US2600788A - Halogen-substituted pyrazolone couplers for color photography - Google Patents

Halogen-substituted pyrazolone couplers for color photography Download PDF

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US2600788A
US2600788A US97701A US9770149A US2600788A US 2600788 A US2600788 A US 2600788A US 97701 A US97701 A US 97701A US 9770149 A US9770149 A US 9770149A US 2600788 A US2600788 A US 2600788A
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compound
halogen
image
silver halide
developing
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Loria Anthony
Paul W Vittum
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Eastman Kodak Co
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Eastman Kodak Co
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    • 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
    • G03C7/36—Couplers containing compounds with active methylene groups
    • G03C7/38—Couplers containing compounds with active methylene groups in rings
    • G03C7/384—Couplers containing compounds with active methylene groups in rings in pyrazolone rings

Definitions

  • invention relates ⁇ to photo raphy and an sticularly :tocompoundswhich form dyes on coupling with the developing agent to produce coloredimages.
  • tkis knownthat colored photographic images may :be formed by using a developerwhich produces a colored image on development.
  • a coupling compound or coupler Such a compound which employed in conjunction with a developing agent for the silver-and which-couples with the oxidation product of the developing agent during development is referred to herein as a coupling compound or coupler.
  • N ONHC- o R Q X]: ⁇ COH2 where'X -is halogen; such as chlorineor bromine,
  • 2,4,6-tribromaniline (Beilstein 12, 663) was diazotized and the cold solution of diazonium salt was added to a cold sodium sulfite solution. The mixture was warmed to 60 C. for 30 minutes and was then esterified with concentrated hydrochloric acid. The reaction mixture was then heated overnight on the steam bath. The 2,4,6-tribromophenylhydrazine hydrochloride was obtained by adding concentrated hydrochloric acid to the hot solution. The hydrochloride was converted washed with col chlorobenzene and petroleum ether.
  • a solution oi sodium ethoxide was prepared from sodium and alcohol and to this was added the ethyl-(2,4,6-tribromophenyl) hydrazine-flimino propionate prepared above. The mixture was refluxed for 15 to 20 minutes, cooled to 50 C., diluted with water and esterified with glacial acetic acid. l-(2',4',6-tribromophenyl)-3- amino-S-pyrasolone se arated as a thick, creamy slurry and this mixture was cooled, filtered and the product washed with water and dried at 100 C.
  • the 1 (2,4,6'-tribromopheny1) 3 amino 5- pyrazolone was dissolved in dry pyridine and two moles of benzoyl chloride were added. The mixture was heated for ten minutes on a steam bath, then cooled -to room temperature and diluted with water. The product which separated was the dibenzoyl derivative. The dibenzoyl derivative was saponified in alcoholic potassium hydroxide and the solution was filtered and acidified with acetic acid. The 1-(2, l,6'tribrom0- phenyl)3-benzamido-5-pyrazolone separated as a solid and was filtered, washed with water and dried and found to have a melting point of 274-276 C.
  • Compound 2 was prepared in the same manher as compound 1 using 2,4,6-trichloroaniline (Beilstein 12, 627) instead of 2,4,6-tribromaniline.
  • Compound 4 was prepared in the same manner as compound 1, using phenylacetyl chloride in place of benzoyl chloride.
  • Compound 11 was prepared by coriderising "1'- veloping solutions containing a primary aromatic amino developing agent. Compounds 1 to 4 may be used in this way.
  • Thefollowing example illustrates a developing solution which may be used with the compounds of our invention.
  • Couplers may be incorporated in sensitive silver halide emulsion layers as described in Mannes and Godowsky U. S. Patent 2,304,940 or Jelley and Vittum U. S. Patent 2,322,027.
  • Compounds 5 to 12 may be used in this way.
  • compound 7 may be incorporated in a silver halide emulsion as described in Example 1 of J elley and Vittum U. S. Patent 2,322,027.
  • the exposed emulsion layer may be developed in a solution having the composition of Part A of the developing solution described above.
  • the aromatic amino developing agents used with the coupler compounds of our invention include the mono-, diand tri-amino aryl compounds and their derivatives formed by substitution in the amino group as well as in the ring such as alkyl phenylene diamines and alkyl toluylene diamines. These compounds are usually used in the salt form such as the hydrochloride or the sulfate which are more stable than the amines themselves.
  • the peamino phenols and theirsubstitutionproduct's may-also be used wherethe amino group is unsubstituted. All of these compounds have an unsubstituted amino group which enables the oxidation'products of the developer to couple with the colorforming compounds to forma. dye image.
  • Qur'development process may be employed for the'production by colored photographic images in layers of gelatin or other carrier for the silver halide "such as collodion, organic esters of cellulose or synthetic resins.
  • the support for the emulsion may be a transparent material such as glassjcllulose ester ora; non-transparent reflectg material such as. paper or anopaque cellulose
  • the emulsion may be Icoated'as a "s'iii'gl'e I yer on the suppers or as superpcsesiayr's-6n one or both sides of the "siip'pdrt.
  • the superposed layers may be difierentially sensitized to form natural color photographic images in the well-known manner. For example, in a multilayer material sensitized "to're'd, green and blue light, respectively, our couplers would ordinarily be used in the green-sensitive emulsion layer to form the magenta image.
  • Dyes formed from the couplers of our inven- 'tio'n f have an absorption m'axiniumin the green spectral ⁇ region which is shifted toward the 'red by-about 50 to20'0 "millimierons as compared with dyes from correspondmg couplers with a simple l-phenylor l chlorophenyl substituent. :Atthe same time, there is little or no 'incre'aseinab- "sorptionin the bluean'd red regions of the spec- "trum.
  • the method of producing a magentacolored image in a silver halide emulsion layer which comprises exposing said layer and developing it with a primary'aromaticamino developing agent in the presence of a 1-phenyl-3- acylamino-5-pyra'iolone coupler compound having at least two halogen substituents on the 1- phenyl radical.
  • COR is an acyl radical
  • COR is an acyl radical
  • a photographic emulsion for forming a magenta-colored image comprising a silver halide emulsion having incorporated therein a coupler compound having the formula:
  • COR is an acyl radical
  • a photographic emulsion for forming a magenta-colored image comprising a silver halide emulsion having incorporated therein a coupler compound having the formula:
  • a photographic emulsion for forming a magenta-colored image comprising a silver halide emulsion having incorporated therein a coupler compound having the formula:

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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)
  • Heat Sensitive Colour Forming Recording (AREA)

Description

Patented June 17, 1952 UNITED sTATEs PATENT OFFICE HALOGEN-SUBSTITUTED IifiQAZQLAQNE COUPLEBIS FOR COLOR rno'roonsrnv Anthony Lori'a, Arnold Weissberger, and Paul W. 'Vittum, Rochester, N. Y., assignors t o Eastman Kodak Company, Rochester, N. Y., a corporation of New J ersey No Drawing. ApplicationJune '7, 1949,
Serial No. 97,701
invention relates {to photo raphy and an sticularly :tocompoundswhich form dyes on coupling with the developing agent to produce coloredimages.
tkis knownthat colored photographic images may :be formed by using a developerwhich produces a colored image on development. The
colored compound thus formed is depositedadvjacent the silver grains of the silver image duringrdevelopment. It'is also known thata colored imagemaybe formed by adding to said. developer sol utionor by incorporating in the silver halide emulsi n before or after exposure ,a compo n which couples during development with :the
oxidation product of the developing agent and which-forms acolored compound which is likewise deposited adjacent "1211B silver grains of the silver image during development. Such a compound which employed in conjunction with a developing agent for the silver-and which-couples with the oxidation product of the developing agent during development is referred to herein as a coupling compound or coupler.
The use ofvariouspyrazolone derivatives for t e p oduction of-the ma nt ma en hr colorphotography is well-known-and theuse of 1 phenyl-3eacylamino 5-pyrazolones forthispurpose is described inflorterand Weissberger U; S. Batent v -2,3(i9.,489 One of the disadvantages of thfise'coupler is that when the coupler is incorporated ,-in the sensitive emulsion layer, tl 1 e residualco l le'rs which vremain after formation of 1 the: dye image is not so stable: as is desired and causesvdiscolorationof the final picture. Ail-1rther vdisadvanta.ge is that the magenta dye thanis desired. H
It i-s' thereforean objector the .presentinven- 'tion toprovioea novel class oicou-plers'for formiiigitheniagentadye image rin color photography. A .fur therobjectijsi to. provide couplers whi ch have improvedstability to light and heat when incorp ratedin-the emulsion layer. Astill further b 'tis'ltoprovidea class of couplers-tor formthan similar, couplersandwhichhave armaximum absorption shifted towards the longer wave lengths. vQtherobjects willappear from thefollowing description oi-our-invention.
These objects ereaccomplished by developing anexposed silver halide emulsion layer twitha nrimaryeromatic amino devel p .esentinth presencect a l.;phenyl--3 acylaminmfi-pyrazolone coupler r-compound having at least two halogen substituents on the "l-rphenyl radical. The: com
10 Claims.
g g .35 01 formed from theycouplers absorbs more blue light J ing -niage'ntasdyes which absorb less blue li ht pounds which we propose to use have the following structural formula:
N=ONHC- o R Q X]: \COH2 where'X -is halogen; such as chlorineor bromine,
10 n is two or more and'COR' is anacyl radical such as benzoyl, phenyl acetyl, etc. Compounds hav ing the above .fcrmula, in which X11 represents three chlorine substituents are especially valuable for use as couplers according to our invention.
The following compounds illustrate the couplerswniehma be us accordin to ou invention.
' '30 1- (2',4,6'-1:richlorophe1iyl) 3 -benzamido-5-pyrazolone (2 f .4',6 -trichlorophenyl) -3-pl1enylacetamido-5- pyrazelone' 1 (2 AC6 -tribromophenyl) 3 -phenylacetarnld0 -5- pliiioiyacetamidoj benzamidol'-5-pyraiolone 1- (2 ',5-dichlorophe11yl) -3- 3' (2' ,4 -di-tert. amylphenoxyacetamido) -benzamldo] -5-pyrazolone NHCOCHzO 1-(2',4',6'-tribromophenyl)-3-[3"-(4"-tert. amylphenoxy) -benzamido] -5-pyrazolone The compounds of our invention are prepared in general by condensing a dihalo or trihalo aryl hydrazine with ethyl-p-ethoxy-p-imino proprionate to form an ethyl-B-(p-haloaryl) hydrazinefi-imino propionate and ring closure of the latter with sodium ethoxide. The imino compound is acylated in the usual manner to form the acylamino pyrazolone.
Compound 1 was prepared as follows:
2,4,6-tribromaniline (Beilstein 12, 663) was diazotized and the cold solution of diazonium salt was added to a cold sodium sulfite solution. The mixture was warmed to 60 C. for 30 minutes and was then esterified with concentrated hydrochloric acid. The reaction mixture was then heated overnight on the steam bath. The 2,4,6-tribromophenylhydrazine hydrochloride was obtained by adding concentrated hydrochloric acid to the hot solution. The hydrochloride was converted washed with col chlorobenzene and petroleum ether.
A solution oi sodium ethoxide was prepared from sodium and alcohol and to this was added the ethyl-(2,4,6-tribromophenyl) hydrazine-flimino propionate prepared above. The mixture was refluxed for 15 to 20 minutes, cooled to 50 C., diluted with water and esterified with glacial acetic acid. l-(2',4',6-tribromophenyl)-3- amino-S-pyrasolone se arated as a thick, creamy slurry and this mixture was cooled, filtered and the product washed with water and dried at 100 C.
The 1 (2,4,6'-tribromopheny1) 3 amino 5- pyrazolone was dissolved in dry pyridine and two moles of benzoyl chloride were added. The mixture was heated for ten minutes on a steam bath, then cooled -to room temperature and diluted with water. The product which separated was the dibenzoyl derivative. The dibenzoyl derivative was saponified in alcoholic potassium hydroxide and the solution was filtered and acidified with acetic acid. The 1-(2, l,6'tribrom0- phenyl)3-benzamido-5-pyrazolone separated as a solid and was filtered, washed with water and dried and found to have a melting point of 274-276 C.
Compound 2 was prepared in the same manher as compound 1 using 2,4,6-trichloroaniline (Beilstein 12, 627) instead of 2,4,6-tribromaniline.
Compound 3 was prepared in the same manner as compound 2, using phenylacetyl chloride in place of benzoyl chloride.
Compound 4 was prepared in the same manner as compound 1, using phenylacetyl chloride in place of benzoyl chloride.
Compound 5 was prepared as follows:
50 grams of l-(2,4-dichlorophenyl)-3-amino- 5-pyrazolone, prepared as in the preparation of compound 1, using 2,4-dichloroaniline in place of 2,4,6-tribromaniline was placed in a round-bottomed flask together with 625 cc. of glacial acetic acid and 93 grams of m-nitrobenzoyl chloride. The mixture was heated to boiling and refluxed for 30 minutes. A clear solution was formed but the product began to separate while still hot. The reaction mixture was cooled to room temperature, filtered, washed with 500 cc. of ethyl alcohol and 500 cc. of ether and dried at 100 C. This formed the diacyl derivative which was sifted, suspended in 70% ethyl alcohol and heated to 70 C. and 40% caustic solution was stirred into the mixture. The stirring was continued vigorously for sixty seconds and the mixture acidified with glacial acetic acid. The monoacyl product separated at once and the slurry was stirred and cooled to room temperature. The product was filtered, washed with 200 cc. of ethyl alcohol, and 200 cc. of ether and dried at 100 C. This formed the mnitrobenzamido derivative and 53 grams of this derivative was placed in a round-bottom flask with 1325 cc. of acetic acid. The mixture was heated to boiling and 53 grams of iron powder were added. The charge was refluxed for fifteen minutes or until all of the nitro compound had dissolved. The solution was then filtered and stirred into two liters of boiling water. This mixture was heated to boiling, cooled to room temcedure as compound 2 using /i-zA-di-tert."amylphenoxy propionyl chloride (Weissberger I et al. U. S. application Serial No. 83,762) instead of benzoyl chloride. It had a melting point of 220-222 Compound was prepared by the same procedure as compound 1 using 5-2.4-di-tert. amylpherfoxy propionyl chloride instead of benzoyl chloride; Ithad 'amelting point of *225 -227C.
"Compound 11 "was prepared by coriderising "1'- veloping solutions containing a primary aromatic amino developing agent. Compounds 1 to 4 may be used in this way. Thefollowing example illustrates a developing solution which may be used with the compounds of our invention.
Grams "p-Xminodiethyl aniline sulfate 2 isoldiumsulfite (anhydrous) .5 Sodium carbonate (anhydrous) Potassium bromide 2 Water to 1 liter.
1-(2',4',6'-trichloro phenyl) -3-benzamido-5- pyrazolone grams 2 Sodium hydroxide (2% solution) cc 50 For use, B is added to A.
Certain of our couplers may be incorporated in sensitive silver halide emulsion layers as described in Mannes and Godowsky U. S. Patent 2,304,940 or Jelley and Vittum U. S. Patent 2,322,027. Compounds 5 to 12 may be used in this way. For example, compound 7 may be incorporated in a silver halide emulsion as described in Example 1 of J elley and Vittum U. S. Patent 2,322,027. When used in this way, the exposed emulsion layer may be developed in a solution having the composition of Part A of the developing solution described above.
The aromatic amino developing agents used with the coupler compounds of our invention include the mono-, diand tri-amino aryl compounds and their derivatives formed by substitution in the amino group as well as in the ring such as alkyl phenylene diamines and alkyl toluylene diamines. These compounds are usually used in the salt form such as the hydrochloride or the sulfate which are more stable than the amines themselves. Suitable compounds are diethyl pephenylene 'diamine hydrochloride, mono- ;ethylepphenylene diamine hydrochloride, dimethylep-phenylene diamine hydrochloride, dimethylspvphenylene sulfate and -2:-a'mino-"5='diethyl amino toluene sulfate. The peamino phenols and theirsubstitutionproduct'smay-also be used wherethe amino group is unsubstituted. All of these compounds have an unsubstituted amino group which enables the oxidation'products of the developer to couple with the colorforming compounds to forma. dye image.
Qur'development process may be employed for the'production by colored photographic images in layers of gelatin or other carrier for the silver halide "such as collodion, organic esters of cellulose or synthetic resins. The support for the emulsion may be a transparent material such as glassjcllulose ester ora; non-transparent reflectg material such as. paper or anopaque cellulose The emulsion may be Icoated'as a "s'iii'gl'e I yer on the suppers or as superpcsesiayr's-6n one or both sides of the "siip'pdrt. The superposed layers may be difierentially sensitized to form natural color photographic images in the well-known manner. For example, in a multilayer material sensitized "to're'd, green and blue light, respectively, our couplers would ordinarily be used in the green-sensitive emulsion layer to form the magenta image.
Dyes formed from the couplers of our inven- 'tio'n f have an absorption m'axiniumin the green spectral {region which is shifted toward the 'red by-about 50 to20'0 "millimierons as compared with dyes from correspondmg couplers with a simple l-phenylor l chlorophenyl substituent. :Atthe same time, there is little or no 'incre'aseinab- "sorptionin the bluean'd red regions of the spec- "trum.
Weclaim:
1. The method of producing a magentacolored image in a silver halide emulsion layer which comprises exposing said layer and developing it with a primary'aromaticamino developing agent in the presence of a 1-phenyl-3- acylamino-5-pyra'iolone coupler compound having at least two halogen substituents on the 1- phenyl radical.
2. 'The method of producing a magentacolored image f in "a silver halide 1 emulsion layer which comprises exposing said layer and developing it with a primary aromatic amino developing agent in the presence of a coupler compound having the formula:
| CO- H:
where COR is an acyl radical.
3. The method of producing a magentacolored image in a. silver halide emulsion layer which comprises exposing said layer and developing it with a primary aromatic amino developing agent in the presence of a coupler compound having the formula:
Br N\ where COR is an acyl radical.
4. The method of producing a magentacolored image in a silver halide emulsion layer which comprises exposing said layer and developing it with a primary aromatic amino developing agent in the presence of a coupler compound having the formula:
l \C Hi 5. The method of producing a magentacolored image in a silver halide emulsion layer Nncocngo aHn which comprises exposing said layer and developing it with a primary aromatic amino developing agent in the presence of a coupler compound having the formula:
sHu
' N=CNHCOR l (51 CO H:
where COR is an acyl radical.
8. A photographic emulsion for forming a magenta-colored image comprising a silver halide emulsion having incorporated therein a coupler compound having the formula:
where COR is an acyl radical.
9. A photographic emulsion for forming a magenta-colored image comprising a silver halide emulsion having incorporated therein a coupler compound having the formula:
01- N I I i NHCOCHQO 1 C OCH2 1 10. A photographic emulsion for forming a magenta-colored image comprising a silver halide emulsion having incorporated therein a coupler compound having the formula:
ARNOLD WEISSBERGER. PAUL W. VI'I'IUM.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Number Name Date 2,213,986 Kendall et a1 Sept. 10, 1940 2,343,702 Porter et al Mar. 7, 1944 2,369,489 Porter et a1. Feb. 13, 1945 FOREIGN PATENTS Number Country Date France Jan. 11, 1939

Claims (1)

1. THE METHODE OF PRODUCING A MAGENTACOLORED IMAGE IN. A SILVER HALIDE EMULSION LAYER WHICH COMPRISES EXPOSING SAID LAYER AND DEVELOPING IT WITH A PRIMARY AROMATIC AMINO DEVELOPING AGENT IN THE PRESENCE OF A 1-PHENYL-3ACYLAMINO-5-PYRAZOLONE COUPLER COMPOUND HAVING AT LEAST TWO HALOGEN SUBSTITUENTS ON THE 1PHENYL RADICAL.
US97701A 1949-06-07 1949-06-07 Halogen-substituted pyrazolone couplers for color photography Expired - Lifetime US2600788A (en)

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US97701A US2600788A (en) 1949-06-07 1949-06-07 Halogen-substituted pyrazolone couplers for color photography
GB14168/50A GB680488A (en) 1949-06-07 1950-06-07 Improvements in colour photographic couplers
FR1099911D FR1099911A (en) 1949-06-07 1950-06-07 New compounds, usable in particular as couplers for color photography and products containing them

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Cited By (59)

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US2852382A (en) * 1955-08-11 1958-09-16 Eastman Kodak Co Coupler dispersions for color photography containing protein polymers
US2865751A (en) * 1956-09-18 1958-12-23 Eastman Kodak Co 1-alkyl-3-acylamido-5-pyrazolone couplers for color photography
US2933391A (en) * 1956-09-06 1960-04-19 Eastman Kodak Co Photographic emulsions containing 5-pyrazolone coupler compounds
US3006759A (en) * 1959-08-03 1961-10-31 Eastman Kodak Co Two-equivalent magenta-forming couplers for color photography
US3311476A (en) * 1962-12-26 1967-03-28 Eastman Kodak Co Two-equivalent couplers for color photography
US3356686A (en) * 1960-04-13 1967-12-05 Du Pont Substituted amidopyrazalones containing a terminal ethylenically unsaturated group
JPS4918327A (en) * 1972-06-12 1974-02-18
US3897254A (en) * 1973-05-11 1975-07-29 Mitsubishi Paper Mills Ltd Silver halide containing pyrazolone magenta coupler
US3952008A (en) * 1973-04-17 1976-04-20 Bayer Aktiengesellschaft Pyrazol-5-ones
US3957814A (en) * 1973-04-17 1976-05-18 Bayer Aktiengesellschaft Pyrazol-5-ones
US3992404A (en) * 1973-04-17 1976-11-16 Bayer Aktiengesellschaft Pyrazol-5-ones
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US4002641A (en) * 1973-12-20 1977-01-11 Bayer Aktiengesellschaft Pyrazole derivatives
US4005215A (en) * 1973-04-17 1977-01-25 Bayer Aktiengesellschaft Pyrazol-5-ones
US4032646A (en) * 1973-04-17 1977-06-28 Bayer Aktiengesellschaft Pyrazol-5-ones
US4045571A (en) * 1973-04-17 1977-08-30 Bayer Aktiengesellschaft Pyrazol-5-ones
US4053621A (en) * 1974-06-06 1977-10-11 Bayer Aktiengesellschaft 1-[2-(βNaphthyloxy)ethyl]-3-methylpyrazolone-(5) and antithrombotic and antithrombolytic compositions and methods utilizing them
US4056533A (en) * 1973-04-17 1977-11-01 Bayer Aktiengesellschaft Pyrazol-5-ones
US4061653A (en) * 1972-06-23 1977-12-06 Bayer Aktiengesellschaft 1-Substituted-3-amino-pyrazol-5-ones
US4069334A (en) * 1973-12-20 1978-01-17 Bayer Aktiengesellschaft Pyrazole derivatives
US4081596A (en) * 1973-04-17 1978-03-28 Bayer Aktiengesellschaft Pyrazol-5-ones
USRE30420E (en) * 1973-04-17 1980-10-21 Bayer Aktiengesellschaft Pyrazol-5-ones
US4288446A (en) * 1973-04-17 1981-09-08 Bayer Aktiengesellschaft Pyrazol-5-ones
WO1982002198A1 (en) * 1980-12-29 1982-07-08 Kodak Co Eastman A method for preparing 2-pyrazolin-5-ones from 1,2,4-oxadiazoles
US4374253A (en) * 1981-09-28 1983-02-15 Eastman Kodak Company Method for preparing 1-aryl-3-arylamino-2-pyrazolin-5-ones from N-aryl-3-arylamino-3-oximinopropionamides
US4409323A (en) * 1980-02-15 1983-10-11 Konishiroku Photo Industry Co., Ltd. Silver halide photographic material
EP0112162A2 (en) 1982-12-13 1984-06-27 Konica Corporation Light-sensitive silver halide photographic material
EP0124795A2 (en) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
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
EP0201033A2 (en) 1985-04-30 1986-11-12 Konica Corporation A method for processing silver halide color photographic materials
EP0200878A1 (en) 1982-02-24 1986-11-12 Konica Corporation Light-sensitive silver halide color photographic material
EP0202616A2 (en) 1985-05-16 1986-11-26 Konica Corporation Method for color-developing a silver halide photographic light-sensitive material
EP0204175A1 (en) 1985-05-09 1986-12-10 Fuji Photo Film Co., Ltd. Silver halide color photographic materials
EP0204530A2 (en) 1985-05-31 1986-12-10 Konica Corporation Method for forming direct positive color image
JPS61292636A (en) * 1985-06-20 1986-12-23 Konishiroku Photo Ind Co Ltd Silver halide color photographic sensitive material
EP0228914A2 (en) 1985-12-28 1987-07-15 Konica Corporation Method of processing lightsensitive silver halide color photographic material
EP0253390A2 (en) 1986-07-17 1988-01-20 Fuji Photo Film Co., Ltd. Photographic support and color photosensitive material
EP0266797A2 (en) 1986-11-07 1988-05-11 Fuji Photo Film Co., Ltd. Method of processing silver halide color photographic material and photographic color developing composition
US4871652A (en) * 1988-09-07 1989-10-03 Eastman Kodak Company Photographic silver halide material and process
EP0452984A1 (en) 1985-09-25 1991-10-23 Fuji Photo Film Co., Ltd. Process for processing silver halide color photographic material for photographing use
US5252446A (en) * 1991-09-25 1993-10-12 Konica Corporation Silver halide color photographic light-sensitive material comprising a 1-pentachlorinated phenyl-5-pyrazolone coupler and specific red sensitizing dyes
US5270156A (en) * 1991-10-11 1993-12-14 Konica Corporation Silver halide color photographic light sensitive material
EP0574090A1 (en) 1992-06-12 1993-12-15 Eastman Kodak Company One equivalent couplers and low pKa release dyes
US5275926A (en) * 1991-09-25 1994-01-04 Konica Corporation Silver halide color photographic light-sensitive material
US5354646A (en) * 1986-03-26 1994-10-11 Konishiroku Photo Industry Co., Ltd. Method capable of rapidly processing a silver halide color photographic light-sensitive material
US5460924A (en) * 1992-12-14 1995-10-24 Eastman Kodak Company Photographic peracid bleaches with ferric 2-pyridinecarboxylate and 2,6-pyridinecarboxylate catalysts
EP0684515A1 (en) 1994-05-27 1995-11-29 Eastman Kodak Company Photographic element and process incorporating a high dye-yield image coupler providing improved granularity
EP0686873A1 (en) 1994-06-08 1995-12-13 Eastman Kodak Company Color photographic element containing new epoxy scavengers for residual magenta coupler
EP0695968A2 (en) 1994-08-01 1996-02-07 Eastman Kodak Company Viscosity reduction in a photographic melt
US5492798A (en) * 1993-12-01 1996-02-20 Konica Corporation Silver halide color photographic light-sensitive material
EP0698816A1 (en) 1994-08-26 1996-02-28 Eastman Kodak Company Photographic paper formed with low molecular weight polyvinyl alcohol having low oxygen permeability
US5565313A (en) * 1993-12-20 1996-10-15 Konica Corporation Silver halide color photographic light-sensitive material
US5571661A (en) * 1994-06-09 1996-11-05 Konica Corporation Silver halide light-sensitive color photographic material
EP0779544A1 (en) 1995-12-11 1997-06-18 Eastman Kodak Company Photographic element containing an improved pyrazolotriazole coupler
EP0779536A1 (en) 1995-12-04 1997-06-18 Konica Corporation Light-and heat-sensitive recording material and recording method by use thereof
EP0779543A1 (en) 1995-12-11 1997-06-18 Eastman Kodak Company Photographic element containing an improved pyrazolotriazole coupler
EP0782044A1 (en) 1995-12-27 1997-07-02 Konica Corporation Silver halide light-sensitive color photographic material
WO2013032827A1 (en) 2011-08-31 2013-03-07 Eastman Kodak Company Motion picture films to provide archival images

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US3006759A (en) * 1959-08-03 1961-10-31 Eastman Kodak Co Two-equivalent magenta-forming couplers for color photography
US3356686A (en) * 1960-04-13 1967-12-05 Du Pont Substituted amidopyrazalones containing a terminal ethylenically unsaturated group
US3311476A (en) * 1962-12-26 1967-03-28 Eastman Kodak Co Two-equivalent couplers for color photography
JPS4918327A (en) * 1972-06-12 1974-02-18
US4061653A (en) * 1972-06-23 1977-12-06 Bayer Aktiengesellschaft 1-Substituted-3-amino-pyrazol-5-ones
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US4081596A (en) * 1973-04-17 1978-03-28 Bayer Aktiengesellschaft Pyrazol-5-ones
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US3897254A (en) * 1973-05-11 1975-07-29 Mitsubishi Paper Mills Ltd Silver halide containing pyrazolone magenta coupler
US4069334A (en) * 1973-12-20 1978-01-17 Bayer Aktiengesellschaft Pyrazole derivatives
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US4053621A (en) * 1974-06-06 1977-10-11 Bayer Aktiengesellschaft 1-[2-(βNaphthyloxy)ethyl]-3-methylpyrazolone-(5) and antithrombotic and antithrombolytic compositions and methods utilizing them
US4409323A (en) * 1980-02-15 1983-10-11 Konishiroku Photo Industry Co., Ltd. Silver halide photographic material
WO1982002198A1 (en) * 1980-12-29 1982-07-08 Kodak Co Eastman A method for preparing 2-pyrazolin-5-ones from 1,2,4-oxadiazoles
US4345085A (en) * 1980-12-29 1982-08-17 Eastman Kodak Company Method for preparing 2-pyrazolin-5-ones from 1,2,4-oxadiazoles
US4374253A (en) * 1981-09-28 1983-02-15 Eastman Kodak Company Method for preparing 1-aryl-3-arylamino-2-pyrazolin-5-ones from N-aryl-3-arylamino-3-oximinopropionamides
EP0200878A1 (en) 1982-02-24 1986-11-12 Konica Corporation Light-sensitive silver halide color photographic material
EP0112162A2 (en) 1982-12-13 1984-06-27 Konica Corporation Light-sensitive silver halide photographic material
EP0124795A2 (en) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
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
EP0201033A2 (en) 1985-04-30 1986-11-12 Konica Corporation A method for processing silver halide color photographic materials
EP0204175A1 (en) 1985-05-09 1986-12-10 Fuji Photo Film Co., Ltd. Silver halide color photographic materials
EP0202616A2 (en) 1985-05-16 1986-11-26 Konica Corporation Method for color-developing a silver halide photographic light-sensitive material
EP0204530A2 (en) 1985-05-31 1986-12-10 Konica Corporation Method for forming direct positive color image
JPS61292636A (en) * 1985-06-20 1986-12-23 Konishiroku Photo Ind Co Ltd Silver halide color photographic sensitive material
EP0452984A1 (en) 1985-09-25 1991-10-23 Fuji Photo Film Co., Ltd. Process for processing silver halide color photographic material for photographing use
EP0228914A2 (en) 1985-12-28 1987-07-15 Konica Corporation Method of processing lightsensitive silver halide color photographic material
US5354646A (en) * 1986-03-26 1994-10-11 Konishiroku Photo Industry Co., Ltd. Method capable of rapidly processing a silver halide color photographic light-sensitive material
EP0253390A2 (en) 1986-07-17 1988-01-20 Fuji Photo Film Co., Ltd. Photographic support and color photosensitive material
EP0266797A2 (en) 1986-11-07 1988-05-11 Fuji Photo Film Co., Ltd. Method of processing silver halide color photographic material and photographic color developing composition
US4871652A (en) * 1988-09-07 1989-10-03 Eastman Kodak Company Photographic silver halide material and process
US5275926A (en) * 1991-09-25 1994-01-04 Konica Corporation Silver halide color photographic light-sensitive material
US5252446A (en) * 1991-09-25 1993-10-12 Konica Corporation Silver halide color photographic light-sensitive material comprising a 1-pentachlorinated phenyl-5-pyrazolone coupler and specific red sensitizing dyes
US5270156A (en) * 1991-10-11 1993-12-14 Konica Corporation Silver halide color photographic light sensitive material
EP0574090A1 (en) 1992-06-12 1993-12-15 Eastman Kodak Company One equivalent couplers and low pKa release dyes
US5460924A (en) * 1992-12-14 1995-10-24 Eastman Kodak Company Photographic peracid bleaches with ferric 2-pyridinecarboxylate and 2,6-pyridinecarboxylate catalysts
US5536625A (en) * 1992-12-14 1996-07-16 Eastman Kodak Company Photographic peracid bleaches with ferric 2-pyridinecarboxylate and 2,6-pyridinecarboxylate catalysts
US5492798A (en) * 1993-12-01 1996-02-20 Konica Corporation Silver halide color photographic light-sensitive material
US5565313A (en) * 1993-12-20 1996-10-15 Konica Corporation Silver halide color photographic light-sensitive material
EP0684515A1 (en) 1994-05-27 1995-11-29 Eastman Kodak Company Photographic element and process incorporating a high dye-yield image coupler providing improved granularity
EP0686873A1 (en) 1994-06-08 1995-12-13 Eastman Kodak Company Color photographic element containing new epoxy scavengers for residual magenta coupler
US5571661A (en) * 1994-06-09 1996-11-05 Konica Corporation Silver halide light-sensitive color photographic material
EP0695968A2 (en) 1994-08-01 1996-02-07 Eastman Kodak Company Viscosity reduction in a photographic melt
EP0698816A1 (en) 1994-08-26 1996-02-28 Eastman Kodak Company Photographic paper formed with low molecular weight polyvinyl alcohol having low oxygen permeability
EP0779536A1 (en) 1995-12-04 1997-06-18 Konica Corporation Light-and heat-sensitive recording material and recording method by use thereof
EP0779544A1 (en) 1995-12-11 1997-06-18 Eastman Kodak Company Photographic element containing an improved pyrazolotriazole coupler
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GB680488A (en) 1952-10-08
FR1099911A (en) 1955-09-14

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