Process of forming silver halide color photographic images

Abstract

 A photographic image-forming process capable of obtaining prints excellent in color reproduction, especially, those in skin and yellow colors is provided, comprising;
   making use of a silver halide color photographic light sensitive material for picture-taking use comprising each of blue-, green- and red-sensitive emulsion layers; and
   printing an original color-image resulted from the light sensitive material on a silver halide color photographic light sensitive material for printing-use comprising yellow-, magenta- and cyan-color developing layers;
   wherein both of the green- and yellow-color developing layers contain the yellow couplers represented by the following Formula [I];

Description

FIELD OF THE INVENTION

[0001] This invention relates to a process of forming silver halide color photographic images and particularly to a process of forming silver halide color photographic images excellent in color-hue reproduction.

BACKGROUND OF THE INVENTION

[0002] In recent years, the image quality of silver halide multilayered color photographic light sensitive materials have remarkably been made higher. To be more concrete, following the recent progress of the color photographic light sensitive materials, the levels of the image-sharpness and graininess thereof, in particular, have considerably been higher and, therefore, there is mostly no complaint on color prints and slide photographs each having the picture sizes of the order of the so-called service-size which generally available to the users.

[0003] Among the four elements of image quality, however, the color-hue fidelity, that has been said so far that the reproduction can hardly be achieved in photography, is still not satisfactorily improved even in the present stage, although it is true that the color purity has been improved to be bright and reproduced to be emphasized to some extent in some cases. For example, purple colors such as purple and reddish purple or green colors such as bluish green and yellowish green each having a high reflectance to the so-called near-infrared radiation longer than 600nm, these colors each are reproduced to be quite different from the very actual colors, so that the users are sometimes disappointed.

[0004] The factors seriously involved in color reproducibility include, for example, the spectral photosensitivity distribution and interimage effect (hereinafter abbreviated to IIE) of color photographic light sensitive materials. The color reproduction improvements made by IIE are disclosed in, for example, Japanese Patent Examined Publication No. 58-7987/1983 and so forth. To be more concrete, in silver halide multilayered color photographic light sensitive materials, it has been known that the improvement effects of a color reproduction can be displayed by the following manner; a development inhibitor is released from a compound which produces imagewise development inhibitor upon reacting with the oxidized products of a developing agent (that is so-called a DIR compound) or a precursor thereof and thereby the developments of other color-sensitive layers can be inhibited by the resulting development inhibitor, so that an IIE can be produced to display the improvement effects of the color reproduction.

[0005] The above-mentioned technique can contribute mainly to the improvements of the color purity among the color reproducibilities. The above-mentioned DIR compounds have also had a defect that a color hue may be varied if the magnitude and range of interimage action thereof cannot be well-controlled, though it can make a color purity higher.

[0006] As for the spectral photosensitivity distribution of a light sensitive materials for photographing use, on the other hand, Japanese Patent Examined Publication No. 49-6207/1974 discloses a technique that the spectral photosensitivity distribution of blue-sensitive and red-sensitive silver halide emulsion layers (hereinafter abbreviated to a blue-sensitive and red-sensitive layers, respectively) are put close to that of a green-sensitive layer so as to reduce the color reproduction variations caused by a difference of light sources used for taking-pictures.

[0007] However, the above-mentioned technique has the following defects; that the technique cannot only be used as a means for improving the colors having the afore-mentioned difficulties in color-hue reproducibility, but also the photosensitivity is seriously lowered; that the color reproducible regions are narrowed because the spectral photosensitivity distributions are overlapped among color-sensitive layers, though the technique can reduce the reproduction variations caused by changes in color-temperature; and, resultingly, that the resulting colors are made dark and dull without reproducing any highly chromatic colors.

[0008] When shifting the photosensitivity of a red-sensitive layer to a shorter wavelength region, the chromaticness is lowered and, when this is the case, a skin-color reproducibility particularly essential for color-photographic reproduction is affected. When this is the case, there causes a defect that a healthy flush peculiar to a skin may be lost to result in a poor color reproduction devoid of animation.

[0009] The technique of specifying a spectral photosensitivity and an IIE is disclosed in Japanese Patent Publication Open to Public Inspection (hereinafter abbreviated to as JP OPI Publication) No. 62-160449/1987, wherein each of the orientation of IIE is specified for every color-sensitive layer.

[0010] Further, JP OPI Publication No. 62-160448/1987 discloses a technique that a cyan photosensitive layer is so provided as to exert the IIE thereof upon a red-sensitive layer, resulting in the photosensitivity resembling falsewise the spectral photosensitivity of the human eye. To be concrete, besides the inherent blue-, green- and red-sensitive layers, an IIE color developable layer (i.e., a cyan photosensitive layer) is required for providing the IIE. Therefore, this technique has such a defect as that a silver amount used is increased or that the production cost is made higher, and it cannot be said that the effects of the technique are satisfactory.

[0011] In every technique described above, the color reproducibility is still not satisfactory, but an image-forming technique excellent in color reproduction has been awaited.

SUMMARY OF THE INVENTION

[0012] This invention is to solve the above-mentioned problems. It is an object of the invention to provide a silver halide color photographic image-forming process excellent in color reproduction and particularly in skin-color and yellow-color reproduction.

[0013] As the results that the present inventors have studied energetically, it was discovered that the above-mentioned objects of the invention can be achieved in the following process, and the invention has been made accordingly.

[0014] The objects of the invention can be achieved with a silver halide color photographic image-forming process comprising;
   making a color original image on a silver halide color photographic light sensitive material for taking-picture use comprising a support having thereon a blue-sensitive silver halide emulsion layer (named B-layer), a green-sensitive silver halide emulsion layer (named G-layer) and a red-sensitive silver halide emulsion layer (named R-layer); and
   printing the color original image resulted from the light sensitive material on a silver halide color photographic light sensitive material for printing use comprising a support having thereon a yellow-dye forming layer (named Y-layer), a magenta-dye forming layer (named M-layer) and a cyan-dye forming layer (named C-layer);
   wherein both of the B- and Y-layer contain an yellow coupler represented by the following Formula [I];


   wherein R¹ represents an alkyl, cycloalkyl or aryl group; R⁰ represents an aryl, alkoxy, aryloxy or trifluoromethyl group; R³ represents a group substitutable to a benzene ring; n is an integer of 0 or 1; X¹ represents a group capable of splitting off when coupling to an oxidized product of a color developing agent; and Y¹ represents a ballast group.

DETAILED DESCRIPTION OF THE INVENTION

[0015] First, the silver halide color photographic light sensitive materials for taking-picture use will be detailed below.

[0016] In the spectral photosensitivity of the B-layer of the silver halide color photographic light sensitive materials for taking-picture use, a wavelength λ_Bmax capable of giving a maximum sensitivity has a relation of, preferably, 400nm ≦ λ_Bmax ≦ 470nm and, more preferably, 410nm ≦ λ_Bmax ≦ 460nm.

[0017] In the spectral photosensitivity of the G-layer, a wavelength λ_Gmax capable of giving a maximum sensitivity has a relation of, preferably, 525nm ≦ λ_Gmax ≦ 560nm. Further, the spectral photosensitivity S_G570 at 570nm of the G-layer is, preferably, not more than 40% of the spectral photosensitivity at λ_Gmax. When this is the case, the skin-color portions of a resulting printed image are pink-like tinted so as to reproduce a preferable skin-color. Spectral photosensitivity S_G570 of a G-layer in the above-mentioned 570nm is to be, preferably, not more than 20% and, more preferably, not more than 15%.

[0018] The spectral photosensitivity of a R-layer shall not be limitative, but wavelength λ_Rmax capable of giving a maximum photosensitivity has a relation of, preferably, 590nm ≦ λ_Rmax ≦ 640nm and, more preferably, 600nm ≦ λ_Rmax ≦ 630nm.

[0019] When setting λ_Rmax within the above-mentioned range, color-hues including particularly purple colors can be reproduced with sufficient fidelity.

[0020] In the inventive silver halide color photographic light sensitive materials for taking-pictures, the spectral photosensitivity of each of B-, G- and R-layers can be selectively obtained by taking any one of the various means. These means include, for example, a means for providing a spectral sensitization for a silver halide with a sensitizing dye having an absorption in an intended-wavelength region; another means for providing an objective spectral sensitization upon suitably optimizing the halide composition or distribution of silver halide; and a further means for controlling a spectral photosensitivity distribution so as to meet the objects by making use of a suitable optical absorbent. In addition to the above-mentioned means, it is also allowed to use the combination use of the above-mentioned means.

[0021] In this invention, a variety of the well-known spectrally sensitizing dyes can be used. Among these dyes, a cyanine dye, a merocyanine dye, a compounded merocyanine dye and so forth are preferably used.

[0022] In this invention, any well-known silver halides can be used for the silver halides of the photosensitive layers of silver halide color photographic light sensitive materials for taking-picture use. The photosensitive silver halides may be preferably comprised of silver iodobromide for use in light sensitive materials for taking-picture use. Besides the silver iodobromide, silver chloroiodobromide, silver bromide, silver chloride and so forth may also be used.

[0023] In this invention, a variety of the well-known couplers may be used in G- and R-layer(s) of silver halide color photographic light sensitive materials for taking-picture use.

[0024] Next, silver halide color photographic light sensitive materials for printing use will be detailed below.

[0025] In silver halide color photographic light sensitive materials for printing use, it is preferable that Y-layer is a blue-sensitive layer, M-layer is a green-sensitive layer and C-layer is a red-sensitive layer. It is preferable that each of the photosensitive layers is applied with a silver halide emulsion containing silver chlorobromide as the halide composition thereof. It is further preferable to use a silver halide emulsion such as a silver chloride emulsion and a silver chlorobromide emulsion, which contains the halides comprising silver chloride in an average amount of not less than 90 mol%.

[0026] In the spectral density distribution S_Y(λ) of the color dye formed from the coupler represented by the foregoing Formula [I] in the Y-layer(s), it is preferable that the wavelength capable of giving a maximum value of S_Y(λ) is to be in a wavelength region within the range of 430nm to 460nm and that the wavelength λ_Y50 is to be within the range of 485nm to 495nm on the longer wavelength side where λ_Y50 corresponds to a wavelength capable of giving 50% of the maximum value of S_Y(λ).

[0027] In the M- and C-layer of a silver halide color photographic light sensitive material for printing use, a variety of the well-known couplers may be used.

[0028] In the present invention, the color developing agents applicable to form images include, for example, the well-known aromatic primary amine color developing agents. Among these agents, a p-phenylene diamine derivative is preferably used for.

[0029] The typical examples of the color developing agents applicable to this invention will be given below. However, they shall not be limited to the examples thereof given below.

D-1

N,N-diethyl-p-phenylenediamine,

D-2

2-amino-5-diethylaminotoluene,

D-3

2-amino-5-(N-ethyl-N-laurylamino)toluene,

D-4

4-[N-ethyl-N-(β-hydroxyethyl)amino]aniline,

D-5

2-methyl-4-[N-ethyl-N-(β-hydroxyethyl)amino]aniline,

D-6

4-amino-3-methyl-N-ethyl-N-[β-(methanesulfonamido)ethyl]-aniline,

D-7

N-(2-amino-5-diethylaminophenylethyl)methanesulfoneamide,

D-8

N,N-dimethyl-p-phenylenediamine,

D-9

4-amino-3-methyl-N-ethyl-N-methoxyethylaniline,

D-10

4-amino-3-methyl-N-ethyl-N-β-ethoxyethylaniline, and

D-11

4-amino-3-methyl-N-ethyl-N-β-butoxyethylaniline,

[0030] Among the above-given p-phenylene diamine derivatives, 4-amino-3-methyl-N-ethyl-N-[β-(methanesulfonamido)ethyl]-aniline is preferably used in particular.

[0031] Next, in the present invention, the yellow couplers represented by the foregoing Formula [I], which are applicable to both of B- and Y-layers, will be detailed below.

[0032] In the yellow couplers represented by the foregoing Formula [I], the alkyl groups represented by R¹ include, for example, a methyl group, an ethyl group, an isopropyl group, a t-butyl group, a dodecyl group and so forth. The alkyl groups represented by R¹ also include those having a substituent. The substituents include, for example, a halogen atom, an aryl group, an alkoxy group, an aryloxy group, an alkylsulfonyl group, an acylamino group and a hydroxyl group.

[0033] The cycloalkyl groups represented by R¹ include, for example, a cyclopropyl group, a cyclohexyl group, an adamantyl group and so forth.

[0034] The aryl groups represented by R¹ include, for example, a phenyl group.

[0035] The group represented by R¹ is preferably, for example, a branched alkyl group.

[0036] In Formula [I], the groups preferably represented by R⁰ include, for example, an aryl group having 6 to 24 carbon atoms (such as a phenyl group, a p-tolyl group, an o-tolyl group and a 4-methoxyphenyl group), an alkoxy group having 1 to 14 carbon atoms (such as a methoxy group, an ethoxy group, a butoxy group, an n-octyloxy group, an n-tetradecyloxy group, a benzyloxy group and a methoxyethoxy group), an aryloxy group having 6 to 24 carbon atoms (such as a phenoxy group, a p-tolyloxy group, an o-tolyloxy group, a p-methoxyphenoxy group, a p-dimethylaminophenoxy group and an m-pentadecylphenoxy group), and a trifluoromethyl group. Among them, an alkoxy group and an aryloxy group are more preferable, and an alkoxy group having 1 to 5 carbon atoms is most preferable.

[0037] In Formula [I], the groups represented by R³ each substitutable to a benzene ring include, for example, a halogen atom (such as a chlorine atom), an alkyl group (such as an ethyl group, an i-propyl group and a t-butyl group), an alkoxy group (such as a methoxy group), an aryloxy group (such as a phenyloxy group), an acyloxy group (such as a methylcarbonyloxy group and a benzoyloxy group), an acylamino group (such as an acetamido group and a phenylcarbonylamino group), a carbamoyl group (such as an N-methylcarbamoyl group and an N-phenylcarbamoyl group), an alkylsulfonamido group (such as an ethylsulfonylamino group), an arylsulfonamido group (such as a phenylsulfonylamino group), a sulfamoyl group (such as an N-propylsulfamoyl group and an N-phenylsulfamoyl group), an imido group (such as a succinimido group and a glutarimido group) and so forth. In the formula, n is an integer of 0 or 1.

[0038] In Formula [I], Y¹ represents a ballast group, for which the groups represented by the following Formula [II] are preferable.

Formula [II]

[0039] 

        -J-R⁴


   wherein R⁴ represents an organic group comprising a linking group having a carbonyl or sulfonyl group.

[0040] The groups each having a carbonyl group include, for example, an ester group, an amido group, a carbamoyl group, a ureido group, a urethane group and so forth. The groups each having a sulfonyl group include, for example, a sulfo group, a sulfonamido group, a sulfamoyl group, an aminosulfonamido group and so forth.

[0041] J represents -N(R⁵)CO- or -CON(R⁵)-, in which R⁵ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

[0042] The alkyl groups represented by R⁵ include, for example, a methyl group, an ethyl group, an isopropyl group, a t-butyl group, a dodecyl group and so forth. The aryl groups represented thereby include, for example, a phenyl group, a naphthyl group and so forth. The heterocyclic groups represented thereby include, preferably, those each having 5- to 7-membered ring, such as a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, a 2-benzothiazolyl group and so forth.

[0043] The alkyl, aryl or heterocyclic groups each represented by R⁵ also include those having substituents. The substituents shall not be limited, but they include, typically, a halogen atom (such as a chlorine atom and so forth), an alkyl group (such as an ethyl group, a t-butyl group and so forth), an aryl group (such as a phenyl group, a p-methoxyphenyl group, a naphthyl group and so forth), an alkoxy group (such as an ethoxy group, a benzyloxy group and so forth), an aryloxy group (such as a phenoxy group and so forth), an alkylthio group (such as an ethylthio group and so forth), an arylthio group (such as a phenylthio group and so forth), an alkylsulfonyl group (such as a β-hydroxyethylsulfonyl group and so forth), and an arylsulfonyl group (such as a phenylsulfonyl group and so forth); also, a carbamoyl group including, for example, those in which an alkyl group, an aryl group (including preferably a phenyl group) or the like is substituted, and those including, concretely, an N-methylcarbamoyl group, an N-phenylcarbamoyl group and so forth; further, an acyl group including an alkylcarbonyl group such as an acetyl group and so forth, an arylcarbonyl group such as a benzoyl group and so forth; still further, a sulfonamido group including, for example, an alkylsulfonylamino group, an arylsulfonylamino group and so forth, such as, concretely, a methylsulfonylamino group, a benzenesulfonamido group and so forth; also, a sulfamoyl group including, for example, those substituted with an alkyl group or an aryl group (such as, preferably, a phenyl group) or the like and those including, concretely, an N-methylsulfamoyl group, an N-phenylsulfamoyl group and so forth; and, in addition, a hydroxyl group, a cyano group and so forth.

[0044] In Formula [I], X¹ represents a group capable of splitting off upon coupling reaction with the oxidized product of a developing agent. The groups are represented by the following Formula [III] or [IV] and, among them, the group represented by Formula [IV] is preferable.

Formula [III]

[0045] 

        -OR⁶


   wherein R⁶ represents an aryl or heterocyclic group including those each having a substituent.


   wherein Z¹ represents the group consisting of non-metal atoms necessary to form a 5- or 6-membered ring upon associating with a nitrogen atom. The atomic groups necessary to form the group consisting of non-metal atoms include, for example, those of methylene, methine or substituted methine and those given below.


(in which R^A is synonymous with the above-denoted R⁵),

        -N-, -O-, -S-, -SO₂-

[0046] The yellow couplers represented by the foregoing Formula [I] are also allowed to form a bis-member upon bonding in the position of R¹, R³ or Y¹.

[0047] The yellow coupler of the present invention is preferably represented by the following Formula [V].


   wherein R¹, R³ and J represent each the same groups as those represented by R¹, R³ denoted in Formula [I] and J denoted in Formula [II]; R² represents an alkyl group having 1 to 5 carbon atoms; n is an integer of 0 or 1; R⁷ represents an alkylene group, an arylene group, an alkylenearylene group, an arylenealkylene group or -A-V¹-B- (in which A and B represent each an alkylene group, an arylene group, an alkylenearylene group or an arylenealkylene group, and V¹ represents a divalent linking group); R⁸ represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group; P⁰ represents a bonding group having a carbonyl or sulfonyl unit; and X¹ represents a group capable of splitting off upon coupling reaction with the oxidized products of a color developing agent.

[0048] In Formula [V], the alkylene groups each represented by R⁷ include, for example, a methylene group, an ethylene group, a propylene group, a butylene group and a hexylene group. These groups also include those having substituents, namely; those substituted with an alkyl group including, for example, a methyl-methylene group, an ethyl-ethylene group, a 1-methylethylene group, a 1-methyl-2-ethyl-ethylene group, a 2-decylethylene group, a 3-hexyl-propylene group and a 1-benzylethylene group; and those substituted with an aryl group including, for example, a 2-phenyl-ethylene group and a 3-naphthyl-propylene group.

[0049] The arylene groups include, for example, a phenylene group and a naphthylene group.

[0050] The alkylenearylene groups include, for example, a methylenephenylene group and so forth. The arylenealkylene groups include, for example, a phenylenemethylene group and so forth.

[0051] The alkylene, arylene, alkylenearylene or arylenealkylene groups represented by A and B are synonymous with those represented by R⁷ denoted in Formula [V]; and the divalent bonding groups represented by V¹ include, for example, -O-, -S- and so forth.

[0052] Among the alkylene, arylene, alkylenearylene and arylenealkylene groups and -A-V¹-B- each represented by R⁷, alkylene groups are particularly preferable.

[0053] In the afore-given Formula [V], the alkyl groups represented by R⁸ include, for example, an ethyl group, a butyl group, a hexyl group, an octyl group, a dodecyl group, a hexadecyl group, an octadecyl group and so forth. These alkyl groups may also be straight-chained or branched. The cycloalkyl groups include, for example, a cyclohexyl group and so forth. The aryl groups include, for example, a phenyl group, a naphthyl group and so forth. The heterocyclic groups include, for example, a pyridyl group and so forth. The alkyl, cycloalkyl, aryl and heterocyclic groups each represented by R⁸ also include those having substituents.

[0054] Any substituents shall be applicable thereto without special limitation. However, the same substituents as those given for the foregoing R⁵ may be given, provided, however, that an organic group having a dissociative hydrogen atom having a pKa value of not higher than 9.5 (such as a phenolic hydrogen atom and so forth) are not preferable for the substituents to R⁸.

[0055] In the foregoing Formula [V], P⁰ represents a linking group having a carbonyl or sulfonyl unit and, among them, the groups represented by the following Formula Group [VI] are preferable.


   and, more preferably, a linking group having a sulfonyl unit.

[0056] wherein R and R' represent each a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, provided, R and R' may also be the same with or the different from each other.

[0057] The groups represented by R and R' include, for example, the same groups as given for R⁵. These groups also include those having the same substituents as given for R⁵.

[0058] R and R' preferably represent each a hydrogen atom.

[0059] The yellow couplers of the invention represented by the foregoing Formula [I] may be ordinarily used in an amount within the range of, preferably, 1x10⁻³ mols to 1 mol per 1 mol of silver halide used and, more preferably, 1x10⁻² mols to 8x10⁻¹ mols.

[0060] The typical examples of the yellow couplers represented by Formula [I] will be given below, provided that they will be exemplified by specifying X¹, R¹, R² and the substituents in each position.

[0061] The couplers of the invention may be used independently or in combination in the form of the mixture. It is also allowed to use them upon mixing them with any known yellow couplers.

[0062] The coupler of the invention can be used in any layers of light sensitive materials. However, it is preferable to be used in light sensitive silver halide emulsions or the layer adjacent thereto and most preferable to be used in light sensitive emulsion layers.

[0063] The coupler of the invention can be synthesized in any conventional well-known synthesizing processes including, typically, the synthesizing process described in JP OPI Publication No. 63-123047/1988.

[0064] The coupler of the invention is used in an amount within the range of 1x10⁻⁵ mols to 1.0⁻² mols, preferably 1x10⁻⁴ mols to 5x10⁻³ mols and more preferably 2x10⁻⁴ mols to 10⁻³ mols, each per sq. meter of a light sensitive material.

[0065] In the invention, a variety of well-known techniques can be used for adding the above-mentioned couplers into light sensitive layers. Ordinarily, these couplers can be added into light sensitive layers in an oil-in-water type dispersion process which are known as an oil-protect process. In this process, for example, a coupler is dissolved in a high-boiling organic solvent including phthalic acid esters such as dibutyl phthalate and dioctyl phthalate and phosphoric acid esters such as tricresyl phosphate and trinonyl phosphate, or the coupler is dissolved in the combination thereof with a low-boiling organic solvent such as ethyl acetate and/or a water-soluble solvent; the resulting solution is then dispersed emulsionwise in an aqueous gelatin solution containing a surfactant; and the resulting coupler dispersion is then added into a photographic emulsion. It is also allowed to prepare a coupler dispersion by adding water or an aqueous gelatin solution into a coupler solution containing a surfactant so that an oil drops-in water type dispersion can be prepared with accompanying a phase inversion. It is further allowed to mix a coupler dispersion with a photographic emulsion in a distillation, noodle-washing or ultrafiltration process, after removing a low-boiling organic solvent and so forth. It is still further allowed to disperse a coupler dispersion and add it into a photographic emulsion, in such a coupler dispersion process as described in U.S. Patent Nos. 4,933,270, 4,957,857, 4,990,431, 4,970,139, 5,013,640, 5,008,179, 5,024,929, 5,087,554, 5,089,380 and 5,091,296.

[0066] The above-mentioned coupler may be used in an amount within the range of 0.05 mols to 0.5 mols and preferably 0.1 mols to 0.4 mols, each per mol of a silver halide content of an emulsion layer. The ratio by weight of a high-boiling organic solvent to a yellow coupler of the invention (hereinafter referred to as HBS/Coupler) is preferably not more than 1.5 and more preferably not more than 1.0.

[0067] The blue-sensitive layer of the invention may be formed of a plurality of layers. Particularly, it is to be formed of, preferably, 2 to 4 layers and, more preferably, 2 to 3 layers.

[0068] The light sensitive silver halide emulsions applicable to the invention include, particularly, a silver iodobromide emulsion, provided, it is to have an average silver iodide content within the range of, preferably 7 mol% or less, more preferably 1.0 to 6.5 mol% and, further preferably 1.5 to 6 mol%.

[0069] The processes of preparing the above-mentioned silver halide emulsions and the additives applicable to the emulsion preparation are described in, for example, Research Disclosure Nos. 17643, 18716 and 308119 (hereinafter abbreviated to RD17643,18716 and 308119, respectively). Table 1 indicates the contents and places of the descriptions given in RD308119.

Table 1

[Contents]	[Page of RD308119]
Iodide composition	p.993 I-A
Preparation process	993 I-A; p.994 I-E
Crystal habit, Regular	993 I-A
Twinned	993 I-A
Epitaxial	993 I-A
Halogen composition, Uniformed	993 I-B
Not uniformed	993 I-B
Halogen conversion	994 I-C
Halogen substitution	994 I-C
Metal content	994 I-D
Monodispersion	995 I-F
Solvent addition	995 I-F
Latent image position, On surface	995 I-G
Inside	995 I-G
Light sensitive material applied,
Negative	995 I-H
Positive (containing grains fogged inside)	995 I-H
Mixed emulsions used	995 I-J
Desalting treatment	995 II-A

[0070] The silver halide emulsions applicable to the invention can be physically or optically ripened and spectrally sensitized. The additives applicable to such a treatment as mentioned above are given in, for example, RD 17643, RD18716 and RD308119. Table 2 indicates the places of the RDs given the information of the additives.

Table 2

[Contents]	[RD308119]	[RD17643]	[RD18716]
Chemical sensitizer	p.996 III-A	p.23	p.648
Spectral sensitizer	996 IV-A,B,C,D II,I,J	23∼24	648∼9
Supersensitizer	996 IV-A-E,J	23∼24	648∼9
Antifoggant	998 VI	24∼25	649
Stabilizer	998 VI	24∼25	649

[0071] The well-known photographic additives applicable to the invention are also given in RD17643, RD18716 and RD308119. Table 3 indicates the places of the related descriptions.

Table 3

[Contents]	[RD308119]	[RD17643]	[RD18716]
Color-stain preventive	p.1002 VII-I	p.25	p.650
Dye-image stabilizer	1001 VII-J	25
Whitening agent	998 V	24
UV absorbent	1003 VIII-C, XIII-C	25∼26
Light absorbent	1003 VIII	25∼26
Light scattering agent	1003 VIII
Filter dye	1003 VIII	25∼26
Binder	1003 IX	26	651
Antistatic agent	1006 XIII	27	650
Layer hardener	1004 X	26	651
Plasticizer	1006 XII	27	650
Lubricant	1006 XII	27	650
Activator·Coating aid	1005 XI	26∼27	650
Matting agent	1007 XVI
Developing agent (contained in light sensitive materials)	1011 XX-B

[0072] The other various types of couplers can also be applied in combination to the invention. The typical examples of these couplers are also given in the following RD17643 and RD308119. Table 4 indicates the places of the descriptions related thereto.

Table 4

[Contents]	[RD308119]	[RD17643]
Yellow coupler	p.1001 VII-D	p.25 VII-C∼G
Magenta coupler	1001 VII-D	25 VII-C∼G
Cyan coupler	1001 VII-D	25 VII-C∼G
Colored coupler	1002 VII-G	25 VII-G
DIR coupler	1001 VII-F	25 VII-F
BAR coupler	1002 VII-F
Other organic residual group releasing coupler	1001 VII-F

[0073] The additives applicable to the invention can be added in such a dispersion process as described in RD308119, p.1007, XIV.

[0074] In the invention, it is allowed to use each of the supports described in the foregoing RD17643, p.28, RD18716, pp.647∼648 and RD308119, p.1009, XIX.

[0075] To the light sensitive materials of the invention, the auxiliary layers such as the filter layers or interlayers each described in the foregoing RD308119, VII-K can be provided.

[0076] The light sensitive materials of the invention are allowed to have a variety of layer arrangements such as the regular, inverse and unit-layer arrangements, each described in RD308119, VII-K.

[0077] As for the supports, it is allowed to use a sheet of paper laminated with polyethylene and so forth, a polyethylene terephthalate film, a sheet of baryta paper, a cellulose triacetate film, and so forth.

[0078] This invention can be applied to a variety of color light sensitive materials typically including a color negative film, a slide or TV color reversal film, a color paper, a color positive film and a color reversal paper.

[0079] For obtaining a dye-images with the use of a light sensitive material of the invention, any generally known color development processes can be utilized.

[0080] The light sensitive materials of the invention can be developed in any ordinary processes such as those described in, for example, the foregoing RD17643, pp.28∼29, RD18716, p.647 and RD308119, XIX.

EXAMPLES

[0081] Some examples of the invention will be described below. It is, however, to be understood that the invention shall not be limited thereto.

Example 1

(Preparation of Color Reversal Film Samples 1 ∼ 5)

[0082] Onto a sublayered triacetyl cellulose film support, the layers having the following compositions were coated in order from the support side, so that Sample 1 was prepared. The amount of each component coated will be shown in terms of g/m², provided, however, that the amounts of silver halide will be shown by converting them into the silver contents.

Layer 1 (An antihalation layer)
Black colloidal silver	0.24
UV absorbent (U-1)	0.14
UV absorbent (U-2)	0.072
UV absorbent (U-3)	0.072
UV absorbent (U-4)	0.072
High boiling solvent (O-1)	0.31
High boiling solvent (O-2)	0.098
Poly-N-vinyl pyrrolidone	0.15
Gelatin	2.02

Layer 2 (Interlayer-1)
Gelatin	0.65

Layer 3 (Interlayer-2)
A fine-grained silver iodobromide emulsion fogged on the surface, (having a silver iodide content of 1.0 mol% and an average grain size of 0.08µm)	0.05
Gelatin	0.50

Layer 4 (A low-speed red-sensitive layer)
A silver iodobromide emulsion spectrally sensitized with red-sensitizing dyes (S-1) & (S-2), (having a silver iodide content of 4.0 mol% and an average grain size of 0.32µm)	0.50
Coupler (C-1)	0.30
High boiling solvent (O-2)	0.090
Poly-N-vinyl pyrrolidone	0.074
Gelatin	0.80

Layer 5 (A medium-speed red-sensitive layer)
A silver iodobromide emulsion spectrally sensitized with red-sensitizing dyes (S-1) & (S-2), (having a silver iodide content of 3.5 mol% and an average grain size of 0.58µm)	0.40
Coupler (C-1)	0.50
High boiling solvent (O-2)	0.016
Poly-N-vinyl pyrrolidone	0.093
Gelatin	0.80

Layer 6 (A high-speed red-sensitive layer)
A silver iodobromide emulsion spectrally sensitized with red-sensitizing dyes (S-1) & (S-2), (having a silver iodide content of 3.0 mol% and an average grain size of 1.3µm)	0.40
Coupler (C-1)	0.75
High boiling solvent (O-2)	0.023
Poly-N-vinyl pyrrolidone	0.093
Gelatin	1.1

Layer 7 (Interlayer-3)
Gelatin	0.60

Layer 8 (Interlayer-4)
A fine-grained silver iodobromide emulsion fogged on the surface thereof (having a silver iodide content of 1.0 mol% and an average grain size of 0.06µm)	0.06
Color-mixing preventive (AS-1)	0.20
High boiling solvent (O-3)	0.25
Matting agent (MA-1)	0.0091
Gelatin	1.0

Layer 9 (A low-speed green-sensitive layer)
A silver iodobromide emulsion spectrally sensitized with green-sensitizing dyes (S-3) & (S-4), (having a silver iodide content of 3.5 mol% and an average grain size of 0.33µm)	0.60
Coupler (M-1)	0.31
Coupler (M-2)	0.060
High boiling solvent (O-3)	0.059
Poly-N-vinyl pyrrolidone	0.074
Gelatin	0.50

Layer 10 (A medium-speed green-sensitive layer)
A silver iodobromide emulsion spectrally sensitized with green-sensitizing dyes (S-3) & (S-4), (having a silver iodide content of 2.8 mol% and an average grain size of 0.60µm)	0.50
Coupler (M-1)	0.29
Coupler (M-2)	0.076
High boiling solvent (O-3)	0.059
Poly-N-vinyl pyrrolidone	0.074
Gelatin	0.60

Layer 12 (Interlayer-5)
Gelatin	0.90

Layer 13 (A yellow-filter layer)
Yellow colloidal silver	0.11
Color-mixing preventive (AS-1)	0.068
High boiling solvent (O-3)	0.085
Matting agent (MA-1)	0.012
Gelatin	0.50

Layer 14 (A low-speed blue-sensitive layer)
A silver iodobromide emulsion spectrally sensitized with blue-sensitizing dyes (S-5) (having a silver iodide content of 2.8 mol% and an average grain size of 0.46µm)	0.60
Coupler (Y-1)	0.60
Image stabilizer (G-1)	0.012
High boiling solvent (O-3)	0.10
Poly-N-vinyl pyrrolidone	0.078
Compound (F-1)	0.020
Compound (F-2)	0.040
Gelatin	0.80

Layer 16 (A high-speed blue-sensitive layer)
A silver iodobromide emulsion spectrally sensitized with blue-sensitizing dyes (S-5) (having a silver iodide content of 3.0 mols and an average grain size of 1.3µm)	0.50
Coupler (Y-1)	0.81
Image stabilizer (G-1)	0.017
High boiling solvent (O-3)	0.12
Poly-N-vinyl pyrrolidone	0.10
Compound (F-1)	0.039
Compound (F-2)	0.077
Gelatin	1.20

[0083] In the above-described Sample 1, there further contained gelatin layer hardeners H-1, H-2 and H-3, water-soluble dyes AI-1, AI-2 and AI-3, antimold DI-1, stabilizer ST-1 and antifoggant AF-1.

[0084] The silver halide emulsions used in each of the light sensitive layers were prepared with reference to the process described in Example 1 given in JP OPI Publication No. 59-178447/1984. The resulting emulsions were the monodisperse type emulsions each having a distribution range of not more than 20%. After desalting and washing the resulting emulsions, they were each subjected to an optimum chemical ripening treatment in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate and were then added with sensitizing dyes, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene and 1-phenyl-5-mercaptotetrazole.

Sensitizing dyes

[0085] 

Coupler

[0086] 

Compounds

[0087] 

Matting agents

[0088] 

MA-1

Colloidal silica particles (having an average particle size of 3.5µm)

MA-2

Polymethyl methacrylate particles (having an average particle size of 3.0µm)

UV absorbents

[0089] 

High boiling solvents

[0090] 

O-1

Di-2-ethylhexyl phthalate

O-2

Di-butyl phthalate

O-3

Tricresyl phosphate

Color-mixing preventive

AS-1

[0091] Mixture (2:3) of

Image stabilizer

[0092] 

Lubricant

[0093] 

Surfactant

[0094] 

Layer hardener

[0095] 

H-2

[0096] 

        [(CH₂=CHSO₂CH₂)₃CCH₂SO₂(CH₂)₂]₂N(CH₂)₂SO₃K

H-3

[0097] 

        (CH₂=CH-SO₂CH₂)₂O

Water-soluble dye

[0098] 

Antimold

[0099] 

[0100] Samples 2 through 5 were each prepared in the same manner as in Sample 1, except that coupler Y-1 used in Layers 14, 15 and 16 of Sample 1 were replaced by the couplers shown in Table 1 in the same mols with those of coupler Y-1.

Table 5

Sample No.	Couplers used in Layers 14 ∼ 16
1	Y-1
2	Exemplified compound 6
3	Exemplified compound 56
4	Exemplified compound 1
5	Exemplified compound 3

(Preparation of Color Reversal Paper Samples 101 ∼ 105)

[0101] Sample 101 was prepared to provide the following layers 1 through 11 on a paper-made support polyethylene coated on the both sides. The amounts of each component coated will be shown in terms of g/m², provide, however, the silver halide used therein will be shown the corresponding silver contents thereof.

Layer 1 (An antihalation layer)
Black colloidal silver	010
High boiling solvent (AO-1)	0.90
Gelatin	1.5

Layer 2 (Red-sensitive layer 1)
Cyan coupler (AC-1)	0.09
Cyan coupler (AC-2)	0.20
Antifading agent (AA-1)	0.15
Antifading agent (AA-2)	0.075
Color-mixing preventive (AAN-1)	0.0060
High boiling solvent (AO-1)	0.22
AgBrI spectrally sensitized with red-sensitizing dyes (AS-1 and AS-2), (having an AgI content of 4.0 mol% and an average particle size of 0.42µm)	0.11
Polyvinyl pyrrolidone	0.06
Gelatin	1.0

Layer 3 (Red-sensitive layer 2)
Cyan coupler (AC-1)	0.15
Cyan coupler (AC-2)	0.08
Antifading agent (AA-1)	0.085
Antifading agent (AA-2)	0.043
Color-mixing preventive (AAN-1)	0.0034
High boiling solvent (AO-1)	0.13
AgBrI spectrally sensitized with red-sensitizers (AS-1 and AS-2), (having an AgI content of 4.0 mol% and an average particle size of 0.80µm)	0.30
AgBrI spectrally sensitized with red-sensitizers (AS-1 and AS-2), (having an AgI content of 2.0 mol% and an average particle size of 0.42µm)	0.05
Polyvinyl pyrrolidone	0.016
Gelatin	1.0

Layer 5 (Green-sensitive layer 1)
Magenta coupler (AM-1)	0.15
Antifading agent (AA-3)	0.03
Antifading agent (AA-4)	0.0056
Antifading agent (AA-6)	0.070
Color-mixing preventive (AAN-1)	0.0046
High boiling solvent (AO-2)	0.092
AgBrI spectrally sensitized with green-sensitizing dyes (AS-3), (having an AgI content of 4.0 mol% and an average particle size of 0.42µm)	0.13
AgBrI spectrally sensitized with green-sensitizing dyes (AS-3), (having an AgI content of 2.0 mol% and an average particle size of 0.27µm)	0.020
Polyvinyl pyrrolidone	0.03
Gelatin	1.0

Layer 7 (Interlayer 2)
Yellow colloidal silver	0.20
Color-mixing preventive (AAN-1)	0.011
Color-mixing preventive (AAN-2)	0.034
High boiling solvent (AO-1)	0.070
Gelatin	0.90

Layer 8 (Blue-sensitive layer 1)
Yellow coupler (AY-1)	0.50
Antifading agent (AA-1)	0.11
Antifading agent (AA-5)	0.057
Color-mixing preventive (AAN-1)	0.0085
High boiling solvent (AO-3)	0.055
AgBrI spectrally sensitized with blue-sensitizing dye (AS-4), (having an AgI content of 4.0 mol% and an average particle size of 0.42µm)	0.11
AgBrI spectrally sensitized with blue-sensitizing dye (AS-4), (having an AgI content of 2.0 mol% and an average particle size of 0.90µm)	0.025
Gelatin	0.80

Layer 10 (A UV absorbing layer)
UV abosorbent (AU-1)	0.15
UV absorbent (AU-2)	0.45
UV absorbent (AU-3)	0.60
Color-mixing preventive (AAN-1)	0.033
Gelatin	1.2

Layer 11 (A protective layer)
Gelatin	0.50
Color-mixing preventive (AAN-2)	0.016
High boiling solvent (AO-1)	0.0033
Silica powder (having an average particle size of 3µm)	0.0015

[0102] In the above-mentioned Sample 101, there further contained surfactant (ASU-1, ASU-2 and ASU-3), layer hardeners (AH-1, AH-2 and AH-3), anti-irradiation dyes (AAI-1, AAI-2, AAI-3 and AAI-4) and antimold (ADI-1).

[0103] The chemical structures of the components used in Sample 101 will be given below.

Color-mixing preventive

[0104] 

AO-1

Di-s-ethylhexyl phthalate

AO-2

Di-isodecyl phthalate

AO-3

Di-nonyl phthalate

AH-2

[0105] 

        [(CH₂=CHSO₂CH₂)₃CCH₂SO₂(CH₂)₂]₂N(CH₂)₂SO₃K

AH-3

[0106] 

        (CH₂=CHSO₂CH₂)₂O

[0107] Samples 102 through 105 were each prepared in the same manner as in Sample 101, except that yellow coupler AY-1 contained in Layers 8 and 9 of Sample 101 were replaced by the yellow couplers shown in Table 6 in the same mols as that of AY-1.

Table 6

Sample No.	Yellow couplers of Layers 8 & 9
101	AY-1
102	Exemplified compound 57
103	Exemplified compound 14
104	Exemplified compound 60
105	Exemplified compound 3

[0108] Next, a color-rendition chart manufactured by Macbeth Co. and a portrait of a woman wearing a red sweater were photographed on Samples 1 through 5 and the samples were each color-developed as follows.

Processing step	Processing time	Processing temperature
First developing	6 min.	38°C
Washing	2 min.	38°C
Reversing	2 min.	38°C
Color developing	6 min.	38°C
Adjusting	2 min.	38°C
Bleaching	6 min.	38°C
Fixing	4 min.	38°C
Washing	4 min.	38°C
Stabilizing	1 min.	At an ordinary temp.
Drying

[0109] The compositions of the processing solutions used in the above-mentioned processing steps were as follows.

<First developper>
Sodium tetrapolyphosphate	2 g
Sodium sulfite	20 g
Hydroquinone·monosulfonate	30 g
Sodium carbonate (monohydrate)	30 g
1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone	2 g
Potassium bromide	2.5 g
Potassium thiocyanate	1.2 g
Potassium iodide (an aqueous 0.1% solution)	2 ml
Add water to make	1000 ml

<Reversing solution>
Hexasodium nitrilotrimethylene phosphate	3 g
Stannous chloride (dihydrate)	1 g
p-aminophenol	0.1 g
Sodium hydroxide	8 g
Glacial acetic acid	15 ml
Add water to make	1000 ml

<Adjusting solution>
Sodium sulfite	12 g
Sodium ethylenediamine tetraacetate (dihydrate)	8 g
Thioglycerol	0.4 ml
Glacial acetic acid	3 ml
Add water to make	1000 ml

<Bleaching solution>
Sodium ethylenediamine tetraacetate (dihydrate)	2 g
Iron (III) ammonium ethylenediamine tetraacetate (dihydrate)	120 g
Ammonium bromide	100 g
Add water to make	1000 ml

<Fixing solution>
Ammonium thiosulfate	80 g
Sodium sulfite	5 g
Sodium bisulfite	5 g
Add water to make	1000 ml

<Stabilizing solution>
Formalin (at 37% by weight)	5 g
Konidux (manufactured by Konica Corp.)	5 g
Add water to make	1000 ml

[0110] The color-rendition chart and portrait were photographed on a color positive film and were then developed. By making use of the resulting developed positive film and in combination thereof with Samples 101 through 105, the charts and portraits were printed thereon and the printed Samples 101 through 105 were each developed, so that the color prints were obtained. Each of the resulting color prints was so printed again as to make the gray of the MacBeth Chart be constant. Separately, when the spectral photosensitivity distribution of Layer B was measured, every Samples 1 to 5 was proved to have a λ_Bmax value of 455nm.

[0111] Further, when the spectral photosensitivity distribution of Layer G was measured, Samples 1 to 5 each gave λ_Gmax of 560nm. The sensitivity at 570nm (S_G570) of each sample was 14% of the sensitivity at λ_Gmax.

Development process
First developing (Black-and-white development)	1min.15sec. (at 38°C)
Washing	1min.30sec.
Light fogging (not less than 100ℓux)	Not shorter than 1 sec.
Second developing (Color development)	2min.15sec. (at 38°C)
Washing	45sec.
Bleach-fixing	2min. (at 38°C)
Washing	2min.15sec.

[0112] The compositions of the processing solutions used in each of the processing steps were as follows.

First Developer
Potassium sulfite	3.0 g
Sodium thiocyanate	1.0 g
Sodium bromide	2.4 g
Potassium iodide	8.0 mg
Potassium hydroxide (in a 48% solution)	6.2 cc
Potassium carbonate	14 g
Sodium hydrogen carbonate	12 g
1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone	1.5 g
Hydroquinone monosulfonate	23.3 g (pH=9.65)

Color developer
Benzyl alcohol	14.6 cc
Ethylene glycol	12.6 cc
Potassium carbonate (anhydride)	26 g
Potassium hydroxide	1.4 g
Sodium sulfite	1.6 g
3,6-dithiaoctane-1,8-diol	0.24 g
Hydroxylamine sulfate	2.6 g
4-N-ethyl-N-(β-methanesulfonamido-ethyl-)-3-methyl-4-amino-aniline sulfate	5.0 g
Add water to make	1000 cc (pH=10.4)

Bleach-fixing solution
Iron (III) ammonium ethylene-diamine tetraacetate (in a 1.56-mol solution)	115 cc
Sodium metabisulfite	15.4 g
Ammonium thiosulfate (in an aqueous 58% solution)	126 cc
1,2,4-triazole-3-thiol	0.4 g
Add water to make	1000 cc (pH=6.5)

[0113] In the spectral density distribution S_Y(λ) of the dye formed from inventive yellow couplers represented by Formula [I] in Y-layers of Samples 102 through 105, a maximum value of S_Y(λ) of each sample was in a wavelength region of 430 to 450nm, and a wavelength λ_Y50 giving 50% of the maximum value of S_Y(λ) of each sample was within the range of 485 to 495nm on the longer wavelength side.

[0114] The color reproducibilities of the resulting prints were visually evaluated with especially paying attention to skin color and yellow color. The results thereof will be shown in Table 7.

[0115] In print A came out of the color reversal paper and film each unsatisfied the constitutional requirements of the invention, the resulting color reproducibilities of both yellow and skin colors were not preferable. As in prints B and C, even when either one of a color light sensitive material for picture-taking use and a color light sensitive material for printing use contains a yellow coupler relating to the invention, any preferable color reproducibility could not be obtained. In contrast to the above, prints D through H satisfying the constitutional requirements of the invention were tinted with a healthy pink on the resulting skin color and excellent in yellow color reproducibility.

ADVANTAGES OF THE INVENTION

[0116] According to the invention, it is possible to obtain the prints excellent in color reproducibilities including, especially, the skin color and yellow color reproducibilities.

Claims

1. A silver halide color photographic image-forming process comprising
   making a color original image on a silver halide color photographic light-sensitive material for picture-taking use comprising a support having thereon a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer; and
   printing the color original image on a silver halide color photographic light-sensitive material for printing use comprising a support having thereon a yellow dye-forming layer, a magenta dye-forming layer and a cyan dye-forming layer;
   wherein both of said blue-sensitive emulsion layer of the photographic light-sensitive material for picture-taking use and said yellow dye-forming layer of the photographic light-sensitive material for printing use contain an yellow coupler represented by the following Formula [I];

wherein R¹ represents an alkyl, cycloalkyl or aryl group; R⁰ represents an aryl, alkoxy or trifluoromethyl group; R³ represnts a substituent; n is 0 or 1; X¹ represents a group capable of splitting off upon reaction with an oxidized product of a color developing agent; and Y¹ represents a ballast group.

2. The color photographic material of claim 1, wherein said yellow coupler is represented by the following Formula [V]

wherein R¹,R³ and X¹ each represent the same group as those represented by R¹, R³ and X¹ denoted in Formula [I] of claim 1; R² represents an alkyl group having 1 to 5 carbon atoms; J represents -N(R⁵)CO- or -CON(R⁵)-, in which R⁵ represents a hydrogen atom, an alkyl, aryl or heterocyclic group; R⁷ represents an alkylene, arylene, alkylenearylene, or arylenealkylene group, or -A-V¹-B-, in which A and B each represent an alkylene, arylene, alkylenearylene or arylenealkylene group, and V¹ represents a divalent linking group; R⁸ represents an alkyl, cycloalkyl, aryl or heterocyclic group; P⁰ represents a linking group having a carbonyl or sulfonyl group.

3. The color photographic material of claim 1, wherein said yellow coupler is contained in an amount of 1x10⁻³ to 1 mol per 1 mol of silver halide.

4. The color photographic material of claim 1, wherein said blue-sensitive emulsion layer has a maximum sensitivity at a wavelength of 400 to 470 nm.

5. The color photographic material of claim 4, wherein said green-sensitive emulsion layer has a maximum sensitivity at a wavelength of 525 to 560 nm, and a sensitivity at a wavelength of 570 nm is 40% or less of the maximum sensitivity thereof.

6. The color photographic material of claim 1, wherein said yellow dye-forming layer has a spectral density distribution in which a maximum density value is in a wavelength region of 430 to 440nm and a density value having 50% of the maximum value is in a wavelength region of 485 to 495 nm.