JP2557252B2 - Silver halide photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material containing a dye, and more particularly to a halogenated silver halide photographic material containing a hydrophilic colloid layer colored with a dye useful as a light absorbing dye. It relates to a silver photographic light-sensitive material.

[Background of the Invention]

Silver halide photographic material (hereinafter referred to as photosensitive material)
It is well known that a photographic material contains a dye for the purpose of absorbing light of a specific wavelength for the purpose of absorbing light of a specific wavelength in order to prevent a filter, antihalation, prevention of irradiation, or sensitivity adjustment of a photographic emulsion. It is common practice to color sexual colloid layers.

The filter layer is usually located above the photosensitive emulsion layer or between the emulsion layer and the emulsion layer, and serves to convert incident light reaching the emulsion layer into light having a preferable spectral composition. Further, for the purpose of improving the sharpness of the photographic image, an antihalation layer is provided between the emulsion layer and the support or on the back surface of the support to prevent harmful effects at the interface between the emulsion layer and the support and the back surface of the support. It is common practice to absorb the reflected light to prevent halation, or to color the emulsion layer to absorb harmful reflected or scattered light from silver halide particles, etc. to prevent irradiation. I have.

A dye used for such a purpose has good absorption spectrum characteristics according to the purpose of use, is completely decolorized during the photographic development process, is easily eluted from the photographic material, and remains after the development process due to the dye. No color contamination, no adverse effects such as fog or desensitization on photographic emulsion, no diffusion from dyed layer to other layers, and
It must satisfy various conditions such as excellent stability over time in a solution or in a photographic material and no discoloration.

To date, a number of efforts have been made and a number of dyes have been proposed with the aim of finding dyes satisfying the above conditions. For example, UK Patent 506,385, U.S. Patent 3,2
No. 47,127, Japanese Examined Patent Publication No. 39-22069, Oxonol dyes described in 43-13168, etc., styryl dyes represented by U.S. Pat.No. 1,845,404, merocyanine dyes represented by U.S. Pat. There are representative cyanine dyes and the like. However, in reality, there are very few good dyes that satisfy all the above conditions and can be used in photographic materials.

[Object of the Invention]

Accordingly, it is an object of the present invention to have good absorption spectrum characteristics, decolorize during photographic development processing, and elute from photographic materials to minimize residual color contamination after processing, and to be inert to photographic emulsions. An object of the present invention is to provide a silver halide photographic material containing a certain dye.

[Structure of Invention]

The above objects of the present invention are 3H-pyrrolopyridine, 4H-thienopyrrole, 6H-thienopyrrole, 4H-furopyrrole and
At least one cyanine dye having at least two acid groups in the dye molecule of a cyanine dye having 6H-furopyrrole as a nucleus or at least two substituents having one or more --CH ₂ CH ₂ OR groups It is achieved by a silver halide photographic light-sensitive material characterized by having a hydrophilic colloid layer containing

 R represents a hydrogen atom or an alkyl group.

The dye compound of the present invention is represented by the following general formulas (I), (II) and (III).

General formula (I) General formula (II) General formula (III) In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ each represent an alkyl group, and Z ₁ and Z ₂ each represent a non-metal atom required to form a pyrrolopyridine, thienopyrrole, and floppyrrole ring. Represents a group.

Y ₁ and Y ₂ represents a non-metallic atomic group necessary for forming a pyrrolopyridine ring, and, in the Y ₁ ring It shall include binding.

R ₁ in the general formula _{(I), R 2, R} 3, R 4, R 5, R 6, Z 1, Z 2, R in the general formula _{(II) 1, R 2,} R 3, R 4, R 5 , R ₆ , Y ₁ , Y ₂ and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , Y ₁ , Z ₂ in the general formula (III) are each an acid having at least two dye molecules. It represents a group makes it possible to have at least two substituents having at least one group or -CH ₂ CH ₂ oR groups makes it possible to have a group.

R represents a hydrogen atom or an alkyl group.

 L represents a methine group; Represents an anion. m is 1
Represents an integer of 5 and n represents an integer of 1 or 2. Dye
N is 1 when forming an intramolecular salt.

Examples of the acid group in the general formulas (I), (II) and (III) include a sulfonic acid group, a carboxylic acid group and a phosphonic acid group, and each of these acid groups includes a salt thereof. Examples of the salt include alkali metal salts such as sodium and potassium, and organic ammonium salts such as ammonium, triethylamine and pyridine.

The alkyl group represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ is preferably a lower alkyl group having 1 to 8 carbon atoms (eg, methyl, ethyl, propyl, i-propyl, butyl). Group) and may have a substituent other than the above-mentioned acid substituent or —CH ₂ CH ₂ OR group.

The alkyl group represented by R is preferably a lower alkyl group having 4 or less carbon atoms.

Examples of the substituent containing a —CH ₂ CH ₂ OR group include a hydroxyethyl group, a hydroxyethoxyethyl group, a methoxyethoxyethyl group, a hydroxyethylcarbamoylmethyl group, a hydroxyethoxyethylcarbamoylmethyl group,
Examples thereof include N, N-dihydroxyethylcarbamoylmethyl group, hydroxyethylsulfamoylethyl group and methoxyethoxyethoxycarbonylmethyl group.

Other substituents that Z ₁ , Z ₂ , Y ₁ and Y ₂ may have include a sulfo group (including a salt), a carboxyl group (including a salt), a hydroxyl group, a cyano group, a halogen atom ( For example, fluorine, chlorine, bromine atom, etc.) can be mentioned.

The methine group represented by L may also have a substituent, and as the substituent, a substituted or unsubstituted lower alkyl group having 1 to 5 carbon atoms (for example, methyl, ethyl, 3-hydroxypropyl, 2-sulfoethyl). Groups, etc.), halogen atoms (eg, fluorine, chlorine, bromine atoms, etc.), aryl groups (eg,
Examples thereof include a phenyl group) and an alkoxy group (eg, methoxy group, ethoxy group, etc.). Also, a 6-membered ring containing three methine groups (for example, 4,
4-dimethylcyclohexene ring) may be formed.

 X The anion represented by
Examples of the body are halogen ion, p-toluenesulfonic acid
Ions, ethylsulfate ions and the like can be mentioned.

Dyes represented by the general formulas (I), (II) and (III) used in the present invention (hereinafter referred to as the dye of the present invention)
Specific examples of the above are shown below, but the present invention is not limited thereto.

Specific compound The dye of the present invention is a product of Journal of the Chemical
It can be synthesized with reference to Society (J. Chem. Soc.) Page 189 (1933), US Pat. No. 2,895,955, and JP-A-62-123454.

Examples of the mother nucleus of the dye of the present invention include the following compounds.

Compound (A) can be synthesized by the method described in J. Chem. Soc., 3202 (1959) and the method described in British Patent 870,753.

Compound (B) can be synthesized by the method described in J. Chem. Soc., 584 (1961).

The compound (C) can be synthesized by the method described in British Patent No. 841,588.

Compound (D) Chemical Abstracts (CA) 62, 104
It can be synthesized by the method described in 38c and CA 71 , 22045m.

Compound (E) can be synthesized by the method described in CA 71 , 22045m.

Compounds (F) and (G) can be synthesized in a similar manner.

Using these mother nuclei, quaternization, sulfonation and the like can be carried out as necessary. Or J. Chem. Soc., 3202 (19
59) and J. Chem. Soc., 584 (1961) according to the synthetic method, N-alkyl-N-pyridylhydrazine is synthesized, cyclized via hydrazone, and treated with an acid as necessary. A 1-alkyl-substituted-3H-pyrrolopyridine derivative can be obtained and used as a starting material.

The compound of the present invention can be easily obtained by reacting an appropriate methine chain donor with the quaternized and optionally sulfonated mother nucleus compound.

If glutaconaldehyde dianyl hydrochloride is used as the methine chain supplier, a heptamethine dye is obtained, and if propenedianyl hydrochloride is used, a pentamethine dye is obtained. In the case of trimethine dye, diphenylformamidine hydrochloride may be used. A monomethine dye can be similarly synthesized by using a mother nucleus compound having an alkylthio group in the active portion according to a conventional method. For nonamethine dyes,
As a methine chain supplier, for example, Harmer, "The Cyanine Soybean and Relayed Compounds" (F.
M.Hamer “The cyanine dyes and related compounds” 19
64, Interscience Publishers), pages 249-251.

 Next, representative synthetic examples of the dye of the present invention will be shown.

Synthesis Example 1 (Synthesis of Compound Example 46) The compound (B) synthesized according to the above-mentioned document was quaternized with propane sultone according to a conventional method, and then 5.0 g of this quaternized product was obtained.
Was dissolved in 40 ml of acetic acid with heating, 1.0 g of glutaconaldehyde dianyl hydrochloride, 9 ml of acetic anhydride and 13 ml of pyridine were added, and the mixture was heated and stirred at a bath temperature of 80 to 85 ° C for 30 minutes.

After cooling, isopropyl ether was added for decantation. Further, methanol, acetone and isopropyl ether were added and decantation was performed for purification to obtain a compound (46).

Synthesis Example 2 (Synthesis of Compound Example 47) The compound (A) synthesized according to the above-mentioned document is quaternized with propane sultone according to a conventional method, then reacted under the same reaction conditions as the compound (46), and then purified. The compound (47) was obtained.

Synthesis Example 3 (Synthesis of Compound Example 20) The above compound (A) was quaternized with propane sultone, and then sulfonated with concentrated sulfuric acid and fuming sulfuric acid. 2.6 g of the sulfonate was dissolved in 10 ml of N, N-dimethylformamide,
Glutaconaldehyde dianyl hydrochloride 1.0 g, pyridine 2 m
1 and 2 ml of acetic anhydride were added, and the mixture was heated and stirred at a bath temperature of about 100 ° C for 20 minutes. Isopropyl ether was added to the reaction mixture, which was decanted and purified to obtain compound (20).

Synthesis Example 4 (Synthesis of Compound Example 48) 2,3,3-Trimethyl-5-chloro-1,4-diazaindene was synthesized according to the above-mentioned document. This was quaternized with propane sultone according to a conventional method, and 0.41 g of the quaternized product was dissolved in 3 ml of acetic acid to give glutaconaldehyde dianyl hydrochloride.
Add 0.19g, acetic anhydride 0.7ml, pyridine 1ml and bath temperature 90-105
The mixture was heated and stirred at ℃ for 1 hour.

After cooling, 40 ml of ethyl acetate was added to the reaction solution, and the mixture was stirred and filtered to obtain 0.36 g of compound (48) as a yellow-green solid.

Synthesis Example 5 (Synthesis of Compound Example 49) 2,3,3-Trimethyl-5-methoxy-1,4-diazaindene was synthesized according to the above-mentioned document. Add this to the compound (4
Similar to the synthesis of 8), it is quaternized and then condensed to give compound (4
9) got.

Synthesis Example 6 (Synthesis of Compound Example 51) In the synthesis of the compound (46) of Synthesis Example 1, after purification by decantation, this was further added with 100 ml of saturated saline solution and 2
After stirring for hours, the mixture was filtered to obtain a yellow-green solid compound (51).

Synthesis Example 7 (Synthesis of Compound Example 56) In the synthesis of the compound (49) of Synthesis Example 5, after decantation purification, the compound (56) was obtained by treating with a saturated saline solution in the same manner as the above compound (51).

In the light-sensitive material of the present invention, the general formulas (I) and (I
The dyes represented by I) and (III) can be contained in a silver halide emulsion to be used as an anti-irradiation dye, or can be contained in a non-photosensitive hydrophilic colloid layer, It can also be used as a filter dye or an antihalation dye. Further, two or more kinds of dyes may be used in combination depending on the purpose of use, or may be used in combination with other dyes. The dye of the present invention can be easily incorporated into the silver halide emulsion layer or other hydrophilic colloid layer by a conventional method. Generally, a dye or an organic / inorganic alkali salt of a dye is dissolved in water to prepare a dye aqueous solution having an appropriate concentration, which is added to a coating solution and coating is carried out by a known method to contain the dye in the light-sensitive material. You can The content of these dyes varies depending on the purpose of use, but is generally used by coating so as to be 1 to 800 mg per 1 m ² of area on the photographic material.

Examples of the photosensitive material to which the present invention is applied include color photographic photosensitive materials in addition to black-and-white photographic photosensitive materials.
Examples of the former include a photosensitive material for printing. At this time, two or more silver halide emulsion layers can be provided. The coated silver amount is preferably in the range of 1 to 8 g / m ² .

Silver halide used in the present invention, for example, silver chloride,
It may be any of silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide and silver chloroiodobromide.

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

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

The silver halide photographic emulsion that can be used in the present invention can be produced by a known method. For example, Research Disclosure (RD), Vol. 176, No. 17643 (December, 1978), pp. 22-23, and N.
o. 18716 (November 1978), p.648.

The silver halide emulsion used in the method of the present invention may or may not be chemically sensitized.

In the case of chemical sensitization, usual sulfur sensitization, reduction sensitization, noble metal sensitization and a combination thereof are used.

More specific chemical sensitizers include sulfur sensitizers such as allyl thiocarbamide, thiourea, thiosulfate, thioether and cystine; and noble metal sensitizers such as potassium chloroaurate, auras thiosulfate and potassium chloroparadate. Reduction sensitizers such as tin chloride, phenylhydrazine and reductone; The silver halide emulsion used in the present invention is optionally spectrally sensitized by a known spectral sensitizing dye. As the spectral sensitizing dye to be used, those described in Research Disclosure (supra) No. 17643, Section IV can be used.

Various compounds can be added to the photographic emulsion of the present invention in order to prevent the deterioration of sensitivity and the occurrence of fog during the manufacturing process, storage or processing of the light-sensitive material. These compounds include nitrobenzimidazole, ammonium chloroplatinate, 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaidene, 1-phenyl-5-mercaptotetrazole, many heterocyclic compounds, and mercury-containing compounds. , Mercapto compounds and metal salts have been known for a long time.

As the binder or protective colloid used for the light-sensitive material, it is advantageous to use gelatin, but hydrophilic synthetic polymers and the like can also be used. As the gelatin, lime-processed gelatin, acid-processed gelatin, derivative gelatin and the like can also be used.

In the photosensitive material of the present invention, in addition to the above, a desensitizer,
Whitening agents, couplers, hardeners, coating aids, plasticizers, slippers, matting agents, high-boiling organic solvents, stabilizers, development accelerators,
An antistatic agent, an antistain agent and the like can be used. As these additives, those described in Research Disclosure (supra) No. 17643, Sections I to XVI can be used.

In the photographic processing of the light-sensitive material of the present invention, any of known methods can be used, and a known processing solution can be used. The processing temperature is usually selected between 18 ° C and 50 ° C, but may be lower than 18 ° C or higher than 50 ° C. Depending on the purpose, either a development process for forming a silver image (black and white photographic process) or a color photographic process including a development process for forming a dye image can be applied.

〔The invention's effect〕

The silver halide photographic light-sensitive material of the present invention has good image quality, does not impair sensitivity, and has little residual color after development processing. Moreover, the hydrophilic colloid layer of the silver halide photographic light-sensitive material of the present invention is colored with a water-soluble dye, has good stability upon storage without adversely affecting the photographic characteristics of the photographic emulsion, and can be easily processed by photographic processing. It is extremely excellent in that it is decolorized.

〔Example〕

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

Example 1 3.5 g of gelatin was added to and dissolved in 35 ml of distilled water.
5 ml of an aqueous solution containing 2.0 × 10 ⁻⁴ mol of each of the exemplary dyes (1), (2) and (3) of the present invention was added, and 1.25 ml of a 10% aqueous saponin solution and 0.75 ml of a 1% formalin solution were added. Water was added to bring the total volume to 50 ml. The dye solution was applied on an acetylcellulose film support and dried to obtain Samples 1, 2 and 3. Comparative Samples 4 and 5 were prepared in the same manner using the following comparative dyes (A) and (B) instead of the dye according to the present invention.

Each of these samples was immersed in a developer having the following composition at 25 ° C. for 1 minute, washed with water for 20 seconds, and then dried.

(Composition of developer) Metol 3.0 g Sodium sulfite (anhydrous) 45.0 g Hydroquinone 12.0 g Sodium carbonate (monohydrate) 80.0 g Potassium bromide 2.0 g Add water to make 1.

The visible spectrum of each sample before and after immersion in the developer was measured, and the decolorization rate was determined from the difference in absorbance at the maximum absorption wavelength. The results are shown in Table 1 below.

(E ₁ is the absorbance before immersion in the developing solution, and E _E represents the absorbance after immersion in the developing solution.) As is clear from Table 1, the dye of the present invention was found to exhibit excellent decolorization properties as compared with the comparative dye.

Example 2 80 mol% of silver chloride, 19.5 mol% of silver bromide and 0.5 of silver iodide
A silver chloroiodobromide gelatin emulsion having an average grain size of 0.32 μm was prepared. 1 kg of this gelatin emulsion (4 silver
Contains 8g and 75g gelatin. ), 2,4-dichloro-6-
After adding 35 ml of hydroxy-1,3,5-triazine sodium salt (1% aqueous solution) and 50 ml of saponin (10% aqueous solution), 50 mg of silver was contained per 100 cm ² on a polyethylene terephthalate film support which had been subjected to subbing treatment. And dried.

Further, a protective layer having the following composition containing the dye (4) exemplified in the present invention was coated on the emulsion layer so that the dry film thickness was 2 μm. (Sample 6) (Protective layer composition) Gelatin 40 g Water 850 ml Exemplified dye of the present invention (4) (2% aqueous solution) 100 ml 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt (1 % Aqueous solution) 20 ml Saponin (10% aqueous solution) 30 ml Similarly, instead of the exemplary dye (4) of the present invention, the exemplary dyes (5) and (6) and the comparative dyes (A) and (B) used in Example 1 were used. ), Make a sample containing
The samples were 7, 8, 9 and 10, respectively.

Each of these samples was cut into small pieces, exposed through a photographic light wedge, and processed using a developing solution and a fixing solution having the following compositions. Development was performed at 20 ° C. for 1.5 minutes, fixing was performed at 20 ° C. for 2 minutes, water washing was performed at 20 ° C. for 5 minutes, and then dried.

(Developer composition) Hydroquinone 15g Formaldehyde sodium hydrogensulfite adduct 55g Anhydrous sodium sulfite 3g Sodium carbonate (monohydrate) 80g Boric acid 5g Potassium bromide 2.5g Ethylenediaminetetraacetic acid disodium 2g Water 1,000g (fixer composition) Sodium thiosulfate 160 g Anhydrous sodium sulfite 14 g Glacial acetic acid 12 ml Borax 12 g Calimyban 5 g 1,000 ml Each sample that had been subjected to development processing by adding water was piled up 10 times, and the presence or absence of colored contamination on the sample was examined. The results obtained are shown in Table 2 below.

In the sample using the comparative sample, coloring stain was observed in the sample, but the dye of the present invention was excellent in the outflow and decoloring properties, and there was no coloring stain at all.

Example 3 A silver chlorobromide emulsion comprising 70 mol% of silver chloride and 30 mol% of silver bromide and having an average grain size of 0.3 μm was prepared. This emulsion 1
Formalin (1 kg / kg (including 48 g of silver and 75 g of gelatin))
% Aqueous solution) and saponin (10% aqueous solution) 50 ml, and then coated on an undercoated polyethylene terephthalate film support, and a protective layer having the following composition was further coated on this emulsion layer.

(Protective layer composition) Gelatin 40 g Water 960 ml Formalin (1% aqueous solution) 12 ml Saponin (10% aqueous solution) 30 ml Next, a gelatin layer containing a dye having the following composition is formed on the back surface of the support coated with the emulsion layer and the protective layer. Dry film thickness is 3
It was applied to have a thickness of μm. (Sample 11) (Ceratin layer composition) Gelatin 50 g Water 835 ml Exemplified dye according to the present invention (7) (2% aqueous solution) 100 ml Formalin (1% aqueous solution) 15 ml Saponin (10% aqueous solution) 50 ml Similarly, the present invention Samples 12 and 13 were prepared by using Exemplified dye (9) and the following dye (C) in place of Exemplified dye (7).

Developing treatment was performed in the same manner as in Example 2, and each sample 10
The sheets were superimposed one by one to evaluate coloring contamination. The results obtained are shown in Table 3 below.

As shown in the above table, in the sample using the comparative dye, coloring contamination was observed, but in the dye of the present invention, no coloring contamination was observed. It was also found that the dye of the present invention can provide a light-sensitive material having an excellent antihalation effect without adversely affecting the photographic emulsion such as fog and desensitization.

Example 4 On a support made of polyethylene-coated paper, the following layers were sequentially provided from the support side to prepare a color photographic material (Sample 14).

First layer: yellow coupler; α-pivalyl-α- (1-benzyl-2-phenyl-3,5-dioxotriazolidine-
4-yl) -2'-chloro-5 '-[γ- (2,4-di-
(t-amylphenoxy) butyramide] acetanilide, a hardener (dichlorotriazine) and a surfactant (saponin) containing a blue-sensitive silver halide emulsion layer (90
A silver chlorobromide emulsion containing mol% of silver bromide and sensitized with a sensitizing dye was provided so that the coated silver amount was 3.5 mg / 100 cm ² .

Second layer: a gelatin layer (intermediate layer) was provided.

Third layer ... Magenta coupler; 1- (2,4,6-trichlorophenyl) -3- [3- (2,4-di-t-amylphenoxyacedamide) benzamide] -5-pyrazolone, hardener Green-sensitive silver halide emulsion layer containing (dichlorotriazine) and a surfactant (saponin) (a silver chlorobromide emulsion containing 80 mol% of silver bromide and sensitized with a sensitizing dye). Was set so that the coated silver amount was 4.5 mg / 100 cm ² .

Fourth layer: A gelatin layer (intermediate layer) was provided.

Fifth layer: cyan coupler; 2,4-dichloro-3-methyl-
6- (2,4-di-t-amylphenoxyacetamide)
Red-sensitive silver halide emulsion layer containing phenol, hardener (dichlorotriazine) and surfactant (saponin) (a silver chlorobromide emulsion containing 75 mol% of silver bromide, sensitized with a sensitizing dye). The coated silver amount was set to 2.0 mg / 100 cm ² .

Sixth layer: A gelatin layer (protective layer) was provided.

Furthermore, a green-sensitive sensitization (third layer coating solution) was prepared by adding 200 ml of a 2% aqueous solution of the exemplified dye (43) of the present invention or the comparative dye (D) to 1 kg of the emulsion, respectively, in the same manner as in the above-mentioned sample 14, Samples 15 and 16 were prepared.

These samples 14, 15 and 16 were exposed and then processed according to the following processing steps.

[Processing step (31 ° C)] Processing time 1. Color development 3 minutes 2. Bleach-fixing 1 minute 3. Water washing 2 minutes 4. Stabilization 1 minute 5. Water washing 2 minutes The composition of the processing solution used in each processing step is , As follows.

[Color developer composition]

 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.8g anhydrous sodium sulfite 4.0g hydroxylamine 1/2 sulfate 2.0g anhydrous potassium carbonate 28.0g potassium bromide 1.5g Potassium hydroxide 1.0g Add water to make 1.

(Bleach-fix solution composition)

 Ethylenediaminetetraacetic acid ferric salt 65.0 g Ethylenediaminetetraacetic acid disodium salt 3.0 g Anhydrous sodium sulfite 9.5 g Sodium thiosulfate 4.0 g Add water to make 1.

(Fixer composition)

 Glacial acetic acid 9ml Sodium acetate 3g Add water to make 1.

 Table 4 shows the density of the unexposed portion of each sample after the treatment.

As is clear from Table 4, in the sample containing the dye of the present invention, no coloring stain due to the residual color of the dye as shown in the sample containing the comparative dye was observed. Further, comparing the sensitivities of the respective samples, it was found that the dye of the present invention had very little adverse effect on the emulsion.

Claims (1)

(57) [Claims] 1. A 3H-pyrrolopyridine, 4H-thienopyrrole,
6H- thienopyrrole, 4H-furopyrrole and 6H- furopyrrole at least a substituent with or -CH ₂ CH ₂ OR group one or more having at least two acid groups in the dye molecule of the cyanine dye to nucleus 2 A silver halide photographic light-sensitive material having a hydrophilic colloid layer containing at least one cyanine dye. R represents a hydrogen atom or an alkyl group.