JPH06313864A - Contact lens having high oxygen permeability - Google Patents
Contact lens having high oxygen permeabilityInfo
- Publication number
- JPH06313864A JPH06313864A JP10320093A JP10320093A JPH06313864A JP H06313864 A JPH06313864 A JP H06313864A JP 10320093 A JP10320093 A JP 10320093A JP 10320093 A JP10320093 A JP 10320093A JP H06313864 A JPH06313864 A JP H06313864A
- Authority
- JP
- Japan
- Prior art keywords
- group
- integer
- oxygen permeability
- chemical
- contact lens
- 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 28
- 239000001301 oxygen Substances 0.000 title claims abstract description 28
- 230000035699 permeability Effects 0.000 title abstract description 19
- 229920001400 block copolymer Polymers 0.000 claims abstract description 17
- 239000004760 aramid Substances 0.000 claims abstract description 16
- 229920003235 aromatic polyamide Polymers 0.000 claims abstract description 16
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- 125000000962 organic group Chemical group 0.000 claims abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims description 30
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 abstract description 2
- 239000011737 fluorine Substances 0.000 abstract description 2
- 125000001153 fluoro group Chemical group F* 0.000 abstract 1
- 125000000547 substituted alkyl group Chemical group 0.000 abstract 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 229920001577 copolymer Polymers 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- -1 polysiloxane Polymers 0.000 description 11
- 229920001296 polysiloxane Polymers 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 5
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 4
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical group CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000007033 dehydrochlorination reaction Methods 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- 239000002954 polymerization reaction product Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 229920005573 silicon-containing polymer Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 125000002030 1,2-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([*:2])C([H])=C1[H] 0.000 description 1
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical group C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000002504 physiological saline solution Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
Landscapes
- Eyeglasses (AREA)
- Polyamides (AREA)
- Silicon Polymers (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、高酸素透過性を有し、
強度や加工性の点においても優れた高酸素透過性コンタ
クトレンズに関する。The present invention has a high oxygen permeability,
The present invention relates to a highly oxygen permeable contact lens excellent in strength and workability.
【０００２】[0002]
【従来の技術】従来より使用されているコンタクトレン
ズ（ＣＬ）には、（１）メチルメタクリレート、シリコ
ン含有メタクリレートなどのモノマーを主成分としたポ
リマーからなるハードコンタクトレンズ（ＨＣＬ）、
（２）ブチルメタクリレートなどを主成分としたセミハ
ードコンタクトレンズ（ＳＨＣＬ）、（３）２−ヒビロ
キシエチルメタクリレートモノマーなどの親水性モノマ
ーを主成分としたソフトコンタクトレンズ（ＳＣＬ）が
ある。これらの中で（１）は、非含水であるためＣＬの
衛生面で優位性を有しているが、目の代謝を良好に行な
い連続装着を可能にするために必要とされる酸素透過性
が不十分である。また（２）では、ある程度の柔らかさ
を有するため装着感に優れているが、酸素透過性の低さ
や形状安定性に欠けるという問題がある。更に（３）で
は、含水性を有するために、装着性の点でＳＨＣＬ、Ｈ
ＣＬより優れているが、衛生面では問題があり面倒な保
守が必要とされるうえ、レンズ中の水分により酸素が運
ばれるため酸素透過性には限度があるという欠点があ
る。これらの問題を解決するため高酸素透過性を付与す
る目的でポリシロキサンやシリコン含有メタクリレート
ポリマーなどのシリコーン系ポリマーがよく使用されて
おり、比較的生体への安全性にも優れている。しかし、
シリコーン系ポリマーは単独では強度が低く、加工性に
も問題があるため、膜厚の増加や補強材の使用が必要で
ある。2. Description of the Related Art Conventionally used contact lenses (CL) include (1) a hard contact lens (HCL) made of a polymer containing a monomer such as methyl methacrylate or silicon-containing methacrylate as a main component,
There are (2) semi-hard contact lenses (SHCL) containing butyl methacrylate as a main component, and (3) soft contact lenses (SCL) containing hydrophilic monomers such as 2-hibiroxyethyl methacrylate monomer as a main component. Among these, (1) is superior in terms of hygiene to CL because it does not contain water, but it has the oxygen permeability required for good eye metabolism and continuous wear. Is insufficient. Further, in (2), although it has a certain degree of softness and is excellent in a feeling of wearing, there is a problem that the oxygen permeability is low and the shape stability is poor. Further, in (3), since it has water content, it is easy to wear SHCL, H
Although it is superior to CL, it has a drawback in that it has a problem in hygiene and requires troublesome maintenance, and that oxygen permeability is limited because oxygen is carried by water in the lens. In order to solve these problems, silicone-based polymers such as polysiloxane and silicon-containing methacrylate polymers are often used for the purpose of imparting high oxygen permeability, and they are relatively excellent in safety to living bodies. But,
Since the silicone polymer alone has low strength and has a problem in workability, it is necessary to increase the film thickness and use a reinforcing material.
【０００３】前記シリコーン系ポリマーの強度を改善す
るための素材としては、特公昭６２−８７６２号公報、
特公昭６３−３６６４６号公報において、シリコン含有
メタクリレートとフッ素含有メタクリレートとを主成分
とする共重合体が提案されており、米国特許第３４１９
６３４号明細書、米国特許第３４１９６３５号明細書に
おいて、シリコーン−ポリカーボネート共重合体が提案
されている。これらの高酸素透過性を有するポリマーは
比較的高強度であるが、酸素透過性がいまだ十分でな
く、さらに密着性の低さの点でも問題がある。As a material for improving the strength of the silicone polymer, Japanese Patent Publication No. 62-8762,
In Japanese Examined Patent Publication No. 63-36646, a copolymer containing a silicon-containing methacrylate and a fluorine-containing methacrylate as main components is proposed and disclosed in US Pat. No. 3,419.
No. 634 and U.S. Pat. No. 3,419,635 propose a silicone-polycarbonate copolymer. These polymers having high oxygen permeability have relatively high strength, but their oxygen permeability is still insufficient, and there is a problem in that they have low adhesion.
【０００４】[0004]
【発明が解決しようとする課題】本発明の目的は、高酸
素透過性であり、透明性が良好で、強度や加工性のも優
れた高酸素透過性コンタクトレンズを提供することにあ
る。SUMMARY OF THE INVENTION An object of the present invention is to provide a highly oxygen permeable contact lens which has high oxygen permeability, good transparency, and excellent strength and workability.
【０００５】[0005]
【課題を解決するための手段】本発明によれば、下記一
般式化２（式中、Ｒ1及びＲ3は同一若しくは異なる基で
あって、二価の芳香族系有機基を示し、Ｒ2は炭素数１
〜６のアルキレン基を示し、Ｙ1及びＹ2は同一若しくは
異なる基であって、炭素数１〜６のアルキル基フッ素置
換アルキル基又はフェニル基を示す。またｍは１０〜２
００の整数、ｎは１〜５０の整数、Ｘは１〜２０の整数
を示す）で表わされる構造単位（以下ブロック構造単位
Ａと称す）を有するポリシロキサン−芳香族ポリアミド
系ブロック共重合体（以下ブロック共重合体Ｂと称す）
を含む高酸素透過性コンタクトレンズが提供される。According to the present invention, the following general formula 2 (wherein R 1 and R 3 are the same or different groups and represent a divalent aromatic organic group; 2 is carbon number 1
~ 6 alkylene groups, Y 1 and Y 2 are the same or different groups, and are alkyl groups having 1 to 6 carbon atoms, fluorine-substituted alkyl groups or phenyl groups. Also, m is 10 to 2
00, n is an integer of 1 to 50, and X is an integer of 1 to 20). A polysiloxane-aromatic polyamide block copolymer (hereinafter referred to as a block structural unit A) having a structural unit Hereinafter referred to as block copolymer B)
A high oxygen permeable contact lens comprising is provided.
【０００６】[0006]
【化２】 [Chemical 2]
【０００７】以下本発明を更に詳細に説明する。The present invention will be described in more detail below.
【０００８】本発明の高酸素透過性コンタクトレンズ
は、前記一般式化２で表わされるブロック構造単位Ａを
有するブロック共重合体Ｂを必須成分として含む。ブロ
ック構造単位Ａにおいて、Ｒ2、Ｙ1及びＹ2の炭素数が
６を超える場合、ｍが２００を超える場合、ｎが５０を
超える場合、Ｘが２０を超える場合には製造が困難であ
り、ｍが１０未満の場合には、所望の酸素透過性が得ら
れない。またＲ1及びＲ3の二価の芳香族系有機基として
は、例えばｐ−フェニレン基、ｍ−フェニレン基、ｏ−
フェニレン基、４，４’−ジフェニレンエーテル基、
４，３’−ジフェニレンエーテル基、４，４’−ビフェ
ニレン基、４，３’−ビフェニレン基、４，４’−フェ
ニレンジメチレン基、１，５−ナフチレン基、１，７−
ナフチレン基、４，４’−チオビフェニレン基、４，
３’−チオビフェニレン基、４，４’−プロピレンジフ
ェニレン基、４，４’−メチレンジフェニレン基、４，
３’−メチレンジフェニレン基等を好ましく挙げること
ができる。Ｒ2における炭素数１〜６のアルキレン基と
しては、例えばメチレン基、エチレン基、プロピレン
基、ブチレン基等を好ましく挙げることができる。更に
前記ブロック共重合体Ｂの粘度は、３０℃のジメチルア
セトアミド１００ｍｌ中０．５ｇにおいて固有粘度（η
inh）０．１〜２の範囲であるのが好ましい。The highly oxygen permeable contact lens of the present invention contains the block copolymer B having the block structural unit A represented by the general formula 2 as an essential component. In the block structural unit A, when the carbon number of R 2 , Y 1 and Y 2 exceeds 6, when m exceeds 200, n exceeds 50, and X exceeds 20, production is difficult. , M is less than 10, the desired oxygen permeability cannot be obtained. Examples of the divalent aromatic organic group for R 1 and R 3 include p-phenylene group, m-phenylene group, o-
Phenylene group, 4,4'-diphenylene ether group,
4,3'-diphenylene ether group, 4,4'-biphenylene group, 4,3'-biphenylene group, 4,4'-phenylenedmethylene group, 1,5-naphthylene group, 1,7-
Naphthylene group, 4,4'-thiobiphenylene group, 4,
3'-thiobiphenylene group, 4,4'-propylenediphenylene group, 4,4'-methylenediphenylene group, 4,
A 3'-methylenediphenylene group and the like can be preferably mentioned. Preferable examples of the alkylene group having 1 to 6 carbon atoms in R 2 include a methylene group, an ethylene group, a propylene group, a butylene group and the like. Furthermore, the viscosity of the block copolymer B is 0.5 g in 100 ml of dimethylacetamide at 30 ° C.
inh) It is preferably in the range of 0.1 to 2.
【０００９】前記ブロック共重合体Ｂを構成するブロッ
ク構造単位Ａとしては、例えば下記構造式化３〜１４等
を好ましく挙げることができる（ただし、式中ｎは１〜
５０の整数を示す）。As the block structural unit A constituting the block copolymer B, for example, the following structural formulas 3 to 14 can be preferably mentioned (where n is 1 to 1).
Indicates an integer of 50).
【００１０】[0010]
【化３】 [Chemical 3]
【００１１】[0011]
【化４】 [Chemical 4]
【００１２】[0012]
【化５】 [Chemical 5]
【００１３】[0013]
【化６】 [Chemical 6]
【００１４】[0014]
【化７】 [Chemical 7]
【００１５】[0015]
【化８】 [Chemical 8]
【００１６】[0016]
【化９】 [Chemical 9]
【００１７】[0017]
【化１０】 [Chemical 10]
【００１８】[0018]
【化１１】 [Chemical 11]
【００１９】[0019]
【化１２】 [Chemical 12]
【００２０】[0020]
【化１３】 [Chemical 13]
【００２１】[0021]
【化１４】 [Chemical 14]
【００２２】前記ブロック構造単位Ａを有するブロック
共重合体Ｂを調製するには、例えば下記一般式化１５
（式中、Ｒ2は炭素数１〜６のアルキレン基、Ｙ1及びＹ
2は同一又は異なる基であって、炭素数１〜６のアルキ
ル基もしくはフェニル基を示す。またｍは１０〜２００
の整数を示す）で表わされる特定のポリシロキサン誘導
体と、To prepare the block copolymer B having the block structural unit A, for example, the following general formula 15
(In the formula, R 2 is an alkylene group having 1 to 6 carbon atoms, Y 1 and Y
2 are the same or different groups and represent an alkyl group having 1 to 6 carbon atoms or a phenyl group. Also, m is 10 to 200
A specific polysiloxane derivative represented by
【００２３】[0023]
【化１５】 [Chemical 15]
【００２４】下記一般式化１６（式中ｎは１〜５０の整
数を示す）で表わされる特定の芳香族ポリアミドとをブ
ロック共重合する方法等により得ることができる。It can be obtained by a method such as block copolymerization with a specific aromatic polyamide represented by the following general formula 16 (n is an integer of 1 to 50).
【００２５】[0025]
【化１６】 [Chemical 16]
【００２６】前記特定のシロキサン誘導体は、分子量９
００〜１５００の両末端にアミノ基を有する前記一般式
化１５で示されるポリシロキサン誘導体であって、具体
的には例えば、下記構造式化１７〜２３で表わされる化
合物等を好ましく挙げることができる。The specific siloxane derivative has a molecular weight of 9
The polysiloxane derivative represented by the general formula 15 having an amino group at both ends of 00 to 1500 and specifically, for example, a compound represented by the following structural formulas 17 to 23 can be preferably mentioned. .
【００２７】[0027]
【化１７】 [Chemical 17]
【００２８】[0028]
【化１８】 [Chemical 18]
【００２９】[0029]
【化１９】 [Chemical 19]
【００３０】[0030]
【化２０】 [Chemical 20]
【００３１】[0031]
【化２１】 [Chemical 21]
【００３２】[0032]
【化２２】 [Chemical formula 22]
【００３３】[0033]
【化２３】 [Chemical formula 23]
【００３４】前記特定のシロキサン誘導体は、公知の方
法で調製することができ、信越化学工業社、東芝シリコ
ーン社、チッソ社等が市販している市販品を用いること
ができる。The above-mentioned specific siloxane derivative can be prepared by a known method, and commercially available products available from Shin-Etsu Chemical Co., Ltd., Toshiba Silicone Co., Chisso Co., etc. can be used.
【００３５】また前記特定の芳香族ポリアミドは、分子
量５００〜１８０００の両末端に酸クロライド基を有す
る前記一般式化１６で示される芳香族ポリアミドであっ
て、具体的に例えば、下記構造式化２４〜２７で表わさ
れる化合物（ただし、式中ｎは１〜５０の整数を示す）
等を好ましく挙げることができる。The specific aromatic polyamide is an aromatic polyamide represented by the general formula 16 and having an acid chloride group at both ends and having a molecular weight of 500 to 18,000. Specifically, for example, the following structural formula 24 To 27 (wherein n represents an integer of 1 to 50)
And the like can be preferably mentioned.
【００３６】[0036]
【化２４】 [Chemical formula 24]
【００３７】[0037]
【化２５】 [Chemical 25]
【００３８】[0038]
【化２６】 [Chemical formula 26]
【００３９】[0039]
【化２７】 [Chemical 27]
【００４０】前記特定の芳香族ポリアミドを調製するに
は、例えばクロロホルム等の溶媒及びトリエチルアミン
等の脱塩化水素剤等の存在下にて、好ましくは−５０〜
３０℃にてジアミンとジカルボン酸クロライドとを反応
させ、発熱反応が終了した後室温程度にて、好ましくは
１〜１０時間反応させる方法等により得ることができ
る。In order to prepare the above-mentioned specific aromatic polyamide, for example, in the presence of a solvent such as chloroform and a dehydrochlorination agent such as triethylamine, etc., preferably -50 to.
It can be obtained by a method of reacting a diamine and a dicarboxylic acid chloride at 30 ° C., and after reacting the exothermic reaction at about room temperature, preferably for 1 to 10 hours.
【００４１】前記ポリシロキサン誘導体と前記芳香族ポ
リアミドとをブロック共重合させるには、例えばクロロ
ホルム等の溶媒及びトリエチルアミン等の脱塩化水素剤
等の存在下にて、好ましくは−５０〜３０℃にて反応さ
せ、発熱反応が終了した後室温程度にて、好ましくは１
〜１０時間重合反応させる方法等により得ることができ
る。この際前記ポリシロキサン誘導体と芳香族ポリアミ
ドとの仕込み量は、モル比で好ましくは５：９５〜９
０：１０、特に好ましくは２０：８０〜８０：２０の範
囲とするのが好ましい。前記ポリシロキサン誘導体の仕
込み量が９５％を超える場合には、強度が低下し、また
５％未満の場合には、酸素透過性が低下するので好まし
くない。また前記ポリシロキサン誘導体及び芳香族ポリ
アミドの分子量を前記分子量の範囲内でかえることによ
り、得られる前記ブロック共重合体Ｂにおける前記ポリ
シロキサン誘導体単位の含有率を３〜９７％の範囲内で
適宜変えることができる。To block-copolymerize the polysiloxane derivative and the aromatic polyamide, for example, in the presence of a solvent such as chloroform and a dehydrochlorination agent such as triethylamine, preferably at -50 to 30 ° C. After the reaction is completed and the exothermic reaction is completed, the reaction is performed at room temperature, preferably 1
It can be obtained by a method such as a polymerization reaction for 10 hours. At this time, the charged amount of the polysiloxane derivative and the aromatic polyamide is preferably 5:95 to 9 in terms of molar ratio.
It is preferably 0:10, particularly preferably 20:80 to 80:20. If the charged amount of the polysiloxane derivative is more than 95%, the strength is lowered, and if it is less than 5%, the oxygen permeability is lowered, which is not preferable. Further, by changing the molecular weights of the polysiloxane derivative and the aromatic polyamide within the range of the molecular weight, the content of the polysiloxane derivative unit in the obtained block copolymer B is appropriately changed within the range of 3 to 97%. be able to.
【００４２】本発明の高酸素透過性コンタクトレンズを
調製するには、前記ブロック共重合体Ｂを適当な溶媒に
溶解して所望のレンズ状、平板状、円盤状等に流延、乾
燥し、そのまま又はコンタクトレンズに切削加工して成
形する方法等により製造することができる。この場合前
記適当な溶媒としては、例えばジメチルホルムアミド、
ジメチルアセトアミド、Ｎ−メチル−２−ピロリドン等
が挙げられる。また他の方法としては溶融成形法等、具
体的には例えば前記ブロック共重合体Ｂを１５０〜３０
０℃の温度範囲で射出成形、押出し後、圧縮機などの加
工機を使用して所望の形状に成形し、そのまま又は切削
加工してコンタクトレンズとする方法等により得ること
もできる。To prepare the highly oxygen permeable contact lens of the present invention, the block copolymer B is dissolved in a suitable solvent, cast into a desired lens shape, a flat plate shape, a disk shape, etc., and dried. It can be manufactured as it is or by a method of cutting and forming a contact lens. In this case, the suitable solvent includes, for example, dimethylformamide,
Examples thereof include dimethylacetamide and N-methyl-2-pyrrolidone. Further, as another method, a melt molding method or the like, specifically, for example, by using the block copolymer B of 150 to 30
It can also be obtained by a method such as injection molding or extrusion in the temperature range of 0 ° C., molding into a desired shape by using a processing machine such as a compressor, and directly or cutting to obtain a contact lens.
【００４３】[0043]
【発明の効果】本発明の高酸素透過性コンタクトレンズ
は、特定の構造単位を有するポリシロキサン−芳香族ポ
リアミド系ブロック共重合体で構成されるので、特に酸
素透過性が１５０×１０~11ｍｌ(ＳＴＰ)ｃｍ／ｃｍ2・
ｓｅｃ・ｍｍＨｇ以上を示し、透明性にも優れており、
かつ強度及び加工性も良好であるので円盤状、棒状等の
種々の形状に容易に成形できる。また組成を変えること
によって、ハードコンタクトレンズ及びソフトコンタク
トレンズのどちらにも使用することができる他、成形法
によっては眼内レンズなどの医療用レンズとして使用す
ることもできる。Since the highly oxygen permeable contact lens of the present invention is composed of a polysiloxane-aromatic polyamide block copolymer having a specific structural unit, it has an oxygen permeability of 150 × 10 to 11 ml. (STP) cm / cm 2
It shows sec.mmHg or more, and has excellent transparency.
Moreover, since it has good strength and workability, it can be easily formed into various shapes such as a disk shape and a bar shape. Further, by changing the composition, it can be used as both a hard contact lens and a soft contact lens, and can also be used as a medical lens such as an intraocular lens depending on the molding method.
【００４４】[0044]
【実施例】以下実施例及び比較例に基づいて本発明をさ
らに詳細に説明するが、本発明はこれらに限定されるも
のではない。The present invention will be described in more detail based on the following examples and comparative examples, but the present invention is not limited thereto.
【００４５】[0045]
【実施例１】５００ｍｌ容量の４つ口フラスコ中にて、
イソフタル酸クロライド１０．１５ｇ（５０ｍｍｏ
ｌ）、トリエチルアミン塩酸塩１１．０１ｇ（８０ｍｍ
ｏｌ）及びクロロホルム８０ｍｌ（１ｍｏｌ）を０℃で
混合撹拌し、さらにこの混合物に、クロロホルム８０ｍ
ｌ（１ｍｏｌ）に溶解した３，４’−ジアミノジフェニ
ルエーテル８．０ｇ（４０ｍｍｏｌ）及びトリエチルア
ミン塩酸塩１１．０１ｇ（８０ｍｍｏｌ）と、クロロホ
ルム８０ｍｌ（１ｍｏｌ）に溶解させたトリエチルアミ
ン１１．１６ｍｌ（８０ｍｍｏｌ）とを２００ｍｌ容量
の滴下ロートを用いて滴下し、０℃にて２時間撹拌しな
がら重合反応を行い、両末端が酸クロライドの重合反応
物を得た。次いで得られた重合反応物に、クロロホルム
８０ｍｌ（１ｍｏｌ）に溶解させた平均分子量１６８０
のビス−（３−アミノプロピル）ポリジメチルシロキサ
ン１６．８ｇ（１０ｍｍｏｌ）、トリエチルアミン塩酸
塩１１．０１ｇ（８０ｍｍｏｌ）及びトリエチルアミン
２．８ｍｌ（２０ｍｍｏｌ）を２００ｍｌ容量の滴下ロ
ートを用いて滴下し、０℃にて４時間撹拌しながら共重
合反応を行い、共重合体を含む溶液を得た。得られた共
重合体を含む溶液を４リットルのメタノールに添加して
共重合体を析出、濾過した後メタノール、四塩化炭素を
用いて洗浄し、減圧下にて乾燥して、下記構造式化２８
（式中ｍは２０、ｎは４を示す）で表わされる繰り返し
単位を有するポリシロキサン−芳香族ポリアミドブロッ
ク共重合体を得た。得られた共重合体の粘度をジメチル
アセトアミド中、８０℃で測定した。その結果を表１に
示す。Example 1 In a 500 ml four-necked flask,
Isophthalic acid chloride 10.15g (50mmo
l), 11.01 g of triethylamine hydrochloride (80 mm
ol) and 80 ml (1 mol) of chloroform were mixed and stirred at 0 ° C., and 80 ml of chloroform was added to this mixture.
8.0 g (40 mmol) of 3,4′-diaminodiphenyl ether dissolved in 1 (1 mol) and 11.01 g (80 mmol) of triethylamine hydrochloride, and 11.16 ml (80 mmol) of triethylamine dissolved in 80 ml (1 mol) of chloroform. The mixture was added dropwise using a dropping funnel having a volume of 200 ml, and the polymerization reaction was carried out at 0 ° C. for 2 hours with stirring to obtain a polymerization reaction product of acid chloride at both ends. Then, the obtained polymerization reaction product had an average molecular weight of 1680 dissolved in 80 ml (1 mol) of chloroform.
16.8 g (10 mmol) of bis- (3-aminopropyl) polydimethylsiloxane, 11.01 g (80 mmol) of triethylamine hydrochloride and 2.8 ml (20 mmol) of triethylamine were added dropwise using a dropping funnel having a capacity of 200 ml, and the temperature was 0 ° C. The copolymerization reaction was carried out while stirring for 4 hours to obtain a solution containing a copolymer. The solution containing the obtained copolymer was added to 4 liters of methanol to precipitate the copolymer, which was filtered, washed with methanol and carbon tetrachloride, and dried under reduced pressure to obtain the following structural formula. 28
A polysiloxane-aromatic polyamide block copolymer having a repeating unit represented by the formula (wherein m is 20 and n is 4) was obtained. The viscosity of the obtained copolymer was measured at 80 ° C. in dimethylacetamide. The results are shown in Table 1.
【００４６】[0046]
【化２８】 [Chemical 28]
【００４７】次いで、得られた共重合体が０．５重量％
となるようにジメチルアセトアミドに溶解した後、キャ
スト法によりコンタクトレンズを作製した。得られたコ
ンタクトレンズの酸素透過性を測定するために、前記共
重合体を溶解したジメチルアセトアミド溶液を用いてキ
ャスト法により厚さ２００μｍのフィルムを作製し、フ
ィルムの酸素透過性を、製科研式フィルム酸素透過測定
器により、３５℃の条件下、０．９重量％生理食塩水を
用いて測定した。結果を表１に示す。Then, 0.5% by weight of the obtained copolymer was obtained.
After being dissolved in dimethylacetamide so as to be, a contact lens was produced by a casting method. In order to measure the oxygen permeability of the obtained contact lens, a film having a thickness of 200 μm was produced by a casting method using a dimethylacetamide solution in which the above copolymer was dissolved. It was measured with a film oxygen permeation measuring device under the condition of 35 ° C. using 0.9 wt% physiological saline. The results are shown in Table 1.
【００４８】[0048]
【実施例２及び３】イソフタル酸クロライド及びビス
（３−アミノプロピル）ポリジメチルシロキサンの種類
及び仕込み量を表１に示す値に代えた以外は、実施例１
と同様に重合反応を行なって、前記化２８においてｍ及
びｎが表１に示す値であるポリシロキサン−芳香族ポリ
アミドブロック共重合体を得た。得られた共重合体の粘
度を実施例１と同様に測定した。結果を表１に示す。次
いで実施例１と同様にコンタクトレンズを作製し、また
得られたコンタクトレンズの酸素透過性を、フィルムを
調製して実施例１と同様に評価した。結果を表１に示
す。[Examples 2 and 3] Example 1 was repeated except that the types and amounts of the isophthalic acid chloride and bis (3-aminopropyl) polydimethylsiloxane were changed to the values shown in Table 1.
Polymerization reaction was carried out in the same manner as above to obtain a polysiloxane-aromatic polyamide block copolymer having the values of m and n in Table 1 shown in Table 1. The viscosity of the obtained copolymer was measured in the same manner as in Example 1. The results are shown in Table 1. Then, a contact lens was prepared in the same manner as in Example 1, and the oxygen permeability of the obtained contact lens was evaluated in the same manner as in Example 1 by preparing a film. The results are shown in Table 1.
【００４９】[0049]
【実施例４】３，４’−ジアミノジフェニルエーテルを
４，４’−ジアミノジフェニルエーテルに代えた以外
は、実施例１と同様に行なって下記構造式化２９で表わ
されるポリシロキサン−芳香族ポリアミドブロック共重
合体を得た。Example 4 A polysiloxane-aromatic polyamide block copolymer represented by the following structural formula 29 was carried out in the same manner as in Example 1 except that 3,4'-diaminodiphenyl ether was replaced with 4,4'-diaminodiphenyl ether. A polymer was obtained.
【００５０】[0050]
【化２９】 [Chemical 29]
【００５１】次いで得られた共重合体の粘度を実施例１
と同様に測定した。結果を表１に示す。次いで実施例１
と同様にコンタクトレンズを作製し、また得られたコン
タクトレンズの酸素透過性を、フィルムを調製して実施
例１と同様に評価した。結果を表１に示す。Next, the viscosity of the obtained copolymer was measured in Example 1
It measured similarly to. The results are shown in Table 1. Then Example 1
A contact lens was prepared in the same manner as above, and the oxygen permeability of the obtained contact lens was evaluated in the same manner as in Example 1 by preparing a film. The results are shown in Table 1.
【００５２】[0052]
【実施例５】３，４’−ジアミノジフェニルエーテルを
１，３−ジアミノベンゼンに代えた以外は、実施例１と
同様に行なって下記構造式化３０で表わされるポリシロ
キサン−芳香族ポリアミドブロック共重合体を得た。Example 5 A polysiloxane-aromatic polyamide block copolymer having the following structural formula 30 was prepared in the same manner as in Example 1 except that 1,3-diaminobenzene was used instead of 3,4'-diaminodiphenyl ether. Got united.
【００５３】[0053]
【化３０】 [Chemical 30]
【００５４】次いで得られた共重合体の粘度を実施例１
と同様に測定した。結果を表１に示す。次いで実施例１
と同様にコンタクトレンズを作製し、また得られたコン
タクトレンズの酸素透過性を、フィルムを調製して実施
例１と同様に評価した。結果を表１に示す。Then, the viscosity of the obtained copolymer was measured in Example 1
It measured similarly to. The results are shown in Table 1. Then Example 1
A contact lens was prepared in the same manner as above, and the oxygen permeability of the obtained contact lens was evaluated in the same manner as in Example 1 by preparing a film. The results are shown in Table 1.
【００５５】[0055]
【比較例１】ポリジメチルシロキサンを用いず、イソフ
タル酸クロライドのみを用いて、仕込み量を表１に示す
値に代えた以外は、実施例１と同様に重合体を得た。得
られた重合体の粘度を実施例１と同様に測定した。結果
を表１に示す。次いで実施例１と同様にフィルムを調製
して酸素透過性を実施例１と同様に評価した。結果を表
１に示す。Comparative Example 1 A polymer was obtained in the same manner as in Example 1, except that polydimethylsiloxane was not used and only isophthalic acid chloride was used and the charged amount was changed to the value shown in Table 1. The viscosity of the obtained polymer was measured in the same manner as in Example 1. The results are shown in Table 1. Then, a film was prepared in the same manner as in Example 1 and the oxygen permeability was evaluated in the same manner as in Example 1. The results are shown in Table 1.
【００５６】[0056]
【比較例２】３，４’−ジアミノジフェニルエーテルを
用いず、またイソフタル酸クロライドの仕込み量を表１
に示す値に代えた以外は、実施例１と同様に共重合体を
含む溶液を得たが、メタノールを添加しても析出物は得
られなかった。[Comparative Example 2] 3,4'-diaminodiphenyl ether was not used, and the charging amount of isophthalic acid chloride is shown in Table 1.
A solution containing the copolymer was obtained in the same manner as in Example 1 except that the value was changed to the value shown in Example 1. However, no precipitate was obtained even when methanol was added.
【００５７】[0057]
【表１】 [Table 1]
───────────────────────────────────────────────────── フロントページの続き (72)発明者 鯉沼 康美 茨城県つくば市東新井32−16 (72)発明者 明石 満 鹿児島県鹿児島市山田町2540−83 (72)発明者 古薗 勉 鹿児島県鹿児島市明和４丁目17−29 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Yasumi Koinuma 32-16 Higashiarai, Tsukuba-shi, Ibaraki (72) Inventor Mitsuru Akashi 2540-83 Yamada-cho, Kagoshima-shi, Kagoshima Prefecture (72) Tsutomu Kozono Meiwa, Kagoshima-shi, Kagoshima Prefecture 4-chome 17-29
Claims (1)
一若しくは異なる基であって、二価の芳香族系有機基を
示し、Ｒ2は炭素数１〜６のアルキレン基を示し、Ｙ1及
びＹ2は同一若しくは異なる基であって、炭素数１〜６
のアルキル基、フッ素置換アルキル基又はフェニル基を
示す。またｍは１０〜２００の整数、ｎは１〜５０の整
数、Ｘは１〜２０の整数を示す）で表わされる構造単位
を有するポリシロキサン−芳香族ポリアミド系ブロック
共重合体を含む高酸素透過性コンタクトレンズ。 【化１】 1. The following general formula 1 (wherein R 1 and R 3 are the same or different groups and represent a divalent aromatic organic group, and R 2 is an alkylene group having 1 to 6 carbon atoms. And Y 1 and Y 2 are the same or different groups and have 1 to 6 carbon atoms.
Is an alkyl group, a fluorine-substituted alkyl group or a phenyl group. Further, m is an integer of 10 to 200, n is an integer of 1 to 50, and X is an integer of 1 to 20.) High oxygen permeation including a polysiloxane-aromatic polyamide block copolymer having a structural unit represented by Sex contact lenses. [Chemical 1]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10320093A JP3246793B2 (en) | 1993-04-28 | 1993-04-28 | High oxygen permeability contact lens |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10320093A JP3246793B2 (en) | 1993-04-28 | 1993-04-28 | High oxygen permeability contact lens |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06313864A true JPH06313864A (en) | 1994-11-08 |
| JP3246793B2 JP3246793B2 (en) | 2002-01-15 |
Family
ID=14347880
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10320093A Expired - Fee Related JP3246793B2 (en) | 1993-04-28 | 1993-04-28 | High oxygen permeability contact lens |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3246793B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08201734A (en) * | 1995-01-26 | 1996-08-09 | Menicon Co Ltd | Ophthalmic lens material |
| JP4547806B2 (en) * | 1998-08-14 | 2010-09-22 | 日油株式会社 | Polysiloxane-polyamide copolymer, production method thereof and various materials |
| JP2016037604A (en) * | 2014-08-07 | 2016-03-22 | アクロン ポリマー システムズ，インク． | Method for producing polyamide |
| CN110452389A (en) * | 2019-08-23 | 2019-11-15 | 山东省科学院新材料研究所 | Low temperature resistant low ventilative silicone coatings composition of one kind and preparation method thereof |
-
1993
- 1993-04-28 JP JP10320093A patent/JP3246793B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08201734A (en) * | 1995-01-26 | 1996-08-09 | Menicon Co Ltd | Ophthalmic lens material |
| JP4547806B2 (en) * | 1998-08-14 | 2010-09-22 | 日油株式会社 | Polysiloxane-polyamide copolymer, production method thereof and various materials |
| JP2016037604A (en) * | 2014-08-07 | 2016-03-22 | アクロン ポリマー システムズ，インク． | Method for producing polyamide |
| CN110452389A (en) * | 2019-08-23 | 2019-11-15 | 山东省科学院新材料研究所 | Low temperature resistant low ventilative silicone coatings composition of one kind and preparation method thereof |
| CN110452389B (en) * | 2019-08-23 | 2021-07-23 | 山东省科学院新材料研究所 | A kind of low temperature resistant and low gas permeability silicone resin coating composition and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3246793B2 (en) | 2002-01-15 |
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