JPS6238419A - contact lens - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a contact lens that has good oxygen permeability and is resistant to dirt.

[Summary of the invention]

The present invention provides contact lenses with fluorine and/or
Alternatively, a copolymer of an acrylate or methacrylate (hereinafter abbreviated as (meth)acrylate) monomer having a siloxanyl group as a substituent and a comonomer containing as an essential component a crosslinkable monomer having fluorine as a substituent is used. This further improves oxygen permeability and reduces protein adhesion.

[Conventional technology]

Contact lenses commonly used today are broadly classified into hard contact lenses and soft contact lenses. Various types of hard contact lenses have been widely known in the past, but one that has been widely used for a long time is a hard contact lens whose main component is polymethyl methacrylate (PMMA). On the other hand, soft contact lenses are made using, for example, 2-hydroxyethyl methacrylate (HI) for the purpose of improving the hydrophilicity of PMMA.
Hydrophilic monomers such as CMA) and N-vinyl-2-pyrrolidone (Nvp) were combined with methyl methacrylate, -) (MMA).
) etc.

In addition, in recent years, research has been actively conducted to improve the oxygen permeability of hard contact lenses.
502. Tokuko Sho 56-39450゜ Tokuko Sho 56-405
No. 24, etc. discloses a contact lens copolymerized mainly with an alkyl methacrylate such as MMA and (meth)acrylate having a siloxane bond in the side chain.
In JP-A-57-211119 etc., fluoroalkyl (
A contact lens made of a copolymer mainly composed of meth)acrylate is also disclosed in Japanese Patent Application Laid-Open No. 59-28127. Hard contact lenses with good oxygen permeability have been disclosed.

[Problems and Objectives to be Solved by the Invention] Each of the above contact lenses has both advantages and disadvantages. That is, the hard contact lenses containing PMMA as a main component have many advantages such as excellent vision correction effects, good durability, easy handling, and good machinability. Since PMMA has poor hydrophilicity, it does not feel comfortable when worn, and furthermore, since it has poor oxygen permeability, wearing it for a long time tends to cause physiological damage to the cornea.
・On the other hand, although the soft contact lenses achieve the initial purpose of providing aqueous water and improve the wearing comfort,
Water content makes it difficult to maintain the shape, reducing the vision correction effect and decreasing durability. In addition, HEMA and MMAD copolymers do not have sufficient oxygen permeability, and to compensate for this, materials with higher water content are more likely to be contaminated with bacteria and are harmful to the cornea and conjunctiva. Clinical results have also shown that it is likely to cause serious complications.

In addition, contact lenses made by copolymerizing alkyl (meth)acrylates and (meth)acrylates having siloxane bonds in their side chains as main components cover some of the drawbacks of hard and soft contact lenses, and have low oxygen permeability. Although there have been some improvements in terms of vision correction effect, durability, and ease of handling, there is some protein adhesion and there is a limit to oxygen permeability, so it is not recommended for long-term continuous wear. While it is insufficient for
7/I/Although copolymers mainly composed of oroalkyl (meth)acrylates are less prone to protein adhesion, they have a disadvantage of poor oxygen permeability compared to (meth)acrylate copolymers with siloxane bonds. There is.

Copolymers that combine (meth)acrylates with siloxane bonds and fluoroalkyl (meth)acrylates have considerably improved the drawbacks of both, but are still not perfect, and have improved oxygen permeability and stain resistance. sexuality is required.

The present invention has been made to solve the above problems.

In other words, the object of the present invention is to have high oxygen permeability,
The object of the present invention is to provide a contact lens that is difficult to adhere to protein and can be worn continuously for a long period of time. This is a contact lens characterized by being composed of fused lenses.

A general formula is (1) X! CH2=CC-0R1=-(1) I [However, xl in the formula is a hydrogen atom or a methyl group.

It represents a fluorine atom or a trifluoromethyl group, and R1 is a linear or branched fluoroalkyl group represented by a general 2〇aHb12a-A+1 (α is an integer of 2 to 18, and b is an integer of 0 to 2α-1). , or general formula (2) % formula % (2) (wherein C is 0 or 1, d is an integer of 1 to 3, x2 and x3 are each independently a methyl group, a bis(trimethylsiloxy)methylsiloxy group or Expression (8), where e and n are each independently an integer of O-S,
f is an integer from 2 to 18, 1 is an integer from 0 to 2f-1, l is 1
an integer of 0 to 2t+1) or a substituent represented by the general formula (4) (in which k
is 0 or 1, t is an integer from 1 to 5, X4, za
,za,X? and x8 are each independently a methyl group, a pentamethyldisiloxanyloxy group, or a bis(
(trimethylsiloxy) methylsiloxy group, m represents an integer of 0 to 3), or
one or more monomers represented by [hydrocarbon group having 1 to 18 carbon atoms]] B general formula (5), (6), (7),
(8) or (9) [However, 5 and q in the formula are each independently an integer of O to 3, P is an integer of 1 to B, and r is 1
an integer of ~10, S and μ each independently represent an integer of 1 to 5, t represents an integer of 1 to 6, zl represents a fluorine atom or a perfluoroalkyl group having 1 to 3 carbon atoms, Y
Five 72, y3, y4, y6
, y 8, Y' , Y' , Y' and Y"
G;t, General 2〇〇) C! H2=OH-〇-A-...00) (in the formula
zl represents a hydrogen atom, a methyl group, a fluorine atom, or a trifluoromethyl group, and A represents an oxygen atom or an NH group. or represents an allyl carbonate group] Component A represented by the general formula (1) used in the present invention includes the following.

When R1 is a fluoroalkyl group, the higher the number of carbon atoms α, the better the acid leaf permeability, but from the viewpoint of polymerization characteristics, the number is 18 or less, and from the viewpoint of monomer stability, 2 or more is used. Although it is more effective to have a larger number of substituted fluorine atoms, in view of the stability of the monomer, it is preferable that the alkyl group has at least a hydrogen atom or a side chain at the α-position carbon. Specific examples include 2,2.2-)lifluoroethyl (meth)acrylate, 2,2.2-trifluoroethyl-α-fluoroacrylate, 2.2.2-
) Ria A/Oro 1-trifluoromethylethyl (meth)acryle), 1,1-dihydroperfluorobutyl-α-trif/L/Oromethyl acrylate), 1,1,
Examples include 2.2-tetrahydroperfluorooctyl (meth)acrylate, 1°1.2.2-tetrahydroperfluorooctadecyl (meth)acrylate, and the like.

When R1 is a substituent represented by general formula (2), +
The part 0H20HOH2-0÷ is included to impart hydrophilicity to the polymer, but if C is too large, the polymerizability and mechanical strength of the copolymer will decrease, so C is 1 or less. is preferred. Further, +OH2+ is a necessary part for the synthesis of Somer, but for the same reason as C, it is preferable that d is small, and is used in the range of 1 to 5. The bulkier the siloxanyl group is, the better the permeability to hydrogen is, but from the viewpoint of balance with polymerization properties, - and h are preferably 0 to 5. The fluoroalkyl group moiety preferably has f of 2 to 18 for the same reason as when R1 is a fluoroalkyl group, and has a hydrogen atom or a side chain at least at the carbon α position of the alkyl group, and (5s3+3 -trifluoropropyldimethylsiloxy)his(trimethylsiloxy)silylmethyl(meth)acrylate, (1,1,2,2-tetrahydroperfluorooctyldimethylsiloxy)bis(trimethylsiloxy)silylpropyl(meth)acrylate, (3゜5, 4,4,5,5.5-hebutafluoropentyldimethylsiloxy) [methylbis(trimethylsiloxy)siloxy]trimethylsiloxysilylprobyl (meth)acrylate.

((1*1+2+2-tetrahydroper 7AI orooctyldimethylsiloxy)dimethylsiloxy]bis(trimethylsiloxy)silylmethyl(meth)acrylate),
(3,3,4,4,5,5,5-hebutafluoropentyldimethylsiloxy)(pentamethyldisiloxanyloxy)trimethylsiloxysilylprobyl (meth)acrylate.

(1,1,2,2-tetrahydroperfluorododecyldimethylsiloxy)bis(pentamethyldisiloxanyloxy)silylmethyl(meth)acrylate, (5,3
,4,4,5,5,5-heptafluoropentyldimethylsiloxy)bis(trimethylsiloxy)silylmethylglycerol(meth)acrylate),(1,1,2,2
-tetrahydroperfluorooctyldimethylsiloxy)bis(trimethylsiloxy)silylpropylglycerol (meth)acrylate, (1,1,2,2-tetrahydroperfluorohexyldimethyl)[methylbis(
trimethylsiloxy]siloxy]trimethylsilylpropylglycerol (meth)acrylate), (1
, 1,2,2-tetrahydroperfluorohebutyldimethylsiloxy) (pentamethyldisiloxanyloxy)
trimethylsiloxysilylprobylglycerol (meth)acrylate), (1,1,2,2-tetrahydroperfluorotridecyldimethylsiloxydimethylsiloxy)bis(trimethylsiloxy)silylethylglycerol (meth)acrylate, (1,1,2 , 2-tetrahydroperfluorooctadecyldimethysiloxy)K.pentamethyldisiloxanyloxy)methylsilylethylglycerol (meth)acrylate.

When R1 is a substituent represented by general formula (4), the above R
For the same reason as when 1 is a substituent represented by general formula (3), k is preferably 0 or 1, t is preferably 1 to 6, voice is preferably 0 to 3, and X't'' e ' tx7 or x
When a hydrocarbon group is used, the number of carbon atoms is preferably 18 or less. Specific examples include tris(trimethylsiloxy)silylpropyl(meth)acrylate, tris(
trimethylsiloxy)silylpropyl-α-fluoroac IJt/-) #)'Js(trimethylsiloxy)silylpropyl-α-trifluoromethylacrylate, methylbis(trimethylsiloxy)silyloxybis(trimethylsiloxy)silylpropyl(meth)acrylate,
Methylbis(trimethylsiloxy)siloxybis(trimethylsiloxy)silylpropyl-α-fluoroacrylate, bis[methylbis(trimethylsiloxysiloxycotrimethylsiloxysilylprobyl(meth)acrylate), methylhis(trimethylsiloxy)siloxy(pentamethyldisiloxanyloxy) )()limethylsiloxy)silylpropyl(meth)acrylate), S-(
Methylbis(trimethylsiloxy)silylpropoxy 2-hydroxypropyl/L/(methaneacryle),
Examples include 5-C methylbis(trimethylsiloxy)silylpropoxy 2-hydroxypropyl-α-fluoroacrylate.

In addition, as a compound of component B, general formula (5) I(6
)t (7) e The monomers represented by (8) and (9) are used, but the higher the fluorine content of the compounds represented by each formula, the better the oxygen permeability and stain resistance, but the polymerization If the distance between the unsaturated bonds is too long, the polymerization will not be completed, so 5 and q in the formula are each 0 to 3.
, P is 1. ~8, r is preferably 1 to 10, S and μ are each 1 to 5, t is preferably 1 to 6, and the substituent z in formula (9)
Although 1 differs depending on the type of raw material of the monomer, a fluorine atom or a perfluorotetraalkyl group having 1 to 5 carbon atoms is preferably used because of its superiority in oxygen permeability, stain resistance, and polymerization properties of the copolymer. Specific examples of component B include 2, 2. S
, 5.4.4-hexafluoro-1,5-pentanediol di(meth)acrylate, 2.2,5,5.4,4
, 5.5-octafluoro-1,6-hexanediol bis(α-fluoroac IJ raton, 1,1,20.
20-tetramethyl-3,6,9,12,15,18-
hexaoxaperfluoroeicosane-1,20-diol di(meth)acrylate), 2,2-bis(4-α-
fluoroacrylaminophenyl) perfluoropropane, 2,2'-(1,5-phenylene)bis[2-(meth)acryloyloxyperfluoropropane'J, 5,
5,4,4,5,5,6.6-octafluoro-2,7
-Shioxaoctane-1,8-diolbis(α-trifluoromethyl acrylate).

The amounts of components A and B to be used are determined by taking into account the oxygen permeability, stain resistance, and shape stability of the resulting copolymer, and the range is A:B=6ci based on the total weight of A and B. :4n～
98:2% by weight is preferred.

That is, when A is less than 60% by weight, the oxygen permeability is rather low, and when it exceeds 98% by weight, the shape stability is decreased.

Furthermore, in the present invention, various hydrophobic monomers or hydrophilic monomers can be added and copolymerized for the purpose of improving the machinability of the copolymer and improving the wearing comfort of contact lenses. Hydrophobic monomers that can be used include methyl (meth)
Commonly used hydrophobic monomers such as acrylate, ethyl A/(meth)acrylate, cyclohexyl (meth)7 acrylate, benzyl (meth)acrylate, styrene, divinylbenzene, allyl (meth)acrylate, vinyl acetate, ethyl vinyl ether, etc. Can be mentioned. Also,
Hydrophilic monomers include 2-hydroxyethyl (meth)acrylate, diethylene glycol heptano(meth)acrylate, N,N-')ylthiAtacrylamide,
Examples include N-vinyl vinyl chloride, (meth)acrylic acid, and the like.

In order to increase the hydrophilicity of a lens, in addition to copolymerizing the hydrophilic monomers described above, it is possible to use a method of making the surface of a contact lens after molding hydrophilic, either in combination or alone. Hydrophilization methods include treatment with acids or alkalis, live pouring with ultraviolet rays, It is done. The hydrophilic monomer used in graft polymerization is copolymerizable with components A and B.
□The same hydrophilic monomers as above are used.

In order to copolymerize the comonomer system in the present invention,
A commonly used radical polymerization initiator is used. Specific examples of radical polymerization initiators that can be used include benzoyl peroxide, diisopropyl peroxydicarbonate, lauroyl peroxide, t
Examples include organic peroxides such as -butyl peroxyvivalate and azo compounds such as azobisisobutyronitrile. The amount to be used is preferably determined by taking into account the polymerization behavior of the seven-layer compound, and is generally preferably used in a range of 0.01 to 50 percent by weight based on the weight of the lens.

It is also possible to polymerize by adding a coloring agent such as a dye or an additive such as an ultraviolet absorber to this raw material system.

Conventional methods are used to copolymerize the above comonomer systems and form them into lenses. In other words, a comonomer containing a polymerization initiator is copolymerized in a suitable container such as a test tube to obtain a round rod or block, which is then processed into lenses that match the prescription through mechanical processing such as cutting and polishing. Just do it.

It is also possible to directly mold a contact lens by injecting a comonomer containing a polymerization initiator into a space created by two molds, such as those used for casting plastic lenses, and performing mold polymerization.

Since this comonomer system has a fast reaction rate, internal strain tends to occur when polymerizing a large volume product. In order to suppress such internal distortion and control the reaction, it is rational to polymerize in water as a heat medium.

[Effect]

It has been considered a problem that when contact lenses are worn, the supply of oxygen from the atmosphere to the cornea is insufficient, increasing the risk of injury. For this reason, attempts have been made to supply more oxygen to the cornea by changing both lens shape and material.

As for materials, as mentioned above, two approaches are being considered: water-containing soft contact lenses and oxygen-permeable hard contact lenses. It is generally known that the oxygen permeability of a hydrous soft contact lens increases as its water content increases, and oxygen is supplied through the lachrymal fluid taken into the lens.

On the other hand, oxygen-permeable hard contact lenses have a poor water absorption effect, and oxygen passes directly through the voids in the material. At this time, the presence of atoms or substituents with low surface energy, such as fluorine atoms, further strengthens the affinity for oxygen and has the effect of increasing the amount of oxygen permeation.

JP-A-59-28127 takes advantage of these effects, and uses a (meth)acrylate that is bulky and has a siloxanyl group that can provide sufficient voids, and a fluoroalkyl (methane acrylate) that lowers the surface energy. However, in contact lens materials, crosslinkable monomers are generally added in order to stabilize the lens shape and improve chemical resistance, and this patent also mentions crosslinkable monomers. However, even with high oxygen permeability materials using siloxanyl (meth)acrylate and fluoroalkyl (meth)acrylate,
Addition of a crosslinking agent inevitably reduces oxygen permeability, and the original effect cannot be maximized.

In contrast, the present invention uses a (meth)acrylate having a siloxanyl group and/or a fluoroalkyl group together with a crosslinkable monomer having a fluorine substituent, thereby making full use of the oxygen permeability of the material. On the other hand, the low surface energy unique to fluorine has the effect of preventing the adhesion of foreign substances such as proteins.

〔Example〕

Hereinafter, the present invention will be described in detail based on Examples, but the present invention is not limited to these scopes.

Examples 1 to 2 are examples of the method for synthesizing component A or B used in the present invention, and monomers not exemplified were also synthesized in substantially the same manner.

Example-1 Synthesis of (1,1,2,2-tetrahydroperfluorooctadecyldimethylsiloxy)bis(trimethylsiloxy)silylpropyl methacrylate trichloromethacryloxypropylsilane 262? was dissolved in anhydrous diethyl ether 5002 and placed in a 5 ton, 5-loop flask equipped with a mechanical stirrer, thermometer and 3 dropping funnels. Triethylamine 5301 was added over 1 hour while maintaining this solution at -50° to -40°C. Furthermore, a mixture of trimethylsilanol 180F, 1.1.2.2-tetrahydroperfluorooctadecyldimethylsilanol 9221 and diethyl ether 4001 was added to this solution at the same temperature.

After the addition, the mixture was stirred at room temperature for 1 hour, and the precipitated triethylamine hydrochloride was collected from door to door. Pour the leakage liquid with 500 ml of water.
After washing twice, and twice each with a 2% aqueous sodium bicarbonate solution and distilled water, it was dried over anhydrous magnesium sulfate. Thereafter, diethyl ether was removed by distillation at normal pressure, and low-boiling substances were distilled off roughly at α5 Torr and 90°C to obtain the desired monomer.

Example-2 (1,1,2,2-tetrahydroperfluorooctyldimethylsiloxy)bis(trimethylsiloxy)(r-
Synthesis of trichlorosilane 140 rpm methylene so.

V-dissolved and placed in a 3t two neck round bottom flask equipped with a magnetic stirrer, thermometer and addition funnel.

Triethylamine 5501 was added over 1 hour while maintaining this solution at -50°C to -40°C. Furthermore, add trimethylsilanol 180? to this solution at the same temperature. ,1,
1,2.2-Tetrahydroperfluorooctyldimethylsilanol 422? A mixed solution of and methylene chloride 4001 was added, and after the addition, the solution temperature was brought to 20° C., and after stirring for 1 hour, the precipitated triethylamine hydrochloride was leaked out.

The leaked liquid was washed three times with 400 d of water, and further washed twice each with a 2% aqueous sodium bicarbonate solution and distilled water, and then dried over anhydrous magnesium sulfate. After that, methylene chloride and unreacted substances were distilled off using an evaporator, and (
1*1*2.2-Tetrahydroperfluorooctyldimethylsiloxy)bis(trimethylsiloxy)silane [
RfS1] was obtained.

(RfSi) 514 r obtained above, acryglycidyl ether sy y s anhydrous benzene 500
500 mt of platinum black was added to the mixture in step 1, and the mixture was heated under reflux for 3 hours while stirring with a magnetic stirrer.

After the reaction mixture was left to cool, it was leaked, and the solvent was distilled off under reduced pressure using an evaporator. Further, low-boiling substances were distilled off at 50°C [11 Torr to obtain the desired product (1,1,2.2-tetrahydroperfluorooctyl). Dimethylsiloxy)bis(trimethylsiloxy)(r-glycidoxypropyl)silane was obtained.

Synthesis of (1,1,2,2-tetrahydroperfluoro,rooctyldimethylsiloxy)bis(trimethylsiloxy)silylpropylglycerol (meth)acrylate (1,1,2,2-tetrahydroperfluorooctyldimethylsiloxy)bis(trimethylsiloxy) Siloxy><r-
Glycidoxypropyl) silane 1861, potassium hydroxide 12, and hydroquinone 12F were placed in a four-bottle flask equipped with a magnetic stirrer, thermometer, dropping funnel, reflux condenser, and nitrogen gas introduction tube, and added dropwise while introducing nitrogen. Methacrylic acid 221 was added dropwise from the funnel into the stirred flask. After the dropwise addition, the reaction solution was gradually heated to 100° C. and reacted for 6 hours. After completion of the reaction, the reaction solution was returned to room temperature, and the precipitated insoluble salt was removed from the hot water. N-hexane was added to the resulting leakage liquid to dissolve it, and the solution was diluted with IJum aqueous solution 5 times and then with saturated saline 5 times.
After washing twice, it was dried with anhydrous magnesium sulfate. After this leaked out, 5-hexane was distilled off under reduced pressure to obtain the target monomer Example-3 2,2,S,5,4.4-hexafluoro-1,5-bentanediol Synthesis of dimethacrylate In a 1 L three-neck flask equipped with a Dimroth reflux condenser, 1 lower funnel, and a thermometer, 2.2,3.5,4.4-hexafluoro-1,5-bentanediol 11.2 S', Dehydrated benzene 430? and Pyridine 2179 were added and mixed well with a magnetic stirrer. While stirring further,
Methacrylic acid chloride 6Z71, which had been synthesized in advance by a conventional method, was added dropwise from the dropping funnel over a period of 1 hour. During this time, the reaction solution was cooled by 7 sq. ml using ice water so that the temperature of the reaction solution did not exceed 15.degree. After the dropwise condensation was completed, the cooling bath was removed, and the mixture was heated while stirring and refluxed for 2 hours to complete the reaction.

After the reaction solution was allowed to cool, pyridine hydrochloride was removed by filtration. After removing unreacted methacrylic acid chloride, pyridine and benzene from the oral fluid under reduced pressure, t-butylcatechol 105f was added and vacuum distillation was performed to obtain the desired 2,2,5,5.4.4-hexane. 7/L/Olow 1.
5-pentanediol dimethacrylate) 25.8 F
(74%) I got it.

The boiling point was 98-b. The purity was 98% or more as determined by chromatography. Engineering R
The spectrum measurement result is 1738c! ! rl (C=Q
), absorption due to methacrylic ester was observed in 1659bi-' (a=c).

Other Component B compounds were also synthesized in a similar manner.

If the product had a high boiling point and could not be distilled, it was purified by silica gel column chromatography using a hexane/ethyl acetate solvent.

Abbreviations in the following examples are based on the abbreviation list at the end of the specification. In addition, all parts in the examples represent parts by weight.

Example 1 This example shows a typical example of producing a copolymer according to the present invention.

IF (80 parts of SMA, 10 parts of HPDMA and HIfi
'Mix 10 parts of MA well at room temperature,
(2,4-dimethylvaleronitrile) (1159) was added and stirred. This mixed solution was poured into a glass test tube, and the inside was replaced with nitrogen and then sealed. The test tube was heated to a temperature controlled by a program controller. Soaked in water tank for 30 minutes
6 hours at ℃, 4 hours at 35℃, 3 hours at 40℃, 45℃
Polymerization was carried out by heating for 2 hours at 50°C, 2 hours at 60°C, 2 hours at 70°C, 2 hours at 90°C, and then 2 hours at 110'C in an air oven. A contact lens was obtained by cutting, cutting and polishing a round rod of the obtained copolymer.The various physical properties of the obtained co-pentapolymer were measured by the following methods.

Oxygen permeability coefficient: Xertex Corporation
MODEL 2110 manufactured by n company (Multi-ra
nge Analyzer for Dissolved
12.7 TIrInl diameter [12
The measurement was carried out on a test piece of mm.

Protein deposition properties: egg white lysozyme in α5% physiological saline solution for 16 hours at 37°C, diameter 12.7 mm, It
[Immerse the test piece of L2rH1, and 280°C before and after
The luminous intensity in nm was measured to determine the amount of egg white lysozyme attached.

Pinkers hardness: Taiyo tester (1!13 Terasawa type MM
- Type 2 ultra-micro hardness meter contact angle: Measured by the underwater bubble method using a Kyowa Kagaku Co., Ltd. 0A-D type contact angle meter.

As a result, the oxygen permeability coefficient (DK) was 5.2
+.

(ml - cml crl ・sec ・rraHf'
), Vickers hardness (HV) was 11.5, contact angle was 69°, and no protein deposition was observed.

Examples 2 to 15 and Comparative Examples 1 to 3 Polymerization and physical property evaluation were performed according to the method of Example 1 using the compositions shown in Table 1. The results of physical property evaluation are shown in Table-1.

Example-16 The lens base material obtained in Example-1 was depressurized to a vacuum degree of α1 Torr in a plasma polymerization apparatus, and while flowing argon gas at 10103 TP/m, the discharge frequency was set to W11556.
Low-temperature plasma treatment was performed at MHz and discharge power of 30 W for 50 seconds. Subsequently, while continuing glow discharge, the temperature was increased to 3a to 35°C.
NVP at 10sTP mj/j Argon gas at 1
NVP was graft-polymerized on the surface of the contact lens for 90 seconds while supplying at 0 STP ml/via.

Example-17 The lens base material obtained in Example-12 was subjected to low-temperature plasma treatment under the same conditions as Example-16. Next, stop the glow discharge and inject HEMA at 12 S T P mA at 30-35 °C.
/m2 and apply H to the contact lens surface for 60 seconds.
A graft polymerized film of EMA was formed.

The characteristics of Examples 16 and 17 are shown in Table 2.
2 Abbreviation list IPAMA: 2,2.2-)Refluoro-1-trifluoromethylethyl methacrylate? 71F5A: 1.1-dihydroperfluorobutyl-α-trifluoromethylacrylate 1F33S4MA: (1,1,2,2-tetrahydroperfluorooctadecyldimethylsiloxy)bis(trimethylsiloxy)silylpropyl methacrylate? 13S4GMA: (1,1,2,2-tetrahydroperfluorooctyldimethylsiloxy)bis(trimethylsiloxy)silylpropylglycerol methacrylatej34MA:)lis(trimethylsiloxy)silylpropyl methacrylate 571FA:Methylbis(trimethylsiloxy)siloxy pentamethyl disiloxanyl oxy trimethylsiloxy silylpropyl-α-fluoroac')1/-toHFDMA: 2,2,3,3,4.4-hexafluoro-1,5-bentanediol dimethacrylate IFBPAA: 2,2-bis(4- α-7/I/Oroacrylaminophenyl) perfluoropropane PBPMA: 2.2'-(1,5-)unicine)bis(
2-methacryloyloxypenefluoropropane) MMA: Methyl methacrylate HKMA: 2-hydroxyethyl methacrylate N
VP: N-vinylpyrrolidone MAA: Methacrylic acid 1! iGDMA: Ethylene glycol dimethacrylate [Effects of the invention] As described above, the present invention has a siloxanyl group and/or
Or, it is a funact lens made of a copolymer of a (meth)acrylate having a fluoroalkyl group and a fumonomer containing as an essential component a crosslinking monomer having a fluorine substituent, and has extremely high oxygen permeability. be.

Furthermore, due to the effect of the fluorine substituents contained in the ingredients, proteins and the like are less likely to adhere. As a result, two of the major problems conventionally associated with long-term continuous wear of contact lenses have been solved, and it has become possible to provide a safer, more comfortable contact lens that can be worn continuously for a long time.

that's all

Claims (1)

[Claims] Contact lens A characterized by being made of a copolymer of comonomers containing the following A and B as essential components: The general formula is (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (1) [However, X^1 in the formula represents a hydrogen atom, a methyl group, a fluorine atom, or a trifluoromethyl group, and R^1 represents the general formula CaHbF_2_a_-_b_+_1 (a is 2 to 1
(integer 8, b represents an integer from 0 to 2a-1), or general formula (2) ▲There are mathematical formulas, chemical formulas, tables, etc.▼……(2 ) {In the formula, c is 0 or 1, d is an integer from 1 to 3, X^2 and X^3 are each independently a methyl group, a bis(trimethylsiloxy)methylsiloxy group, or formula (3) ▲ Numerical formula, chemical formula , tables, etc.▼...(3) where e and h are each independently an integer from 0 to 3,
f is an integer from 2 to 18, g is an integer from 0 to 2f-1, i is 1
An integer of ~18, j represents an integer of 0 to 2i+1} or a substituent represented by the general formula (4) ▲Mathematical formulas, chemical formulas, tables, etc.▼...(4) (In the formula, k is 0 or 1, l is an integer from 1 to 3, X^4,
X^5, X^6, X^7 and X^8 each independently represent a methyl group, a pentamethyldisiloxanyloxy group, or a bis(trimethylsiloxy)methylsiloxy group, and m is an integer of 0 to 3. a substituent represented by
or one or more monomers represented by [C1-C18 hydrocarbon group]] B: General formula (5), (6), (7), (8) or (9
) Y^1-(CH_2)_n-(CF_2)_p-(CH
＿２）＿q－Y＾２...(5) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(6) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(7) ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (8) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(9) [However, n and q in the formula are each independently an integer of 0 to 3, p is an integer of 1 to 8, and r is an integer of 1 to 10. The integers, s and u each independently represent an integer of 1 to 3, t represents an integer of 1 to 6, Z^1 represents a fluorine atom or a perfluoroalkyl group having 1 to 3 carbon atoms, Y^1, Y^ 2.Y^
3, Y^4, Y^5, Y^6, Y^7, Y^8, Y^9
and Y^1^0 are each independently represented by the general formula (10) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(10) (In the formula, Z^2 is a hydrogen atom, a methyl group, a fluorine atom, or a trifluoro a methyl group, A represents an oxygen atom or an NH group); or an allyloxycarbonyl group, a vinyloxycarbonyl group, or an allyl carbonate group; more than one type of body