JP2000112089A - Image forming method for silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image forming method for a silver halide photographic sensitive material by which development is accelerated and an evil influence is hardly exerted on the environment by carrying out development in the presence of a specified compound. SOLUTION: A silver halide photographic sensitive material with at least one photosensitive silver halide emulsion layer on the substrate is developed in the presence of a compound of formula I or II. In the formulae I and II, R1 is H, an alkyl, aryl, hydroxy, amino, thiol, alkoxy or thio-ether and R2 and R3 may be mutually the same or different and are each H or a 1-4 substitutable group. The amount of the compound added is 1×10-6-1×10-2 mol, preferably 5×10--5×10-3 mol, further preferably 1×10-5-1×10-3 mol per 1 mol silver.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for forming an image on a silver halide photographic material, and more particularly to a silver halide photographic material using a developing solution.

[0002]

2. Description of the Related Art Photosensitive materials using photosensitive silver halide emulsions include general black and white photosensitive materials, photosensitive materials for printing plate making, photosensitive materials for microphotography, industrial materials, and various color photographic materials. Widely used in the field. Due to its high light sensitivity and docking with many characteristic functional materials, silver halide photographic materials have been developed which have various characteristics depending on the application. For image formation, a wet development process is required after exposure. Usually, in the case of black and white photosensitive material, a developing bath, a fixing bath,
Wash or stabilize the bath. In the case of a color photographic light-sensitive material, processing of a color developing bath, a desilvering / fixing bath, washing with water, or a stabilizing bath is required. Thereafter, drying is required. The development processing time requires 10 seconds to several minutes, and the total processing time requires 30 seconds to several minutes. In addition, an instant photography method is also known, such as a B & W instant photography by a silver salt diffusion transfer method and an instant color photograph by a color diffusion transfer method. In the case of the diffusion transfer method, it is usually composed of a photosensitive sheet and an image receiving sheet, between which a wet developing solution is developed. All the chemicals are contained in the photosensitive sheet or the image receiving sheet, and an improved system in which a small amount of water is spread and heated to diffuse and transfer is also known. Silver halide photographic light-sensitive materials have extremely excellent photographic performance characteristics, but have the disadvantage that they require development processing in which they are immersed in multiple wet baths. In recent years, there has been an increasing demand.

Hitherto, many development accelerators have been proposed as one of means for accelerating the development processing, and some of them have been put to practical use. Primary to tertiary amine compounds, onium salt compounds, thioether compounds, benzyl alcohols, ethylene glycols and the like are well known. However, in addition to having a high accelerating effect, other adverse effects such as the fact that the treatment liquid is not contaminated even when treated in large quantities, and that it does not evaporate and contaminate the air, rivers, or affect the environment. There is a continuing need for less accelerators.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide an improved method for forming an image on a silver halide photographic material.

[0005]

This object is achieved by any one of the following constitutions (1) to (5). (1) In a method for forming an image using a silver halide photographic material having at least one photosensitive silver halide emulsion layer on a support, a compound represented by the following formula (I) or (II): A method for forming an image on a silver halide photographic light-sensitive material, wherein a development process is performed in the presence of the photographic material.

[0006]

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[Wherein R ₁ is a group selected from a hydrogen atom, an alkyl group, an aryl group, a hydroxy group, an amino group, a thiol group, an alkoxy group and a thioether group.
R ₂ and R ₃ may be the same or different and each is a hydrogen atom or 1 to 4 substitutable groups. (2) The method for forming an image of a silver halide photographic material according to the above (1), wherein the compound represented by the formula (I) or (II) is contained in the silver halide emulsion layer. (3) The above (1), wherein the silver halide photographic material has a non-photosensitive hydrophilic colloid layer, and the compound represented by the formula (I) or (II) is contained in the non-photosensitive hydrophilic colloid layer. Image forming method of silver halide photographic light-sensitive material. (4) The method for forming an image of a silver halide photographic material according to the above (1), wherein the compound represented by the formula (I) or (II) is contained in the image receiving layer of the diffusion transfer method. (5) The method for forming an image of a silver halide photographic material according to the above (1), wherein the compound represented by the formula (I) or (II) is contained in a developing solution.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The method for forming an image of a silver halide photographic light-sensitive material of the present invention comprises forming an image using a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support. In the method of forming, the following formula (I)
Alternatively, the development is performed in the presence of the compound represented by (II).

[0009]

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Here, R ₁ is a group selected from a hydrogen atom, an alkyl group, an aryl group, a hydroxy group, an amino group, a thiol group, an alkoxy group and a thioether group.

R ₂ and R ₃ may be the same or different and each is a hydrogen atom or 1 to 4 substitutable groups.

The alkyl group for R ₁ is an unsubstituted or substituted alkyl group having 1 to 30 carbon atoms. Examples of the substituent include a group consisting of a repeating unit of a hydroxy group, an optionally substituted aryl group, an optionally substituted amino group, a carbonyl group, a carbamoyl group, a thiol group, an alkoxy group, a thioether group, and an ethylenoxy or propylenoxy group. To be elected. As the optionally substituted aryl group, a phenyl group substituted with 1 to 3 hydroxy groups or amino groups is preferable.

Particularly preferred alkyl groups for R ₁ are an alkyl group having a hydroxy group as a substituent, an alkyl group having a phenyl group substituted with 1 to 3 hydroxy groups or amino groups as a substituent, and etherenoxy or An alkyl group having a repeating unit of a propylenoxy group.

The aryl group for R ₁ is an unsubstituted or substituted phenyl group or naphthyl group. Examples of the substituent include a hydroxy group, an amino group which may be substituted,
And 0 is selected from the group consisting of a repeating unit of an alkyl group, a carbonyl group, a carbamoyl group, a thiol group, an alkoxy group, a thioether group, and an ethylenoxy or propylenoxy group. The preferred aryl group for R ₁ is a phenyl group having a hydroxy group or an amino group as a substituent.

Particularly preferred as R ₁ is a hydrogen atom,
An alkyl group having a hydroxy group as a substituent and a phenyl group having a hydroxy group as a substituent.

R ₂ and R ₃ are a hydrogen atom or a substitutable group. The substitutable group can be selected from various substitutable substituents. Preferably, the substituent is an amino group that may be substituted with a hydroxy group, a C1-30 group.
An alkyl group, a carbonyl group, a carbamoyl group, a thiol group alkoxy group, a thioeal group, and a group consisting of a repeating unit of an ethylenoxy or propylenoxy group,
It is selected from a carboxyl group, a cyano group, and a phenyl group. Desirable R ₂ is a hydrogen atom or an alkyl group having 1 to 30 carbon atoms.

These compounds may be incorporated in a silver halide emulsion layer or other non-photosensitive hydrophilic colloid layer (protective layer, interlayer,
It may be added to a color mixing prevention layer, a filter layer (yellow, magenta), an antihalation layer, an undercoat layer, etc. of a multicolor color photographic material.

These compounds are added after being dissolved in water or an organic solvent (eg, methanol, ethanol acetone, DMF, ethyl acetate, etc.). Emulsion dispersion or solid dispersion may be added.

The addition amount of these compounds is from 1 × 10 ^-6 mol to 1 × 10 ^-2 mol, preferably 5 × 10 ^-2 mol, per mol of silver.
^-6 mol to 5 × 10 ^-3 mol, more preferably 1 × 10 ^-5 mol to 1 × 10 ^-3 mol.

These compounds may be added to a developer. In that case, 1 × 10 ^-6 to 1 × 10 per liter
^-2 , preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻³ .

The structures of the formulas (I) and (II) of the present invention have the structure of the formula (II) or the structure of the formula (I) by the addition and elimination of water as represented by the following formulas. . Next, as a specific example, it is represented by the structure of (I), but there is naturally each (II) structure. These are only examples, and the present invention is not limited to these specific compounds.

[0022]

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[0023]

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[0024]

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[0025]

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The silver halide emulsion used in the present invention may have any composition such as silver chloride, silver chlorobromide, silver bromide, silver iodobromide, silver iodochlorobromide and the like.

The average grain size of the silver halide used in the present invention is preferably fine grains (for example, 0.7 μm or less), particularly preferably 0.5 μm or less. The particle size distribution is basically not limited, but is preferably monodispersed. The term “monodisperse” as used herein means that at least 95% by weight or the number of particles is composed of a group of particles having a size within ± 40% of the average particle size.

The silver halide grains in the photographic emulsion are cubic,
It may have a regular crystal such as an octahedron, or an irregular (irregu) such as a sphere or plate.
lar) crystals or a compound of these crystal forms.

In the silver halide grains, the inside and the surface layer may be composed of a uniform phase or different phases. Two or more kinds of silver halide emulsions formed separately may be used as a mixture.

It is particularly preferable to use a silver halide emulsion having a silver chloride content of 50% or more as a photographic material for plate making.

In the case of a light-sensitive contact material, silver chloride is preferably 95% or more.

The silver halide emulsion used in the present invention preferably contains a transition metal complex. Rh as a transition metal,
Ru, Re, Os, Ir, Cr, Fe, Pt, Co, N
i, Pd and the like. The ligands include nitrosyl and thionitrosyl ligands, halide ligands (fluoride, chloride, bromide and iodide), cyanide ligand, cyanate ligand, thiocyanate ligand, selenocyanate ligand. Ligands, tellurocyanate ligands, acid ligands and aquo ligands. If an aquo ligand is present, it preferably occupies one or two of the ligands. Particularly preferred metal complexes are halogen, nitrosyl or thionitrosyl complexes of rhodium or ruthenium.

In order to dope the transition metal ion into the silver halide grains, in addition to the addition as a complex, a metal salt of any form such as a single salt can be added during the preparation of the grains.

Specific examples of the metal complex will be described.

Examples of the rhodium salt include rhodium monochloride, rhodium dichloride, rhodium trichloride, ammonium hexachlororhodate, and the like, preferably a water-soluble trivalent rhodium halide complex compound such as hexachlororhodium (III) acid. Or its salt (ammonium salt, sodium salt, potassium salt, etc.).

The following transition metal complexes are also preferred. 1 [Ru (NO) Cl _5] ^2- 2 [Ru (NO) ₂ Cl _4] ^- 3 _{[Ru (NO) (H 2 O} ) Cl 4 ] ^- 4 [Rh (NO) Cl _5] ^2- 5 [ Re (NO) Cl _5] ^2- 6 [Re (NO) CN _5] ² 7 [Re (NO) ClCN _4: ^2- 8 [Rh (NO) ₂ Cl _4] ^- 9 [Rh (NO) (H ₂ O) Cl _4] ^- 10 [Ru (NO) CN _5] ^2- 11 [Ru (NO) Br _5] ^2- 12 [Rh (NS) CN _5] ^2- 13 [Os (NO) Cl _5] ^{2 -} 14 [Cr (NO) Cl _5] ^3- 15 [Re (NO) ₂ Cl _4] ^- 16 _{[Os (NS) Cl 4 (TeCN} ) ] ^2- 17 [Ru (NS) I _5] ^3- 18 [ Re (NS) Cl ₄ (SeCN)] ^2- 19 [Os (NS) Cl (SCN) ₄ ] ^2-20 [Ir (NO) Cl ₅ ] ^3-

Each of the above complexes 1 to 20 has an ammonium ion, a sodium ion or a potassium ion as a counter ion.

The addition amount of these transition metal complexes is in the range of 1.0 × 10 ^-8 mol to 1.0 × 10 ^-3 mol per mol of silver halide. Preferably, it is 1.0 × 10 ⁻⁷ mol to 1.0 × 10 ⁻⁴ mol.

When the silver halide black-and-white light-sensitive material of the present invention contains a high-contrast agent such as a hydrazine derivative or a tetrazolium salt compound, a super-high contrast image can be obtained.

There are no particular restrictions on the developing agents that can be used in the method of the present invention. Examples thereof include dihydroxybenzenes (eg, hydroquinone) and 3-pyrazolidones (eg, 1-phenyl-3-pyrazolidone, 4,4-dimethyl-1). -Phenyl-3-pyrazolidone), aminophenols (eg, N-methyl-p-aminophenol) and the like can be used alone or in combination.

The silver halide black-and-white light-sensitive material of the present invention is particularly suitable to be processed with a developing solution containing dihydroxybenzenes as a main developing agent and 3-pyrazolidones or aminophenols as an auxiliary developing agent. Preferably, in this developer, dihydroxybenzenes are used in an amount of 0.05 to 0.5 mol / l, and 3-pyrazolidones or aminophenols are used in an amount of 0.06 mol / l or less.

As described in US Pat. No. 4,269,929, the development speed can be increased by adding amines to the developer to shorten the development time.

In the developing solution, pH buffers such as alkali metal sulfites, carbonates, borates and phosphates, bromides, iodides and organic antifoggants (particularly preferably nitroindazoles or (A benzotriazole) or an antifoggant. Further, if necessary, a water softener, a dissolution aid, a color tone agent, a development accelerator, a surfactant (particularly preferably a polyalkylene oxide), an antifoaming agent, a hardening agent, a silver stain preventing agent for a film (for example, 2-mercaptobenzimidazole sulfonic acids).

As the fixing solution, those having a commonly used composition can be used. Thiosulfate as fixing agent,
In addition to the thiocyanate, an organic sulfur compound known to have an effect as a fixing agent can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

The processing temperature of the black and white light-sensitive material in the method of the present invention is usually selected between 18 ° C. and 50 ° C.

It is preferable to use an automatic developing machine for photographic processing. Sufficient photographic characteristics can be obtained when the total processing time from when the photosensitive material is put into the automatic developing machine until it comes out is 30 seconds to 120 seconds.

In the developing solution of the present invention, compounds described in JP-A-56-24347 can be used as silver stain inhibitors. Japanese Unexamined Patent Publication No.
Compounds described in 1-267759 can be used. Further, as a pH buffering agent used in a developer, see JP-A-60
-93,433 or JP-A-62-263.
Compounds described in 186259 can be used.

There are no particular restrictions on other various additives used in the black-and-white light-sensitive material of the present invention, and for example, those described in the following places can be preferably used.

Item The present section 1) Nucleation accelerator JP-A-2-103536, page 9, upper right column, line 13 to page 16, upper left column, line 10, formulas (II-m) through (II) -P) and compounds II-1 to II-22, and compounds described in JP-A-1-179939. 2) Silver halide emulsion and JP-A-2-97937, page 20, lower right column, line 12, line 14 from page 21, lower left column, line 14, page 7, JP-A-2-122236, page 7, upper right column 19 The selenium sensitization method described from the first line to the lower left column, page 12, page 8, and Japanese Patent Application No. 3-189532. 3) Spectral sensitizing dye JP-A-2-12236, page 8, lower left column, line 13 to lower right column, line 4; JP-A-2-103536, page 16, lower right column, line 3 to page 17 Spectral sensitizing dyes described in the lower left column, line 20, and further described in JP-A-1-112235, JP-A-2-124560, JP-A-3-7928, Japanese Patent Application Nos. 3-189532 and 3-411046. 4) Surfactant JP-A-2-12236, page 9, upper right column, line 7 to lower right column, line 7, and JP-A-2-18542, page 2, lower left column, line 13 to page 4, right Lower column, line 18. 5) Antifoggants JP-A-2-103536, page 17, lower right column, line 19 to page 18, upper right column, line 4 and lower right column, line 1 to line 5, and JP-A-1-237538. A thiosulfinic acid compound described in the gazette. 6) Polymer latex JP-A-2-103536, page 18, lower left column, lines 12 to 20. 7) Compound having an acid group: JP-A-2-103536, page 18, lower right column, line 6 to page 19, upper left column, line 1. 8) Matting agent, slip agent, JP-A-2-103536, page 19, upper left column, line 15, plasticizer to page 19, upper right column, line 15; 9) Hardener JP-A-2-103536, page 18, right upper column, 5th line to 17th line. 10) Binder JP-A-2-18542, page 3, lower right column, line 1 to line 20. 11) Black spot inhibitors Compounds described in U.S. Pat. No. 4,956,257 and JP-A-1-118832. 12) Redox compound The compound represented by the formula (I) in JP-A-2-301743 (especially compound examples 1 to 50), and the general formula (3) described in JP-A-3-174143, pp. 3 to 20. (R-1), (R-2), (R-3), Compound Examples 1 to 75, and compounds described in Japanese Patent Application Nos. 3-69466 and 3-156648. 13) Monomethine compounds Compounds of the formula (II) described in JP-A-2-287532 (especially compound examples II-1 to II-26). 14) Dihydroxybenne Compounds described in JP-A-3-39948, page 11, upper left column to first-classes, page 2, lower left column, and EP 452772A. 15) Hydrazine nucleating agent JP-A-2-12236, page 2, upper right column, line 19 to page 7, upper right column, line 3; JP-A-3-174143, page 20, lower right column, line 1 And the formula (II) and the compound examples II-1 to II-54 in the upper right column, line 20, p. A compound represented by the formula (I) of Japanese Patent Application No. 5-3608. Specific examples I-1 to I-28.

The silver halide used when the present invention is applied to a color light-sensitive material includes silver chloride, silver bromide,
(Io) silver chlorobromide, silver iodobromide and the like can be used.
In particular, for the purpose of rapid processing, the silver chloride content substantially containing no silver iodide is 90 mol% or more, more preferably 95% or more, especially 9 mol% or more.
The use of 8% or more silver chlorobromide or silver chloride emulsions is preferred.

The support used in the present invention may be any support such as glass, paper, plastic film, etc., on which a photographic emulsion layer can be coated.

The high-boiling organic solvents for photographic additives such as cyan, magenta and yellow couplers which can be used in the color light-sensitive material of the present invention are compounds having a melting point of 100 ° C. or less and a boiling point of 140 ° C. or more and are immiscible with water. Any good solvent for the coupler can be used. The melting point of the high boiling organic solvent is preferably 80 ° C. or lower. The boiling point of the high-boiling organic solvent is preferably 160 ° C.
And more preferably 170 ° C. or higher.

Details of these high-boiling organic solvents are described in JP-A-62-215272, page 137, right lower column.
It is described in the upper right column on page 144.

Also, cyan, magenta or yellow couplers can be used in the presence or absence of the aforementioned high boiling organic solvents in the presence of loadable latex polymers (eg, US Pat.
4,203,716) or dissolved in a water-insoluble and organic solvent-soluble polymer and emulsified and dispersed in a hydrophilic colloid aqueous solution.

Preferably, homopolymers or copolymers described in US Pat. No. 4,857,449, columns 7 to 15 and WO 88/00723, pages 12 to 30 are used,
More preferably, use of a methacrylate-based or acrylamide-based polymer, particularly, an acrylamide-based polymer is preferable in terms of stabilizing a color image.

In the color light-sensitive material according to the present invention, it is preferable to use a color image preservability improving compound as described in European Patent EP 0,277,589A2 together with a coupler.
In particular, combination use with a pyrazoloazole coupler is preferred.

That is, the compound (F) which chemically bonds to the aromatic amine-based developing agent remaining after the color development to form a chemically inert and substantially colorless compound, and / or
Alternatively, a compound (G) which forms a chemically inert and substantially colorless compound by chemically bonding with an oxidized form of an aromatic amine-based color developing agent remaining after color development processing is used simultaneously or independently. However, it is preferable in order to prevent, for example, the generation of stains and other side effects due to the formation of a coloring dye due to the reaction between the color developing agent remaining in the film or the oxidized product thereof and the coupler during storage after processing.

The light-sensitive material according to the present invention is provided with a fungicide, such as that described in JP-A-63-271247, in order to prevent various molds and bacteria that propagate in the hydrophilic colloid layer and deteriorate the image. It is preferred to add an agent.

The color light-sensitive material according to the present invention may be exposed to visible light or infrared light. The exposure method may be low-illuminance exposure or high-illuminance short-time exposure. In the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 -4 seconds is preferred.

In the exposure, US Pat. No. 4,880,72
It is preferable to use the band stop filter described in No. 6. As a result, light color mixing is removed, and color reproducibility is significantly improved.

The exposed light-sensitive material can be subjected to conventional black-and-white or color development processing. In the case of a color light-sensitive material, bleach-fix processing is preferably performed after color development for the purpose of rapid processing. In particular, when the high silver chloride emulsion is used, the pH of the bleach-fixing solution is adjusted to about 6.5 for the purpose of accelerating desilvering.
Or less, more preferably about 6 or less.

The silver halide emulsion and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) applied to the color light-sensitive material according to the present invention, and the processing applied for processing this light-sensitive material As the method and processing additives, the following patent publications, in particular, European Patent EP 0,355,660A2 (Japanese
No. 2-139544) are preferably used.

[0063]

[Table 1]

[0064]

[Table 2]

[0065]

[Table 3]

[0066]

[Table 4]

[0067]

[Table 5]

Further, as a cyan coupler, JP-A-2-33
In addition to the diphenylimidazole cyan couplers described in EP-A-144, 3-hydroxypyridine cyan couplers described in European Patent EP 0,333,185 A2 (among others, a 4-equivalent coupler of coupler (42) listed as a specific example) 2 equivalents with a leaving group, coupler (6) and
(9) is particularly preferred) and the use of cyclic active methylene cyan couplers described in JP-A-64-32260 (in particular, coupler examples 3, 8, and 34 listed as specific examples) are also preferred.

A method for processing a silver halide color light-sensitive material using a high silver chloride emulsion having a silver chloride content of 90 mol% or more is described in JP-A-2-207250, page 27, upper left column to page 34.
The method described in the upper right column of the page is preferably applied.

[0070]

EXAMPLES Hereinafter, the present invention will be described in more detail by showing specific examples of the present invention.

Example 1 <Preparation of Support> A backing layer and a conductive layer having the following compositions were provided on an undercoated polyester film having a thickness of 100 μm.

Back layer Gelatin 3.3 g / m ² Sodium dodecylbenzenesulfonate 80 mg / m ² Compound (11) 40 mg / m ² Compound (12) 20 mg / m ² Compound (13) 90 mg / m ² 1,3-divinyl Sulfonyl-2-propanol 60 mg / m ² Fine particles of polymethyl methacrylate (average particle size 6.5 μm) 30 mg / m ² Compound (5) 120 mg / m ²

Conductive layer Gelatin 0.1 g / m ² Sodium dodecylbenzenesulfonate 20 mg / m ² SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25 μm) 200 mg / m ²

<Preparation of Emulsion A> 1 liquid 1 liter water 20 g gelatin 20 g sodium chloride 3.0 g 1,3-dimethylimidazolidin-2-thione 20 mg sodium benzenethiosulfonate 8 mg 2 liquid water 400 ml silver nitrate 100 g 3 liquid water 400 ml chloride Sodium 27.1 g Potassium bromide 21.0 g Ammonium hexachloroiridate (III) (0.001% aqueous solution) 20 ml Potassium hexachloroiridate (III) (0.001% aqueous solution) 6 ml

The first and second solutions were added simultaneously to the first solution maintained at 42 ° C. and pH 4.5 for 15 minutes while worshiping.
Core particles formed. Subsequently, the following liquids 4 and 5 were added over 15 minutes. Further, 0.15 g of potassium iodide was added to terminate the particle formation.

Liquid 4 Water 400ml Silver nitrate 100g Liquid 5 Water 400ml Sodium chloride 27.1g Potassium bromide 21.0g Potassium hexacyanoferrate (II) (0.1% aqueous solution) 10ml

Thereafter, the resultant was washed with water by a flocculation method according to a conventional method, and 40 g of gelatin was added.

After adjusting the pH to 5.7 and the pAg to 7.5, sodium thiosulfate (1.0 mg), chloroauric acid (4.0 mg), triphenylphosphine selenide (1.5 mg), sodium benzenethiosulfonate (8 mg), benzenethiosulfinic acid 2 mg of soda was added, and the mixture was chemically sensitized at 55 ° C. to obtain an optimum sensitivity.

Further, 4-hydroxy-6 is used as a stabilizer.
-Methyl-1,3,3a, 7-tetrazaindene 100
mg, phenoxyethanol as a preservative, and finally containing 70 mol% of silver chloride, average particle size 0.25 μm
A silver chloroiodobromide cubic emulsion A was obtained.

<Coating of photosensitive layer> Sensitizing dye (1) was added to emulsion A.
3.8 × 10 ^-4 mol / mol Ag was added for spectral sensitization. Furthermore, KBr 3.4 × 10 ⁻⁴ mol / mol Ag, compound (1) 3.2 × 10 ⁻⁴ mol / mol Ag, compound (2) 8.0.
× 10 ^-4 mol / mol Ag, hydroquinone 1.2 × 10
⁻² mol / mol Ag, citric acid 3.0 × 10 ⁻³ mol / mol Ag, compound (3) 1.0 × 10 ⁻⁴ mol / mol Ag, compound (4) 6.0 × 10 ⁻⁴ Mol / mol Ag, 35 wt% of polyethyl acrylate latex based on gelatin, 20 wt% based on gelatin, colloidal silica having a particle diameter of 10 μm, and 4 wt% based on gelatin were added with compound (5). Ag 3.7 g / m ² , gelatin 1.6 on top
g / m ² . A protective layer upper layer and a protective layer lower layer having the following composition and a UL layer having the following composition were coated thereon (Comparative Sample A).

Upper layer of protective layer Gelatin 0.3 g / m ² Average 3.5 μm silica matting agent 25 mg / m ² Compound (6) (gelatin dispersion) 20 mg / m ² Colloidal silica having a particle size of 10 to 20 μm 30 mg / m ² Compound (7) 5 mg / m ² Sodium dodecylbenzenesulfonate 20 mg / m ² Compound (8) 20 mg / m ² Lower layer of protective layer Gelatin 0.5 g / m ² Compound (9) 15 mg / m ² 1,5-dihydroxy-2 - benzaldoxime 10 mg / m ² of polyethyl acrylate latex 150 mg / m ²

UL layer Gelatin 0.5 g / m ² Polyethyl acrylate latex 150 mg / m ² Compound (5) 40 mg / m ² Compound (10) 10 mg / m ²

[0083]

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[0084]

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<Coating of photosensitive layer of the present invention> Sample 1 in which the compound of the formula (I) of the present invention shown in Table 1 was added in an amount of 1 × 10 ^-4 mol per mol of silver instead of the photosensitive layer of the comparative sample. -1 to 1-6 were prepared.

<Evaluation of Photographic Performance> The above comparative sample and the sample of the present invention were exposed to xenon flash light having an emission time of 10 ⁻⁶ sec through a step wedge through an interference filter having a peak at 633 nm. Using the following developer, AP-56 manufactured by Fuji Photo Film Co., Ltd.
0 With an automatic processor, 35 ° C, 15 sec and 20 sec
After development, fixing, washing and drying were performed.

The sensitivity was represented by a logarithmic value of the reciprocal of the exposure amount giving a density of 1.5, and was represented by a relative value to the 15-second development of the comparative sample. Table 6 shows the results. The higher the value, the higher the sensitivity.

As can be seen from the results in Table 6, the sample of the present invention was developed for 15 seconds, the same sensitivity as the comparative sample of 20 seconds was obtained, and rapid development was possible.

Developer A The composition per liter of the concentrated solution of the developer A is shown below. Potassium hydroxide 60.0 g Diethylenetriamine / pentaacetic acid 3.0 g Potassium carbonate 90.0 g Sodium metabisulfite 105.0 g Potassium bromide 10.5 g Hydroquinone 60.0 g 5-Methylbenzotriazole 0.53 g 4-Hydroxymethyl-4 -Methyl-1-phenyl-3-birazolidone 2.3 g Sodium 2-mercaptobenzimitazole-5-monosulfonate 0.45 g Sodium 3- (5-mercaptotetrazol-1-yl) benzenesulfonate 0.15 g Erythorbin Sodium acid 9.0 g Diethylene glycol 7.5 g Compound (17) 1.5 g Compound (18) 0.5 g pH 10.79

For use, 1 part of water is diluted with 2 parts of the above concentrated liquid. PH of working solution is 10.65
It is.

[0091]

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The fixer used had the following formulation.

(Fixing solution formulation) Ammonium thiosulfate 359.1 g Ethylenediaminetetraacetic acid 2Na dihydrate 0.09 g Sodium thiosulfate pentahydrate 32.8 g Sodium sulfite 64.8 g NaOH 37.2 g Glacial acetic acid 87.3 g Tartaric acid 8.76 g Sodium gluconate 6.6 g Aluminum sulfate 25.3 g Water is added to make up to 3 liters and adjusted to pH 4.85 with sulfuric acid or sodium hydroxide. The replenishment rate was 250 ml / m ² .

[0094]

[Table 6]

Example 2 <Preparation of Sample> A photosensitive element having the structure shown in Table 7 was prepared.

[0096]

[Table 7]

[0097]

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[0098]

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A dye-fixing element having the composition shown in Table 8 was prepared. Using this as a comparative sample, the compound of the formula (I) of the present invention was added to the third layer at 8 × 10 ⁻⁷ mol / m ² . Table 9 shows the correspondence between the sample numbers and the compounds of the formula (I) used.

[0100]

[Table 8]

[0101]

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[0102]

[Table 9]

[0103]

[Table 10]

<Evaluation of Photographic Properties> The above photosensitive elements and dye fixing elements were processed using an image recording apparatus described in JP-A-2-84634. That is, a tungsten bulb is used for the photosensitive element, and B, G,
1/5000 lux through R three color separation filter
Exposure was for 10 seconds. This photosensitive element was immersed in water maintained at 40 ° C. for about 5 seconds, squeezed with a roller, and then immediately superimposed so that the dye fixing element and the film surface were in contact with each other, so that the supplied film surface was adjusted to 80 ° C. Heating was performed for 15 seconds using a heat roller. Next, when the photosensitive element and the dye fixing element were peeled off, yellow, magenta, and cyan color images were obtained on the dye fixing element corresponding to the B, G, and R color separation filters.

The relative sensitivity (the same definition as in Example 1) in comparison with the comparative sample and the maximum image density (Dmax) of the three-color image
Are shown in Table 9. The sample of the present invention has high sensitivity and high Dma
x was given.

Next, the light fastness of these color images was tested. Atlas CI
Using a 65 weather meter, a xenon light (10
10,000 lux) for one week. The dye density before and after irradiation was measured with a Macbeth reflection densitometer, and the residual ratio of the color image was determined. The results are shown in Table 10. As can be seen from the table, the sample of the present invention exhibited a high color image residual ratio. It is a completely unexpected effect that the compounds of the present invention increase the light fastness of color images.

Example 3 The comparative sample of Example 1 was used as a photosensitive film. In the developing solution, the developing solution A of Example 1 was replaced with the formula (I) of the present invention.
A liquid obtained by adding 1 × 10 ⁻⁴ mol of Compound I-1 to 1 L of the working solution was used. As a result of exposure and development processing in the same manner as in Example 1, a sensitivity 0.15 higher than that of the blank was obtained by development at 35 ° C. for 15 seconds. The development was at a high sensitivity of 0.21 at 35 ° C. for 20 seconds.

Claims (5)

[Claims] 1. A method for forming an image using a silver halide photographic material having at least one photosensitive silver halide emulsion layer on a support, represented by the following formula (I) or (II): An image forming method of a silver halide photographic light-sensitive material, wherein the development is carried out in the presence of a compound. Embedded image [Where R ₁ is a group selected from a hydrogen atom, an alkyl group, an aryl group, a hydroxy group, an amino group, a thiol group, an alkoxy group and a thioether group. R ₂ and R ₃ are
Each may be the same or different and is a hydrogen atom or 1 to 4 substitutable groups. ] 2. The method according to claim 1, wherein the compound represented by the formula (I) or (II) is contained in the silver halide emulsion layer. 3. The silver halide photographic light-sensitive material comprises a non-photosensitive hydrophilic colloid layer, and the compound represented by the formula (I) or (II) is contained in the non-photosensitive hydrophilic colloid layer. 1. An image forming method for a silver halide photographic light-sensitive material. 4. The method according to claim 1, wherein the compound represented by the formula (I) or (II) is contained in an image receiving layer of a diffusion transfer method. 5. The method for forming an image on a silver halide photographic material according to claim 1, wherein the compound represented by the formula (I) or (II) is contained in a developing solution.