EP0460008B1 - Verwendung pyrazoltriazol-fotografischer farbkuppler - Google Patents

Verwendung pyrazoltriazol-fotografischer farbkuppler Download PDF

Info

Publication number
EP0460008B1
EP0460008B1 EP90903197A EP90903197A EP0460008B1 EP 0460008 B1 EP0460008 B1 EP 0460008B1 EP 90903197 A EP90903197 A EP 90903197A EP 90903197 A EP90903197 A EP 90903197A EP 0460008 B1 EP0460008 B1 EP 0460008B1
Authority
EP
European Patent Office
Prior art keywords
group
coupler
alkyl
pyrazolo
heterocyclic
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
EP90903197A
Other languages
English (en)
French (fr)
Other versions
EP0460008A1 (de
Inventor
Brian Thomas
Llewellyn James Leyshon
David Clarke
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 EP0460008A1 publication Critical patent/EP0460008A1/de
Application granted granted Critical
Publication of EP0460008B1 publication Critical patent/EP0460008B1/de
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
    • G03C7/32—Colour coupling substances
    • G03C7/36—Couplers containing compounds with active methylene groups
    • G03C7/38—Couplers containing compounds with active methylene groups in rings
    • G03C7/381—Heterocyclic compounds
    • G03C7/382—Heterocyclic compounds with two heterocyclic rings
    • G03C7/3825—Heterocyclic compounds with two heterocyclic rings the nuclei containing only nitrogen as hetero atoms
    • G03C7/3835—Heterocyclic compounds with two heterocyclic rings the nuclei containing only nitrogen as hetero atoms four nitrogen atoms

Definitions

  • This invention relates to the use of 1H-pyrazolo[1,5- b ]-1,2,4-triazole couplers in photographic materials.
  • couplers containing a tertiary butyl group in the 2- or 6-position are disclosed in European Patent Specifications 0 326 406 and 0 271 712, the former document belonging to the state of the art by virtue of Article 54(3) EPC.
  • photographic colour paper processable in the RA4 process is comprised of silver halide emulsions having at least 80% silver chloride and preferably substantially pure silver chloride.
  • Most 1H-pyrazolo[1,5- b ]-1,2,4-triazole couplers when incorporated into silver chloride emulsions provide photographic materials having poor raw stock keeping properties. That is, the material when stored after manufacture but before exposure and processing, shows significantly increased D min compared to freshly coated materials.
  • the present invention is directed to the use of 1H-pyrazolo[1,5- b ]-1,2,4- triazole couplers containing a tertiary carbon group in the 2- or 6- position of the coupler nucleus in photographic silver halide materials of which the halide comprises more than 80% chloride, in order to improve raw stock stability.
  • the silver halide emulsion comprises at least 90% silver chloride especially substantially pure silver chloride.
  • the preferred couplers have the formula
  • R 1 or R 3 are a tertiary alkyl group they preferably contain 4-8 carbon atoms and may be t-butyl, t-pentyl or t-octyl.
  • R 1 and R 3 may otherwise contain 1-25 carbon atoms and may comprise a ballast group to render the coupler non-diffusible in photographic layers.
  • R 4 , R 5 and R 6 are chlorine, bromine and fluorine; alkyl groups containing 1 to 20 carbon atoms, for example, methyl, ethyl, propyl, butyl, pentyl, ethylhexyl and eicosyl; cyclohexyl and cyclopentyl; dioctylamino, dimethylamino and dodecylamino; aryl containing 6 to 20 carbon atoms,for example, phenyl, naphthyl and mesityl; cyano; nitro; a heterocyclic group comprised of atoms selected from carbon, oxygen, nitrogen and sulphur atoms necessary to complete a 5- or 6-membered ring, for example, pyrrolyl, oxazolyl and pyridyl.
  • L examples are: O, S, CO, CO 2 , SO 2 , SO, in which R 8 and R 9 are individually hydrogen, alkyl, such as alkyl containing 1 to 30 carbon atoms, for example, methyl, ethyl, propyl, butyl or eicosyl, or aryl, such as aryl containing 6 to 20 carbon atoms, for example, phenyl or naphthyl; or a heterocyclic group comprised of atoms selected from carbon, nitrogen, oxygen, and sulphur atoms necessary to complete a 5- or 6-member heterocyclic ring, for example, pyrrolyl, oxazolyl and pyridyl.
  • alkyl such as alkyl containing 1 to 30 carbon atoms, for example, methyl, ethyl, propyl, butyl or eicosyl
  • aryl such as aryl containing 6 to 20 carbon atoms, for example, phenyl or naphthy
  • R 7 are an alkyl containing 1 to 30 carbon atoms, for example, methyl, ethyl, propyl, butyl, pentyl and eicosyl; aryl, such as aryl containing 6 to 20 carbon atoms, for example, phenyl and napthyl; or a heterocyclic group, such as a 5- or 6-membered heterocyclic group comprised of atoms selected from carbon, nitrogen, oxygen and sulphur atoms, for example an oxazole, pyridine, pyrrole or thiophene ring.
  • R 4 , R 5 and R 6 form a heterocyclic ring this may be an oxazole, pyridine, pyrrole and thiophene; or when they form an alicyclic ring system, this may be cyclohexyl, norbornyl or adamantyl.
  • the coupling-off group R 2 may be a halogen atom or an aryloxy or arylthio group.
  • the couplers used in the present invention may be prepared by methods known in the art.
  • the couplers are associated with a silver halide emulsion layer coated on a support to form a photographic element.
  • the term "associated with” signifies that the coupler is incorporated in the silver halide emulsion layer or in a layer adjacent thereto where, during processing, it is capable of reacting with silver halide development products.
  • the photographic elements can be single colour elements or multicolour elements.
  • the magenta dye-forming couplers used in this invention would usually be associated with a green-sensitive emulsion, although they could be associated with an emulsion sensitised to a different region of the spectrum, or with a panchromatically sensitised, orthochromatically sensitised or unsensitised emulsion.
  • Multicolour elements contain dye image-forming units sensitive to each of the three primary regions of the spectrum. Each unit can be comprised of a single emulsion layer or of multiple emulsion layers sensitive to a given region of the spectrum.
  • the layers of the element, including the layers of the image-forming units can be arranged in various orders as known in the art.
  • a typical multicolour photographic element comprises a support bearing yellow, magenta and cyan dye image-forming units comprising at least one blue-, green- or red-sensitive silver halide emulsion layer having associated therewith at least one yellow, magenta or cyan dye-forming coupler respectively, at least one of the magenta dye-forming couplers being a coupler of this invention.
  • the element can contain additional layers, such as filter and barrier layers.
  • the silver halide emulsion employed in the elements of this invention can be either negative-working or positive-working. Suitable emulsions and their preparation are described in Research Disclosure Sections I and II and the publications cited therein. Suitable vehicles for the emulsion layers and other layers of elements of this invention are described in Research Disclosure Section IX and the publications cited therein.
  • the elements of the invention can include additional couplers as described in Research Disclosure Section VII, paragraphs D, E, F and G and the publications cited therein.
  • the couplers of this invention and any additional couplers can be incorporated in the elements and emulsions as described in Research Disclosures of Section VII, paragraph C and the publications cited therein.
  • the photographic elements of this invention or individual layers thereof can contain brighteners (see Research Disclosure Section V), antifoggants and stabilisers (see Research Disclosure Section VI), antistain agents and image dye stabiliser (see Research Disclosure Section VII, paragraphs I and J), light absorbing and scattering materials (see Research Disclosure Section VIII), hardeners (see Research Disclosure Section XI), plasticisers and lubricants (see Research Disclosure Section XII), antistatic agents (see Research Disclosure Section XIII), matting agents (see Research Disclosure Section XVI) and development modifiers (see Research Disclosure Section XXI).
  • brighteners see Research Disclosure Section V
  • antifoggants and stabilisers see Research Disclosure Section VI
  • antistain agents and image dye stabiliser see Research Disclosure Section VII, paragraphs I and J
  • light absorbing and scattering materials see Research Disclosure Section VIII
  • hardeners see Research Disclosure Section XI
  • plasticisers and lubricants see Research Disclosure Section XII
  • antistatic agents see Research Disclosure Section XIII
  • matting agents see Research Disclosure
  • the photographic elements can be coated on a variety of supports as described in Research Disclosure Section XVII and the references described therein.
  • Photographic elements can be exposed to actinic radiation, typically in the visible region of the spectrum, to form a latent image as described in Research Disclosure Section XVIII and then processed to form a visible dye image as described in Research Disclosure Section XIX.
  • Processing to form a visible dye image includes the step of contacting the element with a colour developing agent to reduce developable silver halide and oxidise the colour developing agent. Oxidised colour developing agent in turn reacts with the coupler to yield a dye.
  • Preferred colour developing agents are p-phenylene diamines.
  • 4-amino-3-methyl-N,N-diethylaniline hydrochloride 4-amino-3-methyl-N-ethyl-N- ⁇ -(methanesulphonamido)-ethylaniline sulphate hydrate, 4-amino-3-methyl-N-ethyl-N- ⁇ -hydroxyethylaniline sulphate, 4-amino-3- ⁇ -(methanesulphonamido)ethyl-N,N-diethylaniline hydrochloride and 4-amino-N-ethyl-N-(2-methoxyethyl)-m-toluidine di-p-toluene sulphonate.
  • this processing step leads to a negative image.
  • this step can be preceded by development with a non-chromogenic developing agent to develop exposed silver halide, but not form dye, and then uniform fogging of the element to render unexposed silver halide developable.
  • a direct positive emulsion can be employed to obtain a positive image.
  • Couplers were dispersed and coated as follows.
  • the test coupler (3.0 mmol), dissolved in half its weight of di-n-butyl phthalate and ethyl acetate (2.0g), was dispersed in aqueous gelatin (36g, 12.5%) using ultrasonic agitation.
  • the gelatin solution contained a small amount (0.5%) of di-isopropyl-naphthalene sulphonic acid (sodium salt) as a surfactant.
  • the resultant coupler dispersion was diluted to 200g with water and mixed with a green-sensitised silver chloride photographic emulsion (100g, 1.49% Ag, 4.5% gel). The mixture was spread on a resin-coated paper support to give a layer of the following composition: Ag 0.267g.m -2 Coupler 0.54mmol.m -2 Gelatin 1.61g.m -2
  • a protective gel supercoat containing hardener was applied to the coating.
  • Sample strips of the coatings were exposed through a step tablet (density range 0-3, 0.15 increments) and developed in standard "KODAK" RA-4 process solutions.
  • Sample strips from each coating were exposed and processed with RA4 chemistry within a few days of coating. Similar strips were put aside in a light-tight box and stored under ambient conditions for 29 weeks before exposure and processing.
  • Couplers IIa and IIb were examined as described in Example 1, except that the storage time was reduced to 17 weeks. The sensitometric data shown below confirmed the advantage of the 6-t-Bu substituent. Coupler R Fresh D.min Stored D.min IIa Me 0.11 0.20 IIb t-Bu 0.10 0.12
  • Couplers IIIa and IIIb were dispersed with the stabilising compound IV in the following proportions: Coupler 2 Stabiliser 1 Solvent (dibutyl phthalate) 3
  • Coupler 0.57mmole.m -2
  • Silver 2.4mmole.m -2

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)

Claims (5)

  1. Verwendung von 1H-Pyrazolo[1,5-b]-1,2,4-triazol-Kupplern mit einer tertiären Kohlenstoffgruppe in der 3- oder 6-Position des Kupplerkernes in photographischen Silberhalogenidmaterialien, in denen das Halogenid zu mehr als 80 % aus Chlorid besteht, um die Stabilität des Rohmaterials zu verbessern.
  2. Die Erfindung gemäß Anspruch 1, worin der Kuppler die Formel hat:
    Figure imgb0013
    worin R1 und R3 jeweils eine Alkyl- oder substituierte Alkylgruppe darstellen, und
    R2 steht für ein Wasserstoffatom oder eine abkuppelnde Gruppe, wobei mindestens eine der Gruppen R1 und R3 eine tertiäre Kohlenstoffgruppe der Formel ist:
    Figure imgb0014
    worin R4, R5 und R6 einzeln stehen für ein Halogenatom oder eine Alkyl-, Cycloalkyl-, Amino-, Aryl-, Cyano-, Nitro- oder heterocyclische Gruppe oder eine Gruppe -L-R7,
    worin L für eine verbindende Gruppe steht, und
    R7 steht für eine Alkyl-, Aryl- oder heterocyclische Gruppe, und worin beliebige zwei von R4, R5 und R6 einen heterocyclischen oder alicyclischen Ring bilden können,
    wobei jede der Gruppen R4, R5 und R6 gegebenenfalls substituiert sein kann, und wobei sämtliche der obigen Gruppen und Substituenten derart beschaffen sind, daß sie die erwünschten Eigenschaften des Kupplers nicht nachteilig beeinflussen.
  3. Die Erfindung nach Anspruch 2, worin R1 oder R3 für eine tertiäre Alkylgruppe mit 4 - 8 Kohlenstoffatomen stehen.
  4. Die Erfindung nach einem der Ansprüche 1 - 3, worin der Kuppler eine abkuppelnde Gruppe aufweist, die aus einem Halogenatom oder einer Aryloxy- oder Arylthiogruppe besteht.
  5. Die Erfindung nach einem der Ansprüche 1 - 4, worin die Emulsion eine praktisch reine Silberchloridemulsion ist.
EP90903197A 1989-02-22 1990-02-14 Verwendung pyrazoltriazol-fotografischer farbkuppler Expired - Lifetime EP0460008B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB8904004 1989-02-22
GB898904004A GB8904004D0 (en) 1989-02-22 1989-02-22 The use of pyrazolo-triazole photographic colour couplers
PCT/GB1990/000232 WO1990010253A1 (en) 1989-02-22 1990-02-14 The use of pyrazolo-triazole photographic colour couplers

Publications (2)

Publication Number Publication Date
EP0460008A1 EP0460008A1 (de) 1991-12-11
EP0460008B1 true EP0460008B1 (de) 1996-06-05

Family

ID=10652100

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90903197A Expired - Lifetime EP0460008B1 (de) 1989-02-22 1990-02-14 Verwendung pyrazoltriazol-fotografischer farbkuppler

Country Status (6)

Country Link
EP (1) EP0460008B1 (de)
JP (1) JPH0354554A (de)
AT (1) ATE139043T1 (de)
DE (1) DE69027309D1 (de)
GB (1) GB8904004D0 (de)
WO (1) WO1990010253A1 (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9026557D0 (en) * 1990-12-06 1991-01-23 Kodak Ltd Photographic colour couplers and photographic materials containing them

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6363044A (ja) * 1986-09-04 1988-03-19 Fuji Photo Film Co Ltd カラ−画像形成方法
DE3766696D1 (de) * 1986-12-27 1991-01-24 Konishiroku Photo Ind Lichtempfindliches photographisches silberhalogenidmaterial.
JP2540057B2 (ja) * 1988-01-21 1996-10-02 富士写真フイルム株式会社 ハロゲン化銀カラ―写真感光材料の処理方法
JPH01193737A (ja) * 1988-01-28 1989-08-03 Konica Corp ハロゲン化銀写真感光材料

Also Published As

Publication number Publication date
WO1990010253A1 (en) 1990-09-07
GB8904004D0 (en) 1989-04-05
EP0460008A1 (de) 1991-12-11
JPH0354554A (ja) 1991-03-08
ATE139043T1 (de) 1996-06-15
DE69027309D1 (de) 1996-07-11

Similar Documents

Publication Publication Date Title
EP0284240B2 (de) Photographische Silberhalogenidmaterialien und Verfahren, das einen Pyrazoloazolkuppler enthält
EP0528930B1 (de) Verwendung substituierter phenole zur verbesserung der lichtechtheit von magentafarbstoffbildern
EP0529736B1 (de) Farbphotographische Materialien enthaltend einen Magenta-Kuppler, einen DIR-Kuppler und eine Carbonamid-Verbindung
EP0284239B1 (de) Photographische Silberhalogenidmaterialien und Verfahren, das einen Pyrazoloazolkuppler enthält
EP0433947B1 (de) Farbphotographisches Element und Verfahren
US5460927A (en) Activated propenes as color couplers and a method for production of photographic elements therewith
EP0529727B1 (de) Farbphotographische Materialien, enthaltend einen Magenta-Kuppler, eine Carbonamid-Verbindung und eine Anilin- oder Amin-Verbindung
EP0553964A1 (de) Farbstoffstabilitätsverbesserungen
EP0348135B1 (de) Farbphotographische Pyrazolon-Kuppler und photographische Elemente, die diese enthalten
US4876182A (en) Photographic elements containing pyrazolone color couplers
EP0434148B1 (de) Photographisches Material und Verfahren, einen Pyrazolotriazolkuppler umfassend
EP0521019B1 (de) Farbphotographische pyrazolo(1-5a)benzimidazolkuppler
EP0460008A1 (de) Verwendung pyrazoltriazol-fotografischer farbkuppler.
EP0565531A1 (de) Aktivierte Propene als Farbkuppler.
US5374511A (en) Photographic color couplers and photographic materials containing them
JP3089579B2 (ja) ハロゲン化銀カラー写真感光材料及びカラー画像形成方法
US4824771A (en) Photographic acetanilide couplers with novel ballast group and photographic elements containing them
EP0296793B1 (de) Farbphotographische Silberhalogenidmaterialien und Verfahren
EP0410754B1 (de) Farbphotographisches Element und Verfahren
EP0639794A1 (de) Photographische Farbkuppler und photographische Materialien enthaltend diese Kuppler
JPH0262537A (ja) ハロゲン化銀カラー写真感光材料
JPS63177135A (ja) ハロゲン化銀写真感光材料
JPS61120148A (ja) ハロゲン化銀カラ−写真感光材料
JPH0571086B2 (de)
JPH0240648A (ja) ハロゲン化銀カラー写真感光材料

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: 19910906

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB IT LI LU NL SE

17Q First examination report despatched

Effective date: 19940812

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FR GB IT LI LU NL SE

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRE;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.SCRIBED TIME-LIMIT

Effective date: 19960605

Ref country code: ES

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 19960605

Ref country code: BE

Effective date: 19960605

Ref country code: DK

Effective date: 19960605

Ref country code: AT

Effective date: 19960605

REF Corresponds to:

Ref document number: 139043

Country of ref document: AT

Date of ref document: 19960615

Kind code of ref document: T

REF Corresponds to:

Ref document number: 69027309

Country of ref document: DE

Date of ref document: 19960711

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: KIRKER & CIE SA

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

Ref country code: SE

Effective date: 19960905

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

Ref country code: DE

Effective date: 19960906

ET Fr: translation filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

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

Effective date: 19970228

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
REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

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

Ref country code: GB

Payment date: 20050110

Year of fee payment: 16

Ref country code: NL

Payment date: 20050110

Year of fee payment: 16

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

Ref country code: FR

Payment date: 20050202

Year of fee payment: 16

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

Ref country code: CH

Payment date: 20050317

Year of fee payment: 16

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: 20060214

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

Ref country code: CH

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

Effective date: 20060228

Ref country code: LI

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

Effective date: 20060228

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

Ref country code: NL

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

Effective date: 20060901

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: 20060214

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20060901

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20061031

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: 20060228