MX349540B

Amphiphilic polysiloxane prepolymers and uses thereof.

Abstract

The present invention provides an amphiphilic polysiloxane prepolymer comprising hydrophilic monomeric units derived from at least one hydrophilic vinyl monomer, polysiloxane crosslinking units derived from at least one crosslinking polysiloxane having at least two terminal ethylenically unsaturated groups, chains entangled polysiloxane blocks, each of which is terminated with an ethylenically unsaturated group, and chain transfer units derived from a chain transfer agent other than a RAFT agent. A prepolymer of the invention is suitable for making hydrogel contact lenses. The present invention also relates to hydrogel contact lenses made from an amphiphilic polysiloxane prepolymer of the invention, and to processes for the preparation of an amphiphilic polysiloxane prepolymer of the invention and for making silicone hydrogel contact lenses.

MX349540B, drawing sheet 1 — Sheet 1 of 102

Term

4.8 yearsleft in the term

Expires 29 July 2031.

15 claims: 3 independent, 12 dependent

1
CLAIMS REIVINDICACIONES 1. Un prepolímero ramificado anfifílico que se obtiene mediante:one. An amphiphilic branched prepolymer obtained by: (i) polimerizar una composición polimerizable para obtener un copolímero de polisiloxano ramificado anfifílico, en donde < la composición polimerizable comprénde: (i) polymerizing a polymerizable composition to obtain an amphiphilic branched polysiloxane copolymer, wherein <the polymerizable composition comprises: (a) de aproximadamente 10 por ciento a aproximadamente 94 por ciento en peso de un polisiloxano parcialmente funcionalizado etilénicamente, en donde el polisiloxano parcialmente funcionalizado etilénicamente es una mezcla de productos de reacción obtenidos mediante la reacción de un primer monómero vinílico etilénicamente funcionalizante que tiene un primer grupo funcional reactivo, con un compuesto de polisiloxano funcional que tiene dos o más segundos grupos funcionales reactivos, en una proporción equivalente molar, Requivaiente, de aproximadamente 40 a aproximadamente 95 por ciento, en donde cada primer grupo funcional reactivo reacciona con un segundo grupo funcional reactivo en la presencia o en ausencia de un agente de acoplamiento para formar una unión o enlace covalente, en donde la mezcla de productos de reacción comprende cuando menos un reticulante de polisiloxano que tiene cuando menos dos grupos etilénicamente insaturados, y cuando menos un monómero o macrómero vinílico de polisiloxano que tiene cuando menos un segundo grupo funcional reactivo y cuando menos un grupo etilénicamente insaturado, (a) from about 10 percent to about 94 percent by weight of a partially ethylenically functionalized polysiloxane, wherein the partially ethylenically functionalized polysiloxane is a mixture of reaction products obtained by reacting a first ethylenically functionalizing vinyl monomer having a first reactive functional group, with a functional polysiloxane compound having two or more second reactive functional groups, in a required molar equivalent ratio of about 40 to about 95 percent, wherein each first reactive functional group reacts with a second reactive functional group in the presence or absence of a coupling agent to form a covalent bond or bond, wherein the reaction product mixture comprises at least one polysiloxane crosslinker having at least two ethylenically unsaturated groups, and at least one polysiloxane vinyl monomer or macromer having at least one second reactive functional group and at least one ethylenically unsaturated group, 124 124 ΙΝΤΤΓΠΠΟ MEXICAN OF THE PROPERTY (b) at least one monom'dTo ™ *1 viFft + te-σ hydrophilic, ---—- · (c) optionally a hydrophobic vinyl monomer, (d) a chain transfer agent other than a RAFT agent, wherein the chain transfer agent optionally includes a third group reactive functional, and (e) a free radical initiator;and (ii) ethylenically functionalizing the amphiphilic branched polysiloxane copolymer by reacting with a second ethylenically functionalizing vinyl monomer having a fourth reactive functional group that reacts with a second or third reactive functional group in the presence or absence of a coupling agent. to form a covalent bond, thereby forming the amphiphilic branched polysiloxane prepolymer. ΙΝΤΤΓΠΠΟ MEXICANO DE LA PROPIEDAD (b) cuando menos un monóm'dTó™*1 viFft+te-σ hidrofílico, ---—- · (c) opcionalmente un monómero vinílico hidrofóbico, (d) un agente de transferencia de cadena diferente de un agente RAFT, en donde el agente de transferencia de cadena opcionalmente incluye un tercer grupo funcional reactivo, y (e) un iniciador de radicales libres;y (ii) funcionalizar etilénicamente el copolímero de polisiloxano ramificado anfifílico mediante su reacción con un segundo monómero vinílico etilénicamente funcionalizante que tiene un cuarto grupo funcional reactivo que reacciona con un segundo o tercer grupo funcional reactivo en la presencia o en ausencia de un agente de acoplamiento para formar un enlace covalente, formando de esta manera el prepolímero de polisiloxano ramificado anfifílico.
13
A method of making silicone hydrogel contact lenses, which comprises the steps of:13. Un método para hacer lentes de contacto de hidrogel de silicona, el cual comprende los pasos de: (i) obtaining an amphiphilic branched polysiloxane prepolymer comprising;(i) obtener un prepolímero de polisiloxano ramificado anfifílico que comprende;134 134 IMPI ^ iiMiwro micano nt LA nOKEDAD (a) from about 5 percent to about / S percent by weight of monomeric units, hr * Jer * vaJa * s of at least one hydrophilic vinyl monomer, (b) of about 1 percent to about 85 percent by weight of polysiloxane crosslinking units derived from at least one polysiloxane crosslinker having two or more terminal ethylenically unsaturated groups, (c) from about 2 percent to about 48 weight percent pendent polysiloxane chains, each of which is terminated with an ethylenically unsaturated group, and (d) from about 0.25 percent to about 5 weight percent of chain transfer units that is not a RAFT agent, wherein the amphiphilic branched polysiloxane prepolymer is obtained according to a process comprising the steps of: IMPI^ iiMiwro muicano nt LA nOKEDAD (a) de aproximadamente 5 por ciento a aproxima^íamente/S por ciento en peso de unidades monoméricas hí cf roTTlíc as*Jer*váJa*s de cuando menos un monómero vinílico hidrofílico, (b) de aproximadamente 1 por ciento a aproximadamente 85 por ciento en peso de unidades de reticulación de polisiloxano derivadas de cuando menos un reticulante de polisiloxano que tiene dos o más grupos etilénicamente insaturados terminales, (c) de aproximadamente 2 por ciento a aproximadamente 48 por ciento en peso de cadenas de polisiloxano pendientes, cada una de las cuales está terminada con un grupo etilénicamente insaturado, y (d) de aproximadamente 0.25 por ciento a aproximadamente 5 por ciento en peso de unidades de transferencia de cadena que no es un agente RAFT, en donde el prepolímero de polisiloxano ramificado anfifílico se obtiene de acuerdo con un proceso que comprende los pasos de: (a) obtaining a partially ethylenically functionalized polysiloxane, wherein the partially ethylenically functionalized polysiloxane is a mixture of reaction products obtained by reacting a first ethylenically functionalizing vinyl monomer having a first reactive functional group, with a functional polysiloxane compound that has two or more second reactive functional groups, in a molar equivalent ratio of from about 40 percent to about 95 percent, wherein each first reactive functional group reacts with a second reactive functional group in the presence or absence of a coupling agent to (a) obtener un polisiloxano parcialmente funcionalizado etilénicamente, en donde el polisiloxano parcialmente funcionalizado etilénicamente es una mezcla de productos de reacción obtenidos mediante la reacción de un primer monómero vinílico etilénicamente funcionalizante que tiene un primer grupo funcional reactivo, con un compuesto de polisiloxano funcional que tiene dos o más segundos grupos funcionales reactivos, en una proporción equivalente molar de aproximadamente 40 por ciento a aproximadamente el 95 por ciento, en donde cada primer grupo funcional reactivo reacciona con un segundo grupo funcional reactivo en la presencia o en ausencia de un agente de acoplamiento para 135 135 IMPI rWfTTTvro mbucan® DI LA nOTlEDAT INDUSTRIAL form a union or covalent bond, where the mixture of IMPI rWfTTTvro mbucan® DI LA nOTlEDAT INDUSTRIAL formar una unión o enlace covalente, en donde la mezcla de .._— --- ! -y productos de reacción comprende cuando menos un reticulante de polisiloxano que tiene cuando menos dos grupos etilénicamente insaturados, y cuando menos un monómero o macrómero vinílico de polisiloxano que tiene cuando menos un segundo grupo funcional reactivo y cuando menos un grupo etilénicamente insaturado;.._— ---! - and reaction products comprise at least one polysiloxane crosslinking agent having at least two ethylenically unsaturated groups, and at least one polysiloxane vinyl monomer or macromer having at least one second reactive functional group and at least one ethylenically unsaturated group;(b) usar el polisiloxano parcialmente funcionalizado etilénicamente para preparar una composición polimerizable, en donde la composición polimerizable comprende cuando menos un monómero vinílico hidrofílico, un agente de transferencia de cadena que no es un agente RAFT, y opcionalmente incluye un tercer grupo funcional reactivo, y un iniciador de radicales libres, (c) polimerizar la composición polimerizable para formar un copolímero de polisiloxano ramificado anfifílico que comprende unidades monoméricas hidrofílicas derivadas a partir del cuando menos un monómero vinílico hidrofílico, unidades de reticulación de polisiloxano derivadas a partir del polisiloxano reticulante, cadenas de polisiloxano pendientes, cada una terminada con un segundo grupo funcional reactivo y derivado a partir del monómero o macrómero vinílico de polisiloxano que tiene cuando menos un segundo grupo funcional reactivo y cuando menos un grupo insaturado etilénicamente, y unidades de transferencia de cadena con o sin terceros grupos funcionales reactivos derivados a partir del agente de transferencia de cadena, y (d) hacer reaccionar el copolímero de polisiloxano (b) using the partially ethylenically functionalized polysiloxane to prepare a polymerizable composition, wherein the polymerizable composition comprises at least one hydrophilic vinyl monomer, a chain transfer agent that is not a RAFT agent, and optionally includes a third reactive functional group, and a free radical initiator, (c) polymerizing the polymerizable composition to form an amphiphilic branched polysiloxane copolymer comprising hydrophilic monomer units derived from the at least one hydrophilic vinyl monomer, polysiloxane crosslinking units derived from the crosslinking polysiloxane, pendant polysiloxane chains, each terminated with a second reactive functional group and derived from the vinyl polysiloxane monomer or macromer having at least one second reactive functional group and at least one ethylenically unsaturated group, and chain transfer units with or without third reactive functional groups derivatives from the chain transfer agent, and (d) reacting the polysiloxane copolymer 136 136 IMENTUTC M »CANO IMENTUTC M»CANO DE LA PROPIEDAD INDUSTRIAL T— ramificado anfifílico con un segundo monomero vinílico etilénicamente funcionalizante que tiene un cuarto grupo1 funcional reactivo que reacciona con un segundo o tercer grupo funcional reactivo del copolímero de polisiloxano ramificado en la presencia o en ausencia de un agente de acoplamiento para formar un enlace covalente, formando de esta manera el prepolímero de polisiloxano ramificado anfifílico que tiene cadenas de polisiloxano pendientes, cada una de las cuales está terminada con un grupo etilénicamente insaturado;OF INDUSTRIAL PROPERTY T— amphiphilic branched with a second ethylenically functionalizing vinyl monomer having a fourth group1 reactive functional group that reacts with a second or third reactive functional group of the branched polysiloxane copolymer in the presence or absence of a coupling agent to form a covalent bond, thereby forming the amphiphilic branched polysiloxane prepolymer having pendant polysiloxane chains each of which is terminated with an ethylenically unsaturated group;(Ii) using the amphiphilic branched polysiloxane prepolymer to prepare a composition for forming lenses, which comprises: (¡i) usar el prepolímero de polisiloxano ramificado anfifílico para preparar una composición para formar lentes, la cual comprende: de aproximadamente por ciento aproximadamente 99 por ciento en peso del prepolímero de polisiloxano ramificado anfifílico, (b) de aproximadamente of about 99 percent by weight of the amphiphilic branched polysiloxane prepolymer, (b) of about 0.1 percent about 5 percent by weight of a free radical initiator, and from 0 to about 20 percent by weight of at least one polymerizable component selected from the group consisting of a hydrophilic vinyl monomer, a vinyl monomer that contains silicone, a silicone-containing vinyl macromer with a single ethylenically unsaturated group, a hydrophobic vinyl monomer, a linear polysiloxane crosslinker terminated with two ethylenically unsaturated groups, an agent 0.1 por ciento aproximadamente 5 por ciento en peso de un iniciador de radicales libres, y de 0 a aproximadamente el 20 por ciento en peso de cuando menos un componente polimerizable seleccionado a partir del grupo que consiste en un monómero vinílico hidrofílico, un monómero vinílico que contiene silicona, un macrómero vinílico que contiene silicona con un solo grupo etilénicamente insaturado, un monómero vinílico hidrofóbico, un reticulante de polisiloxano lineal terminado con dos grupos etilénicamente insaturados, un agente crosslinking agent having a molecular weight of less than 700 Daltons, an ultraviolet radiation absorbing agent (DV ^ polymerizable, and mixtures thereof;reticulante que tiene un peso molecular de menos de 700 Daltons, un agente absorbente de radiación ultravioleta (DV^polimerizable, y mezclas de los mismos;en donde los porcentajes en peso de los componentes (a) a (c) son en relación con la cantidad total de todos los componentes polimerizables (incluyendo aquéllos no enlistados anteriormente) en la composición para formar lentes;wherein the weight percentages of components (a) to (c) are relative to the total amount of all polymerizable components (including those not listed above) in the lens-forming composition;(iii) introducing the lens-forming composition into a mold, wherein the mold has a first mold half with a first molding surface defining the anterior surface of a contact lens, and a second mold half with a second surface molding that defines the posterior surface of the contact lens, wherein the first and second mold halves are configured to receive one another, such that a cavity is formed to receive the lens-forming material between said first and second molding surfaces;and (iv) polymerizing the lens-forming material in the cavity to form a silicone hydrogel contact lens. (iii) introducir la composición para formar lentes en un molde, en donde el molde tiene una primera mitad de molde con una primera superficie de moldeo que define la superficie anterior de un lente de contacto, y una segunda mitad de molde con una segunda superficie de moldeo que define la superficie posterior del lente de contacto, en donde las primera y segunda mitades de molde se configuran para recibirse una a la otra, de tal manera que se forma una cavidad para recibir al material formador de lentes entre las primera y segunda superficies de moldeo mencionadas;y (iv) polimerizar el material formador de lentes en la cavidad para formar un lente de contacto de hidrogel de silicona.
15
Un lente de contacto de hidrogel de silicona que comprende un material polimérico que es un producto de la fifteen. A silicone hydrogel contact lens comprising a polymeric material that is a product of the 138 138 IMPI tNsrrnToMBtjCAjri IMPI tNsrrnToMBtjCAjri Dt LA rtORWAD Industrial Dt LA rtORWAD Industrial polimerización de una composición para formar lentes que incluye un prepolímero de polisiloxano ramificado anfifílico de la reivindicación polymerization of a lens-forming composition including an amphiphilic branched polysiloxane prepolymer of claim 1. 1. 139 139

Independent claims3

663 paragraphs in 41 sections, as filed

(54) Title: AMPHIFILIC POLYSYLOXANE PRE-POLYMERS AND USES OF THEM.

(54) Title: AMPHIPHILIC POLYSILOXANE PREPOLYMERS AND USES THEREOF.

(57) Summary

(57) Abstract

The present invention provides an amphiphilic polysiloxane prepolymer which comprises hydrophilic monomeric units derived from at least one hydrophilic vinylic monomer, polysiloxane crosslinking units derived from at least one polysiloxane crosslinker having at least two terminal ethylenically-unsaturated groups, dangling polysiloxane chains each of which is terminated with one ethylenically unsaturated group, and chain-transfer units derived from a Chain transfer agent other than a RAFT agent. A prepolymer of the invention is suitable for making hydrogel contact lenses. The present invention is also related to hydrogel contact lenses made from an amphiphilic polysiloxane prepolymer of the invention and to processes for preparing an amphiphilic polysiloxane prepolymer of the invention and for making silicone hydrogel contact lenses.

PATENT TITLE No. 349540

Owner (s): NOVARTIS AG

Address: Lichtstrasse 35, CH-4056, Basel, SWITZERLAND

Denomination: AMPHIFILIC POLYSYLOXANE PRE-POLYMERS AND USES OF THEM.

Classification: CIP: G02C7 / 04; B29D11 / 00; C07F7 / 10; G02B1 / 12

CPC: C08F290 / 068; C08G77 / 00; C08G77 / 458; CO8G2210 / 00; G02B1 / 043

Inventor (s): FRANK CHANG: ROBERT SCOTT; JINYU HUANG; ARTURO N. MEDINA; DAWN A.

SMITH; LAURA ANN SANDERS; JOHN DALLAS PRUITT

REQUEST

Number: International Presentation Date:

MX / a / 2013/001249 July 29, 2011

PRIORITY

Country: Date: Number:

US July 30, 2010 61 / 369,109

Validity: Twenty years

Expiration Date: July 29, 2031

Issue Date: August 2, 2017

The reference patent is granted based on articles 1, 2, section V, 6or Section III, and 59 of the Industrial Property Law,

In accordance with article 23 of the Industrial Property Law, this patent has a validity of twenty years, non-extendable from the date of filing the international application and will be subject to payment in order to keep the rights in force.

Whoever signs this title does so based on the provisions of articles 6or Sections III and 7 bis 2 of the Industrial Property Law (Official Gazette of the Federation (DOF) 06/27/1991, amended on 08/02/1994, 10/25/1996, 12/26/1997, 17 / 05/1999, 26/01/2004, 16/06/2005, 25/01/2006, 06/05 / 2009,06 / 01/2010, 18/06/2010, 28/06/2010, 27/01 / 2012 and 04/09/2012); items 1or, 3or fraction V part a), 4or and 12 »sections I and III of the Regulations of the Mexican Institute of Industrial Property (DOF 12/14/1999, amended on 07/01/2002, 07/15/2004, 07/28/2004 and 09/07/2007) ; Articles 1, 3, 4, 5, section V subsection a), 16 sections I and III and 30 of the Organic Statute of the Mexican Institute of Industrial Property (DOF 12/27/1999, amended on 10/10/2002, 07/29/2004, 08/04/2004 and 09/13/2007), 1st, 3rd and 5th subsection a) of the Agreement that delegates powers to the Deputy General Directors, Coordinator, Divisional Directors, Heads of the Regional Offices. Divisional Deputy Directors, Departmental Coordinators and other subordinates of the Mexican Institute of Industrial Property. (DOF 12/15/1999, amended on 02/04/2000, 07/29/2004 08/04/2004 and 09/13/2007).

This document is signed with an advanced electronic signature (FIEL), based on articles 7 BIS 2 of the Industrial Property Law; 3 of its Regulations, and 1 section III, 2 section V, 26 BIS and 26 TER of the Agreement establishing the guidelines for the use of the Payment and Electronic Services Portal (PASE) of the Mexican Institute of Industrial Property, in the procedures indicated.

THE DIVISIONAL DIRECTOR OF PATENTS

NAHANNY CANAL REYES

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Tax | 1695 || MX / 2017/61590 | MX / a / 2013/001249 | PCT patent title | 1223 | GAGV | Page (s) | DS2AGXHjrJ1 RPG9iFyVpsp7nNM =

Digital stamp:

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ζΑθ ί3 / 7

POLYSYLOXANE PRE-POLYMERS ΑΝFIFÍLicd ^ '^

AND USES OF THE SAME

The present invention relates to a class of amphiphilic polysiloxane prepolymers suitable for making hydrogel contact lenses. The present invention also relates to hydrogel contact lenses made from an amphiphilic polysiloxane prepolymer of the invention, and to processes for the preparation of an amphiphilic polysiloxane prepolymer of the invention and for making silicone hydrogel contact lenses.

BACKGROUND

Currently, silicone hydrogel contact lenses are produced according to a conventional cast molding technique that involves the use of disposable plastic molds and a mixture of monomers in the presence or absence of macromers. However, disposable plastic molds inherently have unavoidable dimensional variations because, during injection molding of plastic molds, fluctuations in the dimensions of the molds can occur as a result of fluctuations in the manufacturing process. production (temperatures, pressures, material properties), and also because the resulting molds can experience non-uniform shrinkage after injection molding. These dimensional changes in the mold can lead to

IMPIOés msTmiTo Mexican

OF INDUSTRIAL PROPERTY fluctuations in the parameters of the contact lenses that are going to be produced (maximum refractive index, diameter, 'cuTva ”·” · basic, central thickness, etc.) and at low fidelity when doubling the lens design complex.

These disadvantages found in a conventional casting technique can be overcome using the so-called Lightstream Technology.MR (CIBA Vision), as illustrated in United States Patent Numbers 5,508,317, 5,789,464, 5,849,810, and 6,800,225, which are incorporated in their entirety by reference. Lightstream TechnologyMR it involves reusable molds produced with high precision, and a cure under a spatial limitation of actinic radiation (eg ultraviolet (UV) radiation). Lenses produced in accordance with Lightstream TechnologyMR can have high consistency and high fidelity to the original lens design, due to the use of reusable high-precision molds. In addition, contact lenses of high quality can be produced at a relatively lower cost, due to the short curing time and high production throughput.

In order to apply the Lightstream TechnologyMR In the manufacture of silicone hydrogel contact lenses, silicone-containing prepolymers have been developed, as described in United States Patent Nos.

6,039,913, 6,043,328, 7,091,283, 7,268,189 and 7,238,750, 7,521,519;

in the Publications of the Patent Applications of the States

United States of North America Numbers US 2008-0015315 A1, US 20080143958 A1, US 2008-0143003 A1, US 2008-0234457 A1, and US 20080231798 A1 collectively owned, and in United States of North America Patent Application Numbers 12 / 313,546 , 12 / 616,166 and 12/616169 collectively owned, which are incorporated by reference in their entirety. However, these types of prepolymers disclosed in the above patents and patent applications may have some practical limitations in their use to make silicone hydrogel contact lenses according to Lightstream Technology.MR.

A Collectively Proprietary Pending United States Patent Application Number 12 / 456,364 (incorporated herein by reference in its entirety) discloses a method for making silicone hydrogel contact lenses from a mixture of monomers. (i.e. a composition to form lenses) according to Lightstream TechnologyMR. However, here it is discovered that, in addition to a relatively longer cure time, relatively significant shrinkage can occur during cure of the monomer mixture in molds which can largely impede the application of Lightstream Technology.MR in the manufacture of silicone hydrogel contact lenses.

Accordingly, there is still a need for new suitable prepolymers to make silicone hydrogel contact lenses according to Lightstream Technology.MR.

IMPI

IRSTTTÜTO MIXKUN * by lAraomnAB

BRIEF DESCRIPTION OF THE INVENTION

The invention provides an amphiphilic branched polysiloxane prepolymer suitable for making silicone hydrogel contact lenses in accordance with Lightstream Technology.MR. The polysiloxane prepolymer comprises hydrophilic monomeric units derived from at least one hydrophilic vinyl monomer , polysiloxane crosslinking units derived from at least one crosslinking polysiloxane having at least two terminal ethylenically unsaturated groups, pendant polysiloxane chains, each one of which is terminated with an ethylenically unsaturated group, and chain transfer units derived from a chain transfer agent other than a RAFT agent.

The invention also provides a method of making silicone hydrogel contact lenses. The method comprises the steps of: (i) obtain an amphiphilic branched polysiloxane prepolymer of the invention (as described above), (i) use the amphiphilic branched polysiloxane prepolymer to prepare a lens-forming composition further comprising a free radical initiator and optionally at least a polymerizable component selected from the group consisting of a hydrophilic vinyl monomer, a silicone-containing vinyl monomer or macromer, a hydrophobic vinyl monomer, a linear polysiloxane crosslinker terminated with two ethylenically unsaturated groups, a crosslinking agent having a molecular weight of less than 700 Daltons, and mixtures thereof; (ii) introducing the lens-forming composition into a mold, wherein the mold has a first mold half with a first molding surface defining the anterior surface of a contact lens, and a second mold half with a second molding surface that defines the posterior surface of the contact lens, wherein the first and second mold halves are configured to receive one another, such that a cavity is formed to receive the lens-forming material between the mentioned first and second molding surfaces; and (ii) polymerizing the lens-forming material in the cavity to form a silicone hydrogel contact lens.

The invention further provides a method of producing an amphiphilic branched polysiloxane prepolymer of the invention.

The invention also further provides a silicone hydrogel contact lens comprising a polymeric material obtained from the polymerization of a lens-forming composition, which comprises an amphiphilic branched polysiloxane prepolymer of the invention.

These and other aspects of the invention will become apparent from the following description of the presently preferred embodiments. The detailed description is merely illustrative of the invention and does not limit the scope of the invention, which is defined by the appended claims and their equivalents. How would it be

Obvious to one skilled in the art, many variations and modifications of the invention can be made without departing from the spirit and scope of the novel concepts of this specification.

DETAILED DESCRIPTION OF THE MODALITIES

OF THE INVENTION

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as is commonly understood by one of ordinary skill in the field to which this invention belongs. Generally speaking, the nomenclature used herein, and laboratory methods are well known and commonly used in the art. Conventional methods are employed for these procedures, such as those provided in the art and in various general references. When a term is provided in the singular, the inventors also contemplate the plural of that term. The nomenclature used herein and in the laboratory procedures described below is well known, and is commonly employed in the art.

"Contact lens" refers to a structure that can be placed on or in the eye of a user. A contact lens can correct, improve, or alter a wearer's vision, but this need not be the case. A "silicone hydrogel contact lens" refers to a contact lens that comprises a silicone hydrogel material.

A "hydrogel" or "hydrogel material" refers to a polymeric material, which can absorb at least 10 percent by weight of water when fully hydrated.

A 'silicone hydrogel'1 refers to a silicone-containing hydrogel, obtained by copolymerizing a polymerizable composition comprising at least one silicone-containing vinyl monomer or macromer, a silicone-containing crosslinker, and / or at least one cross-linked silicone-containing prepolymer you.

A "vinyl monomer" refers to a low molecular weight compound having a single ethylenically unsaturated group. Low molecular weight typically means average molecular weights less than 700 Daltons.

A "vinyl macromer" refers to a medium and high molecular weight compound comprising a single ethylenically unsaturated group. Medium and high molecular weight typically means average molecular weights greater than 700 Daltons.

The term "olefinically unsaturated group or ethylenically unsaturated group" is used herein in a broad sense and is intended to encompass any groups that contain at least one> C = C <group. Exemplary ethylenically unsaturated groups include, without limitation, (meth) acryloyl OO CH3 , _ H_ _ II l_ l_ (C CH — CH2 and / or C Cfy), allyl, vinyl (C styrenyl,

IMPI

It ^ mWOMBUCAXO Dt UH (OHtDAD τ * .ΛΛ (HOUSTIIAl M or other groups containing C = C..

As used herein, "aclinically" with reference to curing, crosslinking, or polymerization of a composition, a prepolymer, or a polymerizable material, means that curing (eg, crosslinking and / or polymerization) is accomplished by means of actinic irradiation, such as, for example, ultraviolet (UV) / visible irradiation, ionizing radiation (for example, gamma ray or X-ray irradiation), microwave irradiation, and the like. Thermal curing or actinic curing methods are well known to a person skilled in the art.

The term "(meth) acrylamide" refers to methacrylamide and / or acrylamide.

The term "(meth) acrylate" refers to methacrylate and / or acrylate.

A "hydrophilic vinyl monomer", as used herein, refers to a vinyl monomer that can be polymerized to form a homopolymer that is soluble in water, or that can absorb at least 10 percent. percent by weight of water.

A "hydrophobic vinyl monomer" refers to a vinyl monomer that can be polymerized to form a homopolymer that is insoluble in water, and that can absorb less than 10 percent by weight of water.

As used herein, the term "amino group" refers to a functional group of -NHR 'where R' is hydrogen or an unsubstituted or substituted linear or branched alkyl group of 1 to 20 carbon atoms.

As used herein, the term "azalactone group"

refers to a functional group having the formula of O, where r is 0 or 1; R1 and R2 independently they can be an alkyl group having 1 to 14 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, an aryl group having 5 to 12 ring atoms, an arenyl group having 6 to 26 carbon and 0 to 3 sulfur, nitrogen and / or oxygen atoms, or Ri and R2 Taken together with the carbon atom to which they are attached, they can form a carbocyclic ring containing 4 to 12 ring atoms.

As used herein, "polysiloxane" refers to a compound or segment that includes at least one radical

<td rowspan="2">r3one S i O one divalent of</td><td rowspan="2">Γ R5 i one -Yes-O-</td><td></td><td rowspan="2">Γ R7 one one Yes orL Re</td><td rowspan="2">R9 1 -Yes- 1 pRw,</td><td rowspan="2">where R3, R4, R5,</td>

<td>Re, R?> Rg> and Rio,</td><td colspan="4">independently ones</td><td>of others, they are alkyl</td>

C 1 to 10 atoms, C 1 -C 10 amino alkyl, C 1 -C 10 hydroxy alkyl, C 1 -C 10 ether, C 1 -C 4 alkyl substituted phenyl or by alkoxy of 1 to 4 carbon atoms, fluoro-alkyl of 10 carbon atoms, fluoro-ether of 1 to 10 carbon atoms, aryl radical of 6 to 18 carbon atoms, cyano- (alkyl of 1 to carbon atoms), -alk- (OCH2CH2) n-ORn, where alk is a

divalent alkylene radical of 1 to 6 carbon atoms, Rn is hydrogen or alkyl of 1 to 6 carbon atoms, and n is an integer of 1 to 10; m and p, independently of each other, are an integer from 0 to 350 and (m + p) is from 1 to 700.

A "crosslinker" refers to a compound that has at least two ethylenically unsaturated groups.

A "crosslinking agent" refers to a compound with two or more ethylenically unsaturated groups and with a molecular weight of less than 700 Daltons. Crosslinking agents can be used to improve structural integrity and strength. The amount of a crosslinking agent used is expressed in the content by weight with respect to the total polymer and is preferably in the range of about 0.05 percent to about 4 percent, and most preferably in the range of about 0.1 percent to about 2 percent. Examples of preferred crosslinking agents include, without limitation, tetraethylene glycol di- (meth) acrylate, triethylene glycol di- (meth) acrylate, ethylene glycol di- (meth) acrylate, diethylene glycol di- (meth) acrylate, trimethacrylate trimethylolpropane, pentaerythrite I tetramethacrylate, bisphenol A dimethacrylate, vinyl methacrylate, allyl (meth) acrylate, ethylenediamine-di- (meth) acrylamide, glycerol dimethacrylate, N, N'-methylenebis- (meth) acrylamide N, N'-ethylene-bis- (meth) acrylamide, N, N'-dihydroxy-ethylene-bis- (meth) acrylamide, triallyl isocyanurate, triallyl cyanurate, allyl (meth) acrylate, 1,3-bis- (methacrylamido-propyl) -1,1,3,311

ΙΝΓΠΤυΤΟ MFX1CAMU CE LA MOHEDA »tetrakis- (trimethyl-silox¡) -dis¡loxane, 1,3-bis- (Wi'ttjaTtffelflidopropyl) -1,1,3,3-tetrakis- (trimetiI-siIoxy) -disiΙοΊ? 3ΤΤϊΓ * T *, WJfS (methacryl licked-bu ti l) -1,1,3,3-te trachis- (trimet¡ls¡lox¡) -d¡s¡loxane, 1,3bis- (methacryloxy-ethyl -uredo-propyl) -1,1,3,3-tetrakis- (trimethylsiloxy) disiloxane, and combinations thereof. A more preferred crosslinking agent is a hydrophilic crosslinking agent, such as, tetra- (ethylene glycol) diacrylate, tri- (ethylene glycol I) diacrylate, ethyl ng I ico I diacrylate, di - (ethyl ng I i co diacrylate. I), glycerol dimethacrylate, N, N'-methylene-bis- (meth) acrylamide, N, N'-ethylene-bis- (meth) acrylamide, N, N'-dihydroxy-ethyl -b¡s- (meth) acrylamide, triallyl isocyanurate, triallyl cyanurate, or a combination thereof.

The term "fluid," as used herein, indicates that a material is capable of flowing like a liquid.

A "prepolymer" refers to a starting polymer that contains two or more ethylenically unsaturated groups and can be aclinically cured (e.g., crosslinked or polymerized) to obtain a crosslinked polymer that has a much higher molecular weight than the polymer of departure.

A "silicone-containing prepolymer" refers to a silicone-containing prepolymer.

"Molecular weight" of a polymeric material (including monomeric or macromeric materials), as used herein, refers to the weight average molecular weight, unless specifically noted otherwise or unless the test conditions do so. indicate otherwise.

"Polymer means a mSTTTVTO MEXICAN ΙΜΤ-ί'Γ-Γ DE LA MONEDAD OMaSUy INDUSTUJAl ***" material formed by the polymerization of one or more monomers.

The term "RAFT" refers to radical addition fragmentation transfer or reversible addition fragmentation chain transfer, as understood by one of ordinary skill in the art.

A "RAFT agent" refers to a dithioester compound of

S

II

Rz θ Rl, where RL it is a leaving group and has its traditional meanings as understood by an expert in the field; Rz it is an activating group and has its traditional meanings as understood by a person skilled in the art.

As used herein, the term "ethylenically functionalized", with reference to a copolymer or a compound, is intended to describe that one or more ethylenically functionalized groups have been covalently attached to a copolymer or compound through the pendent reactive functional groups. or terminals of the copolymer or the compound according to a coupling process.

An "ethylenically functionalizing vinyl monomer" refers to a vinyl monomer having a reactive functional group capable of participating in a coupling (or crosslinking) reaction known to a person skilled in the art.

A "coupling reaction" is intended to describe any reaction between a pair of paired functional groups in the

IMPI • 'Τ'Λρ MUICAN .. ot u woneoAt. • 'DtCTRIAl

presence or absence of an agent of accordion to form covalent bonds or bonds under various reaction conditions well known to a person skilled in the art, such as, for example, oxidation-reduction conditions, dehydration-condensation conditions, addition conditions, substitution (or displacement) conditions, Diels-Alder reaction conditions, cationic crosslinking conditions, ring-opening conditions, epoxy curing conditions, and combinations thereof.

Non-limiting examples of coupling reactions under various reaction conditions between a pair of paired co-reactive functional groups selected from the group preferably consisting of amino group (-NHR 'as defined above), hydroxyl group, group carboxylic acid groups, acid halide groups (—COX, X = Cl, Br, or I), acid anhydrate group, aldehyde group, azalactone group, isocyanate group, epoxy group, aziridine group, thiol group, and amide groups (—CONH2), are given below for illustrative purposes. An amino group reacts with an aldehyde group to form a Schiff's base, which can be further reduced; an amino group -NHR 'reacts with an acid chloride or bromide group, or with an acid anhydride group, to form an amide bond (-CONR'-); an amino group -NHR 'reacts with an isocyanate group to form a urea bond (-NR'-C (O) -NH-); an amino group -NHR 'reacts with an epoxy or aziridine group to form a bond of μ IΜ ΡI ikwrmrro mukamo πε the nopiEDAr. Y

FNIWrrtlAI amine (C-NR '); an amino group reacts (opening OS δΠΊΐΤδΤ'εδί'ΓΐΙΙΤ 'azalactone group to form a bond (-C (O) NH-CR1R2- (CH2)rC (O) -NR'-); an amino group -NHR 'reacts with a carboxylic acid group in the presence of a coupling agent - carbodiimide (e.g., 1-ethyl-3- (3-dimethyl-amino-propyl) -carbodi -imide (EDO), Ν, Ν'-dicyclohexyl-carbodi-imide (DCC), 1-cyclohexyl-3- (2-morpholino-ethyl) -carbod¡ -im¡da, di-isopropyl-carbodi-imide, or mixtures thereof), to form an amide bond; a hydroxyl reacts with an isocyanate group to form a urethane bond; a hydroxyl reacts with an epoxy or aziridine group to form an ether bond (-O-); a hydroxyl reacts with an acid chloride or bromide group, or with an acid anhydride group to form an ester bond; a hydroxyl group reacts with an azalactone group in the presence of a catalyst to form a (-C (O) NH-CRiR bond2- (CH2)r-C (O) -O-); a carboxyl group reacts with an epoxy group to form an ester bond; a thiol group (-SH) reacts with an isocyanate group to form a thiocarbamate bond (-NC (O) -S-); a thiol group reacts with an epoxy or aziridine group to form a thioether bond (-S-); a thiol group reacts with an acid chloride or bromide group, or with an acid anhydride group, to form a thiol ester bond; a thiol group reacts with an azalactone group in the presence of a catalyst to form a bond (-C (O) NH-alkylene-C (O) -S-); a thiol group reacts with a vinyl group based on a thiol-ene reaction under thiol-ene reaction conditions, to form a

IMPI thioether bond (-S-); and a thiol group reacts with an acryloyl or methacryloyl group based on Addiction-'Ve W under appropriate reaction conditions to form a thioether bond.

It is also understood that coupling agents with two reactive functional groups can be used in coupling reactions. For example, a diisocyanate, di-acid halide, di-carboxylic acid, di-azalactone, or di-epoxy compound can be used in the coupling of two hydroxyl groups, two amino groups, two carboxyl groups, two groups epoxies, or a combination thereof; A diamine or dihydroxyl compound can be used in the coupling of two isocyanate groups, two epoxy groups, two aziridine groups, two carboxyl groups, two halide groups, or two azalactone groups, or combinations thereof.

The reaction conditions for the above-described coupling reactions are taught in textbooks and are well known to a person skilled in the art.

As used herein, the term "partially ethylenically functionalized polysiloxane" means a mixture of products obtained as a result of an ethylenically functionalizing reaction between an ethylenically functionalizing vinyl monomer having a reactive first functional group and a functional polysiloxane compound having two or more second reactive functional groups in a molar equivalent ratio, RANDquivaiente, (that is:

[vinyl monomer worksH ^ aiiHjl / T '[linear polysiloxane compound]eq ) of about 0.95 (or 95 percent) or less, wherein a first reactive functional group can react with a second reactive functional group in the presence or absence of a coupling agent according to a known coupling reaction, such as is discussed later, to form a covalent bond. As used herein, the term "xx percent ethylenically functionalized polysiloxane" means a mixture of products obtained wherein the ratio of the ethylenically functionalizing vinyl monomer and a functional polysiloxane compound in a molar equivalent ratio, REquivalent. of xx percent "(that is, a value from about 40 percent to about 97 percent, preferably from about 50 percent to about 95 percent, more preferably from about 60 percent to about 95 percent). 92 percent, still more preferably about 70 percent to about 90 percent).

As an illustrative example, if a functional polysiloxane compound to be ethylenically functionalized is a linear polysiloxane compound having two terminal reactive functional groups and the molar equivalent ratio RANDquivant of an ethylenically functionalizing vinyl monomer to the compound of

polysiloxane is approximately 80 percent, so an 80 · percent ethylenically functionalized ii —— polysiloxane is a mixture of: (a) a linear polysiloxane crosslinker having two terminal ethylenically unsaturated groups, (b) a vinyl polysiloxane monomer or macromer terminated with an ethylenically unsaturated group and a second reactive functional group, and (c) an unreacted linear polysiloxane compound terminated with two second reactive functional groups. The percentages of components (a) to (c) of the 80 percent ethylenically functionalized polysiloxane (after the reaction is substantially complete) can be estimated according to the following formula:

[Component (a)]% = RANDquivalent X ^ Equivalent = 64% [Component (b)]% = 2 x REquivalent X (1 REqu¡valent) = 32% [Component (c)]% - (1 REquivalent) X (1 R Equivalent) — 4% It is to be understood that a polysiloxane compound to be ethylenically functionalized can be a star compound having "n" (eg, 3 to 5) polysiloxane arms, each terminated with a reactive functional group capable of participating in a coupling reaction. The number of ethylenically functionalizing reaction products in the resulting mixture would be (n + 1), and their percentages are, respectively, (REquivalent)> (REquivalent)n1X (1 ”REquivalent) xn> ^ Equivalent) 2χ (1 REquivalent)2 xn> ··· (REquivalent) X (1 REquivalent) X Π, (1 ~ REquivalent)

As used herein, the term "multiples" refers to two or more.

18 IMPI »!» Mexican τπυιυ OF THE PROPERTY «NDUFHUU

A free radical initiator can be either a photoinitiator or a thermal initiator. A "photoinitiator" refers to a chemical that initiates a free radical crosslinking / polymerization reaction through the use of light. Suitable photoinitiators include, without limitation, benzoin methyl ether, diethoxy acetophenone, a benzoyl phosphine oxide, 1-hydroxycyclohexyl phenyl ketone, the Darocure® types of photoinitiators, and the Irgacure® types of photoinitiators, preferably Darocure® 1173 and Irgacure® 2959. Examples of benzoylphosphine oxide initiators include 2,4,6-tri-meth I-be η zoi Id ¡fe ni lfosphina (TPO); bis- (2,6-dichloro-benzoyl) -4-N-propyl-phenyl-phosphine oxide; and bis- (2,6-dichloro-benzoyl) -4-N-butyl-phenyl-phosphine oxide. Reactive photoinitiators that can be incorporated, for example, into a macromer, or that can be used as a special monomer, are also suitable. Examples of reactive photoinitiators are those disclosed in European Patent Number EP 632 329, incorporated herein by reference in its entirety. The polymerization can then be triggered by actinic radiation, for example light, in particular ultraviolet (UV) light of a suitable wavelength. Spectral requirements can be controlled accordingly, if appropriate, by the addition of suitable photosensitizers.

A "thermal initiator" refers to a chemical that initiates the radical crosslinking / polymerization reaction through the use of heat energy. Examples of initiators

Suitable thermals include, but are not limited to, 2,2'-azobis- (2,4-dimethyl-pentane-nitrile), 2,2'-azobis- (2-methyl-propane-nitrile), 2,2 ' azobis- (2-methyl-butane-nitrile), peroxides, such as benzoyl peroxide, and the like. Preferably, the thermal initiator is 2,2'azobls- (super-butyronyron) (AIBN).

A polymerizable ultraviolet (UV) absorbing agent refers to a compound comprising an edenically unsaturated group and an ultraviolet (UV) absorbing fraction or a latent ultraviolet (UV) absorbing fraction.

An "ultraviolet (UV) absorbing moiety" refers to an organic functional group that can absorb or filter ultraviolet (UV) radiation in the range of 200 nanometers to 400 nanometers as understood by a person skilled in this field.

A "polymerizable latent ultraviolet (UV) absorbing agent" refers to a compound comprising an edenically unsaturated group and an ultraviolet (UV) absorbing fraction that has been protected by a labile functional group, such that their coefficients absorption of ultraviolet (UV) radiation in the wavelength region of 200 nanometers to 400 nanometers are approximately 50 percent or less, preferably 70 percent or less, more preferably about 90 percent or less of that of the ultraviolet (UV) absorbing fraction without

IMPI

Π »5ΤΓΤνΤΟ MMUCAKo

ÜE THE INDUSTRIAL METHOD the protected labile functional group.

The term "labile functional group" means a protective functional group that can be removed (dissociated) from another functional group that is being protected by the labile functional group.

A "spatial limitation of actinic radiation refers to an act or process in which radiation of energy in the form of rays is directed, for example, through a mask or screen, or combinations thereof, to strike, in a spatial manner restricted, over an area that has a well-defined peripheral boundary. Ultraviolet (UV) / visible radiation spatial limitation can be obtained by using a mask or screen that has a radiation-permeable region (e.g., ultraviolet (UV) / visible), a radiation-impermeable region (e.g. , ultraviolet (UV) / visible) surrounding the radiation-permeable region, and a projection contour that is the boundary between the radiation-impermeable region and the radiation-permeable region, as schematically illustrated in the drawings of United States Patent Numbers 6,800,225 (Figures 1 to 11), and 6,627,124 (Figures 1 to 9), 7,384,590 (Figures 1 to 6), and 7,387,759 (Figures 1 to 6 ), all of which are incorporated by reference in their entirety. The mask or screen allows a beam of radiation (eg, ultraviolet (UV) / visible radiation) to be spatially projected having a cross-sectional profile defined by the projection contour of the mask or screen. The projected beam of radiation (for example, ultraviolet radiation

(UV) / visibIe) limits radiation (for example, Ia-p & é + aetoη u 111 to \ r I uféfET ~ (UV) visible) striking a lens-forming material located in the path of the beam projected from the first surface of molding to the second molding surface of a mold. The resulting contact lens comprises an anterior surface defined by the first molding surface, an opposite posterior surface defined by the second molding surface, and an edge of the lens defined by the projected ultraviolet (UV) / visible ray sectional profile (ie i.e., a spatial limitation of radiation). The radiation used for crosslinking is radiation energy, especially ultraviolet (UV) / visible radiation, gamma radiation, electron radiation, or thermal radiation, the radiation energy being preferably in the form of a beam substantially parallel, with the object that, on the one hand, a good restriction is achieved, and on the other hand, an efficient use of energy is achieved.

In the conventional cast molding process, the first and second molding surfaces of a mold are pressed against each other to form a circumferential nip that defines the edge of a resulting contact lens. Because the close contact of the molding surfaces can damage the optical quality of the molding surfaces, the mold cannot be reused. In contrast, in Lightstream TechnologyMR, the edge of a resulting contact lens is not defined by the contact of the molding surfaces of a mold, but instead, by a limitation

IMPI

MIXICAN INSTITUTE

OF THE INDUSTRY * spatial radiation. With no contact between the molding surfaces of a mold, the mold can be used repeatedly to produce high-quality contact lenses with high reproducibility.

The term "pendant polysiloxane chains" with reference to an amphiphilic branched polysiloxane copolymer or prepolymer is intended to describe that the copolymer or prepolymer comprises linear polysiloxane chains, each of which comprises one or more polysiloxane segments, and is anchored to the main chain of the copolymer or prepolymer through a single covalent bond at one of the two ends of the polysiloxane chain.

A "tint" means a substance that is soluble in a fluid lens-forming material, and that is used to impart color. Tints are typically translucent and absorb, but do not scatter, light.

A "pigment" means a powdered substance (particles) that is suspended in a composition to form lenses, in which it is insoluble.

Surface modification or surface treatment ", as used herein, means that an article has been treated in a surface treatment process (or in a surface modification process) before or after the formation of the article, wherein (1) a coating is applied to the surface of the article, (2) the chemical species are adsorbed on the surface of the article, (3) the chemical nature (e.g. electrostatic charge) is altered 23 IMPI ^ iNrrnvroMejcAjr, • í THE INtHTSTItlAL rIOREOAD of chemical groups on the surface of the article, or (4) the surface properties of the article are otherwise modified. Exemplary surface treatment processes include, but are not limited to, surface treatment by energy (eg, a plasma, a static electrical charge, irradiation, or other energy source), chemical treatments, the grafting of monomers or macromers. hydrophilic vinyl on the surface of an article, the mold transfer coating process disclosed in United States Patent Number 6,719,929 (incorporated herein by reference in its entirety), the incorporation of wetting agents into a lens formulation for the purpose of make the contact lenses proposed in United States Patent Numbers 6,367,929 and 6,822,016 (incorporated herein by reference in their entirety), the reinforced mold transfer coating disclosed in United States Patent Application Number 60/81 1,949 (incorporated herein by reference in its entirety), and a hydrophilic coating composed of the covalent bond or the physical deposit of one or more layers of one or more hydrophilic polymers on the surface of a contact lens.

"Post-cure surface treatment", with reference to a silicone hydrogel material or soft contact lens, means a surface treatment process that is carried out after the formation (of cure) of the hydrogel material or of the

soft contact lens in a mold.

A "hydrophilic surface" with reference to a silicone hydrogel material or a contact lens means that the silicone hydrogel material or the contact lens has a surface hydrophilicity characterized by having a contact angle with average water about 90 degrees or less, preferably about 80 degrees or less, more preferably about 70 degrees or less, and most preferably about 60 degrees or less.

An “average contact angle” refers to an angle of contact with water (angle measured by the Sessile Drop method, which is obtained by averaging the measurements of at least 3 individual contact lenses.

An "antimicrobial agent", as used herein, refers to a chemical that is capable of decreasing or eliminating or inhibiting the growth of microorganisms, as that term is known in the art. Preferred examples of the antimicrobial agent include, without limitation, silver salts, silver complexes, silver nanoparticles, silver-containing zeolites, and the like. "Silver nanoparticles" refers to particles that are made essentially of silver metal, and that are less than 1 miera in size.

The intrinsic "oxygen permeability", Dk, of a material is the rate at which oxygen will pass through a material. From

IMPI ίΜΤΠνΤΟ MEXICANO · * The ΜοΛεβλει xowniAi according to the invention, the term “oxygen permeability (Dk)” with reference to a contact lens, means an apparent permeability to oxygen, which is measured with a sample (film or lens) having an average thickness over the area that is measured according to a known method. Oxygen permeability is conventionally expressed in units of barrers, where “sweep” is defined as [(cm3 oxygen) (mm) / (cm2) (sec) (mm Hg)] x 10 '10.

The oxygen transmissibility ”, Dk / t, of a lens or material, is the rate at which oxygen will pass through a specific lens or material with an average thickness of t [in units of mm] over the area to be measure. Oxygen transmissibility is conventionally expressed in units of barrers / millimeter, where “barrers / millimeter” is defined as [(cm3 oxygen) / (cm2) (sec) (mm Hg)] x 10 '9.

The "ion permeability" through a lens correlates with the lonoflux Diffusion Coefficient. The lonoflux Diffusion Coefficient, D (in units of [mm2/ minute]), is determined by applying Fick's law as follows:

D = - n '/ (A x dc / dx) where n' = ion transport speed [moles / minute]; A = area of lens exposed [mm2]; de = concentration difference [moles / liter]; dx = lens thickness [millimeters].

In general, the invention relates to a class of amphiphilic branched polysiloxane prepolymer of the invention, to a method

IMPI to make an amphiphilic branched polysiloxane prepolymer of the invention, to a method for making silicone hydrogel contact lenses from a prepolymer of the invention, and to silicone hydrogel contact lenses prepared from a prepolymer of the invention.

In the first aspect, the invention provides an amphiphilic branched polysiloxane prepolymer suitable for making silicone hydrogel contact lenses in accordance with Lightstream Technology.MR. The polysiloxane prepolymer of the invention comprises: (1) from about 5 percent to about 75 percent, preferably from about 10 percent to about 65 percent, more preferably from about 15 percent to about 55 percent, still more preferably from about 20 percent to about 45 percent by weight of hydrophilic monomeric units derived from at least one hydrophilic vinyl monomer, (2) from about 1 percent to about 85 percent, preferably from about 2.5 percent to about 75 percent, more preferably from about 5 percent to about 65 percent by weight of units of crosslinking polysiloxane derived from at least one crosslinking polysiloxane having two or more terminal ethylenically unsaturated groups, (3) from about 2 percent to about 48 percent 27 ΙΜΡΙ ^>

• WJIWUTO MEXICAN

OF THE "V * C ~" * E 'STAY%, preferably from about 3 percent to about 38 percent, more preferably from about 4 percent to about 28 percent by weight of polysiloxane chains earrings, each of which is terminated with an ethylenically unsaturated group, and (4) from about 0.25 percent to about 5 percent, preferably from about 0.5 percent to about 4 percent, more preferably from about 0.75 percent to about 3 percent, still more preferably from about 1 percent to about 2 percent by weight of units of chain transfer derived from a chain transfer agent other than a RAFT agent.

In accordance with the invention, an amphiphilic branched polysiloxane prepolymer is soluble in a solvent or in a mixture of two or more solvents at room temperature, such that a lens-forming composition can be obtained that contains about 5 percent to about 90 weight percent of the amphiphilic branched polysiloxane prepolymer.

Examples of suitable solvents include, without limitation, water, tetrahydrofuran (THF), trlpropylene glycol methyl ether, dipropylene glycol methyl ether, ethylene glycol n-butyl ether, ketones (e.g. acetone, methyl ethyl ketone , etc.), diethylene glycol n-butyl ether, diethylene glycol methyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate,

IMPI '* «STriyro m» k>no o »M« OTIEOAD INOtlSTlUAl di propylene glycol methyl ether acetate I, propylene glycol n-propyl ether, dipro p ileng I ico I n-propyl ether, n-butlTeler d?

tri propi I eng I i col, propylene glycol n-butyl ether, di propylene glycol n-butyl ether, i ng I ico I, tri p ro pi I n-butyl ether in gly i co I , propylene glycol phenyl ether, dipropylene glycol dimethyl ether, dipropyleng I i co I, po I i et i I eng I i co I es, polypropylene glycols, ethyl acetate, butyl acetate, amyl acetate, lactate methyl, ethyl lactate, isopropyl lactate, methylene chloride, 2-butanol, 1-propanol, 2-propanol, menthol, cyclohexanol, cyclopentanol and exonorborneol, 2-pentanol, 3-pentanol, 2-hexanol, 3hexanol, 3-methyl-2-butanol, 2-heptanol, 2-octanol, 2-nonanol, 2decanol, 3-octanol, norborneol, terbutanol, teramyl alcohol , 2-methyl-2-pentanol, 2,3-dimethyl-2-butanol, 3-methyl-3-pentanol, 1-methylcyclohexanol, 2-methyl-2-hexanol, 3,7-dimethyl-3-octanol, 1-chloro -2-methyl-2-propanol, 2-methyl-2-heptanol, 2-methyl-2-octanol, 2-2-methyl-2nonanol, 2-methyl-2-decanol, 3-methyl-3-hexanol, 3-methyl -3-heptanol, 4-methyl-4-heptanol, 3-methyl-3-octanol, 4-methyl-4-octanol, 3-methyl-3nonanol, 4-methyl-4-nonanol, 3-methyl-3-octanol, 3-ethyl-3-hexanol, 3-methyl-3-heptanol, 4-ethyl-4- heptanol, 4-propyl-4-heptanol, 4-isopropyl-4-heptanol, 2,4-dimethyl-2-pentanol, 1-methyl-cyclopentanol, 1-ethylcyclopentanol, 1-ethyl-cyclopentanol, 3-hydrox i-3 - m et i I -1 -butene, 4-hydroxy-4-methyl-1-cyclopentanol, 2-phenyl-2-propanol, 2-methoxy-2-methyl-2-propanol, 2,3, 4-trimethyl-3-pentanol, 3,7-dimethyl-3-octanol, 2-phenyl-2-butanol, 2-methyl-1-phenyl-2-propanol and 3-ethyl-3-pentanol, 1-ethoxy-2-propanol, 1-methyl-2-propanol, teramyl alcohol, isopropanol, 1-methyl-2-pyrrolidone, Ν, Ν- dimethyl-propionamide, dimethyl-formamide, dimethyl29

acetamide, dimethyl-propionamide, N-methyl-pyrrolidinone ^ and axis mixtures thereof.

An amphiphilic branched polysiloxane prepolymer of the invention is obtained by: (i) polymerizing a polymerizable composition to obtain an amphiphilic branched polysiloxane copolymer, wherein the polymerizable composition comprises: (a) a partially Eden-functionalized polysiloxane, wherein the partially Eden-functionalized polysiloxane is a mixture of reaction products obtained by reacting a first Eden-functionalizing vinyl monomer having a reactive first functional group with a functional polysiloxane compound having two or more second reactive functional groups in a molar equivalent ratio, REquivalent, from about 40 percent to about 95 percent, preferably from about 50 percent to about 95 percent, more preferably from about 60 percent to about 92 percent, still more preferably from about 70 percent percent to about 90 percent (Eden-functionalizing vinyl monomer to functional polysiloxane compound), wherein each first reactive functional group reacts with a second reactive functional group in the presence or absence of a coupling agent to form a covalent bond, wherein the reaction product mixture comprises at least one polysiloxane crosslinker having

IMPI Mexican iNSTmrro Λ

OF THE FtOMEDAD

4N r, t «rrw i at least two ethylenically unsaturated groups and at least one polysiloxane vinyl monomer or macromer having at least one second reactive functional group and at least one ethylenically unsaturated group; (b) at least one hydrophilic vinyl monomer; (c) optionally, but preferably, a hydrophobic vinyl monomer, more preferably a bulky hydrophobic vinyl monomer (ie, one having a bulky surrogate group; (d) a chain transfer agent other than a RAFT agent, wherein the chain transfer agent optionally, but preferably, includes a third reactive functional group; and (e) a free radical initiator (a photoinitiator or thermal initiator, preferably a thermal initiator); and (ii) ethylenically functionalizing the amphiphilic branched polysiloxane copolymer by reacting with a second ethylenically functionalizing vinyl monomer having a fourth reactive functional group that reacts with a second or third reactive functional group in the presence or absence of a reactive agent. coupling to form a covalent bond, thereby forming the amphiphilic branched polysiloxane prepolymer.

Preferably, the functional polysiloxane compound in the polymerizable composition is defined by the formula (1) or (2):

FG — PDMS — G2—FG (1)

CR (—G ·, —PDMS — G2—FG)a1 (2) where:

G, and G2 independently of each other, they are a link

ΙΜΡΙ (NsrrruT mexicanc • ε la mohedal 'O-j_ ^:C industrial Sídirecto, a divalent alkylene radical of "1 — to 10-linear or branched carbon atoms, a divalent radical of - (- alk' — O - ^ - alk—, where q is an integer from 1 to 5 , and alk and alk ', independently of each other, are a divalent radical of alkylene of 1 to 6 carbon atoms, or a divalent radical of R' i - X ί - EX2—R ' 2-, where R'-i and R '2 independently of each other, they are a direct bond, a divalent radical of alkylene of 1 to linear or branched carbon atoms, or a divalent radical of

as defined above, Xt and X2 independently of each other, they are a bond selected from the group consisting of -O-, —n—, —C — N—, —N — c—,

R 'oo R' o O pin ii I ii ll II —N - c - NH—, —HN - c - N—, - O - C - NH—, HN - C - O, —S - C - NH—, —O - C—, —C - O -, -S-, and —HN - C - S—, where R 'is H or alkyl of 1 to 8 carbon atoms, E is a di-alkyl radical, a cycloalkyl diradical, a Iq ui I-cycloa I qui lo diradical, an alkyl aryl diradical, or an aryl diradical with up to 40 carbon atoms, which may have ether bonds, thio, or amine in the main chain;

PDMS is a divalent polysiloxane radical of the formula (3):

- Say - U! —D24u2—DskrTTr ' 1 ' \ ' °/ VJW (3)

IMPI

MEXICAN INSTITUTE Μ LA PROPERTY INDUSTRIAL where v is 0 or 1, ω is an integer from 0 to 5, LH and U2 independently of each other, they represent a divalent radical of

-R '1-X1-FORMER2-R,2-, as defined above, or a divalent radical of

, as defined above, Say,

D2 and D3 independently of each other, they are a divalent radical selected from the group consisting of - (CH2CH2OR)tCH2CH2-, where t is an integer from 3 to 40, -CF2- (OCF2)to(OCF2CF2)b-OCF2-, where a and b, independently of each other, are an integer from 0 to 10, with the understanding that a + b is a number in the range from 10 to 30, and a divalent group of the formula (4):

?3 í

Yes O Yes O i _L

R4 Rg

Si-O - ¿ίο nR K8 P K10 (4) where R3, R4, R5, Re, R7, Re, R9, and R10, independently of each other, are alkyl of 1 to 10 carbon atoms, aminoalkyl of 1 to 10 carbon atoms, hydroxy-a Iq ui lo of 1 to 10 carbon atoms, ether of 1 to 10 carbon atoms carbon, phenyl substituted by alkyl of 1 to 4 carbon atoms or by alkoxy of 1 to 4 carbon atoms, fluoroalkyl of 1 to 10 carbon atoms, fluoroether of 1 to 10 carbon atoms, aryl radical of C 6 to 18, cyano- (C 1 to 12 alkyl), -alk- (OCH2CH2)n-OR1 t, where alk is a divalent alkylene radical of 1 to 6 carbon atoms, Rn is hydrogen or alkyl of

IMPI

MEWCANO INSTITUTE

OF THE INDUSTRIAL PtOPiITY to 6 carbon atoms, and n is an integer from 1 to 10; m and p, independently of each other, are an integer from 0 to 350, and (m + p) is from 1 to 700, with the understanding that at least one of Di, D2 and D3 It is represented by the formula (3);

CR is a multivalent organic radical having a valence of 1;

a1 is an integer of 3, 4, or 5; Y

FG is selected from the group consisting of amino group (-NHR as defined above), hydroxyl group, carboxylic acid group, acid halide groups (-COX, X = Cl, Br, or I), group of acid anhydrate, aldehyde group, azalactone group, isocyanate group, epoxy group, aziridine group, thiol (-SH), and amide groups (-CONH2).

Preferably, in formula (1) or (2), PDMS is a divalent polysiloxane radical of formula (3), where: v is 0 or 1, preferably 1, ω is an integer from 0 to 3, preferably 1, UiyU2 are as defined above, D-ι, D2 and D3 independently of each other, they are a divalent radical of formula (4), where R3 to R10 independently of each other, they are methyl, fluoro (alkyl of 1 to 18 carbon atoms), and / or -alk- (OCH2CH2) n-OR1i, where alk is a divalent alkylene radical of 1 to 6 carbon atoms and Rn is alkyl of 1 to 6 carbon atoms, and n is an integer of 1 to 10, m and p, independently of each other, are an integer of 1 to 698 and (m + p) is 2 to 700.

Different polysiloxanes terminated in

Difunctional (reactive) group (ie having polysiloxane mantle of formula (4)) with commercial suppliers (eg at Gelest, Inc., or Fluorochem). Otherwise, a person skilled in the art will know how to prepare these difunctional group terminated polysiloxanes according to procedures known in the art and described in Journal of Polymer Science - Chemistry, 33, 1773 (1995) (incorporated herein for reference in its entirety).

When a functional polysiloxane compound of the formula (1) is a functional extended chain polysiloxane compound, that is, having two to five polysiloxane segments of the formula (4), this functional extended chain polysiloxane compound is can be prepared by reacting a difunctional group terminated (reactive) polysiloxane compound having a single polysiloxane segment of formula (4), and two third reactive functional groups with a coupling agent having two fourth reactive functional groups, wherein the third and fourth reactive functional groups are different from each other, but reactive with each other, and are selected from the group consisting of amino group (-NHR as defined above), hydroxyl group, thiol group, carboxylic acid group, acid halide groups (-COX, X = Cl, Br, or I), acid anhydrate group, aldehyde group, azalactone group, isocyanate group, epoxy group, aziridine group, thiol (-SH), and amide groups (—CONH2). A coupling agent that has two reactive fourth functional groups

It can be a di-isocyanate, a di-acid halide, a di-carboxylic acid compound, a di-acid halide compound, a di-azalactone compound, a di-epoxy compound, a diamine, or a diol . A person skilled in the art is well aware of how to select a coupling reaction (eg, any described above in this application), and the conditions thereof, to prepare a functional extended chain polysiloxane compound.

Any suitable diisocyanates of 4 to 24 carbon atoms can be used in the invention. Examples of preferred di-isocyanates include, without limitation, isophorone di-isocyanate, hexamethyl-1,6-di-isocyanate, 4,4'-dicyclohexyl-methane di-isocyanate, toluene-di-isocyanate, di-isocyanate 4,4'-diphenyl, 4,4'-diphenyl-methane di-isocyanate, p-phenylene di-isocyanate, 4,4'-d ¡fe ni ld i-is or 1,4-phenylene cyan ate, 1,3-bi s- (4,4'isocyanate-methyl) -cyclohexane, di-cyclohexane isocyanate, and combinations thereof.

Any suitable diamines can be used in the invention. An organic diamine may be a straight or branched aliphatic diamine of 2 to 24 carbon atoms, a cycloaliphatic diamine or I ifa ti ca-c ic I or I ifa ti ca of 5 to 24 carbon atoms, or an aromatic or alkyl diamine. -aromatic from 6 to 24 carbon atoms. A preferred organic diamine is N, N'-bis- (hydroxy-ethyl) ethylene-diamine, N, N'-dimethyl-ethylene-diamine, ethylene-diamine, N, N-dimethyl-1, 3-propanediamine, N, N'-diethyl-1,3-propanediamine, pro pan36 iMLT^3

1,3-diamine, butane-1,4-diamine, pentane-1,5-diamine, hexamethylene-, diamine, and isophorone diamine.

Any suitable di-acid halides can be used in the invention. Examples of the preferred di-acid halides include, without limitation, fumaryl chloride, suberoyl chloride, succinyl chloride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, sebacoyl chloride, adipoyl chloride, trimethyl chloride. -adipoyl, azelaoyl chloride, dodecanedioic acid chloride, succinic chloride, glutaric chloride, oxalyl chloride, and dimer acid chloride.

Any suitable di-epoxy compounds can be used in the invention. Examples of preferred diepoxic compounds are neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 6-hexanediol diglycidyl ether, glycerol diglycidyl ether, ethylene diglycidyl ether. -gIicoI, diglycidyl ether of diethylene glycol, diglycidyl ether of polyetiIengIicoI, diglycidyl ether of propylene glycol, and diglycidyl ether of dipropylene ng I i co I. these diepoxic compounds are commercially available (for example, the DENACOL series di-epoxy compounds from Nagase ChemteX Corporation).

Any suitable C2-24 diols (ie, compounds with two hydroxyl groups) can be used in the invention. Examples of preferred diols include, without limitation, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, 1,4-butanediol,

IMPI

1 * 5'1 HUTO MBUCAWC

NIA MOHEDAL INDUSTRIAL different pentanediols, different hexanediols, and different cyclohexanediols.

Any C 3 to 24 dicarboxylic acid compounds can be used in the invention. Examples of preferred di-carboxylic acid compounds include, without limitation, a straight or branched C 3 to 24 aliphatic dicarboxylic acid, a cycloaliphatic dicarboxylic acid or a I if a ti co-cy I or an I if a ti co of 5 to 24 carbon atoms, an aromatic or araliphatic dicarboxylic acid of 6 to 24 carbon atoms, or a dicarboxylic acid containing amino or imido groups or N-heterocyclic rings. Examples of suitable aliphatic dicarboxylic acids are: oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, dimethyl-malonic acid, octadecylsuccinic acid , tri-ethyl-adi pico acid, and dimer acids (the dimerization products of unsaturated aliphatic carboxylic acids, such as oleic acid). Examples of suitable cycloaliphatic dicarboxylic acids are: 1,3-cyclobutane dicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,3- and 1,4-cyclohexanedicarboxylic acid, 1,3- and 1,4-dicarboxylic acid. -methyl-cyclohexane, 4,4'-dicyclohexyl-dicarboxylic acid. Examples of suitable aromatic dicarboxylic acids are: terephthalic acid, isophthalic acid, o-phthalic acid, 1,3-, 1,4-, 2,6- or 2,7-naphthalene dicarboxylic acids, 4,4 'acid -d¡pheniI-dicarboxylic acid, 4,4'-diphenyl-suIfon-dicarboxylic acid, 1,1,3IMPI

INSTITUTO MKXlpAMr o »L» mohedal t * DUST! IAl trimethyl-5-carboxy-3- (p-carboxy-phen¡l) -ndane, acid '4,4'-diphen¡l-etherd i car b οχ í I i co, bis-p- (carboxy-phenyl) -methane. '' ~ '

Any suitable C10-24 di-azalactone compounds can be used in the invention. Examples of the diazalactone compounds are those described in United States Patent Number 4,485,236 (incorporated herein by reference in its entirety).

Any suitable dithiols can be used in the invention. Examples of these dithiols include, without limitation, C2-12 alkyl dimercaptans (e.g., ethyl dimercaptan, propyl dimercaptan, butyl dimercaptan, pentamethylene dimercaptan, hexamethylene dimercaptan, heptamethylene dimercaptan, octamethylene- dimercaptan, nonamethylenedimercaptan, decamethylene-dimercaptan, or combinations thereof), ethyl-cyclohexyl-dimercaptan, dipenten-dimercaptan, benzenedithiol, methyl substituted benzenedithiol, benzenedimethanethiol, Glycol dimercaptoacetate, ethyl ether dimercaptan (diglycol-dimercaptan), triglycol-dimercaptan, tetraglycoldimercaptan, dimercaprol, dimercaptopropanol, dimercaptobutanol, dimercaptopentanol, dimercapto-propionic acid, dihydrolipoic acid, dithioerythercaptan, combinations of the same.

In formula (2), CR is the nucleus of functional multi-arm star polysiloxane and is derived from a

branching, that is, a compound having 3 to 5, preferably 3, fifth reactive functional groups that can participate in any known coupling reaction, and are selected from the group consisting of amine groups, hydroxyl groups, carboxylic groups , isocyanate groups, thiol groups, (meth) acryloyl groups, vinyl groups (i.e. wherein each carbon-carbon double bond is not directly connected to a carbonyl group or an oxygen or nitrogen atom), acid halide groups, epoxy groups, and combinations thereof. Examples of preferred branching agents include, without limitation, glycerol, diglycerol, triglycerol, arabitol, 1,1,1-tris-hydroxymethyl-ethane, 1,1,1-tris-hydroxy-methyl-propane, 1,2 , 4-butanetriol, 1,2,6hexanetriol, erythritol, pentaerythritol, diethylene-triamine, N-2'-amino-ethyl-1,3-propylene-diamine, N, N-bis- (3-amino-propyl) -amine, N, N-bis- (6-amino-hexyl) -amine, triethion-tetramine, the isocyanurate trimer of hexamethylene-di-isocyanate, 2,4,6-toluene-tri-isocyanate, p, p ', p-triphenylmethane-tri-isocyanate, and the trifunctional trimer (isocyanurate) of isophorone diisocyanate, trimesoyl chloride, cyclohexane chloride 1,3,5-t ri car bo ni I o, acid chloride trimeric, triglycidyl isocyanurate (TGIC), trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, triallyl isocyanurate, triallyl cyanurate, aconitic acid, citric acid, 1,3,5-cyclohexane-tricarboxylic acid, acid

1,3,5-trimethyl-1,3,5-cyclohexane-tri-carboxylic acid, 1,2,3-bencentrycarboxylic acid, 1,2,4-benzenetricarboxylic acid, and 1 , 3,5pe n ta n ot rit io I.

IA ........—

A person skilled in the art is well aware of how to prepare a functional multi-arm star polysiloxane of formula (2) according to any of the known coupling reactions. For example, a polysiloxane of the formula (2) can be prepared as follows. A branching agent is reacted with an excessive molar equivalent amount of a di-functionalized polydisiloxane to form a functional multi-arm star polydisiloxane with three or four arms, each having a terminal reactive functional group for further reactions, according with any of the known coupling reactions, including those described above. If each arm comprises more than one polysiloxane segment, a functional extended chain polysiloxane prepared above can be used to react with a branching agent.

In accordance with the invention, any suitable ethylenically functionalizing vinyl monomers can be used in the invention, for the preparation of the partially ethylenically functionalized polysiloxanes and / or for the preparation of an amphiphilic branched polysiloxane prepolymer of the invention. It is understood that the second ethylenically functionalizing vinyl monomer may be different from, but preferably is identical to, the first ethylenically functionalizing vinyl monomer (used in the preparation of the partially ethylenically functionalized polysiloxane). Examples of

IMPI

INSTITUTO MK1CANO DI U non AGE Ethylenically functionalizing vinyl monomers include, without limitation, hydroxy-alkyl carbon (meth) acrylate, hydroxy-alkali of 2 to 6 allyl alcohol atoms, allyl-amine, (meth) acrylate of 2 to 6 carbon atoms- (meth) acrylamide, amino-alkyl of 2 to 6 carbon atoms, (meth) acrylate of alkyl of 1 to 6 carbon atoms-amino-alkyl of 2 to 6 carbon atoms, vinyl amine , amino-C2-C6-alkyl- (meth) acrylamide, C 1 -C 6 alkyl-C 2 -C 6 -alkyl (meth) acrylamide, acrylic acid, C 1 -C 4 alkali-acrylic acid (e.g. methacrylic acid, ethyl-acrylic acid, co, propi Ia c rí I i co acid, butyl-acrylic I co), / V- [tr¡s- (hydroxy-m et i I) -m et i I] acrylamide, acid N, Ν-2-acrylamido-glycolic, beta-methyl-acrylic acid (crotonic acid), alpha-phenyl-acrylic acid, beta-acryloxypropionic acid, sorbic acid, angelic acid, Cinnamic acid, 1-carboxy-4-phenyl-butadiene-1,3-taconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, maleic acid, fumaric acid, 1-12 atom aziridinyl alkyl (meth) acrylate carbon (for example, 2- (1-aziridinyl) -ethyl (meth) acrylate, 3- (1-az¡r¡d¡n¡l) -propyl (meth) acrylate - (1-aziridinyl) -butyl, 6- (1-aziridinyl) -hexyl (meth) acrylate, or 8- (1-aziridinyl) -octyl (meth) acrylate, glycidyl (meth) acrylate, vinylg I i cid i l-ether, a I ii-g I i cid i l-ether r, (meth) acrylic acid halide groups (—COX, X = Cl, Br, or I), (meth) C 1 -C 6 -alkyl isocyanate acrylate, vinyl monomers containing azalactone (for example, 2-vinyl-4,4-dimethyl-1,3-oxazolin-5-one, 2-isopropenyl42

4,4-dimethyl-1,3-oxazolin-5-one, 2-vinyl-4-methyl-4 * 5firT ^ 3-oxazolin-5one, 2-isopropenyl-4-methyl-4-butyl-1 , 3-oxazolin-5-one, 2-v¡n yl-4,4dibutyl-1,3-oxazolin-5-one, 2-¡sopropenyl-4-methyl-4-dodec¡l-1,3oxazolin -5-one, 2-isopropenyl-4,4-diphenyl-1,3-oxazolin-5-one, 2-isopropenyl-4,4-pentamethylene-1,3-oxazolin-5-one, 2-isopropenyl-4,4-tetramethylene -1,3-oxazolin-5-one, 2-vinyl-4,4-di-ethyl-1,3-oxazolin-5-one, 2-vinyl-4-methyl-4-nonyl-1 , 3-oxazolin-5-one, 2-isopropenyl-4-methyl-4-phenyl-1,3-oxazolin-5-one, 2-¡sopropenyl-4-methyl-4-benzyl-1,3-oxazol¡n5-one, 2-vinyl-4,4-pentamethylene-1,3-oxazolin-5-one, and 2-vinyl-4,4d¡methi 1-1,3-oxazolin-6-one, with 2-vinyl-4,4-dimethyl-1,3-oxazolin-5-one (VDMO), and 2-isopropenyl -4,4-dimethyl-1,3-oxazolin-5-one (IPDMO) as the preferred azalactone-containing vinyl monomers), and combinations thereof.

Preferably, the first reactive functional group of the first ethylenically functionalizing vinyl monomer, the fourth reactive functional group of the second ethylenically functionalizing vinyl monomer, the second reactive functional groups of the functional polysiloxane compound, and the third reactive functional group of the chain transfer agent independently of each other, are selected from the group consisting of amino group (-NHR 'as defined above), hydroxyl group, carboxylic acid group, acid halide groups (-COX, X = Cl, Br, or I), group of acid anhydrate, aldehyde group, azalactone group, isocyanate group, epoxy group, aziridine group, amide groups (—CONH2), and combinations thereof, plus

IMPW

ΙΝ5ΤΓΓ <ΠΌΜ «1θΛΝο

OF LA MOHEDA DC / wJ are preferably selected from the group consisting of the amino group (-NHR 'as defined above),' nicfroxyl group, carboxylic acid group, acid halide groups (-COX, X = Cl , Br, or I), azalactone group, isocyanate group, epoxy group, aziridine group, and combinations thereof, with the understanding that a first or fourth reactive functional group may react with a second or third reactive functional group in the presence or absence of a coupling agent to form a covalent bond.

A partially ethylenically functionalized polysiloxane is understood to comprise at least one polysiloxane vinyl monomer or macromer having at least one ethylenically unsaturated group and at least one reactive functional group. This vinyl polysiloxane monomer or macromer having at least one reactive functional group results in the formation of pendant polysiloxane chains, each terminated with a reactive functional group in an amphiphilic branched polysiloxane copolymer, and eventually the formation of chains of pendant polysiloxane, each terminated with an ethylenically unsaturated group in an amphiphilic branched polysiloxane prepolymer of the invention. When a vinyl polysiloxane monomer or macromer has two or more ethylenically unsaturated groups and at least one reactive functional group, a polysiloxane crosslinker may also serve.

Preferably, a functional polysiloxane used for

Preparation of a partially, Eden-functionalized polysiloxane is represented by formula (1). More preferably, an Eden-functionalizing vinyl monomer is reacted with a functional polysiloxane compound of the formula (1) in a molar equivalent of 70 percent to about 90 percent to obtain a partially Eden-functionalized polysiloxane.

In accordance with this aspect of the invention, any suitable hydrophilic vinyl monomers can be used in the preparation of an amphiphilic branched polysiloxane prepolymer of the invention. The hydrophilic vinyl monomers are, without this being an exhaustive list, hydroxyl-substituted C 1-6 alkyl (meth) acrylates, C 1-6 alkyl- (meth) acrylamides substituted by hydroxyl, C 1-6 -Hydroxyl-substituted vinyl ethers, C 1-6 alkyl- (meth) acrylamide, di- (C 1-6 alkyl) - (meth) acrylamide, N-viniI- pyrroI, N-viniI-2-pyrroIidone, 2-vinyl-oxazoline, 2-vinyl-4,4'-dialkyl-oxazolin-5-one, 2- and 4-vinylpyridine, olefinically unsaturated carboxylic acids having a total of 3 to 6 carbon atoms, alkyl of 1 to 6 atoms carbon substituted by amino (where the term amino also includes quaternary ammonium), (meth) acrylates or (meth) acrylamides of mono- (alkyl of 1 to 6 carbon atoms-amino) - (alkyl of 1 to 6 carbon atoms) carbon) and di- (C 1 to 6 alkyl-amino) (C 1 to 6 alkyl), allyl alcohol, vinyl amine, N45

IMPI

ΓΝΠΤΠΓΓΠ MEXICAN vinyl-alkyl of 1 to 6 carbon atoms-amide, N-vinyl-N-alkyl of 1 to 6 carbon atoms-amide, and combinations thereof.

Examples of preferred hydrophilic vinyl monomers are Ν, Ν-dimethyl-acrylamide (DMA), Ν, Ν-dimethyl-methacrylamide (DMMA), 2-acrylolamidoglycolic acid, 3-acryloyl-amino-1-propanol, Nh id roxy-ethyl-acrylamide, / V- [tris- (hydroxy-methyl) -methyl] -acrylamide, N-methyl-3-methylene-2-pyrrolidone, 1-ethyl-3-methylene- 2-p¡rrolidone, 1-methyl-5-methylene-2-pyrrolidone, 1-ethyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone, 5-ethyl-3-methylene-2- pyrrolidone, 1-n-propyl-3methylene-2-pyrrolidone, one -n-prop¡l-5-methylene-2-p¡rrolidone, 1-isopropyl

3-methylene-2-pyrrolidone, 1-isopropyl-5-methylene-2-pyrrolidone, 1 - n-butyl3-methylene-2-pyrrolidone, 1-tert-butyl-3-methylene-2-pyrrolidone, methacrylate 2-hydroxy-ethyl (HEMA), 2-hydroxy-ethyl acrylate (HEA), hydroxy-propyl acrylate, hydroxy-propyl methacrylate (HPMA), 2-hydroxy-propyl-trimethyl-ammonium methacrylate hydrochloride, hydrochloride aminopropyl methacrylate, dimethylaminoethyl methacrylate (DMAEMA), glycerol methacrylate (GMA), N-vinyl-2-pyrrolidone (NVP), Allyl alcohol, vinyl pyridine, a C 1-4 alkoxy (meth) acrylate-polyethylene glycol having a weight average molecular weight of up to 1,500, methacrylic acid, N-vinylformamide, N-vinyl-acetamide, N- vinyl-isopropylamide, N-vinyl-N-methyl-acetamide, N-vinyl-caprolactam, and mixtures thereof. Among the preferred hydrophilic vinyl monomers, those free from any reactive functional groups are particularly preferred for incorporation into the polymerizable composition for

IMPI

MEXICAN INSTITUTE

OF THE PROPERTY

INDUSTRIAL preparation of amphiphilic branched polysiloxane copolymer.

In accordance with this aspect of the invention, any suitable hydrophobic vinyl monomers can be used in the preparation of an amphiphilic branched polysiloxane prepolymer of the invention. Examples of preferred hydrophobic vinyl monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate (, butyl (meth) acrylate, butyl (meth) acrylate secondary, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, styrene, chloroprene, vinyl chloride, vinylidene chloride, acrylonitrile, 1-butene, butadiene, methacrylonitrile, vinyl toluene, vinyl-ethyl-ether, perfluoro-hexyI-ethiI-thiocarboniIamine-ethyl methacrylate, isobornyl methacrylate, trifluoroethyl-isopropyl methacrylate, methacrylate-ethyl-isopropyl methacrylate , hexafluorobutyl methacrylate, a vinyl monomer containing silicone, and mixtures thereof. Most preferably, the polymerizable composition comprises a bulky hydrophobic vinyl monomer. Preferred bulky hydrophobic vinyl monomers include, without limitation, N- [tris- (tri m eti ls i loxy) -si I i lp ro pil] - (m et) a cri I am id a; N [tr¡s- (dimethyl-propyl-siloxy) -silyl-propyl] - (meth) acrylate; N- [tris- (dimephenyl-silox) -silyl-propyl] - (meth) acrylamide; N- [tris- (dimethyl-ethyl-siloxy) silyl-propyl] - (meth) acrylamide; N- (2-hydroxy-3- (3- (bis- (trimethyl-s¡l¡lox¡) meth¡ls¡l¡l) -propylox¡) -propyl) -2-methyl-acrylam gives; N- (2-hydroxy-3- (3- (b¡s (trimethyl-silylox) -methyls¡l¡l) -propylox¡) -propyl) -acrylamide; N, N-bis- [2-

47 IMPI twrrrruTo mkicano DE LA FROREOAE) INlXlsnUAl hydrox¡-3- (3- (b¡s- (tr¡met¡ ls¡ liloxy) -m eti ls¡ l¡l) -prop¡lox¡) -propyl] -2 -m ethylacrylamide; N, Nb¡s- [2-hydroxy-3- (3- (bis- (trimethyl-silaloxy) -methyl-silal) propyloxy) -propyl] -acrylamide; N- (2-hydroxy-3- (3- (tris- (trimethyl-silyloxy) silyl) -propyloxy) -propyl) -2-methyl-acrylamide; N- (2-hydroxy-3- (3- (tris (trimeti l-silyloxy) -silyl) -propyloxy) -propyl) -acrylamide; N, N-bis- [2-hydroxy3- (3- (tris- (trimethyl-silaloxy) -silal) -propyloxy) -propyl] -2-methyl-acrylamide; N, N-bis- [2-hydroxy-3- (3- (tris- (trimethyl-silyloxy) -silyl) -propyloxy) -propyl] acrylamide; N- [2-hydroxy-3- (3- (tert-butyl-dimethyl-l) -propyl-propyl] -2-methyl-acrylamide; N- [2-hydroxy-3- (3- (tert-butyl-dimethyl-silyl) -propyloxy) propyl] -acrylamide; N, N-bis- [2-hydroxy-3- (3- (tert-butyl-dimethyl-silyl) propyloxy) -propyl] -2-methyl-acrylamide; N, N-bis- [2-hydroxy-3- (3- (tert-butyldimethyl-silyl) -propyloxy) -propyl] -acrylamide; 3-methacryloxy-propylpentamethyl-disiloxane; tris- (trimethyl-siIloxy) -siIyl-propylo (TRIS) methacrylate; (3-methacryloxy-2-hydroxy-propyloxy) -propyl-bis- (trimethyl-siloxy) methyl-silane); (3-metacryloxy-2-hydroxy-propyloxy) -p ropil-tris- (tri-methylsiloxy) -silane; 3-methacryloxy-2- (2-hydroxy-ethoxy) -propyloxy) -propyl-bs (trimethylsiloxy) -methyl-silane; Ν-2-methacryloxy-ethyl-O (methylb¡s-trimethyl-siloxy-3-propyl) -silyl carbamate; 3- (trimethylsilyl) propyl vinyl carbonate; 3- (vinyloxy-thocarbonyl) -propyl-tris- (trimethyl-siloxy) -silane; 3- [tri-s- (trimethyl-siloxy) -silyl] -propyl carbamate; 3- [tris- (trimethylsiloxy) -silyl] -propyl-allyl carbamate; 3- [Tris- (trimethylsiloxy) -silyl] -propyl-vinyl carbonate; tert-butyl dimethyl siloxy ethyl vinyl carbonate; trimethylsilyl ethyl vinyl carbonate; trimethylsilyl methylvinyl carbonate; tert-butyl (meth) acrylate, cyclohexyl acrylate, isobornyl methacrylate, a vinyl monomer containing polysiloxane (which

INSTITUTE M £ X! CAN <DE LA MONEDAD INBUST1ML has 3 to 8 silicone atoms), and combinations thereof.

It is believed that the presence of this bulky hydrophobic vinyl monomer in the polysiloxane prepolymer may be capable of minimizing or eliminating optical defects (permanent deformations) resulting from handling during manufacture in lenses made from a composition to form. lenses, which comprises the polysiloxane prepolymer. This deformation or optical defect refers to the permanent crease marks observed on the lens by a Contact Lens Optical Quality Analyzer (CLOQA) after the lens is manually folded as described in Example 1 of the Patent Application United States of America Pending Number 12 / 456,364 (incorporated herein by reference in its entirety). When a bulky hydrophobic vinyl monomer is present, the resulting lenses are believed to exhibit a 'healing' effect that eliminates optical defects (i.e., crease marks become transient and may disappear after a short period of time , for example, about 15 minutes or less).

According to the invention, a chain transfer agent may comprise one or more thiol groups, for example two or more, preferably one thiol group. When a chain transfer agent comprises a reactive functional group (eg, a hydroxyl, amino, or carboxylic acid group) in addition to the thiol group, this chain transfer agent can be

used to provide functionality for the subsequent addition of an ethylenically unsaturated group. Chain transfer agents include organic primary thiols or mercaptans having an additional reactive functional group, such as, for example, hydroxyl, amino, N-C 1 -C 6 -alkyl, amino, carboxyl, or a suitable derivative of the same. A preferred chain transfer agent is a cyc I or I if a ti co, or preferably aliphatic, thiol, having 2 to about 24 carbon atoms, and having an additional reactive functional group selected from amino, hydroxyl and carboxyl; In accordance with the foregoing, the preferred chain transfer agents are aliphatic mercapto carboxylic acids, hydroxy mercaptans, or amino mercaptans. Examples of preferred chain transfer agents are 2-mercaptoethanol, 2-aminoethanethiol (cysteamine), 2-mercapto-propionic acid, thioglycolic acid, thiolactic acid, ethandithiol, propandithiol, and combinations thereof. . In the case of an amine or carboxylic acid, the chain transfer agent may be in the form of the amine or free acid or, preferably, in the form of a suitable salt thereof, for example a hydrochloride in the case of an amine, or a sodium, potassium or amine salt in the case of an acid.

In a preferred embodiment, the polymerizable composition comprises a first hydrophilic vinyl monomer free of any reactive functional group capable of participating in a reaction of

coupling with the second ethylenically functionalizing vinyl monomer, and a second hydrophilic vinyl monomer having a reactive functional group capable of participating in the coupling reaction with the second ethylenically functionalizing vinyl monomer, wherein the first and second hydrophilic vinyl monomers are present in the polymerizable composition in a ratio of about 5: 1 to about 30: 1. The first hydrophilic vinyl monomer is preferably selected from the group consisting of N, N-dimethyl- (meth) acrylamide, N-methyl

3-methylene-2-pyrrolidone, 1-ethyl-3-methylene-2-pyrrolidone, 1-meth I-5-methylene-2-pyrrolidone, 1-ethyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene -2-pyrrolidone, 5-ethyl-3-methylene-2-p¡rrolidone, 1 -n-propyl-3methylene-2-pyrrolidone, 1-n-propyl-5-methylene-2-p¡rrolidone , 1-isopropyl3-methylene-2-pyrrolidone, 1- ¡sopro pil-5-methylene-2-p¡rrolidone, 1-n-butyl3-methylene-2-p¡rrolidone, 1-tertbutyl-3-methylene -2-pyrrolidone, dimethyl-amino-ethyl (meth) acrylate, N-vinyl-2-pyrrolidone, a C 1 -C 4 alkoxy (meth) acrylate-polyethylene glycol, N-vinyl-formamide, N-vinyl-acetamide, N-vinyl-isopropylamide, N-vinyl N-methyl-acetamide, and mixtures thereof ; and the second hydrophilic vinyl monomer is preferably selected from the group consisting of hydroxyl-substituted C 1-4 alkyl (meth) acrylate, hydroxyl-substituted C 1-4 alkyl (meth) acrylamide , C 1-4 alkyl (meth) acrylate substituted by amino, C 1-4 alkyl- (meth) acrylamide substituted by amino, allyl alcohol, allylIMPI MEXICAN INSTITUTE DE LA PROPERTY INDUSTRIA !.

amine, and mixture thereof.

In another preferred embodiment, an amphiphilic branched polysiloxane copolymer is obtained to make an amphiphilic branched polysiloxane prepolymer of the invention, by polymerizing a polymerizable composition, which comprises: (a) from about 10 percent to about 94 percent, preferably from about 20 percent to about 80 percent, more preferably from about 40 percent to about 65 percent, by weight of a polysiloxane partially ethylenically functionalized (40 percent to about 95 percent, preferably about 50 percent to about 95 percent, more preferably from about 60 percent to about 92 percent, still more preferably from about 70 percent to about 90 percent) (ie, a partially functionalized ethylenically polysiloxane); (b) from about 5 percent to about 75 percent, preferably from about 10 percent to about 65 percent, more preferably from about 15 percent to about 55 percent, still more preferably from about 20 percent to about 45 percent by weight of at least one hydrophilic vinyl monomer; (c) 0 to about 55 percent, preferably about 5 percent to about 45 percent

percent, more preferably about 10 percent to about 40 percent, still more preferably about 15 percent to about 30 percent, by weight of a bulky hydrophobic vinyl monomer; (d) from about 0.25 percent to about 5 percent, preferably from about 0.5 percent to about 4 percent, more preferably from about 0.75 percent to about 3 percent, still more preferably from about 1 percent to about 2 percent by weight of a chain transfer agent other than a RAFT agent, wherein the chain transfer agent optionally, but preferably, it includes a reactive functional group; (e) from 0 to 5 percent by weight, preferably from about 0.2 percent to 4 percent by weight, more preferably from about 0.3 percent to about 2.5 percent by weight, still more preferably from about 0.5 percent to about 1.8 percent by weight of a polymerizable ultraviolet (UV) radiation absorbing compound; and (f) from about 0.1 percent to about 5 percent, preferably from about 0.2 percent to about 4 percent, more preferably from about 0.3 percent to about 3 percent, still more preferably from about 0.4 percent to about 1.5 percent by weight of an initiator 53

INSTnVTO MEXICANO 'DE LA FROHWAD industrial free radicals (a photoinitiator or a thermal initiator, preferably a thermal initiator). The percentages by weight of the components listed above are relative to the combined weight of all polymerizable components (which may include additional polymerizable components not listed herein).

Preferred polymerizable ultraviolet (UV) absorbers include, without limitation, 2 - (2-hydroxy-5-vini If eni I) -2 H benzotriazole, 2- (2-hydroxy-5-acryl) l¡loxy-phen¡l) -2H-benzotriazole, 2- (2-hydroxy-3-methacrylam¡do-methyl-5-teroct¡l-phenyl) -benzotriazole, 2- (2 ' hydroxy-5'-m et acrylam do-phenyl) -5-chloro-benzotriazole, 2- (2'-hydroxy-5'-methacrylamido-phenyl) -5-methoxy-benzotriazole, 2- (2 ' -hydroxy-5'm et acryloxy-propyl-3'-useful te rb-phenyl) -5-chloro-benzotriazole, 2- (2'-hydroxy-5'-methacryloxy-ethyl-phenyl) -benzotriazole, 2- (2'-hydroxy-5'-methacryloxypropyl-phenyl) -benzotriazole, 2-hydroxy- 4-acryloxy-alkoxy-benzophenone, 2-hydroxy-4-methacryloxy-alkoxy-benzophenone, allyl-2-hydroxy-benzophenone,

2-hydroxy-4-methacryloxy-benzophenone. A polymerizable ultraviolet (UV) absorbing agent is generally present in the polymerizable composition for the preparation of a polysiloxane copolymer that is ethylenically functionalized to obtain in turn a polysiloxane prepolymer of the invention, in an amount sufficient to provide a contact lens, which is made from a lens-forming material that includes the prepolymer and that absorbs at least about 80 percent of ultraviolet (UV) light in the range of about 280

IMPI ^?

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Dt THE INDUSTRIAL CURRENCY nanometers to approximately 370 nanometers that impinges on the lens. A person skilled in the art will understand that the specific amount of ultraviolet (UV) absorbing agent used in the polymerizable composition will depend on the molecular weight of the ultraviolet (UV) absorbing agent and its extinction coefficient in the range of about 280 to approximately 370 nanometers. In accordance with the invention, the polymerizable composition comprises from about 0.2 percent to about 5.0 percent, preferably from about 0.3 percent to about 2.5 percent, more preferably from about 0.5 percent to about 1.8 percent. weight percent of an ultraviolet (UV) radiation absorbing agent.

The polymerizable composition for the preparation of an amphiphilic branched polysiloxane copolymer may further comprise a polysiloxane-containing vinyl macromer. A polysiloxane-containing vinyl macromer can be prepared according to any known procedures, for example, those described in United States Patent Numbers 4,136,250, 4,486,577, 4,605,712, 5,034,461, 5,416,132, and 5,760,100, incorporated herein by reference. In its whole.

Examples of preferred polysiloxane-containing vinyl monomers or macromers include, without limitation, mono- (meth) acrylate-terminated polydimethylsiloxanes of different weight.

molecular (e.g., mono-3-methacryloxy-propyl terminated poly-dimethyl-siloxane, mono-butyl-terminated or mono- (3-methacryloxy-2-hydroxy-propyloxy) terminated poly-dimethylsiloxane) -propyl, or mono-butyl terminated polydimethylsiloxane); mono-vinyl-terminated, mono-vinyl carbonate-terminated, or mono-vinyl carbamate-terminated poly-dimethyl siloxanes of different molecular weight; monomers po I is i I or xa ni Ia I qui I - (meth) acrí I i co s; hydroxy functionalized siloxane-containing vinyl monomers or macromers; and mixtures thereof. Examples of preferred polysiloxane-containing cross-linkers include, without limitation, di- (meth) acrylated poly-dimethyl siloxanes (or so-called polysiloxane cross-linkers) of different molecular weight; di-vinyl carbonate terminated poly-dimethyl siloxanes (polysiloxane crosslinkers); di-vinyl carbamate terminated poly-dimethyl siloxane (polysiloxane crosslinkers); di-vinyl terminated poly-dimethylsiloxanes (polysiloxane crosslinkers); di- (meth) acrylamide terminated polydimethyl siloxanes (polysiloxane crosslinkers); bs-3-methacryloxy-2-hydroxy-propyloxy-propyl-poly-dimethylsiloxane (crosslinking polysiloxane); N, N, N ', N'-tetrak¡s- (3-methacrylox¡2-hydroxy-propyl) -alpha, omega-bis-3-amino-propyl-poly-dimethyl-siloxane (polysiloxane crosslinkers) ; siloxane-containing macromer selected from the group consisting of Macromer A, Macromer B, Macromer C, and Macromer D described in United States Patent Number US 5,760,100 (incorporated herein by reference in its entirety); the

reaction products of glycidyl methacrylate with amino-functional poly-dimethylsiloxanes; the polysiloxane-containing cross-linkers disclosed in United States Patent Numbers 4,136,250, 4,153,641, 4,182,822, 4,189,546, 4,343,927, 4,254,248, 4,355,147, 4,276,402, 4,327,203, 4,341,689, 4,443,785, 4,341,689, 4,443,798, 4,703,097, 4,833,218, 4,837,289, 4,954,586, 4,954,587, 5,010,141, 5,034,461, 5,070,170, 5,079,319, 5039,761, 5,346,946, 5,358,995, 5,387,632, 5,416,132, 5,451,617, 5,486,579, 5,962,575, 3,981,548, 3,981,548 and 6,762,264 (incorporated herein by reference in their entirety); the polysiloxane-containing crosslinkers disclosed in United States Patent Numbers 4,259,467, 4,260,725, and 4,261,875 (incorporated herein by reference in their entirety); di- and tri-block crosslinkers consisting of poly-dimethyl-siioxane and polyalkylene oxides (for example, polyethylene oxide-blockpoly-dimethylsiloxane-block-polyethylene oxide capped at the end with methacrylate); and mixtures thereof.

A further class of preferred polysiloxane-containing cross-linkers is silicone-containing prepolymers comprising hydrophilic segments and hydrophobic segments. Any silicone-containing prepolymers with suitable hydrophilic segments and hydrophobic segments can be used in the invention. Examples of these silicone-containing prepolymers include those described in

United States Patent Numbers 6,039,913, 6,043,328, 7,091,283, 7,268,189 and 7,238,750, 7,521,519 collectively owned; United States of North America Patent Application Publication Numbers US 20080015315 A1, US 2008-0143958 A1, US 2008-0143003 A1, US 20080234457 A1, and US 2008-0231798 A1 collectively owned, and Patent Applications of the United States Numbers 12 / 313,546, 12 / 616,166 and 12/616169 in collective property; all of which are incorporated herein by reference in their entirety.

The polymerization of a polymerizable composition for the preparation of an amphiphilic branched polysiloxane copolymer is based on well-known radical chain growth polymerization, and can be carried out according to any known methods and in any suitable containers (reactors) for polymerization. The polymerization is preferably thermally initiated. A polymerizable composition for the preparation of an amphiphilic branched polysiloxane can be prepared by dissolving all the components in any suitable solvent known to a person skilled in the art.

The amphiphilic branched polysiloxane copolymer obtained is then ethylenically functionalized by its reaction with a second ethylenically functionalizing vinyl monomer having a fourth reactive functional group to obtain an amphiphilic branched polysiloxane prepolymer of the invention, in the understanding of 58

IWWnrrc MK1CAJ * J Dt ΙΛ MOHEDAL industry ».

that the fourth reactive group can react with one of the second terminal reactive functional groups and the third functional groups (if available) of the amphiphilic branched polysiloxane copolymer, in the presence or absence of a coupling agent, to form a covalent bond . It is understood that, during this ethylenic functionalization step, the unreacted functional polysiloxane, which is inherently present in the partially ethylenically functionalized polysiloxane, is also ethylenically functionalized to form a cross-linking polysiloxane that can be used in conjunction with the amphiphilic branched polysiloxane prepolymer. resulting in the preparation of a lens formulation for making silicone hydrogel contact lenses.

According to the invention, the molar equivalent ratio of the second ethylenically functionalizing vinyl monomer to the amphiphilic polysiloxane copolymer is greater than 1, preferably from about 1 to about 1.2, more preferably from about 1 to about 1.1, still more preferably about 1 to 1.05. It is understood that the calculation of the molar equivalent ratio should count all possible reactive functional groups of the amphiphilic branched copolymer, including those derived from the partially ethylenically functionalized polysiloxane, from the chain transfer agent, from any other polymerizable components. that have a reactive functional group on the

polymerizable composition. This calculation can be made based on the starting materials for the preparation of the amphiphilic branched polysiloxane copolymer. The excess amount of the second ethylenically functionalizing vinyl monomer can be removed (but preferably not removed) from the resulting amphiphilic branched polysiloxane prepolymer before the prepolymer is used in the preparation of a lens formulation for making contact lenses of silicone hydrogel.

In accordance with the invention, the weight percentages of the components of an amphiphilic branched polysiloxane prepolymer are determined by the polymerizable composition or mixture, based on the total weight of all polymerizable components of the composition or mixture used for the preparation of a amphiphilic branched polysiloxane copolymer, which in turn is ethylenically functionalized to form the prepolymer of the invention. For example, if a polymerizable mixture for the preparation of an amphiphilic branched polysiloxane copolymer which in turn is ethylenically functionalized to form the prepolymer of the invention, comprises about 44 weight percent ethylenically functionalized linear poly-dimethylsiloxane 80 percent (which contains 64 percent of a linear polysiloxane crosslinker with two ethylenically unsaturated groups, 32 percent of a linear polysiloxane with an ethylenically unsaturated group and a functional group reactive for ethylenic functionalization, 4 percent of a linear polysiloxane □ »LA nCTIE» AL>

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,,. ,. INDUSTRIAL with two terminal reactive functional groups, which is not incorporated into the amphiphilic branched prepolymer, the percentages are calculated as described above), approximately 28.5 percent by weight of at least one hydrophilic vinyl monomer, approximately 26 percent in weight of a bulky hydrophobic vinyl monomer (eg, TRIS or the like), and approximately 1.5 percent of a chain transfer agent (eg, mercaptoethanol), then the resulting amphiphilic branched prepolymer comprises about 28 percent by weight of polysiloxane crosslinking units (44 percent x 64 percent x 100), about 14 percent by weight of pendant polysiloxane chains, each of which is terminated with an ethylenically unsaturated group (44 percent x 32 percent x

100), about 28.5 weight percent hydrophilic monomer units, about 26 weight percent bulky hydrophobic monomer units, and about 1.5 weight percent chain transfer units. A person skilled in the art will be well aware of how to determine the percentages of each component of an amphiphilic branched prepolymer according to the procedure described above for the illustrative example.

An amphiphilic branched polysiloxane prepolymer of the invention may find particular uses as a lens-forming material for the preparation of contact lenses of

silicone hydrogel. It will be particularly convenient for use as an amphiphilic branched polysiloxane prepolymer of the invention, together with a small amount (i.e. less than 20 weight percent relative to the total amount of all polymerizable components) of one or more vinyl monomers in the preparation of a lens-forming composition for the purpose of making silicone hydrogel contact lenses. Curing of this composition to form lenses in molds would be in addition to a two-stage curing process, with the first being an off-line (or pre-cure) cure of a lens formulation in a container, and the other being a cure. online of a formulation for lenses in molds. This composition for forming lenses can offer the following advantages. First, the concentration of one or more vinyl monomers in the lens-forming composition can be reduced, and as such, the shrinkage that occurs after polymerization of the lens-forming composition in molds for making contact lenses can be substantially reduced. . Second, the ethylenically unsaturated groups of an amphiphilic branched polysiloxane prepolymer are readily accessible for radical chain growth polymerization, because they are located at the termini of the polymer chains. The cure time of the lens-forming composition in molds can be relatively short compared to a lens-forming composition made from a mixture of monomers (i.e., more than 20 percent by weight of one or more

vinyl monomers relative to the total amount of all -o-, u, · »· ** · * ····· polymerizable components). Third, the viscosity of the lens-forming composition can be relatively low compared to a lens-forming composition made of one or more prepolymers, due to the presence of one or more vinyl monomers.

It should be understood that, although various preferred embodiments of the invention may be described separately above, they may be combined in any desirable way to arrive at different preferred embodiments of the invention.

In a second aspect, the invention provides a method of making silicone hydrogel contact lenses. The method comprises the steps of: (i) obtaining an amphiphilic branched polysiloxane prepolymer, wherein the amphiphilic branched polysiloxane prepolymer comprises: (a) from about 5 percent to about 75 percent, preferably from about 10 percent to about 65 percent, more preferably from about 15 percent to about 55 percent, still more preferably from about 20 percent to about 45 percent by weight of hydrophilic monomeric units derived from at least one hydrophilic vinyl monomer, (b) from about 1 percent to about 85 percent, preferably from about 2.5 percent to about 75 percent, more preferably from

IMPI ^

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Df U PROPERTY about 5 percent to about ef ^ T weight percent of polysiloxane crosslinking units derived from at least one crosslinking polysiloxane having two or more terminal ethylenically unsaturated groups, (c) about 2 percent to about 48 percent, preferably from about 3 percent to about 38 percent, more preferably from about 4 percent to about 28 percent by weight of pendant polysiloxane chains, each of which is terminated with an ethylenically unsaturated group, and (d) from about 0.25 percent to about 5 percent. percent, preferably from about 0.5 percent to about 4 percent, more preferably from about 0.75 percent to about 3 percent, still more preferably from about 1 percent to about 2 percent by weight of chain transfer units derived from a chain transfer agent other than a RAFT agent; (ii) using amphiphilic branched polysiloxane prepolymer I to prepare a lens-forming composition comprising: (a) d about 60 percent to about 99 percent, preferably about 75 percent to about 97 percent , more preferably from about 85 percent to about 95 percent by weight of the amphiphilic branched polysiloxane prepolymer,

(b) from about 0.1 percent to about -5 percent, preferably from about 0.3 percent to about 3 percent, more preferably from about 0.4 percent to about 1.5 percent by weight of an initiator free radicals (a photoinitiator or a thermal initiator, preferably a photoinitiator), and (c) 0 to about 20 percent, preferably from about 2 percent to about 16 percent, more preferably from about 4 percent to about 12 percent by weight of at least one polymerizable component selected from the group consisting of a hydrophilic vinyl monomer, a silicone-containing vinyl monomer or macromer, a hydrophobic vinyl monomer, a linear polysiloxane crosslinker terminated with two ethylenically unsaturated groups, a crosslinking agent having a molecular weight of less than 700 Daltons, a polymerizable ultraviolet (UV) radiation absorbing agent, and mixtures thereof, wherein the weight percentages of components (a) to (c) are relative with the total amount of all polymerizable components (including those not listed above) in the lens-forming composition; (ii) introducing the lens-forming composition into a mold, wherein the mold has a first mold half with a first molding surface defining the anterior surface of a contact lens, and a second mold half with a second molding surface that defines the surface

rear of the contact lens, wherein the first and second mold halves are configured to receive each other, such that a cavity is formed to receive the lens-forming material between the mentioned first and second molding surfaces; and (iv) polymerizing the lens-forming material in the cavity to form a silicone hydrogel contact lens.

Different embodiments are described above, including preferred embodiments of amphiphilic branched polysiloxane prepolymers, free radical initiators, chain transfer agents, hydrophilic vinyl monomers, silicone-containing vinyl monomers or macromers, hydrophobic vinyl monomers, crosslinking agents that have a weight molecular weight less than 700 Daltons, polymerizable ultraviolet (UV) absorbing agents, and linear polysiloxane crosslinkers terminated with two ethylenically unsaturated groups, and can be used in this aspect of the invention.

Preferably, an amphiphilic branched polysiloxane prepolymer is obtained according to a process comprising the steps of: (i) obtaining a partially ethylenically functionalized polysiloxane, wherein the partially ethylenically functionalized polysiloxane is a mixture of reaction products obtained by reacting a first functionalizing vinyl monomer having a reactive first functional group with a functional polysiloxane compound having two or more second reactive functional groups in a molar equivalent ratio of

about 40 percent to about 95 percent

WSTtTUTO MEXICAN ·

DF THE INDUSTRIAL PROPERTY

percent, preferably about 50 percent to about 95 percent, more preferably about 60 percent to about 92 percent, still more preferably about 70 percent to about 90 percent (of the monomer ethylenically functionalizing vinyl to functional polysiloxane compound), wherein each first reactive functional group reacts with a second reactive functional group in the presence or absence of a coupling agent to form a bond or covalent bond, wherein the reaction product mixture comprises at least one polysiloxane crosslinker having at least two ethylenically unsaturated groups and at least one vinyl polysiloxane monomer or macromer having at least one second reactive functional group and at least one ethylenically unsaturated group; (ii) using the amphiphilic branched polysiloxane copolymer to prepare a polymerizable composition, wherein the polymerizable composition comprises at least one hydrophilic vinyl monomer, a chain transfer agent that is not a RAFT agent and optionally (but preferably) includes a third reactive functional group, and a free radical initiator; (ii) polymerizing the polymerizable composition to form an amphiphilic branched polysiloxane copolymer comprising hydrophilic monomer units derived from the at least one

IMPI • XTWTO MBCICAN · From INDUSTRIAL noniDAD hydrophilic vinyl monomer, polysiloxane crosslinking units derived from the crosslinking polysiloxane, pendant polysiloxane chains, each terminated with a second reactive functional group and derived from the vinyl polysiloxane monomer or macromer , and chain transfer units with or without reactive third functional groups derived from the chain transfer agent; (iv) reacting the branched polysiloxane copolymer with a second ethylenically functionalizing vinyl monomer having a fourth reactive functional group that reacts with a second or third reactive functional group on the branched polysiloxane copolymer in the presence or absence of a coupling agent to form a covalent bond, thereby forming the amphiphilic branched polysiloxane prepolymer having pendant polysiloxane chains, each of which is terminated with an ethylenically unsaturated group.

Different embodiments, including the various preferred embodiments of functional polysiloxanes with reactive functional groups, ethylenically functionalizing vinyl monomers, hydrophilic vinyl monomers, hydrophobic vinyl monomers, bulky hydrophobic vinyl monomers, free radical initiators, polymerizable ultraviolet (UV) radiation absorbing agents, polymerizable agents chain transfer, and solvents, and the polymerizable compositions for the preparation of an amphiphilic branched polysiloxane copolymer, are described

above (eg, for the first aspect of the invention), and can be used in this aspect of the invention.

According to the invention, the first and second ethylenically functionalizing vinyl monomers may be different from each other, but are preferably identical to each other. Preferably, the molar equivalent ratio of the second ethylenically functionalizing vinyl monomer to the amphiphilic polysiloxane copolymer is greater than 1, preferably from about 1 to about 1.2, more preferably from about 1 to about 1.1, still more preferably from about 1 to 1.05. The amphiphilic branched polysiloxane copolymer can be purified (but preferably not purified) prior to ethylenic functionalization. The excess amount of the second ethylenically functionalizing vinyl monomer can be removed (but preferably not removed) from the resulting amphiphilic branched polysiloxane prepolymer before the prepolymer is used in the preparation of a lens formulation for making contact lenses of silicone hydrogel.

The obtained amphiphilic branched polysiloxane prepolymer can be used directly in the preparation of a lens-forming composition for the purpose of making silicone hydrogel contact lenses. However, if the solvent used in the preparation of the amphiphilic branched polysiloxane prepolymer is not a desired solvent for the preparation of a composition for

To form lenses, it is desired to exchange the solvent according to any suitable techniques known to a person skilled in the art (eg, repeated cycles of condensation and dilution with a desired solvent). Alternatively, the obtained amphiphilic branched polysiloxane prepolymer can be purified by any suitable techniques known to a person skilled in the art.

It should be understood that a composition for forming lenses may also comprise various components, such as, for example, a hydrophilic vinyl monomer, a hydrophobic vinyl monomer, a bulky hydrophobic vinyl monomer, a coloring agent for visibility (e.g., dyes, pigments, or mixtures thereof), a polymerizable ultraviolet (UV) absorbing agent, antimicrobial agents (for example, preferably silver nanoparticles), a bioactive agent, leachable lubricants, tear stabilizing leachable agents, and mixtures thereof, as is known to a person skilled in the art.

The bioactive agent incorporated in the polymeric matrix is any compound that can prevent an eye disease or reduce the symptoms of an eye disease. The bioactive agent can be a drug, an amino acid (eg, taurine, glycine, etc.), a polypeptide, a protein, a nucleic acid, or any combination thereof. Examples of drugs useful herein include, but are not limited to, rebamipid, ketotifen, olaptidine, chromoglycollate, cyclosporine, nedocromil,

levocabastine, lodoxamide, ketotifen, or the pharmaceutically acceptable salts or estersrpg _—— thereof. Other examples of bioactive agents include 2-pyrrolidone-5-carboxylic acid (PCA), alpha-hydroxy acids (eg, glycolic, lactic, malic, tartaric, mandelic, and citric acids, and salts thereof, etc.) , linoleic and gamma linoleic acids, and vitamins (for example, B5, A, B6, etc.).

Examples of leachable lubricants include, without limitation, mucin-type materials (eg, polyglycolic acid) and non-crosslinkable hydrophilic polymers (ie, without ethylenically unsaturated groups).

Any hydrophilic polymer or copolymer without any ethylenically unsaturated group can be used as the leachable lubricant. Preferred examples of non-crosslinkable hydrophilic polymers include, but are not limited to, polyvinyl alcohols (PVAs), polyamides, polyimides, polylactone, a homopolymer of a vinyl lactam, a copolymer of at least one vinyl lactam in the presence or absence of one or more hydrophilic vinyl comonomers, a homopolymer of acrylamide or methacrylamide, a copolymer of acrylamide or methacrylamide with one or more hydrophilic vinyl monomers, polyethylene oxide (i.e., polyethylene glycol (PEG)), a polyoxyethylene derivative, poly-NN-dimethyl acrylamide, polyacrylic acid, poly-2-ethyl oxazolines, heparin polysaccharides, polysaccharides, and mixtures of the same.

Weight average molecular weight Mn of the non-crosslinkable hydrophilic polymer is preferably 5,000 to

10,000 to 300,000 preference, even more preferably 20,000 to 100,000.

Examples of tear stabilizing leachable agents include, without limitation, fo sf or Iipids, monoglycerides, dig I i ceri dos, tri g I i ce rid os, glycolipids, g I i ce ro-g I ico Iipids, sphingolipids, sphingolipids, fatty alcohols, fatty acids, mineral oils, and mixtures thereof. Preferably, a tear stabilizing agent is a phospholipid, a monoglyceride, a diglyceride, a trig I i cer, a glycolipid, a g I i ce ro-g I ic o I pid, an e sf ingo - 1 í p id o, an e sf ing og I i i i pid, a fatty acid having 8 to 36 carbon atoms, a fatty alcohol having 8 to 36 carbon atoms, or a mixture thereof .

A composition for forming lenses can be prepared by dissolving all of the desirable components in any suitable solvent known to a person skilled in the art. Examples of suitable solvents are described above, and can be used in this aspect of the invention.

Lens molds for making contact lenses are well known to one of ordinary skill in the art and are, for example, used in cast molding or centrifugal casting. For example, a mold (for cast molding) generally comprises at least two mold sections (or portions) or mold halves, ie first and second mold halves. The first mold half defines a first surface of

IMPI ^ iwrrruTo muucano μ the currency,,. ,,. . . , ..... . ... INDUSTRIAL - molding (or optical) and the second mold half defines a second molding (or optical) surface. The first and ^ g ^ úT ^ a ^ m ^ KcTeT'HT mold are configured to receive one another, such that a lens-forming cavity is formed between the first molding surface and the second molding surface. The molding surface of a mold half is the surface that forms the mold cavity and is in direct contact with the lens-forming material.

Methods for manufacturing mold sections for casting a contact lens are generally well known to those skilled in the art. The process of the present invention is not limited to any particular method of forming a mold. In fact, any method of forming a mold can be employed in the present invention. The first and second mold halves can be formed through various techniques, such as injection molding or turning. Examples of suitable processes for forming the mold halves are disclosed in US Patent Numbers 4,444,71 to Schad; 4,460,534 to Boehm et al .; 5,843,346 for Merrill; and 5,894,002 to Boneberger et al., which are also incorporated herein by reference.

Virtually all materials known in the art can be used to make molds in order to make the molds for making contact lenses. For example, polymeric materials such as polyethylene, polypropylene,

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INSTITUTO MBUCAMO M LA FRUFIEDAD INDUSTRIAL polystyrene, PMMA, Topas® COC grade 8007-S10 (transparent amorphous copolymer of ethylene and norbornene, from Ticona GmbH of Frankfurt, Germany and Summit, New Jersey), or the like. Other materials that allow transmission of ultraviolet (UV) light could be used, such as quartz and sapphire glass.

In a preferred embodiment, reusable molds are used, and the lens-forming composition is actinically cured (ie, polymerized) under spatial limitation of actinic radiation to form a silicone hydrogel contact lens. Examples of the preferred reusable molds are those disclosed in U.S. Patent Application Nos. 08 / 274,942 filed July 14, 1994, 10 / 732,566 filed December 10, 2003, 10 / 721,913 filed November 25, 2003, and United States Patent Number 6,627,124, both of which are incorporated by reference in their entirety. Reusable molds can be made of quartz, glass, sapphire, CaF2, a cyclic olefin copolymer (such as, for example, Topas® COC grade 8007-S10 (transparent amorphous copolymer of ethylene and norbornene) from Ticona GmbH of Frankfurt, Germany and Summit, New Jersey, Zeonex® and Zeonor® from Zeon Chemicals LP, Louisville, KY), polymethyl methacrylate (PMMA), polyoxymethylene from DuPont (Delrin), Ultem® (polyetherimide) from GE Plastics, PrimoSpire®, etc.

According to the invention, the composition for forming lenses can be introduced (dosed) into a cavity formed by a mold,

according to any known methods.

After it is dosed into the mold ia1 lens-forming composition, polymerizes to produce a contact lens. Crosslinking can be initiated thermally or actinically, preferably by exposing the lens-forming composition in the mold to spatial limitation of actinic radiation to cross-link the polymerizable components of the lens-forming composition. Crosslinking according to the invention can be carried out in a very short time, for example, in £ about 120 seconds, preferably in £ about 80 seconds, more preferably in about £ 50 seconds, still more preferably in £ about 30 seconds, and most preferably in 5 to 30 seconds.

When the lens-forming composition comprises an amphiphilic branched polysiloxane prepolymer having ultraviolet (UV) absorbing moieties and / or a polymerizable ultraviolet (UV) absorbing agent, preferably a benzoyl phosphine oxide photoinitiator is used as the photoinitiator in the invention. Preferred benzoyl phosphine oxide photoinitiators include, without limitation, 2,4,6-trimethyl benzoyldifeni If or sfina oxide; bis- (2,6-dichloro-benzoyl) -4-N-propyl-phenylphosphine oxide; and bis- (2,6-dichloro-benzoyl) -4-N-butyl-phenyl-phosphine oxide. It is understood that any photoinitiators other than benzoyl phosphine oxide initiators can be used in the invention.

The opening of the mold of such a lens molded from the mold, known per se.

way that he can move he can have 10 way

The molded contact lens can be subjected to lens extraction to remove uncured polymerizable components. The extraction solvent can be any solvent known to a person skilled in the art. Suitable examples of the extraction solvent are those described above. After extraction, the lenses can be hydrated in water or in an aqueous solution of a wetting agent (eg, a hydrophilic polymer).

Molded contact lenses can be further subjected to additional processes, such as, for example, surface treatment (for example, such as, plasma treatment, chemical treatments, grafting of hydrophilic monomers or macromers onto the surface of a lens, coating layer by layer (LbL), etc.); the packaging in the lens packages with a packaging solution that can contain approximately the

0.005 percent to about 5 percent by weight of a wetting agent (eg, a hydrophilic polymer described above) and / or a viscosity-increasing agent (eg, methyl cellulose (MC), ethyl cellulose, hydroxy -methyl-cellulose, hydroxy-ethyl-cellulose (HEC), hydroxy-propyl-cellulose (HPC), hydroxypropyl-methyl-cellulose (HPMC), or a mixture thereof); sterilization; and the like.

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The preferred surface treatments are off bSBMEWo layer by layer (LbL), such as those described in l ° 5 PQJQr, tUnited States of North America Tf Numbers 6,451,871, 6,719,929, 6,793,973, 6,81 1,805, 6,896,926 (incorporated herein by reference in their entirety), and plasma treatment. A preferred plasma treatment is for processes where an ionized gas is applied to the surface of an article, as described in United States Patent Nos. 4,312,575 and 4,632,844 (incorporated herein by reference in their entirety ).

A contact lens of the invention has an oxygen permeability of preferably at least about 40 barrers, more preferably at least about 60 barrers, still more preferably at least about 80 barrers. According to the invention, an oxygen permeability is an apparent oxygen permeability (measured directly when testing a sample with a thickness of about 100 microns) according to the procedures described in the Examples.

A contact lens of the invention has an elastic modulus of about 2.0 MPa or less, preferably about 1.5 MPa or less, more preferably about 1.2 or less, still more preferably about 0.4 MPa to about 1.0 MPa.

A contact lens of the invention further has a

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MUÍCANO INSTITUTE

Lonoflux Diffusion Coefficient, D, preferably DaeiNtf ^ wdoS55SÍ5s about 1.5 x 10 '6 square millimeters / nunutQ, ... more preferably at least about 2.6 x 10 '6 square millimeters / minute, even more preferably at least about 6.4 x 10 '6 square millimeters / minute.

A contact lens of the invention further has a water content of preferably about 15 percent to about 70 percent, more preferably about 20 percent to about 50 percent by weight when fully hydrated. The water content of a silicone hydrogel contact lens can be measured according to the Bulk Technique, as disclosed in United States Patent Number US5,849,811.

In a third aspect, the invention provides a silicone hydrogel contact lens obtained by the method of the invention.

In a fourth aspect, the invention provides a method for the preparation of an amphiphilic branched polysiloxane prepolymer, the method comprising the steps of: (i) obtain a partially ethylenically functionalized polysiloxane, wherein the partially ethylenically functionalized polysiloxane is a mixture of reaction products obtained by reacting a first functionalizing vinyl monomer having a first reactive functional group, with a functional polysiloxane compound

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Dt LA FtOHEDAD having two or more second functional groups rO'STTVbsT ^ fF-Jna molar equivalent ratio of about 95 percent to about 95 percent molar equivalent Trterel- ^ O'pui biiiilu er , more preferably from about 60 percent to about 92 percent, still more preferably from about 70 percent to about 90 percent (functionalizing vinyl monomer to linear polysiloxane compound), wherein each first reactive functional group reacts with a second reactive functional group in the presence or absence of an agent. coupling to form a bond or covalent bond, wherein the reaction product mixture comprises one or more vinyl polysiloxane monomers or macromers having at least one second reactive functional group and at least one ethylenically unsaturated group, one or more polysiloxane crosslinkers having at least two ethylenically unsaturated groups , (I) preparing a polymerizable composition, which comprises: (a) the partially ethylenically functionalized polysiloxane, (b) at least one hydrophilic vinyl monomer, (c) a chain transfer agent that is not a RAFT agent and that optionally (but preferably) includes a third reactive functional group, and (d) a free radical initiator; (Ii) polymerizing the polymerizable composition to form an amphiphilic branched polysiloxane copolymer comprising hydrophilic monomer units derived from

at least one hydrophilic vinyl monomer, polysiloxane crosslinking units derived from the polysiloxane crosslinkers, pendant polysiloxane chains derived from the vinyl polysiloxane monomers or macromers, and each terminated with a second reactive functional group, and units chain transfer with or without reactive third functional groups; (ii) reacting the branched polysiloxane copolymer with a second functionalizing vinyl monomer having a fourth reactive functional group that reacts with a second or third reactive functional group on the branched polysiloxane copolymer in the presence or absence of a coupling to form a covalent bond, thereby forming the polysyl prepolymer: pendant polysiloxane chains terminated with an ethylenic group

All the different compositions for forming radiation spatial limiting lenses in the invention described above and aspects of the invention, can be branched amphiphilic having tees, each of which is unsaturated.

Modalities of the molds, and components thereof, and the, and the contact lens of the e for the first and second den use in these two aspects of the invention.

The foregoing description will allow one of ordinary skill in the art to practice the invention. Different modifications, variations, and combinations can be made of the various modalities described in. In order to allow

To better understand the specific modalities and the advantages of them, it is suggested to refer to the following examples. The specification and examples are intended to be considered exemplary.

Although various of the invention have been described using specific terms, devices, and methods, this description is for illustrative purposes only. The words used are words of description rather than limitation. It will be understood that those skilled in the art can make changes and variations without departing from the spirit and scope of the present invention, which is set forth in the following claims. Furthermore, it should be understood that aspects of the various modalities may be interchanged in whole or in part, or may be combined in any way and / or used together. Therefore, the spirit and scope of the appended claims should not be limited to the description of the preferred versions contained therein.

Example 1

Oxygen permeability measurements.

The apparent oxygen permeability of a lens and the oxygen transmissibility of a lens material are determined according to a technique similar to that described in United States Patent Number 5,760,100 and in an article by Winterton et al. (The Cornea: Transactions of the

World Congress on the Cornea 111, HD Cavanagh Editor, Raven

Press: New York 1988, pages 273-280), both incorporated into the

present for reference in its entirety. XJl oxygen fluxes are measured at 34 ° C in a wet cell (i.e. gas streams are maintained at a relative humidity of approximately 100 percent) using a Dk1000 instrument (available from Applied Design and Development Co., Norcross, GA), or a similar analytical instrument. A stream of air, which has a known percentage of oxygen (for example, 21 percent), is passed through one side of the lens at a speed of approximately 10 to 20 cubic centimeters / minute, while doing pass a stream of nitrogen on the opposite side of the lens at a rate of approximately 10 to 20 cubic centimeters / minute. A sample is equilibrated in a test medium (i.e. saline or distilled water) at the prescribed test temperature for at least 30 minutes prior to measurement, but not more than 45 minutes. Any test medium used as the overcoat is equilibrated at the prescribed test temperature for at least 30 minutes prior to measurement, but not more than 45 minutes. The stir motor speed is set at 1,200 + 50 revolutions per minute, corresponding to a reference of 400 + 15 in the step motor controller. The barometric pressure surrounding the system, PIdida- The thickness (t) of the lens in the area exposed for examination is determined by measuring approximately 10 locations with a Mitotoya VL-50 micrometer, or similar instrument, and the measurements are averaged. The oxygen concentration in the nitrogen stream is measured (i.e., the

oxygen diffusing through the lenses) using a DK1000 instrument. Determine the apparent oxygen permeability of the lens material, Dkapp, from the following formula:

Dkapp Jt '(^ oxygen) where:

J = flow of oxygen [microliters of O2 / square centimeter - minute];

Poxygen = (Pmeasure - Steam Pagua) = (% O2 in the air stream);

[mm Hg] = partial pressure of oxygen in the air stream;

Measured P = barometric pressure (mm Hg);

Pagua steam = 0 mm Hg at 34 ° C (in a dry cell) (mm Hg);

Pagua steam = 40 mm Hg at 34 ° C (in a humid cell) (mm Hg);

t = average lens thickness over exposed test area (mm).

DKapp It is expressed in units of barrers.

The apparent oxygen transmissibility (Dk / t) of the material can be calculated by dividing the apparent oxygen permeability (Dktopp) between the average thickness (t) of the lens.

The measurements described above are not corrected for the so-called boundary layer effect, which can be attributed to the use of a water bath or of

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saline solution on top of the contact lens during oxygen flow measurement. The boundary layer effect causes the reported value for the Dkapp apparent value of a silicone hydrogel material is lower than the actual intrinsic Dkj value. Also, the relative impact of the boundary layer effect is greater for thinner lenses than for thicker lenses. The net effect is that the reported Dk appears to change as a function of lens thickness when it should remain constant.

The intrinsic Dk value of a lens can be estimated based on a corrected Dk value for the surface resistance to oxygen flow caused by the boundary layer effect as follows.

The apparent oxygen permeability values (single point) of the reference lenses lotrafilcon A (Focus® N & D® from GIBA VISION CORPORATION) or lotrafilcon B (AirOptix) are measured.MR of CIBA VISION CORPORATION) using the same equipment. Reference lenses are of similar optical power to that of trial lenses, and are measured in a manner concurrent with trial lenses.

Oxygen flux through a series of lotrafilcon A or lotrafilcon B (reference) lens thicknesses is measured using the same equipment according to the procedure for apparent Dk measurements described above, to obtain the intrinsic Dk value (Dk ¡) Of the reference lens. A thickness series should cover a thickness range of approximately 100 microns or more. Preferably, the reference lens thickness range will frame the lens thicknesses tf ^ pTest 'The IDkapp of these reference lenses should be measured on the same equipment as the trial lenses, and ideally should be measured in a manner contemporaneous with the trial lenses. Equipment setup and measurement parameters should be kept constant throughout the experiment. Individual samples can be measured multiple times if desired.

Determine the residual oxygen resistance value, Rr, from the results of the reference lens using equation 1 in the calculations.

R, =

Dk.J (D where t is the thickness (reference lens) under measurement, and n is the number of reference lenses measured. Residual oxygen resistance value, Rr against the data t, and a curve of the form Y = a + bX is fitted, where, for the j-lens, Y, = (ΔΡ / J) j and X = tj. Residual oxygen resistance, Rr equals a.

The residual oxygen resistance value determined above is used to calculate the correct oxygen permeability Dkc (Estimated intrinsic Dk) for the trial lenses, based on Equation 2.

Dkc = t / [(t / Dkto) - Rr] (2)

The estimated intrinsic Dk of the lens to calculate what the apparent Dk would have been (Dkastd) for a lens of a standard thickness in the same test environment, based on Equation 3.

Dkastd= tstd / [(fstd ¡Dkc) + Rr_std] (3)

Ion Permeability Measurements

The ion permeability of a lens is measured in accordance with the procedures described in United States Patent Number 5,760,100 (incorporated herein by reference in its entirety). The ion permeability values reported in the following examples are the relative lonoflux Diffusion Coefficients (D / Dref) with reference to a lens material, Alsacon, as the reference material. Alsacon has a lonoflux diffusion coefficient of 0.314 x 10 '3 mm2/minute.

Water Contact Angle Measurements (WCA)

Water contact angle (WCA) measurements are carried out by the sessile drop method with a DSA 10-drop shape analysis system from Krüss GmbH, Germany, with pure water (Fluka, surface tension 72.5 mN / m at 20 ° C). For measurement purposes, a contact lens is taken out of the storage solution with tweezers, and the

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INSTITUTO MUUCAM 'Di LA MVOHiDAD INDUSTRIAL

excess storage solution by gentle shaking. The contact lens is placed on the male part of a lens mold, and gently dried with a clean, dry cloth. A drop of water (approximately 1 microliter) is then metered onto the apex of the lens, and the change in contact angle over time of this drop of water is monitored (WCA (t), circle setting mode). The water contact angle (WCA) is calculated by extrapolating the graph of WCA (t) for t = 0.

Ultraviolet (UV) radiation absorbency

Contact lenses are manually placed in a specially manufactured specimen holder or the like, which can maintain the shape of the lens as it should be when placed in the eye. This support is then immersed in a 1 centimeter run length quartz cell containing phosphate buffered serum (PBS, pH about 7.0 to 7.4) as the reference. A UV / visible spectrophotometer, such as the Varian Cary 3E UV-Visible Spectrophotometer with a LabSphere DRA-CA-302 beam splitter or similar can be used in this measurement. The percentage of transmission spectra is collected at a wavelength rate of 250 to 800 nanometers with% T values collected at 0.5 nanometer intervals. These data are transcribed into an Excel spreadsheet and used to determine if the lenses conform to Class 1 ultraviolet (UV) absorbency. Ultraviolet (UV) absorbance is calculated using the following equations:

INDUSTRIAL

UVA% T =% Average transmission between 380 and 316 nm x 100

Luminescence% T

UVB% T =% Average Transmission between 280 and 315 nm x 100% Luminescence T

Where% T Luminescence is the average transmission percentage between 380 and 780.

Determination of Bend Mark

A Contact Lens Optical Quality Analyzer (CLOQA) is developed to determine the optical distortions caused by surface deformations and other defects in the contact lens, based on the principle of the eddy razor edge test. A person skilled in this field understands how to select, align, and configure different optical elements to create the collimating light, in order to illuminate a contact lens, and to capture an image with a device (for example, such like a CCD camera). The test involves illuminating the contact lens with near-collimated light, placing an eddy-knife edge near the focal point, moving the razor edge to block most of the focused light, and capturing the image of the contact lens. with a device, for example, a CCD camera, behind Foucault's razor edge. When there is no optical distortion in the contact lens, all light rays passing through

through the contact lens they come to focus on the razor's edge, and most of the well-focused light will be blocked. For areas outside the optical zone that have no focus function, the razor edge will block the light from half of the lens to make it dark, while the other half will appear bright. If the contact lens has no optical distortions in its optical zone, the entire optical zone will be uniformly dark or bright, depending on how much light is blocked by the razor edge. When there are optical distortions on the contact lens, the light that passes through these areas generally does not strike the main focus, and can either be blocked by the razor's edge (appearing dark), or it can pass through of it freely (appearing bright). The level of contrast not only depends on the amplitude of the distortion, but also depends on the fine position of the razor's edge. Defective areas appear as contrast features in the Contact Lens Optical Quality Analyzer (CLOQA) image. The Razor Edge Test with the Contact Lens Optical Quality Analyzer (CLOQA) is designed as a qualitative testing device for optical distortions in the optical zone.

The bend marking study is carried out as follows. Three passed and / or unautoclaved contact lenses are used in the study. First, contact lenses are imaged with the Contact Lens Optical Quality Analyzer (CLOQA).

Second, each lens is bent with the fingers twice (creating two

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perpendicular fold lines), and then your image is taken immediately with the Contact Lens Optical Quality Analyzer (CLOQA). Third, each contact lens is imaged approximately 15 minutes after bending, with the Contact Lens Optical Quality Analyzer (CLOQA). Three types of images are obtained from the Contact Lens Optical Quality Analyzer (CLOQA): an original (that is, no fold), immediately after the fold, and approximately 15 minutes after the fold. The bend mark study allows to determine the appearance of the bend line that changes over time.

Example 2

Ethylenically functionalized polysiloxanes are prepared in various percentages as follows. KF-6001A (a, w-bis- (2-hydroxy, 15 ethoxy-prop,) -poly-dimethyl-siloxane, Mn = 2000, from Shin-Etsu), and KF6002A (a, u-bis- (2-hydroxy-ethoxy-propyl) -poly-di-methyl-loxane, Mn = 3400, ex Shin-Etsu) are dried separately at about 60 ° C for 12 hours (or during the night), under high vacuum in a single neck flask. The OH molar equivalent weights of KF-6001A and KF-6002A are determined by titration of the hydroxyl groups and used to calculate the molar milliequivalent to be used in the synthesis.

A-1. Synthesis of partially ethylenically functionalized polysiloxanes

A one-liter reaction vessel is evacuated during the

night to remove moisture, and the vacuum is broken with dry nitrogen. 75.00 grams (75 milliequivalents) of dry KF6001A is charged to the reactor, and then 16.68 grams (150 milliequivalents) of freshly distilled isophorone di-isocyanate (IPDI) is added to the reactor. The reactor is purged with nitrogen and heated to 45 ° C with stirring, and then 0.30 grams of dibutyltin dilaurate (DBTDL) is added. The reactor is sealed, and a positive flow of nitrogen is maintained. An exotherm occurs, after which the reaction mixture is allowed to cool and is stirred at 55 ° C for 2 hours. After reaching the exotherm, 248.00 grams (150 milliequivalents) of dry KF6002A are added to the reactor at 55 ° C, and then 100 microliters of DBTDL are added. The reactor is stirred for four hours. Heating is discontinued and the reactor is allowed to cool overnight. Nitrogen sparging is stopped, and the reactor is opened to atmosphere for 30 minutes with moderate stirring. A hydroxyl terminated polysiloxane is formed having 3 polysiloxane segments , HO-PDMS-IPDI-PDMS-IPDI-PDMS-OH.

For the 80 percent ethylenically functionalized polysiloxane, 18.64 grams (120 milliequivalents) of isocyanatoethyl methacrylate (IEM) is added to the reactor, along with 100 microliters of DBTDL. The reactor is stirred for 24 hours, and then the product is decanted and stored under cooling. For the preparation of different percentages of ethylenically functionalized polysiloxane, various amounts of IEM are applied according to the following Table 1.

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IWmJUTO MBUCANO u fwnsbad INDUSTRIAL

Table 1

<td></td><td>% Polysiloxane Ethylenically Functionalized</td><td>IEM Weight</td>

A-2. 100 percent (fully) ethylenically functionalized polysiloxane:

A one liter reaction vessel is evacuated overnight to remove moisture, and the vacuum is broken with dry nitrogen. The reactor is charged with 75.00 grams (75 milliequivalents) of dry KF6001A and dried at 60 ° C under high vacuum for 8 hours, and then 23.30 grams (150 milliequivalents) of IEM are added to the reactor under nitrogen. After 30 minutes of stirring, 0.2 grams of DBTDL are added to the mixture. The reactor is stirred at 25 + 3 ° C for about 4 hours, and then the product is decanted and stored under cooling.

Example 3, „

This Example illustrates the effects of the percentage of ethylenic functionalization of polydisiloxane, which is used to prepare a prepolymer that is used in turn to prepare the lens formulation, on the viscosities of the lens formulations.

B-1. Amphiphilic Branched Copolymer Synthesis

A 1 liter jacketed reactor is equipped with a 500 milliliter addition funnel, with top agitation, reflux condenser with nitrogen / vacuum inlet adapter, thermometer, and sampling adapter. 48.55 grams of ethylenically functionalized partially polysiloxane (PDMS) prepared in Example 2, A-1.1 are charged to the reaction vessel. PDMS A-1.1 is degassed under vacuum at less than 1 mbar at room temperature for 30 minutes. After carrying out degassing, the reactor is filled with nitrogen gas awaiting further processing. The monomeric solution composed of 26.06 grams of Ν, Ν-dimethylacrylamide (DMA), 23.14 grams of (tris- (trimethylsilyl)) - siloxy-propyl) acrylamide (TRIS-Am), and 350 grams of ethyl acetate, was charge into the 500 milliliter addition funnel, followed by degassing under vacuum at 100 mbar and at room temperature for 10 minutes, and then backfilling with nitrogen gas. The monomer solution is degassed under the same conditions for two additional cycles. The monomeric solution is then loaded into

ΜΒ »

the reactor. The reaction mixture is heated to 64 ° C. While heating, a solution composed of 1.75 grams of mercaptoethanol (chain transfer agent, CTA), and 0.30 grams of azoisobutyronitriIo (Initiator) is charged into the addition funnel, and 50 grams of ethyl acetate, followed by the same degassing process as in the monomer solution. When the reactor temperature reaches 64 ° C, the initiator / CTA solution is also added to the reactor. The reaction is carried out at 64 ° C for 6 hours. After the copolymerization is finished, the reactor temperature is cooled to room temperature.

B-2. Amphiphilic Branched Prepolymer Synthesis

The copolymer solution prepared above, (B-1), is ethylenically functionalized to form an amphiphilic branched prepolymer by adding 4.52 grams of IEM (or an amount shown in Table 2), and 0.15 grams of DBTDL. The mixture is stirred at room temperature under a sealed condition for 12 hours. The prepared prepolymer is then stabilized with 100 ppm of hydroxy-tetramethylene-piperonyloxy. After the reaction solvent is exchanged to 1-propanol, the solution is ready to use for formulation. Various branched amphiphilic prepolymers are prepared with different combinations of different percentages of ethylenically functionalized polysiloxanes, CTA and IEM levels as indicated in Table 2.

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Table 2

<td>Amphiphilic Branched Prepolymer</td><td>% ethylenically functionalized polysiloxane</td><td>% of CTA</td><td>IEM</td>

<td>B-2a</td><td>Example 2, A-1.1 (60%)</td><td> 1.75 %</td><td>4.52 g</td>

<td>B-2b</td><td>Example 2, A-1.2 (70%)</td><td> 1.75 %</td><td>4.35 g</td>

<td>B-2c</td><td>Example 2, A-1.3 (80%)</td><td> 1.75 %</td><td>4.17 g</td>

<td>B-2d</td><td>Example 2, A-1.4 (100%)</td><td> 1.75 %</td><td>3.83 g</td>

<td>B-2e</td><td>Example 2, A-1.1 (60%)</td><td> 1.25 %</td><td>3.43 g</td>

<td>B-2f</td><td>Example 2, A-1.2 (70%)</td><td> 1.25 %</td><td>3.25 g</td>

<td>B-2g</td><td>Example 2, A-1.3 (80%)</td><td> 1.25 %</td><td>3.08 g</td>

B-3: Preparation of lens formulations

The lens formulations are prepared by dissolving an amphiphilic branched prepolymer prepared above, (B-2a to B-2g), and other components shown in Table 3. Other ingredients in each formulation include 1.0 percent DC1173 (DAROCUR ® 1173), 0.75 percent of DMPC (1,2-dimyrostoyl-sn-glycero-3-phosphocholine), and 23.25 percent of 1PrOH (1-propanol). The photo-rheology of lens formulations

prepared is studied using irradiation nitrayinleta- ^ iiv> mn a, intensity of 16 mW / cm2 with 330 nanometer filter (measured with ESE UV LOG), and are also summarized in Table 3.

Table 3

<td colspan="3">Lens formulation</td><td colspan="3">Photo-rheology</td>

<td>Amphiphilic Branched Prepolymer</td><td>DMA</td><td>TRIS- A.M*</td><td>Cure time, seconds</td><td>G ' kPa</td><td>Viscosity mPa.s</td>

* (tris- (trimetiI-siIiI)) - siloxy-propiI) -acryIamide (TRIS-Am)

Example 4

C-1: Amphiphilic Branched Copolymer Synthesis

A 4 liter jacketed reactor is equipped with a top stirring, reflux condenser with inlet adapter

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OF THE CURRENCY

ÍWDUmUAL

nitrogen / vacuum, thermometer, and sampling adapter. A mixture of 78.35 grams of ethylenically functionalized partially functionalized polysiloxane prepared in Example 2, A-1.3, and 8.71 grams of Example 2, A-2 is charged into the 4-liter reactor, and then degassed under vacuum to less than 10 mbar at room temperature for 30 minutes. After degassing, the reactor is filled with nitrogen gas waiting for further processing. The monomeric solution composed of 52.51 grams of DMA, 56.65 grams of Tris-Am and 390 grams of cyclohexane is transferred to the reactor. The final mixture is degassed at 100 mbar for 5 minutes, and then backfilled with nitrogen gas. This degassing cycle is repeated for 4 more times. The reaction mixture is then heated to 64 ° C, followed by the addition of a degassed initiator / chain transfer agent solution, composed of 0.60 grams of V-601 (2,2'-azobis- (2-methylpropionate dimethyl, from WAKO Specialty Chemicals), 7.50 grams of mercaptoethanol (CTA), and 10 grams of tetrahydrofuran (THE) Copolymerization is carried out at 64 ° C under nitrogen for a full 6 hours. After the reaction is complete, the temperature of the reactor is cooled to room temperature.

C-2. Amphiphilic Branched Prepolymer Synthesis

The copolymer solution prepared above, (C-1), is ethylenically functionalized to form an amphiphilic branched prepolymer by the addition of 7.50 grams of IEM and 0.21 grams of DBTDL, followed by stirring under a sealed dry condition at

orpumtiAL room temperature for 48 hours. The prepared prepolymer is then stabilized with

100 ppm of hydroxy-tetramethylene pi but ni I οχ i I o. After the repeated processes of evaporation of the reaction solvent and 1-propanol addition are carried out, to replace the reaction solvent with 1-propanol, the solution is ready to be used for formulation.

C-3: Preparation of formulations for lenses and photo-rheology

The amphiphilic branched polymer prepared above (C-3) is formulated with the final compositions listed in Table 4. The photo-rheology of the prepared formulations is studied using ultraviolet (UV) irradiation with an intensity of 16 mW / cm2 with 330 nanometer filter.

Table 4

<td colspan="6">Formulation</td><td colspan="3">Photo-rheology</td>

<td>Lot #</td><td>C-2</td><td>DMA</td><td>DC1173</td><td>DMPC</td><td>1-PrOH</td><td>Cure time, (s)</td><td>G ' kPa</td><td>Viscosity mPa.s</td>

DMPC: 1,2-dimyristo¡l-sn-glycero-3-phosphocolm;

DC1173: Darocur 1173

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C-4: Lens Preparation and Characterization

Contact lenses are made by cast molding from a previously prepared lens formulation (C-3.1 and C-3.2) in a reusable mold, similar to the mold shown in Figures 1 to 6 of the US Patents States of North America Numbers 7,384,590 and 7,387,759 (Figures 1 to 6). The mold comprises a female mold half made of CaF2 and a male mold half made of PMMA. The source of ultraviolet (UV) irradiation is a Hamamatsu bulb with the WG335 + TM297 cut-off filter at an intensity of approximately 4 mW / cm2 (measured with ESE UV LOG). The in-mold lens formulation is irradiated with ultraviolet (UV) irradiation for approximately 25 seconds. The prepared lenses are extracted with isopropanol, rinsed in pure water, coated with polyacrylic acid (PAA) (MW: 450kDa, from Lubrizol) by immersing the lenses in a solution of PAA in 1-PrOH (0.1 weight percent , pH of 2.5), and then hydrated with pure water. The coated lenses are packaged in lens packages containing phosphate-regulated serum (PBS), and autoclaved. Oxygen permeability (Dkapp and Dkc), and ion permeability (IP) are determined according to the procedures described in Example 1. The properties, Dk (barrers), IP (relative to Alsacon), elastic modulus (E '), elongation at breakage (EtB), and the water content (weight percent) of the lenses, are reported in Table 5.

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Table 5

<td>Lot #</td><td>E '(MPa)</td><td>EtB (%)</td><td>D kto pp</td><td>Dkc</td><td>IP</td><td>Water %</td>

. Average lens thickness: 113 microns.

center d

2. Average lens center thickness: 115 microns.

# The lenses are used

Lotrafilcon B with an average lens center thickness of 80 microns as the reference lenses, and the

Intrinsic Dk of the reference lenses is 110 barrers.

Example 5

D-1. Amphiphilic Branched Copolymer Synthesis

3- [tris- (trimethyl-siloxy) -silyl] -propyl (TRIS), and 279 grams of ethyl acetate, is charged into the 500 milliliter addition funnel, followed by vacuum degassing at 100 mbar and at room temperature for 10 minutes, and then back-up with nitrogen gas. The monomer solution is degassed under the same conditions for two additional cycles. The monomer solution is then charged into the reactor. The reaction mixture is heated to 67 ° C with stirring. While heating, a solution composed of 1.50 grams of mercaptoethanol (CTA), and 0.26 grams of azoisobutyronitrile (initiator), and 39 grams of ethyl acetate is charged into the addition funnel, followed by the same degassing process as in the monomeric solution. When the reactor temperature reaches 67 ° C, the initiator / CTA solution is also added to the reactor. The reaction is carried out at 67 ° C for 8 hours. After the copolymerization is finished, the reactor temperature is cooled to room temperature.

D-2. Amphiphilic Branched Prepolymer Synthesis

The copolymer solution prepared above, (D-1), is ethylenically functionalized to form an amphiphilic branched prepolymer by the addition of 4.45 grams of IEM (or isocyanatoethyl methacrylate in a desired equivalent molar amount), in the presence of 0.21 grams of DBTDL . The mixture is stirred at room temperature under a sealed condition for 24 hours. The prepared macromonomer is then stabilized with 100 ppm of hydroxy-tetramethylene-piperonyloxy before concentrating the solution.

up to 200 grams (approximately 50 percent through 1-micron pore size filter paper. The solids content is measured by removing the solvent in a vacuum oven at 80 ° C. After the solvent is The reaction is exchanged to 1-propanol, the solution is further concentrated to the desired concentration, and is ready to use for the preparation of lens formulations.

D-3. Preparation of formulation for lenses and photo-rheology

A lens formulation is prepared to have the following composition: 72 weight percent prepolymer D2 prepared above; 6 percent by weight DMA; 1 percent by weight of DC1173; 0.75 weight percent DMPC; and 20.25 weight percent 1-PrOH. Photo-rheology is studied using the Hamamatsu focus with a 330 nanometer long-pass cutoff filter placed just before the sample. Intensity (16 mW / cm2) is measured using ESE UV LOG with a 297 nanometer cutoff filter, long-pass filters are placed before the sample for formulation curing. The results of the photoreology study are: a cure time of approximately 12 seconds, G 'of 165 kPa, and a viscosity of 5550 mPa.s.

D-4: Characterization of lenses

Contact lenses are cast from D3 lens formulation, extracted with isopropanol, rinsed in water, coated with PAA, hydrated in water, packaged / autoclaved in lens packaging, and are characterized by

102

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MEXICAN INSTITUTE DELA MOR EDA »INDUSTRIAL

according to the procedures described in Example 4. The lenses obtained have the following properties: E '= 0.75 MPa; EtB% =

212; Dkapp = 95 (for lenses with an average central thickness of

119 micras); DKC = 172 (using lotrafilcon B lenses as the reference lenses, an average central thickness of 81 microns, and an intrinsic Dk of 110); IP = 3.6; % water = 29.0.

Example 6

E-1: Synthesis of amphiphilic branched copolymer absorbing ultraviolet radiation (UV)

103

The monomeric mixture is then charged to the reactor, the rgp ^ ria is heated to 67 ° C with adequate stirring. While heating, a solution composed of 1.48 grams of mercaptoethanol (chain transfer agent, CTA), and 0.26 grams of az oisobuti ro n it ri I o (initiator), and 38 grams of acetate is charged into the addition funnel. of ethyl, followed by the same degassing process as in the monomeric solution. When the reactor temperature reaches 67 ° C, the initiator / CTA solution is also added to the reactor. The reaction is carried out at 67 ° C for 8 hours. After the copolymerization is finished, the reactor temperature is cooled to room temperature.

E-2: Synthesis of amphiphilic branched prepolymer absorbing ultraviolet radiation (UV)

The copolymer solution prepared above, (E-1), is ethylenically functionalized to form an amphiphilic branched prepolymer by adding 3.84 grams of IEM (or isocyanatoethyl methacrylate in a desired equivalent molar amount), in the presence of 0.15 grams of DBTDL . The mixture is stirred at room temperature under a sealed condition for 24 hours. The prepared prepolymer is then stabilized with 100 ppm of hydroxy-tetramethylene-piperonyloxy before concentrating the solution to 200 grams (approximately 50 percent), and is filtered through a filter paper with a pore size of 1 micron. After the reaction solvent is exchanged to 1-propanol through repeated cycles of evaporation and dilution, the

104 solution is ready solids is measured

to be used for formulation. The content by removing the solvent in a vacuum oven at 80 ° C.

E-3: Preparation of formulation for lenses and photo-rheology

A lens formulation is prepared to have the following composition: 71 percent by weight prepolymer E2 prepared above; 4 weight percent DMA; 1 percent by weight of TPO; 0.75 weight percent DMPC; and 23.25 weight percent 1-PrOH. Photo-rheology is studied using the Hamamatsu focus with a 330 nanometer stack, and 388 nanometer long-pass cutoff filters are placed just before the sample. Intensity (4.6 mW / cm2) is measured using an IL1700 detector using a SED005 sensor with a 297 nanometer cutoff filter from International Light, the long-pass filters are placed before the sample for formulation curing. The results of the photo-rheology study are: a cure time of approximately 22 seconds, G 'of 155 kPa, and a viscosity of 2900 mPa.s.

E-4: Characterization of lenses

Contact lenses are cast from E3 lens formulation, extracted with isopropanol, rinsed in water, coated with PAA, hydrated in water, packaged / autoclaved in lens packaging, and they are characterized according to the procedures described in Example 4. The lenses obtained have the following properties: E '= 0.72 MPa; EtB% =

105

130, Dkapp = 101 (for lenses with an average central thickness of

I »I w '

122 micras); DKC = 181 (using lotrafilcon B as the reference lenses, an average central thickness of 80 microns, and an intrinsic Dk of 110); IP = 2.9; % water = 26.9; and UVA / UVB% T = 4.3 / 0.09.

Example 7

A: Synthesis of 80 percent ethylenically functionalized extended chain polysiloxane

KF-6001A (a, uj-b¡s- (2-hydroxy-ethoxy-propyl) -poly-dimethylsiloxane, Mn = 2000, from Shin-Etsu), and KF-6002A (a, u-bis- (2 hydroxy-ethoxy-propyl) -poly-dimethyl-siloxane, Mn = 3400, from Shin-Etsu), are dried separately at about 60 ° C for 12 hours (or overnight), under a high vacuum in a single neck flask. The OH molar equivalent weights of KF-6001A and KF-6002A are determined by titration of the hydroxyl groups, and are used to calculate the molar milliequivalent to be used in the synthesis.

A one liter reaction vessel is evacuated overnight to remove moisture, and the vacuum is broken with dry nitrogen. 75.00 grams (75 milliequivalents) of the dry KF6001A is charged into the reactor, and then 16.68 grams (150 milliequivalents) of freshly distilled IPDI is added to the reactor. The reactor is purged with nitrogen and heated to 45 ° C with stirring, and then 0.30 grams of DBTDL are added. The reactor is sealed, and a positive flow of nitrogen is maintained. An exotherm occurs, after

which, the reaction mixture is allowed to cool and is stirred at 55 ° C for 2 hours. After reaching the exotherm, 248.00 grams (150 milliequivalents) of the dry KF6002A are added to the reactor, at 55 ° C, and then 100 microliters of DBTDL are added. The reactor is stirred for four hours. Heating is discontinued and the reactor is allowed to cool overnight. Nitrogen sparging is stopped, and the reactor is opened to atmosphere for 30 minutes with moderate stirring. A hydroxyl terminated extended chain polysiloxane is formed having 3 polysiloxane segments, HO-PDMS-IPDI-PDMS-IPDI-PDMS-OH (or HO-CE-PDMSOH).

For the 80 percent ethylenically functionalized polysiloxane, 18.64 grams (120 milliequivalents) of IEM are added to the reactor, along with 100 microliters of DBTDL. The reactor is stirred for 24 hours, and then the product is decanted (CE-PDMS capped with 80 percent IEM) and stored under refrigeration.

B: Synthesis of amphiphilic branched polysiloxane prepolymer not absorbing ultraviolet radiation (UV)

A 1 liter jacketed reactor is equipped with a 500 milliliter addition funnel, top agitation, reflux condenser with nitrogen / vacuum inlet adapter, thermometer, and sampling adapter. The reactor is charged with 45.6 grams of the 80 percent IEM capped CEPDMS prepared above, and sealed. A solution of 0.65 grams of hydroxyethyl methacrylate (HEMA), 25.80 grams of DMA, and 27.80 grams of

(tr¡s- (tr¡methyl-s¡l¡l)) - s¡loxypropyl) methacrylate (TRIS) in 279 ..... grams of ethyl acetate in addition funnel. The reactor is degassed at <1 mbar for 30 minutes at room temperature with a high vacuum pump. The monomeric solution is degassed at 100 mbar and at room temperature (RT) for 10 minutes in three cycles, breaking the vacuum with nitrogen between degassing cycles. The monomeric solution is then charged to the reactor, and then the reaction mixture is stirred and heated to 67 ° C. While heating, a solution of 1.50 grams of mercaptoethanol (chain transfer agent, OTA), and 0.26 grams of azoisobutyronitrile dissolved in 39 grams of ethyl acetate is charged into the addition funnel, and deoxygenated three times at 100 mbar and at room temperature (RT) for 10 minutes. When the reactor temperature reaches 67 ° C, the initiator / CTA solution is added to the PDMS / monomer solution in the reactor. The reaction is allowed to proceed for 8 hours, and then heating is stopped, and the temperature of the reactor is brought to room temperature within 15 minutes.

The resulting reaction mixture is then siphoned into a dry, single neck flask with a tight lid, and 4,452 grams of IEM are added with 0.21 grams of DBTDL. The mixture is stirred for 24 hours at room temperature, forming the non-absorbing ultraviolet (UV) amphiphilic branched polysiloxane prepolymer. To this mixing solution, add 100 microliters of a hydroxy-tetramethylene-piperonyloxy solution.

108

in ethyl acetate (2 grams / 20 milliliters). The solution is then concentrated to 200 grams (approximately 50 percent), using a rotary evaporator at 30 ° C, and filtered through a filter paper with a pore size of 1 micron. After exchanging the solvent to 1-propanol, the solution is further concentrated to the desired concentration.

C. Synthesis of Ultraviolet (UV) Absorbing Amphiphilic Branched Polysiloxane Prepolymer

A 1 liter jacketed reactor is equipped with a 500 milliliter addition funnel, top agitation, reflux condenser with nitrogen / vacuum inlet adapter, thermometer, and sampling adapter. The reactor is then charged with 45.98 grams of the 80 percent IEM capped CE-PDMS prepared above, and the reactor is sealed. A solution of 0.512 grams of HEMA, 25.354 grams of DMA, 1.38 grams of Norbloc methacrylate, 26.034 grams of Tris, in 263 grams of ethyl acetate is charged into the addition funnel. The reactor is degassed at <1 mbar for 30 minutes at room temperature with a high vacuum pump. The monomeric solution is degassed at 100 mbar and at room temperature (RT) for 10 minutes in three cycles, breaking the vacuum with nitrogen between degassing cycles. The monomer solution is then charged into the reactor, and then the reaction mixture is stirred and heated to 67 ° C. While heating, a solution of 1,480 grams of mercaptoethanol (chain transfer agent,

109

CTA), and 0.260 grams

BE LA «O« EDA u of dissolved azoisobutyronitrile willNWl'98 gTa of ethyl acetate, and three vo4> & o <ι · Ί · 0 · 0 irrtrai · y- are deoxygenated at room temperature for 10 minutes. When the reactor temperature reaches 67 ° C, the initiator / CTA solution is added to the PDMS / monomer solution in the reactor. The reaction is allowed to proceed for 8 hours, and then the heating is stopped, and the temperature of the reactor is brought to room temperature within 15 minutes.

The resulting reaction mixture is then siphoned into a dry, single neck flask with a tight lid, and 3,841 grams of isocyanatoethyl acrylate are added with 0.15 grams of DBTDL. The mixture is stirred for 24 hours at room temperature, forming an ultraviolet (UV) absorbing amphiphilic branched polysiloxane prepolymer. To this mixing solution, 100 microliters of a solution of hydroxytetramethylene-piperonyloxy in ethyl acetate (2 grams / 20 milliliters) are added. The solution is then concentrated to 200 grams (approximately 50 percent), using a rotary evaporator at 30 ° C, and filtered through a filter paper with a pore size of 1 micron.

D-1: Lens formulation with polysiloxane prepolymer not absorbing ultraviolet radiation (UV)

In a 100 milliliter amber flask, add 4.31 grams of a macromer solution (which is an 82.39 percent solution in 1-propanol, prepared from the solution of

110

macromers prepared above, by repeated cycles of 1-propanol dilution evaporation). In a 20 milliliter bottle, 0.081 grams of TPO and 0.045 grams of DMPC are dissolved in 10 grams of 1-propanol, and then transferred to the macromer solution. After the mixture is concentrated to 5.64 grams using a rotary evaporator at 30 ° C, 0.36 grams of DMA are added, and the formulation is homogenized at room temperature. 6 grams of a clear lens formulation D-1 are obtained.

D-2: Lens formulation with ultraviolet (UV) absorbing polysiloxane prepolymer (4 percent DMA)

In a 100 milliliter amber flask, add 24,250 grams of a macromer solution (43.92 percent in ethyl acetate). In a 50 milliliter bottle, 0.15 grams of TPO and 0.75 grams of DMPC are dissolved in 20 grams of 1-propanol, and then transferred to the macromer solution. 20 grams of solvent are removed using a rotary evaporator at 30 ° C, followed by the addition of 20 grams of 1-propanol. After two cycles, the mixture is concentrated to 14.40 grams. 0.6 grams of DMA are added to this mixture, and the formulation is homogenized at room temperature. 15 grams of a clear lens formulation D-2 are obtained.

D-3: Ultraviolet (UV) absorbing polysiloxane prepolymer lens formulation (2 percent DMA / 2 percent HEA)

30 ° C, followed by the addition of 20 grams of 1-propanol. After two cycles, the mixture is concentrated to 14.40 grams. 0.3 grams of DMA and 0.3 grams of HEA are added to this mixture, and the formulation is homogenized at room temperature. 15 grams of a clear lens formulation D-3 are obtained.

Example 8

E: Covalent bonding of modified PAE coating polymers

Monomers containing amine groups, N (3-amino-propyl) -methacrylamide hydrochloride (APMAA-HCI) or N- (2-amino-ethyl) -methacrylamide hydrochloride (AEMAA-HCI) are purchased from Polisciences, and used as received. Poly (amidoaminoepichlorohydrin) (PAE) is received from Ashland, as an aqueous solution, and is used as received. Poli- (acrylamide-co-acrylic acid) (poly- (AAm-co-AA) (90/10) from Polisciences, mPEG-SH from Laysan Bio, and poly- (MPC-co-AeMA) (en that is, a copolymer of methacryloyloxy-ethyl-phosphoryl-choline (MPC), and amino-ethyl methacrylate (AeMA)) of NOF, are used as received.

112

The APMAA-HCI monomer dissolves in metheniplin and is eTgTggg **? lens formulations D-1, D-2 and D-3 (prepared in Example 7) to a concentration of 1 percent by weight.

Reactive packing saline is prepared by dissolving the components listed in Table 6, along with the appropriate buffer salts, in deionized (DI) water. After heat pretreatment, the saline solution is allowed to cool to room temperature, and is then filtered using a 0.2 micron ESP filter.

Table 6

<td>Sample saline solution packaging</td><td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td>

113

The lens formulation D-1, D-2 and D3 prepared in Example 7 is modified by the addition of the APMAA-HCl monomer (APMMA-HCL supply solution in methanol). DSM lens cures at 16mW / cm2 with a 330 nanometer filter, while the LS lens cures at 4.6 mW / cm2 with a 380 nanometer filter.

DSM lenses.

The female portions of polypropylene lens molds are filled with approximately 75 microliters of a lens formulation prepared as above, and the molds are closed with the male portion of the polypropylene lens molds (base curve molds). Contact lenses are obtained by curing the molds and closed for approximately 5 minutes with a source of ultraviolet (UV) irradiation (Hamamatsu focus with a 330 nanometer cut-off filter at an intensity of approximately 16 mW / cm2.

LS lenses.

LS lenses are prepared by cast casting

114

from a lens formulation prepared as above in a reusable mold, similar to the mold shown in Figures 1 to 6 of US Patent Numbers 7,384,590 and 7,387,759 (Figures 1 to 6). The mold comprises a female mold half made of quartz (or CaF2), and a male mold half made of glass (or PMMA). The ultraviolet (UV) irradiation source is a Hamamatsu spotlight with a 380 nanometer cut-off filter at an intensity of approximately 4.6 mW / cm2. The in-mold lens formulation is irradiated with ultraviolet (UV) irradiation for approximately 30 seconds.

The APMAA-HCI modified lens formulation D-1 (from Example 7) cures according to the DSM and LS methods described above, while the D-2 or D-3 lens formulation (from Example 7) it is cured according to the method for LS described above.

The molded lenses are extracted into methyl ethyl ketone, hydrated, and packed in one of the saline solutions described in Table 6. The lenses are placed in a polypropylene lens packaging case with 0.6 milliliters of the saline solution. In-Pack Coating (IPC) (half of the saline is added before inserting the lens). The bubble is then sealed with foil and autoclaved for 30 minutes at 121 ° C.

Evaluation of the lens surface shows that none of the test lenses had any dirt adhesion. When

115

seen under the darkfield microscope, there are no visible crack lines after rubbing the lenses between the fingers.

Wettability (WBUT), lubricity, and contact angle of the lens surface are measured, and the results are summarized in Table 7.

Table 7

<td>Lens formulation for making lenses</td><td>Solution Saline1</td><td>WBUT (sec)</td><td>Lubricity</td><td>Contact Angle [°]</td>

<td rowspan="2">D1 as control (free from APMAA)</td><td> 1</td><td> 0</td><td> 4-5</td><td> 114</td>

<td rowspan="2">D1 w / 1% APMAA</td><td> 1</td><td> 10</td><td> 0-1</td><td> 104</td>

<td rowspan="3">D2 as control (free from APMAA)</td><td> 1</td><td> 0</td><td> 4-5</td><td> 115</td>

<td rowspan="2">D2 w / 1% APMAA</td><td> 1</td><td> 5</td><td> 2-3</td><td> 90</td>

<td colspan="5">116 ______ IMPI • «Wall MttlCANO DC THE NOREDAD UVmaSSL</td><td> 5</td>

<td rowspan="2">Lens formulation for making lenses</td><td rowspan="2">Solution Saline1</td><td rowspan="2">WBUT (sec)</td><td></td><td>Angle of</td><td></td>

<td>Lubricity</td><td>Contact [1</td><td rowspan="12"></td>

<td rowspan="5">D3 as control (free from APMAA)</td><td> 1</td><td> 12</td><td> 3-42</td><td> 1052</td>

<td rowspan="5">D3 w / 1% APMAA</td><td> 1</td><td>OR2</td><td> 42</td><td> 1032</td>

<td colspan="4">1 The number is the number of saline c</td><td colspan="2">e packaging</td>

shown in Table 5.

LS lenses.

117

Tested lenses are made according to Je ^ rt ^ '^ e All for

DSM unless otherwise specified. Lubricity is rated against a qualitative scale of 0 to 4, with lower numbers indicating higher lubricity. In general, lens surface properties improve somewhat after application of the coating within the package.

Example 9

Lenses are manufactured using lens formulation D-2 (Example 7) to which APMAA monomer has been added at a concentration of 1 percent. LS lenses are made by cast molding from a lens formulation prepared as above in a reusable mold, similar to the mold shown in Figures 1 through 6 of U.S. Patent Nos. 7,384,590 and 7,387,759 (Figures 1 to 6). The mold comprises a female mold half made of glass and a male mold half made of quartz. The ultraviolet (UV) irradiation source is a Hamamatsu spotlight with a 380 nanometer cut-off filter at an intensity of approximately 4.6 mW / cm2. The in-mold lens formulation is irradiated with ultraviolet (UV) irradiation for approximately 30 seconds.

Cast-molded lenses are extracted with methyl ethyl ketone (MEK), rinsed in water, coated with polyacrylic acid (PAA) by dipping the lenses in a solution of PAA in propanol (0.0044 percent by weight, acidified with acid formic to 118 IMPI ^ ινπτπγγο muicaho

ΓΕ PÍOHEDAD industrial approximately a pH of 2.5), and hydrate in water.

The In-Pack Overlay Saline Solution (IPC) is prepared from a composition containing approximately 0.07 percent PAAm-PAA and enough PAE to provide an initial azetidinium content of approximately 8.8 millimolar equivalents / liter (approximately 0.15 percent PAE), under conditions prior to reaction of 8 hours at about 60 ° C. 10 ppm of hydrogen peroxide is then added to the saline coating solutions inside the package (IPC) to prevent the growth of bioburden, and the in-package coating saline solutions (IPC) are filtered using a 0.22 micron polyether-sulfone (PES) membrane filter. The lenses are placed in a polypropylene lens packaging case with 0.6 milliliters of the 0.22 micron saline solution. In-Pack Coating (IPC) (half of the saline is added before inserting the lens). The bubble is then sealed with foil and autoclaved for 30 minutes at 121 ° C.

Evaluation of the lens surface shows that none of the trial lenses have any dirt adhesion. When viewed under the dark field microscope, there are no visible crack lines after rubbing the lenses between the fingers. The wettability (WBUT) of the lens surface is greater than 10 seconds, the lubricity is rated "1", and the contact angle is approximately 20 °.

119

Example 10

IMPI mrmvr · «maid of INDIRNILAl mold

Synthesis of amphiphilic branched copolymer- gbsurbenLe ife ultraviolet (UV) radiation

A 1 liter jacketed reactor is equipped with a 500 milliliter addition funnel, top agitation, reflux condenser with nitrogen / vacuum inlet adapter, thermometer, and sampling adapter. 89.95 grams of the ethylenically functionalized, partially functionalized polysiloxane prepared in Example 2-1.3 is charged to the reactor, and then less than 1 mbar is degassed under vacuum at room temperature for about 30 minutes. The monomer solution prepared by mixing 1.03 grams of HEMA, 50.73 grams of DMA, 2.76 grams of Norbloc methacrylate, 52.07 grams of Tris, and 526.05 grams of ethyl acetate, is charged into the 500 milliliter addition funnel, followed by degassing under vacuum at 100 mbar and at room temperature for 10 minutes, and then backfilling with nitrogen gas. The monomeric solution is degassed under the same conditions for two additional cycles. The monomer solution is then charged into the reactor. The reaction mixture is heated to 67 ° C with adequate stirring. While heating, a solution composed of 2.96 grams of mercaptoethanol (chain transfer agent, CTA), and 0.72 grams of dimethyl 2,2'azobis- (2-methyl-propionate) (V -601 - initiator), and 76.90 grams of ethyl acetate, followed by the same degassing process as in the monomeric solution. When the

120

IMPI

ΙΜΙΤυτο M * ICAN · Μ the mold ο rNtXISTUIA The temperature of the reactor reaches 67 ° C, the solution, of iriitator / CTA.

it is also added to the reactor. The reaction is carried out at 67 ° C for 8 hours. After the copolymerization is finished, the reactor temperature is cooled to room temperature.

Synthesis of Amphiphilic Branched Prepolymer Absorbing Ultraviolet (UV) Radiation

The copolymer solution prepared above is ethylenically functionalized to form an amphiphilic branched prepolymer by the addition of 8.44 grams of IEM (or 2-isocyanate-ethyl methacrylate in a desired equivalent molar amount), in the presence of 0.50 grams of DBTDL. The mixture is stirred at room temperature under a sealed condition for 24 hours. The prepared prepolymer is then stabilized with 100 ppm of hydroxy-tetramethylene-piperonyloxy before concentrating the solution to 200 grams (approximately 50 percent), and is filtered through a filter paper with a pore size of 1 micron. After the reaction solvent is exchanged to 1-propanol through repeated cycles of evaporation and dilution, the solution is ready to use for formulation. The solids content is measured by removing the solvent in a vacuum oven at 80 ° C.

Preparation of lens formulation

A lens formulation is prepared to have the following composition: 71 percent by weight of the prepolymer prepared above; 4 weight percent DMA; 1 percent by weight of

121

ΤΡΟ; 1 weight percent DMPC; 1 per cent in pe '^^ of é'hpS?

(from Sigma-Aldrich), and 22 percent by weight of 1-ΡΓϋΉ (

Lens Preparation

The lenses are manufactured by cast molding the lens formulation prepared above, using a reusable mold, similar to the mold shown in Figures 1 to 6 of United States Patent Numbers 7,384,590 and 7,387,759 (Figures 1 to 6). , under spatial limitation of ultraviolet (UV) irradiation. The mold comprises a female mold half made of glass and a male mold half made of quartz. The ultraviolet (UV) irradiation source is a Hamamatsu spotlight with a 380 nanometer cut-off filter at an intensity of approximately 4.6 mW / cm2. The in-mold lens formulation is irradiated with ultraviolet (UV) irradiation for approximately 30 seconds.

The cast molded lenses are extracted with methyl ethyl ketone (MEK), rinsed in water, coated with polyacrylic acid (PAA) by immersing the lenses in a solution of PAA in propanol (0.004 percent by weight, acidified with acid formic at about a pH of 2.0), and hydrate in water.

122 (about 0.15 percent PAE), under 6 hour pre-reaction conditions at about 60 ° C. 5 ppm of hydrogen peroxide is then added to the in-pack coating saline solutions (IPC) to prevent bioburden growth, and the in-pack coating saline (IPC) solutions are filtered using a polyether membrane filter. sulfone (PES) of 0.22 microns. The lenses are placed in a polypropylene lens packaging case with 0.6 milliliters of the coating saline solution inside the package (IPC) (half of the saline solution is added before inserting the lens). The bubble is then sealed with foil and autoclaved for 30 minutes at 121 ° C.

Lens characterization

The lenses obtained have the following properties: E '~ 0.82 MPa; DKC~ 159.4 (using lotrafilcon B as the reference lenses, an average central thickness of 80 microns, and an intrinsic Dk of 110); IP ~ 2.3,% water ~ 26.9; and UVA / UVB% T ~ 4.6 / 0.1.

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Abstract

Term

CPC: C08F290 / 068; C08G77 / 00; C08G77 / 458; CO8G2210 / 00; G02B1 / 043

SMITH; LAURA ANN SANDERS; JOHN DALLAS PRUITT

REQUEST

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THE DIVISIONAL DIRECTOR OF PATENTS

NAHANNY CANAL REYES

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IA ........—

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