JPH0279014A - Soft occular lens material - Google Patents

Abstract

PURPOSE:To obtain the lens material which has excellent transparency and non-water absorbing property, is free from surface sticking and is hardly stickable with the stains of lipid by using a copolymer component consisting of fluorine-contg. acrylate, specific alkyl acrylate and acrylate polymer as its essential component. CONSTITUTION:This lens material consists of the copolymer contg. the component consisting of the (meth)acrylate polymer which is the polymer consisting of the monomers contg. the (meth)acrylate, the alkyl (meth)acrylate of <=40 deg.C glass transition point in case of forming the same into a homopolymer, and the fluorine-contg. (meth)acrylate and has average 0.05 to 5 pieces radically polymerizable polymn. groups within the molecule as its essential copolymer component. The transparent occular lens material which is particularly soft, is substantially no water-absorbent, is hardly stickable with the stains of the lipid, etc., is free from surface sticking and has excellent oxygen permeability is obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to soft ophthalmic lens materials. More specifically, the present invention relates to a soft ophthalmic lens material that can be suitably used as a material for contact lenses, intraocular lenses, artificial corneas, and the like.

[Prior Art] Various ophthalmic lens materials have been proposed as contact lens materials, intraocular lens materials, and the like. Such eye lens materials can be broadly classified into soft materials and hard materials, but contact lens materials are comfortable to wear and can be deformed and inserted by simply making a small incision in the eyeball without damaging the eye tissue. It is well known that soft materials are generally preferred for materials for intraocular lenses.

Soft materials can be divided into water-containing materials that absorb water, swell, and become soft, and substantially water-free materials.

Water-containing materials have a drawback of being inferior in mechanical strength because the proportion of water contained in the material itself is relatively small. In addition, bacteria and mold can easily grow in materials that contain water, and when used as contact lenses, complicated operations such as boiling and sterilization are required.

Substantially water-free materials include, for example, silicone rubber materials, copolymers of alkyl acrylates or long-chain alkyl methacrylates, or esterified copolymers of acrylic acid (hereinafter referred to as
(meth)acrylic acid ester soft materials).

Although the silicone rubber material has the advantage of very high oxygen permeability, the surface of the material obtained is extremely water-repellent and does not mix well with the cornea and other ocular tissues, making it difficult to use the material for contact lenses. There have also been reports that some of the materials used as eyewear materials have caused serious damage to eye tissue.

Among the above-mentioned (meth)acrylic acid ester-based soft materials, those made of copolymers containing butyl acrylate as a main component have been put into practical use as contact lenses. However, contact lenses made of such materials have a sticky surface and tend to become cloudy due to the adhesion of dirt such as lipids, do not have very high oxygen permeability, and have unsatisfactory mechanical strength. There were many points that should have been made.

As the (meth)acrylic acid ester soft material,
In addition to the above, acrylic esters, methacrylic esters, and crosslinking monomers that have a cyclic structure and two or more functional groups in the molecule and have two or more atoms between the cyclic structure and the functional groups are used. A water-free soft contact lens made of a copolymer has been proposed (Japanese Unexamined Patent Publication No. 1982-1999).
127823). Although such non-water-containing soft contact lenses have improved mechanical strength and flexibility, they are easily contaminated with dirt such as lipids, and their oxygen permeability is not sufficient to allow continuous wear as a contact lens.

In addition to the above, there are also non-hydrous soft contact lenses made of copolymers of fluorine-containing methacrylic esters, methacrylic esters other than those listed above, acrylic esters, and crosslinking monomers (Japanese Patent Laid-Open No. 127824/1982). , acrylic acid and/or methacrylic acid, and a monomer mixture containing a crosslinking monomer, and a hard copolymer is esterified with a fluorine-containing alcohol to produce a water-free, oxygen-permeable soft contact lens. (Japanese Unexamined Patent Publication No. 82-127825) has been proposed. However, although all of the contact lenses described in these publications have improved mechanical strength to some extent and have somewhat good oxygen permeability, if a large amount of cross-linked 7-mer is used to further improve mechanical strength, However, it has the drawbacks of reduced oxygen permeability, reduced flexibility, and even brittleness.

[Problems to be Solved by the Invention] Therefore, in view of the above-mentioned prior art, the present inventors have determined that: 1) it has excellent transparency, 2) it exhibits substantially no water content or low water content, and 2) As a result of extensive research into a soft eye lens material that does not have a sticky surface, does not easily attract dirt such as lipids, has excellent oxygen permeability, and has mechanical strength that satisfies practical requirements, we have developed this material. This led to the discovery of an ophthalmic lens material that satisfies all physical properties for the first time, leading to the completion of the present invention.

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

[Operations and Examples] The soft ophthalmic lens material of the present invention has a glass transition point of 40° C. or lower when used as a fluorine-containing (meth)acrylic ester and (B) a homopolymer as described above. A polymer consisting of a monomer containing an alkyl (meth)acrylic ester and (C) a fluorine-containing (meth)acrylic ester, and having an average of 0.05 to 5 radically polymerizable polymerizable groups in the molecule ( It consists of a copolymer containing a component consisting of a meth)acrylate polymer as an essential copolymerization component.

The fluorine-containing (meth)acrylic acid ester (hereinafter referred to as a monomer) is a component that provides oxygen permeability to the material and makes it difficult for dirt such as lipids to adhere to the material. Typical examples of such monomers include the general formula (■): (wherein, R1 is a hydrogen atom or CH3, m is an integer of 1 to 15, n is an integer of 1 to (2s+1), and g is θ to (indicating an integer of 2). Specific examples of such monomers include 2,2.2-trifluoroethyl (meth)acrylate, 2.2.3.3-
Tetrafluoropropyl (meth)acrylate, 2,2
．． 3.3-tetrafluoro-pentyl (meth)acrylate, 2.2,3,4.4゜4-hexafluorobutyl (meth)acrylate, 2.2.3.4,4.4-
hexafluoro-1-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-hebutafluorobutyl (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.
5.8.8゜7.7-dodecafluorohebutyl (meth)
Acrylate, 3.3.4, 4.5.5.6.6, 7.
7.8.8-dodecafluorooctyl (meth)acrylate, 3.3.4, 4.5°5.8. [i, 7, 7.8
．． 8.8-) Ridecafluorooctyl (meth)acrylate, 2.2.3, 3.4.4.5.5.8.8゜7
．． 7.7-dodecafluorooctyl (meth)acrylate, 3.3.4.4.5.5.8. B, 7, 7.8.8
．． 9.9. lO.

IO-hexadecafluorodecyl (meth)acrylate, 3.3,4,4,5.5. B, B, 7.7, 8.8.
9.9.10゜10.10-hebutadecafluorodecyl (meth)acrylate, 3,3.4.4.5,5,6,
6.7, 7, 8, 8.9.9. lO.

to, tt, tt-octadecafluoroundecyl (meth)acrylate, 3,3,4,4,5,5,8,6,
7,7. It, 8°9.9. to, 10, 11, 11.
11-nonadecafluoroundecyl (meth)acrylate, 3.3.4,4,5.5.6.6°7.7.8.8
．． 9.9. lO,10,11,11,12,12-eicosafluorododecyl (meth)acrylate, to 2-hydroxy-4,4,5,5,6,7,7,7-octafluoro-〇-trifluoromethyl Butyl (meth)acrylate, 2-hydroxy-4,4,5,5,8,8,7
, 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, etc.

The blending amount of the above-mentioned Shitsummer (8) is the above-mentioned essential copolymer component 1
The amount is 20 to 80 parts, preferably 25 to 75 parts, and particularly preferably 35 to 70 parts per 00 parts by weight. If the amount of the monomer compound is too small than the lower limit, the effect of adding the monomer will not be sufficiently exhibited, and if it is too much than the upper limit, the amount of other copolymer components will be relatively low. The flexibility of the resulting material tends to decrease.

The homopolymer has a glass transition point of 40
The alkyl (meth)acrylic acid ester (hereinafter referred to as monomer (8)), which has a temperature below It is a component that exhibits

The molecular weight of the homopolymer here is approximately 10.00
It is 0 or more. This is because the molecular weight of the homopolymer is to
, ooo or more, the glass transition point of the homopolymer (
This is because Tg (hereinafter referred to as Tg) does not depend on the molecular weight and does not change much.

The requirement that the Tg of the monomer B) be 40°C or less when used as a homopolymer is that the monomer B)
If the Tg of B) is higher than 40°C, monomer (B)
This is because only hard copolymers can be obtained using this method, and flexibility, which is one of the objects of the present invention, is impaired. Therefore, monomers that can yield homopolymers with Tg lower than body temperature, ie, 40° C. or lower, particularly 10° C. or lower, are preferably used. Typical examples of such monomers (Bl include acrylic esters in which the alkyl group has 1 or more carbon atoms or methacrylic esters in which the alkyl group has 8 or more carbon atoms; specific examples thereof include, for example, methyl acrylate. (Tg when made into a homopolymer (hereinafter simply abbreviated as Tg): 10°C), ethyl acrylate (Tg knee 25°C), propyl acrylate (Tg knee 37°C)
, n-butyl acrylate (Tg knee 54°C), isobutyl acrylate (Tg knee 24°C), hexyl acrylate (Tg knee 57°C), 2-methylbutyl acrylate (Tg knee 32°C), heptyl acrylate (Tg knee 32°C)
80℃), octyl acrylate (Tg; -65℃)
), dodecyl acrylate (Tg at 3°C), octyl methacrylate (Tg at -70°C), dodecyl methacrylate (Tg at -70°C), dodecyl methacrylate (Tg at -70°C),
g knee 85℃), 2-cyanoethyl acrylate (Tg
:4°C), benzyl acrylate (Tl::6°C), and the like.

The blending amount of the monomer (B) is the essential copolymer component 1
The amount is 10 to 80 parts, preferably 15 to 65 parts, particularly preferably 20 to 55 parts. If the blending amount is too small than the lower limit, the effect of blending the monomer (B) will not be sufficiently exhibited, and the flexibility of the resulting material will decrease, and if it is too large than the upper limit, the material Not only does the elongation of the material become too large, the surface of the material becomes noticeably sticky, but also the amount of other components blended becomes relatively small, making the resulting material more likely to be contaminated by dirt such as lipids.

A polymer consisting of a monomer containing the fluorine-containing (meth)acrylic acid ester, with an average of 0.0
Having 5 to 5 radically polymerizable polymerization groups (meta)
Acrylate polymer (hereinafter referred to as macromer (C)) strengthens the resulting material without impairing its flexibility or oxygen permeability, and gives the material elastic resilience (toughness or firm resilience). It is a component that improves mechanical strength, eliminates stickiness on the surface of the material being held, and makes it difficult for lipid stains to adhere.

The macromer (C) has an average of 0.05 to 5 in the molecule,
It has <0.1 to 3 polymerizable groups.

When the macromer (C) has, for example, an average of 0.1 polymerizable groups in the molecule, it means that the macromer (C) has an average of 1 polymerizable group for every 10 macromers (C).
means that exists.

The number of polymerizable groups here is determined by first analyzing the amount of monomer-derived units corresponding to polymerizable groups of the macromer (C) by pyrolysis gas chromatography (PGC), and then by gel permeation chromatography (GPC). ) to measure the number average molecular weight of macromer (C) in terms of polystyrene, and from the amount of monomer-derived units corresponding to polymerizable groups and the number average molecular weight, the value calculated as the average number of polymerized groups per macromer (01 (molecule)) Since the molecular weight is determined as an average value, the calculated number of polymerization groups is also necessarily determined as an average value.

However, the molecular weight measured by GPC of macromer (0) is due to the small hydrodynamic volume of macromer (C) compared to polystyrene with the same molecular weight as macromer (C). The measured value of the molecular weight converted to polystyrene is smaller than the molecular weight of the macromer (C).For this reason, the calculated average number of polymerized groups of the macromer (C), that is, the apparent number of polymerized groups, is smaller than the actual number of polymerized groups. Please note that it can only be obtained as a value smaller than the number.

The macromer (C) having the polymerizable group is copolymerized with other copolymerizers and chemically bonded, so that there is no fear that the macromer (0) will be eluted from the material, and physical reinforcement is achieved simply by molecular entanglement. In addition, chemical bonding also provides a reinforcing effect.

The number of polymerizable groups in one molecule of the macromer (C) having the polymerizable group is preferably 5 or less, particularly 3 or less, from the viewpoint of ensuring flexibility of the resulting copolymer.

If the number of polymerizable groups that the macromer (C) has in the molecule is less than 0.05 on average, the reinforcing effect will not be sufficiently expressed and the mechanical strength of the resulting copolymer will be low, If the number exceeds 5, the resulting copolymer tends to have less elongation and become brittle.

The number average molecular weight of the macromer FC) is 1000 to 10
0,000, and preferably < 2,500 to 50,000. If the number average molecular weight is smaller than the above lower limit value, sufficient reinforcing effect will not be imparted to the resulting material, and if it is larger than the above upper limit value, the solubility for other copolymer components will decrease and the resulting material will not be homogeneous. It becomes difficult to change raw materials, and the materials that are reused tend to become cloudy.

The macromer (C) has a fluorine-containing (meth)acrylic ester as a main component, and the blending amount of the fluorine-containing (meth)acrylic ester is the same as the macromer (C).
The amount is 40 to 100 parts, preferably 50 to 1.00 parts, per 100 parts of component C).

If the amount is less than 40 parts, the compatibility between the macromer [C) and the monomer particles may decrease, and the resulting material may become cloudy.

Specific examples of the fluorine-containing (meth)acrylic acid ester include those similar to the monomers described above.

In addition, the constituent components of the macromer (C) may include, for example, a linear component that imparts mechanical strength,
Branched or cyclic alkyl (meth)acrylates, hydrophilic monomers that are components that impart hydrophilicity, and other monomers such as styrene in an amount exceeding 30 parts per 100 parts of the constituent components of the macromer (C). It may be blended within a certain range. If the blending amount exceeds 30 parts, the compatibility between the macromer (C) and the monomer decreases, and the material tends to become cloudy.

Specific examples of the alkyl (meth)acrylate include:
For example, methyl (meth)acrylate, ethyl (meth)
Examples include acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, nonyl (meth)acrylate, dodecyl (meth)acrylate, and cyclohexyl (meth)acrylate.

Specific examples of the hydrophilic monomer include hydroxyl group-containing alkyl (meth)acrylates 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; and the like.

Macromer (C) has an average of 0.05 to 5 radically polymerizable groups in its molecule, but the macromer (
There are mainly the following methods to introduce C).

(a) Macromer=A method in which a monomer having two or more polymerizable groups is included in the macromer (0 constituent) during polymerization of the constituent component (C) and copolymerized.

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

(C) The constituent components of macromer (C) are dissolved in water, hydrogen peroxide and a redox initiator are added to synthesize a polymer having a hydroxyl group at one end, and this is dissolved in a solvent such as pyridine. A method in which a polymerizable group is introduced at the end by reacting with a compound containing a polymerizable group, such as (meth)acrylic acid chloride, which has a functional group that reacts with a hydroxyl group.

(d) A small amount of a monomer having a hydroxyl group as a functional group, such as 2-hydroxyethyl methacrylate, is copolymerized with the constituent components of the macromer (C), and the resulting polymer is added with a functional group that reacts with the hydroxyl group in a suitable solvent. A method in which a polymerizable group is introduced by reacting with a polymerizable group-containing compound having a group, such as (meth)acrylic acid chloride.

Among these methods, in the method of the above aspect and (C),
Since it is always a terminal polymerization group, the number of polymerization groups in one molecule is 2.
Limited to less than 1 piece. However, in the method (a) or (d) above, the number of polymerizable groups in one molecule is not limited. Therefore, the methods (a) and (small) are preferable in that the number of polymerizable groups in one molecule can be arbitrarily introduced as needed, and the methods (a) and (2) are preferable in that the number of polymerizable groups in one molecule can be introduced as desired. The method is preferred.

When a polymerizable group is introduced by the method described above, by copolymerizing a monomer having two or more polymerizable groups with the macromer (0) component, an average of at least 0.05 polymerizable groups can be introduced into the polymer molecule. A polymer having a polymerizable group capable of radical polymerization can be obtained.

In the method (a), specific examples of monomers having two or more polymerizable groups include 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)
Examples include acrylate, dibrobylene glycol di(meth)acrylate, and trimethylolpropane tri(meth)acrylate.

When the macromer (C) is polymerized, especially the above (
In the case of the method ω, all the polymerizable groups of the monomer having two or more polymerizable groups are not subjected to polymerization, in other words, at least one polymerizable group among the two or more polymerizable groups is not subjected to polymerization. First, it is necessary to carry out the polymerization while controlling the polymerization conditions. Therefore, it is preferable to prepare by solution polymerization. The solvent for solution polymerization may be any solvent as long as it dissolves each copolymer component well and does not inhibit polymerization, such as benzene, acetone, and the like. These solvents may be used alone or in combination of 28 or more. Also, since the amount of solvent varies depending on the reaction conditions,
It is preferable to adjust as necessary.

In addition, there is a correlation between the reaction temperature and reaction time, which are the polymerization conditions for polymerizing the constituent components of macromer (O) to obtain macromer (C), and although it is not possible to generally determine such reaction conditions. Practically speaking, it is preferable to carry out the reaction at a relatively low temperature of 50 to 80°C for several minutes to several hours.

In addition, during polymerization, it is common to use a polymerization initiator, and specific examples of such polymerization initiators include azobis compounds such as azobisisobutyronitrile and azobisdimethylvaleronitrile; Examples include peroxides such as benzoyl peroxide.

Among the macromers (0) thus obtained, those having two or more polymerizable groups in the molecule have crosslinking properties. That is, they not only reinforce the material, but also exhibit the same effect as a crosslinking agent.

The blending amount of the macromer (C) is 100% of the essential copolymerization component.
2 to 35 parts, preferably 3 to 30 parts, particularly preferably 4 to 25 parts. If the blending amount is too small than the above lower limit, the effect of blending the macromer (C) will not be sufficiently exhibited, and if it is too large than the above upper limit, other copolymer components will be relatively There is a tendency for less to be used and the resulting material to be less flexible.

In addition, in order to improve shape stability and durability such as chemical resistance, heat resistance, solvent resistance, and shape stability of the material of the present invention, and to reduce eluate, at least 2 It is preferable to use a macromonomer having 1 or more polymerizable groups.

As the crosslinking agent, for example, ethylene glycol di(
meth)acrylate, diethylene glycol di(meth)
Acrylate, triethylene glycol di(meth)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,
2.2-bis(4-(meth)acryloyloxyphenyl)propane, 2,2-bis(3-(meth)acryloyloxyphenyl)propane, 2,2-bis(2-(meth)acryloyloxyphenyl)propane , l, 4-
Bis(2-(meth)acryloyloxyhexafluoroisopropyl)benzene, 1,3-bis(2-(meth)
acryloyloxyhexafluoroisopropyl)benzene, l,2-bis(2-(meth)acryloyloxyhexafluoroisopropyl)benzene, 1゜4-bis(2-(meth)acryloyloxyisopropyl)benzene, l,3- Bis(2-(meth)acryloyloxyisopropyl)benzene, 1,2-bis(2-(meth)
Examples include acryloyloxyisopropyl)benzene, and these crosslinking agents may be used alone or in combination of two or more.

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

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

In addition, in addition to the above-mentioned essential copolymer components, a reinforcing monomer may be further blended for the purpose of imparting mechanical strength to the resulting material. Specific examples of such reinforcing monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, tert-butyl (meth)acrylate, and 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)
Linear, branched, and cyclic alkyl (meth)acrylates such as acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, and cyclohexyl (meth)acrylate; (meth)acrylic acid;
Styrenes such as styrene, methylstyrene, and dimethylaminostyrene; Aromatic ring-containing (meth)acrylates such as benzyl (meth)acrylate; Substituted with alkyl groups such as itaconic acid, crotonic acid, maleic acid, and fumaric acid. Good examples include alkyl esters.

These reinforcing monomers may be 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 above-mentioned essential copolymer components. Specific examples of hydrophilic monomers include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, dihydroxypropyl (meth)acrylate, dihydroxybutyl (meth)acrylate, and diethylene glycol mono(meth)acrylate. ) Acrylate, hydroxyl group-containing (meth)acrylates such as triethylene glycol mono(meth)acrylate, and dipropylene glycol mono(meth)acrylate; (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-ethyl-N
- (meth) such as aminoethyl (meth)acrylamide
Acrylamides Aminoalkyl (meth)acrylates such as niaminoethyl (meth)acrylate, N-methyl-N-aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate; Methoxyethyl (meth)acrylate, ethoxy Examples include alkoxy group-containing (meth)acrylates such as ethyl (meth)acrylate and methoxydiethylene glycol (meth)acrylate.

These hydrophilic monomers may be 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 above-mentioned essential copolymer components. Specific examples of such 7mers include pentamethyldisiloxanyl methyl (meth)acrylate, pentamethyldisiloxanyl propyl (meth)acrylate, and methylbis(trimethylsiloxy).
Silylpropyl (meth)acrylate, tris(trimethylsiloxy)silylpropyl (meth)acrylate,
Mono [Methylbis(trimethylsiloxy)siloxy]
Bis(trimethylsiloxy)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)acrylate, trimethylsilylethyltetramethyldisiloxanylpropylglycerol(meth)acrylate, trimethylsilylmethyl(meth)acrylate, trimethylsilylpropyl (meth)acrylate, trimethylsilylpropylglycerol (meth)
Acrylate, pentamethyldisiloxanylbrobylglycerol (meth)acrylate, methylbis(trimethylsiloxy)silylethyltetramethyldisiloxanylmethyl(meth)acrylate, tetramethyltriisopropylcyclotetrasiloxanylpropyl(meth)acrylate, Silicon-containing (meth)acrylates such as tetramethyltriisopropylcyclotetrasiloxybis(trimethylsiloxy)silylpropyl(meth)acrylate; pentafluorostyrene, trimethylstyrene, trifluoromethylstyrene, (pentamethyl-
Fluorine or silicon-containing styrenes such as 3,3-bis(trimethylsiloxy)trisiloxanyl)styrene and (hexamethyl-3-trimethylsiloxytrisiloxanyl)styrene; fluorine such as itaconic acid, crotonic acid, maleic acid, fumaric acid, etc. Examples include alkyl esters which may be substituted with an alkyl group and/or a siloxanylalkyl group. These monomers may be used alone or in combination of two or more.

The amount of the reinforcing monomer, the hydrophilic monomer, and the monomer imparting oxygen permeability is desirably adjusted depending on the intended use of the resulting material, but is 30 parts per 100 parts of the essential copolymer component. Below the department, Nakazu<2
It is preferably 0 parts or less. If the amount of these monomers is greater than the upper limit, the amount of the essential copolymer component will be relatively small, and the effects of the copolymer component will not be sufficiently exerted.

In addition, when blending the hydrophilic monomer, it is recommended that the blending amount of the hydrophilic monomer be 15 parts or less based on 100 parts of the essential copolymer component to make the material substantially water-free or This is preferable in terms of low water content. For example, when the materials of the present invention are used as contact lenses, it is preferred that such materials have substantially no or very low water content. If the lens is substantially water-free, microorganisms such as bacteria will not invade or reproduce in the lens, so there is no need for complicated lens care such as disinfection, and the water content will increase. The decrease in mechanical strength due to In addition, when used as an intraocular lens, if it is substantially water-free, the decrease in mechanical strength due to an increase in water content will be small, and the shape retention of the lens will not be impaired. .

In addition, the above-mentioned copolymerization components may be added to the essential copolymerization components for the purpose of imparting ultraviolet absorbency to the lens, coloring the lens, or cutting light rays in a part of the wavelength range of visible light. In addition, a polymerizable ultraviolet absorber or a polymerizable dye may be further blended.

Specific examples of the polymerizable ultraviolet absorber include 2
-Hydroxy-4-(meth)acryloyloxybenzophenone, 2-hydroxy-4-(meth)acryloyloxy-5-tθ "t-butylbenzophenone, 2-hydroxy-4-(meth)acryloyloxy-2',4
°-dichlorobenzophenone, 2-hydroxy-4-(
Benzophenone polymerizable ultraviolet absorber such as 2-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, 2-(2'-hydroxy-5'-(meth)acryloyloxypropyl-3°
-tert-butylphenyl)-5-chloro-211-
Benzotriazole polymerizable UV absorbers such as benzotriazole; salicylic acid derivative polymerizable UV absorbers such as phenyl 2-hydroxy-4-methacryloyloxymethylbenzoate; other 2-cyano-3-phenyl-3(3-(meth) ) acryloyloxyphenyl) propenylic acid methyl ester, etc., and these polymerizable ultraviolet absorbers may be used alone or in combination of two or more. Further, as specific examples of the polymerizable dye, for example, l-phenylazo-4
-(meth)acryloyloxynaphthalene, ■-phenylazo 2-hydroxy-3-(meth)acryloyloxynaphthalene, ■-naphthylazo 2-hydroxy-
3-(meth)acryloyloxynaphthalene, l-anthryl azo-2-hydroxy-3-(meth)acryloyloxynaphthalene, 1-((4-(phenylazo)-
phenyl)azo)-2-hydroxy-3-(meth)acryloyloxynaphthalene, 1-(2°,4′-xylylazo)-2-naphthol(meth)acrylate, 1-
(orthotolylazo)-2-naphthol (meth)acrylate, 2-(3-(meth)acryloylamide-anilino)-4,8-bis(1-orthotolylazo-2-naphthylamino)-1,3,5- triazine, 2-(3-
vinylanilino)-4-(4-nitro(phenylazo)
-anilino)-6-chloro-1,L5-) riazine,
2-(1-orthotolylazo-2-naphthyloxy)-
4-(3-vinylanilino)-6-chloro-1,3,5
-triazine, 2-(4-vinylanilino)-4-(orthotolylazo-2-naphthylanilino)-6-chloro-1,3,5-)riazine, N-(1-orthotolylazo-2-naphthyl)-3- vinyl phthalic acid monoamide,
N-(L-orthotolylazo-2-naphthyl)-6-vinylphthalic acid monoamide, 3-vinylphthalic acid-(4-
parasulfophenylazo-1-naphthyl) monoester, B-vinylphthalic acid-(4-parasulfophenylazo-1-naphthyl) monoester, 3-(meth)acryloylamide-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)acryloylamido-4-valatrylazophenol, 2-amino-4-(Ol-(2-hydroxy-1-naphthylazo)anilino>-8-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
-(a+-(4-hydroxy-1-phenylazo)anilino)-6-itubrobenyl-1,3.5-triazine, 2-amino-4-(N-methyl-p-(4-hydroxyphenylazo)anilino)- 8-isopropenyl-1
,3,5-t-riazine, 2-amino-4-(m-(3
-Methyl-■-Phenyl-5-hydroxy-4-pyrazolylazo)anilino)-6-imbrobenyl-1.3.
5-triazine, 2-amino-4-(N-methyl-p-
(3-Methyl-1-phenyl-5-hydroxypyrazolylazo)anilino)-6-imbropenyl 1.3.5
Azo polymerizable compounds such as -triazine, 2-amino-4-(p-phenylazoanilino)-6-itubrobenyl-1,3,5-triazine, 4-phenylazo-7-(meth)acryloylamide-1-naphthol, etc. Dye; 1,5-
Di(meth)acryloylamino-9,1O-anthraquinone, ■-(4-vinylbenzoylamide)-9,10
-Anthraquinone, 4-amino-1-(4'-vinylbenzoylamide)-9,10-anthraquinone, 5-amino-1-(4°-vinylbenzoylamide)-9,1
0-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, ■-(3-vinylbenzoylamide) -9,10-
Anthraquinone, 1-(2-vinylbenzoylamide)
-9,10-anthraquinone, 1-(4°-isopropenylbenzoylamide)-9,10-anthraquinone,
1-(3-isopropenylbenzoylamide)-9,1
0-anthraquinone, 1-(2°-isopropenylbenzoylamide) -9,10-anthraquinone, ■, 4
-bis-(4°-vinylbenzoylamide)-9,10
-anthraquinone, ■,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-anthraquinone, ■-Methylamino-4-(paravinylbenzoyloxyethylamino)-anthraquinone, l-amino-4-(3-vinylphenylamino)-9,10-anthraquinone-2-sulfonic acid, ■-amino-4-(4-vinyl phenylamino)-9,10-anthraquinone-2-sulfonic acid, 1
-amino-4-(2°-vinylbenzylamino)-9,
10-anthraquinone-2-sulfonic acid, l-amino-
4-(3°-(meth)acryloylaminophenylamino)9.10-anthraquinone-2-sulfonic acid, ■-
Amino-4-(3°-(meth)acryloylaminobenzylamino)-9,10-anthraquinone-2-sulfonic acid, L-(β-ethoxycarbonylallylamino)-
9,10-anthraquinone, l-(β-carboxyallylamino)-9,10-anthraquinone, l,5-di(β-carboxyallylamino)-9,10-anthraquinone, 1-(β-impropoxycarbonylallyl Amino)-5-benzoylamide-9,10-anthraquinone, 2-(3-(meth)acryloylamide-anilino)-4-(3-(3-sulfo-4-aminoanthraquinone-1-yl)-amino- anilino)-6-chlor-
1,3,5-triazine, 2-(3-(meth)acryloylamide-anilino)-4-(3-(3-sulfo-4
-aminoanthraquinon-1-yl)-amino-anilino)-6-hydrazino-1,3,5-triazine, 2,
4-bis-((4-methoxyanthraquinon-1-yl)-amino)-8-(3-vinylanilino)-1,3,
5-) Riazine, 2-(2-vinylphenoxy)-4-
(4-(3-sulfo-4-aminoanthraquinone-1-
yl-amino)-anilino)-6-chloro-1,3,5
-) Anthraquinone polymerizable dye such as riazine; 0-
Examples include nitro polymerizable dyes such as nitroanilinomethyl (meth)acrylate; phthalocyanine polymerizable dyes such as (meth)acryloylated tetraamino copper phthalocyanine and (meth)acryloyl (dodecanoylated tetraamino copper phthalocyanine). These polymerizable dyes may be used alone or in combination of two or more.

The amounts of the polymerizable ultraviolet absorber and polymerizable dye are as follows:
Since it is greatly influenced 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 blending amount exceeds 3.0 parts, the physical properties of the lens, such as strength, tend to deteriorate.Also, considering the toxicity of ultraviolet absorbers and dyes, contact lenses that come into direct contact with living tissues and living bodies tend to deteriorate. It cannot be said to be a preferable material for ophthalmic lenses such as intraocular lenses to be implanted. In addition, especially in the case of pigments, if the amount of the pigment is too large, the coloring becomes too deep, the transparency decreases, and it becomes difficult for visible light to pass through.

In addition, in the present invention, lens components other than the essential copolymer components, such as reinforcing monomers, hydrophilic monomers,
Monomer that imparts oxygen permeability, polymerizable ultraviolet absorber,
One or more types of polymerizable dyes may be selected to form a macromonomer, which may be further blended with the essential copolymerization components as one of the lens components other than the essential polymerization components.

The above-described lens components including the essential copolymerization components are suitably adjusted depending on the intended use of the ophthalmic lens, such as a contact lens or an ophthalmic lens, and then subjected to copolymerization.

As a method for obtaining the ophthalmic lens material of the present invention, for example, monomer (2), monomer (B), macromer (C) and other monomer components added as desired are blended, and a radical polymerization initiator is added thereto. and can be obtained by polymerization using a conventional method.

Such conventional methods include, for example, blending a radical polymerization initiator and then gradually heating it in a temperature range of room temperature to about 130°C, or irradiating it with electromagnetic waves such as microwaves, ultraviolet rays, and radiation (γ rays). It's a method. When polymerizing by heating, the temperature may be raised stepwise. Polymerization may be carried out by bulk polymerization, by solvent polymerization using a solvent, or by other methods.

Specific examples of the radical polymerization initiator include azobisisobutyronitrile, azobisdimethylvaleronitrile, benzoyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, etc. Radical polymerization initiators may be used alone or in combination of two or more. In addition, when polymerizing using light, etc., it is preferable to further add a photopolymerization initiator and a sensitizer. The amount of the photopolymerization initiator and sensitizer to be blended is approximately 0.01 to 1 part based on 100 parts of the total monomer mixture to be subjected to polymerization.

When molding into 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 molding methods include cutting methods and molding methods. In the cutting method, polymerization is performed in a suitable mold or container to obtain a rod-shaped, block-shaped, or plate-shaped material (polymer), and then cutting processing is performed.
This is a method of processing into a desired shape by mechanical processing such as polishing. The mold method is a method in which a mold corresponding to the desired shape of the ophthalmic lens is prepared, a monomer mixture is polymerized in this mold to form a molded product, and mechanical finishing processing is applied as necessary. be.

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

Furthermore, when an intraocular lens is to be molded, the lens support part may be manufactured separately from the lens and attached to the lens later, or may be molded at the same time as the lens (inside the body).

In the present invention, the ophthalmic lens material may be subjected to plasma treatment if necessary. As the processing device and processing method, conventionally known normal devices and methods are employed.

Such treatment is performed under an atmosphere of an inert gas such as helium, neon, or argon, or a gas such as air, oxygen, nitrogen, carbon oxide, or carbon dioxide, at a pressure of 0.0001 to several T.
This is carried out by irradiating plasma for several seconds to several tens of minutes under conditions of a power output of about a few seconds to about 10W. A preferred treatment is plasma irradiation for several minutes at a pressure of 0.05 to 3 Torr and a power of 10 to 60 W in an atmosphere of air, oxygen, or argon.

The thus obtained ophthalmic lens material of the present invention is () soft, so it feels comfortable to wear when used as a contact lens, and when used as an intraocular lens, it can be deformed through a small incision without damaging the eye tissue. and can be inserted,
(b) Since it is substantially water-free or has low water content, there is no decrease in mechanical strength due to an increase in water content, and the shape retention of the lens will not be impaired, and bacteria will not grow in the material. Because it is difficult to clean, it does not require complicated treatments such as boiling sterilization when used as contact lenses, and because it has excellent oxygen permeability, it does not impair the metabolic function of the cornea when used as contact lenses. , to)
Because of its excellent mechanical strength, the lens remains stable in shape and will not be damaged by various physical treatments. Since there is no clouding, there is no adverse effect on the eye tissue, and there is no stickiness on the surface of the image, it exhibits the effect that problems such as adhesion to the eye tissue are less likely to occur.

Next, the soft ophthalmic lens material of the present invention will be explained in more detail based on Reference Examples and Examples, but the present invention is not limited by these aspects.

Reference Example 1 [Synthesis of Macromer] 10 g of trifluoroethyl methacrylate 1 0.0 g of ethylene glycol dimethacrylate in a 3-necked round bottom flask.
0747 g and 80 ml of benzene were added.

When the flask was heated and the temperature rose to 83°C,
0.333 g of azobisisobutyronitrile dissolved in 20 ml of benzene was added. The mixture was reacted for about 1 hour while heating under reflux, and then cooled to room temperature with tap water to stop the reaction.

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

The obtained macromer was subjected to pyrolysis gas chromatography (
The composition was analyzed using PGC (hereinafter referred to as PGC), and the molecular weight was measured in terms of polystyrene using gel permeation chromatography (hereinafter referred to as GPC). As a result, regarding the composition, in terms of monomer units, 99.51 mol% of units derived from trifluoroethyl methacrylate;
The unit derived from ethylene glycol dimethacrylate was 0.49 mol %, and the molecular weight was 5700 for the number average molecule, 17700 for the weight average molecule, and 1.347 for the molecular weight dispersion.

In addition, molecular weight measurement by GPC is performed using Trirotor I
Type II GPC analyzer (manufactured by JASCO Corporation), 5hode
x RISB-31 differential refraction detector (manufactured by Showa Denko)
, 5hodex Pak GPC XI'-804 type column (manufactured by Showa Denko ■), using tetrahydrofuran as the solvent, flow rate 1.0 ml/iins column temperature 4
Measured at 0°C.

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

The reason why the value measured by GPC is smaller than the molecular weight measured by vapor pressure osmosis and the molecular weight measured by GPC is that
Since the measured value by CPC is converted to polystyrene, the hydrodynamic volume of the sample is smaller compared to polystyrene of the same molecular weight, and the molecular weight of the sample converted to polystyrene by GPC is smaller than the actual molecular weight.

Therefore, it is considered that the value measured by the vapor pressure osmosis method is closer to the actual molecular weight.

Reference Examples 2 to 10 In the same manner as in Reference Example 1, various macromers were produced by polymerizing the components according to the formulations shown in Table 1.

Composition analysis and molecular weight measurements were carried out in the same manner as in Reference Example 1. The results are also shown in Table 1.

[Margin below] Example 1 [Preparation of ophthalmic lens material] A mold was prepared by sandwiching a fluororesin gasket between polyester films on both sides and sandwiching the outside between glass plates.

2.2,2,2°,2”,2°-hexafluoroisopropyl acrylate) 47.5 parts by weight, butyl acrylate 47.5 parts by weight, Macromer 5 obtained in Reference Example 5
parts by weight and 0.5 parts by weight of ethylene glycol dimethacrylate were uniformly blended, 0.5 parts by weight of azobisdimethylvaleronitrile was added to prepare a blended solution, and the blended solution was poured into the mold.

Transfer the mold to a circulation dryer and dry at 50℃ for 12 hours, then 2 hours.
The temperature was raised at a rate of 10°C per hour to polymerize the components to obtain a film-like copolymer.

The resulting film was punched out to a diameter of 14 mm, used as test pieces, and various physical properties were measured.

Regarding the properties of the obtained test piece, when I touched the surface of the test piece with my fingertips, I could hardly feel any stickiness and it was good, and even if I folded the test piece in half and released it, it immediately returned to its original state. It also had good resilience and flexibility as a soft ophthalmic lens material, and the appearance of the test piece in water when observed with the naked eye was transparent and had no problems at all.

Next, the following physical properties were investigated as physical properties required for soft ophthalmic lens materials. The results are shown in Table 2.

[Pushing strength] (a) Punching load Using an Instron-type compression testing machine, a pressure needle with a diameter of 1/16 inch was applied to the center of the test piece, and the load (g) at the time of breakage of the test piece was measured. .

However, the values listed in Table 2 are based on the thickness of the test piece being 0.
, 2 am.

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

(/~Strength Index The strength of the material depends on both the elongation rate (%) and the punching load (g). Therefore, as a measure of relative strength, the strength index was calculated using the following formula.

2X Thickness of test piece (μ■) (d) Average thickness The average thickness (Illll) of the test piece when the above punching load and elongation rate were measured was measured.

[Oxygen permeability coefficient] The test piece was measured in physiological saline at 35° C. using a Seikaken film oxygen permeability meter manufactured by Rika Seiki Kogyo ■. The unit is: The oxygen permeability coefficient in Table 2 is the value obtained by multiplying the original oxygen permeability coefficient value by 10''.

[Oleic acid swelling rate] Oleic acid is a component of eye oil. The fact that a material swells in oleic acid means that it has a good affinity for oleic acid. Therefore, by measuring the swelling rate of a material in oleic acid, it is possible to determine whether or not lipids are likely to adhere to the material.

Oleic acid swelling ratio was determined 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, according to the formulation shown in Table 2,
A test piece was prepared, and various physical properties were measured in the same manner as in Example 1. The results are shown in Table 2.

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

17PA: 3.3.4.4.5.5.8. B.?
, 7.8.8.9.9. lO, to.

10-Hebutadecafluorodecyl acrylate BuA Nibutyl acrylate EDMA: Ethylene glycol dimethacrylate V
-65: Azobisdimethylvaleronitrile 6FA
: 2.2.2,2°,2°,2゛-hexafluoroisopropyl acrylate 17FM; 3,3,4.4,5,5,8.6.7
．． 7.8.8.9.9. lO, 10゜10-heptadecafluorodecyl methacrylate B1Ph8F: 2,2-bis(4-methacryloyloxyphenyl)hexafluoropropane B16PB: 1,3-bis(2-methacryloyloxyhexafluoroisopropyl)benzeneBuMA Nibutyl Methacrylate MMA: Methyl methacrylate to A-niacrylic acid [blank below] Regarding the properties of the test pieces of the ophthalmic lens materials obtained in Examples 2 to 43, when the surface of the test piece is touched with a fingertip,
It is good with almost no stickiness, and even if the test piece is folded in half and released, it immediately returns to its original state, so it has good repulsion properties, and also has flexibility, which is desirable as a soft ophthalmic lens material. The appearance of the test piece in water when observed with the naked eye was transparent and had no problems at all.

For reference, regarding Example 26 and Example 27 in which hydrophilic monomers were used as other copolymerization components,
As a result of measuring the moisture content and contact angle, the moisture content was 1.37% and 1.48%, and the contact angle was 57″ and 61″, respectively.
Met.

Moisture content and contact angle were measured as follows.

[Moisture content] The moisture content of the test piece was measured according to the following formula.

Moisture content (%) - w - w0 x 100, where V is the weight (g) of the test piece in the equilibrium water content state, W
O 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 using a goniometer type contact angle measuring device (manufactured by Elma Optical) at room temperature (about 20° C.) and in an atmosphere of 50% humidity.

Comparative Example 1 (Commercially available non-water-containing contact lens) Using a commercially available non-water-containing contact lens (trade name: Sofina, manufactured by Ricky Contact Lens Institute) as a test piece, various physical properties were measured in the same manner as in Example 1. . These results are shown in Table 3.

The oleic acid swelling ratios of the samples obtained in Examples 1 to 43 were all 1.08 or less, whereas those obtained in Comparative Example 1 were as high as 1.23, indicating that lipids were likely to adhere to them. Ta.

In addition, the oxygen permeability coefficients obtained in Examples 1 to 43 are all 47. In addition, the surface of the contact lens was sticky, and it could not be said to be a desirable contact lens.

Comparative Example 2 (Casing without Monomer and Macromer (C)) As shown in Table 3, various components were blended and polymerized in the same manner as in Example 1 to produce a film-like test piece. Regarding the obtained test piece, various physical properties were measured in the same manner as in Example 1. The results are shown in Table 3.

Regarding the oleic acid swelling ratio, the swelling ratios 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. Ta.

In addition, the oxygen permeability coefficients obtained in Examples 1 to 43 are all 47X to-n (unit: same) or higher, whereas those obtained in Comparative Example 2 are 38.7X to-n or higher.
It was low at 0-1 (same unit).

Furthermore, regarding the bumping load of the product obtained in Comparative Example 2, all of the products obtained in Examples 1 to 43 were 120 g or more, whereas the contact load of the product obtained in Comparative Example 2 was 55.5 g.
It was as low as g.

Moreover, the properties of the product obtained in Comparative Example 2 were that the surface was extremely sticky and lacked resilience.

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

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

The oleic acid swelling ratios obtained in Examples 1 to 43 were all 1.08 or less, whereas those obtained in Comparative Examples 3 and 4 were as high as 1.58 or more, indicating that the lipid It was easy to adhere.

Comparative Examples 5 and 6 (When macromer (C) is 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. Regarding the obtained test piece, various physical properties were measured in the same manner as in Example 1. The results are shown in Table 3.

Regarding the bumping load, all of the samples obtained in Examples 1 to 47 had a load of 120 g or more, whereas those obtained in Comparative Examples 5 and 6 had a low car of J, 20 r or less.

The oleic acid swelling ratios obtained in Comparative Examples 5 and 6 were slightly lower than those obtained in Examples 1 to 47.

The surface was extremely sticky.

[Margin below] As is clear from a comparison of Examples 1 to 43 and Comparative Examples 1 to 6, the ophthalmic lens material of the present invention is superior to conventionally proposed non-conventional materials due to the mutual effect of the fluorine monomer and macromer. It can be seen that the surface is less sticky than hydrous soft ophthalmic lens materials, is less susceptible to lipid stains, is sufficiently reinforced, and has improved oxygen permeability.

That is, it can be seen that in the prior art, there is no ophthalmic lens material that fully satisfies all of the physical properties targeted by the present invention.

[Effects of the Invention] The ophthalmic lens material of the present invention is particularly soft and substantially water-free or has a low water content, and does not have a sticky surface that prevents dirt such as lipids from adhering to it. A transparent ophthalmic lens material with excellent oxygen permeability and improved mechanical strength.

Therefore, since the ophthalmic lens material of the present invention is soft, it can be used as a flexible contact lens material that is comfortable to wear when used as a contact lens, and when used as an intraocular lens, The present invention has the advantage that it can be made into an intraocular lens material that can be deformed and inserted through a small incision without damaging the eye tissue.

Furthermore, since the ophthalmic lens material of the present invention is substantially water-free or has low water content, there is no decrease in mechanical strength due to an increase in water content, and the effect is that the shape retention of the lens is not impaired. In addition, since it is difficult for bacteria to propagate in the material, when used as contact lenses, there is no need for complicated treatments such as boiling sterilization.

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

Furthermore, since the ophthalmic lens material of the present invention has excellent mechanical strength, it has a stable shape as a lens and is not damaged by various physical treatments.

Furthermore, since the ophthalmic contact lens material of the present invention is resistant to adhesion of dirt such as lipids, the lens does not become cloudy due to such dirt, and the surface is not sticky, so it does not cause problems such as adhesion to ocular tissues. It has an effect that is unlikely to occur.

Patent applicant: Menicon Co., Ltd.

Claims (1)

[Claims] 1 (A) fluorine-containing (meth)acrylic acid ester; (B) glass transition point of 40 when made into a homopolymer;
A polymer consisting of a monomer containing an alkyl (meth)acrylic acid ester and (C) a fluorine-containing (meth)acrylic acid ester, which has a temperature of 0.5°C or lower on average within the molecule.
A soft ophthalmic lens material comprising a copolymer having as an essential component a copolymer component comprising a (meth)acrylate polymer having 05 to 5 radically polymerizable polymer groups. 2. The soft ophthalmic lens material according to claim 1, wherein the copolymerization component contains (D) a crosslinking agent.