JPS60221750A - Formation of image - Google Patents

Abstract

PURPOSE:To improve sharpness and color reproducibility of a color image, to prevent staining of a color developing agent, and to eanble a processing soln. to be repeatedly used by using a DIR compd. capable of reacting with the oxidation product of a developing agent and releasing a specified development inhibitor. CONSTITUTION:A silver halide color photosensitive material contg. a DIR compd. capable of reacting with the oxidation product of a developing agent and utilizing a development inhibitor is processed with a color developing soln. contg. sulfite ions to form an image. In this stage, the development inhibitor having nonaromatic C=N or carbonyl bond in the molecule as a partial structure is allowed to be produced. Such an inhibitor diffuses into an emulsion, and serves as a development inhibitor. A part of it is flows into the color developing soln., and reacts with sulfite ions in the soln., and loses the inhibition action. As a result, the DIR compd. is not accumulated in the processing soln., the soln. can be repeatedly used, and a sufficient amt. of DIR can be added, and hence, a color image superior in sharpness and color reproducibility can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to photographic compounds, particularly novel IR compounds (De
velopment InhibitorReleas
This invention relates to a color photographic light-sensitive material containing ing compounds).

(Background Art) By color-developing silver halide color photographic materials, the oxidized aromatic-grade amine color developing agent and coupler react to form indophenol, indoaniline,
It is known that indami/, azomethine, phenoxazine, phenazine and similar dyes are produced and color images are formed. In this method, a subtractive color method is usually used for color reproduction, and selective exposure to blue, green, and red--yellow, magenta, and cyan color image formation, which are complementary colors to the silver halide emulsion, respectively. agent is used. To form a yellow image, for example, an acylacetanilide or dibenzoylmethane coupler is used, and to form a magenta image, a pyrazolone, pyrazolobenzimidazole, cyanoacetophenone or ingzolone coupler is mainly used. , primarily phenolic couplers such as phenols and naphthols are used to form cyan images.

Normally, color photographic materials are roughly divided into two types: an external mold method in which the coupler is placed in a developing solution, and an internal mold method in which the coupler is contained in each photosensitive layer of the coupler gold photosensitive material so as to maintain its independent function. Ru. In the latter, the dye image-forming coupler is added to the silver halide emulsion.

The coupler added to the emulsion must be non-diffusible (diffusible) in the emulsion binder matrix.

It has been conventionally known that a photographic material contains a compound that releases all of the development inhibitor in accordance with the density of an image during development. This compound generally reacts with the oxidation product of the color developing agent to release a development inhibitor, and typically it is placed in the active position of the coupler, and when released from the active position, it releases a development inhibitor. So-called DIR couplers into which a group having an inhibitory effect is introduced are known.

As a DIR coupler, U.S. Patent No. 3,227゜jt,
No. 744, J, 70/, 71rJ No. 1, No. 3, 4
/j, No. 306, 3, 1. Compounds described in Japanese Patent Publication No. 7,2PI, etc., and compounds described in Japanese Patent Publication No. Shojjt-Jμ233 are known as further improved versions of these compounds.

As is well known from the above-mentioned specifications, DIR couplers are used for purposes such as improving the sharpness of color images due to the edge effect and improving color reproducibility due to the multilayer effect.

Although known DIR couplers have a certain degree of performance, it has been desired to further improve the performance. In particular, known DIR couplers have a drawback in that the development inhibitor released during color development diffuses into the processing solution from the light-sensitive material and accumulates in the processing solution, resulting in the processing solution exhibiting a development inhibiting effect. In a method in which a large amount of sensitive material is processed continuously, that is, in a commercially common processing method, it is difficult to always obtain a constant gradation, and the processing solution is contaminated by the development inhibitor released from the DIR coupler. was a serious problem.

In order to solve this problem, expedient measures have been taken for some time, but all of them have drawbacks, and no fundamental solution is known.For example, methods of limiting the amount of DIR coupler used, These include a method of frequently replacing the developing solution with a new one, or a method of newly providing a fine grain emulsion layer on the photosensitive material to capture the development inhibitor flowing out from the photosensitive layer. These methods have drawbacks such as reducing the improvement in photographic properties provided by the DIR coupler or accompanied by a large increase in cost.

(Objective of the Invention) The DIR compound of the present invention fundamentally improves the above-mentioned problems. That is, the first object of the present invention is to provide a color photographic material with excellent sharpness of color images by using all novel IR compounds.

A second object of the present invention is to provide a color photographic material with excellent color reproducibility by using a novel IR compound.

A third object of the present invention is to provide a color photographic material that does not contaminate the color developer and is suitable for a processing method that continuously reuses the color developer by using a new IR compound. It is in.

(Disclosure of the Invention) These objects of the present invention are to process a silver halide color photosensitive material containing a compound that makes a development inhibitor available by reaction with an oxidized developing agent with a color developing solution containing sulfite ions. The image forming method is characterized in that the development inhibitor has a carbon atom and a nitrogen atom or a carbonyl group bonded by a non-aromatic double bond as a partial structure in the molecule. Ru.

In the compound of the present invention, the development inhibitor produced by the reaction with the oxidized developing agent diffuses in the emulsion and exhibits a development inhibiting effect. A portion of the inhibitor flows out into the color developing solution, but the inhibitor that flows out into the processing solution reacts with the sulfite ions previously included in the processing solution and substantially loses its inhibitory effect. This reaction occurs when the carbonyl group or C
= Nuclear addition reaction of sulfite ion to N bond.

The resulting compound has an extremely high solubility in water (developer) compared to the original development inhibitor, thereby substantially losing its development inhibitory effect.

The reason for the increase in water solubility is that a sulfonic acid group is introduced into the development inhibitor by the addition reaction. Further, the substantial loss of development inhibiting action is a result of the inhibitor's increased water solubility. The addition reaction of sulfite ions to carbon-nitrogen double bonds is described, for example, in “The Che,” edited by S. Patac.
mistgoof the carbon-nitrog
en doublebond”, 2! Page I ~ 2!
It is described in the following page (John Wiley & 5ons). Furthermore, the addition reaction of sulfite ions to carbonyl groups is described in, for example, "Journal of the American
an Chemical 5ociety Volume 10/Volume 3
21rlr page ~ 32P! There is a description on page (/F7F year). Even if there is a subsequent reaction after the nucleation reaction of sulfite ions, the effects of the present invention are the same. That is, it may involve an elimination reaction. For example, when there is a balanced relationship between nucleation and desorption of sulfite ions, the concentration of the development inhibitor decreases and the effects of the present invention can be obtained.

As a result, the compound having development-inhibiting properties produced from the compound of the present invention is not accumulated in the processing solution, which not only makes it possible to repeatedly reuse the processing solution, but also allows it to be contained in a sufficient amount in the photosensitive material. It became possible. As a result, a color photographic material with excellent color image sharpness and excellent color reproducibility could be obtained.

The compound of the present invention is used in various layer configurations in various sensitive materials, and can be used in any of the high-speed layer, low-speed layer, or intermediate layer. Additionally, any treatment method that contains sulfite ions can be used. This is because, in the present invention, the speed at which the development inhibitor is deactivated can be arbitrarily selected depending on the purpose of the photosensitive material, the nature of the processing method, etc. That is, C=N or H present in the development inhibitor molecule produced from the compound of the present invention.
The c=o bond may have various substituents.

The rate at which the inhibitory properties are deactivated can be controlled by selecting the substituent.

The development inhibitor used in the present invention is C
Any combination including =N or UC=0 connections can be used. Known development inhibitors include, for example, a peterocyclic thio group (e.g., tetrazolylthio group, triazolylthio group, imidazolylthio group, benzimidazolylthio group, thiadiazolylthio group, oxadiazolylthio group, etc.) or benzotriazolylthio group. . The effects of the present invention can be obtained if a C═N or Hc═o bond is present in one of the partial structures of the substituents of these development inhibitors.

Any compound that can be used in the present invention can be used as long as it can make the above-mentioned development inhibitor available by reaction with the oxidized product of the color developing agent.

The methods available herein are preferably such that the compound releases the development inhibitor or releases a precursor thereof, after which the development inhibitor is produced. The compound that reacts with the oxidized product of the color developing agent is, for example, a coupler or a hydrononone. In the case of a coupler, it is preferable that the compound that leaves the coupling position is the development inhibitor described above or its precursor.

The present invention also includes cases where, as a result of the coupling reaction, the coupler is released from a part of the coupler other than the coupling position. An example of such is release from a coupler core as described in Japanese Published Patent Application No. JTL-20-7440.

For example, in the method released from hydro-Φnon, US Pat.

No. 1 hydroquinones such as those described in IOT, TT No. 3 can be used.

In the present invention, the group released by the reaction with the oxidized herbal drug for color development may immediately exhibit an fA image inhibitory effect, or may be a precursor of a development inhibitor that does not immediately exhibit a development inhibitory effect. . Examples of releasing the precursor include, for example, US Pat.
No. 72,343 or Japanese Published Patent No. j-7-7J
I,? These methods include a method using a timing fund as described in No. 7, or a method using a coupling-off group as described in U.S. Pat. In such an example, the reaction rate of the coupler with the oxidized color developing agent can be changed without changing the properties of the development inhibitor. After separation, even if the precursor remains in the emulsion or partially flows into the developer, the effects of the present invention can be obtained as long as the development inhibitor of the present invention is produced.

The processing used in the present invention basically consists of steps of bleaching and fixing in addition to color development. Bleaching and fixing may be carried out in the same bath, or a stabilizing bath may be added. Alternatively, the above steps may be performed after first development and reversal development.

The aesthetic treatment method is described, for example, in Research Disclosure/No. 7J, pages t-30. It is essential that the color developer used in the present invention contains phenylene diamines and sulfite ions as a developing agent. Phenylenediamines are preferably μm amino-N
, N-diethylaniline, 3-methyl-p-amino-N
, N-diethylaniline, μm amino-3-methyl-N
-Ethyl-N-β-hydroxyethylaniline module is μm amino-3-methyl-N-ethyl-N-β-methanesulfonamidoethylaniline.

The sulfite ion preferably contains a molar concentration of /x10 to 3X10, more preferably jx70-3 to -2x
The sulfite ion is preferably generated by adding an alkali metal sulfite to the developer.The water temperature during development is zooc from /r'c.
The temperature range is preferably 30°~≠j0
The temperature is C.

It is particularly preferred that the color developer used in the present invention contains, in addition to the above-mentioned components, a calcium masking agent (particularly preferably diethylenetriaminepentaacetic acid pentasodium salt). This compound is known to react with calcium ions to form stable calcinates. That is, commonly used water often contains trace amounts of calcium ions, sometimes in large amounts. Calcium ions react with sulfite ions present in the developer to produce water-insoluble calcium sulfite or air-oxidized calcium sulfite. If the concentration of sulfite ions decreases due to this reaction, a defect occurs in that the effects of the present invention cannot be obtained. When diethylenetriaminepentaacetic acid is added to the developer, calcium ions form a stable chelate with this compound, and the reaction between sulfite ions and calcium ions is substantially suppressed, so that the effects of the present invention are not impaired. The amount of diethylenetriaminepentaacetic acid pentasodium salt added is preferably in the range of /9 to jI for a developer of ij/At. Particularly preferably, the amount is in the range of 2 g to 3 g. It is preferable to add other calcium masking agents in the same amount in molar solution.

In addition to the components described above, the color developer used in the present invention includes a pH buffering agent (e.g., carbonate, borate, etc.), an antifoggant (e.g., potassium bromide, etc.), and a preservative (e.g., hydroxylamine, etc.). ) An auxiliary developer (for example, l-phenyl-3-pyrazolidone) may be included as necessary.

A preferred compound used in the present invention is represented by the following general formula (I).

General formula (I) A-(CONT)n-AF-CCD In the formula, A is (CONT) by reaction with an oxidized developing agent.
n-AF-CCD t-represents a coupler residue or I-idofuquinone residue capable of being released; C0NT
After binding to the coupling position of UA and cleavage from A, AF-
CCD6 represents a control group for cleavage, AF-CC
DHCONT (A when n is 0) represents an atomic group that exhibits a development inhibiting effect after being cleaved; It represents an atomic group containing a nyl group as a partial structure, and n represents Q or l.

A preferred group represented by A in general formula (I) is a coupler residue.

When A represents a yellow image-forming coupler residual group, it is preferably a pivaloylacetanilide type, a benzoylacetanilide type, a malondiester type, a malondiamide type,
Dibenzoylmethane type, benzothiazolylacetamide type, malone ester monoamide type, benzothiazolylacetate type, benzoxacylylacetamide type, penzoxagrilacetate type, benzimidazolylacetamide type or benzimidazolylacetate type coupler residue, US Patent 3. III/, a coupler residue derived from a heterocycle-substituted acetamide or a heterocycle-substituted acetate contained in rrO, or U.S. Patent No. 3,
770. μ-Hiro No. 6, British Patent/, μJ-ri, No. 771, West German Patent (OLS) 2゜103.0 Tata No., Japanese Published Patent No. 10-/3.

Issue 731r or Research Disclosure/! 7
Coupler residues derived from acylacetamides described in No. 37 or US Pat. No. 37, Oμt.

Examples include the hetero image type coupler residue described in No. 57≠.

When the magenta color image-forming coupler residue is present, it is preferably of the oxocopyrazoline type, pyrazolobenzimidazole type, pyrazolotriazole type, cyanoacetophenone type, pyrazoloimidazole type or OLS No. 3 , /2/, Ri! ! N- mentioned in the No.
Examples include heterocyclic-substituted acylacetamide type coupler residues.

When A represents a cyan image-forming coupler residue, it preferably includes a coupler residue having a phenol nucleus or an α-7toll nucleus.

When A represents a coupler residue that does not substantially form a dye, examples of this type of coupler residue include indanone type and acetophenone type coupler residues, and as a medium, US Pat. , same u, orr, ap
No. t, same 3. t32゜3hiro! No. 3. ri 31,223
No. 3. Ritl, Riyo 2, Yosuhiro, θμ4.1717
or 3. 3t, No. 224, etc.

In the general formula (I), the group represented by C0NT binds to the coupling group represented by HA and is used to control the rate of the coupling reaction with the oxidized developing agent. For example, the following example is known. In the present invention, these materials may or may not be used.

General formula (C-/) Connecting group general formula (C-2) ++ Connecting group general formula (C-j) described in No. 1176121 2 General formula (C-≠) 1F″2- Connecting group general formula ( C-t) C) 12- General formula (C-a) In the formula, Xi Its nitro group, alkylsulfonyl group (
For example, methoxycarbonyl group, methoxycarbonyl group)
, alkylsulfonyl group (e.g. methanesulfonyl group,
Preferred examples include phthanesulfonyl group, cyano group, methoxy group, chloro atom, alkyl group, etc. is a preferable example, and X3
is a preferable example of the substituents listed in X2, individually substituted or unsubstituted phenyl group (substituents include chloro atom, methyl group, nitro group, etc.), and X4 is a substituent other than the substituents listed in X2 and X3. Preferred examples include acylamino groups (e.g., acetamido, butanamide, benzamide, etc.) and anilino groups (e.g., a, nilino, 2-chloroanilino, etc.), and Preferred examples include atomic groups forming imidazole, triazole, pyrazole, indole, etc.).

In the formula, j represents O or l.

The group represented by AF in the general formula (I) is preferably the following. It is shown together with the substitution position of CCD.

General formula (P-/) (G1-f General formula (r-2) General formula (P-j) (G3) h-CCD General formula (p-+t) General formula (pt) In the formula, G1 is Hydrogen atoms, halogen atoms, alkyl groups (e.g., methyl groups, ethyl groups, etc.), acylamino groups (e.g., benzamide groups, hexaneamide groups), alkoxy groups (e.g., methoxy groups, pendyloxy groups), sulfonamide groups (e.g., methanesulfonamide groups, benzenesulfonamide group), aryl group (e.g. phenyl group, Hiro-chlorophenyl group), alkylthio group (e.g. methylthio group, butylthio group), alkyl-amino group (cyclohexylamino group, etc.), anilino group (a = IJ) group, μm methoxycarbonylanilino group, etc.), amino group, alkoxycarbonyl group (methoxycarbonyl group, butoxycarbonyl group), acyloxy group (e.g. acetyl group, butanoyl group, benzoyl group, etc.), nitro group, cyano group, sulfonyl group (7' tansulfonyl group, benzenesulfonyl group, etc.), aryloxy group (phenoxy group, naphthyloxy group, etc.), hydroxy group, thioamide group (butanethioamide group, benzenethiocarbonamide group, etc.), carbamoyl group (carbamoyl group, N -Arylcarbamoylated group), sulfamoyl group (sulfamoyl group, N-arylsulfamoyl group, etc.),
It represents a carboxyl group, a ureido group (ureido group, N-ethylureido group, etc.), or an aryloxycarbonyl group (phenoxycarbonyl group, Hiro-methoxycarbonyl group, etc.).

In the formula, 02 represents a substituent listed in 01 that can be a divalent group.

In the formula, 03 is a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group, and in the middle, ether bond, ester bond, thioether bond, amide bond, ureido bond, imide bond, sulfone bond, sulfonamide bond, carbonyl (Also, a plurality of these bonding groups, alkylene groups, and arylene groups may be connected to form a divalent group as a whole.

In the formula, Vx 10 represents a nitrogen atom or methyl/group 5 -N-.

(G3)h-COD The substituents listed for G4UGl in the formula or (G3)h-
Represents CCD. 05 represents a hydrogen atom, an alkyl group (eg, methyl group, ethyl group) or an aryl group (eg, phenyl group, naphthyl group).

In the formula, f represents an integer of l or λ, and h represents O or l. When f is -, the two G's may be the same or different. Which group (both one is ccl) among the groups represented by ■2 and 04 in general formulas (P-4') and (P-1)? : A group containing.

General formula (P-/), (P-2), (P-j), (P
-4') and (p-, t) Gl, G2,
When G3, G4 or G5 contains an alkyl group moiety, the alkyl group has carbon atoms of /-22, preferably ha/~10, and is substituted or unsubstituted, linear or branched, chained or cyclic, saturated or unsaturated. There may be. Furthermore, when G 1 , G 2 , G 3 , G 4 or G 5 contains an aryl group moiety, the aryl group has 6 to 10 carbon atoms and is preferably a substituted or unsubstituted phenyl group.

In general formula (I), the group represented by CCD is preferably a group represented by (D-/), (D--2), (D-J) and (D-μn described below).

General formula (D-/) 1 Zl-C-z2 General formula (D-, 2) General formula (D-J) In the formula, Zl or Z2 represents a bond with AF or the following group: a hydrogen atom, Ruamino group in alkali (e.g. CH3-NH-1CH3
-Table 1 groups), alkyl groups (e.g. methyl group, propyl group, dimethyl group, benzyl group), aryl groups (e.g. phenyl group, q-chlorophenyl group, naphthyl group,
≠-methoxyphenyl group, μm butanamidophenyl group), acylamido group (nitrogen atom may be substituted; e.g. acetamido group, benzamide group), or hetero atom selected from nitrogen atom, sulfur atom, oxygen atom ≠ shell or 7-membered substituted or unsubstituted heterocyclic group (e.g. copyridyl group, -1pyrrolidinyl group,
Terimidazolyl group, 3-chloro-! -pyrazolyl group, etc.).

In the formula, z3 is a hydrogen atom, a terogen atom, an alkyl group (e.g. methyl group, propyl group, etc.), an a17-/' group (e.g. phenyl group, terchlorophenyl group, naphthyl group, etc.), a heterocyclic group ( Nitrogen atom as a heteroatom 1. A ≠ to 7-membered heterocyclic group containing one selected from a sulfur atom and an oxygen atom; for example, a cobiridyl group, a cobirollidinyl group), an alkoxy group (for example, a methoxy group, a butoxy group), and an acyl group. groups (e.g. acetyl group, benzoyl group),
Carbamoyl group (nitrogen atom may be substituted; e.g., t&f, N-butylcarbamoyl group, N-phenylcarbamoyl group), sulfamoyl group (nitrogen atom may be substituted; e.g. N-phenylsulfamoyl group), sulfonyl group 11. (propanesulfonyl group, benzenesulfonyl group), alkoxycarbonyl group (
For example, ethoxycarbonyl group), acylamino group (e.g. acetamido group, benzamide group), sulfonamide group (e.g. &f, Hensensulfonamide group), alkylthio group (e.g. butylthio group) or ureido group
The nitrogen atom may be substituted; for example, 3-phenylureido group, 3-butylureido group).

Zl and Z3 may be combined to form a ring.

In the general formula (D-J), Z4 is! Represents a group of atoms (selected from carbon atoms, hydrogen atoms, nitrogen atoms, oxygen atoms, or sulfur atoms) that form all members or 6-membered unsaturated heterocycles xet, organic sulfonic acid anion, organic carboxylic acid anion, halogen ion or an inorganic anion (eg, tetrafluoroborate). Z
Examples of heterocycles constituted by 4 are as follows. In the following example, Zl is attached at a substitutable position.

Z7 ■ In the formula, Z7U represents the same meaning as the substituent listed above for zl or tri Z 2, and Z6 represents an oxygen atom or a sulfur atom.

General formula (D-4') / 1 where Zl % Z2 is as described above, z5H-C
= carbon atom that forms a j to 7-membered ring with N- and does not impart aromaticity to 1 -C=N-; is an alkylene group (which may be substituted; e.g. -(CH2)4-); % alkenylene group (which may be substituted; e.g. 〇 general formula CD-/), (D-co), (D-J) and(
D-Hiroshi), Zl s zl, za or Z
When 7 contains an alkyl group, the alkyl group has carbon number/
-/A, preferably /-10, may be substituted or unsubstituted, linear or branched, linear or cyclic, saturated or unsaturated. Furthermore, Zl , Z2 , Z
When 3 or Z7 contains an aryl group moiety, the aryl group has t to io carbon atoms and is preferably a substituted or unsubstituted phenyl group.

The general formula (D-/n or D-φ) is zl-Z, , Z
It is bonded to the AF group at the substitutable position of 7 (may be 1).

Furthermore, the present invention is particularly effective in the general formula (I
), A is the following general formula (I[), (1), CM),
(V), (■), (■), (■n, (W),
When it is a coupler residue represented by (,X), -(A) or (Xi[). These couplers are preferred due to their increased coupling speed.

General formula (II) General formula (m) General formula CN) 5 General formula (V) General formula (V[) 6 General formula (■) General formula (■) General formula (■) General formula (X) General formula ( XI) General formula (Xl) RIOCH-R11 In the above formula, the free bond derived from the coupling position represents the bonding position of the coupling-off group. In the above formula, R1, R2% R3% R4, R5, R6, R
7. Daiba in which R8, R9, RIO or R11 contains a diffusion-resistant group, which has a total number of carbon atoms of r to 3, preferably 10
−22, otherwise the total number of carbons is l! The following are preferred.

Next, R1-1ttti of the general formulas (I[) to (XI)
, 1, m and p will be explained.

In the formula, %R1 represents an aliphatic group, an aromatic group, an alkoxy group, or a heterocyclic group, and R2 and R3 each represent an aromatic group or a heterocyclic group.

In the formula, the aliphatic group represented by R1 preferably has a carbon number/
-J 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 /S logen atom, which may themselves have further substituents. Specific examples of useful aliphatic groups as R are: Improvyl group,
Isobutyl group, tert-butyl group, isoamyl group, t
ar t-alkyl group, /, l-dimethicbutyl group, /,
/-dimethylbexyl group 1. ．． ．． /,,/-diethyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, comethoxyisopropyl, corephenoΦdiisopropyl, λ-p-tert-
Butylphenoxyisopropyl group, α-aminoisopropyl group, α-(diethylamino)inpropyl group, α-
(sansinimide) isopropyl group, a-<phthalimide) inpropyl group, α-(benzenesulfonamide)
Examples include isopropyl group.

When R1, R2 or R3 represents an aromatic group (particularly a 7-enyl group), the aromatic group may be substituted. Aromatic groups such as phenyl groups include alkyl groups having 3-2 or less carbon atoms, alkenyl groups, alkoxy groups, alkoxycarbonyl groups, alkoxycarbonylamino groups, aliphatic amide groups,
It may be substituted with an alkylsulfamoyl group, an alkylsulfonamide group, an alkylureido group, an alkyl-substituted sansinimide group, etc. In this case, the alkyl group may have an aromatic group such as phenylene interposed in its chain. Phenyl group also includes aryloxy group, aryloxycarbonyl group,
It may be substituted with an arylcarbamoyl group, an arylamide group, an arylsulfamoyl group, an arylsulfonamide group, an arylureido group, etc., and the aryl group portion of these substituents further has a total number of carbon atoms of /-, 22
may be substituted with one or more alkyl groups.

The phenyl group represented by R1, R2 or R3 further includes an amino group, a hydroxy group, a carboxy group, a sulfo group, a nitro group, a cyano group, a thiocyano group, including those substituted with a lower alkyl group having carbon number/-4. Alternatively, it may be substituted with a halogen atom.

Further, R 1 , R2 or R3 may represent a substituent in which a phenyl group is fused with another ring, such as a naphthyl group, a middle noryl group, an isoquinolyl group, a chromanyl group, a chromanyl group, a tetrahydronaphthyl group, etc. These substituents may themselves have further substituents.

When R1 is an alkoxy radical, the alkyl moiety represents a linear or branched alkyl group, an alkenyl group, a cyclic alkyl group, or a cyclic alknyl group having from 32 carbon atoms, preferably / to λ, and these are halogen It may be substituted with an atom, an aryl group, an alkoxy group, etc.

When R1, R2 or R3 represents a heterocyclic group, the heterocyclic group is the carbon atom of the carbonyl group of the acyl group in alpha acylacetamide or the nitrogen atom of the amide group, respectively, through one of the carbon atoms forming the ring. Combine with.

Examples of such heterocycles include thiophene, furan, pyran, pyrrole, pyrazole, pyridine, pyrazine, pyrimidine, pyritazine, indolizine, indazole, thiazole, oxazole, triazine, thiadiazine, and oxazine. These may further have a substituent on the ring.

In the general formula (W), R5 represents a linear or branched alkyl group having 1 to 32 carbon atoms, preferably 1 to 2-2 carbon atoms (
For example, methyl, isopropyl, tert-butyl, hexyl, dodecyl, etc.), alkenyl groups (for example, allyl group, etc.), cyclic alkyl groups (for example, cyclopentyl group,
(cyclohexyl group, norbornyl group, etc.), aralkyl group (e.g. benzyl, β-phenylethyl group), cyclic alkenyl group (e.g. cyclopentenyl, cyclopentenyl group, etc.), and these are halogen atoms, nitro groups. , cyano group, aryl group, alkoxy group, aryloxy group, carboxy group, alkylthiocarbonyl group, arylthiocarbonyl group, alkoxycarbonyl group, arylthiocarbonyl 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, hydroxy group, mercapto group, etc.

Furthermore, R5 may represent t-aryl group (eg, phenyl group, α- or β-naphthyl group, etc.). The aryl group may have one or more substituents, such as an alkyl group, an alkenyl group, a cyclic alkyl group,
Aralkyl group, cyclic alkenyl group, halogen atom, nitro group, cyano group, aryl group, alkoxy group, aryoloxy group, carboxyl group, alkoxycarbonyl group, arylthiocarbonyl group, sulfo group, sulfamoyl group, carbamoyl group, acylamino group, diacylamino group, ureido group, urethane group, sulfonamide group, heterocyclic group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, sialkylamino group, anilino group, N-alkylamino group lino group, N-arylanilino group, N-acylanilino group,
It may have a hydroxy group, a mercapto group, etc. More preferred as 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 coupler remaining in the film is less likely to change color due to light or heat. It is useful.

Furthermore, R5 is a heterocyclic group (for example, a J-membered or 6-membered heterocyclic ring containing a nitrogen atom, an oxygen atom, or a sulfur atom as a terror 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-mentioned aryl group, aliphatic or aromatic acyl group, alkylsulfonyl group, arylsulfonyl group, alkylcarbamoyl group arylcarbamoyl, alkylthiocarbamoyl or arylthiocarbamoyl groups.

In the formula, R4 is a hydrogen atom, with a carbon number of 1 to 32, preferably 1
to 22 straight-chain or branched alkyl, alkenyl, cyclic alkyl, aralkyl, cyclic alkenyl groups (these groups may have substituents listed for R5 above), aryl groups and heterocyclic groups (these are ), an alkoxycarbonyl group (for example, a methoxycarbonyl group, an ethoxycarbonyl group, a stearyloxycarbonyl group).

Aryloxycarbonyl groups (e.g., phenoxycarbonyl group, naphthoxycarbonyl group, etc.), aralkyloxycarbonyl groups (e.g., benzyloxycarbonyl group, etc.), alkoxy groups (e.g., methoxy group, ethoxy group, heptadecyloxy group, etc.), aryl Oxy groups (e.g., phenoxy, tolyloxy, etc.), alkylthio groups (e.g., ethylthio, dodecylthio, etc.), arylthio groups (e.g., phenylthio, Amino group, J-((λ, 4L-G ter
t-amylphenoxy)acetamide]benza ξ-do group, etc.), diacylamino group, N-alkylamino group (e.g., N-methylpropionamide group, etc.), N-arylacylamino group (e.g., N-phenylacetamide group, etc.), group), ureido group (e.g. ureido, N-ryureido, N-alkylureido group, etc.), urethane group, thiourethane group, arylamino group (e.g. phenylamino, N-methylanilino group, diphenylamino group,
N-acetylanilino group, λ-chloroj-tetradecanamideanilino group, etc.), alkylamino group (e.g. n-butylamino group, methylamino group, cyclohexylamino group, etc.), cycloamino group (e.g. piperidino group, pyrrolidino group, etc.) groups), heterocyclic amino groups (e.g., Hiro-Biridylamino group, Copenzoxazinolamino group, etc.), alkylcarbonyl groups (e.g., methylcarbonyl group, etc.), arylcarbonyl groups (e.g., phenylcarbonyl group, etc.) 1, sulfone Amide groups (for example, alkyl sulfonamide groups, arylsulfonamide groups, etc.), carbamoyl groups (for example, ethyl carbamoyl groups, dimethyl carbamoyl groups, N-phenyl carbamoyl groups,
N-phenylcarbamoyl, etc.), sulfamoyl group 1
1. N-alkylsulfamoyl, N,N-dialkylsulfamoyl, N-arylsulfamoyl, N-fluor-N-arylsulfamoyl, N,
N-diarylsulfamoyl group), cyano group, hydroxy group, mercapto group, halogen atom, or sulfo group.

In the formula, R6 represents a hydrogen atom or a linear or branched alkyl group having 1 to 32 carbon atoms, preferably / to 22 carbon atoms, an alkenyl group, a cyclic alkyl group, an aral group, or a cyclic alkenyl group; It may have the substituents listed for R5 above.

Furthermore, LR6 may represent an aryl group or a heterocyclic group, and these may have the substituents listed for R5 above.

R6 is a cyano group, an alkoxy group, an aryloxy group, a halogen atom, a carboxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group,
Sulfo group, sulfamoyl group, carbamoyl group, acylamino group, diacylamino group, ureido group, urethane group, sulfonamide group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, sialylamino group, anilino group group, N-
It may also represent an arylanilino group, an N-alkylanilino group, an N-acylanilino group, a hydroxy group or a mercapto group.

17% R8 and R9 each represent a group used in a conventional g-equivalent phenol or α-naphthol coupler, and specifically UR7 includes a hydrogen atom, a halogen atom, an alkoxycarbonylamino group, an aliphatic hydrocarbon residue, N -arylureido group, acylamino group, -〇 R12 or -8R12 (however, R12 is an aliphatic hydrocarbon residue), and when two or more R7s exist in the same molecule, 0 or more R7s are They 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 R5 above.

Examples of R8 and R9 include groups selected from aliphatic hydrocarbon residues, aryl groups and heterocyclic residues, or one of these may be a hydrogen atom,
These groups also include those containing substituents. Further, R8 and R9 may jointly form a nitrogen-containing heterocyclic nucleus.

The aliphatic hydrocarbon residues can be either saturated or unsaturated (also straight-chain, branched,
Any ring-shaped one may be used. Preferably, alkyl groups (e.g., methyl, ethyl, propyl, isopropyl, butyl, t-butyl, inbutyl, dodecyl, octadecyl, cyclobutyl, cyclohexyl, etc.), alkenyl groups (e.g., allyl, octenyl, etc.) basis).

Aryl groups include phenyl groups, naphthyl groups, etc.
Representative heterocyclic residues include pyridinyl, intermediate noryl, chain secondary, piperidyl, imidazolyl, and the like. Substituents introduced into these aliphatic hydrocarbon residues, aryl groups and heterocyclic residues include halogen atoms, nitro, hydroxy, carboxyl, amino, substituted amines, sulfo, alkyl, alkenyl, aryl, heterocycles, alkoxy, arylazocy, arylthio, arylazo, acylamino, carbamoyl, ester, acyl, acylamino, sulfonamide, sulfamoyl,
Examples include various groups such as sulfonyl and morpholino.

l represents an integer from / to μ, m represents an integer from 1 to 3, and p represents an integer from / to j.

RIO is an arylcarbonyl group, an alkanoyl group having 2 to 3 carbon atoms, preferably a colcoco alkanoyl group, an arylcarbamoyl group, an alkanecarbamoyl group having 2 to 3 carbon atoms, preferably a colcoco alkanecarbamoyl group, having 1 to 3 carbon atoms, preferably l-coco; The alkoxycarbonyl group represents a dicarbonyl group in an aryl group, which may have a substituent (substituents include an alkoxy group, an alkoxycarbonyl group, an azilai) group, an alkylsulfamoyl group, an alkylsulfamoyl group, and an alkoxycarbonyl group. /amide group, alkyl rusuccinimide group, halogen atom, nitro group, carboxyl group, nitrile group, alkyl group or aryl group.

R1xt! Arylcarbonyl group, alkanoyl group having -2 to 3 carbon atoms, preferably 2 to 22 carbon atoms, arylcarbamoyl group, alkalicarbamoyl group having 2 to 32 carbon atoms, preferably λ to λλ, carbon fi/ to 3 carbon atoms, preferably 7 to 2 alkoxycarbonyl groups or aryloxycarbonyl groups% carbon fJ/~3λ preferably ha/~22 alkanesulfonyl groups, arylsulfonyl groups, aryl groups,
! or R-membered heterocyclic group (the hetero atom is selected from nitrogen atom, oxygen atom, sulfur atom, such as triazolyl group, imidazolyl group, 7-thalimide group, succinimide group,
t-, which is an imido group, a heptal group, a pyridyl group or a benzotriazolyl group, and these may have the substituents mentioned above in the RIO section.

The coupler of the present invention is preferably used in combination with other conventional couplers, and is
~jOmo19b, preferably used at 1% of l-cojmo19b.

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

■ C2)(5 (10) H (+2) H CH3 NHCOC13H27 (18) H 1 N=N \ (@ N=CHC-CR2 (') .□ The compound of the present invention is basically as shown below. It can be synthesized by a synthetic route in which each part is successively connected.

A, A-(CONT)n-A-(CONT)n-AF-
, A-(CONT)n-AF-CCD, where A%C0
NT, AP, CCD and E have the same meanings as stated in the general formula (I), but in the above reaction formula it means that each step proceeds by conversion of a functional group. In the first process, AT
h-Halogenated H-CONT (when n = /) or H-AF (when n = o) a method of reacting to the presence of a base, or the active position hydroxy form of A and the halogen form of C0NT (when n = 7) This is done by a method of reacting.

The process of introducing C0NTvcAF, and AFKCCD'
The process of introducing i may be an amidation reaction, an esterification reaction, or an etherification reaction. When a dehydration condensation agent is required in these reactions, it is selected from, for example, N,N',-dicyclohexylcarbodiimide, carbonyldiimidazole, sulfuric acid, and the like. These reactions proceed smoothly under commonly used reaction conditions.

Next, a representative synthesis method of the present invention will be specifically described.

Synthesis example (1) Synthesis of exemplified compound (1) It was synthesized using the following synthetic route.

α Exemplary Compound (1) Step ■ Synthesis of Intermediate Compound 2 Compound 1 (synthesized by the same synthetic method as similar compounds described in U.S. Pat. No. 3.3,100), to
y was added to 200 ml of io-containing acetic acid and heated to 0°C. Add the iron powder JOY to this solution in three portions while maintaining the temperature between 20° and 100°C. After reacting at this temperature for 30 minutes, the insoluble material was separated and the solution was poured into cold water. By splitting the precipitated crystals and drying them, an intermediate compound, 3'l*x, was obtained.

I got 3J.

Step ■ Intermediate compound obtained in step ■ of synthesis of exemplified compound (1)! , μλ, 39 and benzoylpropionic acid, ri, jE! acetonitrile QO-
mixed with. Add 10% of N,N'-dicyclocarbodiimide to this solution. A solution prepared by dissolving 1.5 g of acetonitrile in 20 ml of acetonitrile was added dropwise at room temperature. After reacting for 3 hours,
The by-produced N,N/-dicyclohexylurea was separated and the oral fluid was concentrated. By recrystallizing the residue from a mixed solvent of acetonitrile and ethyl acetate, the desired exemplary compound (1) fney2/,! I got it.

Synthesis Example (2) Exemplary Compound (Synthesis of 101 Exemplary Compound (1)
0) Compound 3 (compound described in U.S. Pat. No. d, 2, t, 42) s4! , 20rnlf of a chloroform solution in which Compound 4.3/9 was dissolved in 100% of tetrahydrofuran at room temperature was added dropwise to TGL. Furthermore, pyridine 7 is added to this solution.
, added ginseng. After reacting for 1 day and night, add 10 ethyl acetate
0alt- was added and washed with water using a separatory funnel. After washing with water until neutral, the oil layer was dried with magnesium sulfate.

After the solvent was distilled off under reduced pressure, the residue was recrystallized from ethyl acetate and hexane to obtain the desired coupler (10), 39/r.

In the present invention, a known method such as the method described in US Pat. No. 2,322,027 can be used to introduce the compound of the present application and a coupler that can be used in combination into the silver halide emulsion layer. Examples include fucuric acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, diethyl azelate), trimesic acid esters (e.g. tributyl trimesate), etc.; organic solvent at 30°C to 150°C,
For example, lower alkyl acetates such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol,
After being dissolved in methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point TA welding medium may be used in combination.

Also, equity 1sx-39s53, JP 51-5994
The dispersion method using polymers described in No. 3 can also be used.

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

As the binder or protective 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.

In the present invention, the gelatin may be either lime-treated or acid-treated. Details of the method for producing gelatin are described in The Macromolecular Chemistry of Gelatin, written by Arthur Vuis (Academic Press, published in 1964).

Examples of the hydrophilic colloids that can be used include gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; ta derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic
There are a wide variety of synthetic hydrophilic polymeric materials, such as single or copolymers of acids, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and the like.

Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as silver halide in the photographic emulsion layer of the photographic light-sensitive material used in the present invention. The preferred silver halide is silver iodobromide containing up to 15 mole percent silver iodide. Particularly preferred is silver iodobromide containing from 2 mol % to 12 mol % silver iodide.

The average grain size of silver halide grains in photographic emulsions (grain diameter for spherical or approximately spherical grains, grain size for cubic grains, expressed as an average based on projected area) is particularly important. Although it does not matter, it is preferably 3μ or less.

The grain size may be narrow or wide. Silver halide grains in photographic emulsions may have a regular crystal structure such as a cube or hexagonal, or may have a spherical or plate shape. It may have an irregular crystal form or a composite form of these crystal forms. It may also consist of a mixture of particles of various knot shapes.

Further, an emulsion may be used in which ultratabular silver halide grains having a grain diameter of five times or more the grain thickness occupy 50% or more of the total projected area.

The silver halide grains may have different phases inside and on the surface. Further, it may be a particle in which a latent image is mainly formed on the surface or a particle in which a latent image is mainly formed inside two particles.

The photographic emulsion used in the present invention is P, Glaf, kide.
Written by Ch.
que Photographique (Paul M.
onte1, 1967), G, F, Duffi
Photographic Emulsion C by n
hemistry (The Focal Pleas)
(Published, 1966), V. L. Zelikman
Making and Coating by et al.
Photographic Emulsion (T
He Focal Press, 1964). That is,
Any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof.

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

As one type of simultaneous mixing method, a method of keeping I) Ag in the liquid phase in which silver halide is produced constant, ie, the so-called Chondrald double jet method, can also be used.

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

Two or more types of silver halide emulsions formed separately may be mixed and used.

In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be allowed to coexist.

After the emulsion is precipitated or physically ripened, soluble salts are usually removed. For this purpose, the long-known Tardel water washing method, which involves gelling gelatin, may be used. inorganic salts such as sodium sulfate, anionic surfactants, anionic polymers (e.g. polystyrene sulfonic acid), or gelatin derivatives (e.g. aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.). A sedimentation method (flocculation) may also be used.

Silver halide emulsions are usually chemically sensitized.

For chemical sensitization, for example, H, Fr1eser, ed.
ie Grundlagender Photogra
phischen prozesse mit 5il
ber-halogeniden” (Akademi
sclleVerlagsgesellschaft,
1968), pp. 675-734, can be used.

Namely, sulfur sensitization using sulfur-containing compounds that can react with active gelatin and silver (eg, thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (eg, stannous salts);

Reduction sensitization method (amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds)
A noble metal sensitization method using complex salts of metals of the above group can be used alone or in combination.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nidroimiguzoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, Aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), etc.; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadorinthion; azaindenes, For example, triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (1,3,3a)).

7) Tetraazaindenes), pentaazaindenes, etc.; many compounds known as antifoggants or stabilizers can be added, such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. can.

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

For example, No. Bonin (steroid type), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl rayte JL44, hapholyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters) , polyalkylene glycol alkylamines or amides, polyethylene oxide adducts of silicones), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Ionic surfactants; alkyl carboxylates, alkyl sulfonates, alkylbenzenesulfone 17BB, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates anionic interfaces containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc. Activators; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl taurines, amine oxides; alkylamine salts, aliphatic or aromatic quaternary ammonium salts,
The photographic emulsion layer of the photographic light-sensitive material of the present invention may contain a cationic surfactant such as a heterocyclic quaternary ammonium salt such as pyridinium or imidazolium, and a phosphonium or sulfonium salt containing an aliphatic or heterocyclic ring. For the purpose of increasing contrast, increasing contrast, or accelerating development, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium salt compounds,
Urethane derivatives, urea derivatives, imidazole derivatives, 3
- May contain pyrazolidones and the like.

The photographic light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. For example, alkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylamide, vinyl ester (e.g. vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination, or these and acrylic acid, A polymer containing a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth)acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. as a monomer component can be used.

As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfate and thiocyanate, organic sulfur compounds known to be effective as fixing agents can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

In addition to the above, color developers include F and A.

Photo-graphic Process by Mason
ssingchemistry (FocaI Pre
ss publication, 1966), pages 226-229, US Patent 2
, No. 193,015, No. 2,592.364, JP-A-48-64933, etc. may be used.

The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Examples of bleaching agents include iron (■),
Compounds of polyvalent metals such as cobalt (Ill), chromium (Vl), and copper (II), peracids, quinones, and nitroso compounds are used.

For example, ferricyanide, dichromate, iron (I[[
) or Kobal) (III), such as aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, and 1,3-diamino-2-propatoltetraacetic acid, or organic acids such as citric acid, tartaric acid, and malic acid. Complex salts; persulfates, permanganates; nitronephenol, etc. can be used. Of these, potassium ferricyanide, sodium iron (Ill) ethylenediaminetetraacetate, and ammonium iron (Ill) ethylenediaminetetraacetate are particularly useful. Iron ethylenediaminetetraacetate (
2) Complex salts are useful both in stand-alone bleach solutions and in -bath bleach-fix solutions.

The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. In other words, pyrroline nucleus, oxazinone nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus,
Pyridine nuclei, etc.; Nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei; and nuclei in which aromatic hydrocarbon rings are fused to these nuclei, i.e., indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxane nucleus, etc. Dole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2 nucleus having a ketomethylene structure.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbyl scattering, and the like can be applied.

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. Pat. No. 2,933.390, U.S. Pat. No. 3,635,7)
21), aromatic organic acid formaldehyde condensates (such as those described in US Pat. No. 3,743,510), cadmium salts, azaindene compounds, and the like. The invention is also applicable to multilayer, multicolor photographic materials having at least two 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 blue-sensitive emulsion layer on a support.

The order of these layers can be arbitrarily selected as required.

Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case.

In the same or other photographic emulsion layer or non-light-sensitive layer of a photographic material made using the present invention, in addition to the above-mentioned compounds of the present application, other dye-forming couplers, i.e., aromatic primary Compounds that can develop color by oxidative camping with amine developers (eg, phenylene diamine derivatives, aminophenol derivatives, etc.) may also be used. For example, magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazoloimidazole couplers, pyrazolopyrazole couplers, pyrazolotriazole couplers, pyrazolotetrazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, etc. Examples of yellow couplers include acylacetamide couplers (eg, benzoylacetanilides and pivaloylacetanilides), and examples of cyan couplers include naphthol couplers and phenol couplers. These couplers are preferably non-diffusible and have a hydrophobic group called a ballast group in their molecules, or are polymerized. The coupler may be either 4-equivalent or 2-equivalent to silver ions. It may also be a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler).

In addition to DIR couplers, there are also colorless DIR couplers in which the product of the camping reaction is colorless and releases a development inhibitor.
It may also contain a coupling compound. In addition to the DIR coupler, the light-sensitive material may contain a compound that releases a development inhibitor during development.

The coupler of the present invention and the couplers described above can be used in combination of two or more types in the same layer in order to satisfy the characteristics required for a photosensitive material, or the same compound can be added to two or more different layers. Of course it doesn't matter.

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, chromium salts (chromium alum, chromium acetate, etc.)
, aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), activated vinyl compounds (1,3, 5-Triacryloyl-hexahydro-s-triazine, 1,
3-vinylsulfonyl-2-propatol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-
5-) riazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), etc. can be used alone or in combination.

In the photosensitive material produced using the present invention, when dyes, ultraviolet absorbers, etc. are contained in the hydrophilic colloid layer, they may be mordanted with a cationic polymer or the like.

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

The photosensitive material produced using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with aryl groups (e.g., those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (e.g., as described in U.S. Pat. Nos. 3,314,794 and 3,352°681), ), benzophenone compounds (for example, those described in JP-A-46-2784)
, cinnamate ester compounds (e.g. U.S. Pat. No. 3,705)
．． No. 805, as described in No. 3,707,375),
Butadiene compounds (e.g. U.S. Pat. No. 4,045,229)
(as described in US Pat. No. 3,700,455) or benzoxidol compounds (such as those described in US Pat. No. 3,700,455). UV-absorbing couplers (e.g. α-naphthol cyan dye-forming couplers),
A UV-absorbing polymer or the like may also be used. These ultraviolet absorbers may be mordanted in specific layers.

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

In carrying out the present invention, the following known anti-fading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more. Known anti-fading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives and hibisphenols.

Example 1 A multilayer color photosensitive material was prepared on a cellulose triacetate film support, each layer having the composition shown below.

1st layer: antihalation layer (A) iL) black gelatin layer containing colloidal silver λ layer: intermediate layer (ML) gelatin layer containing an emulsified dispersion of λ·j-di-t-octylhydroquinone 3rd layer: First red-sensitive emulsion layer (RLI) Silver iodobromide emulsion (silver iodide: j mol %)... Silver coating amount /, 72 g/-2 Sensitizing dye ■... Silver 1 tsXio for mole
Molar sensitizing dye■・・・・・・For 1 mole of silver/, j×10
-5 mole coupler A...O0θμ mole for 7 moles of silver Coupler C-/...o, oo for 1 mole of silver
iz mole coupler〇-2...0.00 per mole of silver
/j mole of the above compound (3)... o per mole of silver
, ooot mole μth layer: Second red-sensitive emulsion III (RL2) Silver iodobromide emulsion (silver iodide = μmol%)...Silver coating amount /, ug
/ln2 Sensitizing dye... 3 x IO moles per mole of silver Sensitizing dye... /, +2 x 1 per mole of silver
0 mole coupler A...0.001 mole for 7 moles of silver Coupler C-t...o, oo for 1 mole of silver
or molar coupler〇-2・・・・・・o, o per 1 mole of silver
ooza molar coupler C-j... o, oi for 1 mole of silver
z moles of the above compound (3)... o per mole of silver;
oooot mole number! Layer: Intermediate layer (ML) 6th layer same as the 2nd layer: 1st green-sensitive emulsion layer (GLI) Silver iodobromide emulsion (Silver iodide: Hiromorchi) Coated silver amount /,! jq/m2 Sensitizing dye ■・・・3×10 per mole of silver Sensitizing dye ■・・・／×10 per mole of silver Molar coupler B・・・・・・1 silver O per mole, OSS mole converter -/... Cite per mole of silver o, oo
t mol of the above compound (3)... o per 1 mol of silver;
ooiz mole 7th layer: 2nd green-sensitive emulsion layer (GL2) Silver iodobromide emulsion (silver iodide: 5 mol%) Coated silver amount / , A , ) il / m2 Sensitizing dye■ ......λ, zxi for 7 moles of silver
o molar sensitized immune system■... m1 mol f vs. S- o, rxto
Molar coupler B: 0.0 comol coupler M-/: 0.00 per 7 moles of silver
．． 3 mol of the above compound (3)... o per 1 mol of silver;
ooos molar layer: yellow filter single layer (YFL) gelatin aqueous solution with yellow colloidal silver and 2.! - an emulsified dispersion of D-t-octylhydro-beef non.

2nd layer: 1st blue-sensitive emulsion layer (BLl) Silver iodobromide emulsion (silver iodide: t mole)...Coated silver amount /, 1797 m2 Coupler Y-/... Silver 1 0.2j per mole
Mole 10th layer: Second blue-sensitive emulsion layer (BL2) Silver iodobromide (silver iodide = t mole)...Coated silver amount/
, /77/m''2 Coupler Y-/... 0.01 mol per 1 mol of silver 2nd layer: Protective layer (PL) Polymethylmethanoacrylate particles (diameter approximately 1).

! Apply a gelatin layer containing μ).

In addition to the above composition, a gelatin hardener and a surfactant were added to each layer.

The sample prepared as above was designated as sample 10/O sample 10; instead of compound (3) of RLI b RL2 of sample 10/, an equal amount of compound (to)t-(3) was added 1, It was prepared in the same manner as Sample 10/, except that compound (1) was added twice as much as compound (3) instead of compound (3) for GL1 and GL2.

Sample 103; DI instead of compound (3) in sample ioi
It was prepared in the same manner as Sample 10/, except that an equal amount of R-coupler D-/ff1(3) was used.

Sample 1011-' was prepared in the same manner as Sample 10/ except that the same amount of DIR coupler D-2'e (3) was used instead of Compound (3) in Sample 10/.

DIR coupler for comparison]) -/D-coH3 Compound color enhancement s■ used to prepare the sample: Anhydro j -1' -Schiff o o-
3,3'-di(r-sulfopropyl)-2-ethyl-
Thiacarbocyanine hydroside pyridinium salt sensitizing dye II: anhydroterethyl-3,3I--
) −(r-sulfopropyl)−μ・! #See’-! ′−
Dibenzothiacarbocyanine hydroxide/triethylamine salt sensitizing dye ■: Anhydrotor ethyl! -1'-Cycloro3・J /-Si(r-sulfopropyl)carbocyanine sodium salt sensitizing dye ■: Anhydro J
・6・! ' ・4. /-tetrachloro-/・ll-diethyl-3,3'-di(β-[β-(r-sulfopropoxy)ethyl]ethylimidazolocarbocyanine hydroside sodium salt coupler coupler B coupler C- λ force, Puller C-3 0H α Coupler Y-/H3 The obtained sample was processed into a film of 10/-104ct-31mm size and subjected to wedge exposure.
The development treatment shown below was carried out in a development tank.

/ Color development...3 minutes/seconds, bleaching...30 minutes/3 seconds, washing with water...・・・・・・・・・・・・3 minutes/j
Seconds≠, fixed ・・・・・・・・・・・・6 minutes 3
0 seconds! , Wash with water for 3 minutes! Seconds t, stable ・・・・・・・・・・・・・・・3
Minutes/j seconds The composition of the treatment liquid used in each step is as follows.

Color developer Sodium nitrilotriacetate i, og Sodium sulfite Hiroshi, 0g Sodium carbonate 3o, og Potassium bromide 1. Reference I Hydroxylamine sulfur F1M salt i, 4c 17 Hiro-
(N-ethyl-N-β hydroxyethylaminone-2-methyl-aniline sulfate Hiroshi, jji diethylenetriaminepentaacetic acid pentasodium salt, t, 4Ag Add water /11 Bleach solution ammonium bromide /lO,011 Ammonia water ( 21r Chi) Co!, θM Ethylenediamine-Natrilam iron tetraacetate /30 17 Glacial acetic acid lμ ml Add water /1 Fixer Sodium tetrapolyphosphate 2. Ofl Sodium sulfite ≠, OI Ammonium thiosulfate A (70%) / 7!, 0nt1 Sodium bisulfite Hiroshi, 4g Add water /1 Stabilizer formalin r, omz Add water /J Furthermore, the overflow of the developer can be recycled and reused (repeatedly) using the following method. .

The regeneration process was performed in batch mode. First, put the overflow liquid into the electrodialysis tank, and the KBr is 0.7! ! /) Electrodialysis was performed so that the following results were obtained.

This liquid contains sodium nitriloacetate, sodium sulfite, sodium carbonate, potassium bromide, and sulfuric acid sulfate consumed during running, 4! -(N-ethyl-
N-β hydrobovine diethylamino)-comethyl-aniline sulfate was added to adjust the pH flo and 0jVC, and the solution was reused as a replenisher.

Table 1 shows the decrease in sensitivity when the sample was reused 70 times, with an overflow of 1 minute being 7 times.

From the results in Table 1, sample 10/%102 had almost no decrease in sensitivity, while sample 103, IO≠, had a large decrease in sensitivity. This means that even if the leaving group of compounds (1)% (3) and (lol flows out into the color developer, it decomposes into a photographically unaffected compound, so other non-degradable leaving groups As shown in the figure, it does not accumulate in the developer and can be recycled and used repeatedly.

Table 1 △5 ioi ten o, oλ ± o +.

ioλ +0.02 ± 0 ± O lo, 3 -0,2ko -o, it -o, ot104
t-0., /3 -0.03 100 tatami fog + density 0.
The decrease in sensitivity at point 3 is expressed in logE.

Example 2 Sample 201; produced in the same manner as sample ioi except that 1.2 times the amount of compound ('11)'t-(3) was used instead of compound (3) in sample ioi.

Sample 202: Produced in the same manner as sample ioi except that compound (22)'t-λ times the amount of compound (22) was used instead of compound (3) in sample ioi.

Sample 20J: Produced in the same manner as Sample 10/, except that the same amount of DIR coupler D-3 as (3) was used in place of Compound (3) in Sample 10/.

Comparative DIR Coupler 1)-J Sample λθ/~20 j f j , processed into a t m / m size film, wedge exposed, and exposed in the developing solution tank of Example 1 for / 00 m.

The sensitivity of the first part of the processed sample was compared with the sensitivity of the last part, and the decrease in sensitivity of the latter is shown in Table 2.

The results in Table 2 show that the sample using the compound of the present invention shows less decrease in sensitivity than sample #03. This is the compound (9
This shows that the leaving groups of ) and (Corporate) are converted into compounds that have no substantial effect on photographic properties after flowing out into the color developing solution.

Table 2 △S, 10/ -0, 0/ + 0 ± Q202 -0.
02 ± O:+:Q 203 -0. /G -0,10-0,04 tatami Kaburi+
The decrease in sensitivity at a concentration of 0.3 is expressed as 1 ogE.

Claims (1)

[Claims] Contains a compound that makes a development inhibitor available by reaction with an oxidized developing agent - In an image forming method in which a silver halide color photosensitive material is processed with a color developing solution containing sulfite ions, the development inhibitor is has a carbon atom and a nitrogen atom or a carbonyl group bonded by a non-aromatic double bond as a partial structure in the molecule.