US3649285A - Light-sensitive silver halide color photographic materials containing cyan coupler - Google Patents

Light-sensitive silver halide color photographic materials containing cyan coupler Download PDF

Info

Publication number
US3649285A
US3649285A US54625A US3649285DA US3649285A US 3649285 A US3649285 A US 3649285A US 54625 A US54625 A US 54625A US 3649285D A US3649285D A US 3649285DA US 3649285 A US3649285 A US 3649285A
Authority
US
United States
Prior art keywords
coupler
color
couplers
light
silver halide
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
US54625A
Other languages
English (en)
Inventor
Masakuni Iwama
Toshihiko Yamamoto
Keiji Kasai
Yoshinobu Nakagawa
Takaya Endo
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.)
Konica Minolta Inc
Original Assignee
Konica Minolta Inc
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 Konica Minolta Inc filed Critical Konica Minolta Inc
Application granted granted Critical
Publication of US3649285A publication Critical patent/US3649285A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • G03C7/34—Couplers containing phenols
    • G03C7/344—Naphtholic couplers
    • 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

Definitions

  • hydrogen onhalogen is incorporated within alight-sensitive silver halide color photographic emulsion.
  • a composition useful for forming a cyan-colored photographic image is produced. Deposition of the coupler in the emulsion is substantially reduced. The color formation rate of the coupler is close to that of other magenta and yellow couplers. This enables the three colors to be readily balanced in speed. A finely grained color image is obtained upon color development.
  • the present invention relates to a light-sensitive color photographic material incorporated with a novel coupler for forming a cyan-colored photographic image.
  • couplers capable of coupling with an oxide of the N,N-disubstituted p-phenylene-diamine-type developing agent to form yellow, cyan and magenta colors.
  • protect-type couplers which are water-insoluble or difficulty water-soluble and which can be dissolved in organic solvents and dispersed in photographic emulsions.
  • protect-type couplers are water-insoluble or difficulty water-soluble and which can be dissolved in organic solvents and dispersed in photographic emulsions.
  • Particularly important conditions in the case where said protect-type couplers are used are such that the couplers should have sufficient solubilities for organic solvents (hereinafter referred to as coupler solvents" and should not deposit or agglomerate even when dispersed in photographic emulsions and even after coated as light-sensitive materials on supports.
  • An object ofthe present invention is to provide a light-sensitive photographic material incorporated with a cyan coupler, which shows sufficient solubility for a coupler solvent, e.g., din-butyl phthalate, o-tricresyl phosphate, di-n-butyl lauramide or ethyl acetate and which does not deposit or agglomerate after the coupler dispersion has been dispersed in a photographic emulsion or after the coupler-incorporated emulsion has been coated on a support.
  • a coupler solvent e.g., din-butyl phthalate, o-tricresyl phosphate, di-n-butyl lauramide or ethyl acetate
  • Another object of the invention is to provide a novel coupler, which can inhibit the color formation rate of naphtholtype cyan coupler to obtain the balance of 3 layers and, at the same time, can have a dye formed in fine grain state by color development.
  • CONHR X wherein R is a higher alkyl group, and X is a hydrogen or halogen atom, are excellent in formation efiiciency of indoaniline dye images obtained by coupling with oxidation products of N,N -disubstituted p-phenylenediamine type developing agents, and have excellent color tones.
  • the conventional couplers have many such practical drawbacks that they are inferior in solubility for coupler solvents and severely deposit in photographic emulsions, and most of the particles of the formed dyes are coarse.
  • Japanese Pat. Publication No. 11,303/1967 proposes the use of couplers represented by the formula (II) in which has been formed such an oxazine ring as shown below.
  • R is a saturated hydrocarbon
  • X is a hydrogen or halogen atom
  • the couplers of this kind are extremely low in coupling rate at the time of color development and hence are substantially impractical, though they have somewhat been improved in solubility.
  • R is a substituted aryl or aralkyl group or a saturated or unsaturated and substituted or unsubstituted aliphatic hydrocarbon residue having one to 22 carbon atoms; R is an aliphatic hydrocarbon residue having one to six carbon atoms; and X is a hydrogen or halogen atom.
  • the alkoxalyl-type cyan couplers represented by the abovementioned general formula have increased solubilities for coupler solvents.
  • those of the said general formula (III), in which R is an aliphatic hydrocarbon residue having four to six carbon atoms could be easily dissolved in coupler solvents of one-half to one-third of the amounts required in the case of corresponding couplers represented by the general formula (I), and, even when the solutions were allowed to stand at room temperature, they were extremely long in time required for initiation of deposition. Further, they showed improved oil solubilities.
  • the solubility test was carried out in such a manner that l g.
  • CONHCmH V V V V l 7 are increased in solubility for coupler solvents to make it d Jolor t possible to obtain coupler solutions of high concentration. 0 g opmen I hi i n or allowed to stand. the cr stall iven when these so to s e y g g N lization of the couplers lS extremely slow.
  • the photographic emulsion having the 0NHOnHn present coupler dispersed therein is coated on a support, the amount of high boiling solvent per unit area is small, and therefore the emulsion is less afiected by the high boiling 501- I vent and can be easily formed into a thin layer to give such ad- N vantage that the resulting color image is improved in sharp- 4 ness Coupler used 5 5 Formed dye
  • the present coupler of the general formula (III) is somewhat lower in color formation rate than a corresponding coupler of the general formula (I). This, however, results in such advantage that the coupler becomes close in color formation rate to other magenta and yellow couplers, with the result that the 3 colors can easily be balanced in speed.
  • the dye formed by color development becomes finer in grain size than in the case of a corresponding coupler of the general formula (I) to make it possible to obtain a color image with extremely fine grains.
  • the coupler of the present invention has such important significance as set forth below.
  • the coupler is not hindered in function and, moreover, the alkoxalyl group in' the l-position is removed during the step of color development to form the same dye as that formed from a corresponding coupler of the general formula (I), as shown below, for example.
  • Synthesis examples of typical couplers are set forth below.
  • Synthesis Example ll V Synthesis of ethoxalyl chloride 25.3 g. of oxalyl chloride was charged into a three-necked flask. Into this was dropped with stirring 9.2 g. of ethanol over a period of 1 hour while maintaining the inner temperature at below 10 C. The resulting mixture was reacted with stirring at room temperature for 30 minutes and then subjected to distilwas stirred at below 20 C. for 1 hour and at room temperature for additional 1 hour. Subsequently, the pyridine and acetonitrile were removed by means of an aspirator, and the residue was poured into 150 ml.
  • Synthesis Example VI was repeated, except that N-n-o cchloro-Z-naphthamide was treated in the same manner as in mdecyl-lhydroxy-z'naphthamlde and xylem Were used Synthesis Example 111 to obtain white sand-like crystals, yield 40 Place of the yy y yp a and 55 percent mp.
  • EXAMPLE 1 l g. of the exemplified coupler compound 4 was completely dissolved at 60 C. in a mixed liquid comprising 10 ml. of din-butyl phthalate and 20 ml. of ethyl acetate. This solution was mixed with 10 ml. of a 10 percent aqueous solution of Alkanol B (trade name of Du Font) and 200 ml. of a 5 percent aqueous gelatine solution, and the resulting mixture was subjected to a colloid mill to form a dispersion. The dispersion was added to 1,000 ml. of a red-sensitive silver iodobromide photographic emulsion. which was then coated on a film base, followed by drying, to obtain a light-sensitive color photographic material.
  • a mixed liquid comprising 10 ml. of din-butyl phthalate and 20 ml. of ethyl acetate.
  • This solution was mixed with 10 ml. of a 10
  • N.N-Diethyl-p-phenylenediamine hydrochloride 2.0 g.
  • Anhydrous sodium sulfite 2.0 g.
  • Sodium carbonate (monohydrate) 82.0 g.
  • Potassium bromide 2.0 g. Water to make l 000 ml Subsequently, the film was subjected to stopping and fixing according to ordinary procedures, washed with water for 10 to minutes and then treated for 5 minutes with a bleaching solution of the following composition:
  • Red prussiate I00 Red prussiate I00 5. Potassium bromide 50 g. Water to make 1,000 ml.
  • the film was further washed with water for 5 minutes and then fixed for 5 minutes with the following fixing bath:
  • the coupler of the present invention may be used in combination with such a cyan color coupler as represented by the general formula (IV) shown below, e.g., such color coupler for obtaining a color retouching mask as exemplified in U.S. Pat. No. 3,034,892, or in combination with the couplers of the general formulas (l) and (IV), whereby the deposition characteristic of the coupler and the graininess of the resulting image can be improved.
  • the coupler of the general formula (IV) is indicated below:
  • the coupler can be so controlled as to attain adequate masking effects.
  • the coupler of the present invention is an extremely useful cyan coupler.
  • EXAMPLE 2 15 g. of the exemplified coupler compound l was completely dissolved at 60 C. in a mixed liquid comprising 15 ml. of tricresyl phosphate and 45 ml. of butyl acetate. This solution was mixed with 8 ml. ofa 10 percent aqueous solution of Alkanol B and 300 ml. ofa 5 percent aqueous gelatine solution, and the resulting mixture was subjected to a colloid mill to form a dispersion. The dispersion was added to 1,000 ml. of a red-sensitive gelatino silver iodobromide photographic emulsion, which was then coated on a film base, followed by drymg.
  • the film was subjected to ordinary stopping and hardening treatments and water-washing.
  • the thus treated film was further subjected to secondary exposure by use of a white light and then developed at 20 C. for 12 minutes with a developer of the following composition:
  • N.N-Diethyl-p-phenylenediarnine 5.0 g.
  • Anhydrous sodium sulfite 2.0 g.
  • Sodium carbonate (monohydratc) 82.0 g.
  • Potassium bromide 1.0 g. Water to make 1.000 ml.
  • the developed film was stopped, fixed, water-washed and bleached according to ordinary procedures and then washed with running water for 20 minutes, followed by drying, to obtain a positive cyan color image of fine grains having an absorption maximum at 689 ,u and excellent in transparency.
  • EXAMPLE 4 lOO g. of the exemplified coupler compound 12 was completely dissolved at 60 C. in 100 ml. of di-n-butyl phthalate. This solution was added to 5 liters of a percent aqueous gelatine solution kept at 60 C., and further charged with 200 ml. of a 10 percent aqueous sodium alkylbenzenesulfonate solution. The resulting mixture was subjected to a colloid mill at about 60 C. for 10 minutes to form a dispersion. The dispersion was stirred for 10 minutes. This operation was repeated four times with intervals of 1 minute to obtain a coupler dispersion.
  • the thus obtained dispersion was added to 10 liters of a gelatino silver iodobromide emulsion containing a red-sensitive sensitizing dye. After thorough stirring, the emulsion was coated on a film support at 30 to 35 C. and then dried to prepare a light-sensitive color photographic material.
  • This film was exposed and then color-developed, bleached and fixed in the same manner as in Example 1 to obtain a cyan-colored negative image.
  • the film prepared by use of the exemplified coupler compound 13 was quite excellent in transparency and showed an absorption maximum at 690 u.
  • EXAMPLE 5 7 g. of the exemplified coupler compound 12 and 3 g. of N- n-dodecyl-l-hydroxy-4-chloro-2-naphthamide, a coupler corresponding to the general formula (I) were completely dis solved at 60 C. in a mixed liquid comprising 7 ml. of cli-nbutyl phthalate and 15 ml. of ethyl acetate. This solution was mixed with 10 ml. of a 10 percent aqueous solution of Alkanol B and 200 ml. of a 5 percent aqueous gelatine solution. The resulting mixture was subjected to a colloid mill to form a dispersion. The dispersion was added to 1,000 ml. of a redsensitive silver iodobromide emulsion, which was then coated on a film base, followed by drying to prepare a light-sensitive photographic material.
  • a mixed liquid comprising 7 ml. of cli-
  • This film was exposed according to an ordinary procedure and then treated with the same developer as in Example 2 to obtain a cyan color image of fine grains which was excellent in transparency.
  • R is an aryl or aralkyl group or a saturated or unsaturated, aliphatic hydrocarbon residue having one to 22 carbon atoms; R is an aliphatic hydrocarbon residue having one to six carbon atoms; and X is a hydrogen or halogen atom.
  • a light-sensitive silver halide color photographic element which comprises a support and, coated thereon, a light-sensitive silver halide color photographic emulsion as claimed in claim 1.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Indole Compounds (AREA)
US54625A 1969-07-16 1970-07-13 Light-sensitive silver halide color photographic materials containing cyan coupler Expired - Lifetime US3649285A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP44055733A JPS4817890B1 (enrdf_load_stackoverflow) 1969-07-16 1969-07-16

Publications (1)

Publication Number Publication Date
US3649285A true US3649285A (en) 1972-03-14

Family

ID=13007042

Family Applications (1)

Application Number Title Priority Date Filing Date
US54625A Expired - Lifetime US3649285A (en) 1969-07-16 1970-07-13 Light-sensitive silver halide color photographic materials containing cyan coupler

Country Status (4)

Country Link
US (1) US3649285A (enrdf_load_stackoverflow)
JP (1) JPS4817890B1 (enrdf_load_stackoverflow)
DE (1) DE2035014A1 (enrdf_load_stackoverflow)
GB (1) GB1285130A (enrdf_load_stackoverflow)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3808945A (en) * 1971-03-29 1974-05-07 Konishiroku Photo Ind Light-sensitive silver halide color photographic emulsion
US3926631A (en) * 1973-04-13 1975-12-16 Fuji Photo Film Co Ltd Silver halide photographic light-sensitive material
CN101638365B (zh) * 2008-10-31 2010-12-22 海门贝斯特精细化工有限公司 草酰氯单乙酯的生产工艺

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2186850A (en) * 1936-02-27 1940-01-09 Agfa Ansco Corp Color photography
US2476559A (en) * 1946-10-01 1949-07-19 Gen Aniline & Film Corp Oxazine diones
US2860974A (en) * 1954-11-22 1958-11-18 Eastman Kodak Co Photographic color correction process
US3271152A (en) * 1962-09-04 1966-09-06 Eastman Kodak Co Light-sensitive elements for color photography and process therefor

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2186850A (en) * 1936-02-27 1940-01-09 Agfa Ansco Corp Color photography
US2476559A (en) * 1946-10-01 1949-07-19 Gen Aniline & Film Corp Oxazine diones
US2860974A (en) * 1954-11-22 1958-11-18 Eastman Kodak Co Photographic color correction process
US3271152A (en) * 1962-09-04 1966-09-06 Eastman Kodak Co Light-sensitive elements for color photography and process therefor

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3808945A (en) * 1971-03-29 1974-05-07 Konishiroku Photo Ind Light-sensitive silver halide color photographic emulsion
US3926631A (en) * 1973-04-13 1975-12-16 Fuji Photo Film Co Ltd Silver halide photographic light-sensitive material
CN101638365B (zh) * 2008-10-31 2010-12-22 海门贝斯特精细化工有限公司 草酰氯单乙酯的生产工艺

Also Published As

Publication number Publication date
DE2035014A1 (de) 1971-02-11
JPS4817890B1 (enrdf_load_stackoverflow) 1973-06-01
GB1285130A (en) 1972-08-09

Similar Documents

Publication Publication Date Title
US3342597A (en) Color developer precursor
US5284739A (en) Photographic silver halide color material having incorporated therein a ballasted heterocyclic-sulphonhydrazide color developing agent
JPS58162949A (ja) ハロゲン化銀カラ−写真感光材料
US3928041A (en) Development inhibitor yielding compound for silver halide photography
JPS61201247A (ja) ハロゲン化銀写真要素
DE3016727A1 (de) Lichtempfindliches farbphotographisches silberhalogenidmaterial
US4009035A (en) Process for forming cyan dye photographic images
US2414491A (en) Photographic developer
US4438193A (en) Silver halide photosensitive color photographic material
US4012258A (en) Process for forming color photographic images
US3649285A (en) Light-sensitive silver halide color photographic materials containing cyan coupler
US3684514A (en) Light-sensitive silver halide color photographic emulsions
US3770446A (en) Color photographic silver halide material containing acetanilide couplers
US3770436A (en) Process for forming cyan image in light-sensitive color photographic material
GB1564349A (en) Light-sensitive silver halide photographic materials
DE69020431T2 (de) Photographisches Aufzeichnungsmaterial mit einem blaugrünen Farbstoff erzeugenden Kuppler.
DE69323571T2 (de) Farbphotographische Silberhalogenidmaterialien
US3135609A (en) 1-hydroxy-2-naphthamide couplers for color photography
US3667956A (en) Light-sensitive silver halide color photographic materials containing cyan couplers
US3658545A (en) Light-sensitive silver halide color photographic material containing cyan couplers
JPH0497347A (ja) ハロゲン化銀写真感光材料
US3811892A (en) Light-sensitive silver halide color photographic material containing cyancolored couplers
JPS6337350A (ja) ハロゲン化銀カラ−写真感光材料
US4810625A (en) Photographic material with pyrazolone coupler and oil former
US3619196A (en) Light-sensitive color-photographic emulsions