JPS63304254A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a color photographic sensitive material having superior color image quality, that is, sharpness or color reproducibility by incorporating at least one kind of specified compd. CONSTITUTION:A compd. represented by the formula is incorporated into a silver halide photographic sensitive material. In the formula, each of A1 and A2 is a coupler residue freed of one H atom at the active position, Ar is arylene, DI is a photographically useful group and n=1 or 2. The compd. may be incorporated into any of the red-, green- and blue-sensitive emulsion layers and is preferably incorporated into one of the layers by 1X10<-6>-0.5mol. per 1mol. silver present in the layer or an adjacent layer. Since the compd. hardly lowers the sensitivity of the sensitive material and improves the sharpness, a color photographic sensitive material having high sensitivity and superior sharpness is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a color photographic material with excellent color image quality, ie, sharpness or color reproducibility. More specifically, the present invention relates to a color photographic light-sensitive material containing a compound characterized in that a DIR compound is cleaved by reaction with an oxidized product of a natural herbal drug.

(Prior Art) Much research has been carried out on subtractive color photographic materials for the purpose of improving the sharpness of images9.

Examples include research on thinning the emulsion layer for the purpose of preventing light scattering, and research on chemically improving sharpness using the edge effect. The former method of thinning mainly involves MTF in the high frequency range (MTF values are determined by T. H. James (T.
H. James) II “The Theory of the Photographic Bromo
of the Photo-graphic Pr
(see µth Edition Pt 08), but it has little effect on improving sharpness in the low frequency range.

Couplers that release development inhibitors (DIR couplers) are used for the purpose of improving sharpness by the edge effect.

For example, U.S. Patent No. 3. Cocoa, jJa issue, same! ,/AF
, No. 062, same J, fJJ.

Couplers that release a development inhibitor from the coupling position are disclosed in Zoo No. 4477.143. In these couplers, a development inhibitor is bound to the coupling position of the coupler, and therefore, in some cases where a development inhibitor is used, a problem arises in that the coupling reaction between the coupler and the oxidized developing agent is slow. In order to improve this, it is necessary to interpose a linking group between the coupling position of the coupler and the development inhibitor. For example, the couplers are described in U.S. Pat. These couplers do show an improvement in the speed of the coupling reaction and exhibit a certain degree of performance. However, in terms of improvement in sharpness, it has been found that there is almost no difference in sharpness when compared with a DIR coupler in which a development inhibitor is directly attached to the coupling position, compared to a coupler that is inherently highly reactive with the oxidized product of the developing agent.

Additionally, U.S. Patent Nos. μ, μ31,/Pj, 4A
, JJr, No. 393, 4L, 310. tar, British Patent No. 2. //4c, 7≦CoA discloses examples of couplers that emit DIR couplers. The couplers described in these patents, when the coupling speed is moderately large,
Although it was effective in improving graininess, it was found that the improvement in sharpness was due to the opaque component, and as the amount of addition was increased, the decrease in sensitivity was large, and the degree of improvement in sharpness was not large enough. It has been found that there is a limit to the improvement of sharpness.

For recent high-sensitivity photosensitive materials such as 18CJ1400 color negatives, I-type couplers are desired because they improve sharpness without reducing sensitivity. The film used in disc cameras, which are convenient to carry, has a small area and has a large magnification when printing, so it is currently desired to further improve the sharpness of the image.

(Problems to be Solved by the Invention) Therefore, an object of the present invention is to provide a color photographic material with high p-sensitivity and excellent sharpness by using a compound that does not reduce sensitivity and improves sharpness. That's true.

[Means for solving problems]

The purpose of the present invention is to solve the following general formula [! This was achieved by using a silver halide photographic light-sensitive material which contains a compound represented by the following formula: jk%.

General Formula (I) In the formula, A1 and A2 each represent a coupler residue from which one hydrogen atom at the active position is removed.

Ar represents an arylene group.

DI represents a photographically useful group.

n represents 1 or λ.

The reaction process in which the compound represented by general formula (I) releases DI during development is represented by the following reaction formula.

formula, A A Ar%DI and n are general formula C
It has the same meaning as explained in 1), and T (B represents an oxidized developing agent).

In the compound of the present invention, the reaction process in which the dianion released by the reaction of two molecules of To cleaves DI by further reacting with Te can be understood from the above reaction formula.

In general formula (I), A1 and A2 represent all coupler residues except one hydrogen atom at the active position, and known ones can be used as these.

For example, yellow coupler residues (e.g. open-chain ketomethylene type coupler residues), magenta coupler residues (e.g.!-
pyrazo a-type, pyrazoloimidazole-type, pyrazolotriazole-type coupler residues), cyan coupler residues (e.g. phenol-type, naphthol-type coupler residues), and colorless coupler residues (e.g. indan 7m).
% coupler residue such as acetophenone type] U.S. Patent No. 44,3F! , No. 070, 4A, /13,71
λ issue, Dohiro, /7/, 2.23 issue, same≠, -λt.

Examples include coupler residues listed under No. 234.

In the general formula (I), Ar represents an arylene group t-, which includes, for example, a phenylene group and a naphthylene group, which may have a substituent.

Examples of substituents include halogen atoms (chlorine atoms,
bromine atom, etc.), alkyl groups (e.g. methyl group, ethyl group, methoxymethyl group, etc.), alkyl groups (e.g. methoxy group, p-chlorophenoxy group, etc.), aryl groups (e.g. phenoxy group, p-chlorophenoxy group, etc.) group), alkoxycarbonyl group (e.g. methoxycarmenyl group, ethoxycarbonyl group, etc.), aryl-dicarbonyl group (
For example, pheno dicarbonyl group, p-chloropheno dicarbonyl group, etc.), sulfonamide group (for example, methanesulfonamide group, n-butanesulfonamide group, benzenesulfonamide group, etc.), sulfamoyl group (N,
N-diethylsulfamoyl group, ethylsulfamoyl group, etc.), amino group (e.g. ethylamino group, diethylamino group, etc.), carbamoyl group (e.g. diethylcarbamoyl group, etc.), acylamino group (e.g. acetamido group, etc.), sulfonyl groups (such as methylsulfonyl groups), cyano groups, aryl groups (such as phenyl groups), aralkyl groups (such as benzyl groups), nitro groups, hydroxy groups, carboxy groups, acyl groups (such as acetyl groups), etc. An example of this is Ikuki Yomo.

DI represents a photographically useful group, examples of which include development inhibitors, development accelerators, bleach inhibitors, bleach accelerators, developing agents, sterilizing agents, silver oxide solvents, silver-complexing agents, Hardeners, tanning agents, toning agents, capri agents, antifoggants, chemical sensitizers, desensitizers, photographic dyes or their precursors, couplers (e.g. competitive couplers, color forming couplers, f
J4. image suppressor-releasing couplers, etc.).

Among these photographically useful groups, development inhibitors are preferred.

Next, more preferable ranges among the compounds of the present invention will be explained.

Preferred examples of A and A2 represented by the general formula (I) include the following general formula (cp-/), (Cp-2 containing (Cp-3)
, (Op-μ), (Cp-7), (Cp-1, (up-
7), (cp-r>t or (Cp-ta)).These couplers have a high coupling rate and are therefore preferred.

General formula (Up-/) General formula (Cp-, Z) General formula (Cp-J) LsIs General formula (Cp-≠) k'57 General formula (Cp-1) R57 General formula (Cp-4) General formula (Op-7) General formula (Op-r) General formula (Op-2) In the above formula, the free bond derived from the coupling position represents the bond position 11 of the coupling-off group.

In the above formula, R, R, R-几54- R%, RRRH.

555657%58%59%60% If R6□, R62 or R63 contains a diffusion-resistant group, it is selected such that the total number of carbon atoms is l to go, preferably 10 to 30; The total number of numbers is /! The following are preferred.

Bis-type, telomer-type, and polymer-type couplers (in which one of the above substituents extends the divalent group and connects repeating units, etc.). In this case, the range of carbon numbers is It may be outside the regulations.

Below are details about R, d and e.51
6B Explain in detail. In the following, 841 represents an aliphatic group, an aromatic group, or a heterocyclic group, R42 represents an aromatic group or a heterocyclic group, and R% R44 and R415 represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group. represents.

ru and □ have the same meaning as 几 and □.几, 2 and le,
Each 3 represents the same meaning as '42.

几5. represents a group having the same meaning as R41. '56 and 几 each represent a group having the same meaning as the R43 group and a taste group.几 and 9 represent a group having the same meaning as R4□, i.Jt-.

When d is a plural number, a plurality of 859's may represent the same substituent or different substituents t-, and each R59 may become a divalent group and connect to form a cyclic structure. Examples of the ninth divalent group forming the cyclic structure are an integer from O to Hiro, and g is a constant from O to Ko, respectively.几. . represents a group with the same meaning as 几 and □. Ordinary 6,
represents a group having the same meaning as R and □.

几, □ has the same meaning as "41" 1, 几, □C (H- group to J, R4□C) C (JN) i-4, R, □8 (J, NH-
i, R43〇- group, R4□S- group, halogen atom or 5
o2-, x, 几, 3ocu-4, ordinary, 3(J-8(J2
- group, halogen atom, nitro group, cyano group or R,3
e (J-: Represents I&, e represents an integer t- from O to 〆. Plural R6 □ squares are the same when R63 exists, and squares are different. f: represents.

In the above, the aliphatic group is a saturated or unsaturated aliphatic hydrocarbon group having 3 to 1 carbon atoms, preferably 1-coco, and chain (9) being cyclic, straight-chain or branched, substituted or unsubstituted. Typical examples include methyl group, ethyl group, propyl group, inpropyl group, butyl group, (t)-butyl group, (i
]-butyl group, (t)-amyl group, hexyl group, cyclohexyl group, 2-ethylhexyl group, octyl group%/,
I.

3.3-Tetramethylbutyl group, decyl group, dodecyl group, hexadecyl group, or octadecyl group.

The aromatic group is preferably a substituted or unsubstituted phenyl group having 4 to 0 carbon atoms, or a substituted or unsubstituted naphthyl group.

A heterocyclic group is a heterocyclic group having a carbon number of 1 to 01, preferably 1 to 7, and the hetero atom selected from a nitrogen atom, an oxygen atom, or a sulfur atom, preferably a J- to r-membered ring substituted with e or unsubstituted. with a heterocyclic group.

Typical examples of heterocyclic groups include copyridyl group, ≠-pyridyl group, cochenyl group, copyryl group, coimidazolyl group, pyrazinyl group, copyrimidinyl group, l-imidazolyl group, /-indolyl group, phthalimide i%/
1. ? t μm thiadiazole-coyl group, penzoxazole-coyl group, coquinolyl group, λ, Hiro-dioxol, 3-imidazolidine-! -yl group, co, zhen-
Examples thereof include dioxo/, J-imidazolidin-3-yl group, succinimide group, phthalimide crystalline group, tertriazole-choyl group, and l-pyrazolyl group.

When all of the above aliphatic hydrocarbon groups, aromatic groups and heterocyclic groups have substituents, typical substituents include halogen atom, R47〇- group, 46S- group, 几48 R41
Examples include a group having the same meaning as 1 kL47 group%R4., a 502- group, a cyano group, or a nitro group. Here, R46 represents an aliphatic group, an aromatic group, or a polycyclic group, and each of R, R, and R represents an aliphatic group, an aromatic group, a heterocyclic group, or a hydrogen atom. Aliphatic, aromatic or heterocyclic have the same meanings as defined above.

Next, preferred ranges of R, d, and C will be explained.

It is preferable that 几 and □ are aliphatic groups, and 9 is an aromatic group.

R, 2, R, 3 and RIsls are preferably aromatic groups, R is R41C (JNH- group, and #i R, 1- is preferably one group. R and "5?" are fatty 1
゛.

Ordinary 43 A group group, R4□〇- group, or R,18- group is preferred.

几 and 8 are preferably an aliphatic group or an aromatic group. General formula (
In Op-B), 9 is preferably a chlorine atom, an aliphatic group or an R4□C(JN)i- group, and 9 is preferably dFi/. R2O is preferably an aromatic group. In the general formula (Cp-7), R41GON) i- group is preferable, and in the general formula (CE)-7), dFi/force i
Preferably, R6□ is preferably an aliphatic group or an aromatic group. In the general formula (Cp-r), e is preferably 0 or 1.

Generally, RUCONI-1- group, R4, CONH
- group or R4□B02Nk4- group is preferable, and the substitution position thereof is preferably the 3-position of the naphthol ring. B is preferably R, □C0NH- group, or cyano group.

Next, I will explain an example of someone in their 30s.

and □ are (I)-ethyl group, p-methodiphenyl group, phenyl group, J-[λ-(29 μm di-t-amylphenoxy)butanamide)72=l group, □-octadecyloxyphenyl group, or Examples include methyl group.

R32 and Rin, 3 is Coco Kuroro! -dodecyloxycarbonylphenyl group, Cochrolow! - to subclesulfonamidophenyl group, "2-/coro-.t
-Tetradecanamidophenyl group, cochloro-! -1
4'-(co,4A-di-t-amylphenoxy]butanamido)phenyl group, cochloro-! -(ko(ko1μ)
mdi-t-amylphenol)butanamido)phenyl group, diphenyl group in comet, 2-methoxy-! -tetradecylox7 carbonyl phenol group, cochloro-7
-(/-dicarbonyl in ethoxycarzenyleth) phenyl group, copyridyl group, dicarbonylphenyl group in cochloro a-j-octyl, co,≠-dichlorophenyl group, cochloro-2-(/-dicarbonyl in dodecyloxycarbonyleth) Examples include carbonyl) phenyl group, carbonyl phenyl group, and diphenyl group.

As 几, 4, 3-12-(co,≠-di-t-amylphenol)butanamide 1 benzamide group, 3-1≠
-(ko, z-t-amylphenol)butanamide 1 benzamide group, coke c1 ku! -Tetradecanaζdoanilino group,! -(J,!-di-t-amylphenoxyacetamide)benzamide group, Cochrolow! −
Dodecenyl succinimide anilino group, cochloro-!
-(co(J-1-butyl-μm hydroxyphenoxy)tetradecanamide 1anilino group, co,codimethylpropanimide group, co(3-ntadecylphenoxy)zotanamide group, pyrrolidino RIss, co, 4A , a-trichlorophenyl group, co-chlorophenyl group, co, j-di/lorophenyl group, co, 3-dichlorophenyl M, J.

Haruka-dichloro-≠-methoxyphenyl group, ≠-1k(
J, 4I-di-t-amylphenoxy)butanamide 1
A phenyl group or a dichloromethanesulfonylphenyl group is a preferred example. R66 is a methyl group, ethyl group, inglovir group, methoxy group, ethoxy group, methylthio group, ethylthio group, 3-phenylureido group, 3-butylureido group, or 3-(co,
Examples include 4C-di-t-amylphenol group. ``57 is J-(2,μm di monoamylphenoxy)propyl i1.t-(g-(λ-(4'-(
≠-hydro diphenylsulfonyl) phenol tetradecanamido) phenyl propyl group, ethoxy group,
Ethoxy group, methylthio group, ethylthio group, methyl group,
/ ,/
-dimethyl--(co-octyloxy-1-(/,/
,J,! -tetramethylzotyl) phenylsulfonamide 1-ethyl group, and a pigotecylthio group. R
58 includes cochlorophenyl group, pentafluorophenyl group, heptafluoropropyl group, /-(,2,!
-di-t-amylphenoxy)propyl7is,'-(
x*μm di-t-amylphenoxy)propyl group, 22
Examples include μm di-t-amylmethyl group and furyl group. In general, 9 is a chlor atom, a methyl group, an ethyl group, a propyl group, an ethyl group, an inpropyl group, a co(co,
≠-di-t-amylphenol)butanamide group, 2-
(co,4L-di-t-amylphenoxy)hexaneamide group, -1(co,di-t-octylphenoxy)octanamide group, λ-(2-chlorophenoxy)tetradecanamide group, co,codimethylpropanamide basis,
-1(≠-(4L-human phenylsulfonyl)phenoxy1tetradecanamide group, also bar-(co(
J,! -di-t-amylphenoxyacetamide) phenol butanamide group. R6゜ means ≠-cyanophenyl group, -monocyanophenyl group, μm phthylsulfonylphenyl group, Hiro-probylsulfonylphenyl group, l-ethohodicarbonylphenyl H1u-N
, N-diethylsulfamoylphenyl group, J, μm
Examples of the phenyl group include J-methoxycarmenylphenyl group. R6 is a dodecyl group, a nadecyl group, a cyclohexyl group, a butyl group%'-(co,l-di-t-amylphenoxy)propyl group,
Co1μm di-t-amylphenoxy]zotyl group, 3-dodecyloxypropyl group, coatetradecyl-diphenyl group, t-butyl group, co-(2-hexyldecyloxy)phenyl group, co-tetradecyloxy]zotyl group, co-tetradecyl-o-diphenyl group, co-(2-hexyldecyloxy)phenyl group, co-tetradecyl-o-diphenyl group, co-1μm di-t-amylphenoxy]zotyl group, co-tetradecyl-o-diphenyl group, co-(2-hexyldecyloxy) phenyl group, co-metho-polymer group -dodecyl-dicarbonylphenyl group, -1-butycuphenyl group or l
-su7tyl group is mentioned. R6□ is an isozotyloxycarmenylamino group, a butoxycarbonylamino group, a phenylsulfonylamino group, a methanesulfonamide group, a butanesulfonamide group, a p-methylbenzenesulfonamide group, a benzamide group, a trifluoroacetamide group, 3 -phenylureido group, butoxycarbonylamino group, or acetamido group.

R63 includes a 22 μm di-t-amylphenoxyacetamide group, a co(22 μm di-t-amylphenoxy)butanamide group, a hexadecylsulfonamide group,
N-methyl-he-octadecylsulfamoyl group, N,
N-dioctylsulfamoyl group, dodecyl group
Bonyl group, chlorine atom, fluorine atom, etha group, cyano group, N-3-(co,4C-di-t-amylphenoxy)propylsulfamoyl group, methanesulfonyl group or hexadecylsulfonyl group are included.

Preferred DI in the general formula (I) is a compound that has a film-inhibiting effect when cleaved as DI, but after flowing out into a color developing solution, it has no substantial effect on photographic properties. Particularly preferred are development inhibitors that have the property of being decomposed (or changed) into compounds that do not give any effect.

For example, U.S. Patent No. Hiroshi, Hiroshi 77, JlaJ No.
-ko/1. Bu4A- No., Open-O---1.7JO No., Samebu O-ko JJ, Bu30, or Same≦/-//, 7uJ
Examples include development inhibitors described in the following general formulas (D-/), (D-co), (D-j), (D-1
), (D-j), (D-4), (D-7), (D-r
), CD-F), (n-io) or (D-//).

Ordinary! 6 L, -Y.

3-Yi (Ls-Yi)a In the formula, the double mark represents the bonding position with the arylene group in general formula (I), R represents a hydrogen atom or a substituent, and e represents 2t- In the formula, L3 represents a group containing a chemical bond that is cleaved in a developer, and Yl represents a substituent that exhibits a development inhibiting effect and represents an aliphatic group, an aromatic group, or a heterocyclic group.

After the development inhibitor is cleaved, it diffuses through the photographic layer while exhibiting a development inhibitory effect, and some of it flows out into the color developing processing solution. The development inhibitor that has leaked into the processing solution reacts with hydrocyclytic ions generally contained in the processing solution or with diylamine in human e1, and is rapidly decomposed at the chemical bond 4# contained in L3 (for example, the ester bond is (Hydrolysis) The group represented by Y is cleaved to form a compound with high water solubility and low development inhibiting properties, and eventually the development inhibiting effect is substantially eliminated.

A preferred example of R16 is a hydrogen atom, but the substituent 't-
Examples of substituents that may be represented include aliphatic groups (e.g. methyl group, ethyl group), acylamino groups [e.g. acetamido group, bupionamido group], ak '':!Q cy group (
For example, ethoxy group, ethoxy group], halogen atom (e.g., fukuro atom, zoro-hepta atom), dil-a group, is sulfonamide a sulfonamide? A typical example is Ij (for example, a methanesulfonamide group).

The linking group represented by L3 includes a chemical bond that is cleaved in a developer. Such chemical bonds include the examples listed in the table below. These are cleaved by nucleophilic reagents such as human mixi ion or human mixyl amine, which are components in the color developer, respectively.

The chemical bonding mode shown in the above table is linked to the heterocycle constituting the development inhibitor or, in the case of a benzene-fused ring, to the benzene ring portion directly or via an alkylene group or (and) a phenylene group, and on the other hand, Y, Connect directly to When linking via an alkylene group or phenylene group, the intervening divalent group may include an ether suture, an amide bond, a carbonyl group, a thioether bond, a sulfone group,
May contain sulfonamide bonds and urea bonds.

When Yi represents an aliphatic i&t- carbon number 1 to -01, preferably /-10, saturated 19 is an unsaturated, linear or branched, chain or cyclic, substituted or unsubstituted hydrocarbon; In particular, KFF is a hydrocarbon group having a substituent.

If Y represents an aromatic group, it is 1! It is a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group.

When Y represents a fJ1 ring group, the hetero atom is a sulfur atom, an oxygen atom, and a nitrogen atom-containing or t member.
It is a membered heterocyclic group.

Examples of the compound ring include a pyridyl group, an imidazolyl group, a furyl group, a pyrazolyl group, an oxasilyl group, a thiazolyl group, a thiadiazolyl group, a triazolyl group, a diazolidinyl group, and a diazinyl group.

The aliphatic hydrocarbon group, aromatic group, and heterocyclic group are +
When it has the ft substitution i [the substituent is a halogen atom, 2" fis an alkoxy group having 7 to 10 carbon atoms, a carbon number t
Aryloxy group having ~10 carbon atoms, alkanesulfonyl crystal having 1N10 carbon atoms, arylsulfonyl group having 6 to 10 carbon atoms, alkanamide group having 1 to IO carbon atoms, anilino group, benzamide group, lucarpamoyl group having carbon atoms/~IO , carbamoyl s, arylcarbamoyl group having carbon x number of 6 to 10, alkylsulfonamide group having carbon number/-10, aryl sulfonamide group having carbon number jN10, carbon a
/~10 ruthio group in alkali, arylthio group with carbon number O~lO, phthalimide group, succinimide group, imidazolyl group, /, co, gutriazolyl group, pyrazolyl group, benztriazolyl group, furyl group, benzthiazolyl group, carbon number Alkylamino group of 7 to IO, carbon number/-1
0 alkanoyl group, benzoyl group, alkanoyl group with a/~10 carbon atoms, benzoyl group, carbon number 1
Nj perfluoroalkyl group, cyano group, tetrazolyl group, human mixi group, mercapto group, amine group, sulfamoyl number with carbon number/-70, arylsulfamoyl group with 6 to 10 carbon atoms, morpholino group, carbon number t~ 10 aryl group, pyrrolidinyl group, frayed group, urethane group, alkoxycarbonyl group with carbon number l to IO, carbon number j
Examples include an aryloxycarbonyl group of N10, an imidazolidinyl group, or an alkylideneamino group of carbon number/~IO.

In general formula (I), the substituent substituted with Ar is DI
It is preferable to have an electron-withdrawing group at the ortho position of DI or an electron-donating group at the para position of DI.

A r tti p-phenylene i! Takem-7 22lene group is preferred.

The compound represented by the general formula CI) of the present invention can be used in a multilayer, multicolor photographic material having at least three different spectral sensitivities t-V on a support, mainly for improving sharpness, improving color reproducibility, or improving graininess. Can be applied for any purpose. A multilayer multicolor photographic material usually has at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer and a blue-sensitive emulsion layer on a support. The order of these layers can be selected arbitrarily as required; the compounds of the present invention can be added to any of these layers. It can be used not only in the light-sensitive emulsion layer but also in its adjacent layers, such as intermediate layers. Moreover, the compound of the present invention has a high sensitivity layer, a low sensitivity f
- can be added to any sensitive layer.

The amount of the compound of general formula (I) to be added varies depending on the structure of the compound, but it is preferable that silver 7 be present in the same layer or in an adjacent layer.
mol/×IO to 001 mol, particularly preferably/
×10 to 7 × l, 7-1 mole.

When the compound of general formula (I) and the color image-forming coupler are used in complete mixture, the molar ratio used is 0°0//tata,
22 to 307!0, preferably l/tata to J O/70
(Compound of the present invention/color image forming Kagura).

(Examples of chemical substances) Specific examples of the chemical substances of the present invention are listed below, but the present invention is not limited thereto.

CO2C12)i25 (C)13) 3C υ02C1□Pigeon.

11 O Synthesis Example 1 Synthesis of Exemplary Compound (I) J-(/-phenyltetrazolyl-!-thio)-! -Methoxyhydroquinone3. itt<o.

07 mol) IN, dissolved in N-dimethylformamide 30-, and added triethylamine co, 7rd. μ
mo@C without stirring α-chloro-α-piparyl-co-chloro! -Dodecyloxi7carbonylacetanilide, 32f (0.0j mol) was added and reacted for 3 hours.

After cooling to room temperature, 100 d of ethyl acetate and 100 d of water were added.
Added wJ. After washing the organic layer again with water, it was dried over magnesine sulfate, and the solvent was distilled off under reduced pressure to obtain an oily substance t-10.
，! I got f.

The obtained oily substance was subjected to silica gel chromatography,
The portion containing the target product was concentrated under reduced pressure to obtain Exemplified Compound (I) in a powder state.

This is ethyl acetate/n-hexane (//10Vol ratio)
Crystallize the exemplified compound (I) as white crystals! , r
I got f.

The structure is confirmed by elemental analysis, NMR, and mass spectrometry.9 The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is iodobromide containing about 30 molar arcs or less of iodide@k. Silver, silver iodochloride, or silver iodochlorobromide. Preferred for # is silver iodobromide containing from about -molar to about 2j molar of silver iodide.

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

The grain size of the silver halide may be fine grains of about 0.02 microns or less, or large grains with a projected area diameter of up to about 70 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD), A/744tJ
(/F7r/February 1, 2J~, 2J pages, Emulsion preparation (Emulsion prep -ra on
and types)”, and the same/P6ir
7# (/F7P/January), Buhiro page, graphic “
"Physics and Chemistry of Photography", published by Beaumontel (P, G
lafkides, Chemical at Phlsfq
ue Photographique PaulM
ontel, / P A 7), Duffin, “
"Photographic Emulsion Chemistry", published by Focalgus vs. Co., Ltd. (G, F, Du
ffin.

Photographic Emulsion Che
Mistry (Focal Press, / 5F Button)), Zellikman et al. ``Manufacture and Coating of Photographic Emulsions'', Focal Press Publishing (V, L, Zellkman et al.
tal.

Maklng and Coa mouth Photogr
aphicEmulsion, Focal Pres
s, / F1a), etc.

U.S. Patent No. J, J74teJ Cor No. J, t! ! ,3
Monodisperse emulsions such as those described in No. 944 and British Patent No. 1,4113,74Ar are also preferred.

Further, tabular grains having an ascent ratio of about 3 or more can also be used in the present invention. Tabular grains are described by Gutoff, Photographic Science and Engineering.
5science and engineering
ng), y, ia volume, 2141 N2!7 pages (/ri70
year); U.S. Patent No. Hiroshi, Hiroshi 3, Kokobu issue, same da, Q/蓼.

No. 310, 44. AJJ, No. 04411, same≠,≠3
2, F2a and British Patent Nos. CO, //CO, IT7, etc.

The crystal structure is uniform! Alternatively, the inside and outside may have different halogen compositions, or may have a layered structure. Furthermore, silver halides having different compositions may be bonded by epitaxial bonding, or compounds other than silver halide such as silver rhodan or lead oxide may be bonded.

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

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. The additive used in such processes is Research Dis/Meg Y-16.
176411J and 16/171, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also listed in the two Research Discs mentioned above, with the relevant sections listed below.

1 Chemical sensitizer page 23 ≦≠r page right column 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, λ
3 ~ Kohiro page tμl Tei right column ~ Super sensitizer
Right column 4 Brightening agent 2μ Page S Anti-fogging agent 2μ ~ Co J page t≠ Page right column ~ and stabilizer 6 Original absorbent, Fu λ! ~ λbu page Hiro page right column ~
Ilter dye Page 610 Left dermis external line absorption 7 Anti-stin agent Page 23 right column 6t Page 0 left ~
Right column 8 Dye image stabilizer Core page 9 Hardener page 24 61/page Left column 10 Binder Page same as above 11
'CIJ plastics, column lubricants core page /sJ
O-Sada Right Column 12 Coating aid, table Kot-Core page
Same as above Surface active agent 13 Static prevention Core page Same as above
Various color couplers can be used in the present invention, specific examples of which are described in the patents listed in Research Disclosure A/74443, ■-C to G. There is.

As a yellow coupler, for example, U.S. Pat.
3, 10/issue, same? 1lIn4AeO-2λ, No. 420, No. 41,324,02 (No. 4, $44.III/
.

No. 7F, Special Publication No. 5R-IO7I, British Patent No. 1,
Preferably, those described in 4C Co. J, 0 Co. Q, No. 1, 4t7, No. 740, etc.

As a magenta coupler! - Pyrazolone and pyrazoloazole compounds are preferred, U.S. Pat.
0. Bu No. 12, same 8g≠,! 1/.

rP7, European Patent No. 73. tit, U.S. Patent No. J,
D41, 4t32 No. 3,721,067, Research Disclosure I6 Kogou〇 (January 1991), JP-A-1999 AD-331j Ko No., Research Disclosure I6λμko3θ (/yra year as month) ), JP-A-4O-4A! Otsu! ? No., U.S. Patent No. ≠, 100. ≦
No. 30, same No. ≠, j 0.6! Those described in the ≠ number etc. are preferable.

Cyankabu 2-2 includes phenolic and naphthol couplers, and is disclosed in U.S. Patent No. .mu.

OJ Co, No. 172, Same No. μ, / μA, J Riwo No., Same No. 1, Coco R, No. 233, Same No. μ, 2 Ri T, No. 100, No. Ko, 3rd Buri, Octopus No. 2, No. Ko, 10/.

No. 777, No. λ, No. 77λ, No. /j, No. 777.

llij, I Kobu No. 3, 77th, ooλ No., same No. J
, 7! If, Jar No. 1I, J31t, 0/ /
, No. Hiroshi, 3 Core J/No. 73, West German Patent Association Opening No. J,
J Co. No. 2, 7, European Patent No. 1λl.

JAJk, U.S. Patent No. j, 4c44j, IJ
No. J, No. μ, 333,222, No. μ, 81/
, No. 312, ≠, ≠ 47,747, European Patent No. 1
Those described in No. 1/, 1λ, etc. are preferred.

Colored couplers to correct unnecessary absorption of coloring dyes are Research Disclosure A/7 μl ■
-G section, U.S. Patent No. μ, /43,670, Japanese Patent Publication No. 1973
-324AlJ, U.S. Patent No. a, oop, yxy,
Same No. u, /31. Jit No., British Patent No. 1,1 IAA,
The one described in No. 341 is preferred.

Couplers that allow coloring dyes to develop appropriate diffusivity include U.S. Patent No. μ, J4j, 237, British Patent No. Co, lλj
, No. 370, European Patent No. 370, West German Patent (
Public) 3rd. -34L, those described in No. 133 are preferred.

Typical examples of polymerized dye-forming couplers are described in U.S. Patent 1g3. Buddha! /, IkoQ, Dodaihiro, orQ, Ko//
No. ≠, 347. 2, British Patent Nos. 2, 10, 773, etc.

Couplers which release all photographically useful residues upon coupling can also be preferably used in the present invention. The DIRI puller that releases the development inhibitor is the aforementioned LuD/744L3.
, the patents described in sections ■ to F, JP-A-17-17-/! t/f
μμ issue, same! 7-/! μco Jμ, same 40-/rμco a
No. t, U.S. Patent No. FR.

-μl, No. 242 is preferred.

A coupler that releases a nucleating agent or a development accelerator in an m-image form during development is disclosed in British Patent No. 2. O20, No. 1140, No.
Preferably, those described in the same No. Jter/701μθ are preferred.

Other couplers that can be used in the photosensitive material of the present invention include U.S. Pat.
Competitive couplers described in U.S. Pat.

-No. 13,417, No. 1,! 31. JPJ No., Hiroshi JPJ, 310. Multi-equivalent cazolers described in Japanese Patent Application Publication No. 11, etc.; DI redox compound releasing couplers described in JP-A No. 10, etc.; dyes that restore color after separation described in European Patent No. 173.30-A; Examples include couplers that emit light.

The coupler used in the present invention can be introduced into the p-sensitive material by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Patent No. 3λλ047 and others.

Latex dispersion process steps, effects, and specific examples of latex for impregnation are US%M#t/Tata.

No. 363, West German Patent Application (OL8) No. λ,! ≠/.

λ74! No. 1, No. 1411, 230, etc.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, A/7, page 413, page 41, and the right column of page 6≠7 of A/17/6, there is a description of grasping the dermis of the calyx.

The color photographic material according to the present invention is the above-mentioned RIL)
, 4/ 744/LJ (DJr N29 page, Oyohi Do A
4 of /17/l! It can be developed by the usual methods described in the left column to right column.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to a water washing and/or stabilizing process after a desilvering process such as fixing or flossing.

The amount of washing water in the water formation process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the purpose, the washing water temperature, the number of washing tanks (stages), the replenishment method such as countercurrent or forward flow, and various other conditions. can be set over a wide range. Among these, the relationship between the number of flushing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the Society of Motion Picture and Television Engineers (Jo
urnalof the 5ociety of
Motion Picture and Te1e
vision Engineers) Volume ta, P.
2≠! - By the method described in Koj3 (/ri J! Year! Month issue),
You can ask for it.

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be greatly reduced, but due to the growth of the water residence time in the tank, bacteria will multiply, and suspended matter will be deposited on the photosensitive material. Problems such as adhesion may occur. In the processing of the color light-sensitive material of the present invention, as a solution to such problems, the method of reducing calcium and magnesium described in Japanese Patent Application No. 4/131632 can be used very effectively. Also, JP-A-17-r! Inchiazolone compounds and cyabendazoles listed in the μλ issue, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles, Hiroshi Horiguchi's "Chemistry of antibacterial and fungicidal agents," Hygiene Technology Synthetic Textile "Microbial It is also possible to use the disinfectants described in "Sterilization, sterilization, and anti-mold techniques" and "Japan Society of Anti-bacterial and Anti-Mildogistics 1iir Encyclopedia of Anti-bacterial and Antifungal Agents".

The pH of the washing water in the processing of the photosensitive material of the present invention is
? and preferably jr. The washing water temperature and washing time can also be set in various ways depending on the characteristics of the photosensitive material, its use, etc., but generally it is lj-μj@C for 20 seconds to 10 minutes, preferably co! A range of 30 seconds to 3 minutes at 0°C is selected.

Furthermore, the photosensitive material of the engine can be directly processed with a stabilizing solution instead of the water washing described above. In such stabilization treatment, Japanese Patent Application Laid-open No. 17-r! Hiroshi No. 3! ! -/grju
issue,! f-/r4AJIAJ, 40-Jko0381, to-xsrr3x, to-2327144, 4
0-23 Defgeta issue, J/-uO! No. 44, t/-11
All known methods described in No. 17449 and the like can be used. Wait, l-hydroxyethylidene-/,/
-diphosphonic acid,! A stabilizing bath containing λ-methyl-hiro-isothiazolin-3-one, a bismuth compound, an ammonium compound, etc. is preferably used.

Further, following the water washing process, there is also a case where a further stabilization process is carried out; an example of this is to remove the stabilizing bath containing formalin and a surfactant, which is used as the final bath for color photosensitive materials for photography. Can be done.

(Examples) The present invention will be explained in detail below using Examples, but the present invention is not limited thereto.

Example 1 On a subbed cellulose nine triacetate film support,
Sample 10/f, which is a multilayer color photosensitive material consisting of each layer having the composition shown below, was prepared.

(Composition of the photosensitive layer) The coating amount is expressed in silver f/m2 units for silver halide and colloidal silver, and the amount expressed in y/-2 units for couplers, additives and gelatin. For sensitizing dyes, silver halide 1 in the same layer
Expressed in moles per mole.

7th layer (stain prevention layer) Black colloidal silver ・・・・・・・・・O
o, 2 gelatin・・・・・・・・・
・／、3 colored coupler〇−／ ・・・・・・
... o, ot ultraviolet absorber UV-/ ...
......0. IN top UV-co ・
・・・・・・・・・0. Co-dispersion oil (Jil-/
・・・・・・・・・0.0/Same as above (Jil
-J ・・・・・・・・・o, oi 2nd m (intermediate layer) Fine grain silver bromide (average particle size 0°07μ) ・・・・・・・・・0.7
! Gelatin ・・・・・・・・・／
, 0 colored coupler〇-2・・・・・・・・・0. O
Co-dispersion oil (Ji I-/ Old...
o, / 3rd layer (7th red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide λ mole average grain size 0.3μ) ... Trowel O, 4t gelatin ...・・・O1 Sensitizing dye ■ ・・・・・・・・・/, O×10
-'Sensitizing dye n...3.0'
X10' sensitizing dye■ ・・・・・・・・・
/X10-” coupler C-J ・
・・・・・・・・・o, ot coupler C-μ
・・・・・・・・・o, ot coupler C-co
・・・・・・・・・0.03 dispersion oil (Ji
l-/ ・Old...0.03 Same as above 0
11-J ......0.0/2nd layer (first W-sensitive emulsion layer) Silver iodobromide emulsion (fk silver 1 lulu average grain size O13μ) ... ...0.7
Sensitizing dye I ・・・・・・・・・／X/
0-' Sensitizing dye■ ・・・・・・・・・
3×10-' sensitizing dye m ・・・・・・・・・
i×io-'Coupler C-3・・・・・・・・・O
, Co≠Coupler C-a ・・・・・・・
...Q, 2μ coupler C-2...0,1
0 dispersion oil 0il-/ ・・・・・・・・・
O0/! Dispersion oil 0i1-j ・・・・・・
...0.02 J layer (@j red-red sensitive milk layer silver iodobromide emulsion (rumored to be 70 moles of silver iodide, average grain size 0.7μ) ...Silver 1.0 gelatin ° °°°”−°°−/Fist O sensitizing dye l ・・・・・・・・・/X10−
4 sensitized color accumulation■ ・・・・・・・・・3X/
0-' Sensitizing dye■ ・・・・・・・・・
1xio-5 coupler C-4...0.0
! Coupler C-7・・・・・・・・・0. /Coupler C
-2...0.0t dispersion oil 0!1-/
・・・・・・・・・0.0/same as above (J
il-2......O0OSag4 layer (middle layer) Gelatin....../,
0 compound Cpd-person ・・・・・・・・・0
．． 03 Dispersion oil 0il-/・・・・・・・・・
・・0. Ojtj7 layer (first green-sensitive emulsion layer) Silver iodobromide emulsifier (silver iodide reference molar arc, average grain size 0.Jμ) ・・・・・・・・・0. J
O sensitizing dye■ ・・・・・・・・・z×t
o-' Sensitizing dye■ ・・・・・・・・・0. J
Xlo-'sensitizing dye■ ・・・・・・・・・
・Ko x IO” gelatin ・・・・・
・・・・・・／、0 CASOLER C-TA ・・・
...Q, Cocoupler〇-j...
...0.03 coupler C-/
......0.03 dispersion oil 0il-/
・・・・・・・・・0. Jgr layer (second green-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide! molar hata, average grain size 0.jμ) ・・・・・・・・・O0a
Sensitized color search ■ ・・・・・・j! X10-'
Sensitizing dye■ ・・・・・・・・・Xl0
−4 sensitizing color cord Vl ”−−−・−・o,
J X t o -4 Coupler C-ta
......O, Coj coupler C-/-...
...0.03 coupler e-io ・
・・・・・・・・・0.0/J Cabra −U−j
......0.0/dispersed oil 0il-/ ......0.2nd layer (
1st W-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 4 mol%, average grain size o, 7μ) ......silver 0. rJ gelatin, ・・・・・・・・・／, 0 sensitizing dye■ ・・・・・・・・・J, jt×10
”'-'Sensitizing dye■ ・・・・・・・・・／
, 4tX/ 0-' Turnip j-C-// ・
・・・・・・・・・0.0/Coupler e-/-・・・・・・
...0.03 coupler C-IJ ...
・・・・・・0.20 coupler C-/
・・・・・・・・・O1O Cocoupler C-1t
・・・・・・・・・0.02 dispersion oil (Ji
l-/ ・・・・・・・・・O, KoO Same as above
(Jil-2...0.0t first O layer (
Gelatin ・・・・・・・・・1. Yellow colloidal silver ・・・・・・・・・o,
or compound Cpd-B・・・・・・・・・
・0. /Dispersion oil LJil-/ ・・・・・・
...17. J 11th layer (1st W emulsion layer) Monodispersed silver bromide emulsion (silver iodide μmol≦, average grain size 0.Jμ) ...@0./I gelatin ... .../,
0 Sensitizing dye ■ ・・・・・・・・・×1
0-'Kagura C-/4A ・・・・・・・・・
O, Takagura C-z ・・・・・・
... o, o7 dispersion oil (jil-/ - Old... O, co 7th λ layer (second night-sensitive emulsion layer) Silver iodobromide (rumored to be 10 moles of silver iodide, average grain size 1. jμ)・・・Silver O0! Gelatin
−−−−−−−−−o, 4 sensitizing dye■ ・・・・・・・・・／X10-'Coupler C-/# ・・・・・・・・・O,
Co-J dispersion oil 0il-/ …・Old・・0.0
7 13th layer (first protective layer) Gelatin ・・・・・・・・・0.
Ultraviolet absorber UV-/・・・・・・・・・
0.7 Same as above UV-2・・・・・・・・・0.2
Dispersion oil (Jil-/ ・・・・・・・・・
0,0/Dispersion oil〇51-2 ・・・・・・・・・
・・0. Ol Daiichi HiroN (No. 1 protective layer) Fine grain silver bromide (average grain size o.

7μ) ......0. j gelachi,
......00at polymethyl methacrylate particles (diameter/, jμ) ......O, hardening agent) it, -0----o ,
a Formaldehyde scavenger 8-1 ...-1...o,! Formaldehyde scavenger S-co......-0. j In addition to the above components, a surfactant was added to each layer as a coating aid.

Next, the chemical structural formulas or chemical names of the chemotactic compounds used in the examples will be described.

C-co C-J C-≠ (S C-mu □1 -t 0CH2C) i2So2CM3 12 Average molecular weight approximately ko, oo.

C-/ koe-ij c'C-/
C) i3 CpdA CpdB sensitizing color Sensitizing dye Dye ■ Sensitizing dye ■ (C) t2) 3SO8Na Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ (0M2) 12803Nm Sensitizing dye ■ Dye Sensitive ■ Nine samples prepared as described above were designated as Sample 10/9.

Preparation of sample 10/// Sample 10/q:) Coupler C- of TLC green-sensitive emulsion layer
! Sample 9 was prepared in the same manner as Sample 10/, except that the parameters were changed as shown in Table 1.

Sample No. 10/N// was wedge-exposed to sunlight and processed as described below, resulting in nine samples with almost the same sensitivity and gradation. The sharpness of the green sensitive layer of these samples was calculated using the conventional M
Evaluation was performed using TF1'ilt. In addition to the coupler used to prepare Sample 10/, the following couplers were used for comparison.

C-/j (coupler described in U.S. Pat. No. 74C, Hata)C-/'Q U.S. Pat. 3:r,! 2
Coupler described in No. 3) U, ) 10, (t) C-# (Coupler described in US Pat. Coupler described in No.) N ball χ) C, Hl.

Each sample was subjected to the following processing using an automatic analyzer.

Table 1 - Treatment process (temperature Jr"C) Process Processing time Tank capacity Replenishment amount"Color development@
3 minutes 11 extracts /15 /Wtd bleaching ko minutes oo seconds /r (I/ryd water fc ko minutes O
0sho/Irl/1 pair of cooox Arrival 3 minutes/J
Seconds /11JJtxlWash■ /! ;+JO seconds
Pg -Water wash ■ 1 minute JOf) 24 2j - Stable 7 minutes 0j seconds 9ri I
JJtd bone: Photosensitive material Jjm/m width/m length per 9 In the above processing steps, water washing ① and ③ are countercurrent water washing method from ① to ②. Next, the composition of each processing solution is write down

<Color developer> The compositions of the mother liquor and replenisher of the color developer were as follows.

Mother liquid Brightening liquid Diethylenetriaminepentaacetic acid O, RF? 0. rfl
-Hydroxyethylidene-J, Jf J, Jfl, /
- Sodium sulfite diphosphonate, Of 4A, J
f charshun potassium 30.0'W J
f, 0? Potassium bromide 1. Hirof
O, J? Caritum iodide /, 3ki 0
Hydroxylamine sulfate, 4LtJ, Of≠-
(N-ethyl-he-β-da, JP t, 44f hydroxyethylamino) Add monomethylaniline sulfuric acid brine /, O1t/, 04p
H10,010,/J pH adjustment is best done with potassium hydroxide or sulfuric acid.

bleaching solution Mother liquid C? ) Replenisher (f) Ethylenediaminetetraacetic acid ioo ti.

Ferric ammonium salt ethylenediaminetetraacetic acid 10 / disodium salt aqueous ammonia 3 d Co d Ammonium nitrate 10.0 / O ammonium bromide /10 /70 Add water
/l /1p)i
Mother solution Replenisher (f) Ethylenediaminetetraacetic acid /, 0 /, 2 Disodium salt Sodium sulfite Da, OS, O Sodium bisulfite μ, t t, r Ammonium thiosulfate Water / 77 td co00 rxl solution (70 arc) Add water / 1p) 1
14 Stabilizing solution> Formalin (37% w/v) Od
J, (Dinidiethylene in hxl polio 0.3
, IO0μj-monononylphenyl ether (average 11 K/0) Add water to obtain /1 f'Lft,
, MTFii of 23 green-sensitive layers per 1 mm for the sample.
J[ was measured. The results are shown in Table 1.

From the fi/ results, it is clear that when the compound of the present invention is used, the sharpness is significantly improved compared to when the conventional compound is used.

Table 7 Appetizer means a compound added in place of C-s in the seventh green-sensitive layer.

The molar tX of the added amount of Tatami C-7 is expressed as a molar ratio of 7 to 9.

Procedural amendment Showa JJ Meishin Month 2nd

Claims (1)

[Scope of Claims] A silver halide color photographic material containing at least one compound represented by the following general formula (I). General Formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ In the formula, A_1 and A_2 each represent a coupler residue with one hydrogen atom at the active position removed. Ar represents an arylene group. DI stands for a photographically useful group. n represents 1 or 2.