JPH04140739A - Chemically sensitizing method for silver hlaide emulsion - Google Patents

Abstract

PURPOSE:To provide the chemically sensitizing method for the high-sensitivity silver halide emulsion which fogs less by emulsifying and dispersing a soln. mixture prepd. by dissolving a selenium sensitizer and at least one kind of water-insoluble and org. solvent-soluble polymers and adding this dispersion to a silver halide emulsion. CONSTITUTION:The dispersion formed by subjecting the soln. mixture dissolved with the selenium sensitizer and at least one kind of water-insoluble and org. solvent-soluble polymer to emulsion dispersion is previously prepd. and this dispersion is added in a liquid or solid form to the silver halide emulsion to sensitize the emulsion with the selenium. The generation of the fogging is drastically suppressed in this way and simultaneously such desirable results that gradations are increased in contrast and sensitivity is increased, are obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for chemical sensitization of silver halide emulsions. In particular, it relates to a chemical sensitization method for silver halide emulsions with improved fog and sensitivity.

(Prior Art) Silver halide emulsions used in silver halide photographic materials are usually chemically sensitized using various chemical substances in order to obtain desired sensitivity, gradation, etc.

As typical methods, various sensitization methods are known, including sulfur sensitization, selenium sensitization, noble metal sensitization such as gold, reduction sensitization, and combinations thereof.

In recent years, there has been a strong desire for silver halide photographic materials to have high sensitivity, excellent graininess, high sharpness, and rapid processing that accelerates the development process, etc., and various improvements have been made to the above-mentioned sensitization methods. .

Among the above sensitization methods, the selenium sensitization method is described in US Pat.
No. 623499, No. 3297446, No. 3297
No. 447, No. 3320069, No. 3408196
No. 3408197, No. 3442653, No. 3420670, No. 3591385, French Patent No. 2693038, French Patent No. 2093209, Japanese Patent Publication No. 52-34491, No. 52-34492, No. 53
No.-295, No. 57-22090, JP-A-59-18
No. 0536, No. 59-185330, No. 59-181
No. 337, No. 59-187338, No. 59-1922
No. 41, No. 60-150046, No. 60-15163
No. 7, No. 61-246738, Patent Application No. 1-13894
No. 0, No. 1-287380, No. 1-250950,
No. 1-254441, No. 2-34090, No. 2-1
No. 10558, No. 1-130976, No. 2-1391
No. 83, and Fuji Photo Film■ are the applicants 19
Patent application filed in the Philippines on August 30, 1990 (C) Furthermore, British Patent No. 255846, British Patent No. 861984, and H, E,
5pencer et al., Journal of Photo
Graphic 5science magazine, Volume 31, 158~
It is disclosed on page 169 (1983).

(Problems to be Solved by the Invention) However, although selenium sensitization generally has a greater sensitizing effect than sulfur sensitization, which is commonly performed in the industry, it tends to cause greater fogging and tends to soften the tone. There are many. Although many of the above-mentioned known patents are intended to improve these drawbacks, they have not yet yielded satisfactory results, and in particular, fundamental improvements in suppressing the occurrence of fogging have been eagerly awaited.

Further, when gold sensitization is used in combination with sulfur sensitization or selenium sensitization, a remarkable increase in sensitivity can be obtained, but at the same time, fog also increases. Compared to gold-sulfur sensitization, gold-selenium sensitization is
In particular, the increase in fog was large, and there was a strong desire to develop technology to suppress the occurrence of fog.

(Objects of the Invention) The first object of the present invention is to provide a method of chemically sensitizing silver halide emulsions with less fog and high sensitivity. The second objective is to provide a highly sensitive silver halide photographic material that is suitable for rapid processing and has little blur.

(Means for Solving the Problems) The above objects are achieved by the following, and according to the present invention,
It has now become possible to take full advantage of the sensitizing effect of selenium sensitization, which was difficult with conventional techniques. That is, chemical sensitization is carried out by adding a dispersion obtained by emulsifying and dispersing a mixed solution of a selenium sensitizer and at least one water-insoluble and organic solvent-soluble polymer to a silver halide emulsion. This was achieved by chemical sensitization of silver halide emulsions.

Conventionally, selenium sensitizers have been developed by using water or a suitable organic solvent miscible with water (for example, Alcohols such as methanol, ethanol, propatool, ethers such as methyl ether,
Glycols such as ethylene glycol, ketones such as acetone, esters such as ethyl acetate, cellosolves such as methoxyethanol, amides such as dimethylforamide, etc.) and add the solution to the silver halide emulsion. Then, selenium sensitization was usually performed.

However, the present inventors prepared a dispersion in advance by emulsifying and dispersing a mixed solution of a selenium sensitizer and a water-insoluble and organic solvent-soluble polymer, and prepared this dispersion in liquid or solid form with halogen It has been newly discovered that when selenium sensitization is performed by adding it to a silveride emulsion, the occurrence of fog is significantly suppressed. At the same time, in some cases, favorable results such as higher gradations and increased sensitivity were also obtained.

Specific examples of the water-insoluble and organic solvent-soluble polymer used in the present invention will be described in detail below.

(A) Vinyl polymer (including copolymer) Monomers forming the vinyl polymer of the present invention include acrylic esters, specifically methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, 5ec-butyl acrylate, tert-butyl acrylate, amyl acrylate, hequinyl acrylate, 2-ethylhequinyl acrylate, octyl acrylate, tert-octyl acrylate, 2-chloroethyl acrylate, 2-bromo Ethyl acrylate, 4-chlorobutyl acrylate, cyanoethyl acrylate, 2-acetoxyethyl acrylate, dimethylaminoethyl acrylate, benzyl acrylate,
Methoxybenzyl acrylate, 2-chlorocyclohexyl acrylate, cyclohexyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, 5-hydroxypentyl acrylate, 2,2-dimethyl-3-hydroxypropyl acrylate, 2-methoxyethyl acrylate,
3-methoxybutyl acrylate, 2-ethoxyethyl acrylate, 2-iso-propoxy acrylate,
2-butoxyethyl acrylate, 2-(2-methoxyethoxy)ethyl acrylate, 2-(2-butoxyethoxy)ethyl acrylate, ω-methquine polyethylene glycol acrylate (additional mole number n = 9), 1-
Examples include bromo-2-methoxyethyl acrylate, 1,1-dichloro-2-ethoxyethyl acrylate, and the like.

Methacrylic acid esters: Specific examples include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 5e
C-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, stearyl methacrylate, sulfopropyl methacrylate, N-ethyl-N-phenylaminoethyl methacrylate, 2-( 3-phenylpropyloxy)ethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, triethylene glycol mono Methacrylate, dipropylene glycol monomethacrylate, 2-methoxyethyl methacrylate, 3
-methoxybutyl methacrylate, 2-acetoxyethyl methacrylate, 2-acetoacetoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-is
o-propoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2-(2-methoxyethoxy)ethyl methacrylate, 2-(2-ethoxyethoxy)ethyl methacrylate, 2-(2-butoxyethquin)ethyl methacrylate, ω-methquine polyethylene Examples include glycol methacrylate (additional mole number n=6), allyl methacrylate, and dimethylaminoethyl methacrylate methyl chloride salt.

Vinyl esters: Specific examples include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxy acetate, vinyl phenyl acetate, vinyl benzoate, vinyl salicylate. Acrylamides; For example, acrylamide, methylacrylamide, ethyl acrylamide, propylacrylamide, butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide,
Methoxyethyl acrylamide, dimethylamine ethylacrylamide, phenylacrylamide, dimethylacrylamide, diethylacrylamide, β-cyanoethylacrylamide, N-(2-acetoacetoxyethyl)acrylamide, diacetone acrylamide, etc.: Methacrylamides; e.g., methacrylamide, methylmethacrylamide amide, ethyl methacrylamide, propyl methacrylamide, butyl methacrylamide, ter
t-butylmethacrylamide, cyclohexylmethacrylamide, benzylmethacrylamide, hydroxymethylmethacrylamide, methoxyethylmethacrylamide, dimethylaminoethylmethacrylamide, phenylacrylamide, dimethylmethacrylamide, diethylmethacrylamide, β-cyanoethylmethacrylamide,
N-(2-acetoacetoxyethyl) methacrylamide, etc.; Olefinic acid: for example, dicyclopentadiene, ethylene, propylene, l-butene, 1-pentene, vinyl chloride, vinylidene chloride, imprene, chlorobrene, butadiene, 2.3 -Dimethylbutadiene, etc.; Styrenes:
For example, styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene,
Acetoxystyrene, talolstyrene, dichlorostyrene, bromustyrene, vinylbenzoic acid methyl ester, etc.; Vinyl ethers: for example, methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether, etc.; Others include butyl crotonate, Hexyl crotonate, dimethyl itaconate, dibutyl itaconate, diethyl maleate, dimethyl maleate, dibutyl maleate, diethyl fumarate, dimethyl fumarate, dibutyl fumarate, methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, glycidyl acrylate,
Examples include glycidyl methacrylate, N-vinyloxazolidone, N-vinylpyrrolidone, acrylonitrile, methacrylonitrile, vinyldenchlorite, methylenemalonitrile, and vinylidene.

The monomers used in the polymer of the present invention (for example, the above monomers) may be used as a homopolymer, or two or more types of monomers may be used depending on various purposes (for example, improving solubility). They may also be used as comonomers with each other.

Furthermore, in order to adjust the solubility, monomers having acid groups such as those listed below can also be used as comonomers within the range where the copolymer does not become water-soluble.

Acrylic acid, methacrylic acid 4 itaconic acid: maleic acid:
Monoalkyl itaconate, such as monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, etc.; Monoalkyl maleate, such as monomethyl maleate, monoethyl maleate, monobutyl maleate, etc.; citraconic acid, styrene sulfonic acid: vinylbenzyl sulfone Acid divinylsulfonic acid niacryloxyalkylsulfonic acid, such as acryloyloxymethylsulfonic acid, acryloyloxyethylsulfonic acid,
Acryloyloxyethylsulfonic acid and the like; methacryloyloxyalkylsulfonic acid, such as methacryloyloxyethylsulfonic acid, methacryloyloxyethylsulfonic acid, methacryloyloxypropylsulfonic acid, etc.

Acrylamidoalkylsulfonic acids, such as 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methylbutanesulfonic acid, etc.; methacrylamidealkylsulfonic acids, such as 2 -methacrylamido-2-methylethanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylbutanesulfonic acid, etc. These acids are alkali metals (e.g., Na, etc.) or It may also be a salt of ammonium ion.

Among the vinyl monomers mentioned above and other vinyl monomers used in the present invention, wood-philic monomers (
Here, it refers to a substance that becomes water-soluble when made into a homopolymer. ) is used as a comonomer, there is no particular restriction on the proportion of the hydrophilic monomer in the copolymer as long as the copolymer does not become water-soluble, but it is usually preferably 40
It is mol% or less, more preferably 20 mol% or less, still more preferably 10 mol% or less.

The monomers of the invention in the polymer are preferably methacrylates, acrylamides and methacrylamides.

(B) Polyester resin obtained by condensation of polyhydric alcohol and polybasic acid Polyhydric alcohols include HO-R, -0H (R, is a hydrocarbon chain having from 2 to about 12 carbon atoms, especially aliphatic carbon hydrogen chain)
Glycols or polyalkylene glycols having the structure are effective, and polybasic acids and
Those having -R1-COOH (R2 represents a simple bond or a hydrocarbon chain having 1 to about 12 carbon atoms) are effective.

Specific examples of polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol,
, 2-propylene glycol, 1°3-propylene glycol, trimethylolpropane, 1,4-butanediol, isobutylene diol, 1. 5-bentanediol, neopentyl glycol, 1,6-hexanediol, 117-hebutanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, ■, 11-undecanediol, 1゜12-dodecanediol, 1.13-tridecanediol,
(2), 4-diol, glycerin, diglycerin, triglycerin, 1-methylglycerin, erythritol, mannitol, nruvit, and the like.

Specific examples of polybasic acids include oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, corkic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, and fumaric acid. acids, maleic acid, itaconic acid, citraconic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, methaconic acid, isohimelic acid, cyclopentadiene-maleic anhydride adduct, rosin-maleic anhydride adduct, etc. can give.

(C) Others In the formula, m represents an integer of 4 to 7, for example, a polyester obtained by ring-opening polymerization as shown below. The -CH2- chain may be branched.

Suitable monomers that can be used to make this polyester include β-propiolactone, ε-caprolactone, dimethylpropiolactone, and the like.

5. Does the molecular weight and degree of polymerization of the polymer of the present invention have substantially no significant influence on the effects of the present invention? The molecular weight of the polymer is preferably less than 1,000,000 cps, more preferably less than 2,000 cps, and more preferably 40,000 or less.
No. 5,000 or more, more preferably 150,000 or less and 10,000 or more.

The ratio of the polymer of the present invention to the co-solvent varies depending on the type of polymer used, and the solubility in the co-solvent,
It varies over a wide range depending on the degree of polymerization, etc. Typically, at least the selenium sensitizer and one or more polymers dissolved in the cosolvent will be present in an amount necessary to provide a sufficiently low viscosity for the solution to be easily dispersed in water or in an aqueous hydrophilic colloid solution. Co-solvents are used. The higher the polymerization degree of the polymer, the higher the viscosity of the solution, so it is difficult to uniformly determine the ratio of polymer to cosolvent regardless of the polymer type, but it is usually about 1:1 to 1 = 50 ( weight ratio) is preferred.

Some specific examples of the polymer used in the present invention are listed below, but the present invention is not limited thereto.

P-1) Polyvinyl acetate P-2) Polyvinyl propionate P-3) Polymethyl methacrylate P-4) Polymethyl methacrylate P-5) Polymethyl acrylate P-6) Vinyl acetate-vinyl alcohol copolymer (9)
5: 5) Poly-lobyl acrylate poly-n-butyl methacrylate polyisobutyl methacrylate polyisopropyl methacrylate polyoctyl acrylate n-butyl acrylate-acrylamide copolymer (95.5) Stearyl methacrylate-acrylic acid copolymer (90:10 ) 1.4-butanediol-adipic acid polyester P-14) P-7) P-8) P-9) P-1o) P-11) P-12) P-15) Ethylene glycol-sebacic acid polyester -16) P-17) P-18) P-19) P-20) P-21) P-22) P-23) P-24) P-25) Ester polycaprolactone polypropiolactone polydimethylprobiolactone n -Butyl methacrylate-N-vinyl-2-pyrrolidone copolymer (90: 1.0) Methyl methacrylate-vinyl chloride copolymer (70:30) Methyl methacrylate-styrene copolymer (90:10) Methyl methacrylate-ethyl Acrylate copolymer (50:50) n-butyl methacrylate-methyl methacrylate-styrene copolymer (50:30:20) Vinyl acetate-acrylamide copolymer (85:15) Vinyl chloride-vinyl acetate copolymer ( 6 P-26) P-27) P-28) P-29) P-30) P-31) P-32) P-33) Methyl methacrylate-acrylonitrile copolymer (65: 35) Diacetone acrylamide- Methyl methacrylate copolymer (50:50) Methyl vinyl ketone-isobutyl methacrylate copolymer (55:45) Ethyl methacrylate-n-butyl acrylate copolymer (70:30) Diacetone acrylamide-n-butyl acrylate copolymer (60:40) Methyl methacrylate-styrene methyl methacrylate-diacetone acrylamide copolymer (40:40:20) n-butyl acrylate-styrene methacrylate-diacetone acrylamide copolymer (70:20:10) Stearyl methacrylate-methyl Methacrylate-acrylic acid copolymer (50:40:10) P-34) P-35) P-36) P-37) P-38) P-39) P-40) P-41) Methyl methacrylate-styrene -Vinyl sulfonamide copolymer (70:20:10) Methyl methacrylate-phenyl vinyl ketone copolymer (70.30) n-Butyl acrylate-methyl methacrylate-n-butyl methacrylate copolymer (35:35:30) n-Butyl methacrylate-pentyl methacrylate-N-vinyl-2-pyrrolidone copolymer (38:38:24) Methyl methacrylate-〇-butyl methacrylate-isobutyl methacrylate-acrylic acid copolymer (37:2 9:25:9 ) n-Butyl methacrylate-acrylic acid (95: 5) Methyl methacrylate-acrylic acid copolymer (95: 5) Benzyl methacrylate-acrylic acid P-43) P-46) P-47) P-48) P-49 ) copolymer (90:1.0) n-butyl methacrylate-methyl methacrylate-benzyl methacrylate-acrylic acid copolymer (35:35:25.5) n-butyl methacrylate-methyl methacrylate-benzyl methacrylate copolymer ( 35:30:30) Polypentyl acrylate cyclohexyl methacrylate-methyl methacrylate-〇-propyl methacrylate copolymer (37:29:3 Polypentyl methacrylate methyl methacrylate-n-butyl methacrylate copolymer (65: 35) Vinyl acetate -Vinyl propionate copolymer (75: 25) n-butyl methacrylate-3-acryloxybutane-1-sulfonic acid P-51) P-52) P-53) P-54) P-55) P -57) Thorium copolymer (97:3) n-butyl methacrylate-methyl methacrylate-acrylamide copolymer (35:35:30) n-butyl methacrylate-methyl methacrylate-vinyl chloride copolymer (37:36:27) ) n-Butyl methacrylate-styrene copolymer (90:10) Methyl methacrylate-N-vinyl-2-pyrrolidone copolymer (90:10) n-butyl methacrylate-vinyl chloride copolymer (90:10) n- Butyl methacrylate-styrene copolymer (70:30) Poly (N-5ec-butylacrylamide) Poly (N-tert-butylacrylamide) P-58) Diacetone acrylamide methylmethane P-59) P'-60) P -61) P-62) P-63) P-65) P-67) P-68) Tafrylate copolymer (62: 38) Polycyclohexyl methacrylate N-tert-butylacrylamide-methyl methacrylate copolymer (30 Poly(N,N-dibutylacrylamide) Poly(tert-butyl methacrylate) tert-butyl methacrylate-methyl methacrylate copolymer (
70: 30) Poly(N-tert-butylmethacrylamide) N-tert-butylacrylamide-methylphenyl methacrylate copolymer (60: 40) Methyl methacrylate-acrylonitrile copolymer (70:30) Methyl methacrylate-methyl Vinyl ketone copolymer (38: 72) Methyl methacrylate-styrene copolymer (75: 25) P-69) Methyl methacrylate-hexyl methacrylate copolymer (70:30) P-70) Poly(N-n- Butyl methacrylamide) P-71) Poly (N-iso-butylacrylamide) P-72) Poly (N-5ec-butylacrylamide) P-73) Poly (N-tert-octylacrylamide) P-74) Poly(N-phenyl-acrylamide) P-75) Poly(N,N-dibutyl-acrylamide) P-76) Polycyclohexyl methacrylate The polymer of the present invention is at least 10 times the weight of the selenium sensitizer. ,
It is preferably used in an amount of 50 times or more by weight, particularly 100 times or more by weight.

A dispersion containing the selenium sensitizer and polymer of the present invention is prepared as follows.

After the polymer of the present invention and the selenium sensitizer are dissolved together in an auxiliary organic solvent, this solution is dissolved in water, preferably in an aqueous hydrophilic colloid solution, more preferably in an aqueous seratin solution using a dispersion aid such as a surfactant. Emulsify and disperse into fine particles using ultrasonic waves, a colloid mill, a high-speed stirrer, etc. with the help of a reagent. The auxiliary organic solvent may be removed from the prepared dispersion by methods such as distillation, noodle washing, ultrafiltration, or vacuum degassing.

When adding these emulsified dispersions to silver halide emulsions,
It may be either liquid or solid.

Examples of the auxiliary organic solvents include lower alcohols such as ethyl acetate and butyl acetate, acetate, ethyl propionate, secondary butyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, and cyclohexanone. Can be mentioned.

Furthermore, if necessary, organic solvents that are completely miscible with water, such as methyl alcohol, ethyl alcohol, acetone, and tetrahydrofuran, can also be used in part.

Moreover, these organic solvents can also be used in combination of two or more types.

As the selenium sensitizer used in the present invention, (prior art)
The selenium compounds disclosed in the patents described in . In particular, unstable selenium compounds are used which can react with silver nitrate in aqueous solution to form silver selenide precipitates. For example, US Pat. No. 1,574,944, US Pat.
No. 02592, No. 1623499, No. 3297446, Japanese Patent Application No. 130976/1996, and the patent application filed on August 30, 1990 by Fuji Photo Film ■ (
The seleno compounds described in C) are preferred.

More specifically, selenium ureas (e.g. selenourea,
Aliphatic selenoureas such as N, N-dimethylselenourea, N, N-diethylselenourea, tetramethylselenourea; N, N, N')limethyl-N'
-acetylselenourea, N, N, N'trimethyl=N'
-hebutafluoropropylcarbonylselenourea, N,
N,N'-hlimethylN'-4-chlorophenylcarbonylselenourea, N,N,N'-trimethyl, N'-4
-substituted selenoureas such as -nitrophenylcarbonylselenourea, etc.), selenoamides (e.g., selenoacetamide, N, N
-dimethylselenohenzamide, etc.), selenoketones (
For example, selenoacetone, selenoacetophenone, his-(adamantyl)selenoketone, etc.), isoselenocyanates (e.g., allyl isoselenocyanate, etc.), selenocarboxylic acids and esters (e.g., 2-selenopropionic acid, methyl 3-selenocyanate, etc.). butyrate, etc.), selenides (e.g., dimethylselenide, diethylselenide, triphenylphosphine selenide, etc.)
, selenophosphates (for example, tri-p-tolylselenophosphate, etc.), colloidal metal selenium, etc., and preferred among these are selenoureas, selenamides, and selenoketones.

The amount of selenium sensitizer used varies depending on the selenium compound used, silver halide grains, chemical ripening conditions, etc., but is generally 1 O-i to 10-1 mol per mol of silver halide, preferably 10-7 to 10-1 mol per mol of silver halide. −″′ molar level is used.

There are no particular restrictions on the conditions for chemical sensitization in the present invention; pAg is 6 to 11, preferably 7 to 10;
More preferably, it is 7 to 9.5, and the temperature is 40 to 9.5.
95°C, preferably 50-85°C.

In the present invention, it is preferable to use a noble metal sensitizer such as gold, platinum, palladium, or iridium in combination. In particular, it is preferable to use a gold sensitizer in combination, and specific examples thereof include chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, gold selenide, etc. About 1 to 10 −2 moles can be used.

In the present invention, it is also preferable to use a sulfur sensitizer in combination. Specifically, thiosulfates (e.g. hypo),
Known unstable sulfur compounds such as thioureas (e.g., diphenylthiourea, triethylthiourea, allylthiourea, etc.) and rhodanines are mentioned, and about 10-7 to 10-2 mol is used per 1 mol of silver halide. be able to.

In addition, in the present invention, when a gold sensitizer is used in combination,
Particularly preferred is gold-sulfur-selenium sensitization in which these sulfur sensitizers are also used.

In the present invention, it is also possible to use a reduction sensitizer in combination, and specifically, stannous chloride, aminoiminomethanesulfinic acid, hydrazine derivatives, borane compounds,
Examples include silane compounds, polyamine compounds, and the like.

Noble metal sensitizers, sulfur sensitizers, used in combination in the present invention,
The reduction sensitizer and the halogenated solvent described below may be added in the form of a solution in water or an appropriate water-miscible organic solvent.

Further, in the present invention, it is preferable to carry out selenium sensitization in the presence of a silver halide solvent.

Specifically, thiocyanates (e.g., potassium thiocyanate, etc.), thioether compounds (e.g., U.S. Pat. No. 3,021,215, U.S. Pat.
-30571, JP-A-60-136736, etc., especially 3゜6-cythia-1,8-octanediol, etc.), tetrasubstituted thiourea compounds (e.g.,
-11892, U.S. Patent No. 4221.863, etc., particularly tetramethylthiourea, etc.), and further,
1,000 ion compounds described in Japanese Patent Publication No. 11341/1980, mercapto compounds described in Japanese Patent Publication No. 29727/1982, meso ion compounds described in Japanese Patent Publication No. 163042/1983, US Pat. Selenoether compound described in JP-A-2-11856
Examples include the telluroether compound and sulfite described in No. 6. Among these, thiocyanates, thioether compounds, tetrasubstituted thiourea compounds and thione compounds can be preferably used, and thioneanates are particularly preferred. The amount used is 10-5 to 1 mole of silver halide.
About 5x1o-2 moles can be used.

The silver halide emulsions used in the present invention are preferably silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride.

The silver halide grains used in the present invention may have regular crystal shapes such as cubic or octahedral, or irregular crystal shapes such as spherical or plate-like.
ular) crystal form, or a composite form of these crystal forms. It is also possible to use a mixture of particles of various crystal forms, but it is preferable to use regular crystal forms.

Even if the silver halide grains used in the present invention have different phases between the inside and the surface layer (for example, silver iodobromide grains with a double or multilayer structure, in which the grain surface has fewer impurities than the inside of the grain), It may also consist of a homogeneous phase. It may also be a grain in which a latent image is mainly formed on the surface (for example, a negative emulsion), or a grain in which a latent image is mainly formed inside the grain (for example, an internal latent image emulsion, a pre-fogged direct reversal emulsion). It may be. Preferably, the particles are such that a latent image is formed primarily on the surface.

The silver halide emulsion used in the present invention has a thickness of 0.000.
Is it a tabular grain emulsion in which grains of 5 microns or less, preferably 0.3 microns or less, preferably 0.6 microns or more in diameter, and an average aspect ratio of 3 or more occupy 50% or more of the total projected area? A monodisperse emulsion having a theoretical coefficient of variation (the value S/d obtained by dividing the standard deviation S by the diameter a in the distribution expressed by the diameter when the projected area is approximated by a circle) of 20% or less is preferable. Further, two or more kinds of tabular grain emulsions and monodispersed emulsions may be mixed.

The photographic emulsion used in the present invention is P.
, GlafkideS), Chimie er Phys Photography (Chimie er Phys Photography)
ique Pho-tographique) (Published by Paul Montell, / 7 years), G.F. Duffin (
(), F, Duffin)il, photocratic
Emulsion, chemistry (Photo-graph
ic Emulsion Chemistry) (Published by Focal Press, 2013), Making and Coating Photographic ゛Emulsion yy (Maklng and Coatin) by B.L. Zelikman et al.
gPhotographic Emulsion) (7
It can be prepared using the method described in Orcal Press, 2002).

In addition, during the formation of silver halide grains, silver halide solvents such as ammonia, rhodanpotash, rhodanammonium, and thioether compounds (for example, U.S. Pat. No. 3.27/, /!7, and U.S. Pat. , 37g, t-2J', same number j, 704t, /!0
No., No. 3, No. 2P7゜G, No. 3, No. 3, Core 4. j7
), thione compounds (for example, JP-A-Sho! 3-/Ko-1)
73/ri issue, tJ-ri4tor issue, same Jrjt-7
77j7, etc.), amine compounds (for example, JP-A No. 3, No. 1007/7, etc.), etc. can be used.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc group, a thallium clay, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron ring or an iron complex salt, etc. may be present together.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used. Examples include gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfate, etc.
Sugar derivatives such as cellulose derivatives, sodium alginate, and starch derivatives; single or combined polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. A variety of synthetic hydrophilic polymeric materials such as polymers can be used.

In addition to general-purpose lime-processed gelatin, acid-processed gelatin f is available from the Journal of the Japanese Society of Scientific Photography (Bull).

Soc, Sci, Phot, Japan), A/4
Enzyme-treated gelatin as described in JO page (/ritbu) may be used, or a hydrolyzate of gelatin may be used.

In the photosensitive material of the present invention, an inorganic or organic abrasive may be contained in any hydrophilic colloid layer constituting the photographic photosensitive layer or the pack layer. Specific examples include chromium salts, aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), and N-methylol compounds (dimethylol urea, etc.). Active rogen compound [co,pi-dichloro-2-hydroxy-1I
3゜j-) riazine and its sodium salt, etc.] and active vinyl compounds (/13-bisvinylsulfonyl-coufropanol, /, 2-bis(vinylsulfonylacetamido)ethane, bis(vinylsulfonylmethyl)
Vinyl polymers having ether or hahinylsulfonyl group side chains] are preferred because they quickly harden hydrophilic colloids such as gelatin and provide stable photographic properties.

N-carbamoylpyridinium compounds ((/-morpholinocarbonyl-3-pyridinio)methane nulphonate, etc.) and haloamidinium compounds (/-(/-chloro-/-pyridinomethylene)pyrrolidinium, 2-naphthalene nulphonate, etc.) (Nato, etc.) also have a fast curing speed and are excellent.

The silver halide photographic emulsion used in the present invention may be spectrally sensitized with methine dyes or the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar-cyanine dyes, hemicyanine dyes, 2-tyryl dyes, and hemioquinol dyes. Particularly useful dyes include cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the basic heterocyclic rings and nuclei commonly used in cyanine dyes can be applied to these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and Nuclei in which aromatic hydrocarbon rings are fused to these nuclei, namely, indolenine nucleus, induindolenine nucleus, indole nucleus, induoxadol nucleus, naphthoxazole nucleus, (inzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, Applicable are benzimidazole nuclei, quinoline nuclei, etc. These nuclei may have substituents on carbon atoms.

Merocyanine dyes or composite merocyanine dyes contain pyrazoline as a core with a ketomethylene structure! -on nucleus, thiohydantoin nucleus, -monothiooxazolidine-,
≠-dione nucleus, thiazolidine-λ, ≠-dione nucleus, rhodanine nucleus, thiobarbic acid nucleus, etc.! ~ can be applied to the member heterosegmental ring nucleus.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not subtly absorb visible light but exhibits supersensitization. For example, aminostilbenzene compounds which are nitrogen-containing heteroartic ring nuclei groups and are substituted (for example, U.S. Patent Nos.
1), aromatic organic acid formaldehyde condensates (for example, those described in US Patent No. 3.7, Hiro J, J'10), cadmium salts, azaindene compounds, and the like. US Patent 3. Bu/! , ≦No. 73, same J
,t/! , Otsu 4t No. 1, 31bu/7. Jri No. 3, same!
, 43! The combinations described in , No. 7/Issue are particularly useful.

The silver halide photographic emulsion used in this technology is used to prevent fog during the manufacturing process, storage, or photographic processing of light-sensitive materials, or to stabilize photographic performance.
Various compounds can be included. Namely, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. class, incitriazole class,
Nitrobenzotriazoles, mercaptotetrazole term (%/-phenyl-!-mercaptotetrazole)
mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadolinthione; azaindenes, such as triazaindenes, tetraazaindenes (especially ≠-hydroxy substituted (/).

3.3a, 7) tetraazaindenes), hantaazaindenes, etc.; many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. can be added.

The photosensitive material of the present invention contains one or more surfactants for various purposes such as a coating aid, antistatic properties, improved slipperiness, emulsification and dispersion, prevention of adhesion, and improvement of photographic properties (for example, development acceleration, high contrast, and sensitization). But that's fine.

The photographic material prepared using the present invention may contain water-soluble dyes in the hydrophilic colloid layer as filter dyes or for various purposes such as anti-irradiation or anti-halation.

As such dyes, oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, anthraquinone dyes, and azo dyes are preferably used, and in addition, cyanine dyes, azomethine dyes, triarylmethane dyes, and phthalocyanine dyes are also useful. . An oil-soluble dye can also be emulsified by an oil-in-water dispersion method and added to the hydrophilic colloid layer.

The invention is applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support.

Multilayer natural color photographic materials usually have at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on a support. The arrangement order of these layers can be arbitrarily selected as necessary. The preferred layer arrangement is from the support side to red sensitivity, green sensitivity, and blue sensitivity, in that order. The order is a sensitive layer, a green sensitive layer and a red sensitive layer, or a blue sensitive layer, a red sensitive layer and a green sensitive layer. Further, any emulsion layer having the same color sensitivity may be composed of two or more emulsion layers having different sensitivities to improve the attained g[,
The graininess may be further improved by using a three-layer structure.

Furthermore, a non-photosensitive layer may be present between two or more emulsion layers having the same color sensitivity. A configuration may also be adopted in which emulsion layers of different color sensitivity are inserted between emulsion layers of the same color sensitivity. A reflective layer made of fine grain silver halide or the like may be provided under the high-sensitivity layer, particularly the high-g sensitivity layer, to improve sensitivity.

Generally, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used in some cases. can. For example, an infrared-sensitive layer may be combined to provide pseudo-color image quality or semiconductor laser exposure.

In the π-true light-sensitive material of the present invention, the photographic emulsion layer and other layers are made of a flexible support such as plastic film, paper, or cloth, or a rigid support such as glass, ceramic, or metal, which are commonly used in photographic light-sensitive materials. is applied to. Useful as flexible supports are films of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta layers or alpha-olefin polymers. (For example, paper coated with or laminated with polyethylene, polypropylene, ethylene/butene copolymer) or the like.

The support may be colored using dyes or pigments.

It may be made black for the purpose of blocking light. The top surface of these supports is generally subjected to a subbing treatment to improve adhesion with photographic emulsion layers and the like. The support surface may be subjected to glow discharge, corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the undercoat treatment.

For coating the photographic emulsion layer and other hydrophilic colloid layers, various known coating methods such as dip coating, roller coating, curtain coating, and extrusion coating can be used. U.S. patent no.
No., 27. g/7ri No. 7, same No. 33-Otsu j,!
fc described in No. r and No. 360J'94'7, etc.
Depending on the coating method, multiple layers may be applied simultaneously.

The present invention can be applied to various color and black and white photosensitive materials. Color negative film for general use or movies, color reversal film for slides or television, color one-percent, color positive film, color reversal ENO E-1 force 5-diffusion transfer type photosensitive material, heat developable color photosensitive material, etc. This can be cited as a substitute example. Research Day Closure, A/7/Co3 (
U.S. Pat.
The present invention can also be applied to black-and-white photosensitive materials for X-rays and the like by using the black color-forming couplers described in British Patent No. 1, No. 102,734 and the like. Films for plate making such as linu film or scanner film, X-ray film for medical and indirect medical use or industrial use, negative black and white film for photography, black and white stamp paper, COM or regular micro film, silver salt diffusion transfer photosensitive materials and prints. The present invention can also be applied to out-type photosensitive materials.

When the photographic elements of this invention are applied to color diffusion transfer photography, they may be of the peel-apart (beer-apart) type or of the
A-7tJjA No. 4tJ'-33Ari No. 7,! f!
f Kaisho! 0-/30410 and British Patent/,! 30
．． ! Integrated type as described in issue 2≠, JP-A-7-//3μ! It is possible to adopt a structure of a film unit that does not require peeling as described in No.

In either type of format described above, the use of a polymeric acid layer protected by a neutralizing timing layer is advantageous in providing a wider range of processing temperatures. When used in color diffusion transfer photography, it may be used as an additive in any layer of the photosensitive material, or it may be used as a developing solution component in a processing solution container.

Various exposure means can be used for the photosensitive material of the present invention. Any light source that emits radiation corresponding to the sensitivity wavelength of the photosensitive material can be used as the illumination or writing light source. Flash light sources such as natural light (sunlight), incandescent lamps, halogen-filled lamps, mercury lamps, fluorescent lamps, and metal-burning flash bulbs are common.

Gaseous, dye solution or conductor lasers, light emitting diodes, and plasma light sources emitting light in the wavelength range from ultraviolet to infrared can also be conveniently used as recording light sources. In addition, a micro-shutter 7 ray that uses a fluorescent surface (such as a CRT), a liquid crystal (LCD), or a lanthanum-doped lead titanium zirconate (PLZT) emitted from a phosphor excited by an electron beam, etc. It is also possible to use an exposure means that combines a shaped or planar light source. If necessary, the spectral distribution used for exposure can be adjusted using color filters.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. As this color developing agent, amine phenol compounds are also useful, but p-phinidine diamine compounds are preferably used; -Methyl-≠-amino-N-ethyl-N-
β-Hydroxylethylaniline, 3-) f Rouguami/-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-guami/-N-ethyl-N
-β-methoxyethylaniline and their sulfates,
Examples include hydrochloride and p-toluenesulfonate. These diamines are generally more stable in their salt form than in their free state, and are therefore preferably used.

The color developer contains pH-balancing agents such as alkali metal carbonates, borates or phosphates, development inhibitors or antifoggants such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds. Generally, it includes such things as If necessary, preservatives such as hydroxylamine or sulfite rings, organic solvents such as triethanolamine, diethylene glycol,
Development accelerators such as benzyl alcohol, H17 ethylene alcohol, quaternary ammonium chloride, and amines,
Dye-forming couplers, competitive couplers, nucleating agents such as sodium chloride hydride, auxiliary developers such as phenyl-3-pyrazolidone, tackifying agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, Various covering chelating agents such as phosphonocarbic acid, West German patent ratio [(OLS) Kako, 2ko, ? ! The antioxidant described in No. O may be added to the color developing solution.

In the development process for reversal color photosensitive materials, black and white development is usually performed followed by color development. This black and white developer contains dihydroquinone benzenes such as hydroquinone, nophenyl-
3-pyrazolidones such as 3-pyrazolidone or N-
Known black and white developers such as amine phenols such as methyl-p-aminophenol can be used alone or in combination.

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Furthermore, in order to speed up the processing, a bleach-fixing treatment may be performed after the bleaching treatment. Examples of bleaching agents include iron (■), Hupart (■), and chromium (■
), compounds of polyvalent metals such as copper (II), peracids, quinones, nitrone compounds, etc. are used. As an alternative bleaching agent ferricyanide; dichromate; organic complex salts of iron (Its) or nipal (II), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, /, 3-diamino- Aminopolycarmino acids such as pronoξnortetraacetic acid or citric acid,
Complex salts of @acids such as tartaric acid and malic acid; persulfates; manganates; nitrosophenols and the like can be used. Of these, iron(II[) ethylenediaminetetraacetate
Salt, diethylenetriamine 5I! i′! = Seitetsu (I[I
) salts and persulfates are preferred from the viewpoint of rapid processing and environmental pollution. Additionally, the ethylenediaminetetraacetic acid iron(II) complex is particularly useful in both stand-alone bleach solutions and -bath bleach-fix solutions.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Specific examples of useful bleach accelerators are described in U.S. Patent No. 3. 3. rj&' No. 7, West German Patent No. 7. -ta0. /No issue, fFfJJ, 0! the law of nature.

Ri IT issue, Special Public Swamp! No. 3-3273z, same jJ-J7r
, 3/issue, 374'/za issue, same! 3-Otsu! 73.2, fFJjJ-72AJj, 1tlJj-Pjj30
No. J3-2! No. 637, same! J-10≠No. 13-,
same! ! -/j4 to Hiroshi, 24 to issue, same! 3-7μ/Otsu-3
No., same jJ-J! Compounds having a mercapto group or dinulphide group as described in Hirokobu issue, Research Disclosure A/7/Kota issue (/7! July 2013); JP-A-Sho! Thiazolidine derivatives as described in O-/Hiro 0/, No. 2; Tokko Sho 1/L! -1JO1r, JP-A-Sho J
J-J0132, same! Thiourea derivatives as described in No. 3-3273j, US Pat. No. 3,7OA, J'AI;
Nishisho Patent Glad/ , /, No. 27.71j, JP-A-1973-/
4. ．． 23! Iodide described in No. 2; West German patent No. B, 4
No. 10, same j, 7! J', polyethylene oxides described in 4tJO; polyamine compounds described in JP-A No. 4tt-grJt; other JP-A-Sho F? -4j Hiroshi 31. The issue, the same Kota 3rd issue, the same! 3-ta≠2.27,
Same j4t-jj7?7, same! ! - KotJOz issue and 41! The compounds described in No. -/13aO and iodine and bromine ions can also be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred as described in US Pat. No. 131, West German Patent No. 1゜-tao,! /- issue, Tokukai Akira! 3-tajJj
Compounds described in No. O are preferred. Sara K, U.S. Patent No. 4j
j! The compounds described in No.-21314 are also preferred. These bleach accelerators may be added to the photosensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

Examples of the fixing agent include thiosulfates, thiocyanates, thioureas of thioether compounds, and large amounts of iodides, but thiosulfates are commonly used. As a preservative for the bleach-fix solution, sulfite groups, bisulfites, or Carmel bisulfite adducts are preferred.

After the bleach-fixing treatment or the fixing treatment, washing treatment and stabilization treatment are usually performed. Various known compounds may be added for the purpose of preventing precipitation and water conservation during the swimming treatment and stabilization steps. For example, to completely prevent precipitation, use water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, organic aminopolyphosphonic acid, and organic phosphoric acid, and disinfectants and preventive agents that prevent the growth of various bacteria, algae, and molds. A pie agent, a metal barrier such as magnesium clay or aluminum salt bismuth clay, a surfactant to prevent drying load and unevenness, and various hardening agents can be added as necessary. Or Photographic Science and Engineering magazine by Quest (L, E, We
s't, Phot, Sci.

Eng,), Volume J, 3ut,t ~3ty<-di(
/ y) Compounds described in ri etc. may be added. It is particularly effective to add a chelating agent or anti-piping agent.

In the washing process, water is generally flowed in one or more tanks in all directions to conserve water. Furthermore, instead of the water washing process,
- A multistage countercurrent stabilization treatment process as described in J'j Ko No. 3 may be implemented. In the case of this step, a countercurrent column of a tank is required. In addition to the above-mentioned additives, this stabilizing bath contains
One compound each is added for the purpose of stabilizing it. For example, various buffers (e.g., borates, metaborates, borax, phosphates, carbonates, potassium hydroxide, sodium hydroxide, ammonia water, Examples of W9'lJ include aldehydes such as monocarmenic acid, dicarmenic acid, polycarmitic acid, etc.) and formalin. In addition, chelating agents (inorganic phosphoric acid, aminopolycarbo/acid, organic phosphoric acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarmenic acid, etc.), fungicides (benzointhiazolinone, irithiazolone, q-thiazolinebenzimitasole, )-rogenated phenol, sulfanilamide, benzotriazole, etc.), surfactant,
Various additives such as fluorescent brighteners and hardeners may be used, and two or more compounds for the same or different purposes may be used in combination.

In addition, ammonium chloride,
It is preferable to add various ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, triammonium sulfite, and ammonium thiosulfate.

Furthermore, in the case of color sensitive materials for photography, the normally performed post-fixing (washing-stabilization) process can be replaced with the above-mentioned stabilization process and water-washing process (water saving process). At this time, if the amount of magenta coupler is one equivalent, formalin in the stabilizing bath may be removed.

The washing and stabilization processing time of the present invention varies depending on the type of photosensitive material and the processing conditions, but is usually -0 seconds to 10 minutes, preferably 10 seconds to 10 minutes. It's a minute.

The silver halide color light-sensitive material of the present invention may contain all color developing agents for the purpose of simplifying and speeding up processing. For incorporation, it is preferred to use mild precursors of color developing agents.

For example, indoaniline compounds described in U.S. Pat. No. 3,3≠Co, 127, U.S. Pat. /!
The thick base type compound described in No. 9, the fuldol compound described in No. 3P-≠, the metal fence complex described in U.S. Pat. 3-/3! Including the urethane-based compounds described in A Cor.
No. 3, same j Otsu-/bu No. 133, same! Bu-12231,
Same Jbu-bu 7♂4t, No. 2, same! Bu-r373g issue, same JJ-1373! Same issue! Buichi♂37J No. 2, same! t-
♂ No. 2733, No. 1137 of Jj-1, No. !A-!1
No. 71130, lvl! t-10AJ! I1, 4jA
-10723, same 7 futa 7! J/No. and No. 77
Various salt types of precursor tS described in No.-43jAj etc. can be obtained.

The silver halide color light-sensitive material of the present invention may optionally contain 7-phenyl-
3-pyrazolidones may be incorporated. A typical compound is Tokkai Sho! Bu-tri No. 332, same J7-/≠4tJ17
No., J7--///Hiroshi No. 7, same! r-10! JJ issue,
Same j t-j O334, same! r −10J j
J issue, same! ! -403J4', same! ! -! 0! No. 33 and the same! ! -/iru, ir issue, etc.

Various processing solutions in the present invention are used at 10'C-to''c.33''C to 3! Although the temperature of the IC is standard, it is possible to accelerate the processing and shorten the processing time by increasing the temperature to a higher temperature, but it is also possible to improve the image quality and the stability of the processing solution by lowering the temperature to a lower temperature. In addition, in order to save silver on photosensitive materials, treatment using cobalt intensification or hydrogen peroxide intensification as described in West German Patent No. 1, CO-J, No. 770 or U.S. Pat. You can.

Each mild treatment bath may be provided with a heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, a floating pig, a squeegee, etc., as necessary.

Further, during continuous processing, a constant finish can be obtained by using a replenisher for each processing solution to prevent fluctuations in the solution composition. The replenishment amount can be reduced to half or less than the standard replenishment amount to reduce costs.

When the light-sensitive material of the present invention is a color paper, it can be bleach-fixed as required, very generally, and even when it is a color photographic material for photographing.

The present invention will be specifically illustrated below.

Example 1 While stirring, an aqueous silver nitrate solution and an aqueous potassium bromide solution were added to an aqueous gelatin solution containing potassium bromide and ammonia kept at 60°C using a double jet method while maintaining the silver potential at +20 mV with respect to a saturated calomel electrode. .

After the particle formation was completed, the mixture was desalted by a flocculation method, and seratin was added to adjust the pH to 6.3 and the pAg to 8.5.

This silver bromide emulsion had a grain diameter of 0.85 μm (111,
) is a monodispersed tetradecahedral emulsion with a coefficient of variation of particle diameter of 2% (55/45)/(100).

This emulsion was divided into 13 parts, heated to 60°C, sensitizers were added in the form shown in Table 1, and chemical ripening was carried out optimally.

Thereafter, the following compounds were added and coated on a triacetyl cellulose film support having an undercoat layer together with a protective layer by a coextrusion method.

(1) Emulsion layer O emulsion...emulsion shown in Table 1 0 coupler C2H.

o Tricresyl phosphate 0 stabilizer 4-hydroxy-6-methyl-13,3a,
7-Titrasinden 0 Coating aid Sodium dodecylbenzene sulfonate (2) Protective layer 0 Polymethyl methacrylate fine particles 2,4-Cycloro-6-Hydrokiller S -1 Sodium riazine salt 0 Gelatin Sensito on these samples Exposure for measurement (1/100 second) was applied, and the following color development process was performed.

The concentration of the treated sample was measured using a green filter.

The results of the photographic performance obtained are shown in Table 1. Relative sensitivity is expressed as a relative value of the reciprocal of the exposure amount necessary to obtain an optical density of fog value + 0°2, and sample 1 was taken as 100.

The development process used here was carried out at 38°C under the following conditions.

1. Color development...2 minutes 45 seconds 2. Drifting
White...6 minutes 30 seconds 3, wash...
...3 minutes 15 seconds 4, established...
6 minutes 30 seconds5, water washing...3 minutes 15 seconds6, stability...3 minutes 15 seconds The composition of the treatment liquid used in each step is as follows. It is.

Color developer Sodium nitrilotriacetate 1.0g Sodium sulfite 4.0g Sodium carbonate
30.0g potassium bromide
1.4g hydroxylamine sulfate 2.4
g4-(N-Ethyl-N-βhydroxyethylamino)-2-methyl-aniline sulfate 4.5g Add water 11 Bleach solution Ammonium bromide 160.0g Aqueous ammonia (28%) 25.0J Ethylenecyamine -Tetrastic acid sodium salt 1.30 g glacial acetic acid
Add 147nl water
11 Tetrapolyphosphate sodium 2.0g Sodium sulfite 4.0g Ammonium thiosulfate (70%) 175.0ml Sodium bisulfite 4.6g Add water
11 Stabilized liquid formalin 8. 〇-Addition of water A 1β emulsified dispersion was prepared as follows. Selenium sensitizer 1.6XlO- shown in Table 1
'mol and the amount of polymer shown in Table 1 in 1 mol of ethyl acetate.
6-, 95 g of a 12% aqueous gelatin solution and 5+n/ of sodium dodecylbenzenesulfonate (5% aqueous solution) were added thereto, and the mixture was emulsified and dispersed using a homoniser (manufactured by Nippon Seiki).

However, only in the case of sodium thiosulfate, it was dissolved in advance on the side of the aqueous ceratin solution and prepared in the same manner.

/ / / / / / As is clear from Table 1, when the selenium sensitizer is added in the form of emulsion and dispersion with the polymer of the present invention instead of a methanol solution, the occurrence of fog is significantly suppressed, and
A favorable result was obtained in which the sensitivity was almost maintained.

Further, the same results were obtained whether the emulsified dispersion was added in a solid state or in a liquid state after being dissolved in advance.

On the other hand, with a sulfur sensitizer (sodium thiosulfate), there was little fog, but the sensitivity was low, and there was no advantage even if it was made into an emulsified dispersion (reference).

Example 2 To 1.21 g of a 3.0 wt. % seratin solution containing 0.06 mol of potassium bromide, while stirring, a 25 wt. 0. 50cc of 3M silver nitrate solution and 0.06
50 cc of a halogen salt aqueous solution containing 3 mol of potassium iodide and 0.19 mol of potassium bromide was added over 3 minutes using a double jet method. As a result, the projected area equivalent diameter is 0. Nucleation was carried out by obtaining silver iodobromide grains of 2 μm and a silver iodide content of 25 moles. Subsequently, at 75° C., 60 μm of ammonia aqueous solution was added, and 800 ml of a halokene salt solution containing 800 d of 1.5 mol silver nitrate, 0.375 mol potassium iodide, and 1.13 mol potassium bromide was double jetted for 80 minutes. They were simultaneously added by a method to form a first coating layer. The obtained emulsion grains were octahedral silver iodobromide emulsions with an average projection surface ellipse equivalent diameter of 0.95 μm. (Iodide content: 25 mol%).

Subsequently, acetic acid was added to neutralize, and then 1.5 mol silver nitrate solution, 1.5 mol potassium bromide solution, and 2% by weight seratin solution were added to the mixer to form a silver bromide shell (second coating layer). By forming the first coating layer/second coating layer ratio l
1 particles were obtained. The resulting grains were octahedral monodisperse core/shell emulsion grains with a circular phase radius of 1.2 μm.

The resulting emulsion was divided into 5 parts, heated to 56°C, sensitizers were added in the form shown in Table 2, and then chloroauric acid (1,2 x 10
-'1 mol Ag) aqueous solution and potassium thiocyanate aqueous solution (4,0XiO-' mol 1 mol Ag) were added and optimally ripened (the preparation of the emulsified dispersion of the sensitizer is the same as in Example 1). Next, the following sensitizing dyes I-III were added, and a coating aid (sodium dodenlebenzenesulfonate) and a stabilizer (4-hydroxy-6-methyl-1,3,3
a, 7-chitrasinden), antifoggant (1-(m
-Sulfophenyl)-5-mercaptotetrazole monosodium salt) Oil-L2 and an emulsion containing couplers 1 to 4 are added, and a protective layer (ceratin, polymethyl methacrylate particles, and H-1, S-1, 2) is added. (containing) on a triacetylcellulose film support with a subbing layer by a coextrusion method.

Sensitizing dye■ Sensitizing dye■ (CH2)ssO3e (CHz )+5OaNa Sensitizing dye■ Nonacid tricresyl phthalate bis(2-ethylhexyl) Coupler 1 Coupler 2 Coupler 3 H (n)CaH Coupler 4 H cH2=CH -3Q2-CH2-CONHH2 (2) These samples were exposed to light through a yellow filter (1/1.00 second) and subjected to the same color development process as in Example 1.

The concentration of the treated sample was measured using a red filter, and the results shown in Table 2 were obtained.

Relative sensitivity is calculated with sample 14 as 100.

As is clear from Table 2, in the case of gold-selenium sensitization that causes significant fogging, adding a selenium sensitizer together with the polymer of the present invention in an emulsified and dispersed form reduces the fogging, although the sensitivity slightly decreases. The occurrence can be significantly suppressed,
In addition, favorable results were obtained in which fogging could be significantly suppressed by the method of the present invention in the case of gold-selenium-sulfur sensitivity in which a sulfur sensitizer was further used.

A favorable result was also obtained in that sample 15 had a stiffer shoulder in the characteristic curve than sample 14.

Example 3 Potassium bromide, 1,000 onythyl (HO(CHz)2S(CHt)zS(CHz)+OH
) and gelatin were added and dissolved, and a mixed solution of a silver nitrate solution, potassium iodide, and potassium bromide was added to the solution maintained at 70° C. by a double jet method while stirring.

After the addition, the temperature was lowered to 35°C, soluble salts were removed by the usual flocculation method, and then the temperature was lowered to 40°C again.
Raise the temperature to C and add 60 g of gelatin to dissolve and adjust the pH to 6.
Adjusted to 8°.

The obtained tabular silver halide grains had an average diameter of 1.25
The thickness is 0.17 μm, and the average diameter/thickness ratio is 7.4.
The silver iodide content was 3 mol%.

Furthermore, pAg at 40°C was 8.4.

This emulsion was divided into four parts, heated to 62°C, and the sensitizing dye anhydro-5,5'-dichloro-9ethyl-3,3
'-Di(3-sulfopropyl)oxacarbocyanine hydroxide sodium salt (500 µ/AgX 1 mol) and potassium iodide (200 µ/Ag Auric acid (9X10
-' mol 1 mol Ag
was added, and a sensitizer in the form shown in Table 3 was added, followed by chemical ripening for 30 minutes (the method of preparing the emulsified dispersion of the sensitizer was the same as in Example 1).

After the chemical sensitization was completed, 100 g of each emulsion (containing 0.08 mol of Ag) was dissolved at 40 DEG C. and the following solutions (1) to (4) were sequentially added with stirring to prepare a solution.

■ 4-Hydroxy-6-methyl-1,3,3a,, 7-tetrazaindene 3% 2cc■ C17H
-s O(CH+CHO)zs H2% 2.2c
c ■ +CH2-CHf, 2% 1. 6So, 2,4-dichloro-6-hydroxy-5-)-lyazine sodium 2% 3 cc surface protective layer coating solution was added to the solution in sequence at 40 DEG C. with stirring and prepared as follows.

■ 14% Seratin aqueous solution 56.8 g ■ Polymethyl methacrylate fine particles (average particle size 3, 0 μm) 3.9 g ■ Emulsion Seratin 10% 4.24 g CH2C00C
H,CH(C,H5)C,H.

Na03S-CHC○○CH+CH(C2Hs)C-H
-10, 6■ -0H 72% 0.02cc 68゜cc C8H17◇(OCH2CHz+2CH2CH2SO3
Na4, 3% 3cc Together with the emulsion coating solution and the surface protective layer coating solution obtained as above, the coating solution was co-extruded onto a polyethylene terephthalate film support so that the volume ratio at the time of coating was 103:45. Coated. The amount of silver coated is 2.
5g/rr? It is. These samples were exposed to light (1/100 seconds) using a sensitometer through a yellow filter and an optical wedge, and then incubated at 35°C for 30 minutes with an RD-III developer for automatic processors (manufactured by Fuji Photo Film). After developing for seconds, it was fixed, washed with water, and dried by a conventional method, and the photographic sensitivity was measured. Photographic sensitivity is expressed as a relative value of the reciprocal of the exposure amount required to obtain an optical density of fog value + 0.2, and sample 19
was set as 100.

/ / As is clear from Table 3, the method of the present invention was able to significantly suppress the occurrence of selenium sensitization fog even in black-and-white development.

Example 4 (Production method of Em-A) Aqueous solution 1 containing 1.0.5 g of Seratin and 3 g of KBr
000- was stirred at 60°C and A g N Oh (8,
2g) aqueous solution and KBr (5.7g of KBr, 0.7g of Kl)
35g) aqueous solution was added via double jet. Gelatin was added and the temperature was 75°C.

After adjusting the potential to OmV, AgN0. (136°3g
) aqueous solution and KBr (containing 12.0 mol % Kl) aqueous solution were added by double jet. At this time, the silver potential was maintained at OmV with respect to the saturated calomel electrode. silver potential - 60m
After adjusting the temperature to V, the temperature was lowered to 40°C and a silver nitrate aqueous solution (
AgN (0.3.2 g) and KI aqueous solution (2.3 g) were added over 5 minutes. K+IrCj? +7.0X10
−? After adding 1 mol of Ag, a silver nitrate aqueous solution (A g
0.22.3 g of N) and an aqueous KBr solution were added using a double jet over a period of 5° and 35 minutes. At this time, the silver potential was maintained at -100 mV with respect to the saturated calomel electrode.

0.1N thioneanate! After adding A20-,
Desalt by flocculation method, add gelatin, and
Adjusted to H5.5 and pAg8.2.

This emulsion has an average equivalent circle diameter of 1.42 μm and an average thickness of 0.
．． The grains were tabular grains of 21 μm and an average aspect ratio of 6.8. The coefficient of variation of the equivalent circle diameter was 24%.

Em-A was subjected to gold-sulfur-selenium sensitization as follows. The emulsion was heated to 728C and the following sensitizing dye Dye-5 was added.
3.3X10-' mol 1 mol Ag, Dye-6 3.
2X10-'mol 1 mol Ag.

Dye-7 was 1.7X10-5 mol 1 mol Ag, antifoggant V-1 (described later) was 1X10-' mol 1 mol Ag,
and Dye-5 Dye-6 Dye-7 Sodium thiosulfate (2,3XlO-'mol 1 molAg
) aqueous solution, chloroauric acid (9,2XlO-' mol 1 mol Ag
) aqueous solution, potassium thiocyanate (3,0 x 10-' mol 1 mol Ag) aqueous solution, and a selenium sensitizer in the form shown in Table 4 were added to perform optimal chemical sensitization (emulsification of the sensitizer). The method for preparing the dispersion is the same as in Example 1). here"
"Perform chemical sensitization optimally" refers to chemical sensitization that achieves the highest sensitivity when exposed to light for 1/100 seconds after chemical sensitization.

on a subbed cellulose triacetate film support.
Sample 23, which is a multilayer color photosensitive material, was prepared by coating each layer of the composition shown below (Em-A was used for the seventh layer) in multiple layers.
．． 24 was produced.

(Photosensitive layer composition) The numbers corresponding to each component indicate the coating amount expressed in g/, 1 unit, and for silver halide, the coating amount is expressed in terms of silver. However, for sensitizing dyes, the coating amount is expressed in moles per mole of silver halide in the same layer. The structures of various additive compounds are shown below.

1st layer (antihalation layer) Black Koite silver Silver 0.18 Seratin
1.40 Second layer (middle layer) 25-sheet t-pentadecylhydroquinone 0.18EX-10,
07 EX-30,02 EX-120,002 U-10,06 U-20,08 U-30,t.

HBS-10,10 8BS-20,02 Gelatin 1.04 Third layer (donor layer for interlayer effect on red-sensitive layer) Emulsion 9
Silver 1,2 Emulsion 10 Silver 2.0 Sensitizing Dye N 4X10-
'EX-10 B5-1 B5-2 Gelatin 4th layer (intermediate layer) EX-5 B5-1 Gelatin 5th layer (first red-sensitive emulsion layer) Emulsion 1 Emulsion 2 Sensitizing dye I Sensitizing dye ■ Sensitization Dye ■ EX-2 EX-10 B5-1 0゜0゜0゜Silver 0.25 Silver 0,25 1, 5X10-'1.8X10-' 2, 5X10-' 0.335 0.020 0,07 0 , 05 0, 07 0.060 Seratin 6th layer (second red-sensitive emulsion layer) Emulsion 6 Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ EX-2 EX-3 EX-10 Gelatin 7th layer (third red-sensitive emulsion layer) Red-sensitive emulsion layer) m-A EX-3 EX-4 EX-2 EX-8 B5-1 0,87 Silver 1.0 1, 0XIO 1,4X10-' 2.0XI0 0.400 o, os.

O,015 0,07 0,05 0,07 1, 30 B5-2 gelatin 8th layer (middle layer) EX-5 B5-1 Seratin 9th layer (first green emulsion layer) Emulsion 1 Emulsion 2 Sensitizing dye V Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ EX-6 EX-1 EX-7 EX-8 B5-1 B5-3 gelatin 0° 1゜ 0° 0° Q.

silver 0.15 silver 0.15 3.0XIO 1,0XIO 3, 8X10 5. oxi.

Ol 260 0.021 0.030 0.005 0.100 0.010 0, 63 10th layer (second green emulsion layer) Emulsion 3 Sensitizing dye V Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ EX -6 EX-22 EX-7 B5-1 B5-3 Gelatin 11th layer (third green emulsion layer) Emulsion 4 Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ EX-13 EX-11 Silver 0.45 2, lXl0-' 7, OXl, 0 2.6X1.0 5.0X10 0.094 0.018 0.026 0, 160 0.008 0, 50 Silver 1.2 3.5XIO-5 8 ,0XIO 3,0X10 0.5X10-' o,ois O,100 EX-10,025 8BS-10,25 8BS-20,10 Seratin 1.54 12th layer (
Yellow filter layer) Yellow colloidal silver Silver 0.05EX-50
,08 8BS-10,03 Gelatin 0.95 13th layer (
1st blue-sensitive emulsion layer) Emulsion 1 Silver 0.08 Emulsion 2
Silver 0.07 emulsion 5
Silver 0.07 Sensitizing dye ■ 3.5
X10-'EX-90,721 EX-80,042 8BS-10,28 Gelatin 1.10 14th layer (
2nd blue-sensitive emulsion layer) Emulsion 6 Silver 0.45 sensitizing dye■
2. lXl0EX-90,154 EX-100,007 HBS-10,05 Gelatin 0178 15th layer (
3rd blue emulsion layer) Emulsion 7 Silver 0.77 sensitizing dye■
2.2X10-'EX-90,20 HBS-10,07 Gelatin 0.69 16th layer (
1st protective layer) Emulsion 8 Silver 0.20U-40,
11 U-50,17 8BS-10,05 Gelatin 1.00 17th layer (
2nd protective layer) Polymethyl acrylate particles (diameter approximately 1.5 μm) 0.54S-10,
20 Gelatin 1.20 In addition to the above ingredients, each layer contains Seratin hardening agent H-1, EX-1, 4
~21 and a surfactant were added.

／ ／ ／ ／ ／ After exposing the color photographic material as described above, using an automatic processor, use the method described below (until the cumulative replenishment amount of bleaching solution becomes three times the capacity of the mother liquor tank). Processed.

Processing method step Processing time Processing temperature Replenishment amount Tank capacity Color development 3 minutes 15 seconds 38°Cl5ynl 201
Bleach 6 minutes 30 seconds 38°CIOi 4OA
Wash with water 2 minutes 10 seconds 35°C 10d 201
Fixation 4 minutes 20 seconds 38°C2fW 30f
Washing with water (2) 1 minute OO seconds 35°C 20d 10j
2 stable 1 minute 05 seconds 38°C] (W IO
A Drying 4 minutes 20 seconds 55°C The amount of replenishment is indicated as the amount per 35 mm width and 1 meter length.

Next, the composition of the treatment liquid will be described.

(Color developer) Mother solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1-hydroquinethyritine-1,1-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 4-(N-ethyl -N β-hydroxyethylamine) -2- Add methylaniline sulfate solution to pH (bleaching solution) 1.0 3.0 4.0 30.0 1.4 1.5■ 2.4 4.5 1.01 10,05 30.0 1.01 10.10 Mother liquor (g) Replenisher (g) Ethylenediaminetetranodic acid ferric sodium trihydrate Ethylenediamine tetranodic acid disodium chlorideAmmonium bromide Ammonium nitrate Aqueous ammonia (27%) Water (Fixer solution) Disodium ethylenediaminetetranodic acid Sodium sulfite Sodium ammonium thiosulfate aqueous solution (70%) Add water to pH (Washing solution) Mother solution and replenisher common 100, 0 10.0 140, 0 30 .0 6.5d 1.01 6.0 140, 0 11.0 180, 0 40.0 2.5- 1, Ol 5.5 Mother liquor (g) Replenishment solution (g) 0.5 7.0 5. 0 1.0 12.0 9.5 170, Om/ 240.0d 1.01 1.01 6.7 6.5 Tap water was treated with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas ) and an OH type anion exchange resin (Amberlite 1R-400) to reduce the concentration of calcium and magnesium ions to 3 ■/l or less, followed by sodium incyanurate dichloride 20 ■/l and sodium nitrate 1. 5 g/l was added.

The pH of this solution was in the range of 6.5-7.5.

(Stabilizing solution) Formalin (37%) Polyquinoethylene-p-monononylphenyl ether (average degree of polymerization 10%) Add ethylenediaminetetranoic acid disodium salt solution to prepare 1) H Mother solution (g) Replenisher solution (g) 2. 0J 3.0J 0.3 0.45 0.05 0.08 1, Ol 1.01 5, 0-8.0 5, 0-8.0 0 from the fog density and fog density for the characteristic curve of cyan color image ．． Sensitivity is expressed as a relative value of the reciprocal of the exposure amount that gives a higher density. The results obtained are shown in Table 4.

As is clear from Table 4, although the method of the present invention slightly lowered the sensitivity, it was possible to significantly suppress fog in selenium sensitization.

The ability to keep fog low in this way is very significant in this industry. Further, compared to Sample 23, Sample 24 had a favorable result in that the increase in fog over time was small and zero.

X-1 X (i) C, H, 0CNl1 EX-3 EX-4 EX-5 I bH 3(n) EX EX-7 EX-8 H3 C1l□ EX-10 EX-11 H EX-1, 2 EX-13 V-5 B5-1 tricresyl phosphate B5-2 Di-n-butyl phthalate B5-3 Sensitizing dye I Intensifying dye■ Exacerbating pigment■ Exacerbating pigment■ Exacerbating pigment■ Exacerbating pigment■ Exacerbating pigment■ CH.

C) Iz=CH-3Oz-CHz-CONII-CHz
CHz=CH-SCh-CL-CONH-CHzEx
, -14 N-N' Ex-15 Ex-16 Copolymer of polyvinylpyrrolidone and polyvinyl alcohol Ex-11 Ex-18 u? l Ex-19 Benzisothiazolin-3oneEx-20 Butyl-p-hydroxybenzoateEx-21 2-phenoxyethanolEx-22 V-1 (Effects of the Invention) The present invention provides greater beselen sensitization than conventionally known methods. It is possible to suppress the occurrence of fog and achieve almost the same level of high sensitivity.

Claims (1)

[Claims] Chemical sensitization by adding a dispersion obtained by emulsifying and dispersing a mixed solution of a selenium sensitizer and at least one water-insoluble and organic solvent-soluble polymer to a silver halide emulsion. A chemical sensitization method for silver halide emulsions characterized by: