JPH0731379B2 - Silver halide color photographic light-sensitive material - Google Patents

Description

The present invention relates to a silver halide color photographic light-sensitive material, and more specifically to a silver halide color photographic in which sharpness is greatly improved without great desensitization. It relates to a photosensitive material.

BACKGROUND OF THE INVENTION In recent years, development of a color light-sensitive material having high sensitivity and improved sharpness has been strongly proposed. Conventionally, as a method of improving sharpness, a method of reducing the thickness of the emulsion layer of a color light-sensitive material to minimize the light scattered by silver halide crystals of the emulsion layer, or a method of undesiring a certain spectral region is not desirable. A method of adding a substance that absorbs light (dye, UV-absorber) to improve the sharpness is known.

Such substances are known by the concept of filter dyes and can be used directly in the emulsion layer or in a special filter layer of a color light-sensitive material.

The method of improving the sharpness by minimizing the scattered light by using the silver halide crystal of the emulsion layer with the filter layer has a great effect of improving the sharpness (especially the characteristics on the high frequency side), but the sensitivity is high. Has the serious drawback that

[Object of the Invention] An object of the present invention is to provide a silver halide color photographic light-sensitive material capable of obtaining a large sharpness-improving effect with a small decrease in sensitivity when improving sharpness by using a filter layer.

[Structure of the present invention] The present inventor has studied various materials based on the above technical background, and as a result, at least one photosensitive silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid on a support. In a silver halide color photographic light-sensitive material having a layer, at least one of the silver halide emulsion layers contains silver halide grains having an average aspect ratio of 5: 1 or more in which silver iodide is localized therein, and A non-diffusible red absorbing dye and / or at least one layer of the non-photosensitive hydrophilic colloid layer
It has also been found that the object of the present application can be achieved by incorporating a non-diffusible green absorbing dye.

The tabular silver halide emulsion of the present invention has an average aspect ratio of
It contains a silver halide grain group of 5: 1 or more. Aspect ratio refers to the ratio of particle diameter: thickness. Here, the diameter of a silver halide grain means the diameter of a circle having an area equal to the projected area of the grain. The average aspect ratio used in the present invention is preferably 6: 1 or more 100: 1 or less, more preferably 7: 1 or more 50:
It is 1 or less, particularly preferably 8: 1 or more and 20: 1 or less.

In the present invention, the average diameter of the tabular silver halide emulsion is preferably 0.5 to 30 μm, more preferably 1.0 to 20 μm.

In the layer containing the tabular silver halide emulsion of the present invention, 5:
It is preferred that tabular grains having an aspect ratio of 1 or more are present in a weight ratio of 40% or more, particularly 60% or more, based on the total weight of silver halide grains in the layer.

In the present invention, as the halogen composition of the tabular silver halide grains, silver bromide, silver iodobromide, silver chloroiodobromide, silver chlorobromide, silver chloride and the like can be used. Silver iodide is preferable, and silver iodobromide having a silver iodide content of 0 to 18 mol% is more preferable. A particularly preferable silver iodide content is 4 to 12 mol%.

The tabular silver halide emulsion of the present invention is disclosed in JP-A-52-153428,
54-155827, 54-118823, 58-127921, 58-113928
It can be obtained by a known method disclosed in, for example, Japanese Patent Publication.

A particularly preferred tabular silver halide emulsion is one in which the silver iodobromide is localized in the central part of the silver iodobromide.

The high iodine content phase in the central portion is preferably 80% or less, and particularly preferably 60% to 10% of the total volume of the grains.

The silver iodide content in the central portion is preferably 5 to 40 mol%,
10 to 30 mol% is preferable.

The low iodide content phase surrounding the central high iodide content phase has a silver iodide content of 0 to 10 mol%, more preferably 0.1 to 6.0 mol%.
Is preferably silver iodobromide.

A tabular silver halide emulsion in which silver iodide is localized in the central portion can be obtained by a known method disclosed in JP-A-59-99433.

As a method for confirming the halogen composition structure in the silver halide grain of the present invention, JI Goldstein (goldatei
n) and DB Williams “X-ray analysis in TEM / ATEM”, Scanning Electron.
Microscopy (1977), Volume 1, IIT Research Institute, March 1977, P.651. The particles to be examined were placed on a grid and cooled to the temperature of liquid nitrogen. A focused beam of electrons is applied to a 0.2 micrometer spot on each particle to be inspected. 7
Inspect the sample at a 5 kilovolt accelerating voltage. By measuring the intensity and energy of the X-rays generated by the electron beam, the ratio of iodide to bromide in the grain at the spot where the electron hits can be determined.

The non-diffusible green absorbing dye and the non-diffusing red absorbing dye in the present invention are the above-mentioned dyes added at the time of adjusting the non-photosensitive hydrophilic colloid layer in the manufacturing process of the color light-sensitive material, and other layers at the end of the manufacturing. Any substance can be used as long as it is present in the non-photosensitive hydrophilic colloid layer without being diffused into the non-photosensitive hydrophilic colloid layer.

As an example of the non-diffusible dye, for example, a non-diffusible acid dye is used by allowing a diffusible acid dye and a polymer mordant having a basic group to coexist in the same non-photosensitive hydrophilic colloid layer. You can

Examples of the polymer mordant having a basic group include polymers containing imidazole, pyridine, alkylaminoalkyl (meth) acrylate, quaternary salts thereof, aminoguanidine and the like. The base polymer mordant used preferably is described in detail in each of the US patent specifications indicated by the following patent numbers. That is, No. 2,548,564,
No. 2,675,316, No. 2,882,156 and No. 3,706,563 etc., among them, particularly preferred basic polymer mordant in the present invention is Patent No. 2,882,156, and No. 3,7.
Polyvinyl alkyl ketone or poly-N-oxoalkyl (meth) described in US Pat. No. 6,563
It is a condensation product of acrylamide and aminoguanidine.

Next, typical examples of the basic polymer mordant preferably used in the present invention will be given.

The dye used in combination with the basic polymer mordant may be any acidic dye, but is preferably an acidic dye having a sulfo group or a carboxy group, for example, azo type, triphenylmethane type, Acid dyes such as anthraquinone type, styryl type, benzylidene type, merocyanine type and oxonol type dyes can be used.

Next, typical examples of the acid dye used in the present invention will be given.

The above acid dye and basic polymer mordant can be synthesized by a known method, and can be contained in the non-photosensitive hydrophilic colloid layer by a known method.

Examples of particularly preferable non-diffusible green absorbing dyes used in the present invention include reaction products of known magenta couplers and known color developing agents, and particularly preferable examples of non-diffusing red absorbing dyes. Is a reaction product of a known cyan coupler and a known color developing agent.

Specific examples of the magenta couplers include pyrazolone-based, pyrazolotriazole-based, pyrazolobenzimidazole-based, and indazolone-based couplers. As such a magenta coupler, US Pat.
No. 2,600,788, No. 2,983,608, No. 3,062,653, No. 3,127,269, No. 3,311,476, No. 3,419,391,
No. 3,519,429, No. 3,558,319, No. 3,582,322
No. 3,615,506, 3,834,908, 3,891,44
5, West German patent 1,810,464, West German patent (OLS) 2,408,665
No. 2, 2,417,945, 2,418,959, 2,424,467,
JP-B-40-6031, JP-A-49-74027, 49-74028,
49-129538, 50-60233, 50-159336, 51-2
0826, 51-26541, 52-42121, 52-58922,
Examples thereof include those described in Japanese Patent Application No. 53-55122 and Japanese Patent Application No. 55-110943.

Furthermore, examples of the cyan coupler include phenol or naphthol derivatives, and examples of such a cyan coupler include, for example, U.S. Patents 2,423,730 and 2,4.
74,293, 2,801,171, 2,895,826, 3,
No. 476,563, No. 3,737,326, No. 3,758,308, No. 3
3,893,044, JP-A-47-37425, 50-10135
No. 50, No. 50-25228, No. 50-112038, No. 50-117422,
Those described in Japanese Patent Publication No. 50-130441, etc.
The couplers described in JP 98731 are preferred.

As the known color developing agent to be reacted with the above-mentioned coupler, aromatic primary amine compounds, particularly p-phenylenediamine compounds are preferable, and N, N-diethyl-p-phenylenediamine hydrochloride and N-ethyl are used. -P-phenylenediamine hydrochloride, N, N-dimethyl-p-phenylenediamine hydrochloride, 2-amino-5- (N-ethyl-N-dodecylamino) -toluene, N-ethyl-N- (β-methane Sulfonamidoethyl) -3-methyl-4-aminoaniline sulfate, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-N- (2-methoxyethyl) -N-ethyl-3-methylaniline -P-toluenesulfonate, N, N-diethyl-3-methyl-4-aminoaniline, N-ethyl-N- (β-hydroxyethyl) -3-methyl-4-ami It can be mentioned aniline.

Examples of other particularly preferable non-diffusing green absorbing dyes include known color cyan dye couplers.

Known colored cyan couplers include, for example, U.S. Pat.Nos. 2,521,908, 3,034,892, and British Patent 1,255,
Examples thereof include compounds described in JP-A No. 111, JP-A-48-22028 and the like.

Further, U.S. Pat.No. 3,476,563, JP-A-50-10135, 50-
Colored cyan couplers of the type in which the dye flows out into the processing bath upon reaction with the oxidation product of the color developing agent as described in 123341 can also be used.

A particularly preferred colored coupler is represented by the following general formula [I] -a
To a compound represented by [II] -b In the general formulas [I] -a and [I] -b, R ₁ and
R ₂ is a hydrogen atom, a linear or branched alkyl group having 1 to 30 carbon atoms, a mono- or bicycloalkyl group (eg, cyclohexyl group), a terpenyl group (eg, nobornino group), an aryl group (eg, phenyl group, naphthyl) Group, etc.), a heterocyclic group (for example, a benzimidazolyl group, a benzothiazoline group, etc.) or a nonmetal atom necessary for forming a heterocycle such as morpholine and pyridine. The above alkyl group, aryl group and heterocyclic group may be substituted, and examples of the substituent include the following groups. Halogen atom, nitro group, hydroxy group, carboxy group,
(The coupler has at least the number of carbon atoms in the uncoupling position.
12 or equivalent ballast group), amino group, aryl group, substituted amino group (alkylamino, dialkylamino, anilino, N-alkylanilino, etc.), carboxylic ester group (carbalkoxy, carboaryloxy, etc.) , Amide groups (acetamide, butyramide,
Ethyl sulfonamide, N-methylbenzamide, N-
Propylbenzamide, 4-t-butylbenzamide, etc.), carbamyl group (carbamyl, N-octadecylcarbamyl, N, N-dihexylcarbamyl, N-methyl-
N-phenylcarbamyl, 3-pentadecylphenylcarbamyl, etc.), sulfamyl group (in the case where the coupler has at least 12 carbon atoms or a corresponding ballast group at the uncoupling position, N-propylsulfamyl, N-tolyl) Sulfamyl, etc.), alkoxy group (ethoxy, octadecyloxy, etc.), sulfo group (when the coupler has at least 12 carbon atoms or a corresponding ballast group at the uncoupling position), substituted sulfonyl group (methylsulfonyl, octadecylsulfonyl) Ethoxysulfonyl, decyloxysulfonyl, phenylsulfonyl, trisulfonyl, phenoxysulfonyl, etc.) and the like.

R ³ is represented by -COR ₅ and -COOR _5. (Wherein R ₅ represents an alkyl group having 1 to 20 carbon atoms or a substituted alkyl group), and R ₄ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

In the general formulas [II] -a and [II] -b, R ₁ is a hydrocarbon residue, R ₂ is an amino group, an alkyl group, an acylamino group, a ureido group, an alkoxycarbonyl group and their substitution products, a carboxyl group, etc. Indicates. -L- has 1 carbon
~ 6 represents an alkyleneoxy group, and m represents 0 or 1.

[DD] represents a diffusible dye residue, and represents a diffusible dye residue having a known dye moiety such as azo, azomethine, indoaniline, indophenol, and anthraquinone.

A preferable [DD] is represented by the following formula.

Examples of other particularly preferable non-diffusible dyes used in the present invention include compounds represented by the following general formula [III].

General Formula [III] BallXnCol where -Ball represents an organic stabilizing group having a molecular size and arrangement which renders the compound non-diffusible during development in an alkaline processing composition.

Examples of the above organic stable groups include, for example, formulas (I) to (II
It is represented by I).

In the formula (I), Z is a benzene ring to which an OY group is bonded,
Saturated carbocycle (5-membered to 7-membered) that is bonded at the 5th and 6th positions
Represents a group of non-metal atoms required to form Y is most preferably a hydrogen atom, but it may be a group capable of cleaving a bond with an oxygen atom at a hydrogen ion concentration of 10 ^{−5 to} 2 mol / l depending on the use and properties of the photographic element to be added.
Among the latter groups, the more preferable effect is Is a group represented by. Where R ⁽¹⁾ is a carbon atom of 1 to
It represents an alkyl group having 18 carbon atoms, an alkyl group having 1 to 18 carbon atoms substituted with a halogen atom, a phenyl group or a substituted phenyl group.

B represents an organic group which renders the compound represented by the general formula [III] non-diffusible in a color light-sensitive material, and the organic group is a long-chain alkyl group; or an aromatic group such as a benzene group or a naphthalene group. Or a long-chain alkyl group bonded to one end of a suitable divalent group or a benzene-based or naphthalene-based aromatic group as a representative one. The long-chain alkyl group or aromatic group may be substituted here, and a suitable divalent group is -O-; -S-; ^{-CR (3) R (4)} -; - CR (3) = CR (4) - ( here, R ⁽²⁾ represents a hydrogen atom, an alkyl group or an aryl group, R ⁽³⁾ and R
Each of ⁽⁴⁾ represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group. ); And one or more selected from the group consisting of a substituted or unsubstituted aromatic divalent group, a non-aromatic carbocyclic group and a non-aromatic heterocyclic group, and consisting of one of these: It is a divalent group formed by arbitrarily combining a plurality of these groups in a linear form.

In the formula (II), W represents an organic group which renders the compound represented by the general formula [III] non-diffusible in the color light-sensitive material, and is generally an aliphatic group or aromatic group having 8 to 20 carbon atoms. Base,
Examples thereof include an alicyclic group and an organic stabilizing group having a heterocyclic group.
The compounds of the present invention is attached via a nitrogen atom to the 5-position or 6-position of these groups indole ring, but as an aspect through such nitrogen atom, -NHCO- group, -NHSO ₂ -
And a group via a group such as a group, a —NR ₃ — group (R ₃ represents a hydrogen atom or an alkyl group) and the like. The organic stabilizing group is bonded to the 5- or 6-position of the indole ring,
It is preferable to bind to the position.

In the general formula (II), R ₁ represents a monovalent organic group, and examples of the group include an alkyl group and an alkoxy group.
An alkyl group and an alkoxy group having 1 to 3 carbon atoms are preferable.

In the general formula (II), R ₂ represents a low-molecular group bonded through a carbon atom, and the group is preferably a substituent having 1 to 9 carbon atoms, for example, having 1 to 9 carbon atoms. Alkyl group, phenyl group and (R ₄ and R ₅ represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ₄ and R ₅ may simultaneously form a ring.)
Is mentioned.

More preferably as R ₂ , an unsubstituted or halogen atom,
Examples thereof include a phenyl group substituted with a group selected from the group consisting of an acetylamide group, a methylsulfonamide group, a nitro group, a carboxy group, a sulfo group, a methanesulfone group, an alkyl group and an alkoxy group.

In the formula, E is directly attached to the 6-membered aromatic ring or Alkylene group (may be branched), -O-,-
S -, - SO ₂ -, a phenylene group (. May be substituted by an alkyl group) or bonded to have a halogen atom through them becomes by arbitrarily combining group, a sulfo group, a carboxy group, an alkyl Group, aryl group, alkoxy group,
It represents a heterocyclic group such as an aryloxy group, a nitro group, an amino group, a cyano group, an alkylamino group, an arylamino group, a cyano group, an alkylthio group and a pyridyl group, which may be the same or different.

n represents an integer of 0 to 4.

D represents a group represented by -OR ₁ or -NHR ₂ . Here, R ₁ is under the condition of hydrogen atom or hydroxide ion concentration of 10 ⁻⁵ to 2 mol / l.
Represents a group in which the bond between R ₃ and O is cleaved, preferably a hydrogen atom, Is a group represented by. Here, R ₃ is an alkyl group, particularly an alkyl group having 1 to 18 carbon atoms.

X in the general formula [III] represents a suitable divalent group, and as a suitable divalent group, -O-; -S-; −SO ₂ −; −SO−; −NN ¹ CO−; −NR ¹ SO ₂ −; CR ² R ³ −; −
CR ³ = CR ⁴ − and the like. (Here, R ¹ represents a hydrogen atom, an alkyl group or an aryl group, and R ² and R ³ each represent a hydrogen atom, a halogen atom, an alkyl group or an aryl group.) —Col in the general formula [III] is diffusible Of magenta or cyan dye components or precursor components of these dyes.

Such ingredients are well known to those of skill in the art and include azo,
Dyes such as azomethine, azopyrazolone, indoaniline, indophenol, anthraquinone, triarylmethane, alizarin, merocyanine, nitro, quinoline, cyanine, indigoid, phthalocyanine, metal complex forming dyes, as well as leuco dyes, pH value fluctuations,
"Shifted", which changes to a bathochromic or bathochromic color when different ambient environments such as reactions with complex-forming substances are applied
Contains dye precursors such as dyes and the like. Also, −Co
l may be a coupler component such as phenol, naphthol, indazolone, pyrazolone, compounds described in US Pat. No. 2,756,142. These ingredients are
You may have a solubilizing group as needed. .

Examples of -Col include those represented by formulas (IV) to (IX).

In formulas (IV) to (VI), Q is at the 5-position or 8 with respect to G.
Position, the hydroxyl group or the formula --NHCOR ³ or --NHSO ₂ R
³ (wherein R ³ represents an alkyl group having 1 to 6 carbon atoms, a substituted alkyl group having 1 to 6 carbon atoms, a benzyl group, a phenyl group or a substituted phenyl group having 6 to 9 carbon atoms) And G is a hydroxyl group or a salt thereof or a formula (Wherein R ⁴ represents an alkyl group having 1 to 18 carbon atoms, a phenyl group or a substituted phenyl group having 6 to 18 carbon atoms) and represents a hydrolyzable acyloxy group, and r is 1 or 2 Represents an integer of Z, cyano group, trifluoromethyl group, fluorosulfonyl group, carboxy group, formula -COOR ⁴
(Wherein R ⁴ represents the above), a nitro group at the 2- or 8-position with respect to the azo bond, fluorine,
Chlorine or bromine atom, alkyl having 1 to 8 carbon atoms
Or a substituted alkylsulfonyl group, having 6 to 9 carbon atoms
A phenyl- or substituted phenylsulfonyl group, an alkylcarbonyl group having 2 to 5 carbon atoms, and a formula —SO ₂ NR ⁵ R
⁶ (wherein R ⁵ represents a hydrogen atom, an alkyl or substituted alkyl group having 1 to 8 carbon atoms, R ⁶ represents a hydrogen atom, 1 carbon atom)
~ 6 alkyl or substituted alkyl group, benzyl group,
Phenyl group or substituted alkyl group, benzyl group, phenyl group or substituted phenyl group having 6 to 9 carbon atoms, alkyl group having 2 to 7 carbon atoms or substituted alkylcarbonyl group, phenyl group having 7 to 10 carbon atoms or substituted Phenylcarbonyl group, C1-C6 alkyl-
Or a substituted alkylsulfonyl group, having 6 to 9 carbon atoms
A phenyl- or substituted phenylsulfonyl group, or R ⁵ and R ⁶ together with the nitrogen atom to which they are attached represent a morpholine group or a piperidino group) sulfamoyl group, or a formula-CON ( R ⁵ ) ₂ (in the formula, R ⁵ is the same or different and represents the same as above), Z ¹ represents hydrogen or Z, R ¹ represents a hydrogen atom,
Represents an alkyl group having 1 to 4 carbon atoms, a substituted alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a halogen atom, and D represents a cyano group, a sulfo group, a fluorosulfonyl group, a halogen atom, -SO ₃ - phenyl group or a substituted -SO ₃ carbon atoms 6-9 - phenyl group, an alkyl having 1 to 8 carbon atoms - or an alkyl sulfonyl group, a phenyl carbon atoms 6-9 - or a substituted phenyl Sulfonyl group, C1-C8 alkyl- or substituted alkylsulfinyl group, C6-C9 phenyl- or substituted phenylsulfinyl group, formula -SO
₂ NR ⁵ R ^{6 is} a sulfamoyl group or a carbamoyl group of the formula —CON (R ⁵ ) ₂ (wherein R ⁵ and R ⁶ are the same as defined above for Z). There are no more sulfo groups and no more than one carboxy group.

In formulas (VII) to (IX), Y is a hydrogen atom, Represents Here, R ₁₂ represents a hydrogen atom, an alkyl group or an aryl group having 1 to 8 carbon atoms, R ₁₃ represents an acyl group,
It represents a hydroxyalkyl group, an alkoxyalkyl group, an alkoxyalkyllenoxyalkyl group, a carboxyalkyl group, a carboxyphenyl group, a carboxyalkylphenyl group, a hydroxyalkylphenyl group, an alkoxyphenyl group, or a group having the same meaning as the group represented by R ₁₂ .
W represents —CO— or —SO ₂ —, R ₇ represents an alkyl group having 1 to 6 carbon atoms, an aryl group, or Represents (Here, R ₁₄ and R ₁₅ are hydrogen atoms and carbon atoms 1
To 8 represent an alkyl group or an aryl group. However, R
₁₄ and R ₁₅ cannot be hydrogen atoms at the same time. ) R ₈ is an alkyl group having 1 to 6 carbon atoms or 6 carbon atoms
~ 10 represents an aryl group.

R ₉ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or 1 to
8 represents a dialkylamino group having 8 carbon atoms, and R ₁₀ represents an alkyl group having 1 to 8 carbon atoms, an alkylthio group having 1 to 8 carbon atoms, an arylthio group, a halogen atom, or an acylamino group having 1 to 10 carbon atoms.

Here, n is 0, 1 or 2.

R ₁₁ represents an alkyl group having 1 to 6 carbon atoms or an aromatic group (eg, phenyl group).

Next, specific representative examples of the non-diffusing green absorbing dye and the non-diffusing red absorbing dye used in the present invention are shown, but the compounds used in the present invention are not limited to these.

The non-diffusible dye of the present invention is synthesized by a known method. For example, JP-A-48-33826, JP-A-50-115528, and JP-A-57-85
055, 54-54021, U.S. Pat.No. 4,053,312, JP-A-54
-99431, 53-50736 and the like.

Preferred non-diffusible green absorbing dyes and non-diffusible red dyes in the present invention are known high-boiling organic solvents such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, cyclohexane, tetrahydrofuran, carbon tetrachloride and chloroform. After dissolving in a representative low boiling point organic solvent, it was mixed with an aqueous gelatin solution containing a surfactant, and then emulsified and dispersed using a dispersing means such as a stirrer, a homogenizer, a colloid mill, a flow jet mixer, and an ultrasonic dispersing device. Then, it is added to the non-photosensitive hydrophilic colloid layer coating composition for use.

Known high-boiling organic solvents used include organic acid amides, carbamates, esters, ketones, urea derivatives and the like, particularly dimethyl phthalate, diethyl phthalate, di-propyl phthalate, di-butyl phthalate,
Phthalates such as di-n-octyl phthalate, diisooctyl phthalate, diamyl phthalate, dinonyl phthalate, diisodecyl phthalate, tricresyl phosphate, triphenyl phosphate, tri- (2-ethylhexyl) phosphate, triso Nonyl phosphate and other phosphates, dioctyl sebacate, di- (2-ethylhexyl) sebacate, diisodecyl sebacate and other sebacate esters, glycerol tripropionate, glycerol tributyrate and other glycerin esters, and other adipic acid Ester, glutarate ester, succinate ester,
One or more phenol derivatives such as maleic acid ester, fumaric acid ester, citric acid ester, di-tert-amylphenol, and n-octylphenol can be used in combination.

The non-diffusible green absorbing dye and the non-diffusing red absorbing dye used in the present invention are preferably oil-soluble dyes as described above, which are dissolved in a known high-boiling point organic solvent and emulsified and dispersed, followed by non-photosensitive hydrophilicity. It is used by adding it to the colloid layer (filter layer).

The amount of non-diffusible dye to be added to the filter layer is generally such that the transmission density of the filter layer is in the red absorption wavelength range of the red absorption layer and the wavelength range corresponding to the red (600 to 700 nm) color sensitivity of the emulsion layer. The green absorption filter layer is 0.01 to 0.3, preferably 0.03 to 0.1, measured with light having a wavelength range corresponding to the color sensitivity of the green range (500 to 600 nm) of the green-sensitive emulsion layer.
Is. The thickness of the filter layer is 0.1-3.0 μm, especially
0.3 to 1.5 is preferable.

The preferred position of the red absorbing filter layer is any non-photosensitive colloid layer located farther from the support than the red sensitive emulsion layer closest to the support in the red sensitive emulsion layer, and a particularly preferred position of the red absorbing filter layer. Is a non-photosensitive hydrophilic colloid layer which is adjacent to the red-sensitive emulsion layer closest to the support and is distant from the support.

The preferred position of the green absorption filter layer is any non-photosensitive colloid layer located farther from the support than the red-sensitive emulsion layer closest to the support among the green-sensitive emulsion layers,
A particularly preferable position of the green absorption filter layer is the non-photosensitive hydrophilic colloid layer which is adjacent to the green-sensitive emulsion layer closest to the support and is distant from the support.

Light absorption of the red absorption filter layer other than the red region and light absorption of the green absorption filter layer other than the green region are optional, but preferably the performance of each photosensitive layer is changed independently and independently in the design of the color photosensitive material. From the viewpoint that the light absorption is possible, the former absorbs light as little as possible outside the red region and the latter as little as possible outside the green region.

In the present invention, the red absorption filter layer and the green absorption filter layer may be in the form of a filter layer that absorbs red and green, which performs these functions in one layer.

The present invention is effective only when the silver halide grains are combined with the non-diffusible red absorbing dye and / or the non-diffusible dye. Other materials can be used together.

For the silver halide emulsion, any of silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide, silver chloride and the like which are used in ordinary silver halide emulsions can be used. However, silver bromide, silver iodobromide, and silver chloroiodobromide are particularly preferable.

The silver halide grains used in the silver halide emulsion may be those obtained by any of the acidic method, the neutral method and the ammonia method. The grains may be grown at one time, or may be grown after forming seed grains. The method of forming seed particles and the method of growing seed particles may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed at the same time, or the other may be mixed in a liquid containing either one. Alternatively, it may be produced by sequentially adding halide ions and silver ions simultaneously while controlling the pH and pAg in the mixing vessel while considering the critical growth rate of silver halide crystals. By this method, silver halide grains having a regular crystal form and a substantially uniform grain size can be obtained. The conversion may be used at any step in the formation of AgX to change the halogen composition of the grains.

The silver halide grains are cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (including complex salt), rhodium salt (including complex salt) and iron salt (in the process of forming and / or growing the grain). Metal ions are added using at least one selected from the group consisting of complex salts)
Alternatively, these metal elements can be contained on the grain surface, and reduction sensitizing nuclei can be imparted to the inside of the grain and / or the grain surface by placing in a suitable reducing atmosphere.

In the silver halide emulsion, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or may be contained. When removing the salts, Research Disclosure (hereinafter R)
It can be carried out based on the method described in Item 17643, Item II.

The silver halide grain may be one having a uniform silver halide composition distribution within the grain, or may be a core / shell grain having a different silver halide composition between the inside of the grain and the surface layer.

The silver halide grain is preferably a grain in which a latent image is mainly formed on the surface.

The silver halide grain may have a regular crystal form such as a cube, an octahedron or a tetradecahedron, or may have an irregular crystal form such as a sphere or a plate. In these grains, any ratio of {100} plane to {111} plane can be used. Further, it may have a composite form of these crystal forms, and particles of various crystal forms may be mixed.

The size of silver halide grains may be 0.05 to 30 μm, preferably 0.1 to 20 μm.

The silver halide emulsion may have any grain size distribution. An emulsion having a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion having a narrow grain size distribution (referred to as a monodisperse emulsion. The monodisperse emulsion referred to here is the standard deviation of the grain size distribution. When divided by the average grain size, the value is 0.20 or less, where the grain size is the diameter in the case of spherical silver halide and the projected image in the case of grains other than spherical. The diameter when converted to a circular image of the same area is shown).
Further, a polydisperse emulsion and a monodisperse emulsion may be mixed and used.

As the silver halide emulsion, two or more kinds of silver halide emulsions formed separately may be mixed and used.

The silver halide emulsion can be chemically sensitized by a conventional method. That is, sulfur lateral sensitization method, selenium sensitization method, reduction sensitization method,
The noble metal sensitization method using gold or other noble metal compounds can be used alone or in combination.

The silver halide emulsion can be optically sensitized to a desired wavelength range by using a dye known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more. A dye that does not have a spectral sensitizing action by itself with a sensitizing dye, or a compound that does not substantially absorb visible light, and that contains a supersensitizer that enhances the sensitizing action of the sensitizing dye in the emulsion. Good.

As the sensitizing dye, a cyanine dye, a merocyanine dye,
Complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, steryl dyes and hemioxanol dyes are used.

Particularly useful dyes are cyanine dyes, merocyanine dyes,
And a complex merocyanine dye.

Silver halide emulsion, during the manufacturing process of the light-sensitive material, during storage,
Alternatively, for the purpose of preventing fog during photographic processing or maintaining stable photographic performance, during chemical ripening, at the end of chemical ripening, and / or after the completion of chemical ripening, before coating a silver halide emulsion, Compounds known in the art as antifoggants or stabilizers can be added.

As the binder (or protective colloid) of the silver halide emulsion, it is advantageous to use gelatin, but gelatin derivatives, graft polymers of gelatin and other macromolecules, other proteins, sugar derivatives, cellulose derivatives, single Alternatively, a hydrophilic colloid such as a synthetic hydrophilic polymer substance such as a copolymer can also be used.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material using the silver halide emulsion of the present invention include one or more hardeners which crosslink binder (or protective colloid) molecules to enhance film strength. By using it, a dura mater can be obtained. The hardener can be added in such an amount that the photosensitive material can be hardened to the extent that it is not necessary to add the hardener to the processing liquid.
It is also possible to add a hardening agent to the processing liquid.

For example, aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5 -Triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol and the like), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine and the like), mucohalogen acids (mucochloric acid, Mucophenoxycyclo acid, etc.) can be used alone or in combination.

A plasticizer can be added to the silver halide emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material for the purpose of increasing flexibility. Preferred plasticizers are the compounds described in RD 17643, Section XII, A.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material may contain a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability.

For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination, or these and acrylic acid, A polymer having a monomer component of a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid and the like can be used.

In the color development processing, the emulsion layer of the light-sensitive material forms a dye by a coupling reaction with an oxidant of an aromatic primary amine developer (eg, p-phenylenediamine derivative, aminophenol derivative). A coupler is used. The dye-forming couplers are usually selected so that a dye that absorbs the light of the light-sensitive spectrum of the emulsion layer is formed for each emulsion layer. A magenta dye forming coupler is used in the sensitive emulsion layer and a cyan dye forming coupler is used in the red sensitive emulsion layer. However, a silver halide color photographic light-sensitive material may be prepared by a method different from the above combination depending on the purpose.

It is desirable that these dye-forming couplers have a group called a ballast group, which has a carbon number of 8 or more, which makes the coupler non-diffusible. Also, these dye-forming couplers need only reduce 4 molecules of silver ion in order to form 1 molecule of dye, but they need only reduce 2 molecules of silver ion even if they are 4 equivalence. Either of two equivalence may be used. The dye-forming coupler has a color-correcting effect and is coupled with a colored coupler and an oxidation product of a developing agent to develop a development inhibitor, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a toning agent. , Hardeners, antifoggants, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizing compounds that release photographically useful fragments. Among these, a coupler which releases a development inhibitor with development and improves the sharpness of images and the graininess of images is called a DIR coupler. Instead of the DIR coupler, a DIR compound which releases a development inhibitor at the same time as producing a colorless compound by coupling reaction with an oxidized product of a developing agent may be used.

The DIR coupler and the DIR compound used are those in which the inhibitor is directly bonded to the coupling position, and those in which the inhibitor is bonded to the coupling position via a divalent group and which are separated by the coupling reaction. Intramolecular nucleophilic reaction, intramolecular electron transfer reaction and the like so that the inhibitor is released (referred to as timing DIR coupler and timing DIR compound) are included. Further, as the inhibitor, one that is diffusible after withdrawal and one that is not so diffusible can be used alone or in combination depending on the application.

As the yellow dye-forming coupler, a known acylacetanilide type coupler can be preferably used.
Of these, benzoylacetanilide-based and pivaloylacetanilide-based compounds are advantageous. Specific examples of yellow color forming couplers that can be used include, for example, U.S. Pat.No. 2,875,057.
No. 3,265,506, No. 3,408,194, No. 3,551,15
No. 5, No. 3,582,322, No. 3,725,072, No. 3,891,4
45, West German Patent 1,547,868, West German Application Publication 2,219,917
No. 2,261,361, No. 2,414,006, British Patent No. 1,425,
No. 020, Japanese Patent Publication No. 51-10783, JP-A Nos. 47-26133 and 48-73.
No. 147, No. 50-6341, No. 50-87650, No. 50-123342,
50-130442, 51-21827, 51-102636, 52-8
2424, 52-115219, and 58-95346.

As the magenta dye-forming coupler, known 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, open-chain acylacetonitrile couplers, indazolone couplers and the like can be used.

Specific examples of magenta color forming couplers that can be used include, for example, U.S. Pat.Nos. 2,600,788, 2,983,608, and 3,062,653.
No. 3, No. 3,127,269, No. 3,311,476, No. 3,419,39
1, No. 3,519,429, No. 3,558,319, No. 3,582,3
No. 22, No. 3,615,506, No. 3,834,908, No. 3,891,
445, West German patent 1,810,464, West German patent (OLS) 2,408,6
No. 65, No. 2,417,945, No. 2,418,959, No. 2,424,467
No. 4, Japanese Patent Publication No. 40-6031, Japanese Patent Laid-Open Nos. 49-74027, 49-74028.
No., No. 49-129538, No. 50-60233, No. 50-159336, No.
51-20826, 51-26541, 52-42121, 52-58922
No. 53-55122, Japanese Patent Application No. 55-110943, and the like.

As the cyan dye forming coupler, a phenol or naphthol type coupler is generally used. Specific examples of cyan color forming couplers that can be used include, for example, U.S. Pat.
No. 0, No. 2,474,293, No. 2,801,171, No. 2,895,8
No. 26, No. 3,476,563, No. 3,737,326, No. 3,758,
No. 308, No. 3,893,044, JP-A-47-37425,
50-10135, 50-25228, 50-112038, 50-1174
No. 22, No. 50-130441, etc.,
The couplers described in JP-A-58-98731 are preferred.

Of the dye-forming couplers, colored couplers, DIR couplers, DIR compounds, image stabilizers, antifoggants, UV absorbers, optical brighteners, etc. that do not need to be adsorbed on the silver halide crystal surface, hydrophobic compounds are solid. Various methods such as a dispersion method, a latex dispersion method and an oil-in-water type emulsion dispersion method can be used, which can be appropriately selected according to the chemical structure of the hydrophobic compound such as a coupler. The oil-in-water emulsification dispersion method can be a conventionally known method of dispersing a hydrophobic additive such as a coupler, and usually has a low boiling point of about 150 ° C. or higher and a high boiling point organic solvent, and / or an aqueous solution. Using a dispersing means such as a stirrer, homogenizer, colloid mill, flowgit mixer, ultrasonic device, etc., using a surfactant in a hydrophilic binder such as an aqueous gelatin solution. After emulsifying and dispersing, it may be added to the desired hydrophilic colloid liquid. A step of removing the low boiling point organic solvent may be added at the same time as the dispersion or dispersion.

As a high-boiling-point solvent, phenol derivatives, phthalic acid alkyl esters, phosphoric acid esters, citric acid esters, benzoic acid esters, alkylamides, fatty acid esters, trimesic acid esters, etc. that have a boiling point of 150 ° C or higher that do not react with the oxidized product of the developing agent A solvent is used.

A low boiling or water soluble organic solvent can be used with or in place of the high boiling solvent. Examples of the organic solvent having a low boiling point and substantially insoluble in water include ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform, carbon tetrachloride, nitromethane, nitroethane and benzene.

Dye forming coupler, DIR coupler, Colored coupler, D
When the IR compound, the image stabilizer, the color antifoggant, the ultraviolet absorber, the fluorescent whitening agent and the like have an acid group such as carboxylic acid and sulfonic acid, they can be introduced into the hydrophilic colloid as an alkaline aqueous solution. .

Dissolving a hydrophobic compound in a solvent having a low boiling point solvent alone or in combination with a high boiling point solvent, as a dispersion aid when dispersed in water using mechanical or ultrasonic waves, an anionic surfactant, a nonionic surfactant, Cationic and amphoteric surfactants can be used.

Between the emulsions of the light-sensitive material (same color-sensitive layers and / or different color-sensitive layers), the oxidant of the developing agent or the electron transfer agent moves to cause color turbidity, deterioration of sharpness, and graininess. An antifoggant can be used to prevent the property from being conspicuous.

The color antifoggant may be contained in the emulsion layer itself,
An intermediate layer may be provided between adjacent emulsion layers and contained in the intermediate layer.

An image stabilizer that prevents deterioration of a dye image can be used in the light-sensitive material. Compounds that can be preferably used are those described in VII J of RD 17643.

The hydrophilic colloid layers such as the protective layer and the intermediate layer of the photosensitive material may contain an ultraviolet absorber in order to prevent fogging due to discharge caused by charging of the photosensitive material due to friction and the like and to prevent deterioration of the image by ultraviolet rays. Good.

A formalin scavenger can be used in the light-sensitive material in order to prevent deterioration of the magenta dye-forming coupler and the like due to formalin during storage of the light-sensitive material.

When the hydrophilic colloid layer of the light-sensitive material contains a dye, an ultraviolet absorber or the like, they may be mordanted with a mordant such as a cationic polymer.

To the silver halide emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material, a compound such as a development accelerator and a development retarder which changes the developability and a bleaching accelerator can be added. A compound that can be preferably used as a development accelerator is RD 17643.
No. XX43, Item XXI to No. D, and the development retarder is the compound, No. 17643, Item XXI, Item E. A black and white developing agent and / or its precursor may be used for the purpose of promoting development and other purposes.

The emulsion layer of the photographic light-sensitive material comprises a polyalkylene oxide or a derivative thereof such as an ether, ester or amine, a thioether compound, a thiomorpholine compound, a quaternary ammonium compound or a urethane derivative for the purpose of increasing sensitivity, increasing contrast or promoting development. It may include a urea derivative, an imidazole derivative and the like.

A fluorescent brightening agent can be used in the light-sensitive material for the purpose of emphasizing the whiteness of the white background and making the coloring of the white background inconspicuous. Compounds which can be preferably used as the optical brightening agent are described in RD 17643, item V.

The light-sensitive material may be provided with auxiliary layers such as a filter layer, an antihalation layer and an irradiation prevention layer. In these layers and / or in the emulsion layers, dyes which are bleached or bleached from the light-sensitive material during the development processing may be contained. Examples of such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, and azo dyes.

Reduction of gloss of the light-sensitive material, improvement of writing property on the silver halide emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material,
A matting agent can be added for the purpose of preventing sticking of the photosensitive materials to each other. Any matting agent may be used, for example, silicon dioxide, titanium dioxide, magnesium dioxide, aluminum dioxide, barium sulfate, calcium carbonate, polymers of acrylic acid and methacrylic acid and their esters, polyvinyl resins, polycarbonate and styrene. And the copolymers thereof. The matting agent preferably has a particle size of 0.05 μ to 10 μ. The amount to be added is preferably 1 to 300 mg / m ² .

A lubricant may be added to the light-sensitive material to reduce sliding friction.

An antistatic agent for the purpose of antistatic can be added to the light-sensitive material. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and a protective colloid layer other than the emulsion layer on the side where the emulsion layer is laminated on the emulsion layer and / or the support. May be used for. Antistatic agents preferably used are the compounds described in RD 17643 XIII.

For the photographic emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material, coating property improvement, antistatic property, slipperiness improvement, emulsion dispersion,
Various surfactants can be used for the purpose of preventing adhesion, improving photographic properties (acceleration of development, hardening, sensitization, etc.).

The support used in the light-sensitive material of the present invention includes an α-olefin polymer (for example, polyethylene, polypropylene,
Flexible reflection support such as paper laminated with ethylene / butene copolymer), synthetic paper, etc., semi-synthetic or synthetic polymer such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, polyamide. And a flexible support in which a reflective layer is provided on these films, glass, metal, pottery, and the like.

The photosensitive material is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the surface of the support, if necessary, and then directly or on the surface of the support, antistatic property, dimensional stability, abrasion resistance, hardness,
It may be applied via one or more subbing layers to improve antihalation properties, friction properties, and / or other properties.

At the time of applying the light-sensitive material, a thickener may be used to improve the coatability. For a hardener such as a hardener that causes gelation before coating when it is added to the coating solution in advance because it has a high reactivity, it is recommended to mix it with a static mixer or the like immediately before coating. preferable.

As the coating method, extrusion coating and curtain coating, which can simultaneously coat two or more layers, are particularly useful, but packet coating is also used depending on the purpose. Further, the coating speed can be arbitrarily selected.

The surfactant is not particularly limited, and examples thereof include natural surfactants such as saponin, nonionic surfactants such as alkylene oxide-based, glycerin-based, glycidol-based, higher alkylamines, quaternary ammonium salts, pyridine and the like. Heterocycles, cation surfactants such as phosphonium or sulfonium, carboxylic acids, sulfonic acids,
Anionic surfactants containing an acidic group such as phosphoric acid, sulfuric acid ester, phosphoric acid ester, etc., and amphoteric surfactants such as sulfuric acid or phosphoric acid ester of amino acids, aminosulfonic acids, aminoalcohol may be added. Further, it is also possible to use a fluorine-based surfactant for the same purpose.

To obtain a dye image using the light-sensitive material of the present invention, after exposure,
Perform color photo processing. Color processing includes a color development processing step, a bleaching processing step, a fixing processing step, a water washing processing step and a stabilization processing step if necessary, but instead of a processing step using a bleaching solution and a processing step using a fixing solution. In addition, a bleach-fixing treatment step can be carried out using a 1-bath bleach-fixing solution, or a mono-bath processing step using a 1-bath development bleach-fixing solution capable of performing color development, bleaching and fixing in a single bath. You can also do

In combination with these treatment steps, a pre-hardening treatment step, a neutralizing step thereof, a stop fixing treatment step, a post-hardening treatment step and the like may be performed. In these treatments, instead of the color development treatment step, a color developing agent or its precursor may be contained in the material and an activator treatment step in which the development treatment is carried out with an activator solution may be performed, or the monobath treatment may be performed by an activator. Treatments can be applied. Typical processing is shown below among these processings. (These steps include any one of a washing step, a washing step and a stabilizing step as a final step.) ・ Color development processing step-bleaching step-fixing step-Color development processing step-bleach-fixing step Process-Pre-hardening process-Color development process-Stop fixing process-Water washing process-Bleaching process-Fixing process-Water washing process-Post-hardening process-Color development process-Water washing process-Supplement Color development processing step-Stop processing step-Bleaching processing step-Fixing processing step-Activator processing step-Bleaching fixing processing step-Activator processing step-Bleaching processing step-Fixing processing step-Mono bath processing step The processing temperature is usually 10 ° C. ~ 65 ℃, but 65 ℃
The temperature may be higher than that. It is preferably treated at 25 ° C to 45 ° C.

The color developing solution generally comprises an alkaline aqueous solution containing a color developing agent. The color developing agent is an aromatic primary amine color developing agent, and includes aminophenol-based and p-phenylenediamine-based derivatives. These color developing agents can be used as salts of organic acids and inorganic acids, for example, salt acid, sulfate, p-toluenesulfonate, sulfite, oxalate, benzenesulfonate and the like. it can.

These compounds generally account for about 0.1 for Color Developer 1.
It is used in a concentration of .about.30 g, more preferably in a concentration of about 1 to 15 g for color developer 1. If the amount added is less than 0.1 g, sufficient color density cannot be obtained.

Examples of the aminophenol-based developer include o-aminophenol, p-aminophenol, 5-amino-
2-oxy-toluene, 2-amino-3-oxy-toluene, 2-oxy-3-amino-1,4-dimethyl-benzene and the like are included.

Particularly useful primary aromatic amine color developing agents are N, N'-
A dialkyl-p-phenylenediamine compound,
The alkyl and phenyl groups may or may not be substituted. Among them, examples of particularly useful compounds include N-N'-dimethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N, N'-dimethyl-p-phenylenediamine hydrochloride, 2- Amino-5- (N-ethyl-N-dodecylamino) -toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β-hydroxy Ethylaminoaniline, 4-amino-3-methyl-N, N'-diethylaniline, 4-amino-N- (2-methoxyethyl) -N-
Examples thereof include ethyl-3-methylaniline-p-toluenesulfonate.

The color developing agents may be used alone or in combination of two or more kinds. Furthermore, the color developing agent may be incorporated in a color photographic material. In this case, it is also possible to treat the silver halide color photographic light-sensitive material with an alkaline solution (activator solution) instead of the color developing solution,
Immediately after the alkaline solution treatment, a bleach-fixing treatment is carried out.

The color developing solution used in the present invention may contain an alkaline agent usually used in a developing solution, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate or borax. And various additives such as benzyl alcohol, alkali metal halides such as potassium bromide or potassium chloride, or a development modifier such as citrazinic acid, and a preservative such as hydroxylamine or sulfite. You may. Further, various antifoaming agents and surfactants, and an organic solvent such as methanol, dimethylformamide or dimethylsulfoxide, etc. may be appropriately contained.

The pH of the color developer used in the present invention is usually 7 or higher, preferably about 9-13.

In the color developing solution used in the present invention, if necessary, diethylhydroxyamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, an aromatic secondary alcohol, hydroxamic acid, bentose or an antioxidant is used. Hexose, pyrogallol-1,3
-Dimethyl ether and the like may be contained.

In the color developing solution used in the present invention, various chelating agents can be used together as a sequestering agent. For example, as the chelating agent, an amine polycarboxylic acid such as ethylenediaminetetraacetic acid or diethylenetriaminopentaacetic acid, 1
-Organophosphonic acid such as hydroxyethylidene-1,1'-diphosphonic acid, aminopolyphosphonic acid such as aminotri (methylenephosphonic acid) or ethylenediaminetetraphosphoric acid, oxycarboxylic acid such as citric acid or gluconic acid, 2-phosphonobutane-1 Examples thereof include phosphonocarboxylic acids such as 2,2,4-tricarboxylic acid, polyphosphoric acids such as tripolyphosphoric acid and hexametaphosphoric acid, and polyhydroxy compounds.

The bleaching process may be performed simultaneously with the fixing process as described above, or may be performed individually. As the bleaching agent, a metal complex salt of an organic acid is used, and for example, an organic acid such as polycarboxylic acid, aminopolycarboxylic acid or oxalic acid, citric acid, etc., in which metal ions such as iron, cobalt, copper are coordinated are used. . Among the above-mentioned organic acids, the most preferable organic acid is polycarboxylic acid or aminopolycarboxylic acid. Specific examples of these include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N- (β-oxyethyl) -N, N ′, N ′.
-Triacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, dihydroxyethylglycine citric acid (or tartaric acid), ethyletherdiaminetetraacetic acid, glycoletherdiaminetetraacetic acid, ethylenediaminetetrapropionic acid, phenylenediamine Tetraacetic acid etc. can be mentioned.

These polycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

These bleaching agents are 5-450 g / l, more preferably 20-250 g
Use with / l.

As the bleaching solution, in addition to the bleaching agent as described above, a solution having a composition containing sulfite as a preservative is applied if necessary.
Further, it may be a bleaching solution having a composition containing an ethylenediaminetetraacetic acid iron (III) complex salt bleaching agent and adding a large amount of a halide such as ammonium bromide. As the halide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. may be used in addition to ammonium bromide. it can.

The bleaching solution used in the present invention includes JP-A-46-280, JP-B-45-8506, 46-556, and Belgian Patent No. 770,910,
Various bleaching accelerators described in JP-B-45-8836, JP-B-53-9854, JP-A-54-71634 and JP-A-49-42349 can be added.

The bleaching solution is used at a pH of 2.0 or higher, but generally 4.0 to 9.
Used in 5, preferably used in 4.5-8.0, most preferably 5.0-7.0.

The fixer may have a commonly used composition. As the fixing agent, a compound which reacts with a silver halide to form a water-soluble complex salt as used in a usual fixing process, for example, thiosulfate such as potassium thiosulfate, sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate. Typical examples thereof include thiocyanates such as sodium thiocyanate and ammonium thiocyanate, thiourea and thioether. These fixatives
5g / l or more, used in an amount that can be dissolved, but generally
Use at 70-250g / l. A part of the fixing agent can be contained in the bleaching tank, and conversely, a part of the bleaching agent can be contained in the fixing tank.

The bleaching solution and / or the fixing solution are various pH buffers such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide. The agents can be contained alone or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents or surfactants may be contained. Further, hydroxylamine, hydrazine, preservatives such as bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids or stabilizers such as nitroalcohol and nitrates, hardening agents such as water-soluble aluminum salts, methanol,
An organic solvent such as dimethyl sulfamide or dimethyl sulfoxide can be appropriately contained.

The fixer is used at a pH of 3.0 or above, but generally 4.5-10
Is used, preferably 5 to 9.5, and most preferably 6 to 9.

Examples of the bleaching agent used in the bleach-fixing solution include the metal complex salts of organic acids described in the bleaching treatment step, and preferable compounds and concentrations in the processing solution are the same as in the bleaching treatment step.

As the bleach-fixing solution, a solution having a composition containing a silver halide fixing agent in addition to the above-mentioned bleaching agent and, if necessary, a sulfite as a preservative is applied. In addition, a bleach-fixing solution having a composition in which a small amount of a halogenide such as ammonium bromide other than the above-mentioned silver halide fixing agent and an ethylenediaminetetraacetic acid iron (III) complex bleaching agent is added, or conversely, a halogenating agent such as ammonium bromide is used. A bleach-fixing solution having a composition containing a large amount of a halide, and a special bleach-fixing solution having a composition comprising a combination of an ethylenediaminetetraacetic acid iron (III) complex bleaching agent and a large amount of a halide such as ammonium bromide are used. I can do things. Examples of the halide include hydrochloric acid, hydrobromic acid, in addition to ammonium bromide,
Lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide and the like can also be used.

Examples of the silver halide fixing agent that can be contained in the bleach-fixing solution include the fixing agents described in the fixing processing step. The concentration of the fixing agent, the pH buffer which can be contained in the bleach-fixing solution, and other additives are the same as those in the fixing processing step.

The pH of the bleach-fix solution is 4.0 or higher, but it is generally 5.0.
~ 9.5, preferably 6.0-8.5, most preferably 6.5-8.5.

[Examples] Specific examples of the present invention will be described below, but embodiments of the present invention are not limited thereto.

In all the following examples, the addition amount in the silver halide photographic light-sensitive material is per 1 m ² unless otherwise specified. Also, silver halide and colloidal silver are shown in terms of silver.

[Example-1] A multi-layer color photographic element sample 1 was prepared by sequentially forming each layer having the composition shown below from the support side on a triacetyl cellulose roll support.

Sample-1 (Comparative) First layer: Antihalation layer (HC-1) Gelatin layer containing black colloidal silver.

Second layer: intermediate layer (I.L.) A gelatin layer containing an emulsified dispersion of 2,5-di-t-octylhydroquinone.

Third layer; low-sensitivity red-sensitive silver halide emulsion layer (RL-1) Monodisperse emulsion (Emulsion I) consisting of AgBrI with average grain size () 0.30 μm and AgI 6 mol%. m ² Sensitizing dye I: 6 × 10 ^-5 mol per mol of silver Sensitizing dye II: 1.0 × 10 ^-5 mol per mol of silver Cyan coupler (C-1): 1 mol of silver To 0.06 moles Colored cyan coupler (CC-1) ...... to 1 mole of silver
0.003 mol DIR compound (D-1): 0.0015 mol per 1 mol of silver Fourth layer: High-sensitivity red-sensitive silver halide emulsion layer (RH-1) Emulsion shown in Table-1: Silver coating amount: 1.3 g / m ² Sensitizing dye I: 3 × 10 ^-5 mol per mol of silver Sensitizing dye II: 1.0 × 10 ^-5 mol per mol of silver Cyan coupler (C-1): 1 silver 0.02 moles per mole Colored cyan coupler (CC-1) ... per 1 mole silver
0.0015 mol DIR compound (D-2) ... 0.001 mol per mol of silver Fifth layer; Intermediate layer (IL) The same gelatin layer as the second layer.

Fig. 6 Layer; Low-sensitivity green-sensitive silver halide emulsion layer (GL-1) Emulsion-I ... Coating amount of silver 1.5 g / m ² Sensitizing dye III: 2.5 × 10 ^-5 mol per 1 mol of silver Sensitizing dye IV: 1.2 × 10 ^-5 mol / mol silver Magenta coupler (M-1): 0.0050 / mol silver
Molar Colored magenta coupler (CM-1): 0.009 mol per mol of silver DIR compound (D-1): 0.0010 mol per mol of silver DIR compound (D-3): relative to 1 mol of silver 0.0030 mol 7th layer; high-sensitivity green-sensitive silver halide emulsion layer (GH-1) Emulsion-II ... coating amount of silver 1.4 g / m ² sensitizing dye III: 1.5 × 10 ⁻ per mol of silver ⁵ mol Sensitizing dye IV: 1.0 × 10 ^-5 mol for 1 mol of silver Magenta coupler (M-1): 0.020 mol for 1 mol of silver Colored magenta coupler (CM-1): 1 mol of silver 0.002 mol of DIR compound (D-3) ... 0.0010 mol per mol of silver 8th layer; yellow filter layer (YC-1) of yellow colloidal silver and 2,5-di-t-octylhydroquinone A gelatin layer containing an emulsified dispersion.

Layer 9: Low-sensitivity blue-sensitive silver halide emulsion layer (BL-1) Monodisperse emulsion consisting of AgBrI with an average grain size of 0.48 μm and 6 mol% of AgI (Emulsion III) ...... Silver coating amount increased by 0.9 g / m ² Sensitizing dye V: 1.3 × 10 ^-5 mol per 1 mol of silver Yellow coupler (Y-1): 0.29 mol per 1 mol of silver 10th layer: High-sensitivity blue-sensitive emulsion layer (BH-1) Average Monodisperse emulsion consisting of AgBiI containing 0.8 μm grain size and 15 mol% AgI (Emulsion IV) …… Silver coating amount 0.5 g / m ² Sensitizing dye V …… 1.0 × 10 ^-5 mol yellow silver coupler to 1 mol silver (Y-1) ... 0.08 mol per mol of silver DIR compound (D-2) ... 0.0015 mol per mol of silver 11th layer; 1st protective layer (Pro-1) Silver iodobromide ( AgI 1 mol% average particle size 0.07 μm) Silver coating amount 0.5 g / m ² Gelatin layer containing UV absorbers UV-1 and UV-2.

12th layer: 2nd protective layer (Pro-2) Gelatin layer containing polymethylmethacrylate particles (direct diameter 1.5 μm) and formalin cavenger (HS-1) In addition to the above composition, each layer contains a gelatin hardening agent. (H-1)
And surfactants were added.

The compounds contained in each layer of Sample 1 are as follows.

Sensitizing dye I; Anhydro 5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) thiacarbocyanine hydroxide Sensitizing dye II; Anhydro 9-ethyl-3,3'-di -(3-Sulfopropyl) -4,5,4 ', 5'-dibenzothiacarbocyanine hydroxide Sensitizing dye III; Anhydro 5,5'-diphenyl-9-ethyl-3,3'-di- (3 -Sulfopropyl) oxacarbocyanine hydroxide Sensitizing dye IV; Anhydro 9-ethyl-3,3'-di- (3-sulfopropyl) -5,6,5 ', 6'-dibenzoxacarbocyanine hydroxide Sensitizing dye V: anhydro 3,3'-di- (3-sulfopropyl) -4,5-benz-5'-methoxythiacyanine The emulsion used in the fourth layer was prepared by a known method so that the average grain size, the AgI content in the central portion and the asvect ratio shown in Table 1 were obtained.

Using the emulsions shown in Table 1, the red absorbing non-diffusible dye of the present invention was further added to the fifth layer or the twelfth layer, and as shown in Table 2, Sample No. 1 to Sample No. 10 It was created.

Each of the sample Nos. 1 to 10 thus prepared was subjected to wedge exposure using white light and then subjected to the following development processing.

Treatment process (38 ℃) Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Water washing 3 minutes 15 seconds Fixing 6 minutes 30 seconds Water washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Dry Used in each processing step The composition of the treatment liquid is as follows.

[Color developer] 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) -aniline ・ sulfate 4.75g anhydrous sodium sulfite 4.25g hydroxylamine ・ 1/2 sulfate 2.0g anhydrous potassium carbonate 37.5g Sodium bromide 1.3g Nitrilotriacetic acid.3 sodium salt (monohydrate) 2.5g Potassium hydroxide 1.0g Add water to make 1.

[Bleach] Ethylenediaminetetraacetic acid iron ammonium salt 100.0g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid 10.0ml Add water and adjust to pH = 6.0 using ammonia water.

[Fixing solution] Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Add water to make 1 and adjust the pH to 6.0 with acetic acid.

[Stabilizer] Formalin (37% aqueous solution) 1.5 ml Conidax (Konishi Rokusha Kogyo Co., Ltd.) 7.5 ml Add water to make 1.

Next, the sensitivity and sharpness of the color images formed on the above samples were measured. The results are shown in Table 3.

The sensitivity indicates a relative value with the sensitivity value of the cyan image of Sample 1 exposed to white as 100, and the image sharpness is evaluated by MTF (Modulation Transfer Function).
This was done by determining the spatial frequency of%. The higher the spatial frequency, the better the sharpness.
The results are shown in Table 3.

As is clear from Table 3, the samples of the present invention show a small decrease in sensitivity and a marked improvement in sharpness.

Example-2 The seventh layer of Sample No.1 of Example-1 was changed to the emulsion shown in the first layer, and the non-diffusible green absorbing dye of the present invention was further added to the twelfth layer.
Or a sample as shown in Table 4 added to the 8th layer
No.11 to NO.19 were created.

The samples 11 to 19 prepared in this manner were used as examples-
The relative sensitivity and MTF of the green photosensitive layer were measured in the same manner as in 1.

As is clear from Table 5, the samples of the present invention show a small decrease in sensitivity and a marked improvement in sharpness.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP 61-285445 (JP, A) JP 62-32448 (JP, A) JP 62-75436 (JP, A) JP 61- 292636 (JP, A) JP 61-295550 (JP, A) JP 62-47640 (JP, A)

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer and at least one non-light-sensitive hydrophilic colloid layer on a support, at least one layer of said silver halide emulsion layer. Containing a silver halide emulsion having an average aspect ratio of 5: 1 or more, in which silver iodide is localized, and at least one layer of the non-photosensitive hydrophilic colloid layer contains a non-diffusible red absorbing dye and / or
Alternatively, a silver halide color photographic light-sensitive material containing a non-diffusible green absorbing dye.