EP0548124A1 - Stabilisers for rx developers. - Google Patents

Stabilisers for rx developers.

Info

Publication number
EP0548124A1
EP0548124A1 EP91915628A EP91915628A EP0548124A1 EP 0548124 A1 EP0548124 A1 EP 0548124A1 EP 91915628 A EP91915628 A EP 91915628A EP 91915628 A EP91915628 A EP 91915628A EP 0548124 A1 EP0548124 A1 EP 0548124A1
Authority
EP
European Patent Office
Prior art keywords
stabiliser
developer
agent
oxidising agent
redox amplification
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.)
Granted
Application number
EP91915628A
Other languages
German (de)
French (fr)
Other versions
EP0548124B1 (en
Inventor
Amanda Audrey Kodak Tannahill
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.)
Kodak Ltd
Eastman Kodak Co
Original Assignee
Kodak Ltd
Eastman Kodak Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Kodak Ltd, Eastman Kodak Co filed Critical Kodak Ltd
Publication of EP0548124A1 publication Critical patent/EP0548124A1/en
Application granted granted Critical
Publication of EP0548124B1 publication Critical patent/EP0548124B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • G03C7/3017—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials with intensification of the image by oxido-reduction
    • G03C7/302—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials with intensification of the image by oxido-reduction using peroxides

Definitions

  • This invention relates to stabilisers for RX developers.
  • Particularly the invention relates to the processing of photographic materials by redox amplification developer systems in order to ameliorate the inherent instability of such solutions.
  • these acids and their functional salts will stabilise oxidants such as peroxide even in the presence of the normal components of a redox amplification developer system, and that the presence of such acids and/or their functional salts has not only the effect of inhibiting the interaction between the colour developer and the stabiliser, thereby to increase the useful life of the developer solutions, but also beneficially effects the development process to enhance the developed quality of the image by markedly reducing the so of such systems to produce fogged products.
  • uric acid, phosphoric acid or its functional salts may be included in a coating on a photographic paper thereby to give improved fogging levels by inhibiting oxidant/colour developer interaction in situ.
  • a colour developer composition comprising an oxidising agent and a colour developing component, wherein the composition additionally comprises a stabiliser such as uric acid for the oxidising agent.
  • a stabiliser such as uric acid for the oxidising agent.
  • such composition includes at least one nitro-substituted nitrogen containing hetrocyclic anti-fogging compound.
  • a redox amplification colour developer composition comprising an oxidizing agent and a colour developing component, characterised in that said composition comprises a combined stabiliser and anti-fogging agent selected from uric or phosphoric acids. It is thus possible to dispense with separate anti-fogging agent per se.
  • the composition has a ratio of oxidizing agent to combine stabiliser in the range of 1 ml to 2 to 50 mg of the combined stabiliser, and preferably 1 ml of the agent to 5 - 20 mg of the acid.
  • a photographic paper having coated thereupon a stabiliser as set forth above for a redox amplification colour developer, thereby to inhibit fogging due to interaction between the stabiliser and the developer.
  • the figure annexed hereto shows the graph of the effect of uric acid in amplifying developers.
  • a multilayer colour paper, suitable for an "RX” process was prepared.
  • the paper was of a similar construction to current 2001 paper products with respect to the dispersions used, and the gel laydown.
  • "All chloride" emulsions were used and the silver concentrations for each layer were as follows - red sensitive layer 3.0mg/sqft., green sensitive layer 4.0mg/sqft., blue sensitive layer 6.4mg/sqft, giving a total weight of silver 13.4mg/sqft.
  • An initial developer was prepared using a potassium carbonate buffer, to which the required photographic reagents were added. Final developer composition is shown below.
  • the pH was adjusted to 10.3, with dilute NaOH, or H-SO. as required.
  • Blue D min is improved by the incorporation of uric acid in the amplifying developer, the improvement is best at the higher concentrations and is maintained over the test period.
  • Contrasts for the layers show variation, but the magnitude of the uric acid containing samples are reduced compared to the control which is an advantage.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Abstract

L'invention se rapporte à une composition de développement couleur par amplification redox, comprenant un agent oxydant et un constituant de développement couleur; la composition comprend un agent stabilisant destiné au constituant oxydant, qui est également efficace comme agent anti-voile. L'agent oxydant peut être du peroxyde d'hydrogène et l'agent stabilisant combiné peut être de l'acide urique ou phosphorique ou un de ses sels fonctionnels. L'invention se rapporte également à un papier photographique recouvert avec ledit agent stabilisant de révélateur couleur par amplification redox évitant, de ce fait, la formation d'un voile.The invention relates to a color development composition by redox amplification, comprising an oxidizing agent and a color development constituent; the composition comprises a stabilizing agent intended for the oxidizing component, which is also effective as an anti-haze agent. The oxidizing agent can be hydrogen peroxide and the combined stabilizing agent can be uric or phosphoric acid or one of its functional salts. The invention also relates to a photographic paper coated with said stabilizing agent for color developer by redox amplification thereby avoiding the formation of a haze.

Description

STABILISERS FOR RX DEVELOPERS
DESCRIPTION
This invention relates to stabilisers for RX developers. Particularly the invention relates to the processing of photographic materials by redox amplification developer systems in order to ameliorate the inherent instability of such solutions.
In photographic colour development processes, and particularly in the RX, redox amplification, process it is desirable to provide colour development materials which degrade only slowly so that they can be used readily in automatic processing.
In the RX, redox amplification, process "normal sensitometry", is produced fro:n low silver chloride laydown coatings having a coating weight of less than 21mg/sqft, and preferably about 13mg/sgft, by using a combination of a traditional colour developer with an oxidant. Such developer hybrids are inherently unstable since they contain an intimate admixture of the colour developer with an oxidant which is often hydrogen peroxide. This inherent instability restricts the modes of use of the system and makes maintaining good sensitometry quite difficult.
It has been proposed in Organic Chemistry page 867 Sedgewick to use uric or phosphoric acids as stabilisers for hydrogen peroxide per se. Further from Henn & Carpenter, Phot. Sci. Eng. vol 3, page 135, 1959 it is known to use uric acid as a photographic developer.
We have now found that these acids and their functional salts will stabilise oxidants such as peroxide even in the presence of the normal components of a redox amplification developer system, and that the presence of such acids and/or their functional salts has not only the effect of inhibiting the interaction between the colour developer and the stabiliser, thereby to increase the useful life of the developer solutions, but also beneficially effects the development process to enhance the developed quality of the image by markedly reducing the tendance of such systems to produce fogged products. In a further aspect of the invention it has been found that uric acid, phosphoric acid or its functional salts may be included in a coating on a photographic paper thereby to give improved fogging levels by inhibiting oxidant/colour developer interaction in situ.
■ In US-A-4,045,225 there is disclosed a colour developer composition comprising an oxidising agent and a colour developing component, wherein the composition additionally comprises a stabiliser such as uric acid for the oxidising agent. However, such composition includes at least one nitro-substituted nitrogen containing hetrocyclic anti-fogging compound. We have now found that the incorporation of a stabiliser such as uric acid into the photographic paper stabilises the development while also acting as an anti-fogging agent thereby enabling said nitrogen containing compound to be dispensed with.
According to the present invention therefore there is provided a redox amplification colour developer composition comprising an oxidizing agent and a colour developing component, characterised in that said composition comprises a combined stabiliser and anti-fogging agent selected from uric or phosphoric acids. It is thus possible to dispense with separate anti-fogging agent per se.
In a preferred form of the invention the composition has a ratio of oxidizing agent to combine stabiliser in the range of 1 ml to 2 to 50 mg of the combined stabiliser, and preferably 1 ml of the agent to 5 - 20 mg of the acid.
According to another aspect of the present invention there is provided a photographic paper having coated thereupon a stabiliser as set forth above for a redox amplification colour developer, thereby to inhibit fogging due to interaction between the stabiliser and the developer.
It will thus be seen that an incorporation of the stabilisers in accordance with the present invention inhibit the interaction between the colour developer and the oxidising agent for example hydrogen peroxide thereby increasing the useful lifetimes of solutions for use in automatic processing, while also acting an an anti-fogging agent.
The invention will now be described, by way of illustration only, with reference to the accompanying drawing and with reference to the following example;
The figure annexed hereto shows the graph of the effect of uric acid in amplifying developers.
EXAMPLE
A multilayer colour paper, suitable for an "RX" process was prepared. The paper was of a similar construction to current 2001 paper products with respect to the dispersions used, and the gel laydown. "All chloride" emulsions were used and the silver concentrations for each layer were as follows - red sensitive layer 3.0mg/sqft., green sensitive layer 4.0mg/sqft., blue sensitive layer 6.4mg/sqft, giving a total weight of silver 13.4mg/sqft. An initial developer was prepared using a potassium carbonate buffer, to which the required photographic reagents were added. Final developer composition is shown below.
Com onent Concentration:
Key:
EDTA ethylene diamine tetracetic acid CD3 β-methanesulphonamidoethylaminotoluidine sesquisulphate hydrate
The pH was adjusted to 10.3, with dilute NaOH, or H-SO. as required.
Samples of developer above were then prepared with different concentrations of uric acid. Uric Acid was first dissolved in an alkali solution of KoH, (0.5g K
OH plus 0.5g uric acid in 50mls H20) . Subsequently
this solution was used to give developers with various concentrations of uric acid: 0, 25, 50, & 100 mg uric acid/litre of developer.
Control samples of these developers were then taken,
whilst the remaining volume was equilibrated to 35 C in a tank line. Hydrogen Peroxide (100 vol.) was added to each developer, to give an oxidant concentration of 5ml/l of developer. Next, suitably exposed sensitometric strips were processed through each of the four experimental developers at intervals over a period of 2.5 hrs. Processing was 30 sees. development, followed by 30 sees, fix, and 90 sees, wash. After each strip samples of the developers were taken for CD3 analysis. The figure shows a graph of the data from CD3 analysis, clearly the developers with higher uric acid concentrations have more CD3 left than the control sample.
The sensitometric effects of incorporating uric acid into amplifying developers is summarised below, whilst relevant data is given in Tables 1 to 4.
TABLE ONE : EFFECT OF URI C ACID ON AMPLIFYI NG Developer o MG URIC ACID PER LITRE OF Developer
TIME RDHIN GDM N BDMIN DHAX GDMAX BDMAX RCOK SCON BCON
TABLE TWO: EFFECT OF URIC ACID ON AMPLIFYING Developer 25 MG URIC ACID PER LITRE OF Developer
TIME RDMIK GDMIN BDMIN RDMAX GDMAX BDMAX P.CON GCON BCON
TABLE THREE:
EFFECT OF URIC ACID ON AMPLIFYING Developer 50 HG URIC ACID PER LITRE OF Developer
TIME 0 HRS 0.5 HRS 1.0 HRS 2.0 HRS
TABLE FOUR : EFFECT OF URIC ACID OH AMPLIFYING Developer loo MG URIC ACID PER LITRE OF Developer
TIME 0 HRS 0.5 HRS 1.0 HRS 2.0 HRS 2.50 HRS
Red & Green D mins both show a relative increase compared to the control. The highest uric acid concentration shows the most stabilising effect.
Blue D min is improved by the incorporation of uric acid in the amplifying developer, the improvement is best at the higher concentrations and is maintained over the test period.
All three D max densities are improved compared to the control by the incorporation of uric acid in the developer and show reduced variations.
Contrasts for the layers show variation, but the magnitude of the uric acid containing samples are reduced compared to the control which is an advantage.

Claims

1. A redox amplification colour developer composition comprising an oxidising agent and a colour developing component;
characterised in that the composition comprises a combined stabiliser and anti-fogging agent for the oxidising agent selected from uric and phosphoric acids or a functional salt thereof.
2. A composition according to claim 1 characterised in that the ratio of the oxidising agent to the combined stabiliser is 1 ml to 2 - 50 mg of the stabiliser.
3. A composition according to claim 3 characterised in that the ratio is 1 ml to 5 - 20 mg of the stabiliser.
4. A composition according to claim 1 characterised in that the oxidising agent is hydrogen peroxide.
5. A composition according to any preceding claim characterised in that the functional salt is an alkali metal salt.
6. A method of stabilising a redox amplification colour developer comprising an oxidising agent, which comprises adding to said oxidising agent a stabiliser characterised in that the oxidising agent is hydrogen peroxide, and the stabilising agent is selected from uric acid, phosphoric acid, or a functional salt thereof.
7. A method according to claim 5 characterised in that the concentration of the stabilizer with respect to the developer is 5 to 250 mg/1.
8. A photographic paper having coated thereupon a composition according to any of claims 1 to 5 including a stabiliser for a redox amplification colour developer, thereby to inhibit fogging due to interaction between the stabiliser and the developer.
9. A photographic paper according to claim 8 characterised in that the stabiliser is selected from uric acid, phosphoric acid, or a photographically effective salt thereof.
10. A redox amplification colour developer composition substantially as hereinbefore set forth with reference to, and as illustrated in, the accompanying drawing and/or the foregoing example.
11. A method of stabilising a redox amplification colour developer system comprising an oxidising agent substantially as hereinbefore set forth with reference to, and/or as illustrated in the accompanying drawing or in the foregoing Example.
12. A photographic paper comprising a stabiliser substantially as hereinbefore set forth with reference to, and as illustrated in, the accompanying drawing and/or as show in the foregoing Example.
EP91915628A 1990-09-13 1991-08-30 Stabilisers for rx developers Expired - Lifetime EP0548124B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB909020000A GB9020000D0 (en) 1990-09-13 1990-09-13 Stabilisers for rx developers
GB9020000 1990-09-13
PCT/EP1991/001655 WO1992005471A1 (en) 1990-09-13 1991-08-30 Stabilisers for rx developers

Publications (2)

Publication Number Publication Date
EP0548124A1 true EP0548124A1 (en) 1993-06-30
EP0548124B1 EP0548124B1 (en) 1995-02-08

Family

ID=10682130

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91915628A Expired - Lifetime EP0548124B1 (en) 1990-09-13 1991-08-30 Stabilisers for rx developers

Country Status (5)

Country Link
EP (1) EP0548124B1 (en)
JP (1) JPH06500863A (en)
DE (1) DE69107307T2 (en)
GB (1) GB9020000D0 (en)
WO (1) WO1992005471A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5707786A (en) * 1995-07-17 1998-01-13 Agfa-Gevaert Processing of color photographic silver halide materials

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5213336A (en) * 1975-07-23 1977-02-01 Fuji Photo Film Co Ltd Photographic image formation method
JPS613137A (en) * 1984-06-15 1986-01-09 Fuji Photo Film Co Ltd Internal latent image type core/shell direct positive silver halide emulsion and its preparation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9205471A1 *

Also Published As

Publication number Publication date
DE69107307T2 (en) 1995-06-01
GB9020000D0 (en) 1990-10-24
WO1992005471A1 (en) 1992-04-02
EP0548124B1 (en) 1995-02-08
JPH06500863A (en) 1994-01-27
DE69107307D1 (en) 1995-03-23

Similar Documents

Publication Publication Date Title
EP0555423B1 (en) Method for forming a photographic colour image
JP3045311B2 (en) Photo color processing method
EP0600564B1 (en) Method of photographic processing
EP0548124A1 (en) Stabilisers for rx developers.
US6156488A (en) Photographic bleach compositions
EP0561860A1 (en) Method of photographic silver halide processing, silver halide materials and solutions therefor.
JPH051456B2 (en)
EP0529720B1 (en) Method of photographic processing
EP0511999B1 (en) Bleach-fixers with excess sulphite
US5547816A (en) Photographic processing method using bleach solution comprising hydrogen peroxide and halide ions
EP0849633B1 (en) Photographic recording materials and their use in redox amplification
WO1992007299A1 (en) Method of forming a photographic image
EP0654707B1 (en) Photographic developer/amplifier compositions
EP0511288B1 (en) Thiosulphate fixing solutions
WO1991016666A1 (en) Method and apparatus for photographic processing solution replenishment
US5837431A (en) Photographic developer/amplifier compositions
EP0843213B1 (en) Photographic developer/amplifier process and solutions
SU1075227A1 (en) Silver picture intensifier
JPH09197637A (en) Method of forming photographic color image
JPH1062930A (en) Concentrate of conditioning solution, vessel containing same and processing method using same
JPH10133340A (en) Fixing solution
WO2003003116A1 (en) Stabilized cd-4 one-part film developer concentrates
GB1525700A (en) Image-forming intensification process using a photographic material
WO1990013059A1 (en) Method for adding components to photographic processing solutions
EP0795783A1 (en) Photographic developer amplifier composition

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19930301

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE CH DE FR GB IT LI NL

17Q First examination report despatched

Effective date: 19901004

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE CH DE FR GB IT LI NL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19950208

Ref country code: BE

Effective date: 19950208

REF Corresponds to:

Ref document number: 69107307

Country of ref document: DE

Date of ref document: 19950323

ITF It: translation for a ep patent filed

Owner name: BARZANO' E ZANARDO MILANO S.P.A.

ET Fr: translation filed
NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19970702

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19970812

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19970827

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19971014

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980830

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980831

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980831

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19980830

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990601

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050830