US3558700A - Light sensitive color materials - Google Patents

Light sensitive color materials Download PDF

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Publication number
US3558700A
US3558700A US586028A US3558700DA US3558700A US 3558700 A US3558700 A US 3558700A US 586028 A US586028 A US 586028A US 3558700D A US3558700D A US 3558700DA US 3558700 A US3558700 A US 3558700A
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US
United States
Prior art keywords
coupler
color
solution
added
couplers
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US586028A
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English (en)
Inventor
Shiro Kimura
Makoto Yoshida Momotoshi Tsuda
Akio Okumura
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Holdings Corp
Original Assignee
Fuji Photo Film Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Application granted granted Critical
Publication of US3558700A publication Critical patent/US3558700A/en
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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
    • G03C7/333—Coloured coupling substances, e.g. for the correction of the coloured image
    • G03C7/3335—Coloured coupling substances, e.g. for the correction of the coloured image containing an azo chromophore
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/58—Preparation of carboxylic acid halides
    • C07C51/60—Preparation of carboxylic acid halides by conversion of carboxylic acids or their anhydrides or esters, lactones, salts into halides with the same carboxylic acid part
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic 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
    • C07D231/14—Heterocyclic 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
    • C07D231/44—Oxygen and nitrogen or sulfur and nitrogen atoms
    • C07D231/52—Oxygen atom in position 3 and nitrogen atom in position 5, or vice versa
    • 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
    • G03C7/3212—Couplers characterised by a group not in coupling site, e.g. ballast group, as far as the coupling rest is not specific

Definitions

  • couplers capable of forming cyan, magenta and yellow dyes by coupling with the oxidation product of a developer of N,N-di-substituted paraphenylene diamine series have generally been used.
  • Coupler solvent which introduce therein oil-solubilizing groups, or so-called protective couplers, which can be dispersed in emulsions as the solutions thereof in an organic solvent insoluble or weak-soluble in water.
  • coupler solvent such an organic solvent is called coupler solvent.
  • the coupler have an excellent coupling efliciency and the color image obtained from the coupler have excellent photographic properties such as color hue, but the particularly important factors for the couplers are that the coupler have a sulficient solubility to a coupler solvent, and have a good dispersibility in a photographic emulsion as well as in a photographic emulsion layer during or after coating on a support, which prevents the coupler being deposited or aggregated.
  • An object of the present invention is to provide couplers capable of preventing the unevenness of coating and the reduction in image quality.
  • Another object of the present invention is to provide couplers having a sufficiently good solubility to coupler solvents, such as ethyl acetate, butyl phthalate, o-tricresylphosphate, or butylphosphate and causing neither deposition nor aggregation when they are dispersed in emulsions or incorporated in emulsion layers during or after coating the coupler-containing emulsions on a support, or when or after the color photographic material having the emulsion layers containing the couplers are subjected to color development.
  • coupler solvents such as ethyl acetate, butyl phthalate, o-tricresylphosphate, or butylphosphate
  • Still another object of the present invention is to provide a color photographic material containing the abovementioned improved couplers.
  • Q represents a coupler residual group capable of coupling with the oxidation product of a color developer, such as a compound having a phenolic hydroxyl group (e.g., phenol or naphtol), a compound having an active methylene group (e.g., pyrazolone, indazolone, or acylacetanilide), and the derivatives of them; and (S) means secondaryfi
  • a coupler having the above formula can provide a cyan dye by coupling; when Q is a. pyrazolone compound or a indazolone compound, the coupler provides a magenta dye by coupling; and when Q is an acylacetanilide compound, the coupler provide a yellow dye by coupling.
  • couplers one of which however, composed of hydrogen atoms at the coupling positions is substituted with a halogen atom, a thiocyanide group or a sulfone group, have a merit that the amount of silver ions necesasry for forming dye with the coupler may be half the amount thereof in the case of the un substituted coupler, and further, the couplers substituted with an azo compound residual group or aromatic aldehyde residual group have the function of making color correction of unnecessary absorption of the cyan dye or the magenta dye.
  • the color developer there have generally been used mainly p-phenylenediamine and the derivatives thereof, such as N,N diethylaminoaniline, N,N-diethylaminotoluidine, N-ethyl N hydroxyethylaminotoluidine, N- ethyl-N-methylsulfoneaminoethylamino-toluidine, and the salts thereof.
  • the feature of the coupler to be used in the present invention is that it has 2,4-di-secondaryamyl-phenoxyacetamino group as the oil-solubilizing group and Q of the aforementioned formula may be any compound capable of coupling with the oxidation product of a color developer.
  • the coupler of this invention having the oil-solubilizing group may be prepared by using, as the starting material, inexpe'ris'iveand easily available 2,4-di-secondary amylphenol, the cost of a coupler so prepared is low, and as shown in the following examples of preparation, it can be produced very profitably.
  • the coupler used in this invention can be dissolved very highly in an ester type organic solvent such as a phthalic acid ester, a phosphoric acid ester, and an acetic acid ester, and hence, when the organic solution of the coupler is maintained at a super cooled state, the deposition of the crystal of coupler and the aggregation thereof are very slow, which makes the use of the coupler extremely profitable.
  • an ester type organic solvent such as a phthalic acid ester, a phosphoric acid ester, and an acetic acid ester
  • the solubility of the coupler shown in Table 1 is at a normal temperature (25 C.) but the solubility is rapidly increased as the increase of temperature, and hence, a large quantity of the coupler can be dissolved in a small proportion of coupler solvent.
  • Such properties of the coupler that the solubility of the coupler to coupler solvents is high, and the deposition of the coupler crystal and the aggregation thereof are very slow, are very important for the process wherein the coupler is incorporated in a photographic emulsion after dissolving it in the coupler solvent and then dispersing the solution in a gelatin solution. Further, it will be clear that by using the coupler of this invention having such important properties, the color hue, the transparency and the density of the color image of the color photographic material obtained from the coupler, as well as the stability thereof to light, heat and moisture are remarkably improved.
  • the coupler of this invention may be added as a solution of a high boiling point solvent, a low boiling point solvent or a mixture of both solvents.
  • the cou pler of this invention is usually added in a photographic emulsion, as mentioned above, after dissolving on the coupler solvent and then dispersing the solution in gelatin, but the coupler may be added therein by other method. For example, if the melting point of the coupler is low the coupler is melted by heating and the melt is dispersed in a gelatin solution, or the coupler may be added in a photographic emulsion as a solution thereof in an alkaline aqueous solution. These methods will be explained practically in below examples.
  • the color photographic material prepared by applying to a support the photographic silver halide emulsion obtained by the abovementioned various methods is exposed and developed in a color developer mainly consisting of N-N-di-substituted-p-phenylene diamine series developer, which confirms the light sensitive color element having a good photographic property.
  • the use of the coupler of this invention is not limited to only usual color photographic materials, but the coupler may be utilized to obtain two-color images or mono-color images and may be used for printing as well.
  • the obtained 2,4-di-secondary-amyl-phenoxy acetic acid was caused to react with thionyl chloride by a con ventional manner and then by distilling the reaction product under a reduced pressure, 2,4-di-secondary-amylphenoxyacetyl chloride was obtained.
  • the yield and the boiling point thereof were 71% and 150-155 C./200 mm. Hg respectively.
  • the crystals were recovered by filtration, washed with water, dried and then recrystallized from ethanol solution thereof to provide the objective acetanilide.
  • the yield of the product was 54% (30 g.), the melting point thereof was 120l2l C. and the nitrogen analytical value was found to be 5.21% (calculated 5.02%).
  • EXAMPLE 1 Into 4 g. of dibutyl phthalate was added 2 g. of the coupler having the aforementioned structural Formula 6 and dissolved therein by heating. The coupler containing solution was added into 30 ml. of a 7% aqueous gelatin solution containing 0.1 g. of sodium dodecylbenzene sulfonate and emulsion-dispersed therein by stirring at high speed for 10 minutes in a homo-blender at 60 C.
  • the whole proportion of the emulsified dispersion was added in g. of a photographic light-sensitive emulsion containing 5 g. of silver bromide and 6 g. of gelatin and the resulting emulsion was applied to a film base and dried to provide a color photographic material.
  • a photographic light-sensitive emulsion containing 5 g. of silver bromide and 6 g. of gelatin and the resulting emulsion was applied to a film base and dried to provide a color photographic material.
  • a developer having the following composition processed by using the bleaching solution and the mixing solution having the following composition, and dried.
  • EXAMPLE 2 Into a mixture of 2 g. of dibutyl phthalate and 4 ml. of ethyl acetate was dissolved by heating 2 g. of the coupler having afore-stated structural Formula 10 and the resulting solution was added into 30 ml. of a 7% aqueous gelatin solution containing 0.1 g. of sodium dodecylbenzene sulfonate and emulsion dispersed therein by stirring at a high speed in a homo-blender at 50 C.
  • the whole proportion of the emulsified dispersion was added into 100 g. of a gelatino silver iodo-bromide emulsion containing an orthornatic sensitizer and the resulting emulsion was applied to a baryta paper and dried to provide a color photographic material.
  • EXAMPLE 3 The same procedure as in Example 2 was repeated using 6 ml. of ethyl acetate instead of dibutyl phthalate in the example and a color photographic material was 12 obtained. The film was exposed, developed and processed as in Example 2.
  • magenta image has sharp absorption, and no precipitation or aggregation of the coupler was observed.
  • the whole amount of the emulsified dispersion was added into g. of a gelatino silver iodo-bromide emulsion containing a panchromatic sensitizer and the resulting emulsion was applied to a film base followed by drying to provide a color photographic film.
  • the film was exposed and developed and processed as in Example 1.
  • EXAMPLE 5 Into a mixture of 6 ml. of a 1 N aqueous sodium hydroxide solution and 18 ml. of methanol was dissolved heating 2 g. of the coupler having aforementioned Formula 25 and the solution was added with water to make 40 ml. of the aqueous solution. The whole proportion of the coupler containing solution was added into 100 g. of a gelatino silver iodo-bromide emulsion containing a panchromatic sensitizer, and after neutralizing the emulsion with the addtition of a 2% aqueous citric acid solution, the resulting emulsion was applied to a film base followed by drying to provide a color photographic film. The film was exposed and developed and processed as in Example 1.
  • EXAMPLE 6 2 g. of the coupler having the aforementioned structural Formula 14 was dissolved into 16 g. of tricresyl diphosphate by heating. The coupler-containing solution was added into ml. of a 10% gelatin solution containing 0.3 g. of sodium dodecylbenzene sulfonate and emulsion dispersed therein by repeating five times the high speed stirring for five minutes in a homo-blender at 65 C. and interruption for one mintue.
  • Example 1 Into 100 g. of a gelatino silver iodo-bromide emulsion containing an orthornatic sensitizer was added 15 g. of the above prepared emulsion and the resulting mixture was applied to a film base followed by drying to provide a color photographic film. The film was exposed in green light and developed and processed as in Example 1.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US586028A 1965-10-12 1966-10-12 Light sensitive color materials Expired - Lifetime US3558700A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP6216365 1965-10-12

Publications (1)

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US3558700A true US3558700A (en) 1971-01-26

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US (1) US3558700A (enrdf_load_stackoverflow)
BE (1) BE688083A (enrdf_load_stackoverflow)
CH (1) CH468030A (enrdf_load_stackoverflow)
GB (1) GB1149514A (enrdf_load_stackoverflow)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3770445A (en) * 1970-08-08 1973-11-06 Agfa Gevaert Ag Silver halide color photographic material containing couplers substituted with dicyclopentyl phenoxy groups
US4013635A (en) * 1975-02-26 1977-03-22 Eastman Kodak Company Cyan azo dye-providing compounds
US5214141A (en) * 1991-01-18 1993-05-25 Fuji Photo Film Co., Ltd. Azomethine compound and photographic dye comprising the azomethine compound

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3770445A (en) * 1970-08-08 1973-11-06 Agfa Gevaert Ag Silver halide color photographic material containing couplers substituted with dicyclopentyl phenoxy groups
US4013635A (en) * 1975-02-26 1977-03-22 Eastman Kodak Company Cyan azo dye-providing compounds
US5214141A (en) * 1991-01-18 1993-05-25 Fuji Photo Film Co., Ltd. Azomethine compound and photographic dye comprising the azomethine compound

Also Published As

Publication number Publication date
BE688083A (enrdf_load_stackoverflow) 1967-03-16
GB1149514A (en) 1969-04-23
CH468030A (de) 1969-01-31

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