JPS5828738A - Photographic sensitive silver halide material - Google Patents

Abstract

PURPOSE:To prevent a change due to the desorption of a spectrally sensitizing dye with the passage of time by adding a water soluble bromide to a silver chlorobromide emulsion after finishing the chemical aging of the emulsion. CONSTITUTION:After finishing the chemical aging of a blue-sensitive photographic silver chlorobromide emulsion sensitized by a sensitizing dye expressed by the general formulaIor II (where each of X1 and Y1 is Se or S, one of them is Se, R1 is lower alkyl or allyl, L1 is lower alkylene, each of X2 and Y2 is Se or S, L2 is lower alkylene, R2 is lower alkyl or allyl, and each of R3-R6 is H, lower alkyl, alkoxy or the like), a water soluble bromide of Cd, Li, Na or the like is added to the emuslion by 1-80mol% to the amount of the silver chloride. The preferred bromine content of the siver chlorobromide is 15-99mol%. The desorption of the sensitzing dye from the silver halide is prevented, and a sensitivity change is not caused.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silver halide photographic material, and more particularly to an improvement in a silver halide photographic material having a blue-sensitive emulsion layer sensitized with a cyanine dye.

Silver halide photographic materials are generally subjected to chemical sensitization such as sulfur sensitization or noble metal sensitization in order to increase the sensitivity of the blue-sensitive emulsion layer.

However, if the sensitivity inherent to silver halide is sensitized without using a sensitizing dye, there is a problem that the grains become coarser and the sharpness of the photographic image deteriorates. When used as the spectral sensitivity range of a blue-sensitive emulsion layer, depending on the type of silver halide photographic light-sensitive material, a slight defect may occur on the longer wavelength side of the spectral sensitivity required to express the color of the blue-sensitive emulsion layer. It has also been attempted to extend the sensitivity range inherent to silver halide to longer wavelengths by using dyes as sensitizers.

As a sensitizing dye that meets the above purpose,
Cyanine dyes such as those described in No. 538 are particularly useful; however, when the silver halide used in photographic light-sensitive materials is silver chlorobromide, this type of sensitizing dye cannot be used under various conditions. It has the disadvantage of being easily desorbed from silver halide.

Fluctuations in performance due to desorption of sensitizing dyes from silver halide occur during the production of light-sensitive materials, such as changes in sensitivity over time even after spectral sensitization, even when the emulsion is stored in a refrigerator, and changes in performance from the preparation of the emulsion to the coating process. Even when stored at a high temperature suitable for coating, the sensitivity may vary within the same lot if the storage time is prolonged, which is extremely unfavorable in terms of product quality.

As a means for preventing desorption of sensitizing dyes, Japanese Patent Application Laid-Open No. 54-6942
A method of preventing desorption while supersensitizing using two types of sensitizing dyes as described in No. 9, a method of adding azoles, azaindene compounds, etc. known as stabilizers,
Some methods have been proposed, such as adding a reducing agent such as hydroquinones or sulfinic acids, or using a specific copolymer and a fluorescent brightener in combination, as described in JP-A-49-111629. The effect is insufficient for silver chlorobromide.

Therefore, a first object of the present invention is to provide a technique for preventing the desorption of dyes from silver halide that has been spectrally sensitized with cyanine dyes and the like, and for producing emulsions with excellent stability over time.

The second object is to prevent the desorption of dyes from silver halide spectrally sensitized with cyanine dyes and the like, and to provide emulsions with excellent stability over time.

The present inventors have discovered that when a silver chlorobromide emulsion, which is normally used in printing and positive light-sensitive materials, is color-sensitized as a blue-sensitive emulsion using a cyanine dye due to its characteristics, the sensitizing dye As a result of intensive research into means for preventing the attachment and detachment of the material, it has been discovered that the above object can be achieved by the following means.

In a silver halide photographic material having a blue-sensitive emulsion layer containing silver halide grains sensitized with a sensitizing dye represented by the following general formula (I) or ([), the silver halide grains are substantially The purpose is achieved by adding water-soluble bromide in an amount of 1 to 80 mo1% based on the silver chloride constituting the silver halide grains into the blue-sensitive emulsion after chemical ripening. was found to be achieved.

b- (In the formula, xl and Y+ represent a selenium atom or a sulfur atom, one of X and Yl represents a selenium atom, and R1 is a lower alkyl group or an allyl group that may have a substituent. (wherein, Y2 represents a selenium atom or a sulfur atom, R2 represents a linear or branched lower alkylene group, and R2 represents a linear or branched lower alkylene group. represents a lower alkyl group or an allyl group which may have a substituent, and R3, bird, R5 and R6 represent a hydrogen atom, a lower alkyl group, an alkoxy group, a hydroxy group, a halogen atom or an aryl group, but R3, R4 ,R
5 and R6 are not all hydrogen atoms at the same time. ) In the present invention, the timing of addition of water-soluble bromide is specified because the effect of the present invention and the photographic performance of the emulsion vary greatly depending on the timing of addition. (Later or second stage)
It has been found that the effect is significant when added to the emulsion after the completion of ripening and before coating.

In the present invention, as the water-soluble bromide, cadmium, lithium, sodium, potassium, and ammonium bromides are usually used, but there are no particular limitations as long as the bromide is water-soluble.

If the amount of water-soluble bromide added is less than 1 mol % with respect to silver chloride constituting the silver halide, the effect of the present invention will hardly be exhibited, and if it is greater than 80 mol %, the gradation of the emulsion will be undesirably soft.

Therefore, in the present invention, the preferable range is 1 to 80 mo1% based on the silver chloride constituting the silver halide, which is good for both the non-delayering property of the dye and the photographic performance of the emulsion. The case where it is 20 to 50 mo1% is particularly good.

The bromine content of the silver chlorobromide used in the present invention is suitably 15 to 99 m, -+1%, in order to exhibit relatively high contrast photographic characteristics. Further, the emulsion may be produced by any emulsion manufacturing method such as forward mixing, back mixing, simultaneous mixing, compulsion method, acid method, neutral method, ammonia method, thioether method, etc. In addition, the halogenated 111117) particle size is 0.2
The particle size is preferably about μm to 2.0 μm, and the shape of the particles may be regular or irregular, and the particle size distribution may be wide or narrow. However, so-called monodisperse emulsions with a narrow particle size distribution is more effective for the effects of the present invention.

In addition, the above-mentioned silver chlorobromide is active gelatin, water-soluble gold salt, water-soluble bromide, water-soluble palladium clay, water-soluble rhodium salt, water-soluble iridium salt, etc. Noble metal sensitizers: sulfur sensitizers; selenium sensitizers ; Chemical sensitization can be carried out using chemical sensitizers such as polyamines, reduction sensitizers such as stannous chloride, etc. alone or in combination. Further, as other sensitizers, sensitizers such as polyalkylene oxide compounds may be included.

Furthermore, by containing stabilizers such as triazoles and azaindenes, it is possible to more stably prevent changes in photographic properties over time.

Here, explanations and specific examples of the sensitizing dyes (I) and (6) used in the present invention will be given.

The sensitizing dye ([), (2) is represented by the following general formula.

General Formula (1) General Formula (2) Here, xl and Yl represent a selenium atom or a sulfur atom, and either one of Xl and Yl represents a selenium atom. R1 and R2 are lower alkyl groups which may have substituents (for example, methyl group, ethyl group, propyl group, butyl group, β-human tetraxethyl group, β-methoxyethyl group, β-sulfonethyl group, γ- 9- represents a sulfopropyl group, r-sulfobutyl group, 0-sulfobutyl group, etc.) or an allyl group. Ll and R2 represent a linear or branched lower alkylene group (eg, ethylene group, propylene group, butylene group, etc.). R3, R4, R6 and R6 are hydrogen atoms, lower alkyl groups (e.g. methyl group, ethyl MI4),
It represents an alkoxy group (e.g. methoxy group, ethoxy group, etc.), a hydroxy group, a halogen atom (e.g. fluorine atom, chlorine atom, bromine atom) or an aryl group (e.g. phenyl group, etc.), but all of R3, R6 and R6 are It cannot be a hydrogen atom at the same time.

Specific representative examples of the sensitizing dyes represented by the general formulas ([) and proviso) are shown below. For convenience, the symbols used in general formulas (1) and (6) are shown in Tables 1 and 2 below and replaced with specific structural formulas. In the formula, L1 and R2 are a nitrogen atom on the left and a sulfur atom on the right. , dissolved in a solvent such as acetone or water. The amount of the dye added varies depending on the light-sensitive material to which the silver halide photographic emulsion of the present invention is applied, but it is usually used in the range of 5x io-' to L5x10-mole per mole of silver halide. It will be done. .

13- The addition time may be either before or after adding the water-soluble bromide, but it is preferably effective to add it before adding the water-soluble bromide.

In addition to these sensitizing dyes, various conventionally known photographic additives may be added as necessary.

The silver halide photographic emulsion of the present invention is coated on a support,
Form a blue-sensitive emulsion layer. This blue-sensitive emulsion layer may be one layer or two or more layers. Furthermore, it may be constructed by a combination of two or more silver halide photographic emulsion layers each containing a different silver halide. When the emulsion of the present invention contains a yellow coupler, it becomes a nonolar light-sensitive emulsion that forms a so-called internal yellow dye image.

A typical yellow coupler that can be used in the present invention is an open chain ketomethylene compound. For example, 4-equivalent type couplers such as benzoylacetanilide type and Viva pilacetanilide type couplers, or substituted with a -14= substituent (so-called split-off group) in which the hydrogen atom at the coupling position can be separated during the coupling reaction. being done 2
A typical coupler is available. Specific representative examples are shown below.

(YQ-1) α-(4-carboxyphenoxy)-α Hebibaryl-2
-Chloro-5[γ-(2,4-dyl-t-amylphenoxy)butyramide]acetanilide.

(yo-2) α-benzoyl-2-chlorop-5-[:γ-(2゜4-
di-t-amylphenoxy)butyramide diacetanilide.

(:yo-3) α-benzoyl-2-chloro-5-[α-(dodecyloxycarbonyl)ethoxycarbonyl]acetanilide.

(yo-4) α-(4-carboxyphenoxy)-α-Vivalyl 2
-chloro5-(α~(3-bentatecylphenoxy)
Butyramide diacetanilide.

(YO-5) α-(1-Benzyl-2,4-dioxo-3-imidazolysinium)-α-Vivalyl-2-Tarolow 5-[γ-(
2,4-di-t-amylphenoxy)butyramide]acetanilide.

(YO-6') α-[1,4-(]-]benzyru-2-phenyl-35
-dioxy-1,2,4-)lyasolycinyl)]-]
α-Vivalyl-2-chloro-5-γ-(2,4-di-t
-Amylphenoxy)butyramide] amylphenoxy)butylamide.

(YO-7) α-acetoxy-α-(3-[α~(2,4-di-t-
amylphenoxy)butyramide]henzoyl)-2-
Methoxyacetanilide.

(yo-8) α-(3-[α-(2,4-dyl-t-amylphenoxy)butyramide]bency/l/)-2-methoxyacetanilide.

(yo-g) α-(4-(4-benzyloxyphenylsulfonyl)
phenoxy]-α-bivalyl-2-ri p-5-[γ-
(2,4-di-t-amylphenoxy)butyramide diacetanilide.

(YO-10) α-Bivalyl α-(4,5-dichloro-3(2H)-
hyritazol-2-yl)-2-chloro-5-(hexapsyloxycarbonyl)methoxycarbonylacetanilide.

(yo-11) α-Vivalyl α-[:4-(i-chlorophecol)-
5-Oxo-Δゝ-tetrazolin-1-yl]-2-chloro0-5-(α-(dodecyloxycarbonyl)ethoxycarbonyl)acetanilide.

(yo-12) α-(2,4-dioxy-5,5-dimethyloxasoricin-3-yl)-α-pivalyl-2-chloro-5-[
α-(2,4-di-t-amylphenoxy)butyramide diacetanilide.

17- (yo-13) α-vivalyl α-(4-(1-methyl-2-phenyl-3,5-dioxo-1,2,4-)riasoricinyl)
-2-Chloro-5-[γ-(2°4-di-t-amylphenoxy)butyramide]acetanilide.

(yo-14) α-hyhalyl α-(4-(p-ethylphenyl)-5
-Oxo-Δ2-tetrasilyl-1-yl]-2-chloro-5-[γ-(2,4-di-t-amylphenoxy)butyramide In addition to these yellow couplers, Hun heating couplers may also be used depending on the purpose. , development inhibitor-releasing coupler,
Colored couplers for masks can also be added.

Furthermore, various other photographic additives can be added to this silver halide emulsion, such as aldehydes such as formaldehyde, halogen-substituted fatty acids of mucobrome [I, hardeners such as ethyleneimine compounds: saponin, polyethylene, etc. Glycol laurel is a spreading agent or surfactant such as oleyl monoether; a physical property improver such as glycerin or polymer aqueous dispersion (latex); Inhibitors; Dispersants also used as coupler solvents such as tricresyl phosphate, dibutyl phthalate, ethyl acetate, butyl acetate, chloroform, methanol, etc.; Various photographic additives can be included, such as a fluorescent brightener (as described in the above publication), a condensate of phenols and formalin, and the like.

The silver halide photographic emulsion of the present invention is generally coated on a suitable support and dried to produce a 710 silver halide photographic light-sensitive material. nitrate,
A support such as polyester, polyamide, or polystyrene, or a laminate of two or more substrates such as a laminate of paper and polyolefin (polyethylene, polypropylene, etc.) may be used. In order to improve the adhesion to the silver halide emulsion, this support is generally subjected to various surface improvement treatments, such as surface treatment such as electron impact treatment, or subbing treatment to provide a subbing layer. used.

The silver halide photographic emulsion is coated on this support and dried by a commonly known coating method such as dip coating, roller coating, bead coating, curtain flow coating, etc., followed by drying.

The silver halide photographic light-sensitive material according to the present invention is basically constructed as described above, but is further spectrally sensitized to other wavelength regions, that is, green-sensitive and red-sensitive silver halide photographic emulsion layers, an intermediate A color photographic light-sensitive material can be formed by combining various photographic constituent layers selected as necessary from among the following: a layer, a protective layer, a filter FW/j, an antihalation Nj, a packing layer, etc. In the case of so-called internal color light-sensitive materials, the green-sensitive and red-sensitive emulsion layers contain couplers which form magenta and cyan images, respectively, by color development.

After exposing a photographic light-sensitive material using the silver halide photographic emulsion of the present invention, various photographic treatments are used.

The processing temperature and time are set appropriately, and the temperature is room temperature,
Lower than room temperature, e.g. 18℃ or less, or higher than room temperature 3
The temperature may exceed 0°C, for example around 40°C, or even exceed 50°C. Further, depending on the purpose, either black and white photographic processing for producing a silver image or color photographic processing for producing a color image can be applied. Developing agents used in black-and-white photographic processing include methyl-4-aminophenol hemisluaate, dibenzyl-4-aminophenol dichloride, and diethyl-4-aminephenol hydrochloride! , 4-
4-amine phenols represented by aminophenol sulfur salt; 1-phenyl-3-pyrazolidone, 4,4
- 3-pyrazolidones such as dimethyl-1-phenyl-3-virasoliton, 4-methyl-1-phenyl-3-pyrazolidone; 1-ide p-quinone, 2-methylhydroquinone, 2-phenylhydroquinone, 2-chlorohydroquinone Polyhydroxybenzenes such as , hyrocalol, and catechol; p-phenylenediamine hydrochloride 21
- p-phenylenediamines such as NI salt, N-dimethyl-p-phenylenediamine sulfate, ascorbic acid, N-(p-hydroxyphenyl)glycine, etc. can be used alone or in appropriate combinations. For color photographic processing, for example, N,ti-dimethyl-p is used as a color developing agent.
-phenylenediamine, N,N-diethyl-p-phenylenediamine, ■=carbamidomethyl-N-methyl-p
-phenylenediamine, U-carbamidomethyl-tetrahydrofurfuryl-2-methyl-p-phenylenediamine, N-ethyl-N-carboxymethyl-2-methyl-p-phenylenediamine, ■-carbamidomethyl-N-ethyl -2-methyl-p-phenylenediamine, Ken-ethyl/l/-N-tetrahydrofurfuryl-2-methyl-9-aminophenol, 3-acetylamino-4-
Aminodimethylaniline, U-ethyl-N-β-methanesulfonamidoethyl-4-aminoaniline, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline, N-methyl-■- β-22= Sodium salt of sulfonythyl-p-phenylenediamine, etc. can be used.

After development, a fixing process, a bleaching process, and a fixing process are performed.

Bleaching treatment may be carried out simultaneously with fixing treatment. Many compounds are used as bleaching agents, among them iron (6),
Polyvalent metals such as cobalt (1) and copper (6), triacetic acid, N-
Aminopolycarboxylic acids such as hydroxyethylethylenediaminetriacetic acid, metal salts such as malonic acid, tartaric acid, malic acid, diglycolic acid, dithioglycolic acid, or ferricyanide acid, dichromate, etc. alone or in appropriate combinations. is used.

Next, the present invention will be explained in more detail by way of examples.

Example-1 A silver chlorobromide emulsion containing 15 mol 1% of chloride chains (1 kg contains 0.25 mol of silver halide with an average grain size of 0.7 μm and 100 Ii of cetin) was sulfur-sensitized according to a conventional method. 4-hydroxy 6-methy/l/-1,3,3a,
Adding 1 g of 7-tetrazaindene per m01 of silver halide, and further adding 2 x 10-' mol of exemplary sensitizing dye (II-7) per m01 of silver halide,
After dividing into 7 portions, <1iBr was added in varying amounts as shown in Table 3.

To this, a yellow coupler (YC~6) was dissolved in dibutyl phthalate and ethyl acetate and emulsified and dispersed in a gelatin solution using sodium alkylbenzene sulfonate.The emulsified dispersion was added to the above emulsion with a coupler content of 0 per mole of silver halide.
．． A coating solution was prepared by adding 3 moles of the solution. This coating solution was coated on a polyester support (A) immediately after preparation and (B) after being stored at 50°C for 3 hours to give 1 g of halogenated a4F gelatin/d as metallic silver, and after drying, gelatin 177 /i and dried.

These samples were exposed to wedge light using a KS7 type sensitometer (manufactured by Konishiroku Photo Industry Co., Ltd.), and developed at 32°0 with the following color developer.
Developed for 10 minutes, followed by normal bleach-fixing and color sensitometry. The results are shown in Table 3. I-ethyl-N-p-methanesulfonamidoethyl-3 per 1 ml of color developer aqueous solution
-Methylaminoaniline hydrochloride 25g anhydrous sodium sulfite 20p benzyl alcohol 38cc hexametaphosphate sodium
20F carbonated soda water salt 50
0g Brompotash ION Caustic Soda 0.6g Table-3 25- *Sensitivity is relative sensitivity value when Blank 1 is taken as 100 As is clear from Table-3, 1 mo1% or more of KBr is added to Ag0l of silver chlorobromide. It can be seen that the increase in sensitivity is large and the decrease in sensitivity due to aging of the coating liquid is small. On the other hand, if it exceeds 8Q mo'l, sensitization is achieved but the gradation becomes softer and capri increases, which is not preferable.

Example 2 The emulsion used in Example 1 was prepared by changing the timing of addition of water-soluble bromide, and then the sample was processed according to Example 1.

26- It can be seen that by adding a water-soluble bromide after the completion of ripening as in the present invention, sensitivity fluctuations over time are significantly improved.

Example 3 After adding the following sensitizing dye to the emulsion used in Example 1 at 2×10 moles based on silver chlorobromide, 50 mo1% of water-soluble bromide based on Ag0IK of silver chlorobromide was added. was added to prepare an emulsion. The coating liquid preparation process was based on Example-1.

Comparative Compound H3 Table - σ It can be seen that the effect of adding water-soluble bromide becomes significantly greater when combined with the sensitizing dye of the present invention.

Example 4 A photo paper support coated with a polyethylene film containing anatase-type titanium oxide was pretreated with corona discharge to improve the polyethylene film, and the following layers were sequentially layered from the support side. , seven types of color photographic materials were created.

Layer-1 Blue-sensitive silver halide emulsion layer Silver chlorobromide emulsion containing 15 mol% of silver chloride (0.25 mol of silver halide with an average grain size of 0.6 μm per lky, 1 gelatin)
2.5XIO per mole of silver halide in
-'mol of sensitizing dye of exemplary compound (I-6) is added,
Further, 0.3 mol of the yellow coupler YO-5 exemplified above per mol of silver halide, and 0.15 mol of 2,5-di-t-, a color stain inhibitor, per mol of this coupler.
Octylhydroquinone was simultaneously added dispersed with dibutyl phthalate. The amount of coated silver after drying is 0.35 g/m' as gold/l; the amount of gelatin is 1.31/m'.
/G was coated to a film thickness of 2.3 μm.

Layer-2 Intermediate layer After drying, an aqueous gelatin solution was coated at a thickness of 1.0F/75.0.9μ.

Layer-3 Green-sensitive silver halide emulsion layer A silver chlorobromide emulsion containing 20 mol% of silver chloride (0.25 mol of silver halide with an average grain size o, aμ per 1 g, 1 gelatin)
25g) per mole of silver halide. OX1
0-' moles of anhydro-5,5'-diphenyl;
29-9-Ethyl-3,3'-(di-γ-sulfopropyl)oxacarpocyanine hydroxide was added to make it green sensitive, and magenta coupler 1-(2,4,6-1
-lichlorophenyl)-3-(2-chloro-5-octadecenylsuccinimide=lJ/)-5-pyrazolone in butyl phthalate tricresyl phosphate
:1 mixture was used to disperse the mixture, and the mixture was added at a concentration of 0.2 mol per 1 mol of halogenated 11!. The color stain inhibitor 2,5-di-t-octylhydroquinone was dispersed in this using the same mixed solution at 0.3 mol per mol of the coupler, and the antioxidant 2,2.4-)dimethio-6 Monolauryloxy-7-t-octylchroman was added in an amount of 0.5 mol per mol of coupler, and the amount of coated silver after drying was o, 3y/lr? , gelatin amount 1,49/ze, film thickness 2.
It was coated to have a thickness of 4μ.

Layer-4 Intermediate layer A gelatin aqueous solution was coated at a ratio of 2.097 parts of gelatin.

Layer-5 Red-sensitive silver halide emulsion layer 30- Silver chlorobromide containing 20 mol% of silver chloride (0.25 mol of silver chlorobromide with an average grain size of 0.2 μ per 1 g, gelatin 12
3.0 x 10 - per mole of K silver halide (containing 5 g)
4 moles of 3-ethyl-1'-carbamoylmethyl-4,
5-hendithia-4'-carbocyanine chloride, cyan coupler 2,4-dichloro-3-methyl-6-[α-
(2,4-di-t-amylphenoxy)butyramide]
Phenol and 0.1 mol of color stain inhibitor 2,5-di-t-octylhydroquinone per mol of coupler are simultaneously dispersed using dibutyl phthalate, resulting in 0.2 mol of coupler per mol of silver halide. The amount of coated silver after drying was 0.25! 1/rrl, gelatin amount: 1.2 g/m''z, film thickness: 1.5 μm.

Layer-6 Protective layer A gelatin aqueous solution was coated at a rate of 2.0 g/m of gelatin.

The silver halide emulsions used in layers 1, 3, and 5 were sulfur-sensitized with sodium thiosulfate, and in addition to the above materials, the stabilizer 4-hydroxy-6-methyl-
It contained 1,3,3a,7-tetrazaindene sodium salt, bis(vinylsulfonylmethyl)ether as a hardening agent and saponin as an ME fabric aid.

In the experiment, water-soluble bromide was added in varying amounts after ripening at the stage of preparing the emulsion forming layer-1. After exposure to blue light, green light, and red light through the light beams using 1-1, color development processing was performed according to the following processing steps.

Processing process Temperature Time Color development: Bleach fixing at 3°C for 3 minutes and 30 seconds
Wash with water at 33℃ for 1 minute and 30 seconds
Dry at 33°C for 3 minutes and 30 seconds 8
0℃ Color developer Benzyl alcohol 15ml Ethylene glycol 15TLIWhitθX
BP (50% solution) (*Product name of Sumitomo Chemical Co., Ltd.) 2m/Hydroxylamine sulfate 3g3-Methyl-4-amino-U-ethyl-N-(β-methanesulfonamidoethyl)aniline sulfate @ salt
4.59p-toluenesulfonic acid
10.11 Potassium carbonate
311 Potassium sulfite +1
・Potassium dibromide 0.5g
Potassium chloride ゛ 0.5I!
1-Hydroxyethylidene 1,1 diphosphonic acid (60%
Aqueous solution) Add 2ml water and 11! and adjust the pH to 10 with sulfuric acid or potassium hydroxide solution.
．． Adjust to 2.

Bleach-fix solution ethylenediaminetetraacetic acid 40Ii Ammonium sulfite (40% solution) 351 Ammonium thiosulfate (70% solution) 1as*Ethylenediaminetetraacetic acid m1MI)l-) Lium 7
0g ammonia water (28%) 35-3
3- Add water and adjust the pH to 7 using aqueous ammonia or glacial acetic acid.

The reflection density of the dye image of the blue-sensitive emulsion formed in each sample was measured using a Sakura color densitometer model PDA-60 (manufactured by Konishiroku Photo Industry Co., Ltd.) and an attached blue filter.

Table 8 It is clear that even when the multilayer coating samples were stored over time (40° C., relative humidity 80%, 7 days elapsed), the sensitivity fluctuations of the samples to which water-soluble bromide was added were significantly smaller.

Agent Yoshihiro Kuwahara 34- Written amendment September 1980 2411 1 Indication of the case 1983 Patent Application No. 109558 2 Name of the invention Silver halide photographic light-sensitive material 3 Person making the amendment Relationship to the case Patent application Address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name (+27) Representative Director Kawa Konishiroku Photo Industry Co., Ltd.
Nobuhiko Moto 4 Agent Address: 191 Address: 1-5 Sakura-cho, Hino-shi, Tokyo Date of amendment order: 68 Column 7 of “Detailed description of the invention” of the specification to be amended, Contents of the amendment: Detailed description of the invention The explanation has been amended as follows.

2-

Claims (1)

[Scope of Claims] A silver halide photographic light-sensitive material having a blue-sensitive emulsion layer containing silver halide grains sensitized with a sensitizing dye represented by the following general formula (I) or (Company), wherein the halogen The silver oxide grains are substantially silver chlorobromide, and after completion of chemical ripening in the blue-sensitive emulsion, water-soluble particles are added in an amount of 1 to 80 mo1% based on the silver chloride constituting the silver tetragenide grains. A silver halide photographic material characterized by containing bromide. General formula (1) (wherein, X and Y represent a selenium atom or a sulfur atom, one of Xl and Y represents a selenium atom, and R1 is a lower represents an argyl group or an allyl group, and Ll represents a straight-chain or branched lower alkylene group. Represents a lower alkylene group, R2 represents a lower alkyl group or allyl group which may have a substituent, R3, R4, R6 and horse represent a hydrogen atom, a lower alkyl group, an alkoxy group, a hydroxy group,
Represents a halogen atom or an aryl group, but R3, R4,
Not all R5 and R6 are hydrogen atoms at the same time. )