JPS6184646A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve sharpness and graininess by using a specified coupler. CONSTITUTION:The coupler to be used is represented by the formula in which A is a coupler residue to be cleft from X by a reaction with a main development oxidant; X is O or S; Y is H or a substituent; n is 1 or 2, and when n is 2, each of two Y's may be different, or a divalent group and combine with each other to form a ring. Such a coupler is allowed to release aromatic alcohol or thiol substd. by two OH groups by the reaction with the oxidation product of a developing agent. This released compd. has strong reducing action and reduces said oxidation product. The presence of the two OH groups raises water-solubility and the diffusivity of the compd. into an emulsion, and this diffusivity is easily controlled by regulating Y to a proper size, thus permitting proper water solubility and diffusivity to be obtained and the excess of said oxidation product to be effectively removed by reduction, each separate dye cloud not to grow over a certain size, mottles to be prevented, and graininess to be improved.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a silver halide color photographic light-sensitive material containing a photographic coupler for improving sharpness and graininess.

(Prior art) By color-developing a silver halide color photographic material, an oxidized aromatic-grade amine color developer and a coupler react to form indophenol, inodoaniline,
It is known that indamidine, azomethine, phenoxazine, phenazine and similar dyes can be produced to form color images.

In this method, subtractive color method is used for F1 normal color reproduction,
Yellow, magenta and cyan color image-forming agents are used which are complementary colors to a green/red emulsion selectively sensitive to green and red, respectively. To form a yellow color image, for example, a dibenzoylmethane coupler is used as an acylacetanilide, and to form a maze/red color image, a pyrazolone, pyrazolobenzimidazole, chloride, anoacetophenone or ionic coupler is used. /
Dazolone couplers are used, and primarily phenolic couplers such as phenols and naphthols are used to form the cyan 1-me.

In recent years, high image quality has become more important than ever in silver halide photographic materials, especially color photographic materials, due to the spread of disk cameras and /10f size cameras. In particular, it is important to improve sharpness and graininess.

It has been known that couplers are used not only to form dye images but also to release photographically useful groups. Compounds that release photographically useful groups are used for various purposes such as improving color reproducibility, improving graininess, improving sharpness, or increasing sensitivity.

Couplers have been proposed that can release a compound that captures an oxidized color developing agent from the coupling position of the coupler. For example, Tokukai Akira! Norco 13/r, same 5
Compounds described in 7-tiiss'y, J7-/3r634, and the like are known. These couplers are used for the purpose of improving graininess or controlling gradation, but their effects are weak, and further improvements have been desired. In addition, it has been found that the scavengers for the oxidized developing drug released by these known couplers not only have a weak capture ability, but also have low diffusivity. Therefore, it was not possible to improve the sharpness of ti&< or to diffuse to other layers to obtain tP layer young fruit.

(Melting point to be solved by the invention) Therefore, an object of the present invention is to improve graininess and sharpness by incorporating a novel coupler that releases a compound that captures an oxidized developing agent by reaction with the oxidized developing agent. Another object of the present invention is to provide a color photographic material that is excellent in color reproducibility due to a multilayer effect.

(Elaborate means for solving the problem) The above object was achieved by a silver halide color photographic light-sensitive material containing a coupler represented by the following general formula (1). A currently represents all the cazolar residues that are cleaved with X upon reaction with the oxidized main drug, X represents an oxygen atom or a sulfur atom, Y represents a hydrogen atom or a substituent group,
nFi/ or Co, and when n is Co, the λ Ys may be different substituents, and the λ Ys may each be a covalent group and connect to form a cyclic structure. good. ] The coupler of the present invention has the following properties:
Substitution with two hydroxyl groups releases an aromatic alcohol or aromatic thiol. These released compounds have a strong reducing effect and destroy the oxidized crude drug. In addition, two hydroxyl groups of substituents (X is I
! l! Since Fi (7 hydroxyl groups when 2iA atoms) increase water solubility, the diffusivity of the leaving group in the emulsion is increased. Furthermore, diffusivity can be easily adjusted by adjusting the group represented by Y to an appropriate size. In other words, in the present invention, the leaving group released by the reaction between the coupler and the oxidized developing agent exhibits strong reducing properties, and has appropriate water solubility and its diffusivity can be easily adjusted. This is believed to explain the superior performance of the present invention.

This is because the coupler of the present invention can be used to reduce and effectively remove excess oxidized developing agent generated during development. This prevents the individual dyes 1x from increasing beyond a certain level, preventing the occurrence of mottle and improving graininess. Furthermore, when using the coupler of the present invention, an edge effect and a layer effect were observed when the reducing agent released from the coupler had a high diffusivity. This effect was particularly noticeable in color reversal sensitive materials. It is conventionally known to use couplers that release development inhibitors (DIR couplers) for edge effects and Li interlayer effects. However, the current situation is that conventional DI couplers cannot be used in color reversal sensitive materials because they do not have the effect of inhibiting development. Because they used inhibitors,
This is because, in color reversal processing with high development activity, the effect of inhibiting development 1 is not effective. However, Akira's coupler showed vague grain improvement effects and sharpness improvement effects even when used with color reversal photosensitive materials. That is, in the first step of the color reversal process, the compound released from the coupler of the present invention functions as a scavenger for the oxidized developing agent, and the oxidized developing agent is absorbed by 4% of the developing agent. As a result, the developable silver is erased and the a5 primary color is suppressed, so it can be assumed that graininess and sharpness are improved.

The present invention will be explained in detail below.

In the general formula ([), when Y represents a 1〆ty8 group, preferably an aliphatic group, an aromatic group, a heterocyclic group, a halogen atom, an alkoxy group, an arylox7 group, an arylthio group, an alkoxycarbonyl group, thioureido group, acylamino group, sulfonamide group, cyano group, nitro group, carbamoyl group, sulfamoyl group, acyloxy group, alkylthio group, amino group, sulfonyl group, ureido group, aryloxycarbonyl group, alkodicarbonylamino group , a sulfamoylamino group, an acyl group, or a sulfamoylamino group. ). When these substituents contain an aliphatic group, the number of carbon atoms is 1 to 3, preferably 1 to 14, straight chain or chain, branched, chain or cyclic, saturated or unsaturated, substituted or It may be unsubstituted. Also Y
contains an aromatic group, the number of carbon atoms is t~10,
Preferred is a substituted or unsubstituted phenyl group.

In general formula (1), xFi* elementary atoms are preferred.

In the general formula [1], it is preferable that the two OH&s are in the co-position and the position of the x-position with respect to X.

Furthermore, the present invention is particularly effective because the general formula (1
), A is the following general formula [■], [river], (IV),
(V), (Vl), [4], [1], (EK), (X
), a coupler residue represented by (kari) or [store],
These couplers have a large coupling speed and are preferred. 6 formula [11] General formula (il+) General formula (IV) General formula (V) General formula (Vl) General formula [■] General formula [■] General formula (IX) General formula (X) General formula (XI) 〇 General formula [Kari] In the above formula, the free bond derived from the coupling position is the one of the coupling-off group. Indicates the bond position. In the above formula, Ro, R2, R,3, Rt4, aS, a,, %
"7%" 13% B9% "10 or 1 contains a diffusion-resistant group, it means that the total number of carbon atoms is t ~
3 carbons, preferably 10 carbons, otherwise the total number of carbons is /! The following are preferred.

Next, the general formula [■] ~ [store] R-R, 1□, 1, m
and p will be explained.

In the formula, Rt is an aliphatic group, an aromatic group, an alkoxy group t f
C represents a heterocyclic group, and R2 and R each represent an aromatic monocyclic or heterocyclic group.

In the formula, the aliphatic group represented by Ro preferably has a carbon number l
- Here, it may be substituted or unsubstituted, linear or cyclic. Preferred substituents for the alkyl group include an alkoxy group, an aryloxy group, an amino group, an acylamino group, and a halogen atom, which may themselves have further substituents. Specific examples of aliphatic groups useful as R are: isoprobyl, inobutyl, tert-butyl, isoamyl, te.
rt-amyl group, /, l-dimethylbutyl group, /, /-
Dimethylhexyl group, /, l-diethylhexyl group, dodecyl group, hexadecyl group, ophtadefur group, cyclohexyl group, l-methoxyinopropyl group, /-phenoxyisozorobyl group, /E)-tert-glylphenogycyisozolo Bill group, α-aminoinpropyl group, α-(
These include diethylaminone inzolobyl group, α-(succinimide) isozolobyl group, α-(butylimido) inpropyl group, α-(benzenesulfonamido) isopropyl group, and the like.

When Rt2 or EL3 represents an aromatic group (especially a coninyl group), the aromatic group may be substituted.

Aromatic trlP such as phenyl group: group having 3 or less carbon atoms, argyl group, alkenyl group, alkoxy group, alkoxycarbonyl group, alkoxycarbonylamino group, aliphatic amide group, alkylsulfamoyl crystal, alkylsulfonamide group, It may be substituted with an alkylureido group, an alkyl Km succinimide group, etc. In this case, the alkyl group may have an aromatic group such as phenylene interposed in its chain. The phenyl group may also be substituted with an aryloxy group, an aryloxycarbonyl 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 moiety may be further substituted with one or more alkyl groups having a total number of carbon atoms of 7 to -λ.

1(, phenyl l arrearated with FL or FL3
The 2 groups include amino groups, hydroxy groups, carboxyne groups, including those substituted with lower alkyl groups having 1 to t carbon atoms;
Sulfo group, nitro group, cyano group, thiocyano group or
・May be substituted with loge/atom.

It, R2 or FL3 may also represent a substituent in which a phenyl group is fused with another ring, such as a naphthyl group, a quinolyl group, an isoquinolyl group, a chromanyl group, a chromanyl group, a tetrahydronaphthyl group, etc. These substituents may themselves have further substituents.

When R represents an alkoxy group, the alkyl moiety represents a linear or branched alkyl group, an alkenyl group, a concessional alkyl group, or a cyclic alkenyl group having from 1 to 32 carbon atoms, preferably from 1 to λ. , these may be substituted with a halogen atom, an aryl group, an alkoxy group, or the like.

When R1 or R3 represents a heterocyclic group, I
In the case of 2 bonds, each of the 1-branching groups is bonded to the carbon atom of the carbonyl group of the acyl group in the alpha-acylacetamide or the nitrogen atom of the -amide group through one of the carbon atoms forming the ring. Examples of such heterocycles include thiophene, furan, pyran, pyrrole, pyrazole, pyridine, pyrazine, pyrimidine, pyritazine, indolizine, imidazole, thiazole, oxazole, triazine, thiadiazine, oxazizine, and the like. These may further have a substituent on the ring.

In the general formula (mV), R6 is a linear or branched alkyl group having 7 to 3 carbon atoms, preferably 1 to 3 carbon atoms (
For example, methyl, isozolobyl, tert-butyl, hexyl, dodecyl, etc.), alkenyl groups (for example, allyl group, etc.), cyclic alkyl groups (for example, cyclopentyl group,
cyclohenyl group, norbornyl group, etc.), aralkyl group (e.g., benzyl, β-phenylethyl group, etc.), cyclic alkenyl group (e.g., cyclopentenyl, cyclohexenyl group, etc.), and these represent halogen atoms, nitro groups, Cyano group, aryl group, alkoxy group, aryloxy group, carboxyne group, alkylthiocarbonyl group,
Arylthiocarbonyl group, alkoxycarbonyl group,
Aryloxycarbonyl group, sulfo group, sulfamoyl group, carbamoyl group, acylamino group, diacylamino group, ureido group, urethane group, thiourethane group, sulfonamide group, heterocyclic group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group,
alkylamino group, dialkylamino group, anilino group,
N-arylanilino group, N-alkylanilino group, N
- May be substituted with an acylanilino group, a hydroxy group, etc.

Furthermore, R5 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 nine substituents, such as an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group, a cyclic alkenyl group, a halogen atom, a nitro group, a cyano group, and an aryl group. , alkoxy group, aryloki7 group, carboxyne group, alkoxycarbonyl group, aryloki7carbonyl group, sulfo group, sulfamoyl group, carbamoyl group, acylamino group, siafuramino group, ureido group, urethane group, sulfo/amide group, heterocyclic group, Arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, dialkylamino group, anilino group, N-alkylanilino group, N-arylanilino group, N-acylanilino group,
It may have a hydroxy group, etc. A highly preferred R5 is 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 coloration of the cazole remaining in the film by light or heat is prevented. It is small and useful.

Further, R is a heterocyclic group (for example, a !-membered or tN-ring heterocyclic group containing a nitrogen atom, an oxygen atom, an ioc atom as a petro atom, a fused heterocyclic group, a pyridyl group, a quinolyl group, a furyl group, a benzothiazolyl group, oxacylyl group, imidazolyl group, naphthoxacylyl group, etc.), heterocyclic group substituted with the substituents listed for the above aryl group, aliphatic aromatic acyl group, alkylsulfonyl group, arylsulfonyl group, alkylcarbamoyl group. basis,
It may also represent an arylcarbamoyl group, an alkylthiocarbamoyl group or an arylthiocarbamoyl group.

In the formula, L and #: represent a hydrogen atom, a linear or branched alkyl, alkenyl, cyclic alkyl, aralkyl, or cyclic alkenyl group having 1 to 32 carbon atoms, preferably 1 to 2 carbon atoms (
These groups may have the substituents listed for RsK above), aryl groups and Teishinomi groups (these are the substituents listed above for R
may have the substituents listed for 3), alkoxycarbonyl;! ! i (e.g. methoxycarbonyl group,
ethoxycarbonyl group, stearyloxycarbonyl group, etc.), aryloxycarbonyl group (e.g., phenoxycarbonyl group, naphthoxycarbonyl group, etc.), aralkyloxycarbonyl group (e.g., evabenzylox7carbonyl group, etc.), alkoxy group (e.g., methoxycarbonyl group, etc.), ethoxy group, heptadecyloxy group), aryloxy group (e.g. phenoxy group, tolyloxy group, etc.), alkylthio group (e.g. ethylthio group, dodecylthio group, etc.), arylthio group (e.g. phenylthio group, α-
naphthylthio group, etc.), carboxy group, acylamino group (e.g. acetylamino group, 3-((25 μm di t
er t-amylphenoxy)acetamide]benzamide group, etc.), diacylamino group, N-alkylamino group (e.g. N-methylpropionamide group, etc.), N-arylacylamino group (if suitable, N-phenylacetamide group) ), ureido groups (e.g. ureido, N-arylureido, N-alkylureido groups, etc.), urethane groups, thiourethane groups, arylamino groups (
For example, phenylamino, N-methylanilino group, diphenylamino group, N-acetylanilino group, λ-chloro! -tetradecanamide anilino group, etc.), alkylamino group (e.g. n-butylamino group, methylamino group,
cyclohexylamino group, etc.), cycloamino group (e.g., piperidino group, pyrrolidino group, etc.), heterocyclic amino group (e.g., μm pyridylamino group, 2-benzoxasilylamino group, etc.), alkylcarbonyl group (e.g., methylcarbonyl group, etc.) , arylcarbonyl group (e.g., t
), sulfonamide groups (for example, alkylsulfonamide groups, arylsulfonamide groups, etc.), carbamoyl groups (for example, ethylcarbamoyl group, dimethylcarbamoyl group, N-methyl-phenylcarbamoyl, N-phenyl carbamoyl), sulfamoyl 1 (flJt is N-alkylsulfamoyl, N,N-dialkylsulfamoyl group, N-arylsulfamoyl &, N-furkyl-N-arylsulfamoyl group, N,N - diarylsulfamoyl group, etc.), a cyano group, and a hydroxy group; R in the formula represents a hydrogen atom or a linear or branched alkyl group having 1 to 32 carbon atoms, preferably 1 to 3 carbon atoms; Alkenyl group, cyclic alkyl group, aralkyl group, or F
Represents an im-like alkenyl group, which may have the substituents listed above.

Further, R6 may represent an aryl group or a polycyclic group, and these may have the substituents listed for R5 above.

Moreover, EL6 includes a cyano group, an alkoxy group, an aryloxy group, a halogen atom, a carboxy group, and an alkoxy group. 7 Carbonyl group, aryloxycarbonyl group, afluoro:?
72! ! ! :, sulfamoyl group, carbamoyl group, acylamino group, diacylamino group, ureido group, urethane group, sulfo/amide group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group,
alkylamino group, sialgylamino group, anilino group,
N-arylanilino group, N-alkylanilino group, N
-acylanilino group, and may also represent a cylino group.

R7, R, and R8 each represent a group commonly used in an equivalent-type phenol or α-naphthol coupler, and specifically, t and R represent a hydrogen atom, a halogen atom, an alkoxy7carbonylamino group, an aliphatic hydrocarbon residue, N-aryl ureido group, acylamino group, -
0-111□ or -8-R (however, R1□ is an aliphatic hydrocarbon residue), and two or more R
- When 7 is present, two or more 7's may be different groups, and the aliphatic hydrocarbon residues include those having substituents.

Further, when these substituents include an aryl group, the aryl group may have the substituents listed for a5 above.

Examples of R and R3 include groups selected from aliphatic hydrocarbon residues, aryl groups, and heterologous residues, or one of these groups may be a hydrogen atom, and these groups may be substituted with Including those with groups. Mat[
(8 and L may jointly form a j-containing heterocyclic nucleus.

The aliphatic hydrocarbon residue may be f13 or unsaturated, and may be linear, branched, or cyclic. And preferably all alkyl (for example, each group such as methyl, ethyl, zolopyl, isopropyl, butyl, t-butyl, inbutyl, dodecyl, octadecyl, cyclobutyl, cyclohexyl, etc.)
, alkenyl groups (for example, allyl, octenyl, etc.).

Aryl groups include phenyl groups, naphthyl groups, etc.
Representative heterocyclic residues include pyridinyl, quinolyl, chenyl, pyridyl, imidazolyl, and the like. Substituents introduced into these aliphatic hydrocarbon residues, aryl groups, and heterologous residues include halogen atoms, nitro, hydroxyl, carboxyl, amino, substituted amino, sulfo, alkyl, alkenyl, aryl, and foM.
, flukoxy, arylox, arylthio, acylamino, carbamoyl, ester, acyl, acyloxy, sulfonamide, sulfamoyl, sulfonyl, morpholino and the like.

l is an integer of /-4, m is an integer of 7 to 3, pFil~! represents the whole number.

R Yu. is an arylcarbonyl group, an alkanoyl group having 2 to 3 carbon atoms, preferably 2 to 3 carbon atoms, an arylcarbamoyl crystal, having 2 to 3 carbon atoms, preferably tL< is 2 to . 2λ alkanecarbamoyl group, carbon number l to 3), preferably #'1l
-22 represents an alkoxycarbonyl group or an aryloxycarbonyl group, which may have a substituent, and examples of the substituent include an alkoxycarbonyl group, an alkoxycarbonyl group, an acylamino group, an alkylsulfamoyl group, an alkylsulfonamide group, and an alkoxycarbonyl group. Rusuccinimide group, halogen atom, nitro group, carboxyl group, nitrile group,
R0□, which may be an alkyl group or an aryl group, is an arylcarbonyl group, an alkanoyl group having 2 to 3 carbon atoms, preferably 1 to 1 carbon atoms, an arylcarbamoyl group, 2 to 3 carbon atoms, preferably 1 to λλ real Cancarbamoyl group, #, 7 to 3 prime numbers, preferably H/~λ
λ alkoxycarbonyl group or aryloxycarbonyl group, alkanesulfonyl group having 2 to 3 carbon atoms, preferably 1 to 2 carbon atoms, arylsulfonyl group, 7
! J ”a,!-membered or 61-membered heterocyclic group (hetero atom is selected from nitrogen atom, oxygen atom, sulfur atom, such as triazolyl group, imidazolyl group, phthalimide group, succinimide group, furyl group, pyridyl group, and benzyl group) (a triazolyl group), which may have the substituents mentioned in section a. above.

The coupler of the present invention is preferably used in combination with other ordinary couplers, mainly at 0°/mo with respect to the coupler.
l To~If Omo 1%, preferably 10~! O
Used in molti.

Examples of the compounds used in the present invention include, but are not limited to, the following compounds.

(JH OH OH OH U α OH Q C2 OH OH (J) (0■ (JH (JH υH H ULJH LH IJQ! A specific synthesis method for cazoler will be shown below.

Synthesis Example (1) Synthesis of Exemplary Compound (1) Synthesis was carried out by the following synthetic route.

α (JCH3 CH3 OH CH3 μ 0(,”H3 OH OH 70CH3 0H Ut+ Exemplary compound (1) ■Synthesis of compound j: 3ot of compound λ and caustic potash/
2. /f in toluene? By refluxing and distilling off the solvent, the potassium salt of the compound was obtained.

To this was added a solution of Compound 1I7) in about Jt-MiyamtN,N-dimethylformamide and reacted at 20C for 1 hour. In line 7, 1 compound of compound 3 was obtained.

■Synthesis hk of compound l: of compound 3! J9fμ02 was added to lO% aqueous ethanol j00- containing caustic potash and reacted at room temperature for 3 hours. Compound 171 was obtained by post-treatment in a conventional manner.

■Compound! Synthesis: Compound ≠ 272 with ethyl acetate
θOml plus 3 ml of hebutafluorobutanoic anhydride at room temperature.
62 was added dropwise. After reacting for 1 hour, post-treatment was performed by a conventional method to obtain jjf of compound j.

■Synthesis of compound t; Isopronominol≠00. t.

0ft of iron powder was added to a mixed solvent of water 1111 and acetic acid 0111 at room temperature and stirred for 70 minutes at rOoC.

Compound j 369 was added to this, and the mixture was heated under reflux for 1 hour.

Compound t of Vh 329 was obtained by working up in a conventional manner.

■ Combination! 1fI7 mixture g: Compound J-2 was added to 300 ml of acetonitrile and heated under reflux. Cor (
2. λjff of Hiroshi-G tert-amylfuefoxy)hexanoyl chloride was added. After reacting under reflux for 1 hour, post-treatment was carried out by a conventional method to obtain Compound 7 Jll.

■Exemplary compound 'I! ! ! Synthesis of 7(1): Add Jlf of compound 7 to methylene chloride 300'art and add 0°
After cooling to C, boron trib romide tAJf was added dropwise. After dropping, the mixture was reacted for 3 hours at a temperature below to''c. It was gradually added to water/77 saturated with 1 nocum of sodium bicarbonate, neutralized, and then separated using a liquid separation coat. After washing with water, the oil layer was concentrated and a residue was obtained. was recrystallized from ethyl acetate and hexane to obtain the desired coupler [1].

Synthesis Example (2) Synthesis of Exemplified Compound (2) Same as Zengei (1) except that p-77 nophenyl isocyanate was used instead of hebutafluorobutanoic anhydride in step (1) of Synthesis Example (1). It was synthesized using the synthesis method.

Synthesis Example (3) Synthesis of Exemplary Compound (3) bX, ■(
Synthesis example (1
) was synthesized using the same synthesis method.

The coupler of the present invention is preferably used in combination with commonly used photographic couplers. 10" to 7 moles of dye-forming coupler used in the same layer.

The desired effect of the present invention can be obtained by using it in a range of 0 mol, preferably Bo, /-o, r mol.

The coupler of the present invention or the couplers that can be used in combination as described below can be introduced into the light-sensitive material by various known dispersion methods.
Typical examples include a solid dispersion method, an alkali dispersion method, preferably a latex dispersion method, and more preferably an oil-in-water dispersion method. In the oil-in-water dispersion method, the boiling point is i
After dissolving in either a high boiling point organic solvent of 7s'c or more and a low boiling point so-called auxiliary solvent alone or in a mixture of both, fine particles are dissolved in an aqueous medium such as water or gelatin/aqueous solution in the presence of a surfactant. Spread. Examples of high-boiling organic solvents are U.S. Pat. It is described in JJ Co., No. 027, etc. Dispersion may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, noodle washing, or ultrafiltration before use in whole blood.

Specific examples of high boiling point organic solvents include phthalate esters (dibutyl phthalate, dicyclohexyl phthalate),
di-J-ethylhexyl phthalate, didodecyl phthalate, etc.), phosphoric acid or phosphonic acid esters (
triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, triloethylhexyl phosphate, tridodecyl phosphate, driftoxyethyl phosphate, trichloropropyl phosphate, diloethylhexyl phenyl phosphonate, etc.), benzoic acid esters (low ether hexyl benzoate, dodecyl benzony), J-ethyl hexylbenzoate
-Hydroxybenzene/shade, etc.), amides (diethyldodecaneamide, N-tetradecylpyrrolidone, etc.), alcohols such as phenol a (isostearyl alcohol, co-, 4L-di-tert-amylphenol, etc.), aliphatic carboxylic acids Esters (dioctyl azelate, glycerol tributyrate, instearyl lactate, trioctyl citrate, etc.), aniline derivatives (N,N-dibutyl-λ-butoxyj-tert-
octylaniline, etc.), hydrocarbons (paraffin, dobufurbenzene, diisopropylnaphthalene, etc.), etc.As an auxiliary solvent, solvents with a boiling point of about 30° to about 30°/OoC can be used, and a typical example is acetic acid. Examples include ethyl, butyl acetate, ethyl propionate, methyl ethyl keto/, cyclohexanone, -monoethoxyethyl acetate, dimethylformamide, and the like.

The steps and effects of latex dispersion methods and specific examples of latex for impregnation are described in U.S. Pat.

Jbu No. 3, OLS No. 2. ! Buddha 1. Core 4 issue and OL
8, No. 8 Coul, No. 230, etc.

A variety of color couplers can be used in the present invention. The term "color coupler" as used herein refers to a compound capable of producing a dye by reacting with an oxidized product of an aromatic primary amine developer. Typical examples of useful color couplers include naphthol or phenolic compounds, hirazolone or pyrazoloazole compounds, and open chain or heterocyclic ketomethylene compounds. These shears that can be used in the present invention/
, magenta, and yellow couplers are listed in Research Disclosure (L)/744c3 (/7).
It is described in the patent cited in Vll-D Section 117/7 (/7P/July).

The color coupler incorporated in the light-sensitive material is preferably diffusion-resistant by having a pallast group or being polymerized. A two-equivalent color coupler substituted with a leaving group is preferred to a four-equivalent color coupler in which the coupling active position is a hydrogen atom. Couplers in which the coloring dye has appropriate diffusivity, achromatic couplers, and DI kokopo couplers that release development inhibitors along with the coupling reaction, or couplers that release development accelerators are also available! Can be used.

A representative example of the yellow coupler that can be used in the present invention is an oil-protected acylacetamide coupler. A specific example is the US time ff 2. No. 07,210, No.-, 17j, No. 0/7 and No. 3. It is described in Kobuj, No. 604, etc. According to the present invention, the use of two-equivalent yellow couplers is preferred, as described in U.S. Pat. μor, ty hiro issue, same number 3. ψ≠71 Octopus No. J, No. 933.101 and No. Hiroshi No. 02
Ko.

Oxygen atom separation type yellow coupler described in No. 420, etc., or Japanese Patent Publication No. 10732, U.S.
'F'X' No. 21,020, West German Application Publication No. ko, J/P, ?77, No. 2. Colo 7.3≦1, No. 2, 3, No. 317 and Co.

Hiro 33. Typical examples thereof include the nitrogen atom separation type yellow couplers described in No. I/C and the like. α-Piparoylacetanilide couplers have excellent color fastness, especially light fastness, while α-benzoylacetanilide couplers provide high color density.

Magenta couplers that can be used in the present invention include oil-protected indica or anoacetyl couplers, preferably j-pyrazolo and pyrazolotriazole and pyrazoloazole couplers. A pyrazolone coupler in which the 3-position has a 7-arylamino group or an acylamino group is preferable from the viewpoint of the hue of the coloring dye and the degree of color development. , No. 012, No. 2゜3μJ, No. 703, No. 2,4oo, 'yrt
No., same No.-,! P01.173, same No. 3. OI, Ko,
tjJ No. 3. /jJ, No. 194 Oyohi, No. 3゜ri JA, No. 0/j, etc. 2 equivalents//)
J-pyrazolone couplers are preferable because they can provide 0 color development and cylindrical shielding with a small amount of coated silver, and are used as leaving groups in U.S. Patent No. 310. The nitrogen atom leaving group described in No. 1 is U.S. Patent No. μ.

Particularly preferred are the arylthio groups described in European Patent No. 73. A31. The ballast group described in the above has the effect of increasing the degree of ss even when used with j-pyrazolone couplers. As pyrazoloazole couplers, U.S. Patent Nos. 3.3t and t? Virazolobenzimidazoles described in No. 7, preferably US Pat.
Pyrazolo (j, /-c) described in 72jt, 0 Lua issue
](/.

Co, ≠] triazoles, R, D co≠220 (/1+
Examples include pyrazolotetrazoles described in JO (June 2006) and pyrazolo pyrazoles in which the year is month (/Yr). Imidazo (/), which is described in European Patent Pitry, Yet, for its low yellow side absorption and light fastness Ω point of the coloring dye.

[Cob] pyrazoles are preferred, and European Patent No. 11,
Pyrazolo (/, j-b) (/, 2.4
')) Riazole is particularly preferred.

77/ couplers that can be used in the present invention include oil-protected naphthol-based and phenol-based couplers, and US Pat. Hiro 7≠.

Naphthol couplers described in λP3, preferably Fi
U.S. Special Edition No. 1, OI Co., No. 212, No. φ.

iut, Jyt No. 1A, 221r, 2JJ and No. 1.2? A representative example is the oxygen atom dissociating type two-equivalent naphthol coupler described in No. 200. Also, specific examples of phenolic couplers are shown in U.S. Patent No. 2. J4ri, No. 222, same No. I, rot, ty
No. t, No. 2.77, No. 16, No. 2. ♂rij,r
Humidity and temperature robust cyan couplers such as those described in US Pat. cyan coupler,
U.S. Patent No. 77, U.S. Patent No. J, 711
.

No. 301, No. ≠, No. 4.3, No. 6, Hiroshi.

334c, 0t1, 1A, 327,173, West German Patent Publication No. 3.3 Kota, 7 Kota and U; I#=Aki!
The 2,j-diacyl amino substituted phenolic couplers described in Kazuhiro Co.
Third. Sanhiro 6.6λλ, same No. 33J, Tata? issue,
Hirohiro, Hirohiro! / ,! Calling J number, Hiroshi Mukai, Hiroshi 27,7
There is a phenolic colored oak having a phenylureido group at the co-position and an acylamino group at the j-position, as described in No. 47.

The coupler of the present invention and the above-mentioned couplers can be used in combination in the same layer in order to satisfy the % properties required for photosensitive materials, or the same compound can be used in combinations of j'4 and 4.
Of course, it may be added to more than one layer.

In order to correct unnecessary absorption in the short wavelength region of the magenta and cyan coupler chromophores, it is preferable to use Colored Kashi 9- in combination with the photosensitive material 2-2.

U.S. Patent No. μ,/4j, 470 and Japanese Patent Publication No. 7-3
Yellow colored maze/ta coupler described in 24AI No. 3 etc. or U.S. Pat.
1. λ! No. 1 and British Patent No. 1. Typical examples include the magenta-colored cyan coupler described in Iμ4,341.

A polymer containing 11-12% or more of these color couplers may be formed. Typical examples of polymerized oaks are U.S. Pat.

A specific example of the polymerized magenta coupler described in Oro, No. 211 is published in British Special LfF No. 101577.
No. 3 and U.S. Takeko No. 347. Three of his works have been published in the Kotco issue.

In addition, the graininess can be improved by using a chromophore spreading type coupler, and such a coupler is disclosed in the US patent t4! J
l, 34t, ko 37 and British patent No. 2゜lko j, j
Specific examples of magenta couplers are given in No. 70, European Patent No. 173 and OLS 3.32.
Hiroshi, 1.33) describes specific examples of yellow, magenta and cyan.

The dye-forming coupler is used in an amount of 0.00 to 0.1 mole per mole of light-sensitive silver halide in the layer to be superimposed. In color photosensitive materials for photography, photosensitive silver halide 1
The yellow coupler is 0. O7 to 00
5 moles, magenta coupler 0.003 to 0.21
mole, and cyan coupler is 0.00 to 0072
In addition, in color photosensitive materials for printing such as color paper, yellow, magenta, and 7 uncouplers are often used in amounts of 0.1 to 0.05 mol per mol of photosensitive silver halide. It is possible to design photosensitive materials outside this range.

As the binder or reinforcing colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used alone or together with gelatin. .

Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chloride, and silver chloride may be used as the silver halide in the photographic emulsion layer of the photographic light-sensitive material used in the VC of the present invention. Preferred silver halide is silver iodobromide containing silver iodide of less than /j molar ratio. Particularly preferred is silver iodobromide containing silver iodide from comolar to 12 molar.

The silver halide grains in the photographic emulsion may have a regular crystal shape such as a cube, hexagonal, or nohedral, or may have an irregular crystal shape such as a spherical shape, or may have an irregular crystal shape such as a spherical shape. In addition, tabular grains having a thickness of 0.03 microns or less, a diameter of at least 0.4 microns, and an average aspect ratio of ! or more, as described in Research Disclosure Co. 1344, may be used. The emulsion may occupy 50% or more of the total projected area.

The crystal structure may be uniform, the inside and outside may have different compositions, it may have a layered structure, or silver halides with different compositions may be joined by epitaxial bonding, and various crystal structures may be used. It may also consist of a mixture of particles in crystalline form.

Further, the Fi image may be formed mainly on the surface of the particle or may be formed inside the particle.

The grain size of the silver halide may be fine grains of 041 microns or less or large grains with a projected area diameter of up to 3 microns, and may be a monodisperse emulsion with a narrow distribution or a polydisperse emulsion with a wide distribution.

Photographic emulsion rtP used in the present invention, 1Jlafkid
Chimie et Physiqu by es
e Photographique (Paul
Published by Monte 1, 1947) G, l=”.

[) Photographic Emul by uffin
sionChernistry ('l'he F”o
Cal Press, 1244), V, L
, Making by Zelikman et al.
and Coating )'photograph
icEmulsion (The Focal P
The spinning process can be carried out using the method described in ``Res.
Any method such as an ammonia method may be used, and methods for reacting soluble silver salts with soluble halogen salts include one-sided mixing method,
Either a simultaneous mixing method or a combination thereof may be used.

It is also possible to use a method in which particles are formed in excess of recorded ions (so-called back-mixing method).

A method of keeping pAg'r constant in the liquid phase in which silver halogenide is produced as a form of simultaneous mixing method! Alternatively, the so-called Chondral double jet method may also be used.

According to this method, a halogenated emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

28 or more silver halide emulsions formed separately are mixed and C
May be used.

Silver halide grain formation or thing 8! In the process of maturation,
Cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or their 4H! A salt, a rhodium salt or a complex thereof, a salt salt, an iron complex salt, or the like may be present together.

Silver halide holes 4+j　kyu, usually chemically sensitized.

For chemical sensitization, e.g.
raphischenprozesse mit
8i1berhalogeniden” (Akad
e+n1scbe Ver Iagsgesellsc
haft.

t ci b r ) g 7 j~7 J a negative near ar2pd (7) method can be used.

That is, a sulfur enrichment method using sulfur-containing compounds (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines) that can react with active seratin and silver: reducing substances (e.g., stannous salts, Reduction sensitization method using amines, hydrazine conductors, formamidine sulfinic acid, silane compounds;
Periodic table with t, lr, Pd ~ Gold P of group 11 =
Complex salt of 'a) 1- Noble metal sensitization method used alone or I
/'1 Can be used in combination.

The photographic emulsion used in the present invention includes the manufacturing process 1 of the photosensitive material.
, 3. Preventing capri while in a daze or during processing,
Alternatively, various compounds may be included for the purpose of stabilizing photographic performance. That is, azole q1 For example, benzothiazolium salts, nitroimidazoles, 2I-lovenzimidazoles, chlorobenzimidazole fA, spider benzimidazoles, mercaptothiazoles, mercaptobenzotheazoles, mercaptobenzicutazoles mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (
%ItCl-phenyl-yo-mercaptotetrazole)
mercaptopyrimicins; mercaptotriazines; thioketo compounds such as oxadorinthion; azaindenes, such as doriazaindenes, tetraazaindenes (particularly those with pi-hydroxy substitution (' +
3r 3a r 7) Many compounds known as antifoggants or stabilizers such as detraazai/den@), pentaazaindene; benzenethiosulfonic acid, penze/sulfinic acid, benzenesulfonic acid amide, etc. Compounds can be added.

In the photographic emulsion layer of the photographic light-sensitive material of the present invention, for the purpose of increasing sensitivity, increasing contrast, or accelerating development, for example, polyalkylene/oxide or its ether, ester, derivatives such as Nami-7, thioether compounds, thiomorpholines, etc. , quaternary ammonium chloride @ compound, urethane derivative,
It may also contain urea visiting conductors, imidazole derivatives, 3-pyrazolidones, and the like.

The photographic light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or difficult-to-use polymer for the purpose of improving the dimensional stability of the photographic emulsion layer or other hydrophilic colloid layer.

The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. The pigments used include cyanine pigments, merocyanine pigments, and ? JL@/Ani/pigment, Ryotai Melo 7-anine dye, Holopolar cyanine dye,
Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes, which may include hemicyanine dyes, styryl dyes, and hemioxonol dyes. Any of the nuclei commonly used for cyanine pigments can be used as the basic heterocyclic nucleus for this pigment.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion. for example,
Aminostyl compounds substituted with nitrogen-containing heterocyclic groups (for example, U.S. Patent No. 933.32θ, 3,63, 7
21), aromatic organic acid formaldehyde condensates (such as those described in US Pat. No. 3.7'A3,110), cadmium salts, azaindene compounds, and the like. The invention is also applicable to multilayer, multicolor photographic materials having at least λ different spectral sensitivities on the support. A multilayer natural color photographic material usually has at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a W-sensitive emulsion layer on a supporting water. You can choose the order of these layers according to your needs. It is customary to use a cyan-forming coupler in the red-sensitive emulsion layer, a magenta-forming coupler in the green-sensitive emulsion layer, and a yellow-forming coupler in the blue-sensitive emulsion layer, but different combinations may be used depending on the case.

The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer.

For example, activated vinyl compounds (/, J.

j-) lyacryloyl-hexahydro-S-) liazine, 113-vinylsulfonyl-coprobanol, etc.), active...loge/chemicals (co, ≠-dichloro-6-hydroxy-3-triazine/etc.) ), mucohalogen acids (
mucochloric acid, mucophenoxychloric acid, etc.), etc. can be used alone or in combination.

The light-sensitive material produced using the present invention may contain a hydroquinone conductor, an amine phenol derivative, a gallic acid derivative, an ascorbic acid conductor, etc. as a color antifoggant.

The photosensitive material of the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, U.S. Patent No. 3,! 3J, 7
No. 9, 4t, Ko 34. θ/3, Tokko Akira! l-4!
Benzotriazoles substituted with an aryl group as described in Hiro No. 0 and European Watch No. 57, /bu No. 0, etc.
U.S. Patent No. 0 HirojO, Kokota No. and μ, /93
．． Butadines listed on the Tatata, U.S. Clock 3, 7
Cinnamic acid esters described in No. 01° gos and J, No. 707.37j, United States @ff3. Kois, s30
No. 1.12/, 31! Marked on the number NIK
Benzophenones, U.S. Pat. No. 3,74/, 27
2 and Dohiro, Ko. 3/, No. 726, and have the following ultraviolet absorption residual polymer compounds that can be used. U.S. Patent No. 3. ≠? 7Aλ and the same J,
700, Hiroj! Ultraviolet absorbing fluorescent brighteners as described in r-q may also be used. Typical examples of UV absorbers are:
It is described in HJD2μco3ri (Liri♂Hiroshi June 2016).

The photosensitive material made with the present invention can be prepared by using one hydrophilic colloid as a filter dye or as an irradiation dye.
It may contain a water-soluble dye for various purposes such as prevention of yellowing. Such dyes include oquinonol dyes, hemioquinonol dyes, styryl dyes, merocyanine dyes,
7-anine dyes and azo dyes are included. Among them, oquinol dyes; hemioxonol dyes and merocyanine dyes are useful; when carrying out the present invention, the following known antifading agents may also be used in combination;
ll can be used alone or in combination. Examples of anti-fading agents include hydroquinono d4, gallic acid derivatives, p-alkoxy7phenol μj1, p-okinophenol conductor, and bisphenol:j:l'J
There is a W.

Color photographic emulsion Iv forming the dye image layer according to the present invention
I is a support material such as plastic film, paper, or cloth that is commonly used for photographic materials! ζ is applied. Useful as flexible supports are cellulose acetate, cellulose acetate butyrate, polystyrene, polyethylene terephthalate, films consisting of semi-synthetic or synthetic polymers such as Baryta 1 or α-olefin polymers ( (e.g. polyethylene, polypropylene)
The support 7c may be a laminated paper or the like, which may be colored with a dye or pigment, or may be made black for the purpose of blocking light.

When these supports are used for reflective materials, it is preferable to add a white pigment to the support or laminate layer. White pigments include titanium dioxide, barium sulfate,
Examples include zinc oxide, zinc sulfide, calcium carbonate, antimony trioxide, silica white, alumina white, titanium phosphate, etc., and titanium dioxide, barium sulfate, and lead oxide are particularly useful.

The surface of these supports is generally treated with an undercoat to improve contact with photographic emulsions, etc. The surface of the support may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the undercoat treatment. When these branches are used for reflective materials, a colloid is added between the base 14 and the emulsion, in which the white pigment is concentrated in high density, to improve the whiteness and photographic properties. Image/Tsu [+1 Sheep Sharpness can be improved.

In the reflective material having the magenta coupler of the present invention, a polymer-laminated paper fork is used as a support.
Although this is often the case, using a synthetic resin film kneaded with white pigments not only improves smoothness, gloss, and sharpness, but also improves chromatic changes, dark areas, and D rendering. is particularly preferable. These 4 units are synthetic atI! Polyethylene terephthalate and cellulose acetate are used as fill material, and barium sulfate and titanium oxide are used as white pigments.The color 4 true light-sensitive material of the present invention includes, in addition to the above, known materials in this field. Various 6710 agents for Shamaru, such as stabilizers, anti-capri agents, surfactants, anti-caesthesia agents, developing agents, etc., can be added as necessary, and from Example t. (4 of them are listed in J.

In some cases, a silver halide emulsion layer or other hydrophilic layer is added.
A grain silver halide emulsion having substantially no photosensitivity (for example, a silver chloride, silver bromide, or silver chlorobromide emulsion with an average grain size Q of 20 μm or less) may be added to the colloidal layer.

The color developing solution that can be used in the present invention is preferably an aqueous alkaline solution containing an aromatic primary amine color developing agent as a main component. As a color developing agent, Hiro-amino-N, N-diethylaniline, J-methyl-μm amino-N, N-diethylferri/, Hiro-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl =φ
-Amino/-N-ethyl-N-11-human aki7ethylaniline, 3-methyl-φ-amino-N-ethyl-N-β
-Meta/sulfoamide ethylaniline, Hiro-amino-3
Typical examples include -methyl-N-ethyl-N-β-methoxyethylaniline.

Color development # is based on alkali metal sulfites, carbonates, and oxides.1.゛4, and Renoba 1. pH like A 1
1, bromide odor, iodide, support and n-power pre-preventing agent, etc., ILp +ij! It can contain an I agent or an anti-capri agent. Also, feel safe vcor[;Ji, water softener, human aki/ruamine's likeness 1 dumb-j1 be/
M such as dialcohol, diethylene glycol, polyethylene glycol, quaternary ammonium salts, development accelerating additives such as amines, dye-forming couplers, competitive couplers, fogging agents such as sodium boron hydride, /-phenyl - Auxiliary developers such as 3-pyrazolidones, tackifiers, US patents tt, ori.

Polycarboxylic acid-based quenching agent described in No. 7.23, West German Publication (JL8) Ko, T-ko λ, +l described in SO No.
A '1'' anti-oxidizing agent such as an anti-oxidizing agent may also be used.

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 a bleaching agent, it is called ``lit''.
), cobalt (lll), chromium (Vl), copper (11)
Multivalent mineral compounds such as peroxides, quinones, nitroso compounds, etc. may be used, such as ferricia/compounds, point chromates, ill and cobalt (lit).
organic complex salts of, for example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-zolopanoltetraacetic acid, or citric acid;
Acids, complex salts of organic acids such as malic acid; persulfates, manganates: ditronophenol, etc. can be used.

Of these, potassium ferrinanide, sodium ethylenediamine/iron(Ill)tetraacetate, and ammonium ethylenediaminetetraacetate (Ill) are particularly useful. The ethylene diamine ferric iron ([[) complex salt is useful in both stand-alone bleach solutions and -bath bleach-fix solutions.

It may be washed with water after color development or bleach-fixing treatment. Color development can be carried out at any temperature between /I0C and zz"c. Cold color development is preferably carried out at a temperature of 3o0C or higher, particularly preferably sj"C or higher.

The development time t5r5 is preferably about 3 minutes to about 1 minute, and is preferably short. For continuous development processing, it is preferable to replenish at night.
Processing curve per square meter JjOcc/AO
cc, preferably 100 cc or less of liquid is replenished. Current 2. Benzyl alcohol at night is -Q shoulder t/l or more F1
It is preferably 1 olIIl/l or less.

The drift fixed lip can be carried out at any temperature from /r'C to jo'c, but Jo 0 layer or more is preferable. When the temperature is Jj0C or more, the processing time can be reduced by one minute, and the amount of liquid replenishment can be reduced. Washing Fl after color development or floating feet
The r@ time is usually within 3 minutes, and it is also possible to wash with water within 1 minute using a stable bath.

Colored pigments deteriorate and fade due to exposure to heat and temperature, but also due to mold during storage. Cyan images are particularly susceptible to severe deterioration due to mold, so it is preferable to use a mold preventive agent. Specific examples of antifungal agents are listed in Japanese Patent Application Laid-open No. 17-17-/! 72μ
There are corchiazolylbenzimidazoles as described in Hiromu. The antifungal agent may be incorporated into the photosensitive material.
It may be added externally during the development process, and if it coexists with the processed photosensitive material, it can be added at the desired process.

The present invention can be used for general silver halide color light-sensitive materials such as color negative film, color paper, color positive film, slide color reversal film, color reversal film for both picture and screen, and color reno single film for TV. In particular, when used in color negative films that require high sensitivity and high image quality, especially color reversal films, remarkable effects can be obtained in improving sharpness and graininess.

The present invention can be applied to light-sensitive materials that use a single black coupler system or a mixed three-color coupler system. A detailed description of the black coloring coupler system can be found in U.S. Pat. Issue, same da, lko≦, $4/issue, Karikai Sho j5-70!1μ7 issue, same! 2-≠272j and the same! ! -10! The three-color coupler mixing method is described in λHong No. 1, and the three-color coupler mixing method is
A detailed explanation can be found in c1osure/7/.

Example 1 On a triacetyl cellulose support provided with an undercoating layer,
Apply the drilling layer and auxiliary layer in step 11 of F, and prepare sample (1).
2-(heptafluorobutyramide)-j-(J'-(KO", HIRO"-di-t-amylphenoxy)butyramide 1 phenol (in coupler) i
Dissolved in ooy2 tricresyl phosphate/00cc and ethyl acetate 700cc, io4 gelatin aqueous solution 1
kg, surfactant + ill dodesolbe/ze/sodium sulfonate lO2 and emulsion f00f obtained by stirring at a spindle speed was ground with red-sensitive low-sensitivity iodobromide parent emulsion/kg (average grain size of silver halide grains 0°3μ, Iso 702, gelatin toy
Contains legal content of 3 mol%) Japanese gelatin, water, stabilizer,
? 2! Add fabric aids, etc. and mix until the film thickness after drying is 2μ.
It was applied to make it look like this. (Amount of silver 0.49/m) 2nd layer: Emulsification of cyan coupler used in intermediate red-sensitive emulsion layer and α1 layer 4W/kq
k, redness; raw intermediate 1 odor ratio silver milk i'l/k (average grain size of silver halide grains O1jμ silver 70?
A mixture of gelatin (containing gelatin tOf and iodine content of 3 mol), gelatin, water, a stabilizer, a coating aid, etc. was added, and the mixture was coated to a dry film thickness of 1 ml. (Mrs., Io, Hiro2/m)
No. 711 High sensitivity red sensitivity emulsion layer Nine conversion of coupler used in the first layer Silver 70 ta Gelatin 4゜2
(contains legal content 3 mol%) and gelatin, water, stable i11
, mix with a coating aid, etc. to obtain a dry film thickness of lμ. If4 Intermediate lf4! ,! -G5ec-Octylhydroquinone 2007
was dissolved in ethyl acetate-00cc, 70% gelatin water solution 1 &/or 9 and dode/rubet/ze/sulfonic acid soda 0
The emulsion obtained by stirring 1 at high speed is mixed with gelatin, water,
The mixture was mixed with a coating aid, etc., and coated to a dry film thickness of lμ.

1st layer Low green sensitivity emulsion M Mai/Ta coupler /-(co,@,4-trichlorophenyl)-J-(J-(co,4L di-t-amylphenoxyacetamide)benzamide 1-j-pyrazolone was used The rest was an emulsion toor prepared in the same manner as the first layer emulsion, and a green-sensitive, low-sensitivity silver bromide emulsion/kq (average grain size 0.3μ, containing silver 702 and gelatin 7t07).
Gelatin, water, a stabilizer, and a coating aid were mixed and coated to a dry thickness of 11' x 2 μm. (
Silver amount: 0.777 m) No. AID 1/kg of the magenta coupler used in the intermediate green-sensitive emulsion layer π5 layer is a green-sensitive, intermediate silver iodobromide emulsion/kq (average grain size O0Sμ
Silver 709 Gelatin 60? A mixture of gelatin, water, a stabilizer, a coating aid, etc. was applied to give a dry film thickness of lμ. (Nuriginen-0,≠2
7m) 7th layer Highly sensitive green-sensitive emulsion layer Emulsion of magenta coupler used in the 5th layer/kg
Green-sensitive, highly iodine-sensitive silver bromide emulsion/kQ (average grain size 0.7μ, containing 701 silver and 1.Of gelatin, method 1!e)
@-(3 molti) was mixed with gelatin, water, a stabilizer, a coating aid, etc., and coated to a dry film thickness of lμ. (Refu Ginhyo O1 Hiroshi2/m) 2nd Layer The emulsion used in the intermediate 1-th layer was mixed with kQ, gelatin, water, and a coating aid, and coated to a dry film thickness of 06jμ.

2nd layer Cc color filter 1st layer Yellow colloidal silver and gelatin were mixed and coated to a dry film thickness of lμ.

1st Olymers Low sensitivity emulsion layer Yellow coupler, α-(piparoyl)-α-(/-be/girou!-ethoxy-3-hydantoinyl)-1-chloroj-dodefluoroki7carponylacetanilide @/II&j An emulsion prepared by using tricresyl phosphate (i/20 cc) instead of cyan coupler and changing ethyl acetate to 120 cc.
G-type low iodo-sensitive silver bromide emulsion/kgc average grain size 0. j
μ, Sl! The mixture was mixed with gelatin, water, Stable 41, and a coating aid, and coated to a dry film thickness of 0. (Kanfu Gin ψ O6 Bu 97m) 1st/i unit Intermediate office sensitive emulsion layer Emulsion of yellow coupler used in 1st O layer lkQ all W
Sensitive intermediate silver emulsion / kg (average grain size o,
tμ, silver 70ft, gelatin toy, iodine content 3 mol%) mixed with gelatin, water, stabilizer, coating aid, etc.
The coating was applied to give a dry film thickness of r1 lμ.

(Paper elongation O1≠2/m) The yellow coupler emulsion/kq used in the 70th layer of the first high-sensitivity blue-sensitive emulsion layer is
n<high sensitivity Hry silver iodobromide milk i'll / kg
(Average particle size 0.7 μ, silver 70 f, gelatin 40
9, iodine 11 ; 3" k:: j mol %), gelatin, water, stabilizer, Cf fabric aid ￥P are mixed, I:t
・So that the film thickness is lμ: "i3, <5. (4 cloth 4
if'(0,'A?/m)th Hiro layer i company 21
UV absorber instead of coupler, J-ri p-ro 2-(2
-Hydroquine-3,j-di-t-butylphenyl) -
, 2H-pensitrianol/39, co(1-hydroxy-5-t-ytylphenyl)-co)l-benzotriazole 30f, co(cohydroxy-J-sec
-butyl-j-1-butylphenyl)-1) 1-benzotriazole 3j9, dodecyl-1-(N,N-diethylamino)-cobenzenesulfonyl-,≠-pentagenoate 1OOy to tricresyl phosphate 20
0cc, dissolved in p-ethyl vinegar-〇〇cc, sodium dodecylbenzenesulfonate ioy, io% gelatin J kQ
2./kg of the emulsion obtained by rapid stirring was mixed with gelatin, water, a coating aid, etc., and coated to a dry film thickness of 2 μm.

(Total UV absorber application amount 0.197m2) No. 117 @
First holding layer: Fine-grain silver iodobromide emulsion (grain size 0, / p, containing silver 709, gelatin f74Of, containing iodide (i: 1 mol), gelatin, water, stable), which has not been chemically sensitized. agent,
It was mixed with a coating aid, etc., and coated to a dry film thickness of lμ.

(Amount of silver: 0.397 m) The obtained multi-I@coated film was used as a sample.

l/λ of the cyan coupler used in the first to third layers! f+
ft An emulsion was prepared in place of the compound of the present invention (equal mole number). Using this emulsion, Samples A to I were prepared according to the method for preparing Sample I.

Comparative compound NHO2) 17(i) H Sample boiled to 1 for grain size measurement, passed through star/M source, sample 1 after color reversal processing # by micro-density measuring machine)
The granularity at ILIIi image density /, 0 and co, 0 in which R, MS granular dust was measured by & measurement is shown.

Sample A/=A/ was exposed to light through a pattern for MTF measurement, and after color reversal processing, the sample was measured with a microdensity meter, and the MTF value was determined by calculation.

The sharpness is expressed in r4TF1 direct of to lines/mm20 lines/mm.

=-(un+t(, MS granularity) Sharpness MTFA rLke/, OCei, o lo
pcs/mm 20 pcs 1/rnfn/ +23
37 0.7ta o, srJ
II, 2J Ooriλ O
otbuJ 19. 2!
0. ri / 0.41 hiro +20
+2 Hiro O0♂7 0. t3j
Ko / Kojo o, rzo o,
t colo meta co3 0. the law of nature/
0.617 Meta 23
0. ri o o, 6 reference t II
JJ o, rl o, 63ta
22 J5' 0,12 0
．． lll1o i3. 2t
o,xi o,5rii JJ
xr o, rl o, 6°/2
22 J7 0,113
Compared to the 0.60 ratio softening sample using the compound of the present invention, the grain sharpness was greatly improved at the surface.

Processing process 19 hours Temperature 1st IQf%'t' 310C (+0.
3) Wash with water 2'
Transfer-I 〃Color development 4/
//Toning li λ′ 〃 Bleaching 6′ 〃 Setting Ne1 Hiro′ 〃Water washing μ′
〃stable l′ constant
Warm dry first developing water 70
0,/sodium tetrapolyphosphate λ
2 sacrificial sodium sulfate 20? Hydroquinone monosulfonate 309 Sodium carbonate (l hydrate) 3021-Phenyl-
μm Methyl-≠-Hydroxymethyl-3 One pyrazolidone Potassium dibromide9
Mu 2. j2 Potassium thiocyanate 7.22 Potassium iotide (0.7%
Solution) - Add 2 liters of water
1000x1 inverted water 7
00 village nitrilo・N-N-N-)rimethine/phosphonic acid・tNa 3y 1st chloride
Tin (dihydrate/fp-aminophenol o, iy hydroxide, I, lium)
ry ice vinegar enemy
/jg/add water
1000ml color developing water 70
0 Shouldert Sodium Tetrapolyphosphate Co2
Hexatrichum sulphate 72 No. 3
Sodium phosphate (water salt) JAF Potassium bromide / Potassium iodide (O0l solution) Sodium hydroxide 37 Citrazic acid
1.1fN-ethyl-N-(β-methanesulfonamidoethyl) -3-methyl-≠-aminoaniline sulfate iiiy ethylene/diamine 31 Add water
10100O adjusted water 70
Sodium sulfate l around 0 tsl
Core sodium ethylenediaminetetraacetate (dihydrate), rl Thioglycerin O, ≠ Add glacial acetic acid J rgl water 1000ml0 White water 1
00 Shoulderl Ethyleneamine Sodium Tetraacetate (dihydrate) 2602 Ethylenediamine/Tetraacetate C- Iron (It) Ammonium (λ Water Salt) i, Ja, ay Potassium Bromide 100. Of? Add water /, O4 fixing water 10
0 gastric I thiosulfite/monium to, or sodium sulfite z, oy sodium sulfite! , 02 Add water
'・04 stable water t
oo appeasement formalin (37 throat) 1.0
m1 surfactant solution (product name Dryfel)! , add Oal water 1. 01 Example 2 A multi-color photosensitive material (10/) was prepared on a transparent triacetyl cellulose film support with each layer having the composition shown below.

, Hemp/J-thread; Anti-halation layer black colloidal silver ・・・・・・・・・・・・ 0 ,
/ j f / Wl "Ultraviolet absorber U-/ ・
0,0117m” U-co-o, i-coy
Gelatin layer groove 11f1 containing 7 m2: Intermediate layer Co, j-G-t-pentadecylhydroquinone...0.11197 m"Coupler C-t...0, /
/ f / m 3rd gelatin layer; 1st red-sensitive emulsion layer...... t, xf/m2 sensitizing dye l... Silver For 1 mole!, 4LX
10 moles of sensitizing dye 1 o per mole of silver
, uxio mole t4R'v color accumulation■ ......-J, &×lO mole per mole of silver Sensitizing dye■ ......-... ψ per mole of silver
, 0XIO molar coupler C-2... σ, 4Arf/
m"Coupler 03-1 old-0,03197WE"Coupler C-Hiro ...... O1O coif/m2 Kurairomu gelate/1.・・・・・・ /, It/m2 Sensitized color A; 1 ・・・・・・・・・ For 1 mole of silver VC! , co × lθ molar sensitization other system ■ ・・・・・・・・・ 1 per mole of silver
, jXIθ mole increasing I Tachibana dye III ・・・・・・・・・ Ko per 1 mole of sensitizing dye, /
×10 'Molar coupler C-co...'-(' j
Of/m2 coupler C-z ・・・・・・・・・
・・・ 0.070f/m2 Kazolar C-3・・・・・・
... 0. The gelatin layer containing υJ j f/m2! Layer; Medium+HI j even J, j-di-t-pentadecylhydroquinone...0, Or f/m
Gelatin layer z-th layer containing: 'tct green-sensitive emulsion layer...0, If Of/m'
Sensitizing dye V......Hiro, 0x10 mole per mole of silver Sensitizing dye■......J per mole of silver
, OX/σ molar sensitizing dye ■ ・・・・・・・・・ per mole of silver /
, 0x10 Molar coupler C-1... O0≠ry7m
2 Kazolar C-7・・・・・・・・・ 0.1377
m2 coupler cr-r ・・・・・・・・・ 0.0
29/m2 Casoler C-u ・・・・・・・・・
0.0≠f//m2 Gold-containing gelatin layer No. 71; εii Green-sensitive emulsion layer 0. Ijf/ln2 sensitizing dye V
・・・・・・・・・ 2.7X10 for 1 mole of silver
Molar sensitizing dye ■ ・・・・・・・・・ 1 per mole of silver
．． 1xlO mole sensitizing dye ■ 7 for 1 mole of silver
, ! X/ 0 Molar coupler C-6・・・・・・・・・ Q, Ori j f
/ m2 coupler C-7...-----0,0/
! Gelatin layer t# containing f/m2; yellow filter layer yellow colloidal silver 0, 01
f / m ”, j-j-t-be/tadeflu hydroquinone...gelatin layer containing 0.0901/νn2, 1st layer; 1st blue-grained layer... 0.J7f/mz sensitizing dye■ ・
・・・・・・・・・ 1 for 1 mole of silver, ≠X/θ−4
Molar coupler C-2・・・・・・・・・ 0.7/l/m
2 coupler C-Hiro ・・・・・・・・・ 0.07f
Gelatin layer containing /m''ioH@; Second sensitizing emulsion layer...0.jjf/rrL'' sensitizing dye■
・・・・・・・・・ J, OX for 1 mole of silver
I O Molkab 2-C-?・・・・・・・・・ O, ko3 f
Gelatin layer 11R: i; first protective layer ultraviolet absorber U-/...0. /μf/m
"Gelatin layer containing the same U-co-0,2jf/m2; 1st protective layer...O, cot f/m2 polymethacrylate particles (diameter/, jμ) - -----・0.10f/m2
In addition to the above composition, a gelatin hardening agent H-7 and a surfactant were applied to each gelatin layer containing the above composition.

(Sample) Oko, to3) Coupler C-2 of the third layer of sample 10/! Samples 102 and 103 were prepared in the same manner as sample No. 0/, except that 0 molti was replaced with couplers (13) and (14) 00 molti of the present invention, 71c.

These samples were exposed to light for sensitometry through a red filter and subjected to color development processing as described below. Further, the photographic properties and graininess of the sample obtained after performing conventional exposure for R and MS measurement and similar color development were measured using a red filter. The aperture for grain size measurement was μlμ.

The development used here was carried out at 3r 0c as described below.

1 Force 2-Development ・・・・・・・・・ 3 minutes 11 seconds 2
饋white ・・・・・・・・・ minutes 30 seconds 3 water
Washing 3 minutes/J seconds 4 Fixing ・
・・・・・・・・・ 4 minutes 30 seconds 5 Wash with water ・・・・
・・・・・・ 3 minutes/j seconds 6 Stable ・・・・・・・
... 3 minutes/j seconds The specific treatment liquid composition used in each step is as follows.

Color developer sodium nitrilotriacetate i, op11 town sodium sulfate Hiroshi, Of sodium carbonate! 0. Of potassium bromide
1. ≠2hydroxy/ruamine sulfate, 4c2gu (N-ethyl-N-β-
Hydroxyethylamino)-2-methylanili 74m acid salt Hiroshi, zy Add water ll white liquor ammonium bromide /AD, Of ammonia water (1% λj, QCC ethylenediamine-tetraacetic acid sodium iron salt /30.Of glacial acetic acid
Add ginseng and Occ water
llFixer Sodium Tetrapolyphosphate Co,OfSacrificial Sulfur I''
19 Sodium Hiroshi, Of ammonium thiosulfate (717%) /7! , Occ bent sodium sulfate, add tl water
/1 stabilized formalin Add 1.0cc of water / -1 1st table Relative sensitivity: Relative value of sample / 0 / tl-100 as the reciprocal of the exposure that gives fog +0.2 Note: Concentration 0. From Table 1, it can be seen that the samples ioλ, lO3 of the present invention clearly have excellent graininess.

Structure of compound used in Examples U-/ α C-J 80 Na 80sNa C-Reference-z QC) 12C) 128CH, COυh α C2) 1°% Correction Consultant Fuji Photo Film Co., Ltd. Procedural Amendment 1, Display of incident Showa 2nd year patent application No. 20413/
No. 2, Name of the invention Silver halide power 2 - Photographic light-sensitive material 3, Person making the amendment Relationship with the case Patent applicant Location 210-4 Nakanuma, Minamiashigara City, Kanagawa Prefecture Subject of amendment Mei Ia
IP! The description in the column ``Detailed Description of the Invention'' in Column 5 of ``Detailed Description of the Invention'' in ``Detailed Description of the Invention'' in ``Description of the Contents of the Amendment'' is amended as follows.

The description from page 3F, line 7 to line ≠oJjλ is changed to ``The coupler of the present invention is preferably used in the silver halide emulsion layer or a layer adjacent thereto, and is preferably used in combination with ordinary photographic color couplers. Preferably, the amount of the coupler of the present invention to be used (the ratio of the coupler of the present invention/ordinary photographic color coupler) is preferably j/lij~/0010, and 10/90~6
0/4! O is more preferred. ” he corrected.

Claims (1)

[Scope of Claims] A silver halide color photographic material containing a coupler represented by the following general formula. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, A represents a coupler residue that cleaves with X upon reaction with the oxidized developing agent, X represents an oxygen atom or a sulfur atom, and Y represents a hydrogen atom. or represents a substituent, n represents 1 or 2, and when n is 2, the two Y may be different substituents, or the two Y each become a divalent group and are connected to form a cyclic structure. You may. ]