CN1048530C - 聚烯烃聚合物纤维 - Google Patents
聚烯烃聚合物纤维 Download PDFInfo
- Publication number
- CN1048530C CN1048530C CN93121259A CN93121259A CN1048530C CN 1048530 C CN1048530 C CN 1048530C CN 93121259 A CN93121259 A CN 93121259A CN 93121259 A CN93121259 A CN 93121259A CN 1048530 C CN1048530 C CN 1048530C
- Authority
- CN
- China
- Prior art keywords
- fabric
- fiber
- copolymer
- polyamide fiber
- polymer
- 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.)
- Expired - Fee Related
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 118
- 229920000642 polymer Polymers 0.000 title claims description 58
- 229920000098 polyolefin Polymers 0.000 title description 5
- 229920001577 copolymer Polymers 0.000 claims abstract description 39
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004744 fabric Substances 0.000 claims description 82
- 238000000034 method Methods 0.000 claims description 46
- 238000009826 distribution Methods 0.000 claims description 33
- 238000005516 engineering process Methods 0.000 claims description 23
- 230000008569 process Effects 0.000 claims description 22
- -1 octene-1 Natural products 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 8
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 6
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 3
- 229920001038 ethylene copolymer Polymers 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims 13
- 229920002647 polyamide Polymers 0.000 claims 13
- 238000002074 melt spinning Methods 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 description 53
- 239000003054 catalyst Substances 0.000 description 45
- 238000004519 manufacturing process Methods 0.000 description 20
- 238000012360 testing method Methods 0.000 description 19
- 238000009987 spinning Methods 0.000 description 17
- 230000004087 circulation Effects 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 14
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- 238000012545 processing Methods 0.000 description 11
- 210000000689 upper leg Anatomy 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000004698 Polyethylene Substances 0.000 description 7
- 229920001684 low density polyethylene Polymers 0.000 description 7
- 239000004702 low-density polyethylene Substances 0.000 description 7
- 229920000573 polyethylene Polymers 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000004753 textile Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 238000004080 punching Methods 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000004927 fusion Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 206010011416 Croup infectious Diseases 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000004811 fluoropolymer Substances 0.000 description 3
- 229920002313 fluoropolymer Polymers 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 229910000765 intermetallic Inorganic materials 0.000 description 3
- 229920000092 linear low density polyethylene Polymers 0.000 description 3
- 239000004707 linear low-density polyethylene Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 229920005594 polymer fiber Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 2
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- HEAMQYHBJQWOSS-UHFFFAOYSA-N ethene;oct-1-ene Chemical compound C=C.CCCCCCC=C HEAMQYHBJQWOSS-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229950011008 tetrachloroethylene Drugs 0.000 description 2
- 238000006886 vinylation reaction Methods 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- 206010009866 Cold sweat Diseases 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- 229920000433 Lyocell Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004708 Very-low-density polyethylene Substances 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 230000002344 fibroplastic effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229920001866 very low density polyethylene Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 210000003857 wrist joint Anatomy 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/30—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising olefins as the major constituent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
- C08L23/0815—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Ethene-propene or ethene-propene-diene copolymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2915—Rod, strand, filament or fiber including textile, cloth or fabric
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
- Y10T442/681—Spun-bonded nonwoven fabric
Landscapes
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Artificial Filaments (AREA)
- Nonwoven Fabrics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Woven Fabrics (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Organic Insulating Materials (AREA)
- Multicomponent Fibers (AREA)
Abstract
纤维具有独特的弹性特性,它包括乙烯和共聚单体的共聚物,共聚物具有密度范围为0.86至0.91g/m3,MWD范围在2至3.5,熔融指数范围在4至1000,并且SDBI少于28℃。
Description
本发明涉及的是乙烯共聚物纤维,以及由该纤维制成的织物。至今利用聚乙烯来成形纤维束和有用的纺织品已受到现有的聚乙烯树脂加工方法的限制。本申请制得的纤维和织物具有特殊的令人满意的特性,它是通过采用聚合物成形法而实现的,而不是通过一些以前的已经试图的采用众多不便的方法来实现的。
根据过去的方法,自由基引发法和齐格勒-纳塔催化法一直是烯烃聚合和高分子量烯烃聚合物和共聚物制备的有效方法。在40年代已发展使用自由基引发工艺技术。该技术使用高压力、高温度、和自由基引发剂例如过氧化物。当乙烯在自由基引发过程中被聚合时,由这样过程而形成的聚乙烯通常具有约0.91~0.935g/cm3范围的密度,并称之为低密度聚乙烯(LDPE)。由自由基方法而形成的聚乙烯通常具有大量不同长度的分支链。
在50年代末和60年代初,利用“齐格勒-纳塔”(Z-N)催化剂已变得很普通。这些催化剂可被使用在一个较大范围的工艺方法之中,其中包括低、中、高压力的工艺方法。通常,当乙烯使用Z-N催化剂而被聚合时,产生“线性”产品,其聚合物分子基本不分支。这种线性聚烯烃通常具有相对高的密度,其范围大约在0.941~0.965g/ml,这是因为该线性聚烯烃比较于较多支链和较低密度材料,其聚合物分子和最小支链缠结是较致密的。使用Z-N催化剂而生产出的聚合物质的一个特征是他们有非常宽的分子量分布,相同的现象在LDPE′S中已描述过。
Sawyer等人的美国专利US4,830,987;US4,880,691;US4,909,975描述了在某些有限的纤维应用中使用具有0.919密度的乙烯/辛烯(E-O)共聚物来。遗憾的是,在Sawyar等人优先权日时由于使用传统现有的齐格勒-纳塔催化剂,特别低密度聚乙烯的纤维制造非常困难,这是因为在这些聚合物中固有地产生宽广的或宽的分子量分布。Kubo等人的美国专利US5,068,141报道了在Sawyer等人所公开技术中的一些困难。
而提出的具有宽的分子量分布的聚合物在分批加工过程中可能有很大的变化。一种齐格勒-纳塔类型的宽的分子量分布(MWD)材料将包括有分子的有效片断,该分子比标称分子量又较长又较短,这些物质的存在影响于树脂的特性。
聚合物所具有的大片断的短链在相对低温时将非常易于自由游动,但是相同的片断将引起聚合物,或其产物呈粘附或粘结状,在加工过程中具有令人不愉快的气味或味道,或烟,并具有特别低的张力强度。在进行纤维成形期间,由于连续的“粗节”或断裂,纤维是非常难以加工的。某些粗节的出现是由于低分子量聚合物小球体的形成在模具面的表面上或在通过模具而所形成的纤维表面上。这些小球体离开纤维形成部分的表面可能会破碎或冲击纤维的表面,以引起破碎或其它不足。
使用高分子量物质则产生其它一些困难,对于尤其标称分子量的具有大片断的非常长链聚合物物质的聚烯烃树脂将使得形成的纤维非常好,但是他们将是脆性的或手感特别粗糙的,这是由于在其聚合物本自内有很高的结晶度。本发明的纤维将把所述的困难减至最低程度。
Kubo等人在US5,068,141中描述的成形的无纺织物是由乙烯和辛烯的线性低密度聚合物而形成的长丝所构成的。他们指出在使用于所形成纤维的聚合物中共聚单体结合的量而受到限制,这是由于在低的结合百分率时硬化,而在高的共聚单体结合百分率时成形于非常细的长丝是困难的。他们还指出适合于其申请的聚合物的有效范围的密度受到限定,这是由于在其密度下所获得的长丝有不良的强度,而在其密度下本发明使得细纤维产品具有满意的强度并且手感柔软并令人满意。
Fowells的美国专利US.4,644,045,利用在低温时来熔融一种聚合物而用来纤维的纺丝或拉伸,通过调整纺丝或织物成形加工条件情况来克服粗节和破损的加工问题。Kubo等人指出该技术导致不良的拉抻,它还导致时常发生长丝断裂,这是由于在其低温操作中需要高强度而引起的。
Krupp等人的美国专利US4,842,922,描述了一种纺粘织物,它是由线性聚乙烯的混合物在高生产速度下而制备的。Krupp认识到在形成纤维中和后来的由高分子量聚乙烯而形成的无纺织物中常有困难。由Krupp等人所提出解决方法是把一种高分子量聚乙烯,特别是一种线性低密度聚乙烯与一种低分子量的聚乙烯混合。此外,这是一种麻烦多个步骤的工艺过程,目的是用来克服加工的局限性。
Coleman的美国专利US4,612,300描述了一种聚合催化剂,它可生产一种具有稍微窄的分子量分布的聚合物,并给出烯烃催化的已知技术。然而,由此所得到的聚合物将会有相对高的密度,这种材料可用于纤维成形的加工,这是由于它具有高的结晶度和高的熔体强度,但是这种纤维将是刚性的或坚硬的,并将产生一种“手感粗硬”的织物,这是由于晶体结构的实际变形一定出现在提供于所“给出”的织物或外衣上。
Kobayoshi等人的美国专利US5,078,935,描述了连续聚丙烯纤维纺粘成的无纺织物产品,它具有令人满意的“手感”,或尚好的手感,可惜的是,良好的手感是由附加的机械起绉方法而得到的,该方法使得较长纤维暂时仿佛变得较短。以这种方式起绉而产生出织物,由这种织物可制造紧身服装,这种服装具有某些“适应性”。
如果由其它方法而遇到一些困难并尝试一些不太方便的途径,那么清楚地知道,它将对改进聚合物纤维是有用的,该纤维是柔软的并且对人身运动是易变形的,而无需对由于纺丝前聚合物混合的低熔融温度而要求的低的纺丝速度,或对纤维或其所得的织物的机械变形化费巨大精力,而所得到最终的织物对于穿着者来说还是相当好的。理想的是它将有益于纤维形成,该纤维不需要额外的加工步骤,但能仍然提供柔软、舒适的而不发粘的织物。我们对解决这些问题的方法是采用具有明显不同特征的一些共聚物以生产一些纤维和织物。该对策避免了先有技术中所描述的不便的加工步骤。
在一种加工方法中树脂制造商有效地生产具有“柔软度”的纤维和织物,该方法纤维制造商受益非浅。这就去掉了一些费用大的超出纤维和织物制造商的加工技术的额外加工步骤,例如起绉、混合。本发明所要做的正是于此。纤维的生产人员能容易购买聚烯烃树脂,该树脂具有固有的高值特性。容易生产的所希望的纤维和织物具有这样优点,排除了对令人不满意的使用不便的额外加工过程的需要,例如树脂混合,后加工的起绉,或慢速纺丝。
到今对制造低密度,特别低于0.91的LLDPE的纤维是十分困难的。这些低密度的聚合物根据以前观点则基本上是粘的,粘性的并且是不成形的。试图拉伸由这种材料制成的纤维或长丝在最好情况下也是十分困难的。试图拉伸由这种材料制成的纤维或长丝将导致所成形的绳状线股具有小的拉伸强力,它在成形期间将会连续地产生粗节或易断丝并难控制。任何所获得的线股或纤维将继续流动,这样在进一步加工或使用期间会损失其形状。此外,传统受催化的具有低MW片断的聚合物加工过程是十分困难的,这是由于这些低MW材料的挥发作用而引起“烟雾”。
通过本发明的实践,它能制造一些纤维和织物,它们通过单点催化剂所生产的聚合物而制成的,现有可能的是所制造的纤维和织物具有高值特性,而这在以前则是不可能的。由这些高分子量的非常低密度聚乙烯制成良好纤维成形,其聚乙烯是来自于聚合单体的分子量窄分布和适当分布的结合,并且乙烯遍于所使用的聚合物的主链。这些结合的特性来自于通过利用单位点金属茂型催化剂而成形的聚合物,从而使得生产出这些极好的纤维。在纺织应用中利用这些与众不同的纤维而提高成品纺织品,该纺织品是柔软的,“能伸长的”,或具有高弹恢复性(非常低的永久定形),可透气,以及特别令人满意的手感。当这些纺织品用于在成品服装时,他们在长时间内对于穿着者来说是舒适的,柔软的并对于人体是令人满意的,对人体运动有非常好的忍受性,并在连接区域或人体的其它多弯曲部分区域处没有约束。
随着单点催化剂体系的出现和近来快速的发展,例如,该内容已由Welborn的EPA129368,Turner和Hlatky的EPA277003,EPA277004,和US5,153,157和Canich的US5,057,475以及Canich,Hlatky和Turner的WO92/00333中描述,所有这些技术在此可结合参考,对于更精确地制作烯族聚合物的分子量分布,在其聚合物制作时,它已成为可能。其方法使得在这方面材料能够获得非常窄的MWD,而几年前仅有宽的MWD材料存在。LLDPE具有这样窄的MWD,而又有通常的高分子量聚合物,它有效地提供聚合物,该聚合物不会产生有低的MWD片断,其低的MWD片断对于线股成形方面会产生困难。这些窄的MWD产品具有通常较高均匀的结晶度,这是由于他们没有低MW片断。此外,他们不是高度结晶材料,并且不是脆性或刚性的。
其产物是一种聚合物,该聚合物对其形成新的,柔软的,弹性纤维具有显著能力,织物由其所述的纤维可容易地形成。由于纤维可通过传统的熔融纺,纺粘,和熔喷以及挤压,和本领域中已知的其它方面而被形成,目前则有可能的是对其形成的织物能被拉伸,起皱纹,以及穿着舒适。具有非常良好手感的这些长丝,纤维,或线股所形成的这些织物是非常透气的,并且是意外的轻质。这就使得这种织物的服装对于穿着者来说是相当的舒适,这是由于他们拉伸时需要少的作用力并立刻恢复到他们原有形状。由于织物的手感是如此的令人满意,以致于其服装对于穿着者是惊奇的舒适。仅在典型的应用上,这些服装可包括尿布,特别是衬垫和侧面垫布,医用长上衣,以及其它一次性使用或是用完弃掉的物品。其它的例子包括弹性绷带,防护服装,体育服装包括腕关节和头带,或在数层之下芯吸,以及其它应用方面包括医用布,而此处所用的医用布则要求具有弹性和舒适。
除了聚合物树脂的最终分子能够制作为分子量分布所产生非常理想的特性外,在聚合作用期间在其所生产的聚合物主链内,这些新的金属茂型催化剂具有能够容易结合大量不同大小之聚合单体的理想特性。此外,如在以前技术中所描述的,这些催化剂可有利的用于一些不同的聚合作用过程,例如包括高压力,中等压力,低压力,溶体相,块状相,浆相,和气相聚合作用。
聚合物的分子量分布(MWD)被称之为Mw/Mn的此率,它是平均分子量重量除以平均分子量数。“大约”1.8-3.5范围之内的MWD可用于本发明的技术中,明显地用于分子量分布的上限是在约3.5范围,而3或低于3则为较佳上限范围。
在聚合物链内能够结合大量聚合单体,同时仍保持控制聚合物的整个窄的分子量分布则显然是单点催化剂特别是金属茂型催化剂的独特所在。这些新的催化剂体系或催化复合物的有利特性现使得可能来获得用于形成线股或纤维的聚烯烃树脂,其纤维或线股接下来加入到织物里,其织物柔软而不僵硬,并能够起皱纹,手感和穿着令人满意,能够透气,并在需要处具有弹性,而没有由于较短链聚合物质存在而引进的不良气味或粘性。此外,这些单位点催化剂生产的树脂消除了在加工过程期间由低MW物质的挥发而引起的烟雾,而不包括这些低MW物质。
在一种为确定能够赋于具有特性的整个聚合物的聚合单体分布的合理和精确的方法的尝试中已开发了一种新的试验,在试验为“溶解度分布宽度指数”(SDBI),SDBI测量的概述包括了一种认可的类似于早期公开的“组合物分布宽度指数”测量,如在WO90/03414并于1990年4月5日公开的文献中所描述的。
通常,这个试验是为在一种特定溶剂中以变化的温度来测量一个聚合物树脂样品的溶解度而提供的。净有效作用是在聚合物样品中多支链物质通常更多地溶解在较低温度的溶剂中。随着样品和溶剂的温度的增加,较少支化的物质开始溶解。这就使一种检测器来测量已溶解聚合物的数量,其检测器是在洗脱柱的下游,其聚合物在各种温度下洗脱。由所测量的溶解度分布曲线,可计算出平均溶解温度,还能算出所称的溶解度分布宽度指数(SDBI)的数值,它是测量溶解度分布曲线的宽度。在其计算中通过使用四分之一的乘方项,SDBI以这样的方式而确定,其值对聚合物的量敏感,而聚合物是在排除于平均溶解温度的一些温度下增溶。
溶解度分布可通过利用一种圆柱而被测量,该圆柱164cm长并有1.8cm ID(内径),在其内径装有无孔的玻璃小球(20-30目),并浸入在温度程序油浴中。该油浴被用力地摇动,使在油浴中温度增减率减至最小值,并且浴中温度是使用铂阻温度计来测量的。大约1.6g的聚合物放置在一个样品制备腔室中,该腔室反复地抽空,并充装有氮气,以从系统中除去氧气。然后把四氯乙烯溶剂的计量体积注入到样品制备腔室中,此时它被揺动并在3个大气压下于140℃温度下来加热以获得约1%浓度的聚合物溶液。然后把这个溶液计量体积100ml注入到大约120℃的恒温封装圆柱内。
在圆柱内的聚合物溶液通过以大约20℃/min的冷却速度把圆柱冷却到0℃而基本上被结晶。然后用25分钟把圆柱温度保持在0℃。接着通过抽吸纯的溶剂而开始进行洗脱步骤,预热油溶温度,以27cc/min的流速通过圆柱。流出物从圆柱通过一个加热管道而到IR检测器处,其检测器用于测量流出物料流的吸收率。以大约2960cm-1处聚合物碳氢伸张带的吸收率作为在流出物中聚合物的相对重量百分比浓度的连续测量。在经过红外检测器之后,流出物的温度减到约110℃,并在流出物料流入到自动分馏物收集器之前,将压力减到大气压力。按3分钟间隔时间收集分馏物。在洗脱步骤中,纯的四氯乙烯溶剂通过圆柱以0℃,27cc/min用25分钟而被注入。由此洗涤聚合物,该聚合物在圆柱以外冷却期间没有被结晶,以致未结晶聚合物的百分比(即0℃时可溶的聚合物百分比)能够由红外扫描而测定。然后温度按程序以1.0℃/min的速率上升,直到120℃。从而获得溶解度分布曲线,即溶解之聚合物的重量分数作为温度函数的曲线图。
用于计算溶解度分布宽度指数(CDBI)的方法下面将描述。
两个乙烯共聚物的溶解分布已表述在图1中,在此,仅为说明清楚起见,样品X具有窄的溶解度分布,与样品Y比较,样品X在窄的温度范围内洗脱,样品Y具有宽的溶解度分布。溶解度分布宽度指数(SDBI)用于测量溶解度分布曲线的宽度。设定W(T)是在温度T下洗脱(溶解)的聚合物的重量分数,平均溶解温度Tave由下式给出
Tave-∫TW(T)dT,当∫W(T)dT=1时,
SDBI用下列关系式计算出:
(SDBI类似于溶解度分布曲线的标准偏差,但它是对T-Tave的4乘方,而不是2乘方。例如图1中的窄的溶解度分布样品X(单点催化剂(SSC)生产的)和宽的溶解度分布样品Y(多位点催化剂(多)生产的)所具有的SDBI值分别等于14.6和29.4℃。
对本发明的纤维和织物来说SDBI较好的值是小于25℃,更好的是小于20℃。
为清楚描述本发明起见,术语“纤维”是指至少包括于由Sawyer等人的申请文件中所描述的相关术语,其中包括纤维,单根长丝,复丝,短纤维和线股,而不涉及这些产品的任何成形方法。例如,我们考虑到,术语“线股”至少包括一种可由一般方法而形成的纤维以及例如可由片材或带片切割成切断而成的纤维。
为清楚描述本发明起见,术语“共聚单体”是指至少包括:乙烯化不饱和烯烃,或烯烃物质,环状烯烃,乙烯化不饱和非环状不共轭多烯烃,环状不共轭多烯烃,乙炔化不饱和单体,或它们的混合物。
现已研制出由乙烯和共聚单体的共聚物制成的新型纤维,以及含有这些纤维的织物,其共聚物密度范围为约0.86至0.93g/cm3,最好上限为0.91g/cm3,MWD范围为约2至3.5,最好上限为3,熔融指数范围为约4至1000,并且SDBI小于约25℃。这些纤维和织物具有独特的柔软特性,具有永久的弹性恢复性,这种恢复性根据密度的不同而有所差异,而这种差异是在5-30%之间,对穿着者来说它不粘结,不僵硬,可透气并非常舒适。这些特性通过特制的聚合物而实现于纤维中,其纤维是由所述的聚合物而制成,而不是通过不便的混合,后成形机械变形,或其它困难或不经济的加工过程。这些纤维可通过任何方法而生产,它从熔融的聚合物中拉出纤维,其中包括熔纺,熔喷,和纺粘工艺技术,也可以采用非传统方法包括片材切割或填充料卷曲以及本技术领域中可采用的其它方法进行生产。
本发明的一个方面是直接涉及到纤维及该纤维的形成,其纤维是由乙烯和共聚单体的共聚物所构成,所述的共聚物具有大约0.86至0.93g/cm3范围的密度,最好是小于约0.90或0.91g/cm3,即范围的上侧,MWD的范围为约2至3.5,最好是范围的上侧约为3,熔融指数的范围为约4至1000,SDBI小于约25℃。
本发明的另一方面是制造这种纤维的方法,它包括从熔融共聚物的贮存器中拉出纤维。
本发明另一方面包括把熔融共聚物通过至少一个形成装置并同时或随后固化共聚物从而成形纤维。例如,这种方法可包括传统的熔融纺和用纺粘工艺方法使纤维形成。
本发明的另一方面包括通过一种不同于共聚物的流体围绕熔融共聚物运动而形成纤维。例如,这种方法将包括纤维形成在熔喷织物形成的早期阶段。
本发明的另一个重要方面包括由所述方式所生产的纤维而形成织物。
根据本发明,它提供一种由乙烯和一个或多个共聚单体的共聚物而组成的纤维,其共聚物具有约0.86至0.93g/cm3的密度,分子量分布为约2至3.5,熔融指数(MI,ASTM D-1238(E))为约4至1000,并且SDBI小于约25℃。
每一共聚单体最好具有3至20,最好是3至10碳原子,例如可包括丙烯,丁烯-1,己烯-1,辛烯-1,4-甲基-1-戊烯,苯乙烯,或它们的混合物。
通常,MWD越窄越有利于纤维生产,这样较好的MWD范围为2至3。SDBI是沿着共聚物主链而衡量共聚单体单元分布的尺度。一般情况下,更均匀的分布是较好的,即较窄的成分分布均值。于是对于纤维来说,SDBI小于约25℃,较好的是小于约20℃。
在共聚物中共聚单体的性质和比率控制着密度,并且较好是调整共聚单体的类型和含量以产生约0.86至约0.93的密度,更好的是0.86至大约0.92. 0.915,0.910或0.90,最好的是到0.89。这样的密度,连同于所要求的共聚物MWD,MI和SDBI的特性现已发现可生产出具有最佳的生产和使用特性的纤维。
共聚物较好的MI取决于纤维形成的方法,对于由纺粘法而生产的产品,较好的范围是4-60,而对于熔喷法,较好的范围为10-1000。
本发明的纤维较好的用途是用于织物的形成,尤其是无纺织物。由该纤维而形成的织物现已发现具有极好的弹性特性,使得他们适用于服装的许多用途。他们还具有良好的悬垂性。
纤维和织物的某些所希望的特性可用抗拉模量和永久定形来表示。根据本发明,对于一种纺粘型织物,所获得的一些较好特性如下列所述:
抗拉模量(g)(ASTM-1682)(拉伸100%,6次循环,机器方向(MD)):较好的是小于900,更好的是小于800,最好是100到400。
抗拉模量(g)(拉伸50%,6次循环,MD):较好的是小于700,更好的是小于600,最好是100至300;
抗拉模量(g)(拉伸100%,6次循环,横向方向(TD)):较好的是600,更好是小于500,最好是50至300;
抗拉模量(g)(拉伸50%,6次循环,TD)):较好的是小于370,更好的是40至200;
永久定形(%)(通过使用一种改进型的ASTM-D-1682,在其上循环拉伸而获得,由于考虑到织物的损坏,而不是连续的拉伸)(拉伸50%,6次循环,MD):较好的是小于30,更好的是在5-20的范围之内,最好是小于10-20;
永久定形(%)(拉伸50%,6次循环,TD):较好的是小于35%,更好的是在5-25%范围内;
永久定形(%)(拉伸100%,6次循环,TD):最好小于40%,更好的是在约5-35%范围内,最好是8-20%;
永久定形(%)(拉伸100%,6次循环,TD):最好小于40%,更好在约5-35%范围内,更好是在约5-25%范围内;
粘合温度(℃)小于110,更好的是在约35-105范围内,最好是40-80。这些特性是较佳的并且对于本发明所有的织物具有实用性,并且已被根据本发明的纤维而制成的一种织物所证明,其织物具有织物定量约70至80g/m2,较好的是约70g/m2,其织物是由具有直径约25-28μm的纤维所形成。对于熔喷织物,根据本发明,较好的特性如下:
永久定形(%)(拉伸50%,6次循环,MD):较好的是小于25,更好的是在约10-20范围内,最好是15-18;
永久定形(%)(拉伸50%,6次循环,TD):较好的小于25,更好是在约10-20范围内,最好是15-18;
抗拉模量(g)(拉伸50%,6次循环,MD):较好的是不大于300,更好的是在约200-300范围内;
抗拉模量(g)(拉伸50%,6次循环,TD):较好的是小于300,更好的是在约50-150范围内,
综合效果(g):较好的是小于约75,更好的是小于约70,最好的是在约10-20范围内。
这些特性是较佳的并且对本发明的所有织物具有实用性的,例如已被根据本发明的熔喷织物所证明,该织物具有标称织物单位重量70g/m2,它是由根据本发明的具有直径为8-10μm的纤维所制成。
随着近来的发展,在利用已制成的单点催化剂而使烯烃聚合的技术中,生产如在前描述的聚合物是可能的。根据这些单点催化剂而制成的聚合物,我们已生产出独特的纤维,该纤维在此已描述,并且在由这些纤维而生产的织物中产生显著的和有益的效果。对于本发明的目的,金属茂催化剂不仅包括双环戊二烯基的转变金属化合物,而且还包括单环戊二烯基/异质原子转变金属化合物,以及其它类似的与一种活性辅助催化剂结合的催化转变金属化合物。可包括有机金属辅助催化剂,特别是以铝代环氧烷(alurnoxanes)形式的有机铝化合物,或是膨松阴离子催化活化剂,如在EPA277003和277004中所描述的。
通过使用这些催化剂体系和其共聚单体,形成用于本发明技术的聚合物树脂是可能的,其密度范围为0.86至0.93。在该范围内,这些催化剂体系也将产生树脂,它具有特定窄的分子量分布,其分布是集中于任何所希望的一些分子量上。
通常用于生产本发明的纤维或线股的最好途径是从在前描述的一个适当共聚物的熔融贮存器中拉出它们,这些共聚物可通过聚合于具有单点催化剂体系的共聚单体的适当化合物而生产出。尤其是使用的催化剂体系包括金属茂/和单环戊二烯基-异质原子-转变金属/活化剂体系,如在EPA129368,EPA277003,EPA277004,US5,153,157,US5,057,475和WO92/00333中所描述的。正如本技术领域中所已知的,用于这些相类似的催化转变金属化合物的适当活化剂包括各种铝代环氧己烷(alumozanes),尤其是三甲基铝代环氧己烷(alumozanes)和膨松的不稳定阴离子活化剂。
实施例
一些共聚物的一些样品用来形成一些纤维,共聚物密度范围大约为0.86g/cm3到约0.93g/cm2。由这些单点催化剂生产的聚合物纤维或金属茂型催化剂生产聚合物的聚合物纤维以几种方式表现出了惊人的和独特的效果。首先,非常显著的是这些低密度材料将完全被纺成纤维。当与由传统的催化剂而生产的共聚物比较时,如果其共聚物完全被纺丝,那么人们所希望的是这些共聚物会形成粘性的,gooey纤维,这些纤维在一个无用和无定形块状物中会相互粘结。然而,令人惊奇地是,这些树脂纺成纤维非常好,并且实际表现出从质量方面较容易形成纤维。
第二,由所得到的纤维制成的织物具有非常柔软的织物组织和呈现出毫不期望的“粘性”或粘着性,这种低密度聚合物是由传统型催化剂而生产的,如由Sawyer等人所描述的,如果成功地纺成纤维,纤维会是十分难以加工的。
或许最惊人效果是其所说明的这些纤维和由其纤维制成的织物他们显著的弹性性能和悬垂性。比较于较高密度的聚乙烯,这些织物显示较小的张力和永久变形,而人们对于织物所希望的是在经过拉伸应力之后其织物显示出显著的弹性回复,或低的永久定形。
另外,已经发现,这些材料缺少低分子量物质,该物质必定由更多的传统的催化剂来生产。因此,他们缺少短链或低分子量物质,该物质会被料到影响纤维表面特性。没有低MW物质,一点也没有能够以粘性材料形式渗出于纤维的表面,其粘性材料将会有传统催化剂所生产的材料的特性。另一优点在于这些单点催化剂生产的材料,它可说明易于纺丝的质量观察,如后面所述,它让确实缺少低分量(短链)物质不会有问题,在纺丝期间,用有损害的较短链的物质集中于喷丝板孔周围。
在一般加工过程中,这些物质会收集到一点,并且最终脱落以引起在所纺的纤维上的不规则性,并且也许一个破损或一个粗带将会导致纺丝生产线的停止。单点催化剂生产的共聚物用于成形本发明的纤维(实施例1-4,和6-8),以高速的纺丝速度可长时间的自由纺丝而没有粗节。与所述的传统的受催化的材料比较,其受催化材料用于比较实施例5和6中。其比较材料在加工过程中经常呈现粗节,这就使得在试验纺丝期间必需多次停止生产线运转。
与织物柔软度相关的一个特性是“悬垂性”,这个特性是在一个定量样子上测得的。通常,一块织物放置或“悬垂”在一个具有复杂形状的物体上,例如人的手或拳头。具有低悬垂性的织物呈现许多“皱纹”或“硬的”褶皱,它们隐藏下物体的形状,高度可悬垂的织物将几乎没有这样的褶皱,而通常会使外形更接近下物体的形状。尽管是定量测量,但它描述的一种概念和测试可被熟悉纺织技术的人员理解。毫不例外,单点催化剂生产的树脂呈现了高度的悬垂性。在每组试验中,由比较试验树脂构成的织物没有高度可悬垂性。对于穿着来说,可悬垂的织物会感觉十分柔软,而较小悬垂性的织物将感到“粗硬”或刚性的并且对穿着有刺激作用。
由单点催化剂生产的共聚物而呈现的其它显著和有益的效果低的粘合温度,该温度是当所纺成的纤维形成无纺织物时所希望的温度。这就意味着有可能在低温下操作粘合设备,例如一种轧光罗拉。对于无纺织物的生产者,这种低温操作将提供能量储蓄。
乙烯/丁烯(EB)(实施例1-3和6-8)和乙烯/丙烯(实施例4)共聚物是在先前所述的密度范围内以纺粘加工技术而进行试验的。根据已测试的比较数据,这些受乙烯-辛烯(EO)共聚物材料测试,其材料确信在使用一种传统多位点催化剂(实施例5和9)的加工技术中已生产出。比较材料是通过传统的催化剂而生产,这比较材料是Dowlex 2517.25熔融指数,0.917g/m3的材料,该材料类似于Dow Aspun 6801,这两种材料可从DowChemical Company,Midland,Michingan获得。使用在这些试验中的单点催化剂生产的材料可从Exxon Chemical Company获得。
第一次试验是对所形成的纤维和所生产的一种纺粘无纺织物。它是通过使用由Reifenhauser Company制造的一种1米Reicofil线路来完成的。挤压机尺寸是7cm(2.75in.)长径比为30∶1。采用3719冲压喷丝板孔,每孔直径为0.4mm,L/D=4/1。表I提供这些所被试验的聚合物一般数据,包括用于每一聚合物试验的加工条件,和所生产的无纺纺粘织物的试验结果。纺粘加工过程是采用织物生产技术领域中所熟知的技术。通常,挤出连续的纤维,放在一个循环带上,然后相互粘结,常常再通过一个热轧光辊,纺粘的概述可从Wodsworth,L.C.and Goswaini,B.C.无纺织物:“纺粘和熔喷工艺方法”中得知,会刊Eighth Annual NonuovensWorkshop,1990年7月30日-8月3日,由TANDEC,Vnivexsityof Tennessee,Knoxville主办。
表I纺粘实验结果
(比较)实施例 1 2 3 4 5共聚单体 EB EB EB EP EO熔体指数(Dg/min) 31 31 9 20 26密度(g/cm2) 0.921 0.888 0.867 0.863 0.917差示扫描量热计Tm(℃) 107.7 73.3 55.2 52 124.1气相分配色谱Mw(K) 45.5 45.2 61.0 47.8 46.2气相分配色谱Mn(K) 21.4 21.7 31.4 21.8 10.4气相分配色谱Mw/Mn 2.1 2.1 1.95 2.2 4.4SDBI(℃) ≤17.0 ≤17.0 ≤17.0 ≤17.0 26.2催化剂 SSC SSC SSC SSC MULTI
表1(续)方向 MD TD MD TD MD TD MD TD MD TD永久变形(%)50%拉伸循环1(%) 17.5 22.4 12.5 -- 6.87 -- 10.0 15.8 22.5 25.8循环6(%) 27.9 32.9 20 -- 11.25 -- 18.6 22.5 32.5 36.7100%拉伸循环1(%) 31.2 30 21.4 22.4 7.0 9.7 10.6 15.8 32.5 35循环6(%) 45 47.5 31 32.7 9.3 13.7 18.75 25 43.8 46模量(g)50%拉伸循环1(g) 621 417 340 -- 127 -- 159 64 812 395循环6(g) 581 367 299 -- 109 -- 132 45 735 395100%拉伸循环1(g) 907 635 449 268 277 141 195 95 1157 726循环6(g) 794 499 399 240 231 113 150 77 1134 680定量(g/m2) 0 70 0 70 0 70 0 80 0 70纺粘温度(℃) 102 0 70 0 51 0 40 112
表I(续)工艺参数实施例 1 2 3 4 5流动速率(克/孔/分钟) 0.35 0.35 0.35 0.35 0.35冲压熔融浓度(℃) 220 219 227 216 211纺丝泵(rpm) 14.9 15 15 15 15.1冲压压力(Kg/cm2) 32.2 36.3 90.0 56.7 42.3粘合压力(Kg/linear cm) 68.3 70.9 68.6 67.9 67.3挤出速度(rpm) 82.3 79.3 78.5 79.3 86.9纺丝带速度(mpm) 15 15.1 15.2 13.9 15.2压光机速度(mpm) 14.7 14.8 14.9 14.8 15.6卷绕速度(mpm) 16.9 16.2 17 20.8 17.2吸风机速度(mpm) 1903 2115 1898 1512 2156冷却空气(℃) 8 8 9 8 7冷却空气(rpm) 1104 1106 1055 1050 1102粘合温度(℃) 102 70 50 40 112
参看抗拉模量,ASTMD-1682,根据悬垂性和柔软度,或纤维或织物的拉伸容易程度,都以50%和100%拉伸,明显看到的是,当与类似的比较材料(实施例5),该材料具有0.917密度和熔融指数为26进行比较时,0.921密度的共聚物具有熔融指数31(实施例1)表示出了显著的减小了抗拉模量或增加了悬垂性和柔软度。根据测量弹性恢复性来参看永久变形,明显看到是,实施例No 1所示出的具有熔融指数31的密度0.921材料以50%拉伸比以同样50%拉伸的比较实施例No. 5具有适当较大的弹性恢复性,或较小的永久定形。参看对织物实施例No 1 100%拉伸所存在的结果,它不能如此清楚的显示出,以致于从由单点催化剂生产的材料而得到的织物的弹性恢复性是显著的好。然而,在50%拉伸之后,在柔软度和弹性恢复方面显著的益处实际上显示出一些好的特性增量。
永久定形是通过滞后实验来测量的,它是用Instron Model 1122来实施的,它具有一个13cm(5in.)的钳口间隙,13cm(5in.)十字头速度13cm/min,以50和100%拉伸,通过所设计的循环数,以用于纺粘材料。这个试验是ASTM D-1682的改进,考虑到织物的损坏,其中拉伸是循环进行的,而不是连续进行的;在预定量的拉伸之后,根据所指定的循环数,恢复性的损失,或永久定形而被测量。后面所描述的熔喷织物用二个循环而进行试验。在第一和最后循环期间,抗拉模量会遇到峰值力。
对于由单点催化剂所生产的聚合物而产生的材料开始对其密度在0.93范围对其特性方面进行改进时,由实施例Nos. 2、3和4可容易地看到,其所测得的弹性恢复性要比比较材料(实施例5)要好,如测得缺少永久定形。另外,实施例No 2、3和4清楚地表示出的抗拉模量,其所涉及的悬垂性和柔软度,对于这些实施例而得以大大改进,并且相对于密度而能够被满足要求。
对于试验实施例与比较实施例,一个相同的倾向是表示在粘合温度方面。具有0.921密度的实施例No 1显示出比具有0.917密度的比较实施例5低于10℃的粘合温度。随着密度的减小,这个在粘合温度上的差值则更显著,如实施例2、3和4所示。所有这些实施例所表现出的粘合温度比其比较实施例的低于约40-70℃。
另外的试验是用相同的材料使用熔喷工艺通过纺制纤维来进行的。熔喷技术在织物生产的技术领域中是已知的技术。一种工艺概述可从“Meltblown Process”,Meltblow Technology Today,MillerFreeman Publications,Inc.,San Francisco.California,1989,pgs 7-12中得到。此外,把传统多位点催化剂生产的树脂(实施例9)与一些单点催化剂生产的各种密度和熔融指数的乙烯共聚单体(实施例6-8)比较。这个试验是使用一个51cm(20in.)Accurate Products Meltblown线而完成的。挤压机是一个5cm(2in.)Davis Standard,其长径比为30∶1 。冲压喷丝板具有501个冲压孔。每孔直径0.4mm(0.015in.),冲压长度为15∶1,并且空气间隙调整到0.15mm,(0.060in.)。比较传统的材料是Dow Aspun 61800.31,它可从Dow Chemical company,Midland,Michigan获得。每一个其它试验的树脂是单点催化剂生产的乙烯共聚单体并且从Exxon Chemical Company得到。
表II表述了一般聚合物特性,工艺参数,和最终织物试验结果。
表II熔喷滞后结果
(比较)实施例 6 7 8 9共聚单体 EB EB EB EO熔体指数(Dg/min) 105 95 31 150密度(g/cm3) 0.917 0.888 0.888 0.931差示扫描量热计Tm(℃) 102 73.4 73.3 125气相分配色谱Mw(K) 31.03 31.96 45.2 26.8气相分配色谱Mn(K) 11.9 15 21.7 7.44气相分配色谱Mw/Mn 2.61 2.13 2.1 3.6SDBI(℃) ≤17.0 ≤17.0 ≤17.0 26.2催化剂 SSC SSC SSC MULTI方向 MD TD MD TD MD TD MD TD永久变形(%)50%拉伸 22.5 22.5 16.7 16.7 15.8 15.8 30 28.3模量(g)50%拉伸 463 399 286 91 231 104 367 345总的手感(g) 69 15 13 84织物单位重量(g/m2) 70 70 70 70扫描电子显微镜纤维直径(μm) 8.9 9.8 9.1 9.2
表II(续)适当的工艺参数:(熔喷)实施例 6 7 8 9熔融温度(℃) 420 420 430 420流动速率(克/孔/min) 0.4 0.4 0.4 0.4%空气 75 75 75 75空气速度(m3/min) 9.20 9.20 9.20 9.20空气温度(℃) 421 422 418 420DCD(cm) 25.4 33 49.5 25.4压力(Kg/cm2) 21.72 22.78 50.97 15.61线=51M(20in)精确熔体喷射线挤压机=5cm(2in)DAVIS标准,30∶1 L/D模孔=501孔径=0.38mm(0.015in.)模具长=15∶1气隙=1.5mm(0.060in.)
当观察出现于表II的结果时,在实施例Nos 6和9之间比较表明,实施例6的织物比起比较实施例9可测得到更大弹性的恢复,但对抗拉模量的测量似乎显著的不太容易被延长。它是密度0.92-0.93范围内,在该密度内,柔软度和弹性恢复力以及低的纺粘温度的这些优点开始显示在本发明的技术中。正如纺粘试验的结果一样,在熔喷试验结果中可看出一些特性,这些特性是同样实际希望开始表现在这个范围,但这些特性更明确地和完全地存在于较低密度范围内,如由单点催化剂生产的聚合物树脂实施例7和8纺成的纤维而制成的织物所表示的。在两组实验中,随着减少聚合物材料的密度,改善了弹性恢复性,或缺少的永久定形。另一方面,“柔软度”的测量是指总的手感。可容易地看出,实际上实施例6所提供的纤维和织物比由比较实施例9的表示的要柔软。除了实施例6的抗拉模量在外的数据外,明显的是由单点催化剂而生产的共聚物树脂提供于本发明的纤维和织物具有已表明的一些有益特性,这些特性是本发明的优点。根据TAPPI 4998 CM-85试验方法,使用一个0.64cm(0.25in.)缝隙和一个20cm×20cm(8in×8in)的样品,在Thwing,Albert Handlo-O-Meter,Model 211-5上来测量总的手感。
Claims (11)
1.包括至少一种乙烯共聚物和至少一种共聚单体的聚烯烃纤维,聚合物具有的密度在0.86至0.93g/m3范围内,分子量分布是在1.8至3.5范围内,熔融指数是在4至1000范围内,和溶解度分布宽度指数小于25℃,其中共聚单体包括一种或多种丙烯,丁烯-1,己烯-1,辛烯-1,4-甲基-1-戊烯和苯乙烯。
2.根据权利要求1的聚烯烃纤维,其中共聚物的密度是在0.86至0.92范围内。
3.根据权利要求1的聚烯烃纤维,其中共聚物分子量分布是在2.0至2.5范围内。
4.根据权利要求1的聚烯烃纤维,其中共聚物溶解度分布宽度指数小于20℃。
5.根据任一上述权利要求的聚烯烃纤维,其中共聚物密度是在0.86至0.89g/cm3的范围内,并且分子量分布是在2.0至2.2范围内。
6.根据权利要求1的聚烯烃纤维,其中共聚物具有:
a)熔融指数是在10至1000范围之内,并且聚烯烃纤维是由熔喷工艺而形成的;
b)熔融指数是在4至60范围内,并且聚烯烃纤维是由纺粘工艺而形成的;
c)熔融指数是在4至150,并且聚烯烃纤维是由熔融纺工艺而形成的。
7.含有由任一上述权利要求的聚烯烃纤维构成的织物。
8.含有由任一上述权利要求的聚烯烃纤维构成的织物,并且具有:
a)在机器方向上拉伸50%6次循环之后,永久定形小于25%;
b)在横向方向上拉伸50%6次循环之后,永久定形小于25%;
c)在机械方向上拉伸50%6次循环之后,抗拉模量不大于300g;
d)在横向方向上拉伸50%6次循环之后,抗拉模量不大于300g;
e)总的手感小于75g。
9.包括通过纺粘工艺而形成的权利要求1-7之聚烯烃纤维的织物,其中共聚物熔融指数是在4-60范围内。
10.一种可悬垂的织物,包括由权利要求1所述的乙烯与一种或多种共聚单体的共聚物所形成的聚烯烃纤维,共聚物的密度是在0.86至0.93g/cm3的范围内,分子量分布是在2至3.5范围内,熔融指数是在4至1000范围内,溶解度分布宽度指数小于25℃,其中共聚单体包括一种或多种丙烯,丁烯-1,己烯-1,辛烯-1,4-甲基-1-戊烯和苯乙烯。
11.包括权利要求10的织物用于服装或窗帘的用途。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US981,029 | 1992-11-24 | ||
US07/981,029 US5322728A (en) | 1992-11-24 | 1992-11-24 | Fibers of polyolefin polymers |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1095771A CN1095771A (zh) | 1994-11-30 |
CN1048530C true CN1048530C (zh) | 2000-01-19 |
Family
ID=25528045
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN93121259A Expired - Fee Related CN1048530C (zh) | 1992-11-24 | 1993-11-24 | 聚烯烃聚合物纤维 |
Country Status (14)
Country | Link |
---|---|
US (1) | US5322728A (zh) |
EP (1) | EP0670918B1 (zh) |
JP (1) | JP3308272B2 (zh) |
KR (1) | KR100295922B1 (zh) |
CN (1) | CN1048530C (zh) |
AT (1) | ATE220133T1 (zh) |
AU (1) | AU683034B2 (zh) |
CA (1) | CA2150006C (zh) |
DE (1) | DE69332083T2 (zh) |
ES (1) | ES2178647T3 (zh) |
FI (1) | FI952500A (zh) |
MX (1) | MX9307314A (zh) |
NO (1) | NO310571B1 (zh) |
WO (1) | WO1994012699A1 (zh) |
Families Citing this family (264)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5278272A (en) | 1991-10-15 | 1994-01-11 | The Dow Chemical Company | Elastic substantialy linear olefin polymers |
US6194532B1 (en) | 1991-10-15 | 2001-02-27 | The Dow Chemical Company | Elastic fibers |
US5783638A (en) | 1991-10-15 | 1998-07-21 | The Dow Chemical Company | Elastic substantially linear ethylene polymers |
US6448355B1 (en) * | 1991-10-15 | 2002-09-10 | The Dow Chemical Company | Elastic fibers, fabrics and articles fabricated therefrom |
US5997989A (en) * | 1992-02-03 | 1999-12-07 | Bba Nonwovens Simpsonville, Inc. | Elastic nonwoven webs and method of making same |
WO1994025648A1 (en) * | 1993-04-27 | 1994-11-10 | The Dow Chemical Company | Elastic fibers, fabrics and articles fabricated therefrom |
CA2163788C (en) * | 1993-05-25 | 2004-04-27 | G. Allan Stahl | Novel polyolefin fibers and their fabrics |
US5948490A (en) * | 1993-11-18 | 1999-09-07 | Plicon, Inc. | Printed cook-in shrink film |
US5468440B1 (en) * | 1994-05-06 | 1997-04-08 | Exxon Chemical Patents Inc | Process of making oriented film or structure |
US5698480A (en) * | 1994-08-09 | 1997-12-16 | Hercules Incorporated | Textile structures containing linear low density polyethylene binder fibers |
US5883144A (en) | 1994-09-19 | 1999-03-16 | Sentinel Products Corp. | Silane-grafted materials for solid and foam applications |
US5932659A (en) | 1994-09-19 | 1999-08-03 | Sentinel Products Corp. | Polymer blend |
US5929129A (en) | 1994-09-19 | 1999-07-27 | Sentinel Products Corp. | Crosslinked foamable compositions of silane-grafted, essentially linear polyolefins blended with polypropylene |
USH1808H (en) * | 1994-11-17 | 1999-10-05 | Shell Oil Company | Extrudable styrenic block copolymer compositions containing a metallocene polyolefin |
US7153909B2 (en) * | 1994-11-17 | 2006-12-26 | Dow Global Technologies Inc. | High density ethylene homopolymers and blend compositions |
DE69525900T2 (de) | 1994-11-17 | 2002-11-21 | Kraton Polymers Research B.V., Amsterdam | Mischungen aus Block-Copolymeren und Metallocen-Polyolefinen |
US6506866B2 (en) * | 1994-11-17 | 2003-01-14 | Dow Global Technologies Inc. | Ethylene copolymer compositions |
USH1798H (en) * | 1994-12-22 | 1999-07-06 | Shell Oil Company | Soft compounds containing elastomeric metallocene polyolefins and styrenic block copolymers |
US5880241A (en) | 1995-01-24 | 1999-03-09 | E. I. Du Pont De Nemours And Company | Olefin polymers |
MX9705627A (es) * | 1995-01-24 | 1998-07-31 | Du Pont | Polimeros de alfa-olefinas y olefinas y su procesamiento. |
US6897272B1 (en) | 1995-01-24 | 2005-05-24 | E.I. Du Pont De Nemours And Company | α-olefins and olefin polymers and processes therefor |
US5652051A (en) * | 1995-02-27 | 1997-07-29 | Kimberly-Clark Worldwide, Inc. | Nonwoven fabric from polymers containing particular types of copolymers and having an aesthetically pleasing hand |
US5955187A (en) * | 1995-06-06 | 1999-09-21 | Kimberly-Clark Worldwide, Inc. | Microporous film with liquid triggered barrier feature |
US5709921A (en) * | 1995-11-13 | 1998-01-20 | Kimberly-Clark Worldwide, Inc. | Controlled hysteresis nonwoven laminates |
US5681301A (en) * | 1996-01-24 | 1997-10-28 | Johnson & Johnson Worldwide Absorbent Products | Backing web in an absorbent article |
US6117546A (en) * | 1996-03-03 | 2000-09-12 | Hercules Incorporated | Yarns containing linear low density polyethylene fibers |
DK0846793T3 (da) * | 1996-04-25 | 2002-03-04 | Chisso Corp | Polyolenfinfibre og nonwovenstof fremstillet ved anvendelse af disse |
CA2203595A1 (en) | 1996-04-26 | 1997-10-26 | Robert F. Hurley | Cross-linked polyolefin tape |
US5844009A (en) | 1996-04-26 | 1998-12-01 | Sentinel Products Corp. | Cross-linked low-density polymer foam |
JPH09309926A (ja) * | 1996-05-17 | 1997-12-02 | Dow Chem Co:The | エチレン共重合体の製造方法 |
US5882776A (en) | 1996-07-09 | 1999-03-16 | Sentinel Products Corp. | Laminated foam structures with enhanced properties |
US5876813A (en) * | 1996-07-09 | 1999-03-02 | Senitnel Products Corp | Laminated foam structures with enhanced properties |
US6258308B1 (en) | 1996-07-31 | 2001-07-10 | Exxon Chemical Patents Inc. | Process for adjusting WVTR and other properties of a polyolefin film |
US5938878A (en) | 1996-08-16 | 1999-08-17 | Sentinel Products Corp. | Polymer structures with enhanced properties |
US6204208B1 (en) | 1996-09-04 | 2001-03-20 | Kimberly-Clark Worldwide, Inc. | Method and composition for treating substrates for wettability and skin wellness |
US6296936B1 (en) | 1996-09-04 | 2001-10-02 | Kimberly-Clark Worldwide, Inc. | Coform material having improved fluid handling and method for producing |
US6017832A (en) * | 1996-09-04 | 2000-01-25 | Kimberly-Clark Worldwide, Inc. | Method and composition for treating substrates for wettability |
US5849823A (en) * | 1996-09-04 | 1998-12-15 | The Dow Chemical Company | Homogeneously branched ethylene α-olefin interpolymer compositions for use in gasket applications |
US6812289B2 (en) | 1996-12-12 | 2004-11-02 | Dow Global Technologies Inc. | Cast stretch film of interpolymer compositions |
US5947944A (en) * | 1996-12-30 | 1999-09-07 | Kimberly-Clark Worldwide, Inc. | Stretched-thinned films comprising low crystallinity polymers and laminates thereof |
US7338698B1 (en) | 1997-02-28 | 2008-03-04 | Columbia Insurance Company | Homogeneously branched ethylene polymer carpet, carpet backing and method for making same |
US20030211280A1 (en) | 1997-02-28 | 2003-11-13 | Shaw Industries, Inc. | Carpet, carpet backings and methods |
US6117801A (en) * | 1997-03-27 | 2000-09-12 | E. I. Du Pont De Nemours And Company | Properties for flash-spun products |
DE69812946T2 (de) * | 1997-06-20 | 2003-12-18 | The Dow Chemical Co., Midland | Ethylenpolymerzusammensetzungen und daraus hergestellte gegenstände |
US6153551A (en) | 1997-07-14 | 2000-11-28 | Mobil Oil Corporation | Preparation of supported catalyst using trialkylaluminum-metallocene contact products |
US7232871B2 (en) | 1997-08-12 | 2007-06-19 | Exxonmobil Chemical Patents Inc. | Propylene ethylene polymers and production process |
US6635715B1 (en) | 1997-08-12 | 2003-10-21 | Sudhin Datta | Thermoplastic polymer blends of isotactic polypropylene and alpha-olefin/propylene copolymers |
US6921794B2 (en) | 1997-08-12 | 2005-07-26 | Exxonmobil Chemical Patents Inc. | Blends made from propylene ethylene polymers |
US6096668A (en) * | 1997-09-15 | 2000-08-01 | Kimberly-Clark Worldwide, Inc. | Elastic film laminates |
TR200000992T2 (tr) | 1997-10-17 | 2000-11-21 | The Dow Chemical Company | Alfa-olefin monomerleri ile bir veya daha fazla vinil veya viniliden aromatik monomerinden oluşan interpolimerler içeren terkipler. |
DK1025149T3 (da) | 1997-10-31 | 2002-05-27 | Kraton Polymers Res Bv | Skumsammensætning omfattende olie, termoplastisk elastomerer og ekspanderbare partikler |
US6072005A (en) * | 1997-10-31 | 2000-06-06 | Kimberly-Clark Worldwide, Inc. | Breathable films and process for producing them |
US6372172B1 (en) | 1997-12-19 | 2002-04-16 | Kimberly-Clark Worldwide, Inc. | Nonwoven webs having improved softness and barrier properties |
WO1999046435A1 (en) | 1998-03-11 | 1999-09-16 | The Dow Chemical Company | Fibers made from alpha-olefin/vinyl or vinylidene aromatic and/or hindered cycloaliphatic or aliphatic vinyl or vinylidene interpolymers |
AR018359A1 (es) * | 1998-05-18 | 2001-11-14 | Dow Global Technologies Inc | Articulo resistente al calor , configurado, irradiado y reticulado, libre de un agente de reticulacion de silano |
US6709742B2 (en) | 1998-05-18 | 2004-03-23 | Dow Global Technologies Inc. | Crosslinked elastic fibers |
US6376095B1 (en) | 1998-06-11 | 2002-04-23 | The Dow Chemical Company | Elastic films made from alpha-olefin/vinyl aromatic and/or aliphatic or cycloaliphatic vinyl or vinylidene interpolymers |
US6348258B1 (en) | 1998-06-25 | 2002-02-19 | Kimberly-Clark Worldwide, Inc. | Breathable film having organic filler |
AU4962399A (en) | 1998-07-01 | 2000-01-24 | Exxon Chemical Patents Inc. | Elastic blends comprising crystalline polymer and crystallizable polymers of propylene |
WO2000023255A1 (en) | 1998-10-16 | 2000-04-27 | Exxon Chemical Patents Inc. | Process for producing polyolefin microporous breathable film |
US6454989B1 (en) | 1998-11-12 | 2002-09-24 | Kimberly-Clark Worldwide, Inc. | Process of making a crimped multicomponent fiber web |
CN1334845A (zh) | 1998-12-08 | 2002-02-06 | 陶氏化学公司 | 热熔融粘合性聚丙烯/乙烯聚合物纤维以及用于制备该纤维的组合物 |
US6723669B1 (en) * | 1999-12-17 | 2004-04-20 | Kimberly-Clark Worldwide, Inc. | Fine multicomponent fiber webs and laminates thereof |
US6680265B1 (en) | 1999-02-22 | 2004-01-20 | Kimberly-Clark Worldwide, Inc. | Laminates of elastomeric and non-elastomeric polyolefin blend materials |
JP3510156B2 (ja) * | 1999-06-25 | 2004-03-22 | 大和紡績株式会社 | 電池セパレータ並びに電池 |
US6177607B1 (en) | 1999-06-25 | 2001-01-23 | Kimberly-Clark Worldwide, Inc. | Absorbent product with nonwoven dampness inhibitor |
US6673980B1 (en) | 1999-07-16 | 2004-01-06 | Kimberly-Clark Worldwide, Inc. | Absorbent product with creped nonwoven dampness inhibitor |
US7137971B2 (en) * | 1999-08-27 | 2006-11-21 | Kimberly-Clark Worldwide, Inc. | Incontinence garment having pleated extensible liquid retention layer |
US6429350B1 (en) | 1999-08-27 | 2002-08-06 | Kimberly-Clark Worldwide, Inc. | Absorbent article having superabsorbent pockets in a non-absorbent carrier layer |
US6682803B2 (en) | 1999-08-27 | 2004-01-27 | Kimberly-Clark Worldwide, Inc. | Breathable multilayer films with breakable skin layers |
US6663611B2 (en) | 1999-09-28 | 2003-12-16 | Kimberly-Clark Worldwide, Inc. | Breathable diaper with low to moderately breathable inner laminate and more breathable outer cover |
US6632212B1 (en) | 1999-12-14 | 2003-10-14 | Kimberly-Clark Worldwide, Inc. | Breathable laminate permanently conformable to the contours of a wearer |
US6627564B1 (en) | 2000-08-31 | 2003-09-30 | Kimberly-Clark Worldwide, Inc. | Composite elastic in one direction and extensible in another direction |
US7628778B2 (en) | 2000-10-27 | 2009-12-08 | Kimberly-Clark Worldwide, Inc. | Absorbent article with self-forming seals |
US6881205B2 (en) | 2000-10-27 | 2005-04-19 | Kimberly-Clark Worldwide, Inc. | Independence of components in absorbent articles |
US7608069B2 (en) * | 2000-10-27 | 2009-10-27 | Kimberly-Clark Worldwide, Inc. | Absorbent article with captured leg elastics |
US6569225B2 (en) | 2000-12-07 | 2003-05-27 | Kimberly-Clark Worldwide, Inc. | Breathable barrier films containing cavated fillers |
JP2004515664A (ja) * | 2000-12-11 | 2004-05-27 | ダウ グローバル テクノロジーズ インコーポレイティド | 熱接着布およびその製造方法 |
US6946413B2 (en) | 2000-12-29 | 2005-09-20 | Kimberly-Clark Worldwide, Inc. | Composite material with cloth-like feel |
US6818676B2 (en) * | 2001-02-23 | 2004-11-16 | Phat Cushion, Llc | Foam cushion and method of making and using the same |
US7173070B2 (en) * | 2001-02-23 | 2007-02-06 | Phat Cushion Llc | Foam cushion and method of making and using the same |
EP1377698A1 (en) * | 2001-03-15 | 2004-01-07 | The Procter & Gamble Company | Extensible fibers and nonwovens made from large denier splittable fibers |
EP1390417B1 (en) | 2001-04-12 | 2010-10-20 | ExxonMobil Chemical Patents Inc. | Process for polymerizing propylene and ethylene in solution |
US7118639B2 (en) * | 2001-05-31 | 2006-10-10 | Kimberly-Clark Worldwide, Inc. | Structured material having apertures and method of producing the same |
US6869670B2 (en) | 2001-05-31 | 2005-03-22 | Kimberly-Clark Worldwide, Inc. | Composites material with improved high viscosity fluid intake |
US7045029B2 (en) * | 2001-05-31 | 2006-05-16 | Kimberly-Clark Worldwide, Inc. | Structured material and method of producing the same |
US6960635B2 (en) * | 2001-11-06 | 2005-11-01 | Dow Global Technologies Inc. | Isotactic propylene copolymers, their preparation and use |
US6906160B2 (en) | 2001-11-06 | 2005-06-14 | Dow Global Technologies Inc. | Isotactic propylene copolymer fibers, their preparation and use |
EP1461479A1 (en) * | 2001-12-14 | 2004-09-29 | The Procter & Gamble Company | High elongation, low denier fibers using high extrusion rate spinning |
US6835264B2 (en) * | 2001-12-20 | 2004-12-28 | Kimberly-Clark Worldwide, Inc. | Method for producing creped nonwoven webs |
US20030171054A1 (en) * | 2002-03-07 | 2003-09-11 | Vishal Bansal | Multiple component spunbond web and laminates thereof |
ES2322625T3 (es) * | 2002-03-11 | 2009-06-23 | Dow Global Technologies Inc. | Fibras elasticas fijadas por calor, reversibles y metodo para obtenerlas y articulos obtenidos a partir de ellas. |
EP1860214B1 (en) | 2002-03-11 | 2009-04-29 | Dow Global Technologies Inc. | Reversible, heat-set, elastic fibers, and method of making and articles made from same |
WO2004003278A1 (en) * | 2002-06-26 | 2004-01-08 | E.I. Du Pont De Nemours And Company | Multiple component spunbond web and laminates thereof |
AU2003272714A1 (en) * | 2002-10-02 | 2004-04-23 | Dow Global Technologies Inc. | POLYMER COMPOSITIONS COMPRISING A LOW VISCOSITY, HOMOGENEOUSLY BRANCHED ETHYLENE/Alpha-OLEFIN EXTENDER |
US20040096626A1 (en) * | 2002-11-14 | 2004-05-20 | Epoli-Espumas De Polietileno Sa | Layered structures with enhanced properties |
DE50309830D1 (de) | 2002-11-15 | 2008-06-26 | Flooring Technologies Ltd | Einrichtung bestehend aus zwei miteinander verbindbaren Bauplatten und einem Einsatz zum Verriegeln dieser Bauplatten |
US7040706B2 (en) * | 2002-12-09 | 2006-05-09 | Phat Cushion Llc | Seat and method of making same |
US7381666B2 (en) * | 2002-12-20 | 2008-06-03 | Kimberly-Clark Worldwide, Inc. | Breathable film and fabric having liquid and viral barrier |
US7312167B2 (en) * | 2002-12-23 | 2007-12-25 | Kimberly-Clark Worldwide, Inc. | Breathable multilayer films for use in absorbent articles |
US20040122396A1 (en) * | 2002-12-24 | 2004-06-24 | Maldonado Jose E. | Apertured, film-coated nonwoven material |
US20040127873A1 (en) * | 2002-12-31 | 2004-07-01 | Varona Eugenio Go | Absorbent article including porous separation layer with capillary gradient |
US8216203B2 (en) * | 2003-01-01 | 2012-07-10 | Kimberly-Clark Worldwide, Inc. | Progressively functional stretch garments |
US20050106982A1 (en) * | 2003-11-17 | 2005-05-19 | 3M Innovative Properties Company | Nonwoven elastic fibrous webs and methods for making them |
US7671106B2 (en) * | 2004-03-17 | 2010-03-02 | Dow Global Technologies Inc. | Cap liners, closures and gaskets from multi-block polymers |
US8273838B2 (en) * | 2004-03-17 | 2012-09-25 | Dow Global Technologies Llc | Propylene/α-olefins block interpolymers |
CA2559576C (en) * | 2004-03-17 | 2013-02-12 | Dow Global Technologies Inc. | Catalyst composition comprising shuttling agent for ethylene multi-block copolymer formation |
US7795321B2 (en) * | 2004-03-17 | 2010-09-14 | Dow Global Technologies Inc. | Rheology modification of interpolymers of ethylene/α-olefins and articles made therefrom |
US7355089B2 (en) * | 2004-03-17 | 2008-04-08 | Dow Global Technologies Inc. | Compositions of ethylene/α-olefin multi-block interpolymer for elastic films and laminates |
US8816006B2 (en) | 2004-03-17 | 2014-08-26 | Dow Global Technologies Llc | Compositions of ethylene/α-olefin multi-block interpolymer suitable for films |
US7622529B2 (en) * | 2004-03-17 | 2009-11-24 | Dow Global Technologies Inc. | Polymer blends from interpolymers of ethylene/alpha-olefin with improved compatibility |
US7897689B2 (en) * | 2004-03-17 | 2011-03-01 | Dow Global Technologies Inc. | Functionalized ethylene/α-olefin interpolymer compositions |
US7622179B2 (en) * | 2004-03-17 | 2009-11-24 | Dow Global Technologies Inc. | Three dimensional random looped structures made from interpolymers of ethylene/α-olefins and uses thereof |
US7582716B2 (en) * | 2004-03-17 | 2009-09-01 | Dow Global Technologies Inc. | Compositions of ethylene/α-olefin multi-block interpolymer for blown films with high hot tack |
US7514517B2 (en) * | 2004-03-17 | 2009-04-07 | Dow Global Technologies Inc. | Anti-blocking compositions comprising interpolymers of ethylene/α-olefins |
US7662881B2 (en) * | 2004-03-17 | 2010-02-16 | Dow Global Technologies Inc. | Viscosity index improver for lubricant compositions |
NZ549262A (en) * | 2004-03-17 | 2010-08-27 | Dow Global Technologies Inc | Catalyst composition comprising shuttling agent for higher olefin multi-block copolymer formation |
US7714071B2 (en) * | 2004-03-17 | 2010-05-11 | Dow Global Technologies Inc. | Polymer blends from interpolymers of ethylene/α-olefins and flexible molded articles made therefrom |
US7671131B2 (en) | 2004-03-17 | 2010-03-02 | Dow Global Technologies Inc. | Interpolymers of ethylene/α-olefins blends and profiles and gaskets made therefrom |
US7579408B2 (en) * | 2004-03-17 | 2009-08-25 | Dow Global Technologies Inc. | Thermoplastic vulcanizate comprising interpolymers of ethylene/α-olefins |
US7666918B2 (en) * | 2004-03-17 | 2010-02-23 | Dow Global Technologies, Inc. | Foams made from interpolymers of ethylene/α-olefins |
US7608668B2 (en) * | 2004-03-17 | 2009-10-27 | Dow Global Technologies Inc. | Ethylene/α-olefins block interpolymers |
US7687442B2 (en) * | 2004-03-17 | 2010-03-30 | Dow Global Technologies Inc. | Low molecular weight ethylene/α-olefin interpolymer as base lubricant oils |
US7803728B2 (en) * | 2004-03-17 | 2010-09-28 | Dow Global Technologies Inc. | Fibers made from copolymers of ethylene/α-olefins |
US7741397B2 (en) * | 2004-03-17 | 2010-06-22 | Dow Global Technologies, Inc. | Filled polymer compositions made from interpolymers of ethylene/α-olefins and uses thereof |
US7863379B2 (en) * | 2004-03-17 | 2011-01-04 | Dow Global Technologies Inc. | Impact modification of thermoplastics with ethylene/alpha-olefin interpolymers |
EP1730335B1 (en) * | 2004-03-19 | 2019-06-26 | Dow Global Technologies LLC | Propylene-based copolymers, a method of making the fibers and articles made from the fibers |
US7101623B2 (en) * | 2004-03-19 | 2006-09-05 | Dow Global Technologies Inc. | Extensible and elastic conjugate fibers and webs having a nontacky feel |
EP2298976B1 (en) | 2004-04-30 | 2012-08-22 | Dow Global Technologies LLC | Improved fibers for polyethylene nonwoven fabric |
AU2005262843B2 (en) * | 2004-06-21 | 2007-11-15 | Univation Technologies, Llc | Methods for producing polymers with control over composition distribution |
US7157531B2 (en) * | 2004-06-21 | 2007-01-02 | Univation Technologies, Llc | Methods for producing polymers with control over composition distribution |
DE602005013689D1 (de) * | 2004-12-03 | 2009-05-14 | Dow Global Technologies Inc | Verfahren zur verbesserung von ablösungseigenschaften elastischer polyolefinfasern |
US20080011194A1 (en) * | 2004-12-03 | 2008-01-17 | Dow Global Technologies Inc. | Wood Fiber Plastic Composites |
US7651653B2 (en) | 2004-12-22 | 2010-01-26 | Kimberly-Clark Worldwide, Inc. | Machine and cross-machine direction elastic materials and methods of making same |
EP1869095B1 (en) | 2005-03-17 | 2011-04-27 | Dow Global Technologies LLC | Compositions of ethylene/alpha-olefin multi-block interpolymer for elastic films and laminates |
US8084537B2 (en) * | 2005-03-17 | 2011-12-27 | Dow Global Technologies Llc | Polymer blends from interpolymers of ethylene/α-olefin with improved compatibility |
RU2007134418A (ru) * | 2005-03-17 | 2009-03-20 | Дау Глобал Текнолоджиз Инк. (Us) | ВОЛОКНА, ПОЛУЧАЕМЫЕ ИЗ СОПОЛИМЕРОВ ЭТИЛЕНА/α-ОЛЕФИНОВ |
AU2006227348A1 (en) * | 2005-03-17 | 2006-09-28 | Dow Global Technologies Inc. | Adhesive and marking compositions made from interpolymers of ethylene/alpha-olefins |
US8677513B2 (en) | 2005-04-01 | 2014-03-25 | Kimberly-Clark Worldwide, Inc. | Surgical sleeve for glove retention |
DE102005025055B4 (de) * | 2005-05-30 | 2007-12-06 | Fiberweb Corovin Gmbh | Verfahren zur Herstellung eines Vlieses mit hoher Dehnbarkeit aus Polymermischungen mit amphiphilen Blockcopolymeren, Vlies mit hoher Dehnbarkeit und Verwendung sowie Polymermischung zur Herstellung eines Vlieses mit hoher Dehnbarkeit |
US7685649B2 (en) * | 2005-06-20 | 2010-03-30 | Kimberly-Clark Worldwide, Inc. | Surgical gown with elastomeric fibrous sleeves |
US20070000014A1 (en) * | 2005-06-20 | 2007-01-04 | John Rotella | Surgical gown with a film sleeve for glove retention and wearer protection |
EP1940896B1 (en) * | 2005-09-15 | 2014-10-22 | Dow Global Technologies LLC | Catalytic olefin block copolymers via polymerizable shuttling agent |
ES2483591T3 (es) * | 2005-09-15 | 2014-08-06 | Dow Global Technologies Llc | Control de la arquitectura polimérica y distribución de pesos moleculares por medio de un agente de transporte multicentrado |
AR058496A1 (es) * | 2005-10-26 | 2008-02-06 | Dow Global Technologies Inc | Articulos elasticos de multiples capas |
US20070122614A1 (en) * | 2005-11-30 | 2007-05-31 | The Dow Chemical Company | Surface modified bi-component polymeric fiber |
US8153243B2 (en) | 2005-12-09 | 2012-04-10 | Dow Global Technologies Llc | Interpolymers suitable for multilayer films |
JP5502325B2 (ja) * | 2005-12-09 | 2014-05-28 | ダウ グローバル テクノロジーズ エルエルシー | エチレン/α−オレフィン組成物における分子量分布の制御方法 |
US7820001B2 (en) * | 2005-12-15 | 2010-10-26 | Kimberly-Clark Worldwide, Inc. | Latent elastic laminates and methods of making latent elastic laminates |
US8003553B2 (en) * | 2005-12-15 | 2011-08-23 | Kimberly-Clark Worldwide, Inc. | Elastic-powered shrink laminate |
US20100224199A1 (en) * | 2006-05-01 | 2010-09-09 | Kimberly-Clark Worldwide, Inc. | Respirator |
US20080110465A1 (en) * | 2006-05-01 | 2008-05-15 | Welchel Debra N | Respirator with exhalation vents |
US20070251522A1 (en) * | 2006-05-01 | 2007-11-01 | Welchel Debra N | Respirator with exhalation vents |
US7585382B2 (en) * | 2006-06-30 | 2009-09-08 | Kimberly-Clark Worldwide, Inc. | Latent elastic nonwoven composite |
US7803244B2 (en) | 2006-08-31 | 2010-09-28 | Kimberly-Clark Worldwide, Inc. | Nonwoven composite containing an apertured elastic film |
CA2661844A1 (en) * | 2006-09-06 | 2008-03-13 | Dow Global Technologies Inc. | Knit fabrics comprising olefin block interpolymers |
US20080076315A1 (en) * | 2006-09-27 | 2008-03-27 | Mccormack Ann L | Elastic Composite Having Barrier Properties |
US7582178B2 (en) * | 2006-11-22 | 2009-09-01 | Kimberly-Clark Worldwide, Inc. | Nonwoven-film composite with latent elasticity |
US7938921B2 (en) * | 2006-11-22 | 2011-05-10 | Kimberly-Clark Worldwide, Inc. | Strand composite having latent elasticity |
TW200835742A (en) | 2006-11-30 | 2008-09-01 | Dow Global Technologies Inc | Olefin block compositions for stretch fabrics with wrinkle resistance |
EP2087155B1 (en) * | 2006-11-30 | 2017-04-26 | Dow Global Technologies LLC | Fabric comprising elastic fibres of cross-linked ethylene polymer |
TW200902780A (en) * | 2006-11-30 | 2009-01-16 | Dow Global Technologies Inc | Olefin block compositions for heavy weight stretch fabrics |
TW200900545A (en) * | 2007-01-16 | 2009-01-01 | Dow Global Technologies Inc | Colorfast fabrics and garments of olefin block compositions |
CA2674991A1 (en) * | 2007-01-16 | 2008-07-24 | Dow Global Technologies Inc. | Cone dyed yarns of olefin block compositions |
AU2008206334A1 (en) * | 2007-01-16 | 2008-07-24 | Dow Global Technologies Inc. | Stretch fabrics and garments of olefin block polymers |
US7910795B2 (en) * | 2007-03-09 | 2011-03-22 | Kimberly-Clark Worldwide, Inc. | Absorbent article containing a crosslinked elastic film |
EP1972704A1 (en) * | 2007-03-22 | 2008-09-24 | Borealis Technology Oy | Fibre, tapes or filaments comprising a polyethylene composition |
US7879747B2 (en) | 2007-03-30 | 2011-02-01 | Kimberly-Clark Worldwide, Inc. | Elastic laminates having fragrance releasing properties and methods of making the same |
EP3208371B1 (en) | 2007-04-17 | 2022-01-12 | LYCRA Company UK Limited | Elastic composite yarns and woven fabrics made therefrom, and methods and apparatus for making the same |
US20100018641A1 (en) * | 2007-06-08 | 2010-01-28 | Kimberly-Clark Worldwide, Inc. | Methods of Applying Skin Wellness Agents to a Nonwoven Web Through Electrospinning Nanofibers |
WO2009012073A2 (en) * | 2007-07-09 | 2009-01-22 | Dow Global Technologies Inc. | Olefin block interpolymer composition suitable for fibers |
US8460588B2 (en) | 2007-07-30 | 2013-06-11 | Kimberly-Clark Worldwide, Inc. | Cross directional zoned bicomponent films, film laminates, and systems and methods for manufacture of the same |
US9642403B2 (en) | 2007-08-16 | 2017-05-09 | Kimberly-Clark Worldwide, Inc. | Strap fastening system for a disposable respirator providing improved donning |
US20090044811A1 (en) | 2007-08-16 | 2009-02-19 | Kimberly-Clark Worldwide, Inc. | Vent and strap fastening system for a disposable respirator providing improved donning |
US20090105374A1 (en) * | 2007-09-28 | 2009-04-23 | Dow Global Technologies Inc. | Thermoplastic olefin composition with improved heat distortion temperature |
US8399368B2 (en) * | 2007-10-16 | 2013-03-19 | Kimberly-Clark Worldwide, Inc. | Nonwoven web material containing a crosslinked elastic component formed from a linear block copolymer |
US7923391B2 (en) * | 2007-10-16 | 2011-04-12 | Kimberly-Clark Worldwide, Inc. | Nonwoven web material containing crosslinked elastic component formed from a pentablock copolymer |
US8349963B2 (en) | 2007-10-16 | 2013-01-08 | Kimberly-Clark Worldwide, Inc. | Crosslinked elastic material formed from a linear block copolymer |
US7923392B2 (en) * | 2007-10-16 | 2011-04-12 | Kimberly-Clark Worldwide, Inc. | Crosslinked elastic material formed from a branched block copolymer |
EP2799235A1 (en) * | 2007-10-22 | 2014-11-05 | Dow Global Technologies LLC | Multilayer films |
US8287677B2 (en) | 2008-01-31 | 2012-10-16 | Kimberly-Clark Worldwide, Inc. | Printable elastic composite |
US8338508B2 (en) | 2008-05-14 | 2012-12-25 | Kimberly-Clark Worldwide, Inc. | Water-sensitive film containing an olefinic elastomer |
US8709191B2 (en) * | 2008-05-15 | 2014-04-29 | Kimberly-Clark Worldwide, Inc. | Latent elastic composite formed from a multi-layered film |
US8603281B2 (en) * | 2008-06-30 | 2013-12-10 | Kimberly-Clark Worldwide, Inc. | Elastic composite containing a low strength and lightweight nonwoven facing |
US7968479B2 (en) * | 2008-06-30 | 2011-06-28 | Kimberly-Clark Worldwide, Inc. | Elastic multilayer composite including pattern unbonded elastic materials, articles containing same, and methods of making same |
US8679992B2 (en) | 2008-06-30 | 2014-03-25 | Kimberly-Clark Worldwide, Inc. | Elastic composite formed from multiple laminate structures |
JP5600119B2 (ja) | 2008-12-30 | 2014-10-01 | スリーエム イノベイティブ プロパティズ カンパニー | 弾性不織布繊維ウェブ並びに作製及び使用方法 |
US8715630B2 (en) * | 2009-09-15 | 2014-05-06 | Dow Global Technologies Llc | Silicone replacements for personal care compositions |
US8771657B2 (en) * | 2009-09-15 | 2014-07-08 | Union Carbide Chemicals & Plastics Technology Llc | Personal care compositions with ethylene acrylic acid copolymer aqueous dispersions |
KR101651666B1 (ko) * | 2009-12-29 | 2016-08-29 | 코오롱글로텍주식회사 | 고연성 폴리올레핀계 단섬유 및 이의 제조방법과 이를 이용한 서멀본드 부직포 |
CN103189045B (zh) * | 2010-03-26 | 2015-08-26 | 联合碳化化学品及塑料技术公司 | 用于染发的个人护理组合物 |
US20110305653A1 (en) | 2010-06-10 | 2011-12-15 | Jordan Susan L | Personal care compositions with ethylene acrylic acid copolymer aqueous dispersions |
US10753023B2 (en) | 2010-08-13 | 2020-08-25 | Kimberly-Clark Worldwide, Inc. | Toughened polylactic acid fibers |
US8936740B2 (en) | 2010-08-13 | 2015-01-20 | Kimberly-Clark Worldwide, Inc. | Modified polylactic acid fibers |
JP2013540153A (ja) | 2010-10-20 | 2013-10-31 | ユニオン カーバイド ケミカルズ アンド プラスティックス テクノロジー エルエルシー | 毛髪固定剤 |
WO2012061195A2 (en) | 2010-11-04 | 2012-05-10 | Union Carbide Chemicals & Plastics Technology Llc | Skin care compositions |
US8889945B2 (en) | 2010-12-08 | 2014-11-18 | Kimberly-Clark Worldwide, Inc. | Elastic film containing a renewable starch polymer |
EP2652109A2 (en) | 2010-12-17 | 2013-10-23 | Dow Global Technologies LLC | Ethylene acrylic acid copolymer aqueous dispersions for fragrance release in laundry detergents |
US9718258B2 (en) | 2011-12-20 | 2017-08-01 | Kimberly-Clark Worldwide, Inc. | Multi-layered film containing a biopolymer |
US9327438B2 (en) | 2011-12-20 | 2016-05-03 | Kimberly-Clark Worldwide, Inc. | Method for forming a thermoplastic composition that contains a plasticized starch polymer |
US8980964B2 (en) | 2012-02-10 | 2015-03-17 | Kimberly-Clark Worldwide, Inc. | Renewable polyester film having a low modulus and high tensile elongation |
US8637130B2 (en) | 2012-02-10 | 2014-01-28 | Kimberly-Clark Worldwide, Inc. | Molded parts containing a polylactic acid composition |
US20130210621A1 (en) | 2012-02-10 | 2013-08-15 | Kimberly-Clark Worldwide, Inc. | Breathable Film Formed from a Renewable Polyester |
US8975305B2 (en) | 2012-02-10 | 2015-03-10 | Kimberly-Clark Worldwide, Inc. | Rigid renewable polyester compositions having a high impact strength and tensile elongation |
US10858762B2 (en) | 2012-02-10 | 2020-12-08 | Kimberly-Clark Worldwide, Inc. | Renewable polyester fibers having a low density |
US9040598B2 (en) | 2012-02-10 | 2015-05-26 | Kimberly-Clark Worldwide, Inc. | Renewable polyester compositions having a low density |
BR112015006442B1 (pt) | 2012-09-24 | 2019-11-26 | Dow Global Technologies Llc | composição gel tipo óleo para cuidado da pele |
CN103088445A (zh) * | 2013-03-04 | 2013-05-08 | 北京石油化工学院 | 茂金属基低密度聚乙烯亚微米纤维的制备方法 |
US9457115B2 (en) | 2013-05-31 | 2016-10-04 | Avent, Inc. | Recyclable indicator tape for sterilization |
CN105247119B (zh) | 2013-06-12 | 2018-07-06 | 金伯利-克拉克环球有限公司 | 多孔聚烯烃纤维 |
RU2617356C1 (ru) | 2013-06-12 | 2017-04-24 | Кимберли-Кларк Ворлдвайд, Инк. | Многофункциональная ткань |
US11965083B2 (en) | 2013-06-12 | 2024-04-23 | Kimberly-Clark Worldwide, Inc. | Polyolefin material having a low density |
WO2014199276A1 (en) | 2013-06-12 | 2014-12-18 | Kimberly-Clark Worldwide, Inc. | Polymeric material for use in thermal insulation |
US20160130799A1 (en) | 2013-06-12 | 2016-05-12 | Kimberly-Clark Worldwide, Inc. | Building Insulation |
RU2630792C2 (ru) | 2013-06-12 | 2017-09-13 | Кимберли-Кларк Ворлдвайд, Инк. | Методика инициации порообразования |
WO2014199278A1 (en) | 2013-06-12 | 2014-12-18 | Kimberly-Clark Worldwide, Inc. | Garment containing a porous polymeric material |
SG11201510049XA (en) | 2013-06-12 | 2016-01-28 | Kimberly Clark Co | Polyolefin film for use in packaging |
KR102224562B1 (ko) | 2013-06-12 | 2021-03-08 | 킴벌리-클라크 월드와이드, 인크. | 복수모드 포어 크기 분포를 갖는 중합체 물질 |
SG11201601706RA (en) | 2013-08-09 | 2016-04-28 | Kimberly Clark Co | Technique for selectively controlling the porosity of a polymeric material |
JP6030810B2 (ja) | 2013-08-09 | 2016-11-24 | キンバリー クラーク ワールドワイド インコーポレイテッド | 活性薬剤の送達システム |
AU2014304191B2 (en) | 2013-08-09 | 2017-06-01 | Kimberly-Clark Worldwide, Inc. | Microparticles having a multimodal pore distribution |
KR102208200B1 (ko) | 2013-08-09 | 2021-01-27 | 킴벌리-클라크 월드와이드, 인크. | 3차원 인쇄용 중합체 물질 |
CN105492513B (zh) | 2013-08-09 | 2019-03-08 | 金伯利-克拉克环球有限公司 | 各向异性的聚合物材料 |
WO2015019203A1 (en) | 2013-08-09 | 2015-02-12 | Kimberly-Clark Worldwide, Inc. | Flexible polymeric material with shape retention properties |
BR112016010917B1 (pt) | 2013-11-20 | 2022-01-25 | Kimberly-Clark Worldwide, Inc | Artigo absorvente |
EP3071740B1 (en) | 2013-11-20 | 2021-06-02 | Kimberly-Clark Worldwide, Inc. | Soft and durable nonwoven composite |
US10695235B2 (en) | 2013-11-27 | 2020-06-30 | Kimberly-Clark Worldwide, Inc. | Printed 3D-elastic laminates |
US10463222B2 (en) | 2013-11-27 | 2019-11-05 | Kimberly-Clark Worldwide, Inc. | Nonwoven tack cloth for wipe applications |
WO2015095018A1 (en) | 2013-12-16 | 2015-06-25 | Dow Global Technologies Llc | Process to make storage stable polymer formulations |
US9913764B2 (en) | 2013-12-18 | 2018-03-13 | Kimberly-Clark Worldwide, Inc. | Post-bonded grooved elastic materials |
USD746439S1 (en) | 2013-12-30 | 2015-12-29 | Kimberly-Clark Worldwide, Inc. | Combination valve and buckle set for disposable respirators |
RU2648076C2 (ru) | 2014-01-31 | 2018-03-22 | Кимберли-Кларк Ворлдвайд, Инк. | Тонкая нанокомпозитная пленка для применения во впитывающем изделии |
KR101673248B1 (ko) | 2014-01-31 | 2016-11-07 | 킴벌리-클라크 월드와이드, 인크. | 흡수 용품에 사용하기 위한 강성 나노복합체 필름 |
WO2015116958A1 (en) | 2014-01-31 | 2015-08-06 | Kimberly-Clark Worldwide, Inc. | Nanocomposite packaging film |
US20170014328A1 (en) | 2014-03-10 | 2017-01-19 | Dow Global Technologies Llc | Hair care sensory agents |
US11186927B2 (en) | 2014-06-06 | 2021-11-30 | Kimberly Clark Worldwide, Inc. | Hollow porous fibers |
WO2015187924A1 (en) | 2014-06-06 | 2015-12-10 | Kimberly-Clark Worldwide, Inc. | Thermoformed article formed from a porous polymeric sheet |
MX2017006066A (es) | 2014-11-26 | 2017-07-27 | Kimberly Clark Co | Material poroso recocido de poliolefina. |
CN107107431B (zh) | 2014-11-26 | 2020-03-06 | 金伯利-克拉克环球有限公司 | 双轴拉伸的多孔膜 |
MX2017006620A (es) | 2014-12-19 | 2017-08-10 | Kimberly Clark Co | Compuesto no tejido extensible en la direccion transversal a la maquina (cd). |
BR112017015171B1 (pt) | 2015-01-30 | 2022-09-20 | Kimberly-Clark Worldwide, Inc | Película, método para formação da película, e, artigo absorvente |
CN107205854B (zh) | 2015-01-30 | 2019-11-29 | 金伯利-克拉克环球有限公司 | 噪声减小的吸收制品包装 |
JP6720328B2 (ja) | 2015-12-11 | 2020-07-08 | ローム アンド ハース カンパニーRohm And Haas Company | 濃縮ポリオレフィンエマルション及びそれらを含有するパーソナルケア組成物 |
CN108368654B (zh) | 2015-12-11 | 2022-05-10 | 金伯利-克拉克环球有限公司 | 用于形成多孔纤维的多阶段牵伸技术 |
US11155935B2 (en) | 2015-12-11 | 2021-10-26 | Kimberly-Clark Worldwide, Inc. | Method for forming porous fibers |
CN108289798A (zh) | 2015-12-11 | 2018-07-17 | 罗门哈斯公司 | 浓缩聚烯烃乳液和含有其的护发组合物 |
WO2017106267A1 (en) | 2015-12-17 | 2017-06-22 | Kimberly-Clark Worldwide, Inc. | Color-changing polymeric material |
EP3498118B1 (en) | 2016-05-04 | 2020-09-09 | O&M Halyard International Unlimited Company | Laminate material |
JP2019518015A (ja) | 2016-06-15 | 2019-06-27 | ローム アンド ハース カンパニーRohm And Haas Company | 相乗的ヘアケア配合物 |
WO2017218077A1 (en) | 2016-06-15 | 2017-12-21 | Dow Global Technologies Llc | Improved hair care compositions |
AU2017301367B2 (en) | 2016-07-29 | 2022-09-29 | O&M Halyard International Unlimited Company | Collar for a disposable surgical gown |
CA3071320A1 (en) | 2017-08-01 | 2019-02-07 | O&M Halyard International Unlimited Company | Pocket and drape system for providing sterile fields |
US11433158B2 (en) | 2017-12-12 | 2022-09-06 | The Procter & Gamble Company | Recycle friendly and sustainable absorbent articles |
EP3840603B1 (en) | 2018-08-24 | 2023-09-20 | O&M Halyard, Inc. | Personal protection and ventilation system |
US11528947B2 (en) | 2018-08-24 | 2022-12-20 | O&M Halyard, Inc. | Personal protection and ventilation system |
AR117126A1 (es) | 2018-11-20 | 2021-07-14 | Dow Global Technologies Llc | UNA TELA NO TEJIDA QUE TIENE FIBRAS DE POLÍMEROS DE ETILENO / a-OLEFINA |
CA3122206A1 (en) | 2018-12-06 | 2020-06-11 | O&M Halyard, Inc. | Mechanically bonded visor system for surgical hood |
WO2020247563A1 (en) | 2019-06-06 | 2020-12-10 | O&M Halyard Inc. | Pocket and drape system for providing sterile fields |
US11291517B2 (en) | 2019-06-06 | 2022-04-05 | O&M Halyard, Inc. | Pocket and drape system for providing sterile fields |
WO2020247560A1 (en) | 2019-06-06 | 2020-12-10 | O&M Halyard Inc. | Pocket and drape system for providing sterile fields |
US20200383742A1 (en) | 2019-06-06 | 2020-12-10 | O&M Halyard, Inc. | Pocket and Drape System for Providing Sterile Fields |
DE112020006418T5 (de) | 2020-02-24 | 2022-10-27 | Kimberly-Clark Worldwide, Inc. | Nicht-blockierende mehrschichtige elastische zusammensetzung |
US20220195645A1 (en) | 2020-12-21 | 2022-06-23 | O&M Halyard, Inc. | Higher Strength Calcium Carbonate Filled Fiber Spunbond and SMS Nonwoven Material |
FR3146681A1 (fr) | 2023-03-13 | 2024-09-20 | Sterimed Sas | Non tissé poreux utilisé pour la réalisation d’articles de stérilisation |
Family Cites Families (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SE422070B (sv) * | 1980-09-04 | 1982-02-15 | Unifos Kemi Ab | Streckt polyetenbaserat termoplastmaterial och forfarande for dess framstellning |
JPS58191215A (ja) * | 1982-04-28 | 1983-11-08 | Chisso Corp | ポリエチレン系熱接着性繊維 |
ZA844157B (en) * | 1983-06-06 | 1986-01-29 | Exxon Research Engineering Co | Process and catalyst for polyolefin density and molecular weight control |
US4880691A (en) * | 1984-02-17 | 1989-11-14 | The Dow Chemical Company | Fine denier fibers of olefin polymers |
US4909975A (en) * | 1984-02-17 | 1990-03-20 | The Dow Chemical Company | Fine denier fibers of olefin polymers |
US4830907A (en) * | 1984-11-16 | 1989-05-16 | The Dow Chemical Company | Fine denier fibers of olefin polymers |
CA1255065A (en) * | 1984-02-17 | 1989-06-06 | Lawrence H. Sawyer | Fibers of olefin polymers |
US4612300A (en) * | 1985-06-06 | 1986-09-16 | The Dow Chemical Company | Novel catalyst for producing relatively narrow molecular weight distribution olefin polymers |
US4644045A (en) * | 1986-03-14 | 1987-02-17 | Crown Zellerbach Corporation | Method of making spunbonded webs from linear low density polyethylene |
US5068141A (en) * | 1986-05-31 | 1991-11-26 | Unitika Ltd. | Polyolefin-type nonwoven fabric and method of producing the same |
CA1283764C (en) * | 1986-09-29 | 1991-05-07 | Mitsui Chemicals Inc. | Very soft polyolefin spunbonded nonwoven fabric and its production method |
JPS63126912A (ja) * | 1986-11-14 | 1988-05-30 | Unitika Ltd | ポリエチレン繊維とその製造法 |
IL84641A (en) * | 1986-12-19 | 1992-05-25 | Exxon Chemical Patents Inc | Unsaturated ethylene polymers |
US5153157A (en) * | 1987-01-30 | 1992-10-06 | Exxon Chemical Patents Inc. | Catalyst system of enhanced productivity |
PL276385A1 (en) * | 1987-01-30 | 1989-07-24 | Exxon Chemical Patents Inc | Method for polymerization of olefines,diolefins and acetylene unsaturated compounds |
IL85097A (en) * | 1987-01-30 | 1992-02-16 | Exxon Chemical Patents Inc | Catalysts based on derivatives of a bis(cyclopentadienyl)group ivb metal compound,their preparation and their use in polymerization processes |
US4842922A (en) * | 1987-10-27 | 1989-06-27 | The Dow Chemical Company | Polyethylene fibers and spunbonded fabric or web |
US4830987A (en) * | 1987-11-19 | 1989-05-16 | Texas Instruments Incorporated | Contactless annealing process using cover slices |
HUT54722A (en) * | 1988-09-30 | 1991-03-28 | Exxon Chemical Patents Inc | Linear ethylene interpolymer mixtures |
JP2780050B2 (ja) * | 1989-08-21 | 1998-07-23 | 三菱化学株式会社 | 不織布用バインダー繊維 |
US5057475A (en) * | 1989-09-13 | 1991-10-15 | Exxon Chemical Patents Inc. | Mono-Cp heteroatom containing group IVB transition metal complexes with MAO: supported catalyst for olefin polymerization |
EP0672688B2 (en) * | 1990-06-22 | 2002-04-17 | ExxonMobil Chemical Patents Inc. | Aluminum-free monocyclopentadienyl metallocene catalysts for olefin polymerization |
DE4139261A1 (de) * | 1991-11-29 | 1993-06-03 | Basf Ag | Ethylen-copolymerisate niederer dichte |
-
1992
- 1992-11-24 US US07/981,029 patent/US5322728A/en not_active Expired - Lifetime
-
1993
- 1993-11-10 DE DE69332083T patent/DE69332083T2/de not_active Expired - Lifetime
- 1993-11-10 EP EP94901418A patent/EP0670918B1/en not_active Expired - Lifetime
- 1993-11-10 WO PCT/US1993/010913 patent/WO1994012699A1/en active IP Right Grant
- 1993-11-10 JP JP51318394A patent/JP3308272B2/ja not_active Expired - Fee Related
- 1993-11-10 CA CA 2150006 patent/CA2150006C/en not_active Expired - Lifetime
- 1993-11-10 KR KR1019950702083A patent/KR100295922B1/ko not_active IP Right Cessation
- 1993-11-10 ES ES94901418T patent/ES2178647T3/es not_active Expired - Lifetime
- 1993-11-10 AT AT94901418T patent/ATE220133T1/de not_active IP Right Cessation
- 1993-11-10 AU AU56014/94A patent/AU683034B2/en not_active Ceased
- 1993-11-23 MX MX9307314A patent/MX9307314A/es unknown
- 1993-11-24 CN CN93121259A patent/CN1048530C/zh not_active Expired - Fee Related
-
1995
- 1995-05-23 NO NO19952037A patent/NO310571B1/no not_active IP Right Cessation
- 1995-05-23 FI FI952500A patent/FI952500A/fi unknown
Also Published As
Publication number | Publication date |
---|---|
FI952500A (fi) | 1995-07-21 |
CN1095771A (zh) | 1994-11-30 |
KR950704547A (ko) | 1995-11-20 |
NO952037L (no) | 1995-07-12 |
WO1994012699A1 (en) | 1994-06-09 |
AU683034B2 (en) | 1997-10-30 |
JP3308272B2 (ja) | 2002-07-29 |
FI952500A0 (fi) | 1995-05-23 |
EP0670918B1 (en) | 2002-07-03 |
DE69332083T2 (de) | 2003-01-30 |
MX9307314A (es) | 1994-07-29 |
NO310571B1 (no) | 2001-07-23 |
ES2178647T3 (es) | 2003-01-01 |
CA2150006C (en) | 2002-09-24 |
US5322728A (en) | 1994-06-21 |
JPH08503525A (ja) | 1996-04-16 |
KR100295922B1 (ko) | 2001-11-14 |
DE69332083D1 (en) | 2002-08-08 |
NO952037D0 (no) | 1995-05-23 |
ATE220133T1 (de) | 2002-07-15 |
AU5601494A (en) | 1994-06-22 |
CA2150006A1 (en) | 1994-06-09 |
EP0670918A1 (en) | 1995-09-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1048530C (zh) | 聚烯烃聚合物纤维 | |
KR0138657B1 (ko) | 선형 폴리에틸렌의 블렌드로부터 제조한 스펀본드 웹 또는 스펀본드 부직포 및 이들의 제조방법 | |
DE69734508T2 (de) | Fasern und daraus hergestellte faserige formmassen | |
EP0192897B1 (en) | Blend of polyethylene and polypropylene | |
CN1934296B (zh) | 丙烯基的共聚物,制造纤维的方法以及由纤维制造的制品 | |
CN1069707C (zh) | 新型聚烯烃纤维及其织物 | |
CN1094419C (zh) | 包含低熔点丙烯聚合物的纤维和织物 | |
US4632861A (en) | Blend of polyethylene and polypropylene | |
US4909975A (en) | Fine denier fibers of olefin polymers | |
US5112686A (en) | Linear ethylene polymer staple fibers | |
US4990204A (en) | Improved spunbonding of linear polyethylenes | |
JP2578665B2 (ja) | 繊維製品の放射線処理方法 | |
JP2008524460A (ja) | ポリマー・ブレンドおよび該ブレントからの不織布製品 | |
EP1452630A1 (en) | Polypropylene fibres | |
US4880691A (en) | Fine denier fibers of olefin polymers | |
FI109426B (fi) | Joustavia kuituja, kankaita ja niistä valmistettuja tuotteita | |
US6720388B1 (en) | Polypropylene fibres | |
KR100361596B1 (ko) | 이소택틱및아택틱폴리올레핀의블렌드로부터제조된부직포 | |
EP1297203B1 (en) | Polypropylene fibres | |
JP2768461B2 (ja) | ポリエチレンとポリプロピレンのブレンド構造体からなる繊維及びその繊維を用いた不織布 | |
JPH0364519A (ja) | 複合型熱接着性繊維及びこれを用いた不織布 | |
KR101418498B1 (ko) | 고신율 폴리올레핀 섬유 및 이로부터 제조되는 부직포 | |
CN1174129C (zh) | 聚丙烯纤维及其制造方法 | |
KR910004466B1 (ko) | 열접착성섬유 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C19 | Lapse of patent right due to non-payment of the annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |