CN113527613A - 一种聚氨酯弹性体的合成工艺及微孔发泡材料的制备工艺 - Google Patents
一种聚氨酯弹性体的合成工艺及微孔发泡材料的制备工艺 Download PDFInfo
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- CN113527613A CN113527613A CN202110669875.0A CN202110669875A CN113527613A CN 113527613 A CN113527613 A CN 113527613A CN 202110669875 A CN202110669875 A CN 202110669875A CN 113527613 A CN113527613 A CN 113527613A
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- tween
- polyurethane elastomer
- surfactant
- foam
- slurry
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Classifications
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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Abstract
本发明适用化妆品技术领域,提供一种聚氨酯弹性体的合成工艺及微孔发泡材料的制备工艺,所述聚氨酯弹性体包括以下原料:聚合物二元醇、二异氰酸化合物、扩链剂、抗氧化剂、催化剂、反应介质和终止剂;本发明实施例将聚氨酯合成混合浆料,通过物理方法起泡,形成微孔结构,孔与孔互相重叠、连通;表面细腻光滑,弹性好不容易变形,不容易吸粉残留化妆品,本发明实施例所制备的产品的吸水性较小;解决了现有粉扑、美妆蛋等美妆产品,材料表面粗糙,湿水后体积增大,流动性强、容易吸粉的问题。
Description
技术领域
本发明属于化妆品技术领域,尤其涉及一种聚氨酯弹性体的合成工艺及微孔发泡材料的制备工艺。
背景技术
随着人们生活水平的提高,人们越来越重视外在美,化妆的人也越来越多,化妆棉市场呈现增长趋势。现在市场上的化妆棉用品,包括粉扑、美妆蛋等。它们所用的材料一般是天然胶乳和非天然胶乳,其中,因为非天然胶乳的使用寿命长、使用过敏率低等优点,非天然胶乳制备的受欢迎程度较高;其中,非天然胶乳材料中,以聚氨酯居多,聚氨酯回弹性好,耐低温、耐磨性佳、与皮肤接触无致敏性,非常适合用于粉扑、美妆蛋类用品;在其制备工艺中,大多数是化学发泡工艺,由于材质原因,材料表面粗糙,湿水后体积增大15%,流动性强、含水量高的底妆产品上妆比较容易吸粉。
发明内容
本发明实施例的目的在于提供一种聚氨酯弹性体的合成工艺及微孔发泡材料的制备工艺,以解决上述背景技术中提出的问题。
为实现上述目的,本发明实施例提供一种聚氨酯弹性体,所述聚氨酯弹性体包括以下质量组分的原料:
聚合物二元醇12.38-33.42%、二异氰酸化合物3.73%-10.06%、扩链剂0.55-1.48%、抗氧化剂:0.1-0.2%、催化剂0.01-0.03%、反应介质54.87-83.29%、终止剂0.05-0.13%。
优选地,所述聚合物二元醇包括聚酯二醇和聚醚二醇,且所述聚合物二元醇中的聚酯二醇和聚醚二醇之间混合的摩尔数比例为1:5至5:1。
优选地,所述聚酯二醇包括分子量1000-4000为的聚酯二元醇、分子量1000-3000的聚已内酯二醇、分子量500-3000的聚碳酸酯二醇中的一种或两种;聚醚二元醇为分子量500-5000为PPG型、分子量400-2000为聚氧化乙烯二醇、分子量1000-3000为聚四氢呋喃二醇中的一种或两种。上述聚合物二元醇的羟基一般选择在30-200mgKOH/g。
优选地,所述二异氰酸化合物包括二苯基甲烷二异氰酸酯(MDI)、甲苯二异氰酸酯(TDI)、六亚甲基二异氰酸酯(HDI)、异氟尔酮二异氰酸酯(IPDI)。
优选地,所述扩链剂包括胺类扩链剂和醇类扩链剂中的一种;胺类扩链剂为乙二胺、N,N-二羟基(二异丙基)苯胺、莫卡(MOCA)、3,5二乙基甲苯二胺、3,5二甲硫基甲苯二胺、N,N-二仲丁基对苯二胺、N,N-双氨丙基甲胺中的一种或两种;所述醇类扩链剂为乙二醇、1,4丁二醇、乙二醇、1,6已二醇、新戊二醇、2-甲基丙二醇、1,2丙二醇、一缩二乙二醇、一缩二丙二醇、1,4环已二醇、2-丁基-2-乙基-1,3-丙二醇中的一种或两种。
优选地,所述催化剂为三亚乙基二胺、二甲基乙醇胺、二月桂酸二丁基锡、有机铋、三乙胺、辛酸亚锡、二乙酸二丁基锡、异辛酸铋、异辛酸锌中的一种。
优选地,所述反应介质为二甲基甲酰胺,二甲基乙酰胺中的一种或两种。
优选地,所述抗氧化剂为亚磷酸三苯酯、三(壬基化苯基)亚磷酸酯、亚磷酸三(2-乙基己基)酯、亚磷酸十三烷酯、亚磷酸三月桂酯、4,4'-亚丁基双-(3-甲基-6-叔丁苯基)-四(十三烷基)二亚磷酸酯、二异丙醇醚二亚磷酸二苯酯、二硬脂基季戊四醇二亚磷酸酯、氢化双酚a季戊四醇亚磷酸酯中的一种。
上述一种聚氨酯弹性体的合成工艺,包括以下步骤;
按照比例将聚合物二元醇、二异氰酸化合物、扩链剂、抗氧化剂、催化剂和部分反应介质、加入反应罐中,搅拌均匀30分钟以上,再对物料进行加热至75-85℃,反应2-6个小时,期间根据粘度变化,补加反应介质,待粘度达到180万CPS以上,停止加热反应,加入终止剂,冷却后,密封储存好聚氨酯弹性体桨料。
一种包括上述一种聚氨酯弹性体的合成工艺制备而成的聚氨酯弹性体桨料的微孔发泡材料,所述微孔发泡材料包括以下质量组分的原料:
聚氨酯弹性体桨料10.02-16.98%、填料66.65-83.03%、表面活性剂0.73-1.19%、颜料0.002-0.3%、滑爽剂0.04-0.3%和阻燃剂0.05-0.25%。
优选地,所述填料为氯化钠、无水碳酸钙、碳酸钠、碳酸氢钠、无水硫酸钠,聚乙烯醇粉末中的一种及一种以上的混合物。
优选地,所述表面活性剂为非离子型表面活性剂中的一种或一种以上混合物,或者所述表面活性剂为阴离子型表面活性剂和非离子型表面活性剂之间的混合物。
优选地,所述阴离子型表面活性剂为括十二烷基硫酸钠、烷基苯磺酸钠、月桂醇磺基琥珀酸酯二钠、月桂酰胺基、MEA-磺基琥珀酸酯二钠、异构醇醚硫酸钠、脂肪醇醚硫酸钠、辛基酚聚氧乙烯醚硫酸钠、烯丙氧基脂肪醇聚氧乙烯醚硫酸铵中的一种;所述非离子型表面活性剂为吐温20(TWEEN-20)、吐温21(TWEEN-21)、吐温40(TWEEN-40)、吐温60(TWEEN-60)、吐温61(TWEEN-61)、吐温80(TWEEN-80)、吐温81(TWEEN-81)、吐温85(TWEEN-85)、斯盘SP-20、SP-40、SP-60、SP-80、SP-85、辛基酚聚氧乙烯醚、脂肪醇聚氧乙醚、异构醇聚氧乙烯醚中的一种或两种。
优选地,所述颜料为巴斯夫Heliogen颜料、Cinquasia系列颜料、Cromophtal系列颜料、Heliogen颜料、Paliogen系列、Microlith系列颜料中的一种。
优选地,所述滑爽剂为有机硅类滑爽剂,所述有机硅类滑爽剂为二甲基硅油、二乙基硅油、苯甲基硅油、聚醚改性有机硅油、含羟基的聚醚改性有机硅油、氨基硅油、嵌段硅油、乙烯基硅油中的一种及一种以上的混合物。
优选地,所述阻燃剂为三(2-氯乙基)磷酸酯、三(2-氯丙基)磷酸酯、三(二氯丙基)磷酸酯、甲基膦酸二甲酯、乙基膦酸二乙酯、丙基膦酸二甲酯、磷酸三乙酯、磷酸三(丁氧基乙基)酯、异丙基化三苯基磷酸酯、三聚氰胺、氰尿酸三聚氰胺、三聚氰胺(聚)磷酸盐、三(一缩二丙二醇)亚磷酸酯、四苯基二丙二醇二亚磷酸酯、N,N-二(2-羟乙基)氨基亚甲基膦酸二乙酯、N,N-二(2-羟乙基)氨基甲基膦酸二甲酯中的一种及一种以上混合物。
上述微孔发泡材料的制备工艺,包括以下步骤;
(1)投加填料:将颜料、表面活性剂、阻燃剂、滑爽剂和聚氨酯弹性体桨料依次加入分散机中,并混合均匀后,再最后加入相应的填料,持续搅拌2h,变成糊状的浆料混合物A;
(2)挤压:将浆料混合物A通过挤出机挤压到模具里,挤出机各段都保持30-45℃,挤压过程通过抽真空设备避免气泡产生;
(3)泡水:将装在模具里面的桨料浸泡在水中,浸泡时间一般为3-20天,最终形成细微孔的泡棉;
(4)将泡棉从水中取出、用烘箱烘干水分、根据产品需要采用打磨机加工成产品所需的各种形状,之后检测合格后入库。
综上所述,由于采用了上述技术方案,具有以下有益效果:
本发明实施例提供了一种聚氨酯弹性体的合成工艺及微孔发泡材料的制备工艺,本发明实施例的生产工艺区别于传统的双组分形式化学发泡聚氨酯,聚氨酯合成混合浆料,通过物理方法起泡,形成微孔结构,且本发明的微孔粒径较小,孔与孔互相重叠、连通;表面细腻光滑,弹性好不容易变形,不容易吸粉残留化妆品,本发明实施例所制备的产品的吸水性较小。
附图说明
图1为本发明实施例所制备的微孔发泡材料在高倍显微镜检测下的图片。
图2为市场中对比样例产品在高倍显微镜检测下的图片。
具体实施方式
为了使本发明实施例的目的、技术方案及优点更加清楚明白,以下结合具体实施例,对本发明实施例进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明实施例,并不用于限定本发明实施例。
现有的粉扑、美妆蛋类用品在其制备工艺中,大多数是化学发泡工艺,由于材质原因,材料表面粗糙,湿水后体积增大15%,流动性强、含水量高的底妆产品上妆比较容易吸粉;本发明实施例的聚氨酯合成混合浆料,通过物理方法起泡,形成微孔结构,孔与孔互相重叠、连通;表面细腻光滑,弹性好不容易变形,不容易吸粉残留化妆品。
实施例1
制备聚氨酯弹性体桨料:按照对应比例将聚合物二元醇15.09%、二异氰酸化合物9.33%%、反应介质74.87%、扩链剂0.55%、抗氧化剂0.1%和催化剂0.01%加入反应罐中,搅拌均匀30分钟以上,搅拌转速为50转/分钟,再对物料进行加热至75℃,反应2个小时,待粘度达到180万CPS以上,停止加热反应,加入终止剂0.05%,冷却后,密封储存好聚氨酯弹性体桨料;
按照对应比例将颜料0.002%、表面活性剂0.73%、阻燃剂0.05%、滑爽剂0.04%和聚氨酯弹性体桨料10.02%依次加入分散机中,并混合均匀后,再最后加入相应的填料66.65%,持续搅拌2h,变成糊状的浆料混合物A;
将浆料混合物A通过挤出机挤压到模具里,挤出机各段都保持30℃,挤压过程通过抽真空设备避免气泡产生;
将装在模具里面的桨料浸泡在水中,浸泡时间一般为3天,最终形成细微孔的泡棉;
将泡棉从水中取出、用烘箱烘干水分、根据产品需要采用打磨机加工成产品所需的各种形状,之后检测合格后入库。
所述聚合物二元醇包括聚酯二醇和聚醚二醇,且所述聚合物二元醇中的聚酯二醇和聚醚二醇之间混合的摩尔数比例为1:5。
所述聚酯二醇为分子量为1000的聚已内酯二醇。
所述二异氰酸化合物为MDI。
所述扩链剂为胺类扩链剂。
所述催化剂为三亚乙基二胺。
所述反应介质为二甲基甲酰胺。
所述抗氧化剂为亚磷酸三苯酯。
所述终止剂为甲醇。
所述表面活性剂为阴离子型表面活性剂和非离子型表面活性剂之间的混合物,且阴离子型表面活性剂和非离子型表面活性剂之间混合的摩尔数比例为1:1至1:10,所述表面活性剂具有调节微孔的作用。
所述阴离子型表面活性剂为括十二烷基硫酸钠;所述非离子型表面活性剂为吐温20(TWEEN-20)。
所述填料为氯化钠。
所述滑爽剂为二甲基硅油,所述滑爽剂可提高丝滑性。
所述阻燃剂为三(2-氯乙基)磷酸酯。
实施例2
制备聚氨酯弹性体桨料:按照对应比例将聚合物二元醇16.59%、二异氰酸化合物10.06%、反应介质71.59%、扩链剂1.48%、抗氧化剂0.12%和催化剂0.03%加入反应罐中,搅拌均匀30分钟以上,搅拌转速为50转/分钟,再对物料进行加热至85℃,反应6个小时,待粘度达到180万CPS以上,停止加热反应,加入终止剂0.13%,冷却后,密封储存好聚氨酯弹性体桨料;
按照对应比例将颜料0.3%、表面活性剂1.19%、阻燃剂0.25%、滑爽剂0.3%和聚氨酯弹性体桨料16.98%依次加入分散机中,并混合均匀后,再最后加入相应的填料80.98%,持续搅拌2h,变成糊状的浆料混合物A;
将浆料混合物A通过挤出机挤压到模具里,挤出机各段都保持45℃,挤压过程通过抽真空设备避免气泡产生;
将装在模具里面的桨料浸泡在水中,浸泡时间一般为20天,最终形成细微孔的泡棉;
将泡棉从水中取出、用烘箱烘干水分、根据产品需要采用打磨机加工成产品所需的各种形状,之后检测合格后入库。
所述聚合物二元醇包括聚酯二醇和聚醚二醇,且所述聚合物二元醇中的聚酯二醇和聚醚二醇之间混合的摩尔数比例为5:1。
所述聚酯二醇为分子量为1000的聚已内酯二醇和分子量为500的聚碳酸酯二醇;所述聚醚二醇为分子量为400的聚氧化乙烯二醇和分子量为1000的聚四氢呋喃二醇。
所述二异氰酸化合物为TDI。
所述扩链剂为醇类扩链剂。
所述催化剂为二月桂酸二丁基锡。
所述反应介质为二甲基甲酰胺和二甲基乙酰胺之间的混合物。
所述抗氧化剂为亚磷酸十三烷酯。
所述终止剂为乙醇和异丙醇之间的混合物。
所述表面活性剂为阴离子型表面活性剂和非离子型表面活性剂之间的混合物,且阴离子型表面活性剂和非离子型表面活性剂之间混合的摩尔数比例为1:1至1:10,所述表面活性剂具有调节微孔的作用。
所述阴离子型表面活性剂为括月桂醇磺基琥珀酸酯二钠;所述非离子型表面活性剂为吐温20(TWEEN-20)和吐温21(TWEEN-21)之间的混合物。
所述填料为氯化钠和无水碳酸钙之间的混合物。
所述滑爽剂为二甲基硅油和二乙基硅油之间的混合物,所述滑爽剂可提高丝滑性。
所述阻燃剂为三(2-氯乙基)磷酸酯和三(2-氯丙基)磷酸酯之间的混合物。
实施例3
制备聚氨酯弹性体桨料:按照对应比例将聚合物二元醇13.85%、二异氰酸化合物6.9%、反应介质78%、扩链剂1.0%、抗氧化剂0.15%和催化剂0.02%加入反应罐中,搅拌均匀30分钟以上,搅拌转速为50转/分钟,再对物料进行加热至80℃,反应4个小时,待粘度达到180万CPS以上,停止加热反应,加入终止剂0.08%,冷却后,密封储存好聚氨酯弹性体桨料;
按照对应比例将颜料0.2%、表面活性剂1.1%、阻燃剂0.2%、滑爽剂0.2%和聚氨酯弹性体桨料16.3%依次加入分散机中,并混合均匀后,再最后加入相应的填料82%,持续搅拌2h,变成糊状的浆料混合物A;
将浆料混合物A通过挤出机挤压到模具里,挤出机各段都保持40℃,挤压过程通过抽真空设备避免气泡产生;
将装在模具里面的桨料浸泡在水中,浸泡时间一般为15天,最终形成细微孔的泡棉;
将泡棉从水中取出、用烘箱烘干水分、根据产品需要采用打磨机加工成产品所需的各种形状,之后检测合格后入库。
所述聚合物二元醇包括聚酯二醇和聚醚二醇,且所述聚合物二元醇中的聚酯二醇和聚醚二醇之间混合的摩尔数比例为1:5;所述聚酯二醇为分子量为1000-3000的聚已内酯二醇,所述聚醚二醇为分子量为400-2000的聚氧化乙烯二醇;所述二异氰酸化合物为MDI;所述扩链剂为胺类扩链剂,所述胺类扩链剂为N,N-二羟基(二异丙基)苯胺;所述催化剂为三亚乙基二胺;所述反应介质为二甲基甲酰胺;所述抗氧化剂为亚磷酸十三烷酯;所述终止剂为甲醇;所述表面活性剂为阴离子型表面活性剂和非离子型表面活性剂之间的混合物,且阴离子型表面活性剂和非离子型表面活性剂之间混合的摩尔数比例为1:1;所述阴离子型表面活性剂为括十二烷基硫酸钠;所述非离子型表面活性剂为异构醇聚氧乙烯醚;所述填料为氯化钠。所述滑爽剂为二乙基硅油;所述阻燃剂为三(2-氯乙基)磷酸酯。
通过高倍显微镜检测实施例3所制备的产品和市场同类样品,通过高倍显微镜检测实施例3所制备的产品和市场同类样品放大50倍后的视图。结果如图1,图2所示。
由图1可知,本发明实施例3所制备的产品分布着较小密集的孔,孔与孔互相重叠、连通,不容易吸粉残留化妆品。
由图2可知,市场上的样品由于泡孔较大,且稀疏,泡孔之间无连接,易吸收大量化妆品,不耐用。
综上所述,本发明实施例提供了一种聚氨酯弹性体的合成工艺及微孔发泡材料的制备工艺,本发明实施例的生产工艺区别于传统的双组分形式化学发泡聚氨酯,聚氨酯合成混合浆料,通过物理方法起泡,形成微孔结构,孔与孔互相重叠、连通;表面细腻光滑,弹性好不容易变形,不容易吸粉残留化妆品,本发明实施例所制备的产品的吸水性较小,且本发明的微孔粒径较小。
对于本领域技术人员而言,显然本发明实施例不限于上述示范性实施例的细节,而且在不背离本发明实施例的精神或基本特征的情况下,能够以其他的具体形式实现本发明实施例。因此,无论从哪一点来看,均应将实施例看作是示范性的,而且是非限制性的,本发明实施例的范围由所附权利要求而不是上述说明限定,因此旨在将落在权利要求的等同要件的含义和范围内的所有变化囊括在本发明实施例内。
此外,应当理解,虽然本说明书按照实施方式加以描述,但并非每个实施方式仅包含一个独立的技术方案,说明书的这种叙述方式仅仅是为清楚起见,本领域技术人员应当将说明书作为一个整体,各实施例中的技术方案也可以经适当组合,形成本领域技术人员可以理解的其他实施方式。
Claims (7)
1.一种聚氨酯弹性体,其特征在于,所述聚氨酯弹性体包括以下质量组分的原料:
聚合物二元醇12.38-33.42%、二异氰酸化合物3.73%-10.06%、扩链剂0.55-1.48%、抗氧化剂0.1-0.2%、催化剂0.01-0.03%、反应介质54.87-83.29%、终止剂0.05-0.13%。
2.如权利要求1所述的一种聚氨酯弹性体,其特征在于,所述聚合物二元醇包括聚酯二醇和聚醚二醇,且所述聚合物二元醇中的聚酯二醇和聚醚二醇之间混合的摩尔数比例为1:5至5:1。
3.一种如权利要求1-2任一所述的一种聚氨酯弹性体的合成工艺,其特征在于,包括以下步骤;
按照比例将聚合物二元醇、二异氰酸化合物、扩链剂、抗氧化剂、催化剂和反应介质加入反应罐中,搅拌均匀30分钟以上,再对物料进行加热至75-85℃,反应2-6个小时,期间根据粘度变化,补加反应介质,待粘度达到180万CPS以上,停止加热反应,加入终止剂,冷却后,密封储存好聚氨酯弹性体桨料。
4.一种包括权利要求3所述的一种聚氨酯弹性体的合成工艺制备而成的聚氨酯弹性体桨料的微孔发泡材料,其特征在于,所述微孔发泡材料包括以下质量组分的原料:
聚氨酯弹性体桨料10.02-16.98%、填料66.65-83.03%、表面活性剂0.73-1.19%、颜料0.002-0.3%、滑爽剂0.04-0.3%和阻燃剂0.05-0.25%。
5.根据权利要求4所述的微孔发泡材料,其特征在于,所述表面活性剂为非离子型表面活性剂中的一种或一种以上混合物,或者所述表面活性剂为阴离子型表面活性剂和非离子型表面活性剂之间的混合物。
6.根据权利要求4所述的微孔发泡材料,其特征在于,所述阴离子型表面活性剂为括十二烷基硫酸钠、烷基苯磺酸钠、月桂醇磺基琥珀酸酯二钠、月桂酰胺基、MEA-磺基琥珀酸酯二钠、异构醇醚硫酸钠、脂肪醇醚硫酸钠、辛基酚聚氧乙烯醚硫酸钠、烯丙氧基脂肪醇聚氧乙烯醚硫酸铵中的一种;所述非离子型表面活性剂为吐温20(TWEEN-20)、吐温21(TWEEN-21)、吐温40(TWEEN-40)、吐温60(TWEEN-60)、吐温61(TWEEN-61)、吐温80(TWEEN-80)、吐温81(TWEEN-81)、吐温85(TWEEN-85)、斯盘SP-20、SP-40、SP-60、SP-80、SP-85、辛基酚聚氧乙烯醚、脂肪醇聚氧乙醚、异构醇聚氧乙烯醚中的一种或两种。
7.如权利要求4-6任一所述的一种微孔发泡材料的制备工艺,其特征在于,包括以下步骤;
(1)投加填料:将颜料、表面活性剂、阻燃剂、滑爽剂和聚氨酯弹性体桨料依次加入分散机中,并混合均匀后,再最后加入相应的填料,持续搅拌2h,变成糊状的浆料混合物A;
(2)挤压:将浆料混合物A通过挤出机挤压到模具里,挤出机各段都保持30-45℃,挤压过程通过抽真空设备避免气泡产生;
(3)泡水:将装在模具里面的桨料浸泡在水中,浸泡时间一般为3-20天,最终形成细微孔的泡棉;
(4)将泡棉从水中取出、烘干水分、根据产品需要采用打磨机加工成产品所需的各种形状,之后检测合格后入库。
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Application publication date: 20211022 |