JPH01150135A - Heat developable color photosensitive material - Google Patents

Abstract

PURPOSE:To enhance image density and color reproducibility by adding a specific compd. to a photosensitive material for which a dye donative compd. having reducibility is used. CONSTITUTION:The title photosensitive material contains a reducing agent (precursor) and the reducible dye donative compd. (b) which releases a diffusible dye when reduced. Furthermore, said material contains the compd. (a) expressed by formula I. In formula, A denotes a redox base nucleus such as hydroquinone; Time denotes a timing group such as S or N; (t) denotes 0, 1; X denotes a group which functions as a development restrainer when released and the compd. expressed by formula II or the like is usable for the same. The compd. expressed by formula III or the like is usable for the compd. (b). In formula, X, Y denote a divalent combination group; R4 denotes an atom group which forms a heterocycle including X, Y, N; EAG denotes an arom. group which receives electrons from a reducing material; Time denotes a timing group; (t) denotes 0, 1; Dye denotes a dye (precursor).

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a heat-developable color photosensitive material, and in particular a heat-developable color photosensitive material that can produce positive color images with high density and good color reproducibility. It is related to.

(Prior art and its problems) Heat-developable photosensitive materials are well known in this technical field. For information about heat-developable photosensitive materials and their processes, see, for example, "Fundamentals of Photographic Engineering" Non-Silver Salt Photography Edition (1st and 2nd year, published by Corona Publishing). Published) 2 Hiro λ page ~ 2! ! Page, US Patent No. J-00626, etc.

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

For example, in US Pat. A method has been proposed in which the agent is oxidized and the remaining unoxidized reducing agent is used for reduction to release a diffusible dye. Also, European Patent Publication 2207≠
No. 17-Ai9? (Vol. 12, No. 22) describes N as a compound that releases a diffusible dye by a similar mechanism.
A heat-developable color photosensitive material using a non-diffusible compound which releases a diffusible dye by reductive cleavage of a -X bond (X represents an oxygen atom, a nitrogen atom or a sulfur atom) is described.

However, it has been found that 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 high staining of color images.

In order to suppress staining in a photothermographic material for positive image formation using such a reducible dye-donating compound, a diffusible electron transfer agent is used in addition to a diffusion-resistant electron donor as a reducing agent. However, the generated electron transfer agent radicals diffuse into other layers with different color sensitivity and cross-oxidize the electron donors there), causing a decrease in image density and worsening color reproduction. do. For this reason, attempts have been made to provide an intermediate layer between photosensitive layers having different color sensitivities, and to incorporate a reducing substance into this intermediate layer. Regarding materials, there are restrictions on the amount of binder in the intermediate layer and the amount of reducing substance added in terms of image forming speed, resolution, film quality, etc., and further improvements are desired.

(Object of the Invention) An object of the present invention is to increase the image g4 density and improve the color reproducibility of a heat-developable color photosensitive material using a reducible dye-providing compound.

(Structure of the Invention) The object of the present invention is to provide a support with at least a photosensitive silver halide emulsion, a binder, a reducing agent case or its precursor, and a reducible dye donor that releases a diffusible dye when reduced. The present invention has been achieved by a heat-developable color photosensitive material which further contains a compound represented by the following general formula [1].

A - (Time) l -X In the formula, it means an Ati redox mother nucleus, and is an atomic group that makes it possible to release Ip - (Time)t -X' by being oxidized during heat development treatment. It is.

Time represents a typing group connected to a human by S%N, O or Se, and t represents an integer of 0 or l.

X represents a group released from -(Timelt-X and later functions as a development inhibitor).

The compound of general formula (I) of the present invention increases the maximum image density of a heat-developable color photosensitive material using a reducible dye-providing compound and improves color reproducibility.

The compound of general formula (1) used in the present invention will be explained below.

First, A in general formula (I) will be explained in more detail. Examples of redox nuclei exhibited by humans include hydroquinone, catechol, p-abanophenol, 0-abanophenol, l,2-natsuta-1 nondiol, /, 4C-
Natsuta 1/Ndiol, l.

t-naphthalenediol, /, 2-7 nonaphthol, /, 4! -Abanonaphthol and/or 6-7 nonaphthol. At this time, the abano group has carbon number/-
It is preferably substituted with 23 sulfonyl groups or an acyl group with -2j carbon atoms. Examples of the sulfonyl group include substituted or unsubstituted aliphatic sulfonyl groups and aromatic sulfonyl groups. Examples of the acyl group include substituted or tfEt-substituted aliphatic acyl groups and aromatic acyl groups. The hydroxyl group or abano group forming the human redox mother nucleus may be mined with a protective group that can be deprotected during development. Examples of protecting groups include carbon 1! / -2j, such as acyl group, alkoxycarbonyl group, carbamoyl group, and JP-A-39-
/97037, and the protecting groups described in JP-A-19-2010J7. Furthermore, this protecting group may be bonded to the substituents of A described below, if possible, to t,
X or a 7-membered ring may be formed.

The redox nucleus represented by A may be substituted with an appropriate substituent at an appropriate position. Examples of these substituents include those having 2j or less carbon atoms, such as alkyl groups,
-ru group, alkylthio group, arylthio group, alkoxy group, acyloquine group, amine group, hydroquine group, acyloxy group, abate group, sulfonoa is do group, alkoxy group, sulfonylamino group, 1/ide group, carbamoyl group, alkoxy Examples include carbonyl group, sulfamoyl group, sulfonyl group, cyan group, halogen atom, acyl group, carboxyl group, sulfo group, nitro group, heterocyclic residue, and +Time+-tX. These substituents may be further substituted with the substituents described above. These substituents, if possible, may be bonded to each other to form a saturated or unsaturated carbon ring,
Alternatively, a saturated or unsaturated heterocycle may be formed.

Preferred examples of A include hydroquinone, catechol, p-aminophenol, 0-aminephenol, /,
Examples include ≠-naphthalenediol, /, 4'-aminonaphthol, and the like. More preferred examples of A include hydroquinone, catechol, p-aminophenol, and 0-aminephenol. Most preferably as A
It is hydroquinone.

Preferred specific examples of A in general formula [I] are shown below. In each structural formula, (e) indicates the position where +Time+-xX is bonded.

+Time+tX is a group that is released as "+Time+X" only when the redox nucleus represented by A in the general formula [■] undergoes a cross-oxidation reaction during development and becomes an oxidized product.

Time is a timing group connected to A through a sulfur atom, nitrogen atom, oxygen atom, or selenium atom, and includes a group that releases X from e+Time+X released during development through one or more reaction steps. . Ti
Examples of me include, for example, U.S. Patent No. Issue, Public Showayo/-/No. 142r, Publication Showayo 7-! Examples include those described in Al37. Time may be a combination of two or more selected from those listed above.

X means a development inhibitor. Examples of development inhibitors include:
Examples include compounds having a mercapto group bonded to a petero ring or heterocyclic compounds capable of producing iminosilver. Examples of compounds having a mercapto group yk bonded to the petero ring include substituted or unsubstituted mercaptoazoles (e.g. /-phenyl-!-mercaptotetrazole, /-propyl-5-mercaptotetrazole, l-
Butyl-mercaptotetrazole, λ-methylthio! -mercapto/, j, ≠-thiadiazole, 3-
Methyl-Hiro-phenyl! -Mercapto-/ , 2
, 44-) lyazole, /-(≠-ethylcarbamoylphenyl)-2-mercaptoibadazole, λ-mercaptobenzoxazole, 2-mercaptobenzibadazole, 2-mercapto-yo-sulfobenzibadazole, 2-mercapto Benzothiazole, λ-mercapto, monosulfobenzothiazole, 2-mercaptobenzoxasol, 2-phenyl-! -Mercapto 7,3
．． ≠-oxadiazole, 1-(j-(J-methylureido)phenyl)-j-mercaptotetrasol, /-
(≠-nitrophenyl)-yo-mercaptotetrasol,! -(2-ethylhexanoyl)-λ-mercaptobenzimidazole, etc.), substituted or unsubstituted mercaptoazaindenes (e.g., 6-methyl-≠-
Mercapto-' + 3+ 33 + 7-tetrazaindene, Hiroshi.

t-dimethyl-1-mercapto-' + 3+ 321
7-tetrazaindene, etc.), substituted or unsubstituted mercaptopyrimidines (eg, comelkabutopyrimidine, λ-mercapto-methyl-t-hydroxypyrimidine, etc.).

Examples of heterocyclic compounds capable of forming iminosilver include substituted or unsubstituted triazoles (for example, /, 2
．． 41-triazole, benzotriazole,! -Methylbenzotrianol,! -nitrohenzo) l) Azole, r-bromobenzotriazole, t-n-butylbenzotriazole,! , dimethylbenzotriazole, etc.), substituted or unsubstituted indazoles (e.g. indazole, j-nitroindazole, 3-nitroindazole, 3-chloro-!-nitroindazole, etc.), substituted or unsubstituted benzimidazoles kind (
Examples include yo-nitropenzimidazole, j,6-cyclobenzimidazole, etc.).

In addition, after X separates from 'l'ime in the general formula [■] and once becomes a compound that has development inhibiting properties, it further causes a certain chemical reaction with the developer components and substantially inhibits development. It may change into a compound that has no or significantly reduced properties. Examples of functional groups that undergo such chemical reactions include ester groups, carbonyl groups, imino groups, immonium groups, Michael addition acceptor groups,
Another example is an imide group. Examples of such deactivated drugs include /-(3-phenoxycarbonylphenyl)-y-mercaptotetrasol, i-(≠-phenoxycarbonylphenyl)-1-
Mercaptotetrazole, / -(3-maleinimidophenyl)-s-mercaptotetrazole, yo-phenoxycarbonylbenzotriazole,! -(≠-ryanophenoxicah6yl)penztriazole, λ-
phenoxycarbonylmethylthiomercapto/
, j.

Reachiazole, j-nitro-3-phenoxycarbonylimidazole, j-(2,3-dichloropropyloxycarbonyl)benzotriazole, /-(≠-pensoyl-o-dF-/phenyl)-yo-mercaptotetrazole, j,- (dicarbonyl in 2-methanesulfonyletho)-2-mercaptobenzothiazole,! -Cinnamoyl abanobensotriazole, 1-(3-vinylcarbonylphenyl)-! -Mercaptotetrazole,!
-succinibutomethylbenzotriazole, -1 (≠
-Sushi/Iba Biphenyl 1-! -Mercapto-/, J
, u-oxadiazole, 6-funinoxycarponyl-2-mercaptobenzoxazole, and the like.

In order to more specifically describe the contents of the present invention, specific examples of the compound represented by the general formula CI (DIR compound) are shown below, but the compounds that can be used in the present invention are not limited to these. isn't it.

The compound represented by the general formula [I] can generally be synthesized by the following methods. First, Time is just a bond (1
=O), the first is chloroform, J-dichloroethane, carbon tetrachloride, tetrahydrofuran, uncatalyzed or p-) acid such as toluenesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, methanesulfonic acid, etc. This method involves reacting benzoquinone, orthoquinone, quinone monoimine, or quinone diimine derivative with a development inhibitor at a temperature between room temperature and 1000C in the presence of a catalyst.

The second is potassium carbonate in an aprotic polar solvent such as acetone, tetrahydrofuran, dimethylformamide, etc.
In the presence of a base such as hydrogen carbonate, sodium hydride, or triethylamine, a benzoquinone, orthoquinone, quinone monoimine, or quinone diimine derivative substituted with chlorine, bromine, or iodine and a development inhibitor are mixed at 20°C.
This is a method in which a quinone compound obtained by reaction between C and 1000 C is reduced with a reducing agent such as diethylhydroxylamine or sodium hydrosulfide. [Reference: Re5earch Disclosure /
t227 (/ri 7F): Liebigs Ann, Ch
em, 7A! , i Ji (tri7)] Then the type in which X is released via Timet (t=/)
can also be synthesized in almost the same manner as above. That is, instead of the above development inhibitor (X), 'l'ime-X
or a method in which a time group having a substitutable group (e.g., a halogen atom, a hydroxyl group, or a precursor thereof) that can be substituted with It is.

The compound of formula CI) of the present invention may be used in the photosensitive layer, intermediate layer, protective layer or other auxiliary layer. Further, when the silver halide emulsion and the reducible dye-providing compound are added to separate layers, it may be used for either of them.
tlS addition t is Bo per mole of silver halide, ooi-
v mol, preferably 0. at-/, 7 mol, per 1 mol of reducible dye-donating compound l) 0.0/-10 mol, preferably 0.07-7 mol, reducing agent or its precursor 1
#) o per mole, oi-to mole, preferably 01or
-to moles. Moreover, the compound of the general formula (11) of the present invention can also serve as an electron donor. When used in an intermediate layer, it is 0.03 to i.

The preferred range is 0.01 to 1 Oi mol/WL2, 0.01 to 1 Oi mol/WL2.

In the present invention, a reducible dye-providing compound is combined with a reducing agent, a binder, and a silver halide emulsion to form a 1-unit heat-developable 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,
From the viewpoint of sensitivity, it is preferable that the layer containing the reducible dye-providing compound is located below the halogenated emulsion layer.

Normally, in order to reproduce full color, three sets of photosensitive layers with different color sensitivities are provided. For example, there are three layers: a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer.
There are combinations of three sets, a green-sensitive layer, a red-sensitive layer, and an infrared-sensitive layer. Each color-sensitive layer can adopt the arrangement order of seeds known for conventional color light-sensitive materials. Further, each of these color-sensitive layers may be divided into 2# or more as necessary.

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

In the present invention, for the purpose of reducing staining of transferred positive dyes, a compound that releases a group that functions as a fogging agent or a development accelerator for silver halide when oxidized during thermal development processing can be used in combination. Such compounds are generally known as FA compounds in the field of photographic materials, and such compounds can also be used in the present invention. For example, in the present invention, as the FA compound,
No. 112731 (3) Compounds that are described in negative terms (?) can be mentioned.

In addition, in the present invention, the maximum density of the transferred positive image is further increased,
For the purpose of inhibiting staining, a compound that releases a group that functions as a development inhibitor for silver rhodanide upon reduction during thermal development may also be used. Specific examples of these compounds can be found in European Patent Publication λ2074ttk
No. 2, public branch axis r7-1. /No.92, Tokukai Sho t-low 2/
It is described in No. 1270, etc.

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 [L].

几WR-(Time)t-Dye General formula (L)
In the formula, PWR is reduced to = (Time)
Represents a group that releases t-Dye k.

'L"ime is released from PWR as -CPime)t-Dye and then Dye f through subsequent reactions.
Represents a releasing group.

[represents an integer of oi or /.

Dye represents a dye or its precursor.

First, PWR will be explained in detail.

PWR is U.S. Patent≠, /3, No. 3, or U.S. Patent≠, /J, No. 377, Same≠, jA≠,! No. 77,
JP-A No. 39-113333, JP-A-39-113333, J7-R Hiro1l-jJ
It corresponds to the part containing an electron-accepting center and an intramolecular nucleophilic substitution reaction center in a compound that releases all of the photographic reagent through an intramolecular nucleophilic substitution reaction after reduction as disclosed in No. Also, U.S. Patent Publication, 232. to
No. 7, JP-A No. 4/-412!7, Research Disclosure (IQR Hiro) ■, 2≠ No. 021 or JP-A No. 4/-412! It may correspond to a moiety containing an electron-accepting monooid center in a compound that eliminates a photographic reagent through an electron transfer reaction and a carbon atom that connects it to the photographic reagent. Still in Tokukai Akira! E/4t2
! No. 30, U.S. Patent No. 34t3,293, q, Otsu/9. The aryl group substituted with an electron-withdrawing group in the compound whose single bond cleaves and releases the photographic reagent after reduction as disclosed in No. ♂♂q, and the atom (sulfur atom or It may correspond to a moiety containing a carbon atom or a nitrogen atom). Still US Patent 4 (
, <60.223, even if it corresponds to a moiety containing a nitro group in a nitro compound that releases a photographic reagent after electron acceptance and a carbon atom connecting it to a photographic reagent, as disclosed in No. 60.223. Okay, US Patent 11. t09.
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 described in No. tZO.

In addition, a compound having 5O2X (X represents oxygen, sulfur or nitrogen atom) and an electron-withdrawing group in one molecule as described in Japanese Patent Application No. 101,111 of 1982;
L-ri! A compound having a PO-X bond (X has the same meaning as above) and an electron-withdrawing group in one molecule as described in No.
c-X' (X
' has the same meaning as X or -8O2-) and a compound having an electron-withdrawing group can also be used. However, in order to more fully achieve the object of the present invention, among the compounds of general formula (L), those represented by general formula (LII) are preferred.

The general formula (LII) (Time)DYe binds to at least one of R1, R2, or UEAG.

The portion corresponding to PWR in the general formula (LI[) will be explained.

Or a group containing an oxygen atom (, -〇-), a sulfur atom (-8→, or a nitrogen atom (-N(R3)-)).

1, 2 and R3 represent a group other than a hydrogen atom or a primary bond.

Groups other than hydrogen atoms represented by 1, R2, and R3 include alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, acyl groups, sulfonyl groups, carbamoyl groups, and sulfamoyl groups. Examples include. These groups include those having substituents. As a specific example, public branch axis 17-1. /9th issue, pages 2-3
The basis of the description is listed in the left column.

R1 and R3 are substituted or unsubstituted alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups,
An acyl group, a sulfonyl group, etc. are preferred. R1 and R
The number of carbon atoms in 3 is t, and IAO is preferable.

R2 is preferably tm@, an unsubstituted acyl group, or a sulfonyl group. The number of carbon atoms is preferably /-4!0.

Lu, R2, R3 and EAG may be combined with each other to form a ring.

EAG will be described later.

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

The general formula (LI[[) (Time+VDye) binds to at least one of R4 and EAG.

The portion corresponding to PWR in the general formula (Lull') will be explained.

Y is a divalent linking group, preferably -C- or -8
It is 02-. X represents the same meaning as above.

几4 represents an atomic group that is bonded to X1Y to form a monocyclic or condensed heterocyclic ring containing five or more members, including a nitrogen atom.

Preferred examples of the portion corresponding to this heterocycle are listed below.

EAG AG EAG EAG EAGEAG
EAGAG Here, R13, B 9 and BIG are preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, or the like.

几11 is an alkyl group, aryl group, acyl group or su/L
/ylt = represents the group. (Time), Dye
may be bonded to R1 or R1.

EAG carries an aromatic 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 (Al ■ In general formula (A), Z represents -(nee Sub or -N-).

Vn represents an atomic group which together with 21 and z2 forms a tri- or trivalent aromatic group, and n is an integer from 3 to j.

V3U-Za-Ta), V41d-Za-Z4-1Vs
[-Za-Z4-Za-1VaU -z 3-z 4-z 5-z 6-1v7 is Za z
4z5z6Z7 % vs bar Z 3-Z 4-Z s -Z 6-Z 7-Z 8
- Terror. Kokote 22 to Z8 each represent a symbol, Sub represents a simple bond (pi bond),
Represents a hydrogen atom or a substituent described below. Sub may be the same or different, or may be bonded to each other to form a tri- or tri- or trivalent saturated or unsaturated carbocyclic or heterocyclic ring.

In general formula (A), the sum of the Hammett substituent constant sigma para of the substituents is +0.3θ or more, more preferably +0.
70 or more, most preferably 10.

? ! Select the Sub so that the result is as follows.

EAG will be described in more detail.

EAG represents a group that accepts or takes electrons from a reducing substance, and is bonded to a nitrogen atom. 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 compound. Examples of the physical properties of the entire compound include the ease with which it accepts electrons, as well as its water solubility, oil solubility, diffusivity,
It can be used to adjust sublimability, melting point, dispersibility with binders such as gelatin, reactivity with nucleophilic groups, reactivity with electrophilic groups, etc.

A specific example of EAG is described in European Patent Publication No. 220711tk2.

Time is a timing group having the same meaning as described in the above general formula [E].

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

Specifically, EP7j, issue 4492, Tokukai Shoyo? -t
The jL fCD y e disclosed in No. tzoz is available.

Typical specific examples of the reducible dye-providing compound used in the present invention are listed below, but the present invention is not limited thereto, such as European Patent Publication No. 22074CAAJ, Publication Axis r7-1,199, etc. Dye-providing compounds described in can also be used.

Typical specific examples of the reducible dye-donating compound used in the present invention are listed below, but the present invention is not limited thereto. ? Dye-providing compounds such as those described in et al. can also be used.

2tts Each of these compounds can be synthesized by the methods described in the patent specifications cited above.

The use of the dye-donating compound depends on the extinction coefficient of the dye, but o, or ~ j is ethyl/WL2, preferably <uO,/
~3 ethyl/m2.

The dye-donating substances can be used alone or in combination of two or more. Also, in order to obtain images of black color or different hues, Japanese Patent Laid-Open No. 60-/422! As described in No. 2, for example, at least one of each of cyan, magenta, and yellow dye-providing substances is mixed in the layer containing silver rhodanide or in an adjacent layer to have different hues. It is also possible to use a combination of two or more dye-donating substances that release mobile dyes.

The reducing agent used in the present invention is European Patent Publication No. 2207 Ko4A,
No. 2 public branch axis + r7-47 Tata No., Tokukai Sho tko 2/!
Examples include the compounds described in No. 270. It is preferred to use a combination of an electron transfer agent and an electron donor as the reducing agent. In this case, particularly preferred electron donors (or precursors thereof) are compounds represented by the following general formulas [I] and/or (It).

Particularly preferred electron donors (or precursors thereof) are compounds represented by the following general formula (C) or CD).

In the formula, A and A2 each represent a hydrogen atom or a protecting group for a phenolic hydroxyl group that can be deprotected with a nucleophilic reagent.

Here, the nucleophilic reagents include anionic reagents such as OHe, ELOe (R; alkyl group, aryl group, etc.), hydroxamic acid e anions SO, primary or secondary amines, hydrazine, hydroxylamines, Examples include compounds with lone pairs of electrons such as alcohols and thiols.

Preferred examples of A and A2 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-Shojter/Re 7Q, 37 No. 201O
It may be a protecting group disclosed in No.j, or A 1
%A2 may be bonded to R1, R, R and R to form a ring, if possible. Also, 80 and A2 may both be the same or different.

R1, R2, R3 and R4 are each a hydrogen atom, an alkyl group (optionally substituted alkyl group, e.g. methyl group, ethyl group, n-butyl group, cyclohexyl tss
n-octyl group, allyl Lsec-octyl group, ter
t-octyl group, n-dodecyl group, n-tadecyl group, n-hexadecyl group, tert-octadecyl group, 3
-hetesadecanoylaminophenylmethyl group, Hiro-hexadecylsulfonylaminophenylmethyl group, coethoxycarbonylethyl group, 3-carboxypropyl group, N-ethylhexadecylsulfonylaminomethyl group,
N-methyldodecylsulfonylamine ethyl group); aryl group (optionally substituted aryl group, e.g. evaporation, phenyl group, 3-hexadecyloxyphenyl group, 3-methoxyphenyl group, 3-sulfophenyl group, 3-chlorophenyl group); (2-carboxyphenyl group, 3-dodecanoylaminophenyl group, etc.); alkylthio group (optionally substituted alkylthio group, such as n-butylthio group, methylthio group, tert-octylthio group, n-dodecylthio group, (2-hydroxy7ethylthio group, n-hexadecylthio group, 3-ethoxycarbonylpropiothio group, etc.); Arylthio group (optionally substituted arylthio group, such as phenylthio group, chlorophenylthio Lx-n-octyloxy-!- t-butylphenylthio group, Hiro-dodecyloxyphenylthio group, ≠-hexadecanoylamine phenylthio group, etc.); sulfonyl group (optionally substituted aryl or alkylsulfonyl group, etc.) methanesulfonyl group, butanesulfonyl group , p-toluenesulfonyl group, phenylsulfonyl group, 4'-acetylaminophenylsulfonyl group); sulfo group; halogen atom (e.g. fluorine atom, chlorine atom, bromine atom, iodine atom) ;7 ano group; carbamoyl group (optionally substituted carbamoyl group, e.g. methylcarbamoyl group, diethylcarbamoyl group, 3-C2,≠-di-i-hentylphenyloxy)
fluoroylcarbamoyl group, cyclohexylcarbamoyl group, di-n-octylcarbamoyl group, etc.); sulfamoyl group (optionally substituted sulfamoyl group, such as diethylsulfamoyl group, di-n-octylcarbamoyl group, n- hexatecylsulfamoyl group, 3-i
s.

-hexadecanoylaminophenylsulfamoyl group, etc.); amide group (optionally substituted amide group, acetamido group, 1so-butyroylamino group, Hiro-tetradecyloxyphenylbenzamide group, 3-hexadecanoylamino benzamide group, etc.); imide group (optionally substituted imide group, such as succinimide group, 3-laurylconophosphate imide group, phthalimide group); carboxyl group; sulfonamide group (optionally substituted sulfonamide group, etc.); Groups, such as methanesulfonamide group, octanesulfonamide group, hexadecanesulfonamide group, benzenesulfonamide group, toluenesulfonamide group, ≠-
lauryloxybenzenesulfonamide group, etc.).

However, the total carbon number of R1-R4 is r or more. In addition, in general formula [C], R1 and R2 and/or R
3 and R4 are R1, R2, and R2 in general formula [D]
and R3 and/or R3 and R4 may be bonded to each other to form a saturated or unsaturated ring.

Among the electron donors represented by the general formula [C'3 or [D], those in which at least two of R1 to R4 are substituents other than hydrogen atoms are preferred.

Particularly preferred compounds are those in which at least one of R1 and R2 and at least one of R3 and R4 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-/) (ED-2) (ED-3) H (ED-4) (ED-1') (ED-t') (ED-7) (ED-4) (ED-ta) (ED -to) H (ED-//) (ED-/2) The amount of the electron donor (or its precursor) to be used varies within a wide range, but preferably T90,
01 mole~! A preferred range is θ mol, particularly about 0.7 mol to j mol. Also, o, ooi moles per mole of silver rodanide! moles, preferably o, oi moles ~/
, 1 mole.

As the ETA used in combination with these electron donors, any compound can be used as long as it is oxidized by silver agenide and its oxidized form has the ability to cross-oxidize the above electron donor. However, a movable one is preferable.

A particularly preferred ETA is a compound represented by the following general formula [:X-/) or [X-λ].

CX-I) [X-11:1 In the formula, R represents an aryl group. R% RlR% R% R and R represent a hydrogen atom, a halogen atom, an acylamide group, an alkoxy group, an alkylthio group, an alkyl group, or an aryl group, and these may be the same or different.

Examples of the aryl group represented by R in general formulas (X-I) and (X-II) include phenyl group, naphthyl group, tolyl group, xylyl group, etc. These groups may be substituted. For example, halogen atoms (chlorine atoms,
bromine atom, etc.), amine group, alkoxy group, aryloxy group, hydroxyl group, aryl group, carbonamide group, sulfonamide group, alkanoyloxy group, benzoyloxy group, ureido group, carbamate group, carbamoyloxy group, carbamate group, carboxyl group, sulfo group,
It may also be an aryl group substituted with an alkyl group (methyl group, ethyl group, propyl group, etc.).

R, R, R13, R of general formula [X-■], [X-II]
The alkyl group represented by R14, R15 and R16 is an alkyl group having 7 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc.), and these alkyl groups include a hydroxyl group, an amino group, It may be substituted with a sulfo group, a carboxyl group, etc. Further, as the aryl group, phenyl group, naphthyl group, xylyl group, tolyl group, etc. can be used. These aryl groups are
Substituted with a rhodane atom (chlorine atom, bromine atom, etc.), alkyl group (methyl group, ethyl group, propyl group, etc.), hydroxyl group, alkoxy group (methoxy group, ethoxy group, etc.), sulfo group, carboxyl group, etc. Good too.

In the present invention, compounds represented by the general formula (X-II:) are particularly preferred.In the general formula [X-II],
R11, R12, R13 and R14 are preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a substituted alkyl group having 1 to io carbon atoms, and a substituted or unsubstituted aryl group,
More preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a phenyl group, a hydroxyl group, an alkoxy group, a sulfo group,
It is a phenyl group substituted with a hydrophilic group such as a carboxyl group.

Specific examples of compounds represented by general formulas 1:X-1] and [X-II:] are shown below.

(x-/) (X--z)(x-3)
(X-A) (X-<z)
(X-7) (X-j) (X-♂) (X-ta) (X-io) The ETA precursor used in the present invention has no developing effect during storage of the photosensitive material before use. However, it is a compound that can release ETA only by the action of a suitable activator (eg, base, nucleophile, etc.) or heating.

In particular, the ETA precursor used in the present invention is characterized in that the reactive functional group of ETA is 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.

The ETA precursor used in the present invention includes:
2- and 3-acyl derivatives of phenyl-3-pyrazolidinone, 2-aminoalkyl or hydroxylalkyl derivatives, hydroquinone, metal salts such as catechol (lead, cadmium, calcium, barium l, halogenated acyl derivatives of hydroquinone, oxazine and bishydroquinone) In addition to oxazine derivatives, lactone type ETA precursors, hydroquinone precursors having a Hiro-class ammonium group, cyclohex-2-ene-7. Hiro-dione type compounds,
Examples include compounds that release ETA through an electron transfer reaction, compounds that release ETA through an intramolecular nucleophilic substitution reaction, ETA precursors blocked with a phthalide group, and ETA precursors blocked with an indomethyl group.

The ETA precursor used in the present invention is a known compound, for example, US Pat. No. 747.70'A, US Pat. Cog No. 7,267, No. 3, 2 Hiro 6. ri♂♂ No. 3, 2
Riyo, No. 27♂, No. 3. ≠62.2tt No. 3.
j♂t, rots number, same number 3. t/j, Hiroshi 32nd issue, 3rd, 6th! 0, 7≠ri issue, ``A, 20ri, zro issue,
Same No. ≠, 330, t/7 No. 1, 310,412
British Patent No. 1.023.70/, British Patent No. 1.23/
.

No. 230, No. 1, 21♂, No. 7.2≠, No. 1゜3≠
No. 6,220, JP-A-77-4102u! No., same Jl-
//3rd issue, same rr-iipo issue, same tatar/71≠j
R issue, same! Tarl♂2μ Hiroori issue, same! ter/r−≠! O
The developer precursor described in No. 1, etc. can be used.

Especially Akira Tokukai! Tar/7J'Hirojr, same jter/♂λ≠
≠ ri issue, same jter itkohiro! Precursors of (7)/-phenyl-3-pyrazolidinones described in No. Q etc. are preferred.

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 usage amount of the electron donor, ETA or their precursor is 0.0/-30 mol in total per 1 mol of the dye-donating substance, preferably "! L, < n
O, i-z mol, 0 in total per 1 mol of silver halide
．． 00/-7 mol, preferably 06O7~/, 7 mol.

The 7% ETA is less than 60 moles of the total reducing agent, preferably less than 4 AO moles. When ETA is supplied dissolved in water, the concentration of ETA is lo-4 mol/! ~1 mol/l is preferred.

Introducing the compound of general formula CI) of the present invention, reducible, dye-donating substances, electron donors, electron transfer agents or their precursors, and other hydrophobic additives into the hydrophilic colloid layer. is a high-boiling point organic solvent such as phthalic acid alkyl ester (dibutyl 1 note, dioctyl 1 note, etc.), phosphoric acid ester (diphenyl phosphate, triphenyl phosphate, tricyclohexyl phosphate, tric 1/diluphosphate, etc.) Dioctylbutyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), argylats (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate). , dioctyl azelate), trimenoic acid esters (e.g. tributyl trimesate) Patent application Sho A/-23/! Carboxylic acids described in No. 00, JP-A-Shojter 13/! ≠No., same jter/71r≠! /issue,
Same jter/7. S'Hiro! No. 2, same No. 1? -/711733
Same issue! ? -/7r'A! Same as r4L! 9-/71'
A! ! Same issue! U.S. Pat. No. 2,322 using the compounds described in No. 9-/711tj7.

Using the method described in No. 027, or boiling point approximately 300C
/1,00C organic solvents, such as lower alkyl acetates such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone,
After dissolving in 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, if necessary. The amount of high-boiling organic solvent used for the dye-donating substance/7 to 10? Below, preferably below the tag. Moreover, the resistance is below the tag, preferably below the core, for the diffusion-resistant reducing agent/7. Further, a high boiling point organic solvent for the binder 77/7 or less, preferably tL< is o3y or less,
More preferably, it is 0.37 or less. Also, special public Shoj/-32gj No. 3, special public Shoj/-! The polymer dispersion method described in Tatako No. 3 can also be used. It can be directly dispersed in the pore agent, or it can be dissolved in water or alcohols and then dispersed in gelatin or in 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 No. 77≠rJo, same! 3-1
(method described in No. 02733, Tokkoku Akiotsu λ10t♂lrλ, etc.) When dispersing a hydrophobic substance in a hydrophilic colloid, various surfactants can be used. For example, Tokukai Shojter/! The surfactants listed on pages (37) to (3g) of No. 7/y36 can be used.

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 may be a surface latent image type emulsion or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent and a photofog. It may also be a so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different phases.

(d) The silver lodenide 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 high aspect ratio, or any other form.

Specifically, U.S. Pat. No. 4,500,626, column 50;
Research Disclosure Magazine (hereinafter abbreviated as RD) 17029 (1978), No. 4,628.021, JP-A-60-196748, No. 60-192937
Any of the silver halide emulsions described in No. 60-2585357 can be used.

Although the silver halide emulsion may be used unripe, it is usually used after being chemically sensitized. 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-58-126526, JP-A-58-215644).
.

The coating amount of the photosensitive silver halide used in the present invention is in the range of 111 g to 10 g/112 in terms of silver.

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, organic silver salts are particularly preferably used.

Organic compounds that can be used to form the above-mentioned organic silver salt oxidizing agents include U.S. Pat.
There are benzotriazoles, fatty acids and other compounds described in 53Jf4 and the like. Furthermore, silver salts of carboxylic acids having an alkynyl group such as silver phenylprobiol 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 50B to 10g/+ in terms of silver.
2 is appropriate.

Various anticapri agents or photographic stabilizers can be used in the present invention. An example is RD176
43 (1978) 24-25, the nitrogen-containing carboxylic acids and phosphoric acids described in JP-A-59-168442, or the mercapto compounds and mercapto compounds described in JP-A-59-111636. Metal salts, acetylene compounds described in JP-A No. 62-87957, and the like are used.

In the present invention, the photosensitive element may contain an image toning agent if necessary. Specific examples of effective toning agents include compounds described in JP-A-61-147244, page (24).

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, Japanese Patent Publication Nos. 59-180550 and 60-1
No. 40335, RD17029 (1978) 12-1
Sensitizing dyes described on page 3, etc., and JP-A-60-111239
No. 62-32445.

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, US Pat. No. 933.390, 3,635,72
No. 1, No. 3,743,510, No. 3,615,613
No. 3,615,641, No. 3,617,295, No. 3,635,721).

These sensitizing dyes may be added to the emulsion during or before or after chemical ripening.
According to No. 56 and No. 4,225,666, six steps are required before and after nucleation of silver halide grains. The amount added is generally about 10-6 to 10-2 mol per mol of silver halide.

A hydrophilic binder is preferably used in the heat-developable photosensitive element of the present invention. The hydrophilic binder is preferably transparent or translucent, and includes natural compounds such as gelatin, proteins such as gelatin derivatives, cellulose derivatives, starch, polysaccharides such as acacia, dextran, pullulan, polyvinyl alcohol, polyvinyl alcohol, etc. It includes synthetic polymer compounds such as pyrrolidone, partially saponified copolymers of vinyl alcohol and acrylic acid, acrylamide polymers, and other water-soluble polyvinyl compounds described in JP-A No. 62-245260. These binders are 2! It is also possible to use a combination of g1 or more. In addition to these, it is also possible to use dispersed vinyl compounds which are used in latex form and increase the dimensional stability of the photographic material.

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

In the present invention, hydrophobic additives such as reducible dye-donating compounds and electron donors can be incorporated into the layers of the photosensitive element by known methods such as those described in U.S. Pat. No. 2,322,027. . In this case, JP-A-59-83
No. 154, No. 59-178451, No. 59-1784
No. 52, No. 59-178453, No. 59-17845
No. 4, No. 59-178455, No. 59-178457
A high boiling point organic solvent such as that described in
Can be used.

The amount of high-boiling organic solvent is determined by the amount of the dye-providing compound IF used.
The amount is 10 g or less, preferably 5 g or less. Also, ice per 1g of binder, or even 0.5
cc or less, particularly 0.3 cc 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 may also be used.

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

Various surfactants can be used when dispersing hydrophobic compounds in hydrophilic colloids. For example, JP-A-59
-157636, Nos. (37) to (38), those listed as true surfactants can be used.

In the present invention, a compound that activates development and simultaneously stabilizes images can be used in the photosensitive element. For specific compounds preferably used, see U.S. Patent No. 4,500.
, No. 626, columns 51-52.

In systems that form images by diffusion transfer of dyes, dye fixing elements are used in conjunction with light-sensitive materials. The dye fixing element may be coated separately 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 light-sensitive material and the dye fixing element, the relationship with the support, and the relationship with the white reflective layer, the relationships described in column PIS 57 of US Pat. No. 4,500.626 can be applied to the present application.

The dye fixing element preferably used in the present invention has at least one layer containing a mordant and a binder. As the mordant, those known in the photographic field can be used, and specific examples thereof include U.S. Pat. No. 4,500°626 f558-59.
Columns and JP-A No. 1988-88256 (32) to (4l)
Mordant as described in page 60-118834, 6
Examples include those described in Japanese Patent Application No. 0-119557, Japanese Patent Application No. 60-235134, Japanese Patent Application No. 61-87180, and Japanese Patent Application No. 61-87181. Also, U.S. Patent No. 4,463
A dye-receiving polymer compound such as that described in , No. 079 may also be used. .

The dye fixing element can be provided with auxiliary layers such as a retention layer, a release layer, and an anti-curl layer, if necessary.

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

As the binder for the constituent layers of the dye fixing element, natural or synthetic polymeric substances similar to the binders of photosensitive materials can be used.

One or more of the constituent layers of the photosensitive material and the dye fixing element may contain a heat solvent, a plasticizer, an antifading agent, a UV absorber,
A slippery agent, a matting agent, an antioxidant, a dispersed vinyl compound for increasing dimensional stability, a surfactant, a fluorescent whitening resistor, etc. may be included.

Specific examples of these additives are described in JP-A-61-88256, pages (26) to (32). In addition, especially in a system in which thermal development and dye transfer are carried out simultaneously in the presence of a small amount of water, it is preferable for the dye fixing element to contain a base and/or a base precursor, which will be described later, in order to improve the storage stability of the photosensitive material. .

In the present invention, an image formation accelerator can be used in the light-sensitive material and/or the dye-fixing element. 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 1338-40.

Examples of base precursors include salts of organic acids and bases that are decarboxylated by heat, compounds that release amine necks by intramolecular nucleophilic substitution reactions, Rossen rearrangements, or Beckmann rearrangements. Specific examples thereof are described in U.S. Pat. In addition to the above, combinations of poorly soluble metal compounds and compounds capable of complexing reaction with metal ions constituting this poorly soluble metal compound (referred to as complex-forming compounds), as described in European Patent Publication No. 210,660, and special Compounds that generate bases by electrolysis, such as those 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 element separately.

Various development stoppers can be used in the light-sensitive material and/or dye-fixing element 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, an acid precursor that releases acid upon heating;
Examples include electrophilic compounds, nitrogen-containing heterocyclic compounds, mercapto compounds, and their precursors that undergo a substitution reaction with a coexisting base when heated (for example, U.S. Pat. No. 4,677)
No. 0,373, No. 4,656.126, No. 4,610
, No. 957 or No. 4゜626.499, No. 4,67
No. 8,735, No. 4゜639.408, JP-A-61-
No. 147249, No. 61-147244, No. 61-1
No. 84539, No. 61-185743, No. 61-18
No. 5744, No. 61-188540, No. 61-269
No. 148, compounds described in No. 61-269143, etc.).

Preferably, the dye-fixing element is stored at a relative humidity of 25-85%.

The constituent layers (photographic emulsion layer, dye fixing layer, etc.) of the light-sensitive material and/or dye fixing element of the present invention may contain an inorganic or organic hardening agent.

Specific examples of hardeners are given in U.S. Pat. No. 4,678,739, No. 4.
Column 1, those described in JP-A-59-116655 are mentioned, and these can be used alone or in combination.

The support used in the light-sensitive material and/or dye-fixing element of the present invention is one that can withstand processing temperatures.

Common supports include glass, paper, polymer films, metals, and their analogues, as well as those described in JP-A-61-147244, page (25). can.

The photosensitive material or dye fixing element may have a conductive heating layer as a heating means for thermal development or diffusion transfer of the dye.

The transparent or opaque heating element in this case can be made using conventionally known techniques for producing resistive heating elements. As a resistance heating element, there are two methods: one uses Kuroiso material *i which exhibits semiconductivity, and the other uses an organic thin film in which conductive fine particles are dispersed in a binder. Materials that can be used in these methods include those described in JP-A-61-145544 and the like. These conductive layers can also be used as antistatic layers. function.

In the present invention, the method described in U.S. Pat. No. 4,500,626 No. 55 to 5611A can be applied to the coating method of the heat-developable photosensitive layer, protective layer, intermediate layer, undercoat layer, back layer, dye fixing layer, and other layers. .

As a light source for image exposure for recording an image on a photosensitive material, a radiation rope that also includes visible light can be used. In general, light sources used for ordinary color printing, such as tungsten lamps, mercury lamps, halogen lamps such as iodine lamps, xenon lamps, laser light sources, CRT light sources, light emitting diodes (LEDs), etc., are used in US Pat. No. 4.5006.
The light source described in No. 26, No. 564fil can be used.

The heating temperature in the heat development process can be developed at about 0°C to about 250°C, but it is particularly useful to use a heating temperature of about 0°C to about 180°C.The dye diffusion transfer process is performed at the same time as the heat development. Alternatively, it may be carried out after the heat development process is completed. 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 is particularly preferably 50° C. or higher and up to about 10° C. lower than the temperature in the heat development step.

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

Also, JP-A-59-218443, JP-A No. 61-2380
56, 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 5
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 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. Further, a low boiling point solvent, a mixed solution of a low boiling point solvent and water or a basic aqueous solution, etc. 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 a dye fixing element, a light-sensitive material, or both.

The amount used is less than or equal to the weight of the solvent corresponding to the maximum volume of yfBi51 of the entire coated film (especially less than the amount obtained by subtracting the weight of the entire coated film from the weight of the solvent corresponding to the maximum swelling volume of the entire coated film).
A small amount is enough.

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). It is also possible to use the solvent by preliminarily incorporating it into the photosensitive material, the dye fixing element, 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 element. The hydrophilic thermal solvent may be incorporated into either the photosensitive material or the dye fixing element, 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, sulfones, imides, alnyls,
There are 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 element.

As a heating means in the development and/or transfer process, a hot plate, an iron, a hot roller, etc. are used.
There is a method described in No. 7244, pages (26) and (27).

The pressure conditions and method of applying pressure when overlapping the photosensitive material and the dye fixing element and bringing them into close contact are described in Japanese Patent Application Laid-Open No. 61-1472.
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.

The light-sensitive material of the present invention provides a color image in a blur on a dye-fixing element through a heat development-transfer process. In the photosensitive material from which the dye-fixing element has been removed after processing (if any), a dark color image based on the unreacted dye-providing compound remains along with the silver halide and developed silver. Therefore, the photosensitive material of the present invention can be printed onto ordinary color paper or the like using this negative color image. Specifically, the photosensitive material after heat development and transfer processing is desilvered using a known bleach-fix solution or a bleach and fix solution, followed by post-processing such as washing with water, and dried to obtain a negative color. You can get the image. That is, the photosensitive material of the present invention not only provides a positive image through thermal development and transfer processing, but also can be used as a photosensitive material for additional prints.

Example/ The method of preparing emulsion CI) for the first layer will be described.

A well-stirred gelatin aqueous solution (containing 20 f of gelatin and 3 f of sodium chloride in 1000 M water and keeping it warm at 710 C) was mixed with a water bath solution toomi containing 11 um of sodium chloride and potassium bromide and a silver nitrate aqueous solution (water). too
At the same time, 0.1 Y mole of silver nitrate was added at an equal flow rate over ≠θ minutes. In this way, the average particle size is 0.3! A monodisperse cubic silver chlorobromide emulsion (tO mol% of bromine) of μ was prepared.

After washing with water and desalting, sodium thiosulfate 11um, tTn9 and ≠-hydroxy-6-methyl/, 3. Ja,? - Chemical sensitization was carried out at to 0c by adding 20 m9 of tetrazaindene. The yield of emulsion was 6ooy.

Next, how to prepare the emulsion (n) for the third layer will be described.

Gelatin bath solution (1000 rnl of water) with stirring
Contains gelatin Ot and sodium chloride 3f/f 7
j 'C), a water bath solution containing sodium chloride and potassium bromide, a silver nitrate aqueous solution (silver nitrate 0.59 mol dissolved in water 6001), and the following dye solution (1 ) were simultaneously added at equal flow rates over 40 minutes. In this way, a monodisperse cubic chlorobromide raw milk M (bromine 80 mol %) having a dye adsorbed thereon having an average particle size of 0.35 μm was prepared.

After washing with water and desalting, 1 g of sodium thiosulfate 5II and 20 mg of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene were added to perform chemical sensitization at 60°C.

The yield of emulsion was 600 g.

Methanol 400 so 1st 3rd
A method for preparing emulsion (III) for the layer will be described.

Well-stirred gelatin water bath solution (dissolve gelatin 2Of and ammonium in water 10100O
A water bath solution containing potassium iodide and potassium bromide (10100 O) and a silver nitrate aqueous solution (101 O
00O mixed with 1 mol of silver nitrate) at the same time as pA
I added 71G while keeping it at GT speed. In this way, a monodisperse octahedral silver iodobromide emulsion (
Iodine j mol %) was prepared.

After washing with water and desalting, gold and sulfur sensitization was performed by adding chloroauric acid (≠water salt) and sodium thiosulfate (2). What is the yield of emulsion/kI? Met.

Next, we will describe how to make a gelatin dispersion of a dye-donating substance.

Yellow dye-donating substance (1) is ltt% electron donor (ED-P) fcPt1 tricyclohexyl phosphate ft9? It was weighed, cyclohexanone≠6M was added, and the mixture was heated to about 6°C to form a homogeneous solution. 10% bath of this melted and lime-treated gelatin, 1 t of water
After stirring and mixing ocx:: and sodium dodenlebenzenesulfonate i, zt, the mixture was dispersed using a homogenizer at tooorpm for 10 minutes. This dispersion is called a yellow dye-providing substance dispersion.

Similar to the dispersion of yellow dye-providing substance, the dispersion of magenta and cyan dye-providing substances is either magenta dye-providing substance (2) or cyan dye-providing substance (2).
Made using 91y&:.

A photosensitive material 101 having the structure shown in the following table was prepared.

A photosensitive material having the same structure as Photosensitive material 10/, except that the reducing agent (1) in the second layer, the Hiro layer, and the sixth red layer was replaced with equimolar amounts of the compounds of the present invention shown in Table 2. Materials ioλ~tOS were created.

The reducing agent (1) and the compound of the present invention can be added after being dispersed in PO+77-(1)* using the following method.

Reducing agent (ll'l or compound of the present invention λOQ 'I mol and polymer fi+' 7, j f are combined with ethyl acetate)
The mixture was dissolved at about 0°C to form a homogeneous solution. After stirring and mixing this solution with 7 ml of 10% water bath gtooy of lime-treated gelatin and j% water bath solution A of rice and surfactant (5), the mixture was heated at 110,000 f for 70 minutes in a homogenizer.
Dispersed at p.

Next, we will discuss how to make the dye fixing material.

A dye-fixing material R-/f was prepared by coating it on a paper support coated with polyethylene 1/2 in a ten coat composition.

＼Mari
Se! ! 1 can
Color photosensitive material with the above multilayer structure 10/-1
0! The samples were exposed using a tungsten bulb at 200 lux for 1 second through a color separation filter of B, G, R, and G1N with continuously varying densities.

On the emulsion side of this exposed light-sensitive material / j WLl /
Water of rrL2 was supplied with a wire bar, and then the dye fixing material and the membrane surface were overlapped so that they were in contact with each other.

The temperature was adjusted so that the temperature of the film after absorbing water was t5°C, and heated for 13 seconds using a heat roller. Next, when it was peeled off from the dye-fixing material, clear images of blue, green, 1/Tsudo, and G1N were obtained on the fixing material, corresponding to the H, G, R, and G1N color separation filters. .

The maximum density (1) max) and minimum density (Dmin) of each color of cyan, magenta, and yellow in the gray part were measured, and the results are shown in λ.

Furthermore, when the above color photosensitive materials 10/-106 are exposed using a spectrograph through a wedge whose density changes continuously in the direction perpendicular to the wavelength, and processed in the same manner as above, all photosensitive materials have a dye coating λ. The light-sensitive materials in which a reducing agent is added to the intermediate layer and the protective layer all have good color reproducibility, but the light-sensitive material 10/ has a low Dmax. In contrast, the compound of the present invention'? f? WS-added photosensitive material 102-i
A high I)max was obtained for oz.

Example: In the photosensitive material 1oi-tos of Example 1, except for the polymer limmer (1) and the surfactant (5)*, a high boiling point bath medium fi+' (used at 23% by weight based on the reducing agent) was used instead. and a surfactant (1-) to disperse a reducing agent and add it to the second layer, the ≠ layer and the sixth layer to produce a photosensitive material, 20/
-20jr was created. When treated in the same manner as in Example 1, Isun also had good color reproducibility, but photosensitive material 2
At 0/, Dmax was low. However, the photosensitive material λQ-20 containing the compound of the present invention! In this case, a high i)max was obtained.

Furthermore, the photosensitive material is 10/-10! ; and 20/~20!
Part &/! I1. Protective layer) to reducing agent (1)'' or the compound of the present invention, polymer (1)'', surfactant (
Similar results were obtained in the photosensitive rice preparation prepared by omitting 5) and the high-boiling bath medium (1).

Example 3 A photosensitive material 30/ of the structure of Teni (f-stone) was created.

Antifoggant (2) "H Unless otherwise specified, the same one as in Photosensitive Material 10/ was used.

The compound (2j) of the present invention was used instead of the reducing agent (1) used in the third and sixth layers of Photosensitive Material 30/.
A photosensitive material 30-2 having the same structure as the photosensitive material 301 was prepared except that equimolar amounts of the following were added. Also photosensitive material 30/
It has the same structure as photosensitive material 30/, except that the compound (17) of the present invention was added in an equimolar amount instead of the electron donor (ED-b) used in the second layer, third layer, and r-th layer. A photosensitive material of 303 tl was prepared.

All of the dye fixing materials R,-/all described in Example 1 were used.

The color light-sensitive material having the multilayer structure is exposed to 1//Q seconds at 100 lux using a tungsten lamp through a 1/- filter with a continuously changing density to form an emulsion of the light-sensitive material as an exposure source. 20rrLt/1rL2 on the surface
7jC with a wire bar, dye fixing element R-/
and the membrane surfaces were placed in contact with each other. After heating for 2 Q seconds using a heat roller whose temperature was adjusted so that the temperature of the film that absorbed water was 0.degree. C., the photosensitive material was peeled off from the dye fixing material, and an image was obtained on the fixing material. Dmax and Dmin for yellow, magenta and cyan colors
The results of the measurements are shown in Table ≠.

/ Note that the color reproducibility was also good in the photosensitive material of Isu n.

According to Masahiro, it was possible to obtain images with high density by incorporating the silver halide emulsion and the dye-donating substance in separate layers (adjacent layers) and using the compound of the present invention in a friendly material.

Example 1 A color light-sensitive material ≠oi having a multilayer structure as shown in Table J was prepared using the same emulsion, dye-donating substance, electron donor, and electron transfer agent as those used in color light-sensitive material 10/ of Example 1.

Note that unless otherwise specified, the same additives as in Photosensitive Material 10/ were used.

The organic silver salt emulsion was prepared as follows.

Gelatin 209 and ≠-acetylaminophenylpropiolic acid j, 9f in O0l sodium thihydroxide water bath solution 10
0rnl and 200ml of ethanol. This solution was kept at ≠〇〇〇 and stirred.

Dissolve silver nitrate and zt in 20ON of water in this bath solution.
:, 'K was added in 3 minutes. Excess salt was then removed by sedimentation. Then adjust the pH to 6.3 and yield JOO
? An organic silver salt dispersion was obtained.

Further, an antifoggant precursor (110) having the following structure was added at 0.2 times the mole of the dye-donating substance, and the mixture was dispersed in oil according to the method of Example 1 together with the dye-donating substance and the electron donor.

The same as the photosensitive material oi except that the compound (7) or (/l) of the present invention was added in an equimolar amount to the reducing agent (2) used in the second layer and the μ-th layer in Photosensitive Material Kou 01. Photosensitive materials '702 and 'Jt' having the same structure were prepared.

Next, the method of making the dye fixing material (R-J) will be described.

Poly(methyl acrylate-N,N,N-)riftyl-N-vinylbenzylammonium chloride) (The ratio of methyl acrylate and vinylbenzylammonium chloride is t:/) tOf 2001! Dissolve in Ll of water and mix homogeneously with 100f of lime-processed gelatin. A hardener was added to this mixed solution and the paper support was laminated with 1/2 polyethylene in which titanium dioxide was dispersed. Oμ
Next, apply a wet film of m evenly. After drying this sample,
It is used as a dye fixing material (R-, 2) for the mordant layer.

After exposure in the same manner as in Example 1, the film was heated for 30 seconds uniformly on a heat block.

2 (per 1rrL2) on the membrane side of the dye fixing material (R-2).
After supplying uni of water, the heat-treated photosensitive materials were stacked on a fixing material so that the film surfaces were in contact with each other.9.

After that, the linear speed / 2 was applied to the Ubanator heated to ro 0c.
After passing through H/SeG, both materials were peeled off to obtain a positive image on the dye-fixing material.

1) Dm of some cyan, magenta, and yellow colors
Comparison of ax revealed that the photosensitive materials 4A02 and ≠03 obtained by adding the compound of the present invention had a higher density than the photosensitive material Hiroshi Ol.

Patent applicant Fuji Photo Film Co., Ltd. Commissioner of the Patent Office
Record.

1.Display of the incident Showa Otoko year long-awaited request No. 31002r
No. 2. Title of the invention: Heat-developable color photosensitive material. 1. 3. Subject of the amendment: ``Detailed explanation of the invention'' section of the specification. Contents of the amendment. Please correct the description accordingly.

l) Line 2 of page 1 "Because I'm here" “I’m here.” 1 Correct.

2) No. 1/Line “Heat development process in progress” "Developing" to correct.

3) Page 1 O structural formula [ %formula% and correct it.

4) Page 11 Structural formula and correct it.

5) 1st/page structural formula and correct it.

6) Page 76, line ♂ "Immonium group" "Ammonium group" and correct it.

7) No. ≠! Delete the 13th line of the page.

8) Page j3, line 1 "The following general formula (1) and/or [■]" It is corrected as "the following general formula [C] and/or [D]".

9) Delete lines 3 to j on page 33.

10) Page 4j/line 1 r[X-1]," Delete all.

u) 7th/page jth line “Reducibility, dye donation” "Reducible dye donor" I corrected him.

12) Last line of page io "Percentage of particles exceeding lOμ" "Average particle size 10μ" and correct it.

13) Correct the ior page as shown in Attachment l.

14) rti group z rekar on the last line of page 1/7? -(11*≠-chlorophenylsulfonylacetate guanidine" Wora group precursor (1)*Hiroshi-chlorophenylsulfonylacetate guanidine").

Claims (1)

[Scope of Claims] A heat-developable color having on a support at least a photosensitive silver halide emulsion, a binder, a reducing agent or its precursor, and a reducible dye-providing compound that releases a diffusible dye when reduced. In the photosensitive material, the following general formula [I]
A heat-developable color photosensitive material comprising a compound represented by: General formula [I] A-[Time]t-X In the formula, A means a redox mother nucleus, and is an atom that makes it possible to release -[Time]t-X by being oxidized during development processing. It is a group. Time represents a timing group connected to A using S, N, O or Se, and t represents an integer of 0 or 1. X represents a group that functions as a development inhibitor after being released from -[Time]t-X.