EP0501846B1 - Verfahren zur Beschichtung von Papier und Pappe und seine Verwendung zur Herstellung von Papier mit guter Glätte - Google Patents

Verfahren zur Beschichtung von Papier und Pappe und seine Verwendung zur Herstellung von Papier mit guter Glätte Download PDF

Info

Publication number
EP0501846B1
EP0501846B1 EP92400359A EP92400359A EP0501846B1 EP 0501846 B1 EP0501846 B1 EP 0501846B1 EP 92400359 A EP92400359 A EP 92400359A EP 92400359 A EP92400359 A EP 92400359A EP 0501846 B1 EP0501846 B1 EP 0501846B1
Authority
EP
European Patent Office
Prior art keywords
coating
paper
process according
ammonium
polymers
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
EP92400359A
Other languages
English (en)
French (fr)
Other versions
EP0501846A1 (de
Inventor
Claude Trouve
Michel Richard
Jean Cabestany
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.)
Sanofi Aventis France
Original Assignee
Francaise Hoechst Ste
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 Francaise Hoechst Ste filed Critical Francaise Hoechst Ste
Publication of EP0501846A1 publication Critical patent/EP0501846A1/de
Application granted granted Critical
Publication of EP0501846B1 publication Critical patent/EP0501846B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/58—Polymers or oligomers of diolefins, aromatic vinyl monomers or unsaturated acids or derivatives thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/3188—Next to cellulosic
    • Y10T428/31895—Paper or wood

Definitions

  • the present invention relates to a process for coating paper and cardboard and its application to obtaining paper having good smoothness.
  • the present invention also relates to the compositions intended for coating paper containing, as active principle, one of the polymers defined above.
  • compositions are characterized in that they are self-reversible dispersions, the average particle size of which is less than 20 ⁇ m, consisting on the one hand, of an aqueous phase, containing one of the polymers defined above, dispersed in a phase oil, and on the other hand, by at least two emulsifying agents having an overall value of HLB (A definition of HLB is given by WCGRIFFIN in "Classification of surface Active Agents by HLB”]. Soc. Cosmetic Chemists, 1950, page 311 and following) greater than 10, at least one of these emulsifying agents having an HLB value less than 5.
  • the oily phase of the dispersion consists, for example, of one or more hydrophobic hydrocarbons such as hexane, cyclohexane, straight or branched C les-C13 mineral spirits cuts such as paraffinic or paraffinic oils / Commercial naphthenics sold under the name of SHELL white oil, ISOPAR or SOLPAR.
  • hydrophobic hydrocarbons such as hexane, cyclohexane, straight or branched C les-C13 mineral spirits cuts such as paraffinic or paraffinic oils / Commercial naphthenics sold under the name of SHELL white oil, ISOPAR or SOLPAR.
  • the dispersed aqueous phase represents approximately 30 to 75% of the total weight of the emulsion and it contains in solution from 20 to 40% by weight of a polymer defined above.
  • the emulsifying agent with an HLB value of less than 5 is chosen from known emulsifying agents, soluble in oils, such as sorbitan monostearate, monooleate or sesquioleate, and it is contained in the dispersion in proportions of 2 to 8% by weight relative to the total weight of the dispersed aqueous dispersion.
  • the emulsifying agents present in the dispersion must have an overall HLB value greater than 10, it is therefore necessary to use one or more emulsifying agents having an HLB value greater than 10, so as to compensate for the HLB value less than 5 d '. at least one of the emulsifying agents.
  • These emulsifying agents with an HLB value greater than 10 are chosen from known emulsifying agents, soluble in water, such as ethoxylated alkylphenols, sodium dialkylsulfosuccinates, soaps derived from C10-C22 fatty acids.
  • polymers defined above and the aforementioned compositions containing them which would not be known, can be prepared by methods analogous to those described for the preparation of the polymers and the compositions containing them known.
  • the polymers defined above and the aforementioned compositions can be prepared in particular by radical polymerization within a water-in-oil emulsion.
  • This type of polymerization is widely described in the literature, see for example EP-A-0 325 065 and it consists in preparing, in the presence of one or more emulsifiers soluble in oils, a water-in-oil emulsion whose particles have a size less than 20 »m and containing in solution in the dispersed aqueous phase the monomers, then after careful deoxygenation of this emulsion, to carry out the polymerization reaction with an initiation using one or more free radical generators, then finally to cool the dispersion obtained to ambient temperature after having introduced a sufficient quantity of water-soluble surfactant (s) therein, to make it self-reversible.
  • water-soluble surfactant (s) water-soluble surfactant
  • the starting water in oil emulsion is prepared using water in oil emulsifying agents known for this purpose such as monostearate, monooleate, sorbitan sesquioleate. These emulsifying agents must have an HLB value of less than 5 and they are contained in the emulsion in proportions of 2 to 8% by weight relative to the total weight of the aqueous phase.
  • the oily phase of the dispersion consists, for example, of one or more hydrophobic hydrocarbons such as hexane, cyclohexane, straight or branched chain C8-C13 mineral spirits such as commercial paraffinic or paraffinic / naphthenic oils. sold under the name of SHELL white oil, ISOPAR or SOLPAR.
  • the dispersed aqueous phase represents approximately 30 to 75% of the total weight of the emulsion and it contains in solution from 20 to 40% by weight of monomers.
  • the polymerization reaction is initiated by one or more free radical generating agents such as redox couples, azo such as azo-bis acid 4.4 ′ (4-cyano pentanoic).
  • free radical generating agents such as redox couples, azo such as azo-bis acid 4.4 ′ (4-cyano pentanoic).
  • redox couple the couple described in FR-A-2529895 can be used.
  • the polymerization temperature depends on the polymerization initiator chosen and can vary within wide limits, from 5 ° C. to 100 ° C. for example, but in general, the polymerization is carried out at normal pressure at temperatures of 10 to 80 ° C.
  • one or more surfactants whose HLB value is greater than 10 are introduced into the dispersion obtained.
  • These are essentially hydrophilic and water-soluble products such as ethoxylated alkylphenols, sodium dialkylsulfosuccinates, soaps derived from C10-C22 fatty acids.
  • nonylphenols ethoxylated with 6 to 12 moles of ethylene oxide are used.
  • 2 to 8% by weight are incorporated relative to the total weight of the dispersion of several surfactants having an HLB value greater than 10 so that the overall HLB value of the surfactants present in the dispersion is greater to 10.
  • the method according to the invention is particularly advantageous for improving the smoothness of paper supports.
  • the method according to the invention is implemented very simply on a conventional coating device such as, size-press, size-tub, calender sizing, etc., by incorporating into the coating sauce containing the pigments and the binders usual as well as possibly other conventional additives, the necessary quantity of polymer defined above, to obtain the desired smoothness.
  • the polymer is used in the form of the composition defined above.
  • the composition containing the polymer defined above reverses immediately by releasing the polymer swollen with water but insoluble in water into the coating sauce.
  • the use doses expressed in grams of dry polymer relative to the weight of the dry paper medium vary from 0.05 to 0.5%.
  • the improvement in the smoothness of a paper support is in particular a function of the crosslinking rate of the polymer used.
  • a crosslinking rate of less than 0.005 mol% of bisacrylamidoacetic acid there is practically no improvement in the smoothness.
  • a crosslinking rate greater than 0.5 mol% of bisacrylamidoacetic acid no improvement in smoothness is observed.
  • This aqueous solution is then introduced with stirring, at room temperature, into a solution of 226.8 g of white Shell oil 2748 and 21.6 g of sorbitan sesquioleate.
  • the emulsion obtained is then homogenized using a turbine and then it is carefully deoxygenated for one hour by bubbling nitrogen through.
  • the polymerization reaction is then started with stirring, at 10 ° C, by the addition of 0.0136 g of cumene hydroperoxide and 0.024 g of thionyl chloride.
  • the temperature of the reaction medium reaches 80 ° C in 20 minutes. This temperature is maintained for one hour, then it is cooled to 50 ° C.
  • This aqueous solution is then subjected to a water-in-oil emulsion polymerization reaction according to the process described in Example 1. Then, at the end of polymerization, the dispersion obtained is treated as in Example 1. A dispersion is thus obtained, the characteristics of which are given in Table I.
  • column A of Table I the molar concentrations in ppm of bisacrylamidoacetic acid present in the polymer are mentioned.
  • column B are indicated the Brookfield viscosities determined at 20 ° C., with a Brookfield RVT apparatus, at speed 20, of the various dispersions at 1% by weight in water.
  • column C are indicated the Brookfield viscosities determined at 20 ° C., with a Brookfield RVT apparatus at the speed of the various dispersions at 1% by weight in water containing 0.1% by weight of sodium chloride. All viscosities are expressed in Pa.s. All the dispersions have a rate of 30% by weight of active materials and they have excellent stability to sedimentation: no deposit or salting out after one month of storage at 20 ° C.
  • a paper support obtained is treated, either with a chemical pulp B1, or with a mechanical pulp B2, with a coating sauce whose dry matter composition expressed in g is given in Table II, on a MK IV Heliocoater from the Charlestown Engineering Company.
  • the weight of the deposit, as well as the pH and the viscosity of the coating sauce are also mentioned in Table II.
  • the coated paper is then subjected to drying by hot air at 200 ° C. for 20 seconds, then its smoothness is determined with a BEKK measuring device according to French standard NF Q 03-012 of February 1974, and the results are expressed in second. The smoothness is better the longer the time.
  • the weights are expressed in grams and the viscosities, determined on a Brookfield RVT device at 20 ° C, at the speed and with the axis recommended for the value indicated, are expressed in mPa.s.
  • the rheology modifiers of the coating sauce are either the products described in the examples, or carboxymethylcellulose, designated CMC, and sold by the applicant under the reference TYLOSE R VCLL.
  • the binders L1 and L2 are binders commonly used in the coating of paper; the binder L1 is an SBR latex marketed by the company DOW FRANCE under the reference DL 675 SBR and the binder L2 is an acrylic latex marketed by the applicant under the reference MOWILIT DM 595.
  • the pH of the coating sauce is adjusted to the value indicated with 10% sodium hydroxide.
  • the angle of the coating device blade is expressed in degrees.
  • Example 9 gives excellent smoothness
  • Example 8 gives a smoothness slightly lower than that of Example 9
  • Example C1 gives poor smoothness.
  • Examples 8-10 and C1, C2 of comparison show the advantage of the process according to the invention.
  • the method according to the invention allows a significant improvement. smoothness (58 against 46) which represents a savings of 0.75 g / m2 for the same smoothness.
  • Examples 11-14 and C3, C4 and C5 for comparison confirm the advantage of the process according to the invention.
  • the viscosity of the baths using the process according to the invention is higher, but this does not constitute an obstacle to their application on the supports; the deposits obtained are homogeneous and of the same order.
  • the smoothness is better when using the process of the invention.
  • Comparison examples 15-17 and C6 also confirm the advantage of the process according to the invention.
  • Examples 18-21 and C7 for comparison make it possible to highlight the advantage of the process according to the invention: compared with a carboxymethylcellulose, the process according to the invention makes it possible to obtain a smoothness greater by about 40%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)

Claims (6)

  1. Beschichtungsverfahren für Papiere und Pappen, dadurch gekennzeichnet, daß man als Beschichtungsmittel vernetzte, in Wasser unlösliche Polymere verwendet, die in molaren Verhältnissen im polymerisierten Zustand:
    - 50 bis 99,995 % Acrylsäure, von der mindestens 70 % in Form von Ammoniumacrylat vorliegt, und
    - 0,005 bis 0,5 % Bisacrylamidoessigsäure, von der mindestens 70 % in Form von Ammoniumbisacrylamidoacetat vorliegt, enthalten,
    - wobei der an 100 % fehlende Rest Acrylamid enthält.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Polymere in molaren Verhältnissen im polymerisierten Zustand:
    - 65 bis 95 % Acrylsäure, von der mindestens 90 % in Form von Ammoniumacrylat vorliegt, und
    - 0,005 bis 0,5 % Bisacrylamidoessigsäure, von der mindestens 90 % in Form von Ammoniumbisacrylamidoacetat vorliegt, enthalten,
    - wobei der an 100 % fehlende Rest Acrylamid ist.
  3. Verfahren nach einem der Ansprüche 1 und 2, dadurch gekennzeichnet, daß die Polymere in molaren Verhältnissen im polymerisierten Zustand:
    - 70 % mit Ammoniak auf einen pH-Wert von 6,2 eingestellte Acrylsäure, und
    - 0,005 bis 0,5 mit Ammoniak auf einen pH-Wert von 6,2 eingestellte Bisacrylamidoessigsäure enthalten,
    - wobei der an 100 % fehlende Rest Acrylamid enthält.
  4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die verwendeten Polymerein einer autoreversiblen Wasser-in-Öl-Dispersion enthalten sind, wobei die mittlere Teilchengröße weniger als 20 »m beträgt.
  5. Anwendung des Verfahrens nach einem der Ansprüche 1 bis 4 zum Beschichten von Papier und Pappen.
  6. Anwendung des Verfahrens nach Anspruch 5, dadurch gekennzeichnet, daß man, bezogen auf das Gewicht der in der Beschichtungsmasse vorhandenen trockenen Materialien, 0,05 bis 100 Gew.-% der in Anspruch 1 definierten trockenen Polymere verwendet.
EP92400359A 1991-02-25 1992-02-11 Verfahren zur Beschichtung von Papier und Pappe und seine Verwendung zur Herstellung von Papier mit guter Glätte Expired - Lifetime EP0501846B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9102210A FR2673208A1 (fr) 1991-02-25 1991-02-25 Procede d'enduction des papiers et cartons et son application a l'obtention de papier presentant un bon lisse.
FR9102210 1991-02-25

Publications (2)

Publication Number Publication Date
EP0501846A1 EP0501846A1 (de) 1992-09-02
EP0501846B1 true EP0501846B1 (de) 1995-04-26

Family

ID=9410048

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92400359A Expired - Lifetime EP0501846B1 (de) 1991-02-25 1992-02-11 Verfahren zur Beschichtung von Papier und Pappe und seine Verwendung zur Herstellung von Papier mit guter Glätte

Country Status (9)

Country Link
US (1) US5219619A (de)
EP (1) EP0501846B1 (de)
JP (1) JPH05117994A (de)
CA (1) CA2061621A1 (de)
DE (1) DE69202176T2 (de)
ES (1) ES2071444T3 (de)
FI (1) FI117569B (de)
FR (1) FR2673208A1 (de)
NO (1) NO920735L (de)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5266162A (en) * 1990-12-13 1993-11-30 Societe Francaise Hoechst Process for coating papers and its use in flexographic printing
FR2684676A1 (fr) * 1991-12-09 1993-06-11 Hoechst France Nouveaux copolymeres cationiques insolubles dans l'eau, de nouvelles dispersions et leur application dans l'enduction des papiers.
CA2806916C (en) 2012-02-20 2021-04-06 Danco, Inc. Closet collar adaptations
CA2849482C (en) 2013-08-23 2021-05-18 Michael J. Schuster Seals for closet collars
CN104120623B (zh) * 2013-11-28 2017-01-11 海南必凯水性涂料有限公司 一种环保涂布内衬纸及其制造方法
SE544080C2 (en) 2020-05-07 2021-12-14 Stora Enso Oyj Coated paper substrate suitable for metallization

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3872037A (en) * 1970-12-11 1975-03-18 Polysar Ltd Improved carboxylic latex for paper coating utilizing butadiene-styrene-acrylic acid-acrolein tetrapolymers
DE3103463A1 (de) * 1981-02-02 1982-08-26 Basf Ag, 6700 Ludwigshafen Verwendung von emulsionscopolymerisaten auf basis von acrylaten als alleiniges bindemittel fuer papierstreichmassen
DE3277215D1 (en) * 1982-05-03 1987-10-15 Dow Chemical Co Polymeric compositions useful as binders in coating colours and coating colours prepared therefrom
FR2624864B1 (fr) * 1987-12-18 1990-06-01 Hoechst France Dispersions eau dans l'huile de polymeres hydrophiles, a base d'acide acrylique partiellement ou totalement salifie par de l'ammoniac, leur procede de preparation et leur application notamment dans l'impression pigmentaire
US5139614A (en) * 1991-02-06 1992-08-18 American Cyanamid Company Styrene/acrylic-type polymers for use as surface sizing agents

Also Published As

Publication number Publication date
JPH05117994A (ja) 1993-05-14
CA2061621A1 (fr) 1992-08-26
EP0501846A1 (de) 1992-09-02
DE69202176T2 (de) 1995-10-26
US5219619A (en) 1993-06-15
FI920791A0 (fi) 1992-02-24
ES2071444T3 (es) 1995-06-16
DE69202176D1 (de) 1995-06-01
NO920735D0 (no) 1992-02-24
FI920791L (fi) 1992-08-26
FR2673208A1 (fr) 1992-08-28
NO920735L (no) 1992-08-26
FI117569B (fi) 2006-11-30

Similar Documents

Publication Publication Date Title
EP1565504B1 (de) Verwendung eines polymerisats, geppfropftes alkoxy- oder hydroxypolyalkylenglycol enthaltend, als verbesserer beim optischen aufhellen, und die produkte
CA2096083C (fr) Copolymere acrylique partiellement ou totalement hydrosoluble, reticule ou non et son utilisation
CA2097127C (fr) Procede de fabrication d'un papier ou d'un carton a retention amelioree
EP0106763B1 (de) Zusammensetzung und Verfahren zum Streichen von Papier und Pappe, Verfahren zur Herstellung der Zusammensetzung und Papier und Pappe, die auf diese Weise erhalten werden
EP0261039B1 (de) Komplexe Pigmentzusammensetzungen für die Papierbeschichtung
EP2840100B1 (de) NEUE POLYMEISCHE WASSERLÖSLICHE cOMPLEXE UND DEREN VERWENDUNG
EP2078109B1 (de) Verwendung einer Suspension oder wässrigen Dispersion von mineralischen Materialien umfassend ein wasserlösliches Copolymer mit hydrophoben Gruppen zur Herstellung von Papierblättern
EP0892111A1 (de) Wässrige Suspensionen von anorganischen Materialien und ihre Verwendung
EP2780507A1 (de) Streichmassen auf basis von teilweise löslichen dextrinen von hohem molekulargewicht
EP0546879B1 (de) Nicht-wasserlösliche neue kationische Copolymere, neue Dispersionen und deren Verwendung in der Beschichtung von Papier
EP0366569B1 (de) Mischungshilfsmittel für wässrige polypigmente Suspensionen, aus dem ein Pigment hydratiertes Kalziumsulfat ist
EP0068955B1 (de) Beständige Wasser-in-öl dispersionen von Wasserlöslichen kationischen Polymeren von Dimäthylamino Äthylacrylat salzig oder quaternisiert, Verfahren zu deren Herstellung und deren Verwendung als Flockungshilfsmittel
EP0501846B1 (de) Verfahren zur Beschichtung von Papier und Pappe und seine Verwendung zur Herstellung von Papier mit guter Glätte
EP1194454A1 (de) Durch niedrigmolekulare maleimidcopolymere stabilisierte hydrophobe kationische dispersionen für die papierleimung
FR2671352A1 (fr) Nouveaux copolymeres cationiques, de nouvelles emulsions et leur application.
EP1641875B1 (de) Kationische flüssige stärkehaltige zusammensetzung und verwendungen davon
FR2606047A1 (fr) Agent d'encollage du type emulsion de resine
EP1092064B2 (de) Verfahren zur herstellung von papier und pappe
CA2208042C (fr) Collage du papier au moyen de dispersions-latex de copolymeres monomeres hydrophobes / polymeres de type styrene-anhydride maleique a faible masse moleculaire
EP0215044B1 (de) Verfahren zur herstellung eines faserblattes auf papiermacherart
EP2556192B1 (de) Verwendung eines stryrol-latex mit einer partikelgrösse von 100 nm als rheologisches mittel in einer papierbeschichtungszusammensetzung, eine beschichtungszusammensetzung und verfahren zum erzeugen eines beschichteten papiers mit dieser zusamensetzung
FR2560066A1 (fr) Composition stable contenant un anhydride succinique substitue et un emulsionnant et son procede d'utilisation
FR2655875A1 (fr) Agent de dispersion et/ou de broyage pour suspensions aqueuses minerales de potentiel zeta nul.
CA1057872A (fr) Compositions pour couchage de papier
EP0652269A1 (de) Latexharz für Beschichtungszusammensetzung

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): BE CH DE ES GB IT LI NL

17P Request for examination filed

Effective date: 19920922

17Q First examination report despatched

Effective date: 19940810

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

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

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

Effective date: 19950428

REF Corresponds to:

Ref document number: 69202176

Country of ref document: DE

Date of ref document: 19950601

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2071444

Country of ref document: ES

Kind code of ref document: T3

ITF It: translation for a ep patent filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19960205

Year of fee payment: 5

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

Ref country code: ES

Payment date: 19960219

Year of fee payment: 5

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

Ref country code: CH

Payment date: 19960227

Year of fee payment: 5

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

Ref country code: NL

Payment date: 19960229

Year of fee payment: 5

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

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

Ref country code: BE

Payment date: 19960312

Year of fee payment: 5

26N No opposition filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19970211

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: 19970212

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

Ref country code: LI

Effective date: 19970228

Ref country code: CH

Effective date: 19970228

Ref country code: BE

Effective date: 19970228

BERE Be: lapsed

Owner name: SOC. FRANCAISE HOECHST

Effective date: 19970228

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

Ref country code: NL

Effective date: 19970901

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

Effective date: 19970211

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

Effective date: 19970901

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 19990201

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;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.

Effective date: 20050211

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

Ref country code: DE

Payment date: 20060203

Year of fee payment: 15

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: 20070901