JPH0246449A - Thermodevelopable color photosensitive material - Google Patents

Abstract

PURPOSE:To reduce the dependency of the subject material due to a gray viewing light source by incorporating jointly compds. (A) capable of affording a pigment to be reduced, which release the pigment having max. absorption separated from each other by more than a prescribed wavelength, respectively, in the photosensitive material. CONSTITUTION:The photosensitive material contains 3 kinds of the compds. (A) capable of affording a pigment to be reduced which release the pigment of the yellow, the magenta and the cyan diffusible pigment capable of being reduced by an electron donating body, respectively. And, the compds. (A) capable of releasing the pigment having the max. absorption separated from each other by >=5nm respectively, are incorporated jointly in one or more among 3 kinds of the compds. (A) having different hues. Thus, as the spectral absorption region of the material is broaden, the dependency of the material due to the gray viewing light source is reduced. And, the compd. (A) is composed of a compd. shown by the formula, etc. In the formula, X is oxygen or sulfur atom, etc., R<101> and R<102> are each a group other than hydrogen atom or a single bond, Time is a group capable of releasing Dye after being released as a group -(Time)t-Dye by reducing it, (t) is 0 or 1, Dye is a pigment (or its precursor).

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 capable of obtaining a positive image with excellent gray observation light source dependence. It is something.

(Background Art) Heat-developable photosensitive materials are well known in this technical field, and for information about heat-developable photosensitive materials and their processes, see, for example, "Fundamentals of Photographic Engineering" Non-Silver Salt Photography (published by Corona Publishing, 1982), pages 242 to 255. Page, US 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.
A reducing agent or its precursor is made to coexist with an oxidized compound that does not have dye-releasing ability, and the reducing agent is oxidized according to the exposure amount of silver halide by heat development, and the reducing agent that remains unoxidized 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 compound that 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.

In order to obtain a multicolor image, it is necessary to combine dye-providing compounds exhibiting different hues with silver halide emulsions having different color sensitivities, and to stack the respective layers on a support. For example, in order to obtain a wide range of colors in the chromaticity diagram using the three primary colors yellow, magenta, and cyan, it is necessary to use a photosensitive layer containing at least three sets of silver halide emulsions each having a different color sensitivity.

Achieving good color reproducibility is a major issue in such color photosensitive materials, but in subtractive color photography using three dyes: yellow, magenta, and cyan, the color image that should represent gray is difficult to achieve. It is extremely important that the image be observed as gray under various observation light sources without any tint.

Specifically, in the visible spectrum wavelength range of 380 to 780 nm, it is desirable that the integrated density distribution obtained by the combination of three dyes, yellow, magenta, and cyan, be a constant value regardless of the wavelength.

However, it is practically impossible to design the spectral absorption distribution of these three dyes so that the integral concentration distribution is constant regardless of the wavelength.

In addition, recently, observation light sources have become more diverse, and fluorescent lamps with bright line components as their main component, especially red bright line components, are used. has also been developed.

(Problem to be solved by the invention) A new type of daylight white fluorescent lamp, which mainly consists of these emission lines, has recently become widespread in offices and homes, and there are extremely many opportunities to view color photographs under this light source. It is thought that it has become.

Therefore, it has become essential to design the balance of spectral absorption of yellow, magenta, and cyan so that a color image that should represent gray is observed as gray even under such a light source.

An object of the present invention is to provide a heat-developable photosensitive material that has excellent gray dependence on a viewing light source.

(Means for Solving the Problems) An object of the present invention is to reduce yellow, magenta, and cyan, respectively, by reducing photosensitive silver halide, a binder, an electron donor, an electron transfer agent, and the electron donor on a support. A heat-developable color photosensitive material comprising three types of reducible dye-providing compounds that release a diffusible dye,
A heat-developable color photosensitive material characterized in that two or more types of reducible dye-donating metals are used in combination to provide dyes whose absorption maxima are separated from each other by 5 nanometers or more in at least one hue of yellow magenta and cyan. achieved by the material.

For convenience, the present invention will be explained using a model using two types of reducible dye-donating compounds capable of releasing cyan dyes whose absorption maxima are separated from each other by 5 nanometers or more.

Figure 1 shows an ideal gray observation light source with excellent dependence on the light source.
A curve of spectral absorption is shown.

Now, yellow and magenta almost satisfy the conditions, but let us take as an example a case where the spectral absorption curve of cyan deviates from the spectral absorption curve of cyan in FIG.

The spectral absorption curve (cyan) in Figure 2 is for the case where one type of reducible dye-donating compound is used, and although the absorption maximum matches the cyan spectral absorption maximum in Figure 4, shortwave and The problem still remains that the dependence of gray on the observation light source is very poor due to the lack of long-wave absorption.

When using one type of reducible dye-donating compound,
It is extremely difficult to develop and synthesize a dye-donating compound that can cover a wide absorption range as shown in Figure 1.

Therefore, in the present invention, as shown in FIG. 3, reducible dye-donating compounds capable of emitting cyan dyes of relatively short wavelength (1) and long wavelength (O) are mixed and used in appropriate ratios. It has been found that when such a combination is used, a spectral absorption curve as shown by the wavy line O, which is very similar to that in FIG. 1, can be obtained, and results that fully satisfy the observation light source dependence of gray can be obtained.

It has also been found that the above effect can be achieved if the absorption maxima of the short wave (1) and the long wave (O) are separated by 5 nanometers or more.

The second basic concept is not limited to cyan;
Similar effects could be obtained with magenta and yellow.

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 general formula (c-B).

PWR-(Time)t-Dye general formula [C~1
] In the formula, PWR is reduced to (Time)t
-Represents a Dye-releasing group.

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

t represents an integer of 0 or 1.

Dye represents a dye or its precursor.

First, PWR will be explained in detail.

PWR is US Pat. No. 4,139,389, or US Pat. No. 4,139,379, US Pat. No. 4,564.577,
Electron-accepting center and intramolecular nucleophilic substitution reaction in a compound that releases a photographic reagent by an intramolecular nucleophilic substitution reaction after being reduced as disclosed in JP-A-59-185333 and JP-A-57-84453 It may correspond to the part including the center, or as described in U.S. Pat. As disclosed, it corresponds to the part containing the electron-accepting quinonoid center and the carbon atom linking it to the photographic reagent in a compound that releases the photographic reagent by an electron transfer reaction in the molecule after being reduced. It's okay. Also, JP-A-56-14253
No. 0, U.S. Pat. No. 4,343,893, U.S. Pat. No. 4,619.
884, in which the single bond is cleaved to release the photographic reagent, an aryl group substituted with an electron-withdrawing group and the atom connecting it to the photographic reagent (
It may correspond to a moiety containing a sulfur atom, a carbon atom, or a nitrogen atom). Also, U.S. Patent No. 4,450
It may correspond to a moiety containing a nitro group in a diroto compound that releases a photographic reagent after accepting electrons and a carbon atom that connects the photographic reagent with the nitro group, as disclosed in No. 223. , corresponds to the geminal dinitro moiety in the dinitro compound that beta-leaves the photographic reagent after electron acceptance and the moiety containing the carbon atom linking it to the photographic reagent described in U.S. Pat. No. 4,609,610. It's okay.

In addition, compounds having 5o2-X (X represents oxygen, sulfur, or nitrogen) and an electron-withdrawing group in one molecule described in Japanese Patent Application No. 62-10.6885,
106895, a po-x bond (X
has the same meaning as above) and an electron-withdrawing group, a c-x' bond (X' has the same meaning as X or represents 18O□-) in one molecule described in Japanese Patent Application No. 106887/1987 and a compound having an electron-withdrawing group.

In order to more fully achieve the object of the present invention, the general formula (c
Among the compounds represented by -H, those represented by the general formula (CIF) are preferred.

General formula (CII) EAG' (Time (t Dye is bonded to at least one of RIOI, R1112, or EAG).

The portion corresponding to PWR in general formula (C1l) will be explained.

X represents a group (-N (R163)-) containing an oxygen atom (-0-), a sulfur atom (-3-), or a nitrogen atom.

R101, R102 and R103 represent a group other than a hydrogen atom or a simple bond.

Groups other than hydrogen atoms represented by RIDI, R102, and RI03 include alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, sulfonyl groups, carbamoyl groups, and sulfamoyl groups, and these include substituted It may have a group.

1 〇-RI OI and R1°'' are preferably substituted or unsubstituted alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, acyl groups, sulfonyl groups, etc. 1%
The number of carbon atoms in IQ+ and R103 is preferably 1 to 40.

R102 is preferably a substituted or unsubstituted acyl group or sulfonyl group. Examples are the same as the acyl group and sulfonyl group mentioned for R101 and R101. The number of carbons is 1
~40 is preferred.

RIOI, R102 and Rlo:l may be bonded to each other to form a pentagonal or hemagonal ring.

As X, enzymes are particularly preferred.

EAG will be described later.

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

General formula [CITl) BAG' (TimehtDye binds to at least one of Rro4 and E A G.

χ represents the same meaning as above.

R104 represents χ, an atomic group that is bonded to a nitrogen atom to form a five- or six-membered monocyclic or condensed heterocycle including the nitrogen atom.

BAG 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).

General formula (A,) In general formula (A), Z represents -C-3ub or -N-.

■7 is 2. ．． It represents an atomic group which together with 22 forms a 3- to 1-membered aromatic group, and n represents an integer from 3 to 3.

■3;-Zs-・v, 1-L-z,-・■523-2
4-2. ．． -1V6; Zs ZaZ, -Z
6-1V7; Zs Z4 Zs Z6
Z7-1 Vai Zs Za Zs Z
bZ7 Za-.

Each of Sub 5ub Z 2 Z y represents -(, --N--Oub S-1 or -5O2-, and each Sub represents a simple bond (pi bond), a hydrogen atom, or a substituent described below. .Even if each Sub is the same,
Each of them may be different, or each may be bonded to each other to form a three- or he-membered saturated or unsaturated carbocycle or heterocycle.

In general formula [A], the sum of the Hammett substituent constant sigma variations of the substituents is -1-0.50 or more, more preferably +
Select Sub so that it is 0.70 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. It can be used to adjust the properties, reactivity toward electrophilic groups, etc.

A specific example of EAG is European Patent Publication 2207.16A2
No. 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.

Various groups represented by Time are known, for example, JP-A-61-147244, pages (5)-(6), JP-A-61-147244.
No. 36549 (8) page - En page, patent application 1988-88625
Examples include the groups described on pages (36) to (44).

The compound represented by the above general formula [C■] or (cm) must itself be immobile in the photographic layer, and therefore EAGSRlol, RI02R104 or X
It is desirable to have a ballast group having 8 or more carbon atoms at the position (particularly at the EAG position).

The dyes represented by Dy and e include azo dyes, azomethine dyes,
anthraquinone dye, naphthoquinone dye, styryl group,
These include 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.

In this case, the absorption maximum value refers to the value after double coloring.

Specifically, it can be selected and used from the documents shown below. That is, cyan, magenta,
In at least one of the yellow hues, particularly in the cyan hue, dyes whose absorption maximums are separated from each other by 5 nanometers or more or dye precursors that provide such dyes are selected, and each dye has the general formula (C-1 ) as Dye of PWR-(
Timc! Two or more dye-donating compounds bonded to -1 are used.

Examples of cyan dyes: U.S. Pat. No. 3,482,972, U.S. Pat. No. 3,929,760,
4,013,635, 4,268.625, 4,171,220, 4゜242.435, 4
, No. 142,891, No. 4.195,994, No. 4,
No. 147,544, No. 4,148,642; British Patent No. 1,551°138; Japanese Patent Publication No. 51-99431, No. 528827, No. 53-47823, No. 53-14
No. 3323, No. 54-99431, No. 5671061
No.: Europe, PA Patent (RPC) No. 53゜037, 5
3. 04 Q; Re5search 1) iscl
osure17.630 (1978) and 16
No. 475 (1977), JP-A-60-93434, JP-A-62-118343, Patent Application No. 183300-1983
The items listed in the No.

Example of magenta dye: U.S. Pat. No. 3,453,107, U.S. Pat. No. 3,544°545
No. 3,932,380, No. 3931.144,
No. 3,932,308, No. 3954.476, No. 4,233,237, No. 4.255,509, No. 4
, No. 250,246, No. 4,142.891, No. 4.
207 No. 104, No. 4,287,292: Unexamined Japanese Patent Publication No. 5
No. 2-106.727, No. 52-106727, No. 5
No. 323.628, No. 55-36,804, No. 56-
No. 73,057, No. 56-71060, No. 55-13
No. 4, as described in JP-A No. 61-273542.

Example of yellow dye: U.S. Pat. No. 3,597,200, U.S. Pat. No. 3,309°199
No. 4,013,633, No. 4245.028,
4,156,609, 4139.383, 4
, No. 195,992, No. 4.148,641, No. 4,
No. 148,643, No. 4,336,322: Japanese Unexamined Patent Publication No. 1973
No. 1-114930, No. 56-71072: Re5
archDisc1osure I 7630 (
No. 197B), No. 16475 (1977), JP-A-59-123837, JP-A-61-270757,
What is described in Japanese Patent Application Laid-Open No. 61261738.

Solution −佦佃 ← 汽 8 ト・＼ 明 −10へ ← 八 − Σ ＝ ＼/ As a combination of reducible dye-donating compounds of the present invention,
In cyan, a combination of C,-(1) and one or more of C-(2) to C(12), especially C(1) and c-(2), c-
In addition to N) and C-(6), C-(1) and C-(8), C
-(3) and C(8), C-(9) and c-(1,0), C
-(5) and C-(8), C-(7) and C-(IILc(
9) and C-(12). Also, for magenta, M-(1) and M-(3), M-(1) and M-(5L
There are combinations of M-(2) and M-(3), etc. For yellow, Y-(1) and Y-(2), Y-(2) and Y-(4
), a combination of Y-(1) and Y-(5), etc.

It is relatively easy to obtain the ideal spectral absorption characteristics shown in FIG. 1 with one type of dye for yellow magenta, but it is difficult for cyan. The measures of the invention are therefore particularly useful for cyan hues.

For reference, the absorption maximum values of cyan dye obtained from the above-mentioned cyan dye-releasing compounds are shown below.

C~(A) 622nm C~(2) 670nm C~(3) 662nm C~(4) 662nm C~(5) 650nm C~(6) 662nm C~(7) 636nm C~(8) 662nm C~ (9) 636 nm C-(10) 660 nm C-(11) 650 nm C-(12) 646 nm 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/bo, preferably 0.1 to 3 mmol/bo.
It is in the mmol/po range. The dye-donating substances 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 JP-A No. 60-162251, for example, a layer containing at least one cyan, magenta, and yellow dye-providing substance and a silver halide. It is also possible to use a mixture of two or more dye-providing substances that release mobile dyes having different hues, such as by mixing and containing them in the middle or adjacent layers.

In the present invention, an electron donor and an electron transfer agent (IETA) are used, and details of these compounds are described in European Patent Publication No. 220746A2, Technical Report No. 876199, and the like. Particularly preferred electron donors (or precursors thereof) are compounds represented by the following general formula (C) or (D).

General formula (C) OA.

General formula CD) 0AIO In the formula, A I Q 1 and A+oz each represent a hydrogen atom or a protecting group for a phenolic hydroxyl group that can be deprotected with a nucleophilic reagent.

Here, as the nucleophilic reagent, OH○, Roo (R; alkyl group, aryl group, etc.), hydroxamic acid anion 1
Examples include anionic reagents such as sO3"e, and compounds having lone pairs of electrons such as primary or secondary amines, hydrazine, hydroxylamines, alcohols, and thiols.

Preferred examples of A Iol and AlO2 include a hydrogen atom, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a dialkylphosphoryl group, a dialkylphosphoryl group, or JP-A-59-197037; Same 59-
20105 may be used, and AIO+, AlO2 may be R2°1, R2 when possible.
°2, R2O3 and R204 may be combined with each other to form a ring. Further, Al01 and AlO2 may both be the same or different.

R2°! , R202, R2O3 Oyobi R20' C1.
Represents a hydrogen atom, an alkyl group, an aryl group, an alkylthio group, an aryldio group, a sulfonyl group, a sulfo group, a halogen atom, a cyano group, a carbamoyl group, a sulfamoyl group, an amide group, an imide group, a carboxyl group, a sulfonamide group, etc. . These groups may have a substituent if possible.

However, the total carbon number of R201 to R204 is 8 or more. Also, in General 2 CC], R2°1 and R202
and/or R2O3 and R204 may be combined with each other to form a saturated or unsaturated ring.

Among the electron donors represented by the general formula (C) or [D], those in which at least two of R201 to R20' are substituents other than hydrogen atoms are preferred. Particularly preferred compounds are those in which at least one of R2°l and R202 and at least one of R2O3 and R2°4 are substituents other than hydrogen atoms.

A plurality of electron donors may be used in combination, or an electron donor and its precursor may be used in combination. Further, the electron donor may be the same compound as the reducing substance of the present invention. Specific examples of the electron donor will be listed, but the invention is not limited to these compounds.

(ED-4) H (ED-5) H3 (ED-6) 1l (ED-3) 0■ (ED-11) 0H (ED-12) (ED H Ha (ED-13) Electron donor (or The amount of the precursor) to be used has a wide range, but is preferably 0.0 per mole of positive dye-providing substance.
A preferred range is from 1 mol to 50 mol, particularly from 0.1 mol to 5 mol. Also, 0.00% per mole of silver halide.
001 mol to 5 mol, preferably 0.01 mol to 1.5 mol
It is a mole.

As the ETA 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 thereof has the ability to cross-oxidize the above electron donor. Preferably a sexual one.

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

CX-I) (X-U) In the formula, R represents an aryl group. R201, R302Rf
f03, R304, R3+15 and R306 are a hydrogen atom, a halogen atom, an acylamino group, an alkoxy group,
It represents an alkylthio group, an alkyl group or an aryl group, and may be substituted if possible. Further, these may be the same or different.

In the present invention, compounds represented by general formula (xn) are particularly preferred. In the general formula (x-n), R3
01, R302, R'JO3 and R364 are preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a substituted alkyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted aryl group, more preferably a hydrogen atom, A phenyl group substituted with a methyl group, a hydroxymethyl group, a phenyl group, or a hydrophilic group such as a hydroxyl group, an alkoxy group, a sulfo group, or a carboxyl group.

Specific examples of PTA are shown below.

CX-1) (x-2] [X-7] [X-83 (X-3) (X-4) (X-9) (X-1,0) [X-5) [x-6] The ETA precursor used in the present invention refers to the ETA precursor used in the storage of the photosensitive material before use, and does not have a developing effect, but it can be converted into ETA only by the action of an appropriate activator (e.g., base, nucleophile, etc.) or heating. It is a compound that can release .

In particular, the F, TA precursor used in the present invention does not have the function of ETA before development because the reactive functional group of ETA is blocked with a blocking group, but it does not function as ETA under alkaline conditions or when heated. By doing so, the blocking group is cleaved, so that it can function as an ETA.

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 PTA precursors,
Hydroquinone precursors with quaternary ammonium groups, cyclohex-2-ene-1,4-dione type compounds, compounds that release ETA through electron transfer reactions, compounds that release ETA through intramolecular nucleophilic substitution reactions, phthalides Examples include a PTA precursor blocked with a 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, US Pat. No. 767.704, US 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. 4,310.61.2, British Patent No. 1,023,701, British Patent No. 1.231830, British Patent No. 1,258.924, British Patent No. 1.346.920
No., Japanese Patent Publication No. 57-40245, September 58-113,
No. 58-1140, No. 59-178458, No. 51
Developing agent precursors described in Japanese Patent Application No. 182449, No. 59-1132450, 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. 5!11-182450 are preferred.

PTA and an ETA precursor can also be used in combination.

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 (antihalation 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 preferable amount of the electron donor, ETA, or their precursor 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 0.001 per 1 mol of silver halide
-5 mol, preferably 0.01-1.5 mol.

Moreover, ETA is 60 mol% or less, preferably 40 mol% or less of the total reducing agent. When ETA is dissolved in water and supplied, the concentration of ETA is 10-4 mol/2 to 1 mol/
l is preferred.

In order to introduce the reducing substances, dye-donating substances, electron donors, electron transfer agents or their precursors and other hydrophobic additives of the present invention into the hydrophilic colloid layer, high-boiling organic solvents such as alkyl phthalates can be used. Esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphate esters (diphenyl phosphate, triphenyl phosphate, tricyclohexyl phosphate, tricresyl phosphate, dioctyl butyl phosphate, etc.), citric acid esters (e.g. acetyl tributyl citrate) ,
Benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl azelate), trimesic acid esters (e.g. tributyl trimesate) Patent application 1987- Carboxylic acids described in No. 231500, JP-A No. 59-83154, No. 5
No. 9178451, No. 59-178452, No. 59,
-178453, 59-178454, 59-
No. 1784.55, US Pat. No. 59-178457, etc., using the method described in U.S. Pat. After being dissolved in a lower alkyl acetate such as ethyl or butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, cyclohexanone, etc., it is dispersed in a hydrophilic colloid.

The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used. Furthermore, after dispersion, the low boiling point organic solvent can be removed by ultrafiltration or the like as required. The amount of the high-boiling organic solvent is 10 g or less, preferably 5 g or less, per 1 g of the dye-providing substance used. Further, the amount is 5 g or less, preferably 2 g or less per 1 g of the diffusion-resistant reducing agent.

Furthermore, 1 g or less of high boiling point organic solvent per 1 g of binder,
The amount is preferably 0.5 g or less, more preferably 0.3 g or less. Further, the dispersion method using a polymer described in Japanese Patent Publication No. 51-39853 and Japanese Patent Application Laid-Open No. 51-59943 can also be used.

In addition, it can be directly dispersed in an emulsion, or it can be dissolved in water or alcohol and then dispersed in gelatin or an emulsion.

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 binder in addition to the method described above. (For example, JP-A-59-174830, JP-A No. 53-1
02733, Japanese Patent Application No. 62106882, etc.) When dispersing a hydrophobic substance in a hydrophilic colloid, various surfactants can be used. For example, JP-A-59-
The surfactants listed on pages (37) to (38) of No. 157636 can be used.

The heat-developable photosensitive material of the present invention basically has a photosensitive silver halide, a binder, an electron donor, an electron transfer agent, and a reducible dye-donating compound on a support, and if necessary, An organic metal salt oxidizing agent or the like can be contained therein. These components are often added to the same layer, but if they are in a reactable state, they can be divided and added to separate layers. For example, if a colored dye-providing compound is present in the lower layer of the silver halide emulsion, a decrease in sensitivity can be prevented. It is preferable that the reducing agent be incorporated into the photothermographic material, but it may also be supplied from the outside, for example by diffusing it from a dye fixing material, which will be described later.

In order to obtain a wide range of colors in the chromaticity diagram using the three primary colors yellow, magenta, and cyan, at least three silver halide emulsion layers each sensitive to a different spectral region are used in combination.

For example, there are combinations of three layers such as a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, and a combination of a green-sensitive layer, a red-sensitive layer, and an infrared-sensitive layer. Each photosensitive layer can be arranged in various arrangements known for conventional color photosensitive materials.

Further, each of these photosensitive layers may be divided into two or more layers as necessary.

The heat-developable photosensitive material can be provided with various auxiliary layers such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer, an antihalation layer, and a hack layer.

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.

The silver halide emulsion used in the present invention is a surface latent image type emulsion. A surface latent image type emulsion is an emulsion in which a latent image is mainly formed on the grain surface, and is also called a negative type emulsion. The definition of surface latent image type emulsion is described in Japanese Patent Publication No. 513-9410.

The silver halide emulsion of the present invention may be a so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different phases. The silver halide emulsion may be monodisperse or polydisperse, or a mixture of monodisperse emulsions may be used. Particle size is 0.1~
2μ, especially 0.2 to 1.5μ is preferred. The crystal habit of the silver halide grains may be cubic, octahedral, tetradecahedral, tabular with a progeny aspect ratio, or any other form.

Specifically, U.S. Patent No. 4,500,626, column 50, U.S. Pat.
Any of the silver halide emulsions described in JP-A-62-253159 and the like can be used.

Although the silver halide emulsion may be used as is, it is usually chemically sensitized before use. For emulsions for conventional light-sensitive materials, known sulfur sensitization methods, reduction sensitization methods, noble metal sensitization methods, etc. 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-62-2531, 59).

The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg to 100 g/g/g/g/g/g.

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

Among such organic metal salts, organic silver salts are particularly preferably used.

The above [6! Organic compounds that can be used to form the salt oxidizing agent include U.S. Pat.
There are benzo-1-riadules, fatty acids and other compounds described in columns 53 and the like. Furthermore, silver salts of carboxylic acids having an alkynyl 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 a-containing silver salts are 0 per mole of photosensitive silver halide.
．． 0.01 to 10 mol, preferably 0.01 to 1 mol, can be used in combination. The total coating amount of photosensitive silver halide and organic silver salt is 50 mg to 10 g/r in terms of silver.
rr is appropriate.

Various antifoggants or photographic stabilizers can be used in the present invention. An example is RD176
43 (1978) pages 24-25, nitrogen-containing carboxylic acids and phosphoric acids described in JP-A-59-168442, or mercapto compounds and their Metal salts, acetylene compounds described in JP-A-62-87957, and the like are used.

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

Specifically, U.S. Pat.
Examples include the sensitizing dyes described in DI7[) 29 (1978) pages 12-13.

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

Along with the sensitizing dye, the emulsion may contain a dye that does not itself have a spectral sensitizing 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
62.94 etc.).

These sensitizing dyes may be added to the emulsion during or before or after chemical ripening.
It may be carried out before or after nucleation of silver halide grains according to No. 756 and No. 4,225,666. The amount added is generally about 10-8 to 10-2 mol per mol of silver halide.

A hydrophilic binder is preferably used for the constituent layers of the photosensitive material or dye fixing material. Examples include those described on pages (26) 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 pullulan, and polyvinyl alcohol, Examples include polyvinylpyrrolidone, acrylamide polymer, and other synthetic polymer compounds. Also, JP-A-62-24
5260 etc., i.e., -CO
Homopolymers of vinyl monomers having OM or M (M is a hydrogen atom or an alkali metal) or copolymers of these vinyl monomers with each other or with other vinyl monomers (e.g. sodium methacrylate, ammonium methacrylate, Sumikagel L-5H) manufactured by Sumitomo Chemical ■ is also used. Two or more of these binders can also be used in combination.

When employing 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 another material after transfer.

In the present invention, the amount of binder applied is 20 per pot.
The amount is preferably 10 g or less, more preferably 7 g or less.

Constituent layers (including back layers) of photosensitive materials or dye-fixing materials contain 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, Japanese Patent Publication Nos. 62245258 and 62-1366
Any of the polymer latexes described in No. 48, No. 62-110066, etc. can be used. In particular, if a polymer latex with a low glass transition point (40°C or less) is used for the mordant layer, cracking of the mordant layer can be prevented, and if a polymer latex with a high glass transition point is used for the back layer, curling can be prevented. is obtained.

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.
No. 0,626, columns 51-52.

In systems that form images by diffusion transfer of dyes, dye fixing materials are used together with photosensitive materials. The dye fixing material may be individually coated on a support separate from the light-sensitive material, or may be coated on the same support as the light-sensitive material. Regarding the relationship between the photosensitive material and the dye fixing material, the relationship with the support, and the relationship with the white reflective layer, the relationships described in column 57 of U.S. Pat. No. 4,500,626 can be applied to the present application.

The dye fixing material preferably used in the present invention has at least one layer containing a mordant and a binder. As the mordant, those known in the photographic field can be used, and specific examples thereof are described in U.S. Pat. mordant, JP-A No. 62-244043, No. 62-2
Examples include those described in No. 44036 and the like. Further, a dye-receiving polymer compound as described in U.S. 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.

It is especially important to provide a protective layer.

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

Furthermore, for the above purpose, various silicone oils (all silicone oils from dimethyl silicone oil to modified silicone oil in which various types of perforation groups are introduced into dimethylsiloxane) can be used. Examples include various modified silicone oils described in "Modified Silicone Oil" technical data P618B published by Shin-Etsu Silicone ■,
In particular, carboxy-modified silicone (product name X-21-37)
10) etc. are effective.

Also, Japanese Patent Application Publication No. 62-21.5953, Japanese Patent Application No. 62236
The silicone oil described in No. 87 is also effective.

Antifading agents may be used in the photosensitive materials and dye fixing materials. Antifading agents include, for example, antioxidants, ultraviolet absorbers, or certain metal complexes.

Examples of antioxidants include chroman compounds, coumaran compounds, phenol compounds (for example, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. Also, JP-A-61. The compound described in No.-159644 is also effective.

As ultraviolet absorbers, hensitriazole compounds (
U.S. Patent No. 3,533,794, etc.), 4-thiazolidone compounds (U.S. Patent No. 3,352,681, etc.),
Henzphenone compounds (JP-A-46-2784, etc.), other JP-A-54-48535, JP-A-61-136
There are compounds described in No. 64], No. 61-88256, and the like.

Further, the ultraviolet absorbing polymer described in JP-A No. 62-260152 is also effective.

As metal complexes, U.S. Patent No. 4.2/11,155, U.S. Pat. 62-1
．． No. 74741, No. 61-88256 (27) - (2
9) page, Japanese Patent Application No. 61-234103, No. 623109
There are compounds described in Japanese Patent Application No. 62-230596, etc.

Examples of useful antifading agents are described in JP-A-62-21-5272, pages (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.

A fluorescent whitening agent may be used in the photosensitive material or dye fixing material. 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. As an example, K, Veenkataramankg “T
he Chemistry of 5ynthetic
Dyes J Volume V m “The JP-A-61-143
Examples include compounds described in No. 752 and the like. More specifically, examples thereof include stilhene compounds, coumarin compounds, biphenyl compounds, hendioxazolyl compounds, naphthalimide compounds, pyrazoline compounds, and 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 No. 1-18942 and the like. More specifically, examples include aldehyde hardeners (formaldehyde etc.), aziridine hardeners, epoxy hardeners, vinylsulfone hardeners (N,N'-I-J-Reybis(vinylsulfonyl alcohol), cetamide) ethane, etc.), N-
Examples include methylol-based hardeners (such as dimethylol urea) and polymer hardeners (compounds described in JP-A-62-234157, etc.).

Various surfactants can be used in the constituent layers of the photosensitive material and the dye-fixing material for the purposes of coating aids, improving peelability, improving shearability, preventing static electricity, accelerating development, and the like. 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 sheerability,
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, 62-13'5826, etc., or hydrophobic fluorine compounds such as oily fluorine compounds such as fluorine oil or solid fluorine compound resins such as tetrafluoroethylene resin. Examples include compounds.

A matting agent can be used in the photosensitive material and the dye fixing material. As a mantle agent, silicon dioxide, polyolefin, polymethacrylate, etc. are used in JP-A-61-8825.
In addition to the compounds described in No. 6, page (29), benzoguanamine resin beads, polycarbonate resin beads, AS resin beads, etc.
There is a compound described in No. 10065.

In addition, the constituent layers of the light-sensitive material and the dye-fixing material may contain a thermal solvent, an antifoaming agent, an antibacterial and antihyperglycative agent, colloidal silica, and the like. Specific examples of these additives are given in JP-A-61-
No. 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 material. Image formation accelerators include accelerating redox reactions between silver salt oxidizing agents and reducing agents, accelerating reactions such as generation of dyes from dye-donating substances, decomposition of dyes, and release of diffusible dyes, and photosensitive material layers. Physicochemical functions include bases or base precursors, nucleophilic compounds, high-boiling organic solvents (oils), thermal solvents, surfactants, and silver. It is also classified as a compound that interacts with silver ions. However, these substance groups generally have multiple functions and usually have some of the above-mentioned promoting effects. These details are available in U.S. Patent 4,678.
．． No. 739, columns 38-40.

Examples of base precursors include salts of organic acids and bases that are decarboxylated by heat, compounds that release amines by intramolecular nucleophilic substitution reaction, Rossen rearrangement, or Hetzkman rearrangement. 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 incorporate a base and/or a base precursor into the dye fixing material in order to improve the storage stability of the photosensitive material.

In addition to the above, combinations of a poorly soluble metal compound described in European Patent Publication No. 210,660 and a compound capable of forming a complex with a metal ion constituting this hardly soluble metal compound (31 is referred to as a forming compound), Japanese Patent Publication No. 61-2324
Compounds that generate a base by electrolysis as described in No. 51 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 immediately after proper development or reacts with the base to lower the base concentration in the film and stop development, or a compound that inhibits development by interacting with silver and silver salts. It is a compound that

Specifically, acid precursors that release acids when heated, electrophilic compounds that cause a substitution reaction with coexisting bases when heated,
Alternatively, nitrogen-containing heterocyclic compounds, mercapto compounds and their precursors may be mentioned.

For more 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. -For boat fishing, paper and synthetic polymers (films) can be used. Specifically, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene,
Polyimides, celluloses (e.g. triacetyl cellulose), or films containing titanium oxide or the like, as well as film-based synthetic paper made from polypropylene, synthetic resin valves such as polyethylene, and natural barops. Yankee paper, a mixed paper made from
Halique paper, nautical paper (especially cast coated paper), metal, cloth, glass, etc. are used.

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

In addition, JP-A-61-253159 (2) to (3)
The supports described on page 1) can be used.

The surface of these supports may be coated with a hydrophilic binder, a semiconductive metal oxide such as alumina or tin oxide, a carbon blank, or other antistatic agent.

Methods for 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 copying machines. A method of scanning and exposing an original image through a slit using an exposure device, etc. A method of transmitting image information via an electric signal to a light emitting diode, various lasers, etc. for exposure, a method of transmitting image information to a CRT, liquid crystal display, electroluminescent display, etc. There is a method of outputting the image to an image display device such as a sense display or a plasma display, and exposing the image directly or through an optical system.

As mentioned above, light sources for recording images on photosensitive materials include natural light, tungsten lamps, light emitting diodes, laser light sources, CRT light sources, etc., such as U.S. Pat.
The light source described in No. 26, No. 56@ can be used.

Further, image exposure can also be performed using a wavelength conversion element that combines a nonlinear optical material and a coherent 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 optical electric field such as a laser beam is applied, and include lithium niobate, potassium dihydrogen phosphate (KDP) ), lithium iodate, inorganic compounds such as BaB2O,l,
Urea derivatives, nitroaniline derivatives, 21-heropyridine-N-oxide derivatives such as 3-methyl-4-nitropyridine-N-oxyI' (POM), JP-A-61-53462, JP-A-62-21. The compounds described in No. 0432 are preferably used.

As the form of the wavelength conversion element, single crystal optical waveguide type, fiber type, etc. are known, and both are useful.

In addition, the above-mentioned image information includes image signals obtained from a video camera, electronic still camera, etc., a television signal represented by the Nippon Television Signal Standard (NTSC), and an image obtained by dividing an original image into a large number of pixels using a scanner. signal, CG,
Image signals created using a computer such as CAD 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
1-145544 can be used. Note that these conductive layers also function as antistatic layers.

The heating temperature in the heat development step can be developed at about 50'C to about 25'C, and particularly useful is about 80'C to 180'C. The dye diffusion transfer step may be performed simultaneously with the heat development, or may be performed after the heat development step is completed. In the latter case,
The heating temperature in the transfer process can be in the range from the temperature in the heat development process to room temperature, but is particularly preferably 50'C or higher and up to about 10C lower than the temperature in the heat development process.

Although dye migration can be achieved by heat alone, a solvent may be used to promote dye migration.

Also, JP-A-59-218443, JP-A No. 6123805
6, etc., a method in which development and transfer are performed simultaneously or continuously by heating in the presence of a small amount of solvent (particularly water) is also useful. In this method, the heating temperature is 50
It is preferably at least 5°C and at most the boiling point of the solvent; for example, when the solvent is water, it is preferably at least 5°C and at most 100°C.

Examples of solvents used to accelerate development and/or transfer the diffusible dye to the dye fixing layer include water or basic aqueous solutions containing inorganic alkali metal salts or organic bases (these bases may Those described in the section on formation promoters can be used. 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. Further, a surfactant, an antifoggant, a complex-forming compound with a sparingly soluble metal salt, etc. may be included in the solvent.

These solvents can be used in a method of applying them to dye fixing materials, photosensitive materials, 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 (particularly in mass sales, which is calculated by subtracting the weight of the entire coating film from the weight of the solvent corresponding to the maximum swelling volume of the entire coating film).

As a method for applying a solvent to the photosensitive layer or the dye fixing layer, there is, for example, the method described in JP-A-61-147244, page (26). 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 heat solvent may be incorporated into either the photosensitive material or the dye fixing material, or may be incorporated into both. Further, 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 a layer adjacent thereto.

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

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

Heating methods in the development and/or transfer process include contact with a heated block or plate, contact with a hot plate, real presser, heat roller-halogen lamp heater, infrared and far-infrared lamp heater, etc. For example, it may be passed 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. 5975247, No. 59-177547, No. 59181353, No. 60
Apparatuses such as those described in Japanese Utility Model Application Publication No. 18951, Japanese Utility Model Application Publication No. 62-25944, etc. are preferably used.

(Specific Examples of the Invention) Hereinafter, specific examples of the present invention will be shown and the present invention will be explained in further detail.

Example A method for preparing a photosensitive silver halide emulsion will be described.

Photosensitive silver halide emulsion (1) Well-stirred gelatin aqueous solution (1 g of potassium bromide and H○ (CH□), 5 (CH7) 2 in 600 d of water)
S (CH2) 20! (to which 0.5g was added and kept at 50°C), the following (1) solution, (II) solution and (III)
) was added at the same time over a period of 40 minutes.

After washing with water and desalting, 20 g of lime-treated ossein gelatin was added and the pH was adjusted to 6.4 and PAg to 8.2.
Keep warm at C, add 2 mg of sodium thiosulfate, 0 chloroauric acid.
．． 01% water? 8/r9.6 mp was added for chemical sensitization for 30 minutes. In this way, 600 g of a medium-dispersed bromide emulsion with an average grain size of 0.4 μm was obtained.

Dye (a) Dye (b) Photosensitive silver halide emulsion (n) Well-stirred aqueous solution (20 mg of gelatin, 0.30 g of potassium bromide, 6 thorium chloride in 730 ml of water)
g and the following chemical A O, 015 g to make 60.0'
The following solutions (1) and (11) were simultaneously added at equal flow rates over 60 minutes to the solution (which had been kept warm at C). (1) After the addition of the solution, a methanol solution (ITI) of the following mulching dye was added. In this way, a monodisperse cubic emulsion adsorbed with a dye having an average grain size of 0.45 u was prepared.

After washing with water and deacidifying, 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 1.6 mg of triethylthiourea and 1.3.3 mg of 4-hydroxy-6-methyl.
a, 71te 1~Razinden 100mg and ripening time Ll
: It was 55 minutes. Also, the yield of this emulsion is 635
It was g.

(Chemical A) (Sensitizing dye C) Photosensitive silver halide emulsion [I] A well-stirred gelatin aqueous solution (20 g of gelatin, 3 g of potassium bromide, and HO (C
H7)2S (CH2)2s (CH2)20H
(1 g of the solution was added and kept at 75°C), and the following solutions (4) and (U) were added simultaneously over 20 minutes. Thereafter, the following solutions (III) and (IV) were simultaneously added over 30 minutes. After washing with water and desalting, 20 g of ash-treated ossein gelatin was added to adjust the pH to 6.2 and the PAg to 8.5, followed by 4.3 mg of sodium thiosulfate and 0.3 mg of chloroauric acid.
5 ml of 01% aqueous solution, and 2 g of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene O,.
, 4 ml of a 0.1% aqueous solution of polyvinylpyrrolidone (average molecular weight: 100,000) of the present invention was added and chemically sensitized at 60"C for 45 minutes. In this way, the average particle size was 0.9
600 g of a monodispersed octahedral silver iodobromide emulsion (I[[]) of μ was obtained.

Ru.

12.5 g of zinc hydroxide with an average particle size of 0.2 μ;
As a dispersant, 1 g of carboxymethyl cellulose and 0.1 g of sodium polyacrylate were added to 100 mf of a 4% gelatin aqueous solution.
In addition to f1, the mixture was ground for 30 minutes using a glass bead with an average particle size of 0.75 mm. The glass beads were separated to obtain a dispersion of zinc hydroxide.

Next, we will describe how to make a gelatin dispersion of a dye-providing compound.

□□□□□□□□ - Table 1 Composition of Photosensitive Material 101 Yellow, macenta, and cyan were added to cyclohexanone 40 according to the above prescription, and heated and dissolved at about 60°C to form a uniform solution. This solution, 100 g of a 10% aqueous solution of lime-treated gelatin, 0.6 g of sodium dodecylhenzenesulfonate, and 50 ml of water! After stirring and mixing, the mixture was dispersed using a homogenizer at 10,000 rpm for 10 minutes. This dispersion is called a gelatin dispersion of a dye-providing compound.

Using the above, a photosensitive material 101 as described below was produced.

(Note 1) Sodium polyacrylate/polyvinyl alcohol leburonc cocopolymer (Note 2) ■ Screw (vinyl sulfonylaceto amido)ethane (Note 4) (Note 5) (Note 6) (Note 8) (Note 9) Next, we will discuss how to make the dye fixing material.

A dye fixing material R-1 was prepared by coating on a paper support laminated with polyethylene according to the composition shown in the following table.

Table 2 Composition of dye fixing material R-1 Silicone oil *1 CH3 Hff CH3 1h C)13-5i-0)St-0)nr(Si-Oh-3
i-CH3C)13 CH3(CHz)3cOOH
CH3 surfactant "4 Polymer" 7 Aerosol 0T CsF+7SO2NCH2COOK l3 C11H23CONHCH2CH2C:H2N@CH2
C00OH3 Vinyl alcohol sodium acrylate copolymer (ff 5 / 25 molar ratio) Dextran (molecular weight 70,000) Mordant *6 High boiling point organic solvent "8" Rheophos 95 in SO2 (manufactured by Ajinomoto ■) Mantle agent 110 Benzoguanamine resin average particle size 10μ The multilayered color photosensitive material 101 was exposed to light using a tungsten light bulb through a gray color separation filter whose density was continuously changing.

While feeding this exposed photosensitive material at a linear speed of 20 mm/sec, 15 mR/rd of water is supplied to the emulsion surface using a wire bar, and then immediately superimposed so that the film surface is in contact with the dye fixing material R-1. Ta.

After heating for 15 seconds using a heat roller whose temperature was adjusted so that the temperature of the water-absorbed film was 73°C, the dye fixing material was peeled off from the photosensitive material.

The image obtained in the second step of the peeled off dye-fixing material is CIEL'''a *b* L on the chromaticity diagram at F of the color evaluation lamp.
*a *b* values are L2-about 38. a”=-
It was a gray color image with values of 1,,5b''--2,0.

This color image was observed under various observation light sources such as a color evaluation lamp (C light a), Palzuk (manufactured by Matsushita Electric), Sunline Super (manufactured by Hitachi), and visual evaluation of the dependence of gray on the observation light source was performed. I did it.

A photosensitive material 102 having the same structure as the photosensitive material 101 except that the gelatin dispersion of the cyan dye-providing compound used in the first layer is shown in Table 1.
, 1.03, 1.04.105 were created, and similar processing and evaluation were performed. Table 2 shows the results.

Table 2 shows that the dependence of gray on the observation light source can be improved by using two or more of the reducible dye-donating compounds of the present invention in an appropriate ratio.

Note that similar effects were obtained for magenta in the third layer and yellow in the fifth layer.

[Brief explanation of the drawing]

1 to 3 are graphs showing the spectral absorption characteristics of yellow, magenta, and cyan dyes, where the horizontal axis shows wavelength (unit: nm) and the vertical axis shows absorption. Patent Applicant Fuji Photo Film Co., Ltd. Procedural Amendment 4. Subject of amendment: “Detailed Description of the Invention” column of the specification

Claims (1)

[Claims] At least a photosensitive silver halide, a binder, an electron donor, an electron transfer agent, and three types of reducible dye donors that release yellow, magenta, and cyan diffusible dyes when reduced by the electron donor on a support. In the heat-developable color photosensitive material comprising the compound, the yellow;
A heat-developable color photosensitive material characterized in that two or more types of reducible dye-providing compounds are used in combination to provide dyes whose absorption maxima are separated from each other by 5 nanometers or more in at least one hue of magenta and cyan.