TW202231768A - 添加劑混合物 - Google Patents
添加劑混合物 Download PDFInfo
- Publication number
- TW202231768A TW202231768A TW110146090A TW110146090A TW202231768A TW 202231768 A TW202231768 A TW 202231768A TW 110146090 A TW110146090 A TW 110146090A TW 110146090 A TW110146090 A TW 110146090A TW 202231768 A TW202231768 A TW 202231768A
- Authority
- TW
- Taiwan
- Prior art keywords
- bis
- tris
- hydroxy
- tetramethyl
- piperidinyl
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 202
- 239000000654 additive Substances 0.000 title claims abstract description 107
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- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 claims description 3
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Abstract
目前所主張之本發明係關於包含式(1)化合物及式(2)化合物之添加劑混合物。目前所主張之本發明係進一步關於一種包含對氧化、熱或光誘發性降解敏感之有機材料及該等添加劑混合物之組合物。目前所主張之本發明亦係關於一種用於藉由將該等添加劑混合物併入其中或施加至其中來穩定有機材料之方法。此外,目前所主張之本發明係關於該等添加劑混合物作為有機材料之光穩定劑之用途。
Description
目前所主張之發明係關於一種包含式(1)化合物及式(2)化合物之添加劑混合物。目前所主張之本發明係進一步關於包含對氧化、熱或光誘發性降解敏感之有機材料及添加劑混合物的組合物。目前所主張之本發明亦係關於一種藉由將添加劑混合物併入其中或施加至其中來穩定有機材料之方法。此外,目前所主張之本發明係關於添加劑混合物作為有機材料之光穩定劑之用途。
有機材料,即諸如聚烯烴、聚乙烯、聚丙烯及其類似者之合成聚合物由於其易用於製造各種擠壓及模製物品而用於廣泛各種應用中。然而,此等物品時常由於重複曝露於UV光而受一般穩定性影響。此外,電流穩定系統,亦即抗刮痕劑改良之有機材料,在用於製備汽車物品時展示由於此等物品重複曝露於UV光而導致之起霜(bloom)/滲出。起霜/滲出為不合需要的,此係由於其可能破壞用起霜聚合物製成之物品之美感表面特性。在需要清晰之情況下,對於在物品中發生起霜尤其不合需要。起霜亦為不合需要的,因為其會降低用起霜聚合物製成之物品利用黏著劑牢固地結合至其他物品之能力。在一些應用中起霜已公認為嚴重問題,且已搜尋用於緩解其之有效方式多年。
因此,保持諸如聚合物在曝露於UV光時之穩定性的性質及減小聚合物起霜之傾向係特別需要的。
因此,本發明之目標為提供使對氧化、熱或光誘發性降解敏感之有機材料穩定之添加劑混合物。
本發明之另一目標為提供一種添加劑混合物,其在用於有機材料中時會提供對有機材料物品不展示黏性且不展示有機材料物品起霜/滲出的表面。
出人意料地,已發現含有根據目前所主張之本發明之某些化合物之添加劑混合物使對氧化、熱或光誘發性降解敏感之有機材料穩定。目前所主張之本發明之添加劑混合物在用於有機材料時會提供對有機材料物品不展示黏性且不展示有機材料物品起霜/滲出的表面。
因此,在一個態樣中,目前所主張之本發明係關於一種包含式(1)化合物及式(2)化合物之添加劑混合物
,
,
其中
A
1為直鏈或分支鏈、經取代或未經取代之C
1至C
20烷基,且
A
2為直鏈或分支鏈、經取代或未經取代之C
1至C
30烷基。
在另一態樣中,目前所主張之本發明係關於一種組合物,其包含
a)有機材料,其對氧化、熱或光誘發性降解敏感;及
b)添加劑混合物,如上所定義。
在另一態樣中,目前所主張之本發明係關於一種汽車內部或外部材料,其由包含有機材料及如上所定義之添加劑混合物之組合物製成。
在另一態樣中,目前所主張之本發明係關於一種用於穩定對氧化、熱或光誘發性降解敏感之有機材料之方法,其包含將如上文所定義之添加劑混合物併入其中或施加至其中。
在再一態樣中,目前所主張之本發明係關於添加劑混合物作為對光誘發性降解敏感之有機材料之光穩定劑之用途。
在描述本發明組合物及本發明之調配物之前,應瞭解本發明不限於特定組合物及所描述之調配物,因為此類組合物及調配物當然可變化。亦應理解,本文中所使用之術語不意欲為限制性的,因為目前所主張之本發明之範疇將僅受隨附申請專利範圍限制。
若在下文中定義一群組包含至少一定數量之實施例,則其意謂亦涵蓋較佳地僅由此等實施例組成之群組。此外,說明書及申請專利範圍中之術語「第一」、「第二」、「第三」或「(a)」、「(b)」、「(c)」、「(d)」等及其類似者用於類似要素之間的區分且未必描述序列或時間次序。應理解,如此使用之術語在適當情況下可互換,且本文所描述之本發明之實施例能夠以本文所描述或說明的順序之外的其他順序操作。除非如上文或下文所闡述之本申請案另外指示,否則在術語「第一」、「第二」、「第三」、或「(A)」、「(B)」及「(C)」或「(a)」、「(b)」、「(c)」、「(d)」、「i」、「ii」等與方法或使用或分析之步驟相關的情況下,在步驟之間不存在時間或時間間隔一致性,亦即,步驟可同時進行,或在此類步驟之間可存在數秒、數分鐘、數小時、數天、數週、數月或甚至數年之時間間隔。
在以下段落中,更詳細地定義本發明之不同態樣。除非相反地清楚指示,否則如此定義之每一態樣可與任何其他態樣組合。特定言之,指示為較佳或有利之任何特徵可與指示為較佳或有利之任何其他一或多個特徵組合。
貫穿本說明書對「一個實施例」或「較佳實施例」之引用意謂結合實施例描述之特定特徵、結構或特性包括於目前所主張之本發明之至少一個實施例中。因此,貫穿本說明書在各種位置出現之片語「在一個實施例中」或「在一較佳實施例中」或「在另一實施例中」未必皆指代同一實施例,而是可能指代。此外,如熟習此項技術者將自本發明之一或多個實施例顯而易見,特定特徵、結構或特性可以任何適合方式組合。此外,當本文所描述之一些實施例包括一些特徵而非包括於其他實施例中之其他特徵時,不同實施例之特徵之組合意謂在本發明之範疇內且形成不同實施例,如熟習此項技術者所瞭解。舉例而言,在隨附申請專利範圍中,所主張之實施例中之任一者可以任何組合形式使用。
此外,貫穿說明書定義之範圍亦包括端值,亦即1至10之範圍意指1及10皆包括於範圍中。為避免疑義,申請人應授權根據可適用法律獲得任何等效者。
首先定義某些術語使得本發明可更容易理解。除非另外定義,否則本文中所使用的所有技術及科學術語均具有與一般熟習本發明之實施例所屬領域的此項技術者通常所理解相同的含義。
在一態樣中,目前所主張之發明係關於一種包含式(1)化合物及式(2)化合物之添加劑混合物
,
,
其中
A
1為直鏈或分支鏈、經取代或未經取代之C
1至C
20烷基,且
A
2為直鏈或分支鏈、經取代或未經取代之C
1至C
30烷基。
在一較佳實施例中,A
1為直鏈或分支鏈、經羥基取代之C
1至C
20烷基。
在一實施例中,A
1之烷基取代基係選自由以下組成之群:甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一基、十二基、十三基、十四基、十五基、十六基、十七基、十八基、十九基及二十基。
在一較佳實施例中,A
1為2-羥基-2-甲基丙基。
在一較佳實施例中,A
2為直鏈或分支鏈、未經取代之C
1至C
30烷基。
在一實施例中,A
2之烷基取代基係選自由以下組成之群:甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一基、十二烷基、十三基、十四基、十五基、十六基、十七基、十八基、十九基、二十基、二十一基、二十二基、二十三基、二十四基、二十五基、二十六基、二十七基、二十八基、二十九基及三十基。
在一較佳實施例中,A
2係選自十五基及十七基。
在一最佳實施例中,式(2)化合物為1-(2-羥基-2-甲基丙氧基)-4-十八醯氧基-2,2,6,6-四甲基哌啶。
在一實施例中,式(1)化合物與式(2)化合物之重量比在5:95至95:5,較佳地10:90至90:10,更佳地20:80至80:20,甚至更佳地30:70至70:30,仍更佳地40:60至60:40之範圍內,且最佳地50:50。
在目前所主張之本發明之另一個實施例中,添加劑混合物包含式(1)化合物、式(2)化合物及選自受阻胺光穩定劑之群的至少一種化合物。
受阻胺光穩定劑係選自由以下組成之群:碳酸雙(1-十一烷氧基-2,2,6,6-四甲基-4-哌啶基)酯、雙(2,2,6,6-四甲基-4-哌啶基)癸二酸酯、雙(2,2,6,6-四甲基-4-哌啶基)丁二酸酯、雙(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯、雙(1-辛氧基-2,2,6,6-四甲基-4-哌啶基)癸二酸酯、正丁基-3,5-二-三級丁基-4-羥基苯甲基丙二酸雙(1,2,2,6,6-五甲基-4-哌啶基)酯、1-(2-羥基乙基)-2,2,6,6-四甲基-4-羥基哌啶與丁二酸之縮合物、N,N'-雙(2,2,6,6-四甲基-4-哌啶基)六亞甲基二胺及4-三級辛基胺基-2,6-二氯-1,3,5-三𠯤之直鏈或環狀縮合物、參(2,2,6,6-四甲基-4-哌啶基)氮基三醋酸酯、肆(2,2,6,6-四甲基-4-哌啶基)-1,2,3,4-丁烷四羧酸酯、1,1'-(1,2-乙二基)-雙(3,3,5,5-四甲基哌𠯤酮)、4-苯甲醯基-2,2,6,6-四甲基哌啶、4-硬脂醯氧基-2,2,6,6-四甲基哌啶、雙(1,2,2,6,6-五甲基哌啶基)-2-正丁基-2-(2-羥基-3,5-二-三級丁基苯甲基)丙二酸酯、3-正辛基-7,7,9,9-四甲基-1,3,8-三氮雜螺[4.5]癸烷-2,4-二酮、雙(1-辛氧基-2,2,6,6-四甲基哌啶基)癸二酸酯、雙(1-辛氧基-2,2,6,6-四甲基哌啶基)丁二酸酯、N,N'-雙(2,2,6,6-四甲基-4-哌啶基)六亞甲基二胺及4-N-𠰌啉基-2,6-二氯-1,3,5-三𠯤之直鏈或環狀縮合物、2-氯-4,6-雙(4-正丁胺基-2,2,6,6-四甲基哌啶基)-1,3,5-三𠯤與1,2-雙(3-胺基丙胺基)乙烷之縮合物、2-氯-4,6-二(4-正丁胺基-1,2,2,6,6-五甲基哌啶基)-1,3,5-三𠯤與1,2-雙(3-胺基丙胺基)乙烷之縮合物、8-乙醯基-3-十二基-7,7,9,9-四甲基-1,3,8-三氮雜螺[4.5]癸烷-2,4-二酮、3-十二基-1-(2,2,6,6-四甲基-4-哌啶基)吡咯啶-2,5-二酮、3-十二基-1-(1,2,2,6,6-五甲基-4-哌啶基)吡咯啶-2,5-二酮、4-十六烷氧基-2,2,6,6-四甲基哌啶與4-硬脂醯氧基-2,2,6,6-四甲基哌啶之混合物、N,N'-雙(2,2,6,6-四甲基-4-哌啶基)六亞甲基二胺與4-環己胺基-2,6-二氯-1,3,5-三𠯤之縮合物、1,2-雙(3-胺基丙胺基)乙烷及2,4,6-三氯-1,3,5-三𠯤與4-丁胺基-2,2,6,6-四甲基哌啶之縮合物;1,6-己二胺與2,4,6-三氯-1,3,5-三𠯤以及N,N-二丁胺與4-丁胺基-2,2,6,6-四甲基哌啶之縮合物;N-(2,2,6,6-四甲基-4-哌啶基)-正十二烷基丁二醯亞胺、N-(1,2,2,6,6-五甲基-4-哌啶基)-正十二烷基丁二醯亞胺、2-十一基-7,7,9,9-四甲基-1-氧雜-3,8-二氮雜-4-側氧基-螺[4,5]癸烷、7,7,9,9-四甲基-2-環十一烷基-1-氧雜-3,8-二氮雜-4-側氧基螺-[4,5]癸烷及環氧氯丙烷之反應產物、1,1-雙(1,2,2,6,6-五甲基-4-哌啶基氧基羰基)-2-(4-甲氧基苯基)乙烯、N,N'-雙甲醯基-N,N'-雙(2,2,6,6-四甲基-4-哌啶基)六亞甲基二胺、4-甲氧基亞甲基丙二酸與1,2,2,6,6-五甲基-4-羥基哌啶之二酯、聚[甲基丙基-3-氧基-4-(2,2,6,6-四甲基-4-哌啶基)]矽氧烷、順丁烯二酸酐-α烯烴共聚物與2,2,6,6-四甲基-4-胺基哌啶或1,2,2,6,6-五甲基-4-胺基哌啶之反應產物、2,4-雙[N-(1-環己氧基-2,2,6,6-四甲基哌啶-4-基)-N-丁胺基]-6-(2-羥基乙基)胺基-1,3,5-三𠯤、5-(2-乙基己醯基)氧基甲基-3,3,5-三甲基-2-𠰌啉酮、5-(2-乙基己醯基)氧基甲基-3,3,5-三甲基-2-𠰌啉酮、2,4-雙[(1-環己氧基-2,2,6,6-哌啶-4-基)丁胺基]-6-氯-對稱三𠯤與N,N'-雙(3-胺基丙基)乙二胺)之反應產物、1,3,5-參(N-環己基-N-(2,2,6,6-四甲基哌𠯤-3-酮-4-基)胺基)-對稱三𠯤、1,3,5-參(N-環己基-N-(1,2,2,6,6-五甲基哌𠯤-3-酮-4-基)胺基)-對稱三𠯤、4-N-丁基-2-N,4-N-雙(2,2,6,6-四甲基哌啶-4-基)-2-N-[6-[(2,2,6,6-四甲基哌啶-4-基)胺基]己基]-1,3,5-三𠯤-2,4-二胺、N,N'-雙(2,2,6,6-四甲基-4-哌啶基)-N,N-二甲醯基六亞甲基二胺及其混合物。
在一較佳實施例中,受阻胺光穩定劑為以下:
其中a
1為2至10,
,
其中b
1為2至20,較佳地2至10之數目,
其中a
1為2至10,
其中a
1為2至10,
其中X
1、X
2、X
3、X
4、X
5、X
6、X
7及X
8為基團
、
,
其中Y
1彼此獨立地為氫或丙氧基,較佳地丙氧基。
其中n為4至20,
。
在一實施例中,受阻胺光穩定劑係選自N,N'-雙(2,2,6,6-四甲基-4-哌啶基)-N,N'-二甲醯基六亞甲基二胺(C-I-9)、1,6-己二胺與2,4,6-三氯-1,3,5-三𠯤以及N,N-二丁胺與4-丁胺基-2,2,6,6-四甲基哌啶之縮合物(C-I-1)、1-(2-羥基乙基)-2,2,6,6-四甲基-4-羥基哌啶與丁二酸之縮合物及其混合物。
在一較佳實施例中,受阻胺光穩定劑係選自N,N'-雙(2,2,6,6-四甲基-4-哌啶基)-N,N'-二甲醯基六亞甲基二胺(C-I-9)、1,6-己二胺與2,4,6-三氯-1,3,5-三𠯤以及N,N-二丁胺與4-丁胺基-2,2,6,6-四甲基哌啶之縮合物(C-I-1)及其混合物。
在一更佳實施例中,受阻胺光穩定劑為1,6-己二胺與2,4,6-三氯-1,3,5-三𠯤以及N,N-二丁胺與4-丁胺基-2,2,6,6-四甲基哌啶之縮合物(C-I-1)。
在一最佳實施例中,受阻胺光穩定劑為N,N'-雙(2,2,6,6-四甲基-4-哌啶基)-N,N'-二甲醯基六亞甲基二胺(C-I-9)。
在目前所主張之本發明之另一實施例中,添加劑混合物包含式(1)化合物、式(2)化合物及選自羥苯基三𠯤UV吸收劑之群的至少一種化合物。
羥苯基三𠯤UV吸收劑係選自由以下組成之群:2,4,6-參(2-羥基-4-辛氧基苯基)-1,3,5-三𠯤、2-(2-羥基-4-辛氧基苯基)-4,6-雙(2,4-二甲基苯基)-1,3,5-三𠯤、2-(2,4-二羥基苯基)-4,6-雙(2,4-二甲基苯基)-1,3,5-三𠯤、2,4-雙(2-羥基-4-丙氧基苯基)-6-(2,4-二甲基苯基)-1,3,5-三𠯤、2-(2-羥基-4-辛氧基苯基)-4,6-雙(4-甲基苯基)-1,3,5-三𠯤、2-(2-羥基-4-十二烷氧基苯基)-4,6-雙(2,4-二甲基苯基)-1,3,5-三𠯤、2-(2-羥基-4-十三烷氧基苯基)-4,6-雙(2,4-二甲基苯基)-1,3,5-三𠯤、2-[2-羥基-4-(2-羥基-3-丁氧基丙氧基)苯基]-4,6-雙(2,4-二甲基)-1,3,5-三𠯤、2-[2-羥基-4-(2-羥基-3-辛氧基丙氧基)苯基]-4,6-雙(2,4-二甲基)-1,3,5-三𠯤、2-[4-(十二烷氧基/十三烷氧基-2-羥基丙氧基)-2-羥苯基]-4,6-雙(2,4-二甲基苯基)-1,3,5-三𠯤、2-[2-羥基-4-(2-羥基-3-十二烷氧基丙氧基)苯基]-4,6-雙(2,4-二甲基苯基)-1,3,5-三𠯤、2-(2-羥基-4-己氧基)苯基-4,6-二苯基-1,3,5-三𠯤、2-(2-羥基-4-甲氧基苯基)-4,6-二苯基-1,3,5-三𠯤、2,4,6-參[2-羥基-4-(3-丁氧基-2-羥基丙氧基)苯基]-1,3,5-三𠯤、2-(2-羥苯基)-4-(4-甲氧基苯基)-6-苯基-1,3,5-三𠯤、2-{2-羥基-4-[3-(2-乙基己基-1-氧基)-2-羥基丙氧基]苯基}-4,6-雙(2,4-二甲基苯基)-1,3,5-三𠯤、2,4-雙(4-[2-乙基己氧基]-2-羥苯基)-6-(4-甲氧基苯基)-1,3,5-三𠯤、2-(4,6-雙聯苯基-4-基-1,3,5-三𠯤-2-基)-5-(2-乙基-(正)-己氧基)酚及其混合物。
在一更佳實施例中,羥苯基三𠯤UV吸收劑為式(C-II-1)化合物及式(C-II-3)化合物,尤其式(C-II-1)化合物。
在目前所主張之本發明之另一實施例中,添加劑混合物包含式(1)化合物、式(2)化合物及式(C-I-8)化合物。
在另一態樣中,目前所主張之本發明係關於一種組合物,其包含
a)有機材料,其對氧化、熱或光誘發性降解敏感;及
b)添加劑混合物,如前文所定義。
可穩定化之有機材料之實例為:
1.單烯烴及二烯烴之聚合物,例如聚丙烯、聚異丁烯、聚丁-1-烯、聚-4-甲基戊-1-烯、聚乙烯基環己烷、聚異戊二烯或聚丁二烯,以及環烯烴之聚合物,例如環戊烯或降冰片烯之聚合物,聚乙烯(其視情況可交聯),例如高密度聚乙烯(HDPE)、高密度及高分子量聚乙烯(HDPE-HMW)、高密度及超高分子量聚乙烯(HDPE-UHMW)、中密度聚乙烯(MDPE)、低密度聚乙烯(LDPE)、線性低密度聚乙烯(LLDPE)、(VLDPE)及(ULDPE)。
聚烯烴(亦即前段中所例示之單烯烴之聚合物,較佳為聚乙烯及聚丙烯)可藉由不同方法且尤其藉由以下方法製備:
a) 基團聚合(通常在高壓下及高溫下)。
b) 使用通常含有週期表之第IVb族、第Vb族、第VIb族或第VIII族之一種或多於一種金屬的催化劑之催化性聚合。此等金屬通常具有一個或多於一個配位體,通常為氧化物、鹵化物、醇化物、酯、醚、胺、烷基、烯基及/或芳基,其可經π-配位或σ-配位。此等金屬錯合物可呈游離形式或固定於受質上,通常固定於活化氯化鎂、氯化鈦(III)、氧化鋁或氧化矽上。此等催化劑可溶於或不可溶於聚合介質中。在聚合中可單獨使用催化劑或可使用其他活化劑,該等活化劑通常為金屬烷基、金屬氫化物、金屬烷基鹵化物、金屬烷基氧化物或金屬烷基氧烷,該等金屬為週期表之第Ia族、第IIa族及/或第IIIa族元素。活化劑可適宜地經其他酯、醚、胺或矽基醚基團改質。此等催化劑系統通常稱為Phillips、Standard Oil Indiana、Ziegler (-Natta)、TNZ (DuPont)、茂金屬或單一位點催化劑(SSC)。
2.1)項所提及之聚合物之混合物,例如聚丙烯與聚異丁烯、聚丙烯與聚乙烯之混合物(例如PP/HDPE、PP/LDPE)及不同類型的聚乙烯之混合物(例如LDPE/HDPE)。
3.單烯烴及二烯烴彼此或與其他乙烯基單體之共聚物,例如乙烯/丙烯共聚物,線型低密度聚乙烯(LLDPE)及其與低密度聚乙烯(LDPE)之混合物,丙烯/丁-1-烯共聚物、丙烯/異丁烯共聚物、乙烯/丁-1-烯共聚物、乙烯/己烯共聚物、乙烯/甲基戊烯共聚物、乙烯/庚烯共聚物、乙烯/辛烯共聚物、乙烯/乙烯基環己烷共聚物、乙烯/環烯烴共聚物(例如乙烯/降冰片烯,如COC)、乙烯/1-烯烴共聚物(其中1-烯烴係原位生成);丙烯/丁二烯共聚物、異丁烯/異戊二烯共聚物、乙烯/乙烯基環己烯共聚物、乙烯/丙烯酸烷酯共聚物、乙烯/甲基丙烯酸烷酯共聚物、乙烯/乙酸乙烯酯共聚物或乙烯/丙烯酸共聚物及其鹽(離聚物)以及乙烯與丙烯及諸如己二烯、二環戊二烯或亞乙基-降冰片烯之二烯的三元共聚物;及該等共聚物彼此及與以上1)項中所提及之聚合物的混合物,例如聚丙烯/乙烯-丙烯共聚物、LDPE/乙烯-乙酸乙烯酯共聚物(EVA)、LDPE/乙烯-丙烯酸共聚物(EAA)、LLDPE/EVA、LLDPE/EAA及交替或無規聚烯/一氧化碳共聚物及其與例如聚醯胺之其他聚合物之混合物。
4.烴類樹脂(例如C
5至C
9),包括其氫化改質(例如增黏劑)及聚烯與澱粉之混合物。
來自1.)至4.)項之均聚物及共聚物可具有包括間規、等規、半等規或非規之任何立體結構;其中非規聚合物較佳。亦包括立體嵌段聚合物。
5.聚苯乙烯、聚(對甲基苯乙烯)、聚(α-甲基苯乙烯)。
6.衍生自乙烯基芳族單體之芳族均聚物及共聚物,包括苯乙烯、α-甲基苯乙烯、乙烯基甲苯之所有異構體(尤其對乙烯基甲苯),乙基苯乙烯、丙基苯乙烯、乙烯基聯苯、乙烯基萘及乙烯基蒽之所有異構體及其混合物。均聚物及共聚物可具有包括間規、等規、半等規或非規之任何立體結構;其中非規聚合物為較佳。亦包括立體嵌段聚合物。
6a.包括前述乙烯基芳族單體及選自以下之共聚單體之共聚物:乙烯、丙烯、二烯、腈、酸、順丁烯二酸酐、順丁烯二醯亞胺、乙酸乙烯酯及氯乙烯或丙烯酸衍生物及其混合物,例如苯乙烯/丁二烯、苯乙烯/丙烯腈、苯乙烯/乙烯(互聚物)、苯乙烯/甲基丙烯酸烷酯、苯乙烯/丁二烯/丙烯酸烷酯、苯乙烯/丁二烯/甲基丙烯酸烷酯、苯乙烯/順丁烯二酸酐、苯乙烯/丙烯腈/丙烯酸甲酯;具有高衝擊強度之苯乙烯共聚物與另一聚合物,例如聚丙烯酸酯、二烯聚合物或乙烯/丙烯/二烯三元共聚物之混合物;及苯乙烯之嵌段共聚物,諸如苯乙烯/丁二烯/苯乙烯、苯乙烯/異戊二烯/苯乙烯、苯乙烯/乙烯/丁烯/苯乙烯或苯乙烯/乙烯/丙烯/苯乙烯。
6b.衍生自6.)項所提及之聚合物之氫化的氫化芳族聚合物,尤其包括藉由氫化非規聚苯乙烯製備之聚環己基乙烯(PCHE),通常稱為聚乙烯環己烷(PVCH)。
6c.衍生自6a.)項所提及之聚合物之氫化的氫化芳族聚合物。
均聚物及共聚物可具有包括間規、等規、半等規或非規之任何立體結構;其中非規聚合物為較佳。亦包括立體嵌段聚合物。
7.諸如苯乙烯或α-甲基苯乙烯之乙烯基芳族單體之接枝共聚物,例如苯乙烯於聚丁二烯上、苯乙烯於聚丁二烯-苯乙烯或聚丁二烯-丙烯腈共聚物上;苯乙烯及丙烯腈(或甲基丙烯腈)於聚丁二烯上;苯乙烯、丙烯腈及甲基丙烯酸甲酯於聚丁二烯上;苯乙烯及順丁烯二酸酐於聚丁二烯上;苯乙烯、丙烯腈及順丁烯二酸酐或順丁烯二醯亞胺於聚丁二烯上;苯乙烯及順丁烯二醯亞胺於聚丁二烯上;苯乙烯及丙烯酸烷酯或甲基丙烯酸烷酯於聚丁二烯上;苯乙烯及丙烯腈於乙烯/丙烯/二烯三元共聚物上;苯乙烯及丙烯腈於聚丙烯酸烷酯或聚甲基丙烯酸烷酯上、苯乙烯及丙烯腈於丙烯酸酯/丁二烯共聚物上,以及其與6)項所列出之共聚物之混合物,例如稱為ABS、MBS、ASA或AES聚合物之共聚物混合物。
8.含鹵素聚合物,諸如聚氯丁二烯、氯化橡膠、異丁烯-異戊二烯之氯化及溴化共聚物(鹵丁基橡膠)、氯化或磺氯化聚乙烯、乙烯及氯化乙烯之共聚物、表氯醇均聚物及共聚物,尤其含鹵素乙烯基化合物之聚合物,例如聚氯乙烯、聚偏二氯乙烯、聚氟乙烯、聚偏二氟乙烯以及其共聚物,諸如氯乙烯/偏二氯乙烯、氯乙烯/乙酸乙烯酯或偏二氯乙烯/乙酸乙烯酯共聚物。
9.衍生自α,β-不飽和酸及其衍生物之聚合物,諸如聚丙烯酸酯及聚甲基丙烯酸酯;聚甲基丙烯酸甲酯、聚丙烯醯胺及聚丙烯腈,經丙烯酸丁酯衝擊改質。
10.9)項所提及之單體彼此之間或與其他不飽和單體之共聚物,例如丙烯腈/丁二烯共聚物、丙烯腈/丙烯酸烷酯共聚物、丙烯腈/丙烯酸烷氧基烷酯或丙烯腈/鹵化乙烯共聚物或丙烯腈/甲基丙烯酸烷酯/丁二烯三元共聚物。
11.衍生自不飽和醇及胺或其醯基衍生物或縮醛之聚合物,例如聚乙烯醇、聚乙酸乙烯酯、聚硬脂酸乙烯酯、聚苯甲酸乙烯酯、聚順丁烯二酸乙烯酯、聚乙烯縮丁醛、聚鄰苯二甲酸烯丙酯或聚烯丙基三聚氰胺;以及其與以上1)項中所提及之烯烴之共聚物。
12.環醚之均聚物及共聚物,諸如聚伸烷二醇、聚氧化乙烯、聚氧化丙烯或其與雙縮水甘油醚之共聚物。
13.聚縮醛,諸如聚甲醛及含有氧化乙烯作為共聚單體之彼等聚甲醛;經熱塑性聚胺甲酸酯、丙烯酸酯或MBS改質之聚縮醛。
14.聚苯醚及聚苯硫醚,及聚苯醚與苯乙烯聚合物或聚醯胺之混合物。
15.一方面自羥基封端之聚醚、聚酯或聚丁二烯及另一方面自脂族或芳族聚異氰酸酯以及其前體衍生之聚胺甲酸酯。
16.自二胺及二羧酸及/或自胺基羧酸或對應內醯胺衍生之聚醯胺及共聚醯胺,例如聚醯胺4、聚醯胺6、聚醯胺6/6、6/10、6/9、6/12、4/6、12/12、聚醯胺11、聚醯胺12、以間二甲苯二胺及己二酸為起始物之芳族聚醯胺;由六亞甲基二胺及間苯二甲酸或/及對苯二甲酸製備且具有或不具有彈性體作為改質劑之聚醯胺,例如聚2,4,4-三甲基六亞甲基對苯二甲醯胺或聚間伸苯基間苯二甲醯胺;以及上述聚醯胺與聚烯烴、烯烴共聚物、離子聚合物或化學鍵結或接枝之彈性體的嵌段共聚物;或與聚醚之嵌段共聚物,例如與聚乙二醇、聚丙二醇或聚丁二醇之嵌段共聚物;以及經EPDM或ABS改質之聚醯胺或共聚醯胺;及在加工期間縮合之聚醯胺(RIM聚醯胺系統)。
17.聚脲、聚醯亞胺、聚醯胺-醯亞胺、聚醚醯亞胺、聚酯醯亞胺、聚乙內醯脲及聚苯并咪唑。
18.衍生自二羧酸及二醇及/或衍生自羥基羧酸或對應內酯或丙交酯之聚酯,例如聚對苯二甲酸伸乙酯、聚對苯二甲酸伸丁酯、聚-1,4-二羥甲基環己烷對苯二甲酸酯、聚萘二甲酸伸烷酯及聚羥基苯甲酸酯,以及衍生自羥基封端之聚醚之共聚醚酯,以及經聚碳酸酯或MBS改質之聚酯。共聚酯可包含例如(但不限於)聚丁二酸伸丁酯/對苯二甲酯、聚己二酸伸丁酯/對苯二甲酸酯、聚己二酸四亞甲基酯/對苯二甲酸酯、聚丁二酸伸丁酯/己二酸酯、聚丁二酸伸丁酯/碳酸酯、聚-3-羥基丁酸酯/辛酸酯共聚物、聚-3-羥基丁酸酯/己酸酯/癸酸酯三元共聚物。此外,脂族聚酯可包含例如(但不限於)聚(羥基烷酸酯)類,特定言之聚(丙內酯)、聚(丁內酯)、聚(特戊內酯)、聚(戊內酯)及聚(己內酯),聚丁二酸伸乙酯、聚丁二酸伸丙酯、聚丁二酸伸丁酯、聚丁二酸伸己酯、聚己二酸伸乙酯、聚己二酸伸丙酯、聚己二酸伸丁酯、聚己二酸伸己酯、聚草酸伸乙酯、聚草酸伸丙酯、聚草酸伸丁酯、聚草酸伸己酯、聚癸二酸伸乙酯、聚癸二酸伸丙酯、聚癸二酸伸丁酯及聚乳酸(PLA)以及經聚碳酸酯或MBS改質之對應聚酯。術語「聚乳酸(PLA)」表示較佳聚L-乳酸交酯之均聚物及其與其他聚合物之任何摻合物或混合物(alloy);乳酸或乳酸交酯與諸如以下其他單體之共聚物:羥基-羧酸,如(例如)乙醇酸、3-羥基-丁酸、4-羥基-丁酸、4-羥基-戊酸、5-羥基-戊酸、6-羥基-己酸及其環狀形式;術語「乳酸」或「乳酸交酯」包括L-乳酸、D-乳酸、其混合物及二聚體,亦即L-乳酸交酯、D-乳酸交酯、內消旋乳酸交酯及其任何混合物。
19.聚碳酸酯及聚酯碳酸酯。
20.聚酮。
21.聚碸、聚醚碸及聚醚酮。
22.一方面衍生自醛類且另一方面衍生自酚類、脲及三聚氰胺之交聯聚合物,諸如酚/甲醛樹脂、脲/甲醛樹脂及三聚氰胺/甲醛樹脂。
23.乾性及非乾性醇酸樹脂。
24.自飽和及不飽和二羧酸與多元醇之共聚酯且以乙烯基化合物作為交聯劑衍生之不飽和聚酯樹脂,以及其低可燃性的含鹵素改質。
25.自經取代之丙烯酸酯衍生之可交聯丙烯酸樹脂,例如環氧丙烯酸酯、丙烯酸胺基甲酸酯或丙烯酸聚酯。
26.與三聚氰胺樹脂、脲樹脂、異氰酸酯、異氰脲酸酯、聚異氰酸酯或環氧樹脂交聯之醇酸樹脂、聚酯樹脂及丙烯酸酯樹脂。
27.自脂族、環脂族、雜環或芳族縮水甘油基化合物衍生之交聯環氧樹脂,例如雙酚A及雙酚F之二縮水甘油基醚產物,其在存在或不存在促進劑的情況下與習知硬化劑(諸如酸酐或胺)交聯。
28.天然聚合物,諸如纖維素、橡膠、明膠及其經化學改質之同源衍生物,例如乙酸纖維素、丙酸纖維素及丁酸纖維素,或諸如甲基纖維素之纖維素醚;以及松香及其衍生物。
29.前述聚合物之摻合物(聚摻合物),例如PP/EPDM、聚醯胺/EPDM或ABS、PVC/EVA、PVC/ABS、PVC/MBS、PC/ABS、PBTP/ABS、PC/ASA、PC/PBT、PVC/CPE、PVC/丙烯酸酯、POM/熱塑性PUR、PC/熱塑性PUR、POM/丙烯酸酯、POM/MBS、PPO/HIPS、PPO/PA6.6及共聚物、PA/HDPE、PA/PP、PA/PPO、PBT/PC/ABS或PBT/PET/PC。
30.為純單體化合物或此類化合物之混合物的天然存在及合成有機材料,例如礦物油、動物及植物脂肪、油及蠟或基於合成酯(例如鄰苯二甲酸酯、己二酸酯、磷酸酯或偏苯三酸酯)之油、脂肪及蠟以及任何重量比之合成酯與礦物油之混合物,典型地用作自旋組合物之彼等物以及此類材料之水性乳液。
31.天然或合成橡膠之水性乳液,例如羧化苯乙烯/丁二烯共聚物之天然乳膠或膠乳。
聚烯烴、丙烯腈/丁二烯/苯乙烯、聚氯乙烯、聚甲基丙烯酸甲酯、聚醯胺或聚甲醛特別受關注。
在一較佳實施例,有機材料為熱塑性彈性體。
熱塑性彈性體之實例包括聚烯烴熱塑性彈性體及嵌段共聚物型聚苯乙烯熱塑性彈性體。聚烯烴熱塑性彈性體包含聚烯烴樹脂(諸如聚丙烯及聚乙烯)充當硬鏈段及橡膠組合物(諸如乙烯-丙烯-二烯-彈性體(EPDM))充當軟鏈段。嵌段共聚物型聚苯乙烯熱塑性彈性體包含聚苯乙烯充當硬鏈段及聚二烯(諸如聚丁二烯或聚異戊二烯)充當軟鏈段。
可替代地,聚烯烴彈性體及聚苯乙烯彈性體之摻合物亦可用作本發明之熱塑性彈性體。用於在熱塑性彈性體中組合軟鏈段及硬鏈段的方法可粗略地分成簡單摻合、藉由共聚合植入及動態交聯。聚苯乙烯熱塑性彈性體之鏈段組合包括苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)、苯乙烯-異戊二烯-苯乙烯嵌段共聚物(SIS)、苯乙烯-乙烯丁烯-苯乙烯嵌段共聚物(SEBS)、苯乙烯-乙烯丙烯-苯乙烯嵌段共聚物(SEPS)、四種共聚物中之任一者的氫化聚合物、無規SBR (HSBR)之氫化聚合物及聚丙烯與選自此等聚合物中之一或多個任意成員的摻合物(SBR=苯乙烯丁二烯橡膠)。
所關注的係熱塑性聚烯烴,特定言之含有基於乙烯及/或丙烯之橡膠相的聚乙烯或聚丙烯。
本發明之添加劑混合物可以各種比例使用,視待穩定化之有機材料的性質、最終用途及其他添加劑的存在而定。
大體而言,相對於有機材料之重量,適合使用例如0.01%至5.0重量%之本發明之添加劑混合物,較佳地0.01%至2.0%,特定言之0.01%至1.0%。極較佳為0.05%至2.0%,特定言之0.05%至1.0%。
在最佳實施例中,相對於有機材料之重量,使用0.6重量%之本發明之添加劑混合物。
在一實施例中,有機材料與添加劑混合物之重量比在99.99:0.01至1.0:99之範圍內,較佳地99.9:0.05至1.0:99。
在該等材料聚合或交聯之前、期間或之後,可將本發明之添加劑混合物添加至例如聚合材料中。此外,其可以純形式併入至聚合材料中或密封於蠟、油或聚合物中。
應理解,如上文所定義之添加劑混合物之化合物可作為混合物直接添加至有機材料中,或將個別化合物單獨地添加至有機材料中。
大體而言,本發明之添加劑混合物可藉由各種程序併入有機材料中,諸如以粉末形式進行乾式混合,或以溶液或懸浮液形式或亦以母料形式進行濕式混合,該母料含有濃度為0.01至99重量%之本發明之添加劑混合物;在此類操作中,聚合物可以粉末、顆粒、溶液、懸浮液形式或以膠乳形式使用。合適的載體聚合物為例如聚乙烯、聚丙烯或其混合物。
根據本發明之組合物的處理實例為:
注射吹塑模製、擠塑、吹塑模製、旋轉模製、模內裝飾(背部注入)、凝塑模製、注射模製、共注射模製、成型、壓縮模製、按壓、薄膜擠塑(流延薄膜;吹塑薄膜)、纖維紡絲(編織、非編織)、拉伸(單軸、雙軸)、退火、深拉伸、壓延、機械轉變、燒結、共擠塑、塗佈、層合、交聯(輻射、過氧化物、矽烷)、氣相沈積、焊接、膠接、硫化、熱成型、管擠塑、型面擠壓、全張擠壓;全張澆鑄、旋塗、搭接、發泡、再循環/返工、擠壓塗佈、減黏裂煉(過氧化物、熱)、纖維熔噴、紡黏、表面處理(電暈放電、火焰、電漿)、滅菌(藉由γ射線、電子射束)、凝膠塗佈、膠帶擠塑、SMC加工或塑性溶膠。
目前所主張之本發明之組合物進一步包含組分(C)抗刮痕劑、填充劑、顏料及其混合物。
抗刮痕添加劑之實例為飽和或不飽和脂肪酸醯胺,例如芥酸醯胺、油酸醯胺及硬脂醯胺以及聚(有機)矽氧烷及其混合物。
本發明之抗刮痕添加劑為熟習此項技術者已知。
其可以類似於已知方法來製備。其大多數可商購。
較佳可商購聚(有機)矽氧烷抗刮痕添加劑為:
TEGOMER® AntiScratch100,
TEGOMER
®M-Si 2650,
TEGOPREN
®6846,
TEGOMER
®H-Si 6440 P,
TEGOMER
®AntiScratch 200,
GENIOPLAST
®S,
GENIOPLAST®Pellet P及
GENIOPLAST
®Pellet P plus。
較佳聚(有機)矽氧烷抗刮痕添加劑係關於二氧化矽及聚矽氧聚合物之混合物(例如,0至50重量%,較佳地30重量%之煙霧狀二氧化矽及50至100重量%,較佳地70重量%之聚矽氧聚合物)。
另一較佳抗刮痕添加劑為IRGASURF
®SR 100。
目前所主張之本發明之組合物進一步包含習知添加劑。
習知添加劑之實例為:
1.
抗氧化劑
1.1. 烷基化單酚,例如2,6-二-三級丁基-4-甲苯酚、2-三級丁基-4,6-二甲苯酚、2,6-二-三級丁基-4-乙苯酚、2,6-二-三級丁基-4-正丁苯酚、2,6-二-三級丁基-4-異丁苯酚、2,6-二環戊基-4-甲苯酚、2-(α-甲基環己基)-4,6-二甲苯酚、2,6-二(十八基)-4-甲苯酚、2,4,6-三環己基苯酚、2,6-二-三級丁基-4-甲氧基甲苯酚;在側鏈中為直鏈或分支鏈之壬基苯酚,例如2,6-二壬基-4-甲苯酚、2,4-二甲基-6-(1'-甲基十一-1'-基)苯酚、2,4-二甲基-6-(1'-甲基十七-1'-基)苯酚、2,4-二甲基-6-(1'-甲基十三-1'-基)苯酚及其混合物。
1.2. 烷基硫基甲苯酚,例如2,4-二辛基硫基甲基-6-三級丁苯酚、2,4-二辛基硫基甲基-6-甲苯酚、2,4-二辛基硫基甲基-6-乙苯酚、2,6-二-十二基硫基甲基-4-壬苯酚。
1.3. 氫醌及烷基化氫醌,例如2,6-二-三級丁基-4-甲氧基苯酚、2,5-二-三級丁基氫醌、2,5-二-三級戊基氫醌、2,6-二苯基-4-十八烷氧基苯酚、2,6-二-三級丁基氫醌、2,5-二-三級丁基-4-羥基苯甲醚、3,5-二-三級丁基-4-羥基苯甲醚、硬脂酸3,5-二-三級丁基-4-羥苯酯、己二酸雙(3,5-二-三級丁基-4-羥苯基)酯。
1.4. 生育酚,例如α-生育酚、β-生育酚、γ-生育酚、δ-生育酚及其混合物(維生素E)。
1.5. 羥基化硫代二苯醚,例如2,2'-硫基雙(6-三級丁基-4-甲基苯酚)、2,2'-硫基雙(4-辛基苯酚)、4,4'-硫基雙(6-三級丁基-3-甲基苯酚)、4,4'-硫基雙(6-三級丁基-2-甲基苯酚)、4,4'-硫基雙(3,6-二-二級戊基苯酚)、4,4'-雙(2,6-二甲基-4-羥苯基)二硫化物。
1.6. 亞烷基雙酚,例如2,2'-亞甲基雙(6-三級丁基-4-甲苯酚)、2,2'-亞甲基雙(6-三級丁基-4-乙苯酚)、2,2'-亞甲基雙[4-甲基-6-(α-甲基環己基)苯酚]、2,2'-亞甲基雙(4-甲基-6-環己基苯酚)、2,2'-亞甲基雙(6-壬基-4-甲苯酚)、2,2'-亞甲基雙(4,6-二-三級丁苯酚)、2,2'-亞乙基雙(4,6-二-三級丁苯酚)、2,2'-亞乙基雙(6-三級丁基-4-異丁苯酚)、2,2'-亞甲基雙6-(α-甲基甲苯基)-4-壬苯酚]、2,2'-亞甲基雙[6-(α,α-二甲基苯甲基)-4-壬苯酚]、4,4'-亞甲基雙(2,6-二-三級丁苯酚)、4,4'-亞甲基雙(6-三級丁基-2-甲苯酚)、1,1-雙(5-三級丁基-4-羥基-2-甲基苯基)丁烷、2,6-雙(3-三級丁基-5-甲基-2-羥基苯甲基)-4-甲苯酚、1,1,3-參(5-三級丁基-4-羥基-2-甲基苯基)丁烷、1,1-雙(5-三級丁基-4-羥基-2-甲基-苯基)-3-正十二烷基巰基丁烷、乙二醇雙[3,3-雙(3'-三級丁基-4'-羥苯基)丁酸酯]、雙(3-三級丁基-4-羥基-5-甲基-苯基)二環戊二烯、雙[2-(3'-三級丁基-2'-羥基-5'-甲基苯甲基)-6-三級丁基-4-甲基苯基]對苯二甲酸酯、1,1-雙-(3,5-二甲基-2-羥苯基)丁烷、2,2-雙(3,5-二-三級丁基-4-羥苯基)丙烷、2,2-雙(5-三級丁基-4-羥基2-甲基苯基)-4-正十二烷基巰基丁烷、1,1,5,5-四-(5-三級丁基-4-羥基-2-甲基苯基)戊烷。
1.7. O- 苄基、 N- 苄基及 S- 苄基化合物,例如3,5,3',5'-四三級丁基-4,4'-二羥基二苄基醚、十八基-4-羥基-3,5-二甲基苄基巰基乙酸酯、十三基-4-羥基-3,5-二-三級丁基苄基巰基乙酸酯、參(3,5-二-三級丁基-4-羥基苄基)胺、雙(4-三級丁基-3-羥基-2,6-二甲基苄基)二硫對苯二甲酸酯、雙(3,5-二-三級丁基-4-羥基苄基)硫化物、異辛基-3,5-二-三級丁基-4-羥基苄基巰基乙酸酯。
1.8. 羥基苄基化丙二酸酯,例如二(十八基)-2,2-雙(3,5-二-三級丁基-2-羥基苄基)丙二酸酯、二-十八基-2-(3-三級丁基-4-羥基-5-甲基苄基)丙二酸酯、二-十二基巰基乙基-2,2-雙(3,5-二-三級丁基-4-羥基苄基)丙二酸酯、雙[4-(1,1,3,3-四甲基丁基)苯基]-2,2-雙(3,5-二-三級丁基-4-羥基苄基)丙二酸酯。
1.9. 芳族羥基苄基化合物,例如1,3,5-參(3,5-二-三級丁基-4-羥基苄基)-2,4,6-三甲苯、1,4-雙(3,5-二-三級丁基-4-羥基苄基)-2,3,5,6-四甲苯、2,4,6-參(3,5-二-三級丁基-4-羥基苄基)苯酚。
1.10. 三 𠯤 化合物,例如2,4-雙(辛基巰基)-6-(3,5-二-三級丁基-4-羥基苯胺基)-1,3,5-三𠯤、2-辛基巰基-4,6-雙(3,5-二-三級丁基-4-羥基苯胺基)-1,3,5-三𠯤、2-辛基巰基-4,6-雙(3,5-二-三級丁基-4-羥基苯氧基)-1,3,5-三𠯤、2,4,6-參(3,5-二-三級丁基-4-羥基苯氧基)-1,2,3-三𠯤、1,3,5-參(3,5-二-三級丁基-4-羥基苄基)異氰尿酸酯、1,3,5-參(4-三級丁基-3-羥基-2,6-二甲基苄基)異氰尿酸酯、2,4,6-參(3,5-二-三級丁基-4-羥基苯乙基)-1,3,5-三𠯤、1,3,5-參(3,5-二-三級丁基-4-羥基苯丙醯基)-六氫-1,3,5-三𠯤及1,3,5-參(3,5-二環己基-4-羥基苄基)異氰尿酸酯。
1.11. 苄基膦酸酯,例如二甲基-2,5-二-三級丁基-4-羥基苄基膦酸酯、二乙基-3,5-二-三級丁基-4-羥基苄基膦酸酯、二(十八基)3,5-二-三級丁基-4-羥基苄基膦酸酯、二(十八基)-5-三級丁基-4-羥基-3-甲基苄基膦酸酯、3,5-二-三級丁基-4-羥基苄基膦酸單乙酯之鈣鹽。
1.12. 醯胺基酚,例如4-羥基十二醯苯胺、4-羥基硬脂醯苯胺、N-(3,5-二-三級丁基-4-羥苯基)胺基甲酸辛酯。
1.13. β -(3,5- 二 - 三級丁基 -4- 羥苯基 ) 丙酸與以下之酯 :一元醇或多元醇,例如甲醇、乙醇、正辛醇、異辛醇、十八醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫代二乙二醇、二乙二醇、三乙二醇、異戊四醇、參(羥基乙基)異氰尿酸酯、N,N'-雙(羥基乙基)草醯胺、3-硫雜十一醇、3-硫雜十五醇、三甲基己二醇、三羥甲基丙烷、4-羥基甲基-1-磷雜-2,6,7-三氧雜雙環[2.2.2]辛烷。
1.14. β -(5- 三級丁基 -4- 羥基 -3- 甲基苯基 ) 丙酸與以下之酯 :一元醇或多元醇,例如甲醇、乙醇、正辛醇、異辛醇、十八醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫代二乙二醇、二乙二醇、三乙二醇、異戊四醇、參(羥基乙基)異氰尿酸酯、N,N'-雙(羥基乙基)草醯胺、3-硫雜十一醇、3-硫雜十五醇、三甲基己二醇、三羥甲基丙烷、4-羥基甲基-1-磷雜-2,6,7-三氧雜雙環[2.2.2]辛烷;3,9-雙[2-{3-(3-三級丁基-4-羥基-5-甲基苯基)丙醯基氧基}-1,1-二甲基乙基]-2,4,8,10-四氧雜螺[5.5]十一烷。
1.15. β -(3,5- 二環己基 -4- 羥苯基 ) 丙酸與以下之酯:一元醇或多元醇,例如甲醇、乙醇、辛醇、十八醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫代二乙二醇、二乙二醇、三乙二醇、異戊四醇、參(羥基乙基)異氰尿酸酯、N,N'-雙(羥基乙基)草醯胺、3-硫雜十一醇、3-硫雜十五醇、三甲基己二醇、三羥甲基丙烷、4-羥基甲基-1-磷雜-2,6,7-三氧雜雙環[2.2.2]-辛烷。
1.16. 3,5- 二 - 三級丁基 -4- 羥苯基乙酸與以下之酯:一元醇或多元醇,例如甲醇、乙醇、辛醇、十八醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫代二乙二醇、二乙二醇、三乙二醇、異戊四醇、參(羥基乙基)異氰尿酸酯、N,N'-雙(羥基乙基)草醯胺、3-硫雜十一醇、3-硫雜十五醇、三甲基己二醇、三羥甲基丙烷、4-羥基甲基-1-磷雜-2,6,7-三氧雜雙環[2.2.2]辛烷。
1.17. β -(3,5- 二 - 三級丁基 -4- 羥苯基 ) 丙酸之醯胺,例如N,N'-雙(3,5-二-三級丁基-4-羥苯基丙醯基)六亞甲基二醯胺、N,N'-雙(3,5-二-三級丁基-4-羥苯基丙醯基)三亞甲基二醯胺、N,N'-雙(3,5-二-三級丁基-4-羥苯基丙醯基)醯肼、N,N'-雙[2-(3-[3,5-二-三級丁基-4-羥苯基]丙醯氧基)乙基]草醯胺(Naugard
®XL-1,由Uniroyal供應)。
1.18. 抗壞血酸(維生素C)
1.19. 胺化抗氧化劑,例如N,N'-二-異丙基-對苯二胺、N,N'-二-二級丁基-對苯二胺、N,N'-雙(1,4-二甲基戊基)-對苯二胺、N,N'-雙(1-乙基-3-甲基戊基)-對苯二胺、N,N'-雙(1-甲基庚基)-對苯二胺、N,N'-二環己基-對苯二胺、N,N'-二苯基-對苯二胺、N,N'-雙(2-萘基)-對苯二胺、N-異丙基-N'-苯基-對苯二胺、N-(1,3-二甲基丁基)-N'-苯基-對苯二胺、N-(1-甲基庚基)-N'-苯基-對苯二胺、N-環己基-N'-苯基-對苯二胺、4-(對甲苯胺磺醯基)二苯胺、N,N'-二甲基-N,N'-二-二級丁基-對苯二胺、二苯胺、N-烯丙基二苯胺、4-異丙氧基二苯胺、N-苯基-1-萘胺、N-(4-三級辛基苯基)-1-萘胺、N-苯基-2-萘胺、辛基化二苯胺(例如p,p'-二-三級辛基二苯胺)、4-正丁基胺基苯酚、4-丁醯基胺苯酚、4-壬醯基胺苯酚、4-十二醯基胺苯酚、4-十八醯基胺苯酚、雙(4-甲氧基苯基)胺、2,6-二-三級丁基-4-二甲基胺甲基苯酚、2,4'-二胺基二苯基甲烷、4,4'-二胺基二苯基甲烷、N,N,N',N'-四甲基-4,4'-二胺基二苯基甲烷、1,2-雙[(2-甲基苯基)胺基]乙烷、1,2-雙(苯胺基)丙烷、(鄰甲苯基)二胍、雙[4-(1',3'-二甲基丁基)苯基]胺、三級辛基化N-苯基-1-萘胺、單烷基化與二烷基化三級丁基二苯胺/三級辛基二苯胺之混合物、單烷基化與二烷基化壬基二苯胺之混合物、單烷基化與二烷基化十二烷基二苯胺之混合物、單烷基化與二烷基化異丙基二苯胺/異己基二苯胺之混合物、單烷基化與二烷基化三級丁基二苯胺之混合物、2,3-二氫-3,3-二甲基-4H-1,4-苯并噻𠯤、啡噻𠯤、單烷基化與二烷基化三級丁基啡噻𠯤/三級辛基啡噻𠯤之混合物、單烷基化與二烷基化三級辛基-吩噻𠯤之混合物、N-烯丙基啡噻𠯤、N,N,N',N'-四苯基-1,4-二胺基丁-2-烯。
2.
UV
吸收劑
及光穩定劑
2.1. 2-(2'- 羥苯基 ) 苯并三唑,例如2-(2'-羥基-5'-甲基苯基)-苯并三唑、2-(3',5'-二-三級丁基-2'-羥苯基)苯并三唑、2-(5'-三級丁基-2'-羥苯基)苯并三唑、2-(2'-羥基-5'-1,1,3,3-四甲基丁基)苯基)苯并三唑、2-(3',5'-二-三級丁基-2'-羥苯基)-5-氯-苯并三唑、2-(3'-三級丁基-2'-羥基-5'-甲基苯基)-5-氯-苯并三唑、2-(3'-二級丁基-5'-三級丁基-2'-羥苯基)苯并三唑、2-(2'-羥基-4'-辛氧基苯基)苯并三唑、2-(3',5'-二-三級戊基-2'-羥苯基)苯并三唑、2-(3',5'-雙-(α,α-二甲基苄基)-2'-羥苯基)苯并三唑、2-(3'-三級丁基-2'-羥基-5'-(2-辛氧基羰基乙基)苯基)-5-氯-苯并三唑、2-(3'-三級丁基-5'-[2-(2-乙基己氧基)-羰基乙基]-2'-羥苯基)-5-氯-苯并三唑、2-(3'-三級丁基-2'-羥基-5'-(2-甲氧基羰基乙基)苯基)-5-氯-苯并三唑、2-(3'-三級丁基-2'-羥基-5'-(2-甲氧基羰基乙基)苯基)苯并三唑、2-(3'-三級丁基-2'-羥基-5'-(2-辛氧羰基乙基)苯基)苯并三唑、2-(3'-三級丁基-5'-[2-(2-乙基己氧基)羰基乙基]-2'-羥苯基)苯并三唑、2-(3'-十二基-2'-羥基-5'-甲基苯基)苯并三唑、2-(3'-三級丁基-2'-羥基-5'-(2-異辛氧基羰乙基)苯基苯并三唑、2,2'-亞甲基-雙[4-(1,1,3,3-四甲基丁基)-6-苯并三唑-2-基苯酚];2-[3'-三級丁基-5'-(2-甲氧基羰基乙基)-2'-羥苯基]-2H-苯并三唑與聚乙二醇300之轉酯化產物;
,其中R = 3'-三級丁基-4'-羥基-5'-2H-苯并三唑-2-基苯基、2-[2'-羥基-3'-(α,α-二甲基苄基)-5'-(1,1,3,3-四甲基丁基)-苯基]苯并三唑;2-[2'-羥基-3'-(1,1,3,3-四甲基丁基)-5'-(α,α-二甲基苄基)-苯基]苯并三唑。
2.2. 2- 羥基二苯甲酮,例如4-羥基、4-甲氧基、4-辛氧基、4-癸氧基、4-十二烷氧基、4-苄氧基、4,2',4'-三羥基及2'-羥基-4,4'-二甲氧基衍生物。
2.3. 經取代及未經取代之苯甲酸之酯,例如柳酸4-三級丁基-苯酯、柳酸苯酯、柳酸辛基苯酯、二苯甲醯基間苯二酚、雙(4-三級丁基苯甲醯基)間苯二酚、苯甲醯基間苯二酚、3,5-二-三級丁基-4-羥基苯甲酸2,4-二-三級丁基苯酯、3,5-二-三級丁基-4-羥基苯甲酸十六酯、3,5-二-三級丁基-4-羥基苯甲酸十八酯、3,5-二-三級丁基-4-羥基苯甲酸2-甲基-4,6-二-三級丁基苯酯。在一較佳實施例中,經取代及未經取代之苯甲酸之酯為3,5-二-三級丁基-4-羥基苯甲酸2,4-二-三級丁基苯酯及/或3,5-二-三級丁基-4-羥基苯甲酸十六烷基酯。
2.4. 丙烯酸酯,例如α-氰基-β,β-二苯基丙烯酸乙酯、α-氰基-β,β-二苯基丙烯酸異辛酯、α-甲氧基羰基肉桂酸甲酯、α-氰基-β-甲基-對甲氧基肉桂酸甲酯、α-氰基-β-甲基-對甲氧基-肉桂酸丁酯、α-甲氧基羰基-對甲氧基肉桂酸甲酯、N-(β-甲氧基羰基-β-氰基乙烯基)-2-甲基吲哚啉、四(α-氰基-β,β-二苯基丙烯酸新戊酯。
2.5. 鎳化合物,例如2,2'-硫基-雙[4-(1,1,3,3-四甲基丁基)苯酚]之鎳錯合物,諸如1:1或1:2錯合物,其具有或不具有額外配位體,諸如正丁胺、三乙醇胺或N-環己基二乙醇胺;二丁二硫胺甲酸鎳;單烷酯(例如甲酯或乙酯)、4-羥基-3,5-二-三級丁基苄基膦酸之鎳鹽;酮肟(例如2-羥基-4-甲基苯基十一酮肟)之鎳錯合物;1-苯基-4-十二醯基-5-羥基吡唑之鎳錯合物,其具有或不具有其他配位體。
2.7. 草醯胺,例如4,4'-二辛氧基草醯替苯胺、2,2'-二乙氧基草醯替苯胺、2,2'-二辛氧基-5,5'-二-三級丁草醯替苯胺、2,2'-二(十二烷氧基)-5,5'-二-三級丁草醯替苯胺、2-乙氧基-2'-乙基草醯替苯胺、N,N'-雙(3-二甲胺基丙基)草醯胺、2-乙氧基-5-三級丁基-2'-乙草醯替苯胺及其與2-乙氧基-2'-乙基-5,4'-二-三級丁草醯替苯胺之混合物、鄰甲氧基與對甲氧基二取代之草醯替苯胺之混合物及鄰乙氧基與對乙氧基二取代之草醯替苯胺之混合物。
3. 金屬去活化劑,例如N,N'-二苯基草醯胺、N-水楊醛-N'-柳醯基肼、N,N'-雙(柳醯基)肼、N,N'-雙(3,5-二-三級丁基-4-羥基苯丙醯基)肼、3-柳醯基胺基-1,2,4-三唑、雙(亞苄基)草醯基二醯肼、草醯替苯胺、異酞醯基二醯肼、癸二醯基雙苯基醯肼、N,N'-二乙醯己二醯基二醯肼、N,N'-雙(柳醯基)草醯基二醯肼、N,N'-雙(柳醯基)硫基丙醯基二醯肼。
4. 亞磷酸酯及亞膦酸二酯,例如亞磷酸三苯酯、亞磷酸二苯基烷酯、亞磷酸苯基二烷酯、亞磷酸參(壬基苯基)酯、亞磷酸三(十二烷基)酯、亞磷酸三(十八烷基)酯、二硬脂醯異戊四醇二亞磷酸酯、亞磷酸參(2,4-二-三級丁基苯基)酯、異戊四醇二亞磷酸二異癸酯、雙(2,4-二-三級丁基苯基)異戊四醇二亞磷酸酯、雙(2,4-二-茴香基苯基)異戊四醇二亞磷酸酯、雙(2,6-二-三級丁基-4-甲基苯基)異戊四醇二亞磷酸酯、二異癸氧基異戊四醇二亞磷酸酯、雙(2,4-二-三級丁基-6-甲基苯基)異戊四醇二亞磷酸酯、雙(2,4,6-參(三級丁基苯基)異戊四醇二亞磷酸酯、山梨糖醇三亞磷酸三硬脂醯酯、肆(2,4-二-三級丁基苯基)4,4'-聯伸二苯二亞磷酸二酯、6-異辛氧基-2,4,8,10-四-三級丁基-12H-二苯并[d,g]-1,3,2-二氧磷雜八環、亞磷酸雙(2,4-二-三級丁基-6-甲基苯基)甲酯、亞磷酸雙(2,4-二-三級丁基-6-甲基苯基)乙酯、6-氟-2,4,8,10-四-三級丁基-12-甲基-二苯并[d,g]-1,3,2-二氧磷雜八環、2,2',2''-氮基[三乙基參(3,3',5,5'-四-三級丁基-1,1'-聯苯-2,2'-二基)亞磷酸酯]、2-乙基己基(3,3',5,5'-四三級丁基-1,1'-聯苯-2,2'-二基)亞磷酸酯、5-丁基-5-乙基-2-(2,4,6-三三級丁基苯氧基)-1,3,2-二氧雜磷雜環丙烷、2,4-雙(1,1-二甲基丙基)苯基及4-(1,1-二甲基丙基)苯基之混合亞磷酸三酯(CAS:939402-02-5)、具有α-氫-ω-羥基聚[氧基(甲基-1,2-乙烷二基)]、C
10至C
16-烷基酯之亞磷酸聯三苯酯聚合物(CAS:1227937-46-3)。
5. 羥胺,例如衍生自氫化牛脂胺之N,N-二苯甲基羥胺、N,N-二乙基羥胺、N,N-二辛基羥胺、N,N-二(十二烷基)羥胺、N,N-二(十四烷基)羥胺、N,N-二(十六烷基)羥胺、N,N-二(十八烷基)羥胺、N-十六烷基-N-十八烷基羥胺、N-十七烷基-N-十八烷基羥胺、N,N-二烷基羥胺。
6. 硝酮,例如衍生自氫化牛脂胺之N-苄基-α-苯基硝酮、N-乙基-α-甲基硝酮、N-辛基-α-庚基硝酮、N-十二烷基-α-十一烷基硝酮、N-十四烷基-α-十三烷基硝酮、N-十六烷基-α-十五基硝酮、N-十八烷基-α-十七烷基硝酮、N-十六烷基-α-十七烷基硝酮、N-十八烷基-α-十五烷基硝酮、N-十七烷基-α-十七烷基硝酮、N-十八烷基-α-十六烷基硝酮、衍生自N,N-二烷基羥胺之硝酮。
7. 硫代增效劑,例如硫代二丙酸二月桂酯、硫代二丙酸二肉豆蔻酯、硫代二丙酸二硬脂醯酯、異戊四醇肆[3-(十二烷基硫基)丙酸酯]或二硬脂醯基二硫化物。
8. 過氧化物清除劑,例如β-硫代二丙酸之酯,例如月桂酯、硬脂醯酯、肉豆蔻酯或十三基酯,巰基苯并咪唑或2-巰基苯并咪唑之鋅鹽、二丁基二硫代胺基甲酸鋅、二(十八烷基)二硫化物、異戊四醇肆(β-十二烷基巰基)丙酸酯。
9. 聚醯胺穩定劑,例如與碘化物及/或磷化合物組合之銅鹽及二價錳鹽。
10.
鹼性共穩定劑,例如三聚氰胺、聚乙烯吡咯啶酮、二氰二胺、三聚氰酸三烯丙酯、脲衍生物、肼衍生物、胺、聚醯胺、聚胺甲酸酯、高級脂肪酸之鹼金屬鹽及鹼土金屬鹽,例如硬脂酸鈣、硬脂酸鋅、山崳酸鎂、硬脂酸鎂、蓖麻油酸鈉及棕櫚酸鉀、鄰苯二酚銻或鄰苯二酚鋅。
11. 成核劑,例如無機物質,諸如滑石、金屬氧化物(諸如二氧化鈦或氧化鎂)、較佳鹼土金屬之磷酸鹽、碳酸鹽或硫酸鹽;有機化合物,諸如單羧酸或聚羧酸及其鹽,例如4-三級丁基苯甲酸、己二酸、二苯基乙酸、丁二酸鈉或苯甲酸鈉;聚合化合物,諸如離子共聚物(離子聚合物)。尤佳為1,3:2,4-雙(3',4'-二甲基亞苄基)山梨醇、1,3:2,4-二(對甲基二亞苄基)山梨醇及1,3:2,4-二(亞苄基)山梨醇。
12. 填充劑及增強劑,例如碳酸鈣、矽酸鹽、玻璃纖維、玻璃珠、石棉、滑石、高嶺土、雲母、硫酸鋇、金屬氧化物及氫氧化物、碳黑、石墨、木粉及其他天然產物之粉末或纖維、合成纖維。
13. 其他添加劑,例如塑化劑、潤滑劑、乳化劑、顏料、流變添加劑、催化劑、流動控制劑、光學增亮劑、防焰劑、抗靜電劑及發泡劑。
14. 苯并呋喃酮及吲哚啉酮,例如U.S. 4,325,863;U.S. 4,338,244;U.S. 5,175,312;U.S. 5,216,052;U.S. 5,252,643;DE-A-4316611;DE-A-4316622;DE-A-4316876;EP-A-0589839;EP-A-0591102;EP-A-1291384中所揭示之彼等或3-[4-(2-乙醯氧基乙氧基)苯基]-5,7-二-三級丁基苯并呋喃-2-酮、5,7-二-三級丁基-3-[4-(2-硬脂醯基氧基乙氧基)苯基]苯并呋喃-2-酮、3,3'-雙[5,7-二-三級丁基-3-(4-[2-羥基乙氧基]苯基)苯并呋喃-2-酮]、5,7-二-三級丁基-3-(4-乙氧基苯基)苯并呋喃-2-酮、3-(4-乙醯氧基-3,5-二甲基苯基)-5,7-二-三級丁基苯并呋喃-2-酮、3-(3,5-二甲基-4-特戊醯氧苯基)-5,7-二-三級丁基苯并呋喃-2-酮、3-(3,4-二甲基苯基)-5,7-二-三級丁基苯并呋喃-2-酮、3-(2,3-二甲基苯基)-5,7-二-三級丁基苯并呋喃-2-酮、3-(2-乙醯基-5-異辛基苯基)-5-異辛基苯并呋喃-2-酮。
酚類抗氧化劑為較佳的。所關注的係上文項1中所列出之彼等。酚類抗氧化劑及過程穩定劑備受關注,諸如異戊四醇肆[3,5-二-三級丁基-4-羥苯丙酸酯]、十八烷基-3-(3,5-二-三級丁基-4-羥苯基)丙酸酯、1,3,5-參(3,5-二-三級丁基-4-羥基苯甲基)-2,4,6-三甲基苯、N,N'-雙(3,5-二-三級丁基-4-羥基苯丙醯基)六亞甲基-二醯胺、雙(1,2,2,6,6-五甲基哌啶-4-基)-丁基(3,5-二-三級丁基-4-羥基苯甲基)丙二酸酯)及參[2,4-二-三級丁基苯基]亞磷酸酯。
其他較佳添加劑為異戊四醇肆[3-(十二烷基硫基)丙酸酯]及硬脂酸鈣。
諸如TiO
2及碳黑之顏料為較佳的。亦關注諸如滑石之填充劑。滑石為由含水矽酸鎂,如Mg
3Si
4O
10(OH)
2構成之黏土礦物。
碳黑通常表示細微粉碎非晶碳,其一般以碳煙形式自烴之部分燃燒獲得。可使用任何可商購滑石及碳黑顏料。
大體而言,相對於有機材料之重量,適合使用例如0.01重量%至30重量%之習知添加劑,較佳地0.01%至20%,特定言之0.01%至10%。極較佳為0.05%至20%,特定言之0.05%至10%。
本發明之添加劑混合物之化合物與習知添加劑之重量比為例如1:100至100:1,較佳地1:100至10:1,特定言之1:10至10:1。
根據本發明之組合物可有利地用於製備各種成型物。實例為:
I-1)浮動裝置、船舶應用、浮筒、浮標,用於甲板、碼頭、船、小輕艇、槳及海灘加強件之塑膠木。
I-2)汽車應用,特定言之減震器、儀錶板、電池組、後部及前部襯裡、引擎蓋下之模型部份、頂板機箱、後備箱襯裡、內部襯裡、氣囊罩蓋、配件(燈)之電子模型、儀錶盤之面板、前燈玻璃、儀器板、外部襯裡、室內裝飾、汽車燈、前照燈、停車燈、尾燈、刹車燈、內部及外部飾板;門板;油箱;鑲玻璃前側;後窗;座椅背、外部板、導線絕緣、用於密封之型材擠壓、包層、柱蓋、底盤部分、排氣系統、燃料過濾器/填充器、燃料泵、燃料槽、車身側面模製件、敞蓬車頂、外部反射鏡、外部飾板、緊固件/固定件、前端模組、玻璃、鉸鏈、鎖定系統、行李/車頂架、按壓/衝壓部份、密封件、側部衝擊保護件、消音器/隔音器及天窗。
I-3)道路交通裝置,特定言之路標、用於道路標記的柱子、汽車配件、警告三角板、醫療狀況、頭盔、輪胎。
I-4)用於飛機、鐵路、機動車(汽車、摩托車) (包括陳設)之裝置。
I-5)用於太空應用(尤其火箭及衛星)之裝置,例如重返大氣層遮罩。
I-6)用於架構與設計、採礦應用、靜聲系統、街道庇護區及掩蔽所之裝置。
II-1)一般電氣設備、外箱及覆蓋物及電動/電子裝置(個人電腦、電話、便攜式電話、印表機、電視機、音訊及視訊裝置)、花盆、衛星TV槽及面板裝置。
II-2)用於諸如鋼或紡織品之其他材料之護套。
II-3)用於電子工業之裝置,特定言之用於插塞(尤其電腦插塞)之絕緣體、用於電動及電子部件之外殼、印刷板及用於電子資料儲存裝置(諸如芯片、借記卡或信用卡)之材料。
II-4)電動設備,特定言之洗衣機、滾筒、烘箱(微波烘箱)、洗碗機、攪拌機及熨斗。
II-5)用於燈(例如街道燈、燈罩)之外殼。
II-6)在電線及電纜(半導體、絕緣體及電纜護套)中之應用。
II-7)用於電容器、冰箱、加熱裝置、空調、電子器件之密封、半導體、咖啡機及真空吸塵器之箔。
III-1)諸如嵌齒輪(齒輪)、滑動配件、隔片、螺桿、螺釘、手柄及旋鈕之技術物品。
III-2)轉子葉片、通風設備及風車輪葉、太陽能裝置、泳池、泳池覆蓋物、泳池襯裡、水池襯裡、壁櫥、衣櫥、隔牆、槽板、摺疊牆、屋頂、百葉窗(例如捲簾百葉窗)、配件、管道之間的連接件、套管及輸送機帶。
III-3)清潔物品,尤其淋浴隔間、馬桶座、蓋子及水槽。
III-4)衛生物品,特定言之尿布(嬰兒、成人失禁)、女性衛生物品、浴簾、刷子、墊子、浴盆、抽水馬桶、牙刷及便盆。
III-5)用於水、廢水及化學品之管道(交聯或不交聯)、用於電線及電纜保護之管道,用於氣體、油及生活污水之管道,槽管,下流管及排水系統。
III-6)任何幾何結構(窗玻璃板)及板壁之邊框。
III-7)玻璃替代品,特定言之擠壓板、建築物玻璃(整體式、雙層或多層)、飛機、學校、擠壓片材、用於架構玻璃之窗膜、火車、運輸及衛生物品。
III-8)板(牆壁、砧板)、擠壓塗層(感光紙、四角包及管道塗層)、筒倉、木材替代物、塑膠木、木材複合物、牆壁、表面、傢俱、裝飾箔、地板覆蓋物(內部及外部應用)、地板、活動鋪板及瓷磚。
III-9)入口及出口歧管。
III-10)水泥、混凝土、複合應用及覆蓋物、板壁及包層、扶手、欄桿、廚房操作台、屋頂、屋頂片材、瓷磚及防水布。
IV-1)板材(牆壁及砧板)、托盤、人工草坪、阿斯特羅人造草皮(astroturf)、用於體育場環路(體育運動)之人工覆蓋物、用於體育場環路(體育運動)之人工地板,及膠帶。
IV-2)連續編織品及短纖維,纖維(地毯/衛生物品/土工織物/絲狀纖維;過濾器;擦拭物/窗簾(遮光物)/醫藥應用),散纖維(諸如長袍/防護服之應用),網,繩索,電纜,細繩,簾線,紗線,安全座椅帶,衣服,內衣,手套;靴子;橡膠靴,貼身衣物,服裝,游泳衣,運動衣,傘(太陽傘、遮陽傘),降落傘,滑翔傘,帆,「氣球綢」,露營物品,帳篷,氣墊床,日光床,散裝袋及袋子。
IV-3)薄膜、絕緣體、用於屋頂之覆蓋物及密封件、隧道、垃圾場、水池、垃圾場、牆體屋頂薄膜、土工薄膜、泳池、窗簾(遮光物)/日光遮罩、遮篷、罩蓋、牆紙、食品包裝及包裹(彈性及實心)、醫療包裝(彈性及實心)、氣囊/安全帶、扶手及頭枕、地毯、中心控制台、儀錶板、座艙、門、頂置控制台模組、門飾板、車頂襯、內部照明、內鏡、包裹架、後部行李箱蓋、座椅、轉向柱、方向盤、紡織品及軀幹邊條。
V-1)薄膜(封裝、堆放、層壓、捆包、游泳池、廢料袋、牆紙、拉伸薄膜、酒椰葉纖維(raffia)、淡化薄膜、電池組及連接件。
V-2)農業薄膜(溫室覆蓋物、隧道、覆蓋、青貯料、捆包),尤其在農用化學品之密集應用存在下。
VI-1)食品封裝及包裝(可撓性及固態)、BOPP、BOPET、瓶子。
VI-2)儲存系統,諸如盒(板條箱)、行李箱、櫃子、家用盒子、棧板、架子、播放軌、螺釘盒、包裝及罐子。
VI-3)濾筒、注射器、醫療應用、用於任何運輸之容器、廢物筐及廢物箱、廢物袋、箱子、垃圾箱、箱子襯裡、有輪箱、一般容器、用於水/經使用之水/化學物質/氣體/油/汽油/柴油之儲槽;槽襯裡、盒子、板條箱、電池外殼、凹槽、諸如活塞之醫療裝置、眼科應用、診斷裝置及用於藥劑氣泡之包裝。
VII-1)擠壓塗層(相紙、四角包、管道塗層)、任何種類之家庭物品(例如電氣設備、熱水瓶/衣服掛鉤)、諸如插塞之扣接系統、電線及電纜夾、拉鏈、封閉件、鎖及搭扣式封閉件。
VII-2)支撐裝置、用於休閒時間(諸如運動)之物品及健身器件、體操墊、滑雪靴、直列式溜冰鞋、滑雪板、大腳、運動場面(例如網球地面);螺旋蓋、用於瓶子之蓋子及塞子,以及罐子。
VII-3)一般傢俱、發泡物品(墊子、緩衝器)、發泡體、海綿、洗碟布、墊子、花園椅子、體育場座椅、台子、長椅、玩具、建材(板/圖/球)、劇場、幻燈片及玩具汽車。
VII-4)用於光學及磁性資料儲存之材料。
VII-5)廚房器皿(食用、飲用、烹飪、儲存)。
VII-6)用於CD、卡匣及視訊帶之盒子;DVD電子物品、任何種類的辦公用品(鋼珠筆、圖章及打印台、滑鼠、架子、播放軌)、任何體積及含量之瓶子(飲料、清潔劑、包括香料之化妝品)及膠帶。
VII-7)鞋類(鞋/鞋底)、鞋墊、鞋套、黏著劑、結構黏著劑、食品盒(水果、蔬菜、肉、魚)、合成紙、用於瓶子之標籤、長椅、人造關節(人類)、印刷板(柔版)、印刷電路板及顯示器技術。
VII-8)填充聚合物(滑石、白堊、瓷土(高嶺土)、矽灰石、顏料、碳黑、TiO
2、雲母、奈米複合物、白雲石、矽酸鹽、玻璃、石棉)之裝置。
較佳為由根據本發明之組合物製成之汽車內部或外部材料。尤其較佳的成型物品為以上I-2所列出之彼等。所關注的亦係用於車頂、座椅或儀錶板之覆面材料。式(2)之化合物及其製備例如自WO 2008/077830已知。
本發明之添加劑混合物為抵抗不同應用(如但不限於汽車應用)中之光及熱及氧化之有害效應的極佳穩定劑。添加劑混合物尤其適合作為光穩定劑。
因此,在另一態樣中,目前所主張之本發明係關於一種用於穩定對氧化、熱或光誘發性降解敏感之有機材料之方法,其包含將本發明之添加劑混合物併入其中或施加至其中。
在另一態樣中,目前所主張之本發明係關於本發明之添加劑混合物用作對光誘發性降解敏感之有機材料之光穩定劑的用途。
目前所主張之本發明提供以下優勢中之一或多者:
1.本發明之添加劑混合物使對氧化、熱或光誘發性降解敏感之有機材料穩定。
2.本發明之添加劑混合物在用於有機材料中時提供對有機材料物品不展示黏性且不展示有機材料物品起霜/滲出之表面。
在下文中,描述目前所主張之本發明之特定實施例:
1.一種添加劑混合物,其包含式(1)化合物及式(2)化合物
,
,
其中
A
1為直鏈或分支鏈、經取代或未經取代之C
1至C
20烷基,且
A
2為直鏈或分支鏈、經取代或未經取代之C
1至C
30烷基。
2.根據實施例1之添加劑混合物,其中A
1為直鏈或分支鏈、經羥基取代之C
1至C
20烷基,且A
2為直鏈或分支鏈、未經取代之C
1至C
30烷基。
3.根據實施例1或2之添加劑混合物,其中A
1為2-羥基-2-甲基丙基,且A
2為C
15至C
17烷基。
4.根據實施例1至3中一或多項之添加劑混合物,其中式(1)化合物與式(2)化合物之重量比在5:95至95:5之範圍內。
5.根據實施例1至4中一或多項之添加劑混合物,其進一步包含除如在實施例1中所定義之添加劑之以外的添加劑,其選自受阻胺光穩定劑、羥苯基三𠯤UV吸收劑、式(C-I-8)化合物
,
其中n'為14至16範圍內之整數,及
其混合物。
6.根據實施例5之添加劑混合物,其中受阻胺光穩定劑係選自由以下組成之群:碳酸雙(1-十一烷氧基-2,2,6,6-四甲基-4-哌啶基)酯、雙(2,2,6,6-四甲基-4-哌啶基)癸二酸酯、雙(2,2,6,6-四甲基-4-哌啶基)丁二酸酯、雙(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯、雙(1-辛氧基-2,2,6,6-四甲基-4-哌啶基)癸二酸酯、正丁基-3,5-二-三級丁基-4-羥基苯甲基丙二酸雙(1,2,2,6,6-五甲基-4-哌啶基)酯、1-(2-羥基乙基)-2,2,6,6-四甲基-4-羥基哌啶與丁二酸之縮合物、N,N'-雙(2,2,6,6-四甲基-4-哌啶基)六亞甲基二胺與4-三級辛基胺基-2,6-二氯-1,3,5-三𠯤之直鏈或環狀縮合物、參(2,2,6,6-四甲基-4-哌啶基)氮基三醋酸酯、肆(2,2,6,6-四甲基-4-哌啶基)-1,2,3,4-丁烷四羧酸酯、1,1'-(1,2-乙二基)-雙(3,3,5,5-四甲基哌𠯤酮)、4-苯甲醯基-2,2,6,6-四甲基哌啶、4-硬脂醯氧基-2,2,6,6-四甲基哌啶、雙(1,2,2,6,6-五甲基哌啶基)-2-正丁基-2-(2-羥基-3,5-二-三級丁基苯甲基)丙二酸酯、3-正辛基-7,7,9,9-四甲基-1,3,8-三氮雜螺[4.5]癸烷-2,4-二酮、雙(1-辛氧基-2,2,6,6-四甲基哌啶基)癸二酸酯、雙(1-辛氧基-2,2,6,6-四甲基哌啶基)丁二酸酯、N,N'-雙(2,2,6,6-四甲基-4-哌啶基)六亞甲基二胺與4-N-𠰌啉基-2,6-二氯-1,3,5-三𠯤之直鏈或環狀縮合物、2-氯-4,6-雙(4-正丁胺基-2,2,6,6-四甲基哌啶基)-1,3,5-三𠯤與1,2-雙(3-胺基丙胺基)乙烷之縮合物、2-氯-4,6-二(4-正丁胺基-1,2,2,6,6-五甲基哌啶基)-1,3,5-三𠯤與1,2-雙(3-胺基丙胺基)乙烷之縮合物、8-乙醯基-3-十二基-7,7,9,9-四甲基-1,3,8-三氮雜螺[4.5]癸烷-2,4-二酮、3-十二基-1-(2,2,6,6-四甲基-4-哌啶基)吡咯啶-2,5-二酮、3-十二基-1-(1,2,2,6,6-五甲基-4-哌啶基)吡咯啶-2,5-二酮、4-十六烷氧基-2,2,6,6-四甲基哌啶與4-硬脂醯氧基-2,2,6,6-四甲基哌啶之混合物、N,N'-雙(2,2,6,6-四甲基-4-哌啶基)六亞甲基二胺與4-環己胺基-2,6-二氯-1,3,5-三𠯤之縮合物、1,2-雙(3-胺基丙胺基)乙烷與2,4,6-三氯-1,3,5-三𠯤與4-丁胺基-2,2,6,6-四甲基哌啶之縮合物;1,6-己二胺與2,4,6-三氯-1,3,5-三𠯤以及N,N-二丁胺與4-丁胺基-2,2,6,6-四甲基哌啶之縮合物;N-(2,2,6,6-四甲基-4-哌啶基)正十二烷基丁二醯亞胺、N-(1,2,2,6,6-五甲基-4-哌啶基)正十二烷基丁二醯亞胺、2-十一基-7,7,9,9-四甲基-1-氧雜-3,8-二氮雜-4-側氧基-螺[4,5]癸烷、7,7,9,9-四甲基-2-環十一烷基-1-氧雜-3,8-二氮雜-4-側氧基螺-[4,5]癸烷與環氧氯丙烷之反應產物、1,1-雙(1,2,2,6,6-五甲基-4-哌啶基氧基羰基)-2-(4-甲氧基苯基)乙烯、N,N'-雙甲醯基-N,N'-雙(2,2,6,6-四甲基-4-哌啶基)六亞甲基二胺、4-甲氧基亞甲基丙二酸與1,2,2,6,6-五甲基-4-羥基哌啶之二酯、聚[甲基丙基-3-氧基-4-(2,2,6,6-四甲基-4-哌啶基)]矽氧烷、順丁烯二酸酐-α烯烴共聚物與2,2,6,6-四甲基-4-胺基哌啶或1,2,2,6,6-五甲基-4-胺基哌啶之反應產物、2,4-雙[N-(1-環己氧基-2,2,6,6-四甲基哌啶-4-基)-N-丁胺基]-6-(2-羥基乙基)胺基-1,3,5-三𠯤、5-(2-乙基己醯基)氧基甲基-3,3,5-三甲基-2-𠰌啉酮、5-(2-乙基己醯基)氧基甲基-3,3,5-三甲基-2-𠰌啉酮、2,4-雙[(1-環己氧基-2,2,6,6-哌啶-4-基)丁胺基]-6-氯-對稱三𠯤與N,N'-雙(3-胺基丙基)乙二胺)之反應產物、1,3,5-參(N-環己基-N-(2,2,6,6-四甲基哌𠯤-3-酮-4-基)胺基)-對稱三𠯤、1,3,5-參(N-環己基-N-(1,2,2,6,6-五甲基哌𠯤-3-酮-4-基)胺基)-對稱三𠯤、4-N-丁基-2-N,4-N-雙(2,2,6,6-四甲基哌啶-4-基)-2-N-[6-[(2,2,6,6-四甲基哌啶-4-基)胺基]己基]-1,3,5-三𠯤-2,4-二胺、N,N'-雙(2,2,6,6-四甲基-4-哌啶基)-N,N’-二甲醯基六亞甲基二胺及其混合物。
7.根據實施例6之添加劑混合物,其中羥苯基三𠯤UV吸收劑係選自由以下組成之群:2,4,6-參(2-羥基-4-辛氧基苯基)-1,3,5-三𠯤、2-(2-羥基-4-辛氧基苯基)-4,6-雙(2,4-二甲基苯基)-1,3,5-三𠯤、2-(2,4-二羥基苯基)-4,6-雙(2,4-二甲基苯基)-1,3,5-三𠯤、2,4-雙(2-羥基-4-丙氧基苯基)-6-(2,4-二甲基苯基)-1,3,5-三𠯤、2-(2-羥基-4-辛氧基苯基)-4,6-雙(4-甲基苯基)-1,3,5-三𠯤、2-(2-羥基-4-十二烷氧基苯基)-4,6-雙(2,4-二甲基苯基)-1,3,5-三𠯤、2-(2-羥基-4-十三烷氧基苯基)-4,6-雙(2,4-二甲基苯基)-1,3,5-三𠯤、2-[2-羥基-4-(2-羥基-3-丁氧基丙氧基)苯基]-4,6-雙(2,4-二甲基)-1,3,5-三𠯤、2-[2-羥基-4-(2-羥基-3-辛氧基丙氧基)苯基]-4,6-雙(2,4-二甲基)-1,3,5-三𠯤、2-[4-(十二烷氧基/十三烷氧基-2-羥丙氧基)-2-羥苯基]-4,6-雙(2,4-二甲基苯基)-1,3,5-三𠯤、2-[2-羥基-4-(2-羥基-3-十二烷氧基丙氧基)苯基]-4,6-雙(2,4-二甲基苯基)-1,3,5-三𠯤、2-(2-羥基-4-己氧基)苯基-4,6-二苯基-1,3,5-三𠯤、2-(2-羥基-4-甲氧基苯基)-4,6-二苯基-1,3,5-三𠯤、2,4,6-參[2-羥基-4-(3-丁氧基-2-羥丙氧基)苯基]-1,3,5-三𠯤、2-(2-羥苯基)-4-(4-甲氧基苯基)-6-苯基-1,3,5-三𠯤、2-{2-羥基-4-[3-(2-乙基己基-1-氧基)-2-羥基丙氧基]苯基}-4,6-雙(2,4-二甲基苯基)-1,3,5-三𠯤、2,4-雙(4-[2-乙基己氧基]-2-羥苯基)-6-(4-甲氧基苯基)-1,3,5-三𠯤、2-(4,6-雙聯苯基-4-基-1,3,5-三𠯤-2-基)-5-(2-乙基-(正)-己氧基)酚及其混合物。
8.根據實施例1至7中一或多項之添加劑混合物,其進一步包含經取代及未經取代之苯甲酸之酯。
9.一種組合物,其包含
a)有機材料,其對氧化、熱或光誘發性降解敏感;及
b)添加劑混合物,如在實施例1至8中一或多項所定義。
10.根據實施例9之組合物,其中有機材料與添加劑混合物之重量比在99.99:0.01至1.0:99.0之範圍內。
11.根據實施例9或10之組合物,其中該有機材料係選自由以下組成之群:熱塑性彈性體、聚烯烴、丙烯腈/丁二烯/苯乙烯、聚氯乙烯、聚甲基丙烯酸甲酯、聚醯胺或聚甲醛。
12.根據實施例9至11中一或多項之組合物,其中有機材料為熱塑性聚烯烴。
13.根據實施例9至12中一或多項之組合物,其中熱塑性聚烯烴為熱塑性聚乙烯或聚丙烯。
14.根據實施例9至13中一或多項之組合物,其進一步包含組分(c)抗刮痕劑、填充劑、顏料及其混合物。
15.根據實施例9至14中一或多項之組合物,其中抗刮痕劑係選自由以下組成之群:不飽和或飽和脂肪酸醯胺、聚(有機)矽氧烷及其混合物。
16.一種汽車內部或外部材料,其由根據實施例9至14中任一項之組合物製成。
17.一種用於穩定對氧化、熱或光誘發性降解敏感之有機材料之方法,其包含將如實施例1至8中所定義之添加劑混合物併入其中或施加至其中。
18.一種如實施例1至8中所定義之添加劑混合物作為對光誘發性降解敏感之有機材料之光穩定劑的用途。
以下實例更詳細地說明本發明。除非另外陳述,否則本申請案中所提及之所有百分比及部分以重量計。
實例 1:熱塑性聚丙烯之穩定化。
基礎調配物:
1. 89.36重量%之熱塑性聚烯烴(Borealis之Daplen
®EE013 AE;熔體流動速率:11 g/10 min (ISO 1133);密度:905 kg/m
3(ISO 1183),
2. 0.1重量%之80%參(2,4-二-三級丁基苯基)亞磷酸酯)+20%十八烷基-3-[3,5-二-三級丁基-4-羥苯基]丙酸酯之摻合物,
3. 0.05重量%之硬脂酸鈣,
4. 10.0重量%之滑石,
5. 0.03重量%之碳黑,及
6. 0.4重量%之
芥酸醯胺。
其他添加劑混合物(如以下概述)用對於基礎調配物之相同方法併入。在每一種情況下,熱塑性聚丙烯之重量百分比經調整至所有成分的總和為100%。
添加劑混合物:
化合物A:1,3,5-三(3,5-二-三級丁基-4-羥基苯甲基)異氰尿酸酯,
化合物B:1-(2-羥基-2-甲基丙氧基)-4-十八醯氧基-2,2,6,6-四甲基哌啶,
化合物C:N,N'-雙(2,2,6,6-四甲基-4-哌啶基)-N,N'-二甲醯基六亞甲基二胺,及
化合物D:1,6-己二胺與2,4,6-三氯-1,3,5-三𠯤以及N,N-二丁胺與4-丁胺基-2,2,6,6-四甲基哌啶之縮合物
添加劑混合物 | 化合物A | 化合物B | 化合物C | 化合物D |
混合物1 | 0.03% | 0.03% | - | - |
混合物2 | 0.025% | 0.025% | 0.01% | - |
混合物3 | 0.025% | 0.025% | - | 0.01% |
製備測試樣本:
將基礎調配物在Pappermaier® ESK-150混合器中預混合。將此混合物與以上所列出之0.6重量%之添加劑混合物在Mixaco Lab CM12高速混合器中進行合併,且隨後在雙螺桿擠壓機Berstorff® ZE 25x32D中在220℃下進行混合。隨後將全部調配物在240℃下在Engel HL65注射模製機上注射模製。
將注射模製薄板40 mm × 60 mm × 2 mm或25 mm × 60 mm × 2 mm曝露於根據Volkswagen (VW), PV 1303-灰度階及來自Volkswagen, PV 1303-△E之國際標準的人工風化。PV 1303之設定如下:
VW PV 1303, DIN 75 202:
燈: 氙弧
燈之照射: 420 nm下之1.2 W/m
2或300至400 nm中之60 W/m²。
燈周圍之過濾器集: 內部硼矽酸鹽/外部鹼石灰
黑色面板溫度BPT: 100 ± 3℃
乾球溫度: 65 ± 3℃
腔室中之相對濕度(R.H.): 20 ± 10 %
天氣循環: 永久光/無暗相,僅乾燥/無雨水
所量測之參數為根據DIN EN ISO 105-A05之灰度階及根據DIN 6174之ΔE標度上之色差。
結果列於下表1及表2中。
表 1:灰度階(期望較高值。)
表 2:ΔE (期望較低值。)
曝露小時 | 0 | 259 | 493 | 748 | 993 | 1249 | 1505 |
基礎調配物 | 5 | 0.27 | - | - | - | - | - |
基礎調配物+添加劑混合物1 | 5 | 4.76 | 4.78 | 4.87 | 4.83 | - | - |
基礎調配物+添加劑混合物2 | 5 | 4.82 | 4.72 | 4.81 | 4.85 | 4.8 | 0.39 |
基礎調配物+添加劑混合物3 | 5 | 4.74 | 4.81 | 4.81 | 4.8 | 4.72 | 4.54 |
曝露小時 | 0 | 259 | 493 | 748 | 993 | 1249 | 1505 | 1744 |
基礎調配物 | 0 | 32.7 | - | - | - | - | - | - |
基礎調配物+添加劑混合物1 | 0 | 0.4 | 0.37 | 0.22 | 0.28 | 32.9 | - | - |
基礎調配物+添加劑混合物2 | 0 | 0.3 | 0.47 | 0.31 | 0.26 | 0.33 | 35.6 | - |
基礎調配物+添加劑混合物3 | 0 | 0.43 | 0.32 | 0.32 | 0.34 | 0.47 | 0.79 | 35.2 |
自表1及2顯而易見,添加本發明之添加劑混合物提供所測試熱塑性聚丙烯樣本之性質之較佳保留(亦即,當曝露於人工風化時沒有因降解所導致的色彩變化)。
實例 2:熱塑性聚丙烯之穩定化。
類似於實例1中所描述之方法來製備測試樣本,且曝露於根據Volkswagen, PV 3930-灰度階及來自Volkswagen, PV 3930-△E (PV 3930亦已知為『佛羅里達測試』)之國際標準的人工風化。
PV 3930之設定如下:
VW PV 3930:
燈: 氙弧
燈之照射: 340 nm下之0.5 W/m
2燈周圍之過濾器集: 內部硼矽酸鹽/外部硼矽酸鹽
黑色標準溫度BST: 65 ± 3℃
乾球溫度: 40 ± 3℃
腔室中之相對濕度: 70 ± 10 %
天氣循環: 108 min光及乾燥/18 min光及濕潤
所量測之參數為根據DIN EN ISO 105-A05之灰度階及根據DIN 6174之ΔE標度上之色差。
結果列於下表3及表4中。
表 3:灰度階(期望較高值。)
表 4:ΔE (期望較低值。)
曝露小時 | 0 | 283 | 490 | 770 | 999 | 1257 | 1491 | 1980 | 2554 | 3512 | 4277 | 5015 |
基礎調配物 | 5 | 4.83 | 1.04 | - | - | - | - | - | - | - | - | - |
基礎調配物+添加劑混合物1 | 5 | 4.92 | 4.92 | 4.85 | 4.96 | 4.91 | 4.85 | 4.99 | 4.87 | 4.17 | 3.74 | 2.79 |
基礎調配物+添加劑混合物2 | 5 | 4.94 | 4.88 | 4.93 | 4.92 | 4.87 | 4.54 | 4.8 | 4.69 | 4.55 | 4.09 | 2.71 |
基礎調配物+添加劑混合物3 | 5 | 4.93 | 4.89 | 4.93 | 4.96 | 4.9 | 4.89 | 4.93 | 4.78 | 4.15 | 3.49 | 2.66 |
曝露小時 | 0 | 283 | 490 | 770 | 999 | 1257 | 1491 | 1754 | 1980 | 2243 | 2554 | 2745 | 3249 |
基礎調配物 | 0 | 0.29 | 13.2 | - | - | - | - | - | - | - | - | - | - |
基礎調配物+添加劑混合物1 | 0 | 0.14 | 0.13 | 0.26 | 0.06 | 0.16 | 0.26 | 0.07 | 0.02 | 0.11 | 0.22 | 0.35 | 1.05 |
基礎調配物+添加劑混合物2 | 0 | 0.1 | 0.2 | 0.11 | 0.14 | 0.22 | 0.78 | 1.03 | 0.35 | 0.49 | 0.52 | 0.84 | 0.56 |
基礎調配物+添加劑混合物3 | 0 | 0.11 | 0.19 | 0.11 | 0.07 | 0.17 | 0.19 | 0.06 | 0.12 | 0.3 | 0.38 | 0.47 | 1.15 |
自表3及4顯而易見,添加本發明之添加劑混合物提供所測試熱塑性聚丙烯樣本之性質之較佳保留(亦即,當曝露於人工風化時沒有因降解所導致的色彩變化)。
實例 3:熱塑性聚丙烯之穩定化。
在聚合物、填充劑、色彩、穩定劑及抗刮痕試劑之一些組合中,一些添加劑可遷移且呈不適當之組合比率,此等添加劑甚至可起霜至表面上。藉由日光曝露及降解,此等添加劑隨後可形成具有黏性或黏性行為之層。在黏性測試之情況下,其可記錄此黏性如何在表面上產生。
類似於實例1中所描述之方法來製備測試樣本且根據國際標準PV 1306-GS及PV 1306-DE (PV 1306為用於判定聚丙烯部分之黏性之曝露測試)來評估其黏性。根據給定系統評級手指所體驗之黏性且記錄熟化時間。對於吾人之測試,吾人使用如以下所給出之等級系統:
結果列於表5中。
正常 | 1 |
鈍(起霜,但無黏性) | 2 |
輕微黏性 | 3 |
黏性 | 4 |
極具黏性 | 5 |
樹脂化(不再有黏性) | 6 |
蠟質 | 7 |
測試取消,樣本斷裂 | 8 |
曝露小時 | 0 | 225 | 503 | 786 | 997 | 1257 | 1517 | 1756 | 2014 | 2254 | 2517 | 2780 | 2996 | 3284 |
基礎調配物 | - | 2 | 2 | 2 | 2 | - | - | - | - | - | - | - | - | - |
基礎調配物+添加劑混合物1 | - | 2 | 2 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
基礎調配物+添加劑混合物2 | - | 2 | 2 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
基礎調配物+添加劑混合物3 | - | 2 | 2 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
自表5顯而易見,添加添加劑混合物提供對熱塑性聚丙烯樣本不展示黏性且不展示熱塑性聚丙烯樣本起霜/滲出之表面。
Claims (18)
- 如請求項1之添加劑混合物,其中A 1為直鏈或分支鏈、經羥基取代之C 1至C 20烷基,且A 2為直鏈或分支鏈、未經取代之C 1至C 30烷基。
- 如請求項1或2之添加劑混合物,其中A 1為2-羥基-2-甲基丙基,且A 2為C 15至C 17烷基。
- 如請求項1至3中一或多項之添加劑混合物,其中該式(1)化合物與該式(2)化合物之重量比在5:95至95:5範圍內。
- 如請求項5之添加劑混合物,其中該受阻胺光穩定劑係選自由以下組成之群:碳酸雙(1-十一烷氧基-2,2,6,6-四甲基-4-哌啶基)酯、雙(2,2,6,6-四甲基-4-哌啶基)癸二酸酯、雙(2,2,6,6-四甲基-4-哌啶基)丁二酸酯、雙(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯、雙(1-辛氧基-2,2,6,6-四甲基-4-哌啶基)癸二酸酯、正丁基-3,5-二-三級丁基-4-羥基苯甲基丙二酸雙(1,2,2,6,6-五甲基-4-哌啶基)酯、1-(2-羥基乙基)-2,2,6,6-四甲基-4-羥基哌啶與丁二酸之縮合物、N,N'-雙(2,2,6,6-四甲基-4-哌啶基)六亞甲基二胺及4-三級辛基胺基-2,6-二氯-1,3,5-三𠯤之直鏈或環狀縮合物、參(2,2,6,6-四甲基-4-哌啶基)氮基三醋酸酯、肆(2,2,6,6-四甲基-4-哌啶基)-1,2,3,4-丁烷四羧酸酯、1,1'-(1,2-乙二基)-雙(3,3,5,5-四甲基哌𠯤酮)、4-苯甲醯基-2,2,6,6-四甲基哌啶、4-硬脂醯氧基-2,2,6,6-四甲基哌啶、雙(1,2,2,6,6-五甲基哌啶基)-2-正丁基-2-(2-羥基-3,5-二-三級丁基苯甲基)丙二酸酯、3-正辛基-7,7,9,9-四甲基-1,3,8-三氮雜螺[4.5]癸烷-2,4-二酮、雙(1-辛氧基-2,2,6,6-四甲基哌啶基)癸二酸酯、雙(1-辛氧基-2,2,6,6-四甲基哌啶基)丁二酸酯、N,N'-雙(2,2,6,6-四甲基-4-哌啶基)六亞甲基二胺及4-N-𠰌啉基-2,6-二氯-1,3,5-三𠯤之直鏈或環狀縮合物、2-氯-4,6-雙(4-正丁胺基-2,2,6,6-四甲基哌啶基)-1,3,5-三𠯤與1,2-雙(3-胺基丙胺基)乙烷之縮合物、2-氯-4,6-二(4-正丁胺基-1,2,2,6,6-五甲基哌啶基)-1,3,5-三𠯤與1,2-雙(3-胺基丙胺基)乙烷之縮合物、8-乙醯基-3-十二基-7,7,9,9-四甲基-1,3,8-三氮雜螺[4.5]癸烷-2,4-二酮、3-十二基-1-(2,2,6,6-四甲基-4-哌啶基)吡咯啶-2,5-二酮、3-十二基-1-(1,2,2,6,6-五甲基-4-哌啶基)吡咯啶-2,5-二酮、4-十六烷氧基-2,2,6,6-四甲基哌啶與4-硬脂醯氧基-2,2,6,6-四甲基哌啶之混合物、N,N'-雙(2,2,6,6-四甲基-4-哌啶基)六亞甲基二胺與4-環己胺基-2,6-二氯-1,3,5-三𠯤之縮合物、1,2-雙(3-胺基丙胺基)乙烷及2,4,6-三氯-1,3,5-三𠯤與4-丁胺基-2,2,6,6-四甲基哌啶之縮合物;1,6-己二胺與2,4,6-三氯-1,3,5-三𠯤以及N,N-二丁胺與4-丁胺基-2,2,6,6-四甲基哌啶之縮合物;N-(2,2,6,6-四甲基-4-哌啶基)-正十二烷基丁二醯亞胺、N-(1,2,2,6,6-五甲基-4-哌啶基)-正十二烷基丁二醯亞胺、2-十一基-7,7,9,9-四甲基-1-氧雜-3,8-二氮雜-4-側氧基-螺[4,5]癸烷、7,7,9,9-四甲基-2-環十一烷基-1-氧雜-3,8-二氮雜-4-側氧基螺-[4,5]癸烷及環氧氯丙烷之反應產物、1,1-雙(1,2,2,6,6-五甲基-4-哌啶基氧基羰基)-2-(4-甲氧基苯基)乙烯、N,N'-雙甲醯基-N,N'-雙(2,2,6,6-四甲基-4-哌啶基)六亞甲基二胺、4-甲氧基亞甲基丙二酸與1,2,2,6,6-五甲基-4-羥基哌啶之二酯、聚[甲基丙基-3-氧基-4-(2,2,6,6-四甲基-4-哌啶基)]矽氧烷、順丁烯二酸酐-α烯烴共聚物與2,2,6,6-四甲基-4-胺基哌啶或1,2,2,6,6-五甲基-4-胺基哌啶之反應產物、2,4-雙[N-(1-環己氧基-2,2,6,6-四甲基哌啶-4-基)-N-丁胺基]-6-(2-羥基乙基)胺基-1,3,5-三𠯤、5-(2-乙基己醯基)氧基甲基-3,3,5-三甲基-2-𠰌啉酮、5-(2-乙基己醯基)氧基甲基-3,3,5-三甲基-2-𠰌啉酮、2,4-雙[(1-環己氧基-2,2,6,6-哌啶-4-基)丁胺基]-6-氯-對稱三𠯤與N,N'-雙(3-胺基丙基)乙二胺)之反應產物、1,3,5-參(N-環己基-N-(2,2,6,6-四甲基哌𠯤-3-酮-4-基)胺基)-對稱三𠯤、1,3,5-參(N-環己基-N-(1,2,2,6,6-五甲基哌𠯤-3-酮-4-基)胺基)-對稱三𠯤、4-N-丁基-2-N,4-N-雙(2,2,6,6-四甲基哌啶-4-基)-2-N-[6-[(2,2,6,6-四甲基哌啶-4-基)胺基]己基]-1,3,5-三𠯤-2,4-二胺、N,N'-雙(2,2,6,6-四甲基-4-哌啶基)-N,N’-二甲醯基六亞甲基二胺及其混合物。
- 如請求項6之添加劑混合物,其中該羥苯基三𠯤UV吸收劑係選自由以下組成之群:2,4,6-參(2-羥基-4-辛氧基苯基)-1,3,5-三𠯤、2-(2-羥基-4-辛氧基苯基)-4,6-雙(2,4-二甲基苯基)-1,3,5-三𠯤、2-(2,4-二羥基苯基)-4,6-雙(2,4-二甲基苯基)-1,3,5-三𠯤、2,4-雙(2-羥基-4-丙氧基苯基)-6-(2,4-二甲基苯基)-1,3,5-三𠯤、2-(2-羥基-4-辛氧基苯基)-4,6-雙(4-甲基苯基)-1,3,5-三𠯤、2-(2-羥基-4-十二烷氧基苯基)-4,6-雙(2,4-二甲基苯基)-1,3,5-三𠯤、2-(2-羥基-4-十三烷氧基苯基)-4,6-雙(2,4-二甲基苯基)-1,3,5-三𠯤、2-[2-羥基-4-(2-羥基-3-丁氧基丙氧基)苯基]-4,6-雙(2,4-二甲基)-1,3,5-三𠯤、2-[2-羥基-4-(2-羥基-3-辛氧基丙氧基)苯基]-4,6-雙(2,4-二甲基)-1,3,5-三𠯤、2-[4-(十二烷氧基/十三烷氧基-2-羥丙氧基)-2-羥苯基]-4,6-雙(2,4-二甲基苯基)-1,3,5-三𠯤、2-[2-羥基-4-(2-羥基-3-十二烷氧基丙氧基)苯基]-4,6-雙(2,4-二甲基苯基)-1,3,5-三𠯤、2-(2-羥基-4-己氧基)苯基-4,6-二苯基-1,3,5-三𠯤、2-(2-羥基-4-甲氧基苯基)-4,6-二苯基-1,3,5-三𠯤、2,4,6-參[2-羥基-4-(3-丁氧基-2-羥丙氧基)苯基]-1,3,5-三𠯤、2-(2-羥苯基)-4-(4-甲氧基苯基)-6-苯基-1,3,5-三𠯤、2-{2-羥基-4-[3-(2-乙基己基-1-氧基)-2-羥基丙氧基]苯基}-4,6-雙(2,4-二甲基苯基)-1,3,5-三𠯤、2,4-雙(4-[2-乙基己氧基]-2-羥苯基)-6-(4-甲氧基苯基)-1,3,5-三𠯤、2-(4,6-雙聯苯基-4-基-1,3,5-三𠯤-2-基)-5-(2-乙基-(正)-己氧基)酚及其混合物。
- 如請求項1至7中一或多項之添加劑混合物,其進一步包含經取代及未經取代之苯甲酸之酯。
- 一種組合物,其包含 a)有機材料,其對氧化、熱或光誘發性降解敏感;及 b)添加劑混合物,其係如請求項1至8中一或多項所定義。
- 如請求項9之組合物,其中該有機材料與該添加劑混合物之重量比在99.99:0.01至1.0:99.0之範圍內。
- 如請求項9或10之組合物,其中該有機材料係選自由以下組成之群:熱塑性彈性體、聚烯烴、丙烯腈/丁二烯/苯乙烯、聚氯乙烯、聚甲基丙烯酸甲酯、聚醯胺或聚甲醛。
- 如請求項9至11中一或多項之組合物,其中該有機材料為熱塑性聚烯烴。
- 如請求項9至12中一或多項之組合物,其中該熱塑性聚烯烴為熱塑性聚乙烯或聚丙烯。
- 如請求項9至13中一或多項之組合物,其進一步包含組分(c)抗刮痕劑、填充劑、顏料及其混合物。
- 如請求項9至14中一或多項之組合物,其中該抗刮痕劑係選自由以下組成之群:不飽和或飽和脂肪酸醯胺、聚(有機)矽氧烷及其混合物。
- 一種汽車內部或外部材料,其由如請求項9至15中任一項之組合物製成。
- 一種用於穩定對氧化、熱或光誘發性降解敏感之有機材料之方法,其包含將如請求項1至8中所定義之添加劑混合物併入其中或施加至其中。
- 一種如請求項1至8中所定義之添加劑混合物作為對光誘發性降解敏感之有機材料之光穩定劑的用途。
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- 2021-12-08 US US18/265,864 patent/US20240084104A1/en active Pending
- 2021-12-09 TW TW110146090A patent/TW202231768A/zh unknown
Also Published As
Publication number | Publication date |
---|---|
CN116547346A (zh) | 2023-08-04 |
EP4259711A1 (en) | 2023-10-18 |
WO2022122818A1 (en) | 2022-06-16 |
JP2023553074A (ja) | 2023-12-20 |
US20240084104A1 (en) | 2024-03-14 |
CA3201706A1 (en) | 2022-06-16 |
MX2023006824A (es) | 2023-06-21 |
KR20230112727A (ko) | 2023-07-27 |
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