JP2803255B2 - contact lens - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a contact lens, and more particularly, to a contact lens excellent in oxygen permeability and the like.

<Prior Art> At present, as a generally used contact lens, an oxygen-permeable (hereinafter abbreviated as GP) hard contact lens and a water-containing soft contact lens are known. Although the water-containing soft contact lens is excellent in wearing feeling, the oxygen permeability of the material is insufficient. Therefore, it is conceivable to increase the moisture content of the material in order to increase the oxygen permeability, but clinical results have been reported that it is easy to be contaminated by various bacteria and cause serious complications to the cornea and conjunctiva. I have. On the other hand, GP hard contact lenses are highly evaluated in terms of high oxygen permeability, effect of correcting astigmatism, durability and safety, and are becoming the mainstream of contact lenses. Along with this, research on GP hard contact lenses has also been actively conducted, but in each of the above GP contact lenses, only oxygen permeability is pursued, and in fact, other properties required as contact lenses are not sufficient. .

For example, the contact lenses described in JP-B-62-8769, JP-B-62-61928 and JP-B-63-36646 have good oxygen permeability, but have problems in shape stability and stain resistance. is there. On the other hand, dialkyl fumarate used in JP-A-62-99720 and JP-A-62-212618 has poor copolymerizability and even if copolymerization is possible,
It is very brittle and easily breaks and is dangerous. In addition,
The contact lens disclosed in 61-176909 has a low oxygen permeability and is unsuitable for continuous wearing, which has attracted particular attention in recent years.

<Problems to be Solved by the Invention> An object of the present invention is to provide an excellent visual acuity correcting effect, have oxygen permeability that allows long-term continuous wearing, and have shape stability, stain resistance,
An object of the present invention is to provide a contact lens having excellent durability.

<Means for Solving the Problems> According to the present invention, the following general formula (I) (Wherein, A and B is a different from each group, a linear or branched fluoroalkyl group one group represented by _{-C h H k F 2h + 1} -k. However h is An integer from 2 to 18, k is 1 to
Represents an integer of 2 × h. The other group is Wherein X, Y and Z are the same or different groups,
Methyl group, Is shown. M is 0 or 1, n is an integer of 1 to 3, l
Represents an integer of 2 to 4) 1-butene-2, which simultaneously contains a fluorine atom and a silicon atom in the same molecule represented by
A contact lens comprising a copolymer obtained by copolymerizing a 4-dicarboxylic acid diester monomer as an essential raw material monomer is provided.

 Hereinafter, the present invention will be described in more detail.

The contact lens of the present invention has a specific 1-butene-2,
It is characterized by containing a copolymer obtained by copolymerizing a 4-dicarboxylic acid diester monomer as a raw material monomer.

The 1-butene-2,4-dicarboxylic acid diester monomer used in the present invention can be represented by the following general formula (I): In the formula, A and B are respectively different groups, and one group is-
And a linear or branched fluoroalkyl group represented by C _h H _k F _{2h + 1-k} . Where h is an integer of 2 to 18, and k is 1 to 2.
× h represents an integer. The other group is Wherein X, Y and Z are the same or different groups,
Methyl group, Is shown. M is 0 or 1, n is an integer of 1 to 3, l
Represents an integer of 2 to 4.

The case of linear or branched fluoroalkyl group A or B is represented by _{-C h H k F 2h + 1} -k, as h is large,
As the number of branches increases, the oxygen permeability increases. On the other hand, when h increases, the shape stability decreases, and when h is 19 or more, production becomes difficult, so that it cannot be used. Further, in the silicon-containing alkyl group introduced into the same molecule, X,
When the total number of carbon atoms of Y and Z is 13 or more, or when m is 2 or more, n is 4 or more, and 1 is 5 or more, the production is difficult, and even if it can be synthesized, the shape stability decreases. Examples of the 1-butene-2,4-dicarboxylic acid diester monomer containing a fluorine atom and a silicon atom in the same molecule represented by the general formula (I) include 2- (2 ′,
2 ', 2'-trifluoroethoxycarbonyl) -4-
(Trimethylsilylmethoxycarbonyl) -1-butene, 2- (trimethylsilylmethoxycarbonyl) -4
-(2 ', 2', 2'-trifluoroethoxycarbonyl)
-1-butene, 2- (2 ', 2', 2'-trifluoroethoxycarbonyl) -4-pentamethyldisiloxanylmethoxycarbonyl) -1-butene, 2- (pentamethyldisiloxanylmethoxycarbonyl) ) -4- (2 ',
2 ', 2'-trifluoroethoxycarbonyl), 2-
(2 ', 2', 2'-trifluoroethoxycarbonyl)-
4- (tris (trimethylsiloxy) silylpropyloxycarbonyl) -1-butene, 2- (tris (trimethylsiloxy) silylpropyloxycarbonyl) -4
-(2 ', 2', 2'-trifluoroethoxycarbonyl), 2- (3 ', 3', 4 ', 4', 4'-pentafluorobutoxycarbonyl) -4- (pentamethyldisiloxanyl Ethoxycarbonyl) -1-butene, 2- (pentamethyldisiloxanylethoxycarbonyl) -4-
(3 ', 3', 4 ', 4', 4'-pentafluorobutoxycarbonyl) -1-butene, 2- (3 ', 3', 4 ', 4', 4'-
Pentafluorobutoxycarbonyl) -4- (tris (trimethylsiloxy) silylpropyloxycarbonyl) -1-butene, 2- (tris (trimethylsiloxy) silylpropyloxycarbonyl) -4- (3 ',
3 ', 4', 4 ', 4'-pentafluorobutoxycarbonyl) -1-butene, 2- (1', 1 ', 2', 2'-tetrahydroperfluorodecyloxycarbonyl) -4- (trimethylsilylmethoxy Carbonyl) -1-butene, 2
-(Trimethylsilylmethoxycarbonyl) -4-
(1 ′, 1 ′, 2 ′, 2′-tetrahydroperfluorodecyloxycarbonyl) -1-butene, 2- (3 ′, 3 ′,
4 ', 4', 4'-pentafluorobutoxycarbonyl)-
4- (methylbis (trimethylsiloxy) silylmethoxycarbonyl) -1-butene, 2- (methylbis (trimethylsiloxy) silylmethoxycarbonyl) -4-
(3 ', 3', 4 ', 4', 4'-pentafluorobutoxycarbonyl) -1-butene, 2- [1- (2 ', 2', 2'-trifluoroethoxy) -2- (hydroxy ) Propyloxycarbonyl] -4- (trimethylsilylmethoxycarbonyl) -1-butene, 2- (trimethylsilylmethoxycarbonyl) -4- [1- (2 ', 2', 2'-trifluoroethoxy) -2- (hydroxy ) Propyloxycarbonyl] -1-butene, 2- (3 ', 3', 4 ', 4',
4'-pentafluorobutoxycarbonyl) -4- [1
-(Pentamethyldisiloxanylethoxy) -2- (hydroxy) propyloxycarbonyl] -1-butene,
2- [1- (pentamethyldisiloxanylethoxy)-
2- (hydroxy) propyloxycarbonyl] -4-
(3 ', 3', 4 ', 4', 4'-Pentafluorobutoxycarbonyl) -1-butene and the like. When used, they can be used alone or as a mixture. The content of the 1-butene-2,4-dicarboxylic acid diester monomer, which is an essential raw material component, is preferably in the range of 2 to 95% by weight based on all the raw material monomers.
If the content is less than 2% by weight, the oxygen permeability is extremely reduced, and if it exceeds 95% by weight, the strength as a contact lens cannot be maintained, which is not preferable.

In the present invention, 1- represented by the general formula (I)
The butene-2,4-dicarboxylic acid diester can be prepared by a known method. Specifically, for example, it can be obtained by a method in which a silicon-containing acrylate and a fluorine-containing acrylate are dissolved in a solvent such as dioxane, and the reaction is carried out in the presence of a catalyst and in an inert gas atmosphere.

In the contact lens of the present invention, any other copolymer may be used as long as it is a copolymer comprising the 1-butene-2,4-dicarboxylic acid diester monomer represented by the general formula (I) as an essential raw material monomer component. Polymerizable monomers can also be copolymerized, but in view of the thermal stability, mechanical strength, workability, etc. of the resulting contact lens, other copolymerizable monomers such as radically polymerizable vinyl monomers and silicon It is preferable to use a monomer selected from the group consisting of vinyl monomers containing, fluorine-containing vinyl monomers, crosslinkable polyfunctional vinyl monomers and mixtures thereof. Examples of the radical polymerizable vinyl monomer, silicon-containing vinyl monomer, fluorine-containing vinyl monomer or crosslinkable polyfunctional vinyl monomer include, for example, methyl (meth)
Acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, tertiary butyl (meth)
Acrylate, cyclohexyl (meth) acrylate,
Benzyl (meth) acrylate, styrene, p-methylstyrene, p-chlorostyrene, o-chlorostyrene,
Divinylbenzene, vinyl acetate, vinyl propionate,
Vinyl pivalate, vinyl (meth) acrylate, ethyl vinyl ether, n-butyl vinyl ether, (meth) acrylamide, 2-hydroxyethyl (meth)
Acrylate, N-vinylpyrrolidone, vinylpyridine, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth)
Acrylate, dipropylene glycol di (meth) acrylate, diallyl phthalate, diallyl isofumarate, diallyl terephthalate, diethylene glycol bisallyl carbonate, triallyl trimellitate, triallyl cyanurate, diisopropyl itaconate,
Ditertiarybutyl itaconate, ditertiarybutylfumarate, trimethylsilylmethyl (meth) acrylate, pentamethyldisiloxanylmethyl (meth) acrylate, tris (trimethylsiloxy) silylmethyl (meth) acrylate, tris (pentamethyldisiloxanyl) Oxy) silylmethyl (meth) acrylate, trimethylsilylethyl (meth) acrylate, pentamethyldisiloxanylethyl (meth) acrylate, tris (trimethylsiloxy) silylethyl (meth) acrylate, tris (pentamethyldisiloxanyloxy)
Silylethyl (meth) acrylate, trimethylsilylpropyl (meth) acrylate, pentamethyldisiloxanylpropyl (meth) acrylate, tris (trimethylsiloxy) silylpropyl (meth) acrylate,
Tris (pentamethyldisiloxanyloxy) silylpropyl (meth) acrylate, ethyl-trimethylsilylethylitaconate, isopropyl-tris (trimethylsiloxy) silylethylitaconate, isopropyl-tris (pentamethyldisiloxanyloxy) silylethyl Itaconate, ethyl-tris (trimethylsiloxy) silylmethylitaconate, isopropyl-tris (pentamethyldisiloxanyloxy) silylethylitaconate, tert-butyl-trimethylsilylpropylitaconate, isopropyl-tris (trimethylsiloxy) silylpropyl Itaconate, tert-butyl-pentamethyldisiloxanylpropyl itaconate, isopropyl-tris (trimethylsiloxy)
Silylpropyl fumarate, tert-butyl-tris (trimethylsiloxy) silylpropyl fumarate, isopropyl-tris (pentamethyldisiloxanyloxy) silylmethyl fumarate, tert-butyl-pentamethyldisiloxanylpropyl fumarate, 2,2,2-
Trifluoroethyl (meth) acrylate, 3,3,4,4,4
Pentafluorobutyl (meth) acrylate, 2,2,3,
3,4,4,5,5-octafluoropentyl (meth) acrylate, 2,2,2-trifluoro-1-trifluoromethyl (meth) acrylate, 1,1,2,2-tetrahydroperfluorodecyl ( Meth) acrylate, ethyl-2,2,2-
Trifluoroethyl fumarate, isopropyl-3,3,4,
4,4-pentafluorobutyl (meth) acrylate, isopropyl-2,2,3,3,4,4,5,5-octafluoropentyl fumarate, isopropyl-2,2,2-trifluoro-
1-trifluoromethyl fumarate, isopropyl-1,
1,2,2-tetrahydroperfluorodecyl fumarate,
Cyclohexyl-1,1,2,2-tetrahydroperfluorodecyl fumarate, tert-butyl-2,2,2-trifluoro-1-trifluoromethyl fumarate, bis 2,2,
Examples thereof include 2-trifluoroethyl fumarate, methacrylic acid, acrylic acid, and itaconic acid, which can be used alone or as a mixture when used. However, the thermal stability, mechanical strength, and processing of the resulting contact lens can be used. It is desirable to use the most preferable combination from the viewpoints of properties, gas permeability and the like. When the radical polymerizable vinyl monomer, the silicon-containing vinyl monomer, the fluorine-containing vinyl monomer or the crosslinkable polyfunctional vinyl monomer is used, it is preferably less than 95% by weight based on the whole raw material monomer component, and more preferably from 5 to 85%. It is desirable to use in the range of weight%. If it exceeds 95% by weight, the oxygen permeability of the contact lens is significantly reduced, which is not preferable.

The contact lens of the present invention preferably has a DK value of 5 to 20 × 10 ⁻¹⁰ ml · cm / cm ² · sec · mmHg, particularly 8 × 10 ⁻¹⁰ ml · cm / cm ^{2 in} order to provide excellent oxygen permeability.・ Sec ・ mmHg or more is desirable. At this time, if it is less than 5 × 10 ^-10 ml · cm / cm ² · sec · mmHg, oxygen permeability during long-term continuous wearing is insufficient, and 20 × 10 ^-10 ml · cm / cm ² · sec · Those exceeding mmHg are not preferred because physical properties such as strength are reduced as a contact lens.

In order to prepare a contact lens in the present invention, a known preparation method can be used. Specifically, for example,
A method of polymerizing a monomer material together with a polymerization initiator in a suitable container such as a test tube to obtain a round bar or a block, and then performing machining such as cutting and polishing, and starting polymerization on one desired mold. After injecting the monomer together with the agent and directly forming a contact lens by template polymerization or producing a polymer in advance by a radical polymerization method or the like, dissolving the polymer in an appropriate solvent and removing the solvent by a casting method. For obtaining contact lenses. In the above-mentioned preparation method, as a polymerization initiator used when polymerizing a monomer, a selected 10-hour half-life temperature is 120 ° C.
It can be selected from one or more of the group consisting of the following organic peroxides and azo compounds. Examples of the organic peroxide or the azo compound include benzoyl peroxide, diisopropyl peroxydicarbonate,
t-butylperoxy-2-ethylhexanoate, t
Preferred examples include -butylperoxypivalate, t-butylperoxydiisobutyrate, lauroyl peroxide, azobisisovitylonitrile, azobis (2,4-dimethylvaleronitrile), and t-butylperoxyisopropyl carbonate. The amount of the polymerization initiator used is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, based on 100 parts by weight of the raw material monomer.

In the above-mentioned preparation method, it is preferable that the polymerization system is appropriately polymerized under an inert gas, such as nitrogen, carbon dioxide, helium, or the like, or under degassing conditions. The temperature at the time of copolymerization varies depending on the type of polymerization initiator used, but is preferably in the range of 30 to 120 ° C. The total time required for the polymerization is desirably about 10 to 72 hours.

It is also possible to add a coloring agent such as a dye or an additive such as an ultraviolet absorber to the raw material monomer to carry out polymerization.

In the present invention, the contact lens obtained by the above-mentioned preparation method can be subjected to an acid or alkali treatment or a low-temperature plasma treatment to perform a surface modification.
The feeling of wearing can also be improved by performing graft polymerization of a hydrophilic monomer by low-temperature plasma treatment or the like.

<Effect of the Invention> The contact lens of the present invention has a specific 1-butene-2,
Since 4-dicarboxylic acid diester monomer is used, the oxygen permeability is higher than conventional contact lenses, and the deposition of proteins, lipids and inorganic substances on the surface can be prevented. Excellent performance with improved disadvantages.

<Examples> Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

 The middle part in the examples indicates parts by weight.

Example 1 2- (2 ', 2', 2'-trifluoroethoxycarbonyl) -4- (tris (trimethylsiloxy) silylpropyloxycarbonyl) -1-butene 40 parts, 1,1,2,2-
Tetrahydroperfluorodecyl (meth) acrylate
30 parts, 20 parts of methyl (meth) acrylate, 5 parts of vinyl (meth) acrylate and 5 parts of methacrylic acid were mixed with 1.5 parts of azobis (2,4-dimethylvaleronitrile), and the mixture was placed in a glass sealed tube. The inside was repeatedly replaced with nitrogen and degassed, and sealed under vacuum. This sealed tube was left standing for polymerization in a constant temperature bath at 70 ° C. for 24 hours, and further heated at 100 ° C. for 2 hours.
The obtained polymer was cut, polished and polished to prepare a contact lens. Next, various physical properties of the obtained contact lens were measured by the following methods.

Oxygen permeability coefficient (DK value) Xertex Corporatio
n) Product name [MODEL 2110] (Multirange Analyzer
DK value (ml · cm / cm ² · sec · mmHg) was obtained by measuring a test contact lens having a diameter of 12.7 mm and a thickness of 0.2 mm in 0.9% physiological saline at 35 ° C. using Dissolved Oxygen). .

12.7mm diameter, thickness in 0.2% egg white lysozyme aqueous solution
A 0.2 mm test contact lens was immersed at 37 ° C. for 24 hours, and the change in absorbance at 280 nm was measured to determine the amount of the attached lysozyme aqueous solution.

Mechanical strength A separately polymerized flat plate sample having a thickness of 2 mm, a length of 50 mm, and a width of 10 mm was measured in accordance with the bending test method of JIS K7203 for hard plastics.

Examples 2 to 5 and Comparative Examples 1 to 3 Contact lenses after curing raw material monomers having various compositions shown in Table 1 under the radical polymerization initiator and polymerization conditions shown in Table 1 in the same manner as in Example 1. Was prepared and various physical properties were measured. Table 1 shows the monomer compounding ratio.
Table 2 shows the measurement results.

 Next, the abbreviations of the components shown in Table 1 will be described below.

F3Si4-B: 2- (2 ', 2', 2'-trifluoroethoxycarbonyl) -4- (tris (trimethylsiloxy) silylpropyloxycarbonyl) -1-butene F17Si-B: 2- (1 ', 1 ', 2', 2'-Tetrahydroperfluorodecyloxycarbonyl) -4- (trimethylsilylethoxycarbonyl) -1-butene Si2F5-B: 2- (methylbis (trimethylsiloxy) silylmethoxycarbonyl) -4- (3 ', 3 ', 4', 4 ', 4'
-Pentafluorobutoxycarbonyl) -1-butene Si-MA: tris (trimethylsiloxy) silylpropyl methacrylate F3-MA: 2,2,2-trifluoroethyl methacrylate F6-MA: 1,1,1,3,3, 3-hexafluoroisopropyl methacrylate F17-MA: 1,1,2,2-tetrahydroperfluorodecyl methacrylate F17-Fu: isopropyl-1,1,2,2-tetrahydroperfluorodecyl fumarate MMA: methyl methacrylate EMA: ethyl Methacrylate A-MA: Allyl methacrylate V-MA: Vinyl methacrylate MA: Methacrylic acid AA: Acrylic acid ABVN: Azobis (2,4-dimethylvaleronitrile) IPP: Diisopropyl peroxydicarbonate BPO: Benzoyl peroxide From the results in Table 2, it can be seen that the contact lens of the present invention has a higher DK value, better oxygen permeability and stain resistance, and retains appropriate physical strength, as compared with Comparative Examples. Was.

Continuation of front page (56) References JP-A-63-210115 (JP, A) JP-A-62-92914 (JP, A) JP-A-60-32022 (JP, A) (58) Fields studied (Int .Cl. ⁶ , DB name) G02C 7/04

Claims (1)

(57) [Claims] 1. A compound represented by the following general formula (I) (Wherein, A and B is a different from each group, a linear or branched fluoroalkyl group one group represented by _{-C h H k F 2h + 1} -k. However h is An integer from 2 to 18, k is 1 to
Represents an integer of 2 × h. The other group is Wherein X, Y and Z are the same or different groups,
Methyl group, Is shown. M is 0 or 1, n is an integer of 1 to 3, l
Represents an integer of 2 to 4) 1-butene-2, which simultaneously contains a fluorine atom and a silicon atom in the same molecule represented by
A contact lens containing a copolymer obtained by copolymerizing a 4-dicarboxylic acid diester monomer as an essential raw material monomer.