EP0270078B1

EP0270078B1 - Silver halide color photographic material and color photographic print

Info

Publication number: EP0270078B1
Application number: EP19870117764
Authority: EP
Inventors: Yukio Fuji Photo Film Co. Ltd. Aogaki; Yuzo Fuji Photo Film Co. Ltd. Toda; Nobuhiko Fuji Photo Film Co. Ltd. Minagawa
Original assignee: Fuji Photo Film Co Ltd
Current assignee: Fujifilm Holdings Corp
Priority date: 1986-12-02
Filing date: 1987-12-01
Publication date: 1994-05-11
Anticipated expiration: 2007-12-01
Also published as: DE3789800D1; EP0270078A3; EP0270078A2; JPS63264746A; JPH07119964B2

Description

The present invention relates to a silver halide color photographic material and a color photographic print, and more particularly to a color photographic print suitable for use as, for example, an ID card, a cashing card or a telephone card.
Conventional silver halide color photographic materials comprise a silver halide emulsion layer containing a cyan color forming coupler, a silver halide emulsion layer containing a magenta color forming coupler and a silver halide emulsion layer containing a yellow color forming coupler coated on various kinds of supports.
For example, EP-A-0 162 328 discloses a silver halide color photographic light-sensitive material having a good color formability, color reproducibility, image preservability and color balance, said material comprising a support and red-sensitive, green-sensitive and blue-sensitive light-sensitive layers formed on the support.
It is known that as a light transmissive photographic support, a transparent plastic film, for example, a cellulose triacetate film, a polyethylene terephthalate film or a vinyl resin film may be employed, and as a reflective support, for example, baryta coated paper, synthetic paper, polyethylene laminated paper, a plastic sheet containing a white pigment, a glass plate or a metal plate (for example, an aluminium plate having an anodized surface) may be employed.
With respect to reflective supports, it has been proposed that a white pigment be incorporated into a plastic material or that a white pigment containing layer is provided on a surface of a plastic material in order to particularly improve the whiteness of the supports.
When the whiteness of a support is increased, the reproducibility of a white object is improved, however, the sharpness of images usually decreases due to, for example, reflection during exposure and halation. Therefore, attempts have been made to incorporate an irradiation preventing dye into a light-sensitive silver halide emulsion layer provided on the support or to apply an antihalation layer to the support. EP-A-0 065 329 discloses a surface-treated polyvinyl chloride material which may contain pigments including an adhering hydrophilic layer containing a mixture of a hydrophilic colloid binder, gelatin in particular, and dispersed colloidal silica. The surface-treated polyvinyl chloride material is particularly suitable for use in identification document production.
Further, when baryta coated paper or polyethylene laminated paper is employed as a support, the smoothness of the support is poor due to the unevenness of the paper fiber and thus an uneven thickness of the silver halide emulsion layer occurs, resulting in a severe problem with the regularity of the image density obtained after development processing.
Such a problem is particularly noticeable when a sky scene is photographed and especially when it is photographed in color.
It is the object of the present invention to provide a reflective color photographic light-sensitive material having a reflective support with a good smoothness and which forms color images having an improved sharpness as well as a color photographic print having a reflective support with a good smoothness and color images of improved sharpness which, when used as various kinds of cards, can be subjected to embossment with heat processing. According to the present invention this object is attained with a silver halide color photographic material comprising a reflective support composed of a vinyl chloride resin containing a white pigment and having thereon in an appropriate order at least one red-sensitive silver halide emulsion layer containing a cyan color forming coupler represented by the general formula (1) or (2) shown below, at least one green-sensitive silver halide emulsion layer containing a magenta color forming coupler represented by the general formula (3) or (4) shown below, and at least one blue-sensitive silver halide emulsion layer containing a yellow color forming coupler represented by the general formula (5) shown below

wherein R₁, R₄ and R₅ each represents an aliphatic group, an aromatic group, a heterocyclic groups an aromatic amino group or a heterocyclic amino group; R₂ represents an aliphatic group; R₃ and R₆ each represents a hydrogen atom, a halogen atom, an aliphatic groups an aliphatic oxy group or an acylamino group; R₇ and R₈ each represents a substituted or unsubstituted phenyl group; R₉ represents a hydrogen atom or a substituent; R₂ and R₃ or R₅ and R₆ may be connected with each other to form a 5-membered to 7-membered ring; Q represents a substituted or unsubstituted N-phenylcarbamoyl group; Za and Zb, which may be the same or different, each represents a group of -CH=, a group of

or a group of -N=; R₁₀ represents the same substituent as that represented by R₉; and X₁, X₂, X₃, X₄ and X₅ each represents a hydrogen atom or a group capable of being released upon a reaction with an oxidation product of an aromatic primary amine developing agent.
Further, in accordance with the present invention the aforementioned object is attained with a color photographic print comprising a reflective support composed of a vinyl chloride resin containing a white pigment and having thereon in an appropriate order at least one emulsion layer containing a cyan dye obtained by a reaction of a cyan color forming coupler represented by the general formula (1) or (2) shown below with an oxidation product of an aromatic primary amine developing agent, at least one emulsion layer containing a magenta dye obtained by a reaction of a magenta color forming coupler represented by the general formula (3) or (4) shown below with an oxidation product of an aromatic primary amine developing agent, and at least one emulsion layer containing a yellow dye obtained by a reaction of a yellow color forming coupler represented by the general formula (5) shown below with an oxidation product of an aromatic primary amine developing agent

wherein R₁, R₄ and R₅ each represents an aliphatic group, an aromatic group, a heterocyclic group, an aromatic amino group or a heterocyclic amino group; R₂ represents an aliphatic group; R₃ and R₆ each represents a hydrogen atom, a halogen atom, an aliphatic group, an aliphatic oxy group or an acylamino group; R₇ and R₈ each represents a substituted or unsubstituted phenyl group; R₉ represents a hydrogen atom or a substituent; R₂ and R₃ or R₅ and R₆ may be connected with each other to form a 5-membered to 7-membered ring; Q represents a substituted or unsubstituted N-phenylcarbamoyl group; Za and Zb, which may be the same or different, each represents a group of -CH=, a group of

or a group of -N=; R₁₀ represents the same substituent as that represented by R₉; and X₁, X₂, X₃, X₄ and X₅ each represents a hydrogen atom or a group capable of being released upon a reaction with an oxidation product of an aromatic primary amine developing agent.
Hereinafter, the oxidation product of an aromatic primary amine developing agent will be referred to as "CD".
The color photographic print according to the present invention includes a color photographic print obtained by conducting at least the step or processing the silver halide color photographic material of the present invention, after imagewise exposure, with a color developing solution containing an aromatic primary amine color developing agent, and a color photographic print obtained by adhering the above-described color photographic print (but employing a transparent support) on a reflective support composed of a vinyl chloride resin containing a white pigment.
In the general formula (1), (2), (3), (4) or (5), the groups capable of being released represented by X₁, X₂, X₃, X₄ or X₅ include those described in U.S. Patent 4,540,654, column 4, line 30 to column 5, line 24. Among them, a chlorine atom for X₁ or X₂, a hydrogen atom or a group capable of being released containing a sulfur atom as a releasing atom for X₃ or X₄ and a group capable of being released containing an oxygen atom or a nitrogen atom as a releasing atom for X₅ are preferred.
The reflective support which can be employed in the present invention will now be explained in detail below.
The vinyl chloride resin which constitutes the reflective support used in the present invention is a homopolymer or copolymer containing a vinyl chloride monomer as at least one kind of monomer. It is preferred that the vinyl chloride monomer occupies at least 50% by weight of the total monomer component. Suitable examples of comonomer component include, for example, methyl methacrylate, vinyl acetate, acrylonitrile, a fluorinated olefin, a vinyl ether, vinyl bromide, maleic acid, dichlorobutadiene, vinyl fluoride, vinylidene fluoride, trifluorochloroethylene, tetrafluoroethylene, vinylidene chloride, styrene, butadiene and chloroprene. Two or more of these comonomer components may be employed.
To the vinyl chloride resin may be added various fillers, plasticizers and stabilizers. Suitable examples of fillers include starch, wood flour, clay, calcium carbonate and bentonite. Suitable examples of plasticimers include a phthalic ester (e.g., dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, butyllauryl phthalate, dilauryl phthalate, butylbenzyl phthalate), a phosphoric ester (e.g., tricresyl phosphate, trixylenyl phosphate, trioctyl phosphate), a straight chain dibasic acid ester (e.g., dioctyl adipate, dioctyl azelate, dioctyl sebacate) and butylphthalyl butylglycolate. Suitable examples of stabilizers include tribasic lead sulfate, dibasic lead stearate and lead orthostearate.
A filler may be added in an amount of from about 20 parts to 100 parts by weight per 100 parts by weight of the resin material.
The white pigments which can be added to the vinyl chloride resin include, for example, titanium white, zinc white, calcium carbonate, barium sulfate, white lead, white organic pigments or dyes and brightening agents.
Preferred examples of the aforementioned brightening agents include the following compounds.

The white pigments can be employed individually or as a mixture of two or more thereof. The total amount of the white pigment added is preferably from 1 part by weight to 30 parts by weight and more preferably from 5 parts by weight to 15 parts by weight per 100 parts by weight of the vinyl chloride resin material.
The vinyl chloride resin as used in the present invention exhibits resistance to heat deformation, preferably to at least 50°C, more preferably to at least 70°C thereby preventing a dimensional change during the drying step after preparation and development steps of light-sensitive materials or during their use.
It is preferred that the average reflectivity of the reflective support used in the present invention in a visible range is from 80 to 98%.
The thickness of the reflective support is preferably from 50 µm to 500 µm and more preferably from 100 µm to 300 µm.
When a hydrophilic colloid layer such as a silver halide emulsion layer is coated on the reflective support, a subbing treatment may be conducted in order to improve adhesion of both materials. With respect to the subbing treatment, various kinds of methods are known and a suitable method can be appropriately selected therefrom.

For instance, there may be employed a method wherein the surface of the support is etched with acetone to make a rough surface, wood flour (cellulose component) is coated to fill in a concave portion of the surface and to cover a convex portion of the surface and thereby an affinity with gelatin is provided (because of a good affinity between cellulose and protein) and then a subbing solution containing pearl essence is coated thereon as described in Japanese Patent Publication No. 3583/60, a method wherein at least one layer composed of a mixture of cellulose nitrate and a vinyl acetate-vinyl chloride copolymer is coated as a subbing agent as described in Japanese Patent Publication No. 25742/64, a method wherein a support is subjected to corona discharge treatment to a specified degree and then a layer containing a hydrophilic colloidal binder (such as gelatin) and dispersible colloidal silica at a weight ratio of 5/1 to 1/2 is coated thereon as described in European Patent Application (OPI) No. EP 0065329A1 (the term "OPI" as used herein refers to a "published unexamined application"), a method wherein a straight chain polyphosphoric acid ester resin is coated on a support as described in British Patent 742,370, a method wherein a hardened gelatin subbing layer is subjected to corona discharge treatment and then a light-sensitive silver halide emulsion layer is coated as described in British Patent 1,472,854, a method wherein an epoxidated rubbery polymer and a film-forming unsaturated polyester are coated as subbing agents as described in British Patent 1,179,563, a method wherein first a solution of an isobutyl methacrylate polymer dissolved in a solvent which does not affect the vinyl chloride polymer and then a usual subbing layer composed of gelatin and cellulose nitrate is coated thereon as described in U.S. Patent 2,388,817, and a method wherein a subbing solution having the composition shown below is coated on a support as described in U.S. Patent 2,483,966.

Composition of Subbing Solution	Parts by Weight
Cellulose Nitrate (nitrogen content 11%)	5.0 to 7.0
Acetone	40.0 to 50.0
Methyl Ethyl Ketone	9.0 to 10.0
Methanol	25.0 to 35.0
Dioctyl Phosphate	2.5 to 4.2
Ethanol	0.0 to 3.5

It is preferred that a development inhibitor releasing compound (DIR compound) is added to the color photographic light-sensitive material according to the present invention for the purpose of further improving the sharpness.
Suitable DIR compounds include DIR couplers as described in U.S. Patents 3,933,500, 4,187,100 and 4,477,563, British Patent 1,504,094 and Japanese Patent Application (OPI) Nos. 206834/84, 210440/84 and 92556/85.
The dye which is formed upon the coupling reaction of the color image forming coupler represented by the above-described general formula (1), (2), (3), (4) or (5) which is used in the present invention with an oxidation product of an aromatic primary amine color developing agent (CD) will be explained in greater detail below.
As yellow dyes, those dyes formed from pivaloyl acetanilide type couplers are preferred. These dyes have the excellent features that the long wavelength side of their spectral absorptions is sharply cut and that their fastness is excellent. Further, they are easily dispersed in a hydrophilic colloid using a small amount of an organic solvent or using a water-insoluble and organic solvent soluble polymer, in comparison with benzoyl acetanilide type couplers, and thus they enable the provision of a color-forming layer which is thin and has strong physical properties.
The yellow dyes which are preferably employed in the present invention are those represented by the following general formula (5-1):

wherein R₁₄ and R₁₅, which may be the same or different, each represents a hydrogen atom or a substituent which is ordinarily used for a yellow coupler, provided that both R₁₄ and R₁₅ are not hydrogen atoms at the same time; and

represents a coupling residue of an aromatic primary amine developing agent.
Suitable examples of the substituents represented by R₁₄ and R₁₅ include an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, a halogen atom, an alkoxycarbamoyl group, an aliphatic amido group, an alkylsulfamoyl group, an alkylsulfonamido group, an alkylureido group, an alkyl-substituted succinimido group, an aryloxy group, an aryloxycarbonyl group, an arylcarbamoyl group, an arylamido group, an arylsulfamoyl group, an arylsulfonamido group, an arylureido group, a carboxy group, a sulfo group, a nitro group, a cyano group and a thiocyano group. The coupler used may be, for instance, a polymer coupler including a bis coupler.
In the general formula (5-1),

preferably represents a coupling residue of a phenylenediamine derivative represented by the following general formula (6):

wherein R₁₁ and R₁₂ each represents a substituted or unsubstituted alkyl group; and R₁₃ represents one to four hydrogen atoms or one to four substituents.
In the general formula (6), the alkyl group represented by R₁₁ or R₁₂ is preferably an alkyl group having from 1 to 4 carbon atoms. Suitable examples of the substituents for the alkyl group include a hydroxy group, an alkylsulfonamido group and an alkoxy groups. Specific examples of R₁₁ or R₁₂ include an ethyl group, a β-hydroxyethyl group, a β-methanesulfonamidoethyl group and a β-methoxyethyl group. Further, a representative example of the substituent represented by R₁₃ is an alkyl group (for example, a methyl group).
As the magenta dyes used in the present invention, those represented by the following general formula (4-1) or (4-2) are preferred.

wherein

represents a coupling residue of an aromatic primary amine developing agent and R₁₆ and R₁₇, which may be the same or different, each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, a silyloxy group, a sulfonyloxy group, an acylamino group, an anilino group, a ureido group, an imido group, a sulfamoylamino group, a carbamoylamino group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonamido group, a carbamoyl group, an acyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group or an aryloxycarbonyl group. Of these groups, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an acylamino group and an anilino group are particularly preferred. R₁₆ or R₁₇ may also be a divalent group to form a bis compound. Further, the magenta dye represented by the general formula (4-1) or (4-2) may be in the form of a polymer dye in which the dye moiety represented by the general formula (4-1) or (4-2) exists at the main chain or the side chain of the polymer and particularly a polymer derived from a vinyl monomer having the moiety represented by the general formula (4-1) or (4-2) is preferred. In this case, R₁₆ or R₁₇ represents a linking group connected to a vinyl group.
The linking group represented by R₁₆ or R₁₇ in the cases wherein the part represented by the general formula (4-1) or (4-2) is included in a vinyl monomer includes an alkylene group (including a substituted or unsubstituted alkylene group, e.g., a methylene group, an ethylene group, a 1,10-decylene group or -CH₂CH₂OCH₂CH₂-), a phenylene group (including a substituted or unsubstituted phenylene group, e.g., a 1,4-phenylene group, a 1,3-phenylene group,

or

-NHCO-, -CONH-, -O-, -OCO-, and an aralkylene group (e.g.,

or

or a combination thereof.
Specific examples of preferred linking groups include -NHCO-, -CH₂CH₂-,

-CH₂CH₂NHCO-,

-CONHCH₂CH₂NHCO-, -CH₂CH₂OCH₂CH₂NHCO-, and
Further, the vinyl group in the vinyl monomer may further have a substituent in addition to the moiety represented by the general formula (4-1) or (4-2). Preferred examples of these substituents include a chlorine atom or a lower alkyl group having from 1 to 4 carbon atoms (e.g., a methyl group, an ethyl group or a butyl group).
The polymer derived from the vinyl monomer having the dye moiety may be a copolymer with a non-color forming ethylenic monomer.
Suitable examples of the non-color forming ethylenic monomers include an acrylic acid such as acrylic acid, α-chloroacrylic acid, α-alacrylic acid (e.g., methacrylic acid), an ester or an amide derived from an acrylic acid (e.g., acrylamide, n-butylacrylamide, tert-butylacrylamide, diacetoneacrylamide, methacrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, tert-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, vinyl propionate, vinyl laurate), acrylonitrile, methacrylonitrile, an aromatic vinyl compound (e.g., styrene and a derivative thereof, vinyltoluene, divinylbenzene, vinylacetophenone, sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, a vinyl alkyl ether (e.g., vinyl ethyl ether), maleic acid, maleic anhydride, a maleic acid ester, N-vinyl-2-pyrrolidone, N-vinylpyridine and 2- or 4-vinylpyridine. Particularly, an acrylic acid ester, a methacrylic acid ester and a maleic acid ester are preferred.
Two or more non-color forming ethylenically unsaturated monomers can be used together. For example, a combination of n-butyl acrylate and methyl acrylate, styrene and methacrylic acid, methyl acrylate and diacetoneacrylamide can be used.
As is well known in the field of polymer color couplers, the non-color forming ethylenically unsaturated monomer which is used to copolymerize with a solid water-insoluble monomer coupler can be selected in such a manner that the copolymer to be formed has good physical properties and/or chemical properties, for example, solubility, compatibility with a binder in a photographic colloid composition such as gelatin, flexibility and heat stability.
The magenta dyes according to the present invention are characterized by good spectral absorption characteristics wherein the characteristic second absorption on the short wavelength side is not present or, if present, is small and the absorption on the long wavelength side is sharply cut, and by an excellent fastness to high humidity and heat. Further, when polymer magenta dyes are used, they can be dispersed as a latex and thus an organic solvent having a high boiling point is not necessary, or is used only in a reduced amount. As a result, it is possible to decrease the thickness of the color forming layer and to increase the physical strength thereof.
The cyan dyes used in the present invention are most typically dyes which are obtained upon an oxidation coupling reaction of phenol type couplers with paraphenylenediamine color developing agents. These phenol type cyan couplers may be used together with naphthol type cyan couplers. Specific examples of naphthol type couplers include those as described, for example, in U.S. Patent 2,474,293 and preferably those as described, for example, in U.S. Patents 4,052,212, 4,146,396, 4,228,233 and 4,296,200. Specific examples of phenol couplers include those as described, for example, in U.S. Patents 2,396,929, 2,801,171, 2,772,162 and 2,895,826.
Cyan couplers which are stable against humidity and temperature are advantageously used in the present invention. Typical examples of those couplers include phenol cyan couplers having an alkyl group more than a methyl group at the meta-position of the phenol nucleus as described in, for example, U.S. Patent 3,772,002, cyan couplers as described in U.S. Patents 2,772,162, 3,758,308, 4,126,396, 4,334,011 and 4,327,173, West German Patent Application (OLS) No. 3,329,729 and European Patent 121,365 and cyan couplers as described in, for example, U.S. Patents 3,446,622, 4,333,999, 4,451,559 and 4,427,767.
The cyan dyes according to the present invention can cover a wavelength range of 600 µm to 700 µm by using two or more dyes represented by the general formula (1) or (2) in combination. The cyan dyes can provide cyan color images having a small absorption on the short wavelength side and they are excellent in fastness to high humidity and heat.
Specific examples of the dyes which can be used in the present invention are set forth below (compounds (1)-1 to (1)-4, (2)-1 to (2)-14, (4)-1 to (4)-3 and (5)-1 to (5)-6). Also shown below are examples of couplers for use in the present invention (compounds (2)-15 to (2)-18 and (5)-7 to (5)-11).

In the above-described formulae,

may represent

Further,

may represent a coupling residue of a p-phenylenediamine derivative such as, for instance,
The dyes which form images according to the present invention are preferably used in combination with one or more kinds of organic solvents having a high boiling point of at least 160°C represented by the general formula (7), (8), (9), (10) or (11) as shown below. Details of these organic solvents are described in Japanese Patent Application (OPI) No. 215272/87, pages 138 to 144. Further, it is particularly preferred that the dyes are used in combination with water-insoluble, organic solvent-soluble polymers as described in, for example, Japanese Patent Publication No. 30474/73, U.S. Patent 3,619,195 and International Application No. PCT/JP 87/00492 filed July 9, 1987. Moreover, the dyes may be used in combination with loaded polymeric latexes as described in U.S. Patent 4,203,716.

W₁ - COO - W₂ (8)

W₁ - O - W₂ (11)

wherein W₁, W₂ and W₃ each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group; W₄ represents W₁, -O-W₁ or -S-W₁; n represents an integer from 1 to 5, when n is two or more, two or more W₄'s may be the same or different; and W₁ and W₂ in the general formula (11) may be connected with each other to form a condensed ring.
Preferred specific examples of water-insoluble, organic solvent-soluble polymers include polyvinyl acetate, polyvinyl propionate, and polymethyl methacrylate.
Further, the specific examples of polymers (P-4) to (P-158) as described in International Application No. PCT/JP 87/00492, pages 22 to 30, and the specific examples of polymers 1 to 35 as described in Japanese Patent Publication No. 30494/73, pages 4 to 5 are also preferred.
These polymers may be employed together with the above described organic solvent having a high boiling point of at least 160°C.
Furthermore, it is preferred that the dyes according to the present invention are used in combination with color fading preventing agents or antioxidizing agents represented by the general formula (12) or (13) shown below. Of these compounds, those which are soluble in organic solvents are preferred.

wherein R₂₀ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group or a hydrolyzable protective group; R₂₁, R₂₂, R₂₃, R₂₄ and R₂₅, which may be the same or different, each represents a hydrogen atom or a substituent; R₃₀ represents a hydrogen atom, an aliphatic group, an acyl group, a sulfonyl group, a sulfinyl group, an oxy radical group or a hydroxy group; A represents a non-metallic atomic group necessary to form a 5-membered, 6-membered or 7-membered ring; and R₂₆, R₂₇, R₂₈ and R₂₉, which may be the same or different, each represents a hydrogen atom or an alkyl group.
Specific examples of substituents represented by R₂₁ or R₂₅ include a hydrogen atom and an alkyl group, and preferred examples of the alkyl group include a straight chain or branched chain alkyl group having from 1 to 8 carbon atoms, particularly a methyl group, an n-butyl group, a t-butyl group, a t-pentyl group and an n-octyl group. Specific examples of substituents represented by R₂₂, R₂₃ or R₂₄ include a hydrogen atom, an alkyl group, -NHR₃₁, an alkoxy group and -COO-R₃₂, R₃₁ represents a nitrogen-containing heterocyclic group and R₃₂ represents an alkyl group or an aryl group. The above-mentioned alkyl, alkoxy or aryl group means a substituted or unsubstituted alkyl, alkoxy or aryl group.
Of the substituents represented in the general formula (12), R₂₀ and R₂₁ or two of R₂₁, R₂₂, R₂₃, R₂₄ and R₂₅ which are present in ortho-positions of each other may be connected with each other to form a 5-membered, 6-membered or 7-membered ring.
Of the substituents represented in the general formula (13), R₂₆ and R₂₇, R₂₈ and R₂₉ or R₃₀ and R₂₆ may be connected with each other to form a 5-membered, 6-membered or 7-membered ring.
Specific examples of the compounds represented by the general formula (12) or (13) are set forth below.

The color print according to a preferred embodiment of the present invention can be obtained by subjecting to color development processing, after imagewise exposure, a color printing paper which comprises a thin reflective support having thereon a yellow color forming layer containing a blue-sensitive silver halide emulsion and a yellow color forming coupler, a magenta color forming layer containing a green-sensitive silver halide emulsion and a magenta color forming coupler, and a cyan color forming layer containing a red-sensitive silver halide emulsion and a cyan color forming coupler, and optionally further, e.g., an antihalation layer, an intermediate layer, a yellow filter layer and a protective layer, if appropriate for the desired photographic material.
The silver halide emulsion which is used in the present invention is usually prepared by mixing an aqueous solution of a water-soluble silver salt (for example, silver nitrate) with an aqueous solution of a water-soluble halide (for example, potassium bromide, sodium chloride, potassium iodide or a mixture thereof) in the presence of an aqueous solution of a water-soluble polymer (for example, gelatin). As the silver halide thus-prepared, in addition to silver chloride and silver bromide, a mixed silver halide, for example, silver chlorobromide, silver chloroiodobromide and silver iodobromide are representative examples. The silver halide which is preferably employed in the present invention is silver chloroiodobromide, silver iodochloride or silver iodobromide, each containing 3 mol% or less silver iodide.
The silver halide grains may have different layers in the inner portion and the surface portion, multi-phase structures containing junctions, or may be uniform throughout the grains. Further, a mixture of these silver halide grains having different structures may be employed. For instance, with respect to silver chlorobromide grains having different phases, those having nuclei or a single layer or plural layers which are rich in silver bromide as compared with the mean halogen composition in their inner portion, or those having nuclei or a single layer or plural layers which are rich in silver chloride as compared with the mean halogen composition in their inner portion may be employed. Therefore, surface layers of the grains are rich in silver bromide as compared with the mean halogen composition or contrary to this, surface layers are rich in silver chloride.
The average grain size of the silver halide grains (the grain size being defined as the grain diameter if the grain has a spherical or a nearly spherical form and as the length of the edge if the grain has a cubic form, and being averaged based on projected areas of the grains) is preferably from 0.1 µm to 2 µm, and particularly from 0.15 µm to 1 µm. The grain size distribution may be either narrow or broad.
A so-called monodispersed silver halide emulsion having a narrow grain size distribution which comprises at least 90%, particularly at least 95% by number or by weight of the total silver halide grains having a size within the range of the average grain size ±40% is preferably employed in the present invention. Further, in order to achieve the desired gradation of the light-sensitive material, two or more monodispersed silver halide emulsions which have different grain sizes from each other can be mixed in one emulsion layer or can be coated in the form of superimposed layers which have substantially the same spectral sensitivity. Moreover, two or more polydispersed silver halide emulsions or combinations of a monodispersed emulsion and a polydispersed emulsion may be employed in a mixture or in the form of superimposed layers.
The silver halide grains which can be used in the present invention may have a regular crystal structure, for example, a cubic, octahedral, dodecahedral or tetradecahedral structure, an irregular crystal structure, for example, a spherical structure, or a composite structure thereof. Further, tabular silver halide grains can be used. Particularly, a silver halide emulsion wherein tabular silver halide grains having a ratio of diameter/thickness of not less than 5, preferably not less than 8 account for at least 50% of the total silver halide grains present, calculated based on the projected area of the silver halide grains, can be employed. In addition, mixtures of silver halide grains having different crystal structures may be used. These silver halide emulsions may be those of the surface latent image type in which the latent images are formed mainly on the surface thereof, or those of the internal latent image type in which the latent images are formed mainly in the interior thereof.
Dyes are employed in the present invention for various purposes, for example, as filter dyes, for irradiation prevention or for antihalation. Examples of such dyes which are preferably used are oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, anthraquinone dyes and azo dyes. Further, cyanine dyes, azomethine dyes, triarylmethane dyes and phthalocyanine dyes are also useful. Oil-soluble dyes may be added to the hydrophilic colloid layer by emulsification using an oil droplet-in-water dispersing method.
In the color photographic light-sensitive material of the present invention, inorganic or organic hardening agents may be employed in order to harden the hydrophilic colloid layers applied on the support. For example, active halogen compounds (for example, 2,4-dichloro-6-hydroxy-1,3,5-triazine) and active vinyl compounds (for example, 1,3-bisvinylsulfonyl-2-propanol, 1,2-bisvinylsulfonylacetamidoethane or a vinyl type polymer having a vinylsulfonyl group in its side chain) are preferred since they rapidly act on hydrophilic colloid such as gelatin to harden and provide stable photographic properties. Also N-carbamoylpyridinium salts and haloamidinium salts are excellent in view of their high hardening speed.
The color developing solution used for development processing of the color photographic light-sensitive material of the present invention to obtain a color print is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as the main component. As a color developing agent, while an aminophenol type compound is useful, a p-phenylenediamine type compound is preferably used. Typical examples of the p-phenylenediamine type compounds include 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, or a sulfate, hydrochloride or p-toluenesulfonate thereof. These diamines are preferably employed in the form of salts since the salts are generally more stable than their free forms.
The color developing solution generally contains pH buffering agents such as carbonates, borates or phosphates of alkali metals, and development inhibitors or antifogging agents such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds. In addition, if desired, the color developing solution may also contain, for example, preservatives such as, for example, hydroxylamines, derivatives thereof (for example, N,N-dialkyl substituted derivatives) or sulfites; organic solvents such as, for example, triethanolamine, derivatives thereof or diethylene glycol; development accelerators such as, for example, benzylalcohol, polyethyleneglycol, quaternary ammonium salts or amines; competing couplers; nucleating agents such as, for example, sodium borohydride; auxiliary developing agents such as, for example, 1-phenyl-3-pyrazolidone; viscosity imparting agents; various chelating agents as represented, for example, by aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids and phosphonocarboxylic acids; and antioxidants as described in West German Patent Application (OLS) No. 2,622,950.
In the case of development processing for reversal color photographic light-sensitive materials, the color development is usually conducted after the black-and-white development.
After color development, the photographic emulsion layer is usually subjected to bleach processing. The bleach processing can be carried out simultaneously with or separately from fix processing. Further, in order to perform rapid processing, a processing method in which bleach-fix processing is conducted after bleach processing can be employed. As bleaching agents, iron (III) salts of ethylenediaminetetraacetic acid, iron (III) salts of diethylenetriaminepentaacetic acid and persulfates are preferred in view of rapid processing and less environmental pollution. Further, ethylenediaminetetraacetic acid iron (III) complex salts are particularly useful both in an independent bleaching solution and in a mono-bath bleach-fixing solution. Further, thiosulfates are ordinarily employed as fixing agents. In the bleach-fixing solution or the fixing solution, sulfites, bisulfites, carbonylbisulfite adducts, for instance, are preferably employed as preservatives.
After the bleach-fix processing or fix processing, water wash processing and/or stabilization processing are usually conducted. In the water washing step or stabilizing step, various known compounds may be employed, for instance, for the purpose of preventing precipitation or saving water. For example, a water softener such as, for example, an inorganic phosphoric acid, an aminopolycarboxylic acid, an organic aminopolyphosphonic acid, or an organic phosphoric acid for the purpose of preventing the formation of precipitation; a sterilizer or antimold for the purpose of preventing the propagation of various bacteria, algae and molds; a metal salt such as, for example, a magnesium salt, an aluminum salt or bismuth salt; or a surface active agent for the purpose of reducing the drying load or preventing drying marks; and various hardening agents; may be added, if desired. Further, the compounds as described in L.E. West, Photo. Sci. Eng., Vol. 6, pages 344 to 359 (1965) may be added. Particularly, the addition of chelating agents and antimolds is effective.
Further, the color photographic light-sensitive material according to the present invention may contain, if appropriate, various 1-phenyl-3-pyrazolidones for the purpose of accelerating the color development. Typical examples of the compounds include those as described in Japanese Patent Application (OPI) Nos. 64339/81, 144547/82, 211147/82, 50532/83, 50536/83, 50533/83, 50534/83, 50535/83 and 115438/83.
In the present invention, the various kinds of processings described above can be conducted in a temperature range of from 10°C to 50°C. Although the standard temperature is from 33°C to 38°C, it is possible to carry out the processing at higher temperatures in order to accelerate the processing whereby the processing time is shortened, or on the other hand, at lower temperatures in order to achieve an improvement in image quality and to maintain the stability of the processing solutions.
Further, for the purpose of reducing the amount of silver employed in the color photographic light-sensitive material, the photographic processing may be conducted utilizing color intensification using cobalt or hydrogen peroxide as described in West German Patent Application (OLS) No. 2,226,770 or U.S. Patent 3,674,499.
Moreover, in the case of continuous processing, the variation of the composition in each processing solution can be prevented by using a replenisher for each processing solution, whereby a constant finish can be achieved. The amount of replenisher can be reduced to one half or less of the standard amount of replenishment for the purpose of reducing the costs.
Direct positive color prints can be obtained with respect to the color photographic light-sensitive materials by using an internal latent image type emulsion which was not previously fogged as a silver halide emulsion, and performing a fogging treatment after the imagewise exposure but before or during the color development step.
As the fogging treatment, a method conducting fogging exposure or a method using a nucleating agent (a chemical fogging method) are effective. More specifically, a light fogging method and a chemical fogging method (a method using a nucleating agent together with a nucleating accelerator) as described, for example, in U.S. Application Serial No. 60,790 filed June 12, 1987, pages 55 to 88, or European Patent Application No. 87 108489.3 filed June 12, 1987, pages 55 to 88 (corresponding to Japanese Patent Application No. 136949/86) can be utilized.
The color photographic print obtained by development processing of the color photographic light-sensitive material according to the present invention advantageously not only has a good fastness to light, humidity and heat but also has an excellent sharpness of color images.
Further, since it has a good smoothness of the emulsion layer, the irregularity of the color image density is remarkably reduced.
Moreover, the support composed of a vinyl chloride resin used in the present invention is excellent in flexibility and strength and its variation in the degree of elasticity on change in humidity is small and can be ignored in comparison with other photographic supports.
Furthermore, it is easy to emboss a card after printing and thus the color photographic light-sensitive material and the color photographic print according to the present invention can be suitably employed as, for instance, ID cards, cashing cards and telephone cards.
The present invention is explained in greater detail with reference to the following examples.

EXAMPLE 1

On a support composed of a hard vinyl chloride resin (a copolymer containing at least 50 mol% of vinyl chloride monomer component, with the remainder thereof being vinylidene chloride and methyl methacrylate, and further containing 12 parts by weight of TiO₂ per 100 parts of total weight of the copolymer) and having a thickness of 150 µm and an average reflectance in the visible range of 85% or more, provided with subbing treatment, the first layer to the seventh layer described below were coated to prepare a color photographic light-sensitive material which was designated Sample 101. The support used was in conformity with a standard of JIS-K-6734-Class C, No. 1, as described in JIS published by Japanese Standards Association.
The coated amounts shown below are in g/m², and the coated amounts of silver halide shown below are measured as silver.
The following dyes were used as spectral sensitizing dyes in the emulsion layers, respectively.

Blue-sensitive Emulsion Layer:

4-{5-chloro-2-[5-chloro-3-(4-sulfonatobutyl)benzothiazolin-2-ylidenemethyl]-3-benzothiazolino}-butanesulfonatotriethylammonium salt (2x10⁻⁴ mol per mol of silver halide)

Green-Sensitive Emulsion Layer:

3,3ʹ-Di-(γ-sulfopropyl)-5,5ʹ-diphenyl-9-ethoxacarbocyanine sodium salt (2.5x10⁻⁴ mol per mol of silver halide)

Red-Sensitive Emulsion Layer:

3,3ʹ-Di-(γ-sulfopropyl)-9-methylthiacarbocyanine sodium salt (2.5x10⁻⁴ mol per mol of silver halide)
The following dyes were employed as irradiation preventing dyes in the emulsion layers, respectively.

Red-sensitive Emulsion Layer:

Samples 102 and A' were prepared in the same manner as described for sample 101 except for changing couplers as shown in Table 1 below.
These samples were stepwise exposed and then subjected to development processing according to the processing steps as shown below.

Processing Step Temperature Time

Development 33°C 3 min 30 s

Bleach-fixing 33°C 1 min 30 s

Washing with Water 28 to 35°C 3 min

The composition of each processing solution used in the above-described processing steps is as follows:

Developing Solution
Trisodium nitrilotriacetate	2.0 g
Benzyl alcohol	15 ml
Diethylene glycol	10 ml
Sodium sulfite	2.0 g
Potassium bromide	0.5 g
Hydroxylamine sulfate	3.0 g
4-Amino-3-methyl-N-ethyl-N-[β-(methanesulfonamido)ethyl]-p-phenylenediamine sulfate	5.0 g
Sodium carbonate (monohydrate)	30 g
Water to make	1 l
(pH: 10.1)

Bleach-Fixing Solution
Ammonium thiosulfate (54 wt%)	150 ml
Sodium sulfite	15 g
Ammonium iron (III) ethylenediaminetetraacetate	55 g
Disodium ethylenediaminetetraacetate	4 g
Water to make	1 l
(pH: 6.9)

The sharpness of Samples 101, 102 and A' thus-processed was determined. The sharpness is a value indicating clearness of the outlines of images and the ability to duplicate fine images. The value known as CTF was used herein. CTF means the degree of decrease in amplitude against a spatial frequency as a rectangular wave. The sharpness at 15 lines/mm of spatial frequency thus-measured is shown in Table 2 below. The larger value indicates the better sharpness. TABLE 2

Sharpness Sample 101 Sample 102 Sample A'*

B 25.4 27.2 22.4

G 33.0 35.6 29.3

R 34.9 37.1 30.7

* Comparative Sample
An irregularity of the image density was not observed in both Samples 101 and 102.

EXAMPLE 2

Silver Halide Emulsion (7) for a blue-sensitive silver halide emulsion layer was prepared in the following manner.

Solution 8

H₂O 1,000 ml

NaCl 5.8 g

Gelatin 25 g

Solution 9

Sulfuric acid (1N) 20 ml

Solution 11

KBr 0.18 g

NaCl 8.51 g

H₂O to make 130 ml

Solution 12

AgNO₃ 25 g

H₂O to make 130 ml

Solution 13

Pb(CH₃COO)₂·3H₂O (0.1%) 28 ml

Solution 14

KBr 0.70 g

NaCl 34.05 g

H₂O to make 285 ml

Solution 15

AgNO₃ 100 g

H₂O to make 285 ml
Solution 8 was heated at 60°C, Solution 9 and Solution 10 were added thereto and then Solution 11 and Solution 12 were added thereto simultaneously over a period of 60 min. One minute after the completion of the addition of Solution 11 and Solution 12, Solution 13 was added and then after 9 min Solution 14 and Solution 15 were added simultaneously over a period of 25 min. After 5 min, the temperature was dropped and the mixture was desalted. Water and gelatin were added thereto for dispersion and the pH was adjusted to 6.0 whereby a mono-dispersed cubic silver chlorobromide emulsion (having an average grain size of 1.00 µm, a coefficient of variation of 0.11 and a silver bromide content of 1 mol%) was obtained. The emulsion was subjected to optimum chemical sensitization using triethyl thiourea and chloroauric acid. Thereafter, the Spectral Sensitizer (S-1) shown below was added in an amount of 5 x 10⁻⁴ mol per mol of silver halide.
Silver Halide Emulsion (8) for a green-sensitive silver halide emulsion layer and Silver Halide Emulsion (9) for a red-sensitive silver halide emulsion layer were prepared in the same manner as described above except for changing the amounts of chemicals used in Solution 8 and Solution 10, the kinds and amounts of spectral sensitizers, and the temperatures and times for addition. Spectral Sensitizer (S-2) shown below was used for Silver Halide Emulsion (8) and Spectral Sensitizer (S-3) shown below was used for Silver Halide Emulsion (9).

Spectral Sensitizer (S-1):

(5 x 10⁻⁴ mol per mol of silver halide)

Spectral Sensitizer (S-2):

(4 x 10⁻⁴ mol per mol of silver halide)

(7.0 x 10⁻⁵ mol per mol of silver halide)

Spectral Sensitizer (S-3):

(0.9 x 10⁻⁴ mol per mol of silver halide)
Further, to the red-sensitive silver halide emulsion layer, the compound described below was added in an amount of 2.6 x 10⁻³ mol per mol of silver halide.

Moreover, 1-(5-methylureidophenyl)-5-mercaptotetrazole was added to the blue-sensitive emulsion layer, green-sensitive emulsion layer and red-sensitive emulsion layer in the amounts of 8.5 x 10⁻⁵ mol, 7.7 x 10⁻⁴ mol and 2.5 x 10⁻⁴ mol per mol of silver halide present in the layer, respectively.
The average grain sizes, coefficients of variation and halide compositions of Silver Halide Emulsions (7) to (9) are shown in Table 3 below.
Samples 103 and 104 were prepared in the same manner as described for Samples 101 and 102, respectively, except that the silver halide emulsions used in the first layer, the third layer and the fifth layer were changed to Silver Halide Emulsions (7), (8) and (9), respectively. These samples were stepwise exposed in the same manner as described in Example 1 and then subjected to development processing consisting or color development, bleach-fixing and rinse steps as shown below.

Processing Step Temperature Time

Color Development 35°C 45 s

Bleach-Fixing 35°C 45 s

Rinse 28 to 35°C 1 min 30 s

The compositions of each processing solution used in the above-described processing steps are as follows:

Color Developing Solution:
Water	800 ml
Pentasodium diethylenetriaminepentaacetate	1.0 g
Sodium sulfite	0.2 g
N,N-Diethylhydroxylamine	4.2 g
Potassium bromide	0.01 g
Sodium chloride	1.5 g
Triethanolamine	8.0 g
N-Ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate	4.5 g
Potassium carbonate	30.0 g
4,4'-Diaminostilbene type brightening agent (Whitex 4 manufactured by Sumitomo Chemical Co., Ltd.)	2.0 g
Water to make	1,000 ml
pH 10.1

Bleach-Fixing Solution:
Water	700 ml
Ammonium thiosulfate (54% by weight aq. soln.)	150 ml
Sodium sulfite	15 g
NH₄[Fe(III)(EDTA)]	55 g
EDTA·2Na·2H₂O	4 g
Glacial acetic acid	8.61 g
Water to make	1,000 ml
pH 5.4

Rinse Solution:
EDTA·2Na·2H₂O	0.4 g
Water to make	1,000 ml
pH 7.0

The sharpness of the samples thus-processed was measured and it was determined that a further improvement in sharpness was obtained.

EXAMPLE 3

1) Preparation of Emulsions

Emulsions A to H were prepared as follows.

Emulsion A

An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were simultaneously added to a gelatin aqueous solution under vigorous stirring at 75°C over a period of 40 min to obtain a monodispersed silver bromide emulsion containing octahedral grains of 0.4 µm in average grain size. Four mg of sodium thiosulfate and 4 mg of chloroauric acid (4 hydrate) were added to the emulsion per mol of silver, followed by heating at 75°C for 80 min to effect chemical sensitization. The thus obtained silver bromide grains were used as cores, and were allowed to further grow in the same precipitating environment as the first step for 40 min to finally obtain an octahedral monodispersed core/shell silver bromide emulsion of 0.6 µm in average grain size (coefficient of variation : 14%). After washing with water and desalting of the emulsion, 0.9 mg of sodium thiosulfate were added thereto per mol of silver, followed by heating at 65°C for 60 min to effect chemical sensitization. Thus, internal latent image type silver halide emulsion A was obtained.

Emulsion B

30 g of gelatin were added to 1 l of a solution containing 0.5 mol of KBr, 0.2 mol of NaCl and 0.0015 mol of KI and dissolved. To the solution 700 ml of a 1 mol/ℓ silver nitrate aqueous solution were added at 60°C over a period of 20 min, followed by effecting physical ripening for 20 min. The emulsion was washed with water to remove water-soluble halides, then 20 g of gelatin were added thereto, and thereafter water was added thereto to make the total volume 1,200 ml. Thus, an emulsion of 0.4 µm in average grain size was obtained. The emulsion was washed with water and desalted to obtain internal latent image type silver halide emulsion B.

Emulsion C

30 g of gelatin were added to 1 l of a solution containing 0.5 mol of KBr, 0.2 mol of NaCl and 0.0015 mol of KI and dissolved. To the solution 700 ml of a 1 mol/ℓ silver nitrate aqueous solution were added at 60°C over a period of 20 min, followed by effecting physical ripening for 20 min. The emulsion was washed with water to remove water-soluble halides, then 20 g of gelatin were added thereto, and thereafter water was added thereto to make the total volume 1,200 ml. Thus, an emulsion of 0.4 µm in average grain size was obtained. To 300 ml of the emulsion were added simultaneously 500 ml of a 1 mol/ℓ silver nitrate aqueous solution and 500 ml of a 2 mol/ℓ sodium chloride aqueous solution at 60°C to precipitate silver chloride shells, followed by washing with water. Thus, silver halide emulsion C of 0.7 µm in average grain size was obtained.

Emulsion D

An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were simultaneously added to a gelatin aqueous solution under vigorous stirring at 75°C over a period of 40 min to obtain a monodispersed silver bromide emulsion containing octahedral grains of 0.4 µm in average grain size. Four mg of sodium thiosulfate and 4 mg of chloroauric acid (4 hydrate) were added to this emulsion per mol of silver, followed by heating at 75°C for 80 min to effect chemical sensitization. The thus obtained silver bromide grains were used as cores, and were allowed to further grow by adding a 2 mol/ℓ sodium chloride aqueous solution and a 1 mol/ℓ silver nitrate aqueous solution at 75°C for 40 min to obtain a cubic core/shell silver chlorobromide emulsion of 0.6 µm in average grain size (coefficient of variation: 15%). After washing with water and desalting of the emulsion, 0.5 mg of sodium thiosulfate were added thereto per mol of silver, then heated at 55°C for 60 min to effect chemical sensitization, whereby silver halide emulsion D was obtained.

Emulsion E

An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were simultaneously added to a gelatin aqueous solution under vigorous stirring at 75°C over a period of 90 min to obtain a silver bromide emulsion containing octahedral grains of 0.8 µm in average grain size (core grains). In the above procedure, before the precipitation of the silver halide grains of the emulsion 0.65 g of 3,4-dimethyl-1,3-thiazoline-2-thione were added to the aqueous gelatin solution and the pH and the pAg were maintained at 6 and 8.7, respectively, during the precipitation step. To the silver bromide emulsion 3.4 mg of sodium thiosulfate and 3.4 mg of potassium chloroaurate per mol of silver were added to effect chemical sensitization. The thus obtained chemically sensitized grains were allowed to further grow in the same precipitating environment as the core grain formation to finally obtain an octahedral core/shell silver bromide emulsion of 1.2 µm in average grain size. Then, 9.6 x 10⁻⁴ mol of potassium iodide and 4.2 x 10⁻² g of an N-vinylpyrrolidone polymer (weight-average molecular weight : 38,000) were added to the emulsion per mol of silver to obtain silver halide emulsion E.

Emulsion F

An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were simultaneously added to a gelatin aqueous solution under vigorous stirring at 75°C over a period of 60 min to obtain a silver bromide emulsion. Before precipitation, 100 mg of 3,4-dimethyl-1,3-thiazoline-2-thione and 15 g of benzimidazole per mol of silver were added to a precipitation tank. After the completion of precipitation, crystals of 1.1 µm in average grain size were obtained. Then, 5.4 mg of sodium thiosulfate and 3.9 mg of potassium chloroaurate were added to the emulsion per mol of silver, followed by heating at 75°C for 80 min to effect chemical sensitization. To the thus chemically sensitized core emulsion an aqueous solution of potassium bromide and an aqueous solution of silver nitrate were added simultaneously over a period of 40 min in the same manner as the first step to finally prepare a core/shell silver halide emulsion of 1.5 µm in average grain size. Then, 0.32 mg of sodium thiosulfate and 57 mg of poly(N-vinylpyrrolidone) (weight-average molecular weight : 38,000) were added to the core/shell emulsion per mol of silver, followed by heating at 60°C for 60 min to effect chemical sensitization on the surfaces of grains, whereby silver halide emulsion F was obtained.

Emulsion G

An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were simultaneously added to a gelatin aqueous solution containing potassium bromide under vigorous stirring at 75°C over a period of about 60 min to obtain a silver bromide emulsion. Before precipitation (before the simultaneous addition), 150 mg of 3,4-dimethyl-1,3-thiazoline-2-thione as a silver halide solvent and 15 g of benzimidazole per mol of silver were added to the aqueous gelatin solution. After the completion of precipitation, uniform grain size octahedral silver bromide crystals of 0.8 µm in average grain size were obtained. Then, 4.8 mg of sodium thiosulfate and 2.4 mg of potassium chloroaurate were added to the silver bromide emulsion per mol of silver, followed by heating at 75°C for 80 min to effect chemical sensitization. To the thus chemically sensitized inner nucleus (core) silver bromide emulsion an aqueous solution of potassium bromide and an aqueous solution of silver nitrate were added simultaneously over a period of 45 min in the same manner as the first step to precipitate an internal latent image type core/shell emulsion. To the emulsion 2.5 g of hydrogen peroxide per mol of silver were added as an oxidizing agent, the emulsion was heated at 75°C for 8 min and then washed with water to obtain an emulsion of 1.0 µm in average grain size (coefficient of variation : 12%). Then, 0.75 mg of sodium thiosulfate and 20 mg of poly(N-vinylpyrrolidone) per mol of silver were added to the internal latent image type core/shell silver bromide emulsion, followed by heating at 60°C for 60 min to effect chemical sensitization (ripening) on the surfaces of the grains, whereby silver halide emulsion G was obtained.

Emulsion H

An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were simultaneously added to a gelatin aqueous solution containing 0.3 g of 3,4-dimethyl-1,3-thiazoline-2-thione per mol of silver under vigorous stirring at 75°C over a period of 20 min to obtain a monodispersed silver bromide emulsion containing octahedral grains of 0.4 µm in average grain size. 6 mg of sodium thiosulfate and 6 mg of chloroauric acid (4 hydrate) were added to the emulsion per mol of silver, followed by heating at 75°C for 80 min to effect chemical sensitization. The thus obtained silver bromide grains were used as cores, and were allowed to further grow in the same precipitating environment as the first step for 40 min to finally obtain an octahedral monodispersed core/shell silver bromide emulsion of 0.7 µm in average grain size. After washing with water and desalting of the emulsion, 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (4 hydrate) were added thereto per mol of silver, followed by heating at 60°C for 60 min to effect chemical sensitization. Thus, internal latent image type silver halide emulsion H was obtained.

II) Preparation of Direct Positive Color Photographic Printing Paper

Using core/shell type direct positive emulsions A to H as described above, layers were coated on a reflective support composed of a vinyl chloride resin containing white pigments provided with subbing treatment as used in Example 1 to prepare a multilayer direct positive color photographic printing paper having the layer structure shown in Table 4 below. Coating solutions were prepared in the following manner.

Preparation of Coating Solution for First Layer

10 ml of ethyl acetate and 4 ml of solvent (c) were added to 6.4 g of Cyan Coupler (a) and 2.3 g of Color image stabilizer (b) to dissolve them, and the resulting solution was emulsified and dispersed in 90 ml of a 10% gelatin aqueous solution containing 5 ml of a 10% aqueous sodium dodecylbenzenesulfonate solution. On the other hand, 2.0 x 10⁻⁴ mol of a red-sensitizing dye shown below were added per mol of silver halide to the aforesaid silver halide emulsion (containing 70 g of silver/kg) to prepare 90 g of a red-sensitive emulsion. The emulsified dispersion and the emulsion were mixed and dissolved, followed by adjusting the concentration of the dissolved mixture by the addition of gelatin so as to obtain the composition as shown in Table 4 below. Further, 30 mg of Nucleating agent (n) and 5 x 10⁻⁴ mol of Nucleation accelerating agent (o) were added thereto per mol of silver to prepare a coating solution for the first layer.
Coating solutions for the second layer to the seventh layer were also prepared in the same manner as the coating solution for the first layer. Sodium salt of 1-hydroxy-3,5-dichloro-s-triazine was used as a gelatin hardener for each layer. Spectral sensitizers used for individual emulsions are shown below.

Blue-Sensitive Emulsion Layer:

Green-Sensitive Emulsion Layer:

Red-Sensitive Emulsion Layer:

The following dyes were employed as irradiation preventing dyes in the emulsion layers, respectively.

Green-Sensitive Emulsion Layer:

Red-Sensitive Emulsion Layer:

The chemical structures of the compounds such as couplers employed in this example are shown below.

Yellow couper (k)

Color image stabilizer (ℓ)

Solvent (m)

Development controlling agent (x)

Nucleating gent (n)

Nucleation accelerating agent (o)

Color mixing preventing agent (d)

Magenta coupler (e)

Color image stabilizer (f)

Solvent (g)

a mixture (2:1 by weight ratio) of

UV ray absorbent (h)

a mixture (1:5:3 by molar ratio) of

Color mixing preventing agent (i)

Solvent (j)

Cyan coupler (a)

a mixture (1:1 by molar ratio) of

Color image stabilizer (b)

a mixture (1:3:3 by molar ratio) of

and

Solvent (c)

After adjusting the balance of surface tension and viscosity thereof simultaneously the coating solutions for the first layer to the seventh layer were coated on the support to prepare the multilayer silver halide direct positive color photographic printing papers A to H.

III) Development Processing

The direct positive color photographic printing papers A to H thus prepared were imagewise exposed at color temperature of 4,800°K in an amount of 100 CMS at 1/10 second and then subjected to Processing Step A (pH of the color developing solution: 10.2) shown below and Processing Step B (same a Processing Step A except adjusting the pH of the color developing solution to 11.0), respectively. Direct positive color photographic prints having excellent sharpness and no irregularity of image density were obtained.

Processing Step A:

Step	Time	Temperature
Color Development	2 min 30 s	38°C
Bleach-fixing	40 s	38°C
Stabilizing (1)	20 s	38°C
Stabilizing (2)	20 s	38°C
Stabilizing (3)	20 s	38°C

The stabilizing baths were replenished according to a so-called countercurrent replenishing system of adding the replenisher to the stabilizing bath (3), introducing the overflow from the stabilizing bath (3) into the stabilizing bath (2), and the overflow from the stabilizing bath (2) into the stabilizing bath (1).

The composition of each processing solution used in the above described processing steps is as follows:

Color Developing Solution:	Mother Solution
Diethylenetriaminepentaacetic acid	2.0 g
Benzyl alcohol	12.8 g
Diethylene glycol	3.4 g
Sodium sulfite	2.0 g
Sodium bromide	0.26 g
Hydroxylamine sulfate	2.60 g
Sodium chloride	3.20 g
3-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)aniline	4.25 g
Potassium carbonate	30.0 g
Brightening agent (stilbene type)	1.0 g
Water to make	1,000 ml
pH	10.20

The pH was adjusted with potassium hydroxide or hydrochloric acid.

Bleach-Fixing Solution:	Mother Solution
Ammonium thiosulfate	110 g
Sodium hydrogensulfite	10 g
Ammonium iron (III) diethylenetriaminepentaacetate monohydrate	56 g
Disodium ethylenediaminetetraacetate dihydrate	5 g
2-Mercapto-1,3,4-triazole	0.4 g
Water to make	1,000 ml
pH	6.5

The pH was adjusted with aqueous ammonia or hydrochloric acid.

Stabilizing solution:	Mother Solution
1-Hydroxyethylidene-1,1'-di phosphonic acid (60%)	1.6 ml
Bismuth chloride	0.35 g
Polyvinylpyrrolidone	0.25 g
Aqueous ammonia	2.5 ml
Trisodium nitrilotriacetate	1.0 g
5-Chloro-2-methyl-4-isothiazolin3-one	50 mg
2-Octyl-4-isothiazolin-3-one	50 mg
Brightening agent (4,4'-diamino-stilbene type)	1.0 g
Water to make	1,000 ml
pH	7.5

The pH was adjusted with potassium hydroxide or hydrochloric acid.

EXAMPLE 4

The first layer to the eleventh layer as described in Example 1 of Japanese Patent Application (OPI) No. 174760/87, pages 18, upper half portion in the right-hand column to page 21, lower half portion in the right-hand column were coated on a reflective support composed of a vinyl chloride resin containing white pigments provided with subbing treatment in place of the first layer to the seventh layer to prepare a reversal color photographic light-sensitive material. The color photographic material was processed according to the prescribed development processing steps. A reversal color photographic print having excellent sharpness and no irregularity of image density was obtained.

Claims

A silver halide color photographic material comprising a reflective support composed of a vinyl chloride resin containing a white pigment and having thereon in an appropriate order at least one red-sensitive silver halide emulsion layer containing a cyan color forming coupler represented by the general formula (1) or (2) shown below, at least one green-sensitive silver halide emulsion layer containing a magenta color forming coupler represented by the general formula (3) or (4) shown below, and at least one blue-sensitive silver halide emulsion layer containing a yellow color forming coupler represented by the general formula (5) shown below

wherein R₁, R₄ and R₅ each represents an aliphatic group, an aromatic group, a heterocyclic group, an aromatic amino group or a heterocyclic amino group; R₂ represents an aliphatic group; R₃ and R₆ each represents a hydrogen atom, a halogen atom, an aliphatic group, an aliphatic oxy group or an acylamino group; R₇ and R₈ each represents a substituted or unsubstituted phenyl group; R₉ represents a hydrogen atom or a substituent; R₂ and R₃ or R₅ and R₆ may be connected with each other to form a 5-membered to 7-membered ring; Q represents a substituted or unsubstituted N-phenylcarbamoyl group; Za and Zb, which may be the same or different, each represents a group of -CH=, a group of
or a group of -N=; R₁₀ represents the same substituent as that represented by R₉; and X₁, X₂, X₃, X₄ and X₅ each represents a hydrogen atom or a group capable of being released upon a reaction with an oxidation product of an aromatic primary amine developing agent.
A silver halide color photographic material as claimed in Claim 1, wherein X₁ and X₂ each represents a chlorine atom, X₃ and X₄ each represents a hydrogen atom or a group capable of being released containing a sulfur atom as a releasing atom; and X₅ represents a group capable of being released containing an oxygen atom or a nitrogen atom as a releasing atom.
A silver halide color photographic material as claimed in Claim 1, wherein the vinyl chloride resin is a copolymer containing a vinyl chloride monomer.
A silver halide color photographic material as claimed in Claim 3, wherein the vinyl chloride monomer occupies at least 50% by weight of the total monomer component.
A silver halide color photographic material as claimed in Claim 3, wherein a comonomer component is selected from methyl methacrylate, fluorinated olefin, a vinyl ether, vinyl bromide, vinyl acetate, maleic acid, dichlorobutadiene, vinyl fluoride, vinylidene fluoride, trifluorochloroethylene, tetrafluoroethylene, vinylidene chloride, acrylonitrile, styrene, butadiene, and chloroprene.
A sliver halide color photographic material as claimed in Claim 1, wherein the white pigment is selected from titanium white, zinc white, calcium carbonate, barium sulfate, white lead, white organic pigments and dyes, and brightening agents.
A silver halide color photographic material as claimed in Claim 1, wherein the total amount of the white pigment added is from 1 part by weight to 30 parts by weight per 100 parts by weight of the vinyl chloride resin material.
A silver halide color photographic material as claimed in Claim 1, wherein an average reflectivity of the reflective support in a visible range is from 80 to 98%.
A silver halide color photographic material as claimed in Claim 1, wherein the thickness of the reflective support is from 50 µm to 500 µm.
A silver halide color photographic material as claimed in Claim 1, wherein a surface of the reflective support to which a hydrophilic colloid layer is applied is subjected to subbing treatment.
A silver halide color photographic material as claimed in Claim 1, wherein the color photographic material further comprises a development inhibitor releasing compound.
A silver halide color photographic material as claimed in Claim 1, wherein a silver halide emulsion used in the silver halide emulsion layers is a mono-dispersed silver halide emulsion.
A color photographic print comprising a reflective support composed of a vinyl chloride resin containing a white pigment and having thereon in an appropriate order at least one emulsion layer containing a cyan dye obtained by a reaction of a cyan color forming coupler represented by the general formula (1) or (2) shown below with an oxidation product of an aromatic primary amine developing agent, at least one emulsion layer containing a magenta dye obtained by a reaction of a magenta color forming coupler represented by the general formula (3) or (4) shown below with an oxidation product of an aromatic primary amine developing agent, and at least one emulsion layer containing a yellow dye obtained by a reaction of a yellow color forming coupler represented by the general formula (5) shown below with an oxidation product of an aromatic primary amine developing agent
wherein R₁, R₄ and R₅ each represents an aliphatic group, an aromatic group, a heterocyclic group, an aromatic amino group or a heterocyclic amino group; R₂ represents an aliphatic group; R₃ and R₆ each represents a hydrogen atom, a halogen atom, an aliphatic group, an aliphatic oxy group or an acylamino group; R₇ and R₈ each represents a substituted or unsubstituted phenyl group; R₉ represents a hydrogen atom or a substituent; R₂ and R₃ or R₅ and R₆ may be connected with each other to form a 5-membered to 7-membered ring; Q represents a substituted or unsubstituted N-phenylcarbamoyl group; Za and Zb, which may be the same or different, each represents a group of -CH=, a group of
or a group of -N=; R₁₀ represents the same substituent as that represented by R₉; and X₁, X₂, X₃, X₄ and X₅ each represents a hydrogen atom or a group capable of being released upon a reaction with an oxidation product of an aromatic primary amine developing agent.
A color photographic print as claimed in Claim 13, wherein the yellow dye is a dye represented by the following general formula (5-1):
wherein R₁₄ and R₁₅, which may be the same or different, each represents a hydrogen atom or a substituent which is ordinarily used for a yellow coupler, provided that both R₁₄ and R₁₅ are not hydrogen atoms at the same time; and
represents a coupling residue of an aromatic primary amine developing agent.
A color photographic print as claimed in Claim 14, wherein the substituent represented by R₁₄ or R₁₅ is selected from an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, a halogen atom, an alkoxycarbamoyl group, an aliphatic amido group, an alkylsulfamoyl group, an alkylsulfonamido group, an alkylureido group, an alkyl-substituted succinimido group, an aryloxy group, an aryloxycarbonyl group, an arylcarbamoyl group, an arylamido group, an arylsulfamoyl group, an arylsulfonamide group, an arylureido group, a carboxy group, a sulfo group, a nitro group, a cyano group and a thiocyano group.
A color photographic print as claimed in Claim 14, weherein
represents a coupling residue of a phenylenediamine derivative represented by the following general formula (6):
wherein R₁₁ and R₁₂ each represents a substituted or unsubstituted alkyl group; and R₁₃ represents one to four hydrogen atoms or one to four substituents.
A color photographic print as claimed in Claim 16, wherein a substituent for the substituted alkyl group represented by R₁₁ or R₁₂ is selected from a hydroxy group, an alkylsulfonamido group and an alkoxy group, and the substituent represented by R₁₃ is an alkyl group.
A color photographic print as claimed in Claim 13, wherein the magenta dye is a dye represented by the following general formula (4-1) or (4-2):
wherein R₁₆ and R₁₇, which may be the same or different, each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, a silyloxy group, a sulfonyloxy group, an acylamino group, an anilino group, a ureido group, an imido group, a sulfamoylamino group, a carbamoylamino group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonamido group, a carbamoyl group, an acyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group or an aryloxycarbonyl group, or R₁₆ or R₁₇ may be a divalent group to form a bis compound or a linking group to form a polymer dye, and
represents a coupling residue of an aromatic primary amine developing agent.
A color photographic print as claimed in Claim 18, wherein the linking group is connected to a vinyl group from which the polymer is formed.
A color photographic print as claimed in Claim 13, wherein the cyan dye is composed of two or more dyes formed from two or more cyan color forming couplers represented by the general formula (1) or (2).
A color photographic print as claimed in Claim 13, wherein the dyes are used in combination with one or more kinds of organic solvents having a high boiling point of at least 160°C represented by the following general formula (7), (8), (9), (10) or (11):

W₁ - COO - W₂ (8)

W₁ - O - W₂ (11)

wherein W₁, W₂ and W₃ each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group; W₄ represents W₁, -O-W₁ or -S-W₁; n represents an integer from 1 to 5, when n is two or more, two or more W₄'s may be the same or different; and W₁ and W₂ in the general formula (11) may be connected with each other to form a condensed ring.
A color photographic print as claimed in Claim 13, wherein the dyes are used in combination with one or more kinds of water-insoluble, organic solvent-soluble polymers.
A color photographic print as claimed in Claim 13, wherein the dyes are used in combination with one or more kinds of color fading preventing agents or antioxidants represented by the following general formula (12) or (13):
wherein R₂₀ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group or a hydrolyzable protective group; R₂₁, R₂₂, R₂₃, R₂₄ and R₂₅, which may be the same or different, each represents a hydrogen atom or a substituent; R₃₀ represents a hydrogen atom, an aliphatic group, an acyl group, a sulfonyl group, a sulfinyl group, an oxy radical group or a hydroxy group; A represents a non-metallic atomic group necessary to form a 5-membered, 6-membered or 7-membered ring; and R₂₆, R₂₇, R₂₈ and R₂₉, which may be the same or different, each represents a hydrogen atom or an alkyl group, or R₂₀ and R₂₁ or two of R₂₁, R₂₂, R₂₃, R₂₄ and R₂₅ which are present in ortho-positions with respect to each other may be connected with each other to form a 5-membered, 6-membered or 7-membered ring, or R₂₆ and R₂₇, R₂₈ and R₂₉ or R₃₀ and R₂₆ may be connected with each other to form a 5-membered, 6-membered or 7-membered ring.
A color photographic print prepared by conducting at least a step of processing the silver halide color photographic material as claimed in Claim 1, after imagewise exposure, with a color developing solution containing an aromatic primary amine color developing agent.
A color photographic print prepared by adhering a color photographic print obtained by conducting at least a step of processing the silver halide color photographic material as claimed in Claim 1 except using a transparent support instead of the reflective support, after imagewise exposure, with a color developing solution containing an aromatic primary amine color developing agent, on a reflective support composed of a vinyl chloride resin containing a white pigment.