JP2654700B2 - Silver halide photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material capable of providing an image having an excellent S / N ratio, and more particularly, to a silver development by containing a novel antifoggant. A silver halide photographic material having an improved S / N ratio.

(Prior Art) A phenomenon in which the density of an unexposed portion of a silver halide photographic light-sensitive material (hereinafter, also simply referred to as a light-sensitive material) is increased by a development process is referred to as development fog. In general, this phenomenon is more likely to occur in a photosensitive material having a higher sensitivity, and is more likely to occur as the storage period of the photosensitive material is longer and the storage atmosphere is higher in temperature and humidity.

Further, in order to shorten the access time, high-temperature rapid processing and high-activity rapid processing in which the processing time is shortened are often performed, and also in this case, fogging is extremely likely to occur. The occurrence of development fog leads to deterioration of photographic properties such as a decrease in image contrast. Therefore, it is desirable to suppress development fog as much as possible.

As a method for suppressing the occurrence of development fog, conventionally, a method of adding a so-called antifoggant to a photosensitive material has been adopted. As the antifoggant, for example, Stabilization of Photographic Silver
Halide Emulsions (Stirizaion of Ph. By Birr
otographic Silver halide Emalsions '' Focal Press.19
Many compounds have already been known, such as those published in 1974, but compounds with a strong antifogging effect lower the sensitivity of the light-sensitive material, soften the gradation, and There is a bad effect such that color sensitization is easily hindered by inhibiting adsorption, and it has been desired to develop a compound that can prevent fog while maintaining sensitivity and gradation and reducing adverse effects on color sensitization.

(Problems to be Solved by the Invention) The present invention is to solve the above-mentioned drawbacks and to provide an antifoggant which effectively suppresses the occurrence of development fog while minimizing the decrease in sensitivity. An object of the present invention is to provide a silver halide photographic light-sensitive material which gives an image having an excellent S / N ratio by using such an antifoggant.

(Means for Solving the Problem) The present inventors have conducted research to solve the above problems, and as a result, a novel mercapto compound having a phosphonic acid moiety described below has extremely characteristic performance. Have been found to exert a surprising effect in achieving the above object.

That is, an object of the present invention is to provide a support having at least one layer of a photosensitive silver halide emulsion and having the following general formula (I)
This was achieved by a silver halide photographic light-sensitive material containing the compound represented by the formula (1) in the emulsion layer or an adjacent layer thereof.

General formula (I) In the formula, Q is bonded to a carbon atom and a nitrogen atom, and together with these, a non-metallic atomic group necessary for forming an imidazole ring, a triazole ring, a tetrazole ring, a thiadiazole ring, a benzimidazole ring, a benzoxazole ring or a benzothiazole ring. Represents

 L represents a divalent group, and n represents an integer of 0 to 2.

M ¹ represents a hydrogen atom, an ammonium ion, or a metal ion.

R ₁ and R ₂ represent a hydrogen atom, an alkyl group, an ammonium ion or a metal ion, which may be the same or different, and R ₁ and R ₂ are bonded to each other to form a 5- or 6-membered ring May be.

Next, the compound represented by formula (I) will be described in more detail.

Q represents a non-metallic atomic group necessary for bonding to a carbon atom and a nitrogen atom to form an imidazole ring, a triazole ring, a tetrazole ring, a thiadiazole ring, a benzimidazole ring, a benzoxazole ring or a benzothiazole ring.

L represents a divalent group. Examples of L include an alkylene group which may be substituted, an arylene group which may be substituted, and a heteroarylene group which may be substituted. These divalent groups and an ether bond (—O—), a thioether bond (-S-), a urethane bond (-NRCOO-), urea linkages (-NRCONR-), ester bond (-COO-), an amide bond (-CONR-), sulfonamide linkage (-SO ₂ NR
-), A thiourea bond (-NRCSNR-), a carbonate bond (-OCOO-), or another divalent group may be combined.

n represents an integer of 0 to 2, and when n = 0, it represents that a phosphorus atom is directly bonded to the heterocyclic ring formed by Q.

M ¹ represents a hydrogen atom or a cation such as an ammonium ion or a metal ion, and is preferably a hydrogen atom. Examples of ammonium ions include NH ₄ ⁺ , HN (C ₂ H ₅ ) ₃ ⁺ , N (C ₂
H _{9) 4} ^+, and the like. Na ⁺ , K
⁺ , Ag ⁺ , Li ⁺ , Ca ⁺⁺ , Zn ^{++ and the} like.

R ¹ and R ² represent a hydrogen atom, an alkyl group which may be substituted, or a cation such as an ammonium ion or a metal ion.R ¹ and R ² are preferably a hydrogen atom, an ammonium ion, a metal ion or the like. Is a cation. The alkyl group preferably has 5 or less carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a methoxyethyl group. R ¹ and R ² are bonded to each other to form a 1,2-ethylene group or a 1-ethylene group. , 3
-It may be a propylene group or the like. Examples of ammonium ions or metal ions are the same as those described in M ^1.

Further, the heterocyclic ring containing Q and the divalent group corresponding to L may have a substituent, and examples of these substituents include those shown below. When these substituents have carbon, those having 10 or less carbon atoms are preferable.

Hydrogen atom, nitro group, nitroso group, cyano group, carboxy group, sulfo group, mercapto group, hydroxy group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom,
Alkyl group, aralkyl group (optionally substituted alkyl group, aralkyl group, for example, methyl group, trifluoromethyl group, benzyl group, chloromethyl group, dimethylaminomethyl group, ethoxycarbonylmethyl group, aminomethyl Group, acetylaminomethyl group, ethyl group, carboxyethyl group, allyl group, n-propyl group, t-butyl group,
n-pentyl group, cyclopentyl group, n-hexyl group,
Cyclohexyl group, n-octyl group, n-decyl group, n
Alkenyl group (optionally substituted alkenyl group, for example, vinyl group, 2-chlorovinyl group, 1-methylvinyl group, 2-cyanovinyl group, cyclohexen-1-yl group, etc.) alkynyl group (substituted An alkynyl group, for example, an ethynyl group, a 1-propynyl group, a 2-ethoxycarbonylethynyl group, etc. an aryl group (an optionally substituted aryl group, for example,
Phenyl group, naphthyl group, 3-hydroxyphenyl group,
3-chlorophenyl group, 4-acetylaminophenyl group, 2-methanesulfonyl-4-nitrophenyl group, 3
-Nitrophenyl, 4-methoxyphenyl group, 4-acetylaminophenyl group, 4-methanesulfonylphenyl group, 2,4-dimethylphenyl group, etc. Heterocyclic group (optionally substituted heterocyclic group.
Imidazolyl group, 2-furyl group, 2-pyridyl group, 5-
Nitro-2-pyridyl group, 3-pyridyl group, 3,5-dicyano-2-pyridyl group, 5-tetrazolyl group, 5-phenyl-1-tetrazolyl group, 2-benzothiazolyl group,
2-benzimidazolyl group, 2-benzoxazolyl group, 2-oxazolin-2-yl group, morpholino group, etc. Acyl group (optionally substituted acyl group, for example, acetyl group, propionyl group, iso-butyroyl group) , A 2,2-dimethylpropionyl group, a benzoyl group, a 3,4-dichlorobenzoyl group, a 3-acetylamino-4-methoxybenzoyl group, a 4-methylbenzoyl group, etc. a sulfonyl group (a sulfonyl group which may be substituted, for example) Methanesulfonyl group, ethanesulfonyl group, chloromethanesulfonyl group, propanesulfonyl group, butanesulfonyl group, n-octanesulfonyl group, benzenesulfonyl group, 4-toluenesulfonyl group, etc. amino group (optionally substituted amino group). For example, amino group, methylamino group, dimethylamino group, ethyl Amino group, ethyl-3-carboxypropylamino group, ethyl-2-sulfoethylamino group, phenylamino group, methylphenylamino group, methyloctylamino group, etc. alkoxy group (optionally substituted alkoxy group, for example, methoxy Group, ethoxy group, n-propyloxy group,
Aryloxy group, heteroaryloxy group (optionally substituted aryloxy group, heteroaryloxy group, for example, phenoxy group, naphthyloxy group, 4-acetylaminophenoxy group, pyrimidin-2-yloxy group) , 2-pyridyloxy group, etc.) alkylthio group (optionally substituted alkylthio group).
For example, methylthio group, ethylthio group, n-butylthio group, n-octylthio group, t-octylthio group, ethoxycarbonylmethylthio group, benzylthio group, 2-hydroxyethylthio group, etc.) arylthio group, heteroarylthio group (substituted Arylthio, heteroarylthio, such as phenylthio, 4-chlorophenylthio, 2-
n-butoxy-5-t-octylphenylthio group, 4-
Nitrophenylthio group, 2-nitrophenylthio group, 4
-Acetylaminophenylthio group, 1-phenyl-5-
Tetrazolylthio group, 5-methanesulfonylbenzothiazol-2-yl group, etc.) ammonio group (optionally substituted ammonio group, for example, ammonio group, trimethylammonio group, phenyldimethylammonio group, dimethylbenzylammonio group, etc.) Carbamoyl group (carbomoyl group which may be substituted;
For example, carbomoyl group, methylcarbamoyl group, dimethylcarbamoyl group, bis- (2-methoxyethyl) carbamoyl group, cyclohexylcarbamoyl group, etc. sulfamoyl group (optionally substituted sulfamoyl group, for example, sulfamoyl group, methylsulfamoyl group Dimethylsulfamoyl group, bis- (2-methoxyethyl) sulfamoyl group, di-n-butylsulfamoyl group, etc.) acylamino group (optionally substituted acylamino group.
For example, an acetylamino group, a 2-carboxybenzoylamino group, a 3-nitrobenzoylamino group, a 3-diethylaminopropanoylamino group, an acryloylamino group, and the like. An acyloxy group (an optionally substituted acyloxy group).
For example, acetoxy group, benzoyloxy group, 2-butenoyloxy group, 2-methylpropanoyloxy group, etc. sulfonylamino group (optionally substituted sulfonylamino group, for example, methanesulfonylamino group, benzenesulfonylamino group, Methoxy-5-n-methylbenzenesulfonylamino group, etc. alkoxycarbonylamino group (optionally substituted alkoxycarbonylamino group, for example, methoxycarbonylamino group, 2-methoxyethoxycarbonylamino group, iso-butoxycarbonylamino group, Benzyloxycarbonylamino group, t-butoxycarbonylamino group, 2-cyanoethoxycarbonylamino group, etc.) aryloxycarbonylamino group (optionally substituted aryloxycarbonylamino group; for example, E Bruno alkoxycarbonylamino group, 2,4-nitrophenoxy carbonyl amino group) alkoxycarbonyl group (optionally substituted alkoxycarbonyloxy group optionally. For example, a methoxycarbonyloxy group, t-butoxycarbonyl group, 2-
Benzenesulfonylethoxycarbonyloxy group, benzylcarbonyloxy group, etc. aryloxycarbonyloxy group (optionally substituted aryloxycarbonyloxy group, for example, phenoxycarbonyloxy group, 3-cyanophenoxycarbonyloxy group, 4-acetoxyphenoxycarbonyl Oxy group, 4-t-butoxycarbonylaminophenoxycarbonyloxy group, etc. aminocarbonylamino group (optionally substituted aminocarbonylamino group, for example, methylaminocarbonylamino group, morpholinocarbonylamino group, N-ethyl-N- Phenylaminocarbonylamino group, 4-methanesulfonylaminocarbonylamino group, etc.) aminocarbonyloxy group (optionally substituted aminocarbonyloxy group; for example, A methylaminocarbonyloxy group, a pyrrolidinocarbonyloxy group, a 4-dipropylaminophenylaminocarbonyloxy group, etc.) an aminosulfonylamino group (optionally substituted aminosulfonylamino group, for example, diethylaminosulfonylamino group, di-n- Butylaminosulfonylamino group, phenylaminosulfonylamino group, etc. sulfonyloxy group (optionally substituted sulfonyloxy group, for example, phenylsulfonyloxy group, methanesulfonyloxy group, chloromethanesulfonyloxy group, 4-chlorophenylsulfonyloxy group Alkoxy or aryloxycarbonyl group (optionally substituted alkoxy or aryloxycarbonyl group, for example, methoxycarbonyl group, ethoxycarbonyl group, pheno group) (Cicarbonyl group, 2-methoxycarbonyl group, etc.) The compounds represented by the general formula (I) used in the present invention are specifically shown below, but the content of the present invention is limited to these specific examples. Not something.

Next, a method for synthesizing the compound represented by the general formula (I) used in the present invention will be described.

The synthesis of the mercapto compound represented by the general formula (I) used in the present invention can be generally carried out by the following method. A method for synthesizing the phosphonic acid moiety will be described.

For the synthesis of mercapto-substituted heterocycles, see Berichte der Deutschen Chemische Gesellschaf.
t), 22 , 568 pages (1889), 29 , 2483 pages (1896)
Year), Journal of Chemical Society (J. Chem. Soc.), 1932, p. 1806, Journal of American Chemical Society (J. Am. Chem.
Soc.), 71 , 4000 pages (1949), U.S. Patent 2,585,388
No. 2,541,924, Advances in Heterocyclic Chemistry
Chemistry), 9 , p. 165 (1968), organic
Synthesis IV (Org. Synth. IV), p. 569 (1963),
Berichte der Deutschen Chemische Gesellschaf
t), 9 , p. 465 (1976), Journal of American Chemical Society (J. Am. Chem. Sco.),
45 , p. 2390 (1923), Katricky and Lace (Katrit
Comprehensive Heterocyclic Chemi by zky and Rees
stry), 2, 3, 4, 5, and 6. In particular, Comprehensive Heterocyclic Chemistry by Katritzky and Rees
ive Heterocyclic Chemistry), which is exhaustive and helpful.

The synthesis of the phosphonic acid moiety will be described separately for alkylphosphonic acid and arylphosphonic acid.

Alkylphosphonic acids are generally reacted with alkyl halides and phosphites, the so-called Arbuzov reaction (Arbuzov reaction).
Reaction) can synthesize an alkylphosphonate. An alkylphosphonic acid can be synthesized by subjecting this phosphonate to a general hydrolysis reaction with an acid or alkali. For details of the method, see Synthesis, 1979, 6
15 pages, 1980, 456 pages, Chemical Review (Chemi
cal Review), 1981, vol. 81, p. 415, Journal of Organic Chemistry (J. of Org. Chem.).

For arylphosphonic acids, use Synthesi
s), 1979, p. 21, a method of reacting a cyclic-phosphorous chlorite with a diazonium salt to form an arylphosphonate followed by hydrolysis, Journal of
Organic Chemistry (J.Org.Chem.), 24 volumes, 3
On page 612 (1974), a method of reacting an aryl iodide with a dialkyl phosphite under light irradiation to form an arylphosphonate, followed by hydrolysis is known. It can be easily synthesized.

There are numerous methods for linking a mercapto-substituted heterocyclic moiety to a phosphonic acid moiety. A method of connecting via an alkylene group, a method of connecting via an arylene group, a method of connecting with an ester in combination with these methods, a method of connecting with a urethane bond, a method of connecting with a urea bond, a method of connecting with an ether bond It is possible to combine various divalent or more valent groups such as a method of linking with a carbonamide group and a method of linking with a sulfonamide.

Next, the content of the present invention will be described in more detail by describing specific synthesis examples.

Synthesis Example 1 Synthesis of Specific Compound Example 5 1-1 Synthesis of N- (3-acetylaminophenyl) dithiocarbamic acid triethylamine salt (1) 3-Acetonitrile was added to 600 g of 3-aminoacetanilide.
Was added and dissolved, and then 800 ml of triethylamine was added. While cooling this mixture with ice water and keeping it below 20 ° C,
360 ml of carbon disulfide were added dropwise. After about 1.5 hours, the completion of the reaction was confirmed, and the precipitated crystals were exposed to obtain 1170 g (90%) of triethylamine N- (3-acetylaminophenyl) dithiocarbamate (1). The crystals were used for the next reaction without further purification.

1-2 Synthesis of 3-acetylaminophenylisothiocyanate (2) 800 ml of acetone was added to 270 g of N- (3-acetylaminophenyl) dithiocarbamic acid triethylamine salt (1) and suspended. The mixture was cooled with ice water under a nitrogen stream, and 100 ml of ethyl chlorocarbonate was added dropwise while maintaining the temperature at 10 ° C or lower. The generated gas was captured by an aqueous solution of sodium hypochlorite. After completion of the dropwise addition, the crystals were filtered. Water 1 was added to the filtrate, and the precipitated crystals were exposed. The obtained crystals were combined, washed with water, dried, and recrystallized from acetonitrile to obtain 115 g of 3-acetylaminophenylisothiocyanate (2).

Yield: 76% Melting point: 148 ° C. 1-3 Synthesis of 1- (3-acetylaminophenyl) -3-acetylthiosemicarbazide (3) To 30 g of 3-acetylaminophenylisothiocyanate (2) was added 400 ml of ethanol. 13 g of hydrazide was added and stirred at room temperature. Crystals began to precipitate in about 30 minutes. After 4 hours, the precipitated crystals were exposed and dried to obtain 42 g of 1- (3-acetylaminophenyl) -3-acetylthiosemicarbazide (3).

Yield 100% 1-4 Synthesis of 4- (3-acetylaminophenyl) -3-methyl-5-mercaptotriazole (4) To 70 g of 1- (3-acetylaminophenyl) -3-acetylthiosemicarbazide (3) 250 ml of ethanol and 500 ml of potassium hydroxide (10%) were mixed and heated under reflux for 2 hours. After cooling, the pH was adjusted to 6 to 7 using diluted hydrochloric acid, and crystals were precipitated. The crystals were filtered by suction and dried to obtain 53 g of 4- (3-acetylaminophenyl) -3-methyl-5-mercaptotriazole (4). Yield 81%, melting point 225 ° C 1-5 4- (3-phenoxycarbonylaminophenyl) -3-methyl-5-mercaptotriazole (6)
Synthesis of 4- (3-acetylaminophenyl) -3-methyl-
5-mercaptotriazole (4) in 10 g of 12N hydrochloric acid 150
Then, the mixture was heated and refluxed. After 3 hours, the mixture was cooled, and water was distilled off with a rotary evaporator to obtain crude crystals of 4- (3-aminophenyl) -3-methyl-5-mercaptotriazole (5) hydrochloride. Acetonitrile (100 ml) was added to the crystals, followed by pyridine (12 g) and the mixture was stirred. Next, the mixture was cooled with ice water, and 7.5 g of phenyl chlorocarbonate was added dropwise while maintaining the temperature at 5 ° C. or lower. After the reaction was completed for 10 minutes after completion of the dropwise addition, 20 ml of water was added to the reaction solution, and the solvent was removed with a rotary evaporator. The obtained concentrate was extracted with ethyl acetate, and the extract was washed with saturated saline and dried over anhydrous sodium sulfate. The solvent was distilled off to obtain crude crystals of 4- (3-phenoxycarbonylaminophenyl) -3-methyl-5-mercaptotriazole (6). The crude crystals were recrystallized from ethyl acetate to obtain 13 g of compound (6).
Yield 98%, melting point 188 ° C. Synthesis of 1-6 N- (3-bulmopropyl) phthalimide (7) 90 g of potassium phthalimide was added to 300 ml of dimethylacetamide
And stirred. Then 74 ml of 1,3-dibromopropane
Was added and reacted at 120 ° C. for 4 hours. The reaction solution was poured into water 1, and the precipitated crystals were filtered by suction. The crude crystals were recrystallized from ethanol to obtain 100 g of N- (3-bromopropyl) phthalimide (7). 77% yield, melting point 65 [deg.] C 1-7 diethyl 3-aminopropylphosphonate (8)
Synthesis of N- (3-bromopropyl) phthalimide (7) 40 g
To the mixture was added 70 ml of triethyl phosphite and heated to 140 ° C. Ethyl bromide produced as a by-product was removed by distillation. After heating for 4 hours, the pressure was reduced by an aspirator, and excess triethyl phosphite was distilled off. Ethanol and 9 ml of hydrazine hydrate were added to the concentrated solution, and the mixture was heated under reflux for 20 minutes. The formed crystals were removed by filtration, and oxalic acid / acetone (10 g / 50 ml) was added to the filtrate. The crystals formed again were filtered off and the filtrate was concentrated. A small amount of water and acetone were added to the residue, and the precipitated crystals were separated by filtration. When the obtained filtrate was cooled, 3
Oxalate crystals of diethyl aminopropylphosphonate (8) were precipitated. The crystals are collected by filtration, dried under reduced pressure with a vacuum pump, and diethyl 3-aminopropylphosphonate (8)
Was obtained as the oxalate. 12g yield, 34% yield, melting point 54
1-8 Synthesis of 4- [3- {3- (3-diethylphosphonopropyl (ureido) phenyl] -3-methyl-5-mercaptotriazole (9) 4- (3-phenoxy synthesized in 1-5 To 5.0 g of carbonylaminophenyl) -3-methyl-5-mercaptotriazole (6), 40 ml of acetonitrile was added, and 8.2 g of triethylamine was added. Then, the reaction of diethyl 3-aminopropylphosphonate (8) synthesized in 1-7 was performed. Acid salt 4.
1 g was added and reacted at 50 ° C. for 4 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and 100 ml of water was added to the residue.
Crystals of [3- {3- (3-diethylphosphonopropyl (ureido) phenyl] -3-methyl-5-mercaptotriazole (9) were precipitated, and the crystals were collected by suction filtration and dried. Synthesis of 1-9 4- [3- {3- (3-phosphonopropyl) ureido} phenyl] -3-methyl-5-mercaptotriazole (10) (synthesis of specific compound 5) ) 4- [3- {3- (3-diethylphosphonopropyl)
80 ml of 12N hydrochloric acid was added to 2.0 g of ureido diphenyl] -3-methyl-5-mercaptotriazole (9) for 8 hours
The reaction was performed at 90 ° C. After the reaction, hydrochloric acid was distilled off under reduced pressure.
ml was added and dissolved by heating. When salt was added little by little to the solution, crystals precipitated. Salt was added until the solution became slightly cloudy. Then, the cloudy solution was heated to make it homogeneous again, filtered naturally, and left to stand.
[3- {3- (3-phosphonopropyl) ureido} phenyl] -3-methyl-5-mercaptotriazole (1
Crystals of 0) were precipitated. This was collected by filtration and dried. yield
0.58 g, yield: 33%, melting point: 195 ° C. The compound of the present invention is desirably incorporated in the light-sensitive material, particularly in the emulsion layer or other hydrophilic colloid layer during the production process.

The compound of the present invention can be added by dissolving in water or a suitable organic solvent miscible with water (eg, alcohols, ethers, glycols, ketones, esters, amides, etc.).

The amount of the compound of the present invention to be used is preferably an amount that produces an effect of suppressing fog during storage. In general, when added to a photographic material, it is preferably from 10 ^-7 to 10 ^-2 mol per mol of silver, more preferably from 10 ^-6 to 10 ^-2 mol per mol of silver.

In the photographic emulsion layer of the photographic light-sensitive material used in the present invention,
Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used.

Silver halide grains in photographic emulsions are cubic, octahedral,
So-called regular particles having regular crystals such as tetradecahedron may be used, or may have irregular crystal forms such as spheres, crystal defects such as twin planes, or composite forms thereof. May be.

The grain size of the silver halide may be fine grains of 0.1 μm or less or large grains having a projected area diameter of up to 10 μm, and may be a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Grafkid, published by Paul Montell (P. Glafkides, Ch.
imie et Physique Photographique Paul Montel, 196
7), “Digital Photographic Emulsion Chemistry”, published by Focal Press (GFDuffin, Photographic Emulsion Chemistry)
(Focal Press, 1966), "Manufacture and coating of photographic emulsions" by Zerikuman et al., Focus Press (VLZelikman et.
al, Making and Coating Photographic Emulsion, Focal
Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halide is a one-side mixing method, a simultaneous mixing method,
Any of these combinations and the like may be used. A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

Two or more types of silver halide emulsions formed separately may be used as a mixture.

The silver halide emulsion comprising the regular grains,
It is obtained by controlling pAg and pH during particle formation.
For more information, see, for example, Photographic Science and Eng
ineering, Vol. 6, pp. 159-165 (1962);
Journal of Pho
tographic Science), 12, 242-251 (1964), U.S. Pat. No. 3,655,394 and British Patent 1,413,748.

Monodispersed emulsions are described in JP-A-48-8600 and 51-84.
-39027, 51-83097, 53-137133, 54-48
No. 521, No. 54-99419, No. 58-37635, No. 58-49938
And Japanese Patent Publication No. 47-11386, U.S. Pat. No. 3,655,394 and British Patent 1,413,748.

Tabular grains having an aspect ratio of 5 or more can also be used in the present invention. Tabular grains are described in Cleve, Photography Theory and Pra
ctice (1930), p. 131; Gatov, Photographic Science and Engineering (Gutoff, Pho
tographic Science and Engineering), Vol. 14, 248-2
57 pages (1970); U.S. Patent Nos. 4,434,226 and 4,414,310
No. 4,433,048, No. 4,439,520 and British Patent No. 2,
It can be easily prepared by the method described in, for example, No. 112,157. When tabular grains are used, there are advantages such as an increase in covering power and an increase in color sensitization efficiency by a sensitizing dye, and are described in detail in U.S. Pat. No. 4,434,226 cited above.

The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, or may have a layered structure. These emulsion grains are described in GB 1,027,146.
And U.S. Pat. Nos. 3,505,068 and 4,444,877 and Japanese Patent Application No. 58-248469. Further, silver halides having different compositions may be bonded by epitaxial bonding, or may be bonded to a compound other than silver halide such as, for example, silver rhodan or lead oxide. These emulsion grains are described in U.S. Pat.Nos. 4,094,684 and 4,142,900.
No. 4,459,353, UK Patent No. 2,038,792, U.S. Pat.Nos. 4,349,622, 4,395,478, 4,433,501, 4,4
63,087, 3,656,962, 3,852,067, JP-A-59-
No. 162540 and the like.

 Also, a mixture of particles of various crystal forms may be used.

Silver halide solvents are useful to promote ripening.
For example, it is known to have an excess of halogen ions in the reactor to promote ripening. It is therefore clear that ripening can be promoted simply by introducing a halide salt solution into the reactor. Other ripening agents can be used, these ripening agents can be incorporated in their entirety in the dispersion medium in the reactor before adding the silver and halide salts, and one or more ripening agents can be used. And a peptizer may be added and introduced into the reactor. As another variant, the ripening agent can be introduced independently during the halide salt and silver salt addition steps.

As the ripening agent other than the halogen ion, ammonia or an amine compound, a thiocyanate salt, for example, an alkali metal thiocyanate salt, particularly a sodium and potassium thiocyanate salt, and an ammonium thiocyanate salt can be used. The use of thiocyanate ripening agents is taught in U.S. Pat. Nos. 2,222,264, 2,448,534 and 3,320,069. Also U.S. Pat.
Commonly used thioether ripening agents as described in 71,157, 3,574,628 and 3,737,313 can also be used. Or JP-A-53-82408 and JP-A-53-14431.
A thione compound as disclosed in No. 9 can also be used.

The properties of silver halide grains can be controlled by allowing various compounds to be present during the process of silver halide precipitation. Such compounds may be initially present in the reactor or may be added together with one or more salts according to conventional methods. United States Patent 2,
448,060, 2,628,167, 3,737,313, 3,772,0
No. 31, Research Disclosure, 134, 197
Copper, iridium, as described in June 5, 13452,
Controls the properties of silver halide by allowing compounds such as lead, bismuth, cadmium, zinc (chalcogen compounds such as sulfur, selenium and tellurium), gold and compounds of Group VII noble metals to be present during silver halide precipitation. it can. Japanese Patent Publication No. 58-1410, Moisa
r) et al., Journal of Photographic Science, Vol. 25, 1977, pp. 19-27, silver halide emulsions can undergo internal reduction sensitization of grains during precipitation.

Silver halide emulsions are usually chemically sensitized. Chemical Sensitization, by TH James, The Photographic Process, 4th Edition, Macmillan, 1977
Year, (THJames, The Theory of the Photographic Pro
cess, 4th ed, Macmillan, 1977), using active gelatin as described on pages 67-76, and also in Research Disclosure Volume 120, April 1974, 1200.
8; Research Disclosure, Volume 34, June 1975,
13452, U.S. Pat.Nos. 2,642,361, 3,297,446, 3,7
No. 72,031, No. 3,857,711, No. 3,901,714, No. 4,266,01
8 and 3,904,415, and British Patent 1,315,75
PAg 5-10, pH 5-8 and temperature 30 as described in No. 5.
The reaction can be carried out at -80 ° C using sulfur, selenium, chillyl, gold, platinum, palladium, iridium or a combination of a plurality of these sensitizers. Chemical sensitization is optimally carried out in the presence of a gold compound and a thiocyanate compound, and sulfur-containing compounds or hypo, thiourea-based compounds, rhodanine-based compounds described in U.S. Pat.Nos. 3,857,711, 4,266,018 and 4,054,457. And the like in the presence of a sulfur-containing compound. Chemical sensitization can also be performed in the presence of a chemical sensitization aid. The chemical sensitizing aids used include azaindene,
Compounds known to suppress fog and increase sensitivity in the process of chemical sensitization, such as azapyridazine and azapyrimidine, are used. Examples of chemical sensitization aid modifiers are described in U.S. Pat.Nos. 2,131,038, 3,411,914, 3,554,
No. 757, JP-A-58-126526, and the aforementioned "Emulsion Chemistry" by Duffin, pp. 138-143. In addition to or as an alternative to chemical sensitization, reduction sensitization, for example with hydrogen, as described in U.S. Pat.
Using reducing agents such as stannous chloride, thiourea dioxide, polyamines and the like, as described in US Pat. Nos. 6,982, 2,743,182 and 2,743,183, and using low pAg (eg, less than 5) and / or high pH (eg, (Larger than 8) Reduction sensitization can be achieved by the treatment. Also U.S. Patent 3,917,48
The color sensitization can also be improved by the chemical sensitization method described in No. 5 and 3,966,476.

The light-sensitive material of the present invention may contain one or more surfactants for various purposes such as coating aids, prevention of charged brain, improvement of sliding properties, emulsification / dispersion, prevention of adhesion, and improvement of photographic properties (for example, acceleration of development, high contrast, sensitization). May be included.

The silver halide photographic emulsion used in the present invention may be spectrally sensitized with a methine dye or the like. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus,
Such as a tetrazole nucleus and a pyridine nucleus; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, ie, an indolenine nucleus, a benzindolenin nucleus, an indole nucleus , Benzoxadol nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus and the like can be applied. These nuclei may have a substituent on a carbon atom.

In the merocyanine dye or the complex merocyanine dye, pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thiooxazolidine-2,
A 5- to 6-membered heterocyclic nucleus such as a 4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus can be applied.

These sensitizing dyes may be used alone, or a combination thereof may be used.
Often used for supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. For example, a substituted aminostilbenzene compound having a nitrogen-containing heterocyclic nucleus group (for example, those described in U.S. Pat. Nos. 2,933,390 and 3,635,721), an aromatic organic acid formaldehyde condensate (for example, U.S. Pat. No. 3,743,510) ), Cadmium salts,
An azaindene compound 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.

In the present invention, various kinds of compounds are used in combination with the compound of the above general formula (I) for the purpose of preventing fog during the production process, storage or photographic processing of the photosensitive material, or stabilizing photographic performance. Compounds can be included.
That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, promobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazole , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole) and the like; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes such as tria Zaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes), pentaazaindenes, etc .; Chiosurufuon acid, benzenesulfonic fins acid, known as antifoggants or stabilizers such as benzene Huong acid amide, can be added a number of compounds.

As a binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, gelatin is advantageously used, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol , Polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone,
Various synthetic hydrophilic polymer substances such as a single or copolymer such as polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinylpyrazole can be used.

As gelatin, besides general-purpose lime-processed gelatin, acid-processed gelatin and the journal of the Japan Society of Science Photography (Bull. Soc. Sci. Pho.
t. Japa) n, No. 16, page 30 (1966), may be used an enzyme-treated gelatin, or a hydrolyzate of gelatin may be used.

In the light-sensitive material of the present invention, an inorganic or organic hardener may be contained in any hydrophilic colloid layer constituting the photographic light-sensitive layer or the back layer. Specific examples thereof include chromium salts, aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.) and N-methylol-based compounds (dimethylol urea, etc.). Active halogen compounds (2,4-dichloro-6-hydroxy-1,3,5-
Triazines and their sodium salts, etc.) and active vinyl compounds (1,3-bisvinylsulfonyl-2-propanol, 1,2-bis (vinylsulfonylacetamido) ethane or vinyl polymers having a vinylsulfonyl group in the side chain) It is preferable because a hydrophilic colloid such as gelatin hardens quickly and gives stable photographic characteristics. N-
Carbamoylpyridinium salts (such as (1-morpholinocarbonyl-3-pyridinio) methanesulfonate) and haloamidinium salts (such as 1- (1-chloro-1-pyridinomethylene) pyrrolidinium 2-naphthalenesulfonate) also have fast and excellent curing rates. ing.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are formed of a flexible support or glass such as plastic film, paper, cloth, etc., which are usually used for photographic light-sensitive materials, ceramics,
It is applied to a rigid support such as metal. Useful as flexible supports are cellulose nitrate, cellulose acetate,
Cellulose acetate butyrate, polystyrene, polyvinyl chloride,
Examples thereof include a film made of a semi-synthetic or synthetic polymer such as polyethylene terephthalate or polycarbonate, a baryta layer, or paper coated or laminated with an α-olefin polymer (eg, polyethylene, polypropylene, ethylene / butene copolymer). The support may be colored using a dye or a pigment. It may be black for the purpose of shading. The surface of these supports is generally subjected to a subbing treatment in order to improve adhesion with a photographic emulsion layer or the like. The surface of the support may be subjected to glow discharge, corona discharge, ultraviolet irradiation, flame treatment or the like before or after the undercoating treatment.

The present invention can be applied to various color and black-and-white photographic materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers, color diffusion transfer photosensitive materials and heat developable color photosensitive materials. it can. Research Disclosure, No.17123 (1978
July, 1999) or by using a black color coupler described in U.S. Pat. No. 4,126,461 and British Patent No. 2,102,136 to obtain a black-and-white image such as for X-rays. The present invention can be applied to a photosensitive material. Plate making film such as squirrel film or scanner film, direct medical / indirect medical or industrial X-ray film, negative black-and-white film for photography, black-and-white photographic paper, COM or ordinary microfilm, silver salt diffusion transfer photosensitive material and The present invention can be applied to a printout type photosensitive material.

When the present invention is applied to a coupler type color light-sensitive material, various color couplers can be used.
Here, the color coupler refers to a compound capable of forming a dye by a coupling reaction with an oxidized aromatic primary amine developing agent. Typical examples of useful color couplers include naphthol or phenolic compounds, pyrazolone or pyrazoloazole compounds, and open-chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention are described in Research Disclosure (RD) 17643 (December 1978) V
It is described in Sections II-D and in the patents referenced in 18717 (November 1979).

The color coupler incorporated in the light-sensitive material preferably has a ballast group or is diffusion-resistant by being polymerized. A two-equivalent coupler substituted with a coupling-off group is more preferable than a four-equivalent coupler having a hydrogen atom at the coupling active position, since the amount of coated silver can be reduced. Further, a coupler in which the color-forming dye has an appropriate diffusibility, a colorless coupler, or a DIR coupler which releases a development inhibitor or a coupler which releases a development accelerator in association with a coupling reaction can also be used.

Typical examples of the yellow coupler that can be used in the present invention include oil-protected acylacetamide couplers. Specific examples thereof are described in U.S. Pat.
No. 210, No. 2,875,057 and No. 3,265,506. In the present invention, the use of a two-equivalent yellow coupler is preferred, and U.S. Patent Nos. 3,408,194 and 3,44
7,928, 3,933,501 and 4,022,620, etc., and an oxygen atom-elimination type yellow coupler or JP-B-58-10739, U.S. Pat.No. 4,401,752,
No. 326,024, RD18053 (April 1979), British Patent No. 1,425,
No. 020, West German Application No. 2,219,917, No. 2,261,361
And nitrogen atom-elimination type yellow couplers described in JP-A Nos. 2,329,587 and 2,433,812. α-pivaloylacetanilide-based couplers are excellent in the fastness of color-forming dyes, especially in light fastness, while α-benzoylacetoanilide-based couplers can provide high color density.

Examples of magenta couplers that can be used in the present invention include oil-protected, indazolone-based or cyanoacetyl-based, preferably 5-pyrazolone-based and pyrazoloazole-based couplers such as pyrazolotriazoles. 5-pyrazolone couplers are preferably couplers in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye, and typical examples thereof are U.S. Patent Nos. 2,311,082 and 2,343,703. ,
No. 2,600,788, No. 2,908,573, No. 3,062,653
No. 3,152,896 and No. 3,936,015. As a leaving group of the 2-equivalent 5-pyrazolone coupler, a nitrogen atom leaving group described in U.S. Pat. No. 4,310,619 or an arylthio group described in U.S. Pat. No. 4,351,897 is particularly preferred. Further, a 5-pyrazolone-based coupler having a ballast group described in European Patent No. 73,636 can obtain a high color density.

Pyrazoloazole-based couplers include U.S. Pat.
061,432, preferably pyrazolo [5,1-c] [1,2,4] triazoles described in U.S. Pat. No. 3,725,067, Research Disclosure 24220 (June 1984) and JP-A-60-3
And pyrazolopyrazoles described in Research Disclosure 24230 (June 1984) and JP-A-60-43659. The imidazo [1,2] described in U.S. Pat. No. 4,500,630 is low in light of yellow side absorption and light fastness of the coloring dye.
-B] pyrazoles are preferred and are described in U.S. Patent No. 4,540,654.
The pyrazolo [1,5-b] [1,2,4] triazole described in the above item is particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected naphthol couplers and phenol couplers, and naphthol couplers described in U.S. Pat.No. 2,474,293, preferably U.S. Pat.Nos. 4,052,212 and 4,146,396, Nos. 4,228,233 and 4,296,200
The representative examples are the oxygen-equivalent double-equivalent naphthol couplers described in the above publication. Specific examples of phenol couplers are described in U.S. Pat.Nos. 2,369,929 and 2,80
Nos. 1,171, 2,772,162, and 2,895,826. Humidity and temperature-resistant cyan couplers are preferably used in the present invention, and typical examples thereof include phenols having an alkyl group or more at the meta-position of the phenol nucleus described in U.S. Pat.No. 3,772,002. Cyan couplers, U.S. Pat. Nos. 2,772,162, 3,758,308, 4,126,396, 4,334,011,
No. 4,327,173, West German Patent Publication No. 3,329,729 and European Patent No. 121,365, and 2,5-diacylamino-substituted phenolic couplers described in U.S. Pat.
No. 2, No. 4,333,999, No. 4,451,559 and No. 4,4
And phenol couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, and the like. Japanese Patent Application Nos. 59-93605 and 59-264277
Cyan couplers having a 5-position of naphthol substituted with a sulfonamide group or an amide group described in JP-A-59-268135 are also excellent in color image fastness and can be preferably used in the present invention.

In order to correct unnecessary absorption in the short wavelength region of the dye formed from the magenta and cyan couplers, it is preferable to use a colored coupler in combination with the color negative photosensitive material for photography. U.S. Pat.No.4,163,670 and JP-B-57-39413
Typical examples thereof include a yellow-colored magenta coupler described in U.S. Pat. No. 4,049,849 and a magenta-colored cyan coupler described in U.S. Pat. Nos. 4,004,929, 4,138,258 and British Patent 1,146,368.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such blurred couplers are disclosed in U.S. Pat.No. 4,366,237 and British Patent 2,125,5.
No. 70 has a specific example of a magenta coupler, and EP 9
No. 6,570 and German Offenlegungsschrift 3,234,533 describe specific examples of yellow, magenta or cyan couplers.

Dye-forming couplers and the above-mentioned special couplers may form polymers of dimers or more. Typical examples of polymerized dye-forming couplers are described in U.S. Patent Nos. 3,451,820 and 3,080,211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173,
U.S. Pat. Nos. 4,367,282, 60/75041, and 60
-113596.

Various couplers used in the present invention may be used in combination of two or more in the same layer of the photosensitive layer, or the same compound may be used in two or more different layers in order to satisfy the characteristics required for the photosensitive material. Can also be introduced.

The coupler can be introduced into the light-sensitive material by various known dispersion methods, and examples thereof include a solid dispersion method, an alkali dispersion method, preferably a latex dispersion method, and more preferably an oil-in-water dispersion method. In the oil-in-water dispersion method, a high-boiling organic solvent having a boiling point of 175 ° C or higher and a so-called co-solvent having a low boiling point are dissolved in a single solution or a mixture thereof, and then water or gelatin is dissolved in the presence of a surfactant. Finely dispersed in an aqueous medium such as an aqueous solution. Examples of high boiling organic solvents are described in U.S. Pat. No. 2,322,027 and the like. Dispersion may involve phase inversion, and if necessary, may be used for coating after removing or reducing the co-solvent by distillation, noodle washing or ultrafiltration.

Specific examples of the high-boiling organic solvent include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, etc.), and phosphoric acid or phosphonic acid esters (trifel phosphate, tricresyl phosphate) , 2
-Ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate,
Di-2-ethylhexylpheninephosphonate),
Benzoic acid esters (2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl-p-
Hydroxybenzoates, amides (diethyldodecaneamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-teat-amylphenol, etc.), aliphatic carboxylic acid esters ( Dioctyl azelate, glycerol tributyrate, isostearyl lactate,
Trioctyl citrate), aniline derivatives (N, N
-Dibutyl-2-butoxy-5-tert-octylaniline), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.) and the like. As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used,
Typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone,
Ethoxyethyl acetate, dimethylformamide and the like can be mentioned.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in U.S. Pat. No. 4,199,363 and West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

Various photographic additives that can be used in the present invention are described, for example, in Research Disclosure No. 17643, pages 23-28 and No. 18716, pages 648-651. The types of these additives and the places where they are described in detail are shown below. : In the photographic processing of the light-sensitive material of the present invention, any of known methods can be used, and a known processing solution can be used. The processing temperature is usually between 18 ° C and 50 ° C
The temperature may be lower than 18 ° C or higher than 50 ° C. Depending on the purpose, any of a developing process for forming a silver image (black-and-white photographic process) and a color photographic process including a developing process for forming a dye image can be applied.

Known developing agents such as dihydroxybenzenes (for example, hydroquinone), 3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone), and aminophenols (for example, N-methyl-p-aminophenol) are used in the black-and-white developer. They can be used alone or in combination.

The color developer generally comprises an alkaline aqueous solution containing a color developing agent. Color developing agents are known primary aromatic amine developers such as phenylenediamines (for example, 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-methanesulfamidoethylaniline, 4-amino-
3-methyl-N-ethyl-N- [beta] -methyloxyethylaniline) can be used.

"Photographic Processor Chemistry" by LFA Meson, published by Focal Press (1966)
226-229, U.S. Pat.Nos. 2,193,015 and 2,592,364
And those described in JP-A-48-64933.

Other developers include alkali metal sulfites, carbonates,
It may contain pH buffers such as borates and phosphates, brominating agents, iodides, and antifoggants, such as development inhibitors such as organic antifoggants other than the compounds of the present invention. If necessary, water softeners, preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, Fogging agents such as sodium boron hydride; auxiliary developing agents such as 1-phenyl-3-pyrazolidone; viscosity-imparting agents; polycarboxylic acid-based chelating agents described in US Pat. No. 4,083,723; West German publication (OLS)
It may contain an antioxidant described in 2,622,950.

When color photographic processing is performed, the photographic light-sensitive material after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed individually. As the bleaching agent, for example, compounds of polyvalent metals such as iron (III), cobalt (III), chromium (VI), and copper (II), peracids, quinones, and nitroso compounds are used. For example, organic complex salts of ferricyanide, dichromate, iron (III) or cobalt (III), for example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid or Complex salts of organic acids such as citric acid, tartaric acid, and malic acid; persulfates, permanganates, and nitrosophenols can be used. Of these, potassium ferricyanide, sodium iron (III) ethylenediaminetetraacetate and ammonium iron (III) ethylenediaminetetraacetate are particularly useful. The iron (III) complex salt of ethylenediaminetetraacetate is useful both in an independent bleaching solution and in a single-bath bleach-fixing solution.

U.S. Pat.No. 3,042,520 for bleaching or bleach-fixing solution,
No. 3,241,966, JP-B-45-8506, JP-B-45-8836, etc., and various additives can be added in addition to the thiol compounds described in JP-A-53-65732.

The rinsing step may be performed in one tank, but is often performed by a multi-stage countercurrent rinsing method of two or more tanks. The amount of water in the washing step can be arbitrarily set according to the type and purpose of the color photosensitive material. For example, Journal of Motion Picture and Television Engineering, Vol. 64, pp. 248-253 (May, 1955) “Water
"Florents in Immersion Washing of Motion Picture Film" (Water Flow Rates)
in Immersion−Washing of Motion Picture Film, SR
Goldwasser).

When the amount of washing water is reduced, the generation of bacteria and mold becomes a problem. As the reaction, the washing water described in Japanese Patent Application No. 131632/1986, in which calcium and magnesium are reduced, a disinfectant and a deterrent agent are used. See, for example, Journal of Antibacterial and Anfunningal Agents (J. Antibact. Antifug. Agents) vol. 11, No.
5, compounds described in pages 207 to 223 (1983) and compounds described in Hiroshi Horiguchi's "Bactericidal and microbial chemistry"). Further, as a water softener, a chelating agent such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid can be added.

When you save the amount of washing water, as its water, although normally the color light-sensitive material 1 m ² per 100ml~2000ml used, preferably used in terms of the range of 200ml~1000ml is juggle water-saving effect and color image stability, especially .

 The pH in the washing step is usually in the range of 5-9.

When the light-sensitive material of the present invention is applied to a color diffusion transfer photographic method, a peeling (peel-apart) type or JP-B-46
Nos. -16356, 48-33697, JP-A-50-13040 and British Patent 1,330,524, and an integrated type as described in JP-A-57-119345. It is possible to adopt a configuration of a film unit that does not require peeling.

The use of a polymeric acid layer protected by a neutralization timing layer in any of the above formats is advantageous for widening the processing temperature latitude. When used in color diffusion transfer photography, it may be used by adding it to any layer in the light-sensitive material, or may be used by being sealed in a processing solution container as a developing solution component.

In order to obtain a wide range of colors in the chromaticity diagram using three primary colors of yellow, magenta and cyan, at least three silver halide emulsion layers having photosensitivity in different spectral regions are used in combination. For example, there are a combination of three layers of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, and a combination of a green-sensitive layer, a red-sensitive layer, and an infrared-sensitive layer. Each photosensitive layer can adopt various arrangement orders known for color photosensitive materials. Each of these photosensitive layers may be divided into two or more layers as necessary.

When the light-sensitive material of the present invention is used for a photothermographic material, an organic metal salt can be used as an oxidizing agent together with the light-sensitive silver halide. Among such organic metal salts, an organic silver salt is particularly preferably used.

Organic compounds that can be used to form the above-mentioned organic silver salt oxidizing agent include benzotriazoles, fatty acids and other compounds described in U.S. Pat. No. 4,500,626, columns 52-53. Also useful are silver salts of carboxylic acids having an alkynyl group such as silver phenylpropiolate described in JP-A-60-113235 and acetylene silver described in JP-A-61-249044. Two or more organic silver salts may be used in combination.

The above organic silver salts can be used in an amount of 0.01 to 10 mol, preferably 0.01 to 1 mol, per 1 mol of the photosensitive silver halide. The total coating amount of the photosensitive silver halide and the organic silver salt is suitably from 50 mg to 10 g / m ² in terms of silver.

As the reducing agent used in the photothermographic material, those known in the field of photothermographic materials can be used.
Further, a dye-providing compound having a reducing property described later is also included (in this case, another reducing agent may be used in combination). Further, a reducing agent precursor which does not itself have a reducing property but expresses a reducing property by the action of a nucleophilic reagent or heat during the development process can be used.

Examples of the reducing agent used in the photothermographic material or the color diffusion transfer method include U.S. Pat.
No. 4,483,914 No. 30-31, No. 4,330,617,
No. 4,590,152 and JP-A-60-140335, Nos. (17) to (1).
8), p. 57-40245, p. 56-138736, p. 59-178458
Nos. 59-53831, 59-182449, 59-182450
Nos. 60-119555 and 60-128436 to 60-128439
No. 60198540, No. 60-181742, No. 61-259253
Nos. 62-244044 and 62-131253 to 62-131256
Until the use of the reducing agent, there are reducing agents and reducing agent precursors described in EP 220,746 A2, pp. 78-96.

Combinations of various reducing agents can also be used, such as those disclosed in U.S. Pat. No. 3,039,869.

When a diffusion-resistant reducing agent is used, an electron transfer agent and / or an electron transfer agent are optionally added to promote electron transfer between the diffusion-resistant reduction agent and the developable silver halide. Precursors can be used in combination.

The electron transfer agent or its precursor can be selected from the above-mentioned reducing agents or its precursors.
It is desirable that the mobility of the electron transfer agent or its precursor is higher than that of the diffusion-resistant reducing agent (electron donor). Particularly useful electron transfer agents are 1-phenyl-3-pyrazolidones or aminophenols.

The diffusion-resistant reducing agent (electron donor) to be used in combination with the electron transfer agent may be any one which does not substantially move in the layer of the light-sensitive material among the aforementioned reducing agents, and is preferably a hydroquinone, Examples thereof include sulfonamide phenols, sulfonamido naphthols, compounds described as electron donors in JP-A-53-110827, and non-diffusive and reducing dye-providing compounds described later.

In the present invention, the amount of the reducing agent added is based on 1 mole of silver.
It is 0.001 to 20 mol, particularly preferably 0.01 to 10 mol.

A compound that generates or emits a mobile dye in response to this reaction or in reverse, when silver ions are reduced to silver in the thermal development color diffusion transfer method or ordinary color diffusion transfer method That is, a dye-donating compound is used.

First, examples of the dye-donating compound include a compound (coupler) that forms a dye by an oxidative coupling reaction. The coupler may be a 4-equivalent coupler or a 2-equivalent coupler. Further, a 2-equivalent coupler which has a diffusion-resistant group as a leaving group and forms a diffusible dye by an oxidative coupling reaction is also preferable. The diffusion resistant group may form a polymer chain. Specific examples of color developing agents and couplers can be found in James, The Theory of the Photographic Process, 4th Edition (TH James "T
he Theory of the Photographic Process ") 291-334
Pp. 354-361, JP-A-58-123533, JP-A-58-14.
9046, 58-149047, 59-111148, 59-1243
No. 99, No. 59-174835, No. 59-231539, No. 59-231540
No. 60-2950, No. 60-2951, No. 60-14242, No. 6
Nos. 0-23474 and 60-66249.

Further, as another example of the dye-donating compound, a compound having a function of releasing or diffusing a diffusible dye imagewise can be mentioned. This type of compound can be represented by the following general formula [LI].

(Dye-Y) nZ [LI] Dye represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a different bonding or linking group, and Z represents an image-like latent image. (Dye-Y) n-Z to cause a difference in the diffusivity of the compound represented by (Dye-Y) nZ, or to release Dye and to release the released Dye and (Dye- Y) represents a group having a property that causes a difference in diffusivity with n-Z, n represents 1 or 2, and when n is 2, two Dye-Ys are the same but different. Is also good.

Specific examples of the dye donating compound represented by the general formula [LI] include the following compounds. The following (1) to (4) are to form a diffusible dye image (positive dye image) in reverse correspondence to the development of silver halide, and "(1)" is to form a diffusible dye image (positive dye image) in correspondence to the development of silver halide. (A negative dye image).

U.S. Pat.Nos. 3,134,764, 3,362,819, 3,591
No. 7,200, No. 3,544,545, No. 3,482,972, etc., a dye developer in which a hydroquinone-based developer and a dye component are linked, the dye developer is diffusible in an alkaline environment, but halogen When it reacts with silver halide, it becomes non-diffusible.

As described in U.S. Pat. No. 4,503,137, non-diffusible compounds which release a diffusible dye in an alkaline environment but lose their ability when reacted with silver halide can also be used. Examples thereof include compounds that release a diffusible dye by an intramolecular nucleophilic substitution reaction described in U.S. Pat.No. 3,980,479 and the like, and an intramolecular reversion reaction of an isoxazolone ring described in U.S. Pat. Compounds that release diffusible dyes are included.

As described in U.S. Pat.No. 4,559,290, European Patent No. 220,746A2, U.S. Pat.No.4,783,396, Published Technical Report 87-6199, etc. Non-diffusible compounds that release

Examples are U.S. Pat.Nos. 4,139,389 and 4,13
9,379, JP-A-59-185333 and JP-A-57-84453, compounds which release a diffusible dye by a nucleophilic substitution reaction in the molecule after reduction, U.S. Pat.
No., JP-A-59-101649, JP-A-61-88257, RD24025 (19
1984), a compound that releases a diffusible dye by an electron transfer reaction in the molecule after being reduced.
No. 3,008,588A, JP-A-56-142530, U.S. Pat.
Nos. 893, 4,619,884, etc., compounds that release a diffusible dye by cleavage of a single bond after reduction, and release a diffusible dye after electron acceptance, as described in U.S. Pat. Nitro compounds, U.S. Pat.No. 4,609,61
Compounds which release a diffusible dye after electron acceptance described in No. 0 and the like are exemplified.

Also, as more preferred, EP 220,746A
No. 2, Published Technical Report 87-6199, U.S. Pat. No. 4,783,396, JP-A-63-201653, JP-A-63-201654, etc., in which NX bond (X is oxygen, sulfur or nitrogen) in one molecule. Represents an atom)
With a compound having an electron attractive group, compounds SO ₂ -X (X is as defined above) in one molecule described in Japanese Patent Application Sho 62-106885 having an electron attractive group, JP 63-271344 Compound having a PO-X bond (X is as defined above) and an electron-withdrawing group in one molecule described in JP-A-63-271341, and C-X 'bond in one molecule described in JP-A-63-271341. X 'is the same as X or -SO
_2- )) and a compound having an electron-withdrawing group. Further, the compounds described in Japanese Patent Application Nos. 62-319989 and 62-320771, which release a diffusible dye by cleavage of a single bond after reduction by a π bond conjugated to an electron accepting group can also be used.

Among them, a compound having an NX bond and an electron-withdrawing group in one molecule is particularly preferable. An example is EP 220,
Compounds (1) to (3), (7) to (10), (12), (13) described in 746A2 or U.S. Pat. No. 4,783,396
(15), (23)-(26), (31), (32), (35),
(36), (40), (41), (44), (53)-(59),
(64), (70), Compounds (11) to of Published Technical Report 87-6199
(23).

Compounds that have a diffusible dye as a leaving group and release a diffusible dye upon reaction with an oxidized reducing agent (DD
R coupler). Specifically, British Patent No. 1,330,524, JP-B-48-39,165, U.S. Patent Nos. 3,443,940, and 4,47
Nos. 4,867 and 4,483,914.

Is reducible to silver halides or organic silver salts,
A compound that releases a diffusible dye when the partner is reduced (DRR
Compound). Since this compound does not need to use another reducing agent, it is preferable because there is no problem of image contamination due to oxidized decomposition products of the reducing agent. A representative example is U.S. Pat.No. 3,928,312
No. 4,053,312, No. 4,055,428, No. 4,336,32
No. 2, JP-A-59-65839, JP-A-59-69839, JP-A-53-3819
No. 51-104,343, RD17465, U.S. Pat.
No. 2, 3,728,113, 3,443,939, JP-A-58-1
Nos. 16,537, 57-179840 and U.S. Pat. No. 4,500,626. Specific examples of the DRR compound include the compounds described in the above-mentioned U.S. Pat. No. 4,500,626, columns 22 to 44. Among them, compounds (1) to (3) described in the above-mentioned U.S. Pat. (10)-(13), (16)-
(19), (28)-(30), (33)-(35), (38)-
(40), (42) to (64) are preferred. Also U.S. Pat.
The compounds described in 639,408, columns 37-39 are also useful.

Other examples of the above-mentioned couplers and dye-donating compounds other than the general formula [LI] include dye silver compounds in which an organic silver salt is combined with a dye (Research Disclosure Magazine, May 1978, pp. 54-58, etc.); Azo dyes used in the heat-developed silver dye bleaching method (US Pat. No. 4,235,957, Research Disclosure, April 1976, pp. 30-32, etc.), leuco dyes (US Pat. Nos. 3,985,565, 4,022,617 etc.) Etc. can also be used.

In the photothermographic material, a compound which activates development and stabilizes an image at the same time can be used in the photosensitive material. Specific compounds preferably used are described in U.S. Pat. No. 4,500,626 at columns 51-52.

In a system for forming an image by diffusion transfer of a dye, a dye fixing material is used together with a photosensitive material. The dye-fixing material may be in a form separately coated on a support separate from the photosensitive material, or in a form coated on the same support as the photosensitive material. The relationship between the photosensitive material and the dye-fixing material, the relationship with the support, and the relationship with the white reflective layer described in column 57 of US Pat. No. 4,500,626 can be applied to the present invention.

The dye fixing material preferably used in the present invention has at least one layer containing a mordant and a binder. As the mordant, those known in the field of photography can be used, and specific examples thereof include U.S. Pat.
-88256, mordants described on pages (32) to (41);
Nos. 2-244043 and 62-244036. Further, a dye-receiving polymer compound as described in US Pat. No. 4,463,079 may be used.

The dye-fixing material may be provided with an auxiliary layer such as a protective layer, a release layer, and an anti-curl layer, if necessary. It is particularly useful to provide a protective layer.

The constituent layers of the photosensitive material and the dye fixing material include a plasticizer,
A high boiling organic solvent can be used as a slipping agent or an agent for improving the releasability of the photosensitive material and the dye fixing material. Specific examples include those described in JP-A-62-253159, page (25) and JP-A-62-245253.

Further, for the above purpose, various silicone oils (all silicone oils from dimethyl silicone oil to modified silicone oil obtained by introducing various organic groups into dimethyl siloxane) can be used. Examples thereof include various modified silicone oils described in Technical Data “Modified Silicone Oil” published by Shin-Etsu Silicone Co., Ltd., page 6-18B, especially carboxy-modified silicone (trade name: X-22-37).
10) is effective.

The silicone oils described in JP-A-62-215953 and JP-A-63-46449 are also effective.

In the present invention, an image formation accelerator can be used for the light-sensitive material and / or the dye-fixing material. Examples of the image formation accelerator include the promotion of a redox reaction between a silver salt oxidizing agent and a reducing agent, the promotion of a reaction such as the generation of a dye from a dye-providing substance or the decomposition or release of a diffusible dye, and the use of a photosensitive material layer. From the physicochemical function to bases or base precursors, nucleophilic compounds, high-boiling organic solvents (oils), thermal solvents, surfactants, silver Or, it is classified into a compound having an interaction with silver ions. However, these substance groups generally have a composite function and usually have some of the above-mentioned promoting effects. See U.S. Pat.
No. 9, columns 38-40.

Examples of the base precursor that can be used for the photothermographic material include salts of an organic acid and a base which are decarboxylated by heat, compounds which release amines by an intramolecular nucleophilic substitution reaction, Lossen rearrangement or Beckmann rearrangement, and the like. Specific examples thereof are described in U.S. Pat. No. 4,511,493 and JP-A-62-265038.

In a system in which development and transfer of a dye are carried out simultaneously in the presence of water, it is preferable to add a base and / or a base precursor to the dye-fixing material from the viewpoint of improving the storability of the photosensitive material.

In addition to the above, EP 210,660, U.S. Pat.
No. 40,445, a combination of a hardly soluble metal compound and a compound capable of forming a complex with a metal ion constituting the hardly soluble metal compound (referred to as a complex forming compound);
Compounds that generate a base by electrolysis described in JP-A 61-232451 can also be used as the base precursor. In particular, the former method is effective. The sparingly soluble metal compound and the complex forming compound are advantageously added separately to the light-sensitive material and the dye-fixing material.

In the light-sensitive material and / or dye-fixing material of the present invention, various development terminators can be used for the purpose of always obtaining a constant image with respect to fluctuations in processing temperature and processing time during development.

The term "development terminator" as used herein means that after appropriate development, the base is quickly neutralized or reacts with the base to reduce the base concentration in the film, and interact with a compound that stops development or silver and silver salts to suppress development. Compound. Specific examples include an acid polymer, a nitrogen-containing heterocyclic compound, a mercapto compound and a precursor thereof. Examples of the photothermographic material which can be used include an acid precursor which releases an acid upon heating, an electrophilic compound which causes a substitution reaction with a coexisting base upon heating, and more specifically, JP-A No. 62-253159 (31)-
It is described on page (32).

Methods of exposing and recording images on photosensitive materials include, for example, a method of directly photographing landscapes and people using a camera, a method of exposing through a reversal film or a negative film using a printer or a enlarger, and a method of copier. Scanning and exposing the original image through slits using an exposure device, etc., exposing the image information by emitting light from a light emitting diode or various lasers via electrical signals, CRT, liquid crystal display, electroluminescence display And a method of outputting the image to an image display device such as a plasma display and exposing the image directly or via an optical system.

As a light source for recording an image on a photosensitive material, as described above, natural light, a tungsten lamp, a light emitting diode, a laser light source, a U.S. Pat.
The light sources described in the column can be used.

Further, image exposure can be performed using a wavelength conversion element in which a non-linear optical material and a coherent light source of laser optics are combined. Here, a nonlinear optical material is a material that can exhibit nonlinearity between polarization and electric field that appears when a strong optical electric field such as laser light is applied, and includes lithium niobate, potassium dihydrogen phosphate (KDP ), Inorganic compounds represented by lithium iodate, BaB ₂ O _{4 and the} like, urea derivatives, nitroaniline derivatives such as nitropyridine-N-oxide such as 3-methyl-4-nitropyridine-N-oxide (POM). Oxide derivatives, JP-A-61-53462, 6
The compounds described in 2-210432 are preferably used. As a form of the wavelength conversion element, a single crystal optical waveguide type, a fiber type and the like are known, and any of them is useful.

The image information includes an image signal obtained from a video camera, an electronic still camera, a television signal represented by the Nippon Television Signal Standard (NTSC), and an image obtained by dividing an original image into a number of pixels such as a scanner. Signals, image signals created using a computer represented by CG and CAD can be used.

 Hereinafter, a processing method of the photothermographic material will be described.

The photosensitive material and / or the dye-fixing material may have a form having a conductive heating element layer as a heating means for heat development or diffusion transfer of the dye. In this case, as the transparent or opaque heating element, those described in JP-A-61-145544 can be used. Note that these conductive layers also function as antistatic layers.

The heating temperature in the thermal development step can be developed at about 50 ° C. to about 250 ° C., and particularly about 80 ° C. to about 180 ° C. is useful. The dye diffusion transfer step may be performed simultaneously with the heat development, or may be performed after the heat development step. In the latter case, the heating temperature in the transfer step is such that the transfer can be performed in the range from the temperature in the heat development step to room temperature, but it is particularly preferable that the heating temperature is 50 ° C. or higher and about 10 ° C. lower than the temperature in the heat development step.

Dye transfer is caused only by heat, but a solvent may be used to promote dye transfer.

Further, as described in detail in JP-A-59-218443, JP-A-61-238056, etc., a method of performing development and transfer simultaneously or continuously by heating in the presence of a small amount of a solvent (particularly water) is also available. Useful. In this method, the heating temperature is preferably 50 ° C. or higher and the boiling point of the solvent or lower.
100 ° C or less is desirable.

Examples of the solvent used for promoting development and / or transferring the diffusible dye to the dye-fixing layer include water or a basic aqueous solution containing an inorganic alkali metal salt or an organic base (these bases include Those described in the section of the formation accelerator are used. In addition, a low-boiling solvent or a mixed solution of a low-boiling solvent and water or a basic aqueous solution can also be used. Further, a surfactant, an antifoggant, a sparingly soluble metal salt and a complex-forming compound may be contained in the solvent.

These solvents can be used in a method for imparting to the dye fixing material, the photosensitive material, or both. The amount used may be as small as not more than the weight of the solvent corresponding to the maximum swelling volume of the entire coating film (especially not more than the weight of the solvent corresponding to the maximum swelling volume of the entire coating film minus the weight of the entire coating film).

As a method for applying a solvent to the photosensitive layer or the dye fixing layer, there is, for example, a method described in JP-A-61-147244, page (26). Further, the solvent may be contained in the photosensitive material or the dye-fixing material or both in advance, for example, by enclosing the solvent in microcapsules.

In order to promote dye transfer, a method in which a hydrophilic thermal solvent which is solid at normal temperature and dissolves at high temperature is incorporated in the photosensitive material or the dye fixing material can be adopted. The hydrophilic thermal solvent may be incorporated in any of the photosensitive material and the dye fixing material,
It may be built in both. Also, the layer to be incorporated is an emulsion layer,
Any of an intermediate layer, a protective layer, and a dye-fixing layer may be used, but it is preferable to be incorporated in the dye-fixing layer and / or a layer adjacent thereto.

Examples of hydrophilic thermal solvents include ureas, pyridines, amides, sulfonamides, imides, alkenyls,
There are oximes and other heterocycles.

In order to promote dye transfer, a high-boiling organic solvent may be contained in the light-sensitive material and / or the dye-fixing material.

As a heating method in the development and / or transfer step, it is contacted with a heated block or plate, or in contact with a hot plate, hot presser, heat roller, halogen lamp heater, infrared and far infrared lamp heater, For example, passing through a high temperature atmosphere.

The method described in JP-A-61-147244, page 27, can be applied as a pressure condition and a method of applying pressure when the photosensitive material and the dye-fixing material are overlaid and brought into close contact with each other.

Any of a variety of thermal development equipment can be used to process the photographic elements of the present invention. For example, JP-A-59-75247, JP-A-59-75247
-17747, 59-181353, 60-18951, Shokai 6
An apparatus described in, for example, No. 2-25944 is preferably used.

Example 1 A method for preparing a silver halide emulsion (I) of the fifth layer will be described.

A well-stirred aqueous gelatin solution (20 g of lime-treated deionized bone gelatin (Ca content 20 ppm) in 800 ml of water, 4 g of sodium chloride and 0.1 g of potassium bromide) 0.015 g dissolved in water and kept at 65 ° C) and silver nitrate aqueous solution (50 g of AgNO ₃ dissolved in water to make a total of 300 ml)
And an aqueous halogen solution (22.8 g of KBr, 6 g of NaCl dissolved in water to make a total of 300 ml) were simultaneously added over 30 minutes. Next, the temperature of the solution was lowered to 35 ° C., and an aqueous solution of silver nitrate (Ag
50 g of NO ₃ was dissolved in water to make a total of 300 ml) and an aqueous halide solution (31.5 g of KBr, 1.7 g of NaCl dissolved in water to make a total of 300 ml) were added simultaneously over 30 minutes.

After washing with water and desalting, lime-processed bone gelatin (guanine content 50
(ppm) 25 g and water 100 ml were added to adjust the pH to 6.3 and pAg7.9.

Keep the obtained emulsion at 55 ° C and triethylthiourea 0.8m
g, 100 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was used for optimal chemical sensitization. The yield of the emulsion was 650 g.

Next, how to prepare the silver halide emulsion (II) of the third layer will be described.

Lime-processed bone gelatin with good stirring (ash content 0.4%,
Adenine content 0.2ppm) aqueous solution (gelatin 50g in 800ml water)
And sodium chloride (10 g), potassium bromide (0.1 g) and sodium hydroxide (1N) (5 cc).
An aqueous solution of O ₃ (100 g of AgNO ₃ dissolved in water to make a total of 600 ml) and an aqueous halide solution (54.5 g of KBr and 2 g of NaCl dissolved in water to make a total of 600 ml) were simultaneously added over 30 minutes. 1 minute after completion of the addition, 0.2 g of sensitizing dye (A),
(B) A dye solution prepared by dissolving 0.2 g in 120 ml of water and 120 ml of methanol was added, and 5 minutes later, a 1% aqueous solution of potassium iodide was added.
10 ml was added.

After washing and desalting, lime-processed bone gelatin (adenine content 20
ppm) and 50 ml of water were added to adjust the pH to 6.0 pAg7.6.

The obtained emulsion was kept at 60 ° C., and chemically ripened for 50 minutes using 2.5 mg of hypo. The yield of the emulsion was 500 g.

Next, how to prepare the silver halide emulsion (III) of the first layer will be described.

Lime-processed bone gelatin with good stirring (2500pp containing Ca)
m) Aqueous solution (gelatin 20g and sodium chloride 2 in 800ml water)
g and compound 0.015 g was dissolved and kept at 50 ° C.), the following solution I and solution II were simultaneously added, and solution I was added over 12 minutes and solution II over 8 minutes. From 16 minutes after the completion of the addition of the solution I, the solution IV is added over a period of 44 minutes.
Added over minutes. The pAg from the end of the addition of the solution I to the start of the addition of the solution III was 6.7.

After washing with water and desalting, lime-processed bone gelatin (Ca content 4000pp
m) 25 g and 100 ml of water were added to adjust the pH to 6.0 and pAg 7.7. Thereafter, chemical sensitization was optimally performed at 55 ° C. using 1.1 mg of triethylthiourea and 60 mg of 4-hydroxy 6-methyl-1,3,3a, 7-tetrazaindene. The yield of the emulsion was 650 g.

 How to make an organic silver salt is described.

Organic silver salt (1) A method for preparing a silver benzotriazole emulsion will be described.

28 g of gelatin and 13.2 g of benzotriazole were dissolved in 300 ml of water. This solution was kept at 40 ° C. and stirred. A solution prepared by dissolving 17 g of silver nitrate in 100 ml of water was added to this solution over 2 minutes.

The pH of the benzotriazole silver emulsion was adjusted, allowed to settle, and excess salts were removed. Then adjust the pH to 6.30,
A yield of 400 g of silver benzotriazole emulsion was obtained.

Organic silver salt (2) 20 g of gelatin and 5.9 g of 4-acetylaminophenylpropiolic acid were dissolved in 100 ml of a 0.1% aqueous sodium hydroxide solution and 200 ml of ethanol.

 This solution was kept at 40 ° C. and stirred.

To this solution, a solution prepared by dissolving 4.5 g of silver nitrate in 200 ml of water was added over 5 minutes.

The pH of the dispersion was adjusted and settled to remove excess salts. Thereafter, the pH was adjusted to 6.3 to obtain a dispersion of the organic silver salt (2) in a yield of 300 g.

Next, a method of preparing a gelatin dispersion of a dye-providing substance will be described.

15 g of yellow dye-providing substance (A), 1.2 g of reducing agent
g, 0.3 g of mercapto compound (1), surfactant (4)
Was weighed, and 1.5 g of the high-boiling organic solvent (1) was weighed, 45 ml of ethyl acetate was added, and the mixture was heated and dissolved at about 60 ° C. to obtain a uniform solution. This solution and 100 g of a 10% solution of lime-processed gelatin and water
After stirring and mixing 30 ml, 10 minutes with a homogenizer for 10 minutes.
Dispersed at 000 rpm. This dispersion is referred to as a yellow dye-providing substance dispersion.

15 g of magenta dye-providing substance (B) and 0.6 g of reducing agent
g, 0.15 g of mercapto compound (1), surfactant (4)
Was weighed, and 1.5 g of the high boiling organic solvent (2) was weighed, 25 ml of ethyl acetate was added, and the mixture was dissolved by heating at about 60 ° C. to obtain a uniform solution. 100 g of this solution and a 10% solution of lime-processed gelatin and 30
After stirring and mixing the mixture with a homogenizer,
Dispersed at 0 rpm. This dispersion is referred to as a magenta dye-providing substance dispersion.

15 g of cyan dye-donor substance (C) and 0.8 g of reducing agent
g, mercapto compound (1) 0.6 g, surfactant (4)
Was weighed, and 8.3 g of the high-boiling organic solvent (1) was weighed, 30 ml of ethyl acetate was added, and the mixture was heated and dissolved at about 60 ° C. to obtain a uniform solution. 100 g of this solution and a 10% solution of lime-processed gelatin and 30
After stirring and mixing the mixture with a homogenizer,
Dispersed at 0 rpm. This dispersion is referred to as a dispersion of a cyan dye-donating substance.

With these, the photothermographic material 100 as shown in the following table can be formed.

Water-soluble polymer (1) Sumikagel L-5 (H) manufactured by Sumitomo Chemical Co., Ltd. Surfactant (1) Aerosol OT High-boiling point organic solvent (1) Triisononyl phosphate High-boiling point organic solvent (2) Trihexyl phosphate In the above-described photosensitive material 100, the third and fifth layers contain the following compound A at 0.015 g / m ² in each layer. To prepare a photosensitive material 101.

Further, the compound of the present invention was added to the third layer and the fifth layer, respectively.
As shown in No. 1, photosensitive materials 102 to 110 were prepared.

 Next, a method of making the dye fixing material will be described.

The composition was coated on a paper support laminated with polyethylene according to the composition shown in the following table to prepare a dye fixing material R-1.

Surfactant * 2 Aerosol OT Polymer * 5 Vinyl alcohol sodium acrylate copolymer (75/25 molar ratio) Polymer * 7 Dextran (Molecular weight 70,000) High boiling organic solvent * 8 Leofos 95 (manufactured by Ajinomoto Co., Inc.) Matting agent * 10 Benzoguanamine resin (18vol% of particles exceeding 10μ) Using a tungsten light bulb as the multilayered color light-sensitive material, G, R, and IR three-color separation filters with continuously changing density ( G was a band-pass filter of 500 to 600 nm, R was a band pass filter of 600 to 700 nm, and IR was a filter having a transmittance of 700 nm or more.). 15ml on the emulsion side of this exposed photothermographic material
/ m ² of water was supplied by a wire bar, and then superimposed so that the dye-fixing material R-1 was in contact with the membrane surface.

After heating for 25 seconds using a heat roller whose temperature has been adjusted so that the temperature of the water-absorbed film becomes 93 ° C., when the dye fixing material is peeled off from the photosensitive material, G,
Clear images of yellow, magenta and cyan were obtained corresponding to the three color separation filters of R and IR. The densities of the yellow and magenta dye images were measured using a Macbeth reflection densitometer (RD-51).
9), the results shown in Table 1 were obtained.

As can be seen from Table 1, a photothermographic material having a low fog density was obtained by using the compound of the present invention.

Example 2 A silver bromide gelatin emulsion composed of monodisperse tetrahedral grains (average grain size of silver halide grains of about 0.8 μm) was ripened by adding diphenylthiourea, potassium chloroaurate and rhodane ammonium. After 0.1 mol% of potassium iodide was added to the obtained emulsion, 3,3'-disulfopropyl-5-5'-dichloro-9-ethyl-oxacarbocyanine sodium salt was added. And a comparative compound were added as shown in Table 2, and a coating initial agent (sodium dodecylbenzenesulfonate) and a hardening agent (2,4
-Dichloro-6-hydroxy-s-triazine), and applied and dried on a cellulose triacetate support to obtain Samples 201 to 207. These samples were exposed using an optical wedge equipped with a yellow filter using a sensitometer (1/20 second), and then exposed to a PQ developer having the following composition at 35 ° C and 35 ° C.
After developing for 2 seconds, fixing, washing and drying by a usual method, photographic properties (sensitivity and fog) were measured, and the results shown in Table 2 were obtained.

The photographic sensitivity is represented by the reciprocal of the logarithm of the exposure amount required to obtain an optical density of fog value +0.2. In Table 2, the sensitivity of sample 201 is set to 100, and the other values are relatively expressed. Was.

As is clear from Table 2, the compound of the present invention effectively lowers the fog density without lowering the relative sensitivity as compared with the comparative compounds B and C.

Example 3 Sodium thiosulfate was added to a silver iodobromide gelatin emulsion (average size of silver halide grains: 0.5 μm) containing 5 mol% of silver iodide, and ripened by heating at 60 ° C. for 60 minutes.

To the obtained emulsion, the compound of the present invention and a comparative compound were added as shown in Table 3, and further added to a coupler, a spectral sensitizer, a hardener, and a coating aid shown in the following [Additives], and coated and dried. Thus, samples 301 to 306 were obtained. These samples were exposed to light through a yellow filter (1/20 second), and then subjected to the following color development processing, followed by measurement of photographic properties, and the results shown in Table 3 were obtained.

The sensitivity in Table 3 was set to 100 immediately after the application of the sample 301 as in Example 1, and the other values were relatively expressed.

1.Color development 2 minutes 45 seconds (38 ° C) 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.Stable 3 minutes 15 seconds The composition of the processing solution used is as follows.

(Color developer)

Sodium nitrilotriacetate 1.0 g Sodium sulfite 4.0 g Sodium carbonate 30.0 g Potassium bromide 1.4 g Hydroxylamine sulfate 2.4 g 4- (N-ethyl-N-βhydroxyethylamino-2
-Methyl-aniline 4.5g Sulfate 1 Add water [Bleaching solution] Ammonium bromide 160.0g Ammonia water (28%) 25.0ml Ethylenediamine-tetraacetic acid sodium ferric acid 130.0g Glacial acetic acid 14.0ml Add water 1 [Fixation] Liquid] Sodium tetrapolyphosphate 2.0g Sodium sulfite 4.0g Ammonium thiosulfate (70%) 175.0ml Sodium bisulfite 4.6g Water added 1 [Stable liquid] Formalin 8.0ml Water added 1 [Additive] Coupler: 1- (2,4,6-trichlorophenyl) -3-
[3- (2,4-Di-t-amylphenoxy) -acetamido] benzamide-5-pyrazolone Spectral sensitizer: bis- [2- {1-ethyl-3- (3-sulfopropyl) -5, 6-Dichlorobenzimidazole {] trimethine cyanine sodium salt Hardener: 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt As is evident from Table 3, the compounds of the present invention effectively lower the fog density without lowering the relative sensitivity as compared with Comparative Compound B in color development.

 ──────────────────────────────────────────────────の Continuation of the front page (56) References Japanese Patent Publication 5-84507 (JP, B2)

Claims (2)

(57) [Claims] 1. A silver halide photographic light-sensitive material comprising a compound represented by the following general formula (I). General formula (I) In the formula, Q is bonded to a carbon atom and a nitrogen atom, and together with these, an imidazole ring, a triazole ring, a tetrazole ring,
It represents a group of non-metallic atoms necessary for forming a thiadiazole ring, a benzimidazole ring, a benzoxazole ring or a benzothiazole ring. L represents a divalent group, and n represents an integer of 0 to 2. M ¹ represents a hydrogen atom, an ammonium ion, or a metal ion. R ₁ and R ₂ represent a hydrogen atom, an alkyl group, an ammonium ion or a metal ion, which may be the same or different, and R ₁ and R ₂ are bonded to each other to form a 5- or 6-membered ring May be. 2. The method according to claim ₁ , wherein at least one of R ₁ and R ₂ is a hydrogen atom,
3. The silver halide photographic material according to claim 1, which represents an ammonium ion or a metal ion.