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
  • G03C7/3212—Couplers characterised by a group not in coupling site, e.g. ballast group, as far as the coupling rest is not specific
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
• • 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

Definitions

• R is an aliphatic hydrocarbon residue having 8-18 carbon atoms
• B is a coupler residue
• X is a group bonding B to and m and n are 1 or 2.
• This invention relates to a light-sensitive color-photographic material. More particularly, the invention pertains to a light-sensitive color-photographic material containing, as a protected coupler, a novel coupler for forming a yellow, red or blue color dye image which is represented by the general formula wherein R is an aliphatic hydrocarbon residue having 8-18 carbon atoms; B is a coupler residue; X is a group capable of bonding (B) to and m and n are each either 1 or 2.
• a protected coupler is required, in general, to satisfy the following conditions:
• the coupler should be high in purity and should be prepared according to a simple synthetic process from easily obtainable inexpensive materials.
• the coupler and a dye formed by color development should be readily soluble in high boiling solvents, such as tricresyl phosphate, dibutyl phthalate, etc. to give a high concentration solution.
• the coupler should have no detrimental effects, such as fogging, desensitization and the like, on a silver halide emulsion.
• the coupler should give a stable photographic layer without crystallization.
• the coupler should have good dye formation, be excellent in spectral absorption characteristic of the resulting color-developed dye image, and be fast to heat, light, humidity and the like.
• the coupler employed in the present invention has such characteristics as mentioned below.
• the coupler employed in the present invention can be simply and economically prepared by using as a starting material a long chain alkyl mercaptan which is inexpensive and is easily obtainable. Accordingly, the novel coupler employed in the present invention is quite useful as a protected coupler and has substantially avoided the defects of the conventional couplers. Such excellent characteristics of the present coupler as mentioned above are considered ascribable to the existence of the long chain alkylthio fatty acid group.
• the coupler employed in the present invention is obtained, in general, by forming an alkylthio fatty acid chloride from a long chain alkyl mercaptan and a methacrylic acid ester, or from a long chain alkyl mercaptan and a halogenated fatty acid, and then condensing said chloride with a coupler component having an amino group.
• Examples of the thus obtained coupler employed in the present invention are as shown below, but the compounds usable in the present invention are not limited thereto.
• This oily liquid can be converted into the corresponding acid chloride in the same manner as in- Synthesis C.
• the coupler exemplified by (2) is prepared from a-(4-aminobenzoyl)-2-methoxy-5-ethoxycarbonyl acetanilide and t-dodecylthioacetyl chloride
• the coupler exemplified by (3) is prepared from a-(4- aminobenzoyl)-2-methoxyacetanilide and ,B-n-octadecylthio-a-methyl propionic acid chloride.
• the coupleremployedin the present inboiling point of about C. e.g. tricresyl phosphate or dibutyl phthalate
• av low boiling solvent e.g. butyl acetate or butyl propionate
• the mixed solution is emulsified by means of a high speed rotary mixer or a colloid mill.
• the resulting emulsion is added directly to a silver halide photographic emulsion and is then dried to remove a major portion of the low boiling solvent.
• av low boiling solvent e.g. butyl acetate or butyl propionate
• the emulsion is once cold-set, finely cut and water-washed to remove the low boiling solvent, and is then added to a silver halide photographic emulsion.
• the thus obtained photographic emulsion is applied onto a suitable support,
• the amount of the coupler to be added vention are sulfates, sulfites and hydrochlorides of:
• the amount 5 Y -P-P Y of the coupler is not always limited to said range.
• Y -fiy y After exposure to light, the light-sensitive material obaminoaniline, tained in the above manner is developed with a para- N-ethyl-N- y y y Y -Pp y phenylenediamine-type developing agent, and is then N-ethyl-N-hydroxyethyl-p-phenylenediamine, and bleached, fixed and freed from silver to obtain a high 10 N,N-diethyl-2-methyl-p-phenylenediamine.
• Coupler exemplified by (1) Il-C1zH25s CH2?HC ONH- (1) CH; 106-108 0 0m 0 0 NH- Coupler disclosed in US. Pat. 2,875,057 t-mm-Q-o cure ONH OH; 126-127 C1120 ONH TABLE 2.COMPARISON IN MELTING POINT BETWEEN THE COUPLER EXEMPLIFIED BY (8) AMONG THE COU- PLERS EMPLOYED IN THE PRESENT INVENTION AND A KNOWN COUPLER SIMILAR IN STRUCTURE THERETO Coupler Structural formula MP. 0 C.)
• Coupler exemplified by (8) n-C1zHz S'CH2CHCONH 75-77 Coupler disclosed in US. Pat. 2,618,614 t-C H1i 0 CHzC ON H- 138-139 sHn ONH-
• Coupler exemplified by (17) n-C12Hz SOH2GH-OONH -01 57-58 (
• the couplers emcouplers employed in the present invention are excellent ployed in the present invention are far lower in melting in solubility for high boiling solvents are set forth in the point than the known couplers, and hence do not crystables below.
• Each test was effected by measuring the tallize in emulsions or in photographic layers formed by temperature at which 1 g. of a coupler was dissolved in applying the emulsions to suitable support.
• the 2 ml. of dibutyl phthalate, and comparison in solubility light-sensitive photographic materials of the invention between the present couplers and known couplers were are excellent in stability and transparency. made on the basis of the thus measured temperature.
• Coupler exemplified by (17) n-Ci2IIz5- S C H2- CIIC ONH -01 45 l Coupler disclosed in U.S. Int. 2,801.171 t-C H O CHCONH- Cl
• the couplers employed in the present invention are excellent also in solubility for high boiling solvents as compared with the known couplers and hence are quite useful as protected couplers.
• they give such advantages as the increase in developed color density and the reduction in amounts of couplers.
• the light-sensitive photographic materials of the present invention have excellent photographic characteristics in color reproductivity and granularity.
• EXAMPLE 1 200 g. of the coupler exemplified by (1) were added to a liquid mixture comprising 200 ml. of dibutyl phthalate and 600 ml. of butyl acetate, and was completely dissolved by heating to 80 C. The solution was mixed with 100 m1. of a 10% aqueous solution of Alkanol B (alkylnaphthalene sulfonate produced by E. I. du Pont de Nemours & Co.) and 2000 ml. of a 5% aqueous solution of gelatine. Subsequently, the mixture was subjected to a colloid mill to form a coupler dispersion.
• Alkanol B alkylnaphthalene sulfonate produced by E. I. du Pont de Nemours & Co.
• This coupler dispersion was added to kg. of a high speed gelatino silver iodobromide photographic emulsion, and was applied onto a film base, followed by drying, to obtain a light-sensitive photographic material having a stable light-sensitive layer.
• This light-sensitive material was exposed according to an ordinary procedure and was developed at C. for 10 minutes by use of a developer of the following composition:
• N,N-diethyl-p-phenylenediamine hydrochloride 2.5 Anhydrous sodium sulfite 2.0 Sodium carbonate (monohydrate) 82.0 Potassium bromide 2.0
• the developed material was treated with a stopping solution and then with a fixing solution, was washed with water for 10-15 minutes, and was treated for 5 minutes in a bleaching bath of the following composition:
• the bleached material was further washed with Water for 5 minutes and was then fixed for 5 minutes in a fixing bath of the following composition:
• the fixed material was water-washed for 20- minutes and was then dried to obtain a clear yellow dye image having a maximum absorption at 440 m
• the couplers exemplified by (8) and (14) were individually added to silver halide emulsions, were applied onto supports and were then dried to obtain light-sensitive photographic materials. After exposure to light, the thus obtained photographic materials were subjected to the same color development treatment as mentioned above to obtain clear magenta and cyan dye images having maximum absorptions at 540 m and 680 m respectively.
• EXAMPLE 2 100 g. of the coupler exemplified by (2) were added to a mixture comprising 100 ml. of tricresyl phosphate and 300 ml. of butyl acetate, and was completely dis- 12 solved by heating to 60 C. The solution was mixed with 50 ml. of a 10% aqueous solution of alkanol B and 2000 ml. of a 5% aqueous solution of gelatine. Subsequently, the mixture was subjected to a colloid mill to form a coupler dispersion. This coupler dispersion was added to 5 kg. of a high speed gelatino silver iodobromide emulsion and was applied onto a film base, followed by drying, to obtain a light-sensitive photographic material having a stable photographic layer.
• This light-sensitive material was exposed and was developed at 20 C. for 10 minutes by use of a developer having the following composition:
• the developed material was subjected to ordinary stopping and hardening treatment, was washed with water, and was then subjected to re-exposure by use of a white light.
• EXAMPLE 3 g. of the coupler exemplified by (17) were mixed with 200 ml. of dibutyl phthalate and was completely dissolved at 50 C.
• the solution was mixed with 50 ml. of a 10% aqueous solution of Alkanol B and 2000 ml. of a 5% aqueous solution of gelatine.
• the mixture was passed several times through a colloid mill to form an emulsified dispersion. This dispersion was added to 5 kg. of a gelatino silver chlorobromide emulsion, and was applied to a baryta paper, followed by drying, to prepare a light-sensitive material.
• This light-sensitive material was exposed and was the developed at 20 C. for 10 minutes in a bath of the following composition:
• N-ethyl-N-hydroxyethyl-p-phenylenediamine sulfate 2.5 Anhydrous sodium sulfite 2.0 Hydroxyamine hydrochloride 1.0 Sodium carbonate 82.0 Potassium bromide 2.0 Water to make 1000 ml.
• the developed material was dipped in a stop bath comprising 10 ml. of glacial acetic acid, 3.0 g. of caustic soda, and 1000 ml. of water, and was then immediately dipped for 4 minutes in an acidic fixing bath containing a hardener. Subsequently, the fixed material was washed with 13 water for minutes and was then bleached at C. for 8 minutes in a bath of the following composition:
• the bleached material was washed with water for 20 minutes and was then dipped for 2 minutes in a stabilizing bath, followed by drying, to obtain a cyan dye image having a maximum absorption at 680 m which was excellent in resistance to light and humidity.
• a light-sensitive color-photographic material comprising a compound represented by the general formula wherein R is an aliphatic hydrocarbon residue having 8-l8 carbon atoms; B is a coupler residue; X is a group bonding (B) to and m and n are each either 1 or 2, is incorporated as a protected coupler in the color-photographic silver halide emulsion layer of said color-photographic material.
• a light-sensitive color-photographic material as claimed in claim 1, wherein said compound is represented by the chemical formula claimed in claim 1, wherein said compound is represented by the chemical formula 7.
• a light-sensitive color-photographic material as claimed in claim 1, wherein said compound is represented by the chemical formula 8.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Applications Claiming Priority (1)

Publications (1)

Family

ID=13355946

Family Applications (1)

Country Status (5)

Cited By (3)

Families Citing this family (1)

• 1968
  • 1968-10-19 DE DE19681804167 patent/DE1804167A1/de active Pending
  • 1968-10-22 US US769707A patent/US3580721A/en not_active Expired - Lifetime
  • 1968-10-22 BE BE722686D patent/BE722686A/xx unknown
  • 1968-10-23 FR FR1587205D patent/FR1587205A/fr not_active Expired
  • 1968-10-23 GB GB1228041D patent/GB1228041A/en not_active Expired

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