JPS59129849A - Silver halide color photosensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled material high in sensitivity and good in sharpness and color reproducibility by incorporating silver halide particles specified in diameter in silver halide emulsion multilayers on a support and a DIR coupler having a specified diffusivity value of the development inhibitor also in them. CONSTITUTION:A silver halide color photosensitive material is prepared by incorporating flat silver halide particles having particle diameter >= five times the thickness and at least one of DIR couplers, such as compds. of formula I and II, and having 0.4-0.95 diffusivity of its releasable development inhibitor, in at least one of multilayer silver halide emulsion layers coating a support. The combination of the DIR coupler having the development inhibitor having such a high diffusivity as a releasable group makes it possible to attain a sufficient multilayer effect and sharpness even when flat particles are used.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material, and particularly to a multilayer silver halide color photographic light-sensitive material for photographing, which is highly sensitive and has improved sharpness and color reproducibility.

As electronics technology has advanced in recent years, there is a growing possibility that it will expand into the field of photography.

For this reason, there is an urgent need for the conventional conventional photography system to further develop its advantages of high sensitivity and high image quality, which are its major characteristics, and to secure its position.

Regarding high sensitivity / ASA-≠o in 976.

Since the release of color films, there has been a desire to develop color 4 true light-sensitive materials with even higher sensitivity and better image quality.

In general, sensitivity increases as the grain size of a silver halide emulsion becomes thicker, but once the grain size exceeds a certain level, sensitivity generally does not increase even if the grain size is increased.

In addition, even if the amount of spreading silver is increased, the sensitivity generally increases, but as a result of the increased light scattering by the coated silver halide, it has the negative effect of deteriorating the sharpness and has the major disadvantage of increasing the product cost. .

Therefore, as a result of our intensive search for a method to increase sensitivity without increasing the amount of coated silver, we found that for light in the red and green spectral regions, we increased the surface area of the emulsion.
It has been found that increasing the amount of sensitizing dye adsorbed per unit volume of emulsion is effective in increasing sensitivity. In order to increase the surface area of the emulsion, it is preferable to form the emulsion into a flat plate.

The tabular emulsion can be realized by the method described in Japanese Patent Application No. 1987-///''7!i.

However, it has become clear that the use of these tabular silver halide emulsion grains has the drawbacks of decreasing the multilayer effect, which is important for improving image quality, and deteriorating sharpness and color reproduction. As a result of various analyzes to overcome this drawback, we found that the reduction in the interlayer effect is due to the fact that the development inhibitors that have diffused from other layers are more adsorbed on the tabular grains than on the energized emulsion grains. It was concluded that the diffusion of development inhibiting substances in the film is substantially reduced when tabular grains are used.

From this, it has been considered to use a so-called DIR compound that releases a diffusive development inhibitor imagewise.

The only DIR compound known so far is U.S. Patent No.
27! j'1 No. 370/7za No. 3, No. 36/! r!
Compounds described in Japanese Patent Publication No. 06, No. 36/722, etc., and further improved versions of these compounds, published in Japanese Patent Publication No. 6J-3
The compound described in 'Lili No. 33 is known.

However, when tabular grains were used with the DIR compound Kaneko described in these, sufficient multilayer effect and sharpness improvement were not achieved.

However, when a highly diffusible development inhibitor used in the present invention is combined with a DIR coupler having a leaving group, sufficient multilayer effect and sharpness can be obtained even when tabular grains are used.

A development inhibitor containing tabular silver halide grains having a grain size of 5 times or more the grain thickness in at least one layer of a multilayer silver halide emulsion layer coated on a support, and which is a leaving group for a DIR coupler. The object of the present invention can be achieved by containing at least one DIR coupler whose diffusivity is O3≠ or more and O1 or less. The diffusivity of the development inhibitor in the present invention was evaluated by the following method.

A multilayer color photosensitive material having the following composition was prepared on a transparent support and designated as sample B.

1st layer: red-sensitive silver halide emulsion layer Silver iodobromide emulsion (silver iodide I mole %, average size O.

μJK lol The amount of sensitizing dye 1 of Example 1 per mole of silver is X/
A gelatin coating solution containing 0 mole of red-sensitized emulsion and Katzler F per mole of silver was applied, and the amount of silver was /.

♂9/m VCfx (film thickness λμ
Katzler F 1st layer: Silver iodobromide emulsion (non-red color) used in the 7th layer polymethyl methacrylate grains (diameter approximately 1).

5μ) containing gelatin layer (applied silver amount 2g/m2, film thickness/
In addition to the above-mentioned composition, each layer contains a gelatin hardening agent and a surfactant.

Sample A does not contain the silver iodobromide emulsion of the second layer of sample B,
A photosensitive material having the same structure as Sample B except for this was prepared.

After the obtained samples A and B'i wedge exposure, the total development time was 2
Processing recipe of Example/except that the time is 10 seconds). Processed according to. The developer contains a development inhibitor at a concentration of 1 for sample A.
/, was added until it decreased to 2. The degree of density reduction of sample B at this time was used as a measure of the diffusivity in the silver halide emulsion film.

Table 1 shows the results of measurements of typical development inhibitors using the method of the present invention.

A DIR coupler that can release a highly diffusive development inhibitor with a diffusivity of 0.1.1 or more (hereinafter simply referred to as a diffusive DIR coupler)
coupler) is represented by the following general formula.

/) General formula (L) ANY)m The person in the formula represents a coupler component, m represents/or , and Y is bonded to the coupling position of the coupler component A and reacts with the oxidized product of the color developing agent. It represents a highly diffusible development inhibitor or a compound capable of releasing a development inhibitor with a group that leaves off.

A only needs to have the properties of a cazole and does not necessarily need to be coupled to form a dye.

-2 In general formula (1), Y is represented by the following general formula 1ll) to (
V).

General formula (I) General formula (IV) 2 General formula (VI 3 - General formula (nA) - (II B)
VC oil Rfd alkyl group, alkoxy group, anruami 7 group, halogen atom, alkoxycarbonyl group, thiazolylideneamino group, aryloxycarbonyl group, acyloxy group, carbamoyl group, N-alkylcarbamoyl group, ~, N-dialkylcarbamoyl group, nitro group, amino group, he-arylcarbamoyloxy group, sulfamoyl group, he-alkylcarbamoyloxy group, hydroxy group, alkoxycarbonylamino group, alkylthio group, arylthio group, aryl group, heterocyclic group, cyano group , an alkylsulfonyl group also represents a cyclonylamino group. General formula (IIA)-I
In IIBI and (I[), n represents li or 2, when n is 2, Ro may be the same or different, and the total number of carbons contained in n R1 is θ ~ io, In general formula (IV), R2 represents an alkyl group, an aryl group or a heterocyclic group.

In general formula (V), R3 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and R4 represents a hydrogen atom, an alkyl group, an aryl group, a halogen atom, an acylamino group, an alkoxycarbonylamino group. group, aryloxycarbonylamino group, acansulfonamide group, cyano group, heterocyclic group, alkylthio group, or amino group.

When R1, R2, R3 or R4 represents an alkyl group, it may be substituted or unsubstituted, thin or cyclic. Substituents include halogen atom, nitro group, cyano group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group,
Examples include sulfamoyl group, carbamoyl group, hydroxy group, alkanesulfonyl group, arylsulfonyl group, alkylthio group, and arylthio group.

When Ro, R2, R3 or R4 represents an aryl group, the aryl group may be substituted.

Substituents include alkyl groups, alkenyl groups, alkoxy groups, alkoxycarbonyl groups, halogen atoms, nitro groups, amino groups, sulfamoyl groups, hydroxy groups, carbamoyl groups, aryloxycarbonylamino groups, alkoxycarbonylamino groups, acylamino groups, and cyanogen groups. group or ureido group.

When R1, R2, R3 or R4 represents a heterocyclic group, it represents a J-membered or 6-membered monocyclic ring or a 7-membered ring or a fused ring containing a nitrogen atom, an oxygen atom, or a sulfur atom as a heteroatom; Zyl group, quinolyl group, furyl group, benzothiazolyl group, oxazolyl group, imidazolyl group, thiazo 1
Nor group, triazol-11l group, pensitriazol-l) group,
These are selected from imido groups, oxazine groups, etc., and may be further substituted with the substituents listed above for the III-l group.

In the general formula (IV), the number of carbon atoms contained in R2 is 7 to
/6.

In the general formula (v), the total number of carbon atoms contained in R3 and R4 is 7 to 15.

3) In general formula (1), Y represents the following general formula (Vl).

General formula (V[) -TIME-INHIBIT In the formula, the TIME group is a group that is bonded to the cup II ring position of the coupler and can be cleaved by reaction with a color developing agent. It is a group that can be used with a moderate amount of control.

The INHIBIT group is a development inhibitor.

4t) General formula (■ -TIME-IN) IIB
The IT group is represented by the following general formulas (■) to (Xlll)'t-.

General formula (■) General formula (■) CH2-INHIBIT General formula (■) (R5)l C)] 2-INHIBIT General formula (XI) General formula (X[[) General formula (Xlll) 〇General formula (■ ) ~ (R5 in tumor is a hydrogen atom, a haloken atom, an argyl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkanesulfonyl group, an acylamino group, a ureido group, a cyano group, a nitro group, a sulfonamide group) represents a group, sulfamoyl group, carbamoyl group, aryl group, carboxy group, sulfo group, hydroxy group, alkanesulfonyl group, and has the general formulas (■), (■), (IX), (XI, l and (
In X[lI), l represents 1 or 2, and in the general formulas (■n, (Xl), (Xll) and (Ml), k represents an integer from O to 1, and the general formulas (■), (X) and (M), R6 represents an alkyl group, an alkenyl group, an aralkyl group, a cycloalkyl group, or an aryl group, and in general formulas (M) and (X[lI), Bil'' is an oxygen atom or -N
-(R6 has the same meaning as 6 as defined above), and the INHIBIT group has the general formula (IIA) -(DB), (1
), (1'V) and (V) have the same meanings except for the number of carbon atoms.

However, in the general formulas (IIA)-(JIB) and (111), the total number of carbons contained in each R□ in the -molecule is 1 to Ju, and in the general formula (IV'), R2
The number of carbons contained in is / to 32, general formula (v)
In this case, the total number of carbon atoms contained in R3 and R4 is 1 to 32.

When R5 and R6 represent an alkyl group, they may be substituted or unsubstituted, linear, or cyclic. Examples of the substituent include the substituents listed when R1 to R4 are alkyl groups.

When R5 and R6 represent an aryl group, the aryl group may be substituted. Examples of the substituent include the substituents listed when R□ to R4 are aryl groups.

Among the above diffusible DIR compounds, general formula (IIA)-
Particularly preferred are those having a leaving group ranging from (JIB) to mV).

s) Yellow image forming coupler residues represented by A include piparoylacetanilide type, benzoylacetanilide type, malondiester type, malondiamide type, dibenzoylmethane type, benzothiazolylacetamide type, malone ester monoamide type, benzothiazo 11
Coupler residues of the benzimidazo IJ-ruacetamide type, benzimidazo IJ-ruacetamide type, benzimidazo-IJ-ruacetamide type, benzoxazolyl acetate type, benzoxazolyl]ruadoamide type, benzoxazolyl acetate type, malon diester type, benzimidazo IJ-ruacetamide type, U.S. Pat. Coupler residues derived from heterocyclic-substituted acetamides or hetero-it-substituted acetates contained in R.H./, No. 110 or US Pat. No. 3,770.

Hirohiro No. 6, British Patent I, ≠ Jri, No. 777, West German Patent No. 1
0LS)2. so3. o9y, Japanese published patent jθ-
/3, No. 73Ir or a coupler residue derived from the acylacetamides described in Research Disclosure No. 6737, or U.S. Patent No. θμ6,674
Examples include the heterocyclic coupler residues described in item '.

As the magenta color image-forming coupler residue represented by A, 7
is j-oxocobyrazoline nucleus, pyrazolo-[i
r s-a ] Coupler residues having a benzimidazole core or a cyanacetophenone type coupler residue are preferred.

The cyan image-forming coupler residue 5 represented by A is preferably a coupler residue having a phenol nucleus or an α-naphthol nucleus.

Moreover, even if the coupler does not optically form a dye after coupling with the oxidized form of the developing agent and releasing the two development inhibitors, it is still as effective as a DIR coupler. A
This deaf coupler residue represented by U.S. Pat. ．． 2/J issue, Pl≠.

011.4L9/No. 3.63. z, tqj issue, same 3
．． 95, 9y-ts or same 3. Examples include the coupler residues described in Ri-Otsu/Ri-5ri issues.

j) In general formula (1), A is general formula (IAI, (II
A), (F A ), (yA), (VA, l, (VIA
), (■A) and (■A).

General formula (IAl 0 ]111 General formula (IIA,) 0 111 R1□-C-C) I-C-NH-R12 general formula (1 person) 0 111 R13-NH-(,nee CH-U-N)1-R Eng.

■ General formula (IV'A) Summer 15 General formula (VA) General formula (V[A) General formula (■A) General formula (■A) General formula (X[A) In the formula, R, aliphatic group , an aromatic group, an alkoxy group or a heterocyclic group, and R□2 and R□3 each represent an aromatic group or a heterocyclic group.

In the formula, the aliphatic group represented by R1□ preferably has 7 to 22 carbon atoms, is substituted or unsubstituted, linear or cyclic,
It may be either. Preferred substituents for the alkyl group include an alkoxy group, an aryloxy group, an amine group, an acylamino group, and a haloken atom, which may themselves have further substituents. Specific examples of aliphatic groups useful as R are: isopropyl, isobutyl, tert-butyl, inamyl,
tert-amyl group, /, l-dimethylbutyl group, /, /-dimethylhexyl group, /, /-diethylhexyl group, dodecyl group, hegisadecyl group, octadecyl group, cyclohexyl group, comethoxyimbrobyl group, cof Enoxyisoprobyl group, 2-p tert
-butylphenoxyisopropyl group, α-aminoisopropyl group, α-(diethylamino)isopropyl group, α
-(succinimido)inpropyl group, α-(phthalimido)isopropyl group, α-(benzenesulfonamido)isopropyl group, and the like.

When R□□, R12 or R represents an aromatic group (particularly a phenyl group), the aromatic group may be substituted. Aromatic groups such as phenyl groups include alkyl groups having 32 or less carbon atoms, alkenyl groups, alkoxy groups, alkoxycarbonyl groups, alkoxycarbonylamino groups, aliphatic amide groups, alkylsulfamoyl groups, alkylsulfonamide groups, and alkylureido groups. , an argyl-substituted succinimide group, etc., and in this case, the alkyl group may have an aromatic group such as phenylene interposed in the button. The phenyl group may also be substituted with an aryloxy group, an alkylthiocarbonyl group, an arylcarbamoyl group, an arylamido group, an arylsulfamoyl group, an arylsulfonamide group, an arylureido group, etc., and the aryl group of these substituents The total number of carbon atoms in the part is /~22
may be substituted with one or more alkyl groups.

The phenyl group represented by R11, R□2 or R13 further includes an amino group, including one substituted with a lower alkyl group having 7 to 7 carbon atoms, a hydroxy group, a carboxy group, a sulfo group, a nitro group, a cyano group, It may be substituted with a thiocyano group or a halogen atom.

RR or R□3 is a substituent in which a phenyl 11' 12 group is fused with another ring, such as a naphthyl group, a quinolyl group, an isopropyl group, a chromanyl group, a 1-maranyl group, and a tetrahydronaphthyl M'lfc Table bL.

It's okay. These substituents may themselves have further substituents.

When R□□ represents an alkoxy group, the alkyl moiety represents a linear or branched alkyl group, alkenyl group, cyclic furkyl group, or cyclic alkenyl group having carbon atoms of 1 to 4AO1, preferably 1 to λ, These may be substituted with a halogen atom, an aryl group, an alkoxy group, or the like.

When R□□, R1□ or R□3 represents a heterocyclic group, each heterocyclic group is a carbon atom of the carbonyl group of the acyl group in the alpha acylacetamide. Or it bonds with the nitrogen atom of the amide group. Such heterocycles include thiophene, furan,
Examples include bilane, virol, pyrazole, bizine, pyrazine, pyrimidine, pizine, indolizine, imidazole, thiazole, oxazole, triazine, thiadiazine, and oxazine. These may further have a substituent on the ring.

In the general formula [IVA:], RXS represents a linear or branched alkyl group having from 0 carbon atoms, preferably 1 to 22 carbon atoms (for example, methyl, isopropyl, tert-butyl, hexyl, dodecyl group, etc.), alkenyl groups (e.g., allyl group, etc.), cyclic alkyl groups (e.g., cyclopentyl group, cyclohexyl group, norbornyl group), aralkyl groups (e.g., evabenzyl, β-phenylethyl xa, etc.), cyclic alkenyl groups (e.g., cyclopentenyl, cyclohexenyl) It represents a group such as a halogen atom, a nitro group, a cyan group, an aryl group, an alkoxy group, an aryloxy group, a carboxyl group, an alkylthiocarbonyl group, a1]-ruthiocarbonyl group, an alkoxycarbonyl group, Aryloxycarbonyl group, sulfo group, sulfamoyl group, carbamoyl group, acylamino group, diacylamino group, ureido group, urethane group, thiourethane group, sulfonamide group, heterocyclic group, a1]-lsulfonyl group, alkylsulfonyl group , an arylthio group, an alkylthio group, an argylamine group, a dialkylamino group, anilino group, an N-arylayu11no group, a he-acylanilino group, a heacylanilino group, a hydroxy group, a mercapto group, or the like.

Furthermore, R15 may represent an aryl group (eg, phenyl group, α- or β-naphthyl group, etc.). The aryl group may have one or more substituents, such as an alkyl group, an alkenyl group, a cyclic alkyl group,
Aralkyl group, cyclic alknyl group, halogen atom, nitro group, cyano group, aryl group, alkoxy group, aryloxy group, carboxy group, alkoxycarbonyl group, iri-oxycarbonyl group, sulfo group, sulfamoyl group, carbamoyl group, Acylamino group, diacylamino group, ureido group, urethane group, sulfonamide group, heterocyclic group, arylsulfonyl group, alkylsulfonyl group,
Ori-ruthio group, alkylthio group, alkylamino group,
It may have a dialkylamino group, anilino group, healkylanilino group, N-7lylanilino group, N-acylanilino group, hydroxy group, mercapto group, etc. R
□ 5 is a phenyl in which at least one ortho position is substituted with an alkyl group, an alkoxy group, a halogen atom, etc. This is because the coupler remaining in the film does not change color due to light or heat. It is useful because there are few.

Furthermore, R15 is a heterocyclic group (for example, a j-membered or 6-membered heterocyclic group containing a nitrogen atom, an oxygen atom, or a sulfur atom as a hetero atom, a fused heterocyclic group, a pyridyl group, a quinol group,
furyl group, benzothiazol group, oxasilyl group, imidazol group, naphthoxacylyl group, etc.), heterocyclic groups substituted with the substituents listed for the above-mentioned 711-l group, aliphatic or aromatic acyl group, alkylsulfonyl group, arylsulfonyl group, alkylcarbamoyl group, 71J-carbamoyl group, alkylthio group
Lt may represent a hamoyl group or a1]-ruthiocarbamoyl group.

In the formula, R□4 is a hydrogen atom, a straight chain or branched alkyl, alkenyl, cyclic alkyl, aralkyl, cyclic alknyl group having 7 to 7 carbon atoms, preferably 1 to 2λ (
These groups may have the substituents listed for R□5 above), a1)-al groups and heterocyclic groups (which may have the substituents listed for R□5 above) , alkoxycarbonyl group (e.g. methogylcarbonyl group,
Ethoxycarbonyl group, stearylcarbonyl group, etc., aryloxycarbonyl M (e.g., tld phenoxycarbonyl group, naphthogylcarbonyl group, etc.)
, aralkyloxycarbonyl group (for example, penzyloxycarbonyl group), alkoxy group (e.g., methoxy group, ethosoxy group, heptadecyloxy group, etc.), aryl
alkylthio groups (e.g., ethylthio group, dodecyloxy group, etc.),
J, arylthio M (e.g., phenylthio group, α-naphthylthio group, etc.), carboxy group, acylamino group (e.g., acetylamino group, J-C(co), etc./thio group).

≠-tert-amylphenogyl)acetamide]
benzamide group, etc.), diacylamino group, N-argylacylamino group (e.g., N-methylpropionamide group, N-7 lylacyl 7+/amine group (e.g. N-phenylacetamide group, etc.), Ureido groups (e.g. ureido, hairylureido, N-alkylureido,
/ido group, etc.), urethane group, thiourethane group, arylamino group (e.g., phenylamino, N-methylamino group, diphenylamine group, heacetylanilino group, cochloroj-tetradecanamideanilino group, etc.),
Argylamino groups (e.g., l-butylamino group, methylamino group, cyclohexylamino group, etc.), cycloamino groups (e.g., λ piperidino group, pyro-11dino group, etc.),
Heterocyclic amino group (e.g. Oba≠-biII dylamino group, 2-
benzoxacylylamino group), alkylcarbonyl group (for example, hamethyl carbonyl group, etc.), sulfonamide group (for example, argylsulfonamide group, Arylsulfonamide group), carbamoyl group (for example, ethylcarbamoyl group, dimethylcarbamoyl group, N
-methyl-phenylcarbamoyl, hephenylcarpamoyl), sulfamoyl groups (e.g. N-alkylsulfamoyl, N,N-sialgylsulfamoyl, N-irisulfamoyl, IN,N-,furgyl-) -A IJ-Rusulfamoi kM, N, N-Sia) I
-Rusulfamoyl group represents any one of a cyano group, a hydroxy group, a mercapto group, a halogen atom, and a sulfo group.

In the formula, R1□ is a hydrogen atom or a linear or branched alkyl group having from 32 carbon atoms, preferably from / to 22 carbon atoms,
It represents an alkenyl group, a cyclic alkyl group, an aralkyl group, or a cyclic alkenyl group, and these may represent the substituents listed for R□5 above, or R□7 may represent an 17-al group or a heterocyclic group. , these may have the substituents listed for R□5 above.

In addition, R□7 represents a cyan group, an alkoxy group, an aryloxy group, a halogen atom, a carboxy group, an alkylcarbonyl group, an 11-hydroxycarbonyl group, an acyloxy group, a sulfo group, a sulfamoyl group, a carbamoyl group, an acylamino group, and a diacyl group. Amino group, ureido group, urethane group, sulfonamide group, alkylcarbonyl group, alkylsulfonyl group, a1)-ruthio group, alkylthio group,
alkylamino group, sialgylamino group, anilino group,
N-arylanilino group, he-alkylanilino group,
N-acylayl may represent a hydroxyl group or a mercapto group.

R8, R19 and R20 each represent a group used in electrified high-equivalent phenol or α-naphtholkazoler, specifically, R□8 is a hydrogen atom,
Halogen atoms, aliphatic hydrocarbon residues”, -1-panol-゛doζ horn 10, -112□straddle-8-1j
I However, LR2□ is an aliphatic hydrocarbon residue) 1 is η: eclipsed, and if there are 1' or more R in the 4-molecule, there are two or more JIJ, aliphatic hydrocarbon residues are names of substituents. R□9 and R20 are aliphatic hydrocarbon residues, aryl groups, and hetero Examples include groups selected from ring residues, and these groups may be hydrogen atoms, and these groups may have substituents.Also, R□ 9 and R20 may jointly form a nitrogen-containing heterocyclic nucleus, where l is an integer of ~1, nl is an integer of ~3, and n is an integer of ~j. The C7 aliphatic hydrocarbon residue may be either saturated or unsaturated, and may be linear, branched, or cyclic. Preferably, one alkino group (e.g., λ is a group such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, 5-dodecyl, tadecyl, cyclobutyl, cyclo(hexyl, etc.), alkenyl group (for example, an alkyl group), 11, ten thousand cutynyl, etc.). Aryl groups include phenyl, naphthi/L groups, etc. -Also, -\terocyclic residues are C7.
Typical examples include bi1) dinyl, ginolyl, thiene, bipe1jdyl, imidazolyl, and the like. The substituents introduced into these aliphatic hydrocarbon residues, aryl groups, and heterocyclic residues include haloken atoms, nitro, hydroxy, funorbo-sil, ryomino, substituted amino, sulfo, alkyl, Alkenyl, if −/1. Examples include groups such as terocycle, alkoxy, aryloxy, arylthio, arylazo, acylamino, carbamoyl, ester, acyl, acyloxy, sulfonamide, sulfamoyl, sulfonyl, and morpho1().

From the general formula CIAI, whether the R group, R02, nia, R14, RR, RR 15-1718-19S'R20 of the substituents of the coupler represented by [■A] bond with each other,
Alternatively, either of A may become a covalent group to form a symmetrical or asymmetric coupled coupler.

Specific examples of the diffusible DIR coupler of the present invention are shown below.

1)-t -2 -J D-Hiroshi -s -6 H! to iC2”- -7 α -g D-ta D-／　／ 1)-/2 Nti2 lj H3 (B3 O2 D-/7 D-it I)'-/ri 1)-20 D-, zi -22 -23 D-J D-koj D-26 -27 D-2♂ D-Kota υ−31 32 -33 n ])-3! ; -36 I) -3g k J ])-4L/ D−≠λ D-φ3 D−≠j OH D-≠7 These compounds according to the invention are described in US Patent No. φ.

23≠, No. 67, No. J, 227, JJr4'
No. 3.6/7, No. 29/, No. 3. Y! I; 1,9'
No. 13, No. ≠, lhiro, s'rt No. 3,933. s
No. 00, JP-A No. 7-66137, 3/-/J2.3
British Patent No. 072.343, No. 2゜070
．． It can be easily synthesized by the method described in No. 266, Summer 1 Search Disclosure 19th February, No. 2/221, etc.

To introduce the coupler into the silver halide emulsion layer, known methods such as those described in US Pat. No. 32,2,027 can be used. For example, phthalic acid alkyl esters (cyphthyl 7-thaleate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, trichleneruaos 7-11),
--1. ) octyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octene benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate,
dioctyl azelate), trimesate esters (e.g. tributyl trimesate), or a boiling point of about 3
o0c to /300C organic solvents, such as lower alkyl acetates such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl imbutyl ketone, β-ethoxyethyl acetate, methylseron rub acetate, etc. , dispersed in hydrophilic colloids. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used.

Also, Special Publication No. 5/-37,153, Japanese Patent Publication No. 5/-37,153,
The polymer dispersion method described in Tag No. 3 can also be used.

When the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution.

High boiling point organic solvents are, for example, US Pat.
No. λ, 633. ! No. lII, same co, 13! , 577
No., Tokko Sho≠4-. No. Z3.233, U.S. Patent No. 3,2♂
7. /No. 33, British patent license, ≠Hiroshi/No. 1% Kaisho≠7
No.-103/, British patent l.

222.7♂ No. 3, U.S. Patent No. 3,93t, 303, JP-A Shoj/-26,037, Shokai ShojO-♂ 207g, U.S. Patent No. 2.3jr3, 21.2, same, 13-
, l, J♂ No. 3, 3.35≠, 763, 3.
t7t, /37 issue, same 3. t7A, /≠λ No. 3,
700, ≠j′≠ issue, 3.74L completed.

1411%, 3,137. rAE, 0LS2゜j3
1, Nig issue, JP-A-3/-2792/ issue, same! /
-27922, l'il j / -2A 03
J issue, same! /-2t036, same jTO-I! 12 otsu 3
No. 2, Special Publication Sho ≠ 7-λ R 67, U.S. Patent No. 3. ri3o.

It is described in No. 303, No. 3, No. 74'J', No. /≠/, No. 3-3/1999, No. 2721, etc.

The diffusible DIR cazoler has θ per mole of silver.

000/~o, s mol, preferably o, ooi~O,
It is appropriate to add mol of OS.

The diffusible DIIR cazolers of the present invention may be used in combination of two or more. Furthermore, the degree of diffusion defined in the present invention is Q, ≠
It can also be used in combination with the non-diffusible DIR cazolers below.

The tabular silver halide grains of the present invention have a diameter/thickness ratio of j or more and SO or more, particularly preferably 7 or more and 20 or less.

Here, the diameter of a silver particle refers to the diameter of a circle with an area equal to the projected area of the particle.

In the present invention, the diameter of the tabular arsenic grains is O0
j to 10μ, preferably o, s to jμ, especially 1, O to Hiroμ.

In general, tabular silver grains are tabular with λ parallel surfaces, and therefore, "thickness" in the present invention refers to the λ parallel surfaces that form the tabular silver grains. It is expressed as the distance between the planes.

The composition of the tabular arsenic grains is preferably silver bromide or silver iodobromide, particularly silver iodobromide having a silver iodide content of θ to 10 moles.

Next, a method for producing tabular silver halogenide grains will be described.

The tabular silver halide grains can be produced by appropriately combining methods known in the art.

For example, Photographic Journal
l 7 volumes, 330 pages / 3 years (A, PH, 'I'r
ive l 1 i.

W, F, Sm1th) Preparation method using a single jet mounted on K+ and JP-A-52-/! 3≠1 and 5
Tabular silver halide grains can be produced by the preparation method using crystals described in ll-/js No. 127 and J4L-//IIj'23.

Also, pBr/. Seed crystals in which tabular grains are present at ≠θ% or more by weight are formed in an atmosphere with a relatively high pAg value of 3 or less, and the seed crystals are grown while simultaneously adding silver and halogen solutions while maintaining the pBr value at the same level. It can be obtained by growing it.

During this grain growth process, it is desirable to add a silver and halogen solution to prevent the generation of new crystal nuclei.

The size of tabular silver halide grains is determined by temperature control, selection of the type and amount of solvent, and the silver salt used during grain growth.

It can be adjusted by controlling the rate of addition of the halide and the like.

When producing the tabular silver halide grains of the present invention, grain size and shape (diameter/thickness ratio, etc.), grain size distribution, and grain growth rate can be controlled by using a silver halide solvent as necessary. . The amount of solvent to be used is based on the weight of the reaction solution, especially 10" to 10".
1% by weight is preferred.

For example, as the amount of solvent used increases, the particle size distribution becomes monodisperse and the growth rate can be increased. On the other hand, there is also a tendency for the thickness of the particles to increase with the amount of solvent used.

Often used silver halide solvents include ammonia, thioethers and thioureas. Regarding thioethers, U.S. Pat. No. 3,27/,1
No. 37, No. 3,770.3, No. 7, No. 3,57≠,
You can refer to No. 62g etc.

During production of tabular silver halide grains of the present invention, the addition rate, amount, and concentration of silver salt solution (for example, AgNO3 aqueous solution) and halide solution (for example, KBr aqueous solution in 1994) are increased in order to accelerate grain growth. The method is preferably used.

Regarding these methods, for example, British Patent No. 1゜33j,
No. 2, U.S. Patent No. 3. No. t72,900, No. 3
, AIo, 7J'7, same No.≠, -2≠λ,! 447
No., JP-A No. 63-/4L232, same! j-/! The/
You can refer to the descriptions in items 2≠, etc.

In the present invention, tabular silver halide grains are used in at least seven of the plurality of silver halide emulsion layers constituting the entire color photographic light-sensitive material of the present invention.

The tabular halogen ratio silver grains of the present invention can be chemically sensitized if necessary.

An example of a scientific sensitization method is a gold sensitization method using a so-called gold compound (for example, US Pat. No. 2,1, ot).

No. 3,320.0) or iridium, platinum,
Sensitization method using metals such as rhodium and palladium (for example, U.S. Patent No. 2.≠≠r, oto, U.S. Patent No. 2.
J, Ibid., 5Alr, No. 263) or a sulfur sensitization method using a sulfur-containing arsenic compound (for example, U.S. Pat. No. 2,222.
2A≠), or reduction sensitization using tin salts, polyamines, etc. (for example, U.S. Patent No. 2,41r7.J'jO,
Same 2. j/r, l.

It is possible to use a combination of two or more of these.

Particularly from the viewpoint of saving silver, the tabular silver halide grains of the present invention are preferably gold-sensitized, sulfur-sensitized, or a combination thereof.

In the layer containing all the tabular silver halide grains of the present invention,
It is preferable that the tabular grains are present in a weight ratio of ≠ot4 or more, particularly 4 layer % or more, based on all the silver grains in the layer.

The thickness of the layer containing tabular silver halide grains is o, s-
,,j,oμ, especially /, preferably 0 to 3.0μ.

In addition, the coating amount of tabular halogen silver particles is /per layer t)o,
oj-69/rrL2, especially θ, 2-2j9/7rL2
It is preferable that

Other components of the material containing all the tabular silver particles of the present invention, such as a binder, a curing agent, an antifoggant,
Silver halide stabilizers, surfactants, spectral sensitizing dyes,
There are no particular limitations on dyes, ultraviolet absorbers, chemical sensitizers, etc., and, for example, those used in general silver halide emulsions described below can be used.

In addition, as an additive to the tabular emulsion of the present invention,
023.70/ (Q / -7x = /l/
-3-pyrazolidinone derivatives (e.g. l-phenyl-guphenyl-3-pyrazolidinone, /-phenyl-
≠, ≠-dimethyl-3-pyrazolidinone, /-(-p-
(Tolyl)-3-pyrazolidinone, etc.), U.S. Patent 3,
2≠'/, rit7, 4t, 20y, sro@, or 11,310. It may be preferable to use compounds such as those described in TLJ that release the more phenyl-3-pyrazolidinones during color development processing.

Gelatin is advantageously used as a binder or protective colloid in photographic emulsions, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyether cellulose, carboxymethyl cellulose, and cellulose sulfates; sugar derivatives such as sodium alginate starch derivatives; -, 11/, polyhinyl alcohol partial acetal, poly(+)) Various synthetic hydrophilic compounds such as single or copolymers of N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Polymeric substances can be used.

Gelatin includes lime-processed gelatin, acid-processed gelatin, Bull, Soc, Sci, Phot, and Japan.
.

/Fx / A, 30'jii (/P A
4) K Description 7'C Io fZ Enzyme-treated gelatin may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used.

As gelatin derivatives, various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acids, alkanesultones, vinyl sulfo/amides, maleimide compounds, polyalkylene oxides, and epoxy compounds can be added to gelatin. The product obtained by the reaction is used. A specific example is U.S. Patent λ, &/Hiroshi, No. 22g, 3. /32, Rihiro J No. 3.1g Otsu, Za4At No. 3゜3/2,533, British Patent lr4/, 4t/4 No. 4T/4, No. 3.1g Otsu, Za4At No. 3.1g, 033. /l'ri issue, same/, 00! , 7za≠
No., Tokusho tt2-2t,? It is written in ≠J issue etc.

In the present invention, other than the tabular silver halide grains, commonly used silver halides such as those described below may be used simultaneously and/or in other layers.

That is, in the photographic emulsion layer of the photographic light-sensitive material used in the present invention, any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride may be used as silver halide. The preferred silver halide is silver iodobromide containing 75 mol % or less of silver iodide. Particularly preferred is silver iodobromide containing from 1 to 2 mol% silver iodobromide.

The average grain size of the silver halide grains in the photographic emulsion (the grain size is the grain diameter in the case of spherical or approximately spherical grains, the ridge length in the case of cubic grains, and is expressed as an average based on the projected area) is not particularly limited. is preferably 3μ or less.

The particle size distribution may be narrow or wide.

Silver halide grains in photographic emulsions may have regular crystal structures such as cubes and octahedrons, or irregular crystal structures such as spherical and plate shapes.
It may have a crystalline shape (gular), or it may have a composite engraving of these crystalline shapes. It may also consist of a mixture of particles of various crystalline forms.

Halogen (arsenal) particles may have different phases inside and on the surface, or may consist of a uniform phase.

Further, the particles may be particles in which a latent image is mainly formed on the surface, or may be particles in which a latent image is mainly formed inside the particles.

In the process of halogen-1 arsenic particle formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present.

Silver halide emulsions are usually chemically sensitized.

For sensitization, for example) I, Die Grundlagen der Photo edited by Frleser.
ographischenProzesSrnit S
ilberhalogeniden (Akadomis
che verlagsgeSellschaft.

The method described on pages 77j to 7317 can be used.

That is, sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto f
Sulfur sensitization method using sulfur-reducing substances (e.g. stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, 72716 compound); noble metal compounds (For example, a metal sensitization method using a total complex salt or a complex salt of a metal of Group I of the periodic table such as P ts I rsPd) can be used alone or in combination.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazo-A
/a (WK nitro- or /・lokene substituted product) 8 Heteromoniac mercazoto compounds such as mercaptothiazoles, mercazotopenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (%/-phenyl -j-mercaptotetrazole), mercaptopyrimidines; the above-mentioned heterocyclic mercazoto compounds having a water-soluble group such as a carboxyl group or a sulfone group; thioketo compounds such as oxazolinthione; azaindenes such as tetraazaindene (in % ≠-Hydroxy substitution ('/, 3
, 3a, 7) tetraazaindenes); benzenethiosulfonic acids; benzenesulfinic acid; and many other compounds known as antifoggants or stabilizers can be added.

For more detailed examples of these and how to use them, see, for example, U.S. Pat.
ri J'co, tag No. 7, same No. ≠, 02/, 211-r specifications or Japanese Patent Publication No. 2-2T.

The description in the tto publication can be referred to.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsion dispersion, adhesion prevention, and improvement of photographic properties (e.g., development acceleration, high contrast It may contain various surfactants for various purposes such as sensitization, sensitization), etc.

For example, saponins (steroids), alkynon oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl needles, polyethylene glycol esters 'D, 1) ethylene glycol Sorbitan ester m, polyalkylene glycol alkyl amine or amide, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. rkenyl succinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols, alkyl esters of sugars Nonionic surfactants such as alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfate esters, alkyl phosphate esters, N-acyl-he-alkyl toughs Acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc. such as phosphorus, sulfosuccinates, sulfoalkylpolyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc. Anionic surfactants containing groups; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or acid esters, alkyl betaines, amine oxides; alkylamine salts, aliphatic or aromatic ≠ ammonium salts,
Cationic surfactants such as heterocyclic primary ammonium salts such as pyridinium, imidazolium, and aliphatic or heterocyclic phosphonium or sulfonium salts can be used.

The photographic emulsion layer of the photographic light-sensitive material prepared using the present invention contains, for example, polyalkylene oxide or its ether, for the purpose of increasing sensitivity, increasing contrast, or promoting development.
Derivatives such as esters and amines, thioether compounds,
Thiomorpholines, quaternary ammonium salts 18 compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-
It may also contain pyrazolidones and the like.

The photographic light-sensitive material produced using the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. For example, alkyl (meth)acrylates,
Alkoxyalkyl (meth)acrylates, glycidyl (meth)acrylates, (meth)acrylamides, vinyl esters (e.g. vinyl acetate), acrylonitrile, olefins, styrene, etc. alone or in combination, or together with acrylic acid, methacrylic acid, α.

β-unsaturated dicarboxylic acid, hydroxyalkyl (meth)
7. Using a combination of acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. as a monomer component. '51Jmer can be used.

Clear photographic processing comprising photographic emulsions made using the present invention includes, for example, Research Disclosure.
arch Disclosure) / 76 No. 21
- Page 30 (RD-/7 Otsu 4L3) Any of the known methods and known treatment liquids as described above can be applied. This photographic processing may be any photographic processing that forms a dye image (color photographic processing) depending on the purpose.

The processing temperature is selected to be between 0C and 0C, but may be lower than 0C or above 0C.

As a special form of development processing, the developing agent in all photosensitive materials,
For example, it is included in the emulsion layer, and the light-sensitive material is processed in an alkaline aqueous solution to create an image. il+'? You may also use a method that allows you to do so. Among the developing agents, hydrophobic ones are listed in Research Disclosure/&R No. (RD-/1.921), US Patent No. 2.73F, 190, and British Patent No. 1/3.2!3.
They can be incorporated into the emulsion layer by various methods such as those described in West German Patent No. 7J117.763.

Such development treatment may be combined with silver salt stabilization treatment with thiocyanate.

As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used.

The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

When forming a dye image, conventional methods can be applied.

For example, the negative-positive method (for example, 'Journal
of the 5ociety of Motion
Picture and Te1evision Eng
ineers”, Volume 6 (1953), 6A7-70
Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer, such as phenylene diamines (e.g., guamino-, N-ethylani, 3-methyl-μm).
Ryo minnow N, N-diethylaniline, ≠-amino N-
Engineering f-N-β-hydroxyethylaniline, 3-methyl-≠-amino-ethyl-β-hydroxyethylaniline, 3-methyl-Hiro~ryominoh-ethyl-β-methanesulfamide ethylaniline, t-amino -3-Methyl-he-Kote-ruhe-β-methoxyethylaniline, etc.) can also be used.

In addition, Photograph by F. A. Mason
icProcessing (:hemistry
(Published by Focal Press, / 1966) (D22t
-Page 22F, U.S. Patent λ,/ri No. 3,01J, same, j
riλ.

Those described in JP-A No. 3A Hiroshi, JP-A-Sho≠z-6 Ku 6-Hiroshi, No. 3A, etc. may be used.

Color developers can also contain gold, such as pH buffering agents, development inhibitors or anti-capri agents.

In addition, water softeners, preservatives, organic solvents, development accelerators, dye-forming couplers, competitive couplers, fogging agents, auxiliary developers, viscosity-imparting agents, polycarboxylic acid chelating agents, and antioxidants are added as necessary. It may also include.

Specific examples of these additives include Research Disclosure (RD-tit, ≠3) and US Patent No. 'i', 01
No. 3,723, West German Publication (OLS) 2°t22.93
It is written in No. 0, etc.

After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. As bleaching agents, iron (summer), cobalt (
11), compounds of polyvalent metals such as chromium (■), copper CB), peracids, quinones, nitroso compounds, etc. are used.

and λ is Hue-11 cyanide; dichromate; iron(1)
or copal) (1); organic polycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, /, 3-diaminorcobronoξnortetraacetic acid; or organic complexes such as citric acid, tartaric acid, and malic acid. Acid complex salts; persulfates, monopermanganates; nitrosophenols, etc. can be used. Of these, potassium ferricyanide, ferric ethylenediaminetetraacetate (11) and ammonium ethylenediaminetetraacetate (1) are particularly useful.
The 11 complex salts are useful both in stand-alone bleach solutions and in -bath bleach-fix solutions.

For bleaching or bleach-fixing solutions, see U.S. Patent 3.0 Hiroko, 32
No. 0, No. 3.2≠7,766, Special Public Sho≠5-rso6
In addition to the bleaching accelerators described in Japanese Patent Publication No. Sho PS-Do No. 36, and the thial compounds described in JP-A No. 63-1,5732, other additives can also be used.

The photographic emulsion used in the present invention is spectrally sensitized with methine dyes and others.

Examples of useful sensitizing dyes include German Patent No. 722.010,
U.S. Patent No. 93,7≠g, same.

No. 603.776, same, jt/ri, ooi, same,
ri/2, j2ri issue, same J, 6! T,? ! ;9
No. Tsukasa 3,672,127, '1,0125,3'
No. 1, British Patent/, 24t2, No. 61, Special Publication Showa 4t
4L-/! , No. 030.

These sensitizing dyes may be used in a conventional manner, but a combination thereof may also be used, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. A typical example is US Patent 2
．． 611,! 4t6, same Yu.

977,. 2 Kota issue, 3rd issue, 3rd issue 7.060, 3rd issue.
No. 622.062, 3. ! 27. tg No. 1, same 3. /
, /7, 2nd issue 3, same 3, 62J', ? A4' No. 3. AtA, l/-10, same J, A7. ! , J'
yr No. 3, 674i', 1I21, No. 3.
1'/'A.

No. 602, same #, 0.2t, No. 707, British patent/
.

34/, 4t, 21/ issue, special public show +j-41,936
No. 63-/, 2. J7J- issue, JP-A Shoj Co.//θ
.

A/g', same! 2-/09.92! In the issue:
t, I'm sa.

In the photographic light-sensitive material produced using the present invention, the photographic emulsion layer and other layers are made of a flexible support such as plastic film, paper, or cloth, which is commonly used in photographic light-sensitive materials, or a rigid support such as glass, ceramic, metal, etc. applied to the support. Useful flexible supports 7 include cellulose nitrate, cellulose acetate, cellulose acetate butyrate, BoIJ styrene,
Films made of semi-synthetic or synthetic polymers such as polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta layers or α-olefin polymers (e.g.
The material may be coated or laminated with polyethylene, polypropylene, ethylene/butene copolymer, etc., or paper. The support may be colored using dyes or pigments.

In the photographic light-sensitive material produced using the present invention, the photographic emulsion layer and other hydrophilic colloid layers can be coated on the support or on other layers by various known coating methods. Application methods include dip coating, roller coating, curtain coating,
An extrusion coating method or the like can be used. US Patent Co., Ltd.
61r/, 2rihiro No., same λ, ZM;/, 7ri No. 1, same 3
, J'2t, 62r is an advantageous method.

The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support.

Multilayer color photographic materials usually have a red-sensitive emulsion layer on a support,
It has at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer. The order of these layers can be arbitrarily selected as necessary. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case.

Exposure to obtain a photographic image may be carried out using a conventional method. i.e. natural light (sunlight), tungsten electric light,
Fluorescent lamp, mercury lamp, xenon arc lamp, charcoal lamp,
Any of various known light sources such as a xenon flash lamp, a cathode AT flying spot, etc. can be used.

Exposure times include not only exposure times of 171,000 seconds to 7 seconds, which are normally used with cameras, but also exposures shorter than //10' to 1/100 seconds using xenon flash lamps and pole ray tubes. or an exposure longer than 2.1 seconds.

If necessary, the spectral composition of the light used for exposure can be adjusted using a color filter. Laser light can also be used for exposure. Alternatively, exposure may be performed using light emitted from a phosphor excited by electron beams, Xa, γ rays, α rays, or the like.

The photographic emulsion layer of the photographic light-sensitive material prepared using the invention contains color-forming couplers, that is, oxidation with aromatic primary amine developers (e.g., phenylene diamine derivatives, amine phenol derivatives, etc.) during color development processing. cup 1
A compound that can develop a color by coloring may also be used. For example, magenta couplers include j-pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, etc. Yellow couplers include acylacetamide couplers (e.g. benzoylacetanilide chains, pivaloylacetanilides) ), and cyan couplers include naphthol couplers and phenol couplers.

These couplers are preferably non-diffusive and have a hydrophobic group in the molecule that can be used as a ballast group. The coupler may be either μ-equivalent or 2-equivalent to silver ions.

It may also be a colored cover sheet having a color correction effect or a coupler that releases a non-diffusible development inhibitor during development (so-called non-diffusible DIR coupler).

Non-diffusible DIR couplers may also include colorless non-diffusible DIR coupling compounds in which the product of the wiggly reaction is colorless and releases a development inhibitor.

A specific example of a magenta coloring coupler is disclosed in the US patent.

AOo, 71! No. 2,913, 1.01, No. 3
．． 07,2. 3 to lr, same 3. /27,269, 3,3//, l/L76, 3. ≠/ri, 32/ issue,
Same J, f/9', Ri No. 2, Same 3. ! j♂, 3/ri issue,
Same 3, jr12.322, same! ,t/! r.

No. 506, 3. Za31/L, 7ox, same 3. ♂ri l
, Hiroj issue, West German patent l, 10. Ko 6≠, West German patent application (OLS + 2, lIO#, 6A No. 6, same, 1.II/7, 94t No. 3, same, shoes, etc.)
No. +2.11217. LA7, special public official Akito-
T.

3/issue, Tokukaisho, f/-20g26, same j2-6
Za222, Same≠Tar12ri6J1t, Same≠2-7Hiro027, Same50-40233, Samej2-'72/2
/ issue, Dohiro! i'-711028'' No. 50-402
No. 33, same! /-, 26j'4A/ issue, same j3-sJ/
This is what is described in No. 22, etc.

A specific example of a yellow coupler is U.S. Pat. No. 2,173.06.
No. 7, 3, 21. s, No. 506-, 3゜Hiro01. /
Tag number, 3. J-! /, /! j issue, same J,, fr2
．． No. 322, No. 3.723', No. 07.2, No. 3. ♂
ri/, 4 Hiroj, West German Patent/, 64'7゜rttr, West German Application Publication Co., 2/ri, No. 277, 2,26/,
36/issue, same, 4A/! , No. 007゜, British Patent/, Gu2J, No. 02θ, Special Publication Shoj/-10713,
Japanese Patent Publication No. 1. L7-2A/33, L7-73/11
No. 7, same j/-102631r, same! 0-634L1
Same issue! 0-/233≠2, 60-/304L'A
No. 2, J-/-2/1.27, No. 6O-Jr7t!
No. 0, same j'2-121. t21fi issue, same j, 2-/
It was written in the /j2/ri issue, etc.

A specific example of a cyan coupler is US Patent λ, JAS'.

Takota, same, j Hiroj, 272, four, ≠7 Hiro, 2
No. 23, same! 2/, ri oir, same 2゜J'5'j
, No. I2J, No. J, 0J4t, No. 19'2, No. 3.3//, No. 76, No. 3. ≠jza, 3// issue, samej
,! 7A, jt63, same 3, j13.97/
No. 43. Jri/, No. 313, 3,747. Hiroshi／/No., same≠, 00+, Ri2ri No., West German patent application (OLS)
2, +/+, No. 130, 42.41sa.

No. 322, Japanese Patent Publication No. 4 TR-J 1'31, JL-2
6034A issue, same + r-soss issue, same j/-/16♂
2, j2-6ri No. 62, and j coater Ori No. 3.

As a colored coupler, the example is US patent 3°! 7G
, No. 560, 2. ．． ! 2/, Rior issue, 3.034
L, No. 192, Special Publication Showa 4'4'-, 20/l, Issue, @l
No. 3r-2233j, Doko 2-//, No. 30'1, Dou 1
No. 117-32'lt/, JP-A-6/-21r034 in the specification, j, 2-112/2/, West German Patent Application (OLS) 2.41-lr, Rijri No. You can use what is listed.

Non-diffusive DIR couplers include, for example, U.S. Pat.
, 227.56 Hiro issue, 3, 6/7, 2P1 issue, 1nJ
J, 70/, No. 713, TqJ, 79'0゜3
! r≠ issue, same 3. t32, 3≠j, West German patent application (O
LS ), 2, t, ti ≠, oo otsu, same 2.4'j
Hiroshi, No. 307, same, ≠5≠, 327, British patent 3
;3,4L! No. 4', JP-A No. 5-16-62≠, same≠
7-/, No. 22336, and those described in Japanese Patent Publication No. Shoj/-1tiVL can be used.

In addition to the DIR coupler, the light-sensitive material may also contain a compound that releases a development inhibitor upon development; for example, as described in US Pat. Kota 7,4 to Hiroj, 3,37, j2
No., West German Patent Application (OLS) λ, G/7,! /
/j issue, JP-A-62-13271, JP-A-53-71
Those described in No. 11 can be used.

The photographic light-sensitive material produced using the present invention may contain an inorganic or organic hardening agent in the photographic emulsion layer or other hydrophilic colloid layer. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glumeraldehyde, etc.), N-methylol compounds (dimethylonotourea, methyloldimethylhydantoin, etc.), dioxysan derivatives (2,3-dihydroxydiogysanate, etc.) etc.), activated vinyl sword/compound (/, J,
! -) lyacryloyl-hexahydro-s -) IJ
7 syn, l, 3-vinylsulfonyl-2-propatur, etc.), active halokene compounds (2,4+!-dichloro-6-hydroxy-5-triazine, etc.), mucohalogens e (mucochloric acid, mucophenoxychloroic acid, etc.) etc.), etc. can be used alone or in combination.

In the photosensitive material made using the present invention, when dyes, ultraviolet absorbers, etc. are contained in the hydrophilic colloid layer,
They may also be mordanted with cationic polymers and the like.

The photosensitive material produced using the present invention contains hydroquinone conductors, mininophenol derivatives,
It may also contain gallic acid derivatives, ascorbic acid derivatives, etc.

The photosensitive material produced using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with aryl groups, goo acylidone compounds, benzophenone compounds, cinnamic acid ester/L compounds, butadiene compounds, benzoxazo-/L compounds,
Further, a UV-absorbing bomber or the like can be used. These ultraviolet absorbers may be fixed in the hydrophilic colloid layer.

Specific examples of ultraviolet absorbers are given in U.S. Patent 3. j, 3:l.

No. 7 Riwo, No. 3, No. 3, No. 72≠, No. 3, 3j, A
t/also, JP-A-Sho Q6-2,7f≠, US Patent 3.70
! , No. 105, No. 3,707.37j, No. 'l-, 0
11, f, No. 22, 3, 700.

3. Geta No. 2.76λ, West German patent application publication/, J-1, t7. It is written in Za No. 63, etc.

The photosensitive material produced using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for irradiation prevention and other purposes. Such dyes include oxonol dyes, hemioxonol dyes, stylyl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes;
Hemioxonol dyes and merocyanine dyes are useful.

In carrying out the present invention, the following known antifading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more. Examples of known antifading agents include hydroquinone derivatives, gallic acid derivatives, P-alkoxyphenols, 1)-oxyphenol derivatives, and bisphenols.

Specific examples of high%'ry phonone derivatives are disclosed in U.S. Patent No. 2゜31.
．． 0, 2ri No. 0, same co, Kol, 6 no 3, same co, t7
j, 31≠ issue, same co, 'yoi, iri 7, same 2,70
4! ,, 7/3 issue, same page, 7.2 issue, same page,
732, 30θ, 2.73! , Vts No. 2, 7
No. 10,10/, Ibid.:l, r/6°02g, British Patent No. 3A3,92/, etc., and gallic acid derivatives are described in US Pat. '1, No. 7,07, No. 3,06, No. 262, etc., and those of P-alkoxyphenols are described in US Patent λ, No. 73. f,
No. 7Aj, 3.69g, ri09-4-j, Tokko Sho Geta No. 20,777, PJj2-Otsu, No. 623.
The P-J-xyphenol derivatives are described in U.S. Pat. ! ;73,0!0 issue, same 3, j7ri, 6.27+f1 Tou J, 76≠, 337
No. 52-3s, No. 633, PJ! 2/4L
7°g 311. No., same; 2-/! 2. It is described in Noko No. 1, and that of bisphenols (C U.S. Pat. No. 3.7).
00, ≠ It is completely written in the SS number.

Example 1 1. on a polyethylene terephthalate film support. A multilayer color photosensitive material sample ioi consisting of each layer having the composition shown below was prepared.

(Sample 10/) 1st ring: Antihalation layer (AHL) Gelatin layer containing black colloidal silver 2nd layer: Middle layer (ML) Ko,! Gelatin 1 containing an emulsified dispersion of -d-t-octylhydroquinone 3rd @: First red-sensitive emulsion layer (PLI) Monodisperse silver iodine (silver iodine: j molar ratio average particle size 0.3μ) Spherical grains) ... Silver coating amount Q, i/m2 Silver iodobromide (silver iodide: 3 moles) Average grain thickness O8λμ,
Average particle diameter≠, tabular grains of Oμ)...Silver coating amount 0-1#/m2 Sensitizing dye■
・・・・・・AXlo moles per mole of silver Sensitizing dye■・・・・・・i, s×io per mole of silver
Molar coupler (C-/)...O1 per 7 moles of silver
O≠molar coupler (C-,2)...0 per mole of silver
．． 003 mole coupler (C-j)... o per mole of silver,
ooot molar ≠ layer: λth red-sensitive emulsion layer (Rb2) Silver iodobromide emulsion (silver iodide 7 molar average grain size/.

Spherical particles of θμ) ・・・・・・Amount of silver applied λ Q9/rIL2 sensitizing material ■・
...3 per mole of silver! ×10 mol sensitizing dye■・・・・・・・per 1 mol of silver/, O×10
Molar coupler (C-+)...0.0 per mole of silver
20 mole coupler (C-2)...0.0 per mole of silver
02 molar srgl: Intermediate layer (ML) Same as the 2nd layer t4: 1st green-sensitive emulsion layer (GLt) Silver iodobromide emulsion (Silver iodide: ≠ molar ratio Spherical polydisperse emulsion with average grain size O1tμ ) Coated silver amount/. 6i/m2 Sensitizing dye ■・・・3×1O mol per 1 mol of silver Sensitizing dye ■・・・・・・／×/θ per 1 mol of silver
Molar coupler (C-s)...72 per mole of silver
g coupler (c-1...0.0 per mole of silver
0g mole coupler (C-j)...Q for 1 mole of silver,
0075 mol 7th layer: 2nd green-sensitive emulsion 4t (GLz) Silver iodobromide emulsion (silver iodide ginseng molar ratio, average grain thickness 0.2μ
, tabular grains with an average particle diameter of 6.0μ)......Silver coating amount/-4g/m2 Sensitizing dye ■......λ, s×i for 1 mole of silver
o mole sensitizing dye ■・・・o, s for 1 mole of silver
xi o mole coupler (C-7)...0.0% per mole of silver.
02 mole coupler (C-X)...0.02 mole per mole of silver.
003 mol G layer: Yellow filter single layer (YFL) A gelatin layer containing yellow colloidal silver and an emulsified dispersion of 5-1-t-octylhalodoroginone in an aqueous gelatin solution. Layer (BLI) Silver iodobromide emulsion (Silver iodide: A molar ratio, spherical grains with an average grain size of 0°3 μm) ... Coated silver amount/, j9/rrL2 Cazoler (c
-a')...0.26 mole per mole of silver Coupler (D-Hiroshi)...0.26 mole per mole of silver.
07j mol 1st O layer: 2nd back-sensitive emulsion layer (BL2) Silver iodobromide (Silver iodide: mol ratio spherical grains with an average grain size of 0.7 μm)...Amount of coated silver C/,! il/m2 coupler (C-t)... 1 mole of silver to 1 mole of O+Oz 1st/layer: 1st protection 1 layer (PLl) Silver iodobromide (1 mole of silver iodide, average grain Diameter o, o7μ) ... Coated silver amount o, sg
Gelatin layer containing an emulsified dispersion of the ultraviolet absorber UV-1 No. 12: Second protection 1 g (P L 2 ) trimethyl methacrylate particles (diameter approx.

Apply a gelatin layer containing jμ).

In addition to the above composition, a gelatin hardening agent H-/ and a surfactant were added to each 1-.

The sample prepared as described above was designated as sample ioi.

Sensitizing Tomoe ■: Anhydro s-s' ~ dichloro = 3.3
/ , >(γ-sulfozolovir)-terethyl-thiacarbosia, ninhydroxide pyridinium salt sensitizing dye■: Anhydroterethyl-3,3'-c(γ-sulfopropyl)-≠・j-≠′-j '-Dibenzothiacarbocyanine hydroxide/triethylamine salt sensitizing dye ■: Anhydroterethyl s, s'-enchloro 3.3 /-(γ-sulfopropyl)oxacarbocyanine/sodium salt sensitizing dye ■：Anhydro! -1r-j'・1. /-Tetrachloro-/・/'-diethyl-3-3'-1-(β-[β-(γ-sulfoprog7)ethoxy]ethylimidazolocarbocyanine hydroxide sodium salt (Sample 102) Sample 10/ Silver iodobromide (3 mol % silver iodine, average grain thickness 0.2 μ, average grain size ≠, tabular grains Q μ) of RLl was weighed equally with spherical grains with average grain sizes o, s'a μ. The replacement sensitizing dyes ■ and ■ were reduced by 0.3r times to obtain the maximum sensitivity, and silver iodobromide (silver iodide hromolar ratio, average grain thickness Ol, 2μ, average grain size 1.0μ) of GL2 was used. tabular grains)
are replaced with equal weights of spherical particles with an average particle diameter of /, /μ, and sensitizing dyes (■) and (■) are adjusted to 0.0 to obtain maximum sensitivity. It was prepared in the same manner as Sample 10/, except that it was reduced by ≠ times.

(Sample 103) The BLl coupler (D-≠) of sample 102 was replaced with the coupler (
It was produced in the same manner as Sample 102 except for replacing it with C-j).

(Sample 104t) The coupler (D-≠) of BLl of sample 10/
It was produced in the same manner as sample ioi except for replacing it with C-j).

When a sample of 10/~10≠ was wedge-exposed with white light and processed, the results shown in Table 2 were obtained.

Samples 10/ and 10≠ were exposed to uniform green light and then wedge exposed to blue light for processing, resulting in a magenta image as shown in the figure. Here, ΔX is when the blue-sensitive emulsion layer is developed from the unexposed area (point A) to the exposed area (point B),
This figure shows the extent to which a uniformly fogged magenta emulsion is suppressed.

That is, in FIG. 1, curve A--B represents the custom curve for the yellow image of the blue-sensitive layer, and curve a--b represents the magenta density of the green-sensitive layer with uniform green exposure. Point A represents the fogged portion of the yellow image, and point B represents the exposure amount portion that provides the yellow image density λ,j.

The difference between magenta density (a) at exposure amount A and magenta density (b) at exposure amount B (a=b) was taken as a measure of the interlayer effect from blue sensitivity to - to green sensitivity 1-.

Also, the measurement of MTF value is based on The Theory of
Photographic Process jr
d edd.

(Mies, published by Matsuku Millan). The specific sensitivity is expressed relative to the base metal, with that of sample 10/ being set as /, 0.

The development used here was carried out at 310C as described below.

/, Color development・・・・・・・・・3 minutes 75 seconds 2
6 Bleaching・・・・・・・・・・・・・・・6 minutes 3
0 seconds 3, wash with water・・・・・・・・・・・・・・・
Set for 3 minutes/j seconds...
Wash with water for 30 seconds...
...3 minutes/j seconds6. Cheap foot........
3 minutes and 1 seconds The composition of the treatment liquid used in each step is as follows.

Color developer sodium nitrilotriacetate /, 0g sodium sulfite ≠. 0g Sodium carbonate 30.0g Bromination power +1
/, 4'fl Hydroxylamine sulfate
(Hydroxyethylamino)-2-Methyl-Ryonidine Sulfate ≠, Add water ll Bleach solution Ammonium bromide / 1,0, Of
i Aqueous ammonia (21% l 2s, Oyd ethylenediamine-tetraacetic acid sodium iron salt / 30 g glacial acetic acid
l≠... d Add water
/! Fixer Sodium tetrapolyphosphate ko, Og Sodium sulfite ≠・og Ammonium thiosulfate <qotyo) tys, oyn1 Sodium bisulfite ≠, tg Add water
/, 1 stabilized formalin I, 0ml
Table 2 also shows the results when water was added to give uniform red light in the same manner as in /7, and further wedge exposure was performed with blue light.

As is clear from Table 2, the sample ioi of the present invention has high sensitivity, a large interlayer effect, and high sharpness as expressed by the MTF value.

On the other hand, sample IO'l, which uses tabular grains and does not use a diffusive DIR coupler, has a small interlayer effect and a low MTF value.

It can be seen that the sensitivity is low for the 10 samples in which a diffusive DIR coupler was used and no tabular grains were used.

Example 2 For sample 10/ of Example 1, BL coupler ~ (D-4
') was changed as shown in Table 3 to prepare samples 20/~20 Hiro, and the same test as in Example-1 was conducted '4 From the results in Table 3,
It can be seen that compared to samples IO'l and 20/ in which the degree of diffusion of the DIR leaving group is small, samples 10/, θ2.203, and KOH of the present invention have substantially the same sensitivity and a large interlayer effect.

Example 3 (Sample 30/) The following changes were made to sample iohiro.

(1) Coupler (D-2) was added to GL Co in an amount of 0,001 mol per mol of silver to make the silver iodobromide emulsion coating amount 2.
．． Increase to sf7/m.

f21 RL coupler (C-≠) to coupler (C
−//l, respectively, in equimolar amounts.

(Sample 302j) Sample 30/ was prepared in the same manner as Sample 30/, except that spherical particles were used in the same manner as in Samples 10/ to 102.

(Sample 303) Coupler (D-, 2) of sample 30/ is replaced with coupler (C-J
It was produced in the same manner as Sample 30/, except that 1 was replaced with an equimolar amount.

Regarding these samples 30/~303, as in Example/2, the multilayer effect from G to R and the specific sensitivity total foot U of GL
7 The results are shown in Table 1.

Table ≠ This result is also similar to Example 2.

C-7 α -r C-ta C5H□□(1) -10 C-// UV-/ (weight ratio) -1 Na

[Brief explanation of the drawing]

Figure 7 shows the method of measuring the multilayer effect from the blue-sensitive layer to the green-sensitive layer, in which the horizontal axis represents the exposure amount and the axis represents the total density. 5. Applicant for drawing patent: Engraving of surplus drawings from Fuji Photo Film stock (no changes in content) Figure 1 Procedural amendment (receipt) Dear Commissioner of the Japan Patent Office 1. Indication of the case 1939 Patent Application No. 75+
10,000 Title of the invention Relationship with the person who corrected the silver halogenide color photographic light-sensitive material Patent applicant 4 Date of amendment order April 26, 1982 5. Column 6 of “Object of amendment: Description and title of invention in the description”
We will submit a detailed statement of the amendments and an engraving of the drawings (no changes to the content). The name of the invention in the specification “Silver halide photographic light-sensitive material” is changed to 1.
"Silver halide color photographic light-sensitive material". Procedural amendment Showa! Patent application No. 4t734
No. 2, Title of the invention Silver halide color photographic light-sensitive material 3, Relationship with the case of the person making the amendment Patent applicant 4, Subject of the amendment Column 5 of "Detailed Description of the Invention" of the specification, Contents of the amendment ( 1) Page 35 of the specification? Replace with “Attachment-7”. (2) I page j6? “Attachment-λ” (3) I page 110 r “Attachment-3” (4) I page 1//? “Attachment-Hiroshi” [Attachment-l
] 1)-3 D-Hiroshi [Attachment-2] ])-1AI D-Goo α [Attachment-3] -1 N Near-NHCOC (CI-1a) a [Attachment-G] C-7 C-, r procedural amendment showa! Year Month YIEI Mr. Commissioner of the Japan Patent Office 1, Indication of the case Showa J♂ Year Patent Application No. '1714
No. 1, No. 2, Title of the invention Silver halide color photographic light-sensitive material 3, Relationship with the case of the person making the amendment Patent applicant ≠, subject of the amendment ``Detailed description of the invention'' column in the specification! , the statement in the "Detailed Description of the Invention" section of the Description of Contents of the Amendment is amended as follows. (1) Insert "more preferably 4 or more and 30 or less" after "to or less" in No. J, page 2, line 17. (2) On page t3, line io, “o-io mol%” should be changed to “0 to 20 mol% silver iodobromide, especially 3 to 13 mol%”.
Corrected as "mol%". (3) Correct “002-2g” on page 67, line 1 to “o, z-J, 9”.

Claims (1)

[Claims] A development inhibitor containing tabular silver halide grains with a grain size of 5 times or more the grain thickness in at least one layer of a multilayer silver halide emulsion layer coated on a support, and which is a leaving group for a DIR coupler. 1. A silver halide color photographic light-sensitive material comprising at least one DIR cutler having a diffusivity of 0 g to 0 g or less.