WO1999032564A1 - Low toxicity paint stripper - Google Patents
Low toxicity paint stripper Download PDFInfo
- Publication number
- WO1999032564A1 WO1999032564A1 PCT/US1998/026294 US9826294W WO9932564A1 WO 1999032564 A1 WO1999032564 A1 WO 1999032564A1 US 9826294 W US9826294 W US 9826294W WO 9932564 A1 WO9932564 A1 WO 9932564A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- paint
- stripping composition
- stripping
- benzyl alcohol
- weight
- 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
- C09D9/00—Chemical paint or ink removers
Definitions
- This invention relates generally to paint-stripping compositions, and more specifically it relates to a paint-stripping composition having low toxicity and a very low concentration of volatile organic compounds and/or hazardous air pollutants.
- Paint strippers are important industrial chemicals, and are used both in the finishing and refinishing of manufactured articles and in the clean-up of painting facilities. Large amounts of paint-stripping compositions are used in connection with the refinishing of commercial and military aircraft, as well as in the manufacture of motor vehicles.
- a threshold requirement for a good paint-stripping composition is that it efficiently and effectively remove a variety of paints without harming the underlying workpiece. This requirement is particularly important in connection with the aircraft industry, since aircraft are frequently fabricated from aluminum or magnesium based alloys which are easily corroded by acidic or alkaline materials.
- paint-stripping compositions be of relatively low toxicity.
- VOCs volatile organic compounds
- HAPs hazardous air pollutants
- governmental regulations have strictly curtailed the amounts of NOCs and HAPs which an industry can release.
- industry must avoid the use of volatile organic compounds, or install expensive recovery systems.
- paint- stripping compositions are typically employed in large volumes, and distributed over relatively large areas, the escape of NOCs and HAPs therefrom can be significant.
- there is need for paint-stripping compositions which have a low content of volatile and/or hazardous organic compounds.
- cost is always a significant concern with regard to chemicals such as paint-strippers which are used in large volumes, there is a need for a low-cost stripping composition which meets the foregoing criteria.
- Solvents such as benzene, toluene, and halocarbons are effective strippers for many commonly employed paints, but such materials are highly volatile, and in some instances, toxic and/or flammable.
- a number of paint-stripping compositions are known in the prior art.
- U.S. Patent 5,454,985 discloses paint-stripping compositions based upon a mixture of benzyl alcohol and water, which compositions may also include acidic or alkaline accelerators.
- Patent Application Serial No. 08/610,155 discloses paint strippers based upon benzyl alcohol and water which further include peroxide activators.
- Patent 3,355,385 discloses paint-stripping compositions based upon aqueous hydrogen peroxide in combination with various organic solvents, including methylene chloride, and other halocarbons.
- Patents 5,518,661 and 4,445,939 both show paint-stripping compositions based upon specific mixtures of benzyl alcohol and methylene chloride.
- the prior art has made many attempts at fabricating paint-stripping compositions, but to date, there is still a need for a highly effective, non-corrosive, low-toxicity paint- stripping composition having a low concentration of NOCs and HAPs.
- paint-stripping compositions which are highly effective against a variety of paint formulations, and which are capable of operating at a neutral or near neutral pH (typically in the range of 4-8) can be prepared so as to include a relatively small amount of NOC or HAP materials therein.
- paint-stripping composition which comprises, on a weight basis, at least 20% of benzyl alcohol or an alkyl substituted benzyl alcohol, together with 5-30%> of methylene chloride and 1-10% of hydrogen peroxide, together 10-60%> of water.
- the peroxide is added as a 35% aqueous solution, and the solution will thus comprise approximately 2.8- 28.5%o of the stripping composition.
- the composition may also include one or more auxiliary ingredients such as thickeners, evaporation retardants, surfactants, pH control agents, corrosion inhibitors, preservatives, coloring agents, and fragrances; and these auxiliary ingredients may comprise up to 20%> by weight of the composition.
- acidic accelerators may also be included in the composition.
- the benzyl alcohol is present in an amount of 20-50%> by weight
- the hydrogen peroxide is present in an amount of
- the methylene chloride is present in an amount of 15-20% by weight, and the water is present in an amount of 15-30% by weight.
- a method of paint stripping which method involves the use of the aforedescribed compositions.
- methylene chloride, water, peroxides, and a benzyl alcohol interact synergistically to produce a highly effective paint-stripping composition. Because of this synergistic interaction, the amount of methylene chloride in the stripping composition may be kept relatively low, thereby decreasing the level of NOC and/or HAP materials in the stripper. While the various components of the strippers of the present invention may be present in varied concentrations, it has been found that the specified compositional ranges and ratios of the materials provide superior stripping action against a variety of paint compositions, while still maintaining a relatively low level of volatile and/or hazardous materials. Various components of the stripper of the present invention will be discussed individually hereinbelow, and then various examples of the material will be presented; and unless otherwise noted, all compositions presented herein are on the basis of weight. Benzyl Alcohol
- An active component of the composition of the present invention is a benzyl alcohol.
- the benzyl alcohol will be the unsubstituted benzyl alcohol; however, various alkyl substituted benzyl alcohols, such as methyl and ethyl benzyl alcohols (including the alpha, ortho, meta and para isomers) are known in the art, and such materials may also be employed in the present invention.
- a benzyl alcohol refers to unsubstituted benzyl alcohol as well as substituted forms thereof.
- the benzyl alcohol is present on a weight basis of at least 20%.
- the benzyl alcohol composition will be in the range of 20-50%, and more preferably 30-40%>.
- the benzyl alcohol comprises approximately 40%> of the composition.
- the ratio of the benzyl alcohol to the methylene chloride is in the ratio of 2:1 to ⁇ 3:1.
- water is an active component of the stripping composition.
- the water also lowers the cost of the composition and lowers the concentration of undesirable volatile materials therein.
- One particularly preferred range of concentration for the water is 15-30%, and in a specific stripper formulation, water comprises approximately 25%> of the material.
- Peroxide Peroxide is another active component of the stripping composition of the present invention.
- the peroxide is most preferably hydrogen peroxide, and is most typically present in an amount of 1-10% of the composition.
- the hydrogen peroxide component is most typically present in an amount of 2.8-28% by weight of a 35% solution.
- the hydrogen peroxide is present on an absolute basis in an amount of approximately 7%> (20%> of a 35%> solution).
- concentrations of hydrogen peroxide may be similarly employed, depending upon availability and cost.
- the amount of water in this component should be taken into account and the total amount of water in the composition adjusted accordingly.
- other peroxides such as organic peroxides may also be employed in the present invention, and the appropriate amounts thereof calculated on the basis of their molar equivalence to hydrogen peroxide.
- Methylene chloride is the fourth active ingredient of the stripping composition of the present invention.
- the methylene chloride should be present in an amount of at least 5% of the composition. In most instances, amounts of methylene chloride in excess of 30%> are undesirable, since they contribute to the VOC/HAP levels of the composition. In typical compositions, it has been found that approximately 15-20%> methylene chloride provides very good stripping action. In one group of compositions of the present invention, the methylene chloride comprises approximately 19% by weight.
- auxiliary ingredients will also be present in the stripping compositions.
- auxiliary ingredients might include thickeners, evaporation retardants, surfactants, pH control agents, corrosion inhibitors, preservatives, coloring agents and fragrances.
- thickeners such as methyl cellulose, ethyl cellulose and the like may be included to increase the viscosity of the material to produce a stripper capable of clinging to non-horizontal surfaces.
- evaporation retardants in the mixture to further decrease release of volatile materials therefrom.
- evaporation retardants are well known in the art and include materials such as glycerine, wax, high molecular weight esters and the like.
- Surfactants such as Tergitol® and the like may also be advantageously included in the compositions. Surfactants facilitate wetting of the surface being stripped by the compositions, and may also assist in maintaining the homogeneity of the solution by enhancing solubilization, or emulsification of the various materials comprising the stripper.
- compositions of the present invention are active and effective under relatively mild pH conditions, and thereby will not harm reactive aircraft alloys. Most typically, compositions of the present invention operate under neutral to near neutral pH conditions, typically in the range of pH
- acids or alkalis may be included to adjust the pH
- buffers may be included to assure that the pH remains stable.
- Corrosion inhibitors such as octamine and the like may be included in relatively low concentrations to further prevent any corrosion of metal surfaces, and/or to protect reactive metal surfaces from atmospheric corrosion, once stripping is complete.
- Preservatives such as citrates, benzoates, and the like may be included, as in known in the art, to prevent growth of unwanted microbes in the material.
- coloring agents, fragrances and the like may be added to enhance the aesthetic appeal of the stripping composition.
- the auxiliary ingredients will collectively comprise no more that 20% of the weight of the composition.
- compositions of the present invention are useable at neutral to near neutral pH conditions, in some specific instances particular paint formulations may require that accelerators such as acids or alkalis may be added to the composition, as is known in the art, to further enhance the stripping ability thereof.
- One preferred group of acidic accelerators comprises organic acids, with formic acid, acetic acid, propionic acid, glycolic acid, and halogenated forms thereof, being particularly preferred. It has been found, as is demonstrated herein, that the peroxide component of the composition interacts, beneficially, with the acid so as to enhance its effect. Therefore, only relatively small amounts of acid (typically 3-7%) are required to accelerate the stripping action. These low acid concentrations decrease the corrosivity of the acid accelerated strippers, making them particularly suitable for aircraft alloys. Likewise, the presence of the acid allows for a lowering of the peroxide content, thereby enhancing the stability of the composition, while still maintaining good stripping action.
- composition 1 comprised a prior art stripping material which included 40%> benzyl alcohol, 28%> water, and relatively minor amounts of auxiliary ingredients including a cellulose ester thickener, a surfactant, 2% naphtha, wax and approximately 5% glycerine.
- Composition 2 was identical to Composition 1, except that it also included 7% hydrogen peroxide.
- Composition 3 was identical to Composition 1, except that it further included 13.5%) methylene chloride.
- Composition 4 was identical to Composition 1 except that it included 7% hydrogen peroxide and 13.5% of methylene chloride.
- compositions were tested against an aircraft panel from Southwest Airlines which was coated with a commercial coating designated Dexter-Crown Metro coating. These and all other evaluations were carried out at a temperature of 67.6 °F at a relative humidity of 54%.
- Composition 1 required 40 minutes to remove the coating.
- Composition 2 required 24 minutes to remove the coating.
- Composition 3 began removing the coating after 10 minutes, and Composition 4 removed most of the coating after 10 minutes.
- compositions were then evaluated against an aircraft panel which was coated with a first layer of BMS 1079 type I epoxy primer and a second layer of BMS 1060 type II polyurethane top coat, both of which are sold by the Courtaulds Aerospace Corporation.
- Composition 1 required 83 to 85 minutes to strip the panel.
- Composition 2 required 73 minutes to strip the panel.
- Composition 3 required 29 minutes to strip the panel, and Composition 4 stripped the panel in approximately 23 minutes.
- Composition 1 required 240 minutes to strip the panel.
- Composition 2 required 52 minutes to begin stripping and 73 minutes to complete stripping of the panels.
- Composition 3 required 45 minutes to begin stripping of the panels and 70 minutes to complete the stripping; and Composition 4 required 26 minutes to begin stripping of the panels and 33 minutes to complete the stripping. These compositions were then tested against a painted aircraft panel obtained from Nippon Airways. Specific composition of the paint was unknown. Composition 1 produced no stripping whatsoever. Composition 2 produced no stripping after 8 hours contact, but did evidence some coating removal after contact was maintained overnight. Composition 3 produced no stripping and Composition 4 stripped the sample in approximately 6 to 7.5 hours.
- compositions 1-3 produced no stripping whatsoever, while Composition 4 began stripping after 6.5 hours, and complete stripping was obtained after overnight contact.
- compositions containing various concentrations of the active ingredients of the stripper of the present invention were prepared to evaluate the concentration effects of the different components.
- a series of compositions designated Samples 5-18 were prepared, and each was evaluated against a test panel comprising a substrate of 2024-T3 clad aluminum which was treated with Alodine 1200 and painted with a first coat comprising BMS 1079 type II epoxy primer and a top coat of BMS 1060 type II polyurethane top coat. All samples were tested at 74.2° and 55% relative humidity. Each sample was spot applied to the panel and the time for removal of the coating was noted. The results are summarized in Table 1 hereinbelow.
- Samples 14 and 15 demonstrate that stripping efficiency drops to some degree as the water concentration is decreased, even though the amount of benzyl alcohol present is increased, thereby indicating that water is an active component in the composition.
- compositions 16-18 both water and benzyl alcohol are varied.
- Sample 19 included methylene chloride as the solvent, and stripping time
- Sample 20 substituted a proprietary fluorinated solvent sold
- Oxsol 100 by the Occidental Petroleum Company, for the
- Sample 21 substitutes chlorinated solvent sold by the Occidental
- Sample 23 substitutes perchlorethylene for the methylene chloride, and stripping
- Sample 24 includes no methylene chloride
- a fourth experimental series was carried out utilizing the aforedescribed coated panels for the purpose of evaluating the effect of the benzyl alcohol component.
- a group of stripping compositions were prepared which included 19% methylene chloride, 24%> water, 7% hydrogen peroxide and 40%> of the various solvent compounds.
- Sample 25 included benzyl alcohol, and the stripping time was 13.5 minutes.
- Samples 26 and 27 included the aforedescribed Oxsol 100 and 10 solvents, and no stripping action occurred.
- Sample 28 included commercially available solvent material sold under the designation Dibasic Ester, by the DuPont Corporation, and the composition required 113 minutes to strip.
- Sample 29 substitutes nonylphenyl ether material sold under the designation Triton N for the benzyl alcohol, and this composition was not effective as a paint stripper.
- Sample 30 evaluated the effect of substituting methylpropyl ketone for the benzyl alcohol, and it will be noted that this material did not produce a strong stripping action.
- Sample 31 evaluated the effect of substituting N-methyl pyrrolidone for the benzyl alcohol, and again it will be noted that this composition was not a highly effective paint stripper. This is particularly significant since NMP is a widely employed paint-stripping material. In a fifth experimental series, the use of organic peroxides was evaluated.
- Two stripper compositions were prepared; each included 19%> methylene chloride, 40%) benzyl alcohol, 24%> water, and 0.21 moles of total peroxide.
- the first composition employed hydrogen peroxide and the second sample employed t- butylhydroperoxide. Both samples were evaluated against the standard panels described above at 74.2°F and a relative humidity of 55%>.
- the hydrogen peroxide containing material stripped the panels in 13.5 minutes, while the sample containing the organic peroxide required 62 minutes to complete the stripping.
- Sample 32 had 3% peroxide and no formic acid; as such it corresponded to Sample 14 on Table 1 , and as will be noted, it stripped the test panel in 24 minutes.
- Sample 33 was generally similar to Sample 32, except that it also included 5% of formic acid, and it will be noted that the stripping time was decreased to 14 minutes.
- Sample 34 included 7% peroxide and no formic acid, and as such it corresponds generally to Sample 16 of Table 1, and in this experiment, it stripped the panel in 14 minutes.
- Sample 35 included 10% formic acid and no peroxide, and it stripped the test panel in 29 minutes.
- Sample 36 co ⁇ esponded generally to Sample 35, but further included 7% peroxide, and it stripped the panel in 9 minutes.
- Sample 33 stripped the panel in 14 minutes, while Sample 32, which did not include formic acid, required 24 minutes for stripping.
- Sample 34 did not include any formic acid, and it stripped the panel in a time comparable to Sample 33, but required a 7%> peroxide content.
- Sample 35 includes a relatively high acid content, and no peroxide, and this sample required the longest stripping time.
- Sample 36 which includes a relatively high concentration of acid together with 7%> peroxide, produced a very rapid strip time. From the foregoing, it will be seen that the acid and peroxide interact in the stripping composition in a manner which allows for a reduction of the concentration of both of the components thereby decreasing both the corrosive nature of the stripper as well as the peroxide content.
- paint stripping compositions of the type described herein may further include acidic accelerators therein.
- These accelerators typically comprise organic acids.
- Formic acid is one particularly prefe ⁇ ed acid accelerator, since it is relatively low in cost, low in toxicity and highly effective.
- Other accelerators include low molecular weight organic acids such as acetic acid, propionic acid, lactic acid and glycolic acid. In some instances, the acids may be halogenated to further enhance their activity.
- the concentration of the acid will be no more than 10%, and in a particularly prefe ⁇ ed group of compositions, the acid concentration will be
- One particular composition includes formic acid as an accelerator, and the acid is present in a concentration of 5% or less, together with hydrogen peroxide in an amount of 3-7%.
- formic acid is a relatively strong acid, and in the event that other, weaker acids are substituted therefor, the concentration of accelerator may be adjusted upwardly as appropriate.
- paint-stripping compositions having relatively low levels of HAP and or NOC materials may be fabricated a mixture of at least 20%> of a benzyl alcohol together with 5 to 30%> of methylene chloride,
- compositions further include auxiliary ingredients such as thickeners, co ⁇ osion inhibitors, pH control agents, accelerators, colors, preservatives, fragrances, evaporation retardants, surfactants, and the like.
- auxiliary ingredients such as thickeners, co ⁇ osion inhibitors, pH control agents, accelerators, colors, preservatives, fragrances, evaporation retardants, surfactants, and the like.
- the compositions of the present invention are effective against a wide variety of paint formulations, including paint formulations which are utilized in the aircraft industry.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Detergent Compositions (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP98963054A EP1040170A4 (en) | 1997-12-19 | 1998-12-11 | Low toxicity paint stripper |
AU18160/99A AU737274B2 (en) | 1997-12-19 | 1998-12-11 | Low toxicity paint stripper |
BR9813781-6A BR9813781A (en) | 1997-12-19 | 1998-12-11 | Low toxicity paint remover |
CA002315161A CA2315161A1 (en) | 1997-12-19 | 1998-12-11 | Low toxicity paint stripper |
JP2000525492A JP2001527115A (en) | 1997-12-19 | 1998-12-11 | Low toxicity paint remover |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/994,059 US5990062A (en) | 1997-12-19 | 1997-12-19 | Low toxicity paint stripper |
US08/994,059 | 1997-12-19 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1999032564A1 true WO1999032564A1 (en) | 1999-07-01 |
Family
ID=25540247
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1998/026294 WO1999032564A1 (en) | 1997-12-19 | 1998-12-11 | Low toxicity paint stripper |
Country Status (7)
Country | Link |
---|---|
US (1) | US5990062A (en) |
EP (1) | EP1040170A4 (en) |
JP (1) | JP2001527115A (en) |
AU (1) | AU737274B2 (en) |
BR (1) | BR9813781A (en) |
CA (1) | CA2315161A1 (en) |
WO (1) | WO1999032564A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20210348006A1 (en) * | 2020-05-08 | 2021-11-11 | The Boeing Company | Chemical process for stripping surfaces |
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US5728666A (en) * | 1996-12-19 | 1998-03-17 | Napier International Technologies, Inc. | Water-based alcohol hydroxycarboxylic peroxide compositions and their preparation |
US7179774B2 (en) * | 2002-06-19 | 2007-02-20 | Henkel Kommanditgesellschaft Auf Aktien | Flushing solutions for coatings removal |
US7482316B2 (en) * | 2001-01-04 | 2009-01-27 | Henkel Kommanditgesellschaft Auf Aktien | Water-based flushing solution for paints and other coatings |
US6887837B2 (en) * | 2001-01-04 | 2005-05-03 | Henkel Kommandirgesellschaft Auf Aktien | Water-based paint-removing solution |
US6417149B1 (en) | 2001-02-08 | 2002-07-09 | Gerald Wojcik | Paint stripping composition and process containing methyl benzoate and formic acid |
CA2470021A1 (en) * | 2001-12-14 | 2003-06-26 | Aero-Chem, Llc | Cyclic ether based paint remover |
DE10161844A1 (en) * | 2001-12-15 | 2003-06-26 | Henkel Kgaa | Aqueous alkaline paint stripper |
US7091163B2 (en) * | 2002-06-25 | 2006-08-15 | Henkel Kommanditgesellschaft Auf Aktien | Flushing solutions for coatings removal |
US7179775B2 (en) * | 2002-09-11 | 2007-02-20 | Henkel Kommanditgesellschaft Auf Aktien | Coating removal compositions |
US7229953B1 (en) * | 2004-10-25 | 2007-06-12 | Green Oaks Research Laboratories, Inc. | Process for removing a coating from a substrate |
US8383565B2 (en) * | 2005-11-17 | 2013-02-26 | Sunnyside Corporation | Color changing paint and varnish remover |
US7304021B2 (en) * | 2005-11-17 | 2007-12-04 | Dynacraft Industries, Inc | Color changing paint and varnish remover |
JP5464809B2 (en) * | 2008-02-29 | 2014-04-09 | 横浜油脂工業株式会社 | Aqueous release agent for coating film and coating film peeling method |
US9234164B2 (en) | 2014-02-11 | 2016-01-12 | Gregory E Robinson | Graffiti remover comprising a solvent mixture of propylene carbonate and soy methyl ester |
US20200010699A1 (en) * | 2017-03-28 | 2020-01-09 | Neos Co., Ltd. | Coating film stripping composition and method for stripping coating film |
WO2019168919A1 (en) * | 2018-02-28 | 2019-09-06 | The University Of Massachusetts | Composition and method for removing a coating from a surface |
KR102546753B1 (en) * | 2022-12-15 | 2023-06-23 | 정하상 | Gel-type paint stripper containing evaporation inhibitor |
KR102546752B1 (en) * | 2022-12-15 | 2023-06-23 | 정하상 | A thermosetting paint remover composition including an aqueous layer |
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1997
- 1997-12-19 US US08/994,059 patent/US5990062A/en not_active Expired - Fee Related
-
1998
- 1998-12-11 BR BR9813781-6A patent/BR9813781A/en not_active Application Discontinuation
- 1998-12-11 WO PCT/US1998/026294 patent/WO1999032564A1/en not_active Application Discontinuation
- 1998-12-11 AU AU18160/99A patent/AU737274B2/en not_active Ceased
- 1998-12-11 CA CA002315161A patent/CA2315161A1/en not_active Abandoned
- 1998-12-11 JP JP2000525492A patent/JP2001527115A/en active Pending
- 1998-12-11 EP EP98963054A patent/EP1040170A4/en not_active Withdrawn
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20210348006A1 (en) * | 2020-05-08 | 2021-11-11 | The Boeing Company | Chemical process for stripping surfaces |
US11952512B2 (en) * | 2020-05-08 | 2024-04-09 | The Boeing Company | Chemical process for stripping surfaces |
Also Published As
Publication number | Publication date |
---|---|
EP1040170A1 (en) | 2000-10-04 |
AU737274B2 (en) | 2001-08-16 |
US5990062A (en) | 1999-11-23 |
JP2001527115A (en) | 2001-12-25 |
CA2315161A1 (en) | 1999-07-01 |
EP1040170A4 (en) | 2001-07-25 |
BR9813781A (en) | 2000-10-03 |
AU1816099A (en) | 1999-07-12 |
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