EP0386583A1 - Procédé de teinture de matériaux textiles cellulosiques après un blanchiment au peroxyde - Google Patents

Procédé de teinture de matériaux textiles cellulosiques après un blanchiment au peroxyde Download PDF

Info

Publication number
EP0386583A1
EP0386583A1 EP90103745A EP90103745A EP0386583A1 EP 0386583 A1 EP0386583 A1 EP 0386583A1 EP 90103745 A EP90103745 A EP 90103745A EP 90103745 A EP90103745 A EP 90103745A EP 0386583 A1 EP0386583 A1 EP 0386583A1
Authority
EP
European Patent Office
Prior art keywords
acid
dyeing
glyoxal
liquor
mixtures
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
EP90103745A
Other languages
German (de)
English (en)
Other versions
EP0386583B1 (fr
Inventor
Sigismund Dr. Heimann
Michele Dr. Vescia
Rudolf Dr. Krueger
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Publication of EP0386583A1 publication Critical patent/EP0386583A1/fr
Application granted granted Critical
Publication of EP0386583B1 publication Critical patent/EP0386583B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/001—Special chemical aspects of printing textile materials
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
    • D06P1/651—Compounds without nitrogen
    • D06P1/65106—Oxygen-containing compounds
    • D06P1/65112—Compounds containing aldehyde or ketone groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/58—Material containing hydroxyl groups
    • D06P3/60—Natural or regenerated cellulose
    • D06P3/66—Natural or regenerated cellulose using reactive dyes

Definitions

  • the textile goods are usually treated with reducing agents, e.g., after the bleaching process or immediately before dyeing. with sodium sulfite, sodium bisulfite, sodium pyrosulfite or thiourea.
  • reducing agents e.g., after the bleaching process or immediately before dyeing.
  • this method of peroxide removal has the disadvantage that the excess reducing agents must be carefully rinsed out before the fabric is dyed with reactive dyes, because otherwise residues of the reducing agents would destroy or change the reactive dyes.
  • the invention has for its object to provide a method for dyeing bleached textile materials made of cellulose fibers or mixtures of cellulose fibers with synthetic fibers, in which residues of hydrogen peroxide or per-compounds are removed from a previous bleaching process by adding an auxiliary and in which the auxiliary can also be used in excess without adversely affecting the dyeing process.
  • the textile materials consist of cellulose fibers or contain cellulose fibers in a mixture with other fibers. They can be in any processing state, e.g. as flake, card sliver, yarn, skein, fabric or knitted fabric.
  • the cellulose fibers can either be natural or regenerated cellulose, such as cellulose, or polynosic fibers.
  • Synthetic fibers which are present in the textile materials in a mixture with cellulose fibers are, for example, polyester fibers or synthetic polyamide fibers.
  • the textile materials which may contain cellulose fibers mixed with other fibers, are usually pretreated and bleached.
  • Pretreatment is particularly necessary for textile materials that contain raw cotton.
  • the pretreatment generally consists of boiling the textile goods in a liquor containing sodium hydroxide solution, complexing agents and wetting agents. This pretreatment is carried out in order to remove impurities from the raw cotton, which would otherwise be detached from the textile material during the dyeing process and would interfere with the dyeing process.
  • This pretreatment is followed by bleaching of the textile material containing cellulose fibers.
  • the bleaching is also carried out in an aqueous liquor at temperatures up to 100 ° C.
  • the bleaching bath usually contains peroxide stabilizers, sodium hydroxide solution and, as the actual bleaching agent, water peroxide or per-compounds, such as perborate or peracetic acid.
  • the fabric After bleaching, the fabric is rinsed with water and then dyed with reactive dyes in an aqueous liquor.
  • the cellulose fiber material can also be dyed without rinsing or with only one intermediate rinse with reactive dyes directly after the bleaching, if one glyoxal and / or glyoxylic acid is added to the fresh bath according to the invention. It is advantageous to treat the textile material containing cellulose fibers first with the solution of the glyoxal and / or the glyoxylic acid before adding the dyes cold or warm, for example at temperatures up to 50 ° C. of the aqueous liquor.
  • the textile material is then dyed with reactive dyes either in the same bath or in a fresh liquor.
  • the procedure can also be such that the textile material containing bleached cellulose fibers, if appropriate after a single rinse, is introduced directly into a dyeing liquor which contains, as essential components, a reactive dye and 0.05 to 5 g / l glyoxal, glyoxylic acid or mixtures thereof, and in it colors.
  • a loss in color yield and a change in color tone are avoided when dyeing with reactive dyes.
  • the amounts of glyoxal and / or glyoxylic acid to be used depend on the amount of residual peroxides in the textile. In general, 0.05 to 2 g / l glyoxal and / or glyoxylic acid is required for dyeing in a long liquor (liquor ratio 1:10 to 40) and 0.5 to 5 g / l glyoxal and / glyoxylic acid in the pad dyebath for dyeing by the cold residence process (Fleet intake 70-120%). Glyoxal or glyoxylic acid or mixtures thereof can also be added to the dyebath as a constituent of a dyeing aid which contains dispersants, surfactants and / or complexing agents.
  • Suitable dispersants are, for example, homopolymers of acrylic acid, methacrylic acid, maleic acid, copolymers of acrylic acid and methacrylic acid, copolymers of acrylic acid or methacrylic acid and maleic acid, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, C1 to C6 alkyl esters of ethylenically unsaturated C3 to C5 carboxylic acids Itaconic acid, hydrolyzed copolymers of maleic anhydride and styrene, vinyl esters or vinyl ethers or the alkali metal or ammonium salts of the homo- and copolymers mentioned.
  • Homopolymers of maleic acid are also to be understood as meaning hydrolyzed polymers of maleic anhydride which can be obtained, for example, by polymerizing maleic anhydride in aromatic hydrocarbons, such as xylene or toluene, using peroxy esters or customary polymerization initiators, such as tertiary butyl hydroperoxide or ditertiary butyl peroxide.
  • the homopolymers and copolymers or the salts thereof are water-soluble in all cases.
  • the molecular weight of the polymers is 1,000 to 100,000, preferably 50,000 to 80,000.
  • the use of polyacrylic acid or copolymers of acrylic acid and methacrylic acid as a dispersant is particularly preferred. Also suitable as dispersants are condensation products of ⁇ -naphthalenesulfonic acid and formaldehyde.
  • Suitable surfactants are, for example, C12- to C20-alkyl sulfates, C8- to C18-alkylbenzenesulfonates, C3- to C12-alkyl phosphoric acid esters, both mono-, di- or triphosphoric acid esters being suitable, the adducts of 6 to 80 moles of ethylene oxide with 1 mole a C12 to C20 alcohol and sulfuric acid esters of the ethoxylated long-chain alcohols and C8 to C12 sulfosuccinic acid esters.
  • the water-soluble alkoxylation products of these alcohols can be used, which can be obtained by alkoxylation of the alcohols with propylene oxide and ethylene oxide, butylene oxide and ethylene oxide, or ethylene oxide and butylene oxide.
  • the alkylene oxides can be present either in statistical distribution or in blocks.
  • glyoxal and / or glyoxylic acid can also be used in a mixture with complexing agents which are usually used for binding the water hardness in dyeing processes, e.g. Polyphosphates, ethylenediaminetetraacetic acid, nitrilotriacetic acid and the corresponding alkali or ammonium salts of the complexing agents mentioned.
  • complexing agents which are usually used for binding the water hardness in dyeing processes, e.g. Polyphosphates, ethylenediaminetetraacetic acid, nitrilotriacetic acid and the corresponding alkali or ammonium salts of the complexing agents mentioned.
  • Reactive dyes are understood to be those dyes that form a chemical bond with the cellulose during dyeing. They contain, for example, the following reactive anchors: monochlorotriazine, dichlorodiazine, monofluorotriazine, dichloroquinoxaline or vinyl sulfone groups. Reactive dyes are common commercial products. They are described, for example, in the Color Index, 3rd edition, volume 3, pages 3391 to 3560 (1971). Staining with reactive dyes is usually carried out at temperatures from 30 to 90 ° C. Following the dyeing, the dyed textile material is usually rinsed with water and soaped with a wetting agent-containing liquor and then, if appropriate, rinsed once or more with water.
  • the percentages in the examples are percentages by weight.
  • Raw cotton knitwear was in an aqueous liquor in a liquor ratio of 1:20 with 5 g / l caustic soda, 2 g / l of the tetrasodium salt of ethylenediaminetetraacetic acid and 1 g / l of an adduct of 6 mol ethylene oxide with 1 mol of a C13 / C15 alcohol for 2 hours Boiled to 100 ° C, then rinsed twice with hot and twice with cold water.
  • the textile material was then bleached in an aqueous bleaching bath in a liquor ratio of 1:20 for about 45 minutes at 98 ° C.
  • the bleach bath contained 1 g / l of a commercially available peroxide stabilizer (sodium silicate), 1 g / l caustic soda and 6 ml / l 35% hydrogen peroxide.
  • the aqueous bath was drained off and the bleached cotton knitted fabric was rinsed once with water and then added to a fresh aqueous liquor (liquor ratio 1:20) which contained 0.2 g / l glyoxal.
  • a fresh aqueous liquor (liquor ratio 1:20) which contained 0.2 g / l glyoxal.
  • 1%, based on the weight of the cotton knitwear, of the red reactive dye C.I. 18200, 5 g / l sodium carbonate and 30 / l sodium chloride were added.
  • the textile material was dyed in this liquor at 30 ° C. for 30 minutes and then rinsed and soaped as usual.
  • the raw cotton knitwear described in Example 1 was boiled and bleached according to the instructions given there. After the bleaching bath was drained, the cotton knitwear was rinsed once with cold water, the rinsing bath was then drained and fresh water was let into the dyeing vessel. After this treatment, the liquor still contained 0.1 ml of 35% hydrogen peroxide. 1%, based on the weight of the textile goods, of the red reactive dye C.I. 18200, 5 g / l sodium carbonate and 30 g / l sodium chloride were then added to this bath and the textile goods were dyed at 30 ° C. for 90 minutes. It was then rinsed and soaped, as is usual with reactive dyeings.
  • the red color obtained was significantly lighter than a corresponding color on a textile material which was pretreated with 0.5 g / l sodium bisulfite after the peroxide bleaching and then carefully rinsed hot and cold.
  • the color was also significantly lighter than the corresponding color according to Example 1.
  • a raw cotton knitted fabric pretreated and bleached according to Example 1 was rinsed once with cold water after the bleaching.
  • the knitted fabric was then rinsed once and treated with a fresh liquor in the liquor ratio 1:20, which contained 0.2 g / l glyoxal.
  • After a dwell time of 10 minutes in the fleet they were given 0.5%, based on textile, of the orange reactive dye CI18260, 5 g / l sodium carbonate and 30 g / l sodium chloride to.
  • the textile material was dyed in the specified liquor at 30 ° C. for 90 minutes and then rinsed and soaped. The color yield was significantly better than that of a comparison staining carried out in the absence of glyoxal.
  • Raw cotton knitted fabrics were boiled and bleached according to the instructions given in Example 1 and, after bleaching, rinsed once with cold water.
  • the knitted fabric was then rinsed once and treated with a fresh liquor in the liquor ratio 1:20, which contained 0.2 g / l glyoxal.
  • After a dwell time of 10 minutes in the fleet they were given 0.5%, based on textile goods, of the blue reactive dye CI61205, 5 g / l sodium carbonate and 30 g / l sodium chloride and dyed the cotton knitwear at a temperature of 30 ° C. for 90 minutes. After dyeing, rinsing and soaping took place as usual.
  • the color yield was significantly better than that of a comparative coloration which was obtained without the addition of glyoxal.
  • Example 3 was repeated with the exception that the dyeing of the cotton knitwear was carried out after the treatment with glyoxal with a liquor which 0.5%, based on textile, of the yellow reactive dye CI13245 0.8 g / l sodium hydroxide 5 g / l sodium carbonate and 30 g / l sodium chloride contained.
  • the coloring was carried out at 80 ° C. within 60 minutes.
  • the textile material was then rinsed and soaped. The color yield was significantly better than that of a comparative dyeing in which the treatment of the cotton knitted fabric with glyoxal was not carried out.
  • Example 3 was repeated with the only exception that instead of the blue reactive dye mentioned there, the same amount of the red reactive dye C.I.25810 was used. Here, too, it was found that the color yield was significantly better than with a comparative dyeing in which the textile material was not pretreated with a liquor containing glyoxal.
  • Example 3 was repeated with the only exception that 1%, based on textile material, of the blue reactive dye CI61211 was used instead of the reactive dye used there.
  • the color yield of this dyeing was better than that of a comparative dyeing in which the textile material had not been treated with a liquor containing glyoxal under otherwise identical conditions.
  • a bleached cotton knitwear which still contained peroxide residues, was dyed by the cold residence process, in which the material was padded with the following liquor with a liquor absorption of 80%: 10 g / l of the blue reactive dye CI61205, 2 g / l sodium carbonate, 8 g / l sodium bicarbonate, 50 g / l urea and 1 g / l glyoxal.
  • the padded material was wound up, tightly packed with a polyethylene film and stored for 24 hours at room temperature.
  • the dyeing was then rinsed and soaped as usual.
  • the color yield of this dyeing was significantly better than that of a comparative dyeing, in which dyeing was carried out only in the absence of glyoxal.
  • a cheese bobbin made from alkaline-boiled cotton yarn (Nm34 / 2, weight 750 g) was bleached in a liquor ratio 1:20 in a laboratory dyeing machine according to the following recipe: 6 mm / l hydrogen peroxide 35%, 1 g / l of a commercially available peroxide stabilizer and 1 g / l caustic soda.
  • the bleaching liquor was heated from room temperature to 98 ° C. within 30 minutes and left at 98 ° C. for 45 minutes. Then it was cooled to 60 ° C and drained. The textile material was then rinsed with the same amount of cold water for 10 minutes and the rinsing liquor was then drained off. The apparatus was then refilled with cold water, 1 g / l glyoxal and 1 g / l of a polyacrylic acid of molecular weight 60,000 were added to the bath and the yarn was pretreated therein for 10 minutes at room temperature.
  • the coloring was then carried out at a temperature of 80 ° C. within one hour.
  • the dyed material was then rinsed with fresh water, cold and hot as usual, soaped and rinsed again.
  • the blue color obtained was much darker than a comparison color, which was obtained according to the otherwise identical recipe, however, in the absence of glyoxal.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Coloring (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
EP90103745A 1989-03-03 1990-02-26 Procédé de teinture de matériaux textiles cellulosiques après un blanchiment au peroxyde Expired - Lifetime EP0386583B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3906769A DE3906769A1 (de) 1989-03-03 1989-03-03 Verfahren zum faerben von textilen materialien aus cellulosefasern im anschluss an eine peroxidbleiche
DE3906769 1989-03-03

Publications (2)

Publication Number Publication Date
EP0386583A1 true EP0386583A1 (fr) 1990-09-12
EP0386583B1 EP0386583B1 (fr) 1993-08-25

Family

ID=6375420

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90103745A Expired - Lifetime EP0386583B1 (fr) 1989-03-03 1990-02-26 Procédé de teinture de matériaux textiles cellulosiques après un blanchiment au peroxyde

Country Status (3)

Country Link
EP (1) EP0386583B1 (fr)
DE (2) DE3906769A1 (fr)
ES (1) ES2058636T3 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0581657A1 (fr) * 1992-07-29 1994-02-02 Manufacture De Produits Chimiques Protex Perfectionnement au procédé de teinture par des colorants réactifs avec blanchiment préalable
WO2000065144A1 (fr) * 1999-04-22 2000-11-02 Eurodye S.A. Andre Leclerc & Fils Procede et composition de neutralisation de l'eau oxygenee residuelle dans les bains de blanchiment
WO2007101617A1 (fr) * 2006-03-03 2007-09-13 Küsters Textile GmbH Procede de coloration semi-continue de tissus et de tissus tricotes, ainsi qu'installation pour la mise en oeuvre du procede

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6582478B1 (en) 1998-09-19 2003-06-24 A. Monforts Textilmaschinen Gmbh & Co. Process for preparative and reactive dyeing of cellulose material
ITPC20010016A1 (it) * 2001-05-07 2002-11-07 I T A C S R L Metodo di decoloritura del colore del tessuto di un capo e contemporanea coloritura di tale zona, con un colore diverso.

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE487807A (fr) *
FR1217080A (fr) * 1957-11-22 1960-05-02 Ici Ltd Procédé de coloration de produits textiles

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE487807A (fr) *
FR1217080A (fr) * 1957-11-22 1960-05-02 Ici Ltd Procédé de coloration de produits textiles

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 102, no. 10, März 1985 Columbus, Ohio, USA "Printing compositions and their use for printing fabrics" Seite 64; Spalte 2; ref. no. 80201 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0581657A1 (fr) * 1992-07-29 1994-02-02 Manufacture De Produits Chimiques Protex Perfectionnement au procédé de teinture par des colorants réactifs avec blanchiment préalable
FR2694310A1 (fr) * 1992-07-29 1994-02-04 Protex Manuf Prod Chimiq Perfectionnement au procédé de teinture par des colorants réactifs avec blanchiment préalable.
WO2000065144A1 (fr) * 1999-04-22 2000-11-02 Eurodye S.A. Andre Leclerc & Fils Procede et composition de neutralisation de l'eau oxygenee residuelle dans les bains de blanchiment
WO2007101617A1 (fr) * 2006-03-03 2007-09-13 Küsters Textile GmbH Procede de coloration semi-continue de tissus et de tissus tricotes, ainsi qu'installation pour la mise en oeuvre du procede

Also Published As

Publication number Publication date
EP0386583B1 (fr) 1993-08-25
DE59002416D1 (de) 1993-09-30
DE3906769A1 (de) 1990-09-06
ES2058636T3 (es) 1994-11-01

Similar Documents

Publication Publication Date Title
DE2444823C3 (de) Verfahren zum Färben von Cellulosefasern
EP0207003A1 (fr) Polymère greffé soluble ou dispersible dans l'eau, sa préparation et son utilisation
EP0197001B1 (fr) Mélange d'adjuvants et son utilisation comme adjuvant de teinture ou adjuvant textile
EP0110007B1 (fr) Utilisation de protéines du lait comme produits auxiliaires textiles
DE3000382C2 (fr)
DE2926098C2 (fr)
EP0386583B1 (fr) Procédé de teinture de matériaux textiles cellulosiques après un blanchiment au peroxyde
DE700979C (de) Verfahren zum Entschlichten von Textilwaren
EP0094656B1 (fr) Procédé pour le désencollage et le blanchiment simultanés de matières textiles en fibres cellulosiques
DE2608577B2 (de) Verfahren zur Behandlung von textlien Materialien zur Verbesserung der Färbbarkeit und Bedruckbarkeit dieser Materialien
EP0029804B1 (fr) Procédé d'impression ou de teinture par foulardage de matières textiles en fibres cellulosiques ou en mélanges de ces fibres avec des fibres synthétiques, pâtes d'impression ou bains de foulardage pour la mise en oeuvre du procédé
EP0364752B1 (fr) Procédé de teinture de matières textiles en cellulose
EP0660894B1 (fr) Procede de teinture et d'impression de matieres textiles en fibres de cellulose, en presence de cetones hydroxy alpha
DE69321706T2 (de) Färbeverfahren für keratinmaterialien mit verbesserter erschöpfung der badbestandteile
DE4130484A1 (de) Verfahren zum nachbleichen gefaerbter rohcellulose
DE4418833A1 (de) Verfahren zur Vorbehandlung natürlicher Fasern
DE1469745C3 (de) Verfahren zum Färben von Fasermaterialien, die aus hochpolymeren, linearen Polyestern bestehen oder solche enthalten
EP0121887B1 (fr) Procédé de teinture uniforme de fibres synthétiques
DE4207109C2 (de) Nachbehandlungsmittel für Färbungen und Drucke mit Dispersionsfarbstoffen auf textilen Materialien und Verfahren zum Nachbehandeln
EP0214580A2 (fr) Procédé et produit pour la réoxidation et le savonnage en un seul bain de teintures réalisées avec des colorants de cuve ou des colorants de cuve au soufre
DE4406785A1 (de) Verfahren zum diskontinuierlichen Färben von cellulosehaltigem Textilmaterial mit Indigo nach dem Ausziehverfahren
DE2910583A1 (de) Verwendung feinteiliger wasserunloeslicher alkalialuminiumsilikate als seifhilfsmittel fuer faerbungen und drucke auf textilmaterial
DE4133995A1 (de) Verfahren zum faerben von mischfasern aus cellulosehaltigen fasermaterialien und hydrophoben fasermaterialien
AT154116B (de) Verfahren zum Entschlichten von Textilwaren.
DE1769647C3 (de) Verfahren zum Färben von Textilmaterialien

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: 19900721

AK Designated contracting states

Kind code of ref document: A1

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

17Q First examination report despatched

Effective date: 19920318

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

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

ITF It: translation for a ep patent filed
REF Corresponds to:

Ref document number: 59002416

Country of ref document: DE

Date of ref document: 19930930

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19930917

ET Fr: translation filed
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: ES

Ref legal event code: FG2A

Ref document number: 2058636

Country of ref document: ES

Kind code of ref document: T3

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

Ref country code: FR

Payment date: 19970124

Year of fee payment: 8

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

Ref country code: CH

Payment date: 19970203

Year of fee payment: 8

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

Ref country code: GB

Payment date: 19970217

Year of fee payment: 8

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

Ref country code: ES

Payment date: 19970218

Year of fee payment: 8

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

Ref country code: DE

Payment date: 19970225

Year of fee payment: 8

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 THE APPLICANT RENOUNCES

Effective date: 19971218

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: 19980226

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

Ref country code: ES

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

Effective date: 19980227

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

Ref country code: LI

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

Effective date: 19980228

Ref country code: FR

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

Effective date: 19980228

Ref country code: CH

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

Effective date: 19980228

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

Effective date: 19980226

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20000403

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

Ref country code: IT

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

Effective date: 20050226