Silver halide photographic emulsion

BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a silver halide photographic emulsion, and particularly relates to a silver halide photographic emulsion having an elevated spectral sensitivity in green wavelength region. More specifically, the present invention relates to a silver halide photographic emulsion which leads to photographic light-sensitive materials having an elevated spectral sensitivities in green short wavelength region and excellent storage stabilities.
2. Description of the Prior Art
As silver halide photographic emulsions having an elevated spectral sensitivity in a green wavelength region, silver halide photographic emulsions wherein an oxacarbocyanine dye and an imidacarbocyanine dye are used together (for example, Japanese Patent Unexamined Published Application (hereinafter referred to as "J. P. KOKAI") Nos. 59-116646, 59-116647, 59-140443, 59-149346 and the like), those wherein an oxacarbocyanine dye and an oxathiacarbocyanine dye are used together (for example, Japanese Patent Publication for Opposition Purpose (hereinafter referred to as "J. P. KOKOKU") No. 46-11627, J. P. KOKAI No. 60-42750 and the like), those wherein 2 or more oxacarbocyanine dyes are used together (for example, J. P. KOKAI No. 52-23931 and the like), and the like have hitherto been known. However, any of those photographic emulsion has only a low spectral sensitivity in a green short wavelength region, which resulted in a problem on color reproduction.
On the other hand, as sensitizing dyes having a maximal valve of spectral sensitivity between 520 nm and 545 nm, benzimidazolooxazolocarbocyanine dyes (for example, compounds disclosed in J. P. KOKOKU No. 44-14030 and the like) and dimethynemerocyanine dyes (for example, compounds disclosed in U.S. Pat. Nos. 2,493,748, 2,519,001 and 3,480,439 and the like) have hitherto been known. Thus, to solve the above problem, using together a further sensitizing dye having a maximal value of spectral sensitivity between 520 nm and 545 nm may be thought of. However, in emulsions containing a benzimidazolooxazolocarbocyanine or a dimethynemerocyanine, increase of fog owing to a high temperature or a condition of high temperature and high humidity after application of the emulsion, or lowering of sensitivity owing to poorness of stability with time lapse after application of the emulsions is observed. Thus, such a dye does not seem to be suitable for using together.
Under the above circumstances, development of a photographic emulsion which is free from the above drawbacks and has a maximal value of spectral sensitivity in a green short wavelength region, and wherein a new sensitizing dye is used has been desired.
SUMMARY OF THE INVENTION
The present invention relates to spectral sensitization of a silver halide photographic emulsion, and the first object of the present invention is to provide a silver halide photographic emulsion having an elevated spectral sensitivity in a green wavelength region.
The second object of the present invention is to provide photographic light-sensitive materials which have elevated spectral sensitivities in a green short wavelength region and are excellent in storage stability.
The above objects of the present invention have been accomplished by a silver halide photographic emulsion which contains at least one of the compounds represented by the following general formula (I), and at least one of the compounds represented by the following general formula (III):
General formula (I) ##STR2## wherein R.sub.0 and R.sub.1 may be the same or different, and represent hydrogen atoms, alkyl groups, aryl groups, alkoxy groups, aryloxy groups, halogen atoms, alkoxycarbonyl groups, acylamino groups, acyl groups, cyano groups, carbamoyl groups, sulfamoyl groups, carboxyl groups or acyloxy groups, provided that R.sub.0 and R.sub.1 do not represent hydrogen atoms at the same time; R.sub.2 represents a hydrogen atom, or an alkyl or aryl group; R.sub.3 represents an alkyl group having 2 or more carbon atoms, an aryl group, an alkoxy group having 2 or more carbon atoms, an aryloxy group, an acyl group having 3 or more carbon atoms, an acyloxy group having 3 or more carbon atoms, an alkoxycarbonyl group having 4 or more carbon atoms, or an acylamino group having 3 or more carbon atoms, and moreover R.sub.3 is required to be a substituent having such L and B that S value is 544 or less in the equation of
S=3.536L-2.661B+535.4
wherein L represents a STERIMOL parameter (its unit is .ANG.) disclosed in A. Verloop, W. Hoogenstraaten, J. Tipker; "Drug Design, Vol VII", (E. J. Ariens Ed.) Academic Press, New York (1976), pp. 180-185 and the like, and B represents the smaller value among B.sub.1 +B.sub.4 and B.sub.2 +B.sub.3 which are each sums of STERIMOL parameters, provided that R.sub.1 and R.sub.3, or R.sub.0 and R.sub.3 do not represent aryl groups at the same time; R.sub.4 and R.sub.5 may be the same or different, and represent alkyl groups; X.sub.1 .crclbar. represents a counter anion; and l is 0 or 1, and when an innert salt is formed, l is 0; ##STR3## wherein Z.sub.3 and Z.sub.4 may be the same or different, and represent nonmetal atomic groups necessary for formation of naphthalene rings; R.sub.9 and R.sub.11 have the same meanings with R.sub.4 and R.sub.5, R.sub.10 has the same meaning with R.sub.2 ; X.sub.3 .crclbar. has the same meaning with X.sub.1 .crclbar.; and n has the same meaning with l.
DETAILED DESCRIPTION OF THE INVENTION
In the general formula (I), the alkyl groups in the definition of R.sub.0 and R.sub.1 may each be substituted with substituent(s), and preferably include alkyl groups each having 10 or less carbon atoms, for example methyl, ethyl, propyl, isopropyl, butyl, branched butyl (e.g. isobutyl or t-butyl groups), pentyl, branched pentyl (e.g. isopentyl or t-pentyl groups), vinylmethyl, cyclohexyl, benzyl, phenethyl, 3-phenylpropyl or trifluoromethyl groups or the like.
The aryl groups in the definition of R.sub.0 and R.sub.1 may each be substituted with substituent(s), and preferably include aryl groups each having 10 or less carbon atoms, for example phenyl, 4-methylphenyl, 4-chlorophenyl or naphthyl groups or the like.
The alkoxy groups in the definition of R.sub.0 and R.sub.1 may each be substituted with substituent(s), and preferably include alkoxy groups each having 10 or less carbon atoms, for example methoxy, ethoxy, propyloxy, butyloxy, pentyloxy, benzyloxy or phenethyloxy groups or the like.
The aryloxy groups in the definition of R.sub.0 and R.sub.1 may each be substituted with substituent(s), and preferably include aryloxy groups each having 10 or less carbon atoms, for example phenoxy, 4-methylphenoxy, 4-chlorophenoxy or naphthyloxy groups or the like.
Halogen atoms in the definition of R.sub.0 and R.sub.1 and fluorine, chlorine, bromine or iodine atoms.
The alkoxycarbonyl groups in the definition of R.sub.0 and R.sub.1 may each be substituted with substituent(s), and preferably include alkoxycarbonyl groups each having 10 or less carbon atoms, for example methoxycarbonyl, ethoxycarbonyl or benzyloxycarbonyl groups or the like.
The acylamino groups in the definition of R.sub.0 and R.sub.1 may each be substituted with substituent(s), and preferably include acylamino groups each having 8 or less carbon atoms, for example acetylamino, trifluoroacetylamino, propionylamino or benzoylamino groups or the like.
The acyl groups in the definition of R.sub.0 and R.sub.1 may each be substituted with substituent(s), and preferably include acyl groups each having 10 or less carbon atoms, for example acetyl, trifluoroacetyl, propionyl, benzoyl, p-chlorobenzoyl or mesyl groups or the like.
The carbamoyl groups in the definition of R.sub.0 and R.sub.1 may each be substituted with substituent(s), and preferably include carbamoyl groups each having 6 or less carbon atoms, for example carbamoyl, N,N-dimethylcarbamoyl or morpholinocarbonyl groups or the like.
The sulfamoyl groups in the definition of R.sub.0 and R.sub.1 may each be substituted with substituent(s), and preferably include sulfamoyl groups having 6 or less carbon atoms, for example sulfamoyl, N,N-dimethylsulfamoyl, morpholinosulfonyl or piperidinosulfonyl groups or the like.
The acyloxy groups in the definition of R.sub.0 and R.sub.1 may each be substituted with substituent(s), and preferably include acyloxy groups each having 10 or less carbon atoms, for example acetyloxy, trifluoroacetyloxy, propionyloxy or benzoyloxy groups or the like.
Besides the above definition, R.sub.0 and R.sub.1 may further be hydrogen atoms, cyano groups or carboxyl groups, provided that R.sub.0 and R.sub.1 do not represent hydrogen atoms at the same time. In most preferred combination of R.sub.0 and R.sub.1, R.sub.0 is a phenyl group substituted at the 5-position and R.sub.1 is a hydrogen atom.
The alkyl and aryl groups in the definition of R.sub.2 may each be substituted with substituent(s), and preferably include an alkyl group having 4 or less carbon atoms (for example, a methyl, ethyl, propyl, butyl, benzyl, phenethyl or 3-phenylpropyl group or the like) and an aryl group having 10 or less carbon atoms (for example, a phenyl or p-tolyl group or the like). R.sub.2 may also be a hydrogen atom.
The alkyl, aryl, alkoxy, aryloxy, acyl, acyloxy, alkoxycarbonyl and acylamino groups in the definition of R.sub.3 may each be substituted with substituent(s), provided that R.sub.1 and R.sub.3 do not represent aryl groups at the same time.
Examples of preferred R.sub.3 group include ethyl, propyl, isopropyl, branched butyl (e.g., t-butyl, etc.), branched pentyl (e.g., isopentyl, t-pentyl, etc.), branched hexyl (e.g., 3,3-dimethylbutyl, etc.), cyclohexyl, branched octyl (e.g., t-octyl), benzyl, phenethyl and t-butylcarbonyloxy groups and the like. Most preferred examples of R.sub.3 include ethyl, propyl, isopropyl, t-butyl, t-pentyl, cyclohexyl, t-octyl and benzyl groups.
The alkyl groups in the definition of R.sub.4 and R.sub.5 may each be substituted with substituent(s), and preferably include alkyl groups each having 8 or less carbon atoms (for example, methyl, ethyl, propyl, vinylmethyl, butyl, pentyl, hexyl, heptyl or octyl groups or the like); aralkyl groups each having 10 or less carbon atoms (for example, benzyl, phenethyl or 3-phenylpropyl groups or the like); or alkyl groups each having 6 or less carbon atoms each substituted with a substituent selected from the group consisting of a hydroxyl group, a carboxyl group, a sulfo or a cyano group, a halogen atom (e.g., a fluorine, chlorine or bromine atom or the like), an unsubstituted or substituted alkoxycarbonyl group having 8 or less carbon atoms (e.g., a methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl group or the like), an unsubstituted or substituted alkoxy group having 8 or less carbon atoms (e.g., a methoxy, ethoxy, butyloxy, benzyloxy or phenethyloxy group or the like), an aryloxy group having 8 or less carbon atoms (e.g., a phenoxy or p-tolyloxy group or the like), an acyloxy group having 8 or less carbon atoms (e.g., an acetyloxy, propionyloxy or benzoyloxy group or the like), an acyl group having 8 or less carbon atoms (e.g. an acetyl, propionyl, benzoyl or 4-fluorobenzoyl group or the like), an unsubstituted or substituted carbamoyl group having 6 or less carbon atoms (e.g., a carbamoyl, N,N-dimethylcarbamoyl, morpholinocarbonyl or piperidinocarbonyl or the like), an unsubstituted or substituted sulfamoyl group having 6 or less carbon atoms (e.g., a sulfamoyl, N,N-dimethylsulfamoyl, morpholinosulfonyl or piperidinosulfonyl group or the like), and an unsubstituted or substituted aryl group having 10 or less carbon atoms (e.g., a phenyl, p-fluorophenyl, p-hydroxyphenyl, p-carboxyphenyl or p-sulfophenyl group or the like).
One of R.sub.4 and R.sub.5 is preferable to be a sulfoalkyl group or a carboxyalkyl group.
X.sub.1 .crclbar. represents an inorganic or organic acid anion, for example chloride, bromide, iodide, p-toluenesulfonate, p-nitrobenzenesulfonate, methanesulfonate, methylsulfate, ethylsulfate, perchlorate or the like.
In the general formula (III), each naphthalene ring formed containing Z.sub.3 or Z.sub.4 may be substituted by a substituent. Examples of a heterocyclic part formed including Z.sub.3 or Z.sub.4 as expressed as a naphthooxazole include naphtho(1,2-d)oxazole, naphtho(2,1-d)oxazole, naphtho(2,3-d)oxazole, 8-methoxynaphtho(1,2-d)oxazole, 5-acetylaminonaphtho(2,1-d)oxazole, etc.
According to a preferred embodiment of the present invention, the silver halide emulsion of the present invention further contains at least one of the compounds represented by the following general formula (II): ##STR4## wherein Z.sub.1 and Z.sub.2 may be the same or different, and represent nonmetal atomic groups necessary for formation of benzene rings or naphthalene rings, provided that Z.sub.1 and Z.sub.2 are not used for formation of naphthalene rings at the same time, and further provided that when Z.sub.1 and/or Z.sub.2 form benzene rings each having a substituent, the substituent does not represent any of substituents defined as R.sub.3 ; R.sub.7 has the same meaning with R.sub.2 ; R.sub.6 and R.sub.8 have the same meanings with R.sub.4 and R.sub.5, respectively; X.sub.2 .crclbar. has the same meaning with X.sub.1 .crclbar.; and m has the same meaning with l.
Benzene ring or naphthalene ring formed containing Z.sub.1 or Z.sub.2 may be substituted with substituent(s). Examples of a heterocyclic part formed containing Z.sub.1 or Z.sub.2 as expressed as a benzoxazole or naphthooxazole include, for example, benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-bromobenzoxazole, 5-fluorobenzoxazole, 5-phenylbenzoxazole, 5-methoxybenzoxazole, 5-butoxybenzoxazole, 5-nitrobenzoxazole, 5-trifluoromethylbenzoxazole, 5-hydroxybenzoxazole, 5-carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole, 6-nitrobenzoxazole, 6-methoxybenzoxazole, 6-amylbenzoxazole, 6-hydroxybenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 5-ethoxybenzoxazole, naphtho(2,1-d)oxazole, naphtho(1,2-d)oxazole, naphtho(2,3-d)oxazole, 5-nitronaphtho(2,1-d)oxazole, and the like.
Most preferred examples of a heterocyclic part formed containing Z.sub.1 or Z.sub.2 as expressed as a benzoxazole or naphthooxazole include 5-chlorobenzoxazole, 5-bromobenzoxazole, 5-fluorobenzoxazole, 5-phenylbenzoxazole, 5-methoxybenzoxazole, 5,6-dimethylbenzoxazole, naphtho(2,1-d)oxazole, naphtho(1,2-d)oxazole, naphtho(2,3-d)oxazole and the like.
R.sub.6 and R.sub.8 have the same meaning with R.sub.4 and R.sub.5, and R.sub.7 has the same meaning with R.sub.2. The most preferred example of R.sub.7 is an ethyl group. X.sub.2 .crclbar. has the same meaning with X.sub.1 .crclbar., and m has the same meaning with l.
Typical examples of the compounds used in the present invention as represented by the above general formulae (I) to (III) are illustrated below, but the scope of the present invention should not be interpreted as limited only to these compounds.
__________________________________________________________________________ ##STR5##R.sub.0 R.sub.1 R.sub.2 R.sub.3 R.sub.4 R.sub.5 X l__________________________________________________________________________I-1 H ##STR6## H (CH.sub.2).sub.2 CH.sub.3 ##STR7## ##STR8## -- 0I-2 H ##STR9## CH.sub.3 C.sub.2 H.sub.5 ##STR10## C.sub.2 H.sub.5 -- 0I-3 H ##STR11## C.sub.2 H.sub.5 ##STR12## ##STR13## ##STR14## -- 0I-4 H ##STR15## CH.sub.3 ##STR16## ##STR17## ##STR18## -- 0I-5 H ##STR19## C.sub.2 H.sub.5 ##STR20## ##STR21## ##STR22## -- 0I-6 H ##STR23## C.sub.2 H.sub.5 ##STR24## ##STR25## ##STR26## -- 0I-7 H ##STR27## C.sub.2 H.sub.5 ##STR28## ##STR29## ##STR30## -- 0I-8 H Cl CH.sub.3 ##STR31## ##STR32## ##STR33## -- 0I-9 H CH.sub.3 C.sub.2 H.sub.5 ##STR34## C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR35## 1I-10 H (CH.sub.3).sub.2 NSO.sub.2 (CH.sub.2).sub.2 CH.sub.3 CH(CH.sub.3).sub.2 C.sub.2 H.sub.5 ##STR36## -- 0I-11 ##STR37## H C.sub.2 H.sub.5 ##STR38## ##STR39## ##STR40## -- 0I-12 CH.sub.3 (CH.sub.2).sub.4 O H ##STR41## ##STR42## ##STR43## ##STR44## -- 0I-13 HOOC H C.sub.2 H.sub.5 ##STR45## ##STR46## C.sub.2 H.sub.5 -- 0I-14 ##STR47## H H ##STR48## ##STR49## CH.sub.3 -- 0I-15 H ##STR50## C.sub.2 H.sub.5 ##STR51## C.sub.2 H.sub.5 C.sub.2 H.sub.5 Br.sup.- 1I-16 CH.sub.3 O H CH.sub.3 ##STR52## CH.sub.3 ##STR53## -- 0I-17 Cl H H ##STR54## ##STR55## ##STR56## -- 0I-18 H ##STR57## C.sub.2 H.sub.5 ##STR58## ##STR59## ##STR60## -- 0I-19 H ##STR61## C.sub.2 H.sub.5 ##STR62## ##STR63## ##STR64## -- 0I-20 CH.sub.3 CH.sub.3 C.sub.2 H.sub.5 ##STR65## ##STR66## ##STR67## -- 0__________________________________________________________________________
Each L and B values of various substituents R.sub.3 and S value calculated from the equation:
S=3.536L-2.661B+535.4
are exhibited in the following table.
______________________________________Substituent R.sub.3 L(.ANG.) B(.ANG.) S______________________________________--C.sub.2 H.sub.5 4.11 3.80 540--C.sub.3 H.sub.7.sup.(n) 5.05 3.80 543--C.sub.3 H.sub.7.sup.(i) 4.11 5.20 536--C.sub.4 H.sub.9.sup.(t) 4.11 5.56 535--C.sub.5 H.sub.11.sup.(t) 5.05 5.72 538--C.sub.2 H.sub.4 C(CH.sub.3).sub.3 6.17 5.56 542--CH.sub.2 C.sub.6 H.sub.5 3.63 6.22 533--C.sub.6 H.sub.11.sup.(cyclo) 6.17 5.53 543--C.sub.2 H.sub.4 C.sub.6 H.sub.5 4.63 6.22 535--OCOC(CH.sub.3).sub.3 5.96 5.56 542--C.sub.8 H.sub.17.sup.(t) 6.00 5.72 541--C.sub.6 H.sub.5 6.28 3.40 549______________________________________
__________________________________________________________________________ ##STR68## R.sup.10 R.sup.11 R.sup.12 R.sup.13 R.sup.14 R.sup.15__________________________________________________________________________II-1 ##STR69## H ##STR70## C.sub.2 H.sub.5 (CH.sub.2).sub.2 SO.sub.3.sup.- ##STR71##II-2 ##STR72## H Cl C.sub.2 H.sub.5 (CH.sub.2).sub.2 SO.sub.3.sup.- (CH.sub.2).sub.3 SO.sub.3 H.N(C.sub. 2 H.sub.5).sub.3II-3 Cl H Cl C.sub.2 H.sub.5 (CH.sub.2).sub.3 SO.sub.3.sup.- (CH.sub.2).sub.3 SO.sub.3 NaII-4 OCH.sub.3 H OCH.sub.3 C.sub.2 H.sub.5 (CH.sub.2).sub.3 SO.sub.3.sup.- (CH.sub.2).sub.3 SO.sub.3 KII-5 ##STR73## H O(CH.sub.2).sub.3 CH.sub.3 C.sub.2 H.sub.5 (CH.sub.2).sub.3 SO.sub.3.sup.- (CH.sub.2).sub.3 SO.sub.3 KII-6 OCH.sub.3 H OCH.sub.3 CH.sub.3 (CH.sub.2).sub.3 SO.sub.3.sup.- (CH.sub.2).sub.3 SO.sub.3 NaII-7 Cl H Cl H (CH.sub.2).sub.4 SO.sub.3.sup.- (CH.sub.2).sub.4 SO.sub.3 NaII-8 ##STR74## H ##STR75## ##STR76## (CH.sub.2).sub.3 SO.sub.3.sup.- (CH.sub.2).sub.3 SO.sub.3 HII-9 ##STR77## H Cl C.sub.2 H.sub.5 (CH.sub.2).sub.2 SO.sub.3.sup.- C.sub.2 H.sub.5II-10 ##STR78## H ##STR79## C.sub.2 H.sub.5 (CH.sub.2).sub.2 SO.sub.3.sup.- CH.sub.3II-11 ##STR80## H nC.sub.4 H.sub.9 C.sub.2 H.sub.5 (CH.sub.2).sub.2 SO.sub.3.sup.- (CH.sub.2).sub.2 SO.sub.3 NaII-12 nC.sub.4 H.sub.9 H OC.sub.4 H.sub.9 (n) C.sub.2 H.sub.5 (CH.sub.2).sub.3 SO.sub.3.sup.- (CH.sub.2).sub.3 SO.sub.3 KII-13 CH.sub.3 H CH.sub.3 H (CH.sub.2).sub.3 SO.sub.3.sup.- (CH.sub.2).sub.3 SO.sub.3 KII-14 ##STR81## OC.sub.5 H.sub.11 (n) H C.sub.2 H.sub.5 (CH.sub.2).sub.3 SO.sub.3.sup.- (CH.sub.2).sub.4 SO.sub.3 HII-15 OC.sub.4 H.sub.9 (n) H OC.sub.4 H.sub.9 (n) H (CH.sub.2).sub.4 SO.sub.3.sup.- (CH.sub.2).sub.4 SO.sub.3 HII-16 OC.sub.7 H.sub.15 (n) H OC.sub.7 H.sub.15 (n) CH.sub.3 (CH.sub.2).sub.3 SO.sub.3.sup.- (CH.sub.2).sub.3 SO.sub.3 H.N(C.sub. 2 H.sub.5).sub.3II-17 ##STR82## H ##STR83## C.sub.2 H.sub.5 (CH.sub.2).sub.4 SO.sub.3.sup.- (CH.sub.2).sub.4 SO.sub.3 NaII-18 ##STR84##__________________________________________________________________________ ##STR85## R.sup.0 R.sup.10 R.sup.9 R.sup.11__________________________________________________________________________III-1 H C.sub.2 H.sub.5 (CH.sub.2).sub.3 SO.sub.3 K (CH.sub.2).sub.3 SO.sub.3.sup.-III-2 H C.sub.2 H.sub.5 C.sub.2 H.sub.5 (CH.sub.2).sub.3 SO.sub.3.sup.-III-3 OCH.sub.3 H (CH.sub.2).sub.3 SO.sub.3 K (CH.sub.2).sub.3 SO.sub.3.sup.-III-4 H CH.sub.3 (CH.sub.2).sub.3 SO.sub.3 K (CH.sub.2).sub.3 SO.sub.3.sup.-III-5 H H C.sub.2 H.sub.5 (CH.sub.2).sub.3 SO.sub.3.sup.-III-6 H CH.sub.3 C.sub.2 H.sub.5 (CH.sub.2).sub.3 SO.sub.3.sup.-III-7 H H CH.sub.3 (CH.sub.2).sub.3 SO.sub.3.sup.-III-8 H CH.sub.3 CH.sub.3 (CH.sub.2).sub.3 SO.sub.3.sup.-III-9 H C.sub.2 H.sub.5 CH.sub.3 (CH.sub.2).sub.3 SO.sub.3.sup.-__________________________________________________________________________ ##STR86## R.sup.10 R.sup.9 R.sup.11__________________________________________________________________________III-10 C.sub.2 H.sub.5 (CH.sub.2).sub.3 SO.sub.3 K (CH.sub.2).sub.3 SO.sub.3.sup.-III-11 C.sub.2 H.sub.5 (CH.sub.2).sub.4 SO.sub.3 K (CH.sub.2).sub.4 SO.sub.3.sup.-III-12 CH.sub.3 (CH.sub.2).sub.4 SO.sub.3 K (CH.sub.2).sub.4 SO.sub.3.sup.-III-13 CH.sub.3 (CH.sub.2).sub.3 SO.sub.3 K (CH.sub.2).sub.3 SO.sub.3.sup.-III-14 C.sub.2 H.sub.5 (CH.sub.2).sub.3 SO.sub.3.sup.- C.sub.2 H.sub.5III-15 CH.sub.3 (CH.sub.2).sub.3 SO.sub.3.sup.- C.sub.2 H.sub.5__________________________________________________________________________ ##STR87## R.sup.9 R.sup.11__________________________________________________________________________III-16 (CH.sub.2).sub.3 SO.sub.3.sup.- (CH.sub.2).sub.3 SO.sub.3 KIII-17 C.sub.2 H.sub.5 (CH.sub.2).sub.3 SO.sub.3.sup.-III-18 (CH.sub.2).sub.3 SO.sub.3 K (CH.sub.2).sub.3 SO.sub.3.sup.-III-19 (CH.sub.2).sub.4 SO.sub.3.sup.- C.sub.2 H.sub.5__________________________________________________________________________
Sensitizing dyes represented by the general formulae (I), (II) and (III) as used in the present invention, and the like can readily be synthesized according to methods disclosed in F. M. Hamer, "Heterocyclic Compounds - Cyanine dyes and related compounds -" chapters IV, V and VI, pages 86 to 199, John Wiley & Sons (New York, London) (1964); D. M. Sturmer, "Heterocyclic Compounds Special topics in heterocyclic chemistry -" chapter VIII, sec. IV, pages 482 to 515, John Wiley & Sons (New York, London) (1977); and the like.
A sensitizing dye used in the present invention can directly be dispersed in an emulsion. Alternatively, it can first be dissolved in a suitable solvent, for example methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water or pyridine or a mixed solvent thereof, and then added to an emulsion as a solution. Ultrasonic wave can be used to dissolve it. As a method for addition of this sensitizing dye, a method as disclosed in U.S. Pat. No. 3,469,987 or the like wherein a dye is dissolved in a volatile organic solvent, the solution is dispersed in a hydrophilic colloid, and the dispersion is added to an emulsion; a method as disclosed in J. P. KOKOKU No. 46-24185 or the like wherein a water insoluble dye is dispersed in a water soluble solvent without dissolving it, and this dispersion is added to an emulsion; a method as disclosed in U.S. Pat. No. 3,822,135 or the like wherein a dye is dissolved in a surfactant and the solution is added to an emulsion; a method as disclosed in J. P. KOKAI No. 51-74624 wherein a dye is dissolved using a compound capable of red shift, and the solution is added to an emulsion; a method as disclosed in J. P. KOKAI No. 50-80826 wherein a dye is dissolved an acid substantially free from water, and the solution is added to an emulsion; or the like may be used. Furthermore, a method for addition to an emulsion disclosed in U.S. Pat. Nos. 2,912,343, 3,342,605, 2,996,287 or 3,429,835, or the like may also be used further, the above sensitizing dye may uniformly be dispersed in a silver halide emulsion before it is applied on a suitable support, and may of course be dispersed in any step for preparation of a silver halide emulsion.
That is, the sensitizing dye may be added in any step of preparation of a photographic emulsion, or in any stage from after preparation of the emulsion to just before application thereof Examples of the former stage are a silver halide grain-forming step, a physical ripening step, a chemical ripening step and the like
A sensitizing dye of the present invention may be used in an amount sufficient for effectively increasing sensitivity of an emulsion The total amount of the dyes represented by formulas (I), (II) and (III) may widely be changed according to the condition of an emulsion to be used, but may preferably be an amount of 1.times.10.sup.-6 to 5.times.10.sup.31 3 moles, preferably 3.times.10.sup.-6 to 2.5.times.10.sup.-3 moles per 1 mole of the silver halide. Preferably, a molar ratio of the dyes of formulas (I), (II) and (III) is 50.+-.20:30.+-.10:20.+-.10.
Any silver halide among silver bromide, silver bromoiodide, silver bromochloreiodide, silver bromochloride and silver chloride may be used in the photographic emulsion of the present invention.
Silver halide grains in the photographic emulsion may be so-called regular grains which have a regular crystal shape such as cubic, octahedron or tetradecahedron, grains having an irregular crystal shape such as sphere, or grains having crystal defect such as twinning plane, or grains having a composite shape thereof.
Grain size of the silver halide may be a fine size of 0.1 .mu.m or less, or a large size up to 10 .mu.m in diameter of projected area. Further, an emulsion containing such silver halide may be a monodispersed emulsion having a narrow distribution, or a multi-dispersed emulsion having a wide distribution.
A silver halide photographic emulsion of the present invention can be prepared according to a known method, for example a method disclosed in Research Disclosure, No. 17643 (December, 1978), pages 22 to 23 ("I. Emulsion preparation and types"), or ibid. No. 18716 (November, 1979), page 648.
A photographic emulsion cf the present invention can also be prepared using a method disclosed in P. Glafkides, Chimie et Physique Photographique, Paul Montel, 1967; G. F. Duffin, Photographic Emulsion Chemistry, Focal Press, 1966; V. L. Zelikman et al., Making and Coating Photographic Emulsion, Focal Press, 1964, or the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be utilized, and as for a method for reacting a soluble silver salt with a soluble halogen salt, any of a single-jet method, a simultaneous jet method and a combination thereof may be utilized. Further, a method wherein grains are formed using excess silver ions (a so-called reverse-jet method) can also be utilized. Further, a method wherein pAg in a liquid phase where a silver halide is formed is held constant, namely a socalled controlled double-jet method can also be used as a mode of a simultaneous-jet method. According to this method, a silver halide emulsion containing grains having a regular crystal shape and an almost uniform size may be obtained.
Further, it is also possible to mix 2 or more kinds of silver halide emulsions which were separately prepared.
A silver halide emulsion comprising the aforementioned regular grains may be obtained by controlling pAg and pH during formation of grains, as is detailedly described, for example in Photographic Science and Engineering, vol. 6, pages 159 to 165 (1962); Journal of Photographic Science, vol. 12, pages 242 to 251 (1964); U.S. Pat. No. 3,655,394 or U.K. Pat. No. 1,413,748.
Typical monodispersed emulsion is such an emulsion that contains silver halide grains which have an average grain size more than about 0.1 .mu.m and at least 95 weight % of which have grain sizes which fall within .+-.40% of the average grain size. An emulsion which contain silver halide grains which have an average grain size of 0.25 to 2 .mu.m, and at least 95 weight % or at least 95% in number of which have grain sizes which fall within .+-.20% of the average grain size can also be used in the present invention. Processes for preparation of such an emulsion are disclosed in U.S. Pat. Nos. 3,574,628 and 3,655,394 and U.K. Pat. No. 1,413,748. Monodispersed emulsions disclosed in J. P. KOKAI Nos. 48-8600, 51-39027, 51-83097, 53-137133, 54-48521, 54-99419, 58-37635, 58-49938 and the like can also preferably be used in the present invention.
Further, tabular grains having an aspect ratio of 5 or more can also be used in the present invention. Tabular grains can readily be prepared according to a method disclosed in U.S. Pat. Nos. 4,434,226, 4,414,310, 4,433,048 or 4,439,520, U.K. Pat. No. 2,112,157, or the like. When tabular grains are used, various advantages such as enhancement of spectral sensitization efficiency by a sensitizing dye, enhancement of graininess and increase of sharpness are brought about, which is detailedly described in U.S. Pat. No. 4,434,226 referred to above.
Crystals of silver halide may be composed of a uniform structure, a halogen composition heterogenous between inside and outside, or a layer structure. Such various emulsion grains are disclosed in U.K. Pat. No. 1,027,146, U.S. Pat. Nos. 3,505,068 and 4,444,877, J. P. KOKAI No. 60-143331, and the like.
As for halogen distribution in grains, halogen may be either uniformly distributed or distributed with a composition heterogenous between inside and outside, or layers each having a mutually heterogenous halogen composition are superposed. Particularly preferred grains are those having substantially two distinct layer structures (core/shell structure) composed of core part of a higher iodine content and shell part of a lower iodine content.
Further, silver halides mutually having different compositions may be conjugated by epitaxial conjunction, and a silver halide may be conjugated with a compound other than silver halide such as silver rhodanide or lead oxide by epitaxial conjuction. These emulsion grains are disclosed in U.S. Pat. Nos. 4,094,684, 4,142,900 and 4,459,353, U.K. Pat. No. 2,038,792, U.S. Pat. Nos. 4,349,622, 4,395,478, 4,433,501, 4,463,087, 3,656,962 and 3,852,067, J. P. KOKAI No. 59-162540, and the like.
Further, it is possible to use a mixture of grains of various crystal shapes.
Emulsions of the present invention are usually subjected to physical ripening and chemical ripening prior to use. Additives to be used in such steps are disclosed in Research Disclosure Nos. 17643 and 18716, and the relevant parts are summarized in the following table.
Known photographic additives usable in the present invention are also disclosed in the above two Research Disclosure Journals, and the relevant parts are summarized in the following table.
______________________________________Kind of additive RD 17643 RD 18716______________________________________1. Chemically sensitizing page 23 page 648, agent right column (r.c.)2. Sensitivity-enhancing page 648, agent right column (r.c.)3. Spectrally sensitizing pages page 648 r.c. agent 23-24page 649 r.c.4. Antifoggant and pages page 649 r.c. stabilizing agent 24-255. Light-absorbing agent, pages page 649 r.c. Filter dye and UV 25-26page 650 absorbent left column (l.c.)6. Stain inhibitor page 25 pages 650 r.c.7. Hardening agent page 26 page 651 l.c.8. Binder page 26 page 651 l.c.9. Plasticizer and page 27 page 650 r.c. lubricant10. Coating aid and pages do. surfactant 26-2711. Static inhibitor page 27 do.______________________________________
Various color-forming couplers can be used in the present invention, and specific examples thereof are disclosed in patents listed in the above Research Disclosure (RD) No. 17643, VII-C - G. As dye-forming couplers, couplers which respectively give three primary colors (i.e., yellow, magenta and cyan) in substrative color process by color development are important. Examples of nondiffusible 4- or 2-equivalent couplers preferably used in the present invention include couplers disclosed in patents disclosed in the aforementioned RD No. 17643, VII-C and D items as well as couplers described below.
Typical yellow dye-forming couplers usable in the present invention include hydrophobic acylacetoamide type couplers having a ballast group. Specific examples thereof are disclosed in U.S. Pat. Nos. 2,407,210, 2,875,057 and 3,265,506, and the like. 2-Equivalent yellow dye-forming couplers are preferably used in the present invention, and typical examples thereof include oxygen atom-coupling off type yellow dye-forming couplers disclosed in U.S. Pat. Nos. 3,408,194, 3,447,928, 3,993,501 and 4,022,620, and the like, and nitrogen atom-coupling off type yellow dye-forming couplers disclosed in J. P. KOKOKU No. 58-10739, U.S. Pat. Nos. 4,401,752 and 4,326,024, RD No. 18053 (April, 1979), U.K. Pat. No. 1,425,020, German Patent Unexamined Published APPLICATION (OLS) Nos. 2,219,917, 2,261,361, 2,329,587 and 2,433,812, and the like. .alpha.-Pivaloylacetanilide type couplers are excellent in fastness, particularly light fastness of their colored dyes, and on the other hand .alpha.-benzoylacetanilide type couplers give high color densities.
Magenta dye-forming couplers usable in the present invention include indazolone type, cyanoacetyl type, 5-pyrazolone type and pyrazoloazole type couplers which each have a ballast group and are hydrophobic, and 5-pyrazolone type and pyrazoloazole type couplers are preferable. As 5-pyrazolone type couplers, those whose 3-positions are each substituted with an arylamino group or an acylamino group are preferable in view of the hue or color density of their colored dyes, and typical examples thereof are disclosed 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, and the like. As a coupling-off group of a 2-equivalent 5-pyrazolone type coupler, a nitrogen atom - coupling off group disclosed in U.S. Pat. No. 4,310,619, or an arylthio group disclosed in U.S. Pat. No. 4,351,897 is particularly preferred. A 5-pyrazolone type coupler having a ballast group as disclosed in European Pat. No. 73,636 gives a high color density. As pyrazoloazole type couplers, pyrazolobenzimidazoles disclosed in U.S. Pat. No. 3,369,879, pyrazolo(5,1-c)(1,2,4)triazoles disclosed in U.S. Pat. No. 3,725,067, pyrazolotetrazoles disclosed in Research Disclosure No. 24,220 (June, 1984) and J. P. KOKAI No. 60-33552, and pyrazolopyrazoles disclosed in Research Disclosure No. 24,230 (June, 1984) and J. P. KOKAI No. 60-43659 may preferably be used. In view of reduced yellow subabsorption of a colored dye and light fastness of the colored dye, imidazo(1,2-b)pyrazoles disclosed in U.S. Pat. No. 4,500,630 are preferable, and pyrazolo(1,5-b)(1,2,4)triazole disclosed in European Pat. No. 119,860A is particularly preferable.
Cyan dye-forming couplers usable in the present invention include naphthol type and phenol type couplers which are hydrophobic and nondiffusible. Typical naphthol type couplers include naphthol type couplers disclosed in U.S. Pat. No. 2,474,293, and preferably oxygen atom-coupling off type 2-equivalent naphthol type couplers disclosed in U.S. Pat. Nos. 4,052,212, 4,146,396, 4,228,233 and 4,296,200. Specific examples of phenol type couplers are disclosed in U.S. Pat. Nos. 2,369,929, 2,801,171, 2,772,162 and 2,895,826, and the like. Cyan dye-forming couplers fast against humidity and temperature are preferably used in the present invention, and typical examples thereof include phenol type cyan dye-forming couplers having an alkyl group of an ethyl group and up at the meta position of the phenol nucleus as disclosed in U.S. Pat. No. 3,772,002; 2,5-diacylaminosubstituted phenol type couplers disclosed in U.S. Pat. Nos. 2,772,162, 3,758,308, 4,126,396, 4,334,011 and 4,327,173, OLS No. 3,326,729, European Pat. No. 121,365, and the like; phenol type couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position as disclosed in U.S. Pat. Nos. 3,446,622, 4,333,999, 4,451,559 and 4,427,767, and the like; and the like.
In order to correct unnecessary absorption of a colored dye, it is preferable in color light-sensitive materials that masking is carried out by using a colored coupler together. Typical examples of the colored couplers include yellow-colored magenta dye-forming couplers disclosed in U.S. Pat. No. 4,163,670, J. P. KOKOKU No. 57-39413 and the like; magenta-colored cyan dye-forming couplers disclosed in U.S. Pat. Nos. 4,004,929 and 4,138,253, U.K. Pat. No. 1,146,368, and the like; and the like. Other colored couplers are disclosed in the aforementioned RD No. 17643, Items VII - G.
It is possible to improve graininess by using such a coupler that a colored dye derived therefrom has a proper diffusibility.
As such couplers, specific examples of magenta dye-forming couplers are disclosed in U.S. Pat. No. 4,366,237 and U.K. Pat. No. 2,125,570, and specific examples of yellow, magenta or cyan dye-forming couplers are disclosed in European Pat. No. 96,570 and OLS No. 3,234,533.
Dye-forming couplers and the above special couplers may each form polymers of dimer or more. Typical examples of polymerized dye-forming couplers are disclosed in U.S. Pat. Nos. 3,451,820 and 4,080,211. Specific examples of polymerized magenta dye-forming couplers are disclosed in U.K. Pat. No. 2,102,173 and U.S. Pat. No. 4,367,282.
Couplers releasing a photographically useful residue together with coupling can also preferably be used in the present invention. As DIR couplers each releasing a development inhibitor, couplers disclosed in patents disclosed in the aforementioned RD No. 17643, item VII - F are useful.
Preferred DIR couplers to be used in combination with the present invention include developing solution-inactivating type DIR couplers typically disclosed in J. P. KOKAI No. 57-151944; timing type DIR couplers typically disclosed in U.S. Pat. No. 4,248,962 and J. P. KOKAI No. 57-154234; and reaction type DIR couplers typically disclosed in J. P. KOKAI No. 60-184248. Particularly preferred DIR couplers include developing solution-inactivating type DIR couplers disclosed in J. P. KOKAI Nos. 57-151944, 58-217932, 60-218644, 60-225156 and 60-233650, and the like, and reaction type DIR couplers disclosed in J. P. KOKAI No. 60-184248 and the like.
Examples of suitable supports usable for photographic light-sensitive materials having a photographic emulsion of the present invention include those disclosed, for example in the aforementioned RD No. 17643, page 28 and RD No. 18716, page 647 right column to page 648 left column.
Photographic light-sensitive materials to which a photographic emulsion of the present invention is applicable include various color and black-and-white light-sensitive materials. Examples of such light-sensitive materials include color negative films for photographing (for generic use, movie and the like), reversal color films (for slide, movie and the like; couplers are either included or not included), color photographic papers, color positive films (for movie and the like), reversal color photographic papers, color light-sensitive materials for heat development, color light-sensitive materials by use of a silver dye bleaching method, photographic light-sensitive materials for making printing plates (litho-film, scanner film and the like), X-ray photographic light-sensitive materials (for direct or indirect medical use, industrial use, and the like), black-and-white negative films for photographing, black-and-white photographic papers, light-sensitive materials for micro-use (for COM, microfilm and the like), color diffusion transfer light-sensitive materials (DTR), silver salt diffusion transfer light-sensitive materials, print-out light-sensitive materials, and the like.
Exposure to light for obtaining a photographic image by a photographic light-sensitive material using a photographic emulsion of the present invention may be carried out using an usual method. That is, any of various known light sources containing infrared light such as natural light (sunlight), a tungsten lamp, a fluorescent lamp, a mercury lamp, a xenon arc lamp, a carbon arc lamp, a xenon flash lamp, cathode ray tube flying spot, luminescent diode, laser light (e.g., gas laser, YAG laser, dye laser, semiconductor laser and the like), and the like. Exposure to light may also be carried out by light emitted from a fluorescent material excited with electron beams, X-rays, .gamma.-rays, .alpha.-rays or the like. Exposure time may first be 1/1000 to one second used in an ordinal camera, may also be a time shorter than 1/1000 second, for example 1/10.sup.4 to 1/10.sup.6 second in case of using a xenon flash lamp or a cathode ray tube, and may further be a time longer than one second. It is possible, according to necessity, to adjust spectral composition of light used in exposure using a color filter.
A photographic light-sensitive material to which a photographic emulsion of the present invention is applicable can be developed according to a usual method disclosed in the aforementioned RD No. 17643, pages 28 to 29, or RD No. 18716, page 651 left column to right column.
A color developing solution used for developing process of light-sensitive materials of the present invention is preferably an aqueous alkaline solution containing an aromatic primary amine type color developing agent as a main component. As color developing agents, p-phenylenediamine type compounds are preferably used, though aminophenol type compounds are also useful. Representative examples of p-phenylenediamine type compounds include 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-.beta.-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-.beta.-methanesulfonamidoethylaniline and 3-methyl-4-amino-N-ethyl-N-.beta.-methoxyethylaniline, and sulfate, hydrochloride, p-toluenesulfonate and the like thereof. These diamines in salt state are generally stabler than in free state, and preferably used.
A color developing solution generally contains a pH buffer such as carbonate, borate, phosphate or the like of an alkali metal; a development inhibitor or antifoggant such as a bromide, an iodide, benzimidazole, benzothiazole or a mercapto compound. Further, according to necessity, a preservative such as hydroxylamine or a sulfite; an organic solvent such as triethanolamine or diethylene glycol; a development accelerator such as benzyl alcohol, polyethylene glycol, a quaternary ammonium salt or an amine; a dye forming coupler; a competing coupler; a nucleating agent such as sodium borohydride; an auxiliary developing agent such as 1-phenyl-3-pyrazolidone; a thickner; a chelating agent represented by an aminopolycarboxylic acid, an aminopolyphosphonic acid, an alkylphosphonic acid or a phosphonocarboxylic acid; an antioxidant such as one disclosed in OLS No. 2,622,950; or the like may be added to the color developing solution.
In developing process of a reversal color light-sensitive material, color development is generally carried out after black-and white development For preparation of a black-and-white developing solution, known black-and-white developing agents, for example dihydroxybenzenes such as hydroquinone; 3-pyrazolidones such as 1-phenyl-3-pyrazolidone; aminophenols such as N-methyl-p-aminophenol; or the like may be used alone or in combination.
Photographic emulsion layers after color development are usually subjected to bleaching process. Bleaching process may simultaneously be carried out with fixing process, or they may separately be carried out. Further, a process method where bleach-fixing process is carried out after bleaching process may also be adopted for rapid processing. As a bleaching agent, a compound of a polyvalent metal such as iron (III), cobalt (III), chromium (VI) or copper (II); a peracid; a quinone; a nitroso compound; or the like may be used. Representative examples of a bleaching agent which may be used include a ferricyanide; a bichromate; an organic complex salt of iron (III) or cobalt (III), for example a complex salt of an aminopolycarboxylic acid such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid or 1,3-diamino-2-propanoltetraacetic acid, or a organic acid such as citric acid, tartaric acid or malic acid with iron (III) or cobalt (III); a persulfate; a manganate; nitrosophenol; or the like. Among them, an (ethylenediaminetetraacetato)iron (III), a (diethylenetriaminepentaacetato)iron (III) and a persulfate are preferable in view of rapid processing and prevention of environmental pollution. Further, an (ethylenediaminetetraacetato)iron (III) complex salt is particularly useful for a single bleaching solution as well as a single bath bleach-fixing solution.
A bleach accelerator may be used according to necessity for a bleaching solution, a bleach-fixing solution or a pre-bath thereof. Specific examples of useful bleach accelerators include compounds each having a mercapto group or a disulfido group as disclosed in U.S. Pat. No. 3,893,858, West Germany Pat. No. 1,290,812 or 2,059,988, J. P. KOKAI No. 53-32736, 53-57831, 53-37418, 53-65732, 53-72623, 53-95630, 53-95631, 53-104232, 53-124424, 53-141623 or 53-28426, or Research Disclosure No. 17129 (July, 1978) or the like; thiazoline derivatives disclosed in J. P. KOKAI No. 50-140129 or the like; thiourea derivatives disclosed in J. P. KOKOKU No. 45-8506, J. P. KOKAI No. 52-20832 or 53-32735, or U.S. Pat. No. 3,706,561; iodides disclosed in West Germany Pat. No. 1,127,715 or J. P. KOKAI No. 58-16235; polyethylene oxides disclosed in West Germany Pat. No. 966,410 or 2,748,430; polyamine compounds disclosed in J. P. KOKOKU No. 45-8836; and further compounds disclosed in J. P. KOKAI No. 49-42434, 49-59644, 53-94927, 54-35727, 55-26506 or 58-163940, iodine ions and bromine ions. Among them, compounds each having a mercapto group or a disulfido group are preferable in view of large accelerating effects, compounds disclosed in U.S. Pat. No. 3,893,858, West Germany Pat. No. 1,290,812 or J. P. KOKAI No. 53-95630 are particularly preferred. Further, compounds disclosed in U.S. Pat. No. 4,552,834 are also preferred. Such a bleach accelerator may also be added in a light-sensitive material. These bleach accelerators are particularly effective when color light-sensitive materials for photographing are bleached and fixed.
Color photographic light-sensitive materials of the present invention can also be subjected to bleach-fixing process according to a method disclosed in Japanese patent application No. 60-172968.
As a fixing agent, a thiosulfate, a thiocyanate, a thioether type compound, a thiourea, a large amount of an iodide, or the like may be used, but use of a thiosulfate is general. As a preservative for a bleach-fixing solution or a fixing solution, a sulfite, a bisulfite or a carbonylbisulfite adduct may preferably be used.
It is in general that process steps such as water washing and stabilization are carried out after a fixing step or a bleach-fixing step, but it is also possible to use a simple process method such as a method where only water washing is carried out or a method where only stabilizing process is carried out without a substantial water washing step.
In this connection, water washing step is a step for removing processing solution components adhered on or occluded in a color light-sensitive material, or components in a color light-sensitive material which turned to be unnecessary to maintain preservability of the image and physical properties of the film after processing good. On the other hand, stabilizing step is a step for enhancing preservability of the image to a level which can not be attained by water washing.
Water washing step is usually carried out by a multistep counterflow water washing method using 2 or more baths, though the step may also be carried out using a single bath. Water amount to be used in a water washing step can freely be determined according to kind of the color light-sensitive material and object, but can also be calculated out according to a method disclosed in Journal of Motion Picture and Television Engineering, 64, 248-253 (May, 1955) (S. R. Goldwasser, "Water Flow Rates in Immersion-Washing of Motion Picture Film").
Though generation of bacteria or fungi become a problem when water amount for washing is reduced for economy, it is preferable as a countermeasure therefor to use washing water whose calcium and magnesium contents are reduced as disclosed in Japanese patent application No. 61-131632. Further, it is also possible to add a disinfectant or an antifungal agent, for example a compound disclosed in J. Antibact. Antifug. Agents, vol. 11 (No. 5), p 207-223 (1983) or a compound disclosed in Hiroshi Horiguchi, "Bokin Bobai no Kagaku" (Chemistry for antibacterial or antifungal purpose). Further, it is also possible to add a chelating agent such as ethylenediaminetetraacetic acid or diethylenetriaminepentaacetic acid as a water softener.
Water amount to be used as a result of reduction usually ranges from 100 to 2000 ml per 1 m.sup.2 of a color light-sensitive material, and range from 200 to 1000 ml is preferably used for attaining both image stability and water saving effect.
pH in the water washing step is usually 5 to 9. Other various compounds are added to a stabilizing bath for stabilizing the image. For example, various buffers for adjusting pH of the film after processing such as borates, methaborates, borax, phosphates, carbonates, potassium hydroxide, sodium hydroxide, ammonia water, monocarboxylic acids, dicarboxylic acids, polycarboxylic acids or the like in combination; a chelating agent similar to one which may be added to washing water; a disinfectant; and further a fluorescent whitener according to uses can be added to a stabilizing bath, or further various ammonium salts such as ammonium chloride, ammonium sulfite, ammonium sulfate, ammonium thiosulfate and the like may be added.
pH of the stabilizing bath is usually 3 to 8, and in some occasions low pH region of 3 to 5 is preferably used because of difference of light-sensitive material species or use purpose.
The present invention can be applied to various color light-sensitive materials. Representative examples thereof include color light-sensitive materials for photographing such as color negative films for generic use or for movie and color reversal films for slide, movie or television; color internegative films for movie or generic use as used for reproduction of an original image; and the like.
A silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of making processing simple and rapid. As color developing agents for such purpose, various precursors of a color developing agent may preferably be used. Examples of such precursors include, for example, indoaniline type compounds disclosed in U.S. Pat. No. 3,342,597; Schiff base type compounds disclosed in U.S. Pat. No. 3,342,599, or Research Disclosure No. 14850 or 15159; aldol compounds disclosed in Research Disclosure No. 13924; metal salt complexes disclosed in U.S. Pat. No. 3,719,492; and urethane type compounds disclosed in J. P. KOKAI No. 53-135628; and further various salt type precursors disclosed in J. P. KOKAI No. 56-6235, 56-16133, 56-59232, 56-67842, 56-83734, 56-83735, 56-83736, 56-89735, 56-81837, 56-54430, 56-106241, 56-107236, 57-97531 or 57 83565 or the like.
Silver halide color light-sensitive materials of the present invention may contain various 1-phenyl-3-pyrazolidones according to necessity for the purpose of promoting color development. Typical examples of such compounds and disclosed in J. P. KOKAI Nos. 56-64339, 57-144547, 57-211147, 58-50532, 58-50536, 58-50533, 58-50534, 58-50535 and 58-115438 and the like.
Various processing solutions in the present invention are used at 10.degree. to 50.degree. C. Though a temperature of 33.degree. to 38.degree. C. is standard, it is possible to promote processing and shorten processing time by selecting a higher temperature, or to enhance image quality or improve stability of the processing solution by selecting a lower temperature. Further for economy of silver in light-sensitive materials, it is possible to carry out process using cobalt intensifier or hydrogen peroxide intensifier disclosed in West Germany Pat. No. 2,226,770 or U.S. Pat. No. 3,674,499.
Heaters, temperature sensors, liquid level sensors, circulating pumps, filters, floating covers, squeezes or the like may be provided in various processing baths according to necessity.
Further, in continuous process, constant finishing may be obtained by preventing change of solution composition using a replenisher for the processing solution. Amount of a replenisher may be lowered to half or less of standard replenisher amount for cost reduction or the like.
Examples of the present invention are demonstrated below, but the present invention should not be interpreted as limited only to these examples.

EXAMPLE 1
Silver halide grains are formed by a double-jet method, successively followed by physical ripening process, desalting process and chemical ripening process to obtain a silver iodobromide (containing 7.5 mole % iodine) emulsion. The average size of silver halide grains contained in this emulsion was 0.8 .mu.m. Further, 0.55 mol of silver halide was contained in 1 kg of this emulsion.
One kilogram of the emulsion was placed in a pot and dissolved with heating to 40.degree. C. One of methanol solutions of sensitizing dyes listed in Table 1 was added thereto, and the mixture was stirred. Then 10 ml of an aqueous 1.0 weight % 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene solution, 10 ml of an aqueous 1.0 weight % 1-hydroxy-3,5-dichlorotriazine sodium salt solution, and 10 ml of an aqueous 1.0 weight % sodium dodecylbenzenesulfonate solution were successively added thereto, followed by stirring. This complete emulsion was applied onto a cellulose triacetate film base to a dried film thickness of 5 .mu.m, and dried to obtain samples 101 to 123.
Each of these film samples was subjected to wedge exposure using a sensitometer having a light source of color temperature of 4800.degree. K., which was accompanied with a yellow filter (SC-50 manufactured by FUJI PHOTO FILM CO., LTD.).
After exposure to light, each of the film samples was developed at 20.degree. C. for 7 minutes using a developing solution having the following composition, subjected successively to stop and fixing processes, and then washed with water to obtain a strip having a black-and-white image. This strip was subjected to density measurement using a P type densitometer manufactured by FUJI PHOTO FILM CO., LTD. to obtain sensitivity and fog. Reference point of optical density for determination of sensitivity was point of (fog+0.20).
______________________________________Composition of the developing solution______________________________________Water 700 mlMetol 2.0 gAnhydrous sodium sulfite 100.0 gHydroquinone 5.0 gBorax pentahydrate 1.5 gWater to 1 l______________________________________
Results are shown in Table 1 using the fogging value and sensitivity value of sample 101 of fresh performance (i.e., immediately after preparation of the sample), respectively as a standard. Further, samples 101 to 123 were, after preservation for 3 days at 50.degree. C. with 80% RH, similarly exposed to light and developed, and fog and sensitivity were determined. The results are shown in Table 1.
Sensitizing dyes used in comparative examples are as follows. ##STR88##
TABLE 1-1__________________________________________________________________________ After preservation for 3 Fresh performance days (50.degree. C., 80% RH)Sample Sensitizing Sensitizing Sensitizing Relative RelativeNo. dye A dye B dye C Fog sensitivity Fog sensitivity__________________________________________________________________________101 I-2 3.2 .times. 10.sup.-4 III-10 1.6 .times. 10.sup.-4 -- .+-.0 100 +0.01 96(p.i.) mol/mol Ag mol/mol Ag (standard (standard of fog) of sensitivity)102 I-7 3.2 .times. 10.sup.-4 III-10 1.6 .times. 10.sup.-4 -- -0.01 102 +0.01 98(p.i.) mol/mol Ag mol/mol Ag103 I-2 3.2 .times. 10.sup.-4 III-17 1.6 .times. 10.sup.-4 -- +0.01 100 +0.03 96(p.i.) mol/mol Ag mol/mol Ag104 I-7 3.2 .times. 10.sup.-4 III-17 1.6 .times. 10.sup.-4 -- +0.02 103 +0.02 98(p.i.) mol/mol Ag mol/mol Ag105 SD-1 3.2 .times. 10.sup.-4 III-10 1.6 .times. 10.sup.-4 -- +0.09 104 +0.18 87(c.e.) mol/mol Ag mol/mol Ag106 SD-2 3.2 .times. 10.sup.-4 III-10 1.6 .times. 10.sup.-4 -- +0.15 96 +0.29 62(c.e.) mol/mol Ag mol/mol Ag107 SD-3 3.2 .times. 10.sup.-4 III-10 1.6 .times. 10.sup.-4 -- +0.06 90 +0.13 66(c.e.) mol/mol Ag mol/mol Ag108 SD-1 3.2 .times. 10.sup.-4 III-17 1.6 .times. 10.sup.-4 -- +0.11 104 +0.19 89(c.e.) mol/mol Ag mol/mol Ag109 SD-2 3.2 .times. 10.sup.-4 III-17 1.6 .times. 10.sup.-4 -- +0.21 93 +0.32 60(c.e.) mol/mol Ag mol/mol Ag110 SD-3 3.2 .times. 10.sup.-4 III-17 1.6 .times. 10.sup.-4 -- +0.08 90 +0.14 64(c.e.) mol/mol Ag mol/mol Ag111 I-2 2.0 .times. 10.sup.-4 III-10 1.6 .times. 10.sup.-4 II-1 1.2 .times. 10.sup.-4 .+-.0 100 +0.02 96(p.i.) mol/mol Ag mol/mol Ag mol/mol Ag (standard (standard of fog) of sensitivity)112 I-7 2.0 .times. 10.sup.-4 III-10 1.6 .times. 10.sup.-4 II-1 1.2 .times. 10.sup.-4 -0.01 99 0.00 97(p.i.) mol/mol Ag mol/mol Ag mol/mol Ag113 I-2 2.0 .times. 10.sup.-4 III-17 1.6 .times. 10.sup.-4 II-1 1.2 .times. 10.sup.-4 +0.03 102 +0.04 96(p.i.) mol/mol Ag mol/mol Ag mol/mol Ag114 I-7 2.0 .times. 10.sup.-4 III-17 1.6 .times. 10.sup.-4 II-1 1.2 .times. 10.sup.-4 +0.01 102 +0.02 97(p.i.) mol/mol Ag mol/mol Ag mol/mol Ag115 I-7 2.0 .times. 10.sup.-4 III-17 1.6 .times. 10.sup.-4 II-1 2.8 .times. 10.sup.-4 +0.01 97 +0.03 95(p.i.) mol/mol Ag mol/mol Ag mol/mol Ag116 SD-1 2.0 .times. 10.sup.-4 III-10 1.6 .times. 10.sup.-4 II-1 1.2 .times. 10.sup.-4 +0.10 106 +0.19 87(c.e.) mol/mol Ag mol/mol Ag mol/mol Ag117 SD-2 2.0 .times. 10.sup.-4 III-10 1.6 .times. 10.sup.-4 II-1 1.2 .times. 10.sup.-4 +0.17 98 +0.31 64(c.e.) mol/mol Ag mol/mol Ag mol/mol Ag118 SD-3 2.0 .times. 10.sup.-4 III-10 1.6 .times. 10.sup.-4 II-1 1.2 .times. 10.sup.-4 +0.08 92 +0.15 67(c.e.) mol/mol Ag mol/mol Ag mol/mol Ag119 SD-1 2.0 .times. 10.sup.-4 III-17 1.6 .times. 10.sup.-4 II-1 1.2 .times. 10.sup.-4 +0.14 105 +0.21 91(c.e.) mol/mol Ag mol/mol Ag mol/mol Ag120 SD-2 2.0 .times. 10.sup.-4 III-10 1.6 .times. 10.sup.-4 II-1 1.2 .times. 10.sup.-4 +0.26 93 +0.35 62(c.e.) mol/mol Ag mol/mol Ag mol/mol Ag121 SD-3 2.0 .times. 10.sup.-4 III-10 1.6 .times. 10.sup.-4 II-1 1.2 .times. 10.sup.-4 +0.11 90 +0.17 66(c.e.) mol/mol Ag mol/mol Ag mol/mol Ag__________________________________________________________________________ p.i. Present invention c.e. Comparative example
EXAMPLE 2
A silver halide emulsion layer and a gelatin protective layer having the following compositions respectively were applied on a cellulose triacetate film support which had been provided with an undercoat to prepare samples 201 to 221.
(Light-sensitive layer composition)
Figure corresponding to each component means a coated amount represented by a unit of g/m.sup.2, and means a coated amount in term of silver amount for silver halide. However, as for each of the sensitizing dyes, figure corresponding thereto means a coated amount represented by moles per 1 mole of the silver halide in the same layer.
__________________________________________________________________________ Emulsion layer Silver iodobromide emulsion 2.0 silver iodide 6 mole %, variation coefficient (S/F) of grain size = 0.18, aspect ratio 6.0, average grain size (F) = 0.8 .mu.m Gelatin 1.0 Sensitizing dyes (described in Table 2) Cpd-5 0.25 Cpd-15 0.25 Cpd-8 0.03 Cpd-7 0.05 Oil-1 0.50 Oil-4 0.13 Protective layer Gelatin 0.50 Hardening agent H-1 0.40__________________________________________________________________________Cpd-5 ##STR89##n = 50m = 25m' = 25mol. wt. about 20,000Cpd-7 ##STR90##Cpd-8 ##STR91##Cpd-15 ##STR92##Oil-1Tricresyl phosphateOil-4 ##STR93##Hardening agent H-1 ##STR94## Each of the resulting photographic elements was preserved for 3 daysat 50.degree. C. under 80% RH, and then exposed to light with an exposureamount of 10 CMS using a tungsten light source whose color temperaturehad been adjusted to 4800.degree. K. with a filter, and SC-50, an opticalfilter for measuring spectral sensitization speed manufactured by FUJIPHOTO FILM CO., LTD. Then, each element was subjected to the followingdeveloping process. The resulting results are shown in Table 2 togetherwith each fresh performance.______________________________________Color development 2 mins. and 45 secs.Bleaching 6 mins. and 30 secs.Water washing 2 mins. and 10 secs.Fixing 4 mins. and 20 secs.Water washing 3 mins. and 15 secs.Stabilization 1 min. and 05 secs.______________________________________
Compositions of processing solutions used in these steps were as follows.
______________________________________Color developing solutionDiethylenetriaminepentaacetic acid 1.0 g1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 gSodium sulfite 4.0 gPotassium carbonate 30.0 gPotassium bromide 1.4 gPotassium iodide 1.3 mgHydroxylamine sulfate 2.4 g4-(N-Ethyl-N-.beta.-hydroxyethylamino)-2- 4.5 gmethylaniline sulfateWater to 1.0 l pH 10.0Bleaching solutionAmmonium (ethylenediaminetetraacetato) 100.0 giron (III)Disodium ethylenediaminetetraacetate 10.0 gAmmonium bromide 150.0 gAmmonium nitrate 10.0 gWater to 1.0 l pH 6.0Fixing solutionDisodium ethylenediaminetetraacetate 1.0 gSodium sulfite 4.0 gAqueous ammonium thiosulfate 175.0 mlsolution (70%)Sodium bisulfite 4.6 gWater to 1.0 l pH 6.6Stabilizing solutionFormalin (40%) 2.0 mlPolyoxyethyl-p-monononylphenyl ether 0.3 g(Average polymerization degree 10)Water to 1.0 l______________________________________
TABLE 2-1__________________________________________________________________________ After preservation for 3 Fresh performance days (50.degree. C., 80% RH)Sample Sensitizing Sensitizing Sensitizing Relative RelativeNo. dye A dye B dye C Fog sensitivity Fog sensitivity__________________________________________________________________________201 I-2 3.5 .times. 10.sup.-4 III-10 1.5 .times. 10.sup.-4 -- .+-.0 100 +0.02 98(p.i.) mol/mol Ag mol/mol Ag (standard (standard of fog) of sensitivity)202 I-7 3.5 .times. 10.sup.-4 III-10 1.5 .times. 10.sup.-4 -- -0.01 +0.01 94(p.i.) mol/mol Ag mol/mol Ag203 I-2 3.5 .times. 10.sup.-4 III-19 1.5 .times. 10.sup.-4 -- +0.03 102 +0.04 96(p.i.) mol/mol Ag mol/mol Ag204 I-7 3.5 .times. 10.sup.-4 III-19 1.5 .times. 10.sup.-4 -- +0.02 104 +0.04 97(p.i.) mol/mol Ag mol/mol Ag205 SD-1 3.5 .times. 10.sup.- 4 III-10 1.5 .times. 10.sup.-4 -- +0.11 105 +0.20 86(c.e.) mol/mol Ag mol/mol Ag206 SD-2 3.5 .times. 10.sup.-4 III-10 1.5 .times. 10.sup.-4 -- +0.21 98 +0.40 60(c.e.) mol/mol Ag mol/mol Ag207 SD-3 3.5 .times. 10.sup.-4 III-10 1.5 .times. 10.sup.-4 -- +0.09 93 +0.17 63(c.e.) mol/mol Ag mol/mol Ag208 SD-1 3.5 .times. 10.sup.-4 III-19 1.5 .times. 10.sup.-4 -- +0.17 104 +0.23 87(c.e.) mol/mol Ag mol/mol Ag209 SD-2 3.5 .times. 10.sup.-4 III-19 1.5 .times. 10.sup.-4 -- +0.29 94 +0.42 57(c.e.) mol/mol Ag mol/mol Ag210 SD-3 3.5 .times. 10.sup.-4 III-19 1.5 .times. 10.sup.-4 -- +0.13 93 +0.26 62(c.e.) mol/mol Ag mol/mol Ag211 I-2 2.5 .times. 10.sup.-4 III-10 1.5 .times. 10.sup.-4 II-1 1.0 .times. 10.sup.-4 .+-.0 100 +0.03 95(p.i.) mol/mol Ag mol/mol Ag mol/mol Ag (standard (standard of fog) of sensitivity)212 I-7 2.5 .times. 10.sup.-4 III-10 1.5 .times. 10.sup.-4 II-1 1.0 .times. 10.sup.-4 -0.02 101 +101 97(p.i.) mol/mol Ag mol/mol Ag mol/mol Ag213 I-2 2.5 .times. 10.sup.-4 III-19 1.5 .times. 10.sup.-4 II-1 1.0 .times. 10.sup.-4 +0.03 103 +0.06 97(p.i.) mol/mol Ag mol/mol Ag mol/mol Ag214 I-7 2.5 .times. 10.sup.-4 III-19 1.5 .times. 10.sup.-4 II-1 1.0 .times. 10.sup.-4 +0.03 102 +0.04 98(p.i.) mol/mol Ag mol/mol Ag mol/mol Ag215 I-7 2.5 .times. 10.sup.-4 -- -- II-1 2.5 .times. 10.sup.-4 +0.02 96 +0.04 93(p.i.) mol/mol Ag mol/mol Ag216 SD-1 2.5 .times. 10.sup.-4 III-10 1.5 .times. 10.sup.-4 II-1 1.0 .times. 10.sup.-4 +0.15 108 +0.23 86(c.e.) mol/mol Ag mol/mol Ag mol/mol Ag217 SD-2 2.5 .times. 10.sup.-4 III-10 1.5 .times. 10.sup.-4 II-1 1.0 .times. 10.sup.-4 +0.22 99 +0.37 60(c.e.) mol/mol Ag mol/mol Ag mol/mol Ag218 SD-3 2.5 .times. 10.sup.-4 III-10 1.5 .times. 10.sup.-4 II-1 1.0 .times. 10.sup.-4 +0.12 93 +0.18 62(c.e.) mol/mol Ag mol/mol Ag mol/mol Ag219 SD-1 2.5 .times. 10.sup.-4 III-19 1.5 .times. 10.sup.-4 II-1 1.0 .times. 10.sup.-4 +0.19 106 +0.27 87(c.e.) mol/mol Ag mol/mol Ag mol/mol Ag220 SD-2 2.5 .times. 10.sup.-4 III-10 1.5 .times. 10.sup.-4 II-1 1.0 .times. 10.sup.-4 +0.31 94 +0.43 55(c.e.) mol/mol Ag mol/mol Ag mol/mol Ag221 SD-3 2.5 .times. 10.sup.-4 III-10 1.5 .times. 10.sup.-4 II-1 1.0 .times. 10.sup. -4 +0.17 92 +0.23 62(c.e.) mol/mol Ag mol/mol Ag mol/mol Ag__________________________________________________________________________ p.i. Present invention c.e. Comparative example
EXAMPLE 3
Preparation of sample 301
Multi-layered color light-sensitive material, which is herein referred to as sample 301, was prepared by providing each of the layers having the following compositions on a cellulose triacetate film support which had been undercoated.
(Composition of light-sensitive layer)
Coated amounts mean an amount represented by a unit of g/m.sup.2 in terms of silver for silver halide and colloidal silver, an amount represented by a unit of g/m.sup.2 for couplers, additives and gelatin, and moles per 1 mole of the silver halide in the same layer for each of the sensitizing dyes.
______________________________________The 1st layer (Antihalation layer)Black colloidal silver 0.2Gelatin 1.3Colored coupler Cpd-7 0.06Ultraviolet absorber UV-1 0.1Ultraviolet absorber UV-2 0.2Dispersion oil Oil-1 0.01Dispersion oil Oil-2 0.01The 2nd layer (Intermediate layer)Fine grain silver bromide 0.15(Average grain size 0.07 .mu.m)Gelatin 1.0Colored coupler Cpd-27 0.02Dispersion oil Oil-1 0.1The 3rd layer(The 1st red-sensitive emulsion layer)Silver iodobromide emulsion 0.6(g/m.sup.2)Silver iodide 4 mole %, Variationcoefficient of grain size (S/.sup.-- .gamma.) =0.12, Average grain size (.sup.-- .gamma.) = 0.7 .mu.m,which is hereinafter abridged asI.sup.- 4 mole, S/.sup.-- .gamma. = 0.12, 0.7 .mu.m . . . 0.6Silver iodobromide emulsion 0.3I.sup.- 3 mole, S/.gamma. = 0.11, 0.3 .mu.mGelatin 0.6SD-4 4 .times. 10.sup.-4SD-5 4 .times. 10.sup.-5Cpd-9 0.010Cpd-10 0.010Cpd-21 0.50Cpd-27 0.04Oil-1 0.15Oil-3 0.02The 4th layer(The 2nd red-sensitive layer)Silver iodobromide emulsion 0.7I.sup.- 6 mole, S/.sup.-- .gamma. = 0.15, 1.0 .mu.mGelatin 1.0SD-4 4 .times. 10.sup.-4SD-5 5 .times. 10.sup.-5Cpd-24 0.1Cpd-28 0.1Oil-1 0.01Oil-3 0.05The 5th layer (Intermediate layer)Gelatin 0.5Cpd-6 0.10Oil-1 0.05The 6th layer(The 1st green-sensitive emulsion layer)Silver iodobromide emulsion 0.35I.sup.- 4 mole, S/.sup.-- .gamma. = 0.11, 0.6 .mu.mSilver iodobromide emulsion 0.20I.sup.- 3 mole, S/.sup.-- .gamma. = 0.15, 0.3 .mu.mGelatin 1.0I-7 3.5 .times. 10.sup.-4III-10 2.5 .times. 10.sup.-4Cpd-5 0.3Cpd-7 0.07Cpd-13 0.03Oil-1 0.3Oil-4 0.1The 7th layer(The 2nd green-sensitive emulsion layer)Silver iodobromide emulsion 0.8I.sup.- 6 mole, S/.sup.-- .gamma. = 0.18, 0.8 .mu.mGelatin 0.5I-7 3.5 .times. 10.sup.-4III-10 2.5 .times. 10.sup.-4Cpd-5 0.1Cpd-15 0.1CPd-8 0.01CPd-7 0.02Oil-1 0.2The 8th layer (Intermediate layer)Gelatin 0.5Cpd-6 0.05Oil-1 0.03The 9th layer(Donor layer of interlayer effect)Silver iodobromide emulsion 0.35(g/m.sup.2)Silver iodide 2 mole %, Aspectratio 6.0, Average grain size,tabular grains of average grainsize of 1.0 .mu.m, which ishereinafter abridged asI.sup.- 2 mole, A/R = 6.0, 1.0 .mu.m . . . 0.35Silver iodobromide emulsion 0.20I.sup.- 2 mole, A/R = 6.5, 0.5 .mu.mGelatin 0.7I-7 8 .times. 10.sup.-4Cpd-3 0.18Cpd-4 0.05Cpd-5 0.13Oil-1 0.20The 10th layer (Yellow filter layer)Gelatin 0.5Cpd-2 0.25Cpd-6 0.10The 11th layer(The 1st blue-sensitive emulsion layer)Silver iodobromide emulsion 0.3I.sup.- 3 mole, A/R = 7.5, 1.0 .mu.mSilver iodobromide emulsion 0.15I.sup.- 3 mole, A/R = 7.5, 0.5 .mu.mGelatin 1.0SD-6 2 .times. 10.sup.-4Cpd-1 0.05Cpd-8 0.10Cpd-29 0.80Oil-1 0.20The 12th layer(The 2nd blue-sensitive emulsion layer)Silver iodobromide emulsion 0.5I.sup.- 10 mole, S/.sup.-- .gamma. = 0.11, 1.2 .mu.mGelatin 0.5SD-6 1 .times. 10.sup.-4Cpd-29 0.20Cpd-3 0.02Oil-1 0.10The 13th layer(The 1st protective layer)Gelatin 0.8UV-1 0.1UV-2 0.2Oil-1 0.01Oil-2 0.01The 14th layer(The 2nd protective layer)Fine grain silver bromide emulsion 0.5I.sup.- 2 mole, S/.sup.-- .gamma. = 0.2, 0.07 .mu.mGelatin 0.45Polymethyl methacrylate 0.2grain size 1.5 .mu.mHardening agent H-1 0.4Formaldehyde scavenger S-1 0.5Formaldehyde scavenger S-2 0.5______________________________________
Besides the above components, a stabilizing agent of emulsion Cpd-26 and a surfactant were added to each layer as coating aids. ##STR95##
The thus prepared sample was named sample 301. Samples 302 to 314 were each prepared in the same manner as that for preparation of sample 301 using the same composition with sample 301 except of changing the sensitizing dyes for those listed in Table 3.
Each of these photographic elements was exposed to light with an exposure amount of 25 CMS using a tungsten light source whose color temperature had been adjusted to 4800.degree. K. Then, each element was subjected to developing process according to the same steps as in Example 2 except that color development time was made to be 3 minutes and 15 seconds.
The results are shown in Table 3 using fog value and sensitivity value of fresh performance (immediately after preparation of samples) as standard, respectively Further, each of samples 301 to 314 was preserved for 3 days at 50.degree. C. under 80% RH, and then similarly, exposed to light, developed and measured for fog and sensitivity. The results are also shown in Table 3.
TABLE 3__________________________________________________________________________ The 9th After preserva-The 6th layer The 7th layer layer sensi- Fresh tion for 3 dayssensitizing dye sensitizing dye tizing dye preformance (50.degree. C., 80% RH)Sam- Amount Amount Amount Amount Amount Relative Relativeple Spe- mol/mol Spe- mol/mol Spe- mol/mol Spe- mol/mol Spe- mol/mol sensi- sensi-No. cies Ag cies Ag cies Ag cies Ag cies Ag Fog tivity Fog tivity__________________________________________________________________________301 I-7 3.5 .times. III-10 2.5 .times. I-7 3.5 .times. III- 2.5 .times. I-7 8 .times. .+-.0 100 +0.02 95(p.i.) 10.sup.-4 10.sup.-4 10.sup.-4 10 10.sup.-4 10.sup.-4 (standard (standard of fog) of sensi- tivity)302 " 3.5 .times. " 2.5 .times. " 3.5 .times. III- 2.5 .times. I-19 8 .times. -0.01 99 +0.01 93(p.i.) 10.sup.-4 10.sup.-4 10.sup.-4 10 10.sup.-4 10.sup.-4303 I-19 3.5 .times. " 2.5 .times. I-19 3.5 .times. III- 2.5 .times. I-7 8 .times. +0.01 99 +0.02 92(p.i.) 10.sup.-4 10.sup.-4 10.sup.-4 10 10.sup.-4 10.sup.-4304 I-5 3.5 .times. " 2.5 .times. I-5 3.5 .times. III- 2.5 .times. " 8 .times. +0.01 101 +0.02 95(p.i.) 10.sup.-4 10.sup.-4 10.sup.-4 10 10.sup.-4 10.sup.-4305 I-7 3.5 .times. " 2.5 .times. I-7 3.5 .times. III- 2.5 .times. SD-1 8 .times. +0.10 102 +0.25 78(c.e.) 10.sup.-4 10.sup.-4 10.sup.-4 10 10.sup. -4 10.sup.-4306 " 3.5 .times. " 2.5 .times. " 3.5 .times. III- 2.5 .times. SD-7 8 .times. +0.05 86 +0.08 66(c.e.) 10.sup.-4 10.sup.-4 10.sup.-4 10 10.sup.-4 10.sup.-4307 " 3.5 .times. " 2.5 .times. " 3.5 .times. III- 2.5 .times. SD-2 8 .times. +0.13 98 +0.40 70(c.e.) 10.sup.-4 10.sup.-4 10.sup.-4 10 10.sup.-4 10.sup.-4308 " 3.5 .times. " 2.5 .times. " 3.5 .times. III- 2.5 .times. SD-8 8 .times. +0.04 90 +0.09 72(c.e.) 10.sup.-4 10.sup.-4 10.sup.-4 10 10.sup.-4 10.sup.-4309 " 3.5 .times. " 2.5 .times. " 3.5 .times. III- 2.5 .times. SD-3 8 .times. +0.02 88 +0.07 69(c.e.) 10.sup.-4 10.sup.-4 10.sup. -4 10 10.sup.-4 10.sup.-4310 SD-1 3.5 .times. " 2.5 .times. SD-1 3.5 .times. III- 2.5 .times. I-7 8 .times. +0.14 103 +0.30 80(c.e.) 10.sup.-4 10.sup.-4 10.sup.-4 10 10.sup.-4 10.sup.-4311 SD-7 3.5 .times. " 2.5 .times. SD-7 3.5 .times. III- 2.5 .times. " 8 .times. +0.07 86 +0.10 67(c.e.) 10.sup.-4 10.sup.-4 10.sup.-4 10 10.sup.-4 10.sup.-4312 SD-2 3.5 .times. " 2.5 .times. SD-2 3.5 .times. III- 2.5 .times. " 8 .times. +0.18 95 +0.46 63(c.e.) 10.sup.-4 10.sup.-4 10.sup.-4 10 10.sup.-4 10.sup.-4313 SD-8 3.5 .times. " 2.5 .times. SD-8 3.5 .times. III- 2.5 .times. " 8 .times. +0.07 89 +0.12 71(c.e.) 10.sup.-4 10.sup.-4 10.sup. -4 10 10.sup.-4 10.sup.-4314 SD-3 3.5 .times. " 2.5 .times. SD-3 3.5 .times. III- 2.5 .times. " 8 .times. +0.03 86 +0.09 63(c.e.) 10.sup.-4 10.sup.-4 10.sup.-4 10 10.sup.-4 10.sup.-4__________________________________________________________________________
EXAMPLE 4
Multi-layered color light-sensitive material, which is herein referred to as sample 401, was prepared by providing each of the layers having the following compositions on a cellulose triacetate film support which had been undercoated.
The 1st layer (Antihalation layer)
Gelatin layer (dry film thickness 2 .mu.m) containing 0.25 g/m.sup.2 black colloidal silver, 0.04 g/m.sup.2 UV-3, 0.1 g/m.sup.2 UV-4, 0.1 g/m.sup.2 UV-5 and 0.1 cc/m.sup.2 Oil-2
The 2nd layer (Intermediate layer)
Gelatin layer (dry film thickness 1 .mu.m) containing 0.05 g/m.sup.2 H-1 and 0.05 cc/m.sup.2 Oil-1
The 3rd layer (The 1st red-sensitive emulsion layer)
Gelatin layer (dry film thickness 1 .mu.m) containing 0.5 g/m.sup.2 in terms of silver amount of monodispersed silver iodobromide emulsion spectrally sensitized with 1.4 mg/m.sup.2 SD-13 and 0.06 mg/m.sup.2 SD-14 (iodine content 4 mole %, cube, average grain size 0.3 .mu.m), 0.2 g/m.sup.2 Cpd-36, 0.05 g/m.sup.2 Cpd-37 and 0.12 cc/m.sup.2 Oil-1
The 4th layer (The 2nd red-sensitive emulsion layer)
Gelatin layer (dry film thickness 2.5 .mu.m containing 0.8 g/m.sup.2 in terms of silver amount of monodispersed silver iodobromide emulsion spectrally sensitized with 1.6 mg/m.sup.2 SD-13 and 0.06 mg/m.sup.2 SD-14 (iodine content 2.5 mole %, tetradecahedron, average grain size 0.55 .mu.m), 0.55 g/m.sup.2 Cpd-36, 0.14 g/m.sup.2 Cpd-37 and 0.33 cc/m.sup.2 Oil-2
The 5th layer (Intermediate layer)
Gelatin layer (dry film thickness 1 .mu.m) containing 0.1 g/m.sup.2 H-1 and 0.1 cc/m.sup.2 Oil-1
The 6th layer (The 1st green-sensitive emulsion layer)
Gelatin layer (dry film thickness 1 .mu.m) containing 0.7 g/m.sup.2 in terms of silver amount of silver iodobromide emulsion spectrally sensitized with 2.3 mg/m.sup.2 II-3, 1.5 mg/m.sup.2 I-7 and 1.0 mg/m.sup.2 III-10 (iodine content 3 mole %, average grain size 0.3 .mu.m , 0.35 g/m.sup.2 Cpd-20 and 0.26 cc/m.sup.2 Oil-1
The 7th layer (The 2nd green-sensitive emulsion layer)
Gelatin layer (dry film thickness 2.5 .mu.m) containing 0.7 g/m.sup.2 in terms of silver amount of tabular silver iodobromide emulsion spectrally sensitized with 0.8 mg/m.sup.2 II-3, 0.6 mg/m.sup.2 I-7 and 0.4 mg/m.sup.2 III-10 (iodine content 2.5 mole %; grains having a diameter/thickness ratio of 5 or more occupying 50% of projected area of all the grains; average grain thickness 0.10 .mu.m), 0.25 g/m.sup.2 Cpd-38 and 0.05 cc/m.sup.2 Oil-1
The 8th layer (Intermediate layer)
Gelatin layer (dry film thickness 1 .mu.m) containing 0.05 g/m.sup.2 H-1 and 0.1 g/m.sup.2 Oil-1
The 9th layer (Yellow filter layer)
Gelatin layer (dry film thickness 1 .mu.m) containing 0.1 g/m.sup.2 yellow colloidal silver, 0.02 g/m.sup.2 H-1, 0.03 g/m.sup.2 Cpd-41 and 0.04 cc/m.sup.2 Oil-1
The 10th layer (The 1st blue-sensitive emulsion layer)
Gelatin layer (dry film thickness 1.5 .mu.m) containing 0.6 g/m.sup.2 in terms of silver amount of silver iodobromide emulsion spectrally sensitized 1.0 mg/m.sup.2 SD-15 (iodine content 2.5 mole %, average grain size 0.7 .mu.m), 0.5 g/m.sup.2 Cpd-39 and 0.1 cc/m.sup.2 Oil-1
The 11th layer (The 2nd blue-sensitive emulsion layer
Gelatin layer (dry film thickness 3 .mu.m) containing 1.1 g/m.sup.2 in terms of silver amount of tabular silver iodobromide emulsion spectrally sensitized with 1.7 mg/m.sup.2 SD-15 (iodine content 2.5 mole %; grains having a diameter/thickness ratio of 5 or more occupying 50% of projected area of all the grains; average grain thickness 0.13 .mu.m), 1.2 g/m.sup.2 Cpd-39 and 0.23 cc/m.sup.2 Oil-1
The 12th layer (The 1st protective layer)
Gelatin layer (dry film thickness 2 .mu.m) containing 0.02 g/m.sup.2 UV-3, 0.03 g/m.sup.2 UV-4, 0.03 g/m.sup.2 UV-5, 0.2 g/m.sup.2 UV-6 and 0.28 cc/m.sup.2 Oil-2
The 13th layer (The 2nd protective layer)
Gelatin layer (dry film thickness 0.8 .mu.m) containing 0.1 g/m.sup.2 in terms of silver of fine grain silver iodobromide emulsion as superficially fogged (iodine content 1 mole %, average grain size 0.06 .mu.m) and polymethyl methacrylate grains (average grain size 1.5 .mu.m)
Besides the above components, a gelatin hardening agent H-3 and a surfactant were added to each of the above layers.
Compounds used for preparation of the sample are shown below. ##STR96##
The thus prepared sample was named sample 401. Samples 402 to 408 were each prepared in the same manner as that for preparation of sample 401 using the same composition with sample 401 except of changing the sensitizing dye I-7 for those listed in Table 4.
Each of these photographic elements as such or after preservation under the same condition as in Example 3 was exposed to light, followed by the following process, and then measured for fog and sensitivity. The results are shown in Table 4.
In this connection, extent of fog of each sample of fresh performance or after the preservation was relatively expressed by measuring maximum color density of each sample after color development and comparing it with that of sample 401 of fresh performance. Lowering of relative value in comparison with the standard value shows increase of fog.
______________________________________Process stepsStep Time Temperature______________________________________First development 6 minutes 38.degree. C.Water washing 2 minutes "Reversal 2 minutes "Color development 6 minutes "Adjustment 2 minutes "Bleaching 6 minutes "Fixing 4 minutes "Water washing 4 minutes "Stabilization 1 minute Ambient temperatureDrying______________________________________
Compositions of the used process solutions are as follows.
______________________________________The first developing solutionWater 700 mlPentasodium nitrilo-N,N,N- 2 gtrimethylenephosphonateSodium sulfite 20 gHydroquinone monophosphate 30 gSodium carbonate monohydrate 30 g1-Phenyl-4-methyl-4-hydroxymethyl- 2 g3-pyrazolidonePotassium bromide 2.5 gPotassium thiocyanate 1.2 gPotassium iodide (0.1% solution) 2 mlWater to 1000 mlReversal solutionWater 700 mlPentasodium nitrilo-N,N,N- 3 gtrimethylenephosphonateTin (II) chloride dihydrate 1 gp-Aminophenol 0.1 gPotassium hydroxide 8 gGlacial acetic acid 15 mlWater to 1000 mlColor developing solutionWater 700 mlPentasodium nitrilo-N,N,N- 3 gtrimethylenephosphonateSodium sulfite 7 gSodium tertiary phosphate 36 gdodecahydratePotassium bromide 1 gPotassium iodide (0.1% solution) 90 mlSodium hydroxide 3 gCitrazinic acid 1.5 gN-Ethyl-N-.beta.-methanesulfonamidoethyl)- 11 g3-methyl-4-aminoaniline sulfate3,6-Dithiaoctane-1,8-diol 1 gWater to 1000 mlConditioning solutionWater 700 mlSodium sulfite 12 gDisodium ethylenediaminetetraacetate 8 gdihydrateThioglycerine 0.4 mlGlacial acetic acid 3 mlWater to 1000 mlBleaching solutionWater 800 mlDisodium ethylenediaminetetraacetate 2 gdihydrateAmmonium (ethylenediaminetetraacetato) 120 giron (III) dihydratePotassium bromide 100 gWater to 1000 mlFixing solutionWater 800 mlSodium thiosulfate 80.0 gSodium sulfite 5.0 gSodium bisulfite 5.0 gWater to 1000 mlStabilizing solutionWater 800 mlFormalin (37 weight %) 5.0 mlFUJI DRIWELL (a surfactant 5.0 mlmanufactured by FUJI PHOTO FILM CO., LTD.)Water to 1000 ml______________________________________
Similar results were obtained when water washing after fixing was carried out using the following water washing solution in place of water.
______________________________________Water washing solution______________________________________Disodium ethylenediaminetetraacetate 0.4 gdihydrateWater to 1 lWith sodium hydroxide pH 7.0______________________________________
TABLE 4__________________________________________________________________________The 6th layer The 7th layer After preservation forsensitizing dye sensitizing dye Fresh performance 3 days (50.degree. C., 80% RN)Sample Amount Amount Max. color Relative Max. color RelativeNo. Species mg/m.sup.2 Species mg/m.sup.2 density sensitivity density sensitivity__________________________________________________________________________401 I-7 1.5 I-7 0.6 .+-.0 100 -0.05 95(p.i.) (standard of (standard of max. color sensitivity) density)402 I-19 1.5 I-19 0.6 .+-.0 99 -0.06 95(p.i.)403 I-5 1.5 I-5 0.6 -0.02 102 -0.07 97(p.i.)404 SD-1 1.5 SD-1 0.6 -0.25 103 -0.43 75(c.e.)405 SD-7 1.5 SD-7 0.6 -0.15 91 -0.25 66(c.e.)406 SD-2 1.5 SD-2 0.6 -0.32 95 -0.49 63(c.e.)407 SD-8 1.5 SD-8 0.6 -0.15 90 -0.23 67(c.e.)408 SD-3 1.5 SD-3 0.6 -0.08 83 -0.20 65(c.e.)__________________________________________________________________________
EXAMPLE 5
Each of the following 1st to 7th layers was applied on a paper support, both surfaces of which had been laminated with polyethylene to prepare color light-sensitive material samples 501 to 508. Polyethylene on the surface where the 1st layer was applied contains titanium dioxide and a trace amount of ultramarine.
(Constitution of light-sensitive layer)
Figure corresponding to each component means a coated amount represented by a unit of g/m.sup.2, and means a coated amount in terms of silver amount for silver halide.
__________________________________________________________________________The 1st layer (Blue-sensitive layer)Silver chlorobromide emulsion 0.30(Silver bromide 80 mole %)Yellow coupler Cpd-42 0.70Oil-6 0.15Gelatin 0.20The 2nd layer (Intermediate layer)Gelatin 0.90Di-t-octylhydroquinone 0.05Oil-2 0.10The 3rd layer (Green-sensitive layer)Refer to Table 6The 4th layer (Ultraviolet absorptive intermediate layer)Ultraviolet absorber 0.06/0.25/0.25(UV-3/UV-7/UV-5)Oil-6 0.20Gelatin 1.5The 5th layer (Red-sensitive layer)Silver chlorobromide emulsion 0.20(Silver bromide 70 mole %)Cyan coupler (Cpd-43/Cpd-44) 0.2/0.2Coupler solvent (Oil-6/Oil-2) 0.10/0.20Gelatin 0.9The 6th layer (Ultraviolet absorptive intermediate layer)Ultraviolet absorber 0.06/0.25/0.25(UV-3/UV-7/UV-5)Oil-2 0.20Gelatin 1.5The 7th layer (Protective layer)Hardening agent H-2 0.28Gelatin 1.5__________________________________________________________________________Cpd-42 ##STR97##Oil-6(C.sub.9 H.sub.19 O).sub.3POUV-7 ##STR98##Cpd-43 ##STR99##Cpd 44 ##STR100##H-2: ##STR101##The following compounds were used as spectrally sensitizing dyes for theblue-sensitive emulsion layer and red-sensitive emulsion layer,
Blue-sensitive emulsion layer; SD-6
(Added in an amount of 2.times.10.sup.-4 moles per 1 mole of the silver halide) ##STR102##
The following dyes were used as irradiation inhibiting dyes for respective emulsion layers. ##STR103##
The green-sensitive emulsion layer contains a silver chlorobromide emulsion (silver chloride content 30 mole %) comprising monodispersed cubic grains having an average grain size of 0.4 .mu.m, and chemical sensitization was carried out with the addition of 2.0.times.10.sup.-5 moles of sodium thiosulfate per 1 mole of the silver halide. The emulsion layer further contains 300 mg of 4-hydroxy-6-methyl-(1,3,3a,7)-tetrazaindene per 1 mole of the silver halide. Combinations of spectrally sensitizing dyes used were shown in Table 6.
Further, 100 g of a magenta dye-forming coupler, Cpd-20 together with 50 g of a fading inhibitor, Cpd-45 were dissolved in a mixed solvent of 200 ml of a solvent Oil-7 and 100 ml of ethyl acetate. This solution was emulsified and dispersed in 200 g of an aqueous 10% gelatin solution containing 8.0 g sodium dodecylbenzenesulfonate to prepare an emulsified dispersion, which was then used. ##STR104##
The coated amount of the emulsion for the 3rd layer was 200 mg/m.sup.2 in terms of silver amount.
______________________________________Emulsified dispersion Emulsified emulsion 2______________________________________Magenta coupler Cpd-20 600 mg/m.sup.2Fading inhibitor Cpd-45 300 mg/m.sup.2Coupler solvent Oil-7 1.20 ml/m.sup.2(Gelatin was added to the coating solution so that theresulting applied gelatin amount becomes 1800 mg/m.sup.2)______________________________________
In order to confirm preservability of these coated samples, they were examined for change of photographic performance after preservation for 4 weeks in a state of 50.degree. C. and 45% RH as a forced test. The samples before and after preservation were each subjected to gradation exposure to light for sensitometry using an enlarging machine (FUJI COLOR HEAD 690 manufactured by FUJI PHOTO FILM CO., LTD.) through a green filter, and then subjected to developing process comprising the following process steps.
______________________________________ Temperature Time______________________________________Process stepDeveloping solution 33.degree. C. 3.5 minutesBleach-fixing solution 33.degree. C. 1.5 minutesWater washing 28-35.degree. C. 3.0 minutesDeveloping solutionDiethylenetriaminepentaacetic acid 1.0 gBenzyl alcohol 15 mlDiethylene glycol 10 mlNa.sub.2 SO.sub.3 2.0 gKBr 0.5 gHydroxylamine sulfate 3.0 g4-Amino-3-methyl-N-ethyl-N-[.beta.- 5.0 g(methanesulfonamido)ethyl]-p-phenylenediamine sulfateNa.sub.2 CO.sub.3 monohydrate 30 gWater to 1 l (pH 10.1)Bleach-fixing solutionAmmonium thiosulfate (54 wt %) 150 mlNa.sub.2 SO.sub.3 15 gNH.sub.4 [Fe(EDTA)] 55 gEDTA2.2Na 4 gWater to 1 l (pH 6.9)______________________________________
Color density of each sample after the above processing was measured, and sensitivity change after the preservation based on fresh performance, and fog density of each sample were determined. The results are shown in Table 5.
TABLE 5__________________________________________________________________________ After preservation for 4 weeks Fresh performance (50.degree. C., 45% RH)Sample The 3rd layer sensitizing dye Relative RelativeNo. Species Amount Species Amount Fog Sensitivity Fog Sensitivity__________________________________________________________________________501 I-5 1.6 .times. 10.sup.-4 III-10 3.2 .times. 10.sup.-4 .+-.0 100 +0.04 97(p.i.) mol/mol Ag mol/mol Ag (Standard (Standard of of fog) sensitivity)502 I-7 1.7 .times. 10.sup.-4 " 3.2 .times. 10.sup.-4 +0.02 96 +0.04 95(p.i.) mol/mol Ag mol/mol Ag504 SD-1 1.7 .times. 10.sup.-4 " 3.2 .times. 10.sup.-4 +0.12 103 +0.25 88(c.e.) mol/mol Ag mol/mol Ag505 SD-7 1.7 .times. 10.sup.-4 " 3.2 .times. 10.sup.-4 +0.05 90 +0.12 70(c.e.) mol/mol Ag mol/mol Ag506 SD-2 1.7 .times. 10.sup.-4 " 3.2 .times. 10.sup.-4 +0.15 97 +0.38 58(c.e.) mol/mol Ag mol/mol Ag507 SD-8 1.7 .times. 10.sup.-4 " 3.2 .times. 10.sup.-4 +0.06 88 +0.10 65(c.e.) mol/mol Ag mol/mol Ag508 SD-3 1.7 .times. 10.sup.-4 " 3.2 .times. 10.sup.-4 +0.03 86 +0.13 63(c.e.) mol/mol Ag mol/mol Ag__________________________________________________________________________
EXAMPLE 6
Preparation of sample 601
Multi-layered color light-sensitive material 601 was prepared by providing each of the layers having the following compositions on a cellulose triacetate film support which had been undercoated.
(Composition of light-sensitive layer)
Figure corresponding to each component means a coated amount represented by a unit of g/m.sup.2, and means a coated amount in terms of silver amount for silver halide. However, as for each of the sensitizing dyes, figure corresponding thereto means a coated amount represented by moles per 1 mole of the silver halide in the same layer.
______________________________________The 1st layer (Antihalation layer)Black colloidal silver 0.2Gelatin 2.6UV-4 0.2Oil-3 0.02The 2nd layer (Intermediate layer)Fine grain silver bromide 0.15(Average grain size 0.07 .mu.m)Gelatin 1.0The 3rd layer (Low-speed red-sensitive emulsionlayer)Monodispersed silver iodobromide emulsion 1.5(silver iodide 5.5 mole %, averagegrain size about 0.3 .mu.m, variationcoefficiency with respect to grain size(hereinafter merely referred to variationcoefficiency) 19%)Gelatin 3.0SD-17 2.0 .times. 10.sup.-4SD-5 1.0 .times. 10.sup.-4SD-10 0.3 .times. 10.sup.-4Cpd-22 0.7Cpd-48 0.1Cpd-17 0.02Cpd-54 0.01Oil-3 0.8Oil-1 0.2Oil-8 0.1The 4th layer (High-speed red-sensitive emulsionlayer)Monodispersed silver iodobromide emulsion 1.2(silver iodide 3.5 mole %, averagegrain size about 0.7 .mu.m, variationcoefficiency 18%)Gelatin 2.5SD-17 3 .times. 10.sup.-4SD-5 1.5 .times. 10.sup.-4SD-10 0.45 .times. 10.sup.-4Cpd-46 0.15Cpd-47 0.05Cpd-48 0.03Cpd-17 0.01Oil-3 0.05Oil-1 0.3The 5th layer (Intermediate layer)Gelatin 0.8Cpd-56 0.05Oil-2 0.01The 6th layer (Low-speed green-sensitive emulsion layer)Monodispersed silver iodobromide emulsion 0.4(silver iodide 5 mole %, average grainsize about 0.3 .mu.m, variationcoefficiency 19%)Monodispersed silver iodobromide emulsion 0.8(silver iodide 7 mole %, average grainsize about 0.5 .mu.m)Gelatin 3.0II-3 1 .times. 10.sup.-4II-2 3 .times. 10.sup.-4III-10 1 .times. 10.sup.-4I-4 1 .times. 10.sup.-4Cpd-49 0.2CPd-50 0.4Cpd-51 0.16Cpd-53 0.05Oil-1 1.2Oil-8 0.05Oil-9 0.01The 7th layer (High-speed green-sensitiveemulsion layer)Multi-dispersed silver iodobromide 0.9emulsion(silver iodide 3.5 mole %, averagegrain size about 0.8 .mu.m, variationcoefficiency 15%)Gelatin 1.6II-3 0.7 .times. 10.sup.-4II-2 2.1 .times. 10.sup.-4III-10 0.7 .times. 10.sup.-4I-4 0.7 .times. 10.sup.-4Cpd-50 0.05Cpd-51 0.04Cpd-53 0.01Oil-3 0.08Oil-1 0.3Oil-8 0.03The 8th layer (Yellow filter layer)Yellow colloidal silver 0.2Gelatin 0.9Cpd-56 0.2Oil-1 0.1The 9th layer (Low-speed blue-sensitiveemulsion layer)Monodispersed silver iodobromide 0.4emulsion(silver iodide 6 mole %, averagegrain size 0.3 .mu.m, variationcoefficiency 20%)Monodispersed silver iodobromide 0.4emulsion(silver iodide 5 mole %, averagegrain size 0.6 .mu.m, variationcoefficiency 17%)Gelatin 2.9SD-18 1 .times. 10.sup.-4SD-19 1 .times. 10.sup.-4Cpd-52 1.2Cpd-17 0.05Oil-1 0.4Oil-8 0.1The 10th layer (High-speed blue-sensitiveemulsion layer)Monodispersed silver iodobromide 0.5emulsion(silver iodide 6 mole %, average grainsize 1.5 .mu.m, variation coefficiency14%)Gelatin 2.2SD-18 5 .times. 10.sup.-5SD-19 5 .times. 10.sup.-5Cpd-52 0.4Cpd-17 0.02Oil-1 0.1The 11th layer (The 1st protective layer)Gelatin 1.0UV-4 0.1UV-8 0.1UV-3 0.1Cpd-55 0.1Oil-3 0.1Oil-8 0.1The 12th layer (The 2nd protective layer)Fine grain silver bromide emulsion 0.25(average grain size 0.07 .mu.m)Gelatin 1.0Polymethyl methacrylate grains 0.2(diameter 1.5 .mu.m)Cpd-58 0.5______________________________________
Besides the above components, a surfactant Cpd-57 and a hardening agent H-3 were added to each layer. ##STR105##
The thus prepared sample was named sample 601. Samples 402 to 408 were similarly prepared using the same composition with sample 601 except that the sensitizing dye I-4 of the 6th and 7th layers was replaced by those described in Table 6.
Each of these photographic elements as such or after preservation under the same condition as in Example 3 was exposed to light, followed by the following process, and then measured for fog and sensitivity. The results are shown in Table 6.
______________________________________ Process Amount of temperature Process replenisherProcess step (.degree.C.) time (ml/24 Exp)______________________________________Color development 38 .+-. 0.3 3'15" 55Bleaching 30- 38 6'30" 10Fixing 20- 35 3'15" 34.5Rinse 1* 20- 35 1'20" --Rinse 2* 20- 35 1'20" 34.7Stabilization 20- 35 1'20" 34.5Drying 40- 60 2'50"______________________________________ (*cascade system from rinse 2 to rinse 1)
Processing solutions used are as follows.
______________________________________ Tank solution Replenisher______________________________________Color developing solutionDiethylenetriamine- 3.0 g 3.0 gpentaacetic acidPotassium carbonate 37 g 37 gSodium sulfite 3.2 g 4.5 gPotassium bromide 1.2 g 0.95 gHydroxylamine sulfate 2.7 g 3.4 g4-(N-Ethyl-N-.beta.- 4.0 g 5 ghydroxyethylamino)-2-methylamiline sulfatePotassium iodide 5 mg --Water to 1 l 1 lKOH to pH 10.05 10.00Bleaching solutionAmmonium bromide 177 g 177 gAmmonium (ethylene- 120 g 120 gdiaminetetraacetato)iron (III)Ethylenediamine- 10 g 10 gtetraacetic acidAmmonia water 10 ml --Water to 1 l 1 lWith KOH/glacial acetic pH 6.0 5.7acidFixing solutionAmmonia thiosulfate (70%) 180 ml 260 mlSodium sulfite 13 g 18 gEthylenediamine- 5 g 5 gtetraacetic acidWater to 1 l 1 lWith KOH/glacial acetic pH 6.75 7.0acidRinsing solution (the sameformulation between tanksolution and replenisher)2-Methyl-4-isothiazolin-3-one 3 mg5-Chloro-2-methyl-4-isothiazolin-3-one 6 mgEthylene glycol 1.5 mlWater to 1 lStabilizing solution (the sameformulation between tanksolution and replenisher)Formalin (37%) 4.0 mlEthylene glycol 2 gSurfactant 0.4 g ##STR106##Water to 1 l______________________________________
TABLE 6__________________________________________________________________________ After preservation for Fresh performance 3 days (50.degree. C., 80% RH)Sample The 6th layer The 7th layer Relative RelativeNo. sensitizing dye sensitizing dye Fog sensitivity Fog sensitivity__________________________________________________________________________601 I-4 1 .times. 10.sup.-4 I-4 0.7 .times. 10.sup.-4 .+-.0 100 +0.03 95(p.i.) mol/mol Ag mol/mol Ag (standard (standard of of fog) sensitivity)602 I-19 1 .times. 10.sup.-4 I-19 0.7 .times. 10.sup.-4 +0.02 98 .+-.0 95(p.i)603 I-5 1 .times. 10.sup.-4 I-5 0.7 .times. 10.sup.-4 .+-.0 102 +0.03 94(p.i)604 SD-1 1 .times. 10.sup.-4 SD-1 0.7 .times. 10.sup.-4 +0.15 104 +0.30 82(c.e)605 SD-7 1 .times. 10.sup.-4 SD-7 0.7 .times. 10.sup.-4 +0.06 89 +0.11 69(c.e)606 SD-2 1 .times. 10.sup.-4 SD-2 0.7 .times. 10.sup.-4 +0.18 96 +0.48 62(c.e)607 SD-8 1 .times. 10.sup.-4 SD-8 0.7 .times. 10.sup.-4 +0.07 88 +0.12 68(c.e)608 SD-3 1 .times. 10.sup.-4 SD-3 0.7 .times. 10.sup.-4 +0.05 87 +0.11 64(c.e)__________________________________________________________________________
As is seen from the foregoing description, it is possible to increase sensitivity of photographic light-sensitive materials and greatly inhibit increase of fog and lowering of sensitivity thereof during preservation by using in combination a spectrally sensitizing dye of the general formula (I) and a spectrally sensitizing dye of the general formula (III), or by using in combination a spectrally sensitizing dye of the general formula (I), a spectrally sensitizing dye of the general formula (II) and a spectrally sensitizing dye of the general formula (III).

Number	Name	Date
3580723	Sato et al.	May 1971
3864134	Ueda et al.	Feb 1975
4362813	Mihara et al.	Dec 1982
4551424	Ikeda et al.	Nov 1985
4571380	Noguchi et al.	Feb 1986

Silver halide photographic emulsion

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