US3770436A - Process for forming cyan image in light-sensitive color photographic material - Google Patents

Process for forming cyan image in light-sensitive color photographic material Download PDF

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Publication number
US3770436A
US3770436A US00211469A US3770436DA US3770436A US 3770436 A US3770436 A US 3770436A US 00211469 A US00211469 A US 00211469A US 3770436D A US3770436D A US 3770436DA US 3770436 A US3770436 A US 3770436A
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United States
Prior art keywords
coupler
photographic material
light
forming
hydroxy
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Expired - Lifetime
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US00211469A
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English (en)
Inventor
M Fujiwhara
S Matsuo
R Sato
T Koga
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Konica Minolta Inc
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Konica Minolta Inc
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    • 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
    • G03C7/305—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers
    • G03C7/30511—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers characterised by the releasing group
    • G03C7/30517—2-equivalent couplers, i.e. with a substitution on the coupling site being compulsory with the exception of halogen-substitution
    • G03C7/30523—Phenols or naphtols couplers

Definitions

  • References Cited is a group bonded to the UNITED STATES PATENTS p-position of the hydroxyl group of A; and Z is an 2,296,306 9 1942 Peterson 96/565 atomic g p necessary for forming anindazolylgroup, 2,353,754 7/1944 Peterson 96/565 is exposed to light imagewise and subjected to color de- 96/100 velopment, or a light-sensitive color photographic ma- 3,l48,062 9/1964 Whitmore et a]...
  • This invention relates to a process for forming a cyan image in a light-sensitive color photographic material. More particularly, the invention is concerned with a process for forming a cyan dye image in a lightsensitive color photographic material using a twoequivalent cyan dye image-forming coupler.
  • the cyan coupler which forms an indoaniline dye by coupling with the oxidation product of the aromatic primary amine type developing agent, is a phenol or l-naphthol derivative.
  • the said coupler is called a four-equivalent coupler.
  • the hyd r og e niri the 4-position has been subsuthe same dye as in the case of the four-equivalent'coupler.
  • the halogen atom is released during the course of color developmentfind 1 molecl ile o fdye can be formed from 2 molecules of developed silver halide. Accordingly, the said coupler is called a twoequivalent coupler.
  • the two-equivalent coupler is more excellent than the four-equivalent coupler in the following points:
  • the two-equivalent coupler is higher in coupling reactivity than the known four-equivalent coupler.
  • the amount of silver halide required for forming a definite amount of dye may be one half of the amount required in the case of the four-equivalent coupler, so that the cost can be reduced.
  • the emulsion layer can be made thinner, so that the resulting color image is enhanced in resolution and sharpness.
  • Some two-equivalent couplers tend to form color stains and have the property of inhibiting the development.
  • the two-equivalent couplers used in the present invention are colorless and scarcely form stains.
  • cyan dyes obtained by color development from the cyan couplers used in the present invention are not only high in fastness to light, humidity and heat but also sharp in absorption and have an extremely desirable hue for color reproduction.
  • Certain couplers used in the present invention canact as the so-called DIR (development inhibitor-releasing type) couplers which release a substance inhibiting the development at the time of color development,
  • the couplers used in the present invention are twoequivalent couplers having the formula,
  • A is a residue-of a cyan image-forming coupler having an a-naphthol or phenol nucleus from which has been removed the hydrogen inthe p-position to the hy- N/ on l-I-Iydroxy-4-[2-(5-chloroindazolyl)]-N-(ndodecyl )-2-naphthamide CON HCnHas
  • These compounds can easily be obtained by synthesizing a colored cyan from a corresponding l-naphthol type coupler and 2-aminobenzyl alcohol, and heating the colored cyan in 50 percent H 80 Typical synthesis examples are set forth below.
  • the exemplified compound (5) is obtained by acetylating the exemplified compound (1) accord ing to an ordinary procedure.
  • Other compounds are obtained acous gelatin solution containing a surface active agent,
  • the dispersion is added directly to a silver halide photographic emulsion, which is then coated on a support, followed by drying.
  • the said dispersion is set, finely cut, freed from the low boiling solvent by water-washing or the like means, and added to a photoa graphic emulsion, which is then coated on a support,
  • the amount of the coupler to be added to the photographic emulsion is preferably in the range from 10 to 300 .g. per mole of silver halide, but may be varied depending on the application purpose of the resulting photographicmaterial.
  • the photographic emulsions used in the'present invention may be prepared by use of various silver halides such as silver chloride, silver iodobromide and silver chlorobromide. These emulsions may contain chemical sensitizers, e.g. sulfur sensitizers, such natural sensitizer as present in gelatin, reduction sensitizers and noble metal salts. Further, the emulsions may have been incorporated with ordinary photographic additives such as, for example, antifoggants, stabilizers, anti-stain agents, anti-irradiation agents, physical property-improving high polymer additives, hardeners and coating aids, and may contain as known carbocyanine dye, merocyanine dye, etc. as optical sensitizers for the emulsions.
  • chemical sensitizers e.g. sulfur sensitizers, such natural sensitizer as present in gelatin, reduction sensitizers and noble metal salts.
  • the emulsions may have been incorporated with ordinary photographic additives such
  • EXAMPLE 1 2.0 Grams of the exemplified coupler (l) was dissolved in a mixed solvent comprising 2 ml. of dibutyl phthalate and 6 ml. of ethyl acetate. The resulting solution was mixed with 40 ml. of a 6 percent aqueous gelatin solution and 6 ml. of a percent aqueous solution of Alkanol B (produced by Du Pont), and the mixed solution was subjected to ordinary protect dispersion method using a colloid mill to form a coupler dispersion. This dispersion was added to a silver iodobromide emulsion containing 5 g. of silver halide particles, and then the emulsion was coated on a triacetate base and dried to prepare a sample.
  • a mixed solvent comprising 2 ml. of dibutyl phthalate and 6 ml. of ethyl acetate.
  • the resulting solution was mixed with 40 ml. of a
  • the exemplified coupler (1) has prominent characteristics as a coupler bearing an indazolyl 'substituent.
  • samples prepared by using each of the exemplified couplers (5), (9) and (10) in place'of the exemplified coupler (l) were also less in emulsion fog and more excellent in relative speed, gamma and D-max than the sample containing the control coupler.
  • EXAMPLE 2 Samples were prepared in the same manner as in Example l, except that 2.0 g. of the exemplified coupler (,10) was used and the amount of silvgr iodobromide contained in the emulsion was varied to 1.25 g., 2.5 g. and 5.0 g.
  • control samples were prepared in the same manner as above, except that a coupler identical in structure, except its having no indazolyl substituent, with the exemplified coupler (10) was used in such amounts as above. 7
  • EXAMPLE 3 A silver halide emulsion containing 5 g. of silver chlo-' robromide which had been incorporated with 2.0 g. of the exemplified coupler (10) was coated on a support to prepare a sample. This sample was exposed according to an ordinary procedure and then subjected to development. The developer used was identical in composition with that used in Example 1, except that the developing agent was vaired to N-methyl-pphenylenediamine hydrochloride. After the development, the sample was sufficiently washed with water, dried and then treated under such conditions as shown below to obtain the results setforth in Table 3.
  • nucleus manna exeapimea coupler (1) (l-hydroxy-4-(2 '-acetylphenylazo)-N [8-(2 ,4-di-tertamylphenoxy)-butyl]-2-naphthamide) was dissolved in a mixed solvent comprising 2 ml. of tricresyl phosphate 1:3 solvent mixture of tricresylphosphate and ethyl acetate, and the resulting solution was treated in the same manner as in the case of the sample A of Example 4.
  • a sample B was prepared in the same manner as above, except that 1.65 g. ofa coupler identical in structure, except its having no indazolyl substitution, with the exemplified coupler (3) was used in place of the coupler mixture.
  • the samples A and B were exposed according to an ordinary procedure, developed with the same developer as in Example 1, and then subjected to ordinary bleaching, fixing and water-washing treatments to obtain the results shown in the accompanying drawing which is a graph showing the density of cyan dye to red light at each stage described herein in which the horizontal axis represents the amount of exposure (log E) and the vertical axis the density of dye.
  • the sample A is longer in straight line portion of the characteristic curve and somewhat lower in gamma than the sample B, but it is understood that the sample A is entirely free from such detrimental effects as desensitization and the like, and is markedly effecand 7 ml. of ethyl acetate.
  • the resulting solution wasdispersed in 40 ml. of a 5 percent aqueous gelatin solution containing 4 ml. of a 5 percent aqueous sodium n-dodecylbenzenesulfonate solution.
  • This dispersion was added to a red-sensitive photographic emulsion containing 5 g. of silver iodobromide, which was then coated on a cellulose t'riacetate base to a thickness of 5 microns and dried.
  • a sample B was prepared in the same manner as above, except that 0.6 g. of a coupler identical in structure, except its having no indazolyl substitution, with the exemplified coupler (1) was used in place of the exemplified coupler (l).
  • the coupler according to the present invention displays excellent characteristics. Accordingly, when the coupler according to the present invention is used in admixture with couplers which are outside of the scope of the present invention, the resulting photographic material can be controlled in speed, D-max and the like characteristics by merely varying the mixing ratio of the coupiers, without varying the size or amount of silver halide particles.
  • a sample A was prepared in such a mannerthat a coupler mixture composed of 0.20 g. of the exemplified coupler (3) and 1.50 g. of a coupler identical in structure, except its having no indazolyl substitution, with the exemplied coupler (3) was dissolved in 10 ml. of a tive as a socalled DIR (development inhibitor-releasing type) coupler.
  • DIR development inhibitor-releasing type
  • a process for forming a cyan image in a lightsensitive color photographic material characterizedin that a light-sensitive color photographic material having a silver halide emulsion layer incorporated with a compound of the formula my wherein A is a cyan image-forming-coupler residue having an q-naphthol or phenol nucleus;
  • Z is an atomic group necessary for forming an indazolyl group, is exposed to light image wise and subjected to color development, or a lightsensitive color photographic material is exposed to light imagewise and subjected to color development using a color developer incorporated with the compound, of the abovementioned formula, thereby forming a cyan image corresponding to the silver image formed in the photographic material.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US00211469A 1970-12-26 1971-12-23 Process for forming cyan image in light-sensitive color photographic material Expired - Lifetime US3770436A (en)

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JP45119054A JPS4917735B1 (enrdf_load_stackoverflow) 1970-12-26 1970-12-26

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JP (1) JPS4917735B1 (enrdf_load_stackoverflow)
DE (1) DE2163811A1 (enrdf_load_stackoverflow)
GB (1) GB1333819A (enrdf_load_stackoverflow)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3933500A (en) * 1973-03-23 1976-01-20 Fuji Photo Film Co., Ltd. Color photographic light-sensitive material
US4012259A (en) * 1973-05-16 1977-03-15 Fuji Photo Film Co., Ltd. Photographic silver halide emulsion and element and method of forming color photographic images
US4015988A (en) * 1974-03-04 1977-04-05 Fuji Photo Film Co., Ltd. Multilayer color photographic light-sensitive material
USRE29379E (en) * 1973-03-23 1977-08-30 Fuji Photo Film Co., Ltd. Color photographic light-sensitive material
US4049458A (en) * 1974-06-05 1977-09-20 Agfa-Gevaert, A.G. Photographic silver halide material containing 2-equivalent yellow couplers
US4086094A (en) * 1974-06-20 1978-04-25 Fuji Photo Film Co., Ltd. Photographic couplers with N-heterocyclic development inhibiting coupling-off group
US4182630A (en) * 1974-06-26 1980-01-08 Minnesota Mining And Manufacturing Company Pivalyl-acetanilide couplers and photographic elements including them

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
LU83911A1 (fr) * 1982-01-29 1983-09-02 Oreal Produit nettoyant des cheveux et de la peau a base d'acylise thionates et de polymeres cationiques

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2296306A (en) * 1938-10-26 1942-09-22 Eastman Kodak Co Nondiffusing metallic salt coupler compound
US2353754A (en) * 1942-11-07 1944-07-18 Eastman Kodak Co Color photography using metallic salt coupler compounds
US3148062A (en) * 1959-04-06 1964-09-08 Eastman Kodak Co Photographic elements and processes using splittable couplers
US3617291A (en) * 1967-10-10 1971-11-02 Eastman Kodak Co Two-equivalent couplers for photography
US3620745A (en) * 1968-04-01 1971-11-16 Eastman Kodak Co Color photographic silver halide emulsions of different developing speed one layer having a dir coupler
US3620747A (en) * 1968-05-20 1971-11-16 Eastman Kodak Co Photographic element including superimposed silver halide layers of different speeds
US3703375A (en) * 1968-04-01 1972-11-21 Eastman Kodak Co Photographic processes and materials

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2296306A (en) * 1938-10-26 1942-09-22 Eastman Kodak Co Nondiffusing metallic salt coupler compound
US2353754A (en) * 1942-11-07 1944-07-18 Eastman Kodak Co Color photography using metallic salt coupler compounds
US3148062A (en) * 1959-04-06 1964-09-08 Eastman Kodak Co Photographic elements and processes using splittable couplers
US3617291A (en) * 1967-10-10 1971-11-02 Eastman Kodak Co Two-equivalent couplers for photography
US3620745A (en) * 1968-04-01 1971-11-16 Eastman Kodak Co Color photographic silver halide emulsions of different developing speed one layer having a dir coupler
US3703375A (en) * 1968-04-01 1972-11-21 Eastman Kodak Co Photographic processes and materials
US3620747A (en) * 1968-05-20 1971-11-16 Eastman Kodak Co Photographic element including superimposed silver halide layers of different speeds

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3933500A (en) * 1973-03-23 1976-01-20 Fuji Photo Film Co., Ltd. Color photographic light-sensitive material
USRE29379E (en) * 1973-03-23 1977-08-30 Fuji Photo Film Co., Ltd. Color photographic light-sensitive material
US4012259A (en) * 1973-05-16 1977-03-15 Fuji Photo Film Co., Ltd. Photographic silver halide emulsion and element and method of forming color photographic images
US4015988A (en) * 1974-03-04 1977-04-05 Fuji Photo Film Co., Ltd. Multilayer color photographic light-sensitive material
US4049458A (en) * 1974-06-05 1977-09-20 Agfa-Gevaert, A.G. Photographic silver halide material containing 2-equivalent yellow couplers
US4086094A (en) * 1974-06-20 1978-04-25 Fuji Photo Film Co., Ltd. Photographic couplers with N-heterocyclic development inhibiting coupling-off group
US4182630A (en) * 1974-06-26 1980-01-08 Minnesota Mining And Manufacturing Company Pivalyl-acetanilide couplers and photographic elements including them

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JPS4917735B1 (enrdf_load_stackoverflow) 1974-05-02
DE2163811A1 (de) 1972-11-23
GB1333819A (en) 1973-10-17

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