CN107429456B - 层叠无纺布 - Google Patents

层叠无纺布 Download PDF

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Publication number
CN107429456B
CN107429456B CN201680014511.6A CN201680014511A CN107429456B CN 107429456 B CN107429456 B CN 107429456B CN 201680014511 A CN201680014511 A CN 201680014511A CN 107429456 B CN107429456 B CN 107429456B
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China
Prior art keywords
nonwoven fabric
fibers
fiber
laminated
layer
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Application number
CN201680014511.6A
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English (en)
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CN107429456A (zh
Inventor
梶山宏史
大森平
境贤一
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Toray Industries Inc
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Toray Industries Inc
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    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4326—Condensation or reaction polymers
    • D04H1/4334—Polyamides
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4374—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece using different kinds of webs, e.g. by layering webs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/022—Non-woven fabric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/024—Woven fabric
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
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    • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
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    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D04H1/43825—Composite fibres
    • D04H1/43828—Composite fibres sheath-core
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
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    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
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    • D04H1/43825—Composite fibres
    • D04H1/4383—Composite fibres sea-island
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
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    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
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    • D04H1/43835—Mixed fibres, e.g. at least two chemically different fibres or fibre blends
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
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    • D04H1/43838—Ultrafine fibres, e.g. microfibres
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Abstract

本发明提供在低频区域具有优异的吸音性能的层叠无纺布。并且，本发明为一种层叠无纺布，其包含表皮层及基材层，其中，所述表皮层具有无纺布A，所述无纺布A的密度为100～500kg/m3，并由厚度为0.5～2.5mm、透气度为4～40cm3/cm2/s的无纺布形成，所述基材层具有无纺布B，所述无纺布B由单位面积重量200～500g/m2、厚度为5～40mm的无纺布形成。

Description

层叠无纺布
技术领域
本发明涉及层叠而成的无纺布，尤其涉及吸音性优异的无纺布。
背景技术
在汽车、电子制品等中，出于吸音性、隔热性的目的，已在使用无纺布。特别地，在关于汽车用途的方面，为了提高燃油效率，需要轻且薄的无纺布。
专利文献1中公开了一种包含下述层叠无纺布的吸音材料，所述层叠无纺布包含无纺布层(其在表层部由纳米纤维构成)和基底部(其由单纤维直径比纳米纤维大的纤维构成)。
专利文献2中公开了一种吸音材料，其包含由聚酯系纤维的层叠无纺布形成的面材、和作为主要成分的再生毛毡。
现有技术文献
专利文献
专利文献1：日本特开2015-30218公报
专利文献2：日本特开2013-163869公报
发明内容
发明要解决的课题
专利文献1中公开了其中记载的吸音材料在2000Hz的高频区域的吸音系数为85％以上。此外，专利文献2中也公开了其中记载的吸音材料在频率2000～5000Hz下的吸音系数为40％以上。然而，迫切期望低频区域(800～1250Hz)处的吸音性。因此，本发明的课题在于提供在低频区域具有优异的吸音性能的层叠无纺布。
用于解决课题的手段
为了解决上述课题，本申请的发明人进行了深入研究，结果作出了以下这样的发明。
(1)层叠无纺布，其具有表皮层及基材层，其中
所述表皮层具有无纺布A，该无纺布A的密度为100～500kg/m3、厚度为0.5～2.5mm、且透气度为4～40cm3/cm2/s，
所述基材层具有无纺布B，该无纺布B的单位面积重量为200～500g/m2、且厚度为5～40mm。
还有以下优选方式。
(2)如(1)的层叠无纺布，其中，所述无纺布B的厚度为10～40mm。
(3)如(1)或(2)的层叠无纺布，其中，在无纺布A中，以相对于无纺布A整体而言为20～40质量％的量含有单纤维直径为1～5000nm的热塑性纤维。
(4)如(1)～(3)中任一项的层叠无纺布，其硬挺度为300mm以下。
(5)如(1)～(4)中任一项的层叠无纺布，其中，所述无纺布A具有由聚酰胺形成的纤维及/或由聚对苯二甲酸乙二醇酯形成的纤维。
(6)如(1)～(5)中任一项的层叠无纺布，其中，所述无纺布B具有粘合纤维，该粘合纤维的含量相对于所述无纺布B整体而言为10～30质量％。
(7)吸音材料，其具有(1)～(6)中任一项的层叠无纺布。
发明的效果
根据本发明，可得到在低频区域具有优异的吸音性的层叠无纺布。进而，根据本发明的优选方式，可得到柔软性高的层叠无纺布。
具体实施方式
以下，对本发明的实施方式详细地进行说明。
本发明的层叠无纺布具有表皮层及基材层，所述表皮层具有无纺布A，所述无纺布A的密度为100～500kg/m3，所述无纺布A的厚度为0.5～2.5mm，所述无纺布A的透气度为4～40cm3/cm2/s，所述基材层具有无纺布B，所述无纺布B的单位面积重量为200～500g/m2，所述无纺布B的厚度为5～40mm。
即，对本发明的层叠无纺布而言，通过至少将所述表皮层所具有的无纺布A与所述基材层所具有的无纺布B层叠而成，从而得以赋予对800～1250Hz的优异的吸音性。
此处，无纺布A的密度必须为100～500kg/m3。通过使其为100kg/m3以上，表皮层根据声音而发生共振，由此引起所谓的板振动，从而使得低频区域的吸音系数提高。此外，通过使其为500kg/m3以下，从而可成为具有一定柔软性的表皮层。从上述观点考虑，优选为150kg/m3以上，优选为300kg/m3以下。
此外，无纺布A的厚度优选为0.5～2.5mm。当在上述范围内时，得以成为柔软性优异的表皮层。从上述观点考虑，其下限优选为0.6mm，其上限优选为1.6mm以下。
进而，无纺布A的透气度必须为4～40cm3/cm2/s。此处，透气度是指如实施例的项中所述的那样按照JIS L 1096-1999 8.27.1 A法(弗雷泽型(Frazir)法)而测得的值。通过使其为4cm3/cm2/s以上，当声音以一定的流速通过纤维与纤维之间的空隙时，能够利用与空隙周围的纤维材料的空气摩擦将声音高效地转换为热量。此外，能够在不使高频区域的声音反射的情况下使声音通过层叠无纺布内部。另一方面，通过使其为40cm3/cm2/s以下，能够提升低频区域的吸音系数。从上述观点考虑，进一步地，优选为10cm3/cm2/s以上，优选为30cm3/cm2/s以下。
此外，为了增加由空气摩擦导致的能量损失，无纺布A的孔分布也优选在一定的范围内，以细孔径分布度数计，大于0且为10μm以下的孔径分散度为1～20、10～20μm的孔径分散度为15～60是优选的。
此外，无纺布A的单位面积重量优选为100～400g/m2，更优选为130g/m2以上。进一步优选的是150g/m2以上。
作为构成无纺布A的材料，耐热性优异的热塑性树脂是优选的，考虑到获得的容易性、生产率，包含由聚酰胺形成的纤维及/或由聚对苯二甲酸乙二醇酯形成的纤维是优选的。此处，由聚酰胺形成的纤维可以是仅由聚酰胺形成的纤维，也可以在不阻碍本发明的效果的范围内以添加剂等形式包含除聚酰胺以外的成分。此外，由聚对苯二甲酸乙二醇酯形成的纤维可以是仅由聚对苯二甲酸乙二醇酯形成的纤维，也可以在不阻碍本发明的效果的范围内包含除聚对苯二甲酸乙二醇酯以外的成分。
对于无纺布A而言，利用针刺法(needle punch)、水刺(spun lace)法而得到的短纤维无纺布由于容易控制密度、厚度、透气度，故而优选。
在无纺布A中，优选地，以相对于无纺布A整体而言为20～40质量％的量含有由单纤维直径为1～5000nm的热塑性树脂形成的热塑性纤维(以下，有时将该纤维称为纳米纤维)。通过使其为20质量％以上，能够增加无纺布A中的纤维构成根数，由此，得以容易控制无纺布A的密度、透气度。单纤维直径以数均计优选为150nm以上，另一方面，更优选为2000nm以下，进一步优选为700nm以下。
作为无纺布A的构成，可以为由100％纳米纤维形成的构成、将纳米纤维与比纳米纤维粗的纤维(即，单纤维直径大于5000nm的纤维)进行混纤而得到的构成、将纳米纤维层与比纳米纤维粗的纤维的层进行层叠而得到的构成。更优选地，为将纳米纤维层与比纳米纤维粗的纤维的层进行层叠而得到的构成。
此外，也可以为下述构成：准备多片将纳米纤维层与比纳米纤维粗的纤维的层进行层叠而得到的无纺布、并使用低熔点粉末(powder)等将它们贴合而得到的构成。
此外，本发明中的纳米纤维可以是单纤维散乱地分散而成的纳米纤维、单纤维部分结合的纳米纤维、多个单纤维凝聚而成的聚集体(例如，束状的纳米纤维)等具有各种形态的纳米纤维。即，只要为所谓的纤维状形态即可，并不限制纤维的长短、截面形状等。
为了得到纳米纤维，可例举下述方法：由在溶剂中的溶解性不同的2种以上聚合物来制作聚合物合金(polymer alloy)熔融体，所述聚合物合金熔融体中将易溶性聚合物作为海(基质)，将难溶解性聚合物作为岛(畴)的，将聚合物合金熔融体进行纺丝，然后进行冷却固化从而进行纤维化。然后，根据需要实施拉伸及/或热处理，得到聚合物合金纤维，之后由该纤维制成无纺布。然后，用溶剂将易溶解性聚合物除去，由此可得到纳米纤维。
此外，也可将在内部包含相容性差的聚酰胺和聚对苯二甲酸乙二醇酯的纤维制成无纺布，进行针刺、水刺(water jet punch)，分割成聚酰胺和聚对苯二甲酸乙二醇酯，从而进行纳米纤维化。
此外，在不阻碍本发明的效果的范围内，除了无纺布A以外，表皮层还可以具有其他片状物。
接下来，对无纺布B进行说明。无纺布B的单位面积重量为200～500g/m2。通过使单位面积重量为200g/m2以上，可得到具有连续的孔的多孔质的层叠无纺布。此外，通过使单位面积重量为500g/m2以下，可得到轻质且具有柔软性的无纺布。由此，在将层叠无纺布贴附于凹凸部时等情况下，层叠无纺布的追随性好、操作性优异。
此外，无纺布B的厚度为5～40mm。通过使厚度为5mm以上，从而能够在表皮层下方形成具有一定厚度且包含空气的层，能够通过在表皮层与包含空气的层处引起亥姆霍兹共振(Helmholtz Resonance)来吸收低频区域的声音。并且，由于为具有连续孔的多孔质，因此高频区域的吸音性变好。根据上述机制，从不仅低频区域而且高频区域的吸音性进一步提高的观点考虑，无纺布B的厚度优选为10mm以上，更优选为12mm以上。此外，通过使其为40mm以下，从而在汽车等中安装于空隙时等的情况下，作业性变好。无纺布B的厚度的上限更优选为30mm以下。
从生产率、隔热性能的均匀性的观点考虑，无纺布B优选包含热塑性纤维。此外，上述的无纺布B进一步优选含有热塑性粘合纤维。
作为上述的无纺布B中含有的热塑性纤维，可举出聚对苯二甲酸乙二醇酯纤维、聚酰胺6纤维、聚丙烯纤维，其中，从疏水性或耐热性优异、有助于提高耐久性或阻燃性的观点考虑，优选聚对苯二甲酸乙二醇酯纤维。
此外，为了提高层叠无纺布的阻燃性，无纺布B中包含的纤维可使用作为阻燃材料的阻燃聚酯纤维。
无纺布B优选以相对于无纺布B整体而言为5～40质量％的量含有单丝纤度为1.0dtex以下的热塑性纤维。通过使无纺布B以相对于无纺布B整体而言为5质量％以上的量含有单丝纤度为1.0dtex以下的热塑性纤维，可进一步提高吸音性能。另一方面，通过使无纺布B以相对于无纺布B整体而言为40质量％以下的量含有单丝纤度为1.0dtex以下的热塑性纤维，可将细纤度的热塑性纤维的比率抑制在低水平，因此，制作无纺布B时的梳棉工序(card process)中的通过性进一步提高，生产率更为优异。无纺布B更优选以相对于无纺布B整体而言为10质量％以上的量含有单丝纤度为1.0dtex以下的热塑性纤维，更优选以相对于无纺布B整体而言为30质量％以下的量含有单丝纤度为1.0dtex以下的热塑性纤维。
此外，为了提高无纺布B的空气保持性能而提高层叠无纺布的吸音性能，无纺布B优选以相对于无纺布B整体而言为5～30质量％的量含有具有中空结构的热塑性纤维。通过使无纺布B以相对于无纺布B整体而言为5质量％以上的量含有具有中空结构的热塑性纤维，从而无纺布B的空气保持性能进一步提高，层叠无纺布的吸音性能更进一步提高。通过使无纺布B以相对于无纺布B整体而言为30质量％以下的量含有具有中空结构的热塑性纤维，可将中空纤维的比率抑制在低水平，因此，可维持层叠无纺布的优异的隔热性能。另外还能抑制体积变大。无纺布B更优选以相对于无纺布B整体而言为10质量％以上的量含有具有中空结构的热塑性纤维，更优选以25质量％以下的量含有具有中空结构的热塑性纤维。
作为无纺布B中可含有的热塑性粘合纤维的结构，从能够抑制无纺布的热收缩的观点考虑，优选制成芯部由聚对苯二甲酸乙二醇酯形成、鞘部由粘合成分形成的芯鞘结构。
作为粘合成分，没有特别限制，优选使用对苯二甲酸或其酯形成性衍生物、间苯二甲酸或其酯形成性衍生物、低级亚烷基二醇、以及由聚亚烷基二醇及/或其单醚形成的共聚聚酯。
优选以相对于无纺布B整体而言为5～30质量％的量含有热塑性粘合纤维。通过使粘合纤维的含有率为5质量％以上，可将热塑性纤维彼此充分地粘接，可使无纺布B的硬挺度为一定值以上。另一方面，通过使粘合纤维的含有率为30质量％以下，可抑制由热塑性纤维之间的粘接过强而导致的无纺布B变硬，可得到具有更加优异的柔软性的层叠无纺布。
此外，无纺布B中包含的热塑性纤维优选具有卷曲。由此，无纺布B的体积变大，可得到吸音性能、形态保持性优异的层叠无纺布。此外，在梳棉法(carding method)中可被针牢牢地钩住，能够与其他纤维均匀地分散并致密地络合，能够以高收率得到无纺布B。
无纺布B中使用的热塑性纤维的数均纤维长度优选为10～90mm。通过利用粘合纤维将平均纤维长度为10mm以上的热塑性纤维结合，从而无纺布B的硬挺度更加优异，可得到形态保持性更加优异的无纺布B。另一方面，通过使平均纤维长度为90mm以下，从而在具有热塑性纤维和粘合纤维的无纺布B的制造工序(即梳棉法或气流成网法(airlaid method)等纤维分散工序)中，热塑性纤维与粘合纤维均匀地分散并致密地络合，能够具有微细的空隙，可得到吸音性能优异的层叠无纺布。
作为无纺布B的制造方法，可例举以下的方法。将热塑性纤维开纤，或者将根据需要将热塑性粘合纤维混合于热塑性纤维而得到的产物开纤。然后，利用梳棉法或气流成网法得到纤维网。将数片得到的纤维网层叠，进行热处理，由此得到无纺布B。若使用梳棉法或气流成网法，则可得到热塑性纤维与粘合纤维均匀存在的纤维网。热处理可以在比粘合纤维中的粘合成分(低熔点成分)软化或熔融的温度高、且除粘合成分以外的成分熔融的温度下进行。由此，低熔点成分软化或熔融，可牢固地系住热塑性纤维，成为长期形态保持性优异的层叠无纺布。热处理的方法可使用热风干燥机、热风循环式热处理机、红外线加热器、热辊等。
无纺布B的单位面积重量和厚度的调节方法可通过上述的纤维网的层叠工序中的输送速度来确定。通过在热处理工序之前用辊来调节无纺布B的厚度，可得到期望的单位面积重量和厚度。
作为将表皮层与基材层接合的方法，可举出下述方法：将熔点比构成无纺布A及无纺布B的纤维成分低的树脂(例如，聚丙烯等聚烯烃)以粉末形式夹在表皮层与基材层之间，在用加热辊按压的同时将它们进行接合。还可举出下述方法：向基材层以雾状喷射粉末状粘接剂，进而在其上放置表皮层，然后用加热辊进行接合。
接下来，对配合表皮层与基材层而成的层叠无纺布进行说明。
层叠无纺布优选具有优异的柔软性，作为表示柔软性的值的硬挺度优选为300mm以下。若层叠无纺布的柔软性低，则有在弯曲部与层叠无纺布之间产生间隙、褶皱从而导致吸音性能降低的倾向。从上述的观点考虑，硬挺度更优选为150mm以上，另外优选为250mm以下。
此外，在需要消除表面背面的差异的情况下，也可将基材层作为中间层，制成依次为表皮层/中间层/表皮层的结构。
关于层叠无纺布的吸音特性，特别是在800～1250Hz的低频区域可得到高吸音性能，800～1250Hz的平均吸音系数优选为50％以上。若800～1250Hz的平均吸音系数为50％以上，则适合用作汽车等的吸收路面噪声(road noise)的吸音材料。
此外，2000～5000Hz的高频区域的吸音系数也优选为70％以上。
本发明的层叠无纺布适合用作面向汽车、电子设备、住宅等用途的吸音材料。
实施例
以下，基于实施例进一步详细地说明本发明，但本发明并不限定于这些实施例。
(1)基于扫描电子显微镜的无纺布表面观察
针对表层部的无纺布，以1200倍的倍率(日立制作所公司制，扫描电子显微镜(以下称为“SEM”)S-3500NH-7100FA型)观察无纺布表面。
(2)纳米纤维的单纤维直径及纳米纤维的数均单纤维直径
在利用上述的SEM观察无纺布表面时，拍摄所述无纺布表面的照片。从该照片中选取纳米纤维层部分的图像。使用图像处理软件(WinROOF)，以10倍的倍率在同一照片内随机地抽取10处，每处含30根彼此相邻的纳米纤维，对共计300根纳米纤维的单纤维直径进行了测定。此外，求出其算数平均值，将其作为纳米纤维的数均单纤维直径。
(3)单位面积重量
基于JIS L 1913(1998)6.2进行测定。
用钢制尺和刀片从试样中采集3片300mm×300mm的试验片。测定标准状态下的试验片的质量，按照下述式求出每单位面积的质量，并算出平均值。
ms＝m/S
ms：每单位面积的质量(g/m2)
m：试验片的平均质量(g)
S：试验片的面积(m2)。
(4)无纺布A的厚度(mm)
基于JIS L 1096 8.5.1进行测定。厚度测定器使用TECLOCK(株)制的厚度测定器。
(5)无纺布A的密度(kg/m3)
算出单位面积重量/厚度的值，求出每单位容积的质量。
(6)无纺布B的厚度(mm)
用模具尺测定侧面的纵方向上长度作为厚度(mm)。
(7)纤度
基于JIS L 1015(1999)8.5.1A法进行测定。使金属梳从试样中通过，使纤维平行地并丝。将试样载置于毛面纸(所述毛面纸置于切断台上)上，在以适度的力笔直地拉伸试样的状态下压接样板，用安全剃刀等的刀片切成30mm的长度。对纤维进行计数，以300根作为一组，测量其质量，求出表观纤度。根据该表观纤度和另行测得的平衡回潮率，通过下式算出公量纤度(dtex)，求出5次的平均值。
F0＝D’×{(100+R0)/(100+Re)}
F0：公量纤度(dtex)
D’：表观纤度(dtex)
R0：公定回潮率(0.4)
Re：平衡回潮率。
(8)纤维长度
基于JIS L 1015(1999)8.4.1 A法进行测定。用金属梳将试样平行地并丝。用梨形纤维长度分析器制作宽约25cm的短纤维长度分布图。制作时，为了将纤维全部排列在丝绒板上，用夹具夹住无纺布，抽出次数约为70次。在其上放置刻有刻度的赛璐珞板，在方格绘图纸上进行绘图。将用该方法绘制的短纤维长度分布图平均分为50个纤维长度组，测定各分组的边界及两端的纤维长度，两端纤维长度的平均值加上49个边界纤维长度再除以50，算出平均纤维长度(mm)。
(9)强度、伸长率
基于JIS L 1015(1999)8.7.1进行测定。准备长度为30mm的纸，在距离长度方向的两端部5mm的位置处分别沿宽度方向画出分界线。此外，在纸上于宽度方向上以5mm的间隔沿长度方向画出分界线。在空间距离为20mm、于长度方向上沿着每一条分界线缓慢拉伸纤维的状态下，用粘接剂将两端粘贴固定在纸片上，将每个分区作为1个试样。将试样安装于拉伸试验器的夹钳上，在上部夹钳的附近切断纸片，在夹钳间隔为20mm、拉伸速度为20mm/分钟的速度下拉伸，测定负荷(N)及伸长(mm)。根据下式算出拉伸强度(cN/dtex)及伸长率(％)。
Tb＝SD/F0
Tb：拉伸强度(cN/dtex)
SD：断裂时的负荷(cN)(其中，切断时的负荷小于最大负荷时，采用最大负荷。)
F0：试样的公量纤度(dtex)
S＝{(E2-E1)/(L+E1)}×100
S：伸长率(％)
E1：松弛(mm)
E2：切断时的伸长(mm)(其中，切断时的负荷小于最大负荷时，采用最大负荷时的伸长。)
L：夹钳间隔(mm)。
(10)透气度
按照JIS L 1096-1999 8.27.1 A法(弗雷泽型法)进行测定。从试样的5个不同位置采集约20cm×20cm的试验片，使用弗雷泽型试验机，将试验片安装于圆筒的一端(吸气侧)。安装试验片时，将试验片置于圆筒之上，以不堵塞吸气部分的方式从试验片上均等地施加约98N(10kgf)的负荷，防止试验片的安装部中的空气的泄露。安装试验片后，利用变阻器调节吸入风扇使得倾斜型气压计显示125Pa的压力，根据此时的垂直型气压计显示的压力和使用的空气孔的种类，利用试验机附带的表，求出通过试验片的透气量(cm3/cm2/s)，算出5片试验片的平均值。
(11)细孔径分布度数
利用ASTM F316-86中规定的方法进行测定。
作为测定装置，使用了Porous Materials,Inc(美国)公司制“Perm-Porometer”，作为测定试剂，使用了PMI公司制的“ガルヴィック”，气缸压力为100kPa，作为测定模式，以WET UP-DRY UP的条件进行测定。
在由细孔径分布(直方图)得到的间距(级差)为10nm的分布中，求出0～10、10～20的细孔径分布度数(％)的值。需要说明的是，细孔径分布是将y轴设为细孔径分布、x轴设为细孔径的分布图，x轴的范围为0～100nm，将各10nm的间距的度数合计而得到的总度数为100％。
(12)平均吸音系数
按照JIS A 1405：1998来测定垂直入射吸音系数。
从试样中采集3片直径为90mm的圆形试验片。
作为试验装置，使用了电子测器株式会社制的自动垂直入射吸音系数测定器(型号10041A)。将试验片以与金属反射板之间不存在空气层的方式设置于阻抗管的一端。然后，阶段性地向试验片垂直地入射100～5000Hz频率区域的声波，针对该频率的平面波，测定进入试验体中(即，没有返回)的声功率相对于入射声功率之比，并测定吸音系数。测定800、1000、及1250Hz这3点的吸音系数，将得到的值的平均值作为平均吸音系数。
(13)硬挺度
利用JIS L 1096(8.19.1)(2010)中规定的A法(45°悬臂法)，分别以n＝5的方式测定层叠无纺布的任意方向及垂直于上述任意方向的方向的硬挺度，由10个的平均值求出硬挺度(mm)。
[实施例1]
(海岛结构纤维)
分别量取熔融粘度为212Pa·s(262℃、剪切速度121.6sec-1)、熔点为220℃的聚酰胺6(N6)(40质量份)、和重均分子量为12万、熔融粘度为30Pa·s(240℃、剪切速度2432sec-1)、熔点为170℃且光学纯度为99.5％以上的聚L乳酸(60质量份)，并分别供给至下述条件的双螺杆挤出混炼机中，于220℃进行混炼，从而得到聚合物合金片(polymer alloychip)。
螺杆形状：同方向完全啮合型2条螺纹
螺杆：直径为37mm、有效长度为1670mm、L/D＝45.1
混炼部长度为螺杆有效长度的28％
混炼部配置于螺杆有效长度的更靠近排出侧的1/3的范围
中途有3处逆流部
通气口(vent)：2处。
将得到的聚合物合金片供给至短纤维(staple)用纺丝机的单螺杆挤出型熔融装置，以熔融温度为235℃、纺丝温度为235℃(喷嘴面温度220℃)、纺丝速度为1200m/min的条件进行熔融纺丝，得到由聚合物合金形成的纤维。将其进行并丝，然后进行蒸汽拉伸，得到单丝纤度为3.6dtex的丝束。
对由上述聚合物合金的纤维形成的丝束实施卷曲(12个/25mm)，然后切成51mm的短纤维。得到的强度为3.0cN/dtex、伸长率为40％。
(表皮层)
接下来，利用梳棉机进行开纤，以使得成为60g/m2的海岛结构纤维、和60g/m2的平均纤维长度为51mm、单丝纤度为2.2dtex的聚对苯二甲酸乙二醇酯短纤维(东丽(株)“TETORON”(注册商标))这样的两层结构，然后利用交叉铺网机制成纤维网。用水刺机对该纤维网实施加工，得到单位面积重量为120g/m2、厚度为0.8mm的无纺布。
接下来，用1％氢氧化钠水溶液以温度为95℃、浴比为1:40的条件对上述无纺布进行处理，由此将聚乳酸脱海，得到由N6纳米纤维(其单纤维直径为100～250nm、平均纤维直径为150nm)与聚对苯二甲酸乙二醇酯丝形成的单位面积重量为74g/m2、厚度为0.4mm的无纺布1。
进而，在无纺布1的背面载置5g/m2的低熔点粉末，重叠3片并使用130℃的加热辊进行贴合，从而得到无纺布A。无纺布A的厚度为1.2mm、密度为185kg/m3、透气度为21cm3/cm2/s。此外，表皮层中的纳米纤维比率为29质量％。将该无纺布A作为表皮层。
(基材层)
将15质量份的平均纤维长度为35mm、单丝纤度为0.8dtex的聚对苯二甲酸乙二醇酯短纤维(东丽(株)“TETORON”(注册商标))、15质量份的平均纤维长度为51mm、单丝纤度为6.6dtex的中空聚对苯二甲酸乙二醇酯短纤维(东丽(株)“TETORON”(注册商标))、55质量份的平均纤维长度为51mm、单丝纤度为2.2dtex的聚对苯二甲酸乙二醇酯短纤维(东丽(株)“TETORON”(注册商标))作为热塑性纤维；此外，将15质量份的平均纤维长度为51mm、单丝纤度为2.2dtex的聚对苯二甲酸乙二醇酯短纤维的芯鞘复合纤维(鞘成分：低熔点聚对苯二甲酸乙二醇酯(熔点110℃)，芯成分：均聚对苯二甲酸乙二醇酯(熔点255℃)，鞘比率为50质量％，东丽(株)“Safumetto”(注册商标)T9611)作为粘合纤维，以所述的比率进行混纤。
使用梳棉机进行混纤、开纤，成型为均匀的纤维网。接下来，将纤维网层叠以成为规定的厚度，用加压辊进行按压以使得纤维网的厚度成为20mm，同时在具有上下网状传送带的215℃的热处理炉中使纤维之间热熔接，并进行调节以使得单位面积重量成为400g/m2及厚度成为20mm，从而得到无纺布B。将该无纺布B作为基材层。
(层叠无纺布)
以使得先前制作的表皮层(无纺布A)的载置有低熔点粉末的面成为无纺布侧的方式，将表皮层层叠于从加热炉中取出的无纺布B上，在用130℃的加热辊按压的同时将低熔点粉末熔化，从而得到表皮层与基材层接合而成的层叠无纺布。
得到的层叠无纺布的硬挺度为220mm、平均吸音系数为71％，具有非常优异的吸音性和柔软性。
[实施例2]
(表皮层)
除了贴合4片实施例1的无纺布1以外，利用与实施例1相同的方法制作表皮层，得到无纺布A。无纺布A的厚度为1.6mm、密度为185kg/m3、透气度为16cm3/cm2/s。将该无纺布A作为表皮层。
(基材层)
使用与实施例1相同的无纺布B。将该无纺布B作为基材层。
(层叠无纺布)
利用与实施例1相同的接合方法得到层叠无纺布。
得到的层叠无纺布的硬挺度为210mm、平均吸音系数为77％，具有非常优异的吸音性和柔软性。
[实施例3]
(表皮层)
利用梳棉机，将聚酰胺6的区域与多个聚对苯二甲酸乙二醇酯的区域沿长度方向连续排列的割纤复合型短纤维(单丝纤度为3.3dtex、长度为51mm)进行开纤，然后用交叉铺网机制成纤维网。用水刺机对该纤维网实施加工，得到厚度为0.5mm、密度为260kg/m3、透气度为10cm3/cm2/s、单纤维直径为1800～2300nm、平均纤维直径为2000nm的无纺布A。将该无纺布A作为表皮层。
(基材层)
使用与实施例1相同的无纺布B。将该无纺布B作为基材层。
(层叠无纺布)
利用与实施例1相同的接合方法得到层叠无纺布。
得到的层叠无纺布的硬挺度为250mm、平均吸音系数为78％，为高频吸音系数稍差一些的吸音性。
[实施例4]
(表皮层)
在实施例3中使用的无纺布A上载置5g/m2的低熔点粉末，将其2片重叠并使用130℃的加热辊进行贴合，得到无纺布A。该无纺布A的厚度为1.0mm、密度为260kg/m3、透气度为5cm3/cm2/s。将该无纺布A作为表皮层。
(基材层)
使用与实施例1相同的无纺布B。将该无纺布B作为基材层。
(层叠无纺布)
利用与实施例1相同的接合方法得到层叠无纺布。
得到的层叠无纺布的硬挺度为290mm、平均吸音系数为91％，为高频吸音系数稍差一些的吸音性。
[实施例5]
(表皮层)
使用与实施例1相同的无纺布A。将该无纺布A作为表皮层。
(基材层)
将15质量份的平均纤维长度为35mm、单丝纤度为0.8dtex的聚对苯二甲酸乙二醇酯短纤维(东丽(株)“TETORON”(注册商标))、15质量份的平均纤维长度为51mm、单丝纤度为6.6dtex的中空聚对苯二甲酸乙二醇酯短纤维(东丽(株)“TETORON”(注册商标))、55质量份的平均纤维长度为51mm、单丝纤度为2.2dtex的聚对苯二甲酸乙二醇酯短纤维(东丽(株)“TETORON”(注册商标))作为热塑性纤维；此外，将35质量份的平均纤维长度为51mm、单丝纤度为2.2dtex的聚对苯二甲酸乙二醇酯短纤维的芯鞘复合纤维(鞘成分：低熔点聚对苯二甲酸乙二醇酯(熔点110℃)，芯成分：均聚对苯二甲酸乙二醇酯(熔点255℃)，鞘比率为30质量％，东丽(株)“Safumetto”(注册商标)T9611)作为粘合纤维，以所述的比率进行混纤。
使用梳棉机进行混纤、开纤，成型为均匀的纤维网。接下来，将纤维网层叠以成为规定的厚度，将层叠后的纤维网用加压辊按压以使得纤维网的厚度成为20mm，同时在具有上下网状传送带的215℃的热处理炉中使纤维之间热熔接，进行调节以使得单位面积重量成为400g/m2及厚度成为20mm，得到无纺布B。将该无纺布B作为基材层。
(层叠无纺布)
以使得先前制作的表皮层(无纺布A)的载置有低熔点粉末的面成为无纺布面的方式，将表皮层设置于从加热炉中取出的无纺布B上，用130℃的加热辊按压的同时将低熔点粉末熔化，从而得到表皮层与基材层接合而成的层叠无纺布。
得到的层叠无纺布的硬挺度为350mm，平均吸音系数为68％。低频及高频处的吸音系数优异，但由于硬挺度比实施例1的层叠无纺布高，因此略硬，柔软性稍差一些，吸音性良好。
[实施例6]
(表皮层)
接下来，利用梳棉机进行开纤，以使得成为180g/m2的海岛结构纤维、和180g/m2的平均纤维长度为51mm、单丝纤度为2.2dtex的聚对苯二甲酸乙二醇酯短纤维(东丽(株)“TETORON”(注册商标))这样的两层结构，然后利用交叉铺网机制成纤维网。用针刺机对该纤维网实施加工，得到单位面积重量为360g/m2、厚度为0.8mm的无纺布。
接下来，针对上述无纺布，用1％氢氧化钠水溶液以温度为95℃、浴比为1:40的条件进行处理，由此将聚乳酸脱海，得到由N6纳米纤维(其单纤维直径为100～250nm，平均纤维直径为150nm)与聚对苯二甲酸乙二醇酯丝形成的、单位面积重量为252g/m2、厚度为1.8mm的无纺布1。
(层叠无纺布)
利用与实施例1相同的接合方法得到层叠无纺布。
得到的层叠无纺布的硬挺度为200mm、平均吸音系数为71％，为非常良好的吸音性和柔软性。
[实施例7]
(表皮层)
使用了市售的单丝纤度为2.2dtex的纺粘型无纺布(东丽制，型号G2260-1S)。
(层叠无纺布)
利用与实施例1相同的接合方法得到层叠无纺布。
得到的层叠无纺布的硬挺度为坚硬至无法测定的程度。其为平均吸音系数为71％但高频吸音系数稍差一些的吸音性。
[比较例1]
(表皮层)
使用实施例1的无纺布1。无纺布1的厚度为0.4mm、密度为185kg/m3、透气度为64cm3/cm2/s。将该无纺布1作为无纺布A并且作为表皮层。
(基材层)
使用与实施例1相同的无纺布B。将该无纺布B作为基材层。
(层叠无纺布)
利用与实施例1相同的接合方法得到层叠无纺布。
得到的层叠无纺布的硬挺度为230mm、平均吸音系数为41％，为在低频处的吸音系数低的吸音性。
[比较例2]
(表皮层)
利用梳棉机，将单丝纤度为2.2dtex、纤维长度为51mm的聚对苯二甲酸乙二醇酯短纤维(东丽(株)“TETORON”(注册商标))进行开纤，然后用交叉铺网机制成纤维网。用针刺机对该纤维网实施加工，得到厚度为2.9mm、密度为69kg/m3、透气度为142cm3/cm2/s的无纺布A。将该无纺布A作为表皮层。
(基材层)
使用与实施例1相同的无纺布B。将该无纺布B作为基材层。
(层叠无纺布)
利用与实施例1相同的接合方法得到层叠无纺布。
得到的层叠无纺布的硬挺度为170mm、平均吸音系数为38％，为在低频处的吸音系数差的吸音性。
[比较例3]
(表皮层)
利用梳棉机，将单丝纤度为3.3dtex、纤维长度为51mm的聚对苯二甲酸乙二醇酯短纤维(东丽(株)“TETORON”(注册商标))进行开纤，然后用交叉铺网机制成纤维网。用针刺机对该纤维网实施加工，得到厚度为1.2mm、密度为125kg/m3、透气度为200cm3/cm2/s的无纺布A。将该无纺布A作为表皮层。
(基材层)
使用与实施例1相同的无纺布B。将该无纺布B作为基材层。
(层叠无纺布)
利用与实施例1相同的接合方法得到层叠无纺布。
得到的层叠无纺布的硬挺度为150mm、平均吸音系数为21％，为在低频处的吸音系数差的吸音性。
将实施例1～5的层叠无纺布的构成及评价结果总结于表1，将实施例6及7以及比较例1～3的层叠无纺布的构成及评价结果总结于表2。
[表1]
Figure BDA0001402224060000191
[表2]
Figure BDA0001402224060000201

Claims (7)

1.层叠无纺布，其具有表皮层及基材层，其中，
所述表皮层具有无纺布A，所述无纺布A的密度为100～500kg/m3、厚度为0.5～2.5mm、且透气度为4～40cm3/cm2/s，
所述基材层具有无纺布B，所述无纺布B的单位面积重量为200～500g/m2、且厚度为5～40mm，
所述无纺布A是纳米纤维层与比纳米纤维粗的纤维的层的层叠体，
所述无纺布A中，大于0且为10μm以下的孔径分散度为1～20，并且10～20μm的孔径分散度为15～60，
所述无纺布B包含热塑性纤维，
所述热塑性纤维具有卷曲。
2.如权利要求1所述的层叠无纺布，其中，所述无纺布B的厚度为10～40mm。
3.如权利要求1或2所述的层叠无纺布，其特征在于，在无纺布A中，以相对于无纺布A整体而言为20～40质量％的量含有单纤维直径为1～5000nm的热塑性纤维。
4.如权利要求1或2所述的层叠无纺布，其硬挺度为300mm以下。
5.如权利要求1或2所述的层叠无纺布，其中，所述无纺布A具有由聚酰胺形成的纤维及/或由聚对苯二甲酸乙二醇酯形成的纤维。
6.如权利要求1或2所述的层叠无纺布，其中，所述无纺布B还具有粘合纤维，所述粘合纤维的含量相对于所述无纺布B整体而言为5～30质量％。
7.吸音材料，其具有权利要求1～6中任一项所述的层叠无纺布。
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