CN105682983A - 车辆座椅用垫的制造方法 - Google Patents
车辆座椅用垫的制造方法 Download PDFInfo
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- CN105682983A CN105682983A CN201480059046.9A CN201480059046A CN105682983A CN 105682983 A CN105682983 A CN 105682983A CN 201480059046 A CN201480059046 A CN 201480059046A CN 105682983 A CN105682983 A CN 105682983A
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- foam
- vehicle seat
- active hydrogen
- polyurethane foam
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Abstract
本发明的目的在于提供一种固化性良好地制造醛不易扩散的车辆座椅用垫的方法。本发明提供一种车辆座椅用垫的制造方法,是包括工序(I)的车辆座椅用垫的制造方法,上述工序(I)是使活性氢成分(A)和有机聚异氰酸酯(B)在发泡剂(C)、氨基甲酸酯化催化剂(D)、稳泡剂(E)和添加剂(F)的存在下反应而得到软质聚氨酯泡沫的工序,其中,(C)含有水,(F)含有选自下述通式(1)表示的尿素化合物(F1)、氨基酸(F2)和多元酚(F3)中的至少1种,软质聚氨酯泡沫的核密度为25~90kg/m3,回弹性为50~75%,硬度(25%-ILD)为150~400N/cm2。
Description
技术领域
本发明涉及一种车辆座椅用垫的制造方法。
背景技术
近年,由于甲醛等醛类(挥发性有机化合物(VOC))成为病态建筑综合征等的原因,因此在住宅领域,要求这些化合物尽量不扩散。这样的状况在汽车等车辆室内也是同样的,VOC对策成为必要。
例如,车辆座椅用垫中使用缓冲性高的软质氨基甲酸酯泡沫,但是由于这些氨基甲酸酯泡沫成型后,聚氨酯泡沫用原料含有的、或氨基甲酸酯化反应时产生的甲醛或乙醛等会从垫扩散,因此要求减少这些醛类的产生。
以往,已知在防止醛类的挥发时,在座椅用垫的表面涂布醛捕捉剂的方法(专利文献1)。
此外,已知将具有分解醛类的作用的肼化合物与多元醇化合物混合的方法(专利文献2)。
现有技术文献
专利文献
专利文献1:日本特开2005-124743号公报
专利文献2:日本特开2006-182825号公报
发明内容
但是,专利文献1的方法中,发泡成型后,需要在座椅用垫上涂布醛捕捉剂,操作性差,此外专利文献2的方法中存在由于固化性差,座椅用垫制造时需要长时间加热,生产效率低的问题。
本发明的目的在于提供一种利用固化性良好的方法制造醛不易扩散的车辆座椅用垫的方法。
本发明的发明人等为了实现上述目的进行研究,结果完成了本发明。
即,本发明提供一种车辆座椅用垫的制造方法,是包括工序(I)的车辆座椅用垫的制造方法,上述工序(I)是使活性氢成分(A)和有机聚异氰酸酯(B)在发泡剂(C)、氨基甲酸酯化催化剂(D)、稳泡剂(E)和添加剂(F)的存在下反应而得到软质聚氨酯泡沫的工序,其中,(C)含有水,(F)含有选自下述通式(1)表示的尿素化合物(F1)、氨基酸(F2)和多元酚(F3)中的至少1种,软质聚氨酯泡沫的核密度为25~90kg/m3,回弹性为50~75%,硬度(25%-ILD)为150~400N/cm2。
[在通式(1)中,R表示氢、碳原子数1~4的烷基或羟基,各自可以相同也可以不同,至少一个表示氢。n表示0~3的整数。]
本发明的车辆座椅用垫的制造方法能够制造醛的扩散少的车辆座椅用垫。此外,制造时的固化性也良好。
具体实施方式
从成型性和机械物性的观点出发,本发明所用的活性氢成分(A)优选含有数均官能团数为2~8、羟值为14~54(mgKOH/g)、氧化乙烯单元的含量为5~30重量%的聚醚多元醇(A0)。
(A0)的数均官能团数为2~8,从成型性和机械物性的观点出发,优选为2~6,进一步优选为2~5。
应予说明,本发明中,将聚醚多元醇[(A0)和后述的(A1)]的官能团数视为与作为起始物质的含活性氢化合物的官能团数相同。
(A0)的羟值是14~54(mgKOH/g),从固化性和机械物性的观点出发,优选为17~50(mgKOH/g),进一步优选为20~45(mgKOH/g)。
本发明中的羟值利用JISK1557-1规定的方法测定。
(A0)的氧化乙烯单元的含量是5~30重量%,从成型性和机械物性的观点出发,优选为5~25重量%,进一步优选为5~20重量%。
作为(A0),可举出对含有至少2个(优选为2~8个)活性氢的化合物(多元醇、多元酚、胺、聚羧酸和磷酸等)加成环氧烷(以下简写为AO)的结构的化合物等。
作为多元醇,包括碳原子数2~20的二元醇、碳原子数3~20的三元醇和碳原子数5~20的4~8元的多元醇。
作为碳原子数2~20的二元醇,包括直链或支链脂肪族二醇和脂环式二醇等。作为直链或支链脂肪族二醇,包括亚烷基二醇等,具体可举出乙二醇、1,2-和1,3-丙二醇、1,3-和1,4-丁二醇、1,6-己二醇以及新戊二醇等。作为脂环式二醇,包括亚环烷基二醇等,具体可举出环己二醇和环己烷二甲醇等。
作为碳原子数3~20的三元醇,包括脂肪族三醇等。作为脂肪族三醇,包括烷烃三醇等,具体可举出甘油、三羟甲基丙烷、三羟甲基乙烷和己烷三醇等。
作为碳原子数5~20的4~8元的多元醇,包括脂肪族多元醇和糖类。作为脂肪族多元醇,包括烷烃多元醇等,具体可举出季戊四醇、山梨糖醇、甘露糖醇、脱水山梨糖醇、双甘油和二季戊四醇等。此外,作为脂肪族多元醇,也包括烷烃三醇和烷烃多元醇的分子内脱水物、以及烷烃三醇和/或烷烃多元醇的分子间脱水物。作为糖类,具体可举出蔗糖、葡萄糖、甘露糖、果糖和甲基葡萄糖苷等,也包括它们的衍生物。
作为多元(2~8元)酚,包括单环多元酚、双酚、酚与甲醛的缩合物(酚醛清漆)、多酚以及它们的2种以上的合用等。作为单环多元酚,可举出邻苯三酚、氢醌和间苯三酚等。作为双酚,可举出双酚A、双酚F和双酚砜等。作为多酚,可举出美国专利第3265641号说明书记载的多酚等。
作为胺,包括活性氢数为2~8个的胺,包括氨、直链或支链脂肪族胺、芳香族胺、脂环式胺和杂环式胺。
作为直链或支链脂肪族胺,可举出碳原子数2~20的烷醇胺(单乙醇胺、二乙醇胺、三乙醇胺、异丙醇胺和氨基乙基乙醇胺等)、碳原子数1~20的烷基胺(正丁胺和辛基胺等)、碳原子数2~6的亚烷基二胺(乙二胺、丙二胺和六亚甲基二胺等)和碳原子数4~20的聚亚烷基多胺(亚烷基的碳原子数为2~6的聚亚烷基多胺等,具体可举出二亚乙基三胺、三亚乙基四胺等)。
作为芳香族胺,可举出碳原子数6~20的芳香族单或多胺(苯胺、苯二胺、甲苯二胺、二甲苯二胺、二乙基甲苯二胺、亚甲基二苯胺和二苯醚二胺等)等。
作为脂环式胺,可举出碳原子数4~20的脂环式胺(异佛尔酮二胺、亚环己基二胺和二环己基甲烷二胺等)等。
作为杂环式胺,可举出碳原子数4~20的杂环式胺(哌嗪、氨乙基哌嗪和日本特公昭55-21044号公报记载的杂环式胺等)等。
作为聚羧酸,可举出碳原子数4~18的脂肪族聚羧酸(琥珀酸、己二酸、癸二酸、戊二酸和壬二酸等)、碳原子数8~18的芳香族聚羧酸(邻苯二甲酸、对苯二甲酸、间苯二甲酸和偏苯三酸等)等。
这些含活性氢化合物可以将2种以上合用。这些含活性氢化合物中,从固化性和机械物性的观点出发,优选为多元醇。
加成到含活性氢化合物的AO,优选为由碳原子数3以上的1,2-AO和环氧乙烷(以下简写为EO)构成的AO,作为碳原子数3以上的1,2-AO,可举出1,2-环氧丙烷(以下简写为PO)、1,2-环氧丁烷和苯乙烯氧化物等,其中从活性氢成分(A)的生产率的观点出发优选为PO。
AO优选仅由这些碳原子数3以上的1,2-AO和EO构成,但可以在AO中在10重量%以下(进一步优选为5重量%以下)的范围合用其他AO的加成物。作为其他AO,优选为碳原子数4~8的AO,可举出1,3-环氧丁烷、1,4-环氧丁烷和2,3-环氧丁烷等,可以使用2种以上。
作为AO的加成方法,可以是嵌段加成或无规加成的任意一个,至少多元醇的活性氢末端优选为嵌段加成。
作为AO加成时使用的催化剂,除了碱催化剂(KOH和CsOH等)之外,可以使用日本特开2000-344881号公报记载的催化剂(三(五氟苯基)硼烷等)、日本特开平11-120300号公报记载的催化剂(高氯酸镁等)(对于以下的AO加成物也是相同的)。
从固化性和机械物性的观点出发,将活性氢成分(A)的重量作为基准,(A0)的含量优选为8~98重量%,进一步优选为10~97重量%,特别优选为12~95重量%,最优选为20~90重量%。
本发明中,在活性氢成分(A)中,除了聚醚多元醇(A0)以外,可以含有其他活性氢成分,可举出(A0)以外的聚醚多元醇(A1)、聚酯多元醇(A2)、多元醇(A3)、上述以外的多元醇和单醇(A4)、以及这些多元醇中与乙烯基单体聚合得到的聚合物多元醇(A5)、胺(A6)以及它们的混合物等。
作为(A0)以外的聚醚多元醇(A1),可举出是在含有至少2个活性氢的化合物(多元醇、多元酚、胺、聚羧酸和磷酸等)中加成AO的结构的化合物且不属于(A0)的化合物,可以单独使用,也可以将2种以上合用。
作为上述含有活性氢的化合物,可举出与上述聚醚多元醇(A0)中的化合物相同的化合物。
从成型性的观点出发,在这些化合物中优选为多元醇,从固化性和机械物性的观点出发,进一步优选为脂肪族多元醇和脂环式多元醇,特别优选为脂肪族多元醇。
作为对含有活性氢的化合物加成的AO,从成型性的观点出发,优选为碳原子数2~8的AO,可举出EO、PO、1,2-环氧丁烷、1,3-环氧丁烷、1,4-环氧丁烷和2,3-环氧丁烷、苯乙烯氧化物以及这些化合物的2种以上的合用(嵌段和/或无规加成)等。从固化性的观点出发,在这些化合物中优选为PO以及PO和EO的合用,进一步优选为PO和EO的合用。
作为AO加成时使用的催化剂,除了碱催化剂(KOH、CsOH等)之外,可以使用日本特开2000-344881号公报记载的催化剂[三(五氟苯基)硼烷等]、日本特开平11-120300号公报记载的催化剂(高氯酸镁等)。
作为聚酯多元醇(A2),可举出下述(1)~(5)的化合物。
(1)多元醇和聚羧酸或其酯形成性衍生物的酯
多元醇是二元醇(乙二醇、二乙二醇、1,2-丙二醇和1,3-丙二醇、1,3-丁二醇和1,4-丁二醇、1,6-己二醇以及新戊二醇等)、聚醚多元醇(优选为二醇)以及它们与三元以上的多元醇(甘油和三羟甲基丙烷等)的混合物}等。聚羧酸或其酯形成性衍生物是酸酐和低级烷基(烷基的碳原子数:1~4)酯等,可举出己二酸、癸二酸、马来酸酐、邻苯二甲酸酐和对苯二甲酸二甲酯等。
(2)羧酸酐和AO的缩合反应物
(3)上述(1)和(2)的AO(EO、PO等)加成物
(4)聚内酯多元醇
例如,可举出通过将多元醇作为引发剂使内酯(ε-己内酯等)开环聚合得到的化合物等。
(5)聚碳酸酯多元醇
例如,可举出上述多元醇和亚烷基碳酸酯的反应物等。
作为多元醇(A3),可举出碳原子数2~20的二元醇(直链或支链脂肪族二醇(乙二醇、丙二醇、1,3-丁二醇和1,4-丁二醇、1,6-己二醇和新戊二醇等亚烷基二醇;二乙二醇和二丙二醇等聚亚烷基二醇)和脂环式二醇(环己二醇和环己烷二甲醇等亚环烷基二醇))、碳原子数3~20的三元醇{脂肪族三醇(甘油、三羟甲基丙烷、三羟甲基乙烷和己烷三醇等烷烃三醇)};碳原子数5~20的4~8元或其以上的多元醇(脂肪族多元醇(季戊四醇、山梨糖醇、甘露糖醇、脱水山梨糖醇、双甘油和二季戊四醇等烷烃多元醇以及它们或烷烃三醇的分子内或分子间脱水物;以及蔗糖、葡萄糖、甘露糖、果糖和甲基葡萄糖苷等糖及其衍生物))等。这些多元醇可以并用2种以上。
作为上述以外的多元醇和单醇(A4),可举出聚丁二烯多元醇等聚二烯多元醇和它们的氢化物;丙烯酸系多元醇、日本特开昭58-57413号公报和日本特开昭58-57414号公报等记载的含羟基乙烯基聚合物;蓖麻油等天然油脂系多元醇;蓖麻油改性物(多元醇酯交换生成物、氢化物等)等天然油脂系多元醇的改性物;国际公开WO98/44016号公报记载的含末端自由基聚合性官能团的活性氢化合物(也包括单醇);将聚醚多元醇利用亚甲基二卤化物等亚烷基二卤化物等转移的改性多元醇;聚醚多元醇的OH末端预聚物等。
作为聚合物多元醇(A5),可举出在(A0)、和(A1)~(A4)的至少1种中,在自由基聚合引发剂的存在下,将乙烯性不饱和单体(p)聚合,得到的(p)的聚合物在多元醇中稳定分散的混合物。作为(A5),在(A0)或(A1)中聚合(p)得到的物质,在分散稳定性方面优选。作为聚合方法的具体例,可举出美国专利第3383351号说明书、日本特公昭39-25737号公报等中记载的方法。
应予说明,本发明中,作为聚合物多元醇(A5)的原料使用的(A0)、和(A1)~(A4)不包含于(A0)、和(A1)~(A4)。
作为自由基聚合引发剂,能够使用生成自由基而引发聚合的引发剂,可举出2,2’-偶氮二异丁腈、2,2’-偶氮二(2,4-二甲基戊腈)、2,2’-偶氮二(2-甲基丁腈)等偶氮化合物;过氧化二苯甲酰、过氧化二异丙苯、过氧化苯甲酰、过氧化月桂酰和过琥珀酸等有机过氧化物;过硫酸盐和过硼酸盐等无机过氧化物等。应予说明,这些引发剂能够将2种以上合用。
作为乙烯性不饱和单体(p),可举出不饱和腈(p1)、含芳香环的单体(p2)、(甲基)丙烯酸酯(p3)、其他乙烯性不饱和单体(p4)和它们的2种以上的混合物等。
作为(p1),可举出丙烯腈、甲基丙烯腈等。
作为(p2),可举出苯乙烯、α-甲基苯乙烯、羟基苯乙烯、氯苯乙烯等。
作为(p3),可举出由C、H和O原子构成的单体,例如(甲基)丙烯酸烷基酯(烷基的碳原子数为1~24)[(甲基)丙烯酸甲酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸壬基酯、(甲基)丙烯酸癸基酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸二十烷基酯和(甲基)丙烯酸二十二烷基酯等]、(甲基)丙烯酸羟烷基(碳原子数2~5)酯[(甲基)丙烯酸羟基乙酯等]和羟基聚氧化亚烷基单(甲基)丙烯酸酯[亚烷基的碳原子数2~4、聚氧化亚烷基链的数均分子量200~1000等]。
作为(p4),可举出乙烯性不饱和羧酸及其衍生物,具体为(甲基)丙烯酸和(甲基)丙烯酰胺等;脂肪族或脂环式烃单体,具体为烯烃(乙烯、丙烯和降冰片烯等)和二烯烃(丁二烯等)等;氟系乙烯基单体,具体为含氟(甲基)丙烯酸酯(全氟辛基乙基甲基丙烯酸酯和全氟辛基乙基丙烯酸酯等)等;氯系乙烯基单体、具体为偏氯乙烯等;上述以外的含氮乙烯基单体,具体为含氮(甲基)丙烯酸酯(甲基丙烯酸二氨基乙酯和甲基丙烯酸吗啉代乙酯等)等;以及乙烯基改性硅油等。
这些(p)中,从成型性的观点出发,优选为(p1)和(p2),进一步优选为丙烯腈和/或苯乙烯。
乙烯性不饱和单体(p)中的(p1)、(p2)、(p3)和(p4)的重量比率,根据要求的聚氨酯的物性等能够改变,没有特别限制,示出一例时如下所示。
将(p)的总计重量作为基准,(p1)和/或(p2)优选为50~100重量%,进一步优选为80~100重量%。(p1)和(p2)的重量比没有特别限制,优选为100/0~20/80。(p3)优选为0~50重量%,进一步优选为0~20重量%。(p4)优选为0~10重量%,进一步优选为0~5重量%。
从成型性的观点出发,将(A5)的总计重量作为基准,聚合物多元醇(A5)中的(p)的聚合物的含量优选为50重量%以下,进一步优选为3~30重量%。
作为胺(A6),可举出活性氢的数量为2~8元或其以上的胺,可举出氨;作为脂肪族胺,可举出碳原子数2~20的烷醇胺(单乙醇胺、二乙醇胺、三乙醇胺、异丙醇胺和氨基乙基乙醇胺等)、碳原子数1~20的烷基胺(正丁胺和辛基胺等)、碳原子数2~6的亚烷基二胺(乙二胺、丙二胺和六亚甲基二胺等)、碳原子数4~20的聚亚烷基多胺(亚烷基的碳原子数为2~6的二亚烷基三胺~六亚烷基庚胺、二亚乙基三胺和三亚乙基四胺等)。
此外,可举出碳原子数6~20的芳香族单或多胺(苯胺、苯二胺、甲苯二胺、二甲苯二胺、二乙基甲苯二胺、亚甲基二苯胺和二苯醚二胺等);碳原子数4~20的脂环式胺(异佛尔酮二胺、亚环己基二胺和二环己基甲烷二胺等);碳原子数4~20的杂环式胺(哌嗪、氨乙基哌嗪和日本特公昭55-21044号公报记载的杂环式胺等)和它们的2种以上的合用等。
这些多元醇中,从成型性的观点出发,优选为聚醚多元醇(A1)和聚合物多元醇(A5)。
从固化性和机械物性的观点出发,将活性氢成分(A)的总计重量作为基准,(A1)、(A2)、(A3)、(A4)、(A5)和(A6)的总计含量优选为2~92重量%,进一步优选为3~90重量%,特别优选为5~88重量%,最优选为10~80重量%
从聚氨酯泡沫的成型性的观点出发,将(B)的总计重量作为基准,作为本发明中的有机聚异氰酸酯(B),优选包含选自70重量%以上的2,4-甲苯二异氰酸酯和2,6-甲苯二异氰酸酯(以下简写为TDI)、其粗制物、以及它们的改性物中的1种以上的聚异氰酸酯(以下将这些异氰酸酯简写为TDI系聚异氰酸酯)和30重量%以下的其他聚异氰酸酯。TDI系聚异氰酸酯的含量进一步优选为75~95重量%。作为上述改性物,可举出含有氨基甲酸酯基、碳化二亚胺基、脲基甲酸酯基、脲基、缩二脲基、异氰酸酯基和唑烷酮基的改性物等。
作为其他聚异氰酸酯,能够使用聚氨酯泡沫所使用的2元以上(优选为2~8元)的有机聚异氰酸酯,可举出TDI系聚异氰酸酯以外的芳香族聚异氰酸酯、直链或支链脂肪族聚异氰酸酯、脂环式聚异氰酸酯、芳香脂肪族聚异氰酸酯和它们的改性物(例如,上述改性物)。
作为芳香族聚异氰酸酯,可举出碳原子数(不包括NCO基中的碳元素;以下的聚异氰酸酯也是相同的)6~16的芳香族二异氰酸酯、碳原子数6~20的芳香族三异氰酸酯和它们的异氰酸酯的粗制物等。作为具体例,可举出1,3-和1,4-亚苯基二异氰酸酯、2,4’-和4,4’-二苯基甲烷二异氰酸酯(以下简写为MDI)、聚亚甲基聚亚苯基聚异氰酸酯(粗制MDI)、亚萘基-1,5-二异氰酸酯和三苯基甲烷-4,4’,4”-三异氰酸酯等。
作为脂肪族聚异氰酸酯,可举出碳原子数6~10的脂肪族二异氰酸酯等。作为具体例,可举出1,6-六亚甲基二异氰酸酯、2,2,4-三甲基六亚甲基二异氰酸酯和赖氨酸二异氰酸酯等。
作为直链或支链脂环式聚异氰酸酯,可举出碳原子数6~16的直链或支链脂环式二异氰酸酯等。作为具体例,可举出异佛尔酮二异氰酸酯、4,4’-二环己基甲烷二异氰酸酯、1,4-环己烷二异氰酸酯和降冰片烷二异氰酸酯等。
作为芳香脂肪族聚异氰酸酯,可举出碳原子数8~12的芳香脂肪族二异氰酸酯等。作为具体例,可举出亚二甲苯基二异氰酸酯和α,α,α’,α’-四甲基亚二甲苯基二异氰酸酯等。
作为改性聚异氰酸酯的具体例,可举出碳化二亚胺改性MDI等。
从成型性的观点出发,这些其他异氰酸酯中,优选为芳香族聚异氰酸酯,进一步优选为MDI、粗制MDI和这些异氰酸酯的改性物。
有机聚异氰酸酯(B)可以将异氰酸酯和其改性物合用2种以上。
从成型性的观点出发,作为有机聚异氰酸酯(B)整体的异氰酸酯基含量(NCO%)优选为40~50%。
本发明所用的发泡剂(C)含有水。作为(C)优选仅含有水。
作为发泡剂(C)仅使用水时的含量,从发泡倍率和泡沫的崩解性的观点出发,将活性氢成分(A)的总计重量作为基准,优选为1~7重量%,进一步优选为2~6.8重量%。
作为发泡剂(C)优选仅使用水,根据需要可以合用含氢原子的卤化烃、低沸点烃和液化碳酸气体等。
作为含氢原子的卤化烃系发泡剂,可举出HCFC(氢氯氟烃)(HCFC-123、HCFC-141b、HCFC-22和HCFC-142b等);HFC(氢氟烃)(HFC-134a、HFC-152a、HFC-356mff、HFC-236ea、HFC-245ca、HFC-245fa和HFC-365mfc等)等。
这些发泡剂中优选的发泡剂为HCFC-141b、HFC-134a、HFC-356mff、HFC-236ea、HFC-245ca、HFC-245fa和HFC-365mfc以及它们的2种以上的混合物。
从发泡倍率和泡沫的崩解性的观点出发,将活性氢成分(A)的重量作为基准,使用含氢原子的卤化烃时的含量优选为50重量%以下,进一步优选为5~45重量%。
低沸点烃为沸点是-5~70℃的烃,可举出丁烷、戊烷、环戊烷和它们的混合物等。
从发泡倍率和泡沫的崩解性的观点出发,将活性氢成分(A)的总计重量作为基准,使用低沸点烃时的含量优选为30重量%以下,进一步优选为25重量%以下。
从发泡倍率和泡沫的崩解性的观点出发,将活性氢成分(A)的总计重量作为基准,使用液化碳酸气体时的含量优选为30重量%以下,进一步优选为25重量%以下。
作为本发明所用的氨基甲酸酯化催化剂(D),能够使用促进氨基甲酸酯化反应的催化剂,可举出叔胺{三乙二胺、双(N,N-二甲基氨基-2-乙基)醚和N,N,N’,N’-四甲基六亚甲基二胺等}、叔胺的羧酸盐、羧酸金属盐(乙酸钾、辛酸钾和辛酸亚锡等)和有机金属化合物(二月桂酸二丁基锡等)。
从氨基甲酸酯泡沫的反应性的观点出发,将活性氢成分(A)的总计重量作为基准,(D)的含量优选为0.1~0.8重量%,进一步优选为0.15~0.7重量%。
作为本发明所用的稳泡剂(E),能够使用通常聚氨酯泡沫的制造所使用的稳泡剂,可举出有机硅稳泡剂等。
作为有机硅稳泡剂,可举出聚醚改性二甲基硅氧烷系稳泡剂[东丽道康宁株式会社制的“SZ-1328”、“SZ-1346”和“SF-2962”以及MomentivePerformanceMaterials社制的“L-3640”和“L-540”等]、二甲基硅氧烷系稳泡剂[东丽道康宁株式会社制的“SRX-253”等]等。
从成型性的观点出发,将活性氢成分(A)的总计重量作为基准,稳泡剂(E)的用量优选为0.5~3重量%,进一步优选为0.8~2.5重量%。
本发明所用的添加剂(F)含有选自下述通式(1)所示的尿素化合物(F1)、氨基酸(F2)和多元酚(F3)中的至少1种。
本发明中的添加剂(F)是具有作为醛捕捉剂的功能的添加剂。
通式(1)中,R表示氢、碳原子数1~4的烷基或羟基,各自可以相同也可以不同,至少1个表示氢。n表示0~3的整数。
通式(1)中,R可举出氢、碳原子数1~4的烷基(甲基、乙基、丙基、异丙基、正丁基和叔丁基等)、羟基。这些基团中,各自可以相同也可以不同,任意1个表示氢。从醛减少的观点出发,优选为氢、甲基、羟基,进一步优选为氢。
通式(1)中,n表示0~3的整数,从醛减少效果的观点出发,优选为0或1~2的整数,进一步优选为0。
作为通式(1)所示的尿素化合物(F1),可举出尿素、N-甲脲、缩二脲、羰基二脲,从醛减少的效果的观点出发,优选为尿素。
作为氨基酸(F2),可举出甘氨酸、丙氨酸、缬氨酸、亮氨酸、异亮氨酸、天冬酰胺、谷氨酰胺、天门冬氨酸、谷氨酸、赖氨酸、精氨酸、苯丙氨酸、酪氨酸、半胱氨酸、甲硫氨酸、丝氨酸、苏氨酸、组氨酸、色氨酸和脯氨酸等。
这些氨基酸中,从醛减少效果的观点出发,优选为甘氨酸、天门冬氨酸和脯氨酸,进一步优选为甘氨酸和天门冬氨酸。
作为多元酚(F3),可举出官能团数2~20、分子量110~2000的多元酚,具体包括邻苯三酚、氢醌和间苯三酚等单环多元酚;双酚A、双酚F和双酚砜等双酚;酚与甲醛的缩合物(酚醛清漆);美国专利第3265641号说明书记载的多酚;含多酚植物提取物以及它们的2种以上的合用等。
这些多元酚中,从醛减少效果的观点出发,优选为官能团数2~10、分子量110~1000的多元酚,进一步优选为官能团数2~5、分子量110~500的多元酚。
作为添加剂(F)含有(F1)和(F2)时的(F1)和(F2)的含量,从醛减少效果和固化性的观点出发,将(F)的总计重量作为基准,(F1)优选为15~98重量%,(F2)优选为2~85重量%。
含有(F1)和(F3)时的(F1)和(F3)的含量,从醛减少效果和固化性的观点出发,将(F)的总计重量作为基准,(F1)优选为15~98重量%,(F3)优选为2~85重量%。
含有(F2)和(F3)时的(F2)和(F3)的含量,从醛减少效果和固化性的观点出发,将(F)的总计重量作为基准,(F2)优选为2~98重量%、(F3)优选为2~98重量%。
含有(F1)、(F2)和(F3)时的(F1)、(F2)和(F3)的含量,从醛减少效果和固化性的观点出发,将(F)的总计重量作为基准,(F1)优选为8~96重量%,(F2)优选为2~46重量%,(F3)优选为2~46重量%。
应予说明,添加剂(F)中的(F1)、(F2)和(F3)的总计含量优选为60重量%以上,进一步优选为80重量%以上,特别优选为100重量%。
(F)的总计含量,从醛减少效果和适度的固化性的观点出发,将活性氢成分(A)的总计重量作为基准,优选为0.01~3重量%,进一步优选为0.05~3重量%,特别优选为0.1~3重量%。
作为添加剂(F),优选为含有上述通式(1)所示的尿素化合物(F1)的添加剂,进一步优选为含有尿素化合物(F1)、氨基酸(F2)和多元酚(F3)的添加剂。
本发明中,根据需要,可以使用着色剂、阻燃剂、抗老化剂和抗氧化剂等公知的辅助成分,在其存在下反应。作为着色剂,包括染料和颜料。作为阻燃剂,包括磷酸酯和卤化磷酸酯等。作为抗老化剂,包括三唑系和二苯甲酮系抗老化剂等。作为抗氧化剂,包括受阻酚系和受阻胺系抗氧化剂等。
就这些辅助成分的用量而言,将活性氢成分(A)的总计重量作为基准,从固化性和机械物性的观点出发,着色剂优选为1重量%以下,从固化性和机械物性的观点出发,阻燃剂优选为5重量%以下,进一步优选为2重量%以下,从固化性和机械物性的观点出发,抗老化剂优选为1重量%以下,进一步优选为0.5重量%以下,从固化性和机械物性的观点出发,抗氧化剂优选为1重量%以下,进一步优选为0.01~0.5重量%。
本发明的制造方法中,进行车辆座椅用垫的制造时的异氰酸酯指数[(NCO基/含活性氢原子的基团)×100],从成型性的观点出发,优选为70~125,进一步优选为75~120,特别优选为80~115。
应予说明,含活性氢原子的基团为含有来自作为发泡剂的水的物质的基团。
如果示出本发明的车辆座椅用垫的制造方法的一个例子,如下述所示。首先,将活性氢成分(A)、发泡剂(C)、氨基甲酸酯化催化剂(D)、稳泡剂(E)和添加剂(F)、以及根据需要的其他辅助成分以规定量混合,制作混合物。接下来使用氨基甲酸酯发泡机或搅拌机,混合该混合物与有机聚异氰酸酯(B)而得到软质聚氨酯泡沫原液,将该软质聚氨酯泡沫原液注入预先安置有表皮材料的模具型腔内(例如15~70℃),固化规定时间,发泡后脱模,得到座椅用垫。从生产效率的观点出发,优选在将软质聚氨酯泡沫原液发泡成型的腔空间内安置面状的表皮材料,发泡成型为软质聚氨酯泡沫一体粘接于该表皮材料的状态而得到的方法。
含有活性氢成分(A)、发泡剂(C)、氨基甲酸酯化催化剂(D)、稳泡剂(E)和添加剂(F)的混合物以及进一步根据需要含有其他辅助成分的混合物,将这些混合物优选在25℃静置30天后,含有(A)的相和含有水的相不分离为2相。不分离为2相是通过使活性氢成分(A)中的聚醚多元醇(A0)的量比较多来实现,(A0)优选的含量如上所示。
表皮的材料没有特别限制,例如能够例示天然纤维(动物系天然纤维、植物系天然纤维等)、合成纤维(聚丙烯纤维、聚酯纤维、聚酰胺纤维、丙烯酸纤维等)以及它们的混纺纤维。
实施例
以下,通过实施例对本发明作进一步说明,本发明不受其限制。
以下实施例中,多元醇成分的羟值、末端伯羟基化率的测定方法如以下所示。
<羟值>
羟值(mgKOH/g)通过JISK1557-1规定的方法测定。
<末端伯羟基化率>
本发明中,末端伯羟基化率是预先将试样进行酯化的预处理后通过1H-NMR法算出。以下对1H-NMR法的详细内容做具体说明。
·试样调整法
在直径5mm的1H-NMR用试管中秤量测定试样约30mg,添加0.5ml的氘代溶剂溶解。然后,添加0.1ml三氟乙酸酐,25℃下放置约5分钟,将多元醇制成三氟乙酸酯,制成分析用试样。其中,氘代溶剂是氘代氯仿、氘代甲苯、氘代二甲基亚砜、氘代二甲基甲酰胺等,适宜选择能够使试样溶解的溶剂。
·1H-NMR测定
在通常的条件下进行1H-NMR测定。
·末端伯羟基化率的计算方法
末端伯羟基结合的亚甲基来源的信号在4.3ppm附近被观测,末端仲羟基结合的次甲基来源的信号在5.2ppm附近被观测,因此末端伯羟基化率通过下式[1]算出。
末端伯羟基化率(%)=[r/(r+2s)]×100[1]
其中,
r:4.3ppm附近的末端伯羟基结合的亚甲基来源的信号的积分值
s:5.2ppm附近的末端仲羟基结合的次甲基来源的信号的积分值。
实施例1~22和比较例1~3
将含有表1、2所示的活性氢成分(A)、发泡剂(C)、氨基甲酸酯化催化剂(D)、稳泡剂(E)和添加剂(F)的预混料和有机聚异氰酸酯(B),分别装入高压氨基甲酸酯发泡机(PolyurethaneEngineering社制)的原料罐,将液温调节至25℃。然后,在高压氨基甲酸酯发泡机中,将上述预混料和变为异氰酸酯指数100的量的有机聚异氰酸酯(B),在15MPa下高压喷出混合,注入温度调节为65℃的400mm(长度)×400mm(宽度)×100mm(高度)的铝制模具、或者安置有表皮材料的汽车的座椅缓冲垫(シートクッションパッド)成型用铝制模具(塑模(実型)),经过固化时间6分钟成型。
各泡沫的物性值等的测定结果如表1、2所示(由于长方体的铝制模具和塑模中泡沫物性没有大的差异,因此示出长方体的铝制模具中的测定结果)。应予说明,核密度是从泡沫的中心部,切取100mm×100mm×50mm的大小而测定的密度。
[表1]
[表2]
表1、2中各成分的缩写如以下所示。
[聚醚多元醇(A0)]
(A0-1):在季戊四醇1摩尔中,将氢氧化铯作为催化剂,加成PO118.4摩尔,利用常用方法将氢氧化铯除去后,与日本特开2000-344881号公报的实施例1同样地实施,将三(五氟苯基)硼烷作为催化剂加成PO16.0摩尔,进一步将氢氧化钾作为催化剂嵌段加成EO13.6摩尔,通过常用方法将催化剂成分除去而得到的羟值=30.0(mgKOH/g)、环氧乙烷的末端含量8重量%、末端伯羟基化率85%的多元醇
(A0-2):在甘油1摩尔中,将氢氧化钾作为催化剂,加成PO71.8摩尔后,进一步将氢氧化钾作为催化剂,嵌段加成EO15.8摩尔,通过常用方法将氢氧化钾除去而得到的羟值=34.0(mgKOH/g)、环氧乙烷的末端含量14重量%、末端伯羟基化率75%的多元醇
(A0-3):在季戊四醇1摩尔中,将氢氧化钾作为催化剂,加成PO141.8摩尔后,进一步将氢氧化钾作为催化剂,嵌段加成EO25.5摩尔,通过常用方法将氢氧化钾除去而得到设为羟值=24.0(mgKOH/g)、环氧乙烷的末端含量12重量%、末端伯羟基化率75%的多元醇
[(A0)以外的活性氢成分(A)]
(A5-1):在多元醇(A0-2)和(A0-3)(重量比:96/4)中,使丙烯腈和苯乙烯(重量比:70/30)共聚的聚合物多元醇(聚合物含量33.5重量%),羟值=22.0(mgKOH/g)
(A1-1):山梨糖醇的环氧乙烷加成物,羟值=1247(mgKOH/g),环氧乙烷的末端含量33重量%
(A1-2):甘油的环氧丙烷-环氧乙烷加成物,羟值=24.0(mgKOH/g),环氧乙烷的末端含量70重量%
(A6-1):三乙醇胺,羟值=1130(mgKOH/g)
[添加剂(F)]
(F1-1):尿素
(F1-2):N-甲脲
(F2-1):甘氨酸
(F2-2):天门冬氨酸
(F3-1):氢醌
(F3-2):双茶黄素A(ビステアフラビンA)
(F’-1):卡巴肼
[发泡剂(C)]
(C-1):水
[氨基甲酸酯化催化剂(D)]
(D-1):三乙二胺的33重量%二丙二醇溶液[日本AirProductsJapan株式会社制“DABCO-33LV”]
(D-2):双-N,N-二甲基氨基乙醚的70重量%二丙二醇溶液[东曹株式会社制“TOYOCATET”]
[稳泡剂(E)]
(E-1):聚醚改性二甲基硅氧烷系稳泡剂[东丽道康宁株式会社制“SZ-1328”]
[有机聚异氰酸酯(B)]
(B-1):TDI/MDI(重量比)=80/20、NCO%=44.6%[日本聚氨酯工业株式会社制“CE-729”]
<物性试验>
<1>:核密度(kg/m3)
<2>:硬度(25%ILD)(N/314cm2)
<3>:回弹性(%)
<1>~<3>根据JISK6400。
<凝胶时间>
进行自由发泡,使弹球每隔一定时间间隔从泡沫上方落下,将未到达泡沫底面的最初的弹球落下的时间作为凝胶时间。
<醛扩散量测定>
对于得到的各软质聚氨酯泡沫成型体,测定甲醛(以下简写为FA)和乙醛(以下简写为AA)的扩散量。测定为,从上述各成型体切取长100mm×宽80mm×厚度100mm的长方体状的试验片作为样品,将该样品装入取样袋内。将袋内置换为高纯度氮气。用65℃的烤箱加热2小时,将袋内的气体3L收集至DNPH采样管(GLPakminiAERO:GLSciences制)。利用DNPH采样管收集的气体使用乙腈5mL溶出。将该溶液,使用高效液相色谱(Prominence系列:岛津制作所制)进行FA和AA的定量分析。
(测定条件)
使用柱:SUMIPAXODSC-05-4615(住化分析中心制)
检测器:UV检测器(测定波长:360nm)
流动相:乙腈:水=45:55体积%
流速:0.8ml
柱温度:40℃
注入量:20μl
根据表1、2的结果可知,本发明的实施例与比较例相比,醛扩散量非常少,与比较例3相比固化性优异。此外,即便是氨基甲酸酯化催化剂的用量更少时,仍具有优异的固化性。
产业上的可利用性
通过本发明的制造方法得到的车辆座椅用垫,作为能够减少醛类的扩散的座椅用垫是有用的。
Claims (3)
1.一种车辆座椅用垫的制造方法,是包括工序(I)的车辆座椅用垫的制造方法,所述工序(I)是使活性氢成分(A)和有机聚异氰酸酯(B)在发泡剂(C)、氨基甲酸酯化催化剂(D)、稳泡剂(E)和添加剂(F)的存在下反应而得到软质聚氨酯泡沫的工序,其中,(C)含有水,(F)含有选自下述通式(1)表示的尿素化合物(F1)、氨基酸(F2)和多元酚(F3)中的至少1种,软质聚氨酯泡沫的核密度为25~90kg/m3,回弹性为50~75%,硬度(25%-ILD)为150~400N/cm2,
在通式(1)中,R表示氢、碳原子数1~4的烷基或羟基,各自可以相同也可以不同,但至少1个表示氢;n表示0~3的整数。
2.根据权利要求1所述的车辆座椅用垫的制造方法,其中,将活性氢成分(A)的重量作为基准,添加剂(F)的用量为0.01~3重量%。
3.根据权利要求1或2所述的车辆座椅用垫的制造方法,将包含活性氢成分(A)、发泡剂(C)、氨基甲酸酯化催化剂(D)、稳泡剂(E)和添加剂(F)、以及根据需要的其他辅助成分的混合物与有机聚异氰酸酯(B)混合而得到软质聚氨酯泡沫原液,将该软质聚氨酯泡沫原液注入预先安置有面状表皮材料的模具型腔内,使其固化、发泡,以软质聚氨酯泡沫一体地粘接于该表皮材料的状态发泡成型。
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US11001690B2 (en) * | 2017-07-10 | 2021-05-11 | Nhk Spring Co., Ltd. | Cushion material, seat cushion material, and seat |
US10793692B2 (en) * | 2018-10-24 | 2020-10-06 | Covestro Llc | Viscoelastic flexible foams comprising hydroxyl-terminated prepolymers |
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