JP2678816B2 - Silver halide color photographic materials - Google Patents

Description

TECHNICAL FIELD The present invention relates to a silver halide color photographic light-sensitive material which is highly sensitive, has excellent rapid processability, pressure resistance and storage suitability and is easy to handle. In particular, it relates to color photographic paper.

(Prior Art) With the spread of color photographic light-sensitive materials, color development processing has become simpler and faster.

Under such circumstances, research into speeding up processing and factors affecting the processability of color print light-sensitive materials has been conducted more widely than ever before.

It has been found that it is preferable to use a so-called high silver chloride emulsion having a high silver chloride content as silver halide for rapid processing, and it is becoming widespread. Specific examples of this method are described in detail, for example, in JP-A-61-13416 or WO-87 / 04534. However, high silver chloride emulsions are characterized by low sensitivity and easy fog, and many efforts have been made to overcome this point. For example, US Pat. No. 4,269,927 describes a method of increasing sensitivity by doping high silver chloride grains with various metal ions. This patent also indicates that it is preferable to use gold compounds as sensitizers at the same time. Further, JP-A-2-20853 discloses a method of doping a cyano complex of rhenium, osmium and ruthenium. As another method for increasing the sensitivity, a method of introducing a phase having a different silver halide composition into a grain is shown. For example, JP-A-58-1085
No. 33, a high silver chloride emulsion in which a layer mainly consisting of silver bromide is localized on the grain surface, and JP-A-58-95736 discloses a high silver chloride emulsion having a layer mainly consisting of silver bromide inside the grain, OLS. −3
409445A has a silver bromide content of 10 mol% or more and 50 mol% or more.
A high silver chloride emulsion with a core wrapped in the following layers, OLS-3
No. 409442A shows a high silver chloride emulsion having inside the grain a region having a silver bromide content of more than 50%. Further, JP-A-1-26838 discloses a high silver chloride emulsion having a silver bromide-rich region at a corner portion of the grain, and JP-A-64-6941 discloses a method for sensitizing a grain having a silver bromide-rich region with gold sulfur. It is shown. Since each of these sensitizing methods has drawbacks at the same time, in order to put them into practical use as a light-sensitive material, it is necessary to devise a method of compensating for the drawbacks and to use them together. For example,
When a phase mainly composed of silver bromide or a silver bromide-rich region exists as a structure of chloride grains, generally, when a printing pressure is applied before or after the exposure, the photographic sensitivity varies or the fog occurs. Gold sensitization is well known as a method of increasing photographic sensitivity, but it has a drawback that fog is liable to occur particularly when the light-sensitive material is stored for a long period of time.

Triazine compounds having an active halogen are well known as hardeners used for photography.
No. 253147 shows that the storability of a light-sensitive material is improved by a method in which the water content of the light-sensitive material is 7.5% or more and combined with a high silver chloride emulsion. It was not satisfactory when combined with an emulsion. The hardener preferably has a high water content in order to effectively carry out a crosslinking reaction with gelatin, but on the other hand, when the water content is high, the photographic emulsion deteriorates during storage, and the sensitivity varies,
It tends to cause an increase in fog, and it was difficult to achieve both properties at the same time.

(Problems to be Solved by the Invention) The present invention has high sensitivity, rapid processability, and excellent pressure resistance,
And a silver halide color photographic light-sensitive material excellent in storability,
Especially, it is intended to obtain a color photographic paper.

(Means for Solving the Problems) The inventors have found that the above-described objects can be effectively achieved by the following techniques.

(1) In a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a reflective support, at least one layer of the silver halide emulsion layer is rich in silver bromide in at least one position on the grain surface. A silver halide emulsion obtained by ripening in the presence of a gold compound silver halide chlorobromide grains having a region and an average silver chloride content of 90 mol% or more and containing substantially no iodine The layer which is contained and has a film pH of 3.5 to 6.5 and a water content of the photosensitive material of 3 to 7%, and the layer farthest from the support has an isoelectric point.
A silver halide color photographic light-sensitive material comprising a gelatin of 6.0 or more and 10.0 or less and being hardened with a compound represented by the following general formula [I] and / or [II].

General formula [I] [In the formula, R ₁ is a chlorine atom, a hydroxy group, an alkyl group, an alkoxy group, an alkylthio group, an —OM group (M is a monovalent metal atom), an —NR ^a R ^b group (R ^a and R ^b are each hydrogen. Atom, an alkyl group or an aryl group) or a —NHCOR ^c group (R ^c represents a hydrogen atom, an alkyl group or an aryl group, respectively), and R ₂ has the same meaning as R ₁ above except a chlorine atom. Represents a group. General formula [II] [In the formula, R ₃ and R ₄ are each a chlorine atom, a hydroxy group, an alkyl group, an alkoxy group, or an —OM group (M is 1
Valent metal atom). Q and Q ^a are each -O
Represents a linking group representing-, -S- or -NH-, and L represents an alkylene group or an arylene group. _L and _m each represent 0 or 1. ] (2) The pH of the coating solution located farthest from the support is 5.
5. The silver halide color photographic light-sensitive material as described in the above item 1 or 2, which is 5 or more.

(3) The silver halide color photographic light-sensitive material as described in the above item 1 or 2, wherein the ripening of the silver halide emulsion is carried out substantially in the absence of an unstable sulfur compound.

(Detailed Description of the Invention) In the color photographic light-sensitive material of the present invention, at least one blue-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer and at least one red-sensitive silver halide emulsion layer are coated on a support. Can be configured. In general, color printing paper is usually coated on a support in the order described above, but may be in a different order. Further, an infrared-sensitive silver halide emulsion layer can be used in place of at least one of the above-mentioned emulsion layers. 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 is a salt which does not substantially contain silver iodide, has a silver bromide-rich region in at least one position of the grain, and has an average silver chloride content of 90 mol% or more. Silver bromide is used. Here, the term "substantially free of silver iodide" means that the silver iodide content is 1 mol% or less, preferably 0.
Says 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. The silver bromide rich region means a region in which the silver bromide content is 5 mol% or more. It is preferably 10 mol% or more and 60 mol% or less, and particularly preferably 15 mol% or more and 50 mol% or less. As a preferable example of such a silver bromide-rich region, one that is epitaxially grown at a corner portion of a grain can be mentioned. The boundary between the different portions in the halogen composition may be a clear boundary or an unclear boundary due to the formation of a mixed crystal due to a composition difference, and a positive structural change was positively provided. It may be something.

Regarding the halogen composition of these silver chlorobromide emulsions, those having a silver chloride content of 90 mol% or more are used from the viewpoint of rapid processability. Further, it is preferably 95 mol% or more, particularly 98
It is preferably at least mol%.

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 to 2 μm. preferable.

In addition, their particle size distribution has a coefficient of variation (standard deviation of particle size distribution reduced by average particle size) of 20%
In the following, a so-called monodispersed one of desirably 15% or less is preferable. 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 photographic emulsions have a regular (regular, cubic, tetradecahedral or octahedral) shape.
r) Those having a crystal form, those having an irregular crystal form such as a sphere or a plate, or those having a complex form thereof can be used. Also,
It may be composed of a mixture 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 silver chlorobromide emulsion used in the present invention is a Chim by P. Glafkides.
ie et Phisique Photographique (published by Paul Montel, 19
67), by GF Duffin Photographic Emulsion Chemistr
y (Focal Press, 1966), by VLZelikman et al
Making and Coating Photographic Bmuldion (Focal Pr
ess company, 1964). 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.

In the silver halide emulsion used in the present invention, various polyvalent metal ion impurities can be introduced during the process of forming emulsion grains or physical ripening. Examples of the compound to be used include salts of cadmium, zinc, lead, copper, thallium and the like, or salts or complex salts of Group VIII element iron, ruthenium, rhodium, palladium, osmium, iridium and platinum. it can. These can also be doped in the form of complex salts, in which case ligands such as cyano, nitrosyl and thionitrosyl can be 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 can be obtained by ripening in the presence of a gold compound. Examples of the gold compound include chloroauric acid salts (I), chloroauric acid salts (III), bromoaurate salts (I), bromoaurate salts (III), gold thiocyanate salts (I) and gold thiocyanate. Typical examples are salts (III) and the like, but the compounds are not limited to these and various compounds can be used. The amount of gold compound added is
It is preferably 10 ^-8 mol or more and 10 ^-4 mol or less, and more preferably 10 ^-6 mol or more and 5 × 10 ^-5 mol or less, per mol of silver halide.

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. Examples of spectral sensitizing dyes used at this time include, for example, Heterocyclic compo by FM Harmer.
unds-Cyanine dyes and related compounds (John Wil
ey & Sons [New York, London], 1964). As specific examples of the compounds and the spectral sensitization method, those described in the above-mentioned JP-A-62-215272, from page 22, upper right column to page 38, are preferably used.

To the silver halide emulsion used in the present invention, various compounds or their precursors are added for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. be able to. As specific examples of these compounds, those described on pages 39 to 72 of the above-mentioned JP-A No. 62-2151272 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. May be.

In the present invention, the film is hardened using at least one selected from the compounds represented by the general formula [I] and / or the general formula [II].

The compounds represented by the above general formulas [I] and [II] used in the present invention will be described below.

In the general formulas [I] and [II], examples of the alkyl group component of the alkyl group represented by R ₁ and the groups represented by the alkoxy group and the alkylthio group include an alkyl group having 1 to 3 carbon atoms. Examples thereof include a methyl group, an ethyl group, a methoxy group, an ethoxy group, a methylthio group, and an ethylthio group. Also, −OM represented by R ₁
The M representing a monovalent metal atom of the group, such as sodium, have ammonium or the like, -NR ^a: Examples of the alkyl group represented by R ^a and R ^b in R ^b alkyl group having 1 to 3 carbon atoms Examples thereof include a methyl group and an ethyl group, and the aryl group includes a phenyl group. Further, the alkyl group and the aryl group represented by R ^{c of the} —NHCOR ^c group represented by R ₁ are the same groups as the alkyl group and the aryl group represented by the above R ^a and R ^b , respectively.

R ₂ is a group having the same meaning as R ₁ described above except for a chlorine atom as described above.

The groups represented by R ₃ and R ₄ are the same groups as the group represented by R ₁ . The alkylene group represented by L includes an alkylene group having 1 to 3 carbon atoms such as a methylene group and an ethylene group, and the arylene group includes a phenylene group.

Next, specific examples of the compounds represented by the above general formulas [I] and [II] will be described.

In the present invention, the membrane pH needs to be 3.5 to 6.5, preferably 4.0 to 6.0, and particularly preferably 4.5 to 5.5.

If the film pH exceeds the range of the present invention and is too low, there arises inconveniences such as a decrease in sensitivity and a large dependence on the time until development after exposure. On the other hand, if it is too high, fog tends to occur during storage of the light-sensitive material.

The membrane pH is measured by mounting a flat surface GST-5313F manufactured by Toa Denpa Kogyo Co., Ltd. on the electrode of the front pH meter.

The isoelectric point of gelatin can be determined by measuring the pH after subjecting the mixed bed to ion exchange treatment. The details of this method are described in Journal of Colloid Interface Science, Vol. 27, p. 667 (1986).

By combining gelatin having a high isoelectric point as a constituent of the present invention, the occurrence of scratches during processing is reduced and the storability of the light-sensitive material is improved.

The light-sensitive material of the present invention has a water content of 3 to 7%, and more preferably 4 to 6%. The water content is measured by sampling a certain amount of the photosensitive material to be measured, weighing it, and then measuring this weight as W ₁ , drying again at 100 ° C. for 18 hours, and then weighing it again as W _2. Is defined.

Moisture content (%) = (W ₁ -W ₂ ) ÷ W ₁ × 100 When the water content exceeds the range of the present invention, the storage stability of the light-sensitive material is deteriorated, and sensitivity change and fog occur.

In the color light-sensitive material of the present invention, yellow couplers, magenta couplers and cyan couplers which are coupled with an oxidized form of an aromatic amine color developing agent to form yellow, magenta and cyan, respectively, are usually used.

Cyan coupler preferably used in the present invention,
The magenta coupler and the yellow coupler are represented by the following formulas (C-I), (C-II), (M-I), (M-II) and (Y).

In the general formulas (CI) and (C-II), R ₁ , R ₂
And R ₄ represents a substituted or unsubstituted aliphatic, aromatic or heterocyclic group; R ₃ , R ₅ and R ₆ represent a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group or an acylamino group; ₃ may represent a non-metallic atomic group forming a 5- or 6-membered nitrogen-containing ring together with R ₂ . Y ₁ and Y _{2 each} represent a hydrogen atom or a group capable of leaving during a coupling reaction with an oxidized form of a developing agent. n represents 0 or 1.

R ₅ in the general formula (C-II) is preferably an aliphatic group, for example, a methyl group, 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.

Preferred examples of the cyan coupler represented by the general formula (CI) or (C-II) are as follows.

In the general formula (CI), preferred R ₁ is an aryl group,
A heterocyclic group, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group,
More preferably, they are aryl groups substituted by a carbamoyl group, a sulfonamide group, a sulfamoyl group, a sulfonyl group, a sulfamide group, an oxycarbonyl group, or a cyano group.

When R ₃ and R ₂ do not form a ring in formula (CI), R ₂ is preferably a substituted or unsubstituted alkyl group,
It is an aryl group, particularly preferably a substituted aryloxy-substituted alkyl group, and R ₃ is preferably a hydrogen atom.

In formula (C-II), R ₄ is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably a substituted aryloxy-substituted alkyl group.

In the general formula (C-II), preferred R ₅ has 2 to 15 carbon atoms.
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-II), R ₅ is more preferably an alkyl group having 2 to 15 carbon atoms, particularly preferably an alkyl group having 2 to 4 carbon atoms.

Preferred R ₆ in formula (C-II) is a hydrogen atom or a halogen atom, and a chlorine atom and a fluorine atom are particularly preferred. Preferred Y ₁ and Y ₂ in the general formulas (CI) and (C-II) are a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, and a sulfonamide group, respectively.

In the general formula (MI), R ₇ and R ₉ represent an aryl group, R ₈ represents a hydrogen atom, an aliphatic or aromatic acyl group, an aliphatic or aromatic sulfonyl group, and Y ₃ represents hydrogen. Represents an atom or a leaving group. The substituents permitted for the aryl group (preferably phenyl group) of R ₇ and R ₉ are the same as the substituents permitted for the substituent R ₁ , and when there are two or more substituents, they are the same. But they may be different. R ₈
Is preferably a hydrogen atom, an aliphatic acyl group or a sulfonyl group, and particularly preferably a hydrogen atom. Desirable Y ₃ is of a type capable of releasing at any of a sulfur, oxygen or nitrogen atom, and particularly preferred is a type of releasing at a sulfur atom as described in, for example, US Pat. No. 4,351,897 and International Publication WO88 / 04795.

In the general formula (M-II), R ₁₀ represents a hydrogen atom or a substituent. Y ₄ represents a hydrogen atom or a leaving group, particularly preferably a halogen atom or an arylthio group. Za, Zb and
Zc represents methine, substituted methine, = N- or -NH-,
One of the -Zb bond and the Zb-Zc bond is a double bond, and the other is a single bond. The case where the Zb-Zc bond is a carbon-carbon double bond includes the case where it is a part of an aromatic ring. When R ₁₀ or Y ₄ forms a multimeric structure of 2 tatami mats or more, Za,
When Zb or Zc is a substituted methine, it includes the case where the substituted methine forms a multimeric or higher polymorph.

Among the pyrazoloazole couplers represented by the general formula (M-II), the imidazo [1,2-b] pyrazole described in U.S. Pat. No. 4,500,630 has small yellow sub-absorption of a coloring dye and light fastness. Are preferred and are
The pyrazolo [1,5-b] [1,2,4] triazole described in 4,540,654 is particularly preferred.

In addition, a branched alkyl group as described in JP-A-61-65245 is directly linked to the 2-, 3- or 6-position of the pyrazolotriazole ring to form a pyrazolotriazole coupler.
Pyrazoloazole couplers containing a sulfonamide group in the molecule as described in 65246, JP-A-61-147254
Pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group as described in JP-A No. 226,849 and pyrazoloazole couplers having an alkoxy group or aryloxy group at the 6-position as described in EP-A-226,849 and EP 294,785. The use of zorotriazole couplers is preferred.

In the general formula (Y), R ₁₁ represents a halogen atom, an alkoxy group, a trifluoromethyl group or an aryl group, and R ₁₂ represents a hydrogen atom, a halogen atom or an alkoxy group. A is _{-NHCOR 13, -NHSO 2 -R 13,} -SO 2 NHR 13,
−COOR ₁₃ , Represents Here, R ₁₃ and R ₁₄ each represent an alkyl group, an aryl group or an acyl group. Y ₅ represents a leaving group. R ₁₂
And the substituents of R ₁₃ and R ₁₄ are the same as the substituents permitted for R ₁ and the leaving group Y ₅ is preferably of a type capable of leaving at either an oxygen atom or a nitrogen atom. And a nitrogen atom-elimination type is particularly preferable.

Formulas (C-I), (C-II), (M-I), and (M-
Specific examples of the couplers represented by II) and (Y) are listed below.

The couplers represented by the above general formulas (C-I) to (Y) are usually added in the silver halide emulsion layer constituting the photosensitive layer in an amount of 0.1 to 1.0 mol, preferably 0.1 to 1.0 mol per mol of silver halide.
0.50.5 mol.

In the present invention, various known techniques can be applied to add the coupler to the photosensitive layer. Usually, it can be added by an oil-in-water dispersion method known as an oil protection method, and after being dissolved in a solvent, it is emulsified and dispersed in a gelatin aqueous solution containing a surfactant. Alternatively, water or a gelatin aqueous solution may be added to a coupler solution containing a surfactant, and the oil-in-water dispersion may be formed by phase inversion. The alkali-soluble coupler can also be dispersed by a so-called Fisher dispersion method. After removing the low-boiling organic solvent from the coupler dispersion by a method such as distillation, noodle washing or ultrafiltration, it may be mixed with a photographic emulsion.

Dielectric constant (25 ° C) as a dispersion medium for such couplers
It is preferable to use a high boiling point organic solvent having a refractive index (25 ° C.) of 2 to 20 and a refractive index (25 ° C.) of 1.5 to 1.7 and / or a hydrogen insoluble polymer compound.

As the high boiling point organic solvent, preferably, the following general formula (A)
The high-boiling organic solvent represented by (E) is used.

General formula (B) W ₁ -COO-W ₂ Formula (E) W ₁ —O—W ₂ (wherein W ₁ , W ₂ and W ₃ each represent a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocyclic group; W ₄ is W ₁ , OW ₁ or SW
_And n is an integer of 1 to 5, and when n is 2 or more, W ₄ may be the same or different. In the general formula (E), W ₁ and W ₂ represent a condensed ring. May be formed).

The high-boiling organic solvent that can be used in the present invention is a compound that is not miscible with water having a melting point of 100 ° C. or less and a boiling point of 140 ° C. or more other than the general formulas (A) to (E). Can be used. The high boiling point organic solvent preferably has a melting point of 80 ° C. or lower. The boiling point of the high boiling organic solvent is preferably 160 ° C.
And more preferably 170 ° C. or higher.

Details of these high-boiling organic solvents are described in
No. 215272, page 137, lower right column to page 144, upper right column.

These couplers may be impregnated with a loadable latex polymer (for example, U.S. Pat.No. 4,203,716) in the presence or absence of the high-boiling organic solvent or dissolved in a water-insoluble and organic solvent-soluble polymer. It can be emulsified and dispersed in a hydrophilic colloid aqueous solution.

Preferably, pages 12 to 30 of WO 88/00723
The homopolymers or copolymers described on the page are used, and the use of an acrylamide polymer is particularly preferred for stabilizing a color image.

The light-sensitive material prepared by using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, and the like as a color fogging inhibitor.

Various brown inhibitors can be used in the light-sensitive material of the present invention. That is, as an organic browning inhibitor for cyan, magenta and / or yellow images, hydroquinones,
6-hydroxychromans, 5-hydroxycoumarins, spirochromans, p-alkoxyphenols,
Hindered phenols centered on bisphenols, gallic acid derivatives, methine dioxybenzenes,
Representative examples include aminophenols, hindered amines, and ether or ester derivatives in which the phenolic hydroxyl group of each of these compounds is silylated or alkylated. Further, metal complexes represented by (bissalicylaldoximato) nickel complex and (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

Specific examples of organic brown inhibitors are described in the following patent specifications.

Hydroquinones are disclosed in U.S. Pat.Nos. 2,360,290 and 2,4
No. 18,613, No. 2,700,453, No. 2,701,197, No. 2,
No. 728,659, No. 2,732,300, No. 2,735,765, No.
No. 3,982,944, No. 4,430,425, UK Patent No. 1,363,921
No., U.S. Pat.Nos. 2,710,801 and 2,816,028,
6-hydroxychromans, 5-hydroxychromaranes, and spirochromans are described in U.S. Pat.
No. 3,573,050, No. 3,574,627, No. 3,698,909, No. 3,764,337, JP-A-52-152225, Spiroindanes in U.S. Pat.No. 4,360,589, p-Alkoxyphenols in U.S. Pat. UK Patent 2,0
66,975, JP-A-59-10539, JP-B-57-19765, etc., hindered phenols are described in British Patent No. 3,700,455.
No., JP-A-52-72224, U.S. Pat.
No. 52-6623, gallic acid derivatives, methylenedioxybenzenes and aminophenols are described in U.S. Pat.
Nos. 3,457,079, 4,332,886 and JP-B-56-21144, hindered amines are disclosed in U.S. Pat.
No. 4,268,593, British Patent No. 1,326,889, No. 1,354,
No. 313, No. 1,410,846, JP-B-51-1420, JP-A-58
Nos. 1-114036, 59-53846 and 59-78344, metal complexes are disclosed in U.S. Pat.Nos. 4,050,938 and 4,241,155.
And British Patent No. 2,027,731 (A). These compounds can achieve the object by adding usually 5 to 100% by weight of the corresponding color coupler to the photosensitive layer after co-emulsification with the coupler. In order to prevent the deterioration of the cyan dye image due to heat and particularly to light, it is more effective to introduce an ultraviolet absorber into the cyan coloring layer and the layers on both sides adjacent thereto.

Examples of the ultraviolet absorber include benzotriazole compounds substituted with an aryl group (for example, those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (for example, those described in U.S. Pat. Nos. 3,314,794 and 3,352,681),
Benzophenone compounds (for example, those described in JP-A-46-2784) and cinnamate compounds (for example, US Pat.
3,705,805 and 3,707,395), butadiene compounds (described in U.S. Pat. No. 4,045,229),
Alternatively, benzooxide compounds (for example, US Pat.
Nos. 3,406,070 and 3,677,672 and 4,271,307) can be used. UV-absorbing couplers (eg, α-naphthol-based cyan dye-forming couplers)
Alternatively, an ultraviolet absorbing polymer or the like may be used. These ultraviolet absorbers may be mordanted to a specific layer.

Above all, a benzotriazole compound substituted with the above-mentioned aryl group is preferable.

It is particularly preferable to use the following compounds together with the above-mentioned 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.

Preferred as the compound (F) is a compound having a secondary reaction rate constant k ₂ (in trioctyl phosphate at 80 ° C.) of 1.0 / mol · sec to 1 × 10 ⁻⁵ / mol · sec with the second reaction rate constant with p-anisidine. Compound. The secondary reaction rate constant can be measured by the method described in JP-A-63-158545.

If k ₂ is greater than this range, the compound itself becomes unstable, resulting in decomposition reacts with gelatin or water. On the other hand, if k ₂ is smaller than this range, the reaction with the remaining aromatic amine-based developing agent is slow, and as a result, the side effect of the remaining aromatic amine-based developing agent may not be prevented.

More preferable compound (F) can be represented by the following general formula (FI) or (F II).

General formula (FI) R _1- (A) _n -X General formula (F II) In the formula, R ₁ and R ₂ each represent an aliphatic group, an aromatic group, or a heterocyclic group. n represents 1 or 0. A represents a group which reacts with an aromatic amine developing agent to form chemical engagement, and X represents a group which reacts with an aromatic amine developing agent and leaves. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group, and Y represents that an aromatic amine-based developing agent is added to the compound of the general formula (F II). Represents a promoting group. Here, R ₁ and X, Y and R ₂ or B may be bonded to each other to form a cyclic structure.

Representative methods of chemically bonding with the residual aromatic amine-based developing agent are a substitution reaction and an addition reaction.

Specific examples of the compounds represented by formulas (FI) and (F II) are described in JP-A-63-158545, JP-A-62-283338,
Those described in specifications such as European Patent Publication Nos. 298321 and 277589 are preferable.

On the other hand, a more preferred compound (G) which chemically bonds with the oxidation product of the aromatic amine-based developing agent remaining in the color developing solution to form a chemically inactive and colorless compound is represented by the following general formula ( GI).

Formula (GI) RZ In the formula, R represents an aliphatic group, an aromatic group, or a heterocyclic group. Z represents a nucleophilic group or a group which decomposes in the light-sensitive material to release a nucleophilic group. In the compound represented by the general formula (GI), Z is Pearson's nucleophilicity, ⁿ CH ₃ I value (RGPear
Son, et al., J. Am. Chem. soc., 90 , 319 (1968)) is preferably a group of 5 or more, or a group derived therefrom.

Specific examples of the compound represented by the general formula (GI) are described in EP-A-255722, JP-A-62-143048 and JP-A-62-143048.
-229145, Japanese Patent Application Nos. 63-136724 and 62-214681, and European Patent Publications 298321 and 277589 are preferred.

The details of the combination of the compound (G) and the compound (F) are described in EP-A-277589.

The light-sensitive material prepared according to the present invention contains a water-soluble dye or a dye which becomes water-soluble by photographic processing as a filter dye in the hydrophilic colloid layer, or for various purposes such as prevention of irradiation or halation. You may. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.

As the binder or protective colloid that can be used in the emulsion layer of the light-sensitive material of the present invention, gelatin is advantageously used, but other hydrophilic colloids can be used alone or together with gelatin.

In the present invention, gelatin is lime-treated,
Either one treated with an acid may be used. The details of the method for producing gelatin are described in Arthur Wuice, The Macromolecular Chemistry of Gelatin (Academic Press, 1964).

As the support used in the present invention, a transparent film such as a cellulose nitrate film or a polyethylene terephthalate, which is usually used for a photographic light-sensitive material, or a reflective support can be used. For the purposes of the present invention, the use of a reflective support is more preferred.

The term "reflective support" used in the present invention refers to a material which enhances reflectivity and sharpens a dye image formed in a silver halide emulsion layer. Examples include those coated with a hydrophobic resin dispersedly containing a light reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate, and those using a hydrophobic resin dispersedly containing a light reflecting substance as a support. For example, baryta paper, polyethylene-coated paper, polypropylene-based synthetic paper, a transparent support provided with a reflective layer or combined with a reflective substance, such as a glass plate, polyethylene terephthalate, a polyester film such as cellulose triacetate or cellulose nitrate, Examples include a polyamide film, a polycarbonate film, a polystyrene film, and a vinyl chloride resin.

Other reflective supports include specular or secondary
A support having a seed diffuse reflective metal surface can be used. The metal surface has a spectral reflectance of 0.5 in the visible wavelength range.
The above materials are preferred, and the metal surface is preferably roughened or diffusely reflective using metal powder. As the metal, aluminum, tin, silver, magnesium or an alloy thereof is used, and the surface may be the surface of a metal plate, a metal foil, or a metal thin layer obtained by rolling, vapor deposition, plating, or the like.
Above all, it is preferable to obtain a metal by vapor deposition on another substrate. It is preferable to provide a water-resistant resin, especially a thermoplastic resin layer, on the metal surface. An antistatic layer is preferably provided on the side of the support of the present invention opposite to the side having the metal surface. For details of such a support, see, for example, JP-A-61-210346.
Nos. 63-24247, 63-24251 and 63-24255.

 These supports can be appropriately selected depending on the purpose of use.

As the light-reflective substance, it is preferable to sufficiently knead a white pigment in the presence of a surfactant.
It is preferable to use those treated with a to tetravalent alcohol.

The occupied area ratio (%) per defined unit area of the white pigment fine particles is most typically obtained by dividing the observed area into adjacent 6 μm × 6 μm unit areas and projecting the unit area. It can be obtained by measuring the occupied area ratio (%) (R _i ) of the fine particles. Variation coefficient of the occupied area ratio (%) is the ratio of the standard deviation s of R _i to the average value of R _i () s /
Can be obtained by The number (n) of the target unit areas is preferably 6 or more. Therefore the coefficient of variation s / Can be obtained by

In the present invention, the occupied area ratio of the pigment fine particles (%)
Is preferably 0.15 or less, particularly preferably 0.12 or less. 0.08
In the following cases, it can be said that the dispersibility of the particles is substantially “uniform”.

The color photographic light-sensitive material of the present invention is preferably subjected to color development, bleach-fixing, and washing (or stabilization). Bleaching and fixing may be performed separately, instead of in a single bath as described above.

The color developer used in the present invention contains a known aromatic primary amine color developing agent. A preferred example is a p-phenylenediamine derivative, representative examples of which are shown below, but are not limited thereto.

D-1 N, N-diethyl-p-phenylenediamine D-2 2-amino-5-diethylaminotriene D-3 2-amino-5- (N-ethyl-N-laurylamino) toluene D-4 4- [ N-ethyl-N- (β-hydroxyethyl) amino] aniline D-5 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline D-6 4-amino-3-methyl -N-ethyl-N-
[Β- (methanesulfonamido) ethyl] -aniline D-7 N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide D-8 N, N-dimethyl-p-phenylenediamine D-9 4-amino -3-Methyl-N-ethyl-N-methoxyethylaniline D-10 4-Amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-11 4-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline Among the above p-phenylenediamine derivatives, particularly preferred is 4-amino-3-methyl-N-ethyl-N- [β-
(Methanesulfonamido) ethyl] -aniline (Exemplary compound D-6).

In addition, salts of these p-phenylenediamine derivatives and sulfates, hydrochlorides, sulfites, p-toluene sulfonates and the like may be used. The amount of the aromatic primary amine developing agent used is preferably about 0.1 g to about 20 g per developer,
More preferably, the concentration is about 0.5 g to about 10 g.

In the practice of the present invention, it is preferable to use a developer that does not substantially contain benzyl alcohol. Here, the term "substantially free from" means that the concentration of benzyl alcohol is preferably 2 ml / or less, more preferably 0.5 ml / or less, and most preferably benzyl alcohol is not contained at all.

More preferably, the developer used in the present invention does not substantially contain sulfite ions. Sulfite ions have a function of dissolving silver halide and reacting with an oxidized form of the developing agent, and at the same time, function as a preservative of the developing agent to reduce the dye-forming efficiency. Such an effect is presumed to be one of the causes of the increase in the fluctuation of the photographic characteristics due to the continuous processing.
Here, substantially not containing, preferably 3.0 × 10 ^-3
It has a sulfite ion concentration of mol / or less, and most preferably contains no sulfite ion at all. However, in the present invention, a very small amount of sulfite ion used for preventing oxidation of a processing agent kit in which a developing agent is concentrated before preparing a working solution is excluded.

The developer used in the present invention preferably does not substantially contain sulfite ions, and more preferably does not substantially contain hydroxylamine. this is,
This is because hydroxylamine itself has a silver developing activity at the same time as functioning as a preservative of the developer, and fluctuations in the concentration of hydroxylamine are considered to greatly affect photographic characteristics. The term "substantially free of hydroxylamine" as used herein means that the hydroxylamine concentration is preferably 5.0 × 10 ⁻³ mol / or less, and most preferably contains no hydroxylamine at all.

More preferably, the developer used in the present invention contains an organic preservative in place of the hydroxylamine and sulfite ions.

Here, the organic preservative refers to any organic compound that reduces the deterioration rate of an aromatic primary amine color developing agent by being added to a processing solution of a color photographic light-sensitive material. That is, organic compounds having a function of preventing oxidation of a color developing agent by air or the like, among which hydroxylamine derivatives (excluding hydroxylamine; the same applies hereinafter), hydroxamic acids, hydrazines, hydrazides, phenols, α-hydroxy ketones, α-amino ketones,
Sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, condensed amines, and the like are particularly effective organic preservatives. These are disclosed in
−4235, 63−30845, 63−21647, 63−4465
No. 5, 63-53551, 63-43140, 63-56654,
63-58346, 63-43138, 63-146041, 63
-44657, 63-44656, U.S. Patent No. 3,615,503,
No. 2,494,903, JP-A-52-143020, JP-B-48-30496
No., etc.

Other preservatives include JP-A Nos. 57-44148 and 57-5.
Various metals described in 3749, salicylic acids described in JP-A-59-180588, alkanolamines described in JP-A-54-3532, polyethyleneimines described in JP-A-56-94349, U.S. Pat. An aromatic polyhydroxy compound described in 3,746,544 or the like may be contained as necessary. In particular, addition of alkanoamines such as triethanolamine, dialkylhydroxylamine such as diethylhydroxylamine, hydrazine derivatives or aromatic polyhydroxy compounds is preferable.

Among the above organic preservatives, hydroxylamine derivatives and hydrazine derivatives (hydrazines and hydrazides)
Are particularly preferred, and for details, see Japanese Patent Application No. 62-2552.
No. 70, No. 63-9713, No. 63-9714, No. 63-11300 and the like.

It is more preferable to use the hydroxylamine derivative or the hydrazine derivative in combination with an amine in terms of improving the stability of the color developing solution, and further improving the stability during continuous processing.

Examples of the amines include cyclic amines described in JP-A-63-239447, amines described in JP-A-63-128340, and other amines disclosed in Japanese Patent Application No. 63-9713. 63
Amines as described in JP-11300.

In the present invention, 3.5 × 1 chloride ion in the color developer
The content is preferably 0 ^{-2 to} 1.5 × 10 ^-1 mol / mol. Particularly preferably, it is 4 × 10 ^-2 to 1 × 10 ^-1 mol /. When the chloride ion concentration is more than 1.5 × 10 ^-1 to 10 ^-1 mol / mol, it has a disadvantage of delaying the development, and is not preferable for achieving the object of the present invention of rapid and high maximum concentration. Further, if it is less than 3.5 × 10 ⁻² mol / mol, it is not preferable in preventing fog.

In the present invention, the bromine ion in the color developer is 3.0
It is preferable to contain x10 ^-5 mol to 1.0 x 10 ^-3 mol. More preferably, it is 5.0 × 10 ^{-5 to} 5 × 10 ^-4 mol /. If the bromine ion concentration is higher than 1 × 10 ⁻³ mol / mol, the development is delayed, the maximum density and the sensitivity are reduced, and
If it is 0 ^-5 mol / below, it can not be sufficiently prevented fog.

Here, chlorine ions and bromine ions may be directly added to the developer or may be eluted from the photosensitive material into the developer during the development processing.

When directly added to the color developer, examples of the chloride ion supply material include sodium chloride, potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, and cadmium chloride, with the preferred ones being preferred. Are sodium chloride and potassium chloride.

Further, it may be supplied from a fluorescent whitening agent added to the developer.

Sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide, thallium bromide Among them, preferred are potassium bromide and sodium bromide.

When eluted from the light-sensitive material during the development processing, both chloride ions and bromine ions may be supplied from the emulsion, or may be supplied from sources other than the emulsion.

The color developer used in the present invention is preferably pH 9
To 12, more preferably 9 to 11.0, and the color developer may further contain a compound of a known developer component.

In order to maintain the above pH, it is preferable to use various buffers. Buffers include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt,
N, N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-1,3-propanediol salt, valine salt , Proline salts, trishydroxyaminomethane salts, lysine salts, and the like. In particular, carbonate, phosphate, tetraborate, and hydroxybenzoate are soluble and have a high pH of 9.0 or more.
It is particularly preferable to use these buffering agents, because they have an excellent buffering ability in the H region, have no adverse effects on the photographic performance (fogging, etc.) even when added to the color developing solution, and are inexpensive.

Specific examples of these buffers include sodium carbonate,
Potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), tetraborate Potassium, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-
Sodium sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate)
And the like. However, the invention is not limited to these compounds.

The amount of the buffer added to the color developer was 0.1 mol / mol.
It is preferably at least 0.1 mol / -0.4 mol / m.

In addition, various chelating agents can be used in the color developer as a precipitation inhibitor for calcium or magnesium, or for improving the stability of the color developer.
For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine N, N, N ', N'-tetramethylenesulfonic acid, trans-cyclohexanediaminetetraacetic acid, 1, 2-diaminopropane tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N'-bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid and the like can be mentioned.

These chelating agents may be used in combination of two or more as necessary.

These chelating agents may be added in an amount sufficient to block the metal ions in the color developer. Eg 1
It is about 0.1g to 10g per unit.

An optional development accelerator can be added to the color developer as needed.

As development accelerators, JP-B-37-16088 and JP-B-37-598
No. 7, No. 38-7826, No. 44-12380, No. 45-9919, and thioether compounds represented by U.S. Pat. p-phenylenediamine compound, JP-A-50-1377
No. 26, JP-B-44-30074, JP-A-56-156826 and 5
Quaternary ammonium salts represented by 2-43429 and the like, U.S. Pat.Nos. 2,494,903, 3,128,182, 4,230,796,
No. 3,253,919, JP-B-41-11431, U.S. Pat.
Nos. 546, 2,596,926 and 3,582,346, amine compounds described in JP-B-37-16088, JP-B-42-25201, U.S. Pat.No. 3,128,183, JP-B-41-11431, JP-B-42-2388.
No. 3, US Pat. No. 3,532,501, etc., polyalkylene oxides, 1-phenyl-3-pyrazolidones, imidazoles, and the like can be added as necessary.

In the present invention, an optional antifoggant can be added as required. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-
Nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-
Representative examples include nitrogen-containing heterocyclic compounds such as thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developer applicable to the present invention preferably contains a fluorescent whitening agent. 4,4 'as fluorescent whitening agent
-Diamino-2,2'-disulfostilbene compounds are preferred. The amount of addition is 0-5 g / preferably 0.1 g-4 /.

If necessary, various surfactants such as alkyl sulfonic acid, aryl sulfonic acid, aliphatic carboxylic acid and aromatic carboxylic acid may be added.

The processing temperature of the color developer applicable to the present invention is 20 to
The temperature is 50 ° C, preferably 30 to 40 ° C. The processing time is 20 seconds to 5 minutes, preferably 30 seconds to 2 minutes. The amount of replenishment is preferably as small as possible, but ^{20 to} 60 ml is appropriate per 1 m ^{2 of} the light-sensitive material, and preferably 50 to 300 ml. More preferably 60ml-200m
l, most preferably from 60 ml to 150 ml.

Next, the desilvering step applicable to the present invention will be described. As the desilvering step, generally, any steps such as a bleaching step-fixing step, a fixing step-bleach-fixing step, a bleaching step-bleach-fixing step and a bleach-fixing step may be used.

The bleaching solution, bleach-fixing solution and fixing solution applicable to the present invention will be described below.

As the bleaching agent used in the bleaching solution or the bleach-fixing solution, any bleaching agent can be used. In particular, organic complex salts of iron (III) (for example, ethylenediaminetetraacetic acid,
Preferred are aminopolycarboxylic acids such as diethylenetriaminepentaacetic acid and complex salts such as aminopolyphosphonic acid, phosphonocarboxylic acid and organic phosphonic acid) or organic acids such as citric acid, tartaric acid and malic acid; persulfates; hydrogen peroxide and the like. .

Among these, organic complex salts of iron (III) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution. Aminopolycarboxylic acids, aminopolyphosphonic acids, or organic phosphonic acids or salts thereof useful for forming organic complex salts of iron (III) include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropane. Examples thereof include tetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, iminodiacetic acid, and glycol ether diaminetetraacetic acid. These compounds may be any of the sodium, potassium, thylium or ammonium salts.
Among these compounds, iron (III) complex salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, and methyliminodiacetic acid are preferable because of their high bleaching power.
These ferric ion complex salts may be used in the form of a complex salt or a ferric salt such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate. And a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc., to form a ferric ion complex salt in a solution. Also, the chelating agent is second
The iron ion complex salt may be used in excess of the iron salt complex. Among the iron complexes, iron aminopolycarboxylate complexes are preferable, and the amount of addition is 0.01 to 1.0 mol /, preferably 0.05 to 1.0 mol / mol.
~ 0.50 mol /.

In the bleaching solution, the bleach-fixing solution and / or the prebath thereof,
Various compounds can be used as a bleaching accelerator.
For example, U.S. Pat.No. 3,893,858, German Patent No.
Compounds having a mercapto group or a disulfide bond described in 1,290,812, JP-A-53-95630, Research Disclosure No. 17129 (July, 1978), JP-B-45-8506, JP-A-52-50 -20832, 53-327
No. 35, U.S. Pat. No. 3,706,561, and the like, thiourea-based compounds or halides such as iodine and bromine ions are preferred because of their excellent bleaching power.

In addition, the bleaching solution or bleach-fixing solution applicable to the present invention includes bromide (eg, potassium bromide, sodium bromide, ammonium bromide), chloride (eg, potassium chloride, sodium chloride, ammonium chloride) or iodine. A rehalogenating agent such as a compound (for example, ammonium iodide), etc. may be added, if necessary, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, It is possible to add one or more kinds of inorganic acids having a pH buffering ability such as sodium citrate and tartaric acid, organic acids and alkali metal or ammonium salts thereof, or corrosion inhibitors such as ammonium nitrate and guanidine.

Fixing agents used in the bleach-fixing solution or the fixing solution include known fixing agents, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylenebisthioglycolic acid Thioether compounds such as 3,6-dithia-1,8-octanediol and water-soluble silver halide dissolving agents such as thioureas, which can be used alone or in combination of two or more. . Also, a special bleach-fixing solution comprising a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can be used. In the present invention, it is preferable to use thiosulfate, particularly ammonium thioacetate. The amount of the fixing agent per one is preferably from 0.3 to 2 mol, more preferably from 0.5 to 1.0 mol. The pH range of the bleach-fixing solution or fixing solution is preferably 3 to 10, more preferably 5 to 9.

Further, the bleach-fixing solution may contain other various types of fluorescent whitening agents, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

The bleach-fixing solution and the fixing solution include sulfites (for example, sodium sulfite, potassium sulfite, ammonium sulfite, etc.) and bisulfites (for example, ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.) as preservatives, It preferably contains a sulfite ion releasing compound such as metabisulfite (for example, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.). These compounds are converted to sulfite ions
The content is preferably 0.02 to 0.05 mol / mol, more preferably 0.04 to 0.40 mol /.

As a preservative, sulfite is generally added,
In addition, you may add ascorbic acid, a carbonyl bisulfite adduct, a carbonyl compound, etc.

Further, a buffer, an optical brightener, a chelating agent, an antifoaming agent, a fungicide, and the like may be added as necessary.

After desilvering such as fixing or bleach-fixing, washing and / or stabilization are generally performed.

The amount of rinsing water in the rinsing process varies widely depending on the characteristics of the light-sensitive material (for example, depending on the material used such as coupler), application, temperature of rinsing water, number of rinsing tanks (number of ammunition), replenishment method such as countercurrent, forward current, and various other conditions. Can be set to. Among these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent direction is shown in the Journal of the Society of Motion Picture and Television Engineers (Journa
l of the Society of Motion Picture and Television
Engineers), Vol. 64, pp. 248-253 (May, 1955). Usually, the number of stages in the multistage countercurrent system is preferably 2 to 6, particularly preferably 2 to 4.

According to the multi-stage countercurrent method, the amount of washing water can be greatly reduced,
For example, 0.5 to 1 or less per 1 m ^{2 of the} photosensitive material is possible, and the effect of the present invention is remarkable. Problems occur. As a solution to such a problem, the method of reducing calcium and magnesium described in JP-A-62-288838 can be used very effectively. Further, isothiazolone compounds and thiabendazoles described in JP-A-57-8542, 61-12
Chlorinated fungicides such as chlorinated sodium isocyanurate described in JP-A No. 145, benzotriazole described in JP-A-61-26761, copper ions and others, written by Hiroshi Horiguchi, "Bactericidal and antifungal chemistry"
(1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Society of Antimicrobial and Fungicide, "Encyclopedia of Antifungal Agents" (1986) And the bactericides described in (1) and (2).

Further, in the washing water, a surfactant as a draining agent and a chelating agent represented by EDTA as a hardening agent can be used.

It is possible to carry out the treatment with the stabilizing solution directly after the washing step or without the washing step. A compound having an image stabilizing function is added to the stabilizing solution, for example, an aldehyde compound represented by formalin, or a film suitable for stabilizing a dye.
Examples include a buffer for adjusting the pH, and an ammonium compound. Further, in order to prevent the growth of bacteria in the liquid and impart fungicidal properties to the processed photosensitive material, the above-mentioned various bactericides and fungicides can be used.

Further, a surfactant, a fluorescent whitening agent and a hardening agent may be added. In the processing of the light-sensitive material of the present invention, when stabilization is directly performed without going through a washing step, a method disclosed in
All known methods described in No. 8543, No. 60-220345, etc. can be used.

In addition, it is also a preferred embodiment to use a chelating agent such as 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, or a magnesium or bismuth compound.

A so-called rinsing liquid is also used as a washing liquid or a stabilizing liquid used after the desilvering treatment.

The preferred pH of the washing step or the stabilization step is 4 to 10, more preferably 5 to 8. The temperature can be set variously depending on the use and characteristics of the photosensitive material, but is generally 15 to 45 ° C, preferably 20 to 40 ° C. The time can be set arbitrarily, but a shorter time is desirable from the viewpoint of reducing the processing time. Preferably
15 seconds to 1 minute and 45 seconds, more preferably 30 seconds to 1 minute and 30 seconds.
The smaller the replenishment amount, the more desirable it is from the viewpoint of running cost, reduction of discharge amount, handleability and the like.

A specific preferable replenishing amount is 0.5 to 50 times, preferably 3 to 4 times the amount of light-sensitive material and the amount brought in from the previous bath per unit area.
It is 0 times. Alternatively, the amount is 1 or less, preferably 500 ml or less per 1 m ^{2 of the} photosensitive material. Replenishment may be performed continuously or intermittently.

The liquid used in the water washing and / or stabilizing step can be further used in the previous step. As an example of this, the overflow of the washing water is reduced by a multi-stage countercurrent method, and is allowed to flow into a bleach-fix bath preceding the bath, and the bleach-fix bath is replenished with a concentrated solution to reduce the amount of waste liquid.

(Examples) Hereinafter, the present invention will be specifically described with reference to Examples.
The present invention is not limited to this.

Example 1 A multilayer color photographic paper having the following layer constitution was produced on a paper support laminated on both sides with polyethylene.

 The coating solution was prepared as follows.

Preparation of first layer coating solution 19.1 g of yellow coupler (ExY) and color image stabilizer (Cp
d-1) 27.2 cc of ethyl acetate and 8.2 g of a solvent (Solv-1) were added to 4.4 g of the color image stabilizer (Cpd-7) and 0.7 g of the color image stabilizer (Cpd-7) and dissolved, and the resulting solution was dissolved in 10% sodium dodecylbenzenesulfonate 8c.
It was emulsified and dispersed in 185 cc of a 10% gelatin aqueous solution containing c. On the other hand, a silver chlorobromide emulsion was prepared, and the above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the structure shown below. Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer.

Preparation of silver halide emulsion.

Blue-sensitive silver halide emulsion: Add 32 g of lime-processed gelatin to 1000 ml of distilled water, and add 40 ° C.
After dissolving in, add 5.8 g of sodium chloride and raise the temperature to 75 ° C.
Was raised. To this solution, 3.8 ml of N, N'-dimethylimidazolidin-2-thione (1% aqueous solution) was added. Then, a solution of 6.4 g of silver nitrate dissolved in 180 ml of distilled water and a solution of 2.2 g of sodium chloride dissolved in 180 ml of distilled water were added to the above solution while maintaining vigorous mixing for 10 minutes at 75 ° C. Further, a solution prepared by dissolving 153.6 g of silver nitrate in 400 ml of distilled water and a solution prepared by dissolving 52.8 g of sodium chloride in 400 ml of distilled water were added to the above solution with vigorous mixing for 35 minutes while maintaining 75 ° C. After the addition of the aqueous silver nitrate solution and the aqueous sodium chloride solution was completed, the temperature was maintained at 75 ° C for 15 minutes, then the temperature was lowered to 40 ° C, and washing and desalting were performed. further,
The following blue-sensitive sensitizing dye was added to obtain an emulsion (A).

Keep pAg at 7 for emulsion (A) and add 0.1 for 1 minute.
A specified silver nitrate aqueous solution and a 75:25 mixed aqueous solution of sodium chloride and potassium bromide were added to the host particles at 0.5 and 0.5, respectively.
Emulsion (B) was obtained by adding mol%. Emulsion (A),
(B) Emulsions (A-1), (A-2), (A-3), and ((A-1), (A-2), (A-3), and ( B-
1), (B-2), and (B-3). The following additives were added to these emulsions, respectively. Green-sensitive silver halide emulsion: 32 g of lime-processed gelatin was added to 1000 ml of distilled water, and the temperature was 40 ° C.
After dissolving in, 3.3 g of sodium chloride is added and the temperature is 52 ° C
Was raised. To this solution, 3.2 ml of N, N'-dimethylimidazolidin-2-thione (1% aqueous solution) was added. Then, a solution prepared by dissolving 32.0 g of silver nitrate in 250 ml of distilled water and a solution prepared by dissolving 11.0 g of sodium chloride in 250 ml of distilled water were added to the above solution while maintaining vigorous mixing at 52 ° C. for 14 minutes. Further, a solution prepared by dissolving 128.0 g of silver nitrate in 400 ml of distilled water and a solution prepared by dissolving 44.0 g of sodium chloride in 400 ml of distilled water were added to the above solution over 35 minutes while maintaining the temperature at 52 ° C. while vigorously mixing. After the addition of the aqueous silver nitrate solution and the aqueous sodium chloride solution was completed, the temperature was kept at 52 ° C. for 15 minutes, then the temperature was lowered to 40 ° C., and washing and desalting treatment were performed. further,
The following green-sensitive sensitizing dye was added, and this was designated as emulsion (C).

Keep pAg at 7 for emulsion (C) and 0.1 for 1 minute
Emulsion (D) was prepared by adding 0.5 mol% each of a prescribed silver nitrate aqueous solution and a 50:50 mixed aqueous solution of sodium chloride and potassium bromide. Emulsions (C) and (D) were optimally chemically sensitized with chloroauric acid, chloroauric acid and sodium thiosulfate, and sodium thiosulfate, respectively.
1), (C-2), (C-3) and (D-1), (D-
2) and (D-3). The following additives were added to these emulsions, respectively.

Red-sensitive silver halide emulsion: A green-sensitive silver halide emulsion in which the spectral sensitizing dye and the additives were changed was prepared in the same manner to prepare emulsion (E-1),
(E-2), (E-3) and (F-1), (F-2),
(F-3).

 The following were used as the spectral sensitizing dyes in each layer.

Blue-sensitive emulsion layer (2.0 × 10 ^-4 mol per mol of silver halide) Green-sensitive emulsion layer (4.0 × 10 ^-4 mol per mol of silver halide) and (7.0 × 10 ^-5 mol per mol of silver halide) Red-sensitive emulsion layer (0.9 × 10 ⁻⁴ mol per mol of silver halide) The following compounds were added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ⁻³ mol per mol of silver halide.

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

Also, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer in an amount of 1 × 10 ^-4 mol and 2 × 10 mol, respectively, per mol of silver halide. ×
10 ^-4 mol was added.

With respect to the silver halide emulsion thus prepared, the grain shape, average grain size and grain size distribution were determined from electron micrographs. All the silver halide grains contained in the emulsion were cubic. The grain size is represented by the average value of the diameter of the circle equivalent to the projected area of the grain, and the grain size distribution is the standard deviation of the grain size divided by the average grain size. They are summarized in Table 1.

The following dyes were added to the emulsion layer to prevent irradiation.

The total amount of Cpd-10 and Cpd-11 in each layer was 25.0% each.
It was added to a mg / m ² and 50.0 mg / m ^2.

(Layer Configuration) 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 bluish dye (ultra-blue)] First layer (blue sensitive layer) Said silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow coupler (ExY ) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-1) 0.35 Color image stabilizer (Cpd-7) 0.06 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing inhibitor (Cpd-5) 0.08 Solvent ( Solv-1) 0.16 Solvent (Solv-4) 0.08 Third layer (green-sensitive layer) Said silver chlorobromide emulsion 0.12 Gelatin 1.24 Magenta coupler (ExM) 0.20 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer ( Cpd-3) 0.15 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-9) 0.02 Solvent (Solv-2) 0.40 Fourth layer (UV absorbing layer) Gelatin 1.58 UV absorber (UV-1) 0.47 Anti-color mixing agent (Cpd-5) 0.05 Solvent (Solv-5) 0.24 Fifth layer (red sensitive layer) Silver chlorobromide emulsion 0.23 Chin 1.34 Cyan coupler (ExC) 0.32 Color image stabilizer (Cpd-6) 0.17 Color image stabilizer (Cpd-7) 0.40 Color image stabilizer (Cpd-8) 0.04 Solvent (Solv-6) 0.15 Sixth layer (UV ray) Absorption layer) Gelatin 0.53 UV absorber (UV-1) 0.16 Color mixing inhibitor (Cpd-5) 0.02 Solvent (Solv-5) 0.08 Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (Degree of modification) 17%) 0.17 Liquid paraffin 0.03 As the gelatin used for the seventh layer, acid-treated gelatin having an isoelectric point of 7.5 was used.

 0.09 g of (I-2) was used as a hardener.

(ExY) Yellow coupler 1: 1 mixture (molar ratio) with (ExM) magenta coupler 1: 1 mixture (molar ratio) (ExC) cyan coupler 2: 4: 4 mixture by weight of each (Cpd-1) color image stabilizer (Cpd-2) Color image stabilizer (Cpd-3) Color image stabilizer (Cpd-4) Color image stabilizer (Cpd-5) Color mixing inhibitor (Cpd-6) color image stabilizer 2: 4: 4 mixture (weight ratio) (Cpd-7) color image stabilizer Average molecular weight 60,000 (Cpd-8) color image stabilizer (Cpd-9) Color image stabilizer (Cpd-10) Preservative (Cpd-11) Preservative (UV-1) UV absorber 4: 2: 4 mixture (weight ratio) (Solv-1) solvent (Solv-2) solvent 2: 1 mixture (volume ratio) (Solv-4) solvent (Solv-5) solvent (Solv-6) solvent Comparative Hardener Comparative 1 CH ₃ C (CH ₂ OCH ₂ SO ₂ CH = CH ₂ ) ₃ Using the emulsions shown in Table 1, the water content of the hardener (same amount) and the film pH were changed as shown in Table 2 to prepare samples 101 to 123.
I got

After 4 weeks from the completion of coating these samples,
Stored at ℃ for 3 weeks and frozen during that time, using a sensitometer (FWH type manufactured by Fuji Photo Film Co., Ltd., color temperature of light source 3200 ° K) at the same time as a sample for sensitometry through a three-color separation filter. Gradation exposure was given. The exposure at this time was performed so that the exposure amount was 250 CMS with the exposure time of 0.1 seconds.

After exposure, the color density was measured after the following treatment, and the sensitivity and fog value of the blue sensitive layer were read. Calculate the difference between the product stored at 40 ℃ and the frozen product, and take the ratio of the difference and the sensitivity of the frozen product (ΔS
%) It was used as a measure of the storability of the light-sensitive material. The smaller the value of this ratio, the better the storage stability, which is preferable.

For the sensitivity, the exposure amount required for the frozen sample 102 to obtain an optical density of 1.0 is set to 1, and the reciprocal of the exposure amount ratio required for other samples to obtain an equivalent density is multiplied by 100. Used as a scale. The larger this number, the higher the sensitivity and the better.

The image-wise exposure of the sample 102 was carried out using a paper processor, and the capacity of the tank for color development was reduced to 2
A running solution (steady-state solution) was obtained by continuous treatment until double replenishment, and this was used as a treatment solution, which was processed in the following steps to obtain a color image.

Processing temperature Time Replenishment amount ^* Tank capacity Color development 35 ℃ 45 seconds 161ml 17 Bleach fixing 30 to 36 ℃ 45 seconds 215ml 17 Stable 30 to 37 ℃ 20 seconds -10 Stable 30 to 37 ℃ 20 seconds -10 Stable 30 to 37 ℃ 20 seconds -10 Stable 30 to 37 ° C 20 seconds 248ml 10 Drying 70 to 85 ° C 60 seconds * Replenishment amount per 1 m ^{2 of} light-sensitive material (4 tank countercurrent method from stable to) The composition of each processing solution is as follows. Is the street.

Bleach-fixing solution (same as tank solution and replenisher) Water 400ml Ammonium thiosulfate (700g /) 100ml Sodium sulfite 17g Ethylenediaminetetraacetic acid iron (III) ammonium 55g Ethylenediaminetetraacetic acid disodium 5g Glacial acetic acid 9g Water 1000ml pH (25 5.40 Stabilizer (same as tank solution and replenisher) Formalin (37%) 0.1g Formalin-sulfite adduct 0.7g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02g 2-methyl-4 -Isothiazolin-3-one 0.01 g Copper sulphate 0.005 g Water is added to 1000 ml pH (25 ° C) 4.0 In order to evaluate the easiness of scratching the photosensitive material, the photosensitive material under development is manufactured by Cyclone Co., Ltd. The nylon scrubbing brush and the Kikuron of No. 1 were rubbed under a constant load, and after the treatment, the impression finished sample was visually judged, and the severity of the scratch was classified into 5 ranks. The larger the number, the easier the scratches are, and the smaller the number, the harder the scratches are.

 The results are shown in Table 3.

It can be seen that the light-sensitive material of the present invention is excellent in rapid processability, is not easily scratched, and is excellent in storage stability of the light-sensitive material.

(Effects of the Invention) By carrying out the present invention, it was possible to obtain a silver halide color photographic light-sensitive material having high sensitivity, excellent suitability for rapid processing, excellent pressure resistance, and excellent storage stability as a light-sensitive material.

Claims (3)

(57) [Claims] 1. A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a reflective support, wherein at least one of the silver halide emulsion layers comprises
A process of ripening in the presence of a gold compound, substantially iodine-free silver chlorobromide grains having a silver bromide-rich region on at least one surface of the grain and having an average silver chloride content of 90 mol% or more. Containing the silver halide emulsion obtained in the above step, the pH of the photographic constituent layer is 3.5 to 6.5, and the water content of the light-sensitive material is 3 to
7%, and the layer farthest from the support is
A silver halide color photographic light-sensitive material containing gelatin having an isoelectric point of 6.0 or more and 10.0 or less and being hardened with a compound represented by the following general formula [I] and / or [II]. General formula [I] [In the formula, R ₁ is a chlorine atom, a hydroxy group, an alkyl group, an alkoxy group, an alkylthio group, an —OM group (M is a monovalent metal atom), an —NR ^a R ^b group (R ^a and R ^b are each hydrogen. Atom, an alkyl group or an aryl group) or a —NHCOR ^c group (R ^c represents a hydrogen atom, an alkyl group or an aryl group, respectively), and R ₂ has the same meaning as R ₁ above except a chlorine atom. Represents a group. General formula [II] [In the formula, R ₃ and R ₄ are each a chlorine atom, a hydroxy group, an alkyl group, an alkoxy group, or an —OM group (M is 1
Valent metal atom). Q and Q ^a are each -O
Represents a linking group representing-, -S- or -NH-, and L represents an alkylene group or an arylene group. l and m each represent 0 or 1. ] 2. The silver halide color photographic light-sensitive material according to claim 1, wherein the pH of the coating solution for the layer farthest from the support is 5.5 or more. 3. The silver halide according to claim 1 or 2, wherein the ripening of the silver halide emulsion is carried out substantially in the absence of an unstable sulfur compound. Color photographic light-sensitive material.