US2728659A - N-alkylhydroquinone antistain agents - Google Patents

N-alkylhydroquinone antistain agents Download PDF

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Publication number
US2728659A
US2728659A US359422A US35942253A US2728659A US 2728659 A US2728659 A US 2728659A US 359422 A US359422 A US 359422A US 35942253 A US35942253 A US 35942253A US 2728659 A US2728659 A US 2728659A
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United States
Prior art keywords
water
flask
mixture
color
yellow
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
US359422A
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English (en)
Inventor
Loria Anthony
John R Thirtle
Weissberger Arnold
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.)
Eastman Kodak Co
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Eastman Kodak Co
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Filing date
Publication date
Priority to BE529273D priority Critical patent/BE529273A/xx
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to US359422A priority patent/US2728659A/en
Priority to FR1105049D priority patent/FR1105049A/fr
Priority to GB16319/54A priority patent/GB752146A/en
Application granted granted Critical
Publication of US2728659A publication Critical patent/US2728659A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • G03C7/392—Additives
    • G03C7/39208—Organic compounds
    • G03C7/39212—Carbocyclic
    • G03C7/39216—Carbocyclic with OH groups

Definitions

  • This invention relates to color photography'and par. ticularly to a method for preventing the formationi of color fog or stain in photographic emulsions.
  • a difficulty frequently encountered in these processes is the formation of color fog or stain.
  • dye fog is frequently formed'in the emulsion layer. Thisis Because the developing agent has been oxidizedvto-some,
  • antistain agents which are non-difiusing in the photographic layer and which are strong enough reducing agents to react rapidly with oxidized 'color developer.
  • a further object is-to provide antistain agents T which do not form highly colored oxidation products V formula: I
  • an emulsion layer or other layer of a photographic material especially a silver halide emulsion layer in which a colored image is formed -by development in a color-forming developer, of a normal alkyl hydroquinone having the where 'R is a normal alkyl group having from 5 to 18 carbon atoms, e. g., amyl, hexyl, heptyl, octyl, octadecyl, etc., and R- is hydrogen or the same as R, and is attached to the hydroquinone in the 5 or 6 position.
  • V 7 (
  • dialkyl hydroqu'inones availa.-- on able at that time were the di-secondary and di tertiary hydroquinones.
  • the flask was heated on a steam bath for 5-6 hours. After a short time, the mixture, which sets to an orange-yellow mush overnight, formed a deep, orange-red solution and drops of water were ap-- parent in the upper part of the flask. At the end of the heating period the mixture was cooled to room temperature with a stream of cold water. It was then poured, with mechanical stirring, into a room-temperature solution of 615 g. (7.5 moles) of sodium acetate in 3100 ml. of water in a 5-liter, 3-neck flask. An additional 100 ml. of tetrachloroethane was used for rinsing the reaction flask. The mixture was'then stirred at room temperature for 30-40 minutes to complete the hydrolysis.
  • the organic layer was allowed to settle and the supernatant aqueous-layer removed as completely as possible by decantation with suction.
  • the tetrachloroethane solution was washed twice with'2-3 liters of water, by
  • the crude product formed yellow crystals, M. P. 84-86 C., with. preliminary softening at about 75 C.
  • the crude yield was 361 g. (76.5%).
  • the material was recrystallized from a mixture of 4 volumes of methanol and 1 volume ofwater, using 5 ml. per gram, with the addition of Darco (absorbent carbon).
  • the recovery was 327 g. of bright yellow crystals, M. P. 845-86 C., withv some softening at about 80 C. This amounts to a yield of 69% of the theoretical 472 g.
  • the stirrer was started and hydrogen gas from a cylinder was passed into the reaction mixture at such a rate that the 'full pressure determined by the depth of the outlet tube in the cylinder of water was maintained in the flask. (A very slo'w streamof bubbles in the water cylinder indicates a safe rate.
  • the speed of reduction may be estimated by shutting off the hydrogen at the inlet and observing ft'he rate at which the water rises in the exit tube due to the absorption of the hydrogen in the flask.
  • Thecatalyst was removed by gravity filtration, and the flask and filter rinsed with 25 ml. of glacial acetic acid.
  • the light-yellow filtrate was heated to boiling and treated with sma'll portions of zinc dust until no further 'decolori'z'atio'n occurred Z- 3 g.).
  • the zinc dust was filtered oii and washed with 25 ml. of hot glacial acetic acid.
  • the almost colorless (very light yellow) filtrate and washings were treated with 250 ml. of hot Water, mixed thoroughly, and cooled to 0 C.
  • the atflrst oily precipitate soon crystallizes to a white solid.
  • the 2-n-octylhydroquinone formed a slightly oft-white crystalline powder, M. P. 96.598 C., with some prespasms
  • Compound 4.2-caprylyl-5-nbctylhydroziuizipna CHM/ Hmon A one-liter, ,3-necked flask was charged with a mixture of 111 g. (0.5 mole) of 2-n-octylhydroquinone, 108 g. (0.75 mole) of n-caprylic acid and 250 ml. of s-tetrachloroethane.
  • the flask was fitted with a gas inlet tube extending to the bottom of the flask, a thermometer, and gas outlet tube to the hood.
  • the whole apparatus was counterpoised on a balance pan. Boron trifluoride from a cylinder is passed directly into the slurry at such a rate that the temperature was maintained at 40-45 C. -Considerable heat was evolved and the n-octylhydroquinone slowly dissolved to form a dark, yellow-brown solution: When about 62 g.
  • the flask was then heated on the steam bath for 6 hours. The mixture soon became turbid and drops of water-were apparentin the upper partof the flask. At the end of the heating period the mixture was cooled to room temperature and poured, with stirring, into a room temperature solution of 140 g. (1.7 moles) of sodium acetate in 1260 ml. of water. An additional 50 ml. of s-tetrachloroethane was used for rinsing out the reaction flask. The mixture was stirred at room temperature for about 30 minutes to complete the hydrolysis.
  • the filtered solution was concentrated under reduced pressure on the steam bath to a volume of about 300 ml. 600 ml. of petroleum ether was added' and the mixture cooled to C.
  • the precipitate was filtered off, washed free-of dark, oily material with petroleum ether, and dried in the air. -It formed yellow crystals, M. P. 82-83" C., with some preliminary softening at 79 C. Weight: 115 g.
  • the catalys't wa's filtered off and the filtrate poured into a large volume of water.
  • the organic material was extracted into ether, and 't'he ether layer was neutralized with sodium bicarbonate, washed with water, dried over sodium sulfate, and concentrated.
  • the 4-rnethoxy-2- n-octylphenol wascollected at 187-190/ 10 mm. (yield 141 g3, 88%).
  • the-reaction mixture When cool, the-reaction mixture was poured into at least twice its volume of water and chilled under running water for a few hours. The solid was filtered off and the sticky material was slurried carefully in thefunnel with ice-cold petroleum ether, most of the color and stickiness beingremoved by this proceduref
  • the product was recrystallized from a mixture of approximatelyZlS cc. of ligroin (B. P. 90-l20) and 215 cc. of low boiling petroleum ether, giving 15.5 g. (64%).M. P. 81.5-82.5.
  • Patent 2,423,730 when incorporated in this way, produce dyes upon color development which are prone to fading by the action of visible or ultraviolet light, when known antistain agents such as 2,5-di-tert. octyl hydroquinone are used in the emulsion layer. These are the yellow and cyan dyes.
  • the magenta dyes such as those formed from couplers described inLoria, Weissberger and Vittum U. S. Patent 2,600,788 are relatively little affected by the known antistain agents upon the action of light.
  • a quantity of the antistain agent was dissolved with 0.5 g. of coupler in 1.5 cc. of dibutylphthalate.
  • the mixture was passed through a colloid mill three times, and to the resulting dispersion, 32 cc. of a gelatino-silver halide emulsion were added, and the mixture blended and coated on a film support so'that the anti-stain agent was equivalent to 5 mg. per sq. ft. of 2,5-di-tert.-octyl hydroquinone.
  • Two check coatings were made: one containing no anti-stain agent, and one containing 5 mg. per sq. ft. of 2,5-di-tert. octyl hydroquinone.
  • the film strips were exposed on a Ib sensitometer using a silver wedge varying in density from 0 to 3. They were then developed 10 minutes at 68 F. in the following developer:
  • T he antistain agents of our invention may also be used in non-sensitive overcoating or filter layers, such as a colloidal silver interlayer of multilayer photographic material.
  • the antistain agents of our invention are used in the emulsion or other layer in quantities ranging from 0.07 gram to 4.3 grams per liter of emulsion or gelatin solution. These values are, however, merely illustrative.
  • a processing solution such as a prebath, first developer bath,.or color-forming developer used with color film which is developed with a primary aromatic aminodeveloping agent.
  • Our materials are particularly useful with color-forming emulsions coated on paper supports where it is especially important to reduce the minimum or fog densities. This applies both to negative developed paper and to reversal paper as well as to transparency materials.
  • a color-forming photographic emulsion having reduced fogging tendency comprising a silver halide emulsion having incorporated therein a non-diffusing coupler compound capable of coupling with the oxidation product of a primary aromatic amino developing agent and as an where R and R are normal alkyl groups of from 9 to 18 "carbon atoms, and R is attached to the hydroquinone nucleous in a position selected from the class consisting of 5 and 6 positions.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US359422A 1953-06-03 1953-06-03 N-alkylhydroquinone antistain agents Expired - Lifetime US2728659A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BE529273D BE529273A (en, 2012) 1953-06-03
US359422A US2728659A (en) 1953-06-03 1953-06-03 N-alkylhydroquinone antistain agents
FR1105049D FR1105049A (fr) 1953-06-03 1954-06-02 Procédé et produits pour l'obtention d'images photographiques en couleurs
GB16319/54A GB752146A (en) 1953-06-03 1954-06-02 Improvements in light sensitive colour photographic materials

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US359422A US2728659A (en) 1953-06-03 1953-06-03 N-alkylhydroquinone antistain agents

Publications (1)

Publication Number Publication Date
US2728659A true US2728659A (en) 1955-12-27

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US (1) US2728659A (en, 2012)
BE (1) BE529273A (en, 2012)
FR (1) FR1105049A (en, 2012)
GB (1) GB752146A (en, 2012)

Cited By (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2865747A (en) * 1955-12-22 1958-12-23 Eastman Kodak Co Photographic color development process
US3236652A (en) * 1963-01-10 1966-02-22 Eastman Kodak Co Stabilized silver halide emulsions
US3637393A (en) * 1969-07-10 1972-01-25 Konishiroku Photo Ind Light-sensitive color photographic material with reduced fog and no decrease in speed during development
US3960570A (en) * 1973-02-09 1976-06-01 Fuji Photo Film Co., Ltd. Color photographic silver halide light-sensitive materials
US3982944A (en) * 1974-02-06 1976-09-28 Fuji Photo Film Co Ltd Antifoggant dispersion for color photographic materials
US4179293A (en) * 1977-08-09 1979-12-18 Fuji Photo Film Co., Ltd. Color photographic light-sensitive material
DE3021207A1 (de) * 1979-06-04 1980-12-11 Konishiroku Photo Ind Lichtempfindliches (farb)photographisches aufzeichnungsmaterial
US4277553A (en) * 1978-09-20 1981-07-07 Konishiroku Photo Industry Co., Ltd. Light-sensitive color photographic material
JPS5689739A (en) * 1972-11-20 1981-07-21 Eastman Kodak Co Photographic element
EP0112162A2 (en) 1982-12-13 1984-06-27 Konica Corporation Light-sensitive silver halide photographic material
US4485164A (en) * 1983-07-06 1984-11-27 Eastman Kodak Company Oxidants for reducing post-process D-min increase in positive redox dye-releasing image transfer systems
EP0147854A2 (en) 1983-12-29 1985-07-10 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive materials
EP0200502A2 (en) 1985-04-30 1986-11-05 Konica Corporation Light-sensitive silver halide color photographic material
EP0209118A2 (en) 1985-07-17 1987-01-21 Konica Corporation Silver halide photographic material
EP0218266A2 (en) 1984-05-02 1987-04-15 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material
EP0256537A2 (en) 1986-08-15 1988-02-24 Fuji Photo Film Co., Ltd. Color print and a method for producing the same
US4797443A (en) * 1985-04-29 1989-01-10 The B. F. Goodrich Company Stabilized vinyl halide resins and compositions and articles made therefrom
US4927744A (en) * 1988-08-05 1990-05-22 Eastman Kodak Company Photographic element having solid particle dispersion oxidized developer scavenger
US5026634A (en) * 1988-07-21 1991-06-25 Fuji Photo Film Co., Ltd. Color light-sensitive material
US5079133A (en) * 1986-04-11 1992-01-07 Fuji Photo Film Co., Ltd. Silver halide color photographic material
US5198517A (en) * 1991-08-06 1993-03-30 Eastman Kodak Company Polymeric scavengers for oxidized developing agents and photographic elements containing the same
US5264332A (en) * 1990-10-08 1993-11-23 Fuji Photo Film Co., Ltd. Silver halide color photographic material
US5300394A (en) * 1992-12-16 1994-04-05 Eastman Kodak Company Dispersions for imaging systems
US5434041A (en) * 1993-04-02 1995-07-18 Eastman Kodak Company Photographic elements containing particular color couplers in combination with hydroquinone type stabilizers
US5464731A (en) * 1993-03-01 1995-11-07 Fuji Photo Film Co., Ltd. Silver halide color photographic material
US5468604A (en) * 1992-11-18 1995-11-21 Eastman Kodak Company Photographic dispersion
US5478702A (en) * 1992-08-18 1995-12-26 Fuji Photo Film Co., Ltd. Method for forming a color image by scanning exposure using a photographic material containing a specific phenol derivative
EP0724194A1 (en) 1995-01-30 1996-07-31 Fuji Photo Film Co., Ltd. Silver halide color photographic material
EP0786689A1 (en) * 1996-01-29 1997-07-30 Eastman Kodak Company Photographic silver halide element having polyethylene naphthalate support and thin non-imaging bottom layers
EP0800113A2 (en) 1996-04-05 1997-10-08 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material
CN113122100A (zh) * 2021-05-24 2021-07-16 上海涂固安高科技有限公司 一种自抛光防污染防滕壶涂料及其制造方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2360290A (en) * 1941-07-31 1944-10-10 Eastman Kodak Co Preventing formation of color fog in emulsions

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2360290A (en) * 1941-07-31 1944-10-10 Eastman Kodak Co Preventing formation of color fog in emulsions

Cited By (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2865747A (en) * 1955-12-22 1958-12-23 Eastman Kodak Co Photographic color development process
US3236652A (en) * 1963-01-10 1966-02-22 Eastman Kodak Co Stabilized silver halide emulsions
US3637393A (en) * 1969-07-10 1972-01-25 Konishiroku Photo Ind Light-sensitive color photographic material with reduced fog and no decrease in speed during development
JPS5689739A (en) * 1972-11-20 1981-07-21 Eastman Kodak Co Photographic element
US3960570A (en) * 1973-02-09 1976-06-01 Fuji Photo Film Co., Ltd. Color photographic silver halide light-sensitive materials
US3982944A (en) * 1974-02-06 1976-09-28 Fuji Photo Film Co Ltd Antifoggant dispersion for color photographic materials
US4179293A (en) * 1977-08-09 1979-12-18 Fuji Photo Film Co., Ltd. Color photographic light-sensitive material
US4277553A (en) * 1978-09-20 1981-07-07 Konishiroku Photo Industry Co., Ltd. Light-sensitive color photographic material
US4277558A (en) * 1979-06-04 1981-07-07 Konishiroku Photo Industry Co., Ltd. Light-sensitive silver halide color photographic materials
DE3021207A1 (de) * 1979-06-04 1980-12-11 Konishiroku Photo Ind Lichtempfindliches (farb)photographisches aufzeichnungsmaterial
EP0112162A2 (en) 1982-12-13 1984-06-27 Konica Corporation Light-sensitive silver halide photographic material
US4485164A (en) * 1983-07-06 1984-11-27 Eastman Kodak Company Oxidants for reducing post-process D-min increase in positive redox dye-releasing image transfer systems
EP0147854A2 (en) 1983-12-29 1985-07-10 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive materials
EP0218266A2 (en) 1984-05-02 1987-04-15 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material
US4797443A (en) * 1985-04-29 1989-01-10 The B. F. Goodrich Company Stabilized vinyl halide resins and compositions and articles made therefrom
EP0200502A2 (en) 1985-04-30 1986-11-05 Konica Corporation Light-sensitive silver halide color photographic material
EP0209118A2 (en) 1985-07-17 1987-01-21 Konica Corporation Silver halide photographic material
US5079133A (en) * 1986-04-11 1992-01-07 Fuji Photo Film Co., Ltd. Silver halide color photographic material
EP0256537A2 (en) 1986-08-15 1988-02-24 Fuji Photo Film Co., Ltd. Color print and a method for producing the same
US5026634A (en) * 1988-07-21 1991-06-25 Fuji Photo Film Co., Ltd. Color light-sensitive material
US4927744A (en) * 1988-08-05 1990-05-22 Eastman Kodak Company Photographic element having solid particle dispersion oxidized developer scavenger
US5264332A (en) * 1990-10-08 1993-11-23 Fuji Photo Film Co., Ltd. Silver halide color photographic material
US5198517A (en) * 1991-08-06 1993-03-30 Eastman Kodak Company Polymeric scavengers for oxidized developing agents and photographic elements containing the same
US5478702A (en) * 1992-08-18 1995-12-26 Fuji Photo Film Co., Ltd. Method for forming a color image by scanning exposure using a photographic material containing a specific phenol derivative
US5468604A (en) * 1992-11-18 1995-11-21 Eastman Kodak Company Photographic dispersion
US5300394A (en) * 1992-12-16 1994-04-05 Eastman Kodak Company Dispersions for imaging systems
US5464731A (en) * 1993-03-01 1995-11-07 Fuji Photo Film Co., Ltd. Silver halide color photographic material
US5434041A (en) * 1993-04-02 1995-07-18 Eastman Kodak Company Photographic elements containing particular color couplers in combination with hydroquinone type stabilizers
EP0724194A1 (en) 1995-01-30 1996-07-31 Fuji Photo Film Co., Ltd. Silver halide color photographic material
EP0786689A1 (en) * 1996-01-29 1997-07-30 Eastman Kodak Company Photographic silver halide element having polyethylene naphthalate support and thin non-imaging bottom layers
EP0800113A2 (en) 1996-04-05 1997-10-08 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material
CN113122100A (zh) * 2021-05-24 2021-07-16 上海涂固安高科技有限公司 一种自抛光防污染防滕壶涂料及其制造方法

Also Published As

Publication number Publication date
BE529273A (en, 2012)
FR1105049A (fr) 1955-11-25
GB752146A (en) 1956-07-04

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