US3888680A - Light-sensitive silver halide color photographic material containing bis-pyrazolone couplers - Google Patents

Light-sensitive silver halide color photographic material containing bis-pyrazolone couplers Download PDF

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US3888680A
US3888680A US42820773A US3888680A US 3888680 A US3888680 A US 3888680A US 42820773 A US42820773 A US 42820773A US 3888680 A US3888680 A US 3888680A
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light
coupler
sensitive silver
silver halide
halide color
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Mitsuto Fujiwhara
Keiji Kasai
Ryosuke Satoh
Yoshinobu Nakagawa
Tuneo Tanigawa
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Konica Minolta Inc
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Konica Minolta Inc
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Priority to US20779671A priority
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Priority to US42820773 priority patent/US3888680A/en
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Assigned to KONICA CORPORATION reassignment KONICA CORPORATION RELEASED BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: KONISAIROKU PHOTO INDUSTRY CO., LTD.
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/32Colour coupling substances
    • G03C7/36Couplers containing compounds with active methylene groups
    • G03C7/38Couplers containing compounds with active methylene groups in rings
    • G03C7/384Couplers containing compounds with active methylene groups in rings in pyrazolone rings
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D231/00Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/44Oxygen and nitrogen or sulfur and nitrogen atoms
    • C07D231/52Oxygen atom in position 3 and nitrogen atom in position 5, or vice versa

Abstract

A light-sensitive silver halide color photographic material is disclosed which comprises a bis-type coupler of the following general formula:

WHEREIN R is alkyl, aralkyl or aryl X, Y and Z are individually hydrogen, halogen or alkyl or alkoxyl group having 1 to 4 carbon atoms, one of X and Z being a halogen atom; and n is zero or 1.

Description

United States Patent [1 1 Fujiwhara et a1.

[ June 10, 1975 Assignee:

LIGHT-SENSITIVE SILVER HALIDE COLOR PHOTOGRAPHIC MATERIAL CONTAINING BIS-PYRAZOLONE COUPLERS Inventors: Mitsuto Fujiwhara; Keiji Kasai;

Ryosuke Satoh; Yoshinobu Nakagawa; Tuneo Tanigawa, all of Tokyo, Japan Konishiroku Photo Industry Co., Ltd., Tokyo, Japan Filed: Dec. 26, 1973 Appl. No.: 428,207

Related US. Application Data Continuation-impart of Ser. No. 207,796, Dec. 14, 1971, abandoned.

Foreign Application Priority Data Dec. 18, 1970 Japan 45413100 U.S. Cl 96/100; 260/310 A Int. Cl G03c 1/40 Field of Search 96/100, 56.5

[56] References Cited UNITED STATES PATENTS 2,294,909 9/1942 Jennings 96/100 2,403,040 7/1946 Bavley 3,468,666 9/1969 Shiba et a1. 96/100 Primary Examiner- 1. Travis Brown Attorney, Agent, or Firm-Bierman & Bierman [57] ABSTRACT A light-sensitive silver halide color photographic material is disclosed which comprises a bis-type coupler of the following general formula:

having 1 to 4 carbon atoms, one of X and Z being a halogen atom; and n is zero or 1.

4 Claims, No Drawings I 2 LIGHT-SENSITIVE SILVER I-IALIDE COLOR pyrazolone nucleus, with which is concerned the pres- PHOTOGRAPHIC MATERIAL CONTAINING ent invention, is low in solubility for high boiling sol- BIS-PYRAZOLONE COUPLEIRS vent due to the hydrophilic property of the coupler res- This application is a continuation-in-part of applicaidue, and undesirably deposits in a dispersion thereof tion Ser. No. 207,796 filed Dec. 14, 1971, now aban- 5 or in the resulting film. cloned, and it claims priority of Japanese application With an aim to overcome the abovementioned draw- No: l 13100/1970 filed Dec. 18, 1970. backs, the synthesis of bis-pyrazolone type couplers has This invention relates to a light-sensitive color photobeen attempted, and Japanese Patent Publication No. graphic material containing a novel coupler of the py- 26,589/1969 discloses a process for preparing light razolone type for forming a magenta color photograhl0 sensitive photographic materials incorporated with said pic image. couplers. However, the couplers of this type, which has For the formation of color photographic images acth h i al structure cording to the conventional substractive color photography, there have been used, in general, couplers capable of forming yellow, magenta and cyan dye images by R:

coupling with an oxidation product of N,l l'-di- P c u substituted p-phenylenediamine type developing agent. I. ffi

Particularly in the so-called internal color photography 9-05 OH-C in which the above-mentioned couplers are incorpoi rated into photographic emulsions to develop colors, 1 3 R1 there are two processes; a process in which a hydrophilic coupler containing in the molecule a nondiffusing group and a hydrophilic group such as a group are not only undesirable in solubility as shown in the f th f l -COOH or 50 11 i di l d i an test example set forth later, but also slow in color develalkali solution or the like and then dispersed in a photooping rate at the time of color development and low in graphic emulsion, and a process in which an oleophilic Sensitivity of green light Sensitive layer, 50 that the coupler, which contains no hydrophilic group in the dependent use thereof is diffieultm l ule and which h b r d d il l bl b As the result of extensive studies, we have found maintroduction of an oleophilic group (e.g. a higher alkyl genta Couplers which have been improved in Solubility group), is dispersed to extremelyfine oil drops in a high and deposition P p y at the time Of dispersion and boiling solvent such as di-n-butyl phthalate or tricresyl Coating and which Can g p tral absorption characphosphate d th incorporated i a h hi teristics suitable for color reproduction. That is, we emulsion. have found new couplers of the bis-pyrazolone type,

In the former case, the coupler is easily dispersible in Obtained y ensing a Coupler of the general foran aqueous emulsion. However, a coupler having a sulfone group brings about a great variation in viscosity of the emulsion, and the control of film thickness at the time of coating the emulsion becomes extremely difficult. Further, a coupler having a carboxyl group is Q 'J somewhat low in solubility for alkali solution and, in 40 0= c NH (1) case the emulsion, which has been diluted before coat- :6

ing, becomes neutral or weakly acidic, the coupler deposits in the emulsion to deteriorate the transparency of the resulting image. In the latter case, the tendency Y of deposition of the coupler in the emulsion is greatly dominated by the extent of hydrophilic property of the wherein R is an alkyl, aralkyl or aryl group; X, Y and coupler residue, the kinds and amounts of non- Z are individually a hydrogen or halogen atom, or an diffusing group and coupler solvent, etc. This tendency alkyl or alkoxy group having 1 to 4 carbon atoms, eiis observed as well in the case of a magenta coupler, ther one of said X and Z being necessarily a halogen and an internal oleophilic magenta coupler, which has atom; and n is zero or l, with formaldehyde in acetic a S-pyrazolone, pyrazolinobenzimidazole, acid. pyrazoloquinazolone or indazolone ring incorporated The above-mentioned couplers have the following with a non-diffusing group such as a long chain alkyl, chemical structure:

dialkylphenoxy or alkoxy group, is greatly dominated Among the couplers of the above general formula in said tendency by the extent of hydrophilic property (I), those which can give new couplers of the general of the coupler residue, the kind and amount of the nonformula (II) displaying particularly excellent properties diffusing group. Particularly, a coupler having 5"- are compounds of the following structure:

It is to be noted that compounds usable in the present invention are not limited to the above-mentioned compounds.

The accompanying drawing shows variations in density due to amounts of exposure of dye images obtained by subjecting to color development two light-sensitive color photographic materials containing, respectively, a coupler according to the present invention and a known coupler.

Procedures for synthesizing the magenta couplers used in the present invention are set forth below with reference to synthesis examples.

SYNTHESIS EXAMPLE 1 To a solution of 7.3 g. (0.01 mole) of l-(6-chloro- 2,4-dimethylphenyl)-3-(a-3-n-pentadecylphenoxy) butyrylamide-benzamide-S-pyrazolone (the compound 4) in 30 ml. of acetic acid was added 1.5 ml. of 37% formaldehyde, and the resulting mixture was stirred at room temperature and concentrated under reduced pressure to form a gelatinous substance. To this substance was further added a solution of 7.3 g. (0.01 mole) of the said coupler in 30 ml. of acetic acid, and the resulting mixture was boiled under reflux for 20 minutes and then concentrated under reduced pressure. The concentrate was recrystallized from acetonitrile to obtain 12.0 g. (81.6% on theoretical basis) of white crystals, m.p. 107.5108.5C.

Elementary analysis:

C H N Cl Calculated (71) 71.05 7.81 7.62 4.82 Found (7t) 7095 7.63 7.44 4.81

Structural formula:

HEOCBO SYNTHESIS EXAMPLE 2 To a solution of 13.4 g. (1/50 mole) of l-(2,4,6- trichlorophenyl)-3-[3-(2.4-di-t-amylphenoxy) acetamide-bezamide]-5-pyrazo1one (the compound 1) in ml. of acetic acid was added 3 ml. of 37% formaldehyde, and the resulting mixture was stirred for 30 minutes at room temperature (2527C.) and then concentrated under reduced pressure to form a gelatinous substance. To this substance was further added a solution of 13.4 g. (0.02 mole) of the said coupler, and the resulting mixture was boiled under reflux for 30 minutes and then concentrated under reduced pressure. The concentrate was recrystallized from ether to obtain 21.3 g. (79.5% on theoretical basis) of pale yellow crystals, m.p. 238242C.

Elementary analysis:

SYNTHESIS EXAMPLE 3 l3 Grams (0.02 mole) of l-(2,4,6-trichlorophenyl)- on -sc c-mico micccn oQzu r ompound P s n TEST, EXAMPLE The above-mentioned compounds were compared each other in solubility for high boiling solvent and indeposition property after storage by measuring the amount of di-n-butyl phthalate used to dissolve 100 m g. of each coupler in said solvent at 60C. and the time required for deposition of the coupler when the coupler solution was allowed to stand at to 27C.. The re sults obtained were as set forth in Table l.

3-(3-n-dodecylsuccinimide-benzamide)-5-pyrazolone Table 1 (the compound 2) was treated in the same manneras 30 h E l 1 t s nthesize a crude bis-t 6 Amount Tlme for m y e515 xampe 0 y yP Coupler dl-n-butyl deposition coupler. This crude product was recrystallized from phthalate used methanol to obtain 10.5 g. (89.4% on theoretical basis) Compound A 1.2 20 hrs. of a whlte powder, mp. 120 l22 C. Compound B 2.0 ml. 18 hrs. Elementary analysis: compolnd 1) 19 ml .20

Formalmbis derivative of C H N Cl compound (1) 0.15 ml. Non-deposition (Coupler of Calculated 59.31 5.76 8.65 16.41 Synthesis Found 59.18 5.86 8.89 16.15 Example 2) 40 Compound (4) 0.8 ml. 20 hrs.

Formalin-bis derivative of Structural formula? compound (4) 0.5 ml. Non-deposition lnlH c -CH -CO ONHC CH 25 t li g-o-clg-Hc CNHCO-Q CH2 -cO o=c k CO-CH-C H ("l N/ 0 C1 co-cu The couplers synthesized according to the above- (C P 0f Synthesis mentioned procedures are excellent in solubility and Example I) favorable in deposition property after storage as com- Compound 1 1 part pared with such known alkylidene-bis compound $335 2 (compound A disclosed in Japanese Patent Publication i pm shown below, and with the known mono-type compounds (the compounds 1 and 4) Example 2 As is clear from Table 1, the compounds of the present invention are excellent in solubility for high boiling solvent. Moreover, the compounds A and B are extremely low in color developing rate at the time of color development, so that the independent use thereof is considerably difficult, whereas the compounds of the present invention are markedly excellent in color developing rate (refer to the accompanying drawing) and display prominent photographic properties (refer, for example, to Table 2).

Applications of the couplers used in the present invention are set forth below with reference to examples.

EXAMPLE 1 l Grams of the coupler synthesized in Synthesis Example l was completely dissolved at 60C. in a mixed solvent comprising ml. of di-n-butyl phthalate and 20 ml. of ethyl acetate. This solution was mixed with a 10% aqueous solution of Alkanol B (trade name for a surface active agent produced by Du Font) and with 200 ml. of a 5% aqueous gelatin solution, and then subjected to a colloid mill to form a dispersion. The thus formed dispersion was added to and dispersed in 1,000 ml. of a green sensitive silver iodobromide emulsion, which was then coated on a film base and dried to obtain a green sensitive color photographic material. This film was exposed and then developed with a developer of the following composition:

N,N-Diethyl-p-phenylenediamine hydrochloride 2.0 g. Sodium sulfite (anhydrous) 2.0 g. Sodium carbonate (monohydrate) 82.0 g. Potassium bromide 2.0 g. Water to make 1,000 ml.

The developed film was subjected to ordinary fixing and water-washing and then treated for 5 minutes with a bleaching solution of the following composition:

Potassium ferricyanide 100 g. Potassium bromide 50 g. Water to make 1,000 ml.

Subsequently, the film was fixed for 5 minutes with a fixing solution comprising 200 g. of sodium thiosulfate (pentahydrate) and 1,000 of water, washed with water for 20 to 30 minutes and then dried. The film gave a fine-grain magenta color image excellent in transparency and having an absorption maximum at 546 mu.

EXAMPLE 2 Example 1 was repeated, except that the coupler used was replaced by the coupler synthesized in Syn- Rco "(Migthesis Example 2, to obtain a film. This film gave a finegrain magenta color image excellent in transparency and having an absorption maximum at 556 mu.

EXAMPLE 3 Example 1 was repeated, except that the coupler used was replaced by a mixture comprising 5 g. of the coupler synthesized in Synthesis Example 2 and 5 g. of

the exemplified compound (1), to obtain a film. This film gave a fine-grain magenta color image having an absorption maximum at 556 mu.

When the films obtained in the above examples are compared in photographic properties with photographic films incorporated with any of the compounds A, B, l and (4), it is understood that the films according to the present invention are extremely high in durability of dye image and in density of developed color, as seen in Table 2.

Light fastness" in Table 2 represents the ratio of residual color after exposing the film to light for 20 hours by use of Fade-O-meter.

Characteristic curves of the compound A and the compound of Synthesis Example 2 are shown in the accompanying drawing, in which the solid line shows the case of the compound A and the dotted line shows the case of the compound of Synthesis Example 2.

As is clear from Table 2 and the drawing, the couplers of the present invention are excellent not only in color developability but also in storability, and hence are quite useful couplers.

What we claim is:

1. A light-sensitive silver halide color photographic material containing a bis-type coupler of the general formula,

\N =c \N/N XQZ XQVZ Y Y wherein R is an alkyl, aralkyl or aryl group; X, Y and Z are individually a hydrogen or halogen atom or an alkyl or alkoxy group having 1 to 4 carbon atoms, either one of said X and Z being necessarily a halogen atom; and n is zero or 1.

2. A light-sensitive silver halide color photographic 0-0 ,ll NHCOCHO 3,888,680 9 10 3. A light-sensitive silver halide color photographic 4. A light-sensitive silver halide color photographic material as claimed in claim 1, wherein said bis-type material as claimed in claim 1, wherein said bis-type coupler is a compound of the structural formula coupler is a compound of the structural formula lnm c -lcu :o N c H 2 N A-O-CH -HC c um-Q cow H O=C N I 12

Claims (4)

1. A LIGHT-SENSENTIVE SILVDR HALIDE COLOR PHOTGRAPHIC MATERIAL CONTAINING A BIS-TYPE COUPLER OF THE GENERAL FORMULA,
2. A light-sensitive silver halide color photographic material as claimed in claim 1, wherein said bis-type coupler is a compound of the structural formula
3. A light-sensitive silver halide color photographic material as claimed in claim 1, wherein said bis-type coupler is a compound of the structural formula
4. A light-sensitive silver halide color photographic material as claimed in claim 1, wherein said bis-type coupler is a compound of the structural formula
US42820773 1970-12-18 1973-12-26 Light-sensitive silver halide color photographic material containing bis-pyrazolone couplers Expired - Lifetime US3888680A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4171975A (en) * 1977-02-10 1979-10-23 Konishiroku Photo Industry Co., Ltd. Light-sensitive silver halide color photographic materials
US4283472A (en) * 1980-02-26 1981-08-11 Eastman Kodak Company Silver halide elements containing blocked pyrazolone magenta dye-forming couplers
US4310618A (en) * 1980-05-30 1982-01-12 Eastman Kodak Company Silver halide photographic material and process utilizing blocked dye-forming couplers
EP0201033A2 (en) 1985-04-30 1986-11-12 Konica Corporation A method for processing silver halide color photographic materials
EP0711804A2 (en) 1994-11-14 1996-05-15 Ciba-Geigy Ag Latent light stabilizers

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2294909A (en) * 1939-02-13 1942-09-08 Du Pont Chemical process and composition
US2403040A (en) * 1944-07-06 1946-07-02 Gen Aniline & Film Corp Color photography
US3468666A (en) * 1966-05-05 1969-09-23 Fuji Photo Film Co Ltd Color photographic silver halide light-sensitive materials containing bis-pyrazolone couplers

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2294909A (en) * 1939-02-13 1942-09-08 Du Pont Chemical process and composition
US2403040A (en) * 1944-07-06 1946-07-02 Gen Aniline & Film Corp Color photography
US3468666A (en) * 1966-05-05 1969-09-23 Fuji Photo Film Co Ltd Color photographic silver halide light-sensitive materials containing bis-pyrazolone couplers

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4171975A (en) * 1977-02-10 1979-10-23 Konishiroku Photo Industry Co., Ltd. Light-sensitive silver halide color photographic materials
US4283472A (en) * 1980-02-26 1981-08-11 Eastman Kodak Company Silver halide elements containing blocked pyrazolone magenta dye-forming couplers
US4310618A (en) * 1980-05-30 1982-01-12 Eastman Kodak Company Silver halide photographic material and process utilizing blocked dye-forming couplers
EP0201033A2 (en) 1985-04-30 1986-11-12 Konica Corporation A method for processing silver halide color photographic materials
EP0711804A2 (en) 1994-11-14 1996-05-15 Ciba-Geigy Ag Latent light stabilizers

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Effective date: 19871021