Silver halide color photographic material and processing method thereof

FIELD OF THE INVENTION
The present invention relates to a silver halide color photographic material containing a coupler suitable for short-time processing and low-replenishing processing and also to a processing method of the color photographic material.
BACKGROUND OF THE INVENTION
Recently with the requirement of shortening a processing time, a color photographic light-sensitive material is required to give color images of a sufficient density within a shorter developing time. However, conventionally known techniques are not satisfactory and more improvements have been required. In particular, in a multilayer color photographic light-sensitive material, the development of the silver halide emulsion layer(s) disposed near the support is delayed and color images having a sufficient density are not obtained in short-time processing. That is, there is a problem that the development progress differs between the upper emulsion layer(s) and lower emulsion layer(s) and the color balance is unballanced.
As an attempt of obtaining a high color density by accelerating the development, couplers each releasing a color developing agent through a linkage group are known as described, e.g., in JP-A-61-156126 and JP-A-51-26038 (the term "JP-A" as used herein means an "unexamined published Japanese patent application"). However, even in the case of using these couplers, the color density obtained is not yet insufficient and a further improvement has been desired.
On the other hand, for the necessity of preventing the water pollution and the reduction of the processing cost, the technique of reducing the amount of waste liquids in photographic processing has been investigated. As one method thereof, there is a method of reducing the amount of the replenisher for a color developer and the practical use of the method has been investigated. The conventionally practiced replenishing amount of a color developer depends upon the kind of a color photographic material being processed and in the case of, for example, a color photographic negative film for photographing, the replenishing amount for a color developer is generally from 900 to 1200 ml per square meter of the color photographic film but recently with the requirement of low replenishing developing, the color development with a replenishing amount of about 600 ml has begun to be practiced.
However, when the processing time is shortened in the low replenishing processing, it becomes more difficult to obtain color images having a sufficient density.
SUMMARY OF THE INVENTION
A first object of the present invention is to provide a color photographic light-sensitive material capable of giving a sufficient color image density with a shorter time.
A second object of the present invention is to provide a color photographic light-sensitive material capable of giving a sufficient color image density with low replenishing process and with a shortened processing time.
It has now been discovered that the above objects can be achieved by the present invention as described hereinbelow.
That is, according to the present invention, there is provided a silver halide color photographic material having at least one silver halide emulsion layer provided on a support, wherein the color photographic material contains a nondiffusing coupler represented by the following formula (I)
Cp-O--C(.dbd.O)--N(R.sub.1)--Ar--X (I)
wherein Cp represents a coupler residue (residual group) capable of releasing --O--C(.dbd.O)--N(R.sub.1)--Ar--X by causing a coupling reaction with an oxidized color developing agent; Ar represents an arylene group, X represents an amino group, an alkoxy group or a hydroxy group; and R.sub.1 represents a hydrogen atom or a substituent.
DETAILED DESCRIPTION OF THE INVENTION
Then, the present invention is described in detail.
First, the coupler shown by the formula (I) is explained in detail.
When Cp represents a yellow color image-forming coupler residue, as such a coupler residue, there are, for example, pivaloylacetanilide coupler residues, benzoylacetanilide coupler residues, malondiester coupler residues, malondiamide coupler residues, dibenzoylmethane coupler residues, benzothiazolylacetamide coupler residues, malonestermonoamide coupler residues, triazolylacetamide coupler residues, benzimidazolylacetamide coupler residues, and cycloalkanoylaetamide coupler residues. Furthermore, the coupler residue may be the coupler residues described in U.S. Pat. Nos. 5,021,332 and 5,021,330 and European Patent 421,221A.
When Cp represents a magenta color image-forming coupler residue, as the coupler residue, there are, for example, 5-pyrazolone coupler residues, pyrazolobenzimidazole coupler residues, pyrazolotriazole coupler residues, pyrazoloimidazole coupler residues, and cyanoacetophenone coupler residues.
When Cp represents a cyan color image-forming coupler residue, as the coupler residue, there are, for example, phenol coupler residues and naphthol coupler residues. Furthermore, the coupler residues described in U.S. Pat. No. 4,746,602 and European Patent 249,453A may be used as the coupler residue.
Furthermore, Cp may be a coupler residue which does not substantially leave color images. As the coupler residue of this type, there are, for example, indanone coupler residues, acetophenone coupler residues, and also the dissolving out-type coupler residues described in European Patents 443,530A and 444,501A.
The coupler residues which can be preferably used in the present invention are shown by the following formulae (Cp-1), (Cp-2), (Cp-3), (Cp-4), (Cp-5), (Cp-6), (Cp-7), (Cp-8), (Cp-9) and (Cp-10).
These couplers show a particularly high coupling speed and are preferred. ##STR1##
When in the above formulae, R.sub.51, R.sub.52, R.sub.53, R.sub.54, R.sub.55, R.sub.56, R.sub.57, R.sub.58, R.sub.59, R.sub.60, R.sub.61, R.sub.62, or R.sub.63 contains a nondiffusive group, the group is selected so that the total number of the carbon atoms becomes from 8 to 40, and preferably from 10 to 30 and in other cases, the total number of the carbon atoms is preferably not more than 15.
In the above formulae, the free bondings each shows the bonding position of --O--C(.dbd.O)--N(R.sub.1)--Ar--X.
In the case of a bis type coupler, a telomer type coupler, or a polymer type coupler, one of the foregoing groups R.sub.51 to R.sub.63 represents a divalent group and links to a repeating unit, etc. In this case, the range of the carbon number is outside the definition.
Then, R.sub.51 to R.sub.63, b, d, e, and f are explained in detail.
For the convenience of explaining R.sub.51 to R.sub.63, R.sub.41 to R.sub.45 are utilized. That is, R.sub.41 represents an alkyl group, an aryl group, or a heterocyclic group; R.sub.42 represents an aryl group or a heterocyclic group; and R.sub.43, R.sub.44, and R.sub.45 each represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.
In the above formulae, R.sub.51 has the same meansing (definition) as R.sub.41. R.sub.52 and R.sub.53 each has the same meaning as R.sub.43. In the formulae, b represents 0 or 1. R.sub.54 represents the group same as R.sub.41, an R.sub.41 CO(R.sub.43)N-- group, an R.sub.41 SO.sub.2 (R.sub.43)N-- group, an R.sub.41 (R.sub.43)N-- group, an R.sub.41 S-- group, an R.sub.43 O-- group, or an R.sub.45 (R.sub.43)NCON(R.sub.44)-- group.
R.sub.55 has the same meaning as R.sub.41. R.sub.56 and R.sub.57 each represents the group same as R.sub.43, an R.sub.41 S-- group, an R.sub.43 O-- group, an R.sub.41 CO(R.sub.43)N-- group, an R.sub.41 SO.sub.2 (R.sub.43)N-- group, an R.sub.41 (R.sub.43)N--, or an R.sub.45 (R.sub.43)NCON(R.sub.44)-- group. R.sub.58 has the same meaning as R.sub.41. R.sub.59 represents the same group as R.sub.41, an R.sub.41 CO(R.sub.43)N-- group, an R.sub.41 OCO(R.sub.43)N-- group, an R.sub.41 SO.sub.2 (R.sub.43)N-- group, an R.sub.43 (R.sub.44)NCO(R.sub.45)N-- group, an R.sub.41 O-- group, an R.sub.41 S-- group, a halogen atom, or an R.sub.41 (R.sub.43)N-- group. In the formulae, d represents 0 or an integer of from 1 to 3. When d is 2 or 3, plural R.sub.59 S may be same or a different.
R.sub.60 has the same meaning as R.sub.41. R.sub.61 has the same meaning as R.sub.41. R.sub.62 represents the same group as R.sub.41, an R.sub.41 OCONH-- group, an R.sub.41 OCONH-- group, an R.sub.41 SO.sub.2 NH-- group, an R.sub.43 (R.sub.44)NCONH-- group, an R.sub.43 (R.sub.44)NSO.sub.2 NH-- group, an R.sub.43 O-- group, an R.sub.41 S-- group, an R.sub.41 CO(R.sub.43)NSO.sub.2 -- group, a halogen atom, or an R.sub.41 NH-- group.
R.sub.63 represents the same group as R.sub.41, an R.sub.43 CO(R.sub.44)N-- group, an R.sub.43 (R.sub.44)NCO-- group, an R.sub.41 SO.sub.2 (R.sub.43)N-- group, R.sub.41 (R.sub.43)NSO.sub.2 -- group, an R.sub.41 SO.sub.2 -- group, an R.sub.43 OCO-- group, an R.sub.43 O--SO.sub.2 -- group, a halogen atom, a nitro group, a cyano group, or an R.sub.43 CO-- group.
In formulae, e represents 0 or an integer of from 1 to 4 and f represents 0 or an integer of from 1 to 3. When R.sub.62 or R.sub.63 is plural, they may be the same or different.
In the above groups, the alkyl group is a chain or cyclic, straight chain or branched alkyl group preferably having from 1 to 32, more preferably 1 to 22 carbon atoms. Specific examples of the alkyl group are a methyl, cyclopropyl, isopropyl, n-butyl, t-butyp, i-butyl, t-amyl, n-hexyl, cyclohexyl, 2-ethylhexyl, n-octyl, 1,1,3,3,-tetramethylbutyl, n-decyl, n-dodecyl, n-hexadecyl, and n-octadecyl groups.
The aryl group is preferably a substituted or unsubstituted phenyl or naphtyl group preferably having from 6 to 20 carbon atoms.
The heterocyclic group is preferably from 3-membered to 8-membered, substituted or unsubstituted heterocyclic group preferably having at least one of N, O and S atoms as hetero atom and preferably having from 1 to 20, and more preferably from 1 to 7 carbon atoms. The heterocyclic ring may be condensed with a benzene ring. Specific examples of the heterocyclic group are 2-pyridyl, 2-benzoxazolyl, 2-imidazolyl, 2-benzimidazolyl, 1-indolyl, 1,3,4-thiadiazol-2-yl, 1,2,4-triazol-2-yl, and 1-indolynyl.
When the alkyl group, the aryl group, and the heterocyclic group described above have a substituent, as the substituent, there are a halogen atom (e.g., F, Cl, Br and I), an R.sub.47 O-- group, R.sub.46 S-- group, an R.sub.47 CO(R.sub.48)N-- group, an R.sub.47 (R.sub.48)NCO-- group, an R.sub.46 OCO(R.sub.47)N-- group, an R.sub.46 SO.sub.2 (R.sub.47)N-- group, an R.sub.46 SO.sub.2 (R.sub.47)NCO-- group, an R.sub.47 (R.sub.48)NSO.sub.2 -- group, an R.sub.46 SO.sub.2 -- group, an R.sub.47 OCO-- group, an R.sub.47 NCO(R.sub.48)N-- group, an R.sub.47 CONHSO.sub.2 -- group, an R.sub.47 (R.sub.48)NCONHSO.sub.2 -- group, the group same as R.sub.46, an R.sub.47 (R.sub.48)N-- group, an R.sub.46 COO-- group, an R.sub.47 OSO.sub.2 -- group, a cyano group, and a nitro group, wherein R.sub.46 represents an alkyl group, an aryl group, or a heterocyclic group and R.sub.47 and R.sub.48 each represents an alkyl group, an aryl group, a heterocyclic group, or a hydrogen atom. The alkyl group, the aryl group, and the heterocyclic group described above have the same meanings as defined above.
Then, the preferred scopes of R.sub.51 to R.sub.63, b, d, e, and f are explained.
R.sub.51 is preferably an alkyl group, an aryl group, or a heterocyclic group. R.sub.52 and R.sub.55 are preferably an aryl group. R.sub.53 is preferably an aryl group when b is 1 and is preferably a heterocyclic group when b is 0. Preferred b is 0. R.sub.54 is preferably an R.sub.41 CONH-- group or an R.sub.41 (R.sub.43)N-- group. R.sub.56 and R.sub.57 are preferably an alkyl group, an R.sub.41 O-- group, or an R.sub.41 S-- group.
R.sub.58 is preferably an alkyl group or an aryl group. In the formula (Cp-6), R.sub.56 is preferably a chlorine atom, an alkyl group, or an R.sub.41 CONH-- group. Furthermore, d is preferably 1 or 2. R.sub.60 is preferably an aryl group.
In the formula (Cp-7), R.sub.59 is preferably an R.sub.41 CONH-- group. In the formula (Cp-7), d is preferably 1. R.sub.61 is preferably an alkyl group or an aryl group.
In the formula (Cp-8), e is preferably 0 or 1. R.sub.62 is preferably an R.sub.41 OCONH-- group, an R.sub.41 CONH-- group, or an R.sub.41 SO.sub.2 NH-- group. A preferred substitution position is the 5-position of the naphthol ring.
In the formula (Cp-9), e is preferably 1 and R.sub.63 is preferably an R.sub.41 CONH-- group, an R.sub.41 SO.sub.2 NH-- group, an R.sub.41 (R.sub.43)NSO.sub.2 -- group, an R.sub.41 SO.sub.2 -- group, or an R.sub.41 (R.sub.43)NCO-- group.
In the formula (Cp-10), f is preferably 1 and R.sub.63 is preferably an R.sub.43 NHCO-- group, an R.sub.43 OCO-- group, or an R.sub.43 CO-- group.
In the formula (I) described hereinbefore, when R.sub.1 represents a substituent, as the substituent, there are preferably an alkoxycarbonyl group (preferably having from 2 to 30, and more preferably from 2 to 20 carbon atoms, such as, for example, methoxycarbonyl, dodecyloxycarbonyl, and hexadecyloxycarbonyl), an unsubstituted sulfamoyl group, an alkyl-, aryl- and N-acyl- (in the present invention an acyl group or moiety includes an aliphatic and aromatic acyl group or moiety, respectively) sulfamoyl groups (preferably having from 1 to 30 carbon atoms, and more preferably from 1 to 20 carbon atoms, such as, for example, N-butylsulfamoyl, N-dodecylsulfamoyl, N,N-diethylsulfamoyl, N-propanoylsulfamoyl, N-tetradecanoylsulfamoyl, and N-benzoylsulfamoyl), a sulfonyl group such as an alkyl- and aryl-sulfonyl groups (preferably having from 1 to 30 carbon atoms, and more preferably from 1 to 20 carbon atoms, such as, for example, methanesulfonyl, octanesulfonyl, benzenesulfonyl, and dodecanesulfonyl), an alkyl group (a straight chain, branched, or cyclic alkyl group preferably having from 1 to 30, and more preferably from 1 to 20 carbon atoms, such as, for example, methyl, ethyl, isopropyl, cyclopropyl, t-pentyl, t-octyl, cyclopentyl, t-butyl, s-butyl, dodecyl, and 2-hexyldecyl), an aryl group (preferably having from 6 to 20, and more preferably from 6 to 10 carbon atoms, such as, for example, phenyl, naphthyl, and 4-methoxyphenyl), and an acyl group (preferably having from 1 to 30, and more preferably from 2 to 20 carbon atoms, such as, for example, acetyl and benzoyl). As shown in parentheses above these substituents may be further substituted with at least one of these substituents.
In the formula (I), the group shown by Ar is a substituted or unsubstituted arylene group preferably having from 6 to 20, and more preferably 6 to 10 carbon atoms, such as, preferably, 1,4-phenylene, 1,2-phenylene, 1,4-naphthylene, and 1,2-naphthylene.
When the group shown by Ar has a substituent, examples of the substituent are a halogen atom (e.g., fluorine and chlorine), an acylamino group (preferably having from 2 to 30, and more preferably from 2 to 20 carbon atoms, such as, for example, acetamido and benzamido), a sulfonamido group such as an alkyl- and aryl-sulfonamido groups (preferably having from 1 to 30, and more preferably from 1 to 20 carbon atoms, for example, methanesulfonamido and benzenesulfonamido), an alkoxy group (preferably having from 1 to 30, and more preferably from 1 to 20 carbon atoms, such as, for example, methoxy, hexadecyloxy, and isopropoxy), an aryloxy group (preferably having from 6 to 20, and more preferably from 6 to 10 carbon atoms, such as, for example, phenoxy, 4-methoxyphenoxy, and naphthoxy), an alkoxycarbonylamino group (preferably having from 2 to 30, and more preferably from 2 to 20 carbon atoms, such as, for example, ethoxycarbonylamino and tetradecyloxycarbonylamino), --COOM and --SO.sub.3 M (wherein M represents a hydrogen atom, an alkali metal atom such as Li, Na and K, or NH.sub.4), a hydroxy group, an alkylthio group (preferably having from 1 to 30, and more preferably from 1 to 20 carbon atoms, such as, for example, methylthio, dodecylthio, and dodecylcarbamoylmethylthio), a ureido group (preferably having from 1 to 30, and more preferably from 1 to 20 carbon atoms, such as, for example, N-phenylureido and N-butylureido), an aryl group (preferably having from 6 to 20, and more preferable from 6 to 10 carbon atoms, such as, for example, phenyl, naphthyl, and 4-methoxyphenyl), a heterocyclic group (a 3- to 12-membered, and preferably 5- or 6-membered monocyclic or condensed ring (e.g., with a benzene ring) preferably having from 1 to 20, and more preferably from 1 to 10 carbon atoms and containing at least one of, for example, nitrogen, oxygen, and sulfur as a hetero atom, such as, for example, 2-pyridyl, 4-pyridyl, 4-pyrimidinyl, 3-pyrazolyl, 1-pyrrolyl, 2,4-dioxo-1,3-imidazolidin-1-yl, morpholino, and indolyl), an alkyl group (a straight chain, branched, or cyclic alkyl group preferably having from 1 to 30, and more preferably from 1 to 20 carbon atoms, such as, for example, methyl, ethyl, isopropyl, cyclopropyl, t-pentyl, t-octyl, cyclopentyl, t-butyl, s-butyl, dodecyl, and 2-hexyldecyl), an arylthio group (preferably having from 6 to 20, and more preferably from 6 to 10 carbon atoms, such as, for example, phenylthio and naphthylthio), and a sulfamoylamino group such as an alkyl-, aryl and acyl-sulfamoylamono groups (preferably having from 0 to 30, and more preferably from 0 to 20 carbon atoms, such as, for example, N-butylsulfamoylamino, N-dodecylsulfamoylamino, and N-phenylsulfamoylamino). As indicated in parentheses above these substituents may be further substituted with at least one of these substituents.
When the group shown by X in the formula (I) represents an amino group, examples of the amino group are an unsubstituted amino group, an alkyl-substituted amino group (including an N-containing heterocyclic group formed by connecting two substituents of the amino group) (preferably having from 1 to 30, and more preferably from 2 to 10 carbon atoms, such as, for example, dimethylamino, diethylamino, N-ethyl-N-methanesulfonamidoethylamino, N-ethyl-N-hydroxyethylamino, N,N-bis(3-hydroxypropyl)amino, N,N-bis(2-hydroxethyl)amino, dipropylamino, N-methyl-N-ethylamino, morpholino, pyrrolidino, or dibutylamino), and an arylamino group (preferably having from 6 to 20, and more preferably from 6 to 10 carbon atoms, such as, for example, anilino, M-methylanilino, and N-methylnaphthylamino). As shown in parentheses above the alkyl and aryl moieties in the alkyl- or aryl-substituted amino group may be further substituted with at least one of substituents such as those recited as substituents for Ar.
When the group shown by X in the formula (I) represents an alkoxy group, the alkoxy group is a substituted or unsubstituted alkoxy group preferably having from 1 to 30, and more preferably from 1 to 20 carbon atoms. Examples of the alkoxy group are same as those explained above as the substituents for Ar.
The coupler shown by the formula (I) is a nondiffusing coupler. A nondiffusing coupler is a coupler having a group sufficiently increasing the molecular weight of the molecule for making the coupler molecule immobile in the layer containing the coupler. As such a group, an alkyl group having from 8 to 30, and preferably from 10 to 20 total carbon atoms or an aryl group having a substituent having from 4 to 20 total carbon atoms is usually used. Such a nondiffusing group may be substituted to any position of the molecule or the molecule has plural such nondiffusing groups.
Then, the preferred scope of the coupler shown by the formula (I) is explained.
In the formula (I), Cp is preferably a cyan coloring type coupler residue.
When Ar in the formula (I) is an unsubstituted phenylene group or a divalent phenylene group substituted with at least one alkyl group, alkoxy group, or acylamino group, the effect of the present invention is particularly remarkable and thus is preferable in this invention. Ar is preferably 1,4-phenylene.
X in the formula (I) is particularly preferably an amino group substituted with two alkyl groups.
Also, R.sub.1 in the formula (I) is particularly preferably a hydrogen atom or a sulfonyl group.
Then, specific examples of the nondiffusing coupler being used in the present invention are illustrated below but the invention is not limited by the compounds. ##STR2##
The coupler of the present invention shown by the formula (I) described above can be added to any light-sensitive silver halide emulsion layer or a layer adjacent to an emulsion layer but, in particular, it is preferred to add the coupler to a light-sensitive silver halide emulsion layer. When the silver halide emulsion layer is an unit comprising 2 or more silver halide emulsion layers having the same color sensitivity but different photographic speeds, it is preferred that the coupler is incorporated into the emulsion layer having the lowest speed.
The coupler may be added to a hydrophilic colloidal layer adjacent to an emulsion layer. Examples of the hydrophilic colloidal layer include an intermediate layer, an antihalation layer, an irradiation preventing layer and a protective layer.
The total addiion amount of the coupler to the color photographic material is preferably from 0.0001 to 1.50 g/m.sup.2, more preferably from 0.01 to 1.20 g/m.sup.2, and particularly preferably from 0.1 to 1.0 g/m.sup.2.
Then, synthesis examples of the illustrated compounds are shown below.
I. Synthesis of Compound A-1 ##STR3## 1) Synthesis of Compound 3
In 300 ml of dichloromethane was suspended 69.9 g (0.239 mole) of compound 1 (shown in the above scheme) in a vessel and the suspension was ice-cooled and the atmosphere of the vessel was replaced with a nitrogen gas. After adding thereto 66.7 ml (0.478 mole) of triethylamine under the nitrogen gas atmosphere, 30 ml (0.239 mole) of compound 2 (shown in the above scheme) was added dropwise to the mixture. Thereafter, the ice-cooling bath was removed, the reaction mixture was stirred until the reaction system became room temperature and 500 ml of water was added to the reaction system to separate the reaction mixture into an aqueous phase and an organic phase. The aqueous phase separated was extracted 5 times with 300 ml of ethyl acetate and the organic phases (the above organic phase and the extrtacts) obtained were mixed with each other and dried with anhydrous sodium sulfate. Then, by distilling off the solvent from the mixture under reduced pressure, 68.9 g (0.219 mole) of compound 3 (shown in the above scheme) was obtained with a yield of 91.6%.
2) Synthesis of Compound A-1
In a mixed solvent of acetonitrile (300 ml) and N,N-dimethylacetamide (100 ml) were dissolved 60.8 g (0.128 mole) of compound 4 (shown in the above scheme) and 38.4 g (0.128 mole) of the compound 3 obtained in the above synthesis in a vessel and the solution was ice-cooled and the atmosphere in the vessel was replaced with a nitrogen gas. After adding dropwise thereto 19.1 ml (0.128 mole) of 1,8-diazabicyclo-�5,4,0!-7-undecene (hereinafter, is referred to as DBU) under a nitrogen gas atmosphere, the mixture was stirred for 15 minutes while ice-cooling and further after removing the ice-cooling bath, was stirred for one hour. Then, 500 ml of water was added to the reaction system to separate into an aqueous phase and an organic phase and the aqueous phase separated was extracted with 300 ml of ethyl acetate. The extract was mixed with the organic phase separated above, the mixture was dried with anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The residue obtained was purified by a silica gel column chromatography (eluent: dichloromethane/ethyl acetae=9/1 by volume) and then recrystallized from n-hexane/ethyl acetate (1/2 vol/vol) to provide 20.6 g (0.0288 mole) of the compound A-1 with a yield of 22.6%.
II. Synthesis of Compound A-4 ##STR4## 1) Synthesis of Compound 6
In 30 ml of N,N-dimethylacetamide was suspended 19.2 g (0.0399 mole) of compound 5 (shown in the above scheme) in a vessel and the suspension was ice-cooled and the atmosphere in the vessel was replaced with a nitrogen gas. After adding thereto 16.7 ml (0.120 mole) of triethylamine under the nitrogen gas atmosphere, 5 ml (0.0399 mole) of the compound 2 (shown in the scheme 1 described above) was added dropwise to the mixture. Thereafter, the ice-cooling bath was removed and the reaction system was stirred for 3 hours. Then, after adding 100 ml of water and 100 ml of ethyl acetate to the reaction mixture and separating an aqueous phase from an organic phose, the aqueous phase was extracted 3 times with 100 ml of ethyl acetate. The extracts obtained were mixed with the organic phase obtained in the above procedure and after drying the mixture with anhydrous sodium sulfate, the solvent was distilled off from the mixture under reduced pressure to provide 11.5 g (0.0364 mole) of compound 6 (shown in the above scheme) with the yield of 91.4%.
2) Synthesis of Compound A-4
In a mixed solvent of acetonitrile (300 ml) and N,N-dimethylacetamide (100 ml) were dissolved 14.1 g (0.0297 mole) of the compound 4 (shown in the scheme 1) and 9.34 g (0.0297 mole) of the compound 6 obtained in the above step in a vessel and the solution was ice-cooled and the atmosphere in the vessel was replaced with a nitrogen gas. After adding dropwise thereto 4.44 ml (0.0297 mole) of DBU under the nitrogen gas atmosphere, the ice-cooling bath was removed and the mixture was stirred until the temperature of the reaction system became room temperature. After adding 300 ml of water and 300 ml of ethyl acetate to the reaction system and adjusting pH of the reaction system to 5 with diluted hydrochloric acid, an aqueous phase formed was separated from an organic phase. Furthermore, the aqueous phase obtained was extracted with 300 ml of ethyl acetate. The extract was mixed with the organic phase obtained above and after drying the mixture with anhydrous sodium sulfate, the solvent was distilled off from the mixture under reduced pressure. The residue obtained was recrystallized from ethyl acetate to provide 12.3 g (0.0173 mole) of the compound A-4 with the yield of 58.3%.
III. Synthesis of Compound A-6 ##STR5## 1) Synthesis of Compound A-6
In a mixed solvent of acetonitrile (300 ml) and N,N-dimethylacetamide (100 ml) were dissolved 54.1 g (0.113 mole) of compound 7 and 34.0 g (0.113 mole) of the compound 3 obtained according to the scheme 1 in a vessel and the solution was ice-cooled and the atmosphere in the vessel was replaced with a nitrogen gas. After adding dropeise thereto 17.2 ml (0.133 mole) of DBU under the nitrogen gas atmosphere, the mixture was stirred under ice-cooling for 1 hour and further after removing the ice-cooling bath, was stirred for 4 hours. Then, 500 ml of water and 300 ml of ethyl acetate were added to the reaction system and an organic phase formed was separated from an aqueous phoase formed. The organic phase thus separated was washed with water and then washed twice with an aqueous diluted hydrochloric acid solution (about 0.01 mole/liter) and further twice with water. Then, after drying the organic phase with anhydrous sodium sulfate, the organic phase was concentrated under reduced pressure. The residue obtained was filtered with a silica gel, further purified with a silica gel column chromatography (eluent: n-hexane/ethyl acetate=1/1 by volume), and recrystallized from n-hexane/ethyl acetate to provide 31.3 g (0.0449 mole) of the compound A-6 with the yield of 39.7%.
When Cp in formula (I) represents a pyrazoloazole magenta coupler moiety, the coupler of formula (I) can be prepared by reacting compound 7 with compound 8 (which is similar to compound 3 shown in Synthesis of Compound A-1) in the same manner as described hereinabove in the synthesis method.
Compound 7 can be prepared according to the method disclosed in JP-A-4-261529 or U.S. Pat. No. 4,914,209.
The synthesis scheme for production of the magenta coupler (9) is shown below: ##STR6##
Wherein R.sub.71 has the same meaning (definition) as R.sub.56, R.sub.72 has the same meaning as R.sub.57, R.sub.73 represents an aryl group, R.sub.74 and R.sub.75 represents an alkyl group or an aryl group, R.sub.76 represents a substituent, and m represents 0 or an integer of from 1 to 4. Examples of the substituent represented by R.sub.76 are the same as those for Ar in formula (I).
When Cp in formula (I) represents an yellow coupler moiety such as an acylacetanilide coupler moiety, the coupler represented by formula (I) can be prepared by hydrolysing compound 10 to obtain compound 11 and then reacting thus obtained compound 11 with compound 8 according to the synthesis method described hereinabove.
Compound 10 can be prepared according to the method disclosed in U.S. Pat. No. 3,447,928.
The synthesis scheme for production of the yellow ##STR7##
Wherein R.sub.77 has the same meaning as R.sub.51, R.sub.78 has the same meaning as R.sub.52, and R.sub.74, R.sub.75, R.sub.76 and m has the same meaning as discribed hereinabove.
The photographic material of the present invention is not specifically defined, provided that it has at least one light-sensitive layer on a support. As one typical example, there is mentioned a silver halide photographic material having on a support at least one light-sensitive layer composed of plural silver halide emulsion layers each having substantially the same color-sensitivity but having a different sensitivity degree. The light-sensitive layer is a unit light-sensitive layer having a color-sensitivity to anyone of blue light, green light and red light. In a multi-layer silver halide color photographic material, in general, the order of the light-sensitive layer units comprises a red-sensitive layer unit, a green-sensitive layer unit and a blue-sensitive layer unit formed on the support in this order. As the case may be, however, the order may be opposite to the above-mentioned one, depending on the object of the photographic material. As still another embodiment, a different color-sensitive layer may be sandwiched between other two and the same color-sensitive layers. Light-insensitive layers may be provided between the above-mentioned silver halide light-sensitive layers or may be provided as an uppermost layer and/or a lowermost layer. These layers may contain couplers, DIR compounds, color mixing preventing agents and others which will be mentioned hereunder. As described in DE 1,121,470 and GB 923,045, the plural silver halide emulsion layers constituting a respective light-sensitive layer unit, preferably is a two-layered constitution composed of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer arranged on the support in such a way that the sensitivity degree of the layer is to gradually decrease in the direction to the support. As another embodiment, a low-sensitivity emulsion layer is formed remote from the support while a high-sensitivity emulsion layer is formed near to the support, as described in JP-A 57-112751, 62-200350, 62-206541, and 62-206543.
As specific examples of the layer constitution on the support, there are mentioned an order of low-sensitivity blue-sensitive layer (BL)/high-sensitivity blue-sensitive layer (BH)/high-sensitivity green-sensitive layer (GH)/low-sensitivity green-sensitive layer (GL)/high-sensitivity red-sensitive layer (RH)/low-sensitivity red-sensitive layer (RL) from the remotest side from the support; and an order of BH/BL/GL/GH/RH/RL; and an order of BH/BL/GH/GL/RL/RH.
As other examples, there are mentioned an order of blue-sensitive layer/GH/RH/GL/RL from the remotest side from the support, as described in JP-B 55-34932; and an order of blue-sensitive layer/GL/RL/GH/RH from the remotest side from the support, as described in JP-A 56-25738 and 62-63936.
As further example, there is a three-layer unit constitution as described in JP-B 49-15495, where the uppermost layer is a highest-sensitivity silver halide emulsion layer, the intermediate layer is a silver halide emulsion layer having a lower sensitivity than the uppermost layer, and the lowermost layer is a silver halide emulsion layer having a further lower sensitivity than the intermediate layer. That is, in the layer constitution of the type, the sensitivity degree of each emulsion layer is gradually lowered to the direction of the support. Even in such a three-layer constitution having the same color-sensitivity, the layers may be composed of middle-sensitivity emulsion layer/high-sensitivity emulsion layer/low-sensitivity emulsion layer formed in this order from the remotest side from the support, as described in JP-A 59-202464.
As still other examples of the layer constitution of the photographic material of the present invention, there are mentioned an order of high-sensitivity emulsion layer/low-sensitivity emulsion layer/middle-sensitivity emulsion layer/, and an order of low-sensitivity emulsion layer/ middle-sensitivity emulsion layer/high-sensitivity emulsion layer. Where the photographic material of the invention has four or more layers, the layer constitution thereof may be varied in accordance with the manner mentioned above.
In order to improve the color reproducibility, it is desired to provide a doner layer (CL) which has an interlayer effect and which has a color sensitivity distribution different from that of the essential light-sensitive layers of BL, GL and RL, adjacent to or near to the essential light-sensitive layers, in the manner as described in U.S. Pat. Nos. 4,663,277, 4,705,744 and 4,707,436 and JP-A 62-160448 and 63-89850.
Silver halides preferably used in the present invention are silver iodobromides, silver iodochlorides or silver iodochlorobromides having a silver iodide content of about 30 mol % or less. Especially preferred are silver iodobromides or silver iodochlorobromides having a silver iodide content of from about 2 mol % to about 10 mol %.
The silver halide grains in the photographic emulsion constituting the photographic material of the present invention may be regular crystallines such as cubic, octahedral or tetradecahedral grains, or irregular crystallines such as spherical or tabular grains, or irregular crystallines having a crystal defect such as a twin plane, or composite crystallines composed of the above-mentioned regular and irregular crystalline forms.
Regarding the grain size of the silver halide grains, the grains may be fine grains having a small grain size of about 0.2 mictons or less as the diameter of the projected area or may be large ones having a large grain size of up to about 10 microns as the diameter of the projected area. The emulsion of the grains may be either a polydispersed emulsion or a monodispersed emulsion.
The silver halide photographic emulsions to be used in the present invention may be prepared by various methods, for example, those described in Research Disclosure (hereinafter referred to as RD) No. 17643 (December, 1978), pages 22 to 23 (I. Emulsion Preparation and Types); RD No. 18716 (November, 1979), pages 648; RD No. 307105 (November 1989), pages 863 to 865; P. Glafkides, Chimie et Physique Photographique (published by Paul Montel, 1967); G. F. Duffin, Photographic Emulsion Chemistry (published by Focal Press, 1966); and V. L. Zelikman et al, Making and Coating Photographic Emulsion (published by Focal Press, 1964).
Monodispersed emulsions as described in U.S. Pat. Nos. 3,574,628 and 3,655,394 and GB 1,413,748 are also preferably used in the present invention.
Additionally, tabular grains having an aspect ratio of about 3 or more may also be used in the present invention. Tabular grains may easily be prepared in accordance with various methods, for example, as described in Gutoff, Photographic Science and Engineering, Vol. 14, pages 248 to 257 (1970); and U.S. Pat. Nos. 4,434,226, 4,414,310, 4,430,048, and 4,439,520 and GB 2,112,157.
Regarding the crystal structure of the silver halide grains, the grains may have the same halogen composition throughout the whole grain, or they may have different halogen compositions between the inside part and the outside part of one grain, or they may have a layered structure. Further, the grains may have different halogen compositions conjugated by epitaxial bond, or they may conjugated with other compounds than silver halides, such as silver rhodanide or lead oxide. Additionally, a mixture of various grains of different crystalline forms may be employed in the present invention.
The above-mentioned emulsions for use in the present invention may be either surface latent image type ones of forming latent images essentially on the surfaces of the grains or internal latent image type ones of forming latent images essentially in the insides of them, or may also be surface/inside latent image type ones of forming a latent images both on the surfaces of the grains and in the insides of them. Anyhow, the emulsions are needed to be negative emulsions. As an internal latent image type emulsion, it may be a core/shell type internal latent image type emulsion as described in JP-A 63-264740. A methods of preparing such emulsions is described in JP-A 59-133542. The thickness of the shell of the emulsion grains of the type varies depending on the way of developing them, and is preferably from 3 to 40 nm, especially preferably from 5 to 20 nm.
The emulsions are generally physically ripened, chemically ripened and/or spectrally-sensitized. Additives to be used in such a ripening or sensitizing step are described in RD Nos. 17643, 18716 and 307105, and the related descriptions in these references are shown in the table mentioned below.
In the photographic material of the present invention, two or more emulsions which are different from one another in at least one characteristic of light-sensitive silver halide emulsions, such as the grain size, the grain size distribution, the halogen composition, the shape and the sensitivity of the grains, can be incorporated into the same layer.
Surface-fogged silver halide grains as described in U.S. Pat. No. 4,082,553; inside-fogged silver halide grains as described in U.S. Pat. No. 4,626,498 and JP-A 59-214852; as well as colloidal silver may preferably be used into light-sensitive silver halide emulsion layers and/or substantially non-light-sensitive hydrophilic colloid layers. Inside-fogged or surface fogged silver halide grains are such grains that can be non-imagewise uniformly developed irrespective of the non-exposed area and the exposed area of the photographic material. Method of preparing them are described in U.S. Pat. No. 4,626,498 and JP-A 59-214852. The silver halide of forming the inside nucleus of an inside-fogged core/shell type silver halide grain may have a different halogen composition. The inside-fogged or surface-fogged silver halide may be any of silver chloride, silver chlorobromide, silver iodobromide or silver chloroiodobromide. The mean grain size of such fogged silver halide grains is preferably from 0.01 to 0.75 .mu.m, especially preferably from 0.05 to 0.6 .mu.m. The grains may be regular ones. The emulsion containing them may be either a monodispersed one or a polydispersed one. Preferred is a monodispersed one, in which at least 95% by weight or by number of the silver halide grains therein have a grain size to fall within the range of the mean grain size.+-.40%.
The photographic material of the present invention preferably contain non-light-sensitive fine silver halide grains. Non-light-sensitive fine silver halide grains are fine silver halide grains which are not sensitive to the light as imparted to the photographic material for imagewise exposure thereof and are substantially not developed in the step of development processing. These fine grains are desired not previously fogged. The fine silver halide grains have a silver bromide content of from 0 to 100 mol % and, if desired, they may additionally contain silver chloride and/or silver iodide. Preferably, they contain silver iodide in an amount of from 0.5 to 10 mol %. The fine silver halide grains are desired to have a mean grain size (as a mean value of the diameters of the circles corresponding to the projected areas of the grains) of from 0.01 to 0.5 .mu.m, more preferably from 0.02 to 0.2 .mu.m.
The fine silver halide grains may be prepared by the same methods as those of preparing ordinary light-sensitive silver halide grains. The surfaces of the fine silver halide grains do not need to be optically seisitized and spectral sensitization of the grains is unnecessary. However, prior to addition of the fine grains to the coating composition, it is desired to previously add a known stabilizer, such as triazole compounds, azaindene compounds, benzothiazolium compounds, mercapto compounds or zinc compounds, to the coating composition. The fine silver halide grains-containing layer may contain colloidal silver.
The total coated amount of silver (silver in light-sensitive and light-insensitive silver halide and colloidal silver) in the photographic material of the present invention is preferably 6.0 g/m.sup.2 or less, most preferably 4.5 g/m.sup.2 or less.
Various known photographic additives which may be used in the present invention are mentioned in RD's, and the related descriptions therein are shown in the following table.
__________________________________________________________________________Kinds of Additives RD 17643 RD 18716 RD 307105__________________________________________________________________________1 Chemical Sensitizer page 23 page 648, right column page 8662 Sensitivity Enhancer page 648, right column3 Spectrally Sensitizing Agent pages 23 to 24 page 648, right pages 866 to 868 Super Sensitizing Agent column, to page 649, right column4 Brightening Agent page 24 page 647, right column page 8685 Light Absorbent pages 25 to 26 page 649, right column page 873 Filter Dye to page 650, left Ultraviolet Absorbent column6 Binder page 26 page 651, left column page 873 to 8747 Plasticizer, Lubricant page 27 page 650, right column page 8768 Coating Aid pages 26 to 27 page 650, right column pages 875 to 876 Surfactant9 Antistatic Agent page 27 page 650, right column pages 876 to 87710 Mat Agent pages 878 to 879__________________________________________________________________________
Various color couplers can be incorporated into the photographic material of the present invention. The following couplers are especially preferred.
Yellow Couplers
Couplers of formulae (I) and (II) in EP 502,424A; couplers of formulae (1) and (2) in EP 513,496A (especially, Y-28 in page 18); couplers of formula (I) stated in claim 1 of JP-A 5-307248; couplers of formula (I) in U.S. Pat. No. 5,066,576, column 1, lines 45 to 55; couplers of formula (I) in column 0008 in JP-A 4-274425; couplers stated in claim 1 of EP 498,381A1, page 40 especially D-35 in page 18; couplers of formula (Y) in EP 447,969A1, page 4 (especially, Y-1 in page 17 and Y-54 in page 41); couplers of formulae (II) to (IV) in U.S. Pat. No. 4,476,219, column 7, lines 36 to 58 (especially, II-17 and 19 in column 17 and 11-24 in column 19).
Magenta Couplers
In JP-A 3-39737, L-57 (Page 11, right bottom column), L-68 (page 12, right bottom column), L-77 (page 13, right bottom column); in EP 456,257, �A-4!-63 (page 134), �A-4!-73 and �A-4!-75 (page 139); in EP 486,965, M-4 and M-6 (page 26), M-7 (page 27); in JP-A 6-43611, column 0024, M-45; in JP-A 5-204106, column (0036), M-1; in JP-A 4-362631m cikynb (0237) M-22.
Cyan Couplers
In JP-A 4-204843, CX-1, 3, 4, 5, 11, 12, 14 and 15 (page 14 to 16); in JP-A 4-43345, C-7 and C-10 (page 35), C-34 and C-35 (page 37), (I-1) and (I-17) (pages 42 to 43); couplers of formulae (Ia) and (Ib) in claim 1 of JP-A 6-67385.
Polymer Couplers
P-1 and P-5 in JP-A 2-44345, page 11.
Couplers capable of forming colored dyes with pertinent diffusibility may also be used, and those described in U.S. Pat. No. 4,366,237, GB 2,125,570, EP 96,570, and DE 3,234,533 are preferred.
As couplers for correcting unnecessary absorption of colored dyes, are preferably used yellow colored cyan couplers of formulae (CI), (CII), (CIII) and (CIV) described in EP 456,257A1, page 5 (especially, YC-86 in page 84); yellow colored magenta couplers ExM-7 (page 202), Ex-1 (page 249) and Ex-7 (page 251) in EP 456,257A1; magenta colored cyan couplers CC-9 (column 8) and CC-13 (column 10) in U.S. Pat. No. 4,833,069; (2) (column 8) in U.S. Pat. No. 4,837,136; and colorless masking couplers of formula (A) in claim 1 of WO92/11575 (especially compounds illustrated in pages 36 to 45).
As compounds (including couplers) which release a residue of a photographically-useful compound when reacted with an oxidation product of a developing agent, are mentioned the following:
Development Inhibitor-releasing Compounds
Compounds of formulae (I), (II), (III) and (IV) described in EP 378,236A1, page 11 (especially, T-101 in page 30, T-104 in page 31, T-113 in page 36, T-131 in page 45, T-144 in page 51, T-158 in page 58); compounds of formula (I) in EP 436,938A2, page 7 (especially, D-49 in page 51); compounds of formula (1) in Japanese Patent Application No. 4-134523 (especially, (23) in column (0027)); compounds of formulae (I), (II) and (III) in EP 440,195A2, pages 5 to 6 (especially, I-(1) in page 29).
Bleaching Accelerator-releasing Compounds
Compounds of formulae (I) and (I') in EP 310,125A2, page 5 (especially (60) and (61) in page 61); compounds of formula (I) in claim 1 of JP-A 6-59411 (especially, (7) in column (0022)).
Ligand-releasing Compounds
Compounds of LIG-X in claim 1 of U.S. Pat. No. 4,555,478 (especially compounds in column 12, lines 21 to 41).
Leuco Dye-releasing Compounds
Compounds 1 to 6 in U.S. Pat. No. 4,749,641, columns 3 to 8.
Fluorescent Dye-releasing Compounds
Compounds represented by COUP-DYE in claim 1 of U.S. Pat. No. 4,774,181 (especially, Compounds 1 to 11 in columns 7 to 10).
Development Accelerator-releasing or Foggant-releasing Compounds
Compounds of formulae (1), (2) and (3) in U.S. Pat. No. 4,656,123, column 3 (especially, (1-22) in column 25); ExZK-2 in EP 450,637A2, page 75, lines 36 to 38.
Compounds releasing a group that becomes a dye only after released
Compounds of formula (I) in claim 1 of U.S. Pat. No. 4,857,447 (especially, Y-1 to Y-19 in columns 25 to 36).
Preferred additives other than couplers are the following:
Dispersion Media for Oil-soluble Organic Compounds
P-3, 5, 16, 19, 25, 30, 42, 49, 54, 55, 66, 81, 85, 86 and 93 in JP-A 62-215272 (pages 140 to 144).
Latexes for Impregnation of Oil-soluble Organic Compounds
Latexes described in U.S. Pat. No. 4,199,363.
Scavengers for Oxidation Products of Developing Agents
Compounds of formula (I) in U.S. Pat. No. 4,978,606, column, 2, lines 54 to 62 (especially, I-(1), (2), (6) and (12) in columns 4 to 5); compounds of formulae in U.S. Pat. No. 4,923,787, column 2, lines 5 to 10 (especially, Compound 1 in column 3).
Anti-staining Agents
Compounds of formulae (I) to (III) in EP 298,321A, page 4, lines 30 to 33 (especially, I-47 and 72, III-1 and 27 in pages 24 to 28).
Anti-fading Agents
A-6, 7, 20, 21, 23, 24, 25, 26, 30, 37, 40, 42, 48, 63, 90, 92, 94 and 164 in EP 298,321A, pages 69 to 118; II-1 to III-23, especially III-10, in U.S. Pat. No. 5,122,444, column 25 to 38; I-1 to III-4, especially II-2, in EP 471,347A, pages 8 to 12; A-1 to 48, especially A-39 and 42, in U.S. Pat. No. 5,139,931, columns 32 to 40.
Materials for Reducing Effective Amounts of Coloring Enhancers or Color Mixing Preventing Agents
I-1 to II-15, especially I-46, in EP 411,324A, page 5 to 24.
Formalin Scavengers
SCV-1 to 28, especially SCV-8, in EP 477,932A, pages 24 to 29.
Hardening Agents
H-1, 4, 6, 8 and 14 in JP-A 1-214845, page 17; compounds (H-1 to 54) of formulae (VII) to (XII) in U.S. Pat. No. 4,618,573, columns 13 to 23; compounds (H-1 to 76, especially H-14) of formula (6) in JP-A 2-214852, page 8, right bottom column; compounds stated in claim 1 in U.S. Pat. No. 3,325,287.
Development Inhibitor Precursors
P-24, 37 and 39 in JP-A 62-168139, pages 6 to 7; compounds stated in claim 1 in U.S. Pat. No. 5,019,492, especially Compounds 28 and 29 in column 7.
Antiseptics, Antifungal Agents
I-1 to III-43, especially II-1, 9, 10 and 18 and III-25, in U.S. Pat. No. 4,923,790.
Stabilizers, Antifoggants
I-1 to (14), especially I-1 and 60, (2) and (13), in U.S. Pat. No. 4,923,793; Compounds 1 to 65, especially 36, in U.S. Pat. No. 4,952,483, columns 25 to 32.
Chemical Sensitizing Agents
Triphenylphosphine selenide; Compound 50 in JP-A 5-40324.
Dyes
In JP-A 3-156450, a-1 to b-20, especially a-1, 12, 18, 27, 35, and 36, b-5 (pages 15 to 18), and V-1 to 23, especially V-1 (pages 27 to 29); in EP 445627A, F-I-1 to F-II-43, especially F-I-11 and F-II-8 (pages 33 to 55); in EP 457153A, III-1 to 36, especially III-1 and 3, in pages 17 to 28; fine crystalline dispersions of Dye-1 to 124 in WO88/04794, pages 8 to 26; Compounds 1 to 22, especially Compound 1, in EP 319999A, pages 6 to 11; Compounds D-1 to 87 of formulae (1) to (3) in EP 519,306A, pages 3 to 28; Compounds 1 to 22 of formula (I) in U.S. Pat. No. 4,268,622, columns 3 to 10; Compounds (1) to (31) of formula (I) in U.S. Pat. No. 4,923,788, columns 2 to 9.
UV Absorbents
Compounds (18b) to (18r) and 101 to 427 of formula (1) in JP-A 46-3335, pages 6 to 9; in EP 520,938A, Compounds (3) to (66) of formula (I) (pages 10 to 44) and Compounds HBT-1 to 10 of formula (III) (page 14); Compounds (1) to (31) of formula (1) in EP 521,823A, columns 2 to 9.
The present invention may apply to various color photographic materials, such as color negative films for general use or for movie use, color reversal films for slide use or for television use, as well as color papers color positive films and color reversal papers. In addition, it is suitable for lens-combined film units such as those described in JP-B 2-32615 (the term "JP-B" as used herein means an "examined Japanese patent publication") and examined Japanese Utility Model Publication No. 3-39784.
Suitable supports which are usable in the present invention are described in, for example, the above-mentioned RD No. 17643, page 28, RD No. 18716, from page 647, right column to page 648, left column, and RD No. 307105, page 897.
It is desired that the total film thickness of all the hydrophilic colloid layers as provided on the surface of the support of having emulsion layers is 28 microns or less, preferably 23 microns or less, more preferably 18 microns or less, especially preferably 16 microns or less, in the photographic material of the present invention. It is also desired that the photographic material of the invention has a film swelling rate (T.sub.1/2) of 30 seconds or less, preferably 20 seconds or less. The film swelling rate (T.sub.1/2) is defined as follows: 90% of the maximum swollen thickness of the photographic material as processed in a color developer under the condition of 30.degree. C. for 3 minutes and 15 seconds is referred to as a saturated swollen thickness. The time necessary for attaining a half (1/2) of the saturated swollen thickness is defined to be a film swelling rate (T.sub.1/2). The film thickness as referred to herein is one as measured under controlled conditions of a temperature of 25.degree. C. and a relative humidity of 55% (for 2 days); and the film swelling rate (T.sub.1/2) may be measured by a swellometer of the model described in A. Green et al., Photographic Science and Engineering, Vol. 19, No. 2, pages 124 to 129. The film swelling rate (T.sub.1/2) can be adjusted by adding a hardening agent to gelatin used as a binder or by varying the condition of storing the coated photographic material. Additionally, the photographic material of the present invention is desired to have a swelling degree of from 150 to 400%. The swelling degree as referred to herein is calculated from the maximum swollen film thickness as obtained under the above-mentioned condition, on the basis of a formula of:
(maximum swollen film thickness--original film thickness)/(original film thickness).
The photographic material of the present invention may have a hydrophilic colloid layer (this is referred to as a backing layer) having a total dry thickness of from 2 .mu.m to 20 .mu.m on the side opposite to the side having the emulsion layers. It is preferred that the backing layer contains the above-mentioned light absorbent, filter dye, ultraviolet absorbent, antistatic agent, hardening agent, binder, plasticizer, lubricant, coating aid and surfactant. The backing layer is desired to have a swelling degree of from 150 to 500%.
The photographic material of the present invention can be developed by any ordinary method, for example, in accordance with the process described in the above-mentioned RD No. 17643, pages 28 and 29, RD No. 18716, page 615, from left column to right column, and RD No. 307105, pages 880 to 881.
The color developer to be used for development of the photographic material of the present invention is preferably an aqueous alkaline solution consisting essentially of an aromatic primary amine color-developing agent. As the color-developing agent, p-phenylenediamine compounds are preferably used, though aminophenol compounds are also useful. As specific examples and preferred examples, are mentioned the compounds described in EP 556,700A, page 28, lines 43 to 52. These compounds can be used in combination of two or more of them, in accordance with the object.
The color developer generally contains a pH buffer such as alkali metal carbonates, borates or phosphates, and a development inhibitor or anti-foggant such as chlorides, btomides, iodides, benzimidazoles, benzothiazoles or mercapto compounds. If desired, it may also contain various preservatives such as hydroxylamine, diethylhydroxylamine, sulfites, hydrazines (e.g., N,N-biscarboxymethylhydrazine), phenylsemicarbazides, triethanolamine, catechol-sulfonic acids; organic solvents such as ethylene glycol, and diethylene glycol; development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, and amines; dye-forming couplers; competing couplers; auxiliary developing agents such as 1-phenyl-3-pyrazolidone; tackifiers; as well as various chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids. Examples of chelating agents include ethylenediamine-tetraacetic acid, nitrilo-triacetic acid, diethylenetriamine-pentaacetic acid, cyclohexanediamine-tetraacetic acid, hydroxylethylimino-diacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N,N-tetramethylene-phosphonic acid, ethylenediamine-di(o-hydroxyphenylacetic acid) and their salts.
Where the photographic material is processed by a reversal processing, in general, it is first subjected to black-and-white development and then subjected to color development. For the first black-and-white development is used a black-and-white developer, which contains a conventional black-and-white developing agent, for example, dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol, singly or in combination of them. The color developer and the black-and-white developer generally has a pH value of from 9 to 12. The amount of the replenisher to the developer is, though depending upon the color photographic material to be processed, generally 3 liters or less per m.sup.2 of the material to be processed. The effects of the present invention are remarkable when the amount of the replenisher is 600 ml or less per m.sup.2 of the material. It may be reduced to 500 ml or less per m.sup.2 of the material to be processed, by lowering the bromide ion concentration in the replenisher. Where the amount of the replenisher is reduced, it is preferred to reduce the contact area of the surface of the processing solution in the processing tank with air so as to prevent vaporization and aerial oxidation of the solution.
The effect of the processing solution in the processing tank is lowered, when the solution is kept in contact with air in the tank, depending on the opening ratio which is defined by the following formula:
Opening Ratio=(Contact Surface Area (cm.sup.2) of Processing Solution with Air)/(Volume (cm.sup.3) of Processing Solution)
The above-mentioned opening ratio is preferably 0.1 or less, more preferably from 0.001 to 0.05. Various means can be employed for the purpose of reducing the opening ratio, which include, for example, provision of a masking substance such as a floating lid on the surface of the processing solution in the processing tank, employment of the mobile lid described in JP-A 1-82033 and employment of the slit-developing method described in JP-A 63-216050. Reduction of the opening ratio is preferably applied to not only the both steps of color development and black-and-white development but also all the subsequent steps such as bleaching, bleach-fixation, fixation, rinsing and stabilization steps. In addition, the amount of the replenisher to be added may also be reduced by means of suppressing accumulation of bromide ions in the developer. The time for color development is generally within the range of from 2 minutes to 5 minutes, but the processing time may be shortened to 60 seconds or less by elevating the processing temperature, elevating the pH value of the processing solution and/or elevating the concentration of the processing solution.
After color developed, the photographic emulsion layer is generally bleached. Bleaching may be effected simultaneously with fixation (bleach-fixation) or separately therefrom. In order to accelerate the processing speed, a system of bleaching followed by bleach-fixation may also be employed. If desired, a system of using a bleach-fixing bath of continuous two tanks, a system of fixation followed by bleach-fixation, or a system of bleach-fixation followed by bleaching may also be employed, in accordance with the object. As the bleaching agent can be used, for example, compounds of polyvalent metals such as iron(III), as well as peracids, quinones and nitro compounds. Specific examples of the bleaching agent usable in the present invention include organic complexes of iron(III), such as complexes thereof with amino-polycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1, 3-diaminopropanetetraacetic acid or glycol ether-diamine-tetraacetic acid or with organic acids such as citric acid, tartaric acid or malic acid. Among them, aminopolycarboxylato/iron(III) complexes such as ethylenediaminetetraacetato/iron(III) complex and 1,3-diaminopropane-tetraacetato/iron(III) complex are preferred in view of the rapid processability thereof and of prevention of environmental pollution. The aminopolycarboxylato/iron(III) complexes are especially useful both in a bleaching solution and in a bleach-fixing solution. The bleaching solution or bleach-fixing solution containing such aminopolycarboxylato/iron(III) complexes generally has a pH value of from 4.0 to 8.0, but the solution may have a lower pH value for rapid processing.
The bleaching solution, the bleach-fixing solution and the prebath thereof may contain a bleaching accelerating agent, if desired. Various bleaching accelerating agents are known, and examples of the agents which are advantageously used in the present invention include mercapto group- or disulfide group-containing compounds described in U.S. Pat. No. 3,893,858, DE 1,290,812 and 2,059,988, JP-A 53-32736, 53-57831, 53-37418, 53-72623, 53-95630, 53-95631, 53-104232, 53-124424, 53-141623 and 53-28426, RD No. 17129 (July, 1978); thiazolidine derivatives as described in JP-A 50-140129; thiourea derivatives as described in JP-B 45-8506, JP-A 52-20832 and 53-32735 and U.S. Pat. No. 3,706,561; iodide salts as described in DE 1,127,715 and JP-A 58-16235; polyoxyethylene compounds as described in DE 966,410 and 2,748,430; polyamine compounds as described in JP-B 45-8836; other compounds as described in JP-A 49-40943, 49-59644, 53-94927, 54-35727, 55-26506 and 58-163940; and bromide ions. Above all, mercapto group- or disulfide group-containing compounds, in particular, those as described in U.S. Pat. No. 3,893,858, DE 1,290,812 and JP-A 53-95630 are preferred, as having a large accelerating effect. In addition, compounds described in U.S. Pat. No. 4,552,834 are also preferred. These bleaching accelerators may be incorporated into the photographic material of the invention. Where the material of the invention is a picture-taking color photographic material and it is bleach-fixed, these bleaching accelerators are especially effective.
The bleaching solution and bleach-fixing solution may further contain, in addition to the above-mentioned components, various organic acids for the purpose of preventing bleaching stains. Especially preferred organic acids for the purpose are those having an acid dissociating constant (pKa) of from 2 to 5. For instance, acetic acid, propionic acid and hydroxyacetic acid are preferably used.
As the fixing agent in the fixing solution or bleach-fixing solution to be applied to the photographic material of the invention, usable are thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts. Use of thiosulfates is general for the purpose. Above all, ammonium thiosulfate is most widely used. Additionally, combination of thiosulfates and thiocyanates, thioether compounds or thioureas is also preferred. As the preservative to be used in the fixing solution or bleach-fixing solution, preferred are sulfites, bisulfites and carbonyl-bisulfite adduts, as well as sulfinic acid compounds as described in EP 294769A. Further, the fixing solution or bleach-fixing solution may preferably contain various aminopolycarboxylic acids or organic phosphonic acids for the purpose of stabilizing the solution.
It is preferred that the fixing solution or bleach-fixing solution to be used for processing the photographic material of the present invention contains compounds having a pKa value of from 6.0 to 9.0, for the purpose of adjusting the pH value of the solution. As such compounds, preferably added are imidazoles such as imidazole, 1-methylimidazole, 1-ethylimidazole or 2-methylimidazole, in an amount of from 0.1 to 10 mol/liter.
The total time for the desilvering process is preferably shorter within the range of not causing desilvering insufficiency. For instance, the time is preferably from 1 minute to 3 minutes, more preferably from 1 minute to 2 minutes. The processing temperature may be from 25.degree. C. to 50.degree. C., preferably from 35.degree. C. to 45.degree. C. In such a preferred temperature range, the desilvering speed is accelerated and generation of stains in the processed material may effectively be prevented.
In the desilvering process, it is desired that stirring of the processing solution during the process is promoted as much as possible. Examples of reinforced stirring means include a method of running a jet stream of the processing solution to the emulsion-coated surface of the material, as described in JP-A 62-183460; a method of promoting the stirring effect by the use of a rotating means, as described in JP-A 62-183461; a method of moving the photographic material in the processing bath while the emulsion-coated surface of the material is brought into contact with a wiper blade as provided in the processing bath, whereby the processing solution as applied to the emulsion-coated surface of the material is made turbulent and the stirring effect is promoted; and a method of increasing the total circulating amount of the processing solution. Such reinforced stirring means are effective to any of the bleaching solution, bleach-fixing solution and fixing solution. It is considered that reinforcement of stirring of the processing solution would promote application of the bleaching agent and fixing agent into the emulsion layer of the photographic material and, as a result, the desilvering rate would be elevated. The above-mentioned reinforced stirring means is more effective, when a bleaching accelerator is incorporated into the processing solution. Because of the means, therefore, the bleaching accelerating effect could remarkably be augmented, and the fixation preventing effect by the bleaching accelerator could be evaded.
The photographic material of the present invention can be processed with an automatic developing machine. It is desired that the automatic developing machine is equipped with a photographic material-conveying means as described in JP-A 60-191257, 60-191258 and 60-191259. As is noted from the related disclosure of JP-A 60-191257, the conveying means may noticeably reduce the carry-over amount from the previous bath to the subsequent bath and therefore it is extremely effective for preventing deterioration of the processing solution. Because of the reasons, the conveying means is especially effective for shortening the processing time in each processing step and for reducing the amount of the replenisher to each processing bath.
The photographic material of the present invention is generally rinsed in water and/or stabilized, after being desilvered. The amount of the water to be used in the rinsing step can be set in a broad range, in accordance with the characteristic of the photographic material (for example, depending upon the raw material components, such as the coupler and so on) or the use of the material, as well as the temperature of the rinsing water, the number of the rinsing tanks (the number of the rinsing stages), the replenishment system of normal current or countercurrent and other various kinds of conditions. Among these conditions, the relation between the number of the rinsing tanks and the amount of the rinsing water in a multi-stage countercurrent rinsing system can be obtained by the method described in Journal of the Society of Motion Picture and Television Engineers, Vol. 64, pages 248 to 253 (May, 1955). According to the multi-stage countercurrent system described in the above-mentioned reference, the amount of the rinsing water to be used can be reduced noticeably, but because of the prolongation of the residence time of the water in the rinsing tank, bacteria would propagate in the tank so that the floating substances generated by the propagation of bacteria would adhere to the surface of the material as it was processed. Accordingly, the above system would often have a problem. To overcome this problem, the method of reducing calcium and magnesium ions, which is described in JP-A 62-288838, can extremely effectively be used. In addition, isothiazolone compounds and thiabendazoles described in JP-A 57-8542; chlorine-containing bactericides such as chlorinated sodium isocyanurates; and benzotriazoles and other bactericides described in H. Horiguchi, Chemistry of Bactericidal and Fungicidal Agents (1986, by Sankyo Publishing Co., Japan), Bactericidal and Fungicidal Techniques to Microorganisms, edited by Association of Sanitary Technique, Japan (1982, by Kogyo Gijutsu-kai, Japan), and Encyclopeadia of Bactericidal and Fungicidal Agents, edited by Nippon Bactericide and Fungicide Association, Japan (1986), can also be used.
The pH value of the rinsing water to be used for processing the photographic material of the present invention is from 4 to 9, preferably from 5 to 8. The temperature of the rinsing water and the rinsing time can also be set variously in accordance with the characteristics of the photographic material as well as the use thereof, and in general, the temperature is from 15.degree. to 45.degree. C. and the time is from 20 seconds to 10 minutes, and preferably the temperature is from 25.degree. to 40.degree. C. and the time is from 30 seconds to 5 minutes. Alternatively, the photographic material of the present invention may also be processed directly with a stabilizing solution in place of being rinsed with water. For the stabilization, any known methods, for example, as described in JP-A 57-8543, 58-14834 and 60-220345, can be employed.
In addition, the material can also be stabilized, following the rinsing step. As one example of the case, there may be mentioned a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath for picture-taking color photographic materials. Examples of the dye stabilizers include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine and aldehyde-sulfite adducts. The stabilizing bath may also contain various chelating agents and fungicides.
The overflow of the finsing and/or stabilizing solutions caused by addition of replenishers thereto may be re-used in the other steps such as a desilvering step.
Where the photographic material is processed with an automatic developing machine system and the processing solution in the step are evaporated and thickened, it is desired to add water to the solutions so as to compensate the concentration of the solutions.
The photographic material of the present invention can contain a color developing agent for the purpose of simplifying and accelerating the processing of the material. For incorporation of a color developing agent into the photographic material, various precursors of the agent are preferably used. For example, there are mentioned indoaniline compounds described in U.S. Pat. No. 3,342,597, Schiff base compounds described in U.S. Pat. No. 3,342,599 and RD Nos. 14850 and 15159, aldole compounds described in RD No. 13924, metal complexes described in U.S. Pat. No. 3,719,492 and urethane compounds described in JP-A 53-135628, as the precursors.
The photographic material of the present invention can contain various kinds of 1-phenyl-3-pyrazolidones, if desired, for the purpose of accelerating the color developability thereof. Specific examples of these compounds are described in JP-A 56-64339, 57-144547 and 58-115438.
The processing solutions to be used for processing the photographic material of the invention are used at 10.degree. C. to 50.degree. C. In general, a processing temperature of from 33.degree. C. to 38.degree. C. is standard, but the temperature may be made higher than 38.degree. C. so as to accelerate the processing or to shorten the processing time, or on the contrary, the temperature may be made lower than 33.degree. C. so as to improve the quality of images formed and to improve the stability of the processing solution.

The following examples are intended to illustrate the present invention but not to limite it in any way.
EXAMPLE 1
A multilayer color photographic light-sensitive material, sample 101, was prepared by multicoating the layers each having the following composition on a cellulose triacetate film having a subbing layer.
Light-sensitive Layer Composition
The main compounds used for each layer are classified as follows.
Exc: Cyan Coupler
ExM: Magenta Coupler
ExY: Yellow Coupler
ExS: Sensitizing Dye
UV: Ultraviolet Absorbent
HBS: Hogh-boling Organic Solvent
H: Gelatin Hardening Agent
The numeral corresponding to each component is a coated amount shown by a g/m.sup.2 unit and the numeral for the silver halide is shown by the coated amount converted as silver. In this case, however, the numeral for a sensitizing dye is the coated amount shown by a mole unit to mole of the silver halide in the same layer.
(Sample 101)
______________________________________1st Layer (Antihalation Layer)Black Colloid Silver (Ag) 0.18Gelatin 1.40ExM-1 0.11ExF-1 3.4 .times. 10.sup.-3HBS-1 0.162nd Layer (Interlayer)ExC-2 0.030UV-1 0.020UV-2 0.020UV-3 0.060HBS-1 0.05HBS-2 0.020Polyethyl Acrylate Latex 0.080 (solid)Gelatin 0.903rd Layer (Low-Sensitive Red-Sensitive Emulsion Layer)Emulsion A (Ag) 0.23Emulsion B (Ag) 0.23ExS-1 5.0 .times. 10.sup.-4ExS-2 1.8 .times. 10.sup.-5ExS-3 5.0 .times. 10.sup.-4ExC-1 0.050ExC-3 0.030ExC-4 0.14ExC-5 3.0 .times. 10.sup.-3ExC-7 1.0 .times. 10.sup.-3ExC-8 0.010Cpd-2 0.005HBS-1 0.10Gelatin 0.904th Layer (Intermediate-Sensitive Red-Sensitive Emulsion Layer)Emulsion C (Ag) 0.70ExS-1 3.4 .times. 10.sup.-4ExS-2 1.2 .times. 10.sup.-5ExS-3 4.0 .times. 10.sup.-4ExC-1 0.15ExC-2 0.060ExC-4 0.050ExC-5 0.010ExC-8 0.010Cpd-2 0.023HBS-1 0.11Gelatin 0.605th Layer (High-Sensitive Red-Sensitive Emulsion Laye)Emulsion D (Ag) 1.62ExS-1 2.4 .times. 10.sup.-4ExS-2 1.0 .times. 10.sup.-5ExS-3 3.0 .times. 10.sup.-4ExC-1 0.10ExC-3 0.050ExC-5 2.0 .times. 10.sup.-3ExC-6 0.010ExC-8 0.010Cpd-2 0.025HBS-1 0.20HBS-2 0.10Gelatin 1.306th Layer (Intermediate Layer)Cpd-1 0.090HBS-1 0.05Polyethylene Acrylate Latex 0.15 (solid)Gelatin 1.107th Layer (Low-Sensitive Green-Sensitive Emulsion Layer)Emulsion E (Ag) 0.24Emulsion F (Ag) 0.24ExS-4 4.0 .times. 10.sup.-5ExS-5 1.8 .times. 10.sup.-4ExS-6 6.5 .times. 10.sup.-4ExM-1 5.0 .times. 10.sup.-3ExM-2 0.28ExM-3 0.086ExM-4 0.030ExY-1 0.015HBS-1 0.30HBS-3 0.010Gelatin 0.858th Layer (Intermediate-sensitive Green-Sensitive Emulsion Layer)Emulsion G (Ag) 0.94ExS-4 2.0 .times. 10.sup.-5ExS-5 1.4 .times. 10.sup.-4ExS-6 5.4 .times. 10.sup.-4ExM-2 0.14ExM-3 0.045ExM-5 0.020ExY-1 7.0 .times. 10.sup.-3ExY-4 2.0 .times. 10.sup.-3ExY-5 0.020HBS-1 0.16HBS-3 8.0 .times. 10.sup.-3Gelatin 0.809th Layer (High-Sensitive Green-Sensitive Emulsion Layer)Emulsion H (Ag) 1.29ExS-4 3.7 .times. 10.sup.-5ExS-5 8.1 .times. 10.sup.-5ExS-6 3.2 .times. 10.sup.-4ExC-1 0.010ExM-1 0.020ExM-4 0.050ExM-5 0.020ExY-4 5.0 .times. 10.sup.-3Cpd-3 0.050HBS-1 0.20HBS-2 0.08Polyethyl Acrylate Latex 0.26 (solid)Gelatin 1.4510th Layer (Yellow Filter Layer)Yellow Colloid Silver (Ag) 7.5 .times. 10.sup.-3Cpd-1 0.13Cpd-4 7.5 .times. 10.sup.-3HBS-1 0.60Gelatin 0.6011th Layer (Low-Sensitive Blue-Sensitive Emulsion Layer)Emulsion I (Ag) 0.25Emulsion J (Ag) 0.25Emulsion K (Ag) 0.10ExS-7 8.0 .times. 10.sup.-4ExC-7 0.010ExY-1 5.0 .times. 10.sup.-3ExY-2 0.40ExY-3 0.45ExY-4 6.0 .times. 10.sup.-3ExY-6 0.10HBS-1 0.30Gelatin 1.6512th Layer (High-Sensitive Blue-Sensitive Emulsion Layer)Emulsion L (Ag) 1.30ExS-7 3.0 .times. 10.sup.-4ExY-2 0.15ExY-3 0.06ExY-4 5.0 .times. 10.sup.-3Cpd-2 0.10HBS-1 0.070Gelatin 1.2013th Layer (1st Protective Layer)UV-2 0.10UV-3 0.12UV-4 0.30HBS-1 0.10Gelatin 2.5014th Layer (2nd Protective Layer)Emulsion M (Ag) 0.10H-1 0.37B-1 (diameter 1.7 .mu.m) 5.0 .times. 10.sup.-2B-2 (diameter 1.7 .mu.m) 0.15B-3 0.05S-1 0.20Gelatin 0.70______________________________________
Furthermore, each layer suitably contained one or more of W-1 to W-3, B-4 to B-6, F-1 to F-17, an iron salt, a lead salt, a gold salt, a platinum salt, an iridium salt, a palladium salt, and a rhodium salt for improving the storage stability, the process property, the pressure durability, a antifungal-antibacterial property, the antistatic property, the coating property.
In addition, in the case of incorporating Cpd-4 in 10th Layer (yellow filter layer), the compound was dispersed in a solid form according to the method described in PCT Patent Publication (unexamined) No. 88/4794.
The emulsions A to M used for preparing the sample 101 described above were AgBrI emulsion and are shown in Table 1 below in detail.
TABLE 1__________________________________________________________________________ Intergrain iodine Coefficient distribution Mean grain of variation Ratio of Grain Form Average AGI variation size (sphere- relative to diameterEmulsion (Halogen Structure) content (%) coefficient (%) equivalent (.mu.m) grain sizes (%) /thickness__________________________________________________________________________A Circular Tabular 0 -- 0.45 15 5.5 (uniform Structure)B Cubic (Shell high- 1.0 -- 0.20 8 1 iodine, double struct.)C Tetradecahedral 4.5 25 0.85 18 1 (intermediate high- iodine triple struct.)D Hexagonal Tabular 2.0 16 1.10 17 7.5 (outer side high iodine structure)E Circular Tabular 1.0 -- 0.45 15 3.0 (outer side high iodine structure)F Octahedral (core 6.0 22 0.25 8 1 high iodine double struct.)G Tetradecahedral 4.5 19 0.85 19 1 (intermediate high iodine triple struct.)H Hexagonal Tabular 3.5 16 1.10 16 6.8 (outer side high- iodine structure)I Circular Tabular 2.0 15 0.45 15 6.0 (center portion high-iodine structure)J Cubic (uniform 1.0 10 0.30 8 1 structure)K Tetradecahedral 18.0 8 0.80 18 1 (core high- iodine triple structure)L Hexagonal Tabular 12.0 12 1.35 22 12.0 (intermediate high- iodine structure)M Light-insensitive 1.0 -- 0.04 15 1 fine particles (uniform structure)__________________________________________________________________________
In Table 1;
(1) Each of the emulsions I to L was reduction sensitized at the preparation of the silver halide grains using thiourea dioxide and thiosulfonic acid according to the Example in JP-A-2-191938 (corresponding to U.S. Pat. No. 5,061,614).
(2) Each of the emulsions A to L was subjected to a gold sensitization, a sulfur sensitization, and a selenium sensitization in the presence of the spectral sensitizing dyes added into each light-sensitive silver halide emulsion layer and sodium thiocyanate according to the Example in JP-A-3-237450 (corresponding to EP 443,453A).
(3) At the preparation of the tabular silver halide grains, a low-molecular weight gelatin was used according to the Example in JP-A-1-158426.
(4) In the tabular silver halide grains, the transition lines as described in JP-A-3-237450 were observed using a high-voltage electromicroscope.
In addition, in the case of preparing the sample described above, the couplers and the additives for each layer were dispersed in an aqueous gelatin solution by the method shown in Table 2 below and the addition method for each layer is shown in Table 3 below.
TABLE 2______________________________________DispersionMethod Method______________________________________A Method of neutralizing a homogeneous aqueous solution of the couplers, the high-boiling organic solvents, the surface active agent, sodium hydroxide, n-propanol, and other additives to deposite and disperse these additives.B Method of adding a homogeneous n-propanol solution of the couplers, the high-boiling organic solvents, and other additives to an aqueous solution of the suface active agent to deposite and disperse these additives.C Method of mixing a solution of the couplers, the high-boiling organic solvents, the surface active agent, a low-boiling organic solvent, and other additives with an aqueous solution of gelatin and the surface active agent followed by stirring and dispersing by emulsification, and removing the low-boiling organic solvent by distillation.D Method of removing the organic solvents from the mixture by water washing or a ultrafiltration after dispersing in the method______________________________________ C.
TABLE 3______________________________________ Dispersing Mean Dispersed GrainLayer Method Size �nm!______________________________________Layer 3 C 133Layer 4 C 130Layer 5 D 40Layer 7 C 135Layer 8 C 60Layer 9 A 40Layer 11 C 125Layer 12 B 80______________________________________
Then, the compounds used for preparing the Sample 101 described above are shown below. ##STR8##
By following the same procedure as the preparation of the Sample 101, except that an equimolar amount of each of the compounds shown in Table 4 below was used in place of the compound ExC-4 used in the 3rd layer, each of Samples 102 to 107 was prepared.
Each of the Samples 101 to 107 was subjected to a sensitometric exposure according to an ordinary manner under the conditions of a color temperature of 4800.degree. K., 5 CMS, and 1/100 second, processed by the processing conditions shown in the Processing Method 1 shown below, then, the photographic characteristics were evaluated, and the results shown in Table 4 below were obtained.
Processing Method 1
Processing Steps
__________________________________________________________________________ Tank Processing Processing Replenising VolumeStep Time Temperatur Amount (ml) (liter)__________________________________________________________________________Color 3 min. 15 sec. 38.degree. C. 45 10DevelopmentBleach 30 sec. 38.degree. C. 20 4 All of the overflow amount of the bleach liquid was introduced into the blix tankBlix 2 min. 30 sec. 38.degree. C. 30 8Wash (1) 40 sec. 35.degree. C. Countercurrent 4 system from (2) to (1)Wash (2) 60 sec. 38.degree. C. 30 4Stabiliza 45 sec. 38.degree. C. 20 4tionDrying 1 min. 15 sec. 55.degree. C.__________________________________________________________________________ (*): The replenishing amount was per 35 mm .times. 1.1 meters (corresponding to one 24exposure roll film).
Then, the compositions of the processing liquids are shown below.
__________________________________________________________________________ Tank ReplenisherColor Developer liquid (g) (g)__________________________________________________________________________Diethylenetriaminepentaacetic Acid 1.0 1.11-Hydroxyethylidene-1,1-diphosphonic 2.0 2.0AcidSodium Sulfite 4.0 4.4Potassium Carbonate 30.0 37.0Potassium Bromide 1.4 0.7Potassium Iodide 1.5 mg --Hydroxylamine Sulfate 2.4 2.84-�N-Ethyl-N-(.beta.-hydroxyethyl)-amino!- 4.5 5.52-methylaniline sulfateWater to make 1 liter 1 literpH (adjusted with KOH and H.sub.2 SO.sub.4) 10.05 10.10Bleach Liquid (Tank liquid = Replenisher)Ethylenedaminetetraacetic Acid Ferric 120.0 gAmmonium DihydrateEthylenediaminetetraacetic Acid Disodium Salt 10.0 gAmmonium Bromide 100.0 gAmonium Nitrate 10.0 gBleach Accelerator 0.005 mole(CH.sub.3).sub.2 N--CH.sub.2 CH.sub.2 S--S--CH.sub.2 CH.sub.2 --N(CH.sub.3).sub.2.2HClAqeous Aminonia (27%) 15.0 mlWater to make 1.0 literpH (adjusted with aqueous ammonia and HNO.sub.3) 6.3__________________________________________________________________________ ReplenisherBlix Liquid Tank Liquid__________________________________________________________________________Ethylenediaminetetraacetic Acid 50.0 g --Ferric Ammonium DihydrateEthylenediaminetetraacetic Acid 5.0 g 2.0 gDisodium SaltSodium Sulfite 12.0 g 20.0 gAqueous Ammonium Thiosulfate 240.0 ml 400.0 mlSolution (700 g/liter)Aqueous Ammonia (27%) 6.0 ml --Water to make 1.0 liter 1.0 literpH (adjusted with aqueous ammonia 7.2 7.3and CH.sub.3 COOH)__________________________________________________________________________
Wash Water (Tank Liquid=Replenisher)
City water was passed through a mixed bed column packed with a H-type strong acidic cation exchange resin (Amberlite 1R-120B, trads name, made by Rohm and Haas Company) and an OH-type strong basic anion exchange resin (Amberlite IR-400, trade name, made by Rohm and Haas Company) to reduce calcium and magnesium ion concentrations below 3 mg/liter and then 20 mg/liter of sodium dichloroisocyanurate and 0.15 g/liter of sodium sulfate were added thereto. The pH thereof was in the range of from 6.5 to 7.5.
Stabilization Liquid (Tank Liquid=Replenisher)
______________________________________Sodium p-toluensulfinate 0.03 gPolyoxyethylene-p-monononylphenyl ether 0.2 g(average molecular degree 10)Ethylenediaminetetraacetic Acid Disodium Salt 0.05 g1,2,4-Trizole 1.3 g1,4-Bis(1,2,4-triazol-1-ylmethyl)piperazine 0.75 gWater to make 1.0 literpH 8.5 g______________________________________
In Table 4, the color density of RL means the color density of the red-sensitive emulsion layer at the exposure amount corresponding to the exposure amount 100 CMS.
TABLE 4______________________________________Sample Compound Used for RL ColorNo. 3rd Layer RL Dmin Density Remarks______________________________________101 ExC-4 0.28 1.22 Comparative102 Comparative 0.29 1.10 Comparative compound (B-2)103 Compound (A-10) 0.28 1.60 Invention104 Compound (A-6) 0.28 1.67 Invention105 Compound (A-1) 0.29 1.78 Invention106 Compound (A-4) 0.28 1.75 Invention107 Compound (A-3) 0.27 1.65 Invention______________________________________
From the results shown in Table 4, it can be seen that by using the compounds of the present invention, the color density of the red-sensitive emulsion layers is increased, whereby the effect of the present invention is confirmed. Also, since in the comparative examples and the examples of this invention, there is almost no difference in the changes of RL Dmin (minimum densities of the red-sensitive emulsion layers), it can be seen that the effect of the present invention acts imagewise.
EXAMPLE 2
Each of the samples 101 to 107 as prepared in Example 1 was processed under the processing conditions of Processing Method 2 shown below, the same evaluations as in Example 1 were carried out, and the results are shown in Table 5 below.
Processing Method 2
______________________________________Processing Step Temperature Time______________________________________Color Development 45.degree. C. 60 sec.Blix 45.degree. C. 60 sec.Wash (1) 40.degree. C. 15 sec.Wash (2) 40.degree. C. 15 sec.Wash (3) 40.degree. C. 15 sec.Stabilization 40.degree. C. 15 sec.Drying 80.degree. C. 60 sec.______________________________________
For wash step, a 3 tank countercurrent system of from (3) to (1) was employed.
The composition for the each processing liquid was as follows.
Color Developer
______________________________________Diethylenetriaminepentaacetic Acid 1.0 g1-Hydroxyethylidene-1,1-diphosphonic Acid 2.0 gSodium Sulfite 4.0 gPotassium Carbonate 40.0 gPotassium Bromide 1.4 gPotassium Iodide 1.5 mgHydroxylamine Sulfate 2.4 g4-�N-Ethyl-N-(.beta.-hydroxyethyl)amino!-2- 7.0 gmethylaniline SulfateWater to make 1.0 literpH (adjusted with potassium hydroxide and 10.05sulfuric acid)Blix LiquidChelating Agent ({N,N,N'-tris(carboxylmethyl)- 0.17 moleN-(2-carboxyphenyl)}ethylenediamine)Ferric Nitrate 9H.sub.2 O 0.15 moleAmmonium Thiosulfate 1.25 molesAmmonium Sulfite 0.10 moleMetacarboxybenzenesulfinic Acid 0.05 moleWater to make 1.0 literpH (adjusted with acetic acid and ammonia) 5.8______________________________________
Wash Water
Wash water having the same composition as that of wash water described in Example 1 was used.
Stabilization Liquid
The liquid having the same composition as that of the stabilization liquid described in Example 1 was used.
TABLE 5______________________________________Sample Compound Used for RL ColorNo. 3rd Layer RL Dmin Density Remarks______________________________________101 ExC-4 0.28 0.88 Comparative102 Comparative 0.29 0.76 Comparative compound (B-2)103 Compound (A-10) 0.28 1.63 Invention104 Compound (A-6) 0.28 1.62 Invention105 Compound (A-1) 0.29 1.77 Invention106 Compound (A-4) 0.28 1.79 Invention107 Compound (A-3) 0.27 1.75 Invention______________________________________
From the results shown in Table 5, the effect of the present invention is remarkable. Also, from the comparison of the results shown in Table 5 with the results shown in Table 4, the effect of the present invention in the processing method of a short processing time is remarkable. This is assumed to be that in processing of a short time, the diffusion of the color developing agent becomes the rate-determining step of the development rate.
EXAMPLE 3
By following the same procedure as preparing the sample 101 described above except that the equimolar amount of each of the compounds shown in Table 6 below was used in place of compound ExM-2 in the 7th layer, each of samples 108 to 113 was prepared.
Then, each of the Samples 108 to 113 was subjected to a sensitometric exposure according to an ordinary method under the conditions of a color temperature of 4800.degree. K., 5 CMS, and 1/100 second, processed under the processing conditions shown in the Processing Method 1 described in Example 1, then the photographic characteristics of each sample thus processed were evaluated, and the results obtained are shown in Table 6 below.
TABLE 6______________________________________Sample Compound Used for GL ColorNo. 7th Layer GL Dmin Density Remarks______________________________________101 ExM-2 0.53 1.42 Comparative108 Comparative 0.54 1.43 Comparative compound (B-3)109 Compound (A-27) 0.53 1.94 Invention110 Compound (A-24) 0.53 1.95 Invention111 Compound (A-23) 0.53 1.88 Invention112 Compound (A-22) 0.54 1.94 Invention113 Compound (A-26) 0.54 1.92 Invention______________________________________
In Table 6, the color density of GL means the color density of the green-sensitive emulsion layer at the exposure amount corresponding to the exposure amount 100 CMS.
As is clear from the results shown in Table 6, by using the compounds of the present invention, the color density of the green-sensitive emulsion layer is increased, whereby the effect of this invention is confirmed.
EXAMPLE 4
Each of the Sample 101 and the Samples 108 to 113 described in Example 3 was subjected to a sensitometric exposure according to an ordinary method under the conditions of the color temperature of 4800.degree. K., 5 CMS, and 1/100 second, processed under the processing conditions shown in the Processing Method 1 described in Example 1, then the photographic characteristics were evaluated, and the results obtained are shown in Table 7 below. In Table 7, the color density of GL means the color density of the green-sensitive emulsion layers at the exposure amount corresponding to the exposure amount 100 CMS.
TABLE 7______________________________________Sample Compound Used for GL ColorNo. 7th Layer GL Dmin Density Remarks______________________________________101 ExM-2 0.52 1.18 Comparative108 Comparative 0.53 1.20 Comparative compound (B-3)109 Compound (A-27) 0.52 1.86 Invention110 Compound (A-24) 0.52 1.92 Invention111 Compound (A-23) 0.52 1.86 Invention112 Compound (A-22) 0.53 1.97 Invention113 Compound (A-26) 0.52 1.96 Invention______________________________________
From the results shown in Table 7, the effect of the present invention is clear. Also, from the comparison of the results in Table 7 with the results in Table 6, it can be seen that the effect of this invention in the processing method of a short time is remarkable. This is assumed to be that in processing of a short time, the diffusion of the color developer becomes the rate-determining step of the development rate.
EXAMPLE 5
By following the same procedure as the preparation of the Sample 101 described in Example 1 except that the equimolar amount of each of the compounds shown in Table 8 below was used in place of the compound ExY-2 used in the 11th Layer, each of Samples 501 to 503 was prepared.
Then, each of the Samples 501 to 503 was subjected to a sensitometric exposure according to an ordinary method under the conditions of a color temperature of 480.degree. K., 5 CMS, and 1/100 second, processed under the processing conditions shown by the Processing Method 1 described in Example 1, then the photographic characteristics were evaluated, and the results obtained are shown in Table 8 below. In Table 8, the color density of BL means the color density of the blue-sensitive emulsion layers at the exposure amount corresponding to the exposure amount 100 CMS.
TABLE 8______________________________________Sample Compound Used for GL ColorNo. 11th Layer GL Dmin Density Remarks______________________________________101 ExY-2 0.93 1.82 Comparative501 Comparative 0.94 1.72 Comparative compound (B-1)502 Compound (A-2) 0.93 2.35 Invention503 Compound (A-11) 0.93 2.12 Invention______________________________________
From the results shown in Table 8, it can be seen that by using the compounds of the present invention, the color density of the blue-sensitive emulsion layers is increased, whereby the effect of the present invention is confirmed.
EXAMPLE 6
Then, each of the Sample 101 and the Samples 501 to 503 described in Example 5 was subjected to a sensitometric exposure according to an ordinary method under the conditions of a color temperature of 4800.degree. K., 5 CMS, and 1/100 second, processed under the processing conditions shown by the Processing Method 2 described in Example 2, then the photographic characteristics were evaluated, and the results obtained are shown in Table 9 below. In Table 9, the color density of BL shows the color density of the blue-sensitive emulsion layers corresponding to the exposure amount 100 CMS.
TABLE 9______________________________________Sample Compound Used for BL ColorNo. 11th Layer BL Dmin Density Remarks______________________________________101 ExY-2 0.92 1.63 Comparative501 Comparative 0.93 1.52 Comparative compound (B-1)502 Compound (A-2) 0.93 2.30 Invention503 Compound (A-11) 0.92 2.10 Invention______________________________________
From the results shown in Table 9, the effect of the present invention is clear. Also, from the comparison of the results in Table 9 with the results in Table 8, it can be seen that the effect of the present invention in the processing method of a short time is remarkable. This is assumed to be that in processing of a short time, the diffusion of the color developing agent becomes the rate-determining step of the development rate.
EXAMPLE 7
Each of the Samples 101 to 107 described above was processed by the processing method described in JP-A-4-274425 (corresponding to U.S. Pat. No. 5,296,339), whereby the continuous processing property thereof was tested. In this case, however, the processing time for the color development was 2 minutes and 30 seconds. As the result of testing by changing the replenishing amount (1200 ml to 300 ml) as described in Table 1-2 described in foregoing JP-A-4-274425, it was clear that in the samples of the present invention, lowering of the color density was less and low replenishing processing could be employed.
EXAMPLE 8
The sample 103 described in Example 1 of JP-A-4-145433 (corresponding to U.S. Pat. No. 5,264,332) and Sample 801 prepared by using the equimolar amount of the coupler A-31 of the present invention in place of ExY used for the 1st Layer of the sample 103 were prepared. Each of the samples was exposed and processed as described above in Example 1 of JP-A-4-145433. In this case, however, the development process was carried out by changing the processing time of the color development to 35 seconds. The results showed that the Sample 801 of the present invention showed less lowering of the color density as compared with the Comparative Sample 103 and was excellent.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

Number	Name	Date
4409323	Sato et al.	Oct 1983
4526863	Mihayashi et al.	Jul 1985
4678743	Yamada et al.	Jul 1987
4741994	Ichijima et al.	May 1988
4912025	Platt et al.	Mar 1990
4977073	Ishige et al.	Dec 1990
5234800	Begley et al.	Aug 1993
5264330	Yoshida et al.	Nov 1993
5296339	Fujita et al.	Mar 1994
5346809	Takada et al.	Sep 1994
5492796	Ogiyama et al.	Feb 1996

Number	Date	Country
51-26038	Mar 1976	JPX
61-156126	Jul 1986	JPX

Silver halide color photographic material and processing method thereof

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