Silver Halide Photographic Materials

The present invention relates to silver halide photographic materials, in particular, to those containing new compound(s) which, when reduced, can release a photographically useful group which release is triggered by the cleavage of the nitrogen-nitrogen single bond in the compound.

In photographic elements compounds which provide a photographically useful group, which is immobile, ballast stabilized or blocked at the active site thereof include positive image forming compounds as illustrated in Belgian Pat. No. 810,195, U.S. Pat. Nos. 4,199,354, 3,980,479 and 4,139,379 and Japanese patent application (OPI) No. 130972/79. (The term "OPI" as used herein means an "unexamined published application".) These compounds are immobile or photographically inactive but can release a mobile photographically useful group by an intramolecular nucleophilic displacement reaction or an intramolecular electron transfer reaction.

Compounds having the aforesaid function have various merits and improving the characteristics and features of positive forming compounds has been desired to further increase the freedom of planning and the tolerance in the formation of photographic elements and the methods. In photographic elements before and after processing, the possibility of providing compounds with higher stability is desirable. In addition, the provision of more advantageous means for the control of the release of the photographically useful group or component is also desirable.

The present inventors studied reactions for cleaving a single bond in a compound after the compound has received an electron from a reducing substance. Various types of single bonds which may be relatively easily cleaved by reduction are known, including a carbon-sulfur bond and a carbon-halogen bond. However, such single bonds that can be easily cleaved by reduction but which are stable to acids, alkalis and heat are fairly limited. Further, such bonds that are stable to the aforesaid various conditions but which can be reduced by conventional organic reducing agents which are generally used in the field of photography to participate in the release of photographically useful groups are extremely limited. Some compounds are known which act in accordance with the above reaction, for example, as described in European Pat. No. 0045129A2 and West German (OLS) No. 3,008,588. However, it is difficult to conclude that these compounds sufficiently satisfy the desired characteristics of positive forming compounds as well as the necessary tolerance and freedom in the formation or planning of photographic elements, generally because of the chemical properties of the bond to be cleaved or because of difficulties in the synthesis of the compounds.

Also, in U.S. Pat. No. 4,619,884 N'N'-diarylsulfohydrazide compounds which release a photographically useful group by the cleavage of the nitrogen-nitrogen single bond are disclosed but they are yet insufficient in regard to characteristics as positive image forming compounds and the difficulty for synthesis of these compounds.

The objects of the invention is to provide a silver halide photographic material containing novel compound(s) which is/are stable to acids, alkalis, and heat but, when the compound accepts an electron from a reducing substance as is generally used in the field of photography, it releases a photographically useful group which is triggered by the cleavage of the nitrogen-nitrogen single bond in the compound which occurs easily.

The inventors selected the nitrogen-nitrogen bond as the bond which is stable to acids, alkalis and heat and which is easily cleaved by reduction and conducted studies thereon. It is known that the stability of the nitrogen-nitrogen single bond to acids, alkalies and heat largely varies depending upon the substituentes thereon but the inventors have confirmed that said bond is sufficiently stable for use in photographic materials by selecting appropriate substituentes therefore. Furthermore, the inventors have directed intensive studies to facilitating the reductive cleavage of the nitrogen-nitrogen single bond with a compound which is known as a general photographic reducing agent and have found that the nitrogen-nitrogen single bond is easily cleaved by bonding an electron-acceptive aromatic group to at least one nitrogen atom and blocking the nitrogen bonded to the electron-acceptive aromatic group.

The cleavage of the nitrogen-nitrogen single bond in the compounds thus planned and synthesized is substantially irreversible, and therefore, the cleavage reaction proceeds at a surprisingly higher speed than the speed expected from the oxidation-reduction equilibrium system. Accordingly, any stable reducing agent which is sufficiently resistant to oxidation by oxygen in the air can be used for the reduction of the compounds, which is highly advantageous.

The detailed mechanism of the cleavage reaction of the nitrogen-nitrogen bond in this invention has not yet been clarified but it is assumed that the reaction proceeds in a mechanism similar to a series of reactions described in Angewante Chemie International Edition, Vol. 14, No. 11, 735 (1975).

More precisely, the compound of this invention will accept one electron from a reducing substance to become an anion radical and the reducing substance becomes the one-electron-oxidized form. This reaction is considered to be in an equilibrium state but since the formation of the anion radical intermediate proceeds irreversibly to the direction for the cleavage of the nitrogen-nitrogen single bond in the reaction, the reaction itself is considered to easily proceed in the direction of releasing the photographically useful group from the compound.

The present invention is based upon the aforesaid technical background. More precisely, in a compound having a nitrogen-nitrogen single bond with an electron-accepting group bonded thereto, the nitrogen-nitrogen single bond is cleaved when the electron-accepting group accepts an electron, whereupon the de-blocked nitrogen atom acts as a trigger thereby to release a photographically useful group from the compound.

Accordingly, the invention provides a silver halide photographic material comprising a support having provided thereon at least one silver halide emulsion layer containing a compound represented by formula (I): ##STR2##

wherein EAG represents an aromatic group bonding to N.sub.A and N.sub.B capable of accepting an electron;

N.sub.A and N.sub.B each represents a nitrogen atom;

R.sup.1 represents a lone pair, a .pi.-bond, a .sigma.-bond, or a substituent other than a hydrogen atom;

n represents 2 or 3;

m represents 0 when n represents 2, or m represents 1 and Ns has a positive charge when n represents 3;

X.sup..crclbar. represents an anion;

the groups or bonds represented by R.sup.1 may be combined with each other or may be combined with EAG to form a ring;

R.sup.2 represents R.sup.3 --CO--, R.sup.3 --SO.sub.2 --, R.sup.3 --CO--N.dbd.CH--, or R.sup.3 --SO.sub.2 --N.dbd.CH--, wherein R.sup.3 represents an alkyl group, an aryl group, or a heterocyclic group;

the group represented by R.sup.2 may be combined with at least one of R.sup.1 and EAG to form a ring;

Time represents a group releasing PUG via subsequent reaction triggered by the cleavage of the nitrogen-nitrogen bond in said compound represented by formula (I);

PUG represents a photographically useful group;

t represents 0 or 1; and

dotted lines indicate that at least one of them represents a bond.

The invention will now be explained in detail.

In formula (I) described above, examples of the substituent shown by R.sup.1 as substituentes other than hydrogen atom are an alkyl group, an aryl group, and a heterocyclic group and these groups may be further substituted.

R.sup.2 is as defined above.

Examples of the alkyl group, aryl group and heterocyclic group shown by R.sup.1 or by R.sup.3 in R.sup.3 --CO--, R.sup.3 --SO.sub.2 --, R.sup.3 --CO--N.dbd.CH-- or R.sup.3 --SO.sub.2 --N.dbd.CH-- are a substituted or unsubstituted alkyl group (e.g., a methyl group, an ethyl group, a sec-butyl group, a t-octyl group, a benzyl group, a cyclohexyl group, a chloromethyl group, a dimethylaminomethyl group, a n-hexadecyl group, a trifluoromethyl group, a 3,3,3,-trichloropropyl group, a methoxycarbonylmethyl group, etc.), a substituted or unsubstituted 5-membered to 8-membered heterocyclic ring residue (e.g., a 2-pyridyl group, a 1-imidazolyl group, a benzothiazol-2-yl group, a morpholino group, etc.).

X.sup..crclbar. in formula (I) may be an inorganic anion or an organic anion and typical examples thereof are a halogen ion (e.g., a chlorine ion, a bromine ion, a fluorine ion, etc.), an alkylsulfonate ion (e.g., a p-methylsulfonate ion, etc.,), a thiocyanate ion, a perchlorate ion, etc. When n is 2, the ion is unnecessary (m=0).

In the compounds shown by formula (I) described above, the compounds of following formula (II) are particularly preferred for the characteristics as positive image forming compounds in that they are stable to alkali during storage or processing, they quickly release a photographically useful group on reduction, and they give desired effects without detremental effects, as well as for increasing the tolerance and freedom in the synthesis planning thereof. ##STR3## wherein R.sup.10 represents a mere bond (.pi. bond), ##STR4## or R.sup.12 --SO.sub.2 --(wherein R.sup.12 represents an alkyl group, an aryl group, or a heterocyclic group);

R.sup.11 represents an atomic group forming a 3- to 8-membered heterocyclic ring together with N.sub.A and Z;

Z represents >C.dbd.O, >SO.sub.2, >C.dbd.N--CO--R.sup.3, or >C.dbd.N--SO.sub.2 --R.sup.3 ;

and EAG, Time, t, PUG and R.sup.3 are as defined in formula (I).

Examples of the ring formed by R.sup.11, N.sub.A, N.sub.B and Z are as follows. ##STR5##

In the above formulae, R.sup.101 represents ##STR6## or R.sup.12 --SO.sub.2 -- (wherein R.sup.12 is as defined above);

R.sup.13, R.sup.14, and R.sup.15 each represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group (specific examples of the groups are those described above as R.sup.1); and

EAG is bonded to the nitrogen atom and represents an aromatic group which accepts an electron from a reducing substance.

EAG is preferably represented by the following formula (A) ##STR7##

In formula (A), Z.sub.1 represents ##STR8## V.sub.n' represents an atomic group necessary for forming a 3- to 8-membered aromatic ring together with Z.sub.1 and Z.sub.2 ;

n' represents an integer of from 3 to 8; V.sub.n 's thus mean the following;

V.sub.3 : --Z.sub.3 --, V.sub.4 : --Z.sub.3 --Z.sub.4 --, V.sub.5 : --Z.sub.3 --Z.sub.4 --Z.sub.5 --,

V.sub.6 : --Z.sub.3 --Z.sub.4 --Z.sub.5 --Z.sub.6 --, V.sub.7: --Z.sub.3 --Z.sub.4 --Z.sub.5 --Z.sub.6 --Z.sub.7,

V.sub.8 : --Z.sub.3 --Z.sub.4 --Z.sub.5 --Z.sub.6 --Z.sub.7 --Z.sub.8 --.

Z.sub.2 to Z.sub.8 each represents ##STR9## (wherein Sub represents a mere bond (.pi.-bond), a hydrogen atom or a substituent as illustrated below; the Sub's may be the same or different or they may combined with each other to form a 3- to 8-membered saturated or unsaturated carbon ring or a heterocyclic ring.

In formula (A), the Sub's are selected so that the total sum of the Hammett's substituent contents (.sigma..sub.p) of the substituentes is at least +0.50, preferably at least +0.7, and most preferably at least +0.85.

Examples of the substituentes as Sub are illustrated below (wherein the carbon atom number is preferably from 0 to 40).

Substituted or unsubstituted alkyl groups (such as a methyl group, ethyl group, sec-butyl group, t-octyl group, benzyl group, cyalohexyl group, chloromethyl group, dimethylaminomethyl group, n-hexadecyl group, trifluorodimethylaminomethyl methyl group, 3,3,3-trichloropropyl group, methoxycarbonylmethyl group), substituted or unsubstituted alkinyl groups (such as a vinyl group, 2-chlorovinyl group, 1-methylvinyl group), substituted or unsubstituted alkynyl groups (such as an ethynyl group, 1-propinyl group), a cyano group, a nitro group, a halogen atom (such as fluorine, chlorine, bromine, iodine), substituted or unsubstituted heterocyclic groups (such as a 2-pyridyl group, 1-imidazolyl group, benzothiazol-2-yl group, morpholino group, benzoxazol-2-yl group), a sulfo group, a carboxyl group, substituted or unsubstituted aryloxycarbonyl or alkoxycarbonyl groups (such as a methoxycarbopnyl group, ethoxycarbonyl group, tetradecyloxycarbonyl group, 2-methoxycarbonyl group, phenoxycarbonyl group, 4-cyanophenoxylcarbonyl group, 2-chlorophenoxycarbonyl group), substituted or unsubstituted carbamoyl groups (such as a carbamoyl group, methylcarbamoyl group, diethylcarbamoyl group, methylhexadecylcarbamoyl group, methyloctadecylcarbamoyl group, phenylcarbamoyl group, 2,4,6-trichlorophenylcarbamoyl group, N-ethyl-N-phenylcarbamoyl group, 3-hexadecylsulfamoylphenylcarbamoyl group), a hydroxyl group, substituted or unsubstituted azo groups (such as a phenylazo group, p-methoxyphenylazo group, 2-cyano-4-methanesulfonylphenylazo group), substituted or unsubstituted aryloxy or alkoxy groups (such as a methoxy group, ethoxy group, dodecyloxy group, benzyloxy group, phenoxy group, 4-methoxyphenoxy group, 3-acetylaminophenoxy group, 3-methoxycarbonylpropyloxy group, 2-trimethylammonioethoxy group), a sulfino group, a sulpheno group, a mercapto group, substituted or unsubstituted acyl groups (such as an acetyl group, trifluoroacetyl group, n-butyroyl group, t-butyroyl group, benzoyl group, 2-carboxybenzoyl group, 3-nitrobenzoyl group, formyl group), substituted or unsubstituted arylthio or alkylthio group (such as a methylthio group, ethylthio group, t-octylthio group, hexadecylthio group, phenylthio group, 2,4,5-trichlorophenylthio group, 2-methoxy-5-t-octylphenylthio group, 2-acetylaminophenylthio group), substituted or unsubstituted aryl groups (such as a phenyl group, naphthyl group, 3-sulfophenyl group, 4-methoxyphenyl group, 3-lauroylaminophenyl group), substituted or unsubstituted sulfonyl groups (such as a methylsulfonyl group, chloromethylsulfonyl group, n-octylsulfonyl group, n-hexadecylsulfonyl group, sec-octylsulfonyl group, p-toluenesulfonyl group, 4-chlorophenylsulfonyl group, 4-dodecylphenylsulfonyl group, 4-dodecyloxyphenylsulfonyl group, 4-nitrophenylsulfonyl group), substituted or unsubstituted sulfinyl groups (such as a methylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, 4-nitrophenylsulfinyl group), substituted or unsubstituted amino groups (such as a methylamino group, diethylamino group, methyloctadecylamino group, phenylamino group, ethylphenylamino group, 3-tetradecylsulfamoylphenylamino group, acetylamino group, trifluoroacetylamino group, N-hexadecylacetylamino group, N-methylbenzoylamino group, methoxycarbonylamino group, phenoxycarbonylmethyl group, N-methoxyacetylamino group, amidinoamino group, phenylaminocarbonylamino group, 4-cyanophenylaminocarbonylamino group, N-ethylethoxycarbonylamino group, N-methyldodecylsulfonylamino group, N-(2-cyanoethyl)p-toluenesulfonylamino group, hexadecylsulfonylamino group, trimethylammonio group), substituted or unsubstituted sulfamoyl groups (such as a dimethylsulfamoyl group, hexadecylsulfamoyl group, sulfamoyl group, methyloctadecylsulfamoyl group, methylhexadecylsulfamoyl group, 2-cyanoethylhexadecylsulfamoyl group, phenylsulfamoyl group, N-(3,4-dimethylphenyl)N-octylsulfamoyl group, dibutylsulfamoyl group, dioctadecylsulfamoyl group, bis(2-methoxycarbonylethyl)sulfamoyl group), substituted or unsubstituted acyloxy groups (such as an acetoxy group, benzoyloxy group, decyloyloxy group, chloroacetoxy group), and substituted or unsubstituted sulfonyloxy groups (such as a methylsulfonyloxy group, p-toluenesulfonyloxy group, p-chlorophenylsulfonyloxy group).

More specific examples of EAG include aryl groups substituted by at least one electron-attracting group (such as a 4-nitrophenyl group, 2-nitro-4-N-methyl-N-octadectksulfamoyl group, 2-N,N-dimethylsulfamoyl-4-nitrophenyl group, 2-cyano-4-octadecylsulfonylphenyl group, 2,4-dinitrophenyl group, 2,4,6-tricyanophenyl group, 2-nitro-4-N-methyl-N-octadecylcarbamoylphenyl group, 2-nitro-5-octylthiophenyl group, 2,4-dimethanesulfonylphenyl group, 3,5-dinitrophenyl group, 2-chloro-4-nitro-5-methylphenyl group, 2-nitro-3,5-dimethyl-4-tetradecylsulfonylphenyl group, 2,4-dinitronaphthyl group, 2-ethylcarbamoyl-4-nitrophenyl group, 2,4-bisdodecylsulfonyl-5-trifluoromethylphenyl group, 2,3,4,5,6-pentafluorophenyl group, 2-acetyl-4-nitrophenyl group, 2,4-diacetylphenyl group, 2-nitro-4-trifluoromethylphenyl group), substituted or unsubstituted heterocyclic groups having aromaticy (such as a 2-pyridyl group, 2-pyrazyl group, 5-nitro-2-pyridyl group, 5-N-hexadecylcarbamoyl-2-pyridyl group, 4-pyridyl group, 2,5-dicyano-2-pyridyl group, 5-dodecylsulfonyl-2-pyridyl group, 5-cyano-2-pyrazyl group, 4-nitrothiophen-2-yl group, 5-nitro-1,2-dimethylimidazol-4-yl group, 3,5-diacetyl-2-pyridyl group, 1-dodecyl-5-carbamoylpyridinium-2-yl group), substituted or unsubstituted quinones (such as a 1,4-benzoquinon-2-yl group, 3,5,6-trimethyl-1,4-benzoquinon-2-yl group, 3-methyl-1,4-naphthoquinon-2-yl group, 3,6-dimethyl-5-hexadecylthio-1,4-benzoquinon-2-yl group, 5-pentadecyl-1,2-benzoquinon-4-yl group) and vinylogues of the aforesaid groups.

Then, (Time).sub.t and PUG are explained in detail.

Time represents a group which releases PUG via subsequent reaction triggered by the cleavage of the nitrogen-nitrogen single bond and t represents 0 or 1.

Various groups shown by Time are known as described, for example, in Japanese Patent Application (OPI) Nos. 147244/86 (pages 5 and 6) and 236549/86 (pages 8 to 14).

Preferred examples of the timing group (Time) are illustrated below, wherein (*) means the site of bonding the group at the dotted line side in formulae (I) and (II) and (*)(*) are the site of bonding PUG. ##STR10##

PUG means a photographically useful group in the form of Time-PUG or PUG by itself.

Photographically useful groups include, for example, development inhibitors, development accelerators, nucleating agents, couplers, diffusible or non-diffusible dyes, desilvering accelerators, desilvering inhibitors, silver halide solvents, competing compounds, developing agents, developing auxiliaries, fixing accelerators, fixing inhibitors, image stabilizers, toning agents, processing dependence improving agents, dot improving agents, color image stabilizers, photographic dyes, surfactants, hardeners, desensitizers, contrast intensifiers, chelating agents, fluorescent whitening agents, and ultraviolet absorbents as well as precursors thereof.

These photographically useful groups often overlap with one another with respect to the useful characteristics thereof, and typical examples of these groups are specifically given hereafter.

Examples of development inhibitors include compounds having a mercapto group bonded to a hetero-ring, for example, halogen atoms (bromine, iodine, etc.), substituted or unsubstituted mercaptoazoles (such as 1-phenyl-5-mercaptotetrazole, 1-(4- carboxyphenyl)-5mercaptotetrazole, 1-(3- hydroxypheny 1) -5-mercaptotetrazole, 1-(4-sulfophenyl)-5-mercaptotetrazole, 1-(3-sulfophneyl)-5-mercaptotetrazole, 1-(4-sulfamoylphenyl)-5-mercaptotetrazole, 1-(3-hexanoylaminophenyl)-5-mercaptotetrazole, 1-ethyl-5-mercaptotetrazole, 1-(2-carboxyethyl)-5-mercaptotetrazole, 2-methylthio-5-mercapto-1,3,4-thiadiazole, 2-(2-carboxyethylthio)-5-mercapto-1,3,4-thiadiazole, 3-methyl-4-phenyl-5-mercapto-1,2,4-triazole, 2-(2-dimethylaminoethylthio)-5-mercapto-1,3,4-thiadiazole, 1-(4-n-hexylcarbamoylphenyl)-2-mercaptoimidazole, 3-acetylamino-4-methyl-5-mercapto-1,2,4-triazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercapto-6-nitro-1,3-benzoxazole, 1-(1-naphthyl)-5-mercaptotetrazole, 2-phenyl-5-mercapto-1,3,4-oxadiazole, 1- [3-(3-methylureido)phenyl]-5-mercaptotetrazole, 1-(4-nitrophenyl)-5-mercaptotetrazole, 5-(2-ethylhexanoylamino)-2-mercaptobenzimidazole), substituted or unsubstituted mercaptoazaindenes (such as 6-methyl-4-mercapto-1,3,3a,7-tetrazaindene, 6-methyl-2-benzyl-4-mercapto-1,3,3a,7-tetrazaindene, 6-phenyl-4-mercapto-1,3,3a,7-tetrazaindene, 4,6-dimethyl-2-mercapto-1,3,3a,7-tetrazaindene), and substituted or unsubstituted mercaptopyrimidines (such as 2-mercaptopyrimidine, 2-mercapto-4-methyl-6 -hydroxypyrimidine, 2- mercapto-4-propylpyrimidine); as well as imino silver forming heterocyclic compounds, for example, substituted or unsubstituted benzotriazoles (such as benzotriazole, 5-nitrobenzotriazole, 5-methylbenzotriazole, 5,6-dichlorobenzotriazole, 5-bromobenzotriazole, 5-methoxybenzotriazole, 5-acetylaminobenzotriazole, 5-n-butylbenzotriazole, 5-nitro-6-chlorobenzotriazole, 5,6-dimethylbenzotriazole, 4,5,6,7-tetrachlorobenzotriazole), substituted or unsubstituted indazoles (such as indazole, 5-nitroindazole, 3-nitroindazole, 3-chloro-5-nitroindazole, 3-cyanoindazole, 3-n-butylcarbamoylindazole, 5-nitro-3-methanesulfonylindazole), substituted or unsubstituted benzimidazoles (such as 5-nitrobenzimidazole, 4-nitrobenzimidazole, 5,6-dichlorobenzimidazole, 5-cyano-6-chlorobenzimidazole, 5-trifluoromethyl-6-chlorobenzimidazole). The development inhibitors, after released from the oxidation-reduction nucleus of formula (I) by the reaction subsequent to the oxidation-reduction reaction in the development process, yield development inhibitory compounds, which may change to compounds with no substantial development inhibitory activity or to compounds with an extremely reduced development inhibitory activity.

Examples thereof are 1-(3-phenoxycarbonylphenyl)-5-mercaptotetrazole, 1-(4-phenoxycarbonylphenyl)-5-mercaptotetrazole, 1-(3-maleimidophenyl)-5-mercaptotetrazole, 5-(phenoxycarbonyl)benzotriazole, 5-(p-cyanophenoxycarbonyl)benzotriazole, 2-phenoxycarbonylmethylthio-5-mercapto-1,3,4-thiadiazole, 5-nitro-3-phenoxycarbonylindazole, 5-phenoxycarbonyl-2-mercaptobenzimidazole, 5-(2,3-dichloropropyloxycarbonyl)benzotriazole, 5-benzyloxycarbonylbenzotriazole, 5-(butylcarbamoylmethoxycarbonyl)benzotriazole, 5-(butoxycarbonylmethoxycarbonyl)benzotriazole, 1-(4-benzoyloxyphenyl)-5-mercaptotetrazole, 5-(2-methanesulfonylethoxycarbonyl)-2-mercaptobenzothiazole, 1-[4-(2-chloroethoxycarbonyl)phenyl]-2-mercaptoimidazole, 2-3-[thiophen-2-ylcarbonyl]propyl thio-5-mercapto-1,3,4-thiadiazole, 5-cinnamoylaminobenzotriazole, 1-(3-vinylcarbonylphenyl)-5-mercaptotetrazole, 5-succinimidomethylbenzotriazole, 2-[4-succinimidophenyl]-5-mercapto-1,3,4-oxadiazole, 3-[4-(benzo-1,2-isothiazole-3-oxo-1,1-dioxy-2-yl)phenyl]-5-mercapto-4-meth yl-1,2,4-triazole and 6-phenoxycarbonyl-2-mercaptobenzoxazole.

When PUG is a diffusible or non-diffusible dye, examples of the days include azo dyes, azomethine dyes, azopyrazolone dyes, indaniline type eyes, indophenol type dyes, anthraquinone type dyes, triarylmethane type dyes, alizarin, nitro type dyes, quinoline type dyes, indigo type dyes and phthalocyanine type dyes. In addition, the leuco forms of these dyes, dyes with a temporarily shifted absorption wavelength as well as dye precursors such as tetrazolium salts may be used. Further, these dyes may form chelated dyes with metals. These dyes are described, e.g., in U.S. Pat. Nos. 3,880,658; 3,931,144; 3,932,380; 3,932,381 and 3,942,987.

Preferred dyes and dye precursors are azo dyes, azomethine dyes, indaniline type dyes and dye precursors thereof. Examples of preferred dyes and dye precursors are given below. ##STR11##

Examples of silver halide solvents for PUG are meso-ionic compounds as described in Japanese Patent Application (OPI) No. 163042/85 and U.S. Pat. Nos. 4,003,910 and 4,387,424; and amino-substituent-containing mercaptoazoles and azolethiones as described in Japanese Patent Application (OPI) No. 202531/82.

Examples of nucleating agents for PUG are the parts of the split-off groups released from couplers as described in Japanese Patent Application (OPI) No. 170840/84.

For the other PUG groups Japanese Patent Application No. 23013/86 and U.S. Pat. No. 4,248,962 may be referred to.

Examples of the compounds of the present invention are given below, which, however, are not limitative. ##STR12##

The compound of this invention can be synthesized by

(1) reacting an electron acceptive group capable of causing an aromatic nucleophilic substitution reaction (such as a 4-halo-3-nitrobenzenesulfonamide) and hydrazide or sulfonylhydrazine in a nonprotic polar solvent such as dimethyl sulfoxide, dimethylformamide, etc., in the existence of a base, halomethylating, and then bonding a photographically useful group thereto by a substitution reaction or, if the photographically useful group is capable of reacting with hydrazide or sulfonylhydrazine, reacting the product before the above halomethylation with the group or

(2) reacting an electron-acceptive group capable of causing an aromatic nucleophilic substitution reaction, such as a 4-halo-3-nitrobenzenesulfonamide and a heterocyclic compound having a N-N single bond, one of the nitrogen atoms being diisocyable in a non-protic polar solvent as (1), whereby the electron-acceptive group can be bonded to the nitrogen atom of the heterocyclic ring.

By utilizing the reaction described above, the compounds having the photographically useful groups as illustrated above can be obtained by selecting the heterocyclic compounds described above.

Then, specific examples for the synthesis of the compounds of this invention are shown below for understanding more easily the above-described synthesis methods.

1 - 1: Synthesis of 1-(2-Nitro-4-N-methyl-N-hexadecylsulfamoylphenyl)-4-phenyl-1,2,4-triazolin e-5-dione:

In dimethyl sulfoxide were dissolved 10 g of N-methyl-N-hexadecyl-4-chloro-3-nitrobenzenesulfonamide and 4.1 g of 3-phenyl-1,2,4-triazoline-3,5-dione and after adding thereto 4.4 g of potassium carbonate, they were reacted for 4 hours at 60.degree. C. After the reaction was over, the reaction mixture was cooled and poured into ice-water to precipitate crystals, which were collected, dissolved in a mixture of acetonitrile, methanol, and a small amount of water and recrystallized to provide 7.5 g of the aforesaid compound having melting point of 129.degree. to 130.degree. C. with a yield of 57.7%.

1 - 2: Synthesis of 1-(2-Nitro-4-N-methyl-N-hexadecylsulfamoylphenyl)-2-chloromethyl-4-phenyl- 1,2,4-triazoline-3,5-dione:

In acetic acid was dissolved 3 g of the compound prepared in Synthesis Step 1 - 1 described above and after adding thereto 1.0 g of paraformaldehyde, a hydrogen chloride gas was blown into the system. The reaction was gradually raised to 80.degree. C. and the reaction was permitted to run for 5 hours at the same temperature.

After the reaction was over, the reaction mixture was poured in ice-water and the product formed was extracted with ethyl acetate. After distilling off the solvent from the filtrate, the main product was recovered from the residue by silica gel column chromatography to provide 1.2 g of 1-(2-nitro-4-N-methyl-N-hexadecylsulfamoylphenyl)-2-chloromethyl-4-phenyl- 1,2,4-triazoline-3,5-dione with a yield of 37.1%.

1 - 3: Synthesis of Compound 10:

In acetone was dissolved 1.0 g of the compound obtained in Synthesis 1 - 2 described above and after adding thereto 0.32 g of potassium carbonate and then 0.28 g of 1-phenyl-5-mercaptotetrazole, the reaction was permitted to run for 7 hours at room temperature.

After the reaction was over, inorganic materials were removed by filtration, the solvent was distilled off form the residue, and the residue thus formed was recrystallized from a mixture of acetonitrile, methanol, and water to provide 1.0 g of the desired compound having a melting point of 97.degree. to 98.degree. C. with a yield of 82.1%.

The compounds of this invention can release a photographically useful group reversely to the imagewise development of silver halide or reversely corresponding to the development of silver halide, rapidly with good timing and with high efficiency, and therefore, can be applied over a broad field of use in the photographic arts. Some examples of the uses to which the compounds of this invention can be applied are shown below.

(1) In the case the compounds of the present invention involve a diffusible dye as a photographically useful group, they can be used in the formation of color images in a diffusion transfer process or a sublimation transfer process. In this case, when negative emulsions are used, positive images are obtained whereas when autopositive emulsions are used, negative images are obtained.

(2) In the case the compounds of the present invention involve a compound which is a colorless compound or a dye with a changed absorption wavelength when it is bonded to the compound but which is colored or is differently colored after release therefrom as a photographically useful group, color is changed before and after release of the compound. Accordingly, images may be formed by utilization of such color change.

(3) In the case the compounds of the present invention involve a fog inhibitor as a photographically useful group, a larger amount of the fog inhibitor will typically be released in non-developed areas than in developed areas, and, therefore, effective fog inhibition is possible without lowering of sensitization (which is generally unfavorable in photography). In this case, the same effects can be attained by the use of autopositive emulsions or negative working emulsions.

The compounds of the present invention may be applied to various uses over a wide range as mentioned above. Further, the present compounds provide more excellent characteristics than any other known compounds having similar functions.

More precisely:

(1) The compounds of the present invention release a photographically useful group at a sufficient speed even at a temperature of -20.degree. C. or lower and hardly decompose even at higher temperatures. Therefore, they can be used over an extremely broad temperature range. Regarding pH, the reduction reaction of compounds per the present invention is of a controlling step for reaction since the cleavage of the nitrogen-nitrogen bond in the compound seemingly results in the direct release of the photographically useful group from the compound, and, therefore, the compounds may be used almost in any desired pH range where the reduction reaction is possible. The preferred temperature range for the use of the present compounds is from -20.degree. C. to +180.degree. C. and the preferred pH range therefor is from 6.0 to 14.0, based on a consideration of the practical use of such compounds in photography.

(2) The compounds of the present invention are oxidative in nature and, therefore, are completely stable under the oxidative environment of the air during storage of photographic materials. The nitrogen-nitrogen single bond in the compounds is stable to acids and alkalis and, therefore, stability in storage of photographic materials is excellent.

(3) Further merits of the present compounds are that the reduced and decomposed products of the present compounds, or the products formed by the reduction of the present compounds in processing thereof, are chemically inactive and do not have any undesired side-effects during photographic processing. Further, the present compounds have no adverse influence on the stability of formed images in the storage of photographs.

The compounds of the present invention can be incorporated into a silver halide emulsion layer or layers or into a hydrophilic colloid layer provided on the upper or lower side of the emulsion layer(s) or into both layers, whereby the aimed object of the present invention is attained. In the actual use of the compounds, e.g., of formula (I) of the present invention, for the objects described, the selection of a desired PUG group in accordance with the objects is required, and the amount of the compound added to the photographic material varies depending on the kind of the photographic material and the property of the desired PUG. In general, the amount added is preferably within the range of 1.times.10.sup.-7 mole to 1.times.10.sup.3 moles per one mole of silver halide.

The compound(s) of the present invention may be used over a broad range. The preferred amount to be used varies, depending upon the kind of PUG. For instance, in the case PUG is a diffusible dye, the amount is generally 0.05 mmole/m.sup.2 to 50 mmole/m.sup.2, preferably 0.1 mmole/m.sup.2 to 5 mmole/m.sup.2, though this depends upon the absorbancy index of the dye. In the case PUG is a development inhibitor, the amount is preferably 1.times.10.sup.-7 mole to 1.times.10.sup.-1 mole, especially preferably 1.times.10.sup.-3 mole to 1.times.10.sup.-2 mole, per mole of silver halide. In the case PUG is a development accelerator or a nucleating agent, the same is used as in the case of the aforesaid development inhibitor. In the case PUG is silver halide solvent, the amount is preferably within the range of 1.times.10.sup.-5 mole to 1.times.10.sup.3 mole, especially preferably 1.times.10.sup.-4 to 1.times.10 mole, per mole of silver halide.

The compounds of the present invention release a photographically useful group or a precursor thereof, after accepting an electron from a reducing substance. Accordingly, when the reducing substance is imagewise converted into the oxidized form thereof, the compounds reversely imagewise release the photographically useful group or the precursor thereof.

The reducing substances used for the reduction of the compounds can be inorganic compounds or organic compounds, and their oxidation potential is preferably lower than the standard oxidation-reduction potential of silver ion/silver, which is 0.80 V.

Examples of usable inorganic compounds include metals, etc., having an oxidation potential of 0.80 V or less, such as Mn, Ti, Si, Zn, Cr, Fe, Co, Mo, Sn, Pb, W, H.sub.2, Sb, Cu and Hg; ions and complexes thereof having an oxidation potential of 0.80 V or less, such as Cr.sup.2+, V.sup.2+, Cu.sup.+, Fe.sup.2+, MnO.sub.4.sup.2-, I-, Co(CN).sub.6.sup.4-, Fe(CN).sub.6.sup.4-, (Fe-EDTA).sup.2- ; metal hydrides having an oxidation potential of 0.80 V or less, such as NaH, LiH, KH, NaBH.sub.4, LiBH.sub.4, LiAl(O--tC.sub.4 H.sub.9).sub.3 H, LiAl(OCH.sub.3).sub.3 H; sulfur or phosphorus compounds having an oxidation potential of 0.80 V or less, such as Na.sub.2 SO.sub.3, NaHS, NaHSO.sub.3, H.sub.3 P, H.sub.2 S, Na.sub.2 S, Na.sub.2 S.sub.2, etc.

The usable organic compounds include, for example, organic nitrogen compounds such as alkylamines and arylamines, organic sulfur compounds such as alkylmercaptans and arylmercaptans, and organic phosphorus compounds such as alkylphosphines and arylphosphines, and in particular, reducing agents for silver halide following the Kendal-Pelz equation described in James, The Theory of the Photographic Process, 4th edition, pages 299 (1977) are preferred.

Specific examples of the reducing agents are as follows:

3-Pyrazolidones and precursors thereof (e.g., 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone, 1-m-tolyl-3-pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-phenyl-4,4-bis(hydroxymethyl)-3-pyrazolidone, 1,4-dimethyl-3-pyrazolidone, 4-methyl-3-pyrazolidone, 4,4-dimethyl-3-pyrazolidone, 1-(3-chlorophenyl)-4-methyl-3-pyrazolidone, 1-(4-chlorophenyl)-4-methyl-3-pyrazolidone, 1-(4-tolyl)-4-methyl-3-pyrazolidone, 1-(2-tolyl)-4-methyl-3-pyrazolidone, 1-(4-tolyl)-3-pyrazolidone, 1-(3-tolyl)-3-pyrazolidone, 1-(3-tolyl)-4,4-dimethyl-3-pyrazolidone, 1-(2-trifluoroethyl)-4,4-dimethyl-3-pyrazolidone, 5-methyl-3-pyrazolidone, 1,5-diphenyl-3-pyrazolidone, 1-phenyl-4-methyl-4-stearoyloxymethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-lauroyloxymethyl-3-pyrazolidone, 1-phenyl-4,4-bis(lauroyloxymethyl)-3-pyrazolidone, 1-phenyl-2-acetyl-3-pyrazolidone, 1-phenyl-3-acetoxypyrazolidone); hydroquinones and the precursors thereof (e.g., hydroquinone, toluhydroquinone, 2,6-dimethylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, t-octylhydroquinone, 2,5-di-t-octylhydroquinone, pentadecylhydroquinone, sodium 5-pentadecylhydroquinone-2-sulfonate, 2-methyl-4-benzoyloxyphenol, 2-t-butyl-4-(4-chlorobenzoyloxy)phenol), etc.

As other examples of the reducing agents for silver halide, color developing agents are useful and examples thereof are p-phenylene series color developing agent such as N,N-diethyl-3-methyl-p-phenylenediamine described in U.S. Pat. No. 3,531,286.

As examples of more useful reducing agents, there are aminophenols described in U.S. Pat. No. 3,761,270. Particularly useful aminophenol reducing agents are 4-amino-2,6-dibromophenol, 4-amino-2-methylphenol sulfate, 4-amino-3-methylphenol sulfate, 4-amino-2,6-dichlorophenol hydrochloride, etc. Furthermore, as useful reducing agents there are 2,6-dichloro-4-substituted sulfonamidophenols, 2,6-dibromo-4-substituted sulfonamidophenols desribed in Research Disclosure, Vol. 151, No. 15108 and U.S. Pat. No. 4,021,240 and p-(N,N-dialkylaminphenyl)sulfamines described in Japanese Patent Application (OPI) No. 16740/84.

In addition to the aforesaid phenolic reducing agents, naphtholic reducing agents such as 4-aminonaphthol derivatives and also 4-substituted sulfonamidonaphthol derivatives described in Japanese Patent Application No. 100380/85 are particularly useful. Furthermore, as suitable general color developing agents, there are aminohydroxypyrazole derivatives described in U.S. Pat. No. 2,895,825, aminopyrazoline derivatives described in U.S. Pat. No. 2,892,714 and hydrazone derivatives described in Research Disclosure, No. 19412 and No. 19415, pages 227-230 and pages 236-240 (June, 1980). These color developing agents may be used singly or as a combination thereof.

In the case of incorporating a diffusible reducing substance in photographic light-sensitive material, it is preferred to use it in combination with an electron transfer agent (ETA) for accelerating the electron transfer between the reducing substance and a developable silver halide emulsion.

The electron transfer agent (ETA) can be selected from the aforesaid diffusible reducing substances. For attaining the more preferred action of the electron transfer agent (ETA), it is preferred that the transferring property thereof is higher than that of an immobile reducing substance.

Any reducing agent described above can be used as the reducing substance for the combination with ETA if the reducing agent can not substantially transfer in the emulsion layer(s) of the photographic light-sensitive material but specific examples thereof are hydroquinones, aminophenols, aminonaphthols, 3-pyrazolidinones, saccharin and the precursors thereof, picoliniums, and the compounds described in Japanese Patent Application (OPI) No. 110827/78 as electron donative materials.

Practical examples of the reducing agents are illustrated below.

ETA usable in combination with the reducing substances may be any ETA which may be cross-oxidized with said substance. Preferred examples thereof are diffusible 3-pyrazolidinones, aminophenols, phenylenediamines, and reductones.

This invention can be applied to so-called conventional photographic light-sensitive materials which are developed using a developer at temperature of near room temperature or heat-developable light-sensitive materials.

In case the present compounds are applied to conventional silver halide photographic materials, two systems are preferred for the reaction of the aforesaid reducing substance or the combination of the aforesaid reducing substance and ETA with the photographic material. In one system, the reducing substance or the combination of the substance and ETA is applied to the photographic material in the form of a developer in development thereof; and in the other system, the reducing substance is previously incorporated in the photographic material and the ETA is applied to the material in the form of a developer. In the former system, the preferred amount to be used is 0.001 mole/liter to 1 mole/liter, which is the concentration of the substance(s) in the total developer solution. In the latter system of previous incorporation in the element, 0.5 to 5 moles of the reducing substance is preferably incorporated into the material per mole of the present compound(s), and the concentration of ETA in the solution is preferably 0.001 mole/liter to 1 mole/liter.

On the other hand, in case the present compounds are applied to a heat developable photographic material, the reducing substance or the combination of the reducing substance and ETA is preferably previously incorporated into the heat developable photographic material. In this case, the preferred amounts are 0.5 to 5 moles of the reducing substance and 0.1 to 10 moles of ETA, per mole of the present compound(s).

The silver halide which can be used in the present invention may include any of silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide.

A halogen composition in the silver halide grains may be uniform, or the silver halide grains may have a multiple structure in which the composition is different between a surface portion and an inner portion (see Japanese Patent Application (OPI) Nos. 154232/82, 108533/83, 48755/84 and 52237/84, U.S. Pat. No. 4,433,048 and European Pat. No. 100,984, etc.).

Also, a tabular grain silver halide emulsion containing grains having a thickness of 0.5 .mu.m or less, a diameter of at least 0.6 .mu.m and an average aspect ratio of 5 or more (see U.S. Pat. Nos. 4,414,310 and 4,435,499, and West German Patent Application (OLS) No. 3,241,646A1, etc.), and a monodispersed emulsion having a nearly uniform distribution of grain size (see Japanese Patent Application (OPI) Nos. 178235/82, 100846/83 and 14829/83, PCT Application (OPI) No. 83/02338A1, and European Pat. Nos. 64,412A3 and 83,377A1, etc.) may be used in the present invention.

Two or more kinds of silver halides in which a crystal habit, a halogen composition, a grain size and/or a distribution of grain size, etc. are different from each other may be used in mixture. Further, two or more kinds of monodispersed emulsions having different grain size from each other may be employed in mixture to control gradation.

An average grain size of the silver halide used in the present invention is preferably from 0.001 .mu.m to 10 .mu.m, and more preferably from 0.001 .mu.m to 5 .mu.m.

These silver halide emulsions can be prepared by any of an acid process, a neutral process, and an ammonia process. Further, a reaction system of soluble silver salts and soluble halogen salts may be any of a single jet process, a double jet process and a combination thereof. In addition, a reverse mixing process in which silver halide grains are formed in the presence of an excess of silver ions, or a controlled double jet process in which the pAg in the liquid phase is kept constant, can also be utilized.

Moreover, for the purpose of increasing growth of grains, a concentration of addition, the amount of addition and/or speed of addition of silver salts and halogen salts added may be raised (see Japanese Patent Application (OPI) Nos. 142329/80 and 158124/80, and U.S. Pat. No. 3,650,757, etc.).

Furthermore, silver halide grains of epitaxial junction type (see Japanese Patent Application (OPI) No. 16124/81, and U.S. Pat. No. 4,094,684, etc.) may be employed.

In the step for formation of silver halide grains used in the present invention, ammonia, an organic thioether derivative as described in Japanese Patent Publication No. 11386/72, or a compound containing sulfur as described in Japanese Patent Application (OPI) No. 144319/78, etc., can be used as a solvent for silver halide.

In a process of the formation or physical ripening of silver halide grains, a cadmium salt, a zinc salt, a lead salt, or a thallium salt, etc., may coexist. These salts are used for the purposes of improving a change in photographic performance against the pressure, etc. Further, for the purpose of eliminating high- intensity reciprocity failure or low-intensity reciprocity failure, a water-soluble iridium salt such as iridium (III or IV) chloride, ammonium hexachloroiridiate, etc. or a water-soluble rhodium salt such as rhodium chloride, etc., can be used.

Soluble salts may be removed from the silver halide emulsion after precipitate formation or physical ripening, and a noodle washing process or a flocculation process can be used for this purpose.

While the silver halide emulsion may be employed without being subjected to after-ripening, it is usually chemically sensitized. For the chemical sensitization, a sulfur sensitization method, a reduction sensitization method, and a noble metal sensitization method, etc., which are known in the field of emulsions for conventional type photographic light-sensitive materials can be applied alone or in combination therewith. Such a chemical sensitization may be carried out in the presence of a nitrogen-containing heterocyclic compound (see Japanese Patent Application (OPI) Nos. 126526/83 and 215644/83, etc.).

The silver halide emulsion used in the present invention can be that of a surface latent image type in which a latent image is formed mainly on the surface of grains, or that of an internal latent image type in which a latent image is formed mainly in the interior of grains. Further, a direct reversal emulsion in which an internal latent image type emulsion and a nucleating agent are used in combination may be used. Examples of the internal latent image type emulsions suitable for this purpose are described in U.S. Pat. Nos. 2,592,250 and 3,761,276, Japanese Patent Publication No. 3534/83, and Japanese Patent Application (OPI) No. 136641/82, etc. Preferred examples of the nucleating agents suitably used in the present invention are described in U.S. Pat. Nos. 3,227,552, 4,245,037, 4,255,511, 4,266,031 and 4,276,364, and West German Patent Application (OLS) No. 2,635,316, etc.

The silver halide used in the present invention can be spectrally sensitized with methine dyes or other dyes. Suitable dyes which can be employed include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, stytyl dyes, and hemioxonol dyes. Of these dyes, cyanine dyes, merocyanine dyes and complex merocyanine dyes are particularly useful. Any conventionally utilized nucleus for cyanine dyes is applicable to these dyes as a basic heterocyclic nucleus. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazole nucleus, a selenazole nucleus, an aimidazole nucleus, a tetrazole nucleus, a pyridine nucleus, etc., and further, nuclei formed by condensing an alicyclic hydrocarbon ring with these nuclei and nuclei formed by condensing an aromatic hydrocarbon ring with these nuclei, that is, an indolenine nucleus, a benzindolenine nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, etc., are appropriate. The carbon atoms of these nuclei may also be substituted.

To merocyanine dyes and complex merocyanine dyes, as nuclei having a ketomethylene structure, 5- or 6-membered heterocyclic nuclei such as a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidin-2,4-dione nucleus, a thiazolidin-2,4-dione nucleus, a rhodanine nucleus, a thiobarbituric acid nucleus, etc., may also be applicable.

These sensitizing dyes can be employed individually, and can also be employed in combinations thereof. A combination of sensitizing dyes is often used, particularly for the purpose of supersensitization.

The sensitizing dyes may be present in the emulsion together with dyes which themselves do not give rise to spectrally sensitizing effects but which exhibit a supersensitizing effect or materials which do not substantially absorb visible light but which exhibit a supersensitizing effect. For example, aminostilbene compounds substituted with a nitrogen-containing hetero-cyclic group (for example, those described in U.S. Pat. Nos. 2,993,390 and 3,635,721, etc.), aromatic organic acid-formaldehyde condensates (for example, those described in U.S. Pat. No. 3,743,510, etc.), cadmium salts, azaindene compounds, etc., can be present. The combinations as described in U.S. Pat. Nos. 3,615,613, 3,615,641, 3,617,295 and 3,635,721 are particularly useful.

Gelatin is preferably used as the binder or protective colloid in the emulsion layers or intermediate layers of the present photographic materials, but other conventional hydrophilic colloids may be used alone or together with gelatin.

The gelatin may be either a lime treated gelatin or acid treated gelatin in the present invention. Details on the preparation of gelatins are given in The Macro molecular Chemistry of Gelatin, written by Arther Vaise, published by Academic Press (1964).

The photographic emulsions used in the present invention may contain surfactants singly or in the form of a mixture thereof.

These are essentially used as a coating auxiliary and sometimes for some other purposes such as emulsification and dispersion, improvement of photographic characteristic for sensitization, static charge prevention and blocking prevention. These surfactants are classified into natural surfactants such as saponin; nonionic surfactants such as alkyleneoxide type, glycerin type or glycidol type surfactants; cationic surfactants such as higher alkylamines, quaternary ammonium salts, pyridine and the like heterocyclic compounds or phosphonium or sulfonium salts; an anionic surfactants containing an acidic group such as a carboxylic acid, sulfonic acid, phosphoric acid, sulfate or phosphate group; and ampholytic surfactants such as amino acids, aminosulfonic acids or aminoalcohol sulfates or phosphates.

The photographic emulsions used in the present invention may contain various compounds for the purpose of the prevention of fog in manufacture, storage or photographic processing of the photographic materials or for the purpose of stabilization of photographic characteristic of the materials. For these purposes, various compounds which are known as anti-fogging agents or stabilizers may be used, including azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinthione; azaindenes such as triazaindenes, tetrazaindenes (especially 4-hydroxy-substituted (1,3,3a,7-tetrazaindenes), pentazaindenes; as well as benzenethiosulfonic acid, benzenesulfinic acid and benzenesulfonic acid amide.

The photographic emulsion layers of the present photographic materials may contain, for the purpose of increasing sensitivity, intensification of contrast or acceleration of development, for example, thioether compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives or 3-pyrazolidones.

The present photographic materials may further contain, in the photographic emulsion layers or in any other hydrophilic colloid layers, a water insoluble or sparingly soluble synthetic polymer dispersion for the purpose of the improvement of the dimensional stability of the material. Polymers usable for this purpose are homopolymers or copolymers of alkyl (meth)acrylates, alkoxyalkyl (meth)acrylates, glycidyl (meth)acrylates, (meth)acrylamides, vinyl esters (such as vinyl acetate), acrylonitriles, olefins and/or styrenes; as well as copolymers made of a combination of the said monomers and other monomer components such as acrylic acid, methacrylic acid, .alpha.,.beta.-unsaturated dicarboxylic acids, hydroxyalkyl (meth)acrylates, sulfoalkyl (meth)acrylates and styrenesulfonic acids.

Hydrophilic colloids are preferred as the binders used in the emulsion layers or auxiliary layers (such as protective layers, intermediate layers, etc.) of the present photographic materials, and in particular, gelatin is most preferred. Other hydrophilic colloids than gelatin may, of course, be used. For example, gelatin derivatives, graft polymers of gelatin and their high molecular weight compound, albumin, casein or like proteins; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose or cellulose sulfate esters, sodium alginate, starch derivatives or like saccharide derivatives; polyvinyl alcohol, partially acetalized polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinyl pyrazole or like homo- or co-polymers; as well as other various kinds of synthetic hydrophilic high molecular weight substances may be used. In addition, lime treated gelatin, acid treated gelatin or enzyme treated gelatin may also be used.

The present photographic materials may contain in the photographic emulsion layers, or in any other hydrophilic colloid layers, an inorganic or organic hardener. For example, chromium salts (such as chromium alum, chromium acetate), aldehydes (such as formaldehyde, glyoxale, glutaraldehyde), N-methylol compounds (such as dimethylolurea, methyloldimethylhydantoin), dioxane derivatives (such as 2,3-dihydroxydioxane), active vinyl compounds (such as 1,3,5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol), active halogen-containing compounds (such as 2,4-dichloro-6-hydroxy-s-triazine), mucohalogenic acids (such as mucochloric acid, mucophenoxychloric acid) and like hardeners may be used singly or in the form of a combination thereof.

The silver halide photographic materials of the present invention may contain other various conventional additives as are well known in the art, for example, whitening agents, dyes, desensitizers, coating assistants, antistatic agents, plasticizers, sliding agents, matting agents, development accelerators, mordanting agents, ultraviolet light absorbents, discoloration inhibitors and color fog-preventing agents.

Examples of such additives which may be used in the present invention are disclosed, for example, in Research Disclosure, Vol. 176, RD No. 17643 (December, 1978), pp. 22-31.

The compounds of formula (I) of the present invention may be used in various types of silver halide photographic materials, some examples of which are described hereunder.

(1) The present compounds are effective to improve the quality of silver halide photographic materials for photomechanical processing which have a silver chlorobromide or silver chloroiodobromide emulsion layer containing at least 60% silver chloride and 0 to 5% silver chlorobromide (the emulsion preferably being a monodispersed emulsion) and which contain a polyalkyleneoxide(s). For instance, in the case PUG in compound (I) is a development inhibitor, improving toe sharpness is possible without deteriorating dot quality. In the case PUG is a development accelerator, the compounds of formula (I) are effective for intensification of sensitivity and improving dot quality. In such cases, the amount of the present compound used is 1.times.10.sup.-7 mole to 1.times.10.sup.-1 mole, especially preferably 1.times.10.sup.-6 mole to 1.times.10.sup.-2 mole, per mole of silver halide.

(2) The compound of formula (I) of the present invention are effective for improving (or elongating) the dot gradation of photographic materials having monodisperse silver halide emulsion layers capable of forming negative images of ultra-high contrast by development with developers stabilized by the action of hydrazine derivatives described in U.S. Pat. Nos. 4,224,401, 4,168,977, 4,241,164, 4,311,781, 4,272,606, 4,221,857, 4,243,739, 4,272,614, and 4,269,929 without deteriorating the dot quality of the materials.

In the above development, stabilizes developers are those containing at least 0.15 mole/liter of such sulfite ion as a preservative and a pH of 10.0 to 12.3. Such developers containing a large amount of such preservatives are more stable than conventional lith developers (containing only an extremely low amount of the sulfite ion) and having a relatively low pH value, are hardly subjected to oxidation by the air and are more stable, for example, than developers (pH=12.8) in the high contrast image formation systems described in U.S. Pat. No. 2,419,975.

In the present case, PUG in the compounds of formula (I) of this invention is preferably a compound having development acceleration activity in high contract image formation systems containing a hydrazine derivative. Examples of the preferred compound are hydroxytetraazaindene derivatives described in Japanese Patent Application (OPI) No. 83714/78, thiamide compounds described in Japanese Patent Application (OPI) No. 77616/78 and amine compounds described in Japanese Patent Application (OPI) No. 140340/85. In particular, hydroxytetraazaindene derivatives are especially preferred. In this case, the compound of formula (I) of this invention are preferably used in the range of from 1.times.10.sup.-5 mole to 8.times.10.sup.-2 mole, and particularly from 1.times.10.sup.-4 mole to 5.times.10.sup.-2 mole per mole of the silver halide.

(3) The compounds of formula (I) of the present invention may be applied to multi-layer multi-color photographic materials having at least two light-sensitive layers on a support, each with a different spectral sensitivity, mainly for the purpose of fog inhibition, gradation regulation, improving color reproducibilirty and sensitization. Multi-layer natural color photographic materials have, in general, at least one red-sensitive emulsion layer, at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer on a support. The order of provision of these layers may freely be determined in accordance with the necessity thereof. The preferred order for the arrangement of the layers comprises a red-sensitive layer, a green-sensitive layer and a blue-sensitive layer from the support, or a blue-sensitive layer, a red-sensitive layer and a green-sensitive layer from the side of the support. Each of these emulsion layers may comprise two or more emulsion layers which have a different sensitivity, or a non-light-sensitive layer may be provided between or among two or more emulsion layers having the same sensitivity. In general, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler and the blue-sensitive emulsion layer contains a yellow-forming coupler, but, as desired other different combinations may be used per the present invention.

Various color couplers may be used in the present photographic materials. "Color couplers" herein mean compounds capable of forming dyes by a coupling reaction with an oxidized aromatic primary amine developing agent. Typical examples of usable color couplers are naphthol or phenol type compounds, pyrazolone or pyrazoloazole type compounds and open or heterocyclic ketomethylene compounds. Examples of cyan, magenta and yellow couplers which may be used in the present invention are described in the patent publications referred to in Research Disclosure, Vol. 176, RD No. 17643 (December, 1978), Item VII-D and ibid., Vol. 187, RD No. 18717 (November, 1979).

The color couplers to be incorporated in the photographic materials of this invention are preferably non-diffusible and have a ballast group or are polymerized. Two equivalent couplers where the coupling split-off group is substituted are preferred to four equivalent couplers where the coupling active site has a hydrogen atom, because the amount of the silver coated is reduced. Further, couplers capable of forming a dye with a diffusible, non-coloring coupler, a DIR coupler capable of releasing a development inhibitor on coupling or a coupler capable of releasing a development accelerator on coupling may also be used.

Typical yellow couplers used in the present invention are oil protected acylacetamide couplers. Examples are described, e.g., in U.S. Pat. Nos. 2,407,210, 2,875,057 and 3,265,506. Two equivalent yellow couplers are preferably used in the present invention, and examples are oxygen atom-releasing type yellow couplers as described in U.S. Pat. Nos. 3,408,194, 3,447,928, 3,933,501, and 4,022,620; and nitrogen atom-releasing type yellow couplers as described in Japanese Patent Publication No. 10739/83, U.S. Pat. Nos. 4,401,752 and 4,326,024, Research Disclosure, Vol. 180, RD No. 18053 (April, 1979), British Pat. No. 1,425,020 and German Patent (OLS) Nos. 2,219,917, 2,261,361, 2,329,587, and 2,433,812. The .alpha.-pivaloylacetanilide type couplers are excellent in the fastness of the colored dyes, in particular in the light fastness thereof, and the .alpha.-benzoylacetanilide type couplers generally form dyes of high color density.

The magenta couplers which may be used in the present invention are oil protected type indazolone or cyanoacetyl couplers, especially 5-pyrazolone type or pyrazoloazole type couplers, such as pyrazolotriazoles. Among the 5-pyrazolone type couplers, those in which the 3-position is substituted by an arylamino group or an acylamino group are preferred in view of the hue or the color density of the colored dyes; typical examples thereof are described in U.S. Pat. Nos. 2,311,082, 2,343,703, 2,600,788, 2,908,573, 3,062,653, 3,152,896, and 3,936,015. As the releasing group in the two equivalent 5-pyrazolone type couplers, preferred are the nitrogen atom-releasing groups as described in U.S. Pat. No. 4,310,619 and the arylthio groups as described in U.S. Pat. No. 4,351,897. The 5-pyrazolone type couplers with a ballast group as described in European Pat. No. 73,636 also can form dyes with a high color density and are useful herein.

Examples of pyrazoloazole type couplers useful herein are pyrazolobenzimidazoles as described in U.S. Pat. No. 3,061,432, preferably pyrazole(5,1-c)(1,2,4)triazoles as described in U.S. Pat. No. 3,725,067, pyrazolotetrazoles as described in Research Disclosure, Vol. 242, RD No. 24220 (June, 1984) and Japanese Patent Application (OPI) No. 33552/85 and pyrazolopyrazoles as described in ibid., Vol. 242, RD No. 24230 (June, 1984) and Japanese Patent Application (OPI) No. 43659/85. Imidazo(1,2-b)pyrazoles as described in U.S. Pat. No. 4,500,630 are preferable because of the lower yellow side absorption of the colored dyes and the light fastness thereof, and in particular, pyrazolo(1,5-b)(1,2,4)triazoles as described in U.S. Pat. No. 4,540,654 are especially preferred.

Cyan couplers which may be used in the present invention are oil protected type naphthol and phenol couplers; typical examples thereof are naphthol type couplers as described in U.S. Pat. No. 2,474,293, especially oxygen atom-releasing type two equivalent naphthol couplers as described in U.S. Pat. Nos. 4,052,212, 4,146,396, 4,228,233 and 4,296,200. Examples of phenol type couplers are given in, e.g., U.S. Pat. Nos. 2,369,929, 2,801,171, 2,772,162, and 2,895,826. Cyan couplers which are resistant to moisture and temperature are preferably used in the present invention, and typical examples thereof are phenol type cyan couplers having an ethyl or higher alkyl group in the m-position of the phenol nucleus, as described in U.S. Pat. No. 3,772,002; 2,5-diacylamino substituted phenol type couplers, as described in U.S. Pat. Nos. 2,772,162, 3,758,308, 4,126,396, 4,334,011, and 4,327,173, German Patent (OLS) No. 3,329,729 and European Pat. No. 121,365; and phenol type couplers having a 2-phenylureido group and a 5-acylamino group, as described in U.S. Pat. Nos. 3,446,622, 4,333,999, 4,451,559, and 4,427,767. In addition, naphthol type cyan couplers having a sulfonamido or amido group in the 5-position of the naphthol nucleus thereof, as described in Japanese Patent Application (OPI) No. 237448/85 and European Pat. No. 161,626, can preferably be used in the present invention, to form color images of high fastness.

In order to correct unnecessary absorption of dyes formed from the magenta and cyan couplers in the short wavelength region, colored couplers are preferably used in color negative photographic materials for photographing. Typical examples of colored couplers are yellow colored magenta couplers as described in U.S. Pat. No. 4,163,670 and Japanese Patent Publication No. 39413/82; and magenta colored cyan couplers as described in U.S. Pat. Nos. 4,004,929 and 4,138,258 and British Pat. No. 1,146,368.

Couplers forming dyes with an appropriate diffusibility may be used for an improvement of graininess. Regarding smearing couplers, examples of magenta couplers are described in U.S. Pat. No. 4,366,237 and British Pat. No. 2,125,570; and yellow, magenta or cyan couplers are described in European Pat. No. 96,570 and German Patent (OLS) No. 3,234,533.

The dye forming couplers and the aforesaid special couplers may form dimers or higher polymers. Typical examples of polymerized dye forming couplers in general are described in U.S. Pat. Nos. 3,451,820 and 4,080,211. Examples of polymerized magenta couplers are described in British Pat. No. 2,102,173, U.S. Pat. No. 4,367,282 and U.S. patent application Ser. Nos. 849,589 (filed Apr. 8, 1986) and 866,833 (filed May 27, 1986).

Regarding the incorporation of various kinds of couplers into the photographic materials per the present invention, two or more different kinds of couplers may be added to one light-sensitive layer, or the same coupler may of course be added to two or more different layers with no problem.

The compounds of the present invention may be used together with couplers, and may be added to the same emulsion layer together with the couplers, or may be added to an intermediate layer(s) or another photographic auxiliary layer(s) in the form of an independent emulsified dispersion.

The amount of the present compounds to be used is 0.1 to 50 mole %, preferably 0.3 to 15 mole %, based on the coupler in each light-sensitive layer, or the yellow coupler in the blue-sensitive layer, the magenta coupler in the green-sensitive layer or the cyan coupler in the red-sensitive layer, in the color photographic material. The amount is preferably 1.times.10.sup.-5 mole to 8.times.10.sup.-2 mole, especially 1.times.10.sup.-4 mole to 5.times.10.sup.-2 mole, per mole of the silver halide in the layer to which the present compound is to be added.

(4) The compounds of formula (I) of the present invention are effective to improve photographic characteristics, for example, for the regulation of graininess and gradation of black-and-white photographic materials, especially X-ray photographic materials, having a silver chlorobromide or silver chloroiodobromide emulsion layer(s) containing 0 to 50 mole % silver chloride and up to 15 mole % silver iodide on one side or both sides of the support. In the present case, the amount of the present compound used is 1.times.10.sup.-6 mole to 1.times.10.sup.-1 mole, especially 1.times.10.sup.-5 mole to 5.times.10.sup.-2 mole, per mole of the silver halide.

In addition, the compounds of formula (I) of the present invention may be applied to other photographic materials for various uses, for example, photographic materials for electron rays, black-and-white photographic materials of high resolving power, black-and-white photographic materials for use in a diffusion transfer process, color X-ray photographic materials and color photographic materials for use in a diffusion transfer process.

In the case the silver halide photographic materials of the present invention are processed by a conventional wet method, any and every general means may be used. Known processing solutions may thus be used. The processing temperature is generally selected in the range of 18.degree. C. to 50.degree. C., but this may be lower than 18.degree. C. or higher than 50.degree. C. In accordance with the desired use of the photographic materials, any black-and-white photographic processing for development for the formation of silver images or color photographic processing for development for the formation of color images may be applied to the materials.

Details on various useful photographic processing procedures are described in T. H. James, 4th Ed., The Theory of the Photographic Process, pp. 291-436, and Research Disclosure, Vol. 176, RD No. 17643 (December, 1978), pp. 28-30.

For fixing after black-and-white development, conventional fixers of general compositions may be used. The fixers may contain a thiosulfate or thiocyanate as a fixing agent or an organic sulfur containing compound which is known to be effective as a fixing agent. The fixer may contain a water-soluble aluminum salt as a hardener.

After color development, the photographic emulsion layers are generally bleached. The bleaching may be carried out simultaneously with fixing or separately therefrom.

As the bleaching agent there may be used polyvalent metal compounds such as iron(III), cobalt(III), chromium(VI) or copper(II) compounds, peracids, quinones or nitroso compounds. For instance, ferricyanides, bichromates and iron(III) or cobalt(III) organic complexes, for example, with an organic acid such as an aminopolycarboxylic acid (e.g., ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid), citric acid, tartaric acid or malic acid; persulfates and permanganates; and nitrosophenols, etc., may be used. In particular, potassium ferricyanide, sodium ethylenediaminetetraacetate iron(III) and ammonium ethylenediaminetetraacetate iron(III) are especially useful. Ethylenediaminetetraacetate iron(III) complexes are useful either in an independent bleaching solution or in a combined bleach-fix bath.

The bleaching or bleach-fixing solution may contain various additives such as a bleach accelerator as described in U.S. Pat. Nos. 3,042,520 and 3,241,966 and thiol compound as described in Japanese Patent Application (OPI) No. 65732/78.

In particular, the compounds of formula (I) of this invention having introduced therein a diffusible dye as PUG are preferably used for heat developable silver halide photographic materials wherein a mobile dye is formed by heat development and is transferred into a dye-fixing layer described in Japanese Patent Application (OPI) Nos. 149046/83, 154445/84, 165054/84, 180548/84, 218443/84, 133449/85, 238056/86, and U.S. Pat. Nos. 4,503,137, 4,474,876, 4,483,914, 4,455,363, 4,500,626.

In the case of using the invention for heat developable photographic materials, organic metal salts can used as an oxidizing agent together with light-sensitive silver halide.

Among the organic metal salts, organic silver salts are especially preferred.

Organic compounds useful for the formation of the aforesaid organic silver salt oxidizing agents are described, e.g., in Japanese Patent Application (OPI) No. 107243/86 and U.S. Pat. No. 4,500,626 (52nd column and 53rd column). In addition, silver salts of alkynyl group containing carboxylic acids such as silver phenylpropiolate, as described in Japanese Patent Application (OPI) No. 113235/85, are also useful.

The amount of the organic silver salt(s) which may be used is 0.01 to 10 moles, preferably 0.01 to 1 mole, per mole of the light-sensitive silver halide. The total amount of the light-sensitive silver halide and the organic silver salt as coated is suitably 50 mg/m.sup.2 to 10 mg/m.sup.2, calculated in terms of the coated silver amount.

The image forming substances of heat developable photographic materials may be compounds of formula (I) of the present invention which have a dye as PUG, or otherwise, if the compounds of formula (I) where PUG is a photographically useful group other than dyes which are used in heat developable photographic materials. The image forming substances thereof may be silver, or the materials may contain a compound capable of forming or releasing a mobile dye in the reduction of light-sensitive silver halide to silver under high temperature conditions, in accordance with or reversely in accordance with said reaction, i.e., a dye-providing substance.

Examples of the dye-providing substances which may be used in the present invention are, first the aforesaid couplers. In addition, two equivalent couplers which have a non-diffusible group as a split-off group and which form a diffusible dye by reaction with oxidized developer are also preferably used. Examples of these couplers are described in detail in T. H. James, The Theory of the Photographic Process, pp. 291-334 and pp. 354-361; and Japanese Patent Application (OPI) Nos. 123533/83, 149046/83, 149047/83, 111148/84, 124399/84, 174835/84, 231539/84, 231540/84, 2950/85, 2951/85, 14242/85, 23474/85, and 66249/85.

Another example of the dye providing substance is a dye-silver compound in which an organic silver salt is connected to a dye. Specific examples of the dye- silver compounds are described in Research Disclosure, Vol. 169, RD No. 16966 (May, 1978), pp. 54 to 58, etc.

Still another example of the dye providing substance is an azo dye used in a heat developable silver dye bleaching process. Specific examples of the azo dyes and the method for bleaching are described in U.S. Pat. No. 4,235,957, Research Disclosure, Vol. 144, RD No. 14433 (April, 1976), pp. 30 to 32, etc.

A further example of the dye providing substance is a leuco dye as described in U.S. Pat. Nos. 3,985,565 and 4,022,617, etc.

A still further example of the dye providing substance is a compound having a function of imagewise releasing a diffusible dye.

This type of compound can be represented by formula (LI)

wherein Dye represents a dye moiety, a dye moiety temporarily shifted to the short wavelength range or a dye precursor moiety; X represents a chemical bond or a connecting group; Y represents a group having a property such that diffusibilty of the compound represented by (Dye-X).sub.n --Y can be differentiated in correspondence or counter-correspondence to light-sensitive silver salts having a latent image distributed imagewise or a group having a property of releasing Dye in correspondence or counter-correspondence to light-sensitive silver salts having a latent image distributed imagewise, diffusibility of Dye released being different from that of the compound represented by (Dye-X).sub.n --Y; and n represents 1 or 2 and when n is 2, the two Dye X groups are the same or different.

Specific example of the dye providing substance represented by formula (LI) include, for example, dye developers in which a hydroquinone type developing agent (reducing agent) is connected to a dye component are described in U.S. Pat. Nos. 3,134,764, 3,362,819, 3,597,200, 3,544,545 and 3,482,972, etc. Further, substances capable of releasing diffusible dyes upon an intramolecular nucleophilic displacement reaction are described in Japanese Patent Application (OPI) No. 63618/76, etc., and substances capable of releasing diffusible dyes upon an intramolecular rearrangement reaction of an isooxazolone ring are described in Japanese Patent Application (OPI) No. 111628/74, etc.

In any of these processes, diffusible dyes are released in portions where development does not occur. In contrast, in portions where development occurs neither release nor diffusion of dyes take place.

There has been provided a process in which a dye releasing compound is preliminarily converted to an oxidized form thereof which does not have a dye releasing ability, the oxidized form of the compound is coexistent with a reducing agent or a precursor thereof, and after development the oxidized form is reduced with the remaining reducing agent which is not oxidized to release a diffusible dye. Specific examples of dye providing substances which can be used in such a process are described in Japanese Patent Application (OPI) Nos. 110827/78, 130927/79, 164342/81, and 35533/78, etc.

On the other hand, substances capable of releasing diffusible dyes in portions where development occurred are also know. For example, substances capable of releasing diffusible dyes in the releasing groups thereof with oxidation products of developing agents (reducing agents) are described in British Pat. No. 1,330,524, Japanese Patent Publication No. 39165/73, U.S. Pat. No. 3,443,940, etc., and substances capable of forming diffusible dyes upon a reaction of couplers having diffusion resistant groups in the releasing groups thereof with oxidation products of developing agents are described in U.S. Pat. No. 3,227,550, etc.

In these processes using color developing agents, there is a severe problem in that images are contaminated with oxidation decomposition products of the developing agents. Therefore, in order to eliminate such a problem, dye releasing compounds which have reducing property themselves and thus do not need the use of developing agents have been proposed. (As a matter of course, the above-described reducing agents may be auxiliary used.) Such dye providing compounds are described, e.g., in U.S. Pat. Nos. 3,928,312, 4,053,312, 4,055,428, 4,336,322, 3,725,062, 3,728,113, 3,443,939, and 4,500,626 and Japanese Patent Application (OPI) Nos. 65839/84, 69839/84, 3819/78, 104343/76, 116537/83, and 179840/82, and Research Disclosure, Vol. 174, RD No. 17465 (Oct., 1978).

Specific examples of dye providing substances which can be used in the present invention are the compounds as described in aforesaid U.S. Pat. No. 4,500,626 (from the 22nd column to the 44th column), and in particular, Compounds (1)-(3), (10)-(13), (16)-(19), (28)-(30), (33)-(35), (38)-(40) and (42)-(64) among the compounds of the said U.S. Patent are especially preferred. Also, compounds described in Japanese Patent Application No. 2468/84 are useful.

The aforesaid dye providing substances and other hydrophobic additives such as image forming accelerators, which will be described hereafter, may be introduced into the layers of the photographic materials in a conventional manner, for example, by the method described in U.S. Pat. No. 2,322,027. For introduction, high boiling point organic solvents as described in Japanese Patent Application (OPI) Nos. 83154/84, 178451/84, 178452/84, 178453/84, 178454/84, 178455/84, and 178457/84 may be used, optionally together with a low boiling point organic solvent(s) having a boiling point of 50.degree. C. to 160.degree. C.

The amount of the high boiling point organic solvent to be used is generally 10 g or less, preferably 5 g or less, to 1 g of the dye providing substance.

In addition, the dispersion method using polymers described in Japanese Patent Publication No. 39853/76 and Japanese Patent Application (OPI) No. 59943/76 may also be used.

In the case the compounds are substantially insoluble in water, fine particles of the compound may be dispersed in a binder and the resulting dispersion may be introduced into the layers.

For the dispersion of hydrophobic substances into hydrophilic colloids, various surfactants may be used, e.g., those as described in Japanese Patent Application (OPI) No. 157636/84 may be used.

In the present invention, heat developable photographic materials may contain an image forming accelerator. Image forming accelerators have various functions, for example, for the acceleration of the oxidation-reduction reaction of a silver salt oxidizing agent and a reducing agent, acceleration of the formation of dyes from a dyeproviding substances as well as for the decomposition of dyes or for the release of diffusible dyes and the acceleration of the transfer of dyes from light-sensitive material layers to dye fixing layers. These may be classified into the groups of bases or base precursors, nucleophilic compounds, high boiling point organic solvents (oils, thermal solvents, surfactants and compounds having a mutual action with silver or silver ion, in view of the physico-chemical functions thereof. These groups of substances have, in general, composite functions and thus have two or more of the aforesaid acceleration effects. Details on these substances are described in Japanese Patent Application (OPI) No. 93451/86. In addition to the use of the aforesaid image forming accelerators, other materials are known for the generation of bases, and such compounds are usable as a base precursor in the present invention. For instance, U.S. patent application Ser. No. 890,442 (filed July 30, 1986) and European Patent Application No. 86 110568.2 (filed July 30, 1986) describes a method for the generation of bases by blending a sparingly soluble metal compound and a compound capable of reacting with the metal of the sparingly soluble metal compound for complex formation (which is called a complex forming compound); and Japanese Patent Application (OPI) No. 232451/86 describes a method for the generation of bases by electrolysis.

In particular, the former method is very effective. Examples of sparingly soluble metal compounds are zinc, aluminium, calcium and barium carbonates, hydroxides and oxides. The complex forming compounds are described in detail, e.g., in A. E. Martell and R. M. Smith, Critical Stability Constants, Vols. 4 and 5 published by Plenum Press. Specific examples of such compounds are salts of amino carboxylic acids, imidino acetic acids, pyridyl carboxylic acids, amino phosphoric acids, carboxylic acids (including mono-, di-, tri- and tetracarboxylic acids as well as those having a substituent such as a phosphono, hydroxyl, oxo, ester, amido, alkoxy, mercapto, alkylthio, phosphino or salts like group), hydroxamic acids, polyacrylates and polyphosphoric acid salts with alkali metals; guanidines, amidines or quaternary ammonium salts.

These sparingly soluble metal compounds and the complex forming compounds are preferably added separately to the light-sensitive materials and the dye fixing materials, individually.

In the present invention, various kinds of development stopping agents may be used in order to obtain constant images at all times despite variations in processing temperature and processing time in heat development.

The development stopping agents herein are compounds capable of neutralizing a base or reacting with a base after the completion of development, to thereby lower the base concentration in the film, thereby stopping the development, or the compounds may mutually react with silver or a silver salt, after the complete development, to inhibit the development. For example, these agents include acid precursors capable of releasing an acid on heating, electrophilic compounds which react an existing base by a substitution reaction on heating, as well as nitrogen-containing heterocyclic compounds, mercapto compounds and precursors thereof. Examples of these compounds are described, e.g., in Japanese Patent Application (OPI) Nos. 108837/85, 192939/85, 230133/85, and 230134/85.

Further, the compounds which release a mercapto compound by heating are useful and include those described in U.S. patent application Ser. Nos. 774,427 (filed Sept. 10, 1985), 809,627 (filed Dec. 16, 1985), 799,996 (filed Nov. 20, 1985), 827,139 (filed Feb. 7, 1986), 829,032 (filed Feb. 13, 1986), 828,481 (filed Feb. 12, 1986), and 830,031 (filed Feb. 18, 1986), Japanese Patent Application (OPI) No. 53632/86, etc.

In the present invention, the heat-developable photographic materials can contain compounds which activate the development and stabilizing of the formed images at the same time. Examples of preferred compounds are described in U.S. Pat. No. 4,500,626 (51st column to 52nd column).

In the present invention, various kinds of antifogging agents can be employed. Examples of useful antifogging agents include an azole, a carboxylic acid and a phosphoric acid each containing a nitrogen atom as described in Japanese Patent Application (OPI) No. 168442/84, a mercapto compound and a metal salt thereof as described in Japanese Patent Application (OPI) No. 111636/84, etc.

The heat developable photographic materials of the present invention may optionally contain an image toning agent. Examples of usable toning agents are described in U.S. patent application Ser. No. 809,627, filed Dec. 16, 1985.

The supports used for the heat developable photographic materials of the present invention and for the dye fixing materials which are, as the case may be, optionally used in the present invention, are those which are resistant to processing temperatures. In general, conventional supports such as glass, paper, polymer films, metals and analogues thereof may be used, and in addition, those as described in U.S. patent application Ser. No. 809,627, filed Dec. 16, 1985 may also be used.

The heat developable photographic materials of the present invention may contain various additives which are known to be usable in conventional heat developable photographic materials, and in addition, may contain other layers than the light-sensitive layers, such as antistatic layers, electrically conductive layers, protective layers, intermediate layers, antihalation layers, stripping layers and mat layers. Many useful additives are described in Research Disclosure, Vol. 170, RD No. 17029 (June 1978), pp. 9-15 and Japanese Patent Application (OPI) No. 88256/86, which include, for example, plasticizers, sharpness improving dyes, antihalation dyes, sensitizing dyes, matting agents, surfactants, fluorescent whitening agents, ultraviolet light absorbents, slide inhibitors, antioxidants and color fade-preventing agents.

In particular, protective layers generally contain an organic or inorganic matting agent for the purpose of blocking prevention. In addition, the protective layers may optionally contain a mordant and a UV light absorbent. The present photographic materials may have two or more protective layers and two or more intermediate layers.

The intermediate layers may contain a reducing agent for the prevention of color fading or color mixing, a UV light absorbent or a white pigment such as Ti02. The white pigment may be added not only to the intermediate layers, but also to the emulsion layers, for the purpose of intensifying sensitivity.

The photographic elements of the present invention comprise a light-sensitive element capable of releasing or forming a dye(s) on heat development and a dye fixing element for fixing the dyes formed.

Both a light-sensitive element and a dye fixing element are indispensable in a system for the formation of images by diffusion transfer. Such may be classified into two typical systems. In one system, the light-sensitive element and the dye fixing elements are separately provided on two different supports; in the other system, the two elements are provided on the same support.

The relationship between the light-sensitive element and the dye fixing element, between these elements and the support(s) and between these elements and a white reflective layer are described in U.S. patent application Ser. No. 809,627, filed Dec. 16, 1985 (pp. 58-59) and U.S. Pat. No. 4,500,626 (57th column), which may be applied to the present invention.

One representative example of the embodiment in which the light-sensitive element and the dye fixing element are provided on the same support is a type in which the light-sensitive element is not necessary to peel apart from the image receiving element after the formation of transferred images. In such a case, on a transparent or opaque support a light-sensitive layer, a dye fixing layer and a white reflective layer are superposed. Examples of preferred embodiments of layer structure include transparent or opaque support/light-sensitive layer/white reflective layer/dye fixing layer, or transparent support/dye fixing layer/white reflective layer/light-sensitive layer, etc.

Another typical example of the embodiment in which the light-sensitive element and the dye fixing element are provided on the same support is a type in which a part or all of the light-sensitive element is separated from the dye fixing element and a stripping layer is provided on an appropriate position of the element as described, for example, in Japanese Patent Application (OPI) No. 67840/81, Canadian Patent No. 674,082, U.S. Pat. No. 3,730,718, etc.

The light-sensitive element or the dye fixing element may form a structure having an electrically conductive heat generating layer suitable for use as heating means for the purpose of heat development or diffusion transfer of dyes.

In this case, the transparent or opaque heating element (layer) may be formed in a conventional manner for the formation of conventional heating elements

For the formation of a heating element, two methods are generally used. In one method, a thin film of a semiconductive inorganic material is used, and in the other method an organic thin film made of a dispersion of electrically conductive fine particles dispersed in a binder is used. Materials usable in these methods are described in Japanese Patent Application (OPI) No. 29835/86.

The dye fixing element used in the present invention contains at least one layer containing a mordant, and in the case the dye fixing layer is positioned on the surface of the photographic material, a protective layer may optionally be coated thereon.

The layer construction of the dye fixing element, the binder, the additives and the position of the mordant agent containing layer are described in U.S. patent application Ser. No. 809,627, filed Dec. 16, 1985 and in the patent publications referred to therein, which may be applied to the present invention.

The dye fixing element used in the present invention may optionally have, in addition to the aforesaid layers, a stripping layer, a matting agent layer, a curl preventive layer or like auxiliary layers.

One or more of the above mentioned layers may contain, if necessary, bases and/or base precursors for the acceleration of dye transfer, hydrophilic thermal solvents, color fade-preventing agents for inhibition of the discoloration of the dyes, UV light absorbents, sliding agents, matting agents, antioxidants, vinyl compound dispersions for increased dimensional stability and fluorescent whitening agents. Examples of these additives are described in Japanese Patent Application (OPI) No. 88256/86.

The binders in the aforesaid layers are preferably hydrophilic, and transparent or semi-transparent hydrophilic colloids are typical. For example, the binders as mentioned in the aforesaid photographic materials may be used.

The image receiving layers of the present invention are dye fixing layers to be used in the heat developable color photographic materials, and the mordants used in the layers may freely be selected from conventional mordants. In particular, polymer mordants are especially preferred. The polymer mordants include tertiary amino group-containing polymers, nitrogencontaining heterocyclic polymers and quaternary cationic group-containing polymers.

Examples of these polymers are described in U.S. patent application Ser. No. 809,627, filed Dec. 16, 1985 and U.S. Pat. No. 4,500,626 (57th column to 60th column).

The method of providing heat developable light-sensitive layers, protective layers, intermediate layers, subbing layers, backing layers and other layers is described in U.S. Pat. No. 4,500,626 (55th column to 56th column), which may be applied to the present invention.

As the light source for image exposure to record the images on the heat developable photographic materials may use radiation including visible rays, and for example, various light sources as described, e.g., U.S. patent application Ser. No. 809,627, filed Dec. 16, 1985 and U.S. Pat. No. 4,500,626 (56th column) may be used.

The heating temperature for development in heat development is generally about 50.degree. C. to about 250.degree. C., and is preferably about 80.degree. C. to about 180.degree. C. The heating temperature for transfer in the transfer step is generally within a range from a temperature in the heat development to room temperature, and is especially preferably within the range from 50.degree. C. or more to the lower temperature than in the heat development step by about 10.degree. C. For the heating means in the development step and/or the transfer step, there may be used a hot plate, iron, a hot roller or any other heating elements with carbon or titanium white.

The development and transfer may be effectively carried out simultaneously or continuously by heating the material in the presence of a small amount of a solvent, such as water, as described in detail in Japanese Patent Application (OPI) Nos. 218443/84 and 238056/86. In such method, the aforesaid image forming accelerator may earlier be incorporated in either the dye fixing material or the light-sensitive material, or in both, or it may be externally added to the photographic processing system.

In a system where development and transfer are carried out simultaneously or continuously, the heating temperature is preferably from 50.degree. C. or more to the boiling point of the solvent. For instance, when water is used as the solvent, the heating temperature is desirably from 50.degree. C. or higher to 100.degree. C. or lower.

Solvents may be used for the transfer of the mobile dye to the dye fixing layer.

Examples of solvents used for the acceleration of development and/or transfer of the mobile dye to the dye fixing layer are water and a basic aqueous solution containing an inorganic alkali metal salt or an organic base. (The bases, as referred to in the item of the image forming accelerators hereinbefore may be used.) Further, low boiling point solvents as well as mixtures thereof comprising a low boiling point solvent and water or a basic aqueous solution may also be used. Surfactants, antifogging agents and sparingly soluble metal salt complex forming compounds may be incorporated in the solvent(s).

The solvent(s) may be added to either the dye fixing material or the light-sensitive material or to both. The amount added may be small, i.e., to such a degree that the weight of the solvent used is the same as or less than that which corresponds to the maximum swollen volume of the total coated film, especially the same as the weight or less a left by subtracting the weight of the total coated films from the weight of the solvent which corresponds to the maximum swollen volume of the total coated films.

The solvent (for example, water) may accelerate the formation of the images and/or the transfer of the dyes, when applied between the light-sensitive layer of the heat developable photographic material and the dye fixing layer of the dye fixing material, and the solvent may earlier be incorporated into either the lightsensitive layer or the dye fixing layer or into both.

The incorporation of the solvent into the light-sensitive layer and/or the dye fixing layer is described, e.g., U.S. patent application Ser. No. 809,627, filed Dec. 16, 1985.

For the acceleration of dye transfer, hydrophilic thermal solvents which are solid at room temperature but which dissolve at a higher temperature may be incorporated into the light-sensitive materials or the dye fixing materials. The hydrophilic thermal solvents may be incorporated into either the light-sensitive material or the dye fixing material or into both. For incorporation, the solvents may be added to any of the emulsion layer(s), intermediate layer(s), protective layer(s) and dye fixing layer(s), and, in particular, these are especially preferably added to the dye fixing layers and/or an adjacent layer(s).

Examples of thermal solvents are ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes and other heterocyclic compounds.

Exemplary heating means which can be used in the transfer step are described in U.S. patent application Ser. No. 809,627, filed Dec. 16, 1985. For heating, a graphite, carbon black, metal or the like electrically conductive material layer may be coated on the dye fixing material, whereby the electrically conductive layer may directly be heated by imparting an electric current thereinto.

The heat developable light-sensitive material and the dye fixing material are typically laminated under pressure, and typical pressure conditions and the means for the pressure application are described in U.S. patent application Ser. No. 809,627, filed Dec. 16, 1985.

The compounds of the present invention may be used in silver halide photographic materials for color diffusion transfer, which are developed with a developer near room temperature. Such color diffusion transfer is described, e.g., in Belgian Pat. No. 757,959. As the dye providing substances for color diffusion transfer there may be used compounds of formula (I) of the present invention where PUG is a diffusible dye, and in addition, compounds of the following formula (V) may also be used.

in which Dy represents a dye moiety (or precursor thereof); and Y represents a substrate having a function of varying the diffusibility of the dye providing substance (V) as a result of development.

The wording "to vary the diffusibility" as used herein means that: (1) the dye providing substance (V) is initially non-diffusible and this is changed into a diffusible form or a diffusible dye is released thereform; or (2) the dye providing substance (V) is initially diffusible and is changed into a non-diffusible form. The change depends upon the property of Y itself, resulting from the oxidation of Y in one case or from the reduction of the Y in the other case.

In the former case where "the diffusibility varies because of the oxidation of Y", examples of Y are dye releasing redox substrates, which are p-sulfonamidonaphthols (including p-sulfonamidophenols, as described in Japanese Patent Application (OPI) Nos. 33826/73 and 50736/78; European Patent No. 76,492), o-sulfonamidophenols (including o-sulfonamidonaphthols, as described in Japanese Patent Application (OPI) Nos. 113624/76, 12642/81, 161830/81, 16131/81, 4043/82, and 650/82, U.S. Pat. No. 4,053,312, and European Patent No. 76,492), hydroxysulfonamido-heterocyclic compounds (as described in Japanese Patent Application (OPI) No. 104343/76, European Patent No. 76,492), 3-sulfonamidoindoles (as described in Japanese Patent Application (OPI) Nos. 104343/76, 46730/78, 130122/79, and 85055/82, and European Patent No. 76,492), o-sulfonamidoketones (as described in Japanese Patent Application (OPI) Nos. 3819/78 and 48534/79 and European Patent No. 76,492).

Another embodiment is a system where the dye is released by an intranuclephilic attack of the compound after oxidation of Y. Intramolecular assistant type substrates as described in Japanese Patent Application (OPI) Nos. 20735/82 and 65839/84 are the examples of such Y groups.

Still another embodiment involves the use of such a substrate that releases the dye by an intramolecular cyclization reaction under basic conditions but does not substantially release any dye after Y has been oxidized. Examples of the substrates of this kind are described in Japanese Patent Application (OPI) No. 63618/76. Further substrates that release the dye because of a ring rearrangement of an isoxazolone ring in the presence of a nucleophilic reagent may be used, which is a modification of this embodiment. Examples of substrates of this modified case are described in Japanese Patent Application (OPI) Nos. 111628/74 and 4819/77.)

A further embodiment involves the use of substrates that release the dye moiety by dissociation of an acidic proton under basic conditions but do not substantially release any dye after Y has been oxidized. Examples are described in Japanese Patent Application (OPI) Nos. 69033/78 and 130927/79.

In the latter case where "the diffusibility varies because of the reduction of Y", examples of Y are nitro compounds as described in Japanese Patent Application (OPI) No. 110827/78 and quinone compounds as described in Japanese Patent Application (OPI) No. 110827/78 and U.S. Pat. Nos. 4,356,249 and 4,358,525. These are reduced by a reducing agent, which is called an electron donor, remaining without having been consumed in development and, as a result, release the dye because of an intramolecular attack by the resulting nucleophilic group. Further, quinone type substrates capable of releasing the dye moiety because of dissociation of the acidic proton of the reduced form thereof are usable, which are a modification of the present embodiment. Examples of these substrates are described in Japanese Patent Application (OPI) Nos. 130927/79 and 164342/81.

In the case the aforesaid substrates which vary diffusibility because of reduction thereof are used, the pertinent reducing agent (=electron donor) which mediates between exposed silver halide and the dye providing substance is indispensably used, and the examples of such agents are described in the aforesaid publications. So called LDA compounds which per se contain an electron donor in the substrate Y may also be effectively used.

The aforesaid dye providing substances form a mobile dye in imagewise distribution in the photographic material by wet development, which corresponds to exposure of the material, and the dye image is transferred to the dye fixing material by diffusion transfer to obtain a visible image thereon.

Photographic elements for color diffusion transfer will now be explained in greater detail.

Photographic elements for color diffusion transfer are preferably in the form of a film unit comprising a combination of the light-sensitive material (light-sensitive element) and the dye fixing material (image

In one typical embodiment of such a film unit, the image receiving element and the light-sensitive element are laminated on one transparent support, and the light-sensitive element need be peeled off from the image receiving element after the completion of the image transfer. More precisely, the image receiving element comprises at least one mordant layer; and the light-sensitive element preferably comprises the combination of a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer, the combination of a green-sensitive emulsion layer, a red-sensitive emulsion layer and an infrared-sensitive emulsion layer or the combination of a blue-sensitive emulsion layer, a red-sensitive emulsion layer and an infrared-sensitive emulsion layer, and the corresponding yellow dye providing substance, magenta dye providing substance and cyan dye providing substance are incorporated into each of these emulsion layer. An "infrared-sensitive emulsion layer" means an emulsion layer having light sensitivity to light of 700 nm or more, especially 740 nm or more. A white reflective layer containing a solid pigment such as titanium oxide is normally provided between the mordant layer and the light-sensitive layer or the dye providing substance-containing layer, whereby the transferred image may be seen through the transparent support. A light shielding layer may be provided between the white reflective layer and the light-sensitive layer so that the development may be carried out in the light. If necessary, a peeling layer may be provided so that a part of all of the light-sensitive element may be peeled off the image receiving element. Examples of this embodiment are described, e.g., Japanese Patent Application (OPI) No. 67840/81 and Canadian Pat. No. 674,082.

In another non-peeling type embodiment, the light-sensitive element is coated on the transparent support, the white reflective layer is coated thereover and the image receiving layer is further superposed thereover. A system where the image receiving element, the white reflective layer, the peeling layer and the light-sensitive element are laminated on the same support and the light-sensitive element is peeled off the image receiving element is described in U.S Pat. No. 3,730,718.

On the other hand, a system where the light-sensitive element and the image receiving element are separately provided on two different supports is typically classified into two types. One is a peeling type and the other is non-peeling type. These two types will now be explained in detail.

In one preferred embodiment of a peeling-type film unit, a light reflective layer is provided on the back surface of the support and at least one image receiving layer is provided on the front surface thereof. This embodiment is so planned that the light-sensitive element is provided on the support having a light shielding layer and that the light-sensitive layer coated surface is reversed to face to the image receiving layer coated surface after the exposure (or, for example, during development) while the light-sensitive layer coated surface and the mordant layer coated surface are not faced to each other before exposure. After the completion of the image transfer to the mordant layer, the light-sensitive element is immediately peeled off the image receiving layer.

In another preferred embodiment of a non-peeling type film unit, at least one mordant layer is provided on the transparent support and the light-sensitive element is provided on the transparent or light shielding layer coated support, whereupon the light-sensitive layer coated surface and the mordant layer coated surfaces are kept to face to each other.

A photographic element of the aforesaid color diffusion transfer type may optionally be combined with a container (or processing element) which contains an alkaline processing solution and which may be ruptured under pressure. In a non-peeling type film-unit comprising an image receiving element and a light-sensitive element laminated on one support, in particular, the processing element is preferably provided between the light-sensitive element and a cover sheet coated thereon. In another embodiment where the light-sensitive element and the image receiving element are separately provided on respective two supports, the processing element is preferably provided between the light-sensitive element and the image receiving element at latest during development. The processing element preferably contains a light shielding agent (such as carbon black or dye(s) whose color may vary because of variations in pH) and/or a white pigment (such as titanium white). In color diffusion transfer type film units, it is preferred that the cover sheet, the image receiving element or the light-sensitive element be combined with a neutralization timing system comprising the combination of a neutralizing layer and a neutralization timing layer.

The present invention will now be explained in greater detail by reference to the following examples, which, however, are not intended to be interpreted as limiting the scope of the present invention.

The following layers (I) and (II) were coated in that order on a polyethylene terephthalate support to obtain the test samples.

Layer (I):

(a) Gelatin dispersion comprising Compound 1 of the present invention (reducible dye providing substance) (0.27 mmole/m.sup.2) and tricresyl phosphate (0.4 g/m.sup.2),

(b) Gelatin dispersion comprising reducing substance (S-3) (0.52 mmole/m.sup.2) and tricresyl phosphate (0.2 g/m.sup.2),

(c) Guanidine trichloroacetate (0.22 g/m.sup.2), and

(d) The following compound (0.1 g/m.sup.2): ##STR13##

Layer (I) was a color material layer containing the above components (a) through (d), and the gelatin content therein (including the gelatin content in dispersions (a) and (b)) was 1.2 g/m.sup.2.

Layer- (II)

This was a protective layer containing guanidine trichloroacetate (0.37 g/m.sup.2) and gelatin (1 g/m.sup.2).

This was test sample No. 101. Other test samples Nos. 102 to 105 were prepared, in the same manner as for test sample No. 101 but dye providing substance (Compound 1) therein was replaced by Compound 2, 4, and 17 described above or Comparative Compound X shown below.

The formation of the image receiving sheet with the dye fixing layer is now explained.

10 g of poly (methyl acrylate/co-N,N,N- trimethyl-N-vinylbenzylammonium chloride) (ratio of methyl acrylate to vinylbenzylammonium chloride 1:1, molar) was dissolved in 200 ml of water, and the resulting solution was uniformly blended with 100 g of a 10 wt % acid treated gelation emulsion. The resulting mixture solution was uniformly coated on a polyethylene terephthalate laminated paper support to form a film having a wet film thickness of 20 m. This was the image receiving sheet.

Each of the above test samples 101 to 105 was heated on a heat block (block heated to 140.degree. C.) for a determined period of time, and then was intimately attached to the image receiving sheet, to which had been added 8 ml/m.sup.2 of water, so that the coated surfaces of the two elements faced each other. The thus attached sheet was heated at 90.degree. C. for 20 seconds for dye transfer, and then the image receiving sheet was peeled off. The reducible dye releasing compound was reduced by the electron donor in the first heating step, whereby the dye was released and an image of high transferred color density was obtained.

The following Table 1 shows the heating time required for the release of half of the dye from the dye providing substance and the maximum color density (reflection).

The above results prove that the dye providing compounds of the present invention release a dye within an extremely short period of time and that the releasing speed may easily be controlled because of the structures of the substituents in the compounds.

The following layers were coated in the recited order on a transparent polyethylene terephthalate support to obtain light-sensitive element sample (A).

Layer (I):

(a) Light-sensitive silver iodobromide emulsion (0.36 g Ag/m.sup.2),

(b) Benzotriazole silver emulsion (0.18 g Ag/m.sup.2),

(c) Gelatin dispersion comprising Compound 15 of the present invention (0.27 mmole/m.sup.2) and tricresyl phosphate (1 g/m.sup.2),

(d) Gelatin dispersion comprising reducing substance 11 of this invention (0.27 mmole/m.sup.2) and tricresyl phosphate (0.2 g/m.sup.2),

(e) Base precursor of the following structure (0.44 g/m.sup.2): ##STR15## (f) Compound of the following structure (0.1 g/m.sup.2): ##STR16##

Layer (I) was a light-sensitive layer containing the above components (a) through (f), and the gelatin content therein (including the gelatin content in the above (a) through (d)) was 1.2 g/m.sup.2.

Layer (II):

(a) This was a protective layer containing the above base precursor (e) (0.74 g/m.sup.2) and gelatin (1 g/m.sup.2).

In the same manner as above, with the exception that Compound 11 in layer (I) was replaced by one of Compounds 1 and 4, other light-sensitive element samples 202 and 203 were prepared. These samples were exposed to light and then uniformly heated on a hot plate heated at 140.degree. C. for 30 seconds. Next, the sample was intimately attached to the same image receiving sheet as in Example 1, to which had been added 8 ml/m.sup.2 of water, and heated for 20 seconds at 90.degree. C. After heating, the image receiving sheet was peeled off, whereby a positive color image was obtained.

The photographic characteristic of each sample as obtained by sensitometry is shown in the following Table 2.

The following layers were coated in the recited order on a transparent polyethylene terephthalate support to obtain a light-sensitive element sample.

Red-sensitive layer:

Light-sensitive layer comprising the following components (a) through (e):

(a) Red-sensitive silver iodobromide gelatin emulsion (0.36 g Ag/m.sup.2),

(b) Benzotriazole silver gelatin emulsion (0.18 g Ag/m.sup.2), and

(c) Gelatin dispersion comprising Compound 9 (0.27 mmole/m.sup.2), precursor reducing substance (S-11) (0.4 mmole/m.sup.2) and tricresyl phosphate (0.37 g/m.sup.2) ##STR17## (d) 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone (ETA) (0.32 mmole/m.sup.2), and

(e) Gelatin (including the gelatin component in the above (a) through (c))(1.24 g/m.sup.2).

Intermediate layer: Layer comprising 2,5-di(tertpentadecyl)hydroquinone (=compound for preventing color mixing from the interlayer diffusion of ETA) (0.81 g/m.sup.2), polyvinyl acetate (0.79 g/m.sup.2) and gelation (0.38 g/m.sup.2).

Green-sensitive layer: The same layer as the above red-sensitive layer with the exception that (a) is a green-sensitive gelatin emulsion and (c) is Compound 11.

Intermediate layer: The same layer as the above intermediate layer.

Blue-sensitive layer: The same layer as the above red-sensitive layer with the exception that (a) is a blue-sensitive emulsion and (c) is Compound 23.

Protective layer: Layer containing gelatin (0.4 g/m.sup.2).

The sample was, after exposure adhered to the image receiving sheet of the Example 1, which had been dipped in a 1M K.sub.3 PO.sub.4 solution, and heated at 95.degree. C. for 20 seconds, and then the image receiving sheet was peeled off.

The photographic characteristic of the sample as obtained by sensitometry is given in the following Table 3.

The results in the above Table 3 prove that the sample formed an excellent positive image of high quality, having a high maximum density and a low minimum density.

The following layers were coated, in the order recited, on a transparent polyethylene terephthalate support to obtain a light-sensitive element sample.

(I) Image receiving layer containing:

(a) copoly[styrene-n-vinylbenzyl N,N,N-trihexylammonium] (4.0 g/m.sup.2) and

(b) gelatin (4.0 g/m.sup.2).

White reflective layer containing:

(a) titanium dioxide (22 g/m.sup.2) and

(b) gelatin (2.2 g/m.sup.2).

(III) Opaque layer containing:

(a) carbon black (2.7 g/m.sup.2) and

(b) gelatin (2.7 g/m.sup.2).

(IV) Cyan dye providing layer containing:

(a) gelatin dispersion comprising cyan dye providing Compound 9 (0.33 mmole/m.sup.2) and Compound S-11 (0.4 mmole/m.sup.2) and

(b) gelatin (1.1 g/m.sup.2, including the gelatin in the above (a))

(V) Red-sensitive layer containing:

(a) red-sensitive silver iodobromide emulsion (0.5 Ag/m.sup.2) and

(b) gelatin (1.1 g/m.sup.2, including the gelatin in the above (a)).

(VI) Intermediate layer containing:

(a) 2,5-di(t-pentadecyl)hydroquinone (0.82 g/m.sup.2)

(b) vinyl acetate (0.8 g/m.sup.2), and

(c) gelatin (0.4 g/m.sup.2).

(VII) Magneta dye providing layer containing:

(a) gelatin dispersion comprising magenta dye providing Compound 11 (0.3 mmole/m.sup.2) and Compound S-11 (0.4 mmole/m.sup.2) and

(b) gelatin (1.1 g/m.sup.2, including the gelatin in the above (a)).

(VIII) Green-sensitive layer containing:

(a) green-sensitive silver iodobromide emulsion (0.5 g Ag/m.sup.2) and

(b) gelatin (1.1 g/m.sup.2, including the gelatin in the above (a)).

(IX) The same intermediate layer as (VI).

(X) Yellow dye forming layer containing:

(a) gelatin dispersion comprising yellow dye providing Compound 23 (0.5 mmole/m.sup.2) and Compound S-11 (0.6 mmole/m.sup.2) and

(b) gelatin (1.1 g/m.sup.2, including the gelatin in the above (a)).

(XI) Blue-sensitive layer containing:

(a) blue-sensitive silver iodobromide emulsion (0.5 g/m.sup.2) and

(b) gelatin (1.1 g/m.sup.2, including the gelatin in the above (a)).

(XII) Protective layer containing:

(a) polymethyl methacrylate latex (average particle size: 4 m) (0.9 g/m.sup.2),

(b) the following ultraviolet absorbents (A) and (B) (each 0.4 mmole/m.sup.2),

(c) hardener bisvinylsulfonylmethyl ether (0.15 g/m.sup.2), and

(d) gelatin (1.3 g/m.sup.2).

Ultraviolet absorbent (A): ##STR18## Ultraviolet absorbent (B): ##STR19##

Next, the following layers were coated in the recited order on a transparent polyethylene terephthalate film to form a cover sheet.

(I) Acid-neutralizing layer containing:

(a) polyacrylic acid (17 g/m.sup.2),

(b) N-hydroxysuccinimidobenzene sulfonate (0.06 g/m.sup.2), and

(c) ethylene glycol (0.5 g/m.sup.2).

(II) Timing layer of cellulose acetate (acetylation degree: 54%), as coated in a thickness of 2 .mu.m.

(III) Timing layer of a copolymer latex comprising vinylidene chloride and acrylic acid, as coated in a thickness of 4 .mu.m.

Next, a processing solution comprising the following composition was prepared.

The above prepared light-sensitive element sample was exposed through a wedge and the cover sheet was attached thereto, whereupon the processing solution was uniformly spread therebetween in a thickness of 80 m using a pair of parallel rollers.

After development for one hour, the sample was subjected to sensitometry, and the results are given in the following Table 4. The results prove that the sample formed excellent color images of high quality having a high transferred dye density with less color stain in white background areas.

The following layers (1) through (11) were coated in that order on a black support to obtain a light-sensitive element sample.

(1) Layer containing the following cyan DRR compound (0.36 mmole/m.sup.2), tricyclohexyl phosphate (0.09 g/m.sup.2), 2,5-di(t-pentadecyl)hydroquinone (0.1 g/m.sup.2) and gelatin (0.44 g/m.sup.2). ##STR20##

(2) Layer containing a red sensitive internal latent image type direct reversal silver bromide gelatin emulsion (0.5 g Ag/m.sup.2), gelatin (0.78 g/m.sup.2), the following nucleating agent (27 g/m.sup.2) and sodium pentadecylhydroquinone sulfonate (0.06 g/m.sup.2). ##STR21##

Layer containing 2,5-di(tertpentadecyl)hydroquinone (0.71 g/m.sup.2), a copolymer of vinylpyrrolidone and vinyl acetate (molar ratio: 7/3) (0.24 g/m.sup.2) and gelatin (0.4 g/m.sup.2).

(4) Layer containing gelatin (0.3 g/m.sup.2).

(5) Layer containing the following magneta DRR compound (0.49 g/m.sup.2), tricyclohexyl phosphate (0.08 g/m.sup.2), 2,5-di(tert-pentadecyl)hydroquinone (0.01 g/m.sup.2) and gelatin (0.5 g/m.sup.2). ##STR22##

(6) Layer containing a green-sensitive internal latent image type direct reversal silver bromide emulsion (0.34 g Ag/m.sup.2), gelatin (0.66 g/m.sup.2), the same nucleating agent as layer (2) (12.9 g/m.sup.2) and sodium pentadecylhydroquinone sulfonate (0.04 g/m.sup.2).

(7) Layer containing 2,5-di(tertpentadecyl)hydroquinone (0.71 g/m.sup.2), a copolymer of vinylpyrrolidone and vinyl acetate (molar ratio: 7/3) (0.24 g/m.sup.2) and gelatin (0.4 g/m.sup.2).

(8) Layer containing gelatin (0.25 g/m.sup.2).

(9) Layer containing the following yellow DRR compound (0.48 g/m.sup.2), tricyclohexyl phosphate (0.03 g/m.sup.2), 2,5-di(tert-pentadecyl)hydroquinone (0.004 g/m.sup.2) and gelatin (0.43 g/m.sup.2). ##STR23##

Layer containing a blue sensitive internal latent image type direct reversal silver bromide emulsion (0.84 g Ag/m.sup.2), gelatin (0.9 g/m.sup.2), the same nucleating agent as the layer (5) (29 g/m.sup.2) and sodium pentadecylhydroquinone-sulfonate (0.05 g/m.sup.2).

(11) Layer containing gelatin (1.0 g/m.sup.2).

This light-sensitive element was called light-sensitive element sample 501.

A dispersion comprising the following components (a), (b) and (c) was incorporated into each of the red-sensitive emulsion layer, the green-sensitive emulsion layer and the blue-sensitive emulsion layer in sample (1) to obtain a light-sensitive element sample 502.

(a) The antifoggant releasing compound 10 of this invention (0.1 mmole/m.sup.2);

Precursor reducing substance S-45 (0.1 mmole/m.sup.2); and

(c) Trihexyl phosphate (0.01 g/m.sup.2) ##STR24##

On the other hand, the following layers (1) through (5) were coated in that order on the front surface of a white support, which had a carbon black layer and a titanium white layer in that order on the back surface thereof, to obtain a dye receiving sheet.

(1) Layer containing a copolymer of acrylic acid and butyl acrylate (weight ratio: 80/20) (22 g/m.sup.2) and 1,4- bis(2,3-epoxypropoxy)butane (0.44 g/m.sup.2).

(2) Layer containing acetyl cellulose (modified by hydrolysis of 100 g acetyl cellulose to form 39.4 g of acetyl groups) (3.8 g/m.sup.2), a copolymer of styrene and maleic anhydride (weight ratio: 60/40; molecular weight: about 50,000) (0.2 g/m.sup.2) and 5-(.beta.-cyanoethylthio)-1-phenyltetrazole (0.115 g/m.sup.2).

Layer containing a copolymer latex of vinylidene chloride, methyl acrylate and acrylic acid (weight ratio: 85/12/3) (2.5 g/m.sup.2) and a polymethyl methacrylate latex (particle size: 1 to 3 .mu.m) (0.05 g/m.sup.2).

(4) Mordant layer containing the following mordant (3.0 g/m.sup.2) and gelatin (3.0 g/m.sup.2). ##STR25##

(5) Layer containing phthalated gelatin (1 g/m.sup.2).

Next, 0.8 g of the processing solution having the following composition was filled in a rupturable container.

Element samples 501 and 502 were exposed through a wedge, and then the above processing solution was spread between the light-sensitive element sample and the dye receiving sheet in a thickness of 60 m. After development for 2 minutes at 25.degree. C., the dye receiving sheet was peeled off to obtain a transferred color image thereon.

The results of sensitometry on each sample are shown in the following Table 5. The results prove that light-sensitive element sample 502 containing the antifoggant releasing compound of the present invention formed a more excellent image with less fog in white background areas as compared with comparative light-sensitive element sample 501.

An aqueous solution of silver nitrate and an aqueous solution of potassium halides were added to an aqueous gelatin solution by an ordinary ammonia method to provide silver iodobromide grains (AgI: 2 mole %) having a mean grain size of 1.0 .mu.m and after desalting by means of an ordinary flocculation method, gold and sulfur sensitizations using chloroacuric acid and sodium thiosulfate were applied thereto and 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene was added thereto to provide a light-sensitive silver iodobromide emulsion.

By adding each of the compounds shown in Table 6 described below to the emulsion prepared above and coating the emulsion on a support followed by drying, Samples 601 to 611 were obtained. Each of the samples was stepwise exposed to optical wedge using sensitometer, processed by automatic developer RU (trade name, made by Fuji Photo Film Co., Ltd.) using the following developer A and fixing solution A for 90 seconds at 35.degree. C., respectively, and the photographic performance was measured. The results obtained are shown in Table 6.

Compound A (comparison): ##STR26##

The relative sensitivity in Table 6 is the reciprocal of the exposure amount required for obtaining a density of fog +1.0 with the sensitivity of Sample 602 at development temperature of 35.degree. C. being shown as 100.

Furthermore, the fog shown in the above table is the value containing the base density.

As is clear from the results shown in Table 6, it can be seen that in Samples 604 to 611 using the compounds of this invention, fog is effectively inhibited without reducing the sensitivity as compared to Samples 602 and using the comparison compound.

A multilayer color photographic material (Sample was prepared by coating the following layers on a triacetyl cellulose film support having subbing layer.

The coated amount was shown by g/m.sup.2 as silver for silver halide emulsion and colloid silver and by g/m.sup.2 for coupler, additives, and gelatin, and for sensitizing dye by mole number per mole as silver halide in the same layer.

Each layer further contained stabilizer Cpd - 3 (0.04 g/m.sup.2) and surface active agent Cpd - 4 (0.02 g/m.sup.2) s coating aid. Furthermore, each layer contained Cpd - 5 0.5 g/m.sup.2) and Cpd - 6 (0.5 g/m.sup.2).

The compounds used for preparing the color photographic material were as follows. ##STR27##

By following the same procedure as the case of Sample 701 except that each of Comparison compound AF - 1 and Compounds ED - 1 and ED - 2 of this invention was added to Layer 4, Layer 7 and Layer 12 as shown in Table 7 below, Samples 702 to 705 were prepared.

Each of Samples 701 to 705 was subjected to sensitometric exposure using white light and then processed by Process A or Process B shown below. The results obtained are shown in Table 7.

The compositions of the processing solutions used in the process were as follows.

Wash Water:

City water was passed through a mixed bed column filled with a H-type strong acid cation-exchange resin (Amberlite IR-120B, made by Rohm and Haas Company) and OH-type anion-exchange resin (Amberlite IR-400) to reduce the concentrations of calcium and magnesium ions below 3 mg/liter and then 20 mg/liter of sodium dichloroisocyanurate and 1.5 g/liter of sodium sulfate were added thereto. The pH thereof was in the range of 6.5 to 7.5.

A multilayer color photographic material (Sample 801) having the following layers on a triacetyl cellulose film support having subbing layer was prepared.

Layer Composition:

The numeral for each layer was the coated amount shown by g/m.sup.2, which was as silver for silver halide emulsion and colloid silver. Also, about sensitizing dye and coupler, the amount was shown by mole unit per mol of the silver halide in the same layer.

Each layer further contained a gelatin hardening agent H - 1 and a surface active agent.

By following the same procedure as the case of Sample 801 except that each of Comparison compound AF - 1 and Compounds ED - 1 and ED - 2 of this invention was added to Layer 5 of Sample 801, Samples 802 to 804 were prepared.

The compounds used for preparing the above samples were shown below. ##STR32##

Each of the samples thus prepared was imagewise exposed using an argon light source the color temperature of which had been adjusted to 4800.degree. K. with a filter so that the maximum exposure amount became 10 CMS and processed at 38.degree. C. as follows. The results obtained are shown in Table 8 below.

The compositions of the processing solutions used were as follows.

As is clear from the results shown in Table 8, it can be seen that in Samples 803 and 804 containing the antifoggant-releasing compound of this invention and the proper reducing agent, the formation of fog is inhibited without reducing the sensitivity.

While the invention has been described in detail and with reference to specific examples thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.