JPWO2020009747A5

JPWO2020009747A5 -

Info

Publication number: JPWO2020009747A5
Application number: JP2020573441A
Authority: JP
Publication date: 2022-04-06
Anticipated expiration: 2039-05-17

Description

本明細書に開示される実施形態に様々な修正を加えることができることが理解されるであろう。したがって、上記の説明は、限定的と解釈されるべきではなく、好ましい実施形態の例示としてのみ解釈されるべきである。例えば、上述され、本発明を動作させるための最良の態様として実装される機能は、例示目的のみのためである。当業者であれば、本発明の範囲および趣旨から逸脱することなく、他の構成および方法を実施することができる。さらに、当業者は、本明細書に追加される特徴および利点の範囲および趣旨内で他の修正を想定するであろう。
なお、下記［１］から［４１］は、いずれも本発明の一形態又は一態様である。
［１］
モノマー混合物の重合生成物である、水抽出可能な眼科用デバイスであって、前記モノマー混合物が、
（ａ）１つ以上の環状ラクタムと、
（ｂ）１つ以上のシロキサニル単位、および１つ以上のシリルアルキルシロキサニル単位を含む、１つ以上の有機ケイ素含有ブロックコポリマーであって、エチレン性不飽和反応性末端基を有する、１つ以上の有機ケイ素含有ブロックコポリマーと、
（ｃ）１つ以上の嵩高いシロキサンモノマーと、
（ｄ）架橋剤混合物であって、（ｉ）少なくとも２つのエチレン性不飽和反応性末端基を含有する、１つ以上の第１の架橋剤であって、前記少なくとも２つのエチレン性不飽和反応性末端基が、（メタ）アクリレート含有反応性末端基である、１つ以上の第１の架橋剤、および（ｉｉ）少なくとも２つのエチレン性不飽和反応性末端基を含有する、１つ以上の第２の架橋剤であって、前記エチレン性不飽和反応性末端基のうちの少なくとも１つが、非（メタ）アクリレート反応性末端基である、１つ以上の第２の架橋剤、を含む、架橋剤混合物と、を含み、
前記水抽出可能な眼科用デバイスが、少なくとも約５０重量％の平衡水含有量、約５０°未満の接触角、および少なくとも約６０バーラーの酸素透過度を有する、水抽出可能な眼科用デバイス。
［２］
約５０重量％～約７０重量％の平衡水含有量、約３０°～約５０°の接触角、および少なくとも約７０バーラーの酸素透過度を有する、［１］に記載の水抽出可能な眼科用デバイス。
［３］
約５５重量％～約６５重量％の平衡水含有量、約３０°～約４５°の接触角、および少なくとも約７０バーラーの酸素透過度を有する、［１］に記載の水抽出可能な眼科用デバイス。
［４］
約１５重量％未満の水抽出物含有量をさらに有する、［１］～［３］に記載の水抽出可能な眼科用デバイス。
［５］
前記モノマー混合物中に存在する前記１つ以上の環状ラクタムの量が、前記モノマー混合物の総重量に基づいて、約５５重量％以下の量である、［１］～［４］に記載の水抽出可能な眼科用デバイス。
［６］
前記１つ以上の環状ラクタムが、Ｎ－ビニル－２－ピロリドン、Ｎ－ビニルカプロラクタム、Ｎ－ビニル－２－ピペリドン、およびこれらの混合物からなる群から選択される、［１］～［５］に記載の水抽出可能な眼科用デバイス。
［７］
前記１つ以上の有機ケイ素含有ブロックコポリマーが、約３～約２７個のシロキサニル単位、および約１～約１０個のシリルアルキルシロキサニル単位を含む、［１］～［６］に記載の水抽出可能な眼科用デバイス。
［８］
前記１つ以上の有機ケイ素含有ブロックコポリマーが、約５００Ｄａ～約５，０００Ｄａの範囲の数平均分子量を有し得る、［１］～［７］に記載の水抽出可能な眼科用デバイス。
［９］
前記１つ以上の有機ケイ素含有ブロックコポリマーが、式Ｉの構造：

（式中、Ｖは、エチレン性不飽和反応性末端基であり、Ｌは、リンカー基または結合であり、Ｒ ^１、Ｒ ^２、Ｒ ^３、Ｒ ^４、Ｒ ^５、Ｒ ^６、Ｒ ^７、およびＲ ^８は独立して、水素、Ｃ _１－Ｃ _１２アルキル、ハロアルキル、Ｃ _３－Ｃ _１２シクロアルキル、ヘテロシクロアルキル、Ｃ _２－Ｃ _１２アルケニル、ハロアルケニル、またはＣ _６－Ｃ _１２芳香族であり、Ｒ ^９およびＲ ^１０は独立して、水素またはＣ _１－Ｃ _１２アルキルであり、Ｒ ^１１、Ｒ ^１２、およびＲ ^１３は独立して、Ｃ _１－Ｃ _１２アルキルであり、ｙは、３～２１であり、ｘは、１～８であり、ａは、０～４である）、または式ＩＩの構造：

（式中、Ｖは、エチレン性不飽和反応性末端基であり、Ｌは、リンカー基または結合であり、Ｒ ^１４、Ｒ ^１５、Ｒ ^１６、Ｒ ^１７、Ｒ ^１８、およびＲ ^１９は独立して、水素、Ｃ _１－Ｃ _１２アルキル、ハロアルキル、Ｃ _３－Ｃ _１２シクロアルキル、ヘテロシクロアルキル、Ｃ _２－Ｃ _１２アルケニル、ハロアルケニル、またはＣ _６－Ｃ _１２芳香族であり、Ｒ ^２０およびＲ ^２１は独立して、水素またはＣ _１－Ｃ _１２アルキルであり、Ｒ ^２２、Ｒ ^２３、およびＲ ^２４は独立して、Ｃ _１－Ｃ _１２アルキルであり、ｙは、３～２７であり、ｘは、１～１０であり、ａは、２～４である）によって表される、［１］～［８］に記載の水抽出可能な眼科用デバイス。
［１０］
前記１つ以上の嵩高いシロキサンモノマーが、嵩高いポリシロキサニルアルキル（メタ）アクリルモノマー、嵩高いポリシロキサニルアルキルカルバメートモノマー、およびこれらの混合物からなる群から選択される、［１］～［９］に記載の水抽出可能な眼科用デバイス。
［１１］
前記１つ以上の嵩高いシロキサンモノマーが、式ＩＩＩの構造：

（式中、Ｘは、－ＣＯＯ－、－ＣＯＮＲ ^’ －、－ＯＣＯＯ－、または－ＯＣＯＮＲ’－を表し（式中、各Ｒ ^’ は、水素またはＣ _１－Ｃ _４アルキルである）、Ｒ ^２９は独立して、水素またはメチルを表し、各Ｒ ^３０は独立して、Ｃ _１－Ｃ _６アルキルなどの低級アルキルラジカル、フェニルラジカル、または以下によって表される基を表す：

（式中、各Ｒ ^３０’ は独立して、Ｃ _１－Ｃ _６アルキルなどの低級アルキル、またはフェニルラジカルを表し、ｈは、１～１０である））、または式ＩＶの構造：

（式中、Ｘは、－ＮＲ ^’’ －を表し（式中、Ｒ ^’’ は、水素またはＣ _１－Ｃ _４アルキルを表す）、Ｒ ^２９は、水素またはメチルを表し、各Ｒ ^３０は独立して、Ｃ _１－Ｃ _６アルキルなどの低級アルキルラジカル、フェニルラジカル、または以下によって表される基を表す：

（式中、各Ｒ ^３０′ は独立して、Ｃ _１－Ｃ _６アルキルなどの低級アルキル、またはフェニルラジカルを表し、ｈは、１～１０である））によって表される、［１］～［９］に記載の水抽出可能な眼科用デバイス。
［１２］
前記１つ以上の第１の架橋剤が、アルキレングリコール含有ジ（メタ）アクリレート架橋剤、アルキレングリコール含有トリ（メタ）アクリレート架橋剤、アルキレングリコール含有テトラ（メタ）アクリレート架橋剤、およびこれらの混合物からなる群から選択される、［１］～［１１］に記載の水抽出可能な眼科用デバイス。
［１３］
前記１つ以上の第２の架橋剤が、ジ（Ｎ－ビニルカルバメート）含有架橋剤、ジ（Ｎ－アリルカルバメート）含有架橋剤、ジ（Ｏ－ビニルカルバメート）含有架橋剤、ジ（Ｏ－アリルカルバメート）含有架橋剤、ジ（Ｏ－ビニルカルボネート）含有架橋剤、ジ（Ｏ－アリルカルボネート）含有架橋剤、トリ（Ｎ－ビニルカルバメート）含有架橋剤、トリ（Ｎ－アリルカルバメート）含有架橋剤、トリ（Ｏ－ビニルカルバメート）含有架橋剤、トリ（Ｏ－アリルカルバメート）含有架橋剤、トリ（Ｏ－ビニルカルボネート）含有架橋剤、トリ（Ｏ－アリルカルボネート）含有架橋剤、テトラ（Ｎ－ビニルカルバメート）含有架橋剤、テトラ（Ｎ－アリルカルバメート）含有架橋剤、テトラ（Ｏ－ビニルカルバメート）含有架橋剤、テトラ（Ｏ－アリルカルバメート）含有架橋剤、テトラ（Ｏ－ビニルカルボネート）含有架橋剤、テトラ（Ｏ－アリルカルボネート）含有架橋剤、イソシアヌレート含有架橋剤、およびこれらの混合物からなる群から選択される、［１］～［１２］に記載の水抽出可能な眼科用デバイス。
［１４］
前記１つ以上の第２の架橋剤が、式Ｖの構造：

（式中、Ｒは、水素またはメチルであり、Ｘ、Ｙ、およびＺは独立して、ＯまたはＮＨである）によって表される、［１］～［１３］に記載の水抽出可能な眼科用デバイス。
［１５］
前記１つ以上の第２の架橋剤が、式ＶＩの構造：

（式中、Ｒは、水素またはメチルであり、Ｘは、Ｏであり、Ｙは、ＯまたはＮＨであり、Ｚは、ＮＨであり、Ｗは、Ｏであり、ｎは、２～６である）によって表される、［１］～［１４］に記載の水抽出可能な眼科用デバイス。
［１６］
前記１つ以上の第２の架橋剤が、式ＶＩＩの構造：

（式中、ｘは、２～１０である）によって表される、［１］～［１５］に記載の水抽出可能な眼科用デバイス。
［１７］
前記モノマー混合物が、
（ａ）前記モノマー混合物の総重量に基づいて、約４２重量％～約５５重量％の前記１つ以上の環状ラクタムと、
（ｂ）前記モノマー混合物の総重量に基づいて、約５～約３０重量％の前記１つ以上の有機ケイ素含有ブロックコポリマーと、
（ｃ）前記モノマー混合物の総重量に基づいて、約１０～約４５重量％の前記１つ以上の嵩高いシロキサンモノマーと、
（ｄ）前記架橋剤混合物であって、（ｉ）前記モノマー混合物の総重量に基づいて、約０．０５～約２重量％の前記１つ以上の第１の架橋剤、および（ｉｉ）前記モノマー混合物の総重量に基づいて、約０．０５～約２重量％の前記１つ以上の第２の架橋剤、を含む、架橋剤混合物と、を含む、［１］～［１６］に記載の水抽出可能な眼科用デバイス。
［１８］
前記モノマー混合物が、少量の２－ヒドロキシエチルメタクリレート（ＨＥＭＡ）をさらに含む、［１］～［１７］に記載の水抽出可能な眼科用デバイス。
［１９］
前記モノマー混合物が、紫外線（ＵＶ）遮断剤をさらに含む、［１］～［１８］に記載の水抽出可能な眼科用デバイス。
［２０］
前記モノマー混合物が、ＵＶ遮断剤をさらに含む、［１９］に記載の水抽出可能な眼科用デバイス。
［２１］
前記モノマー混合物が、希釈剤をさらに含む、［１］～［２０］に記載の水抽出可能な眼科用デバイス。
［２２］
前記希釈剤が、Ｃ _１－Ｃ _８一価アルコールの１つ以上のホウ酸エステルを含む、［２１］に記載の水抽出可能な眼科用デバイス。
［２３］
前記水抽出可能な眼科用デバイスが、コンタクトレンズおよびヒドロゲルのうちの１つである、［１］～［２２］に記載の水抽出可能な眼科用デバイス。
［２４］
水抽出可能な眼科用デバイスを調製する方法であって、
（ａ）モノマー混合物を鋳型中で硬化させることであって、前記モノマー混合物が、
（ｉ）１つ以上の環状ラクタムと、
（ｉｉ）１つ以上のシロキサニル単位、および１つ以上のシリルアルキルシロキサニル単位を含む、１つ以上の有機ケイ素含有ブロックコポリマーであって、エチレン性不飽和反応性末端基を有する、１つ以上の有機ケイ素含有ブロックコポリマーと、
（ｉｉｉ）１つ以上の嵩高いシロキサンモノマーと、
（ｉｖ）架橋剤混合物であって、（１）少なくとも２つのエチレン性不飽和反応性末端基を含有する、１つ以上の第１の架橋剤であって、前記少なくとも２つのエチレン性不飽和反応性末端基が、（メタ）アクリレート含有反応性末端基である、１つ以上の第１の架橋剤、および（２）少なくとも２つのエチレン性不飽和反応性末端基を含有する１つ以上の第２の架橋剤であって、前記エチレン性不飽和反応性末端基のうちの少なくとも１つが、非（メタ）アクリレート反応性末端基である、１つ以上の第２の架橋剤、を含む、架橋剤混合物と、を含む、硬化させることと、
（ｂ）前記眼科用デバイスを前記鋳型から乾燥離型して、少なくとも約５０重量％の平衡水含有量、約５０°未満の接触角、および少なくとも約６０バーラーの酸素透過度を有する、水抽出可能な眼科用デバイスを提供することと、を含む、方法。
［２５］
前記水抽出可能な眼科用デバイスが、約５０重量％～約７０重量％の平衡水含有量、約３０°～約５０°の接触角、および少なくとも約７０バーラーの酸素透過度を有する、［２４］に記載の方法。
［２６］
前記水抽出可能な眼科用デバイスが、約１５重量％未満の水抽出物含有量をさらに有する、［２４］または［２５］に記載の方法。
［２７］
前記モノマー混合物中に存在する前記１つ以上の環状ラクタムの量が、前記モノマー混合物の総重量に基づいて、約５５重量％以下の量である、［２４］～［２６］に記載の方法。
［２８］
前記１つ以上の環状ラクタムが、Ｎ－ビニル－２－ピロリドン、Ｎ－ビニルカプロラクタム、Ｎ－ビニル－２－ピペリドン、およびこれらの混合物からなる群から選択される、［２４］～［２７］に記載の方法。
［２９］
前記１つ以上の有機ケイ素含有ブロックコポリマーが、約３～約２７個のシロキサニル単位、および約１～約１０個のシリルアルキルシロキサニル単位を含む、［２４］～［２８］に記載の方法。
［３０］
前記１つ以上の有機ケイ素含有ブロックコポリマーが、式Ｉの構造：

（式中、Ｖは、エチレン性不飽和反応性末端基であり、Ｌは、リンカー基または結合であり、Ｒ ^１、Ｒ ^２、Ｒ ^３、Ｒ ^４、Ｒ ^５、Ｒ ^６、Ｒ ^７、およびＲ ^８は独立して、水素、Ｃ _１－Ｃ _１２アルキル、ハロアルキル、Ｃ _３－Ｃ _１２シクロアルキル、ヘテロシクロアルキル、Ｃ _２－Ｃ _１２アルケニル、ハロアルケニル、またはＣ _６－Ｃ _１２芳香族であり、Ｒ ^９およびＲ ^１０は独立して、水素またはＣ _１－Ｃ _１２アルキルであり、Ｒ ^１１、Ｒ ^１２、およびＲ ^１３は独立して、Ｃ _１－Ｃ _１２アルキルであり、ｙは、３～２７であり、ｘは、１～２７であり、ａは、２～４である）、または式ＩＩの構造：

（式中、Ｖは、エチレン性不飽和反応性末端基であり、Ｌは、リンカー基または結合であり、Ｒ ^１４、Ｒ ^１５、Ｒ ^１６、Ｒ ^１７、Ｒ ^１８、およびＲ ^１９は独立して、水素、Ｃ _１－Ｃ _１２アルキル、ハロアルキル、Ｃ _３－Ｃ _１２シクロアルキル、ヘテロシクロアルキル、Ｃ _２－Ｃ _１２アルケニル、ハロアルケニル、またはＣ _６－Ｃ _１２芳香族であり、Ｒ ^２０およびＲ ^２１は独立して、水素またはＣ _１－Ｃ _１２アルキルであり、Ｒ ^２２、Ｒ ^２３、およびＲ ^２４は独立して、Ｃ _１－Ｃ _１２アルキルであり、ｙは、３～２７であり、ｘは、１～４であり、ａは、２～４である）によって表される、［２４］～［２９］に記載の方法。
［３１］
前記１つ以上の嵩高いシロキサンモノマーが、嵩高いポリシロキサニルアルキル（メタ）アクリルモノマー、嵩高いポリシロキサニルアルキルカルバメートモノマー、およびこれらの混合物からなる群から選択される、［２４］～［３０］に記載の方法。
［３２］
前記１つ以上の嵩高いポリシロキサンモノマーが、式ＩＩＩの構造：

（式中、Ｘは－ＣＯＯ－、－ＣＯＮＲ’－、－ＯＣＯＯ－、または－ＯＣＯＮＲ’－を表し（式中、各Ｒ’は、水素またはＣ _１－Ｃ _４アルキルである）、Ｒ ^２９は独立して、水素またはメチルを表し、各Ｒ ^３０は独立して、Ｃ _１－Ｃ _６アルキルなどの低級アルキルラジカル、フェニルラジカル、または以下によって表される基を表す：

（式中、各Ｒ ^３０′ は独立して、Ｃ _１－Ｃ _６アルキルなどの低級アルキル、またはフェニルラジカルを表し、ｈは、１～１０である））、または式ＩＶの構造：

（式中、Ｘは－ＮＲ’’－を表し（式中、Ｒ’’は、水素またはＣ _１－Ｃ _４アルキルを表す）、Ｒ ^２９は、水素またはメチルを表し、各Ｒ ^３０は独立して、Ｃ _１－Ｃ _６アルキルなどの低級アルキルラジカル、フェニルラジカル、または以下によって表される基を表す：

（式中、各Ｒ ^３０′ は独立して、Ｃ _１－Ｃ _６アルキルなどの低級アルキル、またはフェニルラジカルを表し、ｈは、１～１０である））によって表される、［２４］～［３１］に記載の方法。
［３３］
前記１つ以上の第１の架橋剤が、アルキレングリコール含有ジ（メタ）アクリレート架橋剤、アルキレングリコール含有トリ（メタ）アクリレート架橋剤、アルキレングリコール含有テルトラ（ｔｅｒｔｒａ）（メタ）アクリレート架橋剤、およびこれらの混合物からなる群から選択される、［２４］～［３２］に記載の方法。
［３４］
前記１つ以上の第２の架橋剤が、ジ（Ｎ－ビニルカルバメート）含有架橋剤、ジ（Ｎ－アリルカルバメート）含有架橋剤、ジ（Ｏ－ビニルカルバメート）含有架橋剤、ジ（Ｏ－アリルカルバメート）含有架橋剤、ジ（Ｏ－ビニルカルボネート）含有架橋剤、ジ（Ｏ－アリルカルボネート）含有架橋剤、トリ（Ｎ－ビニルカルバメート）含有架橋剤、トリ（Ｎ－アリルカルバメート）含有架橋剤、トリ（Ｏ－ビニルカルバメート）含有架橋剤、トリ（Ｏ－アリルカルバメート）含有架橋剤、トリ（Ｏ－ビニルカルボネート）含有架橋剤、トリ（Ｏ－アリルカルボネート）含有架橋剤、テトラ（Ｎ－ビニルカルバメート）含有架橋剤、テトラ（Ｎ－アリルカルバメート）含有架橋剤、テトラ（Ｏ－ビニルカルバメート）含有架橋剤、テトラ（Ｏ－アリルカルバメート）含有架橋剤、テトラ（Ｏ－ビニルカルボネート）含有架橋剤、テトラ（Ｏ－アリルカルボネート）含有架橋剤、イソシアヌレート含有架橋剤、およびこれらの混合物からなる群から選択される、［２４］～［３３］に記載の方法。
［３５］
前記モノマー混合物が、
（ａ）前記モノマー混合物の総重量に基づいて、約４２重量％～約５５重量％の前記１つ以上の環状ラクタムと、
（ｂ）前記モノマー混合物の総重量に基づいて、約５～約２５重量％の前記１つ以上の有機ケイ素含有ブロックコポリマーと、
（ｃ）前記モノマー混合物の総重量に基づいて、約１０～約４５重量％の前記１つ以上の嵩高いシロキサンモノマーと、
（ｄ）前記架橋剤混合物であって、（ｉ）前記モノマー混合物の総重量に基づいて、約０．０５～約２重量％の前記１つ以上の第１の架橋剤、および（ｉｉ）前記モノマー混合物の総重量に基づいて、約０．０５～約２重量％の前記１つ以上の第２の架橋剤、を含む、前記架橋剤混合物と、を含む、［２４］～［３４］に記載の方法。
［３６］
前記モノマー混合物が、少量のＨＥＭＡをさらに含む、［２４］～［３５］に記載の方法。
［３７］
前記モノマー混合物が、ＵＶ遮断剤をさらに含む、［２４］～［３６］に記載の方法。
［３８］
前記モノマー混合物が、Ｃ _１－Ｃ _８一価アルコールの１つ以上のホウ酸エステルを含む希釈剤をさらに含む、［２４］～［３７］に記載の方法。
［３９］
前記水抽出可能な眼科用デバイスが、コンタクトレンズおよびヒドロゲルのうちの１つである、［２４］～［３８］に記載の方法。
［４０］
前記硬化させるステップが、熱硬化または赤外線硬化のうちの１つを含む、［２４］～［３９］に記載の方法。
［４１］
少なくとも約５０重量％の平衡水含有量、約５０°未満の接触角、および少なくとも約６０バーラーの酸素透過度を有する水抽出可能な眼科用デバイスであって、［２４］～［４０］に記載の方法によって調製される、水抽出可能な眼科用デバイス。
It will be appreciated that various modifications can be made to the embodiments disclosed herein. Therefore, the above description should not be construed as limiting, but only as an example of a preferred embodiment. For example, the functions described above and implemented as the best mode for operating the present invention are for illustrative purposes only. Those skilled in the art can implement other configurations and methods without departing from the scope and gist of the present invention. In addition, one of ordinary skill in the art will assume other amendments within the scope and intent of the features and benefits added herein.
In addition, each of the following [1] to [41] is one form or one aspect of the present invention.
[1]
A water-extractable ophthalmic device that is a polymerization product of a monomer mixture, wherein the monomer mixture is:
(A) One or more annular lactams and
(B) One or more organosilicon-containing block copolymers comprising one or more siroxanyl units and one or more silylalkyl siroxanyl units, one having an ethylenically unsaturated reactive end group. With the above organosilicon-containing block copolymers,
(C) One or more bulky siloxane monomers and
(D) A cross-linking agent mixture, (i) one or more first cross-linking agents containing at least two ethylenically unsaturated reactive end groups, said at least two ethylenically unsaturated reactions. One or more containing a (meth) acrylate-containing reactive end group, one or more first cross-linking agents, and (ii) at least two ethylenically unsaturated reactive end groups. A second cross-linking agent comprising one or more second cross-linking agents, wherein at least one of the ethylenically unsaturated reactive end groups is a non- (meth) acrylate-reactive end group. Containing with a cross-linking agent mixture,
A water-extractable ophthalmic device, wherein the water-extractable ophthalmic device has an equilibrium water content of at least about 50% by weight, a contact angle of less than about 50 °, and an oxygen permeability of at least about 60 barlers.
[2]
The water-extractable ophthalmic use according to [1], which has an equilibrium water content of about 50% by weight to about 70% by weight, a contact angle of about 30 ° to about 50 °, and an oxygen permeability of at least about 70 barler. device.
[3]
The water-extractable ophthalmic use according to [1], which has an equilibrium water content of about 55% by weight to about 65% by weight, a contact angle of about 30 ° to about 45 °, and an oxygen permeability of at least about 70 barler. device.
[4]
The water-extractable ophthalmic device according to [1] to [3], further having a water extract content of less than about 15% by weight.
[5]
The water extraction according to [1] to [4], wherein the amount of the one or more cyclic lactams present in the monomer mixture is about 55% by weight or less based on the total weight of the monomer mixture. Possible ophthalmic device.
[6]
The one or more cyclic lactams are selected from the group consisting of N-vinyl-2-pyrrolidone, N-vinylcaprolactam, N-vinyl-2-piperidone, and mixtures thereof, according to [1] to [5]. The water-extractable ophthalmic device described.
[7]
The water according to [1] to [6], wherein the one or more organosilicon-containing block copolymers contain about 3 to about 27 siroxanyl units and about 1 to about 10 silylalkyl siroxanyl units. Extractable ophthalmic device.
[8]
The water-extractable ophthalmic device according to [1] to [7], wherein the organosilicon-containing block copolymer may have a number average molecular weight in the range of about 500 Da to about 5,000 Da.
[9]
The one or more organosilicon-containing block copolymers have the structure of Formula I:

(In the formula, V is an ethylenically unsaturated reactive end group and L is a linker group or bond, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R8 is independently hydrogen, C1 - ^C12alkyl , haloalkyl, C3 _- _{C12cycloalkyl} , heterocycloalkyl, C2- _C12alkenyl _, _haloalkenyl _, or C6 - _C12 _aromatics . , R ⁹ and R ¹⁰ are independently hydrogen or C ₁ - C ₁₂ alkyl, R ¹¹ , R ¹² and R ¹³ are independently C ₁ - C ₁₂ alkyl and y are 3 to 3 to. 21 and x is 1-8 and a is 0-4), or the structure of formula II:

(In the formula, V is an ethylenically unsaturated reactive end group, L is a linker group or a bond, and R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ are independent. , Hydrogen, C ₁ - C ₁₂ alkyl, haloalkyl, C ₃ - C ₁₂ cycloalkyl, heterocycloalkyl, C ₂ - C ₁₂ alkenyl, haloalkenyl, or C ₆ - C ₁₂ aromatics, R ²⁰ and R ²¹ Are independently hydrogen or C ₁ - C ₁₂ alkyl, R ²² , R ²³ , and R ²⁴ are independently C ₁ - C ₁₂ alkyl, y is 3-27, x is. The water-extractable ophthalmic device according to [1] to [8], which is represented by 1 to 10 and a is 2 to 4).
[10]
The bulky siloxane monomer is selected from the group consisting of bulky polysiloxanylalkyl (meth) acrylic monomers, bulky polysiloxanylalkylcarbamate monomers, and mixtures thereof, [1] to. The water-extractable ophthalmic device according to [9].
[11]
The one or more bulky siloxane monomers form the structure of formula III:

(In the formula, X represents -COO-, -CONR'-, -OCOO-, or -OCONR ^' -(in the formula, _each ^R'is hydrogen or C1- _C4 alkyl ), R ²⁹ . Represents hydrogen or methyl independently, and each R30 independently represents ^a lower alkyl radical such as C1 _- C6 _alkyl , a phenyl radical, or a group represented by:

(In the formula, each R ^{30'independently} represents a lower alkyl such as C1-C ₆ alkyl _, or a phenyl radical, where h is 1-10)) or the structure of formula IV:

(In the formula, X represents -NR ^'' -(in the formula, R ^'' represents hydrogen or C1 _- C4 alkyl), R ²⁹ represents hydrogen or methyl, and each R ₃₀ ^is independent . Represents a lower alkyl radical such as C1 _- C6 _alkyl , a phenyl radical, or a group represented by:

(In the formula, each R ^{30'independently} represents a lower alkyl such as C1-C ₆ alkyl _, or a phenyl radical, where h is 1-10)), [1]-[ 9] The water-extractable ophthalmic device according to.
[12]
The one or more first cross-linking agents are from an alkylene glycol-containing di (meth) acrylate cross-linking agent, an alkylene glycol-containing tri (meth) acrylate cross-linking agent, an alkylene glycol-containing tetra (meth) acrylate cross-linking agent, and a mixture thereof. The water-extractable ophthalmic device according to [1] to [11], which is selected from the group.
[13]
The one or more second cross-linking agents are a di (N-vinyl carbamate) -containing cross-linking agent, a di (N-allyl carbamate) -containing cross-linking agent, a di (O-vinyl carbamate) -containing cross-linking agent, and a di (O-allyl carbamate) -containing cross-linking agent. Carbamate) -containing cross-linking agent, di (O-vinyl carbonate) -containing cross-linking agent, di (O-allyl carbonate) -containing cross-linking agent, tri (N-vinyl carbamate) -containing cross-linking agent, tri (N-allyl carbamate) -containing cross-linking agent Agent, Tri (O-vinylcarbamate) -containing crosslinker, Tri (O-allylcarbamate) -containing crosslinker, Tri (O-vinylcarbonate) -containing crosslinker, Tri (O-allylcarbonate) -containing crosslinker, Tetra ( N-vinyl carbamate) -containing cross-linking agent, tetra (N-allyl carbamate) -containing cross-linking agent, tetra (O-vinyl carbamate) -containing cross-linking agent, tetra (O-allyl carbamate) -containing cross-linking agent, tetra (O-vinyl carbamate) -containing cross-linking agent. The water-extractable ophthalmic agent according to [1] to [12], which is selected from the group consisting of a cross-linking agent contained, a cross-linking agent containing tetra (O-allylcarbonate), a cross-linking agent containing isocyanurate, and a mixture thereof. device.
[14]
The one or more second cross-linking agents have the structure of formula V:

The water-extractable ophthalmology according to [1] to [13], represented by (in the formula, R is hydrogen or methyl and X, Y, and Z are independently O or NH). For devices.
[15]
The one or more second cross-linking agents are the structures of formula VI:

(In the formula, R is hydrogen or methyl, X is O, Y is O or NH, Z is NH, W is O, and n is 2-6. The water-extractable ophthalmic device according to [1] to [14], which is represented by (1).
[16]
The one or more second cross-linking agents are the structures of formula VII:

The water-extractable ophthalmic device according to [1] to [15], which is represented by (where x is 2 to 10 in the formula).
[17]
The monomer mixture is
(A) With about 42% by weight to about 55% by weight of the one or more cyclic lactams based on the total weight of the monomer mixture.
(B) From about 5 to about 30% by weight of the organosilicon-containing block copolymer with the one or more organosilicon-containing block copolymers, based on the total weight of the monomer mixture.
(C) With about 10 to about 45% by weight of the one or more bulky siloxane monomers based on the total weight of the monomer mixture.
(D) The cross-linking agent mixture, (i) the one or more first cross-linking agents of about 0.05 to about 2% by weight based on the total weight of the monomer mixture, and (ii) said. [1]-[16], wherein the cross-linking agent mixture comprises from about 0.05 to about 2% by weight of the one or more second cross-linking agents, based on the total weight of the monomer mixture. Water extractable ophthalmic device.
[18]
The water-extractable ophthalmic device according to [1] to [17], wherein the monomer mixture further comprises a small amount of 2-hydroxyethyl methacrylate (HEMA).
[19]
The water-extractable ophthalmic device according to [1] to [18], wherein the monomer mixture further contains an ultraviolet (UV) blocking agent.
[20]
The water-extractable ophthalmic device according to [19], wherein the monomer mixture further comprises a UV blocking agent.
[21]
The water-extractable ophthalmic device according to [1] to [20], wherein the monomer mixture further contains a diluent.
[22]
21. The water-extractable ophthalmic device according to [21], wherein the diluent comprises one or more boric acid esters of a C1 _- C8 _monohydric alcohol.
[23]
The water-extractable ophthalmic device according to [1] to [22], wherein the water-extractable ophthalmic device is one of a contact lens and a hydrogel.
[24]
A method for preparing a water-extractable ophthalmic device.
(A) Curing of the monomer mixture in a mold, wherein the monomer mixture is
(I) With one or more annular lactams,
(Ii) One or more organosilicon-containing block copolymers comprising one or more siroxanyl units and one or more silylalkyl siroxanyl units, one having an ethylenically unsaturated reactive end group. With the above organosilicon-containing block copolymers,
(Iii) With one or more bulky siloxane monomers,
(Iv) A cross-linking agent mixture, (1) one or more first cross-linking agents containing at least two ethylenically unsaturated reactive end groups, said at least two ethylenically unsaturated reactions. One or more first crosslinkers in which the sex end group is a (meth) acrylate-containing reactive end group, and (2) one or more first groups containing at least two ethylenically unsaturated reactive end groups. A cross-linking agent comprising one or more second cross-linking agents, wherein at least one of the ethylenically unsaturated reactive end groups is a non- (meth) acrylate-reactive end group. With the agent mixture, including, curing and
(B) Water extraction by drying and demolding the ophthalmic device from the mold to have an equilibrium water content of at least about 50% by weight, a contact angle of less than about 50 °, and an oxygen permeability of at least about 60 barlers. Providing possible ophthalmic devices and methods, including.
[25]
The water-extractable ophthalmic device has an equilibrium water content of about 50% by weight to about 70% by weight, a contact angle of about 30 ° to about 50 °, and an oxygen permeability of at least about 70 barr [24]. ] The method described in.
[26]
[24] or [25], wherein the water-extractable ophthalmic device further has a water extract content of less than about 15% by weight.
[27]
The method according to [24] to [26], wherein the amount of the one or more cyclic lactams present in the monomer mixture is about 55% by weight or less based on the total weight of the monomer mixture.
[28]
In [24] to [27], the one or more cyclic lactams are selected from the group consisting of N-vinyl-2-pyrrolidone, N-vinylcaprolactam, N-vinyl-2-piperidone, and mixtures thereof. The method described.
[29]
24. The method of [24]-[28], wherein the organosilicon-containing block copolymer comprises from about 3 to about 27 siroxanyl units and from about 1 to about 10 silylalkyl siroxanyl units. ..
[30]
The one or more organosilicon-containing block copolymers have the structure of Formula I:

(In the formula, V is an ethylenically unsaturated reactive end group and L is a linker group or bond, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R8 is independently hydrogen, C1 - ^C12alkyl , haloalkyl, C3 _- _{C12cycloalkyl} , heterocycloalkyl, C2- _C12alkenyl _, _haloalkenyl _, or C6 - _C12 _aromatics . , R ⁹ and R ¹⁰ are independently hydrogen or C ₁ - C ₁₂ alkyl, R ¹¹ , R ¹² and R ¹³ are independently C ₁ - C ₁₂ alkyl and y are 3 to 3 to. 27, x is 1-27, a is 2-4), or the structure of formula II:

(In the formula, V is an ethylenically unsaturated reactive end group, L is a linker group or a bond, and R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ are independent. , Hydrogen, C ₁ - C ₁₂ alkyl, haloalkyl, C ₃ - C ₁₂ cycloalkyl, heterocycloalkyl, C ₂ - C ₁₂ alkenyl, haloalkenyl, or C ₆ - C ₁₂ aromatics, R ²⁰ and R ²¹ Are independently hydrogen or C ₁ - C ₁₂ alkyl, R ²² , R ²³ , and R ²⁴ are independently C ₁ - C ₁₂ alkyl, y is 3-27, x is. 1 to 4, where a is 2 to 4), according to [24] to [29].
[31]
The bulky siloxane monomer is selected from the group consisting of bulky polysiloxanylalkyl (meth) acrylic monomers, bulky polysiloxanylalkylcarbamate monomers, and mixtures thereof, [24] to. The method according to [30].
[32]
The one or more bulky polysiloxane monomers form the structure of formula III:

(In the formula, X represents -COO-, -CONR'-, -OCOO-, or ^-OCONR '-(in the formula, each R'is hydrogen or C1- _C4 _alkyl ) , where R29 is . Independently represent hydrogen or methyl, and each R30 independently represents ^a lower alkyl radical such as C1 _- C6 _alkyl , a phenyl radical, or a group represented by:

(In the formula, X represents -NR "- (in the formula, R" represents hydrogen or C1 _- C4 alkyl), R ²⁹ represents hydrogen or methyl, and each R ₃₀ ^is independent. Represents a lower alkyl radical such as C1 _- C6 _alkyl , a phenyl radical, or a group represented by:

(In the formula, each R ^{30'independently} represents a lower alkyl such as C1-C ₆ alkyl _, or a phenyl radical, where h is 1-10)), [24]-[ 31].
[33]
The one or more first cross-linking agents are an alkylene glycol-containing di (meth) acrylate cross-linking agent, an alkylene glycol-containing tri (meth) acrylate cross-linking agent, an alkylene glycol-containing tertra (meth) acrylate cross-linking agent, and these. The method according to [24] to [32], which is selected from the group consisting of a mixture of.
[34]
The one or more second cross-linking agents are a di (N-vinyl carbamate) -containing cross-linking agent, a di (N-allyl carbamate) -containing cross-linking agent, a di (O-vinyl carbamate) -containing cross-linking agent, and a di (O-allyl carbamate) -containing cross-linking agent. Carbamate) -containing cross-linking agent, di (O-vinyl carbonate) -containing cross-linking agent, di (O-allyl carbonate) -containing cross-linking agent, tri (N-vinyl carbamate) -containing cross-linking agent, tri (N-allyl carbamate) -containing cross-linking agent Agent, Tri (O-vinylcarbamate) -containing crosslinker, Tri (O-allylcarbamate) -containing crosslinker, Tri (O-vinylcarbonate) -containing crosslinker, Tri (O-allylcarbonate) -containing crosslinker, Tetra ( N-vinyl carbamate) -containing cross-linking agent, tetra (N-allyl carbamate) -containing cross-linking agent, tetra (O-vinyl carbamate) -containing cross-linking agent, tetra (O-allyl carbamate) -containing cross-linking agent, tetra (O-vinyl carbamate) -containing cross-linking agent. The method according to [24] to [33], which is selected from the group consisting of a cross-linking agent contained, a cross-linking agent containing tetra (O-allylcarbonate), a cross-linking agent containing isocyanurate, and a mixture thereof.
[35]
The monomer mixture is
(A) With about 42% by weight to about 55% by weight of the one or more cyclic lactams based on the total weight of the monomer mixture.
(B) With about 5 to about 25% by weight of the organosilicon-containing block copolymer with the one or more organosilicon-containing block copolymers, based on the total weight of the monomer mixture.
(C) With about 10 to about 45% by weight of the one or more bulky siloxane monomers based on the total weight of the monomer mixture.
(D) The cross-linking agent mixture, (i) the one or more first cross-linking agents of about 0.05 to about 2% by weight based on the total weight of the monomer mixture, and (ii) said. [24]-[34] comprising said cross-linking agent mixture comprising from about 0.05 to about 2% by weight of said one or more second cross-linking agents, based on the total weight of the monomer mixture. The method described.
[36]
The method according to [24] to [35], wherein the monomer mixture further comprises a small amount of HEMA.
[37]
The method according to [24] to [36], wherein the monomer mixture further comprises a UV blocking agent.
[38]
The method according to [24] to [37], wherein the monomer mixture further comprises a diluent containing one or more boric acid esters of a C1 _- C8 _monohydric alcohol.
[39]
The method according to [24] to [38], wherein the water-extractable ophthalmic device is one of a contact lens and a hydrogel.
[40]
The method according to [24] to [39], wherein the curing step comprises one of thermosetting or infrared curing.
[41]
A water-extractable ophthalmic device having an equilibrium water content of at least about 50% by weight, a contact angle of less than about 50 °, and an oxygen permeability of at least about 60 barlers, according to [24]-[40]. A water-extractable ophthalmic device prepared by the method of.

Claims

A water-extractable ophthalmic device that is a polymerization product of a monomer mixture, wherein the monomer mixture is:
(A) One or more annular lactams and
(B) One or more organosilicon-containing block copolymers comprising one or more siroxanyl units and one or more silylalkyl siroxanyl units, one having an ethylenically unsaturated reactive end group. With the above organosilicon-containing block copolymers,
(C) One or more bulky siloxane monomers and
(D) A cross-linking agent mixture, (i) one or more first cross-linking agents containing at least two ethylenically unsaturated reactive end groups, said at least two ethylenically unsaturated reactions. One or more containing a (meth) acrylate-containing reactive end group, one or more first cross-linking agents, and (ii) at least two ethylenically unsaturated reactive end groups. A second cross-linking agent comprising one or more second cross-linking agents, wherein at least one of the ethylenically unsaturated reactive end groups is a non- (meth) acrylate-reactive end group. Containing with a cross-linking agent mixture,
A water-extractable ophthalmic device, wherein the water-extractable ophthalmic device has an equilibrium water content of at least about 50% by weight, a contact angle of less than about 50 °, and an oxygen permeability of at least about 60 barlers.

Equilibrium water content of about 50% by weight to about 70% by weight, contact angle of about 30 ° to about 50 °, oxygen permeability of at least about 70 barlers, and water extract content of less than about 15% by weight . The water-extractable ophthalmic device according to claim 1.

The water extractable according to claim 1 or 2 , wherein the organosilicon-containing block copolymer comprises from about 3 to about 27 siroxanyl units and from about 1 to about 10 silylalkyl siroxanyl units. Ophthalmic device.

The one or more organosilicon-containing block copolymers have the structure of Formula I:

(In the formula, V is an ethylenically unsaturated reactive end group and L is a linker group or bond, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R8 is independently hydrogen, C1- ^C12alkyl , haloalkyl, C3 _- _{C12cycloalkyl} , heterocycloalkyl, _C2 _- _C12alkenyl , _haloalkenyl , or C6 _- _C12 aromatics. , R ⁹ and R ¹⁰ are independently hydrogen or C ₁ -C ₁₂ alkyl, R ¹¹ , R ¹² and R ¹³ are independently C ₁ -C ₁₂ alkyl and y are 3 to 3 to. 21 and x is 1-8 and a is 0-4), or the structure of formula II:

(In the formula, V is an ethylenically unsaturated reactive end group, L is a linker group or a bond, and R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ are independent. , Hydrogen, C ₁ -C ₁₂ alkyl, haloalkyl, C ₃ -C ₁₂ cycloalkyl, heterocycloalkyl, C ₂ -C ₁₂ alkenyl, haloalkenyl, or C ₆ -C ₁₂ aromatics, R ²⁰ and R ²¹ Are independently hydrogen or C ₁ -C ₁₂ alkyl, R ²² , R ²³ , and R ²⁴ are independently C ₁ -C ₁₂ alkyl, y is 3-27, x is. The water-extractable ophthalmic device according to any one of claims 1 to 3 , represented by 1 to 10 and a is 2 to 4).

The one or more bulky siloxane monomers are selected from the group consisting of bulky polysiloxanylalkyl (meth) acrylic monomers, bulky polysiloxanylalkylcarbamate monomers, and mixtures thereof. 4. The water-extractable ophthalmic device according to any one of 4 .

The one or more first cross-linking agents are from an alkylene glycol-containing di (meth) acrylate cross-linking agent, an alkylene glycol-containing tri (meth) acrylate cross-linking agent, an alkylene glycol-containing tetra (meth) acrylate cross-linking agent, and a mixture thereof. The water-extractable ophthalmic device according to any one of claims 1 to 5, which is selected from the group.

The one or more second cross-linking agents are a di (N-vinyl carbamate) -containing cross-linking agent, a di (N-allyl carbamate) -containing cross-linking agent, a di (O-vinyl carbamate) -containing cross-linking agent, and a di (O-allyl carbamate) -containing cross-linking agent. Carbamate) -containing cross-linking agent, di (O-vinyl carbonate) -containing cross-linking agent, di (O-allyl carbonate) -containing cross-linking agent, tri (N-vinyl carbamate) -containing cross-linking agent, tri (N-allyl carbamate) -containing cross-linking agent Agent, Tri (O-vinylcarbamate) -containing crosslinker, Tri (O-allylcarbamate) -containing crosslinker, Tri (O-vinylcarbonate) -containing crosslinker, Tri (O-allylcarbonate) -containing crosslinker, Tetra ( N-vinyl carbamate) -containing cross-linking agent, tetra (N-allyl carbamate) -containing cross-linking agent, tetra (O-vinyl carbamate) -containing cross-linking agent, tetra (O-allyl carbamate) -containing cross-linking agent, tetra (O-vinyl carbamate) -containing cross-linking agent. The water extractable according to any one of claims 1 to 6, which is selected from the group consisting of a cross-linking agent contained, a cross-linking agent containing tetra (O-allylcarbonate), a cross-linking agent containing isocyanurate, and a mixture thereof. Ophthalmology device.

The monomer mixture is
(A) With about 42% by weight to about 55% by weight of the one or more cyclic lactams based on the total weight of the monomer mixture.
(B) From about 5 to about 30% by weight of the organosilicon-containing block copolymer with the one or more organosilicon-containing block copolymers, based on the total weight of the monomer mixture.
(C) With about 10 to about 45% by weight of the one or more bulky siloxane monomers based on the total weight of the monomer mixture.
(D) The cross-linking agent mixture, (i) the one or more first cross-linking agents of about 0.05 to about 2% by weight based on the total weight of the monomer mixture, and (ii) said. Any one of claims 1-7, comprising a cross-linking agent mixture comprising from about 0.05 to about 2% by weight of the one or more second cross-linking agents, based on the total weight of the monomer mixture. The water-extractable ophthalmic device described in the section .

The water-extractable ophthalmic device according to any one of claims 1 to 8, wherein the monomer mixture further comprises a small amount of 2-hydroxyethyl methacrylate .

The water-extractable ophthalmic device according to any one of claims 1 to 9 , wherein the monomer mixture further comprises an ultraviolet blocking agent.

A method for preparing a water-extractable ophthalmic device.
(A) Curing of the monomer mixture in a mold, wherein the monomer mixture is
(I) With one or more annular lactams,
(Ii) One or more organosilicon-containing block copolymers comprising one or more siroxanyl units and one or more silylalkyl siroxanyl units, one having an ethylenically unsaturated reactive end group. With the above organosilicon-containing block copolymers,
(Iii) With one or more bulky siloxane monomers,
(Iv) A cross-linking agent mixture, (1) one or more first cross-linking agents containing at least two ethylenically unsaturated reactive end groups, said at least two ethylenically unsaturated reactions. One or more first crosslinkers in which the sex end group is a (meth) acrylate-containing reactive end group, and (2) one or more first groups containing at least two ethylenically unsaturated reactive end groups. A cross-linking agent comprising one or more second cross-linking agents, wherein at least one of the ethylenically unsaturated reactive end groups is a non- (meth) acrylate-reactive end group. With the agent mixture, including, curing and
(B) Water extraction by drying and demolding the ophthalmic device from the mold to have an equilibrium water content of at least about 50% by weight, a contact angle of less than about 50 °, and an oxygen permeability of at least about 60 barlers. Providing possible ophthalmic devices and methods, including.

The monomer mixture is
(A) With about 42% by weight to about 55% by weight of the one or more cyclic lactams based on the total weight of the monomer mixture.
(B) With about 5 to about 25% by weight of the organosilicon-containing block copolymer with the one or more organosilicon-containing block copolymers, based on the total weight of the monomer mixture.
(C) With about 10 to about 45% by weight of the one or more bulky siloxane monomers based on the total weight of the monomer mixture.
(D) The cross-linking agent mixture, (i) the one or more first cross-linking agents of about 0.05 to about 2% by weight based on the total weight of the monomer mixture, and (ii) said. 11. The method of claim 11 , comprising the cross-linking agent mixture comprising from about 0.05 to about 2% by weight of the one or more second cross-linking agents, based on the total weight of the monomer mixture.

The method of claim 11 or 12, wherein the organosilicon-containing block copolymer comprises from about 3 to about 27 siroxanyl units and from about 1 to about 10 silylalkyl siroxanyl units.