JPH07119964B2 - Silver halide color photographic light-sensitive material and color photographic print - Google Patents

Description

TECHNICAL FIELD The present invention relates to a silver halide color photographic light-sensitive material and a color photographic print, and particularly to a color photographic print useful for an ID card, a caching card, a telephone card and the like.

(Prior Art) Conventional silver halide color photographic light-sensitive materials have a cyan color forming coupler-containing silver halide emulsion layer, a magenta color forming coupler-containing silver halide emulsion layer and an arrow color forming coupler-containing silver halide emulsion layer on various supports. It is painted and manufactured.

As the transparent support for photographic use, for example, transparent plastic film such as cellulose triacetate, polyethylene terephthalate, vinyl resin, etc., and as the reflective support, baryta paper, synthetic paper, polyethylene laminated paper, and white pigment are used. Known plastic sheets, glass plates, metal plates (for example, an aluminum plate whose surface is anodized) containing the same are known.

In the reflection type support, it has been proposed to fill the plastic material with a white pigment or to coat the surface thereof with a white pigment-containing layer in order to improve the whiteness of the support.

(Problems to be solved by the invention) However, if the whiteness of the support is usually increased, the white reproducibility of the subject is improved, but the sharpness of the image tends to deteriorate. Therefore, various measures have been taken such as incorporating an anti-irradiation dye in a photosensitive silver halide emulsion layer provided on a support or providing an anti-halation layer.

When a baryta paper or a paper laminated with polyethylene is used as the support, the smoothness of the support is deteriorated due to the unevenness of the paper fibers, which causes uneven thickness of the coating film of the silver halide emulsion. It causes a serious defect that the image density unevenness occurs after the development processing.

This flaw is especially noticeable when you capture the scenery of the sky,
Above all, it was a problem when taking color photographs.

Accordingly, it is a first object of the present invention to provide a reflective color photographic light-sensitive material and a color photographic print which give a color image having excellent sharpness.

The second object is to provide a silver halide color photographic light-sensitive material and a color photographic print having a reflective support having excellent smoothness.

Thirdly, it is to provide a silver halide color photographic light-sensitive material and a support for color photographic prints capable of composing numbers, letters and the like by heat processing when used for various cards.

(Means for Solving the Problems) As a result of earnest studies, the present inventor has found that the above-mentioned general purpose is as follows on a reflective support having a vinyl chloride resin itself containing a white pigment as a support. A red light-sensitive silver halide emulsion layer containing a cyan color coupler represented by formula (1) or (2), and a green light-sensitive silver halide containing a magenta color coupler represented by general formula (3) or (4). A silver halide color photographic light-sensitive material obtained by coating at least one layer of an emulsion layer and a blue light-sensitive silver halide emulsion layer containing a yellow color-forming coupler represented by the general formula (5) in any order, and this light-sensitive material. After the imagewise exposure of the material, a color photographic print obtained through the step of treating with a color developer containing at least an aromatic primary amine color developing agent or vinyl chloride containing a white pigment. Effectively achieved by a color photographic print obtained by sticking the above-mentioned color photographic print (however, the support uses a transparent support) on a reflection type support having a resin itself as a support. Found out.

General formula (1) General formula (2) General formula (3) General formula (4) General formula (5) In the formula, R ₁ , R ₄ and R ₅ are each an aliphatic group, an aromatic group,
Represents a heterocyclic group, an aromatic amino group or a heterocyclic amino group, R ₂ represents an aliphatic group, R ₃ and R ₆ are each a hydrogen atom, a halogen atom, an aliphatic group, an aliphatic oxy group, or an acylamino group. R ₇ and R ₈ represent a substituted or unsubstituted phenyl group, and R ₉ represents a hydrogen atom or a substituent.

R ₂ and R ₃ and R ₅ and R ₆ may be connected to each other to form a 5- to 7-membered ring.

Q represents a substituted or unsubstituted N-phenylcarbamoyl group, Za and Zb represent a -CH = group, Alternatively, -N = represents a group. R ₁₀ represents a substituent. X ₁ ,
X ₂ , X ₃ , X ₄ and X ₅ each represent a hydrogen atom or a group capable of leaving by reaction with an oxidized product of an aromatic primary amino developing agent (hereinafter referred to as CD).

Examples of these leaving groups include those described in U.S. Pat. No. 4,540,654 at column 4, line 30 to column 5, line 24. Especially, for X ₁ and X ₂ , chlorine atom, X ₃ and
A leaving group containing a sulfur atom as a leaving atom is preferable for X ₄ , and a leaving group having oxygen or nitrogen as a leaving atom is preferable for X ₅ .

The present invention is described in detail below.

The vinyl chloride resin constituting the reflective support used in the present invention comprises a homopolymer or copolymer formed by using vinyl chloride as at least one monomer. The vinyl chloride monomer component is preferably 50% (by weight) or more of the total monomer components.

As the comonomer component, for example, methylmethacrylate, vinyl acetate, acrylonitrile, fluorinated olefin,
Vinyl ether, vinyl bromide, vinyl acetate, maleic acid, dichlorobutadiene, vinyl fluoride, vinylidene fluoride, trifluorochloroethylene, tetrafluoroethylene, vinylidene chloride, acrylonitrile, styrene,
Butashen, chloroprene, etc. can be mentioned. You may use 2 or more types of these comonomer components.

Various fillers, plasticizers and stabilizers can be added to the vinyl chloride resin. For example, as the filler, starch,
Wood powder, clay, calcium carbonate, bentonite, etc., as a plasticizer, phthalate ester (eg, dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, butyl lauryl phthalate, dilauryl phthalate, butyl benzyl phthalate). , Phosphates (eg tricresyl phosphate, trixylenyl phosphate, triocryl phosphate), direct dibasic acid esters (eg dioctyl adipate, dioctyl azelate, dioctyl sebacate), other butylphthalyl butyl glycolate In addition, tribasic lead sulfate, dibasic lead stearate, orthostearate and the like can be added as a stabilizer. An appropriate amount of the filler added is about 20 to 100 parts per 100 parts of the resin raw material. Examples of the white pigment added to the vinyl chloride resin include titanium white, zinc white, calcium carbonate, barium sulfate, lead white, white organic pigments and dyes, and fluorescent whitening agents.

The following compounds may be mentioned as preferred specific examples of the above fluorescent whitening agent.

These may be used alone or may be used with rigidity, but the total amount of white pigment added is 1 to 3 parts with respect to 100 parts of vinyl chloride resin.
0 part is preferable, and more preferably 5 to 15 parts.

Further, the heat-resistant temperature of the vinyl chloride resin that can be used in the present invention is preferably 50 ° C. or higher from the viewpoint that the manufacturing process of the light-sensitive material, the drying after the development treatment, or the dimensional change in use does not occur. 70 ° C or higher is more preferable.

The average reflectance in the visible region of the reflective support used in the present invention is preferably 80 to 98%.

The thickness of the reflective support is preferably 50 to 500 μ, more preferably 100 to 300 μ.

In order to coat a hydrophilic colloid layer such as a silver halide emulsion on this reflection type support, an undercoat is applied to improve the adhesion between the two. Various methods are known as this undercoating method, and they can be appropriately applied.

For example, as proposed in Japanese Examined Patent Publication No. 35-3583, the surface of the support is corroded with acetone to make the surface rough and uneven, and the wood powder is left as it is, and the pearl essence is applied onto it. Method of applying an undercoat liquid containing: JP-B-39-257
A method of applying at least one layer of a mixture of cellulose nitrate and a vinyl acetate-vinyl chloride copolymer as an undercoating agent as proposed in No. 42; European Patent Application Publication EP0065329A.
After irradiating a corona discharge on a support to a specified degree as proposed in 1, the hydrophilic colloidal binder (gelatin etc.) and dispersible colloidal silica are mixed at 5/1 to 1/2 (weight ratio). A method of applying a layer containing; a method of applying a linear polyphosphate ester resin as proposed in British Patent 742,370; on a hardened subbed gelatin layer as proposed in British Patent 1,472,854 A corona discharge prior to coating a light sensitive silver halide emulsion layer onto the undercoat layer; an epoxidized rubbery polymer and a film-forming agent as a primer such as proposed in British Patent 1,179,563. Method of coating with unsaturated polyester; US Patent
A method of first applying an isobutyl methacrylate polymer solution in a solvent that does not affect the vinyl chloride polymer, and then applying a conventional gelatin and nitrocellulose subbing layer, as proposed in 2,388,817; US Patent
A method of applying an undercoat liquid having the following composition as proposed in No. 2,483,966 can be mentioned. Undercoating liquid composition parts by weight nitrocellulose (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 Sharpness is suitable for the color light-sensitive material of the present invention. It is preferable to add a development inhibitor-releasing compound (DIR compound) for the purpose of improving the above-mentioned properties.

As a useful DIR compound, DIR represented by the general formula [DI] or [D-II] described in Japanese Patent Application No. 61-169523 can be used.
Couplers, more specifically (D-
I-1) to (D-I-17) and (D-II-1) to (D-II)
-10) and the like, and further, a DIR compound represented by the general formula (I) described in Japanese Patent Application No. 61-199595, more specifically, a compound number (I- 1) ~ (I
-53) and the like.

Next, it is formed by a coupling reaction between the color image forming couplers represented by the above-mentioned general formulas (1) to (5) used in the present invention and an aromatic primary amine type color developing agent oxidant (CD). The color forming dye will be described in detail.

As the yellow coloring dye, a dye obtained from a pivaloyl acetanilide type coupler is preferable. This dye has the characteristics that the long-wave end of spectral absorption is sharply cut and it has excellent fastness. Compared to benzoylacetanilide type mother nucleus, it is easy to disperse in hydrophilic colloid with a small amount of organic solvent, and it is easy to disperse even water-insoluble and organic solvent-soluble polymer, giving a thin and strong physical strength coloring layer. Cheap. The yellow dye according to the present invention is preferably a dye represented by formula (5-1).

General formula (5-1) In the formula, R ₁₄ and R ₁₅ are hydrogen atoms (neither are hydrogen atoms)
Or a substituent usually used for a yellow coupler, such as an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, a halogen atom, an alkoxycarbamoyl group, an aliphatic amide group, an alkylsulfamoyl group, an alkylsulfonamide group, an alkylureido group. , An alkyl-substituted succinimide group, an aryloxy group, an aryloxycarbonyl group, an arylcarbamoyl group, an arylamide group, an arylsulfamoyl group, an arylsulfonamide group, an arylureido group, a carboxy group, a sulfo group, a nitro group, a cyano group, It represents a thiocyano group or the like, and these substituents may be the same or different. The coupler may be a bis or higher polymer coupler.

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

General formula (6) In the formula, R ₁₁ and R ₁₂ each represent a substituted or unsubstituted alkyl group. The alkyl group preferably has 1 to 4 carbon atoms. Specific examples of this substituent include a hydroxyl group, an alkylsulfonamide group, an alkoxyl group and the like. Specific examples of R ₁₁ and R ₁₂ include ethyl group, β-hydroxyethyl group, β-methanesulfonamidoethyl group, β
-Methoxyethyl group and the like can be mentioned. R ₁₃ represents a hydrogen atom or 1 to 4 substituents. An alkyl group (for example, a methyl group) is typical as the substituent.

The magenta dye according to the present invention has the following general formula (4-
The dyes represented by formulas 1) and (4-2) are particularly preferable.

General formula (4-1) General formula (4-2) In the formula, R ₁₆ and R ₁₇ may be the same as or different from each other, and each is 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, carbamoyloxy group, silyloxy group, sulfonyloxy group,
Acylamino group, anilino group, ureido group, imide group,
Sulfamoylamino group, carbamoylamino group, alkylthio group, arylthio group, heterocyclic thio group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, carbamoyl group, acyl group, sulfamoyl group, sulfonyl group, sulfinyl group , An alkoxycarbonyl group, an aryloxycarbonyl group, particularly preferably 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. R ₁₆ or R ₁₇ may be a divalent linking group to form a bis form. Further, the dye residue represented by the general formulas (4-1) and (4-2) may be in the form of a polymer coupler existing in the main chain or side chain of the polymer, and particularly vinyl having a moiety represented by the general formula. Polymers derived from monomers are preferred, in which case R ₁₆ and R ₁₇ represent linking groups that bond to vinyl groups.

When the structure represented by the general formulas (4-1) and (4-2) is contained in the vinyl monomer, the linking group represented by R ₁₆ and R ₁₇ is an alkylene group (a substituted or unsubstituted alkylene group. , For example, a methylene group, an ethylene group, a 1,10-decylene group,
CH ₂ CH ₂ OCH ₂ CH ₂ —, etc.), phenylene group (substituted or unsubstituted phenylene group, for example, 1,4-phenylene group,
1,3-phenylene group, -NHCO-, -CONH-, -O-, -OCO- and aralkylene groups (for example, Includes groups that are formed by combining those selected from.

The following are preferred linking groups.

_{-NHCO -, - CH 2 CH 2} -, -CH ₂ CH ₂ NHCO-, _{-CONH-CH 2 CH 2 NHCO -} , - CH 2 CH 2 O-CH 2 CH 2 -NHCO-, The vinyl group has the general formula (4-1) or (4-
In addition to the residue represented by 2), it may be substituted with other substituents, and a preferable substituent is a chlorine atom or a lower alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group, butyl group, etc.). ).

The polymer derived from the vinyl monomer having a dye may be a copolymerizable polymer with a non-color forming ethylene-like monomer. In this case, the non-color-forming ethylenic monomers include acrylic acid, α-chloroacrylic acid, α-alacrylic acid (for example, methacrylic acid) and esters or amides derived from these acrylic acids (for example, acrylamide, n-butyl acrylamide, t-butyl acrylamide, diacetone acrylamide, methacrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, n- Octyl acrylate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (eg styrene and its derivatives,
Vinyltoluene, divinylbenzene, vinylacetophenone and sulfomethylene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether (eg vinyl ethyl ether), maleic acid, maleic anhydride, maleic acid ester, N-vinyl- 2-pyrrolidone, N-vinylpyrrolidine, and 2-
Alternatively, there is 4-vinylpyridine or the like. Acrylic acid esters, methacrylic acid esters, and maleic acid esters are particularly preferable. Two or more kinds of the non-color-forming ethylenically unsaturated monomers used here can be used together.

For example, n-butyl acrylate and methyl acrylate, styrene and methacrylic acid, methyl acrylate and diacetone acrylamide, and the like.

As is well known in the art of polymer color couplers, the non-chromogenic, ethylenically unsaturated monomers for copolymerization with solid water-insoluble monomer couplers are the physical and / or chemical properties of the copolymer formed. , The solubility, compatibility with the binder of the photographic colloid composition, eg gelatin, its flexibility, thermal stability, etc., can be chosen to be favorably influenced.

The magenta dye according to the present invention is characterized in that it has little or no second absorption on the short-wave side and sharply cuts the absorption on the long-wave side, and has excellent fastness to high humidity and heat. . Further, when the magenta dye is a polymer, it can be dispersed as a latex, so that it is not necessary to use a high boiling point organic solvent, or the amount used can be reduced. Therefore, the thickness of the color forming layer can be reduced and the physical strength can be increased.

The cyan dye of the present invention is most typically obtained by an oxidative coupling reaction between a phenolic coupler and a paraphenylenediamine type color developing agent. This phenol-based cyan coupler may be used in combination with a naphthol-based cyan coupler. As a naphthol coupler,
For example, naphthol couplers described in U.S. Pat.No. 2,474,293, preferably U.S. Pat.Nos. 4,052,212 and 4,14.
6,396, 4,228,233 and 4,296,200. Further, as the phenol-based coupler, for example, U.S. Patent Nos. 2,369,929 and 2,801,171,
No. 2,772,162, No. 2,895,826 and the like. Cyan couplers which are fast to humidity and temperature are preferably used in the present invention, and typical examples thereof include a phenol core meta-formula described in U.S. Pat.No. 3,772,002.
Phenolic cyan coupler having an alkyl group of ethyl group or more at the position, U.S. Pat. Nos. 2,772,162 and 3,758,308
No. 4,126,396, No. 4,334,011, No. 4,327,17
No. 3, West German Patent Publication No. 3,329,729 and European Patent No. 121,
Those described in US Pat. No. 365, etc., and U.S. Pat.
Nos. 4,333,999, 4,451,559 and 4,42
There are couplers described in No. 7,767.

The cyan dye according to the present invention is 600-700 by combining two or more dyes represented by the general formula (1) or (2).
It has an excellent feature that it covers the wavelength region of mμ and can obtain a dye image with little absorption on the short wave side, and is also excellent in fastness to high humidity and heat.

Next, specific examples of the dye according to the present invention will be shown. However, it is not limited to this.

Of the specific examples listed above Represents

Other It may be a coupling residue of a p-phenylenediamine derivative such as

The image forming dye according to the present invention is a combination of one or more high boiling organic solvents represented by the following general formulas (7), (8), (9), (10) and (11). It is preferable to coexist. Details of these are described on pages 440 to 470 of Japanese Patent Application No. 61-32462. Further, Japanese Patent Publication No. 48-30474, U.S. Patent No. 3,619,195 and Japanese Patent Application No. 61-1628.
It is particularly preferable to coexist with a water-insoluble polymer soluble in an organic solvent as described in No. 13 and the like. US patent
You may coexist with the loadable polymer latex of 4,203,716.

General formula (7) General formula (8) W ₁ -COO-W ₂ General formula (9) General formula (10) Formula (11) W ₁ -O-W ₂ (In the formula, W ₁ , W ₂ and W ₃ each represent a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocyclic group, W ₄ is W ₁ , OW ₁ or SW
₁ , n is an integer of 1 to 5, and when n is 2 or more, W ₄ may be the same or different, and in the general formula (11), W ₁ and W ₂ are condensed rings. You may form.

Specific preferred examples of the water-insoluble and organic solvent-soluble polymers are shown below, but the invention is not limited thereto.

(P-1) Polyvinyl acetate (P-2) Polyvinyl propionate (P-3) Polymethyl methacrylate Other specific examples of the polymer described on pages 32 to 39 of Japanese Patent Application No. 61-162813 (P- 4)-(P-69) and Japanese Patent Publication No. 48-30494
Specific Examples 1 to 35 of Polymers Described on Pages 4 to 5 of Japanese Patent Publication No.
Is also mentioned as a preferable example.

These polymers can be used in combination with the above high boiling point organic solvent.

Further, it is preferable that the dye of the present invention coexist with a browning inhibitor or an antioxidant represented by the following general formula (12) or (13). Among these, a compound soluble in an organic solvent is particularly preferable.

General formula (12) General formula (13) In the formula, R ₂₀ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocycle, or a hydrolyzable protecting group. R ₂₁ ,
R ₂₂ , R ₂₃ , R ₂₄ and R _{25, which} may be the same or different, each represents a hydrogen atom or a substituent. R ₃₀ represents a hydrogen atom, an aliphatic group, an allyl group, a sulfonyl group, a sulfinyl group, an oxy radical group or a hydroxyl group.
A represents a group of non-metal atoms necessary for forming a 5-membered, 6-membered or 7-membered ring.

R ₂₆ , R ₂₇ , R ₂₈ and R _{29, which} may be the same or different, each represents a hydrogen atom or an alkyl group.

Among the substituents represented by the general formula (12), R ₂₀ and R ₂₁ or
Of R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ , those in the ortho positions may be bonded to each other to form a 5-, 6- or 7-membered ring.

Of the substituents represented by the general formula (13), R ₂₆ , R ₂₇ and R
₂₈ and R ₂₉ , or R ₃₀ and R ₂₆ may combine with each other to form a 5-, 6-, or 7-membered ring.

Next, specific examples of the compounds represented by the general formulas (12) and (13) are shown, but the compounds are not limited thereto.

A preferred embodiment of the color print according to the present invention has a yellow color-forming layer containing a blue-sensitive silver halide emulsion and a yellow color-forming coupler and a magenta color-containing layer containing a green-sensitive silver halide emulsion and a magenta color-forming coupler on a thin reflective support. Imagewise exposure of a color-forming layer, a cyan color-forming layer containing a red-sensitive silver halide emulsion and a cyan color-forming coupler, to a color photographic paper provided with an antihalation layer, an intermediate layer, a yellow filter layer and a protective layer, if necessary. After that, color development processing can be performed to obtain a color print.

The silver halide emulsion used in the present invention usually comprises a water-soluble silver salt (for example, silver nitrate) solution and a water-soluble halogen salt (for example, potassium bromide, sodium chloride, potassium iodide alone or a mixture thereof) gelatin solution. It is manufactured by mixing in the presence of an aqueous polymer solution. As the silver halide thus produced, in addition to silver chloride and silver bromide, mixed silver halides such as silver chlorobromide and silver chloroiodobromide,
A typical example is silver iodobromide. The silver halide preferably used in the present invention is silver chloroiodobromide, silver iodochloride or silver iodobromide containing no silver iodide or containing 3 mol% or less.
The silver halide grains may have different phases in the inside and the surface layer, may have a multi-phase structure having a junction structure, or may have a uniform phase as a whole. Moreover, they may be mixed. For example, in the case of silver chlorobromide grains having different phases, it may be a grain having a silver bromide-rich nucleus or a single layer or a plurality of layers in the grain, which is higher than the average halogen composition. Further, it may be a grain having a nucleus rich in silver chloride from the average halogen composition or a single or multiple layers in the grain. Therefore, the surface layer of the grains may be covered with a layer richer in silver bromide than the average halogen composition or, conversely, a layer richer in silver chloride. Average grain size of silver halide grains (the grain diameter is the grain size for spherical or near-sphere grains, and the ridge length is the grain size for cubic grains).
Is preferably 2 μ or less and 0.1 μ or more, and particularly preferably 1 μ or less and 0.15 μ or more. The particle size distribution may be narrow or wide. 90% or more of all particles, especially 95% within ± 40% of average particle size by number of particles or weight
It is preferable to use a so-called monodisperse silver halide emulsion having a narrow grain size distribution in the present invention.
In order to satisfy the target gradation of the light-sensitive material, two or more kinds of monodisperse silver halide emulsions having different grain sizes are mixed in the same layer or different layers in an emulsion layer having substantially the same color sensitivity. Can be applied in multiple layers. 2 more
It is also possible to use more than one kind of polydisperse silver halide emulsion or a combination of a monodisperse emulsion and a polydisperse emulsion as a mixture or a multilayer.

The silver halide grains used in the present invention may have a regular crystal such as a cube, octahedron, dodecahedron or tetradecahedron, and may have an irregular shape such as a sphere. It may have an (irregular) crystal form, or may have a composite form of these crystal forms. Further, tabular grains may be used, and an emulsion in which tabular grains having a length / thickness ratio value of 5 or more, particularly 8 or more account for 50% or more of the total projected area of the grains may be used. It may be an emulsion composed of a mixture of these various crystal forms. These various emulsions may be either a surface latent image type which forms a latent image mainly on the surface or an internal latent image type which is formed inside the grain.

Further, the dye can be used for various purposes such as for filters, for prevention of irradiation and for prevention of halation. As such dyes, oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, anthraquinone dyes, azo dyes are preferably used, and in addition, cyanine dyes, azomethine dyes, triarylmethane dyes, phthalocyanine dyes are also useful. . The oil-soluble dye can be emulsified by the oil-in-water dispersion method and added to the hydrophilic colloid layer.

In the color light-sensitive material of the present invention, an inorganic or organic hardener is used to cure the multilayer hydrophilic colloid layer coated on the support. For example, active halogen compounds (2,4
-Dichloro-6-hydroxy-1,3,5-triazine etc.) and active vinyl compounds (1,3-bisvinylsulfonyl-2-propanol, 1,2-bisvinylsulfonylacetamidoethane or vinylsulfonyl group in the side chain) The vinyl-based polymer and the like) are preferable because they rapidly cure the hydrophilic colloid such as gelatin and give stable photographic characteristics. N-carbamoylpyridinium salts and haloamidinium salts are also excellent in fast curing speed.

The color developing solution used in the developing process for obtaining a print from the color light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. As the color developing agent, aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and particularly 3-methyl-4-amino-N, N-diethylaniline and 3-methyl-4-. Amino-N-ethyl-N-β-hydroxylethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-
Amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates are preferable. Salts of these diamines are generally more stable than those in the free state, and are preferably used.

The color developing solution is a pH buffering agent such as an alkali metal carbonate, borate or phosphate, a development inhibitor such as a bromide, an iodide, a benzimidazole, a benzothiazole or a mercapto compound, or an antifoggant. Etc. are generally included. If necessary, preservatives such as hydroxylamine and its derivatives (for example, N, N-dialkyl-substituted compounds) or sulfites, triethanolamine and its derivatives, organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol ,
Quaternary ammonium salts, development accelerators such as amines, competitive couplers, nucleating agents such as sodium boron hydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, Various chelating agents represented by aminopolyphosphonic acid, alkylphosphonic acid, and phosphonocarboxylic acid, West German patent application (OL
S) The antioxidant described in No. 2,622,950 may be added to the color developing solution.

In the development processing of a reversal color light-sensitive material, black and white development is usually performed before color development.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed at the same time as the fixing process, or may be performed individually. Further, in order to speed up the process, a bleach-fixing process may be performed after the bleaching process. As the bleaching agents, ethylenediaminetetraacetic acid iron (III) salt, diethylenetriaminepentaacetic acid iron (III) salt and persulfate are preferable from the viewpoint of rapid treatment and environmental pollution. Further, the ethylenediaminetetraacetic acid iron (III) complex salt is particularly useful in a stand-alone bleaching solution as well as in a one-bath bleach-fixing solution. Thiosulfate is generally used as a fixing agent. As the bleach-fixing solution and the preservative for the fixing solution, sulfite, bisulfite or carbonyl bisulfite adduct is preferable.

After the bleach-fixing treatment or the fixing treatment, a washing treatment and / or a stabilizing treatment are usually performed. Various known compounds may be added to the washing process and the stabilizing process for the purpose of preventing precipitation and saving water. For example, in order to prevent precipitation, water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, organic aminopolyphosphonic acid, and organic phosphoric acid, bactericides and antibacterial agents that prevent the formation of various bacteria, algae, and molds. Agent,
If necessary, a metal salt typified by a magnesium salt, an aluminum salt or a bismuth salt, a surfactant for preventing a drying load or unevenness, and various hardeners can be added. Or West Photographic Science and Engineering magazine (LEWes
t.Phot.Sci.Eng.), Volume 6, pp. 344-359 (1965)
You may add the compound as described in the above. It is particularly effective to add a chelating agent or an antifungal agent.

The color light-sensitive material according to the present invention may contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary. Typical compounds are
56-64339, 57-144547, 57-211147, 58-505
32, 58-50536, 58-50533, 58-50534, 58
-50535 and 58-115438.

The above various treatments are performed at 10 ° C to 50 ° C. A temperature of 33 ° C to 38 ° C is standard, but it is possible to raise the temperature to accelerate the treatment and shorten the treatment time, and conversely to lower the temperature to improve the image quality and improve the stability of the treatment liquid. it can. In addition, West German Patent No. 2,226,707 for saving silver in photosensitive materials.
Alternatively, treatment with cobalt intensification or hydrogen peroxide intensification as described in US Pat. No. 3,674,499 may be performed.

Further, in the case of continuous processing, a constant finish can be obtained by using a replenisher for each processing solution to prevent fluctuations in the liquid composition. The replenishment amount can be reduced to half or less than the standard replenishment amount for cost reduction.

In the color light-sensitive material of the present invention, an internal latent image type emulsion which has not been fogged in advance is used as a silver halide emulsion, and after imagewise exposure, a fog treatment is performed prior to color development processing or during color development. You can get a positive color print directly.

As the fogging treatment, a method of performing fogging exposure or a method of using a nucleating agent (chemical fogging method) is effective. Specifically, for example, Japanese Patent Application No. 61-226292, pages 33 to 57. The optical fogging method or the chemical fogging method (method in which a nucleating agent and a nucleation accelerator are used in combination) described in 1) can be applied.

(Effects of the Invention) The color photographic print obtained by developing the color light-sensitive material of the present invention has not only excellent fastness to light, humidity and heat but also excellent sharpness of color image. Has the advantage that

In addition, the smoothness of the emulsion film was excellent, so that the problem of unevenness in color image density was remarkably improved.

Further, the support made of vinyl chloride resin used in the present invention has excellent flexibility and strength, and the degree of expansion and contraction due to changes in humidity is negligibly small as compared with other photographic supports.

In addition, the color photosensitive material and the color photographic print of the present invention are ID
It is suitable for use in cards, cashing cards, telephone cards, and the like.

Example 1 A hard vinyl chloride resin (containing 12 parts by weight of TiO ₂ and 50 mol% or more of vinyl chloride monomer component based on the total amount of all monomer components, and a copolymer of vinylidene chloride and methyl methacrylate) having a thickness of 150 μm in the visible region. On a support having an average reflectance of 85% or more, an undercoat was applied, and then a photographic layer consisting of the following first to seventh layers was applied to prepare a color light-sensitive material.

* This support complied with the JIS-K-6734-C type 1 standard.

(Structure of Photographic Layer) The number corresponding to each component indicates the coating amount expressed in units of g / m ² , and for silver halide, the coating amount in terms of silver.

First layer (blue-sensitive layer) Silver chlorobromide emulsion (80 mol% silver bromide) ...... Silver 0.30 Yellow coupler (* 1) ...... 0.70 Same as above solvent (TNP) ...... 0.15 Gelatin ...... 1.20 Second layer ( Middle layer) Gelatin: 0.90 Di-t-octylhydroquinone: 0.05 Same as above Solvent (DBP): 0.10 Third layer (green sensitive layer) Silver chlorobromide emulsifier (70 mol% of bromizing agent): Silver 0.45 Magenta Coupler (* 2)… 0.35 Same solvent (TOP) …… 0.44 Anti-fading agent (* 3 / * 4) …… 0.05 / 0.10 Gelatin …… 1.00 4th layer (UV absorbing intermediate layer) UV absorber (* 5) / * 6 / * 7) 0.06 / 0.25 / 0.25 Same as above solvent (TNP) …… 0.20 Gelatin …… 1.50 Fifth layer (red sensitive layer) Silver chlorobromide emulsion (silver bromide 50 mol%) …… Silver 0.20 Cyan Coupler (* 8 / * 9) ...... 0.2 / 0.2 Coupler solvent TNP / DBP ...... 0.10 / 0.20 Gelatin ...... 0.9 6th layer (UV absorbing intermediate layer) UV absorber (* 5 / * 6) / * 7) …… 0.06 / 0.25 / 0.25 Same as above Solvent (DBP) …… 0.20 Gelatin 1.5 7th layer (protective layer) Gelatin …… 1.5 Here, DBP is dibutyl phthalate and TOP is tri (n-).
Octyl phosphate) and TNP represent tri (n-nonyl phosphate).

The following dyes were used as the spectral sensitizer for each emulsion layer.

Blue-sensitive emulsion layer; 4- {5-chloro-2- [5-chloro-3
-(4-Sulfonatobutyl) benzothiazoline-2-ylidenemethyl] -3-benzothiazolio} butanesulfonate triethylammonium salt (2 x 10 ^-4 mol per mol of silver halide) Green-sensitive emulsion layer; 3,3'-di- (Γ-sulfopropyl) -5,
5'-Diphenyl-9-ethyloxacarbocyanine sodium salt (2.5 × 10 ^-4 mol per mol of silver halide) Red-sensitive emulsion layer; 3,3'-di- (γ-sulfopropyl) -9
-Methyl-thiadicarbocyanine sodium salt (2.5 x 10 ^-4 mol per mol of silver halide) The following dyes were used as the anti-irradiation dye in each emulsion layer.

This photosensitive material was used as Sample 101.

Next, Samples 102 and A were prepared in exactly the same manner except that the changes were made as shown in Table 1. After subjecting these samples to gradation exposure, development processing was performed by the following processing steps. Step Temperature Time current image liquid 33 ° C. 3 minutes 30 seconds Bleach-fixing solution 33 ° C. 1 min 30 sec Washing 28 to 35 ° C. 3.0 minutes developer nitrilotriacetic acetate 3Na 2.0 g Benzyl alcohol 15ml diethyleneglycol 10ml Na ₂ SO ₃ 2.0 g KBr 0.5g Hydroxylamine sulfate 3.0g 4-Amino-3-methyl-N-ethyl-N- [β- (methanesulfonamido) ethyl] -p-phenylenediamine sulfate 5.0g Na ₂ CO ₃ (1 Water salt) 30g Add water to make 1 liter (pH 10.1) Bleach and fixer Ammonium thiosulfate (54wt%) 150ml Na ₂ SO ₃ 15g NH ₄ [Fe (EDTA)] 55g EDTA ・ 2Na 4g Add water 1 Turn to liter (pH 6.9) The sharpness of each of the samples -101, -102 and A which were color-developed as described above was measured.

Sharpness is a quantity that represents the sharpness of the outline of an image and the ability to render a fine image. A value called CTF is used here. CTF represents the degree of attenuation of the amplitude with respect to the spatial frequency as a square waveform. Table 2 shows the sharpness at a spatial frequency of 15 lines / mm. The higher the value, the higher the sharpness. Sample-101 Sample-102 Sample-A (for comparison) Sharpness B 25.4 27.2 22.4 G 33.0 35.6 29.3 R 34.0 37.1 30.7 No unevenness in image density was observed in neither Sample-101 nor Sample-102.

Example-2 A silver halide emulsion (7) for a blue-sensitive silver halide emulsion layer was prepared as follows.

(8 solution) H ₂ O 1000cc NaCl 5.8g Gelatin 25g (9 solution) Sulfuric acid (1N) 20cc (10 solution) The following silver halide solvent (1%) 3cc (11 solution) was added to _{KBr 0.18g NaCl 8.51g H 2 O 130cc} (12 fluid) AgNO ₃ 25g H ₂ O was added 130 cc (13 _{fluid) Pb (CH 3 COO) 2} (3 dihydrate) (0.1% ) 28cc (14 solution) KBr 0.70g NaCl 34.05g H ₂ O is added 285cc (15 solution) AgNO ₃ 100g H ₂ O is added and 285cc (8 solution) is heated to 60 ° C, and (9 solution) and (9 solution) 10 solution) was added. After that, (11 solution) and (12 solution) were simultaneously added by spending 60 minutes. 1 minute after the addition of (11 solution) and (12 solution),
Solution), and after a further 9 minutes, (14 Solution) and (15 Solution)
It took 25 minutes and was added simultaneously. Five minutes after the addition, the temperature was lowered and the mixture was desalted. Water and dispersed gelatin were added to adjust the pH to 6.0 to obtain a monodispersed 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%. Triethylthiourea and chloroauric acid were added to this emulsion for optimum chemical sensitization, and then the following spectral sensitizer (l) was added at 5 × 10 ⁻⁴ mol per mol of the silver halide emulsion.

For the silver halide emulsion (8) in the green-sensitive silver halide emulsion layer and the silver halide emulsion (9) in the red-sensitive silver halide emulsion layer, the same procedure as above was used to prepare (8 solution) and (10 solution). It was prepared by changing the chemical amount, the type and amount of the spectral sensitizer, the temperature and the addition time. The spectral sensitizer using the silver halide emulsion (8) is (m) below, and the spectral sensitizer used in the silver halide emulsion (9) is (n).

The following compounds were added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

Further, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to each of the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer per mol of silver halide.
8.5 × 10 ^-5 mol, 7.7 × 10 ^-4 mol and 2.5 × 10 ^-4 mol were added.

Table 3 shows the average grain size, variation coefficient and halogen composition of silver halide emulsions (7) to (9).

Samples in which the silver halide emulsions of the first, third and fifth layers of Samples -101 and -102 of Example 1 were replaced with the above silver halide emulsions (7), (8) and (9), respectively. −10
3 and -104 were prepared and subjected to the same gradation exposure as in Example 1, and then the sharpness was measured by performing the following treatment, and further improvement in sharpness was recognized.

After the exposure, a process including color development, bleach-fixing and rinsing was performed. The temperature, time, and formulation of each step are shown below.

(Processing step) (Temperature) (Time) Color development (formulation B) 35 ° C 45 seconds Bleach fixing (formulation B) 35 ° C 45 seconds Rinse 28 to 35 ° C 1 minute 30 seconds (Color development development-B) Water 800cc Diethylenetriamine pentaacetic acid-5Na salt 1.0g Sodium sulfite 0.2g N, N-diethylhydroxylamine 4.2g Potassium bromide 0.01g Sodium chloride 1.5g Triethanolamine 8.0g N-ethyl-N- (β-methanesulfonamidoethyl)
-3-Methyl-4-aminoaniline / sulfate potassium carbonate 30.0g 4,4'-diaminostilbene-based fluorescent brightener 2.0g (Sumitomo Chemical Co., Ltd. Whitex4) Add water to total 1000cc (pH 10.1 ) (Bleaching solution fixing formulation-B) Water 700cc Ammonium thiosulfate (54wt%) 150cc Sodium sulfite 15g NH ₄ [Fe (III) (EDTA)] 55g EDTA ・ 2Na (dihydrate) 4g Glacial acetic acid 8.61g Add water Total amount 1000 cc (pH 5.4) (Rinse solution formulation) EDTA.2Na (dihydrate) 0.4 g Water was added to total amount 1000 cc (pH 7.0) Example 3 First layer to 7th layer used in Example 1 Instead of layers, Japanese Patent Laid-Open No. 62-1
The first to eleventh layers (using the coupler of the present invention) described on pages 18 to 19 of 74760 publication are applied after undercoating on a reflective support made of vinyl chloride resin while containing a white pigment. Thus, a reversal color photographic print excellent in sharpness and free from unevenness in image density can be obtained by preparing a reversal color light-sensitive material and then processing it according to a predetermined development processing step.

Continuation of the front page (56) Reference JP-A-61-248736 (JP, A) JP-A-59-200234 (JP, A) JP-A-61-120140 (JP, A) JP-B-5-16580 (JP , B2) Japanese Patent Publication 1-224069 (JP, B2)

Claims (2)

[Claims] 1. The following general formula (1) is provided on a reflective support having a vinyl chloride resin itself containing a white pigment as a support.
Or a red light-sensitive silver halide emulsion layer containing a cyan color coupler represented by (2), the general formula (3) or (4)
At least one of a green light-sensitive silver halide emulsion layer containing a magenta color forming coupler represented by and a blue light-sensitive silver halide emulsion layer containing a yellow color forming coupler represented by the general formula (5) is coated in any order. A silver halide color photographic light-sensitive material provided. General formula (1) General formula (2) General formula (3) General formula (4) General formula (5) In the formula, R ₁ , R ₄ and R ₅ are each an aliphatic group, an aromatic group,
Represents a heterocyclic group, an aromatic amino group or a heterocyclic amino group, R ₂ represents an aliphatic group, R ₃ and R ₆ are each a hydrogen atom, a halogen atom, an aliphatic group, an aliphatic oxy group, or an acylamino group. R ₇ and R ₈ represent a substituted or unsubstituted phenyl group, and R ₉ represents a hydrogen atom or a substituent. R ₂ and R ₃ and R ₅ and R ₆ may be connected to each other to form a 5- to 7-membered ring. Q represents a substituted or unsubstituted N-phenylcarbamoyl group, Za and Zb represent a -CH = group, Alternatively, -N = represents a group. R ₁₀ represents a substituent. X ₁ ,
X ₂ , X ₃ , X ₄ and X ₅ each represent a hydrogen atom or a group capable of leaving by reaction with an oxidized product of an aromatic primary amine developing agent (hereinafter referred to as CD). 2. The following general formula (1) is provided on a reflective support having a vinyl chloride resin itself containing a white pigment as a support.
Or an emulsion layer containing a cyan dye obtained by reacting a cyan color forming coupler represented by (2) with a CD, a magenta color forming coupler represented by the following general formula (3) or (4) reacting with a CD. The magenta dye-containing emulsion layer thus obtained and at least one of the yellow dye-containing emulsion layer obtained by reacting the yellow color-forming coupler represented by the following general formula (5) with CD are optionally mixed. Color photo prints that are applied in order. General formula (1) General formula (2) General formula (3) General formula (4) General formula (5) In the formula, R ₁ , R ₄ and R ₅ are each an aliphatic group, an aromatic group,
Represents a heterocyclic group, an aromatic amino group or a heterocyclic amino group, R ₂ represents an aliphatic group, R ₃ and R ₆ are each a hydrogen atom, a halogen atom, an aliphatic group, an aliphatic oxy group, or an acylamino group. R ₇ and R ₈ represent a substituted or unsubstituted phenyl group, and R ₉ represents a hydrogen atom or a substituent. R ₂ and R ₃ and R ₅ and R ₆ may be connected to each other to form a 5- to 7-membered ring. Q represents a substituted or unsubstituted N-phenylcarbamoyl group, Za and Zb represent a -CH = group, Alternatively, -N = represents a group. R ₁₀ represents a substituent. X ₁ ,
X ₂ , X ₃ , X ₄ and X ₅ each represent a hydrogen atom or a group capable of leaving by reaction with an oxidized product of an aromatic primary amine developing agent (hereinafter referred to as CD).