JPH0343735A - Heat developable color photosensitive material - Google Patents

Abstract

PURPOSE:To obtain positive images which of less turbid and bright colors by providing >=1 layers of nonphotosensitive layers contg. at least one kind of specific compds. CONSTITUTION:This photosensitive material is provided with 1 layers of the nonphotosensitive layers contg. at least one kind of the compds. expressed by formula I. In the formula, A means the base nucleus for oxidation reduction and denotes the atom group which can release (Time)tX when oxidized during development processing. Time denotes the timing group connected to A by S, N, O or Se and (t) denotes 0 or 1 integer. X denotes the group to function as a development suppressor after released from (Time)tX. The positive images of the less turbid and bright colors are obtd. in this way.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a heat-developable color photosensitive material,
In particular, the present invention relates to a heat-developable color photosensitive material that can produce clear, positive images without clouding.

(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 Edition (published by Corona Publishing, 1982), Volume 2.
It is described in pages 42 to 255, 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.
An oxidized compound that does not have dye-releasing ability is made to coexist with a reducing agent or its precursor, and the reducing agent is oxidized according to the exposure amount of silver halide by heat development, and the remaining unoxidized reducing agent is A method of reducing and releasing a diffusible dye has been proposed. Also, European Patent Publication No. 22074
No. 6, Kokai Technical Report 87-6199 (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.

(Problems to be Solved by the Invention) However, when the above-mentioned reducible dye-providing compound is used in combination with a silver halide emulsion together with a reducing agent or its precursor, staining is high and the color image is poor. It turns out that there is a problem.

Although it is effective to use a diffusible electron transfer agent as a reducing agent in addition to a diffusion-resistant electron donor in order to suppress the staining, this was not sufficient to achieve the objective. In addition, electron transfer agent radicals generated when the electron transfer agent reduces silver ions to silver diffuse into other layers with different color sensitivities, oxidize the electron donors there, and further promote fog development. There is a problem in that the color image deteriorates due to a decrease in image density.

(Object of the Invention) An object of the present invention is to provide a heat-developable photosensitive material capable of producing a brightly colored positive image with low cloudiness.

(Structure of the Invention) An object of the present invention is to provide a support with at least a photosensitive silver halide, a binder, an electron transfer agent or its precursor, an electron donor or its precursor, and a coating that releases a diffusible dye upon reduction. Reducing dye-donating compounds and hydrazine derivatives (
Preferably, in a heat-developable color photosensitive material having a compound represented by the following general formula (I), a compound represented by the following general formula ([)
This was achieved using a heat-developable color photosensitive material having one or more non-photosensitive layers containing at least one type of compound represented by:

General formula (II) A + Time +,

Time represents a timing group of S, N, O, or Se that connects to A, and t represents an integer of 0 or l.

X represents +Time+, a group that functions as a development inhibitor after being released from X.

The configuration of the present invention will be explained in detail below.

The hydrazine derivative used in the present invention has the following general formula (
Compounds represented by 1) are preferred.

General formula (1) % Formula % In the formula, R1 represents an aliphatic group or an aromatic group, and R2 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a hydrazino group, or a carbamoyl group. group or an oxycarbonyl group, G represents a carbonyl group, a sulfonyl group, a sulfoxy group, a 1 -P- group, or a monomethylene group;

2 Az both represent a hydrogen atom, one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group. In the general formula ([) ,R
The aliphatic group represented by 3 preferably has 1 to 30 carbon atoms, particularly a straight IL-branched or cyclic alkyl group having 1 to 20 carbon atoms. The branched alkyl group herein may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. Further, this alkyl group may have a substituent such as an aryl group, an alkoxy group, a sulfoxy group, a sulfonamyl group, or a carbonamide group.

The aromatic group represented by Ro in general formula (I) is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group.

Here, the unsaturated heterocyclic group may be condensed with a monocyclic or bicyclic aryl group to form a heteroaryl group.

Examples include a Cz benzene ring, a napucrene ring, a pyrimidine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, a henzimidazole ring, a thiazole ring, and a hendithiazole ring, among which those containing a benzene ring are preferred.

Particularly preferred as R is an aryl group, and the aryl group or unsaturated heterocyclic group of R may be substituted; typical substituents include an alkyl group, an aralkyl group, an alkenyl group, Alkynyl group, alkoxy group,
Aryl group, substituted amine group, acylamino group, sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group,
Hydroxyl group, halogen atom, cyano group, sulfo group, alkyloxycarbonyl group, aryloxycarbonyl group, anlu group, alkoxycarbonyl group, aralkyl group, carbonamide group, sulfonate group, carboxyl group, phosphoric acid group There are four types of substituents, such as dando group, diacylamino group, imido group, etc., and preferred substituents include straight, branched, and cyclic argyl groups (preferably carbon atoms 1 to 2).
0 mono), aralkyl groups (preferably monocyclic or bicyclic alkyl moieties having 1 to 3 carbon atoms), alkoxy groups (preferably 1 to 20 carbon atoms), substituted amino groups (preferably carbon atoms) Etl~20 alkyl group substituted amine group), acylamino group (preferably carbon number 2~20)
30 carbon atoms), sulfonamide groups (preferably those having 1 to 30 carbon atoms), ureido groups (preferably those having 1 to 30 carbon atoms), phosphoric acid amide groups (preferably those having 1 to 30 carbon atoms) ) etc.

-C The alkyl group represented by R2 in formula (I) is preferably an alkyl group having 1 to 4 carbon atoms, a halogen atom, a cyano group, a carboxyne group, a sulfo group, an alkoxy group, a phenyl group, a sulfonyl group. It may have substituents such as.

The aryl group is preferably a monocyclic or bicyclic aryl group, such as one containing a benzene ring. This aryl group may be substituted with, for example, a halogen atom, an alkyl group, a cyano group, a carboxyl group, a sulfo group, a sulfonyl group, or the like.

The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, and may be substituted with a halogen atom or an aryl group.

The aryloxy group is preferably a monocyclic ring, and examples of iAW include a halogen atom.

Amino group; unsubstituted akino group; carbon number 1-1
0 alkylamino group and arylamino group are preferred,
It may be substituted with an alkyl group, a halogen atom, a cyano group, a nitro group, a carboxy group, etc.

As the carbamoyl group, an unsubstituted carbamoyl group, an alkylcarbamoyl group having 1 to 10 carbon atoms, and a 71/-carbamoyl group are preferable, and an alkyl group, a halogen atom,
It may be substituted with a cyano group, carboxyne group, etc.

The oxycarbonyl group is preferably an alkoxycarbonyl group or an aryloxycarbonyl group having 1 to 10 carbon atoms, and may be substituted with an argyl group, a halogen pyro, a cyano group, a nitro group, or the like.

Among the groups represented by R2, when G is a carbonyl group, preferred are a hydrogen atom, an alkyl group (for example,
, methyl group, trifluoromethyl group, 3-hydroxypropyl group, 3-methanesulfonamidopropyl group, phenylsulfonylmethyl group, etc.), aralkyl group (e.g. z
y, 0-hydroquinhensyl group, etc.), aryl group (e.g., yo, phenyl 1.3.5-dichlorophenyl group, 0
-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group, etc.), and a hydrogen atom is particularly preferred.

Furthermore, when G is a sulfonyl group, R2 is an alkyl group (e.g., methyl group, etc.), an aralkyl group (e.g., 0
-hydroxyphenylmethyl group), aryl group (e.g. phenyl group etc.) or substituted agono group (e.g.
dimethylamino group, etc.) are preferred.

When G1 is a sulfoxy group, R2 is preferably a cyanobenzyl group, methylthiohensyl group, etc., and when G1 is a -P- group, R2 is a methoxy group, ethoxy group, butoxy group, or phenoxy group. A phenyl group is preferred, and a phenoxy group is particularly preferred.

When G1 is an N-substituted or unsubstituted iminomethylene group,
R2 is preferably a methyl group, an ethyl group, or a substituted or unsubstituted phenyl group.As the substituent for R2, the substituents listed for R1 can be used.

G in general formula (1) is most preferably a carbonyl group.

Also, R2 splits the G, -R1 part from the remaining molecule,
It may be one that causes a cyclization reaction to produce a cyclic structure containing an atom of the Cx Rt moiety, and specifically, one that can be represented by general formula (a).

General formula (a) -R, -Z.

In the formula, Zl nucleophilically attacks G, and G, -R□-
21 is a group that can be split from the remaining molecules, R3 is one hydrogen atom away from R2, Zl makes a nucleophilic attack on G, and G3. , R3, and ZI can form a cyclic structure.

More specifically, Z easily reacts nucleophilically with G when the hydrazine compound of general formula (1) generates the next reaction intermediate by oxidation etc., resulting in R-N=~-G, -1'h. -Z is a group that can split R, -N=N group from 01, specifically OH, SH or NHR, (R4 is a hydrogen atom, an alkyl group, an aryl group, CORs, or -3O2R
s, R3 is a hydrogen atom, an alkyl group, an aryl group,
It may also be a functional group that directly reacts with G such as C0OH (representing a heterocyclic group, etc.) (where OH,
SH, NHR=, C00H are temporarily protected so that these groups are generated by hydrolysis with alkali etc. (R-5Rt is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group) It may be a functional group that can react with 01 by reacting with a nucleophile such as a hydroxide ion or a sulfite ion, such as (representing 01).

Furthermore, the ring formed by G, , R, and Z is preferably 5- or 6-membered.

Among those represented by general formula (a), preferred are those represented by general formulas (b) and (C).

General formula (b) -(-CR' b R"b+, C' il B ZI + CR3b R' b +, C formula, R-1
, ~Ra represents a hydrogen atom, an alkyl group (preferably one having 1 to 12 carbon atoms), or an alkenyl group (preferably one having 2 carbon atoms).
~12 carbon atoms), aryl groups (preferably 6 to 1 carbon atoms),
2) and may be the same or different. B is an atom necessary to complete a 5-membered ring or 6-membered ring that may have a substituent, m, n are 0 or l, (
II+m) is 1 or 2.

Examples of the 5- or 6-membered ring formed by B include a cyclohexene ring, a cycloheptene ring, a benzene ring, a naphthalene ring, a pyridine ring, and a quinoline ring.

Z has the same meaning as in general formula (a).

General formula (C) t +N-)-r-(-CRc I R,"-)-, 2 In the formula, R, ', Rc" represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a halogen atom, etc. may be the same or different.

R% represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group.

p represents 0 or 1, and q represents 1-4.

Rc+5Rc2 and Rc3 may be bonded to each other to form a ring as long as Z can make an intrapentadolar nucleophilic attack on c+.

Rc' and Rc'' are preferably hydrogen atoms, halogen atoms,
or an alkyl group, and Rcl' is preferably an alkyl group or an alkyl group.

q preferably represents 1 to 3; when q is 1, p represents O or 1; when q is 2, p represents O or 1; when q is 3, p represents 0 or 1; when q is 2, p represents O or 1; Or when it is 3, Re'5
Rc2 may be the same or different. Zl is the general formula (
Same as a).

A.1. A2 is a hydrogen atom, an alkylsulfonyl group having 20 or less carbon atoms, and an arylsulfonyl group (preferably a phenylsulfonyl group, or a group in which the sum of Hamesoto's substituent constants is -
0.5 or more), an acyl group having 20 or less carbon atoms (preferably a benzoyl group, or a phenylsulfonyl group substituted so that the sum of Hamesoto's substituent constants is -0.5 or more) benzoyl group, or straight chain
, branched or cyclic unsubstituted and substituted aliphatic acyl groups (
Examples of the substituent include a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxyl group, a carboxy group, and a sulfonic acid group. 〉) A hydrogen atom is most preferable as A+ and At.

R1 or R2 in the general formula (1) may be incorporated with a ballast group or a polymer commonly used in immobile photographic additives such as couplers. A ballast group is a group having a carbon number of 8 or more and is relatively inert to photography, such as a 5-alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group,
It can be selected from alkylphenoxy groups, etc.

Examples of the polymer include Peeling L No. 6 described in JP-A No. 1-100530.

R1 or R2 in the -S formula (1) may have a group incorporated therein to enhance adsorption to the silver halide grain surface. Such adsorption groups include U.S. Pat.
459, 34', issue, JP-A-59-195, 2
No. 33, No. 59-200231, No. 59-201,0
No. 45, No. 59-201.046, No. 59-201,
No. 047, No. 59-201, 048, No. 59-201
．． No. 049, JP-A-61-170,733, JP-A No. 61-
No. 270.744, No. 62-948, Patent Application No. 62-6
No. 7.508, No. 62-67.501, No. 62-67
．． Examples include the groups described in No. 510.

General formula (1) Below is a specific row of compounds shown by Shown below.

However, the present invention is not limited to the following compounds.

■ 1) OCI+.

l-3) it ■-4) Sl+ L ■-6) Sl+ N = N l-7) ■-8) ■ l-9) 1-10) 1-11) 12) Sl+] 13) 11 (Margin below) ) The above hydrazine derivatives are known compounds and can be easily synthesized by known methods.

One type of hydrazine derivative may be used alone, or two or more types may be used in combination.

The layer to which such a compound is added may be any layer in a heat-developable photosensitive material (hereinafter sometimes abbreviated as "photosensitive material"), but it may be added to the photosensitive layer or its adjacent layer (for example, an intermediate layer, protective layers, etc.) are preferred, and photosensitive layers are particularly preferred.

The amount added is 10-' per mol of photosensitive silver halide.
-10-' mol, preferably 10-' to 10 mol.

If the hydrazine derivative is used in too large a quantity, the maximum density will be lowered, but by adding it within the above range, the minimum density can be lowered without impairing the image density.

Next, general formula (It) will be explained in detail.

Examples of the redox nucleus represented by 8 include hydroquinone, catechol, p-aminophenol, 0-aminophenol, 1,2-naphthalenediol, 1,4-naphthalenediol, 1,6-naphthalenediol, 1.2
-aminonaphthol, 1,4-acunonaphthol or 1
．． Examples include 6-aminonaphthol. At this time, the amino group is preferably substituted with a sulfonyl group having 1 to 25 carbon atoms or an acyl group having 1 to 25 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 unsubstituted aliphatic acyl groups and aromatic acyl groups. The hydroxyl group or amino group that forms the redox nucleus of A may be protected with a protecting group that can be removed during development. What is an example of a protecting group? =, those having 1 to 25 carbon atoms, such as acyl group, alkoxycarbonyl group, carbamoyl group, and JP-A-59-197037, JP-A-59-201057
One example is Hokenki, which is described in . Furthermore, if possible, this protecting group may be bonded to the substituent A described below to form a 5, 6- or 7-membered ring.

The redox nucleus represented by A may be substituted with an appropriate substituent at an appropriate position. Examples of these substituents include those having 25 or less carbon atoms, such as alkyl groups,
alkylthio group, arylthio group, alkoxy group, aryloxy group, amino group, hydroxyloxy group, acyloxy group, amide group, sulfonamido group, alkoxycarbonylamino group, ureido group, carbamoyl group, alkoxycarbonyl group, Sulfamoyl group, sulfonyl group, cyano group, halogen atom, acyl group, carboxyl group, sulfo group, nitro group, heterocyclic residue, or -4T
ime'')-LX, etc. These substituents may be further substituted with the substituents mentioned above, and if possible, these substituents may be bonded to each other to form a saturated or unsaturated carbon number, or may form a saturated or unsaturated heterocycle.

Preferred examples of A include hydroquinone, catechol, p-aminophenol, 0-aminophenol, 1,
4-naphthalenediol, 1. Examples include 4-aminonaphthol. More preferred examples of A include hydroquinone, catechol, p-aminophenol, and O-aminophenol. Most preferred as A is hydroquinone.

Preferred specific examples of A in the general formula (ff) are shown below. In each structural formula, (*) indicates the position to which -(Time)-1X is bonded.

<3> (4) CH co CH3 CH.

CH.

(5) 0H (14) (15) (16) (17) ○H ○H (19) (26) (27) (28) ○H H ○H Among these, redox having a group that provides diffusion resistance Mother nucleus is preferred.

-("l"imet, X is O-(Time) -L
It is a group released as

Time is a timing group linked to A with a sulfur atom, nitrogen atom, oxygen atom, or selenium atom, and causes X to be released from e→Time)-tX released during development through one or more steps of reaction. The basics are given.

For example, US Pat. No. 4,248,
No. 962, No. 4.409.323, British Patent No. 2,
No. 096,783, U.S. Patent No. 4,146,396;
JP-A-51-1,16828, JP-A-57-5683
Examples include those listed in No. 7.

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 heterocycle or heterocyclic compounds capable of producing iminosilver. Examples of compounds having a mercapto group bonded to a heterocycle include P'RfA or unsubstituted mercaptoazoles (e.g., 1-phenyl-5-mercaptotetrazole, 1-brobyl-5-mercaptotetrazole,
1-phthyl-5-mercaptotetrazole, 2-methylthio-5-mercapto-1,3,4-thiadiazole,
3-Methyl-4-phenyl-5,-mercap)-1,2
, 4-) Riazole, 1-(4-ethylcarbamoylphenyl)-2-mercaptoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-sulfobenzimidazole, 2-mercaptobenzothiazole, 2 -Mercapto-
5-sulfobenzothiazole, 2-mercaptobenzoxazole, 2-phenyl-5-mercapto-1,3,
4-Oxadiazole, 1-+3-, (3-methylureido)phenyl)-5-mercaptotetrazole, 1
-(4-nitrophenyl)-5-mercaptotetrazole, 5-(2-ethylhexanoylamino)-2-mercaptobenzimidazole, etc.), substituted or unsubstituted mercaptoazaindenes (e.g., 6-methyl-4-
Mercapto-1,3,3a,? -tetrazaindene, 4
．． 6-dimethyl-2-mercapto-1,3,3a.

7-tetrazaindene, etc.), substituted or unsubstituted mercaptopyrimidine R (eg, 2-mercaptopyrimidine, 2-mercapto-4-methyl-6-hydroxypyrimidine, etc.).

Examples of heterocyclic compounds capable of forming iminosilver include substituted or unsubstituted triazoles (for example, l, 2
．． 4-triazole, benzotriazole, 5-methylbenzotriazole, 5-nitrobenzotriazole,
5-bromobenzotriazole, 5-n-butylbenzotriazole, 5,6-dimethylhenzotriazole, etc.), substituted or unsubstituted indazoles (such as intasol, 5-nitroindazole, 3-nitroindazole, 3-nitroindazole, etc.) chloro-5-nitroindazole)
, substituted or rZtA-free benzimidazoles (eg, 5-nitrobenzimidazole, 5,6-cyclopenzimidazole, etc.).

In addition, after X separates from Time in the general formula (It) and once becomes a compound having development-inhibiting properties, it further causes a certain chemical reaction with components in the image forming system, resulting in substantial It may also be a compound that has no or significantly reduced development inhibitory properties. Examples of functional groups that undergo such chemical reactions include ester groups, carbonyl groups, imino groups, ammonium groups, Michael addition-accepting groups, and imide groups. Examples of such deactivated development inhibitors include 1-(
3-phenoxycarbonylphenyl)-5-mercaptotetrazole, 1-(4-phenoxycarbonylphenyl)-5-mercaptotetrazole, 1-(3-maleinimidophenyl)-5-mercaptotetrazole, 5
-phenoxycarbonylbenzotriazole, 5-(4
-dianophenoxycarbonyl)hencytriazole,
2-phenoxycarbonylmethylthio-5-mercapto-1,3,4-thiadiazole, 5-nitro-3=phenoxycarbonylimidazole, 5-(2゜3-dichloropropyloxycarbonyl)benzotriazole,
1-(4-benzoyloxyphenyl)-5-mercaptotetrazole, 5-(2-methanesulfonylethoxycarbonyl>-2=mercaptobenzothiazole, 5-
Cinnamoylaminobenzotriazole, 1-<3-vinylcarbonylphenyl>-5-mercaptotetrazole, 5-succinitomethylbenzotriazole, 2
-(4-succinicamedophenyl) -5-mercapto-1,3,4-oxadiazole, 6-funinoxycarponyl-2-mercaptobenzoxazole, and the like.

Specific examples of the compound represented by general formula (II) are listed below.

H n-10 ■-12 H2 Hff nC, Hq nC=Hl ■-14 ■-15 ■-16 ■-17 n(4H.

■-24 ■ 5 ■-27 ca Hq ■-29 ■-30 H3 H ■-32 C2H5 [[-39 H nC3H1 ■-49 ■-56 ■-59 ■-60 ■-63 ■ 8 General formula (■) The compound represented by can generally be synthesized by the following two methods.

First, if Time is a simple bond (1=0), the first is chloroform or 1. 2-Benzoquinone, orthoquinone, quinone monoimine, quinone diimine in dichloroethane, carbon tetrachloride, tetrahydrofuran without a catalyst or in the presence of an acid catalyst such as p-toluenesulfonic acid, pencenesulfonic acid, trifluoromethanesulfonic acid, methanesulfonic acid, etc. This is a method in which a derivative and a development inhibitor are reacted at a temperature between room temperature and 100°C. The second is potassium carbonate, sodium bicarbonate, in an aprotic polar solvent such as acetone, tetrahydrofuran, dimethylformamide, etc.
A compound obtained by reacting a benzoquinone, orthoquinone, quinone monoimine, or quinone diimine derivative substituted with chlorine, bromine, or iodine with a development inhibitor in the presence of a base such as sodium hydride or triethylamine at a temperature between -20°C and 100°C. This is a method of reducing the resulting quinone body with a reducing agent such as diethylhydroquinolamine or sodium hydrosulfide. [References: (Research
hDisclosure l 8227 (1979
); LiebigsAnn, Chem, 764
．． 131 (1972)) Next, in the case of a type in which X is released via Time (t=1), the synthesis can be performed in substantially the same manner as above. That is, the above development inhibitor (X
) instead of Time-X, or first introduce Time-X having a substitutable group (for example, a halogen atom, a hydroxyl group, or a precursor thereof) into the redox core, and then replace This is a method of linking X through reaction.

The amount of the compound of general formula (II) of the present invention to be added in each layer is from 0.00 mmol to 1 mmol, preferably 0.00 mmol to 1 mmol per 1 d of support. Ol mmol ~ 5 mmol,
In each layer, 0.001 per gram of binder in that layer.
mmol to 1 mmol, preferably 0.01 mmol to 0.5 mmol.

In the non-invention, in addition to photosensitive layers having different color sensitivities, the above general formula (
A non-photosensitive layer containing a compound represented by II) is provided.

When there are three sets of photosensitive layers each having a different color sensitivity, this non-photosensitive layer is preferably provided between each photosensitive layer. When there are a plurality of non-photosensitive layers, the compound of general formula (I) of the present invention added to each non-photosensitive layer may be the same or different.

In the present invention, a reducible dye-donating compound is combined with an electron transfer agent and an electron donor, a binder, and a silver halide emulsion to form a 1-unit photosensitive layer. The reducible dye-providing compound may be added to the same layer as the silver halide emulsion, or may be added separately to adjacent layers.

In the latter case, it is preferable from the viewpoint of sensitivity that the layer containing the reducible dye-providing compound is located below the silver halide emulsion layer.

In this case, the electron transfer agent and electron donor can be added to either the silver halide emulsion layer or the reducible dye-donating compound layer, but at least the electron transfer agent is present in the silver halide emulsion layer. preferable.

In the present invention, at least two sets of such photosensitive layers are used.

Normally, in order to reproduce full color, three sets of photosensitive layers with different color sensitivities are installed. For example, there are three combinations of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, and a three-set combination of a green-sensitive layer, a red-sensitive layer, and an infrared-sensitive layer. Each color-sensitive layer can be arranged in various arrangements known in conventional color-sensitive materials.

Moreover, each of these color-sensitive layers may be divided into two or more layers as necessary.

An example of a preferable layer structure of the heat-developable color light-sensitive material of the present invention is: support - heat-developable red light-sensitive layer - non-light-sensitive layer containing the compound of the present invention - heat-developable green light-sensitive layer - heat-developable green light-sensitive layer Non-photosensitive layer containing - heat-developable blue-sensitive layer - protective layer, transparent support - heat-developable blue-sensitive layer - non-photosensitive layer containing the compound of the present invention - heat-developable green photosensitive layer - containing the compound of the present invention Non-photosensitive layer
Heat-developable red light-sensitive layer - protective layer, support - cyan dye-providing compound layer - red-sensitive emulsion layer (1) non-photosensitive layer containing the compound of the present invention - magenta dye-providing compound layer - line-sensitive emulsion layer (1) of the present invention The layer includes a non-light-sensitive layer, a yellow dye-providing compound layer, a blue-sensitive emulsion layer, a protective layer, etc.

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

The non-photosensitive layer of the present invention may also serve as a yellow filter layer.

In the present invention, a reducing agent may be used in combination with the compound of general formula (II) in the non-photosensitive layer. As the reducing agent used in combination, those described in Japanese Patent Application No. 62-279842 are preferably used. In particular, hydroquinones having a diffusion-resistant group as a substituent are preferably used. That amount of usage! The amount ranges from 0.05 mmol to 10 mmol per 1 rr of support and from 0.01 mmol to 10 mmol per tg of binder.

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-II.

PWR-(Time), -Dye General formula (C-I) In the formula, PWR is reduced by -(Time)
+-Represents a group that releases Dye.

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

t represents an integer of 0 or 1.

pye represents a dye or its precursor.

First, PWR will be explained in detail.

PWR is based on U.S. Pat. No. 4,139,389, or U.S. Pat.
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 a part containing an electron-accepting quinonoid center and a 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.
It may correspond to a moiety containing an aryl group and an atom (sulfur atom, carbon atom, or nitrogen atom) that connects it to a photographic reagent. Also, U.S. Patent 4,45
It may correspond to a moiety containing a nitro group in a nitro 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. 0,223. , corresponds to the geminal dinitro moiety in the dinitro compound that beta-desorbs 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 may be.

Also, more preferably, European Patent No. 220.7
No. 46A2, Publication Axis 87-6199, U.S. Patent No. 4.
783.3'J6, JP-A No. 63-201653, JP-A No. 63-20165.4, etc., N-X in one molecule.
A compound having a bond (X represents an oxygen, sulfur, or nitrogen atom) and an electron-withdrawing group, so! -x (X has the same meaning as above) and a compound having an electron-withdrawing group, JP-A-63-27134
Compound having a P〇-X bond (X has the same meaning as above) and an electron-withdrawing group in one molecule described in No. 4, JP-A-63-2
71341, a c-x' bond (X'
is synonymous with X or represents -Sot) and a compound having an electron-withdrawing group. In addition, the patent application 1986-31
Compounds described in No. 9989 and No. 62-320771 that release a diffusible dye by cleavage of a single bond by a π bond conjugated with an electron-accepting group after reduction can also be used.

In order to more fully relate the object of the present invention, the general formula (C
Among the compounds of -1), those represented by the general formula [C■] are preferred.

General formula (Cu) (Time″Ft [)ye is R"' R”Z Alright binds to at least one of the EAGs.

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

X represents a group containing an oxygen atom (-〇->, a sulfur atom (-S-), or a nitrogen atom (-NCR"')-).

Rlfil, RIOZ and Root represent a group other than a hydrogen atom or a simple bond.

Groups other than hydrogen atoms represented by R1+II, RIOI, and R103 include alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, aryol groups, heterocyclic groups, sulfonyl groups, carbamoyl groups, sulfamoyl groups, etc. These may have a substituent.

RI@I and R1+12 are preferably substituted or unsubstituted alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, acyl groups, sulfonyl groups, etc.@R
The number of carbon atoms in 10'% and Roax is preferably 1 to 40.

R102 is preferably a substituted or unsubstituted acyl group or sulfonyl group, and examples thereof are the same as the acyl group and sulfonyl group described for RIOI and R1112. The number of carbon atoms is preferably 1 to 40.

R101, R102 and R'03 may be bonded to each other to form a five or more ring.

As X, enzymes are particularly preferred.

EAG will be described later.

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

The general formula (CI[[) (T i me), [)ye is bonded to at least one of R"' and EAG.

X has the same meaning as above.

R14 represents an atomic group that is bonded to ×1 nitrogen atom to form a monocyclic or condensed heterocycle of five or more members including the nitrogen atom.

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

General formula (A) In general formula (A), 2 represents -C-3ub or -N-.

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

Vs;Zz-1Van-Zs Z4-1vs;-2,
-2, -2, -1V, -Z3-Z4Zs Zh-1
Vt; Z3 Z4 ZS-26-Z, -1Vs;
Zh 24 25 24 ZvZ, -.

Sub 5ub 22 to Z each represent -〇--N--〇-ub -S-5 or -SO□-, and each Sub represents a simple bond (pi bond), a hydrogen atom, or the substitution described below. Sub represents a group, each of which may be the same or different, and may be bonded to each other to form a saturated or unsaturated carbocyclic or heterocyclic ring of three or more members. You can.

In the general formula (A3), the sum of the Hammett substituent constant sigma para of the substituents is +0.50 or more, more preferably +0.
Select Sub so that it is 70 or more, most preferably +0.85 or more.

EAG is preferably a ring group or a heterocyclic group substituted with at least one electron-withdrawing group. Substituents bonded to the heptadyl 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 an EAG is described in European Patent Publication No. 220746A2, pages 6-7.

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

Various groups represented by Time are known, for example, JP-A-61-147244, pages (5)-(6), JP-A-61-147244.
No. 36549, pages (8)-(2), patent application 1986-886
Examples include the groups described on page 25 (36) = page (44).

The pigments represented by [)ye include Abu pigment, azomethine pigment,
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.

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

The compound represented by the above general formula (CII) or (Cln) must itself be immobile in the photographic layer,
Therefore, it is desirable to have a ballast group having 8 or more carbon atoms at the position of EAGSRIaI, RIO2RI OJ or X (particularly the position of EAG).

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, and is described in European Patent Publication No. 220746A2, Publication Branch Axis No. 87-6199, etc. Dye-providing compounds that have been described can also be used.

Shiku JNH + hHn (II) (6)・ (10) C14H33 (11) (12) (15) (16) C,,H,.

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

The amount of the dye-donating compound used depends on the extinction coefficient of the dye, but is 0.05 to 5 mmol/r+? , preferably 0.1
The dye-providing substances in the range of .about.3 mmol/% can be used alone or in combination of two or more. In addition, in order to obtain images of black or different hues,
As described in No. 2251, for example, at least one of each of cyan, magenta, and yellow dye-providing substances is mixed and contained in a layer containing silver halide or in an adjacent layer. It is also possible to use a mixture of two or more types of dye-providing substances that release dyes.

In the present invention, an electron donor and an electron transfer agent (ETA) are used, and details of these compounds are described in European Patent Publication No. 220746A2, Japanese Patent Publication 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 () General formula (D) In the formula, A1゜l and A and B 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, Roe (R; alkyl group, oryl group, etc.), hydroxamic acid anions S0,20, l or secondary amines, hydrazine, Examples include compounds with lone pairs of electrons such as hydroxylamines, alcohols, and thiols.

Preferred examples of Al0I s AH02 include a hydrogen atom, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, an alkylcarbonyl group, a dialkylphosphoryl group, a dialkylphosphoryl group, or JP-A-59-197037. , 59-
Protecting groups disclosed in No. 20105 may also be used, and A1゜1, A1゜2 may be R2O', . . .
R"", R"co and R"" may be combined with each other to form a ring.Also, A10A+02 may be the same or different.

Rzo+ , Rzoz , Rzos and R204 are each a hydrogen atom, an alkyl group, an aryl group, an alkylthio group, an arylthio group, a sulfonyl group, a sulfo group, a halogen atom, a cyano group, a carbamoyl group, a sulfamoyl group, an amide group, an imido group, a carboxyl group , a sulfonamide group, etc. These groups may have substituents if possible.

However, the total carbon number of R201 to Rzo° is 8 or more. In addition, in general formula (C), R201 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 CD), those in which at least two of R201 to R2Q4 are substituents other than hydrogen atoms are preferred. Particularly preferred compounds are those in which at least one of R2G+ and R212 and at least one of R2O3 and R20' 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.

Specific examples of the electron donor will be listed, but the invention is not limited to these compounds.

(ED-1) (ED 2) (ED-3) (ED-4) (ED-5) (ED-6> CH3 CH.

(ED-13) (Jl-1 The amount of the electron donor (or its precursor) to be used has a wide range, but is preferably 0.0 per mole of the positive dye-donating 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 is the following general formula (X-1) or (
xn).

[X ■〕

(X-n) In the formula, R represents an aryl group. R: BII, R corotR30co, R304, Rgo (Is and R30& are hydrogen atoms, halogen atoms, acylamino groups, alkoxy groups,
It represents an alkylthio group, an alkyl group, or an alkyl group, and may be substituted if possible. Further, these may be the same or different.

In the present invention, compounds represented by general formula (X-If) are particularly preferred. In the general formula (X-n), R co11+ SR coro1, R362 and R1104 are 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. A group is preferable, and more preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a phenyl group, a hydroxyl group, an alkoxy group,
It is a phenyl group substituted with a hydrophilic group such as a sulfo group or a carboxyl group.

Specific examples of ETA are shown below.

(X-1) (X 3) (X=5) (X 2) (X-4) (X-6) (X-73 (X-9) (X-11) (X-8) (X 10 ) (X-12) (X-13) (X-15) (X-1'7) (X-14) (χ-16) The ETA precursor used in the present invention refers to the storage of photosensitive materials before use. Among them, it is a compound that does not have a developing action, but can release ETA only by the action of an appropriate activation 1A (e.g., base, nucleophile, etc.) or heating.

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

Examples of the ETA precursor used in the present invention include 1-
2 and 3-acyl of phenyl-3-pyrazolidinone=i
2-aminoalkyl or hydroxylalkyl derivatives, hydroquinone, metal salts such as catechol (lead, cadmium, calcium, barium, etc.), halogenated acyl conductors of hydroquinone, oxazine and bisoxazine derivatives of hydroquinone, lactone type ETA precursors ,
In addition to 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, and tuclide. Examples include an ETA 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.
゜967, same No. 3. No. 246,988, No. 3.2
No. 95,978, No. 3,462.266, No. 3.
No. 586,506, No. 3,615,439, No. 3
．． 650. No. 749, No. 4,209,580,
British Patent No. 4,330.617, British Patent No. 4.310.612, British Patent No. 1.02'3,701, British Patent No. 1.231
No. 830, No. 1,258,924, No. 1゜346
．． No. 920, JP-A-57-40245, JP-A No. 58-11
The drug precursors described in No. 39, No. 58-1140, No. 59-178458, No. 59-182449, No. 59-182450, etc. can be used.

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

ETA and ETΔ precursor can also be used together.

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 N 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, but the diffusion-resistant electron donor is present in the same layer as the dye-donating substance. Preferably, 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, preferably 0.1 to 5 mol, silver halide 1 mol, L'2ft, per 1 mol of the dye-donating substance. Total amount is 0 per mole
．． 001 to 5 mol, preferably 0.01 to 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/1 to 1 mol/
1 is preferred.

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

There are 8 like this! In the metal salt, there are 8! Silver salts are particularly preferably used.

There are 8 of the above! Organic compounds that can be used to form the silver salt oxidizing agent include benzotriazoles and fatty acid compounds described in U.S. Pat. No. 4,500,626, columns 52-53. Also vF Kaisho f30-1132
Silver salts of carboxylic acids having alkynyl groups such as silver phenylpropiol described in No. 35, and JP-A-61-249
Acetylene silver described in No. 044 is also useful. Two or more types of organic @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. Photosensitive silver halide and 8! The total amount of silver salt applied is 50IIg to IO in terms of silver.
H/m" is appropriate.

Various antifoggants or photographic stabilizers can be used in the present invention. For example, RD176
43 (19784>24-25), the azoles and azaindenes described in VF 1978-168442, the nitrogen-containing carboxylic acids and phosphoric acids described in JP-A-59-111636, and the mercapto compounds and metals thereof described in JP-A-59-111636. Salts, acetylene compounds listed in Vf 62-87957, and the like are used.

Hydrophilic materials are preferably used for the structure of the photosensitive material and the dye fixing material, and for the layer material. Examples include those described on pages (26) to (28) of JP-A-62-2531'59. Specifically, transparent or translucent aqueous binders are preferred, such as proteinaceous materials such as gelatin and gelatin derivatives, or cellulose derivatives,
Natural compounds such as polysaccharides such as starch, gum arabic, dextran, pullulan, etc. and polyvinyl alcohol,
Examples include polyvinylpyrrolidone, acrylamide polymer, and other synthetic polymer compounds. Also, JP-A-62-
Super absorbent polymer, Nana b, described in No. 245260 etc.
Homopolymers of vinyl monomers having (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-58) manufactured by Sumitomo Chemical Co., Ltd. is also used. Two or more of these pine nuts can also be used in combination.

When employing a system that performs thermal development by supplying i amount of water, the use of the above superabsorbent polymer makes it possible to quickly absorb water. In addition, if a highly water-absorbing polymer is used in the dye fixing layer or its protective layer, the transfer a
It is possible to prevent the dye from retransferring from the dye-fixing material to something else.

In the present invention, the amount of banhgu applied is preferably 20 g or less per 1+a'', particularly 10.0 g or less, and more preferably 7 g or less.

The composition N (including the back layer) of the photosensitive material or dye fixing material contains various polymers for the purpose of improving film properties such as dimensional stabilization, prevention of curling, prevention of adhesion, prevention of film cracking, and prevention of pressure sensitivity. It can contain latex. Regarding threads, Japanese Patent Application Laid-open Nos. 62-245258 and 62-136
Any of the polymer latexes described in No. 648, No. 62-110066, etc. can be used. In particular, using a polymer latex with a low glass transition point (below 40°C) for the mordant layer can prevent cracking of the mordant layer, and using a polymer latex with a high glass transition point for the back layer can prevent curling. can get.

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

The amount of high-boiling organic solvent is determined by the amount of the dye-donating compound used.
1011 or less, preferably 5 g or less.

In addition, less than ice per gram of pine goo, and 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 can also be used.

In the case of a compound that is substantially insoluble in water, in addition to the above-mentioned method, it is possible to incorporate the compound in the form of fine particles into a fraction of the compound in the bangu.

Six examples of how various surfactants can be used when dispersing hydrophobic compounds in hydrophilic colloids i1f * Kaisho 5
The surfactants listed in No. 9-157636 cQ, pages (37) to (38) can be used.

In the present invention, a compound that activates development and stabilizes images can be used in the light-sensitive material. For specific compounds preferably used, see U.S. Patent No. 4,50.
No. 0,626, columns 51-52.

In systems that form images by diffusion transfer of dyes, a dye-fixing material is used together with a light-sensitive material.1 Even if the dye-fixing material is coated separately on a support separate from the light-sensitive material, The relationship between the light-sensitive material and the dye-fixing material, the relationship with the support, and the relationship with the white reflective layer may be coated on the same support as described in U.S. Patent No. 4°S OO, 626. The relationship described in column 57 of the above issue is also applicable to the present application.

The dye fixing material preferably used in the present invention has at least one layer containing a mordant and a pineapple. As the mordant, those known in the photographic field can be used, and specific examples thereof include U.S. Pat. The mordant described in JP-A No. 62-244043, No. 62-
Examples include those described in No. 244036 and the like.

Also, dye-receiving polymeric compounds such as those 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.

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

It is recommended to use a high boiling point organic solvent in the constituent layers of the photosensitive material and the dye fixing material as a plasticizer, slip agent, or peelability improver between the photosensitive material and the dye fixing material. No. 62-253159 (25) L 5
There is one described in No. 2-245253.

Furthermore, various silicone oils (
All silicone oils can be used, from dimethylsilicone oil to modified silicone oils in which various organic groups are introduced into dimethylsiloxane. For example,
R-modified silicone oil J published by Shin-Etsu Silicone (Machi)
Various modified silicone oils described in technical material P6-1881m, carboxy-modified silicone (product name X-22)
-3710) etc. are effective.

! ? , :vFl [No. 62-215953, 1M63-4
The silicone oil described in No. 6449 is also effective.

An anti-fading agent may be used in the photosensitive material or the dye-fixing material. Examples of the anti-fading agent C include an antioxidant, an ultraviolet R absorber, or a certain metal complex.

Examples of antioxidants include 1r dicron compounds, coumaran compounds, phenolic compounds (eg II hingudophenols), hydroquinone derivatives, hingudamine derivatives, and spiroin bean threads. Also,
Compounds described in JP-A-61-159644 are also effective.

As ultraviolet M absorbers, benzotriazole compounds (
U.S. Pat. No. 3,533,794, etc.), 4-thiazolidone compounds (U.S. Pat. No. 3,352,681, etc.),
Benzo-7/N-based compounds (Japanese Patent Publication No. 46-2784, etc.), other patent publications No. 48535/1986, 62-136
There are compounds described in No. 641, No. 61-88256, and the like. In addition, ultraviolet #I described in JP-A No. 62-260152
Absorbent polymers are also effective.

As metal complexes, U.S. Patent No. 4,241,155;
No. 4,245,018, columns 3 to 36, No. 4,25
No. 4,195, columns 3 to 8, JP-A-62-174741, JP-A No. 61-88256, pages (27) to (29), JP-A No. 63
-199248, Japanese Patent Application No. 62-234103, No. 6
There are compounds described in No. 2-230595 and the like.

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

The anti-fading agent for preventing fading of the dye transferred to the dye-fixing material may be included in the dye-fixing material in advance, or may be supplied to the dye-fixing material from outside the photosensitive material. Warning 1: The above antioxidants, ultraviolet absorbers, and metal complexes may be used in combination.

A fluorescent brightener may be used in the light-sensitive material or dye-fixing material. In particular, it is preferable to incorporate the fluorescent brightener into the dye-fixing material or to supply it externally to the light-sensitive material. “The
Chemistry or 5ynjhetic D
yesJMV@M Chapter 8, JP-A-61-143752, etc. can be mentioned. More specifically, stilbene compounds, coumarin compounds,
Examples include biphenyl compounds, benzoxacylyl compounds, naphthalimide compounds, pyrazoline compounds, and carbostyryl compounds.

Optical brighteners may be used in combination with antifade agents.

Hardening agents used in the constituent layers of photosensitive materials and dye-fixing materials are disclosed in US Patent '$4. (No. 378,739, column 41, JP-A-59-116655, JP-A-62-245261,
Examples include hardeners described in Japanese Patent No. 61-18942.

More specifically, aldehyde hardeners (such as formaldehyde), 7-noridine hardeners, epoxy hardeners, vinyl sulfone hardeners (N,N'-ethylene-bis(
(vinylsulfonyl heptamide) ethane, etc.), N-methylol type hardeners (dimethylol urea, etc.), and one example is a polymer hardener (compounds described in JP-A No. 62-234157, etc.).

Various surfactants can be used in the constituent layers of the light-sensitive material and the dye-fixing material for the purposes of coating aids, improving peelability, improving slipperiness, preventing bands, promoting development, and the like. Specific examples of surfactants are disclosed in JP-A-62-173463 and JP-A-62-173463.
It is described in No. 183457, etc.

The constituent layers of photosensitive materials and dye-fixing materials include improved slipperiness,
An organic fluoro compound may be included for the purpose of preventing static electricity, improving peelability, etc. Representative examples of method fluoro compounds include Japanese Patent Publication No. 57-9053 No. 8-17i, l [61-2
7) Thread surfactants described in No. 0944, No. 62-13582f3, etc., oily tether-type compounds such as yota or 77-cable oil, or solid fluorine compounds such as 47-fluorinated ethylene 81-fat. Examples include hydrophobic fluorine compounds such as 8f fat.

A matting agent can be used in the photosensitive material and the dye fixing material. As a matting agent, JP-A-61-8825 such as silicon dioxide, polyolefin or polymethacrylate can be used.
In addition to the chemical compounds listed on page 6 (2S), benzoguanamine ti? ! Patent Application No. 110064/1982 for beads, polycarbonate resin beads, AS fat beads, etc.
There is a compound described in No. 110065.

In addition, the constituent layers of the light-sensitive material and the dye-fixing material may contain a thermal solvent, an antifoaming agent, an antifoaming agent, a Frogl silicate agent, and the like.
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. 8! Promotion of reactions such as formation of dyes, decomposition of dyes, and release of diffusible dyes, and promotion of transfer of dyes from the light-sensitive material layer to the dye fixing layer. A capable, physical and chemical 8! ! Bases or base precursors, nucleophilic compounds, high-boiling organic solvents (oils), thermal solvents,
It is classified as a surfactant, a compound that interacts with silver or silver ions, etc. However, these substance groups are generally complex 8! ! It usually has some of the above-mentioned promoting effects. Details of these can be found in U.S. Pat. No. 4,678,739, columns 38-40.

Base precursors include salts of free acids and bases that are decarboxylated by heat, and intramolecular nucleophilic rI! Examples include compounds that release amine molecules by catalysis, Rossen rearrangement, or Beckmann rearrangement. A specific example is US Pat. No. 4,511,493! It is described in Kaimei No. 62-65038 and the like.

In a system in which thermal development and dye transfer are carried out simultaneously in the presence of a small amount of water, a base and/or a base precursor is preferably included in the dye-fixing material in order to improve the storage stability of the light-sensitive material.

In addition to the above, there are also compounds that can react with poorly soluble metal compounds and metal ions constituting these sparingly soluble metal compounds as described in European Patent Publication No. 210,660 and U.S. Patent No. 4,740,445 ( Combinations of complex-forming compounds (referred to as complex-forming compounds) and compounds that generate bases by electrolysis as described in JP-A-61-232451 can also be used as base precursors. The former method is particularly effective.

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

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

The development stopper referred to here is a compound that neutralizes the base or reacts with the base to reduce the base concentration in the film and stop development, or a compound that quickly neutralizes or reacts with the base after proper development, or a compound that can interact with silver or silver salt. A compound that inhibits development.

In the prefecture, acid precursors, which release acids when heated,
Examples include electrophilic compounds that undergo a substitution reaction with a coexisting base when heated, nitrogen-containing heterocyclic compounds, mercapto compounds, and derivatives thereof.

For more details, please refer to +￥ Kaisho 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. Generally, paper and Gokai Takasuko (film) are mentioned. Specifically, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene,
Synthesis of polyimide, cellulose (e.g. triacetyl cellulose) or films containing pigments such as titanium oxide, film method legal paper made from polypropylene, polyethylene, etc. Shibusho class, Yankee paper made from
Baryta slope, two-tired paper (particularly Castfoot Bin), metal, '8r type, 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 to this (Ko, Machi Kai @ No. 62-253159 (29 N ~ (
Using the support described on page 31)→C″c.

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

i! for photosensitive materials! The method of exposing and recording the ff image is as follows:
Example 1! Direct photography of landscapes and people using a camera, exposure through reversal film or negative film using a printer or enlarger, scanning exposure of the original image through a slit, etc. using a photocopy exposure device, etc. A method of exposing image information by emitting light from a light emitting diode, various lasers, etc. via an electrical signal, and outputting image information to an image-attenuating device such as a CRT, liquid crystal display, electroluminescent display, or plasma display. However, there are methods of exposing directly or through an optical system.

Light sources for recording images on photosensitive material include natural light, tungsten lamps, light emitting diodes, laser light sources, CRT light sources, etc. as mentioned above, such as U.S. Pat. No. 4,500,6
The light source described in No. 26, column 56 can be used.

Furthermore, an image 6N light can be obtained 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 cage field that appear when a strong optical electric field such as a laser beam is applied, such as lithium niobate, potassium dihydrogen phosphate ( KDP), lithium iodate, BaB, O, etc. ! Iso compounds, urea derivatives, difluoride derivatives, nitropyridine-N-oxide derivatives such as 3-methyl-4-nitrovirinone-N-oxyto (POM), JP-A-61
Compounds described in No.-53462 and No. 62-210432 are preferably used. As the form of the wavelength conversion element, single crystal optical waveguide type, fiber type, etc. are known, and both of them are useful.

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

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

In this case, the transparent or opaque heating element is
1-145544 + 7/l specification etc. can be used. In addition, these conductive layers can also be used as anti-static layers.
function.

The heating temperature in the heat development process is approximately 50°C to approximately 25°C.
t' development is possible, but it is particularly useful at about 80°C to about 180°C.The diffusion transfer step of the dye may be carried out simultaneously with the heat development or after the heat development process is completed; In this 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 it is more preferably 50° C. or higher and about 10° C. lower than the temperature in the heat development step.

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

Also,'! F! Kaimei No. 59-218443, Kaimei No. 61-
As detailed in No. 238056, etc., development and transfer can be carried out simultaneously or twice by heating in the presence of a small amount of solvent (especially water).
! A sequential method is also useful. In this method,
The heating temperature is preferably 50°C or higher and lower than the boiling point of the solvent.
For example, when the solvent is water, the temperature is preferably 50°C or more and 100°C or less.

Examples of solvents used to accelerate development and/or transfer the diffusible dye to the dye fixing layer include water or a basic aqueous solution containing Kuroiso's alkali metal salt or an organic @ group.
These bases have the image form f1. Those listed in the section on accelerators 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 in which they are applied to dye-fixing materials, photosensitive materials, or both.6The amount used is less than the total M of one solvent, which corresponds to the maximum swelling volume of the entire coated film (particularly when the total coated film is coated). A small amount (less than or equal to the weight of the entire coated film subtracted from the weight of the solvent corresponding to the swollen volume of the film) may be sufficient.

Photosensitivity/! ! As a method of applying 78 medium to F or the dye fixing layer, for example, 1171El! 61-14724
There is a method described in No. 4 (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 thermal solvent may be incorporated into either the photosensitive material or the dye-fixing material, or may be incorporated into both.The layer in which it is incorporated may also be an emulsion layer, an intermediate layer, a protective layer, or a dye-fixing layer. Inner Ji! in the dye fixing layer and/or its adjacent layer! It is preferable to let

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

Further, in order to promote dye transfer, one portion of a high boiling point organic solvent may be included in the photosensitive material and/or the dye fixing material.

The heating method in the development (F/or transfer process) is to contact a heated block or plate, a hot plate, a hot prefuser-1 heat roller, a halogen lamp heater, an infrared lamp heater, a far-infrared lamp heater, etc. For example, it may be passed through a high-temperature atmosphere B.

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 VF Kaikai 1-147.
The method described in No. 244, 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 such as those described in Japanese Patent No. 177547, No. 59-181353, Japanese Utility Model No. 60:18951, Japanese Utility Model Application Publication No. 62-25944, etc. are preferably used.

Example 1 (1) Preparation of silver halide emulsion Emulsion (I) A well-stirred gelatin aqueous solution (20 g of gelatin 1 g of potassium bromide in 800 ml of water, and 0H (CH2
) The following solutions (I), (II), and (I) were simultaneously added at equal flow rates over 30 minutes to IS (added with 5 g of CH2L○H0 and kept at 50°C). In this way, a monodisperse silver bromide emulsion having an average grain size of 0.degree. 42.mu. adsorbed with a dye was prepared.

After washing with water and desalting, add 20g of lime-treated ossein gelatin, adjust the pH to 6.4 and pAg to 8.2, and then
Keep warm at C, add sodium thiosulfate 9■, chlorauric acid 0.0
1% aqueous solution 6Tnl, 4-hydroquine-6-methyl-1
, 3,3a, 7-tetrazaindene (190 mg) was added, and chemical sensitization was performed for 45 minutes. Yield of emulsion is 635g
Met.

Dye (a) Dye [b) Emulsion <H> Well-stirred aqueous solution (gelatin 2 in 730 m water)
0g, potassium bromide 0.30g, sodium chloride 6g, and the following chemical A 0.015g and kept at 60.0°C), the following solutions (I) and (II) were added at the same time for 60 minutes.
Added at equal flow rates over minutes. (I) After finishing adding the liquid,
A methanol solution (I[I)7& of the following sensitizing dye was added. In this way, a monodisperse cubic emulsion adsorbed with a dye having an average grain size of 0.45 μm was prepared.

After washing with water and desalting, add 20g of seratin and adjust the pH to 6.4.
After adjusting the pAg to 7.8, chemical sensitization was performed at 60°0°C. The chemical used at this time was triethylthiourea 1
．． 6mg and 4-hydroxy-6-methyl-1,3,3a
, 100 mg of 7-tetrazaindene and the ripening time was 55 minutes. The yield of this emulsion was 635 g.

CH3 (sensitizing dye C) Emulsion (■) A well-stirred gelatin aqueous solution (20 g of gelatin 1 g of potassium bromide 1 g of potassium bromide and 0H (CH2) in 800 ml of water
Add 0.35 g of 2S(CH2)208 and heat to 50°C
The following (I) solution, (IF) solution, and (II
Solution I) was added simultaneously at equal flow rates over 30 minutes.

In this way, a monodisperse silver bromide emulsion having an average grain size of 0.degree. 35.mu. adsorbed with a dye was prepared.

After washing with water and desalting, add 20 g of lime-treated ossein seratin and adjust the pH to 6.4 and pA and g to 8.2.
Insulated at 16°C, sodium thiosulfate 16cm, chloroauric acid 0.
01% water happy liquid 121nl, 4-hydroxy-6-methyl-1,3,3a,? - 190 mg of tetrazaindene was added and chemical sensitization was performed for 45 minutes. Yield of emulsion is 635g
Met.

Dye (a) Pigment (b) (2) Add 407 nl of cyclohexanone to the above formulation for each of yellow, magenta, and cyan gelatin useful dye-donating compounds and melt by heating to about 60°C to form a homogeneous solution. And so. This solution was stirred and mixed with a 10% aqueous solution of lime-treated ceratin, 0.6 g of sodium dodecylbenzene sulfonate, and 50 g of water, and then mixed with a homogenizer for 10 minutes at l 0000 r.
Dispersed at pm.

This dispersion liquid is called a dispersion of seratin of a dye-providing compound.

Dye-donating compound (1) CON)lc16HIl(II) (2f CONHCI6H33(II) C0NHC+sH++(II) Electron donor H High boiling point solvent 1l (3) Preparation of a small number of large zinc oxide particles with an average particle size of 0.2μ 12.5 g of zinc hydroxide, 1 g of carboxymethyl cellulose as a dispersant, and 0.1 g of sodium polyacrylate were added to 100 g of a 4% aqueous gelatin solution and ground for 30 minutes in a mill using glass beads having an average particle size of 0.75 a+m.

The glass beads were separated to obtain a dispersion of zinc hydroxide.

A heat-developable color photosensitive material 1 having a multilayer structure shown in Table 1 was prepared using the material thus prepared.

In addition, additives other than those mentioned above in Table 1 are shown below.

Water-soluble polymer (1) Sumikagel L-5 (H) Imagery chemistry (made by scooping) Water-soluble polymer (2) SO, to Surfactant (1) Aerosol OT Surfactant (2) Surfactant (3) Surfactant (4) Hardener n+ ■.

2-bis(vinylsulfonylacetamide) Ethane = 190 High boiling point organic solvent (1) Tricyclohexylphosphate NHCOCsH+ 1 (II) Antifoggant (2) Antifoggant (3) H Antifoggant (4) Electron transfer agent (1) Each layer was coated on a polyethylene laminated paper support with the composition shown in Table 2 to produce a dye fixing material.

Table-2 The additives used are shown below.

Corn oil (1) CH.

CH.

CH.

CH, -3i 〇--→S1 Oh. 5tCH+ (CH2)12cOOH H3 CCII□) l 2 C0OH Surfactant (1) Surfactant (2) C,F 7S○, NCH2C00K C,H.

H,,C0NHCH2CH2CH,N@CH,C00e
CH.

Surfactant (4) C, H5 CH2C○○CH,CHC,H.

N a O3S CHC○OCH+CHC, Hi(
, E-(5 Fluorescence enhancer (1) 2゜5bis(5-tert-butylbendioxazole (2)) Surfactant (5) C3H.

C,F 7S○2N-(CH,CH20-h-+CH,+,SO
, Na water-soluble polymer (1) Sumikagel L5 (manufactured by Imagery Chemical Co., Ltd.) Water-soluble polymer (2) Dextran (molecular weight 70,000) Mordant (1) + CH2 cH+-TV+Cl-12 CH←Stone→CH2-CII+ Darkness .2゜Matting agent (1)'' Warpage matting agent (2) 5 Benzoguanamine resin (average particle size 15μ) In the second and fourth layers of photosensitive material 1, the following compound dispersed in seratin by an oil dispersion method was added. 0 each.
Comparative photosensitive material 2 was prepared by adding the compound at a concentration of 0.036 mmol/d.

Compound (I-7) 01 of the present invention] In the photosensitive material 1, in the first layer, the third layer and the fifth layer, the compound (I-7) is added in an amount of 3.0×10 −5 mol per mol of silver halide; The following compound (1) was added to prepare a photosensitive material 3. Further, a photosensitive material 4 was prepared by adding the following compound (2) in the same manner.

Compound (1) II-3 S-order compound (2) II-8 In photosensitive material 1, the compound of general formula (I) of the present invention is dispersed in oil in the second and fourth layers as shown in Table 3. Dispersed in Seratin by method, each layer has a concentration of 0.03
6 mmol/”m, and further the first layer,
The compound of general 2 (■) of the present invention was added to the third and fifth layers in an amount of 3.0XIO-' mol per 5H mol of the halogen, to prepare photosensitive materials 5 to 1O.

The color light-sensitive material having the multilayer structure was exposed using a spectrograph through a wedge whose density was continuously changing in the direction perpendicular to the wavelength.

15ynl on the emulsion side of this exposed color photosensitive material.
/tri of water 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 film was heated for 20 seconds using a heat roller whose temperature was adjusted so that the temperature of the water-absorbed film was 85°C.

Next, when the dye-fixing material was peeled off from the light-sensitive material, a blue, green, and red spectral durum was obtained on the dye-fixing material in accordance with the wavelength.

The densities of cyan, magenta, and yellow in the blue light part, cyan, magenta, and yellow in the green light part, and cyan, magenta, and yellow in the red light part were measured using a 3′, 0 type Ji measuring instrument manufactured by Xrite. The table shows the results converted to analytical concentrations.
Shown in 3.

From Table 3, the sensitive materials to which the compound (X) of the present invention was added are as follows:
It was found that by increasing the concentration and further adding Compound (II) of the present invention, the cloudy concentration of blue, green, and red was lowered, and the colors became more vivid.

Similar results were obtained when the support for the heat-developable color photosensitive material was replaced with a paper support laminated on both sides with polyethylene.

Furthermore, the method of making the ceratin dispersion of the reducing agent (1) added to the second and fourth layers or the compound of general formula (■) of the present invention may be changed from an oil dispersion method to a polymer dispersion method or a fine particle dispersion method. , similar results were obtained.

Details of oil dispersibility, polymer dispersion method, and fine particle dispersion layer are shown below.

Oil dispersion method 20 mmol of the reducing agent (1) or the compound of the present invention was added to 2 g of triisononyl phosphate and 30 mmol of ethyl acetate.
- at about 6 U°C to form a homogeneous solution. This solution, 100 g of a 10% aqueous solution of lime-treated ceratin, and 60 g of water
1.5g Sodium esterbenzene sulfonate
After stirring and kneading, use a homogenizer for 10 minutes.
Dispersed at 100 rpm.

Polymer dispersion method Reducing agent (1) or 30 mmol of the compound of the present invention in PM
7.5 g of MA was dissolved in 40 ml of ethyl acetate at about 60°C to form a homogeneous solution. 6. This solution, 100 g of a 10% aqueous solution of lime-treated gelatin, and a 5% solution of a surfactant with the following structure. After stirring and mixing with 7 ml, the mixture was dispersed using a homogenizer at 1000 rpm for 10 minutes.

Surfactant fine particle dispersion method Reducing agent (1) or uninvented compound 20 i 1) Moles and aerosol ○T0.5g to 1% gelatin aqueous solution 1
In addition to 0.00 g, 100 g of glass beads having an average particle size of about 0.6 mm were added and ground in a mill for 20 minutes. Glass peas were separated by mouth to obtain an aqueous dispersion.

Claims (1)

[Scope of Claims] At least a photosensitive silver halide, a binder, an electron transfer agent or its precursor, an electron donor or its precursor, and a reducible dye-donating property that releases a diffusible dye upon reduction on a support. A heat-developable color photosensitive material containing a compound and a hydrazine derivative, the heat-developable color photosensitive material having one or more non-photosensitive layers containing at least one compound represented by the following general formula (II). General paper (II) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ A in the formula means redox nucleus, and when it is oxidized during the development process, ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ represents an atomic group that makes it possible to Time represents a timing group of S, N, O or Se that is linked to A, and t represents an integer of 0 or 1. X represents a group that functions as a development inhibitor after being released from ▲There are mathematical formulas, chemical formulas, tables, etc.▼.