JP2000169526A - Polymerizable monomer composition, copolymer, and contact lens - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a monomer composition which comprises a phosphorylcholine-like-group-containing(meth)acrylate (A), a polymerizable hydroxyl-containing fluoro monomer (B), and other polymerizable monomers (C) in a specified ratio, is uniform and transparent because of the improved solubility of component A, and gives a polymer having desirable oxygen permeability and staining resistance when polymerized. SOLUTION: This composition comprises 1-25 wt.% component A, 5-70 wt.% component B, and 20-94 wt.% component C. It is desirable that component A is a compound of formula I and component B is a compound of formula II. It is desirable in this composition that component C comprises 20-60 wt.% monofunctional monomers other than components A and B and 0.1-10 wt.% polyfunctional(meth)acrylate. In the formulae, R1, R3, and R4 are each H or methyl; R2 is (CH2CHR3)n (wherein n is 1-8); m is 2-4; X is -CH(OH)CH2- or -CH(CH2OH)-; h is an integer of 0-3; and Rf is at least either of 2-21F linear and branched 1-10C fluoroalkyl groups.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymerizable monomer composition suitable for lenses and a copolymer thereof. Further, the present invention relates to a contact lens using the copolymer. More specifically, a composition of a phosphorylcholine-like group-containing (meth) acrylate, a hydroxyl group-containing fluorine (meth) acrylate, and other monofunctional monomers suitable for a contact lens having excellent hydrophilicity, stain resistance, and oxygen permeability, and a combination thereof. The present invention relates to polymers and contact lenses having both stain resistance and oxygen permeability.

[0002]

2. Description of the Related Art Contact lenses are hard and soft.
Roughly divided into two types. Hard contact lenses include oxygen permeable hard contact lenses, and soft contact lenses include hydrophilic soft contact lenses, for example, high and low water content soft contact lenses. However, contact lenses that are currently commercially available can be roughly divided into (a) a hydrophilic soft contact lens made of a hydrophilic polymer such as a polymer of N-vinylpyrrolidone and 2-hydroxyethyl methacrylate and (b) methyl methacrylate. And oxygen-permeable hard contact lenses comprising a copolymer of fluoroalkyl methacrylate and tristrimethoxysilylpropyl methacrylate. Recent soft contact lenses are disclosed in
As disclosed in JP-A-11, a highly water-containing soft contact lens comprising 2-methacryloyloxyethyl phosphorylcholine as a main component and copolymerizing 2-hydroxyethyl methacrylate and ethylene glycol dimethacrylate is disclosed. The soft contact lens,
It has a phosphorylcholine-like group that is a phospholipid-like structure in the molecule, and has high contamination resistance that does not stain proteins and lipids. This soft contact lens is excellent in wearing feeling because it is water-containing. However, this soft contact lens has less oxygen permeability than a commercially available high oxygen permeability hard contact lens, and may not always be able to supply sufficient oxygen necessary for metabolism of corneal tissue.

[0003] On the other hand, oxygen-permeable hard contact lenses are inferior in wearing feeling when worn on eyes as compared with soft contact lenses, but are widely used because they are excellent in vision correction power, durability, and handleability. However, an oxygen-permeable hard contact lens obtained by polymerizing a specific silicon-based methacrylate having a siloxane bond in a molecule and methyl methacrylate has the above-mentioned advantage, but the tear component in the tear during use is used. In particular, when used for a long period of time after being contaminated by lipids, proteins and the like, the feeling of wearing gradually deteriorates, and the feeling of initial wearing is lost. In addition, although there are a lot of commercially available oxygen-permeable hard contact lenses having an oxygen permeability coefficient of 150 or more, as far as the effect on cell division of corneal epithelial cells is observed, the oxygen-permeable hard contact lens has an oxygen permeability coefficient of 80 or more. It is said that it is enough before and after. Various preservatives for improving the wettability to improve the wearing feeling have been proposed (JP-A-5-107512), but a surface-treated lens material (JP-A-7-72430).
Except for the above, there was hardly any material having wettability by itself and solving the feeling of wearing. In addition, Tokuhyo Hei 6-502
In JP-A-200, using 2-methacryloyloxyethyl phosphorylcholine as an ethylenically unsaturated zwitterionic monomer, an ethylenically unsaturated neutral diluent monomer and a crosslinkable ethylenically crosslinkable monomer are used as copolymerizable monomers. A polymerizing contact lens is disclosed. However, this contact lens material is a technique relating to a hydrous soft contact lens, and has a stain resistance, but a non-hydrous hard contact lens having both oxygen permeability and stain resistance properties is specifically described. Has not been disclosed. Specifically, in Example 3 of the above publication, a contact lens material obtained by polymerizing 2-methacryloyloxyethyl phosphorylcholine, methyl methacrylate, and ethylene glycol dimethacrylate is proposed.
A soft contact lens is disclosed, which is a copolymer obtained by polymerizing a monomer mixture mainly composed of methacryloyloxyethyl phosphorylcholine in a solvent solution, and thereafter removing the solvent under reduced pressure and then containing water. This hydrated soft contact lens has improved wettability and stain resistance,
The oxygen permeability coefficient is around 20. Therefore, a specific technique having both oxygen permeability and stain resistance is not disclosed. As a means for solving the above problem, it is sufficient that a monomer component having a phosphorylcholine group is dissolved in methyl methacrylate or silicon-based (meth) acrylate to obtain a cured product, but a monomer having a phosphorylcholine group is extremely hydrophilic. For this reason, it does not dissolve in silicon-based (meth) acrylates such as methyl methacrylate and tris (trimethylsiloxy) silyl methacrylate or fluorine alkyl methacrylate, and a transparent cured product cannot be obtained.

[0004]

SUMMARY OF THE INVENTION A first object of the present invention is to provide a uniform composition in which a monomer component having a phosphorylcholine group is dissolved in a methyl methacrylate or silicon (meth) acrylate-based hydrophobic monomer. It is in. A second object of the present invention is to provide a copolymer obtained by polymerizing the obtained monomer composition. further,
A third object of the present invention is to provide a contact lens which does not stain with components such as proteins and lipids and has both stain resistance and oxygen permeability.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies in view of the above problems, and as a result, have found that the (meth) acrylate having the phosphorylcholine analogous group of the A component and the hydroxyl group-containing fluorine (meth) acrylate of the B component. When a specific amount of is used, the solubility of the component A is improved and the composition becomes uniform and transparent. Further, when a specific amount of the other monofunctional monomer of the component C and the polyfunctional (meth) acrylate of the component D are used, A It has been found that by improving the solubility of the components and polymerizing the monomer composition described above, a contact lens having favorable oxygen permeability and contamination resistance can be obtained for the contact lens, and the present invention has been completed. . The present invention provides the following (1) to
(8). (1) 1 to 25% by weight of a (meth) acrylate containing a phosphorylcholine-like group as an A component, 5 to 70% by weight of a hydroxyl group-containing fluoropolymerizable monomer as a B component, and 20 to 94% by weight of a polymerizable monomer as other components % Polymerizable monomer composition. (2) A copolymer obtained by polymerizing the polymerizable monomer composition described in (1). (3) As a component A, 1 to 25% by weight of a phosphorylcholine-like group-containing (meth) acrylate, as a B component, 5 to 70% by weight of a hydroxyl group-containing fluorine (meth) acrylate, and as a C component, other monofunctional monomer other than the A and B components 20
A contact lens obtained by polymerizing a polymerizable monomer mixture comprising about 90% by weight and 0.1 to 10% by weight of a polyfunctional (meth) acrylate as a D component.

(4) 1 to 20% by weight of a phosphorylcholine-like group-containing (meth) acrylate as the component A, 5 to 40% by weight of a hydroxyl group-containing fluorine (meth) acrylate as the component B, and other components other than the components A and B as the component C A hard contact lens obtained by polymerizing a polymerizable monomer mixture comprising 20 to 75% by weight of a monofunctional monomer and 1 to 10% by weight of a polyfunctional (meth) acrylate as a D component. (5) The A component has the following formula [1]

[0007]

Embedded image

Wherein R ¹ represents a hydrogen atom or a methyl group, and R ² represents (CH ₂ CHR ³ ) n or (CH ₂ CHR)
³ O) nCH ₂ CHR ³ (where R ³ represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 8). Also,
m shows the integer of 2-4. And a (meth) acrylate containing a phosphorylcholine-like group represented by the formula (B), wherein the B component is represented by the following formula [2]:

[0009]

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(Where R ⁴ is a hydrogen atom or a methyl group, X is —CH (OH) CH ₂ — or —CH (CH ₂
OH)-, h is 0 or an integer of 1 to 3, Rf is 2
It is a linear or branched C1-C10 fluoroalkyl group having -21 fluorine atoms. The contact lens according to the above (3), wherein the contact lens is a hydroxyl group-containing fluorine (meth) acrylate represented by the formula: (6) The A component has the following formula [1]

[0011]

Embedded image

Wherein R ¹ represents a hydrogen atom or a methyl group, and R ² represents (CH ₂ CHR ³ ) n or (CH ₂ CHR)
³ O) nCH ₂ CHR ³ (where R ³ represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 8). Also,
m shows the integer of 2-4. And a (meth) acrylate containing a phosphorylcholine-like group represented by the formula (B), wherein the B component is represented by the following formula [2]:

[0013]

Embedded image

(Where R ⁴ is a hydrogen atom or a methyl group, X is —CH (OH) CH ₂ — or —CH (CH ₂ O
H)-, h is 0 or an integer of 1 to 3, Rf is 2 to
It is a linear or branched C1-C10 fluoroalkyl group having 21 fluorine atoms. The hard contact lens according to the above (4), which is a hydroxyl group-containing fluorine (meth) acrylate represented by the following formula:

(7) A polymerizable monomer comprising 1 to 25% by weight of component A, 5 to 70% by weight of component B, 20 to 90% by weight of component C and 0.1 to 10% by weight of component D The mixture is polymerized, and the C component is one or more monomers selected from the following a, and the D component is one or more monomers selected from the following b: 3) The contact lens according to the above. a; tris (trimethylsiloxy) silylpropyl (meth) acrylate; fluorinated (meth) acrylate containing no hydroxyl group of trifluoroethyl (meth) acrylate and hexafluoroisopropyl (meth) acrylate; methyl (meth) acrylate and ethyl (meth) acrylate )
Alkyl (meth) acrylate of acrylate; 2-hydroxyethyl (meth) acrylate, 2,3-dihydroxyethyl (meth) acrylate, N-vinyl-2-
Pyrrolidone, N, N-dimethylacrylamide. b; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate and trimethylolpropane tri (meth) acrylate.

(8) 1 to 20% by weight of component A, 5% of component B
A polymerizable monomer mixture comprising -40% by weight, 20-75% by weight of component C and 1-10% by weight of component D, wherein the component C is at least one selected from the following a: And the D component is 1 selected from the following b:
The hard contact lens according to the above (4), which is at least one kind of monomer. a; tris (trimethylsiloxy) silylpropyl (meth) acrylate; fluorinated (meth) acrylate containing no hydroxyl group of trifluoroethyl (meth) acrylate and hexafluoroisopropyl (meth) acrylate; methyl (meth) acrylate and ethyl (meth) acrylate )
Acrylate alkyl (meth) acrylate. b; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate and trimethylolpropane tri (meth) acrylate.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. In the present invention, a contact lens means both a hard contact lens and a soft contact lens unless otherwise specified. The polymerizable monomer composition in the present invention is a composition containing a polymerizable monomer of the component A and the component B as a main component, and is suitable for lenses, particularly for contact lenses. Further, the copolymer of the present invention refers to a copolymer obtained by polymerizing the above polymerizable monomer composition with a polymerization initiator. A used in the present invention
The component (phosphorylcholine-like group-containing (meth) acrylate (hereinafter abbreviated as PC monomer 1) is represented by the following formula [1]
(Meth) acrylate represented by

[0018]

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In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents (CH ₂ CHR ³ ) n or (CH ₂ CH
R ³ O) nCH ₂ CHR ³ (where R ³ represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 8). M represents an integer of 2 to 4. Specific examples of the component A include, for example, 2- (meth) acryloyloxyethyl-2 ′-(trimethylammonio) ethyl phosphate and 2- (meth) acryloyloxypropyl-2 ′-(trimethylammonium) in which m is 2. E) Ethyl phosphate, 4- (meth) acryloyloxybutyl-2′-
(Trimethylammonio) ethyl phosphate, 2-
(Meth) acryloyloxyethoxyethyl-2'-
(Trimethylammonio) ethyl phosphate, 2-
(Meth) acryloyloxydiethoxyethyl-2'-
(Trimethylammonio) ethyl phosphate and the like.

Further, 2- (meth) acryloyloxyethyl-2 '-(trimethylammonio) wherein m is 3
Propyl phosphate, 2- (meth) acryloyloxyethyl-2 ′-(trimethylammonio) propyl phosphate, 4- (meth) acryloyloxybutyl-
2 '-(trimethylammonio) propyl phosphate, 2- (meth) acryloyloxyethoxyethyl-
Examples thereof include 2 '-(trimethylammonio) propyl phosphate and 2- (meth) acryloyloxydiethoxyethyl-2'-(trimethylammonio) propyl phosphate. And m is 4.
(Meth) acryloyloxyethyl-2 '-(trimethylammonio) butyl phosphate, 2- (meth) acryloyloxyethyl-2'-(trimethylammonio) butyl phosphate, 4- (meth) acryloyloxybutyl-2'- (Trimethylammonio) butyl phosphate, 2- (meth) acryloyloxyethoxyethyl-2 ′-(trimethylammonio) butylphosphate, 2- (meth) acryloyloxydiethoxyethyl-2 ′-(trimethylammonio) butylphosphate And the like. 2-Methacryloyloxyethyl-2 '-(trimethylammonio) from availability
Ethyl phosphate (hereinafter abbreviated to MPC) is preferably mentioned. These PC monomers 1 of the component A may be used alone or in combination of two or more. Such a PC monomer 1 can impart hydrophilicity and stain resistance to the obtained contact lens. P
The amount of the C monomer 1 is 1 to 25% by weight, preferably 1 to 25% by weight.
20% by weight. If the content is less than 1% by weight, PC of the component A
Since the effect based on the monomer 1 is hardly exhibited, the stain resistance cannot be imparted. When the amount of the PC monomer 1 is more than 25% by weight, the resin does not dissolve in the monomer during the curing and separates, or separates into a polymer and loses transparency, so that a transparent and homogeneous cured product is obtained. Absent.

As the hydroxyl group-containing fluoropolymerizable monomer of the component B used in the present invention, a hydroxyl group-containing (meth) acrylate (hereinafter abbreviated as F-OH monomer 2) is used, and the following formula [2] (Meth) acrylate represented by

[0022]

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Here, R ⁴ is a hydrogen atom or a methyl group,
X is -CH (OH) CH ₂ - or -CH (CH ₂ OH)
-, H is 0 or an integer of 1 to 3, Rf is 2 to 21
A linear or branched fluoroalkyl group having 1 to 10 carbon atoms and having 1 to 10 carbon atoms.

As a specific example of the component B, for example,
(Perfluoro-3-methylbutyl) -2-hydroxypropyl (meth) acrylate, 3- (perfluoro-
5-methylhexyl) -2-hydroxypropyl (meth) acrylate, 3- (perfluoro-7-methyloctyl) -2-hydroxypropyl (meth) acrylate, 3- (perfluoro-8-methyldecyl) -2-hydroxypropyl ( (Meth) acrylate, 3-perfluorobutyl-2-hydroxypropyl (meth) acrylate, 3-perfluorohexyl-2-hydroxypropyl (meth) acrylate, 3-perfluorooctyl-2-hydroxypropyl (meth) acrylate, 2-
(Perfluoro-3-methylbutyl) -3-hydroxypropyl (meth) acrylate, 2- (perfluoro-
5-methylhexyl) -3-hydroxypropyl (meth) acrylate, 2- (perfluoro-7-methyloctyl) -3-hydroxypropyl (meth) acrylate, 2- (perfluoro-8-methyldecyl) -3-hydroxypropyl ( (Meth) acrylate, 2-perfluorobutyl-3-hydroxypropyl (meth) acrylate, 2-perfluorohexyl-3-hydroxypropyl (meth) acrylate, 2-perfluorooctyl-3-hydroxypropyl (meth) acrylate, and the like. The F-OH monomer 2 may be used alone or in combination of two or more. Such F-
The OH monomer 2 dissolves the PC monomer 1 and makes other (meth) acrylates compatible, for example.

The amount of the F-OH monomer 2 is 5 to 70% by weight, preferably 10 to 60% by weight. If the compounding amount of the hydroxyl group-containing fluorine (meth) acrylate of the component B is less than 5% by weight, the (meth) acrylate of the component A cannot be dissolved in a sufficient amount, and if it is more than 70% by weight, the contact lens obtained by polymerization is mechanical. Brittle and difficult to handle, and easily broken. Further, the F-OH monomer 2 is made of PC as described above.
In addition to compatibilizing monomer 1 with other monomers, it also contributes to imparting oxygen permeability to the polymerized contact lens. Other components are 20 to 94% by weight, preferably 40% by weight.
~ 90% by weight.

The C component used in the present invention includes the components A and B described above.
It is a monofunctional monomer copolymerizable with the component (hereinafter abbreviated as monomer 3), and specific examples thereof include (a) a styrene-based monomer, (b) an alkyl (meth) acrylate, and (c) ) Fluorine-containing alkyl (meth) acrylate containing no hydroxyl group, (d) silicon-containing (meth) acrylate,
(E) Vinyl ether monomers and (f) hydrophilic monomers. Examples of the styrene monomer (a) include styrene and methylstyrene.
Examples of the alkyl (meth) acrylate (b) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.
(C) Fluorine-containing alkyl (meth) containing no hydroxyl group
Examples of the acrylate include trifluoroethyl (meth) acrylate and hexafluoroisopropyl (meth) acrylate. (D) Examples of the silicon-containing (meth) acrylate include tristrimethoxysilyl (meth) acrylate. Examples of the vinyl ether-based monomer (e) include ethyl vinyl ether and n-butyl vinyl ether. As the hydrophilic monomer (f), for example, 2-hydroxyethyl (meth) acrylate, 2,2
3-dihydroxypropyl (meth) acrylate, N-
Vinylpyrrolidone, N, N-dimethylacrylamide and the like. These monomers 3 may be used alone or as a mixture of two or more. Among monomers 3, fluorine-containing alkyl (meth) containing no hydroxyl group
Acrylate, silicon-containing (meth) acrylate,
It is mentioned as a particularly preferred monomer in terms of imparting oxygen permeability to the obtained contact lens. N, N-dimethylacrylamide and N-vinylpyrrolidone are particularly preferred monomers from the viewpoint of imparting hydrophilicity to the obtained contact lens. Also, methyl methacrylate is mentioned as a particularly preferred monomer in terms of imparting appropriate hardness and mechanical strength to the processing of the obtained contact lens.

The component D used in the present invention is a polyfunctional (meth) acrylate (hereinafter abbreviated as polyfunctional monomer 4) copolymerizable with the above-mentioned components A, B and C, and specific examples thereof are as follows. Are bifunctional (meth) acrylates such as ethylene glycol di (meth) acrylate, diethylene glycol (meth) acrylate, triethylene glycol (meth) acrylate, and neopentyl glycol (meth) acrylate; trimethylolpropane tri (meth) acrylate and the like And a trifunctional (meth) acrylate. The polyfunctional monomers 4 may be used alone or in combination of two or more. The compounding amount of the component D is 0.1 to 10% by weight, preferably 1 to 10% by weight for hard contact lenses, and 0.1 to 1% by weight for soft contact lenses. These polyfunctional monomers 4
Is cross-linked by copolymerization and imparts appropriate hardness and mechanical strength to processing of the obtained contact lens.

The polymerizable monomer composition of the present invention can be made into a uniform solution by blending the above-mentioned A, B and other monomers in a predetermined amount. Furthermore, the copolymer of the present invention is a transparent copolymer obtained by polymerizing the polymerizable monomer composition with a polymerization initiator described below.

The contact lens of the present invention is characterized in that:
It can be obtained by copolymerizing raw materials of the components B, C and D, and depending on the monomer type and amount of the components A, B and C or the amount of the component D, a water-containing or non-water-containing contact lens can be obtained. The contact lens of the present invention has good wettability irrespective of water content or non-water content, and is excellent in wearing feeling. The stain-resistant and oxygen-permeable contact lens of the present invention may contain a coloring agent such as a pigment, a dye, a pigment, or an ultraviolet absorber, as long as the effects of the present invention are not impaired, in addition to the components described above. Good. Specific examples of pigments, dyes, pigments and the like include, for example, Blue No. 201, Blue No. 204, Purple 20
No. 1, Red No. 404, Green No. 202, Blue No. 404 and the like. Further, as a specific example of the ultraviolet absorber, 2
Preferred are-(2-hydroxy) benzotriazole, 2- (hydroxy) benzophenone and the like.

The polymerization method for producing a contact lens according to the present invention 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, for example, benzoyl peroxide, lauroyl peroxide, diisopropyl peroxydicarbonate,
t-butylperoxy-2-ethylhexanoate, t
-Butylperoxypivalate, t-butylperoxydiisobutyrate, azobisisobutyronitrile, and azobisdimethylvaleronitrile can be used. The amount of the polymerization initiator to be used is generally 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of all monomers. In order to produce the contact lens of the present invention, for example, (a) the raw material monomer is copolymerized in a suitable container such as a test tube based on the radical polymerization conditions, After obtaining, mechanical processing such as cutting and polishing, [b]
A method in which the raw material monomer and the polymerization initiator are injected into a predetermined mold and a contact lens is directly molded by mold polymerization, [c] a method of casting while heating or irradiating light, or [d] a radical polymerization method in advance After producing the polymer by the method described above, the polymer can be obtained by dissolving the polymer in an appropriate solvent and removing the solvent by a casting method.

[0031]

According to the first invention, there is provided a (meth) acrylate having a phospholipid-like structure having a specific structure of the above-mentioned component A;
A polymerizable monomer composition that can be formed into a uniform solution without separation or precipitation by mixing a predetermined amount of a specific hydroxyl group-containing fluorine monomer as a component and further other monomers. Further, a second invention is a transparent copolymer obtained by polymerizing the polymerizable monomer composition with a polymerization initiator. This transparent copolymer can be obtained as a round bar (rod type) or button type, and then further processed into a lens,
Particularly suitable for contact lenses. Still further, a third invention is a contact lens comprising the above-mentioned copolymer, wherein the contact lens obtained by curing the polymerizable monomer composition has hydrophilicity, stain resistance, It is an excellent contact lens having both stain resistance and oxygen permeability properties by maintaining and improving the oxygen permeability by the components and the strength and processability by the other components. In particular, it is a contact lens that has a stain-resistant effect that does not stain proteins and lipids in tears.

[0032]

The present invention will be described below in more detail with reference to specific examples, but the present invention is not limited to these examples. Example 1 2-methacryloyloxyethyl-2 ′-(trimethylammonio) ethyl phosphate (MEP) 5 parts by weight,
30 parts by weight of 3- (perfluoro-3-methylbutyl) -2-hydroxypropyl methacrylate (FMBM) were mixed and dissolved. The obtained mixture is further mixed with tris (trimethylsiloxy) silylpropyl methacrylate (SiM
A) When dissolved in 65 parts by weight, an optically uniform and transparent compound was obtained.

Example 2 Starting monomers shown in Table 1, namely 5 parts by weight of MEP, FM
30 parts by weight of BM, 30 parts by weight of SiMA, 30 parts by weight of methyl methacrylate (MMA), 5 parts by weight of ethylene glycol dimethacrylate (EDMA), and 0.2 parts by weight of azobisisobutyronitrile (AIBN) are poured into a test tube glass tube. After the system was replaced with nitrogen, the system was sealed and heat-cured. Heating to 50-100 ° C in a thermostat,
The temperature was raised over 50 hours. After the polymerization was completed, the cured product was taken out of the mold, and the obtained polymer was colorless and transparent. A test piece having a predetermined shape was prepared from the obtained polymer, and each physical property shown below was evaluated. The results are shown in Table 1.

1. Oxygen permeability; using a Kaken-ken type film oxygen transmission measuring device (K-316, manufactured by Rika Seiki Kogyo)
The oxygen permeability coefficient in physiological saline at 35 ° C. was determined. 2. Shore hardness; Shore hardness tester (manufactured by Asker, D)
Was used to measure the surface hardness of the test piece according to JIS K 7215. 3. Contact angle: The contact angle of the obtained test piece was measured using a contact angle meter (CA-A manufactured by Kyowa Kagaku Co., Ltd.). 4. Evaluation of protein adsorption amount; albumin 0.39% (W /
V), the test piece was immersed in a physiological saline solution containing 0.17% (W / V) of lysozyme and 0.105% (W / V) of γ-globulin, and then lightly rinsed with physiological saline, 1% by weight.
The protein was peeled off from the test piece using a sodium dodecyl sulfate surfactant aqueous solution, a reagent for protein quantification was injected into the solution, and the protein adsorbed on the contact lens was quantified. 4. Protein adsorption amount (μg) = Amount of protein measured after exfoliating protein Evaluation of lipid absorption: A test piece was placed in a sample tube containing 20 g of oleic acid, placed in a thermostat at 60 ° C. for 24 hours, and the absorption of oleic acid was measured. Calculation formula: Oleic acid absorption (%) = {(lens weight after absorption−lens weight before absorption) / lens weight after absorption} × 100

Examples 3 to 11 Polymerization was performed using the compositions shown in Tables 1 and 2 in the same manner as in Example 2 to obtain polymers. Thereafter, the same treatment was performed to obtain a contact lens. The measured results are shown in Tables 1 and 2.

Comparative Example 1 5 parts by weight of MEP was added and dissolved in 95 parts by weight of SiMA, but a transparent compound was not obtained. In addition, 60
A clear formulation was not obtained when placed in an oven and stirred.

Comparative Example 2 45 parts by weight of SiMA, 20 parts by weight of trifluoroethyl methacrylate (3FMA), 25 parts by weight of MMA, 5 parts by weight of methacrylic acid (MA), 5 parts by weight of EDMA, AIBN
0.2 part by weight was poured into a test tubular glass tube, and after the inside of the system was replaced with nitrogen, sealing was performed and heat curing was performed. Heating is
The temperature was raised to 50 to 100 ° C. in a thermostat over 50 hours. After the polymerization was completed, the cured product was taken out of the mold, and the obtained polymer was colorless and transparent. A test piece having a predetermined shape was prepared from the obtained polymer, and each physical property was evaluated in the same manner as described above. Table 3 shows the measurement results.

Comparative Examples 3 to 5 Polymerization was performed in the same manner as in Comparative Example 2 with the composition shown in Table 3 to obtain a polymer. Thereafter, the same treatment was performed to obtain a contact lens. Hereinafter, each physical property was evaluated in the same manner as described above. Table 3 shows the measurement results.

Comparative Example 6 A solution containing 50 parts by weight of ethanol and 50 parts by weight of MMA contained 50 parts by weight of MEP, 2 parts by weight of EDMA, and 0.2 parts of AIBN.
A part by weight was melted, poured into a test tubular glass tube, and the inside of the system was replaced with nitrogen, followed by sealing and heat curing. The heating was performed by raising the temperature to 50 to 100 ° C. in a constant temperature bath over 50 hours. After the polymerization was completed, the cured product was taken out of the mold and heated in a vacuum drier at 80 ° C. for 48 hours to remove ethanol to obtain a cured product. Hereinafter, each physical property was evaluated in the same manner as described above. Table 3 shows the measurement results.

Example 12 10 parts by weight of the starting monomers shown in Table 4, ie, MEP,
49.5 parts by weight of MBM, 30 parts by weight of SiMA, N, N-
Dimethylacrylamide (DMAA) 10 parts by weight, ED
0.5 parts by weight of MA and 0.2 parts by weight of AIBN were injected into a test tubular glass tube, and after purging with nitrogen in the system, sealing was performed.
Heat curing was performed. Heating is 50 ~ 100 ℃ in a thermostat
The temperature was raised over 50 hours. The obtained polymer was colorless and transparent. A test piece having a predetermined shape was prepared from the obtained polymer, and each physical property shown in Table 4 was evaluated. Table 4 shows the results.

Among the physical properties shown in Table 4, the water content was determined as follows. Water content: After immersing in 0.9% by weight of physiological saline to obtain a saturated water content, the weight was measured and calculated by the following equation. Water content (%) = {(W ₁ −W ₂ ) / W ₁ } × 100 where W ₁ : weight at the time of saturated water content, and W ₂ : dry weight.

Examples 13 to 21 Polymerization was carried out in the same manner as in Example 13 using the composition shown in Tables 4 and 5 to obtain polymers. Thereafter, the same treatment was performed to obtain a contact lens. Tables 4 and 5 show the measured results.

Comparative Example 7 The starting monomers shown in Table 6, namely 49.5 parts by weight of FMBM, 20 parts by weight of N-vinylpyrrolidone (NVP), Si
MA 30 parts by weight, EDMA 0.5 parts by weight, AIBN 0.
Two parts by weight were poured into a test tubular glass tube, and after the inside of the system was replaced with nitrogen, the system was sealed and heat-cured. The heating was performed by raising the temperature to 50 to 100 ° C. in a constant temperature bath over 50 hours. The obtained polymer was colorless and transparent. A test piece having a predetermined shape was prepared from the obtained polymer, and each physical property shown in Table 6 was evaluated. Table 6 shows the results.

Comparative Examples 8 to 10 Polymerization was performed in the same manner as in Comparative Example 7 with the composition shown in Table 6 to obtain a polymer. Thereafter, the same treatment was performed to obtain a contact lens. Hereinafter, each physical property was evaluated in the same manner as described above. Table 6 shows the measurement results.

[0045]

[Table 1]

[0046]

[Table 2]

[0047]

[Table 3]

[0048]

[Table 4]

[0049]

[Table 5]

[0050]

[Table 6]

The abbreviations used in Tables 1 to 6 are as follows. MEP; 2-methacryloyloxyethyl-2- (trimethylammonio) ethyl phosphate, MPP; 2-methacryloyloxypropyl-2- (trimethylammonio) ethyl phosphate, MEEP; 2-methacryloyloxydiethoxy-2-
(Trimethylammonio) ethyl phosphate, FMBM; 3- (perfluoro-3-methylbutyl) -2
-Hydroxypropyl methacrylate, FBM; 3-Perfluorobutyl-2-hydroxypropyl methacrylate, FHM; 3-Perfluorohexyl-2-hydroxypropyl methacrylate, MMA; Methyl methacrylate, EMA; Ethyl methacrylate, MA; Methacrylic acid, HEMA 2-hydroxyethyl methacrylate, NVP; N-vinylpyrrolidone DMAA; N, N-dimethylacrylamide, 3FMA; trifluoroethyl methacrylate, 6FMA; hexafluoroisopropyl methacrylate, SiMA; tris (trimethylsiloxy) silylpropyl methacrylate, EDMA; ethylene Glycol dimethacrylate, TMPT; trimethylolpropane triacrylate.

<Evaluation symbol of transparency of blended composition> Transparency of blended composition: 組成 indicates a monomer composition and a transparent composition was obtained. × indicates a monomer composition and a transparent composition was not obtained. <Evaluation Symbol of Transparency of Cured Product> Transparency of cured product; は indicates a monomer composition and a transparent cured product was obtained after polymerization. × indicates a monomer composition, and a transparent cured product was not obtained after polymerization. <Symbol of transparency of cured product after hydration> Transparency of cured product after hydration: は when cured product was hydrated, maintained transparency even after hydration. × indicates when the cured product is hydrated.
The transparency was not maintained even after hydration. The unit of measurement is an oxygen permeability Dk value = 10 ⁻¹¹ ml.
O ₂ · cm / cm ² · sec · mmHg, Shore hardness =
No unit, contact angle = degree, protein adsorption = μg, lipid absorption =
%, Water content =%.

From the above results, it can be seen that the polymerizable monomer composition of the present invention is uniform and transparent. In addition, it can be seen that the contact lenses of Examples obtained by polymerizing the polymerizable monomer composition are excellent in both oxygen permeability and anti-staining properties as compared with Comparative Examples.

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[Procedure amendment]

[Submission date] January 13, 2000 (2000.1.1)
3)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

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[Claims]

Embedded image In the formula, R ¹ represents a hydrogen atom or a methyl group; R ² represents (CH ₂ CHR ³ ) n or (CH ₂ CHR ³ O) nCH ₂
CHR ³ (where R ³ represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 8). M represents an integer of 2 to 4. And a (meth) acrylate containing a phosphorylcholine-like group represented by the formula (B), wherein the B component is represented by the following formula [2]:

Embedded image ｛Where R ⁴ is a hydrogen atom or a methyl group, and X is —CH
(OH) CH ₂ — or —CH (CH ₂ OH) —,
h is an integer of 0 or 1 to 3, and Rf is a linear or branched fluoroalkyl group having 1 to 10 carbon atoms having 2 to 21 fluorine atoms. The contact lens according to claim 3, wherein the contact lens is a hydroxyl group-containing fluorine (meth) acrylate represented by｝.

Embedded image In the formula, R ¹ represents a hydrogen atom or a methyl group; R ² represents (CH ₂ CHR ³ ) n or (CH ₂ CHR ³ O) nCH ₂
CHR ³ (where R ³ represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 8). M represents an integer of 2 to 4. And a (meth) acrylate containing a phosphorylcholine-like group represented by the formula (B), wherein the B component is represented by the following formula [2]:

Embedded image ｛Where R ⁴ is a hydrogen atom or a methyl group, and X is —CH
(OH) CH ₂ — or —CH (CH ₂ OH) —,
h is an integer of 0 or 1 to 3, and Rf is a linear or branched fluoroalkyl group having 1 to 10 carbon atoms having 2 to 21 fluorine atoms. The hard contact lens according to claim 4, which is a hydroxyl group-containing fluorine (meth) acrylate represented by｝.

[Procedure amendment 2]

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[0009]

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[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0013

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[0013]

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[Procedure amendment 4]

[Document name to be amended] Statement

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 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Norio Nakabayashi 5-6-20 Koganehara, Matsudo-shi, Chiba (72) Inventor Kazuhiko Ishihara 3-16-37, Josuihoncho, Kodaira-shi, Tokyo

Claims (8)

[Claims] 1 to 25% by weight of a (meth) acrylate containing a phosphorylcholine-like group as an A component, 5 to 70% by weight of a fluoropolymerizable monomer having a hydroxyl group as a B component, and 20 to 20% by weight of a polymerizable monomer as another component. A polymerizable monomer composition comprising 94% by weight. 2. A copolymer obtained by polymerizing the polymerizable monomer composition according to claim 1. 3. A (meth) acrylate containing a phosphorylcholine-like group in an amount of 1 to 25% by weight as a component A, 5-70% by weight of a hydroxyl group-containing fluorinated (meth) acrylate as a B component, and a component other than the A and B components as a C component. 20 to 90% by weight of functional monomer and polyfunctional (meth) as D component
A contact lens obtained by polymerizing a polymerizable monomer mixture comprising 0.1 to 10% by weight of acrylate. 4. A component (A) having a phosphorylcholine-containing group-containing (meth) acrylate in an amount of 1 to 20% by weight, a component B having a hydroxyl group-containing fluorine (meth) acrylate in an amount of 5 to 40% by weight; 20 to 75% by weight of functional monomer and polyfunctional (meth) as D component
A hard contact lens obtained by polymerizing a polymerizable monomer mixture comprising 1 to 10% by weight of acrylate. 5. The composition according to claim 1, wherein the component A is represented by the following formula [1]: In the formula, R ¹ represents a hydrogen atom or a methyl group; R ² represents (CH ₂ CHR ³ ) n or (CH ₂ CHR ³ O) nCH ₂
CHR ³ (where R ³ represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 8). M represents an integer of 2 to 4. A (meth) acrylate containing a phosphorylcholine-like group represented by the formula (1), wherein the component B is represented by the following formula [2]: ｛Where R ⁴ is a hydrogen atom or a methyl group, and X is —CH
(OH) CH ₂ — or —CH (CH ₂ OH) —,
h is an integer of 0 or 1 to 3, and Rf is a linear or branched fluoroalkyl group having 1 to 10 carbon atoms having 2 to 21 fluorine atoms. The contact lens according to claim 3, wherein the contact lens is a hydroxyl group-containing fluorine (meth) acrylate represented by｝. 6. A component having the following formula [1]: In the formula, R ¹ represents a hydrogen atom or a methyl group; R ² represents (CH ₂ CHR ³ ) n or (CH ₂ CHR ³ O) nCH ₂
CHR ³ (where R ³ represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 8). M represents an integer of 2 to 4. A (meth) acrylate containing a phosphorylcholine analogous group represented by｝, wherein the B component has the following formula [2] ｛Where R ⁴ is a hydrogen atom or a methyl group, and X is —CH
(OH) CH ₂ — or —CH (CH ₂ OH) —,
h is an integer of 0 or 1 to 3, and Rf is a linear or branched fluoroalkyl group having 1 to 10 carbon atoms having 2 to 21 fluorine atoms. The hard contact lens according to claim 4, which is a hydroxyl group-containing fluorine (meth) acrylate represented by｝. 7. Component A comprises 1 to 25% by weight and component B comprises 5 to 5% by weight.
A polymerizable monomer mixture comprising 70% by weight, C-component of 20 to 90% by weight, and D-component of 0.1 to 10% by weight is polymerized, and the C-component is selected from the following a. The contact lens according to claim 3, wherein the monomer is the above monomer, and the D component is at least one monomer selected from the following b. a; tris (trimethylsiloxy) silylpropyl (meth) acrylate; fluorinated (meth) acrylate containing no hydroxyl group of trifluoroethyl (meth) acrylate and hexafluoroisopropyl (meth) acrylate; methyl (meth) acrylate and ethyl (meth) acrylate )
Alkyl (meth) acrylate of acrylate; 2-hydroxyethyl (meth) acrylate, 2,3-dihydroxyethyl (meth) acrylate, N-vinyl-2-
Pyrrolidone, N, N-dimethylacrylamide. b; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate and trimethylolpropane tri (meth) acrylate. 8. The composition according to claim 1, wherein the component A is 1 to 20% by weight, and the component B is 5 to 20% by weight.
A polymerizable monomer mixture comprising 40% by weight, 20 to 75% by weight of the C component and 1 to 10% by weight of the D component is polymerized, and the C component is at least one selected from the following a. The hard contact lens according to claim 4, which is a monomer, and wherein the D component is at least one monomer selected from b below. a; tris (trimethylsiloxy) silylpropyl (meth) acrylate; fluorinated (meth) acrylate containing no hydroxyl group of trifluoroethyl (meth) acrylate and hexafluoroisopropyl (meth) acrylate; methyl (meth) acrylate and ethyl (meth) acrylate )
Acrylate alkyl (meth) acrylate. b; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate and trimethylolpropane tri (meth) acrylate.