EP0351397B1 - Utilisation de précondensat polyamide-polyamine-épichlorhydrine comme moyen d'impregnation pour papier - Google Patents
Utilisation de précondensat polyamide-polyamine-épichlorhydrine comme moyen d'impregnation pour papier Download PDFInfo
- Publication number
- EP0351397B1 EP0351397B1 EP19890890186 EP89890186A EP0351397B1 EP 0351397 B1 EP0351397 B1 EP 0351397B1 EP 19890890186 EP19890890186 EP 19890890186 EP 89890186 A EP89890186 A EP 89890186A EP 0351397 B1 EP0351397 B1 EP 0351397B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- paper
- polyamine
- polyamide
- precondensate
- impregnation agent
- 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
Links
- 238000005470 impregnation Methods 0.000 title description 4
- 239000000123 paper Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 238000004381 surface treatment Methods 0.000 claims description 3
- 159000000007 calcium salts Chemical class 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 claims 2
- 229920005610 lignin Polymers 0.000 claims 1
- 229920000768 polyamine Polymers 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 4
- 229920001732 Lignosulfonate Polymers 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920001281 polyalkylene Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- FOGYNLXERPKEGN-UHFFFAOYSA-N 3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfopropyl)phenoxy]propane-1-sulfonic acid Chemical class COC1=CC=CC(CC(CS(O)(=O)=O)OC=2C(=CC(CCCS(O)(=O)=O)=CC=2)OC)=C1O FOGYNLXERPKEGN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229960001124 trientine Drugs 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003141 primary amines Chemical group 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- HIEHAIZHJZLEPQ-UHFFFAOYSA-M sodium;naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HIEHAIZHJZLEPQ-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/18—Paper- or board-based structures for surface covering
- D21H27/20—Flexible structures being applied by the user, e.g. wallpaper
-
- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
- D21H17/55—Polyamides; Polyaminoamides; Polyester-amides
-
- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
- D21H17/28—Starch
-
- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
- D21H17/56—Polyamines; Polyimines; Polyester-imides
Definitions
- the invention relates to the use of a polyamide-polyamine-epichlorohydrin precondensate as an impregnating agent for paper.
- thermosetting resin A curable aqueous solution of a thermosetting resin has become known from US Pat. No. 4,336,835, which has a relatively high solids content and allows improved wet strength of paper to be achieved.
- the solution is prepared by reacting an aliphatic dicarboxylic acid with a polyalkylene polyamine to form a polyamide polyamine, which is then reacted with epichlorohydrin.
- the first reaction is present at a molar ratio between aliphatic dicarboxylic acid and polyalkylene polyamine of 1: 1.0 to 1.2 executed until a viscosity of 50% aqueous solution at 25 ° ° C of polyamide-polyamine 4-10 dyn.s.cm ⁇ 2 (400 to 1000 cP) is reached, and the second reaction, in which epichlorohydrin is used in an amount of 1.6 to 1.7 moles per mole of the polyamide secondary amine, is as long continued until the viscosity of the 15% solution of the resulting product at 25 ° C reaches a value of 0.3 to 1.5 dyn.s.cm ⁇ 2 (30 to 150 cP).
- Adipic acid recommended and as polyalkylene-polyamine triethylene tetramine.
- polyamide-polyamine-epichlorohydrin precondensate the degree of condensation of which is 500 and corresponds to an active content of 12%
- lignosulfonic acid optionally as the calcium salt of sulfonic acid
- Additive to the impregnation liquid for the surface treatment of paper, in particular corrugated raw paper is used.
- the measure according to the invention mentioned above as an additive to the impregnation liquid, it was possible to achieve adequate swelling resistance and an increase in the strength values of the paper, in particular the CMT value (DIN 53143).
- the chlorine component of the pre-condensate does not pose any difficulties with regard to environmental pollution, because chlorine reacts with the calcium contained in the sulfite waste liquor to form CaCl2 and no free chlorine or hydrochloric acid is formed.
- the polyamide-polyamine-epichlorohydrin precondate can be constructed from the basic materials adipic acid, triethylene tetramine and epichlorohydrin so that an average molecular weight of 20,000 with a chlorine content of 16-18%, preferably 17%, a condensation temperature of 180 ° C. and a reaction time of 45 min results.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paper (AREA)
Claims (1)
- Utilisation d'un pré-condensat polyamide-polyamine-épichlorhydrine mélangé à de l'acide sulfonique de lignine, le cas échéant comme sel de calcium d'acide sulfonique, en tant que liquide d'imprégnation pour le traitement de surface du papier, notamment de papier brut de carton ondulé, le degré de condensation du pré-condensat étant de 500 environ.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT180388A AT392809B (de) | 1988-07-12 | 1988-07-12 | Impraegniermittel fuer papier und verfahren zum impraegnieren von papier |
| AT1803/88 | 1988-07-12 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0351397A2 EP0351397A2 (fr) | 1990-01-17 |
| EP0351397A3 EP0351397A3 (fr) | 1991-05-15 |
| EP0351397B1 true EP0351397B1 (fr) | 1993-12-22 |
Family
ID=3521313
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19890890186 Expired - Lifetime EP0351397B1 (fr) | 1988-07-12 | 1989-07-12 | Utilisation de précondensat polyamide-polyamine-épichlorhydrine comme moyen d'impregnation pour papier |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0351397B1 (fr) |
| AT (1) | AT392809B (fr) |
| DE (1) | DE58906478D1 (fr) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8118976B2 (en) | 2007-05-23 | 2012-02-21 | Akzo Nobel N.V. | Process for the production of a cellulosic product |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113690062B (zh) * | 2021-07-28 | 2022-11-18 | 华南理工大学 | 一种MXene/聚吡咯纸基电极材料及其制备方法与应用 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL110447C (fr) * | 1957-09-05 | |||
| GB1301100A (en) * | 1969-04-18 | 1972-12-29 | Unilever Nv | Treatment of paperboard |
| JPS54159496A (en) * | 1978-06-07 | 1979-12-17 | Sumitomo Chem Co Ltd | Preparation of aqueous solution of cationic thermosetting resin |
| US4240935A (en) * | 1978-12-22 | 1980-12-23 | Hercules Incorporated | Ketene dimer paper sizing compositions |
-
1988
- 1988-07-12 AT AT180388A patent/AT392809B/de not_active IP Right Cessation
-
1989
- 1989-07-12 EP EP19890890186 patent/EP0351397B1/fr not_active Expired - Lifetime
- 1989-07-12 DE DE89890186T patent/DE58906478D1/de not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8118976B2 (en) | 2007-05-23 | 2012-02-21 | Akzo Nobel N.V. | Process for the production of a cellulosic product |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0351397A3 (fr) | 1991-05-15 |
| AT392809B (de) | 1991-06-25 |
| ATA180388A (de) | 1990-11-15 |
| EP0351397A2 (fr) | 1990-01-17 |
| DE58906478D1 (de) | 1994-02-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE69233403T2 (de) | Harze auf der Basis von Epihalohydrin mit verringertem Halogengehalt | |
| DE2951507C2 (fr) | ||
| DE2756431C2 (de) | Amidgruppenhaltige Polyamine | |
| DE2434816C3 (de) | Verfahren zur Herstellung von stickstoffhaltigen Kondensationsprodukten und deren Verwendung als Retentionsmittel, Flockungsmittel und Entwässerungsbeschleuniger bei der Papierherstellung | |
| EP0074558B1 (fr) | Procédé pour la fabrication de produits de condensation soluble dans l'eau et contenant de l'azote et leur usage dans la fabrication du papier | |
| DE3032288C2 (fr) | ||
| KR100346559B1 (ko) | 종이의제조방법 | |
| EP0873371A1 (fr) | Procede de production de condensats et de produits d'addition renfermant des groupes amino hydrosolubles, et leur utilisation | |
| DE69210794T2 (de) | Neue kationische Polyaminen als Hilfsmittel für Entwässerung und als Stabilizatore für Kolophonum enthaltende Leimungsmittel | |
| DE1546344B2 (de) | Verfahren zur herstellung von papier | |
| DE1495538A1 (de) | Loesliche Diphenylaetherpolymerisate und Verfahren zu deren Herstellung | |
| EP0351397B1 (fr) | Utilisation de précondensat polyamide-polyamine-épichlorhydrine comme moyen d'impregnation pour papier | |
| DE2544948B2 (de) | Verfahren zur Herstellung von kationischen Leimungsmitteln für Papier | |
| DE2353430A1 (de) | Herstellung und verwendung von wasserloeslichen papiererzeugungshilfsmitteln auf polyaminoamidbasis | |
| DE1570296A1 (de) | Verfahren zur Herstellung wasserloeslicher Derivate von Polyalkyleniminen | |
| DE3413567A1 (de) | Papierhilfsmittel | |
| DE2502172C3 (de) | Anionische Papierleimungsmittel | |
| DE3927812A1 (de) | Kationische harnstoff-formaldehyd-harze, verfahren zu ihrer herstellung und ihre verwendung in der papierindustrie | |
| DE1771243C3 (de) | Verfahren zum Leimen von Papiererzeugnissen in der Masse und durch Oberflächenbehandlung | |
| DE1226409B (de) | Verfahren zur Herstellung von mindestens teilweise aus Chemiefasern bestehenden Papieren | |
| EP0123196B1 (fr) | Procédé pour la préparation de résines d'urée-formaldéhyde cationiques solubles dans l'eau, et leur utilisation pour la fabrication de papier | |
| DE3316179A1 (de) | Verfahren zur masseleimung von papier | |
| DE2821830A1 (de) | Verfahren zur oberflaechenleimung von papier | |
| EP1135427B1 (fr) | Procede pour preparer des polymeres cationiques reticules a teneur reduite en aox | |
| DE1927599C3 (de) | Verfahren zur Herstellung von kationischen Harzen und deren Verwendung als Mittel zur Verbesserung der Trocken- und Naßfestigkeit und der Pigmentretentionseigenschaften von Papier |
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: A2 Designated state(s): BE DE ES FR GB IT NL |
|
| PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
| AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): BE DE ES FR GB IT NL |
|
| RHK1 | Main classification (correction) |
Ipc: D21H 17/55 |
|
| 17P | Request for examination filed |
Effective date: 19910708 |
|
| 17Q | First examination report despatched |
Effective date: 19920706 |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): BE DE ES 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: 19931222 Ref country code: GB Effective date: 19931222 Ref country code: ES Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY Effective date: 19931222 Ref country code: BE Effective date: 19931222 Ref country code: NL Effective date: 19931222 Ref country code: FR Effective date: 19931222 |
|
| REF | Corresponds to: |
Ref document number: 58906478 Country of ref document: DE Date of ref document: 19940203 |
|
| 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 | ||
| GBV | Gb: ep patent (uk) treated as always having been void in accordance with gb section 77(7)/1977 [no translation filed] |
Effective date: 19931222 |
|
| 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 | ||
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Effective date: 19950401 |