CN1055542A - 包括接触透镜的水凝胶成型制品的制法 - Google Patents
包括接触透镜的水凝胶成型制品的制法 Download PDFInfo
- Publication number
- CN1055542A CN1055542A CN90110408A CN90110408A CN1055542A CN 1055542 A CN1055542 A CN 1055542A CN 90110408 A CN90110408 A CN 90110408A CN 90110408 A CN90110408 A CN 90110408A CN 1055542 A CN1055542 A CN 1055542A
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- Prior art keywords
- acrylate
- methyl
- thinner
- monomer
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- 238000000034 method Methods 0.000 title claims description 37
- -1 alkyl (methyl) acrylate Chemical compound 0.000 claims abstract description 90
- 239000000178 monomer Substances 0.000 claims abstract description 74
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000000203 mixture Substances 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000004327 boric acid Substances 0.000 claims abstract description 32
- 238000000465 moulding Methods 0.000 claims abstract description 27
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000004132 cross linking Methods 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical class 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 8
- 238000005266 casting Methods 0.000 claims abstract description 6
- 239000000499 gel Substances 0.000 claims abstract description 5
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims description 13
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 11
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 5
- 238000009736 wetting Methods 0.000 claims description 5
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical group CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 claims 2
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- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 abstract description 21
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- 229940044192 2-hydroxyethyl methacrylate Drugs 0.000 abstract description 5
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- 229920001577 copolymer Polymers 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 description 26
- 229910052760 oxygen Inorganic materials 0.000 description 26
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 25
- 239000000126 substance Substances 0.000 description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 20
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 11
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
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- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 8
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- 238000002360 preparation method Methods 0.000 description 5
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- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
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- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
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- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 2
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- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
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- 150000001875 compounds Chemical class 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
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- 230000003287 optical effect Effects 0.000 description 2
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
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- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- OFLPBAZQIRUWFV-UHFFFAOYSA-N 2-[3-(5-chlorobenzotriazol-2-yl)-4-hydroxyphenyl]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC1=CC=C(O)C(N2N=C3C=C(Cl)C=CC3=N2)=C1 OFLPBAZQIRUWFV-UHFFFAOYSA-N 0.000 description 1
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- JRCGLALFKDKSAN-UHFFFAOYSA-N 3-hydroxybutyl prop-2-enoate Chemical compound CC(O)CCOC(=O)C=C JRCGLALFKDKSAN-UHFFFAOYSA-N 0.000 description 1
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- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
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- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
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- FIMUXQLLGBMSAI-UHFFFAOYSA-N cyclohexylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CCCCC1 FIMUXQLLGBMSAI-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
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- G—PHYSICS
- G02—OPTICS
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- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/041—Lenses
- G02B1/043—Contact lenses
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D11/00—Producing optical elements, e.g. lenses or prisms
- B29D11/00009—Production of simple or compound lenses
- B29D11/00038—Production of contact lenses
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2033/00—Use of polymers of unsaturated acids or derivatives thereof as moulding material
- B29K2033/04—Polymers of esters
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29K2033/00—Use of polymers of unsaturated acids or derivatives thereof as moulding material
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- B29K2033/12—Polymers of methacrylic acid esters, e.g. PMMA, i.e. polymethylmethacrylate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0002—Condition, form or state of moulded material or of the material to be shaped monomers or prepolymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2707/00—Use of elements other than metals for preformed parts, e.g. for inserts
- B29K2707/02—Boron
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0037—Other properties
- B29K2995/0092—Other properties hydrophilic
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
水凝胶成型制品如软接触透镜的制造:1,模或铸
塑混合聚合物,包括:a,单体混合物,包括:主要量的
亲水(甲基)丙烯酸酯(如2-羟乙基甲基丙烯酸酯,该
烷基含至少4碳原子的烷基(甲基)丙烯酸酯和交联
单体;b,可水替代的稀释剂,该稀释剂的30℃粘度至
少100MPa该稀释剂实质组成有某二元硼酸酯,该二
元醇的Hansen极性(Wp)和Hansen氢键(Wh)粘
附参数落在圆心为Wh=20.5,Wp=13、半径为8.5
的圆内,以生产该单体和稀释剂共聚物的成型凝胶;
2,用水代替该稀释剂。
Description
本申请是1988年11月25日未审查申请276007的部份继续。
本发明涉及包括软接触透镜的水凝胶成型制品的制造,尤其是涉及使用某种硼酸酯作为可水替代稀释剂的直接模塑这些制品的方法
直到最近,水凝胶型的软接触透镜一直是采用车削或旋转铸塑法生产的,在车削方法中,将基本上是无水的亲水聚合物(干凝胶)的块或透镜坯在精密车床上进行机械切削并抛光成透镜形状。然后,与水或盐水接触以便水合聚合物,并形成所需的水凝胶透镜。在车削操作中除了必须留出余量,以便在聚合物的水化过程中透镜的溶胀外,所用的机械步骤与制造硬接触透镜相类似。
在旋转铸塑法中,在凹的光学抛光的模具中放入少量亲水单体混合物,旋转模具并同时聚合单体以形成干凝胶透镜,透明的两个光学表面在聚合过程中同时形成,外表面由凹模具形成,内表面由旋转模具产生的离心力和聚合混合物的表面张力作用而形成的,如车削透镜一样,此透镜是由与水或盐水相接触成水化此聚合物及形成水凝胶透镜所制造的。
最近,开发了一种改进的成型水凝胶接触透镜的方法,该方法不仅比车削方法或旋转铸塑法更为经济,而且具有更精确控制水凝胶透镜最后形状的优点。此方法包括:直接模塑一种单体混合物,其中该单体混合物溶解在非水溶液的可水替代的溶剂中,该混合物放置在具有最终所希望的水凝胶(即水溶胀)透镜形状的模具内,并将单体/溶剂混合物进行处理,即单体的聚合而产生聚合物/溶剂混合物就形成最终所希望的水凝胶透镜。(聚合必须在非水溶液的介质中进行,因为水会阻止聚合反应)聚合完成后,用水代替溶剂,以便生成水化透镜,该透镜的尺寸和形状十分类似于最初模塑的聚合物/溶剂制品的尺寸和形状,这种直接模塑水凝胶接触透镜公开于Larsen的US-4,495,313和Larsen等人的US-4,680,336中。
在Larsen专利中,所用的可水替代的稀释剂是多元醇的硼酸酯,其中多元醇具有3个或更多个羟基,此外,所用的多元醇可以是具有3个或更多个羟基的多元醇和二元醇的混合物,例如上述的第3栏第60行及以下和第4栏第18-22行。
Larsen专利清楚地指明,用来制备硼酸酯(水凝胶接触透镜直接模塑法用的)的多元醇必须具有3个或更多个羟基。同时还公开了二元醇可以与3或更高的多元醇混合起来使用,但是3或更高的多元醇是必要的组份。
本发明的一个重要方面是基于发现硼酸酯和某种二元醇(如下面全面定义的)可用在直接模塑工艺中作为可水替代稀释剂,用于制造成形水凝胶制品,例如软接触透镜,是从含有基本单体的一个或多个亲水的(甲基)丙烯酸酯如甲基丙烯酸2-羟乙基酯(1HEMA)的聚合物混合物制造出来的。本发明提供在直接模塑工艺用于制造成形水凝胶优越工艺包括提高了脱模性(即聚合后采用较小的力打开模的能力),其结果是节省了劳动力费用的经济优点和降低了在模塑制品所引起的表面缺陷而大大地提高了生产率。这就可以相信提高脱模性和大大提高了生产是由于在本发明中使用硼酸酯这一事实有关的,它具有比Laren的专利,US-4,495,313的优选酯具有较低的表面张力,从而降低了聚合物/溶剂混合物对模具的粘结力。
由本发明提供的可水替代的酯赋予直接模塑法的另一个优点是提高了在聚合物混合物中使用疏水单体(例如UV-吸收单体)的能力。当人们试用包括疏水单体如UV-吸收单体于单体/稀释剂混合物作为所述Larsen的专利的优选稀释剂时,可以发现此疏水单体是通常不溶于混合物中。
由于医学上进一步对紫外线(“UV”)射线有害于眼睛的认识从而对眼镜、风镜、接触透镜和眼内透镜的生产中添加有吸收UV射线的物质。从聚合物(通常是丙烯酸聚合物)所制造的接触透镜和眼内透镜,优选的方法从赋予UV吸收能力的共聚物中来制造透镜,即含有共聚的UV-吸收单体的共聚物来制造,这些单体例如已公开在Beard等人的US-4,528,311和Dunks等人的US-4,716,234中,通过在单体/稀释剂混合物中包含UV吸收单体可令人满意地给直接模塑法制造的接触透镜赋予UV吸收性能,本发明达到了这个所希望的实际目的。
由羟烷基(甲基)丙烯酸酯聚合物(例如以HEMA为主的聚合物)制造的软接触透镜已普遍被接受。这些聚合物被用于制造每日摘戴的接触透镜和连续戴的接触透镜。影响连续戴接触透镜在戴时舒适性因素之一是透镜的氧传导性。因为角膜是从空气中直接获得氧而不是从带氧的血液中获得氧。穿过透镜传导氧对于连续戴透镜是非常重要的,对于每日摘戴的透镜也是所希望的,因此总的说穿过透镜传送的氧越多越好。影响接触透镜传导氧因素之一是透镜的厚度,接触透镜的氧传导与透镜厚度成反比,戴镜者的舒适程度也与透镜厚度成反比。由于这两个原因,即最大氧传导量和最佳舒适程度,如果光学认为许可的话,希望制造的接触透镜尽可能地薄。
目前合适的HEMA基水凝胶(水溶胀)态接触透镜的厚度通常在约0.03至约0.6毫米的范围内,这种透镜所能制成的薄的程度受到透镜强度的限制。通常在聚合物中增加多官能交联剂的比例来使它们变得更强(更强就能使它们变得更薄)的努力通常是失败的,因为当交联剂单体在增加到一定点之后,聚合物也就变脆了。
本发明的主要新颖之处在于引入了一个或更多的C6或更高烷基(甲基)丙烯酸酯共聚单体的羟烷基(甲基)丙烯酸酯(例如2-羟乙基甲基丙烯酸酯)的共聚物。已经发现这些共聚物在低应力条件(即:在正常使用条件)下显示出强度增加并且没有并发脆性增加,这样由这些共聚物制造的制品(例如水凝胶接触透镜)可以制作的更薄。
现有技术有在亲水性聚合物(打算用于软接触透镜的)中引入疏水性单体的。例如,这些聚合物公开在Singer等人的美国专利4,620,954号中,和Izumitani等人的美国专利4,625,009中。在这些专利中,亲水性单体是N-乙烯基吡咯烷酮或N,N-二甲基丙烯酰胺。Holcombe在美国专利3,926,892和3,965,063中公开月桂基丙烯酸酯或甲基丙烯酸酯可以是HEMA共聚物中的一个共聚单体,该HEMA共聚物还含有异丁基甲基丙烯酸酯以及或者环已基甲基丙烯酸酯或者N-(1,1-二甲基-3-氧代丁基)丙烯酰胺。Holcombe公开的聚合技术是本体聚合。在由Holcombe完成的共聚物体系中Holcombe并未公开使用月桂基丙烯酸酯的实际操作例子。
除了Holcombe的专利之外,Singer等人的专利,Izumitani等人的专利(所有这些都已叙述如上),日本专利61166516和61205901(转让给Hoya公司,Izumitani等人专利的受让人)都描述了由N,N-二甲基丙烯酰胺或N-乙烯基吡咯烷酮和疏水性单体的共聚物制造接触透镜。
Dunks等人在美国专利4,716,234中描述了在各种聚合物中引入某种苯并三唑(甲基)丙烯酸酯类作为UV吸收剂。上述的这些聚合物之中是HEMA聚合物。苯并三唑(甲基)丙烯酸酯在性质上是疏水性的。
Seiderman在美国专利3,503,942中描述了亲水性塑料接触透镜,是由羟烷基丙烯酸酯或甲基丙烯酸酯和直到约35%重量的烷基丙烯酸酯或甲基丙烯酸酯(其中一部分可以是C5-20的烷基丙烯酸酯或甲基丙烯酸酯)的本体聚合共聚物制造的。
水凝胶成型制品(例如软接触透镜)通过下列步骤制备:
(1)模塑或铸塑一种聚合混合物,该混合物包括:
(a)一种单体混合物,包括主要量的一种或多种亲水性(甲基)丙烯酸酯单体(例如2-羟乙基甲基丙烯酸酯)、一种烷基(甲基)丙烯酸酯(其中烷基含有至少四个碳原子)和一种或多种交联单体;和
(b)一种可水替代稀释剂,其中所述之稀释剂具有在30℃至少100MPa Sec的粘度,并且其中所述之稀释剂实际组成为某种二元醇的硼酸酯。所述之二元醇具有Hansen极性(Wp)和Hansen氢键(Wh)粘性参数落在一个由中心为Wh=20.5Wp=13,半径为8.5确定的园面积内。
以制成所述单体和所述稀释剂的共聚物的成型凝胶,并且
(2)然后用水替代所述之稀释剂。
在本发明的一个重要特征中,软接触透镜通过下列步骤制造:
(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:主要量的亲水性(甲基)丙烯酸酯单体(例如2-羟乙基甲基丙烯酸酯)、一种或多种交联单体及一种烷基(甲基)丙烯酸酯单体(其中烷基含有至少4个C原子);
(b)一种可水替代稀释剂,其中所述之稀释剂具有在30℃至少100Mpa Sec的粘度,并且其中所述之稀释剂实际组成为某种二元醇的硼酸酯,所述之二元醇具有Hansen极性(Wp)和Hansen氢键(Wh)粘性参数落在一个由中心为Wh=20.5 Wp=13,半径为8.5确定的园面积内。
以制成所述单体和所述稀释剂的共聚物的成型凝胶,并且
(2)然后用水替代所述之稀释剂。
上述的Larsen专利(No.4,495,313)是本申请人所知的关于在模塑或铸塑水凝胶制品中使用硼酸酯作为可水替代稀释剂的最相关的现有技术。上述的Seiderman专利(NO.3,503,942)是本申请人所知的关于在制备接触透镜中使用羟烷基(甲基)丙烯酸酯和烷基(甲基)丙烯酸酯的最相关的现有技术。
Larsen等人的专利NO.4,680,336描述了在制造水凝胶制品的直接模塑方法中特定稀释剂的选择应以它们的粘度和它们的Hansen极性及氢键粘性参数为依据。
其它涉及水凝胶制品(例如软接触透镜)的直接模塑的美国专利包括:Larsen的美国专利4,565,348和4,640,489,Ohkada等人的4,347,198,Shepard的4,208,364和Wichterle等人的Re.27,401(NO,3,220,960)
其它描述了由羟烷基(甲基)丙烯酸酯和烷基(甲基)丙烯酸酯制备接触透镜的专利有Masuhara等人的美国专利3,988,274,Tarumi等人的美国专利4,143,017和Kato等人的美国专利4,529,747。
图1是各种二元醇的Hansen粘性参数Wh和Wp的曲线图。
图2是确定软接触透镜杨氏模量所用的标准图:和
图3是用来确定打开模具所需力量的试验设备及装配的部分示意侧视图,包含聚合物/稀释剂混合物中制成的接触透镜。
图4是图3所示同一设备及装置的前视图
本发明的一个主要新颖之处在于将C4或更高的烷基(甲基)丙烯酸酯加到所要用于软接触透镜的羟烷基(甲基)丙烯酸酯共聚物中。〔这里所用的“(甲基)丙烯酸酯”是表示“甲基丙烯酸酯和/或丙烯酸酯”。〕这些C4或更高的(甲基)丙烯酸酯例如包括:
n-丁基丙烯酸酯和甲基丙烯酸酯,
n-己基丙烯酸酯和甲基丙烯酸酯,
2-乙基己基甲基丙烯酸酯和其他辛基丙烯酸酯和甲基丙烯酸酯
n-癸基丙烯酸酯和甲基丙烯酸酯,
异癸基丙烯酸酯和甲基丙烯酸酯,
十二烷基丙烯酸酯和甲基丙烯酸酯,
硬脂酰基甲基丙烯酸酯,
和其它具有4或更多碳原子烷基的烷基丙烯酸酯。最好,在烷基(甲基)丙烯酸酯中的烷基含有至少6个碳原子长到直至例如20个碳原子长的直链。
用于本发明的单体混合物包括作为主要量的羟基(甲基)丙烯酸酯(例如HEMA,2-羟乙基丙烯酸酯,甘油单丙烯酸酯,甘油单甲基丙烯酸酯等等)、一种或多种多官能交联单体,和任选的少量其他单体(例如甲基丙烯酸)以及C6或更高的烷基(甲基)丙烯酸酯。其它能被使用于单体混合物中的亲水性单体包括: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-乙烯基吡咯烷酮等等。既可单独也可混合一起使用的多官能交联单体包括亚乙基二醇二甲基丙烯酸酯,三羟甲基丙烷三甲基丙烯酸酯,聚亚乙基二醇二甲基丙烯酸酯(其中聚亚乙基二醇的分子量直至例如约400)及其他含有二或更多(甲基)丙烯酸酯基的聚丙烯酸酯和聚甲基丙烯酸酯。所用的多官能交联单体的量一般例如是从约0.1至约1.25重量份(每100份重量羟烷基(甲基)丙烯酸酯。其他能够使用的单体包括甲基丙烯酸,它被用来影响水的量(水凝胶在平衡时吸收的)。甲基丙烯酸一般所用的量为从每100份重量羟烷基(甲基)丙烯酸酯约0.25至约7份重量,这部分取决于例如在共聚物中C6或更高烷基(甲基)丙烯酸酯的比例这样的因素。作为一般原则,当烷基(甲基)丙烯酸酯单体的比例增加时,所用的甲基丙烯酸就较多。C6或更高烷基(甲基)丙烯酸酯所用的量应足以提高包括水溶胀共聚物的水凝胶的弹性强度,这个量通常是每100份重量羟烷基(甲基)丙烯酸酯(例如HEMA)从约10至约50份重量,优选是从约10至30份重量。
单体混合物也可以含有一个或多个紫外线吸收单体。这些UV吸收单体例如是苯并三唑(甲基)丙烯酸酯类,如由Beard等人在美国专利4,528,311中描述的2-〔2′-羟基-5′-丙烯酰氧-烷基苯基〕-2H-苯并三唑、Dunks等人在美国专利4,716,234中描述的2-〔2′-羟基-5′-丙烯酰氧-烷氧苯基〕-2H苯并三唑,和Dunks等人在美国专利申请NO.21,096(1987年3月3日申请,并转让给本申请受让人的分公司)描述的2-(2′羟苯基)-5(6)-(丙烯酰烷氧基)苯并三唑。能够用于本发明特别说明的苯并三唑UV吸收(甲基)丙烯酸酯类包括下面的化合物:
2-(2′-羟基-5′-甲基丙烯酰氧基乙基苯基)-2H-苯并三唑;
2-(2′-羟基-5′-甲基丙烯酰基氧乙基苯基)-5-氯-2H-苯并三唑;
2-(2′-羟基-5′-甲基丙烯酰基氧丙基苯基)-5-氯-2H-苯并三唑;
2-(2′-羟基-5′-甲基丙烯酰基氧丙基-3′-叔-丁基苯基)-2H-苯并三唑;
2-(2′-羟基-5′-甲基丙烯酰基氧丙基-3′-叔-丁基苯基)-5-氯-2H-苯并三唑;
2-(2′-羟基-5′-(2-甲基丙烯酰基氧乙氧基)-3′-叔-丁基苯基〕-5-甲氧基-2H-苯并三唑,
2-(2′-羟基-5′-(γ-甲基丙烯酰基氧丙氧基)-3′-叔-丁基苯基〕-5-甲氧基-2H-苯并三唑,和
2-(3′-t-丁基-2′-羟基-5′-甲氧苯基)-5-(3′-甲基丙烯酰基氧丙氧基)苯并三唑。
其他能被包括在聚合反应混合物中的UV吸收单体包括二苯酮的衍生物,等等。
苯并三唑UV吸收(甲基)丙烯酸酯被使用于单体混合物中是以最终透镜产品能有效吸收UV射线的量使用的。通常UV吸收单体的比例是每100份重量的主要的亲水性单体(例如HEMA)从约1至10重量份。
聚合催化剂包括在单体混合物中,该聚合催化剂可以是产生游离基化合物,例如:月桂酰过氧化物,苯甲酰基过氧化物,异丙基过碳酸酯、偶氮双异丁基腈等等,它们可以在中温产生游离基,聚合催化剂或者可以是光引发剂系统,例如:叔胺加二酮。这种光引发剂系统的一个示例是樟脑醌和乙基4-(N,N-二甲基氨基)苯甲酸酯。另一个示例的光引发剂是4-(2-羟基乙氧基)苯基2-羟基-2-丙基酮。用于聚合反应混合物的催化剂是以催化有效量使用的,例如从约0.25至约1.5份重量(每100份羟烷基(甲基)丙烯酸酯)。
在本发明中,硼酸酯是在直接模塑水凝胶制品中同作可水替代稀释剂的,它包括某种二元醇的硼酸酯,所述之二元醇具有Hansen极性(Wp)和Hansen氢键(Wh)粘性参数落在一个由园心为Wh=20.5Wp=13,半径为8.5确定的园面积内。还要求硼酸酯和二羟基化合物在30℃具有至少100MPa Sec的粘度,优选是在30℃下至少约500MPa Sec。
该硼酸酯可按现有技术已知的类似方法制备,例如将硼酸与二元醇(简化起见这里有时将二元醇称为二醇)反应,并通过一般的方法例如真空蒸发除去反应形成的水。硼酸与二元醇的反应是在足以形成酯的温度及时间内完成的,典型的温度是在从约50℃至约120℃的范围内。在这一温度下,反应时间典型的是约2至约12小时,在任何情况下,反应持续直到酯中的水份少于约2%重量。这样选择二元醇与硼酸的比例,是使酯的粘度在30℃下至少是100MPa Sec,下列例子给出了酯产品具有所需粘度的硼酸与二醇相应比例。在某种情况下,在酯化反应混合物中或许希望有少量的二元醇以便控制酯产品的分子量。
用于本发明制造可水替代稀释剂的二元醇是那些Hansen极性(Wp)和Hansen氢键(Wh)粘性参数落在一个由园心为Wh=20.5,Wp=13及半径为8.5确定的园面积内的二元醇。Hansen粘性参数通常由三部份(Wh、Wp、Wd)表示,其中Wh是氢键粘性参数,Wp是极性粘性参数,Wd是分散粘性参数,现已发现对于本发明的目的,二元醇的分散粘性参数实质是同样的(已确定的值在约15.7至17.0之间变化),因此对确定用于本发明的任一特定二元醇的合适性有很小的影响。由此,所要考虑的用于制造硼酸酯稀释剂的二元醇的粘性参数被减少至以极性和氢键粘性参数为基的二维参数。
Hanscn粘性参数是现有技术所知的,参见Allan F.M.Barton.CRC Press,Inc.,Boca Raton,Florida(1983)的“溶解性参数和其他粘性参数的CRC手册”,特别是第85-87页,141页和153-164页;Hansen的”The UNIVERSALITY OF THE SOLUBILITY PARAMETER(溶解性参数的一般性)”,I&EC Product Research and development,第8卷第1号,1969年3月,第2-11页;Wernick的“三维溶解性参数相互关系的主体平画显示”Ind.Eng.Chem.Prod.Res.Dev.,第23卷第2号1984年第240-245页;Kirk-othmer Encyclpedia of Chemical Technology,第2版增补卷,Interscience NY1971,第891页和892页,说明了Hansen粘性参数的讨论及如何确定它们。
所选多元醇的Hansen粘性参数被显示于下面的表Ⅰ中。需要时,报告在CRC手册上的Hansen和Beerbower数据也被使用。对于没有列出的二醇可使用显示在CRC手册第85-87和Kirk-othmer,第891-892页上的Hansen和Beerbower,数据通过组成分计算该值,Wp的值可按照Kirk-othmer建议的简单相加法计算。
表Ⅰ
二元醇的HANSEN参数
二醇 缩写 Wp Wh
乙二醇 EG 11.0 26.0
1,2-丙二醇 1,2-PD 9.4 23.3
1,3-丙二醇 1,3-PD 14.0 23.2
1,2-丁二醇 1,2-BD 7.7 20.8
1,3-丁二醇 1,3-BD 10.0 21.5
1,4-丁二醇 1,4-BD 10.0 21.5
2,3-丁二醇 2,3-BD 7.7 20.8
1,6-己二醇 1,6-HD 8.4 17.8
2,5-己二醇 2,5-HD 8.4 17.8
1,8-辛二醇 1,8-OD 6.3 15.5
表Ⅰ(续)
二元醇的HANSEN参数
二醇 缩写 Wp Wh
1,10-癸二醇 1,10-DD 5.0 13.8
二甘醇 DEG 14.7 20.5
聚乙二醇(400mW) PEG400 11.6 14.5
聚乙二醇(1000mW) PEG1000 10.9 12.6
二丙二醇 DPG 20.3 18.4
三丙二醇 TPG 9.8 16.1
聚丙二醇(400mW) PPG400 8.3 12.9
显示于表Ⅰ的数据在图1中显示成Wh对Wp的曲线。
下面的例子表示了本发明的实践。在这些例子中,除非有相反的指示,所有的份数都按重量计。
例1
说明模塑方法
接触透镜由下面的聚合反应混合物模塑:
组份 重量份数
HEMA 100.0
甲基丙烯酸 2.00
乙二醇二甲基丙烯酸酯 0.4
Darocure 1173①0.35
1,4-丁二醇硼酸酯②102.75
①4-(2-羟基乙氧基)苯基2-羟基-2-丙基酮
②由反应797重量份1,4-丁二醇与203份重量硼酸(在90℃的温度4小时750mmHg柱真空)制成。
聚合反应混合物被放置在Larsen美国专利4,640,489(特别是见Larsen专利的图2)所描述类型的透明聚苯乙烯模具中,并将聚苯乙烯模具的一侧暴露在1.7焦耳/cm2的紫外线辐射下6至12分钟(准确的暴露时间并不严格地限制)。
例2
说明UV吸收透镜的单体/稀释剂配方
使用与上述例1类似的条件,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
乙二醇二甲基丙烯酸酯 0.4
2-(2′-羟基-5′-甲基丙烯酰基氧丙基-
3′-t-丁基苯基)-5-氯-2H-苯并三唑 3.00
樟脑醌 0.40
乙基4-(N,N-二甲基氨基)苯甲酸酯 0.60
1,4-丁二醇硼酸酯①77.45
①在90℃温度4小时在750mmHg柱的真空下将797份重量的1,4-丁二醇与203份重量的硼酸反应而制得。
例3
按照下面的一般方法,制造一系列的硼酸和二元醇的酯:
硼酸和二元醇加至1升的旋转蒸发器中,逐渐升温至90℃(达到90℃的时间是约1小时),同时施加中等真空(100托)。当达到90℃时,施加全真空(10托),并在90℃持续反应3小时。在冷却后,水份由卡尔费歇尔滴定法测量,硼酸酯在30℃的粘度由Brookfield LVF粘度计(6,12,和30rpm)测得。
根据前述一般方法所制得的硼酸酯表示于下列的表Ⅱ中,该表表示了所用的二醇(使用了表Ⅰ的缩写方法)和一种三醇,丙三醇(gly)(用作对比例的),每种组份(醇和硼酸)的摩尔数和用于制备每种酯的反应物的醇与硼酸的摩尔比,在30℃的粘度(以mpa Sec)和酯中水的百分比。表还包括说明栏。
(1)稀释剂固体,但当与单体混合时可用。
(2)当与水混合时形成硼酸晶体。
(3)与水不完全相溶(在1重量份酯对10重量份水的混合物中),但可以使用,因为在用乙醇或乙醇与水的混合物洗涤后可被替代。
(4)既不与水也不与单体混合物(1∶1重量的单体∶稀释剂)不能使用。
表示于上面表Ⅱ中的许多硼酸酯估计可用作下列单体配方的可水替代稀释剂:
组份 重量份数
HEMA 100.00
甲基丙烯酸 2.0
乙二醇二甲基丙烯酸酯 0.4
Darocure 1173 0.35
稀释剂 102.75
这个含有0.4份交联剂单体的单体配方是优选的,因为由这个配方制的水凝胶的杨氏模量值可与应用的接触透镜中具有所希望表现的相比美。并且发现如果使用这个配方(含有0.4份多官能交联剂单体)制造的水凝胶的杨氏模量是至少约0.10-0.12MPa,那么由含有稍高比例交联单体的类似配方制备的水凝胶将可希望强度足以应用作软接触透镜。因为在一般的工业化惯例中,在类似于该例所用的配方中,多官能交联剂(例如:乙二醇二甲基丙烯酸酯和三羟甲基丙烷三甲基丙烯酸酯)的用量一般是从约0.2-1.0份。
在如上述例1所描述的透明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。将每个模具中的单体/稀释剂混合物的一侧在55℃暴露在1.7焦目/cm2的紫外辐射中10分钟(TL09灯350nm的峰值辐射)。
由该稀释剂/单体混合物制备的透镜进行下列评估:
(1)透镜外观,在模具内和脱模后的;
(2)水化透镜的杨氏模量;
(3)模塑透镜的所需脱模力。
上述这些评估结果显示于下面的表Ⅲ和表Ⅳ中。表Ⅲ显示了序号,所用制造硼酸酯稀释剂的二元醇,透镜的外观(C=清楚,W=白色、OS=不透明、SO=稍不透明)和杨氏模量“E”,单位MPa。表Ⅳ显示了在三种不同温度下模塑透镜所需的脱模力。
表Ⅲ
模塑透镜的评价
外观
酯序号 醇类 模具 最后的 E 说明
1 EG C C ·20
2 EG C C ·23
3 1,2-PD C C ·11
4 1,2-PD C C ·18
5 1,2-PD C C/OS ·17 (1)
7 1,3-PD - C/OS - (2)
8 1,2-BD C C ·25
9 1,2-BD OS - - (2)
10 1,3-BD OS - - (2)
11 1,4-BD C C ·24
13 2,3-BD C C ·08
14 2,3-BD OS - - (2)
15 1,6-HD C C ·19
16 2,5-HD C C ·19
18 1,8-OD C SO ·21
20 GLY C C ·25 (对比)
21 DEG C C ·29
22 PEG 400 C C ·34
23 PEG 1000 C C ·30
24 DPG C C ·28
25 DPG C C ·27
26 TPG C C ·27
27 PPG 400 W W -
(1)稍微在聚苯乙烯模具中溶化,而引起稍微不透明表面。
(2)在聚苯乙烯模具中溶化,不能脱模。
模量实验
显示于表Ⅲ中的透镜的杨氏模量值是由下列方法确定的:
范围
本实验对比较几乎完全相同物量尺寸的透镜的非破坏性模量实验是有用的。该实验已经用Larsen等人的美国专利4,680,336(第9-10栏)中描述的一种精确实验对相同的试验透镜进行校准过。
透镜
用于本实验的透镜屈光度为-1.0,8.9+/-0.3mmBC(底曲线),0.15+/-0.01mm中心厚度,14.0+/-0.5mm的直径。
实验
测量透镜尺寸,如果在规格之内,将透镜放在透明丙烯酸园筒(13mm外径、9.8mm内径、7.2mm高)的顶上,由此透镜的前曲线靠在丙烯酸园筒的内(9.8mm直径)顶面上。
该装置浸泡在Optimec JCF/R/SI Contact Lens Analyzer中心厚度测量腔内的0.9%盐水中。将园筒和透镜对中,以便使透镜处于水平位置,调整中心厚度标尺,以便它能测量前曲表面中心的偏差。
将3mm的不锈钢球(重量0.2584克)小心地放在透镜的凹侧上,透镜的中心部分会取决于透镜的模量而发生变形。在中心厚度标尺上以mm读出变形量。模量即可由图2的校准图确定。
同一批最少3个透镜实验,每个透镜的变形测量3次,模量至少是9个测量数据的平均值。
括号中的数据是标准偏差
(1)模具顶半部分的法兰在进行力测量时破裂。
(2)数据不能用
(3)不能脱模、聚合物/稀释剂混合物溶化模具并将模具的两半部粘在一起。
(4)脱模力太低不能测量
脱模试验
用来评估打开生产聚合物/稀释剂混合物模具所需力,并且其结果列于表Ⅳ中的实验如下:
范围
本实验对确定分开模具前后半模所需的最小力是有用的,该模具(如Larsen的美国专利4,640,489所描述的)被含有已知量的稀释剂的聚合物基体粘在一起。对于所有要分析的试样,模具尺寸应保持一定。
设备
用于测量打开模具力的实验装置和装配显示在图3和图4中,在图3中所示的用于测量力的装置是一个实验室张力实验装置10,例如一台Instron model #1122。50磅的负载传感器(未显示)与图表记录器12(满标度20磅)一起使用。
温度由连接到Staco型3PN2210变阻器上的加热枪(未显示),例如Varitemp加热枪(Model VT-750A)来控制。一个T型热电偶(未显示)插到聚合物/稀释剂混合物中,用于测量聚合物/稀释剂混合物的温度。
参见图4装置14在实验过程中是位于夹持着试样16的位置,杆18用于将模具的顶半部20从底半部22中拉出来。
实验程序
试样包括模具16的顶半模部分20和底半模部分22,它们由聚合物/稀释剂基体24粘到一起。实验的试样是新生产出来并充满一定尺寸的模具内。模具在聚合后立即放入干燥器中,以防止聚合物或稀释剂吸收水份。
实验的试样如图3所示放在试样夹持器上,试样装置由具有36PSI压力的Instron的下夹具夹住,整个试样当放置在装置上时,与水平面成20°角放置,模具的底半模部分22在实验过程中由以90°间隔环绕模具底半模部分22的四个插入销(仅仅两个以截面显示)26、28保持在适当位置。
用于将顶半模20拉开底半模22的杆18插入两个半模之间,并由Instron的上夹具30夹在适当位置。杆拉顶半模的速率由Instron的十字头的速度控制。
加热枪的气流直接指向模具的顶半模,以保持一致的加热。气流的温度可用变阻器来控制。
试样的温度监视是通过插入一个热电偶,以这种方法测量聚合物/稀释剂基体24的温度改变。当热电偶测出最希望的温度时,Instron的十字头以1时/分的速度升高。测量在30℃、55℃和80℃的脱模力。
如果用Instron的图表记录器记录,则可以看出,所需用来断开聚合物/稀释剂与顶半模20的粘附作用的力是时间的函数,由这个记录可以确定最小的脱模力。
由上面给出的数据可以发现,仅仅由二醇制造的酯落在所要求的Hansen参数范围内,并给出透明的透镜(作为接触透镜用,这很重要),并且只有那些具有粘度大于100MPa Sec的具有足够高的模量值,强到可用作接触透镜用。
脱模数据清楚地说明,本发明的二醇酯比Larsen的专利4,495,313的优选酯具有更容易的脱模性(脱模需要较少的力)。
改进产率的说明可通过使用本发明的二醇硼酸酯代替丙三醇硼酸酯获得。使用类似于前述例1的配方,三批每批80个透镜,用每种单体/酯混合物测定表面缺陷的数量。当所用的稀释剂是二甘醇/硼酸酯(表Ⅱ中酯序号21)时,表面缺陷是10.4%,当稀释剂是1,4-丁二醇/硼酸酯(表Ⅱ中酯序号12)时,表面缺陷是13.0%,当稀释剂是丙三醇/硼酸酯(表Ⅱ中酯序号20)时,表面缺陷是30.4%。这是超过Larsen专利4,495,313工艺的重要改进。
例4
使用了硼酸酯可水替代稀释剂的烷基(甲基)丙烯酸酯改性的HEMA的制备。
(将20.0g的烷基(甲基)丙烯酸酯或其他甲基丙烯酸的疏水性酯加到下列物质中:)
102.11g羟基乙基甲基丙烯酸酯(HEMA)
3.82g甲基丙烯酸(MAA)
0.85g乙二醇二甲基丙烯酸酯(EGDMA)
0.10g三羟甲基丙烷三甲基丙烯酸酯(TMPTA)
0.36g DAROCURE①
136.75g可水替代的稀释剂②
①4-(2-羟基乙氧基)苯基2-羟基-2-丙基酮。
②在90℃的温度下在10托的压力下在旋转蒸发器中将1094.84份重量的1,4-丁二醇与278.64份重量的硼酸反应2小时而制得。
将单体混合物放置在40mmHg的真空烤箱中3小时以除去氧气。烤箱然后用氮气充满。在充氮的手套箱中用选好的混合物充填如在Larsen的美国专利4,460,489中图2所示类型的透明聚苯乙烯接触透镜模具。填好的模具通过暴露一侧到约1.7焦耳/Cm2的UV光(具有最大输出在365nm的Philips TL 40W/09n荧光灯泡)中进行聚合。暴露在UV光中大约10分钟(准确的时间不极窄地受限制)。聚合以后,聚合物/稀释剂混合物用50∶50乙醇∶水(体积)的混合物洗涤,接着用纯水洗涤以便用水替代稀释剂。透镜然后被装到标准软接触透镜包装溶液(缓冲盐水)中储存。
下面的表Ⅴ显示了甲基丙烯酸酯的疏水性基团、水凝胶(即:用水溶胀的聚合物)的外观,水凝胶中水的百分比,水凝胶的压缩模量(写作“刚性”)和水凝胶的氧传导性。
水凝胶的刚性由下面的方法测量:
用十字头定速运动实验机在压缩方式下获得压缩模量。所要实验的接触透镜试样首先用两个相互垂直的刀片切开,每个刀片通过透镜的中心(由透镜表面看),以形成四个饼形片。这是为了确保试样在实验期间躺平。试样在两个以0.002吋/分钟速率的平盘之间压缩。压缩应力和应变使用带式图表记录器(2吋/分钟图表速度)监视。负载传感器的全标尺偏移是0.110磅,当达到0.005磅的负载值时,假定为零压缩。表中压缩模量的单位是每平方吋磅。
氧的渗透性通过Fatt等人在“水凝胶透镜和材料的氧传导性和渗透性测量”国际接触透镜研讨会。第9卷/第2号三月/四月1982年,第76-88页介绍的方法测量。氧的渗透性表示作“DK”,其中D代表在所要实验的材料中氧的扩散参数。K代表在材料中氧的溶解度,单位是(Cm2/Sec)(mlO2/ml XmmHg)(给在表中的数值应乘以10-11得出实际值)。
表Ⅴ
疏水基 外观 水% 刚性 DK
无(对比例)①透明 60.4 20.2 30
苄基 透明 58.3 32.1 23
2-丁基 透明 64.9 26.8 26
n-丁基 透明 65.0 41.2 42
t-丁基 透明 63.0 27.0 31
n-己基 透明 61.3 43.2 30
2-乙基甲基 透明 59.0 38.1 30
n-辛基 透明 64.4 25.7② 40
n-十二烷基 透明 66.5 43.6 39
①对比例配方如下:
HEMA 488.2份
甲基丙烯酸 8.2份
乙二醇二甲基丙烯酸酯 3.1份
三羟甲基丙烷三甲基丙烯酸酯 0.49份
DAROCURE 1173 1.74份
48份这种混合物与52份前述稀释剂混合。
②该水凝胶所发现的低刚性相信是异常的。
为了说明薄水凝胶接触透镜氧的传导性较大,同样材料所制的但不同厚度的接触透镜被测量氧的传导性DK/L。使用作为疏水基的2-乙基己基和n-十二烷基如上述制造透镜材料。厚度及氧的传导性如下:
疏水基(在聚合物中20%) 中心厚度(微米) DK/L
2-乙基己基 110 18.9×10-9
2-乙基己基 60 29.3×10-9
2-乙基己基 30 37.8×10-9
n-十二烷基 110 20.2×10-9
n-十二烷基 60 29.9×10-9
n-十二烷基 30 43.0×10-9
对比例
通过无稀释剂的本体聚合制备疏水性改性HEMA
将0.2g疏水甲基丙烯酸酯加到下列物质中:
0.8g HEMA(包括0.0016g EGDMA和0.032gMAA)
0.0028g DAROCURE
在20ml的Pyrex闪烁管中制备此混合物。通过吹氮气1分钟以便从混合物中除去氧,并用复合封盖封闭,闪烁管一侧躺在二只Philips TL20W/09N灯泡下,以便让5到6Cm之间的液面照光。
该材料光聚合10分钟。结果列于表Ⅵ:
表Ⅵ
疏水性基团 外观
聚合之前 聚合之后
n-丁基 透明 透明
2-丁基 透明 透明
t-丁基 透明 透明
环己基 透明 透明
n-己基 透明 半透明
苄基 透明 透明
n-辛基 透明 不透明
n-十二烷基 透明 不透明
n-十八烷酰基 透明 不透明
2-乙基己基 透明 稍微模糊
据信这些由本体聚合(其中烷基甲基丙烯酸酯的烷基具有6个或更多碳原子)制造的透镜的明显的透明,不透明或稍微模糊是由聚合过程的不相溶性所造成的。
Claims (16)
1、制备水凝胶成型制品的方法,包括下列步骤:
(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:主要量的亲水性(甲基)丙烯酸酯单体、一种烷基(甲基)丙烯酸酯其中所述的烷基至少含有4个碳原子和一种交联单体,
(b)一种可水替代稀释剂,其中所述的稀释剂在30℃下具有至少100MPaSec的粘度,并且其中所述的稀释剂实质包括某种二元醇的硼酸酯,所述的二元醇具有Hansen极性(Wp)和Hansen氢键(Wh)粘性参数落在由园心为Wh=20.5Wp=13,半径为8.5确定的园面积内,以生产所述单体和所述稀释剂的共聚物的成型凝胶
(2)然后用水代替所述的稀释剂
2、根据权利要求1的方法,其中所述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)丙烯酸酯是2-羟基乙基甲基丙烯酸酯。
4、根据权利要求1的方法,其中所述的烷基(甲基)丙烯酸酯是n-己基甲基丙烯酸酯、n-辛基(甲基)丙烯酸酯、2-乙基己基甲基丙烯酸酯、癸基甲基丙烯酸酯或n-十二烷基甲基丙烯酸酯。
5、根据权利要求1的方法,其中所述的二元醇是1,4-丁二醇。
6、根据权利要求1的方法,其中所述的二元醇是二甘醇。
7、根据权利要求1的方法,其中的单体混合物含有甲基丙烯酸。
8、根据权利要求1的方法,其中成型的水凝胶制品是接触透镜。
9、成型接触透镜的方法,包括:
(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:主要量的亲水性(甲基)丙烯酸酯单体、交联单体和烷基(甲基)丙烯酸酯,其中的烷基含有至少4个碳原子,和一种交联单体;和
(b)一种可水替代的稀释剂,其中所述的稀释剂在30℃下的粘度至少为100MPa Sec,并且其中所述的二元酸具有Hansen极性(WP)和Hansen氢键(Wh)粘性参数落在由园心为Wh=20.5、Wp=13、半径为8.5确定的园面积内,以生产所述单体和所述稀释剂的共聚物的成型凝胶,
(2)然后用水代替所述的稀释剂。
10、根据权利要求9的方法,其中所述的亲水性单体是羟烷基(甲基)丙烯酸酯。
11、根据权利要求10的方法,其中的羟烷基(甲基)丙烯酸酯是2-羟基乙基甲基丙烯酸酯。
12、根据权利要求9的方法,其中所述的稀释剂在30℃下的粘度至少为500MPa Sec。
13、根据权利要求9的方法,其中所述烷基(甲基)丙烯酸酯是n-己基甲基丙烯酸酯、n-辛基甲基丙烯酸酯、2-乙基己基甲基丙烯酸酯或n-十二烷基甲基丙烯酸酯。
14、根据权利要求9的方法,其中所述的二元醇是1,4-丁二醇。
15、根据权利要求9的方法,其中所述的二元醇是二甘醇。
16、根据权利要求9的方法,其中单体含有甲基丙烯酸。
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