JPH05113644A - Silver halide multicolor photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance color fastness of a yellow color developed image and color reproduction performance and storage stability of a raw sample by incorporating a specified water-hardly-soluble epoxy compound in an emulsion layer containing a yellow coupler. CONSTITUTION:The yellow coupler-containing silver halide emulsion layer among silver halide emulsion layers contains at least one kind of water-hardly- soluble epoxy compound represented by formula I, and a weight of hydrophilic component to nonhydrophilic component of 0.90-1.30 in the emulsion layers, and a magenta coupler-containing emulsion layer contains at least one kind of magenta coupler represented by formula II, and the raw paper of a paper base has a pH of 5-9. In formulae I and II, each of R1-R5 is H, alkyl, or the like; R is a substituent; n is an integer of 0-4; Y is a divalent bonding group: X is -0- or the like; R10 is H or the like; Y is a releasable group or the like; each of Za, Zb, and Z, is methine or the like; and one of bondings between Za-Zb Za-Zc has a double bond and the other has a single bond.

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 relates to a silver halide multilayer color photographic light-sensitive material in which a color image storability is improved by using an epoxy compound which is poorly soluble in water. . More specifically, the present invention relates to a rapid-processing type silver halide multilayer color photographic light-sensitive material having improved yellow image fastness, color reproducibility, and raw storage stability of the light-sensitive material.

[0002]

2. Description of the Related Art When a color photographic light-sensitive material is stored semipermanently as a record, the degree of photobleaching and dark fading is suppressed to a minimum and the three-color fading balance of yellow, magenta and cyan dye images is set to an initial state. Is required to hold. However, when stored in a humid environment,
The dark fading of the yellow dye image is larger than that of the other two colors, and the image quality is often deteriorated. In addition, so-called pyrazoloazole type magenta couplers represented by U.S. Pat.Nos. 4,540,654 and 4,882,266 came into practical use, which gave good color reproducibility, and also provided a color print with less stain and excellent image storability. Came to be. On the other hand, the conventionally used yellow couplers are generally benzoylacetanilide type or pivaloylacetanilide couplers. In particular, the latter is mainly used for color paper and color reversal system because of its excellent yellow dye spectral absorption characteristics and fastness.

However, when the above magenta coupler, particularly the magenta coupler having an appropriate coupling speed, and the above yellow coupler are used, the resulting color photograph has high density, low fog and excellent color reproducibility. It has been found that the so-called color mixing problem during image storage, that is, the magenta density in a yellow image becomes high during long-term storage of color photographs, and it is desirable to maintain excellent color reproducibility even during image storage. Was there. In order to solve such a problem, JP-A-64-50048 and 64-64
-50049 and JP-A-61-4041 disclose the use of cyclic ether compounds or epoxy group-containing compounds, but these compounds have some effect in improving the dark fading of yellow color images due to temperature and humidity. Although it is recognized, it has not been sufficiently improved, and it has a problem with side effects such as desensitization and fog during the life of the photosensitive material.

[0004]

SUMMARY OF THE INVENTION Therefore, the first object of the present invention is to provide a silver halide color photographic light-sensitive material capable of forming a dye image having improved color reproduction with improved fading during long-term storage. To provide the material. The second object is to provide a rapidly processable silver halide color photographic light-sensitive material with improved color image storability without causing side effects such as increased fog or desensitization that may occur during the life of the light-sensitive material. is there.

[0005]

[Means for Solving the Problems] As a result of earnest studies on the above-mentioned problems, it was found that the following problems can be solved. That is, in a silver halide multilayer color photographic light-sensitive material having three kinds of light-sensitive silver halide emulsion layers each containing any one of yellow, magenta and cyan couplers on a paper support, The yellow coupler-containing emulsion layer contains at least one poorly water-soluble epoxy compound having a group represented by the following general formula (AO).
And a weight ratio of the non-hydrophilic component to the hydrophilic component in the emulsion layer is 0.90 or more and 1.30 or less,
And the magenta coupler-containing emulsion layer contains at least one magenta coupler represented by the general formula (M-II),
The solution has been achieved by a silver halide multilayer color photographic light-sensitive material characterized in that the base paper of the paper support has a pH of 5 or more and 9 or less.

[0006]

[Chemical 4]

In the above general formula (AO), R ₁ ,
R ₂ , R ₃ , R ₄ and R ₅ may be the same or different and each represents a hydrogen atom, an alkyl group or an aryl group. R represents a substituent, n represents the integer of 0-4. -Y
-Represents a divalent linking group. -X- represents -O-, -S- or -N (R ')-. R'is a hydrogen atom, an acyl group,
An alkylsulfonyl group, an arylsulfonyl group, an aryl group, a heterocyclic group, or _{-C (R 6) (R 7} ) (R 8)
Represents. Here, R ₆ , R ₇ and R ₈ may be the same or different and each represents an alkyl group or the following general formula (A
The group represented by O-1) is shown. R ₆ and R ₇ further represent a hydrogen atom.

[0008]

[Chemical 5]

When n is 2 to 4, a plurality of R's may be the same or different. Any one of R _{1 to} R ₅
, R ′ and R, or two Rs may combine with each other to form a 5- to 7-membered ring. However, when X is -S-, the total number of carbon atoms of the compound is 15 or more. X is -O-,
And -Y- is -SO ₂ - when is or phenylene,
n is an integer of 1 to 4, or at least one of R ₁ to R ₅ is an alkyl group or an aryl group. X
There -O-, and and Y is -O-CO ₂ - when is, R
The total number of carbon atoms of _{1 to} R ₄ and R is 10 or more.

[0010]

[Chemical 6]

In the formula, R ₁₀ represents a hydrogen atom or a substituent. Y ₄ represents a hydrogen atom or a leaving group. Za, Zb and Zc are methine, substituted methine, = N- or -NH-.
And one of the Za-Zb bond and the Zb-Zc bond is a double bond and the other is a single bond. When the Zb-Zc bond is a carbon-carbon double bond, it includes the case where it is part of an aromatic ring. This includes the case where R ₁₀ or Y ₄ forms a dimer or higher multimer, and the case where Za, Zb or Zc is a substituted methine, the substituted methine forms a dimer or higher multimer.

The water-insoluble epoxy compound having a group represented by formula (AO) of the present invention will be described in more detail. At 25 ℃ is a poorly soluble epoxy compound in water,
It is an epoxy compound having a solubility in water of 10% or less and a total carbon number of 9 or more, preferably 18 or more, more preferably 30 or more.

The alkyl group represented by the general formula (AO) is a linear, branched or cyclic alkyl group (for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, cyclohexyl, n-octyl). , T-octyl,
n-decyl, sec-dodecyl, n-hexadecyl, n
-Octadecyl) and may further have a substituent. The aryl group in formula (AO) is an aromatic hydrocarbon group (for example, phenyl or naphthyl) and may have a substituent.

The heterocyclic group represented by the general formula (AO) is a 5- to 7-membered cyclic group in which at least one ring-constituting atom is an atom selected from an oxygen atom, a nitrogen atom and a sulfur atom. It doesn't matter. Further, it may have a substituent. Examples of the heterocyclic group include thienyl, furyl, imidazolyl, pyrazolyl, pyrrolyl,
Indolyl, pyridyl, chromanil, pyrazolidinyl,
Examples thereof include piperazinyl, 4-morpholinyl, triazinyl and the like. The substituent in formula (AO) means an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a hydroxy group, a halogen atom, a cyano group, and a nitro group. Group, acyl group, acyloxy group, silyloxy group, sulfonyl group, sulfonyloxy group, alkoxycarbonyl group, aryloxycarbonyl group, amide group, imide group, carbamoyl group, sulfamoyl group,
Examples thereof include ureido group, urethane group, aminosulfamoyl group, amino group, alkylamino group, arylamino group and heterocyclic amino group.

R ₁ , R ₂ , R ₃ , R ₄ and R ₅ may be the same or different and each represents a hydrogen atom, an alkyl group,
Alternatively, it represents an aryl group. R represents a substituent, n is 0 to
Represents an integer of 4. When n is 2 to 4, plural Rs may be the same or different. -Y- is a divalent linking group (for example, a single bond, -O -, - S -, - SO 2 -, - S- substituted which may imino group, -O-CO ₂ -, the substituents And an phenylene group which may have a substituent, a phenylene group which may have a substituent, a naphthylene group and a divalent heterocyclic group).

X is --O--, --S-- or --N (R ')-.
Represent R'is a hydrogen atom, an acyl group (eg acetyl, acroyl, benzoyl), an alkylsulfonyl group (eg methanesulfonyl, ethanesulfonyl, dotecansulfonyl), an arylsulfonyl group (eg benzenesulfonyl, toluenesulfonyl), an aryl group, a heterocycle group, a _{-C (R 6) (R 7} ) (R 8). Here, R ₆ , R ₇ and R ₈ may be the same or different and each represents an alkyl group or a group represented by general formula (AO-1) shown below. R ₆ and R ₇ further represent a hydrogen atom.

[0017]

[Chemical 7]

R ₁ , R ₂ and R ₃ in the general formula (AO-1) represent the groups defined in the general formula (AO). Further, any two of R _{1 to} R ₅ , R ′ and R or two R
May combine with each other to form a 5- to 7-membered ring. However, when X is -S-, the total number of carbon atoms of the compound is 15 or more. The X is -O-, and and -Y- is -SO ₂
-Or phenylene, n is an integer of 1 to 4, or at least one of R _{1 to} R ₅ is an alkyl group or an aryl group. X is -O- and Y is -O
When it is —CO ₂ —, the total carbon number of R _{1 to} R ₄ and R is 10 or more.

The group represented by the general formula (AO) may have a partner atom bonded to any of a hydrogen atom, a carbon atom, a nitrogen atom, a sulfur atom and an oxygen atom. Among the epoxy compounds having a group represented by the general formula (AO),
From the viewpoint of the effect of the present invention, it is a compound having 3 or more, more preferably 4 or more, and still more preferably 5 or more groups represented by the general formula (AO). On the other hand, the epoxy compound having a group represented by the general formula (AO) preferably has a total sum of benzene rings of 2 or more, more preferably 3 or more, and further preferably 4 or more.
That is all.

Of the epoxy compounds having a group represented by the general formula (AO) of the present invention, the following general formula (A) is preferable.
E-1), (AE-2), (AE-3) and (AE-
4).

[0021]

[Chemical 8]

In the general formulas (AE-1) to (AE-4), E represents the following general formula (AO-2).

[0023]

[Chemical 9]

R _{1 to} R ₅ and X in the general formula (AO-2) represent the groups defined in the general formula (AO). In formulas (AE-1) to (AE-4), R represents a group defined by formula (AO). L ₁ , L ₂ , and L
₃ may be the same or different and each represents a divalent linking group. As L ₁ , L ₂ and L ₃ , an alkylene group which may have a substituent is preferable, and examples thereof include the following structures.

[0025]

[Chemical 10]

N ₁ is 3 to 6, m ₁ is 0 to 3, and n ₂ is 1 to
5, n ₃ is 1 to 4, n ₄ is 1 to 5, m ₂ is 0 to 4, m ₃
Is 0 to 3, m ₄ is 0 to 4, n ₅ is 1 to 5, m ₅ is 0.
4, m ₆ ~m ₉ represents an integer of 0-4. p ₁ and x represent a real number of 0 to 20. p ₂ represents an integer of 3 to 4, A
Represents a trivalent to tetravalent organic group. Examples of A include the following structures.

[0027]

[Chemical 11]

When a plurality of E's and R's are present, the plurality of E's may be the same or different, and the plurality of R's may be the same or different. The compounds represented by the general formulas (AE-2) and (AE-3) may be a mixture of compounds having different numbers of p ₁ and p ₂ .

Among the compounds represented by the general formulas (AE-1) to (AE-4), the general formulas (AE-1) to (AE-3)
Those represented by
Those represented by E-2) to (AE-3), and those represented by the general formula (AE-2) are most preferable. Among those represented by the general formula (AE-2), the general formula (AO-
It is preferable that -X- in 2) is represented by -O-, and p ₁ is 1 to 20, more preferably 2 to 2.
0, more preferably 3 to 20, most preferably 4 to 20
And n _{2 to} n ₄ are preferably 1 to ₂ , m _{2 to} m ₄ are preferably 0 to 3, and most preferably 1 to 2, and R is an alkyl group, a halogen atom or an alkoxy group. preferable.

Specific examples of the compound of the present invention are shown below.
The present invention is not limited to this.

[0031]

[Chemical 12]

[0032]

[Chemical 13]

[0033]

[Chemical 14]

[0034]

[Chemical 15]

[0035]

[Chemical 16]

[0036]

[Chemical 17]

[0037]

[Chemical 18]

[0038]

[Chemical 19]

[0039]

[Chemical 20]

[0040]

[Chemical 21]

[0041]

[Chemical formula 22]

[0042]

[Chemical formula 23]

The variables x and y in the structural formula are real numbers and may be in the range of 0 to 20. The reason why x is not necessarily an integer is that epoxy compounds having several kinds of integer values are mixed in a certain ratio and show the average value thereof. These epoxy compounds may be used alone or in combination of two or more.

The epoxy compound of the present invention is used by emulsifying and dispersing it in a hydrophilic binder such as an aqueous gelatin solution together with a coupler or separately using a surfactant. The epoxy compound of the present invention itself may be used as the high boiling organic solvent, but a high boiling organic solvent having a boiling point of 160 ° C. or higher other than the epoxy compound of the present invention, which is hardly soluble in water, a low boiling auxiliary organic solvent or / and water. You may use together with an insoluble polymer soluble in an organic solvent. As examples of the high boiling point organic solvent and the polymer, those disclosed in JP-A-64-537 are preferable. Further, the coupler and the sparingly water-soluble epoxy compound can be added to different layers, but it is preferable to add them in the same layer, particularly in the same oil droplet.

The epoxy resin used in the present invention is
For example, it can be obtained by reacting bisphenol A and epichlorohydrin in the presence of caustic soda (see Naoshishiro Oishi et al., "Plastic Materials Course (5) Epoxy Resin", Nikkan Kogyo Shimbun). The use amount of the epoxy compound of the present invention is preferably 3% to 100%, and more preferably 5% to 30% by weight with respect to the yellow coupler.

The hydrophilic component in the yellow coupler-containing layer of the present invention is one having a water saturated pumping rate of 60% by weight or more in the ASTM D570 test method, or one whose volume swells by 1.5 times or more due to water absorption. Say. The non-hydrophilic component is one having a 65% RH pumping rate of 10% by weight or less or a water saturated pumping rate of 50% by weight or less in the ASTM D570 test method, or the solubility of water taken into the component. Fifty
It refers to one that is not more than wt%. The solubility of the water in the non-hydrophilic component is preferably 10% by weight or less.

The non-hydrophilic component in the present invention is a silver halide grain, an inorganic matting agent, an oil protect (oil-soluble).
There are couplers, polymer couplers, oligomer couplers, high-boiling organic solvents, oil-soluble polymers for dispersion, anti-foggants, anti-fading agents (or color image stabilizers), anti-color mixing agents, oil-soluble dyes and ultraviolet absorbers. The hydrophilic component in the present invention includes hydrophilic protective colloids which are usually used, such as gelatin, but in addition, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; hydroxyethyl cellulose, carboxymethyl cellulose. , Cellulose derivatives such as cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, polyvinyl pyrazole, etc. There are various kinds of synthetic hydrophilic high molecular substances such as single or copolymers.

Examples of gelatin include lime-processed gelatin, acid-processed gelatin and Bull.Soc.Sci.Phot.Japan.No.16.
, Page 30 (1966), an enzyme-treated gelatin may be used, and a hydrolyzed product or an enzymatically decomposed product of gelatin may also be used. In the present invention, the weight ratio of the non-hydrophilic component to the hydrophilic component in the yellow coupler-containing emulsion layer must be 0.90 or more and 1.30 or less, preferably 0.95 or more and 1.25 or less, and most preferably It is preferably 0.95 or more and 1.20 or less.

Next, the compound represented by the general formula (M-II) will be described. Among the pyrazoloazole couplers, the compound represented by the general formula (M-II) is disclosed in US Pat.
The imidazo [1,2-b] pyrazoles described in 500,630 are preferred, and the pyrazolo [1,5-b] [1,2,4] triazoles described in US Pat. No. 4,540,654 are particularly preferred. In addition, a branched alkyl group as described in JP-A-61-65245 has a pyrazolotriazole ring of 2,3
Alternatively, a pyrazolotriazole coupler directly linked to the 6-position, a pyrazoloazole coupler having an alkoxyphenyl sulfonamide ballast group containing a sulfonamide group in the molecule as described in JP-A-61-65246. It is preferable to use a pyrazolotriazole coupler having an alkoxy group or an aryloxy group at the 6-position as described in European Patent (Publication) Nos. 226,849 and 294,785.
Specific examples of the pyrazoloazole-based coupler represented by the general formula (M-II) are listed below, but the invention is not limited thereto.

[0050]

[Chemical formula 24]

[0051]

[Chemical 25]

[0052]

[Chemical formula 26]

[0053]

[Chemical 27]

[0054]

[Chemical 28]

[0055]

[Chemical 29]

[0056]

[Chemical 30]

The amount of the coupler represented by the general formula (M-II) is usually 0.1 to 1.0 mol, preferably 1 to 1.0 mol per mol of silver halide in the silver halide emulsion layer constituting the photosensitive layer.
0.1 to 0.5 mol is contained.

The pH value of the base paper used for the paper support of the light-sensitive material of the present invention must be 5 or more and 9 or less.
It is more preferably 5.5 or more and 8.5 or less. In the present specification, the pH value of the base paper is a value measured according to the hot water extraction method of JIS-P-8133. The outline of the hot water extraction method of JIS-P-8133 is described below. Approximately 1.0 g of the test piece is weighed out, put it in a 100 ml Erlenmeyer flask, add 20 ml of distilled water, and dip it with a flat stir bar until it becomes evenly moistened to soften it. Next, add 50 ml of distilled water and stir, and attach a condenser to the flask. Then place the flask in a water bath to keep the contents of the flask at 95-100 ° C without boiling water. Shake occasionally at this temperature 1
After heating for a period of time, it is cooled to 20 ° C. ± 5 deg, and the pH value of the extract is measured as it is using a glass electrode pH meter. Details of the above measurement method and the equipment used for the measurement shall comply with the Japanese Industrial Standards of 1963.

The constitution of the paper support used in the present invention and specific means for adjusting the pH value to 5 to 9 will be described below. The base paper used for the paper support is produced by making wood pulp as a main raw material and making paper. As the wood pulp, either softwood pulp or hardwood pulp can be used, but in the present invention, it is preferable to use a large amount of short fiber hardwood pulp. Specifically, of the pulp that makes up the base paper,
It is preferable to use 60% by weight or more of hardwood pulp. If necessary, part of the wood pulp may be replaced with synthetic pulp made of polyethylene, polypropylene or the like, or synthetic fiber made of polyester, polyvinyl alcohol, nylon or the like. The freeness of the pulp used is preferably 150 to 500 cc, more preferably 200 to 400 cc according to CSF regulations. Further, regarding the fiber length after beating, it is preferable that the 24 + 42 mesh residue defined by JIS-P-8207 is 40% by weight or less. In general, a sizing agent is internally added to the base paper, but in the present invention, the pH value of the paper support is 5 to 9
Therefore, epoxidized fatty acid amide, fatty acid anhydride, rosin acid anhydride, alkenyl succinic anhydride,
It is preferable to use a neutral sizing agent such as succinamide, isopropenyl stearate, aziridine compound, and alkyl ketene dimer as the internally added sizing agent. Further, a sizing agent is generally added internally to the base paper, but in the present invention, the pH value of the base paper needs to be 5 to 9, so that a sulfuric acid band (aluminum sulfate) that is usually used as a fixing agent is used. Instead of cationized starch, polyamide polyamine epichlorohydrin, polyacrylamide,
It is preferable to use a neutral or weakly alkaline compound such as a polyacrylamide derivative, or to add a sulfuric acid band and then neutralize with an alkali.

Further, a filler such as calcium carbonate, talc, clay, kaolin, titanium dioxide or urea resin fine particles may be internally added to the base paper for the purpose of improving smoothness. As internal additives other than the above internally added sizing agent, fixing agent and filler, paper strength enhancers such as polyacrylamide, starch and polyvinyl alcohol; reaction products of maleic anhydride copolymer and polyalkylene polyamines; A softening agent such as a quaternary ammonium salt; a colored dye; a fluorescent dye or the like may be added to the base paper if necessary. In principle, these internal additives also have a pH value of the base paper of 5-9.
It is preferable to select and use a drug having a value close to neutrality. Further, it is preferable to use as little acidic or alkaline chemical as possible.

The base paper used for the paper support can be produced by using the raw materials described above and using a Fourdrinier paper machine or a cylinder paper machine. The basis weight of the base paper is 20 to 300 g / m ^2.
Is preferable, and 50 to 200 g / m ² is particularly preferable. The thickness of the base paper is preferably 25 to 350 μm, particularly preferably 40 to 250 μm. The base paper is preferably subjected to a calendering treatment such as an on-machine calender in a paper machine or a super calender after paper making for the purpose of improving smoothness. By the above calendar processing, the density of the base paper is JIS-P-
Preferably to be 0.7 ~1.2 g / m ² at a specified 8118, it is particularly preferable to be 0.85~1.10g / m ^2.

The pH value of the base paper to be produced is adjusted to 5 to 9 by the method for producing the base paper as described above, particularly by selecting the chemicals for internal addition (internal addition sizing agent, fixing agent, etc.) and surface sizing agent. You can In the light-sensitive material of the present invention, the base paper as described above can be used as it is as a paper support. A surface sizing agent may be applied to the surface of the raw paper.
Examples of the surface sizing agent include polyvinyl alcohol, starch, polyacrylamide, gelatin, casein, styrene maleic anhydride copolymer, alkyl ketene dimer, polyurethane, and epoxidized fatty acid amide.

A coating layer may be further provided on one or both surfaces of the above-mentioned base paper (including those coated with a surface sizing agent). There is no particular limitation on the structure of the coating layer,
It preferably comprises a hydrophobic polymer. By providing the coating layer containing the hydrophobic polymer, the water absorption of the paper support is lowered, and the strain of the support which occurs during the coating of the photosensitive layer can be reduced. The hydrophobic polymer may be a homopolymer or a copolymer. Further, in the case of the copolymer, even if it partially has a hydrophilic repeating unit, it may be hydrophobic as a whole. Examples of the hydrophobic polymer include polyethylene, polypropylene, vinylidene chloride, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, styrene-acrylic acid ester copolymer, and styrene-methacrylate-acrylic acid ester copolymer. You can

A pigment may be added to the coating layer for the purpose of improving resolution. As the pigment, a known pigment used for coated paper can be used. Examples of pigments include inorganic pigments such as titanium dioxide, barium sulfate, talc, clay, kaolin, calcined kaolin, aluminum hydroxide, amorphous silica, crystalline silica and synthetic alumina silica;
And organic pigments such as polystyrene resin, acrylic resin and urea formalin resin. The amount of the pigment added is suitably 5 to 60% by weight in the hydrophobic polymer, preferably 8 to 30% by weight, more preferably 14 to 30% by weight. As a method for providing the coating layer, an extrusion coating method, a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a doctor coating method, a gravure coating method, or the like can be used. For the purpose of improving the smoothness of the paper support, it is preferable to carry out a calender treatment such as a gloss calender or a super calender during or after coating.

Next, the silver halide emulsion of the present invention will be described in detail. The silver halide emulsion of the present invention is preferably a so-called high silver chloride emulsion having a silver chloride content of 90 mol% or more,
Further, it is preferable that at least one of the silver halide grains has a silver bromide-rich region in the vicinity of the apex thereof, and the average silver bromide content on the grain surface is 15 mol% or less. Here, the "vicinity of the apex" is preferably about 1/3 (more preferably 1/5) of the diameter of a circle having the same area as the area of the projected cubic or cubic crystal-like normal crystal silver chlorobromide grains. It is within the area of a square whose length is one side and whose vertex is a cube or the intersection of the edges of normal crystal grains regarded as a cube. The content ratio of silver chlorobromide grains having a silver bromide-rich region to all silver halide grains contained in the same emulsion layer is preferably 70 mol% or more.

The host silver halide crystals used to make the emulsions of the present invention are cubic or tetradecahedral crystal grains having substantially (100) faces (these have rounded corners and higher faces). The halogen composition is silver chlorobromide or silver chloride containing silver iodide in an amount of 2 mol% or less or having a silver chloride content of 90 mol% or more, and preferably 95%. A silver halide or pure silver chloride crystal containing at least 99 mol% of silver chloride, particularly preferably at least 99 mol%. The average grain size of the host silver halide grains is preferably 0.2 μm to 2 μm, and the distribution state thereof is preferably monodisperse. The monodisperse emulsion relating to the present invention means
Coefficient of variation (S / r) for grain size of silver halide grains
Is an emulsion having a grain size distribution of 0.25 or less. Where r
Is the average particle size, and S is the standard deviation for the particle size. That is, when the grain size of each emulsion grain is ri and the number is ni, the average grain size r is defined by r = (Σni · ri) / (Σni), and its standard deviation S is S = [{ Σ (r-ri) ² · ni} / {Σni}] ^1/2 is defined.

The grain size in the present invention means a silver halide emulsion as described in "The Theory of the Photographic Pr" by TH Jams et al.
"Ocess", 3rd edition, pages 36-39, published by Macmillan (1966)
(Year), which is the diameter equivalent to the projected area corresponding to the area projected when microscopically photographed by a method well known in the art (usually electron microscope photographing) as described in (1). Here, the diameter equivalent to the projected area of a silver halide grain is defined by the diameter of a circle having an area equal to the projected area of a silver halide grain as described in the above-mentioned book. Therefore, the shape of silver halide grains is not spherical (eg, cubic, octahedral, 14
The average particle size r and its deviation S can be obtained as described above even in the case of a face, a flat plate, a potato, etc. The coefficient of variation with respect to the particle size of the silver halide grains is 0.25 or less, preferably 0.20 or less, more preferably 0.15
Hereafter, it is most preferably 0.10.

Next, bromide ions or high silver bromide fine particles are supplied to the host silver halide grains to deposit a new silver bromide phase rich in silver bromide on the surface of the host silver halide grains. .. This process proceeds by a so-called "halogen conversion" process due to the exchange reaction of the bromide ion with the halogen ion on the surface of the host silver halide grain. The other process using high silver bromide fine particles proceeds due to the reaction between the host silver halide grains and the high silver bromide grains to form a crystal with a more stable composition, and it can be considered separately from the conversion reaction. Is. Despite these two different types of reactions, the effect of selecting the vicinity of the apex of the host grain as the formation site of a new silver bromide-rich phase can be similarly obtained in both reactions.

In order to more effectively achieve the purpose of obtaining a very high sensitivity by concentrating latent images or development nuclei, a compound (CR which suppresses or prevents the initiation of halogen conversion)
Compound) can be used. A CR compound is a substance that functions to retard or completely prevent the initiation of halogen conversion and recrystallization by selectively adsorbing to a specific crystal plane as compared with the case where the compound is not adsorbed. , Especially in the present invention (100)
It is a substance that is mainly (selectively) adsorbed on the surface and acts to suppress the initiation of conversion and recrystallization on the (100) surface. Examples of the CR compound used in the present invention include cyanine dyes, merocyanine dyes, and mercaptoazoles (specific examples thereof include general formulas (XXI) and (XXII) described in detail in EP 0273430).
(Compounds represented by (XXIII)), nucleic acid degradation products (for example, products of deoxyribonucleic acid and ribonucleic acid in the course of degradation, adenine, guanine, uracil, cytosyl, thymine, etc.)
Can be mentioned. In particular, the following general formula [Is],
The compound represented by [IIs] or IIIs is preferable.

[0070]

[Chemical 31]

In the formula, Z ₁₀₁ and Z ₁₀₂ each represent an atomic group necessary for forming a heterocyclic nucleus. As a heterocyclic nucleus,
A 5- to 6-membered ring nucleus containing a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom or a tellurium atom as a hetero atom (a condensed ring may be further bound to these rings, or a substituent is further bound thereto). May be used) is preferred. Specific examples of the heterocyclic nucleus, thiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, selenazole nucleus, oxazole nucleus, benzoxazole nucleus, naphthoxazole nucleus,
Imidazole nucleus, naphthoimidazole nucleus, 4-quinoline nucleus, pyrroline nucleus, pyridine nucleus, tetrazole nucleus, indolenine nucleus, benzindolenine nucleus, indole nucleus, tellurazole nucleus, benzoterrazole nucleus, naphthoterrazole nucleus, etc. it can.

R ₁₀₁ and R ₁₀₂ each represent an alkyl group, an alkenyl group, an alkynyl group or an aralkyl group.
Each of these groups and the groups described below is used in the meaning including the substituted form. For example, when an alkyl group is taken as an example, it includes an unsubstituted alkyl group and a substituted alkyl group, and these groups may be linear, branched or cyclic. The alkyl group preferably has 1 to 8 carbon atoms. Specific examples of the substituent of the substituted alkyl group include a halogen atom (chlorine, bromine, fluorine, etc.), a cyano group, an alkoxy group,
Examples thereof include a substituted or unsubstituted amino group, a carboxylic acid group, a sulfonic acid group and a hydroxyl group, and one or more of these may be substituted together. A specific example of the alkenyl group is a vinylmethyl group. Specific examples of the aralkyl group include a benzyl group and a phenethyl group.

M ₁₀₁ represents an integer of 0, 1, 2 or 3. When m ₁₀₁ represents 1, R ₁₀₃ represents a hydrogen atom, a lower alkyl group, an aralkyl group or an aryl group. Specific examples of the aryl group include a substituted or unsubstituted phenyl group. R ₁₀₄ represents a hydrogen atom.
When m ₁₀₁ represents 2 or 3, R ₁₀₃ represents a hydrogen atom, R ₁₀₄ represents a hydrogen atom, a lower alkyl group or an aralkyl group and may be linked with R ₁₀₂ to form a 5-membered to 6-membered ring. it can. When m ₁₀₁ represents 2 or 3 and R ₁₀₄ represents a hydrogen atom, R ₁₀₃ may _combine with another R ₁₀₃ to form a hydrocarbon ring or a heterocycle. These rings are 5
A ~ 6 membered ring is preferred. j ₁₀₁ and k ₁₀₁ represent 0 or 1, X ₁₀₁ ⁻ represents an acid anion, and n ₁₀₁ represents 0 or 1.

[0074]

[Chemical 32]

In the formula, Z ₂₀₁ and Z ₂₀₂ are the aforementioned Z ₁₀₁ or Z.
Synonymous with ₁₀₂ . R ₂₀₁ and R ₂₀₂ are R ₁₀₁ or R
It has the same meaning as ₁₀₂ , and R ₂₀₃ represents an alkyl, alkenyl, alkynyl or aryl group (such as a substituted or unsubstituted phenyl group). m ₂₀₁ represents 0, 1 or 2. R
₂₀₄ represents a hydrogen atom, a lower alkyl group or an aryl group, and when m ₂₀₁ represents 2, R ₂₀₄ and R ₂₀₄ may combine to form a hydrocarbon ring or a heterocycle. These rings are preferably 5- or 6-membered rings. Q ₂₀₁ is a sulfur atom, an oxygen atom,
It represents a selenium atom or> N-R ₂₀₅ , and R ₂₀₅ has the same _meaning as R ₂₀₃ . _{j 201, k 201, X 201} - and n ₂₀₁ is j _101, k _101, X _101, respectively ^- the same meanings as and n _101.

[0076]

[Chemical 33]

In the formula, Z ₃₀₁ represents an atomic group necessary for forming a heterocycle. Examples of the heterocyclic ring include those mentioned for Z ₁₀₁ and Z ₁₀₂ , and other specific examples thereof include thiazolidine, thiazoline, benzothiazoline, naphthothiazolin, selenazolidine, selenazoline, benzoselenazoline, naphthoselenazoline, benzoxazoline, naphthoxazoline, Cores such as dihydropyridine, benzimidazoline and naphthimidazoline can be mentioned.
Q ₃₀₁ is synonymous with Q ₂₀₁ . R ₃₀₁ is R ₁₀₁ or R
₁₀₂ and R ₃₀₂ have the same _meaning as R ₂₀₃ . m ₃₀₁ is m ₂₀₁
Is synonymous with. R ₃₀₃ has the same _meaning as R _204, and when m ₃₀₁ represents 2 or 3, R ₃₀₃ and another R ₃₀₃ may combine to form a hydrocarbon ring or a heterocycle. j ₃₀₁ is j ₁₀₁
Is synonymous with.

In addition to increasing the selectivity of the initial formation site of the new silver bromide-rich phase over the host grains, the CR compound also causes the newly formed new phase to recrystallize with the surface of the host grains. It is possible to prevent the reaction that causes the formation of a uniform new layer on the entire surface of the host grain by repeating the crystallization, and to grow epitaxially in the vicinity of the apex of the host grain. To form and retain. Then, by forming a new phase limited to this place, a very high sensitivity is achieved. This increase in sensitivity also tends to give pressure desensitization. Pressure desensitization is a phenomenon in which the sensitivity of a photosensitive material decreases when pressure is applied before exposure, but the content of silver bromide in a new phase richer in silver bromide than the host grains increases. The silver bromide content of this phase is preferably higher than that of the host grains and 90 mol% or less. It is more preferably 60 mol% or less.

The silver halide grains in the present invention contain silver chloride in an average value of 90 mol% or more in the same emulsion,
A new phase that is richer in silver bromide than the host particles has grown epitaxially near the apex of the host particles, and there is a transition region with a gradual halogen composition between the new phase and the host particles. There is. The structure of such particles is observed by various analytical methods. First, by observation with an electron microscope, it is observed that a new phase is bonded near the apex of the particle due to the morphological change of the particle.
Further, the halogen composition of the host particle and a new phase can be obtained by the X-ray diffraction method. For the average halogen composition of the surface, see XPS (X-ray Photoelectron Spectros
copy) method, for example, using an ESCA750 spectroscope manufactured by Shimadzu du Pont. About this measuring method, please refer to Someno / Yasumorii "Surface Analysis" Kodansha (Published in 1977).
It is described in. By knowing the halogen composition of the host grain and the new phase by the X-ray diffraction method, and by knowing the average halogen composition of the surface by the XPS method, the proportion of the new phase rich in silver bromide from the host grain on the entire surface can be determined. It can be roughly estimated whether it occupies. Further, in order to identify the existence position of a new phase richer in silver bromide than the host grains and to measure how much it occupies in the vicinity of the apex of the grains, the method by observation with the electron microscope is used. Besides, ED
It can be measured by an X (Energy Dispersive X-ray analysis) method using an EDX spectrometer equipped in a transmission electron microscope. This measuring method is specifically described in "Electron beam microanalysis" by Keiyoshi Soejima, Nikkan Kogyo Shimbun (issued in 1987). The new phase in the present invention is preferably localized near the apex of the host grain, and the average halogen composition of the surface is preferably 15 mol% or less of silver bromide, more preferably 10 mol% or less. .. The increase in the average silver bromide content on the surface means that the degree of localization of the new phase near the apex decreases, and at the same time, the sensitivity decreases. It has been observed by an electron microscope that, in the preferred production method of the present invention, the new phase formed is in the form of being epitaxially bonded and grown at the corner portion of the host grain.

The preferable grain size of the fine grain high silver bromide emulsion used in the present invention may vary depending on the size of the host grain and the halogen composition, but a grain size of 0.3 μm or less is usually used. It is more preferably 0.1 μm or less. It is essential that the halogen composition of the fine grain high silver bromide emulsion has a higher silver bromide content than the host grains, and a bromide concentration of 50 mol% or more is preferable. More preferably 70 mol%
It is desired to contain the above bromide. The fine grain high silver bromide emulsion may contain iodide if necessary. It is also possible to include ions or compounds of heavy metals such as iridium, rhodium and platinum. Fine grain high silver bromide emulsions have a silver content of 50% relative to the host silver halide.
It is mixed in the range of 0.1%. More preferably 0.2 to 20
%, Particularly preferably 0.2 to 8%. The mixing temperature can be freely selected between 30 ° C and 80 ° C. The silver chlorobromide emulsion of the present invention has a concentrated latent image or development center, achieves extremely high sensitivity, and can suppress fog without impairing rapid developability. Further, there are advantages that the gradation is hard and the pressure desensitization is small.

The CR compound in the present invention can be selected from sensitizing dyes. Especially useful C for (100) plane
The R compound has the general formula Is, IIs or III described above.
Since it can be selected from the compounds represented by s and can function as a sensitizing dye, it is also useful for increasing the spectral sensitivity. In particular, partial recrystallization of the surface can also increase the stability of spectral sensitivity. Further, it may be used in combination with other sensitizing dyes for the purpose of further sensitization and stabilization, and may also be used in combination with a supersensitizer. For example, a substituted aminostilbenzene compound having a nitrogen-containing heterocyclic nucleus group (for example, JP-A-62-174).
Compounds of the general formula (I) described in Japanese Patent No. 738, particularly specific compound examples (I-1) to (I-17), US Pat.
2,933,390 and 3,635,721), aromatic organic acid formaldehyde condensates (eg, US Pat. No. 3,743,743).
No. 3,510), cadmium salt, azaindene compound and the like. U.S. Pat.No. 3,615,613,
The combinations described in Nos. 3,615,641, 3,617,295, and 3,635,721 are particularly useful. General formulas Is and IIs
And specific examples of the CR compound represented by IIIs include CR-1 to 55 described in the above-mentioned European Patent EP 0273430. Various polyvalent metal ion impurities can be introduced into the high silver chloride grains having a silver bromide-rich region used in the present invention in the process of emulsion grain formation or physical ripening. Examples of the compound to be used include salts of cadmium, zinc, lead, copper, thallium, etc., or salts or complex salts of group I elements such as iron, ruthenium, rhodium, palladium and platinum. Particularly, the above Group VIII elements can be preferably used. The polyvalent metal ion most preferably used in the present invention is an iridium compound of 10 ^-8 to 1 per mol of silver.
It is preferable that 0 ⁻⁵ mol and further 10 ⁻⁹ to 10 ⁻⁴ mol of an iron compound are contained in order to further enhance the effects of the present invention.

In the present invention, the use of the epoxy compound having a group represented by the general formula (AO) exerted a remarkable effect in improving the fastness of a yellow color image and improving the color reproducibility. However, there arises a problem that the sensitization is lowered or the fog is increased during long-term storage of the photographic material. When various possible factors were examined to investigate the cause, the weight ratio of the non-hydrophilic component such as coupler and oil contained in the yellow color-forming emulsion layer to the hydrophilic component such as gelatin was determined by the present invention. A clear improvement effect was obtained by setting the value within the range. Further, by setting the pH of the base paper of the paper support to 5 to 9 by the method according to the present invention, the above-mentioned improvement effect is remarkably increased, and it is possible to reach the performance which is practically satisfactory for the above problems. It was Each high-silver chloride emulsion having a silver chloride content of 90 mol% or more, particularly an emulsion having a silver bromide-rich region in the vicinity of the apex of a grain (referred to as apex-type emulsion) is preferably used in the present invention. It has been found that, when applied to layers, the improved effect of the invention is even better. It is preferable that this emulsion is further applied to another magenta or cyan coupler-containing emulsion layer in order to improve rapid processing property or color reproducibility.

As the silver halide used in the present invention, silver chloride, silver bromide, silver (iodo) chlorobromide, silver iodobromide and the like can be used. Especially, for the purpose of rapid processing, iodide is used. It is preferable to use a silver chlorobromide or silver chloride emulsion having a silver chloride content substantially free of silver of 90 mol% or more, further 95% or more, and particularly 98% or more.

In the light-sensitive material according to the present invention, for the purpose of improving the sharpness of an image, a hydrophilic colloid layer, a dye which can be decolorized by a treatment (see pages 27 to 76 of European Patent EP 0,337,490A2) is used. Of these, oxonol dyes) are added so that the optical reflection density at 680 nm of the light-sensitive material is 0.70 or more, or 2 to 2 is added to the water-resistant resin layer of the support.
It is preferable to contain 12% by weight or more (more preferably 14% by weight or more) of titanium oxide surface-treated with a tetravalent alcohol (eg, trimethylolethane).

High boiling organic solvents for photographic additives such as cyan, magenta and yellow couplers which can be used in the present invention are water-immiscible compounds having a melting point of 100 ° C. or lower and a boiling point of 140 ° C. or higher, and are good couplers. Any solvent can be used. 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 170 ° C or higher.

Details of these high-boiling point 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 (see, for example, US Pat.
No. 4,203,716) or dissolved with a water-insoluble polymer and an organic solvent-soluble polymer, and emulsified and dispersed in a hydrophilic colloid aqueous solution.

The homopolymers or copolymers described on pages 12 to 30 of US Pat. No. 4,857,449 and WO 88/00723 are preferably used, more preferably a methacrylate-based or acrylamide-based polymer, particularly 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) and // which chemically bond with the aromatic amine developing agent remaining after the color development processing to form a chemically inactive and substantially colorless compound.
Alternatively, the compound (G) which chemically bonds with an oxidized product of an aromatic amine color developing agent remaining after the color developing treatment to form a chemically inactive and substantially colorless compound is used simultaneously or alone. Are preferable, for example, in order to prevent stain generation and other side effects due to the formation of a coloring dye by the reaction of the coupler with the color developing agent remaining in the film or the oxidant thereof during storage after processing.

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 a support used in the light-sensitive material of the present invention, a white polyester support for display or a layer containing a white pigment 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. Especially, the transmission density of the support is 0.35 ~ so that the display can be viewed with both reflected light and transmitted light.
It is preferable to set it in the range of 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 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 exposed light-sensitive material may be subjected to a conventional black-and-white or color development processing, but in the case of a color light-sensitive material, it is preferable to perform bleach-fix processing after color development for the purpose of rapid processing. Particularly when the above high silver chloride emulsion is used, the pH of the bleach-fixing solution is preferably about 6.5 or less, more preferably about 6 or less for the purpose of promoting desilvering.

Silver halide emulsions and other materials (additives and the like) and photographic constituent layers (layer arrangement and the like) applied to the light-sensitive material according to the present invention, and processing methods applied to process the light-sensitive material. The following patent publications, particularly European Patent EP 0,355,660A2 (Japanese Patent Laid-Open No. 2-1395
Those described in No. 44) are preferably used.

[0097]

[Table 1]

[0098]

[Table 2]

[0099]

[Table 3]

[0100]

[Table 4]

Further, as a cyan coupler, JP-A-2-33 is used.
In addition to the diphenylimidazole type cyan coupler described in No. 144, a 3-hydroxypyridine type cyan coupler described in European Patent EP 0,333,185A2 (of which 4-equivalent coupler of the coupler (42) listed as a specific example is a chlorine leaving group). Those having 2 equivalents, couplers (6) and (9) are particularly preferable), and cyclic active methylene cyan couplers described in JP-A-64-32260 (the couplers listed as specific examples). 3,8,34) are particularly preferred).

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. The method described in the section is preferably applied.

[0103]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited to these. (Preparation of emulsion) 3.3 g of sodium chloride was added to a 3% aqueous solution of lime-processed gelatin, and 3.2 ml of N, N'-dimethylimidazolidine-2-thione (1% aqueous solution) was added. An aqueous solution containing 0.2 mol of silver nitrate and an aqueous solution containing 0.15 mol of sodium chloride and 0.05 mol of potassium bromide were added and mixed at 66 ° C. with vigorous stirring. Subsequently, an aqueous solution containing 0.80 mol of silver nitrate and an aqueous solution containing 0.60 mol of sodium chloride and 0.20 mol of potassium bromide were added and mixed at 66 ° C. with vigorous stirring. After the addition of the aqueous solution of silver nitrate and the aqueous solution of alkali halide was completed, the temperature was lowered to 40 ° C. for desalting and washing with water. Further lime processed gelatin 90.0g
Was added to adjust the pAg to 7.2 with sodium chloride, and then 60.0 mg of the blue-sensitive sensitizing dye shown in Table 5 and 4.0 mg of triethylthiourea were added to optimally perform chemical sensitization at 50 ° C. The silver chlorobromide emulsion thus obtained was designated as Emulsion A.

Next, 3.3 g of sodium chloride was added to a 3% aqueous solution of lime-processed gelatin, and 3.2 ml of N, N'-dimethylimidazolidine-2-thione (1% aqueous solution) was added.
While stirring vigorously with this solution, an aqueous solution containing 0.2 mol of silver nitrate and an aqueous solution containing 0.2 mol of sodium chloride were used.
The mixture was added and mixed at 0 ° C. Subsequently, an aqueous solution containing 0.78 mol of silver nitrate and an aqueous solution containing 0.78 mol of sodium chloride were added and mixed at 66 ° C. with vigorous stirring. After the addition of the aqueous solution of silver nitrate and the aqueous solution of alkali halide was completed, the temperature was lowered to 40 ° C. for desalting and washing with water. Further lime-processed gelatin
After 90.0 g was added and the pAg was adjusted to 7.2 with sodium chloride, 60.0 mg of the same blue-sensitizing dye as in Emulsion A and 4.0 mg of triethylthiourea were added and optimal chemical sensitization was carried out at 50 ° C. The silver chloride emulsion thus obtained was designated as Emulsion B.

Next, 3.3 g of sodium chloride was added to a 3% aqueous solution of lime-processed gelatin, and 3.2 ml of N, N'-dimethylimidazolidine-2-thione (1% aqueous solution) was added.
While stirring vigorously with this solution, an aqueous solution containing 0.2 mol of silver nitrate and an aqueous solution containing 0.2 mol of sodium chloride were used.
The mixture was added and mixed at 0 ° C. Subsequently, an aqueous solution containing 0.78 mol of silver nitrate and an aqueous solution containing 0.78 mol of sodium chloride were added and mixed at 66 ° C. with vigorous stirring. One minute after the addition of the aqueous silver nitrate solution and the aqueous alkali halide solution was completed, 60.0 mg of the same blue-sensitizing dye as in Emulsion A was added. After keeping at 56 ° C for 10 minutes, the temperature was lowered to 40 ° C, and desalting and washing were performed. Further, 90.0 g of lime-processed gelatin was added and dissolved at 50 ° C., and then a silver chlorobromide fine grain emulsion (silver bromide content: 75 mol%, silver amount:
0.02 mol, average particle size 0.05 μm) and added for about 20 minutes, then adjust the pAg to 7.2 with sodium chloride,
Optimal chemical sensitization was performed at 50 ° C by adding 4.0 mg of triethylthiourea. The silver chlorobromide emulsion (silver bromide content: 1.5 mol%) thus obtained was designated as emulsion C.

Next, 3.3 g of sodium chloride was added to a 3% aqueous solution of lime-processed gelatin, and 3.2 ml of N, N'-dimethylimidazolidine-2-thione (1% aqueous solution) was added.
While stirring vigorously with this solution, an aqueous solution containing 0.2 mol of silver nitrate and an aqueous solution containing 0.2 mol of sodium chloride were used.
The mixture was added and mixed at 0 ° C. Then, while vigorously stirring an aqueous solution containing 0.78 mol of silver nitrate and an aqueous solution containing 0.78 mol of sodium chloride and 4.2 mg of potassium ferrocyanide at 66 ° C.
Was added and mixed. One minute after the addition of the aqueous silver nitrate solution and the aqueous alkali halide solution was completed, 60.0 mg of the same blue-sensitizing dye as in Emulsion A was added. After keeping at 56 ℃ for 10 minutes, 40 ℃
The temperature was lowered to desalination and washing with water. After further adding 90.0 g of lime-processed gelatin and dissolving at 50 ° C., a silver chlorobromide fine grain emulsion (silver bromide content 75 mol%, silver amount 0.02 mol, average grain size 0.05 μm, iridium ion hexachloroiridium ( VI) equivalent to potassium acid, containing 0.91 mg)
After 20 minutes, the pAg was adjusted to 7.2 with sodium chloride, 4.0 mg of triethylthiourea was added, and optimal chemical sensitization was performed at 50 ° C. The thus obtained silver chlorobromide emulsion (silver bromide content: 1.5 mol%) was designated as Emulsion D.

With respect to the silver halide emulsions A to D thus obtained, the grain shape, grain size and grain size distribution were determined from electron micrographs. All of these silver halide grains are cubic and have a grain size of 0.
The 72 μm coefficient of variation was 0.08. The particle size is represented by the average value of the diameter of the circle equivalent to the projected area of the particle, and the particle size distribution is the standard deviation of the particle size divided by the average particle size. The halogen composition of the emulsion grains was then determined by measuring the X-ray diffraction from the silver halide crystals. The diffraction angle from the (200) plane was measured in detail using a monochromatic CuKα ray as the radiation source. A diffraction line from a crystal having a uniform halogen composition gives a single peak, whereas a diffraction line from a crystal having a localized phase having a different composition gives a plurality of peaks corresponding to those compositions. The halogen composition of the silver halide constituting the crystal can be determined by calculating the lattice constant from the diffraction angle of the measured peak. The average silver bromide content on the surface of emulsion grains was measured by the XPS method. As a result, the halogen composition of Emulsion A was a uniform grain with a silver chloride content of 75% and the surface silver bromide content was 25%.
Met. The halogen composition of emulsion B was 100% uniform grains of AgCl, and the silver bromide content on the surface was 0%. In addition, in both emulsions C and D, a broad diffraction pattern in which the center was at 30% silver bromide and the hem was stretched to around 40% silver bromide in addition to the main peak at 100% AgCl could be observed. The average silver bromide content on the surface was 3%.

(Preparation of paper support) 70 parts LBKP and LBS
P30 parts of wood pulp using a disc refiner C
Beated to SF290 cc and used as a neutral sizing agent for alkyl ketene dimer (Dick Hercules Co., Ltd., Accorpel 12
) 1.0 part, anionic polyacrylamide (Arakawa Chemical Industry Polytron 194-7) 1.0 part, cationic polyacrylamide (Arakawa Chemical Industry Polytron 705) 0.5
And 0.3 parts of polyamide polyamine epichlorohydrin (Kymen 557, manufactured by Dick Hercules) were added at an absolutely dry weight ratio to the pulp. Then, using a Fourdrinier paper machine, paper was made into a base paper having a basis weight of 170 g / m ² and a thickness of 165 μm. The base paper prepared as described above is referred to as (A). The pH value of the base paper (A) was 6.4 when measured by the hot water extraction method of JIS-P-8133. 0.6 parts of epoxidized fatty acid amide (manufactured by Modern Chemical Industry Co., Ltd., NS-715) as a neutral sizing agent on the same beaten pulp as the base paper (A), anionic polyacrylamide (Polystron 194-7 manufactured by Arakawa Chemical Industry Co., Ltd.)
) 1.2 parts, aluminum sulfate 1.0 part, NaOH 0.9
Parts and 1.0 parts of cationized starch were added in an absolutely dry weight ratio to the pulp. Then, in the same manner as the base paper (A), a base paper (B) having a basis weight of 170 g / m ² and a thickness of 165 μm was produced. The pH value of the base paper (B) was 7.3. Then, using the same beaten pulp as that of the base paper (A), 1.0 part of sodium stearate, 1.0 part of anionic polyacrylamide (manufactured by Arakawa Chemical Industry Co., Ltd., Polystron 194-7), and 1.5 parts of aluminum sulfate were all dried to dry weight with respect to the pulp. Added in ratio. Then, the same as the base paper (A), the basis weight is 170 g /
A base paper of m ² and a thickness of 166 μm was formed into a base paper (C). The pH value by the hot water extraction method was 3.8. A base paper (D) was prepared in the same manner as the base paper (C) except that 0.5 part of sodium aluminate was added after the addition of aluminum sulfate to the base paper (C). The pH value by the hot water extraction method was 4.7.

Polyethylene having a density of 0.94 / cm ² containing 10% by weight of titanium oxide was extruded and coated on the surface (the surface on which the light-sensitive material is applied) of each of the base papers (A) to (D) by a thickness of 35 μm, Paper supports (A) to (D) were prepared.

(Preparation of Light-Sensitive Material) After the corona discharge treatment was applied to the surface of the paper support (A) prepared as described above, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and various photographic constitutions were prepared. The layers were applied to prepare a multilayer color photographic paper having the layer constitution shown below. The coating liquid was prepared as follows. Preparation of coating liquid for first layer Yellow coupler (ExY) 153.0 g, color image stabilizer (Cpd-1) 15.
0 g, 7.5 g of color image stabilizer (Cpd-2), 25.0 g of solvent (Solv-2),
Dissolved in 25.0 g of solvent (Solv-2) and 180 cc of ethyl acetate,
Add this solution to 10% sodium dodecylbenzene sulfonate.
1000% 10% gelatin aqueous solution containing 60cc and citric acid 10g
to give an emulsified dispersion A. On the other hand, the silver chlorobromide emulsion (A) was prepared, mixed and dissolved with this emulsified dispersion A, and a coating solution for the first layer was prepared so as to have the following composition.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Further, Cpd-15 and Cpd-16 were added to each layer so that the total amounts were 25.0 mg / m ² and 50.0 mg / m ² , respectively. The following spectral sensitizing dyes were used in each photosensitive emulsion layer.

[0112]

[Table 5]

[0113]

[Table 6]

[0114]

[Table 7]

1- (5-methylureidophenyl) -5-mercaptotetrazole was added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer in an amount of 8.5 × 10 ^-5 mol per mol of silver halide. , 7.7 × 10 ^-4 mol and 2.5 × 10 ^-4 mol were added. Also, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer,
4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added in an amount of 1 × 10 ^-4 mol and 2 mol, respectively, per mol of silver halide.
× 10 ^-4 mol was added. The following dyes (the amount in parentheses represents the coating amount) were added to the emulsion layer to prevent irradiation.

[0116]

[Chemical 34]

(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.

[0118]

[Table 8]

[0119]

[Table 9]

[0120]

[Table 10]

[0121]

[Table 11]

[0122]

[Chemical 35]

[0123]

[Chemical 36]

[0124]

[Chemical 37]

[0125]

[Chemical 38]

[0126]

[Chemical Formula 39]

[0127]

[Chemical 40]

[0128]

[Chemical 41]

Based on the above layer structure, the emulsion of the first layer (blue-sensitive emulsion layer), the epoxy compound, the non-hydrophilic component / hydrophilic component ratio, and the magenta coupler of the third layer (green-sensitive emulsion layer) were used. Samples 101 to 120 changed as shown in Table 12
Was produced.

[0130]

[Table 12]

Comparative compounds ExA and ExM in Table 12
Is as follows.

[0132]

[Chemical 42]

A sensitometer (FWH type, manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200 ° K) was used for each sample, and a three-color separation filter for sensitometry (SP-1, SP-2, manufactured by the same company).
The gradation exposure of SP-3) was applied. The exposure at this time was performed so that the exposure amount was 250 CMS with the exposure time of 0.1 seconds. The exposed sample was subjected to continuous processing (running test) using a paper processor using a liquid having the following processing steps and processing compositions until the tank was replenished with twice the tank capacity for color development.

[0134]

[Table 13]

The composition of each processing liquid is as follows.

[0136]

[Table 14]

[0137]

[Table 15]

The reflection density of each color of B, G, and R was measured for the samples which had been treated, and their characteristic curves were obtained. From this characteristic curve, the logarithm of the reciprocal of the exposure amount at which the density of the minimum density (Dmin) +0.5 is obtained, is taken as the sensitivity, and is shown as the difference from each sample with respect to the sensitivity of the sample 101 for the blue sensitive layer as a reference. .. A + value means a high feeling and a − value means a low feeling. In addition, using a sample obtained by separately performing the above treatment,
The sample was stored for 6 months under the dark condition of 70 ° C and RH, and the density decrease ΔDB from the initial density DB = 2.0 of the blue filter exposed area (yellow density) and the change of the green filter density ΔDB at DB = 2.0. (Amount of magenta color mixture in yellow) was measured. In addition, a color checker (manufactured by Macbeth Co.) was printed on each sample by matching the color tone of the gray portion from a negative film photographed, and the color reproducibility in each hue was sensory evaluated. The vivid ones were marked with O, the clear ones were marked with Δ, and the most vivid ones were marked with ◎. In addition, the long-term raw storability of the prepared sample before exposure processing was
The change in sensitivity after 3 months under the condition of storage at 55 ° C. and 55 ° C. is shown by the same sensitivity value as described above. The results are summarized in Table 16.

[0139]

[Table 16]

According to these results, by using the epoxy compound of the present invention, the fastness of the yellow color image is enhanced and, at the same time, the magenta color mixture in the yellow image is reduced, and the present invention is excellent in color image storability and color reproducibility. It can be seen that the sample of 1 is excellent. However, comparative sample 1 using an acidic paper support
As can be seen from Nos. 06 to 109, the change in sensitivity after long-term storage of the raw sample is considerably inferior. In this respect, Samples 110, 112 to 114 and 116 to 120, which simultaneously combined the neutral paper support and the non-hydrophilic component ratio according to the present invention, unexpectedly solved these problems at once. Particularly, the silver chloride content is 90 mol% or more and the peak
Samples 117 to 1 using development type high silver chloride emulsions C and D
No. 20 had a large improvement in long-term raw storage stability, and was the most excellent in color reproducibility after processing.

[0141]

INDUSTRIAL APPLICABILITY The silver halide multilayer color photographic light-sensitive material of the present invention forms a dye image having excellent color image fastness and long-term storage after processing and excellent color reproducibility. Also,
It is possible to provide a silver halide color photographic light-sensitive material in which long-term storability of a raw sample is further improved even before processing.

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[Procedure amendment]

[Submission date] November 5, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 1

[Correction method] Change

[Correction content]

[Chemical 1] In the above general formula (AO), R ₁ , R ₂ , R ₃ , R ₄
R ₅ and R ₅ may be the same or different and each represents a hydrogen atom, an alkyl group or an aryl group. R represents a substituent, n represents the integer of 0-4. -Y- represents a divalent linking group. -X- is -O-, -S- or -N (R ')-
Represents. R ′ represents a hydrogen atom, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, an aryl group, a heterocyclic group or —C (R ₆ ) (R ₇ ) (R ₈ ). Where R
₆ , R ₇ and R ₈ may be the same or different and each represents an alkyl group or a group represented by general formula (AO-1) shown below. R ₆ and R ₇ further represent a hydrogen atom.

[Chemical 2] When n is 2 to 4, plural Rs may be the same or different. Further, any two of R _{1 to} R ₅ , R ′ and R or two Rs may be bonded to each other to form a 5 to 7 membered ring. However, when X is -S-, the total number of carbon atoms of the compound is 1
It is 5 or more. X is -O- and -Y- is-.
When SO ₂ — or phenylene, n is an integer of 1 to 4 or at least one of R ₁ to R ₅ is an alkyl group or an aryl group. When X is —O— and Y is —O—CO ₂ —, the total carbon number of R _{1 to} R ₅ and R is 10 or more.

[Chemical 3] In the formula, R ₁₀ represents a hydrogen atom or a substituent. Y ₄ represents a hydrogen atom or a leaving group. Za, Zb and Zc represent methine, substituted methine, = N- or -NH-, and Za-
One of the Zb bond and the Zb-Zc bond is a double bond,
The other is a single bond. When the Zb-Zc bond is a carbon-carbon double bond, it includes the case where it is part of an aromatic ring.
When R ₁₀ or Y ₄ forms a dimer or higher multimer,
In addition, when Za, Zb or Zc is a substituted methine, it includes the case where the substituted methine forms a dimer or higher multimer.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction content]

When n is 2 to 4, a plurality of R's may be the same or different. Any one of R _{1 to} R ₅
, R ′ and R, or two Rs may combine with each other to form a 5- to 7-membered ring. However, when X is -S-, the total number of carbon atoms of the compound is 15 or more. X is -O-,
And -Y- is -SO ₂ - when is or phenylene,
n is an integer of 1 to 4, or at least one of R ₁ to R ₅ is an alkyl group or an aryl group. X
There -O-, and and Y is -O-CO ₂ - when is, R
The total number of carbon atoms of _{1 to} R ₅ and R is 10 or more.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0018

[Correction method] Change

[Correction content]

R ₁ , R ₂ and R ₃ in the general formula (AO-1) represent the groups defined in the general formula (AO). Further, any two of R _{1 to} R ₅ , R ′ and R or two R
May combine with each other to form a 5- to 7-membered ring. However, when X is -S-, the total number of carbon atoms of the compound is 15 or more. The X is -O-, and and -Y- is -SO ₂
-Or phenylene, n is an integer of 1 to 4, or at least one of R _{1 to} R ₅ is an alkyl group or an aryl group. X is -O- and Y is -O
When it is —CO ₂ —, the total carbon number of R _{1 to} R ₅ and R is 10 or more.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0120

[Correction method] Change

[Correction content]

[0120]

[Table 10]

[Procedure Amendment 5]

[Document name to be amended] Statement

[Name of item to be corrected] 0127

[Correction method] Change

[Correction content]

[0127]

[Chemical 40]

Claims (2)

[Claims] 1. A silver halide multilayer color photographic light-sensitive material having three kinds of light-sensitive silver halide emulsion layers each containing any one of yellow, magenta and cyan couplers on a paper support. Of the emulsion layers,
The yellow coupler-containing emulsion layer contains at least one water-insoluble epoxy compound having a group represented by the following general formula (AO), and the weight ratio of the non-hydrophilic component to the hydrophilic component in the emulsion layer is 0.90 or more. The emulsion layer having a magenta coupler content of 1.30 or less is represented by the general formula (MI)
A silver halide multilayer color photographic light-sensitive material containing at least one of magenta couplers represented by I) and having a pH of the base paper of the paper support of 5 or more and 9 or less. [Chemical 1] In the above general formula (AO), R ₁ , R ₂ , R ₃ , R ₄
R ₅ and R ₅ may be the same or different and each represents a hydrogen atom, an alkyl group or an aryl group. R represents a substituent, n represents the integer of 0-4. -Y- represents a divalent linking group. -X- is -O-, -S- or -N (R ')-
Represents. R ′ represents a hydrogen atom, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, an aryl group, a heterocyclic group or —C (R ₆ ) (R ₇ ) (R ₈ ). Where R
₆ , R ₇ and R ₈ may be the same or different and each represents an alkyl group or a group represented by general formula (AO-1) shown below. R ₆ and R ₇ further represent a hydrogen atom. [Chemical 2] When n is 2 to 4, plural Rs may be the same or different. Further, any two of R _{1 to} R ₅ , R ′ and R or two Rs may be bonded to each other to form a 5 to 7 membered ring. However, when X is -S-, the total number of carbon atoms of the compound is 1
It is 5 or more. X is -O- and -Y- is-.
When SO ₂ — or phenylene, n is an integer of 1 to 4, or at least one of R ₁ to R ₅ is an alkyl group or an aryl group. X is -O-, and and Y is -O-CO ₂ - when is the total number of the carbon atoms of R ₁ to R ₄ and R is 10 or more. [Chemical 3] In the formula, R ₁₀ represents a hydrogen atom or a substituent. Y ₄ represents a hydrogen atom or a leaving group. Za, Zb and Zc represent methine, substituted methine, = N- or -NH-, and Za-
One of the Zb bond and the Zb-Zc bond is a double bond,
The other is a single bond. When the Zb-Zc bond is a carbon-carbon double bond, it includes the case where it is part of an aromatic ring.
When R ₁₀ or Y ₄ forms a dimer or higher multimer,
Further, when Za, Zb or Zc is a substituted methine, the case where the substituted methine forms a dimer or higher multimer is included. 2. The silver halide multilayer color photographic light-sensitive material according to claim 1, wherein the silver halide emulsion contained in the light-sensitive emulsion layer is a high silver chloride emulsion having a silver chloride content of 90 mol% or more. ..