CN1154685C - 保护聚合物免受紫外光损害的聚合物制品、光稳定添加剂组合物和光稳定添加剂母料 - Google Patents
保护聚合物免受紫外光损害的聚合物制品、光稳定添加剂组合物和光稳定添加剂母料 Download PDFInfo
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- CN1154685C CN1154685C CNB998056596A CN99805659A CN1154685C CN 1154685 C CN1154685 C CN 1154685C CN B998056596 A CNB998056596 A CN B998056596A CN 99805659 A CN99805659 A CN 99805659A CN 1154685 C CN1154685 C CN 1154685C
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- Prior art keywords
- triazine
- hals
- polymer product
- light absorber
- hydroxyl
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- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims abstract description 55
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 28
- -1 pyrrolidyl Chemical group 0.000 claims description 61
- 239000000047 product Substances 0.000 claims description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
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- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 claims description 7
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- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 claims description 5
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- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
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- JMHCCAYJTTWMCX-QWPJCUCISA-M sodium;(2s)-2-amino-3-[4-(4-hydroxy-3,5-diiodophenoxy)-3,5-diiodophenyl]propanoate;pentahydrate Chemical compound O.O.O.O.O.[Na+].IC1=CC(C[C@H](N)C([O-])=O)=CC(I)=C1OC1=CC(I)=C(O)C(I)=C1 JMHCCAYJTTWMCX-QWPJCUCISA-M 0.000 claims description 2
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
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- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34926—Triazines also containing heterocyclic groups other than triazine groups
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Abstract
一种聚合物制品,如挤出或模塑制品或双轴取向的带或膜,和一种稳定这种聚合物制品以保护该制品免受暴露在紫外光下引起降解的方法。该制品是这样制得的,将聚合物材料与约50至5,000ppm的至少一种邻羟基三芳基三嗪光吸收剂和约500ppm至1.25%的至少一种分子量至少约为500的低聚、聚合或高分子量HALS混合,其中HALS与三嗪光吸收剂的重量比约为3∶1至20∶1,形成稳定的聚合物组合物,从该稳定的聚合物组合物制成挤出或模塑制品或双轴取向的带或膜。
Description
发明的领域
本发明涉及保护聚合物材料免受紫外辐射或光(“紫外光”)损害的组合物和方法。具体地说,本发明涉及包含至少一种邻羟基三芳基三嗪紫外光吸收剂和至少一种低聚、聚合或高分子量受阻胺光稳定剂(“HALS”)的协同组合的聚合物制品。
发明的背景
众所周知紫外光或紫外辐射,尤其是来自太阳光的紫外光或辐射会使聚合物发生降解。通常这会使可能是模塑制品、聚合物膜、带、涂料等形式的聚合物变脆或泛黄。然而,这种降解可通过在这种制品中或其上加入紫外光稳定剂和紫外光吸收剂而得以抑制。
分别或结合起来使用HALS和紫外光吸收剂(“UVA”)来稳定聚合物材料在已有技术中通常是已知的。尤其是诸如苯并三唑和二苯甲酮之类的紫外光吸收剂起初是用于稳定聚合物材料,以防止这种材料由于暴露在紫外光下而发生降解。稍后发现用于清除暴露在紫外光下在聚合物材料中产生的自由基的HALS比紫外光吸收剂更为有效,这样目前在大部分常规应用中将紫外光吸收剂与至少一种HALS结合起来使用。
欧洲专利申请EP 0704560披露了厚度不大于50微米的上过颜料的纤维,其中用HALS和紫外光吸收剂的协同混合物来稳定颜料。该申请披露了能有效地稳定纤维中的颜料的HALS和紫外光吸收剂的量为0.05-5重量%,但提供的实施例表明当HALS的量提高到高于紫外光吸收剂的量时没有明显的改进。
欧洲专利EP 0453396披露了包含0.01-5重量%含至少一种2-羟基苯基苯并三唑和至少一种2-羟基苯基三嗪或2-羟基二苯甲酮的紫外光吸收剂混合物的涂料组合物,其中紫外光吸收剂的摩尔比为3∶1-1∶3。该涂料组合物任选地可以包含多烷基哌啶HALS的衍生物,如2,2,6,6-四甲基哌啶。尽管在EP 0453396中披露了多种这样的多烷基哌啶衍生物,但没有提及在所要求的组合物中HALS的用量,并且没有一个实施例具体说明了含HALS的组合物。所有的实施例都说明了暴露在氙气灯耐侯试验机中1,000至2,000小时后或暴露在佛罗里达的日光下约1年后会发生某些降解。
美国专利4,619,956披露了一种稳定聚合物膜、涂料或模塑制品以防日光、潮气和氧气作用的方法。该方法包括在聚合物中加入HALS和三-芳基-2-三嗪紫外光吸收剂。HALS较好是2,2,6,6-四烷基哌啶化合物、盐或金属配合物,而紫外光吸收剂较好是下式的三-芳基-2-三嗪,
其中X、Y和Z分别是芳基、碳环基,至少一个芳基含有与三嗪环连接点是邻位的羟基。R1-R9各自是氢、羟基、烷基、烷氧基、磺基、羧基、卤素、卤代烷基或酰氨基。紫外光吸收剂和HALS的用量分别约为0.01-5重量%,但仅例举了含有等量的紫外光吸收剂和HALS的制剂。该组合物能有效地稳定聚合物材料,使其在暴露在紫外光下约1,000至2,400小时后才开始损失光泽或泛黄。
Hardy的美国专利4,331,586披露了用作光稳定剂的低聚物。在为诸如聚丙烯之类的聚合物材料提供保护时,含所披露的低聚HALS的聚合物膜在暴露在紫外光下约1,700小时后会变脆。
因此,仍然需要稳定聚合物材料并长时间地提供保护免受由于暴露在紫外光下而导致的损害的组合物及其使用方法。本发明提供这种方法和组合物。
发明的概述
本发明涉及聚合物制品,如模塑制品、挤出制品和双轴取向的带和膜,其中该制品包含聚合物材料、约50至5,000ppm的至少一种邻羟基三芳基三嗪光吸收剂和约500ppm至1.25%的至少一种分子量至少约为500的低聚、聚合或高分子量的HALS,其中HALS与三嗪的重量比约为3∶1至20∶1,较好约为5∶1至10∶1,最好约为6∶1至7.5∶1。该聚合物制品较好是厚度不小于约1毫米的模塑或挤出制品。
本发明有用的HALS包括式(I)低聚物:
其中R是吗啉代、C1-C8烷基胺、二(C1-C8)烷基胺、吡咯烷基或环己胺,X和X1可以相同或不同,它们是氢、C1-C20烷基、或式(II)基团
其中R1代表氢、C2-C3羟基烷基、C1-C8烷基、羟基或烃氧基(oxyl);R2代表氢、C1-C8烷基或苄基;R3和R4可以相同或不同,它们是C1-C8烷基、苄基或苯乙基或形成C5-C10环烷基;Z是直链或支化的C2-C20亚烷基或被至少是氧代、硫代或
基团间断的直链或支化的C2-C20亚烷基链,其中R5是氢、C1-C20烷基、或式(II)基团;C5-C10亚环烷基、
或
C6-C12亚芳基或C8-C14芳亚烷基;n是大于1的整数;Y是卤原子、C1-C8烷基胺、二(C1-C8)烷基胺、吡咯烷基、吗啉代、环己胺、或
其中X、X1和Z的定义如上所述;条件是X和X1中的至少一个基团是式(II)基团。最好的是,X和X1可以相同或不同,它们是式(II)基团,其中R是吗啉代或辛胺,R1是H或CH3,R2是H,R3和R4是CH3,Z是C6H12,Y是吗啉代、辛胺或
其中X、X1和Z的定义如上所述。
本发明有用的其它HALS包括,但不局限于下述物质:
1. 双(1-辛氧基-2,2,6,6-四甲基-4-哌啶基)癸二酸酯
2. 与4-羟基-2,2,6,6-四甲基-1-哌啶乙醇的琥珀酸二甲酯聚合物
3. 与4-羟基-2,2,6,6-四甲基-1-哌啶乙醇的琥珀酸二甲酯聚合物和N,N=-双(2,2,6,6-四甲基-4-哌啶基)-1,6-己二胺与2,4,6-三氯-1,3,5-三嗪和2,4,4-三甲基-1,2-五胺的聚合物的共混物
4. 1,3,5-三嗪-2,4,6-三胺,N,N===[1,2-亚乙基双[[[(4,6-双[丁基(1,2,2,6,6-五甲基-4-哌啶基)氨基]-1,3,5-三嗪-2-基]亚氨基]-3,1-亚丙基]]-双[N=N==-二丁基-N=,N==-双(1,2,2,6,6-五甲基-4-哌啶基)
5. 1,3,5-三嗪-2,4,6-三胺,N,N===[1,2-亚乙基双[[[(4,6-双[丁基(1-环己氧基-2,2,6,6-四甲基-4-哌啶基)氨基]-1,3,5-三嗪-2-基]亚氨基]-3,1-亚丙基]]-双[N=N==-二丁基-N=,N==-双(1,2,2,6,6-五甲基-4-哌啶基)
6. 1,3,5-三嗪-2,4,6-三胺,N,N===[1,2-亚乙基双[[[(4,6-双[丁基(1,2,2,6,6-五甲基-4-哌啶基)氨基]-2-基]亚氨基]-3,1-亚丙基]]-双[N=N==-二丁基-N=,N==-双(1,2,2,6,6-五甲基-4-哌啶基)
7. 与2,4,6-三氯-1,3,5-三嗪和2,4,4-三甲基-1,2-五胺的N,N=-双(2,2,6,6-四甲基-4-哌啶基)-1,6-己二胺聚合物
8. 聚-甲基丙基-3-氧代-(4(2,2,6,6-四甲基)哌啶基)硅氧烷
9. 聚-甲基丙基-3-氧代-(4(1,2,2,6,6-五甲基)哌啶基)硅氧烷
10. 四甲基-7-氧杂-3,20-二氮杂-21-氧代-二螺(5.1.11.12)二十一碳烷与表氯醇反应的聚烷基-1-氧杂-二氮杂螺癸烷产物
11. 与2,4,6-三氯-1,3,5-三嗪的1,3-丙二胺,N,N==-1,2-亚乙基双聚合物,与N-丁基-2,2,6,6-四甲基-4-哌啶胺的反应产物。
三嗪光吸收剂一般具有下式(III)的结构
其中A、B和C分别为芳族,A、B和C中的至少一个被与三嗪环连接点是邻位的羟基所取代,R1至R9分别选自氢、羟基、烷基、烷氧基、磺基、羧基、卤素、卤代烷基和酰氨基。三嗪光吸收剂较好具有下式(IV)的结构
其中R10、R11、R12和R13相同或不同,它们各自选自氢、羟基、烷基、烷氧基、磺基、羧基、卤素、卤代烷基和酰氨基,R14是氢或C1-C18烷基。R10、R11、R12和R13最好为H或CH3,R14最好为氢、C6H13或C8H17。
其它有用的三嗪光吸收剂包括,但不局限于2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-(己基)氧基-苯酚、2-(4-((2-羟基-3-十二烷氧基丙基)-烃氧基-2-羟基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪、2-(4-((2-羟基-3-十三烷氧基丙基)-烃氧基-2-羟基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪、2-(4-((2-羟基-3-十三烷氧基丙基)-烃氧基-2-羟基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪和2-(4-((2-羟基-3-异辛氧基丙基)-烃氧基-2-羟基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪和它们的混合物。
光稳定的聚合物制品可从聚合物材料制成,所述聚合物材料例如可以是下述物质中的任何一种,聚烯烃,聚酯,聚醚,聚酮,聚酰胺,天然或合成橡胶,聚氨酯,聚苯乙烯,高抗冲聚苯乙烯,聚丙烯酸酯,聚甲基丙烯酸酯,聚缩醛,聚丙烯腈,聚丁二烯,聚苯乙烯,ABS,SAN(苯乙烯-丙烯腈),ASA(丙烯酸酯-苯乙烯-丙烯腈),乙酸丁酸纤维素(cellulosic acetate butyrate),纤维素聚合物,聚酰亚胺,聚酰胺酰亚胺,聚醚酰亚胺,聚苯硫醚,PPO,聚砜,聚醚砜,聚氯乙烯,聚碳酸酯,聚酮,脂族聚酮,热塑性TPU,氨基树脂交联的聚丙烯酸酯或聚酯,多异氰酸酯交联的聚酯或聚丙烯酸酯,苯酚/甲醛,脲/甲醛或蜜胺/甲醛树脂,干燥或未干燥的醇酸树脂,醇酸树脂,聚酯树脂,与蜜胺树脂、脲树脂、异氰酸酯、异氰脲酸酯、氨基甲酸酯、或环氧树脂交联的丙烯酸酯树脂,得自脂族、环脂族、杂环或芳族缩水甘油基化合物并与酐或胺交联的交联环氧树脂,聚硅氧烷,Michael加成聚合物,胺,含活性不饱和或亚甲基化合物的封端胺,含活性不饱和或亚甲基化合物的酮亚胺,与不饱和丙烯酸类聚乙酰乙酸酯树脂结合起来的聚酮亚胺,与不饱和丙烯酸类树脂结合起来的聚酮亚胺,可辐射固化的组合物,环氧蜜胺树脂,有机染料,化妆品,纤维素基的纸制品,照相膜纸,油墨和它们的混合物。
光稳定的聚合物制品较好是从聚烯烃均聚物、共聚物或三元共聚物制成,更好是从聚乙烯或聚丙烯的均聚物、共聚物或三元共聚物制成,其中聚乙烯或聚丙烯是在至少一种单中心催化剂(single site catalyst)、至少一种齐格勒-纳塔催化剂或齐格勒-纳塔催化剂和至少一种单中心催化剂存在下的聚合产物。
可用于制造本发明制品的其它有用的聚合物材料包括,但不局限于聚酰胺、聚酯、聚缩醛和聚氨酯。
本发明也涉及一种光稳定添加剂组合物,它包含至少一种邻羟基三芳基三嗪光吸收剂和至少一种分子量至少约为500的低聚、聚合或高分子量HALS,其中HALS与三嗪光吸收剂的重量比约为3∶1至20∶1,如上所述,本发明也涉及一种光稳定添加剂母料,它包含约30-98重量%,较好约50-95重量%的聚合物树脂,至少一种邻羟基三芳基三嗪光吸收剂和至少一种分子量至少约为500的低聚、聚合或高分子量HALS,其中HALS与三嗪光吸收剂的重量比约为3∶1至20∶1,该母料可以是粒料、颗粒或锭剂的形式。添加剂组合物可以通过喷雾光吸收剂和HALS的溶液,熔融共混、挤出或通过物理压实制得。
本发明还涉及一种制造稳定聚合物制品的方法。该方法包括将聚合物材料与约50至5,000ppm的至少一种邻羟基三芳基三嗪光吸收剂和约500ppm至1.25%的至少一种分子量至少约为500的低聚、聚合或高分子量HALS混合,其中HALS与三嗪光吸收剂的重量比约为3∶1至20∶1,形成稳定的聚合物组合物,从该稳定的聚合物组合物制成挤出或模塑制品和双轴取向的带或膜。
发明的详细描述
本发明涉及用于稳定聚合物材料如模塑或挤出制品、双轴取向的带和膜以及涂料的组合物,以防止由于暴露在紫外光,尤其是波长约为290-350纳米的紫外光下而发生的降解。意想不到地发现当将约50至5,000ppm(每百万中的份数)的邻羟基三芳基三嗪和约500ppm至1.25%的低聚、聚合或高分子量HALS与聚合物材料混合,其中HALS与三嗪的重量比约为3∶1至20∶1,较好约为5∶1至10∶1,最好约为6∶1至7.5∶1时,可以保护聚合物材料免受由于暴露在紫外光下而损害的时间显著地长于任何已有技术中含HALS、紫外光吸收剂或其组合的光稳定剂组合物所提供的时间。
低聚、聚合或高分子量HALS的分子量较好大于约500,更好大于约1,000。合适的HALS是如美国专利4,331,586中所披露类型的低聚物,所述专利的全部内容在此参考引用。
本发明有用的HALS包括,但不局限于式(I)低聚物
其中R是吗啉代、C1-C8烷基胺、二(C1-C8)烷基胺、吡咯烷基或环己基氨基,较好是吗啉代或辛胺,X和X1可以相同或不同,它们代表氢、C1-C20烷基,或式(II)基团
其中R1代表氢、C2-C3羟基烷基、C1-C8烷基、羟基或烃氧基;R2代表氢、C1-C8烷基或苄基;R3和R4可以相同或不同,它们代表C1-C8烷基、苄基或苯乙基或与它们所连接的碳一起形成C5-C10环烷基;Z代表C2-C20直链或支化的亚烷基,其中碱性链可以被氧代、硫代或
基团间断,其中R5代表氢、C1-C20烷基、或式(II)基团;C5-C10亚环烷基、
C6-C12亚芳基或C8-C14芳亚烷基;n是大于1的整数;Y代表卤原子、C1-C8烷基胺、二(C1-C8)烷基胺、吡咯烷基、吗啉代或
其中X、X1和Z的定义如上所述;条件是在重复单元中存在至少一个式(II)的哌啶基部分。
较好的式(I)组合物是那些其中X和X1是式(II)部分。特别好的式(I)组合物是那些其中X和X1是2,2,6,6-四甲基-4-哌啶基并且Z是六亚甲基。
作为紫外光吸收剂的本发明有用的邻羟基三芳基三嗪是如美国专利4,619,956中披露的那些类型,该专利的全部内容在此参考引用。本发明的三嗪光吸收剂一般具有下式(III)的结构
其中A、B和C分别为芳族,A、B和C中的至少一个被与三嗪环连接点是邻位的羟基所取代,R1至R9分别选自氢、羟基、烷基、烷氧基、磺基、羧基、卤素、卤代烷基和酰氨基。
三嗪光吸收剂较好具有下式(IV)的结构
其中R10、R11、R12和R13如上面R1至R9中所述的那些基团,它们最好为H或CH3,R14为氢或C1-C18烷基,以氢、C6烷基和C8烷基为最佳。
一般来说,聚合物制品如模塑或挤出制品或双轴取向的带或膜可在本发明中通过将约50至5,000ppm本发明的三嗪光吸收剂和约500ppm至1.25%本发明的HALS与用于制备制品的聚合物材料混合而加以稳定。HALS与三嗪光吸收剂之比一般约为20∶1至3∶1,较好约为10∶1至5∶1,最好约为6∶1至7.5∶1。理想地,该比值约为7∶1,即以聚合物材料的重量计,约2,000ppm的HALS和约300ppm的三嗪。
尽管本发明的HALS和三嗪光吸收剂可在用本领域已知的任何方法加工聚合物材料的过程中分别加到聚合物材料中,但在加工之前可以制成两种组分的混合物。一般来说,可以将本发明的添加剂组合物制成含本发明HALS和紫外光吸收剂的粒料、颗粒或锭剂。这可通过下述过程实现,将HALS和三嗪一起熔融,挤出该混合物,一起喷雾两种组分的溶液,在蒸发溶剂后形成混合物的粒料或颗粒,或者通过物理压实。
本发明的光稳定添加剂组合物也可以是母料的形式,该母料包含约2-70%,较好约5-50%的添加剂组合物,而其余的则包含聚合物树脂,其中HALS与三嗪光吸收剂之比一般约为20∶1至3∶1,较好约为10∶1至5∶1。
本发明的光稳定添加剂组合物可用于稳定热塑性基材如聚烯烃、聚酯、聚醚、聚氨酯、聚酰胺、聚苯乙烯、高抗冲聚苯乙烯等的模塑制品、膜等。热塑性基材较好是聚烯烃。
本文所用的术语Apolyolefin@包括α-烯烃均聚物如聚乙烯、聚丙烯、聚丁二烯、聚异戊二烯等;α-烯烃共聚物,它包括乙烯-丙烯共聚物、乙烯-丁烯、乙烯-己烯和乙烯-辛烯共聚物、乙烯-乙酸乙烯酯共聚物、苯乙烯-丁二烯共聚物、丙烯腈-丁二烯-苯乙烯三元共聚物等。较好的聚烯烃包括聚乙烯和聚丙烯。
其它在光的作用下易于降解并且其性能可通过加入本发明的化合物而得到改善的有机材料包括聚苯乙烯、天然和合成橡胶;后者例如包括丙烯腈、丁二烯和苯乙烯的均聚物、共聚物和三元共聚物和它们的共混物。
该组合物任选地可以包含其它添加剂,尤其是用于聚烯烃的添加剂,如抗氧化剂、辅助光稳定剂、增塑剂、阻燃剂、抗静电剂和防滑剂、填料、染料、颜料等。
合适的抗氧化剂包括受阻酚类,如2,6-二叔丁基对甲酚;4,4’-双(2,6-二叔丁基苯酚);四[亚甲基(3,5-二叔丁基)-4-羟基-氢化肉桂酸酯]]甲烷;1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)-1,3,5-三嗪-2,4,6-(1H,3H,5H)-三酮;1,3,5-三(3,5-二叔丁基-4-羟基苄基)-s-三嗪-2,4,6-(1H,3H,5H)-三酮;三(2,4-二叔丁基苯基)亚磷酸酯;双(2,4-二叔丁基苯基)季戊四醇二亚磷酸酯;2[[2,4,8,10-四(1,1-二甲基乙基)二苯并[d,f][1,3,2]二氧杂phosphepin-6-基]氧代]N,N-双[2[[2,4,8,10-四(1,1-二甲基乙基)二苯并[d,f][1,3,2]二氧杂phosphepin-6-基]氧代]乙胺;氧化的双(牛脂烷基)胺;4,4’-双(2,6-二异丙基苯酚);2,4,6-三叔丁基苯酚;2,2’-硫代双(4-甲基-6-叔丁基苯酚);2-(3’,5’-二叔丁基-4’-羟基苯基)丙酸十八烷基酯等;硫代二丙酸酯如硫代二丙酸二月桂酯和硫代二丙酸二硬脂酯等;亚磷酸烃酯如亚磷酸三苯酯、亚磷酸三壬酯、二异癸基季戊四醇二磷酸酯、亚磷酸二苯基癸酯等;和它们的组合。
合适的辅助光稳定剂包括苯并三唑类,如2-(2’-羟基-5-叔辛基苯基)苯并三唑;2-(2’-羟基-3,5-二叔丁基苯基)-5-氯代苯并三唑;羟基二苯甲酮类,如2-羟基-4-甲氧基二苯甲酮;2-羟基-4-辛氧基二苯甲酮;2,2’-二羟基-4,4’-二甲氧基二苯甲酮;受阻酚酯,如3,5-二叔丁基-4-羟基苯甲酸正十六烷基酯和3,5-二叔丁基-4-羟基苯甲酸2’,4’-二叔丁基苯酯;2,2’-硫代双(4-叔辛基苯酚)的金属配合物;双(4-叔辛基苯基)砜的镍配合物;二硫代氨基甲酸二丁酯镍;4-羟基-3,-二叔丁基苄基磷酸一烷基酯的镍盐,其中烷基是甲基、乙基、丙基、丁基等;2-羟基-4-甲基苯基十一烷基酮肟的镍配合物等。
可以用本发明保护以免受紫外光侵害的聚合物制品包括,但不局限于模塑或挤出制品、涂料、带和膜。该制品可经挤出、片材挤出、注塑、吹塑、注坯吹塑、旋转模塑或滚塑、压延、热成形、压塑、真空模塑、压力成型、反应注塑和本领域已知的其它类似方法制成。另外,可经粉末涂布、挤出涂布、电涂、喷涂、浸涂和本领域已知的其它类似方法来施涂涂料。
实施例
下述不受限制的实施例仅是本发明较好实例的例举,不能将它们看作限制本发明,本发明范围由所附的权利要求书确定。
实施例1
按下述步骤制备试验样品:将Irganox 1010(0.5g),一种抗氧化剂、Irgafos168(1.0g),一种作为加工稳定剂的亚磷酸酯和硬脂酸锌(0.25g)与LLDPE(低密度聚乙烯)和表1所列的紫外稳定剂干混。所得的制剂在175EC下在1又1/4英寸的单螺杆挤出机中配混,在200EC下经60EC模温的注塑法将其制成拉伸试条。将该拉伸试条暴露在Atlas Ci65 WOM下,用水喷,测量断裂伸长随时间变化的情况。结果用断裂伸长%来表示,列于表1中,其中认为小于50%的伸长是不合格的。
表1
制剂 | 0小时 | 4,000小时 | 6,000小时 | 8,000小时 | 10,000小时 | 12,000小时 | 14,000小时 | 16,000小时 |
Chimassorb944(0.3%)1 | 514 | 551 | 486 | 361 | 218 | 118 | 67 | 46 |
Tinuvin622(0.3%)2 | 509 | 226 | 152 | 61 | 43 | |||
Cyasorb7 UV3346光稳定剂(0.3%)3 | 501 | 548 | 479 | 410 | 301 | 90 | 85 | 45 |
Cyasorb7 UV3346光稳定剂(0.2%)Cyasorb7 UV1164(0.03%)4 | 502 | 570 | 483 | 440 | 411 | 442 | 527 | 402 |
1. N,N=-双(2,2,6,6-四甲基-4-哌啶基)-1,6-己二胺与2,4,6-三氯-1,3,5-三嗪和2,4,4-三甲基-1,2-五胺的聚合物
2.与4-羟基-2,2,6,6-四甲基-1-哌啶乙醇的琥珀酸二甲酯聚合物
3.聚[(6-吗啉代-s-三嗪-2,4-二基)][(2,2,6,6-四甲基-4-哌啶基)亚氨基]-六亚甲基[(2,2,6,6-四甲基-4-哌啶基)亚氨基]
4.式(IV)化合物,其中R10、R11、R12和R13都是甲基,R14是C8H17
从上述数据可以清楚地看出,经本发明光稳定的组合物比已有技术的组合物优异得多,它能提供免受紫外光侵害的保护长达16,000小时,而此时该组合物仍能保持其初始伸长的80%。相反,用已有技术组合物光稳定的组合物在暴露在紫外光下仅4,000至10,000小时后其断裂伸长就开始明显地下降,这是不合格的,即在10,000至16,000小时时其断裂伸长小于50%。
实施例2
将Susi的美国专利4,619,956(“′956专利”)中披露的光稳定组合物保护聚合物材料免受暴露在紫外光下而发生降解的能力与本发明组合物的相比较。′956专利例举了聚合物材料长期暴露在紫外光下的效果,其中各聚合物材料样品包含等量的光稳定组合物和商购HALS,如Tinuvin7 765、Tinuvin7 440、Tinuvin7 900和Sanduvor7 3050,所述光稳定组合物包含下式三嗪光吸收剂
其中R10、R11、R12和R13都是CH3,R14是C8烷基。在暴露在紫外光下8小时随后不受紫外光照射4小时的交替循环辐照后,聚合物材料样品的光泽明显下降,并且在1,200至2,400小时后其黄度增加。相反,包含本发明组合物的聚合物材料在至少16,000小时后仍保持有用的性能,这清楚地表明与含等量HALS和三嗪的组合物相比,本发明组合物具有更佳的优越性。
实施例3
通过将聚酰胺与约50至5,000ppm的邻羟基三芳基三嗪光吸收剂和约500ppm至1.25%分子量至少为500的低聚、聚合或高分子量HALS混合(其中HALS与三嗪光吸收剂的重量比约为3∶1至20∶1)而光稳定的聚酰胺在明显比与已有技术光稳定剂组合物混合的聚酰胺长的时间下暴露在紫外光下也能保持有用的物理性能。当HALS与三嗪光吸收剂的重量比约为5∶1至10∶1时获得了良好的结果。
实施例4
通过将聚酯与约50至5,000ppm的邻羟基三芳基三嗪光吸收剂和约500ppm至1.25%分子量至少为500的低聚、聚合或高分子量HALS混合(其中HALS与三嗪光吸收剂的重量比约为3∶1至20∶1)而光稳定的聚酯在明显比与已有技术光稳定剂组合物混合的聚酯长的时间下暴露在紫外光下也能保持有用的物理性能。当HALS与三嗪光吸收剂的重量比约为5∶1至10∶1时获得了良好的结果。
实施例5
通过将聚缩醛与约50至5,000ppm的邻羟基三芳基三嗪光吸收剂和约500ppm至1.25%分子量至少为500的低聚、聚合或高分子量HALS混合(其中HALS与三嗪光吸收剂的重量比约为3∶1至20∶1)而光稳定的聚缩醛在明显比与已有技术光稳定剂组合物混合的聚缩醛长的时间下暴露在紫外光下也能保持有用的物理性能。当HALS与三嗪光吸收剂的重量比约为5∶1至10∶1时获得了良好的结果。
实施例6
通过将聚氨酯与约50至5,000ppm的邻羟基三芳基三嗪光吸收剂和约500ppm至1.25%分子量至少为500的低聚、聚合或高分子量HALS混合(其中HALS与三嗪光吸收剂的重量比约为3∶1至20∶1)而光稳定的聚氨酯在明显比与已有技术光稳定剂组合物混合的聚氨酯长的时间下暴露在紫外光下也能保持有用的物理性能。当HALS与三嗪光吸收剂的重量比约为5∶1至10∶1时获得了良好的结果。
尽管显而易见的是在此所披露的本发明的内容能很好地用于实现所述目的,但应明白的是本领域的技术熟练者可以作出多种改进和实施方案。因此,想要说明的是所附的权利要求书覆盖所有这些落在本发明真正精神和范围内的改进和实施方案。
Claims (24)
1.一种聚合物制品,它包含聚合物材料、50至5,000ppm的至少一种邻羟基三芳基三嗪光吸收剂和500ppm至1.25%的至少一种分子量至少为500的低聚、聚合或高分子量的HALS,其中HALS与三嗪的重量比为3∶1至20∶1,聚合物制品是模塑制品、挤出制品或双轴取向的带或膜。
2.如权利要求1所述的聚合物制品,其中HALS与三嗪光吸收剂之比为5∶1至10∶1。
3.如权利要求1所述的聚合物制品,其中HALS与三嗪光吸收剂之比为6∶1至7.5∶1。
4.如权利要求1所述的聚合物制品,其中HALS是式(I)低聚物
其中R是吗啉代、C1-C8烷基胺、二(C1-C8)烷基胺、吡咯烷基或环己胺,X和X1可以相同或不同,它们是氢、C1-C20烷基、或式(II)基团
其中R1代表氢、C2-C3羟基烷基、C1-C8烷基、羟基或烃氧基;R2代表氢、C1-C8烷基或苄基;R3和R4可以相同或不同,它们是C1-C8烷基、苄基或苯乙基或形成C5-C10环烷基;Z是直链或支化的C2-C20亚烷基或被至少是氧代、硫代或基团间断的直链或支化的C2-C20亚烷基链,其中R5是氢、C1-C20烷基、或式(II)基团;C5-C10亚环烷基、
C6-C12亚芳基或C8-C14芳亚烷基;n是大于1的整数;Y是卤原子、C1-C8烷基胺、二(C1-C8)烷基胺、吡咯烷基、吗啉代、环己胺、或
其中X、X1和Z的定义如上所述;条件是X和X1中的至少一个基团是式(II)基团。
6.如权利要求1所述的聚合物制品,其中HALS选自双(1-辛氧基-2,2,6,6-四甲基-4-哌啶基)癸二酸酯、与4-羟基-2,2,6,6-四甲基-1-哌啶乙醇的琥珀酸二甲酯聚合物、与4-羟基-2,2,6,6-四甲基-1-哌啶乙醇的琥珀酸二甲酯聚合物和N,N=-双(2,2,6,6-四甲基-4-哌啶基)-1,6-己二胺与2,4,6-三氯-1,3,5-三嗪和2,4,4-三甲基-1,2-五胺的聚合物的共混物、1,3,5-三嗪-2,4,6-三胺,N,N===[1,2-亚乙基双[[[(4,6-双[丁基(1,2,2,6,6-五甲基-4-哌啶基)氨基]-1,3,5-三嗪-2-基]亚氨基]-3,1-亚丙基]]-双[N=N==-二丁基-N=,N==-双(1,2,2,6,6-五甲基-4-哌啶基)、1,3,5-三嗪-2,4,6-三胺,N,N===[1,2-亚乙基双[[[(4,6-双[丁基(1-环己氧基-2,2,6,6-四甲基-4-哌啶基)氨基]-1,3,5-三嗪-2-基]亚氨基]-3,1-亚丙基]]-双[N=N==-二丁基-N=,N==-双(1,2,2,6,6-五甲基-4-哌啶基)、1,3,5-三嗪-2,4,6-三胺,N,N===[1,2-亚乙基双[[[(4,6-双[丁基(1,2,2,6,6-五甲基-4-哌啶基)氨基]-2-基]亚氨基]-3,1-亚丙基]]-双[N=N==-二丁基-N=,N==-双(1,2,2,6,6-五甲基-4-哌啶基)、与2,4,6-三氯-1,3,5-三嗪和2,4,4-三甲基-1,2-五胺的N,N=-双(2,2,6,6-四甲基-4-哌啶基)-1,6-己二胺聚合物、聚-甲基丙基-3-氧代-(4(2,2,6,6-四甲基)哌啶基)硅氧烷、聚-甲基丙基-3-氧代-(4(1,2,2,6,6-五甲基)哌啶基)硅氧烷、四甲基-7-氧杂-3,20-二氮杂-21-氧代-二螺(5.1.11.12)二十一碳烷与表氯醇反应的聚烷基-1-氧杂-二氮杂螺癸烷产物、与2,4,6-三氯-1,3,5-三嗪的1,3-丙二胺,N,N==-1,2-亚乙基双聚合物,与N-丁基-2,2,6,6-四甲基-4-哌啶胺的反应产物。
7.如权利要求1所述的聚合物制品,其中三嗪光吸收剂具有式(III)结构
其中A、B和C分别为芳族,A、B和C中的至少一个被与三嗪环连接点是邻位的羟基所取代,R1至R9分别选自氢、羟基、烷基、烷氧基、磺基、羧基、卤素、卤代烷基和酰氨基。
9.如权利要求8所述的聚合物制品,其中R10、R11、R12和R13为H或CH3,R11为氢、C6H13或C8H17。
10.如权利要求7所述的聚合物制品,其中三嗪光吸收剂选自2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-(己基)氧基-苯酚、2-(4-((2-羟基-3-十二烷氧基丙基)-烃氧基-2-羟基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪、2-(4-((2-羟基-3-十三烷氧基丙基)-烃氧基-2-羟基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪和2-(4-((2-羟基-3-异辛氧基丙基)-烃氧基-2-羟基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪。
11.如权利要求1所述的聚合物制品,其中聚合物制品是厚度不小于1毫米的模塑或挤出制品。
12.如权利要求1所述的聚合物制品,其中聚合物材料选自聚烯烃,聚酯,聚醚,聚酮,聚酰胺,天然或合成橡胶,聚氨酯,聚苯乙烯,高抗冲聚苯乙烯,聚丙烯酸酯,聚甲基丙烯酸酯,聚缩醛,聚丙烯腈,聚丁二烯,聚苯乙烯,ABS,SAN(苯乙烯-丙烯腈),ASA(丙烯酸酯-苯乙烯-丙烯腈),乙酸丁酸纤维素,纤维素聚合物,聚酰亚胺,聚酰胺酰亚胺,聚醚酰亚胺,聚苯硫醚,PPO,聚砜,聚醚砜,聚氯乙烯,聚碳酸酯,聚酮,脂族聚酮,热塑性TPU,氨基树脂交联的聚丙烯酸酯和聚酯,多异氰酸酯交联的聚酯或聚丙烯酸酯,苯酚/甲醛,脲/甲醛或蜜胺/甲醛树脂,干燥或未干燥的醇酸树脂,醇酸树脂,聚酯树脂,与蜜胺树脂、脲树脂、异氰酸酯、异氰脲酸酯、氨基甲酸酯、或环氧树脂交联的丙烯酸酯树脂,得自脂族、环脂族、杂环或芳族缩水甘油基化合物并与酐或胺交联的交联环氧树脂,聚硅氧烷,Michael加成聚合物,胺,含活性不饱和和亚甲基化合物的封端胺,含活性不饱和和亚甲基化合物的酮亚胺,与不饱和丙烯酸类聚乙酰乙酸酯树脂结合起来的聚酮亚胺,与不饱和丙烯酸类树脂结合起来的聚酮亚胺,可辐射固化的组合物,环氧蜜胺树脂,有机染料,化妆品,纤维素基的纸制品,照相膜纸,油墨和它们的混合物。
13.如权利要求1所述的聚合物制品,其中聚合物材料是聚烯烃均聚物、共聚物或三元共聚物。
14.如权利要求13所述的聚合物制品,其中聚合物材料是聚乙烯或聚丙烯的均聚物、共聚物或三元共聚物。
15.如权利要求14所述的聚合物制品,其中聚乙烯或聚丙烯是在至少一种齐格勒-纳塔催化剂存在下的聚合产物。
16.如权利要求14所述的聚合物制品,其中聚乙烯或聚丙烯是在至少一种单中心催化剂存在下的聚合产物。
17.如权利要求14所述的聚合物制品,其中聚乙烯或聚丙烯是在齐格勒-纳塔催化剂和至少一种单中心催化剂存在下的聚合产物。
18.如权利要求1所述的聚合物制品,其中聚合物材料选自聚酰胺、聚酯、聚缩醛和聚氨酯。
19.如权利要求18所述的聚合物制品,其中HALS与三嗪光吸收剂的重量比为5∶1至10∶1。
20.如权利要求18所述的聚合物制品,其中HALS与三嗪光吸收剂的重量比为6∶1至7.5∶1。
21.一种光稳定添加剂组合物,它包含至少一种邻羟基三芳基三嗪光吸收剂和至少一种分子量至少为500的低聚、聚合或高分子量的HALS,其中HALS与三嗪光吸收剂的重量比为3∶1至20∶1。
22.一种光稳定添加剂母料,它包含30-98重量%的聚合物树脂、至少一种邻羟基三芳基三嗪光吸收剂和至少一种分子量至少为500的低聚、聚合或高分子量的HALS,其中HALS与三嗪光吸收剂的重量比为3∶1至20∶1。
23.如权利要求22所述的光稳定添加剂母料,其中添加剂母料是粒料、颗粒或锭剂的形式。
24.如权利要求22所述的光稳定添加剂母料,其中树脂的量为50-95重量%。
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102939348A (zh) * | 2010-05-14 | 2013-02-20 | 富士胶片映像着色有限公司 | 印刷方法、聚合物和油墨 |
CN110997801A (zh) * | 2017-08-02 | 2020-04-10 | 花王株式会社 | 聚合物乳液 |
CN111690257A (zh) * | 2020-07-02 | 2020-09-22 | 中国地质大学(北京) | 耐紫外辐照无色透明聚酰亚胺薄膜及其制备方法和应用 |
Families Citing this family (63)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE69931792T2 (de) * | 1999-12-01 | 2007-05-16 | Chi Mei Optoelectronics Corp. | UV absorbierender Film und Verwendung als Schutzfolie |
US6468609B2 (en) | 1999-12-01 | 2002-10-22 | Agfa-Gevaert | UV-absorbing film and its use as protective sheet |
CO5231248A1 (es) * | 2000-07-26 | 2002-12-27 | Ciba Sc Holding Ag | Articulos transparentes de polimero de baja consistencia |
US6777470B2 (en) * | 2001-05-29 | 2004-08-17 | Sunoco, Inc. (R&M) | Polyolefin additive packages for producing articles with enhanced stain resistance |
US7297409B2 (en) | 2001-10-12 | 2007-11-20 | Sabic Innovative Plastics Ip Bv | Multilayer, weatherable compositions and method of manufacture thereof |
EP1302309B2 (en) * | 2001-10-12 | 2016-09-07 | SABIC Innovative Plastics IP B.V. | Multi-layer, weatherable compositions and method of manufacture thereof |
US6630527B2 (en) | 2001-10-19 | 2003-10-07 | General Electric Company | UV stabilized, impact modified polyester/polycarbonate blends, articles, and methods of manufacture thereof |
US7090926B2 (en) * | 2001-11-09 | 2006-08-15 | General Electric Company | Multi-layer, weatherable compositions and method of manufacture thereof |
WO2003054083A1 (de) * | 2001-12-20 | 2003-07-03 | Ami - Agrolinz Melamine International Gmbh | Additiv zur inhibierung von photolytischen abbaureaktionen in aminoplasten |
AT411452B (de) * | 2001-12-20 | 2004-01-26 | Agrolinz Melamin Gmbh | Uv-resistenter, thermohärtbarer aminoplastverbund, dessen herstellung und verwendung |
DE10233848A1 (de) * | 2002-07-22 | 2004-02-19 | Agrolinz Melamin Gmbh | Additiv zur Inhibierung von photolytischen Abbaureaktionen in Aminoplasten |
US7482397B2 (en) * | 2003-01-13 | 2009-01-27 | Eastman Chemical Company | Polycarbonate compositions |
US20040143041A1 (en) * | 2003-01-13 | 2004-07-22 | Pearson Jason Clay | Polyester compositions |
US7297735B2 (en) * | 2003-03-05 | 2007-11-20 | Eastman Chemical Company | Polycarbonate compositions |
US7070683B2 (en) * | 2003-02-13 | 2006-07-04 | Ppg Industries Ohio, Inc. | Electrodepositable coating compositions and processes related thereto |
US20040183053A1 (en) * | 2003-03-20 | 2004-09-23 | Pearson Jason Clay | Process for the preparation of a hindered amine light stabilizer salt |
US20050277713A1 (en) * | 2003-03-05 | 2005-12-15 | Pearson Jason C | Polymer blends |
BRPI0407952A (pt) * | 2003-03-05 | 2006-03-07 | Eastman Chem Co | composição polimérica |
US20040192813A1 (en) * | 2003-03-20 | 2004-09-30 | Pearson Jason Clay | Polymer compositions containing an ultraviolet light absorbing compound |
US20040180994A1 (en) * | 2003-03-05 | 2004-09-16 | Pearson Jason Clay | Polyolefin compositions |
US7338992B2 (en) * | 2003-03-05 | 2008-03-04 | Eastman Chemical Company | Polyolefin compositions |
ATE390460T1 (de) * | 2003-03-05 | 2008-04-15 | Eastman Chem Co | Polymerblends |
EP1338622A3 (en) * | 2003-03-14 | 2003-09-10 | Ciba SC Holding AG | Stabilizer mixtures |
CN1875061A (zh) * | 2003-11-04 | 2006-12-06 | Cytec技术有限公司 | 紫外稳定添加剂组合物 |
US20070161741A1 (en) * | 2003-12-09 | 2007-07-12 | Mitsui Chemicals, Inc. | Resin composition for reflector plate and reflector plate |
US7582690B2 (en) * | 2004-11-19 | 2009-09-01 | Eastman Chemical Company | Stabilized aliphatic polyester compositions |
ATE478915T1 (de) * | 2005-04-07 | 2010-09-15 | Cytec Tech Corp | Zusammensetzungen und verfahren zur verhinderung des lichtzerfalls zyklischer olefin-copolymere |
ITMI20052067A1 (it) * | 2005-10-28 | 2007-04-29 | 3V Sigma Spa | Composizione per la stabilizzazione di polimeri sintetici |
US20070174972A1 (en) * | 2005-11-14 | 2007-08-02 | Invista North America S.A R.I. | Spandex having enhanced whiteness, and fabrics and garments comprising the same |
RU2424256C2 (ru) * | 2006-08-04 | 2011-07-20 | Плейтекс Продактс, Инк. | Изделия с хорошей смазываемостью, аппликатор тампона, ствол и плунжер аппликатора тампона |
US20080306188A1 (en) * | 2007-06-06 | 2008-12-11 | Impact Composite Technology, Ltd. | Novel UV inhibitors and stabilizers, derived from a biomass feedstock source, for thermoplastic and thermosetting resins |
CN102292397B (zh) | 2009-01-19 | 2014-12-10 | 巴斯夫欧洲公司 | 有机黑色颜料及其制备 |
JP5556395B2 (ja) * | 2009-08-28 | 2014-07-23 | Jsr株式会社 | 液晶配向剤、液晶配向膜、液晶表示素子 |
GB0915687D0 (en) | 2009-09-08 | 2009-10-07 | Dupont Teijin Films Us Ltd | Polyester films |
KR20130100954A (ko) * | 2010-06-14 | 2013-09-12 | 이 아이 듀폰 디 네모아 앤드 캄파니 | 장기간 옥외 노출 저항성 폴리에스테르 복합 구조체 및 그의 제조 방법 |
JP2012134445A (ja) * | 2010-12-01 | 2012-07-12 | Fujifilm Corp | 保護フィルム |
JP2012116113A (ja) * | 2010-12-01 | 2012-06-21 | Fujifilm Corp | 保護フィルム |
KR102025299B1 (ko) * | 2010-12-13 | 2019-09-25 | 사이텍 테크놀러지 코포레이션 | 가공 첨가제 및 회전 성형에서의 이의 용도 |
US11267951B2 (en) | 2010-12-13 | 2022-03-08 | Cytec Technology Corp. | Stabilizer compositions containing substituted chroman compounds and methods of use |
GB2488787A (en) * | 2011-03-07 | 2012-09-12 | Dupont Teijin Films Us Ltd | Stabilised polyester films |
JP6010108B2 (ja) * | 2011-04-01 | 2016-10-19 | スリーエム イノベイティブ プロパティズ カンパニー | トリアジン系紫外線吸収剤を含むフィルム |
TWI454604B (zh) * | 2011-12-27 | 2014-10-01 | Ind Tech Res Inst | 分散性染料組成物、聚酯纖維材料的染色方法以及染色後的聚酯纖維材料 |
EP2647664A1 (en) * | 2012-04-04 | 2013-10-09 | Cytec Technology Corp. | Method for stabilizing polyolefin films against UV degradation |
GB201310837D0 (en) | 2013-06-18 | 2013-07-31 | Dupont Teijin Films Us Ltd | Polyester film -IV |
CN103289296A (zh) * | 2013-06-21 | 2013-09-11 | 苏州新区佳合塑胶有限公司 | 高耐候性阻燃abs复合材料 |
GB201317551D0 (en) | 2013-10-03 | 2013-11-20 | Dupont Teijin Films Us Ltd | Co-extruded polyester films |
EP3137540A1 (en) * | 2014-05-01 | 2017-03-08 | Cytec Industries Inc. | Stabilizing compositions for stabilizing materials against ultraviolet light and thermal degradation |
MY182679A (en) | 2014-06-24 | 2021-01-29 | Dow Global Technologies Llc | Polyolefin photovoltaic backsheet comprising a stabilized polypropylene layer |
KR101630161B1 (ko) * | 2014-07-25 | 2016-06-14 | 한국화학연구원 | 열안정성이 우수한 탄성 폴리우레탄의 중합 방법 및 이로부터 제조된 탄성 폴리우레탄 중합체 |
CA2968381C (en) | 2014-11-20 | 2023-10-17 | Cytec Industries Inc. | Stabilizer compositions and methods for using same for protecting polymeric organic materials from uv light and thermal degradation |
CN106589514B (zh) * | 2015-10-20 | 2020-03-24 | 天罡新材料(廊坊)股份有限公司 | 一种光稳定剂组合物母粒及其制备方法和应用 |
EP3470465A4 (en) * | 2016-06-09 | 2020-04-15 | Adeka Corporation | RESIN COMPOSITION |
US20200002493A1 (en) * | 2017-02-24 | 2020-01-02 | Solvay Specialty Polymers Usa, Llc | Uv-stabilizer solution for treating the surface layer of a polymer article |
WO2018155396A1 (ja) | 2017-02-27 | 2018-08-30 | 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 |
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 |
MX2019011625A (es) | 2017-03-28 | 2019-12-05 | Basf Se | Mezcla fotoestabilizante. |
CN110709455A (zh) * | 2017-06-26 | 2020-01-17 | Sabic环球技术有限责任公司 | Uv和热稳定的阻燃玻璃填充的聚合物组合物和由其制成的增强制品 |
EP3578599A1 (en) | 2018-06-08 | 2019-12-11 | Cytec Industries Inc. | Granular stabilizer compositions for use in polymer resins and methods of making same |
KR102602854B1 (ko) * | 2018-06-05 | 2023-11-16 | 주식회사 동진쎄미켐 | 폴리이미드 조성물 및 이를 이용하여 제조한 자외선 안정성이 우수한 폴리이미드 필름 |
CN111253655A (zh) * | 2019-12-23 | 2020-06-09 | 浙江瑞堂塑料科技股份有限公司 | 一种高耐候聚乙烯复合材料及其制备方法 |
US20220411646A1 (en) | 2021-06-29 | 2022-12-29 | Cytec Industries Inc. | Compositions and methods for protecting coatings from the deleterious effects of exposure to uv-c light |
AU2022429675A1 (en) | 2022-01-01 | 2024-07-04 | Cytec Industries Inc. | Polymer compositions having densification accelerators and rotational molding processes for making hollow articles therefrom |
WO2024083872A1 (en) | 2022-10-18 | 2024-04-25 | Cytec Industries Inc. | Synergistic stabilizer compositions and methods for using same for protecting organic materials from uv light and thermal degradation |
Family Cites Families (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL302933A (zh) * | 1963-01-24 | |||
US4331586A (en) * | 1981-07-20 | 1982-05-25 | American Cyanamid Company | Novel light stabilizers for polymers |
JPS58113236A (ja) * | 1981-12-28 | 1983-07-06 | Tounen Sekiyu Kagaku Kk | ポリオレフイン組成物 |
JPS61113649A (ja) * | 1984-11-07 | 1986-05-31 | Adeka Argus Chem Co Ltd | 耐光性の改善された高分子材料組成物 |
US4619956A (en) * | 1985-05-03 | 1986-10-28 | American Cyanamid Co. | Stabilization of high solids coatings with synergistic combinations |
US4929653A (en) * | 1987-07-13 | 1990-05-29 | The Bf Goodrich Company | Stabilized pigmented polypropylene fiber resistant to gas fade |
SG49847A1 (en) * | 1989-12-05 | 1999-07-20 | Ciba Sc Holding Ag | Stabilized organic material |
US5786477A (en) * | 1989-12-26 | 1998-07-28 | Cytec Technology Corp. | Stabilization of high solids coatings with liquid compositions of triazine UV absorbers |
CN1040006C (zh) † | 1990-03-23 | 1998-09-30 | 中国科学院长春应用化学研究所 | 耐候性聚乙烯薄膜的制备方法 |
DE59107052D1 (de) * | 1990-03-30 | 1996-01-25 | Ciba Geigy Ag | Lackzusammensetzungen |
DK0483488T3 (da) * | 1990-10-29 | 1997-04-01 | Cytec Tech Corp | Synergistiske ultravioletabsorberende sammensætninger indeholdende hydroxyaryltriaziner og tetraalkylpiperidiner |
US5190710A (en) * | 1991-02-22 | 1993-03-02 | The B. F. Goodrich Company | Method for imparting improved discoloration resistance to articles |
US5200443A (en) * | 1991-03-29 | 1993-04-06 | Kimberly-Clark Corporation | Radiation stabilized fabric having improved odor characteristics containing an hindered amine compound |
US5244947A (en) * | 1991-12-31 | 1993-09-14 | Kimberly-Clark Corporation | Stabilization of polyolefin nonwoven webs against actinic radiation |
ATE175731T1 (de) * | 1994-09-30 | 1999-01-15 | Ciba Geigy Ag | Stabilisierung von pigmentierten fasern mit einer synergistischen mischung von uv-absorber und gehindertem amin |
TW401437B (en) † | 1995-02-10 | 2000-08-11 | Ciba Sc Holding Ag | Synergistic stabilizer mixture |
GB9515048D0 (en) | 1995-07-22 | 1995-09-20 | Ciba Geigy Ag | Sunscreen compositions |
CH692739A5 (de) * | 1996-03-26 | 2002-10-15 | Ciba Sc Holding Ag | Polymerzusammensetzungen enthaltend 2-Hydroxyphenyl-1,3,5-triazine als UV-Absorber sowie neue 2-Hydroxyphenyl-1,3,5-triazine |
JP3932144B2 (ja) † | 1996-07-05 | 2007-06-20 | 株式会社Adeka | トリアジン系化合物、それからなる紫外線吸収剤及びそれを含む高分子材料組成物 |
US5840788A (en) * | 1997-06-20 | 1998-11-24 | Acushnet Company | Ultraviolet light resistant urethane top coat for golf balls |
US5844026A (en) * | 1997-06-30 | 1998-12-01 | Ciba Specialty Chemicals Corporation | N,N',N''-tris{2,4-bis Hydrocarbyloxy-2,2,6,6-tetra-methylpiperidin-4-yl)alkylamino!-s-triazin-6-yl}-3,3'-ethylenediiminodipropylamines, their isomers and bridged derivatives and polymer compositions stabilized therewith |
-
1998
- 1998-04-30 US US09/070,627 patent/US6051164A/en not_active Expired - Lifetime
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1999
- 1999-03-30 CN CNB998056596A patent/CN1154685C/zh not_active Ceased
- 1999-03-30 PT PT40779779T patent/PT1500675E/pt unknown
- 1999-03-30 EP EP99914266A patent/EP1080147B2/en not_active Expired - Lifetime
- 1999-03-30 IL IL13934899A patent/IL139348A0/xx active IP Right Grant
- 1999-03-30 BR BRPI9910062-2A patent/BR9910062B1/pt not_active IP Right Cessation
- 1999-03-30 AU AU32153/99A patent/AU740494B2/en not_active Expired
- 1999-03-30 RU RU2000130235/04A patent/RU2222560C2/ru active
- 1999-03-30 PT PT99914266T patent/PT1080147E/pt unknown
- 1999-03-30 CA CA002330422A patent/CA2330422C/en not_active Expired - Lifetime
- 1999-03-30 ES ES99914266T patent/ES2233030T5/es not_active Expired - Lifetime
- 1999-03-30 AT AT99914266T patent/ATE282061T1/de active
- 1999-03-30 KR KR1020007011989A patent/KR100608439B1/ko not_active IP Right Cessation
- 1999-03-30 WO PCT/US1999/006862 patent/WO1999057189A1/en active IP Right Grant
- 1999-03-30 JP JP2000547154A patent/JP2002513832A/ja not_active Withdrawn
- 1999-03-30 DE DE69921806T patent/DE69921806T3/de not_active Expired - Lifetime
- 1999-03-30 ES ES04077977.9T patent/ES2444366T3/es not_active Expired - Lifetime
- 1999-03-30 EP EP04077977.9A patent/EP1500675B1/en not_active Expired - Lifetime
- 1999-04-01 TW TW088105206A patent/TW555798B/zh not_active IP Right Cessation
- 1999-04-29 ZA ZA9903008A patent/ZA993008B/xx unknown
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2000
- 2000-10-27 NO NO20005413A patent/NO319839B1/no not_active IP Right Cessation
- 2000-10-30 IL IL139348A patent/IL139348A/en not_active IP Right Cessation
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2008
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102939348A (zh) * | 2010-05-14 | 2013-02-20 | 富士胶片映像着色有限公司 | 印刷方法、聚合物和油墨 |
CN110997801A (zh) * | 2017-08-02 | 2020-04-10 | 花王株式会社 | 聚合物乳液 |
CN111690257A (zh) * | 2020-07-02 | 2020-09-22 | 中国地质大学(北京) | 耐紫外辐照无色透明聚酰亚胺薄膜及其制备方法和应用 |
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