CN1045270A - 制备包括接触透镜的成型水凝胶制品的方法 - Google Patents
制备包括接触透镜的成型水凝胶制品的方法 Download PDFInfo
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Abstract
水凝胶成型制品例如软式隐形眼镜,制造步骤为(1)将(a)主要为亲水性(甲基)丙烯酸酯如甲基丙烯酸2-羟乙酯,以及交联剂,(b)可用水置换的稀释剂(其30℃粘度至少100兆帕·秒,主成分为二羟醇硼酸酯,二羟醇的汉森极性δp和汉森氢键δh内聚力参数位于以δh=20.5、δp=13为圆心,半径8.5所成的圆内)的混合物模塑或铸塑聚合成为共聚物的成形凝胶;(2)然后用水置换该稀释剂。
Description
本发明涉及生产成型水凝胶制品(包括软接触透镜)的方法,特别是涉及用某种硼酸酯作可被水置换的稀释剂来直接模塑这类制品的方法。
到目前为止,水凝胶较接触透镜可以通过旋床切割和旋转铸塑的方法制备。在旋床切割方法中,基本上由无水亲水聚合物(干凝胶)组成的透镜坯料或园片在精密的旋床上被机械切割和抛光成透镜形状,然后将其与水或盐水接触,使聚合物水合,形成所需要的水凝胶透镜。在旋床切割操作中所采用的机械加工步骤与生产硬接触透镜中的步骤相似,只是要为聚合物水合而导致的透镜溶胀留有加工余量。
在旋转铸塑的方法中,将少量亲水单体混合物放置在凹面的,光学抛光的模具中,在单体聚合时模具进行旋转,形成干凝胶透镜。在聚合过程中透镜的两个光学表面同时形成。外表面由凹面模具的表面形成,内表面是由于旋转模具产生的离心力和聚合物混合物的表面张力的协同效果而形成。所得的透镜与水或盐水接触,使聚合物水合,形成与旋床切割透镜相似的水凝胶透镜。
最近,发现了一种生产水凝胶透镜的改进工艺,该方法比旋床切割或旋转铸塑都更加经济,而且还具有能更加精确控制水合透镜最终形状的优点。这种新方法包括直接模塑溶解于非水的、可被水置换的溶剂中的单体混合物,该混合物放置于具有最终所需要的水凝胶(水溶胀)透镜形状的模具中,使单体/溶剂混合物处于单体可聚合的条件下,制得具有最终所需要的水凝胶透镜形状的聚合物(聚合反应必须在非水介质中进行,因为水抑制聚合反应。)聚合反应完毕,用水置换溶剂,制得最终大小和形状与起始模塑的聚合物/溶剂制品的形状极为相似的水合透镜,这种直接模塑水凝胶接触透镜的方法在Larsen,美国专利4,495,313和Larsen等美国专利4,680,336中公开。在Larsen专利中,所采用的可被水置换的稀释剂为硼酸多元醇酯,其中的多元醇含有3或更多的羟基。可以任选地使用一种含有3或更多羟基的多元醇和一种二元醇的混合物作为上述的多元醇类化合物。参见第3栏第60行等和第4栏第18~22行。
Larsen专利中明确指出用于制备在直接模塑水凝胶接触透镜的生产工艺中所使用的硼酸酯的多元醇必须含有三个或更多个羟基。虽然其中公开了二元醇可以和三元或多元醇混合使用,但是三元醇或多元醇是基本成份。
本发明以上述发现为基础,即在制备成型水凝胶制品的直接模塑工艺过程中可使用硼酸与某种二羟基醇(更完整的定义见后面)形成的酯类做为可被水置换的稀释剂,由含有一种或多种亲水(甲基)丙烯酸酯如2-羟基基甲基丙烯酸酯(“HEMA”)为基本单体的聚合物混合物制备成型水凝胶制品(如软接触透镜)。本发明为生产成型水凝制品的直接模塑工艺提供了加工操作方面的便利,包括改进了脱模性(即在聚合后使用较小的力打开模具的能力),由此产生了经济效益如节约劳动成本,由于减少了存在表面缺陷的模塑制品的比例(这种缺陷会导致产品的报废),产率大大提高了。显然,脱模性的改进和产率的大大提高与本发明采用硼酸二醇酯有关,这种酯比Larsen专利4,495,313中优选的酯有更小的表面张力,这就降了聚合物/溶剂混合物对模具的粘附。
本发明采用的可被水置换的酯类对直接模塑工艺产生的另一个显著的改进是在聚合混合物中可以增加使用疏水性单体(如吸收UV的单体)。人们发现,在以Larsen专利所说的优选酯类作为稀释剂的单体/稀释剂混合物中使用疏水单体(如吸收UV的单体)时,这种单体常常不溶于该混合物中。
由于医学上更加重视紫外线(“UV”)对眼睛产生的副作用,所以产生了能吸收紫外线的眼镜、眼罩、接触透镜和眼内透镜。对于由聚合物(通常为丙烯酸类聚合物)制备的接触透镜和眼内透镜这两种透镜来说,使用具有吸收UV性能的优选方法是用含有吸收UV的共聚单体的共聚物制造这种透镜。这种单体已经在诸如Beard等、US4,528,311和Dunks等、4,716,234中公开。通过于单体/稀释剂混合物中加入吸收UV的单体,使得由直接模塑工艺制备的接触透镜具有吸收UV的性能,这是人们所期望的,本发明使这一理想变为现实。
成型的水凝胶制品(如软接触透镜)由以下步骤制备:
(1)模塑或铸塑一种聚合混合物,包括:
(a)一种单体混合物,包括作为主要成份的一种或多种亲水性(甲基)丙烯酸酯单体如2-羟乙基甲基丙烯酸酯,和一种或多种交联单体;和
(b)一种可被水置换的稀释剂,其中所说的稀释剂的粘度在30℃至少为100Mpa秒,和其中所说的稀释剂主要由硼酸的某中二羟基醇构成,该二羟基醇的汉森极性(δp)(Hansen polar)和汉森氢键(δh)内聚力参数(Hansen hydrogenbonding cohesion parameters)属于以δh=20.5,δp=13为中心,半径为8.5的园所包括区域。
制得所说单体和稀释剂的共聚物的成型凝胶,和
(2)然后用水置换该稀释剂。
本发明的一个重要方面是由以下步骤制备软接触透镜:
(1)模塑或铸塑一种聚合混合物,包括:
(a)一种单体混合物,包括作为主要成份的一种亲水性(甲基)丙烯酸酯如2-羟乙基甲基丙烯酸酯,一种或多种交联单体,和一种疏水性单体如吸收UV的单体;和
(b)一种可被水置换的稀释剂,其中所说稀释剂的粘度在30℃至少为100Mpa秒,和所说稀释剂主要由硼酸的某种二羟基醇酯构成,该二羟基醇的汉森极性(δp)和汉森氢键(δh)内聚力参数属于以δh=20.5,δp=13为中心,半径为8.5的园所包括的区域。
制得所说单体和稀释剂的共聚物的成型凝胶,和
(2)然后用水置换该稀释剂。
上述的Larsen专利(No,4,495,313)是申请人所知道的最相关的先有技术。
Larsen等专利No,4,680,336公开了在制造水凝胶制品的直接模塑工艺中使用某种稀释剂,这种稀释剂的优选依据其粘度和其汉森极性和氢键内聚力参数。
与直接模塑水凝胶制品(如软接触透镜)有关的其它美国专利包括:Larsen,US4,565,348和4,640,489,Ohkada等,US4,347,198,Shepard,US,4,208,364和Wichterle等Re 27,401(US3,220,960)。
图1是对几个二羟基醇的汉森内聚力参数δh和δp的绘图。
图2是用来确定软接触透镜的杨氏模量的校正图;和
图3是确定打开用于生产包括聚合物/稀释剂混合物的接触透镜的模具所需力的测试装置和设备的侧视图,并有部分示意图。
本发明用硼酸酯作为直接模塑水凝胶制品工艺中的可被水置换的稀释剂,该稀释剂包括某种二羟基醇的硼酸酯,所说的二羟基醇的汉森极性(δp)和汉森氢键(δh)内聚力参数属于以δh=20.5,δp=13为中心,半径为8.5的园所包括的区域。同时还要求硼酸与二羟基化合物所形成的酯具有在30℃至少为100Mpa秒的粘度,优选为在30℃至少为约500Mpa秒。
硼酸酯的制备方法与现有技术所述步骤相似,即使硼酸与二羟基醇(为简便,本发明有时将二羟基醇类简称为“二醇”)反应,并按照通常的方法(如减压蒸馏)除去反应生成的水。硼酸与二羟基醇的反应在一定的温度和一定的时间内进行,以便能够生成酯。通常认为,典型的反应温度范围为约50℃~120℃。在这样温度下,典型的反应时间为约2~12小时。对于任何条件,反应都进行到酯中的水含量少于约2%(重量)。所选择的硼酸对二羟基醇的比例应使所得酯的粘度在30℃至少为100Mpa秒。本发明下述的实施例所给出的硼酸对二羟基醇的典型比例能够得到具有所需粘度的酯。在某些情况下,为了控制得到的酯的分子量,可能还需要在酯化反应的混合物中混入少量的单羟基酯。
本发明用来制备可被水置换的硼酸酯稀释剂的二羟基醇类的汉森极性(δp)和汉森氢键(δh)内聚力参数属以以δh=20.5,δp=13为中心,半径为8.5的园所包括的区域。汉森内聚力参数δ通常用三个部分表示(δh,δp,δd),其中δh为氢键内聚力参数,δp为极性内聚力参数,δd为色散内聚力参数。本发明还发现二羟基醇的色散内聚力参数基本上相同(测定其值在大约15.7和17.0之间),因此,该参数对于确定任一具体的二羟基醇是否适用于本发明作用很小。对于用于制备硼酸酯稀释剂的二羟基醇的汉森内聚力参数的考虑便简化为对极性和氢键内聚力参数所构成的二元函数的研究。
汉森内聚力参数是本领域所公知的,有关的参考资料包括:“CRC Handbook of solubility parameters and Other Cohesion Parameters”,作者 Allan F.M.Barton,CRC出版,Inc.BoCa Raton,Florida(1983),特别是第85~87,141,和153~164页,Hansen,“THE UNIVERSALITY OF THE SOLUBILITY PARAMETERS”,I & EC Product Research and Development,Vol.8,No.1,1969年3月,第2~11页,Wernick“stereog-raphic Display of Three-Dimensional Solubility Parameter Correlations”,Ind.Eng.Chem Prod.Res.Dev.,Vol.23,No.2,1984,第240~245页,和Kirk-Othmer Ency clopedia of Chemical Technology 2nd.ed.,Suppl.Vol.Interscience,NY1971,第891和892页,这些资料阐述了汉森内聚力参数和如何确定这些参数。
选用的这些多元醇的汉森内聚力参数,δh和δp列于下表Ⅰ,在CRC手册中所列出的Hansen和Beerbower数据凡是能查到的均被采用。对于未列出的二元醇,其值由各基团组成用Hansen和Beerbower数据计算得到,如在CRC手册,PP.85~87和Kirk-Othmer,PP.891~892所示。δp值可以按照Kirk-Othmer所建议的简单加和的方法计算得到。
表Ⅰ所示的数据在图1中绘制了δh对δp的图。
用于本发明方法的单体混合物包含一种亲水性单体如HEMA作为主要成份,一种或多种交联单体,还可使用少量其它单体如甲基丙烯酸。HEMA是优选的亲水性单体,其它可以使用的亲水性单体包括2-羟乙基丙烯酸酯,2-羟丙基甲基丙烯酸酯,2-羟丙基丙烯酸酯,3-羟丙基甲基丙烯酸酯,N-乙烯基吡咯烷酮,丙三醇单甲基丙烯酸酯,丙三醇单丙烯酸酯及类似物。可以使用的交联单体(既可单独使用又可结合起来使用)包括乙二醇二甲基丙烯酸酯,三羟甲基丙烷三甲基丙烯酸酯,丙三醇三甲基丙烯酸酯,聚乙二醇二甲基丙烯酸酯(例如其中聚乙二醇的分子量可高达大约400),和其聚丙烯酸酯和聚甲基丙烯酸酯。对于每100份重量的HEMA或其它亲水性单体,交联单体的用量通为大约0.1至3重量份,优选用量为大约0.2到2重量份。它可以用来调节水凝胶在平衡态的吸水量,甲基丙烯酸酯的用量通常为每100份HEMA约0.2到8重量份。在聚合混合物中可以混入的其它单体包括甲氧基乙基甲基丙烯酸酯,丙烯酸等。
如上所述,本发明的一个特点是可以在单体混合物中混入疏水性单体,而不会遇到采用先有技术聚合HEMA类共聚物所遇到的那种程度的互不相溶问题。这种疏水性单体的实例是吸收UV的单体如苯并***(甲基)丙烯酸酯类,例如Beard等在US4,528,311中公开的2-〔2′-羟基-5′-丙烯酰氧基烷基苯基〕-2H-苯并***,Dunks等在US4,716,234中公开的2-〔2′-羟基-5′-丙烯酰氧基-烷基苯基〕-2H-苯并***,和Dunks等在1987年3月3日申请的美国专利申请号为21,096的申请(该申请已转让给受让人的一个机构)中公开的2-(2′-羟基苯基)-5(6)-(丙烯酰氧基)苯并***。可用于本发明的吸收UV的苯并***(甲基)丙烯酸酯类的具体实例包括下列化合物:
2-(2′-羟基-5′-甲基丙烯酰氧基乙基苯基)-2H-苯并***;
2-(2′-羟基-5′-甲基丙烯酰氧基乙基苯基)-5-氯-2H-苯并***;
2-(2′-羟基-5′-甲基丙烯酰氧基丙基苯基)-5-氯-2H-苯并***;
2-(2′-羟基-5′-甲基丙烯酰氧基丙基-3′-叔-丁基苯基)-2H-苯并***;
2-(2′-羟基-5′-甲基丙烯酰氧基丙基-3′-叔-丁基苯基)-5-氯代-2H-苯并***;
2-〔2′-羟基-5′-(2-甲基丙烯酰氧基乙氧基)-3′-叔-丁基苯基〕-5-甲氧基-2H-苯并***;
2-〔2′-羟基-5′-(r-甲基丙烯酰氧基丙氧基)-3′-叔-丁基苯基〕-5-甲氧基-2H-苯并***;和
2-(3′-叔-丁基-2′-羟基-5′-甲氧基苯基)-5-(3′-甲基丙烯酰氧基丙氧基)苯并***。
其它可以包含在聚合反应混合物中的各种用途的疏水性单体包括二苯酮衍生物,长链烷基的(甲基)丙烯酸酯,如正-十二烷基甲基丙烯酸酯,十八烷基甲基丙烯酸酯,正-辛基甲基丙烯酸酯,正-十二烷基丙烯酸酯等。
用于单体混合物中的吸收UV的苯并***(甲基)丙烯酸酯的用量应当使其能够在制造的透镜产品中有效地吸收UV射线。通常,吸收UV的单体的比例在这样的范围内,即对于每100重量份的主要亲水性单体(如HEMA)大约1到10重量份。
单体混合物中包含聚合物催化剂,聚合催化剂可以是能够产生自由基的化合物如月桂酰过氧化物,苯甲酰过氧化物,过碳酸异丙基酯,偶氮二异丁腈,或类似的化合物,在稍高一些的温度下这类化合物会产生自由基,或者,聚合催化剂为光引发剂体系如芳香族α-羟基酮或叔胺与二酮构成的体系。光引发剂体系的实例是4-(2-羟基乙氧基)苯基-2-羟基-2-丙基酮和,樟脑醌与4-(N.N-二甲基氨基)苯甲酸酯构成的体系。在聚合反应混合物中,催化剂的用量应使其能够进行有效的催化作用,如,每100重量份的HEMA约0.1至2重量份的催化剂。
以下提供的实施例用来说明本发明的具体实施。
实施例1
模塑工艺实例
由以下聚合反应混合物模塑接触透镜:
组份 重量份数
HEMA 100.0
甲基丙烯酸 2.00
二甲基丙烯酸乙二醇酯 0.4
Darocure 1173(1)0.35
硼酸1-4-丁二醇酯(2)102.75
(1)4-(2-羟基乙氧基)苯基-2-羟基-2-丙基酮
(2)通过在90℃,750mmHg真空度下,797重量份的1、4-丁二醇与203重量份的硼酸反应4小时制得。
聚合反应混合物放置于Larsen,美国专利4,640,489中所述的透明聚苯乙烯模具中(尤其参见Larsen专利图2),聚苯乙烯模具的一面在1.7焦耳/cm2强度的紫外光照射下曝光6至12分钟(严格的曝光时间并非十分必要)。
实施例2
吸收UV透镜的单体/稀释剂配方实例
与上面实施例1所述的条件相似,由下面的聚合反应混合物模塑接触透镜:
组份 重量份数
HEMA 100.00
甲基丙烯酸 2.04
二甲基丙烯酸乙二醇酯 0.4
2-(2′-羟基-5′-甲基丙烯酰氧基
丙基-3′-叔-丁基苯基)-5-氯-
2H-苯并*** 3.00
樟脑醌 0.40
4-(N,N-二甲基氨基)苯甲酸乙酯 0.60
硼酸1,4-丁二醇酯(1)77.45
(1)通过在90℃,750mmHg基真空度下,797份重量的1,4-丁二醇与203份重量的硼酸反应4小时制得。
实施例3
用下述一般步骤制备一系列硼酸与二羟基醇的酯类:
将硼酸和二羟基醇加入1升的旋转蒸发器中,逐渐加热至90℃(达到90℃所需时间约为1小时),同时保持适中的真空度(100托)。当达到90℃时,调整到最大真空度(10托),在90℃反应继续进行3个小时,冷却后,用Karl Fischer滴定法测定水含量,用Brookfield LVF粘度计(6,12和30rpm)测定硼酸酯在30℃的粘度。
把按上述一般步骤制备的硼酸酯总结归纳在下表Ⅱ中,该表列出了所用的二元醇(用表Ⅰ所述的简写),一种三元醇,丙三醇(“gly”),该三元醇用做控制剂,每个组份(醇和硼酸)的摩尔数和用来制备各种酯的醇与硼酸反应物的摩尔比,30℃时酯的粘度(单位为Mpa秒),酯中水的百分含量。该表还包括一个评述栏目。
(1)固体稀释剂,只是当与单体混合时可以使用。
(2)当与水混合时形成硼酸晶体。
(3)与水不完全相溶(可以形成1份重的酯对10份重的水的混合物),但可以使用,因为用醇或醇和水的混合物洗涤后,可以将其置换。
(4)与水或单体混合物(1∶1单体∶稀释剂,重量)都不相溶,不能使用。
在上面的表Ⅱ中所列出的硼酸酯中,有许多被用做下述单体配方的可被水置换的稀释剂,并对其效果进行评价:
组份 重量份数
HEMA 100.0
甲基丙烯酸 2.0
二甲基丙烯酸乙二醇酯 0.4
Darocure 1173 0.35
稀释剂 102.75
将这种单体配方(其中含0.4份的交联单体)
选出进行评价,是因为由这种配方制得的水凝胶的杨氏模量值与其做为接触透镜时所需要的性能有着密切联系。已经发现,如果用这种配方(其中包含0.4份的多官能团交联单体)制备的水凝胶的杨氏模量至少约为0.10-0.12Mpa,那么,可以认为由含有稍高比例的交联单体的相似配方制备的水凝胶具有足够的强度,可以用做软接触透镜。在通常的工业生产过程中,当使用与该实施例相似的配方时,多官能团交联单体如二甲基丙烯酸乙二醇酯和三羟甲基丙烷三甲基丙烯酸酯的用量一般约为0.2-1.0份。
按照上述实施例1的方法,在透明的聚苯乙烯模具中用上述的单体/稀释剂混合物制备软接触透镜。在55℃,每个模具中单体/稀释剂混合物的一面在强度约为1.7焦耳/cm2的紫外线照射下曝光10分钟(TL09灯,峰值射线位于350nm)。
对于由稀释剂/单体混合物制备的透镜进行以下方面的评价:
(1)在模具中和脱模后透镜的表观性能;和
(2)水合透镜的杨氏模量;和
(3)模塑透镜脱模所需的力。
这些评价的结果列于下面的表Ⅲ和表Ⅳ,表Ⅲ列出了序号,用于制备硼酸酯稀释剂的二羟基醇,透镜的表观性能(C=透明的,W=白色的,OS=不透明的表面,SO=略微不透明),杨氏模量“E”(单位Mpa)。表Ⅳ列出在三种不同温度下模塑透镜脱模所需的力。
模量的测定
表Ⅲ所列透镜的杨氏模量值是由以下步骤来确定的:
范围:
这种测定方法适用于具有几乎相同尺寸的透镜的无损坏模量测试。将这种测定结果对照一些相似透镜进行了校正,这些类似的透镜已经按照Larsen等US4,680,336(第9-10栏)所述的精确测定方法进行了测定。
透镜
适用于这种测定方法的透镜具有-1.0屈光度,8.9+/-0.3mmBC(片基曲度),0.15+/-0.01mm中心厚度,14.0+/-0.5mm直径。
测定
测量透镜的大小,如果其大小在规定的范围之内,将透镜放在一个透明的丙烯酸圆筒(外径13mm,内径9.8mm,高7.2mm)的顶上,使得透镜前曲面依靠在丙烯酸圆筒内部的(内径9.8mm)上表面上。将该圆筒放在Optimec JCF/R/SI接触透镜分析器的中心厚度测量室内,用0.9%的盐水浸没。圆筒和透镜处于同一个中心轴,以便透镜处于水平位置,改变透镜的中心厚度的度数,以测量透镜前曲面中心的挠度。
将一个3mm的不锈钢球(重0.2584克)小心地放在透镜的凹面上,透镜的中心部分将会根据其各自不同的模量发生不同的挠曲。用中心厚度值(mm)表示挠度,即可由图2的校正曲线确定模量。
至少从同一批生产的透镜中取出3个进行测量,对每个透镜的挠度测量3次,模量至少是9次测量的平均值。
圆括号内的数字是标准偏差。
(1)在力的测量过程中,模具上半部的凸缘断裂。
(2)未能获得数据。
(3)不能脱模,聚合物/稀释剂混合物将模具溶解,使模具的两部分连结在一起。
(4)脱模力太小,无法测量。
脱模实验
通过该实验估价打开用于生产聚合物/稀释剂混合物的模具所需的力,结果列于表Ⅳ,实验方法如下:
范围
该实验适用于确定分离模具的前半部和后半部(如Larsen美国专利4,640,489所述)所需要的最小力,模具的两个部分被含有某种已知数量稀释剂的聚合物基质连结在一起,对于所有分析试样,模具的大小应该保持恒定。
测试设备
图3画出了用来测量开启模具的力的测量装置和设备。用于测量这种力的仪器是实验室张力测试仪10,如英斯特朗(Instron)1122型。一个50磅测压元件(未画出)与图形记录仪12联用,该记录仪的最大记录值为20磅。
用空气加热枪(未画出)控制温度,如与Staco型3PN2210变阻器连接的Varitemp空气加热枪(VT-750A型)。将一个T型热电偶***聚合物/稀释剂混合物中,测量聚合物/稀释混合物的温度。
在测量过程中,装置14将试样16固定,杠杆18用来将模具的上半部分20与下半部分22拉开。
测试步骤
试样包括模具16的上半部分20和下半部分22,其中聚合物/稀释剂基质24将这两部分连结在一起。用来测试的试样是刚刚制备的,聚合物充满了恒定尺寸的模具。聚合反应之后,应立即将模具放入干燥器之中,以防止聚合物或稀释剂吸水。
将欲测试的试样放置在图3所示的试样固定装置上,该试样固定装置被下面的36PSI压力的英斯特朗仪固定器牢固握住,放置在固定装置上的整个试样与水平面成20°角。在测试过程中,用四个销(仅图示了两个销的横截面26,28)将模具的下半部分22固定,这四个销间隔90°,分布在模具下半部分22的圆周面上。
用来将上半部分20与下半部分22拉开的杠杆18位于这两部分之间,由上面的英斯特朗仪固定器30固定。杠杆拉起上半部分的速度由该仪器的横梁速度控制。
空气加热枪的气流直接喷射到模具的上半部分,保持连续加热,气流温度可以用变阻器控制。
试样的温度可以通过适当地***一个热电偶来进行监测,测量聚合物/稀释剂基质24的温度变化。当热电偶的测量值为所需要的温度时,英斯特朗的横梁就以1英吋/分的速度上升。测量在30℃,55℃和80℃脱模力。
如果用英斯特朗仪的图形记录仪记录,则消除聚合物/稀释剂与上半部20之间的粘附所需的力为时间的函数。由这种记录结果,可以确定最小脱模力。
从上面列出的数据可见,只有采用那些由属于规定的汉森参数区域的二元醇制备的酯,才能得到透明的透镜(这对于实际应用的透镜来说是最基本的要求),只有采用那些粘度大于100MPa秒的酯,才能得到具有足够高的模量值、足够的强度,可以实际应用的透镜。
脱模数据清楚表明,本发明的二元醇酯使脱模操作远比采用Larsen专利4,495,313中的优选酯易于进行(脱模需要的力更小)。
为了说明用本发明的二元醇硼酸酯代替甘油硼酸酯所获得的产量方面的改进,采用与上面实施例1所列的配方相似的单体/酯混合物,制造三批、每批80个透镜,测量这三批透镜中有表面缺陷的透镜数,当采用乙二醇/硼酸酯(表Ⅱ第21号酯)做为稀释剂时,表面缺陷的百分数为10.4%,当采用1.4-丁二醇/硼酸酯(表Ⅱ第12号酯)做为稀释剂时,表面缺陷的百分数为13%,当采用甘油/硼酸酯做为稀释剂(表Ⅱ第20号酯时,表面缺陷的百分数为30.4%。这是对Larsen专利4,495,313所述方法的有价值的改进。
Claims (10)
1、制备成型水凝胶制品的方法,包括以下步骤:
(1)模塑或注塑聚合混合物,其中包括:
(a)一种单体混合物,包括做为主要成份的亲水性甲基丙烯酸酯单体和交联单体;和
(b)一种可被水置换的稀释剂,其中所说稀释剂的粘度在30℃至少为100Mpa秒,其中所说的稀释剂基本上由某种二羟基醇的硼酸酯组成,所说二羟基醇的汉森极性(δp)和汉森氢键(δh)内聚力参数属于以δh=20.5,δp=13为中心,半径为8.5的圆所包括的区域,
制备所说单体共聚物和所说稀释剂的成型凝胶,和
(2)然后用水置换所说的稀释剂。
2、根据权利要求1的方法,其中所说的亲水性单体是羟烷基(甲基)丙烯酸酯。
3、根据权利要求2的方法,其中羟烷基(甲基)丙烯酸酯为2-羟乙基甲基丙烯酸酯。
4、根据权利要求1的方法,其中所说的二羟基醇选自下列化合物:乙二醇、1,2-丙二醇、1,4-丁二醇、1,6-己二醇、2,5-己二醇、1,8-辛二醇、二甘醇、三甘醇、四甘醇,分子量最高到大约2000的聚乙二醇、二聚丙二醇、和三聚丙二醇。
5、根据权利要求4的方法,其中所说的二羟基醇选自下列化合物:1,4-丁二醇、1,6-己二醇、2,5-己二醇、二甘醇、三甘醇、四甘醇,分子量最高到大约1000的聚乙二醇、二聚丙二醇,和三聚丙二醇。
6、根据权利要求1的方法,其中所说的二羟基醇是1,4-丁二醇。
7、根据权利要求1的方法,其中所说的二羟基醇是二甘醇。
8、根据权利要求1的方法,其中成型水凝胶制品是接触透镜。
9、制备接触透镜的方法,包括下列步骤:
(1)模塑或注塑聚合混合物,其中包括:
(a)一种单体混合物包括做为主要成份的亲水性甲基丙烯酸酯,交联单体,和疏水性单体;和
(b)一种可被水置换的稀释剂,其中所说稀释剂的粘度在30℃至少为100Mpa秒,其中所说稀释剂基本上由某种二羟基醇的硼酸酯构成,所说二羟基醇的汉森极性(δp)和汉森氢键(δh)内聚力参数属于以δh=20.5,δp=13为中心,半径为8.5的圆所包括的区域。
制备所说单体共聚物和所说稀释剂的成型凝胶,和
(2)然后用水置换所说稀释剂。
10、根据权利要求1的方法,其中所说亲水性单体是羟烷基(甲基)丙烯酸酯。
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US07/276,007 US4889664A (en) | 1988-11-25 | 1988-11-25 | Method of forming shaped hydrogel articles including contact lenses |
US276,007 | 1994-07-15 |
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CN1045270A true CN1045270A (zh) | 1990-09-12 |
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US4495313A (en) * | 1981-04-30 | 1985-01-22 | Mia Lens Production A/S | Preparation of hydrogel for soft contact lens with water displaceable boric acid ester |
US4680336A (en) * | 1984-11-21 | 1987-07-14 | Vistakon, Inc. | Method of forming shaped hydrogel articles |
-
1988
- 1988-11-25 US US07/276,007 patent/US4889664A/en not_active Expired - Lifetime
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1989
- 1989-11-24 ZA ZA898998A patent/ZA898998B/xx unknown
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- 1989-11-24 RU SU894742746A patent/RU2060525C1/ru active
- 1989-11-24 GR GR890100783A patent/GR1000757B/el unknown
- 1989-11-24 IL IL92443A patent/IL92443A/xx not_active IP Right Cessation
- 1989-11-24 AU AU45550/89A patent/AU622952B2/en not_active Expired
- 1989-11-24 NO NO894696A patent/NO175901C/no unknown
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- 1989-11-25 KR KR1019890017268A patent/KR0152653B1/ko not_active IP Right Cessation
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- 1989-11-27 JP JP1307384A patent/JP3001594B2/ja not_active Expired - Lifetime
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1993
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CN107109285A (zh) * | 2015-01-15 | 2017-08-29 | 道达尔销售服务公司 | 受控缔合的热缔合添加剂组合物和包含其的润滑剂组合物 |
CN107109285B (zh) * | 2015-01-15 | 2020-10-02 | 道达尔销售服务公司 | 受控缔合的热缔合添加剂组合物和包含其的润滑剂组合物 |
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