JPH053574B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a silver halide photographic light-sensitive material containing a group capable of releasing a photographically useful group through an oxidative process during a photographic processing step. (Prior Art) Many compounds have been known that release photographically effective groups in response to the density of an image during development. Hydroquinone derivatives (e.g.
DIR hydroquinone) is known. As DIR hydroquinone, compounds described in US Pat. No. 3,379,529, US Pat. No. 3,620,746, JP-A-49-129,536, etc. are known. DIR hydroquinone, as known from the above-mentioned patents, is used for the purpose of obtaining so-called DIR effects such as controlling image tone, making images finer, improving image sharpness, and improving color reproduction. However, although the DIR hydroquinone known so far has a certain degree of performance, it has been desired to further improve the performance. In particular, the known DIR hydroquinone has the disadvantage that the development inhibitor released during 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 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 DIR hydroquinone. It was a serious problem. Although expedient measures have been taken in the past to solve this problem, all of them have drawbacks, and no fundamental solution is known. For example, the amount of DIR hydroquinone used may be limited, the processing solution may be frequently replaced with a new one, or a layer of fine particle material that has virtually no photographic sensitivity may be newly added to the photosensitive material to ensure that it does not flow out of the photosensitive layer. This method captures the development inhibitor. However, all of these methods have drawbacks, such as reducing the degree of photographic improvement and significantly increasing costs. (Object of the Invention) The DIR compounds such as DIR hydroquinone of the present invention fundamentally improve the above-mentioned problems. That is, the first object of the present invention is to provide a photographic material with excellent image sharpness by using a novel DIR compound. A second object of the present invention is to provide a photographic material with excellent color reproducibility by using a novel DIR compound. A third object of the present invention is to provide a photographic material that does not contaminate the developer and is suitable for a processing method that continuously reuses the developer by using a new DIR compound. (Structure of the Invention) The object of the present invention is to form a compound that has development inhibiting properties after it is released from the compound by a redox reaction, and furthermore, that it has substantially no or significantly no development inhibiting properties in a developer. This can be achieved by incorporating in the silver halide photographic light-sensitive material at least one compound having a group that changes into a reduced compound. That is, the present invention provides a silver halide photographic light-sensitive material including at least one silver halide photographic emulsion layer on a support. A silver halide photographic photosensitive material containing at least one compound represented by the following general formula () having a group that converts into a compound having substantially no or significantly reduced development inhibiting properties in a developer. Achieved through materials. General formula [] In the formula, A and A' represent a group that can be hydrolyzed with hydrogen or an alkali. X, Y, and Z represent hydrogen, a halogen atom, an alkyl group, an alkoxy group, an aryl group, a thioalkyl group, or an electron-withdrawing group. PUG is a group released by reaction with an oxidized developing agent, and is represented by the following general formula (). The general formula () -AF-CCD -AF-CCD is represented by the following general formulas (P-1) to (P-1) to (P-5). General formula (P-1) General formula (P-2) General formula (P-3) General formula (P-4) General formula (P-5) In the formula, G ₁ is a hydrogen atom, a halogen atom, an alkyl group, an acylamino group, an alkoxy group, a sulfonamide group, an aryl group, an alkylthio group, an alkylamino group, an anilino group, an amino group, an alkoxycarbonyl group, an acyloxy group, a nitro group , a cyano group, a sulfonyl group, an aryloxy group, a hydroxy group, a thioamide group, a carbamoyl group, a sulfamoyl group, a carboxyl group, a ureido group, or an aryloxycarbonyl group. In the formula, G ₂ represents a substituent among the substituents listed for G ₁ that can be a divalent group. In the formula, G ₃ is an alkylene group or an arylene group, and may include an ether bond, ester bond, thioether bond, amide bond, ureido bond, imide bond, sulfone bond, sulfonamide bond, or carbonyl group. In the formula, V ₁ represents a nitrogen atom or a methylene group, and V ₂ represents 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 represents a hydrogen atom, an alkyl group or an aryl group. In the formula, f represents an integer of 1 or 2, and h represents 0 or 1. When f is 2, the two G ₁ 's may be the same or different. At least one of the groups represented by V ₂ and G ₄ in general formulas (P-4) and (P-5) is a group containing CCD. The group represented by CCD in the general formula () is
PUG reacts with developer components in the developer, causing PUG
indicates that it is a group that has substantially no or significantly reduces development inhibitory properties. The compound of general formula [] will be explained in more detail. In the formula, A and A' represent a group that can be hydrolyzed with hydrogen or an alkali. Examples include an acyl group and an alkoxycarbonyl group. X, Y, and Z are hydrogen, halogen atoms (e.g., chromium, bromine, iodo), substituted or unsubstituted alkyl groups (preferably having 1 to 20 carbon atoms, such as methyl, ethyl, propyl, allyl, octyl). group, dodecyl group,
Examples include cyclohexyl group, hydroxyethyl group, sulfoethyl group, and carboxypropyl group. In addition, Y and Z may be bonded via a methylene chain to form a 5- or 6-membered ring), a substituted or unsubstituted alkoxy group (preferably having 1 to 20 carbon atoms, such as a methoxy group, an ethoxy group, Butyloxy group, octyloxy group, hexadecyloxy group,
(methoxyethoxy group, etc.), substitution,
Unsubstituted aryl group (preferably having 6 to 20 carbon atoms, such as dodecylphenyl group, tolyl group, p
-methoxyphenyl group, p-chlorophenyl group, etc.) thioalkyl group (preferably has 1 to 20 carbon atoms, such as methylthio group, butylthio group, octylthio group, hexadecylthio group, etc.) and electron-withdrawing group. represent. Examples of electron-withdrawing groups include

【formula】 【formula】

[Formula] −SO ₂ −R ⁵ ,

[Formula]. Here, R ¹ to ^{R 7} are substituted or unsubstituted alkyl groups (preferably having 1 to 30 carbon atoms, examples include methyl group, ethyl group, propyl group, allyl group, butyl group, octyl group, dodecyl group, Adamantyl group, cyclohexyl group, methoxyethyl group, hydroxyethyl group,
sulfoethyl group, carboxypropyl group, etc.),
Substituted or unsubstituted aryl group (preferably 6 carbon atoms)
~30, examples include dodecylphenyl group, tolyl group, p-methoxyphenyl group, phenyl group,
p-chlorophenyl group, m-nitrophenyl group, etc.), substituted or unsubstituted aralkyl group (preferably having 7 to 30 carbon atoms, examples include benzyl group, phenethyl group, etc.). Further, in the general formula [], PUG is a group released by reaction with an oxidized developing agent, and is preferably represented by the following general formula []. -AF-CCD () In the general formula (), the group represented by AF is preferably the following. Shown along with CCD substitution positions. General formula (P-1) General formula (P-2) General formula (P-3) General formula (P-4) General formula (P-5) 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, hexaneamide group), an alkoxy group (e.g. methoxy group, benzyloxy group), sulfonamide group. groups (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 is a substituted or unsubstituted arylene group, which is a coating, an ether bond, an ester bond, a thioether bond, an amide bond, a ureido bond, an imide bond, a sulfone bond, or a sulfonamide bond. , carbonyl group, etc., or 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, V ₁ represents a nitrogen atom or a methylene group, and V ₂ represents 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 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 1 or 2, and h represents 0 or 1. When f is 2, the two G ₁ 's may be the same or different. At least one of the groups represented by V ₂ and G ₄ in general formulas (P-4) and (P-5) 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 G ₅ When containing an alkyl group moiety, the alkyl group may have 1 to 22 carbon atoms, preferably 1 to 10 carbon atoms, and may be substituted or unsubstituted, linear or branched, chain or cyclic, saturated or unsaturated. good. Furthermore, when a G ₁ , G ₂ , G ₃ , G ₄ or G ₅ aryl group is included, the aryl group has 6 to 10 carbon atoms and is preferably a substituted or unsubstituted phenyl group. The group represented by CCD in the general formula () is
Preferred are those represented by (D-1), (D-2) and (D-3) to (D-16) described below. General formula (D-1) -COOR ⁸ General formula (D-2) R ⁸ and R ⁹ are substituted or unsubstituted alkyl (preferably having 1 to 10 carbon atoms, such as methyl, ethyl,
Substituted or unsubstituted aryl group (preferably carbon number 6～
10, such as phenyl, 3,4-methyleneoxyphenyl, p-methoxyphenyl, p-cyanophenyl, m-nitrophenyl, groups, etc.) Substituted or unsubstituted aralkyl group (preferably 7 to 7 carbon atoms) 12, such as benzyl, p-nitrobenzyl, etc.). General formula (D-3) General formula (D-4) General formula (D-5) In the formula, Z ₁ or Z ₂ represents a bond with AF or the following group; hydrogen atom, alkylamino group (e.g. CH ₃ -NH-,

[Formula] group), alkyl groups (e.g. methyl group, propyl group, methoxymethyl group, benzyl group), aryl group (e.g. phenyl group, 4-chlorophenyl group, naphthyl group, 4-methoxyphenyl group, 4-butanamide group) phenyl group), an acylamido group (the nitrogen atom may be substituted; for example, an acetamide group, a benzamide group), or a 4- to 7-membered substitution containing a hetero atom selected from a nitrogen atom, a sulfur atom, and an oxygen atom. or an unsubstituted heterocyclic group (e.g. 2
-pyridyl group, 2-pyrrolidinyl group, 4-imidazole group, 3-chloro-5-pyrazolyl group, etc.). In the formula, Z ₃ is a hydrogen atom, a halogen atom, an alkyl group (e.g. methyl group, propyl group, etc.), an aryl group (e.g. phenyl group, 4-chlorophenyl group, naphthyl group, etc.), a heterocyclic group (a nitrogen atom as a hetero atom). , sulfur atom, oxygen atom; e.g. 2-pyridyl group, 2-pyrrolidinyl group), alkoxy group (e.g. methoxy group, butoxy group), acyl group (e.g. acetyl group). group, benzoyl group), carbamoyl group (nitrogen atom may be substituted;
For example, N-butylcarbamoyl group, N-phenylcarbamoyl group), sulfamoyl group (nitrogen atom may be substituted; e.g. N-phenylsulfamoyl group), sulfonyl group (e.g. propanesulfonyl group, benzenesulfonyl group) ), alkoxycarbonyl group (e.g. ethoxycarbonyl group), acylamino group (e.g. acetamido group,
(benzamide group), sulfonamide group (e.g. benzenesulfonamide group), alkylthio group (e.g. butylthio group) or ureido group (nitrogen atom may be substituted; e.g. 3-phenylureido group, 3-butylureido group). .
Z ₁ and Z ₃ may be combined to form a ring. In general formula (D-5), Z ₄ is 5-membered or 6-membered
Group of atoms forming an unsaturated heterocycle (carbon atoms,
(selected from nitrogen atom, oxygen atom or sulfur atom), and X represents an organic sulfonic acid anion, an organic carboxylic acid anion, a halogen ion,
Alternatively, it represents an inorganic anion (eg, tetrafluoroborate, etc.). Examples of heterocycles composed of Z ₄ are as follows. In the following example, Z ₁ is bonded at a substitutable position. In the formula, Z ₇ has the same meaning as the substituent listed for Z ₁ or Z ₂ above, and Z ₆ represents an oxygen atom or a sulfur atom. General formula (D-6) Here, Z ₁ and Z ₂ are as described above, and Z ₅ is

Forms a 5- to 7-membered ring with [Formula], and

Represents an atomic group selected from carbon atoms, oxygen atoms, and nitrogen atoms that do not impart aromaticity to [Formula], preferably an alkylene group (which may be substituted; for example, -(CH ₂ ) ₄ -), Alkenylene group (optionally substituted; e.g. _-CH2 -CH=CH- _CH2- ,

In addition to [formula]),

[Formula] is a group, etc. In general formulas (D-3), (D-4), (D-5) and (D-6), when Z ₁ , Z ₂ , Z ₃ or Z ₇ contains an alkyl group moiety, the alkyl group is a carbon Number 1
~16, preferably 1 to 10 substitutions or no substitutions,
It may be straight chain or branched, chain or cyclic, saturated or unsaturated. Furthermore, Z ₁ ,
When Z ₂ , Z ₃ or Z ₇ contains an aryl group, the aryl group has 6 to 10 carbon atoms and is preferably a substituted or unsubstituted phenyl group. General formula (D-7) General formula (D-8) General formula (D-9) General formula (D-10) In addition, in general formulas (D-7) to (D-10), at least one of Z ₁₁ to _{Z 17} is the above-mentioned AF.
group or a group containing an AF group. In the formula, Z ₁₁ and Z ₁₂ are each a hydrogen atom,
Represents an alkyl group, an aryl group, or an AF group. In the formula, Z ₁₃ , Z ₁₄ , Z ₁₅ and Z ₁₆ 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 groups (e.g. methylthio group, butylthio group), alkoxycarbonyl group (e.g. ethoxycarbonyl group, octylcarbonyl group), aryloxycarbonyl group (e.g. phenoxycarbonyl group), alkanesulfone group (e.g. methanesulfonyl group), sulfamoyl group ( For example, 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-membered ring or 6-membered ring selected from nitrogen atom, oxygen atom or sulfur atom as hetero atom) , such as imidazolyl, 1,2,4-triazolyl, thiadiazolyl or oxadiazolyl), acyloxy (e.g. acetyloxy), nitro, cyano, carboxyl, thiocarbamoyl (e.g. phenylthio) carbamoyl group), sulfamoylamino group (e.g. N-fersulfamoylamino group),
diacylamino group (e.g. diacetylamino group)
Alternatively, it represents an arylidene amino group (for example, a benzylidene amino group) or an AF group. Z ₁₇ represents the following group. In Z ₁₇ , 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 amount , diacylamino group, arylsulfonyl group, heterocyclic group, nitro group, cyano group, carboxyl group or sulfonamide group. Specific examples are given for Z ₁₃ to Z ₁₆ . In general formulas (D-7), (D-8), (D-9) and (D-10), Z ₁₁ , Z ₁₂ , Z ₁₃ , Z ₁₄ , Z ₁₅ ,
When Z ₁₆ or Z ₁₇ contains an alkyl group, the alkyl group has 1 to 16 carbon atoms, preferably 1 to 8 carbon atoms, and is substituted or unsubstituted, linear or branched, chained or cyclic, saturated or unsaturated. It's okay to be hot. Furthermore, when Z ₁₁ , Z ₁₂ , Z ₁₃ , Z ₁₄ , Z ₁₅ , Z ₁₆ or Z ₁₇ 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 (D-9), Z ₁₅ and Z ₁₆ are each divalent and are connected, forming a ring (for example, a benzene ring)
may be formed. In general formula (D-10), Z ₁₅ and Z ₁₆ each serve as a divalent group and may be connected to form a ring (for example, a benzothiazolylidene group). General formula (D-11) General formula (D-12) General formula (D-13) General formula (D-14) In the formula, Z ₂₁ represents a saturated or unsaturated 6-membered ring, and k ₁ and k ₂ represent an electron-absorbing group (e.g.

[Formula] −SO ₂ −, etc.), and k ₃ is

[Formula] (where R represents an alkyl group, preferably one having 6 or less carbon atoms). General formula (D-15) (However, h=0 in the above general formulas (P-1) to (P-5)) General formula (D-16) (However, in the above general formulas (P-1) to (P-5), h=0) In the formula, Z ₃₁ represents a group forming a 5- or 6-membered lactone ring or a 5-membered ring imide. Next, specific examples of compounds used in the present invention will be given, but the present invention is not limited thereto. The compound () represented by the general formula can generally be synthesized by the following two methods. That is, the first method is to react a benzoquinone derivative with mercaptoazole or benzoquinone in chloroform, 1,2-dichloroethane, or carbon tetrachloride in the presence of an acid catalyst such as p-toluenesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, or methanesulfonic acid. This is a method in which triazole derivatives are reacted at temperatures between room temperature and 100°C. Second, chlorine,
A method in which a quinone compound obtained by reacting a benzoquinone derivative substituted with bromine or iodine with a photographically useful compound at a temperature between -20°C and 100°C is reduced with a reducing agent such as diethylhydroxylamine or sodium hydrosulfite. be. [References
Research Disclosure 18227 (1979), Liebigs Ann,
Chem, 764, 131 (1972)] Specific examples of synthesis of compounds are shown below. The compounds used in the present invention can be easily synthesized using these methods. Synthesis Example 1 (Synthesis of Compound 1) 20 g of tertiary octibenzoquinone and 22 g of 5-phenoxycarbonylbenzotriazole were mixed in 200 ml of acetonitrile, and after adding a catalytic amount of p-toluenesulfonic acid, about 8 Time circulates. After concentrating the solvent, the residue is purified by silica gel chromatography. The first fraction was concentrated using hexane:ethyl acetate = 4:1 as a solvent, and the residue was crystallized from acetonitrile to obtain 4.3 g of compound 1, m.
p.205-207℃ Synthesis Example 2 (Synthesis of Compound 3) 20 g of p-benzoquinone and 40 g of 1[4-(4-cyanophenoxycarbonyl)phenyl]-5-mercaptotetrazole were mixed in 300 ml of acetonitrile, and the mixture was heated at room temperature. Make it react. The formed crystals are separated from each other, and then the obtained crystals are oxidized with manganese dioxide in acetone. Remove excess oxidant by filtration,
The liquid was concentrated, and the residue was crystallized from a mixture of acetone and water to obtain 20 g of a quinone (mp 173-174°C). 20 g of this quinone and 11 g of (K) hexadecyl mercaptan were mixed in 200 ml of acetonitrile. death,
Furthermore, after adding a catalytic amount of p-toluenesulfonic acid, the mixture was allowed to react at room temperature for 5 hours. The precipitated crystals were removed separately, the liquid was concentrated, and the residue was crystallized from acetonitrile to obtain 8 g of Compound 3. mp98
~99°C Synthesis Example 3 (Synthesis of Compound 5) Mix in the same manner as in Synthesis Example 1, add p-toluenesulfonic acid, and then reflux for 3 hours under a nitrogen stream. After concentrating the acetonitrile, the residue is purified by silica gel chromatography. Using hexane:ethyl acetate=3:1 as a solvent, a small amount of the first fraction was discarded, and the second fraction was concentrated and crystallized from acetonitrile to obtain 3.5 g of compound 5. mp207-209℃ Synthesis Example 4 (Synthesis of Compounds 7 and 14) To a solution of 15 g of 5-methoxy-2-undecanoylbenzoquinone in acetonitrile, add 20 g of 5-phenoxycarbonylbenzotriazole and stir at room temperature for 2 hours. . _{Add excess Na2S2O5 to} the reaction mixture _.
Add dropwise to solution and stir for 1 hour. The precipitated crystals were collected, washed with water, and then crystallized from acetonitrile to initially obtain 3 g of Compound 7. m.
p.162-164°C, and then the liquid was left in the refrigerator to obtain 2g of Compound 14. mp130-133℃ Synthesis Example 5 (Synthesis of Compound 8) Tertiary octylbenzoquinone 10g, 1-
7 g of [4-(4-cyanophenoxycarbonyl)phenyl]-5-mercaptotetrazole and a catalytic amount of p-toluenesulfonic acid are added to acetonitrile and reacted for 5 hours at room temperature under a nitrogen stream. Collect the precipitated crystals, dissolve them in ethyl acetate, wash with water, and separate the crystals. The ethyl acetate layer was dried over anhydrous sodium sulfate, concentrated, and the residue was recrystallized from acetonitrile to obtain 6.5 g of Compound 8. mp199-200℃ Synthesis Example 6 (Synthesis of Compound 34) -Synthesis of phenylsulfonyl-1,4-dihydroxynaphthalene Dissolve 15.8 g of 1,4-naphthoquinone at room temperature in 100 ml of ethyl acetate/acetic acid = 9:1. Add 24.6 g of sodium benzenesulfinate to this. After stirring for 5 hours, the precipitated crystals were collected and washed with a small amount of acetone. Yield 22.5g Synthesis of 2-phenylsulfonyl-1,4-naphthoquinone 10g of the above naphthohydroquinone was added to acetone.
Add an excessive amount of manganese dioxide to 150 ml of Kendakure and reflux for 3 hours. When inorganic substances are removed by heating and the solvent is distilled off, naphthoquinone is obtained as crystals. Yield: 4.5 g 2-sulfophenyl-3-{1-(3-acryloyl phenyl)tetrazol-5-ylthio}-1,4-dihydroxynaphthalene (compound 34) 4 g of the above naphthoquinone compound and 1-(3-acryloyl phenyl) -3 g of 5-mercaptotetrazole is suspended in 80 ml of ethyl acetate and heated under reflux for 4 hours. After removing insoluble materials, the solution is cooled,
Collect the precipitated crystals. Yield 2gm.p.205~
208℃ (decomposition) Synthesis Example 7 (Synthesis of Compound 36) 2-Methyl-5-lauroylbenzoquinone 5g
and 3 g of 5-succinimidobenzotriazole were heated under reflux in 60 ml of acetonitrile for 3 hours, and after cooling, the precipitated crystals were collected. Yield 2gm.p.196
~199℃ Synthesis Example 8 (Compound 45) Synthesis of 2-laurylcarbamoyl-1,4-dihydroxynaphthalene 2-phenoxycarbonyl-1,
28 g of 4-dihydroxynaphthalene was dissolved in 150 ml of acetonitrile, 22.2 g of laurylamine was added dropwise thereto, and the mixture was refluxed for 4 hours. After the reaction is complete, cool and collect the precipitated crystals. Yield 26.8
g 3-chloro-2-laurylcarbamoyl-
Synthesis of 1,4-naphthoquinone 7.4 g of the above naphthohydroquinone was added to 100 ml of chloroform and stirred. Add this to 5-10℃
Slowly drop 5.7 g of sulfuryl chloride while maintaining the temperature. After the reaction is completed, water is added and the mixture is separated. Take the chloroform solution, evaporate the solvent, and quickly purify it by column chromatography using silica gel. Yield 3.4g 2-Laurylcarbamoyl-3-{1-(2-
Synthesis of chloroethyl)-5-ylthio}-1,4-naphthoquinone 4 g of the crystals obtained in the above were dissolved in 70 ml of acetone and cooled to 5°C with ice water. Add to this 1.8 g of 1-(2-chloroethyl)-5-mercaptotetrazole
and then 1.7g of anhydrous potassium carbonate.
Stir for 3 hours. Collect the precipitated crystals. To further remove inorganics, add 200 ml of 10% acetic acid water.
Wash with ml and dry. Quantity 3.5g 2-laurylcarbamoyl-3-{1-(2-
Chloroethyltetrazole)-5-ylthio} 1,4-dihydroxynaphthalene (compound
45) 8.7g of sodium hydrosulfite
An acetonitrile solution of 5.5 g of the naphthoquinone obtained above was dissolved in 80 ml of water at room temperature.
Crystals precipitate immediately and are recrystallized from ethyl acetate. Yield 3.8gm.p.177-181℃ Synthesis Example 9 (Compound 46) 2-methoxy-5-lauroylbenzoquinone 7
g and 5-(3-benzoylpropionamide)
4.5g of benzotriazole in 240ml of acetonitrile
Mix and heat under reflux for 2.5 hours. Insoluble materials are removed by filtration, the solution is cooled, and the resulting crystals are collected. Yield 1.7g m.p. 188-192°C (decomposed). The novel photographic DIR compound of the present invention is disclosed in the U.S. patent
Similar to the DIR hydroquinones described in No. 3379529, etc., it is cross-oxidized by a redox reaction with the oxidized developing agent produced in an imagewise manner during development, releases a development inhibitor in an imagewise manner, and converts into a colorless oxidized product. It is estimated to be. The development inhibiting substance released in an imagewise manner suppresses development in an imagewise manner, and exhibits DIR effects such as making the image finer, softening the image tone, improving image sharpness, and improving color reproduction. Such DIR compounds of the present invention are similar to conventional DIR compounds as described below.
Compared to hydroquinone, it has extremely high activity and shows surprising effects even when added in small amounts. The photographic DIR compounds of the present invention can be equally used in light-sensitive materials to be developed in black and white as well as in light-sensitive materials for forming color images. The amount used is not particularly limited, but preferably 10 ^-6 to 1 mol/molAg, particularly preferably 10 ^-5 to 1 mol/molAg.
It is in the range of 10 ^-1 mol/molAg. The photographic DIR compound of the present invention can be dispersed and introduced into the photographic layer by a known method described below. In this case, the photographic DIR compounds of the present invention may be used alone or in combination of two or more. Further, the photographic DIR compound of the present invention can be used in combination with a coupler and added to the same emulsion layer as the coupler, or can be added as a separate emulsified dispersion to a photographic auxiliary layer such as an interlayer. In the present invention, when the compound of the present application is used or when the coupler described below is used in combination, known methods for introducing it into the silver halide emulsion layer, such as the U.S. patent
The method described in No. 2322027 is used. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, etc.)
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), trimesates (e.g. tributyl trimesate), etc., or organic solvents with a boiling point of about 30°C to 150°C, e.g. Lower alkyl acetates such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-
After being dissolved in 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 carboxymethyl cellulose and cellulose sulfate esters; sugar derivatives such as 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. The average grain size of the silver halide grains in the photographic emulsion (the grain size is the grain diameter in the case of spherical or approximately spherical grains, the ridge length in the case of cubic grains,
Expressed as an average based on projected area. ) is not particularly long, 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 regular crystal structures such as cubic or octahedral shapes, or may have irregular crystal structures such as spherical or plate shapes, or may have irregular crystal structures such as spherical or plate shapes. 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 particle. 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.
Making and Coating Photographic 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). As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called controlled 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. Silver halide emulsions are usually chemically sensitized.
For chemical sensitization, see for example “Die
Grundlagender Photographischen Prozesse
mit Silberhalogeniden” (Akademische
Verlagsgesellschaft, 1968) 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);
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 substitution (1,3,3a,7)
Many compounds known as antifoggants or stabilizers can be added, such as benzenethiosulfonic acid, benzenesulfonic acid, benzenesulfonic acid amide, etc.; can. 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/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycols Nonionic interfaces such as alkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Activator: Alkyl carboxylate, alkyl sulfonate, alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl sulfate, alkyl phosphate, N-acyl-N-alkyl taurine, sulfosuccinic acid Esters, sulfoalkyl polyoxyethylene alkyl phenyl ethers,
Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, such as polyoxyethylene alkyl phosphates; amino acids, aminoalkylsulfonic acids, amino Amphoteric surfactants such as alkyl sulfates or phosphates, alkyl betaines, and amine oxides; alkyl amine salts, aliphatic or aromatic quaternary ammonium salts, and heterocyclic quaternary ammonium salts such as pyridinium and imidazolium. , and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used. For the purpose of increasing sensitivity, increasing contrast, or accelerating development, 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. 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. singly or in combination, or together with acrylic acid, methacrylic acid, α,β-unsaturated dicarboxylic acid, hydroxyalkyl (meth)acrylate, sulfoalkyl (meth)acrylate,
Polymers containing combinations of styrene sulfonic acid and the like as monomer components can be used. 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 a fat-sensitive 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. Merocyanine dyes or complex merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidic-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, and a rhodanine nucleus having a ketomethylene structure. Nuclei, 5- to 6-membered heterocyclic nuclei such as thiobarbituric acid nuclei 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, aminostilbene 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 invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support. Multilayer natural color photographic materials usually have at least one each of a red-sensitive emulsion layer, an edge-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 edge-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 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, cyanoacetylmalone couplers, open-chain acylacetonitrile couplers, etc., yellow couplers include acylacetamide couplers (e.g. benzoylacetanilides, pivaloylacetanilides), etc., and cyan couplers include naphthol couplers, and There are phenol couplers, etc. 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 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. In the photographic light-sensitive material of the present invention, the above-mentioned couplers, etc.
In order to satisfy the characteristics required for photosensitive materials, two or more types can be used together in the same layer, 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. Examples include chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldede, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxy dioxane, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine,
1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,4-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 cuff prevention agent. 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. When carrying out the present invention, the following known antifading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more. Known antifading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives, and bisphenols. Any known method can be used to photographically process the silver halide photographic material of the present invention. A known treatment liquid can be used. The processing temperature is usually chosen between 18°C and 50°C, but temperatures below 18°C or above 50°C may also be used. Depending on the purpose, either a development process that forms a silver image (black and white photographic process) or a color photographic process that consists of a development process that forms a dye image can be applied. The developer used in black-and-white photographic processing can contain conventionally known developing agents. Examples of developing agents include dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. 1-phenyl-3-pyrazolidone), aminophenols (e.g. N-methyl-p-aminophenol), 1-phenyl-3-pyrazoline. Ascorbic acid, and heterocyclic compounds such as those described in US Pat. No. 4,067,872 in which a 1,2,3,4-tetrahydroquinoline ring and an indolene ring are condensed can be used alone or in combination. The developer generally contains other known preservatives,
Contains alkaline agents, PH buffering agents, anti-fogging agents, etc., as well as solubilizing agents, color toning agents, development accelerators, surfactants, antifoaming agents, water softeners, hardeners, viscosity imparting agents, etc. May include. As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur acid compounds known to be effective as fixing agents can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent. When forming a dye image, conventional methods can be applied. For example, negative-positive method (for example, “Journal of the
Society of Motion Picture and Television
Engineers, Volume 61 (1953), pp. 667-701), developed in a developer containing a black and white developing agent to produce a negative silver image, followed by at least one uniform exposure or other suitable fogging. process,
The color reversal method, in which a dye-positive image is obtained by subsequent color development, and the silver dye bleaching method, in which a photographic emulsion layer containing a dye is exposed and developed to create a silver image, and this is used as a bleaching catalyst to bleach the dye, etc. . 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-methanesulfonamidoethylaniline,
4-amino-3-methyl-N-ethyl-N-β-
methoxyethylaniline, etc.) can be used. Other Photography by LFAMason
Processing Chemistry (Focal Press, 1966)
pages 226-229, U.S. Patent No. 2193015, U.S. Patent No. 2592364
JP-A No. 48-64933, etc. may be used. Color developers may also contain pH buffering agents such as alkali metal sulfites, carbonates, borates and phosphates, development inhibitors or antifoggants such as bromides, iodides and organic antifoggants. can. In addition, if necessary, water softeners, preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol, development accelerators such as polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers, and competitive couplers may be added. , fogging agents such as sodium borohydride, auxiliary developers such as 1-phenyl-3-pyrazolidone, viscosity-imparting agents, U.S. Pat. No. 4,083,723.
It may also contain a polycarboxylic acid chelating agent described in No. 1, an antioxidant described in OLS No. 2622950, 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 bleaching agents, compounds of polyvalent metals such as iron (), cobalt (), chromium (), copper (), peracids, quinones, nitroso compounds, etc. are used. For example, phenicyanide, dichromate, organic complex salts of iron () or cobalt (), aminopolcarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid, or citric acid, tartaric acid. , complex salts of organic acids such as malic acid; persulfates, permanganates; nitrosophenols, etc. can be used. Of these, potassium ferricyanide, sodium ferric ethylenediaminetetraacetate, and ammonium ferric ethylenediaminetetraacetate are particularly useful. Ethylenediaminetetraacetic acid iron() complex salts are useful in both stand-alone bleach solutions and single bath bleach-fix solutions. Bleach or bleach-fix solution has US Patent 3042520
No. 3241966, Special Publication No. 1977-8506, Special Publication No. 1973
- Bleaching accelerator described in No. 8836, etc., JP-A-53-
In addition to the thiol compound described in No. 65732, various additives can be added. The photographic DIR compound of the present invention can be used in various silver halide photographic materials, for example, it is useful for both black and white, color, etc. for electron beam, high resolution black and white, diffusion transfer black and white, general color,
It can be applied to silver halide photographic materials for various uses such as color X-ray and diffusion transfer type color. Since the DIR compound of the present invention has high activity, it is oxidized and quickly releases a development inhibitor. Therefore, by adding only a small amount, it is possible to provide DIR effects such as controlling image tone, making images finer, improving image sharpness, and improving color reproduction. Furthermore, the DIR compound of the present invention is stable even in silver halide photographic materials and does not deteriorate storage stability, so it can be used with confidence. Furthermore, even when a large amount of a photosensitive material is processed, the DIR compound of the present invention can produce a desired DIR effect because the development inhibitor will not accumulate in the processing solution and have no adverse photographic effect. Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited thereto. 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 Gelatin layer containing an emulsified dispersion of 2,5-di-t-octylhydroquinone 3rd layer: 1st red-sensitive emulsion Layer (RL ₁ ) Silver iodobromide emulsion (silver iodide: 5 mol%)... Silver coating amount 1.79 g/m ² 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 of the above compound (3)...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/m ² 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: per 1 mol of silver Coupler C-1: 0.0008 mol per mol of silver Coupler C-2: 0.0008 mol per mol of silver Compound (3) above: 0.00006 mol per mol of silver
5th molar layer: Intermediate layer (ML) 6th layer same as the 2nd layer: 1st edge-sensitive emulsion layer (GL ₁ ) Silver iodobromide emulsion (silver iodide: 4 mol%)...coated silver amount 1.5 g / ^m2 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...0.058 mol coupler per 1 mol of silver M-1...0.008 mol per 1 mol of silver The above compound (3)...0.0015 mol per 1 mol of silver 7th layer: Second edge-sensitive emulsion layer (GL ₂ ) Silver iodobromide emulsion (Iodobromide emulsion) Silver oxide: 5 mol%)...Amount of coated silver 1.6 g/ ^m2 Sensitizing dye...2.5 x 10 ^-5 mol per 1 mol of silver Sensitizing dye...0.8 x 10 ^-5 per 1 mol of silver Mol Coupler B...0.02 mol per 1 mol of silver Coupler M-1...0.003 mol per 1 mol of silver Compound (3)...0.0003 mol per 1 mol of silver 8th layer: Yellow filter layer (YEL) Yellow colloidal silver and 2.5-
and an emulsified dispersion of di-t-octylhydroquinone. 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: 1st blue-sensitive emulsion layer (BL ₂ ) Silver iodobromide (silver iodide: 6 mol %)...Amount of coated silver
1.1 g/m ² Coupler Y-1...0.06 mol per 1 mol of silver 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 (7) was added in the same amount as (3) instead of compound (3) in RL ₁ and RL ₂ of sample 101, and compound (14) was added in place of compound (3) in GL ₁ and GL ₂ . Sample 101 was prepared in the same manner as sample 101 except that twice as much as (3) was added. Sample 103: Produced in the same manner as Sample 101 except that DIR-Compound DIR-1 was used in the same amount as Compound (3) in Sample 101 instead of Compound (3). Sample 104: Produced in the same manner as Sample 101 except that DIR compound DIR-2 was used in the same amount as (3) instead of Compound (3) in Sample 101. DIR compound for comparison DIR-2 for comparison 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 films of 35 mm size and subjected to wedge exposure, and each film was subjected to the following development process in two developer tanks. 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 Stability... 3 minutes 15 seconds The composition of the processing solution used in each step is as follows. Color developer Sodium nitrotriacetate 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 solution Sodium tetrapolyphosphate 2.0g Sodium sulfite 4.0g Ammonium thiosulfate (70%) 175.0ml Sodium bisulfite 4.6g Added water 1 Stabilizing liquid formalin 8.0ml Added water 1 Furthermore, the overflow of the developer was recycled by the following method and reused. 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 liquid contains sodium nitrotriacetate, 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 is reused 10 times, with 1 minute of overflow occurring once. 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 (3), (7), and (14) are leaked into the color developing solution, they will react and change into compounds that have no photographic effect; This shows that unlike the base, it does not accumulate in the developer and can be recycled and used repeatedly.

[Table] However, the decrease in sensitivity
Expressed as log E.
Example 2 Sample 201; compound (5) instead of compound (3) in sample 101
It was prepared in the same manner as Sample 101 except that 1.2 times as much as in (3) was used. Sample 202; compound (15) instead of compound (3) in sample 101
It was produced in the same manner as Sample 101 except that twice as much was used. Sample 203: Produced in the same manner as Sample 101 except that DIR compound DIR-3 was used in the same amount as (3) instead of Compound (3) in Sample 101. DIR compound for comparison: DIR-3 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 for 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. According to the results in Table 2, samples 201 and 202 have less decrease in sensitivity than sample 203. This indicates that the leaving groups of compounds (5) and (15) are converted into compounds that have no effect on photographic properties after flowing out into the color developing solution.

[Table] However, the decrease in sensitivity
Expressed as log E.
Example 3 A silver halide emulsion consisting of 80 mol% silver chloride, 19.5 mol% silver bromide, and 0.5 mol% silver iodide was prepared by gold sensitization and sulfur sensitization in a conventional manner. Further, gelatin contained in this emulsion was 45% by weight based on silver halide. 5 in this emulsion
-[3-(δsulfobutyl)-5-chloro-2-oxazolidylideneethylidene]-1-hydroxyethoxyethyl-3-(2-pyridyl)-2-thiohydantoin potassium salt (spectral sensitizer), dodecyl Sodium benzenesulfonate (surfactant),
After adding the polymer latex described in Preparation Example 3 of U.S. Pat. No. 3,525,620, 1,2-bis(vinylsulfonylacetamido)ethane (hardener)
2.6% by weight per total dry gelatin (i.e. per total dry gelatin including the non-photosensitive upper layer described below)
A coating solution for a photosensitive silver halide emulsion layer was prepared by adding the compound of the present invention as a methanol solution as shown in Table 3. At the same time, sodium dodecylbenzenesulfonate (surfactant) and polymethyl methacrylate laix (matting agent) with an average particle size of 3.0 to 4.0 μm were added to the 5% gelatin solution and applied for the non-photosensitive upper layer. I made a liquid. Next, the photosensitive silver halide emulsion layer coating solution and the non-photosensitive upper layer coating solution were coated onto a polyethylene terephthalate support by a two-layer simultaneous coating method. The amount of coated silver was 3.0 g/m ² , and the dry film thickness of the non-photosensitive upper layer was 1.0 μm. These samples were exposed to white tungsten light for 8 seconds through a step wedge with a step difference of 0.1. Further, halftone images were formed on these samples by the following method. That is, a commercially available negative gray contact screen (150 lines/inch) was brought into close contact with the sample, and white tungsten light was exposed to the screen for 10 seconds through a step wedge with a step height of 0.1. The above exposed sample was heated at 38℃ using the following developer.
Develop for 20 seconds, fix by normal method,
Washed with water and dried. Developer composition Sodium sulfite 75g Sodium hydrogen carbonate 7g Hydroquinone 40g 1-phenyl-4,4-dimethyl-3-pyrazolidone 0.4g Sodium bromide 3g 5-methylbenzotriazole 0.8g Ethylenediaminetetraacetic acid disodium salt 1g 3-diethylamino-1 , 2-propanediol 20g Add water and adjust to 1 PH = 11.4 Table 3 shows the evaluation results for relative sensitivity and γ.
Shown below.

[Table] As is clear from Table 3, it can be seen that the compound of the present invention has a desired DIR with a large effect of softening the gradation. Example 4 DIR compound DIR-1 was used in the same amount as (7) instead of compound (7) of sample 302 in Example 3, and the sample
A sample prepared in the same manner as 302 is used as sample 307 for comparison. Samples 301 to 307 were processed into a size of 3 x 15 cm,
After developing 1000 samples each in the same manner as in Example 3, the sensitivity of the first part and the final sensitivity of the processed samples were compared and shown in Table 4.

[Table] Compare.
As is clear from this result, the compounds of the present invention (samples 302 to 306) show less decrease in sensitivity than sample 307. This shows that after the compound of the present invention flows out into the treatment liquid, it changes into a compound that has virtually no effect.

Claims (1)

[Scope of Claims] 1. A silver halide photographic material comprising at least one silver halide photographic emulsion layer on a support,
After being released from the compound by redox reaction,
Contains at least one compound represented by the following general formula (), which has a group that converts into a compound that has development inhibitory properties, and which transforms into a compound that has substantially no or significantly reduced development inhibitory properties in a developer. A silver halide photographic material characterized by: General formula [] In the formula, A and A' represent a group that can be hydrolyzed with hydrogen or an alkali. X, Y, and Z represent hydrogen, a halogen atom, an alkyl group, an alkoxy group, an aryl group, a thioalkyl group, or an electron-withdrawing group. PUG is a group released by reaction with an oxidized developing agent, and is represented by the following general formula (). The general formula () -AF-CCD -AF-CCD is represented by the following general formulas (P-1) to (P-1) to (P-5). General formula (P-1) General formula (P-2) General formula (P-3) General formula (P-4) General formula (P-5) In the formula, G ₁ is a hydrogen atom, a halogen atom, an alkyl group, an acylamino group, an alkoxy group, a sulfonamide group, an aryl group, an alkylthio group, an alkylamino group, an anilino group, an amino group, an alkoxycarbonyl group, an acyloxy group, a nitro group , a cyano group, a sulfonyl group, an aryloxy group, a hydroxy group, a thioamide group, a carbamoyl group, a sulfamoyl group, a carboxyl group, a ureido group, or an aryloxycarbonyl group. In the formula, G ₂ represents a substitutional transformation listed for G ₁ that can become a divalent group. In the formula, G ₃ is an alkylene group or an arylene group, and may include an ether bond, ester bond, thioether bond, amide bond, ureido bond, imide bond, sulfone bond, sulfonamide bond, or carbonyl group. In the formula, V ₁ represents a nitrogen atom or a methylene group, and V ₂ represents an oxygen atom, a sulfur atom, -NG ₅ - or [Formula]. In the formula, G ₄ is the substitution transformation listed in G ₁ or (G ₃ ) _h
−Represents CCD. G ₅ represents a hydrogen atom, an alkyl group or an aryl group. In the formula, f represents an integer of 1 or 2, and h represents 0 or 1. When f is 2, the two G ₁ 's may be the same or different. At least one of the groups represented by V ₂ and G ₄ in general formulas (P-4) and (P-5) is a group containing CCD. The group represented by CCD in the general formula () is
PUG reacts with developer components in the developer, causing PUG
indicates that it is a group that has substantially no or significantly reduces development inhibitory properties.