JPH01200254A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve processing stability by incorporating a phenolic cyan coupler having an ureide group in the 2nd position into at least one layer of silver halide emulsion layers and incorporating the compd. expressed by the specific compsn. formula, etc., into the silver halide emulsion layer contg. said cyan coupler. CONSTITUTION:The silver halide photographic sensitive material having the silver halide emulsion layers on a base contains the phenolic cyan coupler having the ureide group in the 2nd position in at least one layer of the silver halide emulsion layers thereof. The compd. expressed by the formula I or the salt thereof is incorporated into the silver halide emulsion layer contg. said cyan coupler. In the formula, Y denotes an oxygen atom or sulfur atom; X denotes -NHCO(CH2)2COOH or -OC2H5 or -S(CH2)m-Z-OH (Z is CH2 or CO); (a), (b), (g) respectively denote 0 or 1 integer. (c) Denotes 0-3 integer; (d), (e) respective ly denote 0-2 integer; (f) denotes 2-6 integer; (m) denotes 1-6 integer and has >=3 sulfur atoms in the molecule. The example, of the formula I is shown by the formulas II, III.

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 particularly to a silver halide color photographic light-sensitive material with improved processing stability. be.

(Prior Art) Conventionally, as a cyan coupler used in a red-sensitive emulsion layer of a color negative light-sensitive material, which does not cause reduction fading in a bleaching process or a bleach-fixing process, for example, JP-A No. 5
Phenolic Kabra having a ureido group at the 2-position described in No. 6-65134 and No. 58-118643 are known.

However, color light-sensitive materials using such couplers have the drawbacks of slightly high fog and large fluctuations in photographic performance due to changes in development processing conditions.

(Object of the present invention) An object of the present invention is to provide an excellent silver halide color photographic light-sensitive material which has excellent processing stability and has little fog.

(Structure of the Invention) As a result of extensive studies, the present inventors found that in a silver halide photographic light-sensitive material having a silver halide emulsion layer on a support, at least one of the silver halide emulsion layers has a ureido group at the 2-position. A silver halide color photographic light-sensitive material containing a phenolic cyan coupler having the following formula, and a silver halide emulsion layer containing the cyan coupler containing a compound represented by the following general formula (S) or a salt thereof, can be used to produce the above-mentioned I found that the purpose was achieved.

General formula [S] In the formula, Y 1. is an oxygen atom or a sulfur atom, and X is -NH
Co(CH2)2COOH1-〇C2H5 or -3(C
H2) m-Z-OH (Z is CI+2 or CO), a,
b, g are each an integer of 0 or l, C is an integer of 0 to 3, d, e are each an integer of 0 to 2, f is an integer of 2 to 6, m is an integer of 1 to 6. and has 3 or more sulfur atoms in the molecule.

Furthermore, examples of the salt of the compound represented by the general formula [S] include alkali metal salts and ammonium salts.

Among these, X is -5(CH2) l
l1-Z -OH (Z and m are synonymous with general formula [S])
, f is 2, and the molecule has 4 or more sulfur atoms.

Furthermore, the substitution position of the substituent containing a sulfur atom is preferably the ortho position or the meta position.

The amount of these compounds added is preferably 0.001 to Log, more preferably 0.01-1 g per mole of silver halide.

Next, representative examples of the compound represented by the general formula [S] will be shown.

These compounds can be synthesized in various ways.

For example, a method in which a halogenated methyl-substituted benzene derivative is reacted with a mercapto alcohol, a method in which the hydroxy group of the reaction product hydroxyalkylthiomethyl-substituted benzene is halogenated, and then a mercap]-substituted carboxylic acid is reacted with the hydroxyl group, and hydroxybenzene. A method is used in which a halogenated thioether having a hydroxy group or a carpoquine group is reacted with the halogenated thioether.

More specifically, it is described in US Pat. No. 4,713,322 and the like.

There is no particular restriction on the timing of addition of the compound represented by the general formula [S], and examples include before and during silver halide crystal formation, during physical ripening, during chemical ripening, and after chemical ripening until coating. .

As the phenolic cyan coupler having a ureido group at the 2-position, those represented by the general formula CI) are preferred.

General formula (1) In the formula, 6 groups represented by R1 or R2 include those having a substituent, including those forming a dimer or more multimer by R4 or R2, R,, R2 alone, or jointly have a coupler represented by general formula CI) and a shape or size necessary to impart diffusion resistance to a dye formed from the coupler.

The aryl group represented by R1 or R2 includes a phenyl group and a naphthyl group.

Examples of the aliphatic group represented by R2 include an alkyl group and an alkenyl group, and examples of the heterocyclic group represented by R1 include a furyl group, a thienyl group, a pyridyl group, a quinolyl group, an oxacyl group, a tetrazolyl group, Examples include benzothiazolyl group and tetrahydrofuranyl group.

Examples of substituents for the group represented by R1 or R2 include nitro, cyan, halogen, alkyl, aryl, amino, hydroxy, acyl, alkoxycarbonyl, aryloxycarbonyl, alkylsulfonyl, arylsulfonyl, alkoxysulfonyl, and aryloxysulfonyl. , carbamoyl, sulfamoyl, acyloxy, carbonamide, sulfonamide, etc., and the number of substituents is preferably 1 to 5, and when it is 2 or more, each substituent may be the same or different.

Preferred substituents for R are alkylsulfonyl, cyano, and halogen, and preferred as R2 are those represented by general formula (IT).

General formula (If) In the formula, J is an oxygen atom or a sulfur atom, k is an integer from 0 to 4, Q is 0 or 1, and when k is 2 or more, two or more R4s are the same or different. R3
represents an alkylene group, and R represents a substituent.

Examples of the substituent represented by R4 include alkyl, aryl, alkoxy, aryloxy, hydroxy, acyloxy, alkylcarbonyloxy, arylcarbonyloxy, carboxy, alkoxycarbonyl, aryloxycarbonyl, alkylthio, acyl, acylamino, and sulfone. Amide, carbamoyl, sulfamoyl, etc. are mentioned.

Examples of the leaving group represented by Further, specific examples include U.S. Pat.
No. 425, Japanese Patent Publication No. 48-36894, Japanese Patent Publication No. 1977-1
No. 0135, No. 50-117422, No. 50-130
No. 441, No. 5l-jp No. 8841, No. 50-1203
No. 34, No. 52-18315, No. 53-105226
In particular, halogens,
Those bonded through oxygen atoms are preferred.

Next, specific examples of phenolic Kagura having a ureido group at the 2-position will be shown.

(Exemplary compound) I-3 ■-17 OH ■-20 ■-21 ■-23 ■-24 ■-28 ■-32 ■.

■-33 ■-34 ■-35 ■-36 ■-40 ■-43 ■-44 ■-45 A47 ■-48 Knee 50 ■-52 ■-55 ■-56 ■-62 ■-63 sHz (L ) ■-64 l-65 ■-68 ■-72 Shi U ■-73 ■-74 Shi Q ■-7 Ro I -81 ■-88 Knee 89 ■-92 ■-95 ■-96 ■-97 ■-98 ■-99 6H1l-L In the present invention, in order to incorporate the cyan coupler of the present invention into the silver halide emulsion layer, conventionally known methods,
For example, the cyan coupler of the present invention may be added to a mixture of a high boiling point solvent such as known dibutyl heptatarate, tricresyl phosphate, dinonylphenol, etc. and a low boiling point solvent such as butyl acetate, propionic acid, etc., either alone or in combination. After dissolving, it is mixed with an aqueous gelatin solution containing a surfactant, and then emulsified and dispersed using a high-speed rotary mixer, colloid mill, or ultrasonic dispersion machine, and then directly added to the emulsion, or the above-mentioned emulsified dispersion is carried out. After setting the liquid, it may be shredded, washed with water, and then added to the emulsion.

The amount of the uncoupler used in the present invention is usually 1. It ranges from 10-3 moles of OX to 1.0 moles, preferably from 5X 10-' moles to 8X 10-' moles.

The cyan couplers of the present invention may be used alone or in combination of two or more. Furthermore, cyan couplers other than the cyan coupler of the present invention may be used in combination.

The silver halide emulsion used in the light-sensitive material of the present invention can be chemically sensitized by conventional methods, and can be optically sensitized to a desired wavelength range using a sensitizing dye.

Antifoggants, stabilizers, etc. can be added to the silver halide emulsion. Gelatin is advantageously used as binder for the emulsion.

The emulsion layer and other hydrophilic colloid layers can be hardened, or can contain a plasticizer or a dispersion (latte/mixture) of a water-insoluble or sparingly soluble synthetic polymer.

Kabra is used in the emulsion layer of light-sensitive materials for color photography.

Furthermore, by coupling with a colored coupler having a color correction effect, 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, Fogging agent, antifogging agent, chemical sensitizer,
Compounds that release photographically useful fragments such as spectral sensitizers and desensitizers can be used.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, an antiirradiation layer, and the like.

These layers and/or the emulsion layer may contain dyes that are washed out or bleached from the light-sensitive material during the development process.

Photosensitive materials include formalin scavengers, optical brighteners,
A matting agent, a lubricant, an image stabilizer ζ surfactant, a color cast inhibitor, a development accelerator, a development retardant and a bleach accelerator can be added.

As a support, paper laminated with polyethylene, etc.
Polyethylene terephthalate film, baryta paper, cellulose triacetate, etc. can be used.

To obtain a dye image using the photosensitive material of the present invention, after exposure,
Commonly known color photographic processing can be performed.

〔Example〕

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

Example 1 In the Examples, the amount added in the silver halide photographic light-sensitive material indicates + per 1 m2 unless otherwise specified. In addition, silver halide is shown in terms of silver.

] - A multilayer color photographic element sample 1 was prepared by sequentially forming each layer having the composition shown below on a cellulose cellulose film support from the support side.

Sample-1 (comparison) First layer; antihalation layer (IC-1) Gelatin layer containing black colloidal silver.

Dry film thickness: 3 μm Second layer: Intermediate layer (1,L,) Gelatin layer containing an emulsified dispersion of 2.5-di-t-octylhydroquinone.

Dry film thickness 1.0 μm Third layer; low sensitivity red-sensitive silver halide emulsion layer (RL-1)
Monodisperse emulsion consisting of AgBr I with an average grain size (r) of 0.3077 m and containing 3 mol% of Agl (emulsion ■: width of distribution 12%)...silver coating amount 1.8 g/m2 Sensitizing dye I ... 6 x 10-' morph sensitizing dye for 1 mole of silver ■... 1. OX 10-'Morsian coupler (C-1)... 0.06 mol per mol of silver Colored cyan coupler (CC-1)... 0.003 mol DIR compound (D -1)... 0.0015 mol per mol of silver DIR compound (D -2)... 0.002 mol per mol of silver Dry film thickness 3.5 μm 4th layer: High red sensitivity Silver halide emulsion layer (RH-1)
Average particle size (r) 0.5 μm, Agl 3.0 mol%
Monodisperse emulsion consisting of AgBr1 (emulsion ■: width of distribution 12%)...Silver coating amount: 1.3 g/a+" Sensitizing dye I...3 x 10-' mol per 1 mol of silver Sensitizing dye...
- 1.0% per mole of silver. OX 10-' mol Cyan coupler (C-1)... 0.02 mol per 1 mol of silver Colored cyan coupler (CC-1)... 0.0015 mol DIR compound (D -2)... 0.001 mol per mol of silver Dry film thickness 2.5 μm Fifth layer: Intermediate layer (1, L,) Same as the second layer, gelatin layer.

Dry film thickness 1.0 μm 6th layer; low-sensitivity green-sensitive silver halogenide emulsion layer (GL-1
) Emulsion I: Coated silver amount: 1.5 g/m" Sensitizing dye■
... 2.5X 10-' mol sensitizing dye for 1 mol of silver.
... 1.2X 10-' mole magenta coupler (M-1) for 1 mole of silver... o, oso mole colored magenta coupler (CM-1) for 1 mole of silver... 0.009 mol for DIR compound (D-1)... 0.0010 mol for 1 mol of silver DIR compound (D-3)... 0.0030 mol for 1 mol of silver Dry film thickness 3 .5 μm 7th layer: High-sensitivity green-sensitive silver halogenide emulsion layer (GH-1
) Emulsion■...Coating amount silver 1.4g/m" Sensitizing dye■
... 1.5X 10-' mol sensitizing dye for 1 mol of silver.
... 1 mole of silver. OX 10-' mol Magenta coupler (M-1)... 0.020 mol per mol of silver Colored magenta coupler (CM-1)... 0.002 mol DIR compound (D -3)... 0.0010 mol per mol of silver Dry film thickness 2.5 μm 8th layer: Yellow filter layer (YC-1) Emulsion of yellow colloidal silver and 2.5-di-t-octylhydroquinone a gelatin layer comprising a dispersion;

Dry film thickness 1.2 μm 9th layer; low sensitivity blue-sensitive silver halide emulsion layer (BL-1)
Monodispersed emulsion consisting of AgBr1 with an average grain size of 0.48/7 m and containing 3.0 mol% of Agl (emulsion ■: width of distribution 12%)...Silver coating amount 0.9 g/m" Sensitizing dye ■... 1.3X 10-' moles per mole of silver Yellow coupler (Y-1)... 0.29 moles per mole of silver Dry film thickness 3.5 μm 1st O layer: High sensitivity blue Sensitive emulsion layer (BH-1) average grain size 0
．． 8 μm, AgBr I containing 3.0 mol% Agl
Monodispersed emulsion (emulsion ■: width of distribution 12%)... Silver coating amount 0.5 g/m2 Sensitizing dye ■... 1.5 g/m2 per mole of silver. OX 10-'mol Yellow Cabra (Y-1)... 0.08 mol per mol of silver DIR compound (D-2) 0.0015 mol per mol of silver Dry film thickness 2.5 μm 11th Layer: First protective layer (Pro-1) silver iodobromide (Ag
l 2 mol% average particle size 0.07 μm)... Silver coating amount 0
．． 5 g/m" Gelatin layer containing ultraviolet absorbers UV-1 and UV-2 Dry film thickness 2.0 μm 12th layer; 2nd protective layer (Pro-2) polymethyl methacrylate particles (diameter 1.5 μm) and formalin Gelatin layer containing scavenger (H3-1), dry film thickness 1.5 μm In addition to the above composition, each layer also contains gelatin hardening agent (H-1
) and surfactants were added.

The compounds contained in each layer of sample 1 are as follows.

Sensitizing dye ■: Anhydro-5,5'-dichloro-9-ethyl-3,3'-di(3-sulfopropyl)thiacarbocyanine hydroxide Sensitizing dye ■: Anhydro-9-ethyl-3,3'- Di(3-sulfopropyl)-4,5,4',5'-dibenzothiacarbocyanine hydroxide sensitizing dye ■; Anhydro-5,5'-diphenyl-9-
Ethyl-3,3'-di(3-sulfopropyl)oxacarbocyanine hydroxide sensitizing dye ■: Anhydro-9-ethyl-3,3'-di(3-sulfopropyl)-5,6,5',6 '-Dibenzoxacarbonanine hydroxide sensitizing dye V: Anhydro 3.3'-di(3-sulfopropyl)-4,5-benzo-5'-methoxy thiacyanine C-1, Exemplary Compound 1-104 C -1 h 01] H and L M-1 Cθ CO.

V-1 V-2 H3I H1 Next, in sample 1, replace the uncoupler (C-1) of the third and fourth layers as shown in Table 1, and
．． 4.6. At the time of emulsion formation of 7.9 and 10 silver halide emulsion layers, the compound represented by general formula (S) was added as shown in Table-I to prepare samples No. 2 to No. 83. did.

Each sample thus obtained was exposed to wedge light using a conventional method, and then developed as described below.

For development, use a developer with the following color developer composition at 38°C.
Color development is carried out by changing the development time for ±30 seconds around 15 seconds, and bleaching, fixing, and stabilizing treatments are carried out using bleaching solution, fixing solution, and stabilizing solution with the following compositions for the following times. At the same time, washing with water was performed.

Color developer composition Near 4-amino-3-methyl-N-ethyl ■ 1 Hydroquinylamine 1/2 sulfate 2.0 g ゛ Potassium hydroxide 1.0 g Add water to make IQ and adjust pH to 10.0 adjust.

Bleach solution composition: Ni-ethylenediaminetetraacetate iron ammonia water added to I
Q and adjust the pH to 6.0.

Fixer composition: Ammonium thiosulfate 50% aqueous solution 162+n (1\anhydrous sodium sulfite 12.4 m0°) Add water to make Iff and adjust the pH to 6.5.

Stabilizing liquid composition: /Bolf 9f 37% aqueous solution 5.0m (2
＼Cordax (manufactured by Konishiroku Photo Industry Co., Ltd.) 7.5 mQ Add water to make 112.

Development process (38°C) Processing time Color development ・・・・・・・・・・・・ 3 minutes 15 seconds ±
Bleach for 30 seconds...
・ ... Wash with water for 6 minutes and 30 seconds ... ・
・・ ・ ・ ・ ・ ・ 3 minutes 15 seconds fixed ・ ・ ・ ・ ・ ・ 6 minutes 30
Wash with water for seconds ・・・ ・・・ ・ ・
・・Stabilized bath for 3 minutes and 15 seconds・・・・・・・・・・・・・
... 1 minute 30 seconds No. 1 to No. 0 processed as above
．． Table 1 shows the measurement results of the fog, relative sensitivity, and the difference in fog (△ fog) when the red-sensitive layer of No. 83 was developed for 2 minutes and 45 seconds and when it was developed for 3 minutes and 45 seconds.

In Table 1, ■Fog and ■Relative sensitivity are the results of standard development processing (development time 3 minutes 15 seconds), and ■ is the result of development time changes of 2 minutes 45 seconds and 3 minutes 45 seconds. As is clear from No. 1, the samples of the present invention have further reduced fog without substantially lowering sensitivity, and have significantly improved performance with variations in development processing conditions.

Furthermore, even when cyan coupler 1-3 was used in place of cyan coupler 1-104 in Samples 2 and 14, fog and performance due to variations in development processing conditions could be improved.

Claims (1)

[Scope of Claims] In a silver halide photographic material having a silver halide emulsion layer on a support, at least one of the silver halide emulsion layers contains a phenolic cyan coupler having a ureido group at the 2-position. A silver halide color photographic light-sensitive material characterized in that the silver halide emulsion layer containing the cyan coupler contains a compound represented by the following general formula [S] or a salt thereof. General formula [S] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, Y is an oxygen atom or a sulfur atom, and X is -NHCO
(CH_2)_2COOH, -OC_2H_5 or -S
(CH_2)_m-Z-OH (Z is CH_2 or CO
), a, b, g are each an integer of 0 or 1, c is 0 to 3
d and e each represent an integer of 0 to 2, f represents an integer of 2 to 6, m represents an integer of 1 to 6, and has 3 or more sulfur atoms in the molecule. ]