EP0548313B1 - Magenta bildfarbstoff-kuppler mit verbessertem farbton - Google Patents

Magenta bildfarbstoff-kuppler mit verbessertem farbton Download PDF

Info

Publication number
EP0548313B1
EP0548313B1 EP92914038A EP92914038A EP0548313B1 EP 0548313 B1 EP0548313 B1 EP 0548313B1 EP 92914038 A EP92914038 A EP 92914038A EP 92914038 A EP92914038 A EP 92914038A EP 0548313 B1 EP0548313 B1 EP 0548313B1
Authority
EP
European Patent Office
Prior art keywords
coupler
couplers
dye
magenta
alkyl
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
EP92914038A
Other languages
English (en)
French (fr)
Other versions
EP0548313A1 (de
Inventor
Paul Barrett Merkel
Stephen Paul Singer
Bernard Arthur James Clark
Paul Louis Reginald Stanley
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
Publication of EP0548313A1 publication Critical patent/EP0548313A1/de
Application granted granted Critical
Publication of EP0548313B1 publication Critical patent/EP0548313B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • G03C7/384—Couplers containing compounds with active methylene groups in rings in pyrazolone rings
    • 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
    • G03C7/22—Subtractive cinematographic processes; Materials therefor; Preparing or processing such materials
    • G03C7/24—Subtractive cinematographic processes; Materials therefor; Preparing or processing such materials combined with sound-recording
    • 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

Definitions

  • the present invention relates to photographic coupler compositions comprising two-equivalent 3-anilino-1-phenyl-5-pyrazolone magenta dye forming couplers with strong electron-withdrawing substituents on both the 3-anilino and 1-phenyl groups and with arylthio or alkylthio coupling-off groups.
  • the invention also relates to color photographic materials including such coupler compositions and to methods for improving the hue of magenta dyes and for providing high dye formation efficiency in such materials.
  • pyrazolone magenta couplers particularly 3-anilino-1-phenyl-5-pyrazolone couplers
  • imaging couplers for photographic applications.
  • Advantages that may be associated with the use of these couplers include low cost, high reactivity, high dye extinction coefficients and good dispersibility.
  • Two-equivalent pyrazolone magenta dye-forming couplers with coupling-off groups in the 4-position have additional potential advantages including high efficiency of dye formation from oxidized developer, very high reactivity, low sensitivity to process pH variations, formaldehyde insensitivity and resistance to thermally induced reaction with magenta dye.
  • pyrazolone magenta dye forming couplers that previously have been described suffer from disadvantages such as producing dyes with hues that are too hypsochromic upon coupling with commonly used developers, high equivalency, sensitivity to formaldehyde or the tendency to undergo side reactions that do not lead to dye formation.
  • Dye hues that are too hypsochromic can lead to inaccurate and objectionable color reproduction from color negative materials or directly viewed photographic materials such as color prints or color transparencies.
  • magenta dyes that are too hypsochromic produce high amounts of unwanted blue light absorption and can result in prints with inaccurate color or low color saturation.
  • the unwanted blue absorption can also cause other negative effects such as increasing the time required to print from processed negatives by necessitating larger contents of masking couplers to offset the unwanted absorption and by limiting the amounts of other blue absorbers that can be added.
  • the use of four-equivalent couplers or of two-equivalent couplers that undergo side reactions leads to inefficiencies and increases cost.
  • This invention identifies practical two-equivalent magenta dye forming pyrazolone couplers and coupler compositions that have high activity, that are resistant to reaction with formaldehyde or to side reactions and that yield dyes with reduced unwanted blue light absorption for more accurate color reproduction.
  • the coupler compositions used in this invention can be used to produce photographic materials in which continued coupling is suitably low in processes without a stop bath between the development and bleach steps.
  • Patent 3,907,571 describes 3-anilino-5-pyrazolone magenta dye-forming couplers with sulfamoyl substituents in the meta or para positions of the anilino ring.
  • the extent of the bathochromic hue shifts and of the reductions in unwanted blue light absorption by such dyes are less than normally desired for optimum color reproduction.
  • the couplers described in U.K. Patent Application 2,071,647 do not yield dyes that are sufficiently bathochromic for many applications.
  • U.S. Patents 4,351,897 and 4,556,630 disclose two-equivalent 3-anilino-5-pyrazolone couplers with specific arylthio coupling-off groups. These patents do not consider structures that yield bathochromic dyes having low unwanted blue light absorption in accordance with the invention.
  • German Patent Application DE 3,730,557 describes two-equivalent 3-anilino-5-pyrazolone couplers with thio coupling-off groups used in combination with carbonamide oil formers, but also does not deal with structures that yield bathochromic dyes with low unwanted blue light absorption.
  • U.S. Patent 4,595,650 discloses photographic materials containing pyrazolone couplers of the 3-anilino or 3-acylamino types containing an arylthio group at the coupling position with an alkoxy or aryloxy substituent substituted in a specified manner.
  • One of the 50 odd structures exemplified shows a strong electron withdrawing group in both rings but one of these is the undesirable acyl group.
  • the use of acyl ring substituents is undesirable because these groups are difficult to synthesize, and they tend to be deleterious to the photographic properties, particularly light stability. No mention is made in the patent of the advantageous bathochromic properties obtained in this invention. Further, it has been found that arylthio coupling off groups containing an ortho alkoxy substituent exhibit undesirably stable leuco dyes.
  • pyrazolone magenta couplers provide dyes that have the inherent property of absorbing some blue light which is undesirable because these dyes are ideally responsive to green light only.
  • a masking coupler which functions to provide a similar blue absorbance in the non-image areas corresponding to the unwanted blue absorbance in the image area caused by the magenta dye formed.
  • the unwanted blue absorption is a problem which may require the addition of a mask.
  • the unwanted blue absorption adversely affects the ability to include image modifiers for sharpness etc. which generate dyes with unwanted blue absorption and also can prolong the printing time for processed negatives having the excess blue absorbance.
  • An embodiment of this invention relates to employing the photographic materials in combination with a dispersion of magnetic particles.
  • U.S. Patent 4,990,276 and EP 0 459 349 Al provide background on such dispersions and photographic materials.
  • the coupler materials herein provide an effective way of counteracting unwanted blue light absorption by the magnetic layer in processed negatives during the printing of processed negatives.
  • coupler compositions and color photographic materials having useful photographic properties and that yield bathochromic magenta dyes with reduced unwanted blue light absorption, particularly those that have high activity, that have low equivalency and that are free from side reactions, and which may be used for the efficient formation of magenta dyes in color photo; graphic materials. It is further desirable to provide magenta dye forming coupler compositions and photographic materials of low cost, whose dye forming characteristics have low sensitivity to variations in developer pH, exhibit low continued coupling in seasoned bleach solutions, do not require stabilization with formaldehyde solutions and have stable magenta dye images, and which most preferably have a reduced tendency to form stable leuco dyes.
  • the invention encompasses a photographic material comprising a support bearing at least one photosensitive silver halide emulsion layer having associated therewith a magenta dye-forming coupler having the formula: wherein
  • the invention also encompasses a process for improving photographic materials having unwanted blue absorption.
  • the Figure is a graph showing the magenta dye absorption spectra obtained using the coupler of the invention (M11) and a comparison coupler (B5) as more fully described in Example 5.
  • any reference to a substituent by the identification of a group containing a substitutable hydrogen e.g., alkyl, amine, aryl, alkoxy, heterocyclic, etc.
  • a substitutable hydrogen e.g., alkyl, amine, aryl, alkoxy, heterocyclic, etc.
  • the organic substituents have less than 30 carbon atoms and typically less than 20 carbon atoms.
  • Suitable specific substituents include the following: sulfamoyl, such as N-methylsulfamoyl, N-hexadecylsulfamoyl, N, N-dimethylsulfamoyl; N-[3-(dodecyloxy)propyl]sulfamoyl, N-[4-(2,4-di-t-pentylphenoxy)butyl]-sulfamoyl, N-methyl-N-tetradecylsulfamoyl, and N-dodecylsulfamoyl; sulfamido, such as N-methylsulfamido and N-octdecylsulfamido; carbamoyl, such as N-methylcarbamoyl, N-octadecylcarbamoyl, N-[4-(2,4-di- t -pentylphenoxy
  • Alkanesulfonyl such as alkanesulfonyl containing 1 to 30 carbon atoms, for example methanesulfonyl, octanesulfonyl, 2-ethylhexanesulfonyl,and hexadecanesulfonyl; arenesulfonyl, such as benzenesulfonyl, 4-nonylbenzenesulfonyl, and p -toluenesulfonyl;
  • the coupling-off group Q is of the general formula: wherein R4 and R5 are individually selected from alkyl, alkoxy, aryloxy, carbonamido, ureido, carbamate, sulfonamido, carbamoyl, sulfamoyl, acyloxy, alkoxycarbonyl. aryloxycarbonyl, amine, halogen, hydrogen and carboxyl; and wherein q is 0, 1 or 2.
  • R4 and R5, when present, are carbonamido or alkyl.
  • the total number of carbon atoms in R4 and R5 taken together is at least 4 but not greater than 25. It is particularly preferred that R4 has at least one carbon atom.
  • the pi value (as hereafter described) of the combined R4 and R5 substituents is at least 2.5.
  • Pi values are partition coefficients which measure the hydrophilic/hydrophobic nature of a substituent (more positive means more hydrophobic). See for example "Substituent Constants for Correlation Analysis in Chemistry and Biology,” Wiley, New York, N.Y., 1979.
  • couplers with arylthio coupling off groups particularly those with an alkoxy substituent ortho to the sulfur, have a reduced tendency to form stable leuco dyes when the parent contains the electron-withdrawing groups prescribed herein.
  • the couplers used in this invention and the dyes that are generated from them be of sufficient molecular weight and hydrophobicity that they undergo minimal diffusion out of the layers in which they are coated when incorporated into photographic materials. It is also desired that the couplers used in this invention be soluble in and dispersible with high-boiling, hydrophobic, organic solvents referred to as coupler solvents (see below). To accomplish these aims the total number of carbon atoms in R1, R2 and R3 combined is preferably at least 10 and more preferably 12 to 30.
  • Coupler solvents useful for the practice of this invention include aryl phosphates (e.g. tritolyl phosphate), alkyl phosphates (e.g. trioctyl phosphate), mixed aryl alkyl phosphates (e.g.
  • diphenyl 2-ethylhexyl phosphate aryl, alkyl or mixed aryl alkyl phosphonates
  • phosphine oxides e.g. trioctylphosphine oxide
  • esters of aromatic acids e.g. dibutyl phthalate
  • esters of aliphatic acids e.g. dibutyl sebecate
  • alcohols e.g. 2-hexyl-1-decanol
  • phenols e.g. p-dodecylphenol
  • carbonamides e.g.
  • sulfoxides e.g. bis(2-ethylhexyl sulfoxide
  • sulfonamides e.g. N,N-dibutyl-p-toluenesulfonamide
  • hydrocarbons e.g. dodecylbenzene
  • Additional coupler solvents and auxiliary solvents are noted in Research Disclosure, December 1989, Item 308119, p 993.
  • Useful coupler:coupler solvent weight ratios typically range from about 1:0.1 to 1:10.
  • Especially useful coupler solvents for the practice of the invention are phosphates, carbonamides and sulfoxides.
  • the carbonamides are particularly useful in that there are a number of inexpensive carbonamide coupler solvents that produce benefits such as reduced continued coupling in bleach solutions and improved image stability.
  • Dye hues obtained using carbonamide coupler solvents are often more hyposochromic than desirable.
  • the couplers of this invention are used together with carbonamides, excellent dye hues can be obtained along with low continued coupling and good image stability.
  • the couplers of this invention permit a greater choice of coupler solvents and allow construction of improved photographic materials.
  • Carbonamide compounds or coupler solvents useful for the practice of this invention are represented by the generic formula II, wherein, R6, R7 and R8 are individually selected from the group consisting of straight chain, branched or cyclic alkyl groups, straight chain or branched alkenyl groups and straight chain or branched alkylene groups (forming bis compounds or rings), any of which may be substituted with one or more substituents selected from the group consisting of alkoxy, aryloxy, aryl, alkoxycarbonyl, aryloxycarbonyl, acyloxy and halogen; a phenyl group; and a phenyl group containing one or more substituents selected from the group consisting of alkyl, alkoxy, aryloxy, alkoxycarbonyl, aryloxycarbonyl, acyloxy and halogen (e.g.
  • R6, R7 and R8 combined contain at least 12 carbon atoms and preferably 15-30 carbon atoms to minimize volatility, water solubility and diffusivity.
  • R6 and R7 or R7 and R8 may join to form a ring.
  • R6 and R7 may join to form a five-membered pyrrolidinone ring.
  • the coupler compositions used in this invention may contain various addenda for improved photographic performance. These include aniline and amine addenda such as those described in U.S. Patents 4,483,918 and 4,585,728, which may reduce stain from continued coupling and other sources and may also improve image stability. Other stabilizing addenda such as phenols, chromanols and alkoxy benzenes may also be incorporated with the couplers used in this invention.
  • aniline compounds represented by the formula wherein R9 represents an alkyl, aralkyl, cycloalkyl or alkenyl group, any of which may be substituted; R10 is a hydrogen or a substituent defined the same as R9; Ar is a phenyl or substituted phenyl group.
  • Phenyl substituents include one or more alkyl, aralkyl, alkenyl, cycloalkyl, alkoxy, aryloxy, phenyl or acylamino groups.
  • R9 and R10 may be bonded to form a ring.
  • R9 and Ar may also be joined to form a ring. Together R9, R10 and Ar should contain at least 12 carbon atoms and preferably about 20 to 40 carbon atoms. Straight chain or branched alkyl R9 and R10 groups are preferred, and alkyl or alkoxy substituted Ar groups are preferred. Particularly preferred are Ar groups which are substituted with alkoxy groups ortho to the amino group. The latter may have additional substituents on Ar such as straight chain or branched alkyl groups.
  • Examples of two-equivalent 3-anilino-1-phenyl-5 pyrazolone magenta dye forming couplers of this invention include, but are not limited to, the compounds with the "M" prefix:
  • aniline addenda (III) useful in combination with the 3-anilino-1-phenyl-5-pyrazolone couplers used in this invention include A1 and A2:
  • the photographic coupler compositions used in the present invention are employed in color photographic materials in a manner well known in the photographic art.
  • a supporting substrate may be coated with a silver halide emulsion and a coupler composition comprising a two-equivalent 3-anilino-1-phenyl-5-pyrazolone magenta dye forming coupler with suitable electron withdrawing substituents on both the 1-phenyl and 3-anilino groups.
  • the photographic material may then be imagewise exposed and then developed in a solution containing a primary aromatic amine color developing agent in a manner well known in the photographic art.
  • the primary aromatic amine developing agent is oxidized in an imagewise manner by reaction with exposed silver halide grains, and the oxidized developer reacts with coupler to form dye.
  • the development step is followed by bleaching and fixing steps or a bleach-fix step to remove silver and silver halide from the coating.
  • photographic materials of the invention may be employed in conjunction with a photographic material where a relatively transparent film containing magnetic particles is incorporated into the material.
  • the photographic materials of this invention function well in such a combination and give excellent photographic results. Examples of such magnetic films are well known and are described for example in U.S. Patent 4,990,276 and EP 459,349 which are incorporated herein by reference.
  • the particles can be of any type available such as ferro-and ferri-magnetic oxides, complex oxides with other metals, ferrites etc. and can assume known particulate shapes and sizes, may contain dopants, and may exhibit the pH values known in the art.
  • the particles may be shell coated and may be applied over the range of typical laydown.
  • the embodiment is not limited with respect to binders, hardeners, antistatic agents, dispersing agents, plasticizers, lubricants and other known additives.
  • the couplers used in the invention are especially suited for use in combination with these magnetic layers.
  • the layer may suitably be located on the side of the photographic material substrate opposite to the silver halide emulsions and may be employed to magnetically record any desired information.
  • One notable deficiency attributed to such a layer is that the particle layer tends to absorb blue light when light is shined through the processed negative to create a reflective color print. This distorts the color otherwise obtainable without the layer unless needed corrections are made. This also reduces the light transmission during printing so that the printing time must be increased for comparable results.
  • the coupler used in the present invention may be incorporated in the magenta dye forming layer to replace all or part of the conventional coupler since the coupler used in the invention contains less unwanted blue absorption and can therefore help counteract the undesirable impact of the magnetic layer. Also, if a yellow colored magenta mask is employed, the amount of the mask may be diminished. On the other hand, if all or a portion of the blue absorption can be tolerated, considering the reduction achieved by the invention, then additional amounts of photographically useful groups which generate dye with blue absorbance, such as development inhibitors, can be added to improve sharpness, color and other important photographic properties.
  • the coupler is incorporated in a silver halide emulsion and the emulsion coated on a support to form part of a photographic element.
  • the coupler can be incorporated at a location adjacent to the silver halide emulsion where, during development, the coupler will be in reactive association with development products such as oxidized color developing agent.
  • the term "associated therewith" signifies that the coupler is in the silver halide emulsion layer or in an adjacent location where, during processing, the coupler is capable of reacting with silver halide development products.
  • the photographic elements can be single color elements or multicolor elements.
  • Multicolor 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.
  • the emulsions sensitive to each of the three primary regions of the spectrum can be disposed as a single segmented layer.
  • a typical multicolor photographic element comprises a support bearing a cyan dye image-forming unit comprised of at least one red-sensitive silver halide emulsion layer having associated therewith at least one cyan dye-forming coupler, a magenta dye image-forming unit comprising at least one green-sensitive silver halide emulsion layer having associated therewith at least one magenta dye-forming coupler, and a yellow dye image-forming unit comprising at least one blue-sensitive silver halide emulsion layer having associated therewith at least one yellow dye-forming coupler, at least one of the couplers in the element being a coupler used in this invention.
  • the element can contain additional layers, such as filter layers, interlayers, overcoat layers, subbing layers, and the like.
  • the silver halide emulsions employed in the elements used in 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 IV. Color materials and development modifiers are described in Sections V and XXI.Vehicles are described in Section IX, and various additives such as brighteners, antifoggants, stabilizers, light absorbing and scattering materials, hardeners, coating aids, plasticizers, lubricants and matting agents are described , for example, in Sections V, VI, VIII, X, XI, XII, and XVI. Manufacturing methods are described in Sections XIV and XV, other layers and supports in Sections XIII and XVII, processing methods and agents in Sections XIX and XX, and exposure alternatives in Section XVIII.
  • Preferred color developing agents are p-phenylene diamines. Especially preferred are:
  • negative working silver halide a negative image can be formed.
  • positive (or reversal) image can be formed.
  • magenta coupler described herein may be used in combination with other classes of magenta image couplers such as 3-acylamino-5-pyrazolones and heterocyclic couplers (e.g. pyrazoloazoles) such as those described in EP 285,274; U.S. Patent 4,540,654; EP 119,860, or with other 5-pyrazolone couplers containing different ballasts or coupling-off groups such as those described in U.S. Patent 4,301,235; U.S. Patent 4,853,319 and U.S. Patent 4,351,897.
  • the coupler may also be used in association with yellow or cyan colored couplers (e.g.
  • masking couplers such as 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.
  • the masking couplers may be shifted or blocked.
  • the coupler may also 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 (UK Patent 2,097,140; U.K. Patent 2,131,188); electron transfer agents (U.S. 4,859,578; U.S.
  • antifogging and anti color-mixing agents such as derivatives of hydroquinones, aminophenols, amines, Gallic acid; catechol; ascorbic acid; hydrozides; sulfonamidophenols; and non color-forming couplers.
  • the couplers may also be used in combination with filter dye layers comprising colloidal silver sol or yellow and/or magenta filter dyes, either as oil-in-water 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 be blocked or coated in protected form as described, for example, in Japanese Application 61/258,249 or U.S. 5,019,492.
  • the coupler may further be used in combination with image-modifying compounds such as "Developer Inhibitor-Releasing” compounds (DIR's).
  • DIR's useful in conjunction with the couplers used in the invention are known in the art and examples are described in U.S. Patent Nos.
  • DIR Couplers for Color Photography
  • C.R. Barr J.R. Thirtle and P.W. Vittum in Photographic Science and Engineering , Vol. 13, p. 174 (1969).
  • the developer inhibitor-releasing (DIR) couplers include a coupler moiety and an inhibitor coupling-off moiety (IN).
  • the inhibitor-releasing 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.
  • inhibitor moieties are: oxazoles, thiazoles, diazoles, triazoles, oxadiazoles, thiadiazoles, oxathiazoles, thiatriazoles, benzotriazoles, tetrazoles, benzimidazoles, indazoles, isoindazoles, mercaptotetrazoles, selenotetrazoles, mercaptobenzothiazoles, selenobenzothiazoles, mercaptobenzoxazoles, selenobenzoxazoles, mercaptobenzimidazoles.
  • the inhibitor moiety or group is selected from the following formulas: wherein R I is selected from the group consisting of straight and branched alkyls of from 1 to about 8 carbon atoms, benzyl and phenyl groups and said groups containing at least one alkoxy substituent; R II is selected from R I and -SR I ; R III is a straight or branched alkyl group of from 1 to about 5 carbon atoms and m is from 1 to 3; and R IV is selected from the group consisting of hydrogen, halogens and alkoxy, phenyl and carbonamido groups, -COOR V and -NHCOOR V wherein R V is selected from substituted and unsubstituted alkyl and aryl groups.
  • the coupler moiety included in the developer inhibitor-releasing coupler forms an image dye corresponding to the layer in which it is located, it may also form a different color as one associated with a different film layer. It may also be useful that the coupler moiety included in the developer inhibitor-releasing coupler forms colorless products and/or products that wash out of the photographic material during processing (so-called "universal" couplers).
  • the developer inhibitor-releasing coupler may include a timing group which produces the time-delayed release of the inhibitor group such as groups utilizing the cleavage reaction of a hemiacetal (U.S. 4,146,396, Japanese Applications 60-249148; 60-249149); groups using an intramolecular nucleophilic substitution reaction (U.S. 4,248,962); groups utilizing an electron transfer reaction along a conjugated system (U.S. 4,409,323; 4,421,845; Japanese Applications 57-188035; 58-98728; 58-209736; 58-209738) groups utilizing ester hydrolysis (German Patent Application (OLS) No.
  • a timing group which produces the time-delayed release of the inhibitor group such as groups utilizing the cleavage reaction of a hemiacetal (U.S. 4,146,396, Japanese Applications 60-249148; 60-249149); groups using an intramolecular nucleophilic substitution reaction (U.S. 4,248,962); groups utilizing an electron
  • timing group or moiety is of one of the formulas: wherein IN is the inhibitor moiety, Z is selected from the group consisting of nitro, cyano, alkylsulfonyl; sulfamoyl (-SO 2 NR 2 ); and sulfonamido (-NRSO 2 R) groups; n is 0 or 1; and R VI is selected from the group consisting of substituted and unsubstituted alkyl and phenyl groups.
  • the oxygen atom of each timing group is bonded to the coupling-off position of the respective coupler moiety of the DIAR.
  • Suitable developer inhibitor-releasing couplers for use in the present invention include, but are not limited to, the following:
  • Photographic Materials of the invention may be coated on pH adjusted support as described in U.S. 4,917,994; with epoxy solvents (EP 0 164 961); with nickel complex stabilizers (U.S. 4,346,165; U.S. 4,540,653 and U.S. 4,906,559 for example); with ballasted chelating agents such as those in U.S.
  • the coupler compositions used in this invention may be coated on a transparent support or a reflective support, such as a paper support, and may be used in color negative, reversal or color print materials.
  • coupler solvent S1 utilized in many of these examples refers to mixed tritolyl phosphates. Structures of couplers B1-B9 used as comparative examples are shown below.
  • the resulting oil was purified by column chromatography using silica gel and a 1:3 mixture of ethyl acetate and petroleum ether (60-80) as the eluting solvent.
  • the oil (6.2 g) that was obtained was dissolved in 25 mL of acetic acid, and the solution was added to 600 mL of vigorously-stirred water.
  • the white solid which precipitated was filtered off, washed with water and dried in a vacuum oven.
  • NMR and IP spectra and elemental analyses of the product were all consistent with the desired product M4.
  • the yield was 5.8 g (44%). High performance liquid chromatography indicated a purity of >97%.
  • Dispersions of the comparative couplers B1-B3 and B8 and of the couplers used in this invention M1-M3 were prepared by dissolving the coupler in the coupler solvent S1 plus the auxiliary solvent 2-(2-butoxyethoxy)ethyl acetate and then dispersing this oil phase in an aqueous solution of gelatin and surfactant using an ultrasonic probe.
  • the dispersions were chilled and washed for 6 hr at 4C to remove the auxiliary solvent.
  • the dispersions contained approximately 8.8% coupler, 4.4% S1 and 6% gelatin by weight.
  • the dispersions were coated at 1.04 mmole/sq m together with a silver bromoiodide emulsion on a transparent acetate support in the format shown below.
  • Hardened film strips were exposed through a 0-4 neutral density stepwedge and daylight V and WRATTEN 9 filters and subjected to a standard C-41 process at 37.8C.
  • the process consists of 2.5 min in color developer, 4 min in a ferric EDTA/PDTA bleach solution, 2 min wash, 4 min fix and 2 min final wash.
  • Photographic gamma values were obtained from the slopes of plots of status M green density vs. exposure for processed samples.
  • Table I lists ⁇ max values and gamma values for comparative couplers B1-B3 and B8 and for the couplers used in this invention M1-M3. This series illustrates the effects of varying the substituent of the 1-phenyl ring (i.e. R1) on dye hue.
  • Table I Coupler ⁇ max(nm) (+-0.5) Gamma B1 (comparative) 539.5 4.8 B2 " 542.0 5.3 B3 " 546.0 4.7 B8 " 555.0 2.3 M1 (invention) 550.5 4.6 M2 " 551.5 3.9 M3 " 551.0 4.4
  • the maximum effective green sensitivity of commercial color papers is typically near 550 nm (see Fig. 2). It is desirable that the ⁇ max of the magenta dye(s) in the green record(s) of a color negative film designed for printing onto these color papers be close to this same value of 550 nm. Even a para chloro 1-phenyl substituent, as in B3, is not sufficiently electron-withdrawing to result in a dye with a ⁇ max suitably close to 550 nm.
  • couplers M1-M3 possess different coupling-off groups (Q), the absorption spectra of the three films are similar, which illustrates that the couplers used in this invention can provide improved dye spectral absorption characteristics for a variety of coupling-off groups.
  • the coupler M1 used in this invention also yields a desirable high gamma value, which is comparable to those of the comparative couplers B1-B3 with the same coupling-off group.
  • the four-equivalent coupler B8 is used commercially. From the comparative data in Table II it is evident that couplers M1-M3 used in this invention all give gamma values which are higher than that obtained with the commercial magenta dye forming coupler B8. Thus M1-M3 offer activity and efficiency advantages over B8 which had not been anticipated.
  • the developing agent 4-amino-3-methyl-N-ethyl-N-methanesulfonamidoethyl aniline, commonly used in color paper processes (such as the KODAK EKTACOLOR® RA process) yields dyes that are even more hypsochromic than the dyes formed from the C-41 process.
  • the couplers used in this invention are particularly useful in color paper materials for obtaining more bathochromic dyes with the proper visual hues.
  • two-equivalent couplers in principle, require reduction of only two atoms of silver to produce one molecule of dye, they can be much more efficient in forming dye images than four-equivalent couplers.
  • many two-equivalent couplers are inefficient in forming dye images due to poor reactivity with oxidized developer or due to their tendency to undergo side reactions, which do not form dye.
  • Chloro or other coupling-off groups have been used for many classes of couplers.
  • pyrazolone couplers with halogen substituents in the 4-position are not useful because of their tendency to undergo side reactions.
  • Dispersions of couplers B3, M1 and M5 with S1 (1:0.5) were prepared and coated as in Example 2. Film strips of these coatings were exposed, processed and analyzed as in Example 2. ⁇ max values and gamma values associated with these film compositions are listed in Table III. This series further illustrates the use of electron-withdrawing substituents to obtain magenta dyes of the proper hue. Again the couplers M1 and M5 used in this invention with at least two strongly electron-withdrawing substituents (sulfamoyl and cyano) at R1 and at R2 yield suitably bathochromic ⁇ max values, whereas B3 with a chloro substituent at R1 does not. Table III Coupler ⁇ max(nm) (+ -0.5) Gamma B3 (comparative) 546.5 4.5 M1(invention) 551.0 4.4 M5 " 552.0 3.8
  • Couplers B4 and M6-M8 have a strongly electron-withdrawing alkoxycarbonyl substituent in the R2 position and couplers B5 and M9-M11 have a strongly electron-withdrawing alkylsulfonyl group at R2.
  • B4 and B5 which have weaker electron-withdrawing chloro groups at R1, do not yield sufficiently bathochromic dyes.
  • the gamma values obtained with the couplers used in this invention are suitably high to be useful in photographic materials, as indicated by comparison to the gamma obtained from the commercial coupler B8.
  • couplers which yield more bathochromic dyes are desirable not only to maximize absorption in the region of 550 nm but also to minimize unwanted blue light absorption. Often, the effective blue light sensitivity of color paper maximizes in the vicinity of 480 nm. (See Fig. 2 of W.C. Kress and P.J. Alessi, J.
  • Dispersions of the comparison couplers B6 and B7, and of the couplers used in this invention M12-M17 were prepared using the coupler solvent S1 as in Example 2. These were coated as in Example 2, and hardened film strips were exposed, processed and analyzed as in Example 2. The results obtained are summarized in Table V.
  • all of the couplers have sulfamoyl or alkylsulfonyl substituents in the R1 position and the R2 substituent on the 3-anilino ring is varied.
  • Comparative couplers B6 and B7 have chloro substituents at R2, whereas M12-M17 used in this invention have strong electron withdrawing R2 groups.
  • Dispersions of the coupler B3 were prepared with coupler solvents S1 and C2, both at a 1:1 B3:coupler solvent weight ratio.
  • Dispersions of coupler M1 were prepared with C2 at 1:1 and with C2 plus aniline A1 at a 1:0.8:0.2 M1:C2:A1 weight ratio. These dispersions were prepared by dissolving the coupler in a mixture of coupler solvent, aniline Al (optional) and cyclohexanone. The coupler:cyclohexanone weight ratio was 1:3. This mixture was then added to an aqueous solution of gelatin and ALKANOL XC surfactant.
  • the two-phase mixture was then passed through a colloid mill to disperse the coupler-containing oil phase in the aqueous phase in the form of small droplets.
  • the dispersion was then chilled, noodled and washed to remove the auxiliary cyclohexanone solvent.
  • the resulting dispersions contained approximately 2% by weight of coupler and 6% by weight of gelatin.
  • the dispersions were then coated on a transparent support together with a silver bromoiodide emulsion in the format shown below. Coatings were then exposed through a stepwedge and subjected to variants of the KODAK FLEXICOLOR (C-41) process described below.
  • One set of film samples was processed with an acetic acid stop bath between the development and bleach steps (process A).
  • a second set of films was processed without a stop bath and with the bleach pH adjusted to 6.0 instead of the normal 5.25 (process B). This is intended to simulate behavior in a "seasoned” bleach whose pH increases due to carry-over of base from the developer solution.
  • Aniline or amine addenda such as A1 can be added to coupler compositions used in this invention to further reduce continued coupling, while maintaining a desirable dye hue and suitable gamma. This is illustrated by data for the combination of M1, C2 and A1, which yields a delta Dmin of only 0.040.
  • the couplers used in this invention can also be used in combination with any type inhibitor releasing couplers (DIRs and DIARs). The above data illustrate that low continued coupling and desirable bathochromic hues are obtained with a composition consisting of M1, C2 and D1. The gamma value is reduced as expected for a properly functioning DIR coupler.
  • This invention provides a photographic material and process for obtaining a magenta image dye of more bathochromic hue.
  • the use of a specified strongly withdrawing parent with a thio coupling off group provides the advantageous results.

Landscapes

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

Claims (25)

  1. Photographisches Material mit einem Träger, auf dem sich mindestens eine photosensitive Silberhalogenidemulsionsschicht befindet, der ein einen purpurroten Farbstoff liefernder Kuppler mit der Formel zugeordnet ist:
    Figure imgb0077
     worin bedeuten:
    (a) mindestens einer der Reste X1, X2 und R1 und mindestens einer der Reste R2 und R3 ist ein Substituent, der individuell ausgewählt ist aus Carbamoyl, Alkoxycarbonyl, Aryloxycarbonyl, Sulfamoyl, Alkylsulfonyl, Arylsulfonyl, Alkoxysulfonyl, Aryloxysulfonyl, Alkylsulfoxyl, Arylsulfoxyl, Acyloxy, Cyano, Nitro und Trifluoromethyl;
    (b) die Substituenten X1, X2, R1, R2 und R3, die nicht aus der Gruppe (a) ausgewählt sind, können ausgewählt sein aus Halogen, Alkyl, Alkoxy, Aryloxy, Acylamino, Alkylthio, Arylthio, Sulfonamido, Alkylureido, Arylureido, Alkoxycarbonylamino und Aryloxycarbonylamino und im Falle von R3 Wasserstoff;
    (c) die Substituenten R1 und R2 befinden sich in para- oder meta-Stellung zu dem Kohlenstoffatom, das an das Stickstoffatom gebunden ist;
    (d) a und b stehen für 1 bis 3;
    (e) Q ist eine abkuppelnde Alkylthio- oder Arylthiogruppe.
  2. Material nach Anspruch 1, in dem X1, X2 und R3 für Halogenatome stehen.
  3. Material nach Anspruch 1, in dem R1 sich in para-Stellung befindet.
  4. Material nach Anspruch 1, in dem Q für Arylthio steht.
  5. Material nach Anspruch 4, in dem Q eine ortho-substituierte Arylthiogruppe ist.
  6. Material nach Anspruch 5, in dem Q der Formel entspricht:
    Figure imgb0078
     worin R4 und R5 ausgewählt sind aus Alkyl, Alkoxy, Aryloxy, Carbonamido, Ureido, Carbamat, Sulfonamido, Carbamoyl, Sulfamoyl, Acyloxy, Alkoxycarbamoyl, Aryloxycarbamoyl, Amin, Halogen, Wasserstoff und Carboxyl; und worin
    q = 0, 1 oder 2 ist.
  7. Material nach Anspruch 6, in dem die Anzahl von Kohlenstoffatomen in R4 und R5 zusammen mindestens 4 beträgt.
  8. Material nach Anspruch 7, in dem der kombinierte pi-Wert der Thioring-Substituenten R4 und R5 mindestens 2,5 beträgt.
  9. Material nach Anspruch 6, in dem R4 und R5 ausgewählt sind aus Carbonamido und Alkyl.
  10. Material nach Anspruch 9, in dem R4 steht für Alkylcarbonamido.
  11. Material nach Anspruch 9, in dem R5 steht für Alkylcarbonamido.
  12. Material nach Anspruch 9, in dem sowohl R4 als auch R5 für Alkyl stehen.
  13. Material nach Anspruch 1, in dem mindestens einer der Substituenten X1, X2, R1, R2 oder R3 ausgewählt ist aus der Gruppe bestehend aus Alkylsulfonyl, Alkoxycarbonyl, Sulfamoyl und Carbamoyl, Cyano und Trifluoromethyl.
  14. Material nach Anspruch 1, das zusätzlich ein organisches Kupplerlösungsmittel mit einem Carbonamid, einem Sulfoxid, einem Phenol oder einem Phosphat enthält.
  15. Material nach Anspruch 1, das zusätzlich eine Alkyl- oder Arylaminverbindung enthält.
  16. Material nach Anspruch 1, das zusätzlich eine Schicht mit magnetischen Teilchen enthält.
  17. Material nach Anspruch 16, das zusätzlich einen gelb-farbigen, einen Farbstoff liefernden Maskierungskuppler in einer Menge enthält, die geringer ist als diejenige, die im Falle eines purpurroten Kupplers eines hypsochromeren Farbtones benötigt wird.
  18. Material nach Anspruch 16, das zusätzlich eine photographisch geeignete Gruppe enthält mit einer normalerweise unerwünschten blauen Absorption nach der Entwicklung in einer Menge im Überschuß zu derjenigen, die im Falle eines hypsochromeren Purpurrot-Kupplers verwendet wird.
  19. Verfahren zur Verminderung der unerwünschten Blau-Absorption eines mehrfarbigen photographischen Materials mit einem Träger, auf dem sich eine photosensitive Silberhalogenidemulsionsschicht zur Erzeugung eines purpurroten Farbstoffbildes befindet, wobei das Verfahren umfaßt die Verwendung eines Kupplers der Formel von Anspruch 1 in der Emulsionsschicht, die für die Bildung des purpurroten Farbstoffes verantwortlich ist.
  20. Verfahren nach Anspruch 19, zu dem die zusätzliche Stufe der Verwendung eines reduzierten Gehaltes eines gelb-farbigen Maskierungskupplers im photographischen Material gehört.
  21. Verfahren nach Anspruch 19, bei dem zu dem Verfahren die zusätzliche Stufe der Verwendung eines erhöhten Gehaltes eines Entwicklungsinhibitors gehört, der zu einem Farbstoff mit einer normalerweise unerwünschten Blau-Absorption im photographischen Material führt.
  22. Verfahren zur Verminderung der unerwünschten Blau-Absorption eines mehrfarbigen photographischen Materials mit einem Träger, auf dem sich eine Schicht mit magnetischen Teilchen befindet sowie mindestens eine photosensitive Silberhalogenidemulsionsschicht mit einem bekannten Kuppler für die Erzeugung eines purpurroten Bildfarbstoffes sowie ein gelber maskierender Kuppler, wobei das Verfahren die Verwendung eines Kupplers der Struktur von Anspruch 1 umfaßt.
  23. Verfahren nach Anspruch 22, das die zusätzliche Stufe der Verwendung eines verminderten Gehaltes eines gelb-farbigen Maskierungskupplers in dem photographischen Material umfaßt.
  24. Verfahren nach Anspruch 22, das die zusätzliche Stufe der Verwendung eines Entwicklungsinhibitors umfaßt, der zu einem Farbstoff mit einer normalerweise unerwünschten Blau-Absorption im photographischen Material führt, wodurch die Schärfe und die Farbe verbessert und die unerwünschte Blau-Absorption beibehalten wird bei oder unterhalb dem ursprünglichen Niveau.
  25. Verfahren zur Herstellung eines Farbstoffbildes in einem exponierten Element gemäß Anspruch 1, das die Entwicklung des exponierten photographischen Elementes mit einer Farbentwicklerverbindung umfaßt.
EP92914038A 1991-07-17 1992-04-23 Magenta bildfarbstoff-kuppler mit verbessertem farbton Expired - Lifetime EP0548313B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US73167191A 1991-07-17 1991-07-17
US731671 1991-07-17
PCT/US1992/003393 WO1993002392A1 (en) 1991-07-17 1992-04-23 Magenta image-dye couplers of improved hue

Publications (2)

Publication Number Publication Date
EP0548313A1 EP0548313A1 (de) 1993-06-30
EP0548313B1 true EP0548313B1 (de) 1997-07-16

Family

ID=24940500

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92914038A Expired - Lifetime EP0548313B1 (de) 1991-07-17 1992-04-23 Magenta bildfarbstoff-kuppler mit verbessertem farbton

Country Status (4)

Country Link
EP (1) EP0548313B1 (de)
JP (1) JPH06501786A (de)
DE (1) DE69220905T2 (de)
WO (1) WO1993002392A1 (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5350667A (en) * 1993-06-17 1994-09-27 Eastman Kodak Company Photographic elements containing magenta couplers and process for using same

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2128339B1 (de) * 1971-03-08 1976-01-16 Eastman Kodak Cy Us
GB1530272A (en) * 1975-02-21 1978-10-25 Agfa Gevaert 2-pyrazolin-5-ones and their use as colour couplers for silver halide photography
JPS58105147A (ja) * 1981-12-16 1983-06-22 Fuji Photo Film Co Ltd カラ−写真感光材料
JPS59218445A (ja) * 1983-05-25 1984-12-08 Fuji Photo Film Co Ltd カラ−写真感光材料
DE3628318A1 (de) * 1986-08-21 1988-02-25 Agfa Gevaert Ag Farbfotografisches aufzeichnungsmaterial
DE3816873A1 (de) * 1988-05-18 1989-11-30 Agfa Gevaert Ag Farbfotografisches aufzeichnungsmaterial mit 2-aequivalentpurpurkupplern

Also Published As

Publication number Publication date
DE69220905D1 (de) 1997-08-21
JPH06501786A (ja) 1994-02-24
WO1993002392A1 (en) 1993-02-04
DE69220905T2 (de) 1999-01-21
EP0548313A1 (de) 1993-06-30

Similar Documents

Publication Publication Date Title
EP0536387B1 (de) 3-anilinopyrazolon purpurkuppler und verfahren
US5256528A (en) Magenta image-dye couplers of improved hue
US5262292A (en) Photographic elements containing pyrazolone couplers and process
US6096494A (en) Silver halide photographic element containing improved cyan dye-forming phenolic coupler
EP1014185A1 (de) Photographisches Element, Farbkuppler vom Pyrazoloazol-Typ , Verfahren zu ihrer Herstellung und ein Azomethinfarbstoff
US5376519A (en) Photographic material containing a coupler composition comprising magenta coupler, phenolic solvent, and at least one aniline or amine
EP0548347B1 (de) Photographisches element, 2-aequivalent pyrazolon-kuppler enthaltend, sowie verfahren zu deren anwendung
EP0953870B1 (de) Photographisches Element, das einen Acetamido-DIR-Kuppler enthält
EP0548313B1 (de) Magenta bildfarbstoff-kuppler mit verbessertem farbton
EP0953873B1 (de) Photographisches Element, das Acylacetamid-Gelbkuppler enthält
US6143485A (en) Pyrazolotriazle dye-forming photographic coupler
EP0953872B1 (de) Photographisches Element, das einen verbesserten Acylacetamido-Gelbkuppler enthält
EP0545248B1 (de) Verwendung von heterocyclischen Stickstoff-Zusätzen zur Verminderung einer fortgesetzten Kupplung von purpurrote Farbstoffe erzeugenden Kupplern
US6200741B1 (en) Photographic addenda
US5942381A (en) Photographic element and process employing active, stable benzotriazole-releasing DIR couplers
US6040126A (en) Photographic yellow dye-forming couplers
EP0600561B1 (de) Gelbkuppler mit ionisierbare und/oder auflösbare Aryloxy freisetzbare Gruppen
US5851748A (en) Photographic materials and process comprising a particular acylacetanilide yellow dye-forming coupler
GB2326244A (en) Photographic element containing a combination of a magenta dye-forming DIR coupler and a magenta image dye-forming coupler
EP1205795B1 (de) Photographisches Element mit verbesserter Farbstoffstabilität
US6730465B2 (en) Color photographic element containing a heterocyclic dye-forming coupler
EP1016914B1 (de) Photographisches Element, das einen Pyrazolonkuppler enthält, der eine photographisch nützliche Gruppe freisetzt und Bildherstellungsverfahren, in dem dieser Kuppler verwendet wird
EP0884639A1 (de) Photographisches Element und Verfahren, die aktive, stabile Benzotriazol freisetzende DIR Kuppler verwenden
EP1205796A2 (de) Photographisches Element, Verbindung und diesbezügliches Verfahren
EP1016915A1 (de) Photographisches Element, das einen Pyrazolonkuppler enthält, der eine photographisch nützliche Gruppe freisetzt und Bildherstellungsverfahren, in dem dieser Kuppler verwendet wird

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: 19930315

AK Designated contracting states

Kind code of ref document: A1

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

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

17Q First examination report despatched

Effective date: 19960801

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

RBV Designated contracting states (corrected)

Designated state(s): DE GB

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

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): DE GB

REF Corresponds to:

Ref document number: 69220905

Country of ref document: DE

Date of ref document: 19970821

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: IF02

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

Ref country code: GB

Payment date: 20040312

Year of fee payment: 13

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

Ref country code: DE

Payment date: 20040430

Year of fee payment: 13

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: 20050423

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: 20051101

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

Effective date: 20050423