JPH02106741A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the sensitivity, the gradation, the density and the sharpness of the subject material, and to maintain the high performance of the photosensitive material even in the lapse of a long time by incorporating one kind of a specified yellow pigment forming coupler and one kind of a compd. in the photosensitive material, respectively. CONSTITUTION:One kind of the yellow pigment forming coupler shown by formula I or II and one kind of the compd. shown by formula III are incorporated in the photosensitive material. In formulas I-III, R1 is an aromatic, an aliphatic or a heterocyclic ring group, A1 is hydrogen or halogen atom, etc., B1 and B2 are each an antidiffusion group, X1 and X2 are each hydrogen atom or a group capable of being released by allowing it to react with the oxidant of an aromatic primary amine color developing main agent, R2 is a substituting group, (l) is an integer of 0-5, Z1 and Z2 are each oxazole nucleus or benzoxazole nucleus, etc., R3 and R4 are each alkyl or alkenyl group, etc., X3<-> is an acidic anion, (p) is 0 or 1. Thus, the sensitivity and the gradation of the photosensitive material are improved, and the high performance of the photosensitive material is maintained even in the lapse of the long time.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, a silver halide color photographic material that has good sensitivity, gradation, density, and sharpness, and is durable over a long period of time. This invention also relates to a color photographic material having a stable silver halide emulsion layer capable of maintaining high performance.

(Conventional technique) As is well known, in subtractive color photography, aromatic primary amine color developing agents reduce exposed silver halide grains to produce oxidation products of color developing agents. Color images are formed by oxidative coupling in silver halide emulsions with couplers that form yellow, cyan, and magenta dyes.

In such cases, a compound having an active methylene group is generally used as a yellow coupler to form a yellow dye, and a pyrazolone type, a biradurohenzimidazur type as a magenta coupler to form a magenta dye. , viradulazole-based compounds are used, and phenol-based and naphthol-based compounds having hydroxyl groups are used as cyan couplers for forming cyan dyes.

Known skeleton structures of yellow couplers include, for example, pivaloylacetanilide type, henzoylacetanilide type, malondiester type, and malondiamide type.

In conventional yellow couplers, the molar extinction coefficient (ε) of the yellow dye produced is smaller than the ε of magenta and cyan couplers.
Therefore, in order to obtain a predetermined image density, it was necessary to increase only the amount of yellow coupler used. For that purpose, JIJj has a high boiling point to dissolve and disperse the coupler,? Since a large amount of medium is required, the overall thickness of the emulsion layer increases, which causes a deterioration in the sharpness of the image.

Therefore, especially for yellow couplers, a coupler with high color density per unit weight has been desired. As a measure to improve this, bis-type couplers have been proposed that produce 2 equivalents of dye from 1 mole of coupler. This bis-type yellow coupler has two coupling groups in one molecule and each reacts with an oxidized developing agent to form a dye. Therefore, the molecular weight of the coupler required to form a certain amount of dye density is reduced, allowing the light-sensitive emulsion layer to be made thinner and the sharpness of the color image to be improved.

(Problem to be Solved by the Invention) However, it has been found that photographic materials containing a bis-type yellow coupler have the disadvantage that sensitivity and gradation vary when left for a long time, making it difficult to obtain stable quality. Ta.

That is, there is a problem with the raw storage property before exposure.

For example, U.S. Pat.
No. 408,194 discloses a bis-type yellow 2-equivalent coupler represented by the following general formula.

General formula where coup is part of the coupler and LINK
represents the group of atoms that are bonded to this coupler portion through each coupling position.

Although the coupler shown here exhibits a certain degree of coupling activity, since each coup portion has a diffusion-resistant group, the molecular weight of the coupler becomes large, and the characteristics of a bis-type coupler can hardly be found. When the diffusion-resistant group is made smaller in order to lower the molecular weight, the solubility of the coupler deteriorates, and diffusion into other layers occurs, causing color mixing, which is not practically satisfactory.

US Pat. No. 1,248,961 discloses a bis-type yellow coupler having two active sites in one molecule and one surface 1 diffusing group.

Since this coupler has one diffusion-resistant group, its molecular weight is smaller than that of the corresponding coupler, which allows for thinner film thicknesses, but it also has drawbacks such as low sensitivity. It turned out that it was.

On the other hand, JP-A-62-153857 discloses a color photographic material that contains a pivaloylacetanilide type yellow coupler and is characterized by spectral aggravation with cyanine dye, but it has low color density and other problems. It was found that it has some drawbacks.

Furthermore, in JP-A-53-7233, a blue-sensitive color photographic emulsion layer is composed of at least 80 mol% silver bromide and 2 mol% or less silver iodide, and has a halogen halogen having an average grain size of 0.9n or less. A color photographic light-sensitive material has been proposed in which the silver halide grains, including silver halide grains, contain a specific sensitizing dye, but the coupler presented here has a low color density and a film thickness It turned out that it is impossible to reduce the

(Problems to be Solved by the Invention) The present invention has been made in order to improve the above-mentioned drawbacks, and the object of the present invention is to provide a highly reactive and high coloring density per unit weight. An object of the present invention is to provide a stable silver halide color photographic light-sensitive material that has good sensitivity and gradation and can maintain high performance even after being left for a long time.

(Means for Solving the Problem) The above object is to combine at least one yellow dye-forming coupler represented by the following general formula (I) or (II) with the general formula (
This was achieved by a silver halide color photographic light-sensitive material containing at least one compound represented by A).

General formula (I) In the formula, R1 represents an aromatic group, an aliphatic group, or a heterocyclic group, 8 represents a hydrogen atom, a halogen atom, or an alkoxy group, B1 represents a diffusion-resistant group, and X represents a hydrogen atom. Alternatively, it represents a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent.

7～ General formula (TI) R.

In the formula, B2 represents a diffusion-resistant group, R2 represents a substituent, X2 represents a hydrogen atom or a group that can be separated by reaction on an oxidized product of an aromatic primary amine color developing agent, and P is 0 to Represents an integer of 5.

General formula (A) II R3(Xie)pR4 In the formula, Zl and Z2 are each an oxazole nucleus, a henzoxazole nucleus, a naphthoxazole nucleus, a thiazole nucleus,
benzothiazole nucleus, naphthothiazole nucleus, selenazole nucleus, henzoselenazole nucleus, naphthoselenazole nucleus,
Represents an atomic group necessary to form a henzimidazole nucleus, naphthoimidazole nucleus, pyridine nucleus or quinoline nucleus, R3 and R6 each represent an alkyl group, alkenyl group, aralkyl group or aryl group, and x30 represents an acid anion. and p does not represent 0 or 1.

The compound represented by general formula (I) will be explained in detail below.

When R1 represents an aromatic group, it is a substituted or unsubstituted aromatic group having 6 to 16 carbon atoms, preferably 6 to IO. Examples include phenyl or naphthyl.

When R1 represents an aliphatic group, it is a linear or branched, chain or cyclic, saturated or unsaturated, substituted or unsubstituted aliphatic group having 1 to 22 carbon atoms, preferably 1 to 12 carbon atoms. For example, butyl, L~ruamylmethyl, ethyl,
Mention may be made of isopropyl, octyl, ]-decyl or adamantyl.

When R represents a heterocyclic group, the heteroatom is selected from a nitrogen atom, a sulfur atom, or an oxygen atom, and is a substituted or unsubstituted heterocyclic group having 1 to 16 carbon atoms, preferably 1 to 10 carbon atoms. Examples of representative heterocyclic groups include 2-pyridyl, 2-furyl or 2-pyrodinyl.

Examples of preferred substituents for the above-mentioned aromatic groups, aliphatic groups and heterocyclic groups include alkyl groups, halo or bromine atoms)
However, when representing an alkoxy group, the number of carbon atoms is 1 to
22, preferably 1 to 10 alkoxy groups, which may have substituents.

In the format (+), the diffusion-resistant group represented by B1 is a group that increases the molecular weight sufficiently so that the molecules are immobilized in the added photographic layer, and the number of carbon atoms in the relic is 8 or more, preferably. is a group containing 10 or more. Preferably R, O- group, Raooc- group, 118s or R50S
Examples include O□- group. Here, R9 and R6 represent a group or a hydrogen atom having the same meaning as explained for R1 above, and R7 represents a group having the same meaning as explained for R1 above. When R3 and R6 are included in the substituents listed above, they may be linked to form a cyclic structure.

- In form (I), A represents a hydrogen atom, a halogen atom or an alkoxy group, preferably a halogen atom (e.g. a chlorine atom, a fluorine atom or a group such as Il, S
An example is an O□- group.

Here, RIl represents an aliphatic group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms, or an aromatic group having 6 to 10 carbon atoms,
Preferred examples of these having a substituent include those listed as preferred substituents when R1 represents an aliphatic group. R7 represents a group having the same meaning as RIl or a hydrogen atom. As the diffusion-resistant group, for example, U.S. Pat.
No. 443,536, JP-A No. 59-177556, No. 5
Those described in No. 9-177555 or No. 62-297846 may be used.

In the general formula (I), X represents a hydrogen atom or an aromatic group that can be separated by reaction with an oxidized product of a primary amine color developing agent. Preferred examples thereof include the following formats (B) and ( It is a group represented by C).

General formula (B) f Here, Z3 represents a group of nonmetallic atoms forming a 5- or 6-membered heterocycle.

General formula (C) I.G. Lo here represents an aromatic group or a heterocyclic group.

- The compound represented by format (II) will be explained in detail below.

Examples of the diffusion-resistant group represented by 82 in general formula (II) include the diffusion-resistant group represented by 81 in general formula (I).

In general formula (II), R2 does not represent a group that can be substituted for the Hensen nucleus, but preferable examples include substituents for the aromatic group, aliphatic group, and heterocyclic group shown in R above.

! is 2 or more, R2 may be the same or different.

In general formula (II), x2 is x in general formula (+)
Examples include the same groups as l.

The most preferred coupler of general formula (I) used in the present invention is represented by the following format (III).

-Format (III) 1 Shiz 1X,
x.

In the formula, R1, B1 and island have the same meanings as defined in general formula (I).

The most preferred coupler of general formula (II) used in the present invention is represented by the following format (TV).

- Format (IV) B7 In the formula, n represents an integer from 0 to 4, and B2, R2 and x2 have the same meanings as defined in general formula (II).

The compound represented by general formula (A) will be explained in detail below.

As mentioned above, Zl and Z2 are respectively oxazole nucleus, henzoxazole nucleus, naphthoxazole nucleus, thiazole nucleus, hendithiazole nucleus, naphthothiazole nucleus, selenazole nucleus, henzoselenazole nucleus, naphthoselenazole nucleus, henzimidazole nucleus, naphtho imidazole nucleus,
This 2. As the heterocyclic nucleus represented by , 22, thiazole nucleus, henzothiazole nucleus, naphthothiazole nucleus, henzoselenazole nucleus, and naphthoxazole nucleus are preferable, and hendithiazole nucleus, naphthothiazole nucleus, and henzoselenazole nucleus are particularly preferable. preferable.

These nuclei may be substituted with various substituents,
Preferred substituents include halogen atoms (e.g. chlorine atom, bromine atom, fluorine atom), hydroxyl group, cyano group, aryl group (e.g. phenyl, p-chlorophenyl), argyl group (e.g. methyl, ethyl, propyl), alkoxy group ( for example methoxy, ethoxy), an alkoxycarbonyl group (eg methoxycarbonyl), an acylamino group (eg acetamide), a sulfonamide group (eg methanesulfonamide) or an aralkyl group (eg hensyl).

More preferred @ groups include halogen atoms, carbon atoms of 1 to
6 alkyl group, an alkoxy group having 1 to 6 carbon atoms, an aryl group, or a cyano group, and particularly preferably a chlorine atom, methyl, or methoxy.

R3 and R4 represent an alkyl group, an alkenyl group, an aralkyl group, or an aryl group, and the alkyl group represented by R3 and R4 is preferably an alkyl group having 1 to 6 carbon atoms, and ethyl, propyl, and methyl are particularly preferred. This alkyl group may be substituted with various substituents,
As the substituent, a carboxyl group and a sulfo group are preferred.

In this case, a salt may be formed with an alkali metal ion or an ammonium ion. At least one of B13 and R4 is preferably an alkyl group substituted with a sulfo group. Examples of alkenyl groups include allyl, aryl groups include phenyl, and aralgyl groups include hensyl.

X3e represents an acid anion. Preferred are chloride ion, bromide ion, iodide ion, and p-toluenesulfonic acid ion. p is an integer of 0 or 1.

Note that when at least one of R, l, and Ra is a group that itself has a negative charge, such as a carboxyl group or a sulfo group, l is 0.

Specific examples of the compounds of the present invention are shown below, but the compounds used in the present invention are not limited thereto.

-Specific example of format (A) (■ (■ (■ (■ (■ (■ (■ (■ (■ (■ (■ (■ The coupler represented by general formula (I) used in the present invention can be easily synthesized, for example, by the method described in US Pat. No. 4,248,961.

The coupler represented by the general formula (n) used in the present invention is, for example, Japanese Patent Application Nos. 63-33770 and 63-6133.
It can be easily synthesized by the method described in No. 2.

The compound represented by the general formula (A) used in the present invention is
It can be produced by a known method, for example, as described in F.M. Palmer, The Chemistry of Heterocycline Compounds, Volume 18, The Cyanine Soy and Relate Compounds (published by Interscience, New York). , 1964).

The amount of the couplers represented by the general formulas (I) and (II) used in the present invention varies depending on the structure and purpose of the compound, but preferably silver
lXl0-7 to 1 mol per mole, particularly preferably lX
It is 0.5 mole from l0-'.

The amount of the compound represented by the general formula (A) used in the present invention is 2X10-6 to 1X10 per mole of silver halide.
-2 moles are preferred, and 5X]0-6 to 5XIO"' moles are more preferred.

The couplers represented by the general formulas (I) and (II) used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027 and the like.

The boiling point at normal pressure used in the oil-in-water dispersion method is 175°C.
Specific examples of the above-mentioned high boiling point organic solvents include phthalate esters (dibutyl phthalate, dicyclohexyl phthalate,
1., di-2-ethylhexyl fucre-1., desol phthalate, bis(2,4-di-t-amylphenyl) phthalate, bis(24-di-L-amylphenyl) isophthalate, bis(], ]1- phosphoric acid or bosphonic acid esters (triphenyl phosphate, tricresyl phosphate, 2-
Ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2 ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl bosphate, tric+rob[1 pirposphate,
di-2-ethylhexylphenylphosphonate, etc.),
Benzoic acid esters @ (2-ethylhexylhenshade, dodecylhenzoate, 2-ethylhexyl-p-hydroxyhenzoe-1-, etc.), amides (NN-diethyl-24-di-t-amylphenoxyacetamide, N
N-diethyl laurylamide, etc.), alcohols or phenols (isostearyl alcohol, 2.4-
di-amylphenol, etc.), aliphatic carboxylic acid esters (bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N- (dibutyl-2-butoxy-5-t-octylaniline, etc.), hydrocarbons (paraffin, F-decylhenzen, diisopropylnaphthalene, etc.), and the like. In addition, as an auxiliary solvent, the boiling point is about 30°C or higher, preferably 50°C or higher and about 160°C.
Organic solvents of C or lower can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate-I., dimethylformamide, and the like.

When the coupler of the general formula (I) or (I[) used in the present invention is dispersed by the oil-in-water droplet dispersion method, the high-boiling organic solvent used therein is the following formula (V) or (Vl
) or a combination thereof and a co-solvent (
For example, ethyl acetate) is preferably used in combination. The weight ratio of the high boiling point organic solvent to the coupler is 1.0 or less, preferably 0.5 or less, and more preferably 0.3 or less. That is, a method of dispersing using an auxiliary solvent is also preferable.

-Form (V) In the formula, r<, , R52 may be the same or different, and each represents an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group, and the number of carbon atoms in the group represented by Rs+, Rs□ is 4 to 30.

-Form (Vl) In the formula, Rbl-R6□ and R61 may be the same or different and each represents an alkyl group, cycloalkyl group, alkenyl group or aryl group, R6,, R6□,
The total number of carbon atoms in the group represented by R6] is 12 to 60.

Various methods can be used to add the sensitizing dye to the emulsion, including those well known in the art. For example, the sensitizing dye can be dispersed directly in the emulsion, or it can be dispersed in a water-soluble solvent such as pyridine, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, fluorinated alcohols alone or in a mixture, or in a mixture with water. It can also be added as a solution, such as by dissolving it in a solvent or making it into an aqueous solution. Ultrasonic vibration may be used for this dissolution. Additionally, the dye is used in U.S. Patent No. 3.469
, No. 987, a method of dissolving a dye in a volatile organic solvent, partitioning the solution into a hydrophilic colloid, and adding this dispersion to an emulsion, Japanese Patent Publication No. 46-2/11B5 As described in et al., a water-insoluble dye is dispersed in a water-soluble solvent without melting, and the IPi, ? A method of adding & to the emulsion is also used.

The dye can also be added to the emulsion in the form of a dispersion by an acid dissolution/dispersion method. Other additions to emulsions include U.S. Patent Nos. 2.912.345 and 3.342605
No. 2.996.287, No. 3,425,83
The method described in No. 5 etc. can also be used.

The sensitizing dye used in the present invention may be added to the emulsion at any time during the emulsion manufacturing process, but preferably during or after chemical ripening. It is also preferable to add the sensitizing dye before or immediately after adding the sensitizing dye.

The sensitizing dye used in the present invention may be used in combination with other blue-sensitizing dyes to the extent that the effects of the present invention are not impaired.

In addition, examples of dyes that do not themselves have spectral sensitizing effects that can be used with the above-mentioned sensitizing dyes, or substances that exhibit supersensitization even if they do not substantially absorb visible light, include aromatic organic acids, etc. bomaldehyde condensates (e.g., those described in U.S. Pat. No. 3,437.510), cadmium salts, azaindene compounds, aminostilhene compounds substituted with nitrogen-containing heterocyclic groups (e.g., as described in U.S. Pat.
．． No. 933390 and No. 3.635,721). U.S. Patent No. 3,615.6 Layer 3;
The combinations described in US Pat. Nos. 3,615,641, 3,617.295 and 3,635,721 are particularly useful.

The light-sensitive material of the present invention only needs to have at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on the support. There are no particular limitations on the number and order of layers and non-photosensitive layers. A typical example is a silver halide photographic light-sensitive material having on a support at least one photosensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different photosensitivity. The photosensitive layer is a unit photosensitive layer sensitive to blue light, green light, or red light, and in a multilayer silver halide color photographic +A material, generally the unit photosensitive layer is A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are arranged in this order from the support side. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layer.

A non-photosensitive layer such as various intermediate layers may be provided between the two layers, the halogenated photosensitive layer, the uppermost layer, and the lowermost layer.

The intermediate layer includes JP-A Nos. 61-43748 and 59-1.
No. 13438, No. 59-113440, No. 61-20
Coupler, DIR compound, etc. as described in No. 037 and No. 61-20038 may be included,
It may also contain a commonly used color mixing inhibitor.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high-speed emulsion layer and a low-speed emulsion layer, as described in German Patent No. 1.121,470 or British Patent No. 923.045. A two-layer configuration can be preferably used.

Usually, it is preferable to arrange the layers so that the photosensitivity decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also, JP-A-57-
No. 112751, No. 62200350, No. 62-20
As described in No. 6541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side far from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.

As a specific example, from the side farthest from the support, low sensitivity blue sensitive layer (BL) / high sensitivity blue sensitive layer (B) / high sensitivity green sensitive layer (GH) / low sensitivity green sensitive layer ( GL)/
High-sensitivity red-sensitive layer (R1+)/low-sensitivity red-sensitive layer (RL
) or B H/B L/G l,/G
! I/R11/RL order, or BH/BL/
They can be installed in the order of GH/GL/RL/R1+.

Furthermore, as described in Japanese Patent Publication No. 55-34932, from the side farthest from the support, the blue-sensitive layer /G)l/
They can also be arranged in the order of RH/GL/RL. Alternatively, as described in JP-A-56-25738 and JP-A-62-63936, the blue-sensitive layer/GL/RL/Gll/RH may be arranged in this order from the farthest side from the support. .

Furthermore, as described in Japanese Patent Publication No. 49-15495, the two layers are the silver halide emulsion layer with the highest sensitivity, the middle layer is the silver halide emulsion layer with lower sensitivity, and the lower layer is the silver halide emulsion layer with lower sensitivity than the middle layer. In addition, a silver halide emulsion layer having a low sensitivity is disposed, and an arrangement consisting of three layers having different sensitivities, the sensitivities of which are successively lowered toward the support, can be mentioned. Even in the case where the layer is composed of three layers with different photosensitivity, as described in JP-A-59-202464-4111, medium-sensitivity layers are divided from the side remote from the support in the same color-sensitive layer The emulsion layer/high sensitivity emulsion layer/low sensitivity emulsion layer may be arranged in this order.

As mentioned above, various layer structures and arrangements can be selected depending on the purpose of each photosensitive material.

When the photographic light-sensitive material of the present invention is a color negative film or a color reversal film, preferred silver halide contained in the photographic emulsion layer is silver iodobromide, silver iodo, containing about 30 mol% or less of silver iodide. Silver chloride or silver iodochlorobromide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mole percent to about 25 mole percent silver iodide.

When the photographic light-sensitive material of the present invention is a color photographic paper, the silver halide contained in the photographic emulsion layer is composed of silver chlorobromide or silver chloride that does not substantially contain silver iodide. It can be preferably used. Here, "substantially free of silver iodide" means that the silver iodide content is 1 mol % or less, preferably 0.2 mol % or less. Regarding the halogen composition of these silver chlorobromide emulsions, any silver bromide/silver chloride emulsion can be used. This ratio can vary widely depending on the purpose, but the silver chloride ratio is 2 mol%.
The above can be preferably used. For light-sensitive materials suitable for rapid processing, so-called high silver chloride emulsions containing a high silver chloride content are preferably used.

The silver chloride content of these high silver chloride emulsions is preferably 90 mol% or more, more preferably 95 mol% or more. In order to reduce the amount of replenishment of the processing solution, the silver chloride content is 98%.
Emulsions of approximately pure silver chloride, such as 100 mole %, are also preferably used.

Silver halide grains in photographic emulsions include those with regular crystals such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. may have crystal defects, or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.2 microns or less, or large grains with a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

Examples of silver halide photographic emulsions that can be used in the present invention include Research Disclosure (RD) N.

17643 (I978 12JJ), pp. 22-23, “M. Emulsion preparation
tion and types)”, and the same No.
, 187] 6 (November 1979), 648 pages, Graphic "Physics and Chemistry of Photography", Published by Paul Montell (P, GIafkides, Chemic et
Ph1sique Photographique,
Paul Montel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, P,
Duffin.

Photographic Emulsion Cbe
mistry (Focal Press1966))
, Zelikman et al. [Production and coating of photographic emulsions], published by Focal Press (V, L, Zelikmanet a.
l,,Making and Coating Ph
otographic Emulsion Foca
1 Press, 1964).

U.S. Patent Nos. 3,574,628 and 3,655,39
Monodisperse emulsions such as those described in No. 4 and British Patent No. L413,748 are also preferred.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described by Gutoff, Photographic Science and Engineering.
ence and [+nginecring),
Vol. 14, pp. 248-257 (I970); U.S. Patent Nos. 4,434,226, 4,414.310, 4
, 433.048, 4,439,520 and British Patent No. 2.112.157.

The crystal structure may be --like, the inside and outside may have different halogen compositions, it may be a layered structure, or silver halides with different compositions may be joined by epitaxial bonding. It may also be bonded with a compound other than silver halide, such as silver rhodan or lead oxide.

Also, mixtures of particles of various crystal forms may be used.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are listed in Research Disclosure No.
17643 and No. 18716, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant descriptions are shown in the table below.

Added jnU! rd-RD17643 RD187161
Chemical sensitizer page 23 Page 648 right column 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, 2
Pages 3-24 Page 648 Right column - Super sensitizer
Page 649 right column 4 Brightener Page 24 5 Anti-fog agent Page 24-25 Page 649 right column ~ and stabilizer 6 Light absorber, page 25-26 Page 649 right column ~ Filter dye, page 650 left column Ultraviolet absorption Agent 7 Anti-stain agent Page 25, right column Page 650, left to right column 8
Dye image stabilizer page 25 9 Hardener page 26 page 651 left column 10
Binder, page 26 Same as above 11 Plasticizer, lubricant 27 True Page 650 right column 12 Coating aid, pages 26-27 Page 650 right column Surfactant 13 Static Page 27 Same as above Patch Also, photographic performance improvement with formaldehyde gas In order to prevent deterioration, US Patent No. 4,411,987 and US Pat.
It is preferable to add to the photosensitive material a compound that can react with formaldehye and fix it as described in No. 435,503.

Various color couplers can be used in the present invention, specific examples of which can be found in the above-mentioned Research Disclosure.
(RD) No. 17643, ■-C-C.

As a yellow coupler, for example, U.S. Patent No. 3,93
No. 3,501, No. 4.022,620, No. 4.3
No. 26,024, No. 4.401.752, No. 4,
248,961, Japanese Patent Publication No. 5810739, British Patent No. 1.425,020, British Patent No. 1.476, 760,
U.S. Patent No. 3.973,968, U.S. Patent No. 4.314,0
No. 23, No. 4,511.649, European Patent No. 249
, No. 473A, etc. are preferred.

As the magenta coupler, 5-pyraduron-based and pyrazoloazole-based compounds are preferred;
No. 0.619, No. 4.35L897, European Patent No. 7
3.636, U.S. Patent No. 3.061.432, U.S. Patent No. 3725.064, Research Disclosure N
o, 24220 (June 1984), Japanese Patent Application Publication No. 1983-
No. 33552, Research Disclosure No.
24230 (June 1984), JP-A-60-436
No. 59, No. 61-72238, No. 60-35730, No. 55-11.8034, No. 60485951,
U.S. Patent No. 4500.630, U.S. Patent No. 4.540.65
No. 4, No. 4.556.630, WO (PCT) 8
Particularly preferred are those described in No. 8104795 and the like.

Soan couplers include phenolic and naphthol couplers, and are described in U.S. Patent No. 4,052,212.
No. 4,146,396, No. 4,228.23
No. 3, No. 4,296.200, No. 2,369.9
No. 29, No. 2,801.171, No. 2.772,
No. 162, No. 2,895.826, No. 3,77
No. 2.002, No. 3,758.308, No. 4,3
34.011, 4.327,173, West German Patent Publication No. 3329.729, European Patent No. 121.365
No. A, No. 249453A, U.S. Patent No. 3.446,
No. 622, No. 4,333.999, No. 4,753
, No. 871, No. 4,451.559, No. 4,42
No. 7,767, No. 4,690.889, No. 4,
254.

No. 212, No. 4,296,199, JP-A-61-4
Those described in No. 2658 and the like are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are Research Disclosure No.

17643, ■-G section, U.S. Patent No. 4,163,670
No., Special Publication No. 57-39413, U.S. Patent No. 4,004
, No. 929, No. 4,138,258, British Patent No. 1
．． 146,368 is preferred.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2.125.
．． 570, EP 96,570 and DE 3,234,533 are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
No. 4.576°910, British Patent No. 2.102.
It is described in No. 173, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors include the aforementioned 11111764
3. Patents listed in sections ■ to F, JP-A-57-1519
．． No. 14, No. 57-154234, No. 60-1842
No. 48, No. 63-37346, U.S. Patent No. 4,248,
The one described in No. 962 is preferred.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,097,140;
Those described in JP-A No. 2.13L188, JP-A-59-157638, and JP-A-59-170840 are preferred.

Other couplers that can be used in the photosensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. , No. 4,310,618
Multi-equivalent coupler described in JP-A-60-18595
DIR redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR described in No. 0, JP-A-6224252, etc.
Redox-releasing redox compounds, couplers that release dyes that give aftercolor after separation as described in European Patent No. 173゜302A, R, D, No. 11449, European Patent No. 24241, bleaching accelerator releasing as described in JP-A No. 6L201247, etc. Couplers, Gantt-emitting couplers described in U.S. Pat.

Couplers other than the general formulas (I) and (II) used in the present invention can also be introduced into the light-sensitive material by the above-mentioned dispersion method.

These couplers can also be impregnated into loadable latentx polymers (e.g., U.S. Pat. No. 4,203,716) in the presence or absence of the high-boiling organic solvents mentioned above.
Alternatively, it can be dissolved in a water-insoluble but organic solvent-soluble polymer and emulsified and dispersed in an aqueous hydrophilic colloid solution.

Preferably, the homopolymers or copolymers described in International Publication No. WO 88100723, pages 12 to 30 are used. In particular, the use of acrylamide-based polymers is preferred from the viewpoint of color image stabilization.

The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for Sly 1 or television, color paper, color positive film, and color reversal paper.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, No. 17643, page 28, and the same No.
18716, page 647 from right column to page 648, left column.

In the photosensitive material No. 1 of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, and the film swelling rate T1/2 is preferably 30 seconds or less.

The film thickness means the film thickness measured at 25° C. and 55% relative humidity (2 days), and the film swelling rate TI/□ can be measured according to a method known in the art.

For example, A. Green et al., Photographic Science and Engineering (Photogr, Sci, Eng,), 1
It can be measured by using a swellometer (swelling membrane) of the type described in Vol.
/□ is the saturated film thickness, which is 90% of the maximum swelling film thickness reached when treated with a color developing solution at 30°C for 13 minutes and 15 seconds, and this T
It is defined as the time required to reach a film thickness of I/□.

The film swelling rate TI/□ can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions of the coating solution. Further, the swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above according to the formula: (maximum swollen film thickness - film thickness)/film thickness.

The color photographic material according to the present invention includes the above-mentioned RD,
No. 17643, pages 28-29, and No.
Development processing can be carried out by the usual method described in 615 left column to right column of No. 18716.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which are 3-methyl-4-amino-N, N-diethylaniline, 3-methyl -4-amino-N-ethyl-N-
β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-Nβ-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-methoxyethylaniline and their sulfates, hydrochloric acid Examples include salts or pI luenesulfonates. Two or more of these compounds can be used in combination depending on the purpose.

The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
Development inhibitors or antifoggants such as hendzimidazoles, hendithiazoles or mercapto compounds are generally included. In addition, if necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenyl semicarbazides, triethanolamine, catechol sulfonic acids, triethylenediamine (I,4-diazabicyclo(2,2,2)octane), various preservatives such as ethylene glycol, organic solvents such as diethylene glycol, development accelerators such as hensyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, sodium poron hydride, etc. Fogging agents, auxiliary developing agents such as I-phenyl-3-pyrazolidone, viscosity-imparting agents, and various types of dyes such as aminopolycarboxylic acids, aminopolybosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids. Agents, such as ethylenediaminetetraacetic acid, di-1-lylotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hyroxyethylidene-1,1-diphosboxic acid, ditrilo-N, N,N-trimethylenephosboxylic acid, ethylenediamine-N, 11,
Representative examples include N, 11-tetramethylenephosphonic acid, ethylenediamine-di(0-hydroxyphenylacetic acid), and salts thereof.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black-and-white developer contains known black-and-white developing agents such as dihydroxy-Hensen's agents such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-virapritone, or amine phenols such as N-methyl-p-aminophenol. It can be used alone or in combination.

The pl+ of these color developing solutions and black and white developing solutions is 9 to 12.
It is common that Although the amount of replenishment of these developing solutions depends on the color photographic light-sensitive material being processed, it is generally less than 3R per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher,
It can also be set to 0 mR or less. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank. Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

The time for color development processing is usually set between 2 and 5 minutes, but the processing time can be further shortened by using high temperature, high pi (stitching) and a high concentration of color developing agent.

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Furthermore, treatment with two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose. Examples of bleaching agents include iron (■), kohal l-(I
Compounds of polyvalent metals such as II), chromium (■), and copper (II), peracids, quinones, nitro compounds, and the like are used.

Typical bleaching agents include ferricyanide; dichromate: organic complex salts of iron (lit) or cohal III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, and 1,3-diaminopropane. Aminopolycarboxylic acids such as tetraacetic acid, glycol ether diamine tetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc.;
Persulfate; bromate-permanganate, t-nitrohenzene salt, etc. can be used. Among these, aminopolycarboxylic acid iron (I[[) complex salts and persulfates, including ethylenediaminetetraacetic acid iron (III) complex salts, are preferred from the viewpoint of rapid processing and prevention of environmental lη staining. Furthermore, aminopolycarboxylic acid iron(III) complexes are particularly useful in both bleach and bleach-fix solutions. The pu of bleaching solutions or bleach-fixing solutions using these aminopolycarboxylic acid iron (I) complex salts is usually 5.5 to 8, but in order to speed up the processing, processing can be performed at an even lower pH. .

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their pre-bath, if necessary.

US Patent No. 3,893,858, West German Patent No. 1,290,812, West German Patent No. 2,059,988,
JP 53-32736, JP 53-57831, JP 53-37418, JP 53-72623, JP 53-
No. 95630, No. 53-95631, No. 53-104
No. 232, No. 53-124424, No. 53-1416
Compounds having a mercapto group or disulfide group as described in No. 23, No. 53-28426, Research Disclosure No. 17129 (July 1978); Thiazolidine derivatives as described in JP-A-50-140129; No. 45-8506, JP-A-52-208
No. 32, No. 53-32735, U.S. Patent No. 3.706
, 561; West German Patent No. L12
No. 7.715, iodide salts described in JP-A-513-16.235; West German Patent No. 966.410, JP-A No. 2,748
．． Polyoxyethylene compounds described in Japanese Patent Publication No. 430; polyamine compounds described in Japanese Patent Publication No. 45-8836; and others such as Japanese Patent Publication No. 49-42,434, Japanese Patent Publication No. 49-59,644,
Compounds described in No. 53-94,927, No. 54-35,727, No. 55-26.506, and No. 58-163.940; bromide ions, etc. can be used. Among these, as specific examples of bleaching accelerators that are useful with mercapto groups or disulfides, compounds having groups described in the following specification are preferable from the viewpoint of having a large accelerating effect, and in particular, compounds having a group described in the following specification are preferred, and in particular, U.S. Pat. No. 3,893.85
No. 8, West Patent No. 1290.812, JP-A-53-95
, 630 are preferred. Further preferred are the compounds described in US Pat. No. 4,552,834.

These bleach accelerators may be added to the photosensitive material 4+. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

Examples of fixatives include thiosulfates, thiocyanates, dioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, with ammonium thiosulfate being the most widely used. Can be used for As the preservative for the bleach-fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment.

The amount of water used in the washing process depends on the characteristics of the photosensitive material board (e.g., depending on the materials used, such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other factors. It can be set over a wide range depending on the conditions. this house,
The relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is J
our own of the 5ociety
of Motion Picture and
Te1evision Engineers No. 64
It can be determined by the method described in Vol., P, 248-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, grouper terriers breed, and the resulting floating matter adheres to the photosensitive material. The problem arises. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
The method for reducing calcium ions and magnesium ions described in JP-A No. 62-288.838 can be used very effectively. Also, JP-A-57-8,542
Chlorinated disinfectants such as isothiazolone compounds and thiahendazole, chlorinated sodium isocyanurate, and other benzotriazoles listed in the issue, "Chemistry of antibacterial and fungicidal agents" by Hiroshi Horiguchi, Sanitary Technology Association Regulations [sterilization of microorganisms] It is also possible to use the disinfectants described in ``Encyclopedia of Antibacterial and Antifungal Agents,'' edited by Japan Society of Antibacterial and Antifungal Agents, Sterilization and Antifungal Technology J.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 4.
9, preferably 5-8. The washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15 to 45°C, preferably 30 seconds to 5 minutes at 25 to 40°C. A range is selected. Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water.

In such stabilization treatment, Japanese Patent Application Laid-Open No. 57-854
All known methods described in No. 3, No. 5814834, and No. 60-220345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be carried out, such as a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography. .

Various chelating agents and antifungal agents can also be added to this stabilizing bath.

- The overflow liquid from water washing and/or replenishment of the stabilizing liquid can be reused in other processes such as the desilvering process.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate the color developing agent, it is preferable to use various precursors of the color developing agent. For example, U.S. Patent No. 3,342,59
Indoaniline compound described in No. 7, No. 3.342,
No. 599, Research Disclosure 14.850
Symf base-type compounds described in No. and No. 15.159, aldol compounds described in No. 1.3,924, metal salt complexes described in U.S. Pat.
Examples include urethane compounds described in No. 135628.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-
It is also possible to incorporate birapritons.

Typical compounds are JP-A-56-64339 and JP-A No. 57-
No. 144547 and No. 5B-115438.

Various treatment liquids in the present invention are used at 10°C to 50°C. Normally, a temperature of 33°C to 38°C is standard, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. I can accomplish anything.

In addition, West German Patent No. 2,226,7 was developed to save silver on photosensitive materials.
70 or US Pat. No. 3,674,499 using cobalt intensification or hydrogen peroxide intensification.

Further, the silver halide photosensitive material of the present invention is disclosed in U.S. Patent No. 4,
No. 500.626, JP-A No. 60-133449, No. 5
It can also be applied to the heat-developable photosensitive materials described in No. 9-218443, No. 6]-238056, European Patent No. 210.66OA2, and the like.

(Effects of the Invention) The silver halide color photographic light-sensitive material of the present invention forms highly colored images, allows thinning of film thickness, has good sensitivity and gradation, and can be left for a long time. It also has the effect of maintaining high performance.

(Example) Next, the present invention will be explained in more detail based on examples.

Example 1 Sample 101, which is a multilayer color light-sensitive material, was prepared by coating each layer having the composition shown below on an undercoated cellulose triacetate film support.

The numbers corresponding to each component indicate the coating amount expressed in g/r+ (units). For silver halide, the coating amount is expressed in terms of silver. However, for sensitizing dyes, 1 mol of silver halide in the same layer is used. The coating amount is shown in moles.

1st layer (antihalation layer) Black colloidal silver Silver 0.18 Gelatin 0.40 2nd layer (intermediate layer) 2.5-G-mo-pentadecylhydroquinone 0.1SEX-10
,07 EX-30,02 EX-120,002 U-10,06 U-20,08 U-30,10 8B S-10,10 HB S-2 Third gelatin layer (first red-sensitive emulsion layer) Emulsion Δ Emulsion B Sensitizing dye I Sensitizing dye ■ Sensitizing dye ■ X-2 EX-10 HB S-1 Gelatin 4th layer (second red-sensitive emulsion layer) Emulsion C Sensitizing dye I Sensitizing dye ■ Dye x-2 EX-3 EX-]0 0.02 1.04 Silver 0.25 Silver 0.25 6.9X10-5 1.8X10-'3.1X10-' 0.335 0.020 0.030 0.87 Silver 1.0 5, lX10-' 1.4X10-5 2.3X10-' 0.400 0.050 0.015 Gelatin 5th layer (3rd red-sensitive emulsion layer) Emulsion sensitizing dye I Enhancement Sensitizing dye■ Sensitizing dye■ EX-3 EX-4 EX-2 HBS~I B5-2 Gelatin 6th layer (intermediate layer) EX-5 B5-1 Gelatin 7th layer (first green-sensitive emulsion layer) Emulsion A Emulsion B Sensitizing dye V 1.30 Silver 1.60 5.4XIO-5 1,4X10-5 2.4X10-' 0.010 0.080 0.097 0.22 0.10 1.63 0.040 0 .020 0.80 Silver 0.15 Silver 0.15 3.0X10-' Sensitizing dye■ Sensitizing dye■ EX-6 EX-1 EX-7 ■MiX-8 1(BS-1 t(BS -3 Gelatin 8th layer (second green-sensitive emulsion layer) Emulsion C Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ EX-6 EX-8 EX-7 HB S -1 HB S -3 Gelatin 1.0X10- '3.8X10-' 0.260 0.021 0.030 0.025 0.100 0.010 0.63 Silver 0.45 2, lX1O-5 7,0X10-5 2.6X10-' 0.094 0 .018 0.026 0.160 0.00B 0.50 9th layer (third green-sensitive emulsion layer) Emulsion E Sensitizing dye V Sensitizing dye ■ Sensitizing dye ■ EX-13 EX-11 EX-1 B5- 1 B5-2 Gelatin 1st ON (yellow filter layer) Yellow colloidal silver EX-5 HB S-1 Gelatin 11N (first blue-sensitive emulsion N) Emulsion A Emulsion B Emulsion F t 1,2 3.5XIO-' 8 .0xlO-5 3,0X10-' 0.015 0.100 0.025 0.25 0.10 1.54 Silver 0.05 0.08 0.03 0.95 i艮0.08 Silver 007 Silver 0. 07 J Sensitizing dye ■ (Exemplary compound ■ EX-9 (Exemplary coupler I EX-8 I) B5-1 Gelatin 1st +2J scratch (Second blue emulsion layer) Emulsion G Sensitizing dye ■ (Exemplary compound ■ EX-9 (Example coupler I EX-10 1 (BS-1 Gelatin 13th layer (third blue-sensitive emulsion layer) Emulsion + ( Sensitizing dye ■ (Example compound ■) EX-9 (Example coupler I IB5-1 Gelatin 14th layer (First protective layer) Emulsion ■ 1) 3.5X10-' 1) 0.433 0.042 0.28 1.10 ♀艮 0.45 1) 2. lX10-' 1) 0.092 0.007 0.05 0.78 Silver 0.77 1) 2.2X10-' 1) 0.12 0.07 0.69 Silver 0.5 B5-1 Gelatin 15th layer (Second protective layer) Polymethyl acrylate particles (about 1.5 in diameter) Gelatin 0.11 0.17 0.05 1.00 0.54 0.20 1.20 In addition to the above ingredients, each layer contains: Gelatin hardener H-1 and a surfactant were added.

X H X CJII: +(n) X X X X 0 ■ X X X 9 (Ika coupler■ X IO H X C21(.

2H5 C2115O5O3e x:y 70:30 (%) BS Tricresyl phosphate di-n-butyl phthalate Sensitizing dye ■ Sensitizing dye ■ (Preparation of samples 102 to 113) The 11th layer (first blue emulsion layer) and the 12th layer (
EX of 2nd blue-sensitive emulsion layer), 13th layer (3rd blue-sensitive emulsion layer)
(J
It was produced in the same manner as sample 101.

In each layer, the same weight of coupler as in Sample 101 was added, except that the comparative coupler <C> was added in twice the amount. ) The same number of moles of sensitizing dyes were added.

After the samples 101 to 113 prepared as described above were wedge-exposed to internal light, the following development treatments were performed, and the densities were measured and evaluated.

Also, before exposing samples 101 to +13, heat the samples at 45°C180°C.
After being left at %R1+ for 3 days, the light-sensitive material was exposed and developed as described above, and the stability of the light-sensitive material was evaluated.

The results are summarized in Table 2.

Comparison coupler <A> (Described in U.S. Patent No. 4.157.919) <B> (Described in U.S. Patent No. 3,408,194) <C> (Described in JP-A-62-153857) Sensitizing dye for comparison <l> <n> One Yuko” [− color development bleached white Water washing Fixed arrival Washing with water (I) Washing with water (2) stability drying At first glance - 3 minutes 15 seconds 6 minutes 30 seconds 2 minutes 10 seconds 4 minutes 20 seconds 1 minute 05 seconds 1 minute OO seconds 1 minute 05 seconds 4 minutes 20 seconds Captivated i temperature- 38°C 38°C 24°C 38゛C 24°C 24°C 38°C 55°C Next, the composition of the treatment liquid will be shown.

Diethylenetriaminepentaacetic acid 1-hydroxyethylidene 1.1-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 1.0 3.0 4.0 30.0 1.4 1.5mg 2.4 4- (N-Ethyl = N-β human 1 coquinethylamino) Add 2-methylaniline sulfate water and pl+ (bleach solution) Ethyleneaminetetraacetic acid 2-sodium trihydrate Ethylenediaminetetraacetic acid di-I-lium salt odor Ammonium chloride Ammonium nitrate Aqueous ammonia (27%) Add water to pH (fixer) Ethylenediaminetetraacetic acid disodium salt Sodium sulfite 4.5 1.0! 10.05 (unit: g) 100.0 10.0 140.0 30.0 6, 5 ml 1.0! 6.0 (Unit: g) 0.5 7.0 Table 2 Relative Sensitivity - Reciprocal of the amount of exposure required to give a density of minimum sensitivity ±0.2 Relative value when μ 4101 is set as 100 Gamma expressed: A sodium bisulfite ammonium thiosulfate aqueous solution expressed by the slope of the straight line connecting the point with the lowest sensitivity of 40.2 and the point where logE (E4 filling amount) is 1.0 more than that point. (70%) Add water to pH 5.0 170.0 mR 10p.

6.7 Formalin (37%) Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) Add ethylenediaminetetraacetic acid disodium salt water to pl+2.0m! 0.3 0.05 1, Ol 5.0 to 8.0 From Table 2, samples 101 to 107 using the coupler and sensitizing dye of the present invention had excellent color development compared to comparative samples 108 to 113. Moreover, it can be seen that there is no change in gamma or sensitivity even after aging, indicating that the silver halide color photographic material has excellent stability.

Example 2 Example 1 except that the development processing method used in Example 1 was replaced with the processing method described below in order to perform evaluation by rapid processing.
Samples 101 to 113 prepared in Example 1 in the same manner as
was evaluated.

As a result, the same results as in Example 1 were obtained.

*Replenishment amount: 35 mm 1 il per meter length of photosensitive material.

Tetraacetic acid ammonium bromide acetic acid ammonium nitrate add water with acetic acid and ammonia pl+ preparation pl+4.3 pH3,5 (Fixer) Mother 4baml-filter coffin-beat- l-hydroxyethylde -11-diphospho acid Ethylenediaminetetraacetic acid sl/lium salt sodium sulfite sodium bisulfite ammonium thiosulfate water 1111na (700g/fz) 5.0 7.0 0.5 0.7 10.0 12.0 8.0 10.0 170, OmQ 200. Oml Rodan ammonium 100.0 150.0 Thiourea 3.0 5.0 diethylenetriamine pentacholic acid sodium sulfite potassium carbonate potassium bromide potassium iodide hydroxylamine sulfate 4-(N-ethyl-N-β Hydroxyethylamide -2-methylanili sulfate add water pl+ 5.0 4.0 30.0 1.3 1.2mg 2.0 3.6 4.7 6.2 1.0　ρ　　1.0　℃ 10.00 10.1.5 1.3-diaminopropa 13-diaminopropa 36-Sichia 18 octanediol add water Add acetic acid and ammonia tepl+ 3.0 5.0 1.0ffi 1,0ffi 6.5 6.7 (Stable solution) Common to mother solution and replenisher solution Formalin (37%) 5-chloro-2-methyl-4 Isothiazolin-3-one 2-methyl-4-isothiazoli Thor 3-on surfactant 2m11 6.0mg 3.0mg 0.4 g ethylene glycol add water pH 1.0m1 1.ON 5.0-7.0

Claims (1)

[Scope of Claims] A halogenated compound comprising at least one yellow dye-forming coupler represented by the following general formula (I) or (II) and at least one compound represented by the general formula (A) Silver color photographic material. General formula (I) ▲There are numerical formulas, chemical formulas, tables, etc.▼ In the formula, R_1 represents an aromatic group, aliphatic group, or heterocyclic group, A_1 represents a hydrogen atom, a halogen atom, or an alkoxy group, and B_1 represents a It represents a diffusing group, and X_1 represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent. General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, B_2 represents a diffusion-resistant group, R_2 represents a substituent, and X_2 is a hydrogen atom or an oxidized product of an aromatic primary amine color developing agent. represents a group that can be separated by reaction with, and 1 represents an integer of 0 to 5. General formula (A) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the formula, Z_1 and Z_2 are respectively oxazole nucleus, benzoxazole nucleus, naphthoxazole nucleus, thiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, selenazole nucleus, benzoselenium. R_3 and R_4 each represent an alkyl group, an alkenyl group, an aralkyl group, or an aryl group. Representation, X
_3^■ represents an acid anion, and p represents 0 or 1.