JP2001075244A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide color photographic sensitive material containing a two-equivalent yellow coupler excellent in color forming property, having high solubility in a solvent and excellent also in suitability to deposition and dispersion stability. SOLUTION: The silver halide color photographic sensitive material contains at least one two-equivalent yellow coupler of the formula, wherein R1 is a substituent, R2 is a 7-20C branched alkyl, R3 is H or a halogen, (m) is an integer of 1-5, Z1 is >N-R4 or -O-, Z2 is >N-R5 or>C(R6)(R7), R4 and R5 are each H, an alkyl, cycloalkyl, aryl or a heterocyclic group, R6 and R7 are each H or a substituent and R3 may be C1.

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 containing a novel yellow coupler which is excellent in coloring properties, has high solubility in a solvent, and has excellent precipitation properties and dispersion stability. The present invention relates to a silver halide color photographic material.

[0002]

2. Description of the Related Art In recent years, silver halide color photographic materials (hereinafter, also simply referred to as color photographic materials) have
Instead of the conventional 4-equivalent coupler that required 4 atoms of silver to form a molecular dye, an appropriate substituent is introduced at the coupling position (active site) of the coupler that reacts with the developing agent oxide. Accordingly, a two-equivalent coupler in which silver for forming one molecule of a dye is sufficient with two atoms tends to be frequently used.

However, with the advancement of color photographic materials, the demand for couplers is becoming more and more strict, and further improvement in color development is required in terms of high sensitivity, high image quality, and reduction in development processing time. It is becoming required.

By the way, as a yellow coupler, a pivaloyl acetanilide type yellow coupler and a benzoylacetanilide type yellow coupler are typical, and it is generally known that a benzoylacetanilide type yellow coupler has higher color development. . However, conventional benzoylacetanilide-type yellow couplers are inferior in solubility in a solvent, so that in producing a color light-sensitive material, a large amount of a solvent must be used at the time of dispersion. There is a disadvantage that precipitation is likely to occur after being once dispersed in the solvent. Under the conditions for thinning, which has been strongly pursued in recent years, these drawbacks are remarkably emphasized, and it is clear that they become a great obstacle to practical use.

Further, the conventional benzoylacetanilide-type yellow coupler has poor solubility in a solvent as in the case of the synthetic intermediate thereof, similarly to the coupler. However, it has problems such as the use of a halogen-based solvent which is undesired due to its poor dissolving power or environmental suitability.

On the other hand, a benzoylacetanilide type yellow coupler having improved solubility by introducing a branched alkyl group has been proposed in EP 327,348. Although this coupler has improved solubility, it has the disadvantage of poor color development when the pH of the developer is low. Furthermore, Japanese Patent Application Laid-Open No. 3-84546 and European Patent No. 897,133 also propose the introduction of a branched alkyl group, but the color developability is still insufficient and further improvement has been desired.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and a first object of the present invention is to provide a silver halide color photographic photosensitive material containing a novel 2-equivalent yellow coupler having excellent color developing properties. Is to provide the material.

A second object of the present invention is to provide a silver halide color photographic light-sensitive material containing a novel 2-equivalent yellow coupler having high solubility in a solvent, excellent precipitation properties and excellent dispersion stability. .

[0009]

The above object of the present invention is attained by each of the following constitutions.

[0010] 1. A silver halide color photographic light-sensitive material comprising at least one coupler represented by formula (I).

2. 2. The silver halide color photographic light-sensitive material according to 1, wherein in the general formula [I], R ₃ is a chlorine atom.

3. A silver halide color photographic light-sensitive material comprising at least one kind of coupler represented by the general formula [II].

4. 4. The silver halide color photographic light-sensitive material according to 3, wherein in the general formula [II], R ₃ is a chlorine atom.

5. A silver halide color photographic light-sensitive material comprising at least one coupler represented by formula (III).

6. 6. The silver halide color photographic material according to 5, wherein in the general formula [III], R ₃ is a chlorine atom.

[7] 7. The silver halide color photographic light-sensitive material according to 5 or 6, wherein in the general formula [III], R ₁₀ is an unsubstituted alkyl group having 8 to 21 carbon atoms.

8. 7. The silver halide color photographic light-sensitive material according to 5 or 6, wherein in the general formula [III], R ₁₀ is represented by the general formula [IV].

Hereinafter, the present invention will be described in detail. In the general formula [I], examples of the substituent represented by R ₁ include an alkyl group (eg, a methyl group, an ethyl group, an isopropyl group, a t-butyl group, a hexyl group, a dodecyl group, etc.), a cycloalkyl group (Eg, cyclopentyl group, cyclohexyl group, adamantyl group, etc.), aryl group (eg, phenyl group, pt-octylphenyl group, etc.), heterocyclic group (eg, pyridyl group, thiazolyl group, oxazolyl group, etc.), alkoxy group (eg, Methoxy group, etc.), aryloxy group (eg, 2,4-di-t-amylphenoxy group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, etc.), aryloxycarbonyl group (eg, m-pentadecylphenoxycarbonyl group, etc.) , A halogen atom (eg, chlorine atom, bromine atom, etc.), a sulfonyl group (eg, meta Sulfonyl group, etc.), acylamino group (eg, acetylamino group, benzoylamino group, etc.), sulfonylamino group (eg, dodecanesulfonylamino group, etc.), nitro group, cyano group, amino group (eg, dimethylamino group, anilino group, etc.), Examples include an alkylthio group (eg, a methylthio group) and a hydroxy group.

The substituent represented by R ₁ may be further substituted by a substituent. R ₁ is preferably an alkoxy group, particularly preferably a methoxy group.

In the general formula (I), typical examples of the branched alkyl group having 7 to 20 carbon atoms represented by R ₂ are shown below, but the present invention is not limited to these. .

[0021]

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R ₂ may have a substituent. In this case, examples of the substituent include the same groups as the substituents represented by R ₁ in the general formula [I].

In the general formulas [I], [II] and [III], R ₃ represents a hydrogen atom or a halogen atom.

R ₃ is preferably a halogen atom, particularly preferably a chlorine atom. In the general formulas [I] and [II], m represents an integer of 1 to 5.

M is preferably 1, and particularly preferably, the substitution position of R ₁ is the para position of the acyl group in the general formulas [I] and [II].

In the above general formulas [I], [II] and [III], Z ₁ is> NR ₄ (R ₄ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group) Or —O—, and Z ₂ represents> NR ₅ (R ₅ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group) or> C (R ₆ ) (R ₇ ) ( R ₆ and R ₇ represent a hydrogen atom or a substituent).

As the alkyl group, cycloalkyl group, aryl group or heterocyclic group represented by R ₄ and R ₅ , the alkyl group represented by the substituent represented by R ₁ in the aforementioned general formula [I] can be used. The same groups as the group, cycloalkyl group, aryl group and heterocyclic group can be exemplified.

The alkyl group, cycloalkyl group, aryl group or heterocyclic group represented by R ₄ and R ₅ may have a substituent. In this case, examples of the substituent include those represented by the aforementioned general formula [I And the same groups as the substituents represented by R ₁ in the above.

Examples of the substituents represented by R ₆ and R ₇ include the same groups as the substituents represented by R ₁ in the general formula [I].

The substituents represented by R ₆ and R ₇ may be further substituted by substituents.

In the general formula [II], the alkyl group, cycloalkyl group or aryl group represented by R ₈ is represented by an example of the substituent represented by R ₁ in the general formula [I]. Examples include the same groups as the alkyl group, cycloalkyl group and aryl group.

The alkyl group, cycloalkyl group or aryl group represented by R ₈ may have a substituent. In this case, examples of the substituent include those represented by R ₁ in the above general formula [I]. And the same groups as the above substituents.

In the general formula [II], the alkyl group or cycloalkyl group represented by R ₉ is an alkyl group or cycloalkyl group represented by an example of the substituent represented by R ₁ in the general formula [I]. The same groups as the alkyl groups can be exemplified.

The alkyl group or cycloalkyl group represented by R ₉ may have a substituent. In this case, examples of the substituent include the substituent represented by R ₁ in the general formula [I]. And the same groups as described above.

In the general formula [II], the sum of the carbon numbers of R ₈ and R ₉ is 7 to 20. In the general formula (III), examples of the diffusion-resistant alkyl group represented by R ₁₀ include preferably an alkyl group having 8 to 21 carbon atoms, which may be linear or branched. Octyl group, 2-
Examples include an ethylhexyl group, a decyl group, a 2,4-diethylheptyl group, a dodecyl group, an isotridecyl group, a tetradecyl group, a hexadecyl group, a 2-hexyldecyl group, and an octadecyl group.

The diffusion-resistant alkyl group represented by R ₁₀ may have a substituent. In this case, the substituent is represented by, for example, R ₁ in the general formula [I]. The same groups as the substituents can be mentioned. In this case,
The total number of carbon atoms including the substituent is preferably 9 to 30.

In the above general formula [IV], the alkyl group, cycloalkyl group or aryl group represented by R ₁₁ is
Examples of the substituents represented by R ₁ in the general formula [I] include the same groups as the alkyl group, cycloalkyl group and aryl group.

The alkyl group, cycloalkyl group or aryl group represented by R ₁₁ may have a substituent. In this case, examples of the substituent include those represented by R ₁ in the general formula [I]. And the same groups as the above substituents.

In the general formula [IV], the alkyl group or cycloalkyl group represented by R _{12 includes} an alkyl group represented by R ₁ in the general formula [I] and a cycloalkyl group represented by R _1. The same groups as the cycloalkyl group can be exemplified.

The alkyl group or cycloalkyl group represented by R ₁₂ may have a substituent. In this case, examples of the substituent include the substituent represented by R ₁ in the above general formula [I]. And the same groups as described above.

In the general formula [IV], n is 1 to 10
Represents an integer. When n is 2 or more, a plurality of R ₁₁ may be the same or different.

The total number of carbon atoms of the group represented by the general formula [IV] is 9 to 22. In the general formula [III], R
₁₀ is preferably an unsubstituted alkyl group having 8 to 21 carbon atoms.

The couplers of the present invention represented by the general formulas [I], [II] and [III] are bonded at any of the substituents to form a bis-form, a tris-form, a tetrakis-form or a polymer-form. May be.

The compounds of the general formulas [I], [II] and [II]
Among the couplers represented by I], couplers represented by general formula [III] are particularly preferred.

Next, typical specific examples of the couplers represented by the general formulas [I], [II] and [III] of the present invention are shown below.
The present invention is not limited by these.

[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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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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The general formulas [I], [II] and [II] of the present invention
The coupler (I) (hereinafter also referred to as the coupler of the present invention) can be easily synthesized by a conventionally known method. Hereinafter, typical synthesis examples of the coupler of the present invention will be described. Synthesis Example 1 Illustrative coupler I-1 was synthesized according to the following synthesis scheme. Synthesis scheme

[0060]

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I) Synthesis of Compound C 26.1 g of Compound A and 25.0 g of Compound B were combined with 125
The reaction was carried out for 3 hours while heating and refluxing while distilling off the produced ethanol in ml of xylene.

After completion of the reaction, the solvent was recovered under reduced pressure, and
By recrystallizing from 10 ml of acetonitrile, 33.2 g of Compound C (79% yield) was obtained. ii) Synthesis of Compound D 30.0 g of Compound C was dissolved in 90 ml of toluene, and 9.37 g of sulfuryl chloride was slowly added dropwise at about 30 ° C.

After completion of the dropwise addition, the mixture was stirred at the same temperature for 1.5 hours, and then the solvent was recovered under reduced pressure.
Was obtained in an amount of 32.4 g (100% yield).

Compound D was used in the next step without further purification. iii) Synthesis of exemplified coupler I-1 32.4 g of compound D was dissolved in 180 ml of acetone,
12.5 g of potassium carbonate and 11.7 g of compound E were added,
The reaction was carried out for 3 hours while heating under reflux. After completion of the reaction, ethyl acetate and water were added, the organic layer was extracted, further washed with dilute hydrochloric acid, and washed three times with water. Thereafter, the solvent was recovered under reduced pressure, and the residue was recrystallized from 120 ml of methanol to obtain 29.2 g of the exemplified coupler I-1 (yield: 75%). Melting point was 108-109 ° C.

The structure of the exemplified coupler I-1 is represented by NMR, I
Confirmed by R and mass spectrum. Synthesis Example 2 Illustrative coupler II-2 was synthesized according to the following synthesis scheme. Synthesis scheme

[0066]

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I) Synthesis of Exemplified Coupler II-2 25.0 g of Compound F was dissolved in 75 ml of ethyl acetate,
5.64 g of triethylamine and 8.76 g of compound G were added, and reacted under heating and reflux for 5 hours. After the completion of the reaction, add water 10
0 ml was added, and the organic layer was extracted. Then, after washing with dilute sulfuric acid, it was washed three times with water. Thereafter, the solvent was distilled off under reduced pressure. The obtained residue is subjected to column chromatography (silica gel,
(Developing solvent: ethyl acetate / n-hexane)
24.8 g of oily exemplified coupler II-2 (81% yield)
Obtained.

The structure of the exemplified coupler II-2 is represented by NMR, I
Confirmed by R and mass spectrum. Synthesis Example 3 Exemplary coupler III-3 was synthesized according to the following synthesis scheme. Synthesis scheme

[0069]

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I) Synthesis of compound J: 885 ml of 120 g of compound H and 177 g of compound I
The reaction was carried out for 12 hours while heating and refluxing while distilling off the produced ethanol in toluene.

After completion of the reaction, the solvent was recovered under reduced pressure, and
By recrystallization from 80 ml of ethanol, 238 g (yield 92%) of compound J was obtained. ii) Synthesis of Compound K 200 g of Compound J was dissolved in 600 ml of toluene, and 58.8 g of sulfuryl chloride was slowly added dropwise at about 40 ° C.

After completion of the dropwise addition, the mixture was stirred at the same temperature for 3 hours, and then the solvent was recovered under reduced pressure.
5 g (yield 100%) was obtained.

Compound K was used in the next step without further purification. iii) Synthesis of Exemplified Coupler III-3 215 g of Compound K was dissolved in 645 ml of acetone, 78.3 g of potassium carbonate and 108 g of Compound L were added, and the mixture was reacted under heating and reflux for 3 hours. After completion of the reaction, ethyl acetate and water were added, and the organic layer was extracted.
Washed twice. Thereafter, the solvent was recovered under reduced pressure, and
By recrystallizing from 0 ml of methanol, 237 g (yield 84%) of Exemplified Coupler III-3 was obtained. Melting point was 103-104 ° C.

The structure of the exemplified coupler III-3 is represented by NMR,
Confirmed by IR and mass spectrum. Synthesis Example 4 Exemplary coupler III-32 was synthesized according to the following synthesis scheme. Synthesis scheme

[0075]

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I) Synthesis of Illustrative Coupler III-32 10.0 g of Compound M was dissolved in 30 ml of ethyl acetate.
2.15 g of triethylamine and 3.34 g of compound G were added, and reacted under heating and reflux for 5 hours. After the reaction is completed,
ml was added and the organic layer was extracted. Then, after washing with dilute sulfuric acid, it was washed three times with water. Thereafter, the solvent was distilled off under reduced pressure. The obtained residue was purified by column chromatography (silica gel, developing solvent: ethyl acetate / n-hexane), and 8.74 g of oily Exemplary Coupler III-32 (yield: 72) was obtained.
%)Obtained.

The structure of the exemplified coupler III-32 is NM
It was confirmed by R, IR and mass spectrum.

Illustrative couplers I-1, II-2, III-3, I
Illustrative couplers other than II-32 were also synthesized according to the above synthesis examples, starting from the corresponding raw materials.

The couplers of the present invention can be used alone or in combination of two or more. Further, it can be used in combination with any known pivaloylacetanilide-based or benzoylacetanilide-based yellow coupler.

To incorporate the coupler of the present invention in a silver halide photographic emulsion of a color photographic light-sensitive material, for example, a high boiling organic solvent having a boiling point of 175 ° C. or more such as tricresyl phosphate or dibutyl phthalate, ethyl acetate, methanol Dissolved alone or in combination with one or more low boiling organic solvents conventionally used in preparing coupler dispersions, such as acetone, chloroform, methyl chloride or butyl propionate Thereafter, the mixture is mixed with a gelatin aqueous solution containing a surfactant, and then this mixture is emulsified and dispersed by a high-speed rotary mixer or a colloid mill, and the resulting emulsified dispersion is directly added to a silver halide photographic emulsion, Alternatively, after setting the above emulsified dispersion, chopping, and then removing the low boiling organic solvent by means such as washing with water. This may be added in the silver halide photographic emulsion.

The coupler of the present invention is usually preferably added in an amount of about 1 × 10 ⁻³ mol to about 1 mol per mol of silver halide, but the addition amount may be changed to other amounts depending on the application purpose. Is also good.

The silver halide color photographic light-sensitive material of the present invention may be of any type and use.
Examples of the silver halide used include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide.

The silver halide color photographic light-sensitive material of the present invention may contain, in addition to the coupler of the present invention, another color coupler for forming a multicolor image.

In the silver halide color photographic light-sensitive material of the present invention, a color antifoggant, an image stabilizer, a hardener, a plasticizer, a polymer latex, a formalin scavenger, a mordant, a development accelerator, a development retarder, a fluorescent enhancer A whitening agent, a matting agent, a solvent, an antistatic agent, a surfactant and the like can be optionally used.

The durability of the yellow image produced on the silver halide color photographic light-sensitive material containing the coupler of the present invention can be further improved by incorporating an ultraviolet absorber into the light-sensitive material.

[0086]

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

Example 1 1.0 g of each of the couplers of the present invention as shown in Table 1 (indicated by the number of the above-mentioned exemplified couplers) and the following comparative couplers
Was added to a mixed solution of 0.4 g of tricresyl phosphate and 2.6 g of ethyl acetate, and dissolved by heating to 70 ° C.

0.7 g gelatin and 80 g
A solution prepared by dissolving mg of alkanol XC in 13.2 g of water at 45 ° C. was added and emulsified and dispersed using an ultrasonic homogenizer to prepare a yellow coupler dispersion as shown in Table 1.

After the dispersion was completed, water was added to the dispersion to make the total amount 20 g, and the dispersion was stored in a refrigerator for 2 weeks. Thereafter, each yellow coupler dispersion was observed using a microscope to evaluate the precipitation property. did. Table 1 shows the results.

The following couplers were used as comparative couplers.

[0091]

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[0092]

[Table 1]

As is clear from Table 1 above, none of the couplers of the present invention was precipitated, and the dispersion stability of the emulsion over time was superior to the comparative coupler.

Example 2 On a triacetyl cellulose film support provided with an undercoat layer, layers having the following compositions were sequentially formed from the support side to prepare a multilayer silver halide color photographic material sample 201. did.

The amount of addition is expressed in grams per m ² .
However, silver halide and colloidal silver were converted to the amount of silver, and sensitizing dyes (indicated by SD) were shown in moles per mole of silver. First layer (antihalation layer) Black colloidal silver 0.16 UV-3 0.3 CM-1 0.123 CC-1 0.044 OIL-1 0.167 Gelatin 1.33 Second layer (intermediate layer) AS -1 0.160 OIL-1 0.20 Gelatin 0.69 Third layer (low-sensitivity red-sensitive layer) Silver iodobromide a 0.20 Silver iodobromide b 0.29 SD-1 2.37 × 10 ^{− 5} SD-2 1.2 × 10 ^-4 SD-3 2.4 × 10 ^-4 SD-4 2.4 × 10 ^-6 C-3 0.32 CC-1 0.038 OIL-2 0.28 AS -2 0.002 Gelatin 0.73 Fourth layer (medium sensitivity red-sensitive layer) Silver iodobromide c 0.10 Silver iodobromide d 0.86 SD-1 4.5 × 10 ^-5 SD-2 3 × 10 ^-4 SD-3 4.5 × 10 ^-4 C-4 0.52 CC-1 0.06 DI-1 0.047 OIL-2 0.46 AS -2 0.004 Gelatin 1.30 Fifth layer (high-sensitivity red-sensitive layer) Silver iodobromide c 0.13 Silver iodobromide d 1.18 SD-1 3.0 × 10 ^-5 SD-2 5 × 10 ^-4 SD-3 3.0 × 10 ^-4 C-4 0.047 C-5 0.09 CC-1 0.036 DI-1 0.024 OIL-2 0.27 AS-20 006 Gelatin 1.28. 6th layer (intermediate layer) OIL-1 0.29 AS-1 0.23 gelatin 1.00 7th layer (low-sensitivity green-sensitive layer) Silver iodobromide a 0.19 Silver iodobromide b 0.062 SD -4 3.6 × 10 ^-4 SD-5 3.6 × 10 ^-4 M-1 0.21 CM-1 0.033 OIL-1 0.22 AS-2 0.002 AS-3 0.05 Gelatin 0.61 8th layer (intermediate layer) OIL-1 0.26 AS-1 0.054 gelatin 0.80 9th layer (medium-sensitive green-sensitive layer) Silver iodobromide e 0.54 Silver iodobromide f0 .54 SD-6 3.7 × 10 ^-4 SD-7 7.4 × 10 ^-5 SD-8 5.0 × 10 ^-5 M-1 0.17 CM-1 0.024 CM-2 0.029 DI-2 0.024 DI-3 0.005 OIL-1 0.73 AS-3 0.035 AS-2 0.003 Gelatin 1.80 10th layer High speed green-sensitive layer) Silver iodobromide f 1.19 SD-6 4.0 × 10 -4 SD-7 8.0 × 10 -5 SD-8 5.0 × 10 -5 M-1 0.09 CM-2 0.026 CM-1 0.022 DI-3 0.003 DI-2 0.003 OIL-1 0.19 OIL-2 0.43 AS-3 0.017 AS-2 0.014 Gelatin 1 .23 11th layer (yellow filter layer) Yellow colloidal silver 0.05 OIL-1 0.18 AS-1 0.16 gelatin 1.00 12th layer (low-sensitivity blue-sensitive layer) Silver iodobromide b 0.22 Silver iodobromide a 0.08 Silver iodobromide h 0.09 SD-9 6.5 × 10 ^-4 SD-10 2.5 × 10 ^-4 Y-5 0.77 DI-4 0.017 OIL- 1 0.31 AS-2 0.002 Gelatin 1.29 13th layer (high-sensitivity blue-sensitive layer) Silver iodobromide h 0.41 Iodine Silver bromide i 0.61 SD-9 4.4 × 10 ^-4 SD-10 1.5 × 10 ^-4 Y-5 0.23 OIL-1 0.10 AS-2 0.004 Gelatin 1.20 14 layer (first protective layer) Silver iodobromide j 0.30 UV-3 0.055 UV-4 0.110 OIL-2 0.30 gelatin 1.32 15th layer (second protective layer) PM-1 0.15 PM-2 0.04 WAX-1 0.02 AI-5 0.001 gelatin 0.55 ).

Emulsion No. Average particle size (μm) Average AgI amount (mol%) Diameter / thickness ratio Silver iodobromide a 0.30 2.0 1.0 b 0.40 8.0 1.4 c 0.60 7.0 3.0. 1 d 0.74 7.0 5.0 e 0.60 7.0 4.1 f 0.65 8.7 6.5 h 0.65 8.0 1.4 i 1.00 8.0 2.0. 0 j 0.05 2.0 1.0 As a typical example of the formation of the silver halide grains,
Production examples of silver iodobromide d and f are shown below. Regarding silver iodobromide j, JP-A-1-183417 and 1-183.
No. 644, No. 1-183645, No. 2-166442
It was made with reference to the description of the issue.

(Preparation of Seed Emulsion-1) JP-B-58-58
No. 288 and No. 58-58289, a silver nitrate aqueous solution (1.161 mol) and a mixed aqueous solution of potassium bromide and potassium iodide (potassium iodide) were added to the following solution A1 adjusted to 35 ° C. 2 mol%) was added over 2 minutes by a double jet method while keeping the silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) at 0 mV to perform nucleation. Subsequently, the temperature of the solution was raised to 60 ° C. over a period of 60 minutes, and the pH was adjusted to 5.0 with an aqueous sodium carbonate solution.
2 mol) and a mixed aqueous solution of potassium bromide and potassium iodide (potassium iodide 2 mol%) was added over 42 minutes by a double jet method while keeping the silver potential at 9 mV. After the addition was completed, the temperature was lowered to 40 ° C., and desalting and washing were immediately performed using a normal flocculation method.

The resulting seed crystal emulsion had an average sphere-equivalent diameter of 0.24 μm, an average aspect ratio of 4.8, and a maximum side length ratio (maximum side ratio of each grain) of 90% or more of the total projected area of silver halide grains. The emulsion was composed of hexagonal tabular grains having a ratio of a side length to a minimum side length of 1.0 to 2.0. This emulsion is referred to as seed emulsion-1.

[Solution A1] Ossein gelatin 24.2 g Potassium bromide 10.8 g HO (CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) (10% ethanol solution) 6.78 mL 10% nitric acid 114ml H ₂ O 9657ml (preparation of silver iodide fine grain emulsion SMC-1) of 6.0 mass% containing 0.06 mol of potassium iodide While 5 L of the aqueous gelatin solution was vigorously stirred, 2 L of a 7.06 mol aqueous solution of silver nitrate and 2 L of a 7.06 mol aqueous solution of potassium iodide were added over 10 minutes. During this time, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the preparation of the particles, the pH was adjusted to 5.0 using an aqueous sodium carbonate solution. The average particle size of the obtained silver iodide fine particles is 0.05 μm.
Met. This emulsion is designated as SMC-1.

(Preparation of silver iodobromide d) Seed emulsion-1 equivalent to 0.178 mol and HO (CH ₂ CH ₂ O) _m (CH (C
H ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n =
9.77) containing 0.5 ml of a 10% ethanol solution.
700 ml of a 4.5 mass% inert gelatin aqueous solution is added to 75
After adjusting the pAg to 8.4 and the pH to 5.0 while maintaining at ℃, particles were formed by the simultaneous mixing method with vigorous stirring by the following procedure.

1) 3.093 mol of silver nitrate aqueous solution
287 mol of SMC-1 and an aqueous solution of potassium bromide,
The pAg was added while maintaining the pH at 8.4 and the pH at 5.0.

2) Subsequently, the solution was cooled to 60 ° C.
Was adjusted to 9.8. Then, 0.071 mol of SMC
-1 was added and aging was performed for 2 minutes (introduction of dislocation lines).

3) 0.959 mol silver nitrate aqueous solution and 0.1 mol
03 mol of SMC-1 and an aqueous solution of potassium bromide were added to p
Ag was added at 9.8 and the pH was maintained at 5.0.

Each solution was added at an optimum rate throughout the grain formation so as to prevent the formation of new nuclei and Ostwald ripening between grains. After completion of the addition, the resultant is subjected to a water-washing treatment at 40 ° C. using a normal flocculation method, and then gelatin is added and redispersed. The pAg is 8.1 and the pH is 5.8.
Was adjusted.

The obtained emulsion had a particle size (cubic 1 of the same volume).
Tabular grains having a halogen composition having a side length of 0.74 μm, an average aspect ratio of 5.0, and a silver iodide content of 2 / 8.5 / X / 3 mol% (X is a dislocation line introduction position) from the inside of the grains. Emulsion. When this emulsion was observed with an electron microscope, five or more dislocation lines were observed both in the fringe portion and in the inside of the grain in 60% or more of the total projected area of the grain in the emulsion. The surface silver iodide content was 6.7 mol%.

(Preparation of silver iodobromide f) In the preparation of silver iodobromide d, in step 1), pAg was 8.8, the amount of silver nitrate added was 2.077 mol, and the amount of SMC-1 was 0. .218
Silver iodobromide f in exactly the same manner as silver iodobromide d, except that the amount of silver nitrate added in step 3) was 0.91 mol and the amount of SMC-1 was 0.079 mol. did.

The obtained emulsion had a particle size (cubic 1 of the same volume).
Edge length) 0.65 μm, average aspect ratio 6.5, silver iodide content 2 / 9.5 / X / 8.0 mol% from the inside of the grain
The emulsion was composed of tabular grains having a halogen composition of (X is a dislocation line introduction position). When this emulsion was observed with an electron microscope, five or more dislocation lines were observed in both the fringe portion and the inside of the grains in 60% or more of the total projected area of the grains in the emulsion. The surface silver iodide content was 11.9 mol%.

After the above-mentioned sensitizing dyes were added to each of the above emulsions and ripened, triphenylphosphine selenide, sodium thiosulfate, chloroauric acid and potassium thiocyanate were added. Chemical sensitization was applied to optimize.

Silver iodobromide a, b, c, e, h, and i were also prepared according to the above silver iodobromide d and f, and subjected to spectral sensitization and chemical sensitization.

Incidentally, in addition to the above composition, a coating aid SU-
2, SU-4, SU-5, dispersing aid SU-1, viscosity modifier V-1, stabilizers ST-5, ST-6, antifoggant A
F-1 (polyvinylpyrrolidone, weight average molecular weight: 1)
000), AF-2 (polyvinyl pyrrolidone, weight average molecular weight: 100,000), inhibitor AF-3, AF
-4, AF-5, hardeners H-1, H-3 and preservative F-
1 was added.

The structure of the compound used in the above sample is shown below. SU-1:

[0112]

Embedded image

SU-2:

[0114]

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SU-4: C₈F₁₇SO_TwoN (C_ThreeH₇) CH
_TwoCOOK SU-5: C₈F₁₇SO_TwoNH (CH_Two)_ThreeN⁺(CH_Three)_Three
Br^- ST-5: 4-hydroxy-6-methyl-1,3,3
a, 7-Tetrazaindene ST-6: Adenine AF-3: 1-phenyl-5-mercaptotetrazole AF-4: 1- (4-carboxyphenyl) -5-mer
Captotetrazole AF-5: 1- (3-acetamidophenyl) -5-meth
Lcaptotetrazole H-1: C (CH_TwoSO_TwoCH = C
H_Two)_Four H-3: [(CH_Two= CHSO_TwoCH_Two)_ThreeCCH_TwoSO_TwoC
H_TwoCH_Two]_TwoNCH_TwoCH _TwoSO_ThreeK OIL-1: tricresyl phosphate OIL-2: di (2-ethylhexyl) phthalate AS-1: 2,5-bis (1,1-dimethyl-4-hexyl)
Siloxycarbonylbutyl) hydroquinone AS-2: dodecyl gallate AS-3: 1,4-bis (2-tetradecyloxycal
Bonylethyl) piperazine

[0116]

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[0117]

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[0118]

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[0119]

Embedded image

[0120]

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[0121]

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[0122]

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The sample prepared as described above was used for sample 20.
Let it be 1. Further, a comparative sample was prepared in the same manner as in Sample 201 except that the yellow couplers (Y-5) of the twelfth and thirteenth layers of Sample 201 were changed as shown in Table 2 with the coupler of the present invention and the following comparative coupler. Samples 202-206
And samples 207 to 215 of the present invention were produced. The addition amount of the yellow coupler was adjusted to be the same molar amount as the addition amount in the sample 201, and the high boiling solvent was adjusted so that the addition mass ratio of the yellow coupler to the high boiling solvent (OIL-1) became constant. The amount of (OIL-1) was also increased or decreased.

The structure of the comparative coupler used is shown below.

[0125]

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Each of the prepared samples was 1/1 / white light with white light through a step wedge for sensitometry.
After exposure for 00 seconds and development processing [I] according to the following processing steps, an optical densitometer (PDA manufactured by Konica Corporation)
-65 type), the maximum color density Dmax and the minimum color density Dmin were measured.

Development processing [I] Processing step Processing time Processing temperature Replenishment amount * Color development 3 minutes 15 seconds 38 ± 0.3 ° C. 780 ml Bleaching 45 seconds 38 ± 2.0 ° C. 150 ml Fixing 1 minute 30 seconds 38 ± 2 .0 ° C. 830 ml Stabilizing 60 seconds 38 ± 5.0 ° C. 830 ml drying 1 min 55 ± 5.0 ℃ - * the replenishing amount is a value per photosensitive material 1 m ^2.

The following color developing solutions, bleaching solutions, fixing solutions, stabilizing solutions and replenishers were used. <Color developing solution and color developing replenishing solution> Developer replenishing solution Water 800 ml 800 ml Potassium carbonate 30 g 35 g Sodium hydrogen carbonate 2.5 g 3.0 g Potassium sulfite 3.0 g 5.0 g Sodium bromide 1.3 g 0.4 g Potassium iodide 1.2 mg-hydroxylamine sulfate 2.5 g 3.1 g sodium chloride 0.6 g-4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.5 g 6.3 g diethylenetriamine Pentaacetic acid 3.0 g 3.0 g Potassium hydroxide 1.2 g 2.0 g Add water to make 1 liter, and use potassium hydroxide or 20% sulfuric acid to adjust the color developing solution to pH 10.06 and the replenisher to pH 10.18. Adjust to <Bleaching solution and replenishing solution for bleaching> Replenishing solution for bleaching solution Water 700 ml 700 ml 1,3-diaminopropanetetraacetic acid ammonium (III) ammonium 125 g 175 g ethylenediaminetetraacetic acid 2 g 2 g sodium nitrate 40 g 50 g ammonium bromide 150 g 200 g glacial acetic acid 40 g 56 g In addition, make up to 1 liter, and use ammonia water or glacial acetic acid to adjust the bleaching solution to pH 4. In 4, adjust the replenisher to pH 4.0. <Fixing Solution and Fixing Replenisher> Fixing Solution Replenisher Water 800 ml 800 ml Ammonium thiocyanate 120 g 150 g Ammonium thiosulfate 150 g 180 g Sodium sulfite 15 g 20 g Ethylenediaminetetraacetic acid 2 g 2 g The fixing solution is replenished to pH 6.2 using aqueous ammonia or glacial acetic acid. After adjusting the pH of the solution to 6.5, water is added to make 1 liter. <Stabilizing Solution and Stabilizing Replenishing Solution> Water 900 ml p-octylphenol ethylene oxide 10 mol adduct 2.0 g dimethylol urea 0.5 g hexamethylenetetramine 0.2 g 1,2-benzoisothiazolin-3-one 0.1 g siloxane (manufactured by UCC) L-77) 0.1 g ammonia water 0.5 ml After adding water to make 1 liter, the pH was adjusted to 8.0 using ammonia water or 50% sulfuric acid. Adjust to 5.

Table 2 shows the results.

[0130]

[Table 2]

From the results shown in Table 2, in Comparative Samples 201 to 206 using comparative yellow couplers Y-5, Y-6, Y-7, Y-8, Y-9 and Y-10,
It can be seen that the color developability is poor and the fog is high. In contrast, sample 20 of the present invention using the coupler of the present invention
It can be seen that Sample Nos. 7 to 215 have higher maximum color density and lower fog than the comparative sample. In particular, it can be seen that the samples 211 to 215 using the coupler represented by the general formula [III] of the present invention have excellent performance.

Example 3 Samples prepared in the same manner as in Example 2 (Samples 301 to 31)
5), and exposed to white light for 1/100 second through a step wedge for sensitometry, followed by development processing [I] except that the pH of the color developing solution was 9.90. Development processing (Development processing [II]) in the same manner as I)
Was done. These samples were measured for maximum color density Dmax using an optical densitometer (PDA-65 manufactured by Konica Corporation). Table 3 shows the maximum color density and pH variability. The pH variability was determined from the following equation.

[0133]

(Equation 1)

[0134]

[Table 3]

From the results shown in Table 3, the comparative samples 301 to 306 using the comparative yellow couplers Y-5, Y-6, Y-7, Y-8, Y-9 and Y-10 show that: It can be seen that the maximum color density Dmax is greatly reduced. On the other hand, in the samples 307 to 315 of the present invention using the coupler of the present invention, the reduction of the maximum color density Dmax was smaller than that of the comparative sample, and the maximum color density Dmax was lower.
It can be seen that a dye image having less pH variability of max was formed. In particular, it can be seen that the samples 311 to 315 using the coupler represented by the general formula [III] of the present invention have excellent performance.

As described in detail above, the present invention provides a silver halide color photographic light-sensitive material containing a novel yellow coupler which is excellent in color developability, has high solubility in a solvent, and has excellent dispersion stability. Was completed.

[0137]

According to the present invention, a novel 2 having excellent coloring properties
A silver halide color photographic light-sensitive material containing an equivalent yellow coupler can be provided. Further, it is possible to provide a silver halide color photographic light-sensitive material containing a novel 2-equivalent yellow coupler having high solubility in a solvent, excellent precipitation properties and excellent dispersion stability.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Katsuji Ota, Inventor, Konica Stock Company, 1 Sakuracho, Hino-shi, Tokyo In-house (72) Inventor Satoru Satoru 1, Sakuracho, Hino-shi, Tokyo Konica Incorporated, F-term ( Reference) 2H016 BE02 BF08 BG01 BG02

Claims (8)

[Claims] 1. A silver halide color photographic material comprising at least one coupler represented by the following general formula [I]. Embedded image [In the formula, R ₁ represents a substituent, and R ₂ represents a branched alkyl group having 7 to 20 carbon atoms. R ₃ represents a hydrogen atom or a halogen atom, and m represents an integer of 1 to 5. Z ₁ is> NR ₄
(R ₄ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group) or —O—,
Z ₂ is> NR ₅ (R ₅ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group) or> C (R ₆ ) (R ₇ ) (R ₆ and R ₇ are hydrogen Represents an atom or a substituent). ] 2. The silver halide color photographic light-sensitive material according to claim 1, wherein in the general formula [I], R ₃ is a chlorine atom. 3. A silver halide color photographic material comprising at least one coupler represented by the following general formula [II]. Embedded image [Wherein, R ₁ represents a substituent, and R ₈ represents an alkyl group, a cycloalkyl group, or an aryl group. R ₉ represents an alkyl group or a cycloalkyl group, and the sum of the carbon numbers of R ₈ and R ₉ is 7 to 20. R ₃ represents a hydrogen atom or a halogen atom, and m represents an integer of 1 to 5. Z ₁ is> NR ₄ (R ₄
Represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group) or —O—, and Z ₂ represents> NR ₅ (R ₅ is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl Or a heterocyclic group) or> C
(R ₆ ) (R ₇ ) (R ₆ and R ₇ represent a hydrogen atom or a substituent). ] 4. The silver halide color photographic light-sensitive material according to claim ₃ , wherein in the general formula [II], R ₃ is a chlorine atom. 5. A silver halide color photographic material comprising at least one coupler represented by the following general formula [III]. Embedded image [Wherein, R ₁₀ represents a diffusion-resistant alkyl group, and R ₃ represents a hydrogen atom or a halogen atom. Z ₁ is> NR ₄ (R ₄
Represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group) or —O—, and Z ₂ represents> NR ₅ (R ₅ is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl Or a heterocyclic group) or> C
(R ₆ ) (R ₇ ) (R ₆ and R ₇ represent a hydrogen atom or a substituent). ] 6. The silver halide color photographic light-sensitive material according to claim 5, wherein in the general formula [III], R ₃ is a chlorine atom. 7. The silver halide color photographic material according to claim 5, wherein in the general formula [III], R ₁₀ is an unsubstituted alkyl group having 8 to 21 carbon atoms. 8. The silver halide color photographic light-sensitive material according to claim 5, wherein R ₁₀ in the general formula [III] is represented by the following general formula [IV]. Embedded image [Wherein, R ₁₁ represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and R ₁₂ represents an alkyl group or a cycloalkyl group. n represents an integer of 1 to 10;
Is 2 or more, a plurality of R ₁₁ may be the same or different. The sum of the number of carbon atoms of the group represented by the general formula [IV] is 9 to 22. ]