JPH0632855A - Gas-permeable polymeric material - Google Patents

Abstract

PURPOSE:To obtain the subject material, having a high oxygen permeability coefficient, excellent in optical characteristics, fouling resistance, shape holding properties, impact resistance and after tack properties and useful as lenses, etc., by copolymerizing a specific organosiloxane monomer with a monomer copolymerizable with the monomer. CONSTITUTION:The objective material is obtained by copolymerizing (A) preferably 1-99wt.% one or two or more monomers selected from bifunctional organosiloxane monomers expressed by the formula [R is H or methyl; R1 to R6 are alkyl, phenyl, alkylphenyl, fluoroalkyl, etc.; (1) is 1-20; (m) is 1-3; (n) is 1-700] with (B) one or two or more monomers selected from monomers copolymerizable with the component (A) such as alkyl (meth)acrylates.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gas permeable polymer material which can be used as an intraocular lens, a contact lens, and other medical materials.

[0002]

BACKGROUND OF THE INVENTION Contact lenses have traditionally been made of hard materials such as polymethylmethacrylate (PMMA),
It has been proposed to make it from a highly water-containing material such as a polymer such as 2-HEMA or vinylpyrrolidone, or a gas permeable material using a siloxane monomer.

By the way, a material such as PMMA has a problem that it has a low oxygen permeability, is difficult to wear for a long time, and is easily soiled by tear fluid or lipid. Also, 2-HEM
Highly water-containing materials such as A and polymers such as vinylpyrrolidone have low mechanical strength due to high water content, are easily damaged, are inferior in durability, and require boiling sterilization, and are inferior in handling. There is such a problem.

Further, the siloxane-based gas-permeable materials that have been proposed so far have the problems of low mechanical strength, easy breakage, and conspicuous dirt due to lipids and the like. Therefore, not only high oxygen permeability but also high safety such as stain resistance and crack resistance are required, and development of a material having good wearing performance is awaited.

[0005]

DISCLOSURE OF THE INVENTION A first object of the present invention is to provide a material having a very high gas permeability, particularly an oxygen permeability coefficient (DK value). A second object of the present invention is to provide a material having a very high gas permeability, particularly an oxygen permeability coefficient (DK value), excellent optical properties and mechanical properties, and further having excellent stain resistance. Is.

A third object of the present invention is that it can be worn for a long time, has a good wearing feeling, is not easily soiled, is not easily damaged, is easy to handle, and does not stick to the cornea. To provide a lens made of a substantially water-free polymeric material. The above-mentioned object of the present invention has the following general formula:

[0007]

[Chemical 11]

(Wherein R represents a hydrogen atom or a methyl group, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are an alkyl group, a phenyl group, an alkylphenyl group, a fluoroalkyl group or a fluoro group. Alkylphenyl group or trimethylsiloxanyl group (However, alkyl has 1 to 10 carbon atoms.
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are all methyl groups), which may be the same or different. l is an integer of 1 to 20, m is an integer of 1 to 3, and n is an integer of 1 to 700. ) One or more monomers selected from the bifunctional organic siloxane monomer [I] and a monomer copolymerizable with the bifunctional organic siloxane monomer [I]. It is achieved by a gas-permeable polymer material characterized in that it is obtained by copolymerizing at least one kind or two or more kinds of monomers selected from the above.

Further, the following general formula

[0010]

[Chemical 12]

(In the formula, R ₇ represents a hydrogen atom or a methyl group, and R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are an alkyl group, a phenyl group, an alkylphenyl group and a fluoro group. Alkyl group, fluoroalkylphenyl group or trimethylsiloxanyl group (however, the number of carbon atoms of alkyl is 1 to
10), which may be the same or different from each other. Also, R ₁₂ may be X. p is an integer of 0 to 20, q is an integer of 1 to 3, r is an integer of 1 to 700, and u is 1.
Is an integer of -20.

X is the following formula

[0013]

[Chemical 13]

Wherein R ₁₅ represents a hydrogen atom or a methyl group, and R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ represent an alkyl group, a phenyl group, an alkylphenyl group, a fluoroalkyl group or a fluoroalkylphenyl group. Or a trimethylsiloxanyl group (wherein alkyl has 1 to 10 carbon atoms), and these may be the same or different from each other. p
Is an integer of 0 to 20, q is an integer of 1 to 3, w is 0 or 1, and v is an integer of 0 to 700. And one or more monomers selected from the polyfunctional organic siloxane monomer [II] and a monomer copolymerizable with the polyfunctional organic siloxane monomer [II]. It is achieved by a gas-permeable polymer material characterized in that it is obtained by copolymerizing at least one kind or two or more kinds of monomers selected from the above.

Further, the following general formula

[0016]

[Chemical 14]

(In the formula, R represents a hydrogen atom or a methyl group, and R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ are an alkyl group, a phenyl group, an alkylphenyl group, a fluoroalkyl group or a fluoro group. An alkylphenyl group or a trimethylsiloxanyl group (provided that the alkyl has 1 to 10 carbon atoms) is the same or different from each other.
Is an integer of 0 to 20, m is an integer of 1 to 3, n is 1 to 700
Is an integer. ) One or more monomers selected from the bifunctional organosiloxane monomer [III] represented by

[0018]

[Chemical 15]

(In the formula, R ₇ represents a hydrogen atom or a methyl group, and R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are an alkyl group, a phenyl group, an alkylphenyl group and a fluoro group. Alkyl group, fluoroalkylphenyl group or trimethylsiloxanyl group (however, the number of carbon atoms of alkyl is 1 to
10), which may be the same or different from each other. Also, R ₁₂ may be X. p is an integer of 0 to 20, q is an integer of 1 to 3, r is an integer of 1 to 700, and u is 1.
Is an integer of -20.

X is the following formula

[0021]

[Chemical 16]

Wherein R ₁₅ represents a hydrogen atom or a methyl group, and R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ represent an alkyl group, a phenyl group, an alkylphenyl group, a fluoroalkyl group or a fluoroalkylphenyl group. Or a trimethylsiloxanyl group (wherein alkyl has 1 to 10 carbon atoms), and these may be the same or different from each other. p
Is an integer of 0 to 20, q is an integer of 1 to 3, w is 0 or 1, and v is an integer of 0 to 700. ) One or more monomers selected from the polyfunctional organosiloxane monomer [II] represented by the formula (1) and the above-mentioned bifunctional organosiloxane monomer [III] or / and the polyfunctional organosiloxane monomer. A gas-permeable polymer material, characterized in that it is obtained by copolymerizing at least one monomer or two or more monomers selected from copolymerizable monomers with the monomer [II]. Achieved by

Further, the following general formula

[0024]

[Chemical 17]

(In the formula, R represents a hydrogen atom or a methyl group, and R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ are an alkyl group, a phenyl group, an alkylphenyl group, a fluoroalkyl group or a fluoro group. An alkylphenyl group or a trimethylsiloxanyl group (provided that the alkyl has 1 to 10 carbon atoms) is the same or different from each other.
Is an integer of 0 to 20, m is an integer of 1 to 3, n is 1 to 700
Is an integer. ) One or more monomers selected from the bifunctional organosiloxane monomer [III] represented by

[0026]

[Chemical 18]

(In the formula, R ₇ represents a hydrogen atom or a methyl group, and R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are an alkyl group, a phenyl group, an alkylphenyl group or a fluoro group. Alkyl group, fluoroalkylphenyl group or trimethylsiloxanyl group (however, the number of carbon atoms of alkyl is 1 to
10), which may be the same or different from each other. Also, R ₁₂ may be X. p is an integer of 0 to 20, q is an integer of 1 to 3, r is an integer of 1 to 700, and u is 1.
Is an integer of -20.

X is the following formula

[0029]

[Chemical 19]

Wherein R ₁₅ represents a hydrogen atom or a methyl group, and R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ represent an alkyl group, a phenyl group, an alkylphenyl group, a fluoroalkyl group or a fluoroalkylphenyl group. Or a trimethylsiloxanyl group (wherein alkyl has 1 to 10 carbon atoms), and these may be the same or different from each other. p
Is an integer of 0 to 20, q is an integer of 1 to 3, w is 0 or 1, and v is an integer of 0 to 700. ) One or more monomers selected from the polyfunctional organic siloxane monomers [II] represented by the following general formula:

[0031]

[Chemical 20]

(In the formula, R ₂₆ represents a hydrogen atom or a methyl group, and R ₂₇ , R ₂₈ , R ₂₉ , R ₃₀ , R ₃₁ , R ₃₃ and R ₃₄ are a methyl group, a phenyl group or a carbon number of 1 to 10). R ₃₂ and R ₃₅ do not represent a group (bonding chain connecting the r ′ portion and the u ′ portion), or a methyl group, a phenyl group or a fluoroalkyl group having 1 to 10 carbon atoms. Show.
p ′ is an integer of 0 to 20, q ′ is 1, 2 or 3, t ′ and u ′ are 0, 1 or 2, and r ′ is 0 or 1. ) One or more monomers selected from the organosiloxane monomers [IV] represented by the formula (1), and one or more monomers selected from (meth) acrylic acid fluoroalkyl esters Gas, high gas-permeability, characterized in that at least one monomer selected from the group consisting of (meth) acrylic acid alkyl esters and a hydrophilic monomer are used and copolymerized. Achieved by molecular materials.

The proportion of the bifunctional organic siloxane monomer [I] used in the gas-permeable polymer material of the first invention is 1 to 99% by weight, preferably 3 to 90% by weight. And a polyfunctional organosiloxane monomer [II] in the gas-permeable polymer material according to the second invention.
It is preferable that the use ratio of 1 to 99% by weight, desirably 3 to 90% by weight, and the bifunctional organosiloxane monomer [I in the gas-permeable polymer material of the third invention [I
II] and the polyfunctional organosiloxane monomer [II] are used in an amount of 1 to 99% by weight, and more preferably 3 to 90% by weight.
It is particularly preferable that the bifunctional organic siloxane monomer [III] is 3 to 75% by weight and the polyfunctional organic siloxane monomer [II] is 3 to 80% by weight, and The use ratio of the bifunctional organic siloxane monomer [III] in the gas permeable polymer material in the fourth invention is 3 to 80% by weight, preferably 5 to 75% by weight, and the polyfunctional organic siloxane monomer [III] is used. II] is used in a proportion of 3 to 80
%, Preferably 5 to 70% by weight, the proportion of the organosiloxane monomer [IV] used is 3 to 70% by weight, preferably 5 to 60% by weight, and the proportion of the (meth) acrylic acid fluoroalkyl ester is 3%. -60% by weight, preferably 5-
50% by weight, the use ratio of (meth) acrylic acid alkyl ester is 3 to 50% by weight, preferably 5 to 40% by weight,
The proportion of the hydrophilic monomer used is preferably 2 to 20% by weight, more preferably 5 to 15% by weight.

The polymer constituted as described above has a very high gas permeability, particularly an oxygen permeability coefficient (DK value), excellent optical characteristics and mechanical characteristics, and is also excellent in stain resistance. When a contact lens is made of such a material, it can be worn for a long time, has a good feeling of wearing, is hard to get dirty, is not easily damaged, and is easy to handle. It has a number of features such as not sticking to the.

The present invention will be described in detail below. The bifunctional organic siloxane monomer represented by the general formula [I] has a longer intermolecular chain as the molecular weight increases, the oxygen permeability is improved, the cohesive energy is lowered, and the glass transition point is also increased. Get lower. For this reason, great features are exhibited in physical properties such as softness, shape retention, impact resistance, and returnability.

R in the general formula [1] is a hydrogen atom or a methyl group, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R are
₆ is a methyl group, an ethyl group, a propyl group, an isopropyl group, an alkyl group such as _{...... -C 10 H 21, -CF 3} , -C 2
_{F 5, -C 3 F 7,} -C 4 F 9, -C 6 F 13, -C 8 F
₁₇ and the like are fluoroalkyl groups having 1 to 10 carbon atoms, phenyl groups, alkylphenyl groups, fluoroalkylphenyl groups or trimethylsiloxanyl groups, and such bifunctional organic siloxane monomers [ The following can be illustrated as I].

[0037]

[Chemical 21]

These monomers [I] can be used alone or in combination of two or more kinds. The polyfunctional organosiloxane monomer represented by the general formula [II] has more functional groups as the molecular weight increases, so that the hardness of the material increases, the processability improves, and the oxygen permeability also improves. . General formula [I
R ₇ in I] is a hydrogen atom or a methyl group,
₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are a methyl group, an ethyl group, a propyl group, an isopropyl group, ...
₁₀ H ₂₁ alkyl group such _{as, -CF 3, -C 2 F 5} , -C 3
_{F 7, -C 4 F 9,} -C 6 F 13, -C 8 F 17, fluoroalkyl group having 1 to 10 carbon atoms represented by ...... etc., a phenyl group, an alkylphenyl group, a fluoroalkyl phenyl group or It is a trimethylsiloxanyl group, and the following can be illustrated as such a polyfunctional organic siloxane monomer [II].

[0039]

[Chemical formula 22]

These monomers [II] can be used alone or in combination of two or more kinds. The bifunctional organosiloxane monomer represented by the general formula [III] is the same as the bifunctional organosiloxane monomer represented by the general formula [I], and the inter-functional group chain becomes longer as the molecular weight increases. , The oxygen permeability is improved, the cohesive energy is lowered, and the glass transition point is lowered. For this reason, great features are exhibited in physical properties such as softness, shape retention, impact resistance, and returnability.
The following can be illustrated as such a bifunctional organosiloxane monomer [III].

[0041]

[Chemical formula 23]

These monomers [III] may be used alone or
It can be used in combination of two or more species. The monofunctional organosiloxane monomer represented by the general formula [IV] has an effect of improving stain resistance and oxygen permeability. R ₂₆ in the general formula [IV] is a hydrogen atom or a methyl group, and R _{27
R 28, R 29, R 30} , R 31, R 33 and R ₃₄ is a methyl group, a phenyl group or _{-CF 3, -C 2 F 5,} -C 3 F 7, -C
_{4 F 9, -C 6 F 13} , -C 8 F 17, represented by ...... etc. indicates a fluoroalkyl group having 1 to 10 carbon atoms, R ₃₂ and R
₃₅ does not represent a group (bonding chain connecting r ′ and u ′ parts)
Or a methyl group, a phenyl group or a fluoroalkyl group having 1 to 10 carbon atoms, and the following can be exemplified as such a polyfunctional organic siloxane monomer [IV].

[0043]

[Chemical formula 24]

Constituent materials of the gas-permeable polymer material of the present invention, that is, bifunctional organic siloxane monomer [I], difunctional organic siloxane monomer [III], polyfunctional organic siloxane monomer [II], etc. The monomer copolymerizable with
For example, one or more selected from fluoroalkyl esters of acrylic acid such as trifluoroethyl acrylate, tetrafluoroethyl acrylate, tetrafluoropropyl acrylate, pentafluoroethyl acrylate, and hexafluoroisopropyl acrylate, and corresponding methacrylic acid fluoroalkyl esters. Fluorine-containing monomers such as methyl methacrylate, ethyl methacrylate, t-butyl methacrylate, n-butyl methacrylate, n-propyl methacrylate, 1
-Propyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-heptyl methacrylate, n-octyl methacrylate, n-decyl methacrylate, n
-Dodecyl methacrylate, n-tetradecyl methacrylate, n-hexadecyl methacrylate, lauryl methacrylate (preferably n-butyl methacrylate, 2-ethylhexyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, n-heptyl methacrylate, n-octyl Methacrylate,
Methacrylic acid alkyl ester such as n-decyl methacrylate, n-dodecyl methacrylate) and alkoxyalkyl ester groups are —CH ₂ CH ₂ OR and —CH ₂ CH.
₂ (OR) CH ₃ , -CH ₂ CH ₂ CH ₂ OR, -CH
_{(CH 3) CH 2 OR,} -CH 2 CH 2 CH 2 CH 2 O
Methacrylic acid alkoxyalkyl ester having an alkoxyalkyl group represented by R (wherein R is an alkyl group having 1 to 7 carbon atoms), cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, phenoxyethyl methacrylate, tetrahydrofurfuryloxyethyl methacrylate, Examples thereof include acrylate monomers corresponding to these.

Further, for the purpose of adjusting the mechanical strength of the obtained material, for example, styrenes such as styrene and methylstyrene, itaconic acid substituted with an alkyl group, crotonic acid,
Monomers such as alkyl esters of maleic acid and fumaric acid can also be used. Furthermore, for the purpose of imparting ultraviolet absorption, coloring, and cutting light in a part of the visible light wavelength region, ultraviolet absorbers (including polymerizable types), dyes (polymerizable) Type are also included), ultraviolet absorbing dyes (including polymerizable types), and the like may be used.

Examples of the hydrophilic monomer used in the present invention include methacrylic acid, acrylic acid, itaconic acid, fumaric acid, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate and 2-hydroxypropyl acrylate. , Glycerol methacrylate, polyethylene glycol methacrylate, N, N′-dimethylacrylamide, N-methylacrylamide, N-vinylpyrrolidone and the like.

In the present invention, for example, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, bisphenol A dimethacrylate. It is also possible to use methacrylate, vinyl methacrylate, allyl methacrylate, acrylates corresponding thereto, and crosslinkable monomers such as divinylbenzene and triallyl isocyanurate.

Then, with respect to the above monomers,
For example, dimethyl-2,2'-azobisisobutyrate,
2,2'-azobis (4-methoxy-2,4'-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobisisobutylnitrile, benzoyl peroxide , The-tert
-A free radical polymerization initiator such as butyl peroxide, methyl ethyl ketone peroxide, isobutyl peroxide, and diisopropyl peroxydicarbonate is added, and polymerization is performed by a usual radical polymerization method. As the polymerization method, thermal polymerization, ultraviolet polymerization, radiation polymerization or the like can be adopted.

The polymer block thus obtained is cut into the shape of, for example, a contact lens or an intraocular lens, or by using a spin cast method, a static cast molding method, or the like. Can be finished as an intraocular lens.
Hereinafter, the present invention will be specifically described with reference to examples.

[0050]

【Example】

 [Example 1]

[0051]

[Chemical 25]

40 parts by weight of bifunctional organosiloxane monomer represented by n-butyl methacrylate 45 parts by weight N-vinylpyrrolidone 10 parts by weight ethylene glycol dimethacrylate 5 parts by weight 2,2′-azobis- (2,4- Dimethyl valeronitrile) (0.1 parts by weight) was mixed well at room temperature, and this mixed solution was poured into a polyethylene polymerization container, sealed with nitrogen, and then copolymerized in a dryer.

The obtained copolymer was cut and polished to obtain a contact lens. [Example 2]

[0054]

[Chemical formula 26]

40 parts by weight of a bifunctional organic siloxane monomer represented by: n-butyl methacrylate 25 parts by weight 2,2,2-trifluoroethyl methacrylate 20 parts by weight N-vinylpyrrolidone 10 parts by weight ethylene glycol dimethacrylate 5 parts by weight Parts 2,2'-azobis- (2,4-dimethylvaleronitrile) 0.1 parts by weight were mixed well at room temperature, and this mixture was poured into a polyethylene polymerization container, filled with nitrogen, and then dried in a drier. Copolymerized.

The resulting copolymer was cut and polished to obtain a contact lens. [Example 3]

[0057]

[Chemical 27]

70 parts by weight of a bifunctional organic siloxane monomer represented by: n-butyl methacrylate 18 parts by weight N-vinylpyrrolidone 7 parts by weight ethylene glycol dimethacrylate 5 parts by weight 2,2′-azobis- (2,4- Dimethyl valeronitrile) (0.1 parts by weight) was mixed well at room temperature, and this mixed solution was poured into a polyethylene polymerization container, sealed with nitrogen, and then copolymerized in a dryer.

The resulting copolymer was cut and polished to obtain a contact lens. [Example 4]

[0060]

[Chemical 28]

65 parts by weight of bifunctional organosiloxane monomer represented by n-butyl methacrylate 10 parts by weight 2,2,2-trifluoroethyl methacrylate 10 parts by weight N-vinylpyrrolidone 10 parts by weight triethylene glycol dimethacrylate 5 Weight part 2,2'-azobis- (2,4-dimethylvaleronitrile) 0.1 weight part is mixed well at room temperature, and this mixed solution is poured into a polyethylene polymerization container, sealed with nitrogen, and then dried in a dryer. Was copolymerized with.

The obtained copolymer was cut and polished to obtain a contact lens. [Example 5]

[0063]

[Chemical 29]

Polyfunctional organosiloxane monomer represented by 30 parts by weight n-butyl methacrylate 30 parts by weight Tris (trimethylsiloxy) silylpropyl methacrylate 25 parts by weight N-vinylpyrrolidone 10 parts by weight Ethylene glycol dimethacrylate 5 parts by weight 2 , 2'-Azobis- (2,4-dimethylvaleronitrile) 0.1 part by weight was mixed well at room temperature, and the mixture was poured into a polyethylene polymerization container, and after nitrogen was sealed, copolymerization was performed in a dryer. Let

The obtained copolymer was cut and polished to obtain a contact lens. [Example 6]

[0066]

[Chemical 30]

Polyfunctional organosiloxane monomer represented by 30 parts by weight n-butyl methacrylate 15 parts by weight Tris (trimethylsiloxy) silylpropyl methacrylate 25 parts by weight 2,2,2-trifluoroethyl methacrylate 15 parts by weight N- Vinylpyrrolidone 10 parts by weight Ethylene glycol dimethacrylate 5 parts by weight 2,2′-Azobis- (2,4-dimethylvaleronitrile) 0.1 parts by weight were mixed well at room temperature, and this mixture was placed in a polyethylene polymerization container. After injecting and filling with nitrogen, copolymerization was performed in a dryer.

The obtained copolymer was cut and polished to obtain a contact lens. [Example 7]

[0069]

[Chemical 31]

65 parts by weight of polyfunctional organic siloxane monomer represented by: n-butyl methacrylate 10 parts by weight 2,2,2-trifluoroethyl methacrylate 15 parts by weight N-vinylpyrrolidone 9 parts by weight ethylene glycol dimethacrylate 5 parts by weight Parts 2,2'-azobis- (2,4-dimethylvaleronitrile) 0.1 parts by weight were mixed well at room temperature, and this mixture was poured into a polyethylene polymerization container, filled with nitrogen, and then dried in a drier. Copolymerized.

The obtained copolymer was cut and polished to obtain a contact lens. [Example 8]

[0072]

[Chemical 32]

50 parts by weight of a bifunctional organosiloxane monomer represented by

[0074]

[Chemical 33]

Polyfunctional organosiloxane monomer represented by 15 parts by weight n-butyl methacrylate 10 parts by weight 2,2,2-trifluoroethyl methacrylate 15 parts by weight N-vinylpyrrolidone 10 parts by weight 2,2′-azobis 0.1 part by weight of-(2,4-dimethylvaleronitrile) was mixed well at room temperature, and this mixture was poured into a polyethylene polymerization container, sealed with nitrogen, and then copolymerized in a dryer.

The obtained copolymer was cut and polished to obtain a contact lens. [Example 9]

[0077]

[Chemical 34]

5 parts by weight of a bifunctional organosiloxane monomer represented by

[0079]

[Chemical 35]

Polyfunctional organic siloxane monomer represented by 10 parts by weight Methyl methacrylate 10 parts by weight n-butyl methacrylate 10 parts by weight Tris (trimethylsiloxy) silylpropyl methacrylate 25 parts by weight 2,2,2-trifluoroethyl methacrylate 32 parts by weight N-vinylpyrrolidone 8 parts by weight 2,2'-azobis- (2,4-dimethylvaleronitrile) 0.1 parts by weight were mixed well at room temperature, and this mixture was poured into a polyethylene polymerization container. After filling with nitrogen, copolymerization was performed in a dryer.

The obtained copolymer was cut and polished to obtain a contact lens. [Example 10]

[0082]

[Chemical 36]

20 parts by weight of a bifunctional organosiloxane monomer represented by

[0084]

[Chemical 37]

10 parts by weight of a polyfunctional organosiloxane monomer represented by

[0086]

[Chemical 38]

35 parts by weight of bifunctional organic siloxane monomer represented by: n-butyl methacrylate 10 parts by weight 2,2,2-trifluoroethyl methacrylate 15 parts by weight N-vinylpyrrolidone 8 parts by weight triethylene glycol dimethacrylate 5 Weight part 2,2'-azobis- (2,4-dimethylvaleronitrile) 0.1 weight part is mixed well at room temperature, and this mixed solution is poured into a polyethylene polymerization container, sealed with nitrogen, and then dried in a dryer. Was copolymerized with.

The obtained copolymer was cut and polished to obtain a contact lens. [Comparative Example 1]

[0089]

[Chemical Formula 39]

100 parts by weight of a bifunctional organic siloxane monomer represented by: 0.12 part by weight of 2,2′-azobis- (2,4-dimethylvaleronitrile) was mixed well at room temperature, and the mixture was mixed with polyethylene. It was poured into a polymerization vessel, sealed with nitrogen, and then copolymerized in a dryer. The obtained copolymer was cut and polished to obtain a contact lens.

Comparative Example 2 Tris (trimethylsiloxy) silylpropyl methacrylate 40 parts by weight 2,2,2,2 ', 2', 2'-hexafluoroisopropyl methacrylate 55 parts by weight Ethylene glycol dimethacrylate 5 parts by weight 2, 0.1 parts by weight of 2'-azobis- (2,4-dimethylvaleronitrile) was mixed well at room temperature, and this mixture was poured into a polyethylene polymerization container, sealed with nitrogen, and then copolymerized in a dryer. It was

The obtained copolymer was cut and polished to obtain a contact lens.

[0093]

[Characteristics] The contact lenses obtained in each of the above examples were examined for water wettability (contact angle), oxygen permeability, stain resistance (dirt adhesion), machinability and polishing processability. -1. [Contact angle] Contact A manufactured by Kyowa Interface Science Co., Ltd.
It was performed using a single meter. The sample piece was immersed in purified water for 24 hours, the water droplet on the surface was removed with an air brush, and then a water droplet having a diameter of 1 mm was brought into contact with the upper surface of the sample piece with a syringe, and the contact angle was determined by the angle formed by the water droplet.

[Oxygen permeability] Oxygen permeability coefficient was measured in a 25 ° C. atmosphere using Gasperm 100 manufactured by JASCO Corporation. [Stain Adhesion] Journal of Japan Contato Cleanse Society, No. 24
Vol. 277-283 (1982). Width of sample is 5m
m, thickness 2 mm, length 2 mm, and length 30 mm were used. Judgment was based on the adhesion of dirt when a PMMA sample piece was operated in the same manner as a control, and "small" when the degree of dirt adhesion was small by macroscopic observation, "large" when there was much dirt, and "equivalent" when equivalent. And In addition, three types of mucin (bovine stomach mucosa), lysozyme (egg white), and lecithin (egg yolk) were used as the dirt substance models.

[Machinability] Machinability Cutting surface has gloss: Good Cutting surface is not glossy: Poor Polishability Polishing surface has gloss: Good Polishing surface is not glossy: Bad Table-1 Contact Angle (degree) Oxygen Permeability Coefficient Soil Adhesion Machinability Abrasiveness Example 1 67 180 Equivalent Good Example 2 69 200 Equivalent Good Example 3 60 530 Equivalent − − Example 4 58 550 Equivalent − − Example 5 65 200 Equal Good Good Example 6 66 180 Equal Good Good Example 7 60 500 Equivalent --- Example 8 60 480 Equivalent --- Example 9 69 85 Equivalent Good Good Example 10 63 410 Equivalent --- Comparative Example 1 89 600 Many--Comparative Example 2 90 85 Many Many Bad Poor The unit of oxygen permeability coefficient is 10 ⁻¹¹ cc · cm / cm ² · sec · mmHg.

Claims (8)

[Claims] 1. The following general formula: (In the formula, R represents a hydrogen atom or a methyl group, and R ₁ , R
₂ , R ₃ , R ₄ , R ₅ and R ₆ are an alkyl group, a phenyl group, an alkylphenyl group, a fluoroalkyl group, a fluoroalkylphenyl group or a trimethylsiloxanyl group (provided that the alkyl has 1 to 10 carbon atoms). Also, R ₁ ,
R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are all methyl groups), which may be the same or different from each other. l is an integer of 1 to 20, m is an integer of 1 to 3, and n is an integer of 1 to 700. ) One or more monomers selected from the bifunctional organic siloxane monomer [I], and a monomer copolymerizable with the bifunctional organic siloxane monomer [I]. A gas-permeable polymer material, which is obtained by copolymerizing at least one kind or two or more kinds of monomers selected from the above. 2. The gas-permeable polymer material according to claim 1, wherein the proportion of the bifunctional organic siloxane monomer [I] used in the gas-permeable polymer material is 1 to 99% by weight. . 3. The following general formula: (In the formula, R ₇ represents a hydrogen atom or a methyl group, and R ₈ ,
R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are alkyl groups,
A phenyl group, an alkylphenyl group, a fluoroalkyl group, a fluoroalkylphenyl group or a trimethylsiloxanyl group (wherein the alkyl has 1 to 10 carbon atoms) may be the same or different from each other. or,
R ₁₂ may be X. p is an integer from 0 to 20, q is 1
Is an integer of 3; r is an integer of 1 to 700; u is an integer of 1 to 20. X is the following formula: Wherein R ₁₅ represents a hydrogen atom or a methyl group, and R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ represent an alkyl group, a phenyl group, an alkylphenyl group, a fluoroalkyl group, a fluoroalkylphenyl group or trimethyl. It represents a siloxanyl group (provided that the alkyl has 1 to 10 carbon atoms), and these may be the same or different from each other. p is an integer of 0 to 20, q is an integer of 1 to 3, w is 0 or 1, and v is 0 to 7.
00 is an integer. ) One or more kinds of monomers selected from the polyfunctional organic siloxane monomer [II], and a monomer copolymerizable with the polyfunctional organic siloxane monomer [II] A gas-permeable polymer material, which is obtained by copolymerizing at least one kind or two or more kinds of monomers selected from the above. 4. The gas-permeable polymer material according to claim 3, wherein the proportion of the polyfunctional organosiloxane monomer [II] used in the gas-permeable polymer material is 1 to 99% by weight. . 5. The following general formula: (In the formula, R represents a hydrogen atom or a methyl group, and R ₂₀ , R
₂₁ , R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ are each an alkyl group, a phenyl group, an alkylphenyl group, a fluoroalkyl group, a fluoroalkylphenyl group or a trimethylsiloxanyl group (however, the alkyl has 1 to 10 carbon atoms) , Which may be the same or different from each other. l is an integer of 0 to 20, m is an integer of 1 to 3, and n is an integer of 1 to 700. ) A bifunctional organosiloxane monomer [II
I] and one or more monomers selected from the following general formula: (In the formula, R ₇ represents a hydrogen atom or a methyl group, and R ₈ ,
R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are alkyl groups,
A phenyl group, an alkylphenyl group, a fluoroalkyl group, a fluoroalkylphenyl group or a trimethylsiloxanyl group (wherein the alkyl has 1 to 10 carbon atoms) may be the same or different from each other. or,
R ₁₂ may be X. p is an integer from 0 to 20, q is 1
Is an integer of 3; r is an integer of 1 to 700; u is an integer of 1 to 20. X is the following formula: Wherein R ₁₅ represents a hydrogen atom or a methyl group, and R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ represent an alkyl group, a phenyl group, an alkylphenyl group, a fluoroalkyl group, a fluoroalkylphenyl group or trimethyl. It represents a siloxanyl group (provided that the alkyl has 1 to 10 carbon atoms), and these may be the same or different from each other. p is an integer of 0 to 20, q is an integer of 1 to 3, w is 0 or 1, and v is 0 to 7.
00 is an integer. ) One or more kinds of monomers selected from the polyfunctional organosiloxane monomer [II] represented by the formula (1) and the monofunctional organosiloxane monomer [III] or / and the polyfunctional organosiloxane monomer. A gas-permeable polymer material, characterized in that it is obtained by copolymerizing at least one monomer or two or more monomers selected from copolymerizable monomers with the monomer [II]. . 6. The total proportion of the bifunctional organic siloxane monomer [III] and the polyfunctional organic siloxane monomer [II] used in the gas permeable polymer material is 1 to 99% by weight. The gas-permeable polymer material according to claim 5. 7. The following general formula: (In the formula, R represents a hydrogen atom or a methyl group, and R ₂₀ , R
₂₁ , R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ are each an alkyl group, a phenyl group, an alkylphenyl group, a fluoroalkyl group, a fluoroalkylphenyl group or a trimethylsiloxanyl group (however, the alkyl has 1 to 10 carbon atoms) , Which may be the same or different from each other. l is an integer of 0 to 20, m is an integer of 1 to 3, and n is an integer of 1 to 700. ) A bifunctional organosiloxane monomer [II
I] and one or more monomers selected from the following general formula: (In the formula, R ₇ represents a hydrogen atom or a methyl group, and R ₈ ,
R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are alkyl groups,
A phenyl group, an alkylphenyl group, a fluoroalkyl group, a fluoroalkylphenyl group or a trimethylsiloxanyl group (wherein the alkyl has 1 to 10 carbon atoms) may be the same or different from each other. or,
R ₁₂ may be X. p is an integer from 0 to 20, q is 1
Is an integer of 3; r is an integer of 1 to 700; u is an integer of 1 to 20. X is the following formula: Wherein R ₁₅ represents a hydrogen atom or a methyl group, and R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ represent an alkyl group, a phenyl group, an alkylphenyl group, a fluoroalkyl group, a fluoroalkylphenyl group or trimethyl. It represents a siloxanyl group (provided that the alkyl has 1 to 10 carbon atoms), and these may be the same or different from each other. p is an integer of 0 to 20, q is an integer of 1 to 3, w is 0 or 1, and v is 0 to 7.
00 is an integer. ) One or more monomers selected from the polyfunctional organic siloxane monomers [II] represented by the following general formula: (In the formula, R ₂₆ represents a hydrogen atom or a methyl group, and R ₂₇ ,
R ₂₈ , R ₂₉ , R ₃₀ , R ₃₁ , R ₃₃ and R ₃₄ represent a methyl group, a phenyl group or a fluoroalkyl group having 1 to 10 carbon atoms, and R ₃₂ and R ₃₅ do not represent a group (r ′ Or a methyl group, a phenyl group or a fluoroalkyl group having 1 to 10 carbon atoms. p'is 0 to 20
, Q ′ is 1, 2 or 3, t ′ and u ′ are 0, 1 or 2, and r ′ is 0 or 1. ) One or more monomers selected from the organosiloxane monomers [IV] represented by the formula (1), and one or more monomers selected from (meth) acrylic acid fluoroalkyl esters Gas, high gas permeability, which is characterized by being copolymerized by using at least one of a polymer, one or more kinds of monomers selected from (meth) acrylic acid alkyl ester, and a hydrophilic monomer. Molecular material. 8. The proportion of the bifunctional organosiloxane monomer [III] used in the gas permeable polymer material is 3 to 80.
% By weight, the polyfunctional organosiloxane monomer [II] is used in an amount of 3 to 80% by weight, the organosiloxane monomer [IV] is used in an amount of 3 to 70% by weight, and a (meth) acrylic acid fluoroalkyl ester is used. The usage rate is 3 to 60% by weight, and the usage rate of the (meth) acrylic acid alkyl ester is 3 to 50
The gas permeable polymer material according to claim 7, wherein the weight ratio of the hydrophilic monomer is 2 to 20% by weight.