WO1997009356A1 - Resine hydrolysable contenant un aldehyde lie a cette resine et peinture antisalissure et auto-lustrante - Google Patents
Resine hydrolysable contenant un aldehyde lie a cette resine et peinture antisalissure et auto-lustrante Download PDFInfo
- Publication number
- WO1997009356A1 WO1997009356A1 PCT/JP1996/002555 JP9602555W WO9709356A1 WO 1997009356 A1 WO1997009356 A1 WO 1997009356A1 JP 9602555 W JP9602555 W JP 9602555W WO 9709356 A1 WO9709356 A1 WO 9709356A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- aldehyde
- primary amino
- amino group
- vehicle resin
- schiff base
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1637—Macromolecular compounds
- C09D5/165—Macromolecular compounds containing hydrolysable groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/28—Condensation with aldehydes or ketones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
Definitions
- the present invention relates to a hydrolysis-type resin useful as a vehicle resin for an antifouling paint, and an antifouling paint composition containing the resin.
- Antifouling paints using a trialkyltin polymer compound as a vehicle are known.
- This antifouling paint is excellent in that the amount of the antifouling agent eluted is kept to the minimum level that maintains the antifouling property, and that a certain amount is eluted over a long period of time.
- the trialkyltin polymer compound used as a vehicle is hydrolyzed in a slightly alkaline atmosphere of seawater to release tin compounds, and the vehicle becomes water-soluble and the coating film is consumed, so that the unevenness of the coating film is smooth. This reduces the frictional resistance of the ship against seawater and contributes to fuel cost savings.
- the vehicle resin of the self-polishing paint is, for example, a copolymer of triptyltin (meth) acrylate.
- a self-polishing vehicle resin for antifouling paints instead of a trialkyltin polymer is desired.
- an object of the present invention is to provide an antifouling effect by hydrolysis.
- the purpose is to provide a new type of antifouling paint vehicle resin that releases the dehydrate in a controlled manner, while the remaining coating is water soluble and gradually depleted.
- the present invention utilizes these reactions to bind the aldehyde to the vehicle resin in a hydrolyzable form.
- the present invention provides a vehicle resin for an antifouling paint comprising a vinyl polymer containing a plurality of primary amino groups in the form of Schiff bases in the molecule.
- a vinyl polymer containing a primary amino group in the form of a Schiff base can be obtained by reacting an aldehyde with a vinyl polymer having a primary amino group, or a monomer containing a primary amino group. After reacting the aldehyde with
- the present invention also provides an underwater antifouling paint containing the Schiff base vinyl polymer as a vehicle resin.
- the first method for producing a vinyl polymer having a plurality of primary amino groups in the form of a Schiff base in the molecule involves reacting an aldehyde with the corresponding vinyl polymer containing a primary amino group. It is.
- the primary amino group-containing vinyl polymer is obtained by copolymerizing an arylamine or 2-aminoethyl (meth) acrylate, for example, a hydrochloride, with another monomer, and then treating the primary amino with an alkali.
- the compound can be produced by regenerating a thio group.
- the present inventors have proposed aminostyrene (0—, m— and p—) By using it as a monomer containing a amino group, I learned that a vinyl copolymer containing a primary amino group can be directly produced by copolymerization.
- the primary amine monomer described above is an example of a monomer that gives a copolymer having a primary amino group at the terminal of a pendant group of a vinyl polymer, but is not known as an isolated monomer. It is also possible to produce a copolymer containing unreacted vinylamine as a repeating unit, that is, a copolymer in which a primary amino group is directly linked to the main chain of the copolymer.
- N-vinylacrylamide as the monomer.
- the double bond in the hydroxyl group has a relatively low activity, so it behaves like a monofunctional monomer under appropriate conditions, and a vinyl copolymer having an N-acryloylamino pendant group is obtained. can get. Thereafter, the acryloyl group is eliminated by hydrolysis to regenerate the primary amino group.
- the monomers that can be copolymerized include alkyl (methyl) acrylates such as alkyl, methyl, ethyl, n-propyl, n-butyl, t-butyl, 2-ethylhexyl, and the like. And / or other monomers such as styrene, na-methylstyrene, vinyl toluene, (meth) acrylamide, (meth) acrylonitrile, vinyl acetate, vinyl propionate, and vinyl chloride.
- alkyl (methyl) acrylates such as alkyl, methyl, ethyl, n-propyl, n-butyl, t-butyl, 2-ethylhexyl, and the like.
- monomers such as styrene, na-methylstyrene, vinyl toluene, (meth) acrylamide, (meth) acrylonitrile, vinyl acetate, vinyl
- hydroxyl group-containing acryl monomers such as 2—hydroxypropyl (meth) acrylate and 2—hydroxypropyl (meta) acrylate.
- aldehydes that form Schiff bases with primary amino groups of vinyl polymers.
- Formaldehyde is known as an aldehyde having a strong bactericidal action, and glyoxal, succin aldehyde, and glutaraldehyde are also known to have a prominent bactericidal action.
- aliphatic aldehydes containing these monomers and dial aldehydes can be selected.
- aldehyde having no or weak bactericidal action also has an antifouling action against aquatic organisms.
- Benzaldehyde is a typical example, and furthermore, such as p—n—hexylbenzaldehyde, p—octylbenzaldehyde, p—oleilbenzaldehyde, noklinirin, pironar Benzaldehyde derivatives having a substituent on the benzene ring and aromatic aldehydes such as cinnamaldehyde are also effective.
- saturated or unsaturated aliphatic aldehydes having 6 or more carbon atoms such as cabron aldehyde, capryl aldehyde, caprin aldehyde, laurine aldehyde, stearin aldehyde, and olein aldehyde.
- Benzaldehyde and its derivatives, and saturated or unsaturated aliphatic monoaldehydes having 6 or more carbon atoms are preferred from the viewpoint of handling and sustainability of antifouling activity.
- reaction of primary amines of vinyl polymers or monomers with aldehydes can be easily carried out under conditions that remove by-product water out of the system.
- a vinyl polymer having a primary amino group in the form of a Schiff base has a number average molecular weight of 2,000 to 100,000, especially 5,000 to 40,000. It is preferred to have This is necessary to maintain an appropriate balance between film forming properties, workability, and dissolution rate.
- the polymer also It is preferred to contain a primary amino group in the form of a fluorinated base in a concentration of from 0.01 to 1.5 mol / 100 g, in particular from 0.1 to 1.0 mol / 100 g.
- the above-mentioned aldehydes have an antifouling effect even when added to paint as an independent component.
- an aromatic primary amine such as aniline and its nuclear substituent may be added at the same time as an independent component, or may be added in the form of a Schiff base with aldehyde.
- the resin thus obtained is prepared into a self-polishing antifouling paint composition by adding conventional additives including an antifouling agent.
- the antifouling paint composition of the present invention can contain the following conventional components added to the antifouling paint.
- Metal powders or flakes such as copper, zinc and nickel: oxides, hydroxides, halides and other salts such as copper and zinc, especially cuprous oxide and copper rhodan; germicidal organic compounds such as copper naphthenate; Metal carboxylate such as copper stearate, zinc dinutyl dithiocarbamate, bisdimethyldithirubumyl zinc, metal such as ethylenebisdithiocarbamate (Na, K, Zn, Pb, G u, Fe, Ni, Mg, Se) dithiocarbamates; thiuram disulfides, such as tetramethyl thiuramdi sulphide; Methoxin, N, N'-dimethyl-N'-phenyl-N-sulfur such as fluorodichloromethylthiosulfamide Mi earth; glycidyl Ojin, full E Nchizoru, pyrrole such Porisai de, Lee Mi Dazo Le acids; Telazol
- Phthalate ester plasticizers such as dioctyl phosphate, dimethyl phosphate and dicyclohexyl phosphate; dibasic aliphatic acid ester plasticizers such as disodium adipate and dibutyl sebacate; diethylene glycol dibenzo Glycol ester-based plasticizers such as polyester, erythritol alkyl ester; phosphate ester-based plasticizers such as tricresyl and trichloroethyl phosphate; epoxidized soybean oil, epoxy stear Epoxy plasticizers such as octyl phosphate; organotin plasticizers such as dioctyltin laurate and dibutyltin laurate; and others such as trioctyl trimellitate and triacetylene .
- Chlorinated paraffin Chlorinated paraffin, polyvinyl ether, polypropylene sebage Terphenyl, partially hydrogenated terphenyl, polyvinyl acetate, poly (meth) alkyl acrylate, polyether polyol, alkyd resin, polyester resin, polyvinyl chloride, silicone oil, wax, petrolatum And liquid paraffin.
- Precipitating pigments such as sedimentable barium sulfate, talc, crepe, chalk, silica white, alumina white, and bentonite; titanium oxide, zirconium oxide, basic lead sulfate, tin oxide, carbon black, There are coloring pigments such as black, red, chrome yellow, phthalocyanine lean, phthalocyanine blue, and quinacridone.
- Hydrocarbons such as toluene, xylene, ethylbenzene, cyclopentane, octane, captan, cyclohexane, and white spirits: dioxane, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl Ethers such as ether, ethylene glycol dimethyl ether, ethylene glycol monobutyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether; butyl acetate, propyl acetate, benzyl acetate, Esters such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; ethylisobutyl butyl ketone, methylisopropyl Ke tons such as Luque tons; n - butanoate Lumpur, and the like alcohols such as propy
- Organic compounds such as rosin, ⁇ nobutyl phthalate, and ⁇ nooctyl succinate Basic acids, camphor and castor oil.
- composition of the present invention can be prepared by a method known per se in the art of paint production.
- a known machine for example, a ball mill, a pebble mill, a roll mill, a sand grind mill, or the like can be used.
- the coating film or film is gradually hydrolyzed and eluted in an atmosphere of seawater or the like.
- the resin when hydrolyzed in an alkaline atmosphere, the resin is not decomposed into small segments and eluted at once, but instead a hydrophilic group is generated in the side chain, and the resin is eluted only when the concentration reaches a certain critical value Take the form to do. Therefore, when used as a vehicle for ship bottom paint, it is possible to give a coating film with very good properties, which has the characteristic that the antifouling period can be controlled over a long period. Accordingly, the antifouling paint of the present invention is useful for ships such as tankers, funeries, fishing boats, steel boats, wooden boats, FRP boats, underwater structures, fish nets, and water pipes.
- Production Example 5 95 parts of xylene was added to the same flask as in Production Example 1, to which 35 parts of N-vinylacrylamide, 45 parts of methyl methacrylate, 20 parts of styrene, 2,2'-azobis A mixture of 1.3 parts of isoptyronitrile is added dropwise over 4 hours. After 30 minutes, a solution of 5 parts of xylene and 0.2 parts of 2,2′-azobisisobutyronitrile is added dropwise over 30 minutes. After the addition, the temperature was maintained at the same temperature for 90 minutes.
- Varnish B (100 parts) and vanillin (38 parts) were added to the same flask as in Production Example 6, and the mixture was reacted at a reflux temperature of about 130 while distilling off by-produced water for 3 hours. Obtained.
- Each component was dispersed with a disperser according to the formulations shown in Tables 1 and 2, and coated.
- Titanium oxide 10 7 5 5 5 5 5 5 5 5 5 5 5 5 5
- Cuprous oxide 20 20 25 25 15 Zinc white 15 15 15 5 5 7 3 15 Talc 5 5 5 5 5 5 2 5
- Varnishes C to J were used as paints as they were.
- a test plate was prepared by applying such that
- Example 21 The paints (varnishes C to J) of 1 to 28 were applied to a 9 ⁇ 28 cm polyvinyl chloride resin plate so as to have a dry film thickness of about 100 m and tested. A test plate was prepared.
- the paints of the Examples and Comparative Examples were applied to an acrylic resin disk having a diameter of 35 cm so as to have a dry film thickness of about 100 m.
- the sample was continuously rotated for 12 months at 5 knots, and the difference from the initial film thickness over time was measured as the degree of consumption of the coating film. Table 4 shows the results.
- the antifouling paint resin and the antifouling paint of the present invention exhibited performance equivalent to the self-polishing antifouling paint of Comparative Example 4 using an organotin polymer in antifouling properties and self-polishing properties.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DK96929559T DK0849289T3 (da) | 1995-09-08 | 1996-09-06 | Hydrolyserbar harpiks indeholdende dertil bundet aldehyd og selvpolerende antibegroningsmaling |
US09/029,826 US5914357A (en) | 1995-09-08 | 1996-09-06 | Hydrolyzable resin containing aldehyde bounded thereto and self-polishing antifouling paint |
JP51108397A JP3289194B2 (ja) | 1995-09-08 | 1996-09-06 | アルデヒドを結合した加水分解型樹脂および自己研磨型防汚塗料 |
DE69625072T DE69625072T2 (de) | 1995-09-08 | 1996-09-06 | Hydrolysierbares harz, enthaltend daran gebundenes aldehyd und selbstpolierender fäulnisverhindernder anstrich |
EP96929559A EP0849289B1 (en) | 1995-09-08 | 1996-09-06 | Hydrolyzable resin containing aldehyde bonded thereto and self-polishing antifouling paint |
NO19980952A NO316385B1 (no) | 1995-09-08 | 1998-03-05 | Selvpolerende grohindrende maling |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP25693195 | 1995-09-08 | ||
JP7/256931 | 1995-09-08 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1997009356A1 true WO1997009356A1 (fr) | 1997-03-13 |
Family
ID=17299364
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1996/002555 WO1997009356A1 (fr) | 1995-09-08 | 1996-09-06 | Resine hydrolysable contenant un aldehyde lie a cette resine et peinture antisalissure et auto-lustrante |
Country Status (9)
Country | Link |
---|---|
US (1) | US5914357A (ja) |
EP (1) | EP0849289B1 (ja) |
JP (1) | JP3289194B2 (ja) |
KR (1) | KR100254651B1 (ja) |
CN (1) | CN1118486C (ja) |
DE (1) | DE69625072T2 (ja) |
DK (1) | DK0849289T3 (ja) |
NO (1) | NO316385B1 (ja) |
WO (1) | WO1997009356A1 (ja) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6462102B1 (en) | 1999-09-21 | 2002-10-08 | Nippon Paint Co., Ltd. | Resin for use in an antifouling coating and antifouling coating |
WO2009031509A1 (ja) * | 2007-09-07 | 2009-03-12 | Chugoku Marine Paints, Ltd. | 防汚塗料組成物、防汚塗膜、塗膜付き基材、防汚性基材、基材表面への塗膜の形成方法および基材の防汚方法 |
JP2011519968A (ja) * | 2008-05-12 | 2011-07-14 | バイオペイント・ソシエタ・ア・レスポンサビリタ・リミタータ | 防汚塗料用の環境に優しい新規な微生物付着防止剤及び該防止剤を含有する防汚塗料 |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BR9914498A (pt) * | 1998-09-23 | 2001-06-26 | Phycogen Inc | Compostos inibidores de biopelìcula seguros e eficazes e usos dos mesmos relacionados a saúde |
US7482394B2 (en) * | 2003-02-05 | 2009-01-27 | Chemical Investment Ltd. | Antifouling coating |
CA2878680C (en) | 2012-07-23 | 2019-09-17 | Crayola, Llc | Dissolvable films and methods of using the same |
CN103752282B (zh) * | 2013-12-26 | 2016-01-27 | 燕山大学 | 一种利用树脂/席夫碱复合材料去除水中重金属的方法 |
JP6427450B2 (ja) * | 2014-03-31 | 2018-11-21 | 積水化学工業株式会社 | 変性ポリビニルアセタール樹脂 |
CN107987693B (zh) * | 2017-12-15 | 2019-12-17 | 中山市钧纬新材料科技有限公司 | 一种持久抗菌型水性醇酸涂料 |
CN113698561B (zh) * | 2021-09-01 | 2024-04-09 | 中国科学院宁波材料技术与工程研究所 | 主链降解型金属离子络合聚席夫碱防污树脂、制法与应用 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6323906A (ja) * | 1986-07-17 | 1988-02-01 | Mishima Seishi Kk | 新規なリビングポリマ− |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3177171A (en) * | 1959-10-08 | 1965-04-06 | Gen Tire & Rubber Co | Process for reacting ammonia or a primary amine with an acrolein polymer and resulting product |
GB1065595A (en) * | 1963-07-22 | 1967-04-19 | Monsanto Co | Imidazolines and imidazolidines and oil compositions containing the same |
FR1525504A (fr) * | 1966-06-02 | 1968-05-17 | Kyowa Hakko Kogyo Kk | Procédé pour la préparation de bases de schiff de pyridoxal et de polymères de poids moléculaire élevé |
US4178430A (en) * | 1978-11-20 | 1979-12-11 | Hughes Aircraft Company | Polymeric Schiff's bases containing acetylene terminal groups |
DE3023464A1 (de) * | 1980-06-24 | 1982-02-04 | Hoechst Ag, 6000 Frankfurt | Verfahren zur herstellung von formkoerpern und ueberzuegen |
JPS58120678A (ja) * | 1982-01-12 | 1983-07-18 | Mitsubishi Rayon Co Ltd | 防汚塗料用組成物 |
JPH0667975B2 (ja) * | 1986-11-17 | 1994-08-31 | 日本ペイント株式会社 | 金属含有塗料用樹脂の製造方法 |
JPH0791459B2 (ja) * | 1990-09-26 | 1995-10-04 | 住友デュレズ株式会社 | 芳香族炭化水素変性ポリイミド樹脂組成物 |
JP3282905B2 (ja) * | 1993-01-21 | 2002-05-20 | 日立化成工業株式会社 | 防汚塗料組成物 |
-
1996
- 1996-09-06 EP EP96929559A patent/EP0849289B1/en not_active Expired - Lifetime
- 1996-09-06 DE DE69625072T patent/DE69625072T2/de not_active Expired - Fee Related
- 1996-09-06 CN CN96196847A patent/CN1118486C/zh not_active Expired - Lifetime
- 1996-09-06 US US09/029,826 patent/US5914357A/en not_active Expired - Lifetime
- 1996-09-06 DK DK96929559T patent/DK0849289T3/da active
- 1996-09-06 KR KR1019980701728A patent/KR100254651B1/ko not_active IP Right Cessation
- 1996-09-06 WO PCT/JP1996/002555 patent/WO1997009356A1/ja active IP Right Grant
- 1996-09-06 JP JP51108397A patent/JP3289194B2/ja not_active Expired - Lifetime
-
1998
- 1998-03-05 NO NO19980952A patent/NO316385B1/no not_active IP Right Cessation
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6323906A (ja) * | 1986-07-17 | 1988-02-01 | Mishima Seishi Kk | 新規なリビングポリマ− |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6462102B1 (en) | 1999-09-21 | 2002-10-08 | Nippon Paint Co., Ltd. | Resin for use in an antifouling coating and antifouling coating |
WO2009031509A1 (ja) * | 2007-09-07 | 2009-03-12 | Chugoku Marine Paints, Ltd. | 防汚塗料組成物、防汚塗膜、塗膜付き基材、防汚性基材、基材表面への塗膜の形成方法および基材の防汚方法 |
JP5615549B2 (ja) * | 2007-09-07 | 2014-10-29 | 中国塗料株式会社 | 防汚塗料組成物、防汚塗膜、塗膜付き基材、防汚性基材、基材表面への塗膜の形成方法および基材の防汚方法 |
JP2011519968A (ja) * | 2008-05-12 | 2011-07-14 | バイオペイント・ソシエタ・ア・レスポンサビリタ・リミタータ | 防汚塗料用の環境に優しい新規な微生物付着防止剤及び該防止剤を含有する防汚塗料 |
Also Published As
Publication number | Publication date |
---|---|
CN1196063A (zh) | 1998-10-14 |
KR100254651B1 (ko) | 2000-05-01 |
EP0849289A1 (en) | 1998-06-24 |
NO980952L (no) | 1998-03-05 |
CN1118486C (zh) | 2003-08-20 |
KR19990044480A (ko) | 1999-06-25 |
NO980952D0 (no) | 1998-03-05 |
DE69625072T2 (de) | 2003-08-21 |
EP0849289B1 (en) | 2002-11-27 |
DK0849289T3 (da) | 2003-03-17 |
NO316385B1 (no) | 2004-01-19 |
JP3289194B2 (ja) | 2002-06-04 |
DE69625072D1 (de) | 2003-01-09 |
US5914357A (en) | 1999-06-22 |
EP0849289A4 (en) | 2000-06-14 |
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