JP2588945B2 - Soft ophthalmic lens material - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a soft ophthalmic lens material. More specifically, the present invention relates to a soft ophthalmic lens material that can be suitably used as a material for a contact lens, an intraocular lens, an artificial cornea and the like.

[Prior Art] Conventionally, various ophthalmic lens materials have been proposed as materials for contact lenses, materials for intraocular lenses, and the like.
Such ophthalmic lens materials are roughly classified into a soft material and a hard material, but can be deformed and inserted simply by incising the eyeball without damaging the contact lens material or the eye tissue with a good feeling of wearing. It is well known that soft materials are generally preferred as materials for intraocular lenses.

Soft materials are divided into hydrous materials which absorb water and swell and soften, and substantially non-hydrous materials.

The water-containing material has a drawback that the mechanical strength is inferior because the ratio of the material itself occupying the water in the material is relatively small. In addition, bacteria and fungi easily propagate in the material containing water, and when used as a contact lens, complicated operations such as boiling disinfection are required.

Examples of the substantially non-water-containing material include, for example, a material made of silicone rubber, a copolymer of an alkyl acrylate or a long-chain alkyl methacrylate or a copolymer of acrylic acid (hereinafter referred to as (( (Meth) acrylate-based soft material).

Although the material made of silicone rubber has an advantage that oxygen permeability is very high, the surface of the obtained material is extremely strong water repellent, and it does not fit well with the cornea and other eye tissues. It has been reported that some of the materials applied as a material for the eye caused serious damage to ocular tissues.

Among the (meth) acrylate-based soft materials, those made of a copolymer containing butyl acrylate as a main component have been put into practical use as contact lenses. However, a contact lens made of such a material has a sticky surface and is liable to adhere to dirt such as lipids, so that it is likely to be cloudy, oxygen permeability is so high, and mechanical strength is not satisfactory. There were many things to be done.

Examples of the (meth) acrylate-based soft material include, in addition to the above, an acrylate ester, a methacrylate ester and a compound having a cyclic structure and two or more functional groups in the molecule, and A non-water-containing soft contact lens comprising a copolymer using a crosslinkable monomer having two or more atoms has been proposed (Japanese Patent Application Laid-Open No. Sho 62).
-127823). Although such non-hydrous soft contact lenses have improved mechanical strength and flexibility, they are easily contaminated by dirt such as lipids, and their oxygen permeability is not enough to allow continuous wearing as contact lenses.

Further, in addition to the above, fluorine-containing methacrylate,
Non-water-containing soft contact lenses made of copolymers of methacrylates, acrylates and crosslinkable monomers other than those described above (JP-A-62-127824), acrylic acid and / or methacrylic acid and crosslinkable monomers A method for producing a non-water-containing oxygen-permeable soft contact lens obtained by esterifying a hard copolymer obtained by copolymerizing a monomer mixture containing the same with a fluorinated alcohol (Japanese Patent Application Laid-Open No. 62-127825) has been proposed. I have. However, all of the contact lenses described in these publications have improved mechanical strength to some extent, and although oxygen permeability is somewhat good, when a large amount of a crosslinkable monomer is used to further improve mechanical strength, oxygen There are disadvantages in that the permeability is reduced, the flexibility is reduced, and the material becomes brittle.

[Problems to be Solved by the Invention] In view of the above-mentioned prior art, the present inventors have shown that, in addition to being excellent in transparency, they exhibit substantially non-hydrous or low-hydrous content and have a sticky surface. As a result of intensive studies to obtain a soft ophthalmic lens material that is free from dirt such as lipids, has excellent oxygen permeability, and has mechanical strength that is practically satisfactory, all these properties are satisfied. For the first time, the present inventors have found an ophthalmic lens material, and have completed the present invention.

[Means for Solving the Problems] That is, the present invention relates to an alkyl (meth) acryl having a glass transition point of 40 ° C. or lower when (A) a fluorine-containing (meth) acrylate and (B) a homopolymer. A polymer comprising a monomer containing an acid ester and (C) a fluorine-containing (meth) acrylic acid ester, comprising a (meth) acrylate-based polymer having an average of 0.05 to 5 radically polymerizable polymer groups in a molecule. The present invention relates to a soft ophthalmic lens material comprising a copolymer containing a copolymer component as an essential component.

[Functions and Examples] As described above, the soft ophthalmic lens material of the present invention includes:
(A) Fluorine-containing (meth) acrylate, (B)
An alkyl (meth) acrylate having a glass transition point of 40 ° C. or lower when formed into a homopolymer; and (C)
An essential copolymerization component comprising a polymer comprising a monomer containing a fluorine-containing (meth) acrylic acid ester and comprising a (meth) acrylate-based polymer having an average of 0.05 to 5 radically polymerizable polymer groups in a molecule. And a copolymer represented by the following formula:

The fluorine-containing (meth) acrylate (hereinafter, referred to as
The monomer (A) is a component that imparts oxygen permeability to the material and exhibits an effect of making dirt such as lipids hardly adhere to the material. As a typical example of such a monomer (A), for example, a general formula (I): CH ₂ CRCR ₁ COOC _m H _{(2m-n-1 + 1)} F _n (OH) _l (I) (wherein, R ₁ Is a hydrogen atom or CH ₃ , m is an integer of 1 to 15,
n is an integer of 1 to (2m + 1), l is an integer of 0 to 2)
And a monomer represented by the following formula: Specific examples of such a monomer include, for example, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 2,2,3,3-tetrafluoro- t-pentyl (meth) acrylate, 2,2,3,4,4,4-
Hexafluorobutyl (meth) acrylate, 2,2,3,4,
4,4-hexafluoro-t-hexyl (meth) acrylate, 2,3,4,5,5,5-hexafluoro-2,4-bis (trifluoromethyl) pentyl (meth) acrylate, 2,2,
3,3,4,4-hexafluorobutyl (meth) acrylate, 2,2,2,2 ', 2', 2'-hexafluoroisopropyl (meth) acrylate, 2,2,3,3,4,4 , 4-heptafluorobutyl (meth) acrylate, 2,2,3,3,4,4,5,5-octafluoropentyl (meth) acrylate, 2,2,3,3,
4,4,5,5,5-nonafluoropentyl (meth) acrylate, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl (meth) acrylate, 3,3,4,4,5,5,6,6,7,7,8,8
Dodecafluorooctyl (meth) acrylate, 3,3,4,
4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl (meth) acrylate, 2,2,3,3,4,4,5,5,6,6,7 , 7,7-Tridecafluoroheptyl (meth) acrylate, 3,3,4,4,
5,5,6,6,7,7,8,8,9,9,10,10-hexadecafluorodecyl (meth) acrylate, 3,3,4,4,5,5,6,6,7 , 7,8,8,9,
9,10,10,10-heptadecafluorodecyl (meth) acrylate, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11 , 11−
Octadecafluoroundecyl (meth) acrylate,
3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-nonadecafluoroundecyl (meth) acrylate, 3, 3,4,4,
5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12-eicosafluorododecyl (meth) acrylate, 2-hydroxy-4,4,5 , 5,6,7,7,7-octafluoro-6-trifluoromethylheptyl (meth) acrylate, 2-hydroxy-4,4,5,5,6,6,7,7,8,9,9 , 9-Dodecafluoro-8-
Trifluoromethylnonyl (meth) acrylate, 2-
Hydroxy-4,4,5,5,6,6,7,7,8,8,9,9,10,11,11,11-
Hexadecafluoro-10-trifluoromethylundecyl (meth) acrylate and the like.

The compounding amount of the monomer (A) depends on the amount of the essential copolymer component.
20 to 80 parts, preferably 25 to 75 parts, particularly preferably 35 to 70 parts, per 100 parts (parts by weight, hereinafter the same). If the amount of the monomer (A) is less than the lower limit, the effect of compounding the monomer (A) will not be sufficiently exhibited, and if the amount is more than the upper limit, other copolymer components will be relatively present. Tend to reduce the flexibility of the resulting material due to the reduced amount of the compound.

When the above homopolymer is used, the glass transition point is 40 ° C.
The following alkyl (meth) acrylate (hereinafter, referred to as monomer (B)) is a component necessary for obtaining a flexible ophthalmic lens material, but has an effect of further imparting oxygen permeability to the material. It is a component to be exhibited.

The molecular weight of the homopolymer here is about 10,000 or more. This is because if the molecular weight of the homopolymer is 10,000 or more, the glass transition point (hereinafter, referred to as Tg) of the homopolymer does not depend on the molecular weight and does not change much.

When the Tg of the monomer (B) is a homopolymer, it is required that the temperature be 40 ° C. or less. When the Tg of the monomer (B) is higher than 40 ° C., the monomer (B) is used. This is because only a hard copolymer can be obtained and the flexibility, which is one of the objects of the present invention, is impaired. Therefore, a monomer that can obtain a homopolymer having a Tg lower than the body temperature, that is, 40 ° C. or lower, particularly 10 ° C. or lower is preferably used. Typical examples of the monomer (B) include acrylates having an alkyl group of 1 or more carbon atoms or methacrylates having an alkyl group of 8 or more carbon atoms. Specific examples thereof include, for example, methyl Acrylate (Tg as homopolymer (hereinafter simply abbreviated as Tg): 10 ° C), ethyl acrylate (Tg: -25 ° C), propyl acrylate (Tg: -37 ° C), n-butyl acrylate (Tg:- 54 ° C), isobutyl acrylate (Tg: -24
° C), hexyl acrylate (Tg: -57 ° C), 2-methylbutyl acrylate (Tg: -32 ° C), heptyl acrylate (Tg: -60 ° C), octyl acrylate (Tg: -65 ° C)
° C), dodecyl acrylate (Tg: -3 ° C), octyl methacrylate (Tg: -70 ° C), decyl methacrylate (Tg: -70 ° C), dodecyl methacrylate (Tg: -65)
° C) and benzyl acrylate (Tg: 6 ° C).

The amount of the monomer (B) is 10
The amount is 10 to 80 parts, preferably 15 to 65 parts, particularly preferably 20 to 55 parts with respect to 0 parts. If the amount is less than the lower limit, the effect of blending the monomer (B) is not sufficiently exhibited, the flexibility of the obtained material is reduced, and the material is too large than the upper limit. Not only does the elongation of the material become too large, the stickiness of the surface of the material becomes remarkable, but also the blending amount of other components becomes relatively small, and the obtained material tends to be easily contaminated by dirt such as lipids.

A polymer comprising a monomer containing the fluorine-containing (meth) acrylic acid ester, having an average of 0.05
(Meth) acrylate-based polymers having up to 5 radically polymerizable polymer groups (hereinafter referred to as macromers (C)) reinforce the obtained material without impairing its flexibility and oxygen permeability, and give the material an elasticity. It is a component that imparts high resilience (toughness or stiff resilience), improves mechanical strength, eliminates stickiness on the surface of the obtained material, and has an effect of making it difficult for lipid stains to adhere.

The macromer (C) has an average of 0.05 to 5, especially 0.1 to 3 polymer groups in the molecule. The macromer (C) having, for example, an average of 0.1 polymerized groups in the molecule means that an average of 1 macromer (C) per 1
Means that a macromer (C) having a polymer group in a proportion of the polymer is present.

Here, the number of polymer groups is determined by first analyzing the amount of units derived from monomers corresponding to the polymer groups of the macromer (C) by pyrolysis gas chromatography (PGC), and by gel permeation chromatography (GPC). A value obtained by measuring the number average molecular weight of the macromer (C) in terms of polystyrene, and calculating the average number of polymer groups per macromer (C) (molecule) from the amount of the monomer-derived unit corresponding to the polymer group and the number average molecular weight. It is. Since the molecular weight is determined as an average, the calculated number of polymerized groups is necessarily determined as an average.

However, the measured value of the molecular weight of the macromer (C) by GPC is different from the polystyrene of the same molecular weight as the macromer (C) because the hydrodynamic volume of the macromer (C) is different. A molecular weight different from the (real) molecular weight is measured. For that, Macromer (C)
It should be noted that the calculated average number of polymer groups, that is, the apparent number of polymer groups may be different from the number of polymer groups actually present.

The macromer (C) having the polymerizable group is copolymerized with other copolymer components and chemically bonded, so that the macromer (C) does not elute from the material, and is physically reinforced by simple entanglement of molecules. Not only that, they also have a reinforcing effect due to chemical bonding.

The number of polymer groups in one molecule of the macromer (C) having a polymer group is preferably 5 or less, and more preferably 3 or less from the viewpoint of securing the flexibility of the obtained copolymer. When the number of polymer groups contained in the macromer (C) in the molecule is less than 0.05 on average, the mechanical strength of the copolymer, which does not sufficiently exhibit the reinforcing effect, is reduced. If the number is more than one, the obtained copolymer tends to be small in elongation and brittle.

The macromer (C) has a number average molecular weight of 1,000 to 10,000.
0, preferably 2500 to 50000. When the number average molecular weight is smaller than the lower limit, a sufficient reinforcing effect is not imparted to the obtained material, and when the number average molecular weight is larger than the upper limit, the solubility to other copolymer components is reduced and the homogeneity is reduced. It is difficult to obtain a suitable material, and the obtained material tends to be cloudy.

The macromer (C) is mainly composed of a fluorine-containing (meth) acrylate, and the compounding amount of the fluorine-containing (meth) acrylate is 40 to 100 parts of the component of the macromer (C). ~ 100 parts, preferably
50-100 copies. If the amount is less than 40 parts, the compatibility between the macromer (C) and the monomer (A) decreases, and the resulting material may become cloudy. Specific examples of the fluorine-containing (meth) acrylic acid ester include those similar to the monomer (A).

The constituent components of the macromer (C) include, as necessary, for example, linear, branched, or cyclic alkyl (meth) acrylate, which is a component for imparting mechanical strength, and a component for imparting hydrophilicity. A certain hydrophilic monomer, for example, another monomer such as styrene, etc. may be blended within a range not exceeding 30 parts per 100 parts of the component of the macromer (C). If the amount exceeds 30 parts, the compatibility between the macromer (C) and the monomer (A) is reduced, and the material tends to be clouded.

Specific examples of the alkyl (meth) acrylate include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, and nonyl. (Meta)
Acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate and the like can be mentioned.

Specific examples of the hydrophilic monomer include, for example, a hydroxy group-containing alkyl (meth) acrylate such as hydroxyethyl (meth) acrylate; (meth) acrylic acid;
N-substituted acrylamides such as (meth) acrylamide and N, N-dimethyl (meth) acrylamide; N-vinyllactams such as N-vinylpyrrolidone;

The macromer (C) has an average of 0.05 to 5 radical polymerizable groups in the molecule. As a method for introducing such a polymerizable group into the macromer (C), there are mainly the following methods.

(A) A method in which the components of the macromer (C) are copolymerized with a monomer having two or more polymerizable groups in the components of the macromer (C) during polymerization.

(B) The components of the macromer (C) are polymerized in the presence of a chain transfer agent or a polymerization initiator having a carboxylic acid as a functional group, and the obtained polymer is dissolved in a suitable solvent in the presence of a basic catalyst. A method of introducing a polymer group by reacting with a polymer group-containing compound having an epoxy group as a functional group, such as glycidyl (meth) acrylate.

(C) Dissolve or emulsify the components of the macromer (C) in water, add hydrogen peroxide and a redox initiator,
Synthesize a polymer having a hydroxyl group at one end, and in a solvent such as pyridine, having a functional group that reacts with the hydroxyl group,
For example, a method of reacting with a polymer-containing compound such as (meth) acrylic acid chloride to introduce a polymer group into a terminal.

(D) A small amount of a monomer having a hydroxyl group as a functional group, for example, 2-hydroxyethyl methacrylate, is copolymerized with a component of the macromer (C), and the obtained polymer is reacted with a hydroxyl group in a suitable solvent. A method of introducing a polymer group by reacting with a polymer group-containing compound having a group, for example, (meth) acrylic acid chloride.

Of these methods, in the methods (b) and (c), the terminal polymer groups are always formed, so that the number of polymer groups in one molecule is limited to two or less. However, in the method (a) or (d), the number of polymer groups in one molecule is not limited. Therefore, the methods (a) and (d) are preferable in that the number of polymerizable groups in one molecule can be arbitrarily introduced as necessary, and the method ( The method a) is preferred.

When a polymer group is introduced by the method (a), the monomer having two or more polymer groups is converted into the macromer (C)
By copolymerizing together with the constituent component (a), a polymer having an average of at least 0.05 radically polymerizable polymerizable groups in the polymer molecule can be obtained.

In the method (a), specific examples of the monomer having two or more polymerizable groups include, for example, ethylene glycol di (meth) acrylate, allyl (meth) acrylate, vinyl (meth) acrylate, diethylene glycol di (meth) acrylate, Triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth)
Acrylate and trimethylolpropane tri (meth) acrylate.

When the macromer (C) is obtained by polymerization, particularly when the method (a) is used, all the polymer groups of the monomer having two or more polymer groups are not subjected to polymerization, in other words, two or more polymer groups are used. It is necessary to carry out the polymerization while controlling the polymerization conditions so that at least one of the polymer groups is not subjected to the polymerization. Therefore, it is preferably prepared by solution polymerization. As a solvent for solution polymerization, any solvent can be used as long as it can dissolve each copolymer component well and does not inhibit polymerization, and examples thereof include benzene and acetone. These solvents are used alone or in combination of two or more. Since the amount of the solvent varies depending on the reaction conditions, it is preferable to appropriately adjust the amount as needed.

In addition, there is a correlation between the reaction temperature and the reaction time, which are the polymerization conditions for obtaining the macromer (C) by polymerizing the constituents of the macromer (C), and such reaction conditions cannot be determined. Preferably, the reaction is carried out at a relatively low temperature of 50 to 80 ° C. for several minutes to several hours.

In the case of polymerization, it is common to use a polymerization initiator, and specific examples of such a polymerization initiator include, for example,
Examples include azobis compounds such as azobisisobutyronitrile and azobisdimethylvaleronitrile, and peroxides such as benzoyl peroxide.

Among the macromers (C) thus obtained, those having two or more polymerizable groups in the molecule have crosslinkability. That is, it not only reinforces the material, but also exhibits the same action as the crosslinking agent.

The blending amount of the macromer (C) is 100
The amount is from 2 to 35 parts, preferably from 3 to 30 parts, particularly preferably from 4 to 25 parts, per part. When the compounding amount is too small than the lower limit, the effect of compounding the macromer (C) will not be sufficiently exhibited, and when the compounding amount is too large, the other copolymer components will be relatively mixed. There is a tendency that the amount used is reduced and the flexibility of the resulting material is reduced.

In addition, the material of the present invention has improved stability such as shape stability and chemical resistance, heat resistance, solvent resistance and shape stability,
It is preferable to use a cross-linking agent or a macromonomer having at least two or more polymerizable groups in a molecule in order to reduce elution.

Examples of the crosslinking agent include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and triethylene glycol di (meth) acrylate.
Acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, allyl (meth) acrylate, vinyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, methacryloyloxyethyl acrylate, divinylbenzene, diallyl phthalate , Diallyl adipate, triallyl isocyanurate, α-methylene-N
-Vinylpyrrolidone, 2,2-bis (4- (meth) acryloyloxyphenyl) hexafluoropropane, 2,2
-Bis (3- (meth) acryloyloxyphenyl) hexafluoropropane, 2,2-bis (2- (meth) acryloyloxyphenyl) hexafluoropropane,
2-bis (4- (meth) acryloyloxyphenyl)
Propane, 2,2-bis (3- (meth) acryloyloxyphenyl) propane, 2,2-bis (2- (meth) acryloyloxyphenyl) propane, 1,4-bis (2-
(Meth) acryloyloxyhexafluoroisopropyl) benzene, 1,3-bis (2- (meth) acryloyloxyhexafluoroisopropyl) benzene, 1,2-
Bis (2- (meth) acryloyloxyhexafluoroisopropyl) benzene, 1,4-bis (2- (meth) acryloyloxyisopropyl) benzene, 1,3-bis (2- (meth) acryloyloxyisopropyl) benzene, 1 , 2-bis (2- (meth) acryloyloxyisopropyl) benzene and the like, and these crosslinking agents are used alone or as a mixture of two or more.

Among these crosslinking agents, 2,2-bis (4-methacryloyloxyphenyl) hexafluoropropane is
Unlike other crosslinking agents, the resulting material does not cause shrinkage due to polymerization and imparts excellent surface smoothness, so that it can be particularly preferably used.

The amount of the crosslinking agent is based on 100 parts of the essential copolymer component.
0.01 to 10 parts, preferably 0.05 to 8 parts, more preferably
0.1 to 5 parts. If the amount of the crosslinking agent is less than the lower limit, the effect of adding the crosslinking agent is not sufficiently exhibited, and if the amount exceeds the upper limit, the material tends to become brittle.

For the purpose of imparting mechanical strength to the obtained material,
In addition to the essential copolymer component, a reinforcing monomer may be further added. Specific examples of such a reinforcing monomer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, tert-butyl (meth) acrylate, isobutyl (Meth) acrylate, pentyl (meth) acrylate, tert-pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate , Decyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, etc. (Meth) acrylic acid; styrenes such as styrene, methylstyrene, and dimethylaminostyrene; aromatic ring-containing (meth) acrylates such as benzyl (meth) acrylate; itaconic acid, crotonic acid; Examples thereof include alkyl esters which may be substituted with an alkyl group such as maleic acid and fumaric acid. These reinforcing monomers are used alone or in combination of two or more.

Further, for the purpose of imparting hydrophilicity, a hydrophilic monomer may be further blended in addition to the essential copolymer component.
Specific examples of the hydrophilic monomer include, for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, dihydroxypropyl (meth) acrylate, dihydroxybutyl (meth) acrylate, diethylene glycol mono (meth) acrylate. A) acrylates, triethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, and other hydroxyl-containing (meth) acrylates; (meth) acrylic acid; N-vinylpyrrolidone, α-methylene-N-methylpyrrolidone,
Vinyl lactams such as N-vinylcaprolactam and N- (meth) acryloylpyrrolidone; (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-
(Meth) acrylamides such as ethylaminoethyl (meth) acrylamide; aminoethyl (meth) acrylate, N-methylaminoethyl (meth) acrylate,
Aminoalkyl (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate; alkoxy group-containing (meth) acrylates such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, and methoxydiethylene glycol (meth) acrylate And the like. These hydrophilic monomers are used alone or in combination of two or more.

For the purpose of improving oxygen permeability, a monomer that imparts good oxygen permeability may be further blended in addition to the essential copolymerization component. Specific examples of such a monomer include:
For example, pentamethyldisiloxanylmethyl (meth)
Acrylate, pentamethyldisiloxanylpropyl (meth) acrylate, methylbis (trimethylsiloxy) silylpropyl (meth) acrylate, tris (trimethylsiloxy) silylpropyl (meth) acrylate, mono [methylbis (trimethylsiloxy) siloxy] bis (trimethyl) (Siloxy) silylpropyl (meth) acrylate, tris [methylbis (trimethylsiloxy) siloxy] silylpropyl (meth) acrylate, methylbis (trimethylsiloxy) silylpropylglycerol (meth) acrylate, tris (trimethylsiloxy) silylpropylglycerol (meth) acrylate Mono [methylbis (trimethylsiloxy) siloxy] bis (trimethylsiloxy) silylpropylglycerol (meth) ac Rate, trimethylsilylethyl tetramethyl disiloxanyl propyl glycerol (meth) acrylate, trimethylsilylmethyl (meth) acrylate, trimethylsilylpropyl (meth)
Acrylate, trimethylsilylpropylglycerol (meth) acrylate, pentamethyldisiloxanylpropylglycerol (meth) acrylate, methylbis (trimethylsiloxy) silylethyltetramethyldisiloxanylmethyl (meth) acrylate, tetramethyltriisopropylcyclotetrasiloxa Silicon-containing (meth) acrylates such as nylpropyl (meth) acrylate, tetramethyltriisopropylcyclotetrasiloxybis (trimethylsiloxy) silylpropyl (meth) acrylate; pentafluorostyrene, trimethylstyrene, trifluoromethylstyrene, (pentamethyl- 3,3-bis (trimethylsiloxy) trisiloxanyl) styrene, (hexamethyl-3-trimethylsiloxytrisiloxa) F) fluorine or silicon-containing styrenes such as styrene; alkyl esters which may be substituted with a fluorine-containing alkyl group and / or a siloxanylalkyl group such as itaconic acid, crotonic acid, maleic acid, and fumaric acid; can give. These monomers are used alone or in combination of two or more.

The compounding amount of the reinforcing monomer, the hydrophilic monomer and the monomer imparting oxygen permeability is desirably adjusted according to the intended use of the obtained material, and is optional. Parts or less, preferably 20 parts or less. When the amount of these monomers is larger than the upper limit, the amount of the essential copolymer components is relatively small, and the effect of the copolymer components tends to be insufficient.

When the hydrophilic monomer is blended, the amount of the hydrophilic monomer is 15 parts or less based on 100 parts of the essential copolymerization component. It is preferable for low water content. For example, when the materials of the present invention are used as contact lenses, it is preferred that such materials be substantially non-hydrous or very low hydrous. If it is practically non-water-containing, microorganisms such as bacteria will not enter or propagate in the lens, eliminating the need for complicated lens care such as disinfection, and increasing the water content. , The decrease in mechanical strength is reduced. In addition, when used as an intraocular lens, if it is substantially non-water-containing, a decrease in mechanical strength due to an increase in water content is small, and the shape retention and the like as a lens are not impaired. .

In addition, the copolymerization component, for the purpose of imparting ultraviolet absorptivity to the lens or to color the lens, or to cut off light in a partial wavelength range of visible light, the essential copolymerization component In addition, a polymerizable ultraviolet absorber and a polymerizable dye may be further added.

Specific examples of the polymerizable ultraviolet absorber include, for example, 2-hydroxy-4- (meth) acryloyloxybenzophenone, 2-hydroxy-4- (meth) acryloyloxy-5-tert-butylbenzophenone, 2-hydroxy-4 -(Meth) acryloyloxy-2 ', 4'-
Dichlorobenzophenone, 2-hydroxy-4- (2-
Benzophenone-based polymerizable ultraviolet absorbers such as hydroxy-3- (meth) acryloyloxypropoxy) benzophenone; 2- (2'-hydroxy-5 '-(meth) acryloyloxyethylphenyl) -2H-benzotriazole, 2- ( 2'-hydroxy-5 '-(meth) acryloyloxyethylphenyl) -5-chloro-2H-benzotriazole, 2- (2'-hydroxy-5'-(meth) acryloyloxypropylphenyl) -2H-benzotriazole Benzotriazole-based polymerizable ultraviolet absorbers such as 2-, 2'-hydroxy-5 '-(meth) acryloyloxypropyl-3'-tert-butylphenyl) -5-chloro-2H-benzotriazole; 2-hydroxy Salicylic acid induction such as -4-methacryloyloxymethyl phenyl benzoate Systemic polymerizable ultraviolet absorbers; and other polymerizable ultraviolet absorbers such as methyl 2-cyano-3-phenyl-3 (3- (meth) acryloyloxyphenyl) propenylate, and the like. The agents may be used alone or in combination of two or more. Specific examples of the polymerizable dye include, for example, 1-phenylazo-4- (meth) acryloyloxynaphthalene, 1-phenylazo-2-hydroxy-
3- (meth) acryloyloxynaphthalene, 1-naphthylazo-2-hydroxy-3- (meth) acryloyloxynaphthalene, 1-anthrylazo-2-hydroxy-3- (meth) acryloyloxynaphthalene, 1-
((4 '-(phenylazo) -phenyl) azo) -2-
Hydroxy-3- (meth) acryloyloxynaphthalene, 1- (2 ', 4'-xylylazo) -2- (meth) acryloyloxynaphthalene, 1- (o-tolylazo)
-2- (meth) acryloyloxynaphthalene, 2-
(3- (meth) acryloylamide-anilino) -4,6
-Bis (1- (o-tolylazo) -2-naphthylamino) -1,3,5-triazine, 2- (3-vinylanilino) -4-((4-nitrophenylazo) -anilino)
-6-chloro-1,3,5-triazine, 2- (1- (o-
Tolylazo) -2-naphthyloxy) -4- (3-vinylanilino) -6-chloro-1,3,5-triazine, 2-
(4-vinylanilino) -4- (1- (o-tolylazo) -2-naphthylanilino) -6-chloro-1,3,5-
Triazine, N- (1- (o-tolylazo) -2-naphthyl) -3-vinylphthalic acid monoamide, N- (1-
(O-tolylazo) -2-naphthyl) -6-vinylphthalic acid monoamide, 3-vinylphthalic acid- (4-p-sulfophenylazo) -1-naphthyl) monoester, 6-
Vinylphthalic acid- (4- (p-sulfophenylazo)-
1-naphthyl) monoester, 3- (meth) acryloylamido-4-phenylazophenol, 3- (meth)
Acryloylamide-4- (8-hydroxy-3,6-disulfo-1-naphthylazo) -phenol, 3- (meth) acryloylamide-4- (1-phenylazo-2)
-Naphthylazo) -phenol, 3- (meth) acryloylamide-4- (p-tolylazo) phenol, 2-
Amino-4- (m- (2-hydroxy-1-naphthylazo) anilino) -6-isopropenyl-1,3,5-triazine, 2-amino-4- (N-methyl-p- (2-hydroxy- 1-naphthylazo) anilino) -6-isopropenyl-1,3,5-triazine, 2-amino-4- (m-
(4-hydroxy-1-phenylazo) anilino) -6
-Isopropenyl-1,3,5-triazine, 2-amino-
4- (N-methyl-p- (4-hydroxyphenylazo) anilino) -6-isopropenyl-1,3,5-triazine, 2-amino-4- (m- (3-methyl-1-phenyl- 5-hydroxy-4-pyrazolylazo) anilino) -6-isopropenyl-1,3,5-triazine, 2-
Amino-4- (N-methyl-p- (3-methyl-1-phenyl-5-hydroxypyrazolylazo) anilino)-
6-isopropenyl-1,3,5-triazine, 2-amino-4- (p-phenylazoanilino) -6-isopropenyl-1,3,5-triazine, 4-phenylazo-7-
Azo copolymerizable dyes such as (meth) acryloylamide-1-naphthol; 1,5-bis (meth) acryloylamino) -9,10-anthraquinone, 1- (4'-vinylbenzoylamide) -9,10- Anthraquinone, 4-amino-
1- (4'-vinylbenzoylamide) -9,10-anthraquinone, 5-amino-1- (4'-vinylbenzoylamide) -9,10-anthraquinone, 8-amino-1-
(4'-vinylbenzoylamide) -9,10-anthraquinone, 4-nitro-1- (4'-vinylbenzoylamide) -9,10-anthraquinone, 4-hydroxy-1-
(4'-vinylbenzoylamide) -9,10-anthraquinone, 1- (3'-vinylbenzoylamide) -9,10-
Anthraquinone, 1- (2'-vinylbenzoylamide) -9,10-anthraquinone, 1- (4'-isopropenylbenzoylamide) -9,10-anthraquinone, 1-
(3'-isopropenylbenzoylamide) -9,10-anthraquinone, 1- (2'-isopropenylbenzoylamide) -9,10-anthraquinone, 1,4-bis- (4 '
-Vinylbenzoylamide) -9,10-anthraquinone,
1,4-bis- (4'-isopropenylbenzoylamide) -9,10-anthraquinone, 1,5-bis-4'-vinylbenzoylamide) -9,10-anthraquinone, 1,5-
Bis- (4'-isopropenylbenzoylamide) -9,
10-anthraquinone, 1-methylamino-4- (3'-
Vinylbenzoylamide) -9,10-anthraminone, 1
-Methylamino-4- (4'-vinylbenzoyloxyethylamino) -9,10-anthraquinone, 1-amino-
4- (3'-vinylphenylamino) -9,10-anthraquinone-2-sulfonic acid, 1-amino-4- (4'-vinylphenylamino) -9,10-anthraquinone-2-sulfonic acid, 1- Amino-4- (2'-vinylbenzylamino) -9,10-anthraquinone-2-sulfonic acid, 1-
Amino-4- (3 '-(meth) acryloylaminophenylamino) -9,10-anthraquinone-2-sulfonic acid, 1-amino-4- (3'-(meth) acryloylaminobenzylamino) -9,10 -Anthraquinone-2-sulfonic acid, 1- (β-ethoxycarbonylallylamino) -9,10-anthraquinone, 1- (β-carboxyallylamino) -9,10-anthraquinone, 1,5-di- (β
-Carboxyallylamino) -9,10-anthraquinone,
1- (β-isopropoxycarbonylallylamino)-
5-benzoylamide-9,10-anthraquinone, 2-
(3- (meth) acryloylamide-anilino) -4-
(3- (3-Sulfo-4-aminoanthraquinone-1-
Yl) -amino-anilino) -6-chloro-1,3,5-triazine, 2- (3- (meth) acryloylamide-anilino) -4- (3- (3-sulfo-4-aminoanthraquinone-1) -Yl) -amino-anilino) -6-hydrazino-1,3,5-triazine, 2,4-bis-((4-methoxyanthraquinone-1-yl) -amino) -6- (3
-Vinylanilino) -1,3,5-triazine, 2- (2-
Vinylphenoxy) -4- (4- (3-sulfo-4-aminoanthraquinone-1-yl-amino) -anilino)
Anthraquinone-based polymerizable dyes such as -6-chloro-1,3,5-triazine; nitro-based polymerizable dyes such as o-nitroanilinomethyl (meth) acrylate; (meth) acryloylated tetraamino copper phthalocyanine; And phthalocyanine-based polymerizable dyes such as acryloylated (dodecanoylated tetraamino copper phthalocyanine). These polymerizable dyes are used alone or in combination of two or more.

Since the amount of the polymerizable ultraviolet absorber and the polymerizable dye is greatly affected by the thickness of the lens, it is preferably 3.0 parts or less based on 100 parts of the essential copolymer component. If the amount is more than 3.0 parts, the physical properties of the lens, such as strength, tend to decrease, and in consideration of the toxicity of ultraviolet absorbers and dyes, contact lenses or living bodies that come into direct contact with living tissues are used. It is not preferable as a material for an ophthalmic lens such as an intraocular lens to be embedded. In the case of pigments, in particular, if the amount is too large, the coloring becomes too deep, the transparency is reduced, and visible light is hardly transmitted.

In the present invention, one or two types of lens components other than the essential copolymerization component, such as a reinforcing monomer, a hydrophilic monomer, a monomer that imparts oxygen permeability, a polymerizable ultraviolet absorber, and a polymerizable dye, are used. A macromonomer may be selected by selecting one or more species, and this may be further compounded as one of the lens components other than the essential polymerization component in the essential copolymerization component.

The above-mentioned lens components including the above-mentioned essential copolymer components are subjected to copolymerization after being appropriately adjusted according to the intended use of an ophthalmic lens such as a contact lens or an intraocular lens.

As a method for obtaining the ophthalmic lens material of the present invention, for example, a monomer (A), a monomer (B), a macromer (C)
It is obtained by blending a monomer component to be added as required and a radical polymerization initiator, followed by polymerization by a usual method.

Such a usual method is performed, for example, by blending a radical polymerization initiator and then gradually heating the mixture in a temperature range from room temperature to about 130 ° C., or by irradiating electromagnetic waves such as microwaves, ultraviolet rays, and radiation (γ rays). Is the way. In the case of heat polymerization, the temperature may be raised stepwise. The polymerization may be performed by a bulk polymerization method, a solvent polymerization method using a solvent or the like, or may be performed by another method.

Specific examples of the radical polymerization initiator include, for example, azobisisobutyronitrile, azobisdimethylvaleronitrile, benzoyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, and the like. One or more radical polymerization initiators are used in combination. In addition, when polymerizing using light rays etc.,
It is preferable to further add a photopolymerization initiator and a sensitizer. The amount of such a polymerization initiator or sensitizer is suitably about 0.01 to 1 part based on 100 parts of the total monomer mixture to be subjected to polymerization.

When molding as an ophthalmic lens such as a contact lens or an intraocular lens, a molding method commonly used by those skilled in the art is employed. Examples of such a molding method include a cutting method and a mold method. In the cutting method, polymerization is performed in an appropriate mold or container, and a rod-shaped, block-shaped, or plate-shaped material (polymer) is obtained, and then processed into a desired shape by mechanical processing such as cutting or polishing. Is the way. The mold method is a method of preparing a mold corresponding to the shape of a desired ophthalmic lens, polymerizing the monomer mixture in this mold to obtain a molded product, and mechanically finishing as necessary. is there.

Since the ophthalmic lens material of the present invention is a soft material near room temperature, a molding method using a mold method is generally suitable.
As a casting method, a spin casting method, a static casting method, and the like are known.

Further, when the intraocular lens is obtained, the support portion of the lens may be manufactured separately from the lens and attached to the lens later, or may be molded simultaneously (integrally) with the lens.

In the present invention, the lens material for the eye may be subjected to a plasma treatment as necessary. As a processing apparatus and a processing method, conventionally known ordinary apparatuses and methods are employed.

Such a treatment is performed under an atmosphere of an inert gas such as helium, neon, argon or a gas such as air, oxygen, nitrogen, carbon monoxide, carbon dioxide, at a pressure of about 0.0001 to several Torr,
It is performed by irradiating the plasma with the output of about several to 100 W for several seconds to several tens of minutes. A preferred treatment is under an atmosphere of air, oxygen or argon at a pressure of about 0.05-3T.
Irradiating plasma for several minutes under the condition of orr, output of about 10 to 60W.

The ophthalmic lens material of the present invention thus obtained comprises (a)
Since it is soft, it is comfortable to wear when it is made into a contact lens, and when it is made into an intraocular lens, it can be inserted through a small incision without damaging the ocular tissue. Since it is water-containing or low-water-containing, there is no decrease in mechanical strength due to an increase in water content, the shape retention of the lens is not impaired, and bacteria and the like hardly propagate in the material. When it is done, it is not necessary to perform complicated treatment such as boiling disinfection. (C) Since it has excellent oxygen permeability, it does not impair the metabolic function of the cornea when used as a contact lens. Because of its excellent strength, its shape is stable as a lens, it is not damaged by various physical treatments, and (e) it is difficult for dirt such as lipids to adhere. No clouding is also not adversely affect the ocular tissues, is one that exhibits an effect of hardly occurs disorders such as adhesions with respect because, ocular tissue no stickiness (A) surface.

Next, the soft ophthalmic lens material of the present invention will be described in more detail based on Reference Examples and Examples, but the present invention is not limited to each of the examples.

Reference Example 1 [Synthesis of Macromer] In a three-necked round bottom flask, 10 g of trifluoroethyl methacrylate and 0.075 of ethylene glycol dimethacrylate were placed.
g, 80 ml of benzene. Heat the flask to a temperature of 8
When the temperature rose to 3 ° C., 0.11 g of azobisisobutyronitrile dissolved in 20 ml of benzene was charged. The reaction was carried out for about 1 hour while heating under reflux, and then the reaction was stopped by cooling to room temperature with tap water.

After cooling, the reaction solution was dropped into a large amount of hexane to precipitate the polymer. The obtained crude polymer was dried in a dryer at 40 ° C. overnight. The polymer was dissolved in acetone, filtered, dropped into a large amount of hexane, and purified by reprecipitation. The polymer was dried in a dryer at 40 ° C. overnight, and then dried under vacuum for 8 hours to obtain a macromer.

The obtained macromer was subjected to composition analysis by pyrolysis gas chromatography (hereinafter, referred to as PGC), and the molecular weight was measured by gel permeation chromatography (hereinafter, referred to as GPC) in terms of polystyrene. As a result, in terms of the composition, the unit derived from trifluoroethyl methacrylate was 99.51 mol% and the unit derived from ethylene glycol dimethacrylate was 0.49 mol% in terms of the monomer unit, and the number average molecular weight was 5700 , The weight average molecular weight was 7,700, and the molecular weight dispersion was 1.347.

The molecular weight measurement by GPC was performed using a Trirotor III type GPC analyzer (manufactured by JASCO Corporation), a Shodex R1 SE-31 type differential refraction detector (manufactured by Showa Denko KK), and a KF for Shodex Pak GPC.
-804 type column (manufactured by Showa Denko KK), using tetrahydrofuran as solvent, flow rate 1.0 ml / min, column temperature 40
Measured in ° C.

Furthermore, as for molecular weight analysis, the number average molecular weight was about 9,000 as measured by a vapor pressure osmosis method.

Compared to the measured molecular weight by vapor pressure osmosis method and the measured molecular weight by GPC, the value measured by GPC is smaller than that of GPC.
The value measured by is polystyrene equivalent, so the hydrodynamic volume of the sample is smaller than polystyrene of the same molecular weight,
This is because the molecular weight of the sample converted into polystyrene by GPC is smaller than the actual molecular weight. Therefore, it is considered that the measured value of the molecular weight is closer to the actual molecular weight when measured by the vapor pressure osmosis method.

Reference Examples 2 to 10 In the same manner as in Reference Example 1, the components were polymerized with the composition shown in Table 1 to produce various macromers. The composition analysis and the molecular weight were measured in the same manner as in Reference Example 1. The results are shown in Table 1.

Example 1 [Preparation of Ophthalmic Lens Material] A mold was prepared in which a gasket made of a fluororesin was sandwiched between polyester films from both sides, and the outside thereof was sandwiched between glass plates.

3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl acrylate 42.5 parts by weight, butyl acrylate 42.5 parts by weight, reference 15 parts by weight of the macromer obtained in Example 1 and 0.5 parts by weight of ethylene glycol dimethacrylate were uniformly mixed, and azobisdimethyl valeronitrile 0.5
A mixed solution was prepared by adding parts by weight, and the mixed solution was poured into the mold.

The mold was transferred into a circulating drier, and the temperature was increased at 50 ° C. for 12 hours, then at a rate of 10 ° C. per 2 hours, and the components were polymerized to obtain a film-like copolymer.

The obtained film is punched to a diameter of about 14mm with a punch,
These were used as test pieces, and various physical properties were measured.

Regarding the properties of the obtained test piece, the feel of touching the surface of the test piece with a fingertip was good with almost no stickiness, and immediately restored to the original state even when the test piece was folded and released. As a result, the resilience was good, the material had flexibility that was favorable as a soft ophthalmic lens material, and the appearance of the test piece in water was transparent and had no problem at all.

Next, as physical properties required for soft ophthalmic lens materials,
The following physical properties were examined. Table 2 shows the results.

[Punching Strength] (a) Punching Load A 1/16 inch diameter pressing needle was applied to the center of the test piece using an Instron type compression tester, and the load (g) at break of the test piece was measured. However, the values described in Table 2 are values obtained by converting the thickness of the test piece to 0.2 mm.

(B) Elongation The elongation (%) at break of the test piece when the above-mentioned punching load (g) was measured.

(C) Strength index The strength of the material depends on both the elongation (%) and the punching load (g). Therefore, as an index of the relative strength, the strength was calculated as the strength index by the following equation.

(D) Average thickness The average thickness (mm) of the test piece when measuring the above-mentioned punching load and elongation was measured.

[Oxygen Permeability Coefficient] The test piece was measured in physiological saline at 35 ° C. using a Kakenhi type film oxygen permeability meter manufactured by Rika Seiki Industry Co., Ltd. Units, It is.

The oxygen permeability coefficient in Table 2 is a value obtained by multiplying the value of the original oxygen permeability coefficient by 10 ¹¹ .

[Oleic acid swelling ratio] Oleic acid is one component of eye oil. The fact that the material swells in oleic acid means that it has a good affinity for oleic acid. Therefore, by measuring the swelling of the material in oleic acid, it can be used as a measure of whether the lipid is likely to adhere to the material.

Oleic acid swelling was measured by dividing the size of the material in oleic acid at 35 ° C. by the size in saline.

Examples 2 to 43 In the same manner as in Example 1, test pieces were prepared according to the composition shown in Table 2, and various physical properties were measured in the same manner as in Example 1. Table 2 shows the results.

In addition, in Table 2 and Table 3, each abbreviation means the following.

17FA: 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl acrylate BuA: butyl acrylate EDMA: ethylene glycol di Methacrylate V-65: azobisdimethyl valeronitrile 6FA: 2,2,2,2 ', 2', 2'-hexafluoroisopropyl acrylate 17FM: 3,3,4,4,5,5,6,6,7 , 7,8,8,9,9,10,10,10-Heptadecafluorodecyl methacrylate BiPh6F: 2,2-bis (4-methacryloyloxyphenyl) hexafluoropropane Bi6FB: 1,3-bis (2-methacryloyl Oxyhexafluoroisopropyl) benzene BuMA: butyl methacrylate MMA: methyl methacrylate AA: acrylic acid For the properties of the test piece of the ophthalmic lens material obtained in Examples 2 to 43, the feel of touching the surface of the test piece with a fingertip was
It is good with almost no stickiness, and has a good resilience because it restores to its original state immediately after folding and releasing the test piece in two, and it has favorable flexibility as a soft ophthalmic lens material, The appearance of the test piece in water was observed with the naked eye, and was transparent and had no problem.

For reference, as a result of measuring the water content and the contact angle of Example 26 and Example 27 using a hydrophilic monomer as other copolymer components, the water content was 1.
The contact angles were 37% and 1.48%, and the contact angles were 57 ° and 61 °.

 The water content and the contact angle were measured as follows.

[Water content] The moisture content of the test piece was measured according to the following equation.

Here, W is the weight (g) of the test piece in the equilibrium hydrated state,
WO represents the weight (g) of the test piece in a dry state.

[Contact Angle] The contact angle of the test piece with water was measured at room temperature (about 20 ° C.) using a goniometer type contact angle measuring device (manufactured by Elma Optical Co., Ltd.).
° C) and a humidity of 50%.

Comparative Example 1 (commercially available non-water-containing soft contact lens) Commercially available non-water-containing soft contact lens (trade name: Sofina, manufactured by Ricky Contact Lens Laboratory Co., Ltd.)
Was used as a test piece, and various physical properties were measured in the same manner as in Example 1. Table 3 shows the results.

The oleic acid swelling ratio was 1.08 or less for all of those obtained in Examples 1 to 43, whereas that obtained in Comparative Example 1 was as high as 1.23, indicating that lipids were easily attached.

In addition, the oxygen permeability coefficient was 47 × 10 ¹¹ or more (before the same unit) in all of the samples obtained in Examples 1 to 43,
Comparative Example 1 was as low as 30.0 × 10 ¹¹ (same unit before). In addition, the surface was sticky and could not be said to be a preferable contact lens.

Comparative Example 2 (when monomer (A) and macromer (C) are not used) As shown in Table 3, various components were blended and polymerized in the same manner as in Example 1 to prepare a film-like test piece. did. Various physical properties of the obtained test piece were measured in the same manner as in Example 1. Table 3 shows the results.

Regarding the oleic acid swelling ratio, those obtained in Examples 1 to 43 were all 1.08 or less, whereas those obtained in Comparative Example 2 were as high as 1.91, indicating that lipids were easily attached.

In addition, the oxygen permeability coefficient of each of Examples 1-43 is 47 × 10 ¹¹ or more (before the unit), whereas that of Comparative Example 2 is 38.7 × 10 ^11. (Before unit)
Was low.

Also, regarding the punch-through load of the product obtained in Comparative Example 2,
All of those obtained in Examples 1 to 43 weighed 120 g or more, whereas those obtained in Comparative Example 2 were as low as 55.5 g.

Further, the properties obtained in Comparative Example 2 were such that the surface was very sticky and lacked resilience.

Comparative Examples 3 and 4 (In the case where a macromer containing no fluorine was used without using the monomer (A)) As shown in Table 4, various components were blended in the same manner as in Reference Example 1 and polymerized. Then, a macromer was synthesized.

Using these macromers, various components were blended and polymerized in the same manner as in the examples as shown in Table 3 to prepare film-like test pieces. Various physical properties of the obtained test piece were measured in the same manner as in Example 1. Table 3 shows the results.

The oleic acid swelling ratio was 1.08 or less for all of those obtained in Examples 1 to 43, while Comparative Examples 3 and 4
The result was as high as 1.58 or more, and the lipid was easy to adhere.

Comparative Examples 5 and 6 (when no macromer (C) was used) As shown in Table 3, various components were blended and polymerized in the same manner as in Example 1 to produce a film-shaped test piece. Various physical properties of the obtained test piece were measured in the same manner as in Example 1. Table 3 shows the results.

Regarding the punching load, those obtained in Examples 1 to 43 were all 120 g or more, whereas those obtained in Comparative Examples 5 and 6 were as low as 120 g or less.

As for the oleic acid swelling ratio, those obtained in Comparative Examples 5 to 6 were slightly lower than those obtained in Examples 1 to 43.

 The property was very sticky on the surface.

As is clear from the comparison between Examples 1 to 43 and Comparative Examples 1 to 6, the ophthalmic lens material of the present invention is based on the synergistic effect of a fluorine monomer and a macromer, and has been proposed for a non-hydrous soft eye conventionally proposed. It can be seen that it has less tackiness on the surface than the lens material for use, is less likely to be contaminated by lipid stains, is sufficiently reinforced, and has improved oxygen permeability.

That is, it is understood that there is no conventional ophthalmic lens material which sufficiently satisfies all the physical properties aimed at by the present invention.

[Effects of the Invention] The ophthalmic lens material of the present invention is particularly soft, substantially non-hydrous or low-hydrous, hardly adheres dirt such as lipids, has no sticky surface, and has oxygen permeability. It is a transparent ophthalmic lens material with excellent properties and improved mechanical strength.

Therefore, since the ophthalmic lens material of the present invention is soft, it has an effect of being able to be a flexible contact lens material having a good feeling of wearing when it is made into a contact lens, and when it is made into an intraocular lens, An effect can be obtained that an intraocular lens material that can be deformed and inserted through a small incision without damaging the eye tissue.

In addition, since the ophthalmic lens material of the present invention is substantially non-hydrous or low-hydrous, there is no reduction in mechanical strength due to an increase in water content, and the shape retention of the lens is not impaired. In addition, since bacteria and the like hardly propagate in the material, when a contact lens is used, there is an effect that complicated processing such as boiling disinfection is not required.

Further, since the ophthalmic lens material of the present invention is excellent in oxygen permeability, it has an effect of not impairing the metabolic function of the cornea when used as a contact lens.

Further, since the ophthalmic lens material of the present invention has excellent mechanical strength, it has an effect that the shape of the lens is stable and the lens is not damaged by various physical treatments.

Furthermore, the contact lens material for an eye of the present invention does not easily adhere to dirt such as lipids, so that there is no cloudiness of the lens due to the dirt, and since there is no stickiness on the surface, there is no obstacle such as adhesion to eye tissue. Has an effect that is unlikely to occur.

Claims (2)

(57) [Claims] 1. An alkyl (meth) acrylate having a glass transition point of 40 ° C. or lower when (A) a fluorine-containing (meth) acrylate and (B) a homopolymer, and (C) a fluorine-containing ( A polymer consisting of monomers containing (meth) acrylic acid esters, having an average of 0.05
A soft ophthalmic lens material comprising a copolymer having as essential components a copolymer component comprising a (meth) acrylate polymer having up to 5 radically polymerizable polymerizable groups. 2. The soft ophthalmic lens material according to claim 1, wherein the copolymer component contains (D) a crosslinking agent.