CN1047982C - 制作含有硅酮的水凝胶透镜的方法 - Google Patents
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Abstract
一种制作硅酮水凝胶接触透镜的方法,采用机械加工操作,得到具有所需要的最终形状的透镜。该法包括:
制备由含硅酮单体、亲水单体和有机稀释剂组成的单体混合物;
将该单体混合物充入模具中,并在模具中固化该配方组分,得到成形制品;
自成形制品中除去有机稀释剂,以改善该成形制品的机械加工性能;
对成形制品机械加工,得到具有所需外廓形状的接触透镜。
Description
本发明涉及一种改进的制作硅酮水凝胶透镜的方法。
水凝胶是一种接触透镜的理想材料,水凝胶为平衡态时含水的水合交联聚合物系。水凝胶透镜不仅表现出理想的生物适应性和舒适性而且表现出比较高的氧透过性。
传统的水凝胶透镜由主要含诸如2-羟乙基异丁烯酸酯或N-乙烯基吡咯烷酮等亲水单体的单体混合物制成。这些传统水凝胶材料的氧透过性与材料的含水量有关。最近已有报导,用含硅酮的水凝胶单体作成水凝胶以提高水凝胶透镜的透氧性能,因为硅酮基材料比水的氧透过性更高。通常由聚合含有至少一种含硅酮的单体和至少一种亲水性单体的混合物制作硅酮水凝胶(即含硅酮的水凝胶)。含硅酮的单体或亲水性单体均可用作交联剂(交联剂被定义为一种有多种聚合官能度的单体)或者可用做一种单独交联剂。
有多种公知的制作接触透镜时固化单体混合物的方法,包括旋压浇铸和静压浇铸。旋压浇铸法公开在美国专利3,408,429和3,660,545中,而静压浇铸法公开在美国专利4,113,224和4,197,266中。为制备具有所需最终形状的接触透镜,在单体混合物固化之后随之是机械加工工序。
根据几种已知的制作接触透镜的方法,铸塑法可以制出具有所需前透镜表面和后透镜表面的成形制品。例如静压浇铸法,可将单体混合物充入一模具中,这个模具由用来形成所需前透镜表面的形面的第一模件和用来形成所需后透镜表面的形面的第二模件构成。在旋压浇铸法中,可将单体混合物注入一个有形成所需前透镜表面的形面的敞开模具中,并通过模具的转动形成所需的后透镜表面。但是,为得到更适于在眼睛上定位的接触透镜,制品固化以后仍需进行机械加工。这样的机械加工包括为得到所需的边棱的车床磨削磨光透镜边缘或者抛光透镜的边棱或表面。
其他的公知制造方法中,铸塑法可以得到没有所需前和/或后透镜表面的成形制品。因此,铸塑过程之后随之便是机械加工工序,以形成所需的透镜表面。比如,美国专利4,555,732公开了一种方法,将过量的单体混合物在模具中旋压浇铸固化成有前透镜表面和较大厚度的成形制品,而固化的旋压浇铸制品的后表面随后被车床磨削,得到一个有所需厚度和后表面的接触透镜。机械磨削透镜表面之后,可伴有一些机械加工工序,如精修前述之边棱的操作。
但是,在着手采用这种在硅酮凝胶接触透镜制作过程中带有机械加工的方法时,遇到了困难。比如,硅酮凝胶制品一般比传统凝胶制品更难于机械加工,因为用含硅酮单体制出的凝胶比仅用传统单体制出的凝胶更软且更象橡胶,尤其是在有稀释剂的铸塑时,更是如此。
本发明提供了一种制作硅酮凝胶接触透镜的方法,它采用机械加工工序,制造具有所需最终形状的透镜。该方法包括:
制备由含硅酮单体,亲水单体和有机稀释剂组成的单体混合物;
将混合物充入模具并在模具中固化该混合物,得到成形制品;
从成形制品中除去有机稀释剂,以改善制品机械加工性能;以及
机械加工该成形制品,得到具有所需形状的接触透镜。
任何公知的包含至少一种含硅酮单体和至少一种亲水单体的硅酮水凝胶配方均可用于本发明的方法中,这对本领域的技术人员来讲都是显见的。可将单体物质做为单体或预聚物加到形成成形制品的单体混合物中。因此,可将“含硅酮单体”和“亲水单体”两词理解为包含预聚物。可以在美国专利4,136,250;4,153,641;4,740,533;5,034,461;以及5,070,215中找到含硅酮单体的实例。
X表示-O-或-NR-;
每个R分别表示氢或甲基;
每个R1分别表示低烷基或苯基;
f是1或3至10。
这类大的单体包括甲基丙烯氧基丙基三(三甲硅氧基)硅烷,甲基异丁烯酸五甲基二硅氧烷酯,三(三甲基硅氧基)异丁烯氧基丙硅烷,乙酸苯基四甲基二硅氧烷基乙酯,以及甲基二(三甲基硅氧基)异丁烯氧基甲基硅烷。
每个A′分别表示活性不饱和原子团,如丙烯酸或异丁稀酸的酯或氨化物;
每个R3,R4,R5和R6分别选自包括有1到18个碳原子的一价烃基或卤素取代的一价烃基的一组,其碳原子之间有醚链;
R7表示带1至22个碳原了的二价烃基;
n是0或者大于或等于1的整数。
Y′表示-O-,-S-或-NH-;
Ra表示含硅酮的有机原子团;
R8表示氢原子或甲基;d是1,2,3或4;q是0或1。适用的含硅酮有机原子团R1包括下述几种:
-(CH2)n'si[(CH2)m′CH3]3;
R11表示带1到6个碳原子的烷基或氟烷基;
e为1到200;
n′为1,2,3或4;
m′为1,2,3,4或5。
含硅酮的碳酸乙烯酯或氨基甲酸乙烯酯单体特别包括:1,3-双[4-乙烯氧基羰氧基]丁-1-基]四甲基-二硅氧烷;碳酸3-(三甲基硅基)两基乙烯酯;3-(乙烯氧基羰基硫)丙基-[三(三甲基硅氧基)硅烷];氨基甲酸3-[三(三甲基硅氧基)硅基]丙基乙烯酯;氨基甲酸3-[三(三甲基硅氧基)硅基]丙基丙基酯;碳酸3-[三(三甲基硅氧基)硅基]丙基乙烯酯;碳酸权丁基二甲基硅氧基乙基乙烯酯;碳酸三甲基硅基乙基乙烯酯;碳酸三甲基硅基甲基乙烯酯;和“V2D25”,其它优选的含硅酮的单体包括下列通式的单体:
(1V) E(*D*A*D*G)a*D*A*D*E′;或
(V) E(*D*G*D*A)a*D*G*D*E′;
其中:
D表示带6到30个碳原子的烷基双基,烷基环烷基双基,环烷基双基,芳基双基或烷基芳基双基;
G表示带1到40个碳原子的烷基双基,环烷基双基,烷基环烷基双基,芳基双基或烷基芳基双基,它们在主链上可以含醚,硫或胺链;
*表示尿烷或脲键;
a至少为1;
每个Rs分别表示带1到10个碳原子且碳原子之间含有醚链的烷基或氟代烷基;
m至少为1;
p使该部分的重量达到400至10000;
其中
R12是氢原子或甲基;
R13是氢原子,带1到6个碳原子的烷基,或-CO-Y-R15原子团,其中Y为-O-,-S-或-NH-;
R14是带1至10个碳原子的二价亚烃基;
R15是带1到12个碳原子的烷基;
X表示-CO-或-OCO-;
Z表示-O-或-NH-;
Ar表示带6到30个碳原子的芳基;
W是0到6;
x是0或1;
y是0或1;
z是0或1。
含硅酮单体可以和各种各样的亲水性单体进行共聚反应,得出硅酮凝胶透镜。适用的亲水单体包括:不饱和羧酸,如异丁烯酸和丙烯酸;丙烯酸取代的醇,如异丁烯酸2-羟基乙酯和丙烯酸2-羟基乙酯;乙烯基丙酰胺,如N-乙烯基吡咯烷酮;以及丙烯酰胺,如甲基丙烯酰胺和N,N-二甲基丙烯酰胺。进一步的实例还有如美国专利5,070,215所述的亲水的碳酸乙烯酯或氨基甲酸乙烯酸单体,以及美国专利4,910,277所述的亲水噁唑酮单体。其他适用的亲水单体对本领域的技术人员都是显见的。
最初的单体混合物可以包含有机稀释剂。这里所用“有机稀释剂”一词包括使最初单体混合物中组分不相容性达到最小,并且基本上不与最初单体混合物中组分发生反应的有机化合物。此外,有机稀释剂用来使单体混合物聚合所得之聚合产物达到最小的相离析。而且有机稀释剂一般可降低混合物聚合反应的玻璃转化温度,使固化过程的效率更高,最终获得聚合更均匀的产物。最初单体混合物及聚合产物的均匀性对硅酮水凝胶来说是很重要的,这主要是由于包含着含硅酮的单体的缘故。
可以考虑的有机稀释剂包括:带C6-C10直链脂族-羟基醇的一羟基醇,如n-己醇和n-壬醇尤为适宜;二元醇,如乙二醇;多元醇,如丙三醇;醚,如乙二醇单乙醚;酮,如甲基乙基酮;酯,如烯胺甲酯;以及烃,如甲苯。有机稀释剂应有充分的挥发性,以便在环境压力或接近环境压力下通过蒸发,将其从固化制品中除去。其他适用的有机稀释剂对本领域的技术人员都是显见的。
有机稀释剂应包括一定数量。以提供出所需的效应。一般地,稀释剂占单体混合物重量的5-60%,以占10-50%的重量尤为适宜。
按照本发明的方法,采用传统方法如静压浇铸或旋压浇铸固化由至少一种亲水单体,至少一种含硅酮单体和有机稀释剂组成的单体混合物。
随后,从固化的制品中除去足够量的有机稀释剂,以改善制品的机械加工性能。申请人发现,尽管含有有机稀释剂可以将前述的有关单体不相容性,相分离或聚合不均匀的问题减至最小,但过量的剩余稀释剂会使正常的软硅酮水凝胶制品变得愈加发粘或更似橡胶,而更难于机械加工;实际上完全可以避开固化制品的机械加工。令人惊异的是,按照本发明方法的步骤提供了从固化制品中除去有机稀释剂而不使制品形变如使透镜翘卷的办法。
有机稀释剂适宜在环境压力或接近环境压力下通过蒸发而去除,并且可提高温度以缩短蒸发稀释剂所需要的时间。去除步骤的时间、温度和压力条件会随着稀释剂和特殊单体组分的挥发性这些因素改变,这可以由本领域的技术人员很容易地确定。根据一个优选的实施例,在去除步骤中采用温度不低于50℃,最好是不低于55℃。稀释剂去除步骤完成之后的固化制品宜含有不超过20%重量的稀释剂,最好不超过5%的重量更适宜。
接着有机稀释剂去除步骤之后,用各种公知方法对成形的制品进行机械加工。机械加工步骤包括机床磨削透镜表面,机床磨削透镜边棱,磨光透镜边棱或抛光透镜边棱或表面。由于在透镜表面发粘或呈橡胶情况下对该表面的机械加工尤为困难,所以本方法是一个非常便利的方法,其中对透镜表面进行机床磨削。
通常,在制品从模件中脱出之前完成这类机械加工。机械加工工序之后,可以从模件中脱出透镜并进行水合作用。另一方面,也可以在从模件中脱出制品并进行水合之后,再机械加工。
典型的配方列于下表中。
配 方A组分 重量份数TRIS-VC 55NVP 30V2D25 15VINAL 1n-壬醇 15Darocur 0.2着色剂 0.05
配方B组分 重量份数
(或重量百分比)IDS3H 35Tris 35DMA 39MAA In-己醇 40TXN 0.1%MDEA 0.2%着色剂 0.007%
配方C组分 重量份数
(或重量百分比)IDS3H 30Tris 30NVP 27DMA 9VDMO 1HEMAVC 0.15n-己醇 30Darocur 0.5%着色剂 0.03%
配方D组分 重量份数
(或重量百分比)IDS3H 30Tris 30NVP 27DMA 9VDMO 1HEMAVC 0.15n-壬醇 30Darocur 0.5%着色剂 0.03%
配方E组分 重量份数
(或重量百分比)IDS3H 35Tris 35DMA 48MAA 1n-己醇 40TXN 0.1%MDEA 0.2%着色剂 0.007%上面给出以下内容:Darocur Darocur-1173,一种紫外引发剂。DMA N,N-二甲基丙烯酰胺HEMAVC碳酸甲基丙烯氧基乙基乙烯酯IDS3H 从二异氰酸异佛尔酮酯,二乙二醇和α,ω-双(羟
基丁基二甲基硅基)多硅烷衍生的,并用异丁烯酸
2-羟乙酯封端的尿烷预聚物(如美国专利5,034,
461所述。MAA异丁烯酸MDEA甲基二乙醇胺NVP N-乙烯基吡咯烷酮着色剂 1,4-双[4-(2-甲基丙烯氧基乙基)苯氨
基]蒽醌
TRIS异丁烯酸三(三甲基硅氧基)硅基丙基酯
TRIS-VC氨基甲酸三(三甲基硅氧基)硅基丙基乙烯酯
TXN噻吨酮
V2D25如前所述的含硅酮碳酸乙烯酯
VDMO 2-乙烯基-4,4-二甲基-2-噁唑啉-5-酮
VINAL N-乙烯氧羰基丙氨酸
以下的例子进一步说明了本发明的优选实施例。
实例1
在不活泼的氮气氛围中,将20μl的配方A组分加入到清洁的Barex树脂(一种丙烯腈和异丁烯酸酯的改性共聚物橡胶)制成的开口凹形模件中。该模件在有紫外光(用Black紫外光仪测得为1-2.5mw/cm2)存在的情况下,以每分钟320转的速度旋转5分钟,另外再照射大约30分钟的紫外光,完成固化。
将透镜在压力烘箱中于60℃下保持3小时,除去n-壬醇。随后,对透镜修边并以1000转/分的速度和25g的力对模件中的透镜球磨6秒钟。在50℃水中手工将透镜从模件中脱出,并在室温下和异丙醇中最少经48小时的萃取。然后将透镜在85℃水中萃取4小时。最后,在有缓冲盐水的管形瓶中高压灭菌。
实例2
在不活泼的氮气氛围中,将30μl的配方B组分充入一清洁的开口凹形Barex树脂模件中在有紫外光存在的条件下(由Black紫外光仪测得为1-2.5mw/cm2)以341转/分的速度将该模件旋转15分钟,并另外再用紫外光照射大约30分钟,完成固化。
将透镜在室温下放置一夜,除去n-己醇。随后对透镜修边,并以1000转/分的速度用130g力对模块中的透镜球磨3秒。在乙醇/水介质中将透镜从模件中脱出,在室温下于乙醇中对透镜进行最少48小时的萃取,然后在80℃水中再对其进行4小时萃取。最后,清洗透镜并用未经储存的缓冲盐水加热灭菌。
实例3
在不活泼的氮气氛围中,将45μl的配方C的组分注入清洁的Barex树脂凹形半模具上并用聚丙烯树脂凸形半模具盖住。在70磅/平方英寸的压力下将这些半模具压紧,在有紫外光(由Spectronic紫外光仪测得为6-11mw/cm2)的条件下使混合物固化15分钟,并另外对模具照射约5分钟紫外光。
取去上型,并在压力烘箱中于60℃下将透镜保存3小时,除去n-己醇。随后,机械磨削透镜边棱,并以3200转/分的速度用60g力球磨10秒钟。在50℃水中手工将透镜从模具中脱出,随之在室温下于异丙醇中萃取最少48小时,再在85℃水中萃取约4小时。最后用未经储存的缓冲盐水对透镜进行灭菌。
实例4
在不活泼的氮气氛围中,将80μl的配方C的组分充入清洁的凹形开口Barex树脂模具中在有紫外光(用Spectronic紫外光仪测得为6-10mw/cm2)存在的条件下以400转/分的速度将模具旋转约20分钟,并另外在紫外光下照射约12分钟。
将成形的制品在压力烘箱中60℃下放置3小时,除去n-己醇。随后,用车床磨削制品的后表面,再对透镜进行30秒的抛光。在50℃水中手工将透镜从模具中脱出,在异丙醇中萃取最少48小时,再在约85℃水中萃取4小时。最后,在缓冲盐水中高压灭菌。
实例5
除了用含30份重量n-壬醇的配方D组分代替配方C的组分之外,沿用实例4的步骤。
实例6
将配方X-1,X-2和X-3(分别含10,15和20份重量的n-己醇)的每一种在扁平的聚丙稀圆盘模件中静压浇铸,并用紫外光固化。检验固化的扁圆盘。从分别含有15和20份重量n-己醇的配方X-2和X-3所得到的圆盘铸件,由于过多的残留n-己醇对边棱做机械加工而言是太粘了,而由配方X-1所得的圆盘铸件仅含10份重量的n-己醇,所以并不显得粘。
配方,X-1,X-2,X-3组分
重量份数
(或重量百分比)IDS3H 35Tris 35DMA 30n-己醇 10,15,20DME· 0.2%*BME 苯偶姻甲醚,一种紫外引发剂
实例7
透镜为沿用实例1工艺配方A(含15份重量的n-壬醇)的旋压浇铸件。将此旋压浇铸透镜留在模具中,放到温度保持在50℃,55℃和60℃的压力烘箱中。
对于在55℃和60℃下干燥的透镜而言,保留在模具中的两个透镜每隔0(操纵),1、2、3、4、5、6和24小时从炉中取出,再用2ml异丙醇萃取至少12小时。对于在50℃下干燥的透镜,保持在模具中的两个透镜每隔0(操纵),1、6和24小时取出,并且每个样品用2ml异丙醇萃取至少12小时。每个用异丙醇萃取(0.1μl)的样品完成之后,再用毛细管气相色谱法测定其n-壬醇的含量。
在受控条件下,样品在55℃和60℃下干燥2小时后,以及在50℃下干燥6小时后,其中n-壬醇的百分比均低于5%。
实例8
透镜也是沿用实例1的工艺配方A(含15份重量的n-壬醇)的旋压浇铸件。将旋压浇铸透镜留在模具中,放在温度保持为55℃的压力烘箱中。10个模具每隔1、2、3、4、5和6小时以及24小时(作为一种控制形式)取出,并沿用实例1的工艺修边。
在55℃温度下放置1小时的透镜边棱显得粗糙,而且修边后会出现碎裂。而在55℃下保持24小时的透镜可以进行令人满意的修边。透镜中含有过量的n-壬醇,就表现出较差的可修边性。在55℃下放置2小时或再长些时间的透镜就能与在55℃下放置24小时的透镜修边情况相比。因此,要将透镜在55℃温度下至少放置2小时,充分地除去浇铸透镜中的稀释剂,以便对透镜边棱进行机械加工。以实例7的数据为基础,将n-壬醇去除到低于5%,即足以获得满意的边棱加工性。
在已经说明了一些优选实施例的同时,尚应理解,本发明并不限于此,一些改型和变化对于本领域的普通技术人员来讲都是显而易见的。
Claims (20)
1、一种制备硅酮水凝胶接触透镜的方法,所述方法包括:
(a)提供一种由含硅酮单体,亲水单体和有机稀释剂组成的单体混合物;
(b)将该单体混合物充入模具中并在模具中固化配方的组分,得到成形制品;
(c)自成形制品中除去稀释剂,以改善该成形制品的机械加工性能;
(d)对成形制品机械加工,得到具有所需外廓形状的接触透镜。
2、一种如权利要求1所述的方法,其特征在于将单体充入的模具由形成前透镜表面的形面的第一模件和形成后透镜表面的形面的第二模件组成。
3、一种如权利要求1所述的方法,其特征在于通过旋压浇铸来固化。
4、一种如权利要求1所述的方法,其特征在于所说的步骤(d)包括把透镜表面机械加工成所需之外廓形状。
5、一种如权利要求4所述的方法,其特征在于所述之机械加工包括机车磨削后透镜表面。
6、一种如权利要求4所述的方法,其特征在于所述之机械加工包括机车磨削前透镜表面。
7、一种如权利要求4所述的方法,其特征在于所述之机械加工包括磨光透镜表面。
8、一种如权利要求1所述的方法,其特征在于所述之步骤(d)包括把成形的透镜制品边棱机械加工成所需要的边棱外廓形状。
9、一种如权利要求8所述的方法,其特征在于所述之机械加工包括机车磨削该边棱。
10、一种如权利要求8所述的方法,其特征在于所述之机械加工包括磨光该边棱。
11、一种如权利要求1所述的方法,其特征在于,包括:
(a)制备所述之单体混合物;
(b)将过量的这种单体混合物充入一个包含形成所需之前透镜表面的凹形面模具中,并在模具中旋压铸塑固化配方组分,得到具有所需之前透镜表面的成形制品;
(c)自成形制品中除去稀释剂,改善制品的机械加工性能;
(d)机车磨削制品的后表面,得到具有所需厚度的接触透镜。
12、一种如权利要求1所述的方法,包括:
(a)制备所述之单体混合物;
(b)将所述单体混合物充入模具中,所说的模具由形成前透镜表面的形面之第一模件不形成后透镜表面的形面之第二模件组成;再在模具中固化所说的配方组分,得到具有前透镜表面和后透镜表面的成形透镜制品;
(c)除去稀释剂,改善该制品的机械加工性能;
(d)对该制品的边棱机械加工,得到具有所需边棱外廓形状的接触透镜。
13、一种如权利要求1所述的方法,包括:
(a)制备所述之单体混合物;
(b)将所述单体混合物充入具有为形成所需之前透镜表面的阴模面的模具中,并且旋压铸塑在模具中固化单体混合物,得到具有所需之前透镜表面和后透镜表面的成形透镜制品;
(c)除去稀释剂,改善该制品的机械加工性能;
(d)对制品的边棱机械加工,得到具有所需边棱外廓形状的接触透镜。
14、一种如权利要求1所述的方法,其特征在于还包括水合步骤(d)所得的透镜。
15、一种如权利要求1所述的方法,其特征在于有机稀释剂为醇。
16、一种如权利要求15所述的方法,其特征在于有机稀释剂从包括n-己醇和n-壬醇的组中选出。
17、一种如权利要求15所述的方法,其特征在于步骤(c)包括在升高的温度下干燥该成形制品。
18、一种如权利要求17所述的方法,其特征在于将成形制品在不低于50℃温度下至少放置2小时。
19、一种如权利要求1所述的方法,其特征在于含硅酮单体从包括含硅酮的碳酸乙烯酯预聚物和含硅酮的氨基甲酸乙烯酯预聚物的组中选出。
20、一种如权利要1所述的方法,其特征在于含硅酮的单体是含硅酮的尿烷预聚物。
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US07/924,214 US5260000A (en) | 1992-08-03 | 1992-08-03 | Process for making silicone containing hydrogel lenses |
US924,214 | 1992-08-03 |
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CN1085844A CN1085844A (zh) | 1994-04-27 |
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Also Published As
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AU669194B2 (en) | 1996-05-30 |
JP3249123B2 (ja) | 2002-01-21 |
EP0652823A1 (en) | 1995-05-17 |
AU4539693A (en) | 1994-03-03 |
KR100250192B1 (ko) | 2000-04-01 |
EP0652823B1 (en) | 1997-12-03 |
US5260000A (en) | 1993-11-09 |
BR9306910A (pt) | 1998-12-08 |
ES2111754T3 (es) | 1998-03-16 |
JPH08501504A (ja) | 1996-02-20 |
MX9304682A (es) | 1994-03-31 |
HK1005613A1 (en) | 1999-01-15 |
DE69315581T2 (de) | 1998-06-04 |
DE69315581D1 (de) | 1998-01-15 |
CA2141571C (en) | 1998-02-10 |
WO1994003324A1 (en) | 1994-02-17 |
TW285677B (zh) | 1996-09-11 |
CA2141571A1 (en) | 1994-02-17 |
CN1085844A (zh) | 1994-04-27 |
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