CN111851085A - 发泡树脂层及合成皮革 - Google Patents

发泡树脂层及合成皮革 Download PDF

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Publication number
CN111851085A
CN111851085A CN202010330963.3A CN202010330963A CN111851085A CN 111851085 A CN111851085 A CN 111851085A CN 202010330963 A CN202010330963 A CN 202010330963A CN 111851085 A CN111851085 A CN 111851085A
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China
Prior art keywords
layer
foamed resin
resin layer
synthetic leather
present
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Pending
Application number
CN202010330963.3A
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English (en)
Inventor
上村知行
高桥进
小山将平
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.)
Sanya Automotive Interior Technology Co Ltd
Honda Motor Co Ltd
Triple A Co Ltd
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Sanya Automotive Interior Technology Co Ltd
Honda Motor Co Ltd
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Application filed by Sanya Automotive Interior Technology Co Ltd, Honda Motor Co Ltd filed Critical Sanya Automotive Interior Technology Co Ltd
Publication of CN111851085A publication Critical patent/CN111851085A/zh
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Abstract

提供重量轻且耐磨耗性优异的合成皮革以及能够提供该合成皮革的发泡树脂层。本发明的发泡树脂层包括聚氯乙烯系树脂和热塑性聚氨酯弹性体。上述的热塑性聚氨酯弹性体优选邵氏A硬度为50~80。上述的发泡树脂层优选表观密度为0.3~0.7g/cm3。上述的发泡树脂层优选平均单元直径为50~250μm。

Description

发泡树脂层及合成皮革
技术领域
本发明涉及发泡树脂层和合成皮革。更具体地说,本发明涉及适合于车辆内部装饰的合成皮革以及被适用于该合成皮革的发泡树脂层。
背景技术
合成皮革作为天然皮革的替代品,或是比天然皮革更具有良好物性的皮革原材料,而被广泛使用。特别是作为汽车等车辆内装材而使用的合成皮革,为了得到天然皮革风格的触感和手感,一般在纤维质的底布(例如无纺布,织物,针织品等)上涂覆以聚氨酯系树脂或聚氯乙烯系树脂为主体的树脂层是众所周知的。
近年来,被用于车辆座椅的合成皮革被要求轻量化。然而,采用了聚氯乙烯系树脂层的传统合成皮革,由于该树脂层的厚度厚,所以重量较重,并不能满足轻量化的要求。
作为以聚氯乙烯系树脂为主体的合成皮革,以聚氯乙烯系树脂为主要成分的发泡树脂层和在该发泡树脂层上涂覆以聚氯乙烯系树脂或聚氨酯系树脂为主要成分的面层的合成皮革是广为人知的(参照专利文献1,2)。另一方面,以聚氨酯系树脂为主体的合成皮革也是众所周知的(参照专利文献3~5)。
现有技术文献
专利文献
[专利文献1]日本专利公布2017-210703号公报
[专利文献2]日本专利公布2016-87867号公报
[专利文献3]日本专利公布2011-214191号公报
[专利文献4]日本专利公布2011-214192号公报
[专利文献5]日本专利公布2006-77349号公报
发明内容
发明所要解决的技术问题
车辆座椅,尤其是用于汽车座椅的合成皮革被要求严格的耐磨性。但是,根据专利文献1和2的合成皮革,虽然可以通过使用聚氯乙烯系树脂作为发泡层来实现轻量化,但是有关耐磨耗性不充分,并不能满足所要求的水平。另外,虽然考虑通过加厚被层叠在聚氯乙烯系发泡树脂层上的非发泡层的厚度来提高耐磨耗性,但在这种情况下重量会变重,形成与轻量化相反的倾向。另外,由于非发泡层的厚膜化导致手感也显著的降低。
同时,以聚氨酯系树脂为主体的专利文献3~5的合成皮革,虽然满足耐磨耗性,但由于非发泡层的厚度较厚,因此并不能满足被要求的轻量化水平。
本发明是鉴于上述的问题而完成的,其目的在于提供了可提供轻量且耐磨性优秀的合成皮革的发泡树脂层。同时,本发明的另一个目的是提供轻量且耐磨性优异的合成皮革。
解决技术问题的技术方案
本发明的发明者们为了达到上述的目的而进行了专心研究,结果发现,根据含有聚氯乙烯系树脂及热塑性聚氨酯弹性体的发泡树脂层,可以提供轻量且耐磨耗性优秀的合成皮革。同时,本发明的发明者们依次具有底布层,发泡树脂层和表面保护层的顺序,对于以底布层和表面保护层作为两端面的层叠体,采用每单位面积的质量,厚度,耐摩擦性以及BLC值分别是特定范围内的层叠体的合成皮革,我们发现它不仅重量轻而且具有优异的耐磨性。本发明则是基于这些知识和见识而完成的。
也就是说,本发明提供了一种含有聚氯乙烯系树脂和热塑性聚氨酯弹性体的发泡树脂层。根据这样的本发明的发泡树脂层,由于能够在保持聚氯乙烯系树脂物性的同时还可实现轻量化,所以能够得到轻量且耐磨耗性优异的合成皮革。
上述的热塑性聚氨酯弹性体的邵氏A硬度优选为50~80。如果上述的邵氏A硬度在上述的所述范围内,则与聚氯乙烯系树脂的相溶性更好。由此,如果上述的邵氏A硬度为50或以上时,则作为上述的发泡树脂层的前驱体的树脂组合物的加工性以及切割性优异,容易形成粒化。同时,如果上述的邵氏A硬度为80或以下时,采用了上述的发泡树脂层的合成皮革的柔软性及耐弯曲性(特别是耐低温弯曲性)则进一步优化。另外,通过压延法获得作为上述的发泡树脂层的前驱体的非发泡树脂层片材时的加工性优异。
上述的发泡树脂层的表观密度优选为0.3~0.7g/cm3。如果上述的表观密度为0.3g/cm3或以上时,采用了上述的发泡树脂层的上述的合成皮革的耐磨耗性则变得更好。当上述的表观密度为0.7g/cm3或以下时,由于重量会变得更轻,因此可以确保充足的厚度,更优异的柔软性。另外,即使上述的表观密度低至0.7g/cm3或以下时,上述的发泡树脂层也能够保持由聚氯乙烯系树脂的混合而产生的强度。并且,通过使上述的表观密度设置在上述的范围内,采用了上述的发泡树脂层的合成皮革的手感则变得更好。
上述的发泡树脂层优选平均单元直径为50~250μm。如果上述的平均单元直径为50μm或以上时,则柔软性会更好。如果上述的平均单元直径为250μm或以下时,则耐磨耗性会变得更好。
上述的发泡树脂层优选具有独立气泡结构。具有这样结构的本发明的发泡树脂层,耐磨耗性及耐弯曲性(特别是耐低温弯曲性)会变得更好。
在上述的发泡树脂层中,相对于上述的聚氯乙烯系树脂100质量份的上述的热塑性聚氨酯弹性体,其含有量为1~50质量份。当上述的含有量为1质量份或以上时,热塑性聚氨酯弹性体的含有量变得更加充分,耐磨耗性及耐弯曲性(特别是耐低温弯曲性)将变得更优异。如果上述的含有量为50质量份或以下时,则能够充分确保聚氯乙烯系树脂的含有量,并且能够更好地发挥聚氯乙烯系树脂的性能。
上述的发泡树脂层,优选还包括增塑剂。一旦含有增塑剂,柔软性会进一步提高,耐弯曲性(特别是耐低温弯曲性)将会提高。
相对于上述的聚氯乙烯系树脂100质量份的上述的增塑剂,其含有量优选为40~90质量份。如果上述的含有量为40质量份或以上时,柔软性及耐弯曲性(尤其是耐低温弯曲性)则会变得更好。如果上述的含有量为90质量份或以下时,则能够抑制增塑剂向发泡树脂层表面的渗透,由于能够较高的维持与邻接层的粘附力,因此耐磨耗性将更加提高。同时,可以更好地发挥聚氯乙烯系树脂以往所具有的性能。另外,由于上述的发泡树脂层包含热塑性聚氨酯弹性体,因此具有优异的柔软性和耐弯曲性(特别是耐低温弯曲性),因此能够将增塑剂的混合量抑制在90质量份或以下。
上述的发泡树脂层优选用于汽车内部装饰的合成皮革。同时,本发明还提供具有上述的发泡树脂层的第一合成皮革。采用了上述的发泡树脂层的合成皮革,重量轻且耐磨性优异。
上述的第一合成皮革优选以该顺序具备包含了底布层,上述的发泡树脂层和聚氨酯系树脂的表皮层,上述的底布层和上述的发泡树脂层通过以聚氯乙烯系树脂作为主要成分的粘附层进行接合。具有这样结构的上述的第一合成皮革,包含热塑性聚氨酯弹性体的发泡树脂层和包含聚氨酯系树脂的表皮层的粘附力良好,并且包含聚氯乙烯系树脂的发泡树脂层通过以聚氯乙烯系树脂作为主要成分的粘附层与底布层进行接合,由于各层之间的粘附力特别优异,所以很难发生层间的偏差,耐磨耗性则变得极好。
同时,本发明是一种合成皮革,其依次具有底布层,发泡树脂层和位于最表面的表面保护层,包括将上述的底布层和上述的表面保护层位于两端面的层叠体。上述的层叠体在每单位面积的质量为300~500g/m2,厚度为1.0~1.3mm,JIS L0849中所规定的对摩擦的染色牢度试验中,作为负荷1kg,在上述的表面保护层一侧进行3万往返的摩擦试验时,上述的表面保护层的下层提供第二合成皮革,并处于不露出的状态,BLC值为4.0~6.0。具有这样结构的上述的第二合成皮革,重量轻且耐磨性优异。同时,耐弯曲性(特别是耐低温弯曲性)及手感也相当好。在上述的合成皮革中,上述的发泡树脂层优选本发明的发泡树脂层。
发明效果
根据本发明的发泡树脂层,能够提供轻量且耐磨耗性优异的合成皮革。并且,根据本发明的发泡树脂层,可以提供手感及耐弯曲性(特别是耐低温弯曲性)优异的合成皮革。同时,本发明的合成皮革轻量且耐磨耗性优异。并且,本发明的合成皮革在手感及耐弯曲性(特别是耐低温弯曲性)方面优异。
附图说明
图1是显示本发明的合成皮革的一个实施方式的概略图(正面截面图)。
具体实施方式
〔发泡树脂层〕
本发明的发泡树脂层至少包括聚氯乙烯系树脂和热塑性聚氨酯弹性体。上述的聚氯乙烯系树脂及上述的热塑性聚氨酯弹性体可以分别仅使用一种,也可以使用两种以上。
上述的聚氯乙烯系树脂是将氯化乙烯或偏氯乙烯作为必需的单体(单体)成分所构成的聚合物。也就是说,在分子中(1分子中)至少包含来自氯化乙烯或偏氯乙烯的构成单位的聚合物。
作为上述的聚氯乙烯系树脂的实例,可以列举出属于氯化乙烯均聚物的聚氯乙烯,属于偏氯乙烯均聚物的聚偏氯乙烯,氯化乙烯或偏氯乙烯和其他单体形成的聚合物,氯化聚氯乙烯,氯化聚烯烃等。作为上述的氯化聚烯烃的实例,可以举出氯化聚乙烯,氯化聚丙烯等。
作为上述的共聚物的实例,可以列举出氯乙烯-乙酸乙烯酯共聚物,氯乙烯-乙烯共聚物,氯乙烯-丙烯共聚物,氯乙烯-苯乙烯共聚物,氯乙烯-异丁烯共聚物,氯乙烯-偏氯乙烯共聚物,氯乙烯-氨基甲酸乙酯共聚物,氯乙烯-丁二烯共聚物,氯乙烯-异戊二烯共聚物,氯乙烯-氯化丙烯共聚物,氯乙烯-马来酸酯共聚物或氯乙烯-(甲基)丙烯酸酯共聚物等的氯乙烯-乙烯基酯类共聚物,氯乙烯-丙烯腈共聚物,氯乙烯-乙烯基醚共聚物,氯乙烯-苯乙烯-马来酸酐三元共聚物,氯乙烯-苯乙烯-丙烯腈三元共聚物,氯乙烯-偏氯乙烯-乙酸乙烯酯三元共聚物,乙烯-乙酸乙烯酯-氯乙烯共聚物等。作为上述的共聚物的实例,可以列举出嵌段共聚物,无规共聚物,接枝共聚物等。
作为上述的聚氯乙烯系树脂,其中也优选聚氯乙烯(氯乙烯均聚物)。
可以通过众所周知或惯用的聚合方式来获得上述的聚氯乙烯系树脂。作为上述的聚氯乙烯系树脂的聚合方法,虽然没有被特别限定,但可以列举出乳液聚合,悬浮聚合,本体聚合,溶液聚合等。其中,优选通过乳液聚合或悬浮聚合方式所获得的聚氯乙烯系树脂。
有关上述的聚氯乙烯系树脂的平均聚合度(遵循JIS K6721),虽然没有被特别的限定,但优选为1100~3500,更优选为1200~3000,更进一步优选为1300~2800。如果上述的平均聚合度是1100或以上的话,则耐磨耗性及耐弯曲性(特别是耐低温弯曲性)会变得更好。如果上述的平均聚合度是4000或以下的话,通过压延法对作为本发明发泡树脂层的前驱体的未发泡树脂片材进行成型时的加工性则变得更好。
有关上述的聚氯乙烯树脂的平均粒径,虽然没有被特别限定,但优选为0.1~5μm,更优选为0.2~4μm。如果上述的平均粒径是0.1μm或以上的话,则压延加工时的生产性良好。如果上述的平均粒径是5μm或以下的话,则向热塑性聚氨酯弹性体粒子的氯化乙烯组合物的分散性良好。另外,平均粒径是通过激光衍射/散射法测量的值。
上述的热塑性聚氨酯弹性体(TPU)由硬质相(硬段)和软质相(软段)组成。上述的热塑性聚氨酯弹性体通常通过使聚异氰酸酯,长链多元醇,扩链剂和根据需要使其他的异氰酸酯反应性化合物起反应而得到。
上述的聚异氰酸酯是分子内具有2个以上异氰酸酯基的化合物。作为上述的聚异氰酸酯的实例,可以列举出脂肪族聚异氰酸酯,脂环族聚异氰酸酯,芳香族聚异氰酸酯,芳香脂肪族聚异氰酸酯等。作为上述的聚异氰酸酯,还包括上述的脂肪族聚异氰酸酯,脂环族聚异氰酸酯,芳香族聚异氰酸酯及/或芳香脂肪族聚异氰酸酯的二聚物或三聚物,反应生成物或聚合物(例如,二苯基甲烷二异氰酸酯的二聚物和三聚物,三羟甲基丙烷和甲苯二异氰酸酯的反应生成物,三羟甲基丙烷和六亚甲基二异氰酸酯的反应生成物,聚亚甲基聚苯异氰酸酯,聚醚聚异氰酸酯,聚酯纤维聚异氰酸酯等)等。上述的聚异氰酸酯可以仅使用一种,也可以使用两种以上。
作为上述的长链多元醇的实例,可以列举出聚醚多元醇,聚酯多元醇,聚碳酸酯多元醇,聚烯烃多元醇,聚丙烯多元醇等。长链多元醇的数平均分子量通常是500或以上,优选为500~10000,更优选为600~6000,更进一步优选为800~4000。上述的长链多元醇可以仅使用一种,也可以使用两种以上。
作为上述的扩链剂,可以使用通常被用于制造热塑性聚氨酯弹性体的扩链剂,例如低分子量的多元醇,多胺等。扩链剂的分子量通常小于500,优选为300或以下。上述的扩链剂可以仅使用一种,也可以使用两种以上。
上述的热塑性聚氨酯弹性体的邵氏A硬度优选为50~80,更优选为55~75如果上述的邵氏A硬度在上述的的所述范围内,则与聚氯乙烯系树脂的相溶性更好。由此,如果上述的邵氏A硬度为50或以上时,则作为本发明发泡树脂层的前驱体的树脂组合物的加工性以及切割性优异,容易形成粒化。同时,如果上述的邵氏A硬度为80或以下时,采用了本发明发泡树脂层的合成皮革的柔软性及耐弯曲性(特别是耐低温弯曲性)则进一步优化。另外,通过压延法获得作为本发明发泡树脂层的前驱体的未发泡树脂片材时的加工性优异。
上述的热塑性聚氨酯弹性体的熔点优选为140~200℃,更优选为150~180℃。如果上述的熔点是140℃或以上的话,则发泡树脂层的形成变得良好,能够保持作为汽车内部装饰材料而被使用时的耐热性。如果上述的熔点是200℃或以下的话,则与聚氯乙烯树脂的相溶性良好,压延加工性良好。
相对于上述的聚氯乙烯树脂100质量份的上述热塑性聚氨酯弹性体,其含有量优选为1~50质量份,更优选为5~45质量份,更进一步优选为8~35质量份。当上述的含有量为1质量份或以上时,热塑性聚氨酯弹性体的含有量变得更加充分,耐磨耗性及耐弯曲性(特别是耐低温弯曲性)将变得更优异。如果上述的含有量为50质量份或以下时,则能够充分确保聚氯乙烯系树脂的含有量,并且能够更好地发挥聚氯乙烯系树脂的性能。同时,通过压延法对未发泡树脂片材的加工性更好。
本发明的发泡树脂层优选还包括塑性剂。一旦含有增塑剂,本发明的发泡树脂层以及合成皮革的柔软性则会进一步提高,耐弯曲性(特别是耐低温弯曲性)也将会提高。
上述的增塑剂可以使用在聚氯乙烯系树脂中所使用的一般材料。作为上述增塑剂的实例,可以列举出邻苯二甲酸二(2-乙基己)酯,邻苯二甲酸二正辛酯,邻苯二甲酸二异辛酯,邻苯二甲酸二壬酯,邻苯二甲酸二异壬酯,邻苯二甲酸二异癸酯,邻苯二甲酸C9-11混合烷基邻苯二甲酸丁基苄酯,间苯二甲酸二异辛酯等的芳香族羧酸盐;己二酸二异辛酯,己二酸二异癸酯,癸二酸二(2-乙基己)酯等的脂肪族羧酸盐;甲基丙烯酸三丁基锡酯(TBTM),偏苯三酸三辛酯(TOTM)等的偏苯三甲酸酯;二甘醇二苯甲酸酯,二丙二醇二苯甲酸酯,聚氧丙二醇二苯甲酸酯,聚氧乙烯乙二醇二苯甲酸酯等的二苯甲酸盐;磷酸三甲酚酯,磷酸二甲酚酯等的磷酸酯;氯化石蜡,氯化脂肪酸酯等的含卤代系化合物;环氧大豆油,环氧亚麻籽油,环氧红花油,环氧蓖麻油等的含环氧基脂肪酸;聚酯等。上述的增塑剂可以仅使用一种,也可以使用两种以上。
上述的增塑剂的含量相对于上述的聚氯乙烯系树脂100质量份的上述增塑剂,其含有量优选为40~90质量份,更优选为60~90质量份。如果上述的含有量是40质量份或以上时,柔软性及耐弯曲性(特别是耐低温弯曲性)则会变得更好。如果上述的含有量为90质量份或以下时,则能够抑制增塑剂向发泡树脂层表面的渗透,由于能够较高的维持与邻接层的粘附力,因此耐磨耗性将更加提高。同时,可以更好地发挥聚氯乙烯系树脂以往所具有的性能。另外,由于本发明的发泡树脂层包含热塑性聚氨酯弹性体,因此具有优异的柔软性和耐弯曲性(特别是耐低温弯曲性),因此能够将增塑剂的混合量抑制在90质量份或以下。
本发明的树脂发泡体优选还包括填料。通过含有填料,可以提高本发明的发泡树脂层的硬度,也可使耐久性得以提高。
作为上述的填料,虽然没有被特别限定,但是可以列举出碳酸钙,磷酸钙,亚磷酸钙,硫酸钙,亚硫酸钙,硼酸钙,硅酸钙,氧化钙,氢氧化钙,碳酸镁,氧化镁,氢氧化镁,硫酸钡,氢氧化铝,氧化钛,氧化锑,二氧化硅,硼酸锌,锡酸锌,羟基锡酸锌,明矾,滑石,高岭土,黏土,石棉,合成沸石,水滑石等的无机填料。上述的填料可以仅使用一种,也可以使用两种以上。
上述的填料的含量相对于上述的聚氯乙烯系树脂100质量份的上述填料,其含有量优选为1~100质量份,更优选为5~30质量份。如果上述的含有量是1质量份或以上的话,则树脂发泡层更容易形成独立气泡结构。同时,还提高了发泡树脂层的硬度和耐久性。如果上述的含有量是100质量份或以下的话,则可以不影响耐弯曲性,耐磨耗性。
本发明的发泡树脂层可以在不损害本发明效果的范围内,也可含有上述的各成分以外的其他成分。作为上述的其他成分,可以列举出被包含在众所周知或惯用的发泡体中的成分。作为上述的其他成分,可以列举出聚氯乙烯系树脂及热塑性聚氨酯弹性体以外的树脂,加工助剂,增强剂,阻燃剂,着色剂(染料,颜料等),消泡剂,表面调整剂,交联剂,硅烷偶联剂,触变剂,增粘剂,蜡,热稳定剂等稳定剂,耐光色牢度提高剂,紫外线吸收剂,耐风化剂,荧光增白剂,导电剂,抗静电剂,透湿性改善剂,防水剂,防油剂,发泡剂,含结晶水化合物,吸水剂,吸湿剂,消臭剂,发泡稳定剂,防雾剂,防霉剂,防腐剂,藻类控制剂,颜料分散剂,惰性气体,爽滑剂,润滑剂,防粘连剂,水解抑制剂,中和剂,天然油,合成油,增稠剂等。上述的其他成分可以仅使用一种,也可以使用两种以上。
本发明的发泡树脂层优选表观密度为0.3~0.7g/cm3,更优选为0.4~0.5g/cm3。如果上述的表观密度是0.3g/cm3或以上的话,采用了本发明的发泡树脂层的合成皮革的耐磨性则变得更好。当上述的表观密度是0.7g/cm3或以下时,由于重量会变得更轻,因此可以确保足够的厚度,更优异的柔软性。另外,即使上述的表观密度低至0.7g/cm3或以下,本发明的发泡树脂层也能够保持由聚氯乙烯系树脂的混合而产生的强度。并且,通过将上述的表观密度设置在上述的范围内,采用了本发明的发泡树脂层的合成皮革的手感则变得更好。上述的表观密度是将发泡树脂层切成30cm方形的大小,厚度为n=5的平均值,计算出所剪切的发泡树脂层的体积,根据该发泡树脂层的质量和体积来计算。
本发明的发泡树脂层优选平均单元直径为50~250μm,更优选为55~160μm,更进一步优选为60~100μm。如果上述的平均单元直径是50μm或以上的话,则柔软性更好。如果上述的平均单元直径是250μm或以下的话,则耐磨耗性会变得更好。
本发明的发泡树脂层优选最大单元直径为80~400μm,更优选为90~250μm,更进一步优选为100~200μm。如果上述的最大单元直径为80μm或以上的话,则柔软性会更好。如果上述的最大单元直径在400μm或以下的话,则耐磨耗性会变得更好。
本发明的发泡树脂层的发泡倍率优选为1.3~3.0倍,更优选为1.7~2.2倍。如果上述的发泡倍率为1.3倍或以上的话,由于重量会变得更轻,因此可以确保足够的厚度,更优异的柔软性。另外,即使上述的发泡倍率为1.3倍或以上,本发明的发泡树脂层也能够保持由聚氯乙烯树脂的混合而产生的强度。如果上述的发泡倍率为3.0倍或以下的话,采用了本发明的发泡树脂层的合成皮革的耐磨性则会变得更好。并且,通过将上述的发泡倍率设置在上述的范围内,采用了本发明的发泡树脂层的合成皮革的手感则变得更好。
上述的发泡倍率如下所求。将发泡树脂层厚度方向截面的电子显微镜照片(50倍)通过扫描仪读入电脑内,将发泡部分涂成白色后,将发泡部分和非发泡部分的颜色实施二值化为白色和黑色,通过积分计算白色点部分。并且,使用以下公式求出上述的泡沫度。
发泡倍率=(发泡部分的面积+非发泡部分的面积)/非发泡部分的面积
本发明的发泡树脂层的气泡结构虽然可以是独立气泡结构,半独立半连续气泡结构,连续气泡结构的任意一种,但是最好是具有独立气泡结构的。在具有独立气泡结构的情况下,耐磨耗性和耐弯曲性(特别是耐低温弯曲性)则会变得更好。
本发明的发泡树脂层通过含有聚氯乙烯系树脂和热塑性聚氨酯弹性体,能够得到轻量且耐磨耗性优异的合成皮革。并且,特别是通过将聚氯乙烯系树脂的平均聚合度,热塑性聚氨酯弹性体的含有量,增塑剂的含有量,发泡倍率分别调整为优选范围来优化发泡树脂层的硬度平衡,从而将采用了该发泡树脂层的合成皮革可以在轻量化的同时,将耐磨耗性及耐弯曲性(特别是耐低温弯曲性)变得极佳。
根据JIS K7312所测量的本发明的发泡树脂层的ASKER C硬度,虽然没有被特别限定,但是优选为25~55,更优选为30~45,更进一步优选为35~40。如果上述的ASKER C硬度在25或以上的话,则合成皮革的耐磨性会更好。如果上述的ASKER C硬度在55或以下的话,合成皮革的手感则会变得更好,并且耐弯曲性(特别是耐低温弯曲性)会越发的变得更好。
有关本发明的发泡树脂层的厚度,虽然没有被特别限定,但优选为200~650μm,更优选为250~600μm,更进一步优选为300~500μm。如果上述的厚度在200μm或以上的话,则耐磨耗性会变得更好。如果上述的厚度在650μm或以下的话,则会被更加的轻量化。
本发明的发泡树脂层可以如下制作。首先,将聚氯乙烯系树脂,热塑性聚氨酯弹性体以及根据需要将其他树脂加热熔融混合,并且根据需要添加增塑剂,填料,上述的其他成分,发泡剂,泡沫促进剂,单元调整剂等添加剂进行搅拌,然后冷却后制作树脂组合物(颗粒等)。上述的树脂组合物中的聚氯乙烯系树脂,热塑性聚氨酯弹性体等各种成分的优选含有量分别与上述的本发明发泡树脂层中的含有量相同。
作为上述的发泡剂的实例,可以列举出超临界流体;碳酸铵,碳酸氢铵,碳酸氢钠,亚硝酸铵,硼氢化钠,叠氮化物类等的无机系发泡剂;偶氮系发泡剂,亚硝系发泡剂,酰肼系发泡剂,碳酰肼系发泡剂,三嗪系发泡剂等的有机系发泡剂;异丁烷,戊烷等加热膨胀性化合物;上述的加热膨胀性化合物被封装在由聚偏氯乙烯,聚丙烯腈,聚(甲基)丙烯酸酯等热塑性树脂构成的微胶囊中的热膨胀性微粒子(热膨胀性微胶囊)等。上述的发泡剂可以仅使用一种,也可以使用两种以上。
作为上述的偶氮系发泡剂的实例,可以列举出偶氮二甲酰胺,偶氮二异丁腈,重氮氨基苯,偶氮二甲酸二乙酯,偶氮二甲酸二异丙酯,偶氮二异丁腈(六氢苄腈)等。作为上述的亚硝系发泡剂的实例,可以列举出N,N’-二甲基-N,N’-二硝基对苯二甲酸铵,N,N’-二硝基五亚甲基四胺等。作为上述酰肼系发泡剂的实例,可以列举出苯磺酰肼,对甲苯磺酰肼,3,3’-二砜肼苯砜,甲苯二磺酰腙,硫双(苯磺酰肼),p,p’-氧双(苯磺酰肼)等。作为上述的碳酰肼系发泡剂的实例,可以列举出对甲苯磺酰氨基脲,4,4’-氧双(苯磺酰氨基脲)等。作为上述三嗪系发泡剂的实例,可以列举出三肼基三嗪,1,3-双(邻联苯三嗪)等。
本发明的发泡树脂层优选是采用发泡剂制作的,尤其优选采用热膨胀性微胶囊制作而成的。在使用发泡剂的情况下,与通过机械搅拌等使起泡的方法相比,发泡树脂层中的单元直径更均匀。另外,在使用热膨胀性微胶囊的情况下,可以制作具有更微小且均匀的单元直径的发泡树脂层。
有关上述树脂组合物中的发泡剂的含有量,虽然没有被特别限定,但是根据希望得到的发泡树脂层的用途适当地选择,例如,对于聚氯乙烯系树脂100质量份,优选为0.1~10质量份,更优选为1~5质量份。
然后,由上述的树脂组合物制作发泡树脂层。例如,在熔融或溶解含有发泡剂的上述的树脂组合物后,涂在后述的非发泡树脂层或剥离片材等基材上形成涂膜,之后使用烘箱等加热装置,根据需要进行加压并进行热处理,使发泡剂起泡,在含有溶剂的情况下使溶剂挥发,形成发泡树脂层。上述的树脂组合物,可以以众所周知或惯用的方法进行涂敷,例如包括逆辊涂敷法,辊式涂敷法,模具涂敷法,线辊涂敷法,刀具涂敷法等。另外,作为其他方法,并不是将树脂组合物涂在基材上,例如不伴随基材而以片状加工而形成未发泡树脂片材,之后使用烘箱等加热装置,根据需要一边加压一边进行热处理,使发泡剂起泡,在含有溶剂的情况下使用溶剂也可以使溶剂挥发,形成发泡树脂层。上述的未发泡树脂片材的成形方法可以通过众所周知或惯用的方法进行,但是从容易由高粘度的树脂组合物制成片材化,以及容易生产宽的合成皮革的观点来看,最好是压延法。
本发明的发泡树脂层能够提供轻量且耐磨耗性优异的合成皮革,因此优选用于合成皮革,更优选用于车辆内部装饰用合成皮革(特别是用于汽车内部装饰用合成皮革),更进一步优选用于车辆座椅用合成皮革(特别是用于汽车座椅用合成皮革)。
[合成皮革]
具有本发明的发泡树脂层的合成皮革有时被称为“本发明的第一合成皮革”。采用了本发明的发泡树脂层的本发明的第一合成皮革,重量轻且耐磨耗性优异。同时,耐弯曲性(特别是耐低温弯曲性)及手感也同样很好。
本发明的第一合成皮革优选以该顺序具备底布层,本发明的发泡树脂层和表皮层。另外,所谓上述的底布层和上述的发泡树脂层最好是通过粘附层进行接合。
另外,该合成皮革依次具有底布层,发泡树脂层和表面保护层,包括将上述的底布层及上述的表面保护层设置在两端面上的层叠体,上述的层叠体在每单位面积的质量为300~500g/m2,厚度为1.0~1.3mm,JIS L0849中所规定的对摩擦的染色牢度试验中,作为负荷1kg,在上述的表面保护层一侧进行3万往返的摩擦试验时,上述的表面保护层的下层处于不露出的状态,有时将BLC值为4.0~6.0的合成皮革称为“本发明的第二合成皮革”。具有这样结构的上述的第二合成皮革,重量轻且耐磨性优异。同时,耐弯曲性(特别是耐低温弯曲性)及手感也相当好。
在本发明的第二合成皮革中,发泡树脂层优选为本发明的发泡树脂层。同时,本发明的第二合成皮革优选由上述的底布层和上述的发泡树脂层通过粘附层进行接合。另外,本发明的第二合成皮革优选在上述的发泡树脂层和上述的表面保护层之间具有表皮层。
另外,在本说明书中,有时将本发明的第一合成皮革和本发明的第二合成皮革总称为“本发明的合成皮革”。
图1显示出了本发明的合成皮革的一个实施方式。如图1所示,本发明的合成皮革1是依次具备底布层11,本发明的发泡树脂层13,表皮层14和位于合成皮革1的最表面的表面保护层15。底布层11和发泡树脂层13通过粘附层12进行接合。
本发明的合成皮革中的上述的底布层,可以采用织物,针织品,无纺布等纤维质布帛或天然皮革等纤维质基材。构成纤维质布帛的纤维的种类虽然并没有被特别限定,但可以列举出聚酯系树脂,聚酰胺系树脂,聚丙烯腈系树脂,聚烯烃系树脂,聚乙烯醇等合成纤维;棉,麻等天然纤维;人造丝,短纤维,醋酸等再生纤维;半合成纤维等。上述的纤维可以仅使用一种,也可以使用两种以上。其中,从强度和加工性更优秀的观点来看,由合成纤维构成的针织品,特别是由聚酯纤维构成的针织品比较好。上述的底布层可以是单层也可以是多层。
有关上述的底布层的重量,虽然没有被特别限定,但是优选为100~300g/m2,更优选为150~200g/m2。如果上述的重量在100g/m2或以上的话,则作为汽车内部装饰材料,可以得到充分的强度。如果上述的目录在300g/m2或以下的话,则可以作为本发明的合成皮革来实施获得所希望的轻量化。
本发明的合成皮革中的上述的粘附层是用于给予上述的底布层和上述的发泡树脂层的粘附性的层。作为形成上述的粘附层的胶粘剂的实例,虽然没有被特别限定,但可以列举出聚氯乙烯系胶粘剂,聚氨酯系胶粘剂,环氧树脂系胶粘剂,聚酯系胶粘剂,橡胶系胶粘剂,丙烯酸树脂系胶粘剂,脲醛树脂系胶粘剂,酚醛树脂系胶粘剂,三聚氰胺树脂系胶粘剂等。其中,优选为聚氯乙烯系胶粘剂。因此,上述的粘附层优选含有以聚氯乙烯系树脂为主要成分(即,含有以聚氯乙烯系树脂作为胶粘成分)。以聚氯乙烯系树脂作为主要成分的粘附层,能够进一步提高上述的底布层与包含聚氯乙烯系树脂的本发明的发泡树脂层的粘附力。由此,较难发生底布层和发泡树脂层之间的偏差,耐磨耗性极为良好。
作为上述粘附层中的聚氯乙烯系树脂,可以列举出作为包含在上述本发明的发泡树脂层中的聚氯乙烯系树脂进行了举例和说明。作为上述的聚氯乙烯树脂,优选聚氯乙烯。上述的聚氯乙烯树脂可以仅使用一种,也可以使用两种以上。
上述的粘附层的一部分也可以包含在上述的底布层中。通过部分浸渍,上述的底布层和本发明的发泡树脂层的粘接性则变得更好。
上述的粘附层的每单位面积的质量优选为10~50g/m2,更优选为15~30g/m2。如果上述的质量在10g/m2或以上的话,则不仅底布层和发泡树脂层的附着性更好,耐磨耗性也更好。如果上述的质量在50g/m2或以下的话,则本发明的合成皮革会更加轻量化。
本发明的合成皮革中的上述的表皮层,从耐磨耗性进一步提高的观点来看,是非发泡树脂层。上述的表皮层优选含有聚氨酯系树脂。包含聚氨酯系树脂的表皮层与包括热塑性聚氨酯弹性体的本发明的发泡树脂层之间的粘附力更好。由此,表皮层和发泡树脂层之间的层间的偏差更难发生,耐磨耗性极其良好。同时,本发明的合成皮革的手感则变得更好。上述的表皮层(非发泡树脂层)既可以是单层也可以是多层。
上述的聚氨酯系树脂通常是通过使异氰酸酯,长链多元醇,扩链剂和根据需要使其他的异氰酸酯反应性化合物起反应而得到的。上述的聚异氰酸酯,长链多元醇和扩链剂分别作为包含在上述本发明的发泡树脂层中的热塑性聚氨酯弹性体的构成成分进行了举例和说明。上述的聚异氰酸酯,长链多元醇及扩链剂可以分别仅使用一种,也可以使用两种以上。
作为上述的长链多元醇,其中也优选聚碳酸酯多元醇。也就是说,能够包含在上述的表皮层中的聚氨酯系树脂优选为聚碳酸酯系聚氨酯树脂。通过采用了聚碳酸酯系聚氨酯树脂,使本发明的合成皮革的耐磨耗性得到进一步提高。
上述的表皮层中的聚氨酯系树脂优选为水性聚氨酯系树脂。即,上述的聚氨酯系树脂优选为水性聚碳酸酯系聚氨酯树脂。通过具有这样的结构,使其耐磨性更加优异,并且,对于来自皮脂成分中的油酸的耐受性(抗油酸性)也很优异。另外,由于不使用有机溶剂,所以也有助于降低环境负荷。
有关上述表皮中的聚氨酯系树脂(特别是聚碳酸酯系聚氨酯树脂)的含有比例,虽然没有被特别限定,但是相对于上述表皮层的总量100质量份,优选为30质量份或以上,更优选为50质量份或以上。如果上述的含有比例为50质量份或以上,则与本发明的发泡树脂层之间的粘附力较高,本发明的合成皮革的耐磨耗性则变得更好。
上述的表皮层也可以在不损害本发明效果的范围内包含聚氨酯系树脂以外的其他成分。作为上述的其他成分,可以举例说明可以包含上述的本发明的树脂发泡层的其他成分。上述的其他成分可以仅使用一种,也可以使用两种以上。
有关上述的表皮层的厚度,虽然没有被特别限定,但优选为10~100μm,更优选为20~40μm。如果上述的厚度是10μm或以上的话,则合成皮革的耐磨耗性会进一步提高。如果上述的厚度是100μm或以下的话,则本发明的合成皮革则会更加的轻量化。
本发明的合成皮革中的上述的表面保护层,是本发明的合成皮革中形成最表面的一层,是保护上述的表皮层,发泡树脂层等内部层不受摩擦等的保护层,使本发明的合成皮革的耐磨性得到进一步的提高。
上述的表面保护层优选包括聚氨酯系树脂。含有聚氨酯系树脂的表面保护层在与含有聚氨酯系树脂的情况下的上述表皮层的粘附性更加优良。由此,表面保护层和表皮层之间的层间的偏差较难发生,耐磨耗性极为良好。同时,本发明的合成皮革的手感也变得更好。
上述的聚氨酯系树脂通常是通过使聚异氰酸酯,长链多元醇,扩链剂和根据需要使其他的异氰酸酯反应性化合物起反应而得到的。上述的聚异氰酸酯,长链多元醇和扩链剂分别作为包含在上述本发明的发泡树脂层中的热塑性聚氨酯弹性体的构成成分进行了举例和说明。上述的聚异氰酸酯,长链多元醇及扩链剂可以分别仅使用一种,也可以使用两种以上。
作为上述的长链多元醇,其中也优选聚碳酸酯多元醇。也就是说,能够包含在上述的表面保护层中的聚氨酯系树脂优选为聚碳酸酯系聚氨酯树脂。通过采用了聚碳酸酯系聚氨酯树脂,使本发明的合成皮革的耐磨耗性得到进一步提高。
上述的表面保护层中的聚氨酯系树脂优选为水性聚氨酯系树脂。也就是说,上述的聚氨酯系树脂优选为水性聚碳酸酯系聚氨酯树脂。通过具有这样的结构,与包含水性聚氨酯系树脂的情况下的上述表皮层的粘附性变得更好,耐磨耗性也越发的优异,而且,耐油酸性也更出色。另外,由于不使用有机溶剂,所以也有助于降低环境负荷。
有关上述的表面保护层中的聚氨酯系树脂(特别是聚碳酸酯系聚氨酯树脂)的含有比例,虽然没有被特别限定,但相对于上述的表面保护层的总量100质量份,优选为60质量份或以上,更优选为90质量份或以上。如果上述的含有比例在60质量份或以上,本发明的合成皮革的耐磨性则变得非常好。上述的含有比例也可以是100质量份。
上述的表面保护层中的聚氨酯系树脂(特别是水性聚碳酸酯系聚氨酯树脂)优选通过碳化二亚胺系交联剂的交联。作为上述的碳化二亚胺系交联剂的实例,可以列举出二环己基甲烷碳二亚胺,二环己基碳二亚胺,四甲基二甲苯碳二亚胺,尿素改性碳二亚胺等。作为上述的碳化二亚胺系交联剂,优选水性碳化二亚胺系交联剂。上述的碳化二亚胺系交联剂可以仅使用一种,也可以使用两种以上。
上述的表面保护层中,特别是优选水性聚碳酸酯系聚氨酯树脂通过水性碳化二亚胺系交联剂的交联。上述的表面处理层成为耐油酸性高的交联膜,除了耐磨耗性之外,还具有优良的耐油酸性,因此本发明的合成皮革即使对于因发生人体接触而引起的汗液,皮脂,保湿用乳液等附着的地方使用也能保持良好的耐磨耗性。
有关上述的表面保护层中来自碳化二亚胺系交联剂的含有量(即,形成表面保护层时混合的碳化二亚胺系交联剂的含有量),虽然没有被特别限定,但是对于聚氨酯系树脂100质量份,优选0.5~10.0质量份,更好质量在2.0~5.0质量份。
上述的表面保护层优选还包括硅酮系化合物。一旦含有硅酮化合物,则可以提高表面的光滑性的同时,也越发的提高了合成皮革的耐磨耗性。上述的硅酮系化合物可以仅使用一种,也可以使用两种以上。
作为上述的硅酮系化合物,优选硅氧烷键为2000或以下的硅酮系化合物。作为硅酮系化合物的实例,可以列举出硅酮油,改性硅酮油,硅酮树脂等。
作为上述的硅酮油(直硅酮油)的实例,可以列举出二甲基硅酮油,甲基苯基硅酮油等。
作为上述的改性硅酮油的实例,可以列举出聚醚改性硅酮油(聚醚改性二甲基硅酮油等),烷基改性硅酮油(烷基改性二甲基硅酮油等),芳烷基改性硅酮油(芳烷基改性二甲基硅酮油等),高级脂肪酸酯改性硅酮油(高级脂肪酸酯改性二甲基硅酮油等),氟烷基改性硅酮油(氟烷基改性二甲基硅酮油等)等。
作为上述的硅酮树脂的实例,可列举出直硅酮树脂,改性硅酮树脂等。作为直硅酮树脂的实例,可列举出甲基硅酮树脂,甲基苯基硅酮树脂等。另外,作为改性硅酮树脂的实例,可列举出醇酸改性硅酮树脂,环氧改性硅酮树脂,丙烯酸改性硅酮树脂,聚酯改性硅酮树脂等。
有关上述的表面保护层中的硅酮系化合物的含有量,虽然没有被特别限定,但是对于聚氨酯系树脂100质量份,优选为3.0~20.0质量份,更优选为6.0~13.0质量份。
上述的表皮层也可以在不损害本发明效果的范围内包含上述的各成分以外的其他成分。作为上述的其他成分,可以举例说明可以包含上述的本发明的树脂泡沫层的其他成分。上述的其他成分可以仅使用一种,也可以使用两种以上。
有关上述的表面保护层的厚度,虽然没有被特别限定,但优选为5~40μm,更优选为10~20μm。如果上述的厚度是5μm或以上的话,则合成皮革的耐磨耗性会进一步提高。如果上述的厚度是40μm或以下的话,则本发明的合成皮革则会更加的轻量化。
以上,虽然有关本发明的合成皮革的优选实施方式如图1所示进行了说明,但本发明的合成皮革并不限定于这样的方式。同时,本发明的合成皮革并不是将粘附层12和表皮层14作为必要的构成要素,例如也可以是不具有粘附层12的结构,不具有表皮层14的结构,或者不具有粘附层12和表皮层14的结构。另外,本发明的合成皮革也可以在不损害本发明效果的范围内,具有上述的各层以外的其他层。作为上述的其他层,例如可列举出用于提高上述的发泡树脂层和上述的表皮层之间的粘附性的底漆层等。
依次具有本发明的合成皮革中的上述底布层,上述发泡树脂层和上述的表面保护层,有关将上述的底布层和上述的表面保护层设置在两端面上的层叠体(特别是由上述的底布层,上述的粘附层,上述的发泡树脂层,上述的表皮层以及上述的表面保护层构成的层叠体),将在以下描述优选方式。作为上述的层叠体的实例,可列举出由图1所示的底布层11,粘附层12,发泡树脂层13,表皮层14以及表面保护层15构成的合成皮革1。
上述的层叠体优选每单位面积的质量为300~500g/m2,更优选为350~460g/m2。本发明的合成皮革,由于重量轻且耐磨耗性优良,所以在耐磨耗性出色的同时,能够达到上述范围的每单位面积的质量。
上述的层叠体优选厚度为1.0~1.3mm。如果上述的厚度是1.0mm或以上的话,则耐磨耗性较高。此外,使用时不易起皱,工作效率高。如果上述的厚度是1.3mm或以下的话,则更加实现轻量化。另外,可以容易地进行双缝纫法,工作效率优秀。并且,如果上述的厚度在上述的范围内,则座椅成型后外观良好。
上述的层叠体在JIS L0849中所规定的对摩擦的染色牢度试验中,在上述的表面保护层一侧进行负荷1kg3万次往返的摩擦试验时,优选为上述的底布层不露出的状态,尤其是优选上述的表面保护层的下层(例如图1所示的合成皮革中的表皮层14)不露出的状态。由于上述的摩擦试验为负荷1kg且3万次的严酷的学振磨耗试验,因此具有上述的特性,本发明的合成皮革具有非常好的耐磨性。
上述的层叠体优选BLC值为4.0~6.0,更优选为4.5~5.7。如果上述的BLC值是4.0或以上的话,本发明的合成皮革的手感则不会太硬,如果上述的BLC值是6.0或以下的话,本发明的合成皮革的手感则不会太软,因此将上述的范围内的设置,可以作为适度的手感的设置。另外,上述的BLC值是指以500g的负荷压入时的应变测量值,可以采用触觉电子测量仪器(商品名“GT303Leather Softness Tester”(GOTECH TESTING MACHINRS INC.制)进行测量。
有关上述层叠体中上述发泡树脂层的厚度的比例,虽然没有被特别限定,但是相对于上述的层叠体的厚度100%,优选为10~60%,更优选为30~50%。如果上述的比例为10%或以上时,则本发明的合成皮革的耐磨性变得更好的同时,也实现轻量化。如果上述的厚度在60%或以下时,则相对的能够充分确保表皮层的厚度,提高合成皮革的耐磨性。
在本发明的合成皮革中,上述层叠体中的发泡层的厚度与非发泡层的厚度之比(前者/后者)优选为3.0~30.0,更优选为5.0~20.0,更进一步优选为10.0~15.0。如果上述的比率在上述范围内,则本发明的合成皮革能够在耐磨耗性出色的同时更轻量化。作为上述的发泡层的实例包括上述的发泡树脂层。作为上述的非发泡层的实例包括上述的表皮层和上述的表面保护层。另外,最好是上述的发泡树脂层的厚度与上述的表皮层及上述的表面保护层的合计厚度之比〔前者/后者〕在上述的范围内。同时,上述的底布层和上述的粘附层应该不属于上述的发泡层以及非发泡层的任何一种。
作为本发明的合成皮革的一个实施方式的合成皮革1,可以如以下方式制作。首先,将形成表皮层14的树脂组成物涂在实施了脱模处理的剥离片材的脱模处理面上形成涂膜,然后使用烘箱等加热装置,通过促进用于形成聚氨酯系树脂的异氰酸酯和多元醇的反应而形成硬化,溶剂的挥发和交联剂,通过硬化,溶剂的挥发和交联剂而导致的硬化等形成表皮层14。可以采用众所周知或惯用的方法进行上述的树脂组合物的涂敷,例如,可以通过形成上述本发明的发泡树脂层时的举例方式进行。
然后,在表皮层14表面上形成发泡树脂层13。有关发泡树脂层13的形成方法,与上述的本发明的发泡树脂层的形成方法相同。另外,最好是将通过另外的压延法所制作出的发泡树脂层13,在冷却之前保持加热状态,或者通过利用热压接的层压法在表皮层14表面上层叠形成。
接下来,在发泡树脂层13表面涂抹形成粘附层12的胶粘剂组合物,进而层叠底布层11,之后利用烘箱等加热装置,通过溶剂的挥发等使胶粘剂组合物硬化而形成粘附层12,经由粘附层12将底布层11固定在发泡树脂层13上。在胶粘剂组合物硬化之前,由于通过将底布层11层叠在发泡树脂层13上而导致胶粘剂组合物浸入底布层11中,因此通过之后的硬化,可以形成粘附层12浸入底布层11中的结构。
接下来,剥离粘贴在表皮层14上的剥离片材,在表皮层14表面上涂抹形成表面保护层15的树脂组合物而形成涂膜,之后使用烘箱等加热装置,通过促进用于形成聚氨酯系树脂的异氰酸酯和多元醇的反应而形成硬化,溶剂的挥发和交联剂,通过硬化,溶剂的挥发和交联剂而导致的硬化等形成表面保护层15。可以采用众所周知或惯用的方法进行上述的树脂组合物的涂敷,例如,可以通过形成上述本发明的发泡树脂层时的举例方式进行。如上所示,可以按照底布层11,粘附层12,发泡树脂层13,表皮层14以及表面保护层15的顺序制作层叠的合成皮革1。
作为本发明的合成皮革的一个实施方式的合成皮革1,除了上述的方法以外,还可以通过如下方式制作。首先,在底布层11上涂抹形成粘附层12的胶粘剂组合物,然后利用烘箱等加热装置,通过溶剂的挥发等使胶粘剂组合物硬化而形成粘附层12,制作层叠了底布层11和粘附层12的层叠体。根据该方法,胶粘剂组合物浸入底布层11中,因此,通过之后的硬化可以形成粘附层12浸入底布层11中的结构。
接下来,在上述的层叠体的粘附层12表面上形成发泡树脂层13。有关发泡树脂层13的形成方法与上述的本发明的发泡树脂层的形成方法相同。另外,最好是将通过另外的压延法所制作出的发泡树脂层13,在冷却之前保持加热状态,或者通过利用热压接的层压法在粘附层12表面上层叠形成。
接下来,在发泡树脂层13表面上涂抹形成表皮层14的树脂组合物而形成涂膜,之后使用烘箱等加热装置,通过促进用于形成聚氨酯系树脂的异氰酸酯和多元醇的反应而形成硬化,溶剂的挥发和交联剂,通过硬化,溶剂的挥发和交联剂而导致的硬化等形成表皮层14。可以采用众所周知或惯用的方法进行上述的树脂组合物的涂敷,例如,可以通过形成上述本发明的发泡树脂层时的举例方式进行。
接下来,在表皮层14表面上涂抹形成表面保护层15的树脂组合物而形成涂膜,之后使用烘箱等加热装置,通过促进用于形成聚氨酯系树脂的异氰酸酯和多元醇的反应而形成硬化,溶剂的挥发和交联剂,通过硬化,溶剂的挥发和交联剂而导致的硬化等形成表面保护层15。可以采用众所周知或惯用的方法进行上述的树脂组合物的涂敷,例如,可以通过形成上述本发明的发泡树脂层时的举例方式进行。如上所示,可以按照底布层11,粘附层12,泡沫树脂层13,表皮层14以及表面保护层15的顺序制作层叠的合成皮革1。
另外,也可以在表面保护层15表面上采用压花加工方式形成表面的纹理。
根据本发明的发泡树脂层,能够提供轻量且耐磨耗性优异的合成皮革。并且,根据本发明的发泡树脂层,可以提供手感及耐弯曲性(特别是低温耐弯曲性)出色的合成皮革。同时,本发明的合成皮革轻量且耐磨耗性优异。并且,本发明的合成皮革在手感及耐弯曲性(特别是低温耐弯曲性)方面优越。耐低温弯曲性优异的情况下,即使在低温环境下使用也不容易产生裂纹。一般来说,柔软的合成皮革具有高耐弯曲性但耐磨耗性较差的倾向。另一方面,硬质的合成皮革具有耐磨耗性高但耐弯曲性较差的倾向。这样,通常,耐磨耗性和耐弯曲性是权衡的关系。对此,本发明的合成皮革的耐磨耗性和耐弯曲性都是高水平的。
[实施例]
以下将举例详细说明本发明,但本发明不受这些实施例的限制。另外,表中所记载的添加量是各成分的混合量(即各原料中的有效成分的混合量。所谓含量),除非特别记载,否则用“质量份”来表示。
实施例1
在底布(商品名“CU19302”,savings-textile公司生产,目测:185g/m2,厚度:600μm)的一个面上,以涂敷量为15g/m2的方式涂抹聚氯乙烯系胶粘剂,使其干燥并形成粘附层,制作了由底布和粘附层层叠的层叠物。另一方面,添加聚氯乙烯(平均聚合度:2000)100质量份及热塑性聚氨酯弹性体(邵氏A硬度:75,熔点:170℃)10质量份,邻苯二甲酸二烷基系增塑剂90质量份,发泡剂(偶氮二甲酰胺)2.5质量份及添加剂(包括填料,稳定剂,耐光色牢度提高剂,颜料和阻燃剂)15质量份,在160℃℃温度下搅拌5分钟,然后冷却后制作树脂组合物。通过压延法将得到的树脂组合物制成薄片,得到未发泡树脂片材,然后在加热状态下粘贴在上述的层叠体的粘附层表面上,在210℃加热2分钟使发泡剂起泡,制作厚度为500μm的树脂发泡体。接下来,在树脂发泡体表面,采用逆辊涂敷法,将颜料10质量份,湿润性提高剂0.3质量份,消泡剂0.3质量份,以及交联剂3质量份混合后所得到的组合物,涂敷在水性聚碳酸酯系聚氨酯树脂(商品名“ハイドランWLS-210”,DIC株式会社生产)100质量份上而形成涂膜,将该涂膜在130℃的温度下加热5分钟,使涂膜干燥,交联,并形成厚度为30μm的表皮层。然后,采用逆辊涂敷法,将水性聚碳酸酯系聚氨酯树脂(商品名“WF-78-143”,Stahl公司生产),硅酮系化合物(商品名“HM-54-002”,Stahl公司生产),以及碳化二亚胺系交联剂混合后所得到的组合物涂敷在表皮层表面而形成涂膜,在130℃的温度下加热该涂膜5分钟,使涂膜干燥,交联,并形成厚度为20μm的表面处理层。然后,在形成的表面处理层上采用压花加工方式形成表面纹理,从而制作成合成皮革。
实施例2~9,比较例1
除了将聚氯乙烯系树脂的种类,热塑性聚氨酯弹性体的种类以及各成分的混合量等如表中所示变更之外,还采用与实施例1相同的方式制作了合成皮革。
实施例10
除了使用热膨胀微胶囊5.0质量份分作为发泡剂之外,还采用与实施例1相同的方式制作了合成皮革。
<评估>
对于在实施例和比较例中所获得的合成皮革,实施了以下评价。结果如表1所示。另外,实施例及比较例中所得到的泡沫树脂层的表观密度如表所示。
(1)学振磨耗性。
自实施例和比较例中得到的合成皮革中,从纵向(较长的方向)取一张宽度为10mm,长度为150mm的试验片,在背面(底布层面)贴上宽度为10mm,长度为15mm,厚度为3mm的聚氨酯海绵。采用JIS L0849中所规定的“学振形染色摩擦强度试验机”(株式会社大荣科学精机制作所生产),实施了JIS L3102的6号棉布摩擦试验。重量1kg,往返摩擦3万次。然后,用目视观察摩擦后的试验片(表面保护层表面),根据以下判定基准判定学振磨耗性。
[判定基准]
○(良好):表面保护层不会因摩擦而被削掉,不会露出表皮层
△(可使用):表面保护层因摩擦而被削除,但未露出底布层的材料
×(不良):存在底布层的露出
(2)耐低温弯曲性
自实施例及比较例中得到的合成皮革中,分别取1张宽度40mm,长度70mm大小的试验片,纵向(较长的方向),横向(宽度方向)。使用弯曲试验机“FT-1521”(株式会社上岛制作所生产),以符合JIS K6260的一定行程反复向试验片施加弯曲的负荷,重复-10℃×30000次对有无裂纹进行评估。根据以下判定基准进行了判定。裂纹长度是纵向测试片和横向测试片的平均值。
[判定基准]
○(良好):未发生裂纹
△(可使用):无裂纹,但发生白化
×(不良):发生裂纹
(3)B LC值(手感)
自实施例及比较例中得到的合成皮革中采集1张尺寸为150mm四方的试验片,使用“GT303 Leather Softness Tester”(GOTECH TESTING MACHINRS INC.生产),并测量以500g的负荷压入时的应变测量值(BLC值)。应变测量值越大,越显示出柔软的手感。
(4)压延加工性
在实施例和比较例中,根据以下判定基准,对于利用压延法制造用于获得发泡树脂层的未发泡树脂片材时的加工性进行了判定。
[判定基准]
○(良好):从压延辊轮中能够取出厚度均匀的未发泡树脂片材
△(可使用):取出未发泡树脂片材之前的混粘时间需要花费几倍的时间
×(不良):花费两倍以上的搅拌时间,虽然可以取出未发泡树脂片材,但厚度不均匀
(5)ASKER C硬度
对于在实施例和比较例中获得的发泡树脂层,采用ASKER橡胶硬度计C型(高分子仪表株式会社生产),基于JIS K7312测量ASKER C硬度。
[表1]
Figure BDA0002464943510000231
采用了本发明发泡树脂层的本发明合成皮革(实施例),即使一边是500g/m2或以下的轻量,一边通过1kg且3万次的严酷的学振磨耗试验,表面保护层也未被削除,耐磨耗性也完成很好。另外,发泡树脂层中的热塑性聚氨酯弹性体的邵氏A硬度在80以下的情况下(实施例1~7,9),耐低温弯曲性也很好。同时,发泡树脂层的发泡倍率为2.0倍或以上的情况下(实施例1~8),则BLC值适度,手感良好。另一方面,当发泡树脂层不包含热塑性聚氨酯弹性体的情况下(比较例1),则导致耐磨耗性较差。
符号说明
1 合成皮革
11 底布层
12 粘附层
13 泡沫树脂层
14 表皮层
15 表面保护层

Claims (13)

1.含有聚氯乙烯系树脂和热塑性聚氨酯弹性体的发泡树脂层。
2.根据权利要求1中所述的发泡树脂层,其特征在于,上述的热塑性聚氨酯弹性体的邵氏A硬度为50~80。
3.根据权利要求1或2中所述的发泡树脂层,其特征在于,表观密度为0.3~0.7g/cm3
4.根据权利要求1或2中所述的发泡树脂层,其特征在于,平均单元直径为50~250μm。
5.根据权利要求1或2中所述的发泡树脂层,其特征在于,具有独立气泡结构。
6.根据权利要求1或2中所述的发泡树脂层,其特征在于,相对于上述的聚氯乙烯系树脂100质量份的上述的热塑性聚氨酯弹性体,其含有量为1~50质量份。
7.根据权利要求1或2中所述的发泡树脂层,其特征在于,还包括增塑剂。
8.根据权利要求7中所述的发泡树脂层,其特征在于,相对于上述聚氯乙烯系树脂100质量份的上述增塑剂,其含有量为40~90质量份。
9.根据权利要求1或2中所述的发泡树脂层,其特征在于,是用于汽车内部装饰的合成皮革。
10.具有权利要求1~9的任一项中所述的发泡树脂层的合成皮革。
11.根据权利要求10中所述的合成皮革,其特征在于,依次具备底布层,上述的发泡树脂层和包含聚氨酯树脂的表皮层,上述的底布层和上述的发泡树脂层通过以聚氯乙烯系树脂作为主要成分的粘附层进行接合。
12.该合成皮革依次具有底布层,发泡树脂层和位于最表面的表面保护层,包括将上述底布层和上述表面保护层位于两端面的层叠体,
上述层叠体在每单位面积的质量为300~500g/m2,厚度为1.0~1.3mm,JIS L0849中所规定的对摩擦的染色牢度试验中,作为负荷1kg,在上述的表面保护层一侧进行3万往返的摩擦试验时,上述表面保护层的下层是处于不露出的状态,BLC值是4.0~6.0的合成皮革。
13.根据权利要求12中所述的合成皮革,其特征在于,上述的泡沫树脂层是根据权利要求1~9的任一项中所述的发泡树脂层。
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