JPH0259971B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a photographic material containing a novel coupler having a ballast group. By color-developing a color photographic material, an image is generally formed by a coupling reaction between an oxidized aromatic primary amine color developing agent and a color-forming compound generally called a coupler. The dyes formed by coupling are azomethine, indophenol, indoaniline, indamine, phenoxazine, phenazine and similar dyes, depending on the chemical structure of the coupler and developing agent. In this system, subtractive color reproduction is usually used for color reproduction, using silver halide emulsions that are selectively sensitive to blue, green, and red, and yellow, magenta, and cyan color image-forming couplers that are complementary colors, respectively. be done. A large body of patent and technical literature is available regarding compounds that can be used as these couplers. Preferred couplers as yellow image forming agents are acylacetanilides, representative examples of which are listed below. U.S. Patent No. 2875057, U.S. Patent No. 3265506, U.S. Patent No. 3408194
No. 3551155, No. 3582322, No. 3725072,
No. 3891445, No. 4248962, West German Patent No. 1547868,
West German Application No. 2219917, West German Application No. 2261361, West German Publication No.
No. 2414006, British Patent No. 1425020, Special Publication No. 1973-
No. 10783, No. 57-53944, JP-A-47-26133,
No. 48-73147, No. 51-102636, No. 50-6341,
No. 50-123342, No. 50-130442, No. 51-21827
No. 50-87650, No. 52-82424, No. 52-
No. 115219. Preferred couplers as magenta image forming agents include pyrazolone, pyrazolone benzimidazole,
Typical couplers include indazolone, cyanoacetophenone, pyrazolotriazole, and imidazopyrazole, and representative couplers are listed below. US Patent No. 2600788, US Patent No. 2983608, US Patent No. 3062653
No. 3127269, No. 3311476, No. 3419391,
Same No. 3519429, No. 3558319, No. 3582322, Same No.
No. 3615506, No. 3834908, No. 3725067, No.
No. 3891445, No. 4338395, West German Patent No. 1810464,
West German Application Publication No. 2408665, No. 2417945, Special Publication No. 1973
-6031, JP-A-51-20826, JP-A-52-58922,
No. 49-129538, No. 49-74027, No. 50-159336
No. 52-42121, No. 49-74028, No. 50-
No. 60233, No. 51-26541, No. 53-55122, and the applicant's patent application (B) dated February 15, 1982.
Patent application (A) dated March 17, 1958 (applicant: Fuji Photo Film Co., Ltd.). Preferred couplers as cyan image forming agents are phenols and naphthols, representative couplers are listed below. U.S. Patent No. 2369929, U.S. Patent No. 2434272, U.S. Patent No. 2474293
No. 2521908, No. 2895826, No. 3034892,
3311476, 3458315, 3476563, 3458315, 3476563,
No. 3583971, No. 3591383, No. 3767411, No.
No. 4004929, No. 4124396, No. 4333999, No.
No. 4327173, No. 4248962, West German patent application (OLS)
No. 2414830, No. 2454329, JP-A-48-59838,
No. 51-26034, No. 48-5055, No. 51-146828,
No. 52-69624, No. 52-90932, No. 56-80045,
There are also couplers known as black image forming agents, typical examples being resorcinol and m-aminophenol, such as U.S. Pat.
This is described in Japanese Patent Application Laid-open No. 172336/1983. Compounds that couple with oxidized color developing agents in the same manner as couplers but do not form dyes are also known. Compounds of this type modify photographic images by competing with color image-forming agents in reaction with oxidized forms of color developing agents or by releasing photographic active agents such as development inhibitors as a result of coupling reactions. used for In the present invention, these compounds are regarded as couplers because their reaction with the oxidized form of a color developing agent is the same as that of a color image forming agent. Representative compounds are U.S. Patent Nos. 3,632,345, 3,961,959, and U.S. Pat.
It is described in No. 4046574 and No. 4052213. Various methods have been devised for adding couplers such as those mentioned above to photographic emulsion layers.
Introducing a lipophilic ballast group into the coupler molecule,
A method in which the compound is added by dissolving it in an organic solvent and emulsifying it is useful. The following properties are necessary for a coupler having a lipophilic ballast group in order to produce a color light-sensitive material with excellent photographic performance. That is, (1) the coupler and the coloring dye produced during color development have high solubility in the high-boiling organic solvent used for dispersing the coupler (for example, trigreyl phosphate); (2) High stability after dispersion in a silver halide photographic emulsion, and a stable coating film without precipitation of coupler crystals even after coating and drying on a support. (3) It has excellent diffusion resistance and does not diffuse to other layers. (4) Good color development, excellent spectral absorption characteristics of the colored dye image, and high fastness of the dye image to heat, humidity, and light. (5) Easy synthesis from inexpensive raw materials with good reproducibility;
and can be obtained in high yield. etc. Conventionally, many attempts have been made to modify the structure of the balant group in order to improve these properties. As an example of these attempts,
No., Special Publication No. 1977-5391, Special Publication No. 39-27563, U.S. Patent No. 2589004, U.S. Patent No. 2908573, Special Publication No. 1972-3660
No., U.S. Patent No. 2474293, U.S. Patent No. 2039970, U.S. Patent No.
No. 2920961, Special Publication No. 46-36078, Brit No. 944838,
Japanese Patent Publication No. 19026 (1972), US Patent No. 2659329, British Patent No. 1813832, Japanese Patent Publication No. 76834 (1977), Japanese Patent Publication No. 76834 (1977), Japanese Patent Publication No. 76834 (1977),
No. 36856, JP-A-53-82411, OLS2707488,
JP-A-53-139534, JP-A-53-141622, JP-A-54-23528, JP-A-54-48541, JP-A-54-
No. 65035, JP-A-54-99433, JP-A-54-121126
You can list the number etc. However, conventionally known couplers having a ballast group have some defects and do not fully satisfy the above-mentioned necessary properties. these,
Couplers with a lipophilic ballast group are superior to other series of couplers (for example, couplers with an acid group, Although many of these are superior to couplers (which are added to the emulsion layer as a micellar aqueous solution), no one has yet been found that is satisfactory in terms of color development. In high-temperature rapid processing, which has recently become popular, color development is particularly important, and insufficient color development becomes a serious problem. In order to compensate for this insufficient color development, in some cases, an organic solvent such as benzyl alcohol is added to the developer as a color development promoter. However, these organic solvents for promoting color development have several drawbacks. For example, during the development process, it is absorbed into the emulsion layer, so the amount in the developer decreases, resulting in a decrease in color development. It is carried into bleach or bleach-fix solutions, inhibiting desilvering and reducing dye density. It remains in the photosensitive material after processing and reduces color image fastness. It mixes into the treatment liquid and causes an increase in BOD and COD of wastewater. It is highly desirable to remove or reduce the amount of organic solvents used to promote color development. As described in Japanese Patent Application Laid-open No. 58-42045, p.
-Hydroxyphenylenesulfonyl group or p-
Couplers containing a ballast group with a hydroxyphenylene sulfinyl group at the end are improved over conventional couplers in terms of color development, but are still not sufficient and have low solubility in organic solvents for coupler dispersion. It has its drawbacks. The first object of the present invention is to provide a coupler suitable for color photographic materials with excellent photographic properties. A second object of the present invention is to provide a color photographic material having a silver halide emulsion containing a coupler having a novel substituent. The third object of the present invention is to use a coupler having a novel substituent to produce color photographs that have sufficient color development even when organic solvents for promoting color development such as benzyl alcohol are removed or reduced from the color developer. Our purpose is to provide photosensitive materials. A fourth object of the present invention is to provide a color photographic material suitable for rapid processing at high temperatures by using a novel coupler. The present inventors have discovered that the above object can be achieved by a photographic material containing a non-diffusive photographic coupler represented by the following formula (A) or (B). . In both formulas, COUP represents a coupler residue, R represents a hydrogen atom or an organic residue, and when there are two organic residues as R in one formula, they may be the same or different. Also, L indicates (-L ¹ )- _a (-L ² )- _b (-L ³ )- _c , and L ¹ is -O-R ² -, -S-R ² -,

【formula】

[Formula] -R ² - represents a divalent group selected from ^-O- , -S-,

[Formula] -O-R ⁴ -O-,

【formula】

【formula】

[Formula] represents a divalent group, L ³ is -R ⁵ -, -R ⁵ -O-, -R ⁵ -S-,

[Formula] -SO ₂ -,

【formula】

【formula】

It represents a divalent group selected from [Formula], a, b and c each represent 0 or 1, and the coupler residue represented by COUP is any of the coupler residues commonly used in photographic light-sensitive materials. The residue other than COUP that binds to COUP is a group that makes the coupler non-diffusive, and R ² , R ⁴ and R ⁵ are an alkylene group (having 1 to 20 carbon atoms) and an arylene group, respectively. (6 to 22 carbon atoms)
and an aralkylene group (7 to 22 carbon atoms), R ³ is a hydrogen atom, an alkyl group (1 to 18 carbon atoms)
and an aryl group (having 6 to 22 carbon atoms). The organic residue represented by R may be any group commonly used in couplers, such as an alkyl group (having 1 to 18 carbon atoms), an allyl group (having 6 to 10 carbon atoms), or a heterocyclic group. , acyl group, sulfonyl group, hydroxy group, carboxy group, imino group, halogen atom, cyano group, nitro group, amino group, acylamino group, carbamoyl group, sulfonamide group, sulfamoyl group, ureido group, alkoxy group, alkylthio group, These include allyloxy group and allylthio group. Preferred R is a hydrogen atom, an alkyl group (carbon number 1
~18), aryl group (6 to 22 carbon atoms), alkoxy (1 to 18 carbon atoms), allyloxy group (6 to 22 carbon atoms),
22) and halogen atoms, cyano groups, acylamino groups, sulfonamide groups, carbamoyl groups, etc. In each of the above structural formulas, the alkyl group, aryl group, alkylene group, arylene group and heterocyclic group are unsubstituted, or an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, heterocyclic group, Substituted with one or more groups such as heterocyclooxy group, heterocyclothio group, halogen, nitro, amino, hydroxy, carboxy, amide, carbamoyl, sulfonamide, sulfamoyl, sulfamoylamino, ureido, cyano, etc. Good too. Examples of couplers for use in the present invention shown below include ballast groups of the following structural formulas ^B1 - ^B15 .

【table】

【table】

【table】

【table】

【table】

Claims (1)

[Scope of Claims] 1. A photographic material characterized by containing a non-diffusive photographic coupler represented by the following formula (A) or (B). In both formulas, COUP represents a coupler residue, R represents a hydrogen atom or an organic residue, and when there are two organic groups as R in one formula, they may be the same or different. Often, L indicates (-L ¹ )- _a (-L ² )- _b (-L ³ )- _c , and L ¹ is -O-R ² -, -S-R ² -, [Formula] [Formula ] -R ² - represents a divalent group selected from -O-, ^-S- , [Formula] -O-R ⁴ -O-, [Formula] [Formula] [Formula] Indicates a divalent group, L ³ is 2 selected from -R ⁵ -, -R ⁵ -O-, -R ⁵ -S-, [Formula] -SO ₂ -, [Formula] [Formula] [Formula] a, b and c each represent 0 or 1; the coupler residue represented by COUP may be any of the coupler residues commonly used in photographic materials; The bonding residues other than COUP are groups that make the coupler non-diffusive, R ² ,
R ⁴ and R ⁵ are an alkylene group (1 to 20 carbon atoms), an arylene group (6 to 22 carbon atoms), and an aralkylene group (7 to 22 carbon atoms), respectively, and R ³ is a hydrogen atom, an alkyl group (carbon Numbers 1 to 18)
and an aryl group (having 6 to 22 carbon atoms).