CN1127695A - 用耐刮和耐磨薄膜涂覆的、基于丙烯酸聚合物的成型制品的制备方法 - Google Patents

用耐刮和耐磨薄膜涂覆的、基于丙烯酸聚合物的成型制品的制备方法 Download PDF

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CN1127695A
CN1127695A CN95116921A CN95116921A CN1127695A CN 1127695 A CN1127695 A CN 1127695A CN 95116921 A CN95116921 A CN 95116921A CN 95116921 A CN95116921 A CN 95116921A CN 1127695 A CN1127695 A CN 1127695A
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马克·里加蒙蒂
多纳托·斯坦科
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Abstract

使基于热塑性丙烯酸聚合物的成型制品变得耐刮耐磨的方法，包括用组合物涂布制品，该组合物含，(A)55-95％重量的至少有两个双键的(甲基)丙烯酸单体和/或低聚物，(B)5-25％重量的二乙烯基醚和/或环氧化物的单体和/或低聚物，(C)当(A)或(B)不含极性基团时，0-20％重量的、含极性基团的、单官能(甲基)丙烯酸酯和/或单乙烯基醚的单体和/或低聚物，及自由基型和阳离子型的光引发剂混合体系；后在30-70℃紫外照射涂覆制品使涂层就地聚合和交联。

Description

用耐刮和耐磨薄膜涂覆的、基 于丙烯酸聚合物的成形 制品的制备方法
本发明涉及通过用下述混合物进行涂布，然后通过紫外照射而就地聚合和交联，以使基于热塑性丙烯酸聚合物的成形制品、板和薄膜的表面变得耐刮和耐磨的方法；所述的混合物包括：
a)至少有两个可聚合双键的(甲基)丙烯酸单体和/或低聚物，
b)乙烯基醚或环氧化物的单体和/或低聚物，和
c)与自由基光引发剂结合的阳离子光引发剂。
此外，本发明还涉及由上述方法得到的耐刮和耐磨的成形制品。
众所周知，在基于热塑性丙烯酸聚合物如聚甲基丙烯酸甲酯(PMMA)的板和薄膜，特别是透明的板和薄膜的应用中都会遇到的问题之一，是由于它们容易被刮伤和磨伤，因此随之它们的透明度将降低，它们的表面外观将变差。
现有技术已建议了包括丙烯酸聚合物的热塑性聚合物板和成形制品的各种表面处理方法，以避免所述的缺陷。
这些处理方法通常包括在制品或热塑性板(基材)上施用一层通常为丙烯酸的单体层，在自由基聚合引发剂的存在下，通过在80℃至该基材的玻璃化温度(Tg)下加热就地使该单体层聚合和交联。
由于聚合和交联的涂层有足够的硬度，因此用这种方式可得到改善耐磨性的热塑性制品。
然而这些处理方法仍很不方便，这是由于为了避免在高温进行聚合和交联和成形时聚合基材的降解时，由于氧所致的抑制作用，此外还有不希望的黄色外现，它们必须在无氧环境、特别是在惰性气氛(氮)中进行。而且这样得到的涂层并不总是表现出对基材的良好的粘附性和良好的透明度。
因此，在无氧条件下，特别是在连续化生产热塑性聚合物板和薄膜的工业化工厂中进行所述的处理方法将是既困难又复杂。
此外，还建议了一些处理方法，其中，在光引发剂的存在下，通过使用紫外线而使涂覆在聚合物基材上的单体层聚合和交联，这些方法能在环境状态即在空气存在下并在相当低的温度下进行，例如不会影响聚合物基材的尺寸稳定性，以及其机械性能、外观和透明性，或无论哪方面，都是要避免它们的降解。
在以申请人的名义的意大利专利申请MI94/A 001014中描述了这类方法中之一种，其中，用包含下述a)、b)和c)的单体组合物涂布聚甲基丙烯酸甲酯(PMMA)制品和板，然后在20°-65℃用紫外光就地聚合和交联所述的组合物；所述的组合物包括a)至少有两个可聚合双键的(甲基)丙烯酸单体和/或低聚物，b)含极性基团的(甲基)丙烯酸单体和/或低聚物和c)自由基光引发剂。
然而，由于在涂布薄膜中会形成随后还能使薄膜本身破裂的银纹，因此这样的方法还存在缺陷。
特别是当该配方喷涂在复杂结构的表面上和形成约20-30μm的较厚厚度时，这些现象特别容易发生。
沿着这样的方法，现在已进一步并且意想不到地发现，在涂布组合物中，通过除使用至少有两个可聚合两键和含极性基团的(甲基)丙烯酸单体和/或低聚物外，还使用二乙烯基醚和/或环氧化物的单体和/或低聚物，并通过使用含自由基和阳离子光引发剂的混杂的紫外光光引发剂体系，能避免在耐刮和耐磨涂布薄膜中形成银纹。
通过该改进的方法，得到了本发明的物品即丙烯酸聚合物制品，该制品涂有对聚合物基材具有良好粘合力的薄膜，该薄膜具有很好的耐刮和耐磨性能，不会产生银纹，而且使用足够的时间也不会产生可能的破裂。
此外，根据本发明涂布的特别是如PMMA这样的透明制品的丙烯酸制品，基本上能维持其不变的机械性能和透明度而没有不希望的黄色外现。
因此，本发明的目的是关于涂有耐刮和耐磨薄膜的、基于丙烯酸热塑性聚合物的成形制品、板和薄膜的制备方法，其特征在于，在所述制品的表面涂布含下述混合物的一均匀层，并使如此涂布的制品在30°-70℃进行紫外照射，所述混合物包括：
(A)55-95％重量的，至少一(甲基)丙烯酸单体和/或低聚物，具有至少两个可聚合双键，
(B)5-25％重量的，二乙烯基醚和/或环氧化物的单体和/或低聚物，
(C)0-20％重量的、至少含一个极性基团的单官能(甲基)丙烯酸单体和/或低聚物和/或单乙烯基醚，
(D)对每100份(A)＋(B)＋(C)为0.5-6重量份的自由基光引发剂，
(E)对每100份(A)＋(B)＋(C)为0.1-3重量份的阳离子光引发剂，
(F)对每100份(A)＋(B)＋(C)为0-8重量份的胶体二氧化硅或亲水的胶体金属氧化物，
前提条件是，(A)＋(B)＋(C)的总量为100；当组份(A)或(B)不含至少一个极性基团时，组份(C)总是存在。
作为形成要被涂布的成形制品的丙烯酸聚合物，可使用例如，通常是透明的、(甲基)丙烯酸的C1-C4烷基酯的(共)聚物，特别是聚甲基丙烯酸甲酯(PMMA)，所述(共)聚物与聚氯乙烯或聚偏氟乙烯的透明合金，和含在分散相中的丙烯酸弹性体的抗震聚甲基丙烯酸甲酯。
例如，二元醇类，多元醇类，聚乙氧基化的多元醇类以及脂族聚氨酯的多官能(甲基)丙烯酸酯的单体和/低聚物能用作组份(A)。
这类化合物的例子为聚(甲基)丙烯酸酯化的聚氨酯，它们是通过多元醇与异氰酸酯类和羟乙基(甲基)丙烯酸酯类反应而得到的，三丙烯酸季戊四醇酯(PETLA)，四丙烯酸季戊四醇酸(PETTA)，五丙烯酸二季戊四醇酯，二丙烯酸1，6-己二醇酯(HDDA)，三羟甲基丙烷三丙烯酸酯(TMPTA)，三丙二醇二丙烯酸酯(TPDGA)。
业已证明，脂族六丙烯酸酯聚氨酯和三丙烯酸季戊四醇酯，以及它们与HDDA，TMPTA，TPGGA的混合物是特别合适的。
二乙烯基醚类，例如三乙二醇二乙烯基醚和1，4-环己烷二甲醇二乙烯基醚以及脂族环氧化物，优选环脂族的，单体或低聚物可用作组份(B)。
羟烷基(甲基)丙烯酸酯类和羧烷基(甲基)丙烯酸酯类，如2-羟乙基(甲基)丙烯酸酯，2-羟丙基(甲基)丙烯酸酯和2-羧乙基丙烯酸酯，和至少含一个羧基或羟基的单乙烯基醚，如丁二醇单乙烯基醚可用作至少含一个极性基团优选为羟基和/或羧基的组份(C)。
当组份(A)和(B)至少含一个极性基团时，组份(C)不是必须存在的；如在组份(A)为含羟基的PETIA的情况下是这样，然而也在这一情况下，由于组份(C)对混合物的稀释和粘度降低的能力，特别是与聚氨酸-丙烯酸酯一起使用时，也能少量使用。
作为组份(D)可使用现有技术中已知的紫外光可聚合和交联的自由基引发剂，例如，2-羟基-2-甲基-1-苯基-丙-1-酮(DAROCURE-1173，Ciba-Geigy)，1-羟基-环己基-苯酮(IRGACURE-184，Ciba-Geigy)和基于二苯酮的引发剂例如Frate-lliLamberti和ESACURE KIP 100 E，或它们的混合物。
作为组份(E)可使用现有技术中已知的紫外光可聚合和交联的阳离子引发剂，例如三芳基锍盐类，如三芳基锍六氟锑酸盐类(UVI-6974-CYRACURE，Union Carbide)和三芳基锍六氟磷酸盐类(UVI-6990-CYRACURE，Union Carbide)。
这类阳离子光引发剂不被氧所抑制，而且可与自由基光引发剂(D)，优选以(D)/(E)重量比至少为2/1，更佳为3/1的比例结合使用。
通过使用这样的比例，使在相对湿度最高至60％的空气室中得到交联的涂布混合物。
作为涂布混合物粘度调节剂的组份(F)通常以少量、优选为0.1-1％(重量)使用；为此，初始粒径低于20纳米、pH为3-4的胶体二氧化硅将是特别合适的。
在紫外交联前，还可向涂布混合物添加少量紫外光稳定剂，均涂剂和流化剂，如非离子表面活性剂。
用量至多为8％(重量)的紫外稳定剂，在通过紫外光使涂层进行交联期间和在薄膜形成之后的期间，用来保护聚合物基材。
它们通常由苯并三唑和空间位阻的胺组成，例如TINUVIN 1130和TINUVIN 292，Ciba Geigy。
用量至多为3％(重量)的非离子表面活性用作流化剂，特别是如果混合物(A)＋(B)＋(C)几乎没有流动性时，以便消除该混合物的涂布缺陷，并改善该涂布膜外观的美感。
特别适用于此目的的是氟代脂族聚合酯类，如3-M的Fc-430。
在本发明的方法中不使用有机溶剂。
通过改变组份(A)＋(B)＋(C)的百分比，通过使用胶体二氧化硅和/或流化非离子表面活性剂可随意地调节其粘度的涂布混合物，可使用现有技术已知的任一方法涂在基材上，例如使用喷涂或展涂，以便形成均匀的涂层，该涂层能在聚合和紫外交联后形成厚度为0.5-40μm，优选为5-15μm的涂膜。
高厚度的膜通常导致更硬和挠性更差。
涂布混合物层在进行聚合和交联时的温度为30°-70℃，优选为40°-60℃，即远低于PMMA的玻璃化转移温度(103℃)，远低于含有PMMA母料的透明材料的玻璃化转移温度。所使用的单体的沸点必须高于PMMA基材的Tg，并且至少要比交联温度高出60℃。
如果小心地使被制造的制品保持在相对湿度低于55％的室中的话，自进行通过紫外照射的交联后，该薄膜硬化甚至能有效地持续两天。
无需在厌氧室中进行操作，不过在相对湿度低于60％的室中进行操作是可取的。
根据本发明的方法可与支撑成形制品的制备例如成膜和挤出结合起来，连续地进行。
更具体地说，本发明的方法可根据PMMA板的挤出方法，在温度明确低于这种聚合物的Tg(103°-108℃)，即约在60°-70℃的范围的地段内连续地进行。
为了避免由于由通常用于涂层聚合和交联而发射的紫外照射的红外成份所导致的板的过热，可使用具有降低红外辐射的紫外灯，或在紫外灯和板之间放置一能滤掉绝大多数红外射线的过滤器，例如1-3mm厚的PYREX玻璃，和/或使用冷气流(空气和/或氮气)，以维护该体系在上述的温度范围。
本发明的又一目的是根据本发明的方法得到的、具有耐刮和耐磨涂层的、基于热塑性丙烯酸聚合物的成形制品、板和薄膜。
根据本发明方法涂布的成形制品显示出了很高的耐刮和耐磨性能，该涂膜对丙烯酸基材的最佳粘合，维持其不变的原始透明度和其机械特性，该涂膜没有显现出银纹，这类银纹在一段时间后甚至能引起薄膜本身破裂。
由于耐刮性和耐磨性是可区分的，因此，为了检验这两种处理的有效性，可使用两种不同的方向。
为了测量耐刮性，可根据ASTM D3363，利用木笔进行硬度试验。
为了测量耐磨性能，采用将碳化硅落在处理过的板上的方法，然后根据ASTM D673测量透明度的损失。
通过在薄膜上施加一根据ASTM 3359标准的粘合带，型号610(3M)而测定薄膜对支撑体的粘合力。
进行光学试验，从而检验耐刮和耐磨涂料的有效性。
根据ASTM D1003进行透光度和浊度试验。
根据ASTM D1925测定黄度指数。
为了进一步说明本发明，将给出一些实施例。实施例1
通过展涂10μm厚下述混合物层来涂布3mm厚的PMMA板，所述混合物包含50重量份脂族六丙烯酸聚氨酯(EB1290，UCB)，25份二丙烯酸1，6-己二醇酯(HDDA)，15份三乙二醇二乙烯基醚和15份三丙烯酸季戊四醇酯。
向该溶液添加2.5重量份自由基光引发剂(DARO-CURE1173，Ciba Geigy)和0.8重量份阳离子光引发剂(UVI-6990 CYRACURE，Union Carbide)。
利用120W/cm的紫外灯，以2m/min的输送速率使该配方进行聚合。基材的温度不超过60℃。该交联的薄膜显示出了在PMMA板上最佳的粘合。
在PMMA板上涂布薄膜并进行交联的两天后，再进行铅笔硬度试验和摩擦试验(耐擦伤性)。铅笔硬度为7H(未处理的PMMA＝HB)，落下两千克碳化硅后的雾度约为5％(未处理的板＝11.5％)。黄度指数保持不变，薄膜没有出现银纹。
实施例2
通过喷涂10μm厚的下述混合物层来涂布3mm厚的PMMA板；所述混合物包含60重量份三羟甲基丙烷三丙烯酸酯，25重量份三丙烯酸季戊四醇酯和15重量份1，4-环己烷二甲醇二乙烯基醚。
向该溶液中添加2.5重量份自由基光引发剂DAROCURE 1173Ciba Geigy)和0.8重量份阳离子光引发剂(UVI-6990 CYRACURE，Union Carbide)。
向该溶液中添加0.2重量份酸性pH的胶体二氧化硅(例如，HDKT40，Wacker)，和0.05重量份氟化的表面活性剂(FLUORAD FC-430-3-M)。
利用与实施例1相同的步骤，使该配方进行聚合，交联的薄膜显示出了最佳的粘合，在喷涂并交联这样的薄膜两天后，铅笔硬度为7H(未处理的PMMA硬度＝HB)，落下两千克碳化硅后，雾度为4.5％(未处理的PMMA＝11.5％)。
黄度指数保持不变，该薄膜没有出现银纹。
实施例3
通过展涂10μm厚的下述混合物层来涂布3mm厚的PMMA板；所述混合物包含50％的脂族六丙烯酸聚氨酯(EB5129 UCB)，25％的三羟甲基丙烷三丙烯酸酯，10％的甲基丙烯酸2-羟乙基酯和15％的三乙二醇二乙烯基醚。
向该溶液中添加3重量份自由基光引发剂(DAROCURE 1173 CibaGeigy)和1重量份阳离子光引发剂(UVI-6990 CYRACURE，UnionCarbide)。
利用与实施例1相同的步骤使该配方进行聚合。
交联的薄膜显示出最佳的粘合，在展涂并交联这样的薄膜两天后，铅笔硬度为6H(未处理的PMMA＝HB)，落下两千克碳化硅后，雾度为6％(未处理的PMMA＝11.5％)，该薄膜没有出现银纹。实施例4
通过展涂10μm厚的、与例1相同的混合物层来涂布3mm厚的PMMA板。
在这种情况下，采用高压汞灯HPK Philips 125(约25W/cm)进行交联。以10cm的距离将该涂布的板置于这样的灯下面10分钟。
没有产生氧的抑制作用，粘合力值，铅笔硬度和耐磨性(耐擦伤性)与例1的相同，该薄膜没有出现银纹。对比例
a)通过展涂10μm厚的下述混合物来涂布3mm厚的PMMA板；所述混合物包含75重量份三羟甲基丙烷三丙烯酸酯，20重量份三丙烯酸季戊四醇酯和5重量份苄基二甲基酮(自由基光引发剂)。
向该混合物中添加0.3％的酸性非晶形二氧化硅Syloid ED 30″(Grace Chemicals)。利用与例1相同的步骤使该配方进行聚合。
交联的薄膜显示出了最佳的粘合力，在展涂和交联这样的薄膜两天后，铅笔硬度＝7H(未处理的PMMA＝HB)，落下2000g碳化硅后，雾度为4.5％(未处理的PMMA＝11.5％)。黄度指数高于未处理的PMMA板(+0.8)，在薄膜中观察到银纹的存在。
b)利用例4的步骤使用相同的涂层进行交联。由于氧的抑制作用，20分钟后该薄膜的表面不再进行交联。

Claims (12)

1、一种涂有耐刮和耐磨薄膜、基于丙烯酸热塑性聚合物的成形制品、板和薄膜的制备方法，其特征在于在所述制品表面上涂布一层均匀的混合物层，所述混合物包含有：
(A)55-95％重量的，至少一(甲基)丙烯酸单体和/或低聚物，具有至少两个可聚合双键，
(B)5-25％重量的，二乙烯基醚和/或环氧化物的单体和/或低聚物，
(C)0-20％重量的、含至少一个极性基团的单官能(甲基)丙烯酸单体和/或低聚物、和/或单乙烯基醚，
(D)对每100份(A)＋(B)＋(C)为0.5-6重量份的自由基光引发剂，
(E)对每100份(A)＋(B)＋(C)为0.1-3重量份的阳离子光引发剂，
(F)对每100份(A)＋(B)＋(C)为0-8重量份的胶体二氧化硅或亲水的胶体金属氧化物，
前提条件是，(A)＋(B)＋(C)的总量为100，当组份(A)或(B)不含至少一个极性基团时，组份(C)总是存在；然后将如此涂布的制品在30℃-70℃进行紫外照射。
2、根据权利要求1的方法，其中，要被涂布的制品的热塑性丙烯酸聚合物为(甲基)丙烯酸的C1-C4烷基酯的(共)聚合物，或它们与聚氯乙烯或聚偏氟乙烯或与丙烯酸弹性体的混合物。
3、根据权利要求1的方法，其中，该热塑性丙烯酸聚合物为聚甲基丙烯酸甲酯。
4、根据权利要求1的方法，其中，组份(A)为二元醇、多元醇、乙氧基化的多元醇以及脂族聚氨酸的多官能(甲基)丙烯酸酯的单体和/或低聚物。
5、根据权利要求1的方法，其中组份(A)选自：聚(甲基)丙烯酸聚氨酯，三丙烯酸季戊四醇酯，四丙烯酸季戊四醇酯，五丙烯酸二季戊四醇酯，二丙烯酸1，6-己二醇酯和二丙烯酸三丙二醇酯。
6、根据权利要求1的方法，其中组份(A)是脂族六丙烯酸聚氨酯和/或三丙烯酸季戊四醇酯与三羟甲基丙烷三丙烯酸酯或二丙烯酸己二醇酯的混合物。
7、根据权利要求1的方法，基中组份(B)选自：三乙二醇二乙烯基醚，1，4-环己烷二甲醇乙烯基醚和环脂族环氧化物。
8、根据权利要求1的方法，其中组份(C)选自：至少含一个羟基或羧基的羟烷基(甲基)丙烯酸酯，羧烷基甲基丙烯酸酯和至少含一个羟基或羧基的单乙烯基醚。
9、根据权利要求1的方法，其中组份(C)选自：(甲基)丙烯酸2-羟乙基酯，(甲基)丙烯酸2-羟丙基酯，丙烯酸2-羧乙基酯和丁二醇单乙烯基醚。
10、根据权利要求1的方法，其中组份(D)与组份(E)的重量比至少为2。
11、根据权利要求1的方法，其中，在40°至60℃进行该紫外照射。
12、一种涂有耐刮和耐磨薄膜的、基于热塑性丙烯酸聚合物的成形制品和板，它们可通过权利要求1-11的方法得到。
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DE69507224T2 (de) 1999-09-30
IT1274039B (it) 1997-07-14
EP0699704B1 (en) 1999-01-13
ITMI941811A0 (it) 1994-09-02
KR960010731A (ko) 1996-04-20
DE69507224D1 (de) 1999-02-25
US5569498A (en) 1996-10-29
JPH08259719A (ja) 1996-10-08
EP0699704A1 (en) 1996-03-06

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