JP2700737B2 - Silver halide color photographic light-sensitive material and color photographic image forming method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material and a color image forming method, and more particularly to a silver halide color photographic light-sensitive material having excellent rapid processing suitability and excellent image storability after processing. The present invention relates to a color image forming method.

[0002]

2. Description of the Related Art In recent years, in order to respond to the demand for rapid processing, an emulsion having a lower silver bromide content and a higher silver chloride content has been used as a light-sensitive material in conventional color developing solutions of color paper. New systems for processing in combination with developers that do not use sulfites or benzyl alcohol are being developed and introduced to the market. When such rapid processing is applied to color paper, especially under light irradiation, the fading of a specific dye image deteriorates, and the fading balance of the three colors is lost, resulting in a change in color. In some cases, a white background portion, which is a non-image portion, was colored. Naturally, color photographs have a small degree of fading (photobleaching and dark fading) under both light irradiation and storage in a dark place, and the coloring of the white background portion has been kept small, in light of the purpose of recording and preservation. Need to be done. Thus, such changes caused by the application of rapid processing are a major problem. There have been many attempts to improve image preservation,
In particular, in the photobleaching of a cyan image, it is not sufficient to use only the conventionally proposed method. The cyan image has a different fading speed from that of other dye images when exposed to strong light such as direct sunlight and when exposed to weak light such as indoor light for a long time. A desirable result cannot be obtained only by making fading difficult, and a new means for improving both fading with strong light and fading light with good balance has been desired. As a method for improving this point, a method using a dispersion in which a cyan coupler and a polymer latex are dissolved is disclosed in WO 88/00723 and JP-A-63-44658. In this case, the decrease in the density of the cyan image is large and not sufficient. JP-A-3-192347 discloses a method in which a halogen-substituted hydroquinone is added to a cyan coloring layer to simultaneously satisfy processing dependency and photobleaching.
It could not be said to be sufficient, and further improvement was desired.

[0003]

As a result of repeated studies by the present inventors, it has been found that three types of photosensitive materials having different photosensitivities each containing a coupler which develops a yellow, magenta or cyan color on a reflective support. In a silver halide photographic light-sensitive material containing a silver halide emulsion layer, a specific cyan coupler is used, and the cyan coupler-containing silver halide emulsion layer comprises three types of silver halide emulsions each containing a different kind of coupler. The hydrophilic non-photosensitive layer, which is located farthest from the support in the layer and contains the specific hydroquinone compound substantially without coexisting with the ultraviolet absorber, is located below and adjacent to the cyan coupler-containing silver halide emulsion layer. A hydrophilic non-photosensitive layer coated on the (support side) and containing an ultraviolet absorber substantially without coexistence with a hydroquinone compound; By using a silver halide having a silver chloride content of 90% or more by coating above the silver halide emulsion layer, it was found that a photographic material which was capable of rapid processing and improved in cyan fading was obtained. . However, as a result of further studies, it has become clear that in such a configuration, the gradation of the high-density portion is softened, so that a so-called tight image is easily formed. In order to obtain a sharp and vivid image, a means for preventing softening of a high density portion was required. Accordingly, an object of the present invention is to achieve both rapid processing properties and image storability of a high silver chloride photosensitive material excellent in rapid processing suitability, and the photobleaching property of a cyan dye in rapid processing is strong light or weak light. It is hard to fade in balance with other pigments, and there is little coloring of white background in dark fading,
Another object of the present invention is to provide a light-sensitive material and an image forming method in which softening of gradation in a high density portion is small.

[0004]

The object of the present invention has been found to be achieved by the following silver halide color photographic light-sensitive material and an image forming method. [1] In a silver halide color photographic light-sensitive material having three types of photosensitive silver halide emulsion layers having different photosensitivities each containing any one of couplers for yellow, magenta and cyan, respectively, on a reflective support, 1) The cyan coupler is a compound represented by the general formula (C),
Moreover, this cyan coupler-containing silver halide emulsion layer is
Of the three types of silver halide emulsion layers each containing a different type of coupler, located farthest from the support,
(2) A hydrophilic non-photosensitive layer containing a compound represented by the following general formula [I] substantially without coexisting with an ultraviolet absorber is disposed below and adjacent to the cyan coupler-containing silver halide emulsion layer ( (3) a cyan coupler-containing silver halide emulsion comprising a hydrophilic non-photosensitive layer which is coated on the support and contains (3) an ultraviolet absorber substantially without coexistence with a compound represented by the following general formula [I]: (4) silver chlorobromoiodide, silver chlorobromide, silver chloroiodide, coated above the layers, and (4) the silver halide contained in each emulsion layer has an average silver chloride content of 90 mol% or more. Or a silver halide color photographic light-sensitive material, characterized in that silver chloride contained in at least one of the emulsion layers is gold-sensitized with a gold compound.

[0005]

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In the formula, R ₁ represents a substituted or unsubstituted aliphatic group, aromatic group or heterocyclic group. R ₂ is a substituted or unsubstituted aliphatic group having 2 or more carbon atoms, R ₃ is a hydrogen atom, a halogen atom, a substituted or unsubstituted aliphatic group,
Represents an aromatic group or an acylamino group. Y represents a hydrogen atom or a group capable of leaving during a coupling reaction with an oxidized developing agent.

[0007]

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In the formula, R ₁₁ represents a hydrogen atom or a substituent, and R ₁₂ may be the same or different from R ₁₁ and represents a hydrogen atom or a substituent. R ₁₃ may be the same or different and R ₁₄ represents a hydrogen atom or a substituent. However, at least one of R _{11 to} R ₁₄ must be a substituent. [2] A color photographic image forming method, wherein the color photographic light-sensitive material is processed within 4 minutes as a total time from color development to completion of washing or stabilization processing.

In a conventional color light-sensitive material, a layer containing an oil-soluble hydroquinone derivative is provided between each emulsion layer as a color mixture prevention layer in order to prevent color mixture during development processing.
Further, in order to improve image storability, an ultraviolet absorber is contained above and below the cyan color-forming silver halide emulsion layer. In particular, in the conventional high silver chloride color photographic paper, the non-photosensitive layers located above and below the cyan-chromogenic silver halide emulsion layer simultaneously contain an oil-soluble hydroquinone derivative and an ultraviolet absorber. On the other hand, in the present invention, the conventional common sense is violated, and substantially no oil-soluble hydroquinone derivative is contained above the cyan-color-forming silver halide emulsion layer. The object of the present invention was effectively achieved by substantially not containing an ultraviolet absorber below, and by performing rapid processing using such a photosensitive material.

Hereinafter, the present invention will be described in detail. The term “photosensitive” or “non-photosensitive” as used in the present invention is used to mean not only visible light but also sensitivity to electromagnetic waves in the infrared wavelength region. In the present invention, the expression "coated below a silver halide emulsion layer containing a cyan coupler" means that a thin non-photosensitive hydrophilic layer (a coupler or the like may be added) to the emulsion layer. And a non-photosensitive layer containing the compound of the general formula [I] may be coated via the compound. However, the non-photosensitive layer containing the compound of the general formula [I] is preferably provided without such a layer. It means that the layer is applied directly. The color photographic light-sensitive material of the present invention is constituted by coating at least one layer of a yellow-forming silver halide emulsion layer, a magenta-forming silver halide emulsion layer and a cyan-forming silver halide emulsion layer on a support. .
Generally, a yellow-color-forming silver halide emulsion layer, a magenta-color-forming silver halide emulsion layer, and a cyan-color-forming silver halide emulsion layer are coated on a support in the above-mentioned order from the support side. In these light-sensitive emulsion layers, a silver halide emulsion having a sensitivity in each wavelength region and a dye having a complementary color with the light to be exposed, that is, yellow for blue, magenta for green, and cyan for red are formed. By incorporating a so-called color coupler, the color reproduction by the subtractive color method can be performed. However, the photosensitive layer and the color hue of the coupler may not have the above correspondence.

The silver halide emulsion used in the present invention includes silver chloride, silver chlorobromide having a silver chloride content of 90 mol% or more,
Use is made of silver chloroiodide or silver chloroiodobromide. The content of silver iodide in the above-mentioned silver chlorobromoiodide or silver chloroiodide is suitably 0.01 to 3 mol%, and more preferably 0.015 to 2 mol%.
Mol% is preferable, 0.02 to 1 mol% is more preferable, and 0.03 to 0.6 mol% is particularly preferable. The halogen composition of the emulsion may be different or the same between grains, but it is preferable to use an emulsion having the same halogen composition between grains, because it is easy to make the properties of each grain uniform. Regarding the halogen composition distribution inside the silver halide emulsion grains, grains having a so-called uniform structure having the same composition in any part of the silver halide grains, a core inside the silver halide grains and a shell surrounding the core are used. (shell)
[Single or plural layers] grains having a so-called laminated structure having different halogen compositions from each other or a structure having a non-layered portion having a different halogen composition inside or on the surface of the grains. Particles having a structure in which portions having different compositions are joined together) can be appropriately selected and used. In order to obtain high sensitivity, it is advantageous to use one of the latter two particles rather than particles having a uniform structure, and this is also preferable from the viewpoint of pressure resistance. In the case where the silver halide grains have the above-described structure, even if the boundary between different portions in the halogen composition is a clear boundary, it is an unclear boundary by forming a mixed crystal due to a composition difference. It is also possible to employ a structure in which a continuous structural change is positively provided.

A so-called high silver chloride emulsion having a high silver chloride content is preferably used as a light-sensitive material suitable for rapid processing.
In the present invention, those having a silver chloride content of 90 mol% or more are used, but those having a higher silver chloride content can also be preferably used. The silver chloride content is more preferably 95 mol% or more, and particularly preferably 98 mol% or more. Such a high silver chloride emulsion preferably has a structure in which the silver bromide rich phase is localized in the above-mentioned layered or non-layered form inside and / or on the surface of silver halide grains. The halogen composition of the localized phase is preferably at least 10 mol% in terms of silver bromide content, and more preferably more than 20 mol%. These localized phases can be inside the grains, at the edges, corners or planes of the grain surfaces, but those present at the corners of the grains are particularly preferred. On the other hand, for the purpose of minimizing a decrease in sensitivity when the photosensitive material is subjected to pressure, it is also preferable to use particles having a uniform structure having a small distribution of halogen composition in the particles.

The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined by the diameter of a circle equivalent to the projected area of the grain and the number average thereof is taken) is 0.1 μm. ~ 2μ is preferred. The particle size distribution is preferably a so-called monodisperse coefficient of variation (a standard deviation of the particle size distribution divided by the average particle size) of 20% or less, and preferably 15% or less. At this time, for the purpose of obtaining a wide latitude, it is also preferable to use the above monodispersed emulsion by blending it in the same layer, or to perform multi-layer coating. The silver halide grains contained in the photographic emulsion may have a regular crystal form such as cubic, tetradecahedral or octahedral, or an irregular shape such as spherical or tabular. ) Those having a crystal form or those having a composite form thereof can be used. Further, it may be composed of a mixture of those having various crystal forms. In the present invention, among these, the particles having the above-mentioned regular crystal form should be contained in 50% or more, preferably 70% or more, and more preferably 90% or more. In addition, emulsions in which tabular grains having an average aspect ratio (diameter / circle diameter in circle) of 5 or more, preferably 8 or more, as projected area exceeds 50% of all grains can be preferably used.

The emulsion used in the present invention is C. by P. Glafkides.
himie et Phisique Photographique (PaulMontel, 1
967), Photographic Emulsion Ch by GF Duffin
emistry (Focal Press, 1966), VL Zelikma
Making and Coating Photographic Emuldion by n et al
(Focal Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a method of reacting a soluble silver salt and a soluble halide, any method such as a one-side mixing method, a simultaneous mixing method, and a combination thereof may be used. May be used. A method of forming particles in an atmosphere containing excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method of maintaining a constant pAg in a liquid phase in which silver halide is formed, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

The silver halide emulsion used in the present invention has various properties for the purpose of improving sensitivity, reciprocity characteristics, temperature / humidity dependence upon exposure, latent image preservability, etc. in the process of emulsion grain formation or physical ripening. Polyvalent metal ion impurities can be introduced. Examples of compounds used include salts of cadmium, zinc, lead, copper, thallium and the like, or salts or complex salts of Group VIII elements such as iron, ruthenium, rhodium, palladium, osmium, iridium and platinum. it can. In particular, the Group VIII element can be preferably used. The addition amount of these compounds varies widely depending on the purpose, but is preferably from 10 ^-9 to 10 ^-2 mol based on silver halide. The silver halide emulsion used in the present invention is subjected to chemical sensitization and spectral sensitization. That is, the silver halide emulsion of at least one of the emulsion layers of the present invention needs to be chemically sensitized using a gold compound. The gold compound to be used may have a monovalent or trivalent gold oxidation number. Can be used.
Typical examples are tetrachloroauric (III) acid, tetracyanoaurate (III) acid or tetrakis (thiocyanato) aurate (III) acid or an alkali metal salt thereof, bis (thiosulfato) aurate (I) acid salt, dimethyl chloride A complex ion or complex salt of rhodanate gold can be mentioned. The addition amount of these gold compounds may vary widely depending on the case, but is generally about 1 × 1 per mol of silver halide.
0 ^-8 is 1 × 10 ^-2 mols of moles, preferably in the range of 1 × 10 ^-3 mol 1 × 10 ^-7 mol, more preferably 1 × 10 ^-6 mol 1 × 10 ^{- In} the range of ⁴ moles. The addition of these gold compounds is performed during the preparation of the silver halide emulsion, but is preferably performed until the completion of the chemical sensitization. Chemical sensitization using a gold compound can be used in combination with sulfur sensitization typified by addition of an unstable sulfur compound, selenium sensitization, noble metal sensitization using a compound other than a gold compound, or reduction sensitization. The above-mentioned chemical sensitization can be applied alone or in combination to silver halide which is not chemically sensitized using a gold compound. Spectral sensitization is performed for the purpose of imparting spectral sensitivity to a desired light wavelength range to the emulsion of each layer in the light-sensitive material of the present invention. In the present invention, it is preferable to add a dye that absorbs light in a wavelength range corresponding to the intended spectral sensitivity—a spectral sensitizing dye. As the spectral sensitizing dye used at this time, for example,
Heterocyclic compounds −Cyanine dy by FM Harmer
es and related compounds (JohnWiley & Sons (New Yo
rk, London], 1964). Specific examples of compounds and spectral sensitization methods described in JP-A-62-215272, page 22, upper right column to page 38, are preferably used.

The silver halide emulsion used in the present invention contains various compounds or their precursors for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. Can be added. Specific examples of these compounds are described in the above-mentioned JP-A-62-2152.
What is described on page 39-page 72 of the specification of JP-A No. 72 is preferably used. In particular, the silver halide emulsion used in the present invention is prepared by adding at least one mercapto compound described in JP-A-2-123350, page 416, lower right column, line 4 to page 423, upper left column. This is remarkably effective in preventing an increase in the fog, especially when using a gold sensitizer. The addition may be carried out at the grain forming step, desalting step, chemical ripening step or just before coating, but it is preferably added at the grain forming, desalting, chemical ripening step, especially before the addition of the gold sensitizer. The emulsion used in the present invention is any of a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface and a so-called internal latent image type emulsion in which a latent image is mainly formed inside the grain. Is also good. It is preferable to use gelatin which has been subjected to a deionization treatment as the gelatin used in the present invention. Gelatin usually contains a large amount of calcium ions and often contains 5000 ppm or more. Deionized gelatin used in the present invention,
It is preferable to use those having a calcium ion of 500 ppm or less. Deionized gelatin is preferably used in an amount of 10% by weight or more, more preferably 20% or more, and particularly preferably 50% or more based on the total gelatin. Such gelatin may be used in any of the layers.

The compound represented by the general formula [I] used in the present invention is a compound usually used in photographic light-sensitive materials as a color mixing inhibitor, and is preferably an oil-soluble compound. The amount of the compound represented by the general formula [I] in the non-photosensitive layer provided below the cyan coupler-containing layer is 10 mg / m ^{2 to} 400 mg / m ^2.
mg / m ² or less, more preferably 10 mg / m ² or more and 240 mg / m ² or less. The amount of the compound represented by the general formula (I) above the cyan coupler-containing layer, which does not substantially coexist with the ultraviolet absorber,
It is preferably less than 10 mg / m ² , and it is particularly preferred that it is not contained at all.

In the compound represented by the general formula [I], examples of the substituent represented by R ₁₁ and R ₁₂ include an alkyl group, an alkenyl group, an aryl group, an acyl group, a cycloalkyl group and a sulfonic acid group. , A halogen atom or a heterocyclic group are preferred. Examples of the alkyl group include methyl, ethyl, n-propyl, n-butyl, t-butyl, n-amyl, i-amyl, n-octyl, n-dodecyl, and n-octadecyl. An alkyl group having 1 to 32 carbon atoms is preferred. Examples of the alkenyl group include allyl, octenyl, and oleyl groups, and an alkenyl group having 2 to 32 carbon atoms is particularly preferable. Examples of the aryl group include phenyl and naphthyl groups. Examples of the acyl group include acetyl, octanoyl, and lauroyl groups. Examples of the halogen atom include fluorine, chlorine and bromine atoms. Examples of the cycloalkyl group include a cyclohexyl group. Examples of the heterocyclic group include imidazolyl, furyl, pyridyl, triazinyl, and thiazolyl groups. In the general formula [I], the total number of carbon atoms of the group represented by R ₁₁ and R ₁₂ is preferably 8 or more, and the group represented by R ₁₁ and / or R ₁₂ is The group is preferably a group that can impart diffusivity. In the general formula (I),
Examples of the substituent represented by R ₁₃ and R ₁₄ include a halogen atom, an alkyl group, an aryl group, a cycloalkyl group,
Alkoxy group, aryloxy group, arylthio group, acyl group, alkylacylamino group, arylacylamino group, alkylcarbamoyl group, arylcarbamoyl group, alkylsulfonamide group, arylsulfonamide group, alkylsulfamoyl group, arylsulfamoyl Group, an alkylsulfonyl group, an arylsulfonyl group, a nitro group, a cyano group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkylacyloxy group or an arylacyloxy group.

In the general formula [I], R ₁₃ and R ₁₄
Specific examples of the halogen atom, alkyl group, aryl group, acyl group and cycloalkyl group represented by
It can be exemplified similar to those mentioned in ₁₁ and R _12. Examples of the alkoxy group include methoxy, ethoxy, and dodecyloxy groups, examples of the aryloxy group include a phenoxy group, and examples of the alkylthio group include methylthio, n-butylthio, and n.
Each group of -dodecylthio; examples of the arylthio group include a phenylthio group; examples of the alkylacylamino group include an acetylacylamino group; examples of the arylacylamino group include a benzoylamino group; Examples of the alkylcarbamoyl group include a methylcarbamoyl group; examples of the arylcarbamoyl group include a phenylcarbamoyl group; examples of the alkylsulfonamide group include a methylsulfonamide group; Examples of the group include a phenylsulfamoyl group, examples of the alkylsulfamoyl group include a methylsulfamoyl group, and examples of the arylsulfamoyl group include a phenylsulfamoyl group. Examples of the alkylsulfonyl group include a methylsulfonyl group, examples of the arylsulfonyl group include a phenylsulfonyl group, examples of the alkyloxycarbonyl group include a methyloxycarbonyl group, and an aryloxycarbonyl group. Is, for example, a phenyloxycarbonyl group, an alkylacyloxy group is, for example, an acetyloxy group, and an arylacyloxy group is, for example, a benzoyloxy group. These substituents are further substituted by alkyl, aryl, aryloxy, alkylthio, cyano, acyloxy, alkoxycarbonyl, acyl, sulfamoyl, hydroxy, nitro, amino and heterocyclic groups. It may be replaced.
Specific examples of the compound represented by the general formula [I] include the following compounds.

[0020]

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[0021]

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[0022]

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The non-photosensitive layer below the cyan coupler-containing layer preferably contains at least one compound of the above formula [I] dispersed in an oil droplet state. It is also preferred that they are emulsified and dispersed in a form dissolved in a solvent. Furthermore, it is preferable to simultaneously contain the compound of the general formula [I] and a polymer compound such as polyacrylamide. As the ultraviolet absorber used above the cyan coupler-containing layer, any one may be used. Preferred are thiazolidone-based, benzotriazole-based, acrylonitrile-based, and benzophenone-based and aminobutadiene-based ultraviolet absorbers. These UV absorbers are described, for example, in U.S. Pat. No. 1,023,85.
No. 9, No. 2,685,512, No. 2,739,8
No. 88, No. 2,784, 087, No. 2,748,
No. 021, No. 3,004,896, No. 3,05
No. 2,636, No. 3,215,530, No. 3,2
No. 53,921, No. 3,533,794, No. 3,
Nos. 692,525, 3,705,805, 3,707,375, 3,738,837, 3,754,919, British Patent 1,321,35
No. 5 is described.

More preferred are benzotriazole compounds, and furthermore, 2- (2'-hydroxyphenyl) which is a compound represented by the following general formula (II):
Benzotriazole compounds are preferred. This compound may be solid or liquid at room temperature.

A specific example of a liquid ultraviolet absorber is disclosed in
Nos. 5-36984, 55-12587, and
No. 8-214152. R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , and R _{21 of the} ultraviolet absorber represented by the general formula (II)
Details of the atoms and groups represented by R ₂₅ and R ₂₆ are described in JP-A-58-221844 and JP-A-59-46646;
No. 59-109055, Japanese Patent Publication No. 36-10466
Nos. 42-26187, 48-5496, and 4
8-41572, U.S. Pat. Nos. 3,754,919 and 4,220,711. Next, some specific examples of the compound represented by the formula (II) are shown in Table 1, but the present invention is not limited to these.

[0026]

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[0027]

[Table 1]

[0028]

[Table 2]

[0029]

[Table 3]

[0030]

[Table 4]

[0031]

[Table 5]

[0032]

[Table 6]

The amount of the ultraviolet absorber contained in the non-light-sensitive layer provided above the silver halide emulsion light-sensitive layer containing a cyan coupler is 1,000 mg / m ² or less and 150 mg / m ^2.
Or more, preferably 600 mg / m ² or less 150 m
g / m ² or more. In the present invention, the non-light-sensitive layer provided below the cyan coupler-containing silver halide emulsion light-sensitive layer must be substantially free of an ultraviolet absorber with respect to the compound represented by the general formula [I]. It is. “Substantially not coexisting” means less than 150 mg / m ² , preferably 100 mg / m ² or less, and it is particularly preferred that no such compound is contained. An ultraviolet absorber is also preferably contained in a silver halide emulsion photosensitive layer containing a cyan coupler for stabilizing a cyan image. The non-photosensitive layer provided above the cyan coupler-containing layer may contain, in addition to the ultraviolet absorber, a stain inhibitor, a stabilizer for the ultraviolet absorber, and the like. It may be contained as an emulsified dispersion in a form dissolved in a high boiling point organic solvent.

In the present invention, yellow couplers, magenta couplers and cyan couplers which are respectively coupled to an oxidized form of an aromatic amine-based color developing agent to form yellow, magenta and cyan, respectively, are used. Preferred examples of the cyan coupler represented by the general formula (C) are as follows. In formula (C), preferred R ₁ is a substituted or unsubstituted alkyl group or aryl group, particularly preferably a substituted aryloxy-substituted alkyl group. In the general formula (C), preferred R ₂ has 2 to 1 carbon atoms.
5 is an alkyl group and a methyl group having a substituent having 1 or more carbon atoms, and the substituent is preferably an arylthio group, an alkylthio group, an acylamino group, an aryloxy group, or an alkyloxy group. In the general formula (C), R ₂ is more preferably an alkyl group having 2 to 15 carbon atoms, and particularly preferably an alkyl group having 2 to 4 carbon atoms. As R ₂ in the general formula (C), for example, an ethyl group, a propyl group, a butyl group, a pentadecyl group, a tert-butyl group, a cyclohexyl group, a cyclohexylmethyl group,
Examples include a phenylthiomethyl group, a dodecyloxyphenylthiomethyl group, a butanamidomethyl group, a methoxymethyl group, and the like. In formula (C), preferred R ₃ is a hydrogen atom or a halogen atom, and a chlorine atom and a fluorine atom are particularly preferred. Preferred Y in the general formula (C) is a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, or a sulfonamide group. Specific examples of the compound represented by the general formula (C) are shown below.

[0035]

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[0036]

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The light-sensitive material according to the present invention is provided with a dye capable of being decolorized by a treatment described in EP 0,337,490 A2, pp. 27-76, in a hydrophilic colloid layer for the purpose of improving the sharpness of an image. (In particular, oxonol dyes) having an optical reflection density at 680 nm of the photosensitive material of 0.
70% or more, or 12% by weight or more (more preferably 14% by weight) of titanium oxide surface-treated with a divalent or tetravalent alcohol (for example, trimethylolethane) or the like in the water-resistant resin layer of the support. % By weight or more).

The photographic additives such as cyan, magenta and yellow couplers which can be used in the present invention are preferably used by dissolving them in a high boiling organic solvent. The high boiling organic solvent has a melting point of 100 ° C. or less and a boiling point of 140 ° C. Any of the above water-immiscible compounds and a good solvent for the coupler can be used. The melting point of the high boiling organic solvent is preferably 80 ° C. or lower. The boiling point of the high-boiling organic solvent is preferably 160 ° C. or higher,
More preferably, it is 170 ° C. or higher. Details of these high-boiling organic solvents are described in JP-A-62-215272, page 137, lower right column to page 144, upper right column.
Alternatively, cyan, magenta or yellow couplers can be used in the presence or absence of the high boiling organic solvents described above in loadable latex polymers (eg, US Pat. No. 4,203,716).
) Or dissolved together with a water-insoluble and organic solvent-soluble polymer to emulsify and disperse in a hydrophilic colloid aqueous solution. Preferably U.S. Patent 4,857,44
Homopolymers or copolymers described in column 7 to column 15 of the specification No. 9 and pages 12 to 30 of the specification of International Publication WO88 / 00723 are used, and more preferably a methacrylate or acrylamide polymer. In particular, use of an acrylamide-based polymer is preferred for stabilizing a color image.

In the light-sensitive material according to the present invention, it is preferred to use a color image preservability improving compound as described in EP 0,277,589A2 together with a coupler. In particular, combination use with a pyrazoloazole coupler is preferred. That is, the compound (F) which forms a chemically inert and substantially colorless compound by chemically bonding with the aromatic amine-based developing agent remaining after the color developing process and / or the aromatic compound remaining after the color developing process. The compound (G) which forms a chemically inert and substantially colorless compound by chemically bonding with an oxidized form of an aromatic amine color developing agent can be used simultaneously or alone, for example, in storage after processing. It is preferable in order to prevent the generation of stains and other side effects due to the formation of a coloring dye due to the reaction between the color developing agent or its oxidized product and the coupler remaining in the film.

The light-sensitive material according to the present invention is provided with a fungicide as described in JP-A-63-271247 in order to prevent various molds and bacteria that propagate in the hydrophilic colloid layer and deteriorate the image. It is preferred to add an agent.

As a support used for the light-sensitive material according to the present invention, a white polyester-based support or a layer containing a white pigment was provided on a support having a silver halide emulsion layer for a display. A support may be used. In order to further improve the sharpness, an antihalation layer is preferably provided on the support on the side where the silver halide emulsion layer is coated or on the back surface. In particular, the transmission density of the support is set to 0.3 so that the display can be viewed with both reflected light and transmitted light.
It is preferable to set in the range of 5 to 0.8.

The photosensitive material according to the present invention may be exposed to visible light or infrared light. The exposure method may be low-illuminance exposure or high-illuminance short-time exposure. In the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 ^-4 seconds is preferred.

In the exposure, US Pat. No. 4,880,72
It is preferable to use the band stop filter described in No. 6. As a result, light color mixing is removed, and color reproducibility is significantly improved.

The color photographic light-sensitive material of the present invention is preferably subjected to color development, bleach-fix, and washing (or stabilization) after exposure. Bleaching and fixing may be performed separately, instead of in a single bath as described above. When the color photographic light-sensitive material of the present invention is used, processing from color development to washing processing (or stabilization processing) can be performed within 4 minutes. More preferably, it is within 3 minutes.

The silver halide emulsion and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) applied to the light-sensitive material according to the present invention, and processing methods applied for processing this light-sensitive material And the additives for processing include the following patent publications, in particular, European Patent EP 0,355,660A2 (Japanese Patent Laid-Open No. 2-1395).
No. 44) are preferably used.

[0046]

[Table 7]

[0047]

[Table 8]

[0048]

[Table 9]

[0049]

[Table 10]

Further, as the cyan coupler, a coupler of the general formula (C), a diphenylimidazole-based cyan coupler described in JP-A-2-33144, and EP 0,333,18
3-hydroxypyridine cyan couplers described in No. 5A2 (among others, couplers (42) listed as specific examples)
And 2-equivalent couplers having a chlorine leaving group, and couplers (6) and (9) are particularly preferable) and cyclic active methylene cyan couplers described in JP-A-64-32260. However, coupler examples 3, 8, and 34 listed as specific examples are particularly preferred).

As a method for processing a silver halide color light-sensitive material using a high silver chloride emulsion having a silver chloride content of 90 mol% or more, JP-A-2-207250, page 27, upper left column to page 34, upper right column. Are preferably applied.

[0052]

【Example】

Example 1 A surface of a paper support laminated on both sides with polyethylene was subjected to a corona discharge treatment, followed by providing a gelatin subbing layer containing sodium dodecylbenzenesulfonate, and further applying various photographic constituent layers to form a layer shown below. A multilayer color printing paper (sample 101) having the above configuration was produced. The coating solution was prepared as follows. Preparation of first layer coating solution 153.0 g of yellow coupler (ExY) and color image stabilizer (Cp
d-1) 15.0 g, color image stabilizer (Cpd-2) 7.5 g, color image stabilizer
(Cpd-3) 16.0 g of ethyl acetate 180.0 cc and solvent (Solv-
25 g of each of 1) and (Solv-2) were added and dissolved, and this solution was added to 60 cc of 10% sodium dodecylbenzenesulfonate.
Emulsified dispersion A was prepared by emulsifying and dispersing in 1000 g of a 10% aqueous gelatin solution containing 10 g of citric acid. On the other hand, silver chlorobromide emulsion B (a cubic emulsion containing silver chlorobromide grains having an average grain size of 0.70 μm. The variation coefficient of grain size distribution is 0.10,
(0.3 mol% of silver bromide localized on a part of the grain surface) was prepared. The emulsified dispersion A and the silver chlorobromide emulsion B were mixed and dissolved to prepare a first layer coating solution having the following composition. Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Further, Cpd-15 and Cpd-16 were added to each layer so that the total amount was 25.0 mg / m ² and 50.0 mg / m ² , respectively.

Preparation of Emulsion G1 3.3% sodium chloride was added to a 3% aqueous solution of lime-processed gelatin.
g, and 3.2 ml of N, N-dimethylimidazolidin-2-thione (1% aqueous solution) was added. This aqueous solution contains 0.5 mol of silver nitrate and 0.1 ml of sodium chloride.
An aqueous solution containing 5 mol was added and mixed at 69 ° C. with vigorous stirring. Subsequently, an aqueous solution containing 0.45 mol of silver nitrate and an aqueous solution containing 0.45 mol of sodium chloride were added and mixed at 69 ° C. with vigorous stirring. Thereafter, desalting was performed by adding a copolymer of isobutene-maleic acid 1-sodium salt at 40 ° C. and performing precipitation and washing. Further, 90.0 g of lime-processed gelatin was added, and the pH and pAg of the emulsion were adjusted to 6.2 and 6.5, respectively. A silver bromide fine grain emulsion having a grain size of 0.05 μm was added to this emulsion in an amount of 0.008 in terms of silver.
Mol at 50 ° C., and optimally sulfur sensitized with triethylthiourea. The silver bromide fine grains contained 3.54 mg of potassium hexachloroiridate (IV) per 0.022 mol of silver during the formation of the emulsion grains. The thus obtained emulsion composed of high silver chloride grains having a silver bromide rich phase on the grain surface was designated as G1. Preparation of Emulsion G2 An emulsion was prepared which was different from G1 only in that gold was sensitized optimally by adding 2.3 × 10 ⁻⁶ mol of tetrachloroauric acid after sulfur sensitization, and this emulsion was designated as G2. Preparation of Emulsion G3 G1 was optimally gold sensitized by adding 1.6 × 10 ^-6 tetracyanoaurate (III) acid after sulfur sensitization without forming a silver bromide rich phase by adding silver bromide fine particles. An emulsion was prepared, which was different from the above only, and was designated as G3.

The thus prepared G1 to G3
For each type of emulsion, the particle shape,
Particle size and particle size distribution were determined. The particle size was represented by the average value of a circle equivalent to the projected area of the particle, and the particle size distribution was obtained by dividing the standard deviation of the particle diameter by the average particle size. Each of the three types of emulsions G1 to G3 had a grain size of 0.42 μm and a grain size distribution of 0.08.
Was cubic particles. The following spectral sensitizing dyes were used for the silver chlorobromide emulsion of each photosensitive emulsion layer.

[0055]

[Table 11]

[0056]

[Table 12]

[0057]

[Table 13]

The blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer were treated with 1- (5-methylureidophenyl)-
5-mercaptotetrazole was replaced by silver halide 1
3.4 × 10 ^-4 mol, 9.7 × 10 ^-4 mol, 5.5 × 10 per mol
^-4 mol was added. Also, 4-hydroxy-6-methyl-1,3,3a, 7 was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer.
1 × 10 ⁻⁴ mol and 2 × 10 ⁻⁴ mol of tetrazaindene were added per mol of silver halide. Further, the following dyes (in parentheses, the coating amounts are shown) were added to the color mixture prevention layer to prevent irradiation.

[0059]

Embedded image

(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver. Support: polyethylene laminated paper [polyethylene on the first layer side contains white pigment (TiO ₂ ) and blue dye (ultra blue)] First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion B 0.27 gelatin 1.09 Yellow coupler (ExY) 0.79 Color image stabilizer (Cpd-1) 0.08 Color image stabilizer (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0.08 Solvent (Solv-1) 0.08 Solvent (Solv-2) 0.18

Second layer (color mixture preventing layer) Gelatin 0.82 Color mixture inhibitor (Cpd-4) 0.08 Solvent (Solv-2) 0.25 Solvent (Solv-3) 0.25 Third layer (green-sensitive emulsion layer) Silver emulsion G1 0.11 Gelatin 1.42 Magenta coupler (ExM) 0.15 Color image stabilizer (Cpd-6) 0.15 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-7) 0.01 Color image stabilizer (Cpd-8) ) 0.01 Color image stabilizer (Cpd-9) 0.08 Solvent (Solv-3) 0.50 Solvent (Solv-4) 0.15 Solvent (Solv-5) 0.15

Fourth layer (color mixture preventing layer) Gelatin 0.70 Color mixture inhibitor (Cpd-4) 0.04 Color image stabilizer (Cpd-5) 0.02 Solvent (Solv-2) 0.18 Solvent (Solv-3) 0.18 Fifth layer ( Red-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, average particle size 0.58μ, variation coefficient of particle size distribution 0.09, AgBr 0.6 mol% localized in part of the grain surface) 0.20 gelatin 0.74 cyan Coupler (ExC) 0.33 UV absorber (UV-2) 0.18 Color image stabilizer (Cpd-1) 0.35 Color image stabilizer (Cpd-10) 0.15 Color image stabilizer (Cpd-11) 0.15 Color image stabilizer (Cpd -12) 0.01 Color image stabilizer (Cpd-9) 0.01 Color image stabilizer (Cpd-8) 0.01 Solvent (Solv-6) 0.14 Solvent (Solv-1) 0.04 6th layer (UV absorbing layer) Gelatin 0.55 UV absorption Agent (UV-1) 0.40 Color image stabilizer (Cpd-13) 0.15 Color image stabilizer (Cpd-6) 0.02 7th layer (protective layer) Gelatin 1.13 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.15 Liquid paraffin 0.03 Color image stabilizer (Cpd-14) 0.01

The compounds used here are shown below.

[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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Further, Samples 101 to 114 were prepared by changing the composition of the third, fourth and sixth layers from Sample 101 as shown in Table 2. In order to keep the strength of the film of the completed photosensitive material constant, gelatin in each layer was added while changing the ratio to the oil-soluble component so as to be constant.

[0072]

[Table 14]

First, using a sensitometer (FWH type, manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200 ° K) on the sample 101, a gray exposure such that about 30% of the coated silver amount is developed is performed. Gave. The exposed sample was subjected to continuous processing using a paper processing machine using the following processing steps and a liquid having a processing liquid composition to prepare a developing processing state in a running equilibrium state. Processing process Temperature Time Replenisher ^* Tank capacity Color development 35 ° C 45 seconds 161ml 17 liter Bleaching and fixing 30-35 ° C 45 seconds 215ml 17 liter Rinse 30 ° C 90 seconds 350ml 10 liter Drying 70-80 ° C 60 seconds * Replenishment amount is per light-sensitive material 1m ²

The composition of each processing solution is as follows. Color developer Tank solution Replenisher Water 800 ml 800 ml Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid 1.5 g 2.0 g Potassium bromide 0.015 g ト リ Triethanolamine 8.0 g 12.0 g Sodium chloride 1.4 g カ リ ウ ム Potassium carbonate 25 g 25 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g 7.0 g N, N-bis (carboxymethyl) Hydrazine 4.0 g 5.0 g N, N-di (sulfoethyl) hydroxylamine / 1Na 4.0 g 5.0 g Optical brightener (WHITEX 4B, manufactured by Sumitomo Chemical) 1.0 g 2.0 g ───────────── 1000 Add water 1000ml 1000ml pH (25 ℃) 10.05 10.45

Bleach-fix solution (same as tank solution and replenisher) Water 400 ml Ammonium thiosulfate 100 ml (700 g / liter) Sodium sulfite 17 g Ammonium iron (III) ethylenediaminetetraacetate 55 g Disodium ethylenediaminetetraacetate 5 g Brombromide Ammonium 40 g ─────────────────────────── Add water 1000 ml pH (25 ℃) 6.0 Rinse solution (tank solution and replenisher) Is the same) Deionized water (Calcium and magnesium are each 3ppm
Less than)

Next, using a sensitometer (FWH type, manufactured by Fuji Photo Film Co., Ltd.), each of the samples 101 to 114 was subjected to gradation exposure through an optical wedge so as to become almost gray at a color density of 1.0. Was subjected to a color development process. In the color development process, the time from the color development to the completion of the rinsing was 3 minutes, 4 minutes, and 5 minutes, respectively, by changing the time of the rinsing step to 90 seconds, 150 seconds, and 210 seconds. After measuring the optical density of the thus obtained samples in advance, in order to evaluate the light fastness of these samples, a xenon fading tester (about 300,000 lux) was used for one day, and a fluorescent lamp fading tester (about 10,000). After 20 days of light irradiation, the optical density of each sample was measured again. Table 3 shows the reduction rate of the cyan density at the initial density of 2.5. In addition, 80 ° C 70% RH
Was left for 7 days, and the degree of coloring on a white background was examined. The degree of coloring is shown in Table 3 with the change in yellow density in the white background. Further, the gradation of the high density part of magenta was obtained by taking the difference between the logarithms of the respective exposure amounts giving densities of 2.0 and 2.5 of the sample before performing the fading test, and is shown in Table 3. In the samples 106, 109, and 110, although the decrease in the cyan concentration of the sample after the bleaching of the fluorescent lamp is relatively small, the place where the color should be gray originally has a strong magenta taste, which is not preferable. Samples 107 to 110 are not preferable because the yellow stain becomes strong on a white background when the color is faded at 80 ° C. and 70% RH in a short time treatment of 4 minutes or less. The samples 105, 108, and 110 containing the color mixture inhibitor in the sixth layer are not preferable because of large fading of xenon.

[0077]

[Table 15]

As is clear from the results shown in Table 3, Sample 1
In the photosensitive materials of Nos. 01 to 104 and 111 to 114, the color change of the white background is small with the lapse of time after processing.
This is noticeable when the total processing time is within 4 minutes. In addition, it can be seen that the photosensitive material of the present invention is strong against both strong light (xenon) and weak light (fluorescent light) in the photobleaching property of the cyan image. However, no gold sensitized emulsion was used.
In Nos. 1 to 104, the high density part of magenta is soft, and the part which shows black from dark gray is greenish and black is not tight, which is not preferable. Samples 111 to 11 having the configuration of the present invention
For the first time, an image having a hard magenta gradation and a tight black color is obtained in Step 4. Similar effects were obtained by using I-20 or I-23 instead of Cpd-4.

[0079]

According to the present invention, it is possible to rapidly obtain a color print with improved image storability and softening of a high density portion.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical display location G03C 7/34 G03C 7/34 7/392 7/392 A 7/407 7/407

Claims (2)

(57) [Claims] 1. A silver halide color photographic light-sensitive material having three types of photosensitive silver halide emulsion layers having different photosensitivity, each containing a coupler for forming a yellow, magenta or cyan color on a reflective support. ,
(1) The cyan coupler is a compound represented by the general formula (C), and the silver halide emulsion layer containing the cyan coupler is one of three types of silver halide emulsion layers each containing a different type of coupler. And (2) a hydrophilic non-photosensitive layer containing a compound represented by the following general formula [I] substantially without coexisting with an ultraviolet absorber, and A hydrophilic non-aqueous coating which is coated below (support side) adjacent to a silver halide emulsion layer and which contains (3) an ultraviolet absorber substantially without coexisting with a compound represented by the following general formula [I]: A photosensitive layer is provided above the cyan coupler-containing silver halide emulsion layer, and (4) chlorobromoiodide wherein the average silver chloride content of the silver halide contained in each emulsion layer is 90 mol% or more. With silver, silver chlorobromide, silver chloroiodide or silver chloride, The silver halide color photographic material, wherein the silver halide at least to be greater content of the emulsion layer is gold sensitization using a gold compound. Embedded image In the formula, R ₁ represents a substituted or unsubstituted aliphatic group, aromatic group or heterocyclic group. R ₂ represents a substituted or unsubstituted aliphatic group having 2 or more carbon atoms, and R ₃ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted aliphatic group, aromatic group or acylamino group. Y represents a hydrogen atom or a group capable of leaving during a coupling reaction with an oxidized developing agent. Embedded image In the formula, R ₁₁ represents a hydrogen atom or a substituent, and R ₁₂ represents R ₁₁
And may represent the same or different and represent a hydrogen atom or a substituent. R ₁₃ and R ₁₄ may be the same or different and represent a hydrogen atom or a substituent. However, at least one of R _{11 to} R ₁₄ must be a substituent. 2. A silver halide color photographic light-sensitive material having three types of mutually different light-sensitive silver halide emulsion layers containing any one of couplers which respectively develop yellow, magenta and cyan colors on a reflective support. In a color photographic image forming method in which a color developing process is carried out using a silver halide color photographic light-sensitive material, (1) the cyan coupler is a compound represented by the general formula (C), and The silver emulsion layer is located farthest from the support among the three types of silver halide emulsion layers each containing a different type of coupler, and (2) a compound represented by the following general formula [I]: (3) a hydrophilic non-light-sensitive layer containing substantially no coexistence with an ultraviolet absorber and coated below and adjacent to the cyan coupler-containing silver halide emulsion layer; A hydrophilic non-photosensitive layer containing an external light absorbing agent substantially in the absence of a compound represented by the following general formula [I] is provided above the cyan coupler-containing silver halide emulsion layer; A) silver chloroiodide, silver chlorobromide, silver chloroiodide or silver chloride in which the average silver chloride content of the silver halide contained in each emulsion layer is 90 mol% or more, and A silver halide color photographic light-sensitive material characterized in that silver halide contained in one layer has been gold-sensitized using a gold compound, and the total time from color development to completion of washing or stabilization processing. Wherein the photographic processing is performed within 4 minutes. Embedded image In the formula, R ₁ represents a substituted or unsubstituted aliphatic group, aromatic group or heterocyclic group. R ₂ represents a substituted or unsubstituted aliphatic group having 2 or more carbon atoms, and R ₃ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted aliphatic group, aromatic group or acylamino group. Y represents a hydrogen atom or a group capable of leaving during a coupling reaction with an oxidized developing agent. Embedded image In the formula, R ₁₁ represents a hydrogen atom or a substituent, and R ₁₂ represents R ₁₁
And may be the same or different and represent a hydrogen atom or a substituent. R ₁₃ and R ₁₄ may be the same or different and represent a hydrogen atom or a substituent. However, at least one of R _{11 to} R ₁₄ must be a substituent.