JPH0513299B2 - - Google Patents

Description

[Detailed description of the invention]

FIELD OF THE INVENTION The present invention relates to novel DIRs that can react with oxidation products of photographic compounds, particularly developer agents, to form development inhibitors.
Compound (Development Inhibitor Releasing)
This relates to color photographic materials containing compounds. (Background Art) By color-developing a silver halide color photographic material, the oxidized aromatic general amine color developing agent and the coupler react to form indophenol, indoaniline, indamine, azomethine, etc.
It is known that phenoxazine, phenazine and similar dyes can be produced to form color images. In this system, subtractive color reproduction is usually used for color reproduction, with silver halide emulsions selectively sensitive to blue, green, and red, and yellow, magenta, and cyan color image-forming agents, which are complementary colors, respectively. 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 indazolone coupler is mainly used. phenolic couplers, such as phenols and naphthols, are used primarily to form cyan images. Normally, color photographic materials are roughly divided into two types: an external method in which couplers are placed in a developing solution, and an internal method in which couplers are incorporated in each photosensitive layer of the material so as to maintain their independent functions. Ru. In the latter, the dye image-forming coupler is added to the silver halide emulsion. Couplers added to the emulsion must be non-diffusible (diffusion resistant) in the emulsion binder matrix. It is conventionally known that a photographic material contains a compound that releases a 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. 3227554,
Compounds described in Japanese Patent Publication No. 3701783, No. 3615506, No. 3617291, etc., and compounds described in Japanese Patent Publication No. 34933/1983 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, with known DIR couplers, when the development inhibitor released during color development diffuses into the processing solution from the light-sensitive material, it accumulates in the processing solution.
There was a defect that the processing liquid exhibited a development inhibiting effect. In the method of continuously processing a large amount of sensitive material, that is, the processing method commonly used commercially, it is difficult to always obtain a constant gradation, and the processing solution is contaminated by the development inhibitor released from the DIR coupler. It was a serious problem. In order to solve this problem, expedient measures have been taken in the past, but all of them have drawbacks, and no fundamental solution is known. For example, you can limit the amount of DIR coupler used, frequently replace the color developing solution with a new one, or add a new fine-grain emulsion layer to the photosensitive material to capture the development inhibitor that flows out from the photosensitive layer. methods, etc. 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 color image sharpness by using a novel DIR compound. A second object of the present invention is to provide a color photographic material with excellent color reproducibility by using a novel DIR 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 DIR compound. It is in. (Disclosure of the Invention) These objects of the present invention have been achieved by the silver halide color light-sensitive material described below. That is, in a compound that is comprised of a support and at least one photosensitive layer provided thereon, and that is contained in at least one of the photosensitive layers, this compound reacts with an oxidized color developing agent and then removes a development inhibitor from the photographic layer. and that the development inhibitor has two carbon atoms connected by a non-aromatic double bond, at least one of the carbon atoms being an electron-withdrawing group. This was achieved by a silver halide color light-sensitive material characterized by having a partial structure in which . A development inhibitor produced from the compound of the present invention by reaction with an oxidized developing agent diffuses in the emulsion and exhibits a development inhibiting effect. Some of the inhibitor that leaked into the processing solution is a sulfite ion (or hydroxylamine) that is commonly present in the processing solution in the carbon-carbon double bond contained as a partial structure. It undergoes a nucleophilic addition reaction with a nucleophilic reagent such as. The compound produced by this nucleophilic addition reaction has an extremely high solubility in water compared to the original development inhibitor, resulting in a substantial loss of development inhibitory action. The reason for the increase in water solubility is that a substituent that increases water solubility, such as a sulfonic acid group or a hydroxylamino group, is introduced into the development inhibitor by the above-mentioned 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-carbon double bonds is described, for example, in “The Chemistry of
478-479, (John Wiley &
Sons), Journal of the American Chemical
Society Vol. 92, p. 724 (1970), Vol. 97,
5566 pages (1975), edited by S. Patai, “The
"Chemistry of the quinonoid compounds"
part 2, pages 936-939 (John Wiley & Sons)
You can use the examples described in . Furthermore, the present patent also covers the case where, after the nucleophilic addition reaction of sulfite ions, a group previously substituted on a carbon atom having a double bond undergoes an elimination reaction. This is because the sulfo group remains as a base group in the development inhibitor molecule, so the effects of the present invention are the same. Examples of this include Accounts of Chemieal Research.
It is described in Volume 4, page 73 (1971), Volume 14, page 7 (1981), etc. This document describes nucleophiles other than sulfite ions. As a result, even when the compound of the present invention is used, compounds with development inhibiting properties do not accumulate in the processing solution, making it possible not only to repeatedly reuse the processing solution, but also to ensure that a sufficient amount of the compound is present in the photosensitive material. It became possible to include As a result, a color photographic material with excellent color image sharpness and excellent color reproducibility could be obtained. In particular, the sharpness improvement effect was significant. The compound of the present invention can be used in various layer configurations in various sensitive materials, and can be used in any layer, such as a high-speed layer, a low-speed layer, or an intermediate layer. Furthermore, any treatment method containing sulfite ions can be used. That is, the speed at which the development inhibitory property is deactivated can be arbitrarily selected depending on the purpose of the photosensitive material, the nature of the processing method, etc. Therefore, the carbon-carbon double bond present in the compound of the present invention may have various substituents. The rate at which the inhibitory properties are deactivated can be controlled by selecting the substituent. However, in general, when at least one of the substituents is substituted with an electron-withdrawing group, the rate of the nucleophilic addition reaction of sulfite ions is appropriate when applying the coupler to a light-sensitive material, and it is therefore extremely preferable. . An electron-withdrawing substituent is an atom or atomic group that is more electron-withdrawing than a hydrogen atom, and Hammet
The substituent constant is a substituent whose value of σp or σm is greater than 0. For the meaning of Hammet's substituent constant, see Jerry March's “Advanced
Organic Chemistry: Reactions, Mechanisms,
and Structure” 2nd edit., pp. 251-254 (McGRAW-HILL, 1977). Specific examples of electron-withdrawing substituents include nitro group, cyano group, and acyl group. , an alkoxycarbonyl group, a halogen atom, an aryl group, an acylamino group, a sulfonyl group, a heterocyclic group, a sulfamoyl group, a carbamoyl group, an imidoyl group, an acyloxy group, or a sulfonamide group.These substituents include aliphatic groups. These substituents may include aliphatic, aromatic or heterocyclic groups, and carbon-carbon double bonds may exist within the ring. In some cases, the electron-withdrawing group may also be an atomic group constituting a ring. Examples of this include a uracil group, a benzoquinone group, or an α,β-unsaturated lactone group. Any known development inhibitor containing the above-mentioned carbon-carbon double bond can be used as the agent.
Known development inhibitors include, for example, heterocyclic thio groups (e.g., tetrazolylthio groups, triazolylthio groups,
(imidazolylthio group, benzimidazolylthio group, thiadiazolylthio group, oxadiazolylthio group, etc.) or benzotriazolyl group. The effects of the present invention can be obtained if at least one of the substituents of these development inhibitors contains a double bond between carbon atoms substituted with an electron-withdrawing group. Any compound that can be used in the present invention can be used as long as it can make the above-mentioned development inhibitor photographically usable by reaction with the oxidized color developing agent. The compound that reacts with the oxidized color developing agent is, for example, a coupler or hydroquinone. In the case of a coupler, a preferred example is that the development inhibitor or its precursor described above binds to the coupling position and is released by reaction with the oxidized developer. However, as long as the development inhibitor or the like is released as a result of the coupling reaction, the present invention also includes those in which the development inhibitor or the like is not bound to the coupling position. An example of this is JP-A-58-
There are compounds released from coupler cores such as those described in No. 209740. In the case of hydroquinone release, hydroquinones such as those described in US Pat. No. 3,379,529 or US Pat. No. 4,108,663 can be used. In the present invention, the group released by the reaction with the oxidized color developing agent may exhibit a development inhibitory effect immediately after being released, or it may be a precursor of a development inhibitor that does not immediately exhibit a development inhibitory effect. It may be hot. Such examples include, for example, U.S. Patent No.
4248962, a timing group described in British Patent No. 2072363 or Japanese Patent Publication No. 57-56837, or a coupling-off group described in US Patent No. 4146396, Japanese Publication Patent No. 51-146828. be. In such an example, the reaction rate with the oxidized color developing agent can be changed without changing the properties of the development inhibitor. When the precursor of the development inhibitor is released, if it becomes a development inhibitor having a double bond between carbons substituted with an electron-withdrawing group in the emulsion or in the developer that flows out, the present invention can be applied. effect can be obtained. A preferred compound used in the present invention is represented by the following general formula (). General formula () A-(CONT) _o -AF-CCD In the formula, A represents a coupler residue or a hydroquinone residue capable of releasing (CONT) _o -AF-CCD upon reaction with an oxidized developing agent. CONT represents a control group that binds to the coupling position of A and cleaves AF-CCD after being cleaved from A, and AF-CCD is an atom that exhibits a development inhibiting effect after being cleaved from CONT (A when n is 0). CCD has two carbon atoms bonded by a non-aromatic double bond, and an electron-withdrawing group is bonded to at least one of the carbon atoms. It represents an atomic group containing a partial structure, and n represents 0 or 1. When A represents a yellow image-forming coupler residue, it is preferably of the pivaloylacetanilide type, benzoylacetanilide type, malondiester type, malondiamide type, dibenzoylmethane type,
Benzothiazolylacetamide type, malone ester monoamide type, benzothiazolylacetate type, benzoxazolyl acetamide type, benzoxazolyl acetate type, benzimidazolylacetamide type or benzimidazolylacetate type coupler residue, US Patent 3841880 or a coupler residue derived from a heterocycle-substituted acetamide or a heterocycle-substituted acetate included in the above, or U.S. Patent No. 3770446, British Patent No. 1459171, OLS Patent No. 2503099, Japanese Published Patent No.
No. 139738 or Research Disclosure
Examples include coupler residues derived from acylacetamides described in No. 15737 and heterocyclic coupler residues described in US Pat. No. 4,046,574. When A represents a magenta image-forming coupler residue, preferably of the 5-oxo-2-pyrazoline type,
Pyrazolobenzimidazole type, pyrazolotriazole type, cyanoacetophenone type, pyrazoloimidazole type or West German published patent (OLS) No.
Examples include N-heterocycle-substituted acylacetamide type coupler residues described in No. 3121955. When A represents a cyan image-forming coupler residue, it preferably includes a coupler residue having a phenol nucleus or an α-naphthol 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.
No. 4088491, No. 3632345, No. 3958993, No.
It is described in No. 3961959, No. 4046574, or No. 3938996. In the general formula (), the group represented by CONT binds to the coupling group represented by A 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-1) -OCH ₂ - Linking group described in U.S. Patent No. 4146396 General formula (C-2)

[Formula] Described in Japanese Patent Publication No. 51-146828 Linking group with General formula (C-3)

[Formula] Described in U.S. Patent No. 4248962 Linking group with General formula (C-4)

[Formula] Described in British Patent No. 2072363 Linking group with General formula (C-5)

[Formula] Described in British Patent No. 2096783 Linking group with General formula (C-6)

[Formula] Linking group described in Japanese Published Patent _No. 57-188035 In the formula, Preferred examples include a butanesulfonyl group, a butanesulfonyl group, and a _cyano group.
(Methyl group, ethyl group, isopropyl group, butyl group, cyclohexyl group, etc.) are preferred examples, and X ₃ is a substituted or unsubstituted phenyl group in addition to the substituents listed for X ₂ (substituents include chlor atom,
(methyl group, nitro group, etc.) are preferred examples,
X ₄ is an acylamino group ( _{e.g. ,} acetamido group, butanamide group,
Preferred examples include benzamide group, etc.), anilino group (e.g., anilino group, 2-chloroanilino group, etc.), and X ₅ forms a 5- or 6-membered nitrogen-containing heterocycle (e.g., imidazole, triazole, pyrazole, indole, etc.). A preferred example is an atomic group that does. The group represented by AF in the general formula () is preferably the following. Shown along with CCD substitution positions. In the formula, G ₁ is a hydrogen atom, a halogen atom, an alkyl group (e.g. methyl group, ethyl group, etc.), an acylamino group (e.g. benzamide group, hexane amide group), an alkoxy group (e.g. methoxy group, benzyloxy group), a sulfonamide group. (e.g. methanesulfonamide group, benzenesulfonamide group),
Aryl groups (e.g. phenyl group, 4-chlorophenyl group), alkylthio groups (e.g. methylthio group,
butylthio group), alkylamino group (cyclohexylamino group, etc.), anilino group (anilino group,
4-methoxycarbonylanilino group, etc.), amino group, alkoxycarbonyl group (methoxycarbonyl group, butoxycarbonyl group, etc.), acyloxy group (e.g. acetyl group, butanoyl group, benzoyl group, etc.), nitro group, cyano group, sulfonyl group (butanesulfonyl 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-aryl group, etc.) carbamoyl group, etc.), sulfamoyl group (sulfamoyl group, N-arylsulfamoyl group, etc.), carboxyl group, ureido group (ureido group, N-ethylureido group, etc.) or aryloxycarbonyl group (phenoxycarbonyl group, -methoxycarbonyl group, etc.). In the formula, G ₂ represents a substituent listed for G ₁ that can be a divalent group. In the formula, G ₃ is a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group, and an ether bond, ester bond, thioether bond, amide bond, ureido bond, imide bond, sulfone bond, carbonyl group, etc. A plurality of these bonding groups, alkylene groups, and arylene groups may be interposed to form a divalent group as a whole. In the formula, V ₁ represents a nitrogen atom or a methine group,
V ₂ is an oxygen atom, a sulfur atom,

【Formula】or teeth

Represents [formula]. In the formula, G ₄ is a substituent listed for G ₁ or (G ₃ ) _h
−Represents CCD. G ₅ is a hydrogen atom, an alkyl group (e.g. methyl group,
ethyl group) or an aryl group (eg, phenyl group, naphthyl group). In the formula, f represents an integer of 1 or 2, and h is 0
Or represents 1. When f is 2, the two G _1s may be the same or different. In general formulas (P-4) and (P-5)
At least one of the groups represented by V ₂ and G ₄ is
It is a group containing CCD. General formula (P-1), (P-2), (P-3), (P-
4) and (P-5) G ₁ , G ₂ , G ₃ , G ₄
or when G ₅ contains an alkyl group moiety, the alkyl group has 1 to 22 carbon atoms, preferably 1 to 10 carbon atoms, is substituted or unsubstituted, linear or branched, chained or cyclic, saturated or unsaturated; Good too. 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 preferably a substituted or unsubstituted phenyl group. The group represented by CCD in the general formula () is preferably the following. The following Z ₁ , Z ₁ ,
At least one of Z ₃ , Z ₄ , Z ₅ , Z ₆ and Z ₇ is the above-mentioned AF group or a group containing an AF group. In the formula, Z ₁ and Z ₂ each represent a hydrogen atom, an alkyl group, an aryl group, or an AF group. In the formula, Z ₃ , Z ₄ , Z ₅ and Z ₆ each represent a hydrogen atom, an alkyl group, an aryl group, a halogen atom (e.g. chlorine atom), an alkoxy group (e.g. methoxy group, butoxy group), an aryloxy group (e.g. phenoxy group, p-carboxyphenoxy group),
Arylthio group (e.g. phenylthio group), alkylthio group (e.g. methylthio group, butylthio group),
Alkoxycarbonyl group (e.g. ethoxycarbonyl group, octylcarbonyl group), aryloxycarbonyl group (e.g. phenoxycarbonyl group),
Alkanesulfonyl group (e.g. methanesulfonyl group), sulfamoyl group (e.g. sulfamoyl group, methylsulfamoyl group), carbamoyl group (e.g. carbamoyl group, N-phenylcarbamoyl group), ureido group (e.g. N-methylureido group), Acyl group (e.g. acetyl group, benzoyl group), acylamino group (e.g. acetamido group,
benzamide group), arylsulfonyl group (e.g. benzenesulfonyl group), heterocyclic group (5- or 6-membered ring selected from nitrogen atom, oxygen atom or sulfur atom as hetero atom, e.g. imidazolyl group, 1,2,4- triazolyl group, thiadiazolyl group or oxadiazolyl group), acyloxy group (e.g. acetyloxy group), nitro group, cyano group, carboxyl group,
thiocarbamoyl group (e.g. phenylthiocarbamoyl group), sulfamoylamino group (e.g. N
-phenylsulfamoylamino group), diacylamino group (eg, diacetylamino group), marylideneamino group (eg, benzylideneamino group), or AF group. Z ₇ represents the following group. In Z ₇ , AF may be linked via one of the following groups that can be a divalent group: halogen atom, alkoxycarbonyl group, aryloxycarbonyl group, alkanesulfonyl group, sulfamoyl group, carbamoyl group, acyl group , diacylamino group, arylsulfonyl group, heterocyclic group, nitro group, cyano group, carboxyl group or sulfonamide group. Specific examples are given for Z ₃ to Z ₆ . In general formulas (D-1), (D-2), (D-3) and (D-4), Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ , Z ₆ or Z ₇ is an alkyl group When the alkyl group contains 1 to 16 carbon atoms, preferably 1 to 8 carbon atoms, it may be substituted or unsubstituted, linear or branched, chain or cyclic, saturated or unsaturated. Furthermore, when Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ , Z ₆ or Z ₇ contains an aryl group moiety, the aryl group has 6 carbon atoms.
-10, preferably a substituted or unsubstituted phenyl group. In general formula (D-3), Z ₅ and Z ₆ each become divalent and may be connected to form a ring (for example, a benzene ring). In general formula (D-4), Z ₅ and Z ₆ each serve as a divalent group and may be connected to form a ring (for example, a benzothiazolylidene group). Furthermore, the present invention is particularly effective because in the general formula (), A is the following general formula (), (),
(), (), (), (), (), (), (
),
When it is a coupler residue represented by (XI) or (XII). These couplers are preferred because of their high coupling speed. 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, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ ,
If R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ or R ₁₁ contains a diffusion-resistant group, it is selected such that the total number of carbon atoms is 8 to 32, preferably 10 to 22; In this case, the total number of carbon atoms is preferably 15 or less. Next, R ₁ to _{R 11} of the general formulas () to (XII),
l, m, and p will be explained. In the formula, R ₁ represents an aliphatic group, an aromatic group, an alkoxy group, or a heterocyclic group, and R ₂ and R ₃ each represent an aromatic group or a heterocyclic group. In the formula, the aliphatic group represented by R ₁ preferably has 1 to 22 carbon atoms and may be substituted or unsubstituted, chain or cyclic. Preferred substituents for the alkyl group include an alkoxy group, an aryloxy group, an amino group, an acylamino group, and a halogen atom, which may themselves have further substituents. Specific examples of aliphatic groups useful as R ₁ are:
Such as: isopropyl, isobutyl, tert-butyl, isoamyl, tert-
amyl group, 1,1-dimethylbutyl group, 1,1-
Dimethylhexyl group, 1,1-diethylhexyl group, dodecyl group, hexadecyl group, octadecyl group, cyclohexyl group, 2-methoxyisopropyl group, 2-phenoxyisopropyl group, 2-p-
tert-butylphenoxyisopropyl group, α-aminoisopropyl group, α-(diethylamino)isopropyl group, α-(succinimide)isopropyl group, α-(phthalimido)isopropyl group,
α-(benzenesulfonamido)isopropyl group, etc. R ₁ , R ₂ or R ₃ is an aromatic group (especially phenyl group)
In this case, the aromatic group may be substituted. Aromatic groups such as phenyl groups include alkyl groups having 32 or less carbon atoms, alkenyl groups, alkoxy groups, alkoxycarbonyl groups, alkoxycarbonylamino groups, aliphatic amide groups, alkylsulfamoyl groups, alkylsulfonamide groups, and alkylureido groups. , an alkyl-substituted succinimide group, etc., and in this case, the alkyl group may have an aromatic group such as phenylene interposed in the chain. It may be substituted with a phenyl group, an aryloxy group, an aryloxycarbonyl group, an arylcarbamoyl group, an arylamido group, an arylsulfamoyl group, an arylsulfonamide group, an arylureido group, etc., and the aryl group of these substituents The moieties may be further substituted with one or more alkyl groups having a total of 1 to 22 carbon atoms. The phenyl group represented by R ₁ , R ₂ or R ₃ further includes an amino group, including one substituted with a lower alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, a sulfo group, a nitro group, a cyano group, It may be substituted with a thiocyano group or a halogen atom. Further, R ₁ , R ₂ or R ₃ may represent a substituent in which a phenyl group is fused with another ring, such as a naphthyl group, a quinolyl group, an isoquinolyl group, a chromanyl group, a coumaranyl group, a tetrahydronaphthyl group, and the like. These substituents may themselves have further substituents. When R ₁ represents an alkoxy group, the alkyl portion has 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms.
represents a straight-chain or branched-chain alkyl group, alkenyl group, cyclic alkyl group, or cyclic alkenyl group, which may be substituted with a halogen atom, an aryl group, an alkoxy group, or the like. When R ₁ , R ₂ or R ₃ represents a heterocyclic group,
Each of the heterocyclic groups is bonded to the carbon atom of the carbonyl group of the acyl group in alpha acylacetamide or the nitrogen atom of the amide group via one of the carbon atoms forming the ring. Such heterocycles include thiophene, furan, pyran, pyrrole, pyrazole, pyridine, pyrazine, pyrimidine, pyritazine, indolizine, imidazole, thiozole, oxazole, triazine, thiadiazine,
An example is oxazine. These may further have substituents on the ring. In the general formula (), R ₅ has a carbon number of 1 to 32
Preferably 1 to 22 linear or branched alkyl groups (e.g., methyl, isopropyl, tert-butyl, hexyl, dodecyl, etc.), alkenyl groups (e.g., allyl), cyclic alkyl groups (e.g., cyclopentyl, cyclohexyl, etc.). group, norbornyl group, etc.), aralkyl group (e.g., benzyl, β-phenylethyl group, etc.), cyclic alkenyl group (e.g., cyclopentenyl, cyclohexenyl group, etc.), and these represent halogen atoms, nitro groups, cyano groups, aryl groups, alkoxy group,
Aryloxy group, carboxy group, alkylthiocarbonyl group, arylthiocarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfo group, sulfamoyl group, carbamoyl group, acylamino group, diacylamino group, ureido group, urethane group, thiourethane group , sulfonamide group, heterocyclic group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, dialkylamino group,
It may be substituted with an anilino group, an N-arylanilino group, an N-alkylanilino group, an N-acylanilino group, a hydroxy group, a mercapto group, or the like. Furthermore, R ₅ is an aryl group (e.g. phenyl group,
(α- or β-naphthyl group, etc.) may also be represented. The aryl group may have one or more substituents, such as an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group, a cyclic alkenyl group, a halogen atom, a nitro group, a cyano group, an aryl group, and an alkoxy group. group, aryloxy group, carboxy group, alkoxycarbonyl group, aryloxycarbonyl 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, dialkylamino group, anilino group, N-alkylanilino group,
It may be an N-arylanilino group, an N-acylanilino group, a hydroxy group, a mercapto group, or the like. More preferred as R ₅ is phenyl in which at least one ortho position is substituted with an alkyl group, an alkoxy group, a halogen atom, etc.
This is useful because the coupler remaining in the film is less likely to change color due to light or heat. Furthermore, R ₅ is a heterocyclic group (for example, a 5- or 6-membered heterocyclic ring containing a nitrogen atom, an oxygen atom, or a sulfur atom as a heteroatom, a fused heterocyclic group, such as a pyridyl group, a quinolyl group, a furyl group, a benzothiazolyl group) , oxazolyl group, imidazolyl group, naphthoxazolyl group, etc.), a heterocyclic group substituted with the substituents listed for the above aryl group, an aliphatic or aromatic acyl group, an alkylsulfonyl group, an arylsulfonyl group, It may also represent an alkylcarbamoyl group, an arylcarbamoyl group, an alkylthiocarbamoyl group or an arylthiocarbamoyl group. In the formula, R ₄ is a hydrogen atom, a straight or branched alkyl having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms,
alkenyl, cyclic alkyl, aralkyl, cyclic alkenyl groups (which may have the substituents listed above for R ₅ ), aryl groups and heterocyclic groups (which may have the substituents listed above for R ₅ ); ), alkoxycarbonyl groups (e.g. methoxycarbonyl group, ethoxycarbonyl group, stearyloxycarbonyl group, etc.),
Aryloxycarbonyl group (e.g. phenoxycarbonyl group, naphthoxycarbonyl group, etc.),
Aralkyloxycarbonyl groups (e.g., benzyloxycarbonyl group, etc.), alkoxy groups (e.g., methoxy, ethoxy, heptadecyloxy, etc.), aryloxy groups (e.g., phenoxy, tolyloxy, etc.), alkylthio groups (e.g., ethylthio, dodecylthio group, etc.), arylthio group (e.g., phenylthio group, α-naphthylthio group, etc.), carboxy group, acylamino group (e.g., acetylamino group, 3-[(2,4-di-
tert-amylphenoxy)acetamide]benzamide group, etc.), diacylamino group, N-alkylacylamino group (e.g., N-methylpropionamide group, etc.), N-arylacylamino group (e.g., N-phenylacetamide group, etc.) , ureido groups (e.g. ureido, N-arylureido, N
-alkylureido group), urethane group, thiourethane group, arylamino group (e.g. phenylamino, N-methylanilino group, diphenylamino group, N-acetylanilino group, 2-chloro-5
-tetradecanamide anilino group, etc.), alkylamino groups (e.g. n-butylamino group, methylamino group, cyclohexylamino group, etc.), cycloamino groups (e.g. piperidino group, pyrrolidino group, etc.), heterocyclic amino groups (e.g. -pyridylamino group, 2-benzoxazolylamino group, etc.),
Alkylcarbonyl group (e.g. methylcarbonyl group, etc.), arylcarbonyl group (e.g. phenylcarbonyl group, etc.), sulfonamide group (e.g. alkylsulfonamide group, arylsulfonamide group, etc.), carbamoyl group (e.g. ethylcarbamoyl group, dimethylcarbamoyl group, etc.) group, N-
methyl-phenylcarbamoyl, N-phenylcarbamoyl, etc.), sulfamoyl group (e.g. N-phenylcarbamoyl), sulfamoyl group (e.g.
-alkylsulfamoyl, N,N-dialkylsulfamoyl group, N-arylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, N,N-diarylsulfamoyl group, etc.),
Represents any one of a cyano group, a hydroxy group, a mercapto group, a halogen atom, and a sulfo group. In the formula, R ₆ is a hydrogen atom or a carbon number of 1 to 32,
It preferably represents 1 to 22 straight-chain or branched-chain alkyl groups, alkenyl groups, cyclic alkyl groups, aralkyl groups, or cyclic alkenyl groups, which may have the substituents listed for R ₅ above. Furthermore, R ₆ may represent an aryl group or a heterocyclic group, and these may have the substituents listed for R ₅ above. R ₆ 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, a sulfo group, a sulfamoyl group, a carbamoyl group, an acylamino group, a diacylamino group, an ureido group, urethane group, sulfonamide group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, dialkylamino group, anilino group, N-arylanilino group, N-alkylanilino group, N- It may also represent an acylanilino group, a hydroxy group or a mercapto group. R ₇ , R ₈ and R ₉ each represent a group used in a typical 4-equivalent phenol or α-naphthol coupler; specifically, R ₇ is a hydrogen atom, a halogen atom, an alkoxycarbonylamino group, an aliphatic carbonized Hydrogen residue, N-arylureido group, acylamino group, -O-R ₁₂ or -S
-R ₁₂ (wherein R ₁₂ is an aliphatic hydrocarbon residue), and when two or more R ₇ exist in the same molecule, the two or more R ₇ may be different groups,
Aliphatic hydrocarbon residues include those having substituents. In addition, when these substituents contain an aryl group,
The aryl group may have the substituents listed for R ₅ above. R ₈ and R ₉ may include groups selected from aliphatic hydrocarbon residues, aryl groups and heterocyclic residues, or one of these may be a hydrogen atom; Including those with substituents. Further, R ₈ and R ₉ may jointly form a nitrogen-containing heterocyclic nucleus. The aliphatic hydrocarbon residue may be either saturated or unsaturated, and may be linear, branched, or cyclic.
Preferred are alkyl groups (e.g., methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, dodecyl, octadecyl, cyclobutyl, cyclohexyl, etc.) and alkenyl groups (e.g., allyl, octenyl, etc.). . Typical aryl groups include phenyl and naphthyl groups, and representative heterocyclic residues include pyridinyl, quinolyl, thienyl, 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 amino,
Examples include groups such as sulfo, alkyl, alkenyl, aryl, heterocycle, alkoxy, aryloxy, arylthio, arylazo, acylamino, carbamoyl, ester, acyl, acyloxy, sulfonamide, sulfamoyl, sulfonyl, and morpholino. l is an integer from 1 to 4, m is an integer from 1 to 3, p is 1
Represents an integer between ~5. _R10 is an arylcarbonyl group, an alkanoyl group having 2 to 32 carbon atoms, preferably 2 to 22 carbon atoms, an arylcarbamoyl group, an alkanecarbamoyl group having 2 to 32 carbon atoms, preferably 2 to 22 carbon atoms, and preferably 1 to 22 carbon atoms. represents an alkoxycarbonyl group or an aryloxycarbonyl group, which may have a substituent, such as an alkoxy group,
Alkoxycarbonyl group, acylamino group, alkylsulfamoyl group, alkylsulfonamide group, alkylsuccinimide group, halogen atom,
Examples include nitro group, carboxyl group, nitrile group, alkyl group, and aryl group. R ₁₁ is an arylcarbonyl group, an alkanoyl group having 2 to 32 carbon atoms, preferably 2 to 22 carbon atoms, an arylcarbamoyl group, an alkanecarbamoyl group having 2 to 32 carbon atoms, preferably 2 to 22 carbon atoms, and preferably 1 to 22 carbon atoms. alkoxycarbonyl group or aryloxycarbonyl group, carbon number 1-32, preferably 1-22 alkanesulfonyl group, arylsulfonyl group, aryl group, 5- or 6-membered heterocyclic group (heteroatoms include nitrogen atom, oxygen atom,
represents a sulfur atom (for example, a triazolyl group, an imidazolyl group, a phthalimide group, a succinimide group, a furyl group, a pyridine group, or a benzotriazolyl group), which have a substituent as described above for _R10 . Good too. The coupler of the present invention is preferably used in combination with other conventional couplers, and is
It is used in an amount of 0.1 mol% to 30 mol%, preferably 5 to 25 mol%. The effect of the coupler of the present invention is particularly remarkable when sulfite ions and hydroxylamine are present in the developer. Compounds used in the present invention include, but are not limited to, the following compounds. The compound of the present invention can basically be synthesized by a synthetic route in which each part is sequentially connected as shown below. A→A-(CONT) _o →A-(CONT) _o -AF→A
-(CONT) _o -AF-CCD In the formula, A, CONT, AF, CCD and n have the same meanings as stated in the general formula (), but in the above reaction formula, each step proceeds by conversion of the functional group. means. In the first step, A is halogenated and H
- A method of reacting CONT or H-AF in the presence of a base or with the active position hydroxy form of A
This is done by a method such as reacting a halogen substance of CONT. The second and third steps are also carried out using a combination of commonly used organic reactions. In many cases, this reaction is an amidation reaction or an esterification reaction.
As the condensing agent, N,N'-dicyclohexylcarbodiimide, carbonyldiimidazole, etc. are used. Next, a typical method for synthesizing the compound of the present invention will be specifically described. Synthesis Example (1) Synthesis of Exemplary Compound (1) Synthesis was performed using the following synthetic route. Step Synthesis of Compound 2 ~ Add 25 g of dihydrochloride of Compound 2 ~ to 500 ml of N,N-dimethylformamide and add 36.6 g of triethylamine.
added. Add compounds 1 to 1 to this solution at room temperature (25°C),
50 g was added in 3 portions every 10 minutes. After reacting for a day and night, 1 portion of ethyl acetate was added and the mixture was washed with water. Compounds 2 to 18.1 were obtained by concentrating the oil layer and recrystallizing the residue using a mixed solvent of ethyl acetate and hexane.
I got g. Step Synthesis of Exemplified Compound (1) Compound (2), 18.1 g, 4-chlorocinnamic acid, and 4.8 g were dissolved in N,N-dimethylformamide.
Mixed to 200ml. Add N to this solution at room temperature (25℃),
A solution of 5.4 g of N'-dicyclohexylcarbodiimide dissolved in 20 ml of acetonitrile was added dropwise.
After reacting for 3 hours, the by-produced N,N'-dicyclohexylurea was filtered off. Ethyl acetate 1 was added to the reaction mixture, and the mixture was washed with water. The oil layer was concentrated and the residue was recrystallized using a mixed solvent of ethyl acetate and hexane to obtain 13.9 g of Exemplary Compound (1). Synthesis Example (2) Synthesis of Exemplified Compound (27) Synthesis was performed using the following synthetic route. Exemplary Compound (27) Step Synthesis of Compound (4) Compound (3) (synthesized by the same method as the compound described in U.S. Pat. No. 4,076,533), 39.5 g
and 10g of potassium hydroxide in 10% aqueous methanol
The mixture was mixed with 500 ml and stirred at room temperature for 7 hours. Hydrochloric acid was added to the reaction mixture to neutralize it. By filtrating the precipitated crystals, 31.3 g of compound (4) was obtained. Step Synthesis of Exemplified Compound (27) Compound (4) ~, 31.3g obtained in Step and the compound
(5) ~, 5.2g was added to 200ml of acetonitrile, and 8.3g of N,N'-dicyclohexylcarbodiimide was added to this solution.
g was added. After reacting at room temperature for 4 hours, the by-produced N,N'-dicyclohexylurea was filtered off.
The filtrate was concentrated and the residue was crystallized from acetonitrile to obtain 19.4 g of the target exemplary compound (27). 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. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (such as 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., or boiling point approximately 30
organic solvents such as ethyl acetate,
After being dissolved in a lower alkyl acetate such as butyl acetate, ethyl propionate, secondary butyl alcohol, 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 organic solvent may be used in combination. Further, the dispersion method using a polymer described in Japanese Patent Publication No. 51-39853 and Japanese Patent Application Laid-open No. 51-59943 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. Binders or protective colloids that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention include:
Although gelatin is advantageously used, other hydrophilic colloids can also be used alone or in conjunction with gelatin. In the present invention, the gelatin may be either lime-treated or acid-treated. For more information about gelatin production, see Arthur Vuis, The Macromolecular Chemistry of Gelatin, (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; hydroxyethyl cellulose;
Cellulose derivatives such as carboxymethylcellulose and cellulose sulfate esters; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl There are a wide variety of synthetic hydrophilic polymeric materials such as imidazole, polyvinylpyrazole, etc., single or copolymers. 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 preferable is 2
Silver iodobromide containing from mol% to 12 mol% silver iodide. The average grain size of the silver halide grains in the photographic emulsion (the grain size is the grain diameter for spherical or approximately spherical grains, the edge length for cubic grains,
Expressed as an average based on projected area. ) is not particularly limited, but it is preferably 3μ or less. The particle size may be narrow or wide. The silver halide grains in the photographic emulsion may have a regular crystal structure such as a cube or an octahedron, or may have an irregular crystal structure such as a spherical shape or a plate shape, or may have an irregular crystal structure such as a spherical shape or a plate shape. It can also be a composite of shapes. It may also consist of a mixture of particles of various crystalline forms. 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, the particles may be particles in which the latent image is mainly formed on the surface, or may be particles in which the latent image is mainly formed inside the particles. The photographic emulsion used in the present invention is written by P. Glafkides.
Chimie et Physique Photographique (Paul
Montel Publishing, 1967), GFDuffin
Photographic Emulsion Chemistry (The
Focal Press, 1966), VLZelikman et al.
AuthorMaking and Coating Photographic
It can be adjusted using the method described in Emulsion (The 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 any one-sided mixing method, simultaneous mixing method, or a combination thereof. good. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).
One type of simultaneous mixing method is a method of keeping pAg constant in the liquid phase in which silver halide is produced, that is,
A so-called controlled double jet method may 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 Nudel water washing method, which involves gelatinization, may be used. Inorganic salts such as sodium sulfate,
Precipitation methods using anionic surfactants, anionic polymers (e.g. polystyrene sulfonic acid), or gelatin derivatives (e.g. aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.) ) may be used. Silver halide emulsions are usually chemically sensitized.
For chemical sensitization, see for example “Die
Grundlagender Photographischen Prozesse
mit Silber−halogeniden”
(Akademische Verlagsgesellschaft, 1968)
The method described on pages 675-734 can be used. That is, sulfur sensitization using sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds) reduction sensitization method;
Noble metal compounds (e.g., gold complex salts, Pt, Ir,
A noble metal sensitization method using complex salts of metals in the periodic table group such as Pd 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. Namely, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. such as benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; Zaindenes, tetraazaindenes (especially 4-hydroxy substituted (1,3,
3a, 7) tetraazaindenes), pentaazaindenes, etc.; many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfonic acid, benzenesulfonic acid amide, etc. can be added. The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material produced using the present invention contains coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (e.g., development acceleration, high contrast , sensitization)
Various surfactants may be included for various purposes. For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/potipropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene nonionic substances such as glycolalkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, and alkyl esters of sugars. Surfactants; alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosucci acid esters, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphate esters, etc., with acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc. Anionic surfactants containing; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, amine oxides; alkylamine salts, aliphatic or aromatic quaternary ammonium Cationic surfactants such as salts, heterocyclic quaternary ammonium salts such as pyridinium, imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used. The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholins, and quaternary ammonium salts for the purpose of increasing sensitivity, increasing contrast, or accelerating development. compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like. The photographic light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or 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 together with acrylic acid, methacrylic acid, α,β-unsaturated dicarboxylic acid, Hydroxyalkyl (meth)
Polymers containing a combination of acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. as monomer components can be used. For the photographic processing of the layer consisting of the photographic emulsion produced using the present invention, any of the known methods and known processing solutions, such as those described in Research Disclosure No. 176, pages 28-30, can be applied. can do. The treatment temperature is usually chosen between 18°C and 50°C, but it may also be lower than 18°C or above 50°C. As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent. Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer, such as phenylenediamines (e.g., 4-amino-N,N-diethylaniline, 3-methyl-4-amino-N,N-diethylaniline, 4-amino- N-ethyl-N-
β-hydroxyethylaniline, 3-methyl-4
-Amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfamide ethylaniline, 4-amino-3-methyl-N-ethyl-N −
β-methoxyethylaniline, etc.) can be used. Other Photography by LFAMason
Processing Chemistry (Focal Press, 1966)
P226-229, U.S. Patent No. 2193015, U.S. Patent No. 2592364
JP-A No. 48-64933, etc. may be used. The color developer used in the present invention contains sulfite ions (addition amount: 10 ^-3 to 0.5 mol/, preferably 5
×10 ^-3 to 0.2 mol/) or hydroxylamine (addition amount, 0.5 to 10 g/, preferably 1 to 5 g/
), and in addition, PH buffering agents such as alkali metal carbonates, borates, and phosphates, development inhibitors or antifoggants such as brominating agents, iodides, and organic antifoggants. It can also contain agents such as If necessary, water softeners, preservatives, organic solvents such as benzyl alcohol and diethylene glycol, development accelerators such as polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers, competitive couplers, and sodium boron hydride may be added. It may also contain a fogging agent such as a fogging agent, an auxiliary developer such as 1-phenyl-3-pyrazolidone, a viscosity imparting agent, a polycarboxylic acid chelating agent, an antioxidant, and the like. After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. As a bleach,
For example, iron (), cobalt (), chromium (),
Compounds of polyvalent metals such as copper, peracids, quinones, nitroso compounds, etc. are used. For example, ferricyanide, dichromate, organic complex salts of iron () or cobalt (), such as ethylenediaminetetraacetic acid, nitrilotriacetic acid,
Complex salts of aminopolycarboxylic acids such as 1,3-diamino-2-propanoltetraacetic acid or organic acids such as citric acid, tartaric acid, and malic acid; persulfates;
Permanganate; nitrosophenol, etc. can be used. Of these, potassium ferricyanide, sodium ferric ethylenediaminetetraacetate, and ammonium ferric ethylenediaminetetraacetate are particularly useful. Ethylenediaminetetraacetic acid iron() complexes are useful in both stand-alone bleach solutions and single bath bleach-fix solutions. The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. The pigments used include cyanine pigments, merocyanine pigments,
Included are 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. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of Imidazole nuclei, quinoline nuclei, etc. can be applied.
These nuclei may be substituted on carbon atoms. The merocyanine dye or composite merocyanine dye includes a nucleus having a ketomethylene structure such as a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, A 5- to 6-membered heteroartic ring nucleus such as a thiobarbituric acid nucleus 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, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. For example, aminostyl compounds substituted with nitrogen-containing heterocyclic groups (e.g.,
2933390 and 3635721), aromatic organic acid formaldehyde condensates (for example, those described in US Pat. No. 3743510), cadmium salts, azaindene compounds, and the like. The present invention
It is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support. Multilayer natural color photographic materials usually include a red-sensitive emulsion layer on a support,
It has at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer. The order of these layers can be arbitrarily selected as required. a cyan-forming coupler in the red-sensitive emulsion layer, a magenta-forming coupler in the green-sensitive emulsion layer,
It is usual that each 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 layers or non-light-sensitive layers of the photographic light-sensitive materials made using the present invention, in addition to the aforementioned compounds of the present application, other dye-forming couplers,
That is, a compound that can develop color by oxidative coupling with an aromatic primary amine developer (for example, a phenylene diamine derivative, an aminophenol derivative, etc.) may be used in the color development process. For example, magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers,
Pyrazoloimidazole couplers, pyrazolo pyrazole couplers, pyrazolotriazole couplers,
There are pyrazolotetrazole couplers, cyanoacetylcoumarone couplers, open chain acylacetonitrile couplers, etc. Yellow couplers include acylacetamide couplers (e.g. benzoylacetanilides, pivaloylacetanilides),
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. In addition, colored couplers have the effect of color correction,
Alternatively, it may be a coupler that releases a development inhibitor during development (so-called DIR coupler). In addition to the DIR coupler, the coupling reaction product is colorless and may contain a colorless DIR coupling compound that releases a development inhibitor.
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 above-mentioned couplers can be used in combination in the same layer in order to satisfy the characteristics required for a photosensitive material, or the same compound can be added in 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, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.),
Dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,3-dihydroxydioxane, etc.), (4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), and the like 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 (such as those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (such as those described in U.S. Pat.
3314794 and 3352681), benzophenone compounds (for example, those described in JP-A-46-2784), cinnamic acid ester compounds (for example, those described in U.S. Pat. No. 3705805 and 3707375), butadiene Compounds such as those described in US Pat. No. 4,045,229 or benzoxide compounds (such as those described in US Pat. No. 3,700,455) can be used. An ultraviolet absorbing coupler (for example, an α-naphthol cyan dye-forming coupler) or an ultraviolet absorbing polymer may 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
Included are 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 antifading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives, and bisphenols. Next, examples of the present invention will be specifically illustrated. However, it is not limited to this. This will help understand how to apply the technique according to the invention. 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 (AHL) Gelatin layer containing black colloidal silver 2nd layer: Intermediate layer (ML) Gelatin layer containing an emulsified dispersion of 2.5-di-t-octylhydroquinone 3rd layer: 1st red tone Emulsion layer (RL ₁ ) Silver iodobromide emulsion (silver iodide: 5 mol %)...Silver coating amount 1.79 g/ ^m2 Sensitizing dye...6 x 10 ^-5 mol per 1 mol of silver Sensitizing dye ...1.5×10 ^-5 mol per mol of silver Coupler A...0.04 mol per mol of silver Coupler C-1...0.0015 mol per mol of silver Coupler C-2...For 1 mol of silver 0.0015 mol Compound of the present invention (1)...0.0006 mol per mol of silver Fourth layer: Second red-sensitive emulsion layer (RL ₂ ) Silver iodobromide emulsion (silver iodide: 4 mol %)... ...Silver coating amount 1.4 g/ ^m2 Sensitizing dye...3 x 10 ^-5 mol per 1 mol of silver Sensitizing dye...1.2 x 10 ^-5 mol per 1 mol of silver Coupler A...1 mol of silver Coupler C-1...0.0008 mole per mole of silver Coupler C-2...0.0008 mole per mole of silver Coupler C-3...0.015 mole per mole of silver Compound (1)...0.00006 mol per mol of silver 5th layer: Intermediate layer (ML) 6th layer same as the 2nd layer: 1st green-sensitive emulsion layer (GL ₁ ) Silver iodobromide emulsion (iodide Silver: 4 mol%)... Coated silver amount 1.5 g/m ² Sensitizing dye... 3 x 10 ^-5 mol per 1 mol of silver Sensitizing dye... 1 x 10 ^-5 mol per 1 mol of silver Coupler B... 0.05 mol per mol of silver Coupler M-1... 0.008 mol per mol of silver Compound (1) of the present invention... 0.0015 mol per mol of silver 7th layer: Second green Sensitized emulsion layer (GL ₂ ) Silver iodobromide emulsion (silver iodide: 5 mol%)...Amount of coated silver 1.6 g/ ^m2 Sensitizing dye...2.5 x 10 ^-5 mol per mol of silver Sensitization Dye: 0.8×10 ^-5 mol per mol of silver Coupler B: 0.02 mol per mol of silver Coupler M-1: 0.003 mol per mol of silver Compound (1) of the present invention... 0.0003 mol per mol of silver 8th layer: Yellow filter layer (YFL) A gelatin layer containing an emulsified dispersion of yellow colloidal silver and 2.5-di-t-octylhydroquinone in an aqueous gelatin solution. 9th layer: 1st blue-sensitive emulsion layer (BL ₁ ) Silver iodobromide emulsion (silver iodide: 6 mol%)...Amount of coated silver 1.5 g/ ^m2 Coupler Y-1...For 1 mol of silver 0.25 mol 10th layer: Second blue-sensitive emulsion layer (BL ₂ ) Silver iodobromide (silver iodide: 6 mol %)...Amount of coated silver 1.1 g/m ² Coupler Y-1...For 1 mol of silver 0.06mol 11th layer: Protective layer (PL) Polymethylmethanoacrylate particles (diameter approx.
Apply a gelatin layer containing 1.5μ). In addition to the above composition, a gelatin hardener and a surfactant were added to each layer. The sample prepared as described above was designated as sample 101. Sample 102: Compound (26) was added in the same amount as (1) instead of compound (1) in RL ₁ and RL ₂ of sample 101, and GL ₁ , GL ₂
Sample 101 was prepared in the same manner as sample 101 except that compound (19) was added twice as much as compound (1) instead of compound (1). Sample 103; DIR− instead of compound (1) of sample 101
It was prepared in the same manner as Sample 101 except that coupler D-1 was used in the same amount as (1). Sample 104: Produced in the same manner as Sample 101 except that DIR coupler D-2 was used in the same amount as Compound (1) in Sample 101 in place of Compound (1). Compound sensitizing dye used to prepare the sample: anhydro-5.5'-dichloro-
3.3'-di-(γ-sulfopropyl)-9-ethyl-thiacarbocyanine hydroxide pyridinium salt sensitizing dye: anhydro-9-ethyl-3.3'-di-(γ-sulfopropyl)-4.5.4'-5'-dibenzothiacarbocyanine hydroxide triethylamine salt sensitizing dye: anhydro-9-ethyl-5.5'-dichloro-3,3'-di-(γsulfopropyl)
Oxacarbocyanine sodium salt sensitizing dye: anhydro-5,6,5',6'-tetrachloro-1,1'-diethyl-3,3'-di-
{β-[β-(γ-sulfopropoxy)ethoxy]ethylimidazolocarbocyanine hydroxide sodium salt The obtained samples 101 to 104 were processed into 35 mm size films and each film was 600 m long with wedge exposure.
The following development process was carried out in a second development tank. 1 Color development... 3 minutes 15 seconds 2 Bleaching... 6 minutes 30 seconds 3 Washing... 3 minutes 15 seconds 4 Fixing... 6 minutes 30 seconds 5 Washing... 3 minutes 15 seconds 6 Stabilization... 3 minutes 15 seconds each The composition of the treatment liquid used in the process is as follows. Color developer Sodium nitrilotriacetate 1.0g Sodium sulfite 4.0g Sodium carbonate 30.0g Potassium bromide 1.4g Hydroxylamine sulfate 2.4g 4-(N-ethyl-N-βhydroxyethylamino)-2-methyl-aniline sulfate Add 4.5g water 1 Bleach solution Ammonium bromide 160.0g Aqueous ammonia (28%) 25.0ml Ethylenediamine-tetraacetic acid sodium iron salt
130g Glacial acetic acid 14ml Add water 1 Fixer Sodium tetrapolyphosphate 2.0g Sodium sulfite 4.0g Ammonium thiosulfate (70%) 175.0ml Sodium bisulfite 4.6g Add water 1 Stabilizer Formalin 8.0ml Add water 1 More The overflow portion of the developer was recycled and reused by the following method. The regeneration process was performed in batches. First, put the overflow liquid into the electrodialysis tank, and the KBr concentration is 0.7g/
Electrodialysis was performed as follows. This solution contains sodium nitrilotriacetate, sodium sulfite, sodium carbonate, potassium bromide, hydroxylamine sulfate, which was consumed during running.
Add 4-(N-ethyl-N-βhydroxyethylamino)-2-methyl-aniline sulfate and adjust the pH.
It was adjusted to 10.05 and reused as a replenisher. Table 1 shows the decrease in sensitivity when the sample was reused 10 times with 1 minute overflow as one time. The results in Table 1 show that Samples 101 and 102 had almost no decrease in sensitivity, whereas Samples 103 and 104 had a large decrease in sensitivity. This means that even if the leaving groups of compounds (1), (19), and (26) are washed out into the color developing solution, they change into compounds that have no photographic effect, and therefore, like other conventional inhibitors, This shows that it does not accumulate in the developer and can be recycled and used repeatedly.

[Table] Example 2 Sample 201; compound instead of compound (1) of sample 101
It was produced in the same manner as Sample 101 except that (10) was used 1.2 times as much as (1). Sample 202; compound instead of compound (1) in sample 101
It was produced in the same manner as Sample 101 except that (9) was used twice. Sample 203: Produced in the same manner as Sample 101 except that DIR coupler D-3 was used twice as much as Compound (1) in Sample 101. Samples 201 to 203 were processed into 35m/m size films, exposed through a wedge, and subjected to the development process of Example 1 for 5 days.
I used a developer tank of 100m. 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.

[Table] The values in the table above are the sensitivity reduction at fog + density 0.3 expressed in logE. The results in Table 2 show that when using the compound of the present invention,
This shows that there is little decrease in sensitivity. This is because the development inhibitor released from the compound of the present invention changes into a compound that has no photographic effect after flowing out into the developer.

Claims (1)

[Claims] 1. A development inhibitor having a partial structure having two carbon atoms bonded by a non-aromatic double bond and an electron-withdrawing group bonded to at least one of the carbon atoms, A silver halide color photographic light-sensitive material characterized by containing a compound that becomes photographically usable by reaction with an oxidized developing agent.