TW318194B - - Google Patents
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- TW318194B TW318194B TW084107984A TW84107984A TW318194B TW 318194 B TW318194 B TW 318194B TW 084107984 A TW084107984 A TW 084107984A TW 84107984 A TW84107984 A TW 84107984A TW 318194 B TW318194 B TW 318194B
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- Taiwan
- Prior art keywords
- fabric
- paper
- silicone
- fiber
- wrinkle
- Prior art date
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- 229920001296 polysiloxane Polymers 0.000 claims description 74
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- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229910052790 beryllium Inorganic materials 0.000 claims 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims 1
- 239000011230 binding agent Substances 0.000 claims 1
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- 206010016322 Feeling abnormal Diseases 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
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- 229910052802 copper Inorganic materials 0.000 description 2
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- SXAMGRAIZSSWIH-UHFFFAOYSA-N 2-[3-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,2,4-oxadiazol-5-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NOC(=N1)CC(=O)N1CC2=C(CC1)NN=N2 SXAMGRAIZSSWIH-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- 241000473391 Archosargus rhomboidalis Species 0.000 description 1
- YDNKGFDKKRUKPY-JHOUSYSJSA-N C16 ceramide Natural products CCCCCCCCCCCCCCCC(=O)N[C@@H](CO)[C@H](O)C=CCCCCCCCCCCCCC YDNKGFDKKRUKPY-JHOUSYSJSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- CRJGESKKUOMBCT-VQTJNVASSA-N N-acetylsphinganine Chemical compound CCCCCCCCCCCCCCC[C@@H](O)[C@H](CO)NC(C)=O CRJGESKKUOMBCT-VQTJNVASSA-N 0.000 description 1
- 241001674048 Phthiraptera Species 0.000 description 1
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- 238000000944 Soxhlet extraction Methods 0.000 description 1
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- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- ZYXYTGQFPZEUFX-UHFFFAOYSA-N benzpyrimoxan Chemical compound O1C(OCCC1)C=1C(=NC=NC=1)OCC1=CC=C(C=C1)C(F)(F)F ZYXYTGQFPZEUFX-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229940106189 ceramide Drugs 0.000 description 1
- ZVEQCJWYRWKARO-UHFFFAOYSA-N ceramide Natural products CCCCCCCCCCCCCCC(O)C(=O)NC(CO)C(O)C=CCCC=C(C)CCCCCCCCC ZVEQCJWYRWKARO-UHFFFAOYSA-N 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- RFKMCNOHBTXSMU-UHFFFAOYSA-N methoxyflurane Chemical compound COC(F)(F)C(Cl)Cl RFKMCNOHBTXSMU-UHFFFAOYSA-N 0.000 description 1
- 229960002455 methoxyflurane Drugs 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- VVGIYYKRAMHVLU-UHFFFAOYSA-N newbouldiamide Natural products CCCCCCCCCCCCCCCCCCCC(O)C(O)C(O)C(CO)NC(=O)CCCCCCCCCCCCCCCCC VVGIYYKRAMHVLU-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
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- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
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- 239000002244 precipitate Substances 0.000 description 1
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- 239000004576 sand Substances 0.000 description 1
- 150000003335 secondary amines Chemical group 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000015541 sensory perception of touch Effects 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
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Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/146—Crêping adhesives
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/59—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/30—Multi-ply
- D21H27/38—Multi-ply at least one of the sheets having a fibrous composition differing from that of other sheets
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paper (AREA)
- Materials For Medical Uses (AREA)
- Sanitary Thin Papers (AREA)
Description
經濟部中央標準扃負工消费合作社印製 年月ϊ; .; 福充: 7 丨丨 _ . , I _ 丨 _ Μ «!,- 五、發明説明(1 ) 〜 螢明背長 於柔軟薄紙的製造中(如面紙與衛生紙),產業已持 續改進產品之觸覺特性以迎合消費者的需求與渴望。—方 法用以改進薄紙觸感。即結合—添加劑於薄紙’包括—矽 酮(例如衆矽氧烷)。矽酮"包括一廣泛的產品,其 有矽原子鏈爲其核心結構。藉由附著迭定之化學官能基 ,矽酮炙王幹以達成不同之特性。合成之結構通常爲聚矽 .氧’克聚甲基梦氧垸,或聚二有機基>5夕氧貌。梦酮經常爲 疏水的’以及可以純液體、有機溶劑溶液,或水乳膠的型 式獲得。這些乳膠可有一正、中性或負電荷。乳膠微粒的 尺寸也可被調整由約50 nanometers (微乳膠)至約j ^icrori。矽膠可以流體型式被供應,但其通常於水中有低 溶解度,除非一附加之官能基被用以增加親水特性。 已知矽酮可提供一所欲之平滑或柔軟感覺於薄紙表面 且因此改進柔軟的感覺。典型矽膠於薄紙織物形成後被施 加於某處’於乾燥前或後’以喷灑或印刷施加矽酮於薄紙 表面。當此類方法爲有效的,其需要一資金投資於噴灑或 印刷S又備以施加石夕嗣。又,石夕銅爲昂貴的且需要一足量發 銅以給予薄紙所欲的特性。添加量範圍由丨_2乾的wt〇/。 (以纖維重量爲基準)。 ° 加入矽酮於薄紙製造過程之濕端的概念已預先被押 到。但當使用足量(即以喷灑或印刷所需之量)時,發嗣 破壞向下流之皺紋效果,其藉由阻止薄片適當地粘附於乾 燥器表面且因而導致薄片遠離乾燥器。此外,矽酮恢速堆 本紙張尺度適用中國"i家榡準(CNS ) A4规格(2I0X297公^ ~ ' --— -裝------訂------l/Jt f諳先閲讀背面之a意事項再填寫本頁} 4
S同須被除去)導致昂貴矽 ®ίδί9 五、發明説明(2) 聚於濕端水系統處(补由、 酮 X %處疋石夕 之損失。 因此,需要一方祛 站 (請先閱讀背面之注意事項再填寫本頁) 改進薄紙之觸f: #性、、口矽酮材料於薄紙内’其可 的。 X及爲簡單的與於成本上非昂貴 發明搞要 已發現矽酮(特别 加入薄紙製造過程之、、a…石氧烷)可以一非常低的級數 之柔軟度且不會干擾敏::仍可有效地改進合成薄紙產品 低級數㈣,其與纖維素:矣此步驟之完成可藉由使用 過-於㈣本身或^表面之負電荷^鍵結,透 r 祕ύ L ^ 女疋膠態微粒之表面劑上的正電 ,n ^ L B周整至尚速率矽酮添加下出現的矽 酮。完成陽離子鍵結可 _ X纖維素纖維接觸水溶或與水共存 經濟部中央標準局員工消費合作社印製 〈陽離子㈣或以陽離子表面劑處理之石夕酮,其可提供正 ^鍵結位£。此類心連接於㈣錢維㈣現於纖維上 較大的滞留(與非離子或陰離子相比較)。結果,於薄 紙織物形成期間較少矽酮損失於白水系統中,且矽酮實質 地保留於纖維層中。因而製造出柔軟且強度大的薄紙片。 因此於一觀點中,本發明屬於一方法用以製造柔軟薄 、氏片,包含下列步驟:(a)形成纖維素造紙纖維之含水懸 浮液,包含由約〇. 〇 i至約i乾wt% (以纖維重量爲基準) 的陽離子矽酮,(b)沈澱含水纖維懸浮液於多孔成型銅 網,其可保留纖維以形成一濕的織物;(c)脱水或脱水/乾 燥濕的織物;(d)以一製皺粘合劑粘附織物於一製皺圓筒 本紙張尺度適用中國國家榇準(CNS ) A4規格(2丨OX297公嫠)
五、發明説明(3) (如 Yankee 乾燥器、. ,^ ),以及(e)由製皺圓筒製皺織物,β 开^成柔軟薄紙。 於一濕壓梓過程音彳丨士 實】中’薄紙織物可於乾燥器上乾 γ。於一通過乾燥過程實例中,在被附著於製敏圓筒(如 乾燥器)前織物可被部分乾燥或全部乾燥。選擇 地’若陽離子矽酮輿敏維彡 、纖維k供適當的柔軟度,则織物可被 通過乾燥且不需塑鍅 . 。此類未經製皺過程之通過乾燥薄紙 較佳地爲夹層的且至. „ 王乂具有一外層包含主要硬木纖維與 陽離子梦嗣。 幸又佳地’薄紙被形成爲一夹層薄紙’具有一硬木層於 M 'J表面上肖I木(強度)層於兩側表面上。因陽離子 石夕酮:某些方面如同一鬆解劑’較佳爲只添加矽酮於外層 硬木完全紙料以改進合成薄紙之柔軟度,而卻不會降解軟 層強度jl匕外,較佳爲置放包含陽離子石夕嗣之硬木層靠 著製皺圓筒或Yankee乾燥器之表面(於製皺過程中), 以㈣離子石夕酉同落於薄紙側上,使其中平滑且柔軟。—般 而。,薄紙之乾燥器側”比相反側(空氣側)更平滑。 最終薄紙產品有-、二、三或更多層。對多層羞品而言, 個别層較佳爲一兩層結構,即強度層位於内侧而軟的硬木 層於產品之外側。 因此於某些觀點中,本發明屬於一夾層薄紙片包含一 第一層與—第二層’其中第一層爲外層以及包含主要硬木 纖維(如桉樹纖維)與由約〇.〇1至約〇 2乾的wt% (以 外層之纖維重量爲基準)之陽離子矽酮,其中二層包 本紙張尺度適用中國國家棟準(CNS ) A4規格(210x297公釐) I ^ n n n - I -----'^ (锖先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印裝 經濟部中央棣準局員工消費合作社印製 五、發明説明(4 ) 主要軟木纖維。 使用於此之”陽離子矽酮”爲任何矽酮聚合物或齊聚 物,其具有一矽原子主鏈(包括聚矽氧烷),具正電荷, 本身爲砂S同結構或與一表面劑結合。梦酮可被傳送至含水 之造紙纖維懸浮液而成爲矽酮流體、乳膠、懸浮液、或— 固體。矽酮可爲不可取代之聚甲基矽氧烷,其具可取代之 έ能基’如氨基、環氧基、矽烷醇基,季氮等。 對敏紋薄紙而言’加入含水之造紙纖維懸浮液的矽酮 量可由約0.01至約1之乾wt〇/〇 ,更特别地由約〇 〇 5至約 ◦.5之乾wt% ’以及由約〇」至約〇 2乾wt% ;添加量 視所欲之觸覺特性,造紙纖維組成,與製皺粘合劑組成而 定。若薄紙被混合(非夾層),前述之量適用於薄紙之總 重。對未製皺薄紙而言’陽離子矽酮添加量的上限可因經 濟因素有較咼的限制,此由於其缺少石夕g同可干擾之製敏步 驟。 若石夕酮與表面劑結合,合適的表面劑包括可安定所 欲之矽酮化合物乳膠的表面劑。這些表面劑之特殊結構可 爲非常廣泛,但需有至少某些陽離子特性。 關於本發明方法中用以製造製皺薄紙之製皺枯合劑成 分’合適”的製敏枯合劑包含一可塑劑水溶液(使用於此爲 脱模劑”)與—熱固性陽離子聚醯胺樹脂,與較佳爲進一 步包含聚乙埽醇。製敏枯合劑以溶液方式施…包含由 0.1至約1%的固體,其餘爲水。 (請先閲讀背面之注意事項-S填寫本頁} ύ. 訂 -丨^ —^1 am _ 合適的熱固性陽離子聚醯胺樹脂爲表鹵醇,較佳爲表
本纸張尺舰财關家標^nS ) A4規格717^^ 318194 B7 * -v ·,知》 五、發明説明(5 ) 氣醇’以及一水溶性的策醯胺,其具有由聚亞烴基聚醯胺 何生之二級胺基與—内含約31〇碳原子之飽和脂族二元 酸。水溶性的聚醯胺包含循環基團的公式如下: -NH(CnH2nHN)x - CORCO - 基 N與X各爲2或2以上,R爲二元羧酸之二價烴 經濟部中央標準局員工消費合作社印製 這些樹脂之一重要特性爲其與聚乙烯醇爲相位相容 的。此型式足合適材料可爲商標KYMENE (Hercules,Inc ) 與 CASCAMID (Borden)與其被詳述於 Gerald keim,1960 年2月23日公佈之美國專利2 926 1 16與Gerald 等 人1 962年10月16日公佈之美國專利3 05 8 873與Dave S〇erensl 98 5年7月9日公佈之美國專利4 528 3 i6中, 其内容均合併於此以供參考。製敗粘合劑較佳地也包括聚 乙烯醇。 於製皺組成中熱固性陽離子聚醯胺樹脂量(以固體重 量百分比爲基準)可由約1 〇至约8〇 wt%,更特别地由約 20 至約 60 wt%。 合適的可塑劑或脱模劑包括季械化之聚氩基酿胺與山 梨糖醇,雖然山梨糖醇之可塑機構與季鹹化之聚氦基酿胺 大半不同。較佳之季鹹化聚氨基醯胺爲Quaker2〇〇8 (由 Quaker Chemical Company獲得)。足量之脱模劑需被包 含於製皺組成中,以避免薄紙片覆蓋於乾燥器外且實質地 (請先閲讀背面之注意事項再填寫本頁) 表紙張尺度適用中國國家標率(CNS > A4規格(210X297公着 經濟部中央梯準局貝工消费合作社印製 η、 ιΡ: 五、發明説明(6 ) ^ 避免纖維堆積於乾燥器表面。於製皺粘合劑組成中之合適 的脱模劑量由約1 0至約40 wt%,更特别地由约1 5至約 2 5wt% (以固體爲基準)。 存在之聚乙烯醇的量可由約1至約80 wt%,更特别地 由約20至約60 wt% (以固體爲基準)。 若薄紙被製皺,乾燥器溫度爲可使薄紙於乾燥器表面 儘可能乾燥地被製皺。當薄紙織物到達製皺刀片時的溫度 (由紅外溫度感應器測得)爲約2〇〇度或更大,較佳約 220度或更大,以及更佳爲約23 5度。合適的範固由約 225度至約235度。同時,織物於製皺刀口的水分含量爲 约3 %或更小’較佳爲2 5 %或更小。合適的範圍爲由約2 至3%。這些條件提供織物高度附著於乾燥器表面且因此 使製皺刀片均勻地解粘薄紙片。 圈形簡迷 圖1.爲關於本發明薄紙製造過程之操作程序圖,立中
T 兩織物被個别地形成與舖平於一起以形成_夾層織物。 圖2·爲關於本發明濕壓榨薄紙製造過程之操作程序 圖’其中使用一流漿箱形成夾層薄紙。 圖3.爲一手造紙研究結果的長條圖,以纖維素造紙纖 維測得之多種矽酮的留存率,説明了陽離子石夕酮之較大的 留存率。 圖4.爲一手造紙於矽嗣留存率的研究結果長條圖,説 明於手造紙強度上之矽酮沖擊。 圖5.爲矽酮量對製皺粘合劑成分脱模劑量的簡圖,説 1.1: - I - - - I -- I -I ----- - I : . 丁 U3 、τ (請先閱讀背面之注意事項再填寫本頁)
午月 αΜΛ. 15 ______Β7 五、發明説明(7 ) 明兩化學製品劑量的平衡。 圈形之詳述 Ί丨 f靖先閱讀背面之注意事唄再填、寫本耳j 參照圖1,其説明相關於本發明之方法。用以製造濕 壓榨薄紙(通常也稱之爲平舖形成),其中兩個濕織物爲 個别形成與隨後結合成一單一織物。爲了形成第一織物, 一特定纖維(硬木或軟木)以習用於造紙工藝的方式被製 備且被傳送至第一漿池i ’其中纖維被保留於含水懸浮液 中。一漿泵2供應所需之懸浮液量至沖漿录4之抽吸例。 一計量泵5供應一化學製品(如乾強度樹脂或矽酮)於纖 維懸浮液中。額外之稀釋水與纖維懸浮液混合。之後,全 部的混合物被加壓且傳送至流漿箱6。含水懸浮液離開液 漿箱6與被沈澱於抽吸箱8上之無端造紙纖維7上。抽 吸箱被抽眞空以將水抽離懸浮液,因而形成第一織物。於 此實例中’由流漿箱流出之漿料爲”空氣側”層’此層於 乾燥期間被放置於遠離乾燥器表面。 經濟部中央標準局員工消費合作社印製 成型纖維可爲任何成型纖維,較佳爲具有一纖維支持 指數約1 5 0或更大。合適的特定成型纖維包括(非限制) 單層纖維,如 Appleton Wire 94 Μ(由 Albany International Corporation 獲得);雙層纖維,如 Asten 866 (由 Asten Group獲得);以及三層纖維,如Lindsay 3080(由Lindsay Wire獲得)。 保留於流漿箱中之造紙纖維的含水懸浮液濃度可由約 〇· 05至約2wt%,較佳爲約0· 2 wt% 。陽離子石夕酮可於織 物形成前(例如漿池中或流漿箱中)任何一瞬間加入造紙 本紙張尺度適用中國國家標準(CNS > A4規格(210X297公釐)
I ! *乂 ! *乂 補充: 五、發明説明(8 )
纖維之含水懸浮液中。較佳爲㈣被加入完全紙料層,A =敏期間對著乾燥器表面被放置(於此例中爲由第二流 — 層)陽離子矽酮較佳爲被加入硬木纖維 完全紙料十,此紙料用以形成薄紙之一或兩外層。第一流 4相 6可爲一央廢A继γ n . 穴層机桌相,其具有二個或多個夾層内室可 傳送-成層或夾層第一濕織物,或可爲一單夾層流漿箱可 傳送一混合或同相之第—濕織物 爲形成第二織物,—特定纖維(硬木或軟木)以已知 於造紙工藝的方式被製備且被傳送到第二漿池1 1 ,其中 纖維被保留於含水懸浮液中。漿泵12供應所需之懸浮液 量至沖漿泵14之抽吸側。一計量泵5選擇地供應一化學 製品(如乾強度樹脂或矽酮)於纖維懸浮液中。額外之稀 釋水與纖維诸浮液混合。之後,全部的混合物被加壓且傳 送至流製箱16。含水懸浮液離開流漿箱16與被沈澱於抽 吸箱1 8上之無端造紙纖維1 7上。•抽吸箱1 8被抽眞空以將 水抽離懸浮液,因而形成第二織物。於此實例中,由流漿 相1 6流出之漿料爲”空氣側”層,此層於乾燥期間被放 置於與乾燥器表面接觸。合適的成型織物用於第二流漿箱 之成型織物1 7包括前述相關於第一流漿箱成型纖維之相 同的成型纖維。 在第一與第二濕織物初期形成後,兩織物以平舖方兌 接觸在—起’此時濃度由約1 〇至約3 0 wt%。不論濃度;| 否被選定’較佳者爲兩濕織物的濃度爲實質相等的。將| 一濕織物於滾筒1 9處與第二濕織物接觸而達成平舖。 本纸張尺度刺巾關家c叫 (請先閱讀背面之注意事項再填寫本頁) 裝- -a i 於 經濟部中央標準局員工消費合作社印製 * I m
五、發明説明(9 ) 當結合織物於眞空箱Μ處被移轉至 統方式完成結合織物之脱水,乾燥與製 22後,以傳 铺的織物進-步地藉由壓力滾筒3 °更特別地,平 (請先閲讀背面之注意事項再填寫本頁)
Yankee乾燥器30,厭六 脱水與移轉至 壓力浪筒將水由織物中爆 布吸收,而導致織物w孳 免出,水被毛 %切附奢於Yankee乾燦器 織物被乾燥’製皺以及姑拟χ 钱占 表面。隨後’ 入及被捲入滾筒中以轉狻Λ θ 品。 得變成瑕終皺紋產 圖2爲適合用於太益、 万、本發明疋一典型濕壓梓 程的操作程序圖。圖+ A . s ^ 專,氏製造過 吗不爲一夾層流衆箱41 ,__ ▲ 4 2,一点也丨浪簡41 成型織物 ° ,—造紙毛布44,一壓力滾筒,—γ 乾燥器 46,與一製 Yankee 皺刀片47。亦圖不(但未標號 轉輪或張力滾筒,用以服令械 )1 J以限疋織物於簡圖中滑動。於操作中, 一夾層流黎箱41連續地沈澱-夾層製料喷射於成型織物 42與毛布間’毛布部分覆蓋於成型滾筒43外圍。當新成 型之織物通過成型滾筒之弧形面時,因離心力的緣:,透 過成型織物’水可被移出含水衆料懸浮液中。因成型織物 與毛布分離,濕織物停留於毛布上,以及被轉移至Yankee 乾燥器。 經濟部中失標準扃員工消費合作社印裝 於Yankee乾燥器處,製皺化學品被連續地施加於現有 枯合劑頂端’以水溶液的形式。以任何便利裝置施加溶液, 較佳爲使用一噴灑構架,其可將製皺粘合劑溶液平均地噴 灑於乾澡器表面。乾燥器表面的施加處,立即被以製皺刮 刀刀片處理且允許有充足時間喷灑且乾燥新鮮粘合劑薄 膜0 本紙張尺度適用中國國豕標準(CN$ > A4規格(210X297公4 )
五、發明説明(10) 經濟部中央標準局員工消费合作社印製 濕織物以施加力約200 p0Unds/inch 2 (psi)的壓力滚筒 施加於乾燥器表面。於進入之濕織物到達壓力滾筒時,濃 度通常爲約10 wt% (範圍由約8至約20 wt% )。接著 爲壓榨或脱水步驟’織物濃度約3〇 wt%或以上。充足之 Yankee乾燥器蒸氣力與機罩乾燥能力被施加於織物以達 一最終水分含量3%或更小,較佳爲2 5%或更小。以紅外 溫度感應器測量薄片或織物溫度,較佳於約2 3 5度下施加 製皺刀片。 圖3爲長條圖,説明以纖維素造紙纖維(如實例1中 之手造紙)測得之多種矽酮的張力,其説明陽離子矽酮之 較高的張力。圖示之Soxhlet抽提百分比爲特殊石夕g同(已 標示矽酮碼)。如長條圖所示,陽離子矽酮(i 7丨6與i 7 1 8 ) 較其它被測試之矽酮有較高張力値。 圖4爲長條圖,説明手造紙抗張強度之(前述)石夕 嗣留存率。具有陽離子乳膠與Syhlet最高抽提之_g夕嗣 (1716與108)有最大留存率於手造紙抗張力上。” 1 7 1 6 ”矽酮於抗張強度上有5 8 %的縮減。非離子” D S W ”顯示並無明顯改變於抗張強度上。 圖5爲一簡圖’圖示接觸製皺圓筒之纖維内梦酮的濃 度爲製皺粘合劑組成中脱模劑的濃度的函數,圖示製敏函. 數有效地於操作窗中(曲線下的斜線部分)。吾人亦相作 陽離子矽酮作用如一脱模劑,可調整兩化學品以達一適當 的平衡。如圖所示,添加一高級數之陽離子矽酮(約! 乾wt°/。,以矽酮加入之織維重量爲基準),適當的製敏 本紙張尺度適用中國國家橾準(CNS ) A4規格(210X297公釐) Ο ----------裝------訂-------•乂 (请先閱讀背面之注意事項-S填寫本頁) ^ 疋成此無關於製皺粘合劑成分中脱模劑的量。如 *所南級數之脱模劑也無法達成適當的製敏。當操作 (請先閲讀背面之注意事項再填寫本1) :〈精確形狀未知時,#這些限制下仍有機會去平衡以及 使石夕銅與脱模劑的量完善。 實例 ί^1__ι 手ia,..氏研究被元成其用以評估於多種纖維(桉樹、 分散桉樹、與槭樹BCTMp )之物理與觸覺特性上不同石夕 酮的效果。於手造紙之製備過程中,一 50 grams之絶對乾 燥纖維裝料於漿與195〇 g蒸餾水被製備以供個别測試代 碼。 ' 經濟部中央標準局員工消費合作杜印製 於聚隨後以一英式紙漿纖維解離機(BHtish PulPDistintegrator )以3〇〇〇 rpm打漿約5分鐘合成淤 漿以蒸餾水加至8 Hters。製備一 〇 5%活性矽酮溶液且加 入1.8 1 wt%活性矽酮(以纖維重量爲準)於淤漿中。混合 物於進行測試前被允許放置10分鐘。450 wiUinters充分 混合足於漿被用以製造8.5 inches * 8.5 inches手造紙於 Valley Ir〇nwork模中。手造紙被平舖於濾網,置放於吸 收薄片下,且以75 pounds/inch2壓力加壓約ι分鐘,於 蒸氣乾燥器乾燦2分鐘’最後放置於約60-70度的烘箱中 至一怪重(60 grams/m2 ’絶對乾燥)。手造紙被切割成 7.5 inches2 。之後,手造紙於一室中被調整至少48小時, 此室内維持相關於TAPPI 402之恆溫與相對之恒定濕 本纸張尺度適用中國國家標準(CNS ) Λ4規格(2丨〇X:297公釐) 經 濟 部 中 央 標 準 局 員 工 消 費 合 作 社 印 製 \ B7 五、發明説明(12 ) ^ 10個標準手造紙被製造以供個别測試號碼。 —”手造紙研究評估數種不同之矽酮:”軟化劑dsw ”爲 7環氧取代之聚矽氧烷,以PH爲7之非離子水乳膠液形 式,由 D〇WC〇rning ( Midland , Michigan )獲得。” 1716 微乳膠”爲—陽離子矽烷醇取代之聚矽氧烷乳膠,PH爲 I.7 ,可由D〇wC〇rning獲得。” 108乳膠”爲一陽離子 虱基取代聚矽氧烷乳膠,PH値爲4.5-5.5 ,可由Dow C〇rning獲得。” E_67?乳膠”爲一非離子氦基取代之聚 石夕氧燒乳膠’可由Wacker Silic〇nes Corporal (Adrian,Michigan )獲得。 S〇Xhlet抽提百分比(圖3 )與抗張強度(圖4 )之 變化指出陽離子乳膠(D〇wC〇rning,s ” 1〇8乳膠”與” 1 7 1 6微札膠)爲達成適當的保留率於薄紙機器之濕端的 最佳選擇。此證明了保留機構需要一變化的差異介於砍酮 乳膠(陽離子)與纖維(陰離子間。 爲了進一步評估製造薄紙之多種矽酮材料,數個原型 薄紙被製(實例2_7)於一小尺度,連續之試驗機器’,'其 結構如圖1。此機器形成二個分離之薄紙片,與將其平舖 於-起成單-薄片,再加以壓梓,乾燦與製敏。此結構允 浦模擬具高層純度之夾層薄紙片。每一 之聚料系統,包括聚池、計量聚、„、與白水:理= 允許每一層有其本身的纖維配漿與獨立之化學處理。化學 製品可被加入漿池中以產生一濃度之單一配料或計量進 入輸漿管道的量以允許週期性調整。 . 滅------—訂------- (請先閱讀背面之注意事項月填寫本頁) ,^Α7! 五、發明説明(13 ) 實例2 1.2 lbs/MT(0.54%)之 Dow Corning ” 軟化劑 DSW ” 被加入包含约0 · 8 %濃度槭樹之空氣側漿池中。乾燥器側漿 池包含北方軟木牛皮紙纖維(LL 19)。製造一夾層薄紙片, 包含5 0 %經矽酮處理之槭樹B C TMP與5 0 %未經處理之 軟木。 未經處理之軟木靠近乾燥器側。一乾強度澱粉(Redi Bond 2005, National Starch and Chemical company)被力口 入軟木側之漿泵中,以控制抗張強度。薄紙片被疊於硬木 之外側。其後的測試指出並無觸覺之改進,當與控制組 (50%未經處理槭樹BCTMP與50%北方軟木牛皮紙纖 維)作比較時。 實例3 經濟部中央標準局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) 10 1 bs/MT(0.45%) Dow Corning Q4-3667 ” 被加入 包含約0 · 8 %濃度之分散的按樹纖雏的空氣側漿池中。而乾 燥器側漿池包括一軟木纖維(LL 1 9)。包括50%經矽酮處理 之分散的桉樹與50%未經處理之軟木的一夾層薄紙片被 製成。未經處理之軟木靠近乾燥器側。加入一乾強度殿粉 (Redi Bond 2005)於軟木側漿泵以控制抗張強度。當加入 矽酮時,觀測包括基重之增加。此間接的指出矽酮被保留. 於薄片中。(其它的陽離子化學製品也產生此效果,當首 先加入帶電荷分子’其功能爲一保留助劑)。其後之測試 指出了觸覺的改進,當與控制組(5 0 %未經處理之分散按 樹與50%未經處理之軟木)作比較。 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) I y
五、發明説明(14 ) 實例4 10 lbs/MT(0.45%) Dow Corning w Q4-3667 ” 被加入 包含約0.8 %濃度之初散的桉樹纖維的空氣側漿池中。而乾 燥器侧漿池包括一軟木纖維(LL1 9)。包括50%經矽酮處理 之分散的桉樹與5 0 %未經處理之軟木的一夾層薄紙片被 製成。未經處理之軟木靠近乾燥器側。加入一乾強度澱粉 (Redi Bond 2005)於軟木側漿泵以控制抗張強度。於製敏 品質之較小惡化説明石夕酮存在於織物中。薄紙片被疊於硬 木之外側。其後測試顯示較控制組有觸覺上之改進。 實例5 10 lbs/MT(0.45%) Dow Corning ” 1716 微乳膠”被 加入包含約0.8%濃度之分散的桉樹纖維的乾燥器側漿池 中。而空氣側漿池包括一軟木纖維(LL1 9)。包括50%經矽 酮處理之分散的桉樹與50%未經處理之軟木的一夾層薄 紙片被製成。加入一乾強度澱粉(Redi Bond 2005)於軟木 側漿泵以控制抗張強度。於製皴品質之較小惡化指出矽酮 存在於織物中。薄紙片被疊於硬木之外側。其後測試顯示 較控制組有觸覺上的改進。 經濟部中央標準局員工消費合作杜印製 (請先閱讀背面之注意事項再填寫本頁} 實例6 30 lbs/MT(l.36%) Dow Corning ” 1716 微乳膠”被 加入包含約0· 8%濃度之分散的桉樹纖維的乾燥器側漿池 中。而空氣側漿池包括一軟木纖維(LLl 9)。包括50%經矽 酮處理之分散的桉樹與5 0%未經處理之軟木的一夾層薄 紙片被製成。在石夕自同被加入漿料系統後幾分鐘内’製敏品 本紙張尺度適用中國國家椟牟(CNS ) A4規格(210X297公釐) A7 A7 經濟部中央梯準局員工消費合作社印^ 五、發明説明(15 ) 質快速地降低。合成薄片不具敏紋’與相似於單光紙之硬 挺薄片被製成,其用於其它用途。缺乏拉伸而排除其轉換 成一兩層產品。 實例7 1 0 lbs/MT(0.45%) Dow Corning 108 乳膠”被加入 包含約0.8 %濃度之分散的桉樹纖維的乾燥器側漿池中。而 空氣側漿池包括一軟木纖維(LL1 9)。包括5 0 %經矽酮處理 之分散的桉樹與5 0 °/。未經處理之軟木的一夾層薄紙片被 製成。未經處理之軟木靠近乾燥器側。加入一乾強度殺粉 (Redi Bond 2005)於軟木側漿泵以控制抗張強度。於10 lbs/MT下,” 1 08乳膠”於經數個滚筒之後導致最終之 難看的外形與不均勻之乾燥器塗層説明了矽酮存在於織 物中。薄紙片被疊於硬木之外側。其後測試顯示較控制組 有觸覺上的改進。 完成進一步測試梦S同之添加,,如實例8 -1 4,使用_新 月狀的成型器,如圖2之濕壓榨機器。對下列所有實例而 言’加入約5 p0unds/metricton濕強度劑。於長與短纖維 間’被等量地分割。計算” P〇unds/metric ton ”以全部 薄片之基重爲準,即使於許多案例中,化學製品僅被加入 部分薄片中。於所有例子中’矽酮爲陽離子石夕酮( Corningl 08 乳膠)。 實例8 一矽酮乳膠被加入硬木漿料層(乾燥器側層),以〇 b 乾wt% (以硬木層之纖維重量爲準)。矽酮以間歇方式於 l^K- nn tn^l —^n n m n^i m i U3 >T (請先閲讀背面之注意事項再填寫本頁)
經濟部中央標準局員工消費合作社印裂 _____ 抵謹一座毯」___ 五、發明説明(16) 稀釋前(於流漿箱之前)被加入濃漿料中。一乾強度劑 (Parez 63 1 ’ 由 American cyanamid 獲得),約 〇」25 wt〇/0 被加入軟木敢料層(空氣側層)中。於稀釋前(於流漿箱 之前)以連續方式添加乾強度劑於濃漿料中。於此實例中, 乾強度劑與未含矽酮之控制組以相同級數被添加。製敏枯 合劑包含40%聚乙烯醇,40% kymene 557LX與20% Quaker 2008脱模劑(與控制組相同)。此薄紙較控制組 顯現實質的改進於觸覺方面。 實例9 加入砍酮如實例8,除劑量爲〇.〇8 wt%,製皺粘合劑 組成比率也變爲45/45/1 0 。乾強度劑需被增加至約 0.25wt% ,因爲較少脱模劑使得製皺刀片無法於塗層中充 分升起且強度降解也較大。柔軟度並無明顯改進。吾人相 k缺乏柔軟度的改進是由於製皺粘合劑組成與低級數之 石夕鲷(相較於實例8 )的改變。 實例10 加入碎酮如實例8,除劑量爲〇·32 wt%。製皺粘合劑 組成比率也變爲80/20/0 。乾強度被增加至約〇 5wt% , 因爲不含脱模劑’使得製皺刀片無法於塗層中充分升起且 強度降解也較大。柔軟度有輕微地改進。吾人相信缺乏柔 軟度的改進是由於最適宜之製皺條件的偏差所致(相較於 實例8 )。足量矽酮於薄紙上可克服不適當製皺所造成之 負面效果。 ----------ύ------,1Τ------d (請先閲讀背面之注意事項另填寫本頁} 本紙張尺度適 國家榡卜4規格(2|〇><297公幻
>L_n 五、發明説明(17 ) (請先閱讀背面之注意事項為填寫本頁) 如入矽酮如實例8,劑量爲〇 16 wt%。乾燥器基重由 :〇 pounds/2880 feet 2 (實例 8 )降至 5 〇 p〇unds/288〇 feei 。製敏枯合劑組成比率改變至45/45/1〇。乾強度由〇 7〇/( 2至〇.8%(與控制組比較)。柔軟度並無明顯地被改進。 D人相信缺乏柔軟度的改進是由於最適宜之製皺條件改 羑,即本實例之5 p0und薄片與實例8之7 p〇und薄紙的 差别。 Μ 12 對本實例而言,混合長纖維與短纖維於流漿箱之稀釋 步驟之前。通常分隔長與短纖維完全紙料之流漿箱隔板於 其所在位置,但無任何功能。乾燥器基重5 0 pounds/288〇 feet (實例8中爲7· 0 )。短纖維與長纖維混合前於短 纖維中加入0.08 Wt%之矽酮^而短纖維與長纖維混合前加 入〇. 6 %乾強度劑於長纖維中(控刺組中加入〇 〇 5 %乾強 度劑)。製皺粘合劑组成比率也改變爲45/45/1 〇。改進的 柔軟度説明添加陽離子矽酮可改進混合(非夾層)薄片的 柔軟度。 經濟部中央標準局員工消費合作社印製 i例13 對本實例而T,混合長纖維與短纖維於流漿箱之稀释 步驟之前。通常分隔長與短纖維完全紙料之流椠箱隔板於 其所在位置,但無任何功能。乾燥器基重5 0p〇unds/2880 feet2 (實例8中爲7.0 )。短纖維與長纖維混合前於短 纖維中加入0.32 wt%之矽酮。而短纖維與長纖維混合前加 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公廣)
五、發明説明(18 入〇_8%乾強度劑於長纖維中(控制組中加入〇 〇5%乾強 度劑)。製敏枯合劑組成比率也改變爲5〇/5〇/〇。與實例 1 2比較’柔軟度被改進。增加矽酮 的添加導致改進的柔軟 度,即使製皺條件可能不適宜。 上述實例僅爲説明的目的,不可姑初你λt 1 了被解釋爲本發明範圍 的限制,本發明的範圍應由下列申請專利範圍與所有的相 等物來定義。
EKOOI. 02\76-99\0290\PK0290-9.DQC n·—— 11· I —1 --I 良——[----- I I 丁 U3 ,τ (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 表紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 318194 專利申請案號84107984圈矛 祗1.-7修正1 子 Λ 曰. ! 主委部 表符號: 符號 簡要説明 1 第一樂池 2 槳泵 4 沖槳泵 5 計量泵 6 第一流槳箱 7 無端造紙纖維 8 抽吸箱 11 第二槳池 12 槳泵 14 沖槳泵 16 第二流樂箱 17 無端造紙纖維 ^ 18 抽吸箱 19 滾筒 20 眞空箱 22 毛布 30 Yankee乾燥器 31 壓力滾筒 41 一夹層流樂箱 42 一成型織物 43 一成型滾筒 44 一造紙毛布 45 一壓力滾筒 46 一 Yankee乾燥器 47 一製皺刀片
PK0290-7.DOC
Claims (1)
- 中聲蓴ITKli.一種使用陽離子矽酮製造柔軟薄紙的方法,包含下列 步驟: (a) 形成一織維素造紙纖維的含水懸浮液,包含由纖維 總重之0.01至1乾基重量百分比(wt%)陽離子發嗣; 其中一夹層薄紙片包含一第一層與一第二層,其中第 一層爲一外層且包括主要硬木纖維與由〇·〇1至1乾 基重百分比(wt%)之陽離子石夕酮.,以及其中第二層包 括主要軟木纖維; (b) 沈滅;含水懸浮液於一具小孔之成型濾網,其可保留 纖維以形成一濕織物; (c) 將織物脱水或脱水/乾燥; (d) 以製皴粘合劑粘附織物於製敏圆筒;其中製敏粘合 劑包含由20至60乾基重量百分比(wt%)之聚乙埽 醇’及由20至60乾基重量百分比(wt%)之熱固性陽 離子聚醢胺樹脂’以及由15至25乾基重量百分比 (wt%)之四級化矽鹹聚氨基醯胺脱模劑;以及 (e) 以製鈹刀片由製皺園筒製皺織物而形成一軟紙。 2·如申請專利範園第1項之方法,其中陽離子矽酮量由 〇.〇5至〇·5乾基重量百分比(wt%)。 3·如申請專利範圍第丨項之方法,其中陽離子矽酮量由 〇·1至0.2乾基重量百分比(wt%)。 4.如申請專利範園第〗項之方法,其中織物於製敏刀片 處被乾燥至水分含量0.01 %至3%。 如申請專利範圍第丨項之方法,其十造紙纖維爲硬木 PK0290-10 nnr 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) --------—^------.玎-----.ii f請先閲讀背面之注意事項再填寫本頁} 經濟部中央標準局員工消費合作社印製 simrv ^ 公告本 Αί BS cs D£ WK,8·' Θ襦毛 濕織物通過乾燥 量百分比(wt%) 申請專利範圍 纖維,之後沈澱於成型濾網而成爲薄紙織物之外層。 6 ·如申請專利範圍第6項之方法,其中硬木層於製皺過 程中,被置於靠著製皺圓筒之表面。 7·如申請專利範圍第1項之方法,其中矽酮爲聚矽氧 烷。 8. 如申請專利範圍第1項之方法, 、T濕織物以濕壓榨 與粘附於揚基(Yankee)乾燥器的古^ 0 , . ^ ^ 々式被脱水。 9. 如申請專利範圍第1項之方法,其中 與附著於一製皺圓筒上。 1〇·—種軟紙片,包含由〇,〇1至1乾基重 之陽離子·ε夕嗣。 丨I-1 I . I裝 I 訂 I .線 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 PK0290-lO.DOC 本紙張尺度適用中國國家標準(CNS〉A4規格(210X297公釐)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/287,638 US5529665A (en) | 1994-08-08 | 1994-08-08 | Method for making soft tissue using cationic silicones |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| TW318194B true TW318194B (zh) | 1997-10-21 |
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|---|---|---|---|
| TW084107984A TW318194B (zh) | 1994-08-08 | 1995-08-01 |
Country Status (12)
| Country | Link |
|---|---|
| US (2) | US5529665A (zh) |
| EP (1) | EP0775235B1 (zh) |
| JP (1) | JPH10504358A (zh) |
| KR (1) | KR100385273B1 (zh) |
| AU (1) | AU693582B2 (zh) |
| BR (1) | BR9508544A (zh) |
| CA (1) | CA2150790C (zh) |
| DE (1) | DE69528835T2 (zh) |
| PL (1) | PL180701B1 (zh) |
| TW (1) | TW318194B (zh) |
| WO (1) | WO1996005372A1 (zh) |
| ZA (1) | ZA956371B (zh) |
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-
1994
- 1994-08-08 US US08/287,638 patent/US5529665A/en not_active Expired - Fee Related
-
1995
- 1995-06-01 CA CA002150790A patent/CA2150790C/en not_active Expired - Fee Related
- 1995-07-14 JP JP8507321A patent/JPH10504358A/ja active Pending
- 1995-07-14 EP EP95926701A patent/EP0775235B1/en not_active Expired - Lifetime
- 1995-07-14 KR KR1019970700830A patent/KR100385273B1/ko not_active Expired - Fee Related
- 1995-07-14 DE DE69528835T patent/DE69528835T2/de not_active Expired - Fee Related
- 1995-07-14 BR BR9508544A patent/BR9508544A/pt not_active IP Right Cessation
- 1995-07-14 PL PL95318497A patent/PL180701B1/pl unknown
- 1995-07-14 AU AU30991/95A patent/AU693582B2/en not_active Ceased
- 1995-07-14 WO PCT/US1995/008893 patent/WO1996005372A1/en not_active Ceased
- 1995-07-31 ZA ZA956371A patent/ZA956371B/xx unknown
- 1995-08-01 TW TW084107984A patent/TW318194B/zh active
-
1996
- 1996-03-18 US US08/616,952 patent/US5591306A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| MX9700901A (es) | 1998-03-31 |
| AU3099195A (en) | 1996-03-07 |
| US5591306A (en) | 1997-01-07 |
| AU693582B2 (en) | 1998-07-02 |
| PL318497A1 (en) | 1997-06-23 |
| WO1996005372A1 (en) | 1996-02-22 |
| ZA956371B (en) | 1996-03-14 |
| JPH10504358A (ja) | 1998-04-28 |
| EP0775235B1 (en) | 2002-11-13 |
| PL180701B1 (pl) | 2001-03-30 |
| DE69528835T2 (de) | 2003-09-18 |
| EP0775235A1 (en) | 1997-05-28 |
| US5529665A (en) | 1996-06-25 |
| BR9508544A (pt) | 1997-08-12 |
| CA2150790C (en) | 2004-07-13 |
| CA2150790A1 (en) | 1996-02-09 |
| KR100385273B1 (ko) | 2003-08-19 |
| DE69528835D1 (de) | 2002-12-19 |
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