EP0654148B1 - Verwendung von ketogluconaten in der photographie - Google Patents

Verwendung von ketogluconaten in der photographie Download PDF

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Publication number
EP0654148B1
EP0654148B1 EP93916592A EP93916592A EP0654148B1 EP 0654148 B1 EP0654148 B1 EP 0654148B1 EP 93916592 A EP93916592 A EP 93916592A EP 93916592 A EP93916592 A EP 93916592A EP 0654148 B1 EP0654148 B1 EP 0654148B1
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EP
European Patent Office
Prior art keywords
methyl
metal salts
photographic
ketogluconate
pyrazolidone
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
EP93916592A
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English (en)
French (fr)
Other versions
EP0654148A1 (de
Inventor
Herman L. Gewanter
Joseph M. Rashan, Jr.
Larry R. Reitz
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.)
Danisco Finland Oy
Original Assignee
Cultor Oyj
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Publication date
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Publication of EP0654148A1 publication Critical patent/EP0654148A1/de
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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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/29—Development processes or agents therefor
    • G03C5/30—Developers

Definitions

  • the present invention relates to the use of derivatives of ketogluconic acid as photographic agents.
  • Silver halide emulsions are coated on various papers and films for use in photographic applications. When these emulsions have been exposed to radiation, the sensitized emulsion produces a latent image in the silver halide grains. The image is latent because the grains are sensitized to reduction by the formation of minute quantities of free silver in the grains from the exposure. These grains are developed by placing the exposed photosensitive material in an aqueous solution containing one or more specific reducing chemicals. There are very few reducing agents which will only develop the latent image and not reduce the unexposed silver halide. The reducing agents conventionally employed include such organic materials as hydroquinone and other materials meeting the criteria of the Kendall-Pelz rule.
  • Two of these developing agents may be used in the same formulation to produce a result known in the photographic industry as superadditivity, also known as synergy. It is defined as the mixture of two developing agents showing a greater degree of developer activity than the sum of the actions of each agent separately.
  • Figs. 1-6 are graphs showing the effect of various ketogluconates on photographic media.
  • the present invention is directed to a process for the development of a photographic image on a photographic medium comprising reducing the photosensitized silver on said medium with an effective amount of (a) a compound selected from the group consisting of alkali metal salts, alkaline earth metal salts, amine salts of ketogluconic acid, alkali metal salts, alkaline earth metal salts and amine salts of stereoisomers of ketogluconic acid; and C 1 -C 4 alkyl esters of ketogluconic acid and C 1 -C 4 alkyl esters of stereoisomers of ketogluconic acid; and (b) a co-developer.
  • a compound selected from the group consisting of alkali metal salts, alkaline earth metal salts, amine salts of ketogluconic acid, alkali metal salts, alkaline earth metal salts and amine salts of stereoisomers of ketogluconic acid and C 1 -C 4 alkyl esters of ketogluconic acid and C 1
  • the salt of ketogluconic acid is sodium-2-ketogluconate.
  • the ester is the methyl ester.
  • the methyl ester is methyl-2-ketogluconate.
  • the alkaline earth metal salt is calcium-2,5-diketogluconate.
  • the co-developer is selected from the group consisting of 4-methylaminophenol, 1-phenyl-3-pyrazolidone, and para-phenylenediamines.
  • the present invention is directed to a photographic composition
  • a photographic composition comprising (a) an effective amount of a developing agent selected from the group consisting of alkali metal salts, alkaline earth metal salts, amine salts of ketogluconic acid; alkali metal salts, alkaline earth metal salts and amine salts of stereoisomers thereof; C 1 -C 4 alkyl esters of said salts of ketogluconic acid and stereoisomers thereof; and (b) a co-developer.
  • a developing agent selected from the group consisting of alkali metal salts, alkaline earth metal salts, amine salts of ketogluconic acid; alkali metal salts, alkaline earth metal salts and amine salts of stereoisomers thereof; C 1 -C 4 alkyl esters of said salts of ketogluconic acid and stereoisomers thereof; and (b) a co-developer.
  • the co-developer is selected from the group consisting of 4-methylaminophenol, 1-phenyl-3-pyrazolidone, and para-phenylenediamines.
  • the present invention is directed to a process for the development of a photographic image on a photographic medium comprising reducing the photosensitized silver on said medium with an effective amount of methyl-2-ketogluconate.
  • the present invention is directed to a photographic composition containing an effective amount of methyl-2-ketogluconate as a developing agent.
  • ketogluconic acid uses derivatives of ketogluconic acid. These derivatives are used in the form of salts which are hereinafter referred to as either ketogluconates or in the case of the stereoisomers, as ketogulonates.
  • keto-gluconates One class of the present developing agents are the alkali metal salts of keto-gluconates, and stereoisomers thereof.
  • the D, L and DL forms of the keto-gluconates may be used.
  • Stereoisomers of the ketogluconates include the ketogulonates which may also be used in the D, L or DL forms.
  • Preferred alkali metal salts are the sodium and potassium salts.
  • the sodium and potassium salts of the keto-D-gluconates, keto-L-gluconates, and the keto-DL-gluconates may be used in the composition and process of the present invention.
  • the sodium and potassium salts of the keto-D-gulonates, keto-L-gulonates and keto-DL-gulonates may be used in the process and compositions of the present invention.
  • Preferred amine salts are the ammonium salts, the triethanolamine salts, the diethylaminoethyl, cyclohexylamine, and the morpholine salts of the ketogluconates and ketogulonates.
  • Preferred alkaline earth metal salts are the calcium salts of ketogluconates and ketogulonates.
  • ketogluconic acid also exist in the diketo form.
  • salts of ketogluconic acid include the diketo salts and esters include the diketo esters.
  • esters of the ketogluconates and ketogulonates are the C 1 -C 4 alkyl esters. Preferred is the methyl ester.
  • ketogluconic acid is used with a co-developer.
  • co-developers are metol (1-phenyl-3 pyrazolidone), a pyrazolidone derivative, phenidone (4-aminomethylphenol), and para-phenylenediamines.
  • 3-pyrazolidone silver halide developing agents may be used.
  • Examples of such derivatives include: 1-p-tolyl-3-pyrazolidone, 5-phenyl-3-pyrazolidone, 5-met-3-pyrazolidone, 1-p-chlorophenol-3-pyrazolidone, 1-phenyl-5-phenyl-3-pyrazolidone, m-tolyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-p-tolyl-5-phenyl-3-pyrazolidone, 1-m-tolyl-3-pyrazolidone, 1-p-methoxyphenyl-3-pyrazolidone, 1-acetamidophenyl-3-pyrazolidone, 1-phenyl-2-acetyl-4, 4-dimethyl-3-pyrazolidone, 1-phenyl-4, 4-dimethyl-3-pyrazolidone, 1-m-aminophenyl-4-4-propyl-3-pyrazolidone, 1-o-chlorophenol--4.methyl-4-eth
  • phenylenediamine compounds are N,N-diethyl-p-phenylene-diamine, N,N-diethyl-o-methyl-p-phenylenediamine, N,N-diethyl-methoxy-p-phenylenediamine, P-phenylenediamine, N-ethyl-n-hydroxyethyl-p-phenylenediamine, and N-ethyl-N-hydroxyethyl-o-methyl-p-phenylenediamine.
  • photographic media on which images may be developed include black and white print film, color transparencies, black and white transparencies, and color print film.
  • the present invention is also directed to a process for developing a photographic image by using methyl-2-ketogluconate as a developer, and to a photographic composition containing methyl-2-ketogluconate as a developing agent.
  • the exposure and developing of the film took place in total darkness.
  • the film was exposed in a X-Rite 383 sensitometer which has a built in 21 step wedge template.
  • the film was then developed in a test formulation for 4 minutes, stopped for 10 seconds, and fixed (Kodak F-5) for 4 minutes. Again the entire development procedure took place at a constant agitation and a temperature of 20 degree C.
  • the film was then washed in running water for 20 minutes, squeeged, and dried, and a D log E curve was prepared.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Cosmetics (AREA)

Claims (10)

  1. Verfahren zur Entwicklung von fotografischen Bildern auf einem fotografischen Medium, welches darin besteht, fotosensibilisiertes Silber auf besagtem Medium zu reduzieren, mit einer ausreichenden Menge von (a) einer Substanz ausgewählt aus der Gruppe bestehend aus Alkalimetallsalzen, Erdalkalimetallsalzen und Aminsalzen von Ketogluconsäure; Alkalimetallsalzen, Erdalkalimetallsalzen und Aminsalzen von Stereoisomeren von Ketogluconsäure und C1-C4-Alkylestern von Ketogluconsäure, C1-C4-Alkylestern von Stereoisomeren von Ketogluconsäure und (b) einem Co-Entwickler für das fotografische Medium.
  2. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß das Salz der Ketogluconsäure ein Natrium-2-ketogluconat ist.
  3. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß der Ester ein Methylester ist.
  4. Verfahren gemäß Anspruch 3, dadurch gekennzeichnet, daß der Methylester ein Methyl-2-ketogluconat ist.
  5. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß das Erdalkalimetallsalz Calcium-2,5-diketogluconat ist.
  6. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß der Co-Entwickler ausgewählt ist aus der Gruppe bestehend aus Methylaminophenol, 1-Phenyl-3-pyrazolidon und Paraphenylendiaminen.
  7. Fotografisches Material, welches eine ausreichende Menge eines Entwicklungsmittels ausgewählt aus der Gruppe bestehend aus Alkalimetallsalzen, Erdalkalimetallsalzen, Aminsalzen von Ketogluconsäure; Alkalimetallsalzen, Erdalkalimetallsalzen und Aminsalzen von Stereoisomeren davon; C1-C4-Alkylestern von Ketogluconsäure und C1-C4-Alkylestern von Stereoisomeren von Ketogluconsäuren und (b) ein Co-Entwickler in dem fotografischen Medium besteht.
  8. Material gemäß Anspruch 7, dadurch gekennzeichnet, daß der Co-Entwickler ausgewählt ist aus der Gruppe bestehend aus Methylaminophenol, 1-Phenyl-3-pyrazolidon und Paraphenylendiaminen.
  9. Verfahren für die Entwicklung eines fotografischen Bildes auf einem fotografischen Medium bestehend aus der Reduktion des fotosensibilisierten Silbers auf besagtem Medium mit einer ausreichenden Menge von Methyl-2-ketogluconat.
  10. Fotografisches Material enthaltend eine ausreichende Menge von Methyl-2-ketogluconat als Entwicklungsmittel.
EP93916592A 1992-08-05 1993-06-22 Verwendung von ketogluconaten in der photographie Expired - Lifetime EP0654148B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US92609292A 1992-08-05 1992-08-05
US926092 1992-08-05
PCT/US1993/005802 WO1994003834A1 (en) 1992-08-05 1993-06-22 Use of ketogluconates in photography

Publications (2)

Publication Number Publication Date
EP0654148A1 EP0654148A1 (de) 1995-05-24
EP0654148B1 true EP0654148B1 (de) 1997-10-15

Family

ID=25452743

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93916592A Expired - Lifetime EP0654148B1 (de) 1992-08-05 1993-06-22 Verwendung von ketogluconaten in der photographie

Country Status (9)

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EP (1) EP0654148B1 (de)
JP (1) JP2801084B2 (de)
AT (1) ATE159350T1 (de)
AU (1) AU672418B2 (de)
CA (1) CA2140541A1 (de)
DE (1) DE69314652T2 (de)
DK (1) DK0654148T3 (de)
ES (1) ES2111760T3 (de)
WO (1) WO1994003834A1 (de)

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1467007A (en) * 1974-04-18 1977-03-16 Ciba Geigy Ag Photographic processing method
US4551411A (en) * 1984-12-28 1985-11-05 Eastman Kodak Company Sequestrants used in diffusion transfer elements with metallizable dyes
SU1381416A1 (ru) * 1986-03-24 1988-03-15 Ленинградский Институт Киноинженеров Про вл юще-фиксирующий раствор
US5147767A (en) * 1991-04-10 1992-09-15 Knapp Audenried W Gluconic acid-based developer composition

Also Published As

Publication number Publication date
ATE159350T1 (de) 1997-11-15
DK0654148T3 (da) 1998-06-02
DE69314652D1 (de) 1997-11-20
JPH07506200A (ja) 1995-07-06
WO1994003834A1 (en) 1994-02-17
AU672418B2 (en) 1996-10-03
EP0654148A1 (de) 1995-05-24
CA2140541A1 (en) 1994-02-17
ES2111760T3 (es) 1998-03-16
DE69314652T2 (de) 1998-04-16
JP2801084B2 (ja) 1998-09-21
AU4639093A (en) 1994-03-03

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