Contact lenses and contact lens formulations with reduced rippling.

Abstract

The present invention provides a silicone hydrogel contact lens formulation comprising a difunctional siloxane, a hydrophilic N-vinylamide monomer, and at least 0.10% (wt / wt) triphenylphosphine (TPP), a silicone hydrogel contact lens formed from the polymerization of the silicone hydrogel contact lens formulation, and the use of TPP to improve the surface properties of contact lenses prepared from a formulation comprising a difunctional siloxane and a hydrophilic N-vinylamide monomer.

Description

[Technical Field]

[0001] The present invention relates to a polymerizable formulation containing triphenylphosphine for use in the manufacture of contact lenses, and to contact lenses incorporating a polymer matrix formed from the polymerizable formulation. In particular, the present invention relates to a polymerizable formulation that has been shown to impart advantageous properties, such as a reduction in surface rippling, to hydrogel contact lenses. [Background technology]

[0002] Silicone hydrogel contact lenses with good lens properties, such as high water content, low contact angle, and high oxygen permeability (Dk), have been developed. However, when certain polymerizable compositions are cast into silicone hydrogel contact lenses, particularly in polypropylene (PP) molds, surface rippling may be observed. Surface rippling has been found to be particularly severe when the contact lens is cast from a polymerizable composition that contains a relatively high proportion of high molecular weight siloxane components. Reducing surface ripping in silicone hydrogel contact lenses while simultaneously maintaining good lens properties remains a necessity. [Overview of the project]

[0003] In a first aspect, the present invention relates to a silicone hydrogel contact lens formulation, a. A polymerizable siloxane component comprising at least 40% (wt / wt) of polymerizable siloxane components, wherein at least 50% (wt / wt) of the polymerizable siloxane content is a bifunctional siloxane having a molecular weight of at least 5,000 daltons, and particularly at least 8,000 daltons, b. At least 30% (wt / wt) of hydrophilic N-vinylamide monomer, c. At least 0.10% (wt / wt) of triphenylphosphine (TPP) The present invention provides a formulation that includes the above. Furthermore, the silicone hydrogel contact lens formulation of the present invention typically comprises a further polymerizable monomer, an oligomer and / or prepolymer, one or more crosslinking agents, and one or more polymerization initiators.

[0004] It was found that by including at least 0.10% (wt / wt) of TPP in a contact lens formulation comprising (a) a polymerizable siloxane component in which at least 40% (wt / wt) of the polymerizable siloxane content is a relatively high molecular weight component, i.e., a bifunctional siloxane of at least 5,000 daltons, particularly at least 8,000 daltons, and (b) at least 30% (wt / wt) of a hydrophilic N-vinylamide monomer, the resulting formulation exhibits durability against surface rippling compared to similar formulations without TPP, while maintaining good lens properties, such as high water content, low contact angle, and high oxygen permeability (Dk). In a second aspect, the present invention provides a silicone hydrogel contact lens formed from polymerization of the formulation of the first aspect of the present invention. Therefore, the polymer lens material of the silicone hydrogel contact lens of the second aspect of the present invention is a. A polymerizable siloxane component comprising at least 40% (wt / wt) of polymerizable siloxane components, wherein at least 50% (wt / wt) of the polymerizable siloxane content is a bifunctional siloxane having a molecular weight of at least 5,000 daltons, and particularly at least 8,000 daltons; b. At least 30% (wt / wt) of hydrophilic N-vinylamide monomer, c. At least 0.10% (wt / wt) of triphenylphosphine (TPP) This includes polymer products obtained by polymerizing formulations containing the above.

[0005] In a third embodiment, the present invention relates to the use of TPP for improving the surface properties of a contact lens, wherein the contact lens is a. A polymerizable siloxane component comprising at least 40% (wt / wt) of polymerizable siloxane components, wherein at least 50% (wt / wt) of the polymerizable siloxane content is a bifunctional siloxane having a molecular weight of at least 5,000 daltons, and particularly at least 8,000 daltons, b. At least 30% (wt / wt) of hydrophilic N-vinylamide monomer and Provides a use prepared from a formulation containing the following: Advantageously, in a third aspect of the present invention, TPP is used in an amount of at least 0.10% (wt / wt) based on the total mass of the formulation. Advantageously, in the first, second, and third embodiments of the present invention, at least 20% (wt / wt) of the polymerizable siloxane content is a monofunctional siloxane having a molecular weight of less than 3000 daltons.

[0006] The formulation of the present invention was found to reduce the amount of surface rippling present on cast contact lenses compared to lenses cast from the same polymerizable formulation except that it does not contain TPP. The reduction in surface rippling is particularly pronounced in silicone hydrogel contact lenses cast in a polypropylene (PP) mold. It was found that adding TPP to the polymerizable formulation that forms the lens does not adversely affect the properties of the resulting cast lens, such as water content, contact angle, and oxygen permeability (Dk), compared to lenses cast from a polymerizable formulation that does not contain TPP. [Modes for carrying out the invention]

[0007] The Disclosure will be more fully understood and further advantages will become apparent upon reference to the following detailed description of embodiments of the Disclosure. The Invention will be described in more detail with particular reference to the formulation of the first aspect of the Invention, hereafter referred to as “the Formulation of the Invention.” However, since the contact lens of the second aspect of the Invention is available from polymerization of the formulation of the first aspect of the Invention, it should be understood that the components of the formulation of the first aspect of the Invention will therefore exist in a polymerized form within the polymer lens material of the contact lens of the second aspect of the Invention. Similarly, a contact lens in which particular advantages have been found from the use of TPP to improve surface properties according to the third aspect of the Invention is obtained from polymerization of a formulation having the properties described herein with respect to the lens of the second aspect of the Invention and / or the properties described herein with respect to the formulation of the first aspect of the Invention. Therefore, the components of the formulation of the first aspect of the Invention will exist in a polymerized form within the polymer lens material of a contact lens in which TPP is used according to the third aspect of the Invention. The features of formulations or lenses or their components referred to herein, or the features of the use of TPP (depending on the context), may be combined with any combination of the features described herein or thereafter, unless the particular combination of features is mutually exclusive or the context indicates otherwise. Furthermore, as used in this specification, the singular forms "a," "an," and "the" include plural referents (e.g., at least one or more) unless the context clearly indicates otherwise. Thus, for example, a reference to "a contact lens" includes a single lens as well as two or more lenses, one or more of the same or different lenses.

[0008] It has been found that by incorporating at least 40% (wt / wt) of siloxane, where at least 50% is a high molecular weight bifunctional siloxane of at least 5,000 daltons, particularly 8,000 daltons, together with 30% (wt / wt) of an N-vinylamide hydrophilic monomer, a contact lens having advantageously high water content, high surface wettability, and high oxygen permeability (Dk) is provided. It has been found that the mechanical strength of the resulting lens is enhanced by optionally incorporating additional non-siloxane hydrophobic monomers, particularly hydroxybutyl methacrylate and / or isobornyl methacrylate.

[0009] This disclosure is based on further findings that when at least 0.10% (wt / wt) of TPP is included in the polymerizable formulation used to manufacture contact lenses, it is possible to provide contact lenses and their individual formulations that exhibit resistance to surface rippling and have good lens properties. Other equivalent formulations that do not contain TPP have been found to exhibit surface rippling. Surface rippling is an undesirable property for contact lenses because it can cause discomfort to the wearer. Furthermore, surface rippling can degrade the optical properties of contact lenses. Therefore, formulations with little or no surface rippling are preferred. Contact lenses formed from formulations with high viscosity, for example, a viscosity exceeding 250 mm² / s at 25°C, or for example, a viscosity exceeding 300 mm² / s at 25°C, have been found to be particularly susceptible to surface rippling. Similarly, contact lenses formed from formulations containing a high proportion of high molecular weight siloxane components, for example, formulations in which at least 40% (wt / wt) are polymerizable siloxane components, of which at least 50% (wt / wt) are polymerizable siloxanes having a molecular weight of at least 5,000 daltons, particularly at least 8,000 daltons, were found to be particularly susceptible to surface rippling. It was found that including a substantial amount of high molecular weight siloxane, based on the mass of a polymerizable formulation of siloxane having a viscosity of 300 mm² / s or more at 25°C, results in the overall formulation having a relatively high viscosity, for example, 250 mm² / s or more at 25°C. It was found that the inclusion of TPP in such formulations is effective in preventing or reducing surface rippling. The polymerizable components of the formulations of the present invention are typically incorporated into the contact lenses of the present invention.

[0010] References herein to the amount of components or constituents present in a formulation expressed in mass percentage (i.e., %(wt / wt)) are based on the amount of all formulation components except diluents and / or solvents not incorporated into the polymer lens material of the finished contact lens. Therefore, for example, the amount of TPP in a formulation (total 100 parts) prepared by mixing 0.5 parts TPP, 40 parts siloxane components, 30 parts hydrophilic N-vinylamide monomer, 4.5 parts other active ingredients (e.g., polymerization initiators, colorants, oxygen scavengers, etc.) and 25 parts organic solvent and / or water is 0.67%(wt / wt). As used herein, “components” of a formulation refer collectively to all components of a particular type. For example, if a formulation contains 20%(wt / wt) of a first siloxane monomer and 25% of a second siloxane monomer, and no other siloxanes, it may be stated that the formulation contains 45%(wt / wt) of siloxane components.

[0011] The polymerizable formulation of the present invention contains triphenylphosphine (TPP; CAS number: 603-35-0). TPP is a common organophosphorus compound used in the synthesis of organic and organometallic compounds and intermediates for the production of pharmaceuticals, phosphonium salts, and other phosphorus compounds. [ka] The silicone hydrogel contact lens formulation of the present invention contains at least 0.10% (wt / wt) TPP. TPP may be present in the polymerizable formulation in an amount of at least 0.15% (wt / wt), for example, at least 0.20% (wt / wt), and particularly at least 0.25% (wt / wt). For example, TPP may be present in the polymerizable formulation in an amount of about 0.15% (wt / wt) to about 2.0% (wt / wt), for example, 0.20% (wt / wt) to 1.0% (wt / wt), and typically in an amount of about 0.25% (wt / wt) to about 1.0% (wt / wt).

[0012] The contact lens formulation of the present invention is a. A polymerizable siloxane component comprising at least 40% (wt / wt) of polymerizable siloxane components, wherein at least 50% (wt / wt) of the polymerizable siloxane content is a bifunctional siloxane having a molecular weight of at least 5,000 daltons, and particularly at least 8,000 daltons; b. At least 30% (wt / wt) of hydrophilic N-vinylamide monomer, c. At least 0.10% (wt / wt) of the TPP, for example, about 0.20% (wt / wt) to about 2% (wt / wt) of the TPP and This is a silicone hydrogel contact lens formulation containing [a specific ingredient / component]. A "silicone hydrogel" refers to a crosslinked polymer material (i.e., polymer matrix) having a three-dimensional polymer network that is insoluble in water but contains at least 10 mass percent of water in its polymer matrix when fully hydrated. A "silicone hydrogel" is obtained by polymerizing a polymerizable composition containing at least one silicone-containing component, typically at least one silicone-containing monomer or at least one silicone-containing prepolymer or at least one crosslinkable silicone-containing prepolymer.

[0013] A polymerizable contact lens formulation according to a first aspect of the present invention is suitable for forming silicone hydrogel contact lenses. Polymerizable formulations suitable for use in the preparation of silicone hydrogel contact lens bodies are well known in the art. In addition to TPP, polymerizable siloxane components, and hydrophilic N-vinylamide monomers, the silicone hydrogel contact lens formulation according to a first aspect of the present invention may contain other components suitable for forming contact lens bodies. The polymerizable formulation typically includes a crosslinking agent and a polymerization initiator. The polymerizable formulation may also contain additional polymerizable monomers, oligomers, and / or prepolymers.

[0014] Typically, silicone hydrogel contact lenses are formed by a free radical propagation reaction involving the polymerization of terminal ethylenically unsaturated groups, also referred to herein as "polymerizable groups". Exemplary polymerizable groups include (meth)acrylic groups, (meth)acrylamide groups, allyl groups, vinyl groups, and styrene groups. As used herein, a "vinyl-containing monomer" is any non-siloxane monomer having a single polymerizable carbon-carbon double bond (i.e., a vinyl group) present in its molecular structure, and the carbon-carbon double bond of the vinyl group is bonded to a carbon atom of an sp3 hybridized orbital. The vinyl group is less reactive than the carbon-carbon double bond present in an acrylate polymerizable group or a methacrylate polymerizable group under free radical polymerization. The term "(meth)acrylamide" refers to methacrylamide and / or acrylamide. The term "(meth)acrylate" refers to methacrylate and / or acrylate. The term "terminal (meth)acrylic group" refers to one (meth)acrylic group at one of the two ends of the main chain (or backbone) of an organic compound. An "N-vinylamide monomer" refers to an amide compound having a vinyl group CH=CH2 directly bonded to the nitrogen atom of the amide group.

[0015] A "monomer" is a molecule having one or more polymerizable groups that can react with the same or different other monomers in a polymerization process to form a large polymer chain or copolymer chain or three-dimensional matrix. Monomers having two or more polymerizable groups may further be referred to as "crosslinking agents" as described further below. The term "monomer" encompasses macromonomers and polymerizable oligomers, i.e., polymerizable molecules containing one or more chains of repeating units, such as polymerizable polysiloxanes; thus, there is no size restriction (i.e., maximum molecular weight) for monomers unless otherwise indicated. The term "polymer" refers to a material formed by polymerizing and / or crosslinking one or more monomers.

[0016] As used in this application, the term "molecular weight" of a polymeric material containing a component having a plurality of siloxane units refers to the absolute number average molecular weight (in daltons), determined, for example, by GPC using a polystyrene standard or by 1H NMR end group analysis, unless specifically noted otherwise. An "oligomer" is a compound consisting of 2 to 10 repeating units that may be derived, either realistically or conceptually, from monomers. A prepolymer is a partially polymerized polymer containing a plurality of, typically more than 10, monomer units and is capable of reacting to an intermediate molecular weight state that retains the ability to continue reacting to full cure to a high molecular weight polymeric material. The silicone hydrogel contact lens formulations of the present invention may contain other hydrophilic monomers in addition to the N-vinylamide-containing monomers, and may also contain hydrophobic monomers.

[0017] As used herein, a "hydrophilic monomer" refers to a silicone-free monomer that is completely soluble in 1 liter of water at 20 °C (i.e., approximately 5% soluble in water) when visually determined using the standard shake flask method, with at least 50 grams of the monomer. The silicone hydrogel contact lens formulations contain one or more hydrophilic N-vinylamide-containing monomers in an amount of at least 30% (wt / wt), for example, in an amount of at least 35% (wt / wt), particularly in an amount of at least 37% (wt / wt). The formulation may further contain other hydrophilic monomers, such as hydrophilic vinyl ether-containing monomers. The total amount of hydrophilic monomers in the formulations of the first aspect of the present invention is typically 55% (wt / wt) or less, for example 50% (wt / wt) or less.

[0018] In some examples, the hydrophilic N-vinylamide-containing monomer may be selected from N-vinyl-N-methylacetamide (VMA), or N-vinylpyrrolidone (NVP), or N-vinylformamide, or N-vinylacetamide, or N-vinyl-N-ethylacetamide, or N-vinylisopropylamide, or N-vinylcaprolactam, or N-vinyl-N-ethylformamide, or any combination thereof. In some examples, the hydrophilic vinylamide-containing monomer consists of VMA, or NVP, or a combination of VMA and NVP. The vinyl ether-containing monomer may be selected from 1,4-butanediol vinyl ether (BVE), or ethylene glycol vinyl ether (EGVE), or diethylene glycol vinyl ether (DEGVE), or 1,4-cyclohexanedimethanol vinyl ether (CHDMVE), or poly(ethylene glycol) vinyl ether having 4 to 10 ethylene glycol units, or poly(ethylene glycol) vinyl ether having more than 10 ethylene glycol units, or any combination thereof. In some examples, the vinyl ether-containing monomer may be a poly(ethylene glycol) vinyl ether having at least one, two, or three ethylene glycol units and up to four, six, eight, or ten ethylene glycol units. In addition to the hydrophilic N-vinylamide-containing monomer and the hydrophilic vinyl ether-containing monomer, one or more vinyl-containing monomers may be included in the polymerizable formulations of the present invention as described herein. For example, in addition to the N-vinylamide-containing monomer and the vinyl ether-containing monomer, a vinyl monomer having a vinyl ester polymerizable group or an allyl ester polymerizable group may be included in the formulations of the present invention. The hydrophilic monomer may be a (meth)acrylate group or (meth)acrylamide group-containing hydrophilic monomer, examples of which include 2-hydroxyethyl methacrylate (HEMA), 4-hydroxybutyl acrylate glycerol methacrylate, 2-hydroxyethyl methacrylamide, ethoxyethyl methacrylamide (EOEMA), polyethylene glycol monomethacrylate, methacrylic acid (MA), and acrylic acid.

[0019] A formulation according to the first aspect of the present invention contains at least one N-vinylamide hydrophilic monomer in an amount of at least 30% (wt / wt), and particularly at least 35% (wt / wt). A formulation according to the first aspect of the present invention typically contains 55% (wt / wt) or less of an N-vinylamide hydrophilic monomer, for example, less than 50% (wt / wt) of an N-vinylamide hydrophilic monomer. A formulation according to the first aspect of the present invention may contain an N-vinylamide hydrophilic monomer in an amount of 35-55%, and particularly 37-50%. A formulation according to the first aspect of the present invention may contain N-methyl N-vinylacetamide in an amount of 30-55%, for example 35-50%, and particularly 37-50%.

[0020] When more than one hydrophilic monomer is included in the formulation of the present invention, it is advantageous that at least 70% or 80% by mass of the hydrophilic monomers have a solubility of 20% or more in water. In certain examples, 100% of the hydrophilic vinyl-containing monomers in the polymerizable formulation have a solubility of 10% or more in water. The hydrophilic vinyl-containing monomers typically have a molecular weight of about 75 to about 500, more typically about 75 to about 250. The formulations of the present invention may contain hydrophobic monomers that do not have a siloxane group. As used herein, the term "hydrophobic monomer" refers to a monomer that does not have a siloxane group and is less than 5% soluble in water at 20°C as determined by the standard shake flask method.

[0021] The hydrophobic monomer may be a (meth)acrylate group-containing hydrophobic monomer. As used herein, “hydrophobic acrylate-containing monomer” is any nonsiloxane monomer having a single polymerizable acrylate group (e.g., methyl methacrylate, acrylamide, etc.). In certain examples, the hydrophobic acrylate-containing monomer has a polymerizable methacrylate group. Numerous suitable acrylate-containing monomers are known in the art. Exemplary hydrophobic acrylate-containing monomers include methyl acrylate, isopropyl acrylate, cyclohexyl acrylate, methyl methacrylate (MMA), butyl acrylate, tert-butyl methacrylate (tBMA), perfluorohexylethylthiocarbonylaminoethyl methacrylate, isobornyl methacrylate (IBM), trifluoroethyl methacrylate, hexafluoroisopropyl methacrylate, hexafluorobutyl methacrylate, 2-hydroxybutyl methacrylate (HOB), 2-hydroxypropyl methacrylate (HPMA), and ethylene glycol methyl ether methacrylate (EGMA). Preferred nonsiloxane hydrophobic monomers include hydroxybutyl methacrylate, isobornyl methacrylate, or a combination of hydroxybutyl methacrylate and isobornyl methacrylate. Silicone hydrogel contact lens formulations may also contain acrylate-containing hydrophobic monomers to further enhance the mechanical strength and / or rigidity of the lens or to provide other desired properties.

[0022] Hydrophobic monomers that do not contain a siloxane group are not limited to monomers containing a (meth)acrylate group, but may also contain a vinyl group or other ethylenically unsaturated reactive group. Further examples of hydrophobic monomers include vinyl acetate, vinyl propionate, vinyl butyrate, styrene, chloroprene, vinyl chloride, vinylidene chloride, acrylonitrile, and methacrylonitrile. Polymerizable formulations may contain approximately 2% (wt / wt) to approximately 20% (wt / wt), for example, 4% (wt / wt) to 16% (wt / wt), and particularly 6% (wt / wt) to 12% (wt / wt), of nonsiloxane hydrophobic monomer components. Formulations containing 2% to 20% (wt / wt), and particularly 5% to 15% (wt / wt), may contain hydroxybutyl methacrylate, isobornyl methacrylate, or a combination of hydroxybutyl methacrylate and isobornyl methacrylate.

[0023] As used herein, "siloxane monomer" refers to a monomer having at least one siloxane group. Siloxane monomers may contain terminal acrylate groups or methacrylate groups. (Meth)acrylate-containing siloxane monomers that may be used in the formulations of the present invention as described herein are well known in the art. Siloxane monomers may include monofunctional (meth)acrylate-containing siloxanes, difunctional (meth)acrylate-containing siloxanes, or combinations of monofunctional and difunctional (meth)acrylate-containing siloxane monomers. In examples where the (meth)acrylate-containing siloxane monomer consists of one or more monofunctional (meth)acrylate-containing siloxane monomers (i.e., does not contain any polyfunctional (meth)acrylate-containing siloxane monomers), the polymerizable formulation typically further includes (meth)acrylate-containing crosslinking agents as described below. In certain cases, (meth)acrylate-containing siloxane monomers have one or more polymerizable methacrylate groups. Various non-limiting examples of suitable acrylate-containing siloxane monomers include 3-[tris(trimethylsiloxy)silyl]propyl methacrylate ("Tris"), 3-methacryloxy-2-hydroxypropyloxy)propylbis(trimethylsiloxy)methylsilane ("SiGMA"), methyldi(trimethylsiloxy)silylpropylglycerol ethyl methacrylate ("SiGEMA"), and monomethacryloxypropyl functionalized polydimethylsiloxanes, e.g., MCR-M07 and MCS-M11, all of which are available from Gelest (Morrisville, PA, USA).

[0024] The silicone hydrogel contact lens formulation of the present invention contains a polymerizable siloxane component in an amount of at least 40% (wt / wt), for example, at least 42% (wt / wt), and particularly at least 45% (wt / wt). The polymerizable siloxane component typically constitutes 60% (wt / wt) or less of the formulation, for example, 55% (wt / wt) or less of the formulation. Silicone hydrogel contact lens formulations may contain, for example, at least one monofunctional siloxane monomer having a molecular weight of less than 3000 daltons. At least 10% (wt / wt) of the siloxane content may be monofunctional siloxanes having a molecular weight of less than 3000 daltons. Advantageously, at least 20% (wt / wt) of the siloxane content may be monofunctional monomers having a molecular weight of less than 3000 daltons. The formulation may contain between 10 and 30 wt% of monofunctional siloxane monomers, for example, between 10 and 30 wt% of monofunctional siloxane monomers having a molecular weight of less than 3000 daltons. Monofunctional siloxanes typically have a molecular weight of at least 200 daltons.

[0025] In one example, a monofunctional siloxane monomer is given by formula (I) [ka] (In the formula, m is an integer between 3 and 10, n is an integer between 0 and 10, R 1 R is an alkyl group having 1 to 4 carbon atoms. 2 R is a hydrogen or methyl group, 3 (This is either a hydrogen or methyl group.) It may also contain (meth)acrylate-containing siloxane monomers represented by formula I (wherein R 1 is a butyl group, R 2 is hydrogen, R 3 (where is a methyl group, m is 4, and n is 1). A method for producing the siloxane monomer represented by formula (I) is described in U.S. Patent Application Publication No. 2009 / 0299022, which is incorporated herein by reference.

[0026] In another example, monofunctional siloxane monomers are given by formula (II) [ka] (In the formula, n is an integer between approximately 10 and 25, especially between 10 and 20.) It may also contain (meth)acrylate-containing siloxane monomers represented by . Siloxane monomers of formula II and other suitable monomers are described in U.S. Patent No. 6,867,245 and U.S. Patent No. 6,310,169, both of which are incorporated herein by reference.

[0027] Suitable examples of commercially available monofunctional siloxane monomers include 2-propenoic acid, 2-methyl-,2-[3-(9-butyl-1,1,3,3,5,5,7,7,9,9-decamethylpentasiloxane-1-yl)propoxy]ethyl ester, X-22-1622 / KF-1622 (CAS No. 1052075-57-6), methacryloxypropyl-terminated poly(dimethyl)siloxane, FMM, Shin-Etsu Silicones of America, Akron, Ohio, USA (CAS No. 697234-76-7), and 3-methacryloxy-2-hydroxypropyloxypropylbis(trimethylsiloxy)methylsilane, SiGMA, available from Shin-Etsu Chemical Co., Ltd., Tokyo, Japan. [ka] JPEG0007843420000005.jpg39123 JPEG0007843420000006.jpg89130

[0028] Silicone hydrogel contact lens formulations include at least one difunctional siloxane having a molecular weight of at least 5,000 daltons, for example, at least 6,500 daltons, and particularly at least 8,000 daltons. The difunctional siloxane may include or consist of a difunctional (meth)acrylate-containing siloxane monomer, particularly a difunctional (meth)acrylate-containing siloxane, having a molecular weight of at least 5,000 daltons, for example, at least 6,500 daltons, and particularly at least 8,000 daltons. Difunctional siloxanes typically have a molecular weight of less than 25,000 daltons, for example, less than 20,000 daltons, and particularly less than 15,000 daltons. It has been observed that formulations with unacceptably high viscosity may result from the inclusion of siloxanes with higher molecular weights. Silicone hydrogel contact lens formulations may contain at least one difunctional siloxane having a molecular weight of 5,000 to 25,000 daltons, for example, at least one difunctional siloxane having a molecular weight of 6,500 to 20,000 daltons, and in particular at least one difunctional siloxane having a molecular weight of at least 8,000 to 15,000 daltons. At least 50% (wt / wt) of the siloxane content is a difunctional siloxane having a molecular weight of at least 5,000 daltons, in particular a difunctional (meth)acrylate-containing siloxane. At least 50% (wt / wt) of the siloxane content may be a difunctional siloxane having a molecular weight of at least 6,500 daltons, in particular a difunctional (meth)acrylate-containing siloxane. Advantageously, at least 50% (wt / wt) of the siloxane content is a difunctional siloxane having a molecular weight of at least 8,000 daltons, particularly a difunctional (meth)acrylate-containing siloxane. The formulation may also contain 20-45% (wt / wt) of difunctional siloxane, for example, 20-40% (wt / wt) of difunctional siloxane, particularly a difunctional (meth)acrylate-containing siloxane.The formulation may contain a difunctional siloxane between 20% and 45% (wt / wt) having a molecular weight of at least 5,000 daltons, particularly a difunctional (meth)acrylate-containing siloxane, for example, a difunctional siloxane between 20% and 40% (wt / wt) having a molecular weight of at least 5,000 daltons, particularly a difunctional (meth)acrylate-containing siloxane. The formulation may also contain a difunctional siloxane between 15% and 45% (wt / wt) having a molecular weight of at least 8,000 daltons, particularly a difunctional (meth)acrylate-containing siloxane, for example, a difunctional siloxane between 20% and 45% (wt / wt) or between 20% and 40% (wt / wt) having a molecular weight of at least 8,000 daltons, particularly a difunctional (meth)acrylate-containing siloxane. It has been found that the inclusion of TPP is particularly advantageous in formulations containing a large amount of high molecular weight siloxane having a molecular weight of at least 5,000 daltons, and especially at least 8,000 daltons, for example, formulations containing at least 20% (wt / wt), and especially at least 25% (wt / wt), of siloxane.

[0029] In one example, a bifunctional siloxane monomer is given by formula (III) [ka] (In the formula, R1 is selected from either hydrogen or a methyl group; R2 is hydrogen or C 1-4 Selected from any hydrocarbon group; m represents an integer between 0 and 10; n represents an integer between 4 and approximately 15, 4 and approximately 25, or 4 and approximately 100; a and b represent integers greater than or equal to 1; a+b is equal to 20 and 500; b / (a+b) is equal to 0.01 and 0.22. It may contain (meth)acrylate-containing siloxane monomers represented by , and the stereochemistry of the siloxane units includes random stereochemistry.

[0030] For example, M5A of the bifunctional siloxane monomer is represented by formula (III) (where R1 is methyl, R2 is methyl, m is 0, n is about 7, a is about 75, and b is about 10). M5A has a molecular weight between 8,000 and 11,000 Daltons. Another suitable bifunctional siloxane monomer is formula (IV)

Chemical formula

[0031] Yet another suitable bifunctional siloxane monomer is formula (V)

Chemical formula

[0032] In one example, the siloxane monomer may include a combination of monofunctional (meth)acrylate-containing siloxane monomers and difunctional (meth)acrylate-containing siloxane monomers. In one such example, the monofunctional (meth)acrylate-containing siloxane monomer has a molecular weight of less than 3,000 daltons, less than 2,000 daltons, or less than 1,000 daltons, and the difunctional acrylate-containing siloxane monomer has a molecular weight of at least 5,000 daltons, at least 6,500 daltons, or at least 8,000 daltons. In a specific example, the monofunctional (meth)acrylate-containing siloxane monomer has a molecular weight of about 250 to about 1,000 daltons, and the difunctional acrylate-containing siloxane monomer has a molecular weight of about 5,000 to about 16,000 daltons. In further specific examples, monofunctional (meth)acrylate-containing siloxane monomers have a molecular weight of approximately 500 to 1,000 daltons, while difunctional (meth)acrylate-containing siloxane monomers have a molecular weight of approximately 5,000 to 12,000 daltons.

[0033] The silicone hydrogel contact lens formulations of the present invention typically contain one or more polymerization initiators; that is, the formulation may contain an initiator, or may contain two or more polymerization initiators, or initiator components including a combination of polymerization initiators, synergists, and activators. The term "initiator" refers to a chemical substance that initiates a crosslinking / polymerization reaction. Initiators are typically free radical initiators that form radicals that initiate a radical propagation polymerization reaction. Polymerization initiators that may be included in the formulations of the present invention include, for example, azo compounds, or organic peroxides, or both. Initiators may be photoinitiators that are activated when exposed to chemical radiation, for example, UV light, or thermal initiators that are activated when exposed to heat. Potential initiators in polymerizable formulations include, for example, benzoin ethyl ether, or benzyl dimethyl ketal, or alpha,alpha-diethoxyacetophenone, or 2,4,6-trimethylbenzoyldiphenylphosphine oxide, or benzoin peroxide, or t-butyl peroxide, or azobisisobutyronitrile, or azobisdimethylvaleronitrile, or any combination thereof. UV photoinitiators may include, for example, phosphine oxides, such as diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, or benzoin methyl ether, or 1-hydroxycyclohexylphenyl ketone, or Darocur (available from BASF, Florham Park, NJ, USA), or Irgacur (also available from BASF), or any combination thereof. Advantageously, the polymerization initiator is a thermal initiator. Suitable thermal initiators include 2,2'-azobis-2-methylpropanenitrile (VAZO-64, EIDuPont de Nemours & Co., Wilmington, Del., USA), abbreviated as "AIBN", 2,2'-azobis(2,4-dimethylpentanenitrile) (VAZO-52), and 1,1'-azobis(cyanocyclohexane) (VAZO-88, also manufactured by EIDuPont).Polymerization initiators or initiator components may be present in the silicone hydrogel contact lens formulation of the present invention in an amount of about 0.1% (wt / wt) to about 1.5% (wt / wt), or about 0.2% (wt / wt) to about 1.0% (wt / wt), particularly about 0.2% to about 0.8% (wt / wt). The formulation of the first embodiment of the present invention may be a thermosetting formulation containing at least one thermal initiator. Thermosetting methods and chemical beam curing methods are well known to those skilled in the art.

[0034] Silicone hydrogel contact lens formulations may further contain crosslinking agents. Crosslinking agents can react with functional groups on two or more polymer chains to crosslink one polymer to another. As used herein, “crosslinking agent” is any compound having a molecular weight of less than about 2,000 daltons, typically less than 700 daltons, and having two or more polymerizable groups. As used herein, “acrylate-containing crosslinking agent” has at least two polymerizable acrylate groups and no other types of polymerizable groups. “Vinyl-containing crosslinking agent” has at least two polymerizable vinyl groups and no other types of polymerizable groups. Vinyl-containing crosslinking agents and acrylate-containing crosslinking agents may typically have molecular weights of less than 1,500 daltons, less than 1,000 daltons, less than 500 daltons, or less than 250 daltons. Examples of vinyl-containing crosslinking agents that may be used in the formulations of the present invention disclosed herein include, but are not limited to, divinyl ethers, or divinyl sulfones, or triallyl isocyanurate (TAIC), and any combination thereof. Examples of divinyl ethers include diethylene glycol divinyl ether, or triethylene glycol divinyl, or 1,4-butanediol divinyl ether, or 1,4-cyclohexanedimethanol divinyl ether, or any combination thereof. Typically, the vinyl-containing crosslinker may have two or three polymerizable vinyl groups. If present, the total amount of vinyl-containing crosslinker in the silicone hydrogel contact lens formulation is typically about 0.02, about 0.04, or about 0.06 mol.% to about 0.10, about 0.15, or about 0.20 mol.%.Examples of acrylate-containing crosslinking agents that may be used in the formulations of the present invention disclosed herein include, but are not limited to, lower alkylene glycol di(meth)acrylate, poly(lower alkylene) glycol di(meth)acrylate, lower alkylene di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, bisphenol A di(meth)acrylate, methylene bis(meth)acrylamide, and 1,3-bis(3-methacryloxypropyl)tetramethyldisiloxane. In certain examples, the acrylate-containing crosslinking agent is a non-siloxane crosslinking agent. If present, the total amount of acrylate-containing crosslinking agent in the formulations of the present invention is typically about 0.20, about 0.25, about 0.30, or about 0.35 mol.% to about 0.50, about 0.60, about 0.70, about 0.80, or about 1.0 mol.%. To avoid any misunderstanding, polyfunctional polymerizable compounds with a molecular weight exceeding 2,000 daltons are not considered crosslinking agents. Therefore, the bifunctional siloxanes described herein with a molecular weight exceeding 2,000 daltons are not considered crosslinking agents.

[0035] The formulations of the present invention may further contain a chain transfer agent. Chain transfer is a polymerization reaction that transfers the activity of a growing polymer chain to another molecule, thereby reducing the average molecular weight of the final polymer. Examples of chain transfer agents include, for example, thiol compounds, halogenated carbon compounds, or C3-C5 hydrocarbons, such as allyloxyethanol. The formulations of the present invention may contain, in addition to polymerizable components, non-polymerizable components that have been commonly used in contact lens formulations. Additional components, such as organic solvent diluents, may also be included. Non-limiting examples of these and additional components that may be included in the polymerizable formulations are provided in U.S. Patent Application Publication 2007 / 0296914. The formulations of the present invention may contain 2% (wt / wt) or less of non-polymerizable components other than TPP, particularly 1% (wt / wt) or less of non-polymerizable components other than TPP. In particular, the formulations of the present invention may contain 2% (wt / wt) or less of organic solvent diluents, particularly 1% (wt / wt) or less of organic solvent diluents.

[0036] A preferred formulation of the present invention comprises a siloxane component present in an amount of at least 40% (wt / wt), wherein at least 50% of the siloxane content is a bifunctional siloxane having a molecular weight of at least 5,000 daltons; and an N-vinylamide monomer component present in an amount of at least 30% (wt / wt). A contact lens of a second aspect of the present invention preferably comprises a polymer lens material derived from the preferred polymerizable formulation of the first aspect of the present invention, which comprises the above-mentioned monomer and siloxane component. An improved formulation in a third embodiment of the present invention is advantageously the one described above in relation to formulations of other embodiments of the present invention. For example, an improved formulation in a third embodiment of the present invention may contain any or all of the above-mentioned siloxane components, hydrophilic N-vinylamide monomers, any further hydrophilic monomers, any further hydrophobic monomers, any crosslinking agents, any chain transfer agents, and any radical initiators. Alternatively, for example, an improved formulation in a third embodiment of the present invention may contain the siloxane components, hydrophilic N-vinylamide monomers, any further hydrophilic monomers, and any further hydrophobic monomers in the amounts described above in relation to formulations of the present invention. [Examples]

[0037] It should be understood that the following examples illustrate, but are not limiting, certain aspects and advantages of the present invention. Basic formulations A basic polymerizable silicone hydrogel contact lens formulation 1 containing the following was prepared: • 11 wt.% hydrophobic monomer (consisting of 8.29 wt% hydroxybutyl methacrylate and 2.49 wt% isobornyl methacrylate), • 42 wt.% hydrophilic N-vinylamide monomer (consisting of 10.48 wt% N-vinyl N-methylacetamide and 31.44 wt% N-vinylpyrrolidone), • 45 wt.% polymerizable siloxane (the monomer ratio can be varied - as shown in Table 1), • 2 wt.% of other agents including a thermal initiator (azobisisobutyronitrile (AIBN)) and a crosslinking agent (triallyl isocyanate).

[0038] A basic polymerizable silicone hydrogel contact lens formulation 2 was prepared, containing the following: • 9 wt.% hydrophobic monomer (consisting of 9.94% hydroxybutyl methacrylate and 2.09% isobornyl methacrylate), • 39 wt.% hydrophilic N-vinylamide monomer (N-vinyl N-methylacetamide) • High molecular weight bifunctional siloxane (30.23 wt% M5A, Mn 8,000-11,000): Low molecular weight monofunctional siloxane (18.04 wt% FMM and 0.49 wt% KF-1622, Mn < 2,000) in a ratio of 62:38, totaling 49 wt.% polymerizable siloxane. • 3 wt.% of other agents including a thermal initiator (azobisisobutyronitrile (AIBN)) and a crosslinking agent (triallyl isocyanate).

[0039] Evaluation of surface rippling The degree of lens rippling was visually assessed based on zonometer or SAG optimec images and evaluated on a scale of 0 to 5 using the following criteria: • 0-ripple is not accepted. • 1 - A very small, slight ripple. 2. Mild ripple. 3 - Moderate ripple. 4. Severe ripple. 5 - A very severe, long, and deep ripple.

[0040] Surface rip ring without TPP The following examples illustrate the degree of surface rippling that occurs in PP-type formulations and how this can be mitigated by incorporating TPP. The degree of surface ripple was investigated using polymerizable mixtures, which were combined with basic formulation 1, with a fixed silicone content of 46 parts by mass and different silicone ratios between M5A:KF-1622 and M5A:FMM. TPP was not included in the polymerizable mixture, and no further modifications were made to the monomer formulations. All formulations were cast in the same PP mold. The results are summarized in Table 1 below. The table shows that the degree of rippling increased with increasing M5A loading, and the most severe surface rippling was observed in mixture 6, which contained 75:25 M5A:FMM. [Table 1] Severe rippling was also observed in lenses made from mixture 7 containing 81:19 M3U:FMM. No ripple was shown in comparison to Stenfilcon A lenses containing approximately 35% (wt / wt) silicone and 75:25 KF-1622:M5A, and fanfilcon A lenses containing approximately 39% (wt / wt) silicone and 68:32 KF-1622:M5A, which were made using the same process in a PP mold (0).

[0041] The effect of TPP on surface rippling Adding TPP to monomer formulations made it possible to manufacture contact lenses without surface rippling. As the TPP load increased, the degree of rippling observed decreased. Table 2 below shows the addition of TPP to basic formulation 2, which has a total silicone content of 54 parts by mass and consists of a 62:38 bifunctional:monofunctional siloxane formulation. [Table 2]

[0042] The table shows that the degree of rippling decreases as the TPP load increases. Rippling is most pronounced when no TPP is present (mixture 9). When 0.404% TPP is present (mixture 13), rippling is reduced to the point where it is no longer visually observable.

[0043] The disclosures herein refer to certain exemplary examples, and it should be understood that these examples are presented as illustrations and not as limitations. The intent of the foregoing detailed description is to cover all variations, alternatives, and equivalents of the examples that may fall within the spirit and scope of the invention as defined by the additional disclosures, although the exemplary examples are discussed. The entire contents of all references cited in this disclosure are incorporated herein by reference to the extent that they do not conflict with this disclosure.

[0044] Other embodiments of the present invention will be apparent to those skilled in the art from consideration of this specification and the practices of the present invention disclosed herein. This specification and examples are intended to be considered only as illustrative within the true scope and spirit of the invention as set forth by the following claims and equivalents. Another aspect of the present invention may be as follows: [1] A silicone hydrogel contact lens formulation, a. A polymerizable siloxane component comprising at least 40% (wt / wt) of polymerizable siloxane components, wherein at least 50% (wt / wt) of the polymerizable siloxane content is a bifunctional siloxane having a molecular weight of at least 5,000 daltons, b. At least 30% (wt / wt) of hydrophilic N-vinylamide monomer, c. At least 0.10% (wt / wt) of triphenylphosphine (TPP) A formulation containing the above. [2] The preparation according to [1], comprising 35-50% (wt / wt) of N-methyl N-vinylacetamide monomer. [3] The formulation according to [1] or [2], comprising at least 37% (wt / wt) of N-vinylamide monomer. [4] A formulation according to any one of the above items [1] to [3], wherein polymerizable siloxane components are present in an amount of at least 45% (wt / wt). [5] The formulation according to any one of the above [1] to [4], wherein at least 50% (wt / wt) of the polymerizable siloxane content is a bifunctional siloxane having a molecular weight of at least 8,000 daltons. [6] A formulation according to any one of the above [1] to [5], comprising 20-40% (wt / wt) of a bifunctional (meth)acrylate-containing siloxane having a molecular weight of at least 8,000 daltons. [7] The formulation according to any one of the above [1] to [6], wherein 20 to 50% (wt / wt) of the polymerizable siloxane content is a monofunctional siloxane having a molecular weight of less than 3,000 daltons. [8] A formulation according to any one of the above items [1] to [7], comprising 10-30% (wt / wt) of a monofunctional (meth)acrylate-containing siloxane having a molecular weight of less than 3000 daltons. [9] d. Nonsiloxane hydrophobic monomers, especially hydrophobic methacrylate monomers A preparation according to any one of the above items [1] to [8], further comprising:

[10] The formulation according to [9], wherein the nonsiloxane hydrophobic monomer includes or consists of hydroxybutyl methacrylate, isobornyl methacrylate, or a combination of hydroxybutyl methacrylate and isobornyl methacrylate.

[11] The formulation according to [9] or

[10] , wherein at least 5% (wt / wt) is a nonsiloxane hydrophobic monomer.

[12] A formulation according to any one of the above items [1] to

[11] , comprising 0.2% to 2.0% (wt / wt) of TPP.

[13] a1. A siloxane containing a bifunctional (meth)acrylate having a molecular weight of at least 8,000 daltons in an amount of 20-40% (wt / wt), a2. Siloxane containing monofunctional (meth)acrylate with a molecular weight of less than 3000 daltons in an amount of 10-30 (wt / wt), b. 37-50% (wt / wt) of N-methyl N-vinylacetamide, c. At least 0.2% (wt / wt) of the TPP, d. At least 5% (wt / wt) of hydroxybutyl methacrylate, isobornyl methacrylate, or a combination of hydroxybutyl methacrylate and isobornyl methacrylate. The preparation described in [1] above, including the preparation described in [1] above.

[14] Polymerizable siloxane components are of formula (III)

change

[13] , comprising a bifunctional (meth)acrylate-containing siloxane monomer represented by, wherein the stereoconfiguration of the siloxane unit includes a random stereoconfiguration.

[15] The formulation according to any one of the above [1] to

[14] , wherein the polymerizable siloxane component comprises a monofunctional methacrylate-containing siloxane monomer represented by formula (II).

change

[16] A hydrogel or silicone hydrogel contact lens obtained by polymerization of any one of the formulations described in [1] to

[15] above.

[17] Use of TPP to improve the surface properties of contact lenses, wherein the contact lenses a. A polymerizable siloxane component comprising at least 40% (wt / wt) of polymerizable siloxane components, wherein at least 50% (wt / wt) of the polymerizable siloxane content is a bifunctional siloxane having a molecular weight of at least 5,000 daltons, and at least 20% (wt / wt) of the polymerizable siloxane content is a monofunctional siloxane having a molecular weight of less than 3,000 daltons, b. At least 30% (wt / wt) of hydrophilic N-vinylamide monomer and Prepared from a formulation containing the above, for use.

[18] The use according to

[17] , wherein the formulation is as further defined in any one of the preceding paragraphs [2] to

[15] .

Claims

1. A silicone hydrogel contact lens formulation, a. A polymerizable siloxane component comprising at least 40% (wt / wt) of polymerizable siloxane components, wherein at least 50% (wt / wt) of the polymerizable siloxane content is a bifunctional siloxane having a molecular weight of at least 5,000 daltons, b. At least 30% (wt / wt) of hydrophilic N-vinylamide monomer, c. At least 0.10% (wt / wt) of triphenylphosphine (TPP) and A formulation containing the above.

2. The formulation according to claim 1, comprising 35-50% (wt / wt) of N-methyl N-vinylacetamide monomer.

3. The formulation according to claim 1, comprising at least 37% (wt / wt) of an N-vinylamide monomer.

4. The formulation according to claim 1, wherein polymerizable siloxane components are present in an amount of at least 45% (wt / wt).

5. The formulation according to claim 1, wherein at least 50% (wt / wt) of the polymerizable siloxane content is a bifunctional siloxane having a molecular weight of at least 8,000 daltons.

6. The formulation according to claim 1, comprising 20-40% (wt / wt) of a bifunctional (meth)acrylate-containing siloxane having a molecular weight of at least 8,000 daltons.

7. The formulation according to claim 1, wherein 20 to 50% (wt / wt) of the polymerizable siloxane content is a monofunctional siloxane having a molecular weight of less than 3,000 daltons.

8. The formulation according to claim 1, comprising 10-30% (wt / wt) of a monofunctional (meth)acrylate-containing siloxane having a molecular weight of less than 3000 daltons.

9. d. Nonsiloxane hydrophobic monomers The formulation according to claim 1, further comprising:

10. The formulation according to claim 9, wherein the nonsiloxane hydrophobic monomer includes or consists of hydroxybutyl methacrylate, isobornyl methacrylate, or a combination of hydroxybutyl methacrylate and isobornyl methacrylate.

11. The formulation according to claim 9, wherein at least 5% (wt / wt) is a nonsiloxane hydrophobic monomer.

12. The formulation according to claim 1, comprising 0.2% to 2.0% (wt / wt) of TPP.

13. a1. A siloxane containing a bifunctional (meth)acrylate having a molecular weight of at least 8,000 daltons in an amount of 20-40% (wt / wt), a2. A siloxane containing a monofunctional (meth)acrylate having a molecular weight of less than 3000 daltons in an amount of 10 to 30 (wt / wt), b. 37-50% (wt / wt) of N-methyl-N-vinylacetamide, c. At least 0.2% (wt / wt) of the TPP, d. At least 5% (wt / wt) of hydroxybutyl methacrylate, isobornyl methacrylate, or a combination of hydroxybutyl methacrylate and isobornyl methacrylate. The formulation according to claim 1, comprising:

14. The polymerizable siloxane component is of formula (III) 【Chemistry 1】 (In the formula, R 1 R is selected from either a hydrogen or a methyl group; 2 is hydrogen or C 1-4 (Selected from any hydrocarbon group; m represents an integer from 0 to 10; n represents an integer from 4 to 15, 4 to 25, or 4 to 100; a and b represent integers of 1 or greater; a + b is equal to 20 to 500; b / (a + b) is equal to 0.01 to 0.22) The formulation according to claim 1, comprising a bifunctional (meth)acrylate-containing siloxane monomer represented by, wherein the stereoconfiguration of the siloxane unit includes a random stereoconfiguration.

15. The formulation according to claim 1, wherein the polymerizable siloxane component comprises a monofunctional methacrylate-containing siloxane monomer represented by formula (II). 【Chemistry 2】 (In the formula, n is an integer between 10 and 15.)

16. A hydrogel or silicone hydrogel contact lens obtained by polymerization of a formulation according to any one of claims 1 to 15.

17. A method for preparing contact lens formulations, a. A polymerizable siloxane component comprising at least 40% (wt / wt) of polymerizable siloxane components, wherein at least 50% (wt / wt) of the polymerizable siloxane content is a bifunctional siloxane having a molecular weight of at least 5,000 daltons, and at least 20% (wt / wt) of the polymerizable siloxane content is a monofunctional siloxane having a molecular weight of less than 3,000 daltons, b. At least 30% (wt / wt) of hydrophilic N-vinylamide monomer and c. At least 0.10% (wt / wt) of triphenylphosphine (TPP) and The process of mixing to prepare a contact lens formulation, Methods that include...

18. The method according to claim 17, wherein the contact lens formulation is as further defined in any one of claims 2 to 15.

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