JP3453226B2 - Oxygen-permeable hard ophthalmic lens material and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an optically transparent oxygen-permeable hard ophthalmic lens material and a method for producing the same.
More specifically, in addition to having transparency, it has high oxygen permeability and is excellent in mechanical properties such as hardness and bending elasticity, and can be suitably used for ophthalmic lenses such as hard contact lenses. TECHNICAL FIELD The present invention relates to an oxygen-permeable hard eye lens material and a method for producing the same.

[0002]

2. Description of the Related Art In the field of contact lenses, research on hard contact lenses having excellent oxygen permeability has been underway in recent years, and such hard contact lenses having excellent oxygen permeability include, for example, siloxanylalkyl (meth). ) Contact lens materials such as those obtained from acrylate and siloxanyl styrene are used.

However, although such a contact lens material is excellent in oxygen permeability, it does not have sufficient hardness and flexural modulus as a material for obtaining a hard contact lens, and has a drawback that mechanical properties are inferior. Therefore, in general, a monomer component that provides a material having excellent oxygen permeability such as siloxanylalkyl (meth) acrylate or siloxanylstyrene, and hardness and bending elasticity of methyl methacrylate, fluoroalkyl methacrylate, fluorine-containing styrene, etc. The above-mentioned drawbacks are solved by copolymerizing with a monomer component which gives an excellent material.

However, when both monomer components are copolymerized as described above, the mechanical properties of the obtained material are improved, but on the other hand, siloxanylalkyl (meth) acrylate and siloxanylstyrene are obtained. However, there is a problem that the oxygen permeability originally possessed by the material obtained only from the monomer components such as is lowered. A material obtained only from a monomer component that gives such a material having excellent hardness and flexural elasticity generally has poor oxygen permeability, and the greater the amount of these monomer components used, the more remarkable such a phenomenon becomes.

Therefore, it is difficult to obtain a hard ophthalmic lens material having excellent oxygen permeability and mechanical properties such as hardness and flexural elasticity at the same time, and development of such a hard ophthalmic lens material and a method for producing the same. Is awaited.

[0006]

Therefore, the inventor of the present invention
In view of the above-mentioned prior art, as a result of repeated intensive studies to obtain a hard ophthalmic lens material having both excellent oxygen permeability and mechanical properties, surprisingly, the oxygen permeable material, hardness and bending elasticity Only the ophthalmic lens material having a structure in which a reinforcing polymer that can be improved mutually penetrates has not only transparency and high oxygen permeability, but also excellent mechanical properties such as hardness and bending elasticity. Heading, it came to complete the present invention.

[0007]

That is, the present invention is
General formula (I):

[0008]

[Chemical 15]

(In the formula, m and n are each independently 1
An integer of 15 to 15 and p is 0 or 1) and a polymerization component (A) containing 60 to 99.9% by weight of a silicon-containing styrene derivative and 0.1 to 20% by weight of a crosslinkable monomer as main components. A crosslinked oxygen-permeable material comprising a polymer obtained by polymerizing, and a compound represented by the general formula (II):

[0010]

[Chemical 16]

(Wherein R ¹ is a hydrogen atom or a methyl group,
R ² is a linear, branched or cyclic alkyl group having 1 to 7 carbon atoms, an aromatic ring-containing group having 6 to 10 carbon atoms, and 1 carbon atom in which at least one of hydrogen atoms is substituted with a fluorine atom.
To a linear, branched, or cyclic alkyl group having 7 to 7 carbon atoms or an aromatic ring-containing group having 6 to 10 carbon atoms in which at least one of hydrogen atoms is substituted with a fluorine atom, a monomer represented by the general formula ( III):

[0012]

[Chemical 17]

(In the formula, R ³ is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 7 carbon atoms, and 6 carbon atoms.
10 to 10 aromatic ring-containing group, a linear, branched or cyclic alkyl group having 1 to 7 carbon atoms in which at least one of hydrogen atoms is substituted with a fluorine atom, and at least 1 of hydrogen atom
An aromatic ring-containing group having 6 to 10 carbon atoms in which one is substituted with a fluorine atom, and general formula (IV):

[0014]

[Chemical 18]

(In the formula, R ⁴ is a linear, branched or cyclic alkyl group having 1 to 7 carbon atoms, an aromatic ring-containing group having 6 to 10 carbon atoms, and at least one of hydrogen atoms is a fluorine atom. A substituted straight-chain, branched-chain or cyclic alkyl group having 1 to 7 carbon atoms or an aromatic ring-containing group having 6 to 10 carbon atoms in which at least one of hydrogen atoms is substituted with a fluorine atom, a is 0 or A group represented by the general formula (V):

[0016]

[Chemical 19]

(Wherein b represents 0 or an integer of 1 to 4) or a group represented by the general formula (VI):

[0018]

[Chemical 20]

(Wherein q represents 0 or an integer of 1 to 7 and r represents an integer of 1 to 3) and a monomer represented by the general formula (VII):

[0020]

[Chemical 21]

(In the formula, R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom or a fluorine atom;
^5, R ^6, R ^7, at least one of R ⁸ and R ⁹ has been E by polymerizing polymerizable components containing a monomer selected from a monomer represented by a fluorine atom) 60 wt% or more (B) An optically transparent oxygen-permeable hard ophthalmic lens material having an interpenetrating polymer network structure formed from a reinforcing polymer made of a polymer, and a crosslinked oxygen-permeable material impregnated with a polymerization component (B). The present invention also relates to a method for producing the optically transparent oxygen-permeable hard ophthalmic lens material, which comprises polymerizing the polymerization component (B).

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION The optically transparent oxygen-permeable hard eye lens material of the present invention (hereinafter, also referred to as hard eye lens material) has the general formula (I):

[0023]

[Chemical formula 22]

(In the formula, m and n are each independently 1
An integer of 15 to 15 and p is 0 or 1) and a polymerization component (A) containing 60 to 99.9% by weight of a silicon-containing styrene derivative and 0.1 to 20% by weight of a crosslinkable monomer as main components. A crosslinked oxygen-permeable material comprising a polymer obtained by polymerizing, and a compound represented by the general formula (II):

[0025]

[Chemical formula 23]

(In the formula, R ¹ is a hydrogen atom or a methyl group,
R ² is a linear, branched or cyclic alkyl group having 1 to 7 carbon atoms, an aromatic ring-containing group having 6 to 10 carbon atoms, and 1 carbon atom in which at least one of hydrogen atoms is substituted with a fluorine atom.
To a linear, branched, or cyclic alkyl group having 7 to 7 carbon atoms or an aromatic ring-containing group having 6 to 10 carbon atoms in which at least one of hydrogen atoms is substituted with a fluorine atom, a monomer represented by the general formula ( III):

[0027]

[Chemical formula 24]

(In the formula, R ³ is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 7 carbon atoms, and 6 carbon atoms.
10 to 10 aromatic ring-containing group, a linear, branched or cyclic alkyl group having 1 to 7 carbon atoms in which at least one of hydrogen atoms is substituted with a fluorine atom, and at least 1 of hydrogen atom
An aromatic ring-containing group having 6 to 10 carbon atoms in which one is substituted with a fluorine atom, and general formula (IV):

[0029]

[Chemical 25]

(In the formula, R ⁴ is a linear, branched or cyclic alkyl group having 1 to 7 carbon atoms, an aromatic ring-containing group having 6 to 10 carbon atoms, and at least one of hydrogen atoms is a fluorine atom. A substituted straight-chain, branched-chain or cyclic alkyl group having 1 to 7 carbon atoms or an aromatic ring-containing group having 6 to 10 carbon atoms in which at least one of hydrogen atoms is substituted with a fluorine atom, a is 0 or A group represented by the general formula (V):

[0031]

[Chemical formula 26]

(Wherein b represents 0 or an integer of 1 to 4) or a group represented by the general formula (VI):

[0033]

[Chemical 27]

(In the formula, q represents a group represented by 0 or an integer of 1 to 7 and r represents an integer of 1 to 3) and a monomer represented by the general formula (VII):

[0035]

[Chemical 28]

(In the formula, R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom or a fluorine atom;
^5, R ^6, R ^7, at least one of R ⁸ and R ⁹ has been E by polymerizing polymerizable components containing a monomer selected from a monomer represented by a fluorine atom) 60 wt% or more (B) An interpenetrating polymer network structure is formed from a reinforcing polymer made of a polymer.

An interpenetrating polymer network structure is formed in the hard ophthalmic lens material of the present invention. Based on the interpenetrating polymer network structure, the hard ophthalmic lens material of the present invention has a conventional structure. Compared with an ophthalmic lens material made of a copolymer, the following excellent properties are shown.

That is, the conventional copolymer can be obtained by, for example, copolymerizing the monomer A and the monomer B, and the homopolymer A and the monomer B composed of the monomer A can be obtained.
The properties are almost intermediate with those of the homopolymer B consisting of
Therefore, the copolymer sacrifices the inherent properties of the homopolymer A and the homopolymer B, respectively. For example, when copolymerizing methyl methacrylate, for example, in order to improve the elastic modulus of a polymer composed of siloxanyl alkyl methacrylate, the elastic modulus is certainly improved, but siloxanyl alkyl methacrylate is improved. The oxygen permeability imparted by is considerably reduced.

On the other hand, the hard ophthalmic lens material of the present invention has a structure in which the network of the polymer constituting the oxygen permeable material and the reinforcing polymer penetrate into each other to form a network, The excellent oxygen permeability of the oxygen permeable material and the high hardness and high elastic modulus of the reinforcing polymer are effectively exhibited at the same time. As described above, the hard ophthalmic lens material of the present invention has an interpenetrating polymer network structure in which both polymers are appropriately phase-separated to such an extent that optical homogeneity, that is, optical transparency is not impaired. Combines the properties of polymers.

On the other hand, the conventional simple mixture of two or more kinds of different polymers generally tends to become opaque, and most of them are not suitable for optical materials such as ophthalmic lens materials. This is because the compatibility between different polymers is usually poor, so even if you try to evenly mix the two, when each polymer phase-separates and the domain becomes a certain size or more, the difference in the refractive index of each polymer causes It is believed that this is because the material as a whole becomes opaque.

Therefore, conventionally, in order to mix two or more kinds of different polymers into a material having a transparent polymer blend structure, a combination of polymers having a small difference in refractive index is selected or the polymers are compatibilized with each other. It is necessary to let However, in the former case, although there is no problem in terms of optical properties, as described above, the compatibility between polymers is poor, and desired mechanical properties are often not imparted. Further, in the latter case, some compatibilizer is required, and among these compatibilizers, particularly effective ones are often block copolymers or graft copolymers. In order to industrially manufacture the ophthalmic lens material, there are problems in terms of equipment and operability.

On the other hand, according to the method for producing a hard ophthalmic lens material of the present invention, a pre-crosslinked oxygen-permeable material is impregnated with a polymerization component (B) which gives a reinforcing polymer,
With the simple operation of polymerizing, it is possible to obtain a material that has a fine phase-separation structure that does not adversely affect optical homogeneity and mechanical properties, and that has excellent transparency, oxygen permeability, and mechanical properties. it can.

As described above, the hard ophthalmic lens material of the present invention has a structure in which the phases are appropriately separated so that the transparency is not deteriorated, so that the oxygen permeability of the oxygen permeable material is almost impaired. In other words, the reinforcing polymer has excellent mechanical properties such as hardness and bending elasticity.

In the present specification, the interpenetrating polymer network structure means a structure in which the network of the oxygen permeable material and the reinforcing polymer are intermingled with each other, and the reinforcing polymer is a crosslinked network-like structure. It may be linear or non-crosslinked.

The oxygen-permeable material used in the present invention has a three-dimensional network structure with intermolecular cross-linking,
Such intermolecular crosslinks may be any of covalent bonds, ionic bonds, hydrogen bonds and van der Waals forces, as long as they are not destroyed when impregnated with the polymerizing component (B) which gives the reinforcing polymer.

The oxygen permeable material comprises the silicon-containing styrene derivative represented by the general formula (I) (hereinafter referred to as the monomer (A-1)) in an amount of 60 to 99.9% by weight and the crosslinkable monomer in an amount of 0.1 to 20% by weight. % As a main component, the polymer is obtained by polymerizing the polymerization component (A).

In the general formula (I) representing the monomer (A-1), m and n are each independently 1 to 1
Although it represents an integer of 5, when m and n are integers of 16 or more, the oxygen permeable material becomes too soft,
The mechanical properties of the obtained hard ophthalmic lens material will not be sufficiently exhibited. Further, in order to develop oxygen permeability and mechanical properties in a more balanced manner at the same time, m and n
Is preferably an integer of 1 to 10 each independently.

Specific examples of the monomer (A-1) include, for example, tris (trimethylsiloxy) silylstyrene, trimethylsilylstyrene, pentamethyldisiloxanylstyrene, heptamethyltrisiloxanylstyrene, nonamethyltetrasiloxanyl. Styrene, pentadecamethylheptasiloxanyl styrene, heneicosamethyl decasiloxanyl styrene, heptacosamethyl tridecasiloxanyl styrene, hentriacontamethyl pentadeca siloxanyl styrene, bis (trimethylsiloxy) methylsilylstyrene , Trimethylsiloxy (pentamethyldisiloxy) methylsilylstyrene, tris (pentamethyldisiloxy) silylstyrene, (tris (trimethylsiloxy) siloxanyl) bis (trimethylsiloxy) sili Styrene, bis (heptamethyltrisiloxy) methylsilylstyrene, tris (methylbis (trimethylsiloxy) siloxy) silylstyrene, trimethylsiloxy (bis (tris (trimethylsiloxy) siloxy)) silylstyrene, heptakis (trimethylsiloxy) trisiloxanyl Styrene, nonamethyltetrasiloxy (undecamethylpentasiloxy)
Methylsilylstyrene, tris (tris (trimethylsiloxy) siloxy) silylstyrene, (tris (trimethylsiloxy) hexamethyltetrasiloxy) (tris (trimethylsiloxy) siloxy) trimethylsiloxysilylstyrene, nonakis (trimethylsiloxy) tetrasiloxanylstyrene , Bis (tridecamethylhexasiloxy) methylsilylstyrene and the like, and these can be used alone or in admixture of two or more.

In the present invention, the monomer (A-
The content of 1) in the polymerization component (A) is 60% by weight or more,
Although it is 99.9% by weight or less, in order to provide the obtained hard ophthalmic lens material with a better balance of oxygen permeability and mechanical properties such as high hardness and high elasticity, such monomer (A-1 The content of () in the polymerization component (A) is desirably 65% by weight or more, preferably 70% by weight or more, and 99% by weight or less, preferably 95% by weight or less.

In the present invention, the monomer (A-1) and / or a monomer copolymerizable with a crosslinking monomer described below (hereinafter referred to as a copolymerizable monomer (a)) is used as the monomer (A- Silicon-containing monomers other than 1) (hereinafter referred to as monomer (a-1))
For the purpose of further improving oxygen permeability, preferably 3
Within the range of 5% by weight or less, the total amount of the polymerization component (A) is 100.
It may be contained in the polymerization component (A) so that the content of the polymer is (wt).

Typical examples of the monomer (a-1) include, for example, tris (trimethylsiloxy) silylpropyl (meth) acrylate, pentamethyldisiloxanylmethyl (meth) acrylate, pentamethyldisiloxanylpropyl (meta). ) Acrylate, methylbis (trimethylsiloxy) silylpropyl (meth) acrylate, mono (methylbis (trimethylsiloxy) siloxy) bis (trimethylsiloxy) silylpropyl (meth) acrylate, tris [methylbis (trimethylsiloxy) siloxy] silylpropyl (meth) Acrylate, methyl [bis (trimethylsiloxy)] silylpropylglyceryl (meth) acrylate, tris (trimethylsiloxy) silylpropylglyceryl (meth) acrylate, mono (methyl Sus (trimethylsiloxy) siloxy) bis (trimethylsiloxy) silylpropylglyceryl (meth) acrylate, trimethylsilylethyltetramethyldisiloxanylpropylglyceryl (meth) acrylate, trimethylsilylmethyl (meth) acrylate, trimethylsilylpropyl (meth) acrylate, trimethylsilyl Propylglyceryl (meta)
Acrylate, pentamethyldisiloxanylpropylglyceryl (meth) acrylate, methylbis (trimethylsiloxy) silylethyl tetramethyldisiloxanylmethyl (meth) acrylate, tetramethyltriisopropylcyclotetrasiloxanylpropyl (meth) acrylate, tetra Silicon-containing (meth) acrylates such as methyltriisopropylcyclotetrasiloxybis (trimethylsiloxy) silylpropyl (meth) acrylate; bis (trimethylsilylpropyl) fumarate, bis (pentamethyldisiloxanylpropyl) fumarate, bis (tetramethyl ( Trimethylsiloxy) disiloxanylpropyl) fumarate, bis ((trimethylbis (trimethylsiloxy) disiloxanyl) propyl) fumarate, Fluoroethyl (trimethylsilylmethyl) fumarate, trifluoroethyl (trimethylsilylpropyl) fumarate, hexafluoroisopropyl (trimethylsilylmethyl) fumarate, hexafluoroisopropyl (trimethylsilylpropyl) fumarate, octafluoropentyl (trimethylsilylmethyl) fumarate, octafluoropentyl (trimethylsilylpropyl) ) Fumarate, trifluoroethyl (pentamethyldisiloxanylmethyl) fumarate, trifluoroethyl (pentamethyldisiloxanylpropyl) fumarate, hexafluoroisopropyl (pentamethyldisiloxanylmethyl) fumarate, hexafluoroisopropyl (penta Methyldisiloxanylpropyl) fumarate, octafluoropen (Pentamethyldisiloxanylmethyl) fumarate, octafluoropentyl (pentamethyldisiloxanylpropyl) fumarate, trifluoroethyl (tetramethyl (trimethylsiloxy) disiloxanylmethyl) fumarate, trifluoroethyl (tetramethyl (Trimethylsiloxy)
Disiloxanylpropyl) fumarate, hexafluoroisopropyl (tetramethyl (trimethylsiloxy) disiloxanylmethyl) fumarate, hexafluoroisopropyl (tetramethyl (trimethylsiloxy) disiloxanylpropyl) fumarate, octafluoropentyl (tetramethyl (Trimethylsiloxy) disiloxanylmethyl) fumarate, octafluoropentyl (tetramethyl (trimethylsiloxy) disiloxanylpropyl) fumarate, trifluoroethyl (tris (trimethylsiloxy) silylmethyl) fumarate, trifluoroethyl (tris (trimethyl Siloxy) silylpropyl) fumarate, hexafluoroisopropyl (tris (trimethylsiloxy) silylmethyl) fumarate, hexafluoroiso Ropyl (tris (trimethylsiloxy) silylpropyl) fumarate, octafluoropentyl (tris (trimethylsiloxy) silylmethyl) fumarate, octafluoropentyl (tris (trimethylsiloxy) silylpropyl) fumarate, isopropyl (trimethylsilylpropyl) fumarate, cyclohexyl (trimethylsilylpropyl) ) Fumarate, isopropyl (pentamethyldisiloxanylpropyl) fumarate, cyclohexyl (pentamethyldisiloxanylpropyl) fumarate, isopropyl (tetramethyl (trimethylsiloxy) disiloxanylpropyl) fumarate, cyclohexyl (tetramethyl (trimethylsiloxy) ) Disiloxanylpropyl) fumarate, isopropyl ((trimethylbis (trimethylene Siloxy) disiloxanyl) propyl) fumarate, silicon-containing fumarate, such as cyclohexyl ((trimethylbis (trimethylsiloxy) disiloxanyl) propyl) fumarate and the like. These may be used alone or in admixture of two or more.

Polymerization component (A) of the monomer (a-1)
The content thereof is 1% by weight or more, preferably 1% by weight or more, considering the content of the monomer (A-1) in the polymerization component (A) so that desired physical properties are imparted to the obtained hard ophthalmic lens material. Is preferably 5% by weight or more, and 30% by weight or less, preferably 25% by weight or less.

The crosslinkable monomer used in the present invention is a component used for forming a crosslinked structure in the oxygen permeable material.

Typical examples of the crosslinkable monomer include, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,4. -Di (meth) acrylates such as butylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, bisphenol A di (meth) acrylate; ethylene glycol (methacrylate) acrylate, triallyl cyanurate, trimethylol Propane tri (meth) acrylate, diallyl phthalate, N,
Examples thereof include N′-methylenebis (meth) acrylamide, divinylbenzene, vinylbenzyl (meth) acrylate, vinyl (meth) acrylate and allyl (meth) acrylate, which may be used alone or in combination of two or more. it can.

The content of the crosslinkable monomer in the polymerization component (A) is 0.1% by weight or more and 20% by weight or less, but the crosslinking of the polymer constituting the oxygen permeable material should be sufficient. Furthermore, the formation of an interpenetrating polymer network structure of the oxygen-permeable material and the reinforcing polymer comprising the polymerizing component (B) is sufficient, and the transparency and mechanical properties of the finally obtained hard ophthalmic lens material are improved. In order to prevent the strength from decreasing, the content is preferably 1% by weight or more, preferably 5% by weight or more, and the crosslinking density of the oxygen permeable material becomes too large, so that the polymerization component (B 15% by weight or less is preferable in order to prevent the impregnation with).

Further, the polymerization component (A) used in the present invention contains a copolymerizable monomer (a) other than the above-mentioned monomer (a-1), if necessary, preferably within a range of 35% by weight or less. The polymerization component (A) can be contained so that the total amount becomes 100% by weight.

The type of the copolymerizable monomer (a) may be appropriately selected depending on the properties of the intended hard ophthalmic lens material.

For example, when it is desired to impart hydrophilicity to the oxygen permeable material, a hydrophilic monomer (a-2) can be used as the copolymerizable monomer (a).

Typical examples of the hydrophilic monomer (a-2) include (meth) acrylic acid, hydroxyethyl (meth) acrylate and hydroxypropyl (meth).
Hydroxyl group-containing (meth) acrylate such as acrylate, hydroxybutyl (meth) acrylate, dihydroxypropyl (meth) acrylate, diethylene glycol mono (meth) acrylate; (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) (Meth) acrylamide-based monomers such as acrylamide, N-hydroxyethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide; N
Vinyl lactams such as vinylpyrrolidone; vinylbenzyl (3-hydroxy-n-propionate), vinylbenzyl (4-hydroxy-n-butyrate), vinylbenzyl (5-hydroxy-n-valerate), vinylbenzyl (6- Hydroxy-n-hexanoate),
Vinylbenzyl (7-hydroxy-n-heptanoate), vinylbenzyl (3-hydroxy-2-methylpropionate), vinylbenzyl (3-hydroxypivalate), vinylbenzyl (4-hydroxy-3,3-).
Dimethyl butyrate), vinylbenzyl (4-hydroxycyclohexanoate), vinylbenzyl (4-hydroxybenzoate) and other hydroxyl group-containing styrene monomers; maleic acid, fumaric acid, itaconic acid and other dicarboxylic acids, maleic anhydride, etc. And the like. These can be used alone or in admixture of two or more.

The content of the hydrophilic monomer (a-2) in the polymerization component (A) is 1% by weight or more, and preferably 1% by weight or more in order to sufficiently exhibit the effect of imparting hydrophilicity. It is preferably 5% by weight or more, and the effect of imparting oxygen permeability by the monomer (A-1) or the monomer (a-1) is sufficiently exhibited, and the shape change due to water absorption is sufficient. 30% by weight to suppress
It is desirable that the amount is below, preferably 25% by weight or less.

Further, for example, in order to prevent lipids and the like in tears from adhering, a functional monomer (a-3) exhibiting stain resistance can be used as the copolymerizable monomer (a).

Typical examples of the functional monomer (a-3) include 2,2,2-trifluoroethyl (meth) acrylate and 1,1,1,3,3,3-hexafluoroisopropyl (meth). ) Acrylate, 2,2,2
-Trifluoroethyl (p-vinylbenzoate),
1,1,1,3,3,3-hexafluoroisoprovir (p-vinylbenzoate), 2,2,3,3,4
4,5,5-octafluoropentyl (p-vinylbenzoate), 2,2,2-trifluoroethyl (p-vinylphenyl) acetate, 1,1,1,3,3,3-
Hexafluoroisopropyl (p-vinylphenyl) acetate, 2,2,3,3,4,4,5,5-octafluoropentyl (p-vinylphenyl) acetate, p
-Vinylbenzyl-2,4,4,5,5,6,6,6-
Octafluoro-2-trifluoromethyl-3-oxahexyl ether, p-vinylbenzyl-2,4,4
5,7,7,8,8,9,9,9-undecafluoro-
2,5-bis (trifluoromethyl) -3,6-dioxanonyl ether, p-vinylbenzyl-2,4,4
5,7,7,8,10,10,11,11,12,1
2,12-Tetradecafluoro-2,5,8-tris (trifluoromethyl) -3,6,9-trioxadodecyl ether, p-vinylbenzyl-2,4,4,5
7,7,8,10,10,11,13,13,14,1
4,15,15,15-Heptadecafluoro-2,5
8,11-tetrakis (trifluoromethyl) -3,
6,9,12-tetraoxapentadecyl ether, p
-Vinylbenzyl-2,4,4,5,7,7,8,1
0,10,11,13,13,14,16,16,1
7,17,18,18,18-Eicosafluoro-2,
Fluorine-containing monomers such as 5,8,11,14-pentakis (trifluoromethyl) -3,6,9,12,15-pentaoxaoctadecyl ether and 2,3,4,5,6-pentafluorostyrene; glycidyl (Meta)
Acrylate, vinyl chloroacetate, 2-chloroethyl vinyl ether, (meth) acrylonitrile and the like can be mentioned, and these can be used alone or in admixture of two or more kinds.

The content of the functional monomer (a-3) in the polymerization component (A) is preferably 1% by weight or more, so that the effect of imparting stain resistance can be sufficiently exhibited. Is preferably 5% by weight or more, and in order to sufficiently exhibit the effect of imparting oxygen permeability by the monomer (A-1) or the monomer (a-1),
It is desirable that the content is 0% by weight or less, preferably 25% by weight or less.

As a method for producing the oxygen permeable material, for example, a usual radical polymerization method can be adopted. When radical polymerization is carried out, a radical polymerization initiator such as a monomer (A-1) and a crosslinkable monomer, a monomer (a-1), a hydrophilic monomer (a-2), a functional monomer (a-3) is used. ), Etc., may be mixed and dissolved in the polymerization component (A) containing the copolymerizable monomer (a).

Examples of the radical polymerization initiator include azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile) and 2,2'-azobis (4-methoxy-2,4-). Azo polymerization initiators such as dimethyl valeronitrile); organic peroxide polymerization initiators such as benzoyl peroxide, di-t-butyl peroxide, cumene peroxide; sodium persulfate, potassium persulfate, ammonium persulfate, etc. Examples include water-soluble polymerization initiators.

The amount of the radical polymerization initiator used is not particularly limited, but is usually 0.01 to 5 parts by weight, particularly 0.05 to 3 parts by weight, relative to 100 parts by weight of the polymerization component (A). It is preferable to adjust so that.

Considering the oxygen permeability of the obtained hard ophthalmic lens material, the oxygen permeability coefficient of the oxygen permeable material is
100 × 10 ^-11 (cm ² / sec) ・ (mlO ₂ / (m
It is preferably 1 × mmHg)) or more.

The oxygen permeability coefficient in the present invention is
Gas permeability measuring device Model manufactured by Yanagimoto Seisakusho Co., Ltd.
It is a value measured with a GTR-10 at 35 ° C. for a sample (test piece) having a thickness of 0.5 mm.

Considering the heat resistance of the obtained hard ophthalmic lens material, the glass transition temperature (hereinafter referred to as Tg) of the oxygen permeable material is preferably 40 ° C. or higher.

The Tg in the present invention is a value measured for the temperature at which the storage elastic modulus starts to decrease in the dynamic viscoelasticity measurement.

The hard ophthalmic lens material of the present invention has an interpenetrating polymer network structure formed from the oxygen permeable material and the reinforcing polymer.

The reinforcing polymer includes a monomer represented by the general formula (II) (hereinafter referred to as a monomer (B-1)) and a monomer represented by the general formula (III) (hereinafter referred to as a monomer).
By polymerizing a polymerization component (B) containing 60% by weight or more of a monomer selected from a monomer (B-2)) and a monomer represented by the general formula (VII) (hereinafter referred to as a monomer (B-3)). It is composed of the obtained polymer.

Of the alkyl group represented by R ² in the general formula (II) representing the monomer (B-1) and the alkyl group represented by R ³ in the general formula (III) representing the monomer (B-2). The carbon number is more preferably 1 to 5 from the viewpoint that the effect of imparting high hardness and high elasticity exhibited by the reinforcing polymer is greater.

Specific examples of the monomer (B-1) include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl. Alkyl (meth) acrylate such as (meth) acrylate; (meth) acrylate having an aromatic ring-containing group such as benzyl (meth) acrylate; 2,2,2-trifluoroethyl (meth) acrylate, 1,1,1 , 3,3,3-hexafluoroisopropyl (meth) acrylate and other fluorine-containing (meth) acrylates.

Specific examples of the monomer (B-2) include styrene; methylstyrene, ethylstyrene, n-propylstyrene, isopropylstyrene, isobutylstyrene, t-butylstyrene; 2,2,2-
Trifluoroethyl (p-vinylbenzoate), 1,
1,1,3,3,3-hexafluoroisopropyl (p
-Vinylbenzoate), 2,2,3,3,4,4,4
5,5-octafluoropentyl (p-vinylbenzoate), 2,2,2-trifluoroethyl (p-vinylphenyl) acetate, 1,1,1,3,3,3-hexafluoroisopropyl (p-vinyl) Phenyl) acetate, 2,2,3,3,4,4,5,5-octafluoropentyl (p-vinylphenyl) acetate; p-vinylbenzyl-2,4,4,5,5,6,6 6-octafluoro-2-trifluoromethyl-3-oxahexyl ether, p-vinylbenzyl-2,4,4,5
7,7,8,8,9,9,9-undecafluoro-2,
5-bis (trifluoromethyl) -3,6-dioxanonyl ether, p-vinylbenzyl-2,4,4,5,
7,7,8,10,10,11,11,12,12,1
2-tetradecafluoro-2,5,8-tris (trifluoromethyl) -3,6,9-trioxadodecyl ether, p-vinylbenzyl-2,4,4,5,7,7,
8,10,10,11,13,13,14,14,1
5,15,15-Heptadecafluoro-2,5,8,1
1-tetrakis (trifluoromethyl) -3,6,9,
12-tetraoxapentadecyl ether, p-vinylbenzyl-2,4,4,5,7,7,8,10,10,
11,13,13,14,16,16,17,17,1
8,18,18-Eicosafluoro-2,5,8,1
1,14-pentakis (trifluoromethyl) -3,
Examples include 6,9,12,15-pentaoxaoctadecyl ether.

Specific examples of the monomer (B-3) include 2,3,4,5,6-pentafluorostyrene.

The above-mentioned monomer (B-1), monomer (B-2) and monomer (B-3) can be used alone or in admixture of two or more.

In the present invention, the monomer (B-
The content of the monomer selected from 1), the monomer (B-2) and the monomer (B-3) in the polymerization component (B) is 60.
The content of the monomer (B-1), the monomer (B-2) and the monomer (B-3) is at least% by weight, but considering the balance of mechanical properties such as hardness and elasticity of the obtained hard ophthalmic lens material. The content of the monomer selected from the above in the polymerization component (B) is 70% by weight or more and 99.9% by weight or less, preferably 99% by weight or less.

In the present invention, the monomer (B-1), the monomer (B-2) and the monomer (B-
Examples of the monomer copolymerizable with the monomer selected from 3) (hereinafter referred to as the copolymerizable monomer (b)) include (α-methyl) styrene, methyl (α-methyl) styrene, ethyl (α-methyl) styrene. , N-propyl (α
-Methyl) styrene, isopropyl (α-methyl) styrene, isobutyl (α-methyl) styrene, t-butyl (α-methyl) styrene and other alkyl (α-methyl)
Styrene; dimethyl fumarate, diethyl fumarate,
Monomers of dialkyl fumarate such as di-n-propyl fumarate, diisopropyl fumarate, di-n-butyl fumarate, diisobutyl fumarate, di-t-butyl fumarate (hereinafter referred to as monomer (b-1)) 40% by weight, if necessary, for the purpose of further improving the mechanical properties, either alone or in combination of two or more.
Within the following range, the total amount of the polymerization component (B) can be added to the polymerization component (B) such that the total amount thereof is 100% by weight.

Further, the polymerization component (B) used in the present invention is obtained by polymerizing the copolymerizable monomer (b) other than the above-mentioned monomer (b-1) within the range of 40% by weight or less, if necessary. The component (B) may be contained so that the total amount becomes 100% by weight.

The kind of the copolymerizable monomer (b) may be appropriately selected depending on the properties of the target hard ophthalmic lens material.

For example, in order to improve the stain resistance of the obtained hard ophthalmic lens material, the functional monomer (a-3) used for obtaining the oxygen permeable material is used.
Among them, one kind or two or more kinds can be selected and contained in the polymerization component (B) in an amount of 40% by weight or less as the copolymerizable monomer (b).

When hydrophilicity is to be imparted to the obtained hard ophthalmic lens material, the hydrophilic monomer (a-2) used in obtaining the oxygen permeable material is used.
Among them, one kind or two or more kinds are selected, and the copolymerizable monomer (b) is preferably 1% by weight or more, more preferably 5% by weight or more, and preferably 30% by weight or less,
More preferably, it may be contained in the polymerization component (B) within the range of 25% by weight or less.

The reinforcing polymer used in the present invention can, of course, be the monomer (B-1) or the monomer (B-1) as long as it imparts excellent mechanical properties such as high hardness and elasticity to the hard ophthalmic lens material. It may be a homopolymer such as -2) or a copolymer of these with a copolymerizable monomer (b), and is not particularly limited.

Further, in order to improve the dimensional stability and chemical resistance of the obtained hard ophthalmic lens material by forming a crosslinked structure in the obtained reinforcing polymer, the copolymerizable monomer (b) is used. A crosslinkable monomer can be used as the).

Typical examples of the crosslinkable monomer include the crosslinkable monomer contained in the polymerization component (A), and these may be used alone or in combination of two or more.

The content of the crosslinkable monomer in the polymerization component (B) is such that the crosslinking effect is not sufficiently exhibited and there is no possibility that the finally obtained hard ophthalmic lens material will change with time. 0.1% by weight or more, preferably 1
It is preferably not less than 20% by weight, and preferably not more than 20% by weight in order to prevent the hard ophthalmic lens material from becoming brittle.

The type of the polymerization component (A) that gives the oxygen permeable material and the type of the polymerization component (B) that gives the reinforcing polymer are selected according to the purpose and application of the hard ophthalmic lens material of the present invention. It is preferable to use a combination, and a combination may be selected so that the oxygen permeable material is impregnated with the desired amount of the polymerization component (B).

The hard ophthalmic lens material of the present invention is one having an interpenetrating polymer network structure in which a network of an oxygen permeable material and a reinforcing polymer are intermingled with each other, and has optical transparency. However, for example, when a hard ophthalmic lens material having excellent optical properties is to be obtained, it is preferable to minimize the difference between the refractive index of the oxygen permeable material and the refractive index of the reinforcing polymer.

In the present invention, the refractive index can be easily adjusted by adjusting the composition, the blending ratio and the like of the oxygen permeable material and the polymerization component (B), whereby the degree of phase separation can be achieved. Even when the value is slightly larger, the decrease in the transparency of the obtained hard ophthalmic lens material as a whole can be suppressed, and good transparency can be maintained.

For example, when the oxygen permeable material is selected in advance, the polymerization component (B) capable of giving a reinforcing polymer having a refractive index as close as possible to that of the oxygen permeable material may be appropriately selected. On the contrary, when the reinforcing polymer is selected in advance, the polymerization component (A) which can give the oxygen permeable material having a refractive index as close as possible to that of the reinforcing polymer may be appropriately selected. .

Next, a method for producing the oxygen permeable hard eye lens material of the present invention will be described.

First, the monomer (B-1) and the monomer (B
-2), a desired component obtained by polymerizing the polymerization component (A) containing the monomer (A-1) and the crosslinkable monomer in the polymerization component (B) containing the monomer (B-3) and the like in advance. Immerse a crosslinked oxygen permeable material consisting of a polymer having a crosslink density of. The polymerized component (B) gradually impregnates the oxygen permeable material, and the oxygen permeable material swells. After the polymerization component (B) is impregnated into the oxygen permeable material and reaches a completely swollen state (equilibrium swollen state), the polymerization component (B) is polymerized.

The amount of the polymerization component (B) when the polymerization component (B) is impregnated into the oxygen permeable material to reach the equilibrium swelling state is determined by the degree of crosslinking of the oxygen permeable material and the oxygen permeable material. It cannot be unconditionally determined because it depends on the parameter of the interaction between the polymer component (B) and the polymer component (B), but in order to impart sufficient oxygen permeability to the obtained hard ophthalmic lens material, the formed The weight of the ratio of the oxygen permeable material to the reinforcing polymer (oxygen permeable material / reinforcing polymer) in the penetrating polymer network structure is 20/80 or more, preferably 25/75 or more, so that the polymerization component (B )
It is preferable to adjust the type and amount of the. Further, in order to sufficiently impart excellent mechanical properties such as high hardness and high flexural elasticity to the hard ophthalmic lens material, the ratio of the oxygen permeable material to the reinforcing polymer is 80/20 or less in weight ratio. It is preferable to adjust the type and amount of the polymerization component (B) so that it is preferably 75/25 or less.

Polymerization of the above-mentioned polymerization component (B) can be carried out by, for example, an ordinary radical polymerization method, a light irradiation polymerization method, an ultraviolet irradiation polymerization method, a radiation irradiation polymerization method, an anionic polymerization method,
It can be carried out by an ionic polymerization method such as a coordination anionic polymerization method or a cationic polymerization method.

Among these polymerization methods, the radical polymerization method and the ultraviolet irradiation polymerization method are preferable from the viewpoint of easy polymerization operation.

When the polymerization of the polymerization component (B) is carried out by a radical polymerization method, a radical polymerization initiator may be mixed and dissolved in the polymerization component (B).

Examples of the radical polymerization initiator include azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile) and 2,2'-azobis (4-methoxy-2,4-). Azo polymerization initiators such as dimethyl valeronitrile); organic peroxide polymerization initiators such as benzoyl peroxide, di-t-butyl peroxide, cumene peroxide; sodium persulfate, potassium persulfate, ammonium persulfate, etc. Examples include water-soluble polymerization initiators.

The amount of the radical polymerization initiator used should be 0.05 to 100 parts by weight of the polymerization component (B) in order to sufficiently accelerate the progress of the polymerization reaction and to complete the reaction in a short time. It is preferably at least parts by weight. Further, in order to sufficiently increase the molecular weight of the reinforcing polymer to be produced and to sufficiently improve the mechanical strength, the amount of the radical polymerization initiator used is 0.1% with respect to 100 parts by weight of the polymerization component (B).
It is preferably 5 parts by weight or less.

If the polymerization of the polymerization component (B) starts before the oxygen permeable material reaches the equilibrium swelling state by the polymerization component (B), the polymerization component ( There is a possibility that a part which is not completely impregnated with B) will be formed, and the composition will be nonuniform between the outer peripheral portion and the inner portion, and the workability of the obtained hard ophthalmic lens material may be reduced. Therefore, it is desirable to start the polymerization after the oxygen-permeable material reaches the equilibrium swelling state in the polymerization component (B).

After the equilibrium swelling state is reached, the method of initiating the polymerization is, for example, that the oxygen permeable material reaches the equilibrium swelling state in the polymerization component (B), for example, the swelling degree of the oxygen permeable material. Alternatively, a method in which after confirming the change in weight, a radical polymerization initiator is added to the polymerization component (B) to initiate polymerization, the polymerization component (B) is previously prepared.
In order to prevent the radical polymerization initiator from decomposing, the oxygen permeable material is held at a low temperature until the equilibrium swelling state is reached in the polymerization component (B). Then, a method of raising the temperature to start the polymerization can be mentioned.

When the polymerization of the polymerization component (B) is carried out by the ultraviolet irradiation polymerization method, the above-mentioned polymerization component (B) is used.
An ultraviolet polymerization initiator may be mixed and dissolved therein.

Examples of the UV polymerization initiator include benzoin, benzoin ethyl ether, benzoin isobutyl ether, acetophenone, benzophenone,
Biacetyl, benzyl dimethyl ketal, methylbenformate, 1- (4-isopropylphenyl) -2-
Examples thereof include hydroxy-2-methylpropan-1-one and 2-hydroxy-2-methyl-1-phenylpropan-1-one.

The amount of the ultraviolet polymerization initiator used is 0.05 in order to sufficiently accelerate the progress of the polymerization reaction and to complete the reaction in a short time with respect to 100 parts by weight of the polymerization component (B). It is preferably at least parts by weight. Further, in order to sufficiently increase the molecular weight of the produced reinforcing polymer and sufficiently improve the mechanical strength, the amount of the ultraviolet polymerization initiator used is 0.5 with respect to 100 parts by weight of the polymerization component (B).
It is preferably less than or equal to parts by weight.

When the UV irradiation polymerization method is adopted, a UV polymerization initiator is mixed and dissolved in the polymerization component (B) and the oxygen permeable material is immersed in the UV polymerization initiator, for example, in the same manner as described above. After confirming that the permeable material has reached the equilibrium swelling state, irradiation with ultraviolet rays may be carried out, for example, to initiate polymerization in the same manner as described above. Examples of means for irradiating with ultraviolet rays include high-pressure mercury lamps, germicidal lamps, black lights and the like which are generally used in ultraviolet ray irradiation polymerization methods.

The ratio of the oxygen permeable material and the reinforcing polymer in the hard ophthalmic lens material having the interpenetrating polymer network structure formed from the oxygen permeable material and the reinforcing polymer thus obtained (oxygen permeable material / reinforcing material) Polymer)
As described above, the weight ratio is 20/80 or more, especially 25/75 or more, and 80/20 or less, especially 75
It is preferably / 25 or less.

An ophthalmic lens is obtained by processing the hard ophthalmic lens material on which the interpenetrating polymer network structure is formed into a desired ophthalmic lens shape.

In the present invention, the method for processing the obtained hard ophthalmic lens material into a desired ocular lens shape is not particularly limited, and for example, it is cut into a desired ocular lens shape,
Then, a usual method such as a mechanical processing method of polishing the surface can be adopted.

According to the production method of the present invention, a hard ophthalmic lens material having not only optical transparency but also high oxygen permeability and particularly excellent mechanical properties such as hardness and bending elasticity. The hard ophthalmic lens material of the present invention is suitable for use in ophthalmic lenses such as hard contact lenses.

[0110]

EXAMPLES Next, the oxygen permeable hard ophthalmic lens material of the present invention and the method for producing the same will be described in more detail based on examples, but the present invention is not limited to these examples.

Example 1 (Production of Oxygen-permeable Material) Tris (trimethylsiloxy) silylstyrene (hereinafter referred to as SiS) as the polymerization component (A).
t) and 4 mol parts of bisphenol A dimethacrylate (hereinafter referred to as BP-A-DMA), and 2,2'-azobis (2,4-dimethylvaleronitrile) (hereinafter referred to as V as a radical polymerization initiator). −
(Referred to as 65).
mm glass test tube, sealed at the opening, prepolymerized at 30 ° C. for 88 hours and 50 ° C. for 8 hours, and then transferred to a circulation dryer for 1.5 to 5 minutes. The temperature was raised to 120 ° C. at a rate of 10 ° C. per hour to complete the polymerization to obtain a rod-shaped crosslinked oxygen-permeable material.

From the obtained oxygen permeable material, test pieces of the respective dimensions shown below were prepared, and the oxygen permeability coefficient, Tg, Rockwell hardness and flexural modulus as physical properties of the test pieces were examined according to the following methods. . As a result, the oxygen permeability coefficient was 392 × 10 ⁻¹¹ (cm ² / sec) · (mlO ₂ /
(Ml × mmHg)), Tg was 94 ° C., Rockwell hardness was −81, and flexural modulus was 568 MPa.

(Production of lens material for hard eye) 0.05-hydroxy-2-methyl-1-phenylpropan-1-one (ultraviolet polymerization initiator) was added as a polymerization component (B).
Approximately 60 g of 2,2,2-trifluoroethyl methacrylate (hereinafter referred to as 3FEMA) containing 20% by weight has an inner diameter of 20 m
m glass test tube, then diameter 14 mm,
The oxygen permeable material obtained above having a length of about 100 mm,
It was immersed in 3FEMA containing an ultraviolet polymerization initiator.

Then, the test tube made of glass was sealed with an opening, shielded from light by an aluminum foil, and then allowed to stand in a constant temperature water bath at 25 ° C. After confirming that the oxygen permeable material has reached an equilibrium swelling state in 3FEMA containing an ultraviolet polymerization initiator by confirming the change in cross-sectional size and shape of the oxygen permeable material over time, the aluminum foil for light shielding is removed, Polymerization was performed by irradiating a black light from the outside.

The obtained hard ophthalmic lens material was transparent and hard and was preferable as a hard contact lens material. In addition, regarding the obtained material, a gas chromatograph (5890 SER manufactured by Hewlett-Packard Co., Ltd.
As a result of a thermal decomposition chromatography analysis using IES II), it was confirmed that the material contained 61.9% by weight of the oxygen permeable material.

Next, the obtained hard ophthalmic lens material was subjected to machining by cutting and polishing to prepare test pieces of the following dimensions. At this time, the hard ophthalmic lens material could be machined very easily.

As the physical properties of the obtained test piece, transparency, oxygen permeability coefficient, flexural modulus and Rockwell hardness were examined according to the following methods. The results are shown in Table 1.

(A) A transparent surface-polished film having a diameter of 12.7 mm and a thickness of 0.5 mm was visually observed and evaluated based on the following evaluation criteria.

(Evaluation Criteria) A: The field of view on the other side can be sufficiently confirmed, and there is no fog at all. Δ: It is cloudy and the visual field on the other side cannot be clearly confirmed. X: The visual field on the other side cannot be confirmed at all.

(B) Oxygen permeability coefficient Gas permeability measuring device Model manufactured by Yanagimoto Seisakusho Co., Ltd.
Using GTR-10, diameter 12.7mm, thickness 0.5m
The test piece of m was measured at 35 ° C. The unit is (cm ² / sec) ・ (mlO ₂ / (ml × mmHg))
Is.

(C) Flexural modulus Modulus 430, universal testing machine manufactured by Instron
1, the distance between fulcrums is 8 mm and the width is 3 m at a temperature of 23 ° C.
The measurement was performed on a strip-shaped test piece having a thickness of m and a thickness of 0.5 mm. The unit is MPa.

(D) Rockwell Hardness Using a Rockwell Superficial Hardness Tester manufactured by Akashi Seisakusho Co., Ltd., load 30 kg, indenter ¼ inch (about 0.64 cm), temperature 25 ° C., relative humidity 50%. A test piece having a diameter of 12.7 mm and a thickness of 4 mm was measured in a constant temperature and humidity chamber (no unit).

(E) Tg Dynamic viscoelasticity measuring device RSA II manufactured by Rheometrics
Was used to measure the temperature dispersion (frequency 1 Hz) in the tensile mode, and the temperature at which the storage elastic modulus began to decrease was Tg.
(° C).

Comparative Example 1 As a result of the thermal decomposition chromatography analysis of the material obtained in Example 1, as described above, the oxygen permeable material was contained at 61.9% by weight. Therefore, the polymerization component (A) is adjusted so that the composition of the oxygen permeable material component is 61.9% by weight and the homopolymer component of 3FEMA is 38.1% by weight.
And the polymerization component (B) were mixed. That is, SiSt
59.6 parts by weight, BP-A-DMA 2.2 parts by weight, 3
38.1 parts by weight of FEMA and V-6 as a polymerization initiator
A hard ophthalmic lens material was obtained in the same manner as in "Production of oxygen-permeable material" in Example 1 except that 0.1 part by weight of 5 was mixed and dissolved to form a uniform monomer mixture.

Test pieces were prepared from the obtained materials, and the physical properties of the test pieces were examined in the same manner as in Example 1. The results are shown in Table 1.

Table 1 also shows the blending ratio (by weight) of each polymerization component and polymerization initiator.

[0127]

[Table 1]

From the results shown in Table 1, the hard ophthalmic lens material obtained in Example 1 has excellent transparency and is obtained by simply copolymerizing the polymerization components of the same composition of Comparative Example 1. It can be seen that in comparison with the hard ophthalmic lens material, the Rockwell hardness indicating the surface hardness is high and the oxygen permeability coefficient is large, and the oxygen permeability and the mechanical properties are excellent at the same time.

Example 2 (oxygen permeable material) The crosslinked oxygen permeable material obtained in Example 1 was used.

(Production of Hard Eye Lens Material) 3FEMA
In the same manner as in “Production of lens material for hard eye” in Example 1 except that 1,1,1,3,3,3-hexafluoroisopropyl methacrylate (hereinafter referred to as 6FIPMA) was used instead of I got the lens material.

The obtained material was transparent and hard and was preferable as a hard contact lens material. Further, the obtained material was subjected to pyrolysis chromatography analysis in the same manner as in Example 1, and as a result, it was confirmed that the material contained 66.8% by weight of an oxygen permeable material.

Then, a test piece was prepared from the obtained hard eye lens material in the same manner as in Example 1. At this time, the hard ophthalmic lens material could be machined very easily.

Next, the physical properties of the obtained test piece were evaluated in Example 1.
I examined it in the same way. The results are shown in Table 2.

Comparative Example 2 As a result of the thermal decomposition chromatography analysis of the material obtained in Example 2, as described above, the oxygen permeable material was contained at 66.8% by weight. Then, the polymerization component (A) and the polymerization component (B) were mixed so that the composition of the oxygen permeable material component was 66.8% by weight and the homopolymer component of 6FIPMA was 33.2% by weight. That is, Si
St 64.4 parts by weight, BP-A-DMA 2.3 parts by weight, 6FIPMA 33.2 parts by weight and V-65 0.1 part by weight as a polymerization initiator were mixed and dissolved to form a uniform monomer mixture. A hard ophthalmic lens material was obtained in the same manner as in "Production of oxygen-permeable material" in Example 1.

Test pieces were prepared from the obtained materials, and the physical properties of the test pieces were examined in the same manner as in Example 1. The results are shown in Table 2.

Table 2 also shows the blending ratio (by weight) of each polymerization component and polymerization initiator.

[0137]

[Table 2]

From the results shown in Table 2, the hard ophthalmic lens material obtained in Example 2 has excellent transparency and is obtained by simply copolymerizing the polymerization component of Comparative Example 2 having the same composition. Compared with the hard ophthalmic lens material, it has almost the same oxygen permeability coefficient, and the flexural modulus and Rockwell hardness are both large. Especially, the Rockwell hardness indicating the surface hardness is remarkably large and the oxygen permeability is high. It can be seen that the mechanical properties are excellent at the same time.

Example 3 (Production of Oxygen-permeable Material) SiS as Polymerization Component (A)
t 100 parts by mole and BP-A-DMA 4 parts by mole,
And V-65 0.32 as a radical polymerization initiator
The mol part is mixed and dissolved, poured into a glass test tube having an inner diameter of 15 mm, the opening is tightly capped, and the mixture is kept at 35 ° C. for 37 hours.
After preliminarily polymerizing at 0 ° C. for 7 hours, the test tube was transferred into a circulation dryer, and 110 ° C. at a rate of 10 ° C. for 2 to 3 hours.
The temperature was raised to ℃ and the polymerization was completed to obtain a rod-shaped crosslinked oxygen-permeable material.

Test pieces of various sizes were prepared from the obtained oxygen-permeable material, and the physical properties of the test pieces were examined in the same manner as in Example 1. As a result, the oxygen permeability coefficient was 392 × 10 ^-11.
(Cm ² / sec) ・ (mlO ₂ / (ml × mmH
g)), Tg was 94 ° C., Rockwell hardness was −81, and flexural modulus was 568 MPa.

(Production of Hard Ophthalmic Lens Material) As a polymerization component (B), 0.01% of 2-hydroxy-2-methyl-1-phenylpropan-1-one (ultraviolet polymerization initiator) was used.
About 100 g of methyl methacrylate (hereinafter referred to as MMA) containing 10 wt% was injected into a glass test tube having an inner diameter of 20 mm, and then the oxygen permeable material having a diameter of 13 mm and a length of about 80 mm was added with an ultraviolet polymerization initiator. Including MM
It was immersed in A.

Then, the glass test tube was tightly closed at the opening thereof, shielded from light by an aluminum foil, and then allowed to stand in a constant temperature water bath at 25 ° C. Example 1 shows that the oxygen permeable material reached an equilibrium swelling state in MMA containing a UV polymerization initiator.
After confirming in the same manner as above, the aluminum foil for shading was removed, and black light was irradiated from outside to carry out polymerization.

The obtained hard ophthalmic lens material was transparent and hard and was preferable as a hard contact lens material. Further, the obtained material was subjected to pyrolysis chromatography analysis in the same manner as in Example 1, and as a result, it was confirmed that the material contained 58.9% by weight of an oxygen permeable material.

Then, a test piece was prepared from the obtained hard ophthalmic lens material in the same manner as in Example 1. At this time, the hard ophthalmic lens material could be machined very easily.

Next, the physical properties of the obtained test piece were measured in Example 1.
I examined it in the same way. The results are shown in Table 3.

Comparative Example 3 From the result of the thermal decomposition chromatography analysis of the material obtained in Example 3, as described above, the oxygen permeable material was contained in an amount of 58.9% by weight. Then, the polymerization component (A) is adjusted so that the composition of the oxygen permeable material component is 58.9% by weight and the homopolymer component of MMA is 41.1% by weight.
And the polymerization component (B) were mixed. That is, SiSt
56.7 parts by weight, BP-A-DMA 2.1 parts by weight, M
MA 41.1 parts by weight and V-65 as a polymerization initiator
A hard ophthalmic lens material was obtained in the same manner as in "Production of oxygen-permeable material" in Example 1 except that 0.1 part by weight was mixed and dissolved to form a uniform monomer mixture.

Test pieces were prepared from the obtained materials, and the physical properties of the test pieces were examined in the same manner as in Example 1. The results are shown in Table 3.

Table 3 also shows the blending ratio (by weight) of each polymerization component and polymerization initiator.

[0149]

[Table 3]

From the results shown in Table 3, the hard ophthalmic lens material obtained in Example 3 has excellent transparency and is obtained by simply copolymerizing the polymerization components of Comparative Example 3 having the same composition. Compared with the hard ophthalmic lens material, it has almost the same flexural modulus and Rockwell hardness, and has a remarkably large oxygen permeability coefficient, and it has excellent oxygen permeability and mechanical properties at the same time. I understand.

Example 4 (Oxygen-permeable material) The crosslinked oxygen-permeable material obtained in Example 1 was used.

(Manufacture of Lens Material for Hard Eye) 3FEMA
4-tert-butylstyrene (hereinafter, t-
A hard eye lens material was obtained in the same manner as in “Production of hard eye lens material” in Example 1 except that (BuSt) was used.

The obtained material was transparent and hard and was preferable as a hard contact lens material. Further, the obtained material was subjected to pyrolysis chromatography analysis in the same manner as in Example 1, and as a result, it was confirmed that the material contained 57.9% by weight of an oxygen permeable material.

Next, a test piece was prepared from the obtained hard ophthalmic lens material in the same manner as in Example 1. At this time, the hard ophthalmic lens material could be machined very easily.

Next, the physical properties of the obtained test piece are shown in Example 1.
I examined it in the same way. The results are shown in Table 4.

Comparative Example 4 As a result of the pyrolysis chromatography analysis of the material obtained in Example 4, as described above, the oxygen permeable material was contained in an amount of 57.9% by weight. Then, the polymerization component (A) and the polymerization component (B) were mixed so that the composition of the oxygen permeable material component was 57.9% by weight and the homopolymer component of t-BuSt was 42.1% by weight. That is, Si
St 55.8 parts by weight, BP-A-DMA 2.0 parts by weight, t-BuSt 42.1 parts by weight and V-65 0.1 parts by weight as a polymerization initiator were mixed and dissolved to obtain a uniform monomer mixture. A hard eye lens material was obtained in the same manner as in "Production of oxygen permeable material" in Example 1 except for the above.

Test pieces were prepared from the obtained materials, and the physical properties of the test pieces were examined in the same manner as in Example 1. The results are shown in Table 4.

Table 4 also shows the blending ratio (by weight) of each polymerization component and polymerization initiator.

[0159]

[Table 4]

From the results shown in Table 4, the hard ophthalmic lens material obtained in Example 4 has excellent transparency, and is obtained by simply copolymerizing the polymerization component of Comparative Example 4 having the same composition. Compared with hard ophthalmic lens materials, it has a high flexural modulus and a similar Rockwell hardness, and also has a large oxygen permeability coefficient, and it has excellent oxygen permeability and mechanical properties at the same time. .

[0161]

According to the manufacturing method of the present invention, not only it has optical transparency but also high oxygen permeability, and it is an oxygen permeable hard material having excellent mechanical properties such as hardness and bending elasticity. The ophthalmic lens material can be easily obtained.

Since the oxygen-permeable hard eye lens material of the present invention is excellent in oxygen permeability as described above, a contact lens obtained from such a hard eye lens material is worn on the eye. In this case, it does not impose any physiological burden on the cornea, and at the same time it has excellent mechanical properties, so the shape of the contact lens does not change easily, and it is particularly suitable for hard contact lenses. It is profitable.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Toshio Yamazaki, Inventor Toshio Yamazaki, No. 1 Hitomi, Osamu Matsuida-cho, Usui-gun, Gunma Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory (56) Reference JP-A-4-281423 ( JP, A) JP-A-6-214196 (JP, A) JP-A-4-168415 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G02C 7/04 A61F 2/16

Claims (8)

(57) [Claims] 1. A compound represented by the general formula (I): (Wherein, m and n are each independently an integer of 1 to 15, and p is 0 or 1) 60 to 99.9% by weight of a silicon-containing styrene derivative and 0.1 to 20% by weight of a crosslinkable monomer. % As a main component, a cross-linked oxygen-permeable material comprising a polymer obtained by polymerizing a polymerization component (A), represented by the general formula (II): (In the formula, R ¹ is a hydrogen atom or a methyl group, R ² is a carbon atom 1
To a linear, branched or cyclic alkyl group having 7 to 7 carbon atoms, an aromatic ring-containing group having 6 to 10 carbon atoms, a straight chain having 1 to 7 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom,
6 to 10 carbon atoms in which at least one of a branched or cyclic alkyl group or a hydrogen atom is substituted with a fluorine atom
Represents an aromatic ring-containing group), a compound represented by the general formula (III): (In the formula, R ³ is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 7 carbon atoms, an aromatic ring-containing group having 6 to 10 carbon atoms, and at least one of hydrogen atoms is a fluorine atom. A substituted straight-chain, branched-chain or cyclic alkyl group having 1 to 7 carbon atoms, an aromatic ring-containing group having 6 to 10 carbon atoms in which at least one of hydrogen atoms is substituted with a fluorine atom, a general formula (IV ): [Chemical 4] (In the formula, R ⁴ is a linear, branched, or cyclic alkyl group having 1 to 7 carbon atoms, an aromatic ring-containing group having 6 to 10 carbon atoms, and at least one of hydrogen atoms is substituted with a fluorine atom. A linear, branched or cyclic alkyl group having 1 to 7 carbon atoms or an aromatic ring-containing group having 6 to 10 carbon atoms in which at least one of hydrogen atoms is substituted with a fluorine atom, a represents 0 or 1. ), A group represented by the general formula (V): (In the formula, b represents 0 or an integer of 1 to 4) or a group represented by the general formula (VI): (In the formula, q represents 0 or an integer of 1 to 7, r represents an integer of 1 to 3) and a monomer represented by the general formula (VII): (In the formula, R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom or a fluorine atom, and R ⁵ , R ⁶ ,
At least one of R ⁷ , R ⁸ and R ⁹ is a fluorine atom);
An optically transparent oxygen-permeable hard ophthalmic lens material having an interpenetrating polymer network structure formed from a reinforcing polymer made of a polymer obtained by polymerizing a polymerization component (B) contained in an amount of at least wt%. 2. The oxygen permeable hard ophthalmic lens material according to claim 1, wherein the polymerization component (A) contains a silicon-containing styrene derivative and / or a monomer copolymerizable with a crosslinking monomer as the balance. 3. A polymerization component wherein (B) is copolymerizable with a monomer selected from the monomers represented by general formula (II), the general formula (III) and the general formula (VII). The oxygen-permeable hard ophthalmic lens material according to claim 1 or 2, which contains a different monomer as the balance. 4. The weight ratio of the oxygen permeable material to the reinforcing polymer (oxygen permeable material / reinforcing polymer) is 20/8.
The oxygen-permeable hard ophthalmic lens material according to claim 1, 2 or 3, which is 0 to 80/20. 5. General formula (I): embedded image (Wherein, m and n are each independently an integer of 1 to 15, and p is 0 or 1) 60 to 99.9% by weight of a silicon-containing styrene derivative and 0.1 to 20% by weight of a crosslinkable monomer. % As the main component, a cross-linked oxygen-permeable material made of a polymer obtained by polymerizing the polymerization component (A) has the general formula (II): (In the formula, R ¹ is a hydrogen atom or a methyl group, R ² is a carbon atom 1
To a linear, branched or cyclic alkyl group having 7 to 7 carbon atoms, an aromatic ring-containing group having 6 to 10 carbon atoms, a straight chain having 1 to 7 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom,
6 to 10 carbon atoms in which at least one of a branched or cyclic alkyl group or a hydrogen atom is substituted with a fluorine atom
Of the aromatic ring-containing group), represented by the general formula (III): (In the formula, R ³ is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 7 carbon atoms, an aromatic ring-containing group having 6 to 10 carbon atoms, and at least one of hydrogen atoms is a fluorine atom. A substituted straight-chain, branched-chain or cyclic alkyl group having 1 to 7 carbon atoms, an aromatic ring-containing group having 6 to 10 carbon atoms in which at least one of hydrogen atoms is substituted with a fluorine atom, a general formula (IV ): (In the formula, R ⁴ is a linear, branched, or cyclic alkyl group having 1 to 7 carbon atoms, an aromatic ring-containing group having 6 to 10 carbon atoms, and at least one of hydrogen atoms is substituted with a fluorine atom. A linear, branched or cyclic alkyl group having 1 to 7 carbon atoms or an aromatic ring-containing group having 6 to 10 carbon atoms in which at least one of hydrogen atoms is substituted with a fluorine atom, a represents 0 or 1. ), A group represented by the general formula (V): (In the formula, b represents 0 or an integer of 1 to 4) or a group represented by the general formula (VI): (In the formula, q represents 0 or an integer of 1 to 7 and r represents an integer of 1 to 3) and a monomer represented by the general formula (VII): (In the formula, R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom or a fluorine atom, and R ⁵ , R ⁶ ,
At least one of R ⁷ , R ⁸ and R ⁹ is a fluorine atom);
After impregnating the polymerization component (B) contained in an amount of not less than wt%,
An interpenetrating polymer network structure is formed from a cross-linked oxygen-permeable material characterized by polymerizing the polymerizing component (B) and a reinforcing polymer composed of a polymer obtained by polymerizing the polymerizing component (B). A method for producing an optically transparent oxygen-permeable hard ophthalmic lens material formed. 6. The method for producing an oxygen-permeable hard ophthalmic lens material according to claim 5, wherein the polymerization component (A) contains a silicon-containing styrene derivative and / or a monomer copolymerizable with a crosslinking monomer as the balance. . 7. The polymerization component (B) is copolymerizable with a monomer selected from the monomer represented by the general formula (II), the monomer represented by the general formula (III) and the monomer represented by the general formula (VII). The method for producing an oxygen-permeable hard ophthalmic lens material according to claim 5 or 6, wherein the monomer contains the remaining monomer as the balance. 8. A weight ratio of the oxygen permeable material to the reinforcing polymer (oxygen permeable material / reinforcing polymer) is 20/8.
It is 0-80 / 20, The manufacturing method of the oxygen permeable hard ophthalmic lens material of Claim 5, 6 or 7.