JPH10161287A - Silver halide photographic sensitive material and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the silver halide photographic sensitive material and its image forming method capable of restraining deterioration of color reproduction performance due to insufficient desilvering at the time of enhancing the speed of the bleaching and fixing processes after sensitization development processing. SOLUTION: The silver halide photographic sensitive material is provided with at least one color image forming layer containing photosensitive silver halide and a coupler on a support and this color image forming layer contains the sliver halide in an amount of <=0.1g/m<2> in terms of silver and the diffusion resistant coupler to be allowed to release a mobile dye by a coupling reaction with the oxidation product of a color developing agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material and an image forming method in which deterioration in color reproducibility due to poor desilvering is improved when speeding up the bleaching and fixing processing steps after amplification development processing. It is.

[0002]

2. Description of the Related Art Silver halide photographic light-sensitive materials (hereinafter simply referred to as "light-sensitive materials") are extremely superior to other print materials in that they have high sensitivity and excellent gradation. Due to its properties, it is widely used today. It has the features of these photographic materials, furthermore, the amount of silver halide in the photographic material is small (the amount of silver is small), and as a preferable means in terms of effective use of resources, an image is formed by amplifying and developing the photographic material. The method has been known for a long time. As an example of the amplification development processing, there is a method in which an oxidized color developing agent is generated with an oxidizing agent such as hydrogen peroxide / cobalt (III) complex using developed silver as a catalyst, and then an image dye is formed by reaction with a coupler. . A further expectation for the amplification and development processing of such a low silver content photographic material is to speed up the bleaching and fixing steps. However, there is a limit to reducing the amount of silver from the viewpoint of improving print image quality and shortening the amplification development processing time, and a photosensitive material using a sufficient amount of silver halide to obtain satisfactory print image quality within an acceptable amplification development processing time. In addition, when speeding up or omitting the bleaching and fixing processing steps after amplification development, desilvering is not performed sufficiently, and it is difficult to reproduce vivid colors without dullness on printed images. Was.

[0003] US Pat. No. 5,411,848 discloses a technique in which a yellow coupler having a specific structure for forming a mobile dye is applied to a photosensitive material for amplification and development processing. The purpose of the present invention is to prevent a decrease in the maximum density, and there is no description of the effect of the present invention, which can improve the desilvering failure in the bleaching and fixing processing steps after the amplification development processing.

[0004]

SUMMARY OF THE INVENTION The present invention provides a silver halide photographic light-sensitive material and an image forming method in which deterioration in color reproducibility due to poor desilvering is improved when the bleaching and fixing processing steps after the amplification development processing are accelerated. Is provided.

[0005]

The above objects of the present invention have been attained by the following constitutions.

(1) In a silver halide photographic material having at least one color image forming layer having a photosensitive silver halide and a coupler on a support, the amount of silver halide contained in the color image forming layer Is 0.1 g / m in silver equivalent
^{2. The} silver halide photographic material, wherein the color image forming layer contains a diffusion-resistant coupler which forms a mobile dye by a coupling reaction with an oxidized color developing agent.

(2) In a silver halide photographic material having at least one color image forming layer having a photosensitive silver halide and a coupler on a support, the amount of silver halide contained in the color image forming layer Is 0.1 g / m in silver equivalent
² or less, and the color image forming layer forms a dye molecule having no pKa12 or less dissociable group and a molecular weight of 250 or more and 700 or less by a coupling reaction with an oxidized form of a color developing agent. Silver halide photographic material.

(3) In a silver halide photographic material having at least one color image forming layer having a photosensitive silver halide and a coupler on a support, the amount of silver halide contained in the color image forming layer Is 0.1 g / m in silver equivalent
² or less, and the color image forming layer has at least one p-type compound by a coupling reaction with an oxidized color developing agent.
A silver halide photographic light-sensitive material having a dissociable group of ka12 or less and forming a dye molecule having a molecular weight of 450 to 1200.

(4) The halogen as described in any one of (1) to (3) above, wherein the amount of silver halide contained in the color image forming layer is 0.045 g / m ² or less in terms of silver. Silver halide photographic material.

(5) The silver halide photographic material as described in (4) above, wherein the diffusion-resistant coupler forming the mobile dye is a magenta coupler or a cyan coupler.

(6) An image forming method comprising subjecting the silver halide photographic material as described in any one of (1) to (5) to amplification development processing.

Hereinafter, the present invention will be described in detail. The light-sensitive material according to the present invention has at least one color image forming layer having a light-sensitive silver halide and a coupler on a support,
The amount of silver halide contained in the color image forming layer is 0.1 g / m ² or less in terms of silver, and the color image forming layer forms a mobile dye by a coupling reaction with an oxidized color developing agent. It contains a diffusion-resistant coupler to be formed. When the amount of silver halide in the color image forming layer is 0.1
When it is larger than g / m ^2, when desired bleaching and fixing processes are speeded up, poor desilvering tends to occur, and it is difficult to obtain a vivid print image without dullness.

In the present invention, it is particularly preferred that the amount of silver halide in the color image forming layer is smaller than 0.045 g / m ^{2 in} terms of silver. In this case, the bleaching step after the amplification and development is accelerated. However, it is particularly preferable because a vivid print image without dullness can be obtained. The amount of silver halide in the color image forming layer is 0.005 g in terms of silver.
/ M ² or more is preferable because the time required for the amplification and development processing can be shortened and the feeling of roughness in the highlight portion during printing can be reduced.

In the present invention, an action mechanism capable of obtaining a vivid print image without dulling without causing defective desilvering when the desired bleaching and fixing processing steps are accelerated has been clarified. Although not described, since the mobile dye has an appropriate diffusibility as described below,
It is presumed that a decrease in the dye concentration around the developed silver is a main factor for enabling a rapid desilvering reaction.

In the present invention, the migrating dye formed by the coupling reaction between the diffusion-resistant coupler and the oxidized product of the color developing agent is formed by forming a substituent which imparts diffusion resistance to the coupler. Represents a dye which is not present in a dye and has an appropriate diffusion property and can cause an appropriate bleeding. Moderate diffusion and modest bleeding here means
In a processing step such as amplification development, bleaching / fixing, etc., it refers to a state in which the dye is diffused and bleeds to such an extent that the density does not decrease due to the outflow of the formed dye and the sharpness is not significantly deteriorated. Preferably, the size of the dye cloud formed around one developed silver particle is resistant to the formed dye under amplification processing conditions optimized to obtain the appropriate maximum and minimum densities. Dyes that are about 1.5 to 3 times as large as non-migrating dye clouds formed when a diffusing group is introduced.

As a method of designing a mobile dye so as to have an appropriate diffusion property and to generate an appropriate bleeding as described above, the mobile dye is adjusted so that the molecular weight of the dye is in an appropriate range. And a method in which a transferable dye is prepared by providing a dissociable substituent during the stabilization treatment, amplification amplification, bleaching and fixing (the bleaching and fixing may be performed simultaneously) or the like. When the formed dye molecule does not have a dissociable group having a pka of 12 or less, when the molecular weight of the dye molecule is from 250 to 700, the effect of improving color reproducibility deterioration due to poor desilvering is remarkable. is there. Also, the dye molecule formed has at least one p
In the case of having a dissociable group of ka12 or less, the effect of improving color reproducibility deterioration due to poor desilvering is remarkable when the molecular weight of the dye molecule is 450 or more and 1200 or less. Here, pka is defined as pka = l, where ka is an acid dissociation constant.
ogka. Examples of the dissociable group having a pka of 12 or less include a hydroxyl group, a carboxyl group,
And a sulfo group and an aminosulfonyl group.

Preferred examples of the diffusion-resistant coupler which forms a mobile dye by a coupling reaction with an oxidized form of a color developing agent are particularly those represented by the following formulas (1) to (10).
And a coupler represented by the formula:

[0018]

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In the formula, R ₁ represents an alkyl group, an alkylamino group, a heterocyclic group, or an aryl group. R ₂ represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. R ₃
Represents a regulating group. n represents an integer of 1 to 4. Z represents a leaving group.

[0020]

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In the formula, R ₅ represents a phenyl group which may have at least one substituent selected from a halogen atom, an alkyl group, an alkoxy group and an amino group. Also,
R ₅ may have a controlling group. R ₄ represents a controlling group. Z represents a leaving group.

[0022]

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In the formula, one of R ₆ and R ₇ is a regulating group, and the other is a hydrogen atom, an alkyl group, an alkoxy group,
Aryl group, amino group, acylamino group, heterocyclic group, alkylthio group, arylthio group, heterocyclic thio group, alkyloxy group, aryloxy group, heterocyclic oxy group, R ₃₁
—COR ₃₃ N—, R ₃₁ —SO ₂ R ₃₃ N— represents a group (R ₃₁
Represents an alkyl group, an aryl group, or a heterocyclic group. R ₃₃ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group). Z represents a leaving group.

[0024]

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In the formula, one of R ₈ and R ₉ is a control group, and when R ₉ is a control group, R ₈ represents an alkyl group, an aryl group, or a heterocyclic group. When R ₈ is a controlling group, R ₉ is an alkyl group, an aryl group, a heterocyclic group, R ₃₁ —COR ₃₃ N
— Group, R ₃₁ —OCOR ₃₃ N— group, R ₃₁ —SO ₂ R ₃₃ N—
_{Group, R 33 (R 34) NCO} (R 35) N- group, R ₃₁ -O-
Group, R ₃₁ —S— group, a halogen atom, or R ₃₁ (R ₃₃ ) N
- group (. R _31, R ₃₃ has the same meaning as R _31, R ₃₃ in the general formula (3) Further, R _34, R ₃₅ has the same meaning as R _33). When R ₈ is a regulating group, n ₁ represents an integer of 0 to 3, and when R ₉ is a regulating group, n ₁ represents an integer of ₁ to 3. Z
Represents a leaving group.

[0026]

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In the formula, one of R ₁₀ and R ₁₁ is a control group, and when R ₁₁ is a control group, R ₁₀ represents an alkyl group, an aryl group, or a heterocyclic group. When R ₁₀ is a regulatory group,
₁₁ is an alkyl group, an aryl group, a heterocyclic group, R ₃₁ -COR
₃₃ N-group, R ₃₁ -OCOR ₃₃ N-group, R ₃₁ -SO ₂ R ₃₃
N- _{group, R 33 (R 34) NCO} (R 35) N- group, R ₃₁ -O
— Group, R ₃₁ —S— group, halogen atom, or R ₃₁ (R ₃₃ )
Represents an N-group (R ₃₁ , R ₃₃ , R ₃₄ and R ₃₅ are represented by the general formula (5)
R ₃₁ , R ₃₃ , R ₃₄ and R ₃₅ have the same meanings). When R ₁₀ is a regulating group, n ₂ represents an integer of 0 to 3, and when R ₁₁ is a regulating group, n ₂ represents an integer of 1 to 3. Z represents a leaving group.

[0028]

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In the formula, one of R ₁₂ and R ₁₃ is a control group, and when R ₁₃ is a control group, R ₁₂ represents an alkyl group, an aryl group, or a heterocyclic group. When R ₁₂ is a regulatory group,
₁₃ is an alkyl group, an aryl group, a heterocyclic group, R ₃₁ -CON
H-group, R ₃₁ -OCONH- group, R ₃₁ -SO ₂ NH-
Group, R ₃₃ (R ₃₄ ) NCONH— group, R ₃₃ (R ₃₄ ) NSO
₂ NH- group, R ₃₁ -O- groups, R ₃₁ -S- group, a halogen atom, or R ₃₁ of the representative of R ₃₁ NH- group (R _31, R _33, R ₃₄ is formula (5), R ₃₃ , R ₃₄ ). R ₁₂
Is an adjusting group, n ₃ represents an integer of 0 to 4, and when R ₁₃ is an adjusting group, n ₃ represents an integer of 1 to 3. Z represents a leaving group.

[0030]

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In the formula, any one of R ₁₄ , R ₁₅ and R ₁₆ represents a controlling group. R ₁₄ and R ₁₅ each represent an electron-withdrawing group having a Hammett's substituent constant σp value of 0.2 or more and 1.0 or less when it is not a regulating group. R ₁₆ represents an alkyl group, an aryl group, or a heterocyclic group when it is not a regulating group. Z represents a leaving group.

Examples of the electron-withdrawing group having a Hammett's substituent constant σp of 0.2 to 1.0 include acyl, acyloxy, carbamoyl, aliphatic oxycarbonyl, aryloxycarbonyl, cyano, and nitro. Group, dialkylphosphono group, diarylphosphono group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group ,
Alkyl group substituted with at least two or more halogen atoms, alkoxy group substituted with at least two or more halogen atoms, aryloxy group substituted with at least two or more halogen atoms, at least two or more halogen atoms An alkylamino group substituted with at least 2
An alkylthio group substituted with one or more halogen atoms, σ
Examples thereof include an aryl group, a heterocyclic group, a chlorine atom, a bromine atom, an azo group, and a selenocyanate group substituted with another electron-withdrawing group having a p of 0.2 or more.

[0033]

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In the formula, one of R ₁₇ and R ₁₈ represents a controlling group. R ₁₇ and R ₁₈ each represent an alkyl group, an aryl group, a heterocyclic group, a cyano group, a carboxyl group, an acyl group, a carbamoyl group, an alkoxycarbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, or an acylamino group when not a regulating group. Group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, anilino group, ureido group, sulfamoylamino group, amino group, alkoxy group, silyloxy group, heterocyclic oxy group, alkylthio group, arylthio group, hetero Represents a ring thio group. Z represents a leaving group.

In the general formulas (1) to (10), the controlling group is a group having a size and a shape suitable for making the produced dye mobile. However, even with the same control group, the mobility of the dye to be formed depends on the type of the coupler mother nucleus, other substituents introduced into the coupler mother nucleus, and the color developing agent that forms the dye by coupling with the coupler. Affected by For this reason, the adjusting group to be used is not particularly limited except that it imparts the desired mobility to the dye. Preferred adjusting groups include an alkyl group having 1 to 20 carbon atoms, and 6 to 20 carbon atoms. And an aryl group having the following carbon atoms. Further, the controlling group is a dissociable group having a pka of 12 or less, such as a hydroxyl group, a carboxyl group,
It is also possible to contain a sulfo group, an aminosulfonyl group, or the like, and to make a non-migrating dye non-migrating when it does not contain them. Further, the control group has a dissociable group having a pka of 12 or less in the form of a precursor, and generates a dissociable group having a pka of 12 or less by a nucleophilic substitution substitution reaction or the like during amplification and development processing. When the dye does not contain a non-migrating dye, the dye can be made mobile.

These control groups may have a linking group for binding the control group to the coupler nucleus. Examples of such a linking group include -O-, -S-, -CO
-, -COO-, -NR-, -CONR-, -NRCO
_{-, - SO 2 NR -,} - NRSO 2 -, - NRCONR-
(Where R is a hydrogen atom, an alkyl group, or an aryl group) and the like. In addition, when having a linking group,
The term "controlling group" used in the description of the general formulas (1) to (10) also includes a group obtained by combining a linking group and a controlling group.

In the general formulas (1) to (10), the term "leaving group" means a group capable of leaving from the coupler nucleus upon the coupling reaction between the coupler and the oxidized color developing agent. The leaving group represented by Z may be any of conventionally known coupling-off groups. Preferred Z is a nitrogen-containing heterocyclic group (for example, 1) bonded to the coupling position with a nitrogen atom. -Pyrazolyl, 1-imidazolyl, 1,2,4-triazol-2-yl, 1,2,3
-Triazol-1-yl, benzotriazolyl, benzimidazolyl, imidazolidine-2,4-dione-3
-Yl, oxazolidine-2,4-dione-3-yl,
1,2,4-triazolidine-3,5-dione-4-yne, 2-imidazolinone-1-yl, 1-indazolyl), an aryloxy group (preferably a phenoxy group), an arylthio group (preferably phenylthio) A heterocyclic oxy group (e.g., 2-pyridyloxy, 2
-Pyrazolyloxy), a heterocyclic thio group (for example, tetrazolylthio, 1,3,4-thiadiazolylthio, 1,3,
4-oxadiazolylthio, 1,3,4-triazolylthio, benzimidazolylthio, benzothiazolylthio), an aryloxy group (for example, benzoyloxy),
Examples include a carbamoyloxy group (eg, dodecylcarbamoyloxy), or an alkylthio group (eg, tetradecylthio). These Zs may further have a substituent.

In the description of the above general formulas (1) to (10), the alkyl group means a group having 1 to 15 carbon atoms, preferably 1 to 1 carbon atoms.
0 is a saturated or unsaturated, linear or cyclic, linear or branched, substituted or unsubstituted alkyl group, and typical examples are methyl, cyclopropyl, isopropyl, n-butyl,
t-butyl, i-butyl, t-amyl, n-hexyl,
Cyclohexyl, 2-ethylhexyl, n-octyl,
1,1,3,3-tetramethylbutyl, n-decyl, n
-Dodecyl, n-hexadecyl, n-octadecyl and the like. The aryl group has 6 to 1 carbon atoms.
Zero, preferably substituted or unsubstituted phenyl, or substituted or unsubstituted naphthyl groups can be mentioned.
The heterocyclic group has 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms.
Examples of the hetero atom include a substituted or unsubstituted 3- or 8-membered substituted or unsubstituted heterocyclic group selected from a nitrogen atom, an oxygen atom and a sulfur atom. Representative examples of such heterocyclic groups include 2-pyridyl, 2-benzoxazolyl, 2-imidazolyl, 2-benzimidazolyl, 1-indolyl, 1,3,4-thiadiazole-2.
-Yl, 1,2,4-triazol-2-yl or 1-
And substituents such as indolinyl.

The couplers represented by the general formulas (1) to (10) are diffusion-resistant couplers, and the diffusion-resistant group is included in the leaving group Z. The diffusion-resistant coupler refers to a coupler having a group (diffusion-resistant group) in the molecule that increases the molecular weight sufficiently to be immobilized in the layer to which the coupler molecule is added. As the diffusion-resistant group, an alkyl group having 8 to 40 carbon atoms, preferably 10 to 20 carbon atoms, or an aryl group having at least one substituent having 4 to 20 carbon atoms is generally used. These non-diffusible groups are bonded at substitutable positions of the leaving group represented by Z, and may have a plurality of groups.

Hereinafter, specific examples of the diffusion-resistant coupler for forming a mobile dye, which are preferably used in the present invention, are shown, but the present invention is not limited thereto.

[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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Among the couplers represented by the above general formulas (1) to (10), particularly the general formulas (3), (4), (5),
The couplers represented by (8) and (9) have a particularly large effect of improving the color reproducibility deterioration due to poor desilvering at the time of the bleaching and fixing processing steps after the amplification development processing. This is presumably because the structure of the nearby coupler molecule has some influence on the reaction between the developed silver and the bleaching agent or the reaction between the silver halide and the fixing agent.

Next, the amplification and development processing will be described. In the present invention, the amplification development processing means that a latent image generated by exposure of a photosensitive material is developed with a color or black-and-white developer to form developed silver, and an image is formed using a chemical reaction using the developed silver as a catalyst. It is defined as a method of forming or releasing a dye, for example, a method of forming an image dye by a coupling reaction of a coupler with an oxidized developing agent generated by a redox reaction between a developing agent and an oxidizing agent using a developed silver catalyst as a catalyst, and the like. .

Examples of the oxidizing agent include compounds that give hydrogen peroxide, such as hydrogen peroxide and an addition compound of hydrogen peroxide, peroxo compounds such as peroxoborate and peroxocarbonate, and cobalt (III) such as cobalt hexaammine complex.
Complexes, halogenous acids such as chlorous acid, periodic acid and the like can be used. Above all, a method using hydrogen peroxide as an oxidizing agent is advantageous because the effect of amplification is high and the load on the environment is reduced.

In the amplification development processing according to the present invention, a combination of an aromatic primary amine developing agent and hydrogen peroxide is preferably used, and as the aromatic primary amine developing agent,
N, N-diethyl-p-phenylenediamine, 2-amino-5-diethylaminotoluene, 2-amino-5
(N-ethyl-N-laurylamino) toluene, 4-
(N-ethyl-N- (β-hydroxyethyl) amino)
Aniline, 2-methyl-4- (N-ethyl-N- (β-
Hydroxyethyl) amino) aniline, 4-amino-3
-Methyl-N-ethyl-N- (β- (methanesulfonamido) ethyl) -aniline, N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide,
N, N-dimethyl-p-phenylenediamine, 4-amino-3-methyl-N-ethyl-N-methoxyethylaniline, 4-amino-3-methyl-N-ethyl-N- (β
-Ethoxyethyl) aniline, 4-amino-3-methyl-N-ethyl-N- (γ-hydroxypropyl) aniline and the like.

In the present invention, it is possible to supply a processing solution containing the above-mentioned color developing agent and an oxidizing agent for amplification development to a photographic material in combination, and it is also possible to supply a processing solution containing a developing agent and an oxidizing agent for amplification development. A liquid containing the agent is divided into a plurality and prepared,
It is also possible to supply to a photosensitive material.

The amplification and development method according to the present invention is described in, for example, JP-A Nos. 52-13335 and 55-127555.
As described in JP-A-61-77851 and the like, a developing agent and an oxidizing agent are present in the same processing bath (developing / amplifying solution) to produce developed silver as a catalyst and the subsequent amplification development processing. A method performed in the same bath, JP-A-5-216192,
As described in JP-A-5-346647 and the like, a method in which a developing bath containing a developing agent and an amplification bath containing an oxidizing agent are separated, silver is formed in the developing bath, and the developing agent is brought into the amplification bath and amplified and developed. Or JP-A-61-88259,
As described in Japanese Patent Application Laid-Open No. 7-077788, a method of forming a developed silver by processing in a developing bath containing a developing agent, followed by amplifying and developing in a processing bath containing a developing agent and an oxidizing agent is exemplified. Further, as a processing method without using a processing bath, for example, a method of spraying a developing solution or an amplifying solution onto a silver halide photosensitive material in a mist as described in JP-A-61-80150 can be used.

When the developing bath and the amplification bath are separated, the preferred amount of the developing agent in the developer is 0.2 to 10 g / l, particularly preferably 1 to 5 g / l. The amount of hydrogen peroxide (30% solution) in the amplification solution is 0.1 to 100 ml / l.

When the treatment is carried out in a single bath including the developing bath and the amplification bath, the preferred amount of the developing agent in the developing / amplifying solution is 0.5 to
15 g / l, more preferably 1 to 7 g / l, and the preferred amount of hydrogen peroxide (30% solution) is 0.1 to 30 ml
/ L, more preferably 1 to 5 ml / l.

In the present invention, the above-mentioned developer, amplifying solution,
The developing / amplifying solution can be used in an arbitrary pH range, but preferably from pH 9.0 to 12.5, more preferably from pH 9.5 to 11.5 from the viewpoint of rapid processing.

The processing temperature of the amplification development according to the present invention is 20
The temperature is preferably at least 60 ° C and not more than 60 ° C. The higher the temperature, the shorter the processing time is possible, which is preferable. However, from the viewpoint of the stability of the processing solution, it is preferable that the temperature is not too high.

The amplification development time varies depending on the processing temperature, the activity of the processing solution and the like, but is preferably within 180 seconds, more preferably within 90 seconds in the present invention.

To the developing solution, the amplifying solution, and the developing / amplifying solution, a known developer component compound can be added in addition to the color developing agent and the oxidizing agent. Usually, a development inhibitor such as a pH buffer, a chloride ion, and benzotriazole, a preservative, and a chelating agent are used.

As the pH buffer, known buffers can be used. Among them, a buffer composed of a combination of potassium carbonate (or sodium) / potassium hydrogencarbonate (or sodium) can reduce the cost, and Highly environmentally friendly and highly preferred.

Next, couplers that can be used together with the light-sensitive material according to the present invention will be described.

In the light-sensitive material according to the present invention, in addition to the above described diffusion-resistant coupler which forms a mobile dye by a coupling reaction with the oxidized form of the color developing agent, a coupler with the oxidized form of the color developing agent can be used. A non-diffusible coupler which forms a non-migrating dye by a ring reaction can be used in combination.

Couplers that can be used together include:
340 by coupling reaction with oxidized color developing agent
Any compound capable of forming a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than nm can be used.
Yellow dye-forming coupler having a spectral absorption maximum wavelength at 500 nm, magenta dye-forming coupler having a spectral absorption maximum wavelength at 500 to 600 nm, wavelength range 600
Typical are those known as cyan dye-forming couplers having a spectral absorption maximum wavelength at 〜750 nm.

In the light-sensitive material of the present invention, the cyan coupler preferably used in combination is described in JP-A-4-11415.
The general formula (C-I) described in the lower left column of page 4, No. 5, page 5,
The coupler represented by (C-II) can be mentioned.

The magenta coupler preferably used in combination in the light-sensitive material of the present invention is described in JP-A-4-11415.
General formula (MI) described in the upper right column on page 4 of JP-A No. 4
The coupler represented by (M-II) can be mentioned.
More preferred among the above magenta couplers are the couplers represented by the general formula (MI) described in the upper right column on page 4 of the publication, and among them, the RM of the above general formula (MI)
Is a tertiary alkyl group, which is excellent in light resistance and particularly preferred.

The yellow coupler preferably used in combination in the light-sensitive material according to the present invention is described in JP-A-4-114.
General formula (Y-I) described in the upper right column on page 3 of JP-A-154-154
And a coupler represented by the following formula: Of these, couplers in which RY1 in the general formula [Y-1] is an alkoxy group or couplers represented by the general formula [I] described in JP-A-6-67388 can reproduce yellow having a preferable color tone, and thus are preferable. Further, the most preferred compound is described in JP-A No. 4-8.
It is a compound represented by the general formula [Y-1] described in page 1 of JP 1847 and pages 11 to 17 of the same.

The ratio of the diffusion-resistant coupler forming a mobile dye to the diffusion-resistant coupler forming a non-migrating dye contained in one color image forming layer is not particularly limited. It is preferable that the dye-forming coupler is contained in a molar ratio of 15% or more, particularly preferably 30%.
% Or more, the occurrence of poor desilvering in the color image forming layer is greatly improved, which is preferable.

When the oil-in-water type emulsion dispersion method is used to add the couplers and other organic compounds used in the light-sensitive material according to the present invention, the water-insoluble high-boiling organic solvent having a boiling point of 150 ° C. or higher is usually used. If necessary, a low boiling point and / or water-soluble organic solvent is used in combination to dissolve, and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. The high-boiling organic solvent that can be used for dissolving and dispersing the dye-providing substance has a dielectric constant of 3.5 to 3.5.
It is preferably 7.0. Further, two or more kinds of high-boiling organic solvents can be used in combination.

In place of the method using a high-boiling organic solvent or in combination with a high-boiling organic solvent, a water-insoluble and organic solvent-soluble polymer compound may be added, if necessary, to a low-boiling and / or water-soluble organic solvent. In a hydrophilic binder such as an aqueous gelatin solution by using a surfactant and emulsifying and dispersing by various dispersing means.

As a compound preferable as a surfactant used for dispersing a photographic additive or adjusting the surface tension at the time of coating, a hydrophobic group having 8 to 30 carbon atoms and a sulfonic acid group or a salt thereof in one molecule are preferable. Containing. Also, a surfactant in which a fluorine atom is substituted for an alkyl group is preferably used. These dispersions are usually added to a coating solution containing a silver halide emulsion, and the time until the addition to the coating solution after the dispersion and the time from the addition to the coating solution after the addition are preferably 10 hours each. Preferably within 3 hours, more preferably within 20 minutes.

The coupler includes light of the formed dye image,
In order to prevent discoloration due to heat, humidity and the like, it is preferable to use a discoloration inhibitor in combination. Particularly preferred compounds include compounds represented by the general formula I described on page 3 of JP-A-2-66541.
Phenyl ether compounds represented by II, JP-A-3-1
A phenolic compound represented by the general formula IIIB described in JP-A-74150, an amine-based compound represented by the general formula A described in JP-A-64-90445, and JP-A-62-182.
Metal complexes represented by general formulas XII, XIII, XIV and XV described in JP-A-741 are particularly preferable for magenta dyes. Further, compounds represented by the general formula I 'described in JP-A-1-19649 and compounds represented by the general formula II described in JP-A-5-11417 are particularly preferred for yellow and cyan dyes.

For the purpose of shifting the absorption wavelength of the coloring dye, compound (d-11) described in the lower left column of page 9 of JP-A-4-114154 and compound (A'-1) described in the lower left column of page 10 of JP-A-4-114154 are disclosed. And the like. In addition, the fluorescent dye releasing compounds described in U.S. Pat. No. 4,774,187 can also be used.

In the light-sensitive material according to the present invention, a compound which reacts with an oxidized developing agent is added to a layer between the light-sensitive layers to prevent color turbidity, or added to a silver halide emulsion layer. It is preferable to improve fog and the like. The compound for this purpose is preferably a hydroquinone derivative, more preferably a dialkylhydroquinone such as 2,5-di-t-octylhydroquinone.

It is preferable to add an ultraviolet absorber to the light-sensitive material according to the present invention to prevent static fog or improve the light fastness of a dye image. Preferable ultraviolet absorbers include benzotriazoles. Particularly preferred compounds are compounds represented by the formula III-3 described in JP-A-1-250944, and JP-A-64-6664.
6, a compound represented by the general formula III,
UV-1L to UV-27 described in 3-187240
L, compounds represented by the general formula I described in JP-A-4-1633, and compounds represented by the general formulas (I) and (II) described in JP-A-5-165144.

The composition of the silver halide photographic emulsion according to the present invention has an arbitrary halogen composition such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide and silver chloroiodide. It may be something. Among them, a high silver chloride emulsion containing 80 mol% or more of silver chloride is preferable because the effect of the present invention can be obtained without lowering the maximum density due to suppression of amplification and development, and more preferably 90 mol% or more. 95-9
Silver halide emulsions containing 9.9 mol% of silver chloride are particularly preferred. When a silver halide emulsion having a high silver chloride content is used, a clear printed image free of dullness can be obtained with almost no poor desilvering even if the bleaching and fixing processing times are shortened.

As the silver halide emulsion according to the present invention, a silver halide emulsion having a portion containing silver bromide at a high concentration can also be preferably used. In this case, the portion containing a high concentration of silver bromide may be a so-called core / shell emulsion in which a complete layer is formed, or a region in which the complete layer is not formed and the composition is merely partially present. In this case, what is called an epitaxy junction may be used. Also,
The composition may vary continuously or discontinuously. It is particularly preferable that the portion where silver bromide is present at a high concentration is present at the top of silver halide grains.

For obtaining the silver halide emulsion according to the present invention, it is advantageous to include heavy metal ions. Heavy metal ions that can be used for such purposes include iron,
Iridium, platinum, palladium, nickel, rhodium,
Examples include Group 8 to 10 metals such as osmium, ruthenium, and cobalt; Group 12 transition metals such as cadmium, zinc, and mercury; and ions of lead, rhenium, molybdenum, tungsten, gallium, and chromium. Among them, metal ions of iron, iridium, platinum, ruthenium, gallium and osmium are preferred.

These metal ions can be added to the silver halide emulsion in the form of a salt or a complex salt.

When the heavy metal ion forms a complex, the ligand may be a cyanide ion, thiocyanate ion, isothiocyanate ion, cyanate ion, or the like.
Examples include chloride ion, bromide ion, iodide ion, carbonyl, ammonia and the like. Among them, cyanide ion, thiocyanate ion, isothiocyanate ion, chloride ion, bromide ion and the like are preferable.

In order for the silver halide emulsion according to the present invention to contain heavy metal ions, the heavy metal compound is physically added before, during, and after the formation of silver halide grains. What is necessary is just to add in arbitrary places of each process during ripening. In order to obtain a silver halide emulsion satisfying the above conditions, a heavy metal compound can be dissolved together with a halide salt and added continuously over the whole or a part of the grain forming step.

The amount of the heavy metal ion added to the silver halide emulsion is 1 × 10 ^-9 per mol of silver halide.
Mol or more and 1 × 10 ^-2 mol or less, particularly preferably 1 × 10 ⁻² mol or less.
It is preferably at least 10 ^-8 mol and not more than 5 10 ^-5 mol.

The silver halide grains according to the present invention may have any shape. One preferred example is
It is a cube having a {100} plane as a crystal surface. U.S. Pat. Nos. 4,183,756 and 4,225,6
No. 66, JP-A-55-26589, JP-B-55-42
No. 737 and The Journal of Photographic Science (J. Photogr. Sci.) 2
1, 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.

As the silver halide grains according to the present invention, grains having a single shape are preferably used, but it is also preferable to add two or more kinds of monodispersed silver halide emulsions to the same layer.

The particle size of the silver halide grains used in the present invention is not particularly limited, but is preferably 0.1 to 1.10 in consideration of other photographic properties such as rapid processing and sensitivity.
It is 2 μm, more preferably in the range of 0.2 to 1.0 μm.

The size of silver halide grains can be measured by various methods generally used in the art. A typical method is described in Loveland's “Particle Size Analysis Method” (ASTM Symposium on Right Microscopy, pp. 94-122, 195).
5) Or "Theory of Photographic Process Third Edition" (Mies and James, Chapter 2, published by Macmillan, 196)
The method described in 6) can be mentioned.

As the apparatus and method for preparing a silver halide emulsion, various methods known in the art can be used.

The silver halide emulsion according to the present invention may be 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 have been made. The method of producing the seed particles and the method of growing them may be the same or different.

The form in which the soluble silver salt and the soluble halide salt are reacted may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, a combination thereof, and the like. Is preferred. Further, as one type of the double jet method, a pAg controlled double jet method described in JP-A-54-48521 can be used.

Also, JP-A-57-92523 and JP-A-57-92523.
No.-92524, etc., a device for supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide salt from an addition device disposed in a reaction mother liquor, and a water-soluble silver described in DE-A-2,921,164. A device for continuously adding a salt and an aqueous solution of a water-soluble halide salt while changing the concentration,
No. 501776, etc., a reaction mother liquor may be taken out of a reactor and concentrated by an ultrafiltration method to form grains while keeping the distance between silver halide grains constant.

If necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound or a compound such as 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 according to the present invention include:
In order to control the gradation balance, a so-called tabular silver halide is also preferably used. As tabular grains containing silver chloride at a high concentration, grains having a {111} major plane and grains having a {100} major plane are known. Particles having a flat surface are particularly preferably used.

The silver halide emulsion according to the present invention can be used in combination with a sensitization method using a gold compound and a sensitization method using a chalcogen sensitizer.

As the chalcogen sensitizer applied to the silver halide emulsion according to the present invention, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer, etc. can be used, but a sulfur sensitizer is preferable.

The silver halide emulsion according to the present invention contains a known fog for the purpose of preventing fog generated during the preparation of a light-sensitive material, reducing performance fluctuation during storage, and preventing fog generated during development. Inhibitors and stabilizers can be used. Preferred examples of the compound that can be used for such a purpose include a compound represented by the general formula (II) described in the lower section of page 7 of JP-A-2-14636. These compounds are added according to the purpose in a step of preparing a silver halide emulsion, a step of chemical sensitization, at the end of the step of chemical sensitization, a step of preparing a coating solution and the like.

In the light-sensitive material according to the present invention, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. For this purpose, any of the known compounds can be used. In particular, dyes having absorption in the visible region include those described in JP-A-3-25184.
The dyes of AI-1 to 11 described in JP-A No. 308, page 308 and the dyes described in JP-A-6-3770 are preferably used. As the infrared absorbing dye, JP-A 1-28075 is used.
No. 0, page 2, lower left column, formulas (I) and (I)
The compounds represented by I) and (III) have preferable spectral characteristics, and do not affect the photographic characteristics of the silver halide photographic emulsion.
It is also preferable because there is no contamination due to residual color.

In order to improve the sharpness, the amount of these dyes added is 680 nm for an unprocessed sample of a light-sensitive material.
Is more preferably 0.7 or more, and even more preferably 0.8 or more.

It is preferable to add a fluorescent whitening agent to the light-sensitive material according to the present invention because whiteness can be improved. Preferred examples of the compound include a compound represented by the general formula II described in JP-A-2-232652.

When the light-sensitive material according to the present invention is used as a color photographic light-sensitive material, it is combined with a yellow dye-donating substance, a magenta dye-donating substance and a cyan dye-donating substance and spectrally sensitized to a specific region in a wavelength region of 400 to 900 nm. And a layer containing a silver halide emulsion. The silver halide emulsion contains one kind or a combination of two or more kinds of sensitizing dyes.

As the spectral sensitizing dye for use in the silver halide emulsion according to the present invention, any known compounds can be used.
BS-1 to 8 described in page 28 of JP 51840 can be preferably used alone or in combination. Examples of the green photosensitive sensitizing dye include G
S-1 to S-5 are preferably used. RS-1 to 8 described on page 29 of the same publication are preferably used as red-sensitive sensitizing dyes. In the case of performing image exposure with infrared light using a semiconductor laser or the like, it is necessary to use an infrared-sensitive sensitizing dye. The dyes of IRS-1 to 11 described in JP-A No. 6-8 are preferably used. These infrared, red, green, and blue photosensitive sensitizing dyes may be added to supersensitizers SS-1 to SS-9 described in JP-A-4-285950, pp. 8-9, and JP-A-5-66515. Issue 1
It is preferable to use the compounds S-1 to S-17 described on pages 5 to 17 in combination.

The sensitizing dye may be added at any time from the formation of silver halide grains to the end of chemical sensitization.

The sensitizing dye may be added by dissolving it in a water-miscible organic solvent such as methanol, ethanol, fluorinated alcohol, acetone, dimethylformamide or the like or water, or adding it as a solid dispersion. It may be added.

It is advantageous to use gelatin as a binder in the light-sensitive material according to the present invention. If necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, proteins other than gelatin, A hydrophilic colloid such as a sugar derivative, a cellulose derivative, or a synthetic hydrophilic polymer such as a homopolymer or a copolymer can also be used.

As the hardener of these binders, it is preferable to use a vinyl sulfone hardener or a chlorotriazine hardener alone or in combination.
It is preferable to use the compounds described in JP-A Nos. 054 and 61-245153. Further, it is preferable to add a preservative and an antifungal agent as described in JP-A-3-157646 in the colloid layer in order to prevent the growth of mold and bacteria which adversely affect the photographic performance and image storability. Further, in order to improve the physical properties of the surface of the light-sensitive material or the processed sample, a protective layer is disclosed in
It is preferable to add a slip agent or a matting agent described in JP-A-118543 and JP-A-2-73250.

As the support used for the light-sensitive material according to the present invention, any material may be used, such as paper coated with polyethylene or polyethylene terephthalate, a paper support made of natural pulp or synthetic pulp, a vinyl chloride sheet, For example, polypropylene, polyethylene terephthalate support, baryta paper, etc. which may contain a white pigment can be used. Among them, a support having a water-resistant resin coating layer on both sides of the base paper is preferable. As the water-resistant resin, polyethylene, polyethylene terephthalate or a copolymer thereof is preferable.

As the white pigment used for the support, inorganic and / or organic white pigments can be used, and preferably, inorganic white pigments are used.

It is more preferable that the value of the center plane average roughness (SRa) of the support is 0.15 μm or less, more preferably 0.12 μm or less, because the effect of good gloss can be obtained.
In addition, trace amounts of ultramarine, oil-soluble dyes, etc. to adjust the spectral reflection density balance of the white background after treatment in the white pigment-containing water-resistant resin of the reflective support or in the applied hydrophilic colloid layer to improve whiteness It is preferable to add a bluing agent or a reddish agent.

The 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 undercoating (adhesion, antistatic property on the support surface, It may be applied via one or more undercoat layers for improving dimensional stability, friction resistance, hardness, antihalation property, frictional properties and / or other properties.

At the time of coating the light-sensitive material according to the present invention, 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.

In order to form a photographic image using the photosensitive material according to the present invention, the image recorded on the negative may be optically formed on the photosensitive material to be printed and printed. After the image is once converted to digital information, the image may be formed on a CRT (cathode ray tube), and this image may be formed on a photosensitive material to be printed and printed. Printing may be performed by scanning while changing the intensity of the laser beam.

The image forming method of the present invention is particularly preferably applied to a photosensitive material for forming an image for direct viewing. For example, color paper, color reversal paper, a photosensitive material for directly forming a positive image, a photosensitive material for a display, and a photosensitive material for a color proof can be used. It is particularly preferable to apply the invention to a photosensitive material having a reflective support.

In the image forming method of the present invention, after color development, bleaching and fixing may be performed as required. The bleaching process may be performed simultaneously with the fixing process. After the fixing process, a water washing process is usually performed. Further, as an alternative to the water washing treatment, a stabilization treatment may be performed.

The image forming method of the present invention is particularly useful when the bleaching treatment is carried out with a bleaching treatment solution containing hydrogen peroxide or persulfate, because the effect of improving the desilvering defect is large.

The processing apparatus used in the image forming method of the present invention may be a roller transport type in which the photosensitive material is conveyed with rollers interposed in a processing bath. An endless belt method may be used, but a processing bath is formed in a slit shape, and a processing method for supplying a processing liquid to the processing bath and transporting the photosensitive material, and a spray method for spraying the processing liquid,
A web method by contact with a carrier impregnated with the processing solution,
A method using a viscous treatment liquid can also be used.

[0120]

Next, the present invention will be described based on examples, but embodiments of the present invention are not limited to these examples.

Example 1 (Preparation of Blue-Sensitive Silver Halide Emulsion (Em-B1))
In 1 liter of a 2% aqueous gelatin solution kept at 0 ° C., the following (solution A1) and (solution B1) were pAg = 7.3, pH =
The solution was added simultaneously while controlling to 3.0, and the following (solution C1) and (solution D1) were simultaneously added while controlling to pAg = 8.0 and pH = 5.5. At this time, the control of pAg is described in
The control of pH was performed using sulfuric acid or an aqueous sodium hydroxide solution.

(A1 solution) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to 200 ml (Solution B1) Silver nitrate 10 g Water was added to 200 ml (Solution C1) Sodium chloride 102.7 g Potassium hexachloroiridium (IV) ate 4 × 10 ⁻⁸ mol Potassium hexacyanoferrate (II) 2 × 10 ⁻⁵ mol Potassium bromide 1.0 g Add water 600 ml (Solution D1) Silver nitrate 300 g Add water 600 ml after completion of addition, Kao Atlas Demol After desalting was performed using a 5% aqueous solution of N and a 20% aqueous solution of magnesium sulfate, the mixture was mixed with an aqueous gelatin solution to give an average particle size of 0.71 μm.
m, coefficient of variation of particle size distribution 0.07, silver chloride content 99.
A 5 mol% monodispersed cubic emulsion EMP-1A was obtained. Next, in the preparation of EMP-1A, the average particle size was 0.64 μm and the particle size was the same except that the addition time of (A1 solution) and (B1 solution) and the addition time of (C1 solution) and (D1 solution) were changed. A monodisperse cubic emulsion EMP-1B having a distribution variation coefficient of 0.07 and a silver chloride content of 99.5 mol% was obtained.

The above-mentioned EMP-1A was optimally subjected to chemical sensitization at 60 ° C. using the following compounds. EMP-1
Similarly, after optimally chemical sensitizing B, the sensitized EMP-1A and EMP-1B were mixed at a silver amount of 1: 1 to obtain a blue-sensitive silver halide emulsion (Em-B1). I got

Sodium thiosulfate 0.8 mg / mol AgX Chloroauric acid 0.5 mg / mol AgX Stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX Stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent STAB-3 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-2 1 × 10 ⁻⁴ mol / mol AgX STAB-1: 1- ( 3-acetamidophenyl) -5
-Mercaptotetrazole STAB-2: 1-phenyl-5-mercaptotetrazole STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole

[0125]

Embedded image

(Preparation of silver halide photographic light-sensitive material (101)) High-density polyethylene was laminated on both sides of paper pulp having a basis weight of 180 g / m ² to prepare a paper support. However, on the side on which the emulsion layer was applied, a molten polyethylene containing anatase-type titanium oxide having a surface treatment dispersed therein at a content of 15% by weight was laminated. After subjecting this reflective support to a corona discharge treatment, a gelatin undercoat layer was provided, and each layer having the following constitution was further applied thereon to prepare a silver halide photographic material (101). The coating solution was prepared as described below.

First layer coating solution: 12 mmol of magenta coupler (M-1), 6.0 g of dye image stabilizer (ST-3), 5.1 g of (ST-4),
60 ml of ethyl acetate was added to and dissolved in 3.9 g of a high boiling organic solvent (DBP) and 3.9 g of a high boiling organic solvent (DIDP), and this solution was dissolved in 10% gelatin containing 7 ml of a 20% surfactant (SU-1). A 220-ml aqueous solution was emulsified and dispersed using an ultrasonic homogenizer to prepare a magenta coupler dispersion. This dispersion was mixed with the blue-sensitive silver halide emulsion prepared under the above conditions to prepare a first layer coating solution.

The coating solution for the second layer was also prepared so as to have the following coating amount.

Further, (H-1), (H-2)
Was added. Surfactants (SU-
2) and (SU-3) were added to adjust the surface tension. Further, (F-1) was added to each layer so that the total amount became 0.04 g / m ² .

Layer composition Addition amount (/ m ² ) Second layer (protective layer) Gelatin 2.50 g First layer (blue-sensitive layer) Gelatin 1.20 g Blue-sensitive emulsion (Em-B1) 0.04 g Magenta Coupler (M-1) 0.45 mmol Dye image stabilizer (ST-3) 0.14 g Dye image stabilizer (ST-4) 0.12 g DBP 0.09 g DIDP 0.09 g Support Polyethylene laminated paper SU- 1: sodium tri-i-propylnaphthalenesulfonate SU-2: di (2-ethylhexyl) sulfosuccinate sodium salt SU-3: di (2,2,3,3,4,4, sulfosuccinate)
5,5-octafluoropentyl) · sodium salt H-1: tetrakis (vinylsulfonylmethyl) methane H-2: 2,4-dichloro-6-hydroxy-s-triazine · sodium DBP: dibutyl phthalate DIDP: diisodecyl phthalate The values for silver halide emulsions were expressed in terms of the amount of silver.

[0131]

Embedded image

(Silver halide photographic light-sensitive material (102))
(Preparation of (119)) In the preparation of the photosensitive material (101), the photosensitive materials (102) to (11) were prepared in the same manner except that the magenta coupler (M-1) was changed as shown in Table 1.
9) was created.

[0133]

Embedded image

The light-sensitive material (10
For each of 1) to (119), 0.5% with white light.
Prepare three sets of samples exposed to light wedges in seconds, and perform the following processing steps A to
Each treatment was performed with C. For each sample after processing
The reflection density was measured using a reflection densitometer PDA-65 and PDA-65IR (both manufactured by Konica Corporation). For the photosensitive materials (101) to (106) using the magenta coupler, the value of the reflection density by infrared light (wavelength 900 nm) at the point where the reflection density by green light is 1.5 was measured, and ΔAB ((processing The value of step A)-(the value of processing step B)) and ΔAC ((the value of processing step A)-(the value of processing step C)) were determined and used as a scale for evaluating desilvering properties, and are shown in Table 1. . Photosensitive material (107) using yellow coupler
In (110), the reflection density by blue light is 1.5
Measure the value of the reflection density due to infrared light at the point where
Similarly, ΔAB and ΔAC were obtained. In the photosensitive materials (111) to (119) using the cyan coupler, the value of the reflection density by infrared light at the point where the reflection density by red light becomes 1.5 was measured, and ΔAB and ΔAC were similarly calculated.
I asked. Since the bleaching / fixing time is shorter in the processing steps B and C than in the processing step A, the desilvering property tends to be deteriorated.
As the value shown in Table 1 as an evaluation scale of desilvering property is closer to 0,
This indicates that a vivid image without dullness can be reproduced without degrading the desilvering property even when the bleaching / fixing time is shortened. Also, the more negative this value is, the more bleaching and
When the fixing time is shortened, the desilvering property is deteriorated, which means that it is difficult to reproduce a clear image without dullness.

Processing Step A Processing Temperature Amplification Developer (CDA-1) 33.0 ± 0.5 ° C. 45 seconds Bleaching / Fixing Solution (BF-1) 33.0 ± 0.5 ° C. 45 seconds Stable Chemical solution 30-34 ° C 60 seconds Drying 60-80 ° C 30 seconds Processing step B Same as processing step A except that the bleaching / fixing time was 8 seconds Processing step C Except that the bleaching / fixing time was 5 seconds Shows the composition of the treatment liquid as in the treatment step A below.

Amplification developer (CDA-1) Pure water 800 ml Potassium bromide 0.001 g Potassium chloride 0.35 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 4 0.0g N, N-diethylhydroxylamine 4.7g Diethylenetriaminepentaacetic acid sodium salt 2.0g 1-hydroxyethylidene-1,1'-diphosphonic acid 0.35g Fluorescent whitening agent (4,4'-diaminostilbene disulfonic acid derivative 2.0 g Potassium carbonate 20 g Hydrogen peroxide solution (5.99%) 25.0 ml Add water to make the total volume 1 liter, and adjust to pH = 10.3 with sulfuric acid or potassium hydroxide.

Bleaching-fixing solution (BF-1) Pure water 700 ml Diethylenetriaminepentaacetate ammonium ferric dihydrate 35 g Diethylenetriaminepentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml 2-amino-5-mercapto-1,3,4 -Thiadiazole 2.0 g Ammonium sulfite (40% aqueous solution) 27.5 ml Add water to make the total volume 1 liter, and adjust the pH to 5.0 with potassium carbonate or glacial acetic acid.

Stabilizing solution Pure water 800 ml o-phenylphenol 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 0.0 g fluorescent whitening agent (Tinopearl SFP) 2.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g bismuth chloride (45% aqueous solution) 0.65 g magnesium sulfate heptahydrate 0.2 g PVP (polyvinylpyrrolidone) 1.0 g ammonia water (25% aqueous solution of ammonium hydroxide) 2.5 g nitrilotriacetic acid / trisodium salt 1.5 g Water was added to make the total volume 1 liter, and the pH was adjusted to 7.5 with sulfuric acid or ammonia water. .

[0139]

[Table 1]

From the results shown in Table 1, it can be seen that the light-sensitive material (10
3) to (106), (108) to (110), (11)
3) to (119), bleaching after amplification development processing
Even when the fixing time is shortened, the occurrence of poor desilvering is small, which is preferable. In particular, photosensitive materials (10
5), (106), (113), (114), (11)
7) and (118) show that the degree of poor desilvering is small, and it is understood that these couplers are particularly preferably used in the present invention. The closer the values of ΔAB and ΔAC were to zero, the smaller the occurrence of dullness in the maximum density portion, and a better color image could be obtained.

Example 2 (Preparation of photosensitive materials (201) to (215)) In preparing photosensitive materials (101), (105) and (108) of Example 1, the amounts of silver halide were as shown in Table 2. The photosensitive materials (201) to (215) were prepared in the same manner except that the above conditions were changed.

The light-sensitive material (20
For each of 1) to (215), 0.5% with white light.
Prepare three sets of samples that have been exposed to light wedges in seconds.
F. The same concentration measurement as in Example 1 was performed on each of the samples after the treatment, and the same evaluation as in Example 1 was performed based on the treatment step D, and ΔDE ((treatment step D
) − (Value of processing step E)), ΔDF ((processing step D)
) − (Value of treatment step F)). The results are shown in Table 2.

Processing Step D Processing Temperature Time Amplification Developer (CDA-1) 33.0 ± 0.5 ° C. 45 seconds Bleach (BL-1) 25.0 ± 0.5 ° C. 20 seconds Fixer ( FIX-1) 25.0 ± 0.5 ° C. 20 seconds Stabilizing solution 30-34 ° C. 60 seconds Drying 60-80 ° C. 30 seconds Processing step E Same as processing step D except that the bleaching processing time was 10 seconds. Step F The composition of the processing solution is shown below in the same manner as in the processing step D, except that the bleaching time is 5 seconds and the fixing time is 5 seconds.

Bleaching solution (BL-1) Pure water 600 ml Hydrogen peroxide solution (5.99%) 250 ml Potassium hydrogen carbonate 25 g Potassium chloride 3.5 g Water was added to make a total volume of 1 liter, and the pH was adjusted with potassium hydroxide or sulfuric acid. = 8.2.

Fixing solution (FIX-1) Pure water 800 ml Sodium sulfite 100 g Potassium hydrogen carbonate 25 g Water was added to make the total volume 1 liter, and the pH was adjusted to 8.5 with sodium hydroxide or sulfuric acid.

[0146]

[Table 2]

From the results shown in Table 2, the photosensitive materials (201) to (201)
(203) means that the amount of silver halide in the color image forming layer is 0.
1 g / m ² or more, and when the desilvering processing time is shortened,
The occurrence of poor desilvering was remarkable, and the color image became dull. Photosensitive materials (205) and (20) of the present invention
6), (208), (209), (211), (21)
2), (214), and (215) show that the degree of poor desilvering when the desilvering time is shortened is greatly improved. In particular, photosensitive materials (211), (212),
In (214) and (215), the amount of silver halide is in a preferable range, and even when the bleaching and fixing processing steps are significantly shortened, the value indicating an unnecessary increase in density derived from residual silver is close to zero, and the maximum density is high. The occurrence of dullness in the portion was small and a good color image could be obtained.

Example 3 (Preparation of Blue-Sensitive Silver Halide Emulsion Em-B2) Example 1
In the preparation of silver halide emulsion EMP-1A of (A)
1 solution) and (C1 solution) by the following (A2 solution), (C2 solution)
Similarly, except that the average particle size was changed to 0.71 μm,
Coefficient of variation of particle size distribution 0.07, silver chloride content 85 mol%
To obtain a monodispersed cubic emulsion EMP-2A. Next, (A2
Solution) and (B1 solution) and (C2 solution) and (D1 solution)
Liquid), the average particle size was 0.64 μm, and the variation coefficient of the particle size distribution was 0.0.
7. Monodisperse cubic emulsion EMP having a silver chloride content of 85 mol%
-2B was obtained.

(Solution A2) Sodium chloride 2.92 g Potassium bromide 1.05 g Water was added to 200 ml (Solution C2) 87.7 g of sodium chloride Potassium hexachloroiridate (IV) 4 × 10 ⁻⁸ mol Hexacyanoiron (II) Potassium acid acid 2 × 10 ^-5 mol Potassium bromide 31.5 g Water was added and 600 ml The above-mentioned E was added to EMP-2A and EMP-2B.
After optimally chemical sensitizing in the same manner as MP-1A and EMP-1B, the sensitized EMP-2A and EMP-2B were mixed at a silver amount of 1: 1 to obtain a blue-sensitive silver halide emulsion (Em-2).
-B2) was obtained.

(Preparation of Blue-Sensitive Silver Halide Emulsion Em-B3) In the preparation of the silver halide emulsion EMP-1A of Example 1, (Solution A1) and (Solution C1) were replaced by (Solution A3)
(C3 liquid) except that the average particle diameter was 0.1.
A monodisperse cubic emulsion EMP-3A having a particle size distribution of 71 μm, a variation coefficient of 0.07 and a silver chloride content of 75 mol% was obtained. Next, the average particle size was 0.64 μm and the particle size distribution was the same as in EMP-3A, except that the addition times of (A3 solution) and (B1 solution) and (C3 solution) and (D1 solution) were changed. A monodisperse cubic emulsion EMP-3B having a coefficient of variation of 0.07 and a silver chloride content of 75 mol% was obtained.

(Liquid A3) 2.58 g of sodium chloride 1.75 g of potassium bromide 200 ml with water added (Liquid C3) 77.4 g of sodium chloride Potassium hexachloroiridate (IV) 4 × 10 ⁻⁸ mol hexacyanoiron (II) Potassium acid acid 2 × 10 ^-5 mol Potassium bromide 52.4 g Water was added and 600 ml The above-mentioned EMP-3A and EMP-3B were added to EMP-3A and EMP-3B.
After optimal chemical sensitization in the same manner as MP-1A and EMP-1B, the sensitized EMP-3A and EMP-3B were mixed at a silver amount of 1: 1 to obtain a blue-sensitive silver halide emulsion (Em-3).
-B3) was obtained.

(Silver halide photographic light-sensitive material (301))
(Preparation of (310)) Photosensitive material (107) of Example 1,
In the preparation of (108), (110), (112) and (114), the photosensitive material (301) was prepared in the same manner except that the blue-sensitive silver halide emulsion was changed as shown in Table 3.
To (310).

The light-sensitive material (30
1) to (310) and (107), (108), (1)
For each of 10), (112), and (114), three sets of samples that were exposed to white wedge light for 0.5 seconds were prepared, and processed in the processing steps D to F, respectively. The same evaluation as in Example 2 was performed. The results are shown in Table 3.

[0154]

[Table 3]

From the results shown in Table 3, it can be seen that in the light-sensitive material of the present invention, the degree of defective desilvering when the bleaching and fixing processing times are shortened is greatly improved. In particular, when the silver chloride content of the silver halide emulsion is 80 mol% or more, even when the bleaching and fixing steps are greatly shortened, unnecessary increase in density due to residual silver is small, and A good color image with little occurrence of dullness could be obtained.

The light-sensitive materials (108), (110), (114) and (30) satisfying a particularly preferred embodiment of the present invention in which the silver halide content of the silver halide emulsion is 80 mol% or more.
2), (303) and (305) show that even in the processing step F in which the bleaching and fixing processing steps are largely omitted, an unnecessary increase in density due to residual silver is small, and the color dullness in the maximum density portion is small. I especially liked it.

Example 4 (Preparation of photosensitive materials (401) to (405)) The preparation of the photosensitive material (105) of Example 1 was repeated except that the magenta coupler was changed as shown in Table 4. Materials (401) to (405) were prepared.

The thus prepared photosensitive material (40)
For each of 1) to (405), 0.5% with white light.
Prepare three sets of samples that have been exposed to light wedges in seconds.
Each processing was performed by F, and the same evaluation as in Example 2 was performed. The results are shown in Table 4. In Table 4, the added amount of the coupler was shown as mmol / m ² .

[0159]

[Table 4]

From the results in Table 4, it can be seen that the light-sensitive material (4) in which a coupler that forms a mobile dye by a coupling reaction with a developing agent and a coupler that forms a non-mobile dye are used in combination.
02) to (404), it can be seen that the degree of poor desilvering when the bleaching and fixing processing times were shortened was greatly improved. In particular, the photosensitive materials (403) and (404) in which the molar ratio of couplers forming mobile dyes is 15% or more have ΔDE and ΔDF close to zero even when the bleaching and fixing processing steps are greatly shortened. It can be seen that this is a preferred embodiment of the present invention in which the occurrence of dullness in the maximum density portion is small and good color images can be obtained.

Example 5 (Preparation of Green-Sensitive Silver Halide Emulsion (Em-G1)) In the preparation of silver halide emulsion EMP-1A of Example 1, the addition time of (A1 solution) and (B1 solution) and (C1 liquid)
A monodisperse cubic emulsion EMP-11A having an average grain size of 0.25 μm and a silver chloride content of 99.5 mol%, and an average grain size of 0.30 μm were prepared in the same manner as above except that the addition time of (D1 solution) was changed.
A monodispersed cubic emulsion EMP-11B having a thickness of 9 μm and a silver chloride content of 99.5 mol% was obtained. The above-mentioned EMP-11A was optimally subjected to chemical sensitization at 60 ° C. using the following compounds. Similarly, after optimally chemical sensitizing EMP-11B, the sensitized EMP-11A and EMP-11B are mixed at a silver ratio of 1: 1 to obtain a green photosensitive silver halide emulsion ( Em-G1) was obtained.

Sodium thiosulfate 1.5 mg / mol AgX Chloroauric acid 1.0 mg / mol AgX Sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX Stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX Stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX Stabilizer STAB-3 3 × 10 ⁻⁴ mol / mol AgX (Preparation of red-sensitive silver halide emulsion (Em-R1)) Halogenation of Example 1 In the preparation of silver emulsion EMP-1A, the addition time of (A1 solution) and (B1 solution) and (C1 solution)
A monodisperse cubic emulsion EMP-21A having an average particle size of 0.30 μm and a silver chloride content of 99.5 mol%, and an average particle size of 0.38
A monodispersed cubic emulsion EMP-21B having a thickness of 9 μm and a silver chloride content of 99.5 mol% was obtained. The above-mentioned EMP-21A was optimally subjected to chemical sensitization at 60 ° C. using the following compounds. Similarly, after optimally chemical sensitizing EMP-21B, the sensitized EMP-21A and EMP-21B are mixed at a silver amount of 1: 1 to obtain a red-sensitive silver halide emulsion ( Em-R1) was obtained.

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-2 1 × 10 ⁻⁴ mol / mol AgX SS-1 2.0 × 10 ⁻³ mol / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-3 3 × 10 ^-4 mol / mol AgX

[0164]

Embedded image

(Preparation of silver halide photographic light-sensitive material (501)) After the reflective support prepared in Example 1 was subjected to corona discharge treatment, a gelatin undercoat layer was provided, and each layer having the following structure was further provided. To prepare a silver halide photographic light-sensitive material.

Each coating solution was prepared so as to have the following coating amount, and (H-1) and (H-2) were added as hardeners. Surfactants (SU-2), (S
U-3) was added to adjust the surface tension. Further, (F-1) was added to each layer so that the total amount became 0.04 g / m ² .

The coating amount of each layer is shown below.

Layer composition Addition amount (g / m ² ) 7th layer (protective layer) Gelatin 1.00 DIDP 0.002 DBP 0.002 Silicon dioxide 0.003 6th layer (UV absorbing layer) Gelatin 0.40 AI-1 0.01 UV absorber (UV-1) 0.12 UV absorber (UV-2) 0.04 UV absorber (UV-3) 0.16 Stain inhibitor (HQ-5) 0.04 PVP 0.03 Fifth layer (red-sensitive layer) Gelatin 1.30 Red-sensitive emulsion (Em-R1) 0.030 Cyan coupler (C-2) 0.55 mmol Dye image stabilizer (ST-1) 0.10 Anti-stain agent (HQ-1) 0.004 DBP 0.10 DOP 0.20 Fourth layer (ultraviolet absorbing layer) Gelatin 0.94 Ultraviolet absorbing agent (UV-1) 0.28 Ultraviolet absorbing agent (UV -2) 0.09 Ultraviolet absorber (UV-3) 0.38 AI-1 0.02 Stain inhibitor (HQ-5) 0.10 Third layer (green photosensitive layer) Gelatin 1.30 AI-2 0.01 Green photosensitive Emulsion (Em-G1) 0.030 Magenta coupler (M-1) 0.45 mmol Dye image stabilizer (ST-3) 0.20 Dye image stabilizer (ST-4) 0.17 DIDP 0.13 DBP 0.13 Second layer (intermediate layer) Gelatin 1.20 AI-3 0.01 Stain inhibitor (HQ-2) 0.03 Stain inhibitor (HQ-3) 0.03 Stain inhibitor (HQ-4) ) 0.05 Stain inhibitor (HQ-5) 0.23 DIDP 0.04 DBP 0.02 Fluorescent whitening agent (W-1) 0.10 First layer (blue-sensitive layer) Gelatin 1.20 Blue-sensitive Emulsion (Em-B1) 0.055 yellow Coupler (Y-1) 0.95 mmol Dye image stabilizer (ST-1) 0.10 Dye image stabilizer (ST-2) 0.10 Dye image stabilizer (ST-5) 0.10 Stain Inhibitor (HQ-1) 0.01 Image stabilizer A 0.15 DBP 0.10 DNP 0.05 Support Polyethylene laminated paper The silver halide coating amount is shown in terms of silver. Further, only the amount of the coupler is shown in mmol / m ² .

DOP: dioctyl phthalate DNP: dinonyl phthalate HQ-1: 2,5-di-t-octylhydroquinone HQ-2: 2,5-di-sec-dodecylhydroquinone HQ-3: 2,5-di- sec-tetradecylhydroquinone HQ-4: 2-sec-dodecyl-5-sec-tetradecylhydroquinone HQ-5: 2,5-di (1,1-dimethyl-4-hexyloxycarbonyl) butylhydroquinone Image stabilizer A : Pt-octylphenol (Preparation of silver halide photographic light-sensitive materials (502) to (508))
The photosensitive materials (502) to (5) were prepared in the same manner except that the couplers of the layers, the third layer and the fifth layer were changed as shown in Table 5.
(508) was prepared.

The thus prepared photosensitive material (50)
For each of 1) to (508), three sets of samples each of which were subjected to light wedge exposure for 0.5 seconds with blue light, green light and red light were prepared, and processed in the processing steps A and B, respectively. Was done. For each of the processed samples, the density of the yellow image (Y) for the sample exposed to blue light, the magenta image (M) for the sample exposed to green light, and the cyan image (C) for the sample exposed to red light. The measurement was performed, and the same evaluation as in Example 1 was performed. The results are shown in Table 5.

[0171]

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[0172]

Embedded image

[0173]

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[0174]

[Table 5]

From the results in Table 5, it can be seen that, even in a full-color photosensitive material, a color image forming layer satisfying the constitution of the present invention has a low occurrence of poor desilvering due to a shortening of the bleaching / fixing processing time and a color image with less dullness. I got it. Further, in the photosensitive material (508) in which all the photosensitive layers satisfy the constitution of the present invention, when the bleaching / fixing processing time is reduced, the color image with less dullness in any of the Y, M and C color images is obtained. Could be obtained.

Further, photosensitive materials (501) and (508)
Was exposed through a color negative film that had been photographed and developed, and then processed in the processing step B, and the resulting printed images were compared. As a result, in the photosensitive material (501), the whole image had a dull feeling, but in the photosensitive material (508), the dull feeling was reduced.
It was confirmed that the overall image was vivid and the print image was preferable.

[0177]

According to the present invention, it has been possible to provide a silver halide photographic material and an image forming method in which the deterioration of color reproducibility due to poor desilvering is improved when the bleaching and fixing processing steps after the amplification development processing are accelerated. .

Claims (6)

[Claims] 1. A silver halide photographic material having at least one color image forming layer having a photosensitive silver halide and a coupler on a support, wherein the amount of silver halide contained in the color image forming layer is 0.1 g / m ² or less in terms of silver, and the color image forming layer contains a diffusion-resistant coupler which forms a mobile dye by a coupling reaction with an oxidized color developing agent. Silver halide photographic light-sensitive material. 2. A silver halide photographic material having at least one color image forming layer having a photosensitive silver halide and a coupler on a support, wherein the amount of silver halide contained in the color image forming layer is 0.1 g / m ² or less in terms of silver, and the color image forming layer has no dissociable group of pka 12 or less due to a coupling reaction with an oxidized color developing agent and has a molecular weight of 250 to 700. A silver halide photographic light-sensitive material characterized by forming dye molecules. 3. A silver halide photographic material having at least one color image forming layer having a photosensitive silver halide and a coupler on a support, wherein the amount of silver halide contained in the color image forming layer is 0.1 g / m ² or less in terms of silver, and the color image-forming layer has at least one pka1 by a coupling reaction with an oxidized color developing agent.
Having a dissociable group of 2 or less and a molecular weight of 450 to 12
A silver halide photographic light-sensitive material characterized by forming dye molecules of not more than 00. 4. The halogen according to claim 1, wherein the amount of silver halide contained in the color image forming layer is 0.045 g / m ² or less in terms of silver. Silver halide photographic material. 5. The silver halide photographic material according to claim 4, wherein the diffusion-resistant coupler forming the mobile dye is a magenta coupler or a cyan coupler. 6. An image forming method, comprising subjecting the silver halide photographic material according to claim 1 to amplification development processing.