JPH02188748A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the silver halide color photographic sensitive material having good color developability and sufficient color developing density by incorporating a specific coupler into a red photosensitive silver halide emulsion layer. CONSTITUTION:The coupler expressed by the formula I is incorporated into the red photosensitive silver halide emulsion layer. In the formula I, R1 denotes a cyano group, nitro group, perfluoroalkyl group, alkylsulfonyl group, perfluoroalkylsulfonyl group, 2-benzoimidazoryl group, acyl group, 1-tetrazolyl group, perfluoroalkoxy group, sulfamoyl group or hydrogen bondable group. R2 denotes a hydrogen atom or substituent; X denotes the nonmetal atom group necessary for forming 5- to 7-membered satd. heterocyclic groups together with N. The good color developability and the sufficient color developing density are obtd. in this way and the color reproducibility is improved; in addition, the change in the hue of the dyestuff image by heat and humidity is decreased.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, a silver halide color photographic light-sensitive material containing a cyan dye-forming coupler that has active point substitution and excellent color development. Regarding materials.

[Background of the invention]

Phenols or naphthols have been widely used as cyan image forming couplers.

However, cyan images obtained from conventionally used phenols and naphthols have serious problems in terms of color reproduction. The reason is that the absorption is not sharp on the short wavelength side, and there is unnecessary absorption, that is, asymmetric absorption, in the edge region. As a result, in the case of negatives, it is necessary to correct the asymmetric absorption by masking or the like, and in the case of paper, there is no means for correction, and the current situation is that the color reproducibility is considerably deteriorated.

Furthermore, dye images obtained from conventionally used phenols and naphthols still have some problems in their storage stability. For example, US Pat. No. 2,367.
The dye images obtained from the 2-acylaminophenolic cyan couplers described in U.S. Pat. No. 531 and U.S. Pat.
29 and 2,772.162, the dye images obtained with the 2.5-diacylaminophenolic cyan couplers generally have poor light fastness and are
-The dye image obtained from the Natsutamido cyan coupler is
Generally, both light and heat fastness are unsatisfactory.

Also, U.S. Patent No. 4,122,369, JP-A-57-15
2,5-diacylaminophenol cyan couplers described in US Pat. No. 5538 and US Pat. Phenolic cyan couplers have not yet reached a satisfactory level in terms of fastness to light and heat and yellow stain generation in order to preserve dye images for a long period of time.

In order to solve these problems,
No. 3-199352, No. 63-250649, No. 63
A pyrazoloazole type cyan coupler has been proposed in, for example, No. 250650.

However, these couplers all have electron-withdrawing groups and hydrogen-bonding groups introduced in order to satisfy the absorption wavelength of the coloring dye formed, so their coupling activity is greatly reduced. The biggest problem is that the color development is extremely poor compared to conventional phenol and 7-tall cyan couplers.

As a result of various studies regarding the above-mentioned problems, the present inventors succeeded in discovering a pyrazoloazole type cyan coupler having good coloring properties, and completed the present invention.

[Purpose of the invention]

Accordingly, a first object of the present invention is to provide a silver halide color photographic light-sensitive material that has good color development properties and provides sufficient color density.

A second object of the present invention is to provide a silver halide color photographic light-sensitive material that provides a clear cyan image with sharp absorption and little absorption in the blue and edge regions, so-called excellent spectral absorption characteristics. It is in.

A third object is to provide a silver halide color photographic material capable of forming a cyan image that does not change in hue due to heat or humidity.

[Structure of the invention]

The above object of the present invention is to provide a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, in which the red-sensitive silver halide emulsion layer contains a coupler represented by the following general formula (I). This was achieved using a silver halide color photographic light-sensitive material containing .

General formula (I) In the formula, 'RI is a cyano group, a nitro group, a perfluoroalkyl group, an alkylsulfonyl group, a perfluoroalkylsulfonyl group, a carbamoyl group, an alkoxycarbonyl group, a pentafluorophenyl group, a 2-benzoxasilyl group , 2-benzothiazolyl group, 2-benzimidazolyl group, acyl group, l-tetrazolyl group, perfluoroalkoxy group, sulfamoyl group, or a hydrogen-bonding group, R1 represents a hydrogen atom or a substituent, and X is N It represents a group of nonmetallic atoms necessary to form a 5- to 7-membered saturated heterocycle.

[Specific structure of the invention]

The coupler represented by general formula [I] will be explained in detail.

Perfluoroalkyl groups represented by R include trifluoromethyl, pentafluoroethyl, heptafluoropropyl, etc.; alkylsulfonyl groups include methylsulfonyl, butylsulfonyl, dodecylsulfonyl, etc.: perfluoroalkylsulfonyl Examples of the group include trifluoromethylsulfonyl, pentafluoroethylsulfonyl, etc.; carbamoyl groups include methylcarbamoyl, dimethylcarbamoylurbamoyl, etc.; alkoxycarbonyl groups include:
Groups such as methoxycarbonyl and tetradecyloxycarbonyl; Acyl groups include acetyl and benzoyl; Perfluoroalkoxy groups include trifluoromethoxy groups; Sulfamoyl groups include methylsulfamoyl and diethylsulfamoyl , phenylsulfamoyl, etc., and these groups may further have a substituent.

When R1 represents a hydrogen bonding group, typical hydrogen bonding groups include (R a, R h, R C, R d, Re and Rf represent a hydrogen atom or a substituent, Q is 0 or l, m represents l or 2, and n represents an integer of O to 4; however, when n is 2 or more, Rf may be the same or different.

Furthermore, 2 represents a nonmetallic atomic group necessary to form a nitrogen-containing heterocycle. ) etc.

Ra and Rh each represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residue, or the like.

Re represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residue, a sulfonyl group, a sulfinyl group, a carbonyl group, etc.

Rd represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residue, or the like.

Re represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residue, a sulfonyl group, a sulfinyl group, a carbonyl group, etc., and preferably a sulfonyl group, a sulfinyl group, and a carbonyl group.

Rf represents a hydrogen atom and a substituent, but the substituent represented by Rf is not particularly limited.

The above-mentioned substituents may further include substituents such as long-chain hydrocarbon groups and diffusion-resistant groups such as polymer residues.

In the present invention, particularly preferred hydrogen-bonding groups represented by R1 include the following.

■ Preferred ones are -SO2NHRc, -SONHRc
, -CONHRcR, preferred are a perfluoroalkyl group, an alkylsulfonyl group, a perfluoroalkylsulfonyl group, a carbamoyl group, a 2-acylaminophenyl group, and a 2-sulfonamidophenyl group.

There are no particular limitations on the substituent represented by R2. Typically, there are six groups such as alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, and cycloalkyl, but in addition to these, there are halogen atoms and nitro, hydroxyl, cycloalkenyl, alkynyl, and heterocyclic groups. , sulfonyl, sulfinyl,
phosphonyl, acyl, carbamoyl, sulfamoyl,
cyano, alkoxy, aryloxy, heterocyclic oxy,
6 groups of siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, and spiro compound residues, Also included are bridged hydrocarbon compound residues and the like.

The alkyl group represented by R2 preferably has 1 to 32 carbon atoms, and may be linear or branched.

The aryl group represented by R3 is preferably a phenyl group.

Examples of the acylamino group represented by R3 include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group represented by R1 include an alkylsulfonylamino group and an arylsulfonylamino group.

Examples of the alkyl component and aryl component in the alkylthio group and arylthio group represented by R2 include the alkyl group and aryl group represented by R1 above.

The alkenyl group represented by R7 has 2 to 32 carbon atoms.
The cycloalkyl group preferably has 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and the alkenyl group may be linear or branched.

The cycloalkenyl group represented by R2 has 3 carbon atoms.
-12, especially 5-7 are preferred.

Sulfonyl groups represented by R3 include alkylsulfonyl groups, arylsulfonyl groups, etc.; sulfinyl groups include alkylsulfinyl groups, arylsulfinyl groups, etc.; phosphonyl groups include alkylphosphonyl groups, alkoxyphosphonyl groups, and aryloxyphosphonyl groups. , arylphosphonyl group, etc. Niacyl groups include alkylcarbonyl groups, arylcarbonyl groups, etc.; carbamoyl groups include alkylcarbamoyl groups, arylcarbamoyl groups, etc.; sulfamoyl groups include alkylsulfamoyl groups,
Niacyloxy groups such as arylsulfamoyl groups include alkylcarbonyloxy groups, arylcarbonyloxy groups, etc.; carbamoyloxyloxy, etc.; ureido groups include alkylureido groups, arylureido groups, etc.; sulfamoylamino groups include alkylsulfa groups; Moylamino group, arylsulfamoylamino group, etc.; 5- to 7-membered heterocyclic groups are preferable, specifically 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, etc. ; The heterocyclic oxy group preferably has a 5- to 7-membered heterocycle, for example, 3,
4.5.6-tetrahydropyranyl-2-oxy group, l
-Phenyltetrazole-5-oxy group, etc.; The heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, such as 2-pyridylthio group, 2-benzothiazolylthio group, 2.4-diphenoxy-1 , 3,5-triazole-6 monothio group, etc.; Siloxy groups include trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc.; imide groups include succinimide group, 3-heptadecylsuccinimide group, phthalimide group. group, glutarimide group, etc.; spiro compound residues include spiro[3,3]hebutane-! -yl, etc.; Bicyclo[2゜2, l
] Hep 9 Sea 1 Ill, To! J Schiffa I3.3-1
-1'']]decan-1-yl7,7-siphthyrubicyclo[2,2,11butan-1-yl and the like.

Preferred examples of R7 include a halogen atom, anilino, acylamino, sulfonamide, sulfonyl, sulfinyl, acyl, carbamoyl, sulfamoyl,
cyano, alkoxy, aryloxy, acyloxy,
The six groups are carbamoyloxy, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, and nitro, and more preferred are acylamino, sulfonamide, sulfonyl, acyl, carbamoyl, and sulfonyl. There are six groups: moyloxy and aryloxy.

A 5- to 7-membered saturated heterocycle formed by X together with N is formed.

These can further have a substituent, and the substituents include halogen atoms, alkyl, aryl, heterocycle,
Alkylamino, anilino, acylamino, sulfonamide, ureido, alkoxycarbonylamino, carbamoyl, sulfamoyl, acyl, sulfonyl, alkoxycarbonyl, aryloxycarbonyl, alkoxy, aryloxy, alkylthio, arylthio, cyano, nitro, carboxyl, hydroxyl, etc. Representative examples of the compounds of the present invention are shown below.

,・X・, No.

R.

12H21 No.

Rt R.

No.

R1 R8 One inch Z ...Kuji [ C0NHC+, H3i l-8O8 N.J. CIHII(L) Typical synthesis examples of the compounds of the present invention are shown below.

Synthesis Example 1 (Synthesis of Exemplary Compound 2) Reaction Scheme (A) Compound Compound (A) described in JP-A-63-264753
250 mff of acetic acid and 5IIQ of hydrochloric acid were added to 33.1 g of the solution and kept at 15°C. An aqueous solution of 3.5 g of sodium nitrite was added dropwise thereto, and the mixture was stirred for 2 hours. The reaction solution was added to ice water IQ, and the precipitated solid was filtered, washed with water, and dried. This was recrystallized from a mixed solvent of ethyl acetate and hexane, and 27 of (B) was obtained.
．． Obtained 0g.

Next, dissolve 26g of (B) in 500mQ of alcohol,
% palladium-carbon catalyst was added for catalytic hydrogenation. The catalyst was filtered and concentrated under reduced pressure to obtain (C).

Next, (C) 6.8g, n-butanol 30ml, water 3
Add 0+aQ and 2.5g of sodium hydrogen carbonate, 90
℃ and add 3.48 g of 1,5-dibromopentane.
was added dropwise over 10 minutes. The reaction was further carried out at 90°C to 100°C for 4 hours, the aqueous layer was removed, the n-butanol layer was washed with water, and then concentrated under reduced pressure. After the residue was purified by silica gel chromatography, it was recrystallized from a mixed solvent of ethyl acetate and hexane to obtain 4.8 g of Exemplary Compound (2).

The structure of this product was identified by NMR spectrum and mass spectrum.

Synthesis Example 2 (Synthesis of Exemplified Compound 4) To 6.8 g of (C) in Synthesis Example 1, 50 ml of n-butanol was added.
and 1.4 g of vinyl sulfone were added, and the mixture was heated under reflux for 6 hours. After concentrating under reduced pressure, the residue was purified by silica gel chromatography, and then recrystallized from a mixed solvent of ethyl acetate and hexane to obtain 3.6 g of Exemplary Compound (4).

The structure of this product was identified by NMR spectrum and mass spectrum.

In the silver halide photographic light-sensitive material of the present invention, the cyan coupler of the present invention is contained in an amount of 0.1-
It is desirable to add 100 mol%, preferably 5 to 50 mol%, but this can be changed as necessary.

The couplers of the present invention can be used in combination of two or more types, and can also be used in combination with other types of cyan couplers.

The coupler of the present invention can be produced by solid dispersion method, latex dispersion method,
It can be added to silver halide photographic materials using various methods such as oil-in-ice emulsion dispersion method. For example, in the oil-in-water emulsion dispersion method, a hydrophobic additive such as a coupler is usually added to a high-boiling organic solvent with a boiling point of about 150°C or higher, such as tricresyl phosphate or dibutyl phthalate, and if necessary, ethyl acetate, butyl propionate, etc. After dissolving it in combination with a low boiling point and/or water-soluble organic solvent, and emulsifying and dispersing it in a hydrophilic binder such as an aqueous gelatin solution using a surfactant,
It may be added to the desired hydrophilic colloid layer.

When the color photographic light-sensitive material of the present invention is used as a full-color light-sensitive material, a yellow coupler and a magenta coupler are used in addition to the cyan coupler according to the present invention. Yellow coupler There are no particular restrictions on the magenta coupler, and any known magenta coupler can be used.

As the yellow coupler, for example, acylacetanilide couplers can be used, including benzoylacetanilide and pivaloylacetanilide compounds.

As the magenta coupler, for example, 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, and open-chain acylacetonitrile couplers can be used.

The silver halide color photographic light-sensitive material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation.

The silver halide color photographic light-sensitive material of the present invention may contain various other photographic additives. For example, antifoggants, development accelerators, development retarders, bleach accelerators, stabilizers, ultraviolet absorbers, color stain inhibitors, optical brighteners,
Color image fading prevention agent, antistatic agent, hardening agent, surfactant,
Plasticizers, wetting agents, etc. can be used. (research·
You can refer to Disclosure Magazine No. 17643. ) Furthermore, by coupling with a competing coupler and an oxidized form of a developing agent, a development accelerator, a bleach accelerator, a developer, a silver halide solvent, a toning agent, a hardening agent, a fogging agent, an antifogging agent, a chemical sensitizer, Compounds that release photographically useful fragments such as spectral sensitizers and desensitizers can be used.

The support for the silver halide color photographic light-sensitive material of the present invention is
Examples include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plates, polyester films such as cellulose acetate, cellulose nitrate, and polyethylene terephthalate, polyamide films, polycarbonate films, and polystyrene films. In the case of transparent supports, reflective layers are used. May be used together.

These supports are appropriately selected depending on the intended use of the photosensitive material.

For coating the emulsion layer and other constituent layers used in the present invention, a number of coating methods can be used, such as dipping coating, air doctor coating, curtain coating, and hopper coating. Also, U.S. Patent No. 2.781.791, 2
It is also possible to use a simultaneous coating method of two or more layers by the method described in No. 941,898.

In the present invention, the coating position of each emulsion layer can be determined arbitrarily, but the coating positions of the blue-sensitive silver halide emulsion layer, the green-sensitive silver halide emulsion layer, and the red-sensitive silver halide emulsion layer are sequentially applied from the support side. It is preferable to set it as an array.

In the photosensitive material of the present invention, it is optional to provide an intermediate layer with an appropriate thickness depending on the purpose, and a filter layer,
Various layers such as an anti-curl layer, a protective layer, and an antihalation layer can be used in appropriate combinations as constituent layers. Hydrophilic colloids can be used as binders in these constituent layers, and gelatin is preferably used. Further, the various photographic additives mentioned in the explanation of the emulsion layer can be contained in the layer.

There are no particular limitations on the method of processing photographic materials using the silver halide emulsion of the present invention, and any commonly known processing method can be applied. For example, typical methods include a method in which a bleach-fixing process is performed after color development, and further washing and/or stabilization treatment if necessary; a method in which bleaching and fixing are performed separately after color development; The silver halide color photographic light-sensitive material of the present invention may be processed using any method of water washing and/or stabilization processing, but the silver halide color photographic light-sensitive material of the present invention can be processed in the steps of color development, bleach-fixing, and water washing (or stabilization). Suitable for rapid processing.

〔Example〕

Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

Example-1 Here, the present invention was applied to color paper.

That is, on a paper support laminated on both sides with polyethylene, the following layers were sequentially coated from the support side to prepare silver halide color photographic material No. 1''18.

Layer 1 - 1.2 g/m" gelatin, 0.32 g/m"
Blue-sensitive silver chlorobromide emulsion (silver chloride content 99.3 mol%) (in terms of silver, the same applies hereinafter), 0.80 g/m'' of yellow coupler (Y -1) A layer containing.

Layer 2...0.70g/m'' gelatin, 30mg/m
” anti-irradiation dye (Al-1), 20mg
An intermediate layer consisting of (A l-2) of /m''.

Layer 3 - 1.25g/m" gelatin, 0.25g/m"
green-sensitive silver chlorobromide emulsion (silver chloride content 99.5 mol%)
, 0.74 g/m'' of magenta coupler (M-1) dissolved in 0.30 g/l 112 of dioctyl phthalate.

Layer 4: Intermediate layer consisting of 1-20 g/m'' gelatin.

Layer 5 - 1.20 g/m" gelatin, 0.30 g/m"
red-sensitive silver chlorobromide emulsion (silver chloride content 99.7 mol%)
, 0.9 mmol/m dissolved in 0.45 g/m2 of dioctyl phthalate! A layer containing a cyan coupler shown in Table 1.

Layer 6 = 1.00 g/m" gelatin and 0.20 g/m"
0.30 g dissolved in g/m' dioctyl phthalate
/m'' of ultraviolet absorber (UV-1).

Layer 7: A layer containing 0.50 g/m'' of gelatin.

C-1 Shiri C-2 I-1 I Note that sodium 2,4-dichloro-6-hydroxy-S-triazine is added as a hardening agent in layers 2, 4 and 7.
Each was added in an amount of 0.017 g per 1 g of gelatin.

The obtained sample was measured using a sensitometer KS-7 model (manufactured by Konica Corporation).
After wedge exposure using an optical densitometer (Konica Corporation PD
A-65 type) to determine the maximum density (Dmax) of the red photosensitive layer
) was measured.

Processing process Temperature Time color development
34.7±0.3℃ 45 seconds bleach fixing
34.7±0.5℃ Stabilized for 45 seconds
Dry at 30-34℃ for 90 seconds
60-80℃ 60 seconds Color developer Pure water
800mff triethanolamine
8g N,N-diethylhydroxylamine 5g Potassium chloride
2g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 5g sodium tetrapolyphosphate 2g potassium carbonate
30g potassium sulfite
0.2g Fluorescent brightener (4,4'-diaminostilbendisulfonic acid derivative) 1g Add pure water to make a total volume of 1Q, and adjust the pH to 10.2.

Bleach-fixing solution Iron (III) ethylenediaminetetraacetic acid Ammonium dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100ml 12 Ammonium sulfite (40% I solution) 27.5ml Add water to make the total volume Iff, Potassium carbonate Or adjust the pH to 5.7 with glacial acetic acid.

Stabilizing liquid 5-chloro-2-methyl-4-isothiazoline-3-off 1g 1-hydroxyethylidene-1, todiphosphonic acid 2g Add water to make IQ, and adjust pH to 7.0 with sulfuric acid or potassium hydroxide.
Adjust to.

In addition, the color reproducibility of the sample No. 1''18 was evaluated using the following method.

First, color negative film (Konica Color GX-100
: manufactured by Konica Corporation) and camera (Konica FT-l M
OTOR (manufactured by Konica Corporation) was used to photograph a color checker manufactured by Macbeth. Subsequently, a color negative development process (CNK-4: manufactured by Konica Corporation) was performed, and the obtained negative image was printed on the above sample No. 1-18 with a size of 82 mm x 117 mm using a Konica color printer CT-P2000 (manufactured by Konica Corporation). A practical print was obtained by printing in the same size as in Example 1 above. Printer conditions during printing were set for each sample so that gray on the color checker turned gray on the print.

The color reproducibility and blackness of the obtained practical prints were visually evaluated.

Table-1 Δ Color reproducibility (hue, saturation) insufficient 0 Color reproducibility (hue, saturation) good ◎ Color reproducibility (hue, saturation) very good As is clear from Table-1, Samples No. 1 containing the cyan coupler CC-1 outside the present invention have good color development and a high maximum density, but are extremely unsatisfactory in color reproducibility.

On the other hand, sample No. 2 containing cyan coupler CC-2, which is not of the present invention, greatly improves color reproducibility, but
Because the maximum density is low, the blackness is poor.

In contrast, sample N containing the cyan coupler of the present invention
Nos. 0 and 3 to 18 all have good color development, high maximum density, and good color reproducibility and black background.

〔Effect of the invention〕

The silver halide color photographic light-sensitive material using the novel active site substitution type cyan coupler having high reactivity according to the present invention has good color development properties and can obtain sufficient color development density. In addition, absorption in blue and edge regions, which is a drawback of conventionally used cyan couplers, is reduced, and color reproducibility is greatly improved. Furthermore,
There is also little hue change in dye images due to heat and humidity.

Claims (1)

[Scope of Claims] In a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, the red-sensitive silver halide emulsion layer contains a coupler represented by the following general formula [I]. A color photographic material containing silver halide. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. Represents a fluorophenyl group, 2-benzoxazolyl group, 2-benzothiazolyl group, 2-benzimidazolyl group, acyl group, 1-tetrazolyl group, perfluoroalkoxy group, sulfamoyl group, or a hydrogen-bonding group, and R_2 is a hydrogen atom or represents a substituent, and X represents a group of nonmetallic atoms necessary to form a 5- to 7-membered saturated heterocycle together with N. ]