TW546315B - Transparent, non-elastomeric, high hardness, impact resistant polyurethane material and eyewear lens made therefrom - Google Patents

Transparent, non-elastomeric, high hardness, impact resistant polyurethane material and eyewear lens made therefrom Download PDF

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TW546315B
TW546315B TW087119961A TW87119961A TW546315B TW 546315 B TW546315 B TW 546315B TW 087119961 A TW087119961 A TW 087119961A TW 87119961 A TW87119961 A TW 87119961A TW 546315 B TW546315 B TW 546315B
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polyurethane material
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Edwin C Slagel
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Simula Inc
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Description

546315
本發明為美國專利申請 案,該案又為美國專利申 案,二案皆併述於此以供 背景 ~ 案第0 8 /59 5,262號之部份 請案第08/^82, 5 62號之部 參考。 連續 份連續 發明領域 光學透明耐熱及耐衝擊性聚气 本發明係關於一種剛性 基甲酸乙酯。 發明背景 目前 ’全部光學透明塑膠材料比較其耐衝擊性 料為聚碳酸酯。此種材料夕姓%炎y H ^ 之b準材 變之溫度及壓力。聚碳酸酯之埶畸抖進订對 力為約280度F。 du皿度於264PS1纖維應 厚度0· 25吋之聚碳酸酯擠塑薄片具有〇· 22卡規FSp(斷片 模擬投射彈)V-50耐衝擊等級為925f t· /sec。ν-5〇為5〇%22 卡規投射彈經由0 · 2 5吋聚碳酸酯薄片發射貫穿置於聚碳酸 薄片背面後方6吋的22毫米厚度20 24 T6鋁片(”見證片”) 的速度測量值。 美國專利3,8 6 6,2 4 2 (併述於此以供參考)揭示一種聚氨 基甲酸乙酯聚合物保護屏。聚氨基甲酸乙酯之生產方法係 經由: (a) 分子量約700至1,〇〇〇之聚乙二醇或聚酯二醇與亞甲 基-貳(異氰酸環己酯)以約3 NCO對每個羥基之當量比反應。 形成預聚物,及 (b) 預聚物與芳族胺固化劑以〇 · 9 〇對1. 〇4NH9/ 1. 0NCO之
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第5頁 546315 «
當里比反應,該芳族胺固化劑介於二芳族環間有一個亞甲 基橋,如4, 4’ -亞曱基貳(2 -氯苯胺)。 美國專利4, 80 8, 690 (併述於此以供參考)揭示一種由多 兀醇固化預聚物製備之透明聚氨基曱酸乙酯聚合物。預聚 物係由聚異氰酸酯及至少一種多官能含羥基中間物製備。 美國專利4, 20 8, 5 0 7揭示一種撓性聚氨基曱酸乙酯—脲彈 ,體,其製法係經由反應:(A) 一種預聚物,其係經由分子· 量6 0 0至1〇, 〇〇〇之大致雙官能多羥化合物與含有至少一nc〇 , 基鍵結至環月曰知結構的有機二異氰酸酯,以可提供她· NCO比為1:1·2至1:10之數量反應獲得,與(B)3,3/,、5y5,: 四甲基4,4 - 一胺基二苯基曱院’ A及B係以約ι:〇·8至 1 : 1 · 2之莫耳比反應。 · · 發明概沭 本發明之光學澄清聚氨基甲酸乙酯之製法可經由首先生 產預聚物,其係經由一或多種聚酯二醇類,聚己内酯二醇 類’聚ϋ二醇類或聚碳酸酯二醇類具有重均分子量約4〇〇 至約2 0 0 〇與脂族或環脂族二異氰酸酯以對每個⑽約2 · $至 4· 0 NCO之當量比反應生產。然後預聚物與芳族二胺固化 劑如二乙基甲苯二胺,以約〇· 85至1· 02ΝΗ2/1· 〇NCO,較佳❿ 約 〇·90 至 l.〇NH2/l.〇NCO,及更佳約 0.92 至 〇.96NH2/l.〇NC土〇 之當量比反應。 本發明之聚氨基甲酸乙酯特別可用於需要絕佳耐衝擊性 加上高熱畸變溫度之透明用途,例如建築玻璃帷幕牆,汽 車鑲後玻璃,警用盾牌,飛機座艙罩,面罩,帽舌,光與
546315 案號 87119961 五、發明說明(3) 曰 修正 鏡片及太陽鏡片,護目鏡及透明i曱。 ^發明之目的係提供比較先前技術材料具有絕佳光學透 明聚氨基甲酸乙醋類。抗性及南熱崎變溫度之透 耐用於商業用途成本降低之透明 目的係藉由縮短 度及縮短模具停駐時間辦 ^ J降低I私溫 之製造過程。 1 9進透明耐衝擊性聚氨基甲酸乙酯 此等及其它本發明之目的 ”附之申請專利範心月:細節說明、實例 細說明 一進步細即。 本發明之聚氨基甲酸乙,從丄 、 類,含羥基中間物,及二二脂族或環脂族二異氰酸酯 成份之細節說明。 、—私:固化劑製備。後文為各該 金間物 可用於製備本發明之聚_ 包括聚龜二醇類1已内;基!酸乙醋類之含經基中間物 酯二醇類,其具有重均八:=醇類,聚醚二醇類及聚碳酸 約4〇〇至約1〇00。 刀于量由約400至約200 0,及較佳 有用的聚酯二醇類包括一 羧酸(如己二酸,丁二酸及八或夕種含4至10個碳原子之二 碳原子之低分子量二醇類(:一酸)與一或多種含2至10個 醇,1,4- 丁二醇,新戊:(如=醇,丙二醇,二乙二 - x 一知,1,6-己二醇及1,10 -癸二醇) 87119961.ptc 第7頁 修正頁 2_·〇1·21·〇〇7 546315
之酯化產物。較佳聚酯二醇類為己二酸與含2至1〇個碳原 子之二醇類之酯化產物。 有用的聚己内,二醇類包括ε—己内醋與一或多種上列 低分子量二醇類之反應產物。此外,冑用的含羥基中間物 包括由或夕種低分子量二羧酸,如己二酸及己内酯類與 -或多種上列低分子量二醇類生產的過醋類。 較佳聚S旨二醇及聚己内g旨二醇可藉幕所周知之_化或轉 移酯化程序衍生而得,例如述於參考文獻D M. y〇ung,F· Hostettler et al., "Polyesters from Lactone'1,
Union Carbide F-40 , p·147 。 有用的一醇類包括聚四亞甲基醚二醇。 有用的聚碳酸酯二醇類包括脂族聚碳酸酯二醇類。較佳 脂族聚碳酸酯二醇類係由Enichem以商品*Ravecarb 102(分子量=1,〇〇〇)及Ravecarb 106(分子量=2,〇〇〇)製造 出售。 最佳含說基中間物為:(a)己二酸與一或多種選自1,4一丁 二醇,1,6-己二醇,新戊二醇及ι,ι〇_癸二醇之酯化產 物;(b)e -己内酯與一或多種選自1,4 - 丁二醇,1,6-己二 醇,新戊二醇及1,1()-癸二醇之二醇之反應產物;(c)聚四 亞甲基二醇;(d)脂族聚碳酸酯二醇類,及(e)此等含羥基 中間物之混合物。 5異氰酸酯類 可用於製備本發明之聚氨基甲酸乙酯類之脂族或環脂族 二異氰酸酯類包括二環己基甲烷二異氰酸酯,及較佳其異
第8頁 修正買2〇〇0· 01.21. 〇〇8 546315 ----案號87119961 _年月 日 修正 五、發明說明(5) 一 " '〜 構物混合物含有約2 〇 -1 〇 〇 % 4,4,_亞甲基貳(環己基異氰酸 酉旨)之反,反-異構物,後文稱做” PICMH (對異氰酸根環已基 甲烧)。其它本發明有用的通常存在於二環己基曱烷二異 氮酸醋之位置及/或立體異構物混合物之成份為p丨CM之 順’反及順’順-異構物及2, 4,-亞甲基貳(環己基異氰酸 酯)之立體異構物。此等及反,反PICM異構物之存在量可 藉由用於製備二環己基甲烷二異氰酸酯之程序控制。較佳 二異氰酸酿類為異構物p ICM混合物。特佳混合物含有不低 於約20%反,反-異構物及不多於約2〇%4, 4,—亞甲基貳(環 己基異氰酸酯)之順,順—異構物。三種44,—亞甲基貳(環 己基異乱酸S曰)之異構物顯示如後·· 反,反
NCO
^^TNCO 順,反
NCO
NCO 〇 順,順 本發明使用的PICM可藉業界眾所周知之程序以光氣處理 對應4, 4’ -亞甲基貳(環己基胺)(PACM)製備,例如揭示於 美國專利 2, 644, 007,2, 680, 127 及2, 908, 703,併述於此 以供參考。PACM異構物當進行光氣處理反應時,於室溫獲
87119961.ptc 第9頁 修正頁 2000. 〇!. 21. 009 546315 修正 妒由,ί 。卩彳刀液相或固相之1"1CM。P ACM異構物混合物可 下八二#亞曱基一胺基或經由於水及醇如曱醇及乙醇存在 2 ^又…晶PACM異構物混合物獲得。 與二^有用的知私及環脂族二異氰酸酯類包括得自A r c 〇化 二二3一異氰酸根—甲基―3, 5, 5—三甲基環己基異氰酸6旨 (IpDI”),具如下結構式:叫
公司所’間—四甲基二甲苯二異氰酸酯(1,3-貳U- 二,:土一1一甲基乙基)一苯),其商標名為TMXDI ®(間)脂 矢”氰酸酯,及具如下結構式: 巧 。心4^^ 一; 太 Uz 缺t 1明書及申請專利範圍内所參照脂族及環脂族二異氰 2知:、、、欲包含式R—(NC〇、之化合物,R為脂族基、環脂族 土、或為以烷基取代之芳族,其中氮鍵結至烷基取代基, 但不包含此式之下R為芳族基而氮鍵結至芳環上。 -一胺固化齊丨
較佳用於製備本發明之聚氨基甲酸乙酯之芳族二胺固化 劑為2, 4j二胺基一3, 5 -二乙基—甲苯,2, 6一二胺基一3, 5一二 乙基曱苯及其混合物(合稱π二乙基甲苯二胺,,或,,DETDAf,) ,其係由Albemarle公司以商品名Ethacure 100出售。 DETDA於室溫為液體具有黏度於25°C為156cs。DETDA為異 構物’ 2, 4-異構物占75-81%而2, 6-異構物占18-24%。 DETDA具如下結構式:
87119961.ptc 第10頁 修正頁 2000.01.21.010 546315 案號87119961 年月日 修正
87119961.ptc 第21頁 修正頁 2000.01.21.021

Claims (1)

  1. 5_15各泰 1 89· i.f2i , : ^k號87119961_年月曰 修正_絛正太 _ ----------------—y 卜 <*»-·!*« *»«Α-ΛίΜ«·Λί*» 六、申請專利範圍 1. 一種透明、非彈性、高硬度之耐衝擊性聚氨基甲酸乙 酯材料,其包含下列之反應產物: (a) 聚氨基甲酸乙酯預聚物,其係經由脂族或環脂族二 異氰酸酯與至少一種重均分子量4 0 0至2 0 0 0之選自包括聚 酯二醇類,聚己内酯二醇類,聚醚二醇類及聚酸酯二醇 類;其混合物之含羥基中間物以2.5至4.0NCO/1.0 0H當量 比反應製備;及 (b) 至少一種第一芳族二胺固化劑選自包括2, 4_二胺基 , -3,5 -二乙基甲苯,2, 6 -二胺基-3, 5 -二乙基甲苯及其混合 物以0. 85至1. 02ΝΗ2/1· 0 NCO當量比反應。 2. 如申請專利範圍第1項之聚氨基甲酸乙酯材料,其中 該聚氨基曱酸乙酯材料為聚氨基曱酸乙酯預聚物,至少一 種第一芳族二胺固化劑,及至少一種第二二胺固化劑選自 包括下式化合物所得反應產物: Ri Ri I I H2N ^ . nh2
    % 其中匕及匕各自分別選自包括甲基,乙基,丙基及異丙基 及匕係選自包括氫及氯。 3.如申請專利範圍第1項之聚氨基甲酸乙酯材料,其中 該二異氰酸酯係選自包括4, 4’ -亞曱基貳(環己基異氰酸 酯),3-異氰酸根-曱基-3, 5, 5-三曱基環己基異氰酸酯, 間-四曱基二曱苯二異氰酸酯及其混合物。
    87119961.ptc 第22頁 2000.01.21.022 546315 修正 案鍊 8711QQR1 六、申請專利範圍 二ί m利1a圍第1項之聚氨基甲酸乙酯材料,其中 ΐ:二1 L旨材料具有熱畸變溫度於264Psi係於210 度F至3 2 5度F之範圍。 二ΐ Hi利範圍第1項之聚氨基甲酸乙醋材料,其中 度F ^欠乙醋材枓具有熱畸變溫度於264pS 1至少為 二:i : ί利犯圍第1項之聚氨基甲酸乙酯材料,其中 基甲酸乙醋材料具有熱崎變溫度於264psi至少為 範圍第1項之聚氨基甲酸乙醋材料,其中 基曱酸乙醋材料為光學透明具有發光透射率至少 8:=請專利範圍第i項之聚氨基甲酸乙醋材料 咸1乱基曱酸乙醋材料之0.25吋厚度薄片具有^5〇 〇、中 卡規FSP評分至少11〇〇呎/秒。 · 9二如申清專利範圍第1項之聚氨基甲酸乙酯材料,其中 τ間物之重均分子量為40 0至1 000。 > 1^·、〜如申請專利範圍第1項之聚氨基甲酸乙酯材料,复 瀘』3羥基中間物係選自包括:(a)己二酸與一種或多種選白 包括1,4 肛、目 一 一醇,I 6-己二醇,新戊二醇及1,10 —癸二醇 之一醇類之酯化產物;(b) ε -己内酯與一種或多種選自包
    546315 _案號87119961_年月曰 修正_ 六、申請專利範圍 括1,4- 丁二醇,1,6-己二醇,新戊二醇及1,10 -癸二醇之 二醇類之反應產物;(c)聚四亞曱基二醇;(d)脂族聚碳酸 酯二醇類;及(e)此種含羥基中間物之混合物。 1 2.如申請專利範圍第1項之聚氨基甲酸乙酯材料,其中 該環脂族二異氰酸酯為4, 4’ -亞曱基貳(環己基異氰酸酯) 之異構物混合物其包含至少20% 4, 4’ -亞曱基貳(環己基異 氰酸酯)之反,反-異構物。 1 3.如申請專利範圍第1項之聚氨基甲酸乙酯材料,其中 , 該預聚物進一步包含一種紫外光安定劑。 . 1 4.如申請專利範圍第1 3項之聚氨基甲酸乙酯材料,其 f 中該紫外光安定劑係選自包括苯并三唑類,封阻胺光安定 劑,及其混合物。 1 5.如申請專利範圍第1項之聚氨基甲酸乙酯材料,其中 該預聚物進一步包含一種抗氧化劑。 1 6.如申請專利範圍第1 6項之聚氨基甲酸乙酯材料,其 中該抗氧化劑為多官能封阻酚。 1 7.如申請專利範圍第1項之聚氨基甲酸乙酯材料,其中 該聚氨基曱酸乙酯材料當使用異丙醇測量時具有應力耐裂 性大於70 0 0磅/平方吋。 1 8.如申請專利範圍第1項之聚氨基曱酸乙酯材料,其中 該預聚物進一步包含一種三元醇其含量足夠產生1 %交聯, 以反應物之當量為基準。 1 9.如申請專利範圍第1 8項之聚氨基甲酸乙酯材料,其 中該三元醇係選自包括三羥甲基乙烷,三羥曱基丙烷及其
    87119961.ptc 第24頁 2000.01.21.024 546315 案號 87119%1__年月日_ί±£-_—_ — 六、申請專利範圍 混合物。 2 0 · —種透明、非彈性、高硬度之耐衝擊性聚氨基曱酸 乙酯之材料,其包含下述反應產物:
    (a) —種聚氨基曱酸乙酯預聚物,其係經由一種選自包 括4, 4’ -亞曱基貳(環己基異氰酸酯),3-異氰酸根甲基-3, 5, 5-三曱基環己基異氰酸酯,間-四甲基二甲苯二異氰酸 酯及其混合物之二異氰酸酯與至少一種具有重均分子量 400至2000之選自包括:(a)己二酸與一種或多種選自包括 1,4-丁二醇,1,6-己二醇,新戊二醇及1,10 -癸二醇之 二醇類之酯化產物;(b)e -己内酯與一種或多種選自包括 1,4- 丁二醇,1,6-己二醇,新戊二醇及1,10 -癸二醇之二 醇類之反應產物;(c )聚四亞甲基二醇;(d )脂族聚碳酸酯 二醇類’及(e)此種含羥基中間物之混合物以2. 5至4. 0 NCO/1· 0 OH之當量比反應製備; (b) 至少一種二胺固化劑其係選自包括2, 4一二胺基—3, 5-二乙基曱苯,2, 6 -二胺基-3, 5 -二乙基甲苯及其混合物, 以0·95至1·〇2ΝΗ2/1·0 NCO之當量比反應,其中該聚氨基 曱酸乙S旨材料具有熱畸變溫度於Μ 4psi至少為30 0度F。
    2 1 · —種眼鏡鏡片,其係由申請專利範圍第1項之聚氨基 甲酸乙酯材料製得。 2 2 ·如申請專利範圍第21項之眼鏡鏡片,其中該鏡片係 選自由太陽眼鏡鏡片、眼科鏡片及保護鏡片所組成之群。 23. —種眼鏡鏡片,其係由申請專利範圍第2〇項之聚 基甲酸乙酯材料製得。
    第 25 頁 200〇·〇ι·2ΐ·025 546315
    曰 修正 、登白士如申θ請專利範圍第23項之眼鏡鏡片,其中該鏡片係 5 ^太h陽眼鏡鏡片、眼科鏡片及保護鏡片所組成之群。 該- ·胺°申請專利範圍第1項之聚氨基甲酸乙酯材料,1中 2;如化:為經色彩穩定化。 中該-申请專利範圍第20項之聚氨基甲酸乙酯材料,发 ^劑為經色彩穩定化。 ^ 中聚与*申凊專利範圍第20項之聚氨基甲酸乙酯材料,盆 80%。 〇 ®曰材枓為光學透明且具有發光透射率至少 2 8 女 中聚_ 1申清專利範圍第20項之聚氨基曱酸乙醋材料’其 規FSp"練\甲酸乙酿材料之〇· 25吋厚度薄片具有卜5 0 0· 22卡 2 9 °为至少11 0 0呎/每秒。 中該2、,申明專利範圍第2 0項之聚氨基曱酸乙酯材料,其 30.H基/間物之重均分子量為400至1〇〇〇 ° 中該二s /月專利範圍第2 〇項之聚氨基甲酸乙s旨材料’其 構物ί二2 ΐs旨為4,4’ -亞曱基戴(環己基異氰酸_)之異 酉旨)物其包含至少20% 4,4,_亞甲基武(環己基異氰酸 31反,反-異構物。 中該預臂申:、隹專利乾圍第20項之聚氨基甲酸乙酯材料,其 β歎物進一步句冬_ 32·如申杜直w匕3種紫外光安定劑。 3曱δ月專利範圚篦q 1 申明專利la圍第20項之聚氨基甲酸乙酯材料,其
    87ll"6l.ptc t中該紫外光安定劑俾/自V?聚氨基甲酸乙_ ’ ^ 〜及其混合物。 匕括苯开三唑類,封阻胺光安定 第26頁 2000.01.21.026 546315 •… _案號87119961_年月曰 修正_ 六、申請專利範圍 中該預聚物進一步包含一種抗氧化劑。 3 4.如申請專利範圍第33項之聚氨基曱酸乙酯材料,其 中該抗氧化劑為多官能封阻酚。 3 5.如申請專利範圍第2 0項之聚氨基曱酸乙酯材料,其 中該聚氨基甲酸乙酯材料當使用異丙醇測量時具有應力耐 裂性大於70 0 0磅/平方吋。 3 6.如申請專利範圍第20項之聚氨基甲酸乙酯材料,其 中該預聚物進一步包含一種三元醇其含量足夠產生1%交 、 聯,以反應物之當量為基準。 . 37.如申請專利範圍第36項之聚氨基甲酸乙酯材料,其 4 中該三元醇係選自包括三羥甲基乙烷,三羥甲基丙烷及其 混合物。
    87119961.ptc 第27頁 2000.01.21.027
TW087119961A 1998-09-02 1998-12-02 Transparent, non-elastomeric, high hardness, impact resistant polyurethane material and eyewear lens made therefrom TW546315B (en)

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