JP3116196B2 - Silver halide color photographic light-sensitive material and color image forming method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material which is excellent in color reproducibility, can obtain an image having a high color density, and has a small increase in fog with time. The present invention relates to a color photographic light-sensitive material and a color image forming method thereof.

[0002]

BACKGROUND OF THE INVENTION In silver halide photographic materials utilizing a color reduction method such as color photographic paper used for direct viewing, improvement of the image quality of dye images has been increasingly demanded in recent years.
In particular, there is a strong demand for improvements in color reproducibility and white background.

In the color reduction method, magenta couplers such as acylacetamide-based yellow couplers, 5-pyrazolone-based, pyrazoloazole-based, and pyrazolobenzimidazole-based couplers are usually used to form yellow, magenta, and cyan dye images, respectively. Phenolic and naphthol cyan couplers and the like are preferably used. Among them, in the conventional yellow coupler, the maximum absorption wavelength of the coloring dye to be formed is generally located on the longer wavelength side with respect to the preferable absorption characteristics from the viewpoint of color reproducibility, and the maximum absorption wavelength shifts to the shorter wavelength side. JP-A-63-123047, JP-A-63-2314 discloses a yellow coupler having sharp absorption in a long wavelength region.
No. 51, etc.

On the other hand, pyrazoloazoles and the like are preferred as magenta couplers and phenols are preferred as cyan couplers in terms of color reproduction.

[0005] By using the above yellow coupler in combination with the above magenta coupler and cyan coupler, a considerable improvement in hue such as yellow, yellow-green, green, blue-green, orange, and red can be seen. However, on the other hand, the yellow single color is good in color reproduction, but the visual density for human eyes is low, so it is necessary to increase the color density more than before, and it is more advantageous than the conventional one in higher color development. Silver halide color photographic light-sensitive materials have been desired.

On the other hand, in terms of color development of photosensitive materials,
In recent years, in particular, there has been a strong demand for low replenishment and rapid replenishment, and low replenishment treatments for eliminating pollution are described in JP-A No. 1-211750.

However, among the more preferable yellow couplers in terms of the above-mentioned spectral absorption characteristics, color turbidity is liable to occur in a color photographic material containing a compound capable of obtaining a high color density even in rapid and low replenishment processing. It was also found that the fog increased significantly after storage over time.

When the color turbidity occurs, the excellent spectral absorption characteristics of the coupler itself cannot be sufficiently exhibited, and as a result, the color reproducibility is impaired. To prevent color turbidity,
It is known that a color mixture inhibitor is contained in an intermediate layer adjacent to an emulsion layer, but the effect is small with respect to the above-described phenomenon. cause.

On the other hand, it has been found that an increase in fog due to storage over time affects the shape and size of silver halide grains of a silver halide emulsion used in a light-sensitive material, but this is in conflict with the improvement in color development. In addition, although it is improved by an inhibitor or the like, the effect is insufficient and the problem has not been solved.

As described above, it has been difficult to obtain a silver halide photographic light-sensitive material which is compatible with both color reproducibility and high color-forming property and has a small rise in fog during storage over time.

[0011]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide color photographic light-sensitive material which makes full use of the characteristics of a yellow coupler having excellent color reproducibility and high color-forming property and has a small rise in fog with time. Is to do.

[0012]

The above object of the present invention has been attained by one of the following constitutions.

In a silver halide color photographic light-sensitive material having a photographic component layer including at least one light-sensitive silver halide emulsion layer on a support, at least one of the silver halide emulsion layers has a general formula [I] And at least one of the photographic constituent layers contains at least one surfactant selected from a fluorine-containing anionic surfactant and a fluorine-containing cationic surfactant. A silver halide color photographic light-sensitive material, characterized in that:

[0014]

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[Wherein, R ₁ represents an alkyl group or a cycloalkyl group, and R ₂ represents an alkyl group, a cycloalkyl group, and an aryl group. Z ₆ represents a hydrogen atom or a group capable of leaving upon coupling with an oxidized form of the developing agent. W ₂ represents a group represented by the following general formulas [II] and [III].

[0016]

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In the general formula [II], R ₁₉ represents a straight-chain or branched unsubstituted alkyl group having 11 to 21 carbon atoms.

In the above general formula [III], R ₂₀ represents a hydrogen atom or a linear or branched unsubstituted alkyl group having 1 to 6 carbon atoms, preferably an ethyl group, a butyl group and a hexyl group. It is. In addition, the above general formula [II
In I], R ₂₁ and R _{2 2} is a hydrogen atom or a carbon atoms represents a branched alkyl group having from 4 to 12. However, the sum of the number of carbon atoms of R ₂₁ and R ₂₂ is between 4 and 16.

In the general formula [I], Z ₆ represents a group represented by the following general formula [IV].

[0020]

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[0021]

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In the above general formula [IV], Z ₄ is -Y ₁ -N-
Represents a group of nonmetallic atoms necessary for forming a 5- or 6-membered ring in cooperation with CO-. Z ₆ represents a group having the same meaning as the group represented by the above general formula [IV], and represents a group represented by the following general formula [V] (represented by the general formula [I] due to reaction with an oxidized form of a developing agent). (A state in which a hydrogen atom has been added to Z ₆ removed from the compound to be produced), and has a molecular weight of 235 or less. ]

[0023]

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2. The silver halide color photographic light-sensitive material according to claim 1, wherein at least one of the photographic constituent layers contains a compound represented by the following general formula [VI].

[0025]

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Wherein Ar represents an aromatic group and R ₃₁ represents —O
R ₃₂ , —N (R ₃₃ ) SO ₂ R ₃₄ or —COOM ² R ₃₂ represents a hydrocarbon group having 2 or more carbon atoms, R ₃₃ represents a hydrogen atom or a hydrocarbon group, and R ₃₄ represents a hydrocarbon group. M ¹ and M ² represent a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or an ammonium group. The silver halide color photographic material as described above, wherein at least one of the silver halide emulsion layers contains a silver halide emulsion having a silver chloride content of 95 mol% or more.

In the method of forming a color image by processing the silver halide color light-sensitive material with a color developing solution, followed by bleach-fixing and washing or stabilizing, the replenishment amount of the color developing material is 1 m ^{2 of the} light-sensitive material. 20-100m per
l, a color image forming method.

In the method of forming a color image by processing the above silver halide color light-sensitive material with a color developing solution, followed by bleach-fixing and washing or stabilizing, the color developing time is 30 seconds or less. A color image forming method, comprising:

Hereinafter, the present invention will be described in more detail.

First, the compound represented by the general formula [I] will be described.

[0031]

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[Wherein, R ₁ represents an alkyl group or a cycloalkyl group, and R ₂ represents an alkyl group, a cycloalkyl group, and an aryl group. Z ₆ represents a hydrogen atom or a group capable of leaving upon coupling with an oxidized form of the developing agent. W ₂ represents a group represented by the following general formulas [II] and [III].

[0033]

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In the general formula [II], R ₁₉ represents a straight-chain or branched unsubstituted alkyl group having 11 to 21 carbon atoms.

In the above general formula [III], R ₂₀ represents a hydrogen atom or a linear or branched unsubstituted alkyl group having 1 to 6 carbon atoms, preferably an ethyl group, a butyl group and a hexyl group. It is. In addition, the above general formula [II
In I], R ₂₁ and R ₂₂ represent a hydrogen atom or a branched alkyl group having 4 to 12 carbon atoms. However, the sum of the number of carbon atoms of R ₂₁ and R ₂₂ is between 4 and 16.

In the general formula [I], Z ₆ represents a group represented by the following general formula [IV].

[0037]

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[0038]

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In the above general formula [IV], Z ₄ is -Y ₁ -N-
Represents a group of nonmetallic atoms necessary for forming a 5- or 6-membered ring in cooperation with CO-. Z ₆ represents a group having the same meaning as the group represented by the above general formula [IV], and is represented by the following general formula [V] (represented by the general formula [I] by reaction with an oxidized form of a developing agent) (A state in which a hydrogen atom is added to Z ₆ removed from the compound), and has a molecular weight of 235 or less. ]

[0040]

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Among the compounds represented by the general formula [I], a compound represented by the following general formula [VII] is preferable.

[0042]

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In the above general formula [VII], R ₁ and R ₂
Represents a group having the same meaning as the groups represented by R ₁ and R ₂ in the general formula [I].

In the general formula [VII], R ₂₃ represents a group having the same meaning as the group represented by the general formula [II], and R ₁₉ in the general formula [II] has 11 to 21 carbon atoms. Represents a straight-chain unsubstituted alkyl group.

In the general formula [VII], Z ₅ represents a group having the same meaning as the group represented by the general formula [IV], but in the state represented by the general formula [V] (oxidized form of the developing agent). in Z ₅ in a state of being added to the hydrogen atom) from the general formula [VII] a compound represented by the desorbed by reaction with a molecular weight of 130 or less groups.

The two-equivalent yellow coupler represented by the general formula [I] may be bonded at any of the substituents to form a bis-form, a tris-form, a tetrakis-form or a polymer-form.

The yellow coupler of the present invention represented by the general formula [I] is prepared by using a commercially available compound as a starting material, and by a conventionally known method, for example, JP-A-63-123047 and Japanese Patent Application No. It can be easily synthesized according to the method described in -245949.

The leaving group Z ₆ in the general formula [I] of the present invention.
Specific examples are shown below. (Note that the molecular weight in a state where a hydrogen atom is added to Z ₆ released from the compound represented by the general formula [I] by the reaction with the oxidized form of the developing agent is shown in parentheses.)

[0049]

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[0050]

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Next, specific examples of the substituent R ₂₃ in the general formula [I] of the present invention are shown below.

[0052]

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Next, typical specific examples of the bi-equivalent yellow coupler represented by the general formula [I] used in the present invention will be shown, but the present invention is not limited thereto.

[0054]

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[0055]

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The magenta coupler which can be preferably used in the silver halide photographic light-sensitive material according to the present invention includes a compound represented by the general formula (M-C) described in Japanese Patent Application No. 2-234208, p.
Couplers represented by I) and (M-II) can be mentioned. Specific compounds are described in pages 13 to 16 of the same specification.
To MC-11. Among them, MC- described on pages 15 to 16 of the same specification
8 to MC-11 are preferable because they are excellent in reproducing colors ranging from blue to purple and red, and are also excellent in detail description.

Cyan couplers which can be preferably used in the silver halide photographic light-sensitive material of the present invention include:
The general formula (C-) described in Japanese Patent Application No. 2-234208, p.
Couplers represented by I) and (C-II) can be mentioned. Specific compounds are described in pages 18 to 21 of the same specification.
To CC-9.

When an oil-in-water emulsion dispersion method is used to add the coupler used in the silver halide photographic light-sensitive material according to the present invention, it is usually added to a water-insoluble high-boiling organic solvent having a boiling point of 150 ° C. or higher. If necessary, the mixture is dissolved by using a low boiling point and / or water-soluble organic solvent in combination, and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. As a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser, or the like can be used. After or at the same time as the dispersion, a step of removing the low boiling organic solvent may be added. As high-boiling organic solvents that can be used to dissolve and disperse the coupler, phthalic acid esters such as dioctyl phthalate and phosphoric acid esters such as tricresyl phosphate are preferably used.

In place of the method using a high-boiling organic solvent, a coupler and a water-insoluble and organic solvent-soluble polymer compound may be dissolved in a low-boiling and / or water-soluble organic solvent, if necessary, and a gelatin aqueous solution or the like may be used. A method of emulsifying and dispersing by using various kinds of dispersing means using a surfactant in a hydrophilic binder can also be used. Examples of the water-insoluble and organic solvent-soluble polymer used at this time include poly (Nt-butylacrylamide).

For the purpose of shifting the absorption wavelength of the coloring dye, the compound (d-d) described in Japanese Patent Application No. 2-234208, p.
11), compounds such as compound (A'-1) described on page 35 of the same specification can be used.

In the present invention, at least one of the photographic constituent layers constituting the light-sensitive material contains at least one surfactant selected from a fluorine-containing anionic surfactant and a fluorine-containing cationic surfactant. .

The preferred fluorine-containing anionic surfactant used in the present invention is represented by the following general formula (FA).

Formula (FA) Cf- (W) n wherein Cf is at least 3 fluorine atoms and at least 3
W represents -COOM, -SO
₃ M, —OSO ₃ M or —PO ₂ (OM) ₂ , where M represents a cation such as a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or ammonium. n represents 1 or 2.

Among the fluorine-containing anionic surfactants represented by the general formula (FA), more preferred is the general formula (FA ')
It is a compound represented by these.

Formula (FA ') Rf _1- (L ₁ ) n-W In the formula, Rf ₁ represents a fluorine-substituted alkyl group or an aryl group having 3 to 30 carbon atoms, and L ₁ represents --O--CON (R ₁ )-or -SO ₂
N (R ₁ )-having at least one bond having 1 to 1 carbon atoms
Represents a divalent group of 2, R ₁ represents an alkyl group having 1 to 5 carbon atoms, and n represents 1 or 2. W has the same meaning as W in formula (FA).

Specific examples of the compound represented by formula (FA) are shown below.

[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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Of these, sulfonamide-type fluorine-containing anionic surfactants are particularly preferred.

The preferred cationic surfactant used in the present invention is represented by the following general formula (FK).

Formula (FK) Rf ₂ -L ₂ -X ⁺ Y ^{-In the} formula, Rf ₂ represents a hydrocarbon group having 1 to 20 carbon atoms,
At least one hydrogen atom has been replaced by a fluorine atom. L ₂ represents a chemical bond or a divalent linking group. X ⁺ represents a cation, and Y ⁻ represents a counter anion.

Rf ₂ is preferably C _k H _{2k + 1} , and k is preferably 1 to 12, more preferably 3 to 12. Other, C
_{m HF 2m, C m F 2m} -1, C m F 2m-3 is also preferred, in particular m =
1-4 are preferable.

The divalent linking group represented by L ₂ includes -S
O ₂ (NR ¹ ) (CH ₂ ) _P −, − CON (R ¹ ) (CH ₂ ) _P −, − OL ₄ SO ₂ N (R ¹ ) (CH
₂ ) _P −, − OL ₄ CON (R ¹ ) (CH ₂ ) _P −, − OL ₄ O (CH ₂ ) _P −, − OL ₄ (C
H ₂ ) _P −, − O (CH ₂ CH ₂ O) _q (CH ₂ ) _P −, − O (CH ₂ ) _P −, − N (R ¹ ) (C
H ₂ ) _P −, − SO ₂ N (R ¹ ) (CH ₂ ) _P O −, − CON (R ¹ ) (CH ₂ ) _P O −, − OL
^{_{4 SO 2 N (R 1)}} (CHR 2) P OL 4 - groups such like.

Here, L ₄ represents an alkylene group or an arylene group, and R ¹ and R ² each represent a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms.
p represents an integer of 0 to 6, and q represents an integer of 1 to 20.

The following are specific examples of X ⁺ .

[0079]

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Here, R ₃ represents an optionally substituted alkyl group having 1 to 5 carbon atoms, and p represents an integer of 1 to 3.

[0081] Y ^- Examples of ^{I -, Cl -, Br -} , CH 3 SO
_{^{4 -, CH 3 C 6 H}} 4 SO 3 - , and the like.

The following are specific examples of the fluorine-containing cationic surfactant preferably used in the present invention.

[0083]

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[0084]

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Of these, particularly preferred are the sparingly soluble sulfonamide-type fluorine-containing cationic surfactants. The term “poorly soluble” as used herein means that 2 g of a compound is added to 100 ml of pure water at 23 ° C.
After adding, stirring for 1 hour, and allowing to stand at 23 ° C. for 24 hours, a precipitate is formed, or when a suspended matter is observed, it is considered as poorly soluble. For example, FK-1, FK-8, FK-15, FK-16, and the like correspond to, but are not limited to, and can be classified by the above test.

The fluorine-containing anionic or cationic surfactant is described, for example, in US Pat. Nos. 2,559,751 and 2,567,011.
No. 2,732,398, No. 2,764,602, No. 2,806,866,
2,809,998, 2,915,376, 2,915,528, 2,9
34,450, 2,937,098, 2,957,031, 3,472,89
No. 4, 3,555,089, 2,918,501, UK Patent 1143927
No. 1,130,822, JP-B-45-37304, JP-A-47-9613
No. 50-117727, No. 52-41182, No. 51-12392, Journal of the British Chemical Society (J. Chem. Soc.) 1950, 2789, 1957 2574
2640 pages, Journal of the American Chemical Society (J. Amer. Chem. Soc.) 79: 254
9 pages (1957), J. Japan Oil Chemists Soc.
30, p. 3524 (1965). Certain types can be obtained as commercial products as described below.

Megafac F: Fluorad FC manufactured by Dainippon Ink and Chemicals, Inc. Monflor: manufactured by 3M Co., Ltd. Zonyls: Zonyls: manufactured by EI Dupont Co., Ltd. Licovet VPF: total amount of fluorine-containing anionic surfactants or fluorine-containing cationic surfactant used in the Hoechst present invention, 1 m ² per 0.
1-1000 mg is preferred, 0.5-300 mg is more preferred, and 1.0
~ 150 mg is particularly preferred.

Two or more fluorine-containing anionic surfactants or fluorine-containing cationic surfactants can be used in combination.
Further, in addition to the fluorine-containing anionic surfactant or the fluorine-containing cationic surfactant, other anions, cations and nonionic surfactants, and betaine-type surfactants may be used in combination.

The layer containing the fluorine-containing anionic surfactant and the fluorine-containing cationic surfactant of the present invention is not particularly limited, but is preferably a surface protective layer or a back surface layer. Alternatively, it may be provided as a layer further above the surface protective layer of the photosensitive material.

In the present invention, it is preferable that the compound of the general formula [VI] is contained in at least one of the photographic constituent layers.

The compound represented by the general formula [VI] will be described.

In the general formula [VI], Ar represents an aromatic group, and examples thereof include a phenyl group, a naphthyl group and a pyridyl group. These aromatic groups may have a substituent.

When Ar is a phenyl group, the effects of the present invention can be remarkably obtained, which is preferable.

In the general formula [VI], R ₃₁ is -OR ₃₂ ,-
N (R ₃₃ ) SO ₂ R ₃₄ or —COOM ² Here, R ₃₂ represents a hydrocarbon group having 2 or more carbon atoms, for example, an alkyl group such as an ethyl group, a hexyl group, a dodecyl group, a phenyl group, a pt-butylphenyl group, an m-methoxyphenyl group, an o-methoxyphenyl group. And the like. When R ₃₂ is an alkyl group, the effects of the present invention can be remarkably obtained, which is preferable. R ₃₁ is preferably —N (R ₃₃ ) SO ₂ R ₃₄ or —OR ₃₂ .

R ₃₃ represents a hydrogen atom or a hydrocarbon group,
Other methyl groups as examples of the hydrocarbon group include the same groups as R ₃₂ represents. When R ₃₃ is a hydrogen atom, the effects of the present invention can be remarkably obtained, which is preferable.

R ₃₄ represents a hydrocarbon group, for example, the same groups as the hydrocarbon groups represented by R ₃₃ .

In the general formula [VI], M ¹ and M ² represent a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or an ammonium group, and examples of the metal atom include sodium, lithium, potassium, calcium and the like. Is mentioned. When the metal atom is divalent or higher, an anion binds to neutralize the charge. When M ¹ is a hydrogen atom, the effects of the present invention can be remarkably obtained, which is preferable.

The compounds represented by the general formula [VI] are specifically exemplified below. Naturally, the present invention is not limited to these exemplified compounds.

[0099]

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[0100]

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[0101]

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[0102] The above compounds, Journal of Chemical Society (J.Chem.Soc.) 49 .1748 (1927 ), Journal of Organic Chemistry (J.Org.Che
m.) 39 .2469 (1965) , JP-A-50-89034, An'naren Chemie (Ann.Chim.), 44-3,1954, JP-B-40-2849
No. 6, Chemical Berri tae (Chem.Ber.) 20 .231 (1887 ),
It can be synthesized with reference to US Pat. No. 3,259,976.

The compound represented by the general formula [VI] (hereinafter referred to as compound [VI]) can be contained at any place in the light-sensitive material. Preferably, it is contained in the hydrophilic colloid layer in the photographic constituent layer, and more preferably, it is contained in the silver halide emulsion layer.

In order to include the compound [VI] in the silver halide emulsion containing the silver halide grains according to the present invention,
It may be added after dissolving in water or an organic solvent arbitrarily miscible with water (for example, methanol, ethanol or the like). The compound [VI] may be used alone or may have the general formula [V
A compound represented by general formula [V]
It may be used in combination with other stabilizers or antifoggants other than the compound represented by I].

The compound [VI] may be added during the formation of silver halide grains, after the formation of silver halide grains and before chemical sensitization, at the start of chemical sensitization, during chemical sensitization, and during chemical sensitization. It can be added at any time selected from the coating solution preparation step after the completion of the sensitization and after the completion of the chemical sensitization.

The amount of addition is not particularly limited, but is usually 1 × 10 ^-7 mol to 1 × 10 ^-1 mol, preferably 1 × 10 ^-6 mol to 1 × 10 ^-2 mol per mol of silver halide. Is added within the range.

The silver halide used in the silver halide emulsion layer according to the present invention includes silver chloride, silver bromide, silver iodide,
Any silver halide such as silver chlorobromide, silver iodobromide, silver chloroiodide and the like can be mentioned.

The silver halide grains preferably used in the present invention have a silver chloride content of 95 mol% or more, a silver bromide content of 5 mol% or less, and a silver iodide content of 0.5 mol%.
The following is preferred. More preferably, it is silver chlorobromide having a silver bromide content of 0.1 to 2 mol%. The silver halide grains may be used alone or as a mixture with other silver halide grains having different compositions. Further, it may be used by mixing with silver halide grains having a silver chloride content of 95 mol% or less. Further, in a silver halide emulsion layer containing silver halide grains having a silver chloride content of 95 mol% or more, a silver chloride content of 95 mol% of all silver halide grains contained in the emulsion layer is contained. The proportion of the silver halide grains is at least 60% by weight, preferably at least 80% by weight. The composition of the silver halide grains may be uniform from the inside to the outside of the grains, or the inside and outside compositions of the grains may be different. When the inside and outside compositions of the particles are different, the composition may change continuously or may be discontinuous.

The grain size of the silver halide grains is not particularly limited, but is preferably 0.2 to 1.6 μm, more preferably 0.25 to 1.2 in consideration of other photographic properties such as rapid processing and sensitivity.
It is in the range of μm.

The particle size distribution of the silver halide grains may be polydisperse or monodisperse. Monodisperse silver halide grains having a variation coefficient of preferably 0.22 or less, more preferably 0.15 or less, in the grain size distribution of the silver halide grains are preferred. Here, the coefficient of variation is a coefficient indicating the width of the particle size distribution, and is defined by the following equation.

Coefficient of variation = standard deviation of particle size distribution / average particle size The silver halide grains used in the present invention may be those obtained by any of an acidic method, a neutral method, and an ammonia method.
The particles may be grown at one time, or may be grown after seed particles are formed. The method of producing the seed particles and the method of growing them may be the same or different. The form of reacting a soluble silver salt with a soluble halide salt includes a forward mixing method, a reverse mixing method, a simultaneous mixing method, a combination thereof, and the like.
Either one may be used, but one obtained by the simultaneous mixing method is preferable. Further, as one type of the double jet method, a pAg controlled double jet method described in JP-A-54-48521 can be used.

If necessary, a silver halide solvent such as thioether or imidazole may be used. Further, a compound such as a mercapto group-containing compound, a nitrogen-containing heterocyclic compound or a sensitizing dye may be added at the time of forming silver halide grains or after the completion of grain formation.

The silver halide grains used in the present invention may have any shape. One preferable example is a cube having a {100} plane as a crystal surface. U.S. Pat.Nos. 4,183,756 and 4,225,666;
No. 55-26589, Japanese Patent Publication No. 55-42737, etc.
Photographic Science (J.Photgr.Sc
i.), 21 , 39 (1973), etc., particles having an octahedral, tetradecahedral, dodecahedral or the like shape can be prepared and used. Further, particles having a twin plane may be used. The silver halide grains used in the present invention may be grains having a single shape or a mixture of grains having various shapes.

In the present invention, in the process of forming and / or growing silver halide grains, cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (including complex salt), and rhodium salt (including complex salt). ), An iron salt (including a complex salt) to add a metal ion to be contained inside the particle and / or on the surface of the particle. Alternatively, a reduction sensitizing nucleus can be provided on the surface of the grain.

In the emulsion containing silver halide grains, unnecessary soluble salts may be removed after the growth of the silver halide grains has been completed, or may be kept contained.

In the present invention, the silver halide grains used in the emulsion may be grains whose latent image is mainly formed on the surface or grains mainly formed inside the grain. Preferably, the latent image is a particle mainly formed on the surface.

In the present invention, the emulsion is chemically sensitized by a conventional method. That is, a compound containing sulfur capable of reacting with silver ions, a sulfur sensitization method using active gelatin, a selenium sensitization method using a selenium compound, a reduction sensitization method using a reducing substance, a noble metal sensitization using gold or another noble metal compound. Sensing methods or the like can be used alone or in combination.

The emulsion can be optically sensitized to a desired wavelength region by using a sensitizing dye. As the sensitizing dye, a cyanine dye, a merocyanine dye, a composite cyanine dye, a composite merocyanine dye, a holopolar cyanine dye, a hemicyanine dye, a styryl dye, a hemioxanol dye, and the like can be used. Specific examples thereof include, for example, the exemplified compound BS- described in Japanese Patent Application No. 2-76278, pp. 76-82.
1 to BS-9, GS-1 to GS-5, RS-1 to RS-
8 and IRS-1 to IRS-10. Examples of supersensitizers that can be used in combination with these include, for example, the exemplified compounds SS-1 to SS-9 described in Japanese Patent Application No. 2-76278, pp. 84-85.

When exposing the silver halide photographic light-sensitive material according to the present invention to a printer using a semiconductor laser, it is necessary to use a sensitizing dye having sensitivity in the infrared region. For example, Japanese Patent Application No. 3-7361
The dyes of IRS-1 to 11 described in JP-A No. 9-page 12 to 14 are preferably used.

The silver halide photographic light-sensitive material according to the present invention may be exposed using a laser.

As a laser printer device considered to be applicable to such a system, for example, Japanese Patent Application Laid-Open No.
No. 071, JP-A-59-11062, JP-A-63-197947, JP-A-Hei.
2-74942, JP-A-2-36538, JP-B-56-14963, JP-B-56-40822, European wide-area patent 77410, Department of Electronics and Communication Technology Technical Report 80, 244, and Movie Television Technical Journal 1984
/ 6 (382), pp. 34-36.

It is advantageous to use gelatin as a binder in the silver halide photographic light-sensitive material of the present invention. If necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other high polymers, gelatin Other than these, hydrophilic colloids such as proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as homopolymers and copolymers can also be used.

In the present invention, a hardener of a binder is used. As the hardener, a vinyl sulfone type or chlorotriazine type hardener is preferably used. As the vinyl sulfone type hardening agent, compounds described in JP-A-61-249054, page 25, upper right, line 13 to page 27, upper right, second line can be preferably used. Further, compound H-12 described on page 26 of the same specification is more preferable. Chlorotriazine hardeners are described in JP-A-61-245153, page 3, lower left, first line
4th line from bottom right of page 3 and 4th to 5th line from bottom right of page 3
The compounds described at the lower left of the page are preferably used.

Further, the compound represented by XII-1 described on page 4 of the same specification is more preferred.

These hardeners are preferably used in combination of different kinds of compounds, and may be added to any layer. The hardener is preferably used in an amount of 0.1 to 10% by weight based on the binder.

In the present invention, it is preferable to add a fungicide to any of the layers. As preferred fungicides, compounds represented by the general formula II described in page 9 of Japanese Patent Application No. 1-298092 are preferred. Specific examples of the compound include
Compound examples No. 9 to No. 22 described on pages 69 to 70 are exemplified. Among them, a particularly preferred compound is the compound represented by No. 9.

As the reflective support according to the present invention, a white pigment-containing polyethylene-coated paper, a baryta paper, a vinyl chloride sheet, a white pigment-containing polypropylene, a polyethylene terephthalate support, and the like can be used. Among them, a support having on its surface a polyolefin resin layer containing a white pigment is preferable.

As the white pigment used in the reflective support according to the present invention, an inorganic and / or organic white pigment can be used, and preferably, an inorganic white pigment is used. For example, alkaline earth metal sulfates such as barium sulfate, alkaline earth metal carbonates such as calcium carbonate, finely divided silica, silica such as synthetic silicate, calcium silicate, alumina, alumina hydrate, oxidation Examples include titanium, zinc oxide, talc, and clay. The white pigment is preferably barium sulfate or titanium oxide. The amount of the white pigment contained in the water-resistant resin layer on the surface of the reflective support according to the present invention is preferably 10% by weight or more, more preferably 13% by weight, as the content in the water-resistant resin layer. The content is preferably at least the above, and more preferably at least 15% by weight. The degree of dispersion of the white pigment in the water-resistant resin layer of the paper support according to the present invention can be measured by the method described in JP-A-2-28640. When measured in this way,
The degree of dispersion of the white pigment is 0.
It is preferably 20 or less, more preferably 0.15 or less, and even more preferably 0.10 or less.

The silver halide photographic light-sensitive material according to the present invention may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the support surface, if necessary, and then directly or undercoat layer (adhesion of the support surface, (1 or 2 or more subbing layers for improving antistatic properties, dimensional stability, friction resistance, hardness, antihalation properties, friction properties and / or other properties) Good.

In coating a photographic light-sensitive material using a silver halide emulsion, a thickener may be used to improve coatability. Extrusion coating and curtain coating, in which two or more layers can be applied simultaneously, are particularly useful as a coating method.

As the aromatic primary amine developing agent used in the present invention, known compounds can be used. The following compounds can be mentioned as examples of these compounds.

(CD-1) N, N-diethyl-p-phenylenediamine (CD-2) 2-amino-5-diethylaminotoluene (CD-3) 2-amino-5- (N-ethyl-N-lauryl Amino) toluene (CD-4) 4- (N-ethyl-N- [β-hydroxyethyl] amino) aniline (CD-5) 2-methyl-4- (N-ethyl-N- [β-hydroxyethyl] Amino) aniline (CD-6) 4-amino-3-methyl-N-ethyl-N- (β- (methanesulfonamido) ethyl) -aniline (CD-7) N- (2-amino-5-diethylaminophenyl Ethyl) methanesulfonamide (CD-8) N, N-dimethyl-p-phenylenediamine (CD-9) 4-amino-3-methyl-N-ethyl-N-methoxyethylaniline (CD-10) 4-amino 3-methyl-N-ethyl-N- (β-ethoxyethyl) aniline (CD-11) 4-amino-3-methyl-N-ethyl-N- (β-butoxyethyl) aniline Image formation according to the present invention When used in the method, particularly from the viewpoint of a short development process, Compound represented by the formula (2) is more preferably used.

[0133]

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In the formula, R is a linear or branched alkylene group having 3 carbon atoms, m and n each represent an integer of 1 to 4, and HA represents an inorganic or organic acid, for example, hydrochloric acid,
Represents sulfuric acid, nitric acid, p-toluenesulfonic acid and the like.

These color developing agents are described in Journal of the American Chemical Society 73 3100 (1951).
Can be easily synthesized.

Specific examples of the compound represented by the general formula [2] are shown below.

[0137]

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[0138]

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The color developing agent according to the present invention is usually a developer
1 × 10 per liter^-2~ 2 × 10^-1Used in the mole range
From the viewpoint of rapid processing, 1.
5 x 10 ^-2~ 2 × 10^-1It is preferably used in the molar range.

The color developing agent used in the image forming method of the present invention may be used alone, or may be used in combination with other known p-phenylenediamine derivatives. In the image forming method according to the present invention, the compound used in combination with the compound represented by the general formula [I] includes (CD-5), (CD-6),
(CD-9) is preferred.

These p-phenylenediamine derivatives are
It is generally used in the form of salts such as sulfate, hydrochloride, sulfite, nitrate, p-toluenesulfonate and the like.

The color developer according to the present invention may contain the following components in addition to the above components.

As the alkaline agent, for example, sodium hydroxide, potassium hydroxide, sodium metaborate, potassium metaborate, trisodium phosphate, tripotassium phosphate,
Borax, silicate, and the like can be used alone or in combination within a range where precipitation does not occur and the pH stabilizing effect is maintained. In addition, various salts such as disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium bicarbonate, potassium bicarbonate, and borate are used for dispensing purposes or for the purpose of increasing ionic strength. can do.

In the image forming method according to the present invention, chloride ions are used as the color developing solution, and potassium chloride, sodium chloride and the like are used. The amount of chloride ion is 6.0 × 10 ^-2 mol or more per liter of color developing solution,
Preferably it is 8.0 × 10 ^{-2 to} 2.0 × 10 ^-1 mol.

The bromide ion can be used in a range not impairing the effects of the present invention, but since it has a large effect of suppressing the development, it is about 1.10 per liter of the color developing solution.
It is desirably 0 × 10 ⁻³ mol or less, preferably 5.0 × 10 ⁻⁴ mol or less.

Further, if necessary, a development accelerator can be used. As development accelerators, U.S. Pat.
No. 4, 3,671,247, various kinds of pyridinium compounds represented by JP-B-44-9503, other cationic compounds, cationic dyes such as phenosafranine, neutral salts such as thallium nitrate, U.S. Pat. No.2,53
No. 1,832, No. 2,950,970, No. 2,577,127 and Japanese Patent Publication No. 44-
Nonionic compounds such as polyethylene glycol and derivatives thereof and polythioethers described in JP 9504
Organic solvents, organic amines, ethanolamine, ethylenediamine, diethanolamine, triethanolamine and the like described in No. 44-9509 are included. Also, U.S. Patent 2,304,92
No. 5, phenethyl alcohol, acetylene glycol, methyl ethyl ketone, cyclohexanone, pyridine, ammonia, hydrazine, thioethers, amines and the like.

Further, if necessary, the color developing solution according to the present invention may contain ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin, and other JP-B Nos. 47-33378 and 44-9509.
Can be used as an organic solvent for increasing the solubility of the developing agent.

Further, an auxiliary developer can be used together with the developing agent. These auxiliary developers include, for example, N-methyl-p-aminophenol sulfate, phenidone, N, N'-diethyl-p-aminophenol hydrochloride, N, N,
N ', N'-tetramethyl-p-phenylenediamine hydrochloride and the like are known, and the amount of addition is usually 0.01 to 1.0 g per liter of developer. In addition, if necessary, a competitive coupler, a fogging agent, a development inhibitor releasing type coupler (a so-called DIR coupler), a development inhibitor releasing compound and the like can be added.

Further, various additives such as other stain inhibitors, sludge inhibitors, and layering effect promoters can be used.

Each component of the color developing solution can be prepared by sequentially adding and stirring a certain amount of water. In this case, the component having low solubility in water can be added as a mixture with the above-mentioned organic solvent such as triethanolamine. Further, more generally, a concentrated aqueous solution containing a plurality of components each of which can stably coexist, or a solution prepared in advance in a small container in a solid state is added to water and stirred to form a color developer according to the present invention. Can also be prepared.

In the present invention, a color developing solution is added to any p
It can be used in the H range, but the pH is 9.5 to 1 from the viewpoint of rapid processing.
It is preferably 3.0, and more preferably used in the range of 9.8 to 12.0.

The processing temperature of color development according to the present invention is 35 ° C.
As described above, the temperature is preferably 70 ° C. or lower.

The higher the temperature, the shorter the processing time is. However, from the viewpoint of the stability of the processing solution, the higher the temperature, the better.
The treatment is preferably carried out at a temperature of not lower than 60 ° C and not higher than 60 ° C.

Conventionally, the color development time is generally about 3 minutes and 30 seconds, but in the present invention, it is preferably within 30 seconds, further within 20 seconds, and more preferably within the range of 20 to 3 seconds.

In the present invention, the replenishment rate of color development is preferably 20 to 100 ml per 1 m ² of the light-sensitive material.

More preferably, the volume is 20 to 80 ml.

The processing step substantially comprises a color developing step, a bleach-fixing step, and a rinsing step (including a stabilizing treatment in place of rinsing), but steps are added or equivalently provided that the effects of the present invention are not impaired. Can be replaced by a process having For example, the bleach-fixing step can be separated into a bleaching step and a fixing step, or a bleaching step can be performed before the bleach-fixing step. As a processing step used in the image forming method of the present invention, a bleach-fixing step is preferably provided immediately after the color developing step.

The bleaching agent that can be used in the bleach-fixing solution used in the image forming method of the present invention is not limited, but is preferably a metal complex salt of an organic acid. The complex salt is a complex salt in which an organic acid such as polycarboxylic acid, aminopolycarboxylic acid or oxalic acid or citric acid is coordinated to a metal ion such as iron, cobalt or copper. Most preferred organic acids used to form such metal complex salts include polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

Specific examples of the compound include compounds [2] to [20] described in JP-A-1-205262, pp. 58-59.

These bleaching agents are used in an amount of 5 to 450 g, preferably 20 to 250 g, per liter of the bleach-fix solution. As the bleach-fixing solution, a solution having a composition containing a silver halide fixing agent in addition to the bleaching agent as described above and, if necessary, a sulfite as a preservative is applied.

A bleach-fixing solution having a composition in which a large amount of a halide such as ammonium bromide is added in addition to the ethylenediaminetetraacetate (III) acid bleaching agent and the above-mentioned silver halide fixing agent; III) A special bleach-fixing solution having a composition comprising a combination of an acid bleach and a large amount of a halide such as ammonium bromide can be used. As the halide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide and the like can be used in addition to ammonium bromide.

As the silver halide fixing agent contained in the bleach-fixing solution, a compound capable of forming a water-soluble complex salt by reacting with silver halide as used in ordinary fixing processing, such as potassium thiosulfate and sodium thiosulfate Typical examples thereof include thiosulfates such as ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, thiocyanates such as ammonium thiocyanate, thiourea, and thioether. These fixing agents are used in an amount of 5 g or more per liter of the bleach-fixing solution, in an amount that can be dissolved, but generally used in an amount of 70 to 250 g. The bleach-fixing solution contains various pH buffers such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide. They can be contained alone or in combination of two or more. Further, various fluorescent whitening agents, antifoaming agents or surfactants can be added.

Also, preservatives such as hydroxylamine, hydrazine and bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acid and stabilizers such as nitro alcohol and nitrate, methanol, dimethyl sulfonamide, dimethyl sulfoxide And the like can be appropriately contained. The bleach-fixing solution according to the present invention includes JP-A-46-280, JP-B-45-8506, and JP-B-46-55.
No. 6, Belgian Patent No. 770910, Japanese Patent Publication No. 45-8836, No. 53-9
Various bleaching accelerators described in JP-A-854, JP-A-54-71634 and JP-A-49-42349 can be added.

The pH of the bleach-fixing solution is used at 4.0 or higher, but is generally used in the range of 4.0 to 9.5, preferably pH.
Used in 4.5-8.5. Most preferably, it is used in the range of pH 5.0 to 8.5. The temperature of the treatment is below 80 ° C, preferably
Use at 55 ° C or less with evaporation suppressed. The processing time for bleach-fixing is preferably from 3 to 45 seconds, more preferably from 5 to 30 seconds.

In the developing process according to the present invention, a water washing process is performed subsequent to the color developing and bleach-fixing steps.
Hereinafter, a preferred embodiment of the water washing process will be described.

As the compound preferably used in the washing solution, a chelating agent having a chelate stabilization constant for iron ions of 8 or more is preferable. Here, the chelate stabilization constant is defined as “Stability Constant” by LGSillen and AE Martell.
s of Metalion Complexes, '' The Chemical Society, Lon
don (1964), S. Chaberek, AE Martell, `` OrganicSeq
uestering Agents ", Wiley (1959), and the like.

Examples of the chelating agent having a chelating stability constant for iron ions of 8 or more which are preferably used in the washing liquid include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, polyhydroxy compounds and the like. Can be In addition, the said iron ion means ferric ion. Specific compounds of the chelating agent having a chelate stability constant of 8 or more with ferric ion are described in JP-A-1-2051.
The compounds described in page 62, page 63, line 15 to page 64, line 17 can be mentioned.

The amount of the chelating agent to be used is preferably 0.01 to 50 g, more preferably 0.05 to 20 g, per liter of the washing liquid. Further, as a compound to be added to the washing liquid, an ammonium compound is mentioned as a particularly preferred compound. These are supplied by ammonium salts of various inorganic compounds. Specific examples include compounds described in JP-A-1-205162, page 65, line 5 to page 66, line 11. The amount of the ammonium compound added is 1.0 × 1 per liter of the washing solution.
It is preferably from 0 to ⁵ mol or more, more preferably from 0.001 to 5.0 mol, and still more preferably from 0.002 to 1.0 mol.

It is desirable that the washing liquid contains a sulfite within a range that does not cause bacteria or the like. The sulfite to be contained in the washing liquid may be any substance such as an organic substance or an inorganic substance, as long as it releases sulfite ions, but is preferably an inorganic salt, and as a preferable specific compound,
Sodium sulfite, potassium sulfite, ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite and hydrosulfite, cartalaldehyde bisulfite sodium bisulfite, succinic acid Aldehyde bis sodium sulfite and the like.

The above sulfite is preferably added at least 1.0 × 10 ⁻⁵ mol per liter of the washing solution,
^{-5 to} 1.0 × 10 ^-1 mol is more preferred. The method of addition may be directly to the washing solution, but preferably added to the washing replenisher.

The washing liquid used in the present invention desirably contains a fungicide, which can prevent sulfidation and improve image storability. Examples of the fungicide that can be used in the washing liquid according to the present invention include sorbic acid, benzoic acid compounds, phenol compounds, thiazole compounds, pyridine compounds, guanidine compounds, morpholine compounds, and quaternary phosphonium compounds. ,
Ammonium compounds, urea compounds, isoxazole compounds, propanolamine compounds, sulfamide compounds, pyronone compounds and amino compounds. Specific compounds are described in JP-A-1-205162
The compounds described on page 68, line 10 to page 72, line 16 are mentioned.
Among these compounds, particularly preferred compounds are thiazole compounds, sulfamide compounds, and pyronone compounds.

The amount of the fungicide to be added to the washing liquid is preferably in the range of 0.001 to 30 g, more preferably 0.003 to 5 g, per liter of washing liquid.

The washing liquid according to the present invention preferably contains a metal compound in combination with a chelating agent. Such metal compounds include Ba, Ca, Ce, Co, In, La, Mn, Ni, Bi,
Examples include compounds of Pb, Sn, Zn, Ti, Zr, Mg, Al, and Sr. These metal compounds can be supplied as inorganic or organic salts such as halides, sulfates, carbonates, phosphates, acetates, etc., hydroxides or water-soluble chelate compounds. The addition amount of these compounds is preferably 1.0 × 10 ^{−4 to} 1.0 × 10 ⁻¹ mol per liter of the washing solution, and 4.0 × 10 ⁻⁴ mol.
~ 2.0 × 10 ^-2 mol is more preferred.

Compounds having an aldehyde group other than those described above may be used in the washing liquid according to the present invention. Specific compounds include exemplified compounds 1 to 32 described on pages 73 to 75 of JP-A-1-205162.

The compound having an aldehyde group is preferably used in an amount of 0.1 to 50 g, particularly preferably 0.5 to 10 g, per liter of the washing liquid.

Further, as the washing water according to the present invention, ion exchange water treated with an ion exchange resin may be used.

The pH of the washing water applicable to the present invention is 5.5 to 5.5.
It is in the range of 10.0. As the pH adjusting agent applicable to the present invention, any of generally known alkali agents and acid agents can be used.

The treatment temperature of the water washing treatment is preferably from 15 ° C. to 60 ° C., and more preferably from 20 ° C. to 45 ° C. The time of the water washing treatment is preferably 5 to 60 seconds, more preferably 5 to 50 seconds.
In the case of performing the water washing treatment in a plurality of tanks, it is preferable that the treatment is performed in a shorter time in the front tank and the treatment time is longer in the rear tank.
In particular, it is preferable to sequentially perform the treatment with a treatment time that is 20% to 50% longer than that of the preceding tank.

In the method of supplying the washing liquid in the washing treatment step according to the present invention, when a multi-tank counterflow current system is used, it is preferable to supply the washing liquid to a post-bath and overflow the pre-bath. Of course, it can also be processed in a single tank. As a method of adding the above compound, various methods such as adding the above compound and other additives to the washing liquid to be supplied to the washing tank, or adding the compound and other additives to the washing tank to be added to the washing tank, and using this as a washing replenisher. Is used.

The amount of washing water in the washing step according to the present invention is preferably 0.1 to 50 times, more preferably 0.5 to 3 times the carry-in amount of the prebath (usually bleach-fixing solution or fixing solution) per unit area of the photosensitive material.
0 times is preferred.

The washing tank in the washing treatment according to the present invention has one
It is preferably from 5 to 5 tanks, and more preferably from 1 to 3 tanks.

Examples of the apparatus for developing a silver halide photographic light-sensitive material used in the image forming method of the present invention include a roller transport type in which the light-sensitive material is conveyed between rollers arranged in a processing tank, and a light-sensitive material on a belt. An endless belt system in which the paper is fixed and conveyed is used.

In the image forming method of the present invention, the time from exposure to development may be any, but it is preferable that the time is short in order to shorten the entire processing time.

Further, the silver halide photographic light-sensitive material of the present invention has a small change in image density even when the time from exposure to development is 30 seconds or less, so that a high-quality image can be stably obtained. It can be used advantageously.

[0185]

EXAMPLES The present invention will be described below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 On a support in which polyethylene was laminated on one side of a paper support and polyethylene containing titanium oxide was laminated on the other side, each layer having the following structure was replaced with a polyethylene layer containing titanium oxide. This was coated on the side to prepare a multilayer silver halide color photographic material sample 1-1. The coating solution was prepared as follows.

First layer coating solution 26.7 g of yellow coupler (YC-1), 10.0 g of dye image stabilizer (ST-1), dye image stabilizer (ST-2)
Ethyl acetate (60 cc.) Was added to and dissolved in 6.67 g, 0.67 g of the stain inhibitor (HQ-1) and 6.67 g of the high boiling point organic solvent (DNP), and this solution contained 7 cc of a 20% surfactant (SU-1). The mixture was emulsified and dispersed in 220 cc of a 10% aqueous gelatin solution using an ultrasonic homogenizer to prepare a yellow coupler dispersion. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 10 g of silver) prepared under the following conditions to prepare a first layer coating solution.

[0188]

[Table 1]

[0189]

[Table 2]

[0190]

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[0191]

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[0192]

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[0193]

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[0194]

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[0195]

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[0196]

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(Method for Preparing Blue-Sensitive Silver Halide Emulsion) 40
The following (Solution A) and (Solution B) were simultaneously added over 30 minutes to 1000 cc. Of a 2% aqueous gelatin solution kept at ℃ while controlling pAg = 6.5 and pH = 3.0. (D
Liquid) was added simultaneously over 180 minutes while controlling pAg = 7.3 and pH = 5.5.

At this time, pAg was controlled by the method described in JP-A-59-45437, and pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to 200 cc. (Solution B) 10 g of silver nitrate was added to 200 cc. (Solution C) Sodium chloride 102.7 g Potassium bromide 1.0 g Water was added. (D solution) 300 g of silver nitrate was added and 600 cc of water was added. After the addition was completed, desalting was performed using a 5% aqueous solution of Demol N manufactured by Kao Atlas and a 20% aqueous solution of magnesium sulfate, and then mixed with an aqueous gelatin solution. Thus, a monodispersed cubic emulsion EMP-1 having an average particle size of 0.85 μm, a variation coefficient of the particle size distribution of 0.07, and a silver chloride content of 99.5 mol% was obtained.

The following compounds were used for the above EMP-1
Optimum chemical sensitization was performed at 50 ° C. to obtain a blue-sensitive silver halide emulsion (Em-B).

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX sensitization Dye BS-2 1 × 10 ^-4 mol / mol AgX (Preparation method of green-sensitive silver halide emulsion) (solution A) and (B
Liquid) and the addition time of (liquid C) and (liquid D) in the same manner as in EMP-1, except that the addition time was changed.
m, a coefficient of variation of 0.08 and a monodispersed cubic emulsion EMP-2 having a silver chloride content of 99.5% were obtained.

The following compound was used for the above EMP-2
Optimum chemical sensitization was performed at 55 ° C to obtain a green-sensitive silver halide emulsion (Em-G).

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX (red Method for preparing photosensitive silver halide emulsions) (solution A) and (B)
Liquid) and the addition time of (liquid C) and (liquid D) were changed in the same manner as in EMP-1 except that the average particle size was 0.50 μm.
m, a coefficient of variation of 0.08 and a monodisperse cubic emulsion EMP-3 having a silver chloride content of 99.5% were obtained.

The following metal compounds were added to the above (C solution).

K ₂ IrCl ₆ 3.8 × 10 ⁻⁸ mol / mol AgX K ₄ Fe (CN) ₆ 1.2 × 10 ⁻⁵ mol / mol AgX The above EMP-3 was optimally chemically treated at 60 ° C. using the following compound. After sensitization, a red-sensitive silver halide emulsion (Em-
R) was obtained.

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 6 × 10 ^-4 mol / mol AgX sensitizing dye RS-1 1 × 10 ^-4 mol / mol AgX

[0207]

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Next, the yellow coupler (YC-1) in the first layer of Sample 1-1 was changed as shown in Table 1,
Also, samples 1-2 to 1-24 were prepared in the same manner as sample 1-1, except that the surfactant of the seventh layer was changed as shown in Table 1.

Further, in Samples 1-2 to 1-24, the following stabilizer STB-2 was added to the coating solution for the first layer in an amount of 0.2% per m ² of the light-sensitive material.
It was added and adjusted to 3 mg.

[0210]

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[0211]

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Each of the samples thus obtained was exposed according to a conventional method, and then processed according to the following processing steps.

(Processing step) Processing step Processing temperature Time Replenishment amount Color development 38.0 ± 0.3 ° C. 27 seconds 70 cc./m ² Bleaching and fixing 35.0 ± 0.5 ° C. 27 seconds 54 cc./m ² Stable 30-34 ° C. 90 seconds 150 cc./m ² the composition of m ² drying 60-80 ° C. 30 seconds development processing solution shown below.

Color developing solution tank pure water 800 cc. Diethylene glycol 10 g Potassium bromide 0.01 g Potassium chloride 3.5 g Potassium sulfite 0.25 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate Salt 6.5 g N, N-diethylhydroxylamine 3.5 g Ethylhydroxylamine disulfonic acid 3.5 g Triethanolamine 10.0 g Sodium salt of diethylenetriaminepentaacetic acid 2.0 g Optical brightener (4,4'-diaminostilbenesulfonic acid derivative) 2.0 g Carbonic acid Add 30 g of potassium water to make the total volume 1 liter, and adjust the pH to 10.10.

Color developing solution replenisher pure water 800 cc. Diethylene glycol 10 g potassium sulfite 0.5 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 10.5 g N, N-diethylhydroxyl Amine 6.0g Ethylhydroxylamine sulfonate 6.0g Triethanolamine 10.0g Sodium salt of diethylenetriaminepentaacetic acid 2.0g Fluorescent brightener (4,4'-diaminostilbenesulfonic acid derivative) 2.5g Potassium carbonate 30g Add water to make the total amount 1 Liter and adjust the pH to 10.60.

Bleach-fix bleach-fix replenisher tank liquid diethylenetriaminepentaacetic acid ferric ammonium dihydrate 100 g 50 g diethylenetriaminepentaacetic acid 3 g 3 g ammonium thiosulfate (70% aqueous solution) 200 cc. 100 cc. 5-amino-1,3,4-thiadiazole 2-thiol 2.0 g 1.0 g ammonium sulfite (40% aqueous solution) 50 cc. 25 cc. PH 6.5 7.0 Add water to make the total volume 1 liter, and adjust the pH with ammonia water or glacial acetic acid.

Stabilizing tank solution and replenisher orthophenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g diethylene glycol 1.0 g fluorescent brightening Agent (Tinopearl SFP) 2.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g PVP (polyvinylpyrrolidone) 1.0 g ammonia water (25% aqueous ammonium hydroxide) 2.5 g ethylenediaminetetraacetic acid 1.0 g ammonium sulfite (40% aqueous solution) 10 cc. Add water to make the total volume 1 liter, and adjust the pH to 7.5 with sulfuric acid or aqueous ammonia.

The stabilization treatment was replenished by a three-stage multistage countercurrent system.

A running process was performed using the prepared sample and the processing solution. In the running process, the automatic developing machine was filled with the color developing solution, the bleach-fixing tank solution and the stabilizing tank solution, and the continuous replenishing process was performed until the cumulative value of the replenishing amount exceeded twice the amount of the solution at the start. About the obtained sample,
The following performance evaluation test was performed.

<Sensitometry> Each of the treated samples was subjected to PDA-
Using a 65 densitometer (manufactured by Konica Corporation), sensitivity, gradation, and maximum density (Dmax) were determined.

Sensitivity (S) = Reciprocal of exposure amount giving reflection density 0.8 Gradation (γ) = Slope of straight line connecting points of reflection density 0.5 and 1.5 in HD curve obtained by ordinary method <Sharpness> For each sample After the resolution test chart is printed with red light and the above processing is performed, the density of the obtained cyan image is measured with a microdensitometer PDM-5 (manufactured by Konica Corporation), and the value represented by the following formula is calculated. Sharpness.

Sharpness (R) = (Dmax−Dmin of dense line printed image of 5 lines / mm) / (Dmax−Dmin in large area portion) where Dmax: maximum density, Dmin: minimum density The larger the value, the better the sharpness.

<Color turbidity> After the sample was subjected to green separation exposure through a light wedge and developed in the processing steps described above, the green density and the blue density of the magenta color-developed portion were changed to X.
Green density 1.5
(That is, yellow turbid component of magenta dye image, hereinafter abbreviated as DB _{/ G} ).

Similarly, after exposing the sample to blue separation exposure,
After performing the above processing, the blue density 1.5
Of the yellow dye image (hereinafter, abbreviated as DG _{/ B} ),
_{B / G} and DG _{/ B} were evaluated for color turbidity.

<Preservation of raw sample> One sample was stored at 50 ° C./40.
% RH, and the other was stored in a refrigerator at 5 ° C., each of which was developed in the processing steps described above, and the blue density (Dmin ^B ) of the unexposed portion was changed to X.
Measured with Rite310 (manufactured by X-Rite), 50 ℃ / 4
The difference ΔDmin ^B between Dmin ^B (50) of the sample stored under the condition of 0% RH and Dmin ^B (5) of the sample stored in the refrigerator was determined as follows.

[0226] Using ^{ΔDmin B = Dmin B (50)} -Dmin B (5) imaging the developed negative film <color reproducibility> color chart (manufactured by Macbeth Co.) at Konica Color XG100 (manufactured by Konica Corp.), the gray scale portion After adjusting the color tones, the prints obtained by exposing and processing each sample were visually evaluated for color reproducibility in each hue.

Table 3 also shows the evaluation results.

[0228]

[Table 3]

As is clear from the results shown in Table 3, the sample using the yellow coupler of the present invention has a sufficient coloring property as compared with the sample using the comparative coupler, but the color turbidity and the fog increase during storage of the raw sample are reduced. On the other hand, in the sample in which the yellow coupler of the present invention and the surfactant of the present invention are combined, the color turbidity and the fog increase during storage of the raw sample are significantly reduced without impairing the color developing property, and the constitution of the present invention It can be seen that only the sample prepared in the above was excellent in all of the color reproducibility, color development, and fog during storage. The synergistic effect on the important photographic performance of the combination of the specific structure of the yellow coupler and the specific surfactant could not be predicted from the conventional knowledge.

Example 2 In the same manner as in Example 1, the sample No. 1-
Sample No. 3 was changed except that the yellow coupler in the first layer and the type and amount of the stabilizer in the first layer were changed, and the surfactant in the seventh layer was changed as shown in Table 4. Sample Nos. 2-1 to 2-19 were prepared in the same manner as in 1-3, and the obtained samples were processed at a color development processing temperature of 40 ° C. ± 0.3 ° C. Except for 20 seconds, the same processing as in Example 1 was performed, and the same evaluation as in Example 1 was performed.

[0231]

Embedded image

Table 4 also shows the evaluation results.

[0233]

[Table 4]

From the results shown in Table 4, similar to the first embodiment, a great improvement effect of the constitution of the present invention was recognized.

In Examples 1 and 2, it was confirmed that sufficient color reproducibility was obtained in the sample of the present invention.

Continuation of the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) G03C 7/36 G03C 1/38 G03C 7/392

Claims (5)

(57) [Claims] 1. A silver halide color photographic light-sensitive material having a photographic component layer comprising at least one light-sensitive silver halide emulsion layer on a support, wherein at least one of said silver halide emulsion layers has a general formula [ I], and at least one of the photographic constituent layers contains at least one surfactant selected from a fluorine-containing anionic surfactant and a fluorine-containing cationic surfactant. A silver halide color photographic light-sensitive material, characterized in that: Embedded image [In the formula, R ₁ represents an alkyl group or a cycloalkyl group, and R ₂ represents an alkyl group, a cycloalkyl group, and an aryl group. Z ₆ represents a hydrogen atom or a group capable of leaving upon coupling with an oxidized form of the developing agent. W ₂
Represents a group represented by the following general formulas [II] and [III]. Embedded image In the above general formula [II], R ₁₉ has from 11 carbon atoms.
Represents up to 21 straight-chain or branched unsubstituted alkyl groups.
In the above general formula [III], R ₂₀ represents a hydrogen atom or a linear or branched unsubstituted alkyl group having 1 to 6 carbon atoms, preferably an ethyl group, a butyl group, and a hexyl group. In the general formula [III], R ₂₁ and R ₂₂ represent a hydrogen atom or a branched alkyl group having 4 to 12 carbon atoms. However, the sum of the number of carbon atoms of R ₂₁ and R ₂₂ is between 4 and 16. In the above general formula [I], Z ₆ represents a group represented by the following general formula [IV]. Embedded image Embedded image In the above general formula [IV], Z ₄ represents a nonmetallic atom group necessary for forming a 5- or 6-membered ring in cooperation with —Y ₁ —N—CO—. Z ₆ represents a group having the same meaning as the group represented by the above general formula [IV], and represents a group represented by the following general formula [V] (represented by the general formula [I] due to reaction with an oxidized form of a developing agent). (A state in which a hydrogen atom has been added to Z ₆ removed from the compound to be produced), and has a molecular weight of 235 or less. [Chemical formula 5] 2. The silver halide color photographic light-sensitive material according to claim 1, wherein at least one of the photographic constituent layers contains a compound represented by the following general formula [VI]. Embedded image [Wherein, Ar represents an aromatic group, and R ₃₁ represents —OR ₃₂ , —N
(R ₃₃ ) SO ₂ R ₃₄ or —COOM ² R ₃₂ represents a hydrocarbon group having 2 or more carbon atoms, R ₃₃ represents a hydrogen atom or a hydrocarbon group, and R ₃₄ represents a hydrocarbon group. M ¹ and M ² represent a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or an ammonium group. ] 3. At least one of the silver halide emulsion layers
2. A silver halide color photographic light-sensitive material according to claim 1, wherein said layer contains a silver halide emulsion having a silver chloride content of 95 mol% or more. 4. A method for forming a color image by processing the silver halide color light-sensitive material of claim 1 with a color developing solution, followed by bleach-fixing and washing or stabilizing, wherein the color developing replenishment amount is photosensitive material 1m ² per 20~100m
l, a color image forming method. 5. A method for forming a color image by processing the silver halide color light-sensitive material of claim 1 with a color developing solution, followed by bleach-fixing and washing or stabilizing to form a color image. A color image forming method, wherein the time is less than seconds.