CN116867844A - 包含聚合物共混物的不可透气膜及其制备方法 - Google Patents
包含聚合物共混物的不可透气膜及其制备方法 Download PDFInfo
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- CN116867844A CN116867844A CN202280015309.0A CN202280015309A CN116867844A CN 116867844 A CN116867844 A CN 116867844A CN 202280015309 A CN202280015309 A CN 202280015309A CN 116867844 A CN116867844 A CN 116867844A
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- China
- Prior art keywords
- film
- anhydride
- weight
- olefin interpolymer
- carboxylic acid
- Prior art date
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- Pending
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- 238000000034 method Methods 0.000 title claims abstract description 28
- 229920002959 polymer blend Polymers 0.000 title abstract description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000005977 Ethylene Substances 0.000 claims abstract description 49
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 46
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 37
- 239000004711 α-olefin Substances 0.000 claims abstract description 37
- 239000011256 inorganic filler Substances 0.000 claims abstract description 34
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 34
- 229920000092 linear low density polyethylene Polymers 0.000 claims abstract description 28
- 239000004707 linear low-density polyethylene Substances 0.000 claims abstract description 27
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 32
- 238000002844 melting Methods 0.000 claims description 17
- 230000008018 melting Effects 0.000 claims description 17
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 16
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 16
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- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000292 calcium oxide Substances 0.000 claims description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 8
- QXJJQWWVWRCVQT-UHFFFAOYSA-K calcium;sodium;phosphate Chemical compound [Na+].[Ca+2].[O-]P([O-])([O-])=O QXJJQWWVWRCVQT-UHFFFAOYSA-K 0.000 claims description 8
- 239000004927 clay Substances 0.000 claims description 8
- 229910052570 clay Inorganic materials 0.000 claims description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 8
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 8
- 239000001095 magnesium carbonate Substances 0.000 claims description 8
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 8
- 239000000395 magnesium oxide Substances 0.000 claims description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 8
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 8
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 8
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 8
- 239000010445 mica Substances 0.000 claims description 8
- 229910052618 mica group Inorganic materials 0.000 claims description 8
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- 239000000377 silicon dioxide Substances 0.000 claims description 8
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- 239000010457 zeolite Substances 0.000 claims description 8
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- 229920003314 Elvaloy® Polymers 0.000 description 1
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- 229920001400 block copolymer Polymers 0.000 description 1
- XXHCQZDUJDEPSX-KNCHESJLSA-L calcium;(1s,2r)-cyclohexane-1,2-dicarboxylate Chemical compound [Ca+2].[O-]C(=O)[C@H]1CCCC[C@H]1C([O-])=O XXHCQZDUJDEPSX-KNCHESJLSA-L 0.000 description 1
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- 239000002667 nucleating agent Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
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- Manufacture Of Macromolecular Shaped Articles (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
本发明提供了包含特定聚合物共混物的不可透气膜以及用于制备此类膜的方法。该膜包含酸酐和/或羧酸官能化的乙烯/α‑烯烃互聚物、线性低密度聚乙烯和无机填料。制造膜的方法包括挤出酸酐和/或羧酸官能化的乙烯/α‑烯烃互聚物、线性低密度聚乙烯和无机填料以形成膜并拉伸该膜。根据本文公开的实施方案的膜可表现出低WVTR值和改善的模量,同时还掺入大量低规格的无机填料。
Description
技术领域
本公开的实施方案整体涉及膜,并且更具体地涉及包含特定聚合物共混物的不可透气膜。
背景技术
不可透气膜用于广泛多种应用中,包括婴儿尿布、成人失禁产品、手术服以及其它卫生和医疗应用。例如,尿布底片膜可根据膜的微孔形态或水蒸气传输速率(“WVTR”)分类为可透气或不可透气膜。可透气膜通常通过将大量(大于30重量%)无机填料(例如,CaCO3)掺入聚合物中以产生孔、递送透气性并降低成本来制备。尽管不可透气膜可包含填料诸如CaCO3以降低成本,但它们不包含大量(大于30重量%)的填料,因为填料诸如CaCO3可产生孔、递送透气性并损害机械性质。作为替代,不可透气膜通常由高密度聚乙烯(HDPE)、线性低密度聚乙烯(LLDPE)和低密度聚乙烯(LDPE)的共混物形成,其中,概括地讲,HDPE提供刚度,LLDPE提供韧性,并且LDPE提供可加工性。
因此,仍然需要包含无机填料并且表现出改善的或保持的机械性质诸如模量和拉伸性质的节省成本的、不可透气的膜制剂。
发明内容
本公开的实施方案通过提供可具有较高量(40重量%至70重量%)的无机填料和低WVTR(小于1,100g/m2*天)的膜满足前述需要。本发明的膜包含酸酐和/或羧酸官能化的乙烯/α-烯烃互聚物和线性低密度聚乙烯。不受任何理论束缚,酸酐和/或羧酸官能化的乙烯/α-烯烃互聚物与线性低密度聚乙烯和无机填料的组合防止空化并且因此降低或去除透气性,同时保持或改善机械性质。根据本文公开的实施方案的膜可表现出低WVTR值和改善的模量,同时还掺入大量低规格的无机填料。
本文公开了一种膜。膜包含(a)1重量%至15重量%的酸酐和/或羧酸官能化的乙烯/α-烯烃互聚物,其具有小于100℃的熔点;(b)20重量%至59重量%的线性低密度聚乙烯,其具有0.900g/cm3至0.940g/cm3的密度和0.1g/10min至10.0g/10min的熔体指数(I2);以及(c)40重量%至70重量%的无机填料,所述无机填料选自由以下组成的组:碳酸钠、碳酸钙、碳酸镁、硫酸钡、硫酸镁、硫酸铝、氧化镁、氧化钙、氧化铝、云母、滑石、二氧化硅、粘土、玻璃球、二氧化钛、氢氧化铝、沸石、以及它们的组合;并且其中重量%是基于所述膜的总重量计的;并且其中膜具有小于1,100g/m2*天的水蒸气传输速率(WVTR)和至少2:1的拉伸比。
本文还公开了一种用于制造膜的方法。该方法包括提供1重量%至15重量%的酸酐和/或羧酸官能化的乙烯/α-烯烃互聚物,其具有小于100℃的熔点;20重量%至59重量%的线性低密度聚乙烯,其具有0.900g/cm3至0.940g/cm3的密度和0.1g/10min至10.0g/10min的熔体指数(I2);以及40重量%至70重量%的无机填料,所述无机填料选自由以下组成的组:碳酸钠、碳酸钙、碳酸镁、硫酸钡、硫酸镁、硫酸铝、氧化镁、氧化钙、氧化铝、云母、滑石、二氧化硅、粘土、玻璃球、二氧化钛、氢氧化铝、沸石、以及它们的组合;其中重量%是基于所述膜的总重量计的;挤出所述酸酐和/或羧酸官能化的乙烯/α-烯烃互聚物、线性低密度聚乙烯和无机填料以形成所述膜;以及将所述膜拉伸至至少2:1的拉伸比。
在具体实施方式中更详细地描述了这些和其他实施方案。
具体实施方式
下文更详细地描述了所公开的膜的各方面。膜可以具有广泛多种应用,包括例如婴儿尿布、成人失禁产品、手术服以及其它卫生和医疗应用。然而,本公开可以以不同形式实施并且不应被解释为限制于本公开中所阐述的实施方案。相反地,提供这些实施方案以使得本公开将透彻且完整,且将向本领域的技术人员充分传达主题的范围。
如本文所用,术语“聚合物”意指通过使相同或不同类型的单体聚合而制备的聚合化合物。因此通用术语聚合物涵盖术语均聚物(用于指仅由一种类型的单体制备的聚合物)和术语共聚物或互聚物。痕量杂质(例如,催化剂残余物)可以掺入到聚合物中和/或聚合物内。聚合物可以是单一聚合物、聚合物共混物或聚合物混合物,包含在聚合期间原位形成的聚合物的混合物。
如本文所用,术语“聚乙烯”是指包含大部分量(>50mol%)的衍生自乙烯单体的单元的聚合物。
如本文所用,术语“互聚物”是指通过使至少两种不同类型的单体聚合而制备的聚合物。
如本文所用,术语“乙烯/α-烯烃互聚物”是指包含呈聚合形式的大量乙烯单体(基于互聚物的重量计)和至少一种α-烯烃单体的互聚物。
如本文所用,术语“酸酐和/或羧酸官能化的乙烯/α-烯烃互聚物”是指包含通过共价键连接的至少一个酸酐基团和/或至少一个酸基团(例如,通过酸酐的水解形成的-COOH)的乙烯/α-烯烃互聚物。酸酐和/或羧酸官能化的乙烯/α-烯烃互聚物的示例是马来酸酐官能化的乙烯/α-烯烃互聚物。
术语“包含(comprising)”、“包括(including)”、“具有(having)”和其衍生词并不旨在排除任何额外组分、步骤或程序的存在,无论是否具体地公开了所述组分、步骤或程序。为了避免任何疑问,除非相反地说明,否则通过使用术语“包含”所要求保护的所有组合物可以包括任何额外的添加剂、佐剂或化合物,无论是聚合的还是其他方式的。相比之下,术语“基本上由…组成”从任何随后列举的范围中排除任何其他组分、步骤或程序,除对可操作性来说并非必不可少的那些组分、步骤或程序之外。术语“由……组成”排除未具体叙述或列出的任何成分、步骤或程序。
本文公开的膜包含酸酐和/或羧酸官能化的乙烯/α-烯烃互聚物、线性低密度聚乙烯和无机填料。
在实施方案中,膜包含1重量百分比至15重量百分比(“重量%”)的酸酐和/或羧酸官能化的乙烯/α-烯烃互聚物,其中重量%是基于膜的总重量计的。本文公开并包括1重量%至15重量%的所有单独值和子范围。例如,膜可包含1重量%至15重量%、5重量%至15重量%、或8重量%至12重量%的酸酐和/或羧酸官能化的乙烯/α-烯烃互聚物,其中重量%是基于膜的总重量计的。
在实施方案中,酸酐和/或羧酸官能化的乙烯/α-烯烃互聚物具有小于100℃的熔点,其中熔点可根据ISO 3146测量。本文公开并包括小于100℃的所有单独值和子范围。例如,酸酐和/或羧酸官能化的乙烯/α-烯烃互聚物可具有小于100℃、小于95℃、小于90℃、小于85℃、小于80℃、小于75℃、小于70℃或小于65℃的熔点;或可具有在55℃至95℃、55℃至85℃、55℃至75℃、55℃至65℃、60℃至90℃、60℃至80℃、或60℃至70℃范围内的熔点,其中熔点可根据ISO 3146测量。
在实施方案中,酸酐和/或羧酸官能化的乙烯/α-烯烃互聚物具有小于0.910克/立方厘米(g/cm3或g/cc)的密度。本文公开并包括小于0.910g/cc的所有单独值和子范围。例如,酸酐和/或羧酸官能化的乙烯/α-烯烃互聚物可具有小于0.910g/cc、小于0.900g/cc、小于0.890g/cc、小于0.880g/cc、或小于0.870g/cc的密度;或可具有在0.860g/cc至0.910g/cc、0.860g/cc至0.900g/cc、0.860g/cc至0.890g/cc、0.860g/cc至0.880g/cc、或0.865g/cc至0.875g/cc范围内的密度。
在实施方案中,酸酐和/或羧酸官能化的乙烯/α-烯烃互聚物的酸酐或酸含量为0.1重量%至2.0重量%,其中酸酐或酸含量的重量%是基于酸酐和/或羧酸官能化的乙烯/α-烯烃互聚物的总重量计的。本文公开并包括0.1重量%至2.0重量%的所有单独值和子范围。例如,酸酐和/或羧酸官能化的乙烯/α-烯烃互聚物可以具有0.1重量%至2.0重量%、0.3重量%至2.0重量%、0.5重量%至2.0重量%、0.7重量%至2.0重量%、或1.0重量%至2.0重量%的酸酐或酸含量,其中酸酐或酸含量的重量%是基于酸酐和/或羧酸官能化的乙烯/α-烯烃互聚物的总重量计的。
在实施方案中,酸酐和/或羧酸官能团接枝到乙烯/α-烯烃互聚物上。
在实施方案中,酸酐和/或羧酸官能化的乙烯/α-烯烃互聚物是马来酸酐官能化的乙烯/α-烯烃互聚物。例如,在实施方案中,膜包含1重量%至15重量%的具有小于100℃的熔点的马来酸酐官能化的乙烯/α-烯烃互聚物,其中重量%是基于膜的总重量计的。
适用于本发明实施方案中的酸酐和/或羧酸官能化的乙烯/α-烯烃互聚物的示例包括商品名为BYNELTM的某些酸酐和/或羧酸官能化的乙烯/α-烯烃互聚物,包括例如BYNELTM 46E1060,其可从密歇根州米德兰的陶氏化学公司(The Dow Chemical Company,Midland,MI)商购获得。
本文公开的膜包含线性低密度聚乙烯。在实施方案中,膜包含20重量%至59重量%的线性低密度聚乙烯,其中重量%是基于膜的总重量计的。本文公开并包括20重量%至59重量%的所有单独值和子范围。例如,膜可包含20重量%至59重量%、20重量%至50重量%、20重量%至45重量%、30重量%至59重量%、30重量%至50重量%、30重量%至45重量%、35重量%至59重量%、35重量%至50重量%、或35重量%至45重量%的线性低密度聚乙烯,其中重量%是基于膜的总重量计的。
在实施方案中,线性低密度聚乙烯具有0.900g/cm3至0.940g/cm3的密度。本文公开并包括0.900g/cm3至0.940g/cm3的所有单独值和子范围。例如,线性低密度聚乙烯可以具有0.900g/cm3至0.940g/cm3、0.905g/cm3至0.935g/cm3、0.910g/cm3至0.930g/cm3、或0.915g/cm3至0.925g/cm3的密度,其中密度可根据ASTM D792测量。
在实施方案中,线性低密度聚乙烯具有0.1g/10min至10.0g/10min的熔体指数(I2)。本文公开并包括0.1g/10min至10.0g/10min的所有单独值和子范围。例如,线性低密度聚乙烯可具有0.1g/10min至10.0g/10min、0.5g/10min至10.0g/10min、1.0g/10min至10.0g/10min、0.1g/10min至5.0g/10min、0.5g/10min至5.0g/10min、或1.0g/10min至5.0g/10min的熔体指数(I2),其中熔体指数(I2)可根据ASTM D1238测量。
适用于本发明实施方案中的线性低密度聚乙烯的示例包括商品名为DOWLEXTM的某些线性低密度聚乙烯,包括例如可从密歇根州米德兰的陶氏化学公司(The Dow ChemicalCompany,Midland,MI)商购获得的DOWLEXTM 2111GC聚乙烯树脂。
本文所公开的膜还包含无机填料。无机填料选自由以下组成的组:碳酸钠、碳酸钙、碳酸镁、硫酸钡、硫酸镁、硫酸铝、氧化镁、氧化钙、氧化铝、云母、滑石、二氧化硅、粘土、玻璃球、二氧化钛、氢氧化铝、沸石、以及它们的组合。在实施方案中,膜包含40重量%至70重量%的有机填料,该有机填料选自由以下组成的组:碳酸钠、碳酸钙、碳酸镁、硫酸钡、硫酸镁、硫酸铝、氧化镁、氧化钙、氧化铝、云母、滑石、二氧化硅、粘土、玻璃球、二氧化钛、氢氧化铝、沸石、以及它们的组合。本文公开并包括40重量%至70重量%的所有单独值和子范围。例如,组合物可包含40重量%至70重量%、40重量%至60重量%、40重量%至55重量%、45重量%至70重量%、45重量%至60重量%、或45重量%至55重量%的无机填料,其中重量%是基于膜的总重量计的。
在实施方案中,无机填料具有小于5微米(也称为微米(μm))的中值粒度(D50)。本文公开并包括小于5微米的所有个别值和子范围。例如,无机填料可以具有小于4微米、小于3微米、小于2微米、或小于1微米的中值粒度(D50),或可以在0.1微米至4微米、0.1微米至3微米、0.1微米至2微米、或0.1微米至1微米的范围内。
在实施方案中,膜的无机填料是碳酸钙。
本文所公开的膜可掺入添加剂,诸如抗氧化剂(例如,受阻酚,诸如1010或/>1076,由巴斯夫(BASF)供应)、亚磷酸盐(例如,/>168,也由巴斯夫供应)、加工助剂、紫外光稳定剂、热稳定剂、颜料、着色剂、抗静电添加剂、阻燃剂、增滑剂、抗粘连添加剂、生物杀灭剂、抗微生物剂和澄清剂/成核剂(例如,HYPERFORMTMHPN-20E、MILLADTM 3988、MILLADTM NX 8000,可从美利肯化学公司(Milliken Chemical)获得)。添加剂可以以本领域中通常使用的水平包括在膜中,以实现它们所需的目的。在一些示例中,一种或多种添加剂的含量范围是基于膜的总重量计0重量%至10重量%、基于膜的总重量计0重量%至5重量%、基于膜的总重量计0.001重量%至5重量%、基于膜的总重量计0.001重量%至3重量%、基于膜的总重量计0.05重量%至3重量%、或基于膜的总重量计0.05重量%至2重量%。
本文所公开的膜是不可透气的膜。如本文所用,术语“不可透气的”是指具有小于1,100g/m2*天的水蒸气传输速率(WVTR)的膜。本发明的膜可允许较高量的无机填料(40重量%至70重量%的无机填料),同时保持较低的WVTR值(小于1,100g/m2*天)。该结果是出乎意料的,因为较高含量的填料通常导致膜中更大的空化和更高的WVTR值。不受任何理论束缚,酸酐和/或羧酸官能化的乙烯/α-烯烃互聚物与线性低密度聚乙烯和无机填料的组合防止空化并且因此降低WVTR同时保持或改善机械性质。据信,酸酐和/或羧酸官能化的乙烯/α-烯烃互聚物可与无机填料和线性低密度聚乙烯相互作用以防止空化并降低孔形成和WVTR。
本文所公开的膜具有小于1,100g/m2*天的水蒸气传输速率(WVTR)。本文公开并并入小于1,100g/m2*天的所有单独值和子范围。例如,膜可具有小于1,100g/m2*天、小于1,000g/m2*天、小于900g/m2*天、小于800g/m2*天、小于700g/m2*天、小于600g/m2*天、或小于500g/m2*天的WVTR;或膜可具有在400至1,100g/m2*天、400至1,000g/m2*天、400至800g/m2*天、400至600g/m2*天、500至1,100g/m2*天、或500至800g/m2*天范围内的WVTR,其中WVTR可根据ASTM E398测量。
膜的基重不受特别限制,但在一些实施方案中,可以是5gsm至50gsm。膜的基重可以取决于多种因素,包括膜的期望特性、膜的最终用途应用、可用于制造膜的设备、应用所允许的成本以及其它因素。本文包括并公开了5gsm至50gsm的所有单独值和子范围。例如,在一些实施方案中,膜具有5gsm至50gsm、5gsm至40gsm、5gsm至30gsm、5gsm至20gsm、10gsm至50gsm、10gsm至40gsm、10gsm至30gsm、或10gsm至20gsm的基重。
本文所公开的膜具有至少2:1的拉伸比。尽管拉伸膜可提高WVTR,但拉伸可提高或改善膜的机械性质诸如模量和拉伸性质,并可允许降低膜的规格。根据本文所公开的实施方案的本发明的膜允许较高含量的无机填料,同时将WVTR保持在低水平(小于1,100g/m2*天),并且同时保持或改善机械性质诸如模量或拉伸性质。在实施方案中,膜具有至少2:1、至少3:1、至少4:1、或至少5:1的拉伸比,或具有在2:1至6:1、或可选地3:1至6:1范围内的拉伸比。
除了具有小于1,100g/m2*天的WVTR和至少2:1的拉伸比之外,根据本文公开的实施方案的膜在纵向上在5%应变下的力可大于2.000N/15mm膜宽度(或可选地大于2.500N/15mm膜宽度,或大于3.000N/15mm膜宽度,或大于3.500N/15mm膜宽度,或大于4.000N/15mm膜宽度),其中在纵向上在5%应变下的力可根据下述测试方法测量。
根据本文所公开的实施方案的膜可根据其在纵向(MD)上在5%应变下的力、拉伸比、无机填料的重量%和WVTR来定义。例如,以下等式可用于表征该膜:
在实施方案中,膜具有XNBB,其大于或等于0.0060,或者大于或等于0.0080,或者大于或等于0.0100,其中XNBB如上述等式中所指出的那样定义。
还预期了根据本文公开的实施方案的膜可包含共挤出的或作为层合体的附加层。这些层可经过选择以提供另外的功能性,例如提供额外强度、对另一基材(诸如非织造物)的粘附性、和/或美观特性(诸如感觉或外观)的层。
本发明的一些实施方案涉及包含本发明的一个或多个膜的层合体。例如,本发明的膜可以用于膜/非织造物层合体中。用于此类层合体的典型的非织造物可以是纺丝纤网、气流纤网、梳理纤网、或它们的复合材料。用于具有本发明的膜的层合体的典型非织造复合材料包括三束纺粘材料(例如,S/S/S)、纺粘/熔喷/纺粘复合材料(例如,S/M/S)等。用于将膜接合至非织造物的常用方法包括,例如,粘结的热熔融粘合剂层合、超声粘结以及通过压延机或压料辊实现的热粘结。在实施方案中,包含本发明的膜的层合体与非织造物或第二膜粘附接触。
本发明还涉及包括至少一个本文公开的本发明膜的制品。包括本发明膜的制品可以作为液体不可透过的层用于一次性卫生和医用产品中。包括此类膜的制品的示例包括尿布、训练裤、女性卫生产品、成人失禁产品、医用盖布、医用罩衣、手术衣等。可以基于本文的教导,使用本领域技术人员已知的技术将膜掺入到此类制品中。
本文所述的膜可通过多种工艺制备。示例性工艺可包括将膜制成吹塑膜或流延膜,并且膜可通过吹塑、流延或挤出涂布工艺来制造。膜可以通过纵向拉伸、横向拉伸、环轧拉伸、冷拉、或它们的组合进行拉伸。
本文还公开了制造本发明的膜的方法。在实施方案中,用于制造膜的方法包括提供1重量%至15重量%的酸酐和/或羧酸官能化的乙烯/α-烯烃互聚物,该互聚物具有小于100℃的熔点;20重量%至59重量%的线性低密度聚乙烯,其具有0.900g/cm3至0.940g/cm3的密度和0.1g/10min至10.0g/10min的熔体指数(I2);以及40重量%至70重量%的无机填料,所述无机填料选自由以下组成的组:碳酸钠、碳酸钙、碳酸镁、硫酸钡、硫酸镁、硫酸铝、氧化镁、氧化钙、氧化铝、云母、滑石、二氧化硅、粘土、玻璃球、二氧化钛、氢氧化铝、沸石、以及它们的组合;其中重量%是基于所述膜的总重量计的;挤出所述酸酐和/或羧酸官能化的乙烯/α-烯烃互聚物、线性低密度聚乙烯和无机填料以形成所述膜;以及将所述膜拉伸至至少2:1的拉伸比。
在实施方案中,制造膜的方法包括以下步骤:在将材料挤出成膜之前配混酸酐和/或羧酸官能化的乙烯/α-烯烃互聚物、线性低密度聚乙烯和无机填料。例如,在实施方案中,用于制造膜的方法包括提供1重量%至15重量%的酸酐和/或羧酸官能化的乙烯/α-烯烃互聚物,该互聚物具有小于100℃的熔点;20重量%至59重量%的线性低密度聚乙烯,其具有0.900g/cm3至0.940g/cm3的密度和0.1g/10min至10.0g/10min的熔体指数(I2);以及40重量%至70重量%的无机填料,所述无机填料选自由以下组成的组:碳酸钠、碳酸钙、碳酸镁、硫酸钡、硫酸镁、硫酸铝、氧化镁、氧化钙、氧化铝、云母、滑石、二氧化硅、粘土、玻璃球、二氧化钛、氢氧化铝、沸石、以及它们的组合;其中重量%是基于所述膜的总重量计的;配混酸酐和/或羧酸官能化的乙烯/α-烯烃互聚物、线性低密度聚乙烯和无机填料以形成母料制剂;挤出母料制剂以形成膜;以及将所述膜拉伸至至少2:1的拉伸比。
测试方法
密度
密度根据ASTM D792测量,并以克/cm3(g/cc或g/cm3)表示。
熔体指数(I2)
熔体指数(I2)根据ASTM D-1238在190℃下于2.16kg下测量。数值以g/10min报告,其与每10min洗脱的克数相对应。
熔点
根据ISO 3146测量熔点。
水蒸气透过率(WVTR)
水蒸气透过率(WVTR)根据ASTM E398进行测量。
在MD上在5%应变下的力或绝对拉伸
根据ISO 527-3测量在纵向上在5%应变下的力(也称为绝对拉伸)。记录在5%伸长率下的应力。样品的宽度为15mm,其长度为100mm,记录的值为N/15mm膜宽度。
实施例
以下实施例示出本公开的特征,但并不意图限制本公开的范围。
使用的材料
以下材料包括在下文讨论的示例性膜中。
DOWLEXTM 2107GC,其是一种乙烯-辛烯共聚物,密度为0.917g/cm3并且熔体指数(I2)为2.3g/10min,可从密歇根州米德兰的陶氏化学公司(The Dow Chemical Company,Midland,MI)商购获得。
DOWLEXTM 2111GC,其是一种线性低密度聚乙烯,密度为0.920g/cm3并且熔体指数(I2)为3.7g/10min,可从密歇根州米德兰的陶氏化学公司(The Dow Chemical Company,Midland,MI)商购获得。
BYNELTM 46E1060,其是一种马来酸酐官能化的乙烯/α-烯烃互聚物,具有62.8℃的熔点、0.87g/cm3的密度、3g/10min的熔体指数(I2)和1.0重量%至2.0重量%的马来酸酐含量,可从密歇根州米德兰的陶氏化学公司(The Dow Chemical Company,Midland,MI)商购获得。
ELVALOYTM AC 1820,其是一种乙烯/丙烯酸甲酯共聚物,熔点为92℃,密度为0.942g/cm3,熔体指数(I2)为8g/10min,并且丙烯酸酯含量为20重量%,可从密歇根州米德兰的陶氏化学公司(The Dow Chemical Company,Midland,MI)商购获得。
INFUSETM9507,其是一种烯烃嵌段共聚物,密度为0.866g/cm3,熔体指数(I2)为5.0g/10min,可从密歇根州米德兰的陶氏化学公司(The Dow Chemical Company,Midland,MI)商购获得。
OmyaFilm 753,可从Omya AG商购获得的碳酸钙(CaCO3)。
根据以下配方和程序形成最终基重为15gsm的膜。膜的配方与下表1中的描述一致,并命名为比较例1-5和本发明实施例1。
表1-配方
为了形成膜,将比较例2-5和本发明实施例1各自的材料在Buss捏合机配混线上挤出成母料制剂。比较例1没有形成母料制剂,因为它是单一聚合物制剂。然后在Collin流延挤出线上将制剂加工成单层膜。膜的最终膜基重为15gsm。下表2提供了膜加工参数。
表2–膜处理参数
Amps-挤出C(A) | 2.4 |
模头间隙(mm) | 0.8 |
层百分比-挤出A(%) | 0 |
层百分比-挤出C(%) | 100 |
层百分比-挤出E(%) | 0 |
熔体压力-挤出C(bar) | 96 |
熔体温度-挤出C(℃) | 231 |
RPM-挤出C(rpm) | 29 |
结构 | C |
取出速度(m/min) | 7.7 |
总输出(kg/h) | 3.8 |
由每个实施例配方以不同的拉伸比生产膜组。比较例1A、2A和本发明实施例1A是拉伸比为“0”(即,根本没有拉伸)的膜。将比较例2B、3B、4B和本发明实施例1B在纵向上拉伸至最小拉伸比(MSR),该最小拉伸比是各膜固有的。如本领域技术人员已知的,膜具有MSR,其中膜在其整个宽度上被完全拉伸并且没有虎纹。比较例2B的MSR为3.7:1;比较例3B的MSR为3.9:1;比较例4B的MSR为3.7:1;本发明实施例1B的MSR为4.2:1。将比较例2C、3C、4C和本发明实施例1C在纵向上拉伸至5.5:1的拉伸比。
根据下表3中的纵向取向加工参数进行纵向拉伸。
表3:纵向定向加工参数
测量每个实施例膜的WVTR。下表4提供了结果。
表4-WVTR结果
实施例 | 拉伸比 | WVTR(g/(m2*天)) |
比较例1A | 0 | 36 |
比较例2A | 0 | 36 |
比较例2B | 3.7(MSR) | 3392 |
比较例2C | 5.5 | 3853 |
比较例3B | 3.9(MSR) | 3852 |
比较例3C | 5.5 | 4136 |
比较例4B | 3.7(MSR) | 3763 |
比较例4C | 5.5 | 3671 |
本发明实施例1A | 0 | 35 |
本发明实施例1B | 4.2(MSR) | 523 |
本发明实施例1C | 5.5 | 1045 |
本发明实施例1B和1C显示出令人惊奇和意想不到的结果,其中与以相同或类似拉伸比拉伸并具有相同量碳酸钙的相应比较例相比,WVTR值较低。不受任何理论束缚,本发明实施例1的马来酸酐官能化的乙烯/α-烯烃互聚物可与填料和聚合物基质相互作用以降低孔形成、WVTR和透气性。
还测量了在MD上在5%应变下的力。下表5提供了结果。
表5-5%应变MD下的力数据
如表5中所示,与具有相同或类似拉伸比和相同量碳酸钙的比较例相比,本发明实施例1B和1C在MD上在5%应变下具有相对较高的力值。因此,与相应的比较例相比,本发明实施例显示出较低的WVTR和在MD上在5%应变下改善的模量或力。在MD上在5%应变下的改善的力可导致耐流体静压力的增加,这是重要的,例如,在包装过程期间以及对于抵抗当人坐在诸如尿布的制品上时可被捕获在该制品中的液体的压力而言。本发明的膜表现出低的WVTR值和改善的模量,同时还掺入大量低规格的无机填料。
参数XNBB可用于显示本发明和发明实施例1的有利结果。XNBB对应于下式:
计算比较例和本发明实施例的XNBB并提供于下表6中。
表6-XNBB结果
实施例 | 拉伸比 | XNBB |
比较例1A | 0 | 0 |
比较例2A | 0 | 0 |
比较例2B | 3.7(MSR) | 0.0011 |
比较例2C | 5.5 | 0.0030 |
比较例3B | 3.9(MSR) | 0.0010 |
比较例3C | 5.5 | 0.0019 |
比较例4B | 3.7(MSR) | 0.0007 |
比较例4C | 5.5 | 0.0016 |
本发明实施例1A | 0 | 0 |
本发明实施例1B | 4.2(MSR) | 0.0108 |
本发明实施例1C | 5.5 | 0.0113 |
除非明确地排除或以其他方式限制,否则本文引用的每个文献(如果有的话),包括任何交叉引用的或相关的专利或申请以及本申请要求优先权或权益的任何专利申请或专利特此以引用的方式整体并入本文。任何文件的引用均不承认其为本文中所公开或所要求保护的任何发明的现有技术,或其单独或与任一个或多个其他参考文件组合教示、表明或公开任何此类发明。另外,在此文件中的术语的任何意义或定义与以引用方式并入的文件中的相同术语的任何意义或定义冲突的情况下,应以在此文件中赋予所述术语的意义或定义为准。
虽然已经说明和描述了本发明的具体实施方案,但本领域的技术人员将显而易见的是,可在不脱离本发明的精神和范围的情况下作出多种其他改变和修改。因此,旨在于在所附权利要求书中涵盖在本发明的范围内的所有此类改变和修改。
Claims (10)
1.一种膜,包含:
(a)1重量%至15重量%的酸酐和/或羧酸官能化的乙烯/α-烯烃互聚物,其具有小于100℃的熔点;
(b)20重量%至59重量%的线性低密度聚乙烯,其具有0.900g/cm3至0.940g/cm3的密度和0.1g/10min至10.0g/10min的熔体指数(I2);以及
(c)40重量%至70重量%的无机填料,所述无机填料选自由以下组成的组:碳酸钠、碳酸钙、碳酸镁、硫酸钡、硫酸镁、硫酸铝、氧化镁、氧化钙、氧化铝、云母、滑石、二氧化硅、粘土、玻璃球、二氧化钛、氢氧化铝、沸石、以及它们的组合;并且
其中重量%是基于所述膜的总重量计的;并且
其中所述膜具有小于1,100g/m2*天的水蒸气传输速率(WVTR)和至少2:1的拉伸比。
2.根据权利要求1所述的膜,其中所述酸酐和/或羧酸官能化的乙烯/α-烯烃互聚物的酸酐或酸含量为0.1重量%至2.0重量%,其中所述酸酐或酸含量的重量%是基于所述酸酐和/或羧酸官能化的乙烯/α-烯烃互聚物的总重量计的。
3.根据任一前述权利要求所述的膜,其中所述酸酐和/或羧酸官能化的乙烯/α-烯烃互聚物是马来酸酐官能化的乙烯/α-烯烃互聚物。
4.根据任一前述权利要求所述的膜,其中所述无机填料是碳酸钙。
5.根据任一前述权利要求所述的膜,其中所述酸酐和/或羧酸官能化的乙烯/α-烯烃互聚物具有小于65℃的熔点。
6.根据任一前述权利要求所述的膜,其中所述膜具有5克/平方米(gsm)至50gsm的基重。
7.根据任一前述权利要求所述的膜,其中所述膜在纵向上在5%应变下具有大于2.000N/15mm膜宽度的力。
8.根据任一前述权利要求所述的膜,其中XNBB定义为 其大于或等于0.0060。
9.一种层合体,所述层合体包括与非织造物或第二膜粘附接触的根据前述权利要求中任一项所述的膜。
10.一种用于制造膜的方法,所述方法包括:
提供1重量%至15重量%的酸酐和/或羧酸官能化的乙烯/α-烯烃互聚物,其具有小于100℃的熔点;20重量%至59重量%的线性低密度聚乙烯,其具有0.900g/cm3至0.940g/cm3的密度和0.1g/10min至10.0g/10min的熔体指数(I2);以及40重量%至70重量%的无机填料,所述无机填料选自由以下组成的组:碳酸钠、碳酸钙、碳酸镁、硫酸钡、硫酸镁、硫酸铝、氧化镁、氧化钙、氧化铝、云母、滑石、二氧化硅、粘土、玻璃球、二氧化钛、氢氧化铝、沸石、以及它们的组合;其中重量%是基于所述膜的总重量计的;
挤出所述酸酐和/或羧酸官能化的乙烯/α-烯烃互聚物、线性低密度聚乙烯和无机填料以形成所述膜;以及
将所述膜拉伸至至少2:1的拉伸比。
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US (1) | US20240228711A9 (zh) |
EP (1) | EP4298155A1 (zh) |
JP (1) | JP2024508427A (zh) |
KR (1) | KR20230152063A (zh) |
CN (1) | CN116867844A (zh) |
AR (1) | AR124944A1 (zh) |
WO (1) | WO2022182588A1 (zh) |
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US5843057A (en) * | 1996-07-15 | 1998-12-01 | Kimberly-Clark Worldwide, Inc. | Film-nonwoven laminate containing an adhesively-reinforced stretch-thinned film |
KR100773737B1 (ko) * | 2006-05-10 | 2007-11-09 | (주)대명화학 | 소음이 적고, 은폐력이 향상된 위생용 필름 |
ES2419206B1 (es) * | 2012-01-14 | 2014-05-30 | Kloner S.L. | Composición y procedimientro para la obtención de una película de un polímero termoplástico micro-porosa especialmente adecuada para la confección de artículos de higiene personal como los pañales y las compresas |
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2022
- 2022-02-18 US US18/276,974 patent/US20240228711A9/en active Pending
- 2022-02-18 KR KR1020237032005A patent/KR20230152063A/ko unknown
- 2022-02-18 WO PCT/US2022/016972 patent/WO2022182588A1/en active Application Filing
- 2022-02-18 CN CN202280015309.0A patent/CN116867844A/zh active Pending
- 2022-02-18 EP EP22708681.6A patent/EP4298155A1/en active Pending
- 2022-02-18 JP JP2023550060A patent/JP2024508427A/ja active Pending
- 2022-02-23 AR ARP220100379A patent/AR124944A1/es unknown
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AR124944A1 (es) | 2023-05-24 |
JP2024508427A (ja) | 2024-02-27 |
US20240228711A9 (en) | 2024-07-11 |
WO2022182588A1 (en) | 2022-09-01 |
KR20230152063A (ko) | 2023-11-02 |
US20240132680A1 (en) | 2024-04-25 |
EP4298155A1 (en) | 2024-01-03 |
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