JPH05113638A - Silver halide color photographic sensitive material and color image forming method - Google Patents

Abstract

PURPOSE:To enhance rapid processability and storage stability of a processed image by arranging a layer containing a cyan coupler to farthest apart from a support. CONSTITUTION:This cyan coupler is represented by formula I and the silver halide emulsion layer containing this cyan coupler is arranged farthest apart from the support among 3 kinds of emulsion layers each containing a coupler different from each other. A hydrophilic nonphotosensitive layer containing the compounds of formula II is arranged adjacently to the underside of the cyan coupler-containing emulsion layer, and a hydrophilic nonphotosensitive layer containing an ultraviolet absorber is formed over the cyan coupler- containing emulsion layer, and each emulsion layer has an average silver chloride content of >=90 mole %. In formula I, R1 is an aliphatic group or the like; R2 is an aliphatic group; Y is H or the like: and each of R11-R14 is H or a substituent.

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 excellent in rapid processing suitability and excellent in image storability after processing and a method thereof. The present invention relates to a color image forming method.

[0002]

2. Description of the Related Art In recent years, in order to meet the demand for rapid processing, a high silver chloride emulsion is used as a light-sensitive material in combination with a processing solution containing neither sulfite nor benzyl alcohol contained in a color developing solution of a normal color paper. New systems for use are being developed and introduced to the market. In a color photograph, when such a rapid process is applied, the fading balance of the specific dye image is deteriorated and the fading balance is changed particularly under light irradiation, or the white background portion which is a non-image portion is preserved in a dark place. Sometimes it was colored. Naturally, color photographs have a small degree of fading (light fading and dark fading) both under irradiation with light and in the dark, and the coloring of the white background is kept small in light of the purpose of recording and storing. Need to be done. Therefore, such changes caused by applying rapid processing are a big problem. Although many attempts have been made to improve the image storability, the method conventionally proposed for the photobleaching of a cyan image is not sufficient. Cyan images differ from other dye images in the speed of fading when irradiated with strong light such as direct sunlight and when irradiated with weak light such as room light for a long time. A preferable result cannot be obtained only by making fading difficult, and a new means for improving both fading under strong light and fading in a well-balanced manner has been desired. As a means for improving this point, a method using a dispersion in which a cyan coupler and a polymer latex are phase-dissolved is shown in JP-A-3-24541, but it is not sufficient. Japanese Unexamined Patent Publication (Kokai) No. 3-192347 discloses a method in which a halogen-substituted hydroquinone is added to a cyan color-developing layer to satisfy both processing dependence and photobleaching property, but it cannot be said to be sufficient and is further improved. Was desired.

[0003]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to achieve both rapid processing property and image storability of a high silver chloride light-sensitive material having excellent rapid processing suitability, and photobleaching of a cyan dye in the rapid processing. It is to provide a light-sensitive material and an image forming method which have excellent properties and are less likely to be discolored in balance with other dyes under strong light or weak light and in which white background is not easily colored in dark discoloration.

[0004]

It has been found that the objects of the present invention can be achieved by the following silver halide color photographic light-sensitive materials and image forming methods. [1] A silver halide color photographic light-sensitive material having, on a reflective support, three types of photosensitive silver halide emulsion layers having different photosensitivities, each containing any one of couplers which develop yellow, magenta and cyan, respectively. 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 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] without substantially coexisting with an ultraviolet absorber is provided below (adjacent to the cyan coupler-containing silver halide emulsion layer). The hydrophilic non-photosensitive layer, which is coated on the support side) and contains (3) an ultraviolet absorber substantially without coexisting with the compound represented by the following general formula [I], is the cyan coupler-containing silver halide emulsion. (4) A silver halide color photographic light-sensitive material, characterized in that (4) the average silver chloride content of silver halide contained in each emulsion layer is 90 mol% or more.

[0005]

[Chemical 5]

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 splitting off during a coupling reaction with an oxidized product of a developing agent.

[0007]

[Chemical 6]

In the formula, R ₁₁ represents a hydrogen atom or a substituent, and R ₁₂ may be the same as or different from R ₁₁ and represents a hydrogen atom or a substituent. R _{13 and} R ₁₄ may be the same or different and each 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 characterized in that 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. That is, the light-sensitive material of the present invention contains an ultraviolet absorber above the cyan coupler-containing silver halide emulsion layer and a compound represented by the general formula (I) below, and further comprises the ultraviolet absorber and the general formula ( The compound (I) is not substantially contained in the same layer, and the light-sensitive material is rapidly processed.

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

The present invention will be described in detail below. 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 phrase "coating is provided adjacent to the cyan coupler-containing silver halide emulsion layer below" means that this emulsion layer is a thin non-photosensitive hydrophilic layer (a coupler or the like may be added). Although a non-photosensitive layer containing the compound of the general formula [I] may be applied through the layer, it is preferable that the non-photosensitive layer containing the compound of the general formula [I] is not provided via such a layer. This means that the layers are applied directly. The color photographic light-sensitive material of the present invention is constituted by coating at least one yellow color-forming silver halide emulsion layer, magenta color-forming silver halide emulsion layer and cyan color-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 the support in the order from the support side to the above. In these light-sensitive emulsion layers, a silver halide emulsion having sensitivity in each wavelength region and a dye having a complementary color relationship with the light to be exposed, that is, yellow for blue, magenta for green and cyan for red are formed. By incorporating such a so-called color coupler, color reproduction by the subtractive color method can be performed. However, the photosensitive layer and the coloring hue of the coupler may not have the above correspondence.

The silver halide emulsion used in the present invention is composed of silver chloride, silver chlorobromide or silver chloroiodobromide having a silver chloride content of 90 mol% or more. The silver iodide content is 1 mol% or less, preferably 0.2 mol% or less.
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, the so-called uniform structure grains having the same composition in any part of the silver halide grains, or the core inside the silver halide grains and the shell surrounding it. (Shell) [a single layer or a plurality of layers] particles having a so-called laminated structure having a different halogen composition, or a structure having a portion having a different halogen composition inside or on the surface of the particle (edge of the particle when present on the particle surface, It is possible to appropriately select and use particles having a structure in which parts having different compositions are bonded to a corner or a surface. In order to obtain high sensitivity, it is advantageous to use either of the latter two particles rather than the particles having a uniform structure, and it is also preferable from the viewpoint of pressure resistance. When the silver halide grains have the structure as described above, the boundary between different portions in the halogen composition is an unclear boundary because a mixed crystal is formed due to the composition difference even if the boundary is clear. It may also be one that positively has a continuous structural change.

A so-called high silver chloride emulsion having a high silver chloride content is preferably used for 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, particularly preferably 98 mol% or more. In such a high silver chloride emulsion, a structure having a silver bromide-rich phase localized in the inside and / or the surface of the silver halide grain in the form of layer or non-layer as described above is preferable. The halogen composition of the localized phase preferably has a silver bromide content of at least 10 mol%, more preferably more than 20 mol%. These localized phases can be present inside the particles, on the edges, corners or on the surface of the particles, but those present at the corners of the particles are particularly preferred. On the other hand, it is also preferable to use grains having a uniform structure in which the distribution of the halogen composition in the grains is small, for the purpose of suppressing the sensitivity decrease when the photographic material receives pressure.

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. ˜2 μ is preferable. Further, the particle size distribution thereof is preferably a so-called monodisperse coefficient of variation coefficient (standard deviation of particle size distribution divided by average particle size) of 20% or less, preferably 15% or less. At this time, it is also preferable to use the above monodisperse emulsion by blending it in the same layer for the purpose of obtaining a wide latitude, or to perform multi-layer coating. The shape of silver halide grains contained in a photographic emulsion is one having a regular crystal form such as a cube, a tetradecahedron or an octahedron, an irregular shape such as a sphere or a plate. ) Those having a crystalline form or those having a composite form thereof can be used. It may also be a mixture of those having various crystal forms. In the present invention, it is preferable that 50% or more, preferably 70% or more, and more preferably 90% or more of particles having the above-mentioned regular crystal form are contained in the present invention. In addition to these, an emulsion having tabular grains having an average aspect ratio (diameter in terms of circle / thickness) of 5 or more, preferably 8 or more as a projected area exceeding 50% of all grains can be preferably used.

The emulsion used in the present invention is described by P. Glafkides C
himie et Phisique Photographique (published by Paul Montel, 1
967), by GF Duffin Photo- graphic Emulsion Ch
emistry (Focal Press, 1966), VL Zelikma
n et al by Making and Coating Photographic Emuldion
(Focal Press, Inc., 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 for reacting a soluble silver salt and a soluble halogen salt, any method such as a one-sided mixing method, a simultaneous mixing method, and a combination thereof may be used. You may use. It is also possible to use a method of forming particles in an atmosphere in which silver ions are excessive (so-called reverse mixing method). As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, 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 substantially 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 property, temperature / humidity dependency during exposure, latent image storability, etc. in the process of emulsion grain formation or physical ripening. Polyvalent metal ion impurities can be introduced. Examples of the compound used include salts of cadmium, zinc, lead, copper, thallium, etc., or salts or complex salts of Group VIII elements iron, ruthenium, rhodium, palladium, osmium, iridium, platinum and the like. it can. In particular, the above Group VIII element can be preferably used. The addition amount of these compounds may vary over a wide range depending on the purpose, but it is preferably 10 ^-9 to 10 ^-2 mol with respect to the silver halide. The silver halide emulsion used in the present invention is chemically and spectrally sensitized. For the chemical sensitization, sulfur sensitization represented by the addition of an unstable sulfur compound or selenium sensitization, noble metal sensitization represented by gold sensitization, reduction sensitization and the like can be used alone or in combination. Spectral sensitization is carried out for the purpose of imparting spectral sensitivity in a desired light wavelength region 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 desired spectral sensitivity-a spectral sensitizing dye. Examples of the spectral sensitizing dye used at this time include FM Harmer
By Heterocyclic compounds −Cyanine dyes and relat
ed compounds (JohnWiley & Sons 〔New York, London〕
The company publication, 1964) can be mentioned. As specific examples of compounds and the spectral sensitization method, those 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 precursors thereof for the purpose of preventing fog during production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. Can be added. Specific examples of these compounds are described in JP-A-62-2152.
Those described on pages 39 to 72 of the specification of Japanese Patent Publication No. 72 are preferably used. The emulsion used in the present invention may be any type of so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface, or so-called internal latent image type emulsion in which a latent image is mainly formed inside the grain. Is also good. The gelatin used in the present invention is preferably gelatin that has been subjected to deionization treatment. Gelatin usually contains a large amount of calcium ions and is often contained at 5000 ppm or more. The deionized gelatin used in the present invention preferably has a calcium ion content 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 whole gelatin. Such gelatin may be used in any layer.

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

In the compound represented by the general formula [I],
The substituent represented by R ₁₁ and R ₁₂ is preferably, for example, an alkyl group, an alkenyl group, an aryl group, an acyl group, a cycloalkyl group, a sulfonic acid group, a halogen atom or a heterocyclic group. Examples of the alkyl group include methyl, ethyl, n-propyl, n-butyl, t-butyl,
Examples thereof include n-amyl, i-amyl, n-octyl, n-dodecyl, and n-octadecyl groups, and particularly 1 carbon atom.
Alkyl groups of ˜32 are 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. In addition, 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 groups represented by R ₁₁ and R ₁₂ is preferably 8 or more, and the group represented by R ₁₁ and / or R ₁₂ is It is preferably a group capable of imparting diffusibility. 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 Group, an alkylsulfonyl group, an arylsulfonyl group, a nitro group, a cyano group, an alkyloxycarbonyl group, an aryloxycarbonbonyl group, an alkylacyloxy group or an arylacyloxy group.

In the above general formula [I], R ₁₃ and R ₁₄
Specific examples of the halogen atom, the alkyl group, the aryl group, the acyl group, and the cycloalkyl group represented by are R
_The same as those listed for ₁₁ and R ₁₂ can be mentioned. 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.
-Dodecylthio groups, the arylthio group includes, for example, a phenylthio group, the alkylacylamino group includes, for example, an acetylacylamino group, and the arylacylamino group includes, for example, a benzoylamino group. The alkylcarbamoyl group includes, for example, a methylcarbamoyl group, the arylcarbamoyl group includes, for example, a phenylcarbamoyl group, and the alkylsulfonamide group includes, for example, a methylsulfonamide group, and an arylsulfonamide group. Examples of the group include a phenylsulfonamide 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, and examples of the alkyloxycarbonyl group include a methyloxycarbonyl group and an aryloxycarbonyl group. Examples thereof include a phenyloxycarbonyl group, examples of the alkylacyloxy group include an acetyloxy group, and examples of the arylacyloxy group include a benzoyloxy group. These substituents may be further substituted by an alkyl group, an aryl group, an aryloxy group, an alkylthio group, a cyano group, an acyloxy group, an alkoxycarbonyl group, an acyl group, a sulfamoyl group, a hydroxy group, a nitro group, an amino group and a heterocyclic group. It may be replaced.
Specific examples of the compound represented by the general formula [I] include the following compounds.

[0020]

[Chemical 7]

[0021]

[Chemical 8]

[0022]

[Chemical 9]

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

More preferred are benzotriazole compounds, and more preferred are 2- (2'-hydroxyphenyl) benzotriazole compounds represented by the general formula (II). This compound may be solid or liquid at room temperature.

Specific examples of the liquid ultraviolet absorber are described in JP-B-5
5-36984, 55-12587 and JP-A-5-
It is described in, for example, 8-214152. R ₂₁ , R ₂₂ , R ₂₃ , R _{24 of} the ultraviolet absorber represented by the general formula (II),
Details of the atoms and groups represented by R ₂₅ and R ₂₆ are disclosed in JP-A-58-221844 and 59-46646,
No. 59-109055, Japanese Patent Publication No. 36-10466.
No. 42, No. 42-18787, No. 48-5496, No. 4
No. 8-41572, US Pat. Nos. 3,754,919 and 4,220,711. Next, some specific examples of the compound represented by the general formula (II) are shown in Table 1, but the present invention is not limited thereto.

[0026]

[Chemical 10]

[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 to be coated above the cyan coupler-containing silver halide emulsion photosensitive layer, 1000 mg / m ² or less 150 mg / m ²
Or more, preferably 600 mg / m ² or less 150 m
g / m ² or more. In the present invention, it is necessary that the non-photosensitive layer coated below the cyan coupler-containing silver halide emulsion photosensitive layer does not substantially coexist with the compound represented by the general formula [I]. Is. The term "substantially does not coexist" is less than 150 mg / m ² , preferably 100 mg / m ² or less, and it is particularly preferable not to contain them at all. It is also preferable that the ultraviolet absorber is contained in the cyan coupler-containing silver halide emulsion photosensitive layer in order to stabilize the cyan image. The non-photosensitive layer coated on the cyan coupler-containing layer may contain an anti-stain agent, a stabilizer for the ultraviolet absorber, and the like in addition to the ultraviolet absorber. It may be contained as an emulsified dispersion in the form of being dissolved in a high boiling point organic solvent.

In the present invention, there are used yellow couplers, magenta couplers and cyan couplers capable of forming yellow, magenta and cyan colors by coupling with an oxidized product of an aromatic amine color developing agent. Preferred examples of the cyan coupler represented by the general formula (C) are as follows. In formula (C), R ₁ is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably a substituted aryloxy-substituted alkyl group. Preferred R ₂ in the general formula (C) has 2 to 1 carbon atoms.
5 is a methyl group having an alkyl group of 5 and 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 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. Examples of R ₂ in the general formula (C) include ethyl group, propyl group, butyl group, pentadecyl group, tert-butyl group, cyclohexyl group, cyclohexylmethyl group,
Examples thereof include a phenylthiomethyl group, a dodecyloxyphenylthiomethyl group, a butanamidomethyl group and a methoxymethyl group. Preferred R ₃ in the general formula (C) 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 formula (C) are shown below.

[0035]

[Chemical 11]

[0036]

[Chemical 12]

In the light-sensitive material according to the present invention, a hydrophilic colloid layer for the purpose of improving image sharpness and the like, a dye decolorizable by treatment described in European Patent EP 0,337,490A2, pages 27-76. (Among them, oxonol dye) has an optical reflection density of 0.8 at 680 nm.
12% by weight or more (more preferably 14%) of titanium oxide added in an amount of 70 or more, or surface-treated with a dihydric or tetravalent alcohol (eg, trimethylolethane) in the water resistant resin layer of the support. (Wt% or more) is preferable.

The photographic additives such as cyan, magenta and yellow couplers which can be used in the present invention are preferably dissolved in a high boiling point organic solvent, and the high boiling point organic solvent has a melting point of 100 ° C. or lower and a boiling point of 140 ° C. The above-mentioned water-immiscible compound can be used as long as it is a good solvent for the coupler. The melting point of the high boiling point organic solvent is preferably 80 ° C. or lower. The boiling point of the high boiling point 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.
Cyan, magenta or yellow couplers are also loadable latex polymers in the presence or absence of the high boiling organic solvents described above (e.g. US Pat. No. 4,203,716).
No.) or dissolved with a water-insoluble polymer soluble in an organic solvent, and emulsified and dispersed in a hydrophilic colloid aqueous solution. Preferably US Pat.
The homopolymers or copolymers described in columns 7 to 15 of No. 9 and pages 12 to 30 of WO88 / 00723 are used, more preferably methacrylate-based or acrylamide-based polymers. In particular, use of an acrylamide polymer is preferable in terms of color image stabilization and the like.

Further, in the light-sensitive material according to the present invention, it is preferable to use a color image storability improving compound as described in European Patent EP 0,277,589A2 together with a coupler. In particular, it is preferably used in combination with a pyrazoloazole coupler. That is, the compound (F) that chemically bonds with the aromatic amine-based developing agent remaining after the color development processing to form a chemically inactive and substantially colorless compound and / or the fragrance remaining after the color development processing. The use of the compound (G), which forms a chemically inactive and substantially colorless compound by chemically bonding with an oxidant of a group amine color developing agent, simultaneously or solely, for example, in storage after processing. It is preferable in order to prevent stains and other side effects due to the formation of a coloring dye due to the reaction of the coupler with the color developing agent remaining in the film or its oxidant.

In order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image, the light-sensitive material according to the present invention has an anti-mold property as described in JP-A-63-271247. It is preferable to add an agent.

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

The light-sensitive 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, and in the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 ⁻⁴ seconds is preferable.

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, the light color mixture is removed, and the color reproducibility is significantly improved.

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

Silver halide emulsions 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 the light-sensitive material. The following patent publications, particularly European Patent EP0,355,660A2 (JP-A-2-395)
Those described in No. 44) are preferably used.

[0046]

[Table 7]

[0047]

[Table 8]

[0048]

[Table 9]

[0049]

[Table 10]

As the cyan coupler, a coupler represented by formula (C) and a diphenylimidazole type cyan coupler described in JP-A-2-33144, European Patent EP0,333,18
3-hydroxypyridine cyan couplers described in 5A2 (among others, the couplers listed as specific examples (42)
4 equivalents obtained by adding a chlorine-releasing group to 2 equivalents, 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 preferable).

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 is disclosed in JP-A-2-207250, page 27, upper left column to page 34, upper right column. The method described in 1. is preferably applied.

[0052]

【Example】

Example 1 A surface of a paper support laminated on both sides with polyethylene was provided with a gelatin subbing layer containing sodium dodecylbenzenesulfonate after being subjected to corona discharge treatment, and various photographic constituent layers were further applied to form a layer shown below. A multilayer color photographic paper (Sample 101) having the constitution was produced. The coating liquid was prepared as follows. First layer coating solution preparation 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, ethyl acetate 180.0 cc and solvent (Solv-
1) and (Solv-2) (25 g each) were added and dissolved, and this solution was added with 10% sodium dodecylbenzenesulfonate 60 cc.
An 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, a silver chlorobromide emulsion B (a cubic, a 6: 4 mixture of a large size emulsion B1 having an average grain size of 0.88 μ and a small size emulsion B2 having a grain size of 0.70 μ (silver molar ratio). The variation coefficient of the grain size distribution is 0, respectively. .
08 and 0.10, 0.3 mol% of silver bromide was locally contained in a part of the grain surface of each size emulsion). The above emulsified dispersion A and this silver chlorobromide emulsion B were mixed and dissolved to prepare a coating solution for the first layer having the composition shown below. The 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 hardening agent for each layer, 1-oxy-3,
5-Dichloro-s-triazine sodium salt was used.
Also, the total amount of Cpd-15 and Cpd-16 in each layer is 25.0 mg.
/ M ² and 50.0 mg / m ² were added. The following spectral sensitizing dyes were used in the silver chlorobromide emulsion of each photosensitive emulsion layer.

[0053]

[Table 11]

[0054]

[Table 12]

[0055]

[Table 13]

For the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer, 1- (5-methylureidophenyl)-
5-mercaptotetrazole with silver halide 1
3.4 × 10 ^-4 mol, 9.7 × 10 ^-4 mol, 5.5 × 10 per mol
^-4 mol was added. Further, 4-hydroxy-6-methyl-1,3,3a, 7 is added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer.
Tetrazaindene was added in an amount of 1 × 10 ^-4 mol and 2 × 10 ^-4 mol per mol of silver halide, respectively. Further, the following dyes (the amount in parentheses represents the coating amount) were added to the emulsion layer to prevent irradiation.

[0057]

[Chemical 13]

(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver. Support: Polyethylene laminated paper [Polyethylene on the first layer side contains white pigment (TiO ₂ ) and bluish dye (ultraviolet)] First layer (blue sensitive emulsion layer) Silver chlorobromide emulsion B 0.27 Gelatin 1.36 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) 0.13 Solvent (Solv-2) 0.13

Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing inhibitor (Cpd-4) 0.08 Solvent (Solv-2) 0.25 Solvent (Solv-3) 0.25 Third layer (Green-sensitive emulsion layer) Silver chlorobromide emulsion (Cubic, 6: 4 mixture of large size emulsion G1 with average grain size 0.55μ and small size emulsion G2 with 0.39μ (Ag molar ratio). Coefficients of variation of grain size distribution are 0.10 and 0.08, respectively. 0.13 Gelatin 1.45 Magenta coupler (ExM) 0.16 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 mixing prevention layer) Gelatin 0.70 Color mixing 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, 7: 3 mixture of large size emulsion R1 with average grain size 0.58μ and small size emulsion R2 with 0.45μ (Ag molar ratio). Coefficient of variation of grain size distribution Is 0.09
0.11, AgBr 0.6 mol% was locally contained in a part of the grain surface for each size emulsion)
0.20 Gelatin 0.85 Cyan coupler (ExC) 0.33 UV absorber (UV-2) 0.18 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) 0.22 Solvent (Solv-1) 0.01 Sixth layer (UV absorbing layer) Gelatin 0.55 UV absorber (UV-1) 0.40 Color image stabilizer (Cpd-13) 0.15 Color image stabilizer (Cpd-6) 0.02 Seventh 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.

[0062]

[Chemical 14]

[0063]

[Chemical 15]

[0064]

[Chemical 16]

[0065]

[Chemical 17]

[0066]

[Chemical 18]

[0067]

[Chemical 19]

[0068]

[Chemical 20]

Samples 102 to 110 were prepared by changing the composition of the fourth layer and the sixth layer from the sample 101 as shown in Table 2. In order to keep the strength of the film of the completed light-sensitive material constant, the gelatin of each layer was added by changing it so that the ratio with the oil-soluble component was kept constant.

[0070]

[Table 14]

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

The composition of each processing liquid 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 ─── Triethanolamine 8.0 g 12.0 g Sodium chloride 1.4 g ─── 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, Sumitomo Chemical Co., Ltd.) 1.0 g 2.0 g ────────────── ─────────────── Add water 1000ml 1000ml pH (25 ℃) 10.05 10.45

Bleach-fixing solution (same as tank solution and replenisher) Water 400 ml Ammonium thiosulfate 100 ml (700 g / liter) Sodium sulfite 17 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetate disodium 5 g Bromide Ammonium 40 g ─────────────────────────── Add water to 1000 ml pH (25 ℃) 6.0 Rinse solution (tank solution and replenisher) Is the same) Ion-exchanged water (calcium and magnesium are below 3ppm each)

Next, using a sensitometer (FWH type manufactured by Fuji Photo Film Co., Ltd.), each of the samples 101 to 105 is subjected to gradation exposure through an optical wedge so that the color density is almost gray at 1.0, and the above processing steps are performed. Color development processing was performed. In the color development processing, the rinsing process time was changed to 90 seconds, 150 seconds and 210 seconds, and the time from color development to completion of rinsing was 3 minutes, 4 minutes and 5 minutes, respectively. After measuring the optical densities of the samples thus obtained in advance, in order to evaluate the light fastness of these samples, a xenon fading tester (about 300,000 lux) for 1 day and a fluorescent lamp fading tester (about 10,000) were used. After irradiating with light for 20 days, 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. Also, 80 ° C 70% RH
The sample was allowed to stand for 7 days under the above condition, and the degree of coloring on a white background was examined. The coloring degree is shown in Table 3 with the change in the yellow density of the white background. Samples 106, 109, and 110 have a relatively small decrease in the cyan density of the samples after fading with a fluorescent lamp, but the magenta taste is strong, but the shade should be originally gray, which is not preferable. Samples 107 to 110 are not preferable because the yellow stain becomes strong on the white background when fading 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 mixing inhibitor in the sixth layer are not preferable because the xenon fading is large.

[0075]

[Table 15]

As is clear from the results shown in Table 3, the light-sensitive material of the present invention shows little change in coloration of the white background portion with the lapse of time after processing, and this tendency is remarkable when the total processing time is within 4 minutes. .. Further, the light-sensitive material of the present invention has strong light (xenon) and weak light (fluorescent lamp) in the photobleaching property of a cyan image.
It turns out that it is strong against both of. Similar effects were obtained by using I-20 or I-23 instead of Cpd-4.

Example 2 Samples 101 and 105 were prepared by substituting the cyan coupler as shown in Table 4 to prepare samples 101A to C, 1 respectively.
05A to C.

[0078]

[Table 16]

The comparative cyan couplers used are shown below.

[0080]

[Chemical 21]

Gray gradation exposure was performed in the same manner as in Example 1 so that gray was obtained, and a gray color sample was prepared by the same process as in Example 1. The sample thus obtained was tested for photobleaching property in the same manner as in Example 1. The results are shown in Table 5.

[0082]

[Table 17]

From the results shown in Table 5, the following can be seen. That is, 105 and 105A containing a color mixing inhibitor in the sixth layer
~ C is not preferable because of large xenon photobleaching, 101
C and 105C are not preferable due to large discoloration of fluorescent lamps.
1B has a large xenon photobleaching and is not preferred. It can be seen that 101 and 101A according to the usage of the coupler of the present invention and the color mixture preventing agent and the ultraviolet absorber are preferable.

[0084]

According to the present invention, a color print with improved image storability can be rapidly obtained.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] November 5, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0060

[Correction method] Change

[Correction content]

Fourth layer (color mixing prevention layer) Gelatin 0.70 Color mixing 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, 7: 3 mixture of large size emulsion R1 with average grain size 0.58μ and small size emulsion R2 with 0.45μ (Ag molar ratio). Coefficient of variation of grain size distribution Is 0.09
0.11, AgBr 0.6 mol% was locally contained in a part of the grain surface for each size emulsion)
0.20 Gelatin 0.85 Cyan coupler (ExC) 0.33 UV absorber (UV-2) 0.18 Color image stabilizer (Cpd-1) 0.40 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) 0.22 Solvent (Solv-1) 0.01 Sixth layer (UV absorbing layer) Gelatin 0.55 UV absorber (UV-1) 0.40 Color image stabilizer (Cpd-13) 0.15 Color image stabilizer (Cpd-6) 0.02 Seventh layer (protective layer) Gelatin 1.13 Acrylic modified copolymer of polyvinyl alcohol (modified 17%) 0.15 Liquid paraffin 0.03 Color image stabilizer (Cpd-14) 0.01

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0067

[Correction method] Change

[Correction content]

[0067]

[Chemical 19]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location G03C 7/407

Claims (2)

[Claims] 1. Yellow, magenta, and sheer on a reflective support.
Each containing one of the couplers that develop color.
Three types of photosensitive silver halide emulsion layers with different photosensitivity
In the silver halide color photographic light-sensitive material having
(1) The cyan coupler is a compound represented by the general formula (C).
And a cyan coupler-containing silver halide
Emulsion layers contain different types of couplers
Of the three silver halide emulsion layers, farthest from the support
(2) a compound represented by the following general formula [I]
Contains a non-hydrophilic agent that does not substantially coexist with the UV absorber.
The photosensitive layer is adjacent to the cyan coupler-containing silver halide emulsion layer.
Contacted and coated on the lower side (support side), (3) UV absorption
The agent is substantially combined with a compound represented by the following general formula [I]
The hydrophilic non-photosensitive layer contained without the presence of the cyan coupler
Coated above the silver halide emulsion layer, and (4) each
The average silver chloride content of silver halide contained in the emulsion layer is
90% by mol or more of silver halide
Photographic material. [Chemical 1]R in the formula₁Is a substituted or unsubstituted aliphatic group or aromatic group
Or represents a heterocyclic group. R₂Is a substitution of 2 or more carbon atoms
Or an unsubstituted aliphatic group, R₃Is a hydrogen atom, halogen
Atoms, substituted or unsubstituted aliphatic groups, aromatic groups, or
Represents an acylamino group. Y is a hydrogen atom or a developing agent
The groups that can split off during the coupling reaction with the oxidant of
You [Chemical 2]R in the formula₁₁Represents a hydrogen atom or a substituent, R₁₂Is R₁₁
May be the same as or different from
You R₁₃And R₁₄May be the same or different and are hydrogen atoms
Or represents a substituent. However, R₁₁~ R₁₄At least one of
Must be a substituent. 2. A silver halide color photographic light-sensitive material having three types of light-sensitive silver halide emulsion layers having different photosensitivities, each of which contains one of couplers which develop yellow, magenta and cyan, respectively, on a reflective support. In a color photographic image forming method in which color development processing is performed using the silver halide color photographic light-sensitive material, (1) the cyan coupler is a compound represented by the general formula (C), and the cyan coupler-containing halogenated compound is used. 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] is added: A hydrophilic non-photosensitive layer, which is contained substantially without coexisting with the ultraviolet absorber, is provided on the lower side (support side) adjacent to the cyan coupler-containing silver halide emulsion layer, and (3) A hydrophilic non-photosensitive layer containing an external ray absorbing agent substantially without coexistence with a compound represented by the following general formula [I] is provided above the cyan coupler-containing silver halide emulsion layer, and (4 ) A silver halide color photographic light-sensitive material characterized in that the average silver chloride content of silver halide contained in each emulsion layer is 90 mol% or more, from color development to completion of washing or stabilization. The color photographic image forming method is characterized in that the total time is less than 4 minutes. [Chemical 3] 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, an aromatic group or an acylamino group. Y represents a hydrogen atom or a group capable of splitting off during a coupling reaction with an oxidized product of a developing agent. [Chemical 4] In the formula, R ₁₁ represents a hydrogen atom or a substituent, and R ₁₂ represents R ₁₁
Which may be the same as or different from, and represents a hydrogen atom or a substituent. R ₁₃ and R ₁₄ may be the same or different and each represents a hydrogen atom or a substituent. However, at least one of R _{11 to} R ₁₄ must be a substituent.