JP2007009060A - Monomer composition and contact lens - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a contact lens (CL) that has improved protein contamination resistance, high oxygen permeability, hydrophilicity and wearing feeling and excellent softness, etc., and is useful as a soft contact lens and a monomer composition that is useful for the production of the CL and has excellent uniformity and transparency. <P>SOLUTION: The CL monomer composition comprises (A) 5-20 mass% of a (meth)acrylate containing a phosphorylcholine-analogous group represented by formula (1) (R<SP>1</SP>, R<SP>2</SP>and R<SP>3</SP>are each -H or -CH<SB>3</SB>; m is an integer of 1-8; n is an integer of 2-4), (B) ≥10 mass% of a monomer containing a silicon atom and a hydroxy group represented by formula (2) (R<SP>4</SP>is -H or -CH<SB>3</SB>; R<SP>5</SP>is -CH<SB>2</SB>CH(OH)CH<SB>2</SB>- or -CH(CH<SB>2</SB>OH)CH<SB>2</SB>-; p is an integer of 1-10; r is 2 or 3; q is 0 or 1; r+q=3) and (C) 0.1-2 mass% of a crosslinkable monomer. The content of the component (A) is ≤50 mass% of the content of the component (B). The CL is obtained by curing the composition and has excellent oxygen permeability. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention is a contact lens excellent in protein contamination resistance, oxygen permeability, etc., and further contact lens (hereinafter referred to as SCL) such as a soft contact lens excellent in hydrophilicity and flexibility (hereinafter abbreviated as SCL). And a monomer composition used as these raw materials.

Conventionally, SCL is a low water content SCL having a water content of 50% or less, mainly composed of 2-hydroxyethyl methacrylate (HEMA), N-vinylpyrrolidone (NVP) or sodium methacrylate (MANa) and HEMA. A high water content SCL having a polymerization main component and a water content of 50% or more is commercially available.
The former is excellent in mechanical strength and stain resistance against protein adsorption, but has insufficient oxygen permeability. Among the latter, SCL using NVP as a copolymer component has high water content but insufficient mechanical strength, and SCL using MANa as a copolymer component is anionic, so protein adsorption is markedly resistant to protein. There is a problem with pollution. Furthermore, both of these conventional SCLs do not have sufficient oxygen permeability and are not suitable for continuous wear, including mechanical strength and protein contamination. In addition, the high water content SCL has a problem of dry eye because it cannot suppress the transpiration of water from the lens surface at the time of wearing.
Thus, Patent Documents 1 and 2 propose high water content SCL containing 2-methacryloyloxyethyl phosphorylcholine (MPC) as a main component for polymerization. The SCL can suppress the adsorption of proteins or lipids by phosphorylcholine-like groups to improve the stain resistance, and can improve the oxygen permeability by increasing the water content. However, oxygen permeability is still not sufficient. Further, in order to increase the oxygen permeability, when the water content is increased, the mechanical strength is remarkably reduced, and it is further difficult to suppress the transpiration of water from the SCL surface due to the higher water content.

By the way, it is known that monomers that dissolve phosphorylcholine-like group-containing (meth) acrylate are limited to hydrophilic monomers having a hydroxyl group or a carboxyl group. Specifically, a hydroxyl group-containing (meth) acrylate typified by HEMA, a carboxyl group-containing (meth) acrylate typified by methacrylic acid, and the like. Therefore, it is not compatible with a hydrophobic monomer, and in particular is not compatible with a silicone monomer typified by 3-tris (trimethylsilyl) propyl (meth) acrylate (TRIS). As a result, it has been difficult to prepare SCL with excellent wearing feeling having excellent protein contamination resistance of phosphorylcholine-like groups and excellent oxygen permeability of siloxanyl groups.
Therefore, Patent Document 3 proposes CL containing MPC and a hydroxyl group-containing fluoroalkyl methacrylate (FOHMA) as a copolymerization main component. The CL is said to be able to satisfy both contamination resistance and oxygen permeability by improving the solubility of MPC. , Sometimes abbreviated as HCL). The HCL uses less MPC and is clearly inferior to SCL in terms of wearability. In addition, since the CL has a fluorine atom in the structure, when it is used for SCL, the problems of long-term surface wettability, flexibility as SCL and brittleness caused by the fluorine atom cannot be solved. .

Further, Patent Document 4 proposes a silicone hydrogel (hereinafter abbreviated as SiHG) as a material satisfying oxygen permeability and water content. Specifically, SiHG having dimethylacrylamide (DMA), TRIS, and fluoroalkyl methacrylate (FMA) as copolymerized main components has been proposed. Since the SiHG does not have a satisfactory level of oxygen permeability and further has a high ratio of TRIS and DMA, there is a problem in contamination resistance due to adsorption of not only proteins but also lipids. Patent Documents 5 and 6 propose SiHG containing polydimethylsiloxane dimethacrylate (SiMA) and DMA as copolymerized main components. However, although SiHG described in these documents has sufficient oxygen permeability, there remains a problem in contamination resistance such as protein and lipid adsorption.
Japanese National Publication No. 6-502200 JP-A-5-107511 JP 2000-169526 A US Pat. No. 4,954,587 US Pat. No. 5,358,995 US Pat. No. 5,387,632

An object of the present invention is to provide a contact lens excellent in resistance to protein contamination and oxygen permeability necessary for continuous wear, and a monomer composition excellent in uniformity and transparency that can be used in the production of the contact lens. Is to provide.
Another object of the present invention is to provide a contact lens that is excellent in resistance to protein contamination, high oxygen permeability, hydrophilicity, softness that improves wearing feeling, and can be used as a soft contact lens, and the production of the contact lens. An object of the present invention is to provide a monomer composition excellent in uniformity and transparency that can be used.

  As a result of intensive studies in view of the above problems, the present inventors have used the (A) component and the (B) component described below at a specific ratio, thereby improving the solubility of the (A) component and making it uniformly transparent, By adding and curing the component C), the contact lens has a favorable oxygen permeability and protein contamination resistance for the contact lens. Furthermore, by adding a specific hydrophilic monomer, it maintains uniform transparency and is hydrophilic. In addition, the inventors have obtained knowledge that a contact lens having flexibility can be obtained, and have completed the present invention.

(式中、Ｒ¹、Ｒ²及びＲ³は水素原子又はメチル基を示し、mは１〜８の整数を、nは２〜４の整数を示す。)
式(２)で表わされる(B)ケイ素原子及び水酸基含有単量体１０質量％以上と、

(式中、Ｒ⁴は水素原子又はメチル基を示し、Ｒ⁵は-CH₂CH(OH)CH₂-又は-CH(CH₂OH) CH₂-を示し、ｐは1〜１０の整数を示す。ｒは２又は３、ｑは０又は１であり、ｒ＋ｑ＝３である。)
(C)架橋性単量体０．１〜２質量％とを含み、且つ前記(A)成分の含量が、前記(B)成分の含量の５０質量％以下とした単量体組成物又はコンタクトレンズ用単量体組成物が提供される。 That is, according to the present invention, (A) phosphorylcholine-like group-containing (meth) acrylate represented by the formula (1) is 5 to 20% by mass,

(In the formula, R ¹ , R ² and R ³ represent a hydrogen atom or a methyl group, m represents an integer of 1 to 8, and n represents an integer of 2 to 4.)
(B) a silicon atom and hydroxyl group-containing monomer represented by the formula (2) of 10% by mass or more,

(In the formula, R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents —CH ₂ CH (OH) CH ₂ — or —CH (CH ₂ OH) CH ₂ —, and p represents an integer of 1 to 10. R is 2 or 3, q is 0 or 1, and r + q = 3.)
(C) a monomer composition or contact comprising 0.1 to 2% by mass of a crosslinkable monomer, and wherein the content of the component (A) is 50% by mass or less of the content of the component (B) A monomer composition for a lens is provided.

(式中、Ｒ⁶は水素原子又はメチル基を示し、ｐは1〜１０の整数を示す。ｒは２又は３、ｑは０又は１であり、ｒ＋ｑ＝３である。)
且つ前記(B)成分と前記(E)成分との含量の和が組成物全量中、５０質量％以上であるコンタクトレンズ用組成物が提供される。 Further, according to the present invention, there is provided a monomer composition for a contact lens, wherein the composition comprises (D) 0.1 to 75% by mass of a hydrophilic monomer having a hydroxyl group or an amide group in the molecule.
Further according to the present invention, the composition comprises (D) 0.1 to 75% by mass of a hydrophilic monomer having a hydroxyl group or an amide group in the molecule and / or (E) silicon represented by formula (3) Further containing 0.1 to 50% by mass of an atom-containing monomer,

(In the formula, R ⁶ represents a hydrogen atom or a methyl group, p represents an integer of 1 to 10. r is 2 or 3, q is 0 or 1, and r + q = 3.)
And the composition for contact lenses whose sum of the content of the said (B) component and the said (E) component is 50 mass% or more in the composition whole quantity is provided.

Further, according to the present invention, the component (A) is 2- (meth) acryloyloxyethyl-2 ′-(trimethylammonio) ethyl phosphate, and the component (B) is 1-methylbis (trimethylsiloxy) silylpropyl. Oxy-3- (meth) acryloyloxy-2-hydroxypropane, and the component (C) is ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate and polyethylene glycol di It is at least one selected from the group consisting of (meth) acrylates, and the component (D) is selected from the group consisting of 2-hydroxyethyl (meth) acrylate, N-vinyl-2-pyrrolidone and N, N-dimethylacrylamide. The contact lens composition which is at least one selected from the above, or these (A) The composition for contact lenses, wherein the component (E) and the component (E) are tris (trimethylsiloxy) silylpropyl (meth) acrylate, are provided.
Furthermore, according to the present invention, a contact lens obtained by curing the composition and having an oxygen permeability of 25 × 10 ⁻¹¹ [cc (STP) cm] / [cm ² · sec · mmHg] or more, or oxygen Provided is a contact lens having a permeability of 50 × 10 ⁻¹¹ [cc (STP) cm] / [cm ² · sec · mmHg] or more, a moisture content of 35 to 50%, and an elastic modulus of 1 MPa or less.

The monomer composition of the present invention and the monomer composition for contact lenses are blended with a predetermined amount of the component (A) and the component (B), and further contains the component (C), so that they are separated and precipitated. It can be set as a uniform transparent composition without this.
In addition, the monomer composition for contact lenses of the present invention comprising the component (A), the component (B) and the component (C), and further comprising the component (D) and / or the component (E) as necessary. Furthermore, the contact lens of the present invention obtained by curing a composition for contact lenses in which a specific monomer in each of the components (A) to (E) is combined is excellent in protein contamination resistance and oxygen permeability, Furthermore, since it is excellent in hydrophilicity, flexibility, etc., it is suitable for continuous wear, and can also improve problems such as dry eye, and is particularly useful as a soft contact lens.

The present invention is described in further detail below.
The monomer composition of the present invention and the monomer composition for contact lenses (hereinafter abbreviated as the composition of the present invention) contain the above components (A) to (C) in a specific ratio.
The component (A) is a phosphorylcholine-like group-containing (meth) acrylate represented by the above formula (1), and particularly a component that can impart hydrophilicity and resistance to protein contamination when formed into a contact lens.
In said formula (1), R < ¹ >, R < ² > and R < ³ > show a hydrogen atom or a methyl group. m represents an integer of 1 to 8, and n represents an integer of 2 to 4. However, when m is 2 or more, m is an average value. Here, when m exceeds 8, or when n exceeds 4, the ratio of phosphorylcholine group occupying in the molecule is lowered, and there is a possibility that protein resistance is lowered. Moreover, when n is 1, there exists a possibility that it may decompose | disassemble gradually with the water | moisture content contained in tears.

  Examples of the component (A) include 2- (meth) acryloyloxyethyl-2 ′-(trimethylammonio) ethyl phosphate, 2- (meth) acryloyloxyethoxyethyl-2 ′-(trimethylammonio) ethyl phosphate, 2- (meth) acryloyloxydiethoxyethyl-2 ′-(trimethylammonio) ethyl phosphate, 2- (meth) acryloyloxyethyl-3 ′-(trimethylammonio) propyl phosphate, 2- (meth) acryloyloxyethoxy Ethyl-2 ′-(trimethylammonio) propyl phosphate, 2- (meth) acryloyloxydiethoxyethyl-2 ′-(trimethylammonio) propyl phosphate, 2- (meth) acryloyloxyethyl-2 ′-(trimethylammoni E) Butyl phosphate, 2- (meth) acryloyloxyate Examples thereof include xylethyl-2 ′-(trimethylammonio) butyl phosphate and 2- (meth) acryloyloxydiethoxyethyl-2 ′-(trimethylammonio) butyl phosphate. MPC is most preferable from the viewpoint of availability. These can be used alone or as a mixture of two or more.

Component (B) is a silicon atom and hydroxyl group-containing monomer represented by the above formula (2), which dissolves component (A) and other (meth) acrylates. It is a component that also contributes to imparting oxygen permeability to the lens.
The component (B) can be obtained by a known synthesis method such as a method of adding (meth) acrylic acid and a corresponding silicon atom-containing epoxy compound, and is usually obtained as a mixture of isomers. These isomers have the same molecular formula but have slightly different boiling points and are detected separately on a gas chromatograph. However, it is difficult to separate them in industrial methods.
In the above formula (2), R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents —CH ₂ CH (OH) CH ₂ — or —CH (CH ₂ OH) CH ₂ —, and p represents 1 to 10 Indicates an integer. r is 2 or 3, q is 0 or 1, and r + q = 3. When p exceeds 10, or when r and q do not satisfy the above conditions, the ratio of siloxane groups in the molecule decreases, which may cause a decrease in oxygen permeability.

  Examples of the component (B) include 1-tris (trimethylsiloxy) silylpropyloxy-3- (meth) acryloyloxy-2-hydroxypropane, 1-methylbis (trimethylsiloxy) silylpropyloxy-3- (meth) acryloyl Oxy-2-hydroxypropane, 1-dimethyl (trimethylsiloxy) silylpropyloxy-3- (meth) acryloyloxy-2-hydroxypropane, and the like, and these isomers exist. A mixture is expected to have the same effect and can be used in the same manner. Component (B) can be used singly or as a mixture of two or more. From the viewpoint of compatibility and availability, 1-methylbis (trimethylsiloxy) silylpropyloxy-3- (meth) acryloyloxy It is preferable to contain 2-hydroxypropane.

In the composition of the present invention, the content of component (A) is 5 to 20% by mass, preferably 10 to 15% by mass, based on the total amount of the composition, and the content of component (B) is based on the total amount of the composition. 10% by mass or more, preferably 20% by mass or more, more preferably 20 to 80% by mass, and the content of component (A) is 50% by mass or less with respect to the content of component (B). is there.
When the content of the component (A) is less than 5% by mass, the effect based on the component (A) is difficult to be exhibited, so that the protein contamination resistance cannot be imparted. If the content of component (A) is more than 20% by mass, it will not dissolve in other monomers, or even if it can be dissolved, crystals will precipitate over time, or it will separate into the resulting polymer. Therefore, a transparent and homogeneous cured product cannot be obtained.
When the content of component (B) is less than 10% by mass, and when the content of component (A) exceeds 50% by mass relative to the content of component (B), sufficient amount of component (A) cannot be dissolved. .

Component (C) is a cross-linkable monomer, and the composition of the present invention is cross-linked by copolymerization. The resulting cured product, for example, a soft contact lens, retains the shape and is suitable for processing. It is a component that imparts mechanical strength, breaking elongation, and resilience.
Component (C) usually includes monomers having two or more polymerizable functional groups in one molecule, such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di Multifunctional such as (meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,2-bis (3 ′-(meth) acryloyloxy-2′-hydroxypropyloxy) ethane (Meth) acrylate is preferred, and ethylene glycol di (meth) acrylate is preferred because the effect is recognized in a small amount. In use, it can be used alone or as a mixture of two or more.
The content ratio of the component (C) is 0.1 to 2% by mass, preferably 0.2 to 1% by mass, based on the total amount of the composition. If the amount is less than 0.1% by mass, the shape of a cured product, for example, a contact lens, cannot be maintained and an appropriate restoration property cannot be provided. On the other hand, when it exceeds 2% by mass, for example, the flexibility required for the contact lens is lost, and it becomes brittle.

The composition of the present invention can contain other monomers other than the components (A) to (C) as necessary. Examples of the other monomer include (D) a hydrophilic monomer having a hydroxyl group or an amide group in the molecule. The component (D) is a hydroxyl group-containing monomer or an amide group-containing monomer.
Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2 -Hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hydroxymethyl (meth) acrylamide, polyethylene glycol (meth) acrylate and the like. From the viewpoint of hydrophilicity and availability, it is preferable to include 2-hydroxyethyl (meth) acrylate as the component (D).

Examples of the amide group-containing monomer include (meth) acrylamide, N-vinyl-2-pyrrolidone, N, N-dimethylacrylamide, isopropyl (meth) acrylamide, morpholyl (meth) acrylamide, and the like. From the viewpoint of easy availability, further imparting hydrophilicity to the resulting soft contact lens and the like and imparting flexibility and mechanical strength, as component (D), N-vinyl-2-pyrrolidone and In this case, the content ratio of N-vinyl-2-pyrrolidone and / or N, N-dimethylacrylamide is 20 to 39.9% by mass based on the total amount of the composition. It is preferable that
In the composition of the present invention, the content ratio in the case of containing the component (D) is usually 0.1 to 75% by mass, preferably 1 to 50% by mass, based on the total amount of the composition.
If the content of the component (D) is less than 0.1% by mass, the contact lens obtained may not be further improved in moisture content, flexibility, breaking strength, and breaking elongation. If it exceeds 75 mass%, the oxygen permeability may be reduced.

In the composition of the present invention, as the other monomer, in addition to the component (D), a monofunctional monomer copolymerizable with the component (B), for example, represented by the above formula (3) (E And silicon atom-containing monomers.
In formula (3), R ⁶ represents a hydrogen atom or a methyl group, and p represents an integer of 1 to 10. r is 2 or 3, q is 0 or 1, and r + q = 3. When p exceeds 10, or when r and q do not satisfy the above conditions, the ratio of siloxane groups in the molecule decreases, which may cause a decrease in oxygen permeability.

Examples of the component (E) include tris (trimethylsiloxy) silylpropyl (meth) acrylate, 1-methylbis (trimethylsiloxy) silylpropyl (meth) acrylate, 1-dimethyl (trimethylsiloxy) silylpropyl (meth) acrylate, and the like. Can be used alone or as a mixture of two or more. For reasons of oxygen permeability and availability, it is preferable to include tris (trimethylsiloxy) silylpropyl (meth) acrylate as the component (E).
In the composition of the present invention, the content ratio in the case of containing the component (E) is usually 0.1 to 50% by mass based on the total amount of the composition, and the content of the component (B) and the component (E) Is 50% by mass or more, preferably 60% by mass or more in the total amount of the composition. When the sum of the content of the component (B) and the component (E) is less than 50% by mass, for example, when a soft contact lens is used, there is a possibility that the effect of improving oxygen permeability that can be continuously worn may be reduced. is there.

  In the composition of the present invention, for example, other monomers can be further contained as long as desired protein resistance, oxygen permeability, hydrophilicity and flexibility are not impaired. Examples thereof include, but are not limited to, alkyl (meth) acrylate, FMA, polydimethylsiloxane di (meth) acrylate, and the like. The content ratio of these other monomers can be appropriately determined in consideration of the purpose and the like.

The contact lens of the present invention can be obtained by copolymerizing and curing the monomer composition for contact lens containing the above-mentioned components (A), (B) and (C) in the above-mentioned specific ratio. Further, a monomer composition for a contact lens containing the above-mentioned (A) component, (B) component, (C) component and (D) component, and, if necessary, the (E) component in the above-mentioned specific proportion is copolymerized. By curing, it is possible to obtain a soft contact lens and the like that are particularly excellent in protein contamination resistance, high oxygen permeability, hydrophilicity, and flexibility that improves wearing feeling.
The contact lens of the present invention usually has an oxygen permeability of 25 × 10 ⁻¹¹ [cc (STP) cm] / [cm ² · sec · mmHg] or more. The component (A) is 2- (meth) acryloyloxyethyl-2 ′-(trimethylammonio) ethyl phosphate, and the component (B) is 1-methylbis (trimethylsiloxy) silylpropyloxy-3- (meth). Acryloyloxy-2-hydroxypropane, component (C) is ethylene glycol di (meth) acrylate, component (D) is 2-hydroxyethyl (meth) acrylate, N-vinyl-2-pyrrolidone and N, N-dimethyl At least one member selected from the group consisting of acrylamide, and the component (E) is tris (trimethylsiloxy) silylpropyl (meth) acrylate, which is copolymerized with the monomer composition for contact lens containing the above-mentioned specific ratio. in the case of-cured contact lens is usually oxygen permeability ^{50 × 10 -11 [cc (STP} ) cm] / [cm 2 · sec · mmHg] or more, water content 35 0%, and modulus of elasticity can be a contact lens is 1MPa or less.

In addition to the contact lens composition of the present invention described above, the contact lens of the present invention can be produced, for example, by increasing the polymerization rate and dimensional stability, improving the cleanability of the soft contact lens, and separating from the mold after polymerization. In view of improvement in moldability and the like, it can be produced using a solvent as necessary.
Examples of the solvent include water, aliphatic alcohols such as ethyl alcohol, isopropyl alcohol, and butanol, aprotic polar solvents such as dimethylformamide, chlorinated solvents such as chloroform, fatty acids such as octanoic acid and oleic acid, or the like. 2 or more types of suitable mixed solvents. Moreover, surfactants, such as a nonion and a cation, can also be used suitably for a solvent. Among these, ethyl alcohol and isopropyl alcohol can be preferably used.
Although the usage-amount of a solvent can be suitably selected according to the kind etc., normally 30 mass parts or less are preferable with respect to 100 mass parts of monomer compositions for contact lenses, More preferably, 20 mass parts It is as follows. When the amount used exceeds 30 parts by mass, the polymerization rate and dimensional stability of the contact lens are lowered, and the solvent tends to remain.

In the production of the contact lens of the present invention, an appropriate amount of a coloring agent such as a coloring matter, a dye or a pigment, an ultraviolet absorber, or the like can be used as long as the desired effect of the obtained contact lens is not impaired.
Examples of the colorant include blue 201, blue 204, purple 201, red 404, green 202, blue 404, and the like.
Preferred examples of the ultraviolet absorber include 2- (2-hydroxy) benzotriazole, 2- (hydroxy) benzophenone and the like.

In the production of the contact lens of the present invention, the polymerization method is carried out by a radical polymerization method using a general radical polymerization initiator. For example, it can be performed by a known technique such as bulk polymerization.
Examples of the radical polymerization initiator include benzoyl peroxide, lauroyl peroxide, diisopropyl peroxydicarbonate, t-butylperoxy-2-ethylhexanoate, t-butylperoxypivalate, t-butylperoxydiisobutyrate, azo Examples thereof include bisisobutyronitrile, azobisdimethylvaleronitrile, or an appropriate mixture thereof.
The amount of the radical polymerization initiator used is usually 0.01 to 5 parts by mass, preferably 0.05 to 2 parts by mass with respect to 100 parts by mass of all monomers of the contact lens monomer composition of the present invention. is there.

  The contact lens of the present invention can be produced by, for example, injecting a monomer composition for a contact lens, a radical polymerization initiator, and, if necessary, a solvent and various additives into a predetermined mold and heating or light irradiation. Method of directly molding contact lens by mold polymerization, copolymerizing in a suitable container such as a test tube to obtain a round bar (rod) or block, and then molding to contact lens by mechanical processing such as cutting and polishing A method of casting while heating or irradiating with light, a polymer produced in advance by a radical polymerization method, etc., and then dissolving the polymer in an appropriate solvent and removing the solvent by a casting method, etc. it can. In addition, since the contact lens of this invention is excellent in mechanical strength, for example in the state containing water, the method of shape | molding a contact lens directly by the said mold polymerization is suitable among the said methods.

Hereinafter, the present invention will be described in more detail based on specific examples, but the present invention is not limited thereto.
In addition, the symbol used for the table | surface of an Example and a comparative example is as follows.
<(A) component>
MPC; 2-methacryloyloxyethyl-2 '-(trimethylammonio) ethyl phosphate
MEPC; 2-methacryloyloxyethoxyethyl-3 '-(trimethylammonio) propyl phosphate
MTPC; 2-methacryloyloxytetraethoxyethyl-2 '-(trimethylammonio) ethyl phosphate <component (B)>
MSMP; 1-methylbis (trimethylsiloxy) silylpropyloxy-3-methacryloyloxy-2-hydroxypropane
TSMP; 1-tris (trimethylsiloxy) silylpropyloxy-3-methacryloyloxy-2-hydroxypropane <(C) component>
EDMA: Ethylene glycol dimethacrylate, TGDM: Triethylene glycol dimethacrylate <(D) component>
HEMA; 2-hydroxyethyl methacrylate, HBMA; 4-hydroxybutyl methacrylate, NVP; N-vinylpyrrolidone, DMA; N, N-dimethylacrylamide <(E) component>
TRIS; Tris (trimethylsiloxy) silylpropyl methacrylate
MBIS: Methylbis (trimethylsiloxy) silylpropyl methacrylate

<Other monomers>
SiDM: silicon atom-containing compound represented by the following chemical formula (wherein n is approximately 40)

F17MA; Perfluorooctylethyl methacrylate
FMBM; 1- (perfluoro-3'-methylbutyl) -3-methacryloyloxy-2-hydroxypropane, MMA; methyl methacrylate

Example 1
5 parts by mass of MPC was mixed and dissolved in 30 parts by mass of HEMA. When 20 parts by mass of MSMP, 44.7 parts by mass of DMA, 0.3 part by mass of EDMA and 0.5 part by mass of azobisisobutyronitrile (AIBN) were further dissolved in the obtained mixture, an optically transparent and uniform composition was obtained. was gotten. This composition was poured into a cell sandwiched between a glass plate and a polyester film using a Teflon (registered trademark) sheet having a thickness of 0.2 mm as a spacer, followed by nitrogen substitution in the oven, and then at 65 ° C. Heated at 80 ° C. for 3 hours for 3 hours. After the heating, the cured sheet was taken out of the mold and immersed in a large amount of ethyl alcohol for 12 hours, and further immersed in a large amount of ion-exchanged water for 12 hours. The cured sheet was taken out from the ion exchange water and visually evaluated for transparency. The resulting sheet was transparent. A test piece having a predetermined shape was produced from this sheet, and the following physical properties were evaluated. The results are shown in Table 1.

1. Measurement of protein adsorption amount 10 mm x 10 mm in a physiological saline solution of albumin 0.39% (W / V), lysozyme 0.17% (W / V), and γ-globulin 0.105% (W / V) After immersing a test piece of × 0.2 mm, it was lightly rinsed with physiological saline. Next, the protein was peeled from the test piece using an aqueous surfactant solution of 1% by mass sodium dodecyl sulfate, a reagent for protein quantification was injected into the solution, and the protein adsorbed on the test piece was quantified.
Protein adsorption amount (μg / cm ² ) = The amount of protein measured by peeling the protein from the test piece per unit area was taken as the measurement result.
2. Measurement of Oxygen Permeability An oxygen permeability coefficient in ion-exchanged water at 35 ° C. was determined using a Seikaken type film oxygen permeability measuring device (R-Seiki Kogyo K-316). The unit of oxygen permeability (Dk value) in the table is 10 ⁻¹¹ cc (STP) · cm / cm ² · sec · mmHg.

3. Measurement of water content A sheet containing water having a width of 25 mm and a length of 50 mm was immersed in ion-exchanged water to obtain a saturated water content, and then the mass was measured. Then, the mass was measured by drying in an oven at 70 ° C. for 2 hours under reduced pressure. did. The water content was calculated by the following formula. The unit of moisture content in the table is%.
Moisture content (%) = [(W ₁ −W ₂ ) / W ₁ ] × 100 (W ₁ : Mass when saturated with water, W ₂ : Dry mass)
4). Measurement of Elastic Modulus 20 strips having a length of 15 mm and a width of 2 mm were cut out from the water-containing sheet, and the elastic modulus of the water-containing strip was measured using a tensile tester (manufactured by Yamaden Co., Ltd., Leoner Re-3305). The unit of elastic modulus in the table is MPa.

Examples 2-15
After obtaining a polymer using the monomer composition shown in Table 1 in the same manner as in Example 1, a water-containing sheet and a test piece were obtained. The physical properties of the obtained water-containing sheet and test piece were measured in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1
5 parts by mass of MPC was mixed and dissolved in 30 parts by mass of HEMA. When 20 parts by mass of TRIS, 45 parts by mass of DMA and 0.5 parts by mass of AIBN were further dissolved in the obtained mixture, a blended composition separated into two upper and lower layers was obtained. The results are shown in Table 2.

Comparative Examples 2-12
A blended composition was obtained using the monomer composition shown in Table 2 in the same manner as in Comparative Example 1, and a polymer was obtained in the same manner as in Example 1 in the case where the composition was a transparent uniform solution. After that, a water-containing sheet and a test piece were obtained. The physical properties of the obtained water-containing sheet and test piece were measured in the same manner as in Example 1. The results are shown in Table 2.

  From the above results, it can be seen that the monomer composition of the present invention is uniformly transparent. In addition, the water-containing sheet of the example obtained by polymerizing the monomer composition is superior in both resistance to protein contamination and oxygen permeation as compared with the comparative example, and is further a soft contact lens having hydrophilicity and flexibility. It can be seen that this is suitable.

Claims (9)

(A) phosphorylcholine-like group-containing (meth) acrylate represented by the formula (1): 5 to 20% by mass;

(In the formula, R ¹ , R ² and R ³ represent a hydrogen atom or a methyl group. M represents an integer of 1 to 8, and n represents an integer of 2 to 4.)
(B) a silicon atom and hydroxyl group-containing monomer represented by the formula (2) of 10% by mass or more,

(In the formula, R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents —CH ₂ CH (OH) CH ₂ — or —CH (CH ₂ OH) CH ₂ —, and p represents an integer of 1 to 10. R is 2 or 3, q is 0 or 1, and r + q = 3.)
(C) A monomer composition comprising 0.1 to 2% by mass of a crosslinkable monomer, wherein the content of the component (A) is 50% by mass or less of the content of the component (B).   A monomer composition for contact lenses comprising the composition according to claim 1.   (D) The composition of Claim 2 which further contains 0.1-75 mass% of hydrophilic monomers which have a hydroxyl group or an amide group in a molecule | numerator.   The component (A) is 2- (meth) acryloyloxyethyl-2 ′-(trimethylammonio) ethyl phosphate, and the component (B) is 1-methylbis (trimethylsiloxy) silylpropyloxy-3- (meth) Acryloyloxy-2-hydroxypropane, wherein the component (C) is composed of ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate and polyethylene glycol di (meth) acrylate And (D) component is at least one selected from the group consisting of 2-hydroxyethyl (meth) acrylate, N-vinyl-2-pyrrolidone and N, N-dimethylacrylamide. The composition according to claim 2 or 3. Further comprising 0.1 to 50% by mass of the (E) silicon atom-containing monomer represented by the formula (3),

(In the formula, R ⁶ represents a hydrogen atom or a methyl group, p represents an integer of 1 to 10, r is 2 or 3, q is 0 or 1, and r + q = 3).
And the sum total of the content of said (B) component and said (E) component is 50 mass% or more in a composition whole quantity, The composition of any one of Claims 2-4.   The component (A) is 2- (meth) acryloyloxyethyl-2 ′-(trimethylammonio) ethyl phosphate, and the component (B) is 1-methylbis (trimethylsiloxy) silylpropyloxy-3- (meth) Acryloyloxy-2-hydroxypropane, wherein the component (C) is composed of ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate and polyethylene glycol di (meth) acrylate And the component (D) is at least one selected from the group consisting of 2-hydroxyethyl (meth) acrylate, N-vinyl-2-pyrrolidone and N, N-dimethylacrylamide. The component (E) is tris (trimethylsiloxy) silylpropyl (meth) acrylic. Over preparative at a composition of claim 5.   The composition according to claim 6, wherein the component (D) contains 20 to 39.9% by mass of N-vinyl-2-pyrrolidone and / or N, N-dimethylacrylamide. A contact lens obtained by curing the composition according to claim 2, wherein the oxygen permeability is 25 × 10 ⁻¹¹ [cc (STP) cm] / [cm ² · sec · mmHg] or more. . An oxygen permeability of 50 × 10 ⁻¹¹ [cc (STP) cm] / [cm ² · sec · mmHg] or more obtained by curing the composition according to claim 4, 6 or 7, and a water content of 35 to 50 %, And a contact lens having an elastic modulus of 1 MPa or less.