CN103497406A - 新的双组分纤维 - Google Patents

新的双组分纤维 Download PDF

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Publication number
CN103497406A
CN103497406A CN201310105188.1A CN201310105188A CN103497406A CN 103497406 A CN103497406 A CN 103497406A CN 201310105188 A CN201310105188 A CN 201310105188A CN 103497406 A CN103497406 A CN 103497406A
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composition
fiber
nonwoven fabric
conjugate fiber
resin
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Granted
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CN201310105188.1A
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CN103497406B (zh
Inventor
约尔格·达灵格尔
贝恩德·A·布莱齐
维尔纳·斯特法尼
维尔纳·格拉瑟尔
米梅特·德米洛斯
格尔特·克拉森
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Dow Chemical Co
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Trevira GmbH
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    • D01F8/00Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/06Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyolefin as constituent
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    • C08F10/00Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/04Homopolymers or copolymers of ethene
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    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
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Abstract

本发明涉及新的双组分纤维。具体地,本发明涉及新的双组分纤维、包含所述新的双组分纤维的无纺织物以及由其制成的卫生用品。所述双组分纤维含有基于聚乙烯的树脂,所述基于聚乙烯的树脂在纵向上连续地形成纤维的至少一部分表面,并具有下述特征:共聚单体分布常数大于约45,重结晶温度在85℃和110℃之间,0.1rad/sec时的tanδ值为约15至50,以及0.1rad/秒时的复数粘度为1400Pa.sec以下。包含本发明的新双组分纤维的无纺织物不仅柔软性极好,而且强度高,并且由于较高的产量和需要的能量较少,可以以较低成本以商业化规模生产。

Description

新的双组分纤维
本申请是申请日为2010年12月31日、中国国家申请号为201080060615.3、发明名称为“新的双组分纤维”申请的分案申请。
本发明涉及新的双组分纤维、包含所述新的双组分纤维的无纺织物以及由其制成的卫生用品。包含本发明的新的双组分纤维的无纺织物不仅柔软性极好,而且强度高,并且由于较高的产量和需要的能量较少,可以以较低成本以商业化规模生产。
近年来,无纺织物,例如纺粘无纺织物和使用梳理成网、熔喷或气流成网技术制造的无纺织物,已被广泛用于各种应用,由其制成的卫生用品也是如此。
树脂纤维由聚乙烯形成的聚乙烯无纺织物,以其柔软性和良好的触感而著称(EP-A-0,154,197)。然而,聚乙烯纤维难以纺丝,并因此难以使其具有织物获得良好柔软性所需要的细度。由聚乙烯纤维形成的无纺织物在经受压延辊的热/压力处理时容易熔化,并且更糟的是,由于纤维的强度低,它容易将自身缠绕在辊上。已针对上述问题采取降低处理温度的措施;然而,在这种情况下,热粘合容易不充分,从而导致另一个问题,即不能获得具有足够强度和耐摩擦坚牢度的无纺织物。事实上,聚乙烯无纺织物在强度方面不如聚丙烯无纺织物。
为了解决上述问题,已经提出了利用芯-鞘型双组分纤维的技术,所述芯-鞘型双组分纤维使用聚丙烯、聚酯等树脂作为芯,聚乙烯作为鞘(日本专利公开号2-182960和日本专利公开号5-263353)。
然而,由上述芯-鞘型双组分纤维形成的无纺织物尚未同时具有足以用作卫生材料的柔软性和强度。具体来说,当增加作为鞘的组成成分的聚乙烯的量时,无纺织物的柔软性增加,但未提供足够的强度,结果它很可能在加工期间断裂。另一方面,当增加芯的组成成分时,使得无纺织物具有了足够的强度,但柔软性差,并且该无纺织物作为用于卫生产品材料的品质降低。因此,获得具有令人满意的水平的上述两种性能的无纺织物是困难的。
许多这些芯-鞘型双组分纤维包含聚乙烯鞘和聚酯或聚丙烯芯。目前典型用于这种应用中的聚乙烯具有一般高于110℃的重结晶温度。
上述问题的第一种解决方法被公开在EP-A-1,057,916中,EP-A-1,057,916描述了由复合纤维制成的用于一次性卫生用品的纺粘无纺织物。这种具有高熔点芯和低熔点鞘材料的复合纤维可以是并列类型。推荐的低熔点材料是基于聚乙烯的树脂,其具有在120至135℃范围内的第一高熔点和在90至125℃范围内的第二低熔点,第二低熔点材料的熔点比第一高熔点低至少5℃。这种低熔点的基于聚乙烯的树脂制造起来相当复杂,并在纤维纺丝和随后将这种复合纤维用于生产无纺织物、特别是使用梳理、熔喷或气流成网技术制造的无纺织物期间引起问题。
然而,仍然希望降低聚乙烯的熔点,从而提供由于粘合温度降低和能量消耗减少引起的较快的线速度。另一方面,降低聚乙烯的熔点在纤维纺丝期间伴有明显的加工问题。对于用于粘合剂纤维的广泛适用性而言,这种纤维应具有下列特性:良好的纺丝性能,以致纺丝加工期间的发烟、纤维断裂和纤维粘附在一起的情况被最小化;纤维还需要具有低COF,使其能够被卷曲变形;良好的纤维拉伸性质;能够被容易地切断;能够被用在气流成网方法中和能够使用热空气粘合方法在最低温度下将其粘合而不使纤维变粘。此外,双组分纤维的外层应该与内部的芯(基材)以及其他纤维产品具有良好的粘合。
因此,本发明的目的是解决上面提到的问题,具体来说是提供双组分纤维,所述双组分纤维可提供具有极好的柔软性和触感并具有足够的强度并且能够以较低成本在现有的商业化设备上生产的无纺织物。
本发明的主题内容涉及一种双组分纤维,所述双组分纤维由基于聚乙烯的树脂(A)和熔点比上述基于聚乙烯的树脂(A)的熔点高至少10℃的高熔点树脂(B)构成,基于聚乙烯的树脂(A)与高熔点树脂(B)的组分重量比在50/50至10/90的范围内,并且所述基于聚乙烯的树脂(A)在纵向上连续地形成纤维的至少一部分表面,其中基于聚乙烯的树脂(A)具有下列特征:共聚单体分布常数大于约45,重结晶温度在85℃和110℃之间,0.1rad/sec时的tanδ值为约15至50,并且0.1rad/秒时的复数粘度为1400Pa.sec以下。
本发明的另一个主题是包含上述双组分纤维的无纺织物。优选地,这种无纺织物包含本发明的双组分纤维作为卷曲变形的卷曲纤维和/或未卷曲变形的扁平纤维。此外,这种无纺织物包含上述双组分纤维作为短纤维和/或连续长丝纤维。
优选的无纺织物是(i)湿法成网无纺织物、(ii)气流成网无纺织物和(iii)梳理成网无纺织物。
本发明的另一个主题是包含本发明的无纺织物的卫生用品。
定义
所使用的术语“组合物”包括包含组合物的材料以及从组合物的材料形成的反应产物和分解产物的混合物。
所使用的术语“掺混物”或“聚合物掺混物”是指两种以上聚合物的紧密的物理混合物(即未反应)。掺混物可以混溶或可以不混溶(在分子水平上没有相分离)。掺混物可以相分离或可以不相分离。当通过透射电子显微术、光散射、x-射线散射和本技术领域中已知的其他方法测定时,掺混物可以含有或可以不含一个或多个畴结构。通过将两种以上聚合物在宏观水平(例如熔融掺混树脂或复合)或微观水平(例如在同一反应器中同时形成)上进行物理混合可以实现掺混。
术语“长链支化聚合物”是指一类聚合物,其中聚合物的聚合物骨架含有比典型使用的共聚单体更长(例如长于6或8个碳原子)的支链。长链支化聚合物典型地含有大于0.2个长支链/1000个碳原子。
术语“直链”是指一类聚合物,其中聚合物的聚合物骨架缺少可测量或可证实的长支链,例如聚合物可以取代有平均小于0.01个长支链/1000个碳原子。
术语“聚合物”是指通过相同或不同类型的单体的聚合而制备的聚合化合物。因此,聚合物这一通称涵盖了术语“均聚物”和本文中定义的术语“互聚物”,“均聚物”通常用于指代仅由一种类型的单体制备的聚合物。
术语“互聚物”是指通过至少两种不同类型的单体的聚合制备的聚合物。互聚物这一通称包括共聚物,共聚物通常用于指代由两种不同单体制备的聚合物以及由大于两种不同类型的单体制备的聚合物。
术语“基于乙烯的聚合物”是指含有超过50mol%的聚合的乙烯单体(以可聚合单体的总量计)并任选可以含有至少一种共聚单体的聚合物。
双组分纤维
本发明的双组分纤维可以是任何形状并且不限于特定形状。然而,优选的是芯-鞘型双组分纤维和并列型双组分纤维。
树脂(A)基于聚乙烯的树脂
本发明的双组分纤维含有基于聚乙烯的树脂(A),基于聚乙烯的树脂(A)具有大于约45的共聚单体分布常数、在85℃和110℃之间的重结晶温度、0.1rad/sec时约15至50的tanδ值、和0.1rad/秒时1400Pa.sec以下的复数粘度。
基于乙烯的聚合物树脂组合物可以进一步表征为在85℃至110℃的温度范围内具有单个差示扫描量热术(DSC)熔融峰。
基于乙烯的聚合物树脂组合物可以进一步表征为具有大于约45、更优选大于50、最优选大于55并高达400、更优选高达100的共聚单体分布常数。具体来说,优选的基于乙烯的聚合物树脂组合物具有在45至400范围内、最优选在50至100范围内、至多优选在55至100范围内的共聚单体分布常数。
基于乙烯的聚合物组合物是那些在高压反应器中利用自由基聚合方法、优选使用基于过氧化物的自由基引发剂制造的基于乙烯的聚合物组合物。优选的聚乙烯树脂具有在5至25g/10min、更优选5至20范围内的熔体指数(按照ASTM D1238测定,条件为190℃/2.16kg)。
优选的乙烯类树脂具有在0.910至0.930g/cm3、更优选0.915至0.925范围内的密度。
基于乙烯的聚合物组合物还可以被表征为在85℃至110℃、优选90至105℃范围内具有峰值重结晶温度。
基于乙烯的聚合物组合物还可以被表征为具有大于约0.2个长支链/1000个碳原子,优选约0.2至约3个长支链/1000个碳原子。
基于乙烯的聚合物组合物还可以被表征为具有在0.1rad/秒时1400Pa.sec以下、更优选在100rad/秒时500Pa.sec以下的复数粘度。最优选地,本发明的树脂将具有0.1rad/秒时在500至1200范围内并且100rad/秒时在150至450Pa.sec范围内的复数粘度。
优选的基于乙烯的聚合物组合物还可以被表征为在0.1rad/sec时具有约15至50、优选15至40的tanδ值。
在用于生产基于聚乙烯的树脂(A)的某些方法中,在本发明的基于乙烯的聚合物中还可以包含加工助剂例如增塑剂。这些助剂包括但不限于邻苯二甲酸酯例如邻苯二甲酸二辛酯和邻苯二甲酸二异丁酯,天然油类例如羊毛脂和从石油精炼获得的石蜡油、环烷油和芳香油,以及来自于松香或石油原料的液体树脂。可用作加工助剂的油类的示例性类型包括白色矿物油例如KAYDOL油(Chemtura Corp.;Middlebury,Conn.)和SHELLFLEX 371环烷油(Shell Lubricants;Houston,Tex.)。另一种适合的油是TUFFLO油(Lyondell Lubricants;Houston,Tex)。
在某些方法中,将乙烯类聚合物用一种或多种稳定剂例如抗氧化剂进行处理,所述抗氧化剂例如IRGANOX 1010和IRGAFOS 168(CibaSpecialty Chemicals;Glattbrugg,Switzerland)。
一般来说,在挤出或其他熔融处理之前将聚合物用一种或多种稳定剂进行处理。在其他实施方案的方法中,其他聚合添加剂包括但不限于紫外光吸收剂、抗静电剂、颜料、染料、成核剂、填充剂、滑爽剂、阻燃剂、增塑剂、加工助剂、润滑剂、稳定剂、抑烟剂、粘度控制剂、表面改性剂和防结块剂。以实施方案的乙烯类聚合物的重量计,乙烯类聚合物组合物可以含有例如小于10%的一种或多种添加剂的合并重量。
产生的乙烯类聚合物可以被进一步复合。在某些乙烯类聚合物组合物中,可以将一种或多种抗氧化剂进一步复合到聚合物中,并将复合的聚合物造粒。复合的乙烯类聚合物可以含有任何量的一种或多种抗氧化剂。例如,复合的乙烯类聚合物可以包含约200至约600份的一种或多种苯酚类抗氧化剂/一百万份聚合物。此外,复合的乙烯类聚合物可以包含约800至约1200份基于亚磷酸酯的抗氧化剂/一百万份聚合物。
可以使用两个以上的反应器来制造基于聚乙烯的树脂(A),其中一个反应器是具有至少一个反应区的返混反应器,第二个反应器是具有至少两个反应区的层流反应器。有利情况下,也可以在具有两个以上反应区的典型的管式高压过程中制造该产物,所述反应区入口处的乙烯压力在1800巴至3500巴的范围内。有利情况下,第一反应区的入口处的压力可以在2000巴至3000巴的范围内。聚合温度可以起始于110℃至150℃,峰值温度为约280℃至330℃。为了引发反应,正如本技术领域中已知的,使用过氧化物的混合物在给定温度和压力下获得所需要的反应速率。本技术领域的专业人员根据工厂、过程压力、温度和停留时间的情况可以确定自由基过氧化物引发剂混合物的准确组成。为了生产本发明的组合物,有利情况下,可以在反应器的第一反应区中使用约14比3体积比的过氧化辛酸叔丁酯和二叔丁基过氧化物的混合物。也可以在第二反应区中以1比1的体积比使用同样的两种过氧化物。精确的量将取决于反应堆的纯度、反应器特性和其他过程参数,并可以由本技术领域的专业人员根据每种具体情况来确定。
第二反应区的再引发温度可以为约160℃至230℃,峰值温度为约280℃至330℃。可以使用甲乙酮和丙烯的混合物作为链转移剂来控制分子量。典型的范围可以为约百万分之10至5000体积的甲乙酮和约0.1体积%至5体积%的丙烯,这取决于所需的复数粘度范围。然后将聚合物与加工溶剂和未反应的乙烯分离,通过挤出机造粒,并且不用进一步加工即可使用。
也可以在形成后向乙烯类聚合物中加入添加剂和佐剂。适合的添加剂包括填充剂,例如有机或无机粒子包括粘土、滑石粉、二氧化钛、沸石、金属粉末特别是基于银和/或银离子的金属粉末、超级吸收剂材料,有机或无机纤维包括碳纤维、氮化硅纤维、钢丝或钢网、和尼龙绳或聚酯绳,纳米尺寸粒子,粘土等;增粘剂,油增量剂包括石蜡油或环烷油;以及其他天然和合成的聚合物,包括按照实施方案的方法制造或可以按照实施方案的方法制造的其他聚合物。
树脂(B)高熔点树脂
本发明的双组分纤维含有高熔点树脂(B),高熔点树脂(B)典型地形成本发明的芯鞘型双组分纤维的芯部分。这种高熔点树脂(B)是熔点比上述基于聚乙烯的树脂(A)的熔点高至少10℃、优选至少20℃、最优选至少30℃的热塑性树脂。
优选的高熔点树脂(B)包括聚烯烃树脂例如基于丙烯的聚合物,聚酯树脂例如聚对苯二甲酸乙二酯(PET),和聚酰胺树脂例如尼龙。在上述所有树脂中,聚酯树脂例如聚对苯二甲酸乙二酯(PET)、聚对苯二甲酸丁二酯(PBT)、聚对苯二甲酸萘二酯(polynaphthaleneterephthalate,PEN)是最优选的。
在上述基于丙烯的聚合物中,最优选的是丙烯均聚物或丙烯与α-烯烃例如乙烯、1-丁烯、1-己烯、4-甲基-1-戊烯和1-辛烯的共聚物。在上述所有共聚物中,特别优选的是由丙烯和少量乙烯组成的丙烯-乙烯无规共聚物,其中乙烯衍生的结构单元的含量为0.1至5mol%。使用该类型的共聚物为它们的双组分纤维提供了良好的可纺丝性和生产率,并提供具有良好柔软性的无纺织物。这里使用的术语“良好的可纺丝性”是指从喷丝嘴挤出期间和拉延期间既不发生纱线断裂也不发生长丝熔融。
就获得在平衡可纺丝性和纤维强度方面特别优秀的纤维而言,优选上述基于丙烯的聚合物具有在20至100g/10min范围内的熔体流动速率(MFR;按照ASTM D1238在230℃和2.16kg载荷下测定)。
就获得可纺丝性良好并且纤维强度特别优秀的双组分纤维而言,当通过凝胶渗透色谱(GPC)测定时,优选上述基于丙烯的聚合物的分子量分布(Mw/Mn)在2.0至4.0的范围内,更优选Mw/Mn在2.0至3.0的范围内。
芯组分优选可以由常规的可熔纺聚酯材料构成。原则上适用于纤维制造的所有已知类型都可以考虑作为聚酯材料。这种聚酯基本上由源自于芳香族二羧酸和脂族二醇的组分构成。常用的芳香族二羧酸组分是苯二羧酸、特别是对苯二甲酸和间苯二甲酸的二价残基;常用的二醇具有2至4个碳原子,特别适合的是乙二醇。
特别有利的是至少85mol%由聚对苯二甲酸乙二酯构成的聚酯材料。然后剩余的15mol%由二羧酸单元和二元醇单元构成,所述二羧酸单元和二元醇单元充当所谓的改性剂,并使专家能够以特定方式进一步影响所产生的纤维的物理和化学性质。这种二羧酸单元的实例是间苯二甲酸或脂族二羧酸例如戊二酸、己二酸、癸二酸的残基;具有改性作用的二醇残基的实例是那些长链二醇例如丙二醇或丁二醇、二或三乙二醇、或者分子量为500至2000g/mol的聚乙二醇的残基,如果所述聚乙二醇可以以少量获得的话。
特别优选的聚酯含有至少95mol%的聚对苯二甲酸乙二酯,特别是那些未改性的聚对苯二甲酸乙二酯。这种聚酯一般具有相当于在25℃下在二氯乙酸溶液中测得固有粘度(IV)为0.5至1.4(dl/g)的分子量。
添加剂
形成纤维的鞘部分的基于聚乙烯的树脂(A)和/或形成纤维的芯部分的高熔点树脂(B)可以根据情况与添加剂例如着色材料、耐热性稳定剂、润滑剂、成核剂和其他聚合物掺混。
适用于本发明的着色材料例如包括无机着色材料例如氧化钛和碳酸钙,以及有机着色材料例如酞菁。
耐热性稳定剂例如包括基于苯酚的稳定剂,如BHT(2,6-二叔丁基-4-甲基苯酚)。
润滑剂例如包括油酰胺、芥酰胺和硬脂酰胺。在本发明中,特别优选将0.1至0.5wt.%的润滑剂与形成鞘部分的基于聚乙烯的树脂(A)掺混,这是由于以上述方式获得的双组分纤维可以具有增强的耐摩擦坚牢度。
另一种类型的添加剂是促进形成纤维的鞘部分的基于聚乙烯的树脂(A)和/或高熔点树脂(B)之间的粘合的粘合促进剂。适合的粘合促进剂是促进这种粘合的马来酸(MSA)或马来酸酐(MAH)。以重量计的典型的添加量为0.05至3%。最优选地,在双组分纤维纺丝过程中向处于熔体状态的基于聚乙烯的树脂(A)加入粘合促进剂(请核对提到的其他添加剂的量和可能性)。
优选地,基于聚乙烯的树脂(A)与高熔点树脂(B)的组分重量比在50/50至10/90的范围内,并且就获得在平衡柔软性和耐摩擦坚牢度方面优秀的纤维而言,优选在50/50至20/80的范围内,更优选在40/60至30/70的范围内。
当基于聚乙烯的树脂(A)相对于双组分纤维的比例超过50时,可能存在一些在纤维强度方面未提高的部分。另一方面,当基于聚乙烯的树脂(A)相对于双组分纤维的比例低至小于10时,在获得的织物中可能存在一些在柔软性和触感两方面都不良的部分。
在本发明的芯-鞘型双组分纤维的横截面中,鞘部分与芯部分的面积比一般与上述的组分重量比几乎相同,并且在50/50至10/90的范围内,优选在50/50至20/80的范围内,更优选在40/60至30/70的范围内。
本发明的芯-鞘型双组分纤维可以是同心型双组分纤维或偏心型双组分纤维,在同心型双组分纤维中,圆形芯部分和环形鞘部分在纤维的同一横截面中具有相同的中心点,芯部分被包裹在鞘部分中,而在偏心型双组分纤维中,芯部分和鞘部分的中心点彼此不同。此外,芯-鞘型双组分纤维可以是其中芯部分部分暴露在纤维表面上的偏心型双组分纤维。
对于芯-鞘型双组分纤维来说,优选它的细度为0.7至20dtex,并且就获得柔软性更优秀的纤维而言,更优选为0.9至15dtex。
双组分纤维的生产
带有合适的喷嘴的现有技术装置可用于制造本发明的双组分纤维。
除了常见的芯-鞘型之外,具有芯占据偏心位置的芯/鞘型剖面的双组分纤维也是本发明的一部分。US 2005/0093197中更详细地描述了这些所谓的偏心双组分纤维,所述专利在这种偏心双组分纤维的设计方面形成本说明书的一部分。
用于形成本发明的双组分纤维的纺丝速度典型地在600和2,000之间,优选在800和1,500m/min之间。
喷嘴脱离表面上的脱离速度与纺丝速度和拉延比相匹配,使得最终产生的纤维的纤度在0.7至20dtex、优选0.9至15dtex的范围内。
将用于制造本发明的双组分纤维的原材料在挤出机等中独立地熔化,并将每种熔融物挤出穿过带有双组分纤维喷丝嘴的喷丝头,从而纺出双组分纤维,所述喷丝嘴被构造成将熔融物挤出的方式使得能形成所需要的结构例如芯-鞘结构。
然后将纺出的双组分纤维用冷却液冷却,通过吸入空气让其遭受拉力,以获得如上定义的预定细度。
为了生产纺粘无纺织物,将新鲜纺出的本发明的双组分纤维收集在收集带上,在收集带上沉积至预定厚度,从而可以获得双组分纤维的纺粘无纺织物。该纺粘的双组分纤维无纺织物可以被进一步固结,例如通过让无纺织物经受进一步缠结,例如通过使用压花辊的热压成方法或通过已知的针刺/水刺缠结方法。
为了生产其他无纺织物,例如湿法成网无纺织物、气流成网无纺织物和梳理成网无纺织物,需要对新鲜纺出的双组分纤维作进一步处理。
双组分纤维的纺丝后处理
为了生产无纺织物例如湿法成网无纺织物、气流成网无纺织物和梳理成网无纺织物,需要在纺丝后作进一步处理。
典型地使用1.2和4.0之间的各个不同比率将本发明的双组分纤维拉延,所述拉延比以约0.1变化,即它们是1.2、1.3、1.4、……、直至4.0。产生的总拉延比在1.2和4.0之间。
在40和70℃之间的相同或不同温度下、优选在55℃下拉延双组分纤维。
然后,可以将拉延的双组分纤维卷曲,典型地是在填塞箱中。
在填塞箱中卷曲之后,在高达100℃下对双组分纤维进行热处理,保持时间为3至20分钟,最优选12至15分钟。
使用如上所述的偏心双组分纤维可以提高卷曲度。
典型地,卷曲度被表示成卷曲收缩率(K1),用下面的公式计算卷曲收缩率:
K1=(解卷曲长度–卷曲后长度)/解卷曲长度
(标准气候,20℃+/-2℃,60-65%的相对空气湿度)
卷曲数典型地作为卷曲/cm给出。
卷曲变形或未卷曲变形的双组分纤维可以被切成短纤维,然后加工成适合的产品。典型的短纤维长度为0.2cm至15cm,优选0.2cm至8cm,最优选0.3cm至6cm。
为了用于湿法成网无纺织物,本发明的双组分纤维典型地是在纺丝后未卷曲变形的未卷曲变形扁平纤维。优选地,这种扁平纤维的长度为0.2cm至3cm,最优选0.3cm至2.5cm。
为了用于气流成网无纺织物,本发明的双组分纤维典型地是卷曲变形的纤维。优选地,卷曲收缩率(K1)为3至7%,卷曲数为3至6个卷曲/cm。
为了用于梳理成网无纺织物,本发明的双组分纤维典型地是卷曲变形的纤维。优选地,卷曲收缩率(K1)为8至15%,卷曲数为5至8个卷曲/cm。
随后,可以将双组分纤维加工成适合的产品,特别是纺织产品,优选卫生产品、卫生纺织面料、卫生无纺织物、尿布、毛巾或衬垫等,但是也可以加工成棉签等。
作为选择偏心芯-鞘设计的结果,这种双组分纤维被赋予有额外的潜在卷曲,可以在进一步加工期间由超过约100℃的温度下的热处理来引发所述额外的潜在卷曲。
双组分纤维无纺织物
本发明的另一个主题是包含如上所述的双组分纤维的无纺织物。
由于基于聚乙烯的树脂(A)在纵向上连续地形成纤维的至少一部分表面这一性质,其中所述基于聚乙烯的树脂(A)被表征为共聚单体分布常数大于约45、重结晶温度在85℃和110℃之间、0.1rad/sec时tanδ值为约15至50并且0.1rad/秒时的复数粘度为1400Pa.sec以下,因此无纺织物的加工可以得到显著改进。
在形成无纺织物和随后的热粘合时,具体的基于聚乙烯的树脂(A)决定了加工温度。由于基于聚乙烯的树脂(A)低于120℃的较低熔点,因此需要的粘合温度降低和能量消耗减少。此外,可能实现更快的线速度,从而引起生产成本降低。尽管熔点较低,但在纤维纺丝期间不发生明显的加工问题。例如,当本发明的双组分纤维与极其热敏感的基于纤维素的纤维组合用于无纺织物时,可出现这些以及其他优点。由于体积大,加工/热粘合温度即使少量降低也可以具有明显的商业优势。此外,还降低了潜在的着火风险。此外,可以降低或甚至避免与本发明的双组分纤维掺混的其他材料的潜在热损伤。
优选的无纺织物是(i)湿法成网无纺织物、(ii)气流成网无纺织物和(iii)梳理成网无纺织物。
本发明的无纺织物可以与其他纤维材料掺混。
优选地,本发明的无纺织物具有10至500g/m2的基准重量。上述基准重量取决于随后的应用。
优选地,本发明的无纺织物包含卷曲变形或未卷曲变形并被切成短纤维的双组分纤维,优选具有0.2cm至15cm、更优选0.2cm至8cm、最优选0.3cm至6cm的短纤维长度。
优选地,本发明的无纺织物是典型地包含本发明的双组分纤维的湿法成网无纺织物,所述双组分纤维是未卷曲变形的扁平纤维,优选具有0.2cm至3cm、最优选0.3cm至2.5cm的长度。
优选地,本发明的无纺织物是典型地包含本发明的双组分纤维的气流成网无纺织物,所述双组分纤维是卷曲变形的,优选具有3至7%的卷曲收缩率(K1)和3至6个卷曲/cm的卷曲数,优选具有0.2cm至3cm、最优选0.3cm至2.5cm的长度。
优选地,本发明的无纺织物是典型地包含本发明的双组分纤维的梳理成网无纺织物,所述双组分纤维是卷曲变形的,优选具有8至15%的卷曲收缩率(K1)和5至8个卷曲/cm的卷曲数,优选具有2cm至15cm、最优选3cm至8cm的长度。
此外,本发明的无纺织物可以是包含连续长丝或不连续纤维的纺粘无纺织物,所述连续长丝或不连续纤维二者都是由上述基于聚乙烯的树脂(A)和高熔点树脂(B)构成的双组分类型。
可以使用现有技术来形成本发明的无纺织物。
取决于目的用途,本发明的无纺织物可以与其他纤维和/或粒子材料掺混。
对于工业应用来说,本发明的无纺织物包含其他纤维材料,例如有机和/或无机纤维材料,所述其他纤维材料也可以是再循环材料。
术语有机纤维材料除了包括有机聚合物树脂之外还包括天然纤维材料。可以使用有机聚合物树脂中的所有可熔纺材料。特别优选的可熔纺有机聚合物例如为聚烯烃如聚乙烯和/或聚丙烯,聚酯例如聚对苯二甲酸乙二酯(PET)、聚对苯二甲酸丁二酯(PBT)、聚对苯二甲酸萘二酯(PEN)、聚对苯二甲酸丙二酯(PTT),聚酰胺例如尼龙。
对于工业应用来说,本发明的无纺织物包含粒子材料例如无机粒子材料,特别是研磨材料。
术语无机纤维材料除了包括其他材料之外,还包括那些基于玻璃和/或矿物质的无机纤维材料,特别是再循环材料。
工业应用是过滤介质或电池隔膜。
对于纺织应用、优选为卫生和/或保健产品来说,本发明的无纺织物包含其他纤维材料。优选的纤维材料是纸浆、纤维素、棉、基于聚乙烯或聚丙烯、特别是基于再循环材料的均聚物和共聚物。
随后,可以将本发明的无纺织物加工成适合的产品,或加工形成这些产品的组成部分,所述产品特别是纺织产品,优选卫生产品、卫生纺织面料、卫生无纺织物、一次性尿布、卫生巾、尿布、毛巾或衬垫等,但是也可以加工成棉签等。
对于某些纺织应用来说,本发明的无纺织物除了包含其他纤维材料之外,还可以包含粒子材料,例如用于一次性尿布的超级吸收剂材料等。
本发明的无纺织物可以与其他覆盖层或面层组合,以提供甚至更柔软的触感。适合的覆盖层或面层是由直径为1至10pm的纤维形成的熔喷无纺织物。
试验方法
密度:
按照ASTM D 1928制备用于测定密度的样品。在样品压制后1小时内使用ASTM D792方法B进行测定。
熔体指数:
按照ASTM D 1238测定熔体指数或I2,条件为190℃/2.16kg,将熔体指数或I2报告为每10分钟洗脱的克数。按照ASTM D 1238测定I10,条件为190℃/10kg,将I10报告为每10分钟洗脱的克数。
DSC结晶度:
差示扫描量热术(DSC)可用于测定聚合物在一个宽的温度范围内的熔化和结晶行为。例如,使用装备有RCS(机械制冷系统)和自动进样器的TA Instruments Q1000 DSC来执行该分析。在试验期间,使用50ml/min的氮吹扫气流。将每个样品在约175℃下熔化压制成薄膜;然后将熔化的样品空气冷却至室温(~25℃)。从冷却的聚合物中取出3至10mg、直径6mm的样本,称重,置于轻质铝盘(约50mg)中,并锁闭。然后执行分析以确定其热学性质。通过使样品温度匀变上升和下降以产生热流对温度的分布图,来确定样品的热行为。首先,将样品快速加热至180℃并保持等温3分钟,从而消除其受热历程。接下来,以10℃/分钟的冷却速率将样品冷却至-40℃,并在-40℃保持等温3分钟。然后以10℃/分钟的加热速率将样品加热至150℃(这是“第二次加热”匀变过程)。记录冷却曲线和第二次加热曲线。通过设定基线终点从结晶开始至-20℃来分析冷却曲线。通过设置基线终点从-20℃至熔化结束来分析加热曲线。所测定的值是峰值熔化温度(Tm)、峰值重结晶温度(Tp)、熔化热(Hf)(单位为焦耳每克)和用公式2计算的聚乙烯样品的%结晶度:
%结晶度=((Hf)/(292J/g))x100        (公式2)。
从第二次加热曲线报告熔化热(Hf)和峰值熔化温度。从冷却曲线确定峰值重结晶温度Tp
动态力学谱(DMS)频率扫描
使用装备有25mm平行板的TA Instruments ARES流变仪在氮气吹扫下执行熔体流变学恒温频率扫描。在190℃下以2.0mm的间隙和10%的恒定应变来执行所有样品的频率扫描。频率间隔为0.1至100弧度/秒。根据波幅和相位分析应力响应,由此计算储能模量(G’)、损耗模量(G”)和动态熔体粘度(η*)。
CEF方法:
用结晶洗脱分级(CEF)(西班牙的PolymerChar)(B.Monrabal等,Macromol.Symp.257,71-79(2007))来执行共聚单体分布分析。使用含有600ppm抗氧化剂丁基化羟基甲苯(BHT)的邻二氯苯(ODCB)作为溶剂。使用自动取样器在160℃振摇2小时进行样品制备,浓度为4mg/ml(除非另有指明)。进样体积为300μl。
CEF的温度情况为:从110℃到30℃以3℃/min结晶,在30℃热平衡5分钟,从30℃至140℃以3℃/min洗脱。结晶期间的流速为0.052ml/min。洗脱期间的流速为0.50ml/min。以1个数据点/秒收集数据。
CEF柱由Dow Chemical Company用125μm±6%的玻璃珠(MO-SCI Specialty产品)和1/8英寸不锈钢管装填。按Dow ChemicalCompany的要求,MO-SCI Specialty对玻璃珠进行酸洗。柱体积为206ml。使用NIST标准参比材料直链聚乙烯1475a(1.0mg/ml)和二十烷(2mg/ml)在ODCB中的混合物来进行柱温校准。通过调整洗脱加热速率使得NIST直链聚乙烯1475a具有101.0℃的峰值温度并且二十烷具有30.0℃的峰值温度来校准温度。使用NIST直链聚乙烯1475a(1.0mg/ml)和正六十烷(Fluka,纯度≥97.0%,1mg/ml)的混合物来计算CEF柱的分辨率。实现了正六十烷和NIST聚乙烯1475a的基线分离。正六十烷的面积(从35.0至67.0℃)与NIST 1475a从67.0至110.0℃的面积之比为50比50,低于35.0℃时可溶性组分的量<1.8wt%。CEF柱的分辨率被定义为:
Figure BDA00002981172000191
柱分辨率为6.0。
CDC方法:
从通过CEF获得的共聚单体分布图计算共聚单体分布常数(CDC)。CDC被定义为共聚单体分布指数除以共聚单体分布形状因子乘以100(公式1):
Figure BDA00002981172000192
共聚单体分布指数表示从35.0至119.0℃时,共聚单体含量在共聚单体含量中值(C中值)的0.5倍至C中值的1.5倍范围内的聚合物链的总重量分数。共聚单体分布形状因子被定义为共聚单体分布图的半峰宽除以共聚单体分布图相对于峰值温度(Tp)的标准偏差后得到的比值。
按照下列步骤计算CDC:
根据公式2,从CEF获得从35.0℃至119.0℃的温度步阶为0.200℃的每个温度(T)下的重量分数(wT(T))。
&Integral; 35 119.0 W T ( T ) dT = 1 ……公式2
计算累积重量分数为0.500时的温度平均值(T平均值)(公式3)。
Figure BDA00002981172000201
……公式3
使用共聚单体含量校准曲线(公式4)计算在中值温度(T中值)处以mol.%计的相应的共聚单体含量中值(C中值)。
Figure BDA00002981172000202
(3i)通过使用一系列具有已知量的共聚单体含量的参比材料来建立共聚单体含量校准曲线。在CEF实验部分中指定的相同实验条件下,用CEF分析11种具有窄共聚单体分布(在CEF中从35.0至119.0℃具有单峰共聚单体分布)的参比材料,它们的重均分子量为35,000至115,000(通过常规GPC测定),共聚单体含量在0.0mol%至7.0mol%范围内。
(3ii)使用每种参比材料的峰值温度(Tp)及其共聚单体含量来计算共聚单体含量校准。校准为:
R2=0.997
R2是相关性常数。
共聚单体分布指数是共聚单体含量在0.5×C中值至1.5×C中值范围内的总重量分数。如果T中值高于98.0℃,共聚单体分布指数被定义为0.95。
从CEF共聚单体分布图,通过从35.0℃至119.0℃搜索每个数据点以寻找最高峰值,获得最高峰高(如果两个峰相同,则选择较低温度的峰)。半峰宽被定义为在最高峰高一半处的前温度和后温度之间的温度差。从35.0℃向前搜索最高峰高一半处的前温度,从119.0℃向后搜索最高峰高一半处的后温度。在明显的双峰分布情况下,即峰值温度的差等于或大于各峰的半峰宽总和的1.1倍时,聚合物的半峰宽被计算为每个峰的半峰宽的算数平均值。
按照公式5计算温度标准偏差(Stdev):
Stdev = &Sigma; 35.0 119.0 ( T - T p ) 2 * w T ( T ) ……公式5
共聚单体分布图的实例显示在图1中。
从CEF获得峰值温度、半峰宽和温度中值的示意图。
复数粘度(使用动态熔体粘度),也称为η:
如DMS部分中所概述的,从0.1弧度/sec和100弧度/sec之间的DMS测量来计算动态熔体粘度。
Tanδ
从G’和G”计算tanδ,如下所述:
Tanδ=G”/G’
实施例
将参考下面显示的实施例和比较例对本发明进行进一步详细描述:
Figure BDA00002981172000221
总的来说,对于该应用而言,需要一系列性能属性。首先,树脂必须能够以经济上可行的速率以熔融状态形成纤维。
其次,树脂必须足够适合于在芯纤维上形成良好粘合。
第三,为了良好的气流成网过程,以及为了热空气粘合到其他基材例如纤维素上,树脂必须具有足够低的熔点。
如果Tp过高,气流成网过程将受到损害,并且热空气粘合性质差。如果Tp过低,纤维的粘附则变成问题。事实上,相对窄的熔化范围是理想的。
用下列具体反应参数来制造表1中的本发明的实施例:
在双反应区管式高压自由基聚合反应器中,将所有乙烯在2470巴压力下进料到第一反应区中。将14.1%过氧化辛酸叔丁酯(以重量计)和2.8%二叔丁基过氧化物(以重量计)的混合物,在典型用于这种混合物的惰性溶剂中进料到反应器的第一反应区中。第一反应区的引发温度为136℃,并且第一反应区的峰值温度为310℃。此外,向反应器的第一反应区加入百万分之1280体积的甲乙酮和2.1体积%的丙烯在惰性溶剂中的混合物。向第二反应区加入溶解在惰性溶剂中的7%(以体积计)过氧化辛酸叔丁酯和7%(以体积计)二叔丁基过氧化物的混合物。没有向第二反应区加入链转移剂。第二反应区的入口温度为194℃,第二反应区的峰值温度为317℃。以反应区1开始时进料的总乙烯计,在反应器出口处的乙烯总转化率为28.7%。然后除去聚合物的挥发性成分,以去除未反应的乙烯、惰性溶剂和其他杂质,然后将聚合物造粒。颗粒不用进一步改性即可原样使用。
该材料形成了在本发明的双组分纤维中使用的基于聚乙烯的树脂(A)。因为这种树脂(A)最为重要,因此对仅由这种树脂(A)制成的纤维形式的性质进行研究。
比较例1是可以从Dow Chemical Company作为LDPE PT7009商购的低密度聚乙烯树脂。
比较例2是也可以从Dow Chemical Company作为ASPUNTM 6934树脂商购的基于Ziegler Natta的高密度聚乙烯(HDPE)。
比较例3是可以从Dow Chemical Company作为DOWLEXTM 2045树脂商购的Ziegler Natta直链低密度聚乙烯树脂(LLDPE)。
比较例4是可以从Dow Chemical Company作为ATTANETM 4606树脂商购的Ziegler Natta超低密度直链低密度聚乙烯树脂(ULLDPE)。
已发现,只有比较例1、2和本发明的实施例可以令人满意地制成纤维。尽管比较例2由于它的高重结晶温度而在纤维形成方面良好,但它在所希望的低温下不与纤维良好粘合。该比较例只能在较高温度下发生充分粘合。
比较例3和4不足以形成纤维,这是由于它们的η0.1和η100的值对于高速、经济的纤维形成来说过高。
尽管比较例1在纤维形成、气流成网过程以及热空气粘合方面令人满意,但它在卷曲变形方面次于本发明的实施例。已观察到它不能与基材纤维良好粘合。令人吃惊地发现,与基材纤维的良好粘合要求G”与G’的比率(tanδ)必须在一定范围内。如果tanδ太低,则成鞘树脂弹性太高,并且不能提供良好的粘合,正如比较例1的情况。如果tanδ过高,则成鞘树脂的弹性不足以与基材纤维良好粘合。在成鞘树脂与基材纤维之间没有良好的粘合,就不能获得充分的卷曲变形。
此外,我们发现,如果树脂具有小于45的CDC值,则在给定的峰值重结晶温度下出现纤维的粘附。

Claims (12)

1.基于乙烯的聚合物组合物,其特征在于,共聚单体分布常数大于约45,重结晶温度在85℃和110℃之间,0.1rad/sec时的tanδ值为约15至50,并且0.1rad/秒时的复数粘度为1400Pa.sec以下。
2.权利要求1的组合物,其中共聚单体分布常数在45至400的范围内。
3.权利要求1的组合物,其中共聚单体分布常数在50-100的范围内。
4.权利要求1的组合物,其中共聚单体分布常数在55-100的范围内。
5.权利要求1的组合物,其中0.1rad/sec时的tanδ值为约15至40。
6.权利要求1的聚合物组合物,其中所述组合物具有100rad/秒时500Pa.sec以下的复数粘度。
7.权利要求1的聚合物组合物,其中所述组合物具有90℃至105℃的重结晶温度。
8.权利要求1的聚合物组合物,其中所述组合物的特征还在于,其具有约0.2至约3个长支链/1000个碳。
9.权利要求1的聚合物组合物,其还包含单个DSC熔融峰。
10.权利要求1的组合物,其还包含一种或多种另外的聚烯烃材料。
11.权利要求1的组合物,其还包含选自以下的添加剂:增塑剂、稳定剂、紫外光吸收剂、抗静电剂、颜料、染料、成核剂、填充剂、滑爽剂、阻燃剂、增塑剂、加工助剂、润滑剂、稳定剂、抑烟剂、粘度控制剂、表面改性剂、防结块剂及其组合。
12.制造权利要求1的组合物的方法,其中使用两个以上的反应器来制造所述组合物,其中一个反应器是具有至少一个反应区的返混反应器,并且第二个反应器是具有至少两个反应区的层流反应器。
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