US3770447A - Light-sensitive silver halide color photographic material containing indazolone couplers - Google Patents

Light-sensitive silver halide color photographic material containing indazolone couplers Download PDF

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Publication number
US3770447A
US3770447A US00213814A US3770447DA US3770447A US 3770447 A US3770447 A US 3770447A US 00213814 A US00213814 A US 00213814A US 3770447D A US3770447D A US 3770447DA US 3770447 A US3770447 A US 3770447A
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US
United States
Prior art keywords
couplers
light
silver halide
indazolone
photographic material
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Expired - Lifetime
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US00213814A
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English (en)
Inventor
I Boie
W Schulte
D Freitag
F Nittel
W Pelz
H Krimm
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Agfa Gevaert AG
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Agfa Gevaert AG
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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
    • C07D231/54—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings condensed with carbocyclic rings or ring systems
    • C07D231/56—Benzopyrazoles; Hydrogenated benzopyrazoles
    • 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
    • G03C7/3231—Couplers containing an indazolone ring

Definitions

  • ABSTRACT A light-sensitive photographic material with at least one silver halide emulsion layer which contains indazolone derivatives as couplers for the production of the magenta partial image, which indazolone couplers are represented by the following formula:
  • color developers in the presence of suitable color forming couplers, the oxidation product of the developer substances produced in areas corresponding to the silver image reacting with the color coupler to form an image which consists of dye.
  • the color developers commonly used are aromatic compounds which contain primary amino groups, especially those of the p-phenylene diamine type.
  • the mechanical properties of the layers should not be impaired by the color couplers and lastly the dyes produced from the color couplers in the course of chromogenic development should have a suitable absorption curve with a maximum corresponding to the color of the partial image which is required to be produced and at the same time they should have as little side absorption as possible.
  • a magenta dye should be almost completely absorbent to green light and high transmittent to blue and red light.
  • magenta-forming couplers i.e. color couplers which are suitable for producing the magenta color image
  • color couplers which are suitable for producing the magenta color image
  • 2- pyrazolone-S. lndazolone derivatives are also occasionally used as magenta-forming couplers (see US Pat.
  • Indazolone couplers which are readily soluble in ethyl acetate, methylene chloride and similar organic solvents have not previously been known. This property, combined with the usually high melting points, has hitherto made it difficult to use indazolone couplers in photographic layers.
  • indazolone couplers which may be preparedby a new process involving alkylation of the nucleus of anthranilic acid esters with suitably substituted styrene derivatives or the corresponding a-carbinols followed by indazolone ring closure are characterised by exceptionally advantageous properties both as regards their higher sensitivity and as regards their reduced tendency to undergo brown discoloration in the presence of light.
  • the subject of the invention is a lightsensitive color photographic material having at least one silver halide emulsion layer, containing a magenta coupler represented by the following formula NH Ill X and Y may be the same or different and represent hydrogen, halogen, e.g., chlorine, alkyl with l to 18 carbon atoms, thioalkyllwith 1 to 18 carbon atoms,
  • color couplers of the following formula:
  • indazolone derivatives in which at least one of the radicals R,, R X, Y and Z contains a large hydrocarbon radical with at least 12 carbon atoms.
  • at least one of the radicals X and Y is halogen, alkyl, alkoxy, aroxy or acylamino.
  • Coupler Number a suitably Substituted styrene, optionally in the dimeric form, or the corresponding a-carbinol is reacted with anthranilic acid esters with the aid of acid catalysts to aklylate the anthranilic acid esters in the -positio'n. indazolone ring closure in then carried out in a known manner. If desired, a sulfo group may finally be introduced.
  • the method of preparation will now be explained with the aid of a few examples.
  • Coupler 4 is obtained.
  • the new magenta-forming couplers are superior to the known indazolone couplers in three respects. Firstly, their stability is greatly improved, especially their stability to light, and, secondly, the new couplers have a greatly reduced tendency to undergo brown discoloration in the presence of light and, thirdly, the products are much more readily emulsifiable provided the molecule does not contain any group which renders it soluble in alkalis. A particularly remarkable characteristic is the increase in the coupling sensitivity by 3 to 5 DIN, which enables the new components to be used also for highly sensitive photographic material.
  • magenta dyes obtained from the new color coupiers by means of N,N-diethyl-p-phenylene diamine or- N-butyl-n-w-sulfobutyl-p-phenylene diamine as developer have exceptionally good spectral properties.
  • the side densities in the blue region and especially in the red region are very low.
  • the compounds according to the invention are, therefore, valuable color couplers which, on chromogenic development, yield magenta dyes which have excellent stability characteristics. They are eminently suitable for use in light-sensitive silver halide emulsion layers of single layered or multilayered photographic material.
  • magenta-forming couplers need not necessarily be incorporated in light-sensitive layers, but could be introduced into a layer of binder adjacent to a light-sensitive silver halide emulsion layer.
  • the magenta-forming couplers according to the invention may be incorporated with the silver halide emulsion by one of the known methods or they may be incorporated with another binder mixture.
  • the couplers according to the invention are so-called emulsifying couplers, i.e., hydrophobic compounds
  • incorporation of these couplers is carried out in a known manner by dissolving them in suitable organic solvents, e.g., in esters of aliphatic carboxylic acids, especially in ethyl acetate, or in methylene chloride, and emulsifying this solution in the silver halide emulsion which is ready for casting.
  • this method may advantageously be modified by using oily coupler solvents at the same time. This method has been disclosed in [1.8. Pat. Nos. 2,304,940 and 2,322,027.
  • Suitable light-sensitive emulsions are emulsions of silver halides such as silver chloride, silver bromide or mixtures thereof, optionally with a small silver iodide content of up to mols percent, in one of the commonly used hydrophilic binders such as protein binders, especially gelatine, or polyvinyl alcohol, polyvinyl pyrrolidone, cellulose derivatives such as carboxyalkyl cellulose, and especially carboxymethyl cellulose, or derivatives of alginic acid.
  • hydrophilic binders such as protein binders, especially gelatine, or polyvinyl alcohol, polyvinyl pyrrolidone, cellulose derivatives such as carboxyalkyl cellulose, and especially carboxymethyl cellulose, or derivatives of alginic acid.
  • the emulsions may also be chemically sensitized, e.g. by adding compounds which contain sulfur to the process of chemical ripening, for example allyl isothiocyanate, allyl thiourea, and sodium thiosulfate.
  • the chemical sensitizers used may also be reducing agents, e.g., the tin compounds described in Belgian Pat. specificaq N 4 514. 5 331d. 5.6. .16 or o m d ha diethylene triamine or aminomethane sulfinic acid derivatives, e.g. according to British Pat. No. 789,823.
  • Suitable chemical sensitisers are noble metals and noble metal compounds, such as gold, platinum, palladium, iridium, ruthenium or rhodium. This method of chemical sensitisation has been described in the article by R. Kos lowsky, Z. Wiss. Phot.
  • the emulsions may also be sensitised with polyalkylene oxide derivatives, e.g., with polyethylene oxide having a molecular weight of between 1,000 and 20,000 or with condensation products of alkylene oxides and aliphatic alcohols, glycols or cyclic dehydration products of hexitols with alkyl-substituted phenols, aliphatic carboxylic acids, aliphatic amines, aliphatic diamines and amides.
  • the condensation products have a molecular weight of at least 700, and preferably more than 1,000.
  • the emulsions which contain color-forming couplers may also contain spectral sensitizers, e.g., the usual monomethine or polymethine dyes such as cyanines, hemicyanines, streptocyanines, merocyanines, oxonoles, hemioxonoles, and styryl dyes, including also methine dyes which have three or more nuclei, for example rhodacyanines or neocyanines.
  • Sensitizers of this kind have been described, for example, in the work by RM. Hamer, The Cyanine Dyes and Related Compounds (1964), Interscience Publishers, John Wiley and Sons.
  • the color couplers according to the invention are, however, preferably used in emulsions which have been sensitized to green light.
  • the emulsions may contain the usual stabilisers, e.g. homopolar or salt-type compounds'of mercury which have aromatic or heterocyclic rings, such as mercaptotriazoles, simple mercury salts, sulfonium mercury double salts and other mercury compounds.
  • Suitable stabilisers are also azaindenes, especially tetraand pentaazaindenes, and especially those which are substituted with hydroxyl or amino groups. Compounds of this type have been described in the article by Birr, Z. Wiss. Phot. 47, 2-58 (1952).
  • Other suitable stabilisers include heterocyclic mercapto compounds, e.g., phenyl mercaptotetrazole, quaternary benzothiazole derivatives, and benzotriazole.
  • the emulsions may be hardened in the usual manner, for example with formaldehyde or halosubstituted aldehydes which contain a carboxyl group, such as mucobromic acid, diketones, methane sulfonic acid esters, dialdehydes.
  • formaldehyde or halosubstituted aldehydes which contain a carboxyl group, such as mucobromic acid, diketones, methane sulfonic acid esters, dialdehydes.
  • the usual color developers are used for producing the magenta partial image, e.g., the usual aromatic compounds of the para-phenylene type which contain at least one primary amino group.
  • Suitable color developers are, e.g., N,N-dimethyl-p-phenylen diamine, N,N-diethyl-p-phenylene diamine, monomethyl-pphenylene diamine, N-butyLN-w-shlfobutyl-pphenylene diamine.
  • Other suitable color developers have been described, e.g., in J. Am. Chem. Soc. 73, pages 3,100 to 3,125 (1951). It is preferred to use developers in which the two positions adjacent to the primary amino group are unsubstituted.
  • Example 1 tained. Another wedge (b) is prepared by the same method with coupler (l) of the U.S. l at. No.
  • Example 2 is cast on a transparent layer support. After develop-' ment with N,N-diethyl-p-phenylene diamine, the film is bleached and fixed in the usual manner.
  • the coupler is found to be more sensitive by 4 DIN than the coupler in the comparison wedge (Coupler l of the US. Pat. No. 3,199,983).
  • the absorption maximum is in the region of 552 nm.
  • Example 3 g of Coupler(S) are dissolved in 50 ml of ethyl acetate and, after the addition of 10 g of dibutyl phthalate, the solution is worked up as in Example 2. A magenta wedge which has an absorption maximum at 544 my. is obtained. The sensitivity is higher by 4 DIN than that of wedge (b) from Example 1.
  • Example 4 10 g of Coupler (19) are cast as described in Exam ple 2. After exposure, the film strip is subjected to the usual reversal process using N,N'-diethylamino-pphenylene diamine as developer substance. A magenta positive image is obtained.
  • the increase in sensitivity compared with that of a film material which contains Coupler (1) of the US. Pat. No. 3,199,983 and has been developed in the same manner is 3 DIN. Absorption maximum 557 nm.
  • R hydrogen or alkyl with l to 3 carbon atoms
  • R alkyl with up to 17 carbon atoms and R and R may form a cycloalkane ring
  • X and Y may be the same or different and represent hydrogen, halogen, alkyl with 1 to 18 carbon atoms, cycloalkyl, alkoxy with l to 18 carbon atoms, thioalkyl with l to 18 carbon atoms, phenyl, aroxy or acylamino;
  • X or Y may form together with R, or R a cycloalkane ring;
  • Z hydrogen or a group-which. rendersthe compound soluble in alkalis or sulfamyl.
  • R hydrogen or alkyl with l to 3 carbon atoms
  • R and R may together form a cycloalkane ring
  • X and Y may be the same or different and represent hydrogen, halogen, alkyl with l to 18 carbon atoms, alkoxy with l to 18 carbon atoms, aroxy or acylamirfo;
  • Z hydrogen, a group which renders the compound soluble in alkalis or sulfamyl.

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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)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
US00213814A 1970-12-29 1971-12-29 Light-sensitive silver halide color photographic material containing indazolone couplers Expired - Lifetime US3770447A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19702064304 DE2064304A1 (de) 1970-12-29 1970-12-29 Lichtempfindliches farbfotografisches Material

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US (1) US3770447A (enrdf_load_stackoverflow)
BE (1) BE777352A (enrdf_load_stackoverflow)
CA (1) CA982395A (enrdf_load_stackoverflow)
CH (1) CH569309A5 (enrdf_load_stackoverflow)
DE (1) DE2064304A1 (enrdf_load_stackoverflow)
FR (1) FR2121036A5 (enrdf_load_stackoverflow)
GB (1) GB1350229A (enrdf_load_stackoverflow)
IT (1) IT945653B (enrdf_load_stackoverflow)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4067872A (en) * 1975-07-02 1978-01-10 Polaroid Corporation Cyclic derivatives of 1,2,3,4 tetrahydroquinoline and indolene
EP0124795A2 (en) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US4540654A (en) * 1983-03-18 1985-09-10 Fuji Photo Film Co., Ltd. Method of forming color image comprising heterocyclic magenta dye-forming coupler
EP0177765A1 (en) 1984-09-06 1986-04-16 Fuji Photo Film Co., Ltd. Silver halide color photographic material
US4863842A (en) * 1985-09-12 1989-09-05 Konica Technosearch Corporation Silver halide photographic light sensitive material
US5155016A (en) * 1988-07-27 1992-10-13 Fuji Photo Film Co., Ltd. Silver halide color photographic material containing novel pyrazoloazole coupler and method to produce color image
US5229408A (en) * 1988-07-15 1993-07-20 Ici Pharma 4-carbamoyl-1,2-dihydro-3H-indazol-3-one derivatives
EP0686873A1 (en) 1994-06-08 1995-12-13 Eastman Kodak Company Color photographic element containing new epoxy scavengers for residual magenta coupler
US20030158189A1 (en) * 1997-11-04 2003-08-21 Anthony Marfat Therapeutically active compounds based on indazole bioisostere replacement of catechol in PDE4 inhibitors

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7314888B1 (en) 1998-11-05 2008-01-01 Toyama Chemical Co., Ltd. Compounds and medicinal use thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2673801A (en) * 1948-11-23 1954-03-30 Gevaert Photo Prod Nv Production of color photographic images
US3043694A (en) * 1960-05-23 1962-07-10 Eastman Kodak Co Novel class of 3-indazolinone developing agent
US3199983A (en) * 1961-02-01 1965-08-10 Agfa Ag 3-indazolone color couplers

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2673801A (en) * 1948-11-23 1954-03-30 Gevaert Photo Prod Nv Production of color photographic images
US3043694A (en) * 1960-05-23 1962-07-10 Eastman Kodak Co Novel class of 3-indazolinone developing agent
US3199983A (en) * 1961-02-01 1965-08-10 Agfa Ag 3-indazolone color couplers

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4067872A (en) * 1975-07-02 1978-01-10 Polaroid Corporation Cyclic derivatives of 1,2,3,4 tetrahydroquinoline and indolene
US4540654A (en) * 1983-03-18 1985-09-10 Fuji Photo Film Co., Ltd. Method of forming color image comprising heterocyclic magenta dye-forming coupler
EP0124795A2 (en) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
EP0177765A1 (en) 1984-09-06 1986-04-16 Fuji Photo Film Co., Ltd. Silver halide color photographic material
US4863842A (en) * 1985-09-12 1989-09-05 Konica Technosearch Corporation Silver halide photographic light sensitive material
US5229408A (en) * 1988-07-15 1993-07-20 Ici Pharma 4-carbamoyl-1,2-dihydro-3H-indazol-3-one derivatives
US5155016A (en) * 1988-07-27 1992-10-13 Fuji Photo Film Co., Ltd. Silver halide color photographic material containing novel pyrazoloazole coupler and method to produce color image
EP0686873A1 (en) 1994-06-08 1995-12-13 Eastman Kodak Company Color photographic element containing new epoxy scavengers for residual magenta coupler
US20030158189A1 (en) * 1997-11-04 2003-08-21 Anthony Marfat Therapeutically active compounds based on indazole bioisostere replacement of catechol in PDE4 inhibitors

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Publication number Publication date
DE2064304A1 (de) 1972-07-20
IT945653B (it) 1973-05-10
BE777352A (nl) 1972-06-28
CH569309A5 (enrdf_load_stackoverflow) 1975-11-14
CA982395A (en) 1976-01-27
FR2121036A5 (enrdf_load_stackoverflow) 1972-08-18
GB1350229A (en) 1974-04-18

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