[go: up one dir, main page]

EP0510960A1 - Photographisches lichtempfindliches Silberhalogenidmaterial - Google Patents

Photographisches lichtempfindliches Silberhalogenidmaterial Download PDF

Info

Publication number
EP0510960A1
EP0510960A1 EP92303642A EP92303642A EP0510960A1 EP 0510960 A1 EP0510960 A1 EP 0510960A1 EP 92303642 A EP92303642 A EP 92303642A EP 92303642 A EP92303642 A EP 92303642A EP 0510960 A1 EP0510960 A1 EP 0510960A1
Authority
EP
European Patent Office
Prior art keywords
group
represent
hydrogen atom
alkyl group
dye
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
EP92303642A
Other languages
English (en)
French (fr)
Other versions
EP0510960B1 (de
Inventor
Kazuhiro Konica Corporation Murai
Shun Konica Corporation Takada
Yasuhiko Konica Corporation Kawashima
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.)
Konica Minolta Inc
Original Assignee
Konica Minolta Inc
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 Konica Minolta Inc filed Critical Konica Minolta Inc
Publication of EP0510960A1 publication Critical patent/EP0510960A1/de
Application granted granted Critical
Publication of EP0510960B1 publication Critical patent/EP0510960B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
    • G03C1/83—Organic dyestuffs therefor
    • G03C1/832—Methine or polymethine dyes

Definitions

  • the present invention relates to a silver halide photographic light-sensitive material, specifically to a silver halide photographic light-sensitive material which is improved in sharpness and sensitivity, and hardly undergoes fogging when exposed to safe light.
  • a color photographic light-sensitive material (hereinafter often abbreviated as "a color photographic light-sensitive material”) improved in image quality and handling properties.
  • sharpness can be increased by coloring silver halide emulsion layers or other hydrophilic colloidal layers with a dye that absorbs light of specific wavelength, whereby the optical characteristics of a support can be improved and a light-sensitive material can be protected from halation or irradiation.
  • Dyes are employed in a light-sensitive material normally for the following purposes:
  • the spectral sensitivity distribution characteristics of a silver halide emulsion that has been spectrally sensitized and the spectral absorption characteristics of a dye be well-matched. If not, employment of a large amount of a dye will be necessary. Use of a large amount of a dye, however, results in a lowering in sensitivity. If, the spectral sensitivity characteristics of an emulsion and the spectral absorption characteristics of a dye differ considerably, sharpness cannot be improved even when a large amount of a dye is employed.
  • a cyan dye image In the case of a color photographic light-sensitive material for direct appreciation, a cyan dye image must be improved in sharpness to make users feel the photograph has a good image quality.
  • improved cyan dye image sharpness in the negative-to-positive method, it is required that the spectral sensitivity distribution of a red-sensitive emulsion layer of a light-sensitive material for direct appreciation should not differ greatly from the spectral absorption distribution of a cyan dye image of an original.
  • a red-sensitive emulsion layer of a light-sensitive material for direct appreciation is spectrally sensitized such that its spectral sensitivity distribution will culminate within the range of 670 to 720 nm, whereby the spectral sensitivity distribution of a red-sensitive emulsion layer can be prevented from overlapping with the longer wavelength region of the spectral sensitivity distribution of a green-sensitive layer. It is, therefore, preferred that a dye to be contained in a light-sensitive material have an absorption maxima in this wavelength region.
  • Dyes which were found to satisfy the requirement include oxonol dyes (British Patent No. 506,385, U.S. Patent No. 3,247,127, Japanese Patent Examined Publication Nos. 22069/1964 and 13168/1968); styryl dyes (U.S. Patent No. 1,845,404); merocyanine dyes (U.S. Patent No. 2,493,747, British Patent No. 1,542,807); cyanine dyes (U.S. Patent Nos. 2,843,486 and 3,294,539); and anthraquinone dyes (U.S. Patent No. 2,865,752).
  • oxonol dyes Bosh Patent No. 506,385, U.S. Patent No. 3,247,127, Japanese Patent Examined Publication Nos. 22069/1964 and 13168/1968
  • styryl dyes U.S. Patent No. 1,845,404
  • merocyanine dyes U.S. Patent No. 2,49
  • oxonol dyes and anthraquinone dyes have been widely employed in silver halide photographic light-sensitive materials for direct appreciation due to their relatively small negative affects on photographic emulsions.
  • the inventors made extensive studies to find a dye which satisfy all of the requirements, i.e., a dye having spectral absorption distribution characteristics which are well-matched with the spectral sensitivity distribution characteristics of a silver halide emulsion; capable of being bleached completely in a processing liquid and released readily from a light-sensitive material, and hence, unlikely to contaminate a photographic image; producing no adverse effects, such as sensitization and desensitization, on a silver halide emulsion that has been spectrally sensitized; and exhibiting good time stability in a solution or in a light-sensitive material.
  • safe light which has spectral energy distribution characteristics suited to the spectral sensitivity distribution characteristics of the light-sensitive material is normally employed for enhanced working efficiency.
  • a colored filter which has a maximum transmittance at around 590 nm (generally called "a safe light filter”).
  • a light-sensitive material is required to have a higher sensitivity but not to safe light. Having a lower sensitivity to safe light will be referred to as "safe light suitability”.
  • Japanese Patent Publication Open to Public Inspection (hereinafter referred to as "Japanese Patent O.P.I. Publication") No. 20830/1977, U.S. Patent No. 3,746,539 and FDR Patent No. 2,928,184 disclose use of specific oxonol dyes for improved safe light suitability.
  • these oxonol dyes do not fully satisfy the above requirements.
  • these dyes must be employed in a large amount, which results in lowered sensitivity.
  • Another serious problem is that these oxonol dyes tend to sensitize or desensitize a silver halide emulsion.
  • Japanese Patent O.P.I. Publication No. 235046 discloses the use of a specific oxonol dye in combination with other dyes, by which safe light suitability can be improved without adversely affecting a silver halide emulsion.
  • This method is, however, still unsatisfactory in respect of sharpness. In addition, it cannot improve the safe light suitability of a light-sensitive material prepared from an emulsion with a higher silver chloride content, which is suited to rapid processing. In short, this method cannot improve sharpness and safe light suitability without affecting adversely sensitivity.
  • An object of the invention is to provide a silver halide photographic light-sensitive material which is improved in sharpness, sensitivity and safe light suitability.
  • Another object of the invention is to provide a silver halide photographic light-sensitive material which contains a novel dye which does not produce negative effects, such as sensitization, desensitization and fogging, on a silver halide emulsion; exhibits good time stability in a solution or in a light-sensitive material; and is readily released from a light-sensitive material after processing, therefore, arises no fear of contaminating a photographic image.
  • a silver halide photographic light-sensitive material comprising a support and provided thereon at least one light-sensitive silver halide emulsion layer, wherein at least one layer selected from said light-sensitive emulsion layer and other hydrophilic colloidal layers contains at least one dye having an absorption maxima at 630-680 nm (the first dye) and at least one dye having an absorption maxima at 680 to 750 nm (the second dye), as measured when they are present in a gelatin film.
  • the first dye having an absorption maxima at 630-680 nm is preferably a compound represented by any one of Formula I to XI
  • the second dye having an absorption maxima at 680-750 nm is preferably a compound represented by any one of Formula XII to XV. Explanation will be made on these compounds.
  • R1 and R2 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, -CONR5R6, -OR5, -NR5R6, -SR5, -SO2R5, -COR5, -SO2NR5R6, -SOR5 or a cyano group;
  • R3 and R4 each represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group;
  • L1, L2, L3, L4 and L5 each represent a methine group;
  • n1 and n2 each represent 0 or 1; and
  • R5 and R6 each represent a hydrogen atom, an alkyl group, an alkenyl group or a heterocyclic group.
  • R5 and R6 may combine with each other to form a 5- or 6-membered ring.
  • R7 and R8 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, -NR9R10, -N(R9)CONR10R11, -N(R9)COR10 or -N(R9)SO2R10;
  • Z1 and Z2 each represent a group of non-metallic atoms which are necessary to form a 5- or 6-membered ring;
  • L6, L7, L8, L9 and L10 each represent a methine group;
  • n3 and n4 each represent 0 or 1; and
  • R9, R10 and R11 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group or a heterocyclic group.
  • R9 and R10 may combine with each other to form a 5- or 6-membered ring.
  • R10 and R11 each represent an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, -NR16R17, -OR16, -N(R16)COR17, -N(R16)SO2R17, -N(R16)CONR17R18, -COR16, -CONR16R17, -SO2R16, -SO2NR16R17, -COOR16 or a cyano group;
  • R14 and R15 each have the same meaning as R7 or R8;
  • R16, R17 and R18 each have the same meaning as R9, R10 or R11;
  • L11, L12, L13, L14 and L15 each represent a methine group; and
  • n5 and n6 each represent 0 or 1.
  • R19 has the same meaning as R7 or R8;
  • R20 and R21 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group or a heterocyclic group;
  • Z3 and Z4 each represent a group of non-metallic atoms which are necessary to form a 5- or 6-membered ring;
  • L16, L17, L18 and L19 each represent a methine group; and
  • n7 and n8 each represent 0 or 1.
  • R20 and R21 may combine with each other to form a 5- or 6-membered ring.
  • R22 has the same meaning as R1 or R2;
  • R23 has the same meaning as R3 or R4;
  • R24 and R25 each have the same meaning as R9 or R10;
  • R26, R27 and R28 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic group, a cyno group, -COR29, -CONR29R30, -NR29R30, -OR29, -SO2R29, -N(R29)COR30, -N(R29)SO2R30, -N(R29)CONR30R31, -SR29, -COOR29 or -SO2NR29R30;
  • L20, L21 and L22 each represent a methine group; and
  • n9 represents 0 or 1.
  • R24 and R25 may combine with each other to form a 5- or 6-membered ring.
  • R32 has the same meaning as R7 or R8;
  • R33 and R34 each have the same meaning as R9 or R10;
  • R35 and R36 each have the same meaning as R26, R27 or R28;
  • Y2 has the same meaning as Y1;
  • Z5 has the same meaning as Z3;
  • L23 and L24 each represent a methine group;
  • n10 represents 0 or 1;
  • X1 represents a group capable of being dissociated into anions; and
  • n11 represents 0, 1 or 2.
  • R33 and R34 may combine with each other to form a 5- or 6-membered ring wherein R37 and R38 each have the same meaning as R7 or R8; Y3 and Y4 each have the same meaning as Y1; Z6 and Z7 each have the same meaning as Z1 or Z2; L25, L26, L27, L28 and L29 each represent a methine group; n12 and n13 each represent 0 or 1; X2 has the same meaning as X1; and n14 represents 0, 1 or 2.
  • R39, R40, R41, R42, R43 and R44 each have the same meaning as R9 or R10; R45, R46, R47, R48, R49 and R50 each have the same meaning as R26, R27 or R28; X3 has the same meaning as X1; n15 represents 0, 1 or 2; and m represents 0 or 1.
  • R38 and R39 may combine with each other to form a 5-or 6-membered ring. The same can be applied to R40 and R41, and R42 and R43.
  • R51 and R52 each have the same meaning as R7 or R8; Z8 and Z9 each have the same meaning as Z1 or Z2; L30, L31, L32, L33 and L34 each represent a methine group; and n16 and n17 each represent 0 or 1.
  • R53 and R54 each have the same meaning as R7 or R8; Z10 and Z11 each have the same meaning as Z1 or Z2; L35, L36, L37, L38 and L39 each represent a methine group; and n18 and n19 each represent 0 or 1.
  • R55, R56, R57 and R58 each have the same meaning as R7 or R8;
  • X1, X2, X3, X4, X5 and X6 each represent an oxygen atom, a sulfur atom or -NR59R60;
  • R59 and R60 each represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a heterocyclic atom, a hydroxyl group or -OR61;
  • R61 represents an alkyl group or an aryl group; and
  • n20 and n21 each represent 0 or 1.
  • R62 and R63 each have the same meaning as R1 and R2; R64 and R65 each have the same meaning as R3 or R4; L45, L46, L47, L48 and L49 each represent a methine group; and n32 and n33 each represent 1 or 2.
  • R66 and R67 each have the same meaning as R7 or R8; Z12 and Z13 each have the same meaning as Z1 or Z2; L50, L51, L52, L53 and L54 each represent a methine group; and n34 and n35 each represent 1 or 2.
  • R68 and R69 each have the same meaning as R7 or R8;
  • R70 and R71 each have the same meaning as R12 or R13;
  • X7, X8, X9 and X10 each have the same meaning as X1, X2, X3, X4, X5 or X6;
  • L55, L56, L57, L58 and L59 each represent a methine group; and
  • n36 and n37 each represent 1 or 2.
  • R72 and R73 each have the same meaning as R7 or R8;
  • R74, R75, R76, R77, R78, R79, R80 and R81 each have the same meaning as R26, R27 or R28;
  • X11 and X12 each have the same meaning as X1, X2, X3, X4, X5 or X6;
  • L60, L61, L62, L63 orL64 each represent a methine group; and n38 and n39 each represent 0, 1 or 2.
  • alkyl group represented by any one of R1 to R81 examples include methyl, ethyl, propyl, i-propyl, butyl, t-butyl, cyclopentyl and cyclohexyl.
  • These alkyl groups each may be substituted with a hydroxyl group, a cyano group, a sulfo group, a carboxyl group, a halogen atom, an alkoxy group (e.g. methoxy, ethoxy), an aryloxy group (e.g. phenoxy, 4-sulfophenoxy, 2,4-disulfophenoxy), an aryl group (e.g.
  • phenyl 4-sulfophenyl, 2,5-disulfonyl
  • an alkoxycarbonyl e.g. methoxycarbonyl, ethoxycarbonyl
  • an aryloxycarbonyl e.g. phenoxycarbonyl
  • Examples of the aryl group represented by any one of R1 to R81 include phenyl and naphthyl. These aryl groups each may be substituted. Suitable substituents include the alkyl groups represented by any one of R1 to R81 and the groups mentioned above as the substituents for the alkyl group.
  • heterocyclic group represented by any one of R1 to R81 examples include pyridyl, thiazolyl, oxazolyl, imidazolyl, furyl, pyrrolyl, pyrazinyl, pyrizinyl, pyridazinyl, purinyl, selenazolyl, sulforanyl, piperidinyl, pyrazolyl and tetrazolyl. These heterocyclic groups each may be substituted. Suitable substituents include the alkyl groups represented by any one of R1 to R81 and the groups mentioned above as the substituents for the alkyl group.
  • Examples of the alkenyl group represented by any one of R1 to R81 include vinyl, allyl and butenyl. These alkenyl groups may be substituted.
  • Suitable substituents include the alkyl groups represented by any one of R1 to R81 and the groups mentioned above as the substituents for the alkyl group.
  • Examples of the 5- or 6-membered ring formed by any one of Z1 to Z13 include benzene, naphthalene, thiophene, pyrrole, furan, pyrazole, indole, quinoline, pyridine, pyrazine, pyrimidine, cyclohexene and cyclopentene. These rings each may be substituted.
  • Suitable substituents include the alkyl groups represented by any one of R1 to R81 and the groups mentioned above as the substituents for the alkyl group.
  • the methine group represented by any one of L1 to L64 may have a substituent.
  • Suitable substituents include an alkyl group (e.g. methyl, ethyl, i-butyl), an aryl group (e.g. phenyl, p-tolyl, p-carbonxyphenyl), an aralykyl group (e.g. benzyl, phenethyl), alkoxy (e.g. methoxy, ethoxy), an aryloxy group (e.g. phenoxy), a halogen atom and a cyano group.
  • alkyl group e.g. methyl, ethyl, i-butyl
  • an aryl group e.g. phenyl, p-tolyl, p-carbonxyphenyl
  • an aralykyl group e.g. benzyl, phenethyl
  • alkoxy e.g. me
  • the first dye of the invention is characterized in that it has an absorption maxima, as measured when contained in a gelatin film, at 630 to 680 nm, preferably 640 to 670 nm.
  • the second dye of the invention is characterized in that it has an absorption maxima, as measured when contained in a gelatin film, at 680 to 750 nm, preferably 690 to 740 nm.
  • the maximum absorption wavelength of the second dye should be longer than that of the first dye by 20 to 100 nm.
  • the dyes of the invention are contained in a silver halide emulsion layer or in a hydrophilic colloidal layer other than the emulsion layer. Good results can be obtained when these dyes are contained in a layer adjacent to a red-sensitive emulsion layer. If the dyes are diffusible, good results can also be obtained even when they are added to a layer far away from a red-sensitive layer (e.g. an intermediate layer, a protective layer).
  • the amounts of the dyes are not limitative, but preferably 1 to 200 mg/m2 for the first dye, and 3 to 100 mg/m2 for the second dye.
  • the first and second dyes may be added either simultaneously or at an interval. They may be added in the form of two different solutions or dispersions, or in the form of a mixture.
  • the amount ratio of the first dye to the second dye is not limitative, but preferably 1:10 to 5:1.
  • the dyes of the invention are contained in a silver halide emulsion layer or in a hydrophilic colloidal layer other than the emulsion layer by the following method: A dye or its organic or inorganic salt is dissolved in an aqueous solution or an organic solvent (e.g. alcohols, glycols, cellosolves, dimethylformamide, dibutyl phthalate, tricresyl phosphate), and emulsified, if necessary. The resultant is added to a coating composition.
  • an organic solvent e.g. alcohols, glycols, cellosolves, dimethylformamide, dibutyl phthalate, tricresyl phosphate
  • Silver halides usable in the invention include silver iodide, silver iodobromide, silver iodochloride, silver bromide, silver chlorobromide and silver chloride, which have been widely employed in the photographic industry. It is preferable to use silver halide grains having a silver chloride content of 95 mo% or more, a silver bromide content of 5 mol% or less and a silver iodide content of 0.5 mol% or less.
  • a silver halide emulsion layer comprises silver halide grains with a silver chloride content of 95 mol% or more, the amount of such grains accounts for 60 wt% or more, preferably 80 wt% or more, of the total amount of silver halide grains contained therein.
  • the halide composition of a silver halide grain may be uniform within the entire grain.
  • the halide composition may change, either continuously or discontinuously, with the distance from the center of the grain.
  • the size of a silver halide grain is not limitative, but preferably 0.2 to 1.6 ⁇ m, still preferably 0.25 to 1.2 ⁇ m, for the attainment of rapid processing and improved sensitivity.
  • Grain size measurement can be conducted by a known method, such as that described in Labrand: Grain Size Analysis Method (A.S.T.M. Symposium on Light Microscopy, 1955, pp. 94 to 122) or in Mees & James: Theory of Photographic Process (3rd ed., MacMillan Company, 966, Chapter 2).
  • a grain size can be measured by using the area of a projected image of a grain or the approximate value of a grain diameter.
  • An accurate grain size distribution can be obtained based on the project image area or the diameter, as long as grains are in substantially the same shape.
  • the size distribution of silver halide grains to be used in the invention may be either monodispersed or polydispersed.
  • monodispersed silver halide grains having a variation coefficient of 0.22 or less are preferable.
  • Still preferable are monodispersed silver halide grains with a variation coefficient of 0.15 or less.
  • Grain size represents the diameter of a grain when the grain is spherical. In the case of a grain which is cubic or in other shapes, grain size represents the diameter of a circle having the same area as that of the projected image of the grain.
  • Silver halide grains to be employed in the invention can be prepared by any of the neutral method, the acid method or the ammonia method. Use of seed grains is permissible. Formation of seed grains and growing of silver halide grains may be performed by the same method.
  • the shape of a silver halide grain is not limitative. Preferred is a cubic grain having a (100) face as a crystal face. Octahedral, tetradecahedral and dodecahedral silver halide grains may also be employed. Methods of preparing these grains are described in U.S. Patent Nos. 4,183,756, 4,225,666, Japanese Patent O.P.I. Publication No. 26589/1980, Japanese Patent Examined Publication No. 42737/1980 and The Journal of Photographic Science, 21, 39 (1973). Also usable are silver halide grains with a twin crystal face. Silver halide grains may be either identical or different in shape.
  • a metal ion to a silver halide grain during forming and/or growing the grain so that the metal ion can be contained in its inside and/or on its surface.
  • a metal ion can be contained in its inside and/or on its surface.
  • use can be made of cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (or complex salts), rhodium salts (or complex salts) or iron salts (or complex salts).
  • a reduction sensitization nucleous can be formed in the inside and/or on the surface of a grain in a reductive atmosphere.
  • a latent image may be formed in the inside of or on the surface of a silver halide grain.
  • a silver halide emulsion is chemically sensitized by a known method, including the sulfur sensitization method (activated gelatin or a compound containing sulfur which is reactive to a silver ion is used as a sensitizer), the selenium sensitization method, the reduction sensitization method and the noble metal sensitization method. These sensitization methods can be applied either alone or in combination.
  • a silver halide emulsion can be spectrally sensitized to a prescribed wavelength region with a sensitizing dye such as a cyanine dye, a merocyanine dye, a composite cyanine dye, a composite merocyanine dye, a holopolar cyanine dye, a hemicyanine dye, a styryl dye and a hemioxanol dye.
  • a sensitizing dye such as a cyanine dye, a merocyanine dye, a composite cyanine dye, a composite merocyanine dye, a holopolar cyanine dye, a hemicyanine dye, a styryl dye and a hemioxanol dye.
  • a silver halide emulsion for forming a red-sensitive emulsion layer be spectrally sensitized with a sensitizing dye represented by the following Formula RSI or RSII.
  • R1 and R2 each represent an alkyl group or an aryl group
  • L1, L2, L3, L4 and L5 each represent a methine group
  • Y1 and Y2 each represent an oxygen atom, a sulfur atom or a selenium atom
  • R3 and R4 each represent a lower alkyl group
  • A1, A2, B1, B2, C1, C2, D1 and D2 each represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a phenyl group, a cyano group, a nitro group or an alkoxycarbonyl group
  • X+ represents an acid anion
  • n and 1 each represent 0 or 1, provided that 1 is 0 when the compound forms an intramolecular salt
  • sensitizing dyes may be employed either singly or in combination. They also may be used together with a dye which does not have a sensitizing effect or with a supersensitizer consisting of a compound which does not absorb UV rays, which serves to enhance the sensitizing effect of a sensitizing dye.
  • the amount of a sensitizing dye is not limitative, but preferably 1 x 10 ⁇ 7 to 1 x 10 ⁇ 3 mol, still preferably 5 x 10 ⁇ 6 to 5 x 10 ⁇ 4 mol, per mol silver halide.
  • a sensitizing dye may be added by a known method.
  • a sensitizing dye may be added in the form of a solution obtained by dissolving it in a water-soluble solvent such as pyridine, methyl alcohol, ethyl alcohol, methyl cellusolve, acetone or a mixture thereof, and optionally, diluting with water.
  • a water-soluble solvent such as pyridine, methyl alcohol, ethyl alcohol, methyl cellusolve, acetone or a mixture thereof, and optionally, diluting with water.
  • Water may be used instead of a water-solubloe solvent.
  • Use of ultrasonic vibration is advisable to facilitate dissolving.
  • a dye may be added in the form of a dispersion obtained by dissolving it in a volatile organic solvent and dispersing the resulting solution in a hydrophilic colloid.
  • the dye may be added in the form of a dispersion obtained by dispersing it in a water-soluble solvent (see Japanese Patent Examined Publication No. 24185/1971).
  • the sensitizing dyes When two or more sensitizing dyes are employed, it is possible to dissolve them separately in different solvents, and mix the resulting solutions before adding to an emulsion.
  • the dye solutions may be added separately without mixing, in which case the order of addition, timing and interval are determined according to the purpose.
  • a sensitizing dye may be added to a silver halide emulsion at any time during the process of preparing the emulsion, but preferably immediately before, during or immediately after the chemical ripening.
  • the present invention can be applied to both single-colored and multi-colored light-sensitive materials including color negative films, color positive films, color printing paper, light-sensitive materials for display, and the like.
  • the effects of the invention can be produced most satisfactorily when applied to light-sensitive materials for direct appreciation.
  • a dye-forming coupler When the invention is applied to a color photographic light-sensitive material, a dye-forming coupler is normally employed.
  • a silver halide emulsion layer contains a dye-forming coupler which can absorb spectral light to which the emulsion layer is sensitive. Therefore, a yellow dye-forming coupler, a magenta dye-forming coupler and a cyan dye-forming coupler are generally contained in a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer, respectively. Combination of a coupler and an emulsion layer, however, is not limited thereto.
  • acylacetoanilide-based couplers are preferable as a yellow dye-forming coupler.
  • benzoylacetoanilide-based compounds and pivaloylacetoanilide-based compounds in particular, example compound Nos. Y-1 to Y-146 described in Japanese Patent O.P.I. Publication No. 85631/1988, example compound Nos. Y-1 to Y-98 described in Japanese Patent O.P.I. Publication No. 97951/1988, example compound Nos. I-1 to I-50 described in Japanese Patent O.P.I. Publication No. 298943/1990 and example compound Nos. Y-1 to Y-24 described in Japanese Patent O.P.I. Publication No. 156748/1989 are advantageous.
  • magenta dye-forming coupler 5-pyrazolone-based compounds, pyrazoloazole-based compounds and pyrazolobenzimidazole-based compounds can be preferably employed.
  • compound Nos. 1 to 4, 8 to 17, 19 to 24, 26 to 43, 45 to 59, 61 to 104, 106 to 121, 123 to 162, 164 to 233 described from page 18, upper right column to page 32, upper right column of Japanese Patent O.P.I. Publication No. 166339/1987, and compound Nos. M-1 to M-29 described in pages 5 to 6 of Japanese Patent O.P.I. Publication No. 100048/1990.
  • cyan dye-forming coupler naphthol-based compounds and phenol-based compounds are preferable.
  • Examples of a 2,5-diacylaminophenol-based compound include example compound Nos. C-1 to C-25 described in Japanese Patent O.P.I. Publication No. 96656/1988 and examples of a phenol-based compound include example compound Nos. IV-1 to IV-19 described in Japanese Patent O.P.I. Publication No. 196048/1989.
  • phenol-based compounds described in Japanese Patent O.P.I. Publication No. 132437/1990, pages 31 to 32, in each of which a nitrogen-containing heterocyclic ring is condensed to a phenol nucleous, and phenylimidazole-based compounds.
  • a dye-forming coupler is normally added to a hydrophilic colloidal layer in the form of a dispersion obtained by dissolving it in a high-boiling solvent (boiling point: 150°C or more) or a water-insoluble high-molecular substance (if need arises, a low-boiling and/or a water-soluble organic solvent are used in combination), and dispersing the resulting solution in a hydrophilic binder such as an aqueous gelatin solution in the presence of a surfactant.
  • a hydrophilic binder such as an aqueous gelatin solution in the presence of a surfactant.
  • a compound with a dielectric constant (at 30°C) of 6.5 or less such as esters including phosphoric esters, organic acid amides, ketones and hydrocarbons, are preferable. Combined use of two or more different types of high-boiling solvent is possible.
  • a high-boiling solvent is employed in an amount of 0 to 400 wt%, preferably 10 to 100 wt%, based on the amount of a coupler.
  • Gelatin is preferable as a binder.
  • Either lime-treated gelatin or acid-treated gelatin is usable, and there is no restrictions on the raw material (a bone or hide of a cow, a hide of a pig) of gelatin. In the invention, however, it is preferable to use a lime-treated gelatin made from a bone of a cow.
  • Silver halide emulsion layers and other hydrophilic colloidal layers may be hardened by the addition of one or more hardeners.
  • Hardeners serve to allow molecules of a binder (or protective colloid) to be cross-linked, thus making these layers tougher.
  • Hydrophilic colloidal layers such as a protective layer and an intermediate layer may contain a UV absorber, which serves to prevent fogging caused by electric discharge which is generated when a light-sensitive material is electrified by friction, as well as to prevent UV rays from adversely affecting the quality of a photographic image.
  • a UV absorber which serves to prevent fogging caused by electric discharge which is generated when a light-sensitive material is electrified by friction, as well as to prevent UV rays from adversely affecting the quality of a photographic image.
  • a light-sensitive material of the invention may contain auxiliary layers such as a filter layer, an antihalation layer and/or an anti-irradiation layer. These layers and/or silver halide emulsion layers each may contain a dye other than the dye of the invention, which can be released from a light-sensitive material or can be bleached during processing.
  • a light-sensitive material of the invention may contain a fluorescent brightener, such as those described in Japanese Patent O.P.I. Publication No. 71049/1984 and 71050/1984.
  • a fluorescent brightener By the addition of a fluorescent brightener, it is possible to obtain a visually clear photographic image.
  • a fluorescent brightener trapping agent may be added to prevent the brightener from flowing out.
  • hydrophilic polymers such as polyvinyl pyrrolidone, a copolymer containing vinyl pyrrolidone as a repeating unit, a hydrophilic polymer containing a cationic nitrogen-containing active group (described in Japanese Patent O.P.I. Publication No. 42732/1973) and a copolymer of vinyl alcohol and vinyl pyrrolidone (described in Japanese Patent Examined Publication No. 20738/1972).
  • Silver halide emulsion layers and/or other hydrophilic colloidal layers each may contain a matting agent, which serves to make a light-sensitive material less glossy, two improve writability and to prevent a light-sensitive material from adhering to other light-sensitive materials.
  • a light-sensitive material of the invention may contain a lubricant which serves to minimize slide abrasion.
  • a light-sensitive material of the invention may contain an anti-static agent.
  • An anti-static agent may be contained in an anti-static layer provided on the opposite side of a support (where no emulsion layer is provided), or in a silver halide emulsion layer and/or a protective colloidal layer other than an emulsion layer provided on the emulsion layer side of a support.
  • Silver halide emulsion layers and/or other. hydrophilic colloidal layers each may contain a surfactant as a coating aid, an anti-static agent, a lubricant, an emulsifier, and to prevent a light-sensitive material from adhering to other light-sensitive materials, as well as to improve photographic properties (e.g. to accelerate development, to harden the layers of a light-sensitive material, to sensitize emulsions).
  • Silver halide emulsion layers and other component layers of a light-sensitive material of the invention are provided on a variety of supports, in particular, a film of a semisynthetic or synthetic polymer such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate and polyamide, as well as on paper supports, such as those which coated with baryta or a polymer of an ⁇ -olefin (an ⁇ -olefin layer may be one which can be removed readily), flexible reflective supports such as synthetic paper, and a rigid material such as glass, metals and ceramics.
  • An extremely thin reflective support of 120 to 160 ⁇ m in thickness is also usable.
  • a support to be employed in the invention may be either reflective or transparent.
  • a white pigment may be contained in the support, or, a white pigment-containing hydrophilic colloidal layer may be provided on the support.
  • Preferable white pigments include barium sulfate and titanium oxide.
  • a support may be subjected to corona discharge treatment or flame treatment, or exposed to UV rays prior to the provision of layers.
  • an undercoating layer may be formed to increase adhesion between the support and the layers, to prevent a light-sensitive material from getting electrified, as well as to improve the dimensional stability, abrasion resistance, hardness, anti-halation property, frictional characteristics and/or other photographic characteristics of a light-sensitive material. Provision of two or more undercoating layers is possible.
  • conventional color developing agents can be employed.
  • Examples include aminophenol-based compounds and p-phenylenediamine-based compounds. These compounds are normally employed in the form of a salt (e.g. hydrochloride, sulfate), since they are more stable in a salt form than in a free state.
  • the amounts of these compounds are preferably 0.1 to 30 g, still preferably 1 to 15 g, per 1 l of a color developer.
  • the most effective primary aromatic amine-based developing agent is an N,N-dialkyl-p-phenylenediamine-based compound.
  • the alkyl group and the phenyl group each may be substituted with a substituent.
  • a color developer may also contain various known additives, such as an alkalizing agent (e.g. sodium hydroxide, sodium carbonate, potassium carbonate), an alkali metal sulfite, an alkali metal bisulfite, an alkali metal thiocyanate, an alkali metal halide, benzyl alcohol, a water softener and a thickener.
  • an alkalizing agent e.g. sodium hydroxide, sodium carbonate, potassium carbonate
  • an alkali metal sulfite e.g. sodium hydroxide, sodium carbonate, potassium carbonate
  • an alkali metal sulfite e.g. sodium hydroxide, sodium carbonate, potassium carbonate
  • an alkali metal sulfite e.g. sodium hydroxide, sodium carbonate, potassium carbonate
  • an alkali metal sulfite e.g. sodium hydroxide, sodium carbonate, potassium carbonate
  • an alkali metal sulfite e.g.
  • the pH of a color developer is 7 or more, normally 10 to 13.
  • Color developing is performed at 15°C or more, normally 20°C to 50°C. For rapid processing, 30°C or more is preferable. Color developing is performed preferably for 20 to 60 seconds, still preferably 30 to 50 seconds.
  • a light-sensitive material of the invention is subjected to bleaching and fixing after color developing Bleaching may be performed simultaneously with fixing.
  • a stabilizer may contain a pH controller, a chelating agent, a fungicide or other additives.
  • Sample Nos. 1-2 to 1-25 were prepared in substantially the same manner as in the preparation of Sample No. 1-1, except that the type and amount (mg/m2) of dyes contained in the 4th layer were changed to those shown in Table 1.
  • dyes having an absorption maxima at 580 to 630 nm, dyes having an absorption maxima at 630 to 680 nm and dyes having an absorption maxima at 680 to 750 nm are designated as group A, group B and group C, respectively.
  • Coating compositions for the 2nd to 7th layers were prepared in substantially the same manner as in the preparation of the 1st layer coating composition except for ingredients.
  • H-1 and H-2 were added to the 2nd layer coating composition and the 4th layer coating composition, respectively.
  • Surfactants SU-1 and SU-2 were added to each coating composition to adjust the surface tension.
  • the amount of each silver halide emulsion was indicated as the amount of silver contained therein.
  • liquids A and B were added by the double-jet method over a period of 30 minutes, while controlling pAg and pH to 6.5 and 3.0, respectively. Then, liquids C and D were added over a period of 180 minutes, while controlling pAg and pH to 7.3 and 5.5, respectively.
  • pAg was controlled according to the method described in Japanese Patent O.P.I. Publication No. 45437/1983, and pH was controlled by using an aqueous solution of sulfuric acid or sodium hydroxide.
  • EMP-1 was chemically sensitized to an optimum level by using the following compounds, whereby a blue-sensitive silver halide emulsion was obtained (Em-B).
  • An emulsion consisting of monodispersed cubic grains with an average grain size of 0.43 ⁇ m, a variation coefficient of 0.08 and a silver chloride content of 99.5% was prepared in substantially the same manner as in the preparation of EMP-1, except that the addition time of liquids A and B and the addition time of liquids C and D were changed.
  • EMP-2 was then chemically sensitized at 55°C to an optimum level by using the following compounds, whereby a green-sensitive silver halide emulsion (Em-G) was obtained.
  • An emulsion consisting of monodispersed cubic grains with an average grain size of 0.50 ⁇ m, a variation coefficient of 0.08 and a silver chloride content of 99.5% was prepared in substantially the same manner as in the preparation of EMP-1, except that the addition time of liquids A and B and the addition time of liquids C and D were changed, and that the following metallic compounds were added to liquid C.
  • EMP-3 was then chemically sensitized at 60°C to an optimum level by using the following compounds, whereby a red-sensitive silver halide emulsion (Em-R) was obtained.
  • Each of the so-obtained light-sensitive materials was exposed to light in the usual way, and processed according to the following procedure.
  • each light-sensitive material was evaluated for sensitivity, gradation, sharpness, whiteness of background and safe light suitability.
  • Sensitivity and gradation ( ⁇ value) were examined by means of a densitometer (PDA-65, manufactured by Konica Corp.).
  • Each light-sensitive material was subjected to continuous processing using a color printer processor (CL-PP1701QA, manufactured by Konica Corp.).
  • CPK-2-20 manufactured by Konica Corp. was employed as a processing liquid. The processing was continued until the amount of a replenisher exceeded that immediately after the start.
  • the red light reflectance density (D R ) of the non-exposed area was measured by the same method as mentioned above.
  • D R should be 0.02 or less. If it exceeds 0.02, users notice the deteriorated whiteness of the non-exposed area. A D R value exceeding 0.025 makes the photographic image practically unusable.
  • a safe light glass for color printing paper (No. 9B, manufactured by Konica Corp.) was fixed to a tungsten light bulb. The resultant was employed as a light source. Each of the light-sensitive materials was exposed to this safe light through an optical wedge for 20 minutes, followed by the same processing as mentioned above.
  • Safe light sensitivity Reciprocal of the amount of safe light exposure that gives a reflectance density higher than the minimum density by 0.1.
  • Safe light suitability is indicated as a value relative to that of a control sample (set at 0). Smaller rel. SF values represent higher safe light suitability.
  • Sensitivity was indicated as a value relative to that of sample No. 1-4 which was set at 100. Also, safe light suitability was indicated as a value relative to that of sample No. 1-4 which was set at 0.
  • Light-sensitive materials (Sample Nos. 2-1 to 17) were prepared in substantially the same manner as in the preparation of Sample No. 1-1, except that the yellow coupler Y-8, the magenta coupler MC-10 in the 3rd layer and the cyan coupler in the 5th layer were replaced by YC-10, MC-13 and CC-3 (equimolar), respectively, a dye AI-2 was added to the intermediate layer in an amount of 7 mg/m2, the red-sensitive emulsion Em-R in the 5th layer was replaced by those shown in Table 3, and the dye in the 4th layer was changed to those shown in Table 3.
  • liquids A and B were added by the double-jet method over a period of 15 minutes, while controlling pAg and pH to 6.5 and 3.0, respectively.
  • liquids C and D were added also by the double-jet method over a period of 110 minutes, while controlling pAg and pH to 7.5 and 5.5, respectively.
  • EMP-4 was then subjected to chemical ripening to an optimum level at 60°C by using the following compounds, thereby to obtain a red-sensitive silver halide emulsion (Em-R-11).
  • Sensitivity was indicated as a value relative to that of Sample No. 2-9 which was set at 100. Also, safe light suitability was indicated as a value relative to that of Sample No. 2-9 which was set at 0.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP19920303642 1991-04-23 1992-04-23 Photographisches lichtempfindliches Silberhalogenidmaterial Expired - Lifetime EP0510960B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP92176/91 1991-04-23
JP03092176A JP3084454B2 (ja) 1991-04-23 1991-04-23 ハロゲン化銀写真感光材料
JP9217691 1991-04-23

Publications (2)

Publication Number Publication Date
EP0510960A1 true EP0510960A1 (de) 1992-10-28
EP0510960B1 EP0510960B1 (de) 1999-10-20

Family

ID=14047127

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19920303642 Expired - Lifetime EP0510960B1 (de) 1991-04-23 1992-04-23 Photographisches lichtempfindliches Silberhalogenidmaterial

Country Status (3)

Country Link
EP (1) EP0510960B1 (de)
JP (1) JP3084454B2 (de)
DE (1) DE69230157D1 (de)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0563522A1 (de) * 1992-03-31 1993-10-06 Konica Imaging U.S.A., Inc. Farbstoff für eine photographische Filterschicht
EP0697623A1 (de) * 1994-08-17 1996-02-21 Fuji Photo Film Co., Ltd. Photographisches Silberhalogenidmaterial enthaltend einen pyrasolon-pentamethin oxonol Farbstoff
EP0781816A1 (de) * 1995-12-27 1997-07-02 Agfa-Gevaert N.V. Neue Farbstoffe bracubar für verschiedene Anwendungen
US5683860A (en) * 1996-12-18 1997-11-04 Eastman Kodak Company Silver halide light-sensitive element
US6479220B1 (en) 1994-11-22 2002-11-12 Eastman Kodak Company Antihalation/acutance system for photothermographic materials
US8252932B2 (en) * 2000-09-29 2012-08-28 Life Technologies Corporation Modified carbocyanine dyes and their conjugates

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4078933A (en) * 1976-03-16 1978-03-14 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive element containing dye
DE2951789A1 (de) * 1978-12-26 1980-07-17 Fuji Photo Film Co Ltd Fotografische lichtempfindliche materialien mit gefaerbten schichten
US4215030A (en) * 1977-08-31 1980-07-29 Fuji Photo Film Co., Ltd. Photographic polyester film support
US4801525A (en) * 1985-01-29 1989-01-31 Fuji Photo Film Co., Ltd. Infrared sensitized silver halide light-sensitive element with mordant dye over layer
EP0342939A1 (de) * 1988-05-18 1989-11-23 Konica Corporation Photographisches lichtempfindliches Silberhalogenidmaterial
EP0362734A2 (de) * 1988-10-04 1990-04-11 Konica Corporation Photographisches lichtempfindliches Silberhalogenidmaterial

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4078933A (en) * 1976-03-16 1978-03-14 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive element containing dye
US4215030A (en) * 1977-08-31 1980-07-29 Fuji Photo Film Co., Ltd. Photographic polyester film support
DE2951789A1 (de) * 1978-12-26 1980-07-17 Fuji Photo Film Co Ltd Fotografische lichtempfindliche materialien mit gefaerbten schichten
US4801525A (en) * 1985-01-29 1989-01-31 Fuji Photo Film Co., Ltd. Infrared sensitized silver halide light-sensitive element with mordant dye over layer
EP0342939A1 (de) * 1988-05-18 1989-11-23 Konica Corporation Photographisches lichtempfindliches Silberhalogenidmaterial
EP0362734A2 (de) * 1988-10-04 1990-04-11 Konica Corporation Photographisches lichtempfindliches Silberhalogenidmaterial

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 13, no. 185 (P-865)(3533) 2 May 1989 & JP-A-1 013 543 ( KONICA ) 18 January 1989 *
PATENT ABSTRACTS OF JAPAN vol. 14, no. 1 (P-985)(3944) 8 January 1990 & JP-A-1 253 735 ( KONICA ) 11 October 1989 *
PATENT ABSTRACTS OF JAPAN vol. 14, no. 551 (P-1139)(4494) 7 December 1990 & JP-A-2 235 046 ( FUJI ) 18 September 1990 *
PATENT ABSTRACTS OF JAPAN vol. 7, no. 32 (P-174)(1177) 8 February 1983 & JP-A-57 185 038 ( KONISHIROKU ) 15 November 1982 *
PATENT ABSTRACTS OF JAPAN vol. 9, no. 299 (P-408)(2022) 27 November 1985 & JP-A-60 135 936 ( KONISHIROKU ) 19 July 1985 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0563522A1 (de) * 1992-03-31 1993-10-06 Konica Imaging U.S.A., Inc. Farbstoff für eine photographische Filterschicht
EP0697623A1 (de) * 1994-08-17 1996-02-21 Fuji Photo Film Co., Ltd. Photographisches Silberhalogenidmaterial enthaltend einen pyrasolon-pentamethin oxonol Farbstoff
US5563028A (en) * 1994-08-17 1996-10-08 Fuji Photo Film Co., Ltd. Silver halide photographic material containing pyrazolone-pentamethine oxonol dye
US5633390A (en) * 1994-08-17 1997-05-27 Fuji Photo Film Co., Ltd. Silver halide photographic material containing pyrazolone-pentamethine oxonol dye
US6479220B1 (en) 1994-11-22 2002-11-12 Eastman Kodak Company Antihalation/acutance system for photothermographic materials
EP0781816A1 (de) * 1995-12-27 1997-07-02 Agfa-Gevaert N.V. Neue Farbstoffe bracubar für verschiedene Anwendungen
US5683860A (en) * 1996-12-18 1997-11-04 Eastman Kodak Company Silver halide light-sensitive element
US8252932B2 (en) * 2000-09-29 2012-08-28 Life Technologies Corporation Modified carbocyanine dyes and their conjugates
US8614302B2 (en) 2000-09-29 2013-12-24 Life Technologies Corporation Modified carbocyanine dyes and their conjugates

Also Published As

Publication number Publication date
JPH04323646A (ja) 1992-11-12
DE69230157D1 (de) 1999-11-25
JP3084454B2 (ja) 2000-09-04
EP0510960B1 (de) 1999-10-20

Similar Documents

Publication Publication Date Title
US4857446A (en) Filter dye for photographic element
JPH0428095B2 (de)
US5283164A (en) Color film with closely matched acutance between different color records
EP0341958A2 (de) Photographisches Silberhalogenidmaterial
US3833380A (en) Novel photographic elements
EP0683427B1 (de) Heterocyclisch substituierte blausensibilisierende Farbstoffe
EP0510960A1 (de) Photographisches lichtempfindliches Silberhalogenidmaterial
US5126237A (en) Silver halide light-sensitive photographic material
EP0287100B1 (de) Photographisches Silberhalogenidmaterial
EP0286331B1 (de) Photographisches lichtempfindliches Silberhalogenidelement für schnelle Behandlung und Verfahren zur Behandlung dafür
EP0177884B1 (de) Lichtempfindliches photographisches Silberhalogenidmaterial
JPS60221747A (ja) ハロゲン化銀写真感光材料
EP0512496B1 (de) Photographisches Silberhalogenidmaterial
JPS60203936A (ja) ハロゲン化銀写真感光材料
EP0488601A1 (de) Photographisches lichtempfindliches Silberhalogenidmaterial
US5223382A (en) Silver halide photographic material
JPH01145654A (ja) ハロゲン化銀カラー写真感光材料
EP0608017B1 (de) Photographische, grünlichtempfindliche Silberhalogenidelemente
JPH01196033A (ja) ハロゲン化銀写真感光材料
EP0521664A1 (de) Photographisches, lichtempfindliches Silberhalogenidmaterial
US4898809A (en) Silver halide photographic light-sensitive material
JPS5891445A (ja) ハロゲン化銀写真乳剤
US5354651A (en) Hydroxyarylacyl dye compounds and silver halide photographic elements containing such dyes
JP3453714B2 (ja) ハロゲン化銀写真感光材料
JPH01259358A (ja) ハロゲン化銀カラー写真感光材料

Legal Events

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

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE FR GB IT NL

17P Request for examination filed

Effective date: 19930402

17Q First examination report despatched

Effective date: 19970917

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

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 FR GB IT NL

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

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRE;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.SCRIBED TIME-LIMIT

Effective date: 19991020

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19991020

Ref country code: FR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19991020

REF Corresponds to:

Ref document number: 69230157

Country of ref document: DE

Date of ref document: 19991125

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20000121

EN Fr: translation not filed
NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

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

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

Ref country code: GB

Payment date: 20010418

Year of fee payment: 10

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

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: 20020423

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

Effective date: 20020423