CN104937149A - 聚氨酯纤维 - Google Patents
聚氨酯纤维 Download PDFInfo
- Publication number
- CN104937149A CN104937149A CN201480005386.3A CN201480005386A CN104937149A CN 104937149 A CN104937149 A CN 104937149A CN 201480005386 A CN201480005386 A CN 201480005386A CN 104937149 A CN104937149 A CN 104937149A
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- CN
- China
- Prior art keywords
- fragrance
- fiber
- methyl
- acid
- polyurethanes
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 229920006306 polyurethane fiber Polymers 0.000 title claims abstract description 30
- 239000003205 fragrance Substances 0.000 claims abstract description 251
- 239000000835 fiber Substances 0.000 claims abstract description 190
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- 229920002635 polyurethane Polymers 0.000 claims description 146
- 239000004744 fabric Substances 0.000 claims description 106
- 238000005406 washing Methods 0.000 claims description 77
- 230000014759 maintenance of location Effects 0.000 claims description 68
- 238000000034 method Methods 0.000 claims description 68
- 239000003795 chemical substances by application Substances 0.000 claims description 66
- 150000001875 compounds Chemical class 0.000 claims description 34
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 22
- 238000010521 absorption reaction Methods 0.000 claims description 21
- 229910052799 carbon Inorganic materials 0.000 claims description 20
- KJAMZCVTJDTESW-UHFFFAOYSA-N tiracizine Chemical compound C1CC2=CC=CC=C2N(C(=O)CN(C)C)C2=CC(NC(=O)OCC)=CC=C21 KJAMZCVTJDTESW-UHFFFAOYSA-N 0.000 claims description 20
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- 229910052757 nitrogen Inorganic materials 0.000 description 41
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- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 14
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- 239000000470 constituent Substances 0.000 description 13
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 description 13
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- 238000009987 spinning Methods 0.000 description 11
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 11
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 10
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 9
- QMVPMAAFGQKVCJ-UHFFFAOYSA-N citronellol Chemical compound OCCC(C)CCC=C(C)C QMVPMAAFGQKVCJ-UHFFFAOYSA-N 0.000 description 9
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- WEEGYLXZBRQIMU-UHFFFAOYSA-N 1,8-cineole Natural products C1CC2CCC1(C)OC2(C)C WEEGYLXZBRQIMU-UHFFFAOYSA-N 0.000 description 8
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- 239000011734 sodium Substances 0.000 description 8
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- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 7
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- 240000002307 Solanum ptychanthum Species 0.000 description 7
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- 150000001412 amines Chemical class 0.000 description 7
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 7
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Abstract
本发明提供一种在吸收香料成分后经过长时间仍保持香气的留香性纤维。一种留香性聚氨酯类纤维,其特征在于,从吸收香料成分起48小时后的香料成分的总释放量为0.1μg/g·小时以上且1000μg/g·小时以下。
Description
技术领域
本发明涉及对包含香料成分的洗涤用柔顺剂和/或洗涤剂等的香气持续性优良的聚氨酯类纤维。
背景技术
日常生活中想要享受香味的期望高,针对香味易附着于以衣服用布帛为代表的寝具等各种纤维结构物、附着后也不会通过挥发等消失并且即便是少量也有强香味的香料类、香料配方、将香料胶囊化的技术正进行研究和开发。
并且,近年来,喜好在日常洗涤时进行香味的赋予。其代表性的方法是,使用在附加香料后的洗涤柔顺剂或洗涤剂的作用下,布帛或衣物即便在干燥途中以及理所当然在干燥后的长期中也持续有令人舒心的香味的洗涤剂、柔顺剂。已发明了大量的适用于这些洗涤剂、柔顺剂的香料组合物。
作为香味其本身的香料类、香料配方、应用了这些香料类、香料配方的柔顺剂、洗涤剂、洗涤专用香料包、洗涤后喷雾型香料包等香料方面的发明遍及多种多样。
若列举消费者在家庭等中进行洗涤时赋予香味的优点,则首先重要的是随着每次洗涤能够重复赋予作为目标的所喜好的香味。另外,优良的是,通过换穿赋予了不同香料的衣物能够重新设定不同香味。并且,重要的是,近年来的香味的喜好有重视轻快的香味的趋势。轻快的香味成分的香料类大多是低分子且具有高挥发性。即,香水或花露水的情况下,以直接喷雾至皮肤为前提,高挥发性的香料成分立即挥发(前调、几分钟左右的香水的第一印象),难以使其长时间存在,难以使轻快的香味、清爽的优选香味持续。作为香水或花露水的主要功能的香味(中调、基调、香水的余香)被称作厚重香味,据称正式的印象和倾向较强。
然而,对于作为赋予香味的对象物的布帛方面,尚未进行满足上述期望的尝试。也就是说,尚没有目的在于通过追求改良纤维结构物方面的材料来提高香料吸附率、使香味长期持续的技术构思。尤其是完全没有目的在于使轻快的香味长期持续的技术构思。
作为与其接近的尝试,可以列举在制造时预先对纤维、纤维结构物赋予香味成分或除臭成分等的例子(专利文献1和专利文献2)。另外,作为用于芳香剂的香料基材的例子,可以列举专利文献3。
即,从初始起具备特定香料的纤维、纤维结构物。专利文献1和专利文献2中记载了在制造时对纤维物质赋予香料。然而,令人遗憾的是,香味的嗜好性非常高,与个人的感性结合,与其对应地预先准备表现出多种香味的产品是非常不经济的。并且,在制造时预先赋予特定香料还存在在消费者之后在洗涤等时赋予所喜好的香料的情况下由于预先赋予的香料残留而得不到所喜好的香气等损害该目的的情况。此外,该方法也不满足上述反复重新设定香味的要求、对轻快香味的要求。
据申请人所知,尽管有具备香气持续性的香料类的报道,但现状是尚无可得到具备香气持续性的布帛的报道。
现有技术文献
专利文献
专利文献1:日本特开2012-012710号公报
专利文献2:日本特开2011-162906号公报
专利文献3:日本特表2008-519145号公报
发明内容
发明要解决的问题
如上所述,尚无具备令人满足的香气持续性的布帛的报道。
本发明鉴于在制造时未预先附着香料、收容上述香味的纤维结构物方面的问题,其目的在于,通过对构成作为被赋予香味的对象物的布帛的纤维进行改良,提供即便在吸收香料成分后经过长时间(例如48小时左右)香气也会持续的留香性纤维。
用于解决问题的手段
本发明人们发现,包含本发明的聚氨酯类纤维的衣服、尤其是贴身衣服、中衣能够在低于皮肤的温度使香料成分稳定地挥发,通过将这种衣服的构成材料活用作香料的含浸基材、尤其是高挥发性香料吸收基材,可得到使高挥发香料的轻快香味持续的令人吃惊的效果。本发明基于这样的见解,经进一步反复深入开发而完成。即,本发明涉及以下的发明。
[1]一种留香性聚氨酯类纤维,其特征在于,从吸收香料成分起48小时后的香料成分的总释放量为0.1μg/g·小时以上且1000μg/g·小时以下。
[2]如上述[1]所述的留香性聚氨酯类纤维,其特征在于,上述聚氨酯类纤维为聚氨酯纤维和/或聚氨酯脲纤维。
[3]如上述[1]或[2]所述的留香性聚氨酯类纤维,其特征在于,上述聚氨酯类纤维的氨基甲酸基浓度和脲基浓度的合计为1.0mol/kg以上且5.0mol/kg以下。
[4]如上述[1]~[3]中任一项所述的留香性聚氨酯类纤维,其特征在于,上述聚氨酯类纤维每1g的纤维表面积为0.02m2以上且0.2m2以下和/或聚氨酯纤维的单纤维纤度为3分特克斯以上且300分特克斯以下。
[5]如上述[1]~[4]中任一项所述的留香性聚氨酯类纤维,其特征在于,上述香料成分是碳原子数为3以上且15以下、分子量为50以上且350以下、沸点为20℃以上且200℃以下的化合物。
[6]如上述[1]~[5]中任一项所述的留香性聚氨酯类纤维,其特征在于,上述香料成分的吸收来自利用包含香料成分的洗涤用柔顺剂和/或洗涤剂在水浴中的清洗。
[7]如上述[1]~[5]中任一项所述的留香性聚氨酯类纤维,其特征在于,上述香料成分的吸收来自利用包含香料成分的洗涤用柔顺剂和/或洗涤剂在干洗溶剂中的清洗。
[8]如上述[1]~[5]中任一项所述的留香性聚氨酯类纤维,其特征在于,上述香料成分的吸收来自包含香料成分的液体状物质的喷雾。
[9]一种留香性布帛,其特征在于,其具有上述[1]~[8]中任一项所述的留香性聚氨酯类纤维。
[10]如上述[9]所述的留香性布帛,其特征在于,从吸收香料成分起48小时后的香料成分的总释放量为0.01μg/g·小时以上且1000μg/g·小时以下。
[11]如上述[9]或[10]所述的留香性布帛,其特征在于,留香性聚氨酯类纤维的含量为2重量%以上且100重量%以下。
[12]一种留香性聚氨酯类纤维原材料,使上述[1]~[8]中任一项所述的留香性聚氨酯类纤维吸收香料成分而得到。
[13]上述[1]~[8]中任一项所述的留香性聚氨酯类纤维的应用,其特征在于,使其吸收香料成分。
[14]一种留香性聚氨酯类纤维的香气保持方法,其特征在于,具有使上述[1]~[8]中任一项所述的留香性聚氨酯类纤维吸收香料成分的过程。
[15]一种留香性聚氨酯类纤维原材料的制造方法,其特征在于,具有使上述[1]~[8]中任一项所述的留香性聚氨酯类纤维吸收香料成分的工序。
[16]如上述[15]所述的留香性聚氨酯类纤维原材料的制造方法,其特征在于,具有两次以上的上述吸收香料成分的工序。
发明效果
本发明的聚氨酯类纤维有助于优良的留香性、尤其是包含香料成分的洗涤用柔顺剂和/或洗涤剂等的留香功能,该聚氨酯纤维、含有该聚氨酯纤维的布帛和使用该布帛的衣物在洗涤干燥后长期地持续令人舒心的香味。此外,本发明的聚氨酯纤维的这样的优良功能不会劣化或劣化的程度小,例如在对洗涤等的耐久性的方面非常优良。
附图说明
图1是表示为了测定本发明中的香料成分的总释放量,将赋予模型香料或市售香料后的试样保持在玻璃容器内,将通过向该玻璃容器内流通空气而产生的气体捕集于吸附管中的状态的示意图。
图2是实施例19中的GC/MS总离子流色谱图。
图3是实施例20中的GC/MS总离子流色谱图。
图4是比较例19中的GC/MS总离子流色谱图。
图5是比较例20中的GC/MS总离子流色谱图。
具体实施方式
以下,详细地说明本发明的留香性聚氨酯类纤维。
本发明的留香性聚氨酯类纤维的特征在于,从吸收香料成分起48小时后的香料成分的总释放量为0.1μg/g·小时以上且1000μg/g·小时以下。
本发明中,留香性表示所赋予的香气长时间持续。本发明的聚氨酯类纤维具备留香性时,含有本发明的聚氨酯纤维的布帛等中在洗涤时被赋予的优选的香气例如在干燥后经过约24小时以上也能够感知,优选经过48小时以上、更优选经过约72小时以上、进一步优选经过约144小时以上也能够感知。作为本发明的聚氨酯类纤维或布帛的香气被良好感知的指标,可以列举例如下述的基于六级气味强度表示法(感官试验1)的评价为2.5以上、优选为3.0以上。另外,作为下述的基于9级愉快·不愉快度表示法(感官试验2)的评价,优选为2以上、更优选为3以上。作为功能保持耐久试验中的基于9级愉快·不愉快度表示法(感官试验3)的评价,也优选为2以上、更优选为3以上。
另外,上述留香性例如可以由在纤维或布帛被暴露于香料成分并吸收香料成分的工序(例如洗涤工序等)后经过干燥在48小时后的香料成分的总释放量表示。作为这样的总释放量,例如可以使用捕集由纤维或布帛产生的香料成分后利用气相色谱等对捕集量进行分析而得到的值。上述总释放量通常使用在约18℃~45℃测定的值,优选使用在约20℃~25℃测定的值。更优选使用在约22℃~24℃测定的值。上述总释放量优选为0.1μg/g·小时以上且1000μg/g·小时以下、更优选为0.2μg/g·小时以上且500μg/g·小时以下、最优选为0.3μg/g·小时以上且200μg/g·小时以下。其中,μg/g·小时表示本发明的聚氨酯类纤维或具有该纤维的本发明的布帛1g每1小时释放的香料成分的总释放量(μg)。低于0.1μg/g·小时时,不满足所设想的布帛的留香性、气味强度。大于1000μg/g·小时时,气味强度本身过高,因此有时得不到优选的香味。
本发明的聚氨酯类纤维例如可以是由多元醇、二异氰酸酯化合物、二胺化合物和二醇化合物等进行聚合而成的纤维,在本发明中没有特别限定。另外,其合成方法也没有特别限定。上述聚氨酯类纤维例如可以是由聚合物二醇、二异氰酸酯和低分子量二胺等进行聚合而成的聚氨酯脲纤维,另外,也可以是由聚合物二醇、二异氰酸酯和低分子量二醇等进行聚合而成的聚氨酯纤维(聚氨酯氨基甲酸酯纤维,polyurethane urethane)。此外,可以是使用了在分子内具有羟基和氨基的化合物作为增链剂的聚氨酯脲纤维。在不妨碍本发明效果的范围内还优选使用3官能性以上的多官能性的二醇、异氰酸酯等。聚合物二醇优选为聚醚类、聚酯类二醇、聚碳酸酯二醇等。并且,尤其从高效地对丝赋予溶解性不同的亲水性香料和亲油性香料的观点出发,优选使用聚醚类二醇。
在本发明中使用的多元醇优选分子量比约为0.5以上,并且重均分子量/数均分子量之比约为1.8以上。从机械物性的观点、高效地对丝赋予香料的观点、香料吸收释放功能的保持率的观点出发,通过使用这样的多元醇,能够得到优良的聚氨酯类纤维。优选分子量比约为1.5以上且3以下、重均分子量/数均分子量之比约为2以上且10以下。
需要说明的是,多元醇的分子量比能够通过以下的式(1)求出。
分子量比=10(0.493logη+3.0646)/平均分子量 (1)
η:40℃下的粘度(mPa·s)×0.01
(数学式(1)的平均分子量为数均分子量)
并且,重均分子量、数均分子量使用利用GPC测定后根据聚苯乙烯进行换算后的结果。
本发明中使用的多元醇可以是单一一种,也可以通过将分子量不同的两种以上多元醇(相对地为高分子量的多元醇和低分子量的多元醇)混合由此得到上述范围中的所期望的的分子量,优选将分子量不同的两种以上多元醇混合而得到规定的分子量。通过混合易于得到伸长率、应力特性优良的聚氨酯纤维。所混合的多元醇的分子量没有特别规定,例如可以将分子量约低于600的多元醇和分子量约大于1600的多元醇混合,也可以将分子量低于所混合的其它多元醇但分子量为约600以上的多元醇和分子量高于所混合的其它多元醇但分子量约为1600以下的多元醇混合。但是,所混合的多种多元醇的分子量差异大时,多元醇各自的反应性不同,因而优选所混合的多种多元醇的分子量差限制在约1000以内。更优选分子量差约为600以内。
作为聚醚类多元醇,可以列举例如:聚环氧乙烷、聚乙二醇、聚乙二醇的衍生物、聚丙二醇、聚四亚甲基醚二醇(以下简称为PTMG)、作为四氢呋喃(THF)和3-甲基四氢呋喃的共聚物的改性PTMG(以下简称为3M-PTMG)、作为THF和2,3-二甲基THF的共聚物的改性PTMG、日本专利第2615131号公报等中所公开的在两侧具有侧链的多元醇、THF和环氧乙烷和/或环氧丙烷不规则排列的无规共聚物等。可以将它们中两种以上混合或共聚后使用,但从丝的强伸性和回复力的观点出发,优选使用PTMG、3M-PTMG、将这两种混合而成的多元醇等。对于PTMG、3M-PTMG或将这两种混合而成的多元醇等,也可以以不损害特性的程度混合或共聚其它多元醇。
特别是在水系洗涤时收纳亲水性香料的情况下,优选使用含有环氧乙烷的二醇等,适合含有聚环氧乙烷二醇、聚乙二醇的衍生物等,在收纳、吸收亲油性香料的情况下,适合使用聚丙二醇、PTMG、3M-PTMG等。
接着,作为用于本发明的有机二异氰酸酯化合物,可以使用芳香族、脂环族和脂肪族二异氰酸酯化合物等。作为芳香族二异氰酸酯化合物,可以列举例如:二苯基甲烷二异氰酸酯(以下简称为MDI)、甲苯二异氰酸酯、1,4-二异氰酸酯苯、苯二亚甲基二异氰酸酯、2,6-萘二异氰酸酯等。作为脂环族、脂肪族二异氰酸酯,可以列举例如:亚甲基双(环己基异氰酸酯)(以下简称为H12MDI)、异佛尔酮二异氰酸酯、甲基环己烷-2,4-二异氰酸酯、甲基环己烷-2,6-二异氰酸酯、环己烷-1,4-二异氰酸酯、六氢苯二亚甲基二异氰酸酯、六氢甲苯二异氰酸酯和八氢1,5-萘二异氰酸酯等。这些有机二异氰酸酯化合物可以单独使用,也可以并用两种以上。这些有机二异氰酸酯化合物之中,从纤维的强度、耐热性等优良的方面出发,优选使用芳香族二异氰酸酯化合物等、更优选使用MDI等。也可以对MDI混合其它一种或两种以上芳香族二异氰酸酯化合物等后使用。
多元醇和有机二异氰酸酯化合物的反应当量比(摩尔比)优选为约8以下。为该范围时,能够得到不仅强伸性和回复力优良而且加工性也优良的纤维。即,超过约8时,通过聚合工艺而生成凝胶,因此可纺性有可能产生问题。此外,凝胶的部分有时成为弱丝从而品质难以稳定。尤其聚合工艺在溶液中的情况下,优选为约8以下、更优选为约6以下、最优选为约3以下。另一方面,小于1时,耐热性变差且断裂强伸性也容易降低,因此品质有可能产生问题。因此,作为下限,优选为约1以上、更优选为约1.4以上。
接着,作为构成聚氨酯类树脂的结构单元的增链剂,优选使用低分子量二胺和低分子量二醇之中至少一种或两种以上。需要说明的是,可以是像乙醇胺那样的分子中具有羟基和氨基两者的物质。
作为优选的低分子量二醇,乙二醇(以下简称为EG)、1,3-丙二醇、1,4-丁二醇、双羟基乙氧基苯、双羟基对苯二甲酸乙二酯、1-甲基-1,2-乙二醇等是典型例子。特别优选为EG、1,3-丙二醇和1,4-丁二醇等。使用它们时,作为二醇增链的聚氨酯类树脂,耐热性高,并且制成聚氨酯类纤维时能够提高强度。
作为本发明的聚氨酯类纤维的增链剂,列举优选的二胺化合物。通过使用二胺化合物,能够实现高的回复力,并且由于所生成的脲基的强大的氢键合力而连水亲和性的香料类也易于捕捉,能够有助于香气持续性。作为二胺化合物,可以列举低分子量二胺化合物、例如肼、乙二胺、1,2-丙二胺、1,3-丙二胺、2-甲基-1,5-戊二胺、1,2-二氨基丁烷、1,3-二氨基丁烷、1-氨基-3,3,5-三甲基-5-氨基甲基环己烷、2,2-二甲基-1,3-二氨基丙烷、1,3-二氨基-2,2-二甲基丁烷、2,4-二氨基-1-甲基环己烷、1,3-戊二胺、1,3-环己二胺、双(4-氨基苯基)氧化膦、己二胺、1,3-环己二胺、六氢间苯二胺、2-甲基五亚甲基二胺和双(4-氨基苯基)氧化膦等。这些之中,能够使用一种或混合使用两种以上。另外,能够以不损害特性的程度并用乙二醇等低分子量二醇化合物等。二胺化合物中优选的是碳原子数2~5的二胺化合物,若从制造伸长率和弹性回复性等优良的纤维这样的观点出发,则特别优选使用乙二胺等。在这些增链剂以外,如果是不会失去本发明效果的程度则也可并用可形成交联结构的三胺化合物(例如二亚乙基三胺等)等。为了控制所得到的聚氨酯的分子量,优选在增链反应时并用链封端剂。从纺丝后的丝特性稳定的方面出发,增链剂相对于链封端剂的摩尔比优选约为10~20之间。更优选约为14~18之间。
作为该链封端剂,可以使用正丁醇之类的单醇化合物和二甲胺、二乙胺、环己胺、正己胺之类的单胺化合物等。优选为单胺化合物、更优选为二乙胺。链封端剂通常与增链剂混合使用。
由以上的多元醇、有机二异氰酸酯化合物和二胺化合物等聚合的聚氨酯的聚合方法没有特别限定,可以是熔融聚合法、溶液聚合法中的任一种,也可以是其它方法,但更优选的是溶液聚合法。溶液聚合法的情况下,有聚氨酯中凝胶等异物的产生少的优点。
溶液聚合法的情况下,例如可以通过在DMAc、DMF、DMSO和NMP等或以这些为主要成分的溶剂之中使用多元醇和有机二异氰酸酯化合物以及二胺化合物等原料进行聚合,由此得到聚氨酯溶液。其反应方法也没有特别限定,可以列举例如:在溶剂中投入各原料并使之溶解,加热至适当温度使之反应的一步(one shot)法;将多元醇和有机二异氰酸酯化合物首先在无溶剂下反应制成预聚物,此后,使该预聚物溶于溶剂并利用二胺化合物进行增链反应,从而合成聚氨酯的预聚物法等,优选为预聚物法。
需要说明的是,该聚氨酯的合成时,胺类催化剂、有机金属催化剂等催化剂优选使用一种或混合使用两种以上。作为胺类催化剂,可以列举例如:N,N-二甲基环己胺、N,N-二甲基苄基胺、三乙胺、N-甲基吗啉、N-乙基吗啉、N,N,N’,N’-四甲基乙二胺、N,N,N’,N’-四甲基-1,3-丙二胺、N,N,N’,N’-四甲基己二胺、双-2-二甲氨基乙醚、N,N,N’,N’-五甲基二亚乙基三胺、四甲基胍、三乙烯二胺、N,N’-二甲基哌嗪、N-甲基-N’-二甲氨乙基哌嗪、N-(2-二甲氨基乙基)吗啉、1-甲基咪唑、1,2-二甲基咪唑、N,N-二甲基氨基乙醇、N,N,N’-三甲基氨基乙基乙醇胺、N-甲基-N’-(2-羟基乙基)哌嗪、2,4,6-三(二甲氨基甲基)苯酚、N,N-二甲基己醇胺和三乙醇胺等。
另外,作为有机金属催化剂,可以列举辛酸锡、二月桂酸二丁基锡和辛酸二丁基铅等。
所得到的聚氨酯溶液中的聚氨酯的浓度没有特别限定,但从聚氨酯的分子量和溶液粘度、所得到的纤维的伸缩特性出发,优选约为20~60重量%之间。更优选约为30~50重量%之间,进一步优选约为35~45重量%之间。
所得到的聚氨酯溶液中,聚氨酯的来自二胺化合物的端基浓度相对于聚氨酯优选约为5~50meq/kg。更优选约为10~45meq/kg之间。端基浓度高于约50meq/kg时,聚合物的分子量小,应力、回复力反而容易降低,因此有可能形成不适合用于衣服等的纤维。另外,小于约5meq/kg时,分子量提高,因此容易产生如下问题:一部分发生凝胶化而产生伸长率、强度低的部分;品质不稳定;从溶液粘度的观点出发难以提高浓度从而生产率下降。
另外,来自聚氨酯的二胺化合物的端基浓度的测量可如下进行。将DMAc加到聚氨酯溶液中以得到聚氨酯浓度为1.77重量%的溶液。然后,使用由三菱化学株式会社制造的自动滴定装置GT-100,用对甲苯磺酸(0.01N)进行电位差滴定以获得伯胺和仲胺的总含量(A)。接着,将水杨醛(20%异丙醇溶液)添加到同样制备的聚氨酯溶液中且使其与伯胺反应后,用对甲苯磺酸(0.01N)对仲胺进行电位差滴定以获得仲胺含量(B)。来自二胺化合物的端基浓度可根据下式计算。
有效末端胺值(meq/kg)=(A)-(B)
并且,作为本发明中所使用的聚氨酯类树脂,从得到包括在工序通过性在内在实用上没有问题且高耐热性优良的聚氨酯类树脂的观点出发,特别优选为含有使聚合物二醇与二异氰酸酯发生反应来得到的物质,并且高温侧的熔点约为150℃以上且300℃以下的范围的聚氨酯类树脂。在此,高温侧的熔点相当于用差示扫描量热仪(DSC)测定时的聚氨酯或聚氨酯脲的所谓硬段结晶的熔点。
此外,从留香性的观点出发,本发明中所使用的聚氨酯类纤维中的氨基甲酸基浓度和脲基浓度的合计优选约为1.0mol/kg以上且5.0mol/kg以下、更优选约为1.0mol/kg以上且4.5mol/kg以下、更优选约为1.2mol/kg以上且4.0mol/kg以下。该氨基甲酸基浓度和脲基浓能够根据以下式子求出。
氨基甲酸基浓度[mol/kg]=(聚氨酯纤维中含有的聚合物二醇(mol))×2/(聚氨酯纤维的重量(kg))
脲基浓度[mol/kg]=(聚氨酯纤维中含有的二异氰酸酯(mol)-聚氨酯纤维中含有的聚合物二醇(mol))×2/(聚氨酯纤维的重量(kg))
此外,本发明中所使用的聚氨酯中有时优选添加后述的各种添加剂类。
尤其从提高留香性的观点出发,可以列举为了调整构成聚氨酯类树脂的氨基甲酸基浓度和脲基浓度的总计而添加含有含叔氮二醇和/或含叔氮二胺以及有机二异氰酸酯的聚氨酯和/或聚氨酯脲聚合物。此外,还可以列举在这些聚合物等中添加带有N,N-二烷基氨基脲端基的聚合物。即便在主链中具有叔氮且在末端具有N,N-二烷基氨基脲的化合物为低浓度的N,N-二烷基氨基脲,也能够发挥在染色时的高耐热性,与未配合的情况相比能够成为高强伸性。
作为上述含叔氮二醇的优选的具体例,可以使用例如N-甲基-N,N-二乙醇胺、N-甲基-N,N-二丙醇胺、N-甲基-N,N-二异丙醇胺、N-丁基-N,N-二乙醇胺、N-叔丁基-N,N-二乙醇胺、N-十八烷-N,N-二乙醇胺、N-苄基-N,N-二乙醇胺、N-叔丁基-N,N-二异丙醇胺等以及双羟乙基哌嗪、双羟异丙基哌嗪等哌嗪衍生物等。其中特别优选的是N-叔丁基-N,N-二乙醇胺或N-苄基-N,N-二乙醇胺等。
作为上述含叔氮二胺的优选的具体例,可以使用例如N-甲基-3,3’-氨基二丙胺、N-丁基氨基二丙胺、N-甲基氨基二乙胺、N-叔丁基氨基二丙胺、哌嗪-N,N’-双(3-氨基丙基)和哌嗪-N,N’-双(2-氨基乙基)等。其中特别优选的是N-甲基-3,3’-氨基二丙胺或哌嗪-N,N’-双(3-氨基丙基)等。
作为上述的含有含叔氮二醇和/或含叔氮二胺以及有机二异氰酸酯的聚氨酯和/或聚氨酯脲聚合物中的有机二异氰酸酯的优选的具体例,可以使用例如亚甲基双(4-环己基异氰酸酯)、异佛尔酮二异氰酸酯、赖氨酸二异氰酸酯以及由二聚酸衍生的DDI等脂肪族二异氰酸酯等。其中特别优选的是亚甲基双(4-环己基异氰酸酯)或异佛尔酮二异氰酸酯等。
并且,聚氨酯或聚氨酯脲的端基优选形成氨基脲基。与有机二异氰酸酯反应形成末端氨基脲基的情况下,优选使用取代肼等。作为取代肼的优选的具体例,可以使用例如N,N-二甲基肼、N,N-二乙基肼、N,N-二丙基肼、N,N-二异丙基肼、N,N-二丁基肼、N,N-二异丁基肼、N,N-二羟乙基肼和N,N-二羟异丙基肼等。其中特别优选的是N,N-二甲基肼和N,N-二羟乙基肼等。
作为上述的含有含叔氮二醇和/或含叔氮二胺以及有机二异氰酸酯的聚氨酯和/或聚氨酯脲聚合物,特别优选为:通过N-叔丁基-N,N-二乙醇胺与亚甲基双(4-环己基异氰酸酯)的反应而生成的聚氨酯或者使N,N-二甲基肼与通过N-叔丁基-N,N-二乙醇胺与亚甲基-双(4-环己基异氰酸酯)的反应而生成的聚氨酯在末端反应后的聚氨酯;以及通过N-甲基-3,3’-氨基二丙胺与亚甲基双(4-环己基异氰酸酯)的反应而生成的聚氨酯等。N-叔丁基-N,N-二乙醇胺与亚甲基双(4-环己基异氰酸酯)的反应比例只要不妨碍本发明效果就没有特别限定,例如优选通过约1:1.05的反应而生成的聚氨酯,此时的交替共聚物的氨基甲酸基浓度和脲基浓度的总计约为5.1mol/kg。
此外,从提高留香性的观点出发,硬脂酸镁等金属皂、碳酸钙等碳酸盐类也可以作为香料的吸收基材而发挥有用的作用。
此外,从提高留香性的观点出发,优选本发明中所使用的聚氨酯类纤维中含有环糊精和/或其衍生物。可以使用例如α-环糊精、β-环糊精、γ-环糊精、甲基化或羟丙基化后的环糊精中的任何一种。
此外,从提高留香性的观点出发,优选在本发明中所使用的聚氨酯类纤维中配合无机类化合物。特别优选配合层状晶体结构的无机类化合物、层状的粘土矿物、天然和合成沸石、天然和合成水滑石、金属化合物。作为层状无机类化合物,可以列举例如层状无机物及其有机处理物。层状无机类化合物可以是固体,也可以具有流动性。层状无机类化合物可以仅为一种,也可以为两种以上。作为可形成层状无机物的无机物,可以列举例如硅酸盐、粘土矿物等。其中,作为层状无机物,优选层状粘土矿物。作为层状粘土矿物,可以列举例如蒙脱石、贝得石、水辉石、皂石、绿脱石、斯皂石(Stevensite)等蒙皂石;蛭石;膨润土;水硅钠石(Kanemite)、斜水硅钠石(ケニアナイト)、马水硅钠石(Makatite)等层状硅酸钠等。这种层状粘土矿物可以是作为天然矿物而出产的,也可以是通过化学合成方法而制造的。其中可优选列举沸石。沸石的特长是具有无定型或蜂巢状的无数的微细孔从而比表面积大。因此,在水系洗涤工序中,水分被吸进该细孔中,进而各种高挥发性、低分子量香料与水分同时被吸入。例如,作为水滑石类化合物,优选Mg6Al2(OH)16CO3·4H2O和Mg4.5Al2(OH)13CO3·3.5H2O等。另外,也优选碳钙镁石(Huntite)与羟水碳镁石(Hydromagnesite)的混合物、即Mg2Ca(CO3)4和Mg4(CO3)4·Mg(OH)3·4H2O的混合物。另外,金属化合物中,作为选自Ca、Mg、Al或Ba的金属的碳酸盐,优选碳酸钙、碳酸镁、碳酸钡等。作为氧化物,优选为氧化镁、氧化铝等,作为氢氧化物,优选为氢氧化钙、氢氧化镁、氢氧化铝等。作为复合氧化物,优选MgO·Al2O3等。上述无机类化合物之中,特别优选水滑石类化合物Mg6Al2(OH)16CO3·4H2O、碳钙镁石与羟水碳镁石的混合物、复合氧化物MgO·Al2O3。通过含有这样的无机类化合物,由此能够提高留香性的效果。
这些无机类化合物被配合在聚氨酯类纤维的纺丝溶液中,因而从纺丝稳定性的观点出发,优选平均粒径约为2μm以下、平均粒径约为1μm以下。本发明中,平均粒径表示由通过筛分法测定的粒度分布的累积重量达到50重量%的粒径定义的值。另外,出于进一步提高这些无机类化合物在丝中的分散性、使纺丝稳定化等的目的,也优选使用利用例如脂肪酸、脂肪酸酯、磷酸酯、多元醇类有机物等有机物、硅烷类偶联剂、钛酸酯类偶联剂、水玻璃、脂肪酸金属盐或这些的混合物等进行表面处理后的无机类化合物。
各种添加剂类的添加方法可以采用任意的方法。作为其代表性的方法,可以采用通过静态混合器进行的方法、通过搅拌进行的方法、通过均相混合器进行的方法、使用双螺杆挤出机的方法等各种方法。在此,在通过溶液聚合合成聚氨酯类纤维的情况下,从均匀的添加的观点出发,所添加的各种添加剂类优选形成为溶液来添加。
需要说明的是,由于各种添加剂类添加到聚氨酯溶液中,有可能发生添加后的混合溶液的溶液粘度比添加前的聚氨酯溶液粘度高出预期以上的现象。从防止该现象的观点出发,优选使用二甲胺、二异丙胺、乙基甲基胺、二乙胺、甲基丙基胺、异丙基甲基胺、二异丙胺、丁基甲基胺、异丁基甲基胺、异戊基甲基胺、二丁胺、二戊胺等单胺;乙醇、丙醇、丁醇、异丙醇、烯丙醇、环戊醇等一元醇;苯基异氰酸酯等单异氰酸酯等封端剂中的一种或两种以上的混合物。
此外,本发明中所使用的聚氨酯类纤维中在不影响本发明的效果的范围内根据需要可以含有各种稳定剂、颜料等。例如,可以添加或者与聚合物反应而存在二乙烯基苯与对甲酚的加聚物(杜邦公司制“メタクロ一ル”(注册商标)2390)等稳定剂;耐光剂;作为抗氧化剂等的以所谓BHT或住友化学工业(株)制的“スミライザ一”GA-80等为代表的双受阻酚类药剂;チバガイギ一公司制“チヌビン”等苯并三唑类、二苯甲酮类药剂;住友化学工业(株)制的“スミライザ”P-16等磷类药剂;各种受阻胺类药剂;氧化钛、炭黑等无机颜料;氟类树脂粉末或硅氧烷类树脂粉末;含有银、锌或它们的化合物等的杀菌剂;除臭剂;硅氧烷、矿物油等润滑剂;硫酸钡、氧化铈、甜菜碱、磷酸类等各种抗静电剂等。作为抗菌剂,可以列举有机类、无机类等各种抗菌剂,优选为由有机氮硫类化合物、季铵类化合物、磷酸酯类化合物和含有金属离子的无机类化合物等中的任一种以上组成的抗菌剂。作为有机类抗菌剂,可以列举有机氮硫类化合物、酚类化合物、有机锡化合物、有机铜化合物、有机银化合物等具有抗菌性金属离子的有机抗菌剂、各种有机硅氧烷类季铵盐、烷基磷酸酯的季铵盐(例如十六烷基二甲基氯化铵等)、苯扎氯铵、烷基芳基磺酸酯、卤代苯酚和乙酸苯汞等有机类抗菌剂、多元酚类、壳聚糖等。另外,作为除臭剂,可以列举沸石、磷灰石(Apatite)、活性炭、活性氧化铝、活性硅胶、膨润土或海泡石等陶瓷粉末、和丝绸纤维含有物等或铁、铜等金属盐以及它们的混合物等。这些除臭剂兼具除臭作用以及吸湿作用,因此用一种成分可以对布帛赋予脱臭、吸湿两种功能。而且,特别是为了进一步提高对光、各种氧化氮等的耐久性,可以含有例如日本ヒドラジン(株)制的HN-150等氧化氮捕捉剂、住友化学工业(株)制的“スミライザ一”GA-80等热氧化稳定剂、住友化学工业(株)制的“スミソ一ブ”300#622等光稳定剂等。
另外,配合这些无机类添加剂的情况下,出于提高其在丝中的分散性、使纺丝稳定化等目的,也优选使用例如利用脂肪酸、脂肪酸酯、多元醇类有机物等有机物、硅烷类偶联剂、钛酸酯类偶联剂或它们的混合物进行表面处理后的无机药品。
本发明中,聚氨酯类纤维能够利用公知的湿法纺丝法、熔融纺丝法、干法纺丝法中的任一种方法进行纺丝,但从生产率、所得到的弹性纤维的特性的观点出发,优选将聚氨酯进行干式或熔融纺丝。并且,从留香性的观点出发,更优选进行干法纺丝。主要的香料类是亲油性的,由干法纺丝法得到的聚氨酯纤维的纤维表面会成为亲油性,此外,由干法纺丝法得到的聚氨酯纤维易于控制单纤维纤度、易于控制纤维表面积。
另外,在纺丝后可根据需要对本发明的聚氨酯类纤维应用油剂等处理剂。处理剂例如可利用油辊等进行涂布。作为上述油剂,从所得到的纤维的留香性优良的方面出发,优选使用例如有机硅和矿物油等。本发明的聚氨酯类纤维用于在之后利用洗涤等方法吸收所期望的香料成分,因此为了不损害该香料成分的优选的香气,吸收香料成分前的状态下优选不含有其它香料成分。
作为本发明的聚氨酯类纤维,例如优选每1g织物的纤维表面积为约0.02m2以上且0.2m2以下的聚氨酯类纤维、更优选为约0.1m2以上且0.2m2以下的聚氨酯类纤维、进一步优选为约0.12m2以上且0.2m2以下的聚氨酯类纤维。另外,作为本发明的合成纤维,例如优选单纤维纤度为约3分特克斯(dtex)以上且300分特克斯以下的合成纤维、进一步优选为10分特克斯以上且150分特克斯以下的合成纤维。具有上述纤维表面积和/或单纤维纤度能够更长时间地保持轻快的香味。
含有本发明的聚氨酯类纤维的纤维原材料或布帛可以含有其它纤维,尤其优选含有其它合成纤维。作为其它合成纤维,只要不妨碍本发明的效果就没有特别限定,可以列举例如聚酯类纤维、聚酰胺类纤维、聚丙烯酸腈类纤维、聚乙烯醇类纤维和聚氯乙烯类纤维等,可优选列举聚酯类纤维等。
利用与作为吸收香料原因的聚氨酯纤维的组合,聚酯纤维有助于香料吸收、尤其亲油性香料的吸收,对留香性发挥有用的作用。
例如,可以优选使用由聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、或以对苯二甲酸乙二醇酯单元为主要重复成分的聚酯(优选为重复单元的90摩尔%以上)、以对苯二甲酸丁二醇酯单元为主要重复成分的聚酯(优选为重复单元的90摩尔%以上)等形成的纤维。其中,优选为由对苯二甲酸乙二醇酯单元为90摩尔%以上重复成分的聚酯形成的纤维,更优选为由对苯二甲酸乙二醇酯单元为95摩尔%以上重复成分的聚酯形成的纤维。进一步优选为由对苯二甲酸乙二醇酯单元为100摩尔%重复成分的聚酯、即聚对苯二甲酸乙二醇酯形成的纤维。该聚对苯二甲酸乙二醇酯类纤维具有良好的手感、光泽,另外具有不易出褶等免烫性,适合作为构成具有伸缩性的布帛的纤维原材料。另外,聚对苯二甲酸乙二醇酯类纤维优选以与本发明中优选使用的聚氨酯脲纤维的组合来使用,可以形成良好的布帛。
本发明中,聚酯纤维的截面形态为圆形、异形都可。另外,吸水速干性聚酯纤维丝等优选使用。另外,优选使用吸水速干性聚酯纤维丝。作为吸水速干性的聚酯纤维,可以使用为在中空纤维的壁面进而设置有多个小孔的纤维,或者在纤维表面等设置多个槽或孔等而吸水性表现为水分被这些纤维自身的微小孔、纤维表面的槽、纤维间、丝间的空隙所吸收的异形截面形状的纤维等,由合成纤维制造商作为吸水速干性纤维在市场上销售的各种吸水速干性纤维。例如,作为吸水速干性聚酯纤维,可以举出インビスタ公司制“ク一ルマツクス”、东丽株式会社制“セオα”、帝人纤维株式会社制“ウエルキイ”、东洋纺织株式会社制“ドライファスト”、旭化成纤维株式会社制“テクノファイン”等。
对于赋予吸水速干性,可以举出使用如前所述聚酯纤维或丙烯酸纤维等聚合物本身为吸湿性小的原材料,形成中空纤维状并在其壁面进而设置有多个小孔的纤维的形状的纤维,或者在纤维表面等设置多个槽或孔等而吸水性表现为水分被这些纤维自身的微小孔、纤维表面的槽、纤维间、丝间的空隙所吸收的异形截面形状的纤维等设置有吸入水分的微小的孔或空隙的纤维等。
另外,作为根据需要的抗静电性的合成纤维,可以使用聚酯导电性纤维等。作为导电性纤维可以举出例如使用炭黑作为导电性物质的复合聚酯纤维(例如,カネボウ合纤株式会社制“ベルトロン”),使用白色的碘化铜或金属复合氧化物(例如,TiO2·SnO2·Sb2O2)作为导电性物质的复合聚酯纤维等,但不限定于这些。
此外,本发明中使用的聚酯纤维中也与上述聚氨酯同样地在不影响本发明的效果的范围内根据需要可以含有各种稳定剂、颜料等。例如,可以添加或者与聚合物反应而存在二乙烯基苯与对甲酚的加聚物(杜邦公司制“メタクロ一ル”(注册商标)2390)等稳定剂;通过叔丁基二乙醇胺与亚甲基双(4-环己基异氰酸酯)的反应而生成的聚氨酯(杜邦公司制“メタクロ一ル”(注册商标)2462);耐光剂;作为抗氧化剂等的以所谓BHT或住友化学工业(株)制的“スミライザ一”GA-80等为代表的双受阻酚类药剂;チバガイギ一公司制“チヌビン”等苯并三唑类、二苯甲酮类药剂;住友化学工业(株)制的“スミライザ”P-16等磷类药剂;各种受阻胺类药剂;氧化钛、炭黑等无机颜料;氟类树脂粉末或硅氧烷类树脂粉末;硬脂酸镁等金属皂;或含有银、锌或它们的化合物等的杀菌剂;除臭剂;硅氧烷、矿物油等润滑剂;硫酸钡、氧化铈、甜菜碱、磷酸类等各种抗静电剂等。而且,特别是为了进一步提高对光、各种氧化氮等的耐久性,可以含有作为氧化氮捕捉剂的例如日本ヒドラジン(株)制的HN-150、作为热氧化稳定剂的例如住友化学工业(株)制的“スミライザ一”GA-80等、作为光稳定剂的例如住友化学工业(株)制的“スミソ一ブ”300#622等光稳定剂等。
具有本发明的聚氨酯类纤维的布帛也是本发明的一个实施方式。该布帛例如在混用聚酯丝、尼龙丝等的混用弹性布帛中也能够体现出本发明的效果。
本发明的布帛例如可以是由上述聚氨酯类纤维和其它合成纤维等依据常规方法制造布帛而得到的,尤其优选含有上述聚氨酯类纤维,进一步优选含有包含上述聚氨酯类纤维的两种以上合成纤维。本发明的布帛可以是机织物、针织物或无纺布中的任一种。例如,可以对聚氨酯纤维覆盖合成纤维制成覆盖纤维而得到布帛,也可以将聚氨酯纤维保持裸丝(Bare)的状态编织于合成纤维中,由此形成交编织针织布。
在制成布帛时,本发明中使用了氨基甲酸酯浓度和/或脲浓度高的聚氨酯纤维的情况下,能够用纤度为33分特克斯~22分特克斯左右的纤维实现以往如果不是例如44分特克斯的丝就不能实现的着压(着圧)。此时,能够实现用更薄、更轻的布帛进行自如的着压、合身感,布帛能够薄化、轻量化,由此也能够改善衣服的穿着感。
混用布帛中的聚氨酯纤维的混率与对象丝、针织组织、机织组织有关,可以为例如约2%~40%的范围。如果为该混率,则能够制成紧贴感、合身感优良并且与以往相比更薄更轻的布帛。
本发明的布帛为机织物时,可以仅用合成纤维进行织造,另外也可以交织有此外的纤维。作为上述合成纤维,优选含有包含上述聚氨酯类纤维的两种以上。将聚氨酯纤维制成机织物的组织优选为平纹组织、斜纹组织、缎纹组织等三原组织;变化平纹组织、变化斜纹组织、变化缎纹组织等变化组织;蜂巢组织、充纱罗组织、绉纹组织等特殊组织;经二重组织、纬二重组织等单二重组织;双面异色花纹组织、袋织组织、双层丝绒等二重组织、织带(ベルト織)等多层组织、经丝绒、毛巾、海豹绒、法兰绒等经起绒组织;平绒、纬丝绒、立绒、灯芯绒等纬起绒组织;罗、纱、提花纱等纱罗组织等。
织造只要不妨碍本发明的效果就没有特别限定,优选利用有梭织机(滑轮梭子织机等)或无梭织机(剑杆织机、片梭织机、喷水织机、喷气织机等)等进行。
另外,本发明的布帛为针织物的情况下,也可以仅用合成纤维进行编织,另外,也可以交编有此外的纤维。作为上述合成纤维,优选含有包含上述聚氨酯类纤维的两种以上。针织物的种类可以是纬针织物,另外也可以是经针织物等。对于针织物的组织而言,纬编优选平平针编织、罗纹编织、双罗纹针织、双反面组织、集圈组织、浮线编织、半畦编组织、花边网眼组织和绒头组织等,经编优选单梳栉经平组织、单梳栉经缎组织、经绒组织、经绒-经平组织、背面起绒编织和提花组织等。层数可以是单层,也可以是两层以上的多层。
编织只要不妨碍本发明的效果就没有特别限定,优选通过圆编机、横机、柯登机之类的平机、特里科经编机、拉舍尔经编机、米兰尼斯经编机等进行。
此外,本发明的布帛优选用于例如外套、和服、西装、制服、毛衣、裙子、休闲裤、开襟衫、运动衣、连衣裙、休闲装等外衣;紧身裤袜、长袜、连裤袜、短袜等袜子类;睡衣、短裤、女用贴身内衣裤、紧身内衣、针织内衣等内衣类;床单、被罩、被褥的边布、毛布、枕套等就寝用具类;沙发罩、桌布等室内装饰类;以及手袋、领带、围巾、披肩等小件类等,从香料成分的释放的方面考虑,特别优选用于内衣类、袜子类和就寝用具类等。
作为本发明的布帛,例如优选含有约2~100重量%的上述合成纤维,更优选含有约50~100重量%,进一步优选含有约80~100重量%。另外,从香气持续性特别优良的方面出发,纤维成分还优选仅为合成纤维。另外,从香气持续性优良的方面出发,优选相对于合成纤维整体含有约1~30重量%的聚氨酯纤维、进一步优选含有约5~20重量%的聚氨酯纤维。
另外,本发明的布帛从香气持续性特别优良的方面出发,优选克重为80~1000g/m2、更优选为100~500g/m2、进一步优选为100~280g/m2。另外,优选伸长率在经方向和/或纬方向均为5%以上。
作为本发明中的香料成分,只要不妨碍本发明的效果就没有特别限定,但出于可显示出高的香气持续性,优选与脲基、氨基甲酸基具有相互作用的官能团,从布帛释放香料的观点出发,也优选简单的烃类化合物、含氮类化合物、含硫类化合物等。
作为本发明中的香料成分,能够广泛使用公知的香料成分,可以是各种文献、例如“Perfume and Flavor Chemicals(合成香料)”SteffenArctander、Vol.I and II(1994)、“香味的百科”、日本香料协会编、朝仓书店(1989)等中记载的物质。以下列举香料的代表例,但不限于此。
作为醇类化合物,可以列举3-甲基-1-戊醇、香叶醇、柏木醇、香茅醇、玫瑰醇、橙花醇、二氢芳樟醇、芳樟醇、四氢芳樟醇、二甲基辛醇、四氢里哪醇、里哪醇、月桂烯醇、二氢月桂烯醇、罗勒烯醇、四氢月桂烯醇、熏衣草醇、异二氢熏衣草醇、羟基香茅醇、Nonadyl(6,8-二甲基-2-壬醇)、乙基芳樟醇、异蒲勒醇、萜品醇、二氢萜品醇、4-萜品醇、紫苏醇、4-侧柏醇、3-侧柏醇、法尼醇、橙花叔醇、α-没药醇、β-石竹烯醇、檀香醇、香根草醇、柏木烯醇、3-l-薄荷氧基-1,2-丙二醇、广藿香醇、二氢香芹醇、植醇、异植醇、香紫苏醇、香芹醇、薄荷醇、乙醇、丙醇、丁醇、异戊醇、1-庚醇、2-庚醇、3-庚醇、1-辛醇、2-辛醇、3-辛醇、2-乙基己醇、1-壬醇、2-壬醇、异壬基醇(3,5,5-三甲基-1-己醇)、1-癸醇、1-十一醇、2-十一醇、1-十二醇、异戊烯醇(3-甲基-2-丁烯-1-醇)、2-甲基-3-丁烯-2-醇、β-戊烯醇(1-戊烯-3-醇)、叶醇(顺式3-己烯醇)、反式-2-己烯醇、反式-3-己烯醇、顺式4-己烯醇、2,4-己二烯-1-醇、松茸醇(1-辛烯-3-醇)、顺式6-壬烯醇、胡瓜醇(2,6-壬二烯醇)、アンドロール(1-壬烯-3-醇)、ロザルバ(9-癸烯醇)、1-十一烯醇、甲基癸烯醇(Undecavertol)(4-甲基-3-癸烯-5-醇)、オシロール(3,7-二甲基-7-甲氧基-2-辛醇)、Santalinol(2-甲基-4-(2,2,3-三甲基-3-环戊烯-1-基)-2-丁烯-1-醇)、p,α-二甲基苯甲醇、2,2,6-三甲基环己基-3-己醇、1,2-戊二醇、苯甲醇、大茴香醇、β-苯基乙醇、苏合香醇(1-苯基-1-羟基乙烷)、龙葵醇、甲基β-苯基乙醇、α-丙基苯基乙醇、香草醇、十氢β-萘酚、糠醇、3-甲基-1-苯基-3-戊醇、戊基肉桂醇、肉桂醇、苯基异己醇(3-甲基-5-苯基戊醇)、1,2-戊二醇、2-乙基己醇、dimetol(2,6-二甲基庚醇)、3,6-二甲基-3-辛醇、コヒノール(3,4,5,6,6-五甲基-2-庚醇)、ブラハマノール(甲基三甲基环戊烯基丁醇)、バクダノール(2-乙基-4-(2,2,3-三甲基-3-环戊烯-1-基)-2-丁烯-1-醇)、サンダール(3-甲基-5-(2,2,3-三甲基环戊基-3-烯-基)-戊烷-2-醇)、サンダロール(3-甲基-5-(2,2,3-三甲基环戊基-3-烯-1-基)戊烷-2-醇)、环己基乙醇、アポパチョン(对异丙基环己醇)、フロラロール(2,4-二甲基-3-环己烯-1-甲醇)、パチョン(对叔丁基环己醇)、ベルドール(邻叔丁基环己醇)、マイヨー(对异丙基环己基甲醇)、环亚甲基香茅醇、アンブリノール(2,5,5-三甲基-八氢-2-萘酚)、メチルサンデフロール(5’或6’-甲基降冰片-5’-烯-2-基)-2-甲基戊-1-烯-3-醇)、チンベロール(2,2,6-三甲基环己基-3-己醇)、ポリサントール(3,3-二甲基-5-(2,2,3-三甲基-3-环戊烯-1-基)-4-戊烯-2-醇)、羟基香茅醇、Nonadyl(6,8-二甲基-2-壬醇)、异蒲勒醇、异环香叶醇、桃金娘烯醇、ノポール(6,6-二甲基双环[3.1.1]庚-2-烯-2-乙醇)、松香芹醇、α-小茴香醇、冰片、异冰片、パチョミント(2-(3,3-二甲基双环[2.2.1]庚-2-亚基)乙醇)、カメコール(三甲基降冰片烷甲醇)、6-二甲基-3a,4,5,6,7,7a-六氢-1H-4,7-亚甲基-1H-茚-5-醇(ジメチルサイクロモル)、サンタレックスT(异莰基环已醇)、香叶基芳樟醇、枯醇、2-甲氧基苯基乙醇、苯氧基乙醇(1-羟基-2-苯氧基乙烷)、α,α-二甲基苯基乙醇、异丁基苄基甲醇、对甲基苄基甲醇、氢化肉桂醇、センチフォール(1,1-二甲基-3-苯基丙-1-醇)、ミュゲットアルコール(2,2-二甲基-3-苯基丙醇)、苯基己醇、十氢β-萘酚、AR-1(3,6-二甲基辛烷-3-醇)、アビトール(氢化枞醇)、α-丙基苯基乙醇、对甲基二甲基苄基甲醇、ムゲタノール(1-(4-异丙基环己基)乙醇)、フロロール(2-异丁基-4-羟基-4-甲基四氢吡喃)、丙二醇、二丙二醇、己二醇等。
作为酚类和酚醚类化合物,可以列举苯甲醚、蒿脑、佳味醇、茴香脑、甲氧甲酚、香芹酚、对甲酚、对甲酚基甲基醚、β-萘酚甲基醚、β-萘酚乙醚、β-萘酚异丁基醚、藜芦醚(1,2-二甲氧基苯)、1,3-二甲氧基苯、1,4-二甲氧基苯、儿茶酚、间苯二酚、愈疮木酚、バルスパイス(4-甲基愈疮木酚)、4-乙基愈疮木酚、オルシニル3(3-甲氧基-5-甲基苯酚)、麝香草酚、甲基麝香草酚、丙烯基乙基愈疮木酚(反式-2-乙氧基-5-(1-丙烯基)-苯酚)、邻乙基苯酚、间乙基苯酚、对乙基苯酚、2-叔丁基苯酚、シリンゴール(2,6-二甲氧基苯酚)、对苯二酚二甲醚、间苯二酚二甲醚、丁子香酚、异丁子香酚、二氢丁子香酚、甲基丁子香酚、甲基异丁子香酚、乙基异丁子香酚、苄基丁子香酚、苄基异丁子香酚、布枯酚、扁柏酚、バニトロープ(1-乙氧基-2-羟基-4-丙烯基苯)、姜烯酚、姜辣素、乙酰基丁子香酚、乙酰基异丁子香酚黄樟素、异黄樟素、二苯醚、香根草醚(叔丁基对苯二酚二甲醚)等。
作为醛类化合物,可以列举香茅醛、柠檬醛、3,7-二甲基-1-辛醛、羟基香茅醛、甲氧基香茅醛、紫苏醛、桃金娘烯醛、石竹烯醛、正己醛、2-甲基丁醛、异戊醛、正戊醛、乙醛、正庚醛、正辛醛、正壬醛、2-甲基辛醛、3,5,5-三甲基己醛、1-癸醛、十一醛、十二醛、2-甲基癸醛、2-甲基十一醛、十三醛、十四醛、2-戊烯醛、顺式3-己烯醛、反式-2-己烯醛、反式-2-庚烯醛、4-庚烯醛、反式-2-辛烯醛、反式-2-壬烯醛、顺式6-壬烯醛、メロナール(2,6-二甲基-5-庚烯醛)、反式-4-癸烯醛、顺式4-癸烯醛、反式-2-癸烯醛、グリナール(2,5,6-三甲基-4-庚烯醛)、10-十一烯醛、反式-2-十一烯醛、反式-2-十二烯醛、红桔醛(3-十二烯醛)、反式-2-十三烯醛、アドキサール(2,6,10-三甲基-9-十一烯-1-醛)、2,4-己二烯醛、2,4-庚二烯醛、2,4-辛二烯醛、2,4-壬二烯醛、2,6-壬二烯醛、2,4-癸二烯醛、2,4-十一碳二烯醛、2,4-十二碳二烯醛、ゲラルデヒド(5,9-二甲基-4,8-癸二烯醛)、トリメナール(3,7,9-三甲基-2,6-癸二烯-1-醛)、オンシダール(2,6,10-三甲基-5,9-十一碳二烯醛)、ベルガマール(α-亚甲基香茅醛)、龙脑烯醛、环柠檬醛、异环柠檬醛、サフラナール(2,6,6-三甲基-1,3-环己二烯-1-羧醛)、ミュゲアルデヒド(6,10-二甲基-3-氧杂-9-十一烯醛)、香叶基氧基乙醛、トリプラール(二甲基四氢苯甲醛)、クリサンタール(3-丙基双环[2.2.1]-5-庚烯-2-羧醛)、センテナール(甲氧基双环戊二烯羧醛)、デュピカール(4-三环亚癸基丁醛)、4-(4-甲基-3-环己-1-烯亚基)戊醛、柑菁醛(4(3)-(4-甲基-3-戊烯-1-基)-3-环己烯-1-羧基醛)、セトナール(三甲基环己烯甲基丁醛)、イノナール(2-甲基-4-(2,6,6-三甲基-1(2)-环己烯基)-丁烯醛)、テレストラール(4-环辛烯-1-羧醛)、苯甲醛、对甲苯醛、苯乙醛、トリフェルナール(3-苯基丁醛)、枯醛、对甲基苯乙醛、对异丙基苯乙醛、龙葵醛、对甲基龙葵醛、对异丙基龙葵醛、苯基丙醛、β-甲基氢化肉桂醛、ジャスモランジ(2-甲基-3-(4-甲基苯基)-丙醛)、ブルジェオナール(对叔丁基氢化肉桂醛)、仙客来醛(2-甲基-3-(对异丙基苯基)-丙醛)、フロラロゾン(对乙基-α,α-二甲基氢肉桂醛)、スザラール(对异丁基-α-甲基氢化肉桂醛)、肉桂醛、水杨醛、茴香醛、邻甲氧基苯甲醛、邻甲氧基肉桂醛、カントキサール(2-甲基-3-(对甲氧基苯基)-丙醛)、香兰素、乙基香兰素、甲基香兰素(3,4-二甲氧基苯甲醛)、洋茉莉醛、ヘリオナール(α-甲基-3,4-亚甲二氧基氢化肉桂醛)、苯氧基乙醛、对甲基苯氧基乙醛、糠醛、5-甲基糠醛、5-羟甲基-2-糠醛、呋喃基丙烯醛、新铃兰醛(4(3)-(4-羟基-4-甲基戊基)-3-环己烯-1-羧醛)、鲜草醛(ベルンアルデヒド)(1-甲基-4-(4-甲基戊基)-3-环己烯羧基醛)、ホモマイラックアルデヒド(1-甲基-4(4-甲基-3-戊烯基)-3-环己烯羧醛)、ジュニパール(4(5)-甲酰基-7,7,9-三甲基双环[4.3.0]壬烯)、ヴェルトラール(八氢-4,7-甲桥茚基羧醛)、铃兰醛(p-叔丁基-α-甲基氢化肉桂醛)、メフラナール(3-甲基-5-苯基戊醛)、エグランタール(4-甲基-2-苯基-2-戊烯醛)、コカール(5-甲基-2-苯基-2-己烯醛)、α-甲基肉桂醛、α-丁基肉桂醛、α-戊基肉桂醛、α-己基肉桂醛、甲酰基乙基四甲基四氢萘(6-乙基-7-甲酰基-1,1,4,4-四甲基-1,2,3,4-四氢萘)等。
作为缩醛类和缩酮类化合物,可以列举Magnolan(2,4-二甲基-4,4a,5,9b-四氢茚并[1.2d]-1,3-二氧六环)、アントキサン(4-异丙基-5,5-二甲基-1,3-二氧六环)、インドフロール(二氢茚基-2,4-二氧六环)、ボアサンブレンフォルテ(甲醛环十二烷基乙基缩醛)、乙醛二乙缩醛、叶醇缩醛(乙醛乙基己烯基缩醛)、乙醛乙基己基缩醛、香茅基甲基缩醛、エリンタール(乙醛乙基芳樟基缩醛)、ボナロックス(2,4-二氧六环-3-甲基-7,10-甲桥螺[5.5]十一烷)、エフェタール(乙醛乙基苯基缩醛)、乙醛乙基异丁子香基缩醛、缩醛R(乙醛苯乙基正丙基缩醛)、フロロパール(乙醛-2-苯基-2,4-戊二醇缩醛)、スピロフロール(3-乙基-2,4-二氧杂螺[5.5]十一碳-8-烯)、乙基二甲基二氧杂螺十一烯、ヘルボキサン(2-丁基-4,4,6-三甲基-1,3-二氧六环)、カラナール(2-(2,4-二甲基环己-3-烯-1-基)-5-甲基-5-(1-甲基丙基)-1,3-二氧六环)、己醛二甲缩醛、己醛二乙缩醛、己醛丙二醇缩醛、カロティン(4,7-二氢-2-(3-戊基)-1,3-二氧杂环庚烯)、2-己烯醛二乙缩醛、顺式-3-己烯醛二乙缩醛、庚醛二甲缩醛、庚醛二乙缩醛、庚醛乙二醇缩醛、2-己基-5-甲基-1,3-二氧戊环、5-甲基-5-丙基-2-(1-甲基丁基)-1,3-二氧六环、辛醛二甲缩醛、辛醛二乙缩醛、壬醛二甲缩醛、壬醛二乙缩醛、癸醛二甲缩醛、癸醛二乙缩醛、2-甲基十一醛二甲缩醛、十二醛二甲缩醛、柠檬醛二甲缩醛、柠檬醛二乙缩醛、柠檬醛丙二醇缩醛、香茅醛环单二醇缩醛、羟基香茅醛二甲缩醛、羟基香茅醛二乙缩醛、顺式3-己烯醛二乙缩醛、苯甲醛二甲缩醛、苯甲醛二乙缩醛、苯甲醛丙二醇缩醛、苯甲醛甘油缩醛、苯乙醛二甲缩醛、苯乙醛乙二醇缩醛、苯乙醛二异丁缩醛、苯乙醛丙二醇缩醛、苯乙醛-2,3-丁二醇缩醛、苯乙醛甘油缩醛、レセダボディ(苯乙醛-2,4-二羟基-2-甲基戊烷缩醛)、3-苯基丙醛二甲缩醛、龙葵醛二甲缩醛、龙葵醛乙二醇缩醛、オスミナールDMA(戊基肉桂醛二甲缩醛)、オスミナールDEA(戊基肉桂醛二乙缩醛)、洋茉莉醛二甲缩醛、洋茉莉醛二乙缩醛、香兰素丙二醇缩醛、ベルドキサン(2,2,5,5-四甲基-4-异丙基-1,3-二氧六环)、アンバーセージ(4,7-二氢-2-异戊基-2-甲基-1,3-二氧杂环庚烯)、アセトケタール(2,5,5-三甲基-2-苯基-1,3-二氧六环)、ジャスモナン(2-丁基-4-二氧杂螺[4.4]壬酮)、フレイストン(乙基-2,4-二甲基-1,3-二氧戊环-2-乙酸酯)、フルクトン(乙基-2-甲基-1,3-二氧戊环-2-乙酸酯)等。
作为酮类化合物,可以列举乙酰基石竹烯、香芹酮、蒲勒酮、薄荷烯酮、胡椒酮、薄荷醇、樟脑、环氧柏木烷、异长叶烷酮、香柏酮、2-庚酮、2-戊酮、3-己酮、3-庚酮、4-庚酮、2-辛酮、3-辛酮、2-壬酮、3-壬酮、2-十一烷酮、2-十三烷酮、甲基异丙基酮、乙基异戊基酮、异丙叉丙酮、亚丁基丙酮、甲基庚二烯酮、甲基庚烯酮、二甲基辛烯酮、コアボン(4-亚甲基-3,5,6,6-四甲基-2-庚酮)、香叶基丙酮、法尼基丙酮、乙偶姻、ブチロイン(5-羟基-4-辛酮)、甲基薰衣草酮(3-羟甲基-2-壬烷)、双乙酰、2,3-戊二酮、2,3-己二酮、3,4-己二酮、2,3-庚二酮、乙酰基异戊酰、戊基环戊酮、戊基环戊烯酮、2-环戊基环戊酮、己基环戊酮、フルウラモン(2-正庚基环戊酮)、顺式茉莉酮、二氢茉莉酮、异茉莉酮、三甲基戊基环戊酮、セダモン(2-亚丁基-3,5,5(3,3,5)-三甲基环戊酮)、サンデックス(3-甲基-5-(2,2,3-三甲基-3-环戊烯基)-3-戊烯-2-酮)、甲基环戊烯醇酮、コロノール(3,5-二甲基-1,2-环戊二酮)、メチルコリロン(3,4-二甲基1,2-环戊二酮)、ベルドン(2-叔丁基环己酮)、对叔丁基环己酮、ヘルバック(3,3-二甲基环己基甲基酮)、フレスコメンテ(2-仲丁基环己酮)、アルテモン(1-乙酰基-3,3-二甲基-1-环己烯)、セルリーケトン(3-甲基-5-丙基-2-环己烯酮)、氪(4-异丙基-2-环己酮)、オリボン(对叔戊基环己酮)、メチルシクロシトロン(2,3,5-三甲基-4-环己烯基-1-甲基酮)、ネロン(1-(对薄荷烯-6-基)-1-丙烷)、ベチバール(4-环己基-4-甲基-2-戊酮)、ハバノール(2-(1-环己烯-1-基)-环己酮)、麦芽酚、乙基麦芽酚、オキサイドケトン(顺式-2-丙酮基-4-甲基-四氢吡喃)、エモキシフロン(5-乙基-3-羟基-4-甲基-2[5H]-呋喃酮)、ホモフロール(2-乙基-4-羟基-5-甲基-3[2H]-呋喃酮和5-乙基-4-羟基-2-甲基-3[2H]-呋喃酮)、ソトロン(3-羟基-4,5-二甲基-2[5H]-呋喃酮)、フラネオール(2,5-二甲基-4-羟基-3[2H]-呋喃酮)、乙酰基二甲基呋喃、糠醛丙酮、2-乙酰基-5-甲基呋喃、2-乙酰基呋喃、甲基四氢呋喃酮、二苄基酮、二苯甲酮、甲基萘基酮、4-突厥酮(5-苯基-5-甲基-3-己酮)、ベチコン(4-甲基-4-苯基-2-戊酮)、α-甲基茴香叉丙酮、胡椒基丙酮、茴香叉丙酮、茴香基丙酮、对甲氧基苯基丙酮、覆盆子酮(4-(对羟基苯基)-2-丁酮)、ラバンドゾン(3-甲基-4-苯基-3-丁烯-2-酮)、亚苄基丙酮、对甲氧基苯乙酮、对甲基苯乙酮、苯丙酮、苯乙酮、乙位突厥酮、突厥酮、异突厥酮、α-王朝酮(1-(5,5-二甲基环己烯-1-基)-4-戊烯-1-酮)、イリトン(4-(2,4,6-三甲基-3-环己烯-1-基)-3-丁烯-2-酮和4-3,5,6-三甲基-3-环己烯-1-基)-3-丁烯-2-酮)、紫罗兰酮、假紫罗兰酮、甲基紫罗兰酮、メチルイリトン(3-甲基-4-(2,4,6-三甲基-3-环己烯基)-3-丁烯-2-酮)、シクロウッド(2,4-二叔丁基环己酮)、鸢尾酮、烯丙基紫罗兰酮、2,6,6-三甲基-2-环己烯-1,4-二酮、カメクDH(2-乙酰基-3,3-二甲基降冰片烷)、フロレックス(6-亚乙基八氢-5,8-甲桥-2H-1-苯并吡喃-2-酮)、プリカトン(4-甲基三环[6.2.1.02.7]十一烷-5-酮)、环氧柏木烷、ベルトフィックス(9-乙酰基-2,6,6,8-四甲基三环[5.3.11.7.01.5]-8-十一烯)、ベルベノン(4,6,6-三甲基-(1R)-双环庚-3-烯-2-酮)、葑酮、カロン(7-甲基-3,5-二氢-2H-苯并二氧杂环庚烯-3-酮)、トリモフィックスO(2,6,10-三甲基-1-乙酰基-2,5,9-环十二碳三烯)、ビタライド(乙酰基二甲基四氢苯并茚满)、エピトン(7(8)-乙酰基-5-异丙基-2-甲基双环[2.2.2]辛-2-烯)、アトリノン(4(5)-乙酰基-7,7,9(7,7,9)-三甲基双环[4.3.0]-1-壬烯)、カシュメラン(6,7-二氢-1,1,2,3,3-五甲基-4(5H)-茚满酮)、ムスコン(3-甲基环十五碳-1-酮)、ムセノンデルタ(3-甲基十五碳-4-烯酮)、シベトン(环十七碳-9-烯-1-酮)、エキザルトン(环十五酮)、ムスクTM-II(环十六碳烯酮)、ファントリド(5-乙酰基-1,1,2,3,3,6-六甲基茚满)、セレストリド(4-乙酰基-6-叔丁基-1,1-二甲基茚满)、トラセオライド(5-乙酰基-3-异丙基-1,1,2,6-四甲基茚满)、トナリド(6-乙酰基-1,1,2,4,4,7-六甲基四氢萘)、ビタライド(乙酰基二甲基四氢苯并茚满、イソ·イー·スーパー(7-乙酰基-1,2,3,4,5,6,7,8-八氢-1,1,6,7-四甲基萘)、二氢香芹酮、布枯酚、姜油酮等。
作为醚类化合物,可以列举甲基己基醚、癸基甲基醚、癸基乙烯基醚、二乙二醇单甲醚、二乙二醇单乙醚、香茅基乙醚、香叶基乙醚、α-松油基甲基醚、ハーバベルト(3,3,5-三甲基环己基乙醚)、异冰片基甲基醚、三环癸烯基甲基醚、イソプロキセン(2-亚乙基-6-异丙氧基双环[2.2.1]庚烷)、ジュニパローム(甲氧基二甲基三环[5.2.1.02.6]癸烷)、环十二烷基甲基醚、マドロックス(1-甲基环十二烷基甲基醚)、フィゼオール(2-乙氧基-2,6,6-三甲基-9-亚甲基双环[3.3.1]-壬烷)、セドランバー(雪松醇甲基醚)、甲基苄基醚、甲基苯基乙醚、乙基-2-甲氧基苄基醚、烯丙基苯基乙醚、异戊基苄基醚、アンサー(异戊基苯基乙醚)、ジャセン(2-甲基-2-丁烯基苯基乙醚)、二苄基醚、环己基苯基醚、ミロオキサイド(环氧化罗勒烯)、氧化柠檬烯(对薄荷-8-烯-1,2-环氧化物)、ルボフィクス(螺[1,4-甲桥萘-2(1H),2’-环氧乙烷],-3,4,4a,5,8,8a-六氢-3’,7-二甲基和螺[1,4-甲桥萘-2(1H),2’-环氧乙烷],-3,4,4a,5,8,8a-六氢-3’,6-二甲基)、三甲基环十二碳三烯环氧化物、氧化石竹烯、环氧化柏木烯、环氧化异长叶烯、氧化芳樟醇、シトロオキサイド(2,2-二甲基-5(1-甲基-1-丙烯基)-四氢呋喃)、ヘルボオキサイド(5-异丙烯基-2-甲基-2-乙烯基四氢呋喃)、ローズフラン(3-甲基-2-(3-甲基-2-丁烯基)-呋喃)、ヘプタベルト(2-庚基四氢呋喃)、薄荷呋喃、茶螺烷、オキシベット(2-氧杂螺[4,7]十二烷)、ムスコゲン(3-氧杂双环[10.3.0]-6-十五碳烯)、シクランバー(13-氧杂双环[10.3.0]十五烷)、アンブロキサン(十氢-3a,6,6,9a-四甲基萘并[2.1-b]呋喃)、グリサルバ(3a-乙基十二氢-6,6,9a-三甲基萘并[2.1-b]呋喃)、1,8-桉树脑、1,4-桉树脑、ガラクソリド(1,3,4,6,7,8-六氢-4,6,6,7,8,8-六甲基环戊基-γ-2-苯并吡喃)、玫瑰醚、氧化橙花醇、リメトール(2,2,6-三甲基-6-乙烯基四氢吡喃)、ジラン(2-丁基-4,6-二甲基二氢吡喃)、ドレモックス(四氢-4-甲基-2-苯基-2H-吡喃)、ルボフロア(9-亚乙基-3-氧杂三环[6.2.1.02.7]十一烷)、六氢茚并吡喃等。
作为酸类化合物,可以列举香叶酸、乙酸、丙酸、丙酮酸、丁酸、异丁酸、2-甲基丁酸、2-乙基丁酸、戊酸、异戊酸、2-甲基戊酸、3-甲基戊酸、己酸、异己酸、2-己酸、4-戊烯酸、2-甲基-2-戊烯酸、庚酸、2-甲基庚酸、辛酸、壬酸、癸酸、2-癸烯酸、十一烯酸、十二酸、肉豆蔻酸、棕榈酸、硬脂酸、邻氨基苯甲酸、油酸、乙酰丙酸、乳酸、苯甲酸、苯基乙酸、肉桂酸、3-苯基丙酸、香草酸、缬氨酸、松香酸、山梨酸等。
作为内酯类化合物,可以列举ペンタリド(环十五内酯)、ハバノリド(氧杂环十六烯-2-酮)、黄葵内酯、环十六内酯、10-氧杂十六内酯、11-氧杂十六内酯、12-氧杂十六内酯、十二碳二酸乙二醇酯、γ-丁内酯、γ-戊内酯、当归内酯、γ-己内酯、γ-庚内酯、γ-辛内酯、γ-壬内酯、ウイスキーラクトン(3-甲基-4-辛内酯)、γ-癸内酯、γ-十一内酯、γ-十二内酯、γ-茉莉内酯、茉莉内酯、顺茉莉酮内酯、ラクトジャスモン(4-甲基-4-癸内酯)、ジャスモラクトン(四氢-6-(3-戊烯基)-2H-吡喃-2-酮)、メンタラクトン(3,6-二甲基-5,6,7,7a-四氢-2(4H)-苯并呋喃酮)、正丁基苯酞、亚丙基异苯并呋喃酮、亚丁基苯酞、δ-己内酯、δ-辛内酯、トリバロン(4,6,6(4,4,6)-三甲基四氢吡喃-2-酮)、δ-壬内酯、δ-癸内酯、马索亚内酯(δ-2-Decenolactone)、δ-十一内酯、δ-十二内酯、δ-十三内酯、δ-十四内酯、ラクトスカトン(十氢-4,α-羟基-2,8,8-三甲基萘-2-羧酸-δ-内酯)、香豆素、二氢香豆素、环己基内酯、6-甲基香豆素、ε-癸内酯、ε-十二内酯等。
作为酯类化合物,可以列举甲酸乙酯、甲酸丙酯、甲酸丁酯、甲酸戊酯、甲酸异戊酯、甲酸己酯、甲酸顺式-3-己烯酯、甲酸辛酯、甲酸芳樟酯、甲酸香茅酯、甲酸香叶酯、甲酸橙花酯、甲酸玫瑰酯、甲酸松油酯、甲酸柏木酯、甲酸石竹烯酯、Aphermate(甲酸-α,3,3-三甲基环己烷甲酯)、甲酸羟基八氢萘酯(ギ酸オキシオクタリン)、甲酸苄酯、甲酸肉桂酯、甲酸苯基乙酯、甲酸茴香酯、甲酸丁子香酯、甲酸十氢-β-萘基酸甲酯、乙酸乙酯、乙酸丙酯、乙酸异丙酯、乙酸丁酯、乙酸异丁酯、乙酸2-甲基丁酯、乙酸异戊酯、乙酸戊酯、乙酸异戊二烯酯、乙酸己酯、乙酸顺式3-己烯酯、乙酸反式-2-己烯酯、乙酸2-乙基己酯、乙酸庚酯、乙酸辛酯、乙酸3-辛酯、乙酸辛烯酯、乙酸壬酯、乙酸癸酯、乙酸三甲基己酯、乙酸癸烯酯、乙酸壬二醇酯、乙酸十二烷基酯、乙酸二甲基十一碳二烯酯、双乙酰、二醋精、三醋精、乙二醇二乙酸酯、乙二醇单丁醚乙酸酯、烯丙基戊基乙醇酸酯、乙酸罗勒烯酯、乙酸月桂烯酯、乙酸二氢月桂烯酯、乙酸二甲基辛酯、乙酸芳樟酯、乙酸香茅酯、乙酸玫瑰酯、乙酸香叶酯、乙酸橙花酯、乙酸四氢里哪醇酯、乙酸乙酯芳樟酯、乙酸薰衣草酯、乙酸异氢薰衣草酯、乙酸橙花叔醇、乙酸香芹基、乙酸二氢香芹酯、乙酸二氢枯茗酯、乙酸松油酯、乙酸异蒲勒醇酯、乙酸薄荷酯、乙酸柠檬油酯、乙酸桃金娘烯酯、乙酸不蒎酯、乙酸葑酯、乙酸冰片酯、乙酸异冰片酯、乙酸柏木酯、乙酸石竹烯酯、乙酸檀香酯、乙酸岩兰烯酯、乙酸愈疮木酯、亚环戊基乙酸甲酯、乙酸环己酯、乙酸对异丙基环己酯、乙酸叔戊基环己酯、乙酸二氢松油酯、乙酸环己基乙酯、フロラレート(乙酸-2,4-二甲基-3-环己烯基甲酯)、ロザムスク(乙酸-α,3,3-三甲基环己烷甲酯)、ベルテネックス(乙酸对叔丁基环己酯)、ベルドックス(乙酸邻叔丁基环己酯)、乙酸-1-乙炔基环己酯、ジヒドロアンブレート(1-乙酰氧基-2-仲丁基-1-乙烯基环己烷)、酢酸ミラルディル(4(3)-(4-甲基-3-戊烯基)-3-环己烯基甲基乙酸酯)、乙酸三环癸烯酯、乙酸三环癸酯、乙酸苄酯、乙酸对甲酚酯、乙酸苯基乙酯、乙酸苏合香酯、乙酸对甲基苄酯、乙酸茴香酯、乙酸胡椒酯、乙酰基香兰素、结晶玫瑰、乙酸龙葵酯、乙酸2,4-二甲基苄酯、乙酸肉桂酯、乙酸苯基丙酯、乙酸枯茗酯、乙酸二甲基苄基甲酯、苯基二醇二乙酸酯、乙酸二甲基苯基乙基甲酯、乙酸苯基乙基甲基乙基甲酯、ベチコールアセテート(4-甲基-4-苯基-2-戊基乙酸酯)、乙酸α-戊基肉桂酯、ジャスマロール(乙酸反式十氢-β-萘酯)、乙酸糠酯、乙酸四氢糠酯、ジャスマール(乙酸-3-戊基四氢吡喃酯)、ジャスメリア(乙酸-5-甲基-3-丁基四氢吡喃酯)、乙酰乙酸乙酯、ジェッサーテ(2-己基乙酰乙酸乙酯)、苄基乙酰乙酸乙酯、环己基乙酸烯丙酯、环己烯基乙酸异丙酯、丙酸乙酯、丙酸丙酯、丙酸烯丙酯、丙酸甲酯、丙酸异丁酯、丙酸异戊酯、丙酸己酯、丙酸顺式-3-己烯酯、丙酸反式-2-己烯酯、丙酸癸烯酯、丙酸芳樟酯、丙酸香茅酯、丙酸玫瑰酯、丙酸香叶酯、丙酸橙花酯、丙酸香芹酯、丙酸松油酯、丙酸薄荷酯、丙酸冰片酯、丙酸异冰片酯、丙酸三环癸烯酯、丙酸苄酯、丙酸苏合香酯、丙酸茴香酯、丙酸苯基乙酯、丙酸肉桂酯、丙酸苯基丙酯、丙酸二甲基苄基甲酯、丙酸苯氧基乙酯、丙酸丙二醇二丙酸酯、烯丙基环己烷丙酸酯、ラブダナックス(3-羟基-3-苯基丙酸乙酯)、呋喃丙酸异丁酯、丁酸甲酯、丁酸乙酯、丁酸丙酯、丁酸异丙酯、丁酸烯丙酯、丁酸丁酯、丁酸异丁酯、丁酸戊酯、丁酸异戊酯、丁酸己酯、丁酸庚酯、丁酸顺式-3-己烯酯、丁酸反式-2-己烯酯、丁酸辛酯、丙二醇二丁酸酯、丁酸芳樟酯、丁酸香茅酯、丁酸玫瑰酯、丁酸香叶酯、丁酸橙花酯、丁酸松油酯、丁酸环己酯、丁酸苄酯、丁酸肉桂酯、丁酸苯基乙酯、丁酸二甲基苄基甲酯、丁酸四氢糠酯、丁酸檀香酯、异丁酸甲酯、异丁酸乙酯、异丁酸丙酯、异丁酸异丙酯、异丁酸丁酯、异丁酸异丁酯、异丁酸异戊酯、异丁酸己酯、异丁酸顺式-3-己烯酯、异丁酸-2,4-己二烯酯、イソペンチレート(异丁酸-1,3-二甲基-3-丁烯酯)、异丁酸辛酯、异丁酸芳樟酯、异丁酸香茅酯、异丁酸玫瑰酯、异丁酸香叶酯、异丁酸橙花酯、异丁酸松油酯、异丁酸三环癸烯酯、异丁酸苄酯、异丁酸对甲酚酯、异丁酸肉桂酯、异丁酸苯基乙酯、异丁酸苯基丙酯、异丁酸苏合香酯、异丁酸二甲基甲酯、异丁酸二甲基苯基乙基甲酯、フロラノール(异丁酸苯氧基乙酯)、异丁酸十氢-β-萘酯、2-甲基丁酸甲酯、2-甲基丁酸乙酯、2-甲基丁酸-2-甲基丁酯、シドラン(2-甲基丁酸己酯)、2-甲基丁酸顺式-3-己烯酯、2-甲基丁酸苄酯、2-甲基丁酸苯基乙酯、2-乙基丁酸烯丙酯、
3-羟基丁酸乙酯、戊酸甲酯、戊酸乙酯、戊酸丁酯、戊酸异丁酯、戊酸戊酯、戊酸顺式-3-己烯酯、戊酸苄酯、戊酸苯基乙酯、戊酸糠酯、异戊酸甲酯、异戊酸乙酯、异戊酸丙酯、异戊酸异丙酯、异戊酸烯丙酯、异戊酸丁酯、异戊酸异丁酯、异戊酸异戊酯、异戊酸戊酯、异戊酸-2-甲基丁酯、异戊酸顺式-3-己烯酯、异戊酸己酯、异戊酸辛酯、异戊酸芳樟酯、异戊酸香茅酯、异戊酸香叶酯、异戊酸薄荷酯、异戊酸松油酯、异戊酸环己酯、异戊酸苄酯、异戊酸苯基乙酯、异戊酸苯基丙酯、异戊酸肉桂酯、マンザネート(2-甲基戊酸乙酯)、水杨酸苯酯、ペラナト(2-甲基戊酸-2-甲基戊酯)、己酸甲酯、己酸乙酯、己酸丙酯、己酸异丙酯、己酸烯丙酯、己酸丁酯、己酸异丁酯、己酸戊酯、己酸异戊酯、己酸己酯、己酸顺式-3-己烯酯、己酸反式-2-己烯酯、己酸庚酯、己酸芳樟酯、己酸香茅酯、己酸香叶酯、己酸香茅酯、己酸苄酯、异己酸甲酯、2-己烯酸甲酯、反式-2-己烯酸乙酯、3-己烯酸甲酯、3-己烯酸乙酯、3-羟基己酸甲酯、3-羟基己酸乙酯、2-乙基己酸乙酯、メルサット(3,5,5-三甲基己酸乙酯)、ベリフロ(6-乙酰氧基己酸乙酯)、庚酸甲酯、庚酸乙酯、庚酸丙酯、庚酸烯丙酯、庚酸辛酯、辛酸甲酯、辛酸乙酯、辛酸戊酯、辛酸丁酯、辛酸丙酯、辛酸烯丙酯、辛酸异戊酯、辛酸己酯、辛酸庚酯、辛酸辛酯、辛酸芳樟酯、辛酸苄酯、辛酸苯基乙酯、辛酸对甲酚酯、2-辛烯酸乙酯、壬酸甲酯、壬酸乙酯、壬酸苯基乙酯、ブーバルテート(2-壬烯酸甲酯)、3-壬烯酸甲酯、癸酸甲酯、癸酸乙酯、癸酸异丙酯、癸酸丁酯、癸酸异戊酯、2-癸烯酸乙酯、2,4-癸二烯酸乙酯、2,4-癸二烯酸丙酯、十一烯酸甲酯、十一烯酸丁酯、十一烯酸异戊酯、十二酸甲酯、十二酸乙酯、十二酸丁酯、十二酸异戊酯、肉豆蔻酸乙酯、肉豆蔻酸甲酯、肉豆蔻酸异丙酯、棕榈酸乙酯、硬脂酸乙酯、硬脂酸丁酯、油酸甲酯、油酸乙酯、苯甲酸甲酯、苯甲酸乙酯、苯甲酸丙酯、苯甲酸异丙酯、苯甲酸烯丙酯、苯甲酸异丁酯、苯甲酸异戊酯、苯甲酸异戊二烯酯、苯甲酸己酯、苯甲酸顺式-3-己烯酯、苯甲酸芳樟酯、苯甲酸香叶酯、苯甲酸苄酯、苯甲酸苯基乙酯、苯甲酸肉桂酯、茴香酸甲酯、茴香酸乙酯、邻甲氧基苯甲酸甲酯、邻甲氧基苯甲酸乙酯、惕各酸乙酯、惕各酸己酯、惕各酸顺式-3-己烯酯、惕各酸香茅酯、
惕各酸香叶酯、惕各酸苄酯、惕各酸苯基乙酯、惕各酸肉桂酯、当归酸甲酯、当归酸丁酯、当归酸异丁酯、当归酸异戊酯、当归酸异戊二烯酯、当归酸顺式-3-己烯酯、当归酸-3-甲基戊酯、当归酸苯基乙酯、丙烯酸乙酯、甲基丙烯酸苯基乙酯、丁烯酸乙酯、丁烯酸异丁酯、丁烯酸环己酯、フルチナト(巴豆酸-4-甲基-戊烷-2-醇酯)、ピロプルナト(巴豆酸-2-环戊基环戊酯)、ダチラト(巴豆酸-1-环己基乙酯)、乙酰丙酸乙酯、乙酰丙酸丁酯、乙酰丙酸异戊酯、乳酸甲酯、乳酸乙酯、乳酸戊酯、乳酸异丁酯、乳酸顺式-3-己烯酯、丁酰乳酸丁酯、丙酮酸乙酯、香叶酸甲酯、香叶酸乙酯、环香叶酸甲酯、环香叶酸乙酯、杨梅醛、フルテート(三环[5.2.1.02.6]癸烷-2-羧酸乙酯)、ジベスコン(2-乙基-6,6-二甲基-2-环己烯-1-羧酸乙酯和2,3,6,6-四甲基-2-环己烯羧酸乙酯)、エチルサフラネート(脱氢环香叶酸乙酯)、环己基丙酸烯丙酯、シクロガルバネート(环己氧乙酸烯丙酯)、カリクソール(2-甲基-6-戊基-4-氧代环己-2-烯羧酸乙酯)、タクリサーテ(1-甲基-3-环己烯羧酸甲酯)、フロラメート(2-叔丁基环己基碳酸乙酯)、ジャスマシクレート(甲基环辛基碳酸酯)、マハゴネート(1-甲基-4-异丙基-2-甲氧甲酰基双环[2.2.2]-辛-5-烯)、特戊酸苯基乙酯、茉莉酮酸甲酯、ヘディオン(二氢茉莉酮酸甲酯)、ベラモス(3,6-二甲基-β-间二羟苯甲酸甲酯)、呋喃羧酸甲酯、呋喃羧酸乙酯、呋喃丙烯酸丙酯、庚炔酸甲酯、庚炔酸乙酯、庚炔酸异戊酯、辛炔酸甲酯、辛炔酸乙酯、癸炔酸甲酯、グリコメル(3-(双环[2.2.1]庚-5-烯-2-基)-3-甲基环氧乙烷羧酸的甲酯)、苯基缩水甘油酸甲酯、苯基缩水甘油酸乙酯、醛C-16(3-甲基-3-苯基缩水甘油酸乙酯)、醛C-20(对甲基-β-苯基缩水甘油酸乙酯)、甲基对甲苯基缩水甘油酸乙酯、草酸乙基香茅酯、琥珀酸二乙酯、琥珀酸二甲酯、丙二酸二乙酯、酒石酸二乙酯、己二酸二乙酯、癸二酸二乙酯、柠檬酸三乙酯、邻苯二甲酸二甲酯、邻苯二甲酸二乙酯、邻苯二甲酸二丁酯、苯基乙酸甲酯、苯基乙酸乙酯、苯基乙酸异丙酯、苯基乙酸丁酯、苯基乙酸丙酯、苯基乙酸异丁酯、苯基乙酸异戊酯、苯基乙酸己酯、苯基乙酸顺式-3-己烯酯、苯基乙酸香茅酯、苯基乙酸玫瑰酯、苯基乙酸香叶酯、苯基乙酸薄荷酯、苯基乙酸苄酯、苯基乙酸苯基乙酯、苯基乙酸对甲酚酯、苯基乙酸丁子香酯、苯基乙酸异丁子香酯、肉桂酸甲酯、肉桂酸乙酯、肉桂酸丙酯、肉桂酸异丙酯、肉桂酸烯丙酯、肉桂酸异丁酯、肉桂酸异戊酯、肉桂酸芳樟酯、肉桂酸苄酯、肉桂酸肉桂酯、肉桂酸苯基乙酯、水杨酸甲酯、水杨酸乙酯、水杨酸丁酯、水杨酸异丁酯、水杨酸戊酯、水杨酸异戊酯、水杨酸己酯、水杨酸顺式-3-己烯酯、水杨酸环己酯、水杨酸苯酯、水杨酸苄酯、水杨酸苯基乙酯、シクロピデン(环松油烯)、アバリン(松香酸甲酯)、ハーコリン(二氢松香酸甲酯)、水杨酸对甲酚酯、苯氧基乙酸烯丙酯、苯基丙酸乙酯、巴西酸亚乙酯、三醋精等。
作为含氮类化合物,可以列举邻氨基苯甲酸甲酯、邻氨基苯甲酸乙酯、邻氨基苯甲酸丁酯、邻氨基苯甲酸顺式-3-己烯酯、邻氨基苯甲酸苯基乙酯、邻氨基苯甲酸肉桂酯、N-甲基邻氨基苯甲酸甲酯、オーランチオール(羟基香茅醛-邻氨基苯甲酸甲酯的席夫碱)、メバントラール(甲基丙基乙醛-邻氨基苯甲酸甲酯的席夫碱)、ジャスメンチン(α-戊基肉桂醛-邻氨基苯甲酸甲酯的席夫碱)、リガントラール((3,5-二甲基-3-环己烯-1-基)亚甲基邻氨基苯甲酸甲酯)、吲哚、粪臭素、クロナール(十二腈)、タンジェニール(2-十三烯腈)、シトラルバ(香叶腈)、香茅腈、レモニール(3,7-二甲基-2,6-壬二烯腈)、枯茗基腈、シンナマルバ(肉桂腈)、三甲胺、吡啶、3-乙基吡啶、2-乙酰基吡啶、3-乙酰基吡啶、2-异丁基吡啶、3-异丁基吡啶、2-正戊基吡啶、5-乙基-2-甲基吡啶、烟酸甲酯、4-(1,4,8-三甲基-3,7-壬二烯基)吡啶、喹啉、异喹啉、对甲基喹啉、四氢对甲基喹啉、6-异丙基喹啉、异丁基喹啉、2-异丁基喹啉、6-仲丁基喹啉、8-仲丁基喹啉、6-(对)叔丁基喹啉、2-叔丁基喹啉、N-取代对薄荷烷-3-酰胺、吡嗪、2-甲基吡嗪、2,5-二甲基吡嗪、2,6-二甲基吡嗪、2,3,5-三甲基吡嗪、2-乙基吡嗪、2-乙基-3-甲基吡嗪、2-乙基-5-甲基吡嗪、2-乙基-3,5(3,6)-二甲基吡嗪、2,3-二乙基吡嗪、2,3-二乙基-5-甲基吡嗪、四甲基吡嗪、2-甲基-5-乙烯基吡嗪、甲氧基吡嗪、2-甲氧基-3-甲基吡嗪、2-甲氧基-3-乙基吡嗪、2-甲氧基-3-异丙基吡嗪、2-异丁基-3-甲氧基吡嗪、2-乙酰基吡嗪、2-乙酰基-3-乙基吡嗪、甲硫基甲基吡嗪、コリロンピラジン(5-甲基-6,7-二氢环戊并吡嗪)、5-甲基喹喔啉、环己烷并吡嗪(5,6,7,8-四氢喹喔啉)、1-甲基吡咯、2-乙酰基吡咯、吡咯烷、インドレン(吲哚-羟基香茅醛的席夫碱)、2-甲基苯并噁唑、十氢环十二噁唑、5-甲基-3-庚酮肟、ブコキシム(1,5-二甲基二环[3.2.1]辛烷-8-酮肟)、ガルダマイド(N-甲基-N-苯基-2-甲基丁酰胺)、二甲苯麝香、麝香酮、葵子麝香、西藏麝香、麝香、2,6-二甲基吡啶、哌啶、2-(1,4,8-三甲基-3,7-壬二烯基)吡啶、2-(2-蒎烯-10-基甲基)吡啶、4-(2-蒎烯-10-基甲基)吡啶、胡椒碱、辣椒碱、壬酸香草酰胺、奎宁、紫苏葶(L-紫苏醛α-反式醛肟)、2-异丙基-4-甲基噻唑、2-异丁基噻唑等。
作为含硫类化合物,可以列举噻唑、4-甲基噻唑、4,5-二甲基噻唑、三甲基噻唑、2-甲基-5-甲氧基噻唑、2-异丙基-4-甲基噻唑、4-甲基-5-乙烯基噻唑、2-异丁基噻唑、硫噻唑(4-甲基-5-噻唑乙醇)、乙酸硫噻唑酯(4-甲基-5-噻唑乙醇乙酸酯)、2-乙酰基噻唑、5-乙酰基-2,4-二甲基噻唑、苯并噻唑、丙基硫醇、硫化氢、异丙基硫醇、2-甲基-3-丁烷硫醇、烯丙基硫醇、异戊基硫醇、硫代香叶醇、柠檬烯硫醇、スルフォックス(8-巯基薄荷酮)、苯硫醇、邻硫代甲酚、2-乙基苯硫酚、2-萘基硫醇、糠基硫醇、2-甲基-3-呋喃硫醇、二甲基硫醚、二甲基二硫醚、二甲基三硫醚、甲基丙基二硫醚、甲基丙基三硫醚、丙基二硫醚、二丙基三硫醚、二烯丙基硫醚、二烯丙基二硫醚、二丁基硫醚、甲硫基丙醇(3-(甲硫基)-1-丙醇)、3-甲硫基-1-己醇、甲硫基丙醛(3-(甲硫基)丙醛)、薄荷硫醚、二硫代螺呋喃、糠基甲基硫醚、2-甲基-5-甲硫基呋喃、甲基糠基二硫醚、糠基二硫醚、噻吩、四氢噻吩、3-噻吩羧醛、5-甲基-2-噻吩羧醛、四氢噻吩-3-酮、三硫代丙酮、巯基乙酸、甲硫基乙酸甲酯、甲硫基乙酸乙酯、2-巯基丙酸、菠萝硫醇(巯基甲基丙酸甲酯)、3-甲硫基丙酸乙酯、硫代乙酸乙酯、硫代乙酸糠酯、硫代丙酸糠酯、硫代丁酸甲酯、甲基甲烷硫代磺酸、异硫氰酸烯丙酯、异硫氰酸苄酯、噻啶(2,4,6-三甲基-4,5-二氢-1,3,5-二噻嗪)、オキサン(2-甲基-4-丙基-1,3-氧硫杂环己烷)等。
作为天然系香料,可以列举阿魏香树脂、香旱芹油、八角茴香油、冷杉油、阿米香树油、黄秋葵籽油、龙涎香酊剂、依兰油、依兰净油、鸢尾香树脂、鸢尾净油、鸢尾油、冬青油、榄香油树脂、榄香香树脂净油、榄香酊剂、橡苔浸膏、橡苔净油、橡苔树脂、橡苔香树脂、奥寇梯木油、桂花净油、桂花浸膏、红没药香树脂、红没药净油、红没药油、乳香香树脂、乳香净油、乳香油、多香果油、牛至油、牛至油、牛至油树脂、橙油、橙花净油、橙花浸膏、卡南加油、古芸香香膏、古芸香膏油、卡藜皮油、海狸香净油、金合欢净油、金合欢花油、桂油、栀子花净油、康乃馨净油、红檀香油、洋甘菊油、小豆蔻油、格蓬油、格蓬树脂、格蓬香树脂、页蒿子籽油、胡萝卜籽油、愈疮木油、愈疮树脂、愈疮浸膏、樟脑树油、荜澄茄油、时萝油、时萝净油、时萝油树脂、鼠尾草油、葡萄柚油、丁香油、木香油、古巴香胶香膏、古巴香胶香膏油、古巴香胶香膏树脂、芫荽油、檫木油、檀香木油、紫苏净油、紫苏油、香茅油、茉莉油、茉莉净油、茉莉浸膏、杜松子油、麝猫净油、麝猫酊剂、长寿花净油、沉香木油、生姜油、肉桂油、桂皮油、肉桂叶油、孔雀松油、苏合香油、苏合香香树脂、留兰香油、香旱芹油、鼠尾草油、柏木油、柏木叶油、天竺葵油、芹菜籽油、百里香油、タゲット油、龙蒿油、块茎净油、莳萝油、茶树油、树苔净油、吐鲁香膏、肉豆蔻油、水仙净油、橙花油、紫罗兰叶净油、松油、松针油、罗勒油、欧芹叶油、欧芹籽油、欧芹油、广藿香油、日本薄荷油、香草净油、金银花净油、玫瑰草油、缬草油、苦橙油、牛膝草油、罗汉柏油、风信子净油、小茴香油、无花果净油、玳玳叶油、罗勒油、月桂叶油、香根草油、胡薄荷油、胡椒油、薄荷净油、薄荷油、香柠檬油、秘鲁香膏、安息香酊剂、安息香香树脂、花梨木油、芳樟油、蛇麻草油、蛇麻草浸膏、蛇麻草净油、马郁兰油、橘皮油、蜜桔油、含羞草浸膏、含羞草净油、含羞草油、没药香树脂、没药净油、没药油、麝香净油、麝香酊剂、桉树油、柚子油、艾草油、白柠檬油、岩玫瑰油、岩玫瑰香树脂、薰衣草油、薰衣草净油、杂薰衣草油、杂薰衣草净油、里哪油、柠檬油、柠檬草油、玫瑰油、玫瑰净油、玫瑰浸膏、迷迭香油、独活草油、月桂油、月桂叶油、苦艾油、麝香、麝猫香、龙涎香、海狸香、麝鼠香等。
作为烃类化合物,可以列举罗勒烯、二氢月桂烯、金合欢烯、柏木烯、α-蒎烯、β-蒎烯、柠檬烯、双戊烯、莰烯、水芹烯、萜品烯、3-蒈烯、异松油烯、红没药烯、β-石竹烯、杜松烯、朱栾倍半萜、罗汉柏烯、愈疮烯、别罗勒烯、月桂烯、长叶烯、异丙基格蓬(1,3,5-十一碳三烯)、对伞花烃、4-异丙基-1-甲基-2-丙烯基苯、二苯基、二苯基甲烷、橙萜烯、柠檬萜烯、佛手柑萜烯、薄荷萜烯、留兰香萜烯、酸橙萜烯、香根草萜烯、玫瑰蜡、茉莉蜡、柠檬烯二聚物、戊烷、己烷、庚烷、辛烷、壬烷、癸烷、十一烷、十二烷、十三烷、十四烷、十五烷、十六烷、十七烷、十八烷、十九烷、二十烷、二十一烷、二十二烷、二十三烷、二十四烷、二十五烷、二十六烷、二十七烷、二十八烷、二十九烷、三十烷等。
此外,本发明的香料成分可以含有香料用溶剂,作为该香料用溶剂,可以列举水、醇类(乙醇、3-甲氧基-3-甲基丁醇、柠檬酸三乙酯等)、醋精(三醋酸甘油酯)、MMB乙酸酯(乙酸3-甲氧基-3-甲基丁酯)、二丁酸乙二醇酯、己二醇、癸二酸二丁酯、Deltyl Extra(肉豆蔻酸异丙酯)、甲基卡必醇(二甘醇单甲醚)、卡必醇(二甘醇单乙醚)、TEG(三甘醇)、苯甲酸苄酯、丙二醇、邻苯二甲酸二乙酯、三丙二醇、Avolin(邻苯二甲酸二甲酯)、DeltylPrime(棕榈酸异丙酯)、二丙二醇DPG-FC(二丙二醇)、金合欢烯、己二酸二辛酯、甘油三丁酸酯(三丁酸甘油酯)、Hydrolite-5(1,2-戊二醇)、二乙酸丙二醇酯、乙酸鲸蜡基酯(乙酸十六烷基酯)、松香酸乙酯、Abalyn(松香酸甲酯)、Citroflex A-2(乙酰基三乙基柠檬酸酯)、Citroflex A-4(三丁基乙酰基柠檬酸酯)、Citroflex No.2(柠檬酸三乙酯)、Citroflex No.4(柠檬酸三丁酯)、Durafix(二氢松香酸甲酯)、MITD(肉豆蔻酸异三癸酯)、聚柠檬烯(柠檬烯聚合物)、丙二醇和1,3-丁二醇等。
上述溶剂之中,为了调整香气的效价,可以使用乙醇、丁酸乙二醇醇、己二醇、甲基卡必醇(二甘醇单甲醚)、卡必醇(二甘醇单乙醚)、丙二醇、二丙二醇DPG-FC(二丙二醇)、丙二醇、1,3-丁二醇等香料用溶剂。这些溶剂的使用量可以在由上述香料和该溶剂构成的香料组合物中配合约0.1~99质量%,优选配合约1~40质量%。
本发明中的香料配合洗涤剂、柔顺剂、香剂等中通常配合该香料组合物约0.00001~50质量%,优选配合约0.0001~30质量%。配合量低于约0.00001质量%时,有时得不到足够香味,超过约50质量%时,香气过强,有时会使洗涤时的操作性下降。
作为本发明中的香料成分,从对布帛赋予优选的轻快香味的方面出发,优选高挥发性香料成分,尤其优选对轻快的香味产生好感且清爽的香味的香料成分。作为这样的香料,可以优选地列举例如:α-蒎烯、β-蒎烯、芳樟醇、苯乙醇、柠檬烯、乙酸苄酯、香茅醇、香叶醇、萜品醇、乙酸萜品酯、丁子香酚、茉莉酸甲酯、苯甲醇、α-紫罗酮、β-紫罗酮、α-甲基紫罗酮、β-甲基紫罗酮等合成香料。另外,作为天然香料,通过3mmHg左右、约32~100℃的减压蒸馏得到的馏分大致与本发明的香料吻合。
作为高挥发性香料成分,可以列举例如茴香脑、苯甲醛、乙酸苄酯、苯甲醇、甲酸苄酯、乙酸异冰片酯、莰烯、顺式柠檬醛(橙花醛)、香茅醛、香茅醇、乙酸香茅酯、p-枯烯、癸醛、二氢芳樟醇、二氢月桂烯醇、二甲基苯基甲醇、桉叶油素、香叶醛、香叶醇、乙酸香叶酯、香叶腈、乙酸顺式3-己烯酯、羟基香茅醛、d-柠檬烯、芳樟醇、氧化芳樟醇、乙酸芳樟酯、丙酸芳樟酯、邻氨基苯甲酸甲酯、α-甲基紫罗兰酮、甲基壬基乙醛、乙酸甲基苯基甲酯、乙酸L-薄荷酯(酢酸ラエボ-メンチル)、薄荷酮、异薄荷酮、月桂烯、乙酸月桂烯酯、月桂烯醇、橙花醇、乙酸橙花酯、乙酸壬酯、苯乙醇、α-蒎烯、β-蒎烯、γ-萜品烯、α-萜品醇、β-萜品醇、乙酸松油酯、和Vertenex(乙酸对叔丁基环己酯)等。另外,还可以优选地列举:含有高比例的高挥发性香料成分的天然油,例如杂薰衣草油含有芳樟醇、乙酸芳樟酯、香叶醇和香茅醇作为主成分,是优选的。另外,柠檬油和橙萜烯两者均含有例如约95%的d-柠檬烯,也是优选的。
作为中挥发性香料成分,可以列举例如戊基肉桂醛、水杨酸异戊酯、β-石竹烯、柏木烯、肉桂醇、香豆素、乙酸二甲基苄基甲酯、乙基香兰素、丁子香酚、异丁子香酚、乙酸糠酯、洋茉莉醛、水杨酸3-顺式己烯酯、水杨酸己酯、铃兰醛(对叔丁基-α-甲基氢肉桂醛)、γ-甲基紫罗兰酮、橙花叔醇、广霍香醇、苯己醇、β-芹子烯、乙酸三氯甲基苯基甲酯、柠檬酸三乙酯、香兰素和藜芦醛等。柏木萜烯主要由α-柏木烯、β-柏木烯和其它的C15H24倍半萜烯构成。
作为低挥发性香料成分,可以列举例如、二苯甲酮、水杨酸苄酯、巴西酸乙二醇酯、佳乐麝香(1,3,4,6,7,8-六氢-4,6,6,7,8,8-六甲基环戊-γ-2-苯并吡喃)、己基肉桂醛、新铃兰醛(4-(4-羟基-4-甲基戊基)-3-环己烯-10-羧醛)、甲基柏木酮、二氢茉莉酸甲酯、甲基β-萘基酮、麝香茚酮、酮麝香、三甲苯麝香和乙酸苯基乙基苯酯等。
作为本发明中的香料成分,从对布帛赋予优选的轻快香味的方面出发,优选沸点约为250℃以下的化合物、更优选含有沸点约为20℃以上且200℃以下的化合物。另外,还优选为碳原子数约为3以上且15以下的化合物,还优选分子量约为50以上且350以下的程度的化合物。特别优选碳原子数为3以上且5以下、分子量为350以上且350以下并且沸点为20℃以上且200℃以下的香料成分。作为这样的香料成分,只要不妨碍本发明的效果就没有特别限定,可以列举例如1,8-桉树脑、1,4-桉树脑、α-紫罗酮、β-紫罗酮、铃兰醛等。上述沸点和分子量等例如可以参考上述“Perfume and Flavor Chemicals(合成香料))”等公知文献的记载。
上述洗涤用柔顺剂和洗涤剂等只要包含香料成分就没有特别限定,也可以一开始就包含香料成分,也可以添加市售的香剂等香料成分。作为向洗涤用柔顺剂和/或洗涤剂等中添加香料成分的方法,没有特别限定,例如能够预先在洗涤用柔顺剂和/或洗涤剂等中混合后使用。
作为本发明中的洗涤用柔顺剂,能够应用衣料用洗涤柔顺剂组合物等各种柔顺剂,没有特别限定,可以使用例如蜡乳液、两性表面活性剂类、阳离子性表面活性剂类、非离子表面活性剂类、油脂类和多元醇类的柔顺剂等。本发明的洗涤用柔顺剂可以是水系洗涤用,也可以是溶剂洗涤用。
特别优选使用含有含氨基硅氧烷、含氧亚烷基硅氧烷、表面活性剂的柔顺剂。作为表面活性剂,可以列举羧酸盐类的阴离子表面活性剂;磺酸盐类的阴离子表面活性剂;硫酸酯盐类的阴离子表面活性剂;磷酸酯盐类的阴离子表面活性剂(特别是烷基磷酸酯盐)等阴离子表面活性剂;山梨醇酐脂肪酸酯、二乙二醇单硬脂酸酯、二乙二醇单油酸酯、甘油单硬脂酸酯、甘油基单油酸酯、丙二醇单硬脂酸酯等多元醇单脂肪酸酯;N-(3-油烯氧基(オレイロキシ)-2-羟基丙基)二乙醇胺、聚氧乙烯氢化蓖麻油、聚氧乙烯山梨糖醇蜂蜡、聚氧乙烯山梨醇酐倍半硬脂酸酯、聚氧乙烯单油酸酯、聚氧乙烯山梨醇酐倍半硬脂酸酯、聚氧乙烯甘油基单油酸酯、单硬脂酸聚乙二醇、聚氧乙烯单月桂酸酯、聚氧乙烯单油酸酯、聚氧乙烯十六烷基醚、聚氧乙烯月桂醇醚等非离子型表面活性剂;季铵盐、胺盐或胺等阳离子表面活性剂;含有羧基、磺酸酯、硫酸酯的仲胺或叔胺的脂肪族衍生物;以及杂环式仲胺或叔胺的脂肪族衍生物等两性离子表面活性剂等。从留香性的观点出发,最优选的表面活性剂为非离子型表面活性剂。
作为本发明中的洗涤剂,能够应用衣料用洗涤剂组合物等各种洗涤剂,没有特别限定,能够使用例如形成为通常的粉体或液体配合组成的衣料用洗涤剂组合物,可优选地列举含有非离子型表面活性剂的粉体或液体洗涤剂组合物。本发明的洗涤剂可以是水系洗涤用,也可以是溶剂洗涤用。
出于保持上述香料成分的目的的本发明的聚氨酯类纤维的应用也包括在本发明中。通过使本发明的聚氨酯类纤维吸收香料成分,能够有效地保持在上述洗涤用柔顺剂和/或洗涤剂等中含有的具有优选香气的香料成分,其结果显示出优选香气长时间持续的香气持续性。
具有使本发明的聚氨酯类纤维吸收香气成分的过程的、布帛的香气保持方法也包括在本发明中。作为使之吸收香料成分的方法,可优选地列举利用洗涤的方法,该洗涤可以是在水浴中的清洗(水系洗涤),也可以是在干洗溶剂中的清洗(溶剂洗涤),从在各家庭中日常进行的方面考虑,优选水系洗涤。另外,作为使之吸收香料成分的方法的其它方式,可以列举包含香料成分的液体状物质的喷雾等。另外,使本发明的聚氨酯类纤维吸收香料成分而得到的纤维原材料也包括在本发明中。提供本发明品作为这种纤维原材料时,从留香性优良的方面出发,优选进行两次以上使之吸收香料的工序而得到的纤维原材料。
上述洗涤只要不妨碍本发明的效果就没有特别限定,例如可以具有清洗工序、漂洗工序和干燥工序,上述清洗工序和/或漂洗工序可以根据需要进行多次。作为干燥方法,可以列举例如利用悬挂晾干等的自然干燥和滚筒干燥等。作为上述水系洗涤,只要使用含有香料成分的洗涤用柔顺剂和/或洗涤剂就没有特别限定,可以使用洗涤机,也可以手洗。另外,上述溶剂洗涤是指以水以外的溶剂作为介质液体的,可以列举链烷烃、环烷烃和芳香族烃等石油类溶剂;以及四氯乙烯、二氯五氟丙烷等合成溶剂等。关于上述洗涤,温度、时间等各条件根据布帛的种类等而不同,可以适当设定。
另外,通过洗涤使本发明的聚氨酯类纤维吸收香料成分的情况下,该香料成分可以在洗涤剂中,也可以含在洗涤用柔顺剂中,也可以含在这两者中。另外,也可以是将含有香料成分的香剂与洗涤用柔顺剂和/或洗涤剂并用的形态。特别优选在洗涤时的最终漂洗工序中使之吸收香料成分,此时,优选使用含有上述洗涤用柔顺剂的漂洗水等。另外,香料成分优选在上述洗涤用柔顺剂和/或洗涤剂中配合约0.0001~1重量%、更优选配合约0.01~0.5重量%。作为洗涤时间,没有特别限定,例如可以是几分钟至包含干燥工序在内约48小时,优选为几分钟至包含干燥工序在内约24小时。
在本发明中作为洗涤对象的布帛和使用该布帛的衣料只要能作为洗涤对象就没有特别限定。本发明的洗涤方法中,为了防止对含有离子性或离子交换性官能团和包含离子性或离子交换性官能团的添加剂的纤维的影响、即防止因洗涤剂组合物导致的离子性或离子交换性能(离子性香料的吸收能力)的下降,作为使衣料用洗涤剂组合物中含有的表面活性剂,优选使用HLB10~17的非离子型表面活性剂。作为非离子型表面活性剂,可以列举例如直链状或支链型的醇乙氧基化物的环氧乙烷加成物或环氧丙烷加成物或者环氧乙烷-环氧丙烷加成物(嵌段物、无规物)等。
作为这种非离子型表面活性剂,可以列举例如对碳原子数为6~22、优选为8~18的脂肪族醇加成平均3~30摩尔、优选为7~20摩尔的碳原子数为2~4的环氧烷烃后的聚氧亚烷基烷基(或烯基)醚,其中,特别优选为聚氧乙烯烷基(或烯基)醚、聚氧乙烯聚氧丙烯烷基(或烯基)醚、聚氧乙烯烷基(或烯基)苯基醚。另外,可以列举选自在长链脂肪酸烷基酯的酯键间加成有环氧烷烃的化合物、聚氧乙烯山梨糖醇脂肪酸酯、脂肪酸甘油酯、和碳原子数为6~18的脂肪酸与碳原子数为5~6的単糖类或其单烷基醚的酯等的糖酯类非离子型表面活性剂等。
另外,作为此外可使用的非离子型表面活性剂,优选含有环氧乙烷基/环氧丙烷基的非离子型表面活性剂,可以列举由环氧乙烷的平均加成摩尔数n为3~20、n=0的未反应醇的量为10质量%以下表示的非离子型表面活性剂;对碳原子数为10~16的仲醇加成平均5~15摩尔的环氧乙烷后的化合物;对最短支链的碳原子数为5以下的总碳原子数为8~22的具有支链烷基或烯基的伯醇加成平均5~15摩尔的环氧乙烷后的非离子型表面活性剂。
作为进一步可以使用的非离子型表面活性剂,可以列举以脂肪酸酯或氢化蓖麻油为基础骨架的HLB 10~16的非离子型表面活性剂,该表面活性剂是对上述基础骨架加成亲水基团而成的,可以使用例如山梨醇酐脂肪酸酯、聚氧乙烯山梨醇酐脂肪酸酯、聚乙二醇单硬脂酸酯、聚乙二醇异硬脂酸酯、聚氧乙烯甘油异硬脂酸酯、聚氧乙烯甘油三异硬脂酸酯、聚氧乙烯甘油三油酸酯、聚氧乙烯氢化蓖麻油、聚氧乙烯蓖麻油、月桂酸聚氧乙烯氢化蓖麻油、异硬脂酸聚氧乙烯氢化蓖麻油等。
本发明方法中,HLB在10~17的范围以外的非离子型表面活性剂的情况下,对各种污渍的清洗效果下降,是不优选的。HL非离子型表面活性剂的含量优选相对于洗涤剂组合物总量为10~60质量%。需要说明的是,本发明方法中所用的衣料用洗涤剂组合物中,在上述各种HLB10~17的非离子型表面活性剂以外,可以适当配合通常在洗涤剂原料中配合的成分,例如非晶二氧化硅等多孔无机氧化粉体,蒙脱石、水辉石等粘土化合物,铝硅酸盐、碳酸钠等无机碱助洗剂,荧光剂、酶、牛油皂、粉碎助剂、流动性改善剂等。
洗涤剂成分和柔顺剂成分对本发明留香性的影响均较小,但为了有效发挥留香性,优选通过强的漂洗工序或脱水尽可能地除去洗涤剂成分。
通过将包含香料成分的液体状物质喷雾来使本发明的聚氨酯类纤维吸收香料成分的情况下,作为该液体状物质,只要不妨碍本发明的效果就没有特别限定,可以是含有上述香料用溶剂的液体,优选配合约0.0001~1重量%的香料成分的液体,更优选配合约0.01~0.5重量%的香料成分的液体。
实施例
以下,示出实施例和比较例具体说明本发明,但本发明不限于下述实施例。需要说明的是,下文中仅为“%”时是指“重量%”。
各实施例中,各香料的赋予如下所述。
(模型香料的赋予方法)
作为模型香料,使用将桉树脑、α-紫罗酮和铃兰醛各0.15g溶于乙醇100mL后的溶液。使用将该溶液20mL用水980mL稀释后的稀释液作为第二次漂洗水。作为第二次漂洗水90mL中的绝对量,为以下这样的组成。
·桉树脑 2700μg
·α-紫罗酮 2700μg
·铃兰醛 2700μg
·乙醇 1.8g
·纯水 余量
作为洗涤操作,在100mL的螺口瓶中,作为用于赋予模型香料的试样加入作为在后述的实施例和比较例中制作的布帛并将其裁切成3.00±0.10g的布帛(例如若以克重150g/m2的布帛裁切3.00g计,则形成10cm×20cm的方形布帛)的试样3.00g、JAFET标准洗涤剂0.12mL、纯水90mL,利用振荡机在初始温度40℃振荡5分钟。之后,作为脱水操作,以3000rpm进行2分钟离心分离。作为第一次漂洗操作,在100mL的螺口瓶中加入脱水操作后的上述试样和纯水90mL,利用振荡机在初始温度40℃振荡2分钟,从而进行了上述脱水操作。作为第二次漂洗操作,在100mL的螺口瓶加入第一次漂洗操作后的上述试样片和含有上述模型香料的第二次漂洗水90mL,利用振荡机在初始温度23℃振荡2分钟后,从而进行了上述脱水操作。作为功能保持耐久试验,在为了评价功能保持率而进行多次洗涤的情况下,省略第一次漂洗操作的脱水工序,使漂洗操作为一次,除此以外同样地反复进行上述清洗处理。如此进行了清洗处理后,在相对湿度65%、室温下进行24小时悬挂干燥,由此使赋予模型香料后的试样干燥。
(市售香料的赋予方法)
将市售的棉毛巾(棉100%)10条(质量1000±100g)、作为用于赋予市售香料的试样的相当于尺寸LL(男性用)的衬衫状缝制物2条(将衬衫状缝制物的腰部适当裁切除去后调整为合计质量400±40g,相当于对作为洗涤物的衬衫赋予含香料柔顺剂)和洗涤剂投入全自动洗衣机(东芝公司制“AW-80VC(WL)”),将水量设定为12L,将柔顺剂加入柔顺剂盒中,以自动模式进行了依次进行清洗(6分钟)、漂洗2次、脱水(6分钟)的清洗处理。需要说明的是,洗涤中使用的水使用自来水。清洗处理后,在相对湿度65%、室温下进行24小时悬挂干燥,由此使赋予了市售香料的试样干燥。
洗涤剂:JAFET标准洗涤剂(无香料)16mL
Lenor Happiness Aroma Jewel Ruby(P&G公司制的市售香料)5g
柔顺剂:无
各实施例中,各感官试验如下进行。
(感官试验1:6级气味强度表示法)
气味判定者4人基于以下所述的6级气味强度以0.5刻度对各香料赋予试样的气味进行评价,采用各判定者的评价的平均值。需要说明的是,本感官试验对柔顺剂味进行嗅闻分辨,上述气味强度是仅与柔顺剂味有关的强度。评价在干燥后经过24小时的时刻、经过48小时的时刻和经过72小时的时刻这3点进行。
气味强度
0:无味
1:勉强可感知的气味
2:可分辨是什么味的弱气味
3:可轻松感知的气味
4:强的气味
5:强烈的气味
(感官试验2:9级愉快·不愉快度表示法)
气味判定者4人基于以下所述的9级愉快·不愉快度以0.5刻度对各香料赋予试样的气味进行评价,采用了各判定者的评价的平均值。另外,评价气味的性质具体是怎么样的。需要说明的是,本感官试验涉及香料赋予试样的气味整体,含有柔顺剂味和布帛味的气味成为评价对象。评价在干燥后经过48小时的时刻进行。
愉快·不愉快度
+4:极端愉快
+3:非常愉快
+2:愉快
+1:略愉快
0:既不愉快也无不愉快
-1:略不愉快
-2:不愉快
-3:非常不愉快
-4:极端不愉快
(感官试验3:功能保持耐久试验)
将相当于尺寸LL(男性用)的衬衫状缝制物2条(将衬衫状缝制物的腰部适当裁切除去后调整至合计质量400±40g)作为香料赋予试样,依据“模型香料的赋予方法”段落或“市售香料的赋予方法”段落赋予模型香料或市售香料,对该试样实施50次清洗处理后,在相对湿度65%、室温下进行24小时悬挂干燥使之干燥后,进行与感官试验2相同的试验。
(香料成分的总释放量的测定)
各实施例中,香料成分的总释放量的测定如下进行。
设备分析试验通过气相色谱质谱法(以下简称为GC/MS)进行。
具体来说,分别从干燥后经过48小时的香料赋予试样按照3.00±0.10g裁切10cm~20cm见方的布片,进行称量,精确到0.01g,放入玻璃容器(采尘器,impinger)。在该玻璃容器中于室温(23℃±3℃)或40℃以100mL/分钟流通空气(AirzeroA)1小时,将生成气体捕集在吸附管(吸附剂Tenax-GR)中。捕集时使用的装置的示意图示于图1中。即,如图1所示,将赋予了模型香料或市售香料的试样3保持在玻璃容器2内,在该玻璃容器2内流通100mL/分钟的空气,由此将生成的气体捕集在吸附管1中。对于捕集生成气体后的吸附管1,通过热解吸GC/MS法以如下所示的条件进行测定。
关于标准曲线,在100mL容量瓶中采取甲苯的标准品0.1152g,用甲醇进行定容从而制成了标准溶液。从适当稀释该溶液而制成的3水平的标准溶液中采取1μL注入吸附管。将这些吸附管在下述GC/MS测定的条件下进行分析。根据所注入的成分的绝对量(μg)和GC/MS总离子流色谱图的峰面积之间的关系制成了标准曲线。根据试样的通过GC/MS总离子流色谱图检测出的全部峰的总面积,利用甲苯标准曲线求出总释放量。
热解吸装置:JTD-505II型(日本分析工业公司制)
一次热解吸条件:解吸温度260℃,捕集温度-60℃、15分钟
二次热解吸条件:280℃、180秒钟
GC装置:HP5890(Hewlett Packard公司制)
柱:DB-5MS(J&W公司制)30m×0.25mmID膜厚0.5μm
柱温度:40℃(4分钟)280℃(升温速度6℃/分钟)
MS装置:JMS-SX102A质谱仪(日本电子公司制)
离子化方法:EI
扫描范围:m/z 10~500(1.2秒/scan)
TIC质量范围:m/z 29~500”
(评价基准)
关于各实施例品和比较例品,将干燥后经过48小时的时刻的基于感官试验1的气味强度为2.0以上且在室温(23℃±3℃)测定的香料成分的总释放量为0.1μg/g·小时以上的情况定为“○”,将并非如此的情况定为“×”,示于表3和表4中。
[实施例1]
在容器中相对于分子量3500的四亚甲基醚二醇1摩尔投入2.06摩尔的4,4’-MDI,使用三乙胺作为催化剂,在90℃使之反应,将所得到的反应产物在N,N-二甲基乙酰胺(DMAc)中充分搅拌使之溶解而得到了溶液。接着,将包含乙二胺(简称为EDA)作为增链剂的DMAc溶液添加到上述溶解有反应产物的溶液中,进而添加包含二乙胺作为封端剂的DMAc溶液,之后,作为稳定剂以固体成分比例1%添加二乙烯基苯与对甲酚的加聚物(杜邦公司制“メタクロール”(注册商标)2390),从而制备了总固体成分为33重量%的聚氨酯脲溶液PUU-A。所得到的溶液在40℃具有约2800泊的粘度。聚合物在DMAc中以0.5g/100mL的溶液浓度在25℃进行测定时,为0.98的特性粘度。
将PUU-A在高温(350℃)的惰性气体(氮气)中以4根长丝(フィラメント)从纺丝头喷出,通过在该高温气体中的通过而进行干燥,通过喷气式捻丝机使得干燥途中的丝被捻合,使4根长丝结合,经过导丝辊在油辊上赋予了处理剂。需要说明的是,被赋予至油辊的处理剂是由在25℃的粘度为10厘斯的硅油96重量%、硬脂酸镁4重量%构成的油剂。另外,调整油辊的转速使得油剂的附着量相对于纤维为5重量%。以540m/分钟的速度进行卷取,制造了4根长丝的33dtex的聚氨酯脲纤维PUU-1。构成PUU-1的聚氨酯脲的氨基甲酸基浓度和脲基浓度的总和为1.00mol/kg,有效末端胺浓度为34meq/kg。需要说明的是,PUU-1的高温侧熔点为253℃。
仅使用PUU-1,供于320针、筒直径3.5英寸(29针数)的单口圆编机进行编织,在120℃进行1分钟的蒸气定型,得到了宽度约5cm的编织圆筒针织布(38g/m2)。保持不对其进行开幅的状态作为样品(相当于38g/m2的2条针织布重叠)。赋予表3所述的香料后,实施了上述感官试验1~3和香料成分的总释放量的测定。其结果示于表3。经过48小时的时刻的气味强度为4.0。经过48小时的时刻的香料释放量1为3.56μg/g·小时。
[实施例2]
在容器中对于分子量1800的四亚甲基醚二醇1摩尔投入1.70摩尔的4,4’-MDI,在90℃使之反应,将所得到的反应产物在N,N-二甲基乙酰胺(DMAc)中充分搅拌使之溶解而得到了溶液。接着,将包含乙二胺(简称为EDA)作为增链剂的DMAc溶液添加到上述溶解有反应产物的溶液中,进而添加包含二乙胺作为封端剂的DMAc溶液,之后,作为稳定剂以固体成分比例1%添加二乙烯基苯与对甲酚的加聚物(杜邦公司制“メタクロール”(注册商标)2390),从而制备了总固体成分为30重量%的聚氨酯脲溶液PUU-B。所得到的溶液在40℃具有约3000泊的粘度。聚合物在DMAc中以0.5g/100mL的溶液浓度在25℃进行测定时,为1.05的特性粘度。
在PUU-B中以固体成分比例2%添加通过叔丁基二乙醇胺与亚甲基双(4-环己基异氰酸酯)的反应而生成的聚氨酯(杜邦公司制“メタクロール”(注册商标)2462)后,在高温(350℃)的惰性气体(氮气)中以4根长丝从纺丝头喷出,通过在该高温气体中的通过而进行干燥,通过喷气式捻丝机使得干燥途中的丝被捻合,使多根长丝结合,经过导丝辊,与实施例1同样地在油辊上赋予了处理剂。以540m/分钟的速度进行卷取,制作了4根长丝结合的33dtex、44dtex、55dtex、以及2根长丝结合的22dtex的聚氨酯脲纤维PUU-2。构成PUU-2的聚氨酯脲的氨基甲酸基浓度和脲基浓度的总和为1.51mol/kg,有效末端胺浓度为19meq/kg。需要说明的是,PUU-2的高温侧熔点为280℃。
仅使用33dtex的PUU-2,供于320针、筒直径3.5英寸(29针数)的单口圆编机进行编织,在120℃进行1分钟的蒸气定型,得到了宽度约5cm的编织圆筒针织布(38g/m2)。保持不对其进行开幅的状态作为样品(相当于38g/m2的2条针织布重叠)。赋予表3所述的香料后,实施了上述感官试验1~3和香料成分的总释放量的测定。其结果示于表3。经过48小时的时刻的气味强度为5.0。经过48小时的时刻的香料释放量1为22.4μg/g·小时。
[实施例3]
将脱水后的四氢呋喃87.5摩尔和脱水后的3-甲基四氢呋喃12.5摩尔投入带搅拌机的反应器中,在氮封下于温度10℃在催化剂(高氯酸70重量%和乙酸酐30重量%的混合物)的存在下进行8小时聚合反应,用氢氧化钠水溶液对反应结束液进行中和,通过该共聚方法得到数均分子量2000的共聚四亚甲基醚二醇(包含12.5摩尔%的来自3-甲基四氢呋喃的结构单元(a)),将其用作聚亚烷基醚二醇。在容器中相对于该共聚四亚甲基醚二醇1摩尔投入4.9摩尔的MDI,在90℃使之反应,使所得到的反应产物在N,N-二甲基乙酰胺(DMAc)中充分溶解。接着,将包含EDA作为增链剂的DMAc溶液添加到上述溶解有反应产物的溶液中,之后,作为稳定剂以固体成分比例1%添加二乙烯基苯与对甲酚的加聚物(杜邦公司制“メタクロール”(注册商标)2390),从而制备了总固体成分为32重量%的聚氨酯脲溶液PUU-C。
将PUU-C在高温(350℃)的惰性气体(氮气)中以3根长丝从纺丝头喷出,通过在该高温气体中的通过而进行干燥,通过喷气式捻丝机使得干燥途中的丝被捻合,使3根长丝结合,经过导丝辊与实施例1同样地在油辊上赋予了处理剂。以500m/分钟的速度进行卷取,制造了3根长丝结合的33dtex的聚氨酯脲纤维PUU-3。需要说明的是,构成PUU-3的聚氨酯的氨基甲酸基浓度和脲基浓度的总和为3.00mol/kg,有效末端胺浓度为32meq/kg。需要说明的是,PUU-3的高温侧熔点为266℃。
仅使用PUU-3,供于320针、筒直径3.5英寸(29针数)的单口圆编机进行编织,在120℃进行1分钟的蒸气定型,得到了宽度约5cm的编织圆筒针织布(38g/m2)。保持不对其进行开幅的状态作为样品(相当于38g/m2的2条针织布重叠)。赋予表3所述的香料后,实施了上述感官试验1~3和香料成分的总释放量的测定。其结果示于表3。经过48小时的时刻的气味强度为5.0。经过48小时的时刻的香料释放量1为42.5μg/g·小时。
[实施例4]
将脱水后的四氢呋喃85.5摩尔和脱水后的3-甲基四氢呋喃14.5摩尔投入带搅拌机的反应器中,在氮封下于温度10℃在催化剂(高氯酸70重量%和乙酸酐30重量%的混合物)的存在下进行8小时聚合反应,用氢氧化钠水溶液对反应结束液进行中和,通过该共聚方法得到数均分子量1000的共聚四亚甲基醚二醇(包含14.5摩尔%的来自3-甲基四氢呋喃的结构单元(a)),将其用作聚亚烷基醚二醇。在容器中相对于该共聚四亚甲基醚二醇1摩尔投入5.3摩尔的MDI,在90℃使之反应,使所得到的反应产物在N,N-二甲基乙酰胺(DMAc)中充分溶解。接着,将包含二乙胺和EDA作为增链剂的DMAc溶液添加到上述溶解有反应产物的溶液中,之后,作为稳定剂以固体成分比例1%添加二乙烯基苯与对甲酚的加聚物(杜邦公司制“メタクロール”(注册商标)2390),从而制备了总固体成分为32重量%的聚氨酯脲溶液PUU-D。
将PUU-D在高温(350℃)的惰性气体(氮气)中以3根长丝从纺丝头喷出,通过在该高温气体中的通过而进行干燥,通过喷气式捻丝机使得干燥途中的丝被捻合,使3根长丝结合,经过导丝辊与实施例1同样地在油辊上赋予了处理剂。以500m/分钟的速度进行卷取,制造了3根长丝结合的33dtex的聚氨酯脲纤维PUU-4。需要说明的是,构成PUU-4的聚氨酯的氨基甲酸基浓度和脲基浓度的总和为4.50mol/kg,有效末端胺浓度为21meq/kg。需要说明的是,PUU-4的高温侧熔点为288℃。
仅使用PUU-4,供于320针、筒直径3.5英寸(29针数)的单口圆编机进行编织,在120℃进行1分钟的蒸气定型,得到了宽度约5cm的编织圆筒针织布(38g/m2)。保持不对其进行开幅的状态作为样品(相当于38g/m2的2条针织布重叠)。赋予表3所述的香料后,实施了上述感官试验1~3和香料成分的总释放量的测定。其结果示于表3。经过48小时的时刻的气味强度为4.0。经过48小时的时刻的香料释放量1为2.6μg/g·小时。
[实施例5]
在容器中对于分子量1800的四亚甲基醚二醇1摩尔投入2.60摩尔的4,4’-MDI,在80℃使之反应,将所得到的反应产物在N,N-二甲基乙酰胺(DMAc)中充分搅拌使之溶解而得到了溶液。接着,将包含作为增链剂的乙二醇、作为催化剂的乙酸酐的DMAc溶液添加到上述溶解有反应产物的溶液中,进而添加包含丁醇作为封端剂的DMAc溶液,之后,作为稳定剂以固体成分比例1%添加二乙烯基苯与对甲酚的加聚物(杜邦公司制“メタクロール”(注册商标)2390),从而制备了总固体成分为35重量%的聚氨酯氨基甲酸酯溶液PU-E。所得到的溶液在40℃具有约3500泊的粘度。聚合物在DMAc中以0.5g/100mL的溶液浓度在25℃进行测定时,为1.10的特性粘度。
将该聚氨酯氨基甲酸酯溶液PU-E在高温(350℃)的惰性气体(氮气)中以2根长丝从纺丝头喷出,通过在该高温气体中的通过而进行干燥,通过喷气式捻丝机使得干燥途中的丝被捻合,使2根长丝结合,经过导丝辊与实施例1同样地在油辊上赋予了处理剂。以600m/分钟的速度进行卷取,制造了2根长丝结合的33dtex的聚氨酯氨基甲酸酯纤维PU-5。构成PU-5的聚氨酯氨基甲酸酯的氨基甲酸基浓度和脲基浓度的总和为1.95mol/kg。需要说明的是,PU-5的高温侧熔点为220℃。
仅使用PU-5供于320针、筒直径3.5英寸(29针数)的单口圆编机进行编织,在120℃进行1分钟的蒸气定型,得到了宽度约5cm的编织圆筒针织布(38g/m2)。保持不对其进行开幅的状态作为样品(相当于38g/m2的2条针织布重叠)。赋予表3所述的香料后,实施了上述感官试验1~3和香料成分的总释放量的测定。其结果示于表3。经过48小时的时刻的气味强度为5.0。经过48小时的时刻的香料释放量1为10.2μg/g·小时。
[实施例6]
在容器中相对于分子量2000的四亚甲基醚二醇0.5摩尔和分子量2000的聚乙二醇0.5摩尔投入5.30摩尔的4,4’-MDI,在80℃使之反应,将所得到的反应产物在N,N-二甲基乙酰胺(DMAc)中充分搅拌使之溶解而得到了溶液。接着,将包含作为增链剂的乙二醇、作为催化剂的乙酸酐的DMAc溶液添加到上述溶解有反应产物的溶液中,进而添加包含丁醇作为封端剂的DMAc溶液,之后,作为稳定剂以固体成分比例1%添加二乙烯基苯与对甲酚的加聚物(杜邦公司制“メタクロール”(注册商标)2390),从而制备了总固体成分为35重量%的聚氨酯氨基甲酸酯溶液PU-F。所得到的溶液在40℃具有约3500泊的粘度。聚合物在DMAc中以0.5g/100mL的溶液浓度在25℃进行测定时,为0.90的特性粘度。
将该聚氨酯氨基甲酸酯溶液PU-F在高温(350℃)的惰性气体(氮气)中以2根长丝从纺丝头喷出,通过在该高温气体中的通过而进行干燥,通过喷气式捻丝机使得干燥途中的丝被捻合,使2根长丝结合,经过导丝辊与实施例1同样地在油辊上赋予了处理剂。以600m/分钟的速度进行卷取,制造了2根长丝结合的33dtex的聚氨酯氨基甲酸酯纤维PU-6。构成PU-6的聚氨酯氨基甲酸酯的氨基甲酸基浓度和脲基浓度的总和为3.95mol/kg。需要说明的是,PU-6的高温侧熔点为240℃。
仅使用PU-6供于320针、筒直径3.5英寸(29针数)的单口圆编机进行编织,在120℃进行1分钟的蒸气定型,得到了宽度约5cm的编织圆筒针织布(38g/m2)。保持不对其进行开幅的状态作为样品(相当于38g/m2的2条针织布重叠)。赋予表3所述的香料后,实施了上述感官试验1~3和香料成分的总释放量的测定。其结果示于表3。经过48小时的时刻的气味强度为4.5。经过48小时的时刻的香料释放量1为8.28μg/g·小时。
[实施例7]
在实施例1中使用的PUU-A中以固体成分比例20%添加通过叔丁基二乙醇胺与亚甲基双(4-环己基异氰酸酯)的反应而生成的聚氨酯(杜邦公司制“メタクロール”(注册商标)2462)后,在高温(350℃)的惰性气体(氮气)中以4根长丝从纺丝头喷出,通过在该高温气体中的通过而进行干燥,通过喷气式捻丝机使得干燥途中的丝被捻合,使4根长丝结合,经过导丝辊,与实施例1同样地在油辊上赋予了处理剂。以540m/分钟的速度进行卷取,制造了4根长丝结合的33dtex的聚氨酯脲纤维PUU-7。构成PUU-7的聚氨酯脲的氨基甲酸基浓度和脲基浓度的总和为1.82mol/kg,有效末端胺浓度为24meq/kg。需要说明的是,PUU-7的高温侧熔点为246℃。
仅使用PUU-7供于320针、筒直径3.5英寸(29针数)的单口圆编机进行编织,在120℃进行1分钟的蒸气定型,得到了宽度约5cm的编织圆筒针织布(38g/m2)。保持不对其进行开幅的状态作为样品(相当于38g/m2的2条针织布重叠)。赋予表3所述的香料后,实施了上述感官试验1~3和香料成分的总释放量的测定。其结果示于表3。经过48小时的时刻的气味强度为4.5。经过48小时的时刻的香料释放量1为10.3μg/g·小时。
[实施例8]
在实施例2中使用的PUU-B中分别以固体成分比例2%、2%添加通过叔丁基二乙醇胺与亚甲基双(4-环己基异氰酸酯)的反应而生成的聚氨酯(杜邦公司制“メタクロール”(注册商标)2462)、通过N-甲基-3,3’-氨基二丙胺与亚甲基双(4-环己基异氰酸酯)的反应而生成的聚氨酯后,在高温(350℃)的惰性气体(氮气)中以4根长丝从纺丝头喷出,通过在该高温气体中的通过而进行干燥,通过喷气式捻丝机使得干燥途中的丝被捻合,使4根长丝结合,经过导丝辊,与实施例1同样地在油辊上赋予了处理剂。以540m/分钟的速度进行卷取,制造了4根长丝结合的33dtex的聚氨酯脲纤维PUU-8。构成PUU-8的聚氨酯脲的氨基甲酸基浓度和脲基浓度的总和为1.52mol/kg,有效末端胺浓度为19meq/kg。需要说明的是,PUU-8的高温侧熔点为285℃。
仅使用PUU-8供于320针、筒直径3.5英寸(29针数)的单口圆编机进行编织,在120℃进行1分钟的蒸气定型,得到了宽度约5cm的编织圆筒针织布(38g/m2)。保持不对其进行开幅的状态作为样品(相当于38g/m2的2条针织布重叠)。赋予表3所述的香料后,实施了上述感官试验1~3和香料成分的总释放量的测定。其结果示于表3。经过48小时的时刻的气味强度为5.0。经过48小时的时刻的香料释放量1为46.8μg/g·小时。
[实施例9]
在实施例2中使用的PUU-B中分别以固体成分比例2%、2%添加通过叔丁基二乙醇胺与亚甲基双(4-环己基异氰酸酯)的反应而生成的聚氨酯(杜邦公司制“メタクロール”(注册商标)2462)、环糊精(イソエリートP、盐水港精糖公司制)后,在高温(350℃)的惰性气体(氮气)中以4根长丝从纺丝头喷出,通过在该高温气体中的通过而进行干燥,通过喷气式捻丝机使得干燥途中的丝被捻合,使4根长丝结合,经过导丝辊,与实施例1同样地在油辊上赋予了处理剂。以540m/分钟的速度进行卷取,制造了4根长丝结合的33dtex的聚氨酯脲纤维PUU-9。构成PUU-9的聚氨酯脲的氨基甲酸基浓度和脲基浓度的总和为1.48mol/kg,有效末端胺浓度为19meq/kg。需要说明的是,PUU-9的高温侧熔点为280℃。
仅使用PUU-9供于320针、筒直径3.5英寸(29针数)的单口圆编机进行编织,在120℃进行1分钟的蒸气定型,得到了宽度约5cm的编织圆筒针织布(38g/m2)。保持不对其进行开幅的状态作为样品(相当于38g/m2的2条针织布重叠)。赋予表3所述的香料后,实施了上述感官试验1~3和香料成分的总释放量的测定。其结果示于表3。经过48小时的时刻的气味强度为5.0。经过48小时的时刻的香料释放量1为39.2μg/g·小时。
[实施例10]
在实施例2中使用的PUU-B中分别以固体成分比例2%、2%添加通过叔丁基二乙醇胺与亚甲基双(4-环己基异氰酸酯)的反应而生成的聚氨酯(杜邦公司制“メタクロール”(注册商标)2462)、作为金属化合物的将水滑石(户田工业株式会社制NAOX-19)在900℃烧制而得到的复合氧化物MgO·Al2O3后,在高温(350℃)的惰性气体(氮气)中以4根长丝从纺丝头喷出,通过在该高温气体中的通过而进行干燥,通过喷气式捻丝机使得干燥途中的丝被捻合,使4根长丝结合,经过导丝辊,与实施例1同样地在油辊上赋予了处理剂。以540m/分钟的速度进行卷取,制造了4根长丝结合的33dtex的聚氨酯脲纤维PUU-10。构成PUU-10的聚氨酯脲的氨基甲酸基浓度和脲基浓度的总和为1.48mol/kg,有效末端胺浓度为19meq/kg。需要说明的是,PUU-10的高温侧熔点为280℃。
仅使用PUU-10供于320针、筒直径3.5英寸(29针数)的单口圆编机进行编织,在120℃进行1分钟的蒸气定型,得到了宽度约5cm的编织圆筒针织布(38g/m2)。保持不对其进行开幅的状态作为样品(相当于38g/m2的2条针织布重叠)。赋予表3所述的香料后,实施了上述感官试验1~3和香料成分的总释放量的测定。其结果示于表3。经过48小时的时刻的气味强度为5.0。经过48小时的时刻的香料释放量1为44.9μg/g·小时。
[比较例1]
仅使用聚对苯二甲酸乙二醇酯丝(E)(44dtex、36fil)供于320针、筒直径3.5英寸(29针数)的单口圆编机进行编织,在120℃进行1分钟的蒸气定型,得到了宽度约5cm的编织圆筒针织布(55g/m2)pet-1。保持不对其进行开幅的状态作为样品(相当于55g/m2的2条针织布重叠)。赋予表3所述的香料后,实施了上述感官试验1~3和香料成分的总释放量的测定。其结果示于表3。
[比较例2]
仅使用仿毛尼龙(N)(44dtex、36fil),供于320针、筒直径3.5英寸(29针数)的单口圆编机进行编织,在120℃进行1分钟的蒸气定型,得到了宽度约5cm的编织圆筒针织布(55g/m2)ny-2。保持不对其进行开幅的状态作为样品(相当于55g/m2的2条针织布重叠)。赋予表3所述的香料后,实施了上述感官试验1~3和香料成分的总释放量的测定。其结果示于表3。
[比较例3]
使用丰田自动织机公司制环锭精纺机,由进行精练后的棉花原棉纤维(印度棉)制成了30支数英制棉支数的纺纱线。由所制成的纺纱线制成编织圆筒针织布(筒直径38英寸、24针数、114给纱口),在120℃进行1分钟蒸气定型,得到了布帛co-3。赋予表3所述的香料后,实施了上述感官试验1~3和香料成分的总释放量的测定。其结果示于表3。
[比较例4]
在容器中相对于分子量3500的四亚甲基醚二醇1摩尔投入1.05摩尔的4,4’-MDI,使用三乙胺作为催化剂,在90℃使之反应,将所得到的反应产物在N,N-二甲基乙酰胺(DMAc)中充分搅拌使之溶解而得到了溶液。接着,将包含乙二胺(简称为EDA)作为增链剂的DMAc溶液添加到上述溶解有反应产物的溶液中,进而添加包含二乙胺作为封端剂的DMAc溶液,之后,作为稳定剂以固体成分比例1%添加二乙烯基苯与对甲酚的加聚物(杜邦公司制“メタクロール”(注册商标)2390),从而制备了总固体成分为33重量%的聚氨酯脲溶液puu-g。所得到的溶液在40℃具有约2800泊的粘度。聚合物在DMAc中以0.5g/100mL的溶液浓度在25℃进行测定时,为0.98的特性粘度。
将puu-g在高温(350℃)的惰性气体(氮气)中以4根长丝从纺丝头喷出,通过在该高温气体中的通过而进行干燥,通过喷气式捻丝机使得干燥途中的丝被捻合,使4根长丝结合,经过导丝辊在油辊上赋予了处理剂。需要说明的是,被赋予至油辊的处理剂是由在25℃的粘度为10厘斯的硅油96重量%、硬脂酸镁4重量%构成的油剂。另外,调整油辊的转速使得油剂的附着量相对于纤维为5重量%。以540m/分钟的速度进行卷取,制造了2根长丝结合的33dtex的聚氨酯脲纤维puu-4。构成puu-4的聚氨酯脲的氨基甲酸基浓度和脲基浓度的总和为0.50mol/kg,有效末端胺浓度为34meq/kg。需要说明的是,puu-4的高温侧熔点为253℃。
仅使用puu-4供于320针、筒直径3.5英寸(29针数)的单口圆编机进行编织,在120℃进行1分钟的蒸气定型,得到了宽度约5cm的编织圆筒针织布(38g/m2)。保持不对其进行开幅的状态作为样品(相当于38g/m2的2条针织布重叠)。赋予表3所述的香料后,实施了上述感官试验1~3和香料成分的总释放量的测定。其结果示于表3。经过48小时的时刻的气味强度为1.5。经过48小时的时刻的香料释放量1为0.0488μg/g·小时。
[比较例5]
在L/D为40的双螺杆挤出机中于氮封下对分子量2000的PTMG1摩尔连续地供给7.50摩尔的4,4’-MDI、作为增链剂的1,4-丁二醇,通过一步法进行反应。反应温度设为240℃,将生成的聚氨酯以约3mmφ的条状喷出,水冷后,切断从而进行造粒。所得到的聚氨酯(pu-h)的重均分子量以聚苯乙烯换算计为17万,220℃时的熔融粘度在剪切速度1000秒-1下为200泊。
利用真空间歇式干燥机在80℃对所得到的颗粒进行12小时预干燥。干燥后,利用单螺杆挤出机将颗粒熔融,利用齿轮泵进行计量,从纺丝头向流动有冷却空气的纺丝筒喷出,将导丝辊与卷取机的速度比设为1.4,经过导丝辊,与比较例1同样地在油辊上赋予了处理剂。以每分钟220m的速度进行熔融纺丝,卷取2长丝结合的33dtex的丝,在80℃加热老化24小时,制造了聚氨酯氨基甲酸酯纤维(pu-5)。构成pu-5的聚氨酯的氨基甲酸基浓度和脲基浓度的总和为5.50mol/kg,所得到的丝的特性示于表2中。需要说明的是,pu-5的高温侧熔点为245℃。
仅使用pu-5供于320针、筒直径3.5英寸(29针数)的单口圆编机进行编织,在120℃进行1分钟的蒸气定型,得到了宽度约5cm的编织圆筒针织布(38g/m2)。保持不对其进行开幅的状态作为样品(相当于38g/m2的2条针织布重叠)。赋予表3所述的香料后,实施了上述感官试验1~3和香料成分的总释放量的测定。其结果示于表3。经过48小时的时刻的气味强度为2.0。经过48小时的时刻的香料释放量1为0.0673μg/g·小时。
[比较例6]
在L/D为40的双螺杆挤出机中于氮封下对分子量2000的PTMG1摩尔连续地供给9.50摩尔的4,4’-MDI、作为增链剂的1,4-丁二醇,通过一步法进行反应。反应温度设为240℃,将生成的聚氨酯(pu-i)以约3mmφ的条状喷出,水冷后,切断从而进行造粒。220℃时的熔融粘度在剪切速度1000秒-1下为350泊。
利用真空间歇式干燥机在80℃对所得到的颗粒进行12小时预干燥。干燥后,利用单螺杆挤出机将颗粒熔融,利用齿轮泵进行计量,从纺丝头向流动有冷却空气的纺丝筒喷出,将导丝辊与卷取机的速度比设为1.1,经过导丝辊,与实施例1同样地在油辊上赋予了处理剂。以每分钟110m的速度进行熔融纺丝,卷取2长丝结合的33dtex的丝,在80℃加热老化24小时,制造了聚氨酯氨基甲酸酯纤维(pu-6)。构成pu-6的聚氨酯的氨基甲酸基浓度和脲基浓度的总和为7.00mol/kg,所得到的丝的特性示于表2中。需要说明的是,pu-6的高温侧熔点为255℃。
仅使用pu-6供于320针、筒直径3.5英寸(29针数)的单口圆编机进行编织,在120℃进行1分钟的蒸气定型,得到了宽度约5cm的编织圆筒针织布(38g/m2)。保持不对其进行开幅的状态作为样品(相当于38g/m2的2条针织布重叠)。赋予表3所述的香料后,实施了上述感官试验1~3和香料成分的总释放量的测定。其结果示于表3。经过48小时的时刻的气味强度为1.5。经过48小时的时刻的香料释放量1为0.0189μg/g·小时。
[比较例7]
进行与实施例1的聚氨酯脲纤维(PUU-1)相同的操作,仅改变油剂种类。使用由在25℃的粘度为10厘斯的矿物油92重量%、柠檬烯8重量%构成的油剂。
经过48小时的时刻的气味强度为5.0。经过48小时的时刻的香料释放量1为4.63μg/g·小时。然而,在<留香性试验2>9级愉快·不愉快度中为-3.0,作为气味的性质是非常不愉快的熟透了的柑橘类那样的香味。
[比较例8]
进行与实施例1的聚氨酯脲纤维(PUU-1)相同的操作,仅改变油剂种类。使用由在25℃的粘度为10厘斯的矿物油98重量%、桧木醇2重量%构成的油剂。
经过48小时的时刻的气味强度为4.0。然而,在<留香性试验2>9级愉快·不愉快度中为-4.0,作为气味的性质是极端不愉快的气味,显著损害与市售香料的香气平衡。
[比较例9]
利用真空间歇式干燥机在80℃对"Pebax"4033(ARKEMA公司、熔点160℃)的颗粒进行12小时预干燥。干燥后,利用单螺杆挤出机将颗粒熔融,利用齿轮泵进行计量,从纺丝头向流动有冷却空气的纺丝筒喷出,将导丝辊与卷取机的速度比设为2.00,经过导丝辊,与实施例1同样地在油辊上赋予了处理剂。以每分钟110m的速度进行熔融纺丝,卷取2长丝结合的33dtex的丝,在80℃加热老化24小时,制造了pae-9。所得到的丝的特性示于表2中。需要说明的是,pae-9的高温侧熔点为165℃。
仅使用pae-9供于320针、筒直径3.5英寸(29针数)的单口圆编机进行编织,在120℃进行1分钟的蒸气定型,得到了宽度约5cm的编织圆筒针织布(38g/m2)。保持不对其进行开幅的状态作为样品(相当于38g/m2的2条针织布重叠)。赋予表3所述的香料后,实施了上述感官试验1~3和香料成分的总释放量的测定。其结果示于表3。经过48小时的时刻的气味强度为2.0。经过48小时的时刻的香料释放量1为0.0222μg/g·小时。
[比较例10]
利用真空间歇式干燥机在80℃对"Pellethane"2102-90A(DowChemicals公司、熔点214℃)的颗粒进行12小时预干燥。干燥后,利用单螺杆挤出机将颗粒熔融,利用齿轮泵进行计量,从纺丝头向流动有冷却空气的纺丝筒喷出,将导丝辊与卷取机的速度比设为1.30,经过导丝辊,与实施例1同样地在油辊上赋予了处理剂。以每分钟110m的速度进行熔融纺丝,卷取2长丝结合的33dtex的丝,在80℃加热老化24小时,制造了pu-10。所得到的丝的特性示于表2中。需要说明的是,pu-10的高温侧熔点为220℃。
仅使用pu-10供于320针、筒直径3.5英寸(29针数)的单口圆编机进行编织,在120℃进行1分钟的蒸气定型,得到了宽度约5cm的编织圆筒针织布(38g/m2)。保持不对其进行开幅的状态作为样品(相当于38g/m2的2条针织布重叠)。赋予表3所述的香料后,实施了上述感官试验1~3和香料成分的总释放量的测定。其结果示于表3。经过48小时的时刻的气味强度为2.5。经过48小时的时刻的香料释放量1为0.0619μg/g·小时。
[实施例11~18]
使用聚氨酯纤维PUU-2,按照表4所示的各纤维含量的组合制作了布帛。布帛A通过表1的布帛化工序-L制成,布帛B通过表1的布帛化工序-L2制成,布帛C、D通过表1的布帛化工序-M制成,布帛E通过表1的布帛化工序-M2制成,布帛F通过表1的布帛化工序-N制成。对所得到的布帛赋予表4所述的香料后,实施了上述感官试验1和香料成分的总释放量的测定。结果示于表4中。
[比较例11~18]
使用聚氨酯纤维puu-4、pu-5、pu-6,按照表4所示的各纤维含量的组合制作了布帛。布帛x通过表2的布帛化工序-o制成,布帛y通过表2的布帛化工序-p制成,布帛a13~a15通过表2的布帛化工序-t制成。对所得到的布帛赋予表4所述的香料后,实施了上述感官试验1和香料成分的总释放量的测定。结果示于表4中。
[实施例19]
将利用实施例17中使用的检体以及香料赋予条件通过香料总释放量的测定过程中的GC/MS总离子流色谱图所检测出的峰图示于图2中。其中,试样使用2.4±0.1g的量的刚干燥后的试样,在玻璃管中流通空气来捕集生成气体时的温度为40℃、时间设为24小时(干燥后0小时~24小时)。
[实施例20]
在实施例19的“吸附管捕集处理”后,连续地更换成其它吸附管(香料赋予试样使用与原来相同的试样),同样地用时24小时捕集生成气体(干燥后24小时~48小时)。与实施例19同样地,得到了通过GC/MS总离子流色谱图检测出的峰图。将其示于图3中。
[比较例19]
将利用比较例17中使用的样品以及香料赋予条件通过香料总释放量的测定过程中的GC/MS总离子流色谱图所检测出的峰图示于图4中。其中,试样使用2.4±0.1g的量的刚干燥后的试样,在玻璃管中流通空气来捕集生成气体时的温度为40℃、时间为24小时(干燥后0小时~24小时)。
[比较例20]
在比较例19的“吸附管捕集处理”后,连续地更换成其它吸附管(香料赋予试样使用与原来相同的试样),同样地用时24小时捕集生成气体(干燥后24小时~48小时)。与实施例19同样,得到了通过GC/MS总离子流色谱图检测出的峰图。将其示于图5中。
上述图2~图5中,水平轴表示检测时间(分钟)(范围:0~55)。垂直轴表示信号检测强度,图2~图5中设成相同的信号检测强度区域,以范围0~100表示。图2和图3中有明确显示信号检测强度的大峰,而图4和图5中没有看到明确显示信号检测强度的峰。即,将仅布帛不同的实施例19(图2)和比较例19(图4)进行比较时,可知对于从干燥后0小时起至24小时为止的24小时的香料成分的释放程度而言,实施例19显著大于比较例19。同样地,将实施例20(图3)和比较例20(图5)进行比较时,可知对于从干燥后24小时起至48小时为止的24小时的香料成分的释放程度而言,实施例20显著大于比较例20。
产业上的可利用性
本发明的聚氨酯类纤维具有优良的留香性,并且具有优良的机械特性,因而使用该纤维的衣服、材料等具有优良的留香性。由于具有这些优良的特性,因而本发明的聚氨酯类纤维不但能够单独使用,而且能够通过与各种纤维、无纺布进行组合从而得到留香性优良的布帛,适宜于编织、织造、编带、热熔接加工。作为能够使用其的具体用途,可以列举以内衣、寝具为代表的短袜、长筒袜、紧身裤、内衣、滑雪服、高尔夫服、衬衫、套装、紧身潜水衣、胸罩、紧身短裤、工作服、烟火服、手袋、松紧带、毛衣、圆针织物、特里科经编织物、机织物等各种纤维产品、香料吸收用纤维结构物、芳香疗法等使用香料时的纤维结构物、各种内饰用纤维结构物、紧固材料,以及,有时还可得到能够以低应力进行伸长的伸缩性片,纸尿片、卫生巾等卫生用品或用于防止其泄漏的褶裥,以及,各种过滤器类、尤其空调器械、空气清洁机的过滤器、假花、抹布、拷贝清洁器(copy cleaner)、密封垫、宠物用品、电气绝缘材料、相当壁纸的布帛等。
符号说明
1 吸附管
2 玻璃制容器(采尘器)
3 试样
Claims (16)
1.一种留香性聚氨酯类纤维,其特征在于,从吸收香料成分起48小时后的香料成分的总释放量为0.1μg/g·小时以上且1000μg/g·小时以下。
2.如权利要求1所述的留香性聚氨酯类纤维,其特征在于,所述聚氨酯类纤维为聚氨酯纤维和/或聚氨酯脲纤维。
3.如权利要求1或2所述的留香性聚氨酯类纤维,其特征在于,所述聚氨酯类纤维的氨基甲酸基浓度和脲基浓度的合计为1.0mol/kg以上且5.0mol/kg以下。
4.如权利要求1~3中任一项所述的留香性聚氨酯类纤维,其特征在于,所述聚氨酯类纤维每1g的纤维表面积为0.02m2以上且0.2m2以下和/或聚氨酯纤维的单纤维纤度为3分特克斯以上且300分特克斯以下。
5.如权利要求1~4中任一项所述的留香性聚氨酯类纤维,其特征在于,所述香料成分是碳原子数为3以上且15以下、分子量为50以上且350以下、沸点为20℃以上且200℃以下的化合物。
6.如权利要求1~5中任一项所述的留香性聚氨酯类纤维,其特征在于,所述香料成分的吸收来自利用包含香料成分的洗涤用柔顺剂和/或洗涤剂在水浴中的清洗。
7.如权利要求1~5中任一项所述的留香性聚氨酯类纤维,其特征在于,所述香料成分的吸收来自利用包含香料成分的洗涤用柔顺剂和/或洗涤剂在干洗溶剂中的清洗。
8.如权利要求1~5中任一项所述的留香性聚氨酯类纤维,其特征在于,所述香料成分的吸收来自包含香料成分的液体状物质的喷雾。
9.一种留香性布帛,其特征在于,其具有权利要求1~8中任一项所述的留香性聚氨酯类纤维。
10.如权利要求9所述的留香性布帛,其特征在于,从吸收香料成分起48小时后的香料成分的总释放量为0.01μg/g·小时以上且1000μg/g·小时以下。
11.如权利要求9或10所述的留香性布帛,其特征在于,留香性聚氨酯类纤维的含量为2重量%以上且100重量%以下。
12.一种留香性聚氨酯类纤维原材料,使权利要求1~8中任一项所述的留香性聚氨酯类纤维吸收香料成分而得到。
13.权利要求1~8中任一项所述的留香性聚氨酯类纤维的应用,其特征在于,使其吸收香料成分。
14.一种留香性聚氨酯类纤维的香气保持方法,其特征在于,具有使权利要求1~8中任一项所述的留香性聚氨酯类纤维吸收香料成分的过程。
15.一种留香性聚氨酯类纤维原材料的制造方法,其特征在于,具有使权利要求1~8中任一项所述的留香性聚氨酯类纤维吸收香料成分的工序。
16.如权利要求15所述的留香性聚氨酯类纤维原材料的制造方法,其特征在于,具有两次以上的所述吸收香料成分的工序。
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CN108946957A (zh) * | 2018-07-13 | 2018-12-07 | 太原理工大学 | 一种将聚氨酯与水滑石复合提取短链脂肪酸制备缓释碳源的方法 |
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CN110923946A (zh) * | 2019-11-20 | 2020-03-27 | 苏州市雄林新材料科技有限公司 | 一种纳米抗菌透气tpu薄膜及其制备方法 |
CN112147262A (zh) * | 2020-11-02 | 2020-12-29 | 宁夏大学 | 一种鉴别熟制鲜活中华绒螯蟹的方法 |
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US10006151B2 (en) | 2018-06-26 |
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WO2014112588A1 (ja) | 2014-07-24 |
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US20160002827A1 (en) | 2016-01-07 |
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