CN102741364A - 减磨涂层 - Google Patents

减磨涂层 Download PDF

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Publication number
CN102741364A
CN102741364A CN2010800600072A CN201080060007A CN102741364A CN 102741364 A CN102741364 A CN 102741364A CN 2010800600072 A CN2010800600072 A CN 2010800600072A CN 201080060007 A CN201080060007 A CN 201080060007A CN 102741364 A CN102741364 A CN 102741364A
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CN
China
Prior art keywords
clay mineral
aqueous coating
modification
water
coating compsn
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN2010800600072A
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English (en)
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CN102741364B (zh
Inventor
野副次雄
辻裕一
W·布莱克伍德
儿岛和彦
尾崎胜
堀诚司
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DuPont Toray Specialty Materials KK
Dow Silicones Corp
Original Assignee
Dow Corning Toray Co Ltd
Dow Corning Corp
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Publication of CN102741364A publication Critical patent/CN102741364A/zh
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Publication of CN102741364B publication Critical patent/CN102741364B/zh
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
    • B60R21/00—Arrangements or fittings on vehicles for protecting or preventing injuries to occupants or pedestrians in case of accidents or other traffic risks
    • B60R21/02—Occupant safety arrangements or fittings, e.g. crash pads
    • B60R21/16—Inflatable occupant restraints or confinements designed to inflate upon impact or impending impact, e.g. air bags
    • B60R21/23—Inflatable members
    • B60R21/235—Inflatable members characterised by their material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/28—Processes for applying liquids or other fluent materials performed by transfer from the surfaces of elements carrying the liquid or other fluent material, e.g. brushes, pads, rollers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/30—Processes for applying liquids or other fluent materials performed by gravity only, i.e. flow coating
    • B05D1/305—Curtain coating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • C09D5/028—Pigments; Filters
    • C—CHEMISTRY; METALLURGY
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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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/43—Thickening agents
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
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    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • D06M11/70—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 phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with oxides of phosphorus; with hypophosphorous, phosphorous or phosphoric acids or their salts
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    • D06M11/79—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 silicon or compounds thereof with silicon dioxide, silicic acids or their salts
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Abstract

用于减小表面处的摩擦和/或粘连的水性涂层组合物，所述组合物包含固体润滑剂和改性的或合成的粘土矿物，改性的或合成的粘土矿物具有增稠性质，使得2％按重量计的改性的或合成的粘土矿物增稠剂的水分散体具有至少1000mPa.s的粘度。用作增稠剂的优选的粘土矿物优选是蒙脱石粘土，例如皂石、锂蒙脱石、硅镁石、锌蒙脱石、膨润土、贝得石、绿脱石或蒙脱土。

Description

减磨涂层
本发明涉及被设计成应用于表面以减小该表面的摩擦的减磨涂层。具体地，本发明涉及适合于作为顶涂层应用于已涂布有弹性底涂层的气囊和气囊织物上的减磨涂层组合物。
气囊通常由在其至少一侧上被弹性体层覆盖的、用合成纤维制成的编织织物或针织物形成，合成纤维为例如聚酰胺，如尼龙-6，6或聚酯。气囊可由平幅织物制件制成，平幅织物制件可被涂布且然后被缝合在一起以提供充足的机械强度，或气囊可采用整体地织缝以一体式纺织。缝合的气囊通常在气囊的内侧被组装有涂布的织物表面。一体式纺织的气囊是在气囊的外侧上涂布。用于涂布气囊或气囊织物的优选弹性体是硅酮弹性体，其是固化的有机聚硅氧烷组合物，具体地为通过氢化硅烷化固化的硅橡胶涂层，氢化硅烷化为通过一种聚有机硅氧烷的烯基与另一种含硅材料(聚有机硅氧烷或硅烷)的Si-H基团的反应。
用于涂布气囊或气囊织物的可选择的弹性体是有机树脂弹性体，包括氨基甲酸酯聚合物。所谓的“有机树脂”或“有机聚合物”指形成聚合物链的原子中的至少50％的原子为碳原子的聚合物。
美国专利5110666描述了一种涂布有新颖的聚碳酸酯-聚醚型聚氨酯的织物基材，以用作驾驶员的侧面气囊或乘客的侧面气囊。
美国专利6169043描述了包含聚氨酯和聚丙烯酸酯组分的混合物的气囊涂层组合物，以在织物表面上提供低渗透性涂层。
美国专利7543843描述了杂化树脂作为气囊涂层的用途。杂化树脂是与丙烯酸树脂、乙烯基树脂(vinyls)和/或硅酮共混的氨基甲酸酯，其中组分中的至少一种具有20℃或更低的玻璃化转变温度。氨基甲酸酯优选具有聚碳酸酯、聚丁二醇、硅基二醇或烯烃基二醇型。
涂布有硅酮弹性体的气囊描述于许多公开的专利和申请中，例如US专利5789084、5877256、6709752、6425600和6511754以及WO-A-08/020605和WO-A-08/020635。
如果使弹性体底涂层作为气囊上的唯一涂层，这种底涂层的表面性能将导致粘连(在储存期间和汽车中的气囊的密填充期间，尤其在高的环境温度时，弹性体涂布的表面粘附到彼此)和气囊膨胀时的非常高的压力，这将导致在膨胀期间由于撕裂产生的气囊故障或由于弹性体底涂层与织物分离产生的气囊故障。在制造气囊期间当涂布有弹性体的织物储存在辊中时，弹性体表面之间的粘连也是个问题。另外，诸如硅酮弹性体涂层的许多弹性体在固化时具有高的表面摩擦。
此外，已发现，在一些有机树脂底涂层上、尤其在氨基甲酸酯聚合物底涂层或用氨基树脂固化的底涂层上应用可固化的液体硅橡胶顶涂层释放令人不舒服的鱼腥味。
US-A-5945185描述了由其中硅氧烷含量为按重量计5％-40％的硅酮改性的热塑性聚氨酯树脂制成的气囊。这种气囊被认为具有降低的粘连危险，但交通工具制造者偏爱使用涂布织物气囊。
美国专利6239046描述了用粘性聚氨酯层并且然后用弹性聚硅氧烷层涂布针织物、编织或非编织织物基材。然后由被涂布的织物基材形成具有优异的气体容纳性和优异的耐热性的气帘或气囊。
美国专利6177365和美国专利6177366描述了包含至少两个分离层的气囊涂层。与气囊表面接触的第一层(底涂层)包含聚氨酯、聚碳酸酯、聚酰胺、丁基橡胶、氢化丁腈橡胶或乙烯-醋酸乙烯酯共聚物的非硅酮组合物。第二层(顶涂层)是硅酮材料。
美国专利6177366描述了包含至少两个分离的且不同的层的气囊涂层。与气囊表面接触的第一层(底涂层)包含硅酮弹性体。第二层(顶涂层)优选是有机硅树脂。
US专利7198854描述了用于涂布有硅酮弹性体的纺织品的减磨硅酮清漆。该清漆包含可交联的硅酮组合物，其含有在催化剂的存在下相互反应以允许交联的两种硅酮和包含特定组分的粉状(共)聚酰胺。
JP-A-2004-167556公开了一种水性金属浇铸成型涂层剂，其包含作为保温剂的硅藻土、作为脱模剂的滑石和作为粘合剂的膨润土。
根据本发明的用于减小表面处的摩擦和/或粘连的水性涂层组合物包含：固体润滑剂和改性的或合成的粘土矿物，改性的或合成的粘土矿物具有增稠性质，使得2％按重量计的改性的或合成的粘土矿物增稠剂的水分散体具有至少1000mPa.s的粘度。使用具有20mm直径，2°锥度的Wells-Brookfield锥/板粘度计以1s-1的剪切速率在25℃下测量粘度(ASTMD4287)。除非另外指明，本文描述的对于改性的或合成的粘土矿物增稠剂的所有水分散体所给出的粘度均按照与如上描述的方式相同的方式进行测量。
本发明还包括一种气囊，其涂布有一种包含以下物质的防粘连涂层：固体润滑剂和改性的或合成的粘土矿物以及水溶性有机聚合物，改性的或合成的粘土矿物具有增稠性质，使得2％按重量计的改性的或合成的粘土矿物增稠剂的水分散体具有25℃下至少1000mPa.s的粘度。
本发明还包括一种涂布基材以减小摩擦和/或粘连的方法，其中基材涂布有包含以下物质的水性涂层组合物：固体润滑剂和改性的或合成的粘土矿物，改性的或合成的粘土矿物具有增稠性质，使得2％按重量计的改性的或合成的粘土矿物增稠剂的水分散体具有25℃下至少1000mPa.s的粘度。
固体润滑剂优选包括页硅酸盐，还称为层状硅酸盐。适于作为本发明的固体润滑剂的页硅酸盐的实例包括云母、滑石例如滑石微球、高岭土、蒙脱石、绢云母和绿泥石。滑石是广泛可得到的且作为润滑剂是有效的。绿泥石作为润滑剂也是有效的，且具有比滑石可更易于分散在水中的优点。固体润滑剂可另外地或可选择地包括含氟聚合物，例如聚四氟乙烯(PTFE)、固体烃蜡，例如聚烯烃蜡，如微晶化的聚丙烯蜡或PTFE和蜡的混合物、或二硫化钼、石墨、硫化锌或磷酸三钙、或这些中的任意两种或更多种的混合物。
固体润滑剂优选地以按重量计水性涂层组合物的至少1％、可选择地至少3％，例如按重量计水性涂层组合物的5％或10％至高达40％存在。
用作增稠剂的粘土矿物优选地是蒙脱石粘土，例如皂石、锂蒙脱石、硅镁石、锌蒙脱石、膨润土、贝得石、绿脱石或蒙脱土。
根据本发明的一个优选的方面，粘土矿物被水溶性有机聚合物改性。合适的水溶性有机聚合物包括含有羧酸盐基团的聚合物，例如含羧基的加成聚合物，如聚丙烯酸钠或聚甲基丙烯酸钠。
粘土矿物，例如膨润土或蒙脱土，可通过与水溶性有机聚合物预混合而被改性。例如，粘土矿物和水溶性有机聚合物可均匀地混合在水中，随后干燥混合物，例如通过喷雾干燥。如需要，可将所得到的干燥的混合物研磨到期望的粒径，其可以是从1μm至20μm的范围。这种混合物中的水溶性聚合物的含量可例如为0.1wt％至40wt％的范围。
可选择地，诸如膨润土或蒙脱土的粘土矿物可通过用烷基烷氧基硅烷处理而被改性。烷基烷氧基硅烷优选是烷基三烷氧基硅烷，例如甲基三甲氧基硅烷、乙基三甲氧基硅烷、甲基三乙氧基硅烷或乙基三乙氧基硅烷。烷基烷氧基硅烷可例如被以纯液体硅烷或以在有机溶剂中的溶液的形式应用于粘土矿物。
多于一种的方法可用于改性粘土矿物，以使其水溶液更粘。例如，膨润土或蒙脱土与水溶性聚合物的复合材料可被烷基烷氧基硅烷处理。
根据本发明的另一方面，粘土矿物增稠剂可以是人工合成的蒙脱石、例如人工合成的皂石、人工合成的锂蒙脱石和人工合成的硅镁石。合成皂石是由Kunimine Industries Co.，Ltd.在热压釜内通过化学品的水热合成来生产的。合成皂石是雪白色粉末，且其凝胶是无色、透明的且相对于天然蒙脱石凝胶是高度粘性的。可商购的合成锂蒙脱石的实例包括由LaponiteIndustries Ltd.生产的以Laponite商标销售的B、RD和XLG产品。可商购的合成硅镁石的实例是由Mizusawa Chemical Industries Ltd.以Ionite商标生产的。这些产品是白色粉末，且在添加水时易于形成溶胶或凝胶。这样的合成蒙脱石通常具有比天然蒙脱石小的粒径，例如具有仅为天然蒙脱石的平均粒径的5％或10％的平均粒径。合成蒙脱石的这种更小的粒径可能是它们为什么可以以较少量添加就使得水性组合物具有粘性的原因。
合成的粘土矿物可被改性，以使得其水溶液更粘，尽管这通常不是必须的。例如，合成皂石、锂蒙脱石或硅镁石可被烷基烷氧基硅烷处理。
改性的或合成的矿物粘土增稠剂可例如以按重量计涂层组合物的0.1％或0.2％至高达按重量计5％或10％存在。包含0.5％至3％改性的或合成的粘土矿物增稠剂的水性涂层组合物通常是优选的。
水性涂层组合物通常需要有机聚合物粘合剂，以增强固体润滑剂对基材例如气囊织物的粘附。如果水溶性有机聚合物存在于涂层组合物中，例如，如果矿物粘土增稠剂被水溶性聚合物改性，该水溶性聚合物还可充当涂层组合物的有机聚合物粘合剂。可选择地，用于减小表面处的摩擦和/或粘连的涂层组合物还包含以水分散体存在的有机聚合物粘合剂。存在于基材表面上的涂层因此包含分散在有机聚合物粘合剂中的固体润滑剂，其可构成所有或部分水溶性有机聚合物或可以是分散在水性组合物中的有机聚合物。
优选的有机聚合物粘合剂包括聚氨酯、酚醛树脂、环氧树脂、丙烯酸树脂、丙烯酸改性的聚烯烃树脂、聚酯树脂、氨基-甲醛树脂、乙烯基树脂例如聚乙烯醇缩丁醛和聚酰胺酰亚胺树脂。优选的聚氨酯包括聚酯或聚醚型多元醇和芳族或脂族二异氰酸酯的共聚物。有机聚合物粘合剂的水平可例如为按重量计顶涂层组合物的0.2％或0.3％至高达30％的范围内。通常优选的是例如按重量计涂层组合物的5％至高达20％的有机聚合物粘合剂的水平。为了澄清目的，应理解，在提供％值时，例如组合物的总重量％总是合计达100％。
可选择地，粘合剂可以是合适的基于硅酮的乳液，其可固化成弹性产物。分散相可包括例如在水连续相中的合适的羟基化聚二有机硅氧烷和乳化剂，组合物可另外包含例如合适的二氧化硅增强填料，如胶态二氧化硅，和其他成分，如有机锡化合物。这种类型的组合物描述于US4221688中，该专利的内容通过引用包括在本文中。可选择地，粘合剂可由硅氧烷基聚合物和合适的自催化交联剂、表面活性剂和水制成。这种类型的组合物描述于例如US5994459中，该专利的内容通过引用在此公开。
根据本发明的存在于基材上以减小摩擦和/或粘连的干涂层可例如包含按重量计50％至95％的固体润滑剂、按重量计2％至15％的改性的或合成的粘土矿物增稠剂和按重量计高达45％的有机聚合物粘合剂。所提及的基于干涂布或干涂层重量的组合物中的范围意图指不包括水和/或任何其他溶剂所计算的重量。
用于减小摩擦和/或粘连的涂层组合物可含有阻燃剂。例如，气囊不支持燃烧是重要的，因此气囊通常需要添加阻燃剂，以通过适用于气囊的严格的可燃性试验。我们发现，当将本发明的顶涂层应用于硅酮涂布的气囊时，通常不存在可燃性问题，但当将不含有阻燃剂的顶涂层应用于涂布有有机树脂的气囊时，其可能不能通过可燃性试验，例如美国联邦机动车安全标准试验FMVSS#302(下文称为“FMVSS#302”)。如果阻燃剂在顶涂层中，阻燃剂可能是最有效的。优选的阻燃剂的实例是三水合铝，该三水合铝优选地未被进行表面处理。减摩涂层组合物可例如含有按重量计2％至40％、优选5％至25％的三水合铝。可选择的阻燃剂包括其他金属氢氧化物例如氢氧化镁、金属氧化物例如氧化铁和二氧化钛、碳酸盐例如碳酸锌，以及炭黑。
用于减小摩擦和/或粘连的涂层组合物可任选地含有颜料、染料、抗静电剂、表面活性剂、防腐剂、增粘剂和/或气味消除剂，如沸石或活性炭。
可通过多种技术将用于减小摩擦和/或粘连的涂层组合物应用于基材。不同基材可能需要不同的涂布方法。例如，可通过辊涂例如凹版印刷、胶印辊(offset roller)或给液辊(lick roller)，或通过幕涂，或通过喷涂，其可以是空气辅助式喷涂或无气喷涂，或通过辊式刮刀涂布法，以顶涂层的形式将涂层应用于涂布气囊或涂布气囊织物。通常优选辊涂作为在低的涂布重量下均匀涂布的有效方法。转移到织物的涂层组合物的量随辊上的压力和/或凹版印刷中蚀刻的表面深度变化。顶涂层优选以基于干重的0.5g/m2或1g/m2至高达10g/m2或15g/m2的涂布重量被应用。低至1g/m2或2g/m2的涂布重量可给予所需要的低摩擦系数并且防止粘连。
抗磨擦涂层组合物中的水性稀释剂(水加上与水混合的任何共溶剂)的量可根据所需要的涂层粘度和所需要的涂布重量来控制。通常，涂层组合物具有按重量计1.5％至50％的固体含量，并且包含98.5％至50％的水性稀释剂。
本发明的涂层组合物通常可应用于需要减小的摩擦和/或减小的粘连的任何基材。当作为顶涂层应用于气囊上或用于其他类似应用(例如在飞机上的紧急滑道和热气球)时，涂层组合物是尤其有效的，但还可用于其他应用中，例如键盘、模具制造、电线涂层、以及用于改进模制工艺的操纵中，例如硅酮模制工艺。
当将本发明的涂层组合物作为顶涂层应用于涂布气囊或涂布气囊织物时，底涂层可以是在前述专利中描述的涂层中的任何涂层。底涂层可以是有机聚硅氧烷组合物，其优选包含具有脂族不饱和烃或烃氧基取代基的有机聚硅氧烷、具有至少3个硅键合的氢原子的有机硅交联剂、能够促进脂族不饱和烃或烃氧基取代基与Si-H基团反应的催化剂和增强填料。这样的底涂层是高度柔性的且在密封气囊方面是有效的，但具有高的摩擦系数。
在气囊或气囊织物上的底涂层可选择地可以是在前述专利中描述的基于有机树脂的涂层中的任何涂层。有机树脂的一种优选类型是聚氨酯。聚氨酯底涂层可以是例如通过异氰酸酯基团与羟基或胺基的反应在织物上固化的反应性聚氨酯，或可以是热塑性聚氨酯。不论是可固化的还是热塑性的，聚氨酯通常是多元醇与多异氰酸酯的反应产物。所述多元醇可例如是聚醚二醇，如聚丁二醇(polytetramethyleneglycol diol)、聚酯-聚醚二醇、聚碳酸酯-聚醚二醇、硅酮-聚醚二醇或含侧链羟基的聚碳酸酯。多异氰酸酯可以是芳族二异氰酸酯，但优选是脂族或脂环族二异氰酸酯。有机树脂底涂层可以是如在US-A-7543843中描述的包含与丙烯酸树脂、乙烯基树脂和/或硅酮共混的聚氨酯的杂化氨基甲酸酯树脂。这种杂化氨基甲酸酯树脂需要顶涂层来抑制粘连，即在储存期间或交通工具的气囊隔室中的密填充期间涂布的表面到彼此的粘附。虽然这种有机树脂底涂层在外涂布有各种顶涂层时产生气味问题，但我们发现其可外涂布有根据本发明的防粘连涂层而无任何气味问题。
底涂层可以可选择地包括聚丙烯酸酯，例如含有侧链羟基的、可通过诸如三聚氰胺-甲醛树脂的氨基树脂固化的可固化的聚碳酸酯，或乙烯醋酸乙烯酯共聚物。底涂层可以是有机树脂的共混物，例如聚氨酯与聚丙烯酸酯或与乙烯醋酸乙烯酯共聚物的共混物。
如果底涂层是可固化的，其通常在应用防粘连涂层之前被固化，尽管在可选择的方法中，用于减小摩擦和/或粘连的涂层组合物可应用于未固化的底涂层并且底涂层组合物和用于减小摩擦和/或粘连的涂层组合物的组合可被热固化。
当将用于减小摩擦和/或粘连的涂层应用于固化的底涂层时，用于减小摩擦和/或粘连的涂层可在环境温度下固化或可在高温下更快速地固化，例如在50℃至200℃的范围内，特别是100℃至150℃的范围内。在高温下固化的一种可能的方法包括：在热固化底涂层之后立即将用于减小摩擦和/或粘连的涂层组合物应用于热的基材，例如应用于涂布气囊或气囊织物。
本发明的涂层在其所应用的基材上提供低摩擦表面。当应用于具有高摩擦系数的涂层上时，本发明的涂层减小涂布气囊表面的摩擦，且因此降低使用交通工具使气囊经历运动时的气囊的磨损；这种磨损可能导致气囊的减压保持。
本发明的涂层还抑制涂布织物表面的粘连，即在储存期间或交通工具的气囊隔室中的密填充期间涂布表面到彼此的粘附。在气囊膨胀时，这样的粘连会造成非常高的压力，导致由于撕裂产生的气囊故障或由于硅酮底涂层与织物分离产生的气囊故障。
使用本发明的涂层作为气囊顶涂层不产生任何令人不舒服的味道。我们发现当本发明的涂层应用于氨基甲酸酯聚合物底涂层(例如如在US-A-7543843中描述的包含与丙烯酸树脂、乙烯基树脂和/或硅酮共混的氨基甲酸酯聚合物的杂化氨基甲酸酯树脂)上时，未释放鱼腥味或氨气味。
通过下面的实施例阐述了本发明，其中除非另外指明，否则份和百分比指按重量计。
实施例1至4
这些实施例使用包含膨润土和聚丙烯酸钠的改性的粘土矿物增稠剂MCT1，其通过将膨润土均匀地混合到聚丙烯酸钠的水溶液中、干燥混合物然后研磨而形成。MCT1具有约15％含量的碳酸钠和聚丙烯酸钠的混合物。2％的MCT1水溶液具有20,000mpa.s的粘度，使用具有20mm直径2°锥度的Wells-Brookfield锥/板粘度计以1s-1的剪切速率在25℃下测量粘度(ASTM D4287)。
在实施例1和2中，将MCT1分散在水中，且将固体润滑剂(滑石或绿泥石)分散在所得到的分散体中。
在实施例3中，用水稀释聚氨酯乳液PU1，且将MCT1和滑石分散在稀释的乳液中。PU1是脂族-聚酯型聚氨酯自交联乳液，其具有32％的固体含量和400mpa.s的粘度，如按照上面描述测量的。
在实施例4中，用水稀释改性的聚烯烃PO1，且将MCT1和滑石分散在稀释的乳液中。PO1是用丙烯酸树脂改性的聚烯烃的乳液，且具有30％的固体含量和500mpa.s的粘度，如按照上面描述测量的。
所得到的顶涂层组合物的配方示出在表1中。
实施例5至7
这些实施例使用包含用烷基三烷氧基硅烷处理的膨润土的改性的粘土矿物增稠剂MCT2(Betonite SH：Hojun Co.，Ltd.的产品名称)。2％的MCT2水溶液具有4,300mpa.s，的粘度，如按照上面描述测量的。
在实施例5中，将MCT2分散在水中，且将绿泥石分散在所得到的分散体中。在实施例6和7中，用水稀释PU1，且将MCT1和滑石或绿泥石分散在稀释的乳液中。所得到的顶涂层组合物的配方示出在表1中。
实施例8
该实施例使用粘土矿物增稠剂人工皂石，其为日本东京KunimineIndustry以商品名Sumecton SA销售的产品。2％的Sumecton SA水溶液具有7,600mPa.s，的粘度，如按照上面描述测量的。用水稀释PU1，且将Sumecton SA分散在稀释的乳液中。所得到的顶涂层组合物的配方示出在表1中。
在实施例1至8中的每个中，将成分混合并且静止放置1天。目视观察混合物的稳定性并且注释在表1中。“NG”指观察到固体成分的分离。
通过刀涂布(1-10g/m2)将实施例1至8中的每个的涂层组合物应用于硅橡胶的表面上。目视观察涂层的均匀性。如果涂层均匀地覆盖硅橡胶，在表1中记为均匀；如果涂层未均匀地覆盖硅橡胶，在表1中记为不均匀。在180℃干燥涂层10秒。
对具有外涂层的硅橡胶进行180度弯曲。观察到外涂层的任何破裂并且在表1中列为破裂；未显示破裂的外涂层记为良好。
估计了外涂层的减磨性质，通过经验用手指对其触感来评价。“粘性”指与无外涂层时的硅橡胶表面相同的触感。在用手指擦洗外涂层的表面10次后，且在用棉布擦洗外涂层的表面10次后，进行了相同的评价。
还对实施例9和10的顶涂层组合物进行了耐刮擦测试。用指甲刮涂布织物。如果未观察到引起刮痕，则将涂层记为良好，且如果观察到涂层从织物挪动或除去，则记为NG。
比较实施例C1至C8
按照在实施例1至8中使用的程序，制备了含有在实施例1至8中的涂层组合物中使用的一些成分的涂层组合物。配方示出在表2中。在比较实施例C6和C7中使用的2％的膨润土水溶液具有1mPa.s的粘度，如按照上面描述测量的。
以与实施例1至8的涂层组合物相同的方式，对比较实施例C1至C8的涂层组合物进行了测试。结果示出在表2中。
表1请添加刮擦试验：实施例1-8：良好
Figure BDA00001828796500111
表2：请添加刮擦试验：C3、C4和C6：NG
Figure BDA00001828796500121
实施例9和10
按照实施例1的程序，用表3中列出的成分制备顶涂层组合物。这些组合物含有阻燃剂。FR1是未处理的平均粒径1μm的氢氧化铝细粉。FR2是硅烷表面处理的平均粒径1μm的氢氧化铝细粉。
按照上面描述的，对实施例9和10的顶涂层组合物进行了测试，不同之处是代替硅橡胶，通过凹版辊涂将涂层组合物应用于编织尼龙气囊织物的涂布表面，该编织尼龙气囊织物具有由Spartanburg，SC的Milliken &Co.以商标Patina销售并且认为包含杂化氨基甲酸酯树脂的涂层，该杂化氨基甲酸酯包含与乙烯醋酸乙烯酯共聚物共混且固化的氨基甲酸酯聚合物。以10g/m2应用顶涂层并且在140℃下热固化。
除了上面描述的测试外，还对实施例9和10的顶涂层组合物进行了粘连测试。将涂布气囊织物重叠，以使涂布表面面向彼此，并且评价这些涂布织物表面是平滑滑动的或不是平滑滑动的。如果观察到平滑滑动，则将涂层记为良好的，如果表面未平滑滑动或被刮擦，则记为NG。
根据美国联邦机动车安全标准试验FMVSS#302在燃烧试验中对实施例9和10的顶涂层组合物进行了可燃性测试，在燃烧试验中，将火焰应用于织物的边缘并且测量燃烧距离和燃烧时间。对于通过FMVSS#302标准的要求是100mm/min或更低的燃烧速率。
所有上面的试验结果示出在表3中。
在比较实施例C9中，使用硅烷表面处理的氢氧化铝细粉FR2，而无固体润滑剂。以与实施例9和10的涂层相同的方式对比较实施例C9的涂层组合物进行了测试，并且结果示出在表3中。
表3
Figure BDA00001828796500131
实施例11、12和13
实施例11、12和13描述于表4中。以与前述实施例相同的方式制备这些实施例，并且通过刀涂布应用涂层，但并入乳液形式的合适的基于硅酮的粘合剂，其固化成弹性产物(下文称为“硅酮乳胶”)。在实施例11、12和13中使用的硅酮乳胶添加剂是水包油型硅酮基乳液，其具有210nm的平均粒径和约55重量％的非挥发性组分。在实施例11、12和13中使用的硅酮乳胶包含以下成分：
37.0重量％的羟基化聚二甲基硅氧烷，其具有25℃时2,400mPa·s的粘度；
3.0重量％的含二乙基氨氧基的聚二甲基硅氧烷；
重量％的甲基三乙氧基硅烷；
4.0重量％的乳化剂；
21.3重量％的水；
33.重量％的胶态二氧化硅(有效组分＝30重量％)；以及
0.7重量％的作为pH调节剂的二乙胺。
表4
按照上面的描述进行所有测试，且将从表4中看出，所有三个实施例11、12和13均产生良好的结果。
实施例14、15和16
在实施例14、15和16中测试的组合物分别与实施例11、12和13中的相同。然而，同实施例9和10，通过凹版辊涂将它们应用于涂布有硅橡胶涂层的编织尼龙气囊织物的预涂布表面。在140℃下热固化顶涂层。分析固化的顶涂层，并且将结果示出在下表5中。
使用硅酮乳胶代替聚氨酯(PU)顶涂层的一个优点是在涂布测试后仅需要用水湿布清洗凹版辊。当使用PU粘合剂时，使用溶剂来清洗辊。
表5
Figure BDA00001828796500151
在用布擦洗后除去滑石的情况下，用布擦洗顶涂层的表面，并且通过目视观测布擦拭的表面来评价滑石的除去。

Claims (25)

1.一种用于减小表面处的摩擦和/或粘连的水性涂层组合物，所述组合物包含固体润滑剂和改性的或合成的粘土矿物，所述改性的或合成的粘土矿物具有增稠性质，使得2％按重量计的所述改性的或合成的粘土矿物增稠剂的水分散体具有至少1000mPa.s的粘度。
2.根据权利要求1所述的水性涂层组合物，其中所述固体润滑剂是页硅酸盐。
3.根据权利要求2所述的水性涂层组合物，其中所述固体润滑剂选自云母、滑石、高岭土、绢云母和绿泥石。
4.根据权利要求1至3中任一项所述的水性涂层组合物，其中所述固体润滑剂以按重量计总的水性涂层组合物的3％至40％存在。
5.根据权利要求1至4中任一项所述的水性涂层组合物，其中所述粘土矿物增稠剂是皂石、膨润土或蒙脱土。
6.根据权利要求5所述的水性涂层组合物，其中所述粘土矿物增稠剂被水溶性有机聚合物改性。
7.根据权利要求6所述的水性涂层组合物，其中所述水溶性有机聚合物含有羧酸盐基团。
8.根据权利要求7所述的水性涂层组合物，其中所述水溶性有机聚合物是聚丙烯酸钠或聚甲基丙烯酸钠。
9.根据权利要求7或权利要求8所述的水性涂层组合物，其中所述水溶性有机聚合物以按重量计基于所述粘土矿物增稠剂的0.1％至40％存在。
10.根据权利要求1至5中任一项所述的水性涂层组合物，其中所述粘土矿物增稠剂通过用烷基烷氧基硅烷处理而被改性。
11.根据权利要求1至5中任一项所述的水性涂层组合物，其中所述粘土矿物增稠剂是人工合成的皂石。
12.根据权利要求1至11中任一项所述的水性涂层组合物，其中所述改性的或合成的粘土矿物增稠剂以按重量计所述涂层组合物的0.2％至5％存在。
13.根据权利要求1至12中任一项所述的水性涂层组合物，其中所述涂层组合物还包含以水分散体存在的有机聚合物粘合剂或呈基于硅酮的水性乳液的形式的硅酮粘合剂。
14.根据权利要求13所述的水性涂层组合物，其中所述有机聚合物粘合剂包含以水性乳液存在的聚氨酯或丙烯酸改性的聚烯烃。
15.根据权利要求1至14中任一项所述的水性涂层组合物，其中所述涂层组合物还包含阻燃剂。
16.根据权利要求15所述的水性涂层组合物，其中所述阻燃剂是三水合铝。
17.一种制备用于减小表面处的摩擦和/或粘连的水性涂层组合物的方法，包括混合水、固体润滑剂和改性的或合成的粘土矿物增稠剂，所述改性的或合成的粘土矿物增稠剂具有增稠性质，使得2％按重量计的所述改性的或合成的粘土矿物增稠剂的水分散体具有至少1000mPa.s的粘度。
18.根据权利要求17所述的方法，其中将水溶性有机聚合物与所述粘土矿物预混合，以形成改性的粘土矿物增稠剂。
19.根据权利要求18所述的方法，其中在水中预混合所述粘土矿物和水溶性有机聚合物然后干燥。
20.包含以下物质的水性涂层组合物作为基材上的顶涂层以减小摩擦和/或粘连的用途：固体润滑剂和改性的或合成的粘土矿物，所述改性的或合成的粘土矿物具有增稠性质，使得2％按重量计的所述改性的或合成的粘土矿物增稠剂的水分散体具有至少1000mPa.s的粘度。
21.根据权利要求20所述的用途，其中所述基材是气囊或随后形成气囊的涂布织物。
22.一种气囊，其涂布有包含以下物质的防粘连涂层：固体润滑剂和改性的或合成的粘土矿物，所述改性的或合成的粘土矿物具有增稠性质，使得2％按重量计的所述改性的粘土矿物增稠剂的水分散体具有至少1000mPa.s的粘度。
23.一种涂布基材以减小摩擦和/或粘连的方法，其中所述基材涂布有包含以下物质的水性涂层组合物：固体润滑剂和改性的或合成的粘土矿物，所述改性的或合成的粘土矿物具有增稠性质，使得2％按重量计的所述改性的粘土矿物增稠剂的水分散体具有至少1000mPa.s的粘度。
24.根据权利要求23所述的方法，其中涂布有有机树脂的织物在顶面被涂布有所述水性涂层组合物。
25.根据权利要求13所述的水性涂层组合物，其特征在于，所述硅酮粘合剂具有包含羟基化聚二有机硅氧烷和乳化剂的分散相和水连续相，以及任选的二氧化硅增强填料。
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