US3447926A - Color photographic silver halide elements containing 4-substituted urazoles and/or cycloalkane-1,3-diones - Google Patents

Color photographic silver halide elements containing 4-substituted urazoles and/or cycloalkane-1,3-diones Download PDF

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US3447926A
US3447926A US427481A US3447926DA US3447926A US 3447926 A US3447926 A US 3447926A US 427481 A US427481 A US 427481A US 3447926D A US3447926D A US 3447926DA US 3447926 A US3447926 A US 3447926A
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dione
issued
silver halide
cycloalkane
substituted
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Clark Beckett
Everett H Poppink
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Eastman Kodak Co
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Eastman Kodak Co
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    • 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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression

Definitions

  • Multicolor photographic elements containing at least one camera speed spectrally-sensitized emulsion containing a carbocyclic-1,3-dione, preferably in combination with a 4-substituted urazole have greatly reduced tendency to undergo latent image changes during storage between image exposure and photographic processing.
  • This invention relates to photographic elements and more particularly to certain multicolor, multilayer photographic elements containing latent image stabilizers.
  • Multilayer color films normally contain separate emulsion layers which record separate regions of the spectrum, usually blue, green, and red. During development, yellow, magenta, and cyan dyes are formed in these layers respectively. Color negative camera films are frequently exposed and then held for considerable lengths of time before processing. This situation frequently arises with amateur color roll films when a customer may take pictures on a single roll of film over a period of several months before he has the roll processed. Since optimum color quality is obtained only when the separate emulsion layers are balanced for sensitivity and contrast, it is desirable that the latent images produced by exposure do not change during an extended hold before processing. Unless the latent image in each layer changes at the same rate and in the same direction, distortion of the color balance will occur.
  • Another object is to provide novel multicolor photographic elements having silver halide emulsions that have a greatly reduced tendency to undergo latent image changes and a greatly reduced tendency to become fogged during long periods of storage.
  • multicolor, multilayer photographic elements containing at least one camera speed spectrally-sensitized silver halide emulsion containing a carbocyclic 1,3-dione.
  • a 4-substituted urazole can be used in combination with the cycloalkane-l,3-dione.
  • Typical suitable carbocyclic 1,3-diones include those having the formula:
  • Z represents the atoms required to complete a carbocyclic ring, e.g., having 5 to 6 carbons in the nucleus as cyclopentane, cyclohexane, cyclopentene, cyclohexene, etc., such that the said ring may be unsubstituted or substituted with groups, such as an alkyl (e.g., methyl, ethyl, butyl, hexyl, etc.); an aryl, (e.g., phenyl tolyl, methoxyphenyl, hexadecyloxyphenyl, naphthyl etc.); cyano; a carbalkoxy (e.g. carbomethoxy, carboethoxy, carbobutoxy, etc. etc.
  • groups such as an alkyl (e.g., methyl, ethyl, butyl, hexyl, etc.); an aryl, (e.g., phen
  • the preferred carbocyclic 1,3-diones include compounds shown to advantage by formula:
  • R and R each represent a group selected from the class consisting of hydrogen; an alkyl (e.g., methyl, ethyl, butyl, etc.); an aryl (e.g., phenyl, tolyl, naphthyl, etc.); cyano; a carbalkoxy (e.g., carbomethoxy, carboethoxy, etc.) and R and R are each selected from the class consisting of hydrogen, an alkyl (e.g., methyl, ethyl, butyl, amyl, etc.); an aryl (e.g., phenyl, methoxyphenyl ethoxyphenyl hexadecyloxyphenyl, tolyl, naphthyl, etc.).
  • an alkyl e.g., methyl, ethyl, butyl, etc.
  • an aryl e.g., phenyl, tolyl, naphthyl,
  • the cyclohexane-1,3-diones are prepared by the condensation of a,,B-unsaturated ketones with malonic acid esters, cyano acetic acid esters, or aryl acetic acid esters in the presence of basic catalysts such as sodium ethoxide.
  • the resulting compounds which contain carbalkoxy groups can be readily hydrolyzed to the corresponding carboxy compounds and decarboxylated.
  • the starting afi-UHSatIJ- rated ketones are prepared by condensation of ketones with aldehydes and ketones.
  • the preparation of 5,5-dimethylcyclohexane-l,3-dione may be given as an example of the preparation of a typical cyclic 1,3-diketone.
  • the preparation involves the condensation of mesityl oxide with diethyl malonate in the presence of sodium ethoxide. This is followed by hydrolysis of the ester group present in the resulting intermediate and decarboxylation.
  • a number of the cyclopentane-1,3-diones are described in the literature as for example cyclopentane-1,3-dione (Chem. Abstract, 43, 4908), 4,4 dimethylcyclopentane 1,3-dione (Chem. Abstract, 42, 4536c), etc.
  • Typical suitable 4-substituted urazoles including those represented by the formula:
  • R represents a group selected from the class consisting of hydrogen; an alkyl, e.g., methyl, ethyl, propyl, butyl, amyl, octyl, decyl, dodecyl, benzyl, carboxyethyl, sulfopropyl, sulfobutyl, etc; an aryl, e.g., phenyl, tolyl, naphthyl, etc.; R represents a group selected from the class consisting of an alkyl, e.g., methyl, ethyl, octyl, dodecyl, benzyl, carboxylethyl, sulfopropyl, sulfobutyl, etc.; an aryl, e.g., phenyl, tolyl, naphthyl, etc.; and monoacyl and diacyl derivatives of compounds of Formula III, such as the monoand
  • Typical compounds of Formula 111 includes the following: (1) 4-phenyl urazole (2) 4-phenyl-1-ethyl urazole (3) 4-ethyl urazole (4) 4-phenyl urazole, diacetyl derivative (5) 4-(a-naphthyl)urazole (6) 4-octyl urazole
  • a method commonly used for the preparation of 4-substituted urazoles is heating biurea and an amine hydrochloride in the range of 180-240" C.
  • l-substituted urazoles can be prepared by heating substituted hydrazine hydrochlorides with urea at 150-200 C.
  • Acyl derivatives can be prepared by acylation with anhydrides or acid chlorides.
  • the emulsions of our invention contain any of the higher speed silver halides such as silver bromoiodide, silver chlorobromide, and silver chlorobromoiodide desirably containing a predominate amount of bromide and a minor proportionate amount of iodide, (e.g., less than 10 mole percent) namely camera or high speed (e.g., A.S.A.
  • higher speed silver halides such as silver bromoiodide, silver chlorobromide, and silver chlorobromoiodide desirably containing a predominate amount of bromide and a minor proportionate amount of iodide, (e.g., less than 10 mole percent) namely camera or high speed (e.g., A.S.A.
  • emulsions which are typically chemically sensitized with such addenda as sulfur sensitizers and gold sensitizers, dispersed in any of the hydrophilic colloids usually used in photographic emulsions including naturally occurring materials, e.g., gelatin, agar-agar, albumin, gum arabic, alginic acid, etc., and synthetic materials, e.g., polyvinyl alcohol, polyvinyl pyrrolidone, cellulose ethers, partially hydrolyzed cellulose acetate, etc.
  • naturally occurring materials e.g., gelatin, agar-agar, albumin, gum arabic, alginic acid, etc.
  • synthetic materials e.g., polyvinyl alcohol, polyvinyl pyrrolidone, cellulose ethers, partially hydrolyzed cellulose acetate, etc.
  • the concentration of compounds of Formulas I and III used to advantage in our emulsions can be varied over a wide range.
  • the carbocyclic 1,3-diones are more generally used at concentrations of from about 0.1 to about 5 g. per mole of silver halide.
  • the 4-substituted urazoles are generally used in the range of from about 0.01 to about 5 g. per mole of silver halide.
  • the optimum concentrations will depend upon the particular emulsion used, the particular compounds and the results desired, etc., and can be readily determined by methods well known in the art. For example, a concentration series is made using separate portions of the emulsion, coatings are made and exposed. One sample of each coating is then processed and a second sample incubated for a period of time before processing. The effect of concentration on sensitometric changes can then be readily determined.
  • Our photographic silver halide emulsions can also contain such addenda as chemical sensitizers, e.g., sulfur, sensitizers (e.g., allyl thiocarbamide, thiourea, allylisothiocyanate, cystine, etc.), various gold compounds (e.g., potassium chloroaurate, auric trichloride, etc.) (see U.S. patents such as Baldsiefen U.S. 2,540,085, issued Feb. 6, 1951, Damschroder U.S. 2,597,856, issued May 27, 1952, Yutzy et al. U.S.
  • our emulsions are coated to advantage by well known methods on any of the materials usually used including, for example, paper, glass, cellulose acetate, cellulose nitrate, other synthetic film forming resins, eg., the polyesters, the polyamides, polystyrenes, etc.
  • Our multicolor elements are of the type described by Mannes et al. U.S. 2,113,329, issued April 5, 1938, which do not contain color-forming couplers or of the type con taining the color-forming couplers which comprise a support coated with a red-sensitive silver halide emulsion containing a cyan-dye-forming coupler, a green-sensitive silver halide emulsion containing a magenta-dye-forming coupler, a bleachable yellow colored filter layer and a blue-sensitive silver halide emulsion containing a yellow-dye-forming coupler.
  • the layers are often coated in the order listed, however the order can be varied provided the exposing light passes first through the bluesensitive layer and then the yellow-colored filter layer. Additional filter layers, antihalation layers, etc., may be used to advantage in our elements.
  • Example 1 A red-sensitive, high speed silver halide emulsion containing a phenolic cyan-dye-forming coupler was pre- N ethyl-B-methanesulfoamidoethyl 3 methyl-4- aminoanilinesulfate 2.0 Sodium sulfite (anhydrous) .6 Sodium carboniate (anhydrous) 30.
  • Example 2 Table II Cone. of 4-phenyl urazole Fog growth on incubation in g./mole of silver: vs. fresh coatings 0 +.13 +03 5 +.02
  • the 4-substituted urazoles are used to advantage in multilayer, multicolor elements that do not contain color-forming couplers for reducing the amount of fog produced by storage at high temperatures and humidities.
  • Example 3 A series of multilayer color films on a cellulose acetate support were prepared as described in Example 1.
  • the green-sensitive emulsion layer contained a pyrazolone magenta-dye-forming coupler and also in certain cases contained 4-phenyl urazole.
  • the coatings were exposed and processed as described in Example 1. Table III shows the results.
  • any other of our cycloalkane-1,3-diones of Formula I and 4-substitute urazoles of Formula III are used to advantage in spectrally-sensitized photographic silver halide emulsions to minimize latent image changes and fog resulting from storage of an element containing said emulsion.
  • a multicolor, multilayer photographic element containing at least one camera speed silver halide emulsion spectrally sensitized to light in the green or red region of the spectrum, said emulsion containing a carbocyclic-1,3- dione having the formula:
  • Z represents the atoms required to complete a carbocyclic ring having from 5 to 6 carbon atoms in the nucleus such that the said ring is substituted with members selected from the class consisting of hydrogen, an alkyl group, an aryl group, a carbalkoxy group and the cyano group, the said carbocyclic 1,3-dione being incorporated to reduce latent image speed change.
  • a multicolor, multilayer photographic element containing at least one red-sensitized camera speed silver halide emulsion containing a cyan dye-forming coupler and a cycloalkane-1,3-dione having the formula:
  • R and R each represent a group selected from the class consisting of hydrogen, an alkyl, on aryl, cyano, and a carbalkoxy; and R and R each represent a group selected from the class consisting of hydrogen, an alkyl and an aryl, the said cycloa1kane-1,3-dione being incorporated to reduce latent image speed change.
  • a multicolor, multilayer photographic element containing at least one gree-sensitized camera speed silver 7 halide emulsion containing a magenta dye-forming coupler and a. cycloalkane-1,3-dione having the formula:
  • R and R each represent a group selected from the class consisting of hydrogen, an alkyl, an aryl, cyano, and a carbalkoxy; and R and R each represent a group selected from the class consisting of hydrogen, an alkyl and an aryl, the said cycloalkane-1,3-dione being incorporated to reduce latent image speed change.
  • R and R each represent a group selected from the class consisting of hydrogen, an alkyl, an aryl, cyano, and a carbalkoxy; and R and R each represent a group selected from the class consisting of hydrogen, an alkyl and an aryl; and (3) a 4-substituted urazole having the formula:
  • R1NNH wherein R represents a group selected from the class consisting of hydrogen, an alkyl and an aryl; R represents a group selected from the class consisting of an alkyl group, and an aryl group, the said cycloalkane- 1,3-dione and said 4-su'bstituted urazole being used as latent image stabilizers, the said cycloalkane-1,3- dione being used to reduce latent image speed changes and the said 4-substituted urazole being used to reduce latent image fog growth.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
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  • General Physics & Mathematics (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US427481A 1965-01-22 1965-01-22 Color photographic silver halide elements containing 4-substituted urazoles and/or cycloalkane-1,3-diones Expired - Lifetime US3447926A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4334010A (en) * 1980-07-17 1982-06-08 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive element
US4418142A (en) * 1980-10-08 1983-11-29 Agfa Gevaert Aktiengesellschaft Light-sensitive photographic silver halide recording material
EP0200878A1 (en) 1982-02-24 1986-11-12 Konica Corporation Light-sensitive silver halide color photographic material
EP0229721A3 (en) * 1986-01-17 1988-09-07 Eastman Kodak Company Detection of hydrolyzing enzymes
US7014989B1 (en) * 2005-04-18 2006-03-21 Eastman Kodak Company Photothermographic materials containing 4-substituted urazoles

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2708162A (en) * 1954-04-29 1955-05-10 Eastman Kodak Co Urazole stabilizer for emulsions sensitized with alkylene oxide polymers
US2857275A (en) * 1954-11-08 1958-10-21 Polaroid Corp Photographic compositions and processes
US2895827A (en) * 1956-10-24 1959-07-21 Eastman Kodak Co Photographic paper base
US2944899A (en) * 1956-10-04 1960-07-12 Eastman Kodak Co Stabilization of photographic silver halide emulsions
US3140182A (en) * 1963-06-11 1964-07-07 Eastman Kodak Co Non-ionized polymethine sensitizing dyes

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2708162A (en) * 1954-04-29 1955-05-10 Eastman Kodak Co Urazole stabilizer for emulsions sensitized with alkylene oxide polymers
US2857275A (en) * 1954-11-08 1958-10-21 Polaroid Corp Photographic compositions and processes
US2944899A (en) * 1956-10-04 1960-07-12 Eastman Kodak Co Stabilization of photographic silver halide emulsions
US2895827A (en) * 1956-10-24 1959-07-21 Eastman Kodak Co Photographic paper base
US3140182A (en) * 1963-06-11 1964-07-07 Eastman Kodak Co Non-ionized polymethine sensitizing dyes

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4334010A (en) * 1980-07-17 1982-06-08 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive element
US4418142A (en) * 1980-10-08 1983-11-29 Agfa Gevaert Aktiengesellschaft Light-sensitive photographic silver halide recording material
EP0200878A1 (en) 1982-02-24 1986-11-12 Konica Corporation Light-sensitive silver halide color photographic material
EP0229721A3 (en) * 1986-01-17 1988-09-07 Eastman Kodak Company Detection of hydrolyzing enzymes
US7014989B1 (en) * 2005-04-18 2006-03-21 Eastman Kodak Company Photothermographic materials containing 4-substituted urazoles

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BE675347A (cs) 1966-05-16
GB1129623A (en) 1968-10-09
DE1547664C3 (de) 1975-05-22
DE1547664A1 (de) 1969-12-04

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