JPH02271346A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To restrain increase of fog and deterioration of sensitivity due to time lapse till the time of using a sensitive material by regulating the extent of rise of sensitivity due to hydrogen sensitization to a specified value or less and a coating amount of gold to a specified value or less. CONSTITUTION:The photographic sensitive material is a color negative sensitive material having, preferably plural red-sensitive-, green-sensitive-, and blue- sensitive-silver halide emulsion layers, and its extent of rise of sensitivity DELTASn represented by expression I due to the hydrogen sensitization is regulated to <=0.05 using the common logarithmic value of an exposure (lux.sec) as the unit, and its ratio of coating amount of gold to that of silver each contained per unit area of the sensitive material is regulated to <=3.0X10<-5>. This emulsion can be prepared by successively adding, for example, a thiosulfonic acid compound and thiourea dioxide to form silver halide grains and then, using chloroauric acid and sodium thiosulfate to execute the gold.sulfur sensitization.

Description

Detailed Description of the Invention [Industrial Application] The present invention relates to a silver halide photographic light-sensitive material with high sensitivity, less fogging, and good graininess. The present invention relates to a silver halide photographic material that is improved in terms of increase in fog and decrease in sensitivity over time before use.

[Conventional technology]

The basic properties required of silver halide emulsions for photography are high sensitivity, low fog, and fine grain.

In order to increase the sensitivity of an emulsion, (11) increase the number of grains absorbed by one grain, (2) increase the efficiency with which photoelectrons generated by light absorption are converted into silver clusters (latent images), and (3) In order to effectively utilize the formed latent image, it is necessary to increase the development activity.

Increasing the size increases the number of photons absorbed by one particle, but
Decrease image quality. IJ! Increasing image activity is also an effective means for increasing sensitivity, but in the case of parallel type development such as color development, graininess generally deteriorates. In order to increase sensitivity without deteriorating graininess, it is most preferable to increase the efficiency of converting photoelectrons into latent images, that is, to increase quantum sensitivity. It is necessary to eliminate as many inefficient processes as possible. It is known that reduction sensitization, which creates small silver nuclei with no development activity inside or on the surface of silver halide, is effective in preventing recombination.

Attempts at reduction sensitization have been considered for a long time.

Carrall (Carroll) U.S. Patent No. 2.487.
No. 850, a tin compound, L. olle et al., No. 2,512,925, a polyamine compound, Fallena et al., British Patent No. 789,823, a thiourea dioxide-based compound. was disclosed to be useful as a reduction sensitizer. Furthermore, Co11ier (Korea) is a Photographer.
cScience and Engjnearing
Vol. 23, p. 113 (1979) compares the properties of silver nuclei produced by various reduction sensitization methods. She dimethylamine borane, stannous chloride, hydrazine,
A method of high pAg! aging and low pAg! formation was adopted.

The method of reduction sensitization is further described in US Patent No. 2.518゜698.
No. 3,201,254, No. 3゜411.91
No. 7, No. 3,779,777, No. 3,930,8
It is also disclosed in No. 67.

Not only the selection of a reduction sensitizer but also the method of using a reducing agent are disclosed in Japanese Patent Publications No. 57-33572, No. 58-1410, and Japanese Patent Application Laid-open No. 57-i79835.

Furthermore, James et al. performed a type of reduction sensitization in which a coated film of a gold-sulfur sensitized emulsion was vacuum degassed and then heat treated in a hydrogen gas atmosphere.
It has been found that sensitivity can be increased at a lower fog level compared to conventional reduction sensitization. This sensitization method is well known as hydrogen sensitization, and is effective as a means of increasing sensitivity on a laboratory scale.

Furthermore, hydrogen enhancement can be used as an evaluation means for detecting how much reduction sensitization has been applied to an emulsion, depending on the extent of increase in sensitivity.

In other words, in a light-sensitive material coated with a reduction sensitized emulsion, if the reduction sensitization effect is sufficient, the increase in sensitivity due to hydrogen sensitization will be small; if the reduction sensitization effect is insufficient, hydrogen sensitization will increase the sensitivity. The increase in sensitivity is large.

Emulsions that have been reduction sensitized by the various methods described above often have an insufficient increase in sensitivity compared to hydrogen sensitization.

This is a Jour of Imaging 5
science Vol. 29, p. 233 (1985)
It has been reported by Isar (Moyser) et al.

Therefore, the sensitivity of the above-mentioned emulsions is further increased by hydrogen sensitization, and the sensitivity of light-sensitive materials using these emulsions is also further increased by hydrogen sensitization.

On the other hand, the silver halide used here is generally chemically sensitized to obtain desired sensitivity, gradation, etc.

The methods include sulfur sensitization using active gelatin or a sulfur-containing compound that can react with silver ions, reduction sensitization using reducing substances, and noble metal enhancement using gold or other noble metal compounds, either alone or in combination. There are known methods for using it. As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used, and specific examples thereof are described in U.S. Pat.
No. 74.944, No. 2,410.689, No. 2.
No. 278.947, No. 2,728.668, No. 3
．． No. 656,955, No. 4,030°928, and No. 4,067.740.

Recently, it has been desired to increase the sensitivity of silver halide emulsions.
To achieve this purpose, among the chemical sensitization methods mentioned above, the gold-sulfur sensitization method, which usually uses a combination of a sulfur sensitizer and a noble metal sensitizer, especially a gold sensitizer, is used. is considered essential.

In this case, the amount of these sensitizers added depends on the state of the silver halide crystal grains to be chemically sensitized (e.g., grain size and distribution, halogen composition, crystal habit, etc.) and the environment (e.g.,
(amount and type of binder, PHlpAg, reaction temperature, reaction time, etc.), and gold sensitization auxiliaries (e.g., promoters such as thiocyanates and thioether compounds, and fog suppressors such as thiosulfonates) It is determined by the type of sulfur aggravator and gold sensitizer actually used. The method is well known to those skilled in the art.

[Problem to be solved by the invention]

The conventional technology of reduction sensitization has not been sufficient to meet the recent demands for photographic materials with high sensitivity and high image quality. Also,
When ordinary gold/sulfur sensitization is applied, reduction-sensitized emulsions are prone to fogging and are unable to fully demonstrate the sensitizing effect of reduction-sensitization. This deterioration of photographic performance over time, which causes deterioration of photographic performance such as increased fog and decreased sensitivity, is caused by sulfur sensitization compared to silver halide emulsions chemically sensitized only by sulfur sensitization. This is thought to be caused by the interaction between gold and reduction sensitizing nuclei, as it is larger compared to light-sensitive materials using high-sensitivity silver halide emulsions that have been chemically sensitized by combining sensitization and gold sensitization. It will be done. Especially in color negative photosensitive materials, increasing the number of development starting points,
f! In order to improve the contrast ratio, the amount of silver halide grains is generally made to be in excess of the amount of coupler, and an increase in fog results in a decrease in the S/N ratio, which poses a serious problem.

The purpose of the present invention is to provide a halogenated material with high sensitivity, good graininess, less fogging, and improved photographic performance deterioration such as an increase in fogging over time from the time the photosensitive material is manufactured until it is used. It is the preparation of silver photographic materials.

(Means for Solving Problem 1) An object of the present invention is to provide a silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support, in which the lux・The sensitivity increase width △Sn due to hydrogen sensitization in units of the common logarithm of the exposure amount expressed in seconds is 0°05 or less, and the amount of silver applied is equal to the amount of gold contained in the photosensitive material per unit area. 1. A silver halide photographic light-sensitive material having a weight ratio (gold/silver) of 3.0×10 −' or less.

△Sn=　　　’″1 achieved by.

The present invention will be explained in detail below.

First, the increase in sensitivity due to hydrogen sensitization in the present invention ΔSn
The definition of is explained in detail.

Hydrogen sensitization is carried out by leaving the photosensitive material at 30° C. for 30 minutes and 60 minutes in a container that has been vacuum degassed and replaced with hydrogen.

Photographic sensitivity is defined as follows depending on the type of photosensitive material.

Note that the exposure of the photosensitive material shall be carried out within 2 hours after the completion of the hydrogen sensitization process.

1. After leaving the color negative photographic material sample under the conditions of 40° C. and 70% relative humidity for 14 hours, it is exposed to light for 1/100 second through a continuous wedge and subjected to the next color development process.

Processing Steps Color development was carried out at 38° C. according to the following processing steps.

Color development 3 minutes 15 seconds Bleach White 6 minutes 30 seconds Water Wash 2 minutes 10 seconds Fixed arrival time: 4 minutes 20 seconds Water Wash 3 minutes 15 seconds Stability 1 minute 05 seconds The composition of the treatment liquid used in each step is as follows.

Color developer diethylenetriamine pentaacetic acid 1-hydroxyethylidene-1,1-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 4-(N-ethyl-N-β-hydroxyethylamino) -2-methyl Add aniline sulfate and H Bleach solution Ethylenediaminetetraacetic acid ferric ammonium salt Ethylenediaminetetraacetic acid disodium salt Ammonium bromide Ammonium nitrate 1,0g 4,5g 1,(1 10,0 100,0g 10.0g 150.0g 10 Add .0g water and H Fixer ethylenediaminetetraacetic acid disodium salt sodium sulfite ammonium thiosulfate aqueous solution (70%) Add sodium bisulfite water and H Stabilizer formalin (40%) Polyoxyethylene-p-monononylphenyl ether ( Average degree of polymerization 10) Add water 1,01 6.0 1,0g 4,0g 175.0m1 4,6g 1,01 6.6 2,0m 1 0,3g 1,0! Treated sample Measure the density with a red filter, a green filter, and a blue filter.The exposure amount corresponding to a density 0.15 higher than the minimum density of each of red, green, and blue is expressed in lux seconds and is expressed as H++, Ha, and Ha, respectively. and each common logarithm value is S.

Let Ss - Ss.

After hydrogen aggravation, Si+, Sa, and Ss are each S***
, Sawt, Sawz, 63m =S*xt
−5t, Δ5a=S*. -89, △5l-5□2-3°ΔSll +ΔS0 +ΔS.

It is.

2. A color reversal photographic light-sensitive material sample was exposed to light for 1/100 seconds through a continuous wedge, and the following development process was performed.

Processing wedge process Time Temperature first development 6 minutes 38℃ water washing
2 minutes inversion, 2 minutes color development, 6 minutes adjustment, 2 minutes bleaching, 6 minutes fixing, 4 minutes washing, 4 minutes stabilization, 1 minute drying The following processing solution was used.

Kojiya FukuA Water nitrilo-N,N,N-)rimethylenephosphonic acid pentasodium salt Sodium sulfite Hydroquinone monosulfonate Sodium carbonate (-hydrate salt) 1-Phenyl-4methyl-4-hydroxymethyl- 3 Birazolid 38℃ Room temperature 700ml 2g 0g 0g 0g Potassium bromide Potassium thiocyanate Potassium iodide (0.1% aqueous solution) Add water and prepare anti-Hanshin water nitrilo-N,N,N-4 rimethylenephosphonic acid. Sodium salt Stannous chloride (dihydrate) p-Aminophenol Sodium hydroxide Add glacial acetic acid water and add 1 double water nitrilo-N,N,N-trimethylenephosphonic acid pentasodium salt g 2.5 g 1 .2g m1 1 000m1 700m1 g g 0, 1 g g 1 5mj! 1 000ml 700ml g Sodium sulfite Sodium triphosphate (12 hydrate) Potassium bromide Potassium iodide (0.1% aqueous solution) Sodium hydroxide Citrazate N-ethyl-N-(β-methanesulfonamidoethyl)- 3-Methyl-4-aminoaniline sulfate 3.6-cythiaoctane-1. Add 8-diol water and add H Weekly water Sodium sulfite Sodium ethylenediaminetetraacetate (dihydrate) Thioglycerin g 6g g Qm1 g 1, 5g 1g g 1000ml 12, 0 700mj+ 2g g Q, 4ml Add glacial acetic acid water Sodium ethylenediaminetetraacetate (dihydrate) Iron (III) ethylenediaminetetraacetate Ammonium (dihydrate) Add potassium bromide water and add 1 melon water Sodium thiosulfate Sodium bisulfite water Substance melon water formalin (37% by weight) Fuji Drywell (Fujifilm mN 1 000mj! 8 00m! g 20g 00g 1000mj1 800rn1 80, 0g 5, 0g 5, 0g 1 000mA! 800mJ 5, 0 ml ■ Surface active agent) 5.0 m f
i Add water to 1000mj! Measure the concentration of the treated sample using a red filter, green filter, and blue filter. The common logarithmic values of the exposure amount expressed in lux seconds at an optical density of 1.0 for red, green, and blue are Sll and 5GSS, respectively.

After hydrogen sensitization, S, , S, , S, are each S□3
, S*hz , St□, then △Se-SllNg
S@, △5G=SG to x-8Gx△5l=SIN□
-8l68m +ΔS, ÷ΔS.

It is.

3゜ A black and white negative photographic material sample was stored at 25°C and a relative humidity of 65% for 7 days after coating, and then exposed to tungsten light through a continuous wedge for 17 days.
Expose for 10 seconds.

After developing for 7 minutes at 20°C with a developer having the following formulation, the film was stopped, fixed, washed with water, and dried in the usual manner.

Developer Metol 2g Sodium sulfite 100g Hydroquinone
After adding 5g volax・l0F (,02g water) and the 11th development process, the common logarithm value of the exposure amount expressed in lux seconds at a constant density higher than the fog density (optical density of 03l) is S
shall be.

If S after hydrogen sensitization is SWt, △S-”=SngS It is.

In order to reduce the sensitivity increase ΔS7 due to hydrogen sensitization, it is essential to subject the silver halide emulsion to sufficient reduction enhancement.

A preferred reduction sensitization method will be described in detail below.

The manufacturing process of silver halide emulsions is roughly divided into steps such as grain formation, desalting, chemical sensitization, and coating.
It is divided into maturity, growth, etc. These steps are not performed uniformly; the order of the steps may be reversed, or the steps may be repeated. The term "reduction sensitization" being carried out during the production process of the silver halide emulsion basically means that it can be carried out at any step. Reduction sensitization may be performed during nucleation, which is the initial stage of particle formation, during physical ripening, or during growth, and may be performed either before or after chemical sensitization. Here, chemical sensitization preferably refers to gold sensitization or sulfur sensitization. When chemical sensitization is performed in combination with gold sensitization, reduction sensitization is performed prior to chemical sensitization to avoid undesirable fogging. It is preferable to do this. The most preferred method is reduction sensitization during the growth of silver halide grains. Growing refers to methods in which reduction sensitization is performed while the silver halide grains are growing through physical ripening or addition of a water-soluble root salt and a water-soluble alkali halide, and methods in which growth is temporarily stopped during growth. This means that it also includes a method for further growth after performing reduction aggravation in a state.

The reduction sensitization of the present invention is a method of adding a known reducing side to a silver halide emulsion, a method of growing or aging in an atmosphere of low pA of pA of 11 to 7, which is called SR thermal ripening, and a method of growing or aging at a pH of 8, which is called high pHP composition. It is possible to select either a method of growing or aging in an atmosphere with a high PL of 11 to 11.Furthermore, two or more methods can be used in combination.

- The method of adding a reduction sensitizer is a preferable method because it allows the level of reduction sensitization to be finely adjusted.

As reduction sensitizers, stannous salts, amines and polyamines, hydrazine derivatives, formamidine sulfinic acid, silane compounds, borane compounds, etc. are known.9 In the present invention, any of these known compounds can be used. Moreover, two or more kinds of compounds can also be used together. Preferred compounds as reduction aggravating agents are stannous chloride, thiourea dioxide, and dimethylamine borane. The amount of the reduction aggravating agent to be added depends on the emulsion manufacturing conditions and must be selected, but it is suitably in the range of 10@-7 to io-'' moles per mole of silver halide.

Reduction sensitizers include water, alcohols, glycols,
It can be dissolved in a solvent such as ketones, esters, amides, etc. and added during particle formation, before or after chemical sensitization. It may be added at any stage of the emulsion manufacturing process, but it is particularly preferred to add it during grain growth. Although it is possible to add the reduction sensitizer to the reaction vessel in advance, it is preferable to add it at an appropriate time during particle formation. Particles may be formed using an aqueous solution. Also, with particle formation, reduction increase Iv151iq
It is also a preferable method to add the solution in several parts or continuously over a long period of time.

In addition, in the manufacturing process of the silver halide emulsion, reduction sensitization may be performed and at least one compound selected from the compounds represented by the general formula (1), [■] and [■] may be added during the manufacturing process. A method for producing a silver halide emulsion is particularly preferred.

R-3o S-M (n) R-5o, S-R' (I[1) R3Oz S-L, 5SOz -R'' in the formula,
R, R', R'' may be the same or different and represent an aliphatic group, an aromatic group, or a heterocyclic group, M represents a cation, L represents a divalent linking group, and m represents Q or 1.

To explain the compounds of general formulas (1), [■] and (II+) in more detail, when R, R' and R2 are aliphatic groups, preferably an alkyl group having 1 to 22 carbon atoms, and 2 carbon atoms. These are alkenyl groups and alkynyl groups of 22, which may have a W substituent. Examples of alkyl groups include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group. group, 2-ethylhexyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group, cyclohexyl group, isopropyl group, t
-butyl group, etc.

Examples of the alkenyl group include allyl group and butenyl group.

Examples of the alkynyl group include propargyl group and butynyl group.

The aromatic groups for R, R' and R8 preferably have 6 to 20 carbon atoms, such as phenyl and naphthyl groups. These may be substituted.

The heterocyclic group of R, R' and R8 includes nitrogen, oxygen,
A 3- to 15-membered ring containing at least one element selected from sulfur, selenium, and tellurium, such as pyrrolidine ring, piperidine ring, pyridine ring, tetrahydrofuran ring, thiophene ring, oxazole ring, thiazole ring, imidazole ring, and benzothiazole ring. ring, benzoxazole ring, benzimidazole ring, selenazole ring, benzoselenazole ring, tetrazole ring, triazole ring, benzotriazole ring, tetrazole ring, oxadiazole ring, thiadeazole ring, and the like.

Substituents for R, RI and Rt include, for example, alkyl groups (e.g. methyl, ethyl, hexyl), alkoxy groups (e.g. methoxy, ethoxy, octyl), aryl groups (e.g. phenyl, naphthyl, tolyl), hydroxy groups, halogen atoms (fluorine, chlorine, bromine, iodine),
Aryloxy groups (e.g. phenoxy), alkylthio groups (e.g. methylthio, butylthio), arylthio groups (e.g. phenylthio), acyl groups (e.g. acetyl, propionyl, butyryl, valeryl), sulfonyl groups (e.g. methylsulfonyl, phenylsulfonyl) ), acylamino group (e.g. acetylamino, benzamino), sulfonylamino group (e.g. methanesulfonylamino, benzenesulfonylamino), acyloxy group (e.g. acetoxy, benzoxy), carboxyl group, cyano group, sulfo group, amino group, etc. can be given.

L is preferably a divalent aliphatic group or a divalent aromatic group. Examples of the divalent aliphatic group of L include *CHx
+, 1 (n-1~l2), -CHArCH-CH
Examples of the divalent aromatic group of L include a -CH orsilylene group, and examples thereof include a phenylene group and a naphthylene group.

These substituents may be further substituted with the substituents described above.

M is preferably a metal ion or an organic cation. Examples of metal ions include lithium ions, sodium ions, and potassium ions. Examples of organic cations include ammonium ions (ammonium, tetramethylammonium, tetrabutylammonium, etc.), phosphonium ions (tetraphenylphosphonium), guanidyl groups, and the like.

Specific examples of the compound represented by the general formula (13, (I[]) or (III) are listed below, but the compound is not limited thereto.

(11) CH3SO25Na (1-2) Cz Hs Sow SNa(]-9) Cs Hs SCh 5K Ca He SOx S L I C6HezSOt SNa Cm HevSOx 5Na CHs (CHI)3 CHCHz Sot S・
NHaC, H% C+ o Ht + S Ot S NaC+zHz
sSOz 5Na CrhHzsSOz 5Na t-Ca Hq 5otSNa CHs 0CHz CHt 5O1S-NaC (To○x
sNa CH3C0NHGSCh 5Na CH:I ODSOx 5Na H2N ◇so, 5Na CH3Qso, 5Na Hoz C◇SO□5K CHz =CHCHz SOz 5Na (2-1,) Cz Hs So □S-CH3 Cs HuSCh SCH! CHs Cz Hs So□5CI(ICHz CNCz Ha
SO2SCH! CHz Sow 5CHt, CHt
5SOz Cz HsCIIzCIbOH CIl□C) 1.0R Ct Hs SO2SCH! CHt CH yo CHt
The compound of OH general formula (1) can be easily synthesized by the method described in JP-A-54-1019 and British Patent No. 972,271.

The compound represented by the general formula (+), (II) or (III) is 10-7 to 10-' per mole of silver halide.
Preferably, the molar addition is further from 101 to 10-1
In particular, an amount of 10-' to 10-1 mole of Ag is preferred.

-a In order to add the compounds represented by formulas (1) to (III) during the manufacturing process, methods commonly used for adding additives to photographic emulsions can be applied.

For example, for water-soluble compounds, make an aqueous solution of an appropriate concentration,
Compounds that are insoluble or sparingly soluble in water are dissolved in a suitable organic solvent that is miscible with water, such as alcohols, glycols, ketones, esters, amides, etc., and does not adversely affect photographic properties. However, it can be added as a solution.

The compound represented by compound (1), (II) or (II) may be added at any stage during grain formation of the silver halide emulsion, before or after chemical sensitization, preferably during reduction. In this method, a compound is added before or during sensitization. Particularly preferred is a method in which it is added during grain growth.

Although it is possible to add the compounds (1) to (I[ These aqueous solutions may be used to form particles, or even if the solutions of compounds (1) to (Ill) are added in several portions as particles are formed, they may be added continuously for a long time. It is also a preferable method to do so.

The most preferred compound general formula for the present invention is a compound represented by general formula (r).

In order to reduce the sensitivity increase ΔS7 due to hydrogen sensitization, it is also preferable to include a hydrazine derivative in the silver halide emulsion layer, as described in JP-A-62-27731. In this case, it is more effective to use a hydrazine derivative and a spectral sensitizing dye together, as described in Japanese Patent Applications No. 63-97905 and No. 63-175393.

The sensitivity increase range ΔS due to the hydrogen sensitization mentioned above is shown below for the main color negative photographic light-sensitive materials currently on the market as prior art.

The silver halide emulsion contained in the light-sensitive material of the present invention includes:
Chemical sensitization is usually performed using a combination of sulfur sensitizer and gold sensitizer.

If the amount of gold is simply reduced in order to reduce the weight ratio of the total amount of gold coated to the total amount of silver coated, several undesirable problems will occur, such as a decrease in sensitivity and a soft tone. Therefore, it is extremely preferable to combine the present invention with a means for effectively sensitizing gold with a small amount of gold compound.

Specific methods for effectively causing the gold sensitizer to exist in the silver halide grain phase include, but are not limited to, the following methods.

For more information, see Research Disclosure magazine December issue 1
978 Item (Hem) No. 17643, 11A
It is described in the section.

(a) A method in which the emulsion after gold sensitization is treated with a porous adsorbent, an ion exchange resin, etc. before being coated on a support, and the gold sensitizer remaining in the binder phase is adsorbed and removed.

The porous adsorbent mentioned here is a porous solid adsorbent (also called an adsorbent) with a large surface area, and specifically includes activated carbon, activated alumina, activated clay, and silica-based adsorbents (water-resistant (preferably)
, Inorganic porous adsorbents such as zeolite-based adsorbents, porous glass, and porous ceramics.

Among these, activated carbon is most preferred.

In addition, ion exchange resins specifically include cation exchange resins (for example, trade name Amberlite IR-120; manufactured by Rohm and Haas Co., Ltd.), anion exchange resins (for example, trade name Diaion 5A-
2LA, manufactured by Mitsubishi Kasei Co., Ltd. (trade name: DOWEX 1×8; manufactured by Dow Chemical Company, etc.), amphoteric resins and chelate resins (for example, trade name: DIAION CR-20; manufactured by Mitsubishi Chemical Company, etc.).

Many types of these ion exchange resins are commercially available, and one suitable for each purpose can be easily obtained.

Among these, anion exchange resins, amphoteric resins and chelate resins are preferred, and anion exchange resins are most preferred.

For details on how to use these adsorbents and ion exchange resins, see Japanese Patent Application No. 60-61429 and No. 60-6.
1430 in detail.

(b) A method of washing the emulsion after gold sensitization with water before coating it on the support.

As the washing method, a known flocculation method or noodle method may be used. The washing liquid used in this case may be only water, or may be an aqueous solution containing an alkali halide, a thioanate, a sulfite, or the like.

(C) A method in which a necessary amount of the binder phase in which the gold sensitizer remains is removed from the emulsion after gold sensitization by a mechanical method such as centrifugation, and a new required amount of binder is added.

(d) Decreasing the amount of gelatin present in the silver halide emulsion during gold sensitization.

(a) Palladium compounds such as palladium chloride are used in combination with gold compounds.

These methods may be used alone or in combination.

The object of the present invention is achieved by setting the weight ratio of the amount of gold coated to the amount of silver coated per unit area of the photosensitive material (hereinafter referred to as the weight ratio of the total amount to the total silver amount) to 3.0X10-' or less. can. The smaller the amount of gold, the greater the effect of the present invention. However, if the amount of gold is too small, deterioration in photographic properties may not be fully recovered even if effective gold sensitization is performed by the method described above. Therefore, the weight ratio of the total amount of silver to the total amount of gold is 2.0X10-1 to 3.0X10-', preferably 1.0X10-' to 2.0X10-', more preferably 1.0X10-' to 1 .0X10-'.

In the case of a color negative photographic light-sensitive material, the constituent red-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer and blue-sensitive silver halide emulsion layer are used to improve graininess and wide exposure latitude. It consists of at least two photosensitive layers, each having a different sensitivity from the other (British patent 923).
Silver halide grains of various sizes are used in these photosensitive layers.

The amount of the gold compound used is preferably approximately proportional to the total surface area of the silver halide grains (surface area of one grain x number of grains).

The amount of gold is preferably reduced in the highest sensitivity layers of the red-sensitive layer, green-sensitive layer, and blue-sensitive layer, and more preferably in all layers.

It is preferred that 70% or more, more preferably 80% or more of the total amount of gold sensitizer is present in the silver halide grain phase.

The proportion of gold present in the silver halide grain phase is as follows (i)
, (ii), (iii), etc. can be performed for analysis.

(+) The silver halide emulsion dispersion before being coated on the support is separated into a silver halide grain solid phase and a binder phase by centrifugation, and each is analyzed by the analysis method described below to determine the amount of gold sensitizer. Quantify.

(ii) For coatings coated on a support, the silver halide emulsion is peeled from the support by swelling with water and enzymatic decomposition or acid decomposition, and then the silver halide grain solid phase and binder are removed by centrifugation. The amount of gold sensitizer in each phase is determined by the analytical method described below.

(iii) For coatings coated on a support, the coating is directly coated with a dilute aqueous solution of sodium thiosulfate (e.g.
If the gold sensitizer in the binder phase is washed away thoroughly while being careful not to fix the silver halide with an aqueous solution of o.o.i.
By quantifying the amount of total gold sensitizer in the coated material before and after the sodium thiosulfate bath treatment, the amount of gold sensitizer in the silver halide grain solid phase and binder phase can be determined.

For more information on method (iii), please refer to the book by P. A. Fattens, Photography Korresp.
ondenz), 104S.

137-146 (1968).

In particular, it is preferable to determine by method (iii) or (+).

Here, it is preferable to quantify gold by a simple and highly accurate atomic absorption method, and the measurement method is, for example, as described in (III) above.
For coatings coated on a support of
For measurement, Hitachi Polarized Zeeman Atomic Absorption Photometer 180-80
I used a mold.

If the proportion of gold present in the silver halide grain phase is low, that is, the proportion of gold in the binder phase is high, diffusion may occur over time after chemical sensitization, before coating on the support, and even after coating. It is presumed that this causes gold in the binder phase to migrate to the silver halide grain phase, which tends to cause undesirable changes in photographic properties such as sensitivity, gradation, and fog over time.

Note that the total amount of gold in the present invention, that is, the amount of gold coated per unit area of the photosensitive material, refers to the amount of gold included per unit area of all layers including the silver halide emulsion layer in the produced photosensitive material. M (amount of gold measured by atomic absorption spectrometry) of gold and gold compounds.

In the photographic emulsion layer of the photographic light-sensitive material used in the present invention, any silver halide including silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride may be used. Preferred silver halides are silver iodobromide, silver bromide, and silver chlorobromide containing up to 30 mol % of silver iodide.

The silver halide grains used in the present invention may be normal crystals that do not contain twin planes; Select from single twins containing one crystal plane, parallel multiple twins containing two or more parallel twin planes, nonparallel multiple twins containing two or more nonparallel twin planes, etc. depending on the purpose. In the case of normal crystals, it is a cube consisting of (100) planes, an octahedron consisting of (111) planes, and the Japanese Patent Publication No. 55-427.
37, disclosed in Japanese Patent Application Laid-Open No. 60-222842 (l
Dodecahedral particles consisting of I 2 O) planes can be used. Furthermore, Journal of ImagingSc
as reported in 1986, (211) is a representative (hl, 1) plane particle, (331) is a representative (hhl) plane particle, (21)
Although (h k o) plane particles representing the 0) plane and (nkl) plane particles representing the (321) plane require some ingenuity in their preparation methods, they can be selected and used depending on the purpose. (100)
Tedecahedral particles in which a plane and a (111) plane coexist in one particle, particles in which a (100) plane and a (110) plane coexist, or particles in which a (1,11> plane and a (11,0) plane coexist), etc.
Particles having two surfaces or a large number of surfaces coexisting can also be selected and used depending on the purpose.

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

A so-called monodisperse silver halide emulsion having a narrow grain size distribution in which 80% or more of all grains fall within ±30% of the average grain size in terms of grain number or weight can be used in the present invention. In addition, in order to satisfy the target gradation of a light-sensitive material, two or more types of monodisperse silver halide emulsions with different grain sizes are mixed in the same layer or in separate layers in emulsion layers having substantially the same color sensitivity. can be coated with heavy nitrogen. Furthermore, two or more types of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be mixed or layered for use.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Grafkide, published by Paul Montell (P.

Glafkides, Chjsie et Phy
sique Photographque Paul
Montel, 1967), Duffin, “
"Photographic Emulsion Chemistry", published by Focal Press (G, F.

Duffin, Photographic Emul
sion Chemistry (Focal Pres.
s, 1966), “Manufacture and Coating of Photographic Emulsions” by Zelikman et al., published by Focal Press (V, L,
ZeHkman et al., Making and
CoatingPhotographic Emuls
ion, Focal Press+ 1964)
It can be prepared using the method described in et al.

That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble root salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. It is also possible to use a method (so-called back-mixing method) in which good single grains are formed under an excess of silver ions. As one form of the simultaneous mixing method, a method of keeping I) Ag in the liquid phase in which silver halide is produced, ie, the so-called Chondrald double jet method, can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

The silver halide emulsion consisting of the regular grains described above can be obtained by controlling pAg and pH during grain formation. For more information, please see Photographic Science and Engineering (Photographrc).
5science and Engineering>Volume 6, pp. 159-165 (1962); Journal of Photographic ScienceUournalof
Photographic 5ctence),
12, 242-251 (1964), U.S. Patent No. 3.655°394 and British Patent No. 1,413,
It is described in No. 748.

Further, tabular grains having an aspect ratio of 3 or more can also be used in the present invention. Tabular grains are described in Cripe's Theory and Practice of Photography J (C1eve.

Photography Theory and Pr
actice (1930)).

131 pages; Gatoff, Photographic Science
and Engineering (Cutoff + Photo
graphic 5science and engineering
14ti, pp. 248-257 (
1970); U.S. Patent No. 4,434.226, 4
．． 414. No. 310, No. 4,433.048, No. 4. 439°520J+ and British Patent No. 2,112
, No. 157 and the like. The use of tabular grains has advantages such as increased covering power and increased color sensitization efficiency by sensitizing dyes, which are detailed in U.S. Pat. No. 4,434,226 cited above. .

Tabular grains are preferred as emulsions of the present invention.

In particular, particles with an aspect ratio of 3 to 8 account for 50% of the total projected area.
Tabular grains occupying the above amount are preferable.

The crystal structure of these emulsion grains may be --like, the inside and outside may have different halogen compositions, or they may have a layered structure.
No. 46, U.S. Patent No. 3,505.0513, U.S. Patent No. 4,4
44,877 and Japanese Patent Application No. 58-248469.

Further, silver halides having different compositions may be joined by epixaxial joining, and for example, silver halides such as rhodan silver,
It may be bonded with a compound other than silver halide, such as lead oxide.

The silver halide emulsion of the present invention preferably has a distribution or structure regarding the halogen composition in its grains.
Typical examples are JP-B No. 43-13162 and JP-A No. 6.
These are core-shell type or double-structured particles in which the interior and surface layers of the particles have different halogen compositions, as disclosed in JP-A No. 1-215540, JP-A-60-222845, JP-A-61-75337, and the like. In such particles, the shape of the core portion and the overall shape including the shell may be the same or different. Specifically, the core part has a cubic shape, and the shape of the shelled particle may be cubic or octahedral. Conversely, the core may be octahedral and the shelled particle may be cubic or octahedral. Furthermore, although the core portion is a clearly regular particle, the shelled particle may have a distorted or irregular shape. In addition, instead of a simple double structure, it is possible to create a triple structure as disclosed in JP-A No. 60-222844, or a multilayer structure with more than that, or a halogen with a different composition on the surface of the core-shell double structure particle. You can apply a thin layer of silver.

In order to give a structure to the inside of a particle, it is not only possible to create a structure that envelops it as described above (it is also possible to create a particle that has a so-called bonding structure.
0, Japanese Patent Publication No. 58-108526 EP199290A
2. Japanese Patent Publication No. 58-24772, Japanese Patent Publication No. 59-16254
etc. are disclosed. The crystal to be bonded can have a composition different from that of the host crystal and can be formed by bonding to an edge, part of a corner, or surface of the host crystal.

Such a bonded crystal can be formed even if the host crystal is uniform in terms of halogen composition or has a core-shell structure.

Although it is naturally possible to combine silver halides with each other in the case of a bonding structure, a bonding structure can be obtained by combining a silver halide with a silver salt compound that does not have a rock salt structure, such as silver rhodan or silver carbonate. Further, non-silver salt compounds such as PbO may also be used if a bonded structure is possible.

In the case of silver iodobromide grains having these structures, for example, in a core-shell type grain, even if the core part has a high silver iodide content and the shell part has a low silver iodide content, or conversely, the core part has a low silver iodide content. The particles may have a low silveride content and a high shell portion. Similarly, grains having a bonded structure may be grains in which the host crystal has a high silver iodide content and the bonded crystal has a relatively low silver iodide content, or vice versa.

In addition, the boundaries between particles with these structures with different halogen compositions may be clear boundaries, or may be unclear boundaries due to the formation of mixed crystals due to composition differences, or may be actively continuous boundaries. It may also be one with some structural changes.

The silver halide emulsion used in the present invention is EP-009672.
781, EP-0064412B1, etc., or DE-2
The surface may be modified as disclosed in JP-A-60-221320, No. 306447C2.

The silver halide emulsion used in the present invention is preferably a surface latent image type emulsion, but an internal latent image type emulsion can also be used by selecting the developer or development conditions, as disclosed in JP-A-59-133542. can. A shallow internal latent image type emulsion covered with a thin shell can also be used depending on the purpose.

Silver halide solvents are useful to accelerate ripening. For example, it is known to have an excess of halogen ions present in the reactor to promote ripening. It is therefore clear that ripening can be accelerated simply by introducing a halide salt solution into the reactor. Other ripening agents can be used, and these ripening agents can be incorporated in their entirety into the dispersion medium in the reactor before the silver and halide salts are added, and one or more ripening agents can be used. can also be introduced into the reactor along with the addition of halide salts, silver salts or flocculants. As a further variant, the ripening agent can also be introduced independently at the halide salt and silver salt addition stages.

As ripening agents other than halogen ions, ammonia or amine compounds, thiocyanate salts such as alkali metal thiocyanate salts, especially sodium and potassium thiocyanate salts, and ammonium thiocyanate salts can be used.

In the present invention, it is extremely important to perform chemical sensitization such as sulfur sensitization and gold sensitization. The location of chemical sensitization varies depending on the composition, structure, and shape of the emulsion grains, as well as the intended use of the emulsion. When chemical sensitization is embedded inside a single grain, it is necessary to embed the chemical sensitization at a shallow position from the grain surface. Although the effect of the present invention is also effective in cases where chemical sensitizing nuclei are formed on the surface or where chemical sensitizing nuclei are formed on the surface, it is particularly preferable when chemical sensitizing nuclei are formed near the surface. In other words, surface latent image type emulsions are more effective than internal latent image type emulsions.

Chemical exacerbation is James (T, H, James)
The Photographic Process, 4th edition, Macmillan Publishing, 1977, (T. H. James.

The Theory of the Photographer
aphic Process + 4thed,
MacmiHan, l 977) 67 76
This can be done using activated gelatin as described on page 12, or as described in Research Disclosure 12.
Volume 0, April 1974, 12008; Research Disclosure, Volume 34, June 1975, 13452;
U.S. Patent No. 2,642,361, U.S. Patent No. 3,297.44
No. 6, No. 3.772.031, No. 3,857,711
No. 3,901°714, No. 4,266.018, and No. 3904.415, and British Patent No. 1
pAgs~10 as described in , 315°755.
．． It can be carried out using sulfur, selenium, chilli, gold, platinum, palladium, iridium or multiple combinations of these sensitizers at a pH of 5-8 and a temperature of 30-80°C. Chemical sensitization is optimally carried out in the presence of a gold compound and a thiocyanate compound and as described in U.S. Patent No. 3,857,711.
No. 4,266°018 and No. 4,054,45
Chemical sensitization can also be carried out in the presence of a chemical sensitization aid in the presence of a sulfur-containing compound described in No. 7 or a sulfur-containing compound such as hypo, thiourea compound, or rhodanine compound. The chemical sensitization aid used is a compound known to suppress fog and increase sensitivity during the chemical sensitization process, such as azaindene, azapyridazine, and azapyrimidine. Examples of chemical sensitization aid modifiers include U.S. Pat.
No. 1.914, No. 3,554.757, Japanese Unexamined Patent Publication No. 1983-
No. 126526 and the aforementioned "Photographic Emulsion Chemistry" by Duffin.
, pp. 138-143.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles1. mercaptothiazoles,
Mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, penzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially l-phenyl-5-mercaptotetrazole), etc.; mercaptopyrimidines frequently: Mercabutotriazines; thioketo compounds such as oxadorinthion; azaindenes, such as triazaindenes, tetraazaindenes (particularly 4-hydroxy substituted (1,3,3a,7)tetraazaindenes), pentazaindenes; Many compounds known as antifoggants or stabilizers can be added, such as azaindenes and the like. For example, U.S. Patent 3,95
No. 4.474, No. 3,982.947, Special Publication No. 1972-
28,660 can be used.

The photographic emulsion used in the present invention may be spectrally sensitized with methine dyes and others. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, Included are styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyridine nucleus, oxazoline nucleus, thiozoline nucleus, virol nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus,
Pyridine nuclei, etc.; Nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei; and nuclei in which aromatic hydrocarbon rings are fused to these nuclei, i.e., indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxane nucleus, etc. Dole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or complex merocyanine dyes include a core with a ketomethylene structure, such as a birapurin-5-one core, a thiohydantoin core, and a 2-thioxazolidine-2 core.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbyl nucleus, and the like can be applied.

These sensitizing dyes may be used alone or in combination, and combinations of enhancing dyes are often used particularly for the purpose of supersensitization.

A typical example is U.S. Patent No. 2,688,545, 2.9
No. 77.229, No. 3,397,060, No. 3,52
No. 2,052, No. 3,527.641, No. 3,617
, No. 293, 3. 628. No. 964, 3,66
6.480, 3,672゜898, 3,679
, No. 428, No. 3,703.377, No. 3,769,
301, 3゜814.609, 3,837,8
No. 62, No. 4.206,707, British Patent No. 1,344
．． No. 281, No. 1,507,803, Special Publication No. 4349
No. 36, No. 53-12.375, JP-A No. 52-110
, No. 618 and No. 52-109,925.

Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect, or a substance that does not substantially absorb visible light but exhibits supersensitization.

The timing of adding the dye into the emulsion is the emulsion that has been known to be useful! It may be carried out at any stage after chemical sensitization is completed, but before coating, as described in U.S. Pat. No. 3,628,969 and U.S. Pat. It is also possible to perform spectral sensitization at the same time as chemical sensitization by adding it at the same time as a chemical enhancer, as described in JP-A-58-113,928. It can be carried out in advance, or it can be added before the completion of silver halide grain precipitation to start spectral sensitization. Furthermore, it is possible to add these compounds separately as taught in U.S. Pat. It is also possible to add it after the reaction, as described in U.S. Patent No. 4,183.
, 756, at any time during silver halide grain formation.

The amount added is 4X10-' to 8 per mol of halogenated
Although it can be used in an amount of X10'□3 moles, about 5X10-' to 2X10-3 moles are more effective when the silver halide grain size is more preferably 0.2 to 1.2 μm.

The various additives mentioned above are used in the photosensitive material related to the present technology, but other various additives can also be used depending on the purpose.

These additives are described in more detail in Research Disclosure +tem17643 (December 1978) and TLe ■18716 (November 1979), and the relevant sections are summarized in the table below.

2 Sensitivity enhancer 3 Spectral sensitizer, supersensitizer 4 Brightener 5 Anti-fogging agent and stabilizer 6 Light absorber, filter dye ultraviolet absorbing side 7 Anti-stinting agent 8 Dye image stabilizer 9 Hardening agent 10 Binder 11 Plasticizer, lubricant 12 Coating aid, surface active agent 13 Static inhibitor Same as above, pages 23-24 548 right column - 649 page right column 24 pages 24-25 649 page right column pages 25-26 649 right Column ~ 650 left column 25 pages right column 650 pages left to right column 25 pages 26 pages 651 left column 26 pages Same as above 27 pages 650 right column pages 26-27 Same as above 27 pages Same as above Various color couplers are used in the present invention A specific example of this can be found in the aforementioned research disclosure (
RD) No. 17643, described in the patent described in ■-CG.

As a yellow coupler, for example, U.S. Patent Tube 3.93
No. 3,501, No. 4.022,620, No. 4.3
No. 26,024, No. 4.401752, Special Publication No. 1982
-107.39, British Patent No. 1,425,020,
Same 1st. 476, 760, etc. are preferred.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and US Pat.
No. 0,619, No. 4,351°897, European Patent No. 73,636, US Patent No. 3,061,432, No. 3. 725. No. 067, Research Disclosure 1tt24220 (June 1984), JP-A-6
No. 0-33552, Research Disclosure N1
24230 (June 1984, Japanese Patent Publication No. 60-4365
9, U.S. Patent No. 4.500.630, U.S. Patent No. 4.54
Particularly preferred are those described in No. 0.654.

Cyan couplers include phenolic and naphtholic phenols, and are disclosed in U.S. Pat. No. 4,052.21.
No. 2, No. 4,146.396, No. 4.228,2
No. 33, No. 4.296,200, No. 2.369.
No. 929, No. 2,801.171, No. 2,772
．． No. 162, No. 2.895,826, No. 3. 7
72. No. 002, No. 3,758.308, No. 4
, No. 334.011, No. 4,327,173, West German Patent Publication No. 3.329.729, European Patent No. 121.
No. 365A, U.S. Patent No. 3,446.622, U.S. Patent No. 4
．． Preferred are those described in No. 333,999, No. 4.451.559, No. 4.427,767, European Patent No. 161.626A, and the like.

Colored couplers for correcting unnecessary absorption of coloring dyes are listed in Research Disclosure No. 17643.
- Section G, U.S. Patent No. 4.163670, Special Publication No. 1987-
No. 39413, U.S. Patent No. 4,004.929, U.S. Patent No. 4. 138. No. 258, British Patent No. 1,146,3
The one described in No. 68 is preferred.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2,125.
, 570, European Patent No. 96.570, and German Patent Publication No. 3.234.533 are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat. No. 3,451.820, U.S. Pat.
It is described in No. 173, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors include the aforementioned RD17643.
Patent described in Sections 4-2, JP-A-57-151944
Preferred are those described in No. 57-154234, No. 60-184248, and U.S. Pat.

A coupler that releases a nucleating agent or a development accelerator imagewise during development is disclosed in British Patent No. 2. o97.140,
No. 2,131.088, JP 59-157638
No. 59-170840 is preferred.

Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130.427, U.S. Pat. , the multi-equivalent coupler described in JP-A-60-185950, etc.
DIR redox compound or DIR coupler releasing coupler or DIR coupler releasing coupler or redox described in JP-A-6224252 etc., European Patent No. 17
3. Couplers that release dyes that recolor after separation as described in No. 302A, R, D, No. 11449, No. 24241, bleaching accelerator releasing couplers described in JP-A No. 61-201247, etc., U.S. Pat. No. 4,553 Examples include the ligand-releasing couplers described in No. 477 and the like.

Specific examples of color couplers that can be used in the present invention are listed below, but the invention is not limited to these.

C-(6) C-(9) C-(11) C-(12) H +CH* -C hl-HCHt-CH+-T,s C-(19) C-(20) C-(24) c-(26) C-(33) C-(29) C-(37) C (3 days) C-(40) Shil l C2゜)(g+ 4H9 C-<41) C-(42) (t) Cs H.

C-(51) C-(53) C-(54) C-(55) C-(60) The coupler used in the present invention can be introduced into the photosensitive material by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027 and the like.

Specific examples of high-boiling organic solvents with a boiling point of 175°C or higher at normal pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, synchrohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate). , bis(2,4-di-t-amylphenyl) phthalate, bis(2,4-di-L-amylphenyl) isophthalate, bis(1,1-diethylpropyl) phthalate, etc.), esters of phosphoric acid or phosphonic acid (trifel phosphate, tricresyl phosphate, 2-
ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexyl phenyl phosphonate, etc.), benzoic acid esters (2-ethylhexylbenzoate,
dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides @ (N, N-diethyl dodecanamide, N, N-diethyl lauryl amide,
N-tetradecylpicolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-
-amylphenol, etc.], aliphatic carboxylic acid ester M (bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline G4 body (N, N-diptyl-
2-butoxy-5-tert-octylaniline, etc.)
, hydrocarbons (paraffin, dodecylbenzene, diisobrobylnafculene, etc.). In addition, as an auxiliary solvent, the boiling point is about 30°C or higher, preferably 50°C.
Any organic solvent having a temperature above about 160° C. or below can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide, and the like.

Examples of the steps, effects, and latex for impregnation of latex dispersion methods are described in U.S. Pat.
No. 541,230, etc.

The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, and color reversal vapor.

When the present invention is used in color photographic materials, it can be applied to photosensitive materials with various configurations and photosensitive materials in which layer configurations and special color materials are combined.

A typical example is illustrated below. JP 47-49031, JP 49-3843, JP 5o-21248, JP 59-58147, JP 59-60437,
JP 60-227256, JP 61-4043, JP 61-43743, JP 61-42657
A combination of the coupling speed and diffusivity of a color coupler and the structure of the layer, as shown in
No. 95, U.S. Pat. No. 3,843,469, in which the same color-sensitive layer is divided into two or more layers, Japanese Patent Publication No. 53-3701
No. 7, Special Publication No. 53-37018, Japanese Patent Publication No. 51-490
No. 27, JP-A-52-143016, JP-A-53-9
No. 7424, JP-A-53-97831, JP-A-62-
200350 and Japanese Patent Laid-Open No. 59-177551, which stipulate the arrangement of a high-intensity layer and a low-sensitivity layer and the arrangement of layers with different color sensitivities.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, Arashi 17643, page 28, and Arashi 18716, 6
It is described from the right column of page 47 (capital) to the left column of page 648.

The color photographic light-sensitive material according to the present invention is described in the above-mentioned RD, No. 17643, pages 28-29, and Kaimagaku No. 18716, No. 6.
51. Development processing can be carried out by the usual methods described in the left column to right column.

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. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which include 3-methyl-4-amino-N, N-diethylaniline, 3- Methyl-4-amino-N-ethyl-N
-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N
-β-methoxyethylaniline and their sulfates, hydrochlorides, p-)luenesulfonates, and the like. Two or more of these compounds can be used in combination depending on the purpose.

The color developer may contain pHff1 additives such as alkali metal carbonates, borates or phosphates, development inhibitors or foggers such as bromide salts, iodide salts, benzimidazoles, benzothiazoles or mercapto compounds. It generally contains an inhibitor. Also, if necessary,
Hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenylsemicarbazides, triethanolamine, catechol sulfonic acids, triethylenediamine (1,4-diazabicyclo[2°2.2]
Octane) various preservatives such as neck, ethylene glycol,
organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, caprasetting agents such as competing couplers sodium boron hydride, 1-phenyl-3-pyrazolidone. Auxiliary developing agents, viscosity-imparting agents, various oxidizing agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, and diethylenetriamine. Pentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-
1,1-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N'N
Typical examples include '-tetramethylenephosphonic acid, ethylenediamine-di(0-hydroxyphenylacetic acid), and salts thereof.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. Alternatively, they can be used in combination.

The pH of these color developing solutions and black and white developing solutions is generally from 9 to 2. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material to be processed, but it is generally less than 31 per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher,
It can also be set to 6 or less. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank. Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

The time for color development processing is usually set at 2 to 5 minutes, but the processing time can be further shortened by using high temperature, high pH, and high concentration of color developing agent.

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

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process), or separately (bleach-fixing process), or in order to speed up the process, it may be possible to perform a bleach-fixing process after the bleaching process. Depending on the purpose, treatment may be carried out in consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment. e. As one agent, for example, iron (■), cobalt (I)
II), compounds of polyvalent metals such as chromium (Vl), steel (Ill), peracids, quinones, nitro compounds, etc. are used.

Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (ill) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3- Aminopolycarboxylic acids such as diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc.;
Persulfates; bromates; permanganates; nitrobenzenes and the like can be used. Among these, iron aminopolycarboxylate (DI) i! Salt and i! The 1-sulfate salt is preferred from the viewpoint of rapid processing and prevention of environmental pollution, and the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both bleaching solutions and bleach-fixing solutions.

The pH of bleaching solutions or bleach-fixing solutions using these aminopolycarboxylic acid iron (II) complex salts is usually 5.5 to 8, but in order to speed up the processing, it is possible to treat with an even lower pH. You can also do it.

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. Pat. No. 3,893.858, German Pat.
, No. 290.812, No. 2,059.988, JP-A-53-32,736, No. 5357.831, No. 53
-37.418, 53-72.623, 53-
No. 95.630, No. 53-95,631, No. 53-I
Q, No. 4232, No. 53-124, 424, No. 53-
No. 141.623, No. 53-28,426, Research Disclosure Fish No. 17,129 (July 1978)
Compounds having a mercapto group or a disulfide group as described in JP-A-50-140.129; thiazolidine derivatives as described in JP-A-45-8.506, JP-A-52-20,832, No. 53-32,735, thiourea derivatives described in U.S. Pat. No. 3.706.561;
Iodide salt described in No. ゜235; West German Patent No. 966゜41
0, polyoxyethylene compounds described in JP-A No. 2,748.430; polyamine compounds described in JP-A No. 45-8836; other JP-A Nos. 4942-434 and JP-A-49-49-
No. 59,644, No. 53-94.927, No. 54-3
No. 5,72T, No. 55-26,506, No. 58-16
Compounds described in No. 3.940: Bromide ions, etc. can 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, such as U.S. Patent No. 3,893,858 and Western Patent No. 1.290.812.
The compounds described in JP-A-53-95,630 are preferred, and the compounds described in U.S. Pat. No. 4,552,834 are also preferred. These bleach accelerators are effective when bleach-fixing color light-sensitive materials for shadows.

Examples of fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, with ammonium thiosulfate being the most widely used. Can be used for As the preservative for the bleach-fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
Urnalof the 5ociety or Mo
tion Picture and Te1evis
ion [1 Bineers No. 64LP, 248-25
3 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. The problem arises. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
The method for reducing calcium ions and magnesium ions described in Japanese Patent Application No. 61-131,632 can be used very effectively. Also, JP-A-57-8,542
Chlorinated disinfectants such as isothiazolone compounds, cyabendazole, chlorinated sodium isocyanurate, and other benzotriazoles listed in the issue, "Chemistry of antibacterial and fungicidal agents" written by Hiroshi Horiguchi, "Microbial It is also possible to use the disinfectants described in "Sterilization, Disinfection, and Anti-Mildew Techniques" and "Encyclopedia of Antibacterial and Antifungal Agents" published by Japan Antibacterial and Antifungal Science Kinsen.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4-
9, preferably 5-8. The washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15-45°C, preferably 20 minutes.
A range of 30 seconds and 5 minutes at 5-40°C is selected. Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-Open Nos. 57-8,543 and 58-14.83
All known methods described in No. 4, No. 60-220,345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be carried out, such as a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography. .

It is also possible to add various botanical agents and antifungal agents to this stabilizing bath.

The overflow liquid from water washing and/or replenishment of the stabilizing liquid can be reused in other processes such as the desilvering process.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate a color developing agent, it is preferable to use various precursors of the color developing agent. U.S. Patent No. 3,342.59
Indoaniline compounds described in No. 7, No. 3.342.
No. 599, Research Disclosure 14,850
Schiff base-type compounds described in No. 15,159 and aldol compounds described in No. 13.924, U.S. Patent No. 3
．． Metal salt complex described in No. 719.492, JP-A-53-1
Examples include urethane compounds described in No. 35,628.

The silver halide color light-sensitive material of the present invention may optionally contain various 1-phenyl-3
- Typical compounds that may contain pyrazolidones are JP-A-56-64.339 and JP-A-57-144.547.
No. 58-115.438, etc.

The various processing solutions used in the present invention are used at a temperature of 10°C to 50°C. Normally, the temperature is 33°C to 38°C, but higher temperatures may be used to accelerate the processing and shorten the processing time, or vice versa. It is possible to improve the image quality and the stability of the processing solution by lowering the temperature. In addition, in order to save silver on photosensitive materials, West German Patent No. 2.226,770 or U.S. Patent No. 3
．． A treatment using cobalt intensification or hydrogen peroxide intensification as described in No. 674.499 may also be carried out.

Further, the silver halide photosensitive material of the present invention is disclosed in US Patent No. 4.
No. 500.626, JP-A No. 60-133449, No. 5
It can also be applied to the heat-developable photosensitive materials described in European Patent No. 9-218443, European Patent No. 61-238056, European Patent No. 210,660A2, and the like.

(Examples) Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

Example 1 Average iodine content is 20 mol%, average equivalent sphere diameter is 0° 8 μm
The core-shell ratio was 1=2 using the controlled double-jet method in an aqueous gelatin solution using double twinned particles as seed crystals.
An emulsion consisting of twinned grains having an average equivalent sphere diameter of 1.2 μm and having a shell iodine content of 2 mol % was formed.

After grain formation, the emulsion was subjected to a normal desalination washing step and redispersed at 40° C. under the conditions of pAg 8.9 and pH 15.3. The emulsion thus produced is designated as Em-1.

On the other hand, 1 minute before the start of shell formation, the following thiosulfonic acid compounds 1-10.1-6, ■ = 2 were added, and 1 minute after the start of shell formation, the following reduction sensitizers 2-A, 2- B
were added to the reaction pot in optimum amounts as shown in Table 1-1 to form grains, thereby preparing emulsions Em-2 to Em-5.

(Reduction sensitizer) 2-A Thiourea dioxide 2 to B Dimethylamine borane The emulsions Eml to 5 thus prepared were treated with sodium thiosulfate and chloroauric acid to optimally transform each emulsion into gold and gold.
A sulfur-sensitized emulsion was prepared.

on a subbed cellulose triacetate film support.
Sample 101, which is a multilayer color photosensitive material, was prepared by coating layers having the compositions shown below.

(Photosensitive layer composition) The numbers corresponding to each component indicate the coating amount expressed in g/i units, and for silver halide, the coating amount is expressed in m. However, for sensitizing dyes, the halogen in the same layer v
The coating amount is expressed in moles relative to At moles.

(Sample 101) 1st layer; antihalation layer black colloidal silver... silver 0.18 gelatin... 0.40 2nd layer;
Intermediate layer 2.5-di-t-pentadecylhydroquinone...0.188X
-1・ 0.07 EX-3... 0.02 EX-12... 0.002 0-1... 0.6U
-2... 0.08 U-3... 0.10 8BS-1... 0.10) (BS-2... 0.02 Gelatin... 1.04 3rd
Layer (first red-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0)
．． 6μ, coefficient of variation regarding particle size 0°15)
...110.55 Sensitizing dye I
...6.9X10-'sensitizing dye■
・・Bow, 8X10-' sensitizing dye■ ・
・・3.1X10-'sensitizing dye■ ・・
・4.0X10-'EX-2... 0.350 HBS-1... 0.005 EX-10... 0.020 Gelatin... 1.20 4th
Layer (second emulsion layer) Tabular silver iodobromide emulsion (silver iodide 10 mol%, average grain size 0.7μ, average aspect ratio 5.5, average thickness 0.2μ
) Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ X-2 X-3 X-10 Gelatin 5th layer (third red-sensitive emulsion layer) Silver iodobromide emulsion! Sensitizing dye■ Sensitizing dye m Sensitizing dye■ Sensitizing dye■ X-3 X-4 BS-1 HB S-2 Gelatin...Silver 1.0...5. lX10-'...1.4X10-'...2.3X10-'...3.0X10-'...0.400...0.050...0.015...1. 30...ml, 60...1.4X10-'...2, 4X10-'...3. lX10-5 ... 5.4X10-' ... 0.240 ... 0.1 20 ... 0.22 ... 0.10 ... 1.63 6th layer (middle N) EX -5... 0.040 HBS-1... 0.020 Gelatin... 0.80 7th
Layer (first green emulsion layer) Tabular silver iodobromide emulsion (iodide 16 mol%, average grain size 0)
．． 6μ, average aspect ratio 6゜0, average thickness 0.15)
...Silver 0.40 sensitizing dye V
...3.0XIO-'sensitizing dye■
...i, oxio-' sensitizing dye■
...3.8XIO-'EX-6 River 0.2 6
0 EX-1... 0.021 EX-7... 0.030 EX-8... 0.025 HBS-1... 0.100 HBS-4... 0.010 Gelatin... 0.75 8th
Layer (second green-sensitive emulsion layer) Monodispersed silver iodobromide emulsion (silver iodide 9 mol%, average grain size 0)
．． 7μ, coefficient of variation regarding particle size 0゜18)
... i艮 0, 80 sensitizing dye V ...2.
1X10-'sensitizing dye ■...7.0
X10-'sensitizing dye ■...2.6X
IQ-'EX-6... 0.180 EX-8... 0.010 EX-1... 0.008 EX-7... 0.012 HBS-1... 0.160 HB S -4... 0.008 Gelatin River 1.10 9th layer (
3rd green-sensitive emulsion layer) Silver iodobromide emulsion ■...Silver 1.2 sensitizing dye V...3.5X10-' sensitizing dye ■...8.0X10-' sensitizing dye ■
...3.0X10-'EX-6...
・0. O65 EX-11... 0.030 EX-1... 0.025 HBS-1... 0.25 HBS-2... Ol 10 Gelatin... 1.74 1st
0 layer (yellow filter N) Yellow colloidal silver...io, osEX
-5... 0.08 HBS-3... 0.03 Gelatin... 0.95 1st
1 layer (first blue-sensitive emulsion layer) Tabular silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0)
．． 6μ, average aspect ratio 5.7, average thickness 0.15)
...Silver 0.24 sensitizing dye■
...3.5X10-'EX-9...0.8S EX-8...0,12 HBS-1...0.28 Gelatin...1.28 1st
2 layers (second blue-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide 10 mol%, average grain size 0.8μ, coefficient of variation regarding grain size 0°16)
...i
艮 0, 45 sensitizing dye■...2
．． lX10'□'EX~9
... 0.208X-10... 0.
015 HBS-1... 0.03 Gelatin... 0.46 1st
3 layers (third blue-sensitive emulsion layer) Silver iodobromide emulsion ■...Silver 0.77 amplifying dye■...2.2X10-'EX-
9... 0,20 8BS-1... 0.07 Gelatin... 0.69 1st
4 layers (first protection 113i) Silver iodobromide emulsion (silver iodide 1 mol%, average grain size 0.07
μ) ...Silver 0.5U-4...
0,11 t)-5... 0.17 HBS-1... 0.90 Gelatin... l, 00th
5 layers (second protective layer) Polymethyl acrylate particles (diameter approximately 1.5 μm) -= 0.543-
1...0.15S-
2... 0.05 Gelatin... 0.72 In addition to the above components, gelatin hardening agent H-1 and a surfactant were added to each layer.

X-3 X-2 X X
! -CH-3oCHx C0NHCHt Sensitizing dye C,H.

■ z　Hs C,H.

C1Hs (CH) ssO3θ (CHz)s SOs Na C, H5 C,H.

■ zHs 5th layer silver iodobromide emulsion ■, 9th layer silver iodobromide emulsion ■
, Sample 10 except that the silver iodobromide emulsion ■ in the 13th layer was changed.
Samples 102 to 105 were prepared in the same manner as in Example 1.

Furthermore, samples 106 to If(+) were created by changing the gold amounts of samples 101 to 105 as shown in Table 1-2.

The amount of gold was changed as follows.

Gold/sulfur sensitized 4 used to create samples 101 to 105
Add 4.5 g of ion exchange resin (for example, product name DOWEX 1x8; manufactured by Dow Chemical Co., Ltd.) per 500 g of emulsion to a silver halide emulsion at 0°C, and stir for 5 to 20 minutes to determine the amount of gold. was prepared. Thereafter, the ion exchange resin was removed from the silver halide emulsion by passing through a filter, and the pH and pAg were readjusted to their original values.

Table 1 Samples iot to ito were left for 14 hours at 40° C. and 70% relative humidity. After storage under two storage conditions shown in 1-4, sensitivity and fog were measured.

Storage conditions (B) are conditions under which the samples were stored under natural conditions for 60 days. Further, samples 1101 to 110 were subjected to hydrogen sensitization treatment, and the increase in sensitivity ΔS7 was measured. The hydrogen sensitization treatment was performed by placing the sample in a sealed container, purging the container with hydrogen after vacuum degassing, and leaving the container at 30° C. for 30 minutes and 60 minutes.

Amount of increase in sensitivity △S, B, Amount of increase in blue sensitivity, green sensitivity, and red sensitivity under the conditions where the highest sensitivity achieved by hydrogen sensitization △
Measurements of Sl, ΔS6, ΔS, sensitivity, and fog were carried out by exposing the sample to sensitometric light and subjecting it to the following color development process.

Processing method Color development processing was carried out at 38°C according to the following processing steps.

Color development 3 minutes 15 seconds Bleach White 6 minutes 30 seconds Wash with water for 2 minutes! 0 seconds Fixed arrival time: 4 minutes 20 seconds Water wash 3 minutes 15 seconds Stability 1 minute 05 seconds The composition of the treatment liquid used in each step was as follows.

Color developer diethylenetriaminepentavinegar 1. Og]
-Hydroxyethylidene~ 1.1-diphosphonic acid 2.0g Sodium sulfite 4.0g Potassium carbonate
30.0g potassium bromide
1.4g potassium iodide
1. ．． 3ffig hydroxylamine sulfate
Add 2.4g 4-(N-ethyl-N-β-hydroxyethylamino)-2-methylaniline sulfate aqueous p)l Bleach solution ethylenediaminetetraacetic acid ferric ammonium salt ethylenediaminetetraacetic acid disodium salt ammonium bromide ammonium nitrate Add water and H Fixer Ethylenediaminetetraacetic acid disodium salt Sodium sulfite ammonium thiosulfate aqueous solution (70%) 4.5 g 1, Ol 10.0 100.0 g 10.0 g 150.0 g 10.0 g 1, OA 6. 0 1.0g 4.0g 175.0ml Sodium bisulfite Add 4.6g water 1・o'! pl (6,6 Stable liquid formalin (40%) 2.0 m
0.3 g of 1 polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) was added to the sample, and the concentration of the 1.01-treated sample was measured using a red filter, a green filter, and a blue filter. The results obtained are shown in Table 1-4.

Regarding the results of photographic performance, the sensitivities of the red-sensitive layer, green-sensitive layer, and blue-sensitive layer were measured for sample 101 under storage conditions (A).
It is expressed as a relative sensitivity when the sensitivity of is set as 100.

From the results in Table 1-4, sample 102 using a reduction sensitizer
It can be seen that samples Nos. 105 and 107 to 110 have the effect of increasing sensitivity with almost no increase in fog when the photosensitive materials are processed immediately after production. Furthermore, the sensitivity increase ΔS due to hydrogen sensitization is small in these samples, indicating that effective reduction enhancement has been performed.

However, Comparative Samples 102 to 105, in which the amount of gold was not reduced, showed a significant increase in fog and a significant decrease in sensitivity when the light-sensitive materials were allowed to age naturally after being manufactured. On the other hand, it can be seen that Samples 107 to 110 of the present invention, in which the amount of gold was reduced, have a marked improvement in the increase in fog and the decrease in sensitivity after aging, and are excellent in storage stability.

Example 2 On a subbed cellulose triacetate film support,
Sample 201, which is a multilayer color photosensitive material consisting of each layer having the composition shown below, was prepared.

(Composition of photosensitive layer) The coating amount is the amount expressed in g/rd unit of silver for silver halide, colloidal silver and coupler, and the mole per mole of 11% halide in the same layer for sensitizing dye. Shown in numbers.

1st layer: antihalation layer black colloidal silver Silver coating amount 0.2 gelatin
2.2UV-10,l UV-20,2 cpd-io, asSol
v-10,01 Solv-20,01 Solv-30,08 2nd layer; Intermediate layer fine grain silver bromide (equivalent sphere diameter 0.07μ) Silver coating M O,15 Gelatin 1. Qcpdi
o, 2 Third layer: First red-sensitive emulsion layer Silver iodobromide emulsion (AgT 10.0 mol%, internal high Agl type, equivalent sphere diameter 0.7 μ, coefficient of variation of equivalent sphere diameter 14%, 14
(Hedron grain) Silver coated I O,26 Silver iodobromide emulsion (Ag + 4.0 mol%, internal high AgI type,
Equivalent sphere diameter 0.4μ, coefficient of variation of equivalent sphere diameter 22%, tetradecahedral particle) Silver coating amount 0.2 Gelatin 1.0ExS-1
4,5X10-'molExS-21,5xxo-'molExS-30,4xlO-'molExS-40,3xlO-'molExC-10,33 ExC-20,009 ExC-30,023 ExC-60,14 4th N: Second red-sensitive emulsion layer Silver iodobromide emulsion (Ag 116 mol%, internal high Agl type, equivalent sphere diameter 1.0μ, coefficient of variation of equivalent sphere diameter 25%, plate-like grains, diameter/thickness ratio 4. 0) w1 coating amount 0.55 Gelatin 0.7ExS-
13xio-'ExS-21xlO-'ExS-30,3x10-'Ext-40,3XIO-' ExC-30,05 ExC-40,10 ExC-60,08 5th layer: 3rd red-sensitive emulsion layer Silver bromide emulsion I (internal high Agl type, equivalent sphere diameter 1° 2μ)
, coefficient of variation of equivalent sphere diameter 28%) il coating amount 0.9 0.6 2X10-'0.6X10-'0.2X10-' 0,07 0.06 0, l 2 Gelatin xS-I xS-2 xS -3 ExC-4 ExC-5 Solv-I Solv-2 6th N: Intermediate layer gelatin pd-4 7th layer: First green-sensitive emulsion layer Silver iodobromide emulsion (Ag110.0 mol%, internal high Agl type, Equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 14%, 14
(hedral particles)! ! Coating amount 0.2 Silver iodobromide emulsion (Agl 4.0 mol%, internal high Ag
L type, equivalent sphere diameter 0.4 μ, coefficient of variation of equivalent sphere diameter 22%,
(Tedecahedral particles) Silver coating amount 0.1 1.2 5X10-'2X10-'1xio-' 0, 41 0, 10 0.03 0.2 0.1 1, 0 Gelatin X5-5 xS-6 xS-7 ExM-I ExM-2 ExM-5 Solv-1 Solv-50,03 8th layer: 2nd green-sensitive emulsion layer Silver iodobromide emulsion (Ag 110 mol%, internal high iodine type, sphere equivalent diameter 1.0μ, sphere Coefficient of variation of equivalent diameter 25%, plate-shaped particles, diameter/thickness ratio 3.0) Silver coating 10.4 Gelatin 0.35ExS-
53,5X10-'EXS-61,4X10-'ExS-7' 0. vxto-' ExM-10,09 ExM-30,01 Solv-10,15 Solv-50,03 9th layer; intermediate layer gelatin 0.5 10th layer:
3rd green-sensitive emulsion layer Silver iodobromide emulsion ■ (internal high Agl type, equivalent sphere diameter 1° 2μ,
Coefficient of variation of equivalent ball diameter 28%) m coating! 1.0 Gelatin 0.8ExS-5
2xio-' ExS-60, 8X10~4 ExS-7o, axto-' ExM-30, 01 ExM-40, 04 ExC-I Q, 005SQ
IV-10,2 11th layer: Yellow filter layer Cpd-30,05 Gelatin 0.5Solv-
10,1 12th N: Intermediate layer gelatin 0. 5Cpd-
20,1 13th layer: 1st blue emulsion layer Silver iodobromide emulsion (Ag 110 mol%, internal high iodine type, equivalent sphere diameter 0.7 μ, coefficient of variation of equivalent sphere diameter 14%, tetradecahedral grains) Silver coating 310.1 Silver iodobromide hole lfIJ (Ag 14.0 mol%, internal high iodine type, equivalent sphere diameter 0.4 μ, coefficient of variation of equivalent sphere diameter 22%,
Tedecahedral particles) Silver coating amount 0.05 Gelatin 1. 0BXS-
83X10-' ExY-10,53 ExY-20,02 SOIV-10,15 14th layer: 2nd blue-sensitive emulsion layer Silver iodobromide emulsion (Ag119.0 mol%, internal high Agl type, equivalent sphere diameter 1. 0μ, number of fluctuations in equivalent sphere diameter 16%, tetradecahedral particles) Silver coating amount 0.19 Gelatin 0.3ExS-8
2X10-' ExY-10,22 Solv-10,07 15th layer: Intermediate layer fine grain silver iodobromide (Ag+2 mol%, uniform type, equivalent sphere diameter 0
613μ) Silver coating amount 0. 2 Gelatin 0.36 16th layer: 3rd blue-sensitive emulsion layer Silver iodobromide emulsion (internal high AgI type, equivalent sphere diameter 1°2μ, coefficient of variation of equivalent sphere diameter 28%) Silver coating amount 1.0 Gelatin 0 .5ExS-8
1,5xxo-' ExY-10,2 Solv-10,07 17th layer: 1st protective layer gelatin 1.8UV-10
, l UV-20,2 Solv-10,01 Solv-20,01 18th layer: 2nd protective layer fine grain silver bromide (equivalent sphere diameter 0°07μ) 1! Coating amount 0.18 Gelatin polymethyl meccrylate particles (diameter 1.5μ) pd-5 0.7 Hz ExC-3 xM Hs ExC ○1] ExC-4 H (n) C+□I]! .

C+zHzs xY xY ExS-1 ExS-2 ExS-8 ExS-7 olv-1 olv-2 C,H.

tHsC! Hs 0Iv-3 ExS ExS-5 OIV 0IV-5 pd pd z14s Cpd-3 W-1 CHz ``'CH30t CHz C0NH-CHtSilver iodobromide emulsion I in the 5th layer, silver iodobromide emulsion in the 10th layer ■
, Sample 20 except that the silver iodobromide emulsion ■ in the 16th layer was changed.
Samples 202 to 203 were prepared in the same manner as in Example 1.

Furthermore, samples 204 to 206 were prepared by changing the gold amounts of samples 201 to 203 in the same manner as shown in Example 1 as shown in Table 2-1.

Samples 201 to 206 were shown in Example 1 (A) and (B
) Sensitivity and fog were measured after storage under the following storage conditions. Also,
Hydrogen sensitization was performed in the same manner as in Example 1, and the increase in sensitivity ΔS was measured.

Sensitivity and fog measurements were performed using the same exposure, color development, and density measurements as in Example 1. The results obtained are shown in Table 2-2.

Regarding the results of photographic performance, the sensitivities of the red-sensitive layer, green-sensitive layer, and blue-sensitive layer were each expressed as relative sensitivities when the sensitivity of sample 201 was set as 100.

As is clear from Table 2-2, the photosensitive material of the present invention has the effect of increasing sensitivity with almost no increase in fog, and
It can be seen that it has excellent storage stability.

Example 3 On a subbed cellulose triacetate film support,
Sample 301, which is a multilayer color photosensitive material consisting of each layer having the composition shown below, was prepared.

(Composition of photosensitive layer) The coating amount is expressed in g/rd unit of silver for silver halide and Colloid F'' silver, and the amount expressed in g/ld unit for coupler additive and gelatin. Sensitizing dyes are shown in moles per mole of silver halide in the same layer.Symbols indicating additives have the meanings shown below.However, if they have multiple effects, one of them should be used as a representative. I posted it.

Uv; ultraviolet absorber, 5olvH high boiling point organic solvent, Ex
Fi dye, ExtH enhancing dye, ExcH cyan coupler, ExM; magenta coupler Ex Y; yellow coupler, Cpd: Additive 1st layer (antihalation layer) Black colloid primate...0.15
Gelatin...2.9UV-
1...0.03 UV-2-Q, Q5 UV-3...0.07 Solv-2-0,08 Ex F -1-Q. 0I ExF-2-0,01 2nd layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (Ag + 4 mol.%, uniform equivalent sphere diameter.

0.4 μ Coefficient of variation of equivalent sphere diameter 37%, plate-like particle diameter/thickness ratio 3.0) Coating i foot... 0.4...0.8 ・2.3XLO-'...1. 4X10-'...2.3X10-'...8.0X10-' ...0.17 ...0.03 ...0.13 Gelatin xS-1 xS-2 xS-5 X5-7 x C-1
Coefficient of variation of sphere equivalent diameter 25%, plate-like particle, diameter/thickness 2.
0) Coating tl amount...0.65 Silver iodobromide hole m (Ag 14 mol%, uniform Agl type, equivalent sphere diameter 0.4μ, coefficient of variation of equivalent sphere diameter 37%, plate-like grain, diameter/thickness Ratio 3.0) Coated silver amount...0. 1 Gelatin...1.0ExS
-1-= 2X10-' ExS-2・A, 2XIO-' ExS-5-= 2X10-' ExS-7... 7X10-' ExC-7-0, 31 ExC-2-0, 01 ExC-3・”0.06 4th N (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion I (internal high Agl with core-shell ratio of 1:2)
Mold, equivalent sphere diameter 0.75μ, coefficient of variation of equivalent sphere diameter 25%) Coated silver amount...0.9 Gelatin...0.8ExS
-1=4.6X10-'ExS-2"i,6X10-' ExS-5=1.5x 10-'ExS-7-6X10-' ExC-1-0,07 ExC-4-0,05 Solv- 1.=0.07 Solv-2"J, 20 Cpd-1...4.6X10-' 5th layer (middle layer) Gelatin...0.6L7V
-4...0.03 UV-5...0.04 Cpd-1...0. 1 Polyethyl acrylate latex...0.08S
olv-1-0,05 6th layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (Ag 14 mol% uniform type 0 sphere equivalent diameter 0.4
μ, equivalent sphere diameter 0.7 μ, coefficient of variation of equivalent sphere diameter 37%, plate-like particles, diameter/thickness ratio 2° Coated silver amount...0.18 Gelatin...0.4ExS
-3・zxto-'ExS-4-'yxio-' ExS-5 -txlo-'ExM
-5-0,11 ExM-7-0,03 ExY-8=O,0I So Iv-1-0,09 So Iv-4・=0. 01 No. 71! (Medium-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (Ag 14 mol%, surface height Agl type with core-shell ratio 11, equivalent sphere diameter, equivalent sphere diameter 0.5μ, coefficient of variation of equivalent sphere diameter 20%, plate-like grains) , diameter/thickness ratio 4.0) Application 1! Amount...0.27 Gelatin...0.6ExS
-3-zxxo-'ExS-4...-'rx+o-' ExS-5 ・=I X I O
-'ExM-5・0. 17 ExM-7-=0.04 ExY-8-0,02 Solv-1-0,14 Solv-4...0.02 8th layer (high sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion ( Internal height AgI type with core shell ratio 1:2, equivalent sphere diameter 0.75 μ, coefficient of variation of equivalent sphere diameter 25%) Gelatin xS-4 xS-5 xS-FJ xM-5 xM-6 Coating amount...0. 7...0.8...5.2X10-'...IX10-'...0.3XIO-'...0. 1...0.03 ExY-8-0,02 ExC-1-0,02 ExC-4-0,01 Solv-1-0,25 So 1v-2-0,06 So 1v-4-0, OI Cpd-7... 1 'X' 1 0-' 9th layer (middle N) Gelatin...0.6 cpa
-t...0.04 polyethyl acrylate latex...0.123o1v
1...0.02 10th layer (donor layer for interlayer effect on red-sensitive layer) Silver iodobromide emulsion (
Ag+6 mol%, internal high Agl type with core-shell ratio 2:1, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 25%, plate-shaped particles, diameter/thickness ratio 2.0) Coated silver amount...0 .68 Silver iodobromide emulsion (Ag 14 mol% uniform type, coefficient of variation of equivalent sphere diameter 37%, plate-like grains, diameter/thickness ratio 3.0) Coating ≦ Foothold... 0, 19 Gelatin... 1,0ExS
-3---6×10-' ExM -10-0,19 So 1v-1-0,20 11th layer (yellow filter layer) Yellow colloidal silver...0.06 Gelatin...0.8Cpd-
'l...0.13So I
v-1-0, I 3 Cpd-1...0.07 Cpd-5...0.002 H-1...0.13 12th layer (low sensitivity blue-sensitive emulsion layer) Silver iodobromide Emulsion (A6 14.5 mol%, uniform-Agl type, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 15%, plate-like grains, diameter/thickness ratio 7.0) Coated silver amount...0.3 Silver iodobromide emulsion (Ag 13 mol%, uniform Agl type, equivalent sphere diameter 0.3 μ, coefficient of variation of equivalent sphere diameter 30%, plate-like grains, diameter/thickness 7.0) Coated silver amount...0. 15 Gelatin...1.8ExS
-6--9xt O-' ExC-1-0,06 ExC-4-=0.03 ExY-9-0,14 ExY -11-0,89 So 1v-1-0,42 13th layer ( Intermediate layer) Gelatin...0.7ExY
-12-0゜20 Solv-1・=0.34 14th layer (high-sensitivity blue-sensitive emulsion N) Silver iodobromide emulsion (internal high Agl type with core-shell ratio 1:2,
Equivalent sphere diameter 0.75 μ, coefficient of variation of equivalent sphere diameter 25%) Application vAl...0.5 Gelatin...0. 5Ex
S-6=-txxo-' ExY-9-0, OI ExY-11-0, 20 ExC-1-0, 02 Solv-1・=0. 10 15th N (first protective layer) Fine grain silver bromide emulsion (Ag 12 mol%, uniform-Agl type, equivalent sphere diameter 0.07μ) Coated silver amount...0.12 Gelatin...0.9U V
-4・0.11 UV-5...0.16 Sol v-5-0,02 H-1...0.13 Cpd-5...0.10 Polyethyl acrylate latex... 0.09 16th layer (second protective layer) Fine grain silver bromide emulsion (Ag 12 mol%, uniform Agl type, equivalent sphere diameter 0.07.
u> Amount per application... 0.

V-t Gelatin...0.55 Polymethyl methacrylate particle diameter 1゜5μ...0゜I (-1...0゜In addition to the above components, each layer contains emulsion stabilizing agent ulcpd3
(0,07g/n()surfactant(:pd-4(0,
03 g/n (>) was added as a coating aid.

V-2 olv-2 o1v-4 N V-5 o1v-5 Hs Hs Hs Ht Hs ExF ExF xS-4 Month Hs　Cx　Ct　Hs C low H5 CHI-C84 Oi CHI CHI 03 K xS xS-2 xS xS-7 xS-8 tHs So, Na SO3H-N-Ct Hs zHs ExC-1 f3. xc-2 xM-5 Ijs CH) HI Hs I H3 ExC ExC-4 xM xM H ExY-8 EXY pd-1 pd-2 pd-6 -N ExY ■4-1 CHz□CH-S CHt -NH CH.

CH, -NH-C-CH, 5-CII=CI+.

pd-5 CH.

pd pct In Em-1 of Example 1, the average equivalent sphere diameter of the seed crystal was set to 0.
．． 5 μm, so the average equivalent sphere diameter of the final particles is 0.75
Em-11 is an emulsion prepared in the same manner as Em-1 of Example 1, except that the emulsion is μm.

Emulsions 12 and 13 were prepared by adding a thiosulfonic acid compound and a reduction aggravating agent in the amounts shown in Table 3-1 to Em-11 in the same manner as described in Example 1.

Emulsions 12 to 13 of the present invention prepared in this manner and Comparative Example 1
1 was optimally total sulfur sensitized using sodium thiosulfate and chloroauric acid for each emulsion.

4th layer silver iodobromide emulsion I, 8th layer silver iodobromide emulsion ■
, Sample 30 except that the silver iodobromide emulsion ■ in the 14th layer was changed.
Samples 302 to 303 were prepared in the same manner as in Example 1.

Table 3-1 Furthermore, samples 304 to 306 were prepared by changing the gold amounts of samples 301 to 303 in the same manner as shown in Example 1, as shown in Table 3-2.

Samples 301 to 306 were shown in Example 1 (A) and (B
) After storage under storage conditions, sensitivity and fog were measured. Further, hydrogen sensitization was performed in the same manner as in Example 1, and the increase in sensitivity ΔS7 was measured.

Sensitivity and fog measurements were performed using the same exposure, color development, and density measurements as in Example 1. The results obtained are shown in Table 3-3.

Regarding the results of photographic performance, the sensitivities of the red-sensitive layer, green-sensitive layer, and blue-sensitive layer were each expressed as relative sensitivities when the sensitivity of sample 301 was set as 100.

As is clear from Table 3-3, the photosensitive material of the present invention has the effect of increasing sensitivity with almost no increase in fog, and has excellent storage stability.

Claims (2)

[Claims] (1) In a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, the unit is the common logarithm value of the exposure amount expressed in lux seconds, expressed by the following formula (1). Sensitivity increase Δ due to hydrogen sensitization
Sn is 0.05 or less and the ratio of the amount of gold coated to the amount of silver coated in the photosensitive material per unit area (gold/silver)
A silver halide photographic material having a weight ratio of 3.0×10^-^5 or less. Formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (where n is the number of substantially different color-sensitive layers,
ΔSi is the width of increase in sensitivity due to hydrogen sensitization for each color-sensitive layer. ) (2) Claims characterized in that the photographic light-sensitive material is a color negative photographic light-sensitive material having a plurality of red-sensitive silver halide emulsion layers, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer. The silver halide photographic material according to item 1.