JP6358711B2 - 電気化学セルのためのセパレーター材料 - Google Patents
電気化学セルのためのセパレーター材料 Download PDFInfo
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- JP6358711B2 JP6358711B2 JP2015542710A JP2015542710A JP6358711B2 JP 6358711 B2 JP6358711 B2 JP 6358711B2 JP 2015542710 A JP2015542710 A JP 2015542710A JP 2015542710 A JP2015542710 A JP 2015542710A JP 6358711 B2 JP6358711 B2 JP 6358711B2
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- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
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- 229920002313 fluoropolymer Polymers 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical group [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229920004889 linear high-density polyethylene Polymers 0.000 description 2
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- 238000012545 processing Methods 0.000 description 2
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- JMMZCWZIJXAGKW-UHFFFAOYSA-N 2-methylpent-2-ene Chemical compound CCC=C(C)C JMMZCWZIJXAGKW-UHFFFAOYSA-N 0.000 description 1
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- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
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- 229920000578 graft copolymer Polymers 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
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- 229910000483 nickel oxide hydroxide Inorganic materials 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
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- 238000010998 test method Methods 0.000 description 1
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- SZKTYYIADWRVSA-UHFFFAOYSA-N zinc manganese(2+) oxygen(2-) Chemical compound [O--].[O--].[Mn++].[Zn++] SZKTYYIADWRVSA-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
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- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/005—Synthetic yarns or filaments
- D04H3/009—Condensation or reaction polymers
- D04H3/011—Polyesters
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/02—Heat treatment
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/11—Flash-spinning
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/724—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged forming webs during fibre formation, e.g. flash-spinning
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
- D04H3/16—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between thermoplastic filaments produced in association with filament formation, e.g. immediately following extrusion
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
- D04H3/16—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between thermoplastic filaments produced in association with filament formation, e.g. immediately following extrusion
- D04H3/166—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between thermoplastic filaments produced in association with filament formation, e.g. immediately following extrusion the filaments being flash-spun
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
- D06M11/54—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with sulfur dioxide; with sulfurous acid or its salts
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/52—Separators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/02—Diaphragms; Separators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/24—Alkaline accumulators
- H01M10/26—Selection of materials as electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
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Description
本明細書中で用いられるとき、用語「ポリマー」は一般に、限定されないが、ホモポリマー、コポリマー(例えば、ブロック、グラフト、ランダムおよび交互共重合体など)、ターポリマー等、ならびにそれらのブレンドおよび変性物を包含する。さらに、別に具体的に限定されなければ、用語「ポリマー」は、材料の全てのあり得る幾何学配置を包含するものとする。これらの配置には、限定されないが、アイソタクチック、シンジオタクチック、およびランダムシンメトリーなどが含まれる。
本発明は、現在使用されているセパレーターに伴う問題を克服し、アルカリバッテリーにおいて使用可能である、所望の引張強さ、アンモニア吸収特性、電解質吸収性および電気絶縁性を有する湿潤性シート材料を提供する。
(i)ノルマルペンタンとシクロペンタンとの混合物からなる紡糸剤中の12重量%〜24重量%のポリエチレンの溶液を約205℃〜220℃の紡糸温度においてフラッシュ紡糸してプレキシフィラメント状繊維ストランドを形成し、プレキシフィラメント状繊維ストランドを非接着ウェブ状に集める工程と、
(ii)約5cm〜約30cm離して配置された約124℃〜約154℃の温度の加熱引取ロールの間で非接着ウェブを縦方向に一軸延伸して約3%〜25%延伸し、延伸ウェブを形成する工程と、
(iii)延伸ウェブを約124℃〜約154℃の温度の加熱接着ロールの間で接着して不織布シートを形成する工程であって、不織布シートが、約0.5〜約1.5m2/gの表面積および平均流れ細孔径の2.5倍超であり最小細孔径の11倍超である最大細孔径を有する工程とを含む。
KOH電解質中のイオン耐性は、イオン流に対するセパレーターの耐性の尺度であり、以下のように定量される。試料を小片(1インチ×1インチ)に切り分け、35%の水酸化カリウムに一晩浸漬して、完全な湿潤を確実にする。試料を露出する1cm2のウインドウがある2つのテフロン(登録商標)シムの間に試料を挟んだ。テフロン(登録商標)シムと試料とのサンドイッチを2つの白金電極を有する抵抗セル内に置き、ウインドウが2つの電極に対向しているようにした。HPミリオームメーターを使用して1KHzにおいて抵抗を測定した。テフロン(登録商標)シムの間のセパレーターが全く無いままで測定を繰り返した。2つの読取値の間の差は、試料の抵抗(ミリオーム)である。次に、セパレーター抵抗を電極の面積(この場合、1cm2)で乗じ、結果をミリオーム−cm2単位で記録する。
〔1〕ポリマー繊維を含む少なくとも1つの不織布シートを含む電気化学セルのためのセパレーター材料であって、前記不織布シートが、0.5〜1.5m 2 /gの表面積を有し、前記セパレーターが、スルホン化を受けないときの前記材料に比べてその縦方向(MD)の引張強さの少なくとも70%を保持する、セパレーター材料。
〔2〕前記ポリマー繊維がスルホン化され、少なくとも0.67重量%の硫黄を含有する、前記〔1〕に記載のセパレーター材料。
〔3〕前記ポリマー繊維が、ポリオレフィン、ポリエステル、ポリアミド、ポリアラミド、ポリスルホン、ポリイミド、フッ素化ポリマーおよびそれらの組み合わせからなる群から選択されるポリマーを含む、前記〔1〕に記載のセパレーター材料。
〔4〕前記ポリマー繊維が、ポリエチレン、ポリプロピレン、ポリブチレンおよびポリメチルペンテンからなる群から選択されるポリオレフィンポリマーから製造される、前記〔3〕に記載のセパレーター材料。
〔5〕前記ポリマー繊維が、円形でない断面を有する、前記〔1〕に記載のセパレーター材料。
〔6〕前記ポリマー繊維が、プレキシフィラメント状繊維ストランドである、前記〔1〕に記載のセパレーター材料。
〔7〕前記不織布シートが、前記縦方向に一軸延伸された不織布シートである、前記〔1〕に記載のセパレーター材料。
〔8〕前記不織布シートが、0.5〜1.0m 2 /gの表面積を有する、前記〔1〕に記載のセパレーター材料。
〔9〕前記不織布シートが、繊維の100%に対して繊維の数平均直径が1マイクロメートル超である繊維からなる、前記〔1〕に記載のセパレーター材料。
〔10〕前記不織布シートが、0.20mmole/gのアンモニア捕捉量および少なくとも16ニュートン/センチメートル(N/cm)の縦方向引張強さの残率を有する、前記〔1〕に記載のセパレーター材料。
〔11〕前記不織布シートが、平均流れ細孔径の2.5倍以上であり最小細孔径の11倍超である最大細孔径を有する、前記〔1〕に記載のセパレーター材料。
〔12〕電気化学セルのためのセパレーター材料を製造するための方法であって、
ノルマルペンタンとシクロペンタンとの混合物からなる紡糸剤中の12重量%〜24重量%のポリエチレンの溶液を205℃〜220℃の紡糸温度においてフラッシュ紡糸してプレキシフィラメント状繊維ストランドを形成し、前記プレキシフィラメント状繊維ストランドを非接着ウェブ状に集める工程と、
5cm〜30cm離して配置された124℃〜154℃の温度の加熱引取ロールの間で前記非接着ウェブを縦方向に一軸延伸して3%〜25%延伸し、延伸ウェブを形成する工程と、
前記延伸ウェブを124℃〜154℃の温度の加熱接着ロールの間で接着して不織布シートを形成する工程であって、前記不織布シートが、0.5〜約1.5m 2 /gの表面積を有し、平均流れ細孔径の2.5倍超であり最小細孔径の11倍超である最大細孔径を有する工程とを含む、方法。
〔13〕前記延伸ウェブを接着した後に前記不織布シートをスルホン化する工程をさらに含む、前記〔12〕に記載のセパレーター材料を製造するための方法。
〔14〕バッテリーまたはキャパシタのどちらかである、前記〔1〕に記載の電気化学セル。
〔15〕ポリマー繊維を含む少なくとも1つの不織布シートをさらに含むセパレーター材料を含むアルカリバッテリーである電気化学セルであって、前記不織布シートが、0.5〜1.5m 2 /gの表面積を有し、前記不織布シートが、平均流れ細孔径の2.5倍以上であり最小細孔径の11倍超である最大細孔径を有し、前記ポリマー繊維がスルホン化され、少なくとも0.67重量%の硫黄を含有し、前記セパレーターが、スルホン化を受けないときの前記材料に比べてその縦方向(MD)の引張強さの少なくとも70%を保持する、電気化学セル。
Claims (3)
- ポリマー繊維を含む少なくとも1つの不織布シートを含む電気化学セルのためのセパレーター材料であって、前記不織布シートが、0.5〜1.5m2/gの表面積を有し、平均流れ細孔径の2.5倍以上であり最小細孔径の11倍超である最大細孔径を有し、前記セパレーターが、スルホン化を受けないときの前記材料に比べてその縦方向(MD)の引張強さの少なくとも70%を保持する、セパレーター材料。
- 電気化学セルのためのセパレーター材料を製造するための方法であって、
ノルマルペンタンとシクロペンタンとの混合物からなる紡糸剤中の12重量%〜24重量%のポリエチレンの溶液を205℃〜220℃の紡糸温度においてフラッシュ紡糸してプレキシフィラメント状繊維ストランドを形成し、前記プレキシフィラメント状繊維ストランドを非接着ウェブ状に集める工程と、
5cm〜30cm離して配置された124℃〜154℃の温度の加熱引取ロールの間で前記非接着ウェブを縦方向に一軸延伸して3%〜25%延伸し、延伸ウェブを形成する工程と、
前記延伸ウェブを124℃〜154℃の温度の加熱接着ロールの間で接着して不織布シートを形成する工程であって、前記不織布シートが、0.5〜1.5m2/gの表面積を有し、平均流れ細孔径の2.5倍以上であり最小細孔径の11倍超である最大細孔径を有する工程とを含む、方法。 - ポリマー繊維を含む少なくとも1つの不織布シートを含むセパレーター材料を含むアルカリバッテリーである電気化学セルであって、前記不織布シートが、0.5〜1.5m2/gの表面積を有し、前記不織布シートが、平均流れ細孔径の2.5倍以上であり最小細孔径の11倍超である最大細孔径を有し、前記ポリマー繊維がスルホン化され、少なくとも0.67重量%の硫黄を含有し、前記セパレーターが、スルホン化を受けないときの前記材料に比べてその縦方向(MD)の引張強さの少なくとも70%を保持する、電気化学セル。
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US10270074B2 (en) | 2015-02-19 | 2019-04-23 | Hollingsworth & Vose Company | Battery separators comprising chemical additives and/or other components |
US11261543B2 (en) * | 2015-06-11 | 2022-03-01 | Dupont Safety & Construction, Inc. | Flash spinning process |
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2013
- 2013-11-08 JP JP2015542710A patent/JP6358711B2/ja active Active
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- 2013-11-08 KR KR1020217029443A patent/KR20210118212A/ko active Application Filing
- 2013-11-08 KR KR1020227045706A patent/KR20230004962A/ko not_active Application Discontinuation
- 2013-11-08 CN CN201380059560.8A patent/CN104969381B/zh active Active
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Also Published As
Publication number | Publication date |
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KR20210118212A (ko) | 2021-09-29 |
KR102221467B1 (ko) | 2021-03-02 |
WO2014078186A1 (en) | 2014-05-22 |
KR102146811B1 (ko) | 2020-08-21 |
EP2920830A1 (en) | 2015-09-23 |
US20200274122A1 (en) | 2020-08-27 |
KR20230004962A (ko) | 2023-01-06 |
US20160276640A1 (en) | 2016-09-22 |
US20140134498A1 (en) | 2014-05-15 |
CN104969381A (zh) | 2015-10-07 |
CN104969381B (zh) | 2017-07-11 |
EP2920830B1 (en) | 2018-01-03 |
JP2015536550A (ja) | 2015-12-21 |
KR20150084842A (ko) | 2015-07-22 |
KR20210024209A (ko) | 2021-03-04 |
KR20200067926A (ko) | 2020-06-12 |
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