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 color light wavelength region. More specifically, the present invention relates to a silver halide photographic emulsion which can give photographic light-sensitive materials having an elevated spectral sensitivities in green short wavelength region and excellent preservabilities and 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 two 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 emulsions has only a low spectral sensitivity in a green short wavelength region, which resulted in a problem in color reproduction.
On the other hand, as sensitizing dyes having a maximal value 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 dimethinemerocyanine dyes (for example, compounds disclosed in U.S. Pat. Nos. 2493748, 2519001 and 3480439 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 benzimidazolooxazolocarbocyanin or a dimethinemerocyanine, increase of fog after application of the emulsions under a high temperature or a condition of high temperature and high humidity, 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 preservability and 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 compound selected from the group consisting of the compounds represented by the general formula (II) and the compounds represented by the general formula (III): ##STR4## 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, acylamine groups, acyl groups, cyano groups, carbamoyl groups, sulfamoyl groups, carboxyl groups or acyloxy groups under the condition that R.sub.0 and R.sub.1 do not represent hydrogen atoms at the same time; R.sub.2 represents a hydrogen atom, an alkyl group or an 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 "L" (its unit is .ANG.) as a STERIMOL parameter 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 (their units are .ANG.) which are parameters of STERIMOL, under the condition that R.sub.0 and R.sub.3, or R.sub.1 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.sup..crclbar. represents a counter anion; and l is 0 or 1, and when an inner salt is formed, l is 0; ##STR5## wherein Z.sub.1 and Z.sub.2 may be the same or different, and represent nonmetal atomic groups necessary for forming benzene rings or naphthalene rings under the condition that Z.sub.1 and Z.sub.2 do not form naphthalene rings at the same time, and under the further condition that when Z.sub.1 and/or Z.sub.2 represent benzene rings having a substituent, the substituent does not represent a substituent defined as R.sub.3 ; R.sub.7 has the same significances with R.sub.2 ; R.sub.6 and R.sub.8 have the same significance with R.sub.4 and R.sub.5 respectively; X.sub.2.sup..crclbar. has the same significance with X.sub.1.sup..crclbar. ; and n has the same significance with l; ##STR6## wherein Z.sub.3 and Z.sub.4 may be the same or different, and represent nonmetal atomic groups necessary for forming benzene rings; Y represents a sulfur atom or a selenium atom; R.sub.9 and R.sub.11 have the same significances with R.sub.4 and R.sub.5 respectively; R.sub.10 has the same significances with R.sub.2 ; X.sub.3.sup..crclbar. has the same significance with X.sub.1.sup..crclbar., and n has the same significance with l.
Alkyl groups in the definition of R.sub.0 and R.sub.1 may include those having substituent(s). Preferred alkyl groups include those having 10 or less carbon atoms, for example a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a branched butyl group (e.g. an isobutyl group and a t-butyl group), a pentyl group, a branched pentyl group (e.g. isopentyl group and a t-pentyl group), a vinylmethyl group, a cyclohexyl group, a benzyl group, a phenethyl group, a 3-phenylpropyl group, a trifluoromethyl group, and the like.
Aryl groups in the definition of R.sub.0 and R.sub.1 may include those having substituent(s). Preferred aryl groups include those having 10 or less carbon atoms, for example a phenyl group, a 4-methylphenyl group, a 4-chlorophenyl group, a naphthyl group, and the like.
Alkoxy groups in the definition of R.sub.0 and R.sub.1 may include those having substituent(s). Preferred alkoxy groups include those having 10 or less carbon atoms, for example a methoxy group, an ethoxy group, a propyloxy group, a butyloxy group, a pentyloxy group, a benzyloxy group, a phenethyloxy group and the like.
Aryloxy groups in the definition of R.sub.0 and R.sub.1 may include those having substituent(s). Preferred aryloxy groups include those have 10 or less carbon atoms, for example a phenoxy group, a 4-methylphenoxy group, a 4-chlorophenoxy group, a naphthyloxy group and the like.
Halogen atoms in the definition of R.sub.0 and R.sub.1 include fluorine, chlorine, bromine and iodine atoms.
Alkoxycarbonyl groups in the definition of R.sub.0 and R.sub.1 may include those having substituent(s). Preferred alkoxycarbonyl groups include those having 10 or less carbon atoms, for example a methoxycarbonyl group, an ethoxycarbonyl group, a benzyloxycarbonyl group and the like.
Acylamino groups in the definition of R.sub.0 and R.sub.1 may include those having substituent(s). Preferred acylamino groups include those having 8 or less carbon atoms, for example an acetylamino group, a trifluoroacetylamino group, a propionylamino group, a benzoylamino group and the like.
Acyl groups in the definition of R.sub.0 and R.sub.1 may include those having substituent(s). Preferred acyl groups include those having 10 or less carbon atoms, for example an acetyl group, a trifluoroacetyl group, a propionyl group, a benzoyl group, a p-chlorobenzoyl group, a mesyl group and the like.
Carbamoyl groups in the definition of R.sub.0 and R.sub.1 may include those having substituent(s). Preferred carbamoyl groups include those having 6 or less carbon atoms, for example a carbamoyl group, an N,N-dimethylcarbamoyl group, a morpholinocarbonyl group and the like.
Sulfamoyl groups in the definition of R.sub.0 and R.sub.1 may include those having substituent(s). Preferred sulfamoyl groups include those having 6 or less carbon atoms, for example a sulfamoyl group, an N,N-dimethylsulfamoyl group, a morpholinosulfonyl group, a piperidinosulfonyl group and the like.
Acyloxy groups in the definition of R.sub.0 and R.sub.1 may include those having substituent(s). Preferred acyloxy groups include those having 10 or less carbon atoms, for example an acetyloxy group, a trifluoroacetyloxy group, a propionyloxy group, a benzoyloxy group and the like.
R.sub.0 and R.sub.1 may also be hydrogen atoms, cyano groups or carboxyl groups, under the condition that R.sub.0 and R.sub.1 do not represent hydrogen atoms at the same time.
The most preferred combination of R.sub.0 and R.sub.1 is that of R.sub.0 being a hydrogen atom and R.sub.1 being a phenyl group substituted at the 5-position.
Alkyl group and aryl group in the definition of R.sub.2 may each include those having substituent(s). Preferred alkyl groups and aryl groups include alkyl groups having 10 or less carbon atoms, for example a methyl group, an ethyl group, a propyl group, a butyl group, a benzyl group, a phenethyl group, a phenylpropyl group and the like; and aryl groups having 10 or less carbon atoms, for example a phenyl group, a p-tolyl group and the like, respectively.
R.sub.2 may also be a hydrogen atom.
Alkyl group, aryl group, alkoxy group, aryloxy group, acyl group, acyloxy group, alkoxycarbonyl group and acylamino group in the definition of R.sub.3 may each include those having substituent(s), with the condition that R.sub.1 and R.sub.3 do not represent aryl groups at the same time. Preferred R.sub.3 groups include, for example, an ethyl group, a propyl group, an isopropyl group, a branched butyl group (e.g. a t-butyl group), a branched pentyl group (e.g. an isopentyl group and a t-pentyl group), a branched hexyl group (e.g. a 3,3-dimethylbutyl group), a cyclohexyl group, a branched octyl group (e.g. a t-octyl group), a benzyl group, a phenethyl group, a t-butylcarbonyloxy group and the like. Most preferred examples of R.sub.3 include an ethyl group, a propyl group, an isopropyl group, a t-butyl group, a t-pentyl group, a cyclohexyl group, a t-octyl group and a benzyl group.
Alkyl groups in the definition of R.sub.4 and R.sub.5 may include those having substituent(s). Preferred alkyl groups include those having 8 or less carbon atoms such as methyl, ethyl, propyl, vinylmethyl, butyl, pentyl, hexyl, heptyl and octyl groups; aralkyl groups having 10 or less carbon atoms such as benzyl, phenethyl and 3-phenylpropyl groups; and alkyl groups having 6 or less carbon atoms substituted with an alkoxycarbonyl group having 8 or less carbon atoms (e.g. a methoxycarbonyl, ethoxycarbonyl or benzyloxycarbonyl group), an alkoxy group having 8 or less carbon atoms (e.g. a methoxy, ethoxy, butyloxy, benzyloxy or phenethyloxy group), an aryloxy group having 8 or less carbon atoms (e.g. a phenoxy or p-tolyloxy group), an acyloxy group having 8 or less carbon atoms (e.g. an acetyloxy, propionyloxy or benzoyloxy group), an acyl group having 8 or less carbon atoms (e.g. an acetyl, propionyl, benzoyl or 4-fluorobenzoyl group), a carbamoyl group having 6 or less carbon atoms (e.g. a carbamoyl, N,N-dimethylcarbamoyl, morpholinocarbamoyl or piperidinocarbamoyl group), a sulfamoyl group having 6 or less carbon atoms (e.g. a sulfamoyl, N,N-dimethylsulfamoyl, morpholinosulfonyl or piperidinosulfonyl group), or an aryl group having 10 or less carbon atoms (e.g. a phenyl, p-fluorophenyl, p-hydroxyphenyl, p-carboxyphenyl or p-sulfophenyl group).
Further, either R.sub.4 or R.sub.5 is preferably a sulfoalkyl group or a carboxyalkyl group.
X.sub.1.sup..crclbar. represents an inorganic or organic acid anion, for example chloride, bromide, iodide, p-toluenesulfonate, p-nitrobenzenesulfonate, methanesulfonate, methylsulfate, ethylsulfate, perchlorate and the like.
Benzene rings or naphthalene rings which Z.sub.1 and/or Z.sub.2 each form may include those having substituent(s). Examples of heterocyclic part formed by combination with Z.sub.1 or Z.sub.2 as represented as benzoxazoles 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-amyloxybenzoxazole, 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 heterocyclic part formed by combination with Z.sub.1 or Z.sub.2 as represented as benzoxazoles 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 significances with R.sub.4 and R.sub.5 respectively. R.sub.7 has the same significance with R.sub.2. Most preferred ones as R.sub.7 group are, for example, an ethyl group and the like. X.sub.2.sup..crclbar. has the same significance with X.sub.1.sup..crclbar., and m has the same significance with l.
Benzene rings which Z.sub.3 and/or Z.sub.4 each form may include those having substituent(s). Examples of heterocyclic part formed by combination with Z.sub.3 as represented as benzoxazoles 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-amyloxybenzoxazole, 6-hydroxybenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 5-ethoxybenzoxazole, and the like.
Examples of heterocyclic part formed by combination with Z.sub.4 as represented as benzothiazoles or benzoselenazoles include, for example, benzothiazole, benzoselenazole, 5-chlorobenzothiazole, 5-chlorobenzoselenazole, 5-methylbenzothiazole, 5-methylbenzoselenazole, 5-bromobenzothiazole, 5-bromobenzoselenazole, 5-fluorobenzothiazole, 5-fluorobenzoselenazole, 5-phenylbenzothiazole, 5-phenylbenzoselenazole, 5-methoxybenzothiazole, 5-methoxybenzoselenazole, 5-butoxybenzothiazole, 5-butoxybenzoselenazole, 5-nitrobenzothiazole, 5-nitrobenzoselenazole, 5-trifluoromethylbenzothiazole, 5-trifluoromethylbenzoselenazole, 5-hydroxybenzothiazole, 5-hydroxybenzoselenazole, 5-carboxybenzothiazole, 5-carboxybenzoselenazole, 6-methylbenzothiazole, 6-methylbenzoselenazole, 6-chlorobenzothiazole, 6-chlorobenzoselenazole, 6-nitrobenzothiazole, 6-nitrobenzoselenazole, 6-methoxybenzothiazole, 6-methoxybenzoselenazole, 6-amyloxybenzothiazole, 6-amyloxybenzoselenazole, 6-hydroxybenzothiazole, 6-hydroxybenzoselenazole, 5,6-dimethylbenzothiazole, 5,6-dimethylbenzoselenazole, 4,6-dimethylbenzothiazole, 4,6-dimethylbenzoselenazole, 5-ethoxybenzothiazole, 5-ethoxybenzoselenazole, 5-chloro-6-methylbenzothiazole, 5-chloro-6-methylbenzoselenazole and the like.
Typical examples of the compounds represented by the above general formulae (I) to (III) as used in the present invention are enumerated below, but the scope of the present invention should not be construed to be limited thereto.
__________________________________________________________________________ ##STR7##R.sub.0 R.sub.1 R.sub.2 R.sub.3 R.sub.4 R.sub.5 X l__________________________________________________________________________I-1 H ##STR8## H (CH.sub.2).sub.2 CH.sub.3 ##STR9## ##STR10## -- 0I-2 H ##STR11## CH.sub.3 C.sub.2 H.sub.5 ##STR12## C.sub.2 H.sub.5 -- 0I-3 H ##STR13## C.sub.2 H.sub.5 ##STR14## ##STR15## ##STR16## -- 0I-4 H ##STR17## CH.sub.3 ##STR18## ##STR19## ##STR20## -- 0I-5 H ##STR21## C.sub.2 H.sub.5 ##STR22## ##STR23## ##STR24## -- 0I-6 H ##STR25## C.sub.2 H.sub.5 ##STR26## ##STR27## ##STR28## -- 0I-7 H ##STR29## C.sub.2 H.sub.5 ##STR30## ##STR31## ##STR32## -- 0I-8 H Cl CH.sub.3 ##STR33## ##STR34## ##STR35## -- 0I-9 H CH.sub.3 C.sub.2 H.sub.5 ##STR36## C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR37## 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 ##STR38## -- 0I-11 ##STR39## H C.sub.2 H.sub.5 ##STR40## ##STR41## ##STR42## -- 0I-12 CH.sub.3 (CH.sub.2).sub.4 O H ##STR43## ##STR44## ##STR45## ##STR46## -- 0I-13 HOOC H C.sub.2 H.sub.5 ##STR47## ##STR48## C.sub.2 H.sub.5 -- 0I-14 ##STR49## H H ##STR50## ##STR51## CH.sub.3 -- 0I-15 H ##STR52## C.sub.2 H.sub.5 ##STR53## C.sub.2 H.sub.5 C.sub.2 H.sub.5 Br.sup.- 1I-16 CH.sub.3 O H CH.sub.3 ##STR54## CH.sub.3 ##STR55## -- 0I-17 Cl H H ##STR56## ##STR57## ##STR58## -- 0I-18 H ##STR59## C.sub.2 H.sub.5 ##STR60## ##STR61## ##STR62## -- 0I-19 H ##STR63## C.sub.2 H.sub.5 ##STR64## ##STR65## ##STR66## -- 0I-20 CH.sub.3 CH.sub.3 C.sub.2 H.sub.5 ##STR67## ##STR68## ##STR69## -- 0__________________________________________________________________________
The values of L and B of various examples of the substituent R.sub.3, and the values of B calculated using the equation of
S=3.536L-2.66lB+535.4
are shown 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______________________________________
__________________________________________________________________________ ##STR70## R.sup.10 R.sup.11 R.sup.12 R.sup.13 R.sup.14 R.sup.15__________________________________________________________________________II-1 ##STR71## H ##STR72## C.sub.2 H.sub.5 (CH.sub.2).sub.2 SO.sub.3.sup.- ##STR73##II-2 ##STR74## 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 ##STR75## 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 ##STR76## H ##STR77## ##STR78## (CH.sub.2).sub.3 SO.sub.3.sup.- (CH.sub.2).sub.3 SO.sub.3 HII-9 ##STR79## H Cl C.sub.2 H.sub.5 (CH.sub.2).sub.2 SO.sub.3.sup.- C.sub.2 H.sub.5II-10 ##STR80## H ##STR81## C.sub.2 H.sub.5 (CH.sub.2).sub.2 SO.sub.3.sup.- CH.sub.3II-11 ##STR82## 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 ##STR83## 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 ##STR84##__________________________________________________________________________ ##STR85## Y.sub.0 R.sup.0 R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5__________________________________________________________________________III-1 S ##STR86## H Cl (CH.sub.2).sub.3 SO.sub.3.sup.- (CH.sub.2).sub.3 SO.sub.3 Na C.sub.2 H.sub.5III-2 S ##STR87## CH.sub.3 CH.sub.3 (CH.sub.2).sub.3 SO.sub.3.sup.- (CH.sub.2 ).sub.4 SO.sub.3 Na C.sub.2 H.sub.5III-3 S ##STR88## H OCH.sub.3 (CH.sub.2).sub.3 SO.sub.3.sup.- (CH.sub.2).sub.3 SO.sub.3 K C.sub.2 H.sub.5III-4 S Cl H CH.sub.3 (CH.sub.2).sub.3 SO.sub.3.sup.- C.sub.2 H.sub.5 C.sub.2 H.sub.5III-5 S ##STR89## CH.sub.3 Cl (CH.sub.2).sub.2 SO.sub.3.sup.- (CH.sub.2).sub.4 SO.sub.3 H.N(C.sub.2 H.sub.5).sub.3 C.sub.2 H.sub.5III-6 S ##STR90## H ##STR91## (CH.sub.2).sub.2 SO.sub.3.sup.- (CH.sub.2).sub.4 SO.sub.3 Na CH.sub.3III-7 S ##STR92## CH.sub.3 CH.sub.3 (CH.sub.2).sub.2 SO.sub.3.sup.- ##STR93## C.sub.2 H.sub.5III-8 S Cl H H (CH.sub.2).sub.3 SO.sub.3.sup.- C.sub.2 H.sub.5 C.sub.2 H.sub.5III-9 S Cl H OCH.sub.3 (CH.sub.2).sub. 3 SO.sub.3.sup.- ##STR94## C.sub.2 H.sub.5III-10 S ##STR95## H H (CH.sub.2).sub.3 SO.sub.3.sup.- CH.sub.3 HIII-11 S.sub.e Cl H Cl (CH.sub.2).sub.3 SO.sub.3.sup.- (CH.sub.2).sub.3 SO.sub.3 Na C.sub.2 H.sub.5III-10 S.sub.e ##STR96## H H (CH.sub.2).sub.3 SO.sub.3.sup.- C.sub.2 H.sub.5 CH.sub.3__________________________________________________________________________
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 86-199, John Wiley & Sons (New York, London) (1964); D. M. Sturmer, "Heterocyclic Compounds--Special topics in heterocyclic chemistry--" chapter VIII, sec. IV pages 482-515, 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. This amount may widely be changed according to the condition of an emulsion to be used, but may preferably be 1.times.10.sup.-6 to 5.times.10.sup.-3 mole, preferably 3.times.10.sup.-6 to 2.5.times.10.sup.-3 mole per mole of the silver halide.
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 (Dec.. 1978), pages 22 to 23 ("I. Emulsion preparation and types"), or ibid. No. 18716 (Nov., 1979), page 648.
A photographic emulsion of 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 at.; 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 so-called 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 contains 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 as 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. Patent 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 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 conjunction. These emulsions 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.
An emulsion of the present invention is 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.
______________________________________ RD RD Kind of additive 17643 18716______________________________________1 Chemically sensitizing page 23 page 648, agent right column (r.c.)2 Sensitivity-enhancing agent "______________________________________
______________________________________ RD RD Kind of additive 17643 18716______________________________________3 Spectrally sensitizing pages page 648 r.c.- agent 23- 24 page 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- 26 page 650 r.c. absorbent6 Stain inhibitor page 25 pages 650 left r.c. column (l.c.)- r.c.7 Hardening agent page 26 page 651 l.c.8 Binder page 26 "9 Plasticizer and page 27 page 650 r.c. lubricant10 Coating aid and pages " surfactant 26- 2711 Static inhibitor page 27 "______________________________________
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 subtractive 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 color dyes, and on the other hand .alpha.-benzoylacetanilide type couplers give higher color densities.
Magenta dye-forming couplers usable in the present invention include indazolone type, cyanoacetyl type, 5-pyrazolone type and pyrazoloazole type couplers which respectively have a ballast group and are hydrophobic, and 5-pyrazolone type and pyrazoloazole type couplers are preferable. As 5-pyrazolone type couplers, couplers 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 color 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 Patent 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-diacylamino-substituted 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. Patent 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 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. 57-184248. 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 pages, 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 are 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 to right column.

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 were 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 (diameter) 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. Each 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. ##STR97##
TABLE 1__________________________________________________________________________ After preservation for Fresh performance 3 days (50.degree. C., 80% RH)Sample Sensitizing Sensitizing Sensitizing Relative RelativeNo. dye A dye B dye C Fog sensitivity Fog sensitivity__________________________________________________________________________101 I-5 3.2 .times. 10.sup.-4 II-1 1.6 .times. 10.sup.-4 -- .+-.0 100 +0.01 98(Present mol/mol Ag mol/mol Ag (Standard (Standard ofinvention) of fog) sensitivity)102 I-7 3.2 .times. 10.sup.-4 II-1 1.6 .times. 10.sup.-4 -- -0.01 97 +0.01 94(Present mol/mol Ag mol/mol Aginvention)103 I-5 3.2 .times. 10.sup.-4 II-2 1.6 .times. 10.sup.-4 -- +0.02 99 +0.04 97(Present mol/mol Ag mol/mol Aginvention)104 I-7 3.2 .times. 10.sup.-4 II-2 1.6 .times. 10.sup.-4 -- +0.01 101 +0.02 99(Present mol/mol Ag mol/mol Aginvention)105 SD-1 3.2 .times. 10.sup.-4 II-1 1.6 .times. 10.sup.-4 -- +0.09 104 +0.18 88(Comparative mol/mol Ag mol/mol Agexample)106 SD-2 3.2 .times. 10.sup.-4 II-1 1.6 .times. 10.sup.-4 -- +0.15 95 +0.27 62(Comparative mol/mol Ag mol/mol Agexample)107 SD-3 3.2 .times. 10.sup.-4 II-1 1.6 .times. 10.sup.-4 -- +0.06 90 +0.13 65(Comparative mol/mol Ag mol/mol Agexample)108 SD-1 3.2 .times. 10.sup.-4 II-2 1.6 .times. 10.sup.-4 -- +0.11 103 +0.19 89(Comparative mol/mol Ag mol/mol Agexample)109 SD-2 3.2 .times. 10.sup.-4 II-2 1.6 .times. 10.sup.-4 -- +0.21 93 +0.31 60(Comparative mol/mol Ag mol/mol Agexample)110 SD-3 3.2 .times. 10.sup.-4 II-2 1.6 .times. 10.sup.-4 -- +0.08 91 +0.14 64(Comparative mol/mol Ag mol/mol Agexample)111 I-5 2.0 .times. 10.sup.-4 II-1 1.6 .times. 10 .sup.- 4 III-2 1.2 .times. 10.sup.-4 .+-.0 100 +0.02 97(Present mol/mol Ag mol/mol Ag mol/mol Ag (Standard (Standard ofinvention) of fog) sensitivity)112 I-7 2.0 .times. 10.sup.-4 II-1 1.6 .times. 10.sup.-4 III-2 1.2 .times. 10.sup.-4 -0.02 98 0.00 95(Present mol/mol Ag mol/mol Ag mol/mol Aginvention)113 I-5 2.0 .times. 10.sup.-4 II-2 1.6 .times. 10 .sup.-4 III-2 1.2 .times. 10.sup.-4 +0.02 102 +0.03 97(Present mol/mol Ag mol/mol Ag mol/mol Aginvention)114 I-7 2.0 .times. 10.sup.-4 II-1 1.6 .times. 10 .sup.-4 III-2 1.2 .times. 10.sup.-4 +0.00 102 +0.02 98(Present mol/mol Ag mol/mol Ag mol/mol Aginvention)115 I-7 2.0 .times. 10.sup.-4 -- -- III-2 2.8 .times. 10.sup.-4 +0.01 97 +0.03 95(Present mol/mol Ag mol/mol Aginvention)116 SD-1 2.0 .times. 10.sup.-4 II-1 1.6 .times. 10.sup.-4 III-2 1.2 .times. 10.sup.-4 +0.10 106 +0.19 89(Comparative mol/mol Ag mol/mol Ag mol/mol Agexample)117 SD-2 2.0 .times. 10.sup.-4 II-1 1.6 .times. 10.sup.-4 III-2 1.2 .times. 10.sup.-4 +0.17 98 +0.29 64(Comparative mol/mol Ag mol/mol Ag mol/mol Agexample)118 SD-3 2.0 .times. 10.sup.-4 II-1 1.6 .times. 10.sup.-4 III-2 1.2 .times. 10.sup.-4 +0.08 92 +0.15 66(Comparative mol/mol Ag mol/mol Ag mol/mol Agexample)119 SD-1 2.0 .times. 10.sup.-4 II-2 1.6 .times. 10.sup.-4 III-2 1.2 .times. 10.sup.-4 +0.14 103 +0.21 91(Comparative mol/mol Ag mol/mol Ag mol/mol Agexample)120 SD-2 2.0 .times. 10.sup.-4 II-2 1.6 .times. 10.sup.-4 III-2 1.2 .times. 10.sup.-4 +0.26 93 +0.33 62(Comparative mol/mol Ag mol/mol Ag mol/mol Agexample)121 SD-3 2.0 .times. 10.sup.-4 II-2 1.6 .times. 10.sup.-4 III-2 1.2 .times. 10.sup.- 4 +0.11 92 +0.17 66(Comparative mol/mol Ag mol/mol Ag mol/mol Agexample)122 -- -- II-1 2.6 .times. 10.sup.-4 III-2 2.2 .times. 10.sup.-4 -0.01 89 +0.02 86(Comparative mol/mol Ag mol/mol Agexample)123 -- -- II-2 2.6 .times. 10.sup.-4 III-2 2.2 .times. 10.sup.-4 -0.01 86 +0.03 83(Comparative mol/mol Ag mol/mol Agexample)__________________________________________________________________________
EXAMPLE 2
A silver halide emulsion layer and a gelatin protective layer each having the following compositions were applied on a cellulose triacetate film support which had been provided with an undercoat to prepare samples 201 to 223.
(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 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.
__________________________________________________________________________(Emulsion layer)Silver iodobromide emulsion 2.06 mole % silver iodide, variationcoefficient of grain size (S/F) = 0.18,Aspect ratio 6.0, Average grain size (F) = 0.18 .mu.mGelatin 1.0Sensitizing dye (disclosed in Table 2)Cpd-5 0.25Cpd-15 0.25Cpd-8 0.03Cpd-7 0.05Oil-1 0.50Oil-4 0.13(Protective layer)Gelatin 0.50Hardening agent H-1 0.40Cpd-7 0.05Oil-1 0.50Oil-4 0.13(Protective layer)Gelatin 0.50Hardening agent H-1 0.40__________________________________________________________________________ ##STR98## ##STR99## ##STR100## ##STR101## ##STR102##Hardening agent H-1 ##STR103##__________________________________________________________________________
Each of the resulting photographic elements was preserved for 3 days at 50.degree. C. under 80% RH, and then exposed to light with an exposure amount of 10 CMS using a tungsten light source whose color temperature had been adjusted to 4800.degree. K. with a filter, and SC-50, an optical filter for measuring spectral sensitization speed manufactured by Fuji Photo Film Co., Ltd. Then, each element was subjected to the following developing process. The resulting results are shown in Table 2 together with each fresh performance.
______________________________________Color development 2 minutes and 45 secondsBleaching 6 minutes and 30 secondsWater washing 2 minutes and 10 secondsFixing 4 minutes and 20 secondsWater washing 3 minutes and 15 secondsStabilization 1 minute and 05 seconds______________________________________
Compositions of processing solutions used in the respective steps are as follows.
______________________________________Color developing solutionDiethylenetriaminetetraacetic acid 1.0 g1-Hydroxyethylidene-1,1-diphophonic 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 solutionFerric ammonium ethylenediamine- 100.0 gtetraacetateDisodium 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 gAn aqueous ammonium thiosulfate 175.0 mlsolution (70%)Sodium bisulfite 4.6 gWater to 1.0 l pH 6.6Stabilizing solutionFormalin (40%) 2.0 mlPolyoxyethylene-p-monononylphenyl ether 0.3 g(Average polymerization degree 10)Water to 1.0 l______________________________________
TABLE 2__________________________________________________________________________ After preservation for Fresh performance 3 days (50.degree. C., 80% RH)Sample Sensitizing Sensitizing Sensitizing Relative RelativeNo. dye A dye B dye C Fog sensitivity Fog sensitivity__________________________________________________________________________201 I-5 3.5 .times. 10.sup.-4 II-1 1.5 .times. 10.sup.-4 -- .+-.0 100 +0.02 97(Present mol/mol Ag mol/mol Ag (Standard (Standard ofinvention) of fog) sensitivity)202 I-7 3.5 .times. 10.sup.-4 II-1 1.5 .times. 10.sup.-4 -- -0.02 98 +0.01 93(Present mol/mol Ag mol/mol Aginvention)203 I-5 3.5 .times. 10.sup.-4 II-2 1.5 .times. 10.sup.-4 -- +0.03 100 +0.05 97(Present mol/mol Ag mol/mol Aginvention)204 I-7 3.5 .times. 10.sup.-4 II-2 1.5 .times. 10.sup.-4 -- +0.02 103 +0.04 98(Present mol/mol Ag mol/mol Aginvention)205 SD-1 3.5 .times. 10.sup.-4 II-1 1.5 .times. 10.sup.-4 -- +0.11 105 +0.20 86(Comparative mol/mol Ag mol/mol Agexample)206 SD-2 3.5 .times. 10.sup.-4 II-1 1.5 .times. 10.sup.-4 -- +0.21 97 +0.38 60(Comparative mol/mol Ag mol/mol Agexample)207 SD-3 3.5 .times. 10.sup.-4 II-1 1.5 .times. 10.sup.-4 -- +0.09 93 +0.17 61(Comparative mol/mol Ag mol/mol Agexample)208 SD-1 3.5 .times. 10.sup.-4 II-2 1.5 .times. 10.sup.-4 -- +0.17 102 +0.23 87(Comparative mol/mol Ag mol/mol Agexample)209 SD-2 3.5 .times. 10.sup.-4 II-2 1.5 .times. 10.sup.-4 -- +0.29 94 +0.40 57(Comparative mol/mol Ag mol/mol Agexample)210 SD-3 3.5 .times. 10.sup.-4 II-2 1.5 .times. 10.sup.-4 -- +0.13 92 +0.26 62(Comparative mol/mol Ag mol/mol Agexample)211 I-5 2.5 .times. 10.sup.-4 II-1 1.5 .times. 10.sup.- 4 III-2 1.0 .times. 10.sup.-4 .+-.0 100 +0.03 96(Present mol/mol Ag mol/mol Ag mol/mol Ag (Standard (Standard ofinvention) of fog) sensitivity212 I-7 2.5 .times. 10.sup.-4 II-1 1.5 .times. 10.sup.-4 III-2 1.0 .times. 10.sup.-4 -0.01 99 +0.01 95(Present mol/mol Ag mol/mol Ag mol/mol Aginvention)213 I-5 2.5 .times. 10.sup.-4 II-2 1.5 .times. 10.sup.-4 III-2 1.0 .times. 10.sup.-4 +0.03 103 +0.05 98(Present mol/mol Ag mol/mol Ag mol/mol Aginvention)214 I-7 2.5 .times. 10.sup.-4 II-2 1.5 .times. 10.sup.-4 III-2 1.0 .times. 10.sup.-4 +0.02 102 +0.04 98(Present mol/mol Ag mol/mol Ag mol/mol Aginvention)215 I-7 2.5 .times. 10.sup.-4 -- -- III-2 2.5 .times. 10.sup.-4 +0.02 96 +0.04 93(Present mol/mol Ag mol/mol Ag mol/mol Aginvention)216 SD-1 2.5 .times. 10.sup.-4 II-1 1.5 .times. 10.sup.- 4 III-2 1.0 .times. 10.sup.-4 +0.15 108 +0.23 88(Relative mol/mol Ag mol/mol Ag mol/mol Agexample)217 SD-2 2.5 .times. 10.sup.-4 II-1 1.5 .times. 10.sup.-4 III-2 1.0 .times. 10.sup.-4 +0.22 99 +0.36 60(Relative mol/mol Ag mol/mol Ag mol/mol Agexample)218 SD-3 2.5 .times. 10.sup.-4 II-1 1.5 .times. 10.sup.-4 III-2 1.0 .times. 10.sup.-4 +0.12 93 +0.18 61(Relative mol/mol Ag mol/mol Ag mol/mol Agexample)219 SD-1 2.5 .times. 10.sup.-4 II-2 1.5 .times. 10.sup.-4 III-2 1.0 .times. 10.sup.-4 +0.19 105 +0.27 87(Relative mol/mol Ag mol/mol Ag mol/mol Agexample)220 SD-2 2.5 .times. 10.sup.-4 II-2 1.5 .times. 10.sup.-4 III-2 1.0 .times. 10.sup.-4 +0.31 94 +0.43 55(Relative mol/mol Ag mol/mol Ag mol/mol Agexample)221 SD-3 2.5 .times. 10.sup.-4 II-2 1.5 .times. 10.sup.-4 III-2 1.0 .times. 10.sup. -4 +0.17 92 +0.23 62(Relative mol/mol Ag mol/mol Ag mol/mol Agexample)222 -- -- II-1 3.0 .times. 10.sup.-4 III-2 2.0 .times. 10.sup.-4 0.00 87 +0.02 83(Relative mol/mol Ag mol/mol Agexample)223 -- -- II-2 3.0 .times. 10.sup.-4 III-2 2.0 .times. 10.sup.-4 -0.01 86 +0.02 83(Relative mol/mol Ag mol/mol Agexample)__________________________________________________________________________
EXAMPLE 3
Preparation of sample 301
Malti-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 0.06UV absorber UV-1 0.1UV 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 1Colored coupler Cpd-27 0.02Dispersion oil Oil-1 0.1The 3rd layer (The 1st red-sensitiveemulsion layer)Silver iodobromide emulsion 0.6 (g/m.sup.2)4 mole % silver iodide, variation or lesscoefficient of grain size (S/.gamma.) = 0.12,Average grain size (.gamma.) = 0.7 .mu.m(hereinafter is referred to as 0.6)I.sup.- 4 moles, S/.gamma. = 0.12, 0.7 .mu.mSilver iodobromide emulsion 0.3I.sup.- 3 moles, S/.gamma. = 0.11, 0.3.mu.Gelatin 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-sensitiveemulsion layer)Silver iodobromide emulsion 0.7I.sup.- 6 moles, S/.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-sensitiveemulsion layer)Silver iodobromide emulsion 0.35I.sup.- 4 moles, S/.gamma. = 0.11, 0.6 .mu.mSilver iodobromide emulsion 0.20I.sup.- 3 moles, S/.gamma. = 0.15, 0.3 .mu.mGelatin 1.0I-7 5 .times. 10.sup.-4II-2 1 .times. 10.sup.-4Cpd-5 0.3Cpd-7 0.07Cpd-13 0.03Oil-1 0.3Oil-4 0.1The 7th layer (The 2nd green-sensitiveemulsion layer)Silver iodobromide emulsion 0.8I.sup.- 6 moles, S/.gamma. = 0.18, 0.8 .mu.mGelatin 0.5I-7 5 .times. 10.sup.-4II-2 1 .times. 10.sup.-4Cpd-5 0.1Cpd-15 0.1Cpd-8 0.01CPd-7 0.02Oil-1 0.2Oil-4 0.05The 8th layer (Intermediate layer)Gelatin 0.5Cpd-6 0.05Oil-1 0.03The 9th layer (Interlayer effectdonor layer)Silver iodobromide emulsion 0.35 g/m.sup.22 mole % silver iodide, aspect ratio or less6.0, tabular grains having a averagegrain size of 1.0 .mu.m(hereinafter referred to as 0.35)I.sup.- 2 moles, A/R = 6.0, 1.0 .mu.mSilver iodobromide emulsion 0.20I.sup.- 2 moles, 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-sensitiveemulsion layer)Silver iodobromide emulsion 0.3I.sup.- 3 moles, A/R = 7.5, 1.0 .mu.mSilver iodobromide emulsion 0.15I.sup.- 3 moles, A/R = 7.5, 0.5 .mu.mSD-6 2 .times. 10.sup.-4Cpd-1 0.05Cpd-8 0.10Cpd-29 0.80Oil-1 0.20The 12th layer (The 2nd blue-sensitiveemulsion layer)Silver iodobromide emulsion 0.5I.sup.- 10 moles, S/.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 2ndprotective layer)Fine grain silver bromide emulsion 0.5I.sup.- 2 moles, S/.gamma. = 0.2, 0.07 .mu.mPolymethyl methacrylate 0.2Grain diameter 1.5 .mu.mHardening agent H-1 0.4Formaldehyde scavenger S-1 0.5Formaldehyde scavenger S-2 0.5______________________________________
Stabilizing agent for emulsion Cpd-26 and a surfactant was further added as coating aids to each of the above layers besides the above components. ##STR104##
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 After preserva- tion for 3 days The 9th layer Fresh performance (50.degree. C., 80% RH) The 6th layer sensitizing dye The 7th layer sensitizing dye sensitizing dye Relative Relative Sample Amount Amount Amount Amount Amount sensi- sensi- No. Species mol/mol Ag Species mol/mol Ag Species mol/mol Ag Species mol/mol Ag Species mol/mol Ag Fog tivity Fog tivity 301 I-7 5 .times. 10.sup.-4 II-2 1 .times. 10.sup.-4 I-7 5 .times. 10.sup.-4 II-2 1 .times. 10.sup.-4 I-7 8 .times. 10.sup.-4 .+-.0 100 +0.02 95 (Present (standard (standard invention) of fog) of sensi- tivity) 302 " " " " " " " " I-19 8 .times. 10.sup.-4 -0.01 99 +0.01 94 (Present invention) 303 I-19 5 .times. 10.sup.-4 " " I-19 5 .times. 10.sup.-4 " " I-7 8 .times. 10.sup.-4 -0.01 98 +0.02 92 (Present invention) 304 I-5 5 .times. 10.sup.-4 " " I-5 5 .times. 10.sup.-4 " " " " +0.01 101 +0.02 95 (Present invention) 305 I-7 5 .times. 10.sup.-4 " " I-7 5 .times. 10.sup.-4 " " SD-1 8 .times. 10.sup.-4 +0.10 102 +0.25 78 (Compara- tive example) 306 " " " " " " " " SD-7 8 .times. 10.sup.-4 +0.05 86 +0.08 68 (Compara- tive example) 307 " " " " " " " " SD-2 8 .times. 10.sup.-4 +0.12 98 +0.40 70 (Compara- tive example) 308 " " " " " " " " SD-8 8 .times. 10.sup.-4 +0.04 90 +0.08 72 (Compara- tive example) 309 " " " " " " " " SD-3 8 .times. 10.sup.-4 +0.02 88 +0.07 69 (Compara- tive example) 310 SD-1 5 .times. 10.sup.-4II-21 .times. 10.sup.-4 SD-1 5 .times. 10.sup.-4 II-2 1 .times. 10.sup.-4 I-7 8 .times. 10.sup.-4 +0.14 103 +0.30 80 (Compara- tive example) 311 SD-7 5 .times. 10.sup.-4 " " SD-7 5 .times. 10.sup.-4 " " " " +0.07 88 +0.10 67 (Compara- tive example) 312 SD-2 5 .times. 10.sup.-4 " " SD-2 5 .times. 10.sup.-4 " " " " +0.16 95 +0.46 63 (Compara- tive example) 313 SD-8 5 .times. 10.sup.-4 " " SD-8 5 .times. 10.sup.-4 " " " " +0.07 89 +0.12 70 (Compara- tive example) 314 SD-3 5 .times. 10.sup.-4 " " SD-3 5 .times. 10.sup.-4 " " " " +0.03 85 +0.09 63 (Compara- tive example)
EXAMPLE 4
Samples 301 to 314 of Example 3 were evaluated in the same experimental condition as in Example 3 except that the process steps were changed for those shown below, and almost the same results as therein were obtained.
______________________________________Step Process time Process temperature______________________________________Color development 3 min. and 15 sec. 38.degree. C.Bleaching 1 min. and 00 sec. 38.degree. C.Bleaching-fixing 3 min. and 15 sec. 38.degree. C.Water washing (1) 40 sec. 35.degree. C.Water washing (2) 1 min. and 00 sec. 35.degree. C.Stabilization 40 sec. 38.degree. C.Drying 1 min. and 15 sec. 55.degree. C.______________________________________
Compositions of process solutions as shown below:
______________________________________ (Unit g)______________________________________(Color developing solution)Diethylenetriaminetetraacetic acid 1.01-Hydroxyethylidene-1,1-diphosphonic acid 3.0Sodium sulfite 4.0Potassium carbonate 30.0Potassium bromide 1.4Potassium iodide 1.5 mgHydroxylamine sulfate 2.44-(NEthyl-N (.beta.-hydroxyethyl)amino- 4.52-methylnmiline sulfateWater to 1.0 lpH 10.05(Bleaching solution)Ferric ammoniumethylenediaminetetraacetate dihydrate 120.0Disodium ethylenediaminetetraacetate 10.0Ammonium bromide 100.0Ammonium nitrate 10.0Bleach acclerator 0.005 mol ##STR105##Ammonia water (27%) 15.0 mlWater to 1.0 lpH 6.3(Bleach-fixing solution)Ferric ammoniumethylenediaminetetraacetate dihydrate 50.0Disodium ethylenediaminetetraacetate 5.0Sodium sulfite 12.0Aqueous ammonium thiosulfate solution 240.0 ml(70%)Ammonia water (27%) 6.0 mlWater to 1.0 lpH 7.2______________________________________
Water washing solution
Tapwater was passed through a multi-bed column packed with an H-type strongly acidic cation exchange regin (Amberlite IR-120B manufactured by Rohm and Haas Co.) and an OH-type anion exchange regin (Amberlite IR-400 manufactured by Rohm and Haas Co.) to reduce concentrations of calcium and magnesium ions below 3 mg/l. Then, 20 mg/l of sodium dichloroisocyanurate and 1.5 g/l of sodium sulfate were added thereto. The pH of the resulting water washing solution is 6.5 to 7.5.
______________________________________(Stabilizing solution) (Unit g)______________________________________Formalin (37%) 2.0 mlPolyoxyethylene-p-monononylphenyl 0.3ether (Average polymerization degree 10)Disodium ethylenediaminetetraacetate 0.05Water to 1.0 lpH 5.0-8.0______________________________________
EXAMPLE 5
Samples 301 to 314 were evaluated in the same experimental condition as in Example 3 except that process steps were changed for those shown below, and almost the same results as exhibited in Table 3 were obtained.
______________________________________ Process Process Replenisher TankStep time temperature amount* capacity______________________________________Color 3 min. and 38.degree. C. 15 ml 20 ldevelopment 15 sec.Bleaching 6 min. and 38.degree. C. 10 ml 40 l 30 sec.Water 2 min. and 35.degree. C. 10 ml 20 lwashing 10 sec.Fixing 4 min. and 38C. 20 ml 30 l 20 sec.Water 1 min. and 35.degree. C. Counter- 10 lwashing 05 sec. flow piping(1) method from (2) to (1)Water 1 min. and 35.degree. C. 20 ml 10 lwashing 00 sec.(2)Stabiliza- 1 min. and 38.degree. C. 10 ml 10 ltion 05 sec.Drying 4 min. and 55.degree. C. 20 sec.______________________________________ *per a width of 35 mm and a length of 1 m
Compositions of process solutions are described below.
______________________________________ Mother Replenisher(Color developing solution) liquor (g) (g)______________________________________Diethylenetriaminetetraacetic 1.0 1.11-Hydroxyethylidene-1,1- 3.0 3.2diphosphonic acidSodium sulfite 4.0 4.9Potassium carbonate 30.0 30.0Potassium bromide 1.4 --Potassium iodide 1.5 mg --Hydroxylamine sulfate 2.4 3.64-(N--Ethyl-N--(.beta. -hydroxyethyl)- 4.5 7.2amino)-2-methylaniline sulfateWater to 1.0 l 1.0 lpH 10.05 10.10______________________________________ Mother Replenisher(Bleaching solution) liquor (g) (g)______________________________________Ferric sodium ethylenediamine- 100.0 140.0tetraaceate trihydrateDisodiumethylenediaminetetraacetate 10.0 11.0Ammonium bromide 140.0 180.0Ammonium nitrate 30.0 40.0Ammonia water (27%) 6.5 ml 2.5 mlWater to 1.0 l 1.0 lpH 6.0 5.5______________________________________ Mother Replenisher(Fixing solution) liquor (g) (g)______________________________________Disodiumethylenediaminetetraacetate 0.5 1.0Sodium sulfite 7.0 12.0Sodium bisulfite 5.0 9.5Aqueous ammoniumthiosulfate solution (70%) 170.0 ml 240.0 mlWater to 1.0 l 1.0 lpH 6.7 6.6(Water washing solution) common to mother liquor and replenisher______________________________________
Tapwater was passed through a multi-bed column packed with an H-type strongly acidic cation exchange regin (Amberlite IR-120B manufactured by Rohm and Haas Co.) and an OH-type anion exchange regin (Amberlite IR-400 manufactured by Rohm and Haas Co.) to reduce concentrations of calcium and magnesium ions below 3 mg/l. Then, 20 mg/l of sodium dichloroisocyanurate and 1.5 g/l of sodium sulfate were added thereto. The pH of the resulting water washing solution is 6.5 to 7.5.
______________________________________ Mother Replenisher(Stabilizing agent) liquor (g) (g)______________________________________Formalin (37%) 2.0 ml 3.0 mlPolyoxyethylene-p- 0.3 0.45monononylphenyl ether(Average polymerization degree 10)Disodiumethylenediaminetetraacetate 0.05 0.08Water to 1.0 l 1.0 lpH 5.0-8.0 5.0-8.0______________________________________
EXAMPLE 6
Samples 301 to 314 of Example 3 were evaluated in the same experimental condition as in Example 3 except that the process conditions were changed for those shown below, and almost the same results as therein were obtained.
______________________________________ Tank Processing Processing Replenisher ca-Step time temperature amount* pacity______________________________________Color 3 min 37.8.degree. C. 40 ml 10 ldevelopment 15 sec.Bleaching 3 min. 37.8.degree. C. 5 ml 10 lFixing 4 min. 37.8.degree. C. 30 ml 10 lStabilization 45 sec. 35.0.degree. C. Counterflow 5 l(1) piping method from (3) to (1)Stabilization 45 sec. 35.0.degree. C. 5 l(2)Stabilization 45 sec. 35.0.degree. C. 40 ml 5 lDrying 1 min 55.0.degree. C. 20 sec.______________________________________ *per a width of 35 mm and a length of 1 m
Compositions of process solutions are described below.
______________________________________ Mother Replenisher(Color developing solution) liquor (g) (g)______________________________________Diethylenetriaminepentaacetic 5.0 6.0acidSodium sulfite 4.0 4.4Potassium carbonate 30.0 37.0Potassium bromide 1.3 0.9Potassium iodide 1.2 mg --Hydroxylamine sulfate 2.0 2.84-(N--Ethyl-N--(.beta.-hydroxyethyl)- 4.7 5.3amino)-2-methylaniline sulfateWater to 1.0 l 1.0 lpH 10.00 10.05______________________________________ Mother Replenisher(Bleaching solution) liquor (g) (g)______________________________________Ferric ammonium 70.0 120.0ethylenediaminetetraacetatedihydrateFerric 35.0 55.01,3-diaminopropanetetrtaacetateEthylenediaminetetraacetic acid 4.0 5.0Ammonium bromide 100.0 160.0Ammonium nitrate 30.0 50.0Ammonia water (27%) 20.0 ml 23.0 mlAcetic acid (98%) 9.0 ml 15.0 mlWater to 1.0 l 1.0 lpH 5.5 4.5______________________________________ Mother Replenisher(Fixing solution) liquor (g) (g)______________________________________Disodium 0.5 0.7ethylenediaminetetraacetateSodium sulfite 7.0 8.0Sodium bisulfite 5.0 5.5Aqueous ammonium thiosulfate 170.0 ml 200.0 mlsolution (70%)Water to 1.0 l 1.0 lpH 6.7 6.6______________________________________ common to mother liquor(Stabilizing solution) and replenisher______________________________________Formalin (37%) 1.2 ml5-Chloro-2-methyl-4-isothiazolin-3-one 6.0 mg2-Methyl-4-isothiazolin-3-one 3.0 mgSurfactant 0.4 g[C.sub.10 H.sub.21 --O--(CH.sub.2 CH.sub.2 O).sub.10 -- H]Ethylene glycol 1.0 gWater to 1.0 lpH 5.0-7.0______________________________________
EXAMPLE 7
Preparation of sample 401
Malti-layered color light-sensitive material, which is herein referred to as sample 401, was prepared by applying in layers 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.
(Sample 401)
The 1st layer (Antihalation layer)
Black colloidal silver 0.18 as silver, gelatin .040
The 2nd layer (Intermediate layer)
2,5-Di-t-pentadecyl-hydroquinone 0.18, Cpd-30 0.07, Cpd-31 0.02, UV-1 0.08, UV-2 0.08, Oil-1 0.10, Oil-2 0.02, Gelatin 1.04
The 3rd layer (The 1st red-sensitive emulsion layer)
Silver iodobromide emulsion (6 mole % silver iodide, average grain size 0.8 .mu.m) 0.55 (silver), SD-96.9.times.10.sup.-5, SD-5 1.8.times.10.sup.-5, SD-10 3.1.times.10.sup.-4, SD-11 4.0.times.10.sup.-5, Cpd-8 0.350, Oil-1 0.005, Cpd-34 0.008, Gelatin 1.20
The 4th layer (The 2nd red-sensitive emulsion layer)
Silver iodobromide emulsion (8 mole % silver iodide, average grain size 0.85 .mu.m) 1.20 (silver), SD-9 5.1.times.10.sup.-5, SD-5 1.4.times.10.sup.-5, SD-10 2.3.times.10.sup.-4, SD-11 3.0.times.10.sup.-5, Cpd-8 0.300, Cpd-31 0.050, Cpd-9 0.004, Oil-2 0.050, Gelatin 1.30
The 5th layer (The 3rd red-sensitive emulsion layer)
Silver iodobromide emulsion (14 mole % silver iodide, average grain size 1.5 .mu.m) 1.60 (silver), SD-12 5.4.times.10.sup.-5, SD-5 1.4.times.10.sup.-5, SD-10 2.4.times.10.sup.-4, SD-11 3.1.times.10.sup.-5, Cpd-32 0.150, Cpd-31 0.055, Cpd-24 0.060, Cpd-34 0.005, Oil-1 0.32, Gelatin 1.63
the 6th layer (Intermediate layer)
Gelatin 1.06
The 7th layer (The 1st green-sensitive emulsion layer)
Silver iodobromide emulsion (6 mole % silver iodide, average grain size 0.8 .mu.m) 0.40 (silver), II-2 2.2.times.10.sup.-4, III-2 1.0.times.10.sup.-4, I-7 1.8.times.10.sup.-4, Cpd-33 0.260, Cpd-30 0.21, Cpd-4 0.030, Cpd-3 0.025, Oil-1 0.100, Gelatin 0.75
The 8th layer (The 2nd green-sensitive emulsion layer)
Silver iodobromide emulsion (9 mole % silver iodide, average grain size 0.85 .mu.m) 0.80 (silver), II-2 1.9.times.10.sup.-4, III-2 8.3.times.10.sup.-5, I-7 1.5.times.10.sup.-4, Cpd-33 0.150, Cpd-3 0.010, Cpd-30 0.008, Cpd-4 0.012, Oil-1 0.60, Gelatin 1.10
The 9th layer (The 3rd green-sensitive emulsion layer)
Silver iodobromide emulsion (12 mole % silver iodide, average grain size 1.3 .mu.m) 1.2 (silver), II-2 1.5.times.10.sup.-4, III-2 7.0.times.10.sup.-5, I-7 1.3.times.10.sup.-4, Cpd-33 0.065, Cpd-30 0.025, Oil-2 0.55, Gelatin 1.74
The 10th layer (yellow filter layer)
Yellow colloidal silver 0.05 (silver), 2,5-Di-t-pentadecylhydroquinone 0.03, Gelatin 0.95
The 11th layer (The 1st blue-sensitive emulsion layer)
Silver iodobromide emulsion (6 mole % silver iodide, average grain size 0.6 .mu.m) 0.24 (silver), SD-6 3.5.times.10.sup.-4, Cpd-29 0.85, Cpd-3 0.12, Oil-1 0.28, Gelatin 1.28
The 12th layer (The 2nd blue-sensitive emulsion layer)
Silver iodobromide emulsion (10 mole % silver iodide, average grain size 1.0 .mu.m) 0.45 (silver), SD-6 2.1.times.10.sup.-4, Cpd-29 0.20, Cpd-9 0.15, Oil-1 0.03, Gelatin 0.46
The 13th layer (The 3rd blue-sensitive emulsion layer)
Silver iodobromide emulsion (10 mole % silver iodide, average grain size 1.8 .mu.m) 0.77 (silver), SD-6 2.2.times.10.sup.-4, Cpd-29 0.20, Oil-1 0.07, Gelatin 0.69
The 14th layer (The 1st protective layer)
Silver iodobromide emulsion (1 mole % silver iodide, average grain size 0.07 .mu.m) 0.5 (silver), UV-1 0.11, UV-2 0.17, Oil-1 0.90, Gelatin 1.00
The 15th layer (The 2nd protective layer)
Polymethyl acrylate grain (diameter about 1.5 .mu.m) 0.54, S-1 0.05, S-2 0.20, Gelatin 0.72
Besides the above components, gelatin-hardening agent H-1 and a surfacant were added to each of the layers. ##STR106##
The thus prepared sample was named sample 401. Samples 402 to 408 were similarly prepared using the same composition with sample 401 except sensitizing dye I-7 of the 7th, 8th and 9th layers was changed for those described in Table 4.
These photographic elements were, in the same manner as in Example 3, each subjected to exposure to light and development as such or after preservation under the same condition in Example 3, and then measured for fog and sensitivity. The results are shown in Table 4.
TABLE 4__________________________________________________________________________ After a preservation The 7th layer The 8th layer The 9th layer for 3 days sensitizing dye sensitizing dye sensitizing dye Fresh performance (50.degree. C., 80% RH)Sample Amount Amount Amount Relative RelativeNo. Species mol/mol Ag Species mol/mol Ag Species mol/mol Ag Fog sensitivity Fog sensitivity__________________________________________________________________________401 I-7 1.8 .times. 10.sup.-4 I-7 1.5 .times. 10.sup.-4 I-7 1.3 .times. 10.sup.-4 .+-.0 100 +0.04 95(Present (Standard (Standard ofinvention) of fog) sensitivity)402 I-19 1.8 .times. 10.sup.-4 I-19 1.5 .times. 10.sup.-4 I-19 1.3 .times. 10 .sup.-4 -0.02 97 +0.01 93(Presentinvention)403 I-5 1.8 .times. 10.sup.-4 I-5 1.5 .times. 10.sup.-4 I-5 1.3 .times. 10.sup.-4 +0.02 102 +0.05 93(Presentinvention)404 SD-1 1.8 .times. 10.sup.-4 SD-1 1.5 .times. 10.sup.-4 SD-1 1.3 .times. 10.sup.-4 +0.18 104 +0.35 77(Comparativeexample)405 SD-7 1.8 .times. 10.sup.-4 SD-7 1.5 .times. 10.sup.-4 SD-7 1.3 .times. 10.sup.-4 +0.09 86 +0.14 65(Comparativeexample)406 SD-2 1.8 .times. 10.sup.-4 SD-2 1.5 .times. 10.sup.-4 SD-2 1.3 .times. 10.sup.-4 +0.21 93 +0.47 66(Comparativeexample)407 SD-8 1.8 .times. 10.sup.-4 SD-8 1.5 .times. 10.sup.-4 SD-8 1.3 .times. 10.sup.-4 +0.11 87 +0.18 70(Comparativeexample)408 SD-3 1.8 .times. 10.sup.-4 SD-3 1.5 .times. 10.sup.-4 SD-3 1.3 .times. 10.sup.-4 +0.06 83 +0.13 64(Comparativeexample)__________________________________________________________________________
EXAMPLE 8
A multi-layered color light-sensitive material was prepared by providing each of the layers having the following compositions on a cellulose triacetate film support which had been undercoated, and named sample 501.
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 (as silver amount) monodispersed silver iodobromide emulsion which was spectrally sensitized with 1.4 g/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 (as silver amount) monodispersed silver iodobromide emulsion which was spectrally sensitized with 1.6 g/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 (as silver amount) silver iodobromide emulsion spectrally sensitized with 3.3 mg/m.sup.2 II-3 and 1.5 mg/m.sup.2 I-7 (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 (as silver amount) tabular silver iodobromide emulsion spectrally sensitized with 1.2 mg/m.sup.2 II-3 and 0.6 mg/m.sup.2 I-7 (Iodine content 2.5 mole %, grains having a diameter/thickness ratio of 5 or more amounting to 50% of projected area of all the grains, average thickness of grains 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 cc/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 (as silver amount) silver iodobromide emulsion spectrally sensitized with 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 (as silver amount) 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 amounting to 50% of projected area of all the grains, average thickness of grains 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, 0.29 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 (as silver amount) of emulsion of fine silver iodobromide grains whose surfaces were fogged (Iodine content 1 mole %, average grain size 0.06 .mu.m), and 2.7 g/m.sup.2 of polymethyl methacrylate grains (average grain size 1.5 .mu.m)
Besides the above components, gelatin hardening agent H-3 and a surfactant were added to each layer.
Compound used for preparation of the sample are illustrated below. ##STR107##
The thus prepared sample was named sample 501. Samples 501 to 508 were similarly prepared using the same composition with sample 501 except that sensitizing dye I-7 of the 6th and 7th layers were changed for those described in Table 5.
These photographic elements were, in the same manner as in Example 3, each subjected to exposure to light and the following process as such or after preservation under the same condition in Example 3, and then measured for fog and sensitivity. The results are shown in Table 5.
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 501 of fresh performance, howering 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 38.degree. C.Reversal 2 minutes 38.degree. C.Color development 6 minutes 38.degree. C.Adjustment 2 minutes 38.degree. C.Bleaching 6 minutes 38.degree. C.Fixing 4 minutes 38.degree. C.Water washing 4 minutes 38.degree. C.Stabilization 1 minute Ambient temperatureDrying______________________________________
Compositions of the processing solutions used are as follows.
______________________________________(First developing solution)Water 700 mlPentasodium nitrilo-N,N,N-- 2 gtrimethylenephosphonateSodium sulfite 20 gHydroquinone monosulfonate 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 1 l(Reversal solution)Water 700 mlPentasodium nitrilo-N,N,N-- 3 gtrimethylenephosphonateTin (II) chloride dihydrate 1 gp-Aminophenol 0.1 gSodium hydroxide 8 gGlacial acetic acid 15 mlWater to 1 l(Color developing solution)Water 700 mlPentasodium nitrilo-N,N,N-- 3 gtrimethylenephosphonateSodium sulfite 7 gSodium tertiary phosphate dodecahydrate 36 gPotassium bromide 1 gPotassium iodide (0.1% solution) 90 mlSodium hydroxide 3 gCitrazinic acid 1.5 gN--Ethyl-N--(-methanesulfonamidoethyl)- 11 g3-methyl-4-aminoaniline sulfate3,6-Dithiaoctane-1,8-diol 1 gWater to 1 l(Conditioning solution)Water 700 mlSodium sulfite 12 gDisodium ethylenediaminetetraacetate 8 gdihydrateThioglycerine 0.4 mlGlacial acetic acid 3 mlWater to 1 l(Bleaching solution)Water 800 mlDisodium ethylenediaminetetraacetate 2 gdihydrateFerric ammonium ethylenediaminetetra- 120 gacetate dihydratePotassium bromide 100 gWater to 1 l(Fixing solution)Water 800 mlSodium thiosulfate 80.0 gSodium sulfite 5.0 gSodium bisulfite 5.0 gWater to 1 l(Stabilizing solution)Water 800 mlFormalin (37 weight %) 5.0 mlFUJI DRIWEL (Surfactant 5.0 mlmanufactured by FUJI PHOTO FILM CO. LTD.)Water to 1 l______________________________________
Similar results were also obtained when water washing was conducted by using the following water washing solution in place of water.
______________________________________(Water washing solution)______________________________________Disodium ethylenediaminetetraacetate 0.4 gWater to 1 lpH (with sodium hydroxide) 7.0______________________________________
TABLE 5__________________________________________________________________________ The 6th layer The 7th layer After preservation for Sensitizing dye Sensitizing dye Fresh performance 3 days (50.degree. C. 80% RH)Sample Amount Amount Maximum Relative Maximum RelativeNo. Species mg/m.sup.2 Species mg/m.sup.2 color density sensitivity color density sensitivity__________________________________________________________________________501 I-7 1.5 I-7 0.6 .+-.0 100 -0.05 95(Present (standard of (standard ofinvention) max. color sensitivity density)502 I-19 1.5 I-19 0.6 .+-.0 98 -0.06 94(Presentinvention)503 I-5 1.5 I-5 0.6 -0.02 101 -0.08 97(Presentinvention)504 SD-1 1.5 SD-1 0.6 -0.25 103 -0.41 75(Comparativeexample)505 SD-7 1.5 SD-7 0.6 -0.13 90 -0.25 66(Comparativeexample)506 SD-2 1.5 SD-2 0.6 -0.32 95 -0.49 63(Comparativeexample)507 SD-8 1.5 SD-8 0.6 -0.15 90 -0.25 69(Comparativeexample)508 SD-3 1.5 SD-3 0.6 -0.09 84 -0.20 65(Comparativeexample)__________________________________________________________________________
EXAMPLE 9
Light-sensitive layers comprising the following 1st to 7th layers were each provided on a paper support, both surfaces of which had been laminated with polyethylene to prepare color light-sensitive material samples 601 to 608. The polyethylene on the side where the 1st layer was provided contains titanium dioxide and a trace amount of ultramarine blue.
(Light-sensitive layer construction)
Figures corresponding to respective components mean coated amounts represented by the unit of 8/m.sup.2, and mean coated amounts in terms of silver for silver halide.
______________________________________The 1st layer (Blue-sensitive layer)Silver chlorobromide emulsion silver 0.30(80 mole % silver bromide)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 rays-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 silver 0.20(70 mole % silver bromide)Cyan coupler (Cpd-43/Cpd-44) 0.2/0.2Coupler solvent (Oil-6/Oil-2) 0.10/0.20Gelatin 0.9The 6th layer (Ultraviolet rays-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______________________________________ ##STR108##
The following compounds were used as spectrally sensitizing dyes for the blue-sensitive emulsion layer and the red-sensitive emulsion layer.
Blue-sensitive emulsion layer SD-6
(2.times.10.sup.-4 moles thereof was added per 1 mole of silver halide)
Red-sensitive emulsion layer SD-16 ##STR109##
(2.5.times.10.sup.-4 moles thereof was added per 1 mole of silver halide)
The following dyes were used as irradiation-inhibiting dyes for respective emulsion layers. ##STR110##
As for the green-sensitive emulsion layer, silver chlorobromide emulsion (silver chloride content 30 mole %) comprising monodispersed cubic grains having an average grain size of 0.4 .mu.m was used, chemical sensitization was conducted by adding 2.0.times.10.sup.-5 moles of sodium thiosulfate per 1 mole of silver halide, 4-hydroxy-6-methyl-(1,3,3a,7)-tetrazaidene was used as a stabilizing agent in an amount of 300 mg per 1 mole of silver halide, and combination of spectral sensitizing dyes in Table 6 was used.
Further, as an emulsified dispersion, an emulsified dispersion was used which was prepared by dissolving 100 g of Cpd-20, a magenta coupler together with 50 g of Cpd-45, a fading inhibitor in a mixture of 200 ml of Oil-7 (a solvent) and 100 ml of ethyl acetate, and emulsifying and dispersing the solution in 2,000 g of an aqueous 10% gelatin solution containing 8.0 g of sodium dodecylbenzenesulfonate. ##STR111##
Amount of the emulsion applied as the 3rd layer was 200 mg/m.sup.2 in terms of silver amount.
______________________________________Emulsified dispersion______________________________________Emulsified dispersion 2Magenta 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 coated gelatin amount becomes 1800 mg/m.sup.2)
In order to confirm preservability of these coating 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.
______________________________________Process step Temperature Time______________________________________Developing solution 33.degree. C. 3.5 minutesBleach-fixing solution 33.degree. C. 1.5 minutesWater washing 28-35.degree. C. 3.0 minutes______________________________________(Developing solution)Diethylenetriaminepentaacetic 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 lpH 10.1(Bleach-fixing solution)Ammonium thiosulfate (54 wt %) 150 mlNa.sub.2 SO.sub.3 15 gNH.sub.4 [Fe(EDTA)] 55 gDisodium ethylendiaminetetraacetate 4 gdihydrateWater to 1 lpH 6.9______________________________________
The thus treated samples were each measured for color density, and changes of sensitivity and fog after preservation in comparison with fresh performance were determined. The results are shown in Table 6.
TABLE 6__________________________________________________________________________ After preservation for Fresh performance 4 weeks (50.degree. C., 45% RH)Sample The 3rd layer sensitizing dye Relative RelativeNo. Species Amount Species Amount Fog sensitivity Fog Sensitivity__________________________________________________________________________601 I-5 1.7 .times. 10.sup.-4 II-2 3.2 .times. 10.sup.-4 .+-.0 100 +0.04 96(Present mol/mol Ag mol/mol Ag (Standard (standard ofinvention) of fog) sensitivity)602 I-7 1.7 .times. 10.sup.-4 " 3.2 .times. 10.sup.-4 +0.01 98 +0.04 95(Present mol/mol Ag mol/mol Aginvention)604 SD-1 1.7 .times. 10.sup.-4 " 3.2 .times. 10.sup.-4 +0.12 103 +0.25 86(Comparative mol/mol Ag mol/mol Agexample)605 SD-7 1.7 .times. 10.sup.-4 " 3.2 .times. 10.sup.-4 +0.05 90 +0.10 68(Comparative mol/mol Ag mol/mol Agexample)606 SD-2 1.7 .times. 10.sup.-4 " 3.2 .times. 10.sup.-4 +0.15 97 +0.36 60Comparative mol/mol Ag mol/mol Agexample)607 SD-8 1.7 .times. 10.sup.-4 " 3.2 .times. 10.sup.-4 +0.05 86 +0.10 65(Comparative mol/mol Ag mol/mol Agexample)608 SD-3 1.7 .times. 10.sup.-4 " 3.2 .times. 10.sup.-4 +0.03 86 +0.12 61(Comparative mol/mol Ag mol/mol Agexample)__________________________________________________________________________
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 spectrally sensitizing dye(s) of the general formula(e) (II) and/or (III).

Number	Name	Date
2521959	Anish	Sep 1950
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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