JPH0862807A - Heat developable color photosensitive material - Google Patents

Abstract

PURPOSE: To provide a heat developable color photosensitive material made difficult to generate the ununiformity of coating film thickness and prevented from causing the unevenness of image density. CONSTITUTION: The heat developable color photosensitive material contains a photosensitive silver halide, a binder and a compound capable of supplying a dyestuff on a paper supporting body, the total coating quantity of the binder is <=5g/m<2> and in the producing method, one or the combination of following (1)-(4) is applied. (1) The total coating quantity at the time of coating is <=80cc/m<2> . (2) The viscosity of a coating solution for at least one layer is >=80cp (centi poise) to <=200cp at 40 deg.C. (3) The gelatin concn. of the coating solution for at least one layer containing the photosensitive silver halide is >=2.0%. (4) A natural high molecular polysaccharide originating in red algae is contained in at least one layer.

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, and more particularly to a heat-development color light-sensitive material having less uneven image density.

[0002]

2. Description of the Related Art Photothermographic materials are well known in the art, and the photothermographic material and its process are described, for example, in "Basics of Photographic Engineering", Non-silver salt photograph edition (1982, published by Corona Publishing Co., Ltd.), pages 242 to 255. Page, US Patent No. 450062
No. 6, etc.

In addition, for example, a method of forming a dye image by a coupling reaction between an oxidized product of a developing agent and a coupler is described in US Pat. Nos. 3,761,270 and 4,021,240. Further, a method of forming a positive color image by a photosensitive silver dye bleaching method is described in US Pat. No. 4,235,957.

Recently, there has been proposed a method of releasing or forming a diffusible dye imagewise by heat development and transferring the diffusible dye to a dye fixing element. In this method, a negative dye image or a positive dye image can be obtained by changing the kind of dye-donor compound used or the kind of silver halide used. More specifically, U.S. Pat. Nos. 4,500,626, 4,483,914 and 45,
03137, 4559290 and JP-A-58-14.
9046, JP-A-60-133449, 59-2.
No. 18443, No. 61-238056, European Patent Publication 220746A2, Open Technical Report 87-6199, European Patent Publication 210660A2, and the like. [Problems of the Prior Art] A photosensitive material using a paper support is P
Compared with a light-sensitive material using a support using a synthetic polymer such as ET, it has the advantages that it is more disposable and less expensive. In a heat-developable color light-sensitive material using a paper support, one problem is to reduce uneven density in an image. The density in this image is considered to be due to the nonuniformity of the coating thickness due to the unevenness of the support surface. Therefore, the use of a highly smooth PET support or the like often solves the problem. In Japanese Patent Laid-Open No. 3-296736, a water-soluble polymer is used in a method of coating an image receiving material to prevent unevenness in the thickness of a coating layer called leveling. Among them, natural high molecular polysaccharides derived from red algae such as kappa carrageenan have been studied, but introduction into a light-sensitive material has not been studied. Furthermore, JP-A-6
No. -118590 discloses a technique of combining kappa carrageenan and a potassium inorganic salt, but this has not been examined for a light-sensitive material. On the other hand, JP-A-3-
Nos. 242646 and 4-3055 disclose a technique of increasing image density by using a natural high molecular polysaccharide derived from red algae in a positive type photothermographic material, but using a paper support. There has been no discussion about uneven density when doing. Further, in Japanese Patent Application No. 5-127327, the total amount of the binder in the photothermographic material is 5 g / m ² or less to increase the dye transfer rate and the development rate to increase the maximum density and to increase the maximum density. The minimum concentration is lowered (whiteness is good) by making the total amount of the binder contained in the non-photosensitive layer coated farther from the support than the coated photosensitive layer to be 1 g / m ² or more. The technology is disclosed. However, in the production of a light-sensitive material in which the total amount of binder is 5 g / m ² or less, particularly when the photosensitive material has 6 or more layers, unevenness of the coating thickness due to the unevenness of the support is likely to occur. The reason is considered to be that leveling is likely to occur mainly because the concentration of the binder such as gelatin in the layer (emulsion layer) containing the photosensitive silver halide is low and the settability is poor. It will be described later in Japanese Patent Application No. 6-81139.
Although the dye-donating compound represented by (1) is disclosed, it has been known until now that the density unevenness is more likely to be worsened when this compound is used than when a conventional dye-donating compound is used. There wasn't.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to improve image density unevenness in a photothermographic material coated on a paper support with a total binder amount of 5 g / m ² or less.

[0006]

The object is to have at least a photosensitive silver halide, a binder and a dye-donating compound on a paper support, and the total binder coating amount is 5 g / m ² or less. A heat-developable color light-sensitive material characterized by the following (1) to
This is achieved by a photothermographic material characterized by employing any one or combination of (4). (1) The total coating amount during coating is 80 cc / m ² or less. (2) The viscosity of at least one layer coating liquid is 80 cp at 40 ° C.
(Centipoise) or more and 200 cp or less. (3) The gelatin concentration of the coating solution for at least one layer containing photosensitive silver halide is 2.0% or more. (4) At least one layer contains a natural polymeric polysaccharide derived from red algae. Further, the present invention is achieved by the above-mentioned photothermographic material characterized by containing a compound represented by the following general formula (1) as a dye-donating compound. General formula (1)

[0007]

[Chemical 3]

In the formula, Dye represents a dye group or dye precursor group represented by the following general formula (2), and Y corresponds to reduction of a photosensitive silver halide having an imagewise latent image to silver. Represents a group having a property of causing a difference in diffusibility of dye components, X represents a simple bond or a linking group, p represents a natural number of 1 or more, q represents 1 or 2, and p is 2 or more or q is 2 or less. Or Dye or (Dye) _p −
All Xs may be the same or different. General formula (2)

[0009]

[Chemical 4]

In the formula, R ¹ and R ² are hydrogen atom, halogen atom, hydroxyl group, cyano group, nitro group, carboxyl group, substituted or unsubstituted alkyl group, aralkyl group, cycloalkyl group, aryl group, heterocyclic group, An alkoxy group,
Aryloxy group, amino group, acylamino group, sulfonylamino group, acyl group, sulfonyl group, carbamoyl group, sulfamoyl group, ureido group, alkylthio group,
It represents a substituent selected from an arylthio group. R ³
R ^1, excluding hydrogen atoms as defined by R ² others R ¹ is
Synonymous with R ² . n represents an integer of 0 to 5, and n is 2
In the case of ~ 5, R ³ may be the same or different.

The compound represented by the general formula (1) which can be used in the present invention will be described in more detail below.

First, X will be described. X is a bond or a linking group, and when X is a linking group, an alkylene group, a substituted alkylene group, an arylene group, a substituted arylene group, a heterocyclic group, -O-, -SO _2- , -CO- , -NR ¹⁴ -
(R ¹⁴ represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group) and a group formed by combining two or more of these.

Preferred linking groups are -NR ¹⁴ SO _2- , -NR
^{14 CO -, - O-, -SO} 2 - and, also these with a substituted or unsubstituted alkylene group (e.g. methylene, ethylene, propylene, etc.), an arylene group (e.g. o- phenylene,
m-phenylene, p-phenylene, 1,4-naphthylene and the like).

When X has a substituent, preferred groups are an alkyl group and an aralkyl group (an optionally substituted alkyl group and aralkyl group. For example, methyl group, trifluoromethyl group, benzyl group, chloromethyl group, dimethyl group. Aminomethyl group, ethoxycarbonylmethyl group, aminomethyl group, acetylaminomethyl group, ethyl group, carboxyethyl group, allyl group, 3,3,3-trichloropropyl group, n-propyl group, iso-propyl group, n- Butyl group, iso-butyl group, sec-butyl group, t-butyl group, n-benzyl group, sec-pentyl group, t-pentyl group, cyclopentyl group, n-hexyl group, sec-
Hexyl group, t-hexyl group, cyclohexyl group, n-
Octyl group, sec-octyl group, t-octyl group, n
-Decyl group, n-undecyl group, n-dodecyl group, n-
Tetradecyl group, n-pentadecyl group, n-hexadecyl group, sec-hexadecyl group, t-hexadecyl group,
n-octadecyl group, t-octadecyl group, etc.),

Alkenyl group (Alkenyl group which may be substituted. For example, vinyl group, 2-chlorovinyl group, 1-methylvinyl group, 2-cyanovinyl group, cyclohexene-
1-yl group, etc.), alkynyl group (optionally substituted alkynyl group, for example, ethynyl group, 1-propynyl group, 2-ethoxycarbonylethynyl group, etc.),

Aryl group (aryl group which may be substituted. For example, phenyl group, naphthyl group, 3-hydroxyphenyl group, 3-chlorophenyl group, 4-acetylaminophenyl group, 2-methanesulfonyl-4-nitrophenyl group. , 3-nitrophenyl group, 4-methoxyphenyl group, 4-acetylaminophenyl group, 4-methanesulfonylphenyl group, 2,4-dimethylphenyl group, etc.),

Heterocyclic group (heterocyclic group which may be substituted. For example, 1-imidazolyl group, 2-furyl group, 2-
Pyridyl group, 5-nitro-2-pyridyl group, 3-pyridyl group, 3,5-dicyano-2-pyridyl group, 5-tetrazolyl group, 5-phenyl-1-tetrazolyl group, 2-benzthiazolyl group, 2-benz Imidazolyl group, 2-benzoxazolyl group, 2-oxazolin-2-yl group,
Moriholino group, etc.),

Acyl group (acyl group which may be substituted; for example, acetyl group, propionyl group, butyroyl group, i
so-butyroyl group, 2,2-dimethylpropionyl group, benzoyl group, 3,4-dichlorobenzoyl group, 3
-Acetylamino-4-methoxybenzoyl group, 4-methylbenzoyl group, 4-methoxy-3-sulfobenzoyl group, etc.),

Sulfonyl group (a sulfonyl group which may be substituted. For example, methanesulfonyl group, ethanesulfonyl group, chloromethanesulfonyl group, propanesulfonyl group, butanesulfonyl group, benzenesulfonyl group, 4-
Toluenesulfonyl group, etc.),

Carbamoyl group (optionally substituted carbamoyl group, for example, carbamoyl group, methylcarbamoyl group, dimethylcarbamoyl group, bis- (2-methoxyethyl) carbamoyl group, dimethylcarbamoyl group, cyclohexylcarbamoyl group, etc.),

Sulfamoyl group (sulfamoyl group which may be substituted. For example, sulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group, diethylsulfamoyl group, bis- (2-methoxyethyl) sulfamoyl group, di- n-butylsulfamoyl group, 3-ethoxypropylmethylsulfamoyl group, N-phenyl-N-methylsulfamoyl group, etc.),

An alkoxy or aryloxycarbonyl group (alkoxy or aryloxycarbonyl group which may be substituted, for example, methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, 2-methoxyethoxycarbonyl group, etc.),

An alkoxy or aryloxysulfonyl group (alkoxy or aryloxysulfonyl group which may be substituted, for example, methoxysulfonyl group, ethoxysulfonyl group, phenoxysulfonyl group, 2-methoxyethoxysulfonyl group, etc.),

Alkoxy or aryloxy group (optionally substituted alkoxy or aryloxy group.
For example, methoxy group, ethoxy group, methoxyethoxy group, 2-chloroethoxy group, phenoxy group, p-methoxyphenoxy group, etc.),

An alkylthio or arylthio group (an optionally substituted alkylthio group or arylthio group, for example, methylthio, ethylthio, n-butylthio, phenylthio, 4-chlorophenylthio, 2-methoxyphenylthio, etc.),

Amino group (optionally substituted amino group, for example, amino group, methylamino group, N, N-dimethoxyethoxyamino group, methylphenylamino group, etc.),

Ammonio group (ammonio group which may be substituted, for example, ammonio group, trimethylammonio group, phenyldimethylammonio group, dimethylbenzylammonio group, etc.),

Acylamino group (acylamino group which may be substituted, for example, acetylamino group, 2-carboxybenzoylamino group, 3-nitrobenzoylamino group, 3-diethylaminopropanoylamino group, acryloylamino group, etc.),

Acyloxy group (acyloxy group which may be substituted, for example, acetoxy group, benzoyloxy group, 2-butenoyloxy group, 2-methylpropanoyloxy group, etc.),

Sulfonylamino group (a sulfonylamino group which may be substituted. For example, methanesulfonylamino group, benzenesulfonylamino group, 2-methoxy-5- group.
n-methylbenzenesulfonylamino group, etc.),

Alkoxycarbonylamino group (alkoxycarbonylamino group which may be substituted. For example, methoxycarbonylamino group, 2-methoxyethoxycarbonylamino group, iso-butoxycarbonylamino group,
Benzyloxycarbonylamino group, t-butoxycarbonylamino group, 2-cyanoethoxycarbonylamino group, etc.),

An aryloxycarbonylamino group (an optionally substituted aryloxycarbonylamino group, for example, a phenoxycarbonylamino group, a 2,4-nitrophenoxycarbonylamino group, etc.),

Alkoxycarbonyloxy group (alkoxycarbonyloxy group which may be substituted. For example, methoxycarbonyloxy group, t-butoxycarbonyloxy group, 2-benzenesulfonylethoxycarbonyloxy group, benzylcarbonyloxy group, etc.),

Aryloxycarbonyloxy group (an optionally substituted aryloxycarbonyloxy group. For example, phenoxycarbonyloxy group, 3-cyanophenoxycarbonyloxy group, 4-acetoxyphenoxycarbonyloxy group, 4-t-butoxycarbonylamino group. Phenoxycarbonyloxy group, etc.),

Aminocarbonylamino group (Aminocarbonylamino group which may be substituted. For example, methylaminocarbonylamino group, morpholinocarbonylamino group,
N-ethyl-N-phenylaminocarbonylamino group,
4-methanesulfonylaminocarbonylamino group),

An aminocarbonyloxy group (an optionally substituted aminocarbonyloxy group, for example, a dimethylaminocarbonyloxy group, a pyrrolidinocarbonyloxy group, a 4-dipropylaminophenylaminocarbonyloxy group, etc.),

Aminosulfonylamino group (optionally substituted aminosulfonylamino group. For example, diethylaminosulfonylamino group, di-n-butylaminosulfonylamino group, phenylaminosulfonylamino group, etc.),

A sulfonyloxy group (an optionally substituted sulfonyloxy group, for example, a phenylsulfonyloxy group, a methanesulfonyloxy group, a chloromethanesulfonyloxy group, a 4-chlorophenylsulfonyloxy group, etc.),

Further, a carboxyl group, a sulfo group, a cyano group, a nitro group, a hydroxyl group, a halogen atom and the like can be mentioned.

Among these, more preferable groups include an alkoxy group, an amino group, a sulfamoyl group, a sulfonylamino group, a carboxyl group, a sulfo group and a halogen atom.

The Y will be described in more detail below. The expression was described including X. (1) Examples of Y include a negative-acting releaser that releases a photographically useful group in response to development.

A releaser group that releases a photographically useful group from an oxidant is known as Y which is classified as a negative acting releaser. The following formula (Y-1) is mentioned as a preferable example of Y of this type. (Y-1)

[0043]

[Chemical 5]

In the formula, β represents a group of non-metal atoms necessary for forming a benzene ring, and this benzene ring may be condensed with a saturated or unsaturated carbocycle or heterocycle. α-
Represents -OZ ² or -NHZ ³ , wherein Z ² represents a hydrogen atom or a group capable of generating a hydroxyl group by hydrolysis, Z ³ represents a hydrogen atom, an alkyl group, an aryl group, or an amino group by hydrolysis. Represents a group that causes Z ¹ is an alkyl group which may have a substituent, an aryl group, an aralkyl group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, an acyl group, a sulfonyl group,
Acylamino group, sulfonylamino group, carbamoyl group, sulfamoyl group, ureido group, urethane group, heterocyclic group or cyano group, represents a halogen atom, a represents a positive integer, and when Z ¹ is 2 or more, all the same. It may or may not be. Z ⁴ is a group for formula (Y-1) -G is represented by -NHSO ₂ Z ⁴ represents a divalent group.

Among the groups contained in (Y-1), preferable groups include (Y-2) and (Y-3). (Y-2)

[0046]

[Chemical 6]

(Y-3)

[0048]

[Chemical 7]

In the formula, Z ² and G have the same meanings as described in (Y-1). Z ⁵ and Z ⁶ represent an alkyl group, an aryl group or an aralkyl group, and these may have a substituent. Furthermore Z
⁵ is a secondary or tertiary alkyl group, Z ⁵ and Z ⁶
It is preferable that the sum of the number of carbon atoms is 20 to 50.

Specific examples of these are shown in US Pat. No. 4,055,4.
28, 4,336,322, JP-A-51-113.
No. 624, No. 56-16131, No. 56-71061
No. 56, No. 56-71060, No. 56-71072, No. 56-73057, No. 57-650, and No. 57-40.
No. 43, No. 59-60, 439, Japanese Patent Publication No. 56-176
56 and 60-25780.

Another example of Y is (Y-4). (Y-4)

[0052]

Embedded image

In the formula, α, G, Z ¹ and a have the same meanings as described in (Y-1). β'represents a group of non-metal atoms necessary for forming a benzene ring, and this benzene ring may be condensed with a saturated or unsaturated carbocycle or heterocycle.

Of the groups represented by (Y-4), α is -OZ
^{It is 2} that β ′ forms a naphthalene skeleton. Specifically, US Pat. No. 3,928,312
No. 4,135,929.

Further, as a releaser releasing a photographically useful group by a reaction similar to (Y-1) and (Y-2), JP-A Nos. 51-104343, 53-46730 and 54
-130122, 57-85055, 53-3
No. 819, No. 54-48534, No. 49-64436.
No. 57-20735, JP-B-48-32129
No. 48-39165, U.S. Pat. No. 3,443,93.
The groups described in No. 4 are mentioned.

The compound releasing the photographically useful group from the oxidant by another reaction mechanism is represented by the formula (Y-5) or (Y-
Examples include hydroquinone derivatives represented by 6). (Y-5)

[0057]

[Chemical 9]

(Y-6)

[0059]

[Chemical 10]

In the formula, β'is the formula (Y-4) and Z ² is the formula (Y-).
1), and Z ⁷ is the same as Z ² .
Z ⁸ represents a substituent described in Z ¹ or a hydrogen atom. Z ²
And Z ⁷ may be the same or different. Specific examples of this type are described in US Pat. No. 3,725,062.

The hydroquinone derivative releaser of this type having a nucleophilic group in the molecule is also included. Specifically, it is described in JP-A-4-97347.

Another example of Y is US Pat. No. 3,44.
P-hydroxydiphenylamine derivatives described in U.S. Pat. No. 3,939, U.S. Pat. No. 3,844,785, U.S. Pat. D. The hydrazine derivative described in No. 128, page 22 may be mentioned.

Further, the negative acting releaser includes the following formula (Y-7). (Y-7)

[0064]

[Chemical 11]

In the formula, Coup represents a group capable of coupling with an oxidized product of p-phenylenediamines and p-aminophenols, that is, a group known as a photographic coupler. Specific examples are described in British Patent 1,330,524. Next, specific compound examples of the present invention will be shown, but the present invention is not limited thereto.

[0066]

[Chemical 12]

[0067]

[Chemical 13]

[0068]

Embedded image

[0069]

[Chemical 15]

[0070]

Embedded image

[0071]

[Chemical 17]

[0072]

[Chemical 18]

[0073]

[Chemical 19]

[0074]

Embedded image

Specific synthesis examples of these compounds are described in Japanese Patent Application Nos. 5-9811 and 5-109794.

In the present invention, the compound represented by the general formula (1) is preferably added to the same layer as the layer containing silver halide. In the present invention, the above compounds can be used in a wide range of amounts and are used in an amount of 0.01 to 5 mol, preferably 0.05 to 1 mol, based on 1 mol of silver.

[0077] is the total amount of the binder in the photosensitive layer side on the support to the total amount of the binder in the heat-developable color light-sensitive material of the present invention, which in the present invention is 5 g / m ² or less, in particular 1 g / m ² to 5
g / m ² .

Next, the production methods (1) to (4) of the present invention will be described in detail. The improvement of the density unevenness, which is the object of the present invention, is basically carried out by reducing the variation in coating thickness due to the unevenness of the paper support.

It has been found for the first time by the present inventor that in the photothermographic material, when the total coating amount at the time of coating is large, the fluctuation amount is large and the density unevenness is worsened, and when the coating amount is reduced, the density unevenness is improved. However, if the coating amount is too small, it becomes difficult to coat multiple layers. Therefore, the preferable range of the total coating amount during coating is 30 cc / m ² or more and 80 cc / m ² or less, and more preferably 50 cc / m ² or more and 70 cc / m ² or less. Still more preferably 50 cc / m ² or more 60 cc / m ² or less.

Among the variations in the coating thickness, what is called leveling (a phenomenon in which the coating liquid on the convex portion on the support moves in the concave portion and the coating thickness in the concave portion becomes thinner than that in the convex portion) is
It can be reduced by increasing the viscosity of the coating liquid and improving the setting property. Increasing the viscosity of all layers is preferred, but some layers are also effective. It is considered that this is because the leveling of the entire coating liquid is less likely to occur due to the decrease in the fluidity of some layers. In the case of the photothermographic material of the present invention, the coating amount of the binder (especially gelatin) in the intermediate layer and the protective layer is large, and the concentration of the coating solution for the layer is relatively high (4% to 15%).
%) It can be done easily. Of course, it is also possible to increase the viscosity by a method of increasing the viscosity by increasing the addition amount of a water-soluble polymer called a usual thickener or by combining with a method of increasing the binder concentration of the coating liquid.

Further, since the photosensitive layer (emulsion layer) containing a silver halide emulsion has a relatively small binder coating amount, it is necessary to concentrate the coating liquid and increase the thickener. Increasing the viscosity of any layer has the effect of improving the density unevenness, but increasing the viscosity of the emulsion layer is more effective.

Generally, if the viscosity is too high, the operation of the coating solution becomes difficult, so that the preferable viscosity range is 80 cp or more and 200 cp at 40 ° C.
It is the following. Further, the uppermost layer (the layer farthest from the support) and the lowermost layer (the layer closest to the support) may lower the viscosity for the purpose of improving coatability. Therefore, it is more preferable that the viscosity of as many layers as possible, excluding the lowermost layer and the uppermost layer, is most preferably 80 cp or more.
It should be set to cp or less.

The viscosity of the coating solution can be measured by using a commercially available B type viscometer. For example, B manufactured by Tokyo Keiki Co., Ltd.
Viscometer model BL, BL adapter 0.1, rotor N
Viscosity of 100 cp or less can be measured at o.1 and 60 rpm. The measurement is performed by setting the temperature of the coating liquid to 40 ° C.

The binder coating amount of the layer containing photosensitive silver halide has an important meaning. That is, the amount of binder,
In general, a large amount of gelatin hinders the diffusibility of the dye or delays the reaction between the silver halide and the reducing agent. On the other hand, if the amount is too small, the stability of the silver halide emulsion or the dispersion of the dye-donor compound may be deteriorated or the Dmin may be increased. In general, the amount of the binder coated in the layer containing photosensitive silver halide is small, so that the setability is poor as compared with the intermediate layer.

In the present invention, by increasing the concentration of the coating liquid, the coating amount is reduced, the wet coating amount is reduced, or the setting property is improved to improve the density unevenness. Specifically, gelatin concentration is 2.0% or more, preferably 2.5%
As described above, more preferably 3.0% or more improves the density unevenness. The upper limit of gelatin concentration is 1
It is 5% or less.

When the natural high molecular polysaccharide derived from red algae is contained, the settability after coating is improved and the uneven density is improved. In this case, the effect may be remarkable if an inorganic salt such as potassium ion is added.

Examples of natural high molecular polysaccharides derived from red algae used in the present invention include "Food Industry", Vol. 31, (1988),
The natural polymeric polysaccharides obtained by extraction and purification from red algae listed in Table 1 on page 21 can be mentioned. Natural high molecular polysaccharides obtained by extraction and purification from red algae are often various mixtures. In the present invention, this mixture can be used as it is, or can be used as a simpler substance having higher purity. Among the natural macromolecular polysaccharides derived from red algae used in the present invention, those which are particularly passed through the present invention are agar, kappa carrageenan, lambda carrageenan, iota carrageenan, farceleran and the like. These substances are
It is also available as a commercial product. For example, copper carrageenan is available as Taito gelling agent NK-4 manufactured by Taito Co., Ltd., and a mixture of lambda carrageenan and a trace amount of copper carrageenan is available as Taito gelling agent MV manufactured by Taito Corporation. The amount of the naturally-occurring high molecular weight polysaccharide derived from red alga of the present invention can be arbitrarily set, but 0.0005 to ² g / m ² per 1 m ^{2 of} the support, particularly about 0.002 to 1 g / m ² is suitable. is there. The layer containing the natural macromolecular polysaccharide derived from red alga of the present invention may be a layer containing a photosensitive silver halide or a layer containing a diffusible dye-donating compound (the same layer as silver halide may be used. ), A protective layer, an intermediate layer provided between photosensitive layers having different color sensitivities, an undercoat layer, a back layer and the like. These high molecular polysaccharides can be used in combination with various other hydrophilic binders. Specifically, transparent or translucent hydrophilic binders are preferable, for example, gelatin, proteins or cellulose derivatives such as gelatin derivatives, starch, gum arabic, dextran, natural compounds such as polysaccharides such as pullulan, polyvinyl alcohol, Examples include polyvinylpyrrolidone, acrylamide polymer, polyacrylic acid, polyacrylate, and other synthetic high molecular compounds. Further, superabsorbent polymers described in JP-A No. 62-245260, that is, homopolymers of vinyl monomers having --COOM or --SO ₃ M (M is hydrogen atom or alkali metal), or vinyl monomers themselves or others A copolymer of vinyl monomer with (for example, sodium methacrylate,
Ammonium methacrylate, Sumika Gel L-5H manufactured by Sumitomo Chemical Co., Ltd.) is also used. These binders are 2
It is also possible to use a combination of two or more species. Further, it can be used in combination with gums such as roast bean gum, tara gum and guar gum which are natural compounds.

The heat-developable color light-sensitive material of the present invention basically has a photosensitive silver halide, a binder, a reducing agent, and a dye-donating compound on a support, and further, if necessary, an organic metal. A hydrochloric acid agent and the like can be included. These components are often added to the same layer, but if they are in a reactive state, they can be divided and added to separate layers. For example, when a colored dye-donor compound is present in the lower layer of the silver halide emulsion, the reduction in sensitivity can be prevented. The reducing agent is preferably incorporated in the photothermographic material, but it may be supplied from the outside by, for example, a method of diffusing from a dye fixing material described later.

In order to obtain a wide range of colors in the chromaticity diagram by using the three primary colors of yellow, magenta, and cyan, at least three layers of silver halide emulsions having light sensitivity in different spectral regions are combined. To use. In the present invention, a combination of three layers of a blue sensitive layer, a green sensitive layer and a red sensitive layer is adopted. Each of the light-sensitive layers can take various arrangement orders known in a conventional type color light-sensitive material. Further, each of these photosensitive layers may be divided into two or more layers if necessary.

Particularly, it is generally used. A light-sensitive layer containing a yellow dye-donor compound has a wavelength of 400
nm-500 nm spectrally sensitized halogenated emulsion (blue-sensitive emulsion), and the photosensitive layer containing a magenta dye-donating compound is spectrally sensitized in the range of 500 nm-600 nm. Similarly, a light-sensitive emulsion containing a cyan dye-donor compound is used in an amount of 600 nm to 740 nm.
This is a method of incorporating a halogenated emulsion (red-sensitive emulsion) spectrally sensitized to nm. Further, in this case, since the yellow photosensitive layer is colored yellow, it is preferable that the uppermost photosensitive layer is separated from the support.

That is, from the support, a cyan dye-donating compound-containing red-sensitive layer, an intermediate layer, a magenta dye-donating compound-containing green-sensitive layer, an intermediate layer, a yellow dye-donating compound-containing blue-sensitive layer, an intermediate layer and a protective layer. Is a union. The cyan layer and the magenta layer have the same characteristics, even if they are reversed. In addition, each photosensitive layer,
It is composed of two layers, each of which may contain a dye-donor compound and a halogenated emulsion. Alternatively, only the upper layer may contain the halogenated emulsion and the lower layer may contain the dye-donor compound to improve the sensitivity. It is also possible.

The heat-developable color light-sensitive material can be provided with various auxiliary layers such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer, an antihalation layer and a back layer. When the support is polyethylene laminated paper containing a white pigment such as titanium oxide, the back layer must have an antistatic function and be designed to have a surface resistivity of 10 ¹² Ω · cm or less. .

The silver halide emulsion of the present invention in the heat-developable color light-sensitive material of the present invention will be described in detail below.

The silver halide emulsion comprises silver chloride, silver bromide,
Any of silver iodobromide, silver chlorobromide, silver chloroiodide and silver chloroiodobromide may be used. The silver halide emulsion may be a surface latent image type emulsion or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or an optical fogging. Further, a so-called core-shell emulsion having different phases inside the grain and the surface layer of the grain may be used, or silver halides having different compositions may be joined by epitaxial joining. The silver halide emulsion may be monodisperse or polydisperse, and are disclosed in JP-A-1-167,743 and 4-
As described in No. 223,463, a method of mixing a monodisperse emulsion and adjusting the gradation is preferably used. The particle size is preferably 0.1 to 2 μm, particularly preferably 0.2 to 1.5 μm.
The crystal habit of silver halide grains is one having a regular crystal such as a cube, octahedron, or tetrahedron, a sphere, an irregular crystal system such as a flat plate having a high aspect ratio, or a twin plane. Any of those having such twinning defects, a composite system thereof, or the like may be used. Specifically, U.S. Pat. No. 4,500,626, column 50, U.S. Pat. No. 4,628,021.
, Research Disclosure (RD) No. 17,029 (1978), No. 17,
643 (December 1978), pages 22-23, ibid. No. 1
8,716 (November 1979), p.648, ibid. No. 3
07, 105 (November 1989) 863-865,
JP-A-62-253,159 and 64-13,546.
No. 2, JP-A-2-236546, and JP-A-3-110,55.
No. 5, and "Graphide's Physics and Chemistry", published by Paul Monte (P.Glafkides, Chemie et Phisique Phot
Ographique, Paul Montel, 1967), "Photographic emulsion chemistry" by Duffin, published by Focal Press (GFDuffin, Pho
tographic Emulsion Chemistry, Focal Press, 196
6), "Production and Coating of Photographic Emulsions" by Zelikmann et al., Published by Focal Press (VLZelikman et al., Making and C
oating Photographic Emulsion, Focal Press, 196
Any of the silver halide emulsions prepared by the method described in 4) or the like can be used.

In the process of preparing the light-sensitive silver halide emulsion of the present invention, it is preferable to carry out so-called desalting to remove excess salt. As a means for this, a Nudel water washing method in which gelatin is gelled may be used, and inorganic salts (for example, sodium sulfate) composed of polyvalent anions, anionic surfactants, anionic polymers (for example, polystyrene sulfonic acid). The precipitation method using sodium) or a gelatin derivative (eg, aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.) may be used. The sedimentation method is preferably used.

The photosensitive silver halide emulsion used in the present invention may contain heavy metals such as iridium, rhodium, platinum, cadmium, zinc, thallium, lead, iron and osmium for various purposes. These compounds may be used alone or in combination of two or more kinds. The addition amount depends on the purpose of use, but is generally about 10 ^-9 to 10 ^-3 mol per mol of silver halide. When it is contained, it may be uniformly added to the particles, or may be localized inside or on the surface of the particles. Specifically, the emulsions described in JP-A-2-236542, JP-A-1-116637, and JP-A-4-126629 are preferably used.

The amount of iridium used in the present invention is preferably 10 ^-9 to 10 ^-4 mol, and more preferably 10 ^-8 to 10 ^-6 mol, per mol of silver halide. In the case of core-shell emulsion, iridium may be added to the core and / or shell. As the compound, K ₂ IrC
I ₆ and K ₃ IrCl ₆ are preferably used.

The addition amount of rhodium used in the present invention is preferably 10 ^-9 to 10 ^-6 mol per mol of silver halide.

The addition amount of iron used in the present invention is preferably 10 ^-7 to 10 ^-3 mol, and more preferably 10 ^-6 to 10 ^-3 mol, per mol of silver halide.

A part or all of these heavy metals is previously doped in a fine grain emulsion of silver chloride, silver chlorobromide, silver bromide, silver iodobromide, etc., and then this fine grain emulsion is added to halogenate A method of locally doping the surface of the silver emulsion is also preferably used.

In the step of forming grains of the light-sensitive silver halide emulsion of the present invention, rhodan salt, ammonia, 4-substituted thioether compound or JP-B No. 47-1 is used as a silver halide solvent.
The organic thioether derivatives described in 1,386 or the sulfur-containing compounds described in JP-A-53-144,319 can be used.

For other conditions, see Graphide, "Physics and Chemistry of Photography," published by Paul Monte (P.Glaf).
kides, Chemie et Phisique Photographique, Paul Mon
Tel, 1697), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photographic Emulsion C
hemistry, Focal Press, 1966), "Manufacturing and coating of photographic emulsions" by Zelikmann et al., published by Focal Press (V.
L. Zelikman et al., Making and Coating Photographic
Emulsion, Focal Press, 1964) and the like may be referred to. That is, any of an acidic method, a neutral method and an ammonia method may be used, and as a method of reacting a soluble silver salt and a soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. In order to obtain a monodisperse emulsion, a simultaneous mixing method is preferably used. A reverse mixing method in which grains are formed in the presence of excess silver ions can also be used. As one type of double jet method, the pAg in the liquid phase where silver halide is produced is kept constant,
The so-called controlled double jet method can also be used.

Further, in order to accelerate the grain growth, the addition concentration, the addition amount and the addition rate of the silver salt and the halogen salt to be added may be increased (JP-A-55-142,329 and JP-A-55-158). 124, U.S. Pat. No. 3,650,757). Further, the stirring method of the reaction liquid may be any known stirring method. Further, the temperature and pH of the reaction solution during the formation of silver halide grains may be set arbitrarily according to the purpose. The preferred pH range is 2.2 to 8.5, more preferably 2.5 to 7.5.

The photosensitive silver halide emulsion is usually a chemically sensitized silver halide emulsion. For the chemical sensitization of the photosensitive silver halide emulsion of the present invention, a chalcogen sensitizing method such as a sulfur sensitizing method, a selenium sensitizing method, a tellurium sensitizing method, or the like, which is known in emulsions for conventional light-sensitive materials, gold, platinum, A noble metal sensitization method using palladium or the like and a reduction sensitization method can be used alone or in combination (for example, JP-A-3-110,55).
No. 5, Japanese Patent Application No. 4-75,798, etc.). These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-253,159). Further, an antifoggant described below can be added after the completion of the chemical sensitization. Specifically, JP-A-5-45,833 and JP-A-62-4
The method described in No. 0,446 can be used. . The pH during the chemical sensitization is preferably 5.3 to 10.5, more preferably 5.5 to 8.5, and the pAg is preferably 6.
It is 0 to 10.5, and more preferably 6.8 to 9.0.
The coating amount of the photosensitive silver halide emulsion used in the present invention is in the range of 1 mg / m ² to 10 g / m ^{2 in} terms of silver.

In order to provide the photosensitive silver halide used in the present invention with green-sensitive, red-sensitive and infrared-sensitive color sensitivities, the photosensitive silver halide emulsion is spectrally sensitized with a methine dye or the like. . Further, if necessary, the blue-sensitive emulsion may be spectrally sensitized in the blue region. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Specifically, US Pat.
617,257, JP-A-59-180,550, JP-A-64-13,546, JP-A-5-45,828 and JP-A-5-45,834. These sensitizing dyes may be used alone, or a combination thereof may be used, and the combination of sensitizing dyes is often used particularly for the purpose of wavelength adjustment of supersensitization or spectral sensitization. . Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a compound that does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. 615, 641 and those described in JP-A-63-23, 145). These sensitizing dyes may be added to the emulsion at the time of chemical ripening or before or after the chemical ripening, or according to U.S. Pat. Nos. 4,183,756 and 4,225,666 before and after the nucleation of silver halide grains. Good. These sensitizing dyes and supersensitizers may be added as a solution of an organic solvent such as methanol, a dispersion of gelatin or a solution of a surfactant. The addition amount is generally 10 ^-8 to 10 per mol of silver halide.
^-It is about ² mol.

Additives used in such steps and known photographic additives usable in the photothermographic material and dye fixing material of the present invention are described in RD No. 17,643,
It is described in No. 18,716 and No. 307,105, and the corresponding parts are summarized in the table below. Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer, page 23, page 648, right column, page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, page 23 to 24, page 648, right column 866 to 868, strong Color sensitizers-p. 649, right column 4. Fluorescent brighteners, p. 24, 648 pages, right column, 868 pages, 5. Fog prevention, 24-25 pages, 649, right column, 868-870 pages, stabilizers, 6. light absorbers, 25 Page 26 Page 649 Right column Page 873 Filter ~ Page 650 Left column Dye, UV absorber 7. Dye image page 25 650 Page left column 872 Stabilizer 8. Hardener page 26 651 Left column 874-875 page 9. Binder, page 26, page 651, left column, pages 873 to 874, 10. Plasticizer, page 27, page 650, right column, page 876, lubricant 11. Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876, surfactant 12 . Static page 27 page 650 page right column 876-877 page inhibitor 13. Matt agent 878-879 page

A hydrophilic binder is preferably used as the binder of the constituent layers of the photothermographic material and the dye fixing material. Examples thereof include Research Disclosure mentioned above and pages (71) to (75) of JP-A-64-13,546.
The thing described in the page is mentioned. Specifically, a transparent or translucent hydrophilic binder is preferable, and for example, gelatin, proteins such as gelatin derivatives or cellulose derivatives, starch, gum arabic, dextran, natural compounds such as polysaccharides such as pullulan, and polyvinyl alcohol,
Examples thereof include synthetic polymer compounds such as polyvinylpyrrolidone and acrylamide polymers. Also, U.S. Pat. No. 4,96
No. 0,681, JP-A No. 62-245,260 and the like, a superabsorbent polymer, that is, -COOM or -SO
Homopolymers of vinyl monomers having ₃ M (M is a hydrogen atom or an alkali metal) or copolymers of these vinyl monomers or copolymers with other vinyl monomers (for example, sodium methacrylate, ammonium methacrylate,
Sumika Gel L-5H manufactured by Sumitomo Chemical Co., Ltd. is also used. These binders can be used in combination of two or more. A combination of gelatin and the above binder is particularly preferable. The gelatin may be selected from lime-processed gelatin, acid-processed gelatin and so-called demineralized gelatin having a reduced content of calcium etc. according to various purposes, and it is also preferable to use them in combination.

When a system in which a small amount of water is supplied for thermal development is adopted, it is possible to quickly absorb water by using the above superabsorbent polymer. Also, the use of superabsorbent polymers in the dye-fixing layer or its protective layer can prevent the dye from retransferring from the dye-fixing element to another after transfer. In the present invention, the coating amount of the binder is preferably 20 g or less, more preferably 10 g or less, and further preferably 7 g to 0.5 g per 1 m ² .

In the present invention, an organic metal salt may be used as an oxidizing agent together with the photosensitive silver halide emulsion. Among such organic metal salts, organic silver salts are particularly preferably used. Organic compounds that can be used to form the above organic silver salt oxidizing agents include those described in US Pat.
There are benzotriazoles, fatty acids and other compounds described in Nos. 00,626, columns 52 to 53. The acetylene silver described in U.S. Pat. No. 4,775,613 is also useful. Two or more kinds of organic silver salts may be used in combination. The above organic silver salt is 0.01 mol per mol of photosensitive silver halide.
-10 mol, preferably 0.01-1 mol can be used in combination. Total coating amount of light-sensitive silver halide emulsion and the organic silver salt is 0.05 to 10 g / m ² in terms of silver, and preferably from 0.1-4 g / m ^2.

As the reducing agent used in the present invention, those known in the field of photothermographic materials can be used. Further, a dye-donor compound having a reducing property described later is also included (in this case, other reducing agents can be used together). Further, a reducing agent precursor which has no reducing property itself but exhibits reducing property by the action of a nucleophile or heat during the development process can also be used. Examples of reducing agents used in the present invention include US Pat. No. 4,500,626.
No. 49-50, No. 4,839,272, No. 4,
330,617, 4,590,152, 5,0
17,454, 5,139,919, JP-A-60
-140,335, pages (17)-(18), ibid. 57.
-40,245, 56-138,736, 59
-178,458, 59-53,831, 59
-182,449, 59-182,450, 6
0-119,555, 60-128,436, 60-128,439, 60-198,540,
No. 60-181, 742, No. 61-259, 253.
No. 62-201, 434, and No. 62-244, 04.
No. 4, 62-131, 253, 62-131, 62
No. 56, No. 63-10, 151, No. 64-13, 54
No. 6, pages (40) to (57), JP-A-1-120,5
No. 53, No. 2-32, 338, No. 2-35, 451
No. 2-234, 158, 3-160, 443
And EP-A-220,746, pages 78 to 96, and the like. Combinations of various reducing agents such as those disclosed in US Pat. No. 3,039,869 can also be used.

When a diffusion resistant reducing agent is used, if necessary, an electron transfer agent and / or an electron transfer agent may be added in order to promote electron transfer between the diffusion resistant reducing agent and the developable silver halide.
Alternatively, electron transfer agent precursors can be used in combination. Particularly preferably, said US Pat. No. 5,139,
919, European Patent Publication No. 418,743, JP-A-1
Those described in Nos. -138,556 and 3-102,345 are used. Further, a method of stably introducing into a layer as described in JP-A-2-230,143 and JP-A-2-235,044 is preferably used. The electron transfer agent or its precursor can be selected from the above-mentioned reducing agent or its precursor. It is desirable that the mobility of the electron transfer agent or its precursor is higher than that of the diffusion-resistant reducing agent (electron donor). Particularly useful electron transfer agents are 1-phenyl-3-pyrazolidones or aminophenols. The diffusion-resistant reducing agent (electron donor) used in combination with the electron transfer agent may be one that does not substantially move in the layer of the light-sensitive material among the reducing agents described above, and preferably hydroquinone, Sulfonamide phenols, sulfonamide naphthols, JP-A-53-
110827, U.S. Pat. Nos. 5,032,487, 5,026,634, and 4,839,272, and compounds described as electron donors, and a diffusion-resistant and reducing dye described later. Donor compounds and the like can be mentioned. Further, an electron donor precursor as described in JP-A-3-160,443 is also preferably used. Further, the reducing agent can be used in the intermediate layer and the protective layer for various purposes such as prevention of color mixture, improvement of color reproduction, improvement of white background, and prevention of silver transfer to dye fixing material. Specifically, European Patent Publication No. 52
4,649, 357,040, Japanese Patent Laid-Open No. 4-24
No. 9,245, No. 2-64,633, No. 2-46,4
No. 50 and the reducing agents described in JP-A No. 63-186,240 are preferably used. In addition, Japanese Examined Patent Publication No. 3-63,733,
JP-A-1-150,135, 2-110,557
Development inhibitor releasing reducing compounds such as those described in JP-A Nos. 2-64,634, 3-43,735 and EP-A-451,833 can also be used. In the present invention, the total amount of the reducing agent added is 0.01 to 20 mol per mol of silver,
It is particularly preferably 0.1 to 10 mol.

In the present invention, when a silver ion is reduced to silver under a high temperature condition, a compound that produces or releases a mobile dye in response to this reaction or in the opposite reaction, that is, a dye-donor is provided. A sex compound is used. Examples of the dye-donating compound that can be used in the present invention include a compound (coupler) that forms a dye by an oxidative coupling reaction. The coupler may be a 4-equivalent coupler or a 2-equivalent coupler. A 2-equivalent coupler having a diffusion resistant group as a leaving group and forming a diffusible dye by an oxidative coupling reaction is also preferable. The diffusion resistant group may form a polymer chain. Specific examples of color developers and couplers can be found in "The Theory of th" by TH James.
e Photographic Process "Fourth Edition, pages 291-334 and 354-361, RD-307, 105, 871.
Page, JP-A-58-123,533, 58-149,
046, 58-149, 047, 59-11.
1,148, 59-124,399, 59-1
74,835, 59-231,539, 59-
231, 540, 60-2, 950, 60-
No. 2,951, No. 60-14, 242, No. 60-2
3, 474, 60-66, 249 and the like.

As another example of the dye-donating compound,
Examples thereof include compounds having a function of releasing or diffusing a diffusible dye in an image form. This type of compound can be represented by the following general formula [LI]. ((Dye) _m -Y) _n -Z [LI] Dye represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a simple bond or linking group, and Z represents an image-like structure. To produce a difference in the diffusivity of the compound represented by ((Dye) m -Y) n -Z corresponding to or opposite to the photosensitive silver salt having a latent image, or (Dye) m
-Y is released, and the released (Dye) m-Y and ((Dy) m-Y
e) m-Y) n-Z represents a group having a property of causing a difference in diffusibility, m represents an integer of 1 to 5, n represents 1 or 2, and m and n Either one
If not, the plurality of Dyes may be the same or different. Specific examples of the dye donating compound represented by the general formula [LI] include the following compounds (1) to (3). In addition, the following items (1) to (5) are for forming a diffusible dye image (positive dye image) in reverse correspondence to the development of silver halide, and is the diffusible dye image (positive dye image) corresponding to the development of silver halide ( To form a negative dye image).

US Pat. Nos. 3,134,764, 3,362,819, 3,597,200, 3,544,545, 3,482,972 and Japanese Patent Publication No. 3-68. No. 387, etc., a dye developer in which a hydroquinone-based developer and a dye component are linked. This dye developing agent is diffusible in an alkaline environment, but becomes non-diffusible when it reacts with silver halide. As described in U.S. Pat. No. 4,503,137, a non-diffusible compound which releases a diffusible dye in an alkaline environment but loses its ability when reacted with silver halide can also be used. An example is U.S. Pat. No. 3,983.
Compounds releasing a diffusible dye by an intramolecular nucleophilic substitution reaction described in US Pat. No. 4,199,
Compounds that release a diffusible dye by the intramolecular rewinding reaction of the isoxazolone ring described in JP-A No. 354 and the like.

US Pat. No. 4,559,290, European Patent 220,746A2, US Pat. No. 4,783.
No. 396, Open Technical Report 87-6, 199, JP-A-64-1
As described in JP-A-3,546, a non-diffusible compound which itself releases a diffusible dye by reacting with a reducing agent left unoxidized by development can also be used. Examples thereof include US Pat. Nos. 4,139,389 and 4,139,
379, JP-A-59-185, 333 and 57-8.
Compounds that release a diffusible dye by a nucleophilic substitution reaction in the molecule after being reduced, as described in 4,453, etc.,
U.S. Pat. No. 4,232,107, JP-A-59-10
1,649, 61-88,257, RD24,0
25 (1984), which releases a diffusible dye by an intramolecular electron transfer reaction after reduction, West German Patent No. 3,008,588A, JP-A-56-
142,530, U.S. Pat. No. 4,343,893,
Compounds that cleave a single bond after reduction to release a diffusible dye described in U.S. Pat. No. 4,619,884, and diffusibility after electron acceptance described in U.S. Pat. No. 4,450,223. Examples thereof include a nitro compound that releases a dye and a compound that releases a diffusible dye after electron acceptance as described in US Pat. No. 4,609,610.

Further, as more preferable ones, European Patent No. 220,746, Open Technical Report 87-6,199, US Pat. No. 4,783,396, JP-A-63-201,6
No. 53, No. 63-201, 654, No. 64-13, 5
No. 46, etc., a compound having an N—X bond (X represents an oxygen, sulfur or nitrogen atom) and an electron-withdrawing group in one molecule, one molecule described in JP-A-1-26,842. A compound having SO ₂ -X (where X is as defined above) and an electron-withdrawing group within the molecule, and a PO-X bond (where X is as defined above) within one molecule described in JP-A-63-271344. And a compound having an electron-withdrawing group, JP-A-63-271341
The compound having a C—X ′ bond (X ′ has the same meaning as X or represents —SO ₂ —) and an electron-withdrawing group in one molecule described in No. In addition, JP-A-1-161,237
Compounds described in JP-A No. 1-161, 342, which release a diffusible dye by cleavage of a single bond after reduction by a π bond conjugated with an electron-accepting group. Among these, a compound having an N—X bond and an electron-withdrawing group in one molecule is particularly preferable. A specific example is European Patent 220,746.
Or the compounds (1) to (3), (7) to (10), (12), (13), (15), (2) described in U.S. Pat. No. 4,783,396.
3) to (26), (31), (32), (35), (36), (40), (41), (4
4), (53) to (59), (64), (70), Technical Report 87-6, 19
Compounds (11) to (23) described in item 9, JP-A-64-13,
Compounds (1) to (84) described in No. 546 and the like.

A coupler having a diffusible dye as a leaving group, which is a non-diffusible compound itself (DDR coupler) which releases a diffusible dye by a reaction with an oxidant of a reducing agent. Specifically, British Patent No. 1,330,524, Japanese Patent Publication No. 48-
39,165, U.S. Pat. Nos. 3,443,940, 4,474,867, and 4,483,914. Reducible to silver halide or organic silver salt,
It itself is a non-diffusible compound (DRR compound) that releases a diffusible dye when it reduces the other party. Typical examples thereof are U.S. Pat. Nos. 3,928,312, 4,053,312, 4,055,428, 4,336,322, and JP-A-56-65,839. 59-69,839, 53-3,819, 51-104,343, RD
17,465, U.S. Pat. Nos. 3,725,062, 3,728,113, 3,443,939, JP-A-58-116,537, 57-179,840.
And U.S. Pat. No. 4,500,626. Specific examples of the DRR compound include the compounds described in the above-mentioned U.S. Pat. No. 4,500,626, columns 22 to 44. Among them, the compounds (1) to (3), (10) to (13), (16) to (19), (2
8) to (30), (33) to (35), (38) to (40), and (42) to (64) are preferable. Also, U.S. Pat. No. 4,639,408, Nos. 37-3
The compounds described in column 9 are also useful. In addition, as a dye-donating compound other than the above-mentioned coupler and the general formula [LI], a dye silver compound in which an organic silver salt and a dye are bound (Research Disclosure, May 1978, 54-5)
8), azo dyes used in the heat-development silver bleaching method (U.S. Pat. No. 4,235,957, Research Disclosure, 1976, No. 4, pages 30-32, etc.), leuco dyes (U.S. Pat. No. 3,985,565,
No. 4,022,617, etc.) can also be used. In the present invention, this DRR compound is particularly preferably used.

Hydrophobic additives such as dye-donor compounds and diffusion resistant reducing agents can be incorporated into the layer of the photothermographic material by known methods such as the method described in US Pat. No. 2,322,027. it can. In this case, US Pat.
55,470, 4,536,466, 4,53
No. 6,467, No. 4,587, 206, No. 4,55
No. 5,476, No. 4,599,296, Japanese Examined Patent Publication 3-6
A high-boiling point organic solvent such as that described in No. 2,256 can be used in combination with a low-boiling point organic solvent having a boiling point of 50 ° C. to 160 ° C., if necessary. In addition, two or more kinds of these dye donating compounds, diffusion resistant reducing agents, high boiling point organic solvents and the like can be used in combination. The amount of the high boiling point organic solvent is 10 g or less, preferably 5 g or less, and more preferably 1 g to 0.1 g, relative to 1 g of the dye-donor compound used. Also, 1 cc or less per 1 g of binder, further 0.5 cc
Below, 0.3 cc or less is particularly suitable. See also
-39,853 and JP-A-51-59,943, dispersion methods using polymers and JP-A-62-30,2.
The method of adding a fine particle dispersion described in No. 42 etc. can also be used. In the case of a compound which is substantially insoluble in water, fine particles can be dispersed and contained in a binder in addition to the above method. When dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, Japanese Unexamined Patent Publication No. 59-157,636 (3)
The surfactants described in Research Disclosure, pages 7 to 38 can be used. In the photothermographic material of the present invention, a compound capable of activating development and stabilizing an image at the same time can be used. The specific compounds preferably used are described in US Pat. No. 4,500,626, columns 51 to 52.

In a system for forming an image by diffusion transfer of a dye, for the purpose of improving the white background of the obtained image by immobilizing or colorless the unnecessary dye or coloring matter in the constituent layers of the photothermographic material of the present invention. Various compounds can be added. Specifically, European Published Patent No. 353,741
No. 461,416, JP-A-63-163,345.
No. 62-203,158 can be used.

Various pigments and dyes can be used in the constituent layers of the photothermographic material of the present invention for the purpose of improving color separation and increasing sensitivity. Specifically, the compounds described in Research Disclosure and European Published Patent No. 479,1
67, 502,508, JP-A-1-167,83.
No. 8, No. 4-343, 355, No. 2-168, 252
No. 6, JP-A-61-20,943, European Published Patent No. 47
The compounds and layer constitutions described in No. 9,167, No. 502,508 and the like can be used.

In a system for forming an image by diffusion transfer of a dye, a dye fixing material is used together with a photothermographic material. The dye fixing material may be applied separately on a support different from the photosensitive material, or may be applied on the same support as the photosensitive material. Regarding the relationship between the light-sensitive material and the dye fixing material, the relationship with the support, and the relationship with the white reflective layer, the relationship described in column 57 of US Pat. No. 4,500,626 can be applied to the present invention. The dye fixing material preferably used in the present invention has at least one layer containing a mordant and a binder. As the mordant, those known in the photographic field can be used, and specific examples thereof include US Pat. No. 4,500,626, columns 58 to 59, and JP-A-61-161.
88, 256, pages (32) to (41) and JP-A-1-1.
No. 61,236, mordanting agents described on pages (4) to (7), U.S. Pat. Nos. 4,774,162 and 4,619,883.
Nos. 4,594,308 and the like. Further, a dye-receptive polymer compound as described in US Pat. No. 4,463,079 may be used. The hydrophilic binder is preferable as the binder used in the dye fixing material of the present invention. Further, it is preferable to use carrageenans as described in European Patent Publication No. 443,529 and latexes having a glass transition temperature of 40 ° C. or lower as described in Japanese Patent Publication No. 3-74,820. If necessary, the dye fixing material may be provided with auxiliary layers such as a protective layer, a peeling layer, an undercoat layer, an intermediate layer, a back layer and an anti-curl layer. In particular, it is useful to provide a protective layer.

In the constituent layers of the photothermographic material and the dye-fixing material, a high boiling point organic solvent can be used as a plasticizer, a slipping agent or an agent for improving the releasability between the photosensitive material and the dye-fixing material. Specific examples include those described in Research Disclosure and JP-A-62-245,253. Further, various silicone oils (all silicone oils from dimethyl silicone oils to modified silicone oils obtained by introducing various organic groups into dimethyl siloxane) can be used for the above purpose. As examples thereof, various modified silicone oils described in “Modified Silicone Oil” technical data P6 to 18B issued by Shin-Etsu Silicone Co., Ltd., particularly carboxy-modified silicone (trade name X-22-3710) are effective. Silicone oils described in JP-A Nos. 62-215,953 and 63-46,449 are also effective.

An anti-fading agent may be used in the photothermographic material and the dye fixing material. As the anti-fading agent, there are, for example, an antioxidant, an ultraviolet absorber, or a certain kind of metal complex, and the dye image stabilizer and the ultraviolet absorber described in the above Research Disclosure are also useful. Examples of the antioxidant include chroman compounds, coumarane compounds, phenol compounds (for example, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. In addition, JP-A-61
The compounds described in -159,644 are also effective. As the ultraviolet absorber, benzotriazole compounds (US Pat. No. 3,533,794 etc.), 4-thiazolidone compounds (US Pat. No. 3,352,681 etc.), benzophenone compounds (JP-A-46- 2,784) and others, JP-A-54-48,535 and 62-1.
36,641 and 61-88,256. Further, the ultraviolet absorbing polymer described in JP-A-62-260,152 is also effective. Examples of the metal complex include U.S. Pat. Nos. 4,241,155 and 4,245.
No. 018, columns 3 to 36, No. 4,254,195, number 3
Column-8, JP-A-62-174,741 and 61-8
8, 256 (27) to (29), 63-199,
248, JP-A-1-75,568, 1-74,2
There are compounds described in No. 72 and the like.

The anti-fading agent for preventing the fading of the dye transferred to the dye fixing material may be contained in the dye fixing material in advance, or the dye may be externally applied from the photothermographic material or a transfer solvent described later. You may make it supply to a fixing material. The above-mentioned antioxidant, ultraviolet absorber, and metal complex may be used in combination with each other. A fluorescent whitening agent may be used in the photothermographic material and the dye fixing material. In particular, it is preferable to incorporate a fluorescent whitening agent in the dye fixing material or supply it from the outside such as a photothermographic material or a transfer solvent. As an example, K. Veenkataraman edited by "The Chem
istry of Synthetic Dyes ", Volume V, Chapter 8, JP-A-61
The compound described in -143752 etc. can be mentioned. More specifically, a stilbene compound,
Examples include coumarin-based compounds, biphenyl-based compounds, benzoxazolyl-based compounds, naphthalimide-based compounds, pyrazoline-based compounds, and carbostyryl-based compounds.
The fluorescent whitening agent can be used in combination with an anti-fading agent or an ultraviolet absorber. Specific examples of these anti-fading agents, ultraviolet absorbers and fluorescent whitening agents are described in JP-A-62-215,27.
2 (125)-(137), JP-A-1-161,
No. 36, pages (17) to (43).

As the hardener used in the constituent layers of the photothermographic material and the dye fixing material, the above-mentioned Research Disclosure, US Pat. No. 4,678,739, column 41, 4,791,042, JP-A No. Sho 59-116,655
No. 62-245, 261, 61-18, 942.
And the hardeners described in JP-A-4-218,044 and the like. More specifically, aldehyde hardeners (formaldehyde etc.), aziridine hardeners, epoxy hardeners, vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane, etc.),
Examples thereof include N-methylol type hardeners (dimethylolurea etc.) and polymer hardeners (compounds described in JP-A-62-234,157). These hardeners
0.001 to 1 g, preferably 0.005 to 0.5 g, is used per 1 g of coated gelatin. The layer to be added may be any layer of the photosensitive material and the dye-fixing material, or may be divided into two or more layers and added.

Various antifoggants or photographic stabilizers and their precursors can be used in the constituent layers of the photothermographic material or dye fixing material. Specific examples thereof include the aforementioned Research Disclosure, U.S. Pat. Nos. 5,089,378, 4,500,627, 4,614,702, and JP-A-64-13,546 (7). (9) page, (57) to (71) page and (8
1)-(97), U.S. Pat. No. 4,775,610,
No. 4,626,500, No. 4,983,494, JP-A Nos. 62-174,747, 62-239,148.
No. 63-264,747, JP-A-1-150,1.
No. 35, No. 2-110,557, No. 2-178,65
No. 0, RD17, 643 (1978) (24)-(2
5) The compounds described on page etc. are mentioned. These compounds are preferably used in an amount of 5 × 10 ⁻⁶ to 1 × 10 ⁻¹ mol, and more preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻² mol, per mol of silver.

In the constituent layers of the photothermographic material and the dye fixing material, a coating aid, a peeling property improving property, a slip property improving property, an antistatic property,
Various surfactants can be used for the purpose of promoting development and the like. Specific examples of the surfactant include Research Disclosure, JP-A Nos. 62-173,463 and 62-62.
No. 183,457. The constituent layers of the photothermographic material and the dye-fixing material may contain an organic fluoro compound for the purpose of improving slipperiness, preventing electrification, and improving releasability. As typical examples of organic fluoro compounds, JP-B-57-9053, columns 8 to 17, JP-A-61-209 can be used.
No. 44, No. 62-135826, or the like, or a fluorine-containing surfactant such as a fluorine-containing surfactant such as a fluorine-containing compound such as a fluorine oil or a solid fluorine-containing compound resin such as a tetrafluoroethylene resin. Can be mentioned.

A matting agent can be used in the photothermographic material and dye fixing material for the purpose of preventing adhesion, improving slipperiness, and providing a non-glossy surface. As the matting agent, in addition to the compounds described in JP-A-61-88256, page 29, such as silicon dioxide, polyolefin or polymethacrylate, benzoguanamine resin beads, polycarbonate resin beads, AS resin beads and the like are disclosed in JP-A-63-2749.
44, and 63-274952.
In addition, the compounds described in the above Research Disclosure can be used. These matting agents can be added not only to the uppermost layer (protective layer) but also to the lower layer if necessary. In addition, the constituent layers of the photothermographic material and the dye-fixing material may contain a thermal solvent, a defoaming agent, an antibacterial / antifungal agent, colloidal silica and the like. Specific examples of these additives are described in JP-A-61-88256, pages (26) to (32), JP-A-3.
-11,338, Japanese Patent Publication No. 2-51,496 and the like.

In the present invention, an image forming accelerator can be used in the photothermographic material and / or the dye fixing material. The image formation accelerator includes a redox reaction between a silver salt oxidizing agent and a reducing agent, a reaction such as generation of a dye from a dye-donor substance, decomposition of the dye or release of a diffusible dye, and heat development sensitization. It has functions such as accelerating the migration of dyes from the material layer to the dye fixing layer. From the physicochemical functions, bases or base precursors, nucleophilic compounds, high boiling organic solvents (oils), thermal solvents, surfactants. , And compounds that interact with silver or silver ions. However, these substance groups generally have a composite function, and usually have some of the above-mentioned accelerating effects together. Details thereof are described in US Pat. No. 4,678,739, columns 38 to 40. As a base precursor, a salt of an organic acid and a base that is decarboxylated by heat, an intramolecular nucleophilic substitution reaction,
Examples include compounds that release amines by Rossen rearrangement or Beckmann rearrangement. A specific example is U.S. Pat. No. 4,
511, 493, 4,657, 848 and the like.

In a system in which heat development and dye transfer are carried out simultaneously in the presence of a small amount of water, a method of incorporating a base and / or a base precursor into the dye-fixing material is preferable in terms of enhancing the storage stability of the photothermographic material. . Besides the above,
European Patent Publication 210,660, US Pat. No. 4,74
No. 0,445, a combination of a sparingly soluble metal compound and a compound capable of complex-forming reaction with a metal ion constituting the sparingly soluble metal compound (referred to as a complex-forming compound), and JP-A-61-232451. The compounds that generate a base by electrolysis described in 1) can also be used as the base precursor. The former method is particularly effective. The sparingly soluble metal compound and the complex-forming compound are advantageously added separately to the photothermographic material and the dye fixing element as described in the above-mentioned patent.

In the present invention, various development stoppers can be used in the photothermographic material and / or the dye fixing material for the purpose of always obtaining a constant image against variations in the processing temperature and processing time during development. . The term "development terminating agent" as used herein refers to a compound that immediately neutralizes or reacts with a base after proper development to lower the concentration of the base in the film and stops the phenomenon, or interacts with silver and silver salts to suppress development. Compound. Specific examples thereof include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound and a precursor thereof. For more details, see JP-A-6
2-253, 159 (31) to (32).

In the photothermographic material of the present invention, a support containing paper having irregularities on its surface, particularly a support laminated on both sides with polyethylene is used. The light-sensitive material of the present invention is slightly effective even if it is a synthetic polymer (film) support, but its effect is slight since the surface unevenness is originally good.
Further, in the present invention, as the support of the dye fixing material,
A material that can withstand the processing temperature is used. In general, "The Basics of Photographic Engineering -Silver Salt Photo-" edited by The Photographic Society of Japan, published by Corona Co., Ltd. (1979) (223)-
Examples include papers described on page (240) and photographic supports such as synthetic polymers (films). Specifically, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or those containing pigments such as titanium oxide in these films, Film method synthetic paper made from polypropylene etc., mixed paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coated paper (particularly cast coated paper), metal, cloth, glass etc. Is used. These can be used alone or as a support laminated on one or both sides with a synthetic polymer such as polyethylene. This laminated layer contains
If necessary, pigments and dyes such as titanium oxide, ultramarine blue and carbon black can be contained. In addition to this, JP-A-62-253,159 (29) to (31)
Page, JP-A-1-161,236 (14) to (17)
Page, JP-A-63-316,848, JP-A-2-22,
No. 651, No. 3-56,955, US Pat. No. 5,00.
The support described in No. 1,033 can be used.
The surface of these supports may be coated with a hydrophilic binder, a semiconductive metal oxide such as alumina sol or tin oxide, carbon black or another antistatic agent. Specifically, the supports described in JP-A-62-220246 can be used. Further, the surface of the support is preferably subjected to various surface treatments and undercoats for the purpose of improving the adhesion with the hydrophilic binder.

As a method of exposing and recording an image on the photothermographic material, for example, a method of directly photographing a landscape or a person by using a camera or exposing through a reversal film or a negative film by using a printer or an enlarger is used. Method, scanning exposure of the original image through a slit, etc. using an exposure device of a copying machine, scanning exposure by causing image information to emit light through a light emitting diode, various lasers (laser diode, gas laser, etc.) Method (Japanese Patent Application Laid-Open No. 2-129,625, Japanese Patent Application No. 3-33)
8,182, 4-9,388, 4-281,4
No. 42), image information is output to an image display device such as a CRT, a liquid crystal display, an electroluminescence display, and a plasma display, and exposed directly or through an optical system.

As a light source for recording an image on a photothermographic material, as described above, natural light, a tungsten lamp, a light emitting diode, a laser light source, a CRT light source, etc., US Pat. No. 4,500,626, column 56, Special Features Kaihei 2-53,
The light source and the exposure method described in Nos. 378 and 2-54,672 can be used. Image exposure can also be performed using a wavelength conversion element in which a non-linear optical material and a coherent light source such as laser light are combined. Here, the non-linear optical material is a material capable of exhibiting non-linearity between polarization and electrolysis, which appears when a strong optical electric field such as laser light is applied, such as lithium niobate and potassium dihydrogen phosphate (KDP). ), An inorganic compound represented by lithium iodate, BaB ₂ O ₄ or the like, a urea derivative, a nitroaniline derivative, for example, nitropyridine-N-such as 3-methyl-4-nitropyridine-N-oxide (POM). Oxide derivatives, JP-A-61-53462 and JP-A-62-2104
The compound described in No. 32 is preferably used. As a form of the wavelength conversion element, a single crystal optical waveguide type, a fiber type and the like are known, and any of them is useful. Further, the above-mentioned image information is an image signal obtained from a video camera, an electronic still camera, or the like, NTV signal standard (NT
For example, a television signal represented by SC), an image signal obtained by dividing an original image into a large number of pixels such as a scanner, or an image signal created by using a computer represented by CG or CAD can be used.

The photothermographic material and / or dye fixing material of the present invention may have a form having a conductive heating element layer as a heating means for heat development and diffusion transfer of dye. The heat generating element in this case is disclosed in JP-A-61-114.
Those described in No. 5,544 can be used. The heating temperature in the heat development step is about 50 ° C to 250 ° C, and particularly about 60 ° C to 180 ° C is useful. The dye diffusion transfer process may be performed simultaneously with the heat development, or may be performed after the end of the heat development process. In the latter case, the heating temperature in the transfer step can be transferred in the range from the temperature in the heat development step to room temperature, but it is particularly 50 ° C. or higher and about 10 ° C higher than the temperature in the heat development step.
Up to a temperature lower by ℃ is preferred.

Although the migration of the dye occurs only by heat,
Solvents may be used to facilitate dye transfer. Also,
U.S. Pat. Nos. 4,704,345 and 4,740,44
No. 5, JP-A-61-238,056 and the like, a method of performing development and transfer simultaneously or continuously by heating in the presence of a small amount of solvent (particularly water) is also useful. In this system, the heating temperature is preferably 50 ° C. or higher and not higher than the boiling point of the solvent. For example, when the solvent is water, it is preferably 50 ° C. to 100 ° C. Examples of the solvent used for accelerating the development and / or the diffusion transfer of the dye include water, a basic aqueous solution containing an inorganic alkali metal salt or an organic base (these bases are referred to as an image forming accelerator). Those described are used), or a low boiling point solvent or a mixed solution of a low boiling point solvent and water or the above basic aqueous solution. Further, a surfactant, an antifoggant, a complex-forming compound with a sparingly soluble metal salt, an antiseptic, and an antibacterial agent may be contained in the solvent. Water is preferably used as the solvent used in the steps of heat development and diffusion transfer, but any commonly used water may be used. Specifically, distilled water, tap water, well water, mineral water or the like can be used. Further, in the heat developing apparatus using the photothermographic material and the dye fixing material of the present invention, water may be used up, or may be circulated and repeatedly used. In the latter case, water containing the components eluted from the material will be used. Further, JP-A-63-144,354 and JP-A-63-144,355.
No. 62-38,460, JP-A-3-210,55.
You may use the apparatus and water described in No. 5, etc.

These solvents can be used by a method of applying them to the photothermographic material, the dye fixing material or both. The amount used may be not more than the weight of the solvent corresponding to the maximum swelling volume of the entire coated film. As a method of giving this water,
For example, the methods described in JP-A-62-253,159, page (5) and JP-A-63-85,544 are preferably used. Also, the solvent is enclosed in microcapsules,
It may be used by preliminarily incorporating it in the form of a hydrate in the photothermographic material or the dye fixing element or both. The temperature of the applied water may be 30 ° C to 60 ° C as described in JP-A-63-85,544. In particular, it is useful to set the temperature to 45 ° C. or higher for the purpose of preventing the growth of various fungi in water.

In order to promote dye transfer, a system in which a hydrophilic thermal solvent which is solid at room temperature and dissolves at high temperature is incorporated in the photothermographic material and / or the dye fixing material can also be adopted. The layer to be incorporated may be any of a photosensitive silver halide emulsion layer, an intermediate layer, a protective layer and a dye fixing layer, but a dye fixing layer and / or a layer adjacent thereto is preferable. Examples of hydrophilic thermal solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes and other heterocycles.

As a heating method in the developing and / or transferring step, a heating block or plate is brought into contact with a heating plate, a hot presser, a heating roller, a heating drum, a halogen lamp heater, an infrared and far infrared lamp heater. There is a method of contacting with, etc. or passing through in a high temperature atmosphere. The method described in JP-A-62-253,159 and JP-A-61-147,244 (page 27) can be applied to the method of superimposing the heat-developable light-sensitive material and the dye-fixing material.

Any of a variety of heat developing apparatus can be used in processing the photographic elements of this invention. For example, JP-A-59-7
5,247, 59-177,547, 59-1
81,353, 60-18,951, No. 62
-25,944, Japanese Patent Application Nos. 4-277,517 and 4
The devices described in No. 243,072, No. 4-244,693 and the like are preferably used. Further, as a commercially available apparatus, Pictrostat 100, Pictrostat 200, Pictrography 3000, Pictrography 2000, and the like manufactured by Fuji Photo Film Co., Ltd. can be used.

[0141]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. Example

How to make a photosensitive silver halide emulsion

Photosensitive silver halide emulsion (1) [for red-sensitive emulsion layer] Well-stirred aqueous gelatin solution [800 g of gelatin, 12 g of potassium bromide, 80 g of sodium chloride and compound (a) in 27 liters of water]. 2g was added and kept warm at 55 ° C), 1 solution of (I) and (II) of Table 1 at the same time.
Added at equal flow rate for 9 minutes. After 5 minutes, (III) solution and (I
Solution V) was added simultaneously at an equal flow rate for 24 minutes. After washing with water and desalting by a conventional method, 880 g of lime-treated ossein gelatin and 2.8 g of compound (b) were added to adjust pH to 6.2 and pAg to 7.7, and 20.5 g of a ribonucleic acid degradation product, and Methylthiourea (51 mg) was added, and optimal chemical sensitization was performed at 60 ° C for about 70 minutes, and then 4-hydroxy-6-methyl-1,3,3.
90 g of a, 7-tetrazaindene, 3.2 g of dye (a),
After sequentially adding 20.5 g of KBr, the mixture was cooled. Thus, 29.5 kg of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.30 μm was obtained.

[0144]

[Table 1]

[0145]

[Chemical 21]

Photosensitive Silver Halide Emulsion (2) [For Green Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.3 g of potassium bromide and 2 g of sodium chloride in 600 ml of water).
g and 30 mg of the compound (a) were added and kept at 46 ° C.), the solutions (I) and (II) in Table 2 were simultaneously added at an equal flow rate for 10 minutes. After 5 minutes, the liquid (III) and the liquid (IV) shown in Table 2 were further added.
The solution was added simultaneously at the same flow rate for 30 minutes. Also (III), (I
1 minute after the addition of V) solution, 60 ml of dye solution in methanol
(Containing 360 mg of dye (b1) and 73.4 mg of dye (b2)) were added all at once. Rinsing with water and desalting (settling agent (a)
Was carried out at pH 4.0), and then 22 g of lime-treated ossein gelatin was added, and appropriate amounts of NaCl and NaOH were added to adjust the pH to 6.0 and pAg to 7.6 to obtain 1.8 mg of sodium thiosulfate. 4-hydroxy-6-methyl-1,
Add 3,3a, 7-tetrazaindene 180mg to 60
Optimum chemical sensitization at ℃, then antifoggant (1) 90mg
Was added and then cooled. Also, as a preservative compound
(b) 70 mg and compound (c) 3 ml were added. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.30 μm was obtained.

[0147]

[Table 2]

[0148]

[Chemical formula 22]

[0149]

[Chemical formula 23]

Photosensitive silver halide emulsion (3) [For blue-sensitive emulsion layer] Well-stirred aqueous gelatin solution (1582 g of gelatin, 127 g of KBr, 127 g of compound (a) in 29.2 liters of water).
660 mg was added and kept at 70 ° C.), solution I and solution II having the composition shown in Table 3 and solution II were added, and after 10 seconds, solution I was added.
Each was added over 30 minutes. Also, after the addition of solution II is completed, 5
After 4 minutes, the IV solution was added, and 10 seconds after that, the III solution was added over 27 minutes and 50 seconds for the III solution and for 28 minutes for the IV solution.

Then, after washing with water and desalting by a conventional method (performed at pH 3.9 using 32.4 g of the precipitating agent (b)),
1.230 g of lime-treated ossein gelatin and compound (b) 2.
8 g was added to adjust pH to 6.1 and pAg to 8.5. Then, add 27.7 mg of sodium thiosulfate, and add 6
After optimal chemical sensitization at 5 ° C. for about 70 minutes, dye (c) 17.
5 g, antifoggant (1) 2.8 g, compound (c) 117
After adding ml sequentially, it was cooled. The silver halide grains of the obtained emulsion were octahedral, and the grain size was 0.55 μm.
The yield was 29.1 kg.

[0152]

[Table 3]

[0153]

[Chemical formula 24]

Next, a method for preparing a gelatin dispersion of the compound (d) will be described. Compound (d) 0.4 g, high boiling organic solvent (1) 1.1 g, compound (f) 0.1 g, compound
0.2 g of (g) and 0.2 of surfactant (1) were weighed, 9.5 cc of ethyl acetate was added, and the mixture was heated and dissolved at about 60 ° C. to obtain a uniform solution. After stirring and mixing this solution with 60 g of a 16% solution of lime-processed gelatin, it was mixed with a homogenizer for 1 minute for 1 minute.
Dispersed at 0000 rpm. After dispersion, add 29cc of water for dilution
added. This dispersion is referred to as a dispersion of compound (d).

[0155]

[Chemical 25]

A method for preparing a dispersion of zinc hydroxide will be described. Zinc hydroxide with an average particle size of 0.2 μm 12.5
g, 1 g of carboxymethyl cellulose as a dispersant, and 0.1 g of sodium polyacrylate as a 4% gelatin aqueous solution 10
In addition to 0 ml, it was ground in a mill for 30 minutes using glass beads having an average particle size of 0.75 mm. The glass beads were separated to obtain a zinc hydroxide dispersion.

Next, a method for preparing a gelatin dispersion of a dye-donor compound will be described. Cyan dye-donor compound (A
7.3 g of 1) and 1 of cyan dye-donor compound (A2)
1.0 g, surfactant (1) 0.8 g, compound (h) 1
g, 1.3 g of compound (i), 4.4 g of compound (j), 2.2 g of compound (k), 7 g of high boiling point organic solvent (1), 3 g of high boiling point organic solvent (2) , Add 26 ml of ethyl acetate,
It was heated and dissolved at about 60 ° C. to obtain a uniform solution. This solution, 65 g of a 16% lime-processed gelatin solution and 87 cc of water were mixed with stirring, and then a homogenizer was operated at 10,000 rpm for 10 minutes.
Dispersed. After the dispersion, 220 cc of water for dilution was added. This dispersion is called a cyan dye-donor compound dispersion.

[0158]

[Chemical formula 26]

[0159]

[Chemical 27]

The magenta dye-donating compound (B) was added to 4.5
0 g, compound (m) 0.05 g, compound (h) 0.05
g, 0.094 g of surfactant (1), high boiling organic solvent
2.25 g of (2) was weighed, 10 ml of ethyl acetate was added, and the mixture was heated and dissolved at about 60 ° C. to obtain a uniform solution. This solution, 15.2 g of a 16% solution of lime-processed gelatin and 23.5 cc of water
After stirring and mixing, the mixture was mixed with a homogenizer for 10 minutes for 100 minutes.
Dispersed at 00 rpm. After that, 42 cc of dilution water was added.
This dispersion is referred to as a dispersion of the magenta dye-donor compound.

[0161]

[Chemical 28]

The yellow dye-donor compound (C) was used in an amount of 15
g, 3 g of compound (d), 1.5 g of compound (h), 1.4 g of surfactant (1) and 7.5 g of high boiling point organic solvent (2), 40 ml of ethyl acetate was added, and It was heated and dissolved at 60 ° C to obtain a uniform solution. This solution, 53 g of a 16% solution of lime-processed gelatin and 85.7 cc of water were stirred and mixed, and then dispersed by a homogenizer at 10,000 rpm for 10 minutes.
After that, 83.7 cc of water for dilution was added. This dispersion is called a yellow dye-donor compound dispersion.

[0163]

[Chemical 29]

15 g of the compound 15 described in the specification, 4.7 g of the compound (d), 0.9 g of the compound (h), 1.77 g of the surfactant (1) and the high boiling point organic solvent (1) were added. 18.8g,
3.9 g of the compound (n) was weighed, 50 ml of ethyl acetate was added, and the mixture was heated and dissolved at about 60 ° C. to obtain a uniform solution. This solution and 65 g of a 16% solution of lime-processed gelatin and 110 cc of water
After stirring and mixing, the mixture was mixed with a homogenizer for 10 minutes for 100 minutes.
Dispersed at 00 rpm. After that, 90 cc of water for dilution was added.
This dispersion is called a yellow dye-donor compound dispersion.

[0165]

[Chemical 30]

With these, the photothermographic materials 101 and 102 to 109 shown in Tables 4 and 5 were constructed.

[0167]

[Table 4]

[0168]

[Table 5]

[0169]

[Table 6]

[0170]

[Chemical 31]

[0171]

[Chemical 32]

In preparing the light-sensitive material, the coating amount, viscosity and gelatin concentration of the coating liquid for each layer were adjusted as shown in Table 8.
The adjustment method was performed by adjusting the ratio of the coating solution diluted with water and the amount of the following thickener.

[0173]

[Chemical 33]

[0174]

[Table 7]

Photosensitive materials 101 to 109 were prepared by using the coating solutions thus prepared as shown in Table 8. The photosensitive material 108 was prepared in exactly the same manner as the photosensitive material 101 except that 0.57 g / m ² of copper carrageenan was added to the seventh layer.

Each of the obtained light-sensitive materials 101 to 109 was surface-exposed so as to match with a gray having a density of 0.7, and water was uniformly applied to the surface of the light-sensitive material. I put them on top of each other. When heated at 83 ° C. for 30 seconds and peeled off, an image was obtained on the image receiving material. Table 9 shows the results of the visual determination of the density unevenness of the image.

[0177]

[Table 8]

As can be seen from Table 8, the light-sensitive material of the present invention is an excellent light-sensitive material with less uneven density. Next, how to make the image receiving material used above will be described. Image-receiving material R201 having a structure as shown in Tables 10 and 11
made.

[0179]

[Table 9]

[0180]

[Table 10]

[0181]

Embedded image

[0182]

Embedded image

[0183]

Embedded image

[0184]

Embedded image

[0185]

[Chemical 38]

Claims (2)

[Claims] 1. A heat-developable color photosensitive material comprising at least a photosensitive silver halide, a binder, and a dye-donating compound on a paper support, and a total binder coating amount of 5 g / m ² or less. A heat-developable color light-sensitive material characterized by employing any one of the following (1) to (4) or a combination thereof in the manufacturing process. (1) The total coating amount during coating is 80 cc / m ² or less. (2) The viscosity of at least one layer coating liquid is 80 cp at 40 ° C.
(Centipoise) or more and 200 cp or less. (3) The gelatin concentration of the coating solution for at least one layer containing photosensitive silver halide is 2.0% or more. (4) At least one layer contains a natural polymeric polysaccharide derived from red algae. 2. A heat-developable color light-sensitive material according to claim 1, which contains a compound represented by the following general formula (1) as a dye-donor compound. General formula (1) In the formula, Dye represents a dye group or a dye precursor group represented by the following general formula (2), and Y represents a dye component corresponding to reduction of a photosensitive silver halide having a latent image in an image form to silver. Represents a group having a property of causing a difference in diffusibility, X represents a simple bond or a linking group, p represents a natural number of 1 or more, q represents 1 or 2, and p is 2 or more or q is 2. Dye or (Dye) _p -X may be the same or different. General formula (2) In the formula, R ¹ and R ² are hydrogen atom, halogen atom, hydroxyl group, cyano group, nitro group, carboxyl group, substituted or unsubstituted alkyl group, aralkyl group, cycloalkyl group, aryl group, heterocyclic group, alkoxy group, Aryloxy group, amino group, acylamino group, sulfonylamino group,
It represents a substituent selected from an acyl group, a sulfonyl group, a carbamoyl group, a sulfamoyl group, a ureido group, an alkylthio group and an arylthio group. R ³ has the same meaning as R ¹ and R ² except for the hydrogen atom defined by R ¹ and R ² . n represents an integer of 0 to 5, and when n is 2 to 5, R ³ may be the same or different. Dye and X are bonded via any ^one of R ¹ , R ² and R ^{3 in} the general formula (2).