JPH11287971A - Ophthalmic lens materials - Google Patents

Abstract

(57) [abstract] (with correction) [PROBLEMS] Ophthalmic lens materials, such as contact lenses, ophthalmic lens materials that have a good balance of mechanical strength, flexibility, oxygen permeability, shape stability, transparency, and hydrophilicity Offer. A monomer of the formula (I), a monomer of the formula (II) and a compound of the formula
An ophthalmic lens material and an ophthalmic lens made of a copolymer by polymerization of a monomer mixture mainly composed of the monomer (III).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ophthalmic lens material and an ophthalmic lens comprising the same. More specifically, the present invention relates to an ophthalmic lens material and an ophthalmic lens having a good balance of mechanical strength, durability, flexibility, oxygen permeability, shape stability, transparency, and various hydrophilic properties. In addition, the ophthalmic lens material and the ophthalmic lens of the present invention are particularly useful as a contact lens and an intraocular lens utilizing the above-mentioned characteristics.

[0002]

2. Description of the Related Art Contact lenses are generally classified into soft contact lenses and hard contact lenses. Conventionally, as a soft contact lens, a water-containing soft contact lens made of a polymer mainly comprising a structural unit derived from 2-hydroxyethyl methacrylate and / or vinylpyrrolidone is mainly commercially available. Also,
As hard contact lenses, those made of polymers mainly comprising structural units derived from methyl methacrylate, fluoroalkyl methacrylate or silicone methacrylate are mainly commercially available. However, a water-containing soft contact lens is excellent in wearing feeling but low in oxygen permeability, so that it is difficult to wear it for a long time. In addition, water-containing soft contact lenses have the drawback that bacteria and fungi are liable to propagate due to their water-containing properties, which requires complicated sterilization and disinfection, and also has poor mechanical strength. doing. On the other hand, hard contact lenses have relatively high oxygen permeability and can be worn for a long period of time, and do not require disinfection, but have the drawback that they are hard to wear because they are hard.

[0003] In order to solve the above-mentioned drawbacks of the conventional hydrous soft contact lenses and hard contact lenses, non-hydrous soft contact lenses made of silicone rubber have been developed. Non-hydrous soft contact lenses made of silicone rubber have high oxygen permeability,
Since it is non-water-containing and excellent in flexibility, it can be worn for a long time, is excellent in wearing feeling, and does not require disinfection. However, non-hydrous soft contact lenses made of silicone rubber have low mechanical strength, are brittle and have poor durability,
In addition, there has been reported an example in which the contact lens surface has a very high water repellency, which causes adhesion to the cornea and causes serious eye damage.

[0004] Therefore, in order to solve the above-mentioned problems in the non-water-containing contact lens made of silicone rubber, (1) a homopolymer of a bifunctional siloxane monomer having a polymerizable unsaturated group at both ends or A contact lens comprising a copolymer of the above-mentioned bifunctional siloxane monomer and an alkyl (meth) acrylate (JP-A-54-24047); (2) bifunctional having a polymerizable unsaturated group at both ends Non-hydrous soft contact lens comprising a copolymer of a hydrophilic siloxane monomer and a polycyclic ester of (meth) acrylic acid (JP-A-56-5)
No. 1714); and (3) tris (trimethylsiloxy) silylpropyl methacrylate having 2 to 2 carbon atoms
Non-water-containing soft contact lenses comprising a copolymer of a (meth) acrylate of a fluoroalkyl alcohol of 8 and an acrylate of a linear alcohol having 4 to 8 carbon atoms (JP-A-63-37312); And so on. However, the non-water-containing contact lens (1) is excellent in oxygen permeability, but inferior in mechanical strength and flexibility. Further, the non-water-containing contact lenses (2) and (3) have one of oxygen permeability, flexibility and mechanical strength.
One or two or more properties are inferior and do not have a well-balanced property required for a contact lens.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide excellent oxygen permeability, mechanical strength, durability and flexibility, as well as excellent properties such as shape stability, transparency and water wettability. Another object of the present invention is to provide an ophthalmic lens material and a high-quality ophthalmic lens material and an ophthalmic lens having various characteristics required for the ophthalmic lens in a well-balanced manner.

[0006]

The inventors of the present invention have conducted various studies to achieve the above object. As a result, a specific organosiloxane monomer having a polymerizable unsaturated group at both ends of the molecule, a monocyclic carbon Obtained by polymerizing a monomer mixture mainly composed of three monomers, a specific monomer having a monovalent hydrocarbon group derived from hydrogen, and a specific monofunctional organosiloxane monomer. The copolymer has high oxygen permeability,
Excellent mechanical strength, durability, flexibility, shape stability, transparency and water wettability, suitable for ophthalmic lens materials, and contact lenses and intraocular lenses obtained using it The inventors have found that an ophthalmic lens can exhibit excellent effects in correction of visual acuity, wearing feeling, handleability, strength, durability, safety, and the like, and completed the present invention.

That is, the present invention provides (a) the following general formula (I):

[0008]

Embedded image [Wherein R ¹ and R ² are each independently a hydrogen atom or a methyl group, and R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently substituted with a fluorine atom. A monovalent hydrocarbon group having 1 to 10 carbon atoms, A ¹ and A ² each independently represent an oxygen atom, a sulfur atom or a formula: —NR ⁹ — (wherein R ⁹ is substituted with a hydrogen atom or a fluorine atom; X ¹ and X ² each independently represent a single bond or a divalent organic group, and m represents 0 to 0 Indicates an integer of 300. [Hereinafter, this may be referred to as “bifunctional organosiloxane monomer (I)”]; (b) the following general formula (II);

[0009]

Embedded image Wherein, R ¹⁰ is a hydrogen atom or a methyl group, A ³ is an oxygen atom, a sulfur atom or the formula: -NR ¹¹ - (wherein, R ¹¹ is 1 the number of hydrogen atoms or carbon atoms which may be substituted with a fluorine atom
Y represents a monovalent hydrocarbon group derived from a monocyclic hydrocarbon. [Hereinafter referred to as “monocyclic monomer (I
I) "]; and (c) the following general formula (III);

[0010]

Embedded image [In the formula, R ¹² is a hydrogen atom or a methyl group, A ⁴ is an oxygen atom, a sulfur atom or a formula: —NR ¹³ — (wherein, R ¹³ has a carbon number of 1 which may be substituted with a hydrogen atom or a fluorine atom.
A monovalent hydrocarbon group of 10 to 10), X ³
Is a single bond or a divalent organic group, and Z ¹ , Z ² , Z ³ , Z ⁴ and Z ⁵ are each independently a monovalent hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom. , Formula: -OR
^{A group represented by 14} (wherein, R ¹⁴ represents a monovalent hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a fluorine atom) or a formula: —O—SiR ¹⁵ R ¹⁶ R ¹⁷ } Wherein R ¹⁵ , R ¹⁶
And R ¹⁷ are each independently a monovalent hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom or a formula: —O—R ¹⁸ (wherein, R ¹⁸ is substituted with a fluorine atom Represents a monovalent hydrocarbon group having 1 to 10 carbon atoms which may be present)
And n represents an integer of 0 to 300. An organosiloxane monomer [hereinafter sometimes referred to as “monofunctional organosiloxane monomer (III)”] represented by the following formula: An ophthalmic lens material characterized in that:

Further, the present invention is an ophthalmic lens made of the above-mentioned ophthalmic lens material of the present invention, particularly a contact lens and an intraocular lens.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. As described above, the ophthalmic lens material of the present invention comprises a bifunctional organosiloxane monomer (I) represented by the general formula (I) and a monocyclic monosiloxane monomer represented by the general formula (II). It comprises a copolymer obtained by polymerizing a monomer mixture mainly composed of the monomer (II) and the monofunctional organosiloxane monomer (III) represented by the general formula (III).

[0013] Bifunctional organosiloxane monomer (I)
In the above general formula (I), R ¹ and R ² are each independently (individually) a hydrogen atom or a methyl group. R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently have 1 carbon atom which may be substituted by a fluorine atom.
And a monovalent hydrocarbon group of 10 to 10. Among them,
R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ may be each independently an alkyl group, a cycloalkyl group, a monovalent aromatic group or a group substituted with a fluorine atom. Preferred and specific examples include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a phenyl group, and a benzyl group. 2,2,2-trifluoroethyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 1-trifluoromethyl-2,2 2-trifluoroethyl group, 2- (perfluorobutyl) ethyl group, 2- (perfluorohexyl) ethyl group, 2- (perfluorooctyl) ethyl group, 1H, 1H, 5H-octafluorope And a 1H, 1H, 7H-dodecafluoroheptyl group and a pentafluorophenyl group. In particular, R ³ , R ⁴ , R ⁵ , R ⁶ , R ^7, and R ³ are preferred from the viewpoints of ease of production of the bifunctional organosiloxane monomer (I), polymerizability, moldability of an ophthalmic lens material, and the like. ⁸ is more preferably an alkyl group having 1 to 3 carbon atoms or an alkyl group substituted with a fluorine atom;
More preferably, all of ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are methyl groups. When R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are a hydrocarbon group having 11 or more carbon atoms, the production of the bifunctional organosiloxane monomer (I) becomes difficult, and furthermore, the polymerization is carried out. Properties, moldability and hydrophilicity of the ophthalmic lens material are reduced.

In the above general formula (I), A ¹
And A ² each independently represent an oxygen atom, a sulfur atom or a formula: —NR ⁹ — (wherein R ⁹ represents a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a hydrogen atom or a fluorine atom. ). In the group represented by the above formula: —NR ⁹ —, when R ⁹ is a hydrocarbon group having 11 or more carbon atoms, the production of the bifunctional organosiloxane monomer (I) becomes difficult, and furthermore, the polymerization is carried out. Properties, moldability and hydrophilicity of the ophthalmic lens material are reduced. Preferred specific examples of R ^{9 in} the group represented by the above formula: —NR ⁹ — include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-
Butyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, cyclohexyl group, phenyl group, benzyl group, 2,2,2-trifluoroethyl group, 2,2,2
3,3-tetrafluoropropyl group, 2,2,3,3
3-pentafluoropropyl group, 1-trifluoromethyl-2,2,2-trifluoroethyl group, 2- (perfluorobutyl) ethyl group, 2- (perfluorohexyl) ethyl group, 2- (perfluorooctyl) ) Ethyl group, 1H, 1H, 5H-octafluoropentyl group, 1
H, 1H, 7H-dodecafluoroheptyl group, pentafluorophenyl group and the like can be mentioned. A ¹ and A ² represent an oxygen atom or R ⁹ as a hydrogen atom or a carbon atom from the viewpoints of ease of production of the bifunctional organosiloxane monomer (I), polymerizability, moldability of an ophthalmic lens material, and the like. It is more preferably -NR ^9- which is an alkyl group optionally substituted by a fluorine atom of Formulas 1 to 3, and it is preferably -NR ⁹ -wherein an oxygen atom or R ⁹ is a hydrogen atom or a methyl group. More preferably, it is more preferably an oxygen atom or -NH-.

In the above formula (I), X ¹ and X ² are each independently a single bond or a divalent organic group. Preferable examples of the divalent organic group at that time include an alkylene group which may have a substituent such as a hydroxyl group, an oxyalkylene group, a polyoxyalkylene group, and a bond between an alkylene group and a (poly) oxyalkylene group. And the like.

When X ¹ and / or X ² is an alkylene group, it is preferably an alkylene group having 1 to 6 carbon atoms or an alkylene group substituted with a hydroxyl group, and specific examples thereof include a methylene group and an ethylene group. Group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, 1-hydroxy-ethylene group, 1-hydroxy-trimethylene group, 2-hydroxy-trimethylene group,
1-hydroxy-tetramethylene group, 2-hydroxy-
Examples thereof include a tetramethylene group, a 1-hydroxy-pentamethylene group, a 2-hydroxy-pentamethylene group, a 1-hydroxy-hexamethylene group, and a 2-hydroxy-hexamethylene group. When the carbon number of the alkylene group is 7 or more, the moldability and mechanical strength of the ophthalmic lens material tend to be poor.

When X ¹ and / or X ² is an oxyalkylene group or a polyoxyalkylene group,
(Poly) oxyalkylene groups having 1 to 6 carbon atoms in the alkylene group in the oxyalkylene unit are preferred,
Specific examples include (poly) oxymethylene groups, (poly)
Oxyethylene groups, (poly) oxytrimethylene groups,
Examples thereof include a (poly) oxyisopropylene group, a (poly) oxytetramethylene group, a (poly) oxypentamethylene group, and a (poly) oxyhexamethylene group. In this case, the number of repeating oxyalkylene units in the (poly) oxyalkylene group is preferably 1 to 100, and more preferably 1 to 30.
If the number of repeating oxyalkylene units in the (poly) oxyalkylene group exceeds 100, the polymerizability of the bifunctional organosiloxane monomer (I), the moldability of the ophthalmic lens material, and the mechanical strength tend to be reduced.

When X ¹ and / or X ² is a group in which an alkylene group and a (poly) oxyalkylene group are bonded, ease of production of the bifunctional organosiloxane monomer (I), ophthalmic lens From the viewpoints of material moldability, mechanical strength, and the like, the number of carbon atoms of the alkylene group and the number of carbon atoms of the alkylene group in the oxyalkylene unit are 1 to 6, and the number of repeating oxyalkylene units in the (poly) oxyalkylene group is It is preferably from 1 to 100, particularly preferably from 1 to 30. Specific examples of such a group include a methylene (poly) oxyethylene group, an ethylene (poly) oxyethylene group, a trimethylene (poly) oxyethylene group, and a methylene (poly) in which the number of repeating oxyalkylene units is 1 to 100. ) Oxypropylene groups, ethylene (poly) oxypropylene groups, trimethylene (poly) oxypropylene groups, and the like.

Among the above groups, X ¹ and X ¹ are preferably selected from the viewpoints of ease of production of the bifunctional organosiloxane monomer (I), polymerizability, moldability of ophthalmic lens material, mechanical strength and the like. ² is a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a 1-hydroxy-trimethylene group, a 2-hydroxy-trimethylene group, a 1-hydroxy-tetramethylene group, a 2-hydroxy-tetramethylene group, The number of repeating units is 1 to 30
(Poly) oxymethylene group, (poly) oxyethylene group, and (poly) oxytrimethylene group, preferably methylene group, ethylene group, trimethylene group,
-Hydroxy-trimethylene group, 2-hydroxy-trimethylene group, and the number of repeating oxyethylene units is 1 to 3
More preferably, it is 0 (poly) oxyethylene group.

In the general formula (I), m is an integer of 0 to 300, and the bifunctional organosiloxane monomer (I)
It is preferably 0 to 250, more preferably 0 to 200, from the viewpoints of polymerizability, moldability of an ophthalmic lens material, mechanical strength and the like.

In the above general formula (II) representing the monocyclic monomer (II), R ¹⁰ is a hydrogen atom or a methyl group. A ³ is an oxygen atom, a sulfur atom or a formula: —N
R ¹¹ — is a group represented by the formula: (wherein R ¹¹ represents a monovalent hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a hydrogen atom or a fluorine atom). In the group represented by the above formula: —NR ¹¹ —, when R ¹¹ is a hydrocarbon group having 11 or more carbon atoms, production of the monocyclic monomer (II) becomes difficult, and furthermore, the polymerizability and The moldability and hydrophilicity of the ophthalmic lens material decrease. Preferred specific examples of R ^{11 in} the group represented by the above formula: —NR ¹¹ — include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and t-butyl. Group, pentyl group, hexyl group, cyclohexyl group, phenyl group, benzyl group, 2,2,2-
Trifluoroethyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 1-trifluoromethyl-2,2,2-trifluoroethyl group, 2- (perfluorobutyl) ethyl group, 2- (perfluorohexyl) ethyl group, 2- (perfluorooctyl) ethyl group, 1H, 1H, 5H-octafluoropentyl group, 1H, 1H, 7H-dodecafluoroheptyl And a pentafluorophenyl group. A ³ represents an oxygen atom, or R ¹¹ represents a hydrogen atom or a carbon atom having 1 to 4 carbon atoms in view of easiness of production of monocyclic monomer (II), polymerizability, moldability of ophthalmic lens material, and the like.
3 is more preferably -NR ^11- which is an alkyl group optionally substituted by a fluorine atom, and further preferably an oxygen atom or R ¹¹ is -NR ¹¹ -which is a hydrogen atom or a methyl group, More preferably, it is an oxygen atom or -NH-.

In the general formula (II), Y is a monovalent hydrocarbon group derived from a monocyclic hydrocarbon. Here, the “monocyclic hydrocarbon” in the present invention means that the hydrocarbon from which Y is derived has a condensed ring (for example, a naphthalene ring or the like) formed by condensing two or more monocyclic rings. In other words, it means a hydrocarbon having only a monocyclic hydrocarbon ring. The monocyclic hydrocarbon from which Y is derived may be any of an alicyclic hydrocarbon or an aromatic hydrocarbon as long as it is a hydrocarbon having only a monocyclic hydrocarbon ring. In addition, the monocyclic hydrocarbon may be a hydrocarbon having only one monocyclic hydrocarbon ring in the molecule, or may be a hydrocarbon having only one monocyclic hydrocarbon ring in the molecule.
It may be a hydrocarbon having at least two monocyclic hydrocarbon rings.

Specific examples of the group Y derived from a monocyclic hydrocarbon are preferably a cycloalkyl group, a cycloalkylalkyl group, a phenyl group or a phenylalkyl group, and specific examples are a cyclohexyl group and a cyclohexyl group. Methyl group, cyclohexylethyl group, cyclohexylpropyl group, cyclohexylbutyl group, cyclohexylpentyl group, cyclohexylhexyl group, phenyl group, benzyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, phenylpentyl group, phenylhexyl group, etc. These groups may have a substituent (such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a t-butyl group) on the cyclohexyl ring or the phenyl ring as the case may be. , Pentyl group Hexyl group, a cyclohexyl group, a phenyl group, a biphenyl group, a substituent) such as a benzyl group which may have one or more. Y is a group derived from a monocyclic hydrocarbon having a cyclohexyl ring from the viewpoints of easiness of production of the monocyclic monomer (II), polymerizability, mechanical strength of the ophthalmic lens material, flexibility and the like. And more preferably a cyclohexyl group.

In the above general formula (III) showing the monofunctional organosiloxane monomer (III), R ¹² is a hydrogen atom or a methyl group. A ⁴ is an oxygen atom,
A sulfur atom or a formula: —NR ¹³ — (wherein R ¹³ has 1 to 1 carbon atoms which may be substituted with a hydrogen atom or a fluorine atom;
0 represents a monovalent hydrocarbon group). In the group represented by the above formula: —NR ¹³ —, when R ¹³ is a hydrocarbon group having 11 or more carbon atoms, the production of the monofunctional organosiloxane monomer (III) becomes difficult, and furthermore, the polymerization is carried out. Properties, moldability and hydrophilicity of the ophthalmic lens material are reduced. Preferred specific examples of R ^{13 in} the group represented by the above formula: —NR ¹³ — include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and t-butyl. Group, pentyl group, hexyl group, cyclohexyl group, phenyl group, benzyl group, 2,2,2-trifluoroethyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,3,3 -Pentafluoropropyl group, 1-trifluoromethyl-2,2,2-trifluoroethyl group, 2- (perfluorobutyl) ethyl group,
2- (perfluorohexyl) ethyl group, 2- (perfluorooctyl) ethyl group, 1H, 1H, 5H-octafluoropentyl group, 1H, 1H, 7H-dodecafluoroheptyl group, pentafluorophenyl group, etc. Can be. A ⁴ represents an oxygen atom or R ¹³ represents a hydrogen atom or a carbon atom having 1 to 4 carbon atoms in view of easiness of production of monofunctional organosiloxane monomer (III), polymerizability, moldability of an ophthalmic lens material, and the like. 3 is more preferably -NR ^13- which is an alkyl group which may be substituted by a fluorine atom, and more preferably -NR ¹³ -wherein an oxygen atom or R ¹³ is a hydrogen atom or a methyl group. More preferably, it is an oxygen atom or -NH-.

In the general formula (III), X ³ is a single bond or a divalent organic group. When X ³ is a divalent organic group, preferable groups include an alkylene group, an oxyalkylene group, a polyoxyalkylene group, an alkylene group and an (poly) oxyalkylene group which may have a substituent such as a hydroxyl group. And the like bonded to the group.

When X ³ is an alkylene group, it is preferably an alkylene group having 1 to 6 carbon atoms or an alkylene group substituted with a hydroxyl group. Specific examples thereof include a methylene group, an ethylene group, a trimethylene group, Tetramethylene group, pentamethylene group, hexamethylene group, 1-hydroxy-ethylene group, 1-hydroxy-trimethylene group, 2-hydroxy-trimethylene group, 1-hydroxy-tetramethylene group, 2-hydroxy-tetramethylene group, 1 -Hydroxy-pentamethylene group, 2-hydroxy-pentamethylene group, 1-hydroxy-hexamethylene group, 2-hydroxy-hexamethylene group and the like. When the carbon number of the alkylene group is 7 or more, the moldability and mechanical strength of the ophthalmic lens material tend to be poor.

When X ³ is an oxyalkylene group or a polyoxyalkylene group, a (poly) oxyalkylene group having 1 to 6 carbon atoms in the alkylene group in the oxyalkylene unit is preferred.
(Poly) oxymethylene group, (poly) oxyethylene group, (poly) oxytrimethylene group, (poly) oxyisopropylene group, (poly) oxytetramethylene group,
(Poly) oxypentamethylene group, (poly) oxyhexamethylene group and the like can be mentioned. In that case,
The number of repeating oxyalkylene units in the (poly) oxyalkylene group is preferably from 1 to 100,
More preferably, it is 1 to 30. When the number of repeating oxyalkylene units in the (poly) oxyalkylene group exceeds 100, the polymerizability of the monofunctional organosiloxane monomer (III), the moldability of the ophthalmic lens material, and the mechanical strength tend to be reduced.

When X ³ is a group in which an alkylene group and a (poly) oxyalkylene group are bonded to each other, it is easy to produce a monofunctional organosiloxane monomer (III), the moldability of an ophthalmic lens material, In terms of mechanical strength and the like, the number of carbon atoms of the alkylene group and the number of carbon atoms of the alkylene group in the oxyalkylene unit are 1 to 6, and the number of repeating oxyalkylene units in the (poly) oxyalkylene group is 1 to 100, particularly It is preferably 1 to 30. Specific examples of such a group include a methylene (poly) oxyethylene group, an ethylene (poly) oxyethylene group, a trimethylene (poly) oxyethylene group, and a methylene (poly) in which the number of repeating oxyalkylene units is 1 to 100. )
Examples thereof include an oxypropylene group, an ethylene (poly) oxypropylene group, and a trimethylene (poly) oxypropylene group.

Among the above-mentioned groups, X is preferably selected from the viewpoints of ease of production of monofunctional organosiloxane monomer (III), polymerizability, moldability of ophthalmic lens material, mechanical strength and the like.
³ is a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a 1-hydroxy-trimethylene group,
A hydroxy-trimethylene group, a 1-hydroxy-tetramethylene group, a 2-hydroxy-tetramethylene group, a (poly) oxymethylene group having 1 to 30 oxyalkylene repeating units, a (poly) oxyethylene group, ) An oxytrimethylene group, preferably a (poly) oxy group having a methylene group, an ethylene group, a trimethylene group, a 1-hydroxy-trimethylene group, a 2-hydroxy-trimethylene group, and a repeating number of oxyethylene units of 1 to 30; More preferably, it is an ethylene group.

In the general formula (III), Z ¹ , Z ² ,
Z ³ , Z ⁴ and Z ⁵ each independently represent a carbon atom of 1 to 10 which may be substituted by a fluorine atom.
A group represented by the formula: -OR ¹⁴ (wherein, R ¹⁴ represents a monovalent hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a fluorine atom); Or formula: —O—SiR ¹⁵ R ¹⁶ R ¹⁷ , wherein R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently a monovalent hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a fluorine atom. Or the formula: -O
—R ¹⁸ (wherein R ¹⁸ represents a monovalent hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a fluorine atom).
Or a group represented by:

Z ¹ , Z ² , Z ³ , Z ⁴ and / or Z
⁵ has 1 to 1 carbon atoms which may be substituted by a fluorine atom
The hydrocarbon group in the above case, which is a monovalent hydrocarbon group of 0, the hydrocarbon group R ^{14 in} the above case, and even if R ¹⁵ , R ¹⁶ and R ¹⁷ in the above case are substituted with a fluorine atom When the hydrocarbon group is a monovalent hydrocarbon group having a good carbon number of 1 to 10, and the hydrocarbon group R ¹⁸ in the above case is an alkyl group, a cycloalkyl group, a monovalent aromatic group or a fluorine atom. These groups are preferably substituted with, for example, methyl, ethyl, n-propyl, isopropyl, n-
Butyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, cyclohexyl group, phenyl group, benzyl group, 2,2,2-trifluoroethyl group, 2,2,2
3,3-tetrafluoropropyl group, 2,2,3,3
3-pentafluoropropyl group, 1-trifluoromethyl-2,2,2-trifluoroethyl group, 2- (perfluorobutyl) ethyl group, 2- (perfluorohexyl) ethyl group, 2- (perfluorooctyl) ) Ethyl group, 1H, 1H, 5H-octafluoropentyl group, 1
H, 1H, 7H-dodecafluoroheptyl group, pentafluorophenyl group and the like can be mentioned. Among them, the above-mentioned hydrocarbon group is preferably an alkyl group having 1 to 3 carbon atoms in view of easiness of production of monofunctional organosiloxane monomer (III), polymerizability, moldability of ophthalmic lens material, and the like. Alternatively, it is more preferably an alkyl group substituted with a fluorine atom, and further preferably a methyl group.
When the hydrocarbon group is a hydrocarbon group having 11 or more carbon atoms, production of the monofunctional organosiloxane monomer (III) becomes difficult, and furthermore, polymerizability, moldability of the ophthalmic lens material,
The hydrophilicity decreases.

Z ¹ , Z ² , Z ³ , Z ⁴ in the general formula (III)
And Z ⁵ are monofunctional organosiloxane monomers (II
In terms of ease of production of I), polymerizability, moldability of ophthalmic lens materials, hydrophilicity, etc., alkyl groups having 1 to 3 carbon atoms,
A formula in which R ¹⁴ is an alkyl group having 1 to 3 carbon atoms; a group represented by —OR ¹⁴ , a formula in which R ¹⁵ , R ¹⁶ and R ¹⁷ are an alkyl group having 1 to 3 carbon atoms: —O—SiR ¹⁵ R preferably ¹⁶ is a group represented by R ^17, a methyl group, and more preferably either a methoxy group and trimethylsiloxy groups.

In the general formula (III), n is 0 to 3
It is an integer of 00, preferably 0 to 200.
If n exceeds 300, the polymerizability of the monofunctional organosiloxane monomer (III), the moldability of the ophthalmic lens material, the mechanical strength, and the like will decrease.

The ophthalmic lens material of the present invention comprises the above-mentioned bifunctional organosiloxane monomer (I), monocyclic monomer (II) and monofunctional organosiloxane monomer (III).
And a copolymer obtained by polymerizing a monomer mixture mainly composed of The copolymer constituting the ophthalmic lens material of the present invention comprises a bifunctional organosiloxane monomer (I), a monocyclic monomer (II) and a monofunctional monomer based on the total weight of the monomer mixture. Organosiloxane monomer (III)
Is preferably a copolymer obtained by polymerizing a monomer mixture having a total content of 70% by weight or more.
It is more preferably a copolymer obtained by polymerizing a monomer mixture of not less than 80% by weight, and further preferably a copolymer obtained by polymerizing a monomer mixture of not less than 80% by weight. . When the total content of the above three monomers in the monomer mixture is less than 70% by weight based on the total weight of the monomer mixture, a copolymer obtained by polymerizing such a monomer mixture is obtained. The mechanical strength, flexibility and oxygen permeability of ophthalmic lens materials and ophthalmic lenses made of polymers tend to be reduced. The bifunctional organosiloxane monomer (I), the monocyclic monomer (II) and the monofunctional organosiloxane monomer (I) in the monomer mixture used for the production of the copolymer constituting the ophthalmic lens material The upper limit of the total content of III) is not particularly limited, and the monomer mixture may consist of only these three types of monomers (the total content of the three may be 100% by weight). ).

Further, according to the present invention, in the monomer mixture used for producing the copolymer constituting the ophthalmic lens material,
The bifunctional organosiloxane monomer (I), the monocyclic monomer (II) and the monofunctional organosiloxane monomer (II
The mechanical strength and flexibility of the ophthalmic lens material are further improved when each content of I) is within the range of 5 to 80% by weight, based on the total weight of the monomer mixture. Preferred from the point. In particular, when the monomer mixture is composed of only the three members of the bifunctional organosiloxane monomer (I), the monocyclic monomer (II) and the monofunctional organosiloxane monomer (III), The content of the bifunctional organosiloxane monomer (I) is in the range of 10 to 80% by weight based on the total weight of the monomer mixture, and the monocyclic monomer (II)
Is in the range of 5 to 70% by weight, and the content of the monofunctional organosiloxane monomer (III) is 5 to 70% by weight.
It is preferable that the content be in the range of% by weight since the mechanical strength and flexibility of the ophthalmic lens material and the copolymer constituting the ophthalmic lens will be excellent.

The above-mentioned monomer mixture used for the production of the copolymer constituting the ophthalmic lens material comprises a bifunctional organosiloxane monomer (I), a monocyclic monomer (II) and a monofunctional monomer (II). In addition to the organosiloxane monomer (III), another monomer copolymerizable with these monomers may be contained, if necessary. Other monomers that can be used in combination include hydrophilic monomers, hydrophobic monomers, polyfunctional crosslinking monomers, and the like.These monomers may be used alone. Or two or more of them may be used in combination.

When a hydrophilic monomer is used in combination with the bifunctional organosiloxane monomer (I), monocyclic monomer (II) and monofunctional organosiloxane monomer (III), an ophthalmic lens material is obtained. In addition, the hydrophilicity of the ophthalmic lens can be improved. However, if the amount of the hydrophilic monomer used is too large, the water content of the ophthalmic lens becomes too high, and bacteria and molds easily proliferate and require sterilization and disinfection treatment. In order to eliminate the sterilization operation, based on the total weight of the monomer mixture,
The content of the hydrophilic monomer is preferably less than 25% by weight, more preferably less than 20% by weight, and even more preferably less than 15% by weight.

When a hydrophobic monomer is used in combination with the bifunctional organosiloxane monomer (I), monocyclic monomer (II) and monofunctional organosiloxane monomer (III), It is possible to improve the lipid adhesion resistance and the like of the lens material and the ophthalmic lens. However, if the amount of the hydrophobic monomer used is too large, the mechanical strength, flexibility and oxygen permeability of the ophthalmic lens material and the ophthalmic lens tend to decrease, so that the above-mentioned physical properties are good. In order to achieve this, the content of the hydrophobic monomer is preferably less than 30% by weight, based on the total weight of the monomer mixture.
More preferably, it is less than 20% by weight, more preferably less than 20% by weight.

Further, together with the bifunctional organosiloxane monomer (I), the monocyclic monomer (II) and the monofunctional organosiloxane monomer (III), another polyfunctional crosslinking monomer is used. When the body is used in combination, the shape stability of the ophthalmic lens material and the ophthalmic lens can be further improved. However, if the amount of the cross-linking monomer is too large, the flexibility of the ophthalmic lens material and the ophthalmic lens is lost, and the oxygen permeability tends to decrease. For example, when a bifunctional crosslinking monomer is used, its content is preferably less than 20% by weight, and preferably less than 15% by weight, based on the total weight of the monomer mixture. More preferably, it is more preferably less than 10% by weight.

Further, in the present invention, in order to improve the mechanical strength, flexibility, oxygen permeability, shape stability and other properties of the ophthalmic lens material and the ophthalmic lens, a hydrophilic monomer, The total content of other monomers such as a hydrophobic monomer and a crosslinking monomer is 30% based on the total weight of the monomer mixture used for producing the copolymer constituting the ophthalmic lens material. % By weight or less, more preferably 25% by weight or less, and even more preferably 20% by weight or less.

As the above-mentioned hydrophilic monomers, bifunctional organosiloxane monomers (I) and monocyclic monomers (II)
And any hydrophilic monomer which can be copolymerized with the monofunctional organosiloxane monomer (III) and which is not harmful to the living body. Examples thereof include unsaturated carboxylic acids such as (meth) acrylic acid and itaconic acid. Acids and salts thereof; (meth) acrylamides such as (meth) acrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-methylolacrylamide, dimethylaminopropyl (meth) acrylamide and N-acryloylmorpholine; N-vinyl-2-pyrrolidone,
N-vinyl-2-piperidone, N-vinyl-6-hexanelactam, N-vinyl-3-methyl-2-pyrrolidone, N-vinyl-3-methyl-piperidone, N-vinyl-3-methyl-6-hexane N-vinyllactams such as lactams; hydroxyl-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate and polyethylene glycol (meth) acrylate; 2- (dimethylamino) ethyl Amino group-containing (meth) such as methacrylate
Acrylates and the like can be mentioned. These hydrophilic monomers may be used alone or in combination of two or more. Among them, as the hydrophilic monomer, unsaturated carboxylic acids such as (meth) acrylic acid and itaconic acid, and (meth) acrylamides such as N, N-dimethylacrylamide, acrylamide and N-acryloylmorpholine are polymerizable. It is preferably used from the viewpoint of balance between the moldability and the hydrophilicity of the ophthalmic lens material obtained by polymerization.

As the above-mentioned hydrophobic monomers, bifunctional organosiloxane monomers (I) and monocyclic monomers (II)
And any of hydrophobic monomers which are copolymerizable with the monofunctional organosiloxane monomer (III) and which are not harmful to the living body, such as methyl (meth) acrylate,
Ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, t-amyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, C1-C30 alkyl esters of (meth) acrylic acid such as lauryl (meth) acrylate; 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) ) Acrylate, 2,2,3,3,3
Pentafluoropropyl (meth) acrylate, 2,
2,2-trifluoro-1-trifluoromethylethyl (meth) acrylate, 2-hydroxy-4,4,5,
5,6,6,7,7,8,8,9,9,10,11,1
C1-C30 fluorine-substituted alkyl esters of (meth) acrylic acid such as 1,11-hexadecafluoro-10-trifluoromethylundecyl (meth) acrylate; aromatic vinyl compounds such as styrene and methylstyrene; Vinyl esters of aliphatic carboxylic acids such as vinyl acetate; alkyl esters of itaconic acid or crotonic acid such as methyl itaconate and methyl crotonic acid; These hydrophobic monomers may be used alone or in combination of two or more. Among them, from the viewpoint of improving the lipid adhesion resistance, oxygen permeability, and mechanical strength of the ophthalmic lens material and the ophthalmic lens, (meth) acrylic acid has 1 to 3 carbon atoms as the hydrophobic monomer.
0 fluorine-substituted alkyl esters and (meth) acrylic acid having 1 to 30 carbon atoms are preferred.

The above-mentioned polyfunctional crosslinking monomers include a difunctional organosiloxane monomer (I), a monocyclic monomer (II) and a monofunctional organosiloxane monomer.
Any cross-linking monomer that can be copolymerized with (III) to form a cross-linked structure in the copolymer and that is not harmful to living organisms can be used. For example, ethylene glycol di (meth) acrylate, diethylene glycol di- (Meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate,
Tetradecaethylene glycol di (meth) acrylate, allyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, neopentyl glycol di (meth)
Acrylate, 2,2-bis [p- (γ-methacryloyloxy-β-hydroxypropoxy) phenyl] propane, and the like can be used. These crosslinking monomers may be used alone or in combination of two or more. May be used.

In order to obtain a colored ophthalmic lens material (copolymer), a dye may be added to the monomer mixture.

The bifunctional organosiloxane monomer (I), the monocyclic monomer (II), the monofunctional organosiloxane monomer (III) and, if necessary, other polymerizable monomers and dyes By copolymerizing the above-mentioned monomer mixture containing, for example, a known polymerization method such as radical polymerization, anionic polymerization, cationic polymerization, or radiation polymerization, the copolymer constituting the ophthalmic lens material of the present invention is obtained. Can be manufactured.

The type of the polymerization initiator is not particularly limited.
Known ones can be used depending on the polymerization method.For example, when a copolymer constituting an ophthalmic lens material is produced by thermal radical polymerization, benzoyl peroxide, isopropyl percarbonate, laurylyl peroxide, Methyl ethyl ketone peroxide, 2,2 '
-Azobisisobutyronitrile, 2,2'-azobismethylisobutyrate, 2,2'-azobisdimethylvaleronitrile, 2,2'-azobisisobutylamide,
The polymerization may be carried out using a known thermal radical polymerization initiator such as dimethyl 2,2′-azobisisobutyrate according to a conventional method. When producing a copolymer constituting an ophthalmic lens material by photoradical polymerization, for example, diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, phenothiazine, diisopropylxanthogen A photoradical polymerization initiator such as disulfide, benzoin, or benzoin methyl ether may be used to irradiate energy rays such as ultraviolet rays, visible rays, X-rays, and electron beams to carry out polymerization in a conventional manner. In the polymerization, if the amount of the polymerization initiator is too small, it takes a long time to produce the copolymer, while if the amount is too large, the generated copolymer tends to be cracked. It is important to keep the range. Generally, the amount of the polymerization initiator used is preferably in the range of 0.001 to 5% by weight, and more preferably in the range of 0.004 to 4% by weight, based on the total weight of the monomer mixture. And more preferably 0.01 to 3% by weight
Is more preferably within the range.

In producing an ophthalmic lens made of the above-mentioned ophthalmic lens material (copolymer), any of the methods conventionally used for producing a plastic ophthalmic lens can be used without any particular limitation. . For example, ophthalmic lenses include: (1) bifunctional organosiloxane monomer (I), monocyclic monomer (II), monofunctional organosiloxane monomer
(III) and, if necessary, polymerizing and molding a monomer mixture containing other polymerizable monomers and dyes to form a predetermined shape comprising the ophthalmic lens material (copolymer) of the present invention. Products (eg, sheet, plate, block, etc.)
And a molded article is cut and polished to produce an ophthalmic lens. (2) Bifunctional organosiloxane monomer (I), monocyclic monomer (II), monofunctional Organosiloxane monomer
(III) and, if necessary, a monomer mixture containing other polymerizable monomers and dyes is filled into a mold having a mold cavity corresponding to an ophthalmic lens, and polymerized and molded in the mold. (3) a bifunctional organosiloxane monomer (I), a monocyclic monomer (II),
A monomer mixture containing a monofunctional organosiloxane monomer (III) and, if necessary, other polymerizable monomers and dyes is dropped, and the monomer mixture is radially cast on a mold surface. It can be manufactured by employing a method such as a spin casting method of manufacturing an ophthalmic lens by polymerization and molding at the same time as diffusion.

The ophthalmic lens material of the present invention is a highly flexible non-water-containing material. Therefore, in the production of ophthalmic lenses such as contact lenses and intraocular lenses, the molding method (2) and ( Adopting the spin-casting method 3) is preferable because the objective ophthalmic lens can be manufactured with higher dimensional accuracy.

In the ophthalmic lens of the present invention, particularly the contact lens and the intraocular lens, it is preferable that the lens surface is made hydrophilic to improve water wettability. In making the ophthalmic lens hydrophilic, any method capable of hydrophilizing the surface of the ophthalmic lens may be adopted, for example, a method of treating the ophthalmic lens with alkaline water, a plasma treatment by glow discharge under a gas stream. And a method of graft-polymerizing a hydrophilic monomer on the surface of the ophthalmic lens, a method of hydrophilizing the surface of the ophthalmic lens at the same time as the molding of the ophthalmic lens, and the like. In particular, in performing the third method of hydrophilizing the surface simultaneously with the molding of the ophthalmic lens, using a mold having a hydrophilic mold surface, after coating the mold surface with a hydrophilic monomer, A method for producing a molded article having a hydrophilic surface by simultaneously introducing the polymerizable composition into the mold and polymerizing the polymerizable composition and polymerizing the hydrophilic monomer coated on the mold surface, that is, the present method. The method previously developed by the inventors (Japanese Patent Application No. 9-293299) is preferably employed.

[0050]

EXAMPLES The present invention will be described below in more detail with reference to examples and the like, but the present invention is not limited thereto. In the following examples, measurement or evaluation of each physical property of the ophthalmic lens material or the ophthalmic lens (contact lens) was performed as follows. Unless otherwise specified, “parts” in the following Examples and Comparative Examples represents parts by weight.

(1) Oxygen permeability coefficient (Dk): Ophthalmic lens material (copolymer) obtained in the following Examples and Comparative Examples
, Five test pieces (diameter: 15 mm) each having a thickness of 0.2 to 0.7 mm, which are different from each other, are cut out, and the oxygen permeability of the test pieces in distilled water at 35 ° C. is measured by the KAKENHI film oxygen permeation. Measured by a rate meter (manufactured by Rika Seiki Kogyo Co., Ltd.), and the obtained measured values are plotted on a graph having the reciprocal of thickness as the X axis and the reciprocal of oxygen permeability as the Y axis, and a regression line Is read and the reciprocal thereof is calculated as the oxygen permeability coefficient (unit: cc · cm / cm ² · sec · m
mHg).

(2) Elastic modulus: A cubic test piece having a side length of 5.0 mm was cut out from the ophthalmic lens material (copolymer) obtained in the following Examples and Comparative Examples, and this test piece was cut out. Using a test machine (“TMA-
4000 ”), a compression test is performed under a condition of a maximum load of 500 g and a load area of 0.785 mm ² (a circle having a diameter of 1 mm) while gradually increasing the load, and the strain of the test piece (unit:%) Was plotted on the X axis and stress (unit: g / mm ² ) was plotted on the Y axis, and the elastic modulus (unit: MPa) was determined from the slope of the linear portion in this graph.

(3) Ultimate strain: A cubic test piece having a side length of 5.0 mm was cut out from the ophthalmic lens material (copolymer) obtained in the following Examples and Comparative Examples. Using a test machine ("TMA" manufactured by Mac Science)
-4000 "), the test piece was compressed while gradually increasing the load under the conditions of a maximum load of 500 g and a load area of 0.785 mm ² (a circle having a diameter of 1 mm). Displacement [depth of the test specimen (unit: m
m)], and the ultimate strain (%) was determined by the following equation. In addition, when the test piece was not damaged, the displacement at the time when the maximum load was applied (at the time when a load of 500 g was applied) was measured, and the ultimate strain was obtained from the following equation. A larger value of the ultimate strain obtained by this method means that the test piece (ophthalmic lens material) is not brittle and is superior in durability.

[0054]

## EQU1 ## where, h = displacement (mm) of the test piece when the test piece is broken or when the maximum load is applied, H = height of the test piece before the load is applied (Mm)

(4) Transparency: The ophthalmic lens materials (copolymers) obtained in the following Examples and Comparative Examples were visually observed, and those which were transparent and showed no turbidity had good transparency. (◎) and those that were cloudy were evaluated as poor transparency (x).

(5) Contact angle: Using a contact angle measuring device (“GI” manufactured by Elma Optical Co., Ltd.), the contact angle of water on the front surface of the contact lenses obtained in the following Examples and Comparative Examples was 25. It measured by the drop method in the atmosphere of ° C.

(6) Shape stability: The contact lenses obtained in the following Examples and Comparative Examples were prepared by immersing the contact lenses in physiological saline.
After immersion for a month (average water temperature during immersion treatment: about 20 ° C.), the base curve was measured after 6 months, and the fluctuation range was 0.
Those with less than 1 mm have good shape stability (◎) and 0.
Those having a size of 1 mm or more were evaluated as poor shape stability (x).

The abbreviations and contents of the monomers used in the following Examples and Comparative Examples are as follows. (I) MPPS-60 : a bifunctional organosiloxane monomer (I) represented by the following chemical formula (i).

[0059]

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(Ii) MPPS-40 : The following chemical formula (i)
The bifunctional organosiloxane monomer (I) represented by i).

[0061]

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(Iii) MACE : Monocyclic monomer (II) (cyclohexyl methacrylate) represented by the following chemical formula (iii).

[0063]

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(Iv) MPTTS : Monofunctional organosiloxane monomer (III) represented by the following chemical formula (iv).

[0065]

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(V) MPMTS : Monofunctional organosiloxane monomer (III) represented by the following chemical formula (v).

[0067]

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(Vi) MMPPS : Monofunctional organosiloxane monomer (III) represented by the following chemical formula (vi).

[0069]

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Example 1 (1) (i) 65 parts of bifunctional organosiloxane monomer (I) (MPPS-60), monocyclic monomer (II)
(MACE) 15 parts and monofunctional organosiloxane monomer (III) (MPTTS) 20 parts were mixed, and to this was added 0.5 parts of benzoin methyl ether (photopolymerization initiator) to obtain a polymerizable monomer mixture. Was prepared, and after degassing, it was poured onto a quartz glass plate on which a Teflon spacer was placed,
A quartz glass plate was further placed thereon, and light irradiation was performed for 10 minutes with a 150 W high-pressure mercury lamp to produce a copolymer.
As a result, a colorless and transparent copolymer was obtained. (Ii) The copolymer obtained in the above (i) was peeled off from the quartz glass plate to obtain an ophthalmic lens material made of the copolymer. As shown in Table 1 below, this ophthalmic lens material was transparent without any turbidity, and had no optical distortion. (Iii) From the ophthalmic lens material obtained in (ii) above,
Five test pieces (diameter: 15 mm) each having a thickness of 0.2 to 0.7 mm for measuring the oxygen permeability coefficient, and a length of one side for elastic modulus measurement and ultimate strain measurement of 5.
A 0 mm cube-shaped test piece was cut out, and the oxygen permeability coefficient, the elastic modulus, and the ultimate strain were measured by the methods described above. The results are as shown in Table 1 below.

(2) (i) 2-Methacryloyloxyethyl phosphorylcholine (hydrophilic monomer) is placed on the inner surface of a polyvinyl alcohol mold (mold material: “Poval CP-1000” manufactured by Kuraray Co., Ltd.) for producing contact lenses.
Was coated with a 3% isopropanol solution and dried to prepare a mold for producing a contact lens in which a hydrophilic monomer layer was formed on the inner surface of the mold. (Ii) The mold for contact lens production prepared in the above (i) is filled with the same polymerizable monomer mixture as used in the above (1) (i), and irradiated with light from a 150 W high-pressure mercury lamp. After 10 minutes of photopolymerization, the contact lenses were manufactured by immersing the molds in water and dissolving the polyvinyl alcohol molds in water. The resulting contact lens is transparent, has a smooth surface,
Excellent water wettability. The contact angle and shape stability of this contact lens with water were measured by the methods described above, and were as shown in Table 1 below.

Example 2 (1) (i) 65 parts of bifunctional organosiloxane monomer (I) (MPPS-40), monocyclic monomer (II)
(MACE) 15 parts and monofunctional organosiloxane monomer (III) (MPTTS) 20 parts were mixed, and to this was added 0.5 parts of benzoin methyl ether (photopolymerization initiator) to obtain a polymerizable monomer mixture. Was prepared, and after degassing, it was poured onto a quartz glass plate on which a Teflon spacer was placed,
A quartz glass plate was further covered thereon, and light irradiation was performed for 10 minutes from a high-pressure mercury lamp of 150 W to produce a copolymer.
The resulting copolymer was colorless and transparent. (Ii) The copolymer obtained in the above (i) was peeled off from a quartz glass plate to obtain an ophthalmic lens material made of the copolymer. This ophthalmic lens material is shown in Table 1 below.
As shown in Fig. 7, the sample was transparent without any turbidity and had no optical distortion. (Iii) From the ophthalmic lens material obtained in (ii) above,
Five test pieces (diameter: 15 mm) each having a thickness of 0.2 to 0.7 mm for measuring the oxygen permeability coefficient, and a length of one side for elastic modulus measurement and ultimate strain measurement of 5.
A 0 mm cube-shaped test piece was cut out, and the oxygen permeability coefficient, the elastic modulus, and the ultimate strain were measured by the methods described above. The results are as shown in Table 1 below.

(2) (i) A polypropylene mold for contact lens production is prepared, and the same polymerizable monomer mixture as used in (1) (i) is filled in the mold. Then, light irradiation was performed from a high-pressure mercury lamp of 150 W to perform photopolymerization for 10 minutes to produce a contact lens-shaped molded product. (Ii) The contact lens-shaped molded product obtained in the above (i) was subjected to plasma treatment under an oxygen stream to produce a contact lens having a hydrophilic surface. The contact lens thus obtained was transparent, had a smooth surface, and was excellent in water wettability. The contact angle and shape stability of this contact lens with water were measured by the methods described above, and were as shown in Table 1 below.

<< Examples 3 and 4 >> (1) The same monomers as in Example 1, that is, 2
Functional organosiloxane monomer (I) (MPPS-6
0), monocyclic monomer (II) (MACE) and monofunctional organosiloxane monomer (III) (MPTTS), and the compounding amounts of these monomers are shown in Table 1 below. An ophthalmic lens material and a contact lens were manufactured in the same manner as in (1) and (2) of Example 1 except that the composition was changed to (1). (2) Evaluation and measurement of the transparency, oxygen permeability coefficient, elastic modulus and ultimate strain of the ophthalmic lens material obtained in (1) above, and the contact angle and contact angle of water on the contact lens obtained in (1) above. When the shape stability was measured by the above-described method, the results were as shown in Table 1 below.

Examples 5 to 9 (1) As the bifunctional organosiloxane monomer (I), the monocyclic monomer (II) and the monofunctional organosiloxane monomer (III), Ophthalmic lens materials and contact lenses were produced in the same manner as in (1) and (2) of Example 1, except that monomers of the types shown in Table 2 were used in the proportions shown in Table 2. (2) Evaluation and measurement of the transparency, oxygen permeability coefficient, elastic modulus and ultimate strain of the ophthalmic lens material obtained in (1) above, and the contact angle and contact angle of water on the contact lens obtained in (1) above. The shape stability was measured by the method described above, and was as shown in Table 2 below.

Comparative Example 1 As a monomer, a bifunctional organosiloxane monomer (I) (MPPS-60) was used alone, and the others were the same as (1) and (2) in Example 1. Similarly, an ophthalmic lens material and a contact lens were manufactured. The transparency of the ophthalmic lens material obtained thereby,
Evaluation and measurement of the oxygen permeability coefficient, elastic modulus, and ultimate strain, and measurement of the contact angle and shape stability of the contact lens with water by the above-described methods were as shown in Table 3 below.

Comparative Example 2 Monofunctional organosiloxane monomer (III) (MPTTS) was used alone as a monomer, and the other conditions were the same as (1) and (2) in Example 1. Thus, an ophthalmic lens material and a contact lens were manufactured. The transparency and oxygen permeability coefficient of the ophthalmic lens material obtained thereby, the evaluation and measurement of the elastic modulus and ultimate strain, and the measurement of the contact angle and shape stability of water on the contact lens with water were performed by the methods described above. Table 3 below
Was as shown in FIG.

Comparative Example 3 As the monomers, a bifunctional organosiloxane monomer (I) (MPPS-60) and a monocyclic monomer (II) (MACE) were blended as shown in Table 3 below. The ophthalmic lens material and the contact lens were manufactured in the same manner as in (1) and (2) of Example 1 except for using the same amount. The transparency and oxygen permeability coefficient of the ophthalmic lens material obtained thereby, the evaluation and measurement of the elastic modulus and ultimate strain, and the measurement of the contact angle and shape stability of water on the contact lens with water were performed by the methods described above. As shown in Table 3 below.

Comparative Example 4 As monomers, a bifunctional organosiloxane monomer (I) (MPPS-60) and a monofunctional organosiloxane monomer (III) (MPTT
S) was used in the amounts shown in Table 3 below, and the rest of the procedure was the same as (1) and (2) in Example 1 to produce ophthalmic lens materials and contact lenses. The transparency and oxygen permeability coefficient of the ophthalmic lens material obtained thereby, the evaluation and measurement of the elastic modulus and ultimate strain, and the measurement of the contact angle and shape stability of water on the contact lens with water were performed by the methods described above. As shown in Table 3 below.

[0080]

[Table 1]

[0081]

[Table 2]

[0082]

[Table 3]

From the results of Tables 1 to 3, it is mainly composed of the bifunctional organosiloxane monomer (I), the monocyclic monomer (II) and the monofunctional organosiloxane monomer (III). The ophthalmic lens materials and ophthalmic lenses (contact lenses) of Examples 1 to 9 each comprising a copolymer manufactured using the monomer mixture have excellent transparency and high oxygen permeability, It has low elasticity, flexibility, excellent feeling of wearing, high ultimate strain value and excellent durability, good contact angle with water, good water wettability and good hydrophilicity. Despite the fact that it is not excessively hydrophilic, bacteria and molds are not easily propagated and sterilization and disinfection treatment is not required.In addition, it has excellent shape stability, and there is little change in shape and dimensions and deformation even after long-term use. You can see that.

On the other hand, the ophthalmic lens material and the ophthalmic lens (contact lens) of Comparative Example 1 comprising a homopolymer of the bifunctional organosiloxane monomer (I) have extremely low values of ultimate strain. It turns out that it is fragile and lacks in durability, and cannot be practically used as an ophthalmic lens material or an ophthalmic lens. Further, the ophthalmic lens material and the ophthalmic lens (contact lens) of Comparative Example 2 comprising a homopolymer of the monofunctional organosiloxane monomer (III) undergo plastic deformation, shape deformation, and the like, and the ophthalmic lens material Further, it can be seen that it cannot be practically used as an ophthalmic lens. The ophthalmic lens material and the ophthalmic lens (contact lens) of Comparative Example 3 comprising a copolymer of the bifunctional organosiloxane monomer (I) and the monocyclic monomer (II) have extremely low distortion. It can be seen that the wearability is inferior because the value is low and lacks durability, and the elastic modulus is high and flexibility is low. further,
The ophthalmic lens material and the ophthalmic lens (contact lens) of Comparative Example 4 comprising a copolymer of the bifunctional organosiloxane monomer (I) and the monofunctional organosiloxane monomer (III) have an extremely low distortion. The values are low, indicating that the durability is low.

[0085]

The ophthalmic lens material and the ophthalmic lens of the present invention are excellent in oxygen permeability, mechanical strength, durability and flexibility, and have various properties such as shape stability, transparency and moderate water wettability. It has excellent characteristics, and has a good balance of various characteristics required for ophthalmic lens materials and ophthalmic lenses.
Therefore, the ophthalmic lens of the present invention, particularly the contact lens and the intraocular lens, have excellent wearing feeling, handleability, strength, durability, deformation resistance, safety, and have no propagation of microorganisms such as bacteria and molds. No sterilization treatment is required.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Satsuki Kitajima 17 Kyoto-shi, Kyoto, Kyoto Prefecture Kyoto Research Park 17 Teran-cho 17 Kyoto Research Park Kansai New Technology Research Institute Co., Ltd. Ikuo 1621 Sakurazu, Kurashiki City, Okayama Prefecture Kuraray Co., Ltd. (72) Inventor Takumi Fujitani Kuraray Co., Ltd.

Claims (6)

[Claims] (A) The following general formula (I): [Wherein R ¹ and R ² are each independently a hydrogen atom or a methyl group, and R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently substituted with a fluorine atom. A monovalent hydrocarbon group having 1 to 10 carbon atoms, A ¹ and A ² each independently represent an oxygen atom, a sulfur atom or a formula: —NR ⁹ — (wherein R ⁹ is substituted with a hydrogen atom or a fluorine atom; X ¹ and X ² each independently represent a single bond or a divalent organic group, and m represents 0 to 0 Indicates an integer of 300. (B) an organosiloxane monomer represented by the following general formula (II): Wherein, R ¹⁰ is a hydrogen atom or a methyl group, A ³ is an oxygen atom, a sulfur atom or the formula: -NR ¹¹ - (wherein, R ¹¹ is 1 the number of hydrogen atoms or carbon atoms which may be substituted with a fluorine atom
Y represents a monovalent hydrocarbon group derived from a monocyclic hydrocarbon. And (c) the following general formula (III): [In the formula, R ¹² is a hydrogen atom or a methyl group, A ⁴ is an oxygen atom, a sulfur atom or a formula: —NR ¹³ — (wherein, R ¹³ has a carbon number of 1 which may be substituted with a hydrogen atom or a fluorine atom.
A monovalent hydrocarbon group of 10 to 10), X ³
Is a single bond or a divalent organic group, and Z ¹ , Z ² , Z ³ , Z ⁴ and Z ⁵ are each independently a monovalent hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom. , Formula: -OR
^{A group represented by 14} (wherein, R ¹⁴ represents a monovalent hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a fluorine atom) or a formula: —O—SiR ¹⁵ R ¹⁶ R ¹⁷ } Wherein R ¹⁵ , R ¹⁶
And R ¹⁷ are each independently a monovalent hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom or a formula: —O—R ¹⁸ (wherein, R ¹⁸ is substituted with a fluorine atom Represents a monovalent hydrocarbon group having 1 to 10 carbon atoms which may be present)
And n represents an integer of 0 to 300. An ophthalmic lens material comprising a copolymer obtained by polymerizing a monomer mixture mainly composed of an organosiloxane monomer represented by the following formula: 2. The organosiloxane monomer represented by the above general formula (I), the monomer represented by the general formula (II) and the organosiloxane monomer represented by the general formula (III) 2. The ophthalmic lens material according to claim 1, comprising a copolymer obtained by polymerizing a monomer mixture having a total content of 70% by weight or more based on the total weight of the monomer mixture. 3. The organosiloxane monomer represented by the general formula (I), the monomer represented by the general formula (II) and the organosiloxane monomer represented by the general formula (III) The content is 5% each based on the total weight of the monomer mixture.
The ophthalmic lens material according to claim 1, comprising a copolymer obtained by polymerizing a monomer mixture in a range of about 80% by weight. 4. An ophthalmic lens comprising the ophthalmic lens material according to claim 1. 5. The ophthalmic lens according to claim 4, which is a contact lens. 6. The ophthalmic lens according to claim 4, wherein the surface is made hydrophilic.