CN116507609A - 热塑性聚氨酯树脂组合物 - Google Patents
热塑性聚氨酯树脂组合物 Download PDFInfo
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- CN116507609A CN116507609A CN202180081259.1A CN202180081259A CN116507609A CN 116507609 A CN116507609 A CN 116507609A CN 202180081259 A CN202180081259 A CN 202180081259A CN 116507609 A CN116507609 A CN 116507609A
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- Prior art keywords
- polyurethane resin
- thermoplastic polyurethane
- resin composition
- compound
- uva
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- 239000011342 resin composition Substances 0.000 title claims abstract description 52
- -1 benzotriazole compound Chemical class 0.000 claims abstract description 52
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- 239000000203 mixture Substances 0.000 claims description 27
- 239000012948 isocyanate Substances 0.000 claims description 26
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- IAJNXBNRYMEYAZ-UHFFFAOYSA-N ethyl 2-cyano-3,3-diphenylprop-2-enoate Chemical compound C=1C=CC=CC=1C(=C(C#N)C(=O)OCC)C1=CC=CC=C1 IAJNXBNRYMEYAZ-UHFFFAOYSA-N 0.000 description 3
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- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 2
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- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 2
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Abstract
一种热塑性聚氨酯树脂组合物，其包含：热塑性聚氨酯树脂；含苯并***化合物(UVA1)和三嗪化合物(UVA2)的紫外线吸收剂包，其中UVA1与UVA2的质量比为1:1‑3:1；和任选的受阻胺光稳定剂和/或抗氧化剂化合物；和其中当将所述热塑性聚氨酯树脂组合物形成厚度为6mil的膜时，所述热塑性聚氨酯树脂组合物在波长280‑365nm间的最大紫外线透射率≤3％和在波长365‑370nm间的紫外线透射率≤6％，和其中以聚氨酯树脂组合物的总重量计，聚氨酯树脂组合物中UVA1和UVA2的累计重量％为0.5‑0.85wt％。
Description
技术领域
本发明主要涉及具有一定加速耐候性和紫外线透射性能的热塑性聚氨酯树脂组合物。
背景技术
热塑性聚氨酯(“TPU”)树脂经常用于各种需要强度、柔韧性和耐磨性的终端用途。例如，TPU树脂用于保护基质(如涂覆基质)免受物理损伤及阳光紫外线造成的损伤。这就是为什么TPU基薄膜经常应用于汽车行业保护汽车各部件免受操作过程中可能影响车辆的碎片(如岩石或石头)的影响。除了提供防碎屑的物理保护外，TPU基薄膜还用于保护薄膜下方的油漆免受紫外线的损坏作用，紫外线通常会导致油漆随时间变淡或从车辆上剥落。
尽管TPU树脂具有在汽车工业中使用所需的物理性能，但仍需要改进这种树脂以获得更好的性能。
具体实施方式
正如这里所应用，除非另外明确指出，所有数字如表示数值、范围、量或百分比的那些，均可在其前冠有“约”，即使“约”本身并没有出现。复数包括单数，或者反之。
正如这里所应用，“复数”指两个或更多个，而术语"数字"指1或大于1的整数。
正如这里所应用，“包括”和类似术语指“包括但不限于”。
当指任何数值范围时，这种范围应理解为包括所述最小值和最大值范围之间的每一个数字和/或分数。例如，范围“1-10”拟包括在所述最小值1和所述最大值10之间(和包括1和10)的所有子范围。
除非在这里另外指出，“分子量”指按凝胶渗透色谱测量的重均分子量(Mw)。
除非在这里另外指出，当提到任何化合物时，也包括这种化合物的所有异构体(如立体异构体)。
除非在这里另外指出，当提到任何化合物时，也包括这种化合物的所有异构体(如立体异构体)。
热塑性聚氨酯树脂组合物
本发明的热塑性聚氨酯树脂组合物包含：(i)热塑性聚氨酯树脂；(ii)包含苯并***化合物(UVA1)和三嗪化合物(UVA2)的紫外线吸收剂包，其中UVA1与UVA2的质量比为1:1-3:1；和任选的(iii)受阻胺光稳定剂和/或抗氧化剂化合物；其中当所述热塑性聚氨酯树脂组合物形成厚度为6mil的膜时，所述热塑性聚氨酯树脂组合物在波长280-365nm间的最大紫外线透射率≤3％和在波长365-370nm间的紫外线透射率≤6％，和其中以聚氨酯树脂组合物的总重量计，聚氨酯树脂组合物中UVA1和UVA2的累计重量％为0.5-0.85wt％。
在某些实施方案中，热塑性聚氨酯树脂组合物还包含如下进一步详细描述的草酰苯胺化合物(UVA3)。
组分(i)：热塑性聚氨酯树脂
热塑性聚氨酯树脂组合物包含为如下物质的反应产物的热塑性聚氨酯树脂：(a)异氰酸酯化合物、(b)异氰酸酯反应性化合物，和(c)增链剂。这里所公开的热塑性聚氨酯树脂组合物的一个优点是当应用最小量的紫外线稳定剂化合物时，其表现出所需的紫外线透射率和耐候性能。
以热塑性聚氨酯树脂组合物的总重量计，组分(i)可以占95-99wt％。
异氰酸酯化合物
可用作组分(a)的合适异氰酸酯化合物包括脂族、芳脂族和/或芳族聚异氰酸酯。所述异氰酸酯化合物通常具有R-(NCO)x结构，其中x为至少2和R包括芳族、脂族或组合的芳族/脂族基团。合适的聚异氰酸酯的非限定实例包括二苯基甲烷二异氰酸酯(“MDI”)类异氰酸酯(如2,4'、2,2'、4,4'MDI或它们的混合物)、MDI和它们的低聚物的混合物(如聚合的MDI或“粗”MDI)，和聚异氰酸酯与含异氰酸酯反应性氢原子的组分的反应产物(如聚合的聚异氰酸酯或预聚物)。因此，DNR异氰酸酯、/>2185异氰酸酯、M异氰酸酯和/>1840异氰酸酯或它们的组合可以用作异氰酸酯化合物。/>和/>异氰酸酯化合物可由Huntsman International LLC获得。
合适的异氰酸酯化合物的其它实例包括甲苯基二异氰酸酯(“TDI”)(如2,4TDI、2,6TDI或它们的组合)、六亚甲基二异氰酸酯(“HMDI”或“HDI”)、异佛尔酮二异氰酸酯(“IPDI”)、亚丁基二异氰酸酯、三甲基六亚甲基二异氰酸酯、二(异氰酰基环己基)甲烷(如4,4′-二异氰酰基二环己基甲烷)、异氰酰基甲基-1,8-辛烷二异氰酸酯、四甲基二甲苯二异氰酸酯(“TMXDI”)、1,5-萘二异氰酸酯(“NDI”)、对-亚苯基二异氰酸酯(“PPDI”)、1,4-环己烷二异氰酸酯(“CDI”)、联苯二胺二异氰酸酯(“TODI”)或它们的组合。含异氰脲酸酯、碳化二亚胺或脲酮亚胺基团的改性聚异氰酸酯也可用作组分(a)。
封端聚异氰酸酯也可用作组分(a)，条件是反应产物的解封端温度低于组分(a)将与组分(b)反应的温度。合适的封端聚异氰酸酯可以包括如下的反应产物；(x)酚或肟化合物和聚异氰酸酯，或(y)聚异氰酸酯和酸化合物如苄基氯、氢氯酸、氯化亚砜或它们的组合。
异氰酸酯的混合物，例如，TDI异构体的混合物(如2,4-和2,6-TDI异构体的混合物)或通过苯胺/甲醛缩合物的光气化产生的二或更高级聚异氰酸酯的混合物也可以用作组分(a)。
在一些实施方案中，异氰酸酯化合物在室温下为液体。异氰酸酯化合物的混合物可以按本领域中已知的任何技术来生产。如果必要，二苯基-甲烷二异氰酸酯的异构体含量可以通过本领域公知的技术达到所要求的范围。例如，改变异构体含量的一种技术是向聚合MDI含量高于所要求的MDI混合物(如含30-80w％4,4'-MDI和剩余物包括MDI低聚物和MDI同系物的MDI)中添加单体MDI(如2,4-MDI)。
以用于形成热塑性聚氨酯树脂的组合物的总重量计，组分(a)可以占25-75wt％(如40wt％的脂族多官能异氰酸酯化合物)。
异氰酸酯反应性化合物
可用作组分(b)的合适的异氰酸酯反应性化合物包括每个分子含至少两个异氰酸酯反应性部分的有机化合物。异氰酸酯反应性化合物在25℃下通常为液态，其具有60-10,000(如300-10,000或小于5,000)的分子量，至少2的名义羟基官能度，和30-2000(如30-1,500或30-800)的羟基当量重量。
可用作组分(b)的合适多元醇的实例包括聚醚多元醇，如通过环氧烷与每个分子含2-8个活性氢原子的引发剂加成制备的那些。可以用于形成聚醚多元醇的合适环氧烷包括环氧乙烷、环氧丙烷和环氧丁烷或它们的组合。可以应用的合适引发剂包括二醇、甘油、三羟甲基丙烷、三乙醇胺、季戊四醇、山梨醇、蔗糖、亚乙基二胺、乙醇胺、二乙醇胺、苯胺、甲苯二胺(如2,4和2,6甲苯二胺)、聚亚甲基聚亚苯基聚胺、N-烷基亚苯基-二胺、邻-氯-苯胺、对-氨基苯胺、二氨基萘或它们的组合。
可用作组分(b)的其它合适的多元醇化合物包括每个分子具有至少2的名义羟基官能度和至少一个仲或叔胺氮原子的Mannich多元醇。在一些实施方案中，Mannich多元醇是芳族化合物、醛和链烷醇胺的缩合物。例如，Mannich缩合物可以通过(i)酚和/或烷基酚与(ii)甲醛、单乙醇胺、二乙醇胺和/或二异丙醇胺缩合产生。在一些实施方案中，Mannich缩合物为酚或壬基苯酚与甲醛和二乙醇胺的反应产物。在一些实施方案中，所述Mannich缩合物用作烷氧基化的引发剂。对于烷氧基化一种或多种Mannich缩合物来说，可以应用环氧烷(如上述的那些环氧烷)。当聚合完成时，Mannich多元醇包含与脂族碳原子相连的伯位羟基和/或仲位羟基。
可以应用的其它合适多元醇为在多元醇的聚合结构中包含环氧丙烷(“PO”)、环氧乙烷(“EO”)或PO和EO基团或部分的组合的聚醚多元醇。这些PO和EO单元在整个聚合结构中可以随机或以嵌段区块形式排布。在某些实施方案中，以多元醇的总重量计，多元醇的EO含量为0-100wt％(如50-100wt％)。在一些实施方案中，以多元醇的总重量计，多元醇的PO含量为100-0wt％(如100-50wt％)。在另一些实施方案中，多元醇的EO含量可以为多元醇的99-33wt％，而其PO含量为多元醇的1-66wt％。在一些实施方案中，所述EO和/或PO单元可以位于多元醇聚合结构终端，或者位于多元醇的聚合骨架结构的内部区域内。合适的聚醚多元醇包括通过二-或三官能引发剂顺序加成环氧丙烷和环氧乙烷而获得的聚(氧乙烯氧丙烯)二醇和三醇。在一些实施方案中，在本发明中应用的聚醚多元醇包括在多官能引发剂(例如水和低分子量多元醇)的存在下通过环氧乙烷与另一种环状氧化物(如环氧丙烷)聚合而获得的反应产物。可以应用的低分子量多元醇包括乙二醇、丙二醇、二乙二醇、二丙二醇、环己烷二甲醇、间苯二酚、双酚A、甘油、三羟甲基丙烷、1,2,6-己三醇、季戊四醇或它们的组合。在某些实施方案中，组分(b)包括上文提到的二醇或三醇或它们的组合。
可用作组分(b)的聚酯多元醇包括具有线性聚合结构和数均分子量(Mn)为约500-10,000(如优选为约700-5,000或700至约4,000)且酸值通常小于1.3(如小于0.8)的聚酯多元醇。分子量通过分析终端官能基团来确定且与数均分子量相关。聚酯多元醇可以通过如下过程来生产；(1)一种或多种二醇物质与一种或多种二羧酸或酸酐的酯化反应；或(2)酯基转移反应(即一种或多种二醇物质与二羧酸的酯的反应)。二醇与酸的摩尔比通常大于一摩尔的过量是优选的，以获得具有终端羟基的线性聚合链。聚酯多元醇也包括通常由己内酯和双官能引发剂如二乙二醇制得的各种内酯。理想聚酯多元醇的二羧酸可以为脂族、环脂族、芳族或它们的组合。合适二羧酸通常具有4-15个碳原子，包括琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、十二烷二酸、间苯二甲酸、对苯二甲酸、环己烷二羧酸或它们的组合。也可以应用前述二羧酸的酸酐(如邻苯二甲酸酐、四氢邻苯二甲酸酐或它们的组合)。在一些实施方案中，己二酸是优选的酸。用于形成合适的聚酯多元醇的二醇物质包括总共具有2-12个碳原子的脂族和芳族二醇。这种二醇的实例包括乙二醇、1,2-丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、2,2-二甲基-1,3-丙二醇、1,4-环己烷二甲醇、癸二醇、十二烷二醇或它们的组合。
可用作组分(b)的合适多元醇的附加例子包括羟基终端的聚硫醚、聚酰胺、聚酯酰胺、聚碳酸酯、聚缩醛、聚烯烃、聚硅氧烷、和简单二醇如乙二醇、丁二醇、二乙二醇、三乙二醇、丙二醇、二丙二醇、三丙二醇和它们的组合物。
组分(b)也可以包含其它异氰酸酯反应性化合物，包括聚胺和聚硫醇。合适的聚胺包括伯和仲胺终端的聚醚、芳族二胺(例如二乙基甲苯二胺、芳族聚胺)或它们的组合。
以用于形成热塑性聚氨酯树脂的组合物的总重量计，组分(b)可以占25-75wt％(如50wt％的聚己内酯多元醇)。
增链剂
可用作组分(c)的合适化合物包括低分子量二醇和双官能的低分子量二醇醚。合适的低分子量二醇的实例包括乙二醇、1,2-丙二醇、1,3-丙二醇，1,2-丁二醇、1,3-丁二醇、1,4-丁二醇，1,5-戊二醇、1,6-己二醇、二乙二醇、二丙二醇、新戊二醇、3-甲基-1,5-戊二醇、2,2-二乙基-1,3-丙二醇、2-正丁基-2-乙基-1,3-丙二醇、2,2,4-三甲基-1,3-戊二醇、2-乙基-1,3-己二醇，1,4-环己烷二甲醇、1,4-二(2-羟基乙氧基)苯或它们的组合。
以用于形成热塑性聚氨酯树脂的组合物的总重量计，组分(c)可以占2-15wt％(如10wt％的1,4-丁二醇)。
组分(ii)：紫外线吸收剂包
热塑性聚氨酯树脂组合物还包含含苯并***化合物(“UVA1”)和三嗪化合物(“UVA2”)的紫外线吸收剂包。在某些实施方案中，UVA1与UVA2的质量比为1:1-3:1。
可在热塑性聚氨酯树脂组合物中应用的合适苯并***化合物包括2-(2H-苯并***-2-基)-6-(1-甲基-1-苯基乙基)-4-(1,1,3,3-四甲基丁基)苯酚、2-苯酚、2-(2H-苯并***-2-基)-4-(1,1,3,3-四甲基丁基)或它们的组合。在一些实施方案中，UVA1的最大熔点温度可以为141℃。
可在热塑性聚氨酯树脂组合物中应用的合适三嗪化合物包括羟基苯基-三嗪、2-[4,6-二(2,4-二甲基苯基)-1,3,5-三嗪-2-基]-5-[3-[(2-乙基己基)氧]-2-羟基丙氧基]或它们的组合。在一些实施方案中，UVA2的最大熔点温度可以为148℃。
紫外线吸收剂包还可以包含草酰苯胺化合物(“UVA3”)。当存在时，UVA1与UVA2与UVA3的质量比为1:1:0.2至3:1:1。在一些实施方案中，UVA3的最大熔点温度可以为127℃。
以热塑性聚氨酯组合物的总重量计，组分(ii)可以占0.05-0.85wt％(例如0.25wt％的UVA1和0.25wt％的UVA2)。虽然组分(ii)的存在量可以为0.05-0.85wt％，但应注意UVA1和UVA2的实际量可以变化。例如，在一些实施方案中，UVA1的存在量可以为0.25wt％，而UVA2的存在量也为0.25wt％。但在其它实施方案中，UVA1的存在量可以为0.5wt％，而UVA2的存在量为0.2wt％。因此，配制者可以调整UVA1和UVA2的量，以实现想要的或目标的性质。
组分(iii)：其它添加剂
热塑性聚氨酯树脂组合物可以任选地包含其它添加剂，如受阻胺光稳定剂化合物、抗氧化剂化合物或它们的组合。
可在热塑性聚氨酯树脂组合物中应用的合适受阻胺光稳定剂化合物包括可由BASF获得的受阻胺光稳定剂TINUVIN系列的添加剂(包括可由其它生产商获得的结构等同的添加剂)。
可在热塑性聚氨酯树脂组合物中应用的合适抗氧化剂化合物包括可由BASF获得的IRGANOX、IRGAFOS系列抗氧化剂化合物的添加剂(包括可由其它生产商获得的结构等同的添加剂)或它们的组合。
当存在时，以热塑性聚氨酯组合物的总重量计，组分(iii)可以占0.1-1wt％(例如0.25wt％的Tinuvin 622)。
热塑性聚氨酯树脂组合物的制备方法
这里公开的热塑性聚氨酯树脂组合物可以通过使包含异氰酸酯化合物、异氰酸酯反应性化合物和增链剂化合物的反应性混合物反应以形成热塑性聚氨酯树脂来制备。所述反应性混合物还包含含苯并***化合物(UVA1)和三嗪化合物(UVA2)的紫外线吸收剂包，其中UVA1与UVA2的质量比为1:1-3:1。在某些实施方案中，所述紫外线吸收剂包还包含草酰苯胺化合物(“UVA3”)。当存在时，UVA1与UVA2与UVA3的质量比为1:1:0.2-3:1:1。任选地，所述反应性混合物还可以包含一种或多种添加剂，如受阻胺光稳定剂化合物、抗氧化剂化合物或它们的组合。
在某些实施方案中，可以将上文所列的组分全部同时引入到反应容器中。在这些实施方案中，热塑性聚氨酯树脂在反应容器中存在其它添加剂的情况下原位形成。注意的是这些其它添加剂，如上文提到的紫外线吸收剂，将不引入热塑性聚氨酯树脂的聚合物结构中。相反，这些添加剂只简单存在于热塑性聚氨酯树脂组合物的基质中。
在其它实施方案中，在引入上文所述的其它添加剂之前，可以首先向反应容器中加入用于形成热塑性聚氨酯树脂的反应性组分。在一些实施方案中，在引入添加剂之前，聚氨酯树脂可以部分形成。
热塑性聚氨酯树脂组合物的性能
当形成6mil厚的膜(例如通过挤出应用所公开的热塑性聚氨酯树脂组合物制备的TPU粒料形成)时，热塑性聚氨酯树脂组合物在波长280-365nm间的最大紫外线透射率(“UVT”)≤3％(例如≤2％或≤1％)和在波长365-370nm间的紫外线透射率≤6％(例如≤5.8％、≤5.5％或≤5.5％)。在某些实施方案中，除了上文提到的在365-370nm间的UVT性能，热塑性聚氨酯树脂组合物在波长200-315nm间的最大UVT≤5％和在波长315-350nm间的最大UVT≤3％。所述最大UVT可以应用UV-VIS SPEC TEST测量。正如这里所应用，UV-VISSPEC TEST指：(1)提供6mil厚且由热塑性聚氨酯树脂组合物(如这里所公开的)形成的TPU膜；和(2)应用Agilent Technologies Model Cary 300UV/可见光光谱仪获得在各种波长下所述膜的UVT。
除了上文所列的UVT性能外，当形成6mil厚的膜并按ASTM G154经受UV-A和UV-B光照射时，热塑性聚氨酯树脂组合物还表现出优异的UV-A和UV-B耐候性。
在某些实施方案中，当形成6mil厚的膜时，热塑性聚氨酯树脂组合物按ASTM D412测量的最小拉伸强度为6500psi。
油漆保护膜
本发明的热塑性聚氨酯树脂组合物可以用于生产油漆保护膜，其中将由热塑性聚氨酯组合物获得的TPU膜夹在顶涂层和粘合剂层之间。
调整
虽然已详细描述了本发明的具体实施方案，本领域熟练技术人员应理解在考虑本发明总体教导下，可以开发对于所述细节的各种调整和替代方案。因此，这里所公开的方案只是示例性的，和不限制本发明的范围，本发明范围由所附权利要求及其全部等价方案的总范围确定。因此，上面所列的所有特征和/或元素可以彼此间任意组合，并且仍在本发明范围内。
实施例
组分
脂族异氰酸酯：可由Covestro AG获得的H12MDI。
CAPA多元醇：可由Ingevity Corp.获得的聚己内酯。
增链剂：分子量小于200的1,4-丁二醇。
合成
应用脂族异氰酸酯、CAPA多元醇和增链剂通过间歇过程合成热塑性聚氨酯树脂组合物。所述TPU组合物含有紫外线稳定剂添加剂和其它常见的添加剂，如抗氧化剂(AO)、加工稳定剂和受阻胺光稳定剂。
将CAPA多元醇、增链剂和添加剂(抗氧化剂(AO)、加工稳定剂、UV吸收剂和受阻胺光稳定剂)加入反应容器中并混合。然后在搅拌的情况下加入脂族异氰酸酯。反应混合物达到90-100℃后，将其倒入聚四氟乙烯内衬的模具中，并在室温下固化2天。固化后，将产品进一步切成颗粒，且加工成粒料，并挤出为6mil厚的膜，用于UV光谱测试、加速耐候测试(UVA和UVB老化)、水解测试和物理性能测试(例如通过UV-VIS SPEC TEST测试)。
表1所示的实施例1-2是应用UVA1和UVA3合成的，其在6mil厚的膜上产生较差的UVT曲线(在280-370nm间的波长下大于6％的UV透射率)。
表2所示的实施例3-5是应用单一的UVA1吸收剂合成的，其在6mil厚的膜上产生中等的UVT曲线(在280-370nm间的波长下小于4％的UV透射率)。
表3所示的实施例6-8是应用比率为1:1的混合UV吸收剂(UVA 1和UVA 2)合成的，其在6mil厚的膜上产生中等的UVT曲线(在280-370nm间的波长下小于6％的UV透射率)。
表4所示的实施例9-10是应用混合UV吸收剂(UVA 1和UVA 2)合成的，其在6mil厚的膜上在280-370nm的波长下有小于1％的非常好的UVT曲线。
表5所示的实施例11是应用混合UV吸收剂(UVA 1、UVA 2和UVA3)合成的，其在6mil厚的膜上在280-370nm的波长下有小于1％的非常好的UVT曲线。
可以看出，在一定的浓度和比例下选择特定类型的UV吸收剂能提供适合用作油漆保护膜的优异的UVT曲线、良好色彩的膜以及整体良好的耐候性能。
表1：具有较差UVT曲线的配制实施例
| TPU组合物 | 实施例1 | 实施例2 |
| 脂族异氰酸酯 | 39.95 | 39.9 |
| CAPA多元醇 | 48.56 | 48.38 |
| 增链剂 | 10.09 | 10.09 |
| 抗氧化剂 | 0.7 | 0.7 |
| 加工稳定剂 | 0.15 | 0.15 |
| UV吸收剂1 | - | 0.25％Tinuvin 928 |
| UV吸收剂2 | - | - |
| UV吸收剂3 | 0.5％Tinuvin 312 | 0.25％Tinuvin 312 |
| 受阻胺光稳定剂 | 0.25％Tinuvin 622 | 0.25％Tinuvin 622 |
| 合计 | 100 | 100 |
| UVT(6mil膜)(280-365nm) | <50％ | <11％ |
| UVT(6mil膜)(365-370nm) | <60％ | <11％ |
| 最初的YI(6mil膜) | 0.73 | 0.77 |
表2：应用单一UV吸收剂的配制实施例
表3：应用混合吸收剂(UVA1和UVA2)的配制实施例
表4：应用混合吸收剂(UVA1和UVA2)的在280-370nm波长下具有小于1％的优异UVT
曲线的配制实施例
| TPU组合物 | 实施例9 | 实施例10 |
| 脂族异氰酸酯 | 39.9％ | 40.0％ |
| CAPA多元醇 | 48.38％ | 48.35％ |
| 增链剂 | 10.09％ | 10.04％ |
| 抗氧化剂 | 0.7％ | 0.7％ |
| 加工稳定剂 | 0.15％ | 0.15％ |
| UV吸收剂1 | 0.25％Tinuvin 928 | 0.25％Tinuvin 329 |
| UV吸收剂2 | 0.25％Tinuvin 460 | 0.25％Tinuvin 460 |
| UV吸收剂3 | - | - |
| 受阻胺光稳定剂 | 0.25％Tinuvin 622 | 0.25％Tinuvin 622 |
| 合计 | 100 | 100 |
| UVT(6mil膜)(280-365nm) | <1％ | <1％ |
| UVT(6mil膜)(365-370nm) | <1％ | <1％ |
| 最初的YI(6mil膜) | 0.88 | 0.79 |
表5：应用混合吸收剂(UVA1、UVA2和UVA3)的在280-370nm波长下具有小于1％的优
异UVT曲线的配制实施例
| TPU组合物 | 实施例11 |
| 脂族异氰酸酯 | 39.9％ |
| CAPA多元醇 | 48.15％ |
| 增链剂 | 10.06％ |
| 抗氧化剂 | 0.7％ |
| 加工稳定剂 | 0.15％ |
| UV吸收剂1 | 0.3％Tinuvin 329 |
| UV吸收剂2 | 0.3％Tinuvin 460 |
| UV吸收剂3 | 0.1％Tinuvin 312 |
| 受阻胺光稳定剂 | 0.25％Tinuvin 622 |
| 合计 | 100 |
| UVT(6mil膜)(280-365nm) | <1％ |
| UVT(6mil膜)(365-370nm) | <1％ |
| 最初的YI(6mil膜) | 0.87 |
Claims (17)
1.一种热塑性聚氨酯树脂组合物，包含：
热塑性聚氨酯树脂；
含苯并***化合物(UVA1)和三嗪化合物(UVA2)的紫外线吸收剂包，其中UVA1与UVA2的质量比为1:1-3:1；和
任选的受阻胺光稳定剂和/或抗氧化剂化合物；
其中当将所述热塑性聚氨酯树脂组合物形成厚度为6mil的膜时，所述热塑性聚氨酯树脂组合物在波长280-365nm间的最大紫外线透射率≤3％和在波长365-370nm间的紫外线透射率≤6％，和其中以聚氨酯树脂组合物的总重量计，聚氨酯树脂组合物中UVA1和UVA2的累计重量％为0.5-0.85wt％。
2.权利要求1所述的热塑性聚氨酯树脂组合物，其中所述最大紫外线透射率按UV-VISSPEC TEST测量。
3.权利要求1所述的热塑性聚氨酯树脂组合物，其中所述紫外线吸收剂包还包含草酰苯胺化合物(UVA3)。
4.权利要求3所述的热塑性聚氨酯树脂组合物，其中UVA1与UVA2与UVA3的质量比为1:1:0.2-3:1:1。
5.权利要求1所述的热塑性聚氨酯树脂组合物，其中所述膜在波长280-365nm间的最大紫外线透射率≤2％和在波长365-370nm间的最大紫外线透射率≤4％。
6.权利要求1所述的热塑性聚氨酯树脂组合物，其中所述聚氨酯树脂包括异氰酸酯化合物、多元醇化合物和增链剂化合物的反应产物。
7.权利要求1所述的热塑性聚氨酯树脂组合物，其中将所述膜施用于涂覆基质。
8.权利要求7所述的热塑性聚氨酯树脂组合物，其中所述涂覆基质用一个或多个油漆层涂覆。
9.权利要求10所述的热塑性聚氨酯树脂组合物，其中所述一个或多个油漆层为透明涂层，和将所述膜施用于所述透明涂层的表面。
10.一种热塑性聚氨酯树脂的制备方法，所述方法包括：
使包含异氰酸酯化合物、异氰酸酯反应性化合物和增链剂化合物的混合物反应，以形成热塑性聚氨酯树脂；其中所述混合物还包含抗氧化剂化合物和含受阻胺光稳定剂化合物、苯并***化合物(UVA1)和三嗪化合物(UVA2)的紫外线吸收剂包，其中UVA1与UVA2的质量比为1:1-3:1；和
其中当将所述热塑性聚氨酯树脂形成6mil厚的膜时，所述热塑性聚氨酯树脂组合物在波长280-365nm间的最大紫外线透射率≤3％和在波长365-370nm间的最大紫外线透射率≤6％，和其中以聚氨酯树脂组合物的总重量计，聚氨酯树脂组合物中UVA1和UVA2的累计重量％为0.5-0.85wt％。
11.权利要求10所述的方法，其中所述最大紫外线透射率通过UV-VIS SPECT TEST测量。
12.权利要求10所述的方法，其中所述紫外线吸收剂包还包含草酰苯胺化合物(UVA3)。
13.权利要求12所述的方法，其中UVA1与UVA2与UVA3的质量比为1:1:0.2-3:1:1。
14.权利要求10所述的方法，其中所述膜在波长280-365nm间的最大紫外线透射率≤2％和在波长365-370nm间的最大紫外线透射率≤4％。
15.权利要求10所述的方法，还包括在涂覆基质上施用所述热塑性聚氨酯树脂。
16.权利要求15所述的方法，其中所述涂覆基质用一个或多个油漆层涂覆。
17.权利要求16所述的方法，其中所述一个或多个油漆层为透明涂层，和将所述膜施用于所述透明涂层的表面。
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| US63/120,450 | 2020-12-02 | ||
| PCT/US2021/061339 WO2022119885A1 (en) | 2020-12-02 | 2021-12-01 | A thermoplastic polyurethane resin composition |
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| EP (1) | EP4255952A1 (zh) |
| CN (1) | CN116507609A (zh) |
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| GB2361005B (en) * | 2000-04-04 | 2002-08-14 | Ciba Sc Holding Ag | Synergistic mixtures of uv-absorbers in polyolefins |
| MY139524A (en) * | 2004-06-30 | 2009-10-30 | Ciba Holding Inc | Stabilization of polyether polyol, polyester polyol or polyurethane compositions |
| CN101522417B (zh) * | 2006-10-04 | 2013-05-22 | 3M创新有限公司 | 制备多层聚氨酯保护膜的方法 |
| EP2380859B1 (en) * | 2008-12-22 | 2018-08-22 | Sekisui Chemical Co., Ltd. | Laminate for laminated glass and interlayer for laminated glass |
| BR112012003918B1 (pt) * | 2009-08-24 | 2020-12-29 | Sekisui Chemical Co., Ltd | película intermediária para vidro laminado e vidro laminado |
| JP7110606B2 (ja) * | 2017-02-27 | 2022-08-02 | 東ソー株式会社 | 熱可塑性ポリウレタン樹脂組成物、および該樹脂組成物を用いた成形体 |
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| WO2022119885A1 (en) | 2022-06-09 |
| US20240002574A1 (en) | 2024-01-04 |
| CA3202767A1 (en) | 2022-06-09 |
| EP4255952A1 (en) | 2023-10-11 |
| MX2023006296A (es) | 2023-06-14 |
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