CN1074450A - 可湿的聚硅氧烷水凝胶组合物及其制法 - Google Patents
可湿的聚硅氧烷水凝胶组合物及其制法 Download PDFInfo
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Abstract
披露了一种具有高可湿性的改进的含聚硅氧烷
水凝胶,它包含一种含聚硅氧烷单体,至少一种含丙
烯酸基亲水单体,以及至少一种含乙烷基亲水单体。
Description
本发明涉及适用于生产生物医学装置特别是接触镜片的改进的可湿聚合物水凝胶组合物。
水凝胶已经是用于制备生物医学装置的所需要的一类材料,并且至少自Wichterle等人的美国专利U.S.3220960开始已为人们所知晓,该专利披露了包含丙烯酸羟烷基酯或甲基丙烯酸羟烷基酯的含水聚合物并被相应的二酯(聚甲基丙烯酸羟乙酯,它以poly-HEMA而知名)所交联的水凝胶。
在本领域中,任何含水的交联聚合物体系常称作水凝胶。因此,水凝胶的物理性能可以有很大的变化,而且主要取决于它们的水分。因为水凝胶显示优异的生物配伍性,因此人们对把水凝胶用作生物医学装置特别是接触镜片,具有浓厚的兴趣。
在接触镜片领域,各种因素必须综合起来以形成具有合适性能的材料。氧透过性,可湿性,材料强度及稳定性是但只是少数必须仔细平衡的因素,以获得有用的最终结果的接触镜片。因为角膜独自从与大气的接触中获及氧的供应,所以好的氧透过性是任何接触镜片材料的一种关键性能。
人们发现,某些交联聚合物材料可被水化,并维持其水份。人们还进一步发现,由这些交联水凝胶聚合物制成的接触镜片内的水份越高则通过镜片到达眼睛及其角膜氧透过性越大。
高含水水凝胶有时显示出不期望的机械性能。例如,这种水凝胶常常不易生成对水解稳定的镜片。此外,这种材料由于抗张强度不好导致有时被撕裂或破损。需要的是耐用的高可湿的高氧透过性材料。可湿性是重要的,因为假若镜片不是充分可湿的,则它不会保持润滑,因而不能舒服地带在眼中。理想的接触镜片应不仅具有优异的氧透过性,而且具有优异的泪液可湿性。
含聚硅氧烷的材料被试用作为可行的接触镜片材料,并显示出很好的氧透过性及耐久性。然而,大多数含聚硅氧烷的材料是很疏水的,因此不是充分可湿的。此外,人们认为,这种疏水性引引起了类脂类物质高沉积的问题,后者当用某些含聚硅氧烷聚合物制成的镜片时也会导致不舒服。
因此,具有理想刚性、高的氧透过性及高度可湿性的用作生物医学装置例如接触镜片的最理想水凝胶材料,至今尚未为人知晓。
根据本发明,水凝胶例如含聚硅氧烷的水凝胶,更具体说聚氨酯-聚硅氧烷水凝胶及烯属封端的聚硅氧烷水凝胶,经加进含乙烯基亲水单体和含丙烯酸亲水单体,可明显提高其表面可湿性。人们相信这些单体起润湿剂的作用,并与单体混合物中占优势的疏水含聚硅氧烷单体起作用,生成具有理想刚性的高可湿性水凝胶。所得的这类水凝胶特别适用作为接触镜片材料。
图1和图2描绘了当NVP对DMA的组成比例改变时对聚氨酯膜的模数的影响。
图3描绘了当NVP对DMA的组成比例改变时甲基丙烯酸酯封端的聚硅氧烷膜的模数的影响。
本发明涉及改进水凝胶,具体说是具有理想刚性、适用于生物医药应用例如接触镜片的含聚硅氧烷水凝胶的可湿性。
本发明的润湿剂是结合至少一个含乙烯基亲水单体和至少一个含丙烯酸基亲水单体的结果。
术语“含乙烯基”化合物是指含乙烯基(CH2=CH-),并且通常是高活性的化合物。已经知道这类乙烯基是相对易于聚合的。“含丙烯酸基”化合物是指含有丙烯酸基(CH2=CRCOX)的化合物,也已知它们是容易聚合的。
用于本发明的含乙烯基单体包括亲水单体例如N-乙烯基吡咯烷酮,N-乙烯基-N-甲基乙酰胺,N-乙烯基-N-乙基乙酰胺,N-乙烯基-N-甲基甲酰胺,N-乙烯基-甲酰胺,其中N-乙烯基吡咯烷酮(NVP)是最优选的。
用于本发明的含丙烯酸基单体包括亲水单体例如甲基丙烯酸2-羟乙酯,甘油甲基丙烯酸酯,2-羟乙基甲基丙烯酰胺,N,N-二甲基(甲基)丙烯酰胺,二丙酮丙烯酰胺,甲基丙烯酸及丙烯酸,其中N,N-二甲基丙烯酰胺(DMA)是最优选的。
最好加入一种交联剂组合物,后者含有至少一个可聚合乙烯基和至少一个可聚合丙烯酸基或苯乙烯基,它披露在共同待审和共同转让的美国申请序号07/758047和07/758647中,以及在共同待审和共同转让的美国申请中,它们相应于代理备审案件目录号P00904,P00918,P00919(近来提出的申请,它的美国序号尚未给出),此交联剂具有下列通式Ⅰ:
式中:
R1是一个烷基,来自取代的和未取代的烃,聚环氧亚烷基,聚(全氟)环氧亚烷基,二烷基封端的聚二甲基硅氧烷,用氟代烷基或氟代醚基改性的二烷基封端的聚二甲基硅氧烷;
R2-R10各自是H或1至5个碳原子的烷基;
Q是一个含有具有6至30个碳原子芳香组成部份的有机基团;
X,Y和Z各自是0,NH或S;
V是1,或更大一些;以及
α,S各自是大于或等于0,而且α+S≥1
通式Ⅰ交联剂的加入促进了含乙烯基和含丙烯酸基的亲水单体相互之间以及与存在于混合物之中的其他单体的共聚合,这类单体例如是通式Ⅱ的含环恶唑酮化合物:
式中
R11和R12各自代表H或CH3;以及
R13和R14各自代表甲基或环己基
这些可以加至本发明含聚硅氧烷水凝胶中的含环单体具体包括2-异丙烯基-4,4-二甲基-2-恶唑啉-5-酮(IPDMO),2-乙烯基-4,4-二甲基-2-恶唑啉-5-酮(VDMO),环己烷-螺-4'-(2'-异丙烯基-2'-恶唑-5'=酮)(IPCO),环己烷-螺-4'-(2'-乙烯基-2'-恶唑-5'-酮)(VCO),以及2-(1-丙烯基-4,4-二甲基-恶唑-5-酮(PDMO),优选的恶唑酮采用共同转让的美国专利4810764所陈述的已知反应顺序来制取。交联剂的用量是在有用的配制物中含0.01至5%的含乙烯基单体。
我们观察到,含有NVP作为润湿剂的含聚硅氧烷水凝胶,与加有含丙烯酸基单体(例如甘油甲基丙烯酸酯,N,N-二甲基丙烯酰胺(DMA)的聚硅氧烷水凝胶相比,其模数高得多。我们观察到,而且本发明期待,往含聚硅氧烷配制物中加入作为润湿剂的含乙烯基亲水单体及含丙烯酸基亲水单体,所得的水凝胶适用于生物医学方面,特别是接触镜片。
被本发明润湿剂提高了其可湿性的含聚硅氧烷水凝胶包括预聚物,例如如下通式的预聚物:
式中
A指二价的聚合物基,选自通式Ⅶ的化合物:
式中
Rs和Rs'各自代表一个含1至10个碳原子的未取代的或氟取代的低级烷基,碳原子间有醚键;以及
P使得分子量为400-10,000;
D代表含6-30个碳原子的烷基双基,烷基环烷基双基,或芳基双基。
G代表含1-40个碳原子的烷基双基,环烷基双基,烷基环烷基双基,芳香双基,或烷基芳香双基,在主链中可以有硫键或胺键。
*代表氨基甲酸乙酯,脲基,酯,碳酸酯或酰胺的键;而
E及E'各自代表以下面通式Ⅷ所表示的可聚合不饱和有机基;
式中
R21代表带1-10个碳原子的二价亚烷基;
R22代表-H或-CH3基;
Z代表U,S或NH;
Ar代表1个带6-30个碳原子的芳香基;
m大于或等于1;
a至少为1;
w是0至6;
x是0或1;
y是0或1;以及
z是0或1。
属于通式Ⅶ和Ⅷ结构而且它们为本发明所阐述的优选预聚物还可以再用通式Ⅸ进行定义:
式中
M是一个烯属不饱和可聚合部分;
Rs和Rs'各自是带1-10个碳原子的未取代或氟取代的低级烷基,碳原子之间有醚键;
U是0或有氨基甲酸乙酯,脲基,酯,碳酸酯,酰胺或其他键的有机基;
m和x大于或等于1;以及
n当X大于1时n大于5,当X等于1时n大于20。
为本发明所陈述的更优选聚氨酯用通式X进一步表示:
式中
R25是除掉异氰酸酯基后的二异氰酸酯的二价基,而最优选的是异佛尔酮二异氰酸酯的二价基;
m和x各自是大于或等于1的整数,优选是3或4,而最优选是X=1和m=3,或m=4;以及
n至少为5,当X=1时优选为大于20,而最优选的是n=30或更大;
更优选的烯属封端聚硅氧烷预聚物用通式Ⅺ表示:
式中
M是烯属不饱和可聚合成份;
Rs和Rs'各自是带1-10个碳原子的未取代或氟取代的低级烷基,碳原子之间有醚键;
m是大于或等于1;
n优选大于5。
本发明的含聚硅氧烷可湿性水凝胶,当用于接触镜片时,可制成很多类型水凝胶接触镜片。如在这一领域中所知晓的,水凝胶接触镜片的氧透过性DK值应大于约20×10-11厘米3×厘米/秒×厘米2×毫米汞(或20DK单位),而优选大于60DK,它们的杨氏弹性模量应在约5至400g/mm2之间,优选大于约20g/mm2(用ASTM检验法D1938测得)。它们的水份应在约10至80%之间,而优选为20至60%之间,而作为镜片可湿性的度量的接触角应小于约80度,而且应优选小于约40度。
含乙烯基和含丙烯酸基亲水单体的总浓度是聚合物水凝胶混合物的约5重量%至约80重量%,更优选为约20-60重量%。含乙烯基单体对含丙烯酸基单体的重量比例是自约40∶1至约1∶40,而优选值为高于1∶1。
本发明还提供制品,此制品可用作生物医学装置,例如接触镜片,外科手术装置,心脏瓣膜,脉管替代物,子宫内避孕器,膜或其他薄膜,隔膜,外科植入物,血管,人造输尿管,人造乳房组织,以及准备与体外体液接触的膜例如肾透析和心/肺机等所用的膜,导液管,护咀器,假牙衬里,眼内装置,以及特别是接触镜片。
人们知道,当例如血与人造表面接触时,会容易地和迅速地被伤害。对于血液是抗凝血酶原的或非溶血的合成表面设计,对修复术及与血一起使用的装置是必要的。
术语“用于生物医学的已成型物件”或“生物医药装置”指的是这里披露的一种材料,它们具有使它们适于长时间与活体组织,血液和粘液膜接触的物化性能。
虽然现在对于此准确机理尚未完全了解,但本发明的润湿剂看来能减少类脂类沉积的问题,而后者通常与(而且据信是被它引起)含聚硅氧烷疏水单体的高疏水性有关的。
此外,本发明的润湿剂明显降低表面的接触角…这对本领域技术熟练人员来说清楚表明润湿已经提高。所得到的包含本发明润湿剂的新颖水凝胶在可接受的范围内出乎所料地对水解稳定,而仅产生可接受水平的蛋白质沉积。
为本发明所陈述的含聚硅氧烷单体的优选类别是前面所述的含聚氨酯预聚物,以及含烯属封端的聚硅氧烷单体,最优选的是α,ω-双(甲基丙烯酰氧烷基)聚硅氧烷。“预聚体”是含有可聚合基团的中等分子量的反应中间聚合物。
这里所披露的所制得的聚合物或共聚物可以在水中煮沸和/或高压加热而不受损,因而进行了消毒。因此,由所披露的聚合物和共聚物例如可用于外科手术中,在后者需要一种可与活组织或与粘液膜相容的物件。
此外,指出了所制得的本发明聚合物可用传统的车床加工方式或旋转铸造法(如美国专利3408429和3496254所披露的),或者其他传统的方法例如美国专利4084459和4197266所披露的压模法,或者这些公知方法的综合,制成接触镜片。
下列实施例的作用仅在于进一步说明本发明的概貌,而不应理解为限制本发明。
下列缩写定义如下:
NVP 是N-乙烯基吡咯烷酮
DMA 是N,N-二甲基丙烯酰胺
HEMAVC 是碳酸甲基丙烯酰氧乙基·乙烯酯
TRIS 是甲基丙烯酰氧丙基三(三甲基甲硅烷氧基)硅烷
IDS3H 是由异佛尔酮二异氰酸酯,二甘醇,被甲基丙烯酸2-羟乙酯包封起来的聚硅氧烷二醇而得到的氨基甲酸酯预聚物。
M2Dx是α,ω-双(甲基丙烯酰氧烷基)聚硅氧烷
VDMO 是2-乙烯基-4,4-二甲基-2-恶唑啉-5-酮
实施例1-6
聚氨酯-硅氧烷水凝胶
制备了含有下列成份的六种聚氨酯水凝胶:
a)IDS3H,30份;
b)TRIS,30份;
c)NVP,从0至40份而变化;
d)DMA,从40至0份(NVP+DMA=40份)而变化;
e)碳酸甲基丙烯酸羟乙基·乙烯酯(HEMAVα交联剂)NVP数量的0.3%;
f)正己醇,40份;
g)Darocur-1173(uv引发剂),0.2份。
将这些配制物进行uv固化,随后如公知的那样进行乙醇萃取及沸水水化,生成具有下述性质(水含量及模数)的水凝胶膜。
图1描绘了实施例1-6所得的膜,每一种膜分别描出一点。
表1
实施例 1 2 3 4 5 6
NVP/DMA比例 40/0 38/2 35/5 30/10 20/20 0/40
%水 35 46 44 41 41 37
模数 430 281 150 80 79 63
模数/组成关系描述于图1。
实施例7
聚氨酯水凝胶
制备与实施例4相同成份及相同重量比例的配制物,不同的是把3份NVP和1份DMA换成1份VDMO。把配制物铸塑成薄膜,并如实施例1-6那样进行加工。所得水凝胶具有下列性质:水份,40%;模数110克/毫米2。
实施例8-11
聚氨酯-聚硅氧烷水凝胶
制备其成份如实施例1-6,但相对份数不同(如表2所示)的聚氨酯配制物。
a)IDS3H及b)TRIS,每种34份;
c)NVP及d)DMA,共32份;
e)正-己醇,f)HEMAVc和g)Darocure-1173。
与实施例1-6相同的份数。
将配制物浇铸,并按实施例1-6的相同方式进行加工。水份及模数数据示于表2。图2描绘了实施例8-11所得的膜,每一点分别代表每一种膜。
表2
实施例 8 9 10 11
NVP/DMA比例 32/0 24/8 16/16 0/32
水% 25 26 31 25
模数 610 275 107 87
模数/组成关系进一步示于图2。
实施例12-15
M2Dx为基础的水凝胶薄膜
按实施例8-11的方法制备下述聚硅氧烷水凝胶配制物并浇铸加工成水凝胶膜。图3描绘了实施例8-11所得到的膜,每一点分别代表一种膜。配制物中的成份为:
a)M2Dx,13份;
b)TRIS,47份;
c)NVP及d)DMA,共40份;
e)正-己烷,40份;
f)HEMAVc,0.3份NVP总量;
g)Darocur,0.2份
模数-组成关系描绘于图3。
实施例16
水凝胶镜片铸件
将实施例4,9,12所述配制物的单体混合物通过一个可处理的1.2微米微孔过滤器滤进一个清洁小瓶中。在惰性氮气气氛下,将60-90微升混合物注射入一个清洁的塑料半模中,然后用第二个塑料半模合上。之后将这两个模子加压,并在紫外线(4200微瓦/厘米2)下固化90分钟随后用机械方法打开这两个模子,并放入装有含水乙醇的烧杯中。在1小时内把镜片从这两个模子中取出,然后用乙醇萃取48小时,并在蒸馏水中煮沸4小时。检查所得镜片的化装质量,细胞学毒性及尺寸。在进行眼上评估前,把通过检验的镜片进行热消毒。
实施例17
临床评估
在6个至10个患者身上对实施例12所述的铸模聚氨酯镜片进行评估。在每项检测中,把1个聚(HEMA)对照镜片带在一个眼上,而把检测镜片带在另一个眼上。最少经1小时对镜片进行分析,而为了进行可湿性及表面沉积研究,最好是在5小时或更长时间之后。表面可湿性的级别范围是0-4,0表示2/3的前表面不被泪膜润湿,而4表示完全被润湿。沉积的级别也是0-4,0表示无表面沉积,而4表示直径0.5毫米或更大的重复沉积。对比配制物(根据实施例4)镜片的结果是:带5小时后,可湿性为3.0,而沉积为0.4,对于含1份VDMO(实施例7配制物)的镜片,结果表明,在带5小时后,其可湿性级别为3.3,而沉积级别为0.7。
根据这里所指出的,本领域技术熟练实践者可以对本发明作出很多其他的改进或变动。因此应该明白,只要在权利要求的范围内,本发明就可以予以实施而不必再作具体的说明。
Claims (56)
1、一种提高含聚硅氧烷水凝胶组合物的可湿性的方法,它包括加入至少一种含乙烯基亲水润湿单体和一种含丙烯酸基亲水润湿单体到含有聚硅氧烷水凝胶的组合物中。
3、权利要求1的方法,其中该含聚硅氧烷水凝胶组合物包含至少一种含氨基甲酸乙酯预聚物。
4、权利要求1的方法,其中该含聚硅氧烷水凝胶组合物包含至少一种含烯属封端的聚硅氧烷单体。
5、权利要求1的方法,其中该含乙烯基亲水润湿单体可选自N-乙烯基-N-甲基乙酰胺,N-乙烯基-N-乙基乙酰胺,N-乙烯基-N-甲基甲酰胺,以及N-乙烯基甲酰胺。
6、权利要求1的方法,其中该含乙烯基亲水润湿单体是N-乙烯基吡咯烷酮。
7、权利要求1的方法,其中,该含丙烯酸基亲水润湿单体选自:甲基丙烯酸2-羟乙酯,甘油甲基丙烯酸酯,2-羟乙基甲基丙烯酰胺,双丙酮丙烯酰胺,甲基丙烯酸及丙烯酸。
8、权利要求1的方法,其中,该含丙烯酸基亲水润湿单体是N,N-二甲基丙烯酰胺。
12、权利要求1的方法,其中,该含聚硅氧烷水凝胶来自α,ω-双(甲基丙烯酰氧烷基)聚硅氧烷,该含丙烯酸基亲水润湿单体是N,N-二甲基丙烯酰胺,而该含乙烯基亲水润湿单体是N-乙烯基吡咯烷酮。
13、权利要求4的方法,其中,该含烯属封端聚硅氧烷单体是α,ω-(甲基丙烯酰氧烷基)聚硅氧烷。
14、权利要求1的方法,其中,该含聚硅氧烷水凝胶包含含有氨基甲酸乙酯的预聚物,该含丙烯酸基亲水润湿体是N,N-二甲基丙烯酰胺,而该含乙烯基亲水润湿单体是N-乙烯基吡咯烷酮。
15、权利要求1的方法,其中,该含聚硅氧烷水凝胶还包含相对非极性含环化合物,它选自2-乙烯基-4,4-二甲基-2-恶唑啉-5-酮,2-异丙烯基-4,4-二甲基-2-恶唑啉-5-酮,环己烷-螺-4'-(2'-异丙烯基-2'-恶唑-5'-酮),环己烷-螺-4'-(2'-乙烯基-2'-恶唑-5'-酮)以及2-(1-丙烯基)-4,4-二甲基-恶唑-5-酮。
16、权利要求1的方法,其中,该含聚硅氧烷水凝胶是含烯属封端聚硅氧烷单体,该含丙烯酸基亲水润湿单体是N,N-二甲基丙烯酰胺,而该含乙烯基亲水润湿单体是N-乙烯基吡咯烷酮。
18、权利要求17的方法,其中,该含丙烯酸基亲水润湿单体是N,N-二甲基丙烯酰胺,该含乙烯基亲水润湿单体是N-乙烯基吡咯烷酮,而该交联剂是碳酸甲基丙烯酰氧乙基·乙烯酯。
19、权利要求1的方法,其中,该组合物用于制造生物医学装置。
20、权利要求1的方法,其中,该组合物用于制造接触镜片。
21、一种含聚硅氧烷水凝胶组合物,它包含将至少一种含丙烯酸基亲水润湿单体和至少一种含乙烯基亲水润湿单体加至该含聚硅氧烷水凝胶组合物中。
22、权利要求21的组合物,其中,该含聚硅氧烷水凝胶组合物包含至少一种含氨基甲酸乙酯的预聚物。
23、权利要求21的组合物,其中,该含聚硅氧烷水凝胶组合物包含至少一种含烯属封端聚硅氧烷单体。
24、权利要求21的组合物,其中,该含乙烯基亲水润湿单体可选自:N-乙烯基-N-甲基乙酰胺,N-乙烯基-N-乙基乙酰胺,N-乙烯基-N-甲基甲酰胺,以及N-乙烯基甲酰胺。
25、权利要求21的组合物,其中该含乙烯基亲水润湿单体是N-乙烯基吡咯烷酮。
26、权利要求21的组合物,其中,该含丙烯酸基亲水润湿单体选自:甲基丙烯酸2-羟乙酯,甘油甲基丙烯酸酯,2-羟乙基甲基丙烯酰胺,双丙酮丙烯酰胺,甲基丙烯酸和丙烯酸。
27、权利要求21的组合物,其中,该含乙烯基亲水润湿单体是N,N-二甲基丙烯酰胺。
30、权利要求23的组合物,其中,该含烯属封端聚硅氧烷单体用通式表示:
式中
M是烯属不饱和可聚合部分;
Rs和Rs'各自是带1至10个碳原子的未取代或氟取代的低级烷基,碳原子之间有醚键;
m大于或等于1;以及
n大于5。
31、权利要求21的组合物,其中,该含聚硅氧烷水凝胶得自α,ω-双(甲基丙烯酰氧丁基)聚硅氧烷,该含丙烯酸基亲水润湿单体是N,N-二甲基丙烯酰胺,而该含乙烯基亲水润湿单体是N-乙烯基吡咯烷酮。
32、权利要求23的组合物,其中,该含烯属封端聚硅氧烷单体是α,ω-双(甲基丙烯酰氧烷基)聚硅氧烷。
33、权利要求22的组合物,其中,该含丙烯酸基亲水润湿单体是N,N-二甲基丙烯酰胺,而该含乙烯基亲水润湿单体是N-乙烯基吡咯烷酮。
34、权利要求21的组合物,其中,该含聚硅氧烷水凝胶含有相对非极性含环化合物,它选自2-乙烯基-4,4-二甲基-2-恶唑啉-5-酮,2-异丙烯基-4,4-二甲基-2-恶唑啉-5-酮,环己烷-螺-4'-(2'-异丙烯基-2′-恶唑-5′-酮),环己烷-螺-4′-(2′-乙烯基-2′-恶唑-5′-酮)及2-(1-丙烯基)基4,4-二甲基-恶唑-5-酮。
35、权利要求23的组合物,基中,该含丙烯酸基亲水润湿单体是N,N-二甲基丙烯酰胺,而该含乙烯基亲水润湿单体是N-乙烯基吡咯烷酮。
37、权利要求36的组合物,其中,该含丙烯酸基亲水润湿单体是N,N-二甲基丙烯酰胺,该含乙烯基亲水润湿单体是N-乙烯基吡咯烷酮,而该交联剂是碳酸甲基丙烯酰氧乙基·乙烯酯。
38、权利要求21的组合物,其中,该组合物用于制造生物医学装置。
39、权利要求21的组合物,其中,该组合物用于制造接触镜片。
40、一种接触镜片组合物,包含把至少一种含乙烯基亲水润湿单体和一种含丙烯酸基亲水润湿单体加到含聚硅氧烷水凝胶组合物中。
42、权利要求40的接触镜片,其中该含聚硅氧烷水凝胶组合物含有至少一种含氨基甲酸乙酯的预聚物。
43、权利要求40的接触镜片,其中该含聚硅氧烷水凝胶组合物含有至少一种含烯属封端聚硅氧烷单体。
44、权利要求40的接触镜片,其中,该含乙烯基亲水润湿单体可选自:N-乙烯基-N-甲基乙酰胺,N-乙烯基-N-乙基乙酰胺,N-乙烯基-N-甲基甲酰胺,及N-乙烯基甲酰胺。
45、权利要求40的接触镜片,其中,该含乙烯基亲水润湿单体是N-乙烯基吡咯烷酮。
46、权利要求40的接触镜片,其中,该含丙烯酸基亲水润湿单体选自:甲基丙烯酸2-羟乙酯,甘油甲基丙烯酸酯,α-羟乙基甲基丙烯酰胺,双丙酮丙烯酰胺,甲基丙烯酸及丙烯酸。
47、权利要求40的接触镜片,其中,该含乙烯基亲水润湿单体是N,N-二甲基丙烯酰胺。
50、权利要求43的接触镜片,其中,该含烯属封端聚硅氧烷单体用下面通式表示:
式中
M是一个烯属不饱和可聚合部分;
Rs和Rs'各自是带有1至10个碳原子的未取代的或氟取代低级烷基,碳原子之间有醚键;m大于或等于1;以及n大于5。
51、权利要求40的接触镜片,其中,该含聚硅氧烷水凝胶包含α,ω-双(甲基丙烯酰氧丁基)聚硅氧烷,该含丙烯酸基亲水润湿单体是N,N-二甲基丙烯酰胺,而该含乙烯基亲水润湿单体是N-乙烯基吡咯烷酮。
52、权利要求42的接触镜片,其中所述含丙烯酸基亲水润湿单体是N,N-二甲基丙烯酰胺和所述的含乙烯基亲水润湿单体是N-乙烯基吡咯烷酮。
53、权利要求40的接触镜片,其中,该含聚硅氧烷水凝胶还包含一种相对非极性含环化合物,它选自2-乙烯基-4,4-二甲基-2-恶唑啉-5-酮,2-异丙烯基-4,4-二甲基-2-恶唑啉-5-酮,环己烷-螺-4'-(2'-异丙烯基-2'-恶唑-5'-酮,环己烷-螺-4'-(2'-乙烯基-2'-恶唑-5'-酮),及2-(1-丙烯基)-4,4-二甲基-恶唑-5-酮。
54、权利要求43的接触镜片,其中,该含丙烯酸基亲水润湿单体是N,N-二甲基丙烯酰胺,而该含乙烯基亲水润湿单体是N-乙烯基吡咯烷酮。
56、权利要求40的组合物,其中,该含丙烯酸基亲水润湿单体是N,N-二甲基丙烯酰胺,该含乙烯基亲水润湿单体是N-乙烯基吡咯烷酮,而该交联剂是碳酸甲基丙烯酰氧乙基·乙烯酯。
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US78801391A | 1991-11-05 | 1991-11-05 | |
| US788,013 | 1991-11-05 | ||
| US92229292A | 1992-07-30 | 1992-07-30 | |
| US922,292 | 1992-07-30 |
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| Publication Number | Publication Date |
|---|---|
| CN1074450A true CN1074450A (zh) | 1993-07-21 |
| CN1043428C CN1043428C (zh) | 1999-05-19 |
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| CN92114448A Expired - Fee Related CN1043428C (zh) | 1991-11-05 | 1992-11-05 | 可湿的聚硅氧烷水凝胶组合物及其制法 |
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| US (1) | US5486579A (zh) |
| EP (1) | EP0611379B1 (zh) |
| JP (1) | JP3354571B2 (zh) |
| CN (1) | CN1043428C (zh) |
| AU (1) | AU3066392A (zh) |
| BR (1) | BR9206889A (zh) |
| CA (1) | CA2122251C (zh) |
| DE (1) | DE69211152T2 (zh) |
| ES (1) | ES2090710T3 (zh) |
| HK (1) | HK1001564A1 (zh) |
| MX (1) | MX9206379A (zh) |
| WO (1) | WO1993009154A1 (zh) |
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| US9395559B2 (en) | 2005-02-14 | 2016-07-19 | Johnson & Johnson Vision Care, Inc. | Comfortable ophthalmic device and methods of its production |
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| CN105418858B (zh) * | 2015-12-23 | 2018-08-17 | 江苏海伦隐形眼镜有限公司 | 具有高透氧性的硅水凝胶材料、角膜接触镜及其制备方法 |
| CN112262160A (zh) * | 2018-06-04 | 2021-01-22 | 信越化学工业株式会社 | 聚硅氧烷单体及其制造方法 |
Also Published As
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| AU3066392A (en) | 1993-06-07 |
| ES2090710T3 (es) | 1996-10-16 |
| JPH07505169A (ja) | 1995-06-08 |
| MX9206379A (es) | 1994-02-28 |
| BR9206889A (pt) | 1995-05-02 |
| JP3354571B2 (ja) | 2002-12-09 |
| EP0611379B1 (en) | 1996-05-29 |
| CN1043428C (zh) | 1999-05-19 |
| DE69211152T2 (de) | 1997-01-02 |
| EP0611379A1 (en) | 1994-08-24 |
| CA2122251A1 (en) | 1993-05-13 |
| DE69211152D1 (de) | 1996-07-04 |
| HK1001564A1 (zh) | 1998-06-26 |
| WO1993009154A1 (en) | 1993-05-13 |
| US5486579A (en) | 1996-01-23 |
| CA2122251C (en) | 1998-02-03 |
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