JPH02259755A - Heatdevelopable color photosensitive material - Google Patents

Abstract

PURPOSE:To improve the color reproducibility of a positive image by specifying the peak wavelength and spectral form of the spectral sensitivity of each of blue-, green- and red-sensitive layers. CONSTITUTION:When this photosensitive material is exposed for 1/10sec with standard illuminating light C defined by the International Commission on Illumination (CIE) as a light source, the peak wavelength of the spectral sensitivity of the blue-sensitive emulsion layer is 450+ or -40nm and the sensitivity at the peak wavelength+ or -40nm is lower than that at the peak wavelength by log0.2 or above. The peak wavelength of the spectral sensitivity of the green-sensitive emulsion layer is 550+ or -40nm, that of the red-sensitive emulsion layer is 650+ or -40nm and the sensitivity of each of the layers at the peak wavelength+ or -40 nm is lower than that at the peak wavelength by log0.2 or above.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a heat-developable color photosensitive material, and particularly to a heat-developable color photosensitive material that can produce positive images with excellent color reproducibility. .

(Background Art) Heat-developable photosensitive materials are well known in this technical field, and for more information on heat-developable photosensitive materials and their processes, see, for example, "Fundamentals of Photographic Engineering" Non-Silver Salt Photography Horse (published by Corona Publishing, 1982), Volume 2.
42-255j [, described in U.S. Pat. No. 4,500,626, etc.

Many methods have also been proposed for obtaining positive color images by heat development.

For example, US Pat. No. 4,559,290 describes the so-called DRR.
An oxidized compound that does not have dye-releasing ability is made to coexist with a reducing agent or its precursor, and the reducing agent is oxidized according to the exposure amount of silver halide by heat development, and the remaining unoxidized reducing agent is A method of reducing and releasing a diffusible dye has been proposed. Also, European Patent Publication No. 22074
No. 6, Technical Report 87-6199 (Vol. 12, No. 22) describes compounds that release diffusible dyes by a similar mechanism.
A heat-developable color photosensitive material using a non-diffusible compound which releases a diffusible dye upon reductive cleavage of an N--X bond (X represents an oxygen atom, nitrogen atom or sulfur atom) has been described.

(Problems to be Solved by the Invention) However, when the above-mentioned reducible dye-providing compound is used in combination with a silver halide emulsion together with a reducing agent or its precursor, there is a problem of poor color reproducibility. I found out something.

One of the reasons for poor color reproducibility is that in heat-developable photosensitive materials for positive image formation using such reducible dye-donating compounds, a diffusion-resistant electron donor is used as a reducing agent to suppress staining. In addition, it is effective to use a diffusible electron transfer agent, but the generated electron transfer agent radicals diffuse to other layers with different color sensitivities, cross-oxidize the electron donors there, and cause damage to other layers. This is thought to be because it causes a decrease in image density.

In order to solve these problems, attempts have been made to provide an intermediate layer between photosensitive layers with different color sensitivities or to contain a reducing substance in this intermediate layer, but For photosensitive materials, image forming speed, resolution,
From the viewpoint of film quality, etc., there are restrictions on the amount of binder in the intermediate layer and the amount of reducing substance added, so a sufficient improvement effect could not be obtained.

An object of the present invention is to improve color reproducibility in a heat-developable color photosensitive material.

(Means for Solving the Problems) As a result of a precise study of the relationship of sensitivity to the wavelength of exposing light in order to improve color reproducibility in heat-developable photosensitive materials, the present inventor found that a blue-sensitive layer, a green-sensitive layer, We have discovered that color reproducibility can be greatly improved by defining the peak wavelength and spectral shape of the spectral sensitivity of the red-sensitive layer.

The object of the present invention is to have on a support at least a photosensitive silver halide emulsion, a binder, an electron donor, an electron transfer agent, and a reducible dye-donating compound that releases a diffusible dye when reduced. In the heat-developable color photosensitive material,
The light-sensitive material has a blue-sensitive silver halide emulsion layer combined with a reducible dye-donating compound that releases a yellow dye, and a green-sensitive silver halide emulsion layer that is combined with a reducible dye-donating compound that releases a magenta dye. A photographic material having a multilayer structure, comprising a red-sensitive silver halide emulsion layer combined with a red-sensitive silver halide emulsion layer and a reducible dye-donating compound that releases a cyan dye;
and standard illumination light C specified by the International Commission on Illumination (CIB).
The peak wavelength of the spectral sensitivity of the blue-sensitive emulsion layer was 450±40n during exposure for 1/10 second using
m, and furthermore, the sensitivity at a wavelength of the peak wavelength + 40 nm is 0.
2 or more, the peak wavelength of the spectral sensitivity of the green-sensitive emulsion layer is at 550±40 nm, and the peak wavelength is at ±40 nm.
The sensitivity at a wavelength of 100 nm is lower than the sensitivity at a peak wavelength by 0.2 or more in logarithmic units, the peak wavelength of the spectral sensitivity of the red-sensitive emulsion layer is at 650 ± 40 nm, and the wavelength is within ±40 nm of the peak wavelength. This was achieved by a heat-developable color photosensitive material characterized in that the sensitivity at the peak wavelength is 0.2 or more logarithmically lower than the sensitivity at the peak wavelength.

In the present invention, furthermore, the peak wavelength of spectral sensitivity of the blue-sensitive emulsion layer is 450±20 nm.
m, and the peak wavelength of the spectral sensitivity of the green-sensitive emulsion layer is 550±20n.
m, and the peak wavelength of the spectral sensitivity of the red-sensitive emulsion layer is 650±20n.
It is preferable that it is in m.

Furthermore, in the present invention, it is preferable that the difference in sensitivity at the peak wavelength of the spectral sensitivity of the blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer is within 1.0 in logarithmic units.

In the present invention, the standard illumination light C refers to the International Commission on Illumination (
CIE), and the details are described in Mitsuo Ikeda's ``Fundamentals of Color Engineering J'' (Shokusho Shoten, published in 1980).

In addition, in the present invention, sensitivity in logarithmic units means 'OgI
It is determined by e (exposure amount that gives a density of minimum density + 0.6) -.

The peak wavelength of spectral sensitivity and the shape of the spectral spectrum defined above can be achieved by combining various techniques known in the field of silver halide emulsions.

The method for preparing the light-sensitive silver halide emulsion used in the light-sensitive material of the present invention will be described in detail.

Silver halides that can be used in the present invention include silver chloride, silver bromide,
Any of silver iodobromide, silver chlorobromide, silver chloroiodide, and silver chloroiodobromide may be used.

However, in consideration of development speed, spectral sensitization, fog during chemical sensitization, etc., it is preferable to use silver halide containing 50 mol% or more of silver bromide, more preferably 10 mol% or less of iodide. Silver iodobromide containing silver, silver chlorobromide containing 50 mol % or less of silver chloride, or pure silver bromide is preferred, but the present invention is not limited to the preferred range of the halogen composition.

The silver halide emulsion used in the present invention is preferably a surface latent image type emulsion. It may also be a so-called shallow latent type emulsion in which the latent image is mainly distributed within the immediate vicinity of the surface. Regarding the sex law,
For example, it is described in detail in Japanese Patent Application No. 62-326566.

Further, according to the present invention, a negative photosensitive material can be designed using an internal latent image type emulsion.

The internal latent image type emulsion can be used as a direct reversal emulsion by combining it with a nucleating agent or an optical coupler.

Further, the effects of the present invention may be made more effective by using a so-called core/shell emulsion in which the inside of the grain and the surface layer of the grain have different phases. In particular, when silver chlorobromide containing 50 mol% or more of silver chloride is used, it is preferably a core/shell emulsion.
The shell emulsion is, and further requires a combination of chemical sensitization and sensitizing dye suitable for each grain. In the case of a silver chlorobromide emulsion containing silver chloride, the difference in silver bromide content between the core and shell is preferably 40 mol% or less, and the shell preferably contains 60 mol% or more of silver bromide. Preferably, so-called multi-structure particles having a double or triple structure inside the particle are also effective in the present invention.

The silver halide emulsion may be monodisperse or polydisperse, and monodisperse emulsions may be mixed, but a monodisperse emulsion with a coefficient of variation of 20% or less or a mixture of monodisperse emulsions with a coefficient of variation of 20% or less should be used. is preferred.

The particle size is 0°1μ to 2.0μ, especially 0. 1μ～1
．． 0μ is preferred and the most preferred particle size is 0.2μ~
It is 0.7μ.

The crystal habits of silver halide grains are cubic, octahedral, tetradecahedral,
A flat plate with an aspect ratio of 8.0 or more, an aspect ratio of 8.
It is thought that this is due to the appearance of a high index plane when a sensitizing dye is present during grain formation when pure silver bromide or silver iodobromide is used. It may be preferable to use silver halide grains having a spherical or potato-like shape.

However, the present invention is not limited thereto, and in particular, U.S. Pat.
No. 4,628.021, Research Disclosure (hereinafter abbreviated as RD) 17029 (1978
Any of the silver halide emulsions described in JP-A-62-253159 and the like can be used.

Although silver halide emulsions may be used as they are unripe, they are usually chemically sensitized before use.For conventional emulsions for photosensitive materials, well-known sulfur sensitization methods, reduction enhancement methods, noble metal enhancement methods, etc. are used. They can be used alone or in combination. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-253159).

The coating amount of photosensitive silver halide used in the present invention is 111! g to 10 g/rrf.

A preferred chemical sensitization method in the present invention is chemical sensitization in the presence of a sensitizing dye. Specifically, during particle formation,
Adding a sensitizing dye during or after grain formation,
A method in which a sensitizing dye is added before or during chemical sensitization is preferred.

In addition, in the present invention, KBr, K
In addition to L and NaCl, fine particles of AgBr, Ag LAgCl, or a mixed crystal thereof can be added.

The silver halide used in the present invention may be spectrally sensitized with methine dyes and others. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes,
Included are hemicyanine dyes, styryl dyes and hemioxonol dyes. Preferred sensitizing dyes are cyanine dyes.

Specifically, U.S. Pat.
17029 (1978), pages 12-13, and the like.

These sensitizing dyes may be used alone or in combination, and combinations of enhancing dyes are often used particularly for the purpose of supersensitization.

Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral enhancement effect or a compound that does not substantially absorb visible light and exhibits supersensitization (for example, as described in U.S. Pat. No. 615゜641, patent application No. 61-22
6294 etc.).

These sensitizing dyes may be added to the emulsion at or before chemical ripening, or as described in US Pat. No. 4.183.
It may be added before or after nucleation of silver halide grains according to No. 756 and No. 4,225,666, and the amount added is generally about 10-" to 10-" mol per 111 mol of halide.

The most preferred method for preparing a silver halide emulsion of the present invention is as shown below, but the present invention is not limited thereby.

(1) A monodisperse emulsion with an average grain size of 0.3 to 0.6 μm is used.

(2) As the silver halide, pure silver bromide, silver chlorobromide containing 50 mol % or less of silver chloride, or silver iodobromide containing 10 mol % or less of silver iodide is used.

(3) After grain formation or after grain formation or before chemical sensitization, during or after chemical sensitization, add cyanine sensitizing dye having a spectral sensitivity suitable for each photosensitive layer at a rate of 10-10% per mole of silver halide. Add "~to-" moles.

(4) Gold and sulfur sensitization.

(5) 4-hydroxy 6-methyl-1,3,3a.

A stabilizer such as 7-chitrazaindene is added at 10-'-10-' moles per mole of silver genide during or after chemical sensitization.

(6) A mercapto antifoggant is added in an amount of 101 to 10@-1 mol per mol of silver halide.

In the present invention, a reducible dye-donating compound is combined with an electron transfer agent and an electron donor, a binder, and a silver halide emulsion to form one unit of a photosensitive layer. The reducible dye-providing compound may be added to the same layer as the silver halide emulsion, or may be added separately to adjacent layers.
In the latter case, it is preferable from the viewpoint of sensitivity that the layer of the reducible dye-donating compound is located below the silver halide emulsion layer. Although it can be added to any layer of the reducing dye-donating compound layer, it is preferable that at least the electron transfer agent is present in the silver halide emulsion layer. , three sets of red-sensitive layers are used in combination. Each color-sensitive layer can be arranged in various arrangements known in conventional color-sensitive materials. Further, each of these color-sensitive layers may be divided into 2N or more layers if necessary. An example of a preferred layer structure of the heat-developable color photosensitive material of the present invention is: support - heat-developable red photosensitive layer - intermediate layer. - Heat-developable green photosensitive layer - Intermediate layer - Heat-developable blue photosensitive layer - Protective layer, transparent support -
Heat-developable blue light-sensitive layer Intermediate layer - Heat-developable green light-sensitive layer - Intermediate layer - Heat-developable red light-sensitive layer - Protective layer, support - Cyan dye-providing compound layer - Red-sensitive emulsion layer - Intermediate layer - Magenta dye-donor These include a dye-providing compound layer, a green-sensitive emulsion layer, an intermediate layer, a yellow dye-providing compound layer, and a blue-sensitive emulsion layer.

In addition to the above, the heat-developable color photosensitive material can be provided with various auxiliary layers such as an undercoat layer, a yellow filter layer, an antihalation layer, and a back layer.

The intermediate layer may also serve as a yellow filter layer.

Next, the reducible dye-providing compound used in the present invention will be explained.

The reducible dye-providing compound used in the present invention is preferably a compound represented by the following formula (C-1,).

PWR-(Time)t-Dye-Formula (C-1) In the formula, PWR is reduced to -(Time)
Represents a group that releases t-Dye.

Time represents a group that is released from PWR as -(Time)t-Dye and then releases Dye through a subsequent reaction.

t represents an integer of 0 or l.

Dye represents a dye or its precursor.

First, I will explain PWR in detail.

PWR is described in U.S. Pat. No. 4,1.39,389 or U.S. Pat. No. 4,139,3795. 4,564.577
No., JP-A-59-185333, JP-A No. 57-84453
Even if it corresponds to a moiety containing an electron-accepting center and an intramolecular nucleophilic substitution reaction center in a compound that releases a photographic reagent by an intramolecular nucleophilic substitution reaction after being reduced as disclosed in No. Good, U.S. Patent 4,232.10
No. 7, JP-A No. 59-101649, Research Disclosure (1984) IV, No. 24025, or JP-A No. 61-88257, after being reduced, the photographic reagent is released into the molecule by an electron transfer reaction. It may correspond to a moiety containing an electron-accepting quinonoid center in a compound to be released and a carbon atom connecting it to a photographic reagent. Also, JP-A-56-142
530, U.S. Pat. No. 4,343,893, U.S. Patent No. 4,61
No. 9,884, the single bond is cleaved to release the photographic reagent after reduction, and the aryl group substituted with an electron-withdrawing group in the compound and the atom connecting it to the photographic reagent (sulfur atom or carbon or a nitrogen atom), and may also correspond to a moiety containing a nitrogen atom).
It may correspond to a moiety containing a nitro group in a nitro compound that releases a photographic reagent after electron acceptance and a carbon atom that connects the photographic reagent with the nitro group, as disclosed in No. 50,223. , U.S. Patent 4,609.610
It may correspond to the geminal dinitro moiety in the dinitro compound that beta-eliminates the photographic reagent after electron acceptance and the carbon atom-containing moiety that connects it to the photographic reagent, as described in the above issue.

Also, more preferably, European Patent No. 220.7
46 No. 2, Published Technical Report 87-6199, U.S. Patent No. 4,
No. 783.396, Japanese Patent Publication No. 63201653, 63
-201654 etc., N-X bond (
A compound having an electron-withdrawing group (X represents an oxygen, sulfur or nitrogen atom) and an electron-withdrawing group; A compound having a po-π bond (X has the same meaning as above) and an electron-withdrawing group in one molecule described in JP-A-63-271344, JP-A-63-271
Examples include compounds having a c-x' bond (xo has the same meaning as X or represents -3O□-) and an electron-withdrawing group in one molecule as described in No. 341. Also, patent application 1986-319
Compounds described in No. 989 and No. 62-320771 that release a diffusible dye by cleavage of a single bond by a π bond conjugated with an electron-accepting group after reduction can also be used.

To more fully achieve the purpose of the present invention, the general formula CC
Among the compounds of -1), those represented by the general formula (Cn) are preferred.

- Formula (CII) (T im e + r D y e is Rlum,
Binds to at least one of R10 rich or EAG.

- The part corresponding to PWR in the formula (CIO) will be explained.

X represents a group (-N CR"' )-) containing an oxygen atom (-0-), a sulfur atom (-3-), or a nitrogen atom.

Rlum, R1@4 and Rlum represent a group other than a hydrogen atom or a simple bond.

Groups other than hydrogen atoms represented by R1111, Rlum, and R10ff include alkyl groups, aralkyl groups,
alkenyl group, alkynyl group, aryl group, heterocyclic group,
Examples include sulfonyl group, carbamoyl group, and sulfamoyl group, which may have a substituent.

RIOI and RI■ are substituted or unsubstituted alkyl groups, alkenyl groups, alkynyl groups, aryl groups, hetero m
s, acyl group, sulfonyl group, etc. are preferable, R11,
and Rlum preferably has 1 to 40 carbon atoms.

Preferred examples of R1 are substituted or unsubstituted acyl or sulfonyl groups, which are the same as the acyl and sulfonyl groups described for RIOI and R11+3. The number of carbon atoms is preferably 1 to 40.

RIOI, R16! and R103 may be bonded to each other to form a five- to six-membered ring.

As X, enzymes are particularly preferred.

EAG will be described later.

Furthermore, in order to achieve the object of the present invention, general formula (Cn)
Among the compounds represented by the above, those represented by the general formula (CI[I) are preferred.

The general formula (Cull) (Time-)-rDye is bonded to at least one of R"' and BAG.

X has the same meaning as above.

R1114 represents an atomic group that is bonded to X or a nitrogen atom to form a five- or six-membered monocyclic or condensed heterocycle including the nitrogen atom.

EAG represents a group that accepts or takes electrons from a reducing substance, and is bonded to a nitrogen atom. EAG is preferably a group represented by the following general formula (A).

- Formula (A) In the general formula (A), (2) represents an atomic group that forms a three- to six-membered aromatic group together with Z+ SZl, and n represents an integer from 3 to 3.

Vs: Zs-1v, 1-Lz, -1■.

; Zs Z4 Zs-2v, i-L-z.

Z s Z--1Vyi Zs Za Z
s ZaZ, -1■. i Zs' Z-Zs
Z-ZtZs-.

-O--5-1 or -SO,-, each Sub represents a simple bond (pi bond), a hydrogen atom, or a substituent described below. may be different, or may be bonded to each other to form a 3- to 6-membered saturated or unsaturated carbocycle or heterocycle.

- In the catalytic formula (A), the sum of the Hammett substituent constant sigma para of the substituents is +0.50 or more, more preferably +0.
Select Sub so that it is 70 or more, most preferably +0°85 or more.

EAG is preferably an aryl group or a heterocyclic group substituted with at least one electron-withdrawing group. Substituents bonded to the aryl group or heterocyclic group of EAG can be used to adjust the physical properties of the entire chemical compound. Examples of physical properties of the entire compound include ease of accepting electrons, water solubility, oil solubility, diffusibility, sublimation, melting point, dispersibility with binders such as gelatin, and reaction with nucleophilic groups. properties, reactivity towards electrophilic groups, etc.! It can be used to make a clause.

A specific example of an EAG is described in European Patent Publication No. 220746A2, pages 6-7.

Time may lead to the cleavage of nitrogen-oxygen, nitrogen-nitrogen or nitrogen-sulfur bonds, resulting in D
Represents a group that releases ye.

T! Various groups represented by me are known, for example, JP-A-61-147244, pages (5) to (6), and JP-A-61-147244.
No. 36549 (8) pages - 04, patent application No. 61-8862
5 The foundations described on pages (36) to (44) are established.

Dyes include azo dyes, azomethine dyes, anthraquinone dyes, naphthoquinone dyes, styryl groups, nitro dyes, quinoline dyes, carbonyl dyes, and phthalocyanine dyes. Note that these dyes can also be used in the form of a temporarily shortened wavelength that can be multicolored during development.

Specifically, EP76.492A, JP 59-165
Dye disclosed in No. 054 can be used.

Above - Represented by formula (CII) or (CII[).

The compound itself needs to be immobile in the photographic layer, so EAG, R16I, R16! R-0
It is desirable to have a ballast group having 8 or more carbon atoms at the 4 or X position (particularly at the EAG position).

Typical specific examples of the reducible dye-providing compound used in the present invention are listed below, but the present invention is not limited to these, and is described in European Patent Publication No. 220746A2, Technical Report 87-6199, etc. Dye-providing compounds that have been described can also be used.

p R: (l 4) R; Each of these compounds can be synthesized by the methods described in the patent specifications cited above.

The amount of the dye-donating compound to be used depends on the extinction coefficient of the dye, but is 0.05 to 5 mmol/I, preferably O.1 to 3.
The dye-providing substances having a concentration of 0 mmol/I can be used alone or in combination of two or more. In addition, in order to obtain images of black or different hues,
As described in No. 51, mobile dyes having different hues, for example, at least one of cyan, magenta, and yellow dye-providing substances are mixed and contained in a layer containing silver halide or in an adjacent layer. It is also possible to use a mixture of two or more types of dye-providing substances that emit .

In the present invention, an electron donor and an electron transfer agent (PTA) are used, and details of these compounds are described in European Patent Publication No. 220746A2, Technical Report No. 87-6199, and the like. A particularly preferred electron donor (or its precursor) is a compound represented by the following formula (C) or CD).

- Numerical formula (C) General formula (D) In the formula, A, , and A. 2 represents a hydrogen atom or a protecting group for a phenolic hydroxyl group which can be removed by a nucleophilic reagent, respectively.

Here, examples of nucleophilic reagents include anionic reagents such as Ooe, Roe (R; alkyl group, aryl group, etc.), hydroxamic acid anions So, "', primary or secondary amines, hydrazine, hydroxylamine, etc. Examples include compounds with lone pairs of electrons, such as alcohols, thiols, and the like.

Preferred examples of Al61 SA+* are hydrogen atoms,
Acyl group, alkylsulfonyl group, arylsulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, dialkylphosphoryl group, dialkylphosphoryl group, or JP-A-59-197 (No. 137, JP-A-59-197)
The iJ group disclosed in No. 20105 may also be used, or A+or, A+. 8 is Roor if possible,
R1I! , RIs and R2O3 may be combined with each other to form a ring, and Al0I s A+. , may both be the same or different.

Rt6+, R-Tsubasa, R-Op, and R164 are each a hydrogen atom, an alkyl group, an aryl group, an alkylthio group, an arylthio group, a sulfonyl group, a sulfo group, a halokene atom, a cyano group, a carbamoytt4, a sulfamoyl group, an amide group , imide group, carboxyl group, sulfonamide group, etc. These groups may have a substituent if possible.

However, the total number of carbon atoms in R101, and R11k4 is 8 or more. In addition, in formula (C), R1+11 and R211″ and/or R1・3 and R8・4, and in formula (D), R801 and R1−1, R
803 and/or R10! and R164 may combine with each other to form a saturated or unsaturated ring.

Among the electron donors represented by formula (C) or (D), those in which at least two of Rzo+ to R204 are substituents other than hydrogen atoms are preferred. Particularly preferred compounds are at least one of RtoI and Rtax, and at least one of R103 and Rto4 is a substituent other than a hydrogen atom.

A plurality of electron donors may be used in combination, or an electron donor and its precursor may be used in combination. Specific examples of electron donors are listed, but the invention is not limited to these compounds.

(ED-3) (ED-4) (ED-6) (ED-11) (ED (ED-13) (ED-7) υI (ED-8) 0■ (ED-9) (ED-10) The amount of electron donor (or its precursor) used has a wide range, but is preferably 0.0 per mole of positive dye donor.
A preferred range is from 1 mol to 50 mol, particularly from 0.1 mol to 5 mol. Also halogenated fl! 0.001 mol to 5 mol, preferably 0.01 mol to 1 mol per mol
．． It is 5 moles.

As the TA to be used in combination with these electron donors, any compound can be used as long as it is oxidized by silver halide and the oxidized form has the ability to cross-oxidize the electron donor. Preferably something that is movable.

A particularly preferable ETA is the following general formula (X-1) or (
This is a compound represented by X-11).

(X-1) 1:X-n) In the formula, R represents an aryl group, R2m+, R31! R
2. R314, R2@A and R3 fist- are hydrogen atoms,
It represents a halogen atom, an acylamino group, an alkoxy group, an alkylthio group, an alkyl group, or an aryl group, and may be substituted if possible, and each of these may be the same or different.

In the present invention, the compound represented by the formula (X-11) is particularly preferred. In the formula [X-■], Rco@l, Rs*t, Rs.3 and Rs.4 are hydrogen atoms, Preferred are alkyl groups having 1 to 10 carbon atoms, substituted alkyl groups having 1 to 10 carbon atoms, and substituted or unsubstituted 7-aryl groups, and more preferred are hydrogen atoms, methyl groups, hydroxymethyl groups, phenyl groups, hydroxyl groups, and alkoxy basis,
It is a phenyl group substituted with a hydrophilic group such as a sulfo group or a carboxyl group.

Specific examples of ETA are shown below.

(X-1) (X-3) (X-5) (X-8) (X-13) (X-10) (X-15) (X-16) (X-11) (X-12) (X-17) (X-2) (X-4) (X-6) (X-14) The ETA precursor used in the present invention has a developing effect during storage of the photosensitive material before use. However, it is a compound that can only release ETA by the action of an appropriate activator (eg, base, nucleophile, etc.) or heating.

In particular, the ETA precursor used in the present invention has a reactive functional group blocked with a blocking group.
Although it does not function as an ETA before development, it can function as an ETA because the blocking group is cleaved under alkaline conditions or when heated.

Examples of the ETA precursor used in the present invention include 1-
2 and 3-acyl derivatives of phenyl-3-pyrazolidinone, 2-aminoalkyl or hydroxylalkyl derivatives, hydroquinone, metal salts of catechol (lead, cadmium, calcium, barium, etc.), halogenated acyl derivatives of hydroquinone, oxazine of hydroquinone and bisoxazine derivatives, lactone-type ETA precursors,
In addition to hydroquinone precursors having a quaternary ammonium group and cyclobequix-2-ene-1,4-dione type compounds, compounds that release ETA through an electron transfer reaction, compounds that release PTA through an intramolecular nucleophilic substitution reaction, Examples include an ETA precursor blocked with a phthalide group, an ETA precursor blocked with an indomethyl group, and the like.

The ETA precursor used in the present invention is a known compound, for example, U.S. Pat.
, No. 967, No. 3.246.988, No. 3,29
No. 5,978, No. 3.462.266, No. 3,5
No. 86,506, No. 3,615,439, No. 3,
No. 650,749, No. 4,209,580, No. 4
．． 330.617, British Patent No. 4,310.612, British Patent No. 1,023.701, British Patent No. 1,231°830
No. 1.258,924, No. 1゜346.92
No. 0, JP 57-40245, JP 58-1139, JP 5B-1140, JP 59-178458, JP 5
Developer precursors described in No. 9-182449, No. 59-182450, etc. can be used.

In particular, JP-A-59-178458, JP-A No. 59-18244
The precursors of 1-phenyl-3-pyrazolidinones described in No. 9 and No. 59-182450 are preferred.

ETA and ETA precursors can also be used.

In the present invention, the combination of electron donor and ETA is preferably incorporated into the heat-developable color photosensitive material. Electron donors, ETAs, or their precursors can be used in combination of two or more, and can be used in emulsion layers (blue-sensitive layers, green-sensitive layers, red-sensitive layers, infrared-sensitive layers, ultraviolet-sensitive layers, etc.) in light-sensitive materials. It can be added to each emulsion layer or only to some emulsion layers.
Further, it can be added to layers adjacent to the emulsion (haley silane prevention layer, undercoat layer, intermediate layer, protective layer, etc.), or even to all layers. The electron donor and ETA can be added to the same layer or to separate layers. Additionally, these reducing agents can be added in the same layer as the dye-donating substance or in a separate layer; however, it is preferable that the diffusion-resistant electron donor be present in the same layer as the dye-donating substance. preferable,
ETA can be incorporated into the image-receiving material (dye fixing layer), or if a small amount of water is present during thermal development, it can be dissolved in this water. The preferred amount of the dye-donating substance used is 0.01 to 50 mol in total, preferably 0.1 to 50 mol, per 1 mol of the dye-donating substance.
5 mol, total amount o, ooi per 1 mol of silver halide
-5 mol, preferably 0.01-1.5 mol.

Further, PTA accounts for 60 mol% or less, preferably 40 mol% or less of the total reducing agent. When ETA is supplied dissolved in water, the concentration of ETA is preferably 10-4 mol/l-1 mol/l.

In the present invention, an organic metal salt can also be used as an oxidizing agent together with photosensitive silver halide.

Among such organic metal salts, RflA salts are most preferably used.

Organic compounds that can be used to form the above-mentioned organic silver salt oxidizing agents include U.S. Pat. No. 4,500,626;
There are benzotriazoles, fatty acids, and other compounds described in 531a and the like. Further, silver salts of carboxylic acids having a furkynyl group such as silver phenylpropiolate described in JP-A No. 60-113235, and JP-A No. 61-249044
Also useful is acetylene silver, described in No. Two or more types of organic silver salts may be used in combination.

The above-mentioned organic silver salts contain, per mol of photosensitive silver halide,
0.01 to 10 mol, preferably 0.01 to 1
Moles can be used together. The total coating amount of photosensitive silver halide and organic silver salt is 50 mg or IOg/silver equivalent.
+m' is appropriate.

Various anticapri agents or photographic stabilizers can be used in the present invention. For example, RDI 7
643 (1978) 24-25, the azoles and azaindenes described in JP-A-59-168-442, the phosphoric acids described in JP-A-59-168-442, or the mercapto compounds described in JP-A-59-111,636; Metal salts thereof, acetylene compounds described in JP-A No. 62-87957, and the like can be used.

A hydrophilic binder is preferably used for the constituent layers of the photosensitive material or dye fixing material. Examples include those described on pages (2f3)K to (28) of JP-A-62-253159. Specifically, transparent or translucent hydrophilic binders are preferred, and include natural compounds such as proteins or cellulose derivatives such as gelatin and gelatin derivatives, polysaccharides such as starch, gum arabic, dextran, and purufun; polyvinyl alcohol; Examples include polyvinylpyrrolidone, acryl heptamide polymer, and other synthetic polymer compounds. Also, JP-A-62-2
45260 etc., i.e. -
〇〇〇M or 18o, M (M is a hydrogen atom or an alkali metal) homopolymers of vinyl monomers or copolymers of these vinyl monomers with each other or with other vinyl monomers, such as sodium methacrylate, ammonium methacrylate , Resident Chemical Co., Ltd.! ! Sumikagel I,
-5H') is also used. Two or more of these binders can also be used in combination.

When using a system that performs thermal development by supplying a small amount of water, the use of the above-mentioned super absorbent polymer makes it possible to quickly absorb water. Further, when a highly water-absorbing polymer is used in the dye fixing layer or its protective layer, it is possible to prevent the dye from being retransferred from the dye fixing material to other materials after soft copying.

In the present invention, the amount of binder applied is preferably 208 or less per lllI2, particularly 10g or less, and more preferably 7g or less.
It is appropriate to do the following.

The structure NJ of the photosensitive material or dye fixing material (including the pack layer) contains various polymers for the purpose of improving film properties such as dimensional stabilization, prevention of curling, prevention of adhesion, prevention of film cracking, and prevention of pressure sensitivity. It can contain latex. Specifically, JP-A-62-245258 and JP-A-62-13
Any of the polymer latexes described in No. 6648, No. 62-110066, etc. can be used. In particular, using a polymer latex with a low positive transition point (below 40°C) in the mordant layer can prevent cracking of the mordant layer, and using a polymer latex with a high glass transition point in the pack layer can prevent curling. can get.

Hydrophobic additives such as dye-donating compounds and diffusion-resistant reducing agents can be incorporated into the layers of the light-sensitive material by known methods such as those described in U.S. Pat. No. 2,322,027. In this case, Japanese Unexamined Patent Application Publication Nos. 59-83154 and 59-83154,
No. 178451, No. 59-178452, No. 59-1
No. 78453, No. 59-178454, No. 59-17
No. 8455, No. 59-178457, etc., a high boiling point organic solvent with a boiling point of 50°C to 160°C is used as necessary.
It can be used in combination with a low boiling point organic solvent at ℃.

The amount of high-boiling organic solvent is 1 g of the dye-donating compound used.
10 g or less, preferably 5 g or less. Also, less than ice per 1g of banhgu, and even 0.5c
c or less, particularly 0.3ee or less is suitable.

Dispersion methods using polymers described in Japanese Patent Publication No. 51-39853 and Japanese Patent Application Laid-Open No. 51-59943 can also be used.

In the case of a compound that is substantially insoluble in water, it can be dispersed and contained in the form of fine particles in the bangu, in addition to the above-mentioned method.

When dispersing a hydrophobic compound in a hydrophilic colloid, various surfactants can be used.
The surfactants listed on pages (37) to (3rd) of No. 157636 can be used.

In the present invention, a compound that activates development and stabilizes images can be used in the light-sensitive material. For specific compounds preferably used, see U.S. Patent No. 4,50.
It is described in columns ttS51-52 of No. 0,626.

In systems that form images by diffusion transfer of dyes, a dye-fixing material is used together with a light-sensitive material. 6 The relationship between the light-sensitive material and the dye-fixing material, the relationship with the support, and the relationship with the white reflective layer is described in U.S. Pat. No. 4.500.626. The relationship described in Section 57a of the above is also applicable to the present application.

The dye fixing material preferably used in the present invention has at least IN a layer containing a mordant and a binder. As the mordant, those known in the photographic field can be used, and specific examples thereof include U.S. Pat. No. 4,500.4326 No. 58-59
Mordants described in columns and pages (32) to (41) of JP-A-61-88256, JP-A-62-244043 and JP-A-62-62
-244036 etc. can be mentioned. Also, dye-receiving polymeric compounds such as those described in US Pat. No. 4,463,079 may be used.

The dye fixing material may be provided with auxiliary layers such as a protective layer, a release layer, and an anti-curl layer, if necessary.

In particular, it is useful to provide a protective layer.

In the constituent layers of the light-sensitive material and the dye-fixing material, a high-boiling organic solvent can be used as a plasticizer, a slippery agent, or a peelability improver between the light-sensitive material and the dye-fixing material. Specifically, page (25) of JP-A-62-253159;
-245253, etc.

Furthermore, various silicone oils (
All silicone oils can be used, from trimethylsilicone oil to modified silicone oils in which various organic groups are introduced into trimethylsiloxane. For example,
[Modified silicone oil] published by Shin-Etsu Silicone Co., Ltd.
Various modified silicone oils described in technical data P6-18B, especially carboxy-modified silicone (trade name X-22-
3710) etc. are effective.

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

Antifading agents may be used in photosensitive materials and dye fixing materials. Examples of antifading agents include antioxidants, ultraviolet absorbers, and certain complexes.

Examples of antioxidants include chroman compounds, coumaran compounds, 7-enol compounds (for example, hindered phenols), hydroquinone derivatives, hinged amine derivatives, and spiroingene compounds. Compounds described in JP-A-61-159644 are also effective.

Benzotriazole compounds (
U.S. Pat. No. 3,533,794, etc.), 4-thiazolidone compounds (U.S. Pat. 62-1
There are compounds described in No. 36641, No. 61-88256, and the like. Further, the ultraviolet absorbing polymer described in JP-A-62-2GO152 is also effective.

As metal complexes, US Pat. No. 4,241,155,
Same No. 4,245,018 No. 3-36s1 Same No. 4,25
4. i95 No. 3-8IIA, JP-A-62-1747
No. 41, No. 61-88256, pages (27) to (29),
There are compounds described in Japanese Patent Application No. 63-199248, Japanese Patent Application No. 62-234103, Japanese Patent Application No. 62-230595, etc.

Examples of useful anti-fading agents are disclosed in JP-A No. 62-215272 (
125) to (137).

The anti-fading agent for preventing fading of the dye transferred to the dye-fixing material may be included in the dye-fixing material in advance, or may be supplied to the dye-fixing material from outside the photosensitive material.

The above antioxidants, ultraviolet absorbers, and metal complexes may be used in combination.

Optical brighteners may be used in photosensitive materials and dye-fixing materials. In particular, it is preferable to incorporate a fluorescent whitening agent into the dye-fixing material or to supply it from outside the photosensitive material. For example, K. Veenka taraman, rTh
e Chemistry of 5ynthetic
DyesJttSV8158 chapter, JP-A-6L-i437
Examples include compounds described in No. 52 and the like. More specifically, stilbene compounds, coumarin compounds, biphenyl compounds, benzoxacylyl compounds, naphthalimide compounds, pyrazoline compounds,
Examples include carbostyryl compounds.

Optical brighteners can be used in combination with antifade agents.

Hardeners used in constituent layers of photosensitive materials and dye-fixing materials include U.S. Pat.
Examples include hardeners described in Japanese Patent No. 61-18942.

More specifically, aldehyde hardeners (formaldehyde, etc.), acridine hardeners, epoxy hardeners (nylsulfonylacetamide, ethane, etc.), tomethylol hardeners (dimethylol urea, etc.), or Examples include polymeric hardeners (compounds described in JP-A-62-234157 and the like).

Various surfactants can be used in constituent layers of photosensitive materials and dye fixing materials for purposes such as coating aids, improving peelability, improving slipperiness, preventing static electricity, and promoting development. Specific examples of surfactants are given in JP-A-62-173463 and JP-A-62-18.
It is described in No. 3457, etc.

The constituent layers of photosensitive materials and dye-fixing materials include improved slipperiness,
An organic fluoro compound may be included for the purpose of preventing static electricity and improving peelability. Representative examples of organic fluoro compounds include Japanese Patent Publication No. 57-9053, columns 8 to 17,
20944, 62-135826, etc., or hydrophobic fluorine compounds such as oily fluorine compounds such as fluorine oil or solid fluorine compound resins such as tetra7fluoroethylene resin. can be mentioned.

A matting agent can be used in the photosensitive material and the dye fixing material. As a matting agent, silicon dioxide, polyolefin or polymethacrylate may be used.
In addition to the compounds described in No. 6 (page 29), benzoguanamine resin beads, polycarbonate resin beads, ASt34
Patent Application No. 110064/1983 for fat beads, etc. [32
There is a compound described in No.-110065.

In addition, the constituent layers of the light-sensitive material and the dye-fixing material may contain a thermal solvent, an antifoaming agent, an anti-foaming agent, a colloidal silica, etc. Specific examples of these additives are given in JP-A No. 61-1999.
No. 88256! :tS (26) to (32) pages.

In the present invention, it is possible to use an image formation accelerator in the light-sensitive material and/or the dye fixing material. 0M image formation accelerator M has #I salt acceleration of the redox reaction between the oxidizing agent and the reducing agent, and dye-donating property. It has functions such as promoting reactions such as production of dyes from substances, decomposition of dyes, and release of diffusible dyes, and promotion of transfer of dyes from the light-sensitive material layer to the dye fixing layer. It is classified into bases or base precursors, nucleophilic compounds, high-boiling organic solvents (oils), thermal solvents, surfactants, and compounds that interact with silver or silver ions. However, these substance groups are generally complex W1
It usually has some of the above-mentioned promoting effects. Details of these can be found in U.S. Patents 4 and 6.
No. 78,739, PIS columns 38-40.

Examples of base precursors include salts of organic acids and bases that are decarboxylated by heat, compounds that undergo intramolecular nucleophilic substitution reactions, Rossen rearrangement, or Beckmann rearrangement to release amines. Specific examples thereof are described in U.S. Pat.

In a system in which thermal development and dye transfer are performed simultaneously in the presence of a small amount of water, it is preferable to include a base and/or a base precursor in the dye-fixing material in order to improve the storage stability of the photosensitive material.

In addition to the above, poorly soluble metal compounds described in European Patent Publication No. 1Jl 1210,660 and U.S. Patent No. 4,740,445 and compounds capable of complex-forming reactions with metal ions forming this poorly soluble metal compound (referred to as fri-forming compounds) and compounds that generate bases by electrolysis as described in JP-A No. 61-232451 can also be used as base precursors. The former method is particularly effective.

It is advantageous to add the poorly soluble metal compound and the complex-forming compound to the light-sensitive material and the dye-fixing material separately.

Various development stoppers can be used in the light-sensitive material and/or dye-fixing material of the present invention in order to always obtain a constant image despite fluctuations in processing temperature and processing time during development.

The development stopper referred to here is a compound that neutralizes the base or reacts with the base to reduce the base concentration in the film and stop development, or a compound that interacts with silver salt to stop development after proper development. It is an inhibitory compound.

Specifically, an acid precursor that releases acid upon heating;
Examples thereof include electrophilic compounds that undergo a substitution reaction with a shared base when heated, nitrogen-containing heterocyclic compounds, mercapto compounds, and precursors thereof.

For further details, see JP-A No. 62-253159 (31).
It is described on page (32).

As a support for the light-sensitive material or dye-fixing material of the present invention, one that can withstand processing temperatures is used. Common examples include paper and synthetic polymers (films). Specifically, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene,
Polyimide, cellulose M (e.g. triacetylcellulose) or films containing pigments such as titanium oxide, film-based synthetic paper made from polypropylene, synthetic resin pulp such as polyethylene, and natural pulp. Mixed paper, Yankee paper, Baryta paper, Coachite paper (especially cast coated paper), metal, cloth, lath lids, etc. are used.

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

In addition, JP-A-62-253159 (29) to (3)
The supports described on page 1) can be used.

Hydrophilic paint and alumina sol, semiconducting metal oxides such as tin oxide, h-bon black and other materials are applied to the surface of these supports. An rI antistatic agent may be applied.

Methods of exposing and recording images on photosensitive materials include, for example, directly photographing landscapes and people using a camera, exposing through reversal film or negative film using a printer or enlarger, and using a copying machine. A method of scanning and exposing an original image through a slit using an exposure device, a method of exposing an image by emitting light from a light emitting diode, various lasers, etc. via an electric signal, a method of transmitting image information to a CRT, liquid crystal display, electroluminescence, etc. There is a method of outputting the image to an image display device such as a display or a BRA-X display, and exposing the image directly or through an optical system.

Light sources for recording images on photosensitive materials include natural light, tungsten lamps, light emitting diodes, laser light sources, CRTt sources, etc. as mentioned above, such as U.S. Patent No. 4.500.6.
The light source described in No. 26, column 56 can be used.

Further, image exposure can also be performed using a wavelength conversion element that combines a nonlinear optical material and a flexible light source such as a laser beam. Here, nonlinear optical materials are materials that can exhibit nonlinearity between the polarization and electric field that appear when a strong charging field such as laser light is applied, and include lithium niobate, potassium dihydrogen phosphate (KDP) ), lithium iodate, inorganic compounds such as Ba820, urea derivatives, nitroaniline derivatives, such as 3-methyl-
Nitropyridine-N-oxide derivatives such as 4-nitropyridine-N-oxide (POM), JP-A-61-
Compounds described in No. 53462 and No. 62-:10432 are preferably used. The form of the wavelength conversion element is as follows:
A single-crystal optical waveguide type, a 7-eyeper type, and the like are known, and any of them are useful.

In addition, the above-mentioned image information is obtained from image signals obtained from video cameras, electronic still cameras, etc., television signals represented by the Nippon Television Signal Standard (NTSC), and original images obtained by dividing them into a large number of pixels using a scanner. Image signal, CG%C
Image signals created using a computer such as AD can be used.

The photosensitive material and/or the dye-fixing material may have a conductive heating layer as a heating means for heat development or diffusion transfer of the dye.

In this case, the transparent or opaque heating element is
1 145'544 can be used. Note that these conductive layers also function as an antistatic layer.

The heating temperature in the heat development process can be developed at about 0°C to about 250°C, but it is most useful to use a heating temperature of about 0°C to about 180°C.The diffusion transfer process for dyes is carried out at the same time as heat development. In the latter case, the heating temperature in the transfer step can be in the range from the temperature in the heat development step to room temperature, but especially heat development at 50° C. or higher is possible. More preferably, the temperature is up to about 10° C. lower than the temperature in the process.

Dye migration can also be caused by heat alone, but a solvent may be used to promote dye migration.

Also, 1986-218443 and 61-2380
A small amount of solvent (water in vf) as detailed in No. 56 etc.
It is also useful to carry out development and transfer simultaneously or continuously by heating in the presence of
The temperature is preferably 0°C or higher and the boiling point of the solvent or lower. For example, when the solvent is water, the temperature is preferably 50°C or higher and 100°C or lower.

Examples of solvents used to accelerate development and/or transfer the diffusible dye to the dye fixed layer include water or basic aqueous solvents containing inorganic alkali metal salts and organic bases. (
Examples of these bases include those described in the section of image formation accelerators. Furthermore, a low boiling point solvent or a mixed solution of a low boiling point solvent and water or a basic aqueous solution can also be used. In addition, a surfactant, an anti-capri compound, a poorly soluble 4-group salt, a complex-forming compound, etc. may be included in the solvent.

These solvents can be used by attaching them to dye fixing materials, photosensitive materials, or both.

The amount used may be as small as less than the weight of the solvent corresponding to the maximum swelling volume of the entire coating (particularly less than the weight of the solvent corresponding to the maximum swelling volume of the entire coating minus the weight of the entire coating).

As a method of applying a solvent to a photosensitive layer or a dye fixing layer, Teha, Example Ljr, Special 1jl! @ No. 61-147244 (26
There is a method described on page ). Further, the solvent can be incorporated in advance into the photosensitive material, the dye fixing material, or both, such as by encapsulating the solvent in microcapsules.

Furthermore, in order to promote dye transfer, a method may be adopted in which a hydrophilic thermal solvent that is solid at room temperature and dissolves at high temperature is incorporated into the light-sensitive material or dye fixing material. The hydrophilic thermal solvent may be incorporated into either the photosensitive material or the dye-fixing material, or may be incorporated into both.The layer in which it is incorporated may also be an emulsion layer, an intermediate layer, a protective layer, or a dye-fixing layer. It is preferable to incorporate the dye fixing layer into/or a layer adjacent thereto.

Examples of hydrophilic heat solvents include ureas, birinones, amides, sulfonamides, imides, alnyls, oximes, and other heterocycles.

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

Heating methods during the development/transfer process include contact with a heated block or plate, hot plate, hot breather, heat roller-halogen lamp heater, infrared and far-infrared lamp heater, etc. or passing through a high-temperature atmosphere.

The pressure conditions and method of applying pressure when overlapping the photosensitive material and the dye-fixing material and bringing them into close contact are described in Japanese Patent Application Laid-Open No. 1472-1983.
The method described in No. 44, page 27 can be applied.

Any of a variety of thermal development equipment can be used to process the photographic elements of this invention. For example, JP-A No. 59-75247,
Apparatuses described in Japanese Utility Model No. 59-177547, No. 59-181353, No. 60-18951, Japanese Utility Model Application Publication No. 62-25944, etc. are preferably used.

Hereinafter, the present invention will be specifically explained with reference to Examples.

<Example 1> We will describe how to make emulsions ■ to ■.

[Emulsion ■]

A well-stirred gelatin aqueous solution (20 g of gelatin, 3 g of potassium bromide, and HO (CHg) in 800 cc of water)
)t S (CHz)x S (CHz)z 0H(7
) to the following (
Solution 1) and solution (2) were added simultaneously over 30 minutes. Thereafter, the following solutions (3) and (4) were simultaneously added over 20 minutes. Further, after starting the addition of the liquid (3), the following dye solution (A) was added over a period of 18 minutes from 5 minutes.

After washing with water and salting, 20g of lime-treated ossein gelatin was added to adjust the pH to 6.2 and PAg to 8.5, and then sodium thiosulfate and 4-hydroxy6-methyl-1,3,3
a,? -Tetrazaindene was optimally chemically aggravated by adding chloroauric acid. Thus the average particle size, 0.40
600 g of a monodisperse dodecahedral silver iodobromide emulsion of μ was obtained.

Dye solution (A) 0.12g (CHl)4SOs-(CHt)4sOJ・NEt30
．． A solution of 12g dissolved in 160cc of methanol.

[Emulsion ■]

A well-stirred aqueous solution (20 g of gelatin, 0.30 g of potassium bromide, 6 ml of sodium chloride in 730 mj of water)
g and 0.015 g of the following chemical A and kept at 60.0°C), the following solutions (1) and (n) were added at the same time for 60 g.
Added at equal flow rates over minutes. (I) After completion of liquid addition
The following sensitizing dye solution (B) was added. In this way, a monodisperse cubic emulsion adsorbed with a dye having an average grain size of 0.45 μm was prepared.

After washing with water and desalting, add 20g of gelatin and adjust the pH to 6.4.
After adjusting PAg to 7.8, chemical sensitization was performed at 60°0°C. The chemicals used at this time were 1.6μ of triethylthiourea and 4-hydroxy-6-methyl-1,3,3a.
,? - The aging time was 55 minutes using 100 ml of tetrazaindene. The yield of this emulsion was 635 g.

(Chemical A) (Dye B) [Emulsion ■] A well-stirred gelatin aqueous solution (20 g of gelatin, 1 g of potassium bromide, and OH (CHz
)x S (CHz)t Add 0.5g of OH and heat at 50°
The following solution (1), solution (n), and dye solution (C) were added at the same time at the same flow rate over 30 minutes. In this way, a monodisperse silver bromide emulsion having an average grain size of 0.42 μm and adsorbing a dye was prepared.

After washing with water and desalting, add 20g of lime-treated ossein gelatin, adjust the pH to 6.4 and PAg to 8.2, and then
Incubate at temperature C, add 9cm of sodium periosulfate and 0.5cm of chloroauric acid. O
1% aqueous solution 6m! , 4-hydroxy-6-methyl-1,
Add 190 ■ of 3,3a,7-chitrazaindene, 45
Chemical sensitization was performed for minutes. The yield of emulsion was 635 g.

Dye (b) [Emulsion ■] Emulsion ■ was prepared in exactly the same manner as Emulsion I, except that the following dye solution (D) was used in place of the dye solution (A) used in Emulsion ■.

A solution in which 0.19 g of dye solution (D) t was dissolved in a mixture of 80 cc of methanol and 80 cc of water.

[Emulsion ■] [Emulsion ■] Instead of the dye solution used in Emulsion ■, use the following dye solution (E
) (Emulsion 5) and (F) (Emulsion 6) were used, but Emulsion (2) and Emulsion (2) were prepared in exactly the same manner as Emulsion (2).

Dye solution (E) t Dye solution (G) 0.14g to 80mj of methanol! liquid dissolved in.

Dye solution (F) A solution of 0.16g dissolved in methanol LOOmf.

[Emulsion ■]

Emulsion ■ was prepared in 11& ! Shita.

A solution of 0.21g dissolved in a mixture of 80cc of methanol and 80cc of water.

A method for preparing a dispersion of zinc hydroxide will be described.

12.5 g of zinc hydroxide with an average particle size of 0.2 μ 1 1 g of carboxymethyl cellulose as a dispersant, 0.1 g of sodium polyacrylate, and 100 cc of a 4% gelatin aqueous solution
In addition, the mixture was ground for 30 minutes in a mill using glass beads having an average particle size of 0.75. The glass peas were separated to obtain a dispersion of zinc hydroxide.

Next, a method for preparing an activated carbon dispersion will be described.

Activated carbon powder (reagent, special grade) manufactured by Wako Tsumugi Co., Ltd. 2゜5g,
As a dispersant, 0.25 g of Demol N1g1 polyethylene glycol nonylphenyl ether manufactured by Kao Soap Co., Ltd.
was added to 100 cc of a 5% gelatin aqueous solution and ground for 120 minutes in a mill using glass beads with an average particle size of 0.75 m. The glass beads were separated to obtain an activated carbon dispersion with an average particle size of 0.5 μm.

Next, a method for preparing a dispersion of an electron transfer agent will be described.

10g of the following electron transfer agent, 0.0g of polyethylene glycol nonylphenyl ether as a dispersant. 5 g of the following anionic surfactant were added to a 5% aqueous gelatin solution, and the mixture was pulverized for 60 minutes using a mill with an average particle size of 0 and 75 mm diameter Karakara beads. Separate the glass beads and reduce the average particle size to 0.
．． A 3μ electron transfer agent dispersion was obtained.

Electron Transfer Agent Next, we will discuss how to make a gelatin dispersion of a dye-donating compound.

Each of yellow, magenta, and cyan was added to 50 cc of ethyl acetate according to the following recipe and dissolved by heating to about 60°C to form a uniform solution. This solution and 100 g of a 10% aqueous solution of lime-treated gelatin, dodecyl.

Rubenzenesulfonic acid sodium 0.6g and water 50cc
After stirring and mixing, in a homogenizer for 10 minutes at 110
Dispersion was carried out at 000 rpm. This dispersion is called a gelatin dispersion of a dye-providing compound.

Anionic surfactant CHxCOOCHzCH(CzHs)CJgNaOsS
CHCOOCH*CH(CJs)CaL electron donor ■ 5g 1 After stirring and mixing 0.3g of dodecylbenzenesulfonic acid sorter and 30cc of water, 1
Dispersion was performed at 110,000 rpm for 0 minutes. This dispersion is called a gelatin dispersion of electron donor (1).

Electron donor ■ Electron transfer agent precursor ■ Next, we will describe how to make a gelatin dispersion of electron donor (■) for the intermediate layer.

The following electron donor ■23.6g and the above high boiling point solvent ■8
．． 5 g was added to 30 cc of ethyl acetate to form a homogeneous solution.

This solution and 100 g of a 10% aqueous solution of lime-processed gelatin
, sodium bisulfite 0. 2 Note 1) Surfactant ■ Note 7) Electron transfer agent ■ Note 2) Surfactant ■ CHgCOOCHxC)I(CJs)CJwNa03S
-CCHgC00CHxC)I(CJs)CJ Note 8) Electron transfer agent ■ Note 3) Water-soluble polymer Note 4) Antifoggant ■ Note 9) Hardener [phase] l.

2-bis(vinylsulfonylacetamido)ethane Note 5) Surfactant ■ Note 10) Antifoggant O Note 6) Surfactant ■ Silicone oil (1) Surfactant (1) Surfactant (2) CsF+tSOJCHxCOOK CsH? Surfactant (3) Mordant (1) High boiling point solvent (1) Matting agent (1) 0 Silica matting agent (2) 0 Benzoguanamine resin (average particle size 15μ) Surfactant (4) Js CHiCOOCIltCIICntlqNaOsS
CHCOOCHxC11CJ*tHS Fluorescent brightener (1) 2.5bis(5-tert-butylbenzoxazole(
2)) Thiophene surfactant (5) C,H CsFrtSOtN (CHtCHzO+T+-CH
5OaNa water-soluble polymer (1) Sumikagel L5-H (manufactured by Sumitomo Chemical ■) Water-soluble polymer (2) Dextran (molecular weight 70,000) [Exposure] 350 to 800 nm to the photosensitive material (101, 106)
Exposure was carried out for 1/10 second using a spectrophotographic wenge whose wavelength was changed horizontally and the amount of light was continuously changed vertically using a light source with spectral spectra. A tungsten light bulb was used as the light source, and after the light was separated, a color temperature conversion filter was used to adjust the spectral energy distribution to be close to that of standard illumination light C. Furthermore, the relative color temperature of the light obtained by converting the color temperature of the light source used without spectroscopy using the same color temperature conversion filter was approximately 6770.

〔developing〕

While feeding this exposed photosensitive material at a linear speed of 20 a/sec, 15 mj! /n( of water) was supplied with a wire bar, and immediately thereafter, the dye fixing material and the membrane surface were superimposed on the camphor tree in contact with each other.

The film was heated for 15 seconds using a heat roller whose temperature was adjusted so that the temperature of the water-absorbed film was 78°C.

Next, when it is peeled off from the image-receiving material, a blue-sensitive layer appears on the image-receiving material.
Positive spectral images in which the green-sensitive layer and the red-sensitive layer developed blue, green, and red colors at the corresponding wavelengths were evenly obtained.

From this spectrum photograph, the peak wavelength, ΔS*4@+Δs
The value read from −am is the value in Table 3 above.

Next, an experiment was conducted in exactly the same manner as the exposure and development described above, except that blue, green, red, and gray filters were used.

Note that the blue, green, and red filters used were Fuji Filter Bar color printing filters manufactured by Fuji Photo Film Co., Ltd.

Blue is applied to each exposed area through each filter.
Green and red color images are measured using X-Light Density Measuring Instrument
- Reflection density was measured using Light 404.

The results obtained are as follows.

These results show that the photosensitive material of the present invention has less color turbidity (e.g., yellow density in the blue part) and higher density (e.g., magenta and cyan density in the blue part), that is, color reproduction, compared to the comparative material. It shows that you are sexually superior.

Example 2 This section describes how to make emulsion ■～[Stock].

[Emulsion ■]

Emulsion (2) was prepared in exactly the same manner as Emulsion (2) except that emulsion (2) was not chemically sensitized.

[Emulsion ■]

Emulsion (2) was prepared in exactly the same manner as Emulsion (2) except that emulsion (2) was not chemically sensitized.

[Emulsion [Co.]]

Lime-treated bone gelatin (Ca content 250
0 ppm) solution (20 g of gelatin, 6 g of sodium chloride, and 0.015 g of potassium bromide dissolved in 730 d of water and kept at 50 "C") started adding the following solutions (1) and (2) at the same time, and over a period of 30 minutes. From 10 minutes after the addition of liquid (■), liquid (2) and liquid (m) were added over a period of 30 minutes.

Further, 1 minute after the addition of solutions (1) and (2) was completed, the dye solution (B) used in the preparation of emulsion (2) was added. ) The obtained emulsion was washed with water, desalinated, and then lime-treated bone gelatin (Ca content 4000 ppm)
Add 22g and 100d of water to adjust pH to 6.4 and PAg to 7.9.
Adjusted to. Thereafter, optimal chemical sensitization was performed at 60'C using triethylthiourea and 4=hydroxy6-methyl-1,3,3a,7-titrazaindene.

The yield of emulsion was 630 g. The emulsion obtained was cubic monodisperse grains with a grain size of 0.38 μm and a coefficient of variation of 8%.

When examined using X-ray diffraction, XPS method, and EPMA method, it was confirmed that this emulsion was a double structure type grain.

[Emulsion ■]

Emulsion (2) was prepared in exactly the same manner as the emulsion [phase] except that the reaction system kept at 50°C in the emulsion [phase] was changed to 35°C and no chemical sensitization was performed.

Next, Example 10 Table 1 was prepared using these emulsions
Photosensitive materials 201 to 204 having the same structure as above were prepared and the combinations of emulsions used here are as follows.

350-800 for these photosensitive materials (201-204)
Exposure was carried out for 1/10 second using a light source with nm spectra and a wedge for spectrophotography in which the wavelength was changed horizontally and the amount of light was continuously changed vertically.

The type of light source and color temperature conversion were the same as in Example 1.

Next, development was performed in exactly the same manner as in Example, and the peak wavelength, ΔS, 4°, and ΔS-4° were as follows.

Next, Example 1 except that a wedge in which the light amount of yellow, magenta, cyan, and gray continuously changes was used.
Exposure (n light time 1/10 seconds) and development were performed in the same manner as above.

The sensitivity at the peak wavelength of the spectral sensitivity was measured by measuring the density of the spectral image. The color reproducibility was evaluated based on the density of the cloudy component of the 1.0 density portion of yellow, magenta, and cyan single colors.

From this result, the photosensitive material of the present invention is Color reproducibility I can see that it is excellent.

Claims (1)

[Claims] A support comprising at least a photosensitive silver halide emulsion, a binder, an electron donor, an electron transfer agent, and a reducible dye-donating compound that releases a diffusible dye when reduced. In the heat-developable color photosensitive material, the photosensitive material has a blue-sensitive silver halide emulsion layer combined with a reducible dye-providing compound that releases a yellow dye, and a blue-sensitive silver halide emulsion layer combined with a reducible dye-donating compound that releases a magenta dye. It is a light-sensitive material with a multilayer structure having a red-sensitive silver halide emulsion layer combined with a red-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer combined with a red-sensitive silver halide emulsion layer and a reducible dye-donating compound that releases a cyan dye. ) 1/1 using standard illumination light C as the light source
In exposure for 0 seconds, the peak wavelength of spectral sensitivity of the blue-sensitive emulsion layer is at 450±40 nm, and the peak wavelength +
The sensitivity at a wavelength of 40 nm is lower than the sensitivity at the peak wavelength by 0.2 or more in logarithmic units, and the peak wavelength of the spectral sensitivity of the green-sensitive emulsion layer is 550 ± 40 nm.
m, and furthermore, the sensitivity at a wavelength of ±40 nm of the peak wavelength is 0.
2 or higher, and the peak wavelength of the spectral sensitivity of the red-sensitive emulsion layer is 650±40n.
m, and furthermore, the sensitivity at a wavelength of ±40 nm of the peak wavelength is 0.
A heat-developable color photosensitive material characterized by a low sensitivity of 2 or more.