GB2337750A - Image-dye forming couplers based on the active methylene containing 2-sulphonylacetamide skeleton and photographic elements containing them - Google Patents

Image-dye forming couplers based on the active methylene containing 2-sulphonylacetamide skeleton and photographic elements containing them Download PDF

Info

Publication number
GB2337750A
GB2337750A GB9811344A GB9811344A GB2337750A GB 2337750 A GB2337750 A GB 2337750A GB 9811344 A GB9811344 A GB 9811344A GB 9811344 A GB9811344 A GB 9811344A GB 2337750 A GB2337750 A GB 2337750A
Authority
GB
United Kingdom
Prior art keywords
coupler
substituted
nhcocho
group
unsubstituted
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
GB9811344A
Other versions
GB2337750B (en
GB9811344D0 (en
Inventor
Michael William Crawley
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.)
Eastman Kodak Co
Original Assignee
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 Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to GB9811344A priority Critical patent/GB2337750B/en
Publication of GB9811344D0 publication Critical patent/GB9811344D0/en
Publication of GB2337750A publication Critical patent/GB2337750A/en
Application granted granted Critical
Publication of GB2337750B publication Critical patent/GB2337750B/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/44—Sulfones; Sulfoxides having sulfone or sulfoxide groups and carboxyl groups bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/64—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and sulfur atoms, not being part of thio groups, bound to the same carbon skeleton
    • C07C323/65—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and sulfur atoms, not being part of thio groups, bound to the same carbon skeleton containing sulfur atoms of sulfone or sulfoxide groups bound to the carbon skeleton
    • 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
    • G03C7/305—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers
    • G03C7/30511—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers characterised by the releasing group
    • G03C7/30517—2-equivalent couplers, i.e. with a substitution on the coupling site being compulsory with the exception of halogen-substitution
    • G03C7/30535—2-equivalent couplers, i.e. with a substitution on the coupling site being compulsory with the exception of halogen-substitution having the coupling site not in rings of cyclic compounds
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Abstract

The present invention relates to an image dye-forming coupler, and in particular to an image dye-forming coupler, with good spectrophotometric characteristics and excellent light stability, and having the formula (I) [wherein x is a coupling-off group; R<SP>1</SP>, Y and Z are the same or different and are independently selected from alkyl, alkenyl, cycloalkyl, aryl or heterocyclic, each of which is unsubstituted or substituted with one or more coupler-modifying functional groups, or one of Y and Z may be H; or Y and Z taken together with the nitrogen atom form a 5-10 membered heterocyclic ring which may contain one or more further heteroatoms selected from N, O and S, said heterocyclic ring being unsubstituted or substituted with one or more coupler-modifying functional groups] and to a photographic element containing such a coupler. Preferred couplers are those wherein one of Y and X is hydrogen and the other is an optionally substituted phenyl group and wherein the coupling-off group X is a chloro or optionally substituted thioaryl group (-S-Ar).

Description

2337750 1_ IMAGE-DYE-FORMING COUPLERS AND PHOTOGRAPHIC ELEMENTS CONTAINING
THEM
Field of the Invention
The present invention relates to image-dye-forming couplers, specifically yellow dye-forming couplers, hereinafter called yellow couplers, and to photographi elements containing them. in particular the invention relates to a new class of yellow couplers for use with silver halide based photographic emulsions.
Background of the Invention
Photographic layers sensitive to blue light for use in a colour photographic material typically contain a yellow coupler which, on reaction with an oxidised p-phenylenediamine developer, forms a yellow dye. At the time of writing, most commercially available photographic films contain pivaloyl or benzoyl acetanilide yellow couplers. These classes of couplers are, in general, satisfactory, but a person skilled in the art will be aware that even the best examples of these classes are a compromise between coupler activity as measured, for example, by contrast on the one hand and dye stability on the other. Dodecyl 4-chloro-3-[2-(1-benzyl-Sethoxy-2,4-dioxoimidazolidin-3-yl)-2-(2,2-dimethylpropanoyl) acetamidol benzoate, for example, has good dye stability, but has a relatively poor contrast; dodecyl 4-chloro-3-[2-(1benzyl-5-ethoxy-2,4-dioxoimidazolidin-3-yl)-2(4methoxybenzoyl)acetamidol benzoate, on the other hand, has a relatively good contrast but has poor dye stability.
Problem to be Solved by the Invention There is, therefore, a requirement to find new classes of yellow couplers. In each new class discovered, there is a chance that one or more examples may exhibit a combination of parameters which is better than the yellow couplers hitherto available in the art.
Summary of the Invention it has now been found that active methylene compounds containing sulphone and amide activating functions and with appropriate coupling-off groups are a useful new class of yellow coupler providing yellow dyes with good spectrophotometric characteristics, excellent light stability and good dark/wet dye stability. Furthermore these compounds are relatively easy to prepare and use inexpensive starting materials.
According to the present invention therefore there is provided an image dye-forming coupler of formula (I):- 0 0 R'-,, 1/ S NYZ 0 X (I) wherein X is a coupling-of f group, R1, Y and Z are the same or different and are independently selected from alkyl, aryl or heterocyclic, each of which is unsubstituted or substituted with one or more couplermodifying functional groups, or one of Y and z may be H; or Y and Z taken together with the nitrogen atom form a 5-10 membered heterocyclic ring which may contain one or more further heteroatoms selected from N, 0 and S, said heterocyclic ring being unsubstituted or substituted with one or more coupler-modifying functional groups.
In a preferred aspect of the present invention there is 5 provided a yellow coupler of formula (II):- 0 0 R '-,, 1/ S /1 NH 0 \ jj R3 X R2 (II) wherein X and R1 are as def ined above and R2 and R3 are independently selected from hydrogen and one or more coupler-modifying functional groups.
Said coupling-off group is a group adapted to split-off from the coupler as a result of the reaction between the coupler and the oxidation product of an arylamine colour developer. Said coupler-modifying groups are substituents which, by their presence in the coupler structure, influence the photographic or physical properties of the coupler or the dye derived from the coupler.
The present invention also includes a photographic element containing a compound of formula (I) as an image-dye-forming coupler, in association with a lightsensitive silver halide emulsion layer.
In yet another aspect the present invention provides a multi-colour photographic material comprising a support bearing yellow, magenta and cyan image-dye-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, wherein at least one dye-forming coupler is a coupler in accordance with the present invention.
Advantageous Effect of the Invention Couplers of formula (i) are capable of providing dyes with hue characteristics comparable to those obtained from other yellow couplers in current use. In particular the dyes have low secondary absorptions in the green and red regions of the spectrum, narrow halfband width and good light and thermal stability. The couplers themselves have good raw stock- keeping properties and low continued coupling characteristics and are readily prepared from inexpensive precursors in a short number of steps giving advantages in the cost of manufacture.
Detailed Description of-the Invention
Typically R1, R2, R3, X, Y and Z may be selected independently from coupler-solubilising groups, ballasting groups and dye hue-modifying groups. Photographic ballast groups are known in the art and comprise an nrganic group of such size and configuration so as to make the coupler molecule non-diffusible in a coated photographic element. Two or more couplers may be attached to the same ballast group or two or more ballasts may be attached to the same coupler. Generally the sum of the number of carbon atoms in one or more ballast groups is 10.
In particular R1 is selected from an alkyl, aryl or heterocyclic group optionally substituted with one or more coupler-modifying functional groups and is typically alkyl, phenyl, naphthyl, pyridyl or dioxanyl, preferably alkyl and phenyl, especially phenyl.
R1 may contain one or more substituents such as halogen, R, RO, R2N, RHN, H2N, RS, RSO, RS02M RS02, RS020, ROOC, HOOC, RCOO, RNHCO, R2NCO, RNHCONH, RCONH, RNHS02, R2NS02, R2NS02, RCO, N02, CN, CF3, P(OR)3, PO(OR)3, where R has the same definition as R1.
Thus unsubstititued or substituted R1 may be selected from one of the following representative groups, without limitation thereto:- -W -Et -Cl2H2s -CHMe2 -CHMeEt -But -C(Me)2G5H11 --0 cl 0C16H33 O-N 0 fm In compounds of formula (II), R2 and R3 may be selected from H and those groups defined hereinabove for substituents of R1. Some representative examples of the substituted aryl group within the anilide portion of the coupler of formula (I) are as follows, but are not limited thereto.
4C12H25 -Q-COW 12 H25 CC 14% cl NHGOC 15bi NHCO(CF2)GO --D -0 i),-" cl 2C 1 eH33 0OW, 12H 25 oscC16% cl a NW Moreover any of the above substituents of R1 or the groups R2 and R3. other than H and halogen, may be substituted with one or more of the same or different substituents of R1, R2 and R3 as hereinabove defined, which may in turn be further substituted. In a preferred embodiment R1 may be an i-propyl, n-butyl, t-butyl, decyl or dodecyl group or more preferably a phenyl group, optionally substituted with methyl, methoxy, chloro or methylsulfamoyl.
R2 and R3 arG preferably selected from hydrogen, halogen, or substituted or unsubstituted alkoxy, carboxy ester, alkylsulfonyl, alkylcarbamoyl and alkylsulfonamido and alkylsulfamoyl. More preferably one of R2 and R3 is a chloro or alkoxy group in the ortho position.
AS used herein and throughout the specification the term alkyl refers to an unsaturated or saturated straight or branched chain alkyl group having 1-20 atoms and includes cycloalkyl having 3-8 carbon atoms.
-7 It will be appreciated that X may be any coupling-off group known to a person skilled in the art. In some embodiments, X may be selected from halogen, pseudohalogen, RO, RS, RCOO, RS020, RS02NH, RS02NR, (R0)2P(0)0, RN=N, where R has the same meaning as R 1 above, N- heterocycles (attached to the coupling site by the heteroatom), such as, for example, 2,4-oxazolidinedione, pyridone, pyridazone, phthalimido, succinimido, hydantoinyl, triazole, triazoledione, tetrazole, imidazole, pyrazole and benzotriazole and may in particular be one of the following although not limited thereto:- cl, Br, F, SCN, Ome, OPh, NHSO2W, 0COW, 0SO2Ph, OPO(OE%, 1 "=9" 1 1 0=8Q2 / N' 'N (7) 0 0 o N, 0 o BO CH2Ph Me 1 S 1 N 0=t-=0 1 1 U 1) 1 f NHCOBu' 0 CN SCH2CH2COOH 1 N' N > LN 1 b N 1 N-Ph N= Pf 1 U NHCOMe S02Me 1 0= N -'F- 0 - N, CH2Ph 1 b 0 a 1 U 0 SCMe Any of the above substituents, other than halogen, may be substituted with one or more substituents as hereinbefore defined for R1. In some embodiments, X may be chloro. However the coupling-off group is preferably a thioaryl group, optionally substituted with one or more coupler modifying groups and in particular with an alkoxy group or with a substituted or unsubstitued carbamoyl group, especially a thiophenyl group substituted with a 2,4-di-t-pentylphenoxybutyramido group.
In some embodiments, the image-forming coupler may be selected from the following couplers:
Q 0 0 a NH-0 0 a (1) -0 0 a W 1 11 0 a NWO (3) Me me Me CO0C12H25 COOC 12H25 0 0 NH b-SO2C12H25 (5) U 0 0 a NH. SO2C1 0 S NHCOCHO E1 (7) 0 C'0 S 1 NH.
0 a (2) M e(CH 2)3 - 0,NH 0 (4) Me CO0C12H25 COOC 12H 0 0 a NH S f NHCOBO But 9 0 NHO 0 S CO0C12H25 (6) cow 12 NHCOCHO E1 (8) Me NHb-SC2C12H25 S But- 0 0 ' 61 - PNHo, S t, NHCOBut cl.
Me 0 0 S cocci ' 2H 25 NHCOCHO 1 - E (10) But,.0 0 0 S NHCOBut (9) COW12H25 (11) 0 Cl S OW 11 ' 1 (13) o 0 " NH 0 S CO0C12H25 -Ph N=N 0 0 0 (15) CWC12H 25 (17) Me NHCO(CH2 p (12) 1 0 CO 0 NH S WCO(CH2bO IIH%"'OCHO Et (1 4 0 a 0 P>LNHO 0 N 0 1 BO. CH2 Ph NHCCC1Shbl (16) 1 Me(CHJ3.. 0 0 CO i NH 0 0 N COW 12H 25 Mel Me (18) kb Nt 0 0 b 0 p W b,,-S02(:2'L h( N "I) \LN k' 19) 0 goN40-SO2C12P'2,5 0 SO2W 21) C12H25 S NI o 0 'COOC,,H5 0 (23) SO?-O-CH NHSO2W :%;, 1 CC 14H 29 0 0 0 1 1 11 IM i r g M14 (2S) P11-0x 0 0 CO j PLNH N. N Ni AO 0 01 (22) S02- CWC 12H 25 (M) = 12H 25 G 0 0 pr. NH 0 COOC 12H 25 (24) 0 S02-(\ Y/CH 0 H.21 ', p 9,S ocow N H '4 3 1 (265) Me.,9,.0 cl - NWO 1 S COOC 12 H25 j, WCOlCHO cl J 1 Et (27) Qo 0 cl 1 - p NH OYL 0 NHS02C,.3H33 NHCOCHO - 1 - Et '- (28) cl cl 0 NH 0 tl- ? cooc 12 H25 S NHCOCHO Et (29) cl C) 0 iNH- Y/S02NHC12H25 0 NHCOCHO (30) Me 0 cl NH- h,41 0 cooc 12 H25 S &I NHCOCHO 1 - 1 Et (31) 0 NHt cooc 12 H25 NHCOCHO El (32) Control Couplers 0 0 cl Bu 11- NH -0 0 NHS02C.,6H33 p1 S02 -C-OH (m) 00 cl - lk NH CI. M!! > r - 0 MeO N, 0==)--0 N EtO CH2Ph COOC 12 H25 (CC2) i, The photographic element may be a single colour element or a multicolour element. Multicolour elements contain image-dye-forming units sensitive to each of the three primary regions of the visible range of the electromagnetic spectrum. Each unit may comprise a single emulsion layer or a plurality of emulsion layers sensitive to a given region of the spectrum. The layers of the element, including the layers of the imagedyeforming units, may be arranged in various orders as known in the art. In an alternative format, the emulsions sensitive to each of the three primary regions of the spectrum may be disposed as a single segmented layer.
A typical multicolour photographic element comprises a support bearing a cyan image-dye-forming unit comprising a red-sensitive silver halide emulsion layer and a cyan dye-forming coupler; a magenta image-dyeforming unit comprising at least one green-sensitive silver halide emulsion layer and a magenta dye-forming coupler; a yellow image-dyeforming unit comprising at least one blue-sensitive silver halide emulsion layer and a yellow dye-forming coupler. The element may contain additional layers, such for example as filter layers, interlayers, overcoat layers and subbing layers.
If desired, the photographic element can be used in conjunction with an applied magnetic layer as described in Research Disclosure, November 1992, Item 34390 published by Kenneth Mason Publications, Ltd., Dudley Annex, 12a North Street, EMSworth, Hampshire P010 7DO, England, the contents of which are incorporated herein by reference. When it is desired to employ the inventive materials in a small format film, Research DiSClosure, June 1994, Item 36230, provides suitable embodiments.
In the following discussion of suitable materials for use in the emulsions and elements of this invention, reference will be made to Research Disclosure, September
1994, item 36544, available as described above, which will be identified hereafter by the term "Research Disclosure". The contents of the Research Disclosure, including the patents and publications referenced therein, are incorporated herein by reference and the Sections hereafter referred to are Sections of the Research Disclosure.
The silver halide emulsions employed in the elements of this invention can be either negative-working or positive-working. Suitable emulsions and their preparation as well as methods of chemical and spectral sensitization are described in Sections I through V. various additives such as UV dyes, brighteners, antifoggants, stabilizers, light absorbing and scattering materials, and physical property modifying addenda such as hardeners, coating aids, plasticizers, lubricants and matting agents are described, for example, in Sections II and VI through IX. Colour materials are described in Sections X through XIII.
Scan facilitating is described in Section XIV. Supports, exposure, development systems, and processing methods and agents are described in Sections XV to XX. Certain desirable photographic elements and processing steps are described in Research Disclosure, Item 37038,
February 1995.
With negative working silver halide a negative image may be formed. Optionally a positive (or reversal) image may be formed.
The colour developing agent may be selected from pphenylenediamines; typically the agent may be selected from:- 4-amino-N,N-diethylaniline hydrochloride, 4-amino-3-methyl-N,N- diethylaniline hydrochloride, 4-amino-3-methyl-N-ethyl-N-(2- methanesulfonamidoethyl)aniline sesquisulfate hydrate, 4-araino-3-methylN-ethyl-N-(2-hydroxyethyl)aniline sulfate, 4-amino-3-(2-methanesulfonamido ethyl)-N,N-diethylaniline hydrochloride and 4-amino-N-ethyl-N-(2-methoxyethyl)-m-toluidine di-p- toluene sulfonic acid.
is The yellow coupler in accordance with the invention may be used in combination with other classes of image couplers such as 3-acylamino- and 3-anilino-5pyrazolones and heterocyclic couplers (e.g.
pyrazoloazoles) such as, for example, those described in EP 285,274, U.S. Patent 4,540,654 and EP 119,860; and other 5-pyrazolone couplers containing different ballasts or coupling-off groups such as, for example, those described in U.S. Patent 4,301,235, U.S.
Patent 4,853,319 and U.S. Patent 4,351,897. Yellow or cyan coloured couplers (e.g. to adjust levels of interlayer correction) and/or masking couplers such as, for example, those described in EP 213,490, Japanese Published Application 58-172,647, U.S. Patent 2,983,608, German Application DE 2,706, 117C, U.K.
Patent 1,530,272, Japanese Application A-113935, U.S.
Patent 4,070,191 and German Application DE 2,643,965 may also be used. Said masking couplers may be shifted or blocked.
Photographically useful coupling-off groups are wellknown in the art. Such groups can determine the equivalency of the coupler, i.e., whether it is a 2-equivalent or a 4-equivalent coupler, or modify the reactivity of the coupler. Such groups can advantageously affect the layer in which the coupler is coated, or other layers in the photographic recording materialf by performing, after release from the coupler, functions such as dye formation, development acceleration or inhibition, bleach acceleration or inhibition, electron transfer facilitation and colour correction.
Representative classes of coupling-off groups include halo, alkoxy, aryloxy, heteryloxy, sulfonyloxy, acyloxy, acyl, heterocyclyl, sulfonamido, mercaptotetrazole, mercaptopropionic acid, phosphonyloxy, arylthio, and arylazo. These coupling-off groups are described in the art, for example, in U.S. Pat. Nos. 2,455,169, 3,227,551, 3,432,521, 3,476,563, 3,617,291, 3,880,661, 4,052,212 and 4,134,766; and in U.K. Patents and published application Nos. 1,466,728, 1,531,927, 1,533,039, 2,006,755A and 2,017,704A, the disclosure of which are incorporated herein by reference.
Thus, the coupler of the present invention may be used in association with materials that accelerate or otherwise modify the processing steps e.g. of bleaching or fixing to improve the quality of the image. Bleach accelerators described in EP 193,389; EP 301,477; U.S. 4,163,669; U.S. 4,865,956; and U.S. 4,923,784 are particularly useful. Also contemplated is use of the coupler in association with nucleating agents, development accelerators or their precursors (U.K.
Patent 2,097,140; U.K. Patent 2,131,188; electron transfer agents (U.S. 4,859,578; U.S. 4,912,025); antifogging and anti colour-mixing agents such as derivatives of hydroquinones, aminophenols, amines, gallic acid; catechol; ascorbic acid; hydrazides; sulfonamidophenols; and non colour-forming couplers.
The yellow coupler may be used in combination with filter dye layers comprising colloidal silver sol or yellow and/or magenta filter dyes, either as oil-inwater dispersions, latex dispersions or as solid particle dispersions. Additionally, they may be used with "smearing" couplers (e.g. as described in U.S.
4,366,237; EP 96,570; U.S. 4,420,556; and U.S. 4,543,323). Also, the couplers may in some embodiments be blocked or coated in protected form as described, for example, in Japanese Application 61/258,249 or U.S. 5,019,492.
The yellow coupler may further be used in combination with imagemodifying compounds such as "Developer- Inhibitor-Releasing" compounds (DIR's); DIR's useful in conjunction with said couplers are known in the art and examples are described in U.S. Patent Nos. 3,137,578; 3,148,022; 3,148,062; 3,227,554; 3,384,657; 3,379,529; 3,615,506; 3.617,291; 3,620,746; 3,733,201; 4,049,455; 4,095,984; 4,126,459; 4,149,886; 4,150,228; 4,211,562; 4,248,962; 4,259,437; 4,362,878; 4,409,323; 4,477,563; 4,782,012; 4,962,018; 4,500,634; 4,579,634; 4,579,816; 4,607,004; 4,618,571; 4,678,739; 4,746,600; 4,746,601; 4,791,049; 4,857,447; 4,865,959; 4,880,342; 4,886,736; 4,937,179; 4,946,767; 4,948,716; 4,952,485; 4,956,269; 4,959,299; 4,966,835; 4,985,336 as well as in patent publications GB 1,560,240; GB 2,007,662; GB 2,032,914; GB 2,099,167; DE 2,842,063, DE 2,937,127; DE 3,636,824; DE 3,644,416 as well as the following European Patent Publications: 272,573; 335,319; 336,411; 346,899; 362,870; 365,252; 365,346; 378,236; 384,670; 396,486; 373,382; 376,212; 377,463; 401,612; 401,613.
Such compounds are also disclosed in "DeveloperInhibitor-Releasing (DIR) Couplers for Colour Photography", C.R. Barr. J. R. Thirtle and P.W. Vittum. in Photographic Science and Engineering, vol. 13, p.174 (1969), incorporated herein by reference.
Generally, the developer inhibitor-releasing (DIR) couplers may include a coupler moiety and an inhibitor coupling-off moiety (IN). The inhibitorreleasing couplers may be of the time-delayed type (DIAR couplers) which also include a timing moiety or chemical switch which produces a delayed release of inhibitor. Examples of typical inhibitor moieties are: oxazoles, thiazoles, diazoles, triazoles, oxadiazoles, thiadiazoles, oxathiazoles, thiatriazoles, benzotriazoles, tetrazoles, benzimidazoles, indazoles, isoindazoles, mercaptotetrazoles, selenotetrazoles, mercaptobenzothiazoles, selenobenzothiazoles, mercaptobenzoxazoles, selenobenzoxazoles, mercaptobenzimidazoles, selenobenzimidazoles, benzodiazoles, mercaptoaxazoles, mercaptothiadiazoles, mercaptothiazoles, mercapto- triazoles, mercaptothiatriazoles, mercaptotriazoles, mercaptooxadiazoles, mercaptodiazoles, mercaptooxathiazoles, tellurotetrazoles or benzisodiazoles.
The couplers of the invention were prepared by the following general method of synthesis.
ENU C1CH2COC1 C1CE2 COM THF/pyridine (COGWO N+Imp-)0- R1S02CH(COG)COM wherein M+ is an alkali metal cation and COG is an coupling-off group Example 1.
Preipal;ation of dodecyl 3-(2-chlogo-2-phenyl- R1S02M+ /DMF R1S02CH2CONYZ so 2 cl 2 /CH 2 cl 2 R1 S02 CHC1CONYZ sulfonylacetamido)-4-chlorobenzoate Coupler (1) c H2N:
0 cl C)CI-2COCI NH COW12H25 COW 12F5 THF/Pyridirie 502Na cl 0 0 SO2Chi DW NH 0 0 CH2C12 COW 12H25 0 cl NH cl 0 COW 121_25 (1) Preparation of dodecyl 3--(2-chloroacetamido)-4chlorobenzoate Chloroacetyl chloride (113.0g, 1.Omol) in dry tetrahydrofuran (500m1) was cooled and stirred in an ice bath and a solution of dodecyl 3-amino-4-chlorobenzoate (170g, 0.5mol) dissolved in dry tetrahydrofuran (500 ml) and pyridine (79.0g, 1.Omol) was added dropwise over 30 min keeping the temperature below 100C. The mixture was stirred for 1h and then poured into dilute hydrochloric acid (81) and the yellowish solid filtered off, washed and dried. The product was crystallised from ethanol to give colourless crystals, 158.86g. Two further crops of 7.68g and 8.58g were obtained from the filtrate giving a total yield of 185.78g, 89%.
C21H31C12NO3 Requires: C 60.6%, H 7.5%, N 3.4%, Cl 17.0% Found: C 60.8%, H 7.2%, N 3.3%, Cl 17.2% (2) Preparation of dodecyl 3-(2-phenylsulfonvlacetamido)-4-chlorobenzoate Dodecyl 3-(2-chloroacetamido)-4-chlorobenzoate (11.63g, 28.Ommol) was dissolved in dry dimethylformamide (100m1). Sodium benzenesulfinate (6. 88g, 42.Ommole) was added and the reaction mixture stirred for 24h. TLC analysis (1:2 ethyl acetate:petrol) showed some starting material remaining. An additional quantity of sodium benzenesulfinate (2.29g, 14.Ommol) was added and stirring continued for a further 24hr. The mixture was then poured into dilute hydrochloric acid (11) and the brown solid filtered off washed and dried. The solid was purified by column chromatography using 1:4 ethyl acetate:60-800C petroleum ether as eluent on silica gel support. The product was obtained as a white solid, 12.2g, 83%.
C27H36C1NO5S Requires: C 62.1%, H 6.95%, N 2.7% Found: C 61.8%, H 7.1%, N 2.6% (3) Preparation of Coupler (1) Dodecyl 3-(2-phenylsulfonylacetamido)-4-chlorobenzoate (9.78g, 19.Ommol) was dissolved in dichloromethane (40 ml) and sulfuryl chloride (2.53g, 19. Onunol) added dropwise and the mixture stirred overnight. The solvent was removed by rotary evaporation to leave a yellow residue which was purified by column chromatography using 1:4 ethyl acetate:60-800C petroleum ether as eluent on silica gel support. The product was obtained as a white solid, 6.82g, 65%.
C27H35C12NO5S Requires: C 58.3%, H 6.3%, N 2.5% Found: C 58.2%, H 6.3%, N 2.5% Coupler (5) N-(2-chloro-4-dodecvlsulfonylphenvl)-2chloro-2-(4methylphenvlsulfonyl) acetamide was prepared similarly from sodium toluene sulfinate and 2-chloro-N(2-chloro-4- dodecylsulfonylphenyl) acetamide.
C27H37C12NO5S2 Requires: C 54.9%, H 6.3%, N 2.4% Found: C 55.0%, H 6.3%, N 2.35-, Example 2 Preparation of dodecyl 3-(2=-{2-F2-(2,4-di-t-pentvlPhenoxv)butyramidolphenvlthiol-2-phenvlsulfonyl acetamido)-4-chlorobenzoate Coupler (10) r- Me (COGY 0 N+ %--1 0- 0 0 Na0AcCOAc 0 COOC 12H 2s o o NI 0 S COOC 12H 25 NHCOCHO Dodecyl 3-(2-phenylsulfonylacetamido)-4-chlorobenzoate (12.3g, 23.6mmol) (prepared as in Example 1 (2)) was added to a mixture of 2,2-bis-[2-(2,4-di-t-pentyl- phenoxy)butyramidophenyll disulfide (10.05g, 11.8mmol), sodium acetate, (1.94g, 23.6mmol), N-methylmorpholineN-oxide (60% wt/wt in water, 13.8g, 70.8mmol) and ethyl acetate (150 ml). The reaction mixture was heated under reflux for 24h. TLC (1:4 ethyl acetate:petrol) indicated approximately 50% reaction. Another portion of 2,2-bis-[2-(2,4-di-t-pentylphenoxy) butyramidophenyl] disulfide (10.05g, 11.8mmol) was added and refluxing continued for another 24h. No further change was observed by TLC. The mixture was poured into dilute hydrochloric acid (31), extracted with ethyl acetate, washed and dried (M9S04). Removal of the solvent by evaporation gave the crude product which was purified by column chromatography using 1:6 ethyl acetate:60-800C petroleum ether as eluent on silica gel support. The product was obtained as a white glass, 18.75g, 84%.
C53H71C1N207S2 Requires: C 67.2%, H 7.55%, N 3.0% Found: C 67.5%, H 7.6%, N 3.1% Couplers (6),(7),(9),(10),(14),(28),(29) and (31) were prepared similarly with yields and analytical data as below.
(6) Yield 26%, C39H51C1N206S2 Requires: C 63.0%, H 6.9%, N 3.8% Found: C 62.9%, H 6.9%, N 3.7% (7) Yield 40%, C53H73C1N207S3 Requires: C 64.8%, H 7.3%, N 2.9% Found: C 64.5%, H 7.3%, N 2.8% (9) Yield 19%, C38H51C1N206S3 Requires: C 59.8%, H 6.7%, N 3.7% Found: C 59.8%, H 6.7%, N 3.9% (10) Yield 20%, C53H71C1N207S2 Requires: C 67.2%, H 7.55%, N 3.0% Found: C 67,5%, H 7.60%, N 2.9% (14) Yield 36%, C61H80C1N307S2 Requires: C 68.7%, H 7.6%, N 3.9% Found: C 68.8%, H 7.6%, N 3.7% (28) Yield 5%, C56H80C1N307S3 Requires: C 64.7%, H 7.8%, N 4.05% Found: C 64.8%, H 8.0%, N 4.30% (29) Yield 26%, C53H70C12N207S2 (31) Yield 28%, C54H73C1N208S2 Requires: C 64.8%, H 7.2%, N 2.85% Found: C 64.8%, H 7.3%, N 2.80% Requires: C 66.3%, H 7.5%, N 2.9% Found: C 66.2%, H 7.5%, N 2.9% Example 3 Preparation of dodecyl 3-(2-t-butvlsulfonvl-2-chloroacetamido)- 4-chlorobenzoate Coupler (3) 0 Ed 'SQ2 Li But., 0 0 " DMF NH-0 0 CCOC12H2s cc=12 sccb 0 0 NH-0 CH2Cb a CO0C12F' -M Preparation of lithium t-butv1sulfinate Et2 0 ButLi + S02 (liq.) ButS02Li Sulphur dioxide (40m.1, 920mmol) was condensed in a dry round bottomed f lask with side arms at -781C (cardice/acetone bath). Cold (50C) dry ether (100m1) was added and a solution of fresh t-butyl lithium (1,7M in pentane, 50m.1, 85mmol) was added in 5m1 portions by syringe through a septum, cap in one of the side arms over a period of 30 min. The reaction temperature was maintained at -780C for 1h and then allowed to warm up to room temperature overnight. The remaining solvents were removed on a rotary evaporator and the white solid dried under vacuum. The yield of product was 10.55g, 97%. The NMR spectrum of the solid in D2 0 showed one major product containing a t-butyl group. This was used crude in the next stage.
(2) Preparation---og--dodesyl 3-(2-t-butvlsulfonvl-acetamido.).-4?.. chlorobenzoat.e Dodecyl 3-(2-chloroacetamido)-4-chlorobenzoate (10.4g, 25. Ommol) (prepared as in Example 1 (1)) was dissolved 5 in dry dimethylformamide (100m1). Lithium t-butylsulfinate (9.55g, 74Ammol) was added and the reaction mixture stirred for 8 days. TLC analysis (1:2 ethyl acetate:petrol) showed some starting material remaining. The mixture was then poured into dilute hydrochloric acid (11) and the oil extracted with ethyl acetate, washed and dried. After removal of the solvent by evaporation the oil was purified by column chromatography using 1:3 ethyl acetate:60-80'C petroleum ether as eluent on silica gel support. The product was obtained as a white solid, 11.1g, 90%.
C25H40C1NO5 S Requires:
C 59.8%, H 7.45%, N 3.05% Found: C 60.1%, H 7.9%,N 2.7% (3) Preparation of Coupler 3 Dodecyl 3-(2-t-butylsulfonylacetamido)-4- chlorobenzoate (8.0g, 16.0mmol) was dissolved in dichloromethane (150m1) and sulfuryl chloride (4.4g, 32Ammol) added dropwise. The mixture was stirred for two days at room temperature. TLC analysis (2:1 petrol:ethyl acetate) showed a mixture of mono- and di-chlorinated products and starting material. The solvent was removed by evaporation and the the residue chromatographed on silica gel with 4:1 petrol:ethyl acetate to give the dichlorinated product dodecyl 3-(2-t-butylsulfonyl2,2-dichloroacetamido)- 4-chlorobenzoate (3.1g, 34%) and the mono-chlorinated product dodecyl 3(2-t-butylsulfonyl-2-chloro)-4-chlorobenzoate, 3.8g, 44%.
Example 4 Preparation of dodecyl 3-(2-(2-[2-(2,4-di-tpentvlphenoxv)butyramido)phenvlthio)-2-t-butvlsulfonv l--acetamido)-4chlorobenzoate, Coupler (8) B,,, 0 0 Co -jNH 0 r- Me (COG11 0 %.-1 N+ NaOAc/E10Ac C 0 0 W,2, 11 N H - 0 S COOC 12 H21 NHCOCHO 1 ti COOC 12 H25 Dodecyl 3-(2-t-butylsulfonylacetamido)-4-chlorobenzoate (9.59g, 19.1mmol) was added to a mixture of 2,2-bis-[2(2,4-di-t-pentylphenoxy)butyraiaidophenylj disulfide (16.3g, 19.1mmol), sodium acetate, (1.7g, 20.Ommol), N-methylmorpholine-N-oxide (60% wtlwt in water, 12.0g, 60.Ommol) and ethyl acetate (500 ml). The reaction 15 mixture was heated under reflux for 18h. TLC (4:1 petrol:ethyl acetate) indicated approximately 50% reaction. The mixture was poured into dilute hydrochloric acid (41) and the ethyl acetate layer washed and dried(M9S04). Removal of the solvent by evaporation gave the crude product which was purified by column chromatography using 4:1 60-800C petroleum ether:ethyl acetate as eluent on silica gel support. The product was obtained as a white glass, 6.3g, 36%.
C51H7SC1N2 07S2 Requires: C 66.05%, H 8.1%, N 3.0% Found: C 66.1%, H 8.0%, N 2.9% Example 5
Preparation of dodecyl 3-(2-(2-[2-(2,4-di-tRentvlphenoxv)butyramido)phenvlthio)-2-methvlsulfonvlacetamido)-4chlorobenzoate Coupler (27) This was prepared analogously to coupler (8) in 26% yield using sodium methane sulfinate prepared as follows:Preiparation of Sodium methanesulfinate.
Mc-ONa 2 PhSE + MeS02C1 - /1 Me0H PhSSPh + MeS02 Na + NaCl Thiophenol (22g, 0.2mol) was added to a solution of sodium methoxide (10.8g, 0.2mol) in methanol (200m1).
The solution was stirred at room temperature for 5min then methanesulfonyl chloride (11.5g, 0.1 mol) was added and the mixture warmed to 500C for 1h, cooled and the methanol removed by rotary evaporation. Water (50m1) was added to the mixture and it was stirred for 10min, filtered to remove diphenyl disulfide and the water removed by rotary evaporation. The solid was dried under vacuum to give the product as a white solid, 7.2g, 71%. Analysts indicated this to be the required sulfinate with 20-30% of the sulfonate salt. The product was used crude in the next stage.
Photographic Data (1) Test Procedures Compounds of the present invention (and control compounds) were dispersed in coupler solvent and incorporated into photographic coatings containing a silver bromciodide emulsion, on a transparent support,' according to the following coating diagram:
Gel Supercoat Gelatin 1.50 g/M2 EMU1Sion Layer Support Silver bromoiodide Coupler Gelatin Bis(vinylsulphonyl) methane (hardener) Cellulose acetate 0. 81 g/M2 1.932 mmol/m 2.42 g/m 2 0.06 g1M2 Aqueous dispersions of the couplers were prepared by methods known in the art. The yellow dye-forming coupler dispersions contained 6% by weight of gelatin, 9% by weight of coupler and a 1.0:0.5:1.5 weight ratio of coupler to di-n-butyl phthalate coupler solvent to cyclohexanone auxiliary solvent. The auxiliary solvent was included to aid in dispersion preparation and was removed by washing the dispersion for 6 hours at CC and pH 6.0. (i) Sensitometric testIng The experimental photographic coatings prepared in this way were slit and chopped into 30cm, x 35mm test strips.
After hardening the strips were exposed (1.0 sec) through a 0-4.0 neutral density step wedge (0.2 ND step increments) and Daylight V, Wratten 35 + 38A filters and 0.3 ND filter then processed through a standard C-41 process as described in the British Journal of Photography Annual (1988) 196-198 using the following steps and process times:
Developer Bleach Wash Fix Wash 2.5 minutes 4.0 minutes 2.0 minutes 4.0 minutes 2.0 minutes For each test strip, Status m densities were measured as a function of exposure using a spectral array automatic transmission densitometer. Measurements of sensitometric parameters - minimum density (Dmin), maximum density (Enax), contrast (y) and photographic speed (KIT) - were obtained from plots of density vs. log exposure (D1ogE curves).
In addition to the above standard conditions, separate strips of each coating were also developed in a competing process employing the same process steps as above but using a developer modified by the addition of 5.0 g/1 citrazinic acid (CZA) and adjusted to pE 10.0 by the addition of sodium carbonate. The ratio of contrast in the competing process to contrast in the standard process OCZA/YSTD) is quoted as an indication of infilm reactivity of the coupler.
(ii) Spectrophotometric testing 35mm Test strips were exposed as above through a 0-0.9 ND step-wedge (0.3 ND increments) and Daylight V, Wratten 35 + 38A filters and the correct ND filters to give an optical density of ca.1.0. The strips were processed using the standard conditions described above and samples cut from the yellow dye image step with density closest to 1.0. Visible absorption spectra of the resultant yellow dyes (normalised to 1.0 density) were obtained using a Pye-Unicam SP8-100 spectrophotometer. Dye hues are expressed in terms of the wavelength corresponding to the maximum absorption peak (kmax) and the width of the curve at half the peak height - known as the half-bandwidth (HBW).
(iii) Dye stability testing Yellow dye sample patches of density ca.1.0 were prepared as for spectrophotometric testing and their absorption spectra measured as above.
Light stability testing: The dye sample patches, protected with a Wratten 2B gelatin filter, were faded for periods of 100h and 200h accumulated fade using a fadeometer in which the samples were mounted at a fixed distance of 4.0 cm from a pair of 85W, 6ft colour matching fluorescent tubes maintained in strictly controlled conditions of 170C and 50% relative humidity in the EDIE fade test.
Dark/wet stability testing: The dye sample patches were incubated in a dark oven for periods of 1,3 and 6 weeks accumulated fade at a constant 600C and 70% relative humidity.
In both cases the spectrophotometric curves were remeasured after each fade period and the degree of quoted as the percentage decrease in density at the wavelength of maximum absorption (Xmax) relative to initial density prior to fading. 30 (II) PhotograRhic Data The data in Table 1 shows a comparison of the dye hues of couplers of the invention with the control couplers CC1 and CC2. Figure 1 shows a typical dye hue curve compared to the control coupler, wherein the solid line represents coupler (10) of the invention and the dotted line that of control coupler (CC2).
TABLE 1
Coupler No. kmax HBW (6) 459.0 93.5 (7) 462.5 98.0 (8) 449.5 93.5 (9) 467.0 99.0 (10) 448.5 96.0 (14) 448.0 97.5 (27) 450.0 92.5 (29) 452.5 94.0 (30) 460.5 95.5 (31) 450.0 92.5 (32) 451.0 93.5 (Ccl) 448.0 94.5 (CC2) 448.0 91.5 It will be seen that the kmax and dye hues are in the usable range of the spectrum suitable for yellow couplers.
Table 2 shows a comparison of the light stability of the couplers of the invention with the control couplers CC1 and CC2.
TABLE 2
Coupler No. Light Fade EDIE/200h, % (6) -7 (7) -4 (8) -5 (10) -1 (14) -1 (27) -2 (29) -3 (30) -2 (31) -3 (32) -2 (Ccl) -16 (CC2) -22 The couplers of the invention have superior light fade characteristics, with at least a twofold improvement in % fade over 200 hours compared with the control couplers.
Table 3 shows a comparison of the dark/wet stability of the couplers of the invention with the control couplers CC1 and CC2.
TABLE 3
Coupler No. Dark/Wet Fade 6Wk,% (7) -6 (8) -17 (9) -20 (10) -18 (14) -6 (27) -10 (29) -17 (30) -10 (31) -10 (32) -12 (Ccl) -9 (CC2) -15 The dark/wet stability of the couplers of the invention is comparable with that of the control couplers.
Thus the photographic azamethine dyes formed from the novel couplers of the invention exhibit excellent dye light stability which are better than the state of the art control couplers used in current photographic products, have acceptable dark/wet fade characteristics and kmax and dye hues which are appropriate for use as yellow couplers

Claims (14)

  1. CLAIMS:
    An image dye-forming coupler of formula (I):- 0 0 R 1 -,, // S NYZ 1/ 0 X (I) wherein X is a coupling-of f group, R1, Y and Z are the same or different and are independently selected from alkyl, aryl or heterocyclic, each of which is unsubstituted or substituted with one or more coupler modifying functional groups, or one of Y and Z may be H; or Y and Z taken together with the nitrogen atom form a 5-10 membered heterocyclic ring which may contain one or more further heteroatoms selected from N, 0 and S, said heterocyclic ring being unsubstituted or substituted with one or more coupler-modifying functional groups.
  2. 2. A coupler according to claim 1 which has the formula (II) R' 0 0 /4 N H 0 X R3 R 2 (II) wherein R2 and R3 are independently selected from hydrogen and one or more coupler-modifying functional groups.
  3. 3. A coupler according to either of the preceding claims wherein R1, R2 R3, X, Y and Z are selected independently from coupler-solubilising groups, ballasting groups and dye hue-modifying groups.
  4. 4. A coupler according to claim 3 wherein the sum of the number of carbon atoms in one or more ballast groups is 10.
  5. 5. A coupler according to any one of the preceding claims wherein R1 is selected from an alkyl, aryl or heterocyclic group which is unsubstituted or substituted with one or more coupler-modifying functional groups. 6. A coupler according to claim 5 wherein R1 is selected from unsubstituted or substituted alkyl, phenyl, naphthyl, pyridyl or dioxanyl.
  6. 6. A coupler according to claim 6 wherein R1 is i-propyl, n-butyl, decyl, dodecyl or unsubstituted or substituted phenyl.
  7. 7. A coupler according to any one of the preceding claims wherein R2 and R3 are selected f roM E, halogen and unsubstituted or substituted alkoxy, carboxy ester, alkylsulfonyl, alkylcarbamoyl, alkylsulfonamido and alkylsulfamoyl.
  8. 8. A coupler according to claim 7 wherein one of R2 and R3 is selected from o-chloro and o-alkoxy.
  9. 9. A coupler according to any one of the preceding claims wherein X is selected from halogen, pseudohalogen, RO, RS, RCOO, RS020, RS02NH, RS02NR, (R0)2P(O)O, RN=N, where R is as defined for R 1 or from N-heterocycles attached to the coupling site by the heteroatom.
  10. 10. A coupler according to claim 9 wherein X is chloro or a thioaryl group which is unsubstituted or substituted with an alkoxy group or with an unsubstituted or substituted carbamoyl group.
  11. 11. A coupler according to claim 10 wherein X is thiophenyl group substituted with a 2,4-di-t-pentylphenoxybutyramido group.
  12. 12. A coupler according to claim 1 having one of the following formulae:
    0 cl NH S C:5 NHCOBu t COOC 12 H25 W 0 cl PL NH NH-b-- S02C12H25 S NHCOCHO - 1 - Et ' BU', Gt'? d NH S CO0C 12 H25 NHCOCHO 1 - Et cl 0 0 NWO 0 S CO0C12H25 NHCOCHO Et F' me cl 1 NWO 0 S NHCO(CH2)30 NHCOCHO El NH 0 C, COOC 12H25 NHCOCHO Et cl Me U P-0 cl NH-0 0 COOC 12 H25 &NHCOCHO - 1 - Et ' A p 0 C ! NH S02NHC12H25 S &NHCOCHO - 1 - Et _up 0 cl L NH 0 t cooc 12 H25 &NHCOCHO 1 - Et Me 0 cl NH 0 S COM 12 H25 NHCOCHO 1 r=t
  13. 13. A photographic element containing a compound of formula (I) or (II) according to any one of the preceding claims in asssociation with a light-sensitive silver halide emulsion layer.
  14. 14. A multi-colour photographic material comprising a support bearing yellow, magenta and cyan image-dye- 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, wherein at least one dye-forming coupler is a coupler according to any one of claims 1 to 12.
GB9811344A 1998-05-28 1998-05-28 Image-dye forming couplers and photographic elements containing them Expired - Fee Related GB2337750B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
GB9811344A GB2337750B (en) 1998-05-28 1998-05-28 Image-dye forming couplers and photographic elements containing them

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB9811344A GB2337750B (en) 1998-05-28 1998-05-28 Image-dye forming couplers and photographic elements containing them

Publications (3)

Publication Number Publication Date
GB9811344D0 GB9811344D0 (en) 1998-07-22
GB2337750A true GB2337750A (en) 1999-12-01
GB2337750B GB2337750B (en) 2003-10-15

Family

ID=10832761

Family Applications (1)

Application Number Title Priority Date Filing Date
GB9811344A Expired - Fee Related GB2337750B (en) 1998-05-28 1998-05-28 Image-dye forming couplers and photographic elements containing them

Country Status (1)

Country Link
GB (1) GB2337750B (en)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2037751A (en) * 1978-11-24 1980-07-16 Konishiroku Photo Ind Substituted pivaloyl-2-chloroacetanilide yellow couplers and their use in a process for forming dye images
JPS5811543A (en) * 1981-07-13 1983-01-22 Matsushita Electric Works Ltd Phenolic resin molding material
JPS5921044A (en) * 1982-07-26 1984-02-02 Fujitsu Ltd Manufacture of semiconductor device
JPH06186702A (en) * 1992-12-18 1994-07-08 Konica Corp Silver halide color reversal photographic sensitive material
JPH07110559A (en) * 1993-10-12 1995-04-25 Fuji Photo Film Co Ltd Silver halide color photographic sensitive material
JPH07191441A (en) * 1993-12-27 1995-07-28 Fuji Photo Film Co Ltd Silver halide color photographic sensitive material
JPH07311450A (en) * 1994-05-16 1995-11-28 Fuji Photo Film Co Ltd Silver halide color photographic sensitive material
JPH0934071A (en) * 1995-07-14 1997-02-07 Fuji Photo Film Co Ltd Silver halide color photographic sensitive material and image forming method

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58115437A (en) * 1981-12-28 1983-07-09 Konishiroku Photo Ind Co Ltd Blocked magenta dye forming coupler
JPS59210440A (en) * 1983-05-13 1984-11-29 Fuji Photo Film Co Ltd Color photographic sensitive silver halide material

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2037751A (en) * 1978-11-24 1980-07-16 Konishiroku Photo Ind Substituted pivaloyl-2-chloroacetanilide yellow couplers and their use in a process for forming dye images
JPS5811543A (en) * 1981-07-13 1983-01-22 Matsushita Electric Works Ltd Phenolic resin molding material
JPS5921044A (en) * 1982-07-26 1984-02-02 Fujitsu Ltd Manufacture of semiconductor device
JPH06186702A (en) * 1992-12-18 1994-07-08 Konica Corp Silver halide color reversal photographic sensitive material
JPH07110559A (en) * 1993-10-12 1995-04-25 Fuji Photo Film Co Ltd Silver halide color photographic sensitive material
JPH07191441A (en) * 1993-12-27 1995-07-28 Fuji Photo Film Co Ltd Silver halide color photographic sensitive material
JPH07311450A (en) * 1994-05-16 1995-11-28 Fuji Photo Film Co Ltd Silver halide color photographic sensitive material
JPH0934071A (en) * 1995-07-14 1997-02-07 Fuji Photo Film Co Ltd Silver halide color photographic sensitive material and image forming method

Also Published As

Publication number Publication date
GB2337750B (en) 2003-10-15
GB9811344D0 (en) 1998-07-22

Similar Documents

Publication Publication Date Title
JPH031655B2 (en)
JPH0549975B2 (en)
US4503141A (en) Silver halide color photographic light-sensitive materials containing couplers with a hydroxyl substituted aromatic heterocyclic sulfonyl group in the ballast group
US5008180A (en) Photographic recording material containing a cyan dye-forming coupler
EP0284239B1 (en) Photographic silver halide materials and process comprising a pyrazoloazole coupler
US5143821A (en) Color photographic material comprising a 2-alkoxy pyrazolo[1,5-a]benzimidazole color coupler
EP0751428B1 (en) Novel image-dye-forming couplers and photographic elements containing them
EP0240852B1 (en) Silver halide photographic light-sensitive material
GB2359635A (en) Photographic element with a phenolic cyan dye-forming coupler
JPH04124661A (en) Silver halide color photographic sensitive material
EP0622673B1 (en) Photographic colour couplers and photographic materials containing them
EP0618496B1 (en) Photographic elements containing particular color couplers in combination with particular stabilizers
JPH0451149A (en) Silver halide color photographic sensitive material
EP0434148B1 (en) Photographic material and process comprising a pyrazolotriazole coupler
EP0751427B1 (en) Image-dye-forming couplers and photographic elements containing them
EP0399183A1 (en) Photographic recording material containing a cyan dye-forming coupler
GB2337750A (en) Image-dye forming couplers based on the active methylene containing 2-sulphonylacetamide skeleton and photographic elements containing them
JPS61151647A (en) Coupler for silver halide color photography
JPH0756296A (en) Preparation of coloring-matter stabilizer and photograph element
JPS61153640A (en) Silver halide color photographic sensitive material
EP0622672B1 (en) Photographic colour couplers, methods of making them and photographic materials containing them
US4942118A (en) Photographic silver halide materials and process comprising a pyrazoloazole coupler
GB2313834A (en) Improved synthesis of yellow couplers
JPH04149436A (en) Silver halide color photographic sensitive material
US4942117A (en) Photographic silver halide materials and process comprising a pyrazoloazole coupler

Legal Events

Date Code Title Description
PCNP Patent ceased through non-payment of renewal fee

Effective date: 20060528