EP1187793A1 - Composition de fibres de verre - Google Patents

Composition de fibres de verre

Info

Publication number
EP1187793A1
EP1187793A1 EP00932752A EP00932752A EP1187793A1 EP 1187793 A1 EP1187793 A1 EP 1187793A1 EP 00932752 A EP00932752 A EP 00932752A EP 00932752 A EP00932752 A EP 00932752A EP 1187793 A1 EP1187793 A1 EP 1187793A1
Authority
EP
European Patent Office
Prior art keywords
percent
weight
glass
glass fiber
composition according
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.)
Withdrawn
Application number
EP00932752A
Other languages
German (de)
English (en)
Inventor
Frederick T. Wallenberger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
PPG Industries Ohio Inc
Original Assignee
PPG Industries Ohio Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by PPG Industries Ohio Inc filed Critical PPG Industries Ohio Inc
Publication of EP1187793A1 publication Critical patent/EP1187793A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C13/00—Fibre or filament compositions
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics

Definitions

  • This invention relates to continuous glass fibers having glass compositions useful as reinforcement and textile fibers.
  • E-glass The most common glass composition for making continuous glass fibers, designated as E-glass, dates back to 1940. As described in the British Patent Specification No. 520,427, the original E-glass fibers were boron free and were based on glass compositions at or near the eutectic in the quaternary Si0 2 -AI 2 O 3 -CaO-MgO phase diagram.
  • ⁇ T means the difference between the liquidus temperature and the forming temperature.
  • ⁇ T is at least 90°F (50°C), and preferably at least 100°F (56°C) so as to preclude crystal formation in the bushing tips due to inevitable temperature and viscosity fluctuations of the melt and provide for safe and uninterrupted commercial production.
  • Patent 2,571 ,074 by reducing the B 2 0 3 content from about 10.0% to eventually about 5.5% and by reducing the MgO content from about 4.5% to about 0.45%.
  • current boron and fluorine containing E-glass versions with less than about 1 % MgO belong to the quaternary, Si0 2 , AI 2 O 3 , CaO, B 2 0 3 phase diagram, since such small amounts of MgO are not deliberately added but brought into the melt as impurities.
  • boron levels of over 2 wt% and any amount of fluorine present in a glass fiber composition could pose an environmental concern and that fluorine free and low level boron compositions, i.e.
  • compositions of no greater than 2 wt% boron would be preferred in order to meet the needs of the society into the twenty-first century.
  • the effort to achieve compliance with future needs was met by a return to the original boron free quaternary Si0 2 -AI 2 0 3 -CaO-MgO system but modifying it to achieve the required ⁇ T without the beneficial effect of boron.
  • Quaternary compositions of this kind are disclosed in U.S. Patent Nos. 4,542,106 and 5,789,329. These glass compositions met the desired ⁇ T condition, but had a forming temperature at least 100°F greater than earlier produced boron and fluorine free E-glass compositions.
  • the liquidus temperature and therefore the forming temperature required to maintain the desired ⁇ T, can be reduced in the quaternary SiO 2 -AI 2 O 3 -CaO-MgO by optimizing the amounts of each of these principle constituents.
  • such modifications facilitate an up to 50°F reduction in the liquidus temperature
  • small amounts of liquidus temperature reducing materials such as but not limited to B 2 0 3 , Li 2 0, ZnO, MnO and/or Mn0 2 (up to 2 wt%), facilitates a total reduction in liquidus temperature by over 50°F.
  • compositions are essentially modifications of the quaternary SiO 2 -AI 2 O 3 -CaO-MgO system and offer forming temperatures which are 50-100°F above that of borosilicate E-glass.
  • borosilicate E-glass means quinary Si0 2 -Al 2 0 3 - CaO-MgO-B 2 0 3 system and quaternary Si0 2 -AI 2 0 3 -CaO-B 2 O 3 system E-glass compositions as discussed above that include silica as the major constituent, greater than 2 wt% boron, in the form of B 2 O 3 and up to about 4.5 wt% MgO.
  • These glasses have a forming temperature generally ranging from 2100 to 2200°F (1149 to 1204°C) and a liquidus temperature generally ranging from 1970 to 2040°F (1077 to 1116°C).
  • the dominant boron and fluorine containing E-glass compositions are based on either the essentially quaternary Si0 2 -AI 2 0 3 -CaO-B 2 0 3 system or the essentially quinary SiO 2 -AI 2 0 3 -CaO-MgO-B 2 0 3 system, and the emerging fluorine free and essentially boron free E-glass compositions, according to the same ASTM standard, are based on the essentially quaternary SiO 2 -AI 2 O 3 -CaO- MgO system.
  • HS-glass fibers commonly designated as high strength (HS-) fibers can be derived from compositions in the ternary or essentially ternary SiO 2 -AI 2 0 3 -CaO phase diagram, but they require forming temperatures which are 400-500°F higher than that of conventional borosilicate E-glass.
  • HS-glass fibers are premium items of commerce and are aimed at specialty markets requiring high strength, high in-use temperatures, and/or low dielectric constants for premium applications, e.g. printed circuit board in a high temperature environment.
  • the present invention provides a glass fiber composition
  • a glass fiber composition comprising: 55 to 63 percent by weight Si0 2 ; 22 to 26 percent by weight CaO; 12 to 16 percent by weight AI 2 O 3 ; 0 to 1 percent by weight MgO; 0.05 to 0.80 percent by weight Fe 2 0 3 ; 0 to 2 percent by weight Na 2 O; 0 to 2 percent by weight K 2 0; 0 to 2 percent by weight TiO 2 ; 0 to 2 percent by weight BaO; 0 to 2 percent by weight Zr0 2 ; andO to 2 percent by weight SrO, and at least one material selected from the group consisting of: 0.05 to 2 percent by weight B 2 0 3 ; 0.05 to 2 percent by weight Li 2 0; 0.05 to 2 percent by weight ZnO; 0.05 to 2 percent by weight MnO; and ⁇ .05 to 2 percent by weight MnO 2 .
  • the glass composition has a forming temperature of no greater than 2300°F based on an NIST 717A reference standard, a liquidus temperature of no greater than 2160°F, a ratio of SiO 2 to RO of no greater than 2.65, and a ⁇ T of at least 65°F.
  • the ternary or essentially ternary SiO 2 -AI 2 0 3 -CaO compositions of the present invention are formulated to provide only moderately higher forming and liquidus temperatures as compared to those observed with conventional borosilicate E-glass fibers, and more specifically a relatively low eutectic liquidus temperature, e.g. about 2140°F (1171 °C).
  • the Si0 2 -AI 2 0 3 -CaO ternary system of the present invention is essentially free of MgO, i.e. the composition contains no greater than 1 percent by weight MgO.
  • a glass fiber composition with this liquidus temperature and a ⁇ T of at least 100°F would in effect have a forming temperature that is only about 100°F to 150°F (56°C to 83°C) higher than that of typical commercially produced borosilicate E-glass. Given this assumption, its forming temperature would be comparable to that of the fluorine free and essentially boron free quaternary Si0 2 -AI 2 0 3 -CaO-MgO E-glass compositions discussed earlier.
  • Preferred ternary Si0 2 -AI 2 0 3 -CaO compositions of this invention are not only useful as reinforcements for composites but, as discussed earlier, should also provide superior substrates for printed wiring boards because it is believed that they should offer a low dielectric constant K, in combination with a low liquidus temperature and a ⁇ T of at least 100°F. More specifically, E- glass is the currently preferred high-volume low-cost reinforcement for use in the printed wiring board market.
  • this composition is based on an inexpensive essentially quaternary SiO 2 -AI 2 O 3 -CaO-B 2 O 3 system or essentially quinary Si0 2 -AI 2 0 3 -CaO-MgO-B 2 O 3 system, as discussed above, and has a dielectric constant of about 6.11 at 10 10 Hz.
  • D glass an essentially CaO and Al 2 0 3 free glass fiber and, e.g.
  • containing about 74 wt% Si0 2 and about 22 wt% B 2 0 3 has a dielectric constant of about 3.56 at 10 10 Hz
  • S-glass a ternary SiO 2 -AI 2 0 3 -MgO glass fiber, free of trace oxides
  • S-glass has a dielectric constant of about 4.53 at 10 10 Hz (see, Wallenberger at page 150). Because of their low dielectric constant, both D-glass and S- glass afford premium performance in printed circuit boards but at a premium price.
  • Ternary glass fiber compositions of the present invention are believed to have a dielectric constant less than conventional borosilicate glass as well as less than the fluorine and boron free glass discussed earlier.
  • a ternary or essentially ternary SiO 2 -AI 2 0 3 -CaO glass fiber is expected to offer the dielectric properties comparable to that of D-glass and S-glass but at much lower forming temperatures and at a lower cost.
  • glass fibers of the present invention can be prepared in the conventional manner well known in the art, by blending the raw materials used to supply the specific oxides that form the composition of the fibers.
  • typically sand is used for SiO 2 , clay for AI 2 O 3 , and lime or limestone for CaO.
  • the glass compositions disclosed herein can also include small amounts of other materials, for example melting and refining aids, tramp materials or impurities.
  • melting and fining aids such as SO 3
  • the present invention also contemplates the inclusion of other materials in the glass fiber compositions, as will be discussed later in more detail.
  • small amounts of the materials discussed above can enter the glass composition as tramp materials or impurities included in the raw materials of the main constituents.
  • the batch is melted in a conventional glass fiber melting furnace and the resulting molten glass is passed along a conventional forehearth and into a glass fiber forming bushing located along the bottom of the forehearth, as is well known to those skilled in the art.
  • the glass is typically heated to a temperature of at least 2550°F ( 1 400°C).
  • the molten glass is then drawn or pulled through a plurality of holes in the bottom of the bushing.
  • the streams of molten glass are attenuated to filaments by winding a strand of filaments on a forming tube mounted on a rotatable collet of a winding machine.
  • the fiber forming apparatus can be, for example, a forming device for synthetic textile fibers or strands in which fibers are drawn from nozzles, such as but not limited to a spinneret, as is known to those skilled in the art.
  • Typical forehearths and glass fiber forming arrangements are shown in Loewenstein at pages 85-1 07 and pages 1 1 5-1 35, which are hereby incorporated by reference.
  • Tables 1-3 show laboratory examples of ternary and essentially ternary Si0 2 -AI 2 0 3 -CaO glass fiber compositions of the present invention.
  • the glass fiber compositions were prepared from reagent grade oxides (e.g., pure silica or calcia). The batch size for each example was 1000 grams.
  • the individual batch ingredients were weighed out, combined and placed in a tightly sealed jar. The sealed jar was then placed in a paint shaker for 15 minutes to effectively mix the ingredients. A portion of the batch was then place into a platinum crucible, filling no more than 3/4 of its volume. The crucible was then placed in a furnace and heated to 2600°F (1425°C) for 15 minutes. The remaining batch was then added to the hot crucible and heated to 2600°F (1425°C) for 15 to 30 minutes. The furnace temperature was then raised to 2700°F (1482°C) and held there for 4 hours. The molten glass was then fritted in water and dried. Where indicated, the forming temperature, i.e.
  • the glass temperature at a viscosity of 1000 poise was determined by ASTM method C965-81 , and the liquidus temperature by ASTM method C829-81.
  • the weight percent of the constituents of the compositions shown in Tables 1-3 are based on the weight percent of each constituent in the batch. It is believed that the batch weight percent is generally about the same as the weight percent of the melted sample, except for glass batch materials that volatilize during melting, e.g. boron and fluorine. For boron, it is believed that the weight percent of B 2 0 3 in a laboratory samples will be 5 to 10 percent less than the weight percent of B 2 0 3 in the batch composition.
  • the weight percent of fluorine in a lab melt will be about 50 percent less than the weight percent of fluorine in the batch composition. It is further believed that glass fiber compositions made from commercial grade materials and melted under conventional operating conditions will have similar batch and melt weight percents as discussed above, except that the batch and melt weight percents for the volatile components of the composition will actually be closer to each other than the batch and melt wt% of the laboratory melts because in a conventional melting operation, the materials are exposed to the high melting temperatures for less time than the 4 hours of exposure for the laboratory melts.
  • Si0 2 /RO is the ratio of the silica content of the batch, expressed as Si0 2 , to the sum of the calcia and magnesia content, expressed as CaO and MgO, respectively.
  • This ternary Si0 2 -AI 2 0 3 -CaO composition would be very attractive by itself. However this composition exhibits a sharp minimum in the phase diagram surrounded by much higher liquidus temperatures on either side of the composition, and it is a only a fraction of a percentage point removed from such higher liquidus temperature, and therefore implicitly much higher forming temperatures also. While the ⁇ T this specific composition might be satisfactory in a laboratory process, in a typical commercial process the sensitivity toward compositional changes is high and would not well tolerate inevitable temperature and compositional changes. It should be appreciated that derivatives of the ternary glass fiber compositions of the present invention, i.e.
  • essentially ternary compositions can include small amounts of additives that will lower the liquidus temperature and broaden the liquidus temperature range so as to facilitate formation of fibers with a low liquidus temperature and a ⁇ T of at least 100°F.
  • additives include, but are not limited to B 2 O 3 , Li 2 0, ZnO, MnO and/or MnO 2 .
  • the glass composition includes 0.05 to 2 wt% of at least one of these additives, and preferably no greater than 1 wt.
  • the glass composition includes 0.05 to 2 wt% each of two or more of these materials, and preferably no greater than 1 wt% each.
  • the present invention also contemplates the inclusion of other materials in the glass fiber compositions such as, but not limited to, 0 to 2 wt% each of Ti0 2 , BaO, ZrO 2 , NaO, K 2 O and SrO, and preferably no greater than 1 wt% each of these materials.
  • the glass fiber composition can also include small amounts of refining aids or tramp materials that enter the glass composition as impurities in the glass batch materials, as discussed earlier.
  • the glass compositions of the present invention typically include 0.05 to 0.80 wt% Fe 2 0 3 as a refining aid, and preferably up to 0.5 wt%.
  • Table 2 shows essentially ternary compositions of the present invention that further include the addition of minor constituents.
  • selected examples in Table 2 include a forming temperature.
  • the determination of T F0RM was based on the glass samples being compared against physical standards supplied by the National Institute of Standards and Testing (NIST). In Tables 2 and 3, T F0RM is reported based on using NIST 717A which is a borosilicate glass standard. Although not used herein, it is believed that NIST 714, which is a soda lime glass standard, provides a more accurate measure of the forming temperature.
  • the forming temperature (and thus ⁇ T) of the examples shown in Table 2 based on the NIST 714 standard reference will be 20°F to 25°F (11°C to 16°C) higher than the forming temperature as reported based on the NIST 717A reference standard.
  • the liquidus temperature is not affected by the choice of reference standard.
  • Examples 14-16 have ⁇ Ts between 176°F and 210°F (98°C to 1 17°C) at an Si0 2 /RO ratio of 2.66-2.67, and Examples 17-19 have ⁇ Ts between 23°F and 50°F (13°C to 28°C) at an Si0 2 /RO ratio of 2.43.
  • ⁇ T should be maintained in a range sufficient to prevent devitrification of the molten glass in the bushing area of a glass fiber forming operation and stagnant areas of the glass melting furnace.
  • ⁇ T should be at least 65°F (36°C), preferably at least 90°F (50°C), and more preferably at least 1 00°F (56°C).
  • the amounts of SiO 2 and CaO can be modified to change the forming temperature and provide a desired ⁇ T. More specifically, reducing the silica content while simultaneously maintaining or increasing the calcia content (thus reducing Si0 2 /RO ratio) will reduce the forming temperature and thus reduce ⁇ T.
  • This type of modification would be of value if, for example, ⁇ T was much greater than 100°F, as in Ex. 14-16, and could be reduced without adversely affecting the glass melting and forming operation. Conversely, increasing the silica content and while simultaneously maintaining or reducing the calcia content (thus increasing the Si0 2 /RO ratio) will raise the forming temperature and thus increase ⁇ T. This type of modification would be of value if, for example, ⁇ T was too low and had to be increased to at least 100°F, as in Ex. 17-19. Compositional adjustments of silica and/or calcia (and the Si0 2 /RO ratio) in either direction are possible until the ⁇ T is obtained that is deemed to facilitate the pursuit of a safe industrial melt forming process.
  • the ternary glass fiber compositions of the present invention have a base glass composition comprising 55 to 63 weight percent SiO 2 , 22 to 26 weight percent CaO, 12 to 16 weight percent AI 2 O 3 , and preferably 55 to 59 weight percent Si0 2 , 22 to 24 weight percent CaO, and 12 to 14 weight percent AI 2 O 3 .
  • the glass composition also includes no greater than 1 wt% MgO, and preferably no greater than 0.6 wt% MgO.
  • the glass composition further includes 0.05 to 2 weight percent of at least one of the following additives: B 2 0 3 , Li 2 0, ZnO, MnO and/or Mn0 2 , and in nonlimiting embodiment, the glass composition includes 0.05 to 2 wt% each of two or more of these additives. In another nonlimiting embodiment of the invention, the glass composition includes no greater than 1 wt% of at least one of these additives. In another nonlimiting embodiment of the invention, the glass compositions further include 0 to 2 wt% each of Ti0 2 , BaO, ZrO 2 ,Na 2 O, K 2 O and SrO, and preferably no greater than 1 wt% each of these materials. In addition, because of the environmental concerns discussed earlier, although not limiting in the present invention, the glass compositions are preferably low fluorine compositions, and more preferably are fluorine-free.
  • the forming temperature of the glass compositions of the present invention should be no greater than 2300°F (1260°C), and preferably no greater than 2250°F (1232°C), and more preferably no greater than 2220°F (1216°C), based on the NIST 717A reference standard.
  • the liquidus temperature of the glass compositions should be no greater than 2160°F (1182°C), and preferably no greater than 2150°F (1177°C), and more preferably no greater than 2140°F (1171°C).
  • the Si0 2 /RO ratio can be manipulated to achieve the goals of lowering the overall processing temperature, and in particular lowering the forming temperature, while providing a ⁇ T required to facilitate continuous fiber processing.
  • the glass fiber compositions of the present invention have a SiO 2 /RO ratio of no greater than 2.65, preferably no greater than 2.60, and more preferably no greater than 2.55.
  • compositions with a ⁇ T having been properly adjusted to facilitate continuous processing of glass fibers are of great potential commercial utility as reinforcement for composites. It is believed that these compositions will provide good mechanical properties and a low dielectric constant, which is particularly advantageous for applications such as, but not limited to, printed wiring boards

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Glass Compositions (AREA)

Abstract

La présente invention concerne une composition de fibres de verre comprenant: de 55 à 63 % en poids de SiO2; de 22 à 26 % en poids de CaO; de 12 à 16 % en poids de Al2O3; de 0 à 1 % en poids de MgO; de 0,05 à 0,80 % en poids de Fe2O3; de 0 à 2 % en poids de Na2O; de 0 à 2 % en poids de K2O; de 0 à 2 % en poids de TiO2; de 0 à 2 % en poids de BaO; de 0 à 2 % en poids de ZrO2; et de 0 à 2 % en poids de SrO, ainsi qu'au moins un matériau sélectionné dans le groupe comprenant: 0,05 à 2 % en poids de B2O3; de 0,05 à 2 % en poids de Li2O; de 0,05 à 2 % en poids de ZnO; de 0,05 à 2 % en poids de MnO; et de 0,05 à 2 % en poids de MnO2. Dans une forme d'exécution à caractère non limitatif, cette composition de verre présente aqueuses une température de formage inférieure ou égale à 2300 °F par rapport à la norme NIST 717A, une température du liquidus inférieure ou égale à 2160 °F, un rapport SiO2/RO inférieur ou égal à 2,65, et un ΔT d'au moins 65 °F.
EP00932752A 1999-05-27 2000-05-23 Composition de fibres de verre Withdrawn EP1187793A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US13628099P 1999-05-27 1999-05-27
US136280P 1999-05-27
PCT/US2000/014263 WO2000073232A1 (fr) 1999-05-27 2000-05-23 Composition de fibres de verre

Publications (1)

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EP1187793A1 true EP1187793A1 (fr) 2002-03-20

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EP00932752A Withdrawn EP1187793A1 (fr) 1999-05-27 2000-05-23 Composition de fibres de verre

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EP (1) EP1187793A1 (fr)
JP (1) JP2003505318A (fr)
CA (1) CA2375015A1 (fr)
WO (1) WO2000073232A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2867776B1 (fr) * 2004-03-17 2006-06-23 Saint Gobain Vetrotex Fils de verre aptes a renforcer des matieres organiques et/ou inorganiques
CN101503279B (zh) * 2009-03-02 2012-04-11 巨石集团有限公司 一种新型玻璃纤维组合物
TWI392658B (zh) * 2009-06-24 2013-04-11 Glass fiber composition
CN102010134A (zh) * 2010-11-15 2011-04-13 巨石集团有限公司 一种玻璃纤维组合物
EP2956420B1 (fr) * 2013-02-18 2018-07-18 AS Valmieras Stikla Skiedra Fibre de verre d'aluminosilicate thermorésistante et procédé de production et d'utilisation de celle-ci
JP7303486B2 (ja) * 2019-05-10 2023-07-05 日本電気硝子株式会社 ガラス繊維用ガラス組成物
CN110606665B (zh) * 2019-09-25 2020-11-17 巨石集团有限公司 一种电子级玻璃纤维组合物及其玻璃纤维和电子布
CN115304284B (zh) * 2022-09-09 2023-07-25 中国建筑材料科学研究总院有限公司 一种用于光纤传像元件的低折射率皮层玻璃及其制备方法

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Publication number Priority date Publication date Assignee Title
US4542106A (en) * 1983-12-19 1985-09-17 Ppg Industries, Inc. Fiber glass composition
JPS63225552A (ja) * 1987-03-13 1988-09-20 Nitto Boseki Co Ltd 繊維用紫外線吸収ガラス組成物
FR2692248B1 (fr) * 1992-06-16 1995-08-04 Vetrotex France Sa Fibres de verre resistant au milieu acide.
RU2027687C1 (ru) * 1992-12-28 1995-01-27 Александр Иванович Фокин Стекло для стекловолокна
EP0832046B1 (fr) * 1995-06-06 2000-04-05 Owens Corning Fibres de verre sans bore
FR2768144B1 (fr) * 1997-09-10 1999-10-01 Vetrotex France Sa Fils de verre aptes a renforcer des matieres organiques et/ou inorganiques

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Also Published As

Publication number Publication date
CA2375015A1 (fr) 2000-12-07
JP2003505318A (ja) 2003-02-12
WO2000073232A1 (fr) 2000-12-07

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