JPH0545612A - Contact lens material having resistance against contamination - Google Patents

Abstract

PURPOSE:To improve resistance against contamination and to improve the balance in physical properties by using copolymers comprising bifunctional org. siloxane macromers having specified structures and mol.wts. and/or copolymerizable monomers. CONSTITUTION:The polymer used as the material is obtd. by polymn. of one or more kinds of bifunctional org. siloxane macromers expressed by formula I, or polymn. with one or more kinds of copolymerizable monomers. In formula I, R1 is hydrogen or a methyl group, R2-R5 are hydrocarbon groups of 1-12 carbon number or trimethylsiloxane groups, Y is a structural unit expressed by formulae II and III, with the ratio of II:III=1:10 to 10:1, and the total number of the structural units II and III is 7-200. m and n are integers of 1-20, P is an integer of 0-20, X is -NHCOO- group, etc. In formulae II and III, R6 and R7 are hydrocarbon groups of 1-12 carbon number, R8 and R9 are hydrocarbon groups or fluorine-substd. hydrocarbon groups of 1-12 carbon number.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel contact lens material. More specifically, the present invention relates to a material of a substantially water-free soft contact lens, which has a low adhesion of stains such as proteins in tears and a good balance of physical properties such as oxygen permeability.

[0002]

2. Description of the Related Art Soft contact lenses are classified into hydrous soft contact lenses and non-hydrous soft contact lenses. Hydrous soft contact lenses are composed of a copolymer obtained by polymerizing a hydrophilic monomer such as hydroxyethyl methacrylate and N-vinylpyrrolidone as a main component, and a lens is prepared by a cutting or casting method and swelled in physiological saline. The lens has a water content of about 40 to 70%.

As a non-hydrous soft contact lens, for example, a platinum-based catalyst is added to a mixture of polydimethylsiloxane whose both molecular chain ends are blocked with vinyldimethylsilyl groups and methylhydrogenpolysiloxane, and a molding method is used. Intermediate between soft contact lenses and hard contact lenses, which consists of a silicone rubber lens obtained by the method of heating and curing with a polymer and a polymer whose main component is polyperfluoroether with a polymerizable group such as a methacryloxy group added to both ends. Flexible lenses having the above elastic modulus are known (JP-A-54-81363, JP-A-58-127914).

Further, a lens is prepared by cutting from a hard substrate obtained by copolymerizing (meth) acrylic acid and (meth) acrylic acid ester, and the lens is esterified and / or transesterified to give a feeling of wearing. Good non-hydrous soft contact lenses have also been manufactured (JP-A-48-7504).
No. 7). A contact lens material mainly composed of polyfunctional polysiloxane and having high oxygen permeability is also disclosed in JP-A-54-240.
47, JP-A-56-51715, JP-A-5
It is described in JP-A-9-229524 and JP-A-2-188717.

Hydrous soft contact lenses are soft and comfortable to wear, and have advantages such as high oxygen permeability when they are of a high water content type, but they are easily damaged and inferior in durability and lacrimal fluid. It is often inconvenient to handle because it is apt to be contaminated by the ingredients inside and there is a risk of bacterial growth, so that it has to be boiled and disinfected regularly. Non-hydrous contact lenses also have the following problems.

[0006] First, regarding the silicone rubber lens, at the beginning of development, the hydrophilic treatment layer applied to improve the hydrophobicity of the lens surface is peeled off, or the elasticity is too large, so that adhesion to the cornea occurs. Although it has drawbacks, it has not been widely put into practical use, but recently, due to advances in surface hydrophilization treatment technology, changes in lens design, and improvements in mechanical properties, the aforementioned drawbacks have been considerably improved. Yes, but it is still not entirely satisfactory and the reality is that it is not widely used.

Next, since the non-water-containing lens containing polyperfluoroether as a main component is closer to a semi-hard type than a soft contact lens, it does not give a feeling of wearing like a soft contact lens, and it does not come on the cornea. The movement of the lens is not satisfactory either. Also (meta)
A soft contact lens mainly composed of an acrylic ester is inferior in oxygen permeability, and is not suitable for wearing for a long time.

None of the materials containing polyfunctional polysiloxane as a main component is closer to the silicone rubber lens, taking into consideration the contamination by the components in the tear fluid.

[0009]

Under the above circumstances, the present invention is a substantially non-water-containing material having a low dirt adhesion property and an excellent oxygen permeability coefficient (DK value), optical and mechanical properties. The object is to provide a new soft contact lens material.

[0010]

Means for Solving the Problems As a result of intensive studies conducted by the present inventors to develop a non-hydrous soft contact lens material that solves the above problems, a bifunctional organosiloxane having a specific structure and molecular weight is obtained. It was found that the object can be achieved by a material composed of a copolymer obtained by polymerizing a macromer as a main component, and the present invention could be completed based on this finding.

That is, the present invention is as follows. 1. A polymer obtained by polymerizing one or more difunctional organosiloxane macromers represented by the following chemical formula 7 with only the difunctional organosiloxane macromers or with one or more copolymerizable monomers. A contact lens material that consists of a united body.

[0012]

[Chemical 7]

[Wherein R ₁ is hydrogen or a methyl group, R ₂ ,
R ₃ , R ₄ and R ₅ are each a hydrocarbon group having 1 to 12 carbon atoms or a trimethylsiloxy group, Y is composed of the structural units (I) and (II) shown in the following chemical formula 8, and the structural unit (I ): Ratio of structural units (II) is from 1:10 to 1
0: 1 and the total number of structural units (I) and (II) is 7 to 2
00. m and n are the same or different 1-2
Is an integer of 0, and P is an integer of 0-20. X is -N
HCOO- group or -OOCHN-R ₁₀ -NHCOO- group (R ₁₀ represents a hydrocarbon group having 4 to 13 carbon atoms) is. ]

[0014]

[Chemical 8]

2. A polymer obtained by polymerizing one or more difunctional organosiloxane macromers represented by the following chemical formula 9 with only the difunctional organosiloxane macromers or with one or more copolymerizable monomers. A contact lens material that consists of a united body.

[0016]

[Chemical 9]

[Wherein R ₁ is hydrogen or a methyl group, Y is composed of structural units (I ′) and (II ′) shown in the chemical formula 10 below, and structural unit (I ′): structural unit (II ″) Of the structural units (I ') and (I
The total number of I ') is 7 to 200. m and n are the same or different integers of 1 to 20, and P is 0 to 20.
Is an integer. X is a -NHCOO- group or -OOCHN
-R ₂ -NHCOO- group (R ₂ is a hydrocarbon group having 4 to 13 carbon atoms) is. ]

[0018]

[Chemical 10]

3. One or more kinds of bifunctional organic siloxane macromers represented by the following chemical formula 11 and one or two kinds selected from acrylic acid fluoroalkyl ester, methacrylic acid fluoroalkyl ester, acrylic acid alkyl ester, and methacrylic acid alkyl ester. A contact lens material comprising a copolymer containing the above as a main component.

[0020]

[Chemical 11]

[Wherein R ₁ is hydrogen or a methyl group, Y is composed of structural units (I ′) and (II ′) shown in the chemical formula 12 below, and structural unit (I ′): structural unit (II ″) At a ratio of 1:10 to 10: 1 with structural units (I ') and (I
The total number of I ') is 7 to 200. m and n are the same or different integers of 1 to 20, and P is 0 to 20.
Is an integer. X is a -NHCOO- group or -OOCHN
-R ₂ -NHCOO- group (R ₂ is a hydrocarbon group having 4 to 13 carbon atoms) is. ]

[0022]

[Chemical formula 12]

The present invention will be described in detail below. When the molecular weight of the bifunctional organosiloxane macromer represented by the formula (1) increases, the chain between the functional groups becomes longer, so that the oxygen permeability is improved, the cohesive energy is lowered, and the glass transition point is low. Therefore, when used as a soft contact lens, it exerts a great effect on the softness and the shape-retaining property and physical properties indicated by rubber elasticity. The structure of the siloxanyl unit of the macromer, which determines the molecular weight, is shown below.
It is shown by (I) and (II) in 3.

[0024]

[Chemical 13]

The structural units (I) and (II) each have the following characteristics. The structural unit (I) has an effect of increasing oxygen permeability and an effect of lowering the glass transition point as the number of the structural unit (I) increases in the molecule. It is a structure that is indispensable for physical properties such as the property of trying to return to its original state).

However, when the structural unit (I) is continuously present in the molecule, the hydrophobic property of the structural unit (I) causes adsorption of proteins and the like in the lacrimal fluid, which easily causes contamination. Next, in the structural unit (II), at least one of the side chains of the siloxanyl group is a fluorine-substituted hydrocarbon group, and by having a fluorine-substituted hydrocarbon group in the side chain, the critical surface tension caused by the fluorine atom is Will occur. From this, the contact lens material of the present invention has water-repellent and oil-repellent properties,
This has the effect of suppressing the surface of the contact lens from being contaminated by proteins, lipids, inorganic components, etc. in the tear fluid, and has the property of easily peeling off even if contaminants adhere.

However, the structural unit (II) does not tend to increase oxygen permeability as much as the structural unit (I) does, and if too much is present in the molecule, it becomes difficult to obtain the desired oxygen permeability. If the number of the structural unit (I) and the structural unit (II) present in the molecule is too large, the nuclear macromer may be clouded to obtain the compound, or the compatibility with the copolymerizable monomer may be deteriorated, resulting in phase separation. It causes or becomes cloudy during polymerization. If the number is small, not only the oxygen permeability is lowered, but also the softness and flexibility required for a soft contact lens are deteriorated. For the above reason, the abundance ratio and number of structural units (I) and (II) contained in the molecule are such that the ratio of structural unit (I): structural unit (II) is 1:10.
To 10: 1, preferably 1: 8 to 8: 1,
The total number of structural units (I) and (II) is 7 to 200, preferably about 10 to 120.

The side chain of the siloxanyl group of the structural unit (I) is a hydrocarbon group having 1 to 12 carbon atoms, preferably a methyl group. At least one side chain of the siloxanyl group of the structural unit (II) must be a fluorine-substituted hydrocarbon group, for example, 3,3,3-trifluoropropyl group, 1,1,2,2 Examples thereof include a tetrahydroperfluorooctyl group and a 1,1,2,2-tetrahydroperfluorodecyl group, and among them, a trifluoropropyl group is preferable.

Next, X in the formula (1) represents a residue of a monofunctional isocyanate or a bifunctional isocyanate, each of which is --NHCOO-- or --OOOCNH--R ₈ --NHC.
OO- group (R ₈ is a divalent hydrocarbon group having 4 to 13 carbon atoms and is an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group). By including these urethane bonds in the molecular structure, the strength and wettability of the contact lens can be improved.

As the residue of the bifunctional isocyanate, for example, hexamethylene diisocyanate, tetramethylene diisocyanate, 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, 2,6-diisocyanate methyl caproate, 3-isocyanate methyl-
There are residues of 3,5,5-trimethylcyclohexyl isocyanate, dicyclohexylmethane-4,4'-diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, isophorone diisocyanate, among which hexamethylene diisocyanate and isophorone diisocyanate Residues are preferred.

(1) In the formula, R ₁ is hydrogen or a methyl group, and R ₂ , R ₃ , R ₄ and R ₅ each have 1 to 1 carbon atoms.
It is a hydrocarbon group of 2 or a trimethylsiloxy group, and a hydrocarbon group of 1 to 3 carbon atoms or a trimethylsiloxy group is preferable from the viewpoint of softness, elasticity, strength and dirt adhesion of a contact lens. m and n are integers of 1 to 20 and P is an integer of 0 to 20. When they exceed 20 and become large, compatibility with other monomers deteriorates and white turbidity easily occurs, which is not preferable.

The bifunctional organosiloxane macromer represented by the formula (1) is, for example, 1,3-bis- (4-hydroxyalkyl) tetramethyldisiloxane, octamethylcyclotetrasiloxane and 1,3,5-trimethyl. A diol having a polysiloxane structure obtained by a ring-opening insertion reaction with trifluoropropylcyclotrisiloxane is reacted with, for example, an equivalent amount of isocyanate ethyl methacrylate or twice equivalent amount of diisocyanate, and then with hydroxyethyl methacrylate. Obtained by The structure of the obtained bifunctional organosiloxane macromer was analyzed from NMR (nuclear magnetic resonance spectrum) and IR absorption spectrum.

The abundance ratio and the abundance of the structural units (I) and (II) contained in the molecule can be determined by measuring NMR (nuclear magnetic resonance spectrum). For example, when the structural unit (I) is dimethylsiloxane and the structural unit (II) is methyl-trifluoropropylsiloxane, the integrated value of the proton absorption for the methyl group and the proton absorption for the trifluoropropyl group appearing in the NMR spectrum is measured. Furthermore, it can be obtained by measuring the integral value of the proton absorption for the methylene group contained in the same molecule.

The contact lens of the present invention comprises a bifunctional organosiloxane macromer represented by the formula (1), or one or more difunctional organosiloxane macromers alone or as a copolymerizable monomer. It consists of a cross-linked polymer obtained by polymerizing with one or more species. Depending on the target performance of the contact lens, such as the required oxygen permeability, softness, stain resistance, strength, etc., the type and number of bonds of the constituent unit that constitutes Y in the formula (1), and The residues that make up X are selected.

The copolymerizable monomer will be described below.
Acrylic acid fluoroalkyl ester and methacrylic acid fluoroalkyl ester used as copolymerizable monomers in the present invention have water-repellent and oil-repellent properties due to the reduction of the critical surface tension due to the fluorine atom.
This has the effect of suppressing the surface of the contact lens from being contaminated by components such as proteins and lipids in tear fluid. Further, this monomer component preferably has a physical property that the glass transition point is room temperature or lower, and when copolymerized,
It can develop the softness and flexibility required for soft contact lenses.

Specific examples of these acrylic acid fluoroalkyl ester and methacrylic acid fluoroalkyl ester include trifluoroethyl acrylate, tetrafluoroethyl acrylate, tetrafluoropropyl acrylate, pentafluoropropyl acrylate, hexafluorobutyl acrylate and hexafluoroisopropyl acrylate. , Heptafluorobutyl acrylate, octafluoropentyl acrylate, nonafluoropentyl acrylate, dodecafluoropentyl acrylate, dodecafluoroheptyl acrylate, dodecafluorooctyl acrylate, tridecafluoroheptyl acrylate, and methacrylates corresponding to these acrylates. , Preferably trifluoroethyl Acrylate, hexafluoroisopropyl acrylate, geek fluoro pentyl acrylate, dodecamethylene perfluorooctyl acrylate is used. These monomers may be used alone or in combination of two or more.

The acrylic acid alkyl ester monomer and the methacrylic acid alkyl ester monomer used as the copolymerizable monomer in the present invention are composed of a bifunctional organosiloxane macromer and a (meth) acrylic acid fluoroalkyl ester. It has the effect of improving the solubility and plays a role in broadening its range of use. It is preferable to lower the glass transition point of the copolymer to room temperature or 0 ° C. or lower. Since these reduce the cohesive energy, they have the effect of imparting rubber elasticity and softness to the copolymer.

Specific examples of these acrylic acid alkyl esters and methacrylic acid alkyl esters include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, tert-butyl acrylate, isobutyl acrylate, n-hexyl acrylate, n-. Octyl acrylate, n-heptyl acrylate, n-nonyl acrylate, n-decyl acrylate, isodecyl acrylate, n-lauryl acrylate, tridecyl acrylate, n-dodecyl acrylate, cyclopentyl acrylate, cyclohexyl acrylate, n-stearyl acrylate and acrylates thereof. Methacrylates and the like corresponding to the above can be mentioned, and n-butyl acrylate and n-octyl are preferable. Acrylate, n- lauryl methacrylate, n- stearyl methacrylate is used. These monomers may be used alone or in combination of two or more.

Further, in order to improve mechanical properties, surface wettability, dimensional stability of the lens and the like, the following monomers can be copolymerized, if desired. Examples of the monomer for improving the mechanical properties include aromatic vinyl compounds such as styrene, tert-butyl styrene and α-methyl styrene.

Monomers for improving the surface wettability include, for example, methacrylic acid, acrylic acid, itaconic acid, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, Glycerol methacrylate, polyethylene glycol methacrylate, N, N'-dimethylacrylamide, N
-Methyl acrylamide, dimethylaminoethyl methacrylate, methylene bis acrylamide, diacetone acrylamide, N-vinylpyrrolidone and the like can be mentioned.

Monomers for improving the dimensional stability of the lens include, for example, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, Examples thereof include bisphenol A dimethacrylate, vinyl methacrylate, acryl methacrylate and acrylates corresponding to these methacrylates, divinylbenzene, triallyl isocyanurate and the like.

These monomers may be used alone or in combination of two or more. In order to improve the balance of properties such as optical characteristics of contact lenses, oxygen permeability, mechanical strength, deformation recovery, stain adhesion when worn on the eye, dimensional stability in tear fluid and its change over time. Mixed monomer combining copolymerizable monomers
Can be used.

Examples of mixed monomers copolymerizable with the bifunctional organosiloxane macromer of the present invention include trifluoroethyl acrylate, n-butyl acrylate, a combination of methacrylic acid and ethylene glycol dimethacrylate, perfluorooctyl ethyl acrylate. , N-butyl acrylate, methacrylic acid and diethylene glycol dimethacrylate in combination.

The copolymer used as the contact lens material of the present invention is a cast polymerization method in which a monomer mixture is filled in a mold and radical-polymerized by a known method, and the monomer mixture is charged in a rotating half-face mold. To polymerize with,
Alternatively, the copolymer can be formed into a contact lens by a method such as freeze cutting at a low temperature. The method of copolymerization is
Photoinitiators such as benzoin, benzophenone and benzyldimethylketanol are present in the monomer mixture,
A method of polymerizing by irradiating ultraviolet rays or a method of thermally polymerizing by using an azo compound such as azobisisobutyronitrile, benzoyl peroxide, lauroyl peroxide or an organic peroxide is preferable.

[0045]

EXAMPLES The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto. In addition, each physical property and molecular weight were calculated as follows. (1) Oxygen permeability coefficient Gas permeability measuring device K-31 manufactured by Rika Seiki Co., Ltd.
5-N was used. The sample piece has a diameter of 30 mm and a thickness of 0.3 m
A disk-shaped object of m was used for the measurement, and the oxygen permeation coefficient was calculated from the slope of the straight line on the obtained chart.
The measurement was carried out in a thermostatic chamber at 25 ° C. and at a sample piece setting place of 35 ° C. (2) Contact angle Contact Angle manufactured by Kyowa Interface Science Co., Ltd.
Meter CA-A was used. Prior to the measurement, the sample piece was mirror-polished, the surface was cleaned using a surfactant, and the sample piece was immersed in physiological saline for 24 hours and then subjected to the measurement. For the measurement, the sample piece is allowed to stand in pure water, a bubble with a diameter of 1.5 to 2.0 mm is brought into contact with the lower surface of the sample piece with a syringe, the angle formed by the bubble and the sample piece is read, and the contact angle is calculated. I asked. (3) Tensile strength Universal tensile compression tester SV-50 manufactured by Imada Manufacturing Co., Ltd.
Was used. A sample piece having a thickness of 0.3 mm, a width of 5.0 mm and a length of 30 mm was used for the measurement. Tensile speed is 10m
It was m / min. The measurement was performed three times on the same sample piece, and the tensile strength was obtained from the obtained value according to the calculation method described in JIS-K-6301. (4) Staining Adhesion The Journal of Japan Contact Lens Society, 24 (1982) p. Two
A stain adhesion test was conducted by the method described in 77-283. A sample piece having a thickness of 2 mm, a width of 5 mm and a length of 30 mm was used. Judgment was based on the adhesion of dirt when a PMMA sample piece was similarly operated as a control, and when the degree of dirt adhesion was less than that by visual observation, it was "small", when it was large, it was "large", and when it was equivalent, it was " Equivalent ". In addition, three types of mucin (bovine gastric mucosa), lysozyme (egg white), and lecithin (egg yolk) were used as models of the contaminants. (5) Hardness In accordance with the method described in JIS-K-6301, the hardness (Sho
re A) was measured.

[0046]

Example 1 30 g (0.0042 mo) of organosiloxane diol represented by the following chemical formula 14 having hydroxyl groups at both ends
1) was charged into a 500 ml brown round bottom flask equipped with a condenser, a thermometer and a stirrer, and 1.303 g (0.0084 mo) of 2-isocyanatoethyl methacrylate was added thereto.
1), 5 drops of dibutyltin dilaurate and tetrahydrofuran were added, and the mixture was reacted at 70 ° C. for 5 hours while stirring in an N ₂ atmosphere. During the reaction, the infrared absorption spectrum was used to trace the change in absorption based on the isocyanate group, and it was confirmed that there was no change in the absorption.

[0047]

[Chemical 14]

After cooling, about 300 m of tetrahydrofuran
1, activated carbon for decolorization and magnesium sulfate for dehydration were added and left overnight. Then, after filtering through a 0.2 μm Teflon filter, low-boiling substances such as tetrahydrofuran were removed using an evaporator, and 21.6 g of a transparent, slightly viscous liquid was obtained. As a result of analyzing the structure of this liquid by NMR (proton nuclear magnetic resonance spectrum), it was confirmed to be an organic siloxane macromer represented by the following chemical formula 15. The NMR spectrum of this organosiloxane macromer is shown in FIG.

[0049]

[Chemical 15]

55 parts by weight of the organosiloxane macromer containing the urethane bond shown in Chemical formula 15, 25 parts by weight of trifluoroethyl acrylate (hereinafter referred to as 3FA), n-
20 parts by weight of butyl acrylate (hereinafter referred to as n-BA), 6 parts by weight of methacrylic acid (hereinafter referred to as MAA), ethylene glycol dimethacrylate (hereinafter referred to as ED) 4
1 part by weight and 0.5 part by weight of benzyl dimethyl ketanol (Ciba-Geigy, trade name I-651) were added, and the mixture was dissolved and mixed by stirring for about 1 hour with a magnetic stirrer in a nitrogen atmosphere.

Then, in a nitrogen atmosphere, two glass plates (thickness: 10) with a silicone rubber gasket interposed therebetween.
mm, width 60 mm, length 90 mm), the reaction solution was injected into a cell, and the cell was irradiated with ultraviolet rays at a temperature of 40 to 50 ° C. for 2 hours to obtain a transparent copolymer. The oxygen permeability coefficient, contact angle, tensile strength, stain adhesion and hardness of the thus obtained copolymer were measured. The results are shown in Table 1.

Next, the above-mentioned reaction liquid was injected and filled into a polypropylene concave-convex mold (lens diameter: 13.7 mm) prepared by injection molding, and irradiated with ultraviolet rays for 2 hours. The lens taken out from the mold after the irradiation was transparent and showed flexibility, and had good strength.

[0053]

Example 2

[0054]

[Chemical 16]

The organosiloxane diol represented by the chemical formula 16 above was reacted with a 2-molar amount of 2-isocyanatoethyl methacrylate in the same manner as in Example 1 and purified to obtain an organosiloxane macromer containing a urethane bond represented by the following chemical formula 17. Obtained.

[0056]

[Chemical 17]

55 parts by weight of the organosiloxane macromer represented by the chemical formula 17 above, 25 parts by weight of 3FA, and n-BA2
0 parts by weight, 6 parts by weight of MAA, 4 parts by weight of ED, and 0.5 parts by weight of benzyldimethylketanol were added, and the mixture was polymerized in the same manner as in Example 1 to obtain a transparent copolymer. The results of measuring the physical properties of the obtained copolymer are shown in Table 1.

[0058]

Example 3 50 parts by weight of the macromer represented by Chemical formula 17 obtained in Example 2, 20 parts by weight of perfluorooctylethyl acrylate (hereinafter referred to as FA-8), n-BA
Example 1 was blended with 30 parts by weight, 4 parts by weight of MAA, 2 parts by weight of ED, and 0.5 parts by weight of benzyldimethylketanol.
A copolymer was prepared and its physical properties were measured in the same manner as in. The results are shown in Table 1.

[0059]

Example 4

[0060]

[Chemical 18]

The organosiloxane diol represented by the above chemical formula 18 was reacted with a 2-fold molar amount of 2-isocyanatoethyl methacrylate in the same manner as in Example 1 and purified to obtain an organosiloxane macromer containing the urethane bond represented by the following chemical formula 19. Obtained.

[0062]

[Chemical 19]

The organosiloxane macromer represented by the chemical formula 19 above, FA-8, n-BA, and MAAED were blended in the same composition as in Example 3, and the same amount of benzyl methyl ketanol was added to prepare a copolymer. Was measured. The results are shown in Table 1.

[0064]

[Embodiment 5] Used in Embodiment 2
Machine siloxane diol-30g (0.00472mo
l) was added to 500 ml of brown equipped with a condenser, thermometer and stirrer.
A colored round-bottomed flask was charged with isophorone diisocyanate.
Nate 2.09 g (0.00944 mol), triethyl
Ruamine 0.01 g and tetrahydrofuran were added to add N
₂React at 60 ° C for about 5 hours with stirring in the atmosphere
It was Next, in the reaction liquid, 2-hydroxyethyl meta
1.23 g (0.00944 mol) of acrylate and jib
Add 5 drops of chill tin dilaurylate and add N₂atmosphere
The reaction was carried out at 70 ° C. for 5 hours.

After cooling, about 300 ml of tetrahydrofuran
Was added, activated carbon for decolorization and magnesium sulfate for dehydration were added, and the mixture was left for 2 nights. After filtering with a 0.2μ Teflon filter and removing low-boiling substances such as tetrahydrofuran with an evaporator, a viscous transparent liquid of about 23g
was gotten. The structure of this liquid was analyzed by NMR (proton nuclear magnetic resonance spectrum), and as a result, it was confirmed to be the following Chemical formula 20.

55 parts by weight of the organosiloxane macromer represented by the following chemical formula 20 was added to 25 parts by weight of 3FA and 20 parts of n-BA.
Parts by weight, 6 parts by weight of MAA, 4 parts by weight of ED and 0.5 part by weight of benzyl dimethyl ketanol were added and polymerized in the same manner as in Example 1 to obtain a transparent copolymer. The results of measuring the physical properties of the obtained copolymer are shown in Table 1.

[0067]

[Chemical 20]

[0068]

[Comparative Example 1]

[0069]

[Chemical 21]

The organosiloxane macromer represented by the chemical formula 21 and having hydrogen groups at both ends was reacted and purified with 2-isocyanatoethyl methacrylate in the same manner as in Example 1 and the structure was analyzed by NMR. It was confirmed to be the indicated organosiloxane macromer.

[0071]

[Chemical formula 22]

55 parts by weight of the macromer represented by the chemical formula 22 above, 25 parts by weight of 3FA, 20 parts by weight of n-BA, MAA
6 parts by weight, ED 4 parts by weight and benzyl dimethyl ketanol 0.5 parts by weight were added and polymerized in the same manner as in Example 1 to obtain a transparent copolymer. The results of measuring the physical properties of the obtained copolymer are shown in Table 1.

[0073]

[Table 1]

[0074]

INDUSTRIAL APPLICABILITY The contact lens material of the present invention has a stain resistance comparable to that of a polymethylmethacrylate-based hard contact lens, and is excellent in balance of physical properties such as oxygen permeability and mechanical strength. is there.

[Brief description of drawings]

1 is an NMR spectrum diagram of the bifunctional organosiloxane macromer obtained in Example 1. FIG.

Claims (3)

[Claims] 1. A monomer which is capable of copolymerizing one or more difunctional organosiloxane macromers represented by the following chemical formula 1 with the difunctional organosiloxane macromers alone or.
A contact lens material comprising a polymer obtained by polymerizing one or more of the above. [Chemical 1] [Wherein R ₁ is hydrogen or a methyl group, R ₂ , R ₃ , R ₄ and R ₅ are each a hydrocarbon group having 1 to 12 carbon atoms or a trimethylsiloxy group, and Y is a structure represented by the following chemical formula 2. Units (I) and (II), the ratio of structural unit (I): structural unit (II) is 1:10 to 10: 1 and the total number of structural units (I) and (II) is 7 to 200. is there. m
And n are the same or different integers of 1 to 20, and P is an integer of 0 to 20. X is -NHCOO- group or -OOCHN-R ₁₀ -NHCOO- group (R ₁₀ represents a hydrocarbon group having 4 to 13 carbon atoms) is. ] [Chemical 2] 2. The contact lens material according to claim 1, wherein the bifunctional organosiloxane macromer is represented by the following chemical formula 3. [Chemical 3] [Wherein R ₁ is hydrogen or a methyl group, Y is composed of structural units (I ′) and (II ′) shown in the following chemical formula 4, and the ratio of structural unit (I ′): structural unit (II ″) is The total number of structural units (I ′) and (II ″) is from 1:10 to 10: 1 and 7 to 200. m and n are the same or different integers of 1 to 20, and P is an integer of 0 to 20. X
Is -NHCOO- group or -OOCHN-R ₂ -NHCO
It is an O-group (R ₂ is a hydrocarbon group having 4 to 13 carbon atoms). ] [Chemical 4] 3. One or more difunctional organosiloxane macromers represented by the following chemical formula 5 and selected from fluoroalkyl esters of acrylic acid, fluoroalkyl esters of methacrylic acid, alkyl esters of acrylic acid and alkyl esters of methacrylic acid. A contact lens material made of a copolymer containing one or more main components. [Chemical 5] [Wherein R ₁ is hydrogen or a methyl group, Y is composed of structural units (I ′) and (II ′) shown in the following chemical formula 6, and the ratio of structural unit (I ′): structural unit (II ″) is The total number of structural units (I ′) and (II ′) is 1:10 to 10: 1 and 7 to 200. m and n are the same or different integers of 1 to 20 and P is 0 to 20. Is an integer of X.
Is -NHCOO- group or -OOCHN-R ₂ -NHCO
It is an O-group (R ₂ is a hydrocarbon group having 4 to 13 carbon atoms). ] [Chemical 6]