous solution of polymer (2P-4).
In addition, the mixed solution was adjusted to pH 5.0 with 2N sulfuric acid. 70 g of a 10% aqueous solution of polymer (2P-2) was added to this liquid, and mixed at 60 ° C. for 30 minutes. This mixed solution was added to the above-mentioned photosensitive composition (PB-1), and the mixture was stirred with a 40φ dissolver at 60 ° C. at 8000 rpm for 20 minutes, and W /
An emulsion in the form of an O / W emulsion was obtained. Separately, 5% of 37% aqueous formaldehyde solution was added to 31.5 g of melamine.
2.2 g 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 the melamine-formaldehyde initial condensate.

25 g of this initial condensate was added to the emulsion in the state of the above W / O / W emulsion cooled to 40 ° C.,
The pH was adjusted to 5.0 with 2N sulfuric acid while stirring at 1200 rpm with a propeller blade. Next, the temperature of this liquid was raised to 70 ° C. in 30 minutes, and further stirred for 30 minutes. To this, add 10.3 g of 40% aqueous solution of urea and add 2N sulfuric acid.
The pH was adjusted to 3.5 and stirring was continued at 70 ° C. for another 40 minutes. After cooling this solution to 40 ° C., K-carrageenan 3
% Aqueous solution 9 g, stirred for 10 minutes, adjusted to pH 6.5 with a 2N aqueous sodium hydroxide solution, and dispersed in a photosensitive microcapsule having a volume average particle diameter of 9 μm (CB-
1) was prepared.

Photosensitive microcapsule dispersion (CG-
Preparation of 1) 16 g of water was added to 4 g of 15% aqueous solution of polymer (2P-4).
In addition, the mixed solution was adjusted to pH 5.0 with 2N sulfuric acid. To this solution, 80 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 the mixed solution, and the mixture was stirred at 60 ° C. for 20 minutes at 8,000 rpm using a 40φ dissolver, and was then heated to W.
An emulsion in the form of a / O / W emulsion was obtained. Then, in the same manner as in the preparation of (CB-1), the volume average particle diameter is 9.5 μm.
m photosensitive microcapsule dispersion (CG-1) was prepared.

Photosensitive microcapsule dispersion (CR-
Preparation of 1) 26 g of water was added to 4 g of 15% aqueous solution of polymer (2P-4).
In addition, the mixed solution was adjusted to pH 5.0 with 2N sulfuric acid. 70 g of a 10% aqueous solution of polymer (2P-2) was added to this liquid, and mixed at 60 ° C. for 30 minutes. The above-mentioned photosensitive composition (PR-1) was added to this mixed liquid, and the mixture was stirred at 60 ° C. for 20 minutes at 8,000 rpm using a 40φ dissolver, and was then heated to W.
An emulsion in the form of a / O / W emulsion was obtained. Then, in the same manner as in the preparation of (CB-1), a photosensitive microcapsule dispersion liquid (CR-1) having a volume average particle diameter of 9 μm was prepared. Polymer (2P-4): Potassium polyvinylbenzene sulfinate-co-acrylamide Polymer (2P-2): Polyvinylpyrrolidone K-9
0

Preparation of Microcapsule Dispersion Liquid (CA-1) Encapsulating Oily Liquid 104 g of a 3% aqueous solution of Metroses 65SH50 (manufactured by Shin-Etsu Chemical, hydroxypropylmethylcellulose) was added with 97 g of the polymerizable compound (MN-1) and Takenate D110.
A mixture of 6 g of N (manufactured by Takeda Pharmaceutical Co., Ltd., polyisocyanate) was added, and a 40φ dissolver was used at 25 ° C. for 150 minutes per minute
The mixture was stirred at 0 rotation for 5 minutes to obtain an emulsion in the state of O / W emulsion. After adding 12 g of a 2% aqueous solution of diethylenetriamine to this solution, use a propeller blade to make it 4 ° C at 4 ° C.
The mixture was stirred at 00 rpm for 90 minutes. After cooling this capsule liquid to 25 ° C., the pH was adjusted to 6 with 2N sulfuric acid to obtain MN-1-containing polyurea capsules. Volume average particle size is 9 μm
Met.

The photosensitive microcapsules of the present invention (CB-
15 g of (1), 15 g of (CG-1), and 15 g of (CR-1) were taken out, respectively, heated to 40 ° C. without stirring and melted, and then mixed, to give 5 parts of the surfactant (WW-1). % Aqueous solution 6.5 g, and microcapsules of the present invention (CA-1)
18 g and 7 g of water were added and mixed by stirring at 40 ° C. for 10 minutes to prepare a microcapsule solution (CD-1).

Next, the microcapsules of the present invention (CA-
1) 17 g of water was added to 44 g, and this was heated to 40 ° C. to melt, and then a 5% aqueous solution of a surfactant (WW-1) 2
7 g was added and mixed by stirring at 40 ° C. for 10 minutes to prepare a microcapsule liquid (CD-2).

Two layers of the photosensitive microcapsule liquid (CD-1) and the microcapsule liquid (CD-2) are simultaneously coated on the aluminum vapor-deposited surface of a support obtained by vapor-depositing aluminum on a polyethylene terephthalate film having a thickness of 25 μm. At this time, 40 cc / m ^{2 of} microcapsule liquid (CD-2) was used for the lower layer, and photosensitive microcapsule liquid (CD-) was used for the upper layer.
1) was applied at 90 cc / m ² , dried at 60 ° C., and then wound up at 25 ° C. and 65% with the coated surface facing inside. This photosensitive material was sealed in a moisture-proof bag laminated with aluminum under the conditions of 25 ° C. and 55% to obtain a photosensitive material 101.

Preparation of image receiving material (RS-1) Calcium carbonate (PC700, manufactured by Shiraishi Industry Co., Ltd.) 24
0 g, surfactant (Poise 520, manufactured by Kao Corporation) 5.
After stirring and mixing 6 g and 354.4 ml of water, a disperser (trade name: Ultra Disperser (LK-41
Type), manufactured by Yamato Scientific Co., Ltd.) and dispersed at 8000 rpm for 3 minutes. 52 g of this dispersion and 10% polyvinyl alcohol (PVA-117, manufactured by Kuraray Co., Ltd.) aqueous solution 4
0g and 1% of surfactant (WW-3)
An aqueous solution (4 ml) and water (22 ml) were added to prepare a coating solution for forming an image receiving layer.

This coating solution was applied to a paper support having a basis weight of 80 g / m ² (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 calculated as follows. Using a base paper having a fiber length distribution such as 30 to 60%, a paper support [JP-A 63-18623]
No. 9)]) was uniformly coated on the surface of the plate at 65 g / m ² and then dried at 60 ° C. to prepare an image receiving material (RS-1).

[0123]

[Chemical 7]

The following experiments were carried out under the conditions of 25 ° C. and 50%. The exposure temperature of the exposed material taken out from the moisture-proof bag was adjusted to 310
Using a halogen lamp adjusted to 0 ° K, a wedge having a continuously changing transmission density of 0 to 4.0 and an ND filter having a density of 1.0, and a CC filter of yellow and magenta to match the gray balance (Fuji The film was exposed through 20,000 lux for 1 second. After 30 seconds from the exposure, heat development was carried out for 2 seconds by a heat developing machine equipped with an exhaust device, which was heated to 150 ° C. from the side opposite to the coated photosensitive material.

Two seconds after heating, the light-sensitive material in which the image-receiving material (RS-1) and the coated surface were superposed on each other was transferred at a speed of 3 m / min to a pressure transfer roller having a diameter of 15 mm and heated at 70 ° C. With the support surface of the light-sensitive material in contact with each other, pressure 25
Passage was carried out at 0 kg / cm ² to perform heating and pressure transfer. When the image receiving material was peeled off from the light-sensitive material immediately after passing, a clear positive image was obtained on the image receiving layer material. With this transferred image, an excellent image having no roughness and a high maximum density was obtained.

Example 2 In the microcapsules (CA-1) of Example 1, instead of the polymerizable compound MN-1, a phosphoric acid ester (MN) was used.
A photosensitive material 102 was obtained in the same manner as in Example 1 except that (2) was used. At this time, the polyurea capsule dispersion liquid containing MN-2 was (CA-2), and the volume average particle diameter of the present capsule liquid was 9.5 μm. Phosphate ester (MN-2): tri-isopropyl-phenoxyphosphate In the same manner as in Example 1, a transfer image excellent in maximum density and roughness was obtained also in this photosensitive material 102.

Comparative Example 1 As in Example 1, the photosensitive microcapsule dispersion liquid (CG
-1, CR-1, CB-1), 36 g of non-photosensitive microcapsules (CA-1) and 14 g of water were added thereto, and the mixture was stirred and mixed in the same manner as in Example 1 to prepare a microcapsule liquid ( CD-3) was prepared. Microcapsule liquid (C
In the same manner as in Example 1, D-3) was applied on the support on which aluminum was vapor-deposited to form a single layer at 120 cc / m ^2, and
Drying and winding were carried out in the same manner as in 1. to obtain a photosensitive material 103.
When the photosensitive material 103 having no non-photosensitive microcapsule layer below the photosensitive microcapsule-containing layer was subjected to the same exposure, heat development, and transfer as in the example, there was no roughness in the transferred image, but it was the highest. An image with a slightly inferior density was obtained.

Comparative Examples 2 and 3 The photosensitive microcapsule dispersion liquid of Example 1 (CB-
In the preparation of 1), (CG-1) and (CR-1), the concentration of the polymer (2P-2) is reduced and emulsified to obtain a volume average particle diameter of 13 μm (CB-2), 14 μm (CG-2), 12
A μm (CR-2) photosensitive microcapsule solution was prepared. The photosensitive microcapsule dispersion liquid of Example 1 (CB-
Photosensitive material 104 was obtained in the same manner as in Example 1 except that the photosensitive microcapsule dispersion liquids (CB-2, CG-2, CR-2) were used instead of 1, CG-1, CR-2). It was (Comparative Example 2) Instead of the photosensitive microcapsule dispersions (CB-1, CG-1, CR-1) of Comparative Example 1, photosensitive microcapsule dispersions (CB-2, CG-2, C) were used.
A light-sensitive material 105 was obtained in the same manner as in Comparative Example 1 except that R-2) was used. (Comparative Example 3) Regarding the photosensitive materials 104 and 105 having large particle diameters of photosensitive microcapsules,
When a transfer image was obtained in the same manner as in the example, the transfer image density was high in 104 and slightly low in 105. However, with regard to graininess of the image, the first embodiment is used.
Was inferior to

Comparative Example 4 In Comparative Example 1, the non-photosensitive microcapsules (CA-
Instead of 1) non-photosensitive microcapsules (CA-2)
In the same manner as in Comparative Example 1 except for using
Got 6. When a transferred image was obtained from this photosensitive material 106 in the same manner as in Example 2, there was no image roughness,
The maximum density of the transferred image was inferior to that of Example 2. Table 1 summarizes the performances of the above Examples and Comparative Examples.

[0130]

[Table 1]

Claims (1)

[Claims] 1. A lower layer containing a non-photosensitive microcapsule containing a polyurea resin as a wall material, which contains an oily liquid on a support, and at least a silver halide, a reducing agent, a color image-forming substance and a polymerizable compound. Volume average particle size is 3
A photothermographic material comprising a photosensitive microcapsule having a size of 10 μm or more and an oily liquid, and an upper layer containing a non-photosensitive microcapsule having a polyurea resin as a wall material.