CA1103838A - Polymer for contact lens and contact lens made thereof - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
A polymerization product suitable for contact lenses comprising (a) an organosiloxane monomer having the following general formula wherein n is an integer of 1 to 3, X is

Description

The present inventlon relates ~o novel copolymers suitable for preparing contact lenses and contact lenses made thereof which do not substantially absorb water and have an excellent oxygen permeability enough to wear them continuously for a long period of time.
Contact lenses put presently Oll the market are c1assified illtO two large groups o water-nonabsorptive contact lenses and water-absorptive contact lenses.
The water-nonabsorptive contact lenses are further classified into hard contact lenses made of polymethyl methacrylate and soft contact lenses made of silicor.e rubber Also t as the water-absorptive contact lenses, soft contact lenses made of poly-2-hydroxyethyl methacrylate and high water content contact lenses made of polyvinyl pyrrolidone are ~nown.
The water-nonabsorptive hard contact lenses made of polymethyl methacrylate have a history of several tens of years, but are still insufficient for use in a clinical viewpoint. That is to-say, although such contact lenses have excellent optical property and durabili~y, they give a strong foreign body sensation to persons in an early stage of the wear due to being poor in hydrophilic property of the lens surface and, there~ore, require a long term for accommodation to the lenses. Moreover, since the oxygen permeability is poor, it is impossible to wear them continu-ously for a long period of time in corneal physiology.
The silicone rubber soft contact lenses are very water-repellent and are grea~ly different from cornea in thermal properties such as thermal conductivity and thermal diffusivity. Therefore, they give a foreign body

- 2 -~- sensation, particularly a burning sensation, despite of having a very lar~e oxygen permeability. A stronger patience than tile case of polymethyl methacrylate lenses is required for accommodating thereto. Also, silicone l~ubber is soft and elastic, and precise mechanical trea~mellts s~lch as cuttin~, grinding and polishing are very dificult. On the other hand, many attempts to make the surface of silicone rubber lenses hydrophilic have been reported, but satisfactory silicone rubber contact lens has never been developed.
The water-absorptive contact lenses made of poly-2-hydroxyethyl methacrylate are good in a sensation of ~ear 9 but since -the water content of the lens is at most 40 % by weight, the permeation of oxygen through water as a medium is insufficient and it is impossible to continuously wear the lenses for a long period of time.
The high water content contact lenses made of polyvinyl pyrrolidone have an excellen~ oxygen permeability.
~lowever, they have the disadvantages that the durability is poor, and also that the water content of the lens changes depending on external environment at the time of wearing ~; the lenses and ~he lens contour changes with the change of ~ the water content so as to lower the visual Gorrection - abili~y.
Also, there is a serious problem in these water-absorptive contact lenses that they are contaminated by bacteria. Although boiling treatmen~, chemical sterilization treatment, etc. are considered as a means for preventin~ the contamination by bacteria9 these treatments are troublesome. Moreover, the boiling treatment accelerates the deterioration in quality of lens material and the chemiccll sterilization treatment incurs danger to eyes.
~s stated above, convcntional contact lenses ~lave variolls defects, and a contact lens having no such deE~cts are clesired.
It is thereore an object of the present invention to provide a novel contact lens material.
Another object of the invention is to provide a contact lens material which has an excellent oxygen permeability and a proper hydrophilic property and is substantially water-nonabsorptive.
A further object of the invention is to provide a contact lens which has an oxygen permeability enough for the continuous wear for a long period of time and moreover has a proper hydrophilic property.
A still further object of the invention is to provide a contact lens which can be comfortably worn continuously for a long period of time without giving a foreign body sensation.
A more still further object of the invention is to provide a contact lens which is substantially water-nonabsorptive, and has an excellent optical property and is not contaminated by bacte~ia.
These and other objects of the invention will become apparent from the description hereinafter.
It has now been found that the above-mentioned objects can be attained by using as a contact lens material a polymer containing at least 30 % by weight of an organosiloxane monomer having the following general formula ,,~,,~r~g3~

[1]:

1~13 yl 1~13 C~-lz=C-C-O-~~C~12 I~l-c~l2 o ~c1l2)11 1 I CI]
O 0~1 y2 C~13 whcreln 11 is 111 Lnteger of l to 3, X is--~(C~12)p-0 ~ in ~hic11 p is an integ~er of 2 to 4 and q is 0 or an integer of l to 3, and Y1J y2 and Y3 are metllyl group or -0-Si-(CH3)3.
According to the present invention, there is provided a novel polymerization product of at least one organosiloxane monomer, or of at least one organosiloxane monomer with a hydrop}1ilic monomer and/or a hydrophobic monomer, which is suited for contact lens material. The polymerization product which is cross-linked is also useful as a contact lens material.
According to a further feature of the invention, there is provided a contact lens made of the above polymerization product.
The polymerization product has an excellent oxygen permeability and a proper hydrophilic property and is substantially water~nonabsorptive and, therefore, the contact lenses prepared therefrom have an excellent optical property and can be safely, comfortably worn continuously for a long period of time without giv1ng a foreign body sensation and be1ng not contaminated by bacteria.
Compounds employed as an organosiloxane monomer in the present invention, having the following general formula ~I]:

l~3 yl CH3 C~12=C-6--X-C~l2-l~l-c~2-o-(c~l2)n I f [I]
O O~l Y C~l3 w}lerein n is all integer of 1 to 3, X is -~(Cll2)p-O ~ in whlcll 1) is an intcger of 2 to ~ an(l ~l is O or an integer of l to 3, and yl~ y2 and Y3 are me~hyl group or -O-Si-(C~13)3, are novel compo-lnds~
It is known that silicone rubber has an excellent oxygen per~eability, and as disclosed in Japanese Patent Publication No. 33502/1977 that the utilization of an alkylsiloxy group is an available means for increasing the oxygen permeability.
In contrast to such a known art, the feature of the present invention lies in the use o particular methacrylic acid ester derivatives having not only alkyl-siloxy group, but also hydrophilic group ln the molecule.
That is to say, the organosiloxane monomers shown by the general ormula [I~ have hydroxyl group which is a hydrophilic group, and some of them have also a polyether group which is a hydrophilic group. This has a very ; significant meaning in adaptation of the obtained copolymers as contact lens materials.
As stated above, it is useful to utllize the alkylsiloxy group in increasing the oxygen permeability, but the obtained polymer shows undesirable water~repelling property with increase of the number of the alkylsiloxy groups in the polymer. For instance, a polymer consisting essentially of polyslloxanylalkyl ester of acrylic or me~hacrylic acid having no hydrophilic group as disclosed 30 in Japanese Patent Publication No. 33502/1977 has a very strong water repelling property, and is not suitable -for contact lens materials in spite of having high oxygen permeability. In order to offset this defect, the polysilo~anylcllkyl estcr monomer may be copolymerized with a l~ydrol)hilic monomer ~o provicle tile obtained copolymer witll a proper hydrophilic property, but since it is hard to copolymerize witll the hydrophillc monomer, the copolymer is liable to become opaque. This is fatal defect for use as contact lens materials. Therefore, the polymerization ratio of the hydrophilic monomer to the polysiloxanylakyl ester monomer is limited to produce a transparent copolymer, and it is very difficult to decrease the water repelling property by copolymerizing with a hydrophilic monomer.
In case of such a polysiloxanylalkyl ester monomer, when the water repelling property is repressed by reducing the number of the alkylsiloxy groups in the obtained polymer, the oxygen permeability becomes low, and when the oxygen permeability is raised by increasing the number of the alkylsiloxy groups in ~he obtained polymer, the water repelling property becomes strong. In any case, there cannot be obtained a polymer suited for preparing a contact lens which can be comfortably worn continuously for a long period of time.
On the other hand, according to the present invention, it is posslble to obtain polymers having an excellent hydrophilic property and moreover a high oxygen permeability withou~ copolymerizing with a hydrophilic monomer, since the compounds of the general formula [I]
employed in the present invention have hydrophilic hydroxyl group and some of them further have a polyether group . ~.

which is hyclrophilic group. Therefore, contact lenses which can be comfortably worn continuously for a long period of time can be obtained from the polymers obtained according -to the present invention.
'I`he novel compounds o:~ the general formula [I]
employed in the present invention are classified into the following three types;
polysiloxanyl(alkylglycerol) monomethacrylates having the following geIleral ~ormula CII]:
fi~3 Yl Ci13 c~2=c-c-o-cll2-lci-l-c~l2-o-(cil2)n 7i 7 [II]
O Oil y2 Cil3 wherein n is an integer of 1 to 3, and yl~ y2 and Y3 are methyl group or -O-Si-(CH3)3, polysiloxanyl(alkylglycerol)alkyleneglycol monomethacrylates having the following general formula [III]:
C1~l3 ~1,1 C~l3 Cii =c-6-o-(c}l2) -O-Cil2-fH-Cil2-O-(C~l2)n 1 7 :: O Oll Y CII3 wherein n is an integer of l to 3, p is an integer of 2 to 4, and Y1J y2 and Y3 are methyl group or -O-Si-(CH3)3, and polysiloxanyl~alkylglycerol)polyalkyleneglycol monomethacry-lates having the following general formula [IV]:
CH3 Iyl CH3 2 1l t(CH2)p O ~ CH2~1CH~CH2~~(CH2)n~si~~7i-Y3 tIV]

~herein n is an integer of 1 to 3, p is an integer of 2 to ~, q' is 2 or 3, and yl~ y2 and Y3 are methyl group or -O-Si- (Cll ) Tl~ese particular organosiloxalle monomers sho~n by tlle g~ller~ll Eorm~ll.ls ~II], ~ and rIVJ are prepared by reactillg a polysiloxanylaLkyloxypro~ylelle oxide Wit}l metllacrylic acld, an alkyleneglycol monomethacrylate or a polyalkyleneglycol monomethacrylate. For instance, polysiloxanyl(alkylglycerol) monomethacrylates shown by the general formula [II] are prepared as follows:
One mole of the polysiloxanylalkyloxypropylenc oxide having the following general formula rVII~:
11 fll3 \2~C~l-C~l2-o-(cl~2)n-lsi-o-si-y3 ~VII]
O Y C~l 3 wherein n is an integer of 1 to 3, and yl~ y2 and Y3 are methyl group or -O-Si-(Cll3) 3 2 moles of methacrylic acid, about 0.1 mole of potassium hydroxide and about 0.01 mole of hydroquinone or hydroquinone monomethyl ether are added to a reaction vessel~ and the reaction i5 then carrled out at a temperature of 80 ~o 105C. for 8 to 24 hours with agita~ion. When the reactlon temperature is high, the reaction is complete in about 10 hours, but by-products are increased. On the other hand, when the reaction temperature is low, it is required to conduct the reaction for about 30 hours, but by-products are reduced. Since the desired reaction product has a high boiling point and is polymerizable, it is difficult ~o remove the by-products by distillation and, therefore, .~

' ' ' .

3$~

it is desirable to conduct the reaction at a temperature in the vicinity of 90C. for more than 20 hours. After the completion of the reaction, the reaction mixture is allowed to cool and is filtered. The iltrate is then clissolved in n-llexane and is washed several times with a 0.5N a~lueous solution of sodiul~ ydroxi.de by employing a separatory Eunnel until the aqueous sol~ltion becomes colorless, and after further washing with a saline water until it shows neutral, is dehydrated for a day and night by employing a drying agent such as anhydrous sodium sulfate.
After removing anhydrous sodium sulfate by filtration, n-hexane is distilled away, for instance, by means of an evaporator to give the desired reaction product. When the thus obtained reaction product is still tinged with yellow, the product is preferab1y further treated with active carbon. The identification of the product is conducted by means of gas chromatography, elemental analysis, infrared spectroscopy, etc. The polysiloxanyl-~alkylglycerol)alkyleneglycol monomethacrylates shown by the general formula [III] and polysiloxanyl(alkylglycerol)~
polyalkyleneglycol monomethacrylate shown by the general formula [I~] are prepared in the same manner as the above, respectively by employing an alkyleneglycol monomethacrylate for the former and a polyalkyleneglycol monomethacrylate for the latter instead of methacrylic acid.
Examples of the polysiloxanyl(alkylglycerol) monomethacrylates of the general formula [II~ employed in the present invention are pentamethyldisiloxanyl(methyl-glycerol) monomethacrylate, pentamethyldisiloxanyl(ethyl-glycerol) monomethacrylate, pentamethyldisiloxanyl(propyl-glycerol) monomethacrylate ~these compounds being expressed as pcntamcthyldisiloxaTIyl-(methylglycerol~ ethylglycerol or propylglycerol) monomet]lacrylate, and hereinafter the nallle oE comlo~ ds being e~xl-ressed in thc same manller], hcptametilyltrisilo~anyl-(met}lylglycerol~ ethylglycerol or propylglycerol) monolllethacrylate, methyldi(trimethylsiloxy)-sylyl-(methylglycerol, ethylg:Lycerol or propylglycerol) monomethacrylate, tris(trimethylsiloxy)sylyl-(methylglycerol, ethylglycerol or propylglycerol) monomethacrylate, and pentamethyldisiloxydi(trimethylsiloxy)sylyl-(methylglycerol, ethylglycerol or propylglycerol) monomethacrylate.
Examples of the polysiloxanyl(alkylglycerol)alkylene-glycol monomethacrylates employed in the present invention are pentamethyldisiloxanyl-(methylglycerol, ethylglycerol or propylglycerol)-ethyleneglycol monomethacrylate, hepta-methyltrisiloxanyl-(methylglycerol, ethylglycerol or propylglycerol)-ethyleneglycol monomethacrylcLte, methyldi-(trimethylsiloxy)sylyl-(methylglycerol, ethylglycerol or propylglycerol)-ethyleneglycol monomethacrylate, tris-(trimethylsiloxy)sylyl-(me~hylglycerol, ethylglycerol or propylglycerol)-ethyleneglycol monomethacrylate, penta-methyldisiloxydi(trimethylsiloxy)sylyl-(methylglycerol, ethylglycerol or propylglycerol)-ethyleneglycol monometha-crylate, pentamethyldisiloxanyl-(methylglycerol, ethylglycerol or propylglycerol)-propyleneglycol monomethacrylate 9 heptamethyltrisiloxanyl-(methylglycerol, ethylglycerol or propylglycerol)-propyleneglycol monomethacrylate, methyldi(trimethylsiloxy)sylyl-(methylglycerol, ethylglycerol or propylglycerol)-propyleneglycol monomethacrylate, tris(trimethylsiloxy)sylyl-(methylglycerol, ethylglycerol .. .

or propylglycerol)-propyleneglycol monomethacrylate, pentamethyldisiloxydi(trimethylsiloxy)sylyl-(methylglycerol, ethylglycerol or propylglycerol)-propyleneglycol monometha-crylate, pentamethyldisiloxanyl-(methylglycerol, ethylglycerol or propylglycerol)-butyleneglycol mollometllacrylate, hepttlmetlly].trisiloxanyl-(methylglycerol, ethylglycerol or propylglycerol)-butyleneglycol monomethacrylate, methyldi-(trimethylslloxy)sylyl~ let}lylglycerol, ethylglycerol or propylglycerol)-butyleneglycol monomethacrylate, tris(tri-methylsiloxy)sylyl-(methylglycerol, ethylglycerol or propyl-glycerol)-butyleneglycol monomethacrylate, and pentamethyl-disiloxydi(trimethylsiloxy)sylyl-(methylglycerol~ ethyl-glycerol or propylglycerol)-butylelleglycol monomethacrylate.
Examples of the polysiloxanyl(alkylglycerol)poly-alkyleneglycol monomethacrylates employed in the presentinvention are pentamethyldisiloxanyl-(me~hylglycerol, ethylglycerol or propylglycerol)-diethylenglycol monometha-crylate~ heptamethyltrisiloxanyl-(methylglycerol, ethylglycerol or propylglycerol)-diethyleneglycol monomethacrylate, methyldi(trimethylsiloxanyl)sylyl-(methyl-glycerol, ethylglycerol or propylglycerol)-diethyleneglycol monomethacrylate, tris(trimethylsiloxy)sylyl-(methylglycerol, ethylglycerol or propylglycerol)-diethyleneglycol mono-methacrylate~ pentamethyldisiloxydi(trimethylsiloxy)sylyl-(methylglycerol, ethylglycerol or propylglycerol)-diethylene-glycol monomethacrylate, pentamethyldisiloxanyl-(methyl-glycerol ethylglycerol or propylglycerol)-triethyleneglycol monomethacrylate, heptamethyltrisiloxanyl-(methylglycerol, ethylglycerol or propylglycerol)-triethyleneglycol monomethacrylate, methyldi(trimethylsiloxy)sylyl-(methyl-glycerol, ethyl~lycerol or propylglycerol)-triethylene-glycol monomethacrylate, tris(trimethylsiloxy)sylyl-(methyl-glycerol, ethylglycerol or propylglycerol)-triethylene-glycol monolllet}lacrylate, pentamethyldisiloxydi(trimethyl-s:iloxy)sylyl-(lllethylglycerol, e-thylglyce~rol or propylglycerol)-triethylelleglycol monometllacrylate, pentametllyldisiloxanyl-(methylglycerol, ethylglycerol or propylglycerol)-dipropylelleglycol monomèthacrylate, heptamet.hyltrisiloxanyl-(methylglycerol, ethylglycerol or propylglycerol)-dipropyleneglycol monomethacrylate, methyldi(trimethylsiloxy)-sylyl-(methylglycerol, ethylglycerol or propylglycerol)~
dipropyleneglycol monomethacrylate, tris(trilnethylsiloxy)-sylyl-(metllylglycerol, ethylglycerol or propylglycerol)-dipropyleneglycol monomethacrylate, pentamethyldisiloxydi-(trimethylsiloxy)sylyl-(methylglycerol, ethylglycerol or propylglycerol)-dipropyleneglycol monomethacrylate, pentamethyldisiloxanyl-(methylglycerol, ethylglycerol or propylglycerol)-tripropyleneglycol monomethacrylate, ; heptamethyltrisiloxanyl-(methylglycerol, ethylglycerol or propylglycerol)-tripropyleneglycol monomethacrylate, methyldi(trimethylsiloxy)sylyl-(methylglycerol, ethylglycerol or propylglycerol)-tripropyleneglycol monomethacrylate, tris(trimethylsiloxy)sylyl-(methylglycerol~ ethylglycerol or propylglycerol)-tripropyleneglycol monomethacrylate, pentamethyldisiloxanyl-(methylglycerol, ethylglycerol or propylglycerol)-dibutyleneglycol monomethacrylate, heptamethyltrisiloxanyl-(methylglycerol, ethylglycerol or propylglycerol)-dibutyleneglycol monomethacrylate, methyldi(trimethylsiloxy)sylyl-(methylglycerol, ethylglycerol ~0 or propylglycerol)-dibutyleneglycol monomethacrylate, tris(trimethylsiloxy)sylyl-(methylglycerol, ethylglycerol or propylglycerol)-dibutyleneglycol monomethacrylate, pentamethyldisiloxydi(trimethylsiloxy)sylyl-(methylglycerol, ethylglycerol or propylglycerol)-dlbutyleneglycol mo~olllethacrylate, pentamet}lyldisiloxanyl-(metllylglycerol, ethylglyceroL or propylglycerol)-tributyleneglycol monometllacryla~e, l~eptamcthyltrisiloxanyl-(methylglycerol, ethylglycerol or propylglycerol)-tributyleneglycol monomethacrylate, methyldi(trimethylsiloxy)sylyl-(methyl-glycerol, ethylglycerol or propylglycerol)-~ributylene-glycol monomethacrylate 9 tris(trime~hylsiloxy)sylyl-(methyl-glycerol, ethylglycerol or propylglycerol)-tributyleneglycol monomethacrylate, and pentamethyldisiloxydi(trimethyl-siloxy)sylyl-(methylglycerol, ethylglycerol or propylglycerol)-tributyleneglycol monomethacrylate.
The organosiloxane monomers may be employedsingly or in admixture thereof, and the obtained homopolymers and copolymers of these organosiloxane monomers have an excellent oxygen permeability and a good hydrophilic property.
Therefore, contact lenses prepared from such polymers can be worn continuously for a long period of time without feeling of foreign body sensa~ion. Further, since these polymers are substantially water-nonabsorptive, the contact lenses made thereof are excellent in optical property and also there is no problem of contamination by bacteria. In case of some organosiloxane monomers, the obtained polymers show a tendency to be inferior in mechanical processing property, particularly polishing property. In that case, cast polymerization using a mold having a shape of contact lens is preferably adopted, since a contact lens can be directly 33~

prepared.
In order to provide the obtained polymer with the mechanical ~rocessing property and stiffness, or with further hydropllilic l-ropcrty, the organosiloxane monomers may be copolymerized with other monomers. In that case, it is llecessary to employ the organosiloxane monomer in an amount oE at leas~ 30 % by ~eight based on the total weight of the monomers eml)loyed. W}lell the amount of the organosiloxane monomer is less than the above range, the oxygen permeability of the o~tained copolymer becomes low.
The organosiloxane monomer may be copolymerized with a hydrophobic monomer to provide the obtained copolymer with the stiffness and mechanical processing property.
As the hydrophobic monomer, there are preferably employed a methacrylic acid alkyl ester of which homopolymer has a glass transitioll temperature higher than room temperature.
Examples of the hydrophobic methacrylic acid alkyl ester monomer employed in the present invention are methyl methacrylate, ethyl methacrylate and cyclohexyl methacrylate.
These hydrophobic monomers may be employed singly or in admixture thereof. The amount of the hydrophobic monomer is selected from 5 % to 70 % by welght, preferably from 10 % to 60 % by weight, based on the total weight of the monomers employed. When the amount of the hydrophobic monomer is less than the above range, it is difficult to raise the mechanical processing property and stiffness, and when the amount is larger than the above range, the copolymer having a sufficient oxygen permeability cannot be obtained.
Since the particular organosiloxane monomers employed in the present invention have hydroxyl group or , . , ' ., ' : ' ': , . ......................... ' - . ~ . .

~ 3 ~

fllrther have a polyether group, the obtained polymers have a good hydrophilic property in acldition to a good oxygen permeability, even if not copolymerized with a hydrophilic monomer and, thercfore, the wear oE the contact lenses prepared thererom is very com~ortable and moreover it is possible to wear continuously for a long period of time.
Ilowever, in order to ~urther raising the hydrophilic property, for instance, with the object of providing the materials of contact lens suited for very nervous persons, the organo-siloxane monomer may be copolymerized with a hydrophilicmonomer. Examples of the hydrophilic monomer employed for this purpose are ethylene glycol monomethacrylate, ethylene glycol monoacrylate, diethylene glycol monomethacrylate, diethylene glycol monoacrylate, triethylene glycol mono-methacrylate, triethylene glycol monoacrylate, N-vinly pyrrolidone and dimethyl acrylamide. These hydrophilic monomers may be employed singly or in admixture thereof.
The amount of the hydrophilic monomer is selected from 1 %
to 20 % by weight, preferably from 3 % to 18 % by weight, based on the total weight of the monomers employed. When the amount of the hydrophilic monomer is less than the above range, it is impossible to attain the object, and when the amount is larger than the above range, the obtained copolymers become water-absorptive and become soft by : 25 absorbing water.
It is proposed that in order to improve the hydrophilic property of contact lenses) the surface of the contact lens is applied with a wetting agent such as a dilute aqueous solution of an alkyldimethylbenzylammonium chloride, or is subjected to an electric discharge treatment 3~3~

or a chemical treatment with a strong oxidizing agent such as nitric acid. As stated beore, the copolymers of the present invention have a good hydrophilic property and, therefore, req~llre no such a treatment. Ilowever, with the same object as the before-mentioned, it is of course possible to subject the contact lenses o~ the present invention to such trea~ments instead of or in additiorl to the means by the copolymerization with a hydrophilic monomer.
~or the purpose of improving the mechanical processing property of the lens materials such as cutting, grinding or polishing, or lmproving the solvent resistance and the shape stability of the contact leneses, the polymers may be cross-linked in a conventional manner. In general, in order to make the polymers possess the cross-linked structure, the polymerization is carried out in the presence of a cross-linking agent. Particularly, it is desirable to employ a polyfunctional monomer as the cross-linking agent which is previously added to the polymerization system, and then the polymerization is carried out. As the polyfunctional monomer employed in the present invention, in addition to known cross-linking agents generally employed in the polymerization of a vinyl monomer, such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, allyl methacrylate, trimethylolpropane trimethacrylate, divinyl benzene and diallyl phthalate, there are preferably employed polyfunctional monomers having siloxane bond, namely a poly-siloxanylbis(alkylglycerol acrylate) and polysiloxanylbis-(alkylglycerol methacrylate) having the following general .

3~
formula [V]:

R CH CH
I 1 3 ~ 1 3\
C~2 c b C~l2 IH Cll2 O (Cll2)n li t li tm O ~l-l Cil3 Cll3 l~2 (Cl12)l~-C112-fll-cll2-o-6-c-cll2 ~V]
0~1 0 wherein n and n' are an integer of 1 to 3, m is 1 or 2, and Rl and R2 are hydrogen or methyl group, and a polysiloxanylbis(alkyl acrylate) and polysiloxanylbis(alkyl methacrylate) having the following general formula rvI ]

Rl CH CH R2 Cl~2 C 6-O-(CH2)n-~ O-Si ~ (CH2)n~ O ll C=CH2 [VI]

wherein n and n' are an integer of 1 to 3, m is 1 or 2, and Rl and R2 are hydrogen or methyl group.
Since these cross-linking agents of the general formulas [V] and [VI] have siloxane bond in their molecule, the oxygen permeability of the obtained cross-linked polymers is maintained still high and, thereforeg they are preferably employed in the present invention. The polysiloxanylbis(alkylglycerol acrylate) and polysiloxanylbis-(alkylglycerol methacrylate) of the general formula [V] have not only siloxane bond, but also hydroxyl group which is a hydrophilic group. Therefore, since the hydrophilic property of the obtained cross-linked polymers can also be main~ained, the use is particularly useful.
The polysiloxanylbis(alkylglycerol acrylate) and 38~

polysiloxanylbis(alkylglycerol methacrylate) of the formula rV] are novel compound, and are prepared, for instance, by the followlng method.
Olle mole of a ~olysiloxal~ylbis(alkyloxypropylene oxide) having the followillg general ormula rVIII~:

C~l Cll 1 3 f 1 3 \2/ C~l2 (C~l2)n~li t-~ C~l2)-ll o-C~I2-C, - ,~l2 rvIII]
O C~l3 CH3 O

~herein n and n' are an integer of 1 to 3~ and m is 1 or 2, 3 moles of acrylic or methacrylic acid, about 0.2 mole of potassium hydroxide and about 0.02 mole of hydroquinone or hydroquinone monomethyl ether are added to a reaction vessel, and the reaction is then carried out at a temperature of 80 to 100C. for 10 to 30 hours with agitation.
After the completion of the reaction~ the reaction mixture is allowed to cool and is filtered to remove the precipitated potassium acrylate or methacrylate. The filtrate is then dissolved in n-hexane and is washed several times with 0.5N aqueous solution of sodium hydroxide by employing a separatory funnel until the aqueous solution becomes colorless.
When the filtrate is hard to dlssolve in n-hexane, the filtrate may be washed as it is or after dissol~ing in an ether.
After -further washing the filtrate with a saline water until it shows neutral 9 the filtrate is dehydrated for a day and night by employing a drying agent such as anhydrous sodium sulfate. The drying agent is then removed by filtration, and n-hexane is distilled away, for instance, by means of an evaporator to give the desired product.
Examples of ~he cross-linking agent shown by the ~ ~ 3~ ~8 general formula rV] are tetramethyldisiloxanylbis(methyl-glycerol acrylate), tetramethyldisiloxanylbis(methylglycerol methacrylate) [herei.nafter acrylate and methacrylate being referred to as (meth)acrylatc], hexamethyltrisiloxanylbis-(methylgl~cerol (metll)acrylate), tetramethyldisiloxanylbis(ethylglyc~arol (meth)acrylate), hexamethyltrislloxanylbis-(ethylglyc.erol (meth)acrylate), tetramethyldisiloxanylbis-(propylglycerol (meth)acrylate), hexamethyltrisiloxanylbis-(propyl~lycerol (meth)acrylate), tetramethyldisiloxanylmethyl-ethyldiglycerol di(meth)acrylate, hexamethyltrisiloxanyl-methylethyldiglycerol di(meth)acrylate, tetramethyldisiloxa-nylmethylpropyldiglycerol di(meth)acrylate, hexamethyltri-siloxanylmethylpropyldiglycerol di(meth)acrylate, tetra-methyldisiloxanylethylpropyldiglycerol di(meth)acrylate, and hexamethyltrisiloxanylethylpropyldiglycerol di(meth)acrylate.
Examples of the cross-linking agent shown by the general formula rVI] are tetramethyldisiloxanylbis(methyl (meth)acrylate), hexamethyltrisiloxanylbis(methyl (meth)--~ acrylate), tetramethyldisiloxanylbis(ethyl (meth)acrylate), - 20 hexamethyltrisiloxanylbis(ethyl (meth)acrylate), tetramethyldisiloxanylbis(propyl (meth)acrylate), hexamethyltrisiloxanylbis(propyl (meth)acrylate), tetramethyldisiloxanylmethylethyl di(meth)acrylate9 hexamethyltrisiloxanylmethylethyl di(meth)acrylate, 25 tetramethyldisiloxanylmethylpropyl di.(meth)acrylate, hexamethyltrisiloxanylmethylpropyl di(meth)acrylate, tetramethyldisiloxanylethylpropyl di(meth)acrylate, and hexamethyltrisiloxanylethylpropyl di(meth)acrylate.
The cross-linking agents may be employed singly : 30 or in admixture thereof. The amount of the cross-linking 3~
agent is selected from 0.5 to 25 parts by weight, preferably 1 to 20 parts by IYeight, to 100 parts by weight of the total amount of the employed monomer or monomers.
I~hell the amount of the cross-linking agent is less than 5 ` th~ above range, thc cross-linking does not sufficiently proceed, a~ld whell the amount is larger than the above range, the obtclirled polymer is hard and fragile and is poor in mechanical processing property.
~he polymerization is carried out by employing free radical polymerization initiators which are convention-ally employed in the polymerization of unsaturated hydrocarbons~ such as benzoyl peroxide, azobisisobutyronitrile and azobisdimethylvaleronitrile. The polymerization initiator is usually employed in an amount of 0,03 to 0.30 part by weight t~ 100 parts by weight of the monomer or the monomer mixture.
In the present invention, any polymerization systems are applicable, and the bulk polymerization is particularly preferred by the reason that the obtained polymer can be directly employed as a material of contact lens as it is.
The polymerization is carried out in a conventional manner. For instance, in case of the polymerization using ultraviolet ray, the monomer or monomers are first poly-merized under the ultraviolet irradiation at a temperatureof 15 to 50C. for about 30 to about 40 hours, and then thermally polymerized without the ultraviolet irradiation at a temperature of 50 to 140C. for about 30 to about 40 hours. In that case, the polymerization may be carried out by stepwise raising the temperature. For instance, the polymerization is carried out first at 15C. for about 16 hours, and at 40C. for about 8 hours and finally at 50C.
Eor about 8 hours under the ultraviolet irradiation, and then carried out ~ithout the ultraviolet lrradiation at 60C, for about 24 hours, at 80C. ~or about 4 hours, at 100C. for about 4 hours nnd at 120C. or about 4 hours.
Also, ~hen carrying out the polymerization by only thermal polymerization technique, the polymerization is usually carried out at a temperature of 4~ to 140C. for about 60 to about 110 hours, and may be, of course, carried out ste~wise. For instance, the polymerization is carried out first at ~10C. for about 64 hours, at 60C. for about 24 hours, at 80C. for about ~ hours and finally at 120C.
for about 4 hours. The polymerization has been explained above with reference to some instances, but it is to be understood that the polymerization conditions are not limited to such temperature and time conditions and the use of ultraviolet ray.
The cast polymerization is suitable or preparing contact lenses. The polymerization may be conducted in a mold having a shape of contact lens by the bulk polymerization technique Contact lenses having the desired shape are directly obtained in this manner. The ~hus obtained contac~ lenses may be fur~her subjected to a usual mechanical processing to give precise contact lenses. Also, the polymerization may be conducted in an appropriate mold or vessel to give a contact lens material in the form of block, sheet or rod9 and the contact lens material may be then mechanically treated in a conventional manner to give contact lenses of a desired shape.

- ~2 The thus prepared polymers have approximately the same composition as that of the monomers employed.
The polymers of the present invention have an improved oxygen permeability as compared with a conventional polymet}lyl metl~acrylate lens material t~hich is a typical lens material for water-nonabsorptivc contact lens. For instance, the copolymer preparecl according to the present inven1:ion ~y polymerizing 55 g. of methyldi(trimethylsiloxy)-sylylpropylglycerol monomethacrylate, 40 g. of methyl methacrylate and 5 g. of ethylene glycol dimethacrylate has the oxygen permeability of about 12.5 X 10 10 ml.cm./
cm.sec.cmllg. On the other hand, the oxygen permeability of a polymethyl methacrylate lens material is about 0.05 X 10-1 ml.cm./cm.sec.cmHg. Therefore, the copolymer of the invention containing about 55 ~ by weight of methyldi(trimethylslloxy)-sylylpropylglycerol monomethacrylate has the oxygen permeability of about 250 times that of a conventional polymethyl methacrylate contact lens material. Also, a conventional poly-2-hydroxyethyl methacrylate lens material which is a lens material for water-absorptive contact lens has the oxygen permeability of about 5.6 X 10 l0 ml.cm./
cm.sec.cmHg in a state of containing water in saturation and, thereore, the copolymer of the present invention has the oxygen permeability of about 2.2 times that of the poly-2-hydroxyethyl methacrylate lens material. This means ; that the copolymers of the present invention have the oxygen permeability necessary for enabling the contact lenses made thereof to be worn continuously for a long period of time, because it is reported that a poly-2-hydroxyethyl methacrylate contact lens having a thickness of 0.2 mm.

can permeate oxygen of about 1/2 time the required oxygen.
In fact, according to the present inventor's clinical study in ~hich contact lenses having a thickness of 0.15 mlll. 9 a size o~ 11.5 111111. ancl a radius of curvature of inner s~lrfacc o 7.90 mm. were prepared from the copolymer of the invelltion and wcre continuously worn on albino rabbit eyes for 21 days, no change ~as observed on corneal surfaces and there was no decrease of glycogen, and also in respect of the histological observation, there was no vascularization, substantial edema and infiltration of inflammatory cells and like this, no morphologically significant change was observed. The reason that ~he continuous wear ~as conducted for 21 days is that it is known that the cycle of metabolism of cornea is about 18 days.
The oxygen permeability of the novel polymers of the present invention i5 in proportion to the content of the before-mentioned particular organosiloxane, and falls within the range of about 2.5 ~ 10 10 to about 45 X 10 10 ml.cm./cm.2sec.cmHg. The reractive index of the polymers of the present invention varies depending on the kind and amowlt of the employed monomer or monomers and is not critical, but usually falls within the range of nD5 = 1.40 to 1.50. Also, the polymers of the present invention have a specific gravity of from 1.01 ~o 1.21, a ; visible ray percent transmission of not less than 90 ~ and a Vickers hardness number of 1.5 to 19Ø
The thus prepared polymers and cross-linked polymers of the present invention have an excellent oxygen permeability and a good hydrophilic property. Iherefore, ~ ~f~ 8 the contact lenses prepared therefrom can be worn continuously for a long period of time withou~ giving a foreign body sensation, ~lso, the polymers and cross-linked polymers oE the invention are substantially water-nonabsorptive and, there~ore, the contclc~ lenses have an excellent optical ~ operty alld there is no problem of contamination by bacteria, In the instant specification the values of the oxygen permeability, refractive index and visible ray percent transmission are those measured as follows:
The oxygen permeability is measured by an oxygen gas permeameter made by Rikaseiki Kogyo Co., Ltd. by employing specimens having a ~iameter of 15 mm. and a thickness of 0.2 mm.
The refractive index is measured by Abbé's refractometer made by Erma Optical Works Co., Ltd.
` The visible ray percent transmission is measured by Double-Beam Spectro Photometer U~-210 made by Shimadzu Seisakusho Ltd. by employing film specimens having a thickness of 0.15 mm.
The present invention is more particularly described and explained by means of the following Examples, - In order to illustrate the preparation of the organosiloxane monomer and ~he cross-linking agent having siloxane bond, the following Reference Examples are also presente~.

Reference Examples 1 to 3 [Synthesis of Polysiloxanyl(alkylglycerol) Monomethacrylate]
Methyldi(trimethylsiloxy)sylyl~propylglycerol) monomethacrylate having the following formula [IX]:

;' C1-13-Si-C~13 1~13 C~l2=c-c-o-cll2-f~l-cllz-o-c~l2-cl-l2-c~l2-li C 3 [IX]

C113-1i-C~13 C~13 was prepared as follows:
A one liter four neck round bottom flask equipped Wit]l a stirrer, a ~hermometer, a tube for introducing nitrogen gas, a dropping funnel and a reflux condenser was charged with 336 g. of methyldi(trimethylsiloxy)-sylylpropyloxypropylene oxide, 6.5 g. of potassium hydroxide and 0.8 g. of hydroquinone, and was placed on an oil bath.
IYith introducing nitrogen gas into the flask, 172 g. of methacrylic acid was added dropwise to the flask through the dropping funnel with stirring. After the completion of the addition, the mixture was gradually heated to 93C.
and at this temperature the reaction was carried out for about 22 hours. After the completion of the reactlon~
the reaction mixture was allowed to cool and filtered to remove the precipitated potassium methacrylate.
The filtrate was then dissolved in n-hexane in an amount of about lO times the volume of the filtrate and the resulting solution was washed several times with a O.SN
aqueous solution of sodium hydroxide by employing a separatory funnel, until the aqueous solution became colorless. The filtrate dissolved 1n n-hexane was further washed with a saline water until it became neu~ral, and was then dehydrated by employing anhydrous sodium sulfate for a day and night. ~fter removing anhydrous sodium sulfate by filtration, n-hexane was cListil:l.ed away by an evaporator.
l`lle th~ls puri:Eied reaction product was a slightly visco~s, transl~arent :Liquid. I~ccording to the qualltitative allalysis by gas chromatography, the purity of the obtained product was over 98 5~.
The refractive index n25 of the product was 1.440.
The infrared absorption spectrum of the product indicated absorptions of -O~l group at 3,420 cm.l~ of double bond at 1,640 cm.l, of ester bond at 1,720 cm.l! of Si-O-Si bond at 1,080 cm.l and 1,040 cm.l, of -CH3 group at 2,950 cm.l, 1,400 cm.~l and 1,300 cm.l, and of -Si-(CH3)3 group at 845 cm.l No absorption of epoxy group was observed at 910 cm.l The result of the elemental analysis was as follows:
Calculated for C17ll38O6Si3: C 48.3 %; H 9.0 ~O
Found: C 49.7 ~o; H 9.3 ~o From the above results, it was confirmed that the product was methyldi(trimethylsiloxy)sylyl(popylglycerol) monomethacrylate (hereinafter referred to as S2) (Reference Example 2).
The procedures of Reference Example 2 were repeated except that instead of methyldi(trimethylsiloxy)sylyl-propyloxypropylene oxide, pentamethyldisiloxanylpropyloxy-propylene oxide and tris(trimethylsiloxy)sylylpropyloxy-propylene oxide were employed respectively to give pen.tamethyldisiloxanyl(propylglycerol) monomethacrylate (hereinafter referred to as Sl) (Reference Example 1) having the following formula [X]:
cl l-13 I f C1-12=C-C-O-CI-12-fEI-cEl2-O-cl-l2-cEl2 C~12 1 i 1 3 rX]
O Ol-l Cl 1 3 (,1 1 3 and tris~trimethylsiloxy)sylyltr)ropylglycerol) mono-mcthacrylate (herelnatcr rcferrecl to as S3) (Reference E'xample 3) having the :Eollowi.ng formula [XI]:

CH3-Si-CE13 CIEI 3 - IClI 3 Cl-l 2 = C - C - O - CE-I 2 - CH - CE 12 - - CE 12 - CH 2 CE I 2 1 1 3 [ X I ]

CH3-Si- CE13 15The analytical results of Sl and S3 compounds are shown in Table 1 together with the results of S2 compound.

Reference Examples 4 to 6 [Synthesis of Polysiloxanyl(alkylglycerol)alkyleneglycol Monomethacrylate]
Methyldi(trimethylsiloxy)sylyl(propylglycerol)-ethyleneglycol monomethacrylate having the following formula [XII]:

25CH3-Si- CE-13 CH2=C-C-O-CE12 -CH2-o-cH2-cH-cH2-o-cH2-cH2-cH2-si- CH3 [XII ]
O OH O

CH3-li- CH3 :

~ 3 was prepared as follows:
A one liter four neck round bottom flask equipped ~ith a stirrer, a thermometer, a tube for introducing nitrogen gas, a dropping ~unnel and a re~lux condenser was chclrlJcd ~ith 260 g. o ethylene glycol monometllacrylate, 7 g. oE trlethylamille and 4 g. of hyclrocluinonc. With introducing nitrogen gas into the Elask, 336 X- of methyldi(trimethylsiloxy)sylylpropyloxypropylene oxide was added dropwise to the flask through the dropping funnel with stirring. The mixture was then gradually heated to 85C. and at this temperature the reaction was carried out for about 6 hours. After the completion of the reaction, the reaction mixture was allowed to cool and then dissolved in a large quantity of n hexane. The resulting solution was washed several times with a 0.5N aqueous solution of sodium hydroxide by employing a separatory funnel until the aqueous solution became colorless, and was further washed with a saline water until it became neutral. After dehydrating by employing anhydrous sodium sulfate for a day and night and removing anhydrous sodium sulfate by filtration, n-hexane was removed by an evaporator.
The thus purified reaction produc~ was a slightly viscous, transparent liquid. According to the quantitative analysis by gas chromatography, the purity of the obtained product was over 93 %
The refractive index nDS of the product was 1.439.
The infrared absorption spectrum of the product indicated absorptions of -O~l group at 3,420 cm.l, of double bond at 1,640 cm.l, of ester bond at 1,720 cm.l, of Si~O-Si bond at 1,080 cmOl, and 1,040 cm.l, of -C~13 group ~ 3~ ~ ~

at 2,950 cm.l, 1,400 cm.l and 1,300 cm.l, and of -Si-(CH3)3 group at 845 cm.l The result of the elemental analysis ~as as follows:
('alcula~d for C19~ 27S13 ( 48-~ %; ll 9-0 l~ound: C 47.2 ~; ll 8.7 %
Fronl the~ above results, it was confirmed that the product was met}lyldi(trimethylsiloxy)sylyl(propylglycerol.)-ethyleneglycol monomethacrylate (hereinafter referred to as S5) (Reference Example 5).
The procedures of Reference Example 5 were repeated except that instead of methyldi(trimethylsiloxy)sylyl-propyloxypropylene oxide, pentamethyldisiloxanylpropyloxy-propylene oxide and tris(trimethylsiloxy)sylylpropyloxy-propylene oxide were employed respectively to give 15 pentamethyldisiloxanyl(propylglycerol)ethyleneglycol monomethacrylate (hereinafter referred to as S4) (Reference Example 4) having the following formula rXIII]:
C1~l3 IC~l3 IH3 CH2=c-lcl-o-(cH2)2-o-cH2-lcH-cH2-o-(cH2)3-fi-o-sli-cH3 [XIII]

and tris(trimethylsiloxy)sylyl(propylglycerol)ethyleneglycol monomethacrylate (hereinafter referred to as S6) (Reference Example 6) having the following form.ula [XIV]:
fH3 CH3-Sl-CH3 CH3 C1~3 2¦¦ ( 2)2 C~l2 1CH-CH2-O-(CH2)3 si o-si-cH3 [XIV]
O OH f CH3 CH3-Si-CH3 3~38 The analytical results of S4 and S6 compounds are shown in Table 1 together with the results of S5 compound.

Reference Example 7 rsyntllesis o Polysiloxanyl(cl:lkylglycerol)polyalkylene-glycol MoncJmethacrylate]
Methylcli(trimethylsiloxy)sylyl(propylglycerol)-diethyleneglycol monomethacrylate (hereinater referred to as S7) having the following formula rxv]
cl~l3 CH3-Si-CH3 CH3 o C~l2=c-6-o-(cH2-cH2-o)2-c~l2-clH C~12 ( 2 3 1 3 rxv]
O OH f Cl-13-7i-C~13 was prepared in the same manner as in Reference Example 5 except that diethylene glycol monomethacrylate was employed instead of ethylene glycol monomethacrylate~
The analytical results of S7 compound are shown in Table 1.

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Refercnce E.Yample 8 rSynthesis of Cross-Linking Agent }laving Siloxane Bond;
Polysilo~anylbis(alkyl~lycerol ~lethacrylate)]
[`etramethyld;siloxanylbis(propylglycerol S methacrylate) having the following formulll rxvI]
l~-13 lll3 Cll-l3 C~2 C 11 0 C~12 1}1 C~2 (C~12)3 li O li -(C~32)3-O-C~l2-CI~l-CH2-O-C-C=Cl32 [XVI]
OH O
was prepared as follows:
A one liter four neck flask equipped with a stirrer, a thermometer, a tube for introducing nitrogen gas, a dropping funnel and a reflux condenser was charged with 362 g. of tetramethyldisiloxanylbis(propyloxypropylene oxide), 112 g. of potassium hydroxide and 2 g. of hydroquinone. With introducing nitrogen gas into the flask, 258 g. of methacrylic acid was added dropwise to the flask through the dropping funnel with stirring.
After the cornpletion of the addition, the mixture was gradually heated to 95C. and at this temperature the reaction was carried out for about 20 hours. After the completion of the reaction, the reaction mixture i~as allowed to cool and was filtered to remove the precipita~ed potassium methacrylate. The filtrate was then dissolved in a large quantity of ether, and was washed several times with an aqueous solution of sodium hydroxide by employing a separatory funnel until the aqueous solution became colorless. After further washing with a saline water and ~ . .

then dehydrating by employing anhydrous sodium sulfate for a day and night, anhydrous sodium sulfate was removed by filtration and ether was disti.lled away to give the desired product.
'I'he thus obtained ~rocluct ~as a sli~htly viscous, colorless, transparent :liquid. 'I`he specific gravity d4 was 1.054 and the refractive index n25 was 1.466.
The infrared absorption spectrum of the product indicated absorptions of -O~l group at 3,420 cm.l, of double bolld at 1,640 cm.l, of ester bond at 1,720 cm.l, of Si-O-Si bond at l,OS0 cmOl, and of -Si-(CH3)2 at 1,260 cm.l The result of the elemental analysis was as follows:
Calculated for C24~'l469Si2 C S3.9 %; ~l 8-6 %
Found: C 55.6 %; H 8.9 %
From the above results, it was confirmed that the product was tetramethyldisiloxanylbis(propylglycerol methacrylate).

Example 1 A polypropylene tes~ tube was charged with a mixture of 100 g. of ~he Sl monomer, pentamethyldisiloxanyl-(propylglycerol) monomethacrylate and O.lS g. of azobisiso-butyrontirile dissolved in the Sl monomer. After stoppering 25 the test tube, the thermal polymerization was carried out stepwise at 35C. for ~8 hours, at 50C. for 8 hours, at 70C. for 6 hours, at 90C. for S hours, at 110C. for S
; hours and at 130C. for S hours to give a slightly hard, - colorless, transparent polymer in the form of rod.
Cutting, grinding and polishing of the thus ~31~3~

obtained contact lcns material in the form of rod were possible and the mechanical processing property was good.
'I'ile refractive index, specific gravity, oxygen permeabili~y and visible ray percent transmission were also metlsured~
'I`he results are shown in 'rable 2, Examples 2 to 7 The procedures of Example 1 were repeated except that the S~, 53, S4, S5~ S6 and S7 monomers were employed respectively instead of the Sl monomer.
The results are also shown in Table 2.

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Example 8 To 90 g. of the Sl monomer was added 10 g. of tetramethyldisiloxanylbis(propylglycerol methacrylate) as a cross-linking agent, an~ then 0.2 g, o azohisdimethyl-valeronitrile was clissolved in the resulting mixture. Afterplacing the mixutre in a polypropylene test tube and stoppering the test tube, the thermal polymerization was carried out stepwise at 35C. for 48 hours, at 50C. for 8 hours, at 70C. for 6 hours, at 90C. for 5 hours, at 11~C.
for 5 hours and at 130C. for 5 hours to give a slightly hard, colorless, transparent polymer in the form of rod.
Cutting, grinding and polishing of the thus obtained contact lens material in the form of rod were possible and the mechanical processing property was good.
The refractive index, specific gravity, oxygen permeability and visible ray perc~nt transmission were also measured .
The results are shown in Table 3.
. ~ .
Examples 9 to 14 The procedures of Example 8 were ~repeated except that the S2, S3, S4, S5~ S6 and S7 monomers were employed respectively instead of the Sl monomer ~o give cross-linked polymers.
The results are also shown in Table 3.

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Example lS
Ninety-three grams of the Sl monomer, 7 g. of trimethylolpropane trimethacrylate (hereinafter referred to as T~IT~) as a cross-linking agent and 0.2 g. o:~ azobisdi-metllylvaleronitrilc were thoroughly admixed and then placed:in a polypropylelle test t:ube. /~fter stopperillg the test tube, ullder the ultraviolet irradi.atioll the polymerization was carried out stepwise at 35(:. for 16 hours and at 50C. for 8 hours, and the thermal polymerization was carried out without the ultraviolet irradiation stepwise at 70C. for 6 hours, at ~0C. for S hours, at 110C. for 5 hours and 130C. for 5 hours to give a slightly hard, colorless, transparent rod.
The properties of the obtained cross-linked polymer are shown in Table 4.

Examples 16 to 21 The procedures of Example 15 were repeated except tha~ the S2, S3, S4, S5, S6 and S7 monomers were employed respectively instead of the Sl monomer.
The results are also shown in Table 4.

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Example 22 Forty grams of the Sl monomer, pentamethyldi-siloxanyl(propylglycerol) monome-thacrylate, 55 g. of metllyl metllacryl<lte (ller~inatcr re~crr~d to as ~ ), 5 g.
of cthylellc glycol dlmcthacrylate (hereinafter referred to ns ED~) ancl 0.2 g. of a~obisisobutyronitrile were thorougllly adlllixed and then placed in a polypropylene test tube. After stoppering the test tube, under the ultraviolet irradiation the polymerization ~as carried out stepwise at 35C. for 16 hours and at 50C. for 8 hours, and then the ultraviolet irradiation was stopped and the -thermal polymerization was further carried out stepwise at 70C. for 6 hours, at 90C. for 5 hours, at 110C. for S hours and at 130C. for 5 hours to give a hard, colorless, transparent rod.
Cutting, grinding and polishing of the thus obtained contact lens material were possible and the mechanical processing property was good.
The refractive index, specific gravity, oxygen permeability, visible ray percent transmission and Vickers hardness number were also measured.
The results are shown in Table 5.

Examples 23 to 28 The procedures of Example 22 were repeated except that the S2 9 S3, S4, S5, S6 and S7 monomers were employed respectively instead of the Sl monomer.
The results are also shown in Table 5.

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Example 29 Forty-five grams of the S2 monomer, methyldi-(trimethylsiloxy)sylyl(propylglycerol) monomethacrylate, 49 g. of ~l~, 6 g. o~ lMT~ ancI 0.05 g. of azobisdimethyl-S valeronitrilc were thorug}Ily admixed and then placed in apolypropylcne test ~ube. After stoppering the tes~ tube, the thermal polymerization was carried out stepwise at 32C.
for 48 hours, at 50C. for 8 hours, at 70C. for 6 hours, at 90C. for S hours, at 110C. for 5 hours and 130C. for 5 hours to give a hard, colorless, transparent rod.
The properties of the obtained copolymer are shown in Iable 6.

.
Examples 30 to 34 The procedures o ~xample 29 were repeated except that the S2 monomer, MMA and TMTMA were employed in amounts shown in Table 6.
The properties of the obtained copolymers are shown in Table 6.

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~'3~8 Example 35 Forty grams of the S2 monomer, methyldi-(trimethylsiloxy)sylyl(propylglycerol) monome~hacrylate, 60 g. o~ and 0.15 g. of azobisisobutyronitrile were thoroughly admixed alld then placed in a polypropylene test: tube. ~fter stoppering the test tube, the thermal polymeri.zation was curried out stepwise at 32C. for 48 hours, at 50C. for 8 hours, at 70C. for 6 hours, at 90C. for 5 hours, at 110C. for 5 hours and at 130C. for 5 hours to give a hard, colorless, transparent rod.
The properties of the obtained copolymer are shown in Table 7.

Examples 36 to 40 The procedures of Example 35 were repeated except that the monomers shown in Table 7 were employed.
The properties of the obtained copolymers are shown in Table 7.

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Example 41 Fifty-five grams of the S2 monomer, methyldi(tri-methylsiloxy)sylyl(propylglycerol) monomethacrylate, 40 g.
of MMA, S g. of allyl methacrylate (hereinafter reerred to as A~IA) and 0.15 g. of azobisisobutyronitrile were thoroughly admixed and then placed in a polypropylene test tube, After stopperin~ the test tube, under the ultraviolet irradiation the polymerization was carried out stepwise at 32C. for 16 hours and at 50C. for 8 hours, and then the ultraviolet irradiation was stopped and the thermal polymerization was further carried out stepwise at 70C.
for 6 hours, at 90C. for 5 hours, at 110C. for 5 hours and at 130C. for 5 hours to give a hard, colorless, transparent rod.
The properties of the thus obtained copolymer are shown in Table 8.

Examples 42 to 46 The procedures of Example 41 were repeated except that the monomers as shown in Table 8 were employed.
The properties of the obtained copolymers are shown in Table 8.

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~ 3~ 3 Example 47 Fifty-five grams of the S2 monomer, 35 g. of h~lA, 5 g. o ethylene glycol monomethacrylate (hereinafter referred to as EG~IA), 5 g. o EDMA and 0.09 g. of azobis-dimethylvaleronitrile were thoroughly admixed and thenplace~d in a polypropylene test tube. ~fter stoppering the test tube, the thermal polymer:ization was carried out stepwise at 32C. for 48 hours, at 50C. for 8 hours at 70C. for 6 hours, at 90C. for 5 hours, at 110C. for S hours and at 130C. for 5 hours to give a colorless, transparent rod.
The properties of the thus obtained polymer are shown in Table 9.

Examples 48 to 52 The procedures of Example 47 were repeated except that the kind and amount of the hydrophobic monomer, hydro-philic monomer and cross-linking agent were changed as shown in Table 9.
The results are also shown in Table 9.

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l 00 O~ O r~ S`l ~ ~ e~ d- Ln Ir)L~7 3~3 Example 53 Ninety-five grams of the S2 monomer, S g. of EGMA
and 0.09 g. fo azobisdimethylvaleronitrile were thoroughiy admixed and then placecI in a polypropylene test tube.
~fter stopperiIlg the tes-t tube, un(ler the ultraviolet irracllation thc polymerizatioIl was carried out stepwise at 32C for lG houls, at 50C. or 8 hours, and then the ultraviolet irradiation was stopped and the thermal poly-merization was further carried out stepwise at 70C. for 6 hours, at 90C. for 5 hours, at 110C. for 5 hours and at 130C. for 5 hours to give a colorless, transparent rod.
The properties of the thus obtained copolymer are shown in Table 10.

Examples 54 to 58 The procedures of Example 53 weTe repeated except that the monomers as shown in Table 10 were employed.
The results are also shown in Table 10.

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Example_59 Fifty grams of the Sl monomer, pentamethyldi-silo~anyl(propylglycerol) monomethacrylate, 50 g. of the S2 monomer, methyldi(trimethylsiloxy)sylyl(propylglycerol) morlomethacrylclte, and 0.10 g. of azobisclimethylvaleronitrile ~ere thorollgllly admixecl and then placed :in a polypropylene test tube. ~ter stoppering the test tube, the thermal polymerization was carried out stepwise at 35C. Eor 48 hours, at 50C. for 8 hours, at 70C. for 6 hours, at 90C. for 5 hours, at 110C. for 5 hours and at 130C. for 5 hours to give a hard, colorless, transparent rod.
The properties of the thus obtained copolymer are shown in Table 11.

Example 60 to 65 The procedures of Example 59 were repeated except that the monomers as shown in Table 11 were employed.
In Examples 62 to 65, 0.15 g. azobisisobutyronitrile was employed instead of 0.10 g. of azobisdimethylvaleronitrile.
The properties of the obtained copolymers are shown in Table 11.

bl O O O O O O O
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Example 66 Porty grams of the Sl monomer, pentamethyldi-siloxanyl(propylglycerol) monomethacrylate, 10 g. of the ; cross-linking agent obtained in Re:Eerence Example 8, 50 g.
of h~ an(l 0.2 g. of azobisclimethylvalerollitrile were thoroughly admixe~cl and then placed in a polypropylene test tube. ~fter stoppering the test tube, the termal polymeri-zation was carried Ollt stepwise at 35C. for 40 hours, at 50C. for 8 hours, at 70C. for 6 hours, at 90C. for 5 hours, at 110C. for 5 hours and at 130C. for 5 hours to give a hard, colorless, transparent rod.
The properties of the obtained copolymer are shown in Table 12.

Examples 67 to 72 The procedures of Example 66 were repeated except that the S2, S3, S4, S5, S6 and S7 monomers were employed respectively instead of the Sl monomer.
The results are shown in Table 12.
.

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:

E.xam~le 73 Forty-five grams of the S5 monomer, methyldi-(trimet}lylsiloxy)sylyl(propylglycerol)ethyleneglycol monoIIletllacrylate~ 49 g. of M~, fi g. of I~IThIA and 0.2 g.
o:E azobisdimetilylvalcronitrile were thoroughly admixed and then placed in a polypropyleIle test tube. After stopperin~ the test tube, the thermal polymeri2ation was carried out stepwise at 35C. for 40 hours, a~ 50C. for 8 hours, at 70C. ~or 6 hours, at 90C. for S hours, 110C. or 5 hours and at 130C. for S hours to give a hard, colorless, transparent rod.
The properties of the obtained copolymer are shown in Table 13.

Examples 74 to 78 The procedures of Example 73 were repeated except tllat the S5 monomer, MMA and TMTMA were employed in amounts shown ln Table 13.
The properties of the obtained copolymers are shown in Table 13.

bO

O V\
h ~rl O O O O O O
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Exam~les 79 to 85 The procedures of Examples 22 to 28 repeated except that the amounts of the monomers t~ere changed as shown in Table 14.
The results are shown in 'I`able l~l.

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Examples 86 to 92 The procedures of Examples 22 to 28 were repeated except that the amounts of the monomers ~ere changed as sho~n in l`able 15.
'I`lle results are shown in Table 15.

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~l~earing Tes~ of Contact l,enses~
'I'lle contact lens materials obtained in the foregoing Examples werc classified into four groups with resl)ect to the oxygen ~er!lleal)llity~ and werc subjectecl to a usual mecllarlical plocessin~ to give contact lenses Eor rabbit eye having a base-curve of 7.90 mm., a front-curve of 8.10 min., a lens size of 11.5 mm. and a center thickness being in inverse proportion to the oxygen permeability as shown in the following Table 16.
Table 16 Oxygen permeability Base- Front- Lens Center (ml.cm./cm2sec.cmHg) (cnu~m,vej curve s(mme.) (mm.) more th~n 15 X 10 10 7,90 8.10 11.5 0.Z to 0.3 (10 to 15) X 10~1 7,90 8.10 11.5 0.15 to 0.2 (5 to 10) X 10 10 7,90 8.10 11.5 0.08 to 0.15 (2.5 to 5) X 10-1 7.90 8.10 11.5 0.05 to 0.08 .
The thus prepared contact lenses were worn on rabbit eyes continuously for 21 days, and observation of eye was conducted.
Contact lenses having a center thickness of not more than 0.25 mm., which were prepared from the lens materials having an oxygen permeability of more than 15 X 10 10 ml.cm./cm,2sec.cmHg, could be continuously worn without change in eyes.
Contact lenses having a center thickness of not more than 0.18 mm., which were prepared from the lens materials having an oxygen permeability of (10 to 15) X 10 10 ml.cm./cm2sec.cmHgj could be continuously worn without change in eyes.

~ ~ 3~ ~ ~

Contact lenses havillg a center thickness of not more than 0.10 mm., whic}l were prepared from the lens m.lterlals having an oxygen perlneabili.ty of (5 to 10) X 10 10 ml.clll./clll~sec,clllllg, cou:ld be continl.lous].y worn Wit]lOUt change S ln c~yes.
('ontact lenses having a center thickness of not more than 0.06 mm~, which were prepared from the lens ma-teria].s having an oxygen permeability of (2.5 to 5) X 10-1 ml.cm./cm.2sec,cm~lg, could be continuously worn without change :in eyes.
From the above results, it would be further understoocl that the contact lens materials having an improved oxygen permeability are particularly suited for lens requiring a large lens thickness SUC}I as high-plus lens.

~-.

Claims (26)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A polymer suited for a contact lens material selected from a homopolymer of an organosiloxane monomer having the following general formula [I]:

[I]

wherein n is an integer of 1 to 3, X is in which p is an integer of 2 to 4 and q is O or an integer of 1 to 3, and yl, y2 and Y3 are methyl group or -O-Si-(CH3)3, and a copolymer of said organosiloxane monomer and at least one monomer selected from the group consisting of a hydropholic monomer;
hydrophobic monomer and a polyfunctional monomer as cross-linking agent.

2. A polymer as claimed in claim 1, wherein said organosiloxane monomer is a compound having the following general formula [II]:

[II]

wherein n is an integer of 1 to 3, and yl, y2 and Y3 are methyl group or -O-Si-(CH3)3.

3. A polymer as claimed in claim 1, wherein said organosiloxane monomer is a compound having-the following general formula [III]:

[III]

wherein n is an integer of 1 to 3, p is an integer of 2 to 4, and Yl, Y2 and Y3 are methyl group or -O-Si-(CH3)3.

4. A polymer as claimed in Claim 1 wherein said organosiloxane monomer is a compound having the following general formula [IV]:

[IV]

wherein n is an integer of 1 to 3, p is an integer of 2 to 4, q' is 2 or 3, and Yl, Y2 and Y3 are methyl group or -O-Si-(CH3)3.

5. A polymer as claimed in Claim 1, wherein the polymer is a homopolymer of said organosiloxane monomer.

6. A polymer as claimed in Claim 1, wherein the polymer is a copolymer of said organosiloxane monomer and at least one member selected from the group consisting of a hydrophilic monomer and a hydrophobic monomer.

7. A polymer as claimed in Claim 6, weherin said hydrophilic monomer is employed in an amount of 1 % to 20 %
by weight based on the total weight of the employed monomers.

8. A polymer as claimed in Claim 6, wherein said hydrophobic monomer is employed in an amount of 5 % to 70 %
by weight based on the total weight of the employed monomers.

9. A polymer as claimed in Claim 6, wherein said hydrophilic monomer is at least one member selected from the group consisting of ethylene glycol monomethacrylate, diethlene glycol monomethacrylate, triethylene glycol monomethacrylate, ethylene glycol monoacrylate, diethylene glycol monoacrylate, triethylene glycol monoacrylate, N-vinyl pyrrolidone and dimethylacrylamide.

10. A polymer as claimed in Claim 6, wherein said hydrophobic monomer is a methacrylic acid alkyl ester, of which homopolymer has a glass transition temperature higher than room temperature.

11. A polymer as claimed in Claim 10, wherein said methacrylic acid alkyl ester is at least one member selected from the group consisting of methyl methacrylate, ethyl methacrylate and cyclohexyl methacrylate.

12. A polymer as claimed in Claim 1, wherein the polymer is a cross-linked polymer prepared by polymerizing at least one said organosiloxane monomer in the presence of said cross-linking agent.

13. A polymer as claimed in Claim 12, wherein the cross-linked polymer is one prepared by polymerizing said organosiloxane monomer and at least one member selected from the group consisting of said hydrophilic monomer and said hydrophobic monomer in the presence of said cross-linking agent.

14. A polymer as claimed in Claim 12 or 13, wherein said cross-linking agent is employed in an amount of 0.5 to 25 parts by weight per 100 parts by weight of the whole monomers employed.

15. A polymer as claimed in Claim 12 or 13, wherein said cross-linking agent is at least one polyfunctional monomer selected from the group consisting of ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacry-late, allyl methacrylate, trimethylolpropane trimethacrylate, divinyl benzene, diallyl phthalate, compounds having the following general formula [V]:

[V]

wherein n and n' are an integer of 1 to 3, m is 1 or 2, and Rl and R2 are hydrogen or methyl group, and compounds having the following general formula [VI]:

[VI]

wherein n and n' are an integer of 1 to 3, m is 1 or 2, and R1 and R2 are hydrogen or methyl group.

16. A polymer as claimed in any of Claims l, 2 or 3, having an oxygen permeability of 2.5 X 10 to 45 X 10 -10 m1.cm./cm.2sec.cmHg, a refractive index of n? = 1.40 to 1.50, a specific gravity of d? = 1.01 to 1.21, a visible ray percent transmission of not less than 90 % and a Vickers hardness number of 1.5 to 19Ø

17. A contact lens made of a polymer selected from a homopolymer, an organosiloxane monomer having the following general formula [I]:

[I]

wherein n is an integer of 1 to 3, X is in which p is an integer of 2 to 4 and q is O or an integer of 1 to 3, and Y1, Y2 and Y3 are methyl group or -O-Si-(CH3)3, and a copolymer of said organo siloxane monomer and at least one monomer selected from the group consisting of a hydropholic monomer; hydrophobic monomer and a polyfunctional monomer as cross-linking agent.

18. A contact lens as claimed in claim 17, wherein said polymer is a homopolymer of said organosiloxane monomer.

19. A contact lens as claimed in Claim 17, wherein said polymer is a copolymer of said organosiloxane monomer and at least one member selected from the group consisting of a hydrophilic monomer and a hydrophobic monomer.

20. A contact lens as claimed in Claim 19, wherein said hydrophilic monomer is at least one member selected from the group consisting of ethylene glycol monomethacrylate, diethylene glycol monomethacrylate, triethylene glycol monomethacrylate, ethylene glycol monoacrylate, diethylene glycol monoacrylate, triethylene glycol monoacrylate, N-vinyl pyrrolidone and dimethylacrylamide, and is employed in an amount of 1 % to 20 % by weight based on the total weight of the employed monomers.

21. A contact lens as claimed in Claim 19, wherein said hydrophobic monomer is at least one member selected from the group consisting of methyl methacrylate, ethyl methacrylate and cyclohexyl methacrylate, and is employed in an amount of 5 % to 70 % by weight based on the total weight of the employed monomers.

22. A contact lens as claimed in Claim 17 wherein said polymer is cross-linked by means of a cross-linking agent, said cross-linking agent being at least one polyfunctional monomer selected from the group consisting of ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacry-late, triethylene glycol diacrylate, triethylene glycol dimethacrylate, allyl methacrylate, trimethylolpropane trimethacrylate, divinyl benzene, diallyl phthalate, compounds having the following general formula [V]:

[V]

wherein n and n' are an integer of 1 to 3, m is 1 or 2, and R1 and R2 are hydrogen or methyl group, and compounds having the following general formula [VI]:

[ VI]

wherein n and n' are an integer of 1 to 3, m is 1 or 2, and R1 and R2 are hydrogen or methyl group.

23. A contact lens as claimed in Claim22, wherein said cross-linking agent is employed in an amount of 0.5 to 25 parts by weight per 100 parts by weight of the whole monomers employed.

24. A contact lens made of a copolymer comprising (a) 30 % to 95 % of units of an organosiloxane monomer having the following general formula [I]:

[I]
wherein n is an integer of 1 to 3, X is in which p is an integer of 2 to 4 and q is O or an integer of 1 to 3, and Y1, Y2 and Y3 are methyl group or -O-Si-(CH3)3, and (b) 70 % to 5 % of hydrophobic methacrylic acid alkyl ester monomer units, of which homopolymer has a glass transition temperature higher than room temperature, said % of (a) and (b) being % by weight based on the total weight of (a) and (b).

25. A contact lens as claimed in Claim 24, wherein said copolymer further contains units of a cross-linking agent in a weight ratio of 0.5 to 25 against 100 of the components (a) and (b), said cross-linking agent being at least one polyfunctional monomer selected from the group consisting of ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, allyl methacrylate, trimethylolpropane trimethacrylate, divinyl benzene, diallyl phthalate, compounds having the following general formula [V]:

[V]

wherein n and n' are an integer of 1 to 3, m is 1 or 2, and R1 and R2 are hydrogen or methyl group, and compounds having the following general formula [VI]:

[VI]

wherein n and n' are an integer of 1 to 3, m is 1 or 2, and R1 and R2 are hydrogen or methyl group.

26. A contact lens as claimed in Claim 17, 18 or 19, having an oxygen permeability of 2.5 X 10 -10 to 45 X 10 -10 m1.cm./cm.2sec.cmHg, a refractive index of n? = 1.40 to 1.50, a specific gravity of d? = 1.01 to 1.21, a visible ray percent transmission of not less than 90 % and a Vickers hardness number of 1.5 to 19Ø