WO2018223710A1 - 聚合物多元醇及其光致变色涂层组合物 - Google Patents

聚合物多元醇及其光致变色涂层组合物 Download PDF

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WO2018223710A1
WO2018223710A1 PCT/CN2018/073738 CN2018073738W WO2018223710A1 WO 2018223710 A1 WO2018223710 A1 WO 2018223710A1 CN 2018073738 W CN2018073738 W CN 2018073738W WO 2018223710 A1 WO2018223710 A1 WO 2018223710A1
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parts
photochromic
polymer polyol
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French (fr)
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甘家安
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上海甘田光学材料有限公司
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Priority to US16/619,833 priority Critical patent/US20200190240A1/en
Publication of WO2018223710A1 publication Critical patent/WO2018223710A1/zh

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Abstract

本发明涉及一种聚合物多元醇及其组合物和用途。所述聚合物多元醇是：由含羟基的丙烯酸酯与不含羟基的丙烯酸酯经共聚获得的共聚物。所述组合物包括：基体树脂、本发明所述的聚合物多元醇和光致变色化合物，且所述组合物中羟基固含量为1.0％～6.0％。本发明提供的的组合物是一种耐候性好及与其它功能性涂层(如有机硅烷硬涂层或/和防反射涂层等)相容性好的光致变色涂层组合物(或称为光致变色涂层)，其适合于制备眼科用途的光致变色涂层制品。

Description

聚合物多元醇及其光致变色涂层组合物 技术领域
本发明涉及一种聚合物多元醇及其组合物和用途，具体地说，涉及一种由含羟基的丙烯酸酯与不含羟基的丙烯酸酯的共聚物及其组合物和用途。
背景技术
将含有光致变色化合物的涂料在透明塑料上设置变色层的方法称为涂敷法，该法理论上不管何种透镜的基材都可以简单地赋予光致变色特性，由于其没有透镜基材要求的制约，该方法得到了快速发展。
将光致变色涂层涂敷到塑料基底表面时，由于物理接触，清洗和光致变色涂层与外部环境的接触，会导致划伤和其它类似的缺陷。某些情况下，灰尘杂质等污染涂层表面时，生产商需要用含有醇类如乙醇、异丙醇的清洗液进行清洗，清洗时发现光致变色层产生了缺陷，因而需要涂覆耐磨涂层于光致变色涂层表面。另外，在光致变色镜片的生产过程中，常常会发现涂覆在光致变色层表面的耐磨涂层或涂覆在耐磨涂层上的防反射涂层无法满足产品要求，或不符合眼科镜片的商业标准。涂层镜片的缺陷包括斑点，划伤，杂质点，水波纹，裂纹，龟裂。当这些缺陷出现时，如果希望经济有效地去除有缺陷的有机硅烷硬涂层，一般通过用烧碱水溶液或掺混烧碱水溶液的清洗液去除有机硅烷硬涂层，并涂覆新的硬涂层。但在去除有缺陷的有机硅烷硬涂层时，会损坏有机硅烷硬涂层下的光致变色层，无法重新涂覆新的有机硅烷硬涂层，从而使制品失去其商业价值。有机硅烷硬涂层和防反射涂层涂覆是镜片诸多制造步骤中的结尾工序，在生产光致变色镜片的过程中，每增加一步工序，都为镜片额外提升价值和增加成本。如果所涂覆的涂层不能符合产品要求而最终废弃镜片，会使得制造成本大大提高并降低产品利润，将使生产商承受大幅度的经济损失。
此外，有些光致变色镜片生产商是直接从其它生产光致变色涂层的生产商购买，需要涂覆自己拥有所有权的特殊有机硅烷硬涂层和防反射涂层，而在此准备及转移过程中的包装、运输、解包、清洗、擦洗等过程都可能会导致光致变色层的划伤、玷污、腐蚀，因而要求光致变色层是耐划伤和耐溶剂。
综上，本领域迫切需要一种耐候性好及与其它功能性涂层(如特殊有机硅烷硬涂层或/和 防反射涂层等)相容性好的光致变色涂层(或称为光致变色涂层组合物)。同时，这也是本发明需要解决的技术问题。
发明内容
本发明的发明人通过对变色机理以及光致变色热固化组合物进行了深入和广泛地研究发现：当在光致变色热固化组合物中添加一种内柔性基团和硬性基团均匀分布的聚合物多元醇时，可以得到强度高、固化速度快、同时变色、褪色性能优异的光致变色热固化组合物。将同样的技术用于黏附于光致变色层上的热固化涂层，得到了变色、褪色性能优异，硬涂层与黏附于光致变色层的热固化涂层密合性强，耐候性、耐擦伤性能良好的光致变色制品，从而克服了现有技术中存在的缺陷。
因此，本发明一个目的在于，提供一种新颖的聚合物多元醇(共聚物)。
本发明所述的聚合物多元醇，其由主要步骤如下制备方法制得：
在有惰性气体及引发剂存在条件下，由式Ⅰ所示化合物、式Ⅱ所示化合物和式Ⅲ所示化合物按质量比为(0.5～2.0)∶1∶1混合，并于110℃～150℃聚合反应2小时～3小时，所得共聚物即为目标物(本发明所述的聚合物多元醇)；
Figure PCTCN2018073738-appb-000001
其中，R 1,R 2和R 3分别独立选自：氢(H)或C 1～C 4直链或支链烷基中一种，R 4为C 4～C 10直链或支链烷基，n为1～5的整数。
本发明另一个目的在于，提供一种热固化光致变色的组合物。
所述组合物包括：基体树脂、本发明所述的聚合物多元醇和光致变色化合物，且所述组合物中羟基固含量为1.0％～6.0％；
所述的基体树脂主要包括：聚氨酯，羟基丙烯酸树脂，氨基树脂或/和有机硅树脂；
其中，所述聚氨酯选自：由六亚甲基二异氰酸酯(HDI)，异佛尔酮二异氰酸酯(IPDI)，苯二亚甲基二异氰酸酯(XDI)，二环己基甲烷二异氰酸酯(H12MDI)，甲苯二异氰酸酯(TDI)，或二甲烷二异氰酸酯(MDI)封端所获聚氨酯中一种或两种以上(含两种)；
所述光致变色化合物选自：萘并吡喃类光致变色化合物，菲并吡喃类光致变色化合物，苯并吡喃类光致变色化合物，茚并萘并吡喃类光致变色化合物，螺吡喃类光致变色化合物，俘精酸酐类光致变色化合物或二芳基乙烯类光致变色化合物中一种或两种以上(含两种)；
所述有机硅树脂由主要步骤如下的制备方法制得：
将10重量份数～30重量份数的本发明所述的聚合物多元醇，5重量份数～30重量份数的硅烷，5重量份数～20重量份数的正硅酸酯，15重量份数～50重量份数的硅烷偶联剂，0.5重量份数～1.0重量份数的催化剂，10重量份数～30重量份数的醇溶剂，5重量份数～20重量份数的水置于反应器中，于25℃～50℃反应2小时～5小时，蒸除醇溶剂和水后，所得残余物即为本发明所述的有机硅树脂；
其中，所述的硅烷的结构式如式IV所示：
Figure PCTCN2018073738-appb-000002
式IV中，R 5～R 8分别独立选自：C 1～C 4直链或支链的烃基或C 1～C 4直链或支链的烷氧基中一种，且R 5～R 8中至少有一个为C 1～C 4直链或支链的烷氧基；
所述的催化剂为三(乙酰丙酮)铝或盐酸；
所述的醇溶剂选自：C 1～C 4直链或支链的一元脂肪醇中一种或两种以上(含两种)混合物。
在所述的热固化光致变色的组合物中，除聚合物多元醇(共聚物)和有机硅树脂为自制品外，其它组分均为市售品。
本发明还有一个目的在于，揭示上述聚合物多元醇和热固化光致变色的组合物的一种用途。即：上述聚合物多元醇在制备眼科用途的光致变色涂层制品中的应用，和上述热固化光致变色的组合物作为眼科用途的光致变色涂层制品的应用。
具体实施方式
在本发明一个优选的技术方案中，R 1,R 2和R 3分别独立选自：H或甲基中一种，R 4为C 4～C 6直链或支链烷基；
更优选的技术方案是：R 1为H，R 2和R 3均为甲基，R 4为正丁基。
在本发明另一个优选的技术方案中，本发明所述的聚合物多元醇，其由主要步骤如下制备方法制得：
在有氮气及偶氮二异庚腈(引发剂)存在条件下，由式Ⅰ、Ⅱ和Ⅲ所示化合物按质量比为(0.5～2.0)∶1∶1混合，并于110℃～150℃(优选130℃～140℃)在二乙二醇丁醚(反应介质)中聚合反应2小时～3小时，所得共聚物即为目标物(本发明所述的聚合物多元醇)。
在本发明又一个优选的技术方案中，本发明提供一种热固化光致变色的组合物，其包括：基体树脂、本发明所述的聚合物多元醇、光致变色化合物和其它助剂，且所述组合物中羟基固含量为1.3％～3.5％；
其中，基体树脂与本发明所述的聚合物多元醇的质量为1：(0.5～5.0)。
在本发明又一个优选的技术方案中，在所述热固化光致变色的组合物中，所用的基体树脂可以是：聚氨酯(优选甲基乙基酮肟为封端剂的聚氨酯)和羟基丙烯酸树脂的混合物，氨基树脂(其包括：全烷基醚化氨基树脂303或/和部分烷基醚化氨基树脂)，有机硅树脂(自制品)；或，
由上述树脂组成的混合物(即：由上述聚氨酯(优选甲基乙基酮肟为封端剂的聚氨酯)，羟基丙烯酸树脂，氨基树脂和有机硅树脂(自制品)组成的混合物)。
在本发明又一个优选的技术方案中，R 5～R 8分别独立选自：甲基，乙基，正丙基，异丙基，正丁基，异丁基，乙烯基，丙烯基，丁烯基，甲氧基，乙氧基，丙氧基或丁氧基中一种，且R 5～R 8中至少有一个为甲氧基，乙氧基，丙氧基或丁氧基。
在本发明又一个优选的技术方案中，在制备前文所述的有机硅树脂时，所用的正硅酸酯可以是正硅酸甲酯，正硅酸乙酯，正硅酸正丙酯或正硅酸正丁酯等正硅酸烷酯。
在本发明又一个优选的技术方案中，在所述热固化光致变色的组合物中，所述其它助剂包括：光稳定剂，表面活性剂和非质子极性溶剂；
其中，所述的光稳定剂可以是现有适用于眼科用途的光致变色涂层制品的光稳定剂；
所述表面活性剂可以是：阳离子型表面活性剂，阴离子型表面活性剂或非离子型表面活性剂(如现有技术中较为常用的聚醚改性有机硅表面活性剂V-2245等)。
以下通过实施例对本发明作进一步阐述，其目的仅在于更好理解本发明的内容。因此，所举之例不限制本发明的保护范围。
聚合物多元醇的制备
实施例1
将式Ⅰ A、Ⅱ A、Ⅲ A所示化合物和二乙二醇丁醚置于带有搅拌及加热装置的反应器中，向反应器中通入氮气，启动搅拌及加热装置，滴加偶氮二异丁腈(引发剂)，并在130℃～140℃状态保持2小时～3小时，冷却至室温，转移到合适的容器中，蒸除溶剂，残余物即为目标物(简记为“聚合物多元醇-1”)。
Figure PCTCN2018073738-appb-000003
以所加物料总重量为100％，其中，式Ⅰ A所示化合物占29.5wt％，式Ⅱ A所示化合物占25wt％，式Ⅲ A所示化合物占25wt％，二乙二醇丁醚占20wt％，引发剂占0.5wt％。
实施例2
除改变所加物料的占比(即：以所加物料总重量为100％，其中，式Ⅰ A所示化合物占24.5wt％，式Ⅱ A所示化合物占27.5wt％，式Ⅲ A所示化合物占27.5wt％，二乙二醇丁醚占20wt％，引发剂占0.5wt％)外，其余步骤和条件与实施例1相同，得到目标物(简记为“聚合物多元醇-2”)。
有机硅树脂(OSEM)的制备
实施例3
将15重量份数的聚合物多元醇-1，15重量份数的甲基三乙氧基硅烷，15重量份数的正硅酸乙酯，25重量份数的KH560，3重量份数的KH550，6.5重量份数的乙烯基三甲氧硅烷，10重量份数的甲醇和叔丁醇等比例的混合物，10重量份数的水和0.5重量份数的三(乙酰丙酮)铝置于带有搅拌即控温装置的反应器中，向该反应器中通入氮气，加热并开启搅拌，在40℃～50℃状态保持3小时～5小时，减压蒸除所加入的醇溶剂及水，残余物即为目标物(本发明所述的有机硅树脂，简记为“OSEM-A”)。
实施例4
将15重量份数的聚合物多元醇-2，20重量份数的甲基三乙氧基硅烷，10重量份数的正硅酸乙酯，20重量份数的KH560，8重量份数的KH550，6.5重量份数的乙烯基三甲氧硅烷，10重量份数的甲醇和叔丁醇等比例的混合物，10重量份数的水和0.5重量份数的0.1N盐酸置于带有搅拌即控温装置的反应器中，向该反应器中通入氮气，加热并开启搅拌，在40℃～50℃状态保持3小时～5小时，减压蒸除所加入的醇溶剂及水，残余物即为目标物(本发明所述的有机硅树脂，简记为“OSEM-B”)。
光致变色组合物的制备
实施例5～15
将组成所述热固化光致变色的组合物的各组分于60℃条件下混合均匀即可。具体见表1.。
表1.
Figure PCTCN2018073738-appb-000004
Figure PCTCN2018073738-appb-000005
Figure PCTCN2018073738-appb-000006
Figure PCTCN2018073738-appb-000007
光致变色涂层制品的制备及其性能测试
实施例16
(1)实验用透镜的清洗和干燥
在下列实施例中，使用了平光型聚碳酸酯半成品塑料透镜。实验用透镜用12％氢氧化钠在60℃下浸蚀10分钟后用去离子水清洗干净。然后，透镜用温肥皂水洗涤、用去离子水清洗并真空干燥。
(2)热固化光致变色涂层表干时间的测定
分别将光致变色组合物(组合物A～K)通过旋涂法施涂于等离子体处理过的透镜上并热固化，测定其表干时间。具体步骤如下：
组合物A～K的各组分在60℃下混合30分钟，涂覆之前在环境温度下混合1小时，然后旋转涂覆于透镜上，涂层在烘箱中120℃下烘60分钟，该光致变色涂层的厚度大约20微米，分别在室温(15℃-25℃)条件下，测定其表干时间，结果见表2.。
(3)附着层表干时间的测定
将树脂Tires 2854(纽佩斯树脂有限公司出品)按(2)所述方法施涂于热固化光致变色涂层上，得到附着层。同时，按(2)所述的表干时间测定法，测定附着层的表干时间，结果见表2.。
(4)制品加硬镀膜前后性能测试
将涂覆有热固化涂层(组合物A～K)的透镜置于硬涂层清洗液(10％的氢氧化钠水溶液)中，在60℃状态下保持至少5分钟，取出透镜，经目测，涂层均未发现破坏。用十字格剥离实验测试热固化涂层与透镜的粘合力，绝大多数合格(详见表2)。使用Bayer磨损实验和钢丝棉划擦实验进行测试，Bayer磨损实验的结果列入表2中。
为了进一步增强透镜的耐划擦性能，在所述热固化涂层表面涂覆了基于硅氧烷的抗磨损的硬涂层(热固型丙烯酸树脂1757，纽佩斯树脂有限公司出品)。涂覆方法是镜片用等离子体处理5分钟，将抗磨损硬涂层涂覆到实验透镜上，在100℃加热3小时进行固化。并用Fisherscope HCV(H-100)仪测定，镜片表面在10N/mm 2的压力下坚持15秒后，在其2微米深度做硬度测定，取每个镜片做3～5次测定后得到的平均数据值(具体见表2)。
(5)防反射涂层生纹温度的测试
测试方法：将涂有防反射涂层制品置于烘箱中，在50℃状态保持1小时，冷却至室温，检查有无细纹。若无细纹，则将烘箱温度升高10℃，并重复上述步骤，直至产生细纹，此时的温度即为生纹温度。
分别在涂有组合物A～K的透镜和未涂有组合物A～K的透镜(空白对照物)上涂覆相同的防反射涂层(度恩，光学镜片镀膜材料)，具体涂覆方法参见(4)中涂覆基于硅氧烷的抗磨损的硬涂层的方法。将所得制品分别上述测试方法测试其防反射涂层生纹温度，具体结 果见表2。
(7)显色浓度及褪色半衰期的测定
在室温下由氙灯(L-2480(300w)SHL-100)隔着aero mass filter用365nm的紫外光照射被测样品(涂覆组合物A～K的样品，下同)180秒使其显色。用分光光度计，测出此时的最大吸收波长。显色浓度是：ε(140)-ε(0)＝1.0(ε(140)-ε(0)＝1.0一种参比，在这个1.0左右的都可以视作在显色浓度内)；
对被测样品(光致变色镜片)照射140秒后，停止照射，测定其最大波长下的吸光度降低至上述{ε(140)-ε(0)}的值的1/2时所需的时间(褪色半衰期，简记为“T 1/2”)。
被测样品的显色浓度及褪色半衰期的具体测试结果见表2。
(8)被测样品的耐久性能的测试
测试方法：用ZG-P氙灯耐候试验机(无锡市苏瑞试验设备有限公司)使被测样品在70℃下进行48小时加速老化。分别测试其老化实验前后的显色浓度(A 0)和(A 200)，通过下式计算可得出表示耐久性的被测样品的重复残余率(％)：
重复残余率(％)＝(A 200/A 0)×100％
被测样品的具体重复残余率及黄色指数见表2，其中，所述的黄色指数可通过Cary 4000仪器测得。
表2.
Figure PCTCN2018073738-appb-000008
续表2.
Figure PCTCN2018073738-appb-000009
*CE为对比制品(CE为现有市场化的标准，即可以作为合格品出售的商品)，其制备方法是：将40毫克的萘并吡喃变色粉加入到烧瓶中，分别加入74克二乙氧化双酚A二甲基丙烯酸酯，20克聚乙二醇，600克二甲基丙烯酸酯，6克甲基苯乙烯二聚体。加热溶解冷却后加入0.23克V65(偶氮二异庚腈)。混合均匀，倒入直径70mm的圆形平光镜片的玻璃膜具中，厚度2mm，密封膜具，放置在水平空气气流的程序控制烘箱中，在18小时内，从35℃升温至100℃，并在100℃保温2小时。打开膜具，镜片在110℃烘箱中二次固化2小时，再根据通用实施例的步骤四进行清洗、涂覆硅氧烷的抗磨损硬涂层、防反射涂层得到制品。
由表2可知：由本发明提供的热固化光致变色的组合物制成的光致变色涂层制品有：较高的Bayer磨损比率，较高的表面硬度，较高的生纹温度，较高的显色浓度，较高的重复残余率，较小黄变指数及较短的褪色半衰期。
因此，本发明提供的热固化光致变色的组合物是一种耐候性好及与其它功能性涂层(如特殊有机硅烷硬涂层或/和防反射涂层等)相容性好的光致变色涂层(或称为光致变色涂层组合物)，其适合于制备眼科用途的光致变色涂层制品。

Claims (10)

  1. 一种聚合物多元醇，其由主要步骤如下制备方法制得：
    在有惰性气体及引发剂存在条件下，由式Ⅰ所示化合物、式Ⅱ所示化合物和式Ⅲ所示化合物按质量比为(0.5～2.0)∶1∶1混合，并于110℃～150℃聚合反应2小时～3小时，所得共聚物即为目标物；
    Figure PCTCN2018073738-appb-100001
    其中，R 1,R 2和R 3分别独立选自：氢或C 1～C 4直链或支链烷基中一种，R 4为C 4～C 10直链或支链烷基，n为1～5的整数。
  2. 如权利要求1所述的聚合物多元醇，其特征在于，其中，R 1,R 2和R 3分别独立选自：H或甲基中一种，R 4为C 4～C 6直链或支链烷基。
  3. 如权利要求2所述的聚合物多元醇，其特征在于，其中，R 1为H，R 2和R 3均为甲基，R 4为正丁基。
  4. 如权利要求1～3中任意一项所述的聚合物多元醇，其特征在于，其中，所用引发剂为偶氮二异庚腈。
  5. 一种热固化光致变色的组合物，其包括基体树脂、权利要求1～4中任意一项所述的聚合物多元醇和光致变色化合物，且所述组合物中羟基固含量为1.0％～6.0％；
    其中，所述光致变色化合物选自：萘并吡喃类光致变色化合物，菲并吡喃类光致变色化合物，苯并吡喃类光致变色化合物，茚并萘并吡喃类光致变色化合物，螺吡喃类光致变色化合物，俘精酸酐类光致变色化合物或二芳基乙烯类光致变色化合物中一种或两种以上；
  6. 如如权利要求5所述的组合物，其特征在于，其中，基体树脂与权利要求1～4中任意一项所述的聚合物多元醇的质量为1：(0.5～5.0)。
  7. 如权利要求5或6所述的组合物，其特征在于，其中所述的基体树脂主要包括：聚氨酯，羟基丙烯酸树脂，氨基树脂或/和有机硅树脂；
    其中，所述聚氨酯选自：由六亚甲基二异氰酸酯，异佛尔酮二异氰酸酯，苯二亚甲基二异氰酸酯，二环己基甲烷二异氰酸酯，甲苯二异氰酸酯或二甲烷二异氰酸酯封端所获聚氨酯中一种或两种以上；
    所述有机硅树脂由主要步骤如下的制备方法制得：
    将10重量份数～30重量份数的本发明所述的聚合物多元醇，5重量份数～30重量份数的硅烷，5重量份数～20重量份数的正硅酸酯，15重量份数～50重量份数的硅烷偶联剂，0.5重量份数～1.0重量份数的催化剂，10重量份数～30重量份数的醇溶剂，5重量份数～20重量份数的水置于反应器中，于25℃～50℃反应2小时～5小时，蒸除醇溶剂和水后，所得残余物即为目标物；
    其中，所述的硅烷的结构式如式IV所示：
    Figure PCTCN2018073738-appb-100002
    式IV中，R 5～R 8分别独立选自：C 1～C 4直链或支链的烃基或C 1～C 4直链或支链的烷氧基中一种，且R 5～R 8中至少有一个为C 1～C 4直链或支链的烷氧基；
    所述的催化剂为三(乙酰丙酮)铝或盐酸；
    所述的醇溶剂选自：C 1～C 4直链或支链的一元脂肪醇中一种或两种以上混合物。
  8. 如权利要求7所述的组合物，其特征在于，其中，所述聚氨酯选自：由六亚甲基二异氰酸酯，异佛尔酮二异氰酸酯，苯二亚甲基二异氰酸酯，二环己基甲烷二异氰酸酯，甲苯二异氰酸酯或二甲烷二异氰酸酯封端所获聚氨酯中一种或两种以上，且封端剂甲基乙基酮肟。
  9. 如权利要求1～4中任意一项所述的聚合物多元醇在制备眼科用途的光致变色涂层制品中的应用。
  10. 如权利要求5～8任意一项所述的组合物作为眼科用途的光致变色涂层制品的应用。
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