JPH083620B2 - Photothermographic material having a layer containing a novel blue light absorbing dye - Google Patents

Description

TECHNICAL FIELD The present invention relates to a heat-developable color light-sensitive material which transfers a diffusible dye formed by heat development to form a color image, and more particularly to a heat-developable color light-sensitive material having a multilayer structure. The present invention relates to a heat-developable color light-sensitive material for obtaining a heat-development color diffusion transfer image having a layer containing a novel blue light absorbing dye in the development light-sensitive material.

[Background of the Invention]

A light-sensitive material (heat-developable light-sensitive material) for obtaining an image simply and quickly by performing a dry process with heat is known, and the heat-developable light-sensitive material and the image forming method are described, for example, in JP-B-43-4921. 43-4924, Fundamentals of Photographic Engineering (19
593 to 555 (published by Corona Publishing Co., Ltd. in 1979), and research
Disclosure, June 1978, pages 9-15 (RD-17
029) and the like.

In recent years, development of a heat-developable color light-sensitive material for obtaining a color image using various dye-providing substances has been attempted. Among these, a method of obtaining a color image by transferring or transferring a dye after releasing or forming a diffusible dye by thermal development is considered in terms of image stability and sharpness and simplicity and speed of processing. It is excellent. This transfer type heat-developable color light-sensitive material and image forming method are described in, for example, JP-A-59-12431 and JP-A-
9-159159, 59-181345, 59-229556, 60
-2950, 61-52643, 61-61158, 61-6115
No. 7, No. 59-180550, No. 61-132952, No. 61-139842
Nos. 4,595,652, 4,590,154 and 4,58.
4,267 and the like.

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

In these heat-developable light-sensitive materials, a light-sensitive layer having two or more different silver halides having a blue-sensitive silver halide and another color-sensitive, for example, a layer having red-sensitive or green-sensitive silver halide. When a multi-layered multicolor color light-sensitive material is prepared by using, a blue-sensitive silver halide-containing layer is provided as an upper layer and another color-sensitive silver halide-containing layer as a lower layer in the normal exposure direction. It is necessary to provide a layer containing a compound that absorbs blue light (blue light absorbing dye) between the two layers. As the blue light absorbing dye which can be used in the photothermographic material, the blue light absorbing dye immobilized during the heat development described in JP-A-60-209734 and JP-A-61-159643 is known. There is. However, the dyes described in each of these specifications are derived from the addition of the dye (presumably because the dye reacts with the oxidant of color development (coupling reaction)), and the transfer density is reduced or the transfer is reduced. There is a drawback that unevenness occurs, and there is a demand for a blue light absorbing dye for a heat-developable color light-sensitive material which is improved in these points.

[Object of the Invention]

Therefore, the object of the present invention is to solve the problems of the blue light absorbing dyes used in the above known heat developable color light-sensitive materials.

That is, an object of the present invention is to provide a heat-developable color light-sensitive material capable of obtaining a high-density transferred image.

Another object of the present invention is to provide a heat-developable color light-sensitive material having a non-light-sensitive layer (yellow filter layer) having a blue light-absorbing dye that does not undergo a coupling reaction in the heat-developable color light-sensitive material. .

Still another object of the present invention is to provide a heat-developable color light-sensitive material capable of obtaining a color image without transfer unevenness.

[Structure of Invention]

As a result of earnest research to achieve the above-mentioned objects, the present inventors have
On the support, silver halide, dye-donor,
It has a red photosensitive layer consisting of a reducing agent and a binder, a green photosensitive layer, a blue photosensitive layer, and a blue photosensitive layer as an upper layer in the exposure direction,
In a heat-developable color photosensitive material having another photosensitive layer as a lower layer and further having at least a non-photosensitive layer between the blue photosensitive layer and the other photosensitive layer, the non-photosensitive layer is represented by at least the following general formula (1). It was found to be achieved by a heat-developable color light-sensitive material characterized by containing a blue light absorbing dye.

General formula (1) In the formula, X represents an electron-withdrawing group, R ¹ represents an aryl group, R ² represents a 5- or 6-membered aromatic carbocycle or heterocycle, and at least one of R ¹ , R ² or X is The general formula (1)
The blue light absorbing dye represented by is substituted with a ballast group capable of being immobilized during thermal development.

[Specific configuration of the invention]

The blue light absorbing dye of the present invention will be described in more detail. In the general formula (1), X represents an electron withdrawing group, and preferably a cyano group or a carbamoyl group. R ¹ represents an aryl group, preferably a phenyl group,
R ² represents a 5- or 6-membered aromatic carbocycle or heterocycle (these rings may form a condensed ring with other carbocycles or heterocycles), preferably a phenyl group or a pyridyl group. Represents Further, at least one of R ¹ , R ^{2 and} X is substituted with a ballast group capable of substantially immobilizing the blue light absorbing dye represented by the general formula (1) during thermal development.

The ballast group has 8 or more carbon atoms (preferably 12 carbon atoms).
The above) organic groups and polymer residues are preferred. Also,
Hydrophilic groups (eg, sulfo groups) can also act as immobilizable ballast groups in the present invention, having 8 carbon atoms.
The blue light absorbing dye of the present invention having the above organic group and hydrophilic group is more preferable in terms of immobility, and the blue light absorbing dye of the present invention having a polymer structure having a hydrophilic group is also preferable.

When the ballast group is a polymer residue, the dye represented by the general formula (1) is a substituent on the ring represented by X, or at least one of R ¹ and R ² is an ethylenically unsaturated group. It is preferable that the polymer dye has a repeating unit derived from the dye monomer.

In the present invention, the ethylenically unsaturated group is preferably a group represented by the following general formula (2).

General formula (2) In the formula, R ₁ represents a hydrogen atom, a carboxy group or an alkyl group (for example, a methyl group, an ethyl group, etc.), and this alkyl group may have a substituent, and the substituent is, for example, a halogen atom ( For example, a fluorine atom, a chlorine atom, etc.), a carboxyl group, etc. The carboxyl group represented by R ₁ and the substituent carboxyl group may form a salt. J ₁ and J ₂ each represent a divalent linking group,
Examples of the divalent linking group include -NHCO-, -CONH
-, -COO-, -OCO-, -SCO-, -COS-, -O-,-
S -, - SO -, -, and the like - SO _2. X ₁ and X ₂ each represent a divalent hydrocarbon group, and examples of the divalent hydrocarbon group include an alkylene group, an arylene group, an aralkylene group, an alkylenearylene group or an arylenealkylene group. For example, a methylene group, an ethylene group, a propylene group, etc., an arylene group, for example, a phenylene group, etc., an aralkylene group, a phenylmethylene group, etc., and an alkylenearylene group, for example, methylenephenylene group, etc. Examples of the arylenealkylene group include a phenylenemethylene group and the like. k, l ₁ , m ₁ , l ₂ and m ₂ each represent 0 or 1.

When the dye represented by the general formula (1) of the present invention is a polymer dye, even if it is a so-called homopolymer of repeating units consisting of only one kind of pigment monomer, it is represented by the general formula (1). It may be a copolymer in which two or more kinds of the above-mentioned monomers are combined, and may be a copolymer composed of at least one other comonomer having a copolymerizable ethylenically unsaturated group.

Specific examples of the dye represented by formula (1) (in the case of a polymer dye, a dye monomer) of the present invention are shown in Table 1.

Hereinafter, specific synthesis examples of the blue light absorbing dye of the present invention will be shown.

Synthetic Example Y-3 Synthesis 6.16 g of sodium nitrite was slowly added to 40 ml of concentrated sulfuric acid, and after the addition, the mixture was heated to 70 ° C. to completely dissolve it to obtain a nitrosyl sulfuric acid solution. Separately, 280 ml of acetic acid was added to the following amine (A). 25.4 g was dissolved, the whole amount of the nitrosyl sulfuric acid solution was added to this solution at 20 ° C. or lower, and the mixture was stirred at room temperature for 30 minutes to obtain a diazonium solution. 1
-P-Sulfophenyl-3-cyano-5-pyrazolone 24
g was dissolved in water (800 ml) containing 150 g of sodium hydroxide, and the total amount of the diazonium solution was added dropwise at 20 ° C. or lower. After dropping, the mixture was stirred for 1 hour at room temperature, adjusted to pH 3.0 or lower with dilute sulfuric acid, and the precipitated yellow solid was filtered off. The yellow solid was further washed with water and cetone and dried to obtain the desired product. Yield 74% Amine (A) Table 2 shows specific examples of the polymer dye of the present invention.

The blue light absorbing dye of 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, whether it is used alone or in combination of two or more kinds. For example, the amount used is 1 m ² of the support.
0.01 g to 10 g, preferably 0.04 to 1.5 g can be used.

Examples of the dye-donor substances used in the present invention include JP-A-62-44737, JP-A-60-271117, and JP-A-61-115.
Non-diffusible dye forming couplers described in 63, for example leuco dyes described in U.S. Pat.No. 475,441,
Alternatively, for example, an azo dye used in the heat-development dye bleaching method described in U.S. Pat. No. 4,235,957 can be used as the dye-donor substance, but more preferably a diffusion-type dye-donor substance that forms or releases a diffusible dye. Is preferably used, and it is particularly preferable to use a compound which forms a diffusible dye by a coupling reaction.

Hereinafter, the diffusion type dye-providing substance that can be used in the present invention will be described. The diffusion-type dye-providing substance may be any one as long as it can participate in the reduction reaction of the photosensitive silver halide and / or the organic salt used as necessary and can form or release a diffusible dye as a function of the reaction. ,
Depending on the reaction form, a negative-working dye-donor that acts on a positive function (that is, one that forms a negative dye image when negative-working silver halide is used) and a positive working on a negative function. Type dye-donor (ie, those that form a positive dye image when a negative-working silver halide is used).

Examples of the negative dye-providing substance include, for example, U.S. Pat.
463,079, 4,439,513, JP-A-59-60434, 59
-65839, 59-71046, 59-87450, 59-887
No. 30, 59-123837, 59-124329, 59-165054
And the reducing dye-releasing compounds described in JP-A No. 59-164055 and the like.

As another negative dye-providing substance, for example, U.S. Pat.No. 4,474,867, JP-A-59-12431, 59-48765,
59-174834, 59-776642, 59-159159, 59
Examples thereof include coupling dye-releasing compounds described in No. 59-231540.

Still another particularly preferable negative dye-providing substance is a coupling dye-forming compound represented by the following general formula (3).

General formula (3) CpJB In the formula, Cp represents an organic group capable of forming a diffusible dye by reacting (coupling reaction) with an oxidant of a reducing agent, and B represents a ballast group. Here, the ballast group is
A substance that does not substantially diffuse a dye-donor substance during thermal development processing, and has a function (such as a sulfo group) depending on the nature of the molecule or a function (such as a large number of carbon atoms) having the function depending on the size. Group). 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.

The ballast group is preferably a group having 8 or more, more preferably 12 or more carbon atoms, or a sulfo group. A group including both is more 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 the monomer represented by the general formula (4) as the above group.

General formula (4) CpJY _l ZL In the formula, Cp, J has the same meaning as defined in general formula (3), Y represents an alkylene group, an arylene group or an aralkylene group, and l represents 0 or 1. , Z represents a divalent organic group, and L represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group.

Specific examples of the coupling dye-forming compound represented by the general formulas (3) and (4) include JP-A-59-124339 and JP-A-59-124339.
59-181345, 60-2950, 61-57943, 61-5
9336, U.S. Pat.Nos. 4,631,251, 4,650,748, and 4,
656,124, etc., especially US Pat.
The polymeric dye-donor materials described in 6,124, U.S. Pat. Nos. 4,631,251 and 4,650,748 are preferred.

Examples of positive type dye-donor substances include, for example, JP-A-59-
55430, dye developer compounds described in 59-165054 and the like, for example, compounds releasing a diffusible dye by an intramolecular nucleophilic reaction described in JP-A-59-154445, 59-766954 and the like, For example, cobalt complex compounds described in JP-A-59-116655 and the like, or for example, JP-A-59-124327 and JP-A-59-1524.
There are compounds described in No. 40, etc. that lose their dye releasing ability when oxidized.

The residue of the diffusible dye in the dye-donor substance used in the present invention, in order to improve the diffusibility of the dye, preferably has a molecular weight of 800 or less, more preferably 600 or less, an azo dye, Examples thereof include residues of azomethine dyes, anthraquinone dyes, naphthoquinone dyes, styryl dyes, nitro dyes, quinoline dyes, carbonyl dyes, phthalocyanine dyes, and the like. These dye residues may be in a short-wavelength form capable of restoring color during thermal development or transfer. Further, one of these dye residues is also a chelateable dye residue described in JP-A-59-48765 and JP-A-50-124337 for the purpose of improving the light resistance of an image. Is.

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, a single use or a combination use of two or more kinds, or whether the photographic constituent layer of the light-sensitive material of the present invention is a single layer or two or more kinds of multilayers. The amount used may be 0.005 to 50 g, preferably 0.1 g to 10 g per 1 m ^2.
Can be used.

The method for incorporating the dye-donor substance used in the present invention into the photographic constituent layer of the photothermographic material is arbitrary and includes, for example, a low-boiling point solvent (methanol, ethanol, ethyl acetate, etc.) or a high-boiling point solvent (dibutyl phthalate, dioctyl phthalate, tris). Cresyl phosphate, etc.) and then ultrasonically dispersed, or dissolved in an alkaline aqueous solution (eg, 10% sodium hydroxide aqueous solution) and then neutralized with an acid (eg, citric acid or nitric acid). Or an aqueous solution of a suitable polymer (eg gelatin, polyvinyl butyral, polyvinyl pyrrolidone, etc.)
It can be used after being dispersed together with a ball mill.

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. The photosensitive silver halide can be prepared by any method such as a single jet method generally used in the field of photographic technology. According to a preferred embodiment, a silver halide emulsion having silver halide grains having a shell can be used.

In the present invention, 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, core / shell type silver halide grains in which the halogen composition is changed stepwise,
Alternatively, a silver halide emulsion having continuously changing grains can be used.

The shape is a cube, sphere, octahedron, dodecahedron,
Either one having a distinctive crystal habit such as a tetradecahedron or the like may be used. Examples of this type of silver halide are those described in JP-A-60-215948.

Further, for example, JP-A-58-111933, 58-111934,
No. 58-108526, Research Disclosure 22534, etc., a grain having two parallel crystal faces, each of which has a larger area than the other single crystal of this grain. It is also possible to use a silver halide emulsion containing tabular silver halide grains 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 an internal latent image type silver halide grain whose surface is not previously fogged can be used. For internal latent image type silver halide whose surface is not previously fogged, see, for example, US Pat.
2,592,250, 3,206,313, 3,317,322, 3,51
1,622, 3,447,927, 3,761,266, 3,703,584
No. 3,736,140, etc., and an internal latent image type silver halide grain whose surface is not previously fogged, as described in each of the above specifications, is more sensitive than the surface sensitivity of the silver halide grain. It is a silver halide grain having a higher internal sensitivity. Also described in U.S. Pat.Nos. 3,271,157, 3,447,927 and 3,531,291 are silver halide emulsions having silver halide grains containing polyvalent metal ions, or U.S. Pat.No. 3,761,276. Silver halide emulsions containing weakly chemically sensitized grain surfaces of silver halide grains containing a known dopant, or JP-A-50-8524.
And silver halide emulsions comprising grains having a laminated structure described in JP-A No. 50-38525, and others.
And the silver halide emulsions described in JP-A-156614 and JP-A-55-127549.

The photosensitive silver halide emulsion may be chemically sensitized by any method in the photographic art.

The silver halide in the above light-sensitive emulsion may be coarse particles or fine particles, but the preferable grain size is about 0.001 μm to about 1.5 μm, and more preferably about 0.01 μm to about 0.01 μm. It is 0.5 μm.

In the present invention, as another method for preparing a light-sensitive material silver halide, a light-sensitive silver salt forming component may be allowed to coexist with an organic silver salt described below to form light-sensitive silver halide in a part of the organic silver salt. .

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 preferably 0.001 g to 50 g per 1 m ^{2 of the} support, and more preferably , 0.1 to 10 g.

Typical spectral sensitizing dyes used in the present invention include:
Examples include dyes such as cyanine, merocyanine, complex (that is, trinuclear or tetranuclear) cyanine, holopolar cyanine, styryl, hemicyanine, and oxonol.

The preferable addition amount of these sensitizing dyes is 1 × 10 ⁻⁴ per mol of the photosensitive silver halide or the silver halide-forming component.
Mol to 1 mol. More preferably, 1 × 10 ⁻⁴ to 1 ×
It is 10 ^-1 mol.

In the photothermographic material of the present invention, various organic silver salts can be used, if necessary, for the purpose of increasing sensitivity and improving developability.

Examples of organic silver salts that can be used in the photothermographic material of the present invention include JP-A-53-4921, JP-A-49-52626,
52-141222, 53-36224 and 53-37626,
No. 52-141222, No. 53-36224 and No. 53-37610, and U.S. Patent Nos. 3,330,633, 3,794,496, and No.
4,105,451 etc. long-chain aliphatic carboxylic acid silver salt or a heterocyclic carboxylic acid silver salt,
For example, silver laurate, silver myristate, silver palmitate, silver stearate, silver arachidonic acid, silver behenate, α
-(1-Phenyltetrazolethio) acetic acid silver, etc., and aromatic carboxylic acid silver salts such as silver benzoate, silver phthalate, etc., Japanese Patent Publication Nos. 44-26282, 45-12700 and 45-18416.
No. 45-22185, JP-A-52-137321, JP-A-58-1.
18638, 58-118639 and U.S. Pat. No. 4,123,274 are silver salts of imino groups.

Other silver complex compounds having a stability constant of 4.5 to 10.0 as described in JP-A-52-31728, U.S. Pat.
The silver salt of imizoline thione as described in JP-A No. 1994-242, etc. is used.

Of 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. Triazole and its derivatives are preferred.

The organic silver salt used in the present invention may be used alone or in combination of two or more kinds. The silver salt may be prepared in a suitable binder and used as it is without isolation, or the isolated salt may be dispersed in a binder by a suitable 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.

As a method for preparing an organic silver salt, a method of dissolving silver nitrate and a raw material organic compound in water or an organic solvent and mixing them is generally used, but a binder may be added or sodium hydroxide may be added as necessary. It is also effective to add an alkali such as to accelerate the dissolution of the organic compound, or to use an ammoniacal silver nitrate solution.

The amount of the organic silver salt used is usually preferably 0.01 to 500 mol, and more preferably 0.1 to 100 mol, per mol of the photosensitive silver halide. More preferably, it is 0.3 to 30 mol.

As the reducing agent used in the photothermographic material of the present invention (the reducing agent precursor in the present specification is also included in the reducing agent), those commonly used in the field of photothermographic materials can be used. .

Examples of the reducing agent that can be used in the present invention include U.S. Pat.Nos. 3,531,286, 3,761,270, and 3,764,
No. 328, RD (Research Disclosure) No. 12
No. 146, No. 15108, No. 15127, and JP-A-56-27132.
U.S. Pat.Nos. 3,342,599 and 3,719,492.
53-135628, 57-79035, and the like, p-phenylenediamine-based and p-aminophenol-based developing agents, phosphoroamidophenol-based, sulfonamideaniline-based developing agents, and hydrazone-based color developing agents and those Precursors, or phenols, sulfonamidephenols, or polyhydroxybenzenes, naphthols, hydroxybinaphthyls and methylenebisnaphthols, methylenebisphenols, ascorbic acid, 3-pyrazolidones, and pyrazolones can be used.

Particularly preferred reducing agents include N- (pN, N-dialkyl) phenylsulfamate salts described in JP-A-56-146133 and JP-A-61-71683.

 Two or more reducing agents may be used at the same time.

The amount of the reducing agent used in the photothermographic material of the present invention depends on the type of photosensitive silver halide used, the type of organic acid silver salt and the type of other additives, and is not always constant. However, it is usually preferably in the range of 0.01 to 1500 mol, more preferably 0.1 to 200 mol, per mol of the photosensitive silver halide.

As the binder that can be used in the photothermographic material of the present invention, polyvinyl butyral, polyvinyl acetate, ethyl cellulose, polymethyl methacrylate, cellulose acetate butyrate, polyvinyl alcohol, polyvinyl pyrrolidone, gelatin, gelatin derivatives such as phthalated gelatin, There are synthetic or natural polymer substances such as cellulose derivatives, proteins, starch, gum arabic, etc., and one or more of them can be used in combination. In particular, it is preferable to use gelatin or a derivative thereof together with a hydrophilic polymer such as polyvinylpyrrolidone or polyvinyl alcohol, and more preferably to use a mixed binder of gelatin and polyvinylpyrrolidone described in JP-A-59-229556. Is.

The binder is preferably used in an amount of 0.05 g to 50 g, and more preferably 0.1 g to 10 g per 1 m ^{2 of the} support.

The binder is 0.1 to 1 for 1 g of the dye-donor substance.
It is preferable to use 0 g, and more preferably 0.25 to 4 g.

The photothermographic material of the invention can be obtained by forming a photographic constituent layer on a support, and examples of the support that can be used here include a polyethylene film, a cellulose acetate film, a polyethylene terephthalate film, and a poly. Synthetic plastic films such as vinyl chloride, photographic base papers, printing papers, paper supports such as baryta papers and resin-coated papers, and supports obtained by coating and curing the electron beam curable resin composition on these supports. The body etc. are mentioned.

When the heat-developable photosensitive material of the present invention, and further when the photosensitive material is a transfer type and an image-receiving member is used, it is preferable to add various thermal solvents to the heat-developable photosensitive material and / or the image-receiving member. The thermal solvent is a compound that promotes thermal development and / or thermal transfer. Examples of these compounds include U.S. Pat. Nos. 3,347,675 and 3,667,959, RD (Research Disclosure) No. 17643 (XII), JP-A-59-22955.
No. 6, No. 59-68730, No. 59-84236, No. 60-191251
No. 60, No. 60-232547, No. 60-14241, No. 61-52643, etc., Japanese Patent Application No. 60-218768, No. 60-181965, No. 60-1846.
No. 37, U.S. Pat.Nos. 3,438,776, 3,666,477, 3,
667,959, JP-A-51-19525, JP-A-53-24829, JP-A-5
3-60223, 58-118640, the organic compounds having a polarity as described in 58-198038 and the like,
Particularly useful in the practice of the present invention are, for example, urea derivatives (eg, dimethylurea, diethylurea, phenylurea, etc.), amide derivatives (eg, acetamide, benzamide, p-toluamide, p-butoxybenzamide, etc.). , Sulfonamide derivatives (eg benzenesulfonamide, α-toluenesulfonamide etc.), polyhydric alcohols (eg 1,5-pentanediol, 1,6-hexanediol, 1,2-cyclohexanediol, pentaerythritol, tri- Examples include methylolethane) and polyethylene glycols.

As the hot solvent, a water-insoluble solid hot solvent is more preferably used. Here, the water-insoluble solid thermal solvent is a compound that is solid at room temperature, but becomes liquid at high temperature (60 ° C or higher, preferably 100 ° C or higher, particularly preferably 130 ° C or higher and 250 ° C or lower) Ratio of organicity (“organic conception diagram”)
Kouda Yoshio, Sankyo Publishing Co., Ltd., 1984) refers to a compound in the range of 0.5 to 3.0, preferably 0.7 to 2.5, and particularly preferably 1.0 to 2.0.

Specific examples of the water-soluble hot solvent include, for example, Japanese Patent Application No.
-278331 and 60-280824.

Examples of the layer to which the thermal solvent is added include a photosensitive silver halide emulsion layer, an intermediate layer, a protective layer, an image receiving layer of an image receiving member, and the like, and the layers are added so that the effect can be obtained depending on each layer.

The preferable addition amount of the hot solvent is usually 10% by weight to 500% by weight, more preferably 30% by weight to 200% by weight of the binder amount.

The photothermographic material of the invention may contain various additives in addition to the above components, if necessary.

What is known as a toning agent in the photothermographic material may be added to the photothermographic material of the invention as a development accelerator. As the color tone adjusting agent, for example, JP-A-46-4928 is used.
No. 46, No. 46-6077, No. 49-5019, No. 50-2524, No. 50
-67132, 50-67641, 50-114217, 52-33
No. 722, No. 52-99813, No. 53-1020, No. 53-55115
No. 53-76020, No. 53-125014, No. 54-156523
No. 54-1565324, No. 54-156525, No. 54-156526
No. 55-4060, No. 55-4061, No. 55-32015, etc. and West German Patent Nos. 2,140,406, 2,141,063, and No.
2,220,618, U.S. Patents 3,847,612, 3,782,941
No. 4,201,582, etc., and JP-A-57-207244
No. 57, No. 57-207245, No. 58-1896328, No. 58-193541.
There are compounds described in the publication.

Other development accelerators include JP-A-59-177550 and 59-177550.
The compound described in -111636 is mentioned. Japanese Patent Application Sho 59
The development accelerator releasing compounds described in -280881 can also be used.

Examples of the antifoggant include U.S. Pat. No. 3,645,739.
Higher fatty acids described in JP-B No. 47-11113, mercuric salts described in JP-B No. 47-11113, N-halogen compounds described in JP-A No. 51-47419, US Pat. No. 3,700,457, and JP-A No. 51-507.
No. 25, mercapto compound-releasing compounds, 49-12
Aryl sulfonic acids described in 5016, lithium carboxylic acid salts described in 51-47419, British Patent No. 1,455,271
No. 53-19825, oxidizers described in JP-A No. 50-101019.
The sulfinic acids or thiolauryls,
51-81124, disulfide and polysulfide compounds described in 55-93149, rosin or diterpenes described in 51-57435, and free carboxyl groups or sulfonic acid groups described in 51-104338 Polymeric acid, thiazoline thione described in U.S. Pat.No. 4,138,265, 1,54,518, 1,2,4-triazole or 5-mercapto 1,2,4-described in U.S. Pat.
Triazole, 1,2,3,4-described in JP-A-55-142331
Thiatriazoles, 59-46641, 59-57233,
No. 59-57234 dihalogen compounds or trihalogen compounds, further 59-111636 thiol compounds, 60-198540 hydroquinone derivatives, 60-227255 hydroquinone derivatives and benzo described. Combination use with a triazole derivative and the like can be mentioned.

As other particularly preferable antifoggants, inhibitors having a hydrophilic group described in Japanese Patent Application No. 60-218169, polymer inhibitors described in Japanese Patent Application No. 60-262177, and Japanese Patent Application No. The inhibitor compounds having a ballast group described in 60-263564 can be mentioned.

In addition, inorganic or organic bases or chlorine based precursors can be added. Examples of the base precursor include a compound that releases a basic substance by heating to decarbonize (eg, guanidinium trichloroacetate), a compound that decomposes by a reaction such as an intramolecular nucleophilic substitution reaction, and releases an amine, For example, JP-A-56-130745,
No. 56-132332, British Patent No. 2,079,480, U.S. Patent No.
4,060,420, JP-A-59-157637, 59-166943,
Examples thereof include base releasing agents described in Nos. 59-180537, 59-174830, and 59-195237.

In addition, various additives used in the photothermographic material as required, for example, antihalation dyes, fluorescent brighteners, hardeners, antistatic agents, plasticizers, extenders, matting agents,
Surfactants, anti-fading agents, etc.
(Research Disclosure), Vol. 170, June 1978, No. 17029, Japanese Patent Application No. 60-276615.

In the heat-developable color light-sensitive material of the present invention, basically, in one light-sensitive layer, (1) light-sensitive silver halide,
It contains (2) a reducing agent, (3) a dye-providing substance, (4) a binder, and optionally (5) an organic silver salt, and has at least three photosensitive layers, each of which is blue-sensitive. , Green sensitivity and red sensitivity are spectrally sensitized. Then, a layer containing the blue light absorbing dye of the present invention is provided between the blue-sensitive layer and the green-sensitive layer or between the blue-sensitive layer and the red-sensitive layer.

Furthermore, the arrangement of the blue-sensitive layer, the layer containing the blue-light absorbing dye, and the other photosensitive layers (green-sensitive layer and red-sensitive layer) are such that the blue-sensitive layer and the blue-light absorbing layer are seen from the light intrusion side during exposure. It is composed of a dye-containing layer and other light-sensitive layers (the green-sensitive layer and the red-sensitive layer may be in any order). Here, each of the above-mentioned photosensitive layers does not necessarily need to contain the above-mentioned components (1) to (5) in a single photographic constituent layer. For example, the photosensitive layer is divided into two layers, and the above-mentioned (1)
The components (2), (4), and (5) are contained in the photosensitive layer on one side, and the dye-donor (3) is contained in the layer on the other side adjacent to the photosensitive layer. If possible, it may be contained separately in two or more photographic constituent layers.

The photothermographic material of the present invention is usually preferably used after imagewise exposure.
In the temperature range of 80 ° C to 200 ° C, more preferably 100 ° C to 170 ° C, preferably 1 second to 180 seconds, more preferably 1.5.
It is developed only by heating for ~ 120 seconds. The transfer of the diffusible dye to the image-receiving layer may be carried out simultaneously with the heat-development by bringing the image-receiving member into close contact with the photosensitive surface of the photosensitive material and the image-receiving layer during the heat-development. Alternatively, the transfer may be performed by closely contacting after supplying water and further heating if necessary. Further, pre-heating may be performed in a temperature range of 70 ° C. to 180 ° C. before exposure.
Further, as described in JP-A-60-143338 and Japanese Patent Application No. 60-3644, in order to enhance mutual adhesion, the photosensitive material and the image-receiving member are heated at 80 ° C to 250 ° C immediately before heat development transfer. You may preheat at each temperature.

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

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

When the present invention is a transfer type photothermographic material, the image receiving member is provided as described above. In that case, the image-receiving layer of the image-receiving member effectively used may have a function of receiving the dye in the photothermographic layer which is released or formed by thermal development, for example, a tertiary amine or a quaternary ammonium salt. Polymers containing, those described in US Pat. No. 3,709,690 are preferably used. A typical image-receiving layer for diffusion transfer can be 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. Other useful dye receiving substances include those formed of heat-resistant organic polymer substances 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 a support as an image receiving layer, or may be used as a support itself.

Examples of the heat-resistant polymer, polystyrene,
A polystyrene derivative having a substituent having 4 or less carbon atoms,
Polyacetals such as polyvinylcyclohexane, polydivinylbenzene, polyvinylpyrrolidone, polyvinylcarbazole, polyallylbenzene, polyvinylalcohol, polyvinylformal and polyvinylbutyral, polyvinyl chloride, chlorinated polyethylene, polytrifluoroethylene, polyacrylonitrile, poly- N, N-
Dimethylallylamide, polyacrylate having p-cyanophenyl group, pentachlorophenyl group and 2,4-dichlorophenyl group, polyacrylchloroacrylate,
Polymethylmethacrylate, polyethylmethacrylate, polypropylmethacrylate, polyisopropylmethacrylate, polyisobutylmethacrylate, poly-
Polyesters such as tert-butyl methacrylate, polycyclohexyl methacrylate, polyethylene glycol dimethacrylate, poly-2-cyano-ethyl methacrylate and polyethylene terephthalate, polycarbonates such as polysulfone and bisphenol A polycarbonate, polyanhydrides, polyamides and cellulose acetates. Is mentioned. Also, "Polymer Handbook, Second Edition" (Edited by Joy Brand Wrap, EH Inmargat) John Willi & Sons Publishing {Polymer Handbook 2
nd ed. (J. Brandrup, EHImmergut) John Wiley & S
ons} having a glass transition temperature of 540 ° C. or higher are also useful. Generally, 2,000 to 200,000 is useful as the molecular weight of the polymer substance. These polymeric substances may be used alone or as a mixture of two or more kinds, or may be used as a copolymer by combining two or more kinds.

Particularly preferred image-receiving layers are layers made of polyvinyl chloride described in JP-A-59-223425 and JP-A-60-19138.
And a layer comprising a polycarbonate and a plasticizer described in the above publication.

These polymers can be used as an image receiving layer (image receiving member) which also serves as a support. 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, any support such as a transparent support or an opaque support may be used, but examples thereof include films such as polyethylene terephthalate, polycarbonate, polystyrene, polyvinyl chloride, polyethylene and polypropylene, and supports thereof. Supports containing pigments such as oxygen titanium, barium sulfate, calcium carbonate, talc, baryta paper, RC paper laminated with a thermoplastic resin containing pigment on paper, cloth, glass, aluminum, etc. And the like, and a support obtained by coating and curing an electron beam curable resin structure product containing a pigment on these supports, and a coating layer containing a pigment provided on these supports. A support etc. are mentioned. Further, the cast coated paper described in Japanese Patent Application No. 61-216972 is also useful as a support.

Further, an electron beam curable resin composition containing a pigment is coated on a paper and cured, or a pigment coating layer is provided on the paper, and the electron beam curable resin composition is formed on the pigment coating layer. Since the resin layer can be used as an image receiving layer by itself, the support coated with and cured can be used as it is as an image receiving member.

The photothermographic material of the present invention includes RD (Research Disclosure) No. 15108, JP-A Nos. 57-198458 and 57-207.
It can be a so-called monotone type photothermographic material in which the light-sensitive layer and the image-receiving layer are provided on the same support, as described in JP-A Nos. 250 and 61-80148.

The photothermographic material of the present invention is preferably provided with a protective layer.

Various additives used in the field of photography can be used in the protective layer. As the additive, various matting agents,
Colloidal silica, sliding agent, organic fluoro compound (especially fluorine-based surfactant), antistatic agent, ultraviolet absorber, high boiling organic solvent, antioxidant, hydroquinone derivative, polymer latex, surfactant (polymer surfactant) Agents), hardeners (including polymer hardeners), organic silver salt particles, non-photosensitive silver halide particles, and the like.

Regarding these additives, RD (Research Disclosure Magazine) Vol.170, June 1978 No.17029, Japanese Patent Application No.
No. 60-276615.

〔Example〕

Examples of the present invention will be shown below, but the embodiments of the present invention are not limited thereto.

Example-1 <Preparation of silver iodobromide emulsion> At 50 ° C., 20 g of ossein gelatin, 1000 ml of distilled water and ammonia were dissolved using a mixing stirrer disclosed in JP-A-57-92523 and 57-92524. Solution (A) was mixed with 500 ml of an aqueous solution containing 11.6 g of potassium iodide and 131 g of potassium bromide and 500 ml of an aqueous solution containing 1 mol of silver nitrate and ammonia at the same time. The pAg was added while keeping it constant. The shape and size of the emulsion particles to be prepared
It was adjusted by controlling the pH, pAg, and the addition rates of solutions B and C. In this way, the silver iodide content is 7 mol% and the positive 8
A core emulsion having a facer and an average particle size of 0.25 μm was prepared.

Then, in the same manner as described above, the shell of silver halide having a silver iodide content of 1 mol% was destroyed to prepare a regular octahedron core / shell type silver halide emulsion having an average grain size of 0.3 μm. . (The variation coefficient of the particle size distribution was 9%.) The emulsion thus prepared was washed with water and desalted. The emulsion yield was 800 ml.

Further, using the above-prepared silver halide emulsion, spectral sensitization and the like were performed as described below to prepare red-sensitive, green-sensitive and blue-sensitive photosensitive silver halide emulsions.

a) Preparation of red-sensitive silver iodobromide emulsion 700 ml of the above silver halide emulsion 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 0.4 g gelatin 32 g sodium thiosulfate 10 mg The following sensitizing dye (a ) Methanol 1% solution 80 ml Distilled water 1200 ml Sensitizing dye (a) b) Preparation of green-sensitive silver iodobromide emulsion 700 ml of the above silver halide emulsion 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 0.4 g gelatin 32 g sodium thiosulfate 10 mg The following sensitizing dye (b) ) Methanol 1% solution 80 ml Distilled water 1200 ml Sensitizing dye (b) c) Preparation of blue-sensitive silver iodobromide emulsion 700 ml of the above silver halide 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 0.4 g Gelatin 32 g Sodium thiosulfate 10 mg Sensitizing dye (c) below Methanol 1% solution 80 ml Distilled water 1200 ml Sensitizing dye (c) <Organic Silver Salt Dispersion> 2-Methylbenzotriazole silver (28.8 g) obtained by reacting 5-methylbenzotriazole and silver nitrate in a water-alcohol mixed solvent, poly (N-vinylpyrrolidone) 16.0 g, and 4 1.33 g of sulfobenzotriazole sodium salt was dispersed in an alumina ball mill to adjust the pH to 5.5 to 200 ml.

<Dye-providing substance dispersion> 122 g of the following dye-providing substance A, 5.0 g of 2,4-di (t) octylhydroquinone and 1.0 g of the following antifoggant were added to ethyl acetate.
Dissolved in 300 ml, alkanol XC (manufactured by DuPont) 248 ml of 5% by weight aqueous solution, photographic gelatin 26.4 g and phenylcarbamoylated gelatin (Russlaw type 17819PC) 34.
After mixing with 1440 ml of an aqueous gelatin solution containing 6 g and dispersing with an ultrasonic homogenizer, the ethyl acetate was distilled off, and the pH was adjusted to 5.
It was 5 to 1590 ml.

Dye donating substance A Antifoggant <Preparation of reducing agent solution> Water was added to 22.3 g of the following reducing agent (a), 10.5 g of the following reducing agent (b), and 1.0 g of the following surfactant to dissolve them, and the pH was adjusted to 7.0 with an aqueous citric acid solution, Make up to 150 ml of solution.

Reducing agent (a) Reducing agent (b) Surfactant <Preparation of hot solvent dispersion> 430 g of p-toluamide and polyvinylpyrrolidone 1.
1410 ml of 0 wt% aqueous solution was dispersed by a ball mill to obtain a hot solvent dispersion.

<Preparation of Coating Solution for Layer Containing Blue Light Absorption Dye of the Present Invention> Gelatin 20 wt% aqueous solution 10 ml Polyvinylpyrrolidone 20 wt% aqueous solution 7.5 ml Organic silver salt dispersion 46 ml Hot solvent dispersion 20 ml H-1 4 ml The following blue light absorption dye dispersion Liquid 25.5 ml (H-1) Tetra (vinylsulfonylmethyl) methane and taurine were reacted at a molar ratio of 1: 0.75, and this reaction product was added to a 1.0% by weight aqueous solution of phenylcarbamoylated gelatin to obtain 30% by weight of the reaction product. Hardener liquid designed to be.

The above solution and dispersion were mixed to prepare a coating solution for a blue light absorbing dye-containing layer of the present invention.

Blue light absorbing dye dispersion Blue light absorbing dye Y-1 2.0 g was dissolved in 1N sodium hydroxide aqueous solution 3.0 ml and water 14.0 ml to prepare photographic gelatin 10w.
Add t% aqueous solution, and then add 20% sodium di (2-ethylhexyl) -2-sulfosuccinate aqueous solution 0.1 ml, add 5% citric acid until pH becomes 6.0 while stirring well, and further add 30 ml water. Finished.

<Preparation of Photothermographic Material> The following coating solution was applied onto a transparent photographic polyester terephthalate film having a thickness of 180 μm and having a subbing layer at a wet film thickness of 65 μm and dried to form a first photosensitive layer.

(Coating liquid composition) Organic silver salt dispersion liquid 64 ml Red-sensitive silver halide emulsion liquid 30.7 ml Reducing agent liquid 38.4 ml Hot solvent dispersion liquid 94.8 ml Dye donor dispersion liquid 101 ml Photographic gelatin 10 wt% aqueous solution 27.7 ml Citric acid aqueous solution (pH 5 .5) and water 89 ml H-1 13.3 ml total 459.9 ml A first intermediate layer having the following composition was coated on the first photosensitive layer.

The following dye-providing material a dye providing material of the first photosensitive layer on a gelatin 0.6 g / m ² Polyvinyl pyrrolidone 0.3 g / m ² methylbenzotriazole silver 0.6 g / m ² p-toluamide 1.0 g / m ² first intermediate layer B (the addition amount is an equimolar amount to the dye-donor substance in the first photosensitive layer), and the silver halide was changed to green-sensitive silver halide.
The second photosensitive layer was formed by coating with a thickness of 45 μm.

Dye donating substance B On the second photosensitive layer, a coating solution having a composition of the first intermediate layer and an exemplary blue light absorbing dye YP-1 (addition amount 0.4 g / m ² ) was applied at a wet film thickness of 22 μm A layer (second intermediate layer) containing the blue light absorbing dye of the invention was applied.

Further, on the second intermediate layer, the dye-donor substance of the first photosensitive layer is changed to the following dye-donor substance C (the addition amount is an equimolar amount to the dye-donor substance of the first photosensitive layer), and the silver halide is blue-sensitive halogenated. A coating solution having the same composition as that of the first photosensitive layer except that the silver was changed to a wet film thickness of 75 μm was applied to form a third photosensitive layer.

Dye donating substance C Further, a protective layer having the following composition was coated on the third photosensitive layer to obtain a multilayer photosensitive material (Sample No. 1).

Gelatin 0.28g / m ² Polyvinylpyrrolidone 0.14g / m ² SiO ₂ 0.36g / m ² Saffron (Asahi Glass Co., Ltd., fluorine-based surfactant)
Table blue light absorbing dye of 05G / m ² p-toluamide 0.42 g / m ² second intermediate layer of the multilayer photosensitive material -
Multilayer photosensitive materials (Sample Nos. 2 to 10) were prepared in the same manner as Sample No. 1 except that the dyes shown in 3 were used.

<Preparation of image receiving member> Polyethylene (Mw 25,000, L-1250 Teijin Chemicals) in ethylene chloride solution was used for photographic baryta paper (thickness 170
μm, weight 190 g / m ² ) and dried, and then the following image receiving layer coating solution was applied and dried at a wet film thickness of 137.2 μm to prepare an image receiving element.

Image-receiving element coating liquid Polyvinyl chloride (n = 1: 100 manufactured by Wako Kayaku) 21.0 g UV absorber below 0.8 g Tetrahydrofuran 190 ml UV absorber <Evaluation of Photosensitive Material> The photosensitive material obtained by the above method was subjected to 800 CMS blue exposure and green exposure through a step wedge.

Then, the polycarbonate coated surface of the image receiving member and the photosensitive layer surface of the exposed photosensitive material are overlaid at 150 ° C.
After 90 seconds of thermal development, the transfer densities (Dmax and Dmin) of the yellow and magenta dyes were measured with blue light and green light, respectively. Further, the unevenness of the obtained image was visually evaluated. The results are shown in Table-3.

As shown in Table 3, it is a surprising effect that the transfer image does not become uneven due to the addition of the blue light absorbing dye. Furthermore, it can be seen that the density decrease due to the dye is small.

〔The invention's effect〕

The heat-developable color light-sensitive material having a multilayer structure in which the blue light absorbing dye of the present invention is used for the blue light absorbing filter layer has improved density unevenness of the transferred color image and does not cause density decrease by the dye.

Claims (1)

[Claims] 1. A red light-sensitive layer comprising a silver halide, a dye-donor, a reducing agent and a binder on a support, respectively.
It has a green photosensitive layer and a blue photosensitive layer, and has a blue photosensitive layer as an upper layer and another photosensitive layer as a lower layer in the direction of exposure, and a non-photosensitive layer between the blue photosensitive layer and the other photosensitive layer. A heat-developable color light-sensitive material having at least the blue-light absorbing dye represented by the following general formula (1) in the non-light-sensitive layer. General formula (1) [In the formula, X represents an electron-withdrawing group, R ¹ represents an aryl group, R ² represents a 5- or 6-membered aromatic carbocycle or heterocycle, and at least one of R ¹ , R ^{2 and} X. One is substituted with a ballast group capable of immobilizing the blue light absorbing dye represented by the general formula (1) during thermal development. ]