CN109384878B - 含吡唑啉类或/及苯丙烯酸类化合物之防蓝光系统 - Google Patents

含吡唑啉类或/及苯丙烯酸类化合物之防蓝光系统 Download PDF

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CN109384878B
CN109384878B CN201710674417.XA CN201710674417A CN109384878B CN 109384878 B CN109384878 B CN 109384878B CN 201710674417 A CN201710674417 A CN 201710674417A CN 109384878 B CN109384878 B CN 109384878B
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CN109384878A (zh
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胡汉民
曾裕峰
魏海涛
姜方园
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Jiangsu Yushida New Material Technology Co ltd
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Priority to JP2020529789A priority patent/JP7505760B2/ja
Priority to KR1020207006818A priority patent/KR102458704B1/ko
Priority to PCT/CN2018/076390 priority patent/WO2019029148A1/zh
Priority to US16/637,271 priority patent/US20200181363A1/en
Priority to TW107127489A priority patent/TWI737927B/zh
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Abstract

本发明关于防蓝光系统,特征在于,其中的防蓝光剂具有式(I)吡唑啉或/及式(II)苯丙烯酸化合物结构。式(I)或/及式(II)化合物可对短波长蓝光作全面吸收,以保护眼睛；也可对长波长的蓝光做选择性的吸收,使得穿透光具有特佳的视觉感受。本发明可应用于例如光学膜、光学镜片、护目镜、护肤、照明、涂料、粘合剂、或面板等产品。该等产品具有浅色外观且穿透光具有绝佳视觉感受。
Figure DDA0001373905900000011

Description

含吡唑啉类或/及苯丙烯酸类化合物之防蓝光系统
技术领域
本发明涉及防蓝光系统,包括防蓝光组合物及防蓝光膜。防蓝光膜系由防蓝光组合物加工制成,防蓝光组合物或防蓝光膜包括新颖的防蓝光剂,可对短波长蓝光作全面吸收,以保护眼睛；也可对长波长的蓝光做选择性的吸收,使得穿透光具有特佳的视觉效果。本发明具色浅与选择性吸收蓝光的特殊优点,可应用于例如光学膜、光学镜片、护目镜、护肤、照明、涂料、粘合剂、或面板等领域。
背景技术
可见光分红、橙、黄、绿、蓝、靛、紫光，红光波长最长、紫光最短，波长越短、能量越高。蓝光可以引发体内自由基Investigative Ophthalmology&Visual Science(20140731),55(7),pp.4119-4127。3C屏幕散发的蓝光，易在昏暗中穿透眼睛，会使睫状肌痉挛致老花眼，长期会出现黄斑部病变。目前过滤蓝光剂主要是染料类与无机荧光粉类化合物,作为防蓝光剂缺点包括颜色太深。例如茶色的眼镜(CN106466925,CAPLUS AN 2017:351046),并不适用于室内。
优良的防蓝光剂必须具有1.可以过滤蓝光2.本身浅色的两个基本条件,此外,还需要具有3.可以选择性吸收蓝光的特性。因为无选择性的吸收全部波段蓝光,会造成视觉上不自然的感觉。在高端的应用上,防蓝光剂对特定的蓝光波段的吸收度,需要随着波长增加而呈现逐渐的减小,也就是说,较长波长的蓝光必需有较大的穿透度。例如光学透镜,在410nm到450nm波段,所透过的蓝光需要具有 50％到100％渐增的穿透度。如此,可造成视觉上较佳的感觉。因此，做为防蓝光剂的条件是非常严峻的，市面上极少有符合1.可以过滤蓝光、2.本身浅色、3. 可以选择性吸收蓝光,三个特性的防蓝光产品。
曾有结构与本发明式(II-1)化合物极为相近的式(II-5)化合物,二甲基(对甲氧基亚苄基)丙二酸酯(商品名Eusorb-1988或Clariant hostavin pr 25),被揭示。
Figure GDA0003893710680000011
式(II-5)化合物最大吸收峰在314nm,被广泛应用于UVB(290-320nm)紫外线吸收剂,例如JP 4822129(CAPLUS AN 2008:1039270)。但并无防蓝光功效(本发明表1)。已知本发明对位胺基苯丙烯酸乙酯化合物(式II-1),被揭示的最大吸收在380nm以下,例如US2004126700表1,所揭露最大吸收在338-339nm(EC13)。因此,不论OCH3或N(CH3)2取代的对位2-亚苄基丙二酸二甲基酯(式II-1或式II-5 化合物),在过去未曾被应用于抗蓝光,也不被认为适用于防蓝光。
Figure GDA0003893710680000021
曾有结构与本发明式(II-2)化合物极为相近的式(II-7)化合物,氰基对甲氧基肉桂酸酯,被揭示。(II-7)的最大吸收峰在340nm,被应用于紫外线吸收剂。例如 JP09221583(CAPLUS AN 1997:571294)和US4284621(CAPLUS AN 1980:116437)的权利要求第1项,都揭示在UVA紫外线吸收应用。已知发明式 (II-2)化合物的用途是作为光引发剂,揭示于J.App.Polym.Sci.Photosensitive resins containing p-dimethyl-aminobenzylidenederivatives and diphenyliodonium salt as photoinitiators,1987,34(8),p.2747-56或 JP03062163B(CAPLUS AN 1986:79233)。其作用在于引起自由基并产生系列光化学反应。该作用与本发明防蓝光剂的保护有机体的作用完全不同,也从未被应用或预测在防蓝光功能。
本发明式(I)吡唑啉化合物原系用于印刷电路板的光刻胶(光阻)中当作光引发剂、或在电荷传输材料印刷电路板的不透光加纤树脂层中当反射作用荧光增白剂(whitening agent)、或在电子照相(electrophotography)领域中当成电荷传输(chargetransfer)功用、或当作抗菌剂。例如CN102012634A第5页(或 US8198008B2第4栏)揭示化合物(I-1)作为光引发剂、US8361697揭示化合物 (I-1)在h-line(405nm)作为高感度光引发剂、JP 63033481(CAPLUS AN 1981:10007)揭示化合物(I-2)、(I-3)作为光引发剂。又如JP3121096(CAPLUS AN 1994:43960)揭示化合物(I-1)在印刷电路板的不透光加纤树脂中,当成反射作用的荧光增白剂、Ganguang Kexue Yu Guang Huaxue(2000),18(2),160-164(CAPLUS AN 2000:417529)揭示化合物(I-2)、(I-3) 的发光性质。再例如US3837851中揭示化合物(I-2)、(I-3)在电子照相 (electrophotography)领域当成电荷传输功用。再例如在 Chemical&Pharmaceutical Bulletin,46(8),1998,p.1254中揭示(I-2)、(I-3)具抗菌功效。以上的作用与本发明防蓝光的过滤与保护功能完全无关,也从未被应用或预测在防蓝光功能。
发明内容
优良的防蓝光产品,应具有过滤蓝光基本功能和良好的颜色外观。特佳的防蓝光产品,对特定波段的蓝光更需具有不同吸收能力,使得透过光呈现较佳蓝光的视觉感受。因此,作为优良防蓝光剂的条件是相当严峻的。
为达此目的,本发明特别设计与筛选防蓝光化合物。令人惊讶地,发明人设计出式(I)与式(II)化合物,可应用做为特佳的防蓝光剂。本发明并设计出一种单独使用(I)或式(II)或合并使用(I)或式(II)防蓝光剂的防蓝光系统。本发明克服了传统防蓝光剂的缺点。例如,克服了传统深色染料或无机荧光粉防蓝光剂所造成产品颜色太深的缺点。又例如,克服了传统防蓝光剂会过度吸收长波长蓝光而造成视觉感受不佳的缺点。
本发明防蓝光剂系统最基本的设计是单独使用式(I)或单独使用式(II)防蓝光化合物。因为在约400±20nm,式(I)或式(II)都有最大吸收峰。防蓝光化合物也可组合使用,例如是(I-1)、式(I-2)、式(I-3)三个类似物间的组合,或例如是式(II-1)、式(II-2)两个类似物间的组合。其优点是,一方面,类似物间具有良好的相容性,另一方面,藉由调整类似物间的比例,可对不同波段的蓝光选择性地吸收,使得穿透的蓝光具有较佳的视觉感受。
(I-1)、(I-2)、(I-3)在蓝光区最大吸收各约为390nm、380nm、420nm(不同溶剂中略有不同)。以特定比例相混合,可达成不同的过滤蓝光功效。(I-1)、(I-2)、 (I-3)化合物的结构相近,几乎可以以任何比例相混合。因此藉由控制(I-1)、(I-2)、 (I-3)化合物的比例,可对不同波段的蓝光选择性地吸收,使得穿透的蓝光具有较佳视觉感受。同理,本防蓝光剂系统也可以是式(II)化合物的组合,例如式(II-1)、式 (II-2)化合物的组合。(II-1)、(II-2)的蓝光区最大吸收各约为380nm、420nm(不同溶剂中略有不同),藉由控制(II-1)和(II-2)的比例,可对不同波段的蓝光选择性地吸收,使得穿透的蓝光具有较佳视觉感受。本防蓝光剂系统也可是式(I)与式(II)化合物的组合,例如式(I-1)、式(I-2)、式(I-3)、式(II-1)、式(II-2)化合物之间的组合。(I-1)、式(I-2)、式(I-3)、式(II-1)、式(II-2)化合物在约400±20nm都有最大吸收峰,五者皆可有效去除有害的较短波长蓝光。且(I-1)、式(I-2)、式(I-3)、式(II-1)、式(II-2) 化合物从410nm到450nm之间的吸收值,都有接近线性的递减,可使得穿透的蓝光具有较佳视觉感受。式(I)与式(II)化合物结构虽不相近,但式(I)与式(II)化合物之间可共享溶剂包括甲苯、丁酮、异丙醇、乙酸乙酯、乙腈等。因此,式(I)与式(II)化合物可以各种比例相混合,达成过滤蓝光功效。
本防蓝光剂系统可以与其他防紫外线化合物组合使用,达到同时防止紫外与蓝光的功能。例如,二甲基(对甲氧基亚苄基)丙二酸酯(即式II-5化合物,UV吸收最大吸收峰314nm)、2,2'-(1,4-苯二亚甲基)二丙二酸四乙酯(即式II-6化合物,UV吸收最大吸收峰320nm)、和氰基对甲氧基肉桂酸酯(即式II-7化合物,UV 吸收的最大吸收峰在340nm)。
UVA(约320-400nm)紫外光可穿透玻璃,是主要室内的紫外光波段。 UVB(约290-320nm)紫外光则是太阳辐射对皮肤引起光生物效应的主要紫外光波段。在许多应用中,同时吸收UVA(约320-400nm)和全波段蓝光(约 380nm-450nm)是被期待的。同时吸收UVAB(约290-400nm)和全波段蓝光(约 380nm-450nm)的防UV-蓝光系统也是被期待的。410nm-450nm,是较低能量的长波长蓝光。从410nm起到450nm间,吸收渐减的防蓝光系统是被期待的,因为所造成的穿透光,可呈现较佳的视觉感受。具有吸收UVAB(约290-400nm)且同时具有选择性吸收蓝光(从410nm起到450nm吸收渐减)的防UV-蓝光系统,更是被深切期待的。例如(I-1)、式(I-2)、式(I-3)式(II-1)、式(II-2)、式(II-5)、式(II-6)、式(II-7)中一种或多种化合物的特定组合。
本发明化合物:
Figure GDA0003893710680000041
其中,R1～R3各自独立地选自H、直链或支链C1～C6烷基、OR3、和 N(R3)2,R4～R6各自独立地选自H、和直链或支链C1～C6烷基,R7～R8各自独立地选自COOR9、CONR10R11、COR12、和CN,R9选自H、直链或支链的C1～C18烷基、和聚乙二醇基,R10～R12各自独立地选自H、直链或支链的C1～C6烷基、和苯基。
较佳的方案,其中R1～R2各自独立地选自C1～C5烷基、OCH3、和 N(CH3)2,R3～R4为H,R5～R6为各自独立直链或支链的C1～C4烷基,R7～R8各自独立地选自COOR9、CONR10R11、COR12、和CN,R9为H或直链或支链的C1～ C18烷基或分子量40～500的聚乙二醇基,R10～R12各自独立地选自H、直链或支链的C1～C4烷基、和苯基。
更佳的方案,R1～R2各自独立选自叔丁基、甲氧基、二甲基胺基,R3～R4为H,R5～R6为各自独立直链或支链的C1～C4烷基,R7～R8各自独立地选自COOR9和CN,R9为直链或支链的C1～C4烷基或分子量40～350的聚乙二醇基。
特佳的方案,包括(I-1)、式(I-2)、式(I-3)式(II-1)、式(II-2)化合物。
Figure GDA0003893710680000042
特佳的方案,还包括(I-1)、式(I-2)、式(I-3)式(II-1)、式(II-2)一种或多种化合物的组合。另一个特佳的方案中,包括例如(I-1)、式(I-2)、式(I-3)式(II-1)、式(II-2)、式(II-5)、式(II-6)、式(II-7)一种或多种化合物的组合。其中,式(II-5)、式(II-6)、式 (II-7)为防紫外线化合物。
Figure GDA0003893710680000051
防紫外线化合物可以是二甲基(对甲氧基亚苄基)丙二酸酯(式II-5化合物)、 2,2'-(1,4-苯二亚甲基)二丙二酸四乙酯(式II-6化合物)、氰基对甲氧基肉桂酸酯(式II-7化合物)、(2-苯并三唑-2-基)-4,6-双(1-甲基-1-苯基乙基)苯酚、2,2'-亚甲基双 (4-叔辛基-6-苯并三唑苯酚)、或其他防紫外线化合物。
本发明防式(II)化合物的聚乙二醇和脂肪酯的取代基,在应用上,具有优异的低迁移性和高相容性。且本发明所述的式(II)苯丙烯酸类化合物，可与各种树脂、单体或预聚合物反应,达到低迁移性和高相容性的优点。
本发明的防蓝光组合物可以选择加入自由基捕捉剂或抗氧剂或阻聚剂,使不预期的光反应被阻止。此外,调节组合物中的pH质,也可使不预期的光反应被阻止。在防蓝光组合物的聚合反应中,选择适当的波段的引发剂,也可以避免产生不预期的光反应。
如前述,已知的式(I)和式(II)化合物,作为印刷电路板的光刻胶中的光引发剂,其作用在于引起自由基以产生系列光化学反应。其属于破坏性作用,与本发明防蓝光剂滤光的保护功用完全不同。此外,本发明防蓝光系统之应用则是滤去蓝光, 一方面使得穿透的光线不具有对人体具伤害的短波长蓝光,另一方面,对短波长蓝光以外的可见光线,仍须具有高穿透力。这与印刷电路板中不透光层的加纤树脂的反射或阻断光线的作用完全不同。再者,本发明防蓝光系统之滤蓝光与电荷传输功能亦完全不同。
式(I-1)化合物的合成路径(实施例1):
Figure GDA0003893710680000052
式(II-1)化合物的合成路径(实施例4):
Figure GDA0003893710680000061
本发明防蓝光系统，其基本结构包括一或多个防蓝光膜层、及/或基底层、及/或离型层。基本上是将防蓝光组合物涂布在基底层或离型层后干燥。或采用转移涂布工艺，先涂布在离型膜上，再转移到基底层上。防蓝光膜上、下层各贴合一层离型薄膜则是OCA光学胶(Optically Clear Adhesive)。涂布方式是习知技艺,包括传统刷式涂布、喷雾涂布、帘式涂布、辊式涂布、狭缝式涂布、气刀涂布、刮刀涂布、计量棒涂布。干燥方法包括自然干燥、微波干燥、紫外线干燥、红外线干燥、热空气干燥。基底层包括聚酯、玻璃、聚乙烯、聚丙烯、聚碳酸酯、聚酰胺、聚丙烯酸酯、聚甲基丙烯酸酯、聚醋酸乙烯、聚氯乙烯之一种或多种混合。离型膜包括硅氧化合物型和非硅氧化合物材质。非硅氧化合物包括例如聚乙烯、聚丙烯，聚脲、聚丙烯酸、聚酯及氟碳类之一种或多种混合。OCA光学胶按照厚度不同可应用于不同的领域，例如透明器件粘结、显示器组装、镜头组装、面板、玻璃或聚碳酸脂等塑料材料的贴合。防蓝光膜还可以包括其它膜层,例如,UV吸收膜层、防雾膜层、抗静电膜层。防蓝光膜可应用于光学或电子产业, 例如光学镜片、护目镜、镜头、显示器、面板、照明防护。
热引发防蓝光组合物,通常包括防蓝光剂、热引发剂、单体、溶剂、助剂。热引发剂按照引发剂的使用温度范围，分为高温(100℃以上)引发剂,如烷基过氧化物、烷基过氧化氢化合物、过氧化酯化合物之一种或多种混合。中温(40～ 100℃)引发剂，如偶氮化合物、过氧化二酰、过硫酸盐等。低温(0～40℃)引发剂,如氧化还原引发体系。热引发剂按分子结构主要可分为偶氮化合物和过氧化物两类。常用的偶氮化合物包括偶氮二异丁腈(ABIN)、偶氮二异庚腈(ABVN)、和带羧基或磺酸基的偶氮化合物。常用的过氧化物包括过氧化苯甲酰(BPO)、过氧化二(2，4-二氯苯甲酰)、过氧化二乙酰、过氧化二辛酰、过氧化二月桂酰、二异丙苯过氧化物(DCP)、二叔丁基过氧化物(DTBP)、过氧化苯甲酸叔丁酯 (BPB)、异丙苯过氧化氢(CHP)和叔丁基过氧化氢(TBH)、过氧化二碳酸二异丙酯(IPP)、过氧化二碳酸二异丁酯(IBP)、过氧化二碳酸、甲乙酮过氧化物、环己酮过氧化物、过硫酸盐和过氧化氢。单体为含有双键或其他活性官能基的小分子化合物。双键类单体包括丙烯酸类、丙烯酸酯类、甲基丙烯酸类、甲基丙烯酸酯类、羟基丙烯酸酯类、甲基丙烯酸羟基酯类、双丙酮丙烯酰胺类、乙烯类、苯乙烯类、二烯类、氟乙烯类、氯乙烯类、丙烯腈类、及醋酸乙烯酯类、有机硅丙烯酸酯类、环氧丙烯酸酯类、聚氨酯丙烯酸酯类。丙烯酸或丙烯酸酯类单体,包括丙烯酸酯软单体、丙烯酸酯硬单体、丙烯酸功能单体、交联单体。较佳的丙烯酸酯软单体,例如是丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-乙基己酯、丙烯酸异辛酯。较佳的丙烯酸硬单体,例如是丙烯酸甲酯、甲基丙烯酸甲酯。较佳的丙烯酸功能单体,例如是丙烯酸、甲基丙烯酸。较佳的交联单体,例如是丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、己二酸二酰肼(ADH)。应用于防蓝光膜的热固性树脂,例如是聚氨酯树脂、环氧树脂、酚醛树脂、聚脲树脂、不饱和聚酯树脂、醇酸树脂。其单体可以是异氰酸酯类、环氧氯丙烷、酚类、醛类、多元醇类、脂肪酸类、多元酸类、酸酐类、多元硫醇类、多元胺类、醇胺类、硫醇胺类。溶剂包括乙腈、丙酮、甲乙酮、丁酮、环己酮、苯、甲苯、二甲苯、乙酸乙酯、乙酸丁酯、甲基异丁酮、甲醇、乙醇、异丙醇、丁醇、乙二醇、丙二醇、丁二醇、氯乙烯、二氯甲烷、三氯甲烷、二硫化碳、四氢呋喃、二甲基甲酰胺(DMF)、聚乙二醇甲醚(EGMME)之。聚氨酯是聚酯多元醇或聚醚多元醇和异氰酸酯反应所生成。具体实施方式,例如将多元醇和异氰酸酯、扩链剂、和催化剂(例如二甲胺基环己烷)混合,然后注入模具中固化成型。或是异氰酸酯与多元醇先反应形成预聚物,再加入扩链剂。环氧树脂单体是环氧氯丙烷和双酚A类化合物反应所生成。具体实施方式包括将双酚A和环氧氯丙烷反应,然后加入硬化剂, 例如双氰胺(Dicy)或己二酸二酰肼(ADH)、及加速剂2-甲基咪唑。醇酸树脂的单体包括多元醇和脂肪酸。具体实施方式,例如将甘油、间苯二甲酸酐及脂肪酸放入反应釜内,加热至200-250℃直至所要的粘度及酸价。不饱和聚酯树脂是具有酯键和不饱和双键的线型高分子化合物。单体包括不饱和二元酸和不饱和二元醇, 或饱和二元酸和不饱和二元醇。具体实施方式,例如将丙二醇，丁烯二酸酐，及邻苯二甲酸酐在反应釜中进行缩合聚合反应。所生成不饱和聚酯，加入苯乙烯单体成为黏液状树脂,使用时再加入过氧化环己酮。助剂可包含稳定剂、偶合剂、流平剂、消泡剂、分散剂、溶剂、链转移剂、催化剂、增韧剂、增粘剂、增塑剂、增稠剂、稀释剂、阻燃剂、阻聚剂、防腐剂、硬化剂、酸碱调和剂之一种或多种混合。常用链转移剂,例如脂肪族硫醇和十二烷基硫醇。常用稳定剂,例如UV吸收剂、受阻胺、抗氧化剂、抗水解剂、过氧化物捕捉剂、自由基捕捉剂。热引发防蓝光组合物,可包括防蓝光剂质量含量为0.01％～20％、引发剂质量含量为 0.01～10％、单体或预聚合物或聚合体含量为50～99.98％、助剂质量含量为0～ 80％。其中防蓝光剂质量含量,较佳为0.05％～10％,更佳为0.1％～5％。具体实施方式,例如,将丙烯酸软单体、丙烯酸硬单体、丙烯酸功能单体、和丙烯酸交联单体混合，形成单体混合物。将单体混合物、引发剂和溶剂加入反应釜，升温反应，反应完成后降至室温，出料，均匀涂在基底层即可。
光引发防蓝光组合物,通常包括防蓝光剂、聚合单体或/及预聚合物、光引发剂、助剂。光引发剂主要有自由基型光引发剂和阳离子型光引发剂，其中自由基型光引发剂又分为裂解型光引发剂和夺氢型光引发剂。裂解型自由基型光引发剂以芳基烷基酮类化合物为主,包括安息香衍生物、二烷氧基苯乙酮、α－羟烷基苯酮、α－胺烷基苯酮、酰基膦氧化物、酯化肟酮化合物、芳基过氧酯化合物、卤代甲基芳酮、有机含硫化合物、苯甲酰甲酸酯之一种或多种混合。夺氢型自由基型光引发剂，包括活性胺、二苯甲酮、硫杂蒽酮及其衍生物、蒽醌、活性胺、香豆酮及樟脑醌之一种或多种混合。阳离子型光引发剂，包括重氮盐、二芳基碘鎓盐、三芳基硫鎓盐、烷基硫鎓盐、铁芳烃盐、磺酰氧基酮及三芳基硅氧醚之一种或多种混合。预聚合物,可以是含有官能基并可进一步反应的寡聚物,例如甲基丙烯酸酯低聚物、丙烯酸酯低聚物、环氧丙烯酸酯低聚物、聚氨酯丙烯酸酯低聚物、有机硅丙烯酸酯低聚物、氨基丙烯酸酯低聚物、羧基丙烯酸酯低聚物、磷酸酯类丙烯酸酯低聚物、羟基聚丙烯酸酯低聚物、聚酯丙烯酸酯低聚物、聚醚丙烯酸酯低聚物之一种或多种混合。聚合单体,可以是各种加成或缩合聚合的小分子之一种或多种混合。其中双键类单体包括丙烯酸类、丙烯酸酯类、甲基丙烯酸类、甲基丙烯酸酯类、羟基丙烯酸酯类、甲基丙烯酸羟基酯类、双丙酮丙烯酰胺类、乙烯类、苯乙烯类、二烯类、氟乙烯类、氯乙烯类、丙烯腈类、及醋酸乙烯酯类、有机硅丙烯酸酯类、环氧丙烯酸酯类、聚氨酯丙烯酸酯类。丙烯酸或丙烯酸酯类单体,包括丙烯酸酯软单体、丙烯酸酯硬单体、丙烯酸功能单体、交联单体。较佳的丙烯酸酯软单体,例如是丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-乙基己酯、丙烯酸异辛酯。较佳的丙烯酸硬单体,例如是丙烯酸甲酯、甲基丙烯酸甲酯。较佳的丙烯酸功能单体,例如是丙烯酸、甲基丙烯酸。较佳的交联单体,例如是丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、己二酸二酰肼。其中式(I)防蓝光剂质量含量0.01％～20％,较佳为0.05％～10％,更佳为0.1％～5％。助剂可包含稳定剂、偶合剂、流平剂、消泡剂、分散剂、溶剂、链转移剂、催化剂、增韧剂、增黏剂、增塑剂、增稠剂、稀释剂、阻燃剂、阻聚剂、防腐剂、硬化剂、酸碱调和剂之一种或多种混合。常用助剂包括偶联剂,例如硅烷偶联剂。常用助剂包括稳定剂,例如UV吸收剂、受阻胺、抗氧化剂、自由基捕捉剂之一种或多种混合。光引发防蓝光组合物包括防蓝光剂质量含量为0.01％～20％、引发剂质量含量为0.01～10％、单体及/或预聚合物为5～99.98％、助剂质量含量为0～95％。较佳地,防蓝光剂质量含量为0.05％～10％、引发剂质量含量为0.05～5％、单体及/或预聚合物为5～99.9％、助剂质量含量为0～50％。具体实施方式,可将光引发防蓝光组合物(例如丙烯酸酯单体、丙烯酸酯预聚体、蓝光吸收剂、引发剂Photocure84的组合)混合,均匀地涂至洁净的基底层上，然后用 UV光固化即得到防蓝光膜。
非反应型防蓝光组合物,其组成包括防蓝光剂、聚合体、溶剂、及/或助剂。其主要是利用涂膜中的溶剂或其它分散介质的挥发，而形成固态的薄膜。聚合体可选自但不限于聚丙烯酸酯、聚甲基丙烯酸酯、聚乙烯、聚丙烯、聚氯乙烯、聚苯乙烯、聚丙烯腈、聚对苯二甲酸乙二酯，聚对苯二甲酸丁二酯、聚碳酸酯、聚酰胺、乙烯-醋酸乙烯酯共聚合物、聚乙烯醇、丙烯腈-苯乙烯共聚合体、热塑性聚氨酯、聚酰亚胺、纤维素、聚硫化苯、聚氧化二甲苯、聚甲醛、聚砜、聚醚醚酮、聚酰胺-酰亚胺、聚醚酰亚胺、聚醚砜、聚醚酰亚胺之一种或多种混合。非引发防蓝光组合物可包括防蓝光剂质量含量为0.01％～20％、聚合体含量为5～99.99％、助剂质量含量为(0～95％)。具体实施方式,以聚苯乙烯为例,将聚苯乙烯塑料烘干,然后粉碎成小块,投入二甲苯/乙酸乙酯混合溶剂中,搅拌至完全溶解。再加入增塑剂(例如邻苯二甲酸二丁酯)、防蓝光剂加热搅拌,即得到组合物。涂布并干燥去除溶剂后，得到防蓝光膜。聚苯乙烯的增塑剂包括邻苯二甲酸酯类、双萜烯、环氧大豆油、环氧大豆油酸辛酯、烷基苯磺酸酯。
本发明防蓝光光学镜片或护目镜,包括玻璃及高分子材料的镜片,如聚碳酸酯(PC)、聚甲基丙烯酸甲酯(PMMA)、尼龙(PA)、TPX(Polymethylpentene)、聚苯乙烯、二甘醇双烷基碳酸酯树脂(PEDC)。防蓝光剂可按特定的比例添加树脂中共同成型,蓝光剂质量含量0.01％～20％,较佳为0.05％～10％,更佳为 0.1％～5％。本发明也可采用含浸工艺,将镜片浸于含防蓝光剂溶液。本发明也可采用薄膜工艺,在镜片表面形成防蓝光膜。本发明也可采用转移涂布工艺，例如先涂布在离型膜上，再转移到光学镜片上。
附图说明
图1本发明(I-1)和(II-1)化合物的UV-VIS吸收图
图2防蓝光膜侧面示意图:其中,1.离型层,2.防蓝光层,3.基底层
图3防蓝光OCA光学胶(Optically Clear Adhesive)侧面示意图:其中,1.离型层,2.防蓝光层,3.离型层。
具体实施方式
以下对本发明的具体实施方式进行说明，但不限于这些实施方式。
实施例1合成式(I-1)化合物,1-苯基-3-(4-丁基苯乙烯基)-5-(4-叔丁基苯基)吡唑啉
Figure GDA0003893710680000091
4-叔丁基苯甲醛16.2g及丙酮3.0g，加入新鲜制备甲醇钠溶液中进行室温搅拌3小时。水洗干燥,得到产物双(2-(4-叔丁基)苯基乙烯基)酮。取7g双(2-(4- 叔丁基)苯基乙烯基)酮和2.2g苯肼，在醋酸中反应4小时。冷却后，纯化产物，得到1-苯基-3-(4-丁基苯乙烯基)-5-(4-叔丁基苯基)吡唑啉,熔点192-197℃。 UV-VIS(ETOH.max.)387nm。
实施例2合成(I-2)化合物,1-苯基-3-(对甲氧基苯乙烯基)-5-(对甲氧基苯基)吡唑啉
Figure GDA0003893710680000101
同实施例1方法,但以对甲氧基苯甲醛代替4-叔丁基苯甲醛,得到1-苯基 -3-(对甲氧基苯乙烯基)-5-(对甲氧基苯基)吡唑啉(I-2)化合物，熔点159℃。 UV-VIS(ETOH.max.)381nm。
实施例3合成式(I-3)化合物,苯基-3-(对甲氧基苯乙烯基)-5-(对二甲基胺基苯基)吡唑啉
Figure GDA0003893710680000102
同实施例1方法,但以对二甲基胺基苯甲醛代替4-叔丁基苯甲醛,得到苯基 -3-(对甲氧基苯乙烯基)-5-(对二甲基胺基苯基)吡唑啉，熔点 192℃,UV-VIS(ETOH.max.)419nm。
实施例4合成(II-1)化合物,二甲基2-(4-(二甲基氨基)亚苄基)丙二酸二甲酯
Figure GDA0003893710680000103
将15g的4-(二甲基胺基)苯甲醛及及14.5g丙二酸二甲酯溶解于二氯甲烷搅拌之,加入分子筛除水并装置氯化钙管以防水。加入1ml哌啶和0.6ml醋酸，并加热回流温度反应2小时，反应期间补充新鲜分子筛。反应完成后除去溶剂, 酸洗、干燥后得到二甲基2-(4-(二甲基氨基)亚苄基)丙二酸二甲酯(I-1)化合物,熔点87-88℃。UV-VIS(CH3CN max.)384nm。
实施例5合成(II-2)化合物,2-乙基-2-氰基-3-(4-(二甲氨基)苯基)丙烯酸乙酯
Figure GDA0003893710680000111
同实施例4方法,但以2-氰基乙酸乙酯代替丙二酸二甲酯，得到2-乙基-2- 氰基-3-(4-(二甲氨基)苯基)丙烯酸乙酯(II-2)化合物,熔点125-126℃。
UV-VIS(CH3CN max.)420nm。
实施例6合成(II-3)化合物,2-氰基-3-(4-(二甲基氨基)苯基)丙烯酸十八烷基酯式
Figure GDA0003893710680000112
将24克化合物II-2溶于甲苯中在冷凝分水器中110℃下加热回流。向甲苯溶液中加入27克硬脂醇和1.5g对甲苯磺酸。HPLC监控反应,反应完成后,通过真空抽滤干燥得到化合物(II-3)。MS(M/Z:468.4)。
实施例7合成式(II-4)化合物,2-乙基-2-氰基-3-(4-(二甲氨基)苯基)丙烯酸聚醚酯
Figure GDA0003893710680000113
同实施例6方法,以Methoxypolyethylene glycol 350代替硬脂醇,产物经 GPC纯化,得到2-乙基-2-氰基-3-(4-(二甲氨基)苯基)丙烯酸聚醚酯式(II-4)化合物。
实施例8-防蓝光组合物和防蓝光膜
将丙烯酸丁酯150g、甲基丙烯酸甲酯95g、丙烯酸15g、防蓝光剂5.8g、过氧化苯甲酰6g、在乙酸乙酯/甲苯溶剂中混合,加入反应釜，升温至75℃，反应2小时后，缓慢滴加额外的6g过氧化苯甲酰(溶剂中),继续反应约6小时,监控粘度,反应完成后,降至室温。涂布于PET膜上,干燥去除溶剂后，得到防蓝光剂的防蓝光膜(100μm)。测量蓝光波段400nm穿透度,结果如表1。
表1实施例8的产品的蓝光穿透度
Figure GDA0003893710680000121
实施例9-防蓝光剂之组合
表2是式(I)化合物单独或组合(I-1)、(I-2)、和(I-3)的防蓝光的应用。表3 是式(II)化合物单独或组合(II-1)、(II-2)、(II-5)的防蓝光的应用。表4是组合(I-1)、 (II-1)和(II-5)的防蓝光应用。表2～4中“380-400nm吸收”表示对较短波长蓝光(较高能量)的吸收。吸收愈大,表示对较短波长蓝光的防护效果愈好。表2中“UVA1&380nm-450nm吸收”,表示对长波长紫外光UVA1(约340-400nm)和 380nm-450nm的蓝光都吸收。吸收愈大,表示对长波长紫外光(UVA1)和全波段蓝光的防护效果愈好。表3、4中“UVAB&380nm-450nm吸收”,表示对UVAB(约 290-400nm)的紫外光和380nm-450nm全波段的蓝光都吸收。吸收愈大,表示对紫外光(UVAB)和全波段蓝光的防护效果愈好。表2～4中“410nm-450nm吸收渐减”表示从410nm起到450nm的吸收渐减。所穿透的蓝光具有较佳的色彩视觉效果。“-”表示效果不佳,“+”表示效果尚可,“++”表示效果佳,“+++”表示效果很好。
表2式(I)化合物防蓝光试剂之组合
Figure GDA0003893710680000122
1 100 O 0 ++ +++ +++
2 0 100 0 ++ +++ ++
3 0 0 100 ++ +++ ++
4 0 40-60 40-60 +++ +++ ++
5 40-60 40-60 0 ++ +++ +++
6 40-60 0 40-60 +++ +++ ++
7 30-40 30-40 30-40 +++ +++ ++
表3式(II)化合物防蓝光试剂之组合
Figure GDA0003893710680000131
表4式(I)和式(II)化合物防蓝光试剂之组合
Figure GDA0003893710680000132
上述实施例不以任何形式限制本发明，本发明各种不同组合，凡等同替换或等效变换所获得的技术方案，均落在本发明的保护范围。

Claims (4)

1.一种防蓝光系统，其系光学膜或光学镜片，具有吸收波长290-400nm的UVAB且同时具有选择性吸收蓝光， 即从410nm起到450nm吸收渐减特性， 特征在于， 包括以下式(I-1)或式
(II-2)化合物:
Figure FDA0003895095540000011
2.根据权利要求1所述的防蓝光系统， 其特征在于， 式(I-1)和式(II-2)化合物系合并使用。
3.根据权利要求2所述的防蓝光系统， 另包括式(II-1)化合物，
Figure FDA0003895095540000012
4.权利要求1的式(I-1)或式(II-2)化合物在防蓝光系统的用途， 该系统为光学膜或光学镜片，特征在于， 具有吸收波长290-400nm的UVAB且同时具有选择性吸收蓝光， 即从410nm起到450nm吸收渐减特性。
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