JPS63250645A - Thermal developing color photosensitive material - Google Patents

Abstract

PURPOSE:To improve the density of a color image and to reduce the generation of fogging of the titled material by providing with a layer contg. a photosensitive silver halide, a reducing agent, a dye donating compd. and a precursor of a specified development restrainer on a supporting body. CONSTITUTION:The titled material is provided with the layer contg. the photosensitive silver halide, the reducing agent, the dye donating compd. and the precursor of the specified development restrainer on the supporting body. In formula I, PWR is a group capable of releasing (Time)-AF group at the time of reducing, Time is a group capable of releasing AF group, AF is a group of a development restrainer, t is 0, 1. The precursor of the development restrainer shown by formula II is preferable in the compd. shown by formula I. In formula II, EAG is a group capable of accepting an electron, X is -O-, -S- or -NR<3>- group, R<1>, R<2> and R<3> are each a single binding group or a group except hydrogen atom., Time is a group capable of releasing AF group by cleaving a N-X binding. Accordingly, as a said precursor is incorporated in the titled material, the increase of the max. and the min densities of the color image is lessened, even in case of changing a developing temp., and the generation of fogging can be reduced.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a heat-developable color photosensitive material, and more particularly to a heat-developable color photosensitive material that forms an imagewise distribution of a diffusive dye.

(Prior art and its problems) Various proposals have been made regarding the method of obtaining a dye image by heat development, but among these, there is a method that can be easily and completely separated from a silver image. , on a dye-donating compound that completely forms or releases a diffusible dye upon thermal development, and the diffusible dye is diffused into a dye-fixing element (also called an image-receiving element) by the action of heat and/or a solvent. Methods for obtaining dye images are attracting attention.

(U.S. Patent No. 14,1AtJ, 07P, US Pat. No. 1 AtJ, 4L
7! , f67 issue, same issue≠, Ko 7! , Pλ No. 7, same No.
307.310, same number a, zoo, tat number, same @4
A, ur3. ri/≠No. 1% Kaisho 71-/Hiro PO4<J No., same! I-/41P0147, same! P-1rozur
No. 419-/1r4AJP, No. 419-/1r4AJP, same! tar/71tr
JJ issue, same! ? -/74ArJJ No., same JP-/7(I
r341, same! Tar/74113! No., same jF-2/
No. 144443, No. 4/-2jrOjJ, EPaiO
A40A etc.].

Heat development processing is advantageous in that images can be obtained quickly, but it also has the problem that photographic properties tend to change due to slight changes in processing temperature and processing time during development. In order to solve this problem, various development stoppers have been proposed.

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, the acid precursor that releases Fff'6 upon heating, and the 'R' that undergoes a substitution reaction with the coexisting base upon heating.
Examples include It-1-H compounds, nitrogen-containing heterocyclic compounds, mercapto compounds, and their precursors (for example, JP-A No. 37, JP-A No. 2003-13002, To-/Fλ 3-3),
Compounds described in the same to-co JOIJJ issue or the same 60-λJO/J≠ issue).

Compounds that release all of the mercapto compound upon heating are also useful, for example, JP-A-67-78', No. t1, No. 6
/-l Gua J4t4! No., same t/-7λμ tag No., same 6
1-/117143, j/-/J'2037, ≦/-/rj74A'1, 4/-/r4tJJ, 41-/71j4-9, Otsu/-1363λ It is a compound described in .

However, since these compounds utilize a thermal decomposition reaction, the release rate of the development inhibitor is slow.

Therefore, in order to sufficiently suppress capri, it is necessary to add a large amount, and there is a problem that the concentration tends to decrease.

(Objective of the Invention) Therefore, the object of the present invention is to provide color 1 with high density and low capri.
IfIi1!9. How to obtain heat-developable color photosensitive materials? It is to provide. Another object of the present invention is to control the processing temperature during development;
An object of the present invention is to provide a heat-developable color photosensitive material that provides images that are stable against fluctuations in processing time.

(Structure of the Invention) The object of the invention is to provide at least a photosensitive silver halide, a reducing agent, a binder, and a dye-donating property that provides a mobile dye on a support in response to a reaction in which silver ions are reduced to silver. This was achieved by a heat-developable color photosensitive material characterized by forming a compound and a development inhibitor precursor represented by the following general formula (1).

General formula (1) %formula% By reducing PWRi in the formula (Time+TAF represents a group that releases k.

'f' i me is (T ime-)-1 from PWR
After AF and I are released, the subsequent reaction Kanakura and AF
Represents a fund that releases.

t represents the arrangement a of O casing or /.

AF represents a fund that functions as a development inhibitor after being released.

First, PW'kL will be explained in detail.

PWR is a U.S. citizen permit μ, /JF, No. 312 or U.S. patent≠, /3F, No. 372, JP-A-32-/r-333, JP-A-P-/PO/72, JP-A-7- 1≠4t
! It corresponds to the part containing an electron-accepting center and an intramolecular nucleophilic substitution reaction center in a compound that releases a photographic reagent by an intramolecular nucleophilic substitution reaction after being reduced as disclosed in No. 3. is also good, US patent≠, λ3 co,
lθ7, JP-A-7F-10/l-data Rurui, JP-A/-1♂λ37, Research Disclosure (
/91 Hiromu) ■, Muichi≠O-! It corresponds to the electron-accepting quinonoid center in a compound that eliminates the photographic reagent by an intramolecular electron transfer reaction after reduction and the carbon atom-containing moiety that connects it to the photographic reagent, as disclosed in . It may be something. Also 0LSJ, 0
0 r.

JRY issue, Japanese Patent Publication No. Showa J6-/Reference λJ30, US time FF4
T,! No. 443,193, 13% allowance for rice! , 4/ri.

IM with an electron-withdrawing group in a compound whose single bond cleaves and releases a photographic reagent after reduction, as shown in ry4I-.
It may correspond to a moiety containing a substituted aryl group and an atom (sulfur atom, carbon atom, or nitrogen atom) that connects it to a photographic reagent. U.S. patent≠
, μ! It corresponds to the nido a group in a nitro compound that releases a photographic reagent after electron acceptance, as disclosed in No. 0,2co No. 3, and the part that combines the carbon atom that connects it with the photographic reagent gold. Also good, US clock 4c, tori, 4
It may correspond to the geminal dinitro moiety in the dinitro compound that leaves the photographic reagent 11-B after accepting electrons described in No. 70 and the carbon atom moiety that connects it to the photographic reagent. . But what is the purpose of this invention? In order to more fully achieve this, among the compounds of general formula (1), those represented by general formula (It) are preferred.

General formula 11) In general formula (n) AG Corresponds to the PWR of RO.

(T'me h AF binds to at least one of Bl, kL2, or EWG.

The portion corresponding to PWR in general formula (11) will be explained.

X represents a group containing an oxygen atom (-C)-), a sulfur atom (-S-), or a nitrogen atom (-N-).

R1, R2 and 几3 are groups other than hydrogen atoms, and represent mere bonds.

R1 and R3 are preferably substituted or unsubstituted alkyl groups, aryl groups, heterocyclic residues, acyl groups, sulfonyl groups, and the like.

R2 is preferably a substituted or unsubstituted acyl group or sulfonyl group. R1, 2 and R3 are bonded to each other to form 3-
! A negative ring may also be formed.

EAG will be described later. Furthermore, in order to achieve the object of the present invention, among the compounds represented by the general formula (ID), those represented by the general formula (Ill) are preferred.

General formula (ill) corresponds to EAG. (Time-)-A k' is R', E
AG(7) binds to at least -10,000.

The portion corresponding to PWkL in general formula (III) will be explained. Y is a divalent linking group and is preferably -C-6 or -8O2-. X has the same meaning as above, but preferably represents an oxygen atom.

几4 represents the atomic group 7 which is bonded to X and Y to form a j to r-membered monocyclic or condensed heterocycle including a nitrogen atom.

Preferable examples including the bonding position of % Tr me # AF will be described.

蓼EAG EAG EAG EAG ■ EAG EAG EAG EAG ・EAG 囼AG EAG Quantity EAG EAG EAG 星 EAG EAG C) EAG ■ EAG EAG is preferably a group represented by the following general formula (A) or CB).

(A) CB) In the general formula (A), [Jn/ is 3~ together with Zo and Z2! The atomic group r that forms a negative ring represents r1/, which represents an integer of J −r, v ;-Z3-1V4i-Z3-Z,, v ;-Z
3-Z4-Z, -1V, -Z3-Z4-z -z,
, V, E-Z3-Z4-Z5-Z6-z v ,
-z3-z4-z5-z, -z7-■ -Deru, z2
~v8 each represents Sub Sub, where Sub is a simple bond (π bond), a hydrogen atom,
Alternatively, it represents a substituent described below.

Sub#:t may be the same or different, or may be bonded to each other to form a negative saturated or unsaturated carbocycle or heterocycle. In general formula (A),
The sum of the Hammett substituent constants σp of the substituents is +o, oP or more, especially 10,! Above, even 10, ≠! K Subt- is selected so that it is equal to or higher than that.

In general formula (B), n" represents all integers from / to B, U□;-Y□, U2.-Y□-Y2, U, -Y
-Y, -Y3, U4. -Y□-Y2-Y -Y
U, -Y -Y2-Y3-Y434%5
1 -YU; -Y□-Y2-Y3-Y, -Y5-Y, each of Y -Y is Sub'
Sub and Sub' represent a simple bond (σ bond or π bond), a hydrogen atom, or a substituent 7 described below. In general formula CB), the Hammett substituent constant σp of the substituent is +0.02 or more, particularly +0.3 or more,
Moreover -4-o, μ! KSub' so that it is more than that? select.

Examples when Sub is a substituent are listed below. (The number of carbon atoms is preferably 0-UO each.) ft-substituted or non-substituted alkyl groups (e.g., methyl group, ethyl group, 5ec-butyl group, t-octyl group, benzyl group, cyclohexyl group,
chloromethyl group, dimethylaminomethyl group, n-hexadecyl group, trifluoromethyl group, 3,3,3-tricaapropyl group, methoxycarbonylmethyl group, etc.),
Substituted or unsubstituted alkenyl groups (e.g. vinyl i,
J-refinyl group, l-methylvinyl group, etc.), substituted or unsubstituted alkynyl group [e.g. ethynyl group,
/-propynyl group], cyan group, nitro group, halogen atom (fluorine, chlorine, bromine, iodine), substituted or unsubstituted heterocyclic residue (g-pyridyl group, l-imidazolyl group, benzodeazole group) 2-yl group, morpholino group, benzoxazole-koyl group, etc.), sulfo group,
Carboxyl group, substituted or unsubstituted aryloxycarbonyl group, alkoxycarbonyl group (e.g., methoxycarbonyl group, ethoxycarbonyl group, tetradecyloxycarbonyl group, comethoxyether group, phenoxycarbonyl group, ≠-cyanocarbonyl group) (phenylcarbonyl group, carbonyl carbonyl group, etc.)
, a substituted or unsubstituted carbamoyl group (e.g. carbamoyl group, methylcarbamoyl group, diethylcarbamoyl group, methylhexadecylcarbamoyl group, methyloctadecylcarbamoyl group, phenylcarbamoyl group,
French, 4-)lichlorolupamoyl group, N-ethyl-N-
phenylcarbamoyl group, 3-hegisadecylsulfamoylphenylrupamoyl group, etc.), humanmixyl group,
Substituted or unsubstituted azo groups (e.g. phenylazo group,
p-methoxyphenylazo group, λ-cyan-methanesulfonylphenylazo group, etc.), substituted or unsubstituted-
- alkoxy or alkoxy groups (e.g. methoxy, ethoxy, dodecyloxy, benzyloxy, phenoxy, methoxyphenoxy, 3-acetylaminophenoxy, J-methoxypropyloxy, trimethylammonioethoxy group, etc.), sulfino group, sulfeno group, mercapto group, substituted or unsubstituted acyl group (e.g. acetyl group, trifluoroacetyl group, n-i teroyl group, t-i teroyl group, benzoyl group, λ-carboxybenzoyl group, 3
-nitrobenzoyl group, formyl group), substituted or unsubstituted aryl or alkylthio group (e.g. ethelthio group, ethelthio group, t-octylthio group, hexadecylthio group, phenylthio group, -1 Buddha, J-trichlorothio group, -1 methoxoj-1-octylphenylthio group, λ-acetylaminophenylthio group, etc.), substituted or unsubstituted aryl group (e.g. phenyl group, naphthyl group, 3-sulfophenyl group, Hiro-methodiphenyl group, 3-laurylaminophenyl group), substituted #'i unsubstituted sulfonyl group (e.g., methylsulfonyl group, chloromethylsulfonyl group, n-octylsulfonyl group, n-hexadecylsulfonyl group, 88cm octylsulfonyl group) group, p-) luenesulfonyl group, ≠-
am or unsubstituted sulfinyl groups (e.g. methylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group,
≠-nitrophenylsulfinyl group, etc.), substituted or unsubstituted amino groups (e.g. methylamino group, diethylamino group, methyloctadecylamino group, phenylamino group, eterphenylamino group, 3-tetradecylsulfamoylphenylamino group) group, acetylamino group, trifluoroacetylamino group, N-hexadecyl acetylamino group, N-methylbenzoylamino group, methoxycarbonylamino group, phenoxycarbonylmethyl group, N
-Methoxyacetylamino group, amidiamino group, phenylamino group, phenylamino group, French-cyanophenylaminocalnylamino group, N-ethylethoxycarbonylamino group, N-methyldodecylsulfonylamino group, N
-(λ-cyanoethyl)-p-) luenesulfonylamino group, hexadecylsulfonylamino group, etc.), substituted or unsubstituted sulfamoyl group (for example, dimethylsulfamoyl group, hexadecylsulfamoyl group, sulfamoyl group) , methyloctadecylsulfamoyl group, methylhexadecylsulfamoyl group, -monocyanoethylhexadecylsulfamoyl group, phenylsulfamoyl group, he-('+''-dimethylphenyl)-N-octylsulfamoyl group , diptylsulfamoyl group, dioctadecylsulfamoyl group, bis(2-methoxycarpyl ether)sulfamoyl group, etc.), substituted or unsubstituted acyloxy groups (such as acetoxy group, benzoyloxy group, decyloxy group, chloroacetyloxy group, etc.) (coconut group, etc.), substituted or unsubstituted sulfonyloxy group (
Examples include methylsulfonyloxy M, p-4 luenesulfonyloxy group, p-triT:11:+phenylsulfonyloxy7 group, etc.).

A more specific example of EAG is an aryl group substituted with at least one electron-withdrawing group (e.g., tJfμ-
Nitrophenyl group, 2-nitro-μ-N-methyl-N-
octadecylsulfamoylphenyl group, x-N+N-
dimethylsulfamoyl-μm nitrophenyl group, coquano-μm octadecylsulfonylphenyl group, i,
≠l dinitrophenyl group, λ, 4L, & -t! jri7
/7 enyl group, 2-nitro-μ-N-methy/L-N-octadecylcarbamoylphenyl group, cornitro! −
Octylthiophenyl group, co-dimethanesulfonylphenyl group, 3. z-dinitrophenyl group, λ-chloro≠-nitro7-/terphenyl group, 2-nido O-J
, j-dimethyl-l-tetradecylsulfonylphenyl group, co,≠-dinitronaphthyl group, coethyl group 4-nitrophenyl group%-2,4'-bis-
dodecylsulfonyl-j-toIJ fluoromethylphenyl&,' +3, μ, j, j-pentafluorophenyl group, co7 ceteru μm nitrophenyl group, λl≠l
diacetylphenyl group, -12troμm trifluoromethylphenyl group, etc.), substituted or unsubstituted heterocycles (e.g., cobiridyl group, 2-pyrazyl group, j-ditrocopyricyl group, z-
Decyl power to N-lupamoyl-λ-pyridyl group, ≠-
pyridyl group, 3. j-dicyanocobiridyl group,! −
Dodefursulfonyl-λ-pyridyl group,! -Cyanor 2
-pyrazyl group, 4L-nitrothiophen-2-yl group,
! -nitro/, λ-dimethylimidazole-μmyl group, 3,! -diacetyl-copyridyl group, l-dodecyl-j-carpamoylpyridinium-coyl group, etc.), substituted or unsubstituted quinones (e.g. l2μm
benzoquinone-λ-yl M, 3t j +butytrimethyl-7,4L-benzoino-yl group, 3-methyl-/, pina-7-toquinone-coyl M, j, j-dimethyl-! -hexadecylthio/, μm penzoquinone-1-yl group,! -pentadecyl7. (lambda-benzo non-glyl group, etc.), vinyloglynes, nitroalkanes, and α-diketo compounds listed above.

Next, +Time+TAF will be explained in detail.

Time represents a group that releases AF=2 through the subsequent reaction, potentially causing cleavage of the nitrogen-oxygen single bond.

t represents O or/of course.

Various groups represented by Time are known, for example, JP-A-47-747 λμ≠ pages (j) to (4), pages A/-
Examples include the groups described in uJjj4'P No. CI) pages to (/4')X.

Examples of development inhibitors that can be used in AF include compounds having a mercapto group bonded to a heterocycle, such as unsubstituted or unsubstituted mercaptoazoles (specifically l-phenyl-!-mercaptotetrasol, 1 -(p-carboxyphenyl)-!-mercagutotetrazole, /-(
J-hydroxyphenyl)-! -mercaptotetrazole, l-(≠-sulfophenyl)-j-mercaptotetrazole, 1-(3-sulfophenyl)-1-mercaptotetrazole, /-(<<-sulfamoylphenyl)-! -Merkaftotetrasol, /-(3-hexanoylaminophenyl)-! - mercaptotetrazole,
1-Ethyl-3-mercaptotetrazole, 1-(-1carpoxyethyl Q/)-! - mercaptotetrazole,
λ-Methylthio j-mercapto i, 3.4t-thiadiazole, 2-(2-diethylthio in carbo)-! −
Mercapto 7,39 μm thiadiazole, 3-methyl-l-phenyl-! -Mercapto/, 2. gutriazole, co(λ-dimethylamineethylthio)-j-
Mercapto-1,! , 4t-thiadiazole, /-(&
-n-hexylcarbamoylphenyl)-2-mercaptoimidazole, 3-acetylamino-≠-methyl-3
-Mercapto! .

-J-nitro-
/, 3-benzoquinazole, /- (/- Nafti Q/)
-j-mercaptotetrazole, λ-phenyl! -Mercapto-7,3゜Hiro-oxadiazole, /-(J-
(J-methylfried) phenyl 1-3-mercaptotetrazole, /-(4A-nitrophenyl)-7-mercaptotetrazo-z-(J-ethylhexanoylamino)-comelcabutobenzimidazole, etc.) , substituted or unsubstituted mercaptoazaindenes (specifically, 6-methyl-mercapto/, J, Ja, 7
-Chitrazainden, t-Mef Roux J-Benzyl-
Hiroshi Merck) 'Tot.

3, ja, 7-chitrazaindene, 6-phenyl-≠-
Mercaptotetrazaindene, μ,6-cymethyl-2-
mercapto-/, J, 3a, 7-titrazaindene, etc.), substituted or unsubstituted mercaptopyrimidines 7 (specifically, #'iJ-mercaptopyrimidine, λ-mercapto≠-methyl-, monohydroxy 7-pyrimidine/, λ −
mercapto-propylpyrimidine, etc.). Heta-a-ring compounds capable of producing iminosilver, such as substituted or unsubstituted be/citriazoles (specifically, be/citriazoles)
Citriazole! - Nitropenzotriazole,! −
Methylbenzotriazole,! , 6-dichlorobenzotriazole, ! -bromobenzotriazole,! -Methoxybenzotriazole,! -acetelaminobe/citriazole, j-n-butylbenzotriazole,!
-2) (2-4-chlorobenzotriazole,!, 6-
Dimeterbenzotriazole, ≠,! , 6.7-titrathalolbenzotriazole, etc.), substituted or substituted indazoles (specifically indazole, !-nitroindazole, 3-nitroindazole, 3-ria!-nitroindazole, 3 - cyanointasol,
3-n-butylcarbamoyl intersol,! -Nitro-3-methanesulfonyl/dazole, etc.], substituted or unsubstituted benzimidazoles (specifically, !-
Nitropenzimidazole, Hiro-Nitropenzimidazole,! , t-jiku mouth pent imita sole,! -cyanobu-chlorbenzimidazole,! -triple ormethyl-t-trilorbenzimidazole, etc.), specifically /-(J-phenogicalzenylphenyl-j-mercaptotetrazole, /-(Hiro-phenoxycarbonylphenyl)3-mercapto). Tetrazole,
/-(J-maleinimidophenyl)J-mercaptotetrazole,! -(phenoxylbenzotriazole, r-(p-cyanopheno-?7carbonyl)
Benzotriazole, copeenoxycarbonylmethylthio-j-mercapto-/, 3. ≠−The Asiazo k,
j-nitro-3-phenoxycarbonylindazole,
! -Phenoxycarbonyl-2-mercabutobenzimidazole, j-(u, J-dichloropropyloxycarbonyl)bencitriazo k, J-penzyloxycarbonylbenztriazole, j-(butylcarbamoylmethoxycarbonyl)benzotriazole,! -(cycarzenyl in butoxycarbonylmeth)benzotria l-
/-C≠-diphenyl in benzoyluo)-3-mercaptotetrazole, 3-(2-methanesulfonylethoxycarbonyl)-J-J Kabutobe/zothiazole,
/-(a-(λ-alethoxycarbonyl)phenyl 1-2-mercazotoimidazole, λ-(J-(thiophene-choylcarnyl-1propyl)thio-3-mercapto-/, j , μmthiadiazole, !-cinnamoylaminobe/citriazole, '(J-vinylcarbonylphenyl)-!-mercaptotetrazole, !-succinimidomethylbenzotria 1-k, J-111-succinimidophenyl 1-j-mercapto- /, 31μ
m-oxadiazole, 3(μm(benzo-7,coisotheazole-3-oxo-1l/-dioxy-coyl)7enyl)-j-mercapto-methyl-7,2,
Examples include μ-triazole, 4-carbonyl-2-mer-triazole/tuoxazole, and the like.

These development inhibitors have a site (-8H) that causes development inhibition.
(S atom of , N atom of imino group, etc.) to Time or 1, 2, 4, or EAG.

Specific examples of the development inhibitor precursor of the present invention represented by general formula (1) are shown below.

AF-/ O2 AF-J AF-j A　　　　　-7 AP-2 AP-// AF, -/　λ AP-/J AP-t4t No.

AP-/r AF-/P AlI’-koO AP-22 AP-26 SCJ, N (CH2CH20CH3 N2AP-27 AF-1! AF-22 NO□ AF-3° AF-J/ AF-JJ A　P　−j　μ Ai”-31 NO□ AP-36 O2CH3 AP'-J AF-san〇 5(J2C)i3 N　C+　2 AF-≠3 N(J2 AF-μ≠ AJ’−≠6 sleep H3 AP-μI C (JNHC□6H33 AF-μ2 C (JNHC16H33 5O2C14H19 C(JN)101. H33 AP-t 3 A　F　−j≠ AP-! ! AF-jA AF-77 C(JN)Icm6H33 AF-! r (J AF-to AF-bu 3 CUNHC: □6H33 AF-bug C(JOH A　P　-44 AF-47α No.

AP-br AF-42 S (J2C) (3NHCOe, H engineering AP-7θ AF-7/ AF-7J AF-73 AP-7≠ eocnc engineering. F133 AF-73 AP-74 AF-77 A k ' -7I O2 AF-7F N(J2 AFzu3゜AF-r&O2 P-4J AF-r7 S(J2L:)i3 AF-, rP AF-ta/AF-tacho N(J2 Ak'-PJ A P -P4t SO2C16'33 O2 The method for synthesizing the compound of the present invention is described in Japanese Patent Application No. Sho tl-rr42j, No. 6/-4772/, Fuji Photo Film.

Patent application dated 1935 (λ) month IT filed with Lum Co., Ltd. as the applicant and the name of the invention as "silver halide photosensitive material" (B
) and (C).

Part 8 of the present invention will be explained more clearly and in part 9, specific synthesis examples will be shown below.

(1) Synthesis of Compound AF-j Synthesis Example 1 Synthesis of N-methyl-N-octadecyl-3-nitrol-aa-penzamide 10j, 75! 3-ditro-μm chlorobenzoic acid and 1
00g of acetonitrile were mixed, thionyl chloride tr and tt were added thereto, and the mixture was heated under reflux for μ hours. After cooling, the solvent was distilled off and the residue was dissolved in chloroform. Triethylamine 4J, jtk7JO, and z"c were added to this solution.Next, the entire chloroform solution of N-methyloctadecylamine was added dropwise to this solution.After the reaction was completed, water was added and the organic phase was separated. was dried over anhydrous sodium sulfate. After filtering off the inorganic substances, the solvent was distilled off and recrystallized from acetonitrile-methanol (/:J). Yield/rz1, Yield 7 J, 0%, Melting point: J~74 °C0 synthesis example 2
Synthesis of j-1-butyl-3-human isoxazole human mixylamine hydrochloride! rJ, 7? f! ! :41N
- Pour the sodium hydroxide aqueous solution into IKW, add ethanol solution under water cooling, and then add sN-sodium hydroxide water-
Add ethanol (/:/) mixed bath solution to adjust the pH of the bath solution to 1.
Adjust to 0.0 friend. Add this solution to piparoyl acetate ethyl ester/310? and <zN-sodium hydroxide water-ethanol (/:/) mixed solution, the pH of the reaction solution is io+o
, and were added dropwise at the same time so that the temperature was 0-j °C.

After completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour, then poured into concentrated hydrochloric acid at 6°C and left for 72 hours. The precipitated crystals were collected by filtration, thoroughly washed with water, and then dried. Yield 77or, yield 4F,
1, Melting point 2P'C-10/'C Synthesis Example 31-1-Butyl-λ-(≠-N-methyl-N-octadecylcarbamoyl-λ-nitrophenyl) -J-Isoxacilone sweet acid 34t, /f N -Methyl-N-octadecyl-3-nidroder-chloropenzamide, /co, France? z-t-
Methyl-3-hydroxyinoxazole, /2. ≠2
Dimethylformamide JOOrdf was added to potassium carbonate, and the mixture was reacted at 10°C for 1 hour. After the solvent was completely distilled off under reduced pressure, ethyl acetate and water were added and stirred, the organic phase was separated and the main product was collected using silica gel column chromatography.

Recrystallized from n-hex/ethyl acetate. Yield/I
, Of, yield μ3. /%, melting point 4μOC0 Synthesis Example 4
Goochloromethyl-1-1-butyl-λ-(4t-N
Synthesis of -methyl-N-octadecylcarbamoyl-λ-ditophenyl)-3-isoxacilone 1-1-zoteluko(μ-N-methyl-N-octadecylcarbamoyl-nitrophenyl)-3-inoxazolo7Jtf, paraformaldehyde! , 7. Mix 10.J? of zinc chloride with 10.0L of acetic acid, blow in hydrogen chloride gas, and react for 10o'c.After the reaction is complete, cool and add the ashes mixture to ice water. The precipitated solid was collected by filtration, dissolved in chloroform, and purified by column chromatography to give a yield of 23.
4%, melting point 77aC.

Synthesis Example 5 Synthesis of Compound AF-J Synthesis Example Synthesis in France
-Methyl-N-octadecyl (lupamoyl)-3-isooxacillone Hiroo? And/-phenyl-! -Mercaptotetrazole/249? ! -Dissolved in acetone. Next, potassium carbonate/1lfp was added to this, and the mixture was stirred at room temperature for 3 hours.

After filtering out inorganic substances, recrystallization was performed from methanol to obtain 33 feet of colorless crystals. Yield t7%, melting point 44-4r'
C.

The compound of the present invention is made to contain V in the halog/silver oxide photographic light-sensitive material by the Sona method described below, and is reduced along the migration path of the ``Silver'' represented by the arrow shown in the following formula (1), thereby inhibiting the present iron production. All of the agent is released.

Formula (1) + (几EOX) This reducing agent (R, E) is the normally used negative type 1
When a silver halide emulsion is used, silver halide is used for reduction and consumed depending on the degree of exposure, so the reaction with the compound of general formula (1) of the present invention corresponds inversely to the degree of exposure. That is, only the amount of the supplied reducing agent (RE) that remains unused for reducing silver halide is used. Therefore, a larger amount of the development inhibitor is released in areas that are less exposed.

Furthermore, when an autopositive emulsion is used, the reduction of silver halide occurs on the unexposed side, contrary to a negative emulsion, so the reducing agent is consumed on the unexposed side. Therefore, the general formula (1
The reaction between the compound () and the reducing agent occurs in larger amounts in areas exposed to more light, and a larger amount of the development inhibitor is also released.

As described above, the compound of the present invention releases a small amount of development inhibitor in the developing area (the area where silver halide and a reducing substance react) and a large amount in the non-developing area, but the development inhibitor in the developing area and the non-developing area is For the purpose of adjusting the ratio of the amount of inhibitor released (usually to improve this ratio), a reducing agent called an electron transfer agent (ETA) as expressed by the following formula (2) may be used in combination. good.

The amount of the development inhibitor precursor expressed by general formula (1) depends on the type of AP, but silver halide 1 per mole/×10
mol-1 mol, preferably in the range of /X10-3 mol to /x10' mol. Also, per 7 mol of the positive dye-donating substance described below / x 10-3 mol ~ / x 70
2 mol, and preferably t[/×10 mol to 70 mol. The development inhibitor precursor may be used alone or in combination of two or more. In the present invention, a reducing agent is used.

The reducing agent may be an inorganic compound or an organic compound, but its oxidation potential is preferably lower than the silver ion/silver standard acid reduction potential o, rV.

Examples of inorganic compounds include metals having an oxidation potential of o, roV or less, such as Mn, Ti, 8i, Zn, Cr, Fe, and Go.

Mo, Sn,, Pb, W, H, sb, Cu,
Hg.

etc., ions with an oxidation potential of o, rv or less, or complex compounds thereof,
For example, C, 2+, y 2 +, cu+, p,
2 +.

Nl no 2. I-*Co(CN)
a' -F e (CN) 6- (F e h
D T A ) 2-, etc., metal hydrides with oxidation potentials of o, rV or less, such as NaH,
LiH, KH, NaBHLiBH,.

I LiA#(0-tC,Ho)3H.

Sulfur or metal phosphide with oxidation potential o, rv or less, such as LiAi (QC) (3)3)1, e.g. Na80NaH8, NaH803,)i3F
.

2 3% HS Na S Na 2 S 22
I 2 1 and the like.

As a reducing agent for the NU compound, nitrogen compounds such as alkylamines or arylamines, organic sulfur compounds such as alkylmercaptans or arylmercaptans, or organic phosphorus compounds such as alkylphosphines or arylphosphines may also be used. Preferred are silver halide reducing agents according to the Kendal-Pelz formula described in "The Theory of the Photographic Process" by James, 1st Edition (177), P, 2P.

Examples of more preferable reducing agents include the following.

3-Pyrazolidores and their precursors
-phenyl-3-virazolido/, l-phenyl-μ, 4
L-dimethyl-3-pyrazolidone, Hiro-hydro-dimethyl-≠-methyl-/-7enyl-3-pyrazolidone, /
-m-) Zyl-3-pyrazolidone, /-p-1'lylu J-pyrazolidoes l-phenyl-! -Methyl-J-Hira/IJ)''n, /-phenyl-≠lF-bis(hydroxymethyl)-3-pyrazolidone, /,4!-di-methyl-3-pyrazolidone, Hiro-methyl-3-pyrazolidone, 4t+Hiro-dimethyl-3-pyrazolidone, /-(3
-rialophenyl]-μm methyl-3-birasoliton,
' (≠-chlorophenyl)-g-methyl-3-pyrazolidone, /-(Hiro-tolyl)-μm methyl-3-pyrazolidone, /-(λ-tolyl)-μm methyl-3-pyrazolidone, /-(4Z-tolyl) )-3-pyrazolidone,
/-(J-)lyl)-3-pyrazolidone, /-(J-tolyl)-g, ≠-dimethyl-3-pyrazolidone, /-(
j-trifluoroethyl)-≠, Hiro-dimethyl-3-pyrazolidone,! -Methyl-3-pyranolidone, /,! −
Diphenyl-3-pyrazolidone, /-phenyl-≠-methyl-Hiro-stearoyloxymethyl-J-pyrazolidone, /-phenyl-≠-methyl-coulauroyloxymethyl-3-pyrazolidone, /-phenyl-μ, 4t-
Bis-(lauroyl-o-dimethyl)-3-pyrazolidone, /-phenyl-coaceter-3-pyrazolidone, /
-Phenyl-3-acetoxypyrazolidone] hydroquinones and their precursors [e.g., eva, hydroquinone, toluhydroquinone, co.

-dimethylhydroquinone, t-bunalhydroquinone, 2. J-di-t-butylhydroquino7, t-
Octylhydroquinone, ko! -D-t-octylhydroquinone, interdecylhydroginone,! - antadecylhydroquino/- sodium course sulfonate,
p-benzoyloxyphenol, cometer-≠-benzoyloxyphenol, coat-t-phthyl≠-(I
A-chlorobenzoyloxy)phenol], color developers are also useful as other examples of silver halide reducing agents, and are described in U.S. Patent No. J,! j／
, N to 2rt,, N-shiy-ru-3-methyl-p
- p-phenylene color developers represented by phenylene V/diamine are described.

Further useful reducing agents include those described in U.S. Pat.
No. 70 describes amine phenols. Particularly useful amine phenol reducing agents include ≠-amino-1-dibromophenol, μm-aminoco, t-dibromophenol, qua-amino-co-meterphenol sulfate, Hiro-amino-3-methylphenol sulfate, ≠- Examples include aminoco, 6-cyclophenol hydrochloride, etc. Furthermore, Research Disclosure Magazine / J / Issue No. Sales / 610! , U.S. Patent No. 0,
2/, No. 2410, λ,6-dichloroμ-substituted sulfo/amidophenols, j,A-dibromo-≠-substituted sulfonamidophenols, JP-A-Sho! Tar/767≠
θ number is p-(N,N-cyfuru+ruaminophenyl)
Sulfamine and the like have been described and are useful. In addition to the above phenolic reducing agents, naphthol reducing agents, such as μm amino-naphthol conductors and
Particularly useful are the Gu-substituted sulfonamide naphthol derivatives described in No. 00310. Furthermore, as a general color developer that can be applied, US Patent No. 2. IPj
, No. 123, the abanopyrazolino derivatives described in U.S. Pat.
Hydrazone derivatives are described in the P2O year month issue - λ7~230%Co3tN-≠θ page (Kariichi/Pμ7ko, )LD-/P4t/j). These color developers may be used alone or in combination of λ or more.

When compounding the expansion-resistant reducing agent with all photosensitive materials,
An electron transfer agent (ETA) is added to promote electron transfer between the reducing substance and the developable silver emulsion.
It is preferable to use them in combination.

゛α electron transfer agent ETA) is selected from among the above-mentioned reducing agents.
I can move. In order for an electron transfer agent (ETA) to have a more favorable effect, it is desirable that its mobility be greater than that of an inactive reducing agent.

In this case, the reducing agent used in combination with B'rA may be any reducing agent as long as it does not substantially migrate in the layer of the photosensitive material, but preferably hydroquinones, Aminophenols, aminonaphthols, J-pyrazolidinones, saccharin and their precursors, picoliniums, JP-A-Sho! ! -// 012
Examples include compounds described in No. 7 as electron donors.

ETA used in combination with these is ETA
Any oxidant can be used as long as it cross-oxidizes with these, but preferred examples include 3-pyrazolidinones, amine phenols, phenyl/diamines, and reductones, each of which is diffusible. .

When applied to heat-developable color photosensitive materials, the reducing agent is incorporated into the heat-developable color photosensitive materials.

In this case, the preferable usage amount is 0.0/~! of the reducing agent in total per mole of the dye-donating substance. O mole, preferred tt, < is O, / ~ J mole, o, ooi per mole of silver halide
mol to J mol, preferably 0°0/ to 1 mol.

The dye-providing compound that can be used in the present invention is a compound that provides a mobile dye in response to a reaction in which silver ions are reduced to silver.

As such a dye-donating compound, diffusion-resistant foundation film #
Diffusible dye due to the coupling reaction with the oxidized form of the reducing agent? Two-equivalent couplers that form (including those that are polymerized) are mentioned. A specific example of this coupler is given in "The Theory of the Photographic Process" by James, 1st edition (T. H. James
The Theory of the Photo
graphicProcess”) Kota/~331
1 page, and 3jt~36/page, Tokukai Sho! I-/23j
No. 33, same! r-/IAPOI-, same jf-/4A
No. 7047, 3rd/l//Hiroshi, same! Tar/Kohiro 32nd issue, same! Tar/74L13! No. JP-23/
! 3P No., JP-23/1410, 60-2
'1lJO, tO-29j1-75, 40-/1
7241-, 4O-uJ4t74A, tO-butco≠, etc., are detailed accounts of theft.

Another example of the dye-donating substance is a compound that has the function of releasing or diffusing a diffusible dye in an imagewise manner. This type of compound has the following general formula (LI) (Dye-X) -Y (LI) Dye represents a dye group, a temporarily shortened dye group, or a dye precursor group, and X is a simple bond or linkage. represents a group, Y
(Dye
-X)n-Y, or release Dye and create a difference in diffusivity between the ejected Dye and (Dye-X)n-Y. represents a group having the property of producing , n represents/or 2, and when n is 2, two Dye-Xs may be the same or different.

A specific example of the dye-donating substance represented by the general formula (LI) is one in which Y represents a coupler residue having a diffusible dye as a leaving group, and the diffusible dye becomes Examples include substances that emit (DDR couplers). This DDK coupler is described in British Patent No. 1,330. j
2≠, Special Publication Showa 4#-3P, No. 163, British Patent No. 3.
≠4L3°Pμθ, etc., and is preferably used in the present invention.

Another example is one in which Y represents a reducing group in the general formula (LI), and as a result of a redox reaction with the exposed silver halide directly or via a reducing agent, all of the diffusible dye is released (DRR accessories). Typical examples are U.S. Pat.
J, No. 312, @a, ojs, par, No. 1I,
No. 336, 32λ, Tokukai Sho! ? -61132, same JP
-421rj? Same issue! J-31/W issue, same! /-10
4A.

3 Hiroshi No. 3, Research Disclosure Magazine/7≠tj
No. 3,72! , 0bu No. 1, same No. 3,728
', //jq Same No. J, $4j,? , 5'jri issue, Tokukai Sho! r-//l,! No. 37, same j7-/7ri r4to
It is a dye-donating substance described in U.S. Pat. Specific examples of such dye-donating substances include the above-mentioned rice, 8% alcohol, and jo.
o, column *22 of issue J2J to u1. .

Compounds listed in the "G" column can be mentioned.

Specific examples of dye-providing compounds useful in the present invention are listed below, but the present invention is not limited thereto.

(2) U)1 001. H3, (n) H OC,6)i33(n) OCl 6'33(n) H OC□6)i33(n) (JH H N)icOc,, H3□ ■ C12H25 饅α H (To) H a Force (J)i H(J C)12 CU□H t Word0H C5) ill Hydrophobic additives, such as immobile reducing agents and imaging promoters described below, can be incorporated into the layers of the photosensitive element by known methods, such as those described in U.S. Pat. .In this case, Tokkai Sho!tarr3/!gu issue, same number 3
ter/71≠J1, samej F-/7♂4tjJ,
Same jP-/71 Hiroj No.3, same! Tar/71≠jμ issue, same! ter No. 7711411, same, t5'-1711417
A high boiling point organic solvent such as those described in No. 1, etc. can be used in combination with a low boiling point organic solvent having a boiling point of jo 0c to /lO'c, if necessary.

The amount of the 5ifJe point organic solvent is less than iot, preferably less than jfIIfi, relative to the dye-donating substance/f used.

Maku Tokko Sho J/-391! No. 3, Toku Kai Sho J/-! ? 2μ
The dispersion method using a polymer described in No. 3 can also be used.

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

When dispersing a hydrophobic substance into a hydrophilic colloid, a number of surfactants can be used.
The surfactants listed on pages (37) to (3♂) of No. 117636 can be used.

Silver halides that can be used in the present invention include silver chloride, silver bromide,
Alternatively, silver chlorobromide, silver chloroiodide, or silver chloroiodobromide may be used.

Specifically, U.S. Patent≠, 300. tco whistle jO column,
Research Disclosure Magazine / June 7th issue, pages 2-10Q (RD/702F), JP-A-4/-107≠
No. Q, No. 317 to-λ, No. 40-221247
Any of the silver halide emulsions described in No. 1, etc. can be used.

The silver halide emulsion used in the present invention may be of the surface temperature image type, in which the IW image is mainly formed on the grain surface, or may be of the internal m-image type, in which the IW image is formed inside the grains. It may also be a so-called core-shell emulsion in which the interior of the grains and the grain surface have different phases. In addition, in the present invention, internal fllfI
A direct inversion emulsion that combines a J-type emulsion and a nucleating emulsion? You can also use

Although the silver halide emulsion may be used unheated, it is usually used after being chemically sensitized. For emulsions for conventional light-sensitive materials, known methods such as sulfur sensitization, reduction sensitization, and noble metal N sensitization can be used alone or in combination. These chemical sensitizations can also be carried out in the presence of a containing heterocyclic compound (Japanese Patent Application Laid-open No. 31-1989/λ6j2, JP-A No. 1987-2/1J41).

The coating amount of the photosensitive silver halide used in the present invention is in the range of 7 to /ot/m in terms of silver.

In the present invention, along with photosensitive silver halide, a sentient metal salt kl! It can also be used in combination as a curing agent.

In this case, it is necessary that the photosensitive silver halide and the organic metal salt are in contact with each other or are close to each other at a distance of a certain distance.

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 agent include (10) of JP-A-4/-107λ≠O.
Bottom left corner of page ~ (//n Page top left column U.S. Patent≠, 300.t
Ko≦No.@32 column~No.! There are compounds listed in column 3, etc. Also useful are silver salts of carboxylic acids having an alkynyl group, such as silver phenylpropiolate, described in Japanese Patent Application No. 1973-1973, No. 3J, and silver acetylene, described in Japanese Patent Application No. 1983-1993. Two or more types of organic silver salts may be used in combination.

The above organic silver salts contain 1 mol of photosensitive silver halide,
0.0/ to 10 mol, preferably 0.07 to 1
Moles can be used together. The total coating amount of photosensitive silver halide and organic silver salt is jOη or /Of in terms of silver.
/ m is appropriate.

The silver halide used in the present invention may be spectrally sensitized with methine dyes and others. The dyes used include cyania dyes, merocyanif dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyania dyes,
Included are hemicyania dyes, styryl dyes and hemiogisonol dyes.

Specifically, % Kaishojy-irortQ No. 40-/
P03Jj issue, Research Disclosure Y- Magazine/9
The sensitizing dyes described in February 1971 issue, page 3 (RD/7029), etc., and the sensitizing dyes described in JP-A-10-1989-//, No. 23, t
! ! ! Examples include thermally decolorizable sensitizing dyes described in Japanese Patent Application No. 60-7-247.

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, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance that exhibits supersensitization? It may be included in the emulsion (for example, U.S. Pat. No. 9233,390, U.S. Pat. t/j.

Bu 4th layer No. 1, 3,617. λri No. 3, same 3.63! ,
7λ1).

These sensitizing dyes can be added to the emulsion during or before chemical ripening, or is it possible to add them to the emulsion in the US patent? JII, /1
It may be carried out before or after nucleation of silver halide grains according to No. 3,7!6, No. 41,22j, Att4.

The amount added is generally IO to 1 mol per mole of silver halide.
It is about 0 mole.

In the present invention, a compound sound can be used in the photosensitive element to activate the development and stabilize the image at the same time. For specific compounds preferably used, see US Pat.
No. 100,416! It is written in the /~j column.

Any of a variety of antifoggants or photographic stabilizers can be used in the present invention. An example of this is research
Disclosure M/ri 7th layer December issue Kopi-ko!
Azoles and azaindenes described on page JP-A-Shojter/ArlA4! Nitrogen-containing carboxylic acids and phosphoric acid gradients described in No. J, or mercapto compounds and metal salts thereof described in JP-A No. 111634/1999, Japanese Patent Application No.
--Acetele/compounds described in Coco t7, etc. are used.

In the present invention, the photosensitive element may contain an image toning agent if necessary. For specific examples of effective dramatizing agents, see the compounds described in the upper right column to the lower left column of the patent application No. 724tμ (-≠).

A wide range of colors in the chromaticity diagram using the three primary colors yellow, magenta, and cyan? In order to obtain at least 3j- each sensitive to a different spectral region? A light-sensitive element having a silver halide emulsion layer may be used. For example, Yoi W&
There are combinations of three layers: a green-sensitive layer, a red-sensitive layer, and a combination of a green-sensitive layer, a red-sensitive layer, and an infrared-sensitive layer. Each of these photosensitive layers may be divided into two or more layers, if necessary.

The light-sensitive materials produced using the present invention contain hydroquino/wire conductors, amine phenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless foggers, etc. as color antifogging agents or mixing inhibitors.
, sulfo/amide phenol derivatives, etc. It is particularly preferable to add these compounds to the intermediate layer.

The photographic element of the present invention is comprised of a light-sensitive element that completely forms or releases a dye upon heat development and a dye-fixing element that fixes the dye.

Typical forms that the photosensitive element and the dye fixing element can take include a form in which the photosensitive element and the dye fixing element are separately coated on λ support bodies, and a form in which the photosensitive element and the dye fixing element are coated on the same support. It is broadly divided into. The relationship between the photosensitive element and the dye fixing element, the relationship with the support, and the relationship with the white reflective layer is disclosed in Japanese Patent Application Laid-open No. 4/-/!
72 μ≠ issue (/j) left and right lower columns ~ (/l) negative pressure upper column and US patent μ,! 00゜4.2j issue! The relationship described in column 7 is also applicable to the present application.

The dye fixing element preferably used in the present invention has at least seven layers of lvI containing a mordant and a pie/goo. As the mordant, those known in the photographic field can be used, and specific examples include those described in Japanese Patent Application Laid-Open No. 2002-4123 No. (3) left and right lower columns to (!/) left and right lower columns. Can be done.

The dye fixing element can 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. The above-mentioned layer/casing or multiple layers contain a hydrophilic heat solvent, a plasticizer, an anti-fading agent,
It may contain UV absorbers, slip agents, matting agents, antioxidants, fractional vinyl compounds for increasing dimensional stability, surface active 4jS fluorescent brighteners, and the like. In addition, in a system that simultaneously performs heat development and dye transfer in the presence of a small amount of water, it is recommended that the dye fixing element contain a base and/or a base precursor, which will be described later, to increase the shelf life of the photosensitive element. preferred in meaning. Specific examples of these additives can be found in the upper left and right columns of JP-A No. 4c-(32).
) written in the lower left column.

In the present invention, the photosensitive element and/or the dye fixing element can be used as an image formation accelerator. Image formation accelerators include accelerating redox reactions between silver salt oxidizing agents and reducing agents, accelerating reactions such as the production of dyes from dye-donating substances or the release of dye fractions or diffusible dyes, and photosensitizers. It has functions such as promoting the movement of dye from the material layer to the dye fixed layer, and from a physicochemical function, it is a base-!Friend is a base precursor,
Interaction with nucleophilic compounds, high boiling organic solvents (oils), thermal solvents, surfactants, silver or silver ions? It is classified as a compound that has As a matter of fact, these objects/λ groups generally have multiple functions, and usually have some of the above-mentioned promoting effects. For details on these please refer to JP-A-Sho J/-
It is written in the lower left column of J'♂λJ No. 6 (/7) to the upper left and right columns of (,2O).

There are other methods for generating all bases, and any of the compounds vlJ used in these methods will be useful as a jl group precursor. For example, patent application 1986-/4 Pj
1! By mixing the poorly soluble metal compound listed in No. ζ and a compound that can form a complex with the metal ions that make up this poorly soluble metal compound (referred to as a complex-forming compound), you can create a base. There are a method of generating a base, and a method of generating a base by electrolysis as described in JP-A No. 17 of 1983.

The former method is particularly effective. Examples of poorly soluble metal compounds include carbonates, hydroxides, and oxides of zinc, aluminum, calcium, barium, and the like. Regarding complex-forming compounds, for example, N. E.-Martill, R. M. Haismith (A, E., Martell, R.
M, Sm1th) co-author, “Critical Stability Constances”
A detailed explanation is given in ``Contents'' J, Volumes μ and 3, Plenum Press. Specifically, aminocarboxylic acids, imidinoacetic acids, pyridylcarboxylic acids, aminophosphoric acids, carboxylic acids (mono, di, tri, and tetracarboxylic acids, as well as phosphono, human mixi, o-chuso, estehairamide, alcoholic acid, mercapto, and alcoholic acids) compounds with substituents such as luteo and phosphino), hydroxamic acids, polyacrylates, polyphosphoric acids, etc. and alkali metals,
Examples include salts with guanidines, amidines, μ-class ammonium salts, and the like.

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

In the photosensitive element and/or dye fixing element of the present invention, various known development stoppers are used in combination with the compound of the present invention in order to always obtain a constant image despite fluctuations in processing temperature and opening during development. can do.

A hydrophilic type can be used as the 2-inder of the photosensitive element and/or dye-fixing element of the present invention.

Hydrophilic binders are typically transparent or translucent, such as proteins such as gelatin and gelatin derivatives, cellulose derivatives, and natural substances such as starch, dextran, pullula, and polysaccharides such as gum arabic. and synthetic polymeric materials such as water-soluble polyvinyl compounds such as polyvinyl alcohol, polyvinylpyrrolide/acrylamide polymers, and the like. However, it is also possible to use dispersed vinyl compounds which are used in latex form and increase the overall dimensional stability of the photographic material. These inders can be used alone or in combination.

In the present invention, the binder should be applied in an amount of 20 to 1 ml or less, preferably 7 to 1 ml or less, more preferably 7 to 1 ml.

The ratio of the binder to the high boiling point incubator bath medium, which is dispersed in the binder together with a hydrophobic fraction such as a dye-donating substance, is binder/? less than or equal to solvent/g, preferably 0. j
A suitable value is less than 0.3 rttl, more preferably less than 0.3 rttl.

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

A specific example of the hardening agent is % Ganshoj/-/≠7λ4 on page 2μ to page 1 of the specification, No. 6O-231O93! Page to T page, Tokukaisho! Tah/! Examples include those described in No. 743, page 3t, and these can be used alone or in combination.

The supports used in the dye-fixing elements and/or dye-fixing elements of the present invention are those that can withstand processing temperatures. Common supports include glass, paper, polymeric films, metals and their analogs. For example, JP-A-Sho t/-//3117! r issue, same t/-/! 7 to IrJ2
No. t/-/10/J! No. j/-/74PJ/ can be used.

The photosensitive element and/or the 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 a thin film of an inorganic material exhibiting semiconductivity, and the other uses an organic material film in which conductive fine particles are dispersed in a binder. Materials that can be used in these methods include Material Kaisho t/-Kota r3, Same t/-/≠j
3≠No. 1, 61-λO and μ≠ can be used.

In the present invention, the coating method for the heat-developable photosensitive layer, fa-retaining layer, intermediate layer, undercoat layer, pack layer, dye fixing layer, and the like is described in US Pat. No. 100,424, No. 3j~! The method described in the column can be applied.

Radiation, including visible light, can be used as a light source for imagewise exposure for imagewise recording on the photosensitive element. In general, light sources used for normal 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.
No. 44' and U.S. patent μ, zoo, T26! The light sources listed in the column can be used.

The heating temperature in the heat development process is approximately 10°C to approximately 10°C.
It can be developed at a temperature of about 0.degree. C. to about 1 ro.degree. C., but is particularly useful. The dye diffusion transfer step may be performed simultaneously with the heat development, or may be performed after the heat development step is completed. In the latter case, the heating temperature in the transfer process can range from the temperature in the heat development process to room temperature, but
More preferably, the temperature is about 10 LIC lower than the temperature in the heat development step.

Pigment migration can also be caused by heat alone, but pigment migration? A solvent may also be used to promote the process.

Shota, JP-A-ShojP-rirua No. 3, same 4/-, z3r
It is also useful to carry out simultaneous development and transfer by heating in the presence of a small amount of solvent (water in M), as described in detail in No. ozt et al. In this method, the heating temperature is preferably 30°C or higher and lower than the boiling point of the solvent, for example when the solvent is water! o'C or more and too@c or less is desirable.

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 Are the ones listed in the section on formation accelerators used? can be mentioned. A casing, 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 anti-capri agent, a poorly soluble metal salt and a complex-forming compound may be included in the entire solvent.

These solvents can be used in a method in which they are applied to a dye-fixing element, a photosensitive element, or both.

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

A solvent (e.g. water) is applied between the photosensitive layer of the photosensitive element and the dye fixing layer of the dye fixing element to form an image and/'! Although it fully promotes the movement of the bamboo dye, it can also be used by incorporating it in advance into the photosensitive element, the dye fixing element, or both.

As a method of applying a solvent to the dye fixing layer, for example, the method of applying a solvent to the dye fixing layer is described in Japanese Patent Application Laid-Open No. 144724 (2003)
t) Negative pressure There are methods described in the lower column to the lower right column.

Furthermore, in order to fully promote dye transfer, a method may be adopted in which a hydrophilic thermal solvent, which is solid at room temperature and dissolves at high temperature, is built into the photosensitive element or dye fixing element. The hydrophilic thermal solvent may be incorporated into either the photosensitive element or the dye fixing element.
It may be built into both. The layer that contains it is also an emulsion layer,
Although it may be an intermediate layer, a protective layer, or a dye fixing layer, it is preferably incorporated in the dye fixing layer and/or its adjacent layer.

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

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

As heating means in the development and/or transfer step, there are means such as a hot plate, an iron, and a hot roller described in the left and right lower columns of JP-A-6/-/Hiroshi 72≠≠ No. (2μ). Alternatively, the photosensitive element and/or the dye fixing element may be coated with layers of conductive material such as graphite, carbon black, metal, etc., and the conductive material may be directly heated by passing an electric current through the conductive material. good.

What is a photosensitive element and a dye fixing element? ! -The pressure conditions and method of applying pressure when overlapping and applying lfi are JP-A-61-
/Da7ko41.4 The method described in No. (27) Negative pressure upper column to upper right column can be applied.

Any of a variety of thermal development equipment can be used to process the photographic elements of this invention. For example, Tokukai Akira! Turf! Ko≠7,
same! Tar/No. 771447, same! Tar/lr/J! ! No. 40-/19! / issue, Jitsugan 40-//4734c
Preferably, the devices described in No. 1, etc. are used.

Example 1 The method of preparing the silver halide emulsion for the j-th layer will be described.

A well-stirred gelatin aqueous solution (dissolve gelatin, 20? and ammonia in 1000 cc of water! 00 CK t
A bath solution containing potassium iodide and potassium bromide (1,000 liters) and a silver nitrate solution (1,000 liters of water)
1 mol of silver nitrate dissolved in yd) and p at the same time.
It was added while keeping Agk constant. In this way, a monodisperse silver iodobromide octahedral emulsion (iodine 3
Mol%)''I&: Prepared.

After washing with water and desalting, gold and sulfur sensitization was carried out at 6°C by adding 2 parts of hydrogenated gold acid (gluate) and 2 parts of sodium thiosulfate. The yield of the emulsion was /.014.

Next, we will discuss how to prepare the emulsion for the third layer.

A well-stirred gelatin aqueous solution (containing 20 f of gelatin and 3? of sodium chloride in 1,000 atm of water and keeping warm at 7J'C) is mixed with an aqueous solution containing sodium chloride and potassium bromide and a silver nitrate aqueous solution (in water). t00
rd and the following dye solution (1) were simultaneously added in equal drop amounts over μθ minutes. In this way, the average particle size is 0.33μ
A monodispersed cubic silver chlorobromide emulsion (bromine 2
0 mol%)! f”v!4$111.ri.

Sodium thiosulfate after washing with water and desalting! Chemical sensitization was carried out with Ao''C by adding (2) and goohydroxy-6-mether/, J, Ja, 7-chitrazaindenko omy''. The yield of the emulsion was tooy.

Dye solution (1) Next, the method of preparing the emulsion for the first layer will be described.

A well-stirred gelatin aqueous solution (containing gelatin λO? and 3ff of sodium chloride in 1000d of water, 7jt0CK)
An aqueous solution AOOml containing all sodium chloride and potassium bromide (kept warm) and an aqueous silver nitrate solution (water A00ml)
rd, silver nitrate O0j tamol total bath solution total bath ratio) Of course, at the same time ≠ θ minutes, the power U was calculated as f#J+jk. In this way, the average particle size is 0.3! A monodisperse cubic silver chlorobromide emulsion (bromine rO mol %) of .mu. purple was prepared.

Sodium thiosulfate after washing with water and desalting! η and goohydroxy-6-methyl-/, 3. Ja, 7-tetrazaindene 2
7 lines of chemical sensitization at 60@C with the addition of 01η. The following describes the production of an oud/citriazole silver emulsion with an emulsion yield of 90,000 yen.

Gelatin 21? and benzotriazole/3.22 water J
9. Dissolve in 00 ml of this solution and keep stirring at 0°C.9. Add silver nitrate/7t to this solution? 1100 tnl of water was added over 2 minutes using 9 liters of VC.

What is the pH of this benzotriazole silver emulsion? AM, sedimentation, and excess platform removal. Then pHkt, 30
In accordance with the above, the yield is ≠ooy nobe/cito IJ azole silver emulsion? Obtained.

Next, how to make a gelatin dispersion of a dye-donating substance will be described.

Yellow dye-donating substances (17) all 3?, succinic acid-coethylhexyl ester sulfonic acid sodium o, zf, triisononyl phosphate r as surfactants
, weigh yztw and add ethylco 0ralt,
The mixture was heated and dissolved at about tO°C to form a homogeneous solution. This solution and lime-treated gelade/of! % solution/001 and completely stirred to remove moisture, then stirred with a homogenizer for 70 minutes at 10,00 Or
Dispersed at pm. This liquid is called a dispersion of a yellow dye-providing substance.

A gelatin dispersion (1l14) was prepared in the same manner using a cyan dye-providing substance (W)k as the magenta dye-providing substance (it)-1'a.

Using these, color photosensitive material 10/ shown in fig/table.
I created a meeting.

Further, a photosensitive material ioλ~ having the same structure as the photosensitive material ioi except that the compound r of the present invention shown in Table 4 was added to the second layer and the μth layer of the photosensitive material 10/m2, respectively. 706 gold was created.

Director 1 ; (I soc, Ht gO) a P
-C) Pot 3; Base precursor (A) Tatami 4: H Next, how to prepare the dye fixing material will be described.

The lime-treated gelate was dissolved in 00ml of water, and a 0.jM aqueous solution of lead acetate/1ml was added thereto and mixed uniformly. Coat the white film support uniformly to a wet film thickness of 1 jμm, then prepare the following coating solution thereon, apply it uniformly to a wet film thickness of 03 m, and dry to obtain the dye fixing material R- /All produced.

Dye fixing layer coating liquid formulation> Polyvinyl alcohol (degree of polymerization: ooo) Ice water solution / Cooy urea
KoyN-methylurea
20? The color photosensitive materials 10/-104 having the above-mentioned multifiltration structure were exposed to light at 2000 lux for 7 seconds using a tungsten light bulb through a three-color separation filter of B, G, and R whose temperature was continuously changing.

This 16-element material and the previously exploded dye fixing material R- were placed on top of each other so that their film surfaces were in contact with each other, and the dye fixing material was heated for μO seconds with a heat roller of /Jθ0C, and then the dye fixing material was exposed to light. When peeled off from the material, yellow, magenta, and cyan color images corresponding to the B, G, and H three-color separation filters were obtained on the dye-fixing material, respectively. The maximum and minimum densities of each color were measured using a total Macbeth reflection densitometer (RDj/P). The results are as follows.

Example 2・ The same silver halide emulsion as in Example 1 was used.

A method for dispersing a dye-donating substance (polymer coating) will be described.

Dissolved in polymer coupler (2J)/l-μd.

Add io% gelatin water bath solution JWLl to this solution and 10ml of water.
and surfactant were whole eggs and dispersed with a homogenizer.

A similar method was used to prepare a dispersion of polymer Kagura ('')% (λr).

With these, color photosensitive material 2 with a multilayer structure as shown in the table below.
Create 0 and then.

Also, the chemical compound of the present invention (AF-/7) or (AP-J3
) was added to the second layer and the first layer to the extent of /X/(1)' mol/m, respectively, to prepare photosensitive materials 202 to 0Jf.

Ao 1; Polyethylene terephthalate film tatami with carbon black dispersion fully applied to the pack surface 3;
; size .mu.m -1F6;

First, gelatin hardener H-/0.7Jf, H-λ
O, Coj2 and water/10ml and 100tk of 10% lime treated gelatin were mixed uniformly. This mixed solution was laminated with polyethylene in which t-acid oxidized meta was dispersed and coated uniformly on a good paper support to form a wet film of to μm, and then dried.

Gelatin hardener H-/0M2c)tsO□C1(2e(JN)10H2C1-
12N) iC country H2・SO□C grip CH2 gelatin hardener H-2 CH2=CHs(J2C)12CON)1cH2・CH
2CH2NHCOCH2So2C1-1==cH2 Next, a polymer with the following structure/! Dissolve 2 in Mizuko 00 door 1,
O% lime-treated gelatin/00? and then mix evenly. This mixture 0. On top of all the above applications! ! It was applied uniformly to form a wet film with a thickness of μm. This sample? It was dried to obtain a dye fixing material R-λ.

Polymer A tungsten light bulb is used for the above-mentioned multilayered color photosensitive material Q/-203, and the density changes continuously B and G
, H through a three-color separation filter at 2000 lux for 7 seconds, and heated uniformly for 2θ seconds or 30 seconds on a heat block heated to 710°C.

Dye-fixing material 几−λ? After soaking in water, the above-mentioned heated photosensitive materials 20/-203f are stacked so that their film surfaces are in contact with each other.

! After heating on a heat block at θ0C for 3 seconds, the dye-fixing material was peeled off from the light-sensitive material, and a negative magenta color image was obtained on the dye-fixing material. The density of this negative image was measured at 1Ill1 using a Macbeth reflection densitometer (RD-Jl).
Then, the following results were obtained.

The above results show that even if the holding time is increased by 10 seconds by using the compound of the present invention, both the maximum and minimum concentrations increase little. On the other hand, in the Comparative Example without addition, the fog increases significantly. Therefore, it can be seen that the compound vIJ of the present invention has a high development stopping effect.

Example 3 How to prepare silver halide emulsions for the third layer and the first J- layer will be described.

A well-stirred gelatin solution (1000 dlF' of water)
Contains gelatinco O1 and sodium chloride 32, 71
An aqueous solution containing sodium chloride and potassium bromide and a silver nitrate aqueous solution (
Silver nitrate in too much water. At the same time, add JP mole (dissolved in a bath) at the same flow rate throughout the UO separation. In this way, a monodisperse cubic silver chlorobromide emulsion (30 mol % of bromine) with an average grain size of 01 UO .mu.m was prepared.

After washing with water and desalting, 20 ml and 1 k of sodium thiosulfate and Hiro-hydroxy-6-medellup'p' e J a , 7-chitrazaindene were added, and chemical sensitization was carried out with Ao'C. The yield of emulsion was 6002.

Next, we will explain how to make a silver halide emulsion for the third layer.

A well-stirred gelatin aqueous solution (water ioo.

Contains gelatin 20f and sodium chloride Ji in d, 7
Sodium chloride and potassium bromide? Containing aqueous solution AOOrttl and silver nitrate water m
The solution (too ml of water to dissolve the nitric mercury, and the following) was added at the same time and at equal flow rates over 4 LQ minutes. In this way, a monodisperse cubic silver chlorobromide emulsion (to mol % of iron) having an average grain size of 0.3 J μm was prepared.

After washing with water and desalting, sodium thiosulfate! Chemical sensitization was carried out by adding Cape and ≠-hydroxy-t-methyl-/, J, Ja, 7-chitrazaindenko Oki. Our emulsion company is 600? Derotsukori.

Next, how to make a gelatin dispersion of a dye-donating substance will be described.

A dye-donating substance (1) t-/JP, an auxiliary developer with the following structure, at 0.71? , surfactant and shite, amber mash - λ-ethyl - medium syl ester sulfonic acid powder 0
．． ! ? , triinononyl 7 phosphate 7, JP was weighed, ethyl acetate JOd was added thereto, and the mixture was dissolved by heating to about θoC to form a homogeneous solution. 7 solutions of this bath liquid and lime-treated gelatin 70? After stirring and mixing, the mixture was dispersed using a homogenizer for 70 minutes at 1,100,001p. This dispersion is called a dispersion of a yellow dye-providing substance.

A dispersion of a magenta dye-donating substance was prepared in the same manner as described above, except that the magenta dye-donating substance (co)t was used and tricresyl 7 phosphate was used as the high point solvent. .

A dispersion of a cyan dye-providing substance was prepared using a cyan dye-providing substance (3) in the same manner as a yellow dye dispersion.

Auxiliary developer (reducing agent) Gelatin and ≠-acetylaminophenyl acetylene, 4 ff water/000rd toethanol 0
Dissolve in 0tttl.9.

This solution was kept at μo@C and stirred.

Silver nitrate in this bath liquid! 9. Add the solution dissolved in 00ml of tri water for 3 minutes.9.

Adjust the pH of this dispersion and remove excess salt by settling. Thereafter, a dispersion of an acetylene silver compound with a yield of 3009 was obtained by adjusting the pH to 1J.

Using these materials, a color photosensitive material 30/ having a multilayer structure as shown in Table 3 was prepared and compared.

Also, the compound of the present invention (AF-,?)'! Taha (AF'-
27) All of the photosensitive materials 302 to 303 having the same structure were prepared except that 3 mol % of the dye-donating substance was added to each of the WJ1 layer, the third layer, and the third layer of the total photosensitive material 30/.

(D-/) CD--1) l　　　　　　　E t Next, we will discuss how to make the dye-fixing material.

Gelatin 631, mordant with the following structure/301 and guanidipicolinate/rO? and f/300πg of water and placed on a paper support laminated with polyethylene! It was coated to a wet film thickness of μm and then dried.

A mordant and further gelatin 3jf,/, 2-bis(vinylsulfonylacetamidoethane)/.

1f/7μm of solution dissolved in 100yd of water in 0jtf/
Apply and dry the dye fixing material R to a wet film thickness of
I made -j pieces.

o and g, in which a tungsten light bulb is used in the above-mentioned multilayered color photosensitive material, and the density changes continuously.

It was illuminated for 7 seconds at 1000 lux through an IR color separation filter.

/ J at / m on the emulsion side of this exposed light-sensitive material
The film was supplied using a blurred wire bar No. 2, and then superimposed on the dye fixing material No. 3 so that the film surfaces were in contact with each other.

The film was heated for 23 seconds using a heat roller whose temperature was adjusted so that the temperature of the film after absorbing water was OoCm9pj'c. Next, when it is peeled off from the dye fixing material, yellow and yellow color corresponding to the G, R, and IRQ color separation filters appear on the fixing material.
Clear magenta and cyan images were obtained.

Maximum density (Dmax) and minimum density (Dmin) i of each color
The measured results are shown in Table t.

From the above results, even if the development temperature is increased by 2j'C by using the compound of the present invention, there is little increase in both the maximum density and the minimum density. On the other hand, in the Comparative Example without addition, the fog increases significantly. Therefore, it can be seen that the compound of the present invention has a high development stopping effect.

Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment 1933 - Year of the year/Suke Beha

Claims (4)

[Claims] (1) At least a photosensitive silver halide, a reducing agent, a binder, a dye-donating compound that provides a mobile dye in response to a reaction in which silver ions are reduced to silver on a support, and the following general formula [I] A heat-developable color photosensitive material comprising a development inhibitor precursor represented by: General formula [I] PWR-(Time)-_tAF In the formula, PWR is a group that releases (Time)-_tAF upon reduction, and AF represents a group that functions as a development inhibitor after being released. Time represents a group that is released from PWR as -(Time)-_tAF and then releases AF through a subsequent reaction. t represents an integer of 0 or 1. (2) In claim 1, general formula [I]
A heat-developable color photosensitive material characterized in that the compound represented by formula [II] is represented by formula [II]. General formula [II] ▲There are numerical formulas, chemical formulas, tables, etc.▼ In the general formula [II], EAG represents an electron-accepting group. N represents a nitrogen atom, and X represents an oxygen atom (-O-), a sulfur atom (-S-), or a nitrogen atom (▲numerical formula, chemical formula, table, etc. available▼). R^1, R^2 and R^3 each represent a simple bond or a group other than a hydrogen atom. R^1, R^2, R^3, and EAG may be bonded to each other to form a ring. Time represents a group that releases AF through a subsequent reaction triggered by cleavage of the N-X bond, and t represents an integer of 0 or 1. Further, a solid line in the formula represents a bond, and a broken line represents that at least one of them is bonded. AF and EAG have the same meaning as stated in claim 1. (3) A heat-developable color photosensitive material, characterized in that the compound of general formula [II] in claim 2 is represented by general formula [III]. General formula [III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the general formula [III], Y represents a divalent linking group, and R
^4 represents an atomic group that combines with X and Y to form a 5- to 8-membered heterocycle with the nitrogen atom. N, X, EAG, Time, t, and AF have the same meanings as stated in claim 2. (4) The heat-developable color photosensitive material according to claim 2 or 3, wherein X is an oxygen atom.