JPH0545831A - Heat developable color photosensitive material - Google Patents

Abstract

PURPOSE:To obtain the heat-developable photosensitive material capable of forming a transfer image small in color mixing and stains and high in density and superior in sharpness by incorporating a specified metal complex salt dye. CONSTITUTION:The photosensitive material contains photosensitive silver halide, an organic silver salt, a reducing agent, a binder, a color donor, and the metal complex salt dye represented by formula I in which R1 is H, halogen, OH, <=13C monovalent organic group, a 5- or 6-membered heteroring, or a hydrocarbon ring, and such a ring may condense with the benzene ring free of R1; X1 is a counter ion for forming the complex salt, such as H<+>, H3O<+>, an alkali metal or alkaline earth metal ion, or halogen ion; Y1 is -O-, -COO-, -NH-, -SO2N(R2)-; R2 is alkyl or aralkyl: n1 is 0-4; P1 is 1 or 2; and M1 is a metal atom.

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 in which a dye or the like is formed by heat development, and more specifically, a heat development for obtaining a color image by diffusively transferring the formed dye or the like to an image receiving layer The present invention relates to a color light-sensitive material.

[0002]

2. Description of the Related Art Photosensitive materials (heat-developable light-sensitive materials) for obtaining an image simply and quickly by carrying out a development process by a dry process with heat are known. No. 43-4921, No. 43-4924, 553 of "Basics of Photographic Engineering", Silver Salt Photography (published by Corona Publishing Co. in 1879)
Pp.-555, and Research Disclosure, 1978.
June issue, pages 9 to 15 (RD-17029) and the like.

There are two types of heat-developable light-sensitive materials for obtaining a black and white image and ones for obtaining a color image. In recent years, development of a heat-developable color light-sensitive material for obtaining a color image using various dye-donor substances has been attempted. ing.

There are various types of heat-developable color light-sensitive materials. For example, a system in which a diffusible dye is released or formed by heat development and then the dye is transferred to obtain a color image (hereinafter referred to as a transfer system). , Which requires an image-receiving member for transfer, is excellent in terms of image stability and sharpness, and easiness and speed of processing. This transfer type heat-developable color light-sensitive material and image forming method are disclosed in, for example, JP-A-50-12431, 59-159159, and 59-181345.
No. 59, No. 229556, No. 60-2950, No. 61-52643, No. 61
-61158, 61-61157, 59-180550, 61-132952
No. 61-139842, U.S. Pat.
4,590,154 and 4,584,267, etc.

Among these, JP-A-59-124339 and JP-A-5-124339.
9-181345, 60-2950, 59-182507, U.S. Patent 4,
No. 631,251, 4,650,748, a dye is formed by a coupling reaction, and a heat-developable color light-sensitive material capable of forming a color image by transferring the formed dye has high density and low fog. It is excellent in that color images can be easily obtained.

In these heat-developable color light-sensitive materials,
Using a light-sensitive layer having two or more different silver halides each having blue-sensitive silver halide and other color-sensitive, for example, red-sensitive or green-sensitive silver halide In the case of a multi-layer multicolor color light-sensitive material,
A compound that absorbs blue light (blue light absorbing dye) is provided between the two layers by providing a blue color sensitive silver halide layer as an upper layer and another color sensitive silver halide-containing layer as a lower layer in the direction of exposure. It is common practice to provide a layer containing). As a blue light absorbing dye that can be used in the heat-developable color photosensitive material,
JP-A-60-209734, JP-A-63-298338, JP-A-2-2713
Blue light absorbing dyes described in No. 53 are known.

However, the dye described in the above specification is not completely fixed in the layer to which the dye is added immediately after coating, and diffuses to some extent in the upper layer or the lower layer, so that the sensitivity of the blue-sensitive layer is lowered. However, there is a drawback that the difference in sensitivity with other photosensitive layers becomes small and color mixing occurs.
Further, the blue light absorbing dye has a drawback that it is transferred to the image receiving layer to cause stains, and development of a heat-developable color light-sensitive material in which these points are improved has been earnestly desired.

On the other hand, there has been conventionally known a method of incorporating a dye into a heat-developable color light-sensitive material to adjust photographic sensitivity and improve sharpness. For example, there is known a method of adding a dye described in JP-A-61-48854 or a dye used in a conventional photographic light-sensitive material to a heat-developable color light-sensitive material.

However, since the dyes described in the above specification and the dyes used in conventional photographic light-sensitive materials are not fixed in the added layer, a large amount of coating is required or fogging is increased by heat development. The drawbacks that cause
It has a drawback that it is transferred to the image-receiving layer to generate stains, and development of a heat-developable color light-sensitive material in which these points are improved has been earnestly desired.

[0010]

Therefore, the present invention is intended to solve the problems of the heat-developable color light-sensitive material containing the above-mentioned known blue light absorbing dye and the dye used for adjusting the sensitivity or improving the sharpness. It is a thing.

A first object of the present invention is to provide a heat-developable color light-sensitive material capable of obtaining a transferred image with less color turbidity (less color mixing).

A second object of the present invention is to provide a heat-developable color light-sensitive material capable of obtaining a transferred image with less stain.

A third object of the present invention is to provide a heat-developable color light-sensitive material having high density, low fog and excellent sharpness.

[0014]

[Means for Solving the Problems] In order to achieve the above object, the inventors of the present invention have conducted intensive studies and found that the above object can be achieved by the following.

(1) At least a photosensitive silver halide, an organic silver salt, a reducing agent, a binder, a dye-providing substance and a metal complex salt dye represented by the general formula [I] are contained on a support. A heat-developable color photosensitive material.

[0016]

[Chemical 4]

In the formula, R ₁ is a hydrogen atom, a halogen atom, a hydroxyl group, a sulfo group, a mercapto group, a nitro group, a cyano group, a monovalent organic group having 13 or less carbon atoms, a 5-membered or 6-membered heterocyclic group. , Represents a hydrocarbon ring group. The heterocyclic group or the hydrocarbon ring group may form a condensed ring with the benzene ring to which R ₁ is bonded.

X ₁ is a counter ion constituting a complex salt and represents H ⁺ , H ₃ O ⁺ , an alkali metal ion, an alkaline earth metal ion, or a halogen ion.

Y ₁ is --O--, --COO--, --NH--, --SO ₂ N
(R ₂ )-, where R ₂ represents an alkyl group or an aralkyl group. n ₁ represents an integer of 0 to 4, and P ₁ represents an integer of 1 or 2. M ₁ represents a metal atom.

(2) The support contains at least a photosensitive silver halide, an organic silver salt, a reducing agent, a binder, a dye-providing substance and a metal complex dye represented by the general formula [II]. A heat-developable color photosensitive material.

[0021]

[Chemical 5]

In the formula, R ₃ , M ₂ and n ₂ have the same meanings as R ₁ , M ₁ and n ₁ in the formula [I].

(3) The support contains at least a photosensitive silver halide, an organic silver salt, a reducing agent, a binder, a dye-providing substance and a metal complex dye represented by the general formula [III]. A heat-developable color photosensitive material.

[0024]

[Chemical 6]

In the formula, R ₄ , X ₂ , Y ₂ , n ₃ , P ₂ and M ₃ are respectively R ₁ , X ₁ , Y ₁ , n ₁ , P ₁ and M ₁ in the general formula [I]. Are synonymous.

The present invention will be described in detail below.

The metal complex salt dye in the present invention is a dye containing a metal in the form of an intramolecular complex salt, and it is Zenichi Yoshida, Journal of Synthetic Organic Chemistry, 16 (5), 240-251 (1958), Iida. Hirotada, Journal of Synthetic Organic Chemistry, 18 (11), 779-785 (1960),
Yutaka Hosoda, New Dye Chemistry, 155-163, 281-290 (Gihodo)
And the like.

The dyes according to the present invention can be classified as follows.

(A) Metal complex dye represented by the general formula [I] A compound having a coordination atom group at the ortho position of the azo group,
Specifically, Neolan, Palatin Fast system and Irgalan, Cibal
an-type chromium complex salt dye, Benzo Fast Copper dye, Chlor
Examples include antin Fast dye, Coprotin dye, and copper complex salt type serious dye. Specifically, Patatin Fast Yellow 3GN, Fa
ratine Fast Bordeaux RN, PalatineFast Red R, Palat
ine Fast Violet 5RN, Palatine Fast Orange GEN, Pal
atineFast Yellow GRN, Palatine Fast Blue BN, Neola
n Blue B, Palatine Fast BlueGGN, Neolan Blue 2G, B
enzo Fast Copper Navy Blue RL, Sirius Supra BlueG
L, Benzo Fast Copper Blue FBL, Benzo Fast Chrom Ye
llow etc. are mentioned.

(B) Metal complex salt dye represented by the general formula [II] A metal complex salt of phthalocyanine, which is copper phthalocyanine,
Copper phthalocyanine disulfonic acid (Sirius Light Turquoi
s Blue GL), polychloro-substituted tetrasulfonic acid of copper phthalocyanine, sulfonated copper tetracyanophthalocyanine, tri- or tetrachloro-substituted nickel phthalocyanine disulfonic acid, copper tetra (5) benzamide phthalocyanine tetrasulfonic acid, Sirius Supra Gre
en FFG, Alcian Blue 8 GX, Sulfogen Brilliant Green
J, Thiocyanocopper phthalocyanine, Indanthren Brilliant
Blue 4G, etc., and other central metals are Na, K, Be, Mg,
Included are phthalocyanine dyes substituted with Ca, Ba, Cd, Hg, Cr, Fe, Co, Zn, Pt and Pd.

(C) Metal Complex Salt Dye Represented by General Formula [III] A metal complex salt of an azomethine dye, which is a compound having a coordination atom group at the ortho position of the azomethine group.

In the general formula [I], examples of the halogen atom represented by R ₁ include chlorine, bromine, iodine and the like.

Typical organic groups having 13 or less carbon atoms represented by R ₁ are shown below.

Alkyl group (eg methyl, ethyl, butyl, octyl, dodecyl etc.), alkoxy group (eg methoxy, ethoxy, butoxy, dodecyloxy etc.), aryloxy group (eg phenoxy, chlorophenoxy, naphthoxy etc.), alkylsulfur Famoyl group (eg ethylsulfamoyl, octylsulfamoyl etc.), arylsulfamoyl group (eg phenylsulfamoyl, naphthylsulfamoyl etc.), alkylcarbonyl group (eg ethylcarbonyl, dodecylcarbonyl etc.), alkyl Oxycarbonyl group (eg methoxycarbonyl, decyloxycarbonyl etc.), alkylsulfonyl group (eg ethylsulfonyl, dodecylsulfonyl etc.), alkylsulfonamide group (eg ethanesulfonamide, dodeca) Sulfonamide), alkylamino group (e.g. dimethylamino, dipropylamino, etc.), an acylamino group (e.g. acetamido, butanamide, dodecane amide).

Examples of the heterocyclic group represented by R ₁ include furyl group, pyrrolyl group, pyridyl group and pyrazolyl group.

Examples of the hydrocarbon ring group represented by R ₁ include a cyclopentyl group, a cyclohexyl group, a phenyl group and a tolyl group.

Examples of the alkali metal ion represented as X ₁ e.g. K ^+, Na ⁺ is, for example Mg ⁺⁺ as the alkaline earth metal ions, Ba ^++, and examples of the halogen ion such as chlorine ion, bromine Ions and iodine ions are mentioned.

In -SO ₂ N (R ₂ ) -represented by Y ₁ , the alkyl group represented by R ₂ is, for example, a methyl group,
Examples thereof include an ethyl group, propyl group and butyl group, and examples of the aralkyl group include a benzyl group and a phenethyl group.

In the metal complex salt dyes represented by the general formulas [I], [II] and [III], the metal forming the complex salt can be freely selected, but transition metals are preferred, and chromium, manganese, and Examples include iron, cobalt, nickel, copper and zinc.

General formulas [I], [II] and [II] according to the present invention
Specific examples of the dye represented by I] are shown below, but the invention is not limited thereto.

[0041]

[Chemical 7]

[0042]

[Chemical 8]

[0043]

[Chemical 9]

[0044]

[Chemical 10]

[0045]

[Chemical 11]

[0046]

[Chemical formula 12]

The dye according to the present invention can be easily obtained as a commercial product or can be produced by a method known in the art.

The dye according to the present invention may be used alone or in combination of two or more kinds. The amount used is not limited, and may be determined depending on the type of the dye, single use or use of two or more types in combination. For example, the amount used is 0.01 g per 1 m ² of the support. -10g, preferably 0.04
~ 1.5 g can be used.

The above dye may be contained in any of the layers constituting the light-sensitive material. Among them, the blue light absorbing dye is preferably contained in at least one non-photosensitive layer which is present in a stacked relationship with the photosensitive layer containing the blue-sensitive silver halide.

More preferably, at least one non-photosensitive layer contained in a non-photosensitive layer disposed between the blue color-sensitive layer and another color-sensitive layer, and particularly present in direct contact with the light-sensitive layer. It is preferably contained in the layer. The non-photosensitive layer containing the blue light absorbing dye may be on the support side or the side opposite to the support as viewed from the blue color-sensitive layer, but is exposed from the photosensitive layer side, for example. In this case, the non-photosensitive layer containing the blue light absorbing dye is preferably on the support side as viewed from the blue color-sensitive layer, and when exposed from the support side, it is on the side opposite to the support as viewed from the blue color-sensitive layer. Preferably.

On the other hand, when the dye according to the present invention is used for the purpose of improving the sharpness, it can be used in either the photosensitive layer or the non-photosensitive layer.

The dye according to the present invention is dispersed by a ball mill, a sand mill, etc., dissolved in a solvent such as water or methanol acetone, dissolved in a solvent such as ethyl acetate, and added with an aqueous gelatin solution and a surfactant to prepare a super dye. It can be added by a method of forming an aqueous dispersion with a sonic disperser or the like.

Reducing agent used in the photothermographic material (in this specification, the reducing agent precursor is also included in the reducing agent)
What is usually used in the field of a photothermographic material can be used. Examples of the reducing agent that can be used in the present invention include, for example, U.S. Patents 3,531,286 and 3,761,270.
Nos. 3,764,328, Research Disclosure (RD) No. 12146, No. 15108, No. 15127 and JP-A-56-27132, U.S. Patents 3,342,599, 3,719,492.
Nos. Each specification, JP-A-53-135628, JP-A-57-79035, etc., p-phenylenediamine-based and p-aminophenol-based developing agents, phosphoroamidophenol-based and sulfonamideaniline-based developing agents, and Hydrazone color developing agents and their precursors, or phenols, sulfonamide phenols, or polyhydroxybenzenes, naphthols, hydroxybisnaphthyls and methylenebisnaphthols, methylenebisphenols, ascorbic acid, 3-pyrazolidones , Pyrazolones can be optionally used. Particularly preferable reducing agents include N- (pN, N-dialkyl-aminophenol) sulfamate salts described in JP-A-56-146133 and JP-A-62-227141.

A dye-providing substance can be used in the photothermographic material of the invention. Examples of dye-donor substances that can be used in the photothermographic material of the invention include those disclosed in JP-A-62-62.
-44737, 62-129852, 62-169158 couplers forming non-diffusible dyes, for example, leuco dyes described in U.S. Pat.No. 475,441, or described in U.S. Pat. Examples of the azo dyes used in the heat development bleaching method include a diffusible dye-providing substance that forms or releases a diffusible dye, more preferably a compound that forms a diffusible dye by a coupling reaction. It is preferable to use.

The diffusion type dye-providing substance that can be used in the present invention will be described below. As the diffusion-type dye-providing substance, any substance that can form or release a diffusible dye as a function of the reaction corresponding to the reduction reaction of the photosensitive silver halide and / or the organic silver salt optionally used Often, it can be classified into a negative type dye-providing substance and a positive type dye-providing substance according to the reaction form.

Examples of the negative dye-providing substance include, for example, US Pat. Nos. 4,463,079 and 4,439,513, and JP-A-59-60434.
Issue 59-65839, Issue 59-71046, Issue 59-87450, Issue 59
-88730, 59-123837, 59-124329, 59-16505
The reducing dye-releasing compounds described in the specifications such as No. 4 and No. 59-165055 are mentioned.

Other negative type dye-providing substances include, for example, US Pat. No. 4,474,867, JP-A-59-12431 and 59-48.
765, 59-174834, 59-776642, 59-159159
No. 59-231040 and the like, and the coupling dye-releasing compounds described therein. Still another particularly preferable negative-type dye-providing substance of the coupling dye-forming compound is represented by the following general formula (a).

[0058]

[Chemical 13]

In the formula, Cp represents an organic group (coupler residue) capable of reacting (coupling reaction) with an oxidant of the reducing agent to form a diffusible dye, and J represents an oxidant of the reducing agent. Represents a divalent linking group bonded to the reactive position to react,
B represents a ballast group. Here, the ballast group is a group that prevents the dye-donor substance from substantially diffusing during the heat development treatment. It shows a group that exhibits its action depending on the nature of the molecule (such as a sulfo group), or shows its action depending on the size. A group (group having a large number of carbon atoms, etc.) and the like. The coupler residue represented by Cp preferably has a molecular weight of 700 or less, more preferably 500 or less, in order to improve the diffusibility of the dye formed. As the ballast group, a group having preferably 8 or more, more preferably 12 or more carbon atoms is preferable, and a group which is a polymer chain is more preferable. The coupling dye-forming compound having a group which is a polymer chain is preferably a compound having a polymer chain having a repeating unit derived from a monomer represented by the following general formula (b) as the above group.

[0060]

[Chemical 14]

In the formula, Cp and J have the same meanings as defined in the general formula (a), Y represents an alkylene group, an arylene group or an aralkylene group, 1 represents 0 or 1, and Z represents a divalent group. Represents an organic group, and L represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group.

Specific examples of the coupling dye-forming compounds represented by the general formulas (a) and (b) include JP-A-59-124.
339, 59-181345, 60-2950, 61-57943,
61-59336 and other publications, U.S. Pat.Nos. 4,631,251 and 4,6
There are those described in each specification of 50,748 and 4,656,124, in particular, U.S. Patents 4,656,124, 4,631,251,
Polymer type dye-donor substances described in the respective specifications of No. 4,650,748 are preferable.

Examples of positive type dye-donor substances include:
JP 59-55430, 59-165054, 59-154445,
59-766954, 59-116655, 59-124327, 59-15
There are compounds described in publications such as 2440. These dye-providing substances may be used alone or in combination of two or more. The amount used is not limited, depending on the type of the dye-donating substance, single use or two or more combined use, or whether the photographic constituent layer of the light-sensitive material of the present invention is a single layer or two or more layers. Although it may be determined by, for example, 0.005 to 50 per m ²
g, preferably 0.1 g to 10 g can be used.

The method of incorporating the dye-donor substance used in the present invention into the photographic constituent layers of the photothermographic material is arbitrary, and examples include low-boiling point solvents (methanol, ethanol, ethyl acetate, etc.) and / or HBS (dibutyl phthalate, dioctyl). Phthalate, tricresyl phosphate, etc.) and then emulsified and dispersed, or dissolved in an alkaline aqueous solution (eg, 10% sodium hydroxide aqueous solution) and then neutralized with an acid (citric acid, nitric acid, etc.) It can be used after being used as a solid or dispersed in an aqueous solution of a suitable polymer (eg, gelatin, polyvinyl butyral, polyvinyl pyrrolidone, etc.).

Next, the photosensitive silver halide used in the present invention will be described. Any silver halide can be used, and examples thereof include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, and silver iodobromide. Further, an emulsion containing grains having a multilayer structure in which the halogen composition of the grains is different from that on the surface can be used. For example, a silver halide emulsion having core / shell type silver halide grains in which the halogen composition is changed stepwise, or grains in which the halogen composition is continuously changed can be used. The shape of photosensitive silver halide is cubic, spherical,
Those having a clear crystal habit such as octahedron, dodecahedron and tetradecahedron and those not having such a crystal habit can be used. Examples of this type of silver halide are those described in JP-A-60-215948. In addition, for example, JP-A-58-111933
No. 58-111934, No. 58-108526, Research Disclosure 22534, etc., and have two parallel crystal planes, and these crystal planes are different from each other. It is also possible to use a silver halide emulsion containing tabular silver halide grains having an area larger than that of the crystal plane and having an aspect ratio, that is, a ratio of grain diameter to thickness of 5: 1 or more.

Further, in the present invention, a silver halide emulsion containing internal latent image type silver halide grains whose surface is not previously fogged can be used. Regarding the internal latent image type silver halide in which the surface is not fogged in advance, for example, U.S. Patents 2,592,250, 3,206,313, 3,317,322,
3,511,622, 3,447,927, 3,761,266, 3,7
It is described in each specification such as 03,584 and 3,736,140. An internal latent image type silver halide grain whose surface is not fogged in advance is a silver halide grain whose sensitivity inside the grain is higher than that of the surface of the silver halide grain as described in the above specification. US Pat. Nos. 3,271,157 and 3,4
47,927 and 3,531,291, a silver halide emulsion having a silver halide grain containing a polyvalent metal ion, or a silver halide grain containing a doping agent described in U.S. Pat. Silver halide emulsion in which the grain surface of the above is weakly chemically sensitized, or JP-A-50-8524
And silver halide emulsions composed of grains having a laminated structure described in JP-A No. 50-38525 and the like, and others.
The silver halide emulsions described in JP-A-52-156614 and JP-A-55-127549 can be used.

The silver halide in the above light-sensitive emulsion may be coarse grains, but the preferred grain size is from about 0.005 μm to about 1.5 μm, and more preferably about 0.01 μm.
It is μm to 0.5 μm.

In the present invention, as another method for preparing photosensitive silver halide, a photosensitive silver salt-forming component is allowed to coexist with an organic silver salt described below to form photosensitive silver halide on a part of the organic silver salt. You can also

These light-sensitive silver halide and light-sensitive silver salt-forming components can be used in combination in various forms, and the amount used is from 0.001 g to 50 g per 1 m ^{2 of} support.
Is preferable, and more preferably 0.1 g to 10 g.

The photosensitive silver halide emulsion may be chemically sensitized by any method used in the photographic art.
The photosensitive silver halide emulsion used can be spectrally sensitized with a known spectral sensitizing dye in order to impart sensitivity to blue, green, red and near infrared light. Representative spectral sensitizing dyes that can be used include, for example, cyanine,
Examples thereof include merocyanine, complex (that is, trinuclear or tetranuclear) cyanine, holopolar cyanine, styryl, hexianine, and oxonol. The preferred addition amount of these sensitizing dyes is 1 × 10 ⁻⁶ mol to 1 mol per mol of the photosensitive silver halide or the silver halide-forming component. More preferably, it is 1 × 10 ^-5 to 1 × 10 ^-1 mol.

The sensitizing dye may be added at any stage during the preparation of the silver halide emulsion. That is, it may be at any time such as during formation of silver halide grains, removal of soluble salts, before start of chemical sensitization, during chemical sensitization, or after completion of chemical sensitization. In the photothermographic material of the present invention, it is preferable to use various organic silver salts for the purpose of increasing sensitivity and improving developability, if necessary.

Organic silver salts that can be used in the photothermographic material of the present invention include those disclosed in JP-A-53-4921 and JP-A-49-52626.
No. 52-141222, No. 53-36224 and No. 53-37626,
No. 53-37610 and other publications and U.S. Pat.
Nos. 3,794,496 and 4,105,451 etc., long-chain silver salts of aliphatic carboxylic acids and silver salts of carboxylic acids having a heterocycle, such as silver behenate, as described in each specification.
α- (1-Phenyltetrazolethio) acetic acid silver, etc., Japanese Patent Publication Nos. 44-26582, 45-12700, 45-18416, 45-221
No. 85, JP-A Nos. 52-137321, 58-118638, and 58-11863.
There are silver salts of imino groups described in each publication of No. 9 and US Pat. No. 4,123,274. Among the above organic silver salts, silver salts of imino groups are preferable, particularly silver salts of benzotriazole derivatives, more preferably 5-methylbenzotriazole and its derivatives, sulfobenzotriazole and its derivatives, N-alkylsulfamoylbenzo. It is a silver salt of triazole and its derivatives.

The organic silver salt used in the present invention may be used alone or in combination of two or more kinds. Further, the silver salt may be prepared in an appropriate binder and used as it is without isolation, or the isolated salt may be dispersed in the binder by an appropriate means before use. Examples of the dispersing means include, but are not limited to, a ball mill, a sand mill, a colloid mill, and a vibration mill. The amount of the organic silver salt used is usually preferably 0.01 to 500 mol per mol of the photosensitive silver halide,
It is more preferably 0.1 to 100 mol. More preferably 0.
It is 3 to 30 mol.

Examples of the binder that can be used in the photothermographic material of the present invention include polyvinyl butyral, polyvinyl acetate, ethyl cellulose, polymethyl methacrylate, cellulose acetate butyrate, polyvinyl alcohol, polyvinyl pyrrolidone, gelatin, phthalated gelatin, and the like. There are synthetic and natural polymer substances such as gelatin derivative, cellulose derivative, protein, starch, gum arabic, etc. These can be used alone or in combination of two or more. In particular, it is preferable to use gelatin or a derivative thereof and polyvinylpyrrolidone, and a hydrophilic polymer such as polyvinyl alcohol in combination, and more preferably, a mixed binder of gelatin described in JP-A-59-229556 and polyvinylpyrrolidone is used. That is.

The preferred amount of the binder used is usually 0.05 to 50 g, and more preferably 0.2 per m ^{2 of the} support.
g to 20 g. Also, the binder is 1 g of the dye-donating substance.
It is preferable to use 0.1 g to 10 g, more preferably 0.2 g to 5 g.

The photothermographic material of the present invention can be obtained by forming a photographic constituent layer on a support. Examples of the support that can be used here include polyethylene film, cellulose acetate film and polyethylene terephthalate film. , Synthetic plastic films such as polyvinyl chloride, photographic base paper, printing paper, baryta paper and range coated paper, and the like. Further, an electron beam curable resin composition is applied and cured on these supports. And a support or the like.

The heat-developable light-sensitive material of the present invention may contain, in addition to the above-mentioned components, various additives such as a development accelerator, an antifoggant, an inorganic or organic base, or a base precursor, if necessary. .. As the development accelerator, compounds described in JP-A-59-177550, JP-A-59-111636 and JP-A-59-124333, or JP-A-61-159642 and Japanese Patent Application No. 62-203908. The development accelerator releasing compound described in JP-A-63-104645 or the electronegativity of 4 described in JP-A-63-104645.
The above metal ions can also be used. The antifoggant is not particularly limited, but particularly preferable antifoggants include those having a hydrophilic group described in JP-A-62-78554, JP-A-62-121452. And polymers having a ballast group described in JP-A-62-123456. Examples of the base precursor include a compound that decarboxylates by heating to release a basic substance (eg, guanidinium trichloroacetate), a compound that decomposes by a reaction such as an intramolecular nucleophilic substitution reaction to release an amine, and the like. For example, JP-A-56-1
30745, 56-132332, British patents 2,079,480
U.S. Pat. No. 4,060,420, each specification, JP-A-59-157637
No. 59-166943, 59-180437, 59-174830,
Examples thereof include base releasing agents described in JP-A-59-195237, JP-A-62-108249, JP-A-62-174745 and the like. In addition, various additives used in the photothermographic material as required, for example, antihalation dyes, fluorescent whitening agents, hardeners, antistatic agents, plasticizers, extenders, matting agents, surfactants, Can contain anti-fading agent etc.,
These are specifically described in Research Disclosure Vol. 170, June 1978 No. 17029, JP-A-62-13.
It is described in Japanese Patent No. 5825. These various additives may be added not only to the photosensitive layer but also to a non-photosensitive layer such as an intermediate layer, a protective layer or a backing layer.

In the photothermographic material of the present invention, in addition to (a) a photosensitive silver halide, (b) a thermal solvent, (c) a dye-donor substance, which is usually used in a photothermographic material, and (d) an organic material. A silver salt and (e) a reducing agent may be contained. These may be basically contained in one photothermographic layer, but they are not necessarily contained in a single photographic constituent layer. For example, the photothermographic layer may be divided into two layers, and a) a photosensitive silver halide, (d) an organic silver salt, and (e) a reducing agent component are contained in one heat-developable photosensitive layer, and (b) a thermal solvent is contained in the other layer adjacent to the photosensitive layer. (C) The dye-providing substance may be contained in the composition, or may be contained in two or more constituent layers as long as they can react with each other. or,
The heat-developable photosensitive layer may be divided into two layers of a low-sensitivity layer and a high-sensitivity layer, a high-concentration layer and a low-concentration layer, or more.

The photothermographic material of the present invention has one or more photothermographic layers. A full-color light-sensitive material is generally provided with three heat-developable photosensitive layers having different color sensitivities, and in each photosensitive layer, dyes having different hues are formed or released by heat development. Usually, a yellow dye is combined with the blue color-sensitive layer, a magenta dye is combined with the green color-sensitive layer, and a cyan dye is combined with the red color-sensitive layer, but not limited thereto. It is also possible to combine a near-infrared color-sensitive layer.

In the heat-developable photosensitive material of the present invention, in addition to the heat-developable photosensitive layer, a non-photosensitive layer such as an undercoat layer, an intermediate layer, a protective layer, a filter layer, a backing layer and a peeling layer is optionally provided. be able to. For coating the heat-developable photosensitive layer and these non-photosensitive layers on a support, the same methods as those used for coating and preparing a general silver halide photosensitive material can be applied.

The photothermographic material of the present invention can be exposed by an appropriate light source, and examples of the exposure light source include a tungsten lamp, a halogen lamp, a xenon lamp, a mercury lamp, a cathode ray tube flying spot, a light emitting diode and a laser (for example, a gas laser). , YAG laser, dye laser, semiconductor laser, etc.), CRT light source and FOT
Etc., and various other materials can be used alone or in combination. A semiconductor laser and a second harmonic generation element (SHG element) or the like can also be used. others,
It may be exposed by light emitted from a phosphor excited by an electron beam, X-ray, γ-ray, α-ray or the like. The exposure time is not limited to 1 / 1,000 second to 1 second normally used in cameras, but is shorter than 1 / 1,000 second, for example, 1 / 1,000 to 1/10 ^-8 using a xenon flash lamp or a cathode ray tube.
Second exposures can also be used. If necessary, the spectral composition of the light used for exposure can be adjusted with a color filter. The light-sensitive material of the present invention can be used for scanner exposure using a laser or the like.

After imagewise exposure, the photothermographic material of the present invention is usually preferably 80 to 200 ° C, more preferably 100 to 170 ° C.
The development can be carried out by heating in the temperature range of 1 to 180 seconds, more preferably 1.5 to 120 seconds. The transfer of the diffusible dye to the image-receiving layer may be carried out simultaneously with the development by bringing the image-receiving member into close contact with the photosensitive surface of the photosensitive material and the image-receiving layer during heat development. Alternatively, the transfer may be performed by supplying water, then closely contacting the same, and further heating if necessary. In addition, preheating may be performed in the temperature range of 70 ° C to 180 ° C before exposure. Further, as described in JP-A-60-143338 and JP-A-61-162041, in order to enhance mutual adhesion, the photosensitive material and the image receiving member are heated at a temperature of 80 ° C to 250 ° C immediately before heat development transfer. May be preheated respectively.

Various heating means can be used in the photothermographic material of the present invention.

As the heating means, all the methods applicable to ordinary photothermographic materials can be used, for example, contact with a heated block or plate, contact with a heat roller or heat drum, or in a high temperature atmosphere. Or
Alternatively, high frequency heating may be used, or a Joule heat generated by energization may be utilized by providing a conductive layer containing a conductive substance such as carbon black on the back surface of the photosensitive material of the present invention or the back surface of the thermal transfer image receiving member. it can. The heating pattern is not particularly limited, and includes a method of preheating after preheating, and then heating again at a high temperature for a short time or at a low temperature for a long time. It is also possible to lower the temperature or repeat them, and discontinuous heating is also possible, but a simple pattern is preferable. Alternatively, a method in which exposure and heating proceed simultaneously may be used.

When the present invention is a transfer type photothermographic material, the image receiving member is used as described above. In that case, the image-receiving layer effectively used in the image-receiving member may be one having a function of receiving the dye in the heat-developable photosensitive layer released or formed by heat development, for example, tertiary amine or 4
Polymers containing quaternary ammonium salts, US Pat. No. 3,709,69
Those described in the specification No. 0 are preferably used. As a typical image-receiving layer for diffusion transfer, there is one obtained by mixing a polymer containing an ammonium salt, a tertiary amine or the like with gelatin, polyvinyl alcohol or the like and coating the mixture on a support. Another useful dye-receptive substance is a substance formed of a heat-resistant organic polymer substance having a glass transition temperature of 40 ° C. or higher and 250 ° C. or lower as described in JP-A-57-207250.

These polymers may be carried on the support as an image receiving layer, or may be used as the support itself. As a polymer, "Polymer Handbook, Second Edition" (edited by Joy Brand Wrap, EH Inmargat) John Willi & Sons Publishing {Polymer Handbook 2nd ed. (J.
A synthetic polymer having a glass transition temperature of 40 ° C. or higher described in “John Wiley & Sons” by Brandrup, EHImmergut) is also useful. Generally, 2,000 to 200,000 is useful as the molecular weight of the polymer substance. These polymer substances may be used alone or in combination of two or more kinds, or may be used in combination of two or more kinds as a copolymer.

A particularly preferable image receiving layer is disclosed in JP-A-59-2.
Examples thereof include a layer made of polyvinyl chloride described in JP-A-23425 and a layer made of polycarbonate and a plasticizer described in JP-A-60-19138. It is also possible to use these polymers as an image receiving layer (image receiving member) which also serves as a support, and at that time, the support may be formed of a single layer or a plurality of layers. Good.

As the support for the image receiving member, a transparent support,
Any material such as an opaque support may be used. For example, films of polyethylene terephthalate, polycarbonate, polystyrene, polyvinyl chloride, polyethylene, polypropylene, etc., and titanium oxide, barium sulfate, calcium carbonate, talc in these supports may be used. Supports containing pigments such as etc., baryta paper, range coated papers laminated with a thermoplastic resin containing pigments on papers, cloths, glasses, metals such as aluminum, etc., and these supports Examples of the support include a support in which an electron beam curable resin composition containing a pigment is applied and cured, and a support in which a coating layer containing a pigment is provided on these supports. Furthermore, JP-A-62-28333
Various coated papers such as the cast coated paper described in No. 3 are also useful as the support.

Further, a support obtained by coating and curing an electron beam curable resin composition containing a pigment on paper or a pigment coating layer on the paper has an electron beam curing property on the pigment coating layer. The support coated with the resin composition organism and cured can be used as it is as an image receiving member because the resin layer itself can be used as an image receiving layer.

Appropriate additives, for example, various known additives can be added to the image receiving member. Examples of such additives include, for example, ultraviolet absorbers, image stabilizers,
Development accelerator, antifoggant, pH adjuster (various acids and acid precursors, or bases and base precursors, etc.)
And hot solvents. Representative examples of the ultraviolet absorber include benzotriazole compounds and benzophenone compounds. As the image stabilizer, for example, hindered amine type, hindered phenol type, dialkoxybenzene type, chroman type, indane type, thioether type, hydroquinone type,
Examples thereof include chloro-substituted s-triazine compounds. The development accelerator and antifoggant can be appropriately selected and used from the compounds added to the photothermographic material.

The photothermographic material of the present invention is described in RD (Research Disclosure Magazine) No. 15108, JP-A-57-198458.
No. 57-207250, No. 61-80148, and a so-called monosheet type photothermographic material in which the photosensitive layer and the image receiving layer are provided on the same support. it can.

A protective layer is preferably provided on the photothermographic material of the invention. Various additives used in the field of photography can be used in the protective layer. Examples of the additive include various matting agents, colloidal silica, sliding agents, organic fluoro compounds (particularly fluorine-based surfactants), antistatic agents, ultraviolet absorbers, high boiling organic solvents, antioxidants, hydroquinone derivatives, polymers. Latex, surfactants (including polymeric surfactants), hardeners (including polymeric hardeners), organic silver salt particles, non-photosensitive silver halide particles, antifoggants, development accelerators, etc. Can be mentioned.

Regarding these additives, RD (Research Disclosure Magazine) Vo.170, June 1978 No.1702
No. 9, JP-A-62-135825.

[0094]

EXAMPLES Specific examples of the present invention will be described below, but the present invention is not limited to the examples described below.

Example-1 Preparation of Silver Iodobromide Emulsion (Em-1) The silver iodobromide emulsion (Em-1) was prepared by using the following five kinds of solutions.
-1) was prepared. The seed emulsion contained 2 mol% of silver iodide and had an average grain size (indicated by the length of one side of a cube having the same volume; the same applies in the following description), a silver iodobromide emulsion (SE-
1) was used.

(Solution A-1) Ocein gelatin 0.45 g Polyisopropylene-polyethyleneoxy-disuccinate ester sodium salt 10% methanol solution 5.0 ml 28% ammonia water 29 ml Seed emulsion (SE-1) 0.071 mol equivalent amount Ion Exchanged water 1750 ml (Solution B-1) Ocein gelatin 5.0 g KBr 200.0 g Kl 5.8 g Make up to 500 ml with ion exchange water (Solution C-1) AgNO ₃ 246.3 g 28% ammonia water 200.9 ml Make up to 414 ml with ion exchange water (Solution D-1) 50% KBr aqueous solution pAg adjustment required amount (Solution E-1) 56% acetic acid aqueous solution pH adjustment required amount At 40 ° C, the mixing shown in JP-A-57-92523 and 57-92524. Using a stirrer, (Solution B-1) and (Solution C-1) were added to (Solution A-1) at the same flow rate by the simultaneous mixing method.

The pH during the simultaneous mixing was adjusted by changing the flow rate with a roller tube pump having a variable flow rate (solution E-1).
Was added to control at 8.0. pAg was adjusted to 8.8 at the time of starting the addition of (Solution B-1) and (Solution C-1), and then continuously changed in proportion to the addition amount of (Solution B-1), At the end of the addition of (-1) and (solution C-1), it was controlled to be 9.3. The pAg is controlled by a roller tube pump with variable flow rate (solution D-1).
The flow rate was changed.

Addition of (Solution B-1) and (Solution C-1) was carried out at an allowable maximum speed (critical speed) without generation of small particles, and when 296 ml of (Solution C-1) was added, 4.5 ×
10 ⁻⁷ mol of potassium hexachloroiridium (IV) ate (K ₂ IrCl ₆ ) was added as an aqueous solution. Further (solution B-
1) and (solution C-1) were continuously added, and the process was completed when (solution C-1) was completely added. Then (Solution D-
1) and (solution E-1) were used to adjust pAg 10.4 and pH to 6.0, and desalting and washing were performed by a conventional method. Then, it was dispersed in an aqueous solution containing 45.65 g of ossein gelatin, 0.21 g of compound ST-2 shown below was added, and the total amount was 1200 with distilled water.
The solution was adjusted to have a volume of ml, and then (solution D-1) and (solution E-1) were used to adjust the pAg to 8.5 and the pH to 5.8 at 40 ° C.

[0099]

[Chemical 15]

Emulsion (Em-1) thus obtained
Was a silver iodobromide emulsion having a silver iodide content of 2 mol%, and as a result of electron microscope observation, it was found to be a monodisperse emulsion having an average grain size of 0.25 μm. The shape of the obtained silver iodobromide grains was almost cubic, but the corners and sides were slightly rounded.

Preparation of Light-Sensitive Silver Halide (a) Preparation of Red Color Sensitive Emulsion (R-1) 300 ml of silver iodobromide emulsion Em-1 was kept warm at 52 ° C. and stirred,
50 mg of the following sensitizing dye (a) and 100 mg of the following sensitizing dye (b)
Was added as a 1% methanol solution, 10 minutes later, 15 μmol of sodium thiosulfate was added as a 0.1% aqueous solution, and 60 minutes later, 10 μmol of chloroauric acid (as a 0.05% aqueous solution) and ammonium thiocyanate (0.1%) were added. 20 μmol was added (as an aqueous solution). After keeping the temperature at 52 ° C and stirring for the optimum time (30 to 80 minutes), the temperature was lowered to 40 ° C and 4-hydroxy-6-methyl-1,3,3a, 7-
Tetraazaindene 250 mg, 1-phenyl-5-mercaptotetrazole 5 mg and the following antifoggant ST-1 25 mg were added as a 5% methanol solution to stabilize the emulsion, and the total amount was adjusted to 540 ml with deionized water. Color-sensitive emulsion R-
Got 1.

(B) Preparation of green color-sensitive emulsion (G-1) 300 ml of silver iodobromide emulsion Em-1 was kept warm at 52 ° C. and stirred,
150 mg of the following sensitizing dye (c) was added as a 1% methanol solution, and 10 minutes after that, 15 μmol of sodium thiosulfate was added.
Add as a 0.1% aqueous solution, and after 60 minutes, add chloroauric acid (0.0
5 μmol (as a 5% aqueous solution) and 10 μmol of ammonium thiocyanate (as a 0.1% aqueous solution) were added. Keep the temperature at 52 ℃ as it is, continue aging for 75 minutes with stirring, then cool to 40 ℃, and then add 4-hydroxy-6-methyl-1,3,3
250 mg of a, 7-tetraazaindene, 5 mg of 1-phenyl-5-mercaptotetrazole and 25 of the antifoggant ST-1
mg was added as a 5% methanol solution to stabilize the emulsion, and the total amount was adjusted to 540 ml with ion-exchanged water to obtain a green color-sensitive emulsion G-1.

(C) Preparation of blue-sensitive emulsion (B-1) 300 ml of silver iodobromide emulsion Em-1 was kept warm at 52 ° C. and stirred,
150 mg of the following sensitizing dye (d) was added as a 1.00 methanol solution, and 10 minutes after that, 15 μmol of sodium thiosulfate was added.
Add as a 0.1% aqueous solution, and after 60 minutes, add chloroauric acid (0.0
5 μmol (as a 5% aqueous solution) and 10 μmol of ammonium thiocyanate (as a 0.1% aqueous solution) were added. Keep the temperature at 52 ℃ as it is, continue aging for 55 minutes with stirring, then cool to 40 ℃, and then add 4-hydroxy-6-methyl-1,3,3
250 mg of a, 7-tetrazaindene, 5 mg of 1-phenyl-5-mercaptotetrazole and 25 mg of the antifoggant ST-1
Is added as a 5% methanol solution to stabilize the emulsion,
The total amount was adjusted to 540 ml with deionized water and the blue color emulsion B was prepared.
-1 was obtained.

The structures of the sensitizing dye and the stabilizer used in the preparation of the above emulsions are shown below.

[0105]

[Chemical 16]

Preparation of benzotriazole silver salt emulsion At 50 ° C., using a mixing stirrer disclosed in JP-A Nos. 57-92523 and 57-92524, gelatin amino groups
300 g of modified gelatin 90% or more of which was substituted with a phenylcarbamoyl group, 2400 ml of ion-exchanged water, 9.18 g of benzotriazole, 51 ml of 28% ammonia water were dissolved in an aqueous solution (OA-1), 250 g of benzotriazole, 28% of ammonia. 1420 ml of an aqueous solution (O containing 169 ml of water
B-2) and 1420 ml of an aqueous solution (OC-1) containing 360 g of silver nitrate and 336 ml of 28% aqueous ammonia were added at an equal flow rate by the simultaneous mixing method. PH 9.3 and pH 1 during mixing
Controlled to 1. 90% of the amino groups of gelatin after the addition
60 g of modified gelatin, which was substituted with the phenylcarbamoyl group as described above, was added as a 20% aqueous solution, and then the pH was adjusted to 5.5 with 56% acetic acid, and the excess soluble salts dissolved by sedimentation were removed. Add 4800 ml of deionized water and add 10%
After adjusting the pH to 6.0 with potassium hydroxide aqueous solution and dispersing for 5 minutes, 30 g of the above-mentioned modified gelatin was made into 20% aqueous solution and added, and then the pH was adjusted to 4.5 with 3.5N sulfuric acid to cause precipitation and excess solubility. The salts were removed. Thereafter, the pH was adjusted to 6.0, 0.45 g of the compound ST-2 was added, the total amount was changed to 2520 ml with ion-exchanged water, and dispersed at 50 ° C. for 30 minutes to prepare a courageous silver salt emulsion.

Preparation of hot solvent dispersion 750 g of the following hot solvent-1 was added to 2000 ml of a 0.5% polyvinylpyrrolidone aqueous solution containing 20 g of Surfactant-1 (Alkanol XC, manufactured by DuPont), and then added to a stirrer. hand
While stirring at 500 revolutions / minute, a Dyno-Mill disperser (capacity 1400 ml, glass beads 1100 ml with an average particle size of about 0.5 mm was added by a metering pump, manufactured by Shinmaru Enterprises Co., Ltd.) at a rate of 60 ml / min. Then, it was continuously dispersed for 30 minutes. Dispersed particles of the hot solvent in the obtained dispersion, particle size 0.
About 50% for 1 μm to 1.0 μm, about 70 for 1.5 μm or less
%Met. (The particle size was observed and measured with a microscope. The same applies hereinafter.)

[0108]

[Chemical 17]

-(1) Preparation of Dye Donor Dispersion-1: 35.5 g of the following polymer dye-donor (1) and 2.4 g of the following color stain inhibitor W-1 were added to 200 ml of ethyl acetate and di- (2- Ethylhexyl) phthalate 10.0 g and tricresyl phosphate 10.0 g dissolved in a 5 wt% aqueous solution of surfactant-1.
124 ml and 720 ml of 6% gelatin aqueous solution were mixed, emulsified and dispersed by an ultrasonic homogenizer, ethyl acetate was distilled off, and the total amount was adjusted to 795 ml with ion-exchanged water to obtain a dye-providing substance dispersion liquid-1.

-(2) Dye-providing substance dispersion liquid-2 Dye-providing substance in the same manner as Dye-providing substance dispersion liquid-1 except that the polymer dye-donating substance (1) was changed to the following polymer dye-providing substance (2). The substance dispersion liquid-2 was obtained.

-(3) Dye-providing substance dispersion liquid-3: Dye-donating substance dispersion liquid-1 was prepared in the same manner as Dye-providing substance dispersion liquid-1, except that the polymer dye-donating substance (1) was changed to the following polymer dye-providing substance (3). A substance dispersion liquid-3 was obtained.

The structures of the polymeric dye-donor substance and the color stain inhibitor used in the preparation of the above-mentioned dye-donor substance dispersions are shown below.

[0113]

[Chemical 18]

[0114]

[Chemical 19]

Preparation of reducing agent solution 20.0 g of the following reducing agent (R-11) and the following reducing agent (R-33) 1
3.3g, the following surfactant-2 0.50g is dissolved in water, pH
Was adjusted to 7.0 to obtain 250 ml of the reducing agent solution.

[0116]

[Chemical 20]

Preparation of Photosensitive Material Using the prepared silver halide emulsion, benzotriazole silver salt dispersion liquid, hot solvent dispersion liquid, dye-donor substance dispersion liquid, and reducing agent solution, the layer compositions and the layer compositions shown in Tables 1 and 2 were obtained. A color photosensitive material sample No. 1 having a multilayer structure was prepared.

[0118]

[Table 1]

[0119]

[Table 2]

For coating, two layers of backing layer-1 and backing layer-2 are simultaneously coated and dried on a support coated with a double-sided subbing layer, and then the first layer to the first layer are coated on the opposite surface. Three
Three layers were simultaneously coated and dried, and then four to seven layers were simultaneously coated by four layers.

The first to seventh layers, and the backing layer-1,
2 contains the following surfactant-3 as a coating aid, and each layer contains a reaction product of tetrakis (vinylsulfonylmethyl) methane and potassium taurine as a hardening agent (reaction ratio 1: 0.75 ( Molar ratio)) was added at a rate of 0.04 g per 1 g of gelatin.

The first to seventh layers were applied after adjusting the coating solution to pH 6.0. Next, the structures of the additives, coating aids, irradiation preventing dyes, blue light absorbing dyes and the like used in the first to seventh layers are shown.

[0123]

[Chemical 21]

[0124]

[Chemical formula 22]

Sample Nos. 2 to 2 were prepared in the same manner as Sample No. 1 except that the blue light absorbing dye YF-1 of the fifth layer (second intermediate layer) of the above-mentioned multilayer color light-sensitive material was changed as shown below. No.11 was created.

Sample No. Blue light absorbing dye Sample No. Blue light absorbing dye 1 YF-1 (Comparison) 7 Example (14) 2 Example (4) 8 〃 (15) 3 〃 (5) 9 〃 (16) 4 〃 (11) 10 YF-2 (comparative) 5 〃 (12) 11 YF-3 (comparative) 6 〃 (13) The structures of comparative dyes YF-2 and YF-3 are shown below.

[0127]

[Chemical formula 23]

The coating liquid of the dye according to the present invention was prepared as follows.

Water and a surfactant alkanol XC (alkylnaphthalene sulfonate, manufactured by DuPont) were put in a ball mill container, each dye was added, zirconium oxide beads were put, and the container was sealed and ball-mill dispersed for 1 day. Then, an aqueous gelatin solution was added and mixed for 10 days, the beads were removed, and a coating solution was obtained.

Preparation of Image Receiving Member The following compounds (SA-1) and (SA
-2), a polyvinyl chloride layer (image receiving layer) containing (TP-1) and (AC-1) was applied to prepare an image receiving member.

[0131]

[Chemical formula 24]

<Evaluation of Photosensitive Material> The photosensitive materials Nos. 1 to 11 obtained by the above method were exposed to 800 CMS of blue light and green light through a step wedge.

Then, after heating the photosensitive material at 150 ° C. for 80 seconds, the image receiving members were overlaid and heated at 120 ° C. for 30 seconds to transfer the image dye formed of the photosensitive material to the image receiving member.

The transfer densities (maximum density Dmax and minimum density Dmin) of the yellow and magenta dye images were determined from the characteristic curves measured with blue light and green light. Further, in order to evaluate the color mixing property, the ratio G / B of the yellow dye image density B and the magenta dye image density G in the blue light exposed portion was determined. Further, the blue light sensitivity is represented by the reciprocal of the exposure amount required to obtain the minimum density + 0.3, and is shown as a relative value with the sensitivity of Sample No. 1 being 100. The obtained results are shown in Table 3.

[0135]

[Table 3]

From the results in Table 3, it can be seen that Samples No. 2 to No. 9 using the blue light absorbing dye of the present invention have a low degree of color mixing and exhibit a good yellow filter effect. On the other hand, in Comparative Samples No. 1 and No. 11, it can be seen that the blue light absorbing dye diffuses into the upper blue photosensitive layer and reduces the sensitivity of the blue photosensitive layer.

Example-2 The light-sensitive materials No. 1 to No. 11 obtained in Example-1 were superposed with the above-mentioned image-receiving member without exposure and heated at 120 ° C. for 30 seconds. The transfer density (stain) was measured with blue light. The results obtained are shown below.

[0138] From this result, sample No. using the blue light absorbing dye of the present invention.
It can be seen that Nos. 2 to 9 have a low stain and are a good white background. Further, since development does not occur when heated at 120 ° C., it is understood that this stain is a difference in transferability of the blue light absorbing dye to the image receiving layer.

Example 3 A silver halide emulsion, a benzotriazole silver salt dispersion, a thermal solvent dispersion dye-providing substance dispersion, and a reducing agent solution used in Example 1 were used, and the following single-layer photosensitive material was used. Sample No.12
It was created.

First layer Blue-sensitive layer Benzotriazole silver 0.29 g Ag reducing agent 0.40 g Polymeric dye-donor (2) 1.00 g TCP 0.40 g Blue-sensitive silver halide emulsion 0.30 g Ag gelatin 1.90 g Stabilizing agent (W-1) 0.03 g Polyvinylpyrrolidone 0.28 g Thermal solvent 3.00 g Antifoggant (ST-1) 0.006 g Blue light absorbing dye of the present invention (Exemplary 14) 0.05 g Support Latex-undercoated 180 μm thick transparent Polyethylene terephthalate film Next, Sample Nos. 13 to 20 were prepared in the same manner as Sample No. 12 except that the following dye was added to the blue photosensitive layer of Sample No. 12.

Sample No. 21 containing no dye was also prepared.

Sample No. Blue light absorbing dye Sample No. Blue light absorbing dye 12 Example (14) 17 Example (16) 13 〃 (4) 18 YF-2 14 〃 (6) 19 YF-1 15 〃 (11) 20 YF-316 16 (13) 21 None Each of the obtained samples was exposed to 800 CMS of blue light through a step wedge. After being combined with the image receiving member and subjected to heat development at 155 ° C. for 45 seconds, the photosensitive element and the image receiving element were rapidly peeled off. For this cyan image,
The reflection density was measured with red light, and Dmax and
Dmin, sensitivity was calculated. The sensitivity was shown as a relative value with the sensitivity of Sample No. 14 as 100. Further, in order to evaluate the stain, the unexposed portion was measured with blue light.

On the other hand, the sample was brought into close contact with a rectangular wave resolution chart having spatial frequencies of 3,5,7 Cycle / mm, exposed with the blue light, and subjected to heat treatment in the same manner as above to obtain a sample. The reflection density of the sample is measured with a microdensitometer, and CTF is a measure of sharpness.
(Contrast Tranfer Function) was calculated. The results obtained are shown in Table 4.

[0144]

[Table 4]

As is clear from Table 4, the light-sensitive material samples of the present invention showed no increase in fog and stain,
It can be seen that the sharpness (CTF value) is improved.

Example-4 Same as Sample No. 1 except that the irradiation preventing dye-2 of the second layer red photosensitive layer of the photosensitive material sample No. 1 of Example-1 was changed to the dye shown below. Layered Photosensitive Material Sample No.22
~ No.35 was created.

Sample No. Red light absorbing dye Sample No. Red light absorbing dye 22 Irradiation prevention dye-2 29 Exemplification (7) 23 Palatin Fast Blue GGN 30 〃 (8) 24 Palatin Fast Blue BN 31 〃 (9) 25 Neolan Blue B 32 〃 (10) 26 Benzo Fast Copper Navy Blue RL 33 Dye A 27 Sirius Supra Blue GL 34 〃 B 28 Benzo Fast Copper Navy Blue FBL 35 None Used for Sample Nos. The structure of the dye is shown below.

[0148]

[Chemical 25]

[0149]

[Chemical formula 26]

[0150]

[Chemical 27]

For each of the samples obtained, a red light exposure of 800 CMS was applied through a step wedge. After being combined with the image receiving member and subjected to heat development at 155 ° C. for 40 seconds, the photosensitive element and the image receiving element were rapidly peeled off. The reflection density of this cyan image was measured with red light, and Dmax, Dmin, and sensitivity were obtained in the same manner as in Example-1. Sample No. 2 sensitivity
It was shown as a relative value with the sensitivity of 1 being 100.

On the other hand, the sharpness of the above sample was determined in the same manner as in Example-3. The results are shown in Table 5.

[0153]

[Table 5]

From Table 5, samples No. 29 to No. 32 according to the present invention are shown.
Is clearly a color image with good sharpness without increasing fog compared to the comparative sample.

[0155]

According to the present invention, a heat-developable color light-sensitive material having a high density, low fog and excellent sharpness, which can obtain a transferred image with less color and stain is obtained.

Claims (3)

[Claims] 1. A support comprising at least a photosensitive silver halide, an organic silver salt, a reducing agent, a binder, a dye-providing substance and a metal complex salt dye represented by the general formula [I]. Thermal development color photosensitive material. [Chemical 1] [Wherein R ₁ is a hydrogen atom, a halogen atom, a hydroxyl group, a sulfo group, a mercapto group, a nitro group, a cyano group, a monovalent organic group having 13 or less carbon atoms, a 5-membered or 6-membered heterocyclic group,
Represents a hydrocarbon ring group. The heterocyclic group or hydrocarbon ring group is R
_A condensed ring may be formed with _1- bonded benzene ring. X ₁ is a counter ion that constitutes a complex salt, and is H ⁺ , H ₃
Represents O ⁺ , alkali metal ion, alkaline earth metal ion, and halogen ion. Y ₁ represents —O—, —COO—, —NH—, —SO ₂ N (R ₂ ) —,
R ₂ represents an alkyl group or an aralkyl group. n ₁ represents an integer of 0 to 4, and P ₁ represents an integer of 1 or 2. M ₁ represents a metal atom. ] 2. A support comprising at least a photosensitive silver halide, an organic silver salt, a reducing agent, a binder, a dye-providing substance and a metal complex salt dye represented by the general formula [II]. Thermal development color photosensitive material. [Chemical 2] [In the formula, R ₃ , M ₂ and n ₂ are respectively synonymous with R ₁ , M ₁ and n ₁ in the general formula [I]. ] 3. A support comprising at least a photosensitive silver halide, an organic silver salt, a reducing agent, a binder, a dye-providing substance and a metal complex salt dye represented by the general formula [III]. Thermal development color photosensitive material. [Chemical 3] [Wherein R ₄ , X ₂ , Y ₂ , n ₃ , P ₂ and M ₃ are synonymous with R ₁ , X ₁ , Y ₁ , n ₁ and P ₁ and M ₁ in the general formula [I], respectively. is there. ]