JPH02268821A - Production of hollow fiber membrane of polysulfone - Google Patents
Production of hollow fiber membrane of polysulfoneInfo
- Publication number
- JPH02268821A JPH02268821A JP9108189A JP9108189A JPH02268821A JP H02268821 A JPH02268821 A JP H02268821A JP 9108189 A JP9108189 A JP 9108189A JP 9108189 A JP9108189 A JP 9108189A JP H02268821 A JPH02268821 A JP H02268821A
- Authority
- JP
- Japan
- Prior art keywords
- polysulfone
- water
- hollow fiber
- fiber membrane
- spinning
- 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.)
- Granted
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 27
- 229920002492 poly(sulfone) Polymers 0.000 title claims abstract description 23
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000009987 spinning Methods 0.000 claims abstract description 11
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000011550 stock solution Substances 0.000 claims description 2
- 238000001891 gel spinning Methods 0.000 claims 2
- 239000011148 porous material Substances 0.000 abstract description 12
- 230000035699 permeability Effects 0.000 abstract description 10
- 239000012633 leachable Substances 0.000 abstract 2
- 238000002386 leaching Methods 0.000 abstract 1
- 238000002166 wet spinning Methods 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 7
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- -1 glycerin fatty acid esters Chemical class 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000578 dry spinning Methods 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000012854 evaluation process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Artificial Filaments (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、ポリスルホン中空糸膜の製造方法に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to a method for manufacturing polysulfone hollow fiber membranes.
更に詳しくは、透水性にすぐれたポリスルホン中空糸膜
の製造方法に関する。More specifically, the present invention relates to a method for producing a polysulfone hollow fiber membrane with excellent water permeability.
現在、分離膜用に採用されている素材の中では、耐熱性
、耐薬品（酸、アルカリ）性にすぐれたポリスルホン樹
脂が多く用いられている。ポリスルホン樹脂から製造さ
れた中空糸は、中空糸の外側あるいは内側のいずれか一
方あるいは両方に緻密層が存在し、膜内部には空孔率の
高いフィンガースドラクチャ−が形成された構造を有し
ているが、−設面に透水性は低く、透水速度として５０
０ Ｑ １ｍ”・Ｋｇ／ａＪ−ｈｒ以下の値を示すにす
ぎない。このため、膜厚を小さくするなどして透水性を
高めようとすると、今度は耐圧性が低くなるため実用性
に欠けるようになる。Among the materials currently being used for separation membranes, polysulfone resin is often used due to its excellent heat resistance and chemical (acid, alkali) resistance. Hollow fibers made from polysulfone resin have a structure in which a dense layer exists on either the outside or inside of the hollow fiber, or both, and fingers structures with high porosity are formed inside the membrane. However, the water permeability of the construction surface is low, and the water permeation rate is 50%.
0 Q 1m"・Kg/aJ-hr or less. Therefore, if you try to increase water permeability by reducing the membrane thickness, the pressure resistance will decrease and it will be impractical. It becomes like this.
そこで、耐圧性を保持したまま、換言すれば必要な膜厚
を維持しながら透水性を左右する親水性を高めるために
、製膜後エタノール中に浸漬する方法、膜表面（膜内部
の細孔表面を含む）にグリセリンや比較的親水性の高い
界面活性剤を吸着させる方法、グラフト化、スルホン化
などの化学的表面改質方法など種々の方法が提案されて
いるが、エタノール中への浸漬、グリセリン、界面活性
剤の吸着などの改善処理法は効果の持続性に欠け、また
化学的表面改質法は工程が複雑になり、コスト増も避け
られない。Therefore, in order to increase the hydrophilicity, which affects water permeability, while maintaining pressure resistance, or in other words, maintaining the required film thickness, we have developed a method of immersing the membrane in ethanol after film formation, and a method of immersing the membrane surface (inside the pores inside the membrane). Various methods have been proposed, including methods for adsorbing glycerin or relatively highly hydrophilic surfactants on the surface (including the surface), and chemical surface modification methods such as grafting and sulfonation. Improvement treatment methods such as adsorption of glycerin, surfactants, etc. lack long-lasting effects, and chemical surface modification methods require complicated processes and inevitably increase costs.
本発明の目的は、透水性ならびにその持続性にすぐれた
ポリスルホン中空糸膜の製造方法を提供することにある
。An object of the present invention is to provide a method for producing a polysulfone hollow fiber membrane with excellent water permeability and durability.
かかる本発明の目的は、親水性を有しかつ水に溶出し難
い非イオン性界面活性剤を添加したポリスルホン紡糸原
液を乾湿式紡糸、好ましくは低級アルコールまたはその
水溶液を芯液として乾湿式紡糸することにより達成され
る。The object of the present invention is to perform wet-dry spinning using a polysulfone spinning dope to which a nonionic surfactant that is hydrophilic and difficult to dissolve in water is added, preferably using a lower alcohol or an aqueous solution thereof as a core liquid. This is achieved by
ポリスルホンは、これをジメチルホルムアミド、ジエチ
ルホルムアミド、ジメチルアセトアミド、ジエチルアセ
トアミド、ジメチルスルホキシド、Ｎ−メチル−２−ピ
ロリドン、トリエチルホスフェートなどの有機溶媒に溶
解させて調製した濃度約１０〜３０重量％の紡糸原液（
ドープ液）として用いられる。Polysulfone is a spinning stock solution with a concentration of about 10 to 30% by weight prepared by dissolving it in an organic solvent such as dimethylformamide, diethylformamide, dimethylacetamide, diethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, or triethylphosphate. (
used as a dope solution).
この紡糸原液中には、原液の溶媒和効果、増粘効果など
を増大させる変性剤としてのポリエチレングリコールな
どが添加されるが１本発明においては、このような変性
剤が一般に用いられるものの、更に親水性を有しかつ水
に溶出し雅い非イオン性界面活性剤が必須成分として添
加される。Polyethylene glycol and the like are added to this spinning dope as a modifier that increases the solvation effect, thickening effect, etc. of the dope.1 In the present invention, although such modifiers are generally used, A nonionic surfactant that is hydrophilic and easily dissolves in water is added as an essential ingredient.
かかる界面活性剤としては、食品添加物の界面活性剤と
しても用いられているグリセリン脂肪酸エステル、ソル
ビタン脂肪酸エステルなどが好んで用いられるが、この
他にもしよ糖脂肪酸エステル、プロピレングリコール脂
肪酸エステルなどの高級脂肪酸エステル基を疎水性基と
して有するものなどが用いられる。As such surfactants, glycerin fatty acid esters, sorbitan fatty acid esters, etc., which are also used as surfactants in food additives, are preferably used, but in addition, sucrose fatty acid esters, propylene glycol fatty acid esters, etc. Those having a higher fatty acid ester group as a hydrophobic group are used.
これらの界面活性剤は、親水性を有しているので、形成
された膜表面（膜内部の細孔表面を含む）に親水性を付
与する。このため、界面活性剤はポリスルホン樹脂に対
して約５〜３０重量２、好ましくは約１０〜３０重量メ
の割合で添加して用いられる。Since these surfactants have hydrophilicity, they impart hydrophilicity to the surface of the formed membrane (including the surface of pores inside the membrane). Therefore, the surfactant is added in an amount of about 5 to 30 weights, preferably about 10 to 30 weights, based on the polysulfone resin.
添加割合がこれより少ないと、所期の親水性付与効果が
発揮されず、一方これより多い割合で添加すると、親水
性効果は十分に発揮されるものの、界面活性剤が余分に
存在することにより細孔径が小さくなり、孔径の微小化
、透水性の低下を招くようになり、また水の口過初期に
界面活性剤が溶出してくる可能性がある。If the addition ratio is lower than this, the desired hydrophilicity imparting effect will not be exhibited, while if the addition ratio is higher than this, although the hydrophilic effect will be sufficiently exhibited, due to the presence of excess surfactant. The pore size becomes smaller, leading to miniaturization of the pore size and lowering of water permeability, and the surfactant may be eluted at the early stage of water permeation.
このような余分な界面活性剤を除去するために、紡糸時
に芯液として低級アルコール、好ましくはエタノールを
用いることにより、紡糸された中空糸膜の洗浄と同時に
不必要な界面活性剤が洗い流される。また、芯液にエタ
ノールを用いることは、中空糸膜内側表面に孔径的０．
０１〜０．２μ墓という比較的大きな孔を開けるのに有
効である。この孔径をｉＪｌさくしようとする場合には
、低級アルコールをその水溶液、一般には濃度が約５０
重量％以上の水溶液として用いることもできる。In order to remove such excess surfactant, by using a lower alcohol, preferably ethanol, as a core liquid during spinning, unnecessary surfactant is washed away simultaneously with cleaning the spun hollow fiber membrane. Moreover, using ethanol as the core liquid means that the inner surface of the hollow fiber membrane has a pore diameter of 0.
It is effective for making relatively large holes of 01 to 0.2 μm. When attempting to reduce this pore size by iJl, a lower alcohol is added to its aqueous solution, generally at a concentration of about 50%.
It can also be used as an aqueous solution containing more than % by weight.
乾湿式紡糸は１通常の方法および条件に従って行われる
。Wet-dry spinning is carried out according to conventional methods and conditions.
本発明方法によれば、形成されたポリスルホン中空糸膜
中に親水性を有しかつ水に溶出し難い非イオン性界面活
性剤が含有されているため、エタノール浸漬による親水
性処理を行わなくとも、その膜表面に恒久的な親水性が
付与され、更にそこに含有される界面活性剤は、紡糸時
に芯液として低級アルコールを用いて洗浄した場合には
通水初期に余分な溶出分がなく、孔径が不必要に小さく
ならないため通水性は一段と向上する。また、芯液のア
ルコールを水溶液として用い、その濃度を種々に変更す
ることにより、細孔径の調節も可能である。According to the method of the present invention, since the formed polysulfone hollow fiber membrane contains a nonionic surfactant that is hydrophilic and difficult to dissolve in water, it is not necessary to perform hydrophilic treatment by immersion in ethanol. , permanent hydrophilicity is imparted to the surface of the membrane, and the surfactant contained therein eliminates excess elution during the initial water flow when cleaning with lower alcohol as the core liquid during spinning. Since the pore diameter does not become unnecessarily small, water permeability is further improved. In addition, the pore diameter can be adjusted by using the core liquid alcohol as an aqueous solution and varying its concentration.
得られたポリスルホン中空糸膜は、一般に約０．０１〜
０．２μｍの細孔径を有する精密口過膜として、あるい
は分画分子量的５０００〜１，０００，０００の限外口
過膜などとして、有効に使用することができる。The resulting polysulfone hollow fiber membrane generally has a
It can be effectively used as a precision filtration membrane having a pore diameter of 0.2 μm or as an ultrafiltration membrane having a molecular weight cut-off of 5,000 to 1,000,000.
次に、実施例について本発明を説明する。 Next, the present invention will be explained with reference to examples.
比較例
ポリスルホン１３重量部、ポリエチレングリコール（分
子量的６０００） １０重量部およびジメチルホルムア
ミド７７重量部からなる紡糸原液を内径０．３ｍｍ、外
径０．５＋ａ＋ａの環状吐出部から、また７５重量ｒジ
メチルホルムアミド水溶液を直径０．１２ｍｍの円形吐
出部からそれぞれ吐出させ、この環状ノズル面から１０
ｃｍ下に水面が位置する水凝固浴（２０℃）中に浸漬ゲ
ル化せしめ、水洗した後、８０℃で乾燥した。Comparative Example A spinning dope consisting of 13 parts by weight of polysulfone, 10 parts by weight of polyethylene glycol (molecular weight 6000) and 77 parts by weight of dimethylformamide was fed from an annular discharge part with an inner diameter of 0.3 mm and an outer diameter of 0.5+a+a, and 75 parts by weight of dimethylformamide. The aqueous solution is discharged from each circular discharge part with a diameter of 0.12 mm, and 10
The gel was gelled by immersion in a water coagulation bath (20° C.) with the water surface located 1 cm below the surface, washed with water, and then dried at 80° C.
得られたこのポリスルホン中空糸膜は、平均細孔径が約
０．０１μ厘で、これはそのままでは水を透過しないの
で、エタノール浸漬した後透水速度を測定すると、外径
基準で３２００ Ｑ ／ｒｓ” ・Ｋｇ／ｃｍ” ・ｈ
ｒの値が得られた。The obtained polysulfone hollow fiber membrane has an average pore diameter of approximately 0.01 μm, which does not allow water to pass through as it is, so when the water permeation rate was measured after being immersed in ethanol, it was 3200 Q/rs based on the outer diameter.・Kg/cm"・h
The value of r was obtained.
実施例１
比較例において、更にグリセリン高級脂肪酸エステル２
重量部を添加した紡糸原液を用いると、得られたポリス
ルホン中空糸膜は、エタノール浸漬による親水化処理な
しで、外径基準で３８０００ ／ｓ＋”・Ｋｇ、１ｃｍ
２・ｈｒの透水速度を示した。Example 1 In the comparative example, further glycerin higher fatty acid ester 2
When using a spinning dope containing 100% by weight, the obtained polysulfone hollow fiber membrane has an outer diameter of 38000/s+"・Kg, 1cm without hydrophilic treatment by immersion in ethanol.
It showed a water permeation rate of 2.hr.
実施例２ 実施例１において、芯液をエタノールに変更した。Example 2 In Example 1, the core liquid was changed to ethanol.
得られたポリスルホン中空糸膜は、平均細孔径が約０．
０１μｍで、これを親水化処理することなく、そのまま
の状態で透水速度を測定すると、外径基準で５０００Ｑ
／１１２・Ｋｇ／ｃＩｍ２・ｈｒの値を示した。The obtained polysulfone hollow fiber membrane has an average pore diameter of about 0.
01μm, and when the water permeation rate was measured as it was without any hydrophilic treatment, it was 5000Q based on the outer diameter.
/112·Kg/cIm2·hr.
また、このポリスルホン中空糸膜は、口過、乾燥をくり
返しても、その効果を維持していることが確認された。It was also confirmed that this polysulfone hollow fiber membrane maintained its effectiveness even after repeated rinsing and drying.
即ち５この膜を５０℃で２４時間乾燥した後、再度通水
評価したところ、透水速度は初期とほぼ同じであった。That is, 5. After drying this membrane at 50° C. for 24 hours, the water permeation rate was evaluated again, and the water permeation rate was almost the same as that at the initial stage.
更に、このような通水評価と乾燥のくり返しを３回目迄
行っても、透水速度は初期の９６％以上に保たれており
、はぼ恒久的な親水化処理がなされたことが確認された
。Furthermore, even after repeating this water permeation evaluation and drying process up to the third time, the water permeability rate was maintained at 96% or more of the initial value, confirming that a permanent hydrophilic treatment had been achieved. .
Claims (1)
性剤を添加したポリスルホン紡糸原液を乾湿式紡糸する
ことを特徴とするポリスルホン中空糸膜の製造方法。 ２、親水性を有しかつ水に溶出し難い非イオン性界面活
性剤を添加したポリスルホン紡糸原液を、低級アルコー
ルまたはその水溶液を芯液として乾湿式紡糸することを
特徴とするポリスルホン中空糸膜の製造方法。[Scope of Claims] 1. A method for producing a polysulfone hollow fiber membrane, which comprises dry-wet spinning a polysulfone spinning dope to which a nonionic surfactant that is hydrophilic and difficult to dissolve in water is added. 2. A polysulfone hollow fiber membrane characterized in that a polysulfone spinning stock solution containing a nonionic surfactant that is hydrophilic and difficult to dissolve in water is subjected to dry-wet spinning using a lower alcohol or an aqueous solution thereof as a core liquid. Production method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1091081A JP2803142B2 (en) | 1989-04-11 | 1989-04-11 | Method for producing polysulfone hollow fiber membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1091081A JP2803142B2 (en) | 1989-04-11 | 1989-04-11 | Method for producing polysulfone hollow fiber membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02268821A true JPH02268821A (en) | 1990-11-02 |
| JP2803142B2 JP2803142B2 (en) | 1998-09-24 |
Family
ID=14016565
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1091081A Expired - Fee Related JP2803142B2 (en) | 1989-04-11 | 1989-04-11 | Method for producing polysulfone hollow fiber membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2803142B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107754618A (en) * | 2017-08-28 | 2018-03-06 | 杭州水处理技术研究开发中心有限公司 | A kind of preparation method of novel lasting hydrophily polysulphone super-filter membrane |
| CN113648842A (en) * | 2021-08-23 | 2021-11-16 | 苏州中色德源环保科技有限公司 | Polyether sulfone hollow fiber membrane aperture adjusting method applied to material separation |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61107909A (en) * | 1984-11-01 | 1986-05-26 | Sumitomo Bakelite Co Ltd | Manufacture of hollow fibrous separation film |
-
1989
- 1989-04-11 JP JP1091081A patent/JP2803142B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61107909A (en) * | 1984-11-01 | 1986-05-26 | Sumitomo Bakelite Co Ltd | Manufacture of hollow fibrous separation film |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107754618A (en) * | 2017-08-28 | 2018-03-06 | 杭州水处理技术研究开发中心有限公司 | A kind of preparation method of novel lasting hydrophily polysulphone super-filter membrane |
| CN113648842A (en) * | 2021-08-23 | 2021-11-16 | 苏州中色德源环保科技有限公司 | Polyether sulfone hollow fiber membrane aperture adjusting method applied to material separation |
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| JP2803142B2 (en) | 1998-09-24 |
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