US3761274A - Light sensitive color photographic material - Google Patents

Light sensitive color photographic material Download PDF

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Publication number
US3761274A
US3761274A US00161953A US3761274DA US3761274A US 3761274 A US3761274 A US 3761274A US 00161953 A US00161953 A US 00161953A US 3761274D A US3761274D A US 3761274DA US 3761274 A US3761274 A US 3761274A
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US
United States
Prior art keywords
group
coupler
photographic material
lower alkyl
color photographic
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Expired - Lifetime
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US00161953A
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English (en)
Inventor
I Inoue
T Hanzawa
T Endo
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Konica Minolta Inc
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Konica Minolta Inc
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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/32—Colour coupling substances
    • G03C7/36—Couplers containing compounds with active methylene groups
    • G03C7/38—Couplers containing compounds with active methylene groups in rings
    • G03C7/384—Couplers containing compounds with active methylene groups in rings in pyrazolone rings

Definitions

  • ABSTRACT on THE DISCLOSURE A light-sensitive silver halide colorphotographic material containing a compound of the general formula,
  • W is a hydrogen atom, or a phenylazo group
  • X, Y and Z which may be same or diflerent, are individually a hydrogen or halogen atom, a lower alkyl group, a lower alkoxy group, a phenoxy group or a group of the formula COOR, (where R is a lower alkyl group);
  • A is a divalent group of the formula NH-e NH or s V (where R, is a hydrogen or halogen atom);
  • ml is an integer of 1 or 2;
  • R is a hydrogen atom or a lower alkyl group; and R is an aliphatic hydrocarbon residue having 8 to 16 carbon atoms.
  • X, Y and Z which may be same or difierent, are individually: ahydrogen or a halogen :"atom'; a lower alkyl group, a lower alkoXy "group; a phenoxy” group or a 3,761,274 Patented Sept. 25, 1973 group of the formula COOR (where R is a lower alkyl group); A is a divalent group of the formula NH- (where R, is a hydrogen or halogen atom); in is an integer of 1 or 2; R is a hydrogen atom or a lower alkyl group; W is a hydrogen atom or a phenylazo group; and R is an aliphatic hydrocarbon residue having 8 to 16 carbon atoms.
  • H2C HJ NHCOC1EHS1 the coupler disclosed in US. Pat. No. 2,694,703 which has the general formula
  • couplers can be synthesized easily and at relatively low cost. These couplers, however, have low solubility in high boiling solvents and are readily crystallizable, so that it is extremely difficult to use them as couplers of the protect type.
  • the coupler of the aforesaid general formula which is used in the present invention can be prepared simply and economically by utilizing a certain color-forming nucleus and by using as starting materials alkyl bromide and catechol which can be obtained com- .merically with ease and at low cost.
  • the thus prepared coupler is easily soluble in a high boiling solvent such as phthalate or tricresyl phosphate, so that the amount of solvent for the coupler can bedecreased to make it possible to obtain a highly concentrated dispersion.
  • the coupler synthesized in the above'manner has a low melting point and hence has the characteristic that it is diflicultly crystallized in a photographic emulsion or in a film formed by coating and drying the emulsion.
  • the light-sensitive color photographic material according to the present invention which has been incorporated with said coupler is favorable in durability and easily soluble in a high boiling solvent, so that the photographic material is excellent in spectral absorption characteristic and can give a color image which is favorable in transparency and high in density.
  • the coupler used in the present invention may be synthesized according to, for example, the following procedures:
  • a long chain alkyl bromide and catechol are condensed with in dimethylformamide in the presence of potassium bicarbonate to form a catechol monoalkyl ether, which is then condensed with a halogeno-fatty acid to obtain a long chain alkoxyphenoxy fatty acid. Subsequently, this acid is treated with phosphorus pentachloride to form the corresponding acid chloride, which is then condensed with a coupler component having an amino group, whereby the coupler used in the present invention can be synthesized.
  • couplers having the aforesaid general formula are set forth below, but couplers usable in the present invention are not limited to these examples.
  • the thus obtained long chain alkoxyphenoxy fatty acid is formed into an acid chloride by treament with phosphorus pentachloride.
  • a suspension of 36.4 g. of 2-dodecyloxyphenoxy acetic acid in ml. of chloroform is charged with 23 g. of phosphorus pentachloride, allowed to stand for 30 minutes and then heated for 30 minutes in a water bath kept at 60 C. Thereafter, by-produced phosphorus oxychloride and chloroform are removed by distillation under reduced pressure, and the residual chloride is used in the subsequent acylation step.
  • the oily substance was dissolved in ethyl acetate and dried with anhydrous sodium sulfate, and then the solvent was removed by distillation under reduced pressure.
  • the residual brown oily substance was dissolved in 200 ml. of hexane to deposit a white precipitate, which was then recovered by filtration, washed with a small amount of hexane and then dried to obtain 12.0 g. (57.4%) of a White powder, M.P. 667 C.
  • the exemplified Compounds 2 to 14 could be synthesized by the condensation of acid chloride having a different alkayl chain with nuclei having different substituents.
  • the solubility in high boiling solvent is represented by the amount (ml.) of dibutyl phthalate necessary to dissolve 1 g. of each coupler.
  • test results showing the fact that the low boiling solvent by water-washing or the like treatment and incorporated into a silver halide photographic emulsion, which is then coated on such a support as mentioned above and dried to prepare a light-sensitive color photographic material.
  • the above-mentioned incorporation procedure is illustrative and is not limitative.
  • the amount of the coupler to be incorporated into the photographic emulsion is ordinarily to 100 g. per mole of the silver couplers according to the present invention give color 10 halide contain! therein, but is P ye lifflited to images excellent in spectral absorption characteristics Sald range and 1S Varlable aceofdlng t0 applleatlon P are set forth in Table 2.
  • AM A a chemical sensitizer
  • the results set forth in Table 2 are measured values of a noble metal salt.
  • the emulsion may further contain, color images'formed according to Example 1.
  • ordinary photographic additives such as, for example,
  • the antifoggant, stabilizer, anti-stain agent, anti-irradiation couplers used in the present nvention give color Images agent, physical property-improving high polymer ddiexcelleht specfral Ql characterfstlctive, film hardener, coating aid, etc.
  • the F P fh couPlers used f P emulsion may contain a known carbocyanine dye, merolnventloninto llght-sensltlve color photographic materials, cyanine dye or the like as an optical sensitizer for the there may be adopted any of the known procedures. For emulsion.
  • the resulting solution is mixed dFVekPPmg and then sublected bleiichmg with an aqueous gelatin-solution containing a surfactant sllvemfg and fixmg
  • a surfactant sllvemfg and fixmg to obtam 3' hlgh denvslty and than emulsified by means of a high speed rotary color image excellent in spectral absorption charactermixer or a colloid mill.
  • a $0101 p e p ie contamhalide photographic emulsion and coated on a support 2 the e p 0f the P e e lIlventlel'l can glve a 90101 such as a glass plate, synthetic resin plate, film base or image of Improved durablhty when the photogra hic m alaminated paper, and then a major proportion of the low terial is incorporated with an ultraviolet absorber of the boiling solvent is removed by drying to prepare a light-senbenzophenone type, e.g.
  • 2-hydroxy-4-dodecyloxybenzo sitive color photographic material 2-hydroxy-4-dodecyloxybenzo sitive color photographic material.
  • the said phenone, or of the triazole type, e.g. 2-(2'-hydroxy-3',5'- coupler emulsion is once set, finely cut, freed from the di-tert-butylphenyl)benzotriazole.
  • Typical examples of the deveolping agent used for de velopment of the light-sensitive color photographic material of the present invention are sulfates, sulfites and hydrochlorides of the following:
  • the color developer used for development of the photographic material may contain, in addition to the above-mentioned developing agent, a developmentcontrolling agent such as citrazinic acid or the like.
  • EXAMPLE 1 10.0 grams of the exemplified coupler (9) was added to a mixed solvent comprising 10 ml. of dibutyl phthalate and 30 ml. of butyl acetate and then heated to 60 C., whereby the coupler was completely dissolved to form a solution.
  • This solution was mixed with ml. of a aqueous solution of Alkanol B (alkylnaphthalene sulfonate produced and sold by Du Pont) and with 100 ml. of a 5% aqueous gelatin solution, and the mixed solution was subjected to a colloid mill to prepare a dispersion.
  • Alkanol B alkylnaphthalene sulfonate produced and sold by Du Pont
  • This coupler dispersion was incorporated into 1 kg. of a high speed light-sensitive gelatinous silver iodobromide photographic emulsion, which was then coated on a film base and dried to obtain a light-sensitive photographic film.
  • the developed photographic film was subjected to ordinary stopping and fixing treatments, washed with water for 10 to minutes and then treated for 5 minutes with a bleaching solution of the following composition:
  • the thus treated photographic film was washed with water for 5 minutes, fixed for 5 minutes in a fixing bath comprising 250 g. of sodium thiosulfate and 1,000 ml. of water, washed with water for to mm utes and then dried to obtain a clear magenta color image having an absorption maximum at 550 mu.
  • EXAMPLE 2 subjected to a colloid mill to prepare a coupler dispermen.
  • This dispersion was incorporated into 500 g. of a gelatin silver iodobromide emulsion, which was then coated on a film base and dried to obtain a photographic film.
  • the developed photographic film was subjected to ordinary stopping, hardening and water-washing treatments, and then to secondary exposure by use of a white light. Thereafter, the photographic film was developed at 21 C. for 13 minutes with a developer of the following composition:
  • the thus developed photographic film was subjected to ordinary stopping, water-washing, bleaching and fixing treatments, washed with running water for 20 minutes and then dried to obtain a positive magenta color image having an absorption maximum at 540 me which was excellent in transparency.
  • EXAMPLE 3 10 grams of the exemplified coupler (l) was mixed with 20 ml. of dibutyl phthalate and then heated to 50 C., whereby the coupler was completely dissolved to form a solution. This solution was mixed with 5 ml. of a 10% aqueous solution of Alkanol B and with 200 ml. of a 5% aqueous gelatin solution, and the mixed solution was subjected several times to a colloid mill to prepare a coupler dispersion. This dispersion was incorporated into 500 g. of a gelatin silver chlorobromide emulsion, which was then coated on a baryta paper and dried to produce a lightsensitive photographic material.
  • the developed photographic material was dipped for 2 to 4 minutes in a stopping and fixing bath of the following composition:
  • EXAMPLE 4 2.0 grams of the exemplified coupler (15) was added to a mixed solvent comprising 2 ml. of dibutyl phthalate and 6 ml. of butyl acetate, and then heated to 60 C., whereby the coupler was completely dissolved to form a solution. This solution was mixed with 1 ml. of a 10% aqueous solution of Alkanol B and with 20 ml. of a 5% aqueous gelatin solution, and then emulsified to prepare a coupler dispersion. Subsequently, the coupler dispersion was incorporated into 100 g. of a high speed silver iodobnomide photographic emulsion, which was then coated on a film base and dried to produce a lightsensitive photographic film.
  • This photographic film was exposed according to an ordinary procedure and then treated according to the same color development procedures as in Example 1 to obtain a yellow positive image having an absorption maximum at 440 mg and a magenta color image having an absorption maximum at 550 me.
  • a light-sensitive silver halide color photographic material characterized by containing a compound of the general formula,
  • W is a hydrogen atom, or a phenylazo group
  • X, Y and Z which may be same or different, are individually a hydrogen or halogen atom, a lower alkyl group, a lower :alkoxy group, a phenoxy group or a group of the formula COO R (where R is a lower alkyl group);
  • A is a divalent group of the formula NH- NH- (where R is a hydrogen or halogen atom);
  • m is an integer of 1 or 2;
  • R is a hydrogen atom or a lower alkyl group; and R is an aliphatic hydrocarbon residue having 8 to 16 carbon atoms.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Plural Heterocyclic Compounds (AREA)
US00161953A 1970-07-10 1971-07-09 Light sensitive color photographic material Expired - Lifetime US3761274A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP45059863A JPS4916057B1 (enExample) 1970-07-10 1970-07-10

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US3761274A true US3761274A (en) 1973-09-25

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JP (1) JPS4916057B1 (enExample)
DE (1) DE2133655C3 (enExample)
GB (1) GB1313270A (enExample)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3930866A (en) * 1973-04-25 1976-01-06 Fuji Photo Film Co., Ltd. Silver halide color photographic materials containing 3-anilino-5-pyrazolone couplers
US3935016A (en) * 1973-04-13 1976-01-27 Fuji Photo Film Company, Ltd. Silver halide color photographic materials containing 3-anilino-5-pyrazolone couplers
US3960571A (en) * 1973-09-27 1976-06-01 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material
US3973979A (en) * 1973-05-19 1976-08-10 Agfa-Gevaert, A.G. Color photographic materials containing diffusion fast pyrazolone couplers

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3935016A (en) * 1973-04-13 1976-01-27 Fuji Photo Film Company, Ltd. Silver halide color photographic materials containing 3-anilino-5-pyrazolone couplers
US3930866A (en) * 1973-04-25 1976-01-06 Fuji Photo Film Co., Ltd. Silver halide color photographic materials containing 3-anilino-5-pyrazolone couplers
US3973979A (en) * 1973-05-19 1976-08-10 Agfa-Gevaert, A.G. Color photographic materials containing diffusion fast pyrazolone couplers
US3960571A (en) * 1973-09-27 1976-06-01 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material

Also Published As

Publication number Publication date
GB1313270A (en) 1973-04-11
DE2133655A1 (de) 1972-01-13
JPS4916057B1 (enExample) 1974-04-19
DE2133655C3 (de) 1979-11-08
DE2133655B2 (de) 1979-03-15

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