JPH07333784A - Silver halide photographic material - Google Patents

Abstract

PURPOSE:To allow a silver halide photographic material to be excellent in preservation stability and reduce remaining colors after an image forming process by having a hydrophilic colloid layer that contains a specific dye. CONSTITUTION:This silver halide photographic material has a hydrophilic colloid layer containing a dye represented by the formula. I n the formula, Z<1>, Z<2> represent the nonmetal atom group required to form a benzo condensed. ring and a naphtho condensed ring, respectively; L<4>, L<5> each represent an alkylene group of 1-4 carbons; R<1>, R<2> represent -CONH-A and -SO2NH-A, respectively; A represents -COR<7> or -SO2R<7>; R<7> represents an alkyl group; R<3>-R<6> each represent an alkyl group; R<3> and R<4>, and R<5> and R<6> may bond together to form rings; L<1>-L<3> each represent a methine group; the methine groups may bond together to form a five-or six-membered ring; M<1>, M<2> each represent an alkali metal salt, an ammonium salt, or negative charge; X represents an anion; and (n) represents 1 or 2.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material having a dyed hydrophilic colloid layer, and more specifically, it has absorption in the infrared region and is stable in the photographic material. The present invention relates to a silver halide photographic light-sensitive material having a hydrophilic colloid layer containing a dye which is chemically inert and is easily decolorized in the course of photographic processing.

[0002]

2. Description of the Related Art In a halogenated photographic light-sensitive material, a photographic emulsion layer or other layers are often colored for the purpose of absorbing light having a specific wavelength. When it is necessary to control the spectral composition of the light to be incident on the photographic emulsion layer, a coloring layer is provided on the side of the photographic photosensitive material farther from the support than the photographic emulsion layer. Such a colored layer is called a filter layer. When there are a plurality of photographic emulsion layers as in a multi-layer color light-sensitive material, the filter layer may be located between them.

Light scattered during or after passing through the photographic emulsion layer is reflected at the boundary between the emulsion layer and the support or at the surface of the light-sensitive material opposite to the emulsion layer and re-enters the photographic emulsion layer. A coloring layer is provided between the photographic emulsion layer and the support or on the surface opposite to the support and the photographic emulsion layer for the purpose of preventing image blurring based on the above, that is, halation. Such a colored layer is called an antihalation layer. In the case of a multi-layer color light-sensitive material, an antihalation layer may be placed in the middle of each layer. The photographic emulsion layer is also colored in order to prevent a reduction in image sharpness due to light scattering in the photographic emulsion layer (this phenomenon is generally called irradiation).

These layers to be colored are often composed of hydrophilic colloids and are therefore usually used for their coloring.
A water-soluble dye is contained in the layer. This dye is required to satisfy the following conditions. (1) It has a proper spectral absorption according to the purpose of use. (2) Photochemically inactive. In other words, the performance of the silver halide photographic emulsion layer should not be adversely affected in a chemical sense, such as a reduction in sensitivity, latent image regression, or fog. (3) It should not be decolorized or dissolved and removed in the course of photographic processing to leave no harmful coloring on the photographic light-sensitive material after processing. (4) Excellent stability over time in solution or photographic material.

Many dyes which absorb visible light or ultraviolet rays are known to satisfy such conditions, and for the purpose of image improvement in conventional photographic elements sensitized to wavelengths of 700 nm or less, these dyes are known. Suitable for In particular, benzylidene, triarylmethane and oxonol dyes are widely used in this context. on the other hand,
In recent years, development of antihalation and antiirradiation dyes that absorb in the infrared region of the spectrum for photographic light-sensitive materials as recording materials that have been sensitized to infrared wavelengths, for example, recording materials that record the output of near-infrared laser, have been developed. Is requested.

For example, one of such exposure methods for a photographic light-sensitive material is to scan an original image, and the silver halide photographic light-sensitive material is exposed on the basis of the image signal to expose a negative image or a negative image corresponding to the image of the original image. An image forming method using a so-called scanner method for forming a positive image is known. In this method, a semiconductor laser is most preferably used as a scanner type recording light source. This semiconductor laser is small in size, inexpensive, easy to modulate, has a longer life than other He-Ne lasers, argon lasers, and emits light in the infrared region. Therefore, a photosensitive material having photosensitivity in the infrared region is used. And, since a bright safelight can be used, there is an advantage that handling workability is improved.

[0007]

However, the above-mentioned conditions (1), (2), (3) and (4) having absorption in the infrared region of the spectrum, especially (3) due to rapid processing recently, are present. Since there are no suitable dyes that satisfy the condition of (4), there are few excellent photosensitive materials having high photosensitivity in the infrared region and preventing halation and irradiation, and therefore excellent as described above. The reality is that the characteristics of semiconductor lasers with high performance cannot be fully utilized.
To date, many efforts have been made to find dyes satisfying the above conditions, and a large number of dyes have been proposed.

For example, the tricarbocyanine dyes described in JP-A-62-123454, JP-A-1-147451, EP568,022A or US Pat. No. 3,282,933 are known. However, at present, there are very few dyes that can satisfy all the above conditions.

The object of the present invention is to provide the above (1) and (2).
It is to develop a dye satisfying the conditions (3) and (4). In particular, it is to provide an infrared-sensitive silver halide photographic light-sensitive material which is stable during storage and has little residual color after development.

[0010]

It has been found that the object of the present invention can be achieved by a silver halide photographic light-sensitive material containing at least one dye represented by the following general formula [I].

[0011]

[Chemical 2]

In the formula, Z ¹ and Z ² each represent a nonmetallic atom group necessary for forming a benzo condensed ring or a naphtho condensed ring. L ⁴ and L ⁵ each represent an alkylene group having 1 to 4 carbon atoms. R ¹ and R ² are each -CONH-
A or -SO ₂ NH-A, A is -COR ⁷ or-
Represents SO ₂ R ⁷ , and R ⁷ represents an alkyl group. R ³ , R
⁴ , R ⁵ and R ⁶ each represent an alkyl group, and R ³ and R ⁴ , and R ⁵ and R ⁶ may be connected to each other to form a ring. L ¹ , L ² and L ³ each represent a methine group, and the methine groups may be linked to each other to form a 5- or 6-membered ring. M ¹ and M ² each represent an alkali metal salt, an ammonium salt or an anion. X represents an anion, and n represents 1 or 2. N is 1 when the dye forms an inner salt.

The general formula [I] will be described in detail. Z ¹
And a benzo-condensed ring or a naphtho-condensed ring formed by a non-metal atom group represented by Z ² are —SO ₃ M ¹ , —SO ₃ M ²
However, a plurality of these may be substituted.

L ⁴ and L ⁵ each represent an alkylene group having 1 to 4 carbon atoms, and examples thereof include methylene, ethylene, 1,3-propylene, 1,2-propylene and 1,4-butylene. L ⁴ and L ⁵ preferably have 1 carbon atom.
~ 2 alkylene groups (methylene, ethylene). R
¹ and R ² are -CONH-A or -SO ₂ NH-, respectively.
Represents A, and A represents —COR ⁷ or —SO ₂ R ⁷ . R
¹ , R ² are —CONHCOR ⁷ , —CONHSO
₂ R ^7, -SO ₂ NHCOR ⁷ or -SO ₂ NHSO
₂ represents R ⁷ . R ⁷ represents an alkyl group, preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group or an ethyl group.

R³, R^Four, R^FiveAnd R⁶Are each
Represents a alkyl group, preferably an alkyl group having 1 to 4 carbon atoms
And particularly preferably a methyl group and an ethyl group. Well
R ³And R^Four, R^FiveAnd R⁶Are connected to each other and
It is preferably a 3- to 6-membered saturated hydrocarbon ring. For example, cyclohex
Sun) may be formed.

The methine group represented by L ¹ , L ² and L ³ is a substituted or unsubstituted alkyl group (total carbon atom number is preferably 1-8, more preferably 1-5. For example, methyl, Ethyl, 3-hydroxypropyl, benzyl, 2-sulfoethyl, etc.), halogen atom (eg, F, Cl, Br, etc.), substituted or unsubstituted aryl group (total carbon atom number is preferably 6 to 15, and more preferably 6 to 8. For example, phenyl, 4-chlorophenyl, etc., and a substituted or unsubstituted alkoxy group (total carbon number is preferably 1 to 8, more preferably 1).
~ 5. For example, methoxy, ethoxy, etc.), a substituted or unsubstituted phenoxy group (total carbon atom number is preferably 6 to 8. For example, 4-sulfophenyloxy),
Substituted amino group (the total number of carbon atoms is preferably 1 to
8. For example, 2-carboxyethylamino, 4-sulfoanilino, morpholino), a substituted or unsubstituted alkylthio group (the total number of carbon atoms is preferably 1-8,
More preferably 1-5. For example, 2-sulfoethylthio, carboxymethylthio), a substituted or unsubstituted arylthio group (total carbon atom number is preferably 6 to 15, more preferably 6 to 10. 2-carboxythiophenol, 4-carboxythio It may be substituted with (phenol) or the like. The meso-position-substituted product is preferable. Further, the substituents of the methine group may be bonded to each other to form a 5- or 6-membered ring containing three methine groups (for example, cyclopentene ring, cyclohexene ring, 4,4-dimethylcyclohexene ring, etc.).

M ¹ and M ² are each an alkali metal salt (eg, sodium, potassium), ammonium salt (eg, organic ammonium salt such as triethylammonium, tributylammonium, pyridinium) or anion.

Examples of the anion represented by X, a halogen ion (Cl, Br, I), p- toluenesulfonate ion, ethyl sulfate _{^{ion, PF 6 -, BF 4 -}} , ClO
₄ ^- etc. n represents 1 or 2, and is 1 when the dye forms an intramolecular salt.

In the present invention, the dye represented by the general formula [I] is particularly preferable when represented by the following general formula [I-1].

[0020]

[Chemical 3]

Where L⁴¹And L⁵¹Are methylene groups
Or represents an ethylene group. R¹¹, R ^{twenty one}Is -CO
NH-A¹Or-SO₂NH-A¹Represents A¹Is -C
OR ⁷¹Or-SO₂R⁷¹Represents R⁷¹Has 1 to 3 carbon atoms
Represents an alkyl group. L¹, L ², L³, M¹, M²,
X and n have the same meanings as those in formula [I].
Is.

Specific examples of the present invention are shown below, but the scope of the present invention is not limited to these.

[0023]

[Chemical 4]

[0024]

[Chemical 5]

[0025]

[Chemical 6]

[0026]

[Chemical 7]

The compounds of the present invention are described in US 3,282,93
3, JP-A-62-123454, JP-A-6-4358.
It can be synthesized with reference to No. 3 and the like.

Synthesis Example (Synthesis of Compound 1) N-Bromacetylmethanesulfone
6.4 g of amide, 4.8 g of 5-sulfoindolenin and
A mixture of 2.8 ml of triethylamine and 100 ° C.
Heated at 120 ° C. for 5 hours. After the reaction is complete, methylalco
(100 ml) was added, and the precipitated quaternary salt was filtered off.
Yield: 2.6 g m.p. p: 250 ° C. or higher 2 g of the quaternary salt obtained above, 10 ml of methyl alcohol, and
To a mixture of 1.9 ml triethylamine,
1 g of rudehydr dianneal hydrochloride followed by 1 ml of acetic anhydride
Was added and stirred at room temperature for 1 hour. After completion of the reaction, potassium acetate
2 g of um was added, and the precipitated crystals were filtered off, then water / methyl
Recrystallization was performed from rualcohol = 1/1. Yield: 1g
 m.p .: 250 ℃ or more λmax 743.6nm ε: 2.16
× 10^Five(H ₂O) Other compounds can be similarly synthesized.

The dye represented by the general formula [I] of the present invention (hereinafter referred to as the dye of the present invention) is a suitable solvent [for example, water, alcohol (for example, methanol, ethanol, etc.), methyl cellozoble, etc., or a mixed solvent thereof]. Dissolved in
Alternatively, it is preferably added as an aqueous decomposition product to the photosensitive or non-photosensitive hydrophilic colloid layer coating liquid. These dyes can be used in combination of two or more kinds. The amount of the dye of the present invention used is generally 10 per 1 m ² of the light-sensitive material.
^A preferred amount can be found in the range of ^-3 g to 2.5 g, especially 10 ^-3 g to 1.0 g.

The dye of the present invention is particularly effective for the purpose of preventing irradiation, and when it is used for this purpose, it is mainly added to the emulsion layer. The dye of the present invention is also particularly effective as a dye for preventing halation, in which case it is added to the back surface of the support or a layer between the support and the emulsion layer. The dye of the present invention can be advantageously used as a filter dye.

In the present invention, the dye represented by the general formula [I] is preferably used together with the binder. Hydrophilic colloid materials used as binders include gelatin, gelatin substitutes, collodion, gum arabic, alkyl esters of carboxylated cellulose, cellulose ester derivatives such as hydroxyethyl cellulose, carboxymethyl hydroxyethyl cellulose, 1960 8
There are synthetic resins such as the amphoteric copolymers described in Clavier et al., U.S. Pat. No. 2,949,442, issued Mar. 16, polyvinyl alcohol and other materials well known in the art. Examples of polymeric gelatin substitutes include copolymers of allylamine and methacrylic acid, copolymers of allylamine and acrylic acid and acrylamide, hydrolyzed copolymers of allylamine and methacrylic acid and vinyl acetate, copolymers of allylamine and acrylic acid and styrene, Examples include copolymers of allylamine, methacrylic acid, and acrylonitrile.

Examples of the light-sensitive material of the present invention include silver halide black-and-white photographic light-sensitive materials and silver halide color photographic light-sensitive materials. The silver halide emulsion used in the present invention may have any silver halide composition,
From the viewpoint of sensitivity, the silver chloride content is preferably 0 mol% or more and 50 mol% or less, and examples thereof include silver bromide, silver chlorobromide, and silver iodochlorobromide having a silver chloride content of 0 mol% or more and 50 mol% or less. . Particularly, silver chlorobromide having a silver chloride content of 5 mol% or more and 40 mol% or less is preferable.

Others, silver halide emulsions, photographic emulsions, sensitizers, sensitizing dyes, antifoggants, dyes and other additives used in the present invention, various processing solutions for development, automatic developing machines, etc. JP-A-5-313305 (1
3) p. 24 column 50 line to (19) p. 36 column 16 line and JP-A-3-13
No. 937 (8), upper right column, first line to (14) lower left column, line 9 and the like apply. Among them, when the light-sensitive material of the present invention is a color light-sensitive material, the cyan, magenta and yellow couplers described on pages 100 to 129 of JP-A-2-285345 are preferable. The dispersion medium and dispersion method of the coupler are described in JP-A-2-285345, No. 1
Pages 29 to 132 apply. Regarding the processing of color light-sensitive materials, JP-A-2-285345, No. 1
The description on page 44, line 8 to page 168, line 11 applies. Regarding the scanning exposure light source, etc., JP-A-2-285345
The description on page 168, line 12 to page 170, line 9 applies. For the layer structure of the color light-sensitive material, see JP-A-2-2
The description of No. 85345, page 171, line 1 to page 172 applies.

The photosensitive material of the present invention has a total processing time of 10 seconds to
It shows excellent performance in rapid development processing by an automatic processor, which is 60 seconds. In the rapid development process of the present invention, the temperature and time for development and fixing are each 25 seconds or less at about 25 ° C to 50 ° C, preferably 30 ° C to 40 ° C for 4 seconds to 15 seconds. Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

[0035]

【Example】

Example 1 1. Preparation of silver halide emulsion 34 g of gelatin was dissolved in 850 ml of H ₂ O, and 1.7 g of sodium chloride, 0.1 g of potassium bromide and the following compound (A) were placed in a container heated at 65 ° C.

[0036]

[Chemical 8]

After adding 70 mg of the above, 500 ml of an aqueous solution containing 170 g of silver nitrate, potassium hexachloroiridium (III) such that the molar ratio of iridium to the finished silver halide is 5 × 10 ^-7 , 12 g of sodium chloride and bromide. 500 ml of an aqueous solution containing 98 g of potassium was added by the double jet method to prepare cubic monodispersed silver chlorobromide grains having an average grain size of 0.35 μm. After desalting this emulsion, 50 g of gelatin was added, pH 6.5, pAg
In accordance with 8.1, 2.5 mg of sodium thiosulfate and 5 mg of chloroauric acid were added and chemically sensitized at 65 ° C., followed by 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaine. 0.2 g of den was added and rapidly solidified (Emulsion A). Next, 0.3 μm cubic monodispersed silver chlorobromide grains were prepared in the same manner as in Emulsion A except that the gelatin solution was heated at 40 ° C. After desalting, 50 g of gelatin was added to pH 6.5. ,
Matched to pAg 8.1. To this emulsion were added 2.5 mg of sodium thiosulfate and 5 mg of gold chloride, and after chemical sensitization at 65 ° C,
Emulsion B was prepared by adding 0.2 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and rapid solidification.

2. Preparation of emulsion coating solution Emulsions (A) and (B) were mixed at a weight ratio of 1: 1 and the following additives were added per mol of silver halide to prepare an emulsion coating solution.

(Formulation of emulsion coating solution) a. Spectral sensitizing dye [2] 1.0 × 10 ⁻⁴ mol. Supersensitizer [3] 0.7 × 10 ⁻³ mol c. Shelf life improving agent [4] 1 × 10 ⁻³ mol. Polyacrylamide (molecular weight 40,000) 7.5 g e. Dextran 7.5 g f. Trimethylolpropane 1.6 g. Polystyrene sulfonate Na 1.2 g H. Poly (ethyl acrylate / methacrylic acid) latex 12 g Re. N, N'-ethylenebis- (vinyl sulfone acetamide) 3.0 g Nu. 1-phenyl-5-mercapto-tetrazole 50mg

Spectral sensitizing dye [2]

[0041]

[Chemical 9]

Supersensitizer [3]

[0043]

[Chemical 10]

Storability improver [4]

[0045]

[Chemical 11]

3. Preparation of Coating Solution for Surface Protecting Layer of Emulsion Layer A container was heated to 40 ° C., and additives were added in the following formulation to prepare a coating solution. (Formulation of coating solution for emulsion layer surface protection layer)

B. Gelatin 100 g d. Polyacrylamide (molecular weight 40,000) 12 g c. Sodium polystyrene sulfonate (molecular weight 600,000) 0.6 g D, N, N'-ethylenebis- (vinyl sulfone acetamide) 2.2 g E. Polymethylmethacrylate fine particles (average particle size 2.0 μm) 2.7 g f. Sodium t-octylphenoxyethoxyethane sulfonate 1.8 g. _{C 16 H 33 O- (CH 2} CH 2 O) 10 -H 4.0g Ji. Sodium polyacrylate 6.0 g Re. C ₈ F ₁₇ SO ₃ K 70 mg Nu. _{C 8 F 17 SO 2 N (} C 3 H 7) (CH 2 CH 2 O) 4 (CH 2) 4 -SO 3 Na 70mg Le. 6 ml of NaOH (1N). Methanol 90 ml Wa. Compound [5] 0.06 g

[0048]

[Chemical 12]

4. Preparation of Back Layer Coating Liquid A container was heated to 40 ° C., and additives were added in the formulation shown below to prepare a back layer coating liquid.

(Prescription of Back Layer Coating Liquid) a. Gelatin 100 g b. Dye [A] 4.2 g c. Polystyrene sodium sulfonate 1.2 g d. Poly (ethyl acrylate / methacrylic acid) latex 5 g e. N, N'-ethylenebis- (vinyl sulfone acetamide) 4.8 g f. Compound [5] 0.06 g g. Dye 1 0.3 g J. Dye 2 0.05 g Colloidal silica 15g

Comparative dye [A]

[0052]

[Chemical 13]

Dye 1

[0054]

[Chemical 14]

Dye 2

[0056]

[Chemical 15]

5. Preparation of Back Surface Protective Layer Coating Solution A container was heated to 40 ° C., and additives were added in the following formulation to prepare a coating solution. (Back surface protective layer coating liquid formulation)

B. Gelatin 100 g b. Polystyrene sodium sulfonate 0.5 g c. N, N'-ethylenebis- (vinyl sulfone acetamide) 1.9 g d. Polymethylmethacrylate fine particles (average particle size 4.0 μm) 4 g e. Sodium t-octylphenoxyethoxyethane sulfonate 2.0 g f. NaOH (1N) 6 ml. Sodium polyacrylate 2.4 g h. _{C 16 H 33 O- (CH 2} CH 2 O) 10 -H 4.0g Li. C ₈ F ₁₇ SO ₃ K 70 mg Nu. _{C 8 F 17 SO 2 N (} C 3 H 7) (CH 2 CH 2 O) 4 (CH 2) 4 -SO 3 Na 70mg Le. 150 ml of methanol. Compound [5] 0.06 g

6. Preparation of Photographic Material The coating solution for the back layer was coated on the side of the polyethylene terephthalate support together with the coating solution for the surface protective layer of the back layer so that the total coating amount of gelatin was 3 g / m ² . Subsequently, the emulsion coating liquid and the surface protective layer coating liquid described above were applied to the opposite side of the support so that the coating Ag amount was 2.3 g / m ² and the gelatin coating amount of the surface protective layer was 1 g / m ² . Was applied (Photographic material 1).

Further, instead of the dye [A], the comparative dyes [B], [C] and [D] and the dye (1) of the present invention,
Photographic materials 2 to 7 were prepared in exactly the same manner except that the same amounts of (4), (6) and (9) were used. Comparative dye [B] is described in JP-A-1-147451, Comparative dye [C] is described in European Patent Publication No. 568,022A1, and comparative dye [D] is described in U.S. Pat. No. 3,282,933. Is.

[0061]

[Chemical 16]

7. Evaluation of Storage Stability The photosensitive materials shown in Table 1 prepared by the above method were treated with a humidity of 70
%, After leaving it at 50 ° C. for 10 days, the reflection spectrum is measured, and the rate of change of the light absorption rate at the absorption maximum wavelength of each dye (absorption rate after leaving at 50 ° C., 70% RH / 50 ° C., 70%
The absorption rate before standing in% RH) and the residual rate are shown in Table 1.

8. Evaluation of Decoloring Property The light-sensitive materials shown in Table 1 were subjected to the following image forming treatment, and the reflection spectrum of a white background portion was measured. The residual color ratio of the dye was calculated by comparing the light absorption ratio of the dye absorption maximum before and after the image forming treatment, and the results are shown in Table 1.

The photographic materials 1 to 7 were kept at a temperature and humidity of 25 ° C. and 60%, left for 7 days after coating, and subjected to scanning exposure for 10 ⁻⁷ seconds using a semiconductor laser of 830 nm at room temperature, and a roller-conveying type automatic developing machine. By using the following developer [I],
Development processing was performed with the fixing solution [I]. The developing time is 7 seconds, the fixing is 7 seconds, the water washing is 4 seconds, and the water draining / drying is 11 seconds. At this time, the transport speed was 3000 mm / min.

Developer [I] Composition Potassium hydroxide 29 g Sodium sulfite 31 g Potassium sulfite 44 g Ethylenetriaminetetraacetic acid 1.7 g Boric acid 1 g Hydroquinone 30 g Diethylene glycol 29 g 1-Phenyl-3-pyrazolidone 1.5 g Glutaraldehyde 4.9 g 5- Methylbenzotriazole 60 mg 5-Nitroindazole 0.25 g Potassium bromide 7.9 g Acetic acid 18 g Water was added to 1000 ml pH 10.3

Fixing Solution [I] Composition Ammonium thiosulfate 140 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid disodium dihydrate 20 mg Sodium hydroxide 7 g Aluminum sulfate 10 g Boric acid 10 g Sulfuric acid 3.9 g Acetic acid 15 g Water 1000 ml pH 4.30 The results obtained are shown in Table 1.

[0067]

[Table 1]

From the results in Table 1, it is clear that the dyes of the present invention are effective in stability and residual color.

[0069]

The light-sensitive material of the present invention is excellent in storage stability and, at the same time, has little residual color after image forming processing.

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[Procedure amendment]

[Submission date] July 28, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 1

[Correction method] Change

[Correction content]

[Chemical 1] In the formula, Z ¹ and Z ² each represent a nonmetallic atom group necessary for forming a benzo condensed ring or a naphtho condensed ring. L ⁴
And L ⁵ each represent an alkylene group having 1 to 4 carbon atoms. R ¹ and R ² are each -CONH-A or -SO
₂ NH-A, A represents -COR ⁷ or -SO ₂ R ⁷ , and R ⁷ represents an alkyl group. R ³ , R ⁴ , R ⁵ and R ⁶ each represent an alkyl group, and R ³ and R ⁴ or R ⁵ and R ⁶ may be linked to each other to form a ring. L ¹ and L ²
And L ³ each represent a methine group, and the methine groups may be linked to each other to form a 5- or 6-membered ring. M ¹ and M ²
Each represents an alkali metal salt, an ammonium salt or a negative charge. X represents an anion, and n represents 1 or 2.
N is 1 when the dye forms an inner salt.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0012

[Correction method] Change

[Correction content]

In the formula, Z ¹ and Z ² each represent a nonmetallic atom group necessary for forming a benzo condensed ring or a naphtho condensed ring. L ⁴ and L ⁵ each represent an alkylene group having 1 to 4 carbon atoms. R ¹ and R ² are each -CONH-
A or -SO ₂ NH-A, A is -COR ⁷ or-
Represents SO ₂ R ⁷ , and R ⁷ represents an alkyl group. R ³ , R
⁴ , R ⁵ and R ⁶ each represent an alkyl group, and R ³ and R ⁴ , and R ⁵ and R ⁶ may be connected to each other to form a ring. L ¹ , L ² and L ³ each represent a methine group, and the methine groups may be linked to each other to form a 5- or 6-membered ring. M ¹ and M ² each represent an alkali metal salt, an ammonium salt or a negative charge. X represents an anion, n is 1
Or represents 2. When the dye forms an inner salt, n is 1
Is.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0016

[Correction method] Change

[Correction content]

The methine group represented by L ¹ , L ² and L ³ is a substituted or unsubstituted alkyl group (total carbon atom number is preferably 1-8, more preferably 1-5. For example, methyl, Ethyl, 3-hydroxypropyl, benzyl, 2-sulfoethyl, etc.), halogen atom (eg, F, Cl, Br, etc.), substituted or unsubstituted aryl group (total carbon atom number is preferably 6 to 15, and more preferably 6 to 8. For example, phenyl, 4-chlorophenyl, etc., and a substituted or unsubstituted alkoxy group (total carbon number is preferably 1 to 8, more preferably 1).
~ 5. For example, methoxy, ethoxy, etc.), a substituted or unsubstituted phenoxy group (total carbon atom number is preferably 6 to 8. For example, 4-sulfophenyloxy),
Substituted amino group (the total number of carbon atoms is preferably 1 to
8. For example, 2-carboxyethylamino, 4-sulfoanilino, morpholino), a substituted or unsubstituted alkylthio group (the total number of carbon atoms is preferably 1-8,
More preferably 1-5. For example, 2-sulfoethylthio, carboxymethylthio), a substituted or unsubstituted arylthio group (the total number of carbon atoms is preferably 6 to 15, and more preferably 6 to 10. 2-carboxyphenylthio, 4-carboxyphenyl Thio) and the like. The meso-position-substituted product is preferable. Further, the substituents of the methine group are bonded to each other to contain three methine groups.
Alternatively, a 6-membered ring (eg, cyclopentene ring, cyclohexene ring, 4,4-dimethylcyclohexene ring, etc.) may be formed.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0017

[Correction method] Change

[Correction content]

M ¹ and M ² are each an alkali metal salt (for example, sodium, potassium), an ammonium salt (for example, an organic ammonium salt such as triethylammonium, tributylammonium and pyridinium) or a negative charge.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having a hydrophilic colloid layer containing at least one dye represented by the following general formula [I]. [Chemical 1] In the formula, Z ¹ and Z ² each represent a nonmetallic atom group necessary for forming a benzo condensed ring or a naphtho condensed ring. L ⁴
And L ⁵ each represent an alkylene group having 1 to 4 carbon atoms. R ¹ and R ² are each -CONH-A or -SO
₂ NH-A, A represents -COR ⁷ or -SO ₂ R ⁷ , and R ⁷ represents an alkyl group. R ³ , R ⁴ , R ⁵ and R ⁶ each represent an alkyl group, and R ³ and R ⁴ or R ⁵ and R ⁶ may be linked to each other to form a ring. L ¹ and L ²
And L ³ each represent a methine group, and the methine groups may be linked to each other to form a 5- or 6-membered ring. M ¹ and M ²
Each represents an alkali metal salt, an ammonium salt or an anion. X represents an anion, and n represents 1 or 2. N is 1 when the dye forms an inner salt.