JPH087396B2 - Silver halide photosensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide photosensitive material,
In particular, the present invention relates to a silver halide light-sensitive material containing a compound in which an active group or an adsorption group of a dye elution accelerator is blocked and having improved residual color.

(Background Art) In recent years, a sensitizing technique using a sensitizing dye has been developed, and it has been attempted to produce a silver halide light-sensitive material using a large amount of the sensitizing dye. In particular, the method using tabular silver halide grains is suitable for obtaining a highly sensitive silver halide light-sensitive material by using a large amount of sensitizing dye.

U.S. Pat.Nos. 4,434,226, 4,439,520 and 4,41
No. 4,310, No. 4,433,048, No. 4,414,306, No. 4,4
59,353, JP-A-59-99433, JP-A-62-209445, etc., disclose a method for producing tabular grains and a technique for using the same. Improvement in sensitivity including improvement in color sensitization efficiency by a sensitizing dye, sensitivity / graininess It is known to have advantages such as improvement of the relationship of properties, improvement of sharpness due to peculiar optical properties of tabular grains, and improvement of covering power.

(Problems to be Solved by the Invention) However, the problem that the sensitizing dye contained in the silver halide light-sensitive material does not elute during processing and remains colored in the light-sensitive material (so-called residual color) becomes large. .

Therefore, an object of the present invention is to provide a silver halide light-sensitive material which solves the problem of residual color due to a sensitizing dye.

(Means for Solving the Problems) An object of the present invention is to have at least one silver halide emulsion layer on a support, and the emulsion layer or other hydrophilic colloid layer may have the following general formula (I): It was achieved by a silver halide light-sensitive material characterized by containing at least one compound represented by

General formula (I) AD In the formula, A is a blocking group capable of releasing D upon treatment and represents a group represented by the following general formula.

R ₈ represents a hydrogen atom or a substitutable group, and Y ₁ is R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each represent a hydrogen atom or a substitutable group, and Z ₁ represents a group of atoms necessary for forming a carbocycle or a heterocycle. D represents a dye elution accelerator group represented by the following general formula (III).

General formula (III) In the formula, R ₁ is a divalent to tetravalent aliphatic group having 1 to 8 carbon atoms, And Z and W are -N = or The stands, R ₄ represents a hydrogen atom, a halogen atom, an amino group, a hydroxyl group, group, an alkenyl group, an aryl group, an aralkyl group, L ₁ represents a divalent to tetravalent aliphatic group having 1 to 8 carbon atoms, L ₂ represents a divalent to tetravalent aliphatic group having 1 to 8 carbon atoms,
X ₂ is -S-, -O-, R ₅ and R ₆ represent a hydrogen atom or a lower alkyl group, l ₂ represents 0 or 1, R ₂ and R ₃ represent a hydrogen atom,
It represents an alkyl group or an acyl group, and R ₂ and R ₃ may be linked to each other to form a nitrogen-containing heterocycle. l ₁ represents ₁ , 2 or 3.

 Hereinafter, the general formula (I) will be described in detail.

There are several known blocking groups. For example, JP-B-48-9968 and JP-A-52-8,828.
No. 57-82,834, U.S. Pat.No. 3,311,476, Japanese Patent Publication No. 47-4
Those utilizing a blocking group such as an acyl group or a sulfonyl group described in 4,805 (US Pat. No. 3,615,617); JP-B-55-17,369 (US Pat. No. 3,888,677), 55-9,696
No. (US Patent 3,791,830), No. 55-34,927 (US Patent
4,009,029), JP-A-56-77,842 (US Pat. No. 4,307,17)
No. 5), Nos. 59-105,642, and 59-105,640, which utilize the so-called reverse Michael reaction;
9,727, U.S. Pat.Nos. 3,674,478, 3,932,480, 3,993,661, JP-A-57-135,944, 57-135,945.
Block groups that utilize the formation of quinone methide or quinone methide compounds by intramolecular electron transfer described in JP-A Nos. 57-136,640; use of the intramolecular ring closure reaction described in JP-A-55-53,330 and 59-218,439 JP-A-57-76,541 (US Pat. No. 4,335,200), JP-A-57-135,949, JP-A-57-179,
842, 59-137,945, 59-140,445, 59-219,74
Those utilizing the 5- or 6-membered ring opening described in JP-A No. 1 and 60-41,034: or JP-A-59-201,057 and 61-43,73
9. Blocking groups utilizing the addition of a nucleophile to an unsaturated bond described in Nos. 61-95,347. The block group of the present invention is represented by A as described above.

The dye elution accelerator has a heteroatom and, by itself, has a dye elution promoting effect, but when contained in the silver halide light-sensitive material, harmful fog is generated or the sensitivity is lowered, Change the photographic characteristics (sensitivity, gradation, fog, etc.) of the light-sensitive material during storage. However, in the present invention, the above-mentioned inconvenience does not occur because it can be detached from A by directly binding to A through a hetero atom of D and performing photographic processing (development, fixing, etc.).

In the dye elution promoter represented by D, the aliphatic group having 1 to 8 carbon atoms and represented by R ₁ and L ₁ and L ₂ is saturated, unsaturated, straight chain, branched chain or cyclic. It may be either.

The following examples are given as typical examples.

_{-CH 2 -, - CH 2 CH} 2 -, CH 2 3 CH 2 4, -CH = CH-, The substituted or unsubstituted alkyl group represented by R ₂ and R ₃ preferably has an alkyl group moiety having 1 to 5 carbon atoms (eg, methyl, ethyl, propyl), and the substituent is a halogen atom (chlorine atom). , Bromine atom, etc.), hydroxyl group, alkoxy group (eg methoxy, ethoxy), sulfonyl group (eg methanesulfonyl, ethanesulfonyl), carbomoyl group, sulfamoyl group, carboxyl group, sulfo group, amino group (eg acetylamino) or sulfonamide Groups such as methanesulfonylamino are included. Examples of the ring formed by connecting R ₂ and R ₃ include a pyrrole ring, an imidazole ring, a pyrazole ring, a piperidine ring, a pyrrolidine ring, a piperazine ring and a morpholine ring.

The acyl group represented by R ₂ and R ₃ preferably has 3 or less carbon atoms, and specific examples thereof include a methoxycarbonyl group, an acetyl group and a benzoyl group.

R ₈ represents a hydrogen atom or a substitutable group, and as the substitutable group, a halogen atom (fluorine, chlorine, bromine), an alkyl group (preferably having 1 to 20 carbon atoms), an aryl group (preferably carbon) C6 to C20), alkoxy group (preferably C1 to C20), aryloxy group (preferably C6 to C20), alkylthio group (preferably C1 to C20) , An arylthio group (preferably having 6 to 20 carbon atoms), an acyloxy group (preferably having 2 to 20 carbon atoms), an amino group (unsubstituted amino, preferably alkyl having 1 to 20 carbon atoms, or 6 carbon atoms) To secondary or tertiary amino substituted with aryl of 20 to 20), carbonamide group (preferably alkylcarbonamide having 1 to 20 carbon atoms, arylcarbonamide having 6 to 20 carbon atoms), ureido group (preferably Alkyl ureido having 1 to 20 carbon atoms, aryl ureido having 6 to 20 carbon atoms),
Carboxy group, carbonic acid ester group (preferably having a carbon number of 1 to
20 alkyl carbonate ester, C 6-20 aryl carbonate ester), oxycarbonyl group (preferably C 1-20 alkyloxycarbonyl, C 6-20 aryloxycarbonyl), carbamoyl group (preferably carbon) Alkylcarbamoyl having 1 to 20 carbon atoms, 6 to 20 carbon atoms
Arylcarbamoyl), an acyl group (preferably an alkylcarbonyl group having 1 to 20 carbon atoms, an arylcarbonyl having 6 to 20 carbon atoms), a sulfo group, a sulfonyl group (preferably an alkylsulfonyl group having 1 to 20 carbon atoms, an carbon number 6). To arylsulfonyl), a sulfinyl group (preferably an alkylsulfinyl having 1 to 20 carbons, an arylsulfinyl having 6 to 20 carbons), a sulfamoyl group (preferably an alkylsulfamoyl having 1 to 20 carbons). , Carbon number 6-20
Arylsulfamoyl), a cyano group, and a nitro group.

These substituents represented by R ₈ may have one or more substituents, and when there are two or more substituents, they may be the same or different, and specific substituents include the substituents of R ₈ described above. The same as the group can be mentioned.

R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ may be the same or different and each represents a hydrogen atom or a substitutable group, and a specific substituent is an alkyl group (preferably having a carbon number of 1 to 1).
20), alkenyl group (preferably having 2 to 20 carbon atoms), aryl group (preferably having 6 to 20 carbon atoms), alkoxy group (preferably having 1 to 20 carbon atoms), aryloxy group (Preferably having 6 to 20 carbon atoms), acyloxy group (preferably having 2 to 20 carbon atoms), amino group (unsubstituted amino, preferably 1 to 1 carbon atoms)
20-alkyl or secondary or tertiary amino substituted with aryl having 6 to 20 carbons, carbonamide group (preferably alkyl carbonamide having 1 to 20 carbons, carbon number 6)
To 20 arylcarbonamides, ureido groups (preferably alkyl ureido groups having 1 to 20 carbon atoms, 6 to 20 carbon atoms)
Aryl ureido), an oxycarbonyl group (preferably an alkyloxycarbonyl having 1 to 20 carbon atoms, a carbon number 6)
~ 20 aryloxycarbonyl), carbamoyl group (preferably alkylcarbamoyl having 1 to 20 carbon atoms, arylcarbamoyl having 6 to 20 carbon atoms), acyl group (preferably alkylcarbonyl having 1 to 20 carbon atoms, 6 to 6 carbon atoms)
20 arylcarbonyl), sulfonyl group (preferably alkylsulfonyl having 1 to 20 carbon atoms, arylsulfonyl having 6 to 20 carbon atoms), sulfinyl group (preferably alkylsulfinyl having 1 to 20 carbon atoms, 6 to carbon atoms) 20 arylsulfinyl) and a sulfamoyl group (preferably alkylsulfamoyl having 1 to 20 carbons, arylsulfamoyl having 6 to 20 carbons). Of these, R ₁₃ and R ₁₄
Examples of preferred substituents include a oxycarbonyl group, a carbamoyl group, an acyl group, a sulfonyl group, a sulfamoyl group, a sulfinyl group, a cyano group, and a nitro group. These substituents may have one or more substituents, and when there are two or more substituents, they may be the same or different, and specific substituents are the same as those described above for R _8. Can be mentioned.

Z ₁ represents a group of atoms necessary for forming a carbocycle or a heterocycle.

Specifically, for example, a 5-, 6-, or 7-membered carbocyclic ring, or a 5-, 6-, or 7-membered heterocyclic ring containing at least one nitrogen, oxygen, sulfur atom, or the like These carbocycles or heterocycles include those forming a condensed ring at an appropriate position.

Specifically, cyclopentenone, cyclohexenone,
Cycloheptenone, benzocycloheptenone, benzocyclopentenone, benzocyclohexenone, 4-pyridone, 4-quinolone, 2-pyrone, 4-pyrone, 1-thio-2-pyrone, 1-thio-4-pyrone, coumarin, Cromon, Uracil, etc. And so on.

(R ₁₃ and R ₁₄ have the same meanings as those in formula (I)) R ₁₅ , R ₁₆ and R ₁₇ represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an acyl group or the like.

Here, these carbocycles or heterocycles may have one or more substituents, and when there are two or more substituents, they may be the same or different. Specific examples of the substituent include the same as the above-mentioned substituents of R ₈ .

The selection of R ₈ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ in the general formula (I) depends on the pH, composition and the processing solution pH in which the photographic element having the general formula (I) is processed. Selected according to the timing time.

Further, the compound of the present invention can be used for photographic processing (for example, development,
In addition to the pH of (fixing, etc.), especially sulfite ion hydroxylamine, thiosulfate ion, metabisulfite ion, JP-A-59
-198453 and hydroxamic acid and its green compounds, the oxime compounds described in JP-A-60-35729 and the dihydroxybenzene-based developing agent described below, 1-phenyl-
3-pyrazolidone developing agent. By using a nucleophilic substance such as a p-aminophenol-based developing agent, the release rate of the dye elution accelerator can be widely controlled.

The addition amount is usually 1 to 10 ⁸ with respect to the compound of the present invention.
The molar amount is about twice, preferably about 10 ² to 10 ⁶ times.

Next, specific examples of the compound of the present invention are shown, but the invention is not limited thereto.

As the compound represented by the general formula (I), those described in the following publications may be used in addition to the above-mentioned ones.

JP-A-59-201057, JP-A-61-43739, JP-A-61-95
Issue 347.

The compound represented by the general formula (I) can be synthesized according to the method described in the above-mentioned patent, or can be easily synthesized according to the following synthetic method or according to it.

Synthesis of Exemplified Compound (1) 6-Chloro-1,3-dimethyluracil was added to Liebigs Ann.C.
It was synthesized by the following method described in hem.Bd.612,161 (1958).

276 g (3.14 mol) of 1,3-dimethylurea and 376 malonic acid
g (3.62 mol) is dissolved in 600 ml glacial acetic acid at 60-70 ° C.

Then, 1250 ml of acetic anhydride is added, and the temperature is gradually raised to 90 ° C. After stirring for 6 hours, the mixture is left at room temperature overnight, and glacial acetic acid and acetic anhydride are distilled off under reduced pressure. The residue was poured into 500 ml of ethanol while hot, the precipitated crystals were separated, heated under reflux with concentrated hydrochloric acid (380 ml) and water (400 ml) for 2 hours, and then allowed to stand under ice cooling for 6 hours. Separate the precipitated crystals and wash with a small amount of ethanol to obtain 360 g of 1,3-dimethylbarbituric acid.
Was synthesized.

To 110 g of this 1,3-dimethylbarbituric acid, 32 ml of water is added, and further 800 ml of phosphorus oxychloride is gradually added dropwise. After heating and refluxing for 1.5 hours, phosphorus oxychloride is distilled off under normal pressure, and the residue is poured into ice while hot. The precipitated crystals are separated, the liquid is extracted with chloroform (× 3), and dried over anhydrous sodium sulfate. Then chloroform is distilled off,
The resulting residue was combined with the above crystals and recrystallized from water to synthesize 6-chloro-1,3-dimethyluracil 80g.

16 g of N-chlorosuccinimide was added to 70 ml of an acetonitrile solution containing 21 g of 6-chloro-1,3-dimethyluracil under ice cooling (internal temperature: 5 ° C.). The internal temperature gradually rises to 35 ° C
After reaching, the mixture was further stirred for 1 hour. 70 ml of water was added to the reaction solution, the precipitated crystals were collected by filtration, and cold acetonitrile 18 ml,
Wash with a mixed solution of 18 ml of water, dry and mix with 5,6-dichloro-1,3
18 g of dimethyluracil were obtained. Then, to a solution of 2-dimethylaminoethanethiol hydrochloride 8 g and methanol 15 ml was added dropwise sodium methoxide (28% methanol solution) 24 g under nitrogen, and the mixture was stirred at room temperature for 10 minutes and then filtered. The filtrate was concentrated under reduced pressure to dryness, and acetonitrile was added.
Dissolve in 15 ml, and from the dropping funnel, 5,6-dichloro-1,3-
11.8 g of dimethyluracil was added dropwise at room temperature into a system in which 20 ml of acetonitrile was dissolved.

The reaction mixture was stirred for 2 hours and then filtered. The filtrate was concentrated under reduced pressure. After adding 20 ml of ethanol and 12 ml of 20% hydrochloric acid ethanol solution to the residue, ethanol was removed under reduced pressure, ethyl acetate was added to the residue, and the precipitated crystals were collected by filtration,
13.2 g of the hydrochloride salt of the exemplified compound (1) was synthesized. Melting point 163-
166 ° C. Synthesis of Exemplified Compound (7) In a 300 ml reaction vessel equipped with a distillation tool, 50 g of 2-ethylhexylamine, 29 g of methyl carbamate, and 10 parts of toluene.
0 ml was added, 0.1 g of a catalyst amount of dibutyltin oxide was added, and the mixture was heated and stirred. Excluding methanol generated during the reaction,
When the reflux temperature reached 110 ° C. (boiling point of toluene), the distillation tool was removed, a reflux tool was attached instead, the mixture was stirred for 30 minutes, and then allowed to cool. Toluene was removed under reduced pressure, the residue was washed with n-hexane, collected by filtration, and N- (2-ethylhexyl) urea was collected.
I got 61g.

A solution of 50 g of the obtained N- (2-ethylhexyl) urea, 36 g of malonic acid and 100 ml of acetic acid was heated to 80 ° C and stirred for 4 hours. After cooling, acetic acid was removed under reduced pressure, and 100 ml of water and 500 ml of chloroform were added for extraction.

The organic layer was washed with a saturated sodium hydrogen carbonate solution and then with a saturated saline solution, dried over anhydrous magnesium sulfate, chloroform was removed under reduced pressure, and the residue was washed with n-hexane to collect N- (2-ethylhexyl) barbitur. Acid 64g
I got

Obtained N- (2-ethylhexyl) barbituric acid 40
120 ml of phosphorus oxychloride is added to g and 3 ml of water is gradually added dropwise. After heating under reflux for 2 hours, phosphorus oxychloride is distilled off under normal pressure, and the residue is poured into ice while hot. Further, it is extracted three times with 200 ml of chloroform, and the organic layers are collected and dried over anhydrous magnesium sulfate. Then, chloroform was removed under reduced pressure, n-hexane was added to the obtained residue, and the precipitated crystals were collected by filtration. Recrystallized with ethyl acetate and 6-chloro-
32 g of 3- (2-ethylhexyl) uracil was obtained as yellow crystals.

To a solution of 20 g of 6-chloro-3- (2-ethylhexyl) uracil thus obtained in 50 ml of dimethylformamide, 11 g of potassium carbonate was added, 12.1 g of iodomethyl was further added, and the mixture was stirred at room temperature for 1 hour. The reaction solution was filtered, the filtrate was poured into water, and extracted twice with 100 ml of chloroform. The organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate, chloroform was removed under reduced pressure, and 6-chloro- was obtained as an oil.
21 g of 3- (2-ethylhexyl) -1-methyl-uracil
I got

Obtained 6-chloro-3- (2-ethylhexyl) -1
-Methyl-uracil 20g in acetonitrile solution 50ml N
-8.6 g of chlorosuccinimide was added, heated to 40 ° C, and stirred for 2 hours. After cooling, remove acetonitrile under reduced pressure,
Water was added to the residue and extracted with 100 ml of chloroform. The organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate, chloroform was removed under reduced pressure, and the residue was purified by silica gel chromatography to give 5,6-dichloro-3- (2-ethylhexyl)-as an oil. 22 g of 1-methyluracil
I got

Then, to a solution of 1- (2-dimethylaminoethyl) -5-mercaptotetrazole hydrochloride 10 g and methal 20 ml,
Sodium methoxide (28% methanol solution) under nitrogen
20 g was added dropwise, the mixture was stirred at room temperature for 10 minutes, and then filtered. The filtrate was concentrated to dryness under reduced pressure and dissolved in 20 ml of acetonitrile. From the dropping funnel, 14.6 g of 5,6-dichloro-3- (2-ethylhexyl) -1-methyluracil was dissolved in 20 ml of acetonitrile. It was added dropwise to the system at room temperature. The reaction mixture was stirred for 1 hour 30 minutes and then filtered. The filtrate was concentrated under reduced pressure. After 20 ml of ethanol and 20% hydrochloric acid-ethanol solution were added to the residue, ethanol was removed under reduced pressure, ethyl acetate was added to the residue, and the precipitated crystals were collected by filtration to synthesize 17.6 g of hydrochloride salt of Exemplified compound (7). . Melting point 124-126 ° C Synthesis of Exemplified Compound (10) 2-benzoyl-3-chlorocyclohexenone-2
It was synthesized by the following method described in Chem.Pharm.Bull 29 (5), 1312-1320 (1981).

Cyclohexane-1,3-dione 14.6 g, chloroform 30
10 g of pyridine was added to the 0 ml solution, and further 18 g of benzoyl chloride was added dropwise. After stirring at room temperature for 4 hours, the reaction mixture was poured into ice water. The organic layer was washed with dilute hydrochloric acid, then saturated sodium hydrogen carbonate solution, and then with brine, dried over anhydrous magnesium sulfate, and then concentrated to dryness under reduced pressure to give 3-
Benzoyloxycyclohexenone-2 was obtained as a crude product. The obtained 3-benzoyloxycyclohexenone-2 was purified with anhydrous aluminum chloride without purification.
g, added to a solution of 320 ml of dichloroethane. After stirring at room temperature for 17 hours, the reaction mixture was poured into cold hydrochloric acid water (10%), the organic layer was separated, and the aqueous layer was extracted twice with dichloroethane.

The organic layers were collected, washed with brine, dried over anhydrous magnesium sulfate, and dichloroethane was removed under reduced pressure. The minimum amount of diethyl ether, which can be dissolved in the residue, 1N sodium hydroxide solution was added. The aqueous layer was acidified with concentrated hydrochloric acid, extracted with diethyl ether, the organic layer was dried over anhydrous magnesium sulfate, and the diethyl ether was removed under reduced pressure. When n-hexane was added to the residue and recrystallized, 13 g of 2-benzoylcyclohexane-1,3dione was obtained.

Oxalyl chloride (4 ml) was added to the obtained 2-benzoylcyclohexane-1,3-dione (5 g) under ice-cooling and the mixture was stirred for 3 hours. Then, excess oxalyl chloride was removed under reduced pressure. The reaction mixture was distilled under reduced pressure to obtain 4.2 g of 2-benzoyl-3-chlorocyclohexenone-2. bp.185 ~ 19
6 ° C, 10.1 mmHg Next, under a nitrogen stream, 5-mercapto-1- {2- (1-
To a solution of 5 g of imidazoyl) ethyl] tetrazole and 15 ml of acetonitrile, 10 ml of an acetonitrile solution of 46 g of 1,8-diazabicyclo {5,4,0} undecene-7 (DBU) was added dropwise, and the mixture was stirred at room temperature for 5 minutes, and then 2- 10 ml of an acetonitrile solution containing 2,6 g of benzoyl-3-chlorocyclohexenone was added, and the mixture was stirred at room temperature for 2 hours. Then, under reduced pressure, acetonitrile was removed, 3 ml of hydrochloric acid and 30 ml of water were added, and chloroform 1
It was extracted with 00 ml. The organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate, chloroform was removed under reduced pressure, ethyl acetate was added to the residue, and the precipitated crystals were collected by filtration to give 7.3 g of Exemplified compound (10).

Melting point 168 to 171 ° C. Synthesis of Exemplified Compound (14) 3,4,6-Trichloro-coumarin was added to J. Am. Chem. Soc, 81, 22.
It was synthesized by the following method described in 66 (1959).

Carbon disulfide (120 ml) was added to aluminum chloride (39 g) to give a slurry, 4-chlorophenol (19 g),
It was gradually added to a solution of carbon disulfide (50 ml) and stirred at room temperature until hydrogen chloride gas was not generated. Next, 56.2 g of hexachloropropane was added dropwise over 20 minutes, and the mixture was stirred at room temperature until hydrogen chloride was not generated, then carbon disulfide was distilled off under normal pressure, and cold sulfuric acid water (concentrated sulfuric acid 20 ml, water was added to the residue). 100 ml) was added and the mixture was stirred for 10 minutes, and then the precipitated crystals were collected by filtration and recrystallized from diethyl ether to obtain 18.2 g of 3,4,6-trichloro-coumarin. Melting point 133-135 ° C. Next, sodium methoxide (28% methanol solution) 3. was added to a solution of 5-mercapto-1- (2-dimethylaminoethyl) tetrazole 3 g in methanol 10 ml under a nitrogen stream.
After adding 6 g and stirring at room temperature for 5 minutes, the mixture was concentrated under reduced pressure. 10 ml of acetonitrile was added to the residue, and 3,4,6-trichloro-
10 ml of a solution of 4.3 g of coumarin in acetonitrile was added dropwise. After stirring at room temperature for 2 hours, the mixture was filtered, and the filtrate was concentrated to dryness under reduced pressure. After adding 5 ml of ethanol to the residue and further adding 4 ml of hydrochloric acid ethanol solution (20%), ethanol was removed under reduced pressure. Ethyl acetate was added to the residue, and the precipitated crystals were collected by filtration to obtain 5.1 g of hydrochloride salt of Exemplified compound (14). Melting point 171 to 173 ° C. The compound of the general formula (I) of the present invention may be added to any layer such as a photosensitive emulsion layer and a non-photosensitive layer. It is preferably contained in the non-photosensitive layer.

The addition amount of the compound of the present invention is 0.001 mol% of the total coated silver amount.
To 100 mol%, preferably 0.001 to 50 mol%, and particularly preferably 0.01 to 20 mol%.

The compounds of the present invention are alcoholic water such as methanol, TH
It can be dissolved and dispersed in F, acetone, gelatin, a surfactant, etc. and added to the coating solution. Further, like the coupler, it can be dissolved in a high boiling organic solvent and emulsified and dispersed by a homogenizer.

The method of the present invention exhibits a remarkable effect when a black and white silver halide light-sensitive material spectrally sensitized with a sensitizing dye is rapidly processed, preferably for 90 seconds or less, particularly for 70 seconds or less.

The development processing method of the present invention basically comprises steps of black-and-white development, fixing, washing with water, drying or developing, fixing, stabilizing and drying an exposed silver halide light-sensitive material.

The combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones is most preferable in that a good performance is easily obtained for the developing agent used in the developing solution used in the developing treatment of the present invention. Of course, a p-aminophenol-based developing agent may be contained in addition to the above.

Examples of the dihydroxybenzene developing agent used in the present invention include hydroquinone, chlorohydroquinone, bromhydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone,
There are 2,5-dimethylhydroquinone and the like, but hydroquinone is particularly preferable.

Examples of the p-aminophenol type developing agent used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol and N- (4-hydroxyphenyl). Glycine, 2
There are -methyl-p-aminophenol, p-benzylaminophenol and the like, among which N-methyl-p-aminophenol is preferable.

The 3-pyrazolidone-based developing agents used in the present invention include 1-phenyl-3-pyrazolidone and 1-phenyl-4,4.
-Dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-
Phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-
p-aminophenyl-4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-4,4-dimethyl-3-pyrazolidone, 1
-p-tolyl-4-methyl-4-hydroxymethyl-3-
Pyrazolidone, etc.

The developing agent is usually preferably used in an amount of 0.01 mol / l to 1.2 mol / l.

As a preservative of sulfite used in the developing treatment of the present invention, sodium sulfite, potassium sulfite, lithium sulfite,
Ammonium sulfite, sodium bisulfite, potassium metabisulfite, and the like. The sulfite is preferably 0.2 mol / l or more, and particularly preferably 0.4 mol / l or more. The upper limit is preferably up to 2.5 mol / l.

The pH of the developer used in the development processing of the present invention is preferably in the range of 9 to 13. More preferably, the pH is in the range of 10 to 12.

Alkaline agents used to set the pH include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium triphosphate, potassium triphosphate, etc.
Contains pH regulator.

A buffer agent such as Japanese Patent Application No. 61-28708 (borate), JP-A No. 60-93433 (for example, saccharose, acetoxime, 5-sulfosalicylic acid), phosphate and carbonate may be used.

A hardener may be used in the developer. As the hardener, a dialdehyde hardener or a bisulfite adduct thereof is preferably used, and specific examples thereof include glutaraldehyde, or a bisulfite adduct thereof.

As additives used in addition to the above components, development inhibitors such as sodium bromide, potassium bromide, potassium iodide: ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol, methanol Organic solvents such as: 1-phenyl-5-mercaptotetrazole, mercapto-based compounds such as 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, indazole-based compounds such as 5-nitroindazole, and benz such as 5-methylbenztriazole. Anti-foggants such as triazole compounds may be included in Research Disclos
ure Volume 176, No.17643, Item XXI (December issue, 1978), development accelerators, and if necessary, toning agents, surfactants, defoaming agents, water softeners, JP-A The amino compounds described in Japanese Patent Publication No. 56-106244 may be included.

In the development processing of the present invention, a silver stain inhibitor in the developer,
For example, the compounds described in JP-A-56-24347 can be used.

The developer of the present invention includes European Patent No. 0136582,
Amino compounds such as alkanolamines described in JP-A-56-106244 can be used.

In addition to this, LFA Mason's "Photographic Processing Chemistry", published by Focal Press (19
Pp. 226-229, U.S. Pat.Nos. 2,193,015 and 2,59
Those described in 2,364, JP-A-48-64933 and the like may be used.

The fixer is an aqueous solution containing thiosulfate as a fixer and has a pH of 3.8 or higher, preferably 4.2 to 7.0. The pH is more preferably 4.5 to 5.5.

Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, and ammonium thiosulfate is particularly preferable from the viewpoint of fixing speed. The amount of the fixing agent used can be appropriately changed and is generally about 0.1 to about 6 mol / l.

The fixing solution may contain a water-soluble aluminum salt which acts as a hardening agent, and they include, for example, aluminum chloride, aluminum sulfate and potassium alum.

Tartaric acid, citric acid, gluconic acid or their derivatives may be used alone or in combination of two or more in the fixing solution. These compounds are 0.00 per fixing solution
Those containing 5 mol or more are effective, and particularly 0.01 mol / l to 0.03 mol / l are particularly effective.

Preservatives (eg, sulfites, bisulfites), pH buffers (eg, acetic acid, boric acid), pH adjusters (eg, sulfuric acid), chelating agents having a softening effect on water, and Japanese Patent Application The compounds described in JP-A-60-218562 may be included.

In the development processing of the present invention, it is more preferable to reduce the swelling percentage of the light-sensitive material (preferably 150% to 50%) and to weaken the processing hardened film, since rapid processing can be performed. That is, it is more preferable that there is no hardening during development, and it is more preferable that there is no hardening during fixing. However, the hardening reaction may be weakened by setting the pH of the fixing solution to 4.6 or more. By doing so, a replenisher consisting of one liquid for each of the developing solution and the fixing solution can be constituted, and there is an advantage that the replenishing solution can be prepared by simply diluting with water.

In the development processing method of the silver halide photographic light-sensitive material of the present invention, the development and fixing steps are followed by washing with washing water or a stabilizing solution. Here, the stabilizing solution is the same as the water washing, and is different only in the name.

The replenishing amount of washing water or stabilizing solution is 2 liters per 1 m ² of light-sensitive material.
The following (including 0; that is, washing with water) is preferable.

By doing so, not only the water saving process can be performed, but also the piping for installing the automatic processing machine can be eliminated.

As a method for reducing the replenishment amount, a multi-stage countercurrent system (for example, two-stage, three-stage) has been known for a long time. If this multi-stage countercurrent method is applied to the present invention, the light-sensitive material after fixing is gradually processed in a cleaner direction, that is, the processing solution which is not contaminated with the fixing solution is sequentially processed, so that the efficiency is further improved. Washed with water.

In order to make the above-mentioned development processing of the present invention water-saving processing or pipe-less processing, it is preferable to provide washing water or a stabilizing solution with an antifungal means.

As the antifungal means, an ultraviolet irradiation method described in JP-A-60-263939, a method using a magnetic field described in 60-263940, and an ion exchange resin described in 61-131632 are used. How to make pure water, Japanese Patent Application No. 60-253807, No. 60-295894,
The methods using the antibacterial agents described in JP-A-61-63030 and JP-A-61-51396 can be used.

Furthermore, LEWest, “Water Quality Criteria” Photo.
Sci, & Eng. Vol.9 No.6 (1965), MWBeach, “Microbi
ological Growths in Motion-Picture Processing "SMPT
E Journal Vol.85, (1976), RODeegan, “Photo Proc
essing Wash Water Biocides "J. Imaging Tech 10, No.6
(1984) and JP-A-57-8542, 57-58143, and 58-10.
5145, 57-132146, 58-18631, 57-97530
Nos. 57-157244 and the like can be used in combination with antibacterial agents, antifungal agents, surfactants and the like.

Further, the washing bath or stabilizing bath of the present invention includes RTKreima.
n, J. Image. Tech 10, (6) p. 242 (1984), isothiazoline compounds, Research Disclosure No. 205.
Volume, No. 20526 (May 1981, May), isothiazoline compounds, Volume 228, No. 22845 (April, 1983), isothiazoline compounds, Japanese Patent Application No. 61- Five
The compounds described in No. 1396 are used as antibacterial agents (Microbiocid
It can also be used together as e).

Others, "The Chemistry of Antibacterial and Antifungal", Hiroshi Horiguchi, Sankyo Publishing (Akira
57), "Handbook of antibacterial and antifungal techniques", compounds such as those described in Japanese Society of Antibacterial and Antifungal, Hakuhodo (Showa 61) may be included.

In the method of the present invention, when washing with a small amount of washing water or stabilizing with a stabilizing solution, it is more preferable to provide the squeeze roller washing tank described in Japanese Patent Application No. 61-163217. Further, it is also preferable to adopt a structure of a water washing step as in Japanese Patent Application No. 61-290619.

Further, in the method of the present invention, a part or all of the overflow liquid from the washing or stabilizing bath produced by supplementing the washing or stabilizing bath with antifungal means depending on the treatment is disclosed. As described in JP-A-60-235133, it can also be used for a processing solution having a fixing ability which is a processing step before that.

When the silver halide light-sensitive material of the present invention is processed by an automatic processor including at least the steps of developing, fixing, washing with water or stabilizing and drying, the steps from development to drying are 90
Time within a second, that is, the time from when the tip of the photosensitive material starts to be immersed in the developing solution to when the tip is dried through a fixing and washing (or stabilization) process until the tip comes out of the drying zone. (Dry to Dry time) is preferably within 90 seconds, particularly preferably within 70 seconds. More preferably, the Dry to Dry time is within 60 seconds.

In the present invention, the "development process time" or "development time" means the time from when the leading edge of the photosensitive material to be processed as described above is immersed in the developing tank solution of the developing machine until it is immersed in the next fixing solution, The "fixing time" is the time from the immersion in the fixing tank liquid to the next immersion in the washing tank liquid (stabilizing liquid). The "washing time" is the time of immersion in the washing tank liquid.

The "drying time" is usually 35 ° C to 100 ° C, preferably 4 ° C.
A drying zone to which hot air of 0 ° C to 80 ° C is blown is installed in the automatic developing machine, and it means the time to enter the drying zone.

In order to achieve the above rapid processing within 90 seconds, the developing time is within 30 seconds, preferably within 25 seconds, and the developing temperature is preferably 25 ° C to 50 ° C, more preferably 30 ° C to 40 ° C. preferable.

According to the present invention, the fixing temperature and time are preferably about 20 ° C to about 50 ° C for 6 seconds to 30 seconds, more preferably 30 ° C to 40 ° C for 6 seconds to 20 seconds.

Rinse or stabilize bath temperature and time from 0 to 50 ° C for 6 seconds
It is preferably 20 seconds, more preferably 6 to 15 seconds at 15 ° C to 40 ° C.

According to the method of the present invention, the developed, fixed and rinsed or stabilized photographic material is squeezed out of the rinse water, i.e. dried through a squeeze roller. Drying is about 40 ° C to about 100
C., and the drying time may be appropriately changed depending on the surrounding conditions, but it is usually about 5 seconds to 30 seconds, and particularly preferably 40 ° C. to 80 ° C. for about 5 seconds to 20 seconds.

In the dry-to-dry development processing of 90 seconds or less with the light-sensitive material / processing system of the present invention, as described in Japanese Patent Application No. 61-297672, in order to prevent development unevenness peculiar to rapid processing. Applying a roller made of rubber material to the roller at the outlet of the developing tank, and as described in Japanese Patent Application No. 61-297673, the discharge flow rate for stirring the developing solution in the developing solution tank is 10 m / min or more. In addition to that, Japanese Patent Application Sho 61
As described in JP-A-315537, it is more preferable to stir more strongly than during standby at least during the development processing. Further, for the rapid processing as in the present invention, it is more preferable that the roller of the fixing solution tank has a high fixing speed or a facing roller. By using the opposed rollers, it is possible to reduce the number of rollers and the processing tank. That is, the automatic processing machine can be made more compact.

The photosensitive material development processing method of the present invention is not particularly limited as a photographic photosensitive material, and general black and white photosensitive materials are mainly used. Especially for medical images such as photographic materials for laser printers, scanner sensitive materials for printing, and direct medical photography X
-Ray sensitive material, medical indirect photography X-ray sensitive material, CRT image recording sensitive material, printing contrast sensitive material, etc.

The production of the light-sensitive material suitable for the rapid development processing according to the present invention can be realized by, for example, one of the following methods or a combination of two or more methods.

A silver halide having a low or no iodine content is used. That is, silver chloride having a silver iodide content of 0 to 5 mol%,
Silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide and the like are used.

The silver halide emulsion contains a water-soluble iridium salt.

Reduce the amount of coated silver in the silver halide emulsion layer.
For example 1 to 5 g / m ² on one side, preferably 1 to 4 g / m ^2.
More preferably from 1 to 3 g / m ^2.

Reduce the average grain size of the silver halide in the emulsion. For example, 1.0 μ or less, preferably 0.7 μ or less.

As the silver halide grains in the emulsion, tabular grains having an aspect ratio of 4 or more, preferably 5 or more are used.

The swelling percentage of the silver halide light-sensitive material is set to 200% or less.

Silver halide grains in photographic emulsions are cubic, octahedral,
It may be a so-called Regular particle having a regular crystal such as a tetradecahedron, an irregular crystal shape such as a sphere, a crystal defect such as a twin plane, a tabular grain or A composite form of them may be used.

The tabular grain aspect ratio is given by the ratio of the average value of the diameter of a circle having an area equal to the projected area of each tabular grain and the average value of the grain thickness of each tabular grain.
In the present invention, the tabular grains preferably have an aspect ratio of 4 or more and less than 30 and more preferably 5 or more and less than 20. Furthermore, the particle thickness is preferably 0.3 μm or less, and particularly preferably 0.2 μm or less.

The tabular grains are preferably present in an amount of 30% by weight, more preferably 50% by weight or more based on the total grains.

The grain size of silver halide may be a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution.

The silver halide photographic emulsion that can be used in the present invention can be produced by a known method, for example, Research Disclosure, No. 1764.
3 (Dec. 1978), pp. 22-23, "I. Emulsion production (Emulsion
preparation and types) ”and ibid., No. 18716 (1979)
November, 2004), page 648.

The photographic emulsion used in the present invention is described in "Graphic Chemistry and Physics" by Graphide, published by Paul Montel (P.Glafkides, Ch.
imie et Physique Photographique Paul Montel, 196
7), “Photoemulsion Chemistry” by Duffin, published by Forcal Press (GFDuffin.Photographic Emulsion Chemistry
(Focal Press, 1996), "Production and Coating of Photographic Emulsions" by Zelikmann et al., Published by Forcal Press (VLZelikman et.
al, Making and Coating Photographic Emulsion, Focal
Press, 1964) and the like.

When the silver halide grains used in the present invention are formed, as a silver halide solvent for controlling the growth of the grains, for example, ammonia, rodancali, rodanammon,
Thioether compounds (eg US Pat. No. 3,271,157,
No. 3,574,628, No. 3,704,130, No. 4,297,439
No. 4,276,374), thione compounds (for example, JP-A-54-144,319, JP-A-53-82,408, JP-A-55-77,737, etc.), amine compounds (for example, JP-A-54-100,717, etc.) Etc. can be used.

In the present invention, a water-soluble rhodium salt or a water-soluble iridium salt as described above can be used. As the method for reacting the soluble silver salt and the soluble halogen salt in the present invention, any of a one-sided mixing method, a simultaneous mixing method, a combination thereof and the like may be used.

A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. PA in the liquid phase in which silver halide is formed as a form of simultaneous mixing method.
A method of keeping g constant, that is, a so-called controlled double jet method can be used, and this method provides a silver halide emulsion having a regular crystal form and a substantially uniform grain size.

The silver halide emulsion used in the method of the present invention is preferably chemically sensitized.

For chemical sensitization, normal sulfur sensitization, reduction sensitization,
Noble metal sensitization and combinations thereof are used.

More specific chemical sensitizers include sulfur sensitizers such as allyl thiocarbamide, thiourea, thiosulfate, thioether and cystine;
Potassium chloroaurate, aurous, thiosulfate and Potassium chloroparadate
Noble metal sensitizers such as Palladete): reduction sensitizers such as tin chloride, phenylhydrazine and reductone.

The silver halide emulsion used in the present invention is optionally spectrally sensitized with a known spectral sensitizing dye. Examples of the spectral sensitizing dye to be used include, for example, Hamer, “Heterocyclic Compounds-The Cyanine Soybean.
And Related Compounds ", John Wheelie & Sons (1964) (FMHamer," He
terocyclic Compounds-The Cyanine Dyes and Related
Compounds ", John Wiley & Sons (1964). And Starmer," Heterocyclic Compounds-Special Topicals in Heterocyclic Chemistry, "Jyon Wheelie and Sons (1977) (DMSturmer," Heterocyclic Compounds-Specia
l Topics in Heterocyclic Chemistry ", John Wiley &
Sons (1977). , Cyanine, merocyanine, rhodacyanine, styryl, hemicyanine,
Oxonol, benzylidene, holopolar and the like can be used, but cyanine and merocyanine are particularly preferable.

Examples of the sensitizing dye that can be preferably used in the present invention include JP-A Nos. 60-133442, 61-75339, 62-6251, and 59-212.
Examples thereof include cyanine dyes and merocyanine dyes represented by the general formulas described in Nos. 827, 50-122928, 59-1801553 and the like. Specifically, pages (8) to (11) of JP-A-50-133442 and pages (5) to (61) of JP-A-61-75339.
Page (7), pages (24) to (25), pages (10) to (15) of JP-A-62-6251, page (5) of JP-A-59-212827,
Page (7), pages (7) to (9) of JP-A No. 50-122928,
A sensitizing dye for spectrally sensitizing silver halide in the blue region, green region, red region or infrared region of the spectrum described in JP-A-59-180553, pages (7) to (18), etc. Can be mentioned.

These sensitizing dyes may be used alone, or a combination thereof may be used.
Often used for the purpose of supersensitization. Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance that does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion. For example, aminostilbene compounds substituted with a nitrogen-containing heterocyclic nucleus group (for example, those described in U.S. Pat.Nos. 2,933,390 and 3,635,721), aromatic organic acid formaldehyde condensates (for example, U.S. Pat. Listed)), cadmium salt,
An azaindene compound or the like may be included. U.S. Patent No. 3,
615,613, 3,615,641, 3,617,295, 3,635,7
The combination described in No. 21 is particularly useful.

The above-mentioned sensitizing dye is used in an amount of 5 × 10 ^{−7 to} 5 × 10 ⁻¹ mol, preferably 1 × 10 ^{−5 to} 5 × 10 ⁻² mol per mol of silver halide.
It is contained in the silver halide photographic emulsion in a molar ratio of from 2.times.10.sup.- ⁵ mol to 5.times.10.sup.- ³ mol.

The above sensitizing dye can be directly dispersed in the emulsion layer. Further, these may be first dissolved in a suitable solvent such as methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine or a mixed solvent thereof, and added to the emulsion in the form of a solution. Also, ultrasonic waves can be used for dissolution. Further, as a method of adding the sensitizing dye, as described in U.S. Pat.No. 3,469,987, the dye is dissolved in a volatile organic solvent, and the solution is dispersed in a hydrophilic colloid. And a method in which a water-insoluble dye is dispersed in a water-soluble solvent without being dissolved and the dispersion is added to the emulsion, as described in JP-B-46-24185.
As described in JP-B-61-45217, a method of mechanically pulverizing and dispersing a water-insoluble dye in an aqueous solvent and adding this dispersion to an emulsion; as described in US Pat. No. 3,822,135, A method in which a dye is dissolved in a surfactant and the solution is added to an emulsion; a method in which a compound for redshifting is used, as described in JP-A-51-74624, and the solution is added to the emulsion; A method in which a dye as described in JP-A-50-80826 is dissolved in an acid containing substantially no water and the solution is added to the emulsion is used. In addition, U.S. Pat.Nos. 2,912,343, 3,342,605, and
The methods described in 2,996,287 and 3,429,835 can also be used. The above sensitizing dyes may be uniformly dispersed in the silver halide emulsion before coating on a suitable support,
Of course, it can be dispersed in any step of preparing a silver halide emulsion.

The above sensitizing dye can be used in combination with other sensitizing dyes. For example, U.S. Patent No. 3,703,377, No. 2,688,545, No. 3,397,060, No. 3,615,635,
No. 3,628,964, British Patent No. 1,242,588, No. 1,293,
862, Japanese Patent Publication No. 43-4936, 44-14030, 43-10773
No. 3, U.S. Patent No. 3,416,927, Japanese Patent Publication No. 43-4930, U.S. Patent Nos. 2,615,613, 3,615,632, 3,617,295,
The sensitizing dyes described in No. 3,635,721 can be used.

In order to rapidly process the silver halide light-sensitive material, it is preferable that the swelling percentage of the silver halide light-sensitive material is 200% or less.

On the other hand, if the swelling percentage is too low, the speed of development, fixing, washing with water, etc. will decrease, so it is not preferable to lower it more than necessary.

The preferred percentage is 200% or less, 30% or more, and especially 150.
% Or less and 50% or more is preferable.

Those skilled in the art can easily control the swelling percentage to 200% or less by, for example, increasing the amount of the hardener used in the light-sensitive material.

The percentage of swelling was determined by (a) incubating the photographic material at 38 ° C. and 50% relative humidity for 3 days, (b) measuring the thickness of the hydrophilic colloid layer, and (c) distilling the photographic material at 21 ° C. It can be determined by immersing in water for 3 minutes and (d) measuring the percentage change in layer thickness compared to the thickness of the hydrophilic colloid layer measured in step (b).

Examples of the hardener that can be used in the present invention include aldehyde compounds, compounds having an active halogen described in U.S. Pat.No. 3,288,775, and reactive ethylenically unsaturated groups described in U.S. Pat. Are known, organic compounds such as epoxy compounds described in US Pat. No. 3,091,537, halogenocarboxaldehydes such as mucochloric acid, and the like are known. Of these, vinyl sulfone type hardeners are preferable. Further, a polymer hardener can also be preferably used.

As the polymer hardener, a polymer having an active vinyl group or a group serving as a precursor thereof is preferable.
Especially preferred are polymers in which the active vinyl group or its precursor group is attached to the polymer backbone by a long spacer, as described in 56-142524. The amount of these hardeners added to achieve the above swelling percentage depends on the type of hardener used and the type of gelatin.

In the rapid processing of the present invention, it is preferred that the emulsion layer and / or the other hydrophilic colloid layer contain an organic substance which flows out in the development processing step. When the substance that flows out is gelatin, a gelatin species that is not involved in the crosslinking reaction of gelatin with a hardening agent is preferable, and examples thereof include acetylated gelatin and phthalated gelatin, and those having a small molecular weight are preferable. On the other hand, as a high molecular substance other than gelatin, polyacrylamide as described in U.S. Pat.No. 3,271,158, or also polyvinyl alcohol, hydrophilic polymers such as polyvinylpyrrolidone can be effectively used, dextran and Satsuka rose, Sugars such as pullulan are also effective. Among them, polyacrylamide and dextran are preferable, and polyacrylamide is a particularly preferable substance. The average molecular weight of these substances is preferably 200,000 or less.
In addition to this, Research Disclosure Volume 176, No.17643,
The antifoggants and stabilizers described in Section VI (December issue, 1978) can be used.

The developing method of the present invention is U.S. Pat.Nos. 4,224,401, 4,168,977, 4,166,742, and 4,311,781,
Nos. 4,272,606, 4,221,857, and 4,243,739 can be applied to image formation processing of a silver halide photosensitive material capable of obtaining high photographic characteristics with high sensitivity by using a hydrazine derivative described in the same. .

Next, specific examples of the present invention will be shown, but the present invention is not limited thereto.

Example 1 Preparation of Emulsion 30 g of gelatin and 6 g of potassium bromide were added to 1 part of water, and a silver nitrate aqueous solution (as silver nitrate) was added while stirring in a container kept at 60 ° C.
An aqueous solution of potassium bromide containing 5 g) and 0.15 g of potassium iodide was added by the double jet method over 1 minute. Further, an aqueous solution of silver nitrate (145 g as silver nitrate) and an aqueous solution of potassium bromide containing 4.2 g of potassium iodide were added by the double jet method. At this time, the flow rate was accelerated so that the flow rate at the end of the addition was 5 times that at the start of the addition. After the addition is complete, the sedimentation method
After removing the soluble salts at 40 ° C, the temperature was raised to 40 ° C and 75 g of gelatin was added to adjust the pH to 6.7. The resulting emulsion was tabular grains having a projected area diameter of 0.98 μm and an average thickness of 0.138 μm, and the silver iodide content was 3 mol%. In this emulsion,
Chemical sensitization was performed by combining gold and sulfur sensitization.

Preparation of photographic material 101 As a surface protective layer, in addition to gelatin, polyacrylamide having an average molecular weight of 8000, sodium polystyrene sulfonate,
Polymethylmethacrylate fine particles (average particle size 3.0
μm), polyethylene oxide, 200 ml / 1 mol Ag of a 10 ⁻³ mol methanol solution of the compound of the present invention (see Table 1), and a gelatin aqueous solution containing a hardener and the like were used.

Anhydro-5,5'-dichloro-9-ethyl-3,3'-di (3-sulfopropyl) oxacarbocyanine hydroxide sodium salt as a sensitizing dye was added to the above emulsion at a ratio of 500 ml / 1 mol Ag. 200 ml / 1 mol of potassium iodide
It was added in the proportion of Ag. Further, as stabilizers, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and 2,6bis (hydroxyamino) -4-diethylamino-1,3,5
-Triazine and nitrone, trimethylolpropane as a dry antifoggant, a coating aid, a film hardener to form a coating solution, which is coated and dried on both sides of a polyethylene terephthalate support at the same time as a surface protective layer, thereby forming a photographic material It was created. The coated silver amount of this photographic material is 2 g / m ² per side. The swelling rate according to the above definition was 120%.

This light-sensitive material was exposed to X-rays and developed with the following developer fixing solution and water washing solution formulations.

<Developer> Potassium hydroxide 24g Sodium sulfite 40g Potassium sulfite 50g Diethylenetriaminepentaacetic acid 2.4g Boric acid 10g Hydroquinone 35g Diethylene glycol 11.2g 4-Hydroxymethyl-4-methyl-1-phenyl-3
-Pyrazolidone 3.3g 5-methylbenzotriazole 60mg Potassium bromide 2g Adjust to 1 with water (adjust to pH 10.50).

<Fixing solution> Ammonium thiosulfate 140g Sodium sulfite 15g Ethylenediaminetetraacetic acid / disodium dihydrate 25mg Sodium hydroxide 6g Adjust to 1 with water (adjust pH to 4.90 with acetic acid) <Stabilizing solution> (Squeeze roller cleaning) Also used for layers) Ethylenediaminetetraacetic acid disodium salt / dihydrate (antifungal agent) 0.5g / l Automatic developing machine Dry to Dry processing for 60 seconds.

Development tank 7.5l 35 ° C x 11.5 seconds (opposing roller) Fixing tank 7.5l 35 ° C x 12.5 seconds (opposing roller) Stabilization tank 6l 20 ° C x 7.5 seconds (opposing roller) Squeeze roller cleaning layer 200ml (Japanese Patent Application No. 61- No. 163217) Drying (50 ° C) 15 seconds Total processing time 55 seconds However, the heater was used to maintain the temperature of both the developing and fixing tanks, but the cooling water was not used.

When the light-sensitive material was developed, the circulating stirring liquid amount of the developing solution was set to 20 l / min, and when it was not developed, it was set to 6 l / min.

The residual color after processing was expressed by measuring the transmission optical density of the non-image area with green light.

 The results are shown below.

It can be seen that the light-sensitive material containing the compound of the present invention has less residual color after processing.

Example 2 In the same manner as in Example 1, a light-sensitive material having a swelling ratio of 220% was prepared and processed with the following developer formulation.

 The time for the automatic processing machine and each process is the same as that in the first embodiment.

<Developer preparation method> 20 liters of water was put into a replenisher stock tank of about 50 liters, and then Part A, Part B, and Part C were added and dissolved while sequentially stirring, and finally made up to 38 liters with water to obtain a developer replenisher (pH 10. 3
0).

The developing solution added at a ratio of 20 ml of the starter to the developing solution replenishing solution 1 was first filled in a developing processing tank of an automatic developing machine (pH 10.15), and then the developing solution was processed every time the photosensitive material was processed. 45 ml of replenisher / 1 piece (4 inch) (10inch x 12i
nch) replenished.

<Fixing solution preparation method> 20 l of water was put into a stock tank of a replenishing solution of about 50 l, and then Part A and Part B were sequentially added with stirring, dissolved and finally made up to 38 l with water to prepare a fixing solution replenishing solution.

The same fixer replenisher was first filled into the fixing tank of the automatic developing machine (pH 4.25).

After that, each time the light-sensitive material is processed, 60 ml of the above fixer replenisher is added.
/ I replenished one sheet (10inch x 12inch).

The residual color after processing is shown by measuring the transmission optical density of the non-image area with green light.

It can be seen that the photosensitive material to which the compound of the present invention is added has a reduced residual color after processing.

Example 3 In the same manner as in Example 1, a light-sensitive material prepared by adding the same amount of various compounds of the present invention to a milk material was prepared, exposed to X-rays, and developed in the same manner as in Example 1, a fixing solution, And a washing solution formulation was developed.

The residual color after processing is shown by measuring the transmission optical density of the non-image area with green light.

It can be seen that the light-sensitive material containing the compound of the present invention has less residual color after processing.

Example 4 (1) Preparation of silver halide emulsion (i) Preparation of tabular silver halide emulsion (A) (aspect ratio 13) The tabular silver halide emulsion was prepared by preparing the following types of solutions. .

Solution D was mixed with Solution A at 75 ° C by double jet method.
And H were added. Then, the solutions E and I were added by the double jet method over 28 minutes.

Then solution B was added. After that, when solution F is added,
The addition rate was gradually increased from 0.96 cc / min, and the addition was continued for 60 minutes. After that, the solution C was added, and then the solutions G and K were added by the double jet method.

 After the addition was completed, desalting was performed by a conventional method. Then chloride
Gold / Sulfur Sensitization Method Using Auric Acid and Sodium Thiosulfate
Chemical sensitization is carried out by a photosensitive silver iodobromide emulsion A
I Distribution of triple structure particles) was obtained. Sensitizing dye-1 is chemical
Add before sensitization^*did.

* The addition amount is shown in Table-4.

(Ii) Preparation of silver halide emulsion (B) (aspect ratio 2.
7) Potassium bromide and potassium iodide and silver nitrate were added to an aqueous gelatin solution with vigorous stirring to prepare plate-shaped silver iodobromide (average iodine content 6 mol%) having an average particle size of 1 μm. Then, it was washed with water by a usual precipitation method, and then chemically sensitized by a gold / sulfur sensitization method using chloroauric acid and sodium thiosulfate to obtain a photosensitive silver iodobromide emulsion B. Sensitizing dye-1 was added before chemical sensitization (addition amount 4.8 × 10 ⁻⁴ mol / Ag mol).

(2) Preparation of coating sample Samples 8 to 21 were prepared by sequentially providing each layer of the following formulation on the triacetyl cellulose support from the support side.

(3) Sensitometry These samples were applied at 25 ° C. and 65% RH temperature and humidity, and stored for 7 days. Each sample was exposed to 400 lux tungsten light through an optical wedge for 1/10 second and then processed as follows.

(A) Automatic developing machine development HPD developing machine (manufactured by Fuji Photo Film Co., Ltd.) was used for Versamat 5AN automatic developing machine manufactured by US Kodak Company for 26.5
Development was performed at 4 ft / min.

However, as the Fix solution, Super Fuji Fix (manufactured by Fuji Photo Film Co., Ltd.) was used.

(B) Sensitivity measurement The sensitivity value was obtained as the common logarithm of the reciprocal of the exposure amount required to obtain a transmission blackening density of fog + 0.1.

(C) Evaluation of residual color The treatment is carried out by the method of (a) (however, without exposure), and the amount of the sensitizing dye (residual color) is visually evaluated.

○: Good △: Slightly bad (but within practical range) ×: Bad (outside practical range) Samples 9, 10, 12, 13, 15-21 using compounds of the invention
It can be seen from Table 5 that the residual color can be improved without lowering the sensitivity.

However, in Samples 9 and 10 containing less sensitizing dye, the residual color of Comparative Example 8 was not so bad and the effect was small.

Claims (1)

[Claims] 1. A support having at least one silver halide emulsion layer, and the emulsion layer or another hydrophilic colloid layer containing at least one compound represented by the following general formula (I). A silver halide light-sensitive material characterized by the above. General formula (I) AD In the formula, A is a blocking group capable of releasing D upon treatment and represents a group represented by the following general formula. R ₈ represents a hydrogen atom or a substitutable group, and Y ₁ is R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each represent a hydrogen atom or a substitutable group, and Z ₁ represents a group of atoms necessary for forming a carbocycle or a heterocycle. D represents a dye elution accelerator group represented by the following general formula (III). General formula (III) In the formula, R ₁ is a divalent to tetravalent aliphatic group having 1 to 8 carbon atoms, And Z and W are -N = or The stands, R ₄ represents a hydrogen atom, a halogen atom, an amino group, a hydroxyl group, group, an alkenyl group, an aryl group, an aralkyl group, L ₁ represents a divalent to tetravalent aliphatic group having 1 to 8 carbon atoms, L ₂ represents a divalent to tetravalent aliphatic group having 1 to 8 carbon atoms,
X ₂ is -S-, -O-, R ₅ and R ₆ represent a hydrogen atom or a lower alkyl group, l ₂ represents 0 or 1, R ₂ and R ₃ represent a hydrogen atom,
It represents an alkyl group or an acyl group, and R ₂ and R ₃ may be linked to each other to form a nitrogen-containing heterocycle. l ₁ represents ₁ , 2 or 3.