JPH06242546A - Heat developing color photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a photosensitive material which has excellent picture density, capable of decreasing fogging and excellent in other photographic characteristics by incorporating a specified ortho-or para-sulfonamide phenols and an acetylene compd. respectively on a photosensitive layer. CONSTITUTION:This material has a photosensitive silver halide, a reducing agent, the compd. expressed by formula I or II and the dye donative compd. which releases a diffusion type dye in accordance with silver-developing on a supporting body, and is incorporated with the compd. expressed by formula II in the photosensitive layer. In formula I and II, Ball is the org. ballast group which is capable of converting the compd. to a nondiffusion type, Y is the atom group necessary to form benzene neucleus and naphthalene nucleus, R1 is alkyl, aralkyl group, etc., R2 is hydrogen atom, cycloalkyl group, etc., (n) is integer 0-5. In formula III, L is a single bond or bivalent connecting group, (n) is integer 1-4, when (n) is 1, R1 is hydrogen atom. carboxyl group, etc., when (n) is 2-4, R1 is 2-4 valent residual group, R2 is hydrogen atom, alkyl group, etc.

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-developable color light-sensitive material having excellent image density and low fog when heat-developed.

[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.

[0005]

Problems of the Prior Art A method of using the general formula (I) or (II) alone is described in JP-A-62-247358, but it has an excellent image density in heat development and further reduces fog. Is not enough to let you. In the present invention, by containing the general formula (I) or (II) in the photosensitive silver halide and further using the general formula (III) in combination, it is possible to impart excellent image density and reduce fog. Realized successfully.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a heat-developable color light-sensitive material which has an excellent image density in heat development, can reduce fog, and is excellent in other photographic characteristics. Especially.

[0007]

Such an object is achieved by the following constitution.

A photosensitive silver halide, a reducing agent, and
In a heat-developable color light-sensitive material having a compound represented by formula (I) or (II), a binder, and a dye-donor compound, at least one light-sensitive layer containing the light-sensitive silver halide has a general formula ( A heat-developable color light-sensitive material containing at least one of the compounds represented by III).

[0009]

[Chemical 3]

[In the general formulas (I) and (II), Bal
l represents an organic ballast group capable of rendering the compounds represented by these formulas diffusible. However, when R ₁ is non-diffusible, Ball may be omitted. Y represents a carbon atom group necessary for completing a benzene nucleus or a naphthalene nucleus. R ₁ is a substituted or unsubstituted alkyl group,
It represents a cycloalkyl group, an aralkyl group, an aryl group, an amino group or a heterocyclic group. R ₂ is a hydrogen atom, a halogen atom or a substituted or unsubstituted cycloalkyl group, aralkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, acyl group, alkyloxycarbonyl group, aryloxycarbonyl group, carbamoyl group Represents a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an acylamino group, an alkylthio group, or an arylthio group. n represents an integer of 0 to 5, n
When ₂ is 2 to 5, R _{2 s} may be the same or different, and may combine with each other to form a ring. In addition, when Y represents an atomic group necessary for completing the naphthalene nucleus, Ba
11 and R ₂ can be attached to any of the ring systems so formed. ]

[0011]

[Chemical 4]

[In the general formula (III), L represents a simple bond or a divalent linking group. n represents an integer of 1 to 4. When n = 1, R ₁ represents a hydrogen atom, a carboxyl group, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group or a heterocyclic group. When n = 2, 3 or 4, R ₁ represents a divalent, trivalent or tetravalent residue. R ₂ represents a hydrogen atom, a carboxyl group, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, an aryl group, a heterocyclic group or a carbamoyl group. When n is 2, 3 or 4, the respective combinations of L and R ₂ may be the same or different. However, the case where L is a bond and n 1 is ₁ and both R ₁ and R ₂ are hydrogen atoms is excluded. ]

The present invention relates to a heat-developable color light-sensitive material having on a support a light-sensitive silver halide, a reducing agent, a compound represented by formula (I) or (II), a binder, and a dye-providing compound. Since at least one photosensitive layer containing the photosensitive silver halide contains at least one of the compounds represented by the general formula (III), it has an excellent image density in heat development,
Moreover, fogging can be reduced.

The specific structure of the present invention will be described in detail below. The heat-developable color light-sensitive material of the present invention comprises at least one light-sensitive layer containing a light-sensitive silver halide, a reducing agent, a compound represented by formula (I) or (II), a binder, and a dye-donating compound. It contains at least one compound of the general formula (III).

First, general formulas (I) and (II) will be described in detail.

In the general formulas (I) and (II), R ₁ represents a substituted or unsubstituted alkyl group, cycloalkyl group, aralkyl group, aryl group, amino group or heterocyclic group. Preferred examples of R ₁ include substituted or unsubstituted alkyl groups having 1 to 30 carbon atoms, such as methyl group, ethyl group and dodecyl group; substituted or unsubstituted cycloalkyl groups having 5 to 30 carbon atoms, such as cyclohexyl. Group, etc .; substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, for example, benzyl group, β-phenethyl group, etc .; carbon number 6
A substituted or unsubstituted aryl group having from 30 to 30, such as a phenyl group, a naphthyl group, a tolyl group, a xylyl group, etc .; a substituted or unsubstituted amino group having from 0 to 30 carbon atoms, such as an amino group, a methylamino group, an isopropylamino group. , Cyclohexylamino group, phenylamino group, benzylamino group, N, N-dimethylamino group, N-methyl-N-ethylamino group, N, N-diisopropylamino group, N, N
-Dicyclohexylamino group, N, N-diphenylamino group, N, N-dibenzylamino group; substituted or unsubstituted heterocyclic groups such as pyridyl group, furyl group and thienyl group.

The substituent of the aryl group will be described in detail. As the substituent, for example, a halogen atom (chlorine atom,
Bromine atom, etc.), amino group, alkoxy group, aryloxy group, carbonamido group, alkanoyloxy group, benzoyloxy group, ureido group, carbamate group, carbamoyloxy group, carbonate group, carboxy group, alkyl group (methyl group, ethyl group) Groups, propyl groups, etc.), acylamino groups, sulfamoyl groups, ester groups, alkylsulfonyl groups, alkylsulfonylamino groups, arylsulfonylamino groups, and the like.

R ₂ is hydrogen atom, halogen atom, substituted or unsubstituted alkyl group, cycloalkyl group, aralkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, acyl group, alkyloxycarbonyl group, aryl It represents an oxycarbonyl group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an acylamino group, an alkylthio group, or an arylthio group.

Preferred examples of R ₂ include a hydrogen atom; a halogen atom such as a bromine atom and a chlorine atom;
20 substituted or unsubstituted alkyl groups, for example, methyl group, ethyl group, isopropyl group, t-butyl group and the like; substituted or unsubstituted cycloalkyl groups having 5 to 20 carbon atoms,
For example, cyclopentyl group, cyclohexyl group and the like; substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms, such as benzyl group, β-phenethyl group and the like; substituted or unsubstituted aryl group having 6 to 20 carbon atoms, such as phenyl group, Naphthyl group and the like listed in R ₁ ; substituted or unsubstituted heterocyclic group, such as pyridyl group, furyl group, thienyl group, etc .; substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, such as methoxy group. , Butoxy group, methoxyethoxy group and the like; substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms, for example, phenoxy group and the like; 1 to 20 carbon atoms
A substituted or unsubstituted acyl group such as acetyl group,
Balmitoyl group and the like; substituted or unsubstituted alkyloxycarbonyl group having 1 to 20 carbon atoms, such as methoxycarbonyl group; aryloxycarbonyl group having 1 to 20 carbon atoms, such as phenoxycarbonyl group and the like; carbon number 1 to 2
0 substituted or unsubstituted carbamoyl group, for example, methylcarbamoyl group, dimethylcarbamoyl group, diisopropylcarbamoyl group and the like; substituted or unsubstituted sulfamoyl group having 1 to 20 carbon atoms, for example, dimethylsulfamoyl group and the like; carbon number 1 ~ 20 substituted or unsubstituted alkylsulfonyl groups such as methylsulfonyl group;
A substituted or unsubstituted arylsulfonyl group having 1 to 20 carbon atoms, such as phenylsulfonyl group, p-methylphenylsulfonyl group and the like; a substituted or unsubstituted acylamino group having 2 to 20 carbon atoms, such as acetylamino group, N-
A methylacetylamino group, a palmitoylamino group, etc .; a substituted or unsubstituted alkylthio group having 1 to 20 carbon atoms,
For example, methylthio group, ethylthio group, etc .; C6-30
And a substituted or unsubstituted arylthio group such as phenylthio group and m-methoxycarbonylphenylthio group.

N represents an integer of 0 to 5, and when n is 2 to 5, R _{2 s} may be the same or different, and may combine with each other to form a ring.

As such a ring, bicyclo [2.2.
1] Hept-2-ene, cyclohexene and the like.

Ball represents an organic ballast group capable of rendering the compounds represented by these formulas non-diffusible. However, when R ₁ is non-diffusible, Ball may be omitted.

The nature of the ballast group (Ball) is not critical as long as the ballast imparts diffusion resistance to the compound. Common ballast groups are straight or branched straight chain alkyl groups that are directly or indirectly attached to the compound, and are either indirectly attached to or directly attached to the benzene nucleus. Benzene-based and naphthalene-based aromatic groups are included. Effective ballast groups are generally groups having a minimum of 8 carbon atoms.

For example, a substituted or unsubstituted alkyl group having 8 to 30 carbon atoms, an acylamino group having 8 to 30 carbon atoms, an acyl group having 8 to 30 carbon atoms,
Acyloxy group having 8 to 30 carbon atoms, 8 to 8 carbon atoms
Examples thereof include an alkoxy group having 22 carbon atoms, an alkylthio group having 8 to 30 carbon atoms, an alkoxy group having an alkoxycarbonyl group having 8 to 30 carbon atoms, and the like. In addition, as an example of the indirect bond, a bond is formed through a carbamoyl group or a sulfamoyl group represented by the general formulas (IV) and (V) (the nitrogen atom contained in these groups is bonded to the ballast group). What has been done is preferable.

[0025]

[Chemical 5]

In the general formulas (IV) and (V), R ₃ is a hydrogen atom, an alkyl group having 1 to 7 carbon atoms (for example, a methyl group,
An ethyl group and the like), a cycloalkyl group (for example, a cyclohexyl group) and an aryl group (for example, a phenyl group) are preferable.

L represents a divalent group (for example, an alkylene group, a phenyl group, a divalent arylthio group, etc.), and m represents 0 or 1.

Y represents a carbon atom group necessary for completing a benzene nucleus or a naphthalene nucleus. In addition, when Y represents an atomic group necessary for completing the naphthalene nucleus, Bal
l and R ₂ can be attached to any of the ring systems so formed.

Specific examples of the compounds represented by formulas (I) and (II) are shown below, but the compounds in the present invention are not limited thereto.

[0030]

[Chemical 6]

[0031]

[Chemical 7]

[0032]

[Chemical 8]

[0033]

[Chemical 9]

[0034]

[Chemical 10]

[0035]

[Chemical 11]

[0036]

[Chemical 12]

[0037]

[Chemical 13]

[0038]

[Chemical 14]

[0039]

[Chemical 15]

[0040]

[Chemical 16]

The compounds of the present invention may be used alone or in combination of two or more kinds. And in the light-sensitive material, emulsion layer, intermediate layer,
Although it can be contained in any layer such as a protective layer,
It is particularly effective to add it to the dispersion of the dye-providing substance so that it is contained in the emulsion layer.

The addition amount is 0.0005 to 20 times mol, and particularly effective addition amount range is 0.001 to 4 times mol.

Next, the compound of the general formula (III) will be described in detail. The alkyl group of R ₁ and R ₂ may be linear or branched, and examples of the alkyl group include a butyl group, an isobutyl group, a hexyl group, a heptyl group, an octyl group, a dodecyl group and a pentadecyl group, Examples of the substituent of the substituted alkyl group include an alkoxy group (for example, a methoxy group), an aryloxy group, an acyloxy group, a heterocyclic oxy group, a hydroxy group, a carboxyl group or a salt thereof, a formyl group, an acyl group, a substituted or Unsubstituted carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, mercapto group, alkylthio group, arylthio group, sulfino group or salt thereof, sulfo group or salt thereof, alkylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, substituted or Unsubstituted sulfamoyl group, alkoxys Honyl group, aryloxysulfonyl group, acylamino group, substituted or unsubstituted ureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, nitro group, nitroso group, cyano group, halogen atom, alkylsulfonylamino group, arylsulfonylamino group Group, substituted or unsubstituted amino group, cycloalkyl group, alkenyl group, aryl group, aralkyl group, heterocyclic group, alkynyl group (eg ethynyl group) and the like. There may be two or more of these substituents.

Examples of the cycloalkyl group of R ₁ and R ₂ are cyclopentyl group, cyclohexyl group, decahydronaphthyl group and the like; Examples of alkenyl group are propenyl group, isopropenyl group, styryl group and the like; Examples thereof include an ethynyl group and a phenylethynyl group; examples of the aralkyl group include a benzyl group and a phenethyl group. These groups may have the substituents described in the alkyl group. Further, there may be two or more substituents.

Examples of the aryl group of R ₁ and R ₂ include a phenyl group and a naphthyl group, and examples of the substituent of the substituted aryl group include an alkyl group (methyl group, dodecyl group, etc.) and an alkenyl group. , Aryl groups, cycloalkyl groups, aralkyl groups, alkynyl groups, cyano groups, nitro groups, nitroso groups, substituted or unsubstituted amino groups, acylamino groups, alkylsulfonylamino groups, arylsulfonylamino groups, substituted or unsubstituted sulfones. Famoylamino group, hydroxyl group, alkoxy group, aryloxy group,
Alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxy group, acyloxy group, heterocyclic (5-6
Membered rings, especially nitrogen-containing heterocycles), alkoxysulfonyl groups, aryloxysulfonyl groups, alkylsulfinyl groups, arylsulfinyl groups, alkylthio groups, arylthio groups, mercapto groups, formyl groups, acyl groups, alkylsulfonyl groups, aryl Sulfonyl group, carboxylic acid group or salt thereof, sulfonic acid group or salt thereof, sulfino group or salt thereof, halogen atom (fluorine, bromine, chlorine, iodine), substituted or unsubstituted ureido group, carbamoyl group, sulfamoyl group, etc. Is. These substituents may be further substituted. Also, there may be two or more substituents as exemplified above.

The heterocyclic group for R ₁ and R ₂ is preferably a 5- or 6-membered one, and examples thereof include a furyl group, a thienyl group, a benzothienyl group, a pyridyl group and a quinolyl group. These heterocyclic groups may have the same substituent as the above-mentioned substituted aryl group.

Examples of the aryloxycarbonyl group for R ₂ include a phenoxycarbonyl group and the like; examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

Examples of the carbamoyl group for R ₃ include -CONH _{2 and} carbamoyl groups substituted with the above-mentioned substituted or unsubstituted alkyl group, aryl group or heterocyclic group.

When n is 2, 3 or 4, each R ₁ is 2
It represents a monovalent, trivalent or tetravalent residue, and examples thereof include _one hydrogen atom from the monovalent group of R ₁ or R ₂ described above.
The groups excluding 2, 2 or 3 are mentioned. Also n =
When R is 2, R ₁ also includes —NH—.

L represents a mere bond or a divalent linking group (preferably --O--CO-- group or --CONH-- group).

N is preferably 1 or 2.

Of these, compounds in which either R ₁ or R ₂ is a hydrogen atom and the other is a group other than a hydrogen atom are preferred.

More preferably, either R ₁ or R ₂ is a hydrogen atom, and the other is a phenyl group or a substituted phenyl group. In particular, the compound represented by the following general formula is preferable.

[0054]

[Chemical 17]

In the above formula, m is 1 or 2. R
When m = 1, ₃ represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group or a heterocycle having 1 to 20 carbon atoms, and when m = 2, an alkylene group or an arylene group. Represents a cycloalkylene group. Further, these substituents may be further substituted with other substituents.

Hereinafter, R ₃ will be described in detail.

The alkyl group may be linear or branched, and examples of the alkyl group include propyl group, isopropyl group, butyl group, isobutyl group, tertiary butyl group, pentyl group, hexyl group, heptyl group. Group, isoheptyl group, octyl group, nonyl group, decyl group, dodecyl group, pentadecyl group. Examples of the substituent of the substituted alkyl group include cycloalkyl group, alkenyl group, alkynyl group, aryl group, aralkyl group, heterocyclic group, halogen atom (fluorine, bromine, chlorine, iodine), hydroxyl group,
Alkoxy group, aryloxy group, acyloxy group, heterocyclic oxy group, carboxyl group or salt thereof, formyl group, acyl group, substituted or unsubstituted carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group, mercapto group, Alkylthio group, arylthio group, sulfino group or salt thereof, sulfo group or salt thereof, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, substituted or unsubstituted sulfamoyl group, alkoxysulfonyl group, aryloxysulfonyl group , Substituted or unsubstituted amino group, acylamino group, substituted or unsubstituted ureido group, alkoxycarbonylamino group, aryloxycarbonylalkylsulfonylamino group, arylsulfo group Arylamino group, a substituted or unsubstituted sulfamoylamino group, a nitro group, a nitroso group. Two or more of these groups may be present, or the substituents may be further substituted.

Examples of cycloalkyl groups include cyclopentyl group, cyclohexyl group, decahydronaphthyl group and the like; examples of alkenyl groups include propenyl group, isopropenyl group, styryl group and the like. These groups may have the substituents described for the alkyl group. Further, there may be two or more substituents.

Examples of the aryl group include a phenyl group and a naphthyl group, and examples of the substituent of the substituted aryl group include an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group and an aralkyl group. A heterocyclic group (5- or 6-membered ring, preferably nitrogen-containing heterocycle),
Halogen atom (fluorine, bromine, chlorine, iodine), hydroxyl group, alkoxy group, aryloxy group, acyloxy group, heterocyclic oxy group, carboxyl group or salt thereof,
Formyl group, acyl group, substituted or unsubstituted carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group, mercapto group, alkylthio group,
Arylthio group, sulfino group or salt thereof, arylsulfonyl group, substituted or unsubstituted sulfamoyl group, alkoxysulfonyl group, aryloxysulfonyl group, substituted or unsubstituted amino group, acylamino group, substituted or unsubstituted ureido group, alkoxy Carbonylamino group, aryloxycarbonylamino group,
Alkylsulfonylamino group, arylsulfonylamino group, substituted or unsubstituted sulfamoylamino group,
Examples thereof include a nitro group and a nitroso group. These substituents may be further substituted. Also, there may be two or more substituents as exemplified above.

Examples of the aralkyl group include a benzyl group and a phenethyl group. These substituents may have one or more substituents described in the alkyl group or aryl group, and the substituents may be further substituted.

The heterocyclic group is preferably a 5- or 6-membered one, and examples thereof include a furyl group, a thienyl group, a benzothienyl group, a pyridyl group and a quinoline group. These heterocyclic groups may have the same substituent as the above-mentioned substituted aryl group.

Examples of the alkylene group are methylene group, ethylene group, trimethylene group, propylene group and the like; examples of the arylene group are (o-, m-, p-) phenylene group, (1,4- etc.). There are naphthylene groups and the like; examples of cycloalkylene groups include cycloalkylene groups and the like. The divalent residue may have one or more of the substituents described for the alkyl group or the aryl group, and the substituent may be further substituted.

Of these, a compound in which R ₃ is an alkyl group having 3 or more carbon atoms or a cycloalkyl group is preferable. More preferably, R ₃ is a compound having an alkyl group having 3 to 10 carbon atoms or a cycloalkyl group.

Further, m is particularly preferably 1.

Specific examples of the compound represented by formula (III) in the present invention are shown below.

[0066]

[Chemical 18]

[0067]

[Chemical 19]

[0068]

[Chemical 20]

[0069]

[Chemical 21]

[0070]

[Chemical formula 22]

[0071]

[Chemical formula 23]

The acetylene compound of the general formula (III) of the present invention can be easily obtained from the condensation reaction of 4-ethynylaniline with an acid chloride of a carboxylic acid, as shown below.

[0073]

[Chemical formula 24]

The starting material 4-ethynylaniline is HELVET
It can be synthesized by the method described in ICA CHIMICA ACTA Vol. 54, p. 2066 (1971).

The content of the acetylene compound represented by the general formula (III) is preferably 10 ^-4 to 1 mol, particularly 10 ^{-3 to} 5 × 10 ^-1 mol per 1 m ² of the additive layer.

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 silver halide emulsion layers having light sensitivity in different spectral regions are combined. To use. For example, the blue layer,
There are a combination of three layers of a green-sensitive layer and a red-sensitive layer, a combination of a green-sensitive layer, a red-sensitive layer and an infrared-sensitive layer. 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.

In particular, a light-sensitive layer containing a yellow dye-donor compound, which is generally used, has a wavelength of 400 nm.
A halogenated emulsion (blue-sensitive emulsion) having a spectral sensitivity in the range of 500 nm to 500 nm, and a light-sensitive layer containing a magenta dye-donating compound in the photosensitive layer are spectrally sensitized in the range of 500 nm to 600 nm. Emulsion to the photosensitive layer containing a cyan dye-donor compound in the same manner.
This is a method of incorporating a halogenated emulsion (red-sensitive emulsion) spectrally sensitized to 700 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 blue sensitive layer, an intermediate layer, a magenta dye-donating compound-containing green sensitive layer, an intermediate layer, a yellow dye-donating compound-containing red 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. Each photosensitive layer is composed of two layers, each of which may contain a dye-donor compound and a halogenated emulsion, or only the upper layer may contain the halogenated emulsion and the lower layer may contain the dye-donor compound. It is also possible to achieve high sensitivity.

The heat-developable color light-sensitive material may 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 method for preparing the silver halide emulsion used in the present invention will be described in detail below.

(Basic Structure of Silver Halide Grain and Preparation Method) The silver halide which can be used in the present invention includes silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver iodochloride and chloroiodo. Any of silver bromide may be used, but silver iodobromide, silver chloride, silver bromide and silver chlorobromide containing 30 mol% or less of silver iodide are preferable.

The silver halide emulsion used in the present invention may be either a surface latent image type or an internal latent image type. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or an optical fogging. Further, so-called multi-structured particles having different halogen compositions inside and inside the particle may be used. Of the multi-structure grains, those having a double structure are sometimes called a core-shell emulsion.

The silver halide used in the present invention is preferably a multi-structured grain, and a core-shell emulsion is more preferable. However, the present invention is not limited to this.

The silver halide emulsion used in the present invention is preferably a monodisperse emulsion and is disclosed in JP-A-3-110555.
The coefficient of variation described in No. 20 is preferably 20% or less.
More preferably 16% or less, further preferably 10%
It is the following. However, the present invention is not limited to this monodisperse emulsion.

The average grain size of the silver halide grains used in the present invention is 0.1 μm to 2.2 μm, preferably 0.1 μm to 1.2 μm. The crystal habit of the silver halide grains may be cubic, octahedral, flat plate with a high aspect ratio, potato-like, or any other form. A cubic emulsion is more preferred.

Specifically, US Pat. No. 4,500,626, column 50, US Pat. No. 4,628,012, Research Disclosure (hereinafter abbreviated as RD) 17029 (197).
8 years), any of the silver halide emulsions described in JP-A No. 62-25159 can be used.

In the process of preparing the silver halide emulsion of the present invention, when a so-called desalting step for removing an excess salt is carried out, as a means for this purpose, gel washing of gelatin which has been known for a long time is carried out by Nudell water washing. Inorganic salts composed of polyvalent anions, such as sodium sulfate, anionic surfactants, anionic polymers (such as polystyrene sulfonic acid), or gelatin derivatives (such as aliphatic acylated gelatin, aromatic compounds) may be used. A precipitation method (flocculation) using acylated gelatin, aromatic carbamoylated gelatin, etc. may be used. Preferably, a precipitation method using a compound represented by a precipitation agent (a) or a precipitation agent (b) described later is used, but the present invention is not limited thereto. An ultrafiltration method may be used without using any of the above-mentioned settling agents. The removal of excess salt may be omitted.

The silver halide emulsion used in the present invention may contain heavy metals such as iridium, rhodium, platinum, cadmium, zinc, thallium, lead, iron and chromium for various purposes. These compounds may be used alone,
Moreover, you may use it in combination of 2 or more type. The addition amount depends on the purpose of use, but is generally about 10 ^-9 to 10 ^-3 mol per mol of silver halide. Further, when it is contained, it may be uniformly added to the particles, or may be localized on the surface or inside of the particles.

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.

Further, the preferable addition amount of iron used in the present invention
Is 10 per mol of silver halide. ^-7-10^-3In moles
More preferably 10^-6-10^-3It is a mole.

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 silver halide grains, a rhodan salt as a silver halide solvent, NH ₃ and a tetra-substituted thioether compound represented by the compound (a) described later or an organic thioether derivative described in JP-B-47-11386. Alternatively, the sulfur-containing compounds described in JP-A-53-144319 can be used.

At the stage of forming silver halide grains, nitrogen-containing compounds as described in JP-B-46-7781, JP-A-60-222842, JP-A-60-122935 and the like can be added. .

Gelatin is advantageously used as the protective colloid used in the preparation of the emulsion of the present invention and as the binder for other hydrophilic colloids, but hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, cellulose sulfates; sodium alginate, starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetals, poly -N-vinylpyrrolidone, polyacrylic acid,
Various synthetic hydrophilic polymer substances such as single or copolymers such as polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. can be used.

Examples of gelatin include lime-processed gelatin, acid-processed gelatin, bulletin, and society of gelatin.
The Scientific, Photography of Japan (Bull.Soc.Sci.Phot., Japan), No16: Page
30 (1966), an enzyme-treated gelatin may be used, and a hydrolyzed product or an enzymatically decomposed product of gelatin may also be used.

For other conditions, see the graph
(P.Glafkides), "Chemie et Physique Photographique"
[Published by Paul Montel, 1967),
GF Duffin, Photographic Emulsion Chemistry
Emulsion Chemistry) "(The Focal Press Th
e Focal Press, 1966), VL Zelikman et al, "Making and Coating Photographic Emulsion" (The Focal Press, 196).
4 years) and the like. Ie the acidic method,
Either the neutral method or the ammonia method may be used, and the method of reacting the soluble silver salt with the soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof.

A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one type of simultaneous mixing method, a method of keeping pAg constant in a liquid phase in which silver halide is produced, that is, a so-called controlled or double jet method can be used.

Further, in order to accelerate the grain growth, the addition concentration, the addition amount or the addition rate of the silver salt and the halogen salt to be added may be increased (JP-A-55-142329, JP-A-55-158124, US Pat. No. 3650757).

During or after grain formation, the surface of the silver halide grain may be replaced with halogen which forms a hardly soluble silver halide grain.

The reaction solution may be stirred by any known stirring method. The temperature and pH of the reaction solution during the formation of silver halide grains may be set arbitrarily. Preferred pH
The range of 2.2 to 6.0, more preferably 3.0 to
It is 5.5.

As the blue-sensitive layer emulsion used in the present invention, an emulsion as described in Japanese Patent Application No. 3-308225 is particularly preferable.

(Method of Adding Sensitizing Dye) The method of adding the sensitizing dye may be basically any time. That is, at the beginning of the formation of silver halide emulsion grains (may be added before nucleation),
On the way, after formation, or at the beginning, on the way, or after the desalting step, at the time of redispersion of gelatin, further before or after chemical sensitization, during, or at the time of preparing a coating solution. It is preferably added during or after the formation of silver halide grains or before or after the chemical sensitization. The addition after the chemical sensitization is to add the sensitizing dye after all the chemicals necessary for the chemical sensitization are added.

It may be present in the reaction system of a soluble silver salt (eg silver nitrate) and a halide (eg potassium bromide) before the silver halide grains are formed as described in US Pat. No. 4,183,756. U.S. Pat. No. 42
As described in No. 25666, it may be present in the above reaction system after nucleation of silver halide grains and before completion of the silver halide grain formation step. A sensitizing dye may be present in the reaction solution at the same time as the formation of silver halide grains, that is, at the same time when the silver salt and the halide are mixed. It is more excellent in storage stability and gradation under high temperature conditions.

Concentration of the added liquid, solvent, time of addition (addition at once or addition over time), temperature, pH
May be any condition. Further, it may be added on the liquid surface or in the liquid. These conditions are described in JP-A 3-1
It is described in detail in No. 10555.

(Type of Sensitizing Dye) The sensitizing dyes used in the emulsion used in the present invention include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and Hemioxonol dyes are included.

Specifically, US Pat. No. 4,617,257
No. 59-180550, 60-14033.
No. 5, RD17029 (1978) pages 12 to 13 and the like.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization.

Along with the sensitizing dye, a dye having no spectral sensitizing effect by itself or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (eg, US Pat. No. 3615641, Japanese Patent Application No. 6
No. 1-222694, etc.).

In the present invention, in any of the above-mentioned addition methods, the total addition amount of the sensitizing dye may be added at one time,
Also, it may be added in several divided portions. Further, the sensitizing dye may be added in the form of a mixture with a soluble silver salt and / or a halide.

The sensitizing dye is added by dissolving it in an organic solvent or water (which may be alkaline or acidic) which is compatible with water, such as methanol, ethanol, propanol, fluorinated alcohol, methyl cellosolve, dimethylformamide and acetone. Or two or more of the above may be used in combination. It may also be added in the form of dispersion in a water / gelatin dispersion or in the form of freeze-dried powder. Further, it may be added in the form of powder or solution dispersed with a surfactant.

The sensitizing dye used in the emulsion of the present invention may be those described in, for example, JP-A-3-296745 and 4-31854.

The amount of the sensitizing dye used is appropriately 0.001 g to 20 g, preferably 0.01 to 2 g, per 100 g of silver used for producing an emulsion.

In the present invention, the compound represented by Chemical formula 17 can be included. The compound represented by Chemical formula 17 is often used for supersensitization, improvement of storage stability, and suppression of change in sensitivity of the coating solution over time. The light-sensitive material of the present invention has more effective effects.

[0116]

[Chemical 25]

In the above formula, A represents a divalent aromatic residue. R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are each a hydrogen atom, hydroxy group, alkyl group, alkoxy group, aryloxy group, halogen atom, heterocyclic nucleus, heterocyclylthio group, alkylthio group, arylthio group, amino group, substituted or It represents an unsubstituted alkylamino group, a substituted or unsubstituted arylamino group, a substituted or unsubstituted aralkylamino group, a heterocyclylamino group, an aryl group, a heterocyclyloxy group, or a mercapto group. However, A,
At least one of R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ has a sulfo group.

W ₁ and W ₂ are each -CH = or -N
Represents =. However, at least _one of W ₁ and W ₂ represents -N =.

The compounds represented above are known compounds as supersensitizers of sensitizing dyes in general light-sensitive materials for wet development processing (US Pat. No. 2875058, US Pat. No. 3,695,888, JP Kaisho 59-192242
And Japanese Patent Application Laid-Open No. 59-191032) and also known as supersensitizers in heat-developable color light-sensitive materials (See Japanese Patent Application Laid-Open No. 59-180550).

Details and specific examples of the above-mentioned compounds are described in Japanese Patent Application No.
-310985.

(Chemical Sensitization) The silver halide emulsion used in the present invention can be used as it is without being chemically sensitized, but it is preferable to chemically sensitize to increase the sensitivity. The chemical sensitization may be sulfur sensitization, gold sensitization, reduction sensitization, or a combination thereof.

In addition, chemical sensitization with a compound containing a chalcogen element other than sulfur such as selenium and tellurium, or chemical sensitization with a noble metal such as palladium and iridium may be combined with the above chemical sensitization.

Also, 4-hydroxy-6-methyl-
A method of adding an inhibitor such as a nitrogen-containing heterocyclic compound represented by (1,3,3a, 7) -tetraazaindene is also preferably used. The preferred range of addition is silver halide 1
It is 10 ⁻¹ to 10 ⁻⁵ mol per mol.

The pH during chemical sensitization is preferably 5.3 to.
It is 10.5, and more preferably 5.5 to 9.5.

The sulfur sensitizer is a compound containing sulfur capable of reacting with active gelatin or silver, and includes, for example, thiosulfate, allylthiocarbamide, thiourea, allylisothiacyanate, cystine, p-toluenethiosulfonic acid. ,
Rhodan, mercapto compounds and the like are used. Others, US Pat. Nos. 1,574,944 and 2,410,689
Nos. 2278947, 2728668, 3656955 and the like can also be used.

The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg / m ^{2 to} 10 g / m ² in terms of silver.

A hydrophilic binder is preferably used for the binder of the constituent layers of the light-sensitive material and the dye fixing element. Examples thereof include those described on pages (26) to (28) of JP-A-62-253159. Specifically, a transparent or translucent hydrophilic binder is preferable, and for example, gelatin, a protein such as gelatin derivative, or a cellulose derivative,
Natural compounds such as polysaccharides such as starch, gum arabic, dextran, pullulan and polyvinyl alcohol,
Examples thereof include polyvinylpyrrolidone, acrylamide polymer, and other synthetic polymer compounds. In addition, JP-A-62-1
No. 245260 and the like, a superabsorbent polymer, that is, a homopolymer of a vinyl monomer having —COOM or —SO ₃ M (M is a hydrogen atom or an alkali metal), or a copolymerization of the vinyl monomers with each other or with other vinyl monomers. Combined (for example, sodium methacrylate, ammonium methacrylate, Sumika Gel L- manufactured by Sumitomo Chemical Co., Ltd.)
5H) is also used. These binders can be used in combination of two or more.

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 1
The amount is preferably 20 g or less per m ² , particularly 10 g or less, and more preferably 7 g or less.

The constituent layers (including the back layer) of the light-sensitive material or the dye-fixing element are used for the purpose of improving physical properties of the film such as dimensional stabilization, curl prevention, adhesion prevention, film cracking prevention and pressure increase / decrease prevention. Various polymer latices can be included. Specifically, any of the polymer latexes described in JP-A Nos. 62-245258, 62-136648, 62-110066 and the like can be used. In particular,
When a polymer latex having a low glass transition point (40 ° C. or less) is used in the mordant layer, cracking of the mordant layer can be prevented, and when a polymer latex having a high glass transition point is used in the back layer, a curl preventing effect can be obtained. .

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 the reducing agent used in the present invention include:
U.S. Pat. No. 4,500,626, columns 49-50, 44
No. 83, col. 31, columns 31-43;
No. 4,590,152, JP-A-60-140335
(17)-(18), ibid. 57-40245, ibid. 56-138.
No. 736, No. 59-178458, No. 59-5383.
No. 1, 59-182449, 59-182450.
Nos. 60-119555, 60-128436 to 60-128439, 60-19854.
No. 0, No. 60-181742, No. 61-259253.
Nos. 62-244044, 62-131253 to 62-131256, European Patent No. 2207.
There are reducing agents and reducing agent precursors described on pages 78 to 96 of No. 46A2.

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.

The electron transfer agent or its precursor can be selected from the above-mentioned reducing agents or its precursors. It is desirable that the electron transfer agent or its precursor has a mobility higher than that of the diffusion resistant reducing agent (electron donor). A particularly useful electron transfer agent is 1-phenyl-3
-Pyrazolidones or aminophenols.

The diffusion-resistant reducing agent (electron donor) used in combination with the electron transfer agent may be any one of the above-mentioned reducing agents which does not substantially move in the layer of the light-sensitive material.
Hydroquinones, sulfonamide phenols, sulfonamide naphthols, JP-A-53-11 are preferred.
Examples thereof include compounds described as electron donors in No. 0827, and dye-donating compounds having diffusion resistance and reducing properties described below.

Further, these reducing agents are represented by the general formula (I) above.
You may use together with the compound shown by and (II).

In the present invention, the reducing agent is added in an amount of 0.01 to 20 mol, and particularly preferably 0.1 to 1 mol of silver.
10 to 10 mol.

The dye-donor compound (also referred to as dye-donor substance) used in the present invention forms a diffusible (mobile) dye corresponding to this reaction when reduced to silver ion under high temperature conditions. It is a compound that does or releases.

Examples of the dye-donating compound that can be used in the present invention include a compound (coupler) which 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 are TH James
"The Theory of the Photographic Process" Fourth Edition 2
91-334 pages, and 354-361 pages, JP-A-58
-123533, 58-149046, 58-
No. 149047, No. 59-111148, No. 59-1
24399, 59-174835, and 59-23.
1539, 59-231540, 60-295.
No. 0, No. 60-2951, No. 60-14242, No. 60-23474, No. 60-66249 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-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 a photosensitive silver salt having an imagewise latent image. Or, conversely, a difference is caused in the diffusivity of the compound represented by (Dye-Y) _n -Z, or Dye is released, and the released Dye and (Dye-Y) _n -Z Represents a group having a property of causing a difference in diffusibility between them, n represents 1 or 2, and when n is 2, two Dye-Y may be the same or different.

Specific examples of the dye donating compound represented by the general formula [LI] include the following compounds. And form a diffusible dye image (negative dye image) corresponding to the development of silver halide.

A compound (DDR coupler) which is a coupler having a diffusible dye as a leaving group and releases the diffusible dye by a reaction with an oxidized form of a reducing agent. Specifically, British Patent No. 1330524, Japanese Patent Publication No. 48-39165, U.S. Patent Nos. 3443940, 4474867, 448.
3914 and the like.

A compound (DRR compound) which is reducible to a silver halide or an organic silver salt and releases a diffusible dye when its partner is reduced. Since this compound does not need to use another reducing agent, it is preferable because there is no problem of image contamination due to oxidative decomposition products of the reducing agent. Typical examples thereof are U.S. Pat. Nos. 3,928,312, 4,053,312 and 405.
No. 5428, No. 4336322, JP-A-59-658.
No. 39, No. 59-69839, No. 53-3819,
51-104343, RD17465, U.S. Pat. Nos. 3,725,062, 3,728,113 and 3,443.
939, JP-A-58-116537, 57-17.
9840, U.S. Pat. No. 4,500,626 and the like. 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 which the compounds (1) to (3) described in the U.S. patents, (10) ~ (13), (16) ~ (19), (28)
To (30), (33) to (35), (38) to (40), and (42) to (64) are preferable. Further, the compounds described in US Pat. No. 4,639,408, columns 37 to 39 are also useful.

Other than the above-mentioned couplers and dye-donating compounds other than the general formula [LI], dye silver compounds in which an organic silver salt and a dye are bound (Research Disclosure, May 1978, pp. 54-58). , Etc., azo dyes used in the heat developable silver dye bleaching method (US Pat.
957, Research Disclosure, 1976.
, April issue, pages 30 to 32), leuco dyes (US Pat. Nos. 3,985,565 and 4,022,617), and the like can also be used.

Hydrophobic additives such as dye-donating compounds and antidiffusive reducing agents can be incorporated into the layer of the photographic material by known methods such as the method described in US Pat. No. 2,322,027. In this case, JP-A-59-83154,
59-178451, 59-178452, 59-178453, 59-178454, 5
9-178455, 59-178457 and the like, a high boiling point organic solvent, if necessary, a boiling point of 50 ° C.
It can be used in combination with an organic solvent having a low boiling point of up to 160 ° C.

The amount of the high boiling point organic solvent is 10 g or less, preferably 5 g or less based on 1 g of the dye-donor compound used. Further, 1 cc or less, more preferably 0.5 cc or less, and especially 0.3 cc or less is suitable for 1 g of the binder.

JP-B-51-39853, JP-A-51-
The dispersion method using a polymer described in 59943 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, those listed as surfactants on pages (37) to (38) of JP-A-59-157636 can be used.

In the present invention, a compound capable of activating development and stabilizing an image at the same time can be used in the light-sensitive material. 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, a dye fixing element is used together with a light-sensitive material. The dye fixing element may be applied separately on a support different from the light-sensitive material, or may be applied on the same support as the light-sensitive material. Regarding the relationship between the light-sensitive material and the dye fixing element, 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 application.

The dye fixing element 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. Specific examples thereof include US Pat. No. 4,500,626, columns 58 to 59 and JP-A-61-88256, (32) to (41).
The mordant described in the above pages, JP-A Nos. 62-244043 and 6
Examples thereof include those described in No. 2-244036. Further, a dye-receptive polymer compound as described in US Pat. No. 4,463,079 may be used. If necessary, the dye fixing element can be provided with auxiliary layers such as a protective layer, a peeling layer and an anti-curl layer. In particular, it is useful to provide a protective layer.

In the constituent layers of the light-sensitive material and the dye-fixing element, a plasticizer, a slipping agent, or a high boiling point organic solvent can be used as an agent for improving the releasability of the light-sensitive material and the dye-fixing element. A specific example is (25) of JP-A-62-253159.
Page, No. 62-245243 and the like.

Further, various silicone oils (all silicone oils from dimethylsilicone oil to modified silicone oils obtained by introducing various organic groups into dimethylsiloxane) can be used for the above purpose. As examples thereof, various modified silicone oils described in "Modified Silicone Oil" technical materials p.6 to 18B issued by Shin-Etsu Silicone Co., Ltd., particularly carboxy modified silicone (trade name X-22-3710) are effective. .

Further, JP-A-62-215953 and 63
The silicone oil described in No. 46449 is also effective.

An anti-fading agent may be used in the light-sensitive material and the dye fixing element. As the anti-fading agent, there are, for example, an antioxidant, an ultraviolet absorber, or a kind of metal complex.

Examples of antioxidants include chroman compounds, coumarane compounds, phenol compounds (eg hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. The compounds described in JP-A-61-159644 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-46-2784)
Etc.) and others, JP-A Nos. 54-48535 and 62-
There are compounds described in Nos. 136641 and 61-88256. Further, the ultraviolet absorbing polymer described in JP-A-62-260152 is also effective.

Examples of metal complexes include US Pat. No. 4,2411,
No. 55, No. 4245018, Columns 3 to 36, No. 4254.
195, columns 3 to 8, JP-A Nos. 62-174741, 61-88256, pages (27) to (29), 63-19924.
No. 8, JP-A-1-75568, and JP-A-1-74272.

Examples of useful anti-fading agents are disclosed in JP-A-62-21.
5272 (125)-(137). An anti-fading agent for preventing fading of the dye transferred to the dye fixing element may be contained in the dye fixing element in advance,
The dye fixing element may be supplied from the outside such as a light-sensitive material.

The above-mentioned antioxidant, ultraviolet absorber and metal complex may be used in combination.

A fluorescent whitening agent may be used in the light-sensitive material and the dye fixing element. In particular, it is preferable to incorporate a fluorescent whitening agent in the dye fixing element or supply it from the outside such as a light-sensitive material. For example, see “The Chemis” edited by K. Veenkataraman.
try of Synthetic Dyes ", Volume V, Chapter 8, JP-A-61-
The compound described in 143752 etc. can be mentioned. More specifically, stilbene compounds, coumarin compounds, biphenyl compounds, benzoxazolyl compounds, naphthalimide compounds, pyrazoline compounds, carbostyryl compounds and the like can be mentioned. The fluorescent whitening agent can be used in combination with an anti-fading agent.

As the hardener used in the constituent layers of the light-sensitive material and the dye fixing element, US Pat. No. 4,678,739, No. 41 is used.
Column, JP-A-59-116655 and JP-A-62-24526.
The hardeners described in No. 1 and No. 61-18942 are listed. More specifically, aldehyde hardeners (formaldehyde etc.), aziridine hardeners, epoxy hardeners, vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane, etc.), N-
Examples thereof include methylol type hardeners (dimethylolurea etc.) and polymer hardeners (compounds described in JP-A-62-234157).

In the constituent layers of the light-sensitive material and the dye-fixing element, various surfactants can be used for the purpose of coating aid, improvement of peeling property, improvement of sliding property, antistatic property, acceleration of development and the like. Specific examples of the surfactant are disclosed in JP-A-62-173463.
No. 62-183457 and the like.

The constituent layers of the light-sensitive material and the dye-fixing element may contain an organic fluoro compound for the purpose of improving slipperiness, preventing electrification, improving releasability and the like. Typical examples of organic fluoro compounds include Japanese Patent Publication No. 57-9053, columns 8 to 17,
Fluorine-based surfactants described in JP-A-61-29444, JP-A-62-135826 and the like, oil-like fluorinated compounds such as fluorinated oil, or solid fluorinated compound resins such as tetrafluoroethylene resin Hydrophobic fluorine compounds may be mentioned.

A matting agent can be used in the light-sensitive material and the dye fixing element. Matting agents such as silicon dioxide, polyolefins, polymethacrylates, etc.
In addition to the compounds described on page 1-88256 (29), benzoguanamine resin beads, polycarbonate resin beads, A
Japanese Patent Laid-Open Nos. 63-274944 and 6-96, such as S resin beads.
There are compounds described in 3-274952.

In addition, the constituent layers of the light-sensitive material and the dye-fixing element 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 No. 61-88256, pages (26) to (32).

In the present invention, an image formation accelerator can be used in the light-sensitive material and / or the dye fixing element.
The image forming accelerator includes a silver salt oxidizing agent and a reducing agent, which promotes oxidation-reduction reaction, formation of dye from dye-donor substance, decomposition of dye or release of diffusible dye, and light-sensitive material layer. It has functions such as promoting the migration of dyes to the dye-fixing layer. From the physicochemical functions, bases or base precursors, nucleophilic compounds, high boiling organic solvents (oils), thermal solvents, surfactants, silver or It is classified into compounds that interact with silver ions. However, these substance groups generally have a composite function, and usually have some of the above-mentioned accelerating effects together. These details are described in US Pat. No. 4,678,739, columns 38 to 40.

Examples of the base precursor include salts of organic acids and bases that are decarboxylated by heat, compounds that release amines by intramolecular nucleophilic substitution reaction, Rossen rearrangement or Beckmann rearrangement. A specific example is US Pat. No. 45114.
93, JP-A-62-65038 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, it is preferable to add a base and / or a base precursor to the dye-fixing element in order to improve the storability of the light-sensitive material.

In addition to the above, European Patent Publication 210660
No. 4,740,445, and combinations of sparingly soluble metal compounds and compounds capable of complex-forming reaction with metal ions constituting the sparingly soluble metal compounds (referred to as complex-forming compounds), and JP-A-61-232451. Compounds that generate a base by electrolysis as described in No. 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 light-sensitive material and the dye fixing element.

In the present invention, various development terminators can be used in the light-sensitive material and / or the dye fixing element for the purpose of always obtaining a constant image against variations in processing temperature and processing time during development.

The term "development stopping agent" as used herein means, after proper development,
It is a compound that rapidly neutralizes or reacts with a base to lower the concentration of the base in the film to stop development, or a compound that interacts with silver and a silver salt to suppress development. In particular,
Examples thereof include acid precursors that release an acid upon heating, electrophilic compounds that undergo a substitution reaction with a coexisting base upon heating, or nitrogen-containing heterocyclic compounds, mercapto compounds and precursors thereof. For more details, see JP-A-62-2531.
No. 59 (31) to (32).

In the present invention, the support for the light-sensitive material and the dye-fixing element is one that can withstand the processing temperature. Generally, paper, synthetic polymer (film)
Is mentioned. Specifically, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or those films containing pigments such as titanium oxide, and polypropylene are used. The film method synthetic paper, 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 and the like are used.

These can be used alone or
It can also be used as a support having one or both sides laminated with a synthetic polymer such as polyethylene.

In addition to this, JP-A-62-253159 (2
The supports described on pages 9 to 31 can be used.

On the surface of these supports, a hydrophilic binder and a semiconductive metal oxide such as alumina sol or tin oxide,
You may apply carbon black and other antistatic agents.

As a method for exposing and recording an image on a light-sensitive material, for example, a method of directly photographing a landscape or a person by using a camera, a method of exposing through a reversal film or a negative film by using a printer or an enlarger, A method of scanning and exposing an original image through a slit or the like using an exposure device of a copying machine, a method of exposing image information by emitting light from a light emitting diode or various lasers through an electric signal, a CRT, a liquid crystal display of image information, There is a method of outputting to an image display device such as an electroluminescence display and a plasma display, and exposing directly or through an optical system.

In the light-sensitive element of the present invention, the layer containing the yellow dye-donor compound has blue light-sensitivity, the layer containing the magenta dye-donor compound has green light-sensitivity, and the layer containing the cyan dye-donor compound has red color. In the case of having photosensitivity, the following methods of exposing and recording the image can be considered. If the light sensitivity is high, for example, if it is ISO 10 or more (if it is a still object, it is possible to shoot even if the sensitivity is lower), it is possible to put it in a camera and shoot. In this case, if the support of the image-receiving paper for receiving an image from the photosensitive element is transparent, it can be used as a color negative film, and a color print material for receiving an image from this negative is also designed by the heat-developable photosensitive element of the present invention. it can.

In this case, it is possible to design a minilab heat-development mold which is generally used in the present industry. In general, a negative film type photothermographic material that has been photographed is coated with water, transferred by heat development, and dried to obtain a negative film, using a transparent image-receiving film. This negative film is continuously or intermittently placed in an automatic exposure unit. A negative image is stretched to the required size and exposed on a print-type photosensitive element that is optimally designed for photographic properties (spectral sensitivity, gradation, color reproduction, sensitivity, etc.) for color printing. The exposed roll- or sheet-shaped photosensitive element can be coated with water, transferred by heat development, and dried to obtain a photographed color image on the image receiving paper.

Further, by using the processed negatives of the photographic industry companies such as Fuji Photo Film, Eastman Kodak, Konica, Agfagewald, etc., the image is exposed to the print type photosensitive element continuously or intermittently and the heat is applied. Developing is a potential application. Further, a process for processing a negative with a commercially available device for developing the above negative, and using this negative, continuously or intermittently automatically performing exposure, water coating, heat development transfer, and drying on the photosensitive element of the present invention. It is also possible to design the machine. Naturally, it is necessary to design the thermal development processor for printing in accordance with the processing speed or the transport speed of the negative processing machine. Whether it is continuous or intermittent, the faster the negative processing speed is, the more the negative processing speed and the processing time for heat development need to be calculated, and the size of the heat development transfer section needs to be designed. Further, providing a reservoir for speed matching between the negative processor and the heat-developable print processor is one solution.

As a light source for recording an image on a photosensitive material,
As described above, the natural light, tungsten lamp, light emitting diode, laser light source, CRT light source, etc.
The light source described in 500626, column 56 can be used.

Image exposure can also be performed using a wavelength conversion element in which a nonlinear 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 an electric field that appears when a strong optical electric field such as laser light is applied, and includes lithium niobate and potassium dihydrogen phosphate (KD).
P), lithium iodate, BaB ₂ O _{4 and} other inorganic compounds, urea derivatives, nitroaniline derivatives, for example, nitropyridine-N such as 3-methyl-4-nitropyridine-N-oxide (POM). -Oxide derivatives, JP-A-61-53462 and JP-A-62-210432
The compounds described in No. 10 are preferably used. As the form of the wavelength conversion element, a single crystal high waveguide type, a fiber type and the like are known, and any of them is useful.

[0187] Further, the image information is a video camera,
An image signal obtained from an electronic still camera or the like, a television signal represented by Nippon Television Signal Standard (NTSC),
An image signal obtained by dividing an original image into a large number of pixels such as a scanner, or an image signal created by using a computer represented by CG and CAD can be used.

The light-sensitive material and / or the dye fixing element are
It may have a form having a conductive heating element layer as a heating means for heat development or dye diffusion transfer. In this case, the transparent or opaque heating element is disclosed in
Those described in, for example, the specification of 145544 can be used.
Note that these conductive layers also function as antistatic layers.

The heating temperature in the heat development step is about 50 ° C. to about 2 ° C.
It can be developed at 50 ° C, but especially from about 80 ° C to about 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 set within the range from the temperature in the heat development step to room temperature, but especially 50 ° C.
Above all, it is more preferable that the temperature is lower by about 10 ° C. than the temperature in the heat development step.

Although the migration of the dye occurs only by heat,
Solvents may be used to facilitate dye transfer. Also,
As described in detail in JP-A-59-218443 and JP-A-61-238056, 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. is there. In this method, the heating temperature is 50 ° C.
As described above, the boiling point of the solvent or less is preferable.

Examples of the solvent used for accelerating the development and / or transferring the diffusible dye to the dye-fixing layer include water or a basic aqueous solution containing an inorganic alkali metal salt or an organic base (these bases). Examples thereof include those described in the section of the image formation accelerator). Further, a low boiling point solvent, or a mixed solution of a low boiling point solvent and water or a basic aqueous solution can be used. Further, a surfactant, an antifoggant, a sparingly soluble metal salt and a complex-forming compound, etc. may be contained in the solvent.

These solvents can be used by a method of applying them to the dye fixing element, the light-sensitive material or both.
The amount used may be as small as the weight of the solvent corresponding to the maximum swelling volume of the entire coating film or less (particularly the amount of the solvent corresponding to the maximum swelling volume of the entire coating film less the weight of the total coating film).

A method for applying a solvent to the photosensitive layer or the dye fixing layer is described in, for example, JP-A-61-147244 (2).
There is a method described on page 6). Alternatively, the solvent may be contained in microcapsules, and may be incorporated in the light-sensitive material or the dye-fixing element or both in advance.

In order to promote dye transfer, a method in which a hydrophilic thermal solvent that is solid at room temperature and dissolves at high temperature is incorporated in the light-sensitive material or the dye fixing element can also be used. The hydrophilic thermal solvent may be incorporated in either the light-sensitive material or the dye fixing element, or may be incorporated in both. The layer to be incorporated may be any of an emulsion layer, an intermediate layer, a protective layer and a dye fixing layer, but it is preferably incorporated in the dye fixing layer and / or its adjacent layer. Examples of hydrophilic thermal solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes, and other heterocycles.

Further, in order to promote dye transfer, a high-boiling point organic solvent may be contained in the light-sensitive material and / or the dye-fixing element.

As a heating method in the developing and / or transferring step, a heated block or plate is contacted, or a hot plate, a hot presser, a heat roller, a halogen lamp heater, an infrared or far infrared lamp heater, etc. is contacted. And passing through a high temperature atmosphere.

The pressure conditions and the method of applying pressure when the light-sensitive element and the dye-fixing element are superposed and brought into close contact with each other are described in JP-A No. 6-63.
The method described in page 1-147244 (27) can be applied.

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
No. 5247, No. 59-177547, No. 59-181.
No. 353, No. 60-18951, No. 62-259.
The device described in No. 44 is preferably used.

[0199]

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

Light-Sensitive Silver Halide Emulsion (1) [For Red-Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (20 g of gelatin in 480 ml of water, 0.5 g of potassium bromide, 3 parts of sodium chloride).
g and 30 mg of the compound (a) were added and kept at 45 ° C.), the solutions (I) and (II) in Table 1 were simultaneously added at an equal flow rate for 20 minutes. After 5 minutes, solution (III) and solution (IV) in Table 1 were added simultaneously at the same flow rate for 25 minutes. In addition, 10 minutes after the start of addition of the liquids (III) and (IV), an aqueous solution of a gelatin dispersion of the dye (containing 105 g of water, 1 g of gelatin, 70 mg of the dye (a), 139 mg of the dye (b), and 5 mg of the dye (c)) was added. (Incubated at 45 ° C.) was added over 20 minutes.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin and 70 mg of compound (b) were added,
The pH was adjusted to 6.2 and the pAg was adjusted to 7.7, and 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 2
60 mg, sodium thiosulfate 4.2 mg, and chloroauric acid 1.8 mg were sequentially added for optimum chemical sensitization at 60 ° C., and then antifoggant (1) 230 mg was added, followed by cooling. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.30 μm was obtained.

[0203]

[Table 1]

[0204]

[Chemical formula 26]

[0205]

[Chemical 27]

[0206]

[Chemical 28]

Photosensitive Silver Halide Emulsion (2) [For Red-sensitive Emulsion Layer] Well-stirred gelatin aqueous solution (gelatin 20 g, potassium bromide 0.5 g, sodium chloride 6 in 783 ml of water).
g and 30 mg of the compound (a) were added and kept at 65 ° C.), the solutions (I) and (II) in Table 2 were simultaneously added at an equal flow rate for 30 minutes. After 5 minutes, solution (III) and solution (IV) in Table 2 were further added simultaneously at an equal flow rate for 15 minutes. Also (III), (IV)
Two minutes after the start of the addition of the solution, an aqueous solution of a gelatin dispersion of a pigment (0.9 g of gelatin in 76 ml of water, 76 mg of pigment (a),
The dye (b) (150 mg) and the dye (c) (5 mg) which had been kept at 50 ° C.) were added over 18 minutes.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin and 100 mg of compound (b) were added to adjust pH to 6.2 and pAg to 7.8, and 4-hydroxy-6-methyl- 178 mg of 1,3,3a, 7-tetrazaindene, 2.8 mg of sodium thiosulfate and 1.2 mg of chloroauric acid were sequentially added every few minutes, and optimal chemical sensitization was performed at 60 ° C. (about 60 minutes). Antifoggant (2) 16
After adding 5 mg, it was cooled. Thus, a monodisperse cubic silver chlorobromide emulsion 635 having an average grain size of 0.50 μm
g was obtained.

[0209]

[Table 2]

[0210]

[Chemical 29]

Light-Sensitive Silver Halide Emulsion (3) [For Red-Sensitive Emulsion Layer] Well-stirred gelatin aqueous 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 45 ° C.), the solutions (I) and (II) in Table 2 were simultaneously added at an equal flow rate for 20 minutes. After 5 minutes, solution (III) and solution (IV) in Table 2 were simultaneously added at the same flow rate for 25 minutes.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin and 90 mg of compound (b) were added,
The pH was adjusted to 6.2 and the pAg was adjusted to 7.7, 500 mg of a ribonucleic acid degradation product and 2 mg of trimethylthiourea were added, and the temperature was 60 ° C.
After optimum chemical sensitization for about 50 minutes, 4-hydroxy-6
-Methyl-1,3,3a, 7-tetrazaindene 225
mg, dye (d) 64 mg, and KBr 500 mg were sequentially added, and then cooled. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.30 μm was obtained.

[0213]

[Table 3]

[0214]

[Chemical 30]

Light-Sensitive Silver Halide Emulsion (4) [For Red-Sensitive Emulsion Layer] The same procedure as in Photosensitive Silver Halide Emulsion (3) except that the liquid of Table 4 was used instead of the liquid of Table 4. 640 g of a monodisperse cubic silver chlorobromide emulsion having a size of 0.3 μm was obtained.

[0216]

[Table 4]

Light-Sensitive Silver Halide Emulsion (5) [For Red-Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 2 g of sodium chloride and compound (a) 3 in 600 ml of water).
0 mg was added and kept at 45 ° C.) except that the solution of Table 5 was used in place of Table 4 in the photosensitive silver halide emulsion (3). 640 g of dispersed cubic silver chloride emulsion was obtained.

[0218]

[Table 5]

Light-Sensitive Silver Halide Emulsion (6) [For Red-Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (20 g of gelatin in 630 ml of water, 0.3 g of potassium bromide and 2 g of sodium chloride).
g and 15 mg of the compound (a) were added and kept at 45 ° C.), the solutions (I) and (II) in Table 6 were simultaneously added at an equal flow rate for 15 minutes. After 5 minutes, solution (III) and solution (IV) in Table 6 were further added simultaneously at an equal flow rate for 35 minutes. In addition, 75 minutes of a 0.5% methanol solution of the sensitizing dye (a) was added from 25 minutes after 18 minutes after the addition of the solution (III) was started.

After washing with water and desalting by a conventional method (using the precipitating agent (a) at pH = 4.1), 22 g of lime-treated ossein gelatin and 90 mg of the compound (b) were added to adjust the pH to 6. 0, pAg was adjusted to 7.9, and then sodium thiosulfate 6 mg 4-hydroxy-6-methyl-at 60 ° C.
Optimal chemical sensitization was performed with 120 mg of 1,3,3a, 7-tetrazaindene. Thus, the average particle size is 0.3
630 g of a monodisperse cubic silver chlorobromide emulsion having a size of 1 μm and a coefficient of variation of 10.2% was obtained.

[0221]

[Table 6]

[0222]

[Chemical 31]

Photosensitive Silver Halide Emulsion (7) [For Green Sensitive Emulsion Layer] Well-stirred gelatin aqueous solution (gelatin 20 g, potassium bromide 0.5 g, sodium chloride 4 in 690 ml of water).
g and 15 mg of the compound (a) and the mixture was kept at 48 ° C.), the solutions (I) and (II) in Table 7 were simultaneously added at an equal flow rate for 8 minutes. After 10 minutes, solution (III) and solution (IV) in Table 7 were added simultaneously at the same flow rate for 32 minutes. Also (III), (IV)
One minute after the end of the addition of the solution, an aqueous solution of a gelatin dispersion of dye (2.5 g of gelatin in 100 ml of water, 250 of dye (e))
which contained mg and was kept warm at 45 ° C.) were added all at once.

After washing with water and desalting by a conventional method, 20 g of lime-treated ossein gelatin and 50 mg of compound (b) were added,
The pH was adjusted to 6.0 and the pAg was adjusted to 7.6, and 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 2
66 mg and 2.8 mg of sodium thiosulfate were sequentially added for optimum chemical sensitization at 68 ° C., and antifoggant (2) 165
After adding mg, the mixture was cooled. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.27 μm
Got

[0225]

[Table 7]

[0226]

[Chemical 32]

Photosensitive Silver Halide Emulsion (8) [For Green Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (20 ml of gelatin, 0.3 g of potassium bromide and 6 g of sodium chloride in 700 ml of water).
g and 15 mg of the compound (a) were added and kept at 55 ° C.), the solutions (I) and (II) in Table 8 were simultaneously added at an equal flow rate for 20 minutes. After 10 minutes, the liquids (III) and (IV) in Table 8 were further added.
The solution was added simultaneously at an equal flow rate for 20 minutes. Also (III), (I
One minute after the end of the addition of the liquid V), an aqueous solution of a gelatin dispersion of the dye (1.8 g of gelatin in 180 ml of water, 180 mg of the dye (e))
Which was kept at 45 ° C.) was added all at once.

After washing with water and desalting by a conventional method, 20 g of lime-treated ossein gelatin was added to adjust pH to 6.0 and pAg to 7.6, and sodium thiosulfate 1 mg and 4-hydroxy-6-methyl-1 were added. , 3,3a, 7-Tetrazaindene (47 mg) and chloroauric acid (0.6 mg) were added for optimum chemical sensitization at 68 ° C., and then antifoggant (2) (165 mg) was added, followed by cooling. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.45 μm was obtained.

[0229]

[Table 8]

Photosensitive Silver Halide Emulsion (9) [For Green Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (20 ml 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 45 ° C.), the solution (II) in Table 9 was added 10 seconds after the addition was started, and the solution (I) was added over 9 minutes. The end is simultaneous. Five minutes after that, the addition of the solutions (III) and (IV) in Table 9 was started at the same time. After 33 minutes, the addition of solution (IV) was completed, and 10 seconds later, the addition of solution (III) was completed. Three minutes after the completion of this addition, a dye solution in methanol (450 mg of dye (e) in 90 ml of methanol) was added all at once.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin and 90 mg of compound (b) were added,
The pH was adjusted to 6.0 and the pAg was adjusted to 7.8, and sodium thiosulfate 4.8 mg and 4-hydroxy-6-methyl-1,
3,3a, 7-Tetrazaindene was added and optimal chemical sensitization was performed at 68 ° C, and then 150 mg of antifoggant (2) was added, followed by cooling. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.30 μm was obtained.

[0232]

[Table 9]

Light-Sensitive Silver Halide Emulsion (10) [For Blue-Sensitive Emulsion Layer] Well-stirred gelatin aqueous solution (gelatin 20 g, potassium bromide 0.5 g, sodium chloride 5 in 690 ml of water).
g and 15 mg of the compound (a) and the mixture was kept at 51 ° C.), the solutions (I) and (II) in Table 10 were simultaneously added at an equal flow rate for 8 minutes. After 10 minutes, liquid (III) and (I
Solution V) was added simultaneously at an equal flow rate for 32 minutes. Also (III),
One minute after the addition of the liquid (IV) was completed, 220 mg of the dye (f) and 1 g of the dye (g) were dissolved in 95 ml of water and 5 ml of methanol.
(Containing 10 mg and kept at 45 ° C.) was added all at once.

After washing and desalting in the usual way, 22 g of lime-treated ossein gelatin and 100 mg of the compound (b) were added to adjust pH to 6.0 and pAg to 7.8, and sodium thiosulfate (4.8 mg and 4 mg) was added. -Hydroxy-6-methyl-
1,3,3a, 7-Tetrazaindene was added for optimum chemical sensitization at 68 ° C, and then an antifoggant (2) was added, followed by cooling. Thus, the average particle size is 0.30
635 g of a monodisperse cubic silver chlorobromide emulsion having a size of μm was obtained.

[0235]

[Table 10]

[0236]

[Chemical 33]

Photosensitive Silver Halide Emulsion (11) [For Blue Sensitive Emulsion Layer] Well stirred gelatin aqueous solution (gelatin 20 g, potassium bromide 0.3 g, sodium chloride 9 in 695 ml of water).
g and 15 mg of the compound (a) were added and kept at 63 ° C.), the solutions (I) and (II) in Table 11 were simultaneously added at an equal flow rate for 10 minutes. After 10 minutes, with the liquid (III) in Table 11
Solution (IV) was added simultaneously at an equal flow rate for 30 minutes. Also (III)
1 minute after the addition of the (IV) solution, an aqueous dye solution (66 ml of water)
Then, 155 mg of the dye (f) and 78 mg of the dye (g) contained in 4 ml of methanol and kept at 60 ° C.) were added all at once.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust the pH to 6.0 and pAg to 7.8, and sodium thiosulfate and 4-hydroxy- were added.
6-Methyl-1,3,3a, 7-tetrazaindene and chloroauric acid were added for optimum chemical sensitization at 68 ° C, and then an antifoggant (2) was added, followed by cooling. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.55 μm was obtained.

[0239]

[Table 11]

Photosensitive Silver Halide Emulsion (12) [For Blue Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (gelatin 20 g, KBr 0.3 g: NaCl 2 g, compound (a) 15 mg in 630 ml of water was added to give 75). Table 1 for those kept at ℃)
Solution I and Solution II having the composition shown in 2 were added to Solution II, and after 30 seconds, Solution II was added over 30 minutes each, and 5 minutes after the completion of Solution II addition, Solution III was added. After 30 seconds, solution IV was added over 30 minutes each. Then, the solutions III and IV having the compositions shown in Table 12 were added over 35 minutes. afterwards,
19 cc of 1N sodium hydroxide solution was added to neutralize the solution, and the pH of the solution was adjusted to 6. Then add sodium thiosulfate
Add 1.4mg, and after 3 minutes add 1.2mg chloroauric acid for 60 minutes at 75 ℃
Kept at. Then, a liquid prepared by dissolving 430 mg of dye (f) in 80 cc of methanol was added, and 5 minutes after that, the temperature was lowered to 35 ° C.

Then, the solution v was added over 5 minutes.
Then, after washing with water and desalting by a conventional method (performed with 1 g of the precipitating agent (b) at pH 3.9), 6 g of lime-treated ossein gelatin and 68 mg of the antifoggant (1) were added to P.
H was adjusted to 6.0. PAg is 8.5, electric conductivity is
It was 4000 μS. The silver halide grains of the resulting emulsion were octahedral and the grain size was 0.4 μm.

[0242]

[Table 12]

[0243]

[Chemical 34]

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 making a gelatin dispersion of the dye-donor compound will be described. Cyan dye-donor compound (A
1) 7.3 g, cyan dye-donor compound (A2) 10.6 g, surfactant (1) 0.8 g, high-boiling organic solvent (1) 7 g, high-boiling organic solvent (2) 3 g 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. 71% of this solution and 14% of lime-processed gelatin
g and 80 cc of water by stirring and mixing, and then 10 with a homogenizer
Dispersed at 10,000 rpm for minutes. After the dispersion, 180 cc of water for dilution was added. This dispersion is referred to as a dispersion of a cyan dye-donor compound.

[0246]

[Chemical 35]

[0247]

[Chemical 36]

[0248]

[Chemical 37]

[0249]

[Chemical 38]

One magenta dye-donating compound (B) was used.
4.93 g, 0.38 g of surfactant (1) and 7.4 g of high boiling organic solvent (1) were weighed and added with 50 ml of ethyl acetate and dissolved by heating at about 60 ° C. to obtain a uniform solution. 71 g of this solution and a 14% solution of lime-processed gelatin and 100 cc of water
After stirring and mixing, the mixture was mixed with a homogenizer for 10 minutes for 100 minutes.
Dispersed at 00 rpm. Then, 120 CC of dilution water was added. This dispersion is referred to as a dispersion of a magenta dye-donor compound.

[0251]

[Chemical Formula 39]

1 of the yellow dye-donor compound (C) was used.
8.8 g, compound (1) 3.8 g, surfactant (1) 1.74 g, high boiling organic solvent (2) 9. -G 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, 71 g of a 14% solution of lime-processed gelatin and 73 cc of water were stirred and mixed, and then dispersed by a homogenizer at 10,000 rpm for 10 minutes. After that, 105 CC of water for dilution was added. This dispersion is referred to as a yellow dye-donor compound dispersion.

[0253]

[Chemical 40]

10 g of reducing agent (A), surfactant (1)
3 g, high-boiling organic solvent (1) 6.3 g, and ethyl acetate 16 g were heated and dissolved at 60 ° C. to form a uniform solution. This solution and 1
71.4 g of 4% acid-treated gelatin was mixed with 70.6 g of water, added to the liquid kept at 55 ° C., stirred, and then dispersed with a homogenizer at 10,000 rpm for 10 minutes. This dispersion is referred to as a reducing agent dispersion.

[0255]

[Chemical 41]

By these, the photothermographic materials 101 shown in Tables 13 and 14 were constructed.

[0257]

[Table 13]

[0258]

[Table 14]

[0259]

[Table 15]

[0260]

[Chemical 42]

[0261]

[Chemical 43]

[0262]

[Chemical 44]

[0263]

[Chemical formula 45]

Next, a method for producing the image receiving material will be described. Image-receiving material R20 having the constitution as shown in Table 16, Table 17, and Table 18
Made one.

[0265]

[Table 16]

[0266]

[Table 17]

[0267]

[Table 18]

[0268]

[Chemical formula 46]

[0269]

[Chemical 47]

[0270]

[Chemical 48]

[0271]

[Chemical 49]

[0272]

[Chemical 50]

[0273]

[Chemical 51]

[0274]

[Chemical 52]

Preparation of Photosensitive Material 102 When a dispersion of magenta dye-donor compound is prepared, 0.20 g of antifoggant (3) is added at the same time as the dye-donor compound.
A dispersion was made in the same manner except that it was added. A cyan dye-donor compound dispersion was prepared in the same manner except that 0.234 g of the antifoggant (3) was added when the cyan dye-donor compound dispersion was prepared. Except for these, the same material as the photosensitive material 101 was used. Similarly,
Photosensitive materials 103 to 116 shown in Table 19 were prepared. The compounds shown in Table 19 such as the compounds of the present invention were added in the amounts corresponding to the coating amounts shown in Table 20 when preparing dispersions of each dye-donor compound.

[0276]

[Table 19]

Next, the above light-sensitive materials 101 to 116 were subjected to the following exposure and processing. Using a tungsten bulb, B.
G / R three-color separation filter (R: 600-700n
m, G: 500 to 590 nm, B: 400 to 490 nm
It was constructed using the band pass filter of. ) Through 2
Exposure was carried out at 1/10 ″ at 500 lux. Damping water was supplied to the emulsion surface of the exposed light-sensitive material with a wire bar, and then superposed so that the image-receiving material 201 and the film surface were in contact with each other. After heating at 30 ° C. for 30 seconds, the image-receiving material was peeled off from the light-sensitive material to obtain an image on the image-receiving material, and the image was measured for reflection density with a filter Status A using a reflection densitometer X-Rite 310. The results are shown in Table 2.
It shows in 0.

[0278]

[Table 20]

From these results, in the light-sensitive material of the present invention, fog is suppressed in each layer and a high maximum density is realized. Further, the light-sensitive material and the image-receiving material of the present invention were processed into a roll type and set on a Fujix Pictrostat 200 released in Japan from Fuji Film in December 1992. In addition, the processed negative of Fuji Color Super HG400 was set in the slide enlarging unit. The development processing time was all set under the standard conditions of Fujix Pictrostat 200, such as water application conditions, transport conditions, and exposure control, except that the development time was set to 28 seconds at 83 ° C. Printed images from the negatives were obtained with all the light-sensitive materials. Especially, the light-sensitive materials 112 to 116 of the present invention were excellent in the white background and the maximum density, and an image having a much higher image quality was obtained. Further, excellent images were obtained with the light-sensitive material of the present invention even with negatives such as HG100 other than Fujicolor Super HG400 and Super Gold 100/200/400 from Eastman Kodak Company.

In Comparative Light-sensitive Material 101, a light-sensitive material 117 using the same photosensitive silver halide (1) as the red-sensitive layer except for the light-sensitive silver halide of the red-sensitive layer and a light-sensitive material for the red-sensitive layer was used. Light-sensitive material using photosensitive silver halide (2) 118, light-sensitive material using photosensitive silver halide (4) in the red-sensitive layer 119,
A light-sensitive material 120 and a light-sensitive material 121 using light-sensitive silver halide (6) in the red-sensitive layer were prepared, except that light-sensitive silver halide (5) was used in the red-sensitive layer.

Further, in the light-sensitive material 112 of the present invention, a light-sensitive material 122 which has exactly the same constitution except the light-sensitive silver halide of the red-sensitive layer and uses light-sensitive silver halide (1) in the red-sensitive layer,
Photosensitive material using photosensitive silver halide (2) for the red-sensitive layer 12
3, photosensitive material 124 using photosensitive silver halide (4) for the red-sensitive layer, photosensitive material 125 except using photosensitive silver halide (5) for the red-sensitive layer, and photosensitive halogenated for the red-sensitive layer A light-sensitive material 126 and the like using silver (6) were made.

Exposure, heat development treatment and measurement were carried out in the same manner with the R, G and B filters attached in the same manner as above. In all cases, the light-sensitive material of the present invention achieved an excellent white background and the highest density as compared with the comparative light-sensitive material.

In a system in which a processing solution is used in a light-sensitive material for ordinary color printing, halogen is released during color development in a silver halide developing section. Therefore, when a silver iodobromide emulsion containing a very strong inhibitory iodine and a silver chlorobromide emulsion or a silver chloride emulsion are used together, the released iodine suppresses the development of the silver chlorobromide or silver chloride emulsion, Avoid combination as much as possible. However, in the photothermographic material, a photosensitive material using a photosensitive silver halide (5) which is silver chloride in the red-sensitive layer is used.
20 and Photosensitive Material 125, the blue-sensitive layer uses silver iodobromide, but no inhibitory effect is observed.In the composition of Photosensitive Material 125, the photosensitive silver halide emulsion (12) of the blue-sensitive layer was used instead. Even when compared with the light-sensitive materials 127 and 128 using the photosensitive silver halide (10) and the photosensitive silver halide (11), the development of the red-sensitive layer was not suppressed. Further, in the light-sensitive material 112, an excellent white background and a high maximum density were obtained when the green light-sensitive emulsion was used as the light-sensitive silver halide emulsion (7) and the light-sensitive silver halide emulsion (9).

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] April 23, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 1

[Correction method] Change

[Correction content]

[Chemical 1] [In the general formulas (I) and (II), Ball represents an organic ballast group capable of making the compounds represented by these formulas non-diffusible. However, when R ₁ is non-diffusible, Ba
11 may not be necessary. Y represents a carbon atom group necessary for completing a benzene nucleus or a naphthalene nucleus. R ₁ represents a substituted or unsubstituted alkyl group, cycloalkyl group, aralkyl group, aryl group, amino group or heterocyclic group. R ₂ is a hydrogen atom, a halogen atom, a substituted or unsubstituted cycloalkyl group, an aralkyl group,
Aryl group, heterocyclic group, alkoxy group, aryloxy group, acyl group, alkyloxycarbonyl group, aryloxycarbonyl group, carbamoyl group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, acylamino group, alkylthio group, or arylthio group Represents n represents an integer of 0 to 5, and when n is 2 to 5, R _{2 s} may be the same or different, and may combine with each other to form a ring. When Y represents an atomic group necessary for completing the naphthalene nucleus, Ball and R
₂ can be attached to any of the ring systems so formed. ]

[Chemical 2] [In the general formula (III), L is a mere bond or 2
Represents a valence linking group. n represents an integer of 1 to 4. When n = 1, R ₁ represents a hydrogen atom, a carboxyl group, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group or a heterocyclic group. When n = 2, 3 or 4, R ₁ represents a divalent, trivalent or tetravalent residue. R ₂ represents a hydrogen atom, a carboxyl group, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, an aryl group, a heterocyclic group or a carbamoyl group. When n is 2, 3 or 4, the respective combinations of L and R ₂ may be the same or different. However, the case where L is a bond and n 1 is ₁ and both R ₁ and R ₂ are hydrogen atoms is excluded. ]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0082

[Correction method] Change

[Correction content]

(Basic Structure of Silver Halide Grain and Preparation Method) The silver halide which can be used in the present invention includes silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver iodochloride and chloroiodo. Any of silver bromide may be used, but silver iodobromide, silver chloride, silver bromide and silver chlorobromide containing 20 mol% or less of silver iodide are preferable.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0105

[Correction method] Change

[Correction content]

It may be present in the reaction system of a soluble silver salt (eg silver nitrate) and a halide (eg potassium bromide) before the silver halide grains are formed as described in US Pat. No. 4,183,756. U.S. Pat. No. 42
As described in No. 25666, it may be present in the above reaction system after nucleation of silver halide grains and before completion of the silver halide grain formation step. A sensitizing dye may be present in the reaction solution at the same time as the formation of silver halide grains, that is, at the same time when the silver salt and the halide are mixed, and the light-sensitive material containing the emulsion thus prepared is It is more excellent in storage stability and gradation under high temperature conditions.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0115

[Correction method] Change

[Correction content]

In the present invention, the compound represented by Chemical formula 25 may be included. The compound represented by Chemical formula 25 is often used for supersensitization, improvement of storage stability, and suppression of change in sensitivity of the coating solution over time. The light-sensitive material of the present invention has more effective effects.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Name of item to be corrected] 0195

[Correction method] Change

[Correction content]

Further, a high-boiling point organic solvent may be contained in the light-sensitive material and / or the dye fixing element in order to promote dye transfer.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0201

[Correction method] Change

[Correction content]

Light-Sensitive Silver Halide Emulsion (1) [For Red-Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (20 g of gelatin in 480 ml of water, 0.5 g of potassium bromide, 3 parts of sodium chloride).
g and 30 mg of compound (a) and kept at 45 ° C.), solution (I) and solution (II) in Table 1 were simultaneously added at an equal flow rate for 20 minutes, and after 5 minutes, (III) in Table 1 was further added. Solution) and solution (IV) were added simultaneously at an equal flow rate for 25 minutes. In addition, 10 minutes after the start of addition of the liquids (III) and (IV), an aqueous solution of a gelatin dispersion of the dye (containing 105 g of water, 1 g of gelatin, 70 mg of the dye (a), 139 mg of the dye (b), and 5 mg of the dye (c)) was added. (Incubated at 45 ° C.) was added over 20 minutes.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0211

[Correction method] Change

[Correction content]

Light-Sensitive Silver Halide Emulsion (3) [For Red-Sensitive Emulsion Layer] Well-stirred gelatin aqueous 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 compound (a) were added and kept at 45 ° C.), solution (I) and solution (II) in Table 3 were simultaneously added at an equal flow rate for 20 minutes. After 5 minutes, solution (III) and solution (IV) shown in Table 3 were added simultaneously at the same flow rate for 25 minutes.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0212

[Correction method] Change

[Correction content]

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin and 90 mg of compound (b) were added,
The pH was adjusted to 6.2 and the pAg was adjusted to 7.7, 500 mg of a ribonucleic acid degradation product and 2 mg of trimethylthiourea were added, and the temperature was 60 ° C.
After optimum chemical sensitization for about 50 minutes, 4-hydroxy-6
-Methyl-1,3,3a, 7-tetrazaindene 225
mg, dye (d) 64 mg, and KBr 500 mg were sequentially added, and then cooled. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.30 μm was obtained.

[Procedure Amendment 9]

[Document name to be amended] Statement

[Name of item to be corrected] 0213

[Correction method] Change

[Correction content]

[0213]

[Table 3]

[Procedure Amendment 10]

[Document name to be amended] Statement

[Name of item to be corrected] 0216

[Correction method] Change

[Correction content]

[0216]

[Table 4]

[Procedure Amendment 11]

[Document name to be amended] Statement

[Correction target item name] 0218

[Correction method] Change

[Correction content]

[0218]

[Table 5]

[Procedure Amendment 12]

[Document name to be amended] Statement

[Correction target item name] 0231

[Correction method] Change

[Correction content]

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin and 90 mg of compound (b) were added,
The pH was adjusted to 6.0 and the pAg was adjusted to 7.8, and sodium thiosulfate 4.8 mg and 4-hydroxy-6-methyl-1,
3,3a, 7-Tetrazaindene was added and optimal chemical sensitization was performed at 68 ° C, and then 150 mg of antifoggant (2) was added, followed by cooling. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.30 μm was obtained.

[Procedure Amendment 13]

[Document name to be amended] Statement

[Correction target item name] 0232

[Correction method] Change

[Correction content]

[0232]

[Table 9]

[Procedure Amendment 14]

[Document name to be amended] Statement

[Correction target item name] 0240

[Correction method] Change

[Correction content]

Photosensitive Silver Halide Emulsion (12) [For Blue Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (gelatin 20 g, KBr 0.3 g: NaCl 2 g, compound (a) 15 mg in 630 ml of water was added to give 75). Table 1 for those kept at ℃)
Solution I and solution II having the composition shown in 2 were added to solution II, and after 30 seconds, solution I was added over 30 minutes each, and solution IV was added 5 minutes after the completion of addition of solution II. After 30 seconds, the liquid III was added over 30 minutes. After that, 19 cc of a 1N solution of sodium hydroxide was added for neutralization, and the pH of the solution was adjusted to 6. Then, 1.4 mg of sodium thiosulfate was added, and after 3 minutes, 1.2 mg of chloroauric acid was added, and the mixture was kept at 75 ° C. for 60 minutes. Then, a liquid prepared by dissolving 430 mg of dye (f) in 80 cc of methanol was added, and 5 minutes after that, the temperature was lowered to 35 ° C.

[Procedure Amendment 15]

[Document name to be amended] Statement

[Correction target item name] 0241

[Correction method] Change

[Correction content]

Then, the solution v was added over 5 minutes.
Then, after washing with water and desalting by a conventional method (performed with 1 g of the precipitating agent (b) at pH 3.9), 6 g of lime-treated ossein gelatin and 68 mg of the antifoggant (1) were added to P.
H was adjusted to 6.0. PAg is 8.5, electric conductivity is
It was 4000 μS. The silver halide grains of the resulting emulsion were octahedral and the grain size was 0.4 μm.

[Procedure Amendment 16]

[Document name to be amended] Statement

[Correction target item name] 0245

[Correction method] Change

[Correction content]

Next, a method for preparing a gelatin dispersion of a dye-donor compound will be described. Cyan dye-donor compound (A
1) 7.3 g, cyan dye-donor compound (A2) 10.6 g, surfactant (1) 0.8 g, high-boiling organic solvent (1) 7 g, high-boiling organic solvent (2) 3 g 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. 71% of this solution and 14% of lime-processed gelatin
g and 80 cc of water by stirring and mixing, and then 10 with a homogenizer
Dispersed at 10,000 rpm for minutes. After the dispersion, 180 cc of water for dilution was added. This dispersion is called a cyan dye-donor compound dispersion.

[Procedure Amendment 17]

[Document name to be amended] Statement

[Correction target item name] 0247

[Correction method] Change

[Correction content]

[0247]

[Chemical 36]

[Procedure 18]

[Document name to be amended] Statement

[Correction target item name] 0250

[Correction method] Change

[Correction content]

One magenta dye-donating compound (B) was used.
4.93 g, 0.38 g of surfactant (1) and 7.4 g of high boiling organic solvent (1) were weighed and added with 50 ml of ethyl acetate and dissolved by heating at about 60 ° C. to obtain a uniform solution. 71 g of this solution and a 14% solution of lime-processed gelatin and 100 cc of water
After stirring and mixing, the mixture was mixed with a homogenizer for 10 minutes for 100 minutes.
Dispersed at 00 rpm. Then, 120 CC of dilution water was added. This dispersion is referred to as a dispersion of the magenta dye-donor compound.

[Procedure Amendment 19]

[Document name to be amended] Statement

[Correction target item name] 0251

[Correction method] Change

[Correction content]

[0251]

[Chemical Formula 39]

[Procedure amendment 20]

[Document name to be amended] Statement

[Correction target item name] 0252

[Correction method] Change

[Correction content]

1 of the yellow dye-donor compound (C) was used.
Weigh 8.8g, compound (1) 3.8g, surfactant (1) 1.74g, high boiling organic solvent (2) 9.4g, add ethyl acetate 50ml and dissolve by heating at about 60 ° C. To give a uniform solution. This solution, 71 g of a 14% solution of lime-processed gelatin and 73 cc of water were stirred and mixed, and then dispersed by a homogenizer at 10,000 rpm for 10 minutes. After that, 105 CC of water for dilution was added. This dispersion is called a yellow dye-donor compound dispersion.

[Procedure correction 21]

[Document name to be amended] Statement

[Correction target item name] 0254

[Correction method] Change

[Correction content]

10 g of reducing agent (A), surfactant (1)
3 g, high boiling organic solvent (1) 6.3 g, ethyl acetate 16
cc was heated and dissolved at 60 ° C. to form a uniform solution. This solution was mixed with 71.4 g of 14% acid-treated gelatin and 70.6 g of water, added to the solution kept at 55 ° C., stirred, and then dispersed with a homogenizer at 10,000 rpm for 10 minutes. This dispersion is referred to as a reducing agent dispersion.

[Procedure correction 22]

[Document name to be amended] Statement

[Correction target item name] 0265

[Correction method] Change

[Correction content]

[0265]

[Table 16]

[Procedure amendment 23]

[Document name to be amended] Statement

[Correction target item name] 0269

[Correction method] Change

[Correction content]

[0269]

[Chemical 47]

[Procedure correction 24]

[Document name to be amended] Statement

[Correction target item name] 0279

[Correction method] Change

[Correction content]

From these results, in the light-sensitive material of the present invention, fog is suppressed in each layer and a high maximum density is realized. Further, the light-sensitive material and the image-receiving material of the present invention were processed into a roll type, and set in a Fujix Pictrostat 200 which was released in Japan from Fuji Film in December 1992. In addition, the processed negative of Fuji Color Super HG400 was set in the slide enlarging unit. The development processing time was set to 28 seconds at 83 ° C, except for water application conditions.
Processing was performed under the standard conditions of the Fujix Pictrostat 200, such as transportation conditions and exposure control. Printed images from the negatives were obtained with all the light-sensitive materials. Especially, the light-sensitive materials 112 to 116 of the present invention were excellent in the white background and the maximum density, and an image having a much higher image quality was obtained. Further, excellent images were obtained with the light-sensitive material of the present invention even with negatives such as HG100 other than Fujicolor Super HG400 and Super Gold 100/200/400 from Eastman Kodak Company.

[Procedure correction 25]

[Document name to be amended] Statement

[Correction target item name] 0280

[Correction method] Change

[Correction content]

In Comparative Light-sensitive Material 101, a light-sensitive material 117 using the same photosensitive silver halide (1) as the red-sensitive layer except for the light-sensitive silver halide of the red-sensitive layer and a light-sensitive material for the red-sensitive layer was used. Light-sensitive material using photosensitive silver halide (2) 118, light-sensitive material using photosensitive silver halide (4) in the red-sensitive layer 119,
Photosensitive material using photosensitive silver halide (5) in the red-sensitive layer 12
0, a photosensitive material 121 using photosensitive silver halide (6) in the red-sensitive layer was prepared.

[Procedure Amendment 26]

[Document name to be amended] Statement

[Name of item to be corrected] 0281

[Correction method] Change

[Correction content]

Further, in the light-sensitive material 112 of the present invention, a light-sensitive material 122 which has exactly the same constitution except the light-sensitive silver halide of the red-sensitive layer and uses light-sensitive silver halide (1) in the red-sensitive layer,
Photosensitive material using photosensitive silver halide (2) for the red-sensitive layer 12
3, photosensitive material 124 using photosensitive silver halide (4) for the red-sensitive layer, photosensitive material 125 using photosensitive silver halide (5) for the red-sensitive layer, photosensitive silver halide ( 6) I made a light-sensitive material such as 126.

[Procedure Amendment 27]

[Document name to be amended] Statement

[Correction item name] 0283

[Correction method] Change

[Correction content]

In a system in which a processing solution is used in a light-sensitive material for ordinary color printing, halogen is released during color development in a silver halide developing section. Therefore, when a silver iodobromide emulsion containing a very strong inhibitory iodine and a silver chlorobromide emulsion or a silver chloride emulsion are used together, the released iodine suppresses the development of the silver chlorobromide or silver chloride emulsion, Avoid combination as much as possible. However, in the photothermographic material, a photosensitive material using a photosensitive silver halide (5) which is silver chloride in the red-sensitive layer is used.
20 and photographic material 125, silver iodobromide is used in the blue-sensitive layer, but no inhibitory effect is observed, and in the composition of photographic material 125, instead of the photosensitive silver halide emulsion (12) in the blue-sensitive layer, Even when compared with the light-sensitive materials 127 and 128 using the photosensitive silver halide (10) and the photosensitive silver halide (11), the development of the red-sensitive layer was not suppressed. Further, in the light-sensitive material 112, an excellent white background and a high maximum density were obtained when the light-sensitive silver halide emulsion (7) and the light-sensitive silver halide emulsion (9) were used as the green light-sensitive emulsion.

Claims (1)

[Claims] 1. A photosensitive silver halide, a reducing agent, a compound represented by the general formula (I) or (II), a binder, and a dye-donor which releases a diffusible dye corresponding to silver development on a support. Development color photosensitive material containing a photosensitive compound, characterized in that at least one photosensitive layer containing said photosensitive silver halide contains at least one compound represented by formula (III) Photosensitive material. [Chemical 1] [In the general formulas (I) and (II), Ball represents an organic ballast group capable of making the compounds represented by these formulas non-diffusible. However, when R ₁ is non-diffusible, Ba
11 may not be necessary. Y represents a carbon atom group necessary for completing a benzene nucleus or a naphthalene nucleus. R ₁ represents a substituted or unsubstituted alkyl group, cycloalkyl group, aralkyl group, aryl group, amino group or heterocyclic group. R ₂ is a hydrogen atom, a halogen atom or a substituted or unsubstituted cycloalkyl group aralkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an acyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, It represents a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an acylamino group, an alkylthio group, or an arylthio group. n represents an integer of 0 to 5, and when n is 2 to 5, R _{2 s} may be the same or different, and may combine with each other to form a ring. When Y represents an atomic group necessary for completing the naphthalene nucleus, Ball and R
₂ can be attached to any of the ring systems so formed. ] [Chemical 2] [In the general formula (III), L is a mere bond or 2
Represents a valence linking group. n represents an integer of 1 to 4. When n = 1, R ₁ represents a hydrogen atom, a carboxyl group, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group or a heterocyclic group. When n = 2, 3 or 4, R ₁ represents a divalent, trivalent or tetravalent residue. R ₂ represents a hydrogen atom, a carboxyl group, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, an aryl group, a heterocyclic group or a carbamoyl group. When n is 2, 3 or 4, the respective combinations of L and R ₂ may be the same or different. However, the case where L is a bond and n 1 is ₁ and both R ₁ and R ₂ are hydrogen atoms is excluded. ]