JP2003311762A - Method for separating mold - Google Patents

Method for separating mold

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Publication number
JP2003311762A
JP2003311762A JP2002118029A JP2002118029A JP2003311762A JP 2003311762 A JP2003311762 A JP 2003311762A JP 2002118029 A JP2002118029 A JP 2002118029A JP 2002118029 A JP2002118029 A JP 2002118029A JP 2003311762 A JP2003311762 A JP 2003311762A
Authority
JP
Japan
Prior art keywords
group
medical device
molding die
polymer
water
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
Application number
JP2002118029A
Other languages
Japanese (ja)
Other versions
JP3640934B2 (en
Inventor
Tsuneo Hogi
恒夫 保木
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Asahi Kasei Aime Co Ltd
Original Assignee
Asahi Kasei Aime Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Asahi Kasei Aime Co Ltd filed Critical Asahi Kasei Aime Co Ltd
Priority to JP2002118029A priority Critical patent/JP3640934B2/en
Publication of JP2003311762A publication Critical patent/JP2003311762A/en
Application granted granted Critical
Publication of JP3640934B2 publication Critical patent/JP3640934B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for taking out a medical instrument molded by polymerization and reduced in the content of an unpolymerized material and impurities by simply separating a mold in producing the medical instrument, especially a contact lens, in the mold. <P>SOLUTION: The medical instrument is taken out from the mold after impurities are extracted from the medical instrument molded by polymerization in the mold. The method includes a process for bringing the medical instrument into contact with a subcritical or supercritical liquid, and a process for separating the mold to take out the medical instrument molded by polymerization. <P>COPYRIGHT: (C)2004,JPO

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【発明の属する技術分野】本発明は、医療用具として使
用するポリマーの成形品を成形用鋳型の中で重合成形し
て、重合後に当該成形型から分離して取り出す方法に関
する。更に詳細には、本発明は、成形用型において重合
成形された医療用具から不純物を抽出後、医療用具を成
形用型から取り出す方法であって、該成形用型に医療用
具が内蔵した状態で亜臨界ないしは超臨界流体に接触さ
せる工程、成形用型を分離し重合成形された医療用具を
取り出す工程を含むことを特徴とする方法である。多く
のポリマー成形品は、モノマー、オリゴマー、マクロマ
ー又はプレポリマーなど重合性の材料を成形用型内に配
置し、次いでその材料を重合させることにより製造され
る。典型的にこのようにして成形された成形品は、その
表面および内部に取り除くことが出来るか、抽出するこ
とが出来る未重合材料及び不純物を含む。医療用具とし
てポリマー成形品を使用するためには、これら取り除く
ことが出来るか抽出することが出来る材料を取り除くこ
とは、生物学的悪影響を出来るだけ少なくする上で重要
である。また、成形用型で重合して医療用具を製造する
上で、成形用鋳型で形成された重合物は、その表面、端
部などその外観形状を損傷することなく、成形用型から
分離、開放されることが重要である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for polymerizing and molding a polymer molded article used as a medical device in a molding mold, and after polymerizing, taking out the polymer separately from the molding die. More specifically, the present invention is a method for extracting a medical device from a molding die after extracting impurities from the medical device polymerized and molded in the molding die, wherein the medical device is built in the molding die. The method is characterized by including a step of contacting with a subcritical or supercritical fluid and a step of separating a molding die and taking out a polymerized medical device. Many polymeric moldings are made by placing a polymerizable material such as a monomer, oligomer, macromer or prepolymer in a mold and then polymerizing the material. Molded articles thus molded typically contain unpolymerized material and impurities that can be removed or extracted on the surface and inside. For the use of polymer moldings as medical devices, the removal of these removable or extractable materials is important for minimizing the adverse biological effects. Further, in producing a medical device by polymerizing with a molding die, the polymer formed with the molding mold is separated from the molding die and opened without damaging the appearance shape such as the surface or the end. It is important to be done.

【０００２】一方、これら医療用具はその生体適合性を
高めるために、その表面が親水性であることが求めら
れ、多くの場合そのポリマー組成物に親水性のモノマー
成分を含有させて重合されるが、重合成形型がポリプロ
ピレン、塩化ビニルなど疎水性ポリマーで出来ていると
成形品の表面が疎水性となり、重合後に成形品の表面を
プラズマ処理等で親水性を付与する工程が必要となる。
これを解決するために、重合成形型を極性基を有するポ
リマーにすると成形品の表面が親水性となり、後処理を
しなくても優れた親水性を有する成形品が得られるが、
重合成形型とポリマー成形品が強固に密着し、重合物の
表面、端部に分離、開放時の微細な損傷が生じ易くな
る。本発明は、成形用型に医療用具が内蔵した状態で亜
臨界ないしは超臨界流体に接触させる工程、成形用型を
剥離し重合成形された医療用具を取り出す工程を含むこ
とを特徴とする方法に関する。On the other hand, these medical devices are required to have a hydrophilic surface in order to enhance their biocompatibility, and in many cases, the polymer composition is polymerized by containing a hydrophilic monomer component. However, if the polymerization mold is made of a hydrophobic polymer such as polypropylene or vinyl chloride, the surface of the molded product becomes hydrophobic, and a step of imparting hydrophilicity to the surface of the molded product by plasma treatment or the like after the polymerization is required.
In order to solve this, when the polymerization mold is made of a polymer having a polar group, the surface of the molded product becomes hydrophilic, and a molded product having excellent hydrophilicity can be obtained without post-treatment,
The polymerization mold and the polymer molded product are firmly adhered to each other, and the surface and end portions of the polymer are likely to be separated and finely damaged when opened. The present invention relates to a method characterized by including a step of contacting with a subcritical or supercritical fluid in a state where a medical device is built in a molding die, and a step of peeling the molding die and taking out a polymerized medical device. .

【０００３】[0003]

【従来の技術】成形用型で医療用具特にコンタクトレン
ズを成形後、コンタクレンズを分離、開放するための慣
用の方法は、例えば米国特許第５、２６４、１６１号明
細書に開示されているように、加熱した水中でレンズを
徐々に分離し、手で取り出す方法がある。しかしなが
ら、レンズの分離が十分でなく取扱いの注意不足により
欠陥品になり易く、手間もかかるものであった。また、
離形剤、例えばワックス又はシリコーン製剤が成形用型
に塗布されてから重合しうる材料を注入し重合成形する
方法があるが、重合過程でこれら離形剤が重合しうる材
料中に溶解し、十分な作用を発揮しなくなり用いること
ができない。2. Description of the Related Art A conventional method for separating and opening contact lenses after molding medical devices, particularly contact lenses with a molding die is disclosed in, for example, US Pat. No. 5,264,161. Another method is to gradually separate the lens in heated water and remove it by hand. However, the separation of the lens is not sufficient, and due to lack of care in handling, it tends to be a defective product, which is time-consuming. Also,
There is a method of injecting a polymerizable material after a release agent, for example, a wax or a silicone preparation is applied to a molding die, and polymerizing and molding.However, in the polymerization process, these release agents are dissolved in the polymerizable material, It cannot be used because it does not exert a sufficient action.

【０００４】特表２００１−５０２３６４号公報、特表
平１１−５０００７８号公報、特表平９−５１１０００
号公報には、成形された物品を抽出溶媒に接触させる工
程、及びガスが液化した液体に接触させて物品を取り出
し、かつ抽出する方法が記載されているが、抽出媒体に
接触させるために成形用型を開放させてから行う必要が
あり、重合性の材料と成形用型との界面が簡単に開放出
来る場合に限られ、例えば、成形型がポリプロピレンで
形成された場合には適用できるが、ポリプロピレンなど
非極性材料の成形型で重合成形したコンタクトレンズ
は、その表面が疎水性となっておりそのままではコンタ
クトレンズとして必要な親水性が無く、装用時に涙液が
はじかれ曇りの原因となるためプラズマ処理などのレン
ズの後処理が必要であった。また、極性基をもつポリマ
ーで形成された成形型では、レンズが型に強固に結合し
成形型を開放することが出来ず適用できない。Japanese Patent Publication No. 2001-502364, Japanese Patent Publication No. 11-500078, and Japanese Patent Publication No. 9-511000.
Japanese Unexamined Patent Publication (Kokai) describes a step of bringing a molded article into contact with an extraction solvent, and a method of taking out and extracting the article by bringing the gas into contact with a liquefied liquid. It is necessary to open after the mold has been opened, and it is limited to the case where the interface between the polymerizable material and the molding die can be easily opened.For example, when the molding die is made of polypropylene, it can be applied. Contact lenses polymerized with a non-polar material such as polypropylene have a hydrophobic surface and do not have the hydrophilicity required for contact lenses as they are, and tear fluid is repelled during wearing, causing fog. Post-treatment of lenses such as plasma treatment was required. Further, a molding die formed of a polymer having a polar group cannot be applied because the lens is firmly bonded to the mold and the molding die cannot be opened.

【０００５】[0005]

【発明が解決しようとする課題】本発明者は、成形用型
内で医療用具、特にコンタクトレンズを重合し製造する
にあたり、成形用型を簡便に分離し、重合成形された未
重合材料および不純物の含有量が少ない医療用具を欠陥
なく取り出す方法について鋭意検討し、本発明を完成す
るに至った。DISCLOSURE OF THE INVENTION In polymerizing and manufacturing a medical device, particularly a contact lens, in a molding die, the present inventor simply separates the molding die to form a polymerization-molded unpolymerized material and impurities. The present invention has been completed by intensively studying a method for taking out a medical device containing a small amount of the above without defect.

【０００６】[0006]

【課題を解決するための手段】本発明は、医療用具とく
にコンタクトレンズを製造するにあたり、成形用型に医
療用具が内蔵した状態で亜臨界ないしは超臨界流体に接
触させる工程、成形用型を分離し重合成形された医療用
具を取り出す工程を含むことを特徴とする方法である。
本発明の成形用型は上下二つの鋳型からなり、その二つ
の鋳型の間に重合性モノマー、オリゴマー、マクロマー
等のポリマー組成物を入れて重合させ、その重合後の成
形用型が合わさった状態、すなわち成形用型に医療用具
が内蔵した状態で亜臨界ないしは超臨界流体に接触させ
るものである。成形用型は重合性モノマー、オリゴマ
ー、あるいはマクロマー等に侵されない材質であれば任
意のものが使用されるが、極性基を有するポリマーから
選択された１種以上のポリマーからなるものが得られる
医療用具の表面の親水性が優れるため好ましい。According to the present invention, in manufacturing a medical device, particularly a contact lens, a step of contacting with a subcritical or supercritical fluid in a state where the medical device is built in the molding die, the molding die is separated. And a step of taking out the polymerized and molded medical device.
The molding die of the present invention is composed of upper and lower two molds, a polymerizable monomer, an oligomer, a polymer composition such as a macromer is put between the two molds and polymerized, and the molding molds after the polymerization are combined. That is, the mold is brought into contact with a subcritical or supercritical fluid in a state where the medical device is built in the mold. Any molding material can be used as long as it is a material that is not attacked by polymerizable monomers, oligomers, macromers, etc., but a molding material comprising one or more polymers selected from polymers having polar groups can be obtained. This is preferable because the surface of the tool is excellent in hydrophilicity.

【０００７】極性基を有するポリマーとしては、水酸
基、ニトリル基、カルボキシル基、ポリオキシエチレン
基、アミド基、ウレタン基、エステル基などの基を含有
するポリマーがあり、水との接触角が９０°以下のもの
が好ましい。その例としては、例えば、ポリアミド、ポ
リイミド、ポリウレタン、ポリエチレンテレフタレート
あるいはポリブチレンテレフタレートなどのポリエステ
ル、エチレンビニルアルコール共重合体、アクリロニト
リル−スチレン共重合体あるいはアクリロニトリル−メ
チルアクリレート共重合体などのアクリルニトリル共重
合体、スチレン−マレイン酸共重合体から選ばれた１種
以上のポリマーが挙げられる。特に接触角が７０°〜７
５°のものが得られる医療用具の親水性が優れるため好
ましく、この例としてはエチレンビニルアルコール共重
合体、ポリエチレンテレフタレートが挙げられる。As the polymer having a polar group, there is a polymer containing a group such as a hydroxyl group, a nitrile group, a carboxyl group, a polyoxyethylene group, an amide group, a urethane group and an ester group, and a contact angle with water is 90 °. The following are preferred. Examples thereof include, for example, polyester such as polyamide, polyimide, polyurethane, polyethylene terephthalate or polybutylene terephthalate, ethylene vinyl alcohol copolymer, acrylonitrile-styrene copolymer or acrylonitrile-methyl acrylate copolymer, etc. One or more polymers selected from coalesce and styrene-maleic acid copolymers. In particular, the contact angle is 70 ° to 7
A 5 ° -obtaining medical device is preferable because it is excellent in hydrophilicity, and examples thereof include ethylene vinyl alcohol copolymer and polyethylene terephthalate.

【０００８】本発明で使用する亜臨界ないしは超臨界流
体は、医療用具を侵食しないものであれば使用可能で特
に制約はなく、メタン、エタン、エチレン、クロロトリ
フルオロメタン、モノフルオロメタン、キセノン、亜酸
化窒素、二酸化炭素などが挙げられるが、材料に残留し
ないこと、入手が容易であり、安全性が高く取り扱い易
いことから二酸化炭素が好ましい。また、亜臨界ないし
は超臨界流体として、二酸化炭素９９．７重量％〜５０
重量％、及び超臨界二酸化炭素に溶解可能な有機物で、
極性を付与して流体の溶解能力を高める働きをするもの
（以下「エントレーナー」と称する）０．３重量％〜５
０重量％からなる流体も使用が可能で、エントレーナー
としては、水、メチルアルコール、エチルアルコール、
イソプロピルアルコールから選ばれた１種以上が使用で
きる。The subcritical or supercritical fluid used in the present invention can be used as long as it does not corrode medical devices and is not particularly limited, and methane, ethane, ethylene, chlorotrifluoromethane, monofluoromethane, xenon, Nitric oxide, carbon dioxide and the like can be mentioned, but carbon dioxide is preferred because it does not remain in the material, is easily available, is highly safe and is easy to handle. Further, as a subcritical or supercritical fluid, carbon dioxide 99.7% by weight to 50%
Wt%, and organic matter soluble in supercritical carbon dioxide,
0.3% by weight to 5 which imparts polarity and functions to enhance the dissolving ability of the fluid (hereinafter referred to as "entrainer")
A fluid containing 0% by weight can also be used, and as an entrainer, water, methyl alcohol, ethyl alcohol,
One or more selected from isopropyl alcohol can be used.

【０００９】本発明の亜臨界ないしは超臨界流体は、そ
の流体の特性に合わせて種々の温度、圧力で使用される
が、二酸化炭素を使用する場合、亜臨界流体は１５．８
℃〜３１℃の温度で、少なくとも４．９ＭＰａの圧力で
使用され、超臨界流体は３１℃超〜６０℃の温度で、少
なくとも７．４ＭＰａの圧力で使用される。接触させる
流体は亜臨界状態あるいは超臨界状態のいずれか一方だ
けでも良く、またその両方の状態で処理しても良い。処
理時間は成形型の形状、大きさ、医療用具の材質及びそ
の形状等に応じて決定されるが、一般的には３分以上処
理される。本発明で亜臨界ないしは超臨界流体に接触さ
れた成形用型は、その処理後に成形用型は分離され重合
成形された医療用具を取り出す。分離の方法は、二つに
合わさった型を逆にして内型を離脱する方法、真空吸引
機で内型を吸引して持ち上げて分離する方法、てこの原
理で内型をめくって外す方法等が使用できる。医療用具
はこの時に同時に分離されるか、一方の成形型に同伴さ
れて分離される。医療用具はそのまま、あるいは水によ
る膨潤工程など次工程に受け渡されて最終製品となる。The subcritical or supercritical fluid of the present invention is used at various temperatures and pressures according to the characteristics of the fluid. When carbon dioxide is used, the subcritical fluid is 15.8.
The supercritical fluid is used at a temperature of from 31 ° C to 31 ° C and a pressure of at least 4.9 MPa, and the supercritical fluid is used at a temperature of from 31 ° C to 60 ° C at a pressure of at least 7.4 MPa. The fluid to be contacted may be in either the subcritical state or the supercritical state, or may be treated in both of them. The treatment time is determined according to the shape and size of the molding die, the material of the medical device and its shape, etc., but generally 3 minutes or more is processed. In the present invention, the molding die brought into contact with the subcritical or supercritical fluid is separated from the molding die after the treatment, and the polymerized medical device is taken out. The method of separation is to remove the inner mold by reversing the two combined molds, suck the inner mold with a vacuum suction machine and lift it up, separate the inner mold by the lever principle, etc. Can be used. At this time, the medical devices are separated at the same time, or they are separated together with one of the molds. The medical device is passed through to the next process such as the process of swelling with water as it is, or the final product.

【００１０】本発明の医療用具は、上記の亜臨界ないし
は超臨界流体による処理時に同時にその中に残留してい
る、未重合モノマー、マクロマー、低分子生成物などの
不純物も抽出される。その抽出度合いは、医療用具の材
質、亜臨界ないしは超臨界流体の種類、使用温度、圧力
により異なるが、本発明の目的である成形用型の分離の
為には低分子成分のみの抽出が行われる条件が好まし
い。例えば、二酸化炭素を使用する場合、１６℃〜５０
℃の温度範囲、５Ｍｐａ〜２０Ｍｐａの圧力範囲で処理
される。特に、２５℃〜４０℃の温度範囲、６ＭＰａ〜
１６ＭＰａの圧力範囲で処理するのが、医療用具の形状
への影響が少なく、型分離性が良く好ましい。温度が高
すぎると、また圧力が２０ＭＰａを越えて高い条件で
は、逆に成形用型の分離性が悪くなり、医療用具を分離
し、取り出す時に表面に微少の欠陥が生じ易くなる。こ
の理由は定かではないが、これら条件では高分子成分ま
で抽出され、それにより医療用具特にコンタクトレンズ
の様に厚みが薄くかつ曲率を有する成形物は、抽出によ
り収縮が起きるため成形用型に吸着してしまう為と考え
られる。In the medical device of the present invention, impurities such as unpolymerized monomers, macromers and low molecular products which remain in the medical device at the time of treatment with the above-mentioned subcritical or supercritical fluid are also extracted. The degree of extraction depends on the material of the medical device, the type of subcritical or supercritical fluid, the operating temperature, and the pressure, but only the low molecular component is extracted for the purpose of separating the molding die, which is the object of the present invention. The conditions described are preferred. For example, when using carbon dioxide, 16 ° C to 50 ° C
It is processed in a temperature range of 5 ° C. and a pressure range of 5 Mpa to 20 Mpa. In particular, a temperature range of 25 ° C to 40 ° C, 6 MPa to
It is preferable that the treatment is carried out in the pressure range of 16 MPa because it has little influence on the shape of the medical device and the mold separation property is good. On the other hand, if the temperature is too high or the pressure exceeds 20 MPa and is high, the separability of the molding die is adversely affected, and minute defects are likely to occur on the surface when the medical device is separated and taken out. The reason for this is not clear, but under these conditions, even high molecular weight components are extracted, and as a result, molded products that have a thin thickness and a curvature, such as medical devices, particularly contact lenses, will shrink due to extraction and will be adsorbed to the molding die. It is thought to be because it does.

【００１１】本発明は、その表面の親水性が重要となる
医療用具一般に使用され、コンタクトレンズ、眼内レン
ズ、心臓弁、人工血管、人工輸尿管、横隔膜、腎臓透析
膜、人工肺、カテーテルなどに使用出来るが、特にコン
タクトレンズに有用である。コンタクトレンズとして
は、ハードレンズ、含水ソフトレンズおよび非含水ソフ
トレンズに使用でき、中でも酸素透過性が高いハードコ
ンタクトレンズ及びソフトコンタクトレンズに使用でき
る。特に、酸素透過係数が４０以上で、含水率が９％以
上である含水ソフトコンタクトレンズに好ましい。その
コンタクトレンズの素材には特に制限はないが、例え
ば、親水性シロキサニルメタアクリレート、親水性モノ
マー及び架橋剤を含む重合体からなるソフトコンタクト
レンズ、親水性シロキサニルマクロマー、親水性モノマ
ーび架橋剤を含む重合体からなるソフトコンタクトレン
ズなどが挙げられる。その具体例としては、例えば、少
なくとも以下のａ）の１種または２種以上およびｂ）の
１種または２種以上を重合してなる材料が挙げられる。INDUSTRIAL APPLICABILITY The present invention is generally used for medical devices in which hydrophilicity of the surface is important, and is used for contact lenses, intraocular lenses, heart valves, artificial blood vessels, artificial urinary tracts, diaphragms, renal dialysis membranes, artificial lungs, catheters, etc. It can be used, but is particularly useful for contact lenses. As the contact lens, it can be used for a hard lens, a water-containing soft lens and a non-water-containing soft lens, and especially for a hard contact lens and a soft contact lens having high oxygen permeability. In particular, it is preferable for a water-containing soft contact lens having an oxygen permeability coefficient of 40 or more and a water content of 9% or more. The material of the contact lens is not particularly limited, but examples thereof include soft siloxanyl methacrylate, a soft contact lens made of a polymer containing a hydrophilic monomer and a crosslinking agent, a hydrophilic siloxanyl macromer, and a hydrophilic monomer. Examples thereof include soft contact lenses made of a polymer containing a crosslinking agent. Specific examples thereof include, for example, materials obtained by polymerizing at least one or two or more of the following a) and one or more of the following b).

【００１２】ａ）式（１）で表される親水性ポリシロキ
サンモノマーA) Hydrophilic polysiloxane monomer represented by the formula (1)

【化１】 式中、Ｒ1 、Ｒ2 、Ｒ3 、Ｒ4 はそれぞれ炭素数１〜１
２の炭化水素基またはトリメチルシリル基から選ばれた
基である。[Chemical 1] In the formula, R 1 , R 2 , R 3 and R 4 each have 1 to 1 carbon atoms.
2 is a group selected from a hydrocarbon group or a trimethylsilyl group.

【００１３】Ｘは、次の式（２）で表される重合性置換
基である。X is a polymerizable substituent represented by the following formula (2).

【化２】 （ここで、Ｒ5 は水素又はメチル基、Ｚ1 は−ＮＨＣＯ
Ｏ−、−ＮＨＣＯＮＨ−、−ＯＣＯＮＨ−Ｒ6 −ＮＨＣ
ＯＯ−、−ＮＨＣＯＮＨ−Ｒ7 −ＮＨＣＯＮＨ−および
−ＯＣＯＮＨ−Ｒ8 −ＮＨＣＯＮＨ−、から選ばれた連
結基（Ｒ6 、Ｒ7、Ｒ8 は炭素数２〜１３の炭化水素
基）であり、ｍは０〜１０、ｎは３〜１０、ｐはｍが０
のとき０であり、ｍが１以上のとき１である。ｑは０〜
２０の整数である。）[Chemical 2] (Here, R 5 is hydrogen or a methyl group, Z 1 is —NHCO
O -, - NHCONH -, - OCONH-R 6 -NHC
OO -, - NHCONH-R 7 -NHCONH- and -OCONH-R 8 -NHCONH-, from selected linking groups (R 6, R 7, R 8 represents a hydrocarbon group having 2 to 13 carbon atoms), and m is 0 to 10, n is 3 to 10, and p is m
Is 0, and is 1 when m is 1 or more. q is 0
It is an integer of 20. )

【００１４】構造Ｙは下記式で表される構造単位［Ｉ］
および［II］が結合してなり、構造単位［Ｉ］と［II］
の結合数の比率は［Ｉ］／［II］＝０．１〜２００であ
り、［Ｉ］と［II］の合計数は１０〜１０００である。The structure Y is a structural unit [I] represented by the following formula.
And [II] are combined to form structural units [I] and [II]
The ratio of the number of bonds of [I] / [II] = 0.1 to 200, and the total number of [I] and [II] is 10 to 1000.

【化３】 （ここで、Ｒ9 及びＲ10は、それぞれ炭素数１〜１２の
炭化水素基、炭素数１〜１２のフッ素置換炭化水素基及
びトリメチルシロキシ基から選択された基であって、同
一でも異なっていてもよい。Ｒ11及びＲ12は、それぞれ
炭素数１〜１２の炭化水素基、トリメチルシロキシ基又
は親水性置換基からなる基であって、Ｒ11又はＲ12の少
なくとも一方は親水性置換基である。ここでいう親水性
置換基とは、水酸基、オキシアルキレン基から選ばれた
置換基が少なくとも１個結合してなる鎖状又は環状の炭
化水素基である。） ｂ）Ｎ−ビニル基を有するアミド基含有モノマー[Chemical 3] (Here, R 9 and R 10 are groups selected from a hydrocarbon group having 1 to 12 carbon atoms, a fluorine-substituted hydrocarbon group having 1 to 12 carbon atoms, and a trimethylsiloxy group, and they may be the same or different. R 11 and R 12 are each a hydrocarbon group having 1 to 12 carbon atoms, a trimethylsiloxy group or a hydrophilic substituent, and at least one of R 11 and R 12 is a hydrophilic substituent. The hydrophilic substituent as used herein is a chain or cyclic hydrocarbon group formed by bonding at least one substituent selected from a hydroxyl group and an oxyalkylene group.) B) N-vinyl group Amide group-containing monomer having

【００１５】具体的には以下の材料などが挙げられる。
上記式（１）における構造Ｙが下記式で表される構造単
位［Ｉ’］、［II’］および［III ’］が結合してなる
材料。Specifically, the following materials are listed.
A material obtained by combining the structural units [I ′], [II ′] and [III ′] represented by the following formula with the structure Y in the above formula (1).

【化４】 式中、Ｒ13は、親水性基であって、水酸基、オキシアル
キレン基から選ばれた置換基が少なくとも１個結合して
なる鎖状又は環状の炭化水素基である。上記の構造Ｙに
おいて、構造単位［Ｉ’］［II’］［III ’］の結合数
の比率が（［Ｉ’］＋［II’］）／［III ’］＝０．５
〜１００、［II’］／［Ｉ’］＝０〜１であり、さらに
［Ｉ’］と［II’］と［III ’］の合計数は１０〜１０
００である。[Chemical 4] In the formula, R 13 is a hydrophilic group, which is a chain or cyclic hydrocarbon group formed by bonding at least one substituent selected from a hydroxyl group and an oxyalkylene group. In the above structure Y, the ratio of the number of bonds of the structural units [I ′] [II ′] [III ′] is ([I ′] + [II ′]) / [III ′] = 0.5
˜100, [II ′] / [I ′] = 0 to 1, and the total number of [I ′], [II ′] and [III ′] is 10 to 10
00.

【００１６】上記式（１）の親水性ポリシロキサンモノ
マーの親水性置換基が次の式（３）または式（４）で表
される基である材料。A material in which the hydrophilic substituent of the hydrophilic polysiloxane monomer of the above formula (1) is a group represented by the following formula (3) or formula (4).

【化５】 −Ｒ14（ＯＨ）a （３） （ここで、Ｒ14は、炭素数３〜１２の炭化水素基であっ
て、炭素炭素間に、−Ｏ−、−ＣＯ−、−ＣＯＯ−から
なる基を挟んでいてもよく、−ＯＨ基は同一炭素原子上
には１個のみ置換され、ａは１より大きい数である。）Embedded image —R 14 (OH) a (3) (wherein R 14 is a hydrocarbon group having 3 to 12 carbon atoms, and among carbon carbons, —O—, —CO—, —COO A group consisting of-may be sandwiched, and only one -OH group is substituted on the same carbon atom, and a is a number larger than 1.)

【化６】 −Ｒ15−（ＯＲ16）b −ＯＺ2 （４） （ここで、Ｒ15は、炭素数３〜１２の炭化水素基であっ
て、炭素炭素間に、−Ｏ−、−ＣＯ−、−ＣＯＯ−から
なる基を挟んでいてもよい。Ｒ16は、炭素数２〜４の炭
化水素基であって、ｂが２以上の場合、異なる炭素数で
あってもよい。ｂは１〜２００であり、Ｚ2 は水素原
子、炭素数１〜１２の炭化水素基又は−ＯＣＯＲ17（Ｒ
17は炭素数１〜１２の炭化水素基）から選ばれた基を示
す。）Embedded image —R 15 — (OR 16 ) b —OZ 2 (4) (wherein R 15 is a hydrocarbon group having 3 to 12 carbon atoms, and between carbon carbons, —O—, — R 16 may be a hydrocarbon group having 2 to 4 carbon atoms, and when b is 2 or more, R 16 may have different carbon numbers. Is 1 to 200, Z 2 is a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or —OCOR 17 (R
17 represents a group selected from a hydrocarbon group having 1 to 12 carbon atoms). )

【００１７】上記式（１）の親水性ポリシロキサンモノ
マーの親水性置換基が次の式（５）、式（６）、式
（７）より選ばれてなる材料。A material in which the hydrophilic substituent of the hydrophilic polysiloxane monomer of the above formula (1) is selected from the following formulas (5), (6) and (7).

【化７】 −Ｃ3 Ｈ6 ＯＨ （５） −Ｃ3 Ｈ6 ＯＣＨ2 ＣＨ（ＯＨ）ＣＨ2 ＯＨ （６） −Ｃ3 Ｈ6 ＯＣ2 Ｈ4 ＯＨ （７） 上記式（１）の親水性ポリシロキサンモノマーの親水性
基が次の式（８）または（９）式より選ばれてなる材
料。Embedded image —C 3 H 6 OH (5) —C 3 H 6 OCH 2 CH (OH) CH 2 OH (6) —C 3 H 6 OC 2 H 4 OH (7) Hydrophilicity of the above formula (1) A material in which the hydrophilic group of the polysiloxane monomer is selected from the following formula (8) or (9).

【化８】 −Ｃ3 Ｈ6 （ＯＣ2 Ｈ4 ）c ＯＨ （８） −Ｃ3 Ｈ6 （ＯＣ2 Ｈ4 ）d ＯＣＨ3 （９） （ｃ、ｄは２〜４０である。）Embedded image —C 3 H 6 (OC 2 H 4 ) c OH (8) —C 3 H 6 (OC 2 H 4 ) d OCH 3 (9) (c and d are 2 to 40)

【００１８】化合物ｂ）のＮ−ビニル基を有するアミド
基含有モノマーが、Ｎ−ビニルホルムアミド、Ｎ−ビニ
ルアセトアミド、Ｎ−ビニルイソプロピルアミド、Ｎ−
ビニル−Ｎ−メチルアセトアミド、Ｎ−ビニルピロリド
ン、Ｎ−ビニルカプロラクタムから選ばれてなる材料。 化合物ａ）親水性ポリシロキサンモノマーが１０〜９９
重量％、化合物ｂ）Ｎ−ビニル基を有するアミド基含有
モノマーが１〜８０重量％である共重合体からなる材
料。The amide group-containing monomer having an N-vinyl group of the compound b) is N-vinylformamide, N-vinylacetamide, N-vinylisopropylamide, N-
A material selected from vinyl-N-methylacetamide, N-vinylpyrrolidone, and N-vinylcaprolactam. Compound a) hydrophilic polysiloxane monomer is 10 to 99
%, Compound b) A material comprising a copolymer having an N-vinyl group-containing amide group-containing monomer in an amount of 1 to 80% by weight.

【００１９】本発明の材料には架橋性モノマーを含んで
も良く、たとえば、式（１０）に示す架橋性モノマーを
含んで共重合してなる材料。The material of the present invention may contain a crosslinkable monomer, for example, a material obtained by copolymerizing the crosslinkable monomer represented by the formula (10).

【化９】 ［ここで、Ｒ16及びＲ18は、水素原子又はメチル基でで
あり、同じでも異なっていてもよい。Ｚ3 は、−ＮＨＣ
ＯＯ−連結基であり、Ｒ17は炭素数２〜１０の炭化水素
基又は−（ＣＨＯ）ＣＨ−で表されるポリオキシエチレ
ン基（ｇは２〜４０を表す）から選択され、ｆは０〜１
０、ｅはｆが０のとき０であり、ｆが１以上のとき１で
ある。］[Chemical 9] [Here, R 16 and R 18 are a hydrogen atom or a methyl group, and may be the same or different. Z 3 is -NHC
Is an OO-linking group, R 17 is selected from a hydrocarbon group having 2 to 10 carbon atoms or a polyoxyethylene group represented by — (CHO) CH— (g represents 2 to 40), and f is 0. ~ 1
0 and e are 0 when f is 0 and 1 when f is 1 or more. ]

【００２０】下記式（１１）で示す架橋性モノマーを含
んで共重合してなる材料。A material obtained by copolymerization containing a crosslinkable monomer represented by the following formula (11).

【化１０】 [Chemical 10]

【００２１】[0021]

【実施例】以下に実施例、比較例を用いて本発明を更に
詳細に説明する。なお、実施例、比較例におけるレンズ
特性の評価方法は以下の通りである。 １．含水率 レンズを生理食塩水に３７℃で７２時間静置した後、レ
ンズを取り出し表面付着水を拭き取り秤量した。次に８
０℃で真空下で恒量になるまで乾燥し、その重量を秤量
し重量変化から下式により求めた。 含水率（％）＝（重量変化／乾燥前重量）×１００ ２．酸素透過係数 コンタクトレンズ協会標準Ｄｋ値測定法に準じて理化精
機工業（株）製のＫ−３１６−Ｉ；ＰＩ型フィルム酸素
透過測定装置を使用して電極法により測定した。試料片
は直径約１４ｍｍ、厚さ約０．１〜０．５ｍｍのレンズ
を鋳型で作製し測定に供した。測定は３５℃で生理食塩
水中で測定した。試料厚みに対する酸素透過量の傾きか
ら酸素透過係数を求めた。単位は（ｍｌ・ｃｍ／ｃｍ2
・ｓｅｃ・ｍｍＨｇ）×１０-11 で表した。EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples. The evaluation methods of the lens characteristics in the examples and comparative examples are as follows. 1. The water content lens was allowed to stand in physiological saline at 37 ° C. for 72 hours, and then the lens was taken out and water adhering to the surface was wiped off and weighed. Then 8
It was dried under vacuum at 0 ° C. until a constant weight was obtained, the weight was weighed, and the change in weight was determined by the following formula. Water content (%) = (weight change / weight before drying) × 100 2. Oxygen Permeability Coefficient K-316-I manufactured by Rika Seiki Co., Ltd .; PI type film oxygen permeation measuring device was used to measure by the electrode method according to the standard Dk value measuring method of the Contact Lens Association. As a sample piece, a lens having a diameter of about 14 mm and a thickness of about 0.1 to 0.5 mm was prepared using a mold and provided for measurement. The measurement was carried out at 35 ° C. in physiological saline. The oxygen permeability coefficient was determined from the slope of the oxygen permeability with respect to the sample thickness. The unit is (ml ・ cm / cm 2
・ Sec · mmHg) × 10 -11

【００２２】３．水濡れ性 精製水中に浸漬していたレンズを取り出し、表面の付着
水をふき取った後、２５℃で１０分間放置。続いて精製
水中に１０秒間浸漬した後、垂直に引き上げ水濡れ性を
評価した。水膜が５秒以上保持される水濡れ性を良好、
１〜５秒のものを可、１秒以下の場合を不可とした。 ４．接触角 接触角測定装置（協和界面科学（株）製ＣＡ−ＤＴ型）
を用い、２５℃で材料表面と水滴との接触角を測定し
た。 ５．光学的透明性 目視による。曇りなく透明性なものを良好、曇りがあり
半透明なものを可、白濁し不透明ないものを不可とし
た。3. The lens that had been immersed in purified water was taken out, the water adhering to the surface was wiped off, and the lens was left at 25 ° C for 10 minutes. Then, after immersing in purified water for 10 seconds, it was pulled up vertically and water wettability was evaluated. Good water wettability that keeps water film for 5 seconds or more,
The case of 1 to 5 seconds was acceptable, and the case of 1 second or less was not acceptable. 4. Contact angle Contact angle measuring device (CA-DT type manufactured by Kyowa Interface Science Co., Ltd.)
Was used to measure the contact angle between the material surface and the water droplets at 25 ° C. 5. Optical transparency Visual inspection. Those that were transparent without clouding were rated as good, those that were cloudy and translucent were acceptable, and those that were cloudy and not opaque were rated as unusable.

【００２３】[0023]

【実施例１】［ヒドロシラン基含有ポリシロキサンジオ
ール（Ａ１）の合成］オクタメチルシクロテトラシロキ
サン１５０ｇ、１，３，５−トリメチルトリフルオロプ
ロピルシクロトリシロキサン２２．６ｇ、１，３，５，
７−テトラメチルシクロテトラシロキサン１７．４ｇ、
１，３−ビス（４−ヒドロキシプロピル）テトラメチル
ジシロキサン７．２ｇ、クロロホルム２００ｇ、トリフ
ルオロメタンスルホン酸１．５ｇ、をフラスコ中で２５
℃、２４時間撹拌後、ｐＨが中性になるまで精製水で繰
り返し洗浄する。水を分離後、クロロホルムを減圧下で
留去した。残液をイソプロパノールに溶解、メタノール
で再沈澱し分離した液を真空下で揮発分を除いたとこ
ろ、透明粘凋液が得られた。下記式で表されるヒドロシ
ランを有するシロキサンジオール（Ａ１）を９８ｇ得
た。なお、連結基Ｙの構造式が各シロキサンのブロック
体であるかのような式を示しているが、実際はランダム
構造を含んでおり、ここでは各シロキサンの割合のみを
表す。以下の合成例においても同様である。[Example 1] [Synthesis of hydrosilane group-containing polysiloxane diol (A1)] Octamethylcyclotetrasiloxane 150 g, 1,3,5-trimethyltrifluoropropylcyclotrisiloxane 22.6 g, 1,3,5
17.4 g of 7-tetramethylcyclotetrasiloxane,
25 g of 1,3-bis (4-hydroxypropyl) tetramethyldisiloxane 7.2 g, chloroform 200 g, trifluoromethanesulfonic acid 1.5 g were placed in a flask.
After stirring at ℃ for 24 hours, repeatedly wash with purified water until the pH becomes neutral. After separating water, chloroform was distilled off under reduced pressure. The residual liquid was dissolved in isopropanol, reprecipitated with methanol, and the separated liquid was subjected to removal of volatile components under vacuum to obtain a transparent viscous liquid. 98 g of siloxane diol (A1) having hydrosilane represented by the following formula was obtained. Although the structural formula of the linking group Y is shown as if it is a block of each siloxane, it actually includes a random structure, and only the proportion of each siloxane is shown here. The same applies to the following synthesis examples.

【００２４】[0024]

【化１１】 [Chemical 11]

【００２５】［ヒドロシラン基含有ポリシロキサンジメ
タクリレート（Ｂ１）の合成］上記ポリシロキサンジオ
ール（Ａ１）５０ｇ、メタクリロイルオキシエチルイソ
シアネート３．９ｇ、乾燥アセトン１００ｇ、ジブチル
チンジラウリレート０．０２ｇ、を褐色フラスコ中に加
え、窒素雰囲気下で２５℃、２４時間撹拌した後、精製
水１．４ｇを加えさらに３時間撹拌する。アセトンを減
圧下で留去し、残液をメタノールで洗浄後、再度真空下
で揮発分を除去したところ、透明な粘凋液が得られた。
下記式で表されるヒドロシラン基を有するポリシロキサ
ンジメタクリレート（Ｂ１）４８．７ｇが得られた。[Synthesis of Hydrosilane Group-Containing Polysiloxane Dimethacrylate (B1)] 50 g of the above polysiloxane diol (A1), methacryloyloxyethyl isocyanate 3.9 g, dry acetone 100 g, and dibutyltin dilaurylate 0.02 g were placed in a brown flask. In addition, the mixture is stirred under a nitrogen atmosphere at 25 ° C. for 24 hours, 1.4 g of purified water is added, and the mixture is further stirred for 3 hours. Acetone was distilled off under reduced pressure, the residual liquid was washed with methanol, and then the volatile matter was removed again under vacuum, whereby a transparent viscous liquid was obtained.
48.7 g of polysiloxane dimethacrylate (B1) having a hydrosilane group represented by the following formula was obtained.

【００２６】[0026]

【化１２】 [Chemical 12]

【００２７】［アルコール基含有ポリシロキサンジメタ
クリレート（Ｃ１）の合成］上記ポリシロキサンジメタ
クリレート（Ｂ１）４８ｇ、アリルアルコール１１．６
ｇ、イソプロピルアルコール９６ｇ、酢酸カリウム０．
０４ｇ、塩化白金酸１０ｍｇ、ジ−ｔ−ブチルクレゾー
ル１０ｍｇを還流冷却器付きフラスコに仕込み、窒素雰
囲気下で５０℃で３時間加熱撹拌した。反応液をろ別
後、イソプロパノールを減圧下で留去したのち、メタノ
ール／水混合液で洗浄した。さらに真空下で、揮発分を
除去したところ、透明な粘凋液が得られた。下記式で示
されるアルコール基含有ポリシロキサンジメタクリレー
ト（Ｃ１）であった。[Synthesis of polysiloxane dimethacrylate (C1) containing alcohol group] 48 g of the above polysiloxane dimethacrylate (B1), 11.6 of allyl alcohol
g, isopropyl alcohol 96 g, potassium acetate 0.
04 g, 10 mg of chloroplatinic acid, and 10 mg of di-t-butylcresol were charged into a flask equipped with a reflux condenser, and heated and stirred at 50 ° C. for 3 hours under a nitrogen atmosphere. After separating the reaction solution by filtration, isopropanol was distilled off under reduced pressure, followed by washing with a methanol / water mixed solution. Further, when the volatile matter was removed under vacuum, a transparent viscous liquid was obtained. It was an alcohol group-containing polysiloxane dimethacrylate (C1) represented by the following formula.

【００２８】[0028]

【化１３】 [Chemical 13]

【００２９】上記合成例に記載のアルコール基含有ポリ
シロキサンジメタクリレート（Ｃ１）８０重量部、Ｎ−
ビニル−Ｎ−メチルアセトアミド（以下「ＶＭＡ」と称
す）１０重量部、イソボルニルメタクリレート（以下
「ＩＢＭ」と称す）５重量部、テトラエチレングリコー
ルジメタクリレート（以下「４ＥＤ」と称す）５重量部
及び２，４，６−トリメチルベンゾイルジフェニルホス
フィンオキサイド（以下「ＴＰＯ」と称す）０．５重量
部を添加し、撹拌混合させた。その後、ポリエチレンビ
ニルアルコール樹脂（以下「ＥＶＯＨ」樹脂と称す）
（日本合成化学工業株式会社製；ソワライトＳ）からな
るコンタクトレンズ成形用鋳型中にモノマー混合液を入
れ、光照射装置内で１時間紫外線を照射したところ、レ
ンズ状の重合体を得た。80 parts by weight of the alcohol group-containing polysiloxane dimethacrylate (C1) described in the above synthesis example, N-
10 parts by weight of vinyl-N-methylacetamide (hereinafter referred to as "VMA"), 5 parts by weight of isobornyl methacrylate (hereinafter referred to as "IBM"), 5 parts by weight of tetraethylene glycol dimethacrylate (hereinafter referred to as "4ED") And 0.5 part by weight of 2,4,6-trimethylbenzoyldiphenylphosphine oxide (hereinafter referred to as "TPO") were added and mixed with stirring. After that, polyethylene vinyl alcohol resin (hereinafter referred to as "EVOH" resin)
When a monomer mixture liquid was placed in a contact lens molding mold made of (Nippon Gosei Kagaku Kogyo Co., Ltd .; Sowarite S) and irradiated with ultraviolet rays for 1 hour in a light irradiation device, a lens-shaped polymer was obtained.

【００３０】得られた重合体を内包する成形用型１０個
を超臨界流体処理設備（サーモセパレーションプロダク
ツ（株）製；Ｘ−１０型）にて、二酸化炭素で４０℃の
温度、１２ＭＰａの圧力で８分間処理した。取り出した
成形用型を逆さにするか、てこで軽く開くと型が分離
し、レンズは片方の型に付着して得られた。続いてレン
ズが付着した型を水に浸漬してレンズを剥離し、９０℃
にて３時間加熱して完全に含水したレンズを得た。得ら
れたレンズは欠け、割れ等の欠陥が無く、透明で柔軟性
があり、水濡れ性も良好であった。物性を評価したとこ
ろ含水率１０％、酸素透過係数（Ｄｋ）は２５６×１０
-11 であった。なお、用いたＥＶＯＨ樹脂の水との接触
角は７３°であった。Ten molding dies containing the obtained polymer were placed in a supercritical fluid treatment facility (Thermo Separation Products Co., Ltd .; Model X-10) with carbon dioxide at a temperature of 40 ° C. and a pressure of 12 MPa. For 8 minutes. When the molding die taken out was turned upside down or lightly opened with a lever, the molds were separated, and the lens was obtained by adhering to one mold. Then, the mold to which the lens is attached is immersed in water to peel off the lens,
After that, the lens was heated for 3 hours to obtain a lens containing water completely. The obtained lens was free from defects such as chipping and cracking, was transparent and flexible, and had good wettability with water. When the physical properties were evaluated, the water content was 10% and the oxygen permeability coefficient (Dk) was 256 × 10.
It was -11 . The contact angle of the EVOH resin used with water was 73 °.

【００３１】[0031]

【実施例２】実施例１において、超臨界流体の処理を５
０℃の温度、１０ＭＰａの圧力で行った他は同様の方法
でレンズを得た。型の分離は容易に行われ、得られたレ
ンズは欠陥が無く透明なレンズで、水濡れ性は良好であ
った。[Embodiment 2] In Embodiment 1, the treatment of the supercritical fluid is carried out 5 times.
A lens was obtained in the same manner except that the temperature was 0 ° C. and the pressure was 10 MPa. The molds were easily separated, and the obtained lens was a defect-free transparent lens and had good water wettability.

【実施例３】実施例１において、超臨界流体の処理を３
３℃の温度、１６ＭＰａの圧力で行った他は同様の方法
でレンズを得た。型の分離は容易に行われ、得られたレ
ンズは全て欠陥が無く透明なレンズで、水濡れ性は良好
であった。[Embodiment 3] In Embodiment 1, the treatment of the supercritical fluid is performed 3 times.
A lens was obtained by the same method except that the temperature was 3 ° C. and the pressure was 16 MPa. The molds were separated easily, and all the obtained lenses were defect-free and transparent and had good water wettability.

【００３２】[0032]

【実施例４】実施例１において、超臨界流体の処理を３
０℃の温度、６ＭＰａの圧力で３０分間行った他は同様
の方法でレンズを得た。型の分離は容易に行われ、得ら
れたレンズは全て欠陥が無く透明なレンズで、水濡れ性
は良好で、含水率１１％、酸素透過係数（Ｄｋ）は２５
０×１０-11 であった。[Fourth Embodiment] In the first embodiment, the treatment of the supercritical fluid is performed three times.
A lens was obtained in the same manner except that the temperature was 0 ° C. and the pressure was 6 MPa for 30 minutes. The molds were easily separated, all the obtained lenses were transparent without defects, had good water wettability and had a water content of 11% and an oxygen permeability coefficient (Dk) of 25.
It was 0 × 10 -11 .

【実施例５】実施例１において、超臨界流体の処理を２
５℃の温度、６．５ＭＰａの圧力で１０分間、次いで３
５℃の温度、１２．５ＭＰａの圧力で１０分間行った他
は同様の方法でレンズを得た。型の分離は容易に行わ
れ、得られたレンズは全て欠陥が無く透明なレンズで、
水濡れ性は良好で、含水率１１％、酸素透過係数（Ｄ
ｋ）は２６０×１０-11 であった。[Fifth Embodiment] In the first embodiment, the treatment of the supercritical fluid is performed in two.
10 minutes at a temperature of 5 ° C. and a pressure of 6.5 MPa, then 3
A lens was obtained in the same manner except that the temperature was 5 ° C. and the pressure was 12.5 MPa for 10 minutes. The molds are easily separated, and all the obtained lenses are defect-free and transparent lenses.
Good water wettability, water content 11%, oxygen permeability coefficient (D
k) was 260 × 10 -11 .

【００３３】[0033]

【比較例１】実施例１において、重合後得られた重合体
を内包する成形用型を、超臨界流体で処理することに変
えて、そのまま型を分離する試みをしたが、２つの成形
型は強固に接合し容易に分離できなかった。分離できて
もレンズが破損し製品は得られなかった。[Comparative Example 1] In Example 1, an attempt was made to separate the molds as they were, instead of treating the molding mold containing the polymer obtained after polymerization with a supercritical fluid. Was strongly bonded and could not be easily separated. Even if they could be separated, the lens was damaged and no product was obtained.

【比較例２】実施例１において、重合後得られた重合体
を内包する成形用型を、超臨界流体で処理することに変
えてエチルアルコール中に浸漬した。３０分浸漬しても
型の分離は不可能で、無理に分離させるとレンズが破損
した。エチルアルコール中に一晩浸漬して同様にレンズ
を得た。得られたレンズは実施例１とほぼ同じ品質のレ
ンズであったが、一部のレンズではレンズ端部に微細な
欠けが認められた。型の分離が可能になるまでにアルコ
ール中に一晩浸漬する必要があることが明らかとなっ
た。Comparative Example 2 The molding die containing the polymer obtained after the polymerization in Example 1 was immersed in ethyl alcohol instead of being treated with a supercritical fluid. The molds could not be separated even after soaking for 30 minutes, and the lenses were damaged if they were forcibly separated. A lens was similarly obtained by immersing it in ethyl alcohol overnight. The obtained lens had almost the same quality as that of Example 1, but some of the lenses had fine cracks at the lens end. It became clear that it was necessary to soak in alcohol overnight before the molds could be separated.

【００３４】[0034]

【比較例３】実施例１において、超臨界流体処理を二酸
化炭素の５０℃の温度、２５ＭＰａの圧力で１２０分間
行った他は同様に処理した。得られた成形用型を分離し
ようと試みたが、１０個中８個は型が強く接合し分離は
困難で、分離してもレンズが破損した。２個は比較的容
易に分離可能であったが、レンズ端部に微少な欠け、キ
ズが認められた。Comparative Example 3 The same treatment as in Example 1 was carried out except that the supercritical fluid treatment was carried out at a temperature of 50 ° C. of carbon dioxide at a pressure of 25 MPa for 120 minutes. Attempts were made to separate the obtained molding dies, but 8 out of 10 dies were strongly bonded and the separation was difficult, and the lenses were damaged even if they were separated. The two could be separated relatively easily, but slight chipping and scratches were observed at the end of the lens.

【比較例４】実施例１において、使用した成形用型をポ
リプロピレン製のものに変えた他は同様にしてレンズを
製作した。超臨界流体で処理した成形型は簡単に分離
し、レンズも一部が型から剥離していた。含水したレン
ズには欠け、割れ等の欠陥が無く、透明で柔軟性があ
り、物性を評価したところ含水率１０％、酸素透過係数
（Ｄｋ）は２５５×１０-11 であった。しかし、水濡れ
性は不可でレンズ表面はほとんど水濡れが無い様態であ
った。なお、用いたポリプロピレン樹脂の水との接触角
は１１０°であった。COMPARATIVE EXAMPLE 4 A lens was manufactured in the same manner as in Example 1 except that the molding die used was made of polypropylene. The mold treated with the supercritical fluid easily separated, and the lens partly peeled from the mold. The hydrated lens was free from defects such as chipping and cracking, was transparent and flexible, and was evaluated for its physical properties to have a water content of 10% and an oxygen permeability coefficient (Dk) of 255 × 10 -11 . However, the wettability was not possible, and the lens surface was in a state that there was almost no wettability. The contact angle of the polypropylene resin used with water was 110 °.

【００３５】[0035]

【発明の効果】本発明は、医療用具として使用するポリ
マーの成形品を成形用鋳型の中で重合成形して、重合後
に当該成形型から容易に分離して取り出す方法に関す
る。更に詳細には、本発明は、重合成形された医療用具
の中の未重合物などの不純物をその成形型ごと抽出し、
成形型の分離を容易にし、かつ取り出す方法で従来２４
時間以上の処理時間が必要であった型分離工程を数分で
可能とし、得られる製品の品質も優れたものとする方法
を提供する。INDUSTRIAL APPLICABILITY The present invention relates to a method of polymer-molding a polymer molded article used as a medical device in a molding mold, and easily separating and taking it out from the molding die after polymerization. More specifically, the present invention extracts impurities such as unpolymerized substances in the polymerized and molded medical device together with its molding die,
Conventionally, the method for facilitating the separation of the molding die and taking it out is 24
Provided is a method for enabling a mold separation step, which required a processing time longer than time, in a few minutes and improving the quality of the obtained product.

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｂ２９Ｋ 77:00 Ｂ２９Ｋ 77:00 79:00 79:00 Ｂ２９Ｌ 11:00 Ｂ２９Ｌ 11:00 ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) B29K 77:00 B29K 77:00 79:00 79:00 B29L 11:00 B29L 11:00

Claims (11)

【特許請求の範囲】[Claims] 【請求項１】 成形用型において重合成形された医療用
具から不純物を抽出後、医療用具を成形用型から取り出
す方法であって、該成形用型に医療用具が内蔵した状態
で亜臨界ないしは超臨界流体に接触させる工程、成形用
型を分離し重合成形された医療用具を取り出す工程を含
むことを特徴とする方法。1. A method for extracting impurities from a medical device which is polymerized and molded in a molding die and then removing the medical device from the molding die, wherein the molding tool has a subcritical or supercritical state. A method comprising the steps of contacting with a critical fluid and separating a molding die and taking out a polymerized medical device. 【請求項２】 成形用型が極性基を有するポリマーから
選択された１種以上のポリマーからなることを特徴とす
る請求項１に記載の方法。2. The method according to claim 1, wherein the mold comprises one or more polymers selected from polymers having polar groups. 【請求項３】 亜臨界ないしは超臨界流体が二酸化炭素
である請求項１又は２に記載の方法。3. The method according to claim 1, wherein the subcritical or supercritical fluid is carbon dioxide. 【請求項４】 医療用具がコンタクトレンズである請求
項１〜３のいずれかに記載の方法。4. The method according to claim 1, wherein the medical device is a contact lens. 【請求項５】 極性基を有するポリマーが、水酸基、ニ
トリル基、カルボキシル基、ポリオキシエチレン基、ア
ミド基、ウレタン基、エステル基のいずれかの基を含有
するポリマーである請求項２〜４のいずれかに記載の方
法。5. The polymer having a polar group is a polymer containing any one of a hydroxyl group, a nitrile group, a carboxyl group, a polyoxyethylene group, an amide group, a urethane group and an ester group. The method described in either. 【請求項６】 極性基を有するポリマーが、水との接触
角が９０°以下のものである請求項２〜５のいずれかに
記載の方法。6. The method according to claim 2, wherein the polymer having a polar group has a contact angle with water of 90 ° or less. 【請求項７】 極性基を有するポリマーが、ポリアミ
ド、ポリイミド、ポリウレタン、ポリエチレンテレフタ
レート、ポリブチレンテレフタレート、エチレンビニル
アルコール共重合体、アクリロニトリル−スチレン共重
合体、アクリロニトリル−メチルアクリレート共重合
体、スチレン−マレイン酸共重合体から選ばれた１種以
上のポリマーである請求項２〜６のいずれかに記載の方
法。7. The polymer having a polar group is polyamide, polyimide, polyurethane, polyethylene terephthalate, polybutylene terephthalate, ethylene vinyl alcohol copolymer, acrylonitrile-styrene copolymer, acrylonitrile-methyl acrylate copolymer, styrene-malein. The method according to any one of claims 2 to 6, which is one or more polymers selected from acid copolymers. 【請求項８】 亜臨界ないしは超臨界流体が二酸化炭素
９９．７重量％〜５０重量％及びエントレーナー０．３
重量％〜５０重量％からなる請求項１〜７のいずれかに
記載の方法。8. The subcritical or supercritical fluid comprises 99.7% to 50% by weight of carbon dioxide and 0.3 of an entrainer.
The method according to any one of claims 1 to 7, which comprises 50% by weight to 50% by weight. 【請求項９】 エントレーナーが、水、メチルアルコー
ル、エチルアルコール、イソプロピルアルコールから選
ばれた１種以上である請求項８に記載の方法。9. The method according to claim 8, wherein the entrainer is one or more selected from water, methyl alcohol, ethyl alcohol and isopropyl alcohol. 【請求項１０】 亜臨界ないし超臨界流体が、１６℃〜
６０℃の温度で、少なくとも４．９Ｍｐａの圧力である
請求項１〜９のいずれかに記載の方法。10. The subcritical or supercritical fluid has a temperature of 16 ° C. or higher.
10. A method according to any of claims 1 to 9 at a temperature of 60 <0> C and a pressure of at least 4.9 Mpa. 【請求項１１】 医療用具が酸素透過係数が４０以上で
であり、含水率が９％以上である含水ソフトコンタクト
レンズである請求項１〜１０のいずれかに記載の方法。11. The method according to claim 1, wherein the medical device is a water-containing soft contact lens having an oxygen permeability coefficient of 40 or more and a water content of 9% or more.
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007160706A (en) * 2005-12-14 2007-06-28 Asahi Kasei Aimii Kk Resin mold for polymerization
JP2007526946A (en) * 2004-03-05 2007-09-20 ジョンソン・アンド・ジョンソン・ビジョン・ケア・インコーポレイテッド Wet hydrogel containing acyclic polyamide
JP2010020330A (en) * 1995-04-04 2010-01-28 Novartis Ag Extended wear ophthalmic lens
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US20140004609A1 (en) * 2012-06-29 2014-01-02 Johnson & Johnson Vision Care, Inc. Method of quantifying uv disinfecting doses using indicators
US8696115B2 (en) 2005-02-14 2014-04-15 Johnson & Johnson Vision Care, Inc. Comfortable ophthalmic device and methods of its production
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JP2010020330A (en) * 1995-04-04 2010-01-28 Novartis Ag Extended wear ophthalmic lens
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US8022158B2 (en) 2004-03-05 2011-09-20 Johnson & Johnson Vision Care, Inc. Wettable hydrogels comprising acyclic polyamides
US8222353B2 (en) 2004-03-05 2012-07-17 Johnson & Johnson Vision Care, Inc. Wettable hydrogels comprising acyclic polyamides
US10267952B2 (en) 2005-02-14 2019-04-23 Johnson & Johnson Vision Care, Inc. Comfortable ophthalmic device and methods of its production
US8696115B2 (en) 2005-02-14 2014-04-15 Johnson & Johnson Vision Care, Inc. Comfortable ophthalmic device and methods of its production
US11953651B2 (en) 2005-02-14 2024-04-09 Johnson & Johnson Vision Care, Inc. Comfortable ophthalmic device and methods of its production
US11150383B2 (en) 2005-02-14 2021-10-19 Johnson & Johnson Vision Care, Inc. Comfortable ophthalmic device and methods of its production
US9395559B2 (en) 2005-02-14 2016-07-19 Johnson & Johnson Vision Care, Inc. Comfortable ophthalmic device and methods of its production
JP2007160706A (en) * 2005-12-14 2007-06-28 Asahi Kasei Aimii Kk Resin mold for polymerization
US9052529B2 (en) 2006-02-10 2015-06-09 Johnson & Johnson Vision Care, Inc. Comfortable ophthalmic device and methods of its production
JP2011051098A (en) * 2009-08-31 2011-03-17 Olympus Corp Method of manufacturing optical element, and the optical element
US20140004609A1 (en) * 2012-06-29 2014-01-02 Johnson & Johnson Vision Care, Inc. Method of quantifying uv disinfecting doses using indicators
RU2578452C2 (en) * 2012-06-29 2016-03-27 Джонсон Энд Джонсон Вижн Кэа, Инк. Method for quantitative determination of disinfectant uv- radiation dose using indicators
US9244013B2 (en) * 2012-06-29 2016-01-26 Johnson & Johnson Vision Care, Inc. Method of quantifying UV disinfecting doses applied to an ophthalmic lens using indicators

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