CN112567092B - 人造革基材、其制造方法及立毛人造革 - Google Patents
人造革基材、其制造方法及立毛人造革 Download PDFInfo
- Publication number
- CN112567092B CN112567092B CN201980053504.0A CN201980053504A CN112567092B CN 112567092 B CN112567092 B CN 112567092B CN 201980053504 A CN201980053504 A CN 201980053504A CN 112567092 B CN112567092 B CN 112567092B
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- Prior art keywords
- fiber
- fibers
- artificial leather
- web
- leather substrate
- Prior art date
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Classifications
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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
- D04H1/4382—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
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/004—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using flocked webs or pile fabrics upon which a resin is applied; Teasing, raising web before resin application
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
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- 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
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- 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
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- 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
- B32B5/026—Knitted fabric
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- 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
- B32B5/06—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 characterised by a fibrous or filamentary layer mechanically connected, e.g. by needling to another layer, e.g. of fibres, of paper
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- 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
- B32B5/08—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 the fibres or filaments of a layer being of different substances, e.g. conjugate fibres, mixture of different fibres
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- 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
- B32B5/10—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 characterised by a fibrous or filamentary layer reinforced with filaments
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- 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
- B32B5/22—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
本发明提供一种人造革基材,其包含无纺布和赋予至无纺布的内部的高分子弹性体,所述无纺布为纤维(A)和纤维(B)的抱合体,其中,所述纤维(A)是由特性粘度相互不同的2种树脂形成的卷曲纤维、且是0.6dtex以上的长纤维,纤维(B)是小于0.6dtex的极细纤维。
Description
技术领域
本发明涉及伸缩性(stretch)优异的人造革基材及立毛人造革。
背景技术
目前,已知有将对无纺布的内部赋予高分子弹性体而成的人造革基材的表面立毛处理为麂皮状、牛巴戈状的立毛人造革、在人造革基材的表面层叠聚氨酯树脂层而成的粒面人造革。这样的人造革广泛地用作衣料、鞋、家具、汽车座椅、杂货产品等的原材料。作为这样的人造革,近年来从衣料用途的穿着感、材料用途的成型加工性、以及缝制的容易性、裁剪良好等的观点考虑,要求伸缩性优异的人造革,所述伸缩性是通过拉伸而伸长的性质。
下述专利文献1公开了一种粒面人造革,其包含由平均单纤维直径为0.1~10μm的极细纤维及多孔化的弹性聚合物构成的基材层、以及在基材层的至少一面形成的树脂层,其中,基材层具有由极细纤维形成的纤维束相互抱合而成的结构,在基材层与树脂层相接一侧的表面与厚度方向垂直的截面,基材的极细纤维具有卷曲。另外,专利文献1公开了,这样的粒面人造革保持高剥离强度、以及作为伸缩性的指标的高伸长率和高伸长回复率。
另外,下述专利文献2公开了一种伸缩性优异的人造革,其是由包含单纤维纤度1.1dtex以下的极细纤维的纤维交缠体和高分子弹性体构成、且表面立毛的人造革,其中,极细纤维是具有0.05~0.40(dl/g)的特性粘度差的2种聚对苯二甲酸丙二醇酯相互以并排型复合而成的潜在卷曲表现性聚酯复合纤维。
另外,下述专利文献3公开了一种伸缩性优异的片状物,其由编织物和平均单纤维纤度为0.001dtex以上且0.5dtex以下的极细纤维制成,且含有自乳化型聚氨酯,所述编织物包含含有具有特性粘度(IV)差的2种以上聚对苯二甲酸乙二醇酯类聚合物形成的并排型或偏心芯鞘型的复合纤维而形成的丝。
另外,下述专利文献4公开了一种伸缩性优异的片状物,其是具有伸缩性的人造革,根据按照JIS L 1096(1999)8.14.1A法中记载的方法测定的纵向的强度伸长率曲线,(1)伸长率5%时的强度F5%为0.1~10N/2.5cm,(2)在伸长率20%时的强度F20%与上述F5%的关系中,F20%/F5%为5以上。
另外,下述专利文献5虽然不是与人造革相关的技术,但公开了一种多层无纺布,其是由存在纤维末端的短纤维形成的短纤维层、和以基本上不存在纤维末端的长丝纤维为主成分的长丝纤维主成分层交缠一体化而成的多层无纺布,其中,短纤维的纤维末端具有:短纤维相互交缠在一起的状态的交缠纤维末端、渗透至长丝纤维主成分层并交缠在一起的交缠纤维末端、以及贯穿长丝纤维主成分层并从长丝纤维主成分层的表面露出的状态的露出纤维端末。
现有技术文献
专利文献
专利文献1:日本特开2018-003181号公报
专利文献2:日本特开2003-286663号公报
专利文献3:日本特开2009-7730号公报
专利文献4:日本特开2013-194327号公报
专利文献5:日本特开2017-193794号公报
发明内容
发明要解决的课题
目前,提出了伸缩性优异的人造革。但是,难以平衡性良好地保持高伸缩性、高机械特性、以及立毛时的立毛感。
本发明的课题在于提供用于得到平衡性良好地具备高伸缩性、高机械特性、以及立毛时的立毛感的人造革的人造革基材、其制造方法、以及使用该人造革基材得到的立毛人造革。
解决课题的方法
本发明的一个方面为人造革基材,其包含无纺布和赋予至无纺布的内部的高分子弹性体,所述无纺布为纤维(A)和纤维(B)的抱合体,其中,纤维(A)是由特性粘度相互不同的2种树脂形成的卷曲纤维,且是具有0.6dtex以上的平均纤度的长纤维,纤维(B)是具有小于0.6dtex的平均纤度的极细纤维。需要说明的是,以下,平均纤度有时也简称为纤度。
纤维(A)表现出强烈的蜷曲(crimp),纤维(A)是所述由特性粘度相互不同的2种树脂形成的卷曲纤维。由这样的卷曲纤维形成的无纺布变得蓬松。另外,具有强烈蜷曲的卷曲纤维在人造革基材中表现出优异的伸缩性。另外,长纤维的纤维(A)不容易脱落、伸缩性不容易降低。
需要说明的是,在使用了仅由卷曲纤维形成的无纺布的情况下,难以得到兼顾高机械特性和优异的伸缩性的人造革基材。例如,对于仅纤维(A)的无纺布而言,其纤维的抱合度过高时,虽然机械特性增高但伸缩性降低,抱合度过低时,虽然伸缩性增高但机械特性降低。这样,在使用了仅由卷曲纤维形成的无纺布的情况下,无法得到兼顾高伸缩性和高机械特性的人造革基材。
另一方面,如上所述,根据使纤维(B)与纤维(A)抱合而形成的无纺布,可以得到兼顾高伸缩性和高机械特性的人造革基材,所述纤维(B)是具有低于0.6dtex的平均纤度的极细纤维,所述纤维(A)是具有0.6dtex以上的平均纤度的长纤维的卷曲纤维。通过使用作为具有强烈蜷曲的卷曲纤维的纤维(A),易于通过该蜷曲使纤维(A)与纤维(B)抱合。其结果是,可实现兼顾高伸缩性和高机械特性的人造革基材。另外,作为极细纤维的纤维(B)通过使人造革基材的表面的纤维变得致密而赋予优异的立毛外观。此外,在使作为卷曲纤维的纤维(A)与作为极细纤维的纤维(B)抱合而成的无纺布中,纤维(B)还具有以一定的伸长范围固定纤维(A)的作用,所述纤维(A)是在反复伸长时丝容易变得逐渐完全伸长展开而难以回复的卷曲纤维。
从保持高伸缩性的观点考虑,纤维(A)的平均弯曲率优选为10%以上,更优选为15%以上。特别优选纤维(A)的平均弯曲率为15%以上,纤维(B)的平均弯曲率小于15%。
另外,从梳棉通过性优异的观点考虑,优选纤维(B)为平均纤维长度小于100mm的短纤维。
另外,从容易得到平均弯曲率高的卷曲纤维的观点考虑,优选纤维(A)为2种树脂的特性粘度之差为0.05(dl/g)以上的并排型纤维或偏芯芯鞘型纤维。
另外,作为形成纤维(A)的2种树脂,优选为聚酯。
另外,从得到高伸缩性和高机械特性的平衡性更优异的人造革基材的观点考虑,优选纤维(A)与纤维(B)的配合比例((A)/(B))为10/90~90/10。
另外,从得到具有高伸缩性的人造革基材的观点考虑,优选被施加1kg负载5分钟时的平均伸长率为10%以上。
需要说明的是,对于使包含卷曲纤维的无纺布含有高分子弹性体而成的伸缩性优异的人造革而言,存在反复伸长时,丝逐渐完全伸长展开而难以回复的问题。即,使用了包含卷曲纤维的无纺布的人造革难以在反复进行伸长后保持高伸缩性。另外,例如,如专利文献1所示,在无纺布中大量含有多孔化的弹性聚合物的情况下,通过弹性聚合物的回复力,在反复进行伸长后,也可以保持高伸缩性。但是,在由于能够减少溶剂用量而在无纺布中大量含有水性聚氨酯的情况下,变得如橡胶那样硬,存在伸缩性降低的倾向。
对于人造革基材而言,特别优选高分子弹性体为水性聚氨酯,水性聚氨酯的含有比例为8~15质量%,厚度方向的截面的空隙的平均面积为300~1000μm2。这样的人造革基材在反复伸长后,伸缩性也不容易降低。
通过使水性聚氨酯的含有比例为8~15质量%,不会使人造革基材变得如橡胶那样硬,可适度束缚纤维而保持伸缩性。因此,使纤维(A)与纤维(B)充分抱合,将厚度方向的截面的空隙的平均面积调整为300~1000μm2,使平均一个空隙为适度的大小,由此,可以得到即使在反复伸长后也具备一定以上的伸长率和伸长回复率的伸缩性优异的人造革基材。
另外,本发明的另一方面为立毛人造革,其包含上述任意的人造革基材,且其一面经过了立毛处理。这样的立毛人造革的伸缩性和机械特性的平衡性优异,且具有带有致密立毛的立毛面。
另外,本发明的另一方面为人造革基材的制造方法,其是上述人造革基材的制造方法,该方法至少包括:准备第1纤维网的工序,所述第1纤维网包含用于形成纤维(A)的、由特性粘度相互不同的2种树脂形成的0.6dtex以上的长纤维的卷曲型纤维(A1);准备用于形成纤维(B)的极细纤维发生型纤维(B1)的第2纤维网的工序;将第2纤维网层叠于第1纤维网的至少一面而形成层叠网的工序;形成抱合纤维片的工序,所述抱合纤维片是使形成层叠网的卷曲型纤维(A1)与极细纤维发生型纤维(B1)进行抱合处理而成的;使抱合纤维片热收缩而形成热收缩纤维片的工序;通过对形成热收缩纤维片的极细纤维发生型纤维(B1)进行极细纤维化处理而形成作为卷曲型纤维(A1)和纤维(B)的抱合体的无纺布的工序;对热收缩纤维片或无纺布含浸赋予高分子弹性体的工序。需要说明的是,卷曲型纤维是形成作为卷曲纤维的纤维(A)的纤维,包括在成网的时刻具有卷曲的显在卷曲型纤维、以及在成网的时刻未表现出卷曲而通过后续的工序的热处理发生卷曲的潜在卷曲型纤维。根据这样的方法,可以得到上述那样的兼顾高伸缩性、高机械特性、以及立毛时优异的立毛感的人造革基材。
另外,从得到高伸缩性和机械特性的平衡性优异的人造革基材的观点考虑,优选的层叠网是在第1纤维网的两面层叠有第2纤维网的层叠体。
另外,含浸赋予高分子弹性体的工序优选为通过在使聚氨酯水性乳液含浸于热收缩纤维片或无纺布后使其干燥而生成水性聚氨酯的工序。通过在使聚氨酯水性乳液含浸于热收缩纤维片或无纺布后使其干燥而生成非海绵状聚氨酯,可以减少溶剂用量。需要说明的是,水性聚氨酯容易束缚纤维,在使配合比例过高的情况下,伸缩性容易降低。因此,作为水性聚氨酯的含有比例,优选低于20%。另一方面,在含浸溶剂类聚氨酯而生成海绵状聚氨酯的情况下,可以在人造革基材中赋予弹性高的高分子弹性体。因此,对于溶剂类聚氨酯而言,由于不容易牢固束缚纤维,因此即使含有20%以上,也容易得到兼顾高伸缩性和高机械特性的人造革基材。
另外,从容易得到反复伸长后也不使伸缩性过度降低的人造革基材的观点考虑,优选卷曲型纤维(A1)为以纺丝牵伸比400以上进行纺丝而成的平均纤度0.6dtex以上的卷曲型纤维,制造的人造革基材是水性聚氨酯的含有比例为8~15质量%、且厚度方向的截面的空隙的平均面积为300~1000μm2的人造革基材。
发明的效果
根据本发明,可以得到平衡性良好地具备高伸缩性、机械特性、以及立毛时的立毛感的人造革基材。
附图说明
图1是对平均弯曲率进行说明的说明图。
图2是对厚度方向的截面的空隙的平均面积进行说明的说明图。
符号说明
1 纤维
具体实施方式
本实施方式的人造革基材包含无纺布和赋予至无纺布的内部的高分子弹性体,所述无纺布是纤维(A)和纤维(B)的抱合体,其中,纤维(A)是由特性粘度相互不同的2种树脂形成的卷曲纤维,且是具有0.6dtex以上的平均纤度(以下,也简称为纤度)的长纤维,纤维(B)是具有低于0.6dtex的平均纤度的极细纤维。
以下,基于制造方法的一例对本实施方式的人造革基材详细进行说明。
上述的人造革基材例如可以通过至少具备以下各工序的制造方法来制造。
工序(1):准备第1纤维网的工序,所述第1纤维网包含由特性粘度相互不同的2种树脂形成的0.6dtex以上的长纤维的卷曲型纤维(A1)。
工序(2):准备用于形成作为低于0.6dtex的极细纤维的纤维(B)的极细纤维发生型纤维(B1)的第2纤维网的工序。
工序(3):将第2纤维网层叠于第1纤维网的至少一面而形成层叠网的工序。
工序(4):形成抱合纤维片的工序,所述抱合纤维片是使形成层叠网的卷曲型纤维(A1)与极细纤维发生型纤维(B1)进行抱合处理而成的。
工序(5):使抱合纤维片热收缩而形成热收缩纤维片的工序。
工序(6):通过对形成热收缩纤维片的极细纤维发生型纤维(B1)进行极细纤维化处理,从而形成作为卷曲型纤维(A1)与纤维(B)的抱合体的无纺布的工序。
工序(7):对热收缩纤维片或无纺布含浸赋予高分子弹性体的工序。
(1)第1纤维网的准备工序
在本实施方式的人造革基材的制造中,制造包含卷曲型纤维(A1)的第1纤维网,所述卷曲型纤维(A1)是由特性粘度相互不同的2种树脂形成的具有0.6dtex以上的平均纤度的长纤维。
作为第1纤维网的制造方法,例如,使用所谓的纺粘法,使用熔融纺丝法对卷曲型纤维(A1)进行纺丝,不将其切断而捕集至网上,形成连续纤维的长纤维的网的方法;使用熔融纺丝法对卷曲型纤维(A1)进行纺丝,并拉伸,然后进一步根据需要赋予卷曲,将切成平均纤维长度100mm以上的原棉通过梳棉机而成网的方法。卷曲型纤维(A1)是形成纤维(A)的纤维,所述纤维(A)是由特性粘度相互不同的2种树脂形成的卷曲纤维,可以是在成网的时刻具有卷曲的显在卷曲型纤维,也可以是在成网的时刻未表现出卷曲而通过后续工序的热处理发生卷曲的潜在卷曲型纤维。其中,从易于进一步提高机械特性的观点考虑,优选为使用纺粘法形成连续纤维的长纤维的网的方法。需要说明的是,将切断后的原棉通过梳棉机而成网的方法具有难以通过梳棉机的倾向。
卷曲型纤维(A1)为长纤维。本实施方式中的长纤维的平均纤维长度为100mm以上,优选为200mm以上,进一步优选为通过纺粘法制造的连续纺丝而成的、例如数m、数百m、特别是数km以上的纤维长度的连续纤维。通过使卷曲型纤维(A1)为长纤维,卷曲型纤维不容易脱落,表现出高伸缩性。在纤维(A)为平均纤维长度小于100mm的短纤维的情况下,纤维(A)变得容易脱落,人造革基材的伸缩性变得容易降低。在本实施方式中,作为代表例,对于使用纺粘法制造第1纤维网的方法详细进行说明。
作为用于形成由特性粘度不同的2种树脂形成的卷曲型纤维(A1)的树脂,可以列举例如:作为对苯二甲酸单元与乙二醇单元的共聚物的聚对苯二甲酸乙二醇酯(PET)、作为对苯二甲酸单元与1,4-丁二醇单元的共聚物的聚对苯二甲酸丁二醇酯(PBT)、聚对苯二甲酸丙二醇酯(PTT)、聚酯弹性体等聚酯类树脂、或者它们的改性体等改性聚酯类树脂、聚酰胺6、聚酰胺66、聚酰胺610、芳香族聚酰胺、聚酰胺弹性体等聚酰胺类树脂、或者它们的改性体等改性聚酰胺类树脂。其中,从易于得到表现出高蜷曲的纤维的观点考虑,优选为聚酯类树脂。
需要说明的是,改性体是为了调整树脂的特性粘度、熔点、结晶性而将主要的聚合物形成单元的一部分用其它少量的单体单元取代而成的聚合物。例如,作为对聚酯进行改性的少量单体单元,可以列举例如:间苯二甲酸,邻苯二甲酸、间苯二甲酸-5-磺酸钠等非对称型芳香族羧酸、己二酸等脂肪族二羧酸、乙二醇、丁二醇、新戊二醇、环己烷二甲醇、聚乙二醇、聚丙二醇等二醇类等。通过将这些单体单元导入聚酯,可以调整聚酯的特性粘度、熔点、结晶性。
作为由特性粘度不同的2种树脂形成的卷曲型纤维(A1),可以举出并排型纤维、具有偏心芯鞘型截面的偏心芯鞘型纤维。并排型纤维是在熔融纺丝时将特性粘度相互不同的2种树脂沿纤维的长度方向贴合而形成的纤维。另外,偏心芯鞘型的纤维是在熔融纺丝时,在特性粘度相互不同的2种树脂中,以一种树脂作为芯部,以另一种树脂作为鞘部,具有芯鞘型截面,且在芯鞘型截面中芯部偏离中心而非对称地配置的纤维。这样的卷曲型纤维在纺丝后或通过随后的热处理而表现出强烈蜷曲。
作为形成卷曲型纤维的2种树脂的组合,可以根据与想要表现出的伸缩性的程度、用途所对应的无纺布的抱合状态的要求而适当选择。具体而言,例如,可以根据要求特性而适当选择PET和PBT、PET和PET、PBT和PBT、PBT和PTT等。需要说明的是,这些中的至少任一者可以为改性体。其中,从因纤维(A)表现出强烈蜷曲而易于得到伸缩性优异的人造革基材的观点考虑优选为PET和PBT的组合。
作为2种树脂的特性粘度之差,从纤维(A)表现出有助于表现伸缩性的强烈蜷曲的观点考虑,优选为0.05dl/g以上,更优选为0.1~0.6dl/g。在特性粘度之差过小时,难以表现出强烈蜷曲,在特性粘度之差过大时,从喷嘴喷出后喷嘴面的倾斜变得严重,因此具有熔融纺丝性降低的倾向。
另外,作为特性粘度不同的2种树脂的特性粘度,从熔融纺丝性、机械特性优异的观点考虑,特性粘度高的树脂的特性粘度优选为0.6~1.2dl/g,更优选为0.62~1.1dl/g。
作为2种树脂中的高粘度树脂的比例,从易于表现出强烈卷曲的观点考虑,优选为30~70质量%,更优选为40~60质量%。
另外,根据需要,2种树脂分别可以含有有机粒子、无机粒子、阻燃剂、抗静电剂等添加剂。
第1纤维网可以通过纺粘法来制造,所述纺粘法为使从排列有2种树脂的熔融复合纺丝用喷丝头的各喷嘴孔喷出且熔融的2种树脂接触,进一步从纺丝喷嘴以给定的喷出速度连续地喷出,一边使用高速气流进行冷却,一边使其拉伸而堆积在传送带状的移动式的网上。另外,为了赋予形态稳定性,可以对堆积在网上的长纤维的网进行热压。
熔融纺丝条件没有特别限定,从可以得到易于保持反复伸长后的伸缩性的人造革基材的观点考虑,优选例如在以下的条件的情况下得到表现出高蜷曲的纤维(A)。
可以举出例如在设定为如下条件下进行熔融纺丝,所述条件为:将从纺丝喷嘴1个孔喷出的熔融树脂的喷出速度设为A(g/min)、树脂的熔融密度设为B(g/cm3)、1个孔的面积设为C(mm2)、纺丝速度设为D(m/min)时,根据下式计算出的纺丝牵伸比为400以上、进一步为400~1600、特别为700~1600的范围。
·纺丝牵伸比=D/(A/B/C)
卷曲型纤维(A1)及作为卷曲纤维的纤维(A)的平均纤度为0.6dtex以上,优选为0.6~2.5dtex,更优选为0.6~2dtex,特别优选为0.6~1.5dtex。在卷曲型纤维(A1)及作为卷曲纤维的纤维(A)的平均纤度小于0.6dtex时,抱合不足,机械特性容易降低。
通过这样的方法,可以得到包含由特性粘度相互不同的2种树脂形成的纤度0.6dtex以上的长纤维的卷曲型纤维(A1)的第1纤维网。卷曲型纤维(A1)是在该工序中为卷曲纤维的显在卷曲纤维,或者是作为通过随后的热处理表现出卷曲的潜在卷曲纤维的纤维、且是具有0.6dtex以上的平均纤度的长纤维。
(2)第2纤维网的准备工序
准备包含极细纤维发生型纤维(B1)的第2纤维网,所述极细纤维发生型纤维(B1)用于形成作为小于0.6dtex的极细纤维的纤维(B)。
作为第2纤维网的制造方法,可以列举例如:使用熔融纺丝法对极细纤维发生型纤维进行纺丝、拉伸,然后,进一步根据需要赋予蜷曲,将切断后的原棉通过梳棉机而成网的方法;使用纺粘法,使用熔融纺丝法对极细纤维发生型纤维进行纺丝,不将其切断而捕集至网上,形成连续纤维的长纤维的网的方法。极细纤维发生型纤维可以是短纤维,也可以是长纤维,从梳棉通过性优异、而且易于得到机械特性和立毛时的立毛感特别优异的人造革基材的观点考虑,特别优选为短纤维网。在本实施方式中,以制造短纤维网的情况作为代表例详细进行说明。
极细纤维发生型纤维(B1)是通过对纺丝后的纤维实施化学性后处理或物理性后处理而形成纤度小的极细纤维的纤维。作为具体例,可以列举例如:海岛型复合纤维、剥离分割型复合纤维等。海岛型复合纤维是如下的复合纤维:在纤维截面,在成为基质的海成分的树脂中分散有与海成分不同种类的成为微区的岛成分的树脂,且通过去除海成分而产生以岛成分的树脂作为主体的纤维束状的极细纤维。另外,剥离分割型复合纤维是如下的复合纤维:多种不同树脂交替配置在纤维外周并形成花瓣形状、重叠形状,且通过物理性处理将各树脂剥离,从而被分割而形成束状的极细纤维。根据海岛型复合纤维,可以形成内部保持空隙的极细纤维的纤维束,因此易于得到柔顺的人造革基材,而且易于获得高机械特性。在本实施方式中,以使用海岛型复合纤维形成极细纤维的情况作为代表例详细进行说明。
海岛型复合纤维是由至少2种聚合物形成的多成分类复合纤维,通过在随后的适当阶段提取或分解海成分而将其去除,从而形成由岛成分构成的纤维束状的极细纤维。
作为海岛型复合纤维的岛成分的热塑性树脂的具体例子,可以列举例如:PET、PBT、PTT、聚酯弹性体等聚酯类树脂;聚酰胺6、聚酰胺66、聚酰胺610、芳香族聚酰胺、聚酰胺弹性体等聚酰胺类树脂;丙烯酸树脂;烯烃树脂等。这些树脂可以为改性体。另外,这些树脂可以单独使用,也可以组合2种以上使用。
另一方面,作为海成分的热塑性树脂的具体例,可以列举例如:聚乙烯醇类树脂、聚乙烯、聚丙烯、聚苯乙烯、乙烯丙烯共聚物、乙烯乙酸乙烯酯共聚物、苯乙烯乙烯共聚物、苯乙烯丙烯酸共聚物等。其中,从在湿热处理、热水处理中容易收缩的观点考虑,优选为具有水溶性的聚乙烯醇类树脂,特别优选为乙烯改性聚乙烯醇树脂。
作为海岛型复合纤维的海成分与岛成分的质量比例,优选海成分∶岛成分=5∶95~80∶20的范围。
海岛型复合纤维的网具体可以举出以下的方法:使用以给定的图案配置有大量喷嘴孔的复合纺丝用喷丝头,利用熔融纺丝法对海岛型复合纤维进行纺丝、拉伸,然后,进一步根据需要赋予蜷曲,将切断后的原棉通过梳棉机而成网。另外,根据需要,为了对海岛型复合纤维的网赋予形态稳定性,可以实施热压。
在纤维(B)由海岛型复合纤维形成的情况下,例如优选5~200根、更优选10~50根、特别优选10~30根极细纤维形成纤维束。
网中的极细纤维发生型纤维(B1)随后通过极细纤维化处理而转变为纤维(B),所述纤维(B)是具有小于0.6dtex的平均纤度的极细纤维。
纤维(B)的平均纤维长度没有特别限定,可以是小于100mm的短纤维,可以为100mm以上,进一步可以为200mm以上,特别是可以为通过纺粘法从纺丝连续地制造成为网的例如数m、进一步为数百m、特别是数km以上的纤维长度。在纤维(B)为平均纤维长度小于100mm的短纤维的情况下,从梳棉通过性优异的观点考虑,优选为40~75mm。另外,从得到机械特性更优异的人造革基材的观点考虑,纤维(B)优选为在纺丝后进行了拉伸的纤维。
(3)形成在第1纤维网的至少一面层叠有第2纤维网的层叠网的工序
接下来,将第1纤维网和第2纤维网重合进行层叠,由此形成层叠网。
作为层叠网的制造方法,可以列举例如,以在第1纤维网的至少一面、优选为两面配置第2纤维网的方式使用叠布装置叠合4~100片左右的交叉铺网。另外,只要不损害本发明效果,可以根据需要叠合织物、编物、其它的无纺布等。
需要说明的是,在交叉铺网时,为了防止针刺时发生断针、损伤,优选对待使用的纤维的表面或纤维网的表面赋予防断针油剂、抗静电剂等。
第1纤维网与第2纤维网的比例没有特别限定,优选为最终得到的无纺布中纤维(A)与作为极细纤维的纤维(B)的比例((A)/(B))成为10/90~90/10、进一步成为15/85~85/15的比例。
(4)使层叠网的卷曲型纤维(A1)与极细纤维发生型纤维(B1)抱合而形成抱合纤维片的工序
接下来,通过使形成层叠网的第1纤维网的卷曲型纤维(A1)与第2纤维网的极细纤维发生型纤维(B1)抱合,形成抱合纤维片。抱合纤维片可以通过使用针刺、高压水流处理等公知的无纺布制造方法对层叠网实施抱合处理而形成。在本实施方式中,以基于针刺的抱合处理作为代表例详细进行说明。
对层叠网赋予防断针油剂、防静电油剂、抱合提高油剂等有机硅类油剂或矿物油类油剂。然后,进行通过针刺使卷曲型纤维(A1)和极细纤维发生型纤维(B1)三维抱合的抱合处理。
在针刺处理中,例如,从一面或两面同时或交替交互地以至少1个以上钩贯穿的条件进行针刺。针刺密度根据层叠网的单位面积重量、纤维密度等而不同,从使纤维适度抱合、保持高伸缩性、而且也保持高机械特性的观点考虑,优选为1000~3000针/cm2,更优选为1200~2500针/cm2。
作为由极细纤维发生型纤维(B1)形成的具有小于0.6dtex的平均纤度的极细纤维的纤维(B)有助于兼顾得到的人造革基材的高机械特性和高伸缩性。
在使用了不包含作为极细纤维的纤维(B)而仅包含作为卷曲纤维的纤维(A)的层叠网的情况下,难以兼顾高机械特性和高伸缩性。具体而言,在使用了仅包含纤维(A)的层叠网的情况下,机械特性不足时想要提高针刺密度来进一步束缚纤维而提高机械强度时,存在伸缩性降低、而且想要提高针刺密度也会发生断丝而无法充分提高机械强度的倾向。另外,在伸缩性不足的情况下,想要降低针刺密度放松纤维的束缚而提高伸缩性时,机械特性降低。在本实施方式的人造革基材的制造中,使用了包含纤维(B)和纤维(A)的层叠网的情况下,可以兼顾人造革基材的高机械特性和高伸缩性。
作为使这样制造的层叠网的纤维(A1)与极细纤维发生型纤维(B1)抱合而成的抱合纤维片的单位面积重量,没有特别限定,从能够得到兼具高机械特性和高伸缩性的人造革基材、而且可获得适度的工序通过性的观点考虑,优选为100~1000g/m2,进一步优选为200~900g/m2。
(5)使抱合纤维片热收缩而形成热收缩纤维片的工序
接下来,通过使抱合纤维片热收缩,可以提高抱合纤维片的纤维密度及抱合程度,而且使纤维(A1)表现出蜷曲、或增强已表现出的蜷曲。作为热收缩处理的具体例,可以列举例如:使抱合纤维片连续地接触水蒸气的方法、在对抱合纤维片赋予水后用热空气、红外线等电磁波对水进行加热的方法等。另外,为了将通过热收缩处理而致密化的抱合纤维片进一步致密化,并且使形态固定、使表面平滑,可以根据需要进一步进行热压处理。
作为热收缩处理工序中的抱合纤维片的单位面积重量的变化,与热收缩处理前的单位面积重量相比,优选为1.1倍(质量比)以上,更优选为1.3倍以上,且优选为2倍以下,更优选为1.6倍以下。
作为由此制造的热收缩纤维片的单位面积重量,没有特别限定,从可以得到机械特性和伸缩性的平衡性优异的人造革基材、获得适度的工序通过性的观点考虑,优选为200~2000g/m2,更优选为400~1800g/m2。
(6)通过对形成热收缩纤维片的极细纤维发生型纤维(B1)进行极细纤维化处理而形成作为卷曲型纤维(A1)与具有小于0.6dtex的平均纤度的纤维(B)的抱合体的无纺布的工序
在本工序中,通过对热收缩纤维片中的极细纤维发生型纤维进行极细纤维化处理,形成无纺布,所述无纺布是由特性粘度相互不同的2种树脂形成的0.6dtex以上的长纤维的卷曲型纤维(A1)、和作为具有小于0.6dtex的平均纤度的极细纤维的纤维(B)的抱合体。在本实施方式中,以极细纤维发生型纤维为海岛型复合纤维的情况作为代表例详细进行说明。
通过用水、溶剂等从热收缩纤维片中包含的海岛型复合纤维中提取或分解去除海成分而转变为纤维束状的极细纤维,由此形成无纺布,所述无纺布是卷曲型纤维(A1)和作为极细纤维的纤维(B)的抱合体。例如,在海成分中使用了水溶性聚乙烯醇类树脂的海岛型复合纤维的情况下,通过用水、碱性水溶液、酸性水溶液等进行热水加热处理,可以去除作为海成分的水溶性聚乙烯醇类树脂。
作为极细纤维的纤维(B)为具有小于0.6dtex的平均纤度的极细纤维,优选具有0.01~0.55dtex、更优选具有0.05~0.5dtex的平均纤度。这样的作为极细纤维的纤维(B)在对人造革基材的表面进行了立毛时,表现出细致的纤维的立毛感。
另外,对于作为由海岛型复合纤维形成的极细纤维的纤维(B)而言,例如,优选5~200根、更优选10~50根、特别优选10~30根极细纤维形成纤维束而存在。纤维(B)通过以极细纤维的纤维束的形式存在,表现出更高的机械强度。
作为这样形成的卷曲型纤维(A1)和纤维(B)的抱合体的无纺布的单位面积重量没有特别限定,例如,优选为100~1000g/m2,更优选为200~600g/m2。
(7)对热收缩纤维片或无纺布含浸赋予高分子弹性体的工序
在人造革基材的制造中,为了对人造革基材赋予形态稳定性、而且提高充实感,对工序(5)中得到的热收缩纤维片或工序(6)中得到的无纺布含浸赋予高分子弹性体。在对工序(5)中得到的热收缩纤维片含浸赋予了高分子弹性体的情况下,由于在赋予了高分子弹性体之后,在工序(6)中对极细纤维发生型纤维进行极细纤维化处理,因此,形成的极细纤维的纤维(B)不受高分子弹性体的束缚,从可以得到伸缩性更高的人造革基材的观点考虑,是优选的。
作为高分子弹性体的具体例,可以列举例如:聚氨酯、丙烯酸类弹性体、聚酰胺弹性体等聚酰胺类弹性体、聚酯弹性体等聚酯类弹性体、聚苯乙烯类弹性体、聚烯烃类弹性体等。
从可以得到形态稳定性及充实感优异、且伸缩性也优异的人造革基材的观点考虑,相对于与作为纤维(A)和纤维(B)的抱合体的无纺布的总量,高分子弹性体的含有比例优选为5~50质量%,更优选为5~40质量%,特别优选为10~30质量%。在高分子弹性体的含有比例过低时,存在因形态稳定性降低、纤维脱落而使伸缩性降低的倾向。另外,在高分子弹性体的含有比例过高时,存在成为类似橡胶的手感、伸缩性降低的倾向。另外,相对于与作为纤维(A)和纤维(B)的抱合体的无纺布的总量,在高分子弹性体的含有比例为8~15质量%时,重复伸长后的伸长回复率特别优异。
从柔软性和充实感优异的观点考虑,在高分子弹性体中,特别优选为聚氨酯。作为聚氨酯的性状,可以列举:制备成水性乳液的水性聚氨酯、溶解于包含N,N-二甲基甲酰胺(DMF)的溶剂而制备成溶液的溶剂类聚氨酯。
作为含浸赋予高分子弹性体的方法,可以举出在对热收缩纤维片或无纺布含浸赋予溶剂类聚氨酯之后,通过湿法凝固而赋予海绵状聚氨酯的方法。在使用了这样的方法的情况下,可以在人造革基材中赋予弹性优异的高分子弹性体。需要说明的是,由于溶剂类聚氨酯不容易牢固束缚纤维,因此,即使含有例如20%以上,也容易得到兼具高伸缩性和高机械特性的人造革基材。
另外,作为含浸赋予高分子弹性体的方法,可以举出通过在对热收缩纤维片或无纺布含浸聚氨酯水性乳液之后使其干燥,从而赋予水性聚氨酯的方法。在使用了这样的方法的情况下,可以减少溶剂用量。需要说明的是,水性聚氨酯易于束缚纤维,在使配合比例过度增高的情况下,伸缩性容易降低。因此,作为水性聚氨酯的含有比例,优选小于20%。
在本实施方式的人造革基材的制造中,尽管没有限定,但从能够在较短时间进行处理、可以尽量减小不必要的张力、从而获得高伸缩性、对环境的负担小的观点考虑,特别优选为水性聚氨酯。
水性聚氨酯可以以水性乳液、水性悬浮液的形式制备。另外,为了提高耐水性、耐磨损性及耐水解性,水性聚氨酯可以进行交联。用于使水性聚氨酯交联的交联剂可以是相对于水性聚氨酯作为第3成分而添加的外交联剂,另外,也可以是在水性聚氨酯的分子结构内预先导入待形成交联结构的反应点的内交联剂。作为交联剂,可以列举具有异氰酸酯基、唑啉基、碳二亚胺基、环氧基、三聚氰胺树脂、以及硅烷醇基等的化合物。
通过使水性聚氨酯的含有比例相对于与作为纤维(A)和纤维(B)的抱合体的无纺布的总量为8~15质量%,可以得到形态稳定性及充实感优异、而且重复伸长后的伸长回复率也优异的人造革基材。在水性聚氨酯的含有比例小于8质量%时,存在形态稳定性降低、因纤维容易脱落而使重复伸长后的伸长回复率降低的倾向。另外,在水性聚氨酯的含有比例过高时,存在成为类似橡胶的手感的倾向。
作为对热收缩纤维片或无纺布含浸赋予高分子弹性体的方法,例如在使用水性聚氨酯的乳液的情况下,可以优选使用在用水性聚氨酯的乳液充满的浴中浸渍热收缩纤维片或无纺布后,进行1次或多次用加压辊等以达到给定的含浸状态的方式进行挤压的处理的浸渍夹持法。另外,作为其它方法,可以使用棒涂法、刮刀涂布法、辊涂法、缺角轮涂布法(comma coating)、喷涂法等。
通过将水性聚氨酯的乳液、悬浮液含浸于热收缩纤维片或无纺布并使水性聚氨酯干燥凝固的干法使其凝固,可以对热收缩纤维片或无纺布含浸赋予水性聚氨酯。需要说明的是,为了使凝固后的水性聚氨酯交联,优选在干燥后进一步实施热处理,进行固化(cure)处理。
高分子弹性体中可以根据需要含有炭黑等颜料、染料、防霉剂及抗氧剂、紫外线吸收剂、以及光稳定剂等耐光剂、阻燃剂、渗透剂、润滑剂、二氧化硅、氧化钛等防粘连剂、防水剂、粘度调整剂、抗静电剂等表面活性剂、有机硅等消泡剂、纤维素等填充剂、凝固调整剂、以及二氧化硅、氧化钛等无机粒子等。
通过以上的工序可以得到人造革基材。对于得到的人造革基材而言,在干燥后,通过在与厚度方向垂直的方向上切片成多张、进行磨削,从而进行厚度调节、调整表面状态,进行精加工。进一步可以形成对人造革基材的至少一面进行立毛处理而成的立毛面、粒面状的树脂层。从进行立毛处理而形成的立毛面的立毛感优异的观点考虑,本实施方式的人造革基材特别优选用于至少一面经过了立毛处理的立毛人造革的制造。
在立毛处理中,通过使用砂纸等对人造革基材的表层进行打磨处理、立毛处理,可以得到麂皮状、牛巴戈状的手感。另外,除立毛处理以外,还可以根据需要实施揉捏软化处理、逆密封的刷毛处理、防污处理、亲水化处理、润滑剂处理、柔软剂处理、抗氧剂处理、紫外线吸收剂处理、荧光剂处理、阻燃处理等精加工处理。
由此得到的人造革基材优选进一步进行染色。染色可以根据纤维的种类而适当选择以分散染料、反应染料、酸性染料、金属络合染料、硫化染料、硫化还原染料等为主体的染料,可以使用浸轧机(padder)、卷染机(jigger)、液流染色机(circular)、绳状染色机(winch)等纤维染色所通常使用的公知的染色机来进行。例如,在极细纤维为聚酯类极细纤维的情况下,优选使用分散染料通过高温高压染色进行染色。
通过上述的本实施方式的制造方法得到的人造革基材或使用了其的人造革包含作为纤维(A)和纤维(B)的抱合体的无纺布、以及赋予至无纺布内部的高分子弹性体,纤维(A)是由特性粘度相互不同的2种树脂形成的卷曲纤维、且是具有0.6dtex以上的平均纤度的长纤维,纤维(B)是具有小于0.6dtex的平均纤度的极细纤维。
对于通过本实施方式得到的人造革基材或使用了其的人造革而言,至少纤维(A)强烈卷曲,并通过强烈卷曲发挥伸缩性。这里,卷曲纤维是指如后所述测定的平均弯曲率为10%以上的纤维。从发挥高伸缩性的观点考虑,优选纤维(A)的卷曲的平均弯曲率为14%以上,特别优选为15%以上,更优选为20%以上。
另外,纤维(B)优选为微弱卷曲的极细纤维。这里,微弱卷曲是指,如后所述测定的平均弯曲率小于14%,进一步小于13.5%,特别是小于11%。在人造革基材中,通过将纤维(B)与纤维(A)抱合成为一体,以一定的范围固定纤维(A)伸长。
根据通过本实施方式得到的人造革基材,可以得到平衡性良好地具备伸缩性、机械特性、以及立毛时的立毛感的人造革。作为人造革基材或使用了其的人造革的伸缩性,从制成伸缩性优异的人造革基材或人造革的观点考虑,优选被施加1kg负载5分钟时的平均伸长率为10%以上,更优选为15%以上,特别优选为20%以上。需要说明的是,被施加1kg负载5分钟时的平均伸长率是指,相当于沿生产线方向的纵向及与纵向正交的横向的伸长率的平均值。
另外,作为人造革基材或使用了其的人造革的伸缩性,从保持各向异性小的伸缩性的观点考虑,优选施加了1kg负载5分钟时的纵向及横向的伸长率均为10%以上。
另外,作为本实施方式的人造革基材,从能够得到在反复伸长后也具备一定以上的伸长率和伸长回复率的伸缩性优异的人造革基材的观点考虑,特别优选为如下所述的人造革基材,其包含无纺布和赋予至无纺布的内部的水性聚氨酯,所述无纺布为纤维(A)和纤维(B)的抱合体,其中,纤维(A)是由特性粘度相互不同的2种树脂形成的平均弯曲率为15%以上的卷曲纤维,且是具有0.6~2.5dtex的平均纤度的长纤维,纤维(B)是具有小于0.6dtex的平均纤度的极细纤维,水性聚氨酯的含有比例为8~15质量%,厚度方向的截面的空隙的平均面积为300~1000μm2。
在使作为卷曲纤维的纤维(A)与作为具有小于0.6dtex的平均纤度的极细纤维的纤维(B)抱合而成的无纺布中,作为极细纤维的纤维(B)具有以一定的伸长范围固定纤维(A)的作用,所述纤维(A)是反复伸长时丝完全伸长展开而容易变得难以回复的卷曲纤维。但是,在纤维(A)与纤维(B)的抱合状态不充分的情况下,存在作为极细纤维的纤维(B)以一定的伸长范围固定作为卷曲纤维的纤维(A)的移动的作用降低的倾向。如果使用作为平均弯曲率为15%以上的卷曲纤维的纤维(A),则容易因其蜷曲而使纤维(A)与纤维(B)充分抱合。另外,通过使卷曲纤维为长纤维,变得不容易脱落,伸缩性不容易降低。另外,通过使作为极细纤维的纤维(B)的外观状态变得致密,可赋予优异的立毛外观。另外,通过使水性聚氨酯的含有比例为8~15质量%,可以适度束缚纤维来保持伸缩性,而不会使人造革基材如橡胶那样变得过硬。因此,通过使纤维(A)和纤维(B)充分抱合,将厚度方向的截面的空隙的平均面积调整为300~1000μm2,并使每一个空隙为适度大小,由此可以得到在反复伸长后也具备一定以上的伸长率和伸长回复率的伸缩性优异的人造革基材。
厚度方向的截面的空隙的平均面积优选为300~1000μm2,更优选为350~950μm2,特别优选为400~900μm2。这里,厚度方向的截面的空隙的平均面积是指如后所述计算出的厚度方向上每一个空隙的面积的平均值。通过使空隙的平均面积为这样的范围,即使包含纤维(A),也可以以空隙减小的方式进行抱合,所述纤维(A)是蓬松、容易***的平均弯曲率高的卷曲纤维。在空隙的平均面积超过1000μm2时,作为纤维(A)和纤维(B)的抱合体的无纺布的抱合不充分且空隙多,因此具有反复伸长后的伸缩性的持续性降低的倾向。另外,在空隙的平均面积小于300μm2时,作为纤维(A)和纤维(B)的抱合体的无纺布的抱合变得过强、水性聚氨酯过多而使纤维难以移动,因此具有伸缩性降低的倾向。
这样的人造革基材在反复伸长后的伸缩性的持续性优异。具体而言,例如,可以实现如后所述测定的20次伸长后的平均伸长率为18%以上且平均伸长回复率为55%以上的人造革基材,进一步可以实现20次伸长后的平均伸长率为20%以上且平均伸长回复率为60%以上的人造革基材。
作为通过本实施方式得到的人造革基材或人造革的表观密度,从可以得到机械特性和高伸缩性特别优异的人造革的观点考虑,优选为0.20~0.7g/cm3,更优选为0.25~0.5g/cm3。
实施例
以下,通过实施例对本发明更具体地进行说明。需要说明的是,本发明的范围并不受实施例的任何限定。
首先,以下对本实施例所使用的评价方法进行说明。
〈平均纤度〉
平均纤度如下所述进行测定。以3000倍拍摄了人造革基材的截面的扫描电子显微镜(SEM)照片。然后,从SEM照片随机选择10个纤维的截面来测定截面积,计算出该截面积的平均值。然后,使用各树脂的密度将截面积的平均值换算为平均纤度。需要说明的是,在SEM照片中,将并排型的聚酯纤维作为纤维(A),将除此以外的纤维作为纤维(B),区别开来进行测定。
〈特性粘度〉
使用苯酚/四氯乙烷(体积比1/1)混合溶剂作为溶剂,在30℃下使用乌氏粘度计(林制作所制HRK-3型)进行了测定。
〈平均弯曲率〉
将人造革基材的厚度方向的中央部分切片后,以100倍的倍率对下层侧表面进行电子显微镜观察。然后,如图1所示,测定从纤维1的弯曲部的100μm长度的弦至与垂下垂线相交的纤维的距离A,通过下式计算出弯曲率。然后,随机测定10个部位的弯曲率的平均值作为平均弯曲率。
平均弯曲率(%)=A(μm)/100(μm)×100
〈聚氨酯比例〉
测定待层叠的纤维(A1)和纤维(B1)的单位面积重量,根据其总单位面积重量W(g/m2)及其中的纤维(A)和纤维(B)各自的比例,计算出纤维(A)和纤维(B)的单位面积重量X(g/m2)。接着,将水性聚氨酯液浓度设为Y(%)、将含浸于无纺布时的轧液率设为Z(%)时,根据下式求出了水性聚氨酯的比例。
水性聚氨酯比例(%)=
[W×Z/100×Y/100]/[W×Z/100×Y/100+X]×100
〈表观密度〉
按照JIS L1913测定厚度(mm)及单位面积重量(g/cm2),根据这些值计算出表观密度(g/cm3)。
〈伸长率及伸长回复率〉
伸长率表示恒定负载下进行拉伸时的伸长率。另外,伸长回复率表示恒定负载下伸长、并在去除负载后的回复率。将人造革基材切成2.5cm宽度,在长度5cm之间加入3cm间隔的基准线,对施加1kg负载5分钟后的基准线伸长的长度L1进行测定,通过下式测定了伸长率。
·伸长率(%)=[L1(cm)-3(cm)]/3(cm)×100
另外,在解除负载5分钟后,测定基准线间的长度L2,通过下式测定了伸长回复率。
·伸长回复率(%)=[L1(cm)-L2(cm)]/[L1(cm)-3(cm)]/×100
〈立毛感〉
通过肉眼观察及触感,按照以下基准对得到的立毛人造革的外观进行了判定。
A:纤维细致地散开,具有均匀的长度,为柔软光滑的触感的立毛面。
B:纤维粗略地散开,具有不均匀的长度,为粗糙触感且没有光泽的立毛感。
〈手感〉
将得到的立毛人造革,按照以下基准对刚性、柔软性的触感进行了判定。
A:具有充实感,没有死折,为柔软性优异的手感。
B:符合缺乏充实感,有死折、硬中任意一种以上的手感。
〈伸缩感〉
对得到的立毛人造革进行拉伸,按照以下基准对此时的力的程度、回复容易程度的触感进行了判定。
A:用很弱的力容易伸长,解除力后伸长的回复快。
B:符合以下的任意情况:用很弱的力难以伸长且解除力后伸长的回复慢、或用很弱的力容易伸长但在解除力后伸长的回复慢、或用很弱的力难以伸长且解除力后伸长的回复快。
〈撕裂强度〉
从人造革的原料卷切下纵10cm×横4cm的试验片。然后,在试验片的短边的中央与长边平行地切开5cm的切口。然后,使用拉伸试验机将各切片夹于夹具的卡盘,以10cm/min的拉伸速度测定了s-s曲线。对于原料卷的纵向和与纵向垂直的横向,测定各3个试验片,分别求出了平均值。
[实施例1]
使用特性粘度[η]=1.025(dl/g)的聚对苯二甲酸丁二醇酯(PBT)和特性粘度[η]=0.585(dl/g)的聚对苯二甲酸乙二醇酯(PET),在275℃下利用熔融复合纺丝用喷丝头喷出,调整喷射器压力,使得纺丝速度为4000m/min,将长纤维捕集至网上,得到了包含平均纤度1.5dtex的并排型的聚酯纤维的第1纤维网。
另一方面,将水溶性热塑性聚乙烯醇类树脂(PVA;海成分)和改性度6摩尔%的间苯二甲酸改性聚对苯二甲酸乙二醇酯(岛成分)以海成分/岛成分为50/50(质量比)的方式在260℃下利用熔融复合纺丝用喷丝头(岛数:12岛/纤维)喷出,以纺丝速度800m/min进行了纺丝。接着,进行拉伸,得到平均纤度7.7dtex的纤维后,赋予卷曲。将得到的卷曲后纤维切断为51mm,通过梳棉机,得到了第2纤维网。
接着,将得到的网以第2纤维网/第1纤维网/第2纤维网=1/2/1的重量比进行层叠,形成了层叠网。然后,使用1个钩的针以1840P/cm2的针刺密度对层叠网进行针刺处理,由此形成了单位面积重量220g/m2的抱合纤维片。
接着,在110℃、23.5%RH的条件下对抱合纤维片进行了蒸气处理。然后,在90~110℃的烘箱中进行干燥后,进一步在115℃下进行热压,由此得到了单位面积重量312g/m2、表观密度0.52g/cm3、厚度0.60mm的经热收缩处理的热收缩纤维片。
接者,以轧液率(pick up)50%使水性聚氨酯的乳液(固体成分18%)含浸于热收缩纤维片。需要说明的是,水性聚氨酯为聚碳酸酯类无黄变聚氨酯。另外,在乳液中相对于聚氨酯100质量份添加碳二亚胺类交联剂4.9质量份和硫酸铵6.4份,将聚氨酯的固体成分调整为10%。然后,将含浸有乳液的热收缩纤维片在115℃、25%RH气体氛围中进行干燥处理,并进一步在150℃下进行了干燥处理。
然后,一边对赋予了聚氨酯的热收缩纤维片进行夹持处理及高压水流处理,一边在95℃的热水中浸渍10分钟,由此溶解去除PVA,形成了平均纤度0.3dtex的PET的极细纤维。然后,通过进行干燥,得到了人造革基材。
然后,在人造革基材的背面使用#120纸,在正面使用#240、#320纸,对两面进行磨削,由此精加工成形成有立毛面的人造革基材。然后,使用分散染料在120℃下对形成有立毛面的人造革基材进行高压染色,由此得到了具有麂皮状立毛面的立毛人造革。得到的立毛人造革的单位面积重量为240g/m2,表观密度为0.282g/cm3,厚度为0.85mm。
然后,按照上述评价方法对立毛人造革的各种特性进行了评价。将以上的结果示于下述表1。
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[实施例2]
如表1所示,在实施例1中,使用特性粘度[η]=0.775(dl/g)的PET代替特性粘度[η]=1.025(dl/g)的PBT,使用特性粘度[η]=0.52(dl/g)的PET代替特性粘度[η]=0.585(dl/g)的PET,除此以外,同样地得到立毛人造革,并进行了评价。将结果示于表1。
[实施例3]
如表1所示,在实施例1中,使用特性粘度[η]=0.52(dl/g)的PET代替特性粘度[η]=0.585(dl/g)的PET,并进一步变更了水性聚氨酯的含有比例,除此以外,同样地得到立毛人造革,并进行了评价。将结果示于表1。
[实施例4]
如表1所示,在实施例1中,形成平均纤度0.5dtex的PET的极细纤维来代替形成平均纤度0.3dtex的PET的极细纤维,并进一步变更了水性聚氨酯的含有比例,除此以外,同样地得到立毛人造革,并进行了评价。将结果示于表1。
[实施例5]
将实施例3的第2纤维网变更为如下制造的第2纤维网,并变更为表1所示的长纤维的极细纤维,除此以外,与实施例3同样地得到立毛人造革,并进行了评价。将结果示于表1。
(第2纤维网的制造)
将水溶性热塑性聚乙烯醇类树脂(PVA;海成分)和改性度6摩尔%的间苯二甲酸改性聚对苯二甲酸乙二醇酯(岛成分)以海成分/岛成分为25/25(质量比)的方式在260℃下利用熔融复合纺丝用喷丝头(岛数:12岛/纤维)喷出,调整喷射器压力,使得纺丝速度达到3500m/min,将长纤维捕集至网上,得到了包含长纤维的平均纤度3.0dtex的海岛型复合纤维的第2纤维网。
[实施例6]
如表1所示,在实施例3中,使用了包含平均纤度0.6dtex的并排型的聚酯纤维的第1纤维网来代替包含平均纤度1.5dtex的并排型的聚酯纤维的第1纤维网,除此以外,同样地得到立毛人造革,并进行了评价。将结果示于表1。
[比较例1]
如表1所示,在实施例2中,使用特性粘度[η]=1.025(dl/g)的PBT代替特性粘度[η]=0.775(dl/g)的PET,仅用第1纤维网形成相同单位面积重量的层叠网代替以第2纤维网/第1纤维网/第2纤维网=1/2/1的重量比进行层叠而形成层叠网,并进一步变更水性聚氨酯的含有比例,除此以外,同样地得到立毛人造革,并进行了评价。将结果示于表1。
[比较例2]
如表1所示,在比较例1中,变更为以2760刺/cm2对层叠网进行针刺等来代替以1840刺/cm2进行针刺,除此以外,同样地得到立毛人造革,并进行了评价。将结果示于表1。
[比较例3]
如表1所示,在实施例1中,使用包含由特性粘度[η]=0.615(dl/g)的PET形成的聚酯纤维的第1纤维网代替包含平均纤度1.5dtex的并排型的聚酯纤维的第1纤维网,以3680刺/cm2对层叠网进行针刺代替以1840刺/cm2进行针刺,并进一步变更水性聚氨酯的含有比例,除此以外,同样地得到立毛人造革,并进行了评价。将结果示于表1。
[比较例4]
如表1所示,在实施例1中,形成平均纤度0.6dtex的PET的纤维来代替形成平均纤度0.3dtex的PET的极细纤维,除此以外,同样地得到立毛人造革,并进行了评价。将结果示于表1。
参照表1,本发明的实施例1~6中得到的立毛人造革均具有纵向及横向上均显示出10%以上的伸长率及10%以上的平均伸长率的伸缩性,撕裂强度也在纵向及横向均显示出3kg以上,而且立毛感也优异。另一方面,虽然不包含作为具有小于0.6dtex的平均纤度的极细纤维的纤维(B)的比较例1的立毛人造革在纵向及横向上均显示出10%以上的伸长率及10%以上的平均伸长率,但撕裂强度低。另外,在基于比较例1的立毛人造革为了提高撕裂强度而增加针刺密度并提高抱合度的比较例2中得到的立毛人造革的情况下,虽然撕裂强度提高,但伸缩性降低。另外,相对于实施例1,提高了纤维(B)的纤度的比较例4中得到的立毛人造革的立毛感差。
[实施例7]
以50/50的比率使用特性粘度[η]=1.025(dl/g)的聚对苯二甲酸丁二醇酯(PBT)和特性粘度[η]=0.52(dl/g)的聚对苯二甲酸乙二醇酯(PET),在275℃下利用1个孔的面积C为0.08mm2的熔融复合纺丝用喷丝头以喷出速度A0.25(g/min)喷出。需要说明的是,此时,树脂的熔融密度B为1.21(g/cm3)。然后,调整喷射器压力,使得纺丝速度D为3987m/min,以纺丝牵伸比为1544的方式进行纺丝,将长纤维捕集至网上,由此得到了包含平均纤度0.63dtex的并排型的聚酯纤维的第1纤维网。
另一方面,将水溶性热塑性聚乙烯醇类树脂(PVA;海成分)和改性度6摩尔%的间苯二甲酸改性聚对苯二甲酸乙二醇酯(岛成分)以海成分/岛成分为50/50(质量比)的方式在260℃下利用熔融复合纺丝用喷丝头(岛数:12岛/纤维)喷出,以纺丝速度800m/min进行了纺丝。接者,进行拉伸,在得到了平均纤度7.7dtex的纤维之后,赋予卷曲。将得到的卷曲后纤维切断为51mm,通过梳棉机,得到了第2纤维网。
接着,将得到的网以第2纤维网/第1纤维网/第2纤维网=1/2/1的质量比进行层叠,形成了层叠网。然后,使用1个钩的针以1840P/cm2的针刺密度对层叠网进行针刺处理,由此形成了单位面积重量410g/m2的抱合纤维片。
接着,在110℃、23.5%RH的条件下对抱合纤维片进行了蒸气处理。然后,在90~110℃的烘箱中进行干燥后,进一步在115℃下进行热压,由此得到了单位面积重量511g/m2、表观密度0.63g/cm3、厚度0.81mm的经热收缩处理的热收缩纤维片。
接者,以轧液率50%使水性聚氨酯的乳液(固体成分10%)含浸于热收缩纤维片。水性聚氨酯为聚碳酸酯类无黄变聚氨酯。另外,使用了相对于水性聚氨酯100质量份配合碳二亚胺类交联剂1.5质量份和硫酸铵7.5质量份、并以水性聚氨酯的固体成分为10%的方式进行了调整的乳液。然后,将含浸有乳液的热收缩纤维片在115℃、25%RH气体氛围中进行干燥处理,并进一步在150℃下进行干燥处理。
然后,一边对赋予了聚氨酯的热收缩纤维片进行夹持处理及高压水流处理,一边在95℃的热水中浸渍10分钟,由此溶解去除PVA,形成了平均纤度0.3dtex的PET的极细纤维。然后,通过进行干燥,得到了人造革基材。
然后,在人造革基材的背面使用#120纸,在正面使用#240、#320纸,对两面进行磨削,由此精加工成形成有立毛面的人造革基材。然后,使用分散染料在120℃下对形成有立毛面的人造革基材进行高压染色,由此得到了具有麂皮状立毛面的立毛人造革。得到的立毛人造革的单位面积重量为352g/m2,表观密度为0.314g/cm3,厚度为1.12mm。
另外,聚氨酯含有比例为10质量%。
然后,按照上述评价方法对立毛人造革的各种特性进行了评价。需要说明的是,“卷曲型纤维(A1)的纺丝牵伸比”如下所述进行计算。
〈卷曲型纤维(A1)的纺丝牵伸比〉
在卷曲型纤维(A1)熔融纺丝时,将从纺丝喷嘴1个孔喷出的聚合物的喷出速度设为A(g/min)、聚合物的熔融密度设为B(g/cm3)、1个孔的面积设为C(mm2)、纺丝速度设为D(m/min),通过下式计算出纺丝牵伸比。
·纺丝牵伸比=D/(A/B/C×104)
需要说明的是,对于树脂的熔融密度B(g/cm3)而言,将熔融纺丝时分别喷出特性粘度不同的2种树脂时的喷出体积(cc/rpm)设为E1、E2,将喷出它们时的各齿轮泵的转速(rpm)分别设为F1和F2,测定1分钟喷出的聚合物喷出量(g/min)G1和G2,根据下式进行计算。
·熔融密度(g/cm3)=G1/E1/F1×G1/(G1+G2)+G2/E2/F2×G2/(G1+G2)另外,“厚度方向的截面的空隙的平均面积”如下所述进行了评价。
〈厚度方向的截面的空隙的平均面积〉
厚度方向的截面的空隙的平均面积如下所述进行了测定。
用扫描电子显微镜以40倍的倍率对人造革基材的厚度方向的截面的整个层进行观察,拍摄了其图像。然后,对于得到的图像,使用图像分析软件Popimaging(Digitalbeing kids公司制)利用动态阈值法将图像二值化。然后,用image pro premier(NIPPONROPER公司制)读取二值化后的图像,用计数工具提取了面积为5点以上的空隙部。在整体上选择的3个部位的截面进行了测量。然后,测定用测量工具提取到的各空隙部的面积,求出了平均值。图2示出了实施例7中得到的图像的一例。各黑色部位为空隙部。
另外,对于“伸长率及伸长回复率”、“手感”及“伸缩感”而言,分别获得了重复“伸长率及伸长回复率”的操作时的第1次及第20次的结果。
将以上的结果示于下述表2。
表2
[实施例8]
在实施例7中,使用如下所述制造的第1纤维网,除此以外,同样地得到立毛人造革,并进行了评价。
以50/50的比率使用特性粘度[η]=1.025(dl/g)的聚对苯二甲酸丁二醇酯(PBT)和特性粘度[η]=0.52(dl/g)的聚对苯二甲酸乙二醇酯(PET),在275℃下利用1个孔的面积C为0.08mm2的熔融复合纺丝用喷丝头以喷出速度A0.51(g/min)喷出。然后,调整喷射器压力,使得纺丝速度D为4048m/min,以纺丝牵伸比为768的方式进行纺丝,将长纤维捕集至网上,由此得到了包含平均纤度1.18dtex的并排型的聚酯纤维的第1纤维网。
将结果示于表2。
[实施例9]
在实施例7中,使用如下所述制造的第1纤维网,除此以外,同样地得到立毛人造革,并进行了评价。
以50/50的比率使用特性粘度[η]=1.025(dl/g)的聚对苯二甲酸丁二醇酯(PBT)和特性粘度[η]=0.52(dl/g)的聚对苯二甲酸乙二醇酯(PET),在275℃下利用1个孔的面积C为0.08mm2的熔融复合纺丝用喷丝头以喷出速度A1.0(g/min)喷出。然后,调整喷射器压力,使得纺丝速度D为4132m/min,以纺丝牵伸比为400的方式进行纺丝,将长纤维捕集至网上,由此得到了包含平均纤度2.42dtex的并排型的聚酯纤维的第1纤维网。
将结果示于表2。
[实施例10]
在实施例7中,使用如下所述制造的第2纤维网,形成平均纤度0.5dtex的PET的极细纤维来代替形成平均纤度0.3dtex的PET的极细纤维,除此以外,同样地得到立毛人造革,并进行了评价。
将水溶性热塑性聚乙烯醇类树脂(PVA;海成分)和改性度6摩尔%的间苯二甲酸改性聚对苯二甲酸乙二醇酯(岛成分)以海成分/岛成分为50/50(质量比)的方式在260℃下利用熔融复合纺丝用喷丝头(岛数:12岛/纤维)喷出,以纺丝速度800m/min进行了纺丝。接着,进行拉伸,得到了平均纤度11.8dtex的纤维,然后赋予了卷曲。将得到的卷曲后纤维切断为51mm,通过梳棉机,得到了第2纤维网。
将结果示于表2。
[实施例11]
在实施例7中,将以第2纤维网/第1纤维网/第2纤维网=1/2/1的质量比进行层叠而形成层叠网替换为以1/8.5/1的质量比进行层叠而得到层叠网,除此以外,同样地得到立毛人造革,并进行了评价。将结果示于表2。
[实施例12]
在实施例7中,将以第2纤维网/第1纤维网/第2纤维网=1/2/1的质量比进行层叠而形成层叠网替换为以0.7/1/0.7的质量比进行层叠而得到层叠网,除此以外,同样地得到立毛人造革,并进行了评价。将结果示于表2。
[实施例13]
在实施例8中,以轧液率50%使水性聚氨酯的乳液(固体成分11%)含浸于热收缩纤维片来代替以轧液率50%含浸水性聚氨酯的乳液(固体成分10%),将聚氨酯含有比例变更为8.5质量%来代替10质量%,除此以外,同样地得到立毛人造革,并进行了评价。
将结果示于表2。
[实施例14]
在实施例8中,以轧液率50%使水性聚氨酯的乳液(固体成分18.8%)含浸于热收缩纤维片来代替以轧液率50%含浸水性聚氨酯的乳液(固体成分10%),将聚氨酯含有比例变更为13质量%来代替10质量%,除此以外,同样地得到立毛人造革,并进行了评价。将结果示于表2。
[实施例15]
在实施例13中,使用如下所述制造的第1纤维网,除此以外,同样地得到立毛人造革,并进行了评价。
以50/50的比率使用特性粘度[η]=1.025(dl/g)的聚对苯二甲酸丁二醇酯(PBT)和特性粘度[η]=0.52(dl/g)的聚对苯二甲酸乙二醇酯(PET),在275℃下利用1个孔的面积C为0.08mm2的熔融复合纺丝用喷丝头以喷出速度A1.0(g/min)喷出。然后,调整喷射器压力,使得纺丝速度D为4065m/min,以纺丝牵伸比为393的方式进行纺丝,将长纤维捕集至网上,由此得到了包含平均纤度2.46dtex的并排型的聚酯纤维的第1纤维网。
将结果示于下述表3。
表3
[比较例5]
在实施例7中,仅用如下所述制造的第1纤维网形成了层叠网,并进一步将水性聚氨酯含有比例变更为6质量%来代替10质量%,除此以外,同样地得到立毛人造革,并进行了评价。
以50/50的比率使用特性粘度[η]=1.025(dl/g)的聚对苯二甲酸丁二醇酯(PBT)和特性粘度[η]=0.52(dl/g)的聚对苯二甲酸乙二醇酯(PET),在275℃下利用1个孔的面积C为0.08mm2的熔融复合纺丝用喷丝头以喷出速度A0.51(g/min)喷出。然后,调整喷射器压力,使得纺丝速度D为3643m/min,以纺丝牵伸比为691的方式进行纺丝,将长纤维捕集至网上,由此得到了包含平均纤度1.4dtex的并排型的聚酯纤维的第1纤维网。
将结果示于下述表3。
[比较例6]
在实施例7中,使用包含平均纤度1.32dtex的常规型的聚酯纤维的第1纤维网代替包含并排型的聚酯纤维的第1纤维网,仅用第1纤维网形成层叠网,并进一步将水性聚氨酯含有比例变更为6质量%来代替10质量%,除此以外,同样地得到立毛人造革,并进行了评价。将结果示于表3。
[实施例16]
在实施例8中,以轧液率50%使水性聚氨酯的乳液(固体成分6.6%)含浸于热收缩纤维片来代替以轧液率50%含浸水性聚氨酯的乳液(固体成分10%),将聚氨酯含有比例变更为5质量%来代替10质量%,除此以外,同样地得到立毛人造革,并进行了评价。将结果示于表3。
[实施例17]
在实施例8中,以轧液率50%使水性聚氨酯的乳液(固体成分10.2%)含浸于热收缩纤维片来代替以轧液率50%含浸水性聚氨酯的乳液(固体成分10%),将聚氨酯含有比例变更为7.5质量%来代替10质量%,除此以外,同样地得到立毛人造革,并进行了评价。将结果示于表3。
[实施例18]
在实施例8中,以轧液率50%使水性聚氨酯的乳液(固体成分24%)含浸于热收缩纤维片来代替以轧液率50%含浸水性聚氨酯的乳液(固体成分10%),将聚氨酯含有比例变更为16质量%来代替10质量%,除此以外,同样地得到立毛人造革,并进行了评价。将结果示于表3。
参照表2,厚度方向的截面的空隙的平均面积为300~1000μm2的实施例7~14中得到的立毛人造革均具有重复伸长后回复力高的伸缩性,重复伸长后也保持了高伸缩性。另一方面,参照表3,对于纤维(A)的平均弯曲率稍低、以纺丝牵伸比393制造的实施例15的人造革而言,厚度方向的截面的空隙的平均面积超过1000μm2,重复伸长后的伸长回复率稍低。另外,对于仅用第1纤维网形成了层叠网的比较例5而言,厚度方向的截面的空隙的平均面积也超过1000μm2,重复伸长后的伸长回复率低,撕裂强度也低。另外,使用包含平均纤度1.32dtex的常规型聚酯纤维的第1纤维网代替包含并排型的聚酯纤维的第1纤维网、且仅用第1纤维网形成了层叠网的比较例6的伸缩性低。另外,聚氨酯的含有比例为5%的实施例16的重复伸长后的伸长回复率低。聚氨酯的含有比例为7.5%的实施例17的重复伸长后的伸长回复率也低。聚氨酯的含有比例为16%的实施例18的伸长率低。
Claims (14)
1.一种人造革基材,其包含无纺布和赋予至所述无纺布的内部的水性聚氨酯,所述无纺布为通过纺粘法得到的纤维(A)的纤维网和纤维(B)的纤维网的抱合体,所述纤维(A)为连续纤维的长纤维,其中,
所述纤维(A)是由相互特性粘度之差为0.05dl/g以上的2种聚酯类树脂形成的卷曲纤维、且具有0.6~2.5dtex的平均纤度,
所述纤维(B)是由具有小于0.6dtex的平均纤度的聚酯类树脂形成的极细纤维,
相对于所述无纺布和所述水性聚氨酯的总量,所述水性聚氨酯的含有比例为8~15质量%。
2.根据权利要求1所述的人造革基材,其中,所述纤维(A)的平均弯曲率为10%以上。
3.根据权利要求1所述的人造革基材,其中,所述纤维(A)的平均弯曲率为15%以上。
4.根据权利要求3所述的人造革基材,其中,所述纤维(B)的平均弯曲率小于15%。
5.根据权利要求1所述的人造革基材,其中,所述纤维(B)为平均纤维长度小于100mm的短纤维。
6.根据权利要求1所述的人造革基材,其中,所述纤维(A)为并排型纤维或偏芯芯鞘型纤维。
7.根据权利要求1所述的人造革基材,其中,所述纤维(A)与所述纤维(B)的配合比例((A)/(B))为10/90~90/10。
8.根据权利要求1所述的人造革基材,其被施加1kg负载5分钟时的平均伸长率为10%以上。
9.根据权利要求1~8中任一项所述的人造革基材,其中,
所述人造革基材的厚度方向的截面的空隙的平均面积为300~1000μm2。
10.一种立毛人造革,其包含权利要求1~9中任一项所述的人造革基材,且其一面经过了立毛处理。
11.一种人造革基材的制造方法,其是权利要求1所述的人造革基材的制造方法,该方法至少包括:
准备第1纤维网的工序,所述第1纤维网通过纺粘法得到,包含用于形成所述纤维(A)的、由相互特性粘度之差为0.05(dl/g)以上的2种树脂形成的0.6~2.5dtex的长纤维的卷曲型纤维(A1);
准备用于形成所述纤维(B)的极细纤维发生型纤维(B1)的第2纤维网的工序;
将所述第2纤维网层叠于所述第1纤维网的至少一面而形成层叠网的工序;
形成抱合纤维片的工序,所述抱合纤维片是使形成所述层叠网的所述卷曲型纤维(A1)与所述极细纤维发生型纤维(B1)进行抱合处理而成的;
使所述抱合纤维片热收缩而形成热收缩纤维片的工序;
通过对形成所述热收缩纤维片的所述极细纤维发生型纤维(B1)进行极细纤维化处理而形成作为所述卷曲型纤维(A1)和所述纤维(B)的抱合体的无纺布的工序;以及
对所述热收缩纤维片或所述无纺布含浸赋予所述水性聚氨酯的工序。
12.根据权利要求11所述的人造革基材的制造方法,其中,所述层叠网是在所述第1纤维网的两面层叠有所述第2纤维网的层叠体。
13.根据权利要求11所述的人造革基材的制造方法,其中,含浸赋予所述水性聚氨酯的工序是使聚氨酯水性乳液含浸于所述热收缩纤维片或所述无纺布之后进行干燥,由此生成所述水性聚氨酯的工序。
14.根据权利要求13所述的人造革基材的制造方法,其中,
所述卷曲型纤维(A1)为以纺丝牵伸比400以上进行纺丝而成的纤度0.6dtex以上的卷曲型纤维,
利用该制造方法制造的人造革基材是所述水性聚氨酯的含有比例为8~15质量%、厚度方向的截面的空隙的平均面积为300~1000μm2的人造革基材。
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WO2020044911A1 (ja) | 2020-03-05 |
EP3845704A4 (en) | 2022-06-22 |
JPWO2020044911A1 (ja) | 2021-08-12 |
EP3845704B1 (en) | 2023-07-19 |
KR20210025100A (ko) | 2021-03-08 |
JP7249352B2 (ja) | 2023-03-30 |
EP3845704A1 (en) | 2021-07-07 |
TW202027994A (zh) | 2020-08-01 |
TWI821370B (zh) | 2023-11-11 |
US20210310186A1 (en) | 2021-10-07 |
KR102652060B1 (ko) | 2024-03-28 |
CN112567092A (zh) | 2021-03-26 |
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