CN101405453A - 包含陶瓷颗粒的织物和制备它们的方法 - Google Patents
包含陶瓷颗粒的织物和制备它们的方法 Download PDFInfo
- Publication number
- CN101405453A CN101405453A CNA2007800098898A CN200780009889A CN101405453A CN 101405453 A CN101405453 A CN 101405453A CN A2007800098898 A CNA2007800098898 A CN A2007800098898A CN 200780009889 A CN200780009889 A CN 200780009889A CN 101405453 A CN101405453 A CN 101405453A
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- Prior art keywords
- fabric
- crosslinked
- base fabric
- processing
- polymer
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- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
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- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
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- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 1
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- FJQXCDYVZAHXNS-UHFFFAOYSA-N methadone hydrochloride Chemical compound Cl.C=1C=CC=CC=1C(CC(C)N(C)C)(C(=O)CC)C1=CC=CC=C1 FJQXCDYVZAHXNS-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
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- DRKVIJXWFGFHDK-UHFFFAOYSA-N n,n,4-trimethylpiperazin-1-amine Chemical compound CN(C)N1CCN(C)CC1 DRKVIJXWFGFHDK-UHFFFAOYSA-N 0.000 description 1
- NXHXNTAEDQTBLD-UHFFFAOYSA-N n,n-dimethyl-3-(triazinan-1-yl)propan-1-amine Chemical group CN(C)CCCN1CCCNN1 NXHXNTAEDQTBLD-UHFFFAOYSA-N 0.000 description 1
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- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- GQCLFTGMXCYYHT-UHFFFAOYSA-N phosphanium;hydroxymethyl sulfate Chemical compound [PH4+].OCOS([O-])(=O)=O GQCLFTGMXCYYHT-UHFFFAOYSA-N 0.000 description 1
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- 125000005496 phosphonium group Chemical group 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000412 polyarylene Polymers 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
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- 229940080818 propionamide Drugs 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000007378 ring spinning Methods 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
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- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910021521 yttrium barium copper oxide Inorganic materials 0.000 description 1
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates
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- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/49—Oxides or hydroxides of elements of Groups 8, 9,10 or 18 of the Periodic Table; Ferrates; Cobaltates; Nickelates; Ruthenates; Osmates; Rhodates; Iridates; Palladates; Platinates
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- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
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Abstract
提供了抗熔融金属的织物,其包含用含有可聚合的聚氨酯单体和陶瓷颗粒的组合物处理的非熔化底基织物。
Description
发明领域
本发明涉及防护织物领域,特别是用于保护穿戴者防熔融金属溅出物的涂层织物。
发明背景
工业劳动者需要保护他们防熔融金属溅出物和防止对熔融金属飞溅的长期暴露。
为了防熔融金属,服装应该理想地用不可燃的纤维制成,并且还应该阻挡熔融金属和抗熔融金属的吸收、转移或渗透。传统上,熔融金属劳动者穿有由织物制成的抗磨服装,其中织物由非熔化纤维制成,如棉制品。可以由含磷组合物向织物提供阻燃性能,含磷组合物如四羟甲基氯化鏻、四羟甲基硫酸鏻和正-羟甲基-3-(二甲基膦酰基)丙酰胺(例如,由Ciba-Geigy公司以商品名PYROVATEX CP出售)。这类服装,虽然是阻燃的,但通常不能足够地阻挡熔融金属,这表示熔融金属在接触时停留在服装上,甚至可以被吸收,并因此具有足够的时间向穿戴者转移大量的热,导致严重的燃烧。
解决这个问题的尝试被公开在美国专利no.4,446,202(Mischutin)中。阻燃性溴化化合物与高分子量聚合物或胶乳一起被分散在水介质中,该水介质具有表面活化剂或乳化剂和胶体(作为粘结剂或增稠剂)。获得的组合物被施用在织物上,一旦通过加热或通过在环境温度下将其暴露在空气中而进行干燥,则形成膜。该膜被认为充分地封闭在纤维之间的空隙足以显著地抑制喷溅或飞溅的熔融金属的颗粒渗入纤维中。
使织物抗熔融金属的另一个尝试被描述在美国专利no.4,631,224,其公开了抗熔融金属的涂层织物组合物,其包括:
(a)底基织物,和(b)在该织物表面上的涂层,其包含(i)无机粘结剂组合物胶态氧化硅、单铝磷酸盐、水合氯化铝和一定量的有效增强所述无机粘结剂组合物与所述织物的粘合的烷基卤化锡催化剂,(ii)有机粘结剂,(iii)具有碟形结构的金属片,粒度范围为约30-约150微米和厚度为约0.5-约1.5微米,所述无机粘结剂组合物和所述有机粘结剂的量为有效地将所述金属片粘合到所述织物上。
还存在对抗熔融金属的替代织物的需求。
发明概述
在第一方面,本发明提供用于使织物抗熔融金属的组合物,该组合物包含:
可交联聚合物;
陶瓷颗粒;
阻燃剂;和任选地
硅酮(silicone)弹性体和/或乙二醛。
在第二方面,本发明提供防熔融金属的处理过的织物,该处理过的织物包含含有非熔化纤维的底基(base)织物,该底基织物用交联的可交联聚合物在其一侧或两侧进行处理以形成具有底基织物的纤维、悬浮在其中的陶瓷颗粒、阻燃剂和任选地硅酮弹性体和/或乙二醛的基体(matrix)。
在第三方面,本发明提供保护穿戴者防熔融金属的服装,该服装包含处理过的织物,该处理过的织物含有非熔化纤维的底基织物,该底基织物用交联的可交联聚合物在其一侧或两侧进行处理以形成具有底基织物的纤维、悬浮在其中的陶瓷颗粒、阻燃剂和任选地硅酮弹性体和/或乙二醛的基体。
在第四方面,本发明提供制造防熔融金属的织物的方法或工艺,该方法包括如下步骤:
(1)提供包含非熔化纤维的底基织物;
(2)用以下物质处理该底基织物:
可交联聚合物;
交联剂;
陶瓷颗粒;
阻燃剂;和任选地
硅酮弹性体和/或乙二醛;
(3)交联所述聚合物以形成具有底基织物纤维的基体,并有陶瓷颗粒悬浮在其中。
在第五方面,本发明提供处理过的保护穿戴者防熔融金属的织物的用途,其中处理过的织物包含含有非熔化纤维的底基织物,该底基织物用包含交联的聚合物的组合物在其一侧或两侧进行处理以形成具有底基织物的纤维、和悬浮在基体中的陶瓷颗粒的基体。
在第六方面,本发明提供保护人防熔融金属的方法,包括向人提供包含处理过的织物的服装的步骤,其中该处理过的织物包含含有非熔化纤维的底基织物,该底基织物用包含聚合的聚合物在其一侧或两侧进行处理以形成具有该底基织物的纤维和悬浮在基体中的陶瓷颗粒的基体。
在第七方面,本发明提供处理过的织物用于制造保护穿戴者防熔融金属的服装的用途,其中该处理过的织物包含非熔化纤维的底基织物,该底基织物用包含交联的可交联聚合物的组合物在其一侧或两侧进行处理以形成具有该底基织物的纤维和悬浮在其中的陶瓷颗粒的基体。
在第八方面,本发明提供制造陶瓷涂层组合物的方法或工艺,包括在水性溶剂中混合以下物质:
可交联聚合物;
陶瓷颗粒;
阻燃剂;和任选地
硅酮弹性体和/或乙二醛。
在第九方面,本发明提供陶瓷涂层组合物用于制造抗熔融金属的织物的用途,其中陶瓷涂层组合物包含:
可交联聚合物;和
陶瓷颗粒。
优选实施方案的详细说明
缩写
PU:聚氨酯
M5:聚吡啶并二咪唑(polypyridobisimidazole),由下式表示:
HMDI:1,6-己二异氰酸酯
本发明提供抗熔融金属吸收的使熔融金属从织物上流掉的处理过的织物,同时它也是阻燃的和抗热传递的。本发明的织物可用来制造防护服装,其保护穿戴者防熔融金属溅出物和飞溅物。整个服装可以由处理过的织物制成,或高危险区域可以用处理过的织物制成,而较低危险区域由其他织物制成。
本发明的织物包含由非熔化纤维制成的底基织物。措辞“非熔化纤维”包括当温度升高在熔化之前或非常接近于熔化时,会碳化的那些纤维。特别优选的非熔化纤维包括有机的非熔化纤维,例如纤维素纤维(例如,棉制品、木质纤维、亚麻布、粘胶纤维、人造纤维)、毛、芳族聚酰胺纤维(例如,对-芳族聚酰胺,如和间-芳族聚酰胺,如)、聚苯并咪唑、聚酰亚胺、多环芳烃(polyarenes)、人造纤维(例如lyocell)、聚吡啶并二咪唑(M5,参看以上缩写)和它们的混合物。优选的用于本发明的织物的非熔化纤维选自粘胶纤维、芳族聚酰胺(例如,对-芳族聚酰胺、间-芳族聚酰胺)、M5和毛。这些纤维可以以100wt%或作为它们的共混物进行使用。
在一些实施方案中,非熔化纤维可以与熔化纤维(如聚酯、聚酰胺和聚丙烯)共混。
该底基织物用陶瓷组合物进行处理,该组合物包含可交联聚合物,例如,聚氨酯、聚氯乙烯、氟亚乙基丙烯(fluoroethyleneprpylene)、硅酮、三聚氰胺和聚丙烯酸酯。优选地该可交联聚合物是聚氨酯。
当可交联聚合物是聚氨酯时,优选地它是通过交联将产生柔性或弹性聚氨酯的聚氨酯。这改善了该处理过的织物的柔软性和抗磨性。
聚氨酯是由多异氰酸酯(通常为二异氰酸酯)和多元醇(通常为二醇)制成的聚合物。可以使用的多异氰酸酯的实例包括芳族的多异氰酸酯、如苯撑二异氰酸酯、甲苯二异氰酸酯(例如2,4-和2,6-)、二异氰酸四甲基二甲苯酯(tetramethylxylenediisocyanate)、二异氰酸二甲苯酯(xylenediisocyanate)、二异氰酸亚甲基二苯酯(MDI)以及脂肪族和环脂族的多异氰酸酯,如二环己基甲烷-4,4’-二异氰酸酯、1,6-己二异氰酸盐、二异氰酸四亚甲酯、二异氰酸三甲基六亚甲酯、异氟尔酮二异氰酸酯和它们的任意混合物。还可以使用聚合的异氰酸酯(如聚合的MDI)。还合适的是这些多异氰酸酯的“预聚合物”,其包含多异氰酸酯和聚醚或聚酯多元醇部分预反应的混合物。一般地,上述多异氰酸酯以相对于多元醇确定的异氰酸酯指数为80-400的量进行使用。
多元醇可以是优选具有2-25个碳原子的多元醇、聚醚或者聚酯。实例包括乙二醇、丙二醇、丁二醇、戊二醇、己二醇、癸二醇、二甘醇、2,2,4-三甲基戊二醇、2,2-二甲基丙二醇、二甲基环己二醇、2,2-双(4-羟苯基)-丙烷(双酚A)、2,2-双(4-羟苯基)丁烷(双酚B)、1,1-双(4-羟苯基)-3,3,5-三甲基环己烷(双酚C)、芳族的聚酯多醇、聚己酸内酯、聚(环氧乙烷)和聚(氧化丙烯)聚合物和带有端羟基的共聚物,该端羟基来源于多羟基化合物,例如二醇和/或三醇。上述二醇和三醇包括,作为非限制性实例,乙二醇、丙二醇、1,3-丁二醇、1,4-丁二醇、1,6-己二醇、新戊二醇、二甘醇、二丙甘醇、季戊四醇、甘油、双甘油、三羟甲基丙烷、糖如蔗糖及其他低分子量多元醇。还有用的是胺聚醚多元醇,其可以通过使胺(如乙二胺、二亚乙基三胺、甲苯二胺、二苯基甲烷二胺、三乙醇胺等等)与环氧乙烷或氧化丙烯反应进行制备。
用于聚氨酯形成的合适催化剂是位阻胺,例如二氮杂双环[2.2.2]辛烷(DABCO)、二[2-(N,N-二甲基氨基乙基)]醚、双(3-二甲酰氨基丙基)氨基-2-丙醇胺、五甲基二亚丙基三胺、N,N-二甲基环己胺(DMCHA)、三(二甲氨基甲基)苯酚、1,3,5-三(二甲胺丙基(dimethylinpropyl))六氢三嗪、DMDEE、二吗啉聚氧乙烯醚、1-甲基-4-二甲氨基哌嗪、五甲基二亚丙基三胺、1,8-二氮杂双环[5,4,0]十一碳烯-7、二甲胺丙基二丙醇胺、三乙烯-二胺-1,4-二醇。催化剂的其他实例是叔胺、有机锡化合物和羧酸盐氨基甲酸酯(carboxylate urethane)催化剂(胶凝和/或发泡)。有用的催化剂的典型实例是胺催化剂,如三亚乙基二胺、二甲基环己胺、四甲基己烷二胺、双(二甲氨基乙基)醚、三(二甲氨基丙基)六氢三嗪、1-异丁基-2-甲基咪唑、1,2-二甲基咪唑、二甲氨基乙醇、二乙氨基乙醇、五甲基二亚乙基三胺、五甲基二亚丙基三胺、甲基吗啉、乙基吗啉、季铵盐、有机酸的盐,和锡催化剂如二月桂酸二丁基锡等等。
有利地,用于陶瓷组合物和本发明织物的聚氨酯具有以下组分:
20-60wt%的至少一种异氰酸酯;
5-50wt%的至少一种聚醚二醇;
0-10wt%的一种或多种脂肪族或环脂族二醇;
0-50wt%,优选地5-50wt%的一种或多种聚酯二醇;
优选的用于本发明的陶瓷组合物的聚氨酯用单体1,6-己二异氰酸酯(HMDI)和具有直链或支链的聚酯组分的聚酯多元醇制成。优选的聚氨酯具有1,000-10,000g/mol的重均分子量。合适的聚氨酯可以商品名Alberdingk-(Alberdingk)、(Bayer)和(Stahl)商业获得。
聚氨酯链具有未反应的羟基末端,其可以通过加入另外的多异氰酸酯交联剂进行交联以形成链间键。本发明的陶瓷组合物通过将他们施用在底基织物的表面上,优选地使用交联剂和任选的催化剂开始链间交联而进行使用。优选的交联剂是上述的多异氰酸酯。特别优选地,多异氰酸酯交联剂用例如肟基团进行封端。封端基团在升高的温度下(例如约140-200℃)掉落,开始交联。优选的肟封端基团是丁烷肟。优选地交联剂具有多于两个的异氰酸酯基,特别优选地它具有三个异氰酸酯基。基于陶瓷涂料组合物的总重量(减去溶剂),交联剂优选地以或大约以1-10wt%,更优选地以或大约以3-8wt%存在。
用于本发明的陶瓷组合物的可交联聚氨酯可以选自在不会损坏底基织物的条件下可以被交联的那些聚氨酯。交联可以用加热和/或通过利用催化剂开始。如果加入催化剂,优选地它在临陶瓷组合物被施用在底基织物之前被加入。交联剂可以被加入到陶瓷组合物中,并且该陶瓷组合物在低温下(即,低于20℃或大约20℃,更优选地低于4℃或大约4℃)储存,直到施用。在将陶瓷涂料组合物施用在底基织物之后,对处理过的织物加热以引起交联。或者,交联剂和/或催化剂可以在临陶瓷组合物被施用在底基织物之前被加入到陶瓷组合物中。
陶瓷组合物包含陶瓷颗粒。术语陶瓷指各种硬的、易碎的、耐热的并且不锈的材料中的任何一种,其通过成形然后在高温下烧制非金属矿物(如粘土)进行制造。陶瓷包括但不限于:
四氮化三硅(Si3N4)
碳化硼(B4C)
碳化硅(SiC)
二硼化镁(MgB2)
氧化锌(ZnO)
铁氧体(Fe3O4)
滑石
硅酸铝
钇钡铜氧化物(YBa2Cu3O7-x)
氮化硼
钛酸钡(通常与钛酸锶混合)
锆酸钛酸铅
氧化锆
铁氧体(Fe3O4)
滑石
硅酸铝
优选的陶瓷颗粒是碳化硅。
颗粒的粒度分布优选地为或大约为0.1-10微米。
优选的陶瓷颗粒是碳化硅,特别是粒度分布为0.1-10微米的碳化硅颗粒。
陶瓷组合物通过将可交联聚合物和陶瓷颗粒悬浮在合适的溶剂中(例如水、甲醇、乙醇、丙醇、甲苯、乙酸乙酯等等,优选地为水)进行制备。可以加入交联剂和/或催化剂并且陶瓷组合物被储存直到使用,或交联剂和/或催化剂可以临组合物被施用到底基织物之前被加入到陶瓷组合物中。基于陶瓷组合物的总重量(减去溶剂),可交联聚合物优选地以或大约以25-65wt%,更优选地以或大约以33-53wt%存在。基于陶瓷组合物的总重量(减去溶剂),陶瓷颗粒有利地以或大约以1-40wt%,优选地以2.75-30wt%存在。
本发明的陶瓷组合物和织物可以另外包含乙二醛。乙二醛对纤维素纤维、上述粘胶纤维特别有用,降低收缩(shrinking)和膨胀(swelling)。加入乙二醛改善了得到的处理过的织物耐受湿气和潮湿的能力。将处理过的织物暴露在湿气时,可以产生底基织物的膨胀。如果固化的陶瓷组合物不是足够有回弹力的,底基织物的膨胀可能使固化组合物破裂。加入乙二醛降低了这种破裂现象。乙二醛可以存在于陶瓷涂料组合物中,或它可以在施用该陶瓷涂料之前或之后被施用在处理过的织物上。优选地,它在施用陶瓷涂料之前进行施用。
本发明的陶瓷组合物和织物有利地包含硅酮弹性体。硅酮弹性体也被称为硅酮橡胶,并且例如通过二氯硅烷R2SiCl2的聚合反应获得,其中R是例如甲基、乙基、乙烯基或苯基。优选的硅酮弹性体是聚二甲基硅氧烷。加入硅酮弹性体改善了处理过的织物的柔软性和回弹力,得到较好的悬垂性(drape)和改善的穿戴者感觉。如果存在硅酮弹性体,基于陶瓷组合物的总重量(减去溶剂),优选地它以或大约以2-15wt%,更优选地以或大约以5-10wt%的浓度进行使用。
本发明的陶瓷组合物和织物可以有利地包含阻燃剂。阻燃剂优选地选自含磷阻燃剂,例如,红磷、磷酸酯,如磷酸三甲酯、磷酸三乙酯、磷酸三氯丙基酯、膦酸四(2-氯乙基)亚乙基酯、五溴联苯醚、三(1,3-二氯丙基)磷酸酯、三(β-氯乙基)磷酸酯、磷酸铵、磷酸三甲苯酯。
合适的含卤素有机阻燃剂包括在本领域中已知的用作阻燃剂的含卤素有机化合物。含卤素的有机阻燃剂的实例是含卤素的芳族阻燃剂,如溴化二苯醚(例如,五溴联苯醚和十溴联苯醚)、聚三溴苯乙烯、三氯甲基四溴苯、四溴双酚A和可从Ethyl公司以SAYTEX8010获得的芳族溴化阻燃剂。其他阻燃剂包括二溴丙醇、六溴环十二烷、二溴乙基二溴环己烷、磷酸三(2,3-二溴丙基)酯和磷酸三(β-氯丙基)酯、二溴季戊四醇、六溴环十二烷和磷酸三氯丙酯。
优选的阻燃剂是红磷。
还可能使用选自这些种类(groups)的一类或几类的几种组分的混合物作为阻燃剂。
如果使用阻燃剂,基于陶瓷组合物的总重量(减去溶剂),优选地它以或大约以2-20wt%,更优选地以5-15wt%存在。
或者,如在例如美国专利no.4,022,718(Russo)所公开,聚氨酯可以包含向聚氨酯提供阻燃性的单体,该文件在此以引用的方式并入本文。上述单体的实例是2,3-二溴-2-丁烯二醇-1,4。
陶瓷组合物可以有利地包含硅酮消泡剂。基于陶瓷组合物的总重量(减去溶剂),硅酮消泡剂优选地以或大约以0.1-0.4wt%,更优选地以或大约以0.5-2wt%存在。
陶瓷组合物可以另外地包含增稠剂,其有助于将组合物施用在织物上。如果组合物被增稠到形成糊剂的程度,它可以通过铺展(例如使用刮刀或抹刀)被施用在织物上。增稠剂还帮助组合物依附在织物上直到聚氨酯被聚合。合适的增稠剂选自聚丙烯酸酯和聚氨酯。特别优选的是聚丙烯酸酯,其包括丙烯酸和/或甲基丙烯酸任选地与乙烯基型不饱和共聚单体的均-和共-聚物。对于用刮刀铺展,陶瓷组合物的优选的粘度在或大约在5000-7000mPa.s的范围之内,更优选地在或大约在6000±500mPa.s的范围内。基于陶瓷组合物的总重量(减去溶剂),增稠剂优选地以或大约以0.1-4wt%,更优选地以或大约以0.2-2wt%的浓度被加入。
除了通过铺展施用以外,陶瓷组合物,如果被制备成具有较低的粘度(例如400-1,000mPa.s),则可以通过喷射、浸泡、涂漆或浸渍进行施用。
在将陶瓷组合物施用在底基织物的一个或两个表面上之后,必需交联聚氨酯分子。这可以通过加热到足以开始交联的温度(例如在或大约在100-200℃)而进行。加热可以在拉幅架(tentering frame)上,或通过压延或使用另一种合适的设备进行。压延优选地在或大约在120-300℃,更优选地在或大约在150℃,和使用在或大约在15-45吨,更优选地在或大约在30吨的压区压力(nip pressure)进行。
除了交联该可交联聚合物以外,加热驱除出用于制造陶瓷组合物的一种或多种溶剂。在加热和/或压延处理过的织物(和涂布在其上的陶瓷组合物)之前,可以使用例如强制通风进行干燥。
当将陶瓷组合物施用于织物时,如果陶瓷组合物中不存在乙二醛,它可以在加热和/或压延之前被施用于该处理过的织物以交联可交联聚合物。
本发明的处理过的织物提供优异的对熔融金属溅出物的防护性。织物可以有利地用来制造用来保护穿戴者避免熔融金属的溅出物的服装。该服装可以使用已知的制造服装的方法进行制备。对于一些使用,可能希望使仅仅服装的高危险部分由本发明的处理过的织物制成。例如,裤子和衬衫(或工作服)的袖口通常被暴露于小熔融金属飞溅物,因此可能希望仅仅使这些区域由本发明的处理过的织物制成。
实施例
该实施例举例说明了陶瓷涂料对熔融金属性能的影响。所有百分比是以重量计的,除非另有说明。
底基织物
将40%的可变长度的短毛纤维(staple wool fibre)、28%的具有在8-12cm范围内可变纤维长度的粘胶短纤维(用阻燃剂处理的)、29%的卷曲聚(间亚苯基间苯二甲酰胺(metaphenyleneisophthalamide))(MPD-I)短纤维(也具有在8-12cm范围内的可变纤维长度)、1%的对-芳族聚酰胺()纤维和2%的P-140碳芯聚酰胺片状纤维通过精梳工艺共混在一起以制造短纤维的精密共混物。
毛通过使用常规的酸性染色工艺进行初步套染(top dye)。
然后通过环锭纺纱工艺使用常规的长纤维精纺加工设备将短纤维的共混物纺成短纤维纱。然后将该短纤维纱使用两步加捻工艺捻合在一起并且用蒸汽处理以稳定纱线防止起皱。获得的捻合线具有50tex的线密度。纱线被织成具有28.0经(ends)/cm和19.5纬(picks)/cm的247g/m2 2×1斜纹编织织物,其宽度为165cm。织物被洗涤、在100℃在拉幅机中用最大过装料进行干燥,并机械预缩整理。
成品织物具有28.5经/cm和22.0纬/cm和最终被提高到269g/m2,其宽度为160cm。
陶瓷涂料组合物
制备糊剂,其包含:
(1)70wt%的由单体HMDI和具有直链或支链聚酯组分的聚酯多醇制成的PU-基粘结剂。该粘结剂PU具有5,000g/mol的重均分子量。
(2)30wt%的由粒度分布为0.1-10微米的碳化硅颗粒组成的陶瓷颗粒。
向该糊剂加入:
5wt%的由用丁烷肟封端的三异氰酸酯组成的交联剂。
6wt%的红磷;
1wt%的硅酮消泡剂;
7wt%的硅酮弹性体(聚二甲硅氧烷);
5wt%的colour imperon navy K-fr;和
0.6wt%的聚丙烯酸酯增稠剂。
加入水以形成具有6000mPa.s+/-500的粘度的溶液,pH为7-9。
基底织物的涂布
将陶瓷涂料组合物施用于底基织物:使用配备有1mm涂布刮刀的工业用涂布机。织物处理速率被设定为15m/min。机器与拉幅机连接以干燥涂层。拉幅机温度起始为第一箱100℃和结束为最后一个(第5个)箱160℃,曝露时间为90秒。
施用于织物上的陶瓷涂料组合物的量为干燥后60g/m2。
然后使涂布的织物在含有低甲醛的乙二醛反应整理剂中浸轧。该过程产生纤维的交联,特别是包含在织物中的粘胶纤维,以获得更好的洗涤收缩性能和当潮湿时降低纤维的膨胀。
织物在拉幅机上进行干燥。
织物在150℃用30吨压力进行压延以得到本发明的处理过的织物的实例。
未经处理的底基织物的抗熔融金属性(对比例)
根据标准EN531:1995第6.6条熔融铁飞溅(Molten iron splash),通过使用测试法EN 373:1993和使用铁作为金属对底基织物(即未经处理的)进行抗熔融铁测试。
在这个测试中,织物样品被固定覆盖在板上的PVC层上面。将板在与水平面规定的角度倾斜并使规定量的熔融金属从规定高度倒在织物的面上。冷却后,熔融金属飞溅指数(splash index)通过以下的评价进行赋值:
对PVC膜检测该PVC膜的平滑度、熔化或穿孔。如果任何这些缺陷出现,并且缺陷的宽度大于或等于5毫米,织物被判为没有通过熔融金属测试。如果出现离散点缺陷,如果这些点的总宽度大于或等于5毫米,织物被判为没有通过测试。
可以被倒在织物上的熔融金属的克数越大(而没有损坏PVC外皮(即″没有通过″测试)),织物抗熔融金属性越好。
试验条件为:
金属 | 铁 |
倾倒温度 | 1400±20℃ |
熔融金属的量 | 200-208g |
倾倒高度 | 225±5mm |
样品与水平面的角度 | 75±1° |
底基织物(即未经处理的)的性能列在表1中。
本发明的处理过的织物的抗熔融金属性
根据标准EN531:1995第6.6条熔融铁飞溅,通过使用测试法EN373:1993和使用熔融铁,对本发明的处理过的织物进行抗熔融铁测试。试验条件为对底基(未经处理的)织物的测试条件。
通过使用测试法EN373:1993和使用熔融铝,还对处理过的织物进行抗标准EN531:1995第6.6条熔融铁飞溅测试。试验条件为:
金属 | 铝 |
倾倒温度 | 780±20℃ |
熔融金属的量 | 203-204g |
倾倒高度 | 225±5mm |
样品与水平面的角度 | 60±1° |
处理过的织物在两个测试中的性能列在表2中。织物在重复洗涤之后也进行测试。洗涤条件列在下面:
表2表明根据本发明的处理过的织物对于熔融铁飞溅评为E3。这明显地好于具有指数E1的未经处理的织物。这表明本发明的织物更防护熔融铁飞溅物。该防护效果甚至在25次洗涤之后仍被保持。
本发明的处理过的织物也显示出防护熔融铝。
洗涤条件
对于本发明的处理过的织物,抗熔融金属性优选地得到保持,甚至在重复洗涤之后也如此。
根据Operating Procedure No:EFL-028和根据标准ISO 5077,洗涤如上所述的处理过的织物。在每5个洗涤周期之后,进行1个干燥周期。
洗涤:
温度:60±3℃
洗涤剂:1g/l的IEC
根据标准ISO6330(方法A2)和Operating Procedure No:EFL-029,使用前装载水平滚筒机(drum machine)(型号A1)进行洗涤。
干燥:
根据标准ISO 6330和Operating Procedure EFL-029,使用滚筒机(tumbling machine)进行干燥,
温度:60±3℃
本发明的处理过的织物的其他性质
本发明的处理过的织物还根据以下进行测试:
根据标准EN ISO 12947-2,通过直至破裂的循环次数进行磨损测定(Martindale)。
测试条件:
●环境:20±3℃,65±5%相对湿度
●施用压力:12kPa
断裂强度和伸长率(elongation)的测定(Strip方法)(ISO 5081 1977)
限制火焰蔓延(limited flame spread)的测定(ISO 15025-2003-方法B)
表3总结了性质并且显示陶瓷涂料没有负面影响织物的纺织品物理性能和可燃性并且改善了抗磨性。
Claims (22)
1.防熔融金属的处理过的织物,该处理过的织物包含含有非熔化纤维的底基织物,该底基织物用交联的可交联聚合物在其一侧或两侧进行处理以形成基体,该基体具有底基织物的纤维、悬浮在基体中的陶瓷颗粒、阻燃剂和任选的硅酮弹性体和/或乙二醛。
2.权利要求1的处理过的织物,其中底基织物包含芳族聚酰胺纤维。
3.权利要求1的处理过的织物,其中底基织物包含对-芳族聚酰胺纤维。
4.权利要求1的处理过的织物,其中所述交联的聚合物是交联的聚氨酯。
5.权利要求1的处理过的织物,其中所述交联的聚合物是交联的聚氨酯,其包含单体1,6-己二异氰酸酯(HMDI)和含有直链或支链聚酯组分的聚酯多醇,并具有1,000-10,000g/mol的重均分子量。
6.权利要求1的处理过的织物,其中所述交联的聚合物用选自多异氰酸酯的交联剂进行交联。
7.权利要求1的处理过的织物,其中陶瓷颗粒是碳化硅并且粒度分布为或大约为0.1-10微米。
8.用于保护穿戴者防熔融金属的服装,该服装包含权利要求1的处理过的织物。
9.用于制造防熔融金属的织物的方法,该方法包括以下步骤:
(1)提供包含非熔化纤维的底基织物;
(2)用以下物质处理该底基织物:
可交联聚合物;
交联剂;
陶瓷颗粒;
阻燃剂;
和任选的硅酮弹性体;和/或乙二醛;
(3)交联所述聚合物以形成具有底基织物纤维的基体,并有陶瓷颗粒悬浮在其中。
10.权利要求9的方法,其中底基织物包含芳族聚酰胺纤维。
11.权利要求9的方法,其中底基织物包含对-芳族聚酰胺纤维。
12.权利要求9的方法,其中交联的聚合物是交联的聚氨酯。
13.权利要求9的方法,其中交联的聚合物是交联的聚氨酯,其包含单体1,6-己二异氰酸酯(HMDI)和含有直链或支链聚酯组分的聚酯多醇,并具有1,000-10,000g/mol的重均分子量。
14.权利要求9的方法,其中交联的聚合物用选自多异氰酸酯的交联剂进行交联。
15.权利要求9的方法,其中陶瓷颗粒是碳化硅并且粒度分布为或大约为0.1-10微米。
16.保护人防熔融金属的方法,包括向人提供包含处理过的织物的服装的步骤,其中该处理过的织物包含含有非熔化纤维的底基织物,该底基织物用包含交联的可交联聚合物的组合物在其一侧或两侧进行处理以形成具有底基织物的纤维、和悬浮在基体中的陶瓷颗粒的基体。
17.权利要求16的方法,其中底基织物包含芳族聚酰胺纤维。
18.权利要求16的方法,其中底基织物包含对-芳族聚酰胺纤维。
19.权利要求16的方法,其中交联的聚合物是交联的聚氨酯。
20.权利要求16的方法,其中交联的聚合物是交联的聚氨酯,其包含单体1,6-己二异氰酸酯(HMDI)和含有直链或支链聚酯组分的聚酯多醇,并具有1,000-10,000g/mol的重均分子量。
21.权利要求16的方法,其中交联的聚合物用选自多异氰酸酯的交联剂进行交联。
22.权利要求16的方法,其中陶瓷颗粒是碳化硅并且粒度分布为或大约为0.1-10微米。
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- 2007-03-06 CN CN2007800098898A patent/CN101405453B/zh active Active
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103732824A (zh) * | 2011-08-04 | 2014-04-16 | 可隆工业株式会社 | 超吸收性纱线以及制备该纱线的方法 |
CN106400505A (zh) * | 2015-09-22 | 2017-02-15 | 浙江新达经编有限公司 | 一种纤维混纺高弹面料的制备方法 |
CN106400505B (zh) * | 2015-09-22 | 2018-10-09 | 浙江新达经编有限公司 | 一种纤维混纺高弹面料的制备方法 |
Also Published As
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JP2009530511A (ja) | 2009-08-27 |
CA2641807C (en) | 2012-09-18 |
MX2008011859A (es) | 2008-09-30 |
WO2007108948A1 (en) | 2007-09-27 |
CA2641807A1 (en) | 2007-09-27 |
KR101425685B1 (ko) | 2014-08-01 |
KR20080104166A (ko) | 2008-12-01 |
JP5324421B2 (ja) | 2013-10-23 |
BRPI0709337A2 (pt) | 2011-07-12 |
US7772140B2 (en) | 2010-08-10 |
CN101405453B (zh) | 2012-09-05 |
EP1996761A1 (en) | 2008-12-03 |
EP1996761B1 (en) | 2015-09-09 |
US20080038972A1 (en) | 2008-02-14 |
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