TW201800548A - 聚氨酯型高分子紫外線吸收劑 - Google Patents

聚氨酯型高分子紫外線吸收劑 Download PDF

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TW201800548A
TW201800548A TW105120500A TW105120500A TW201800548A TW 201800548 A TW201800548 A TW 201800548A TW 105120500 A TW105120500 A TW 105120500A TW 105120500 A TW105120500 A TW 105120500A TW 201800548 A TW201800548 A TW 201800548A
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group
ultraviolet absorber
diol
polyol
polyurethane
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TW105120500A
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TWI656199B (zh
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盧梅婷
楊蕙禎
潘垣賓
柯子衡
周德綱
賴寶昆
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臺灣永光化學工業股份有限公司
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Priority to TW105120500A priority Critical patent/TWI656199B/zh
Priority to CN201610757179.4A priority patent/CN107540806A/zh
Priority to US15/610,673 priority patent/US10005958B2/en
Priority to EP17001062.3A priority patent/EP3263761A1/en
Priority to KR1020170082535A priority patent/KR101903896B1/ko
Priority to JP2017126987A priority patent/JP2018009164A/ja
Publication of TW201800548A publication Critical patent/TW201800548A/zh
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Publication of TWI656199B publication Critical patent/TWI656199B/zh

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Abstract

本發明係關於一種聚氨酯型高分子紫外線吸收劑，其聚合物係由：具有一可反應活性氫之紫外線吸收劑，與一多異氰酸酯(Polyisocyanate)及一雙醇或多元醇(Polyol)反應而得；其中，該聚氨酯型高分子紫外線吸收劑之重量平均分子量介於10,000至200,000的範圍。

Description

聚氨酯型高分子紫外線吸收劑
本發明係關於一種聚氨酯型高分子紫外線吸收劑，尤指一種可提高日光牢度及具有耐水洗特性的聚氨酯型高分子紫外線吸收劑。
一般而言，染整製程大致可分成染前處理、印染過程及染後處理。更具體地，染前處理例如：燒毛(Singeing)、退漿(desizing)、精練(Scouring)、漂白(Bleaching)、絲光(Mercerizing)、熱定型(heat setting)，印染過程如染色、印花，以及染後處理如整理加工(finishing)。染前處理的目的在於去除紗線或織物上的天然雜質、以及來自紡織過程的漿料、助劑和沾污物，以免影響後續的印染作業。而染後處理則是為了增加織物的使用性或特殊性能(例如：提升色牢度、改善外觀、改善手感、防縮、防皺、防靜電、防火、防水、撥水、撥油等)，其會隨著織物材質及需求的不同而有不同的處理方式。
為了避免織物因日光(紫外線)曝曬而分解，通常在染後處理的步驟中，添加日光牢度增進劑(例如，紫外線吸收劑、光安定劑等)，以維持織物之使用壽命。目前已有各種材料被應用以增加產品之日光牢度，例如含有具紫外線吸收功效之氧化鋅(ZnO)及二氧化鈦(TiO2 )的溶液、苯并三唑衍生物、二苯甲酮衍生物等，然而，部份材料因親水性不佳，僅適用於特定種類纖維及染料；部份材料雖親水性佳，但牢度不佳；部分材料亦有附著牢度差、不耐水洗等缺點；以及部分材料使用時需伴隨大量有機溶劑或添加界面活性劑，因而極不符合環保需求。尤其，現今日光牢度增進劑經水洗後的耐UV效果大幅降低，故耐水洗性差而使用壽命較短。
有鑑於此，為符合產業的需求，仍亟需研發具良好之水分散性、耐水洗性、環保、且能廣泛應用於多種材質目標物的日光牢度增進劑。
為了解決上述問題，本發明提供一種聚氨酯型高分子紫外線吸收劑，俾能增進目標物之日光牢度同時具有良好的耐水洗特性。
本發明提供一種聚氨酯型高分子紫外線吸收劑，其聚合物係由：具有一可反應活性氫之紫外線吸收劑，與一多異氰酸酯(Polyisocyanate)及一雙醇或多元醇(Polyol)反應而得；其中，該聚氨酯型高分子紫外線吸收劑之重量平均分子量介於10,000至200,000的範圍，較佳為介於10,000至170,000的範圍，更佳為介於10,000至150,000的範圍。
於本發明中，該紫外線吸收劑並無特別限制，僅需具有一可反應之活性氫，該可反應之活性氫可選自由：-OH、-NH2 、及-NH-所組成之群組。更具體地，該紫外線吸收劑可選自由：苯並三唑類(Benzotriazole) 紫外線吸收劑、二苯酮類(Benzophenone) 紫外線吸收劑、三嗪類(Triazine) 紫外線吸收劑、草醯苯胺類(Oxanilide)紫外線吸收劑、及氰基丙烯酸酯類(Cyanoacrylate)紫外線吸收劑所組成之群組。較佳地，該紫外線吸收劑可為苯並三唑類(Benzotriazole) 紫外線吸收劑。
於本發明中，該多異氰酸酯可包含兩個以上的-NCO官能基，較佳為具有三個-NCO官能基。據此，該紫外線吸收劑與該多異氰酸酯進行反應後，該紫外線吸收劑的可反應之活性氫可連接至該多異氰酸酯的-NCO官能基。更具體地，該多異氰酸酯可選自由：異佛爾酮二異氰酸酯(Isophorone diisocyanate；IPDI)、氫化二苯基甲烷二異氰酸酯( 4,4’-dicyclohexylmethane diisocyanate；HMDI)、六亞甲基二異氰酸酯(Hexamethylene diisocyanate；HDI)、苯二亞甲基二異氰酸酯(1,3-Bis(isocyanatomethyl)benzene；XDI)、四甲基間苯二亞甲基二異氰酸酯(Tetramethyl xylylene diisocyanate；TMXDI)、2,2,4-三甲基六亞甲基二異氰酸酯(2,2,4-trimethylhexamethylene diisocyanate；HDI TRIMER)、六亞甲基二異氰酸酯縮二脲(Hexamethylene diisocyanate biuret；HDB)及其混合物所組成之群組。較佳地，該多異氰酸酯可選自由：2,2,4-三甲基六亞甲基二異氰酸酯(HDI TRIMER) 、六亞甲基二異氰酸酯縮二脲(Hexamethylene diisocyanate biuret；HDB)及其混合物或多聚體所組成之群組。
於本發明中，該雙醇或多元醇可包含兩個以上的-OH官能基，據此，該雙醇或多元醇與該多異氰酸酯進行反應後，該雙醇或多元醇的-OH官能基可連接至該多異氰酸酯的-NCO官能基。該雙醇或多元醇可選自由：陰離子型雙醇或多元醇、陽離子型雙醇或多元醇、非離子型雙醇或多元醇及其混合物所組成之群組。更具體地，該陰離子型雙醇或多元醇可選自由：2,2-雙(羥甲基)丁酸(2,2-Bis(hydroxymethyl)butyric acid；DMBA)、2,2-雙(羥甲基)丙酸(2,2-Bis(hydroxymethyl)propionic acid；DMPA)、1,4-丁二醇-2-磺酸鈉(1,4-butanediol-2-Sodium )及其混合物所組成之群組；該陽離子型雙醇或多元醇可選自由：N-甲基二乙醇胺(N-methyldiethanolamine；MDEA)、甲基二乙醇胺(methyldiethanolamine； MPEDEA)、三乙醇胺(Triethanolamine)及其混合物所組成之群組；以及該非離子型雙醇或多元醇可選自由：乙二醇(ethylene glycol； EG)、一縮二乙二醇(Diethylene glycol； DEG)、1,4-丁二醇((1,4-butanediol；BDO)、聚四氫氟喃醚二元醇(Polytetramethylene ether glycol；PTMEG)、聚環氧乙烷二醇(Polyethylene glycol；PEG)、聚環氧丙烷二元醇(Polypropylene glycol；PPG)、聚己二酸乙二醇酯二元醇( polyethylene adipate；PEA)、聚己二酸丁二醇酯二醇(polypropylene adipate；PBA)及其混合物所組成之群組。較佳地，該雙醇或多元醇可選自由：2,2-雙(羥甲基)丁酸(DMBA)、聚環氧乙烷二醇(PEG)、N-甲基二乙醇胺(MDEA)、及其混合物所組成之群組。
於本發明中，聚氨酯型高分子紫外線吸收劑可更包括一鏈延長劑。該鏈延長劑可選自由包含兩個以上的活性氫之多元胺及其混合物所組成之群組，該活性氫可選自由：-OH、-NH2 、及-NH-所組成之群組。據此，該鏈延長劑與該多異氰酸酯進行反應後，該鏈延長劑的活性氫可連接至該多異氰酸酯的-NCO官能基。更具體地，該鏈延長劑可選自：乙烯胺(ethyleneamines)類多元胺、聚醚胺(polyetheramines) 類多元胺、親水型多元胺及疏水型多元胺所組成之群組，乙烯胺類多元胺可舉例如：乙二胺(ethylene diamine；EDA)、二亞乙基三胺(diethylene triamine；DETA)、三亞乙基四胺( triethylene tetramine；TETA)、四亞乙基五胺(tetraethylene pentamine；TEPA)和五亞乙基六胺(pentaethylene hexamine；PEHA)、氨基乙基乙醇胺(Aminoethylethanolamine；AEEA)；聚醚胺類多元胺可舉例如：JEFFAMINE(商品名，購自Huntsman) ；親水型多元胺，可舉例如：乙二胺基乙(丙)基磺酸鈉(aliphatic diamine sulphonate)、胺基酸(amino acid )、二氨基苯甲酸(Diaminobenzoic acid)；以及疏水型多元胺可舉例如：1-氨基-3-氨基甲基3,5,5-三甲基-甲烷(1-amino-3-aminomethyl-3,5,5- trimethylcyclohexane)、雙-(4-氨基 - 環己基)-甲烷( bis-(4-amino- cyclohexyl)-methane)、雙-（4-氨基-3-甲基環己基）-甲烷(bis-(4-amino-3-methylcyclohexyl)-methane)、1,6-二氨基己烷(1,6-diaminohexane)。較佳地，該鏈延長劑可選自由：乙二胺(EDA)、氨基乙基乙醇胺(AEEA)、二亞乙基三胺(DETA)、三亞乙基四胺(TETA)、乙二胺基乙(丙)基磺酸鈉及其混合物所組成之群組。更佳地，該鏈延長劑可選自由乙二胺(EDA)、氨基乙基乙醇胺(AEEA)、及其混合物所組成之群組。
本發明之聚氨酯型高分子紫外線吸收劑之聚合物，其單體結構可舉例由下式(I)表示：
Figure TW201800548AD00001
(I)
於式(I)中，A為具有可反應活性氫之紫外線吸收劑，B為多異氰酸酯，C為雙醇或多元醇。
在本發明之聚氨酯型高分子紫外線吸收劑更包含鏈延長劑之情況下，本發明之聚氨酯型高分子紫外線吸收劑之聚合物，其單體結構可舉例由下式(II)表示：
Figure TW201800548AD00002
(II)
於式(II)中，A、B、C的定義與式(I)相同，D為鏈延長劑。
本發明更提供一種增進日光牢度之組成物，其包括上述之聚氨酯型高分子紫外線吸收劑，可應用在彈性體(elastomers)、密封劑(sealants)、膠黏劑(adhesives) 及塗料(coatings)等。此外，該增進日光牢度之組成物可更包括一添加劑係選自由：一中和劑、一載體、一稀釋劑、一賦形劑、及一穩定劑所組成之群組。
本發明提供的聚氨酯型高分子紫外線吸收劑及包含其之增進日光牢度之組成物，對織物具有良好的表面附著能力，用於處理多種材質目標物，能加強其日光牢度以及具有優異耐水洗性，極符合產業之需求。此外，利用本發明之聚氨酯型高分子紫外線吸收劑，未使用毒性化學物質，僅需使用含量極低之有機溶劑，並且不需額外添加界面活性劑，符合環保趨勢。
以下係藉由特定的具體實施例說明本發明之實施方式，熟習此技藝之人士可由本說明書所揭示之內容輕易地了解本發明之其他優點與功效。本發明亦可藉由其他不同的具體實施例加以施行或應用，本說明書中的各項細節亦可針對不同觀點與應用，在不悖離本創作之精神下進行各種修飾與變更。
除非文中另有說明，否則說明書及所附申請專利範圍中所使用之單數形式「一」及「該」包括複數個體。
除非文中另有說明，否則說明書及所附申請專利範圍中所使用之術語「或」通常包括「及/或」之含義。
本文所使用之術語「重量平均分子量」，係利用凝膠滲透層析(GPC)溶劑：四氫呋喃(THF)，所測定之換算成聚苯乙烯之重量平均分子量(Mw)的值。
詳細的製備方法於後文之實施例中描述，也可使用與實施例類似之方法製備聚氨酯型高分子紫外線吸收劑。本發明之聚氨酯型高分子紫外線吸收劑的製備方法(例如：合成方法、反應條件、順序等)及使用材料，並不限於本文中所提及者。
本發明之聚氨酯型高分子紫外線吸收劑具有優良之水分散性、滲透性、儲存安定性等，且應用範圍廣泛。本發明之聚氨酯型高分子紫外線吸收劑適用於各種基材，例如但不限於：纖維材料、皮革材料(例如，天然皮革、合成皮革)、發泡棉、木材等。尤其是，適用於纖維材料，包括：天然纖維(例如，植物性纖維、動物性纖維(如羊毛)及礦物性纖維)及人造纖維(例如再生纖維、半合成纖維及合成纖維(如聚酯纖維、尼龍纖維))。較佳的纖維材料為天然纖維素纖維(如：棉、麻、亞麻、大麻、苧麻等等)、動物性纖維(如羊毛)、再生纖維(如：黏液嫘縈等等)及合成纖維(如聚酯纖維、尼龍纖維)；更佳為棉。本發明之聚氨酯型高分子紫外線吸收劑亦適用於含上述纖維材料之混合纖維、混紡織物及混合織物等。
本發明之用於增進日光牢度之組成物中，可視需要，含有其他助劑，例如，但不限於：紫外線吸收劑、光穩定劑、抗氧化劑、界面活性劑、流平劑、增黏劑、消泡劑等，及其組合。
本發明將藉由實施例更具體地說明，但該等實施例並非用於限制本發明之範疇。除非特別指明，於下列實施例與比較例中用於表示成份含量以及物質量的「%」係以重量為基準。
[ 實施例 1] 製備化合物 1
取68.2g的α-[3-[3-(2H-苯并三唑-2-基)-5-(1,1-二甲基乙基)-4-羥苯基]-1-酮基丙基]-ω-羥基聚(酮基-1,2-乙烷二基) (α-[3-[3-(2H-Benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropyl]-ω-hydroxypoly(oxo-1,2-ethanediyl)，台灣永光化學工業股份有限公司)置入反應瓶，加入50.5g HDI TRIMER，升溫至65~75℃，當滴定NCO反應官能基莫耳數達到反應終點後（此時，Free NCO%=7%），加入5.4g DMBA，再反應至滴定NCO官能基莫耳數達到反應終點後（此時，Free NCO%=3.99%），加入16.0g 丙酮及5.4克N,N-二甲基乙基胺(N,N-Dimethylethylamine)，即製備出預聚物1。
將預聚物1加入300.0g去離子水中，並以攪拌機高速分散，全部加入後，再加入2.8g EDA及1.6g AEEA作為鏈延長劑，並攪拌至其穩定，即製備出化合物1，此高分子化合物1經GPC測量其重量平均分子量(Mw)為43,800。
[ 實施例 2] 製備化合物 2
取70.0g的α-[3-[3-(2H-苯并三唑-2-基)-5-(1,1-二甲基乙基)-4-羥苯基]-1-酮基丙基]-ω-羥基聚(酮基-1,2-乙烷二基) (α-[3-[3-(2H-Benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropyl]-ω-hydroxypoly(oxo-1,2-ethanediyl)，台灣永光化學工業股份有限公司)置入反應瓶，加入50.5g HDI TRIMER，升溫至65~75℃，當滴定NCO反應官能基莫耳數達到反應終點後（此時，Free NCO%=6.6%），加入2.2g DMBA、10.5g PEG300(聚乙二醇(Polyethylene Glycol)，Mw＝300)，再反應至滴定NCO官能基莫耳數達到反應終點後（此時，Free NCO%=2.8%），加入16.0g 丙酮及2.6g N,N-二甲基異丙胺(N,N-Dimethylisopropylamine)，即製備出預聚物2。
將預聚物2加入300.0g去離子水中，並以攪拌機高速分散，全部加入後，再加入2.4g EDA及1.4g AEEA作為鏈延長劑，並攪拌至其穩定，即製備出化合物2，此高分子化合物2經GPC測量其重量平均分子量為13,200。
[ 實施例 3] 製備化合物 3
取70.0g的α-[3-[3-(2H-苯并三唑-2-基)-5-(1,1-二甲基乙基)-4-羥苯基]-1-酮基丙基]-ω-羥基聚(酮基-1,2-乙烷二基) (α-[3-[3-(2H-Benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropyl]-ω-hydroxypoly(oxo-1,2-ethanediyl)，台灣永光化學工業股份有限公司)置入反應瓶，加入50.5g HDI TRIMER，升溫至65~75℃，當滴定NCO反應官能基莫耳數達到反應終點後（此時，Free NCO%=7.1%），加入1.79g MDEA、10.5g PEG300，再反應至滴定NCO官能基莫耳數達到反應終點後（此時，Free NCO%=3.67%），加入16.0g丙酮及1.8g乙酸(Acetic acid)，即製備出預聚物3。
將預聚物3加入300.0g去離子水中，並以攪拌機高速分散，加入後攪拌至其穩定即製備出化合物3，此高分子化合物3經GPC測量其重量平均分子量為131,700。
[ 實施例 4] 製備化合物 4
取70.0g的α-[3-[3-(2H-苯并三唑-2-基)-5-(1,1-二甲基乙基)-4-羥苯基]-1-酮基丙基]-ω-羥基聚(酮基-1,2-乙烷二基) (α-[3-[3-(2H-Benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropyl]-ω-hydroxypoly(oxo-1,2-ethanediyl)，台灣永光化學工業股份有限公司)置入反應瓶，加入50.5g HDI TRIMER，升溫至65~75℃，當滴定NCO反應官能基莫耳數達到反應終點後（此時，Free NCO%=6.67%），加入3.57g MDEA，再反應至滴定NCO官能基莫耳數達到反應終點後（此時，Free NCO%=3.7%），加入16.0g 丙酮及4.32g乙酸(Acetic acid)，即製備出預聚物4。
將預聚物4加入300.0g去離子水中，並以攪拌機高速分散，加入後攪拌至其穩定即製備出化合物4，此高分子化合物4經GPC測量其重量平均分子量為74,400。
[ 實施例 5] 製備化合物 5
取70.0g的α-[3-[3-(2H-苯并三唑-2-基)-5-(1,1-二甲基乙基)-4-羥苯基]-1-酮基丙基]-ω-羥基聚(酮基-1,2-乙烷二基) (α-[3-[3-(2H-Benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropyl]-ω-hydroxypoly(oxo-1,2-ethanediyl)，台灣永光化學工業股份有限公司)置入反應瓶，加入47.8g HDB，升溫至65~75℃，當滴定NCO反應官能基莫耳數達到反應終點後（此時，Free NCO%=7.2%），加入2.2g DMBA、10.5g PEG300，再反應至滴定NCO官能基莫耳數達到反應終點後（此時，Free NCO%=3.5%），加入16.0g 丙酮及2.6g N,N-二甲基乙基胺(N,N-Dimethylethylamine)，即製備出預聚物5。
將預聚物5加入300.0g去離子水中，並以攪拌機高速分散，加入後攪拌至其穩定即製備出化合物5，此高分子化合物5經GPC測量其重量平均分子量為91,900。
由上述實施例1至5所製備之化合物，其中化合物1和2的單體結構可由下式(II)表示，化合物3至5的單體結構可由下式(I)表示：
Figure TW201800548AD00003
(I)
Figure TW201800548AD00004
(II)
其中，A、B、C、D及各化合物之重量平均分子量(Mw)係整理於下表1。
表1
Figure TW201800548AD00005
[ 比較例 1]
取55.67g的α-[3-[3-(2H-苯并三唑-2-基)-5-(1,1-二甲基乙基)-4-羥苯基]-1-酮基丙基]-ω-羥基聚(酮基-1,2-乙烷二基)(α-[3-[3-(2H-Benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropyl]-ω-hydroxypoly(oxo-1,2-ethanediyl)，台灣永光化學工業股份有限公司)置入250毫升(ml)分離式反應瓶，攪拌升溫至50℃，接者加入HDI TRIMER22.20 g、以及DMAc(二甲基乙醯胺(N,N-Dimethylacetamide)) 19.50g，升溫至90℃，反應2~3小時(hr)(滴定NCO官能基莫耳數達到反應終點)，接者於降溫至70℃後，加入預先以1.30g之AcOH(醋酸)做酸鹼中和的MDEA(N-甲基二乙醇胺(N-methyldiethanolamine)) 2.59g、DMAc 7.20g，升溫至90℃反應2~3hr(滴定NCO官能基莫耳數達到反應終點)後，降溫至50℃，以獲得比較例1之化合物。
上述比較例1所製備之化合物單體結構可由下式(III)表示：
Figure TW201800548AD00006
(III)
其中，A為α-[3-[3-(2H-苯并三唑-2-基)-5-(1,1-二甲基乙基)-4-羥苯基]-1-酮基丙基]-ω-羥基聚(酮基-1,2-乙烷二基)，B為HDI TRIMER，C為MDEA。比較例1之化合物之重量平均分子量(Mw)約為3608.4。
[ 測試例 1] 日光牢度測試
取上述實施例及比較例所得之化合物之溶液 (80 g/l ~ 120 g/l)，及染色樣品布(13cm x 5cm)，將溶液倒入壓染機之滾輪上，在控制壓吸率80%的條件下，對染色樣品布作壓吸處理，處理後放至烘箱，於60℃乾燥15分鐘，乾燥後樣品布分為未水洗組及水洗5次組，未水洗組依據AATCC 16-2010方法3測試日光牢度(採用20個日照單位)，以分光光度計判斷經過人工日光照射後的色變情況，以儀器所測得級數作為判級標準。水洗5次組進行以下測試例2之水洗測試後，再進行日光牢度測試。
[ 測試例 2] 水洗測試
取測試例1之水洗5次組之樣品布，加入陪洗布至總重為1.8KG，陪洗布為大小92cm x 92cm，材質為聚酯纖維/棉混紡(50/50)的布樣。加入66g洗衣粉(1993年AATCC的洗衣粉)，水洗溫度為49℃±3℃，洗衣程序設定標準洗法：洗衣機水位18±0.5gal；攪動速度179±2spm；洗衣時間12分鐘；旋轉速度645±15rpm；以及最後旋轉時間6分鐘。每一次水洗完後不用烘乾，直接再倒入66g洗衣粉進行下一次水洗，直到5次水洗為止。於此進行的水洗測試係根據AATCC 135-2004’ 法進行。
未水洗組的實驗結果如下表2所示，水洗5次組的實驗結果如下表3所示，其中以未添加任何溶液之樣品布作為空白試驗(blank)：
表2
Figure TW201800548AD00007
表3
Figure TW201800548AD00008
由表2結果可知，樣品布添加了上述實施例及比較例所得之化合物之溶液後，日光牢度提升1級。再由表3結果可知，在經過5次水洗後，添加比較例1之化合物溶液之樣品布，其日光牢度降低1級；相較之下，添加本案實施例之化合物1-5溶液之樣品布，其耐日光牢度仍提升0.5-1級。因此，可證明本案請求之化合物能賦予基材優異之日光牢度及耐水洗性。此外，本案實施例之化合物1-2包含鏈延長劑，化合物3-5不包含鏈延長劑，相較之下，兩者皆能賦予基材優異之日光牢度及耐水洗性。
上述實施例僅係為了方便說明而舉例而已，本發明所主張之權利範圍自應以申請專利範圍所述為準，而非僅限於上述實施例。
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Claims (14)

  1. 一種聚氨酯型高分子紫外線吸收劑，其聚合物係由：具有一可反應活性氫之紫外線吸收劑，與一多異氰酸酯(Polyisocyanate)及一雙醇或多元醇(Polyol)反應而得； 其中，該聚氨酯型高分子紫外線吸收劑之重量平均分子量介於10,000至200,000的範圍。
  2. 如申請專利範圍第1項所述之聚氨酯型高分子紫外線吸收劑，其中，該紫外線吸收劑包含可反應活性氫係選自由：-OH、-NH2 、及-NH-所組成之群組。
  3. 如申請專利範圍第1項所述之聚氨酯型高分子紫外線吸收劑，其中，該紫外線吸收劑係選自由：苯並三唑類(Benzotriazole) 紫外線吸收劑、二苯酮類(Benzophenone) 紫外線吸收劑、及三嗪類(Triazine) 紫外線吸收劑、草醯苯胺類(Oxanilide)紫外線吸收劑、氰基丙烯酸酯類(Cyanoacrylate)紫外線吸收劑所組成之群組。
  4. 如申請專利範圍第1項所述之聚氨酯型高分子紫外線吸收劑，其中，該多異氰酸酯係選自由：異佛爾酮二異氰酸酯(Isophorone diisocyanate；IPDI)、氫化二苯基甲烷二異氰酸酯( 4,4’-dicyclohexylmethane diisocyanate；HMDI)、六亞甲基二異氰酸酯(Hexamethylene diisocyanate；HDI)、苯二亞甲基二異氰酸酯(1,3-Bis(isocyanatomethyl)benzene；XDI)、四甲基間苯二亞甲基二異氰酸酯(Tetramethyl xylylene diisocyanate；TMXDI)、2,2,4-三甲基六亞甲基二異氰酸酯(2,2,4-trimethylhexamethylene diisocyanate；HDI TRIMER)、六亞甲基二異氰酸酯縮二脲(Hexamethylene diisocyanate biuret；HDB)及多聚體與其混合物所組成之群組。
  5. 如申請專利範圍第1項所述之聚氨酯型高分子紫外線吸收劑，其中，該雙醇或多元醇係選自由：陰離子型雙醇或多元醇、陽離子型雙醇或多元醇、非離子型雙醇或多元醇及其混合物所組成之群組。
  6. 如申請專利範圍第5項所述之聚氨酯型高分子紫外線吸收劑，其中，該陰離子型雙醇或多元醇係選自由：2,2-雙(羥甲基)丁酸(2,2-Bis(hydroxymethyl)butyric acid；DMBA)、2,2-雙(羥甲基)丙酸(2,2-Bis(hydroxymethyl)propionic acid；DMPA)、1,4-丁二醇-2-磺酸鈉(1,4-butanediol-2-Sodium )及其混合物所組成之群組。
  7. 如申請專利範圍第5項所述之聚氨酯型高分子紫外線吸收劑，其中，該陽離子型雙醇或多元醇係選自由：N-甲基二乙醇胺(N-methyldiethanolamine；MDEA)、甲基二乙醇胺(methyldiethanolamine； MPEDEA)、三乙醇胺(Triethanolamine)及其混合物所組成之群組。
  8. 如申請專利範圍第5項所述之聚氨酯型高分子紫外線吸收劑，其中，該非離子型雙醇或多元醇係選自由：乙二醇(EG)、一縮二乙二醇(DEG)、1,4-丁二醇(BDO)、聚四氫氟喃醚二元醇(PTMG)、聚環氧乙烷二醇(PEG)、聚環氧丙烷二元醇(PPG)、聚己二酸乙二醇酯二元醇(PEA)、聚己二酸丁二醇酯二醇(PBA)及其混合物所組成之群組。
  9. 如申請專利範圍第1項所述之聚氨酯型高分子紫外線吸收劑，更包括一鏈延長劑。
  10. 如申請專利範圍第9項所述之聚氨酯型高分子紫外線吸收劑，其中，該鏈延長劑可選自由包含兩個以上的活性氫之多元胺及其混合物所組成之群組，其活性氫可選自由：-OH、-NH2 、及-NH-所組成之群組。
  11. 如申請專利範圍第10項所述之聚氨酯型高分子紫外線吸收劑，其中，該鏈延長劑係選自由：乙烯胺(ethyleneamines)類多元胺、聚醚胺(polyetheramines) 類多元胺、疏水型多元胺及親水型多元胺及其混合物所組成之群組。
  12. 一種用於增進日光牢度之組成物，其係包括如申請專利範圍第1項所述之聚氨酯型高分子紫外線吸收劑。
  13. 如申請專利範圍第12項所述之組成物，更包括一添加劑係選自由：一中和劑、一載體、一稀釋劑、一賦形劑、及一穩定劑所組成之群組。
  14. 如申請專利範圍第12項所述之組成物，其係用於塗料、膠黏劑、密封劑與彈性體。
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EP2935373A4 (en) * 2012-12-20 2016-07-27 3M Innovative Properties Co COPOLYMERS WITH ULTRAVIOLETT LIGHT-ABSORBENT GROUPS AND FLUOROLPOLYMER COMPOSITIONS THEREWITH
KR102194159B1 (ko) * 2012-12-20 2020-12-22 쓰리엠 이노베이티브 프로퍼티즈 캄파니 자외선 흡수 기를 갖는 올리고머를 포함하는 플루오로중합체 조성물
TWI530555B (zh) * 2014-09-02 2016-04-21 臺灣永光化學工業股份有限公司 柔軟劑組成物
CN104452307B (zh) * 2014-12-15 2016-06-22 辽宁恒星精细化工有限公司 一种透气、抗紫外线、抗静电聚氨酯树脂涂层胶及其制备方法
CN105131565A (zh) * 2015-07-22 2015-12-09 东莞市雄林新材料科技股份有限公司 一种高色牢度热塑性聚氨酯、热塑性聚氨酯合成革及其制备方法

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