GB2216674A

GB2216674A - Heat-developable color photographic materials

Info

Publication number: GB2216674A
Application number: GB8827616A
Authority: GB
Inventors: Toshiki Taguchi; Takeshi Nakamine; Ken Kawata; Hiroyuki Hirai
Original assignee: Fuji Photo Film Co Ltd
Current assignee: Fujifilm Holdings Corp
Priority date: 1987-11-26
Filing date: 1988-11-25
Publication date: 1989-10-11
Anticipated expiration: 2008-11-25
Also published as: DE3839696A1; JPH087427B2; GB8827616D0; GB2216674B; DE3839696C2; JPH01138556A

Description

1 - 1 11 ad "" 16674 HEAT-DEVELOPABLE COLOR PHOTOGRAPHIC MATERIALS The

present invention relates to heat-developable color photographic materials and, in particular, to those which are excellent in the raw stock stability and which may form positive color images of high image density with little stain.

Heat-developable photographic materials are known, and the materials as well as methods of processing the same are described in, for example, Shashin Koqaku no Kiso (Bases of Photoengineering), Volume of Non-silver Photography, pages 242 to 255 (published by Corona Co., Ltd., 1982) and U. S. Patent 4,500,626.

Numerous methods have been proposed for formation of positive color images by heat-development.

For instance, U.S. Patent 4,559,290 has proposed a method of using a socalled DRR compound in the form of an oxidized compound having no dyereleasing ability together with reducing agent, in which the reducing agent is oxidized in accordance with the exposure of the silver halide in a photographic material by heatdevelopment and the DRR compound is reduced by the remaining reducing agent which has not been oxidized to 2 - release a diffusible dye. European Patent 220,746A and Disclosure Bulletin 87-6199 (Disclosure Bulletin, Vol. 12, No. 22) mention a method of forming a positive image by heat-development using a novel compound which may release a diffusible dye by a similar mechanism.

In the positive image-forming method mentioned above where a reducible dye-forming compound is used, in general, an electron-donating agent and an electrontransferring agent are used together as a reducing composition. However, the use of such a combination has been found problematic in that the electron-transf erring agent will gradually decompose to be lost during storage. As a result of the decomposition and loss of the electrontransferring agent during storage, the image to be obtained is increasingly -stained. In order to overcome the prdblem, a means of using an electrontransferring agent precursor which is stable during storage is helpful. However, the use of such electrontransferring agent precursor has a drawback in that a color image with sufficient SIN ratio can not be obtained.

1 An object of the present invention is to provide a positive heatdevelopable color photographic material which is excellent in raw stock stability and, more J - 3 1 precisely, to provide a heat-developable color photographic material whLch may form a positive color image of high image density with little stain both immediately after preparation and after storage for a long period of time.

other objects and effects of invention will be apparent from description.

The present invention provides a heatdevelopable color photographic material comprising a support having thereon at least a light-sensitive silver halide, a binder, at least one of an elect ron-donat ing agent and a precursor thereof, a reducible dye-forming compound which releases a iffusible dye by reduction and an electron-transferring agent, wherein an electrontransferring agent precursor co-exists together with the electrontransferring agent.

the present the following In accordance with the present invention, an electron-transferring agent precursor is inco rporated into the photographic material together with an electron-transferring agent, whereby the material may form a positi,; la image with high SIN ratio and may have the function of preventing an increase of stains upon storage. Such an effect of raw stock stability could 4 not be attained by the separate use of the electrontransferring agent or the electron-transferring agent precursor alone.

As the electron-transferring agent, any compound capable of being oxidized with a silver halide to form an oxidized product which has an ability of crossoxidizing the co-existing electron-donating agent may be used in the present invention, and it is desired that the electron-transf erring agent for use in the present invention is mobile.

As examples of the electron-transf erring agent for use in the present invention, there are hydroquinone, alkyl-substituted hydroquinones such as tbutylhydroquinone and 2,5-dimethylhydroqui'none, catechols, pyrogallols, halogen-substituted hydroquinones such as chlorohydroquinone and dichlorohydroquinone, alkoxy-substituted hydroquinones such as methoxyhydroquinone, and polyhydroxybenzene derivatives such as methylhydroxynaphthalene. In addition, there are further mentioned methyl gallate, ascorbic acid, ascorbic acid derivatives, hydroxylamines such as N,N1di-(2-ethoxyethyl)hydroxylamine, pyrazolidones such as 1-phenyl-3pyrazolidone and 4-methyl-4-hydroxymethyl-lphenyl-3-pyrazolidone, aminophenols such as p-methylaminophenol, p-dimethylaminophenol, ppiperidinoamino- At.' phenol and enediamines 4-dimethylamino-2,6-dimethoxyphenol, phenyl- N-methyl-p-phenylenediamine, and 4-diethvl- such as N,N,NI,N1-1t-etramethyl-p-phenylenediamine a mino-2,6-dimethoxyaniline, reductones such as piperi dinohexose-reductone and pyrrolidinohexose-reductone, and hydroxytetro.nic acids. In particular. compounds of the following general formula (X-I) or (X-II) are especially useful as the electron-transf erring agent in the present invention.

OH R2 1 R4 R' R3 N R6 "' '_'RS (X-I) R7 1 O= HN C-R9 N 1 R10 R (X-II) 2 3 4 in which R represents an aryl group; and R', R, R, R p R5, R6r R7, R8, R9, and R10, which may be the same or different, each represents a hydrogen atom, a halogen atom, a hydroxyl group, an acylamino group, an alkoxy group, an alkylthio group, an alkyl group, a substituted alkyl group or an aryl group.

In the formulae (X-I) and (X-II), the aryl group for R includes, for example, a phenyl group, a naphthyl group, a tolyl group and a xylyl group which may optionally be substituted. For example, the group may be an aryl group substituted by substituent(s) 'selected from a halogen atom (e.g., chlorine, bromine), an amino group, an alkoxy group, an aryloxy group, a hydroxyl group, an aryl group, a carbonamido group, a sulfonamido group, an alkanoyloxy group, a benzoyloxy group, a ureido group, a carbamate group, a carbamoyloxy group, a carbonate group, a carboxyl group, a sulfo group and an alkyl group (e.g., methyl, ethyl, propyl).

In the formulae (X-I) and (X-II), the alkyl group for R1, R2, R3r R4, R-9, R6, R7, R8, R9, and R10 is preferably an alkyl group having from 1 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl), and. the alkyl group may optionally be substituted by substituent(s) selected from a hydroxyl group, an amino group, a sulfo group and a carboxyl group. As the aryl group, there may be mentioned a phenyl group, a naphthyl group, a xylyl group and a tolyl group, which may optionally be substituted by substituents(s) selected from a halogen atom (e.g., chlorine, bromine), an alkyl group (e.g., methyl, ethyl, propyl), a hydroxyl group, an alkoxy group (e.g., methoxy, ethoxy), a sulfo group and a carboxyl group. In the present invention, the compounds of the formula (X-II) are especially preferred. In the 11 i1 7 - formula (X-II), R 7, R8, R9, and R10 each are preferably a hydrogen atom, an alkyl group having from 1 to 10 carbon atoms, a substituted alkyl group having from 1 to 10 carbon atoms or a substituted or unsubstituted aryl group, and more preferably a hydrogen atom, a methyl group, a hydroxymethyl group, an unsubstituted phenyl group Or a phenyl group substituted by hydrophilic group(s) such as a hydroxyl group, an alkoxy group, a sulfo group and a carboxyl group.

Specific examples of the compounds of the formulae (X-I) and (X-II) are given below, but are not to be construed as limiting the invention.

Specific examples of the compounds of the Formula (X-I) OH R2 R4 1 R' R3 R6 "' H 11 1 If 11 to 19 p ' #1 to 11 9 9 9 1 111 R5 No. _R' R2 R3 R4 R5 _ X-1 H x-2 go x-3 X-4 X-5 X-6 H 11 11 to of H 19 to 99 go cl -CH, -cl -CH3 11 -NHCOCH3 H -CH3 HCl -CH2CH2NHSO2CH3 -CH3 -H03S-C,2H25 -CH3'1/21,2S04 0 #1 0 R6 H -CH31/2H2S04 -CH3-1,03S--C12H25 1 00 1 No. R' _ _R2 R3 R4 R5 R6 9 X-7 91 $1 91 -CH3 -CH3 -CH3 -C- S03M X-8 -CI-13 91 11 -CH3 H -CH3 1 I'D 1 Specific examples of the compounds of the Formula (X-II) R7 0 R8 HZ R9 N R10 No. R7 R8 R9 R'() R X-9 H H H H X-10 -CH3 -CH3 X-11 -CH3 -CH3 11 11 -0 -CH3 X-12 -CH3 -CH20H of 1 X-13 H H 91 11 -CYCH3 X-14 -CH3 -CH20H II p (0) 91 X "?A v U No. R7 R8 R9 Rlo R X-15 -CH3 -CH20H H H -0- c 1 X-16 -CH20H -CH20H % X-17 -CH3 -CH3 cl X-18 -CH3 -CH20H If 19 OCH3 1 -C,- X-19 -CH3 -CH20CCH3 11 I.i X-20 -CH20H -CH20H 19 11 X-21 -CH3 -CH3 91 11 -0-cl X-22 -CH3 -CH20H 11 91 -0- OCH3 No. R7 - R8 R9 _ Rlo R X-23 -CH3 CH20CCH3 H 0 X-24 11 -CH20C Ii -p 0 CH, X-25 H -CH20C / \1 11 -0 0 X-26 @1 -CH20CCH3 11 0 f 1 11 11 9 1 11 1 11 11 X-27 -CH CH 20C 3 0 X-28 -CH3 -CH oc 2 11 0 X-29 11 of -C3H7 -CH20C--n ll \--/ 0 i 1 btli 1 K, fi r (f 1 k No. R7 R8 R9 Rlo R X-30 H H -CH3 H JF-\\ X-31 11 to -CH3 ll X-32 05 H -0-C02C2H5 19 X-33 -C-C02H X-34 X-35 CH3 X-36 @I ll 21 fl -0- cl X-37 11 1% fl 11 -0- OCH3 No.

X-38 X-39 R7 RB R9 _ H H H 11 %I -n\ _n H -0-NCCH3 11 U X-40 ll 19 1@ --O-OC4H9 X-41 of R1 VC 1 -p OCH3 1 X-42 of 11 1% -p -n\ HO X-43 11 11 11 -Q 1% 1 OH X-44 11 19 11 -0- oli -C- cl X-45 It ll 19 P----\\ -p -\--j OCH3 il 'd) ?1 1, 1, No. R7 R8 R9 Rlo R X-46 H H H OCH3 X-47 If 99 -a-OCH3 X-48 11 11 If OCH3 R@ o 1 OCH3 X-49 -G-OCH3 CH3 X-50 C.H1. (n) X-51 C18H37 X-52 91 19 19 O(CH2C11207)2CH3 No. R7 R8 R9 R10 R X-53 H H H 0__1'-"0t2CH3 X-54 11 1 ?1 -d -----OCH3 11 -0- cl X-55 If O-2CH3 cl CN 1 X-56 l@ 19 --o 11-p S02NH2 X-57 11 11. C02H go -n\ X-58 H3 cl c 0) il, 0 y ' 1 1 No. R7 R8 R9 R10 R X-59 H H NHS02CH3 H X-60 11 to -C- 0 OH 19 -0- c 1 X-61 -CH3 X-62 -OH of te -0-NHS02CH3 X-63 H H 0 91 -n\ 11 \---i -c -112-"4H2 X-64 '---SONH3 No. R7 _ _ R8 R9 Rlo R X-65 H H - 3 H -C- OCH3 CH3 1 X-66 -CH3 -CH3 H 11 -0- cl X-67 H H 0C4H9 X-68 co 6::) 1 X-69 -CH CH OH 3 2 X-70 -CH3 X-71 11 -OH 11 11 91 X-7 2 19 H X-73 H 10 -CH3 -CH3 i, t 1 1, v) j, 1 i No. R7 -RB R9 R10 R X-74 H H -CH3 H X-7 5 -CH20COCH3 H X-76 -CH20COC6H5 11 X-77 -CH20H -CH20H it It X-78 -CH3 CH20COCH3 H X-79 H H 19 6),1_ 6 X-80 -CH3 -CH20H 91 99 X-81 -CH20H -CH20H if X-82 -CH20H H 19 1 %I 9 1 f 9 1 No. R7 R8 R9 _ Rlo R X-83 -CH3 -OH H X-84 19 -CH3 11 X-85 to H X-86 -CH20H If X-87 -CH3 -CH20H X-88 -CH20H of X-89 -OH H X-90 -CH3 -OH X-91 H 1 9 f c No. R7 _ _RB R9 Rlo R X-92 H -n\ CH3 615 X-93 -CH3 91 H 11 It X-94 -CH20H 11 1@ to to 22 - These electron-transferring agents are known and avairable in the art.

In accordance with the present invention, the electron-ttransf erring agent may be used in a concentration range that can be determined by the skilled artisan. A suitable concentration range in mols is from 0.001 time to 4 times per mol of silver, and an especially useful concentration range in mol is from 0.003 time to 0.5 time per mol of silver.

As the electron-transferring agent precursor for use in the present invention, there are, for example, 2or 3-acyl derivatives or 2-aminoalkyl or hydroxyalkyl derivatives of l-phenyl-3-pyrazolidinone, metal salts (e. g., lead, cadmium, calcium or barium salt) of hydroquinone or catechol, acyl derivatives of hydroquinone, oxazine or bisoxazine derivatives of hydroquinone, lactone-tYpe electron-transferring agent precursors, quaternary ammonium group-containing hydroquinone precursors, cyclohex-2en-1,4-dione type compounds, as well as compounds capable of releasing an electrontransferring agent by an electron transfer reaction, compounds capable of releasing an electron-transf erring agent by an intramolecular nucleophillic substitution reaction, phthalide group-blocked electrontransferring z Y1 agent precursors and imidomethyl group-blocked electrontransferring agent precursors.

The electron-transf erring agent precursors for in the present invention are known compounds, and example, the developing agent - precursors described Patents 3,767,704, 3,241,967, 3,246,988, 3,586,506, 3,615,439, 3,650,749, and 4,310,612, British Patent 1,258,924 and 1,346,920, JP-A-55 JP-A-58-1139, JP-A-58-1140, JP-A JP-A-59 term "JP- use for in U. S.

3,295,978, 3,462,266, 4,209,580, 4,330,617 1,023,701, 1,231,830, 53330, JP-A-57-40245, 59-93442, JP-A-59-121328,JP-A-59-140445, 178458, JP-A-59-182449 and JP-A-59-182450 (the A" as used herein means an "unexamined published Japanese patent application") can be used. In particular, the 1-phenyl-2-pyrazolidinone precursors described in JP-A-5553330, JP-A-59-140445, JP-A-59-178458, JPA-59-182449, JP-A-59-182450 and JP-A-62-235949 are especially preferred.

Specific examples of preferred electron-transferring agent precursors for use in the present invention are compounds of the following general formulae (W-I) through (W-III):

(W-I) (W-II) (W-III) R7 Y-O R 7 4 3 1 1 R R o =-- C ,-, R Y -0 N __ Y-N N"R.9 N 5 1 ', R10 1N'j<R9 ^ R' R 1 1 R10 R K R In the formulae (W-I) to (W-III), R and R1 to R10 have the same meaning as described above for R and R1 to R10 in the general formulae (X-I) and (X-II).

In the formulae (W-I) to (W-III), Y represents a substituted alkyl group, preferably -CH2-K in which K represents a halogen aom, an alkoxy group, an aryloxy group, an acyloxy group,, a carbonic acid ester group, an amino group, a carbonamido group, a sulfonamido group, a ureido group, an aminosulfonamido group, a carbamate group, a carboxyl group, an oxycarbonyl group, a carbamoyl group, an acyl group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a cyanc, group or a nitro group; an acyl group, an alkoxycarbonyl group; an aryloxycarbonyl group; a carbamoyl group; a substitued carbamoyl group, a sulfamoyl group; a substituted sulfamoyl group; a group having the following formula:- - 25 H (z)m 1 0 p 00 (L)M in which Z represents a divalent linking group bonded to the phthalido nucleus via an oxygen atom, L represents a halogen atom, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, a carbonic acid ester group, an amino group, a carbonamido group, a sulfonamido group, a ureido group, an amino sulfonamido group, a carbamate group, a carboxyl group, an oxycarbonyl group, a carbamoyl group, an acyl group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a cyano group or a nitro group, and m represents 0 or 1; or a group of the the following formula:

0 0 11 11 R" R12 R13 1 1 1 in which M represents -(CI%_ or -C = C- (where n repre- sents 2 or 3, R11 represents a hydrogen atom, an alkyl group, a phenyl group, a halogen atom or an alkoxy group, R12 and R13 each represents a hydrogen atom, a 26 - halogen atom, an alkyl group or a phenyl gr.oup, or R12 and R13 may be ring-closed to form a benzene ring), and Q represents a R14 I hydroxyl group, -N-Rl-9 or R16 (where R14 represents a hydrogen atom, an aryl group or an alkyl group, R15 represents a hydrogen atom or an acyl group, and R16 represents a hydrolyzable group).

As examples of the hydrolyzable group for R16, R26 25-C-, 25 2 there are R R -0-C- and N-C-. R 5 represents 11 11 7 11 U 0 R 0 an aliphatic group having from 1 to 22 carbon atoms, aromatic group having from 6 to 10 carbon atoms or heterocyclic group; R26 and R27 may be the same different and each represents a hydrogen atom, aliphatic group having from 1 to 22 carbon atoms, aromatic group having f rom 6 to 10 carbon atoms or a heterocyclic group. The aliphatic group for R25, R26 and R27 may be substituted or unsubstituted and may be linear or cyclic.

Preferred substituents for the aliphatic group include, for example, an alkoxy group, an aryloxy group, an acylamino group, a carbamoyl group, a halogen atom, a sulfonamido group, a sulfamoyl group, a carboxyl group, an alkanoYloxy group, a benzoyloxy group, a cyano group, an a or an an t a hydroxyl group, a ureido group, a carbonyl group, an ar yl group, an alkylsulfonyl group, an alkoxycarbonyl group, an alkylureido group, an imidazolyl group, a furyl group, a nitro group, a phthalimido group, a thiazolyl group, an alkanesulfonamido group, an alkanesulfamoyl group, an arylcarbonyl group, an imido group and an alkoxycarbonylamino group.

When R25, R26 or R27 represents an aromatic group (especially a phenyl group), the aromatic group may optionally be substituted. The aromatic group such as a phenyl group may be substituted by substituent(s) selected from a halogen atom, a nitro group, a hydroxyl a cyano group, a carboxyl group, an alkyl group 32 or less carbon atoms, an alkenyl group, an group, an alkoxycarbonyl group, an alkanoyloxy an alkoxycarbonylamino group, an aliphatic amido group, having alkoxy group, group, an alkylsulfamoyl group, an alkylsulfonamido group, an alkylureido group, an alkylsulfonyl group and an alkyl-substituted succinimido group. The alkyl moiety in these substituents may have an aromatic group such as a phenylene group in the chain. The phenyl group may optionally be substituted by substituent(s) selected from an aryloxy group, an aryloxycarbonyl group, an arylcarbamoyl group, an arylamido group, an arylsulfamoyl group, an arylsulfonamido group and an 28 - arylureido group. The aryl moiety in these substituents may optionally be substituted by one or more alkyl -oms in total.- groups having from 1 to 22 carbon at When R25, R26 or R27 represents a 'heterocyclic group, the heterocyclic group is bonded to the linking group having an auxiliary developing agent, via one carbon atom which constitutes the hetero-ring. Examples of the hetero-ring include thiophene, furan, pyran... pirazine, pyrimidine imidazole. thiazole, pyrrole, pyrazole, pyridine I pyridazine, indolidine, oxazole, triazine, thiadiazine and oxazine rings. These rings may optionally have substituent(s) thereon.

In the formulae (W-I) to (W-III), the substituent Y may further be substituted by substituent(s) (for example, selected from the substituents mentioned for L in the above).

Specific examples of the substituent Y in the formulae (W-I) to (W-III) are set forth in the following Tables A and B. However, the substituent Y in the electron-transferring agent precursors for use in the present invention are not limited to only these examples.

c TABLE A

No. Formula Substituent Y 0 1 W-I 11 - -C-CH3 0 0 2 11 CCH3 0 0 3 HS C-COC2 0 11 4 11 -CH20CCH3 00 51 fl 1111 -CH20CCOC2H5 -C 6 11 J1 -0 U 7 8 9 11 11 ll 0 -d 0 0 0 P 11 -C CCH.

0 0 11 11 -C CCH2F - 30 NO._ Fo.-mula Substituent Y W-I -CH2C1 11 11 -CH.20H CF 3 12 -CH2N ow 0 13 -C-OCH2-C- OCCF3 14 -CC(CH3)3 11 U lr--\ 11 -CH3-N \-/ 0 16 11 0 -CH3-N S02 0 17 -CH2-N 0 0 18 02N 0 No. Formula Substituent Y 19 W-I -CH20 0 0 B11 0 0 20 N02 0 0 21 cl N02 0 22 it 0 0 cl NH 11 11), A.' -C/X,,C-N-O N 0 1 1 CE3 Ch3 23 W-II 0 11 --y -C OCE3 24 W-I 0 11 -C-N (CH3) 2 It 0 11 -C-C7H15(n) 32 - NO._ Formula Substituent Y 26 W-II 0 11 C-N cl I-C- H 27 99. 0 cl 11 -C-N-N - Cl 1 H H 28 0 C2H 11 1 1 -C-CH-C4H.(n) 29 0 11 -C-N (CH3) 11 0 CH3 11 1 -C-C-C3H7(n) 1 CH, 31 W-I H cl 1 CH OC-N- 3 2 11 0 cl 32 -CH20C-O-- N02 33 -CH20C-G- CN 11 U 34 33 No. Formula Substituent Y 11 -CH oc 2 11 -( - W -CH20C-0- COOCH3 11 0 36 -CH20C-// 37 -CH OC-CH ---2 3 38 11 -CH20CN(CH3)2 11 0 39 9 1 0 -CH2 'N.--0 6 11 -CH20-C-0- cl 11 U 41 -CH20Co-o 42 -CH20COC4H.(n) - 34 No. Formula Substituent Y 43 W-1 -CH20C NHSO CH' 11 -C- 2 3 0 44 11 11 -CH20c -G- OH 1) 0 0 11 -CH,OCCH,NHCO-O 11 0 46 11 -CH20CCH2CH2C1 11 U 47 48 11 11 -CH20CNH-C 11 U 0 i -CCH2CH2C-OH 11 U 49 91 0 11 -CCH2CH2WOH 11 1 U NO, CH, t 1 0 11 _ftCH2t3C-OH 0 -I I- 51 No. Formula Subst-ituent Y -==CHC-OH 11 - U 52 12 C12H25 1 -CCH,Cli-COOH 11 U 53 W-II -C-OC4H.(n) 11 U 54 CH3 1 n) C2H5 it -C S02CH3 -G 11 0 56 -C-C-OC2H5 11 H 0 0 57 -C-CH3 11 58 11 0 -C/\.-C-OH 11 U 59 11 -C -n\ - 36 No. Formula Substituent Y W-II -C-C-(CF3)3 11 U 61 91 -CH2 -p NHS02 - CH3 62 -C-N--p 0 CH3 CH 2N-C-CF3 1 CH, 11 0 CH 63 11 1 3 1 64 11 0 0%d--, N,-,--o 1 .;'-13 -CU(-;2H5 11 0 11 -CO-O 66 11 0 67 C 12 11 -L;u, \/OCH3 0 11 37 No. Formula Substituent Y 68 W-II 0 11 -LNtibu2-- CH3 69 11 0 11 -0 -CNH 91 0 11 0 -C-N-CH3 11 -..n\ CH2N-C ', 1 1 Ir CH3 71 11 -C-Cl3H27(n) 11 0 Z 7 4 38 - TABLE B

No. Formula Subst-ituent Y -C-CH C 72 W-M -C-CH3 73 11 CH3 1 0 C 1 C -" M C113 0 0 11 -CCH2CH2CCH3 -C-OC2H5 76 0 0 77 -d 78 -CH2CH2W In accordance with the present invention, compounds produced by puit.ibly combining the substituent Y shown in the aforesaid Tables A and-B and the above- C - 39 mentioned electron-transferring agent are used as the electrontransferring agent precursor.

Specific examples of electron-transferring agent precursors for use in the present invention are set forth below, which, however, are not. a-t. all limitative.

The symbol and the number for the structural formula of the respective electron-transferring agent precursors mentioned below have the following meanings.

ETP-34-11:

ETP: This means an electron-transferring agent precursor.

34: This means that the precursor releases the aforesaid electrontransferring agent X-34..

This means the precursor is protected by th substituent No. 11 in the aforesaid Table A or 13.

ETP - 34 - 11 0 HO-CH -N-0 2 N 'N 1b E T P - 8 7 - 3 4 CH:3 CHAH COOCHzi\ 1 C"), J1 C N 1 61 E T P - 3 6 - 6 0 t - C 1 H 9 - C - 0 E T P - 3 4 - 3 5 0 5: 1 1 cooc 0 N>- C CO0CHA N::

H 3 a C 41 - E T P - b 9 - 5 9 0 11 E T P - 3 4 - 5 0 CH3 C H z 0 H HO -C M C -NI N 0 E T P - 9 - 3 6 0 C-O-CHz - N J " N Cl : 1 6 - 42 E -1 P - 9 6 3 E T P - 8 - 7 1 0 H 3 C - N C - 0 0 11 1 H3C-N 1 0 H 3 C H 1 C 9 CHz -C - 0 - o- N - CH3 il 0 E T P - 7 - 7 6 H 3 C 0 0 =8 - 0 - 3- N CH3 N / CH3 \\ CHz - C) SO3H Ci 43 - E T P - 1 5 - 6 E T P - 1 2 - 5 3 0 n-H9C4-OCO E T P - 3 4 - 6 5 4 0 l! Hr,Cz-OCO CHzOH - CH3 NI -I- ", 1 1 c CHzOH I C H3 "". N : 1 6_.1, 0 G11 OCOC-) 1 _.1, - 44 E T P - 9 - 3 2 0 COO -C H N) rl L',j 1 1 N 0 2 E T P - 3 4 - 5 4 CH, 0 1 11 n-H9C4-C - OCO 1 CzHs E T P - 1 2 - 7 1 Z 7 N 61 0 n-HZ7C13CO CHAH CH3 C E T P - 4 6 - 2 5 n-HisC7-0-C E T P - 4 6 - 1 4 E T P - 4 6 - 6 8 0 0 OCH 3 -N N 0 0 OCH3 11 - t - H9 C 4 - C- N N 0 11 H 3C - 0-50,z-NHCO OCH3 N -"-,Nl : 1 6 46 1 E T P - 3 4 - 6 4 H 5 E T P - 3 4 - 5 3 E T P - 3 6 - 6 5 0 11 cz-0co 0 n-H9C4-OCO 0 c11 oco r th /1 X -3 N "' N / N 0 : 1 6 : 1 6_., 1 c ie E T P - 3 5 - E T P - 6 9 - 6 3 2 COO-CHz N H rs C z - 0 C 0 E T P - 4 3 - 5 3 0 n-H9C4-0co U 1 C H 3 CHzOH CH3 N -(3 J, 0..J - 48 E T P - 4 9 - 6 5 0 c;I oco 1-1 r - 0 c I 1 CH3 E T P - 6 8 - 3 2 E T P - 4 6 - 5 4 COO-CHz - 1 1 N0z N CH3 0 1 11 n-H9C4-C - OCO OCH:i N N c z H 5 H 3 d 1 F- T p - 6 8 - 7 1 0.li n-HZ7C13C0 E T p - 2 1 - 2 5 E T p - 1 8 - 1 4 N) 0 0 CH3 CH3 H IS C7-O- C - 61.., 1 C ie 0 0 CH2OR 11 CH3 t-H9C4-C - OCH3 1 E T P - 1 3 - 6 8 0 ii H3C - 0 -SOz-NHO E T P - 1 3 - 6 6 0 H3COChCh0C0 E T P - 1 2 - 3 4 COO-CHz - N 1 1 C N N N CH3 : 1 6 1 Ch 0 CHzOH _--- - CH3 N 51 E T P - 3 6 - 6 0- E T P - 3 4 -.3 1 E T P - 3 4 - 4 7 HN - C 1 C---, 11 N 0 z 0 C -N 0 C P 0 HN-CO O-CHZ - C C ú N 0 OOCHz-k,.N 52 - E T P - 3 6 - 6 6 0 H3COUZChoco E T P - 1 3 - 6 E T P - 4 6 - 2 3 H3C0 - (3_ c 1 0' N 1 1 1 c 2 0 c - 0- 11 0 ::1 6 - 1 CH3 0 Z "-N :: 1 6 li, 1 CH3 53 - E TIP - 3 4 1 ETP - 1 5 - 6 7 E T P - 1 3 - 6 0 0 H:;C-C - N 11 "' N 0 0 (Hr,Cz) zIN-C-0 0 t - H9 C 4 - C 0 CH2091 , ' CH3 1 : 1 -1,6 1 C ú 1) : 1 6_.1, C H 3 54 - 0- ELETP-13-64 E T P - 6 9 - 5 3 0 n-H9 C 4- 0 C E T P - 1 8 - 6 5 0 HsCz-OCO 61 _.1, 1 CH3 0 CB20H C H3 N 0 11 ULU C H3 (:y _--- L_ C H z 0 H k 'N) 61 _., 1 o C ll 3 ii - E T P - 4 6 - 3 2 COO-CHz 1 1 E T P - 1 2 - 6 0 0 C H NI\ 0- C E T P - 1 3 - 2 3 0 C H z 0 H CH3 N N 0 0 H3co-o- c11 0 1 1 - 56 E T P - 1 5 - 1 E T P - 3 4 - 6 7 0 UsCz)zN-C-0 E T P - 4 3 - 6 0 0 k, 1 CHzOH Z7) C H3 H3C-C - C ::: 1 6 0 t-H9C4-co OH /7-- N - 57 1 E T P - 3 4 - 6 6 0 il H:;COCHzCHzOCO E T P - 1 4 - E T P - 9 - 2 3 "'. N:

61 1 6 0 ', z 0, CH3 - c- 0 11 0 : 1 6 1 CH3 H3co- c - z 0- 11 0 ::: 1 6 58 - E T P - 3 6 - 1 E T P - 3 6 - 6 7 0 UsCz),zN-C-0 E T P - 3 4 - 6 0 1 t E 3 C - C - N 11 '' N o C 2 0 t - H9 C 4 - C 0 :1 1 C ie J -0 1 4z - 59 ET P - 1 8 - 5 4 ETP-356-71 C H3 0 1 il n- H 9 U 4- U - UCO 1 C 0 n-HZ7C13C0 E T P - 3 4 - 2 5 CHzOH CH3 zHs 0 C H 3 1 1 C 9 0 0 n-HisCi-O-C -N - ET P - 4 5 - 1 4 t - H 9 C 4 - E T P - 3 5 - 6 8 0 0 ' OCH3 11 Y- C N 11 H3C -0-SOz-N. HCO E T P - 1 5 - 6 6 0 H3COCHZCHZOCO N "- N CH3 _ C H z 0 H (- CH3 : 1 6_.1, 1 C ú - 61 1 E T P - 4 6 - 6 E T P - 3 4 - 2 3 0 C-N / 0 C H 3 C 0 C- NI "-N 0 E T P - 2 1 - 1 0 C H 3 C H 3 N "'N, H3c-c- 11 0 : 1 6 1 62 - E T P - 6 8 - 6 7 0 (H5CZ)2N-C-0 E T P - 1 5 - 6 0 E T P - 2 1 - 5 4 CH3 0 n-Hgc,t-c -OCO 1 c N) 0 t-H9C4-CO CHAH CH3 c 9 CH3 CH3 CJs : 1 6 1 c - 63 ET P - 3 4 - 7 1 0!1 n-HZ7C13C0 E T P - 1 5 - 2 5 n-HiSC7-0-C- E T P - 1 3 - 1 4 N N 0 0 'kl CHzOH / N) CH3 N c ie 0 0 t-H9C4-C - N : 1 6 1 c H 3 E T P - 3 4 - 6 8 0 E T P - 6 8 - 6 6 0 H3COCH2CHZOCO ET P - 1 2 - 5 4 11 H3C-O-SOz-NHO k ' IN) N -C) J, ol 1 L," JI -111 : 1 601 CH3 0 nH9C4-COCO CHAH CH3 C z H rs 6 C - E T P - 1 2 - 6 8 0 (:y CH3 H:,C - S02NHCO CHzOH N 57, 5, 1 E T P - 3 6 - 1 4 E T P - 4 7 6 4 0 tH 9 C 4- C - N 11 ',' IN 0 C ie 0 H5C2AC0 OCH3 N 66 E T P - 9 - 5 3 E T P - 4 6 - 6 5 0 ill oco E T P - 3 4 - 3 2 0 5 n-H9C,-OCO X) N 0 1-11 : ' 1 6 COO-CHZ - 1 : G")1 1 1 N 0 2 0 c H 3 C - 67 E T P - 1 2 - 5 4 E T P - 1 5 - 7 1 E T P - 6 9 - 2 5 CH3 0 1 ii n-H9C4-C -OCO., CHzOH 1 C11 3 c z H 5 0 n-h7Ci3C0 CHzOH CH:i c A 0 0 CHzOH 1 CH3 n-HisC7-0-C E T P - 3 4 1 4 0 0 t-H9C4-C - E T P - 6 8 - 6 8 - H3c-0 E T P - 3 4 - 6 c h - 0 0 -SOz-NHCO N 0 -c 11 0 tu :. 1 -1,6 -1 t 1 - - 69 E T P - 1 5 - 2 3 E T P 4 6 - 1 E T P - 1 2 - 6 7 0 'k-- 1 C H z 0 H C H 3 H3C0 11 N o C 9 0 OCH3 H 3 C - C ll N 0 0 UsCz)zN-C-0 CHzOH C H 3 9 - 70 E T P - 4 6 - 6 0 0 11 t ' H9 C 4, - C 0 E T P - 4 6 - 6 6 0 H3COChCHAC0 E T P - 5 2 - 6 0 0 N N CH3 OCH3 N C-Z - 0 ^V V\.ACH3 0- 0 1 6 C im 71 - E T P - 3 4 - 4 E T P - 5 2 - 3 4 COO-CHz - 1 )l - CN E T P - 5 2 - 6 6 3 0 COOCHz N NHSOZCH3 0 /v 0 0 C H N 0 t - H9 C 4 - C 0 0 ^'v 0 0 C H N 1 The electron-transferring incorporated into the photographic present invention may be decomposed to release an electron-transferring agent therefrom aL a pertinent speed during storage of the material, while the electron-transferring agent originally incorporated into the photographic material is gradually oxidized to be lost during storage of the material, whereby the concentration of the electron-transf erring agent in the material mav be keDt within a suitable range.

- The range of the concentration of the electrontransferring agent precursor to be used for the purpose together with an electron-transf erring agent is in mols from 0.01 time to 20 times the mols of the electrontranserring agent. Especially advantageously, the concentration range is, in mols, from 0.1 time to 5 times the mols of the electrontransferring agent.

In order that the electron-transferring agent precursor may be decomposed to release. an electrontransferring agent in accordance with the speed of the decomposition of the originally existing electrontransferring agent to be lost whereby the concentration of the electron-transf erring agent in the photographic material may always be kept constant, the decomposition speed of the electron-transferring agent precursor in agent precursor material of the 1C, i- t t 1 73 - the material is preferably within the range of from 0.01 to 100 times the decomposition speed of the originally ly existing electron-transferrina agent, more prefferab.

within the range of from 0.1 to 5 times thereof.

The electron-transf erring agent to be released from the elect ron-transf erring agent precursor foruse in the present invention may be the same as or different from the electron-transferring agent originally incor porated in the photographic material. Preferably, the former is the same as the latter.

The compounds for use in the present invention may be produced by the methods descr-ibed in the patent publications referred to hereinbefore as examples for the electron-transferring agent precursor, The amount of the dye-forming compound to be incorporated into the photographic material of the present invention is within the range of from 0.05 to 5 2 2 mmol/m, preferably from 0.1 to 3 mmol/m., although this depends upon the absorbancy index of the dye formed therefrom. The dye-forming compound may be used either singly or in the form of a mixture of two or more differentkinds of compounds. In order to obtain a black image or images with different hues, two or more kinds of dye-forming substances each releasing a mobile dye with a different hue are used as a mixture, for example, at least one cyan dye-forming substance, at X 74 - least one magenta dye-forming substance and at least one yellow dye- forming substance are incorporated into the silver halide-containing layer or the adjacent layer in A photographic material, as described in JP A-60-162251.

In accordance with the present invention, at least one of an elect rondonat ing agent and a precursor thereof is incorporated into the photographic material, and the details of the compounds are described in European Patent 220,746A. and Disclosure Bulletin 876199. Especially preferred electron-donating agents (substances) (as well as precursors thereof) for use in the present invention are compounds of the following general formula (C) or (D).

(C) (D) R17 OA, R19 1 R18 R20 0A2 OA, R17 0A2 1 R18 R20 R19 i i i 1 i i 1 i j i 4L - in which A, and A2 each represent a hydrogen atom or a protective group for a phenolic. - hydroxyl group capable of being de-protected by a nucleophilic reagent.

As the nucleophilic reagent as herein referred to, there may be mentioned, for example, anionic reagents having OH-, R'O- (where R' is an alkyl group or an aryl group), a hydroxamic acid anion or S03 2-, as well as non-covalent electron pair-containing compounds such as primary or secondary amines, hydrazines, hydroxylamines, alcohols and thiols.

Preferred examples of A, and A2 include a hydrogen atom, an acyl group, an alkylsulfonyl group, an arylsulfonyl group,- an alkoxy-carbonyl group, an aryloxycarbonyl group, a dialkylphosphoryl group, a diarylphosphoryl group and the protected groups described in JP-A-59-197037 and JP-A-59- 20105. if 2 possible, A, and A2 may form a ring together with R', R, R3 or R4. A, and A2 may be same or different In the formulae,. R17, R18, represents a hydrogen atom, an alkyl group (which may optionally be substituted, for example, methyl, ethyl, n- buthyl, cyclohexyl, n-octyl, allyl, sec-octyl, tertoctyl, n-dodecyl, n- pentadecyl, n-hexadecyl, tert-octadecyl, 3-hexadecanoylaminophenylmethyl, 4-hexadecylsulfonylaminophenylmethyl, 2-ethoxycarbonylethyl, 3- R19 and R20 each - 75 - 76 carboxypropyl, N-ethylhexadecylsulfonylaminomethyl, N methyldodecyisulfonylaminoethyl); an aryl group (which may optinally be substituted, for example, phenyl, 3 hexadecyloxyphenyl, 3-methoxyphenyl, 3-sulfophenyl, 3 chlorophenyl, 2-carboxyphenyl, 3-dodecanoylaminophenyl); an alkylthio group (which may optionally be substituted, for example, n-butylthio, methylthio, tert-octhylthio, n-dodecylth..o, 2-hydroxyethylthio, n-hexadecylthio, 3 ethoxycarbonylpropiothio); an arylthio group (which may optionally be substituted, for example, phenylthio, 4 chlorophenylthio. 2-n-o-ct.yloxy-5-t-butylphenylthio, 4 dodecyloxyphenylthio, 4-hexadecanoylaminophenylthio); a sulfonyl group (which is an optionally substituted aryl or alkylsulfonyl group, for example, methanesulfonyl, butanesulfonyl, p-toluenesulfonyl, 4-dodecyloxyphenyl sulfonyl, 4-acetylaminophenylsulfonyl); a sulfo group; a halogen atom (e.g., fluorine, chlorinei bromine, iodine); a cyano group; a carbamoyl group (which may optionally be substituted, for example, methylcarbamoyl, diethylcarbamoyl, 3-(2,4-di-t-pentylphenyloxy)propyl- carbamoyl, cyclohexylcarbamoyl, rdi-n-octylcarbamoyl); a sulfamoyl group (which may. op.tionally be substituted', for example, diethylsulfamoyl, di-n-octylsulfamoyl, n hexadecylsulfamoyl, 3-iso-hexadecanoylaminophenylsulfa- MOY1); an amido group (which may optionally be v L substituted, for example, acetamido, iso-butyroylamido, 4- tetradecyloxyphenylbenzamido, 3-hexadecancylam:Lnobe.nzamido); an imido group (which may optionally be substituted, for example, succinic acid imido, 3-1aurylsuccinic acid imido, phthalimido);.a carboxyl group; or a sulfonamido group (which may optionally be substituted, for example, methanesulfonamido, octane sul f onamido, hexadecanesulfonamido, benzenesulfonamido, toluenesulfonamido, 4-lauryloxybenzenesulfonamido). The total number of carbon atoms in R17 to R20 must be 8 or more. R17 and R18, and/or R19 and R20 in the formula (C) and R17 and R18. R18 and R19, and/or R19 and R20 in the formula (C) may be bonded together to form a saturated or unsaturated ring.

Among the electron-donating substances of the above-mentioned formulae (C) and (D), those where at least two of R17 to R20 are other substituents than hydrogen are preferred. In particular, those where at least one of R17 and R18 and at least one of R19 and R20 are other substituents than hydrogen are especially preferred.

Two or more kinds of different electron-donating substances may be used togethery or these may be used together with precursors thereof. The electron-donating substances may be same as the reducing substances for 77 - 78 use in the present invention. Specific examples of the electron-donating substances for use invention are mentioned below, which, limitative.

(ED-1) OH C,H17 (n) (n) H C zll 1 J 17 8 OH (ED-2) OH 1 C.H17 (sec) _-11 1 (sec)H17C.1 1 OH (ED-3) in the present however 'are not OH CI-12 NHCOC1.H31(n) OH -lj Q ik 1 (E D - 4) (E D - 5) OH 1 1 -- CHzCHz- H3 C 1 0 H 0 H 1 C H --CHzCHz H3C - CHz - Cj 1 1 C H 3 OH ( E D - 6) CH3 OH C H z H:3C - CHz - C OH CH3 -NHSOzCjb-H-33(n) 0--- NHSOzCsHi7(n) NHSOzCsHi,i(n) 1 - ( E D - 7) (ES - 8) ( E D - 9) 0 H i WH33C,6-f::: 1 S03Na 1 0 H OH 1 WH33Cii.S' 1 1 - OH 0 H S03K CH3 CH z N H C 0 Cz H 1 rs (n) C - C -CHz H 3 C CH3 OH (E D - 1 0) OH 1 1 CHZ - 1 (sec)HtiCEi 1 OH NHCOC,,His(n) t 81 (ED-11) 0 0 11 11 C2H50-C-C-0 CH2CH2-,G-NHSO2C16H33 (n) (n)H1.C.

OH (ED-12) 0 0 11-1 (n)H33C16 1 C02C2H5 H7C3 CH3 OH The amount of the electron-donating subsance (or a precursor thereof) may be in a broad range but is preferably within a range of from 0.01 mol to 50 mols, especially from 0.1 mol to 5 mols, per mol of the positive dye- forming substance. This is from 0.001 mol to 5 mols, preferably from 0.01 mol to 1.5 mols, per mol of the silver halide in the photographic material.

In accordance with the present invention, the above-mentioned electrontransferring agent and electron-transf erring agent precursor are combined with a binder and a silver halide emulsion together with the 1 above-mentioned reducible dye-forming compound and elect ron-donati ng agent to form a light-sensitive layer of one unit. The reducible dyeforming compound may be added to the same layer as that containing a silver halide emulsion, but this may be added to the adjacent layer separately from the silver halide emulsion. In the latter case, it is preferred that the reducible dyeforming compound-containing layer is positioned below the silver halide emulsion-containing layer in view of the sensitivity of the photographic material. In this case, the electrontransf-erring agent and electrontransferring agent precursor and the electron-donating substance may be added to either the silver halide emulsion-containing lay, er or the reducible dye-forming compoundcontaining layer, but it is preferred that at least the electron-transf erring agent and the electrontrasferring agent precursor are present in the silver halide emulsion layer. In the present invention, at least one of light-sensitive- layer -units of the kind described above is used in preparation of the photographic material. In general, three groups of lightsensitive layers each having a different color-sensitivity are provided in the photographic material for reproduction of full color. For instance, there is a combination of three groups of a blue-sensitive layer, a t 1 1 83 - green-sensitive layer and a red-sensitive layer and a combination of three groups of a green-sensitive layer, a red-sensitive layer and an infrared-sensitive layer. The respective color-sensitive layers may be arranged in various orders which are known in. the field of conventional color photographic materials. The respective color-sensitive layers may optionally comprise two or more layers, if desired.

In accordance with the present invention, it is preferred to provide a substantially non-light-sensitive interlayer which contains a nondiffusible reducible substance which may be cross-oxidized with the oxidation product of an elect ron-t rans fer ring agent, between the light-sensitive layers each having a different colorsensitivity, so as to prevent any possible coloring defects which are called color transferring or color mixing. When the photographic material has three groups of lightsensitive layer units each having a different color-sensitivity, the interlayer Ls preferably--- provided between the respective lightsensitive layer units. When the photographic material has plural interlayers, the aforesaid reducible substance to be added to the respective interlayers may be the same or different.

84 Next, the reducible dye-forming compounds for use in the present invention will be explained in detail.

The reducible dye-forming compounds for use in the present invention are preferably compounds represented by the following general formula (L):

PWR-(Time)t-Dye (L) in which PWR represents a group capable of releasing -(Time)t-Dye by reduction; Time represents a group which may release Dye by the subsequent reaction, after having been released from PWR in the form of -(Time)t-Dye-; t represents an integer of 0 or 1; and Dye represents a dye or a precursor thereof.

-First, PWR is explained in detail.

PWR may be a group which corresponds to a moiety containing an electronaccepting center and an intramolecular nucleophilic reaction center in a compound capable of releasing a photographic reagent by an intramolecular nucleophilic substitution reaction after reduction, as illustrated in U.S. Patents 4,139,389, 4,139,379 and 4,564,577 and JP-A-59-185333 and JP-A5784453, or a group which corresponds to a moiety containing an -elect ron-accept i ng quinoid center and a C - 85 carbon atom to bond the center to a photographic reagent in a compound capable of releasing the photographic reagent by an intramolecular electron transfer -reaction after reduction, as illustrated in U.S. Patent 4,232,107, JP-A-59-101649, Research Disclosure (1984), IV, 24025 and JP-A-61-99257. In addition, this may also be a group which corresponds to a moiety containing an electron-attracting group- substituted aryl group and an atom (sulfur, carbon or nitrogen atom) to bond the group to a photographic reagent in a compound capable of releasing the photographic reagent by cleavage of the single bond after reduction, as illustrated in JP-A-56142530, U.S. Patents 4,343,893 and 4, 619,884. Further, this may also be a group which corresponds to a moiety containing a nitro group and a carbon atom to bond the group to a photographic reagent in a nitro compound capable of releasing the photographic reagent after acceptance of an electron, as illustrated in U. S. Patent 4,450,223, or a group which corresponds to a moiety containing a dieminal-dinitro group and a carbon atom to bond the group to a photographic reagent in a dinitro compound capable of beta-releasing the photographic reagent after acceptance of an electron, as described in U.S. Patent 4,609,610.

Q 86 - Further, there are mentioned the compounds having S02-X" (where X" represents anyone of oxygen, sulfur and nitrogen atoms) and an elect ronattract ing group in one molecule as described in JI-A-62-'91-06885; the compounds having a PO-X" bond (where X" has the same meaning as mentioned above) and an electron-attracting group in one molecule as described in JP-A-62-106895; and the compounds having a C-X' bond (where X' has the same meaning as X" or represents -S02_) and an electronattracting group in one molecule as described in JP-A62-106887.

Among the compounds of the formula (L), those represented by the following formula (L-II) are preferred so as to more sufficiently attain the object of the present inVention.

(L-II) X / \N R21....

1 EAG--- (Time -tDy in which (Time)t-Dye is bonded to at least one of p21, R22 and EAG.

k 4 87 - The moiety which corresponds to PWR in the formula (L-II) will be explained hereunder.

X represents an oxygen atom (-0-), a sulfur atom ("S-) or a nitrogencontaining group (-N(R23)_).

R21 z R 22 and R23 each represents a substituent except a hydrogen atom or R21, R22 and R23 represent a chemical bond.

Substituents except a hydrogen atom for R21, R22 and R23 include an alkyl or aralkyl group (which may optionally be substituted, for example, methvl, trifluoromethyl, benzyl, chloromethyl, dime thylami nome thyl, ethoxycarbonylmethyl, aminomethyl, acetylaminomethyl, ethyl, 2-(4dodecanoylaminophenyl)ethyl, carboxyethyl, allyl, 3,3,3-trichloropropyl, n-propyl, iso-propyl, nbutyl, iso-butyl, sec-butyl, t-butyl, n-pentyl, secpentyl, t-pentyl, cyclopentyl, n-hexyl, sec-hexyl, thexyl, cyclohexyl, n-octyl, sec-octyl, t-octyl, n-decyl, n-undecyl, n-dQdecyl, n-tetradecyl, n-pentadecyl, nhexadecYl, sec-hexadecyl, t-hexadecyl, n-octadecyl, toctadecyl); an alkenyl group (which may optionally be substituted, for example, vinyl, 2-chlorovinyl, 1methylvinyl, 2-cyanovinylr cyclohexen-lyl); an alkynyl group (which may optionally be substituted, for example, ethynyl, 1-propynyl, 2-ethoxycarbonylethynyl); an aryl group (which may optionally be substituted, for example, 88 - phenyl, naphthyll 3-hydroxyphenyl, 3-chlorophenyl, 4acetylaminophenyl, 4hexadecanesulfonylaminophenyl,.2methanesulfonyl-4-nitrophenyl, 3nitrophenyl, 4-methox-vphenyl, 4-acetylaminophenyl, 4methanesulfonylphenyl, 2,4-dimethylphenyl, 4-tetradecyloxyphenyl); a he'%erocyclic group (which may optionally be substituted, for example, 1imidazolyl, 2-furyl, 2-pyridyl, 5-nitro-2pyridyl, 3-pyridyl, 3,5-dicyano2-pyridyl, 5-tetrazolyl, 5-phenyl-l-tetrazolyl, 2-benzothiazolyl, 2benzimidazolyl, 2-benzoxazolyl, 2-oxazolin-2-yl, morpholino); an acyl group (which may optionally be substituted, for example, acetyl, propionyl, butyroyl, iso-butyroyl, 2,2dimethylpropionyl, benzoyl, 3,4dichlorobenzoyl, 3acetylamino-4-methoxybenzoyl, 4-methylbenzoyl, 4methoxy3-sulfobenzoyl)-; a sulfonyl group (which may optionally be substituted, for example, methanesulfonyl, ethanesulfonyl, chloromethanesulfonyl, propanesulfonyl, butanesulfonyl, n-octanesulfonyl, n-dodecanesulfonyl, nhexadecanesulfonyl, benzenesulfonyl, 4-toluenesulfonyl, 4-n-dodecyloxy benzenesulfonyl); a carbamoyl group (which may optionally be substituted, for example, carbamoyl, methylcarbamoyl, dimethyl carbamoyl, bis(2methoxyethyl)carbamoyl, diethylcarbamoYl, cyclohexylcarbamoyl, di-noctylcarbamoyl, 3-dodecyloxypropylcarbamoyl, hexadecylcarbamoyl, 3-(2,4di-t-pentyl- K IR 89 - phenoxy)propylcarbamoyl, 3-octanesulfonylaminophenylcarbamoYl, di-n- octadecylcarbamoyl); a sulfamoyl group (which may optionally be substituted, for example, sulfamoyl, methyl sulf amoyl, dimethylsulfamoyl, dielChylsulfamoyl, bis(2-methoxyethyl)sulfamoyl, di-n-butylsulfamoyl, methyl-n-octylsulfamoyl, n-hexadecylme."khylsulfamoyl, 3ethoxypropylmethylsulfamoyl, N-phenyl-Nmethylsulfamoyl, 4decyloxyphenylsulfamoyl, methyloctadecylsulfamoyl).

R21 and R23 each are preferably a substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heterocyclic, acyl or sulfonyl group. The number of the carbon atoms in R21 and R23 is preferably from 1 to 40.

R22 is preferably a substituted or unsubstituted acyl or sulfonyl group. The number of the carbon atoms in the group is preferably from 1 to 40.

R21, R22, R23 and EAG may be bonded to each other to form a 5-membered to 8-membered ring.

EAG will be explained below in the context of the formula (L-III).

Among the compounds of the formula (L-II), those represented by the following formula (L-III) are more preferred in order to more satisfactorily attain the object of the present invention.

1-4- - (L-III) iR 24 1 X \ N / 1 EAG Y 1 (Timet-tz---Dye in which (Time)t-Dye is bonded to at least one of R24 and EAG.

The moiety which corresponds to PWR in the formula (L-III) will be mentioned below.

Y' is a divalent linking group and is preferably -CO-, or -S02-. X has the same meaning as defined above for the formula (L-II). R24 forms a 5membered tb 8membered (inclusive of nitrogen, Y' and X in the formula) mono-cyclic or condensed-cyclic hetero-ring.

Preferred examples of the hetero-ring moiety in the formula are mentioned below.

A b 91 O'-N 01, N ',A__0 1 EAG R R25 0,r R26 O"N 0 1 EAG R25 26 CH3 R N EAG 0 N 1-, 1- 1 01-1 NS02 1 EAG R25 R25 i R26 Q 11 0 1 N 1 EAG R25 R2 W._ S 0.1 N "I"o 1 EAG - 92 R25 CH R2 0 EAG R25 26 R -r- N 01, 0 N 1 EAG m 0 N 0 i EAG R26 R25 27 N NCOR 1 EAG R25 ' R26 0" N N-S02R27 R25 R 2 6 0 N 0 1 EAG R26 R25 -S02 I.E..G R25 1 R26 sl, N 0 1 EAG P i ji t 1 - 93 R25 5;, 1 R26 i L N 1-11 S-, N 'I'Lo 1 EA.G R 5 2 R S SINI'LIO 1 EAG R25 N.5 11 SS'_? N 0 1 EAG R 27 R25 R26 S,,, 27 N N-COR 1 EAG R25 R2 7.

R2 N s, N '11,110 1 EAG R25 2 R 0 j S"N"L-zO 1 EAG 1. R25 R26 I.

S-, N 1 EAG R25 "'I- /R2 6 s, N -IS02 1 EAG R25 R26 -9s,' 0 IN 1 EAG R2-R25 S ",N N-R27 1 EAG 0 N.1 _ 1 s, N,so 1 EAG R25 R - N S,, N,o 1 EAG R25 R26 - L S k's "N 1 - EAG 0 R25 1.11 N S 0 N i 0 R25 R26 k N 0 1 EAG N-R25 S-, N -IS02 1 EAG R25 R26 R28 0 N"'N i EAG 0 R26 ---IT- R28-N A, N 0 1 EAG R25 R26 l- N.I N,, N '111 0 1 EAG R25 0 "I N,, N 0 1 EAG R25 R26 ""r- R28 N_, -S02 1 EAG 0 R26 N 28 1 R N S 0 N, 2 1 EAG R 26 R 25 R 2 8 --N R- 0 N 1 EAG R25 R26 l- 1 N, N1N-S02-R27 1 EAG R25 R26 ",IF, - N.11 N,_ N J":N-CO-R27 1 EAG 0' R25 R26 N R28,-- ""N) 1 EAG R26 0 R28,- "N 1 EAG 0 R25 R28-N N EAG R26 R25 -I S N,, N 0 EAG S R25 R26 1 R28,-' N:o 1 EAG R R26 ]i R27 [7N::( N 0 1 EAG 97 - In these formulae, R2S.. R26 and R27 each are preferably a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. R28 represents 'an alkyl group, an aryl group, an acyl group or a sul-fonyl group. (Time)t- Dye may be bonded to R25, R6 or R27.

EAG has an aromatic group capable of accepting an electron from a reducible substance and is bonded to a nitrogen atom. EAG is preferably a group represented by the following formula (A):

(A) ki \ Vp Z2 In the formula (A), Z, and Z2. which are the I I same or different, represent -C-Sub or -N-; Vn repreI sents an atomic group necessary to form a 3- to 8membered aromatic group together with Z, and Z2; and n represents an integer of from 3 to 8.

V. means -Z3-; V4 means -Z3-Z4-; V5 means -Z3Z4-ZS-; V6 means -Z3-Z4-Z5Z6-; V7 means -Z3-Z4-Z5-Z,Z7-; V. means -Z3-Z4-Z,-Z6-Z7-Z-' Z3 to Z. each repre- 98 - Sub Sub 1 1 sents -C-, -N-, -0-, S- or -S02-7 Sub independently Sub represents a chemical bond (7-bond), a hydrogen atom or a substituent mentioned below. Sub's may be the same or different and they may be bonded to each other to form a 3-membered to 8-membered, saturated or unsaturated carbon-ring or hetero-ring.

In the formula (A), Sub's are so selected that the total of the Hammett's substituent. constants (sigma para) of all the substituents may be +0.50 or more, preferably +0.70 or more, most preferably +0.85 or more.

EAG will be explained in more detail hereunder.

EAG represents a group capable of accepting an electron from a reducible substance and is bonded to a nitrogen atom. EAG is preferably an aryl group or heterocyclic group substituted by at least one electronattracting group. The substituents to be bonded to the aryl group or heterocyclic group for EAG may be utilized for adjusting the total properties of the compounds. More precisely, the substituents may be utilized for adjusting the total properties of the compounds, for example, the easy acceptability of electrons, as well as the water-solubility, the oil-solubility, the diffusibility, the sublimability, the melting point, the -1 1 dispersibility in binders such as gelatin, the reactivity with nucleophilic groups and the reactivity w.,Lth electrophilic groups.

Specific examples of EAG are set forth below, but do not limited the invention. - As examples of aryl groups substituted by at least one or more electron attracting groups, there are a 4-nitrophenyl group, 2nitrophenyl group, 2-nitro-4-N-methyl-N-n-butylsulfamoylphenyl group, 2nitro-4-N-methyl-N-n-octylsulfamoylphenyl group, sulfamoylphenyl group, sulfamoylphenyl group, 2-nitro4-N-methyl-N-n-dodecyl2-nitro-4-N-methyl-Nn-hexadecyl2-nitro-4-Nmethyl-N-n-octadecylsulfamoylphenyl group, 2-nitro-4-N-methyl-N-(3carboxypropyl)sulfamoylphenyl group, 2-nitro-4-N-eLhyl-N(2sulfoethyl)sulfamoylphenyl group, 2-nitro-4-N-n-hexadecyl-N-(3sulfopropyl)sulfamoylphenyl group, 2-nitro-4N-(2-cyanoethyl)-N-((2hydroxyethoxy)ethyl)sulfamoylphenyl group, 2-nitro-4diethylsulfamoylphenyl group, 2nitro-4-di-n-butyl-sulfamoylpheny1 group, 2-nitro-4-din-octylsulfamoylphenyl group, 2-nitro-4-di-noctadecylsulfamoylphenyl group, 2-nitro-4-methylsulfamoylphenyl group, 2nitro-4n-hexadecylsulfamoylphenyl group, 2nitro-4-N-methyl-N-(4dodecylsulfonylphenyl)sulfamoylphenyl group, 2-nitro-4-(3methylsulfamoylphenyl)sulfamoylphenyl group, 4-nitro-2-N-methyl-N-n-butyl- 100 sulfamoylphenyl group, 4-nitro-2-N-methyl-N-n-octylsulfamoylphenyl group, 4nitro-2-N-methyl-N-ndodecylsulfamoylphenyl group, 4-nitro-2-N-methyl-N-n- hexadecylsulfamoylphenyl group, 4-nitro-2-N-methyl-N-n- octadecylsulfamoylphenyl group, 4-nitro-2-N-methyl-N-(3- carboxypropyl)sulfamoylphenyl group, 4-nitro-2-N-ethyl-N- (2sulfoethyl)sul'lamoylphenyl group, 4-nitro-2-N-n-hexadecyl-N-(3- sulfopropyl)sulfamoylphenyl group, 4-nitro-2N-(2-cyanoethyl)-N-((2- hydroxyethoxyethyl)sulfamoylphenyl group, 4-nitro-2- diethylsulfamoylpheny1 group, 4nit ro-2-di-n-butylsulf amoylphenyl group, 4-nitro-2-dinoctylsulfamoylphenyl group, 4-nitro-2-di-n- octadecylsulfamoylphenyl group, 4-nitro-2-methylsulfamoylphenyl group, 4nitro-2-n-hexAdecylsulfamoylphenyl group, 4nitro-2-N-methyl-n-(4dodecylsulfonylphenyl)sulfamoylphenyl group, 4-nitro-2-(3methylsulfamoylphenyl)sulfamoylphenyl group, 4-nitro-2chlorophenyl group, 2nitro-4-chlorophenyl group, 2-nitro-4-N-methyl-N-nbutylcarbamoylphenyl group, 2-nitro-4-N-methyl-N-n2-nitro-4-N-methyl-N-n2-nitro-4-N-methyl-Nn2-nitro-4-N -methyl-N-n2-nitro-4-N-methyl-N-(32-nitro-4-N-methyl2-nitro4-N-n- octylcarbamoylphenyl group, dodecylcarbamoylphenyl group, hexadecylcarbamoylphenyl group, octadecylcarbamoylphenyl group, carboxypropyl)carbamoylphenyl group, N-(2-sulfoethyl)carbamoylphenyl group, ti - 101 hexadecyl-N-(3-sulfopropyl)carbamoylphenyl group, 2nitro-4-N-(2- cyanoethyl)-N-((2-hydroxyethoxy)ethyl)carbamoylphenyl group, 2-nitro-4-. diethylcarbamoylr)henyl group, 2-nitro-4-di-n-but--ylcarbamoylphenyl group, 2nitro-4-di-n-ocli--ylcarbamoylpheny1 group, 2-nitro-4-dinoctadecylcarbamoylphenyl group, 2-nitro-4-methylcarbamoylphenyl group, 2nitro-4-n-hexadecylcarbamoylphenyl group, 2-nitro-4-N-methyl-N-(4dodecylsulfonylphenyl)carbamoylphenyl group, 2-nitro-4-(3methylsulfamoylphenyl)carbamoylDhenyl methyl-N-n-butylcarbamoylphenyl methylN-n-octylcarbamoylphenyl methyl-N-n-dodecylcarbamoylpheny1 group, group, group.. group.

4-nitro-2-N4-nitro-2-N4-nitro-2-N4-nitro-2-N methyl-N-n-hexadecylcarbamoylphenyl group, 4-nitro-2-Nmethyl-N-nactadecylcarbamoylphenyl group, 4-nitro-2-Nmethyl-N-(3carboxypropyl)carbamoylphenyl group, 4nitro-2-N-ethyl-N-(2sulfoethyl)carbamoylphenyl group, 4-nitro-2-N-n-hexadecyl-N-(3sulfopropyl)carbamoylpheny1 group, 4-nitro-2-N-(2-cyanoethyl)-N-((2hydroxyethoxy)ethyl) carbamoylphenyl group, 4-nitro-2diethylcarbamoylphenyl group, 4-nitro-2-di-n-butylcarbamoylphenyl group, 4-nitro-2-di-n-octylcarbamoylphenyl group, 4-nitro-2-dinoctadecylcarbamoylphenyl group, 4-nitro-2-methylcarbamoylphenyl group, 4nitro-2-n-hexadecylcarbamoylphenyl group, 4-nitro-2-N-methyl-N-(4dodecylsulfonyl- 102 - phenyl)carbamoylphenyl group, 4-nitro-2-(3methylsulfamoylphenyl)carbamoylphenyl group, 2,4-dimethanesulfonylphenyl group, 2-methanesul.'Lonyl-4-benzenesul'Lonylphenyl group, 2-noctanesulfonyl-4-methanesulfonylphenyl group, 2-n-tetradecanesulfonyl-4meklhanesul'Lonylphenyl group, 2-n-hexadecanesulfonyl-4methanesulfonylphenyl- group, 2,4-di-n-dodecanesulfonylphenyl group, 2,4didodecanesulfonyl-5-trifluOromethylphenyl group, 2n-dedanesulfonyl-4cyanotrifluoromethylphenyl group, 2cyano-4-methanesulfonylphenyl group, 2, 4,6-tricyanophenyl group, 2,4-dicyanophenyl group, 2-nitro4methanesulfonylphenyl group, 2-nitro-4-n-dodecanesulfonylphenyl group, 2nitro-.4-(2-sulfoek-hylsulfonyl)phenyl group, 2-nitro-4carboxymethylsulfonylphenyl group, 2nitro-4-carboxyphenyl group, 2-nitro4-ethoxycarbonyl-Sn-butoxyphenyl group, 2-nitro-4-ethoxycarbonyl-Snhexadecyloxyphenyl group, 2-nitro-4-diethylcarbomyl-SnhexadecYloxyphenyl group, 2-nitro-4-cyano-5-ndodecylphenyl group, 2,4dinitrophenyl group, 2-nitro-4n-decylthiophenyl group, 3,5-dinitrophenyl group, 2nitro-3,5-dimethyl-4-n-hexadecanesulfonyl group, 4methanesulfonyl2-benzenesulfonylpheny1 group, 4-noctanesulfonyl-2-methanesulfonylphenyl group, 4-ntetradecanesulfonyl-2-methanesulfonylphenyl group, 4nhexadecanesuifonyl-2-methanesulfonylphenyl group, 2,5- sz w.

- 103 didodecanesulfonyl-4-trifluoromethylpheny1 group, 4-ndecanesulfonyl-2- cyano-5-trifidoro,T.ethylphenyl group, 4cyano-2-methanesulfonylphenyl group, 4-nitro-2-methanesulfonylphenyl group, 4-nitro-2-n- dodecanesulL'onylphenyl group, 4-nitro-2-(2-sulfoethylsulfonyl)pheny1 group, 4nitro-2-carboxymethylsulfonylphenyI group, 4-nitro-2carboxyphenyl group, 4-nitro-2-ethoxycarbonyl-S-nbutoxyphenyl group, 4-nitro-2ethoxycarbonyl-5-n-hexadecyloxyphenyl group, 4-nitro-2-diethylcarbamoyl-5nhexadecyloxyphenyl group, 4-nitro-2-cyanc-5-n-dodecylphenyl group, 4nitro-2-n-decylthiophenyl group, 4nitro-3,5-dimethyl-2-nhexadecanesulfonyl group, 4nitronaphthyl group, 2,4-dinitronaphthyl group, 4-nitro2-n-octadecylcarbamoylnaphthyl group, 4-nitro-2-dioctylcarbamoylS-(3-sulfobenzenesulfonylamino)naphthyl group, 2,3,4,5,6pentafluorophenyl group, 2-nitro-4-benzoylphenyl group, 2,4diacetylphenyl group, 2-nitro-4trifluoromethylphenyl group, 4-nitro-2trifluoromethylphenyl group, 4-nitro-3-trifluoromethylphenyl group, 2,4,5tricyanophenyl group, 3,4-dicyanophenyl group, 2chloro-4,5-dicyanaphenyl group, 2-bromo-4,5-dicyanophenyl group, 4-methanesulfonyl group, 4-nhexadecanesulfonylphenyl group, 2-decanesulfonyl-S-trifluoromethylphenyl group, 2-nitro-5-methylphenyl group, 2 nitro-5-n-octadecyloxyphenyl group, 2-nitro-4-N-(vinyl- - 104 sulfonylethyl)-N-methylsulfamolypheny1 group, 2-methyl6-nitrobenzoxazol-5- yl group.

As examples of heterocyclic groups, there are a 2-pyridyl group, 3pyridyl group, 4-pyridyl group, 5nitro-2-pyridyl group, 5-nitro-Nhexadecylcarbamoyl-2pyridyl group, 3, 5-dicyano-2-pyr idyl group, 5dodecanesulfonyl-2-pyridyl group, 5-cyano-2-pyrazyl group, 4nitrothiophen2-yl group, 5-nitro-1,2-dimethylimidazol4-yl group, 3,5-diacetyl-2pyridyl group, 1-dodecyl-5carbamoylpyridinium-2-yl group, 5-nitro-2-Luryl group, and 5-nitrobenzothiazol-2-yl group.

Time represents a group which may release Dye -via the subsequent reaction triggered by the cleavage of the nitrogen- oxygen, nitrogen-nitrogen or nitrogensulfur bond.

The groups for Time are known, and for example, there may be mentioned the groups described in JP-A-61147244, pages 5 to 6, JP-A-61-236549, pages 8 to 14 and Japanese Patent Application No. 61-88625, pages 36 to 44.

Examples of the dye for Dye include azo dyes, azomethine dyes, anthraquinone dyes, naphthoquinone dyes, styryl dyes, nitro dyes, quinoline dyes, carbonyl dyes, and phthalocyanine dyes. These dyes may be used 1 t, - 105 - also in a form in which they have been temporarily changed SO as to absorb at a shorter wavelength range and which may be re-colored in development.

Specifically, the dyes as illustrated in European Patent 76,492A and JP-A59-165054 can be used for Dye in the present invention.

Specific examples of the reducible dye-forming compounds for use in the present invention are set forth below, which, however are not whatsoever limitative. In addition to them, the dye-forming compounds described in European Patent Application 220,746A2. and Disclosure Bulletin 87-6199 may also be used.

1 (1) (2) C14 3 1 -1; LH3 1 LI-I 3 0 2 N CH3 CH2-0 NHS02 ' 1 N=N-7j7-, CN -a - GL, 1 FI 15 N5 16-1,1 C ONH C 16 H 33(n) 0 CH 3 1 -CH2S02 -0, (1-13-( - - 0 Cl-1 2 C' 12 0 CH 3 I-T T NI-1 SO 2 CH3 'N 0 S02N /C 2 H.5 C 2 115N01-1 0 2' 1 1 y 4, oy CO NH C 16 1-1 33(n) CH 3 S 0 2 NIT" /, I P.

1 CD C)1 1 V.

(3) (4) 1 Cl.' 3 1 --/ CM 2 -0 -Q 0 /- NI-I So 2 0 3 N 0 2 N 'S 0 2 NI-1 \ N=N \ l' '01-1 /Cl-' 3 CH 3 So 2 CON \C 18 1 37 -CY p OCH3 0 2 CH2-0 N=N-aNO 2 OCH3 0 2 N,, 55,, S02N/ CH3 \C B H 37 NHCOC2H5 1 CD _i 1 1 i (5) 1 NHCO CH3 1 CH 2 _Ol CH3 S ce r', -A', N -0 02N o' Cl-' 3 S 0 2 Cl.' 3 1 CH -C Cl-' 2 -0- - N=N- >NO OCH3 C H 3 CN 02N, J 1 S02N/ CI-1 CH3 NHS SO 2 C 14 H 29 CN 0 2-0-N=N 1-1 T' N C- V A 1 (7) (8) k O."

--V/ C F' 2-o-aNI-I SO 2 -- 0 2 N -;-1 1 1 -- 1 1 SO 2N/ \ C 181137 CH 3 CH3 CH 3 CH3 CH3 0 2 OCH3 S 0 N=N. \110 1-1 -3 CH 3 SO 2 NI-I- - G\/ CH2 -OP-NI-1 SO 2 S02N/ CH 3 C 18 1137 2N/ C 2 1-15 C 2 1-15 So 2NI-1CH3S02-QN 01-1 N 1-1 C 0 C 21-15 1.1 1 0 I'D 1 (9) CH3 \1 /CH20C CH3-C:

1 1.13 0 2 N \NHSO 2 NH NC 02 NC N=N-\ OH ONH(CH2)3 0 C 141-129 ce CH3 CH20-aNHS02 - qJ SO 2 N H-\//\ "0 N 0 2 N,, S02N/ CH 3 \C 18 H 37 NI-ICO C 2 1" 5 02 N-QN=N OH SO 2 CH3 CO N-aMISO 2 CH 3 1 2115 0 #> 1 1 1 0 C 3 H 7 R R. C 16 H 33 0 R:

CH3 1 -CH2NCOO-G j NHS02 - 0 C 3 H 7'-1 R R C16H33 0 CH R: -C OCH2C1-120C113 =N OH C113S02N H 1 J H2NCOO- NHS02- a NH-N I,- oi 6 S02N' /C2H5 \ C 2 H 5 CN 1 1 1 112 Q3) R:

0 C 13 '-'T 27 1 CH3",CH-R CH 3Jt,, l! C 3 H 7 11 0 OCH3 -so 2 NHS02-// S-NH- 02 N lN N OH 2 S02CH3 1 1, - 113 The silver halide for use in preparation of the photographic material of the present invention may be anyone of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide and silver chloroiodobromide.

The silver halide emulsion for use in the present invention may be either a surface latent image type emulsion or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent and a photofoggant. A so-called core/shell emulsion in which the grains have different phases in the inside (core) and the surface part (shell) may also be used in the present invention. The silver halide emulsion may be either monodispersed or polydispersed, or a mixture of monodispersed emulsions may also be used. The grain size is preferably from 0.1 to 2 pm, especially preferably from 0.2 to 1.5 pm. Regarding the crystal- habit of the silver halide grains, the grains may be cubic, octahedral or tetradecahedral, or they may even be tabular grains having a high aspect ratio.

Specifically, any of the silver halide emulsions described in U.S. Patent 4,500,626, Re,search Disclosure, (hereinafter referred to as "RD") 17029 (1978), U.S. Patent

114 4,628,021 and JP-A-60-196748, JP-A-60-192937 and JP-A60-2585357 may be used in the present invention.

- The silver halide emulsion may be used in the form of a primitive emulsion but is generally chemically sensitized before use. For chemical sensitization of the emulsion, sulfur sensitization, reduction sensitization or noble metal sensitization which is known for emulsion for conventional photographic materials may be utilized singly or in combination. Such chemical sensitization may be effected in the presence of a nitrogencontaining heterocyclic compound (JP-A-58-126526 and JPA-58-215644).

In preparation of the photographic material of the present invention, the amount of the-light-sensitive silver halide to be coated is from I Mg/M2 to 10 g/M2 as silver.

In accordance with the present invention, an organic metal salt may be used as an oxidizing agent together with the light-sensitive silver halide. For such organic metal salts, organic silver salts are especially preferred.

As organic compounds which may be used for forming the organic silver salt oxidizing agents, there are the benzotriazoles, fatty acids and other compounds described in U.S. Patent 4,500,626, columns 52 and 53.

1 1 In addition, the silver salts of alkynyl group-containing carboxylic acids such as silver phenylpropionate described in JP-A-60-113235 and the silver acetylene described in JP-A-61-249044 are also useful. The organic silver salts may be used in combinations of two or more kinds.

The said organic silver sal may be used in an amount of from 0.01 to 10 mols, preferably from 0.01 to 1 mol, per mol of the light-sensitive silver halide. The total of the light-sensitive silver halide and the organic silver salt to be coated is suitably from 50 rng/M2 to 10 9/M2 as silver.

Various kinds of anti-foggants or photographic stabilizers may be incorporated into the photographic materials of the present invention. As examples of such additives, there may be mentioned the azoles and azaindenes described in RD 17643 (1978), pages 24 to 25, the nitrogencontaining carboxylic acids and phosphoric acids described -in JP-A-59168442, the mercapto compounds and metal salts thereof described in JP-A59111636, and the acetylene compounds described in JP-A62-87957.

In accordance with the present invention, an image toning agent may be incorporated into the lightsensitive element, if desired. As examples of effective 1 - 116 - toning agents, there are the compounds described in JPA-61-147244, page 24.

The silver halides for use in preparation of the photographic material of the present invention may be spectrally sensitized with methine dyes or the like dyes. Dyes which may be used for the purpose include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonole dyes.

Specifically, there may be mentioned the sensitizing dyes described in JPA-59-180550 and JPA-60-140335 and RD 17029 (1978) pages 12 to 13, as well as the heat-discoloring sensitizing dyes described in JP-A-111239 and JPA-62-32445.

These sensitizing dyes may be used singly or in combinations of two or more. The combinations of the sensitizing dyes are often used for the purpose of supersensitization.

Dyes which do not have a spectrally sensitizing action by themselves or compounds which do not substantially absorb visible light but show a supersensitizing action may also be incorporated into the emulsions for use in the present invention, together with the sensitizing dyes. (For examples, the compounds described in U.S. Patents 2,933,390, 3,635,721, I; t 1 - 117 3,743,510, 3,615,613, 3,615,641, 3,617,295 and 3,635,721 can be used for the purpose.) The time of adding the sensitizing dye to the emulsion may be during chemical ripening of'the emulsion or before or after chemical ripening thereof, or alternatively, the dye may also be added-to the emulsion before -or after the formation of the nuclei of silver halide grains in accordance with U.S. Patents 4,183,756 and 4,225,666. The amount of the dye to be added is generally f rom 10-8 to 10-2 Mol or so per mol of the silver halide.

As the binder for the heat-developing lightsensitive element- of the present invention, a hydrophilic substance is preferably used. As the hydrophilic binder, a transparent or semi-transparent substance is preferred. As examples of preferred binders, there may be mentioned natural compounds such as gelatin, gelatin derivatives and the like proteins as well as cellulose derivatives, starches, gum arabic, dextran, pullulane and the like polysaccharides; and synthetic polymer compounds such as polyvinyl alcohol, polyvinyl pyrrolidone, partial saponified products of vinyl alcohol/acrylic acid copolymer, acrylamide polymer and the water-soluble polyvinyl compounds described in JP-A62-245260. The binders may be used in the form of a 9 - 118 combination of two or more kinds. In addition to the binder, a vinyl compound dispersion may also be incorporated into the photographic material so as to increase the 4imensional stability of the material, the dispersion being used in the form of a latex.

In accordance with the present ' invention, the amount o'L the binder to be coated is preferably 20 g or less, especially preferably 10 g or less, more preferably 7 g or less, per M2 of the material.

In preparation of the photographic material of the present invention, the hydrophobic additives such as the reducible dye-forming compgund and the electrondonating substance may be incorporated into the lightsensitive element by a known method, for example, in accordance with the method described in U.S. Patent 2,322,027. In this case, the high boiling point organic solvents described in JP-A-59-83154, JP-A-59-178451, JPA-59178452, JP-A-59-178453, JP-A-59-178454, JP-A-59178455 and - JP-A-59178457 may- be used optionally together with a low boiling point organic solvent having a boiling point of from 500C to 1600C.

The amount of the high boiling point organic solvent to be used is 10 g or less, preferably 5 g or less, per g of the dye-forming compound used. This is 118 - - 119 - suitably 1 cc or less, especially 0.5 cc or less, more suitably 0.3 cc or less, per g of the binder used.

The dispersion method using a polymer described in JP-B-51-39853 (the term 11jP-B" as used herein means an "examined Japanese patent publication") and jP-A-5159943 may also be used in preparation of the photographic material of the present invention.

When the additives to be added to the photographic material of the present invention are substantially insoluble in water, these may be dispersed in a binder in the form of fine grains and the resulting dispersion may be added to the coating emulsion, in addition to the above- mentioned methods.

When the hydrophobic compound is dispersed in a hydrophilic colloid, various surfactants may be used. For example, the surfactants described in JP-A-59157636, pages 37 to 38 may be used for the purpose.

In the present invention, compounds which may improve the developability and which may improve the stability of images formed may be added to the lightsensitive element. Examples of such compounds which are preferably used for the purpose are described in U.S. Patent 4,500,626, columns 51 to 52.

in a system of forming an image by diffusion transfer of a dye, a dyefixing element is used together - with the light-sensitive element. The dye-fixing element may be in the form of being coated on_ a different support separetely from the light-s- ensitive element or alternatively this may be in the form of being coated on the same support having the lightsensitive element. Regarding the relation between the light-S'ensitive element and the dye-fixing element, the relation between the elements and the support and the relation between the elements and a white reflective layer, the description of U.S. Patent 4,500,626, column 57 may apply to the present invention.

The dye-fixing element which is preferably used in the present invention has at least one layer containing a mordant agent and a binder-. As the mordant agent, substances which are known in the photographic field can be used. As specific examples of the agents, there may be mentioned the mordant agents described in U.S. Patent 4,500,626, columns 58 to 59 and JP-A-61-88256, pages 32 to 41; and the compounds described in JP-A-60118834, JP-A-60119557, JP-A-60-235134 and Japanese Patent Application Nos. 61-87180 and 61-87181. In addition, the dye-accepting polymer compounds described in U.S. Patent 4,463,079 may also be used.

The dye-fixing element may optionally have auxiliary layers such as a protective layer, a peeling - 121 layer and a curling preventing layer. In particular, provision of a protective layer in the element is advLntageous.

As the binder for the constituting layers in the dye-fixing element, the same natural or synthetic polymer substances as the binders for the lightsensitive element may be used.

The light-sensitive element and the dye-fixing element may have, in one or more constituting layers thereof, a heat solvent, a plasticizer, an antifading agent, a UV-absorbent, a lubricant, a mat agent, an antioxidant, a vinyl compound dispersion for improving dimensional stability, a surfactant and a brightening agent, if desired. Examples of these additives are described in JP-A-61-88256, pages 23 to 26. In the case of a system where heat development and dye transference are effected simultaneously in the presence of a small amount of water, it is preferred to incorporate a base and/or a base precursor which will be mentioned hereinafter into the dye-fixing element so as to improve the storage stability of the light-sensitive element.

In the practice of the present invention, the light-sensitive element and/or the dye-fixing element may contain an image formation accelerator. The image formation accelerator has various functions of 122 accelerating the oxidation-reduction reaction between a silver salt oxidizing agent and a reducing agent, accelerating the formation of a dye from a dye'-forming substance, the decomposition of the dye therefrom and the reaction of releasing a diffusible dye from a dyereleasing substance, and accelerating the movement of the dye from the light-sensitive layer to the dye-fixing layer. From the physico-chemical functions, the image formation accelerator is classified into a group of bases or base precursors, a group of nucleophilic compounds, a group of high boiling point solvents (oils), a group of heat solvents, a group of surfactants, and a group of compounds having a mutual reactivity with silver or silver ion. However,. the substances of the groups generally have two or more functions at a time, and it is general that these substances have two or more of the said acceleration capacities. The details of these substances are described in U.S. Patent 4,678,739, pages 38 to 40.

As base precursors, there are salts of organi acids which may be decarboxylated under heat and bases, and compounds capable of releasing amines by intra molecular nucleophilic substitution reaction, Lossen re arrangement or Beckmann rearrangement. Specific examples of these compounds are described in U.S. Patent QI 123 - 4r511,493 and JP-A-62-65038. In addition to these compounds, the combination of a hardly soluble meal compound and a compound capable of reacting With the metal ion which constitutes the hardly soluble metal compound formation of a complex. (the compound being called a "complex- forming compound") as described in European Patent Application Laid-Open No. 210,660, as well as the compounds capable of generating a base by electrolysis described in JP-A-61-232451 may also be used as a base precursor. In r)articular, the former combination is effective. It is advantageous that the hardly soluble metal compound and the complex- forming compounds are separately added to the light-sensitive element and the dye-fixing element, individually.

The light-sensitive element and/or the dyefixing element for use in the present invention may contain various kinds of development stopping agents for the purpose of always obtaining a constant image irrespective of the processing temperature and the processing time in development.

The development stopping agent as referred to herein means a compound which may immediately neutralize a base or react with a base, after necessary development, to lower the base concentration in the photographic film processed so as to step the development, or 124 a compound which mutually reacts with silver or a silver salt to control the development. Suitable types of compound include, for example, an acid precursor which may release an acid under heat, an electrophilic compound which may react with the coexisting base under heat for substitution reaction, as well as a nitrogen-containing hererocyclic compound and a mercapto compound and precursors thereof. Specifically, the compounds described in U.S. Patents 4,670,373, 4,656,126, 4,610,957, 4,626,499, 4, 678,735 and 4,639,408, JP-A-61-147249, JP-A-61-147244, JP-A-61-188540, JP- A-61-269148 and JP-A-61-269143 ma y be used for the purpose.

The dyefixing element is preferably stored under the condition of a relative humidity of from 25 to 85%.

In the light-sensitive element and/or the dyefixing element of _the present invention, the constitut ing layers (photographic emulsion layer, dye-fixing layer) may contain an inorganic or organic hardening agent.

Specific examples of the hardening agent which may be used in the present invention are described in U.S. Patent 4,678,739, column 41 and JP-A-59116655, and t, 7 the compounds can be used singly or in combinations of two or more.

The support for the light-sensitive 'element and/or the dye-fixing element of the present. invention must be such that it is durable to the processing temperature. As sultat-le. supports. not only glass, paper, polymer films.' metals and analogues thereof but also the supports described in JP-A-61-147244, page 25 may be used for the materials of the present invention.

The light-sensitive element and/or the dyefixing element may be in the form that has- therein an electroconductive heater layer as a heating means for heat development or diffusion transfer of the dye formed.

In -this case, a transparent or opaque heating element may be prepared in accordance with a conventional technique which is known for formation of a resistance heater. For formation of a resistance heater, a method of using a thin film of a semiconductive inorganic material as well as a method of using a thin film of an organic substance which contains fine elect roconductive grains as dispersed in a binder may be employed.

The materials which may be utilized in the methods are described in JP-A-61-145544.The electro- - 126 - conductive layer thus formed may also function as an antistatic layer.

In preparation of the photographic materials of the present invention, the method described in U.S. Patent 4,500,626 may be employed for coating the heatdeveloping light-sensitive layer, the protective layer, the interlayer, the subbing layer, the blacking layer, the dye-fixing layer and other layers on a support.

As a light source for imagewise exposure of the photographic material of the present invention to record an imager thereon, radiations inclusive of visible rays may be used. In general, various light sources which are used in general color prints, for example, a tungsten lamp, mercury lamp, halogen lamp such as an iodine lamp, xenon lamp, laser ray, CRT ray, lightemitting diode (LED) as well as the light sources described in U.S. Patent 4,500,626, can be used for the photographic materials of the present invention.

The heating temperature in the heat development step can be from about 500C to about 2500C, and advantageously from about 800C to about 180C. The diffusion transference of the dye formed may be effected simultaneously with heat development or may be effected after heat development. In the latter case, the heating temperature in the transfer step may be from the Q1 127 temperature in the heat development step to room temperature but is more preferably from 501C up to the temperature which is lower than the temperature in the heat development by about 101C.

The transference of the dye formed may be effected solely by heating, but a solvent may also be used so as to accelerate the transference of the dye.

In addition, a method of simultaneous or continuous development and transfer by heating in the presence of a small amount of a solvent (especially water) is also advantageous, which is detail in JP-A-59218443 and JP-A-61-238056.

described in In accordance with the system, the heating temperature is preferably from 501C to the boiling point of the solvent. For instance, when water is used as a solvent, the temperature is desirably from 500C. to 100"C.

As examples of the solvent to be used for acceleration of development and/or transference of the diffusible dye to the dye-fixing layer, there may be mentioned water and an aqueous basic solution containing an inorganic alkali metal salt or an organic base. As the bases to be incorporated into the solution, those mentioned for the aforesaid image formation accelerators I may be used. In addition, a low boiling point solvent as well as a mixed solution comprising a low boiling 128 - solvent and water or an aqueous base-containing solution may also be used. If desired, a surfactant, an an.tifoggant, a difficultly soluble metal salt and a complexforming compound may be incorporated into the solvent.

The solvent may be applied to either the dyefixing element or the lightsensitive element or to both of them. The amount of the solvent to be added thereto may be small, or that is, less than the weight of the solvent which corresponds to the maximum swollen volume of the total coated film (and in particular, less than the amount obtained by subtracting the weight of the total coated film from the weight of the solvent which corresponds to the maximum swollen volume of the total coated film).

As a method for applying a solvent to the lightsensitive layer or the dyefixing layer, for example, there is the method described in JP-A-61147244, page 26. As another method, a solvent may previously be incorporated into the light-sensitive- element or the dye-fixing element or into both of them in the form of solvent-containing microcapsules.

In order to accelerate the transference of the dye to the dye-fixing layer, a hydrophilic heat solvent which is solid at normal temperature but may be melted at a high temperature may be incorporated into the - 128 -1 1 - 129 light-sensitive element or the dye-fixing element. The hydrophilic heat solvent may be incorporated into eiter the light-sensitive element or the dye-fixing element or may also be incorporated into both of them. For incorporation of the solvent into.the said element (s) the solvent may be added toany one of the emulsion layer,' interlayer, protective layer and dye-fixing layer, but is preferably added to the dye- fix.,ng layer and/or the adjacent layers.

As example,s of the hydrophilic heat solvents which may be used for the purpose, there are ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes and other heterocyclic compounds.

In order to accelerate the dye transfer, a high boiling point organic solvent may be incorporated into the light-sensitive element and/or the dye-fixing element.

As a heating means in the development and/or transfer steps, the means described in JP-A-61-147244, pages 26 to 27, such as hot plate, iron and hot roller, may be used.

When the light-sensitive element and the dyefixing element are attached to each other under pressure, the pressure condition and the means of applying a pressure to the attached elements described - 130 in JP-A-61-147244, page 27 nay apply to the case of the present invention.

Any and every heat development apparatus may be used for processing the photographic materials of the present invention. For example, the apparatus described in JP-A-59-75247, JP-A-59-177547, JP-A-59-181353 and JPA-60-18951 and JP-A-U-62-25944 (the term "JP-A-Ul' as used herein means an "unexamined published Japanese utility model application") are preferably used for the photographic materials of the present invention.

The photographic material of the present invention may give a positive color image on the dyefixing element by a heat development-transfer step. The processed photographic 'material (in the case having a lightsensitive element and a dye-fixing element on the same support, the dyefixing element is peeled off from the light-sensitive element after the material has been processed) still has a negative image based on the silver halide and developed silver together with the non-reacted dyeforming compound. Accordingly, using the negative image, the processed photographic material of the present invention may be printed onto a usual. color paper. More precisely, the photographic material as processed by heat development and dye transfer is desilvered with a known bleach-fixing solution or a C i 131 bleaching solution and a fixing solution and thereafter this is post- treated (e.g., rinsed with water) and dried to obtain a negative color image. That is, the photographic material of the present invention may be utilized not only for giving a positive image by heatdevelopment and dye transfer process but also as a negative photographic material for extra prints.

The following examples are intended to illustrate the present invention in more detail but not to limit it in any way.

Unless otherwise indicated, ratios, parts, etc. are by weight. EXAMPLE 1 all percents, Multilayer color photographic material samples each having the composition mentioned below were prepared.

Emulsion (I) for the first layer was prepared as f ollows.

600 M1 of an aqueous solution containing sodium chloride and potassium bromide and an aqueous silver nitrate solution (formed by dissolving 0.59 mol of silver nitrate in 600 ml of water) were simultaneously added to a well stirred aqueous gelatin solution (containing 20 g of gelatin and 3 g of sodium chloride in 1000 ml of water and kept at 75OC), at the same flow - 132 rate over a period of 40 minutes. Thus a monodispersed cubic silver chlorobromide emulsion (bromine 80 mol%) having a mean grain size of 0.35 pm was prepared.

After being washed with water and desalted, 5 mg of sodium thiosulfate and 20 mg of 4-hydroxy-6-methyl1,3,3a,7-tetrazaindene were added to the emulsion to chemically sensitize the same at 601C. The yield of the_ emulsion was 600 9.

Emulsion (II) for the third layer was prepared as follows.

600 ml of an aqueous solution containing sodium chloride and potassium bromide, an aqueous silver nitrate solution (formed by dissolving 0.59 mol of silver nitrate in 600 ml of water) an.d the dye solution (I) mentioned below were simultaneously added to a well stirred aqueous gelatin solution (containing 20 9 of gelatin and 3 9 of sodium chloride in 1000 ml of water and kept at 75C), at the same flow rate over a period of 40 minutes. Thus a dye-adsorbed monodispersed cubic silver chlorobromide emulsion (bromine 80 mol%) having a mean grain size of 0.35 pm was prepared.

After being washed with water and desalted, 5 mg of sodium thiosulfate and 20 mg of 4-hydroxy-6-methyl1,3,3a,7-tetrazaindene were added to the emulsion to -i . 1 1 133 chemically sensitize the same at 600C. The yield of th emulsion was 600 9. Dye Solution (I):

Dye having the following structure formula: 160 mg C2H5 1 0 CH-C=CII-<'.

E) tCI12)3SO3H tCI2)3S03 N C--"l Methanol: 400 ml Emulsion (III) for the fifth layer was prepared as follows.

1000 ml of an aqueous solution contaning potassium iodide and potassium bromide and an aqueous silver nitrate solution (formed by dissolving 1 mol of silver nitrate in 1000 ml of water) were simultaneously added to a well stirred aqueous gelatin solution (containing 20 g of gelatin and ammonia in 1000 ml of water and kept at 500C), whereupon the pAg value in the reaction system was kept constant. Thus a monodispersed octahedral silver iodobromide emulsion (iodine 5 mol%) having a mean grain size of 0. 5 pm was prepared.

- 133 - 134 - After being washed with water and desalted, 5 mg of chloroauric acid (tetra-hydrate) and 2 mg of sodum thiosulfate were added to the emulsion for gold and sulfur sensitization of the same at 600C. The yield of the emulsion was 1 kg.

Next, a gelati n dispersion containing a dyeforming( substance was prepared as follows.

18 g of Yellow Dye-forming Substance (1), 9 g of Elect ron-donat ing Substance (ED-9) and 9 g of tricyclohexyl phosphate were weighed, and 46 ml of cyclohexanone was added thereto and heated to dissolve them at about 600C to prepare a uniform solution. The resulting solution was blended with 100 g oj_ a 10% lime-processed gelatin solution, 60 cc of water and 1.5 g of sodium dodecylbenzenesulfonate with stirring and then the resulting mixture was homogenized in a homogenizer at 10000 rpm for 10 minutes. The dispersion thus obtained was called an yellow dye-forming substance dispersion.

In the same manner as preparation of the yellow dye-forming substance dispersion, except that Magenta Dye-forming Substance (2) or Cyan Dyeforming Substance (9) was used in place of the Yellow Dye-forming Substance (1), a magenta dye-forming substance dispersion and a cyan dyeforming substance dispersion were prepared. -a - Using the thus prepared emulsions and compositions, various

multilayer color photographic material samples having the layer constitution mentioned below were prepared.

The amount of the elect r.on-t ransfe r ring agent and that of the electron-transferring agent precursor in the first layer, third layer and fifth layer were varied as shown in Table 1 below. Thus photographic material samples Nos. 101, 102 and 103 were prepared.

Layer Constitution:

Sixth Layer: Protective Layer Gelatin Mat agent (Silica) Water-soluble polymer (l) Surfactant (l) Surfactant (2) Hardening agent (l) ZnS04.71120 Fifth Layer: Blue-sensitive Layer Emulsion (III) Gelatin Anti-foggant (l) Yellow Dye-forming substance (1) High boiling point organic solvent (l) (g/M2) 0.91 0.03 0.23 0.06 0.13 0.01 0.06 (g/M2) 0.58 as Aq 0.68 1. 36x10-3 0.50 0.25 - 136 Electron-donating substance (ED-9) Surfactant (3) Electron-transferring agent (X-34) Electron-transferring agent precursor (ETP-34-34) Hardening agent (l) Water-soluble polymer (2) Fourth Layer: Interlayer Gelatin Zn(OH)2 Reducing agent (l) Surfactant (l) Surfactant (4) Water-soluble polymer (2) Hardening agent (l) Third Layer: Green-sensitive Layer Emulsion (II) Gelatin Anti-foggant (l) Magenta Dye-forming substance (2) High boiling point organic solvent (l) Electron-donating substance (ED-9) Surfactant (3) Electron-transferring agent (X-34) See 0.25 0.05 See Table 1

See Table 1

0.01 0.02 (g/M2) 0.75 0.32 0.11 0.02 0.07 0.02 0. 01:

(g/M2) 0.41 as Ag 0.47 1.25x10-3 0.37 0.19 0.14 0.04 Table 1

137 - Electron-transferring agent precursor (ETP-34-34) Hardening agent (l) Waterr-soluble polymer (2) Second Layer: Interlayer Gelatin Zn(OH)2 Reducing agent (l) Surfactant (l) Surfactant (4) Water-soluble polymer (2) Hardening agent (l) First Layer: Red-sensitive Layer Emulsion (I) Sensitizing dye (l) Gelatin Anti-foggant (l) Cyan dye-forming substance (9) High boiling point organic solvent (l) Electron-donating substance (ED-9) Surfactant (3) Electron-transferring agent (X-34) Electron-transferring agent precursor (ETP-34-34) Hardening agent (l) Water-soluble polymer (2) See Table 1

0.01 0.02 (g/M2) 0.80 0.31 0.11 0.06 0.10 0.03 0.01 (g/M2) 0.36 as Aq 1.07x10-3 0.49 1.25x10-3 0.40 0.18 0.14 0.04 See Table 1

See Table 1

0.01 0.02 17 - 138 support:

Polyethylene terephthalate (thickness 100 jim) Backinq Layer:

Carbon black g/mI) 0.44 Polyester 0.30 Polyvinyl chloride 0.30 -The components used were as follows.

Water-soluble Polymer (1):

Sumika Gel L-5 (H)(manufactured by Sumitomo Chemical) Water-soluble Polymer (2):

-CH2-CH- S03K Surfactant (l): Surfactant (2) Surfactant (3); Surfactant (4) Aerosol OT -Q C9H19 0 (C112CH20) 30H C12H25 -C- S03Na C9H19 -0- 0 (CH2CH20) 8H z - 139 Hardening Agent (l):

1,2-bis(vinylsulfonylacetamido)ethan High Boiling Point Organic Solvent (l):

Tricyclohexyl Phosphate Anti-foggant (l) Sensitizing Dye (1 Reducing Agent (l):

SH Na03S"'C C2H5 61 "1 1 1 CH=C-CH-- N e (CH2)3-SO3 (CH2h-SO3EN(C2H5)3 OH nCl4H29,, 5;, zll bu3ra OH Next, a dye-fixing material sample (R-1) was prepared by forming the layers each having the composition mentioned below on a polyethylene- laminated paper support.

- 140 - Layer Constitution: Third Layer:.Gelatin Matt agent (Silica) Silicone oil (1) Surfactant (2) Surfactant (3) Surfactant (4) Guanidine picolinate Polymer (5) Second Layer: Mordant agent (6) Polymer (7) Gelatin Polymer (5) High boiling point organic solvent (8) Guanidine picolinate Surfactant (2) First Layer: Gelatin Surfactant (4) Polymer (5) Hardening agent (9) (g/M2).

0.05 0.02 0.04 0.001 0.02 0.10 0.45 0.24 (g/M2) 2.35 0.60 1.40 0.21 1.40 1.80 0.02 (g/M2) 0.45 0.01 0.04 0.30 - 141 Support:

Polyethylene-laminat - 170 PM) First Backinq Layer:

Gelatin Hardening agent (9) Second Backinq Layer:

Gelatin Silicone oil (1) Surfactant (5) Matt agent (10) The compounds used were as follows.

Silicone Oil (1):

CH3 CH3 CH3 1 1 1 CH3 1 C113-Si-O-tSi-0) 20 (Si-0) 4 Si-CH3 1 1 1 1 C113 CH3 Surfactant (2): Aerosol OT Surfactant (3):

C8F17S02NCI-12COOK 1 C3117 ed Paper Support (thickness (g/M2) 3.25 0.25 (g/M2) 0.44 0.08 0.002 0.09 (CM3) 3LUU1-1 -113 i 142 - Surfactant (4) Surfactant (5) C113 1 C11H23CONHCH2CH2CH2NeCH2COO0 CH3 C3H7 1 C8F5S02N(CH2CH20) 4 (CH2 -4S04Na Polymer (5): Vinyl Alcohol/Sodium acrylate Copolymer (75/25, by mol) Polymer (7): Dextran (molecular weight 70,000) Mordant Agent (6):

High Boiling Point Organic Solvent (8):

tCH2-CH).,.(CH2-CH) 30 H2-CHj10 1 N CH =0 S S02K Reofos 95 (manufactured by Ajinomoto Co.) Hardening Agent (9):

* / 0 \ (CH2t-4tO-CH2-CH-CHJ-2 1 LlattAgent (10): Benzoquanamine Resin (mean grain size lim) IN 4 le 143 - The multilayer color photographic material samples were exposed with a tungsten lamp (5000 lux) through a blue-green-red-gray color separation filter with continuous color density variation, for 1/10 second.

After exposure, water (15 the emulsion surface of the thus wire bar, while the sample was velocity of 20 mm/sec, and then attached to the image-receiving material (R-1)) with both coated other.

The thus attached sample was heated with a heat roller which was so adjusted that the temperature of the water-absorbed layer could be 850C, for 15 seconds. Next, the image-receiving material was peeled off, whereby a sharp image with blue, green, red and green colors corresponding to the color separation filter was evenly formed on the material.

The maximum density (Dmax) and the minimum density (Dmin) of each of the cyan, magenta and yellow colors in the gray part were measured, and the results obtained are shown in Table 1 below.

M1/M2) was applied to exposed sample with a conveyed at a linear immediately this was material (dye-fixing surfaces facing each 0.

Electron Sample transferrinq Aqent Aqent Precursor Dmax Dmin No. lst, 3rd and 5th layers lst, 3rd and 5th layers Yellow Maqenta Cyan Yellow Maqenta Pyan TABLE 1

Electron-transferring 1 101 102 103 (g/M2) 0.03 0.06 0 (g/M2) 0 0 0.05 2.10 2.00 2.25 0.18 0.16 0.15 2.00 1.98 2.31 0.16 0.15 0.15 2.05 2.06 2.23 0.60 0.61 0.58 1 A cl 1 From the results shown in Table 1 above, it is understood that the use of the electron-transferring agent precursor alone resulted in a high Dnin value so that an image with a good SIN ratio could not be obtained. On the contrary, images which were satisfactory both in Dmax and Dmin were obtained in the samples Nos. 101 and 102.

Next, the composition of the electron-transferring agent and the electrontransferring agent precursor in the first, third and fifth layers in the sample No. 101 was varied as indicated in Table 2 below, while the others were same as those in the sample No. 101. Thus other photographic material sample Nos. 104 to 109 were prepared. The samplis ' Nos. 101 and 104 to 109 were stored for 7 days under the conditions of a temperature of 400C and a humidity of 70% (storage condition (A)) or under the condition of a temperature of 50C and a humidity of 30% (storage condition (B)). The thus stored samples were processed in the same manner as described above, and the Dmax and Dmin values of the cyan, magenta and yellow colors in the gray part in the images obtained-.were measured analogously. The results obtained are shown in Table 3.

The photographic properties of samples Nos. 104 to 109 in a Eresh state immediately after preparation wer.e same as those of the fresh sample No. 101.

- 145 - TABLE 2

Amoun of Electron Electron-trans- Electron-transferring Amount of Electron- transferring Agent Sample No. ferrinq Aqent Aqent Precursor transferrinq Aqent Precursor (g/M2) (g/rn2) 101 X-34 0.03 0 104 ETP-34-11 0.03 ETP-34-34 0.05 106 ETP-34-43 0.06 107 ETP-34-31 0.06 108 ETP-34-50 0.04 109 ETP-34-47 0.06 lst, 3rd and 5th layers 1 X,.

4 4- 4 1 1 1 TABLE 3 f Storage Dmax Dmin Sample No. condition Yellow Maqenta Cyan Yellow Magenta. CYan 101 2.09 2.05 2.32 0.45 0.41 0.43 104 A 2.03 2.05 2.23 0. 28' 0.23 0.25 400C 2.08 2.06 2.25 0.19 0.18 0.17 70% 106 7 days 2.05 2.03 2.27 0.27 0.24 0.26 107 2.06 2.05 2.31 0.18 0.17 0.18 108 2.05 2.07 2.30 0.19 0.17 0.18 109 2.07 2.04 2.29 0.18 0.18 0.17 101 2.01 2.04 2.12 0.48 0.49 0.47 104 B 2.00 2.02 2.04 0.30 0.25 0.26 5TOC 2.00 2.00 2.03 0.20 0.18 0.16 40% 106 7 days 1.97 2.01 2.02 0.29 0.25 0.27 107 2.01 2.03 2.10 0.20 0.19 0.16 108 1.98 2.04 2.11 0.21 0.18 0.17 109 1.99 2.00 2.09 0.19 0.18 0.17 148 - As is obvious f rom the result-ts shown in Table 3 above, Dmin was lower in sample Nos. 104 to 109 containing both electron-transt=rring agent and electron-transferring agent precursor than in sample No. 101 having electron-t- ransf erring agent only, when the samples were photographically processed after being stored.' Accordingly, it is understood that heatdeveloping color photographic materials containing both electron-transferring agent and electron-transferring agent precursor may give an image with a low Dmin value and a good SIN ratio, even when they are photographically processed after being stored for a certain period of time.

Regarding the time-dependent Dmin value in_ the samples Nos. 164 to 109, it is noted from the results in Table 3 that the Dmin value in the samples 105 and 107 to 109 was lower than that in the samples 104 and 106. The relative decomposition speed of the electron-transferring agent precursor used in samples Nos. 104 to 109 to the electron-transferring agent X-34 in the layer of the photographic material is shown in Table 4 below.

T 149 - TABLE 4

Electron- Decomposition Decomposition.

Transferring Speed Speed Sample Agent (400C, 70%r (500C, 40%, No. (Precursor) 7 days) 7 days) X-34 1 1 104 ETP-34-11 150 90 108 ETP-34-50 4.8 5 107 ETP-34-31 1.6 1.8 ETP-34-34 0.9 0.9 109 ETP-34-47 0.2 0.3 106 ETP-34-43 0.01 0.02 From the results in Tables 3 and 4, it is understood that the combination of electron-t-ransf erring agent and electron-transf erring agent precursor in which the relative decomposition speed of the precursor is from 0.1 to 5 times or so of the corresponding electrontransferring agent is especially preferred.

EXAMPLE 2

In the same manner as preparation of the sample No. 105, except that the electron-transferring agent precursor ETP-34-34 was replaced by the same molar amount of another electron-transf erring agent precursor ETP-34-32, ETP-34-33, ETP-34-35, ETP-34-36 or ETP-34-40, which has a relative decomposition speed of from 0.1 to 5 times of the corresponding electrontransf erring agent - 150 - X-34, other photographic material sample Nos. 201 to 205 were prepared. These samples were stored under he conditions (A) or (B) described in Example 1 and then photographically processed in the same manner as in)Q; Example 1. As a result, all the sample! gave an image with a good SIN ratio. EXAMPLE 3 In the same manner as preparation of sample No. 101, except that the electron-transferring agent and electron-tran'sf erring agent precursor were added to the layers as indicated in Table 5 below, other photographic material sample Nos. 201 to 206 were prepared.

1 t;.

1 Ilk TABLE 5 v Amount added per one layer_ Amount added to lst, 3rd_and 5th layer Amount added to 2nd and 4th layers Sample Electron-transElectrontransferring No. ferrinq Aqent Aqent Precursor 201 202 203 204 205 206 X-34 0.03 X-34 0.03 ETP-34-34 0.05 ETP-34-43 0.06 Electron-transElectron-transferring ferrinq Aqent___ Aqent Precursor X-34 0.045 X-34 0.045 X-34 0.045 X-34 0.045 ETP-34-34 0.08 ETP-34-34 0.08 ETP-34-43 0.09 ETP-34-43 0.09 1 b_ Ln b_ 1 152 - Sample Nos. 201 to 206 were stored under the same conditions as described in Example 1 and then photographically processed - in the same mafiner as described in Example 1. As a result, all the samples gave a positive image with a good S/N ratio.

EXAMPLE 4

In the same manner as preparation of sample No. 105, except that the electron-transferring agent X-34 and the elect ron-transf erring agent precursor ETP-34-34 were replaced by the compounds indicated in Table 6 below, other photographic material sample Nos. 301 to 309 were prepared.

TABLE 6

Electron-transferring Acient Electron-transferring Aqent Precursor Sample Amount added to Amount added to No. lst, 3rd and 5th layers lst, 3rd and Sth layers 301 302 303 304 305 306 307 308 309 (g/M2) X-12 11 11 X-36 11 t 9 X-52 11 1 t 0.03 11 11 0.06 el 9 1 0.05 21 11 (g/M2) ETP-12-54 ETP-12-34 ETP-12-68 ETP-36-14 ETP-36-6 ETP-36-66 ETP-52-6 ETP-52-34 ETP-52-60 0.08 0.07 0.09 0.06 0.07 -0.07 0.08 0.08 0.06 t i 1 i 1 i i i 1 N5F 1 - 153 The samples were processed, immediately after being prepared and after being stored under the cQndilt-ions (A) or (B), in the same manner as described in Example 1. As a result, these gave a positive color image with a good SIN ratio under any condition.

EXAMPLE 5

Using the same emulsions, dye-forming sub7 stances, electron-transferring substance and electrontransferring agent as those in sample No. 101 in Example 1, a multilayer color photographic material (sample No. 401) having the layer constitution mentioned below was prepared.

Unless otherwise specifically indicated, the additives were same as those used in sample No. 101._ The organic silver salt emulsion was prepared as f ollows.

g of gelatin and 5.9 g of 4-acetylaminophenylpropiolic acid were dissolved in 1000 ml of an aqueous 0.1% sodium hydroxide solution and 200 ml of ethanol. The resulting solution was stirred at 400C. A solution of 4.5 g of silver nitrate as dissolved in 200 ml of water was added thereto over a period of 5 minutes. Next, the excess salts were removed by flocculation. Then the pH value of the dispersion was z 154 - adjusted to 6.3. Thus 300 9 of an organic silver salt dispersion was obtained.

Anti-foggant Precursor (1) (1) having the following structural formula was added to the dyeforming substance in an amount in - mols of 0. 2 time that of the latter, and the precursor, the dye-forming substanbe and the electron-donating substance were oildispersed before use. Layer Constitution: Sixth Layer: Protective Layer Gelatin Mat agent (Silica) Surfactant (l) 1 Surfactant (2) Hardening agent (l) Base precursor (l) Fifth Layer: Blue-sensitive Layer Emulsion (III) Organic silver salt emulsion Gelatin Anti-foggant precursor (l) Yellow dye-forming substance (1) High boiling point organic solvent (l) Electron-donating substance (ED-6) I (g/m2) 0.91 0.03 0.06 0.13.

0.01 0.30 (g/M2) 0.30 As Aq 0.25 As Aq 1.00 0.07 0.50 0.75 0.35 I I 1 1 1 1 1 1 i - Surfactant (3) Electron-transferring agent precursor (ETP-34-34) Electron-transferring agent (X-34) Heat solvent (l) Hardening agent (l) Base precursor (l) Water-soluble polymer (2) Fourth Layer: Interlayer Gelatin Reducing agent (2) Surfactant (l) Surfactant (4) Water-soluble polymer (2) Hardening agent (l) Base precursor (l) Third Layer: Green-sensitive Layer Emulsion (II) Organic silver salt emulsion Gelatin Anti-foggant precursor (l) Magenta dye-forming substance (2) High boiling point organic solvent (l) Electron-donating substance (ED-6) 0.05 0.06 0.04 0.20 0.01 0.27 0.02 (g/M2) 0.75 0.24 0.02 0.07 0.02 0.01 0.25 (g/M2) 0.20 As Ag 0.20 As Ag 0.85 0.04 0.37 0.55 0.20 - 156 Surfactant (3) Electron-transferring agent precursor (ETP34-34) Electron-transferring agent (X-34) Heat solvent (l) Hardening agent (l) Base precursor (l) Water-soluble polymer (2) Second Layer: Interlayer Gelatin Reducing agent (2) Surfactant (l) Surfactant (4) Water-soluble polymer (2) Base precursor (l) Hardening agent (l) First Layer: Red-sensitive Layer Emulsion (I) Organic silver salt emulsion Sensitizing dye (l) Gelatin Anti-foggant precursor (l) Heat solvent (l) Base precursor (l) 0.04 0.06 0.04 0.16 0.01 0.25 0.02 (g/M2) 0.80 0.24 0.06 0.10 0.03 0.25 0.01 (g/M2) 0.20 As Ag 0.20 As Aq 1. 07x10-3 0.85 0.04 0.16 0.25 T i 1 i i 1 I i i i 1 157 v 1 Cyan dye-forming substance (9) High boiling point organic solvent (l) Electron-donating substance (ED-6) Surfactant (3) Electron-transferring agent precursor (ETP-34-34) Electron-transferring agent (X-34) Hardening agent (1) Water-soluble polymer (2) Support:

Polyethylene terephthalate (thickness 100 jim) Backinq Layer: (g/m2) 0.40 0.60 0.20 0.04 0.06 0.04 0.01 0.02 Carbon black Polyester Polyvinyl chloride The components used were as follows.

Anti-foggant Precursor (l) CH3 -N C H 2 S --/ Ii k13( -C N-N 0 -z, 0 CH3 "N 6 02N 5., CONHC16H33 (n) Heat Solvent (l): Benzenesulfonamide 0.44 0.30 0.30 d i 1 158 Base Precursor (l):

Reducing Agent (2):

Guanidine 4-chlorophenylsulfonyl acetate OH., S03Na (n)H33C16 f OH In the same manner as preparation of sample No. 401, except that the electron-transferring agent X-34 was replaced by the same molar amount of the electrontransferring agent X-37, another photographic material sample No. 402 was prepared. Also in the same manner as preparation of sample No. 401, except that the electrontransferring agent precursor ETP-34-34 was replaced.by a 1.5. times molar amount of the electrontransferring agent precursor ETP-34-31, still another photographic material sample No. 403 was prepared. For comparison, a comparative sample No. 404 was prepared in the same manner as preparation of sample No. 401 except that the electron-transferring agent precursor was not added.

Next, a dye-fixing material (R-2) was prepared as follows.

g of poly(methyl acrylate-co-N,N,N-trimethylN-vinylbenzylammonium chloride) (in which the ratio of 1 1 i W i - 159 - V v methyl acrylate to vinylbenzylammonium chloride was 1/1) was dissolved in 200 ml of water and then uniformly blended with 100 9 of a 10% lime- processed gelatin.. A hardening agent was added to the resulting blend, which was then evenly coated on a titanium dioxide dispersioncontaining polyethylene-laminated paper support in a wet thickness of 90 pm. The thus prepared sample was dried and used as a dye-fixing material (R2) having a mordant layer.

The previously prepared photographic material samples were exposed in the same manner as described in Example 1 and then uniformly heated on a heat block heated at 1400C for 30 seconds.

Water was applied to the coated surface of the dye-fixing material (R-2) in an amount'of 20 M1/M2,_ and then the heated photographic material sample was attached to the wetted fixing material (R-2) with both surfaces facing each other.

Afterwards, the thus attached sample was passed through a laminater heated to 800C at a linear velocity of 12 mm/sec. Then both sheets were peeled away from each other, whereby a positive image with a good SIN ratio was formed on the dye-fixing material in every case.

Next, samples Nos. 401 to 404 were stored under the same conditions as described in Example 1 and then processed in the same manner as described above. As a result, the Dmin value in the image from sample No. 404 containing no electron- transferring agent precursor increased in an amount of 0.4 to 0.5 in every color of yellow, magenta and cyan. However, in the images from sample Nos. 401 to 403, the increase of the Dmin value was only 0.05 to 0. 15. It is understood from these results that the combination of electron- transf erring agent and electron-transferring agent precursor is effective for improving -the raw stock stability of photographic materials.

1 1 :z 1.

1 v V - 161

Claims

CLAIMS:

1. A heat-developable color photo.graphic material comprising a support having thereon at least a light-sensitive silver halide, a binder, at least one of an electron-donating agent and a precursor thereof, a reducible dye-forming compound which releases a diffusible dye by reduction and an electron-transferring agent, wherein an electrontransferring agent precursor co-exists together with said electrontransferring agent.

2. A heat-developable color photographic material as claimed in claim 1, wherein said electrontransferring agent is a compound represented by formula (X-I) or (X-II):

OH R2 'k 5;, 1 R' 3 R' R N R6.11 111 R.5 (X-I) 7 R 1 0 C -c-x1 1 9 H1q, N R10 (X-II) wherein R represents an aryl group; and R1, R2, R3, R4, R5, R6, R7, RS, R9 and R10, which may be the same or different, each represents a hydrogen atom, a halogen atom, a hydroxyl group, an acylamino group, an 162 - alkoxy group, an alkylthio group, an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group.

3. A heat-developable color photographic I material as claimed in claim I or 2, wherein the concentration of said electron-transferring agent by mole is from 0.001 to 4 times the concentration of said lightsensitive silver halide.

4. A heat-developable color photographic material as claimed in claim 3, wherein the concentration of said electron-transf erring agent by mole is from 0.003 to 0.

5 times the concentration of said light-sensitive silver halide.

A heat-developable color photographic material as claimed in any preceding claim, wherein said electron-transf erring agent precursor is a compound repre- sented by formula (W-1), (W-II) or (W-III):

(W-I) (W-II) (W-III) R7 Y-O R7 R4 R3 1 1 1R

6 0- -C-R' C-C-R8 1 9 11 Y-O N Y-N R N R9 R5 N 10 N 2 1 R 1 R10 R R 1 m m i 163 :j v wherein R represents an aryl group; R1,-R2r R3, R4, RS, R6, R7, R8, R9 and R10, which may be the same or different, each represents a hydrogen atom, a halogen atom, a hydroxyl group, an acylamino group, an alkoxy group, an alkylthio group, an dlkyl group, a substituted alkyl group, an aryl group or a substituted aryl group; and Y represents a substituted alkyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a substituted carbamoyl group, a sulfamoyl group, a substituted sulfamoyl group, a group having a formula as folloQs:, P 1 /P no (L) In 0 (Z)Mwherein Z represents a divalent linking group, bonded to the phthalide nucleus via an oxygen atom; L represents a halogen atom, an alkyl group, an alkenYl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, a carbonic acid ester group, an amino group, a carbonamido group, a sulfonamido group, an ureido group, an aminosulfonamido group, a carbamate group, a 164 carboxyl group, an oxycarbonyl group, a -carbamoyl group, an acyl group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a cyano group or a nitro group; and m represents 0 or 1, or a group having a formula as follows:

0 0 11 11 -C-M-C-Q 1 R11 R12 R13 1 1 wherein m represents -(CH)n- or -C = C-; n represents 2 or 3; R11 represents a hydrogen atom, an alkyl group, a phenyl group, a halogen atom or an alkoxy group; R12 and R13, which may be the same or different, each represents a halogen atom, an alkyl group or a phenyl group, or R12 and R13 may be ring-closed to form a benzene ring; and R14 I Q represents a hydroxyl group, - N - OR15 or R16; R14 represents a hydrogen atom, an aryl group or an alkyl group; R15 represents a hydrogen atom or an acyl group; and R16 represents a hydrolyzable group.

31 T W - 165 6. A heat-developable color photographic material as claimed in any preceding claim, wherein the concentration of said electron-transf erring agent -precursor by mole is from 0.01 to 20 times the concentration of said co-existing electron-transferring agent.

7. A heat-developable color photographic material as claimed in claim 6, wherein the concentratiofi of said electron-transf erring agent precursor by mole is from 0.1 to 5 times the concentration of said co-existing electron-transferring agent.

8. A heat-developable color photographic material as claimed in any preceding claim, wherein the decomposition speed of said electrontransferring agent precursor in said material is from 0.01 to 100 times the decomposition speed of said electron-transferring agent existing in said material.

9. A heat-developable color photographic material as claimed in claim 8, wherein the decomposition speed of said electron-transferring agent precursor in said material is from 0.1 to 5 times the decomposition speed of said electron-transferring agent existing in said material.

10. A heat-developable coloK photographic material as claimed in claim 1, wherein said at least one - 166 of elect ron-dona ting agent or- a precursor thereof is a compound represented by formula (C) or (D):

(C) (D) R17 OA, R19 1 R18 R70 0A2 OA, P17 0A2 1 R18 R 20 R19 wherein Al and A2. which may be the same or different, each represents a hydrogen atom or a protective group for phenolic hydroxyl group capable of being deprotected by nucleophilic agent; and R17r R18, R19 and R20, which may be the same or different, each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkylsulfonyl group, a sulfo group, a halogen atom, a cyano group, a substituted or 7 v r 1 t k 1 v - 167 unsubstituted carbamoyl group, a substituted or unsubstituted sulfamoyl group, a substituted unsubstituted amido group, a substituted or unsubstituted imido group, a carboxyl group or a substituted or unsubstituted sulfonamido group, provided that the total number of carbon atoms in R17. R18r R19 and R20 is 8 or more; and at least one combination of R17 and R18, and R19 and R20 in formula (C), and at least one combination of R17 and R18, R18 and R19, and R19 and R20 in formula (D) may be bonded to each other to form a saturated or unsaturated ring.

11. A heat-developable color photographic material as claimed in any preceding claim, wherein said reducible dye-forming compound is a compound represented by formula (L):

PWR (Time)t - Dye (L) wherein PWR represents a group capable of releasing -(Time)t-Dye by reduction; Time represents a group which releases Dye by the subsequent reaction, after having been released from PWR in the form of -(Time)t-Dye; t represents 1 or 0; and Dye represents a dye or a precursor thereof.

1 i - 168 -

12. A heat-developable color photographic material as claimed in claim 11, wherein said reducible dye-forming compound is a compound represented by formula (L-II):

(L-II) X / N 1 EAG--- R21.

(Time-y-tDye wherein (Time)t-Dye is bound to anyone of R21, R22 or EAG; X represents an oxygen atom, a sulfur atom or a nitrogencontaining group NR23-; R21, R22 and R23, which may be the same or different, each represents a bond or a substituent other than hydrogen; and EAG represents an aromatic group which accepts an electron from a reducing substance.

13. A heat-developable color photographic material as claimed in claim 12, wherein said reducible dye-forming compound is a compound represented by formula (L-III):

i i 11 i 169 (L-III) x\ /.

1 ".... EAG R 24 1 --------- Y1 (Timej -tDye wherein (Time) t-Dye is bound to any one of R24 and EAG; Y1 represents a divalent linking group; X and EAG have the same meanings as in claim 10; and R24 represents an atomic group which is bonded to X and YI to form a 5-membered to 8-membered monocyclic or condensed heterocyclic ring including nitrogen.

14. A heat-developable color photographic material as claimed in Claim 1, substantially as hereinbefore described in any of the Examples.

15. A method of forming a colored recording which comprises imagewise exposing to light and overall heat development of a material as claimed in any preceding claim.

Published 1989 at The Patent Office, State House, 66/71 High Holborn, London WCIR 4TP. Further copies maybe obtained from The Patent Offlce. Sales Branch, St Mary Cray, Orpington, Rent BRS 3RD. Printed by Multiplex techniques ltd, St Mary Cray, Kent, Con. 1/87