WO2004015200A1 - Verfahren zur herstellung von papier, pappe und karton - Google Patents
Verfahren zur herstellung von papier, pappe und karton Download PDFInfo
- Publication number
- WO2004015200A1 WO2004015200A1 PCT/EP2003/008037 EP0308037W WO2004015200A1 WO 2004015200 A1 WO2004015200 A1 WO 2004015200A1 EP 0308037 W EP0308037 W EP 0308037W WO 2004015200 A1 WO2004015200 A1 WO 2004015200A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- paper stock
- microparticle system
- cationic
- paper
- polymers
- Prior art date
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
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
- D21H23/04—Addition to the pulp; After-treatment of added substances in the pulp
- D21H23/06—Controlling the addition
- D21H23/14—Controlling the addition by selecting point of addition or time of contact between components
- D21H23/18—Addition at a location where shear forces are avoided before sheet-forming, e.g. after pulp beating or refining
-
- 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
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
- D21H17/375—Poly(meth)acrylamide
-
- 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
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
- D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
- D21H17/45—Nitrogen-containing groups
- D21H17/455—Nitrogen-containing groups comprising tertiary amine or being at least partially quaternised
-
- 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
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
-
- 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
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/06—Paper forming aids
- D21H21/10—Retention agents or drainage improvers
Definitions
- the invention relates to a process for the production of paper, cardboard and cardboard by shearing the paper stock, adding a microparticle system consisting of a cationic polymer and a finely divided inorganic component to the paper stock after the last shear stage before the headbox, dewatering the paper stock with sheet formation and drying the sheets.
- EP-A-0 223 223 discloses a process for the production of paper and cardboard by dewatering a paper stock, first adding bentonite to a paper stock with a stock concentration of 2.5 to 5% by weight, then diluting the paper stock , a highly cationic polymer with a charge density of at least 4 meq / g is added and finally a high molecular weight polymer based on 'acrylamide is added and the pulp thus obtained is dewatered after mixing.
- an essentially linear synthetic cationic polymer with a molecular weight of more than 500,000 in an amount of more than 0.03 is first metered into an aqueous fibrous suspension wt .-%, based on dry paper stock, then subjecting the mixture to the action of a shear field, wherein the initially formed flakes in micro-, 'flakes are broken, which carry a cationic charge, then do- Siert bentonite and dewatered, the pulp thus obtained without further action from shear forces.
- EP-A-0 335 575 describes a paper production process in which 2 different water-soluble, cationic polymers are added to the pulp, followed by at least one
- EP-A-0 885 328 describes a process for the production of paper, in which a cationic polymer is first metered into an aqueous fiber suspension, and the mixture is then subjected to the action of a shear field. finally an activated bentonite dispersion is added and the pulp thus obtained is dewatered.
- EP-A 0 711 371 Another process for the production of paper is known from EP-A 0 711 371.
- a synthetic, cationic, high molecular polymer is added to a thick cellulose suspension.
- a coagulant consisting of an inorganic coagulant and / or a second, low-molecular and highly cationic water-soluble polymer is added before dewatering.
- EP-A-0 910 701 describes a process for the production of paper and cardboard, wherein the paper pulp is followed in succession by a low-molecular or medium-molecular cationic polymer based on polyethyleneimine or polyvinyla and then with a high-molecular cationic polymer such as polyacrylamide , Polyvinylamine or cationic starch. After this pulp has been subjected to at least one shear stage, it is flocked by adding bentonite and the paper stock is dewatered.
- EP-A-0 608 986 it is known that a cationic retention agent is metered into the thick material in papermaking.
- a further process for the production of paper and cardboard is known from US-A-5, 393, 381, WO-A-99/66130 and WO-A-99/63159, whereby a microparticle system made of a cationic polymer is also used and bentonite are used.
- a water-soluble, branched polyacrylic acid is used as the cationic polymer.
- WO-A-01/34910 describes a process for producing paper in which a polysaccharide or a synthetic, high-molecular polymer is metered into the paper stock suspension. The paper stock must then be sheared mechanically. The reflocculation is carried out by dosing an inorganic component such as silica, bentonite or clay and a water-soluble polymer.
- an inorganic component such as silica, bentonite or clay and a water-soluble polymer.
- the present invention has for its object to provide a further process for the production of paper using a microparticle system, wherein in comparison to the known processes, lower amounts of polymers and bentonite are required, and at the same time improved retention and drainage are obtained and papers are obtained that are less prone to yellowing.
- the object is achieved according to the invention with a process for the production of paper, cardboard and cardboard by shearing the paper stock, adding a microparticle system composed of a cationic polymer and a finely divided inorganic component to the paper stock after the last shear stage before the headbox, dewatering the paper stock below Sheet formation and drying of the sheets if cationic polyacrylamides, polymers containing vinylamine units and / or polydiallyldimethylammonium chloride with an average molecular weight Mw of at least 500,000 daltons and a charge density of at most 4.0 meq./g each are used as cationic polymers of the microparticle system, where the microparticle system used as a retention agent is free of polymers with a charge density of more than 4 meq. / g is.
- All paper qualities can be produced by the method according to the invention, for example cardboard, single / multi-layer folding boxboard, single / multi-layer liner, corrugated material, papers for newspaper printing, so-called medium-fine writing and printing papers, natural gravure papers and lightweight coating base papers.
- To produce such papers one can start from wood pulp, thermomechanical material (TMP), chemo-thermo-mechanical material (CTMP), pressure cut (PGW), wood pulp as well as sulphite and sulphate pulp.
- TMP thermomechanical material
- CTMP chemo-thermo-mechanical material
- PGW pressure cut
- wood pulps can be short-fiber as well as long-fiber.
- Wood-free grades produced by the process according to the invention, which give bright white paper products.
- the papers can optionally contain up to 40% by weight, mostly 5 to 35% by weight, of fillers.
- Suitable fillers are e.g. Titanium dioxide, natural and precipitated chalk, talc, kaolin, satin white, calcium sulfate, barium sulfate, clay or aluminum oxide.
- the microparticle system consists of a cationic polymer and a fine-particle anionic component.
- Cationic polymers include cationic polyacrylamides, polymers containing vinylamine units, polydiallyldimethylammonium chlorides or mixtures thereof, each having an average molecular weight Mw of at least 500,000 Daltons and one
- the polyvinylamines are preferably produced by hydrolysis of homopolymers of vinylformamide, the degree of hydrolysis being, for example, 70 to 95%.
- Cationic polyacrylamides are, for example, copolymers which are obtained by copolymerizing acrylamide and at least one di-C-bisC-alkylamino-C-bisC 4 -alkyl (meth) acrylate or a basic acrylamide in the form of the free bases, the salts with organic or inorganic acids or of the compounds quaternized with alkyl halides are available.
- Examples of such compounds are dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyloacrylate, dimethylaminopropyl methacrylate, dirnethylaminopropyl acrylate, diethylaminopropyl methacrylate, diethylaminopropyl acrylate and / or dimethylaminoethyl acrylamide.
- Further examples of polymers containing cationic polyacrylamides and vinylamine units can be found in the references mentioned in the prior art, such as EP-A-0 910 701 and US-A-6, 103, 065.
- Both linear and branched polyacrylamides can be used. Such polymers are commercially available products. Branched polymers which can be prepared, for example, by copolymerizing acrylamide or methacrylamide with at least one cationic monomer in the presence of small amounts of crosslinking agents are described, for example, in the prior art References US-A-5, 393, 381, WO-A-99/66130 and OA-99/63159 are described.
- Suitable cationic polymers are polydiallylclimethylammonium chlorides (PolyDADMAC) with an average molecular weight of at least 500,000 daltons, preferably at least 1 million daltons. Polymers of this type are commercial products.
- the cationic polymers of the microparticle system are added to the paper stock in an amount of 0.005 to 0.5% by weight, preferably in an amount of 0.01 to 0.2% by weight.
- Bentonite, colloidal silica, silicates and / or calcium carbonate are examples of inorganic components of the microparticle system.
- Colloidal silica is to be understood as meaning products based on silicates, for example silica microgel, silica sol, polysilicates, aluminum silicates, borosilicates, polyborosilicates, clay or zeolite.
- Calcium carbonate can be used, for example, in the form of chalk, calcium carbonate or precipitated calcium carbonate as the inorganic component of the microparticle system.
- Bentonite is generally understood to mean layered silicates which are swellable in water.
- clay mineral montmorrillonite and similar clay minerals such as nontronite, hectorite, saponite, sauconite, beidellite, AIlevard.it, II-lit, halloysite, attapulgite and sepiolite.
- These layered silicates are preferably activated before use, ie converted into a form which is swellable in water, in which the schicrite silicates are treated with an aqueous base, such as aqueous solutions of sodium hydroxide solution, potassium hydroxide solution, soda ash or potash. Bentonite in the form treated with sodium hydroxide solution is preferably used as the inorganic component of the microparticle system.
- the platelet diameter of the bentonite dispersed in water in the form treated with sodium hydroxide solution is, for example, 1 to 2 ⁇ m, the thickness of the platelets is approximately 1 nm.
- the bentonite has a specific surface area of 60 to 800 m 2 / g.
- Typical bentonites are described, for example, in EP-B-0235893.
- bentonite is typically added to the cellulose suspension in the form of an aqueous bentonite slurry. This bentonite slurry can contain up to 10% by weight of bentonite.
- the slurries normally contain approx. 3 - 5% by weight bentonite.
- Aluminum silicates, borosilicates, polyborosilicates or zeolites can be used. These have a specific surface of 50-1000 m 2 / g and an average particle size distribution of 1-250 nm, normally in the range 40-100 nm. The production of such components is described, for example, in EP-A-0041056, EP-A-0185068 and US-A-5176891 ,
- Clay or kaolin is a water-containing aluminum silicate with a platelet structure.
- the crystals have a layer structure and an aspect ratio (diameter to thickness ratio) of up to 30: 1.
- the particle size is at least 50% less than 2 ⁇ m.
- Natural calcium carbonate ground calcium carbonate, GCC
- precipitated calcium carbonate precipitated calcium carbonate, PCC
- GCC is manufactured by grinding and classifying processes using grinding aids. It has a particle size of 40 - 95% less than 2 ⁇ , the specific surface is in the range of 6 - 13 m 2 / g.
- PCC is made by introducing carbon dioxide into calcium hydroxide solution. The average particle size is in the range of 0.03 - 0.6 ⁇ m, the specific surface can be strongly influenced by the choice of the precipitation conditions. It is in the range of 6 - 13 m 2 / g.
- the inorganic component of the microparticle system is added to the paper stock in an amount of 0.01 to 1.0% by weight, preferably in an amount of 0.1 to 0.5% by weight.
- the consistency of the pulp is, for example, 1 to 10 g / 1, preferably 4 to 30 g / 1.
- the aqueous fiber slurry is subjected to at least one shear step. It goes through at least one cleaning, mixing and / or pumping stage.
- the pulp can be sheared, for example, in a pulper, sifter or in a refiner.
- the microparticle system is metered according to the invention.
- a method of operation is particularly preferred in which the cationic polymer and then the inorganic component of the microparticle system are metered into the paper stock which was sheared beforehand.
- the process chemicals usually used in paper production can be added to the paper stock in the usual amounts, for example fixatives, dry and wet strength agents, bulk sizes, biocides and / or dyes.
- First pass retention was determined by determining the ratio of the solids content in the white water to the solids content in the headbox. The information is given in percent.
- FPA retention (first-pass ash retention) was determined in the same way as FP retention, but only the ash content was taken into account.
- a paper stock made from a wood-free, bleached cellulose with a consistency of 7 g / 1 and a filler content of 30% calcium carbonate was processed on a Fourdrinier machine with hybrid former to a paper with writing and printing quality.
- the following arrangement of mixing and shearing devices was used: mixing chest, dilution to 7 g / 1, mixing pump, cleaner, headbox pump, screen and headbox. 32 t of paper were produced per hour.
- the example was repeated with the exceptions that 410 g / t of the cationic polyacrylamide were metered in before the screen and pump and 3000 g / t of bentonite after the screen before the headbox. These amounts were necessary to achieve the same good formation as in the example.
- the FP retention was 79.9% and the FPA retention was 59.1%.
- the saving in polymer was 30% and the saving in bentonite was 17%.
- an improvement in retention could be achieved in the example according to the invention.
- the improvement in sieve dewatering was approx. 10%.
- a wood-containing paper pulp made from pulp and pulp with a consistency of 7 g / 1 and a filler content of 30% of a mixture of clay and calcium carbonate (1: 1) was processed on a paper machine with a gap former to a paper with LWC quality , The following arrangement of mixing and shearing devices was used: mixing chest, dilution, deculator, pump, screen, headbox. 30 tons of paper were produced per hour.
- Example 2 was repeated with the exception that 280 g / t of the cationic polyacrylamide were metered in before the pump and the screen and 1400 g / t bentonite after the screen before the headbox. This amount was necessary to achieve an equally good retention.
- the FP retention was 69%, the FPA retention 40%.
- Example 2 As a comparison of the results of Example 2 with the results of Comparative Example 2 shows, the saving in polymer was approximately 30%. Although a smaller amount of retention aid was used in Example 2 than in Comparative Example 2, it was possible to achieve an equally good formation and paper properties in Example 2.
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Abstract
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Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP03784048A EP1529133B1 (de) | 2002-08-07 | 2003-07-23 | Verfahren zur herstellung von papier, pappe und karton |
AU2003250139A AU2003250139A1 (en) | 2002-08-07 | 2003-07-23 | Method for the production of paper, paperboard, and cardboard |
ES03784048T ES2380321T3 (es) | 2002-08-07 | 2003-07-23 | Procedimiento para la fabricación de papel, cartulina y cartón |
AT03784048T ATE546587T1 (de) | 2002-08-07 | 2003-07-23 | Verfahren zur herstellung von papier, pappe und karton |
US10/523,417 US7306701B2 (en) | 2002-08-07 | 2003-07-23 | Production of paper, board and cardboard |
JP2004526759A JP4518492B2 (ja) | 2002-08-07 | 2003-07-23 | 紙、厚紙、およびボール紙の製造方法 |
CA2494648A CA2494648C (en) | 2002-08-07 | 2003-07-23 | Method for the production of paper, paperboard, and cardboard |
BR0313051-7A BR0313051A (pt) | 2002-08-07 | 2003-07-23 | Processo para a produção de papel, papelão e cartolina |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10236252.1 | 2002-08-07 | ||
DE2002136252 DE10236252B4 (de) | 2002-08-07 | 2002-08-07 | Verfahren zur Herstellung von Papier, Pappe und Karton |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2004015200A1 true WO2004015200A1 (de) | 2004-02-19 |
Family
ID=7714828
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2003/008037 WO2004015200A1 (de) | 2002-08-07 | 2003-07-23 | Verfahren zur herstellung von papier, pappe und karton |
Country Status (12)
Country | Link |
---|---|
US (1) | US7306701B2 (de) |
EP (1) | EP1529133B1 (de) |
JP (1) | JP4518492B2 (de) |
CN (1) | CN1291104C (de) |
AT (1) | ATE546587T1 (de) |
AU (1) | AU2003250139A1 (de) |
BR (1) | BR0313051A (de) |
CA (1) | CA2494648C (de) |
DE (1) | DE20220979U1 (de) |
ES (1) | ES2380321T3 (de) |
PT (1) | PT1529133E (de) |
WO (1) | WO2004015200A1 (de) |
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WO2006027242A1 (de) | 2004-09-10 | 2006-03-16 | Basf Aktiengesellschaft | Verfahren zur herstellung von papier, pappe und karton |
WO2007031442A1 (de) * | 2005-09-13 | 2007-03-22 | Basf Se | Verfahren zur herstellung von papier, pappe und karton |
JP2008525654A (ja) * | 2004-12-22 | 2008-07-17 | アクゾ ノーベル エヌ.ブイ. | 紙材の製造のための方法 |
US7955473B2 (en) | 2004-12-22 | 2011-06-07 | Akzo Nobel N.V. | Process for the production of paper |
US8273216B2 (en) | 2005-12-30 | 2012-09-25 | Akzo Nobel N.V. | Process for the production of paper |
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WO2014001222A1 (de) * | 2012-06-25 | 2014-01-03 | Clariant Produkte (Deutschland) Gmbh | Verfahren zur herstellung von gefülltem papier und pappe unter verwendung von koazervaten |
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DE102004013007A1 (de) | 2004-03-16 | 2005-10-06 | Basf Ag | Verfahren zur Herstellung von Papier, Pappe und Karton |
US7473334B2 (en) * | 2004-10-15 | 2009-01-06 | Nalco Company | Method of preparing modified diallyl-N,N-disubstituted ammonium halide polymers |
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2002
- 2002-08-07 DE DE20220979U patent/DE20220979U1/de not_active Expired - Lifetime
-
2003
- 2003-07-23 CA CA2494648A patent/CA2494648C/en not_active Expired - Fee Related
- 2003-07-23 BR BR0313051-7A patent/BR0313051A/pt active Search and Examination
- 2003-07-23 CN CNB038189895A patent/CN1291104C/zh not_active Expired - Fee Related
- 2003-07-23 EP EP03784048A patent/EP1529133B1/de not_active Revoked
- 2003-07-23 AT AT03784048T patent/ATE546587T1/de active
- 2003-07-23 JP JP2004526759A patent/JP4518492B2/ja not_active Expired - Fee Related
- 2003-07-23 PT PT03784048T patent/PT1529133E/pt unknown
- 2003-07-23 ES ES03784048T patent/ES2380321T3/es not_active Expired - Lifetime
- 2003-07-23 WO PCT/EP2003/008037 patent/WO2004015200A1/de active Application Filing
- 2003-07-23 AU AU2003250139A patent/AU2003250139A1/en not_active Abandoned
- 2003-07-23 US US10/523,417 patent/US7306701B2/en not_active Expired - Fee Related
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Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8029647B2 (en) | 2004-09-10 | 2011-10-04 | Basf Aktiengesellschaft | Method for the production of paper, paperboard and cardboard |
WO2006027242A1 (de) | 2004-09-10 | 2006-03-16 | Basf Aktiengesellschaft | Verfahren zur herstellung von papier, pappe und karton |
US8308903B2 (en) * | 2004-12-22 | 2012-11-13 | Akzo Nobel N.V. | Process for the production of paper |
US8790493B2 (en) | 2004-12-22 | 2014-07-29 | Akzo Nobel N.V. | Process for the production of paper |
US7955473B2 (en) | 2004-12-22 | 2011-06-07 | Akzo Nobel N.V. | Process for the production of paper |
JP2008525654A (ja) * | 2004-12-22 | 2008-07-17 | アクゾ ノーベル エヌ.ブイ. | 紙材の製造のための方法 |
US20110247773A1 (en) * | 2004-12-22 | 2011-10-13 | Akzo Nobel N.V. | Process for the production of paper |
US9562327B2 (en) | 2004-12-22 | 2017-02-07 | Akzo Nobel N.V. | Process for the production of paper |
US8613832B2 (en) | 2005-05-16 | 2013-12-24 | Akzo Nobel N.V. | Process for the production of paper |
US9139958B2 (en) | 2005-05-16 | 2015-09-22 | Akzo Nobel N.V. | Process for the production of paper |
WO2007031442A1 (de) * | 2005-09-13 | 2007-03-22 | Basf Se | Verfahren zur herstellung von papier, pappe und karton |
CN101263263B (zh) * | 2005-09-13 | 2012-11-28 | 巴斯夫欧洲公司 | 生产纸、卡片纸板和纸板的方法 |
US7918965B2 (en) | 2005-09-13 | 2011-04-05 | Basf Aktiengesellschaft | Method for the production of paper, cardboard and card |
US8888957B2 (en) | 2005-12-30 | 2014-11-18 | Akzo Nobel N.V. | Process for the production of paper |
US8273216B2 (en) | 2005-12-30 | 2012-09-25 | Akzo Nobel N.V. | Process for the production of paper |
WO2014001222A1 (de) * | 2012-06-25 | 2014-01-03 | Clariant Produkte (Deutschland) Gmbh | Verfahren zur herstellung von gefülltem papier und pappe unter verwendung von koazervaten |
US11337800B2 (en) | 2015-05-01 | 2022-05-24 | Jenavalve Technology, Inc. | Device and method with reduced pacemaker rate in heart valve replacement |
Also Published As
Publication number | Publication date |
---|---|
JP2005534824A (ja) | 2005-11-17 |
CN1675432A (zh) | 2005-09-28 |
BR0313051A (pt) | 2005-06-14 |
US20050247420A1 (en) | 2005-11-10 |
CA2494648C (en) | 2011-10-04 |
US7306701B2 (en) | 2007-12-11 |
ATE546587T1 (de) | 2012-03-15 |
EP1529133A1 (de) | 2005-05-11 |
AU2003250139A1 (en) | 2004-02-25 |
CN1291104C (zh) | 2006-12-20 |
CA2494648A1 (en) | 2004-02-19 |
JP4518492B2 (ja) | 2010-08-04 |
DE20220979U1 (de) | 2004-10-14 |
PT1529133E (pt) | 2012-03-30 |
ES2380321T3 (es) | 2012-05-10 |
EP1529133B1 (de) | 2012-02-22 |
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