JPS5961816A - Silicon-containing contact lens material and contact lens made thereof - 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 Contact lenses that derive oxygen permeability from organosiloxanes require substantial amounts of organosiloxane to provide sufficient oxygen transport to the cornea.

In general, organosiloxane molecules tend to be incompatible in many compositions containing other monomers.

For example, dissolving organosiloxanes in methyl methacrylate and polymerizing the solution often results in opaque materials that are unsuitable for use in contact lenses.

The prior art has shown that short organoloxane units chemically bonded to unsaturated polymerizable groups can be used to copolymerize such organoroxane monomers with other monomers into compatible and therefore transparent materials. It shows that it provides a means to reach

On the other hand, organosiloxane units containing only one unsaturated polymerizable group often do not give random copolymers when copolymerized with other monomers, especially hydrophilic monomers. This condition leads to phase separation and opaque materials. In certain cases, phase separation is not visually detectable, but the physical properties of the material have been demonstrated. This condition can cause materials to exhibit brittle behavior and resistance to fragmentation.

The physical properties of highly cross-linked polymers prepared from dimeterne loxane diacrylate oligomers are known in the art. Generally, microphase separation is suppressed when the amount of dimethylsiloxane groups in the Bun polymer increases.

This phenomenon is due to the deletion of long organic sequences. Overall, Katz's work [J, Polym, S
ci, Ohem, E(1,16(3) 597(1
978) teaches against the copolymerization of such reactive organosiloxane monomers because the organic order provides a prelude to phase separation.

However, it is known that in contact lens materials it is desirable to include one or more copolymers to achieve the proper balance of physical properties.

Therefore, it is desirable to provide random copolymers containing substantial amounts of organosiloxane units that are compatible with contact lens applications.

The present invention utilizes branched organosiloxane structures containing multiply unsaturated polymerizable groups. These materials, when copolymerized with other monomers, provide clear, highly oxygen permeable and durable compositions. The random nature of the polymerization process is enhanced by the presence of multiple unsaturated polymerizable groups. Compatibility of the disclosed organopolysiloxane monomers is improved by the utilization of highly branched organoborinoxane moieties.

It is an object of this invention to provide new unsaturated polyfunctional organopolysiloxanes useful alone or in combination with other organic materials to form contact lenses.

Another object of the present invention is to provide polymerized unsaturated polyfunctional organopolysiloxanes in the form of contact lenses in which the siloxanes can be used alone or in combination with other organic materials.

A further object of the invention is to provide contact lens materials and contact lenses according to the invention that are oxygen permeable, dimensionally stable, hydrophilic and have good optical clarity and brightness.

Yet another object of the present invention is that a significantly hard or semi-hard oxygen permeable lens is formed with reduced brittleness and good strength when compared to conventional organoxane-containing contact lenses. Our goal is to provide purpose-based contact lenses.

According to the present invention, contact lenses have the formula (wherein R is hydrogen or methyl, R' is a divalent alkylene group having 1 to 5 carbon atoms, A monovalent hydrocarbon group having carbon atoms, a substituted monovalent hydrocarbon group having 1 to 5 carbon atoms, a phenyl group, and a cyclohexyl group spanning a substituted phenyl group.
It is formed from an unsaturated polyfunctional organopolysiloxane having a'', b'' and -c''=1, and a'', @b'' and -cl- are each more than 0.

Preferably, the unsaturated polyfunctional organopolysiloxane of the present invention has the following composition.

(In the formula, "a" + "b" ten "C":=:1 and "a7"b
``and C'' are each greater than 0) This organopolysiloxane is a branched structure composed of three distinct structural units. The first unit is preferably a reactive organofunctional tririnloxane, such as gamma-methacryloxypropylsiloxane. The second unit is preferably a chain extender such as dimethylsiloxane, while the third unit acts as a cap or end group and is preferably a trimethylsiloxane unit.

Preferably, the unsaturated polyfunctional organosiloxane of the present invention is A
It has a viscosity of 7 to 7 centistokes at 25°C as measured with a capillary viscometer in STM Test 11 & 1D-446.

The preferred molar fraction range for each of the three units is a
==0.10-0.40-Fnyl7lac'/yon, b=
0.25~α80 mol 7 Rakuyon and C=0.1
0-0.40 mole fraction.

In certain preferred embodiments, the contact lens material comprises a
= [12[1~α35 mole 7 lactation, b=0.
40-0.60 mol 7 lac'/yon, c = 0.20
~0.40 mole fraction, 30-60% by weight,
the first component of the above formula in an amount of 169 to 40 i% by weight of methylmethacrine and 1 to 10 percent by weight of vinylpyrrolidone, acrylic acid, methacrylic acid or mixtures thereof;
with a mixture of components polymerized to 95 or more by free radical polymerization.

Contact lenses made from the materials of the invention are preferably rigid or semi-rigid, are easily assembled and finished by conventional means, have excellent dimensional stability, and are inherently wettable with a suitable refractive index. It is a feature of the present invention that the material is hard and has good light transmission properties. Such lenses are durable, have good oxygen permeability, are biocompatible with the eye, are substantially non-hydratable, are chemically stable, and have reasonable It has scratch resistance as well as resistance to protein accumulation. These allow the user to wear them safely and comfortably for extended periods of time, while providing the user with good vision.

This reduces the trouble of handling lenses and greatly improves future life.

Any of the novel organopolysiloxanes of this invention are composed of a wide variety of molecules and are not described as one particular composition and therefore as an average or typical composition, possibly having one or more polymerizable groups. You should understand that Such structures are known and described as mixed structures or otherwise known and described as resins.

The six unitary unsaturated polyfunctional organomonopolysiloxanes of the present invention, which can be described as resins or resin systems, can be prepared using a variety of reaction techniques well known in the art. Most preferred is the co-hydrolysis route where chlorosilane or alkoxysilane intermediates are used. The cohydrolysis reaction can be carried out in the presence of water-miscible solvents such as methanol or ethanol and in the presence of water-soluble solvents such as diethyl ether, dibutyl ether, toluene, naphtha or chloroform.

The use of an acetoxysilane intermediate in conjunction with an ethanol/sulfuric acid catalyst system is also used to prepare the unsaturated multifunctional organopolysiloxanes of this invention.

In cohydrolysis, a mixture of reactants is selected with amounts of each selected to provide the desired mole fraction in the final product. Thus, as described above for "b" and "C", molar clarification reveals structural constraints in each particle composition. Sufficient time to complete the hydrolysis and condensation process.
J is taken. A typical time period of 2 hours to 2 days is 120
-98° C. and more preferably at room temperature. The organic phase carries the product formed and separates from the water since the organic phase is immiscible with water. Low molecular weight by-product? Removed from the organic phase, preferably by utilizing heat and vacuum as known in the art, to give about 2
Molecular weights below 00 are excluded. The crude product remaining after removal of by-products is extracted with a basic solution, washed with water and then dried. And that is the purified end product referred to as the resin product that can be further reacted to form the final high molecular weight polymer that can be formed into contact lenses and serves as the contact lens material.

Such co-hydrolysis operations are well known in the art.

Preferably, an ethanol-sulfuric acid catalyst is used when alkoxysilanes and acetoxysilanes are used as reactants. Preferably the silane is mixed as in the previous procedure using an ethanol sulfuric acid catalyst containing a small amount of water. The reaction times and temperatures are preferably as described above and for the preparation of the crude product. Such reactions are detailed in US Pat. No. 3.80a178.

Typically, the starting material of the present invention is a reactive silane of the type F'2SiX2 R"3iX, where R is hydrogen or methyl, and R' is 1 to about 5
is a divalent alkylene group having R' carbon atoms;
is a monovalent hydrocarbon having 1 to about 5 carbon atoms;
a substituted monovalent hydrocarbon group having about 5 carbon atoms, phenyl, substituted phenyl, or cyclohexyl, where "X" is chloro, methoxy, ethoxy,
easily hydrolyzable groups such as methoxyethoxy or acetoxy).

The molar ratios of the various reactants greatly control the molecular weight and structure of the reactant organopolysiloxane. Other factors such as the temperature of the reaction and the presence of solvent also influence the composition of the product organopolysiloxane.

None of the novel organopolysiloxanes of the present invention are of any particular composition but of a variety of molecules and therefore
It should be understood that an average or typical composition having more than one polymerizable group must be described. Such structures are known and are referred to as mixed structures or sometimes known as resins.

Preferably the contact lens composition is solely polymerized,
Alternatively, it can be composed of an unsaturated polyfunctional organic polysiloxane copolymerized with other monomers. The copolymer may incorporate wetting agents such as hydrophilic monomers and hardness modifiers such as hardeners such as methyl methacrylate or certain other acrylates or softeners such as methacrylates. can.

The physical properties of the compositions disclosed in this invention can be altered by structural changes in the multifunctional organopolysiloxane components and/or by varying the type and percentage of comonomers.

In one embodiment of the invention, an oxygen transporting transparent
Intrinsically wettable contact lenses are made from the polymerized organopolysiloxane resins of this invention only.

In another embodiment of the invention, the polymeric composition comprises an organopolysiloxane resin of the invention copolymerized with one or more other monomers.

Such other copolymers are preferably hardening or softening agents or hydrophilic agents. For example, the hardness modifier is
may be an ester of a monohydric or polyhydric alkanol or phenol with an acid selected from the group consisting essentially of acrylic acid, methacrylic acid, itagonic acid and mixtures thereof. , the hydrophilic monomer can be comprised of many different materials, as discussed below.

When comonomers are used, the polymeric compositions of the invention are preferably prepared by conventional free radical polymerization techniques. Free radical initiators are incorporated in amounts from 0.01 to ZO weight percent of the total composition at reaction temperatures of 25°C to 125°C to initiate and complete the polymerization. Conventional bulk polymerization operations can be used to produce castings that can be machined and polished in conventional operations to make contact lenses.

Alternatively, polymerization can be carried out directly in the contact lens mold. The starting resin system is preferably free-radically catalyzed to achieve 9954 or higher.

Multifunctional organopolysiloxane resins can provide a high degree of oxygen permeability, while strength and biocompatibility can be provided by other parts of the copolymer when comonomers are used. The use of methacrylates or acrylate esters provides strength and hardness or elasticity in some cases. Incorporation of hydrophilic monomers can greatly increase the wettability of the material to achieve biocompatibility.

The novel resin compositions of this invention are prepared from organopolysiloxanes containing a plurality of unsaturated polymerizable groups. Optical contact lenses are constructed from polymers of these resinous monomers, preferably incorporating other comonomers to provide the contact lens with the appropriate balance of desired physical and chemical properties. . Typically, the multifunctional organopolysiloxane resin systems useful in the present invention can be polymerized alone and to form contact lenses, or can be copolymerized with other organic components and have the following formula: where R is hydrogen or methyl, and R' is 1 to about 5
is a divalent alkynone group having R# carbon atoms;
a monovalent hydrocarbon group having from 1 to about 5 carbon atoms, 1
~ a substituted monovalent hydrocarbon group having about 5 carbon atoms, a phenyl group, a substituted phenyl group or a cyclohexynyl group with sb, ``a'' 1 in 1 in ``b'' + ``c'' −
a', "b" and -cm are all 0 and shi is also large)
have.

The comonomers used with the multifunctional organopolysiloxanes in the lens compositions of the present invention are capable of undergoing free radical polymerization and are capable of any of the following to enhance desirable properties such as mechanical suitability, durability, and biocompatibility. It can be a polymerizable monomer.

A description of comonomers that can be usefully used in accordance with the present invention is given below.

Preferably the comonomer is a hardener or softener, such as an ester of a C1-atO mono- or polyhydric alkanol or phenol with an acid selected from the class consisting essentially of acrylic acid and methacrylic acid. obtain. Hydrophilic curing agents such as itaconate mono- or di-esters may also be used.

Methyl, ether, propyl, n-butyl, inglovir, hexyl, peptyl, nclohexyl, 2-ethylhexyl, ethoxyethyl, futoquinether, 2-hydroxyethyl, 21&h3-hydroxypropyl, 3-methoxy-2-hydroxypropyl, tetrahydrofurfuryl, Derivatives of acrylic, methacrylic and itaconic acids such as aryl, allyl, glycidoxy are useful.

Other comonomers include N-vinylcarbazole, N-vinylpyrrolidone, hydroxynaphthyl methacrylate, steryls such as styrene, methylstyrene, methkinstyrene, and acetkinstyrene.

Allylic monomers, such as diallyl diglycol dicarbonate, diallyl phthalate, diallyl carbonate, and triallyl cyanurate, are also useful comonomers.

The wettability of the compositions disclosed in this invention can be enhanced by the incorporation of hydrophilic neutral monomers, hydrophilic cationic monomers and hydrophilic anionic monodispersions and mixtures thereof. All of these act as humectants. These classes of compounds are hydrophilic acrylates and methacrylates, acrylamide, methacrylamide and vinyl-lactams.

Typical hydrophilic neutral monomers that impart hydrophilic properties to the surface of the contact lens materials of the invention iN-vinylpyrrolidone, acrylamide, methacrylamide, N,N-dimethylacrylamide or methacrylamide, 2-hydroxyethyl acrylate or methacrylate, 2- or 3-hydroquine propyl acrylate or methacrylate, glyceryl acrylate or methacrylate v-
Glycidyl acrylate or methacrylate, with the general formula HO(CnH2nO)XH6, where wn" is a number from 1 to about 4 (1) and "X' is a number from 2 to about 10. )
3 of polyether and acrylic acid and methacrylic acid
-Methoky 2-hydroxyethyl acrylate or methacrylate monoester.

The cationic hydrophilic monomers can initially be in a charged state or can be subsequently converted to a charged state after formation of a contact lens. These classes of compounds are derived from basic or cationic acrylates, methacrylates, acrylamide, methacrylamide, vinylpyridine, vinylimidazole and diallyldialkylammonium polymerizable groups.

Such monomers include 1% N-dimethylaminoethyl acrylate and methacrylate, 2-methacryloquinethyl trimetherammonium chloride and methyl sulfate, 2-. 4- and 2-methyl-5-vinylpyridine, 2-24- and 2-methyl-5-vinylpyridinium chloride and methyl sulfate, N-
(3-methacrylamidopurpyr)-N,N-dimethylamine, N-(3-methacrylamidopurpyr)-N
, N-
(3-methacryloquine 2-hydroquinluprovir)
-N,N,N-trimethylammonium chloride, diallyldimethylammonium chloride and methyl sulfate.

Anionic hydrophilic monomers are initially in a neutral state or are later converted to an anionic state. These classes of compounds include active boxes, sulfonates, and phosphates or polymerizable monomers containing phosphate groups. Such monomers include acrylic acid, methacrylic acid, sodium acrylate and methacrylate, vinyl sulfonic acid, sodium vinyl sulfonate, p-styrene sulfonic acid, sodium p-styrene sulfonate,
Represented by 2-methacryloyloxyethylsulfonic acid, 3-methacryloyloxy-2-hydroxyglopylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, arylsulfonic acid, 2-phosphatoethyl methacrylate .

When comonomers are used with the resin systems of the present invention, they are used in varying amounts. The following table describes possible percentages and formulations.

Oxygen Permeable Material Hardness Modifier of the Invention 075-2% 75-1% Hydrophilic Agent 0 0 1-10 Cross-linking agent in some cases compositions based on the novel organopolysiloxanes disclosed herein It is desirable to mix it with

Examples of cross-linking agents include, but are not limited to, acrylic acid, methacrylic acid, acrylamide, methacrylamide, and polyfunctional derivatives of polyvinyl-substituted benzene.

Ethylene glycol diacrylate or dimethacrylate, diethylene glycol diacrylate or dimethacrylate, tetraethylene glycol diacrylate or methacrylate, polyethylene glycol diacrylate or methacrylate, trimethylolbroban triacrylate or trimethacrylate,
Bisphenol A diacrylate or dimethacrylate, ethoxylated bisphenol A diacrylate or dimethacrylate, pentaerythritoltri and tetraacrylate or methacrylate, tetramethylene diacrylate or dimethacrylate, methylene bisacrylamide or methacrylamide, dimethylene bisacrylamide or methacrylamide ,
N,N'-dihydroxyethylenebisacrylamide or methacrylamide, hexamethylenebisacrylamide or fC is methacrylamide, decamethylenebisacrylamide or methacrylamide divinylbenzene.

The copolymers described in this invention are prepared by polymerization of groups with the incorporation of free radical initiators. The initiators are selected from those commonly utilized for polymerizing vinyl type monomers and include the following representative initiators.

2.2'-Azo-bis-isobutyronitrile, 4.4'
-Azo-bis-(4-cyanopentanonic acid), t-buter peroctoate, benzoyl peroxide, lauroyl peroxide, methyl ethyl ketone peroxide,
Diisopropyl peroxycarbonate.

Free radical initiators are normally used at 0.01 to 2% by weight of the total compound. Polymerization is preferably carried out to 95 or more parts of the starting material by a reaction driven as close to 100 parts as possible.

The materials of the present invention can be polymerized directly in a suitable mold to form contact lenses. All of the materials are thermosetting, so a variety of assembly methods can be used. Preferably, the contact lenses are polymerized into sheet or rod stock so that they can be machined.

It is preferred to use methods conventional in forming contact lenses such as those used for polymethernotacrine (PMMA). In this method, the formulation is directly polymerized into sheets or rods and the contact lenses are cut into buttons, discs or other pre-molded forms and then machined to obtain the lens surface.

The resulting polymerizable button material has the optical qualities necessary to produce aberration-free, oxygen-permeable rigid contact lenses according to the present invention.

The polyfunctional organopolysiloxane monomers of this invention offer many benefits when utilized as the basis for contact lens materials. The disclosed monomers are essentially organopolysiloxanes, but contain polyfunctional groups that permit their incorporation into the copolymer system by free radical polymerization. Furthermore, due to the presence of the polyfunctional polymerizable group, the organopolysiloxane moieties become compatible in the copolymer structure.

The oxygen requirements of the human cornea are well established and contact lenses made from the polymers and copolymers of the present invention can meet and easily exceed this requirement.

Due to the unique properties of the composition, contact lenses formed with this method have a high degree of oxygen permeability, while maintaining clarity,
Other essential properties such as wettability and durability! ! ,
is maintained. Oxygen permeability is 4X 10-” tnl
It is meant to include polymeric materials having an oxygen permeability greater than 0.2 cm2/θecm+aHg.

The following examples are given to illustrate the invention, but the invention is not limited thereto.

Example 1 γ-methacryloxypropyltrimethoxysilane 15
0me (0,632 mol), trimethylchlorosilane 1
A crystalline mixture of 55-(1,264 moles) and 155 rnl (1.264 moles) of dimethyldichloro7rane was added to 600 ml of water with stirring. The temperature of hydrolysis was maintained at approximately 40-50°C during mixing.

After stirring overnight, the aqueous phase was separated and the organic phase was washed with an equal volume of water. The volatiles are then removed using high vacuum at a temperature of about 70-75°C. The organic phase was removed. The crude product was then extracted with sodium hydroxide/sodium sulfate solution and then washed with sodium sulfate solution. The organopolysiloxane was then dried over magnesium sulfate to form product 23.
I got 0d5c.

This material, having a viscosity of 13.2 centistokes at 25°C, was designated Ps-1. Nuclear magnetic resonance (silicon 29) analysis showed the presence of the following groups in the indicated molar proportions:

0H2-0-0-OCIJ201hCjHzB10s7
[1,20[1,32(OH3)2sio
Q, 40 0.42(aH3)3Siol
AO, 40o, 26 Example 2 r-methacryloxyprobyltrimethoxy'/silane 1
A mixture of 50#l7I (11,632 mol), 155 mg (1,264 mol) of trimethylchlorosilane and 155d (1,264 mol) of dimethyldichlorosilane, 300 ml of diethyl ether, and 30' of water.
Om/ was added to the slurry. The temperature of hydrolysis was maintained at about 40°C by refluxing the ether.

After stirring overnight, the aqueous phase was separated and the organic phase was washed with an equal volume of water. The organic phase was then devolatilized using high vacuum at a temperature of about 70-75°C. The crude product was then extracted with sodium hydroxide/sodium sulfate,
Washed with sodium sulfate solution. The organopolysiloxane was then dried with magnesium sulfate to produce the product 230#+7!
I got it.

This material, having a viscosity of 14.8 centistokes at 25°C, was designated PS-2. Nuclear magnetism 111 ('/
29) Analysis showed the presence of the following groups in the indicated molar ratios:

0H2-0-0-00H20H20H2SiOv20.
20 0.29(OH3), SiOO,400,
44(0H3)3810xAO,400,27 Example 3 γ-methacryloxypropyltrimethoxysilane 15
0 mg (0,632 mol), trimethylchlorosilane 1
A mixture of 55-(1,264 mol) and dimethylcyclolonane 155-(1,264 mol) was added with stirring to a solution of 30% methanol and 30% water. The temperature of hydrolysis is around 40-50℃ during mixing.
was maintained.

- After stirring overnight, the aqueous phase was separated and the organic phase was washed with an equal amount of water. The volatiles were then removed from the organic phase using high vacuum at a temperature of about 70-75°C. The crude product was then extracted with sodium hydroxide/sodium sulfate solution and then washed with sodium sulfate solution. The organopolysiloxane was then dried over magnesium sulfate to form product 20.
I got 0-.

This material has a viscosity of 24.4 Senna Stoke at 25°C'! It was named zPs-3. Nuclear magnetic resonance (silicon 29) analysis showed the presence of the following groups in the indicated molar proportions:

((J(3)28i0 0.4[]
0.46(CH3)3SiotAO,4
00,30 Example 4 γ-methacryloxypropyltrimethoxine run 15
0d (0,632 mol), trimethylchlororanf 8
A mixture of m/(11632 mol) and dimethyldichlorosilane 233d (1,896 mol) was added to 600 ml of water with stirring.

The temperature of hydrolysis was maintained at approximately 40-50°C during mixing.

After stirring overnight, the aqueous phase was separated and the organic phase was washed with an equal volume of water. Volatiles were then removed from the organic phase using high vacuum at a temperature of about 70-75°C. The crude product was then hydroxylated) extracted with IJum/sodium sulfate solution and then washed with sodium sulfate solution. The product 220d was then dried with organic polysiloxane III:gnesium sulfate.

This material, having a viscosity of 30.2 centistokes at 25°C, was designated PS-4. Nuclear magnetic resonance (silicon 29) analysis showed the presence of the following groups in the indicated molar proportions:

CH2-C-0-00H20H2C! H2S103AO
,200,16(C4H6)2 SiOO,600,5
9(0H3)35iotAO,200,25Example 5 γ-methacryloxypropyltritquinsilane 1s
od (0,632 mol), trimethylchlorosilane 78
-(0,632 mol) and dimethyldichlorosilane 2
33Wd! , (1,896 mol) was slowly added to a slurry of 300 ml of diethyl ether and 300 ml of water. The temperature of hydrolysis was maintained at about 40°C by refluxing the ether.

After stirring overnight, the aqueous phase was separated and the organic phase was washed with an equal volume of water. The organic phase was then devolatilized using high vacuum at a temperature of 70-75°C. The crude product was then extracted with sodium hydroxide/sodium sulfate and washed with sodium sulfate solution. The organic polysiloxane was then dried over magnesium sulfate to obtain 225 ml of product.

This material had a viscosity of 2 aO centistokes at 25°C and was designated as 1 ps-s. Nuclear magnetic resonance (silicon 2
9) Analysis showed the presence of the following groups in the indicated molar proportions:

CH30 11 C! H2=O-000HzOHzCH281OAO,2
00,17(aHs)2SiOa, /lo O,
57(CHs)s 5i01AQ, 20 0.26
Example 6 γ-notacryloxyglopyltrimethquine silane 15
0d (0,632 mol), trimethylchlorosilane 78
mg (0,632 mol) and dimethyldichlorosilane 2337! (1,896 mol) was added with stirring to a solution of 300 ml of methanol and 300 ml of water.The temperature of hydrolysis was approximately 40-5 ml during mixing.
The temperature was maintained at 0°C.

- After stirring overnight, the aqueous phase was separated and the organic phase was washed with an equal amount of water. Volatiles were then removed from the organic phase using high vacuum at a temperature of about 70-75°C. The crude product was then extracted with sodium hydroxide/sodium sulfate solution and then washed with sodium sulfate solution. The polysiloxane was then dried over magnesium sulfate to obtain product 105-.

This material was designated tl-PS-6 with a viscosity of 657 centistokes at 25°C. Nuclear magnetic resonance (silicon 29) analysis showed the presence of the following groups in the indicated molar proportions:

0H2-0-0-OCH20H20HzSiO3AO,
200,10(C4H6)2S10 0.6
0 [165(OHs)s 5iOIAQ, 20
0.25 Example 7 γ-methacryloxyglobil trimethoxy 7 run 15
0m (0,632 mol), trimethylchlorosilane 11
A mixture of 6d (0,948 mol) and 194 ml (1,580 mol) of dimethyldichloro7rane was slowly added to 600 ml of water with stirring. The hydrolysis temperature was maintained at approximately 40-50'C during mixing.

After stirring overnight, the aqueous phase was separated and the organic phase was washed with an equal volume of water. The volatiles were then removed from the organic phase using high vacuum at a temperature of about 70-75°C. The crude product was then extracted with sodium hydroxide/sodium sulfate solution and then washed with sodium sulfate solution. Next, the organic polysiloxane was dried with magnesium sulfate to produce product 205d.
'I got it.

This material with a viscosity of 21.6 centistokes at 25°C was designated '1iPs-7. Nuclear magnetic resonance (silicon 29) analysis showed the presence of the following groups in the indicated molar proportions:

Base Calculated value Actual value OH30 11 CH2-0-0-00H20H2C! H2S Sat 03/
0.20 0.27 (OH3)
2SiOG, 50 0.49(OH3)3SiO,
AO,300,24 Example 8 γ-methacryloxyglobyltrimethoxysilane 15
0ml (0,632mol), trimethylchlororane 1
A mixture of 194m (0,948 mol) of dimethyldichlorosilane and 194m (1,580 mol) of dimethyldichlorosilane was slowly added to 300 ml of methanol and 300 ml of water with stirring. The temperature of hydrolysis was maintained at approximately 40-50°C during mixing.

- After stirring overnight, the aqueous phase was separated and the organic phase was washed with an equal amount of water. The volatiles were then removed from the organic phase using high vacuum at a temperature of about 70-75°C. The crude product was then extracted with sodium hydroxide/sodium sulfate solution and then washed with sodium sulfate solution. The organopolysiloxane was then dried over 6+ft bQ) magnesium to yield product 225d.

This material with a viscosity of 1 & 5 centistokes at 25°C was designated PS-8. Nuclear magnetic resonance (silicon 2
9) Analysis showed the presence of the following groups in the indicated molar proportions:

0H2-0-C-00kCEzOH2EliO3AO,
200,27(aH3)2sto o,
so o, 51(OH3)3SiO1/20,3
0 0.2.4 Example 9 r-methacryloquinebropyltrimethquine silane 15
0d ([1632 mol), trimethylchlororane 25
A mixture of 2rnt (1,896 mol) and dimethyldichlorosilane 252rnt (1,896 mol) was added to 600 ml of water with stirring. The temperature of hydrolysis was maintained at approximately 40-50°C during mixing.

After stirring overnight, the aqueous phase was separated and the organic phase was washed with equal amounts of water. Volatiles were then removed from the organic phase using high vacuum at a temperature of about 70-75°C. The crude product was then extracted with sodium hydroxide/sodium sulfate solution and then washed with sodium sulfate solution. The organoborinoxane was then dried over magnesium sulfate to produce product 24.
5#+7! I got it.

This material, having a viscosity of 1@7 centistokes at 25 DEG C., was designated PS-9. Nuclear magnetic resonance (silicon 29) analysis showed the presence of the following groups in the indicated molar proportions:

0H2-C-C-OCH20H20H2Si03Aa1
4 0.57(OH3)z13i0 0
．． 43 0.45(OHs)3sioIAO,43
0,20 Example 10 γ-methacryloquineprobyltrimethoxysilane 15
0ml (0,632mol), trimethylchlororane 2
A mixture of 32 ml (1,896 moles) and 232 sd (1,896 moles) of dimethyldichlorosilane was slowly added to the solution of 60 ml of methanol and 300 ml of water with stirring. The temperature of hydrolysis is about 40 to 5
The temperature was maintained at 0°C.

- After stirring overnight, the aqueous phase was separated and the organic phase was washed with an equal amount of water. Volatiles were then removed from the organic phase using high vacuum at a temperature of about 70-75°C. The crude product was then extracted with sodium hydroxide/sodium sulfate solution and then washed with sodium sulfate solution. The organopolysiloxane was then dried over magnesium sulfate to obtain product 275-.

This material was designated IP8-10, having a viscosity of a1 centistokes at 25°C. Nuclear magnetic resonance (silicon 2
9) Analysis showed the presence of the following groups in the indicated molar proportions:

0Hz-00-00HzOHzOH2Si03A0.1
4 0J6(aH3)2s1o o,
4s 0.44(OHs)ssios%
0.45 (L20 Example 11 γ-methacryloxyglobyltrimethoxysilane 75
m7! (0,316 mol), trimetherc o.

A mixture of 78 m/(0,632 mol) of silane and 267 m/(2,212 mol) of dimethyldichlorosilane was slowly added to 600 ml of water with stirring.

The temperature of hydrolysis was maintained at approximately 40-50°C during mixing.

After stirring overnight, the aqueous phase was separated and the organic phase was washed with an equal volume of water. The volatiles were then removed from the organic phase using high vacuum at a temperature of about 70-75°C. The crude product was then extracted with sodium hydroxide/sodium sulfate solution and then washed with sodium sulfate solution. The organopolysiloxane was then dried over magnesium sulfate to form the product 112-
I got it.

This material with a viscosity of 13.1 Senna Stoke at 25°C was designated PS-11. Nuclear magnetic resonance (silicon 29) analysis showed the presence of the following groups in the indicated molar proportions:

Base Calculated value Actual value 0H2-0-0-00, H2CH2OH2S1OqAO
,100,21(CH3),El(OO,700,63
(CH3)3EIiO,% 0.20
0.16 Example 12 γ-methacryloxypropyltrimethoxysilane 75
m/(0,316 mol), trimethylchloro7ran78
7! (α632 mol) and dimethylcyclolonan2
A mixture of 67d (2,212 moles) is slowly stirred, 300d of methanol and 300d of water, 117! added to. The temperature of hydrolysis was maintained at approximately 40-50°C during mixing.

- After stirring overnight, the aqueous phase was separated and the organic phase was washed with an equal amount of water. The volatiles were then removed from the organic phase using high vacuum at a temperature of about 70-75°C. The crude product was then extracted with sodium hydroxide/sodium sulfate solution and then washed with sodium sulfate solution. The organopolysiloxane was then dried over magnesium sulfate to form product 14.
7 ml was obtained.

This material with a viscosity of 94 centistokes at 25°C was designated PS-12. Nuclear magnetic resonance (silicon 29) analysis showed the presence of the following groups in the indicated molar proportions:

(CHa)2SiOO,700,60 (C!)13) 36110/20.20 0.1
8 Example γ-methacryloxypropyltrimethoxysilane 75
mA (0,316 mol), trimethylchloro7 run 39
+++g (0,316 mol) and dimethyldichloro7
A mixture of Run 300*d (2,528 moles) was slowly added to 600 rnt of water with stirring.

The temperature of hydrolysis was maintained at approximately 40-50°C during mixing.

After stirring overnight, the aqueous phase was separated and the organic phase was washed with an equal volume of water. The volatiles were then removed from the organic phase using high vacuum at a temperature of about 70-75°C. The crude product was then extracted with a sodium hydroxide/sodium sulfate solution and then washed with a botrium sulfate solution. Next, the organic polysiloxane was dried with magnesium sulfate to produce product 1.
The total volume was 25 ml.

This material with a viscosity of 16.8 Senne Stoke at 25°C was designated PS-13. Nuclear magnetic resonance (silicon 29) analysis showed the presence of the following groups in the indicated molar proportions:

(OH3)2 SiOO,800,74(OH3)3s
iot/IO,100,14 Example 14 γ-methacryloxypropyltrimethoxysilane 75
d (0,316 mol), trimethylchlorosila 7397
! (0,316 mol) and 300 ml (2,528 mol) of dimetheloxsilane were slowly added to methanol 300 and water 300 with stirring. The temperature of hydrolysis is around 40-50℃ during mixing.
was maintained.

- After stirring overnight, the aqueous phase was separated and the organic phase was washed with an equal amount of water. The volatiles were then removed from the organic phase using high vacuum at a temperature of about 70-75°C. The crude product was then extracted with sodium hydroxide/sodium sulfate solution and then washed with sodium sulfate solution. The organopolysiloxane was then dried over magnesium sulfate to yield product 144.
m'! I got 5.

This material, having a viscosity of 13.6 Senna Stoke at 25°C, was designated PS-14. Nuclear magnetic resonance (silicon 29) analysis showed the presence of the following groups in the indicated molar proportions:

OH2OH2-0-C-00H20H20HzSiO,
100,10(OH3)2 SiOO,800,76(
OHs) 3siotAO, 100, 14 Example 15 Hard oxygen-permeable Vulcan resin t Methyl methacrylate (M
The free radical initiator 2,2'-azobisinbutyronitrile (A 13N). The formulation ingredients (shown in parts by weight in Table 1) were thoroughly mixed, flushed with nitrogen, and transferred to test tubes sealed with serum caps. This test tube is then 40
℃ and allowed to polymerize for 3 days.

The test tubes are then placed in an oven at 65°C for an additional 2 days, after which the polymerized rods are removed from the test tubes. The rigid transparent rods are then conditioned under vacuum at 100°C for approximately 24 hours to complete the polymerization process. and remove the presence of any mechanical strain. The adjusted rods are then machined into contact lens blanks (diameter difference in inches,
disk with thickness i = inches).

Oxygen permeability values for contact lenses made from the materials described herein are as low as AI'ETM D except when plan contact lenses are used instead of large flat disc materials.
1434.

The permeability device is constructed in such a way as to accept actual contact lenses and is calibrated according to the other polymeric oxygen permeability data reported in Table 1.

Polymethyl methacrylate, polycarbonate and polystyrene are respectively 1,22 and 35α3? Il+II
/cnn2sec-X 10-10 .

Table 1 6035---50.2 57 120So 45-
-,--50.2 147 11360'--35-
-50,25512050--45-50,21401
18 60---3550,270119 50---4550,2, 1701174) cm
'mm/err? sea cm Hg, X 10
16 Utilizing the experimental procedure of Example 15, this example describes a method for preparing a suitable coating material for manufacturing hard contact lenses.
! ! Explain its manufacture and properties.

50 45 - - 5 0.2 1145
0-45-5 0.2
11450 - - 45 5
0.2 111 Practical Example 17 Utilizing the experimental procedures of Example 15, this example describes the preparation and properties of materials suitable for making rigid contact lenses.

50 45 - 5 0.2
11650 - 45 5 0.2
115 Example 18 Experimental operation of Example 15? This example illustrates the preparation and properties of materials suitable for making rigid contact lenses.

50 45 - 5 0.2
10850-45
5 α2 103 Example 1
9 Utilizing the experimental procedures of Example 15, this example illustrates the preparation and properties of materials suitable for making rigid contact lenses.

55 45 - -0.2
T0n 45 -
50.2 NT55 -
4s -0,2T0n -45
S α2 NTT - Transparent NT - Haze Example 20 Utilizing the experimental procedures of Example 15, this example describes the preparation and properties of materials suitable for making rigid contact lenses.

55 45 - 0.
2 760 55
5 U, 2 NT55
- 45 - α2
T0n-3550,2NT T-Transparent NT-Hazy The foregoing examples illustrate the preparation and incorporation and copolymerization of the resin system of the present invention with methyl methacrylate and methacrylic acid. As previously discussed, other comonomers can be used with the resin system to form a polymerized product. In some cases, the resin system can polymerize itself to form a rigid contact lens material. When the resin of the present invention is homopolymerized and used for contact lenses,
It is preferred to surface treat such lenses by conventional oxidation or grafting to render the surface wettable.

Claims (1)

[Scope of Claims] 1) The following formula (wherein R is hydrogen spanning methyl, and R'I''i1~
A divalent alkylene group having 5 carbon atoms, R
' is a monovalent hydrocarbon group having 1 to 5 carbon atoms, 1
Substituted monovalent hydrocarbon group having ~5 carbon atoms, phenyl group, substituted phenyl group or cyclohexyl group V), -a"1'"b#+@"C"=1 in,
"a-,""b" and °c are each greater than 0,
where "a" has a molar fraction value of 0.10 to α40, sb" has a molar fraction value of Q, 25 to 0.80, and "c" has a molar fraction value of 0.10 to 0.40. fraction value), has good oxygen permeability and is polyfunctional, which can be polymerized into transparent, optically bright polymerizable materials suitable for use in contact lens manufacturing. An organopolysiloxane resin system. 2) A resin system according to claim 1 having a viscosity of 7 to 70 centistokes at 25° C. 3) A resin system according to claim 1, in which the units mentioned in the first part are the reactive organofunctional group tririnloxane. 4) The resin system according to claim 2, wherein the second mentioned unit is a chain extender and the third mentioned unit is a terminal group. Claim 3, characterized in that the tririnloxane is γ-methacryloquine globylsiloxane, the linear extrinsist is dimethaneloxane sb, and the terminal group is trimethylsiloxane. 5) A resin system for use in a contact lens material polymer having the formula: 6) "a" f) i Q, having a molar fraction value of 10 to 0.40, and -b" Resin system according to claim 5, characterized in that the resin system has a molar fraction value of Q, 25 to α80 and c'' has a molar fraction value of from 0.10 to (140).7) 7. The resin system of claim 6 having a viscosity of 7 to 70 centistokes at 25°C. 8) The starting materials co-hydrolyze to a viscosity of 7 to 70 centistokes at 25°C.
A polyfunctional organopolysiloxane resin system characterized in that it consists of a reactive vinyl group-type silane, a di-substituted 7-lane, and a tri-substituted silane, forming a resin system with a viscosity of 70 centistokes. 9) The reactive vinyl group type silane is a gamma meth phmethyl siloxane unit, and the molecular ratio of each is 0.10 to 0.
Resin system according to claim 1, characterized in that the molar fraction is between 40.0625 and 0.80 and between 0.10 and 0.40. 10) The resin is formed from mono-, di- and tri-substituted reactive siloxane units, characterized in that the resin consists of mono-, di- and tri-substituted organosiloxane units in which at least one vinyl group-type moiety is present per molecule. Multifunctional organic polysilane resin system. 1. A resin-based polymer and a hardness modifier according to claim 1. 12. A polymer described in claim 11, further comprising a hydrophilic agent. 16) The polymer according to claim 11, characterized in that the resin system is 25 to 98% by weight. 1. The hardness modifier is an ester of a C'20 monohydric or polyhydric alkanol or phenol with an acid selected from the group consisting essentially of acrylic acid, methacrylic acid, itaconic acid and mixtures thereof. Claim 13 characterized in that the field can be selected from the group consisting of
Polymers described in Section. 15) The polymer according to claim 14, wherein the hardness modifier is methyl methacrylate. 16) A contact lens comprising the resin-based polymer according to claim 1. 17) A contact lens comprising a polymer made of the resin system according to claim 5. 1a) A) The following formula (where a==[l, 10-0.40 molar fraction, b=α25-0.80 molar fraction, C=0.1
0~Q, resin system with 40 mole fraction) 25~
98% by weight, B) 01=C! esters of mono- or polyhydric alkanols or phenols with acids selected from the group consisting essentially of acrylic acid, methacrylic acid, itaconic acid and mixtures thereof; and C) hydrophilic agents 1-10%. formed by free radical polymerization. A contact lens characterized in that a material is polymerized to a degree of achievement of 5 or more. 19) A) is in the range of 30 to 60% by weight, a
= (L 20~0.55 mole 7 rak'/yo"/1
) = Q, 4Q ~ 0.60 mol fraction c = o,
Contact lens according to claim 18, characterized in that the 20-0.40 molar fraction B) is 69-40% by weight and is methyl methacrylate, and ``a) is 1-10% by weight. Material. 20) The contact lens material according to claim 19, characterized in that C is vinylpyrrolidone. 21) The contact lens material according to claim 19, characterized in that C is acrylic acid. Contact lens material. 22) The contact lens material according to claim 19, characterized in that C is methacrylic acid.