JP2005516702A - High refractive index flexible silicone - Google Patents

Abstract

The present invention discloses a high refractive index polysiloxane (co) polymer comprising refractive index modifying groups chemically bonded in clusters to the polysiloxane backbone. The present invention also discloses a method of forming such a high refractive index polysiloxane (co) polymer. The polysiloxanes according to the invention are very suitable for use as a material for the production of eye lenses.

Description

  The present invention relates to a high refractive index silicone material, and more specifically, a high refractive index flexible silicone material used as an ocular lens material, an ocular lens formed from a high refractive index polysiloxane, and a silicone material. And an eyeball lens manufacturing method.

  Artificial implant lenses are widely used to replace human lenses with cataracts. Cataracts are a leading cause of blindness in industrial and developing countries. The standard medical procedure for treatment is to remove the clouded human lens by local cataract surgery and replace it with an eye lens.

  At present, conventional polymethylmethacrylate (PMMA) materials and polymers derived therefrom are gradually being replaced by flexible silicones as ocular lens implant materials. With ongoing research on cataract surgery, new techniques have been developed to remove the human lens through a self-suturing incision that is so small that sutures are not required. The thin, flexible and foldable implant material allows the implant lens to be inserted through a small, self-sutured incision for cataract surgery, greatly reducing the risk of complicated post-operative problems. There is an important advantage.

  In addition to the favorable requirement of high flexibility, the ophthalmic lens material must be clear, highly transparent and capable of producing a lens with a high refractive index. An eye lens having a high refractive index has the advantage that it can be thinner than a low refractive index eye lens for the same refractive power.

  In order to increase the refractive index of the eye lens, a polymer of polysiloxane and polymethacrylate may be formed. A sulfur compound may be introduced into the siloxane polymer. However, even with these modifications, the refractive index of the silicone material is limited and high optical performance cannot be obtained with its thin lens.

  As disclosed in US Pat. No. 3,996,189, it is known that a polymer having a high refractive index can be obtained by including diphenylsiloxane or phenyl-methylsiloxane in the polysiloxane. At present, introduction of an aromatic group is a general method for increasing the refractive index of an ocular lens material while maintaining biological compatibility. Optionally, other refractive index modifying groups such as cycloalkyl groups and aromatic groups may be used in combination with a phenyl group (Japanese Patent No. 2000017176) or a phenol group (US Pat. No. 5,541,278), for example For eyeball lenses as described in US Pat. No. 5,147,396, Japanese Patent 10305092, European Patent 0353122, WO93 / 21245, WO95 / 17460, US Pat. This conventional copolymer consists of a dimethylsiloxane-phenylmethylsiloxane copolymer or a dimethylsiloxane-diphenylsiloxane copolymer.

  Thus, it is generally known that a silicone material having a high refractive index can be obtained by increasing the amount of the phenyl component of the silicone (co) polymer. When the amount of the phenyl component is about 15 mol%, the polydimethylsiloxane / methylphenylsiloxane copolymer has a refractive index of 1.462 (Gu & Zhou, Eur. Polymer J. 34, pages 1727 to 1733 ( 1998)). A certain level of refractive index can be achieved by using polymers known from the prior art and their manufacturing methods, but with a wide range of refractive indices, i.e. high and low refractive indices. There is a need for materials that can be manufactured.

  Despite the positive effect on the refractive index, it is known that introducing refractive index modifying groups, such as phenyl groups, into polysiloxanes has several significant drawbacks.

  One major drawback is associated with the low flexibility of polymers modified as described above or the long cross-linked polymer structure. The presence of phenyl groups bonded to an alternating backbone of siloxane silicon and oxygen makes the (co) polymers relatively rigid and, despite their high refractive power, these The compatibility of the polymer as a material for eyeball lenses is greatly reduced. In general, by introducing aromatic groups such as phenyl groups into polysiloxanes, the glass transformation temperature, or Tg, of the polymer is increased so that the material is harder, more brittle and less flexible over a wide temperature range. Become. As a result, the material is easily broken or broken during bending, and the compatibility of the phenylated polysiloxane as a material for an eyeball lens is lowered. This is because the eyeball lens must be folded and inserted through a self-suturing incision.

  A well-known solution to the problem of breakage is to strengthen the lens and improve its mechanical properties by combining the polymer with a solid filler. Most commonly, finely pulverized silica is used as a filler for such purposes. This filler has a refractive index of 1.46. In the case of optical lenses, there should be no difference in refractive index between the filler and the polymer, so the maximum refractive index of a lens containing such a filler is 1.46 after all.

  Thus, the use of silicones as ocular lens implant materials and the development of silicones with excellent material properties, especially extending such applications, is determined by the maximum achievable refractive index and flexibility of the material. In order to obtain high flexibility, the glass transformation temperature of the material must be lowered. One way to reduce the glass transformation temperature of polysiloxanes modified with phenyl groups is to bond the phenyl groups to the silicon-oxygen backbone by alkanedyl crosslinking. Such a modification of polysiloxane is known from U.S. Pat. No. 4,780,510, in which a hydride / vinyl reaction pair is used. In US Pat. No. 5,233,007, WO 93/21258, and US Pat. No. 5,420,213, a phenyl group is introduced into tetramethylcyclotetrasiloxane by addition reaction with styrene, whereby tetramethylstyrylcyclotetrasiloxane monomer A process for producing a body is described.

  However, another drawback of introducing refractive index modifying groups into the polysiloxane is related to the molecular weight of the polymer and the achievable mechanical strength of the polymer structure in the silicone material. Polysiloxanes with a high content of phenyl groups generally exhibit a relatively low molecular weight after crosslinking and are therefore relatively inflexible. Thus, due to the relatively low molecular weight, the mechanical strength of the polymer structure after crosslinking of the (co) polymer is reduced. In general, polysiloxanes modified with styrene and polysiloxanes with a high content of phenylsiloxanes have a lower molecular weight than unmodified (ie low refractive index) polysiloxane materials. Therefore, it is difficult to increase the flexibility, elasticity, and mechanical strength of the rubber after crosslinking. Since the reaction from the ring to the chain hardly occurs thermodynamically, it is not easy to polymerize, for example, diphenylcyclosiloxane to a high molecular weight polymer (Journal of Polymer Science Part A: Polymer Chemistry, v35 (10), p1973). Although the desired product can only be produced by applying non-equilibrium reaction conditions, such conditions are not considered suitable for large scale production.

  Thus, when refractive index modifying groups are introduced into the polysiloxane, the flexibility of the silicone produced from the polysiloxane is due to the presence of a relatively low molecular weight polysiloxane and the low flexibility of the polymer chain itself. Property and mechanical strength are lowered.

  Yet another important point to consider when making polysiloxanes for ophthalmic lenses relates to the presence of free reactive groups in the final material. According to the method described in U.S. Pat. No. 4,780,510, the presence of unreacted free vinyl groups in the polymer after the completion of the addition and crosslinking reactions is unavoidable as well as controlled. Products that cannot be manufactured. This material causes allergies, irritation and discomfort to the patient and is not suitable for eye lens applications.

  Surprisingly, when the refractive index modifying groups are attached in clusters to the siloxane backbone via alkanediyl bridges, the refractive index of the siloxane polymer is significantly increased without sacrificing the mechanical properties of the material. It turns out that you can. In spite of the large number of refractive index correcting groups, a high refractive index polysiloxane (co) polymer is obtained in which mechanical properties are hardly adversely affected. The advantageous material properties of the silicone material thus formed are substantially maintained.

  The mechanical properties of the individual (co) polymers are slightly adversely affected, but the influence is slight, and thus the silicone material formed by crosslinking of the individual polymers has beneficial properties and Polysiloxane can be suitably used for the production of ocular lenses.

Basically, the polysiloxane may be formed by either of the following two methods.
i) A method in which an addition reaction is carried out between the cluster-like refractive index correcting group and the cyclic siloxane monomer, and then any of several polymerization methods for forming a (co) polymer is performed. In the following explanation, it is called a monomer method.
ii) A method in which an addition reaction is carried out between the cluster-like refractive index correcting group and the (co) polymer (prepolymer). In the following description, this method is called a polymer method.

  Thus, the present invention provides a clustered refractive index modification chemically bonded to the polysiloxane backbone via an alkanedyl bridge so that one alkanezyl crosslink binds at least two refractive index modifying groups to the polysiloxane backbone. High refractive index (cyclic) siloxane monomers containing groups are provided.

  The present invention also provides a clustered refractive index modification in which one alkanedyl crosslink is chemically bonded to the polysiloxane backbone via an alkanedil crosslink so that at least two refractive index modifying groups are bonded to the polysiloxane backbone. A high refractive index siloxane (co) polymer containing a group is provided.

  By introducing more than one refractive index modifying group at each alkanedyl bridge, a relatively high refractive index can be achieved with only a limited number of modifications required. For example, if three clustered phenyl groups are bonded to the siloxane backbone via an alkanedyl bridge, the degree of contribution to the refractive index per correction is greater than when styrene is bonded to the siloxane backbone. About 3 times.

  The achievable refractive index of the high refractive index polysiloxane (co) polymer material of the present invention is very high, so that the eyeball while maintaining a relatively high refractive index in the resulting (co) polymer. When used in lenses, it can be polymerized with conventional or unmodified polysiloxanes, and such polymerization may be necessary. It is also possible to directly form a high refractive index polysiloxane (co) polymer material.

  The (co) polymers of the present invention exhibit a high molecular weight and thus the resulting material is strong and flexible after crosslinking. This material achieves excellent strength and flexibility, and the refractive index modification groups are clustered via the alkanediyl crosslinks so that one alkanediyl crosslink bonds at least two refractive index modification groups to the siloxane backbone. It has a high refractive index because it is bonded to the siloxane backbone.

  The polymers of the present invention are not substantially cross-linked so that they can be handled and processed during the production of eye lenses.

  Since the number of unreacted crosslinkable groups remaining in the polymer upon precipitation is very small, these groups are substantially completely eliminated during or after crosslinking of the polymer. This is necessary to obtain a biologically compatible material.

  Thus, based on the high refractive index polysiloxanes of the present invention, high refractive index silicone materials having good mechanical strength and a wide range of refractive index values, i.e. very high and low values, can be obtained. Such silicone materials constitute an excellent material for eyeball lenses, for example.

  The present invention relates to an eyeball lens comprising a polysiloxane (co) polymer having a high refractive index, wherein one polysiloxane (co) polymer has at least two refractive index modifying groups having at least two refractive index modifying groups. An ophthalmic lens is provided that includes a clustered refractive index modifying group that is chemically bonded to the polysiloxane backbone via an alkanedyl bridge to bond to the siloxane backbone. Such an ocular lens achieves a high refractive index and is flexible enough to be folded.

  The present invention also provides a method for forming a high refractive index siloxane monomer and siloxane (co) polymer according to the present invention, and a method for forming a high refractive index siloxane (co) polymer with these materials. Is. The method of forming the high refractive index siloxane (co) polymer is relatively easily controllable, and the quality of each batch does not vary greatly. These methods and the materials formed by those methods are necessary for mass production of eyeball lenses. Therefore, the present invention also provides a method for manufacturing an eyeball lens.

  In this application, the term alkyl group refers to a linear or side chain alkyl radical containing 1 to 20, preferably 1 to 10, more preferably 1 to 3 carbon atoms. The alkyl radical may be optionally substituted with one or more substituents containing elements such as oxygen, nitrogen, sulfur, halogen (Cl, Br, I, F), hydrogen, phosphorus, and an alkoxy group, It may contain a hydroxy group, an amino group, a nitro group or a cyano group.

  The term (cyclo) alkyl group refers to an alkyl radical or cyclic alkyl. Cyclic alkyl includes fully or partially saturated monocyclic, bicyclic, or tricyclic alkyl radicals in which each ring moiety contains 3 to 8, preferably 4 to 8, carbon atoms. Such radicals include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secbutyl, terbutyl, pentyl, isoamyl, hexyl, octyl, cyclopentyl, cyclopentenyl, cyclohexenyl, cyclohexyl, oxygen, nitrogen, sulfur, A (cyclo) alkyl group which may be optionally substituted with a substituent containing an element such as halogen, hydrogen or phosphorus, and may contain an alkyl group, an alkoxy group, a hydroxy group, an amino group, a nitro group or a cyano group Is included.

  The term aromatic group also refers to monocyclic or polycyclic aromatic hydrocarbons, ie arenes and their substituted products such as benzene, naphthalene, toluene, and heteroaromatic structures such as thiophene and pyridine. Or aromatic heterocyclic structure.

  The term aryl group refers to a radical containing an aromatic or heteroaromatic system derived from an arene by removing a hydrogen atom from a ring carbon atom such as a phenyl, naphthyl, or anthracene radical. , Sulfur, halogen (Cl, Br, I, F), hydrogen, phosphorus, and the like may optionally carry one or more substituents, and may be an alkyl group, an alkoxy group, a hydroxy group, an amino group. Group, nitro group, cyano group may be contained. Examples of such radicals are pentyl, p-tolyl, 4-methoxyphenyl, 4- (ter-butoxy) phenyl, 4-chlorophenyl, 4-hydroxyphenyl, 1-naphthyl, 2-naphthyl. Also included are fused and bonded rings such as cyclopentadienyl, imidazolyl, thiophenyl, thienyl, and 5-8 rings. In the present invention, the aryl group includes a divalent arylene group derived from an arene such as o-phenylene and an arylene such as benzine.

The term arylalkyl group means an alkyl radical as described above in which one hydrogen atom is substituted with an aryl radical, such as benzyl or 2-phenylethyl.
Allyl refers to the propene radical (CH ₂ ) ₂ CH.

  The high refractive index siloxane (co) polymer according to the present invention comprises a carrier component (X in FIG. 2) containing at least two refractive index modifying groups (Y in FIG. 2) in the presence of an addition reaction catalyst. May be prepared by chemically modifying the monomeric cyclic siloxane precursor by a vinyl / hydride addition reaction using and then (co) polymerizing the modified monomeric siloxane precursor. Monomeric cyclic siloxane precursors containing reactive groups such as hydride groups and vinyl groups may be used as precursor materials for high refractive index siloxane (co) polymers. Such precursors are commercially available (eg, Petrarch® sold by United Chemical Technologies, Inc., Bristol, Pennsylvania, USA), and such precursors provide a well-controlled addition reaction of the present invention. Can be carried out in the manner described above.

The monomeric cyclic siloxane precursor used in the examples of the present invention comprises three or more, alternately arranged with oxygen atoms in the cyclic structure as shown in FIG. Preferably it contains 3 to 6, more preferably 3 or 4 silicon atoms. In FIG. 1, n is preferably 0 or 1 or 2 or 3, more preferably 0 or 1, R is individually alkyl or vinyl or hydride, and R ₁ is hydride or another embodiment. In the case of vinyl. The monomeric cyclic siloxane precursor according to the invention may comprise 1 to 12, preferably 2 to 6, more preferably 2 to 4 reactive groups in the form of vinyl or hydride groups.

  The carrier component (X) can be bonded to the precursor silicon atom by a vinyl / hydride addition reaction such as a hydrosilylation reaction. To allow such bonding, the precursor may contain one or more hydride groups bonded to the silicon atom of the cyclic siloxane, in which case the carrier component contains a reactive vinyl group. .

  In other embodiments, a precursor monomer containing one or more reactive vinyl groups bonded to the silicon atom of the cyclic siloxane can be used, and the refractive index relative to the cyclic siloxane. The carrier component having the correction group (Y) can be effectively bonded. In such a case, the carrier component preferably contains a vinyl reactive hydride group.

  The position and distribution of reactive groups in the precursor monomer is not critical.

  One or more carrier components (X) containing at least two refractive index modifying groups (Y) may be bound to each precursor monomer. In one embodiment, the cyclic siloxane precursor is modified by bonding only one carrier component (X) containing at least two refractive index modifying groups (Y) via an alkanedyl bridge. .

  In another embodiment, two carrier components (X) are bonded to some or all of the silicon atoms in the cyclic siloxane precursor molecule, each carrier component being at least two via an alkanedyl bridge. Two refractive index correcting groups (Y) are carried. In this latter situation, the polysiloxane contains a large number of refractive index modifying groups to form a high refractive index silicone. The number of carrier components bonded to the precursor monomer is selected so that the desired refractive index is obtained in the polysiloxane material produced.

  Also in accordance with the present invention, a cluster-like refractive index modification in which one alkanedyl bridge is chemically bonded to the siloxane backbone via an alkanedil bridge so that at least two refractive index modifying groups are bonded to the siloxane backbone. Monomeric cyclosiloxanes containing groups are obtained. Such monomeric cyclosiloxanes are very useful in preparing the (co) polymers of the present invention.

  Based on the foregoing, one skilled in the art can identify a large number of precursor materials that are useful in the production of high refractive index siloxane (co) polymers according to the present invention. Such precursor materials include cyclic siloxane monomer precursors containing hydride groups. Cyclic siloxane precursors containing vinyl groups such as pentavinylpentamethylcyclopentasiloxane may also be used in the embodiments of the present invention. Particularly useful precursors are tetrahydrotetramethylcyclosiloxane and tetravinyltetramethylcyclotetrasiloxane.

  As noted above, in one preferred embodiment, a carrier component bearing at least two refractive index modifying groups is reacted with a monomeric cyclic siloxane precursor as described above (FIG. 3A).

  The combination of the carrier component (X) comprising at least two refractive index modifying groups (Y) preferably forms a situation in which the carrier component is isolated from the silicon atom to which it is directly bonded. Such sequestration is achieved very advantageously by employing an alkanedyl bridge between the carrier component and the silicon atom. Thus, a very useful reaction pair is formed by a hydride / vinyl reaction pair according to which one of the reaction pairs is present on the side of the monomeric cyclic siloxane precursor and the other of the reaction pairs is the refractive index. Present on the side of the carrier component containing the modifying group. This is because such a reaction pair forms an alcandiyl crosslink, especially an ethanediyl crosslink.

  Another reaction pair is the hydride / allyl reaction pair, which forms an alkanedyl bridge, in particular a propanzyl bridge.

  In view of the above, other suitable reaction pairs will be apparent to those skilled in the art.

  A large number of refractive index modifying groups (Y) can be used to produce high refractive index siloxane (co) polymers according to the present invention. Cyclic and straight chain and side chain hydrocarbons are preferred. In the embodiments of the present invention, it is preferable to use an aromatic group, an aryl group, an arylalkyl group, a cycloalkyl group, or a side chain alkyl group as the refractive index modifying group (Y). In particular, a phenyl group is preferably used as the refractive index correction group.

  One carrier component (X) may carry two or more, preferably three, refractive index modifying groups (Y). The carrier component (X) may be a single atom structure or a multi-atom structure. The carrier component (X) may contain a silicon atom to which the refractive index modifying group (Y) is bonded. In this case, the silicon atom acts as a central atom of the cluster-like refractive index modifying group. The carrier component (X) may be composed of other elements. For example, phosphorus, nitrogen, germanium, or carbon may be used in place of silicon as the central atom of the cluster-like refractive index correction group. As long as at least two refractive index modifying groups (Y) can be bonded to the carrier component (X) and the carrier component (X) can be bonded to the silicon atom of the cyclic siloxane via an alkanedyl bridge, the carrier component ( The choice of X) is not important.

  The carrier component is preferably bonded to the cyclic siloxane monomer with the refractive index modifying group already bonded to the carrier component. Therefore, the cluster-like refractive index correcting group according to the present invention preferably includes a carrier component (X) to which the refractive index correcting group (Y) is already bonded. The clustered refractive index modifying groups (X + Y) according to the present invention are compounds such as triphenylsilane, diphenylsilane, triphenyldimethyldisiloxane, diphenylalkyldimethyldisiloxane which all react easily with vinyl-containing siloxane precursors. ) And a carrier and a refractive index correcting group are combined and appropriately introduced into the cyclic siloxane monomer.

  Further, very suitable compounds for introducing a cluster-like refractive index correcting group into a cyclic siloxane monomer include triphenylvinylsilane, diphenylalkylvinylsilane, phenyldialkylvinylsilane, triphenyldimethylvinyldisiloxane, diphenylethene, 3 , 3,3-triphenyl-1-propene, 3,3-diphenyl-1-propene, or any other vinyl reactive polyphenyl compound, all of which are readily hydride-containing siloxane precursors. react.

  Triphenylsilane and triphenylvinylsilane are preferred compounds, and according to these compounds, a cluster-like refractive index correcting group can be introduced into the polysiloxane precursor or polysiloxane according to the present invention. From the above description, those skilled in the art can easily determine which compound is used to introduce a cluster-like refractive index correcting group into a cyclic siloxane monomer.

In one embodiment, the method for producing the high refractive index siloxane (co) polymer of the present invention comprises:
a) a step of chemically modifying a cyclic siloxane by causing an addition reaction in the presence of an addition reaction catalyst, wherein at least two cluster-like refractive index modifying groups are bonded via one alkanedyl bridge. Attaching an index modifying group to the backbone via an alkanedyl crosslink by an addition reaction so that it is attached to the backbone of the cyclic siloxane;
b) accelerating subsequent polymerization of the resulting reaction product, thereby forming a high refractive index siloxane (co) polymer;
Is included.

  The preferred method described above for producing high refractive index siloxane (co) polymers provides a number of advantages over conventional methods, and the preferred method described above provides a high refractive index suitable for the production of eyeball lenses. It can be suitably used for producing a siloxane (co) polymer.

  In another embodiment, an addition reaction can be performed on polysiloxane (see FIG. 3B). In order to perform such an addition reaction on the polymer, the viscosity of the raw material may be lowered by a solvent such as methanol or toluene. Since the reactive groups present in the reaction mixture are diluted with a solvent and the reaction rate is reduced, the reaction temperature may be increased or the reaction time may be increased.

  In the method of the present invention, addition reaction to polysiloxane is very suitable, but such addition reaction generally requires more appropriate control than the addition reaction to the above-mentioned cyclic monomer. Furthermore, the reaction efficiency, that is, the degree of occurrence of the addition reaction is generally lower than in the case of the addition reaction with respect to the cyclic monomer. In addition, the polymer material of the present invention having a high refractive index value may be formed by using an addition reaction of the above-described monomer to cyclic siloxane. On the other hand, the molecular weight of each molecule of the polysiloxane polymer of the present invention is generally well controllable when cluster-like refractive index modifying groups are added to a siloxane (co) polymer having a predetermined molecular weight. The higher the molecular weight obtained by this example, the higher the strength of the crosslinked high refractive index polymer. In general, the amount of polymer material to be modified, the molecular weight of the polymer, the distribution of reacted groups in the polymer, and thus the refractive index and mechanical properties of the material produced will be based on the description herein. It may be properly controlled by a vendor.

  To produce the polysiloxanes of the present invention suitable for use in eyeball lenses, one skilled in the art can select a suitable siloxane (co) polymer in combination with a carrier group. The reactive group on the polysiloxane side may be appropriately selected according to the addition reaction employed. One very suitable (co) polymer is, for example, a combination of dimethylsiloxane and vinylmethylsiloxane. The (co) polymer as a starting material must be of high molecular weight so that the modified (co) polymer is a strong and flexible material. The solvent is preferably dried and removed by distillation before use. In order to minimize adverse effects such as contamination and non-uniform cross-linking during modification, it is preferred that reactive groups such as vinyl groups are randomly arranged in the polymer and uniformly distributed. This may be accomplished, for example, by setting a reaction time sufficient for copolymerization to occur between cyclosiloxanes (eg, octamethylcyclotetrasiloxane, tetravinyltetramethylcyclotetrasiloxane).

  It is preferred that the ratio and amount of reactive groups such as vinyl groups in the copolymer used in the polymer-based process for producing high refractive index polysiloxanes of the present invention be optimized. The amount of reactive groups should be high enough that the refractive index modifying group (eg, triphenylsilane group) is sufficiently bound (meaning that the desired refractive index is obtained) during the modifying reaction (addition reaction). preferable. However, the amount of reactive groups is low enough to produce an almost complete correction reaction, i.e. a small amount of unreacted groups remain in the polymer that allows the polymer molecules to properly crosslink during the crosslinking reaction. It is preferable that the amount is small. The reaction time at a certain reaction temperature may be optimized so that the reactive groups remaining in the polymer have values suitable for carrying out a crosslinking reaction therebetween.

  When a clustered refractive index modifying group such as triphenylsilane is reacted with a cyclic siloxane precursor such as tetravinyltetramethylcyclotetrasiloxane according to one method of the present invention, the precursor reactive group is highly Subjected to the addition reaction in a controlled manner. By appropriately selecting the values of reaction parameters such as time, temperature and addition reaction catalyst concentration, the reactive groups of the precursor can be modified to the desired level and even substantially completely.

  One advantage of the addition reaction to the cyclic monomers of the present invention is that the product of the addition reaction (the cyclic monomer is modified by the addition of a carrier compound having a refractive index modifying group) is produced by conventional methods. It is easier to purify than the highly viscous polysiloxanes. When the polysiloxane of the present invention is formed under conditions optimal for the addition reaction to the cyclic monomer, usually only a few unreacted reactive groups remain. In such a situation, in order to make the amount of free vinyl groups advantageous for proper crosslinking in a high molecular weight (usually about 1 to 5 mol%) polymer, for example, Additional vinyl siloxane is required.

  In contrast, polysiloxanes having refractive index modifying groups formed by conventional methods generally have free unreacted reactive groups in a non-uniformly distributed state or to an uncontrolled extent. Effective control of the crosslinking reaction and addition reaction is hindered. Accordingly, the present inventor first completed the addition reaction between the clustered refractive index modifying group and the polysiloxane polymer in order to be suitable for use in an ocular lens, and then a high refractive index silicone material. By cross-linking the polymer to obtain a polysiloxane containing cluster-like refractive index modifying groups that are chemically bonded to the polysiloxane backbone via alkanediyl crosslinks, For example, the amount of unreacted reactive groups can be reduced as compared with the conventional method, and undesirable side reactions such as premature gelation due to the presence of a large amount of unreacted reactive groups do not occur. I found out. Another important advantage of this method is that the high refractive index polysiloxane polymer produced is suitable for application in injection molding for the production of eye lenses.

  In one embodiment of the method of the present invention, an addition reaction is carried out on the monomer precursor to make the distribution of reactive refractive index modifying groups uniform. Furthermore, the reaction takes place at a relatively low temperature and for a relatively short time compared to the addition reaction to the polymer, thereby reducing the possibility of unwanted crosslinking between the reactive groups of each precursor. .

  When the polysiloxane production process according to the present invention is carried out on several combinations of cyclic siloxane monomers and siloxane monomers modified with clustered refractive index modifying groups, (co) polymerization A catalyst is used.

  While not intending to be bound by the exact mechanism of reaction, a high refractive index siloxane (co) polymer or siloxane oligomer or monomer is one aspect of the present invention. In fact, in this application the terms “modified monomer”, “siloxane (co) polymer”, “polymer” in relation to the product obtained by the modification reaction of the monomeric cyclic siloxane as described above are , Defined as the reaction product of an addition reaction in which a cyclic siloxane monomer is modified with a clustered refractive index modifying group in any state.

  In one preferred embodiment, the reaction mixture for carrying out the addition reaction according to the present invention has a molar ratio of about 10: 1 to about 1:10, more preferably about 1: 1 to about 1:10. It is preferred to include the cyclic siloxane and the clustered refractive index modifying group in a molar ratio, more preferably in a molar ratio of about 1: 4. Further, the reaction mixture preferably contains a certain amount of addition reaction catalyst depending on the type of catalyst, but in the case of platinum divinyltetramethyldisiloxane, an amount of about 1 to 200 ppm, preferably about 10 ppm is employed. May be. The reaction mixture may also contain additives such as vinyl reactive or hydride reactive UV screening agents. It is preferred to remove air from the reaction mixture. The reaction preferably occurs in an inert atmosphere such as a nitrogen atmosphere.

  Suitable reaction conditions include a reaction temperature of about 30-150 ° C, preferably about 70-100 ° C, more preferably about 90 ° C. The mixture is preferably stirred at the reaction temperature and the reaction is carried out for about 6 to 168 hours, preferably about 72 to 120 hours. The reaction may also be stopped at 50 to 99% of the maximum level of addition.

  A particularly suitable method for the production of the high refractive index siloxane (co) polymer of the present invention is to modify tetravinyltetramethylcyclotetrasiloxane as a cyclic siloxane precursor with triphenylsilane, Example 1 Is exemplified. An example of modification of trivinylpentamethyltetrasiloxane with triphenylsilane is illustrated in FIG. 3A.

  As the addition reaction catalyst, any catalyst for hydrosilylation such as a platinum group metal component or a Speiers catalyst may be used. In one preferred embodiment, Karstedt catalyst (platinum divinyltetramethyldisiloxane) is used.

  Another reactant used in the production of the high refractive index siloxane (co) polymer of the present invention produces a clustered refractive index modifying group as a Grignard reagent, which is used as a cyclic hydride-containing siloxane precursor. Formed by contact with the body. Such methods are well known in the art.

  Addition reaction to cyclic siloxane monomer, specific refractive index, high flexibility, high mechanical strength, or various functional groups (for example, vinyl group, hydride group or alkoxy group under Pt catalyst) In order to obtain a (co) polymer having a group that promotes crosslinking, the monomer may be converted to another cyclic siloxane monomer (hereinafter referred to as a comonomer) or other (low refractive index). ) By copolymerizing with polysiloxane, a high refractive index siloxane (co) polymer may be formed according to the preferred method of the present invention.

  One important feature of this (co) polymer is that their degree of polymerization is sufficiently high. In that case, the density of crosslinking may be low, and an elastic material having sufficient strength to be used for a foldable eye lens can be obtained. After crosslinking, a transparent material having a tensile strength of 1 MPa (minimum value) and an elongation at break of 50% (minimum value) is obtained. Another important feature is that in both cases where monomers are used and polymers are used, refractive index modifying groups are introduced into the (co) polymer before crosslinking occurs. That is. It is also possible to purify the (co) polymer before the high refractive index (co) polymer is used. The non-crosslinked polymer of the present invention is applicable to injection molding. In a typical two-component system, a cross-linking material is added to one component and a catalyst is added to the other component. Curing takes place in the mold.

  Thus, according to the present invention, a high refractive index siloxane (co) polymer or monomer can be derived from a high refractive index siloxane (co) polymer in any of several ways.

  For example, a high refractive index siloxane (co) polymer is mixed and copolymerized with another polysiloxane in the presence of a (co) polymerization catalyst (and optionally a solvent), thereby producing a high refractive index polysiloxane. (Co) polymers may be formed. Also, a (co) polymer or a modified monomer according to the present invention is formed, and the (co) polymer or the modified monomer is converted to a cyclic siloxane copolymer in the presence of a (co) polymerization catalyst. A high refractive index polysiloxane may be formed by reacting with a monomer.

  A number of cyclic comonomers are suitable for use in the copolymerization described above to form the high refractive index siloxane (co) polymers according to the present invention. The comonomer itself may or may not contain a refractive index modifying group. The comonomer may or may not contain a reactive group such as a hydride group or a vinyl group. Examples of copolymerizable cyclic comonomers include tetravinyltetramethylcyclotetrasiloxane, trivinyltrimethylcyclotrisiloxane, octamethylcyclotetrasiloxane, hexamethylcyclotrisiloxane, trimethyltriphenylcyclotrisiloxane, tetra Group consisting of methyltetraphenylcyclotetrasiloxane, trifluoropropylmethylcyclotrisiloxane, hexaphenylcyclotrisiloxane, octaphenylcyclotetrasiloxane, or (co) polymers derived from these cyclic (co) monomers There are cyclic comonomers or comonomers that are more selected.

One method for producing the (co) polymer according to the invention is by stirring the siloxane monomer modified with triphenyl in boiling methanol, recovering by precipitation and discharging the boiling methanol. Purifying siloxane monomers modified with triphenyl. The resulting white paste is dried in a vacuum oven until it becomes a transparent material. This material appears to be a glassy solid at room temperature. This material is then mixed with octamethylcyclotetrasiloxane and a small amount of tetravinyltetramethylcyclotetrasiloxane. A (co) polymerization catalyst such as potassium cyanolate dissolved in purified and dried dimethyl sulfoxide (DMSO) is then added. In this case, it is preferred to use 10 ⁻⁶ to 10 ⁻⁵ mol of potassium cyanolate per g of mixture. The mixture is reacted in an inert atmosphere (nitrogen) at a reaction temperature of 10 to 200 ° C., preferably 150 to 200 ° C. In that case, the reaction is preferably carried out in an inert atmosphere for 1 to 400 hours until a transparent viscous material is formed. In particular, the reaction time is preferably 96 hours or longer so that the siloxane groups are completely randomly distributed in the copolymer. Instead of potassium cyanolate, other basic catalysts such as potassium hydroxide or sodium hydroxide may be used as the (co) polymerization catalyst. The presence of DMSO is not essential, but the presence of DMSO improves the reaction rate for potassium salts. Tetravinyltetramethylcyclotetrasiloxane is added after the copolymerization of octamethylcyclotetrasiloxane with the modified monomer to prevent gel formation due to the high concentration of reactive vinyl groups. In this step, it may be copolymerized at about 100 ° C.

  When the polymer of the present invention is produced by another method, that is, a polymer method as shown in FIG. 3B, any polysiloxane homopolymer having a high molecular weight as a cluster-like refractive index modifying group. More preferably, it may be reacted with a siloxane (co) polymer. The molecular weight should be 5,000 to 1,000,000 g / mol, more preferably 10,000 to 500,000 g / mol.

  For example, the addition reaction of triphenylsilane as a cluster-like refractive index correction group may be performed on a siloxane (co) polymer containing a limited number of vinyl groups. The number of vinyl groups in the (co) polymer must be selected so as to obtain a modified (co) polymer with a relatively small number of unreacted vinyl groups remaining, Substantially completely removable by a suitable crosslinking reaction between the modified (co) polymer and a suitable crosslinking material for forming the silicone material. The amount of unreacted vinyl groups remaining before cross-linking should be from 1 to 10 mol%, most preferably from 2 to 5 mol%.

  The high refractive index (co) polymers of the present invention may be converted to other high refractive index (co) polymers of the present invention or other polysiloxanes to form (co) polymers having the desired refractive index. It may be copolymerized or rearranged with cyclosiloxane.

  By copolymerizing a highly phenylated siloxane polymer with a siloxane polymer having low aromatic substitution or a phenyl-free siloxane polymer using the method described above, 1.4-1. A (co) polymer having a refractive index of 6 can be produced.

ここにＲはアルキルラジカル、置換されたアルキルラジカル、アリールラジカル、置換されたアリールラジカル、ナフチルラジカルの如き芳香族ラジカル、シクロアルキルラジカル、アリールアルキルラジカル、アリルラジカル、ビニル、ヒドリドよりなる群より個別に選択される。 The copolymer according to the present invention has the following chemical formula:

Where R is independently selected from the group consisting of alkyl radicals, substituted alkyl radicals, aryl radicals, substituted aryl radicals, aromatic radicals such as naphthyl radicals, cycloalkyl radicals, arylalkyl radicals, allyl radicals, vinyl and hydrides. Selected.

  R1 is an alkyl radical, a substituted alkyl radical, an aryl radical, a substituted aryl radical, an aromatic radical such as a naphthyl radical, a cycloalkyl radical, an arylalkyl radical, an allyl radical, vinyl, hydride, a monovalent having a large number of bonds Selected from the group consisting of monovalent hydrocarbon radicals having a hydrocarbon radical or a substituted equivalent thereof, a silicon hydride group and a triphenylsiloxane group, but containing a vinyl group or a hydride group preferable.

  R2 is preferably a triphenylsilylalkyl radical, but a triarylsilylalkyl radical, diarylalkylsilylalkyl radical, aryldialkylsilylalkyl radical, trialkylalkylsilyl radical, tricycloalkylsilylalkyl radical, dicycloalkylalkylsilylalkyl It may be selected from the group consisting of radicals, cycloalkyldialkylsilylalkyl radicals.

  R3 is individually selected from the group consisting of alkyl radicals, substituted alkyl radicals, aryl radicals, substituted aryl radicals, aromatic radicals such as naphthyl radicals, cycloalkyl radicals, arylalkyl radicals, allyl radicals, vinyl, hydrides. However, an alkyl radical is preferable, and a methyl radical is more preferable.

m is from 10 to about 2,000,000, preferably from about 100 to about 100,000.
n is from 10 to about 2,000,000, preferably from about 100 to about 500,000, in particular m and n have a molecular weight high enough to be a strong and flexible material after crosslinking of the polymer. It is a value that forms a polymer.

For example, divinyltetramethyldisiloxane may be used as the end group.
In order to improve the material properties in accordance with the related application, the polymer resin is further terminated with an end group (empirical formula is R ₃ SiO _0.5 ), branch point, T resin (empirical formula is RSIO _1.5 ), The group (empirical formula is SiO ₂ ), may include structures known to those skilled in the art. These organopolysiloxane (co) polymers are known as MQ resins.

  The polymer resin may contain an alkyl group between the polysiloxane chains, such as a crosslinking group obtained by terminal crosslinking.

  The presence of unreacted vinyl groups as part of the siloxane (co) monomer or (co) polymer allows the (co) polymer to be crosslinked as described above. Further, unreacted vinyl groups may be intentionally introduced by selecting reaction conditions so that not all reactive groups (for example, hydride groups and vinyl groups) on the precursor monomer side will react. Therefore, such unreacted vinyl groups are intentionally introduced into the polysiloxane of the present invention so that a crosslinking reaction can be performed. Thus, additional crosslinking is performed to form a polymer with good mechanical properties suitable for use in ocular lenses.

  As the crosslinking agent, any siloxane (co) polymer having a hydride group or a vinyl group may be used in the process of the present invention, depending on the composition of the polymer to be crosslinked. For example, a (co) polymer of methylhydrosiloxane and phenylmethylsiloxane, a (co) polymer of methylhydrosiloxane and diphenylsiloxane, a (co) polymer of methylvinylsiloxane and phenylmethylsiloxane, or a combination of these compounds May be. Further, for example, tetrakis (dimethylsiloxy) silane, dimethylsilane, methylsilane, or 1,1,3,3-tetramethyldisiloxane may be used as a crosslinking agent. Other crosslinking agents may also be used.

  Functional groups that contribute to crosslinking may be introduced into the (co) polymer. Examples include alkoxy, acetoxy, ketoxime, amine, (meth) acrylate, and epoxy functional siloxane (co) polymer. (Meth) acrylates containing structural units such as acryloxypropyl can be crosslinked with ultraviolet and visible light in the presence of a suitable light inhibitor. For example, siloxane units modified with epoxy can be electron beam cured.

  It is preferred that the crosslinking does not proceed too quickly at room temperature. For example, 1,2,3,4-tetramethyl-1,2,3,4-tetravinyl-to improve the handling time and control processing time required for mixing different (co) polymer components and injection molding. Crosslink inhibitors such as cyclotetrasiloxane may be used. Such inhibitors may be added to the reaction mixture of the addition reaction in an amount of 0.01 to 10 wt% based on the weight of the polymer.

  During or prior to polymerization or copolymerization or crosslinking, additives such as UV screening agents and other additives such as dyes may be introduced into the reaction mixture. As an ultraviolet blocking agent, vinyl functional or hydride functional benzotriazole, vinyl functional or hydride functional 2-hydroxybenzophenone, allylbenzophenone (monoallylbenzophenone), vinyl in an amount of 0.01 to 5 wt% based on the weight of the polymer Functional or hydride functional benzotriazoles may be used.

  High refractive index siloxane (co) polymers and modified monomer precursors according to the present invention exhibit a refractive index of at least 1.4, preferably at least 1.65. According to the invention, the refractive index is measured with an Abbe refractometer.

  The high refractive index siloxane (co) polymers according to the invention are very suitable for use in numerous applications. In particular, optical lenses, optical fibers, eye lenses for surgery for cataracts, refractive index and recovery, ocular devices such as occlusion devices, lacrimal gland devices, contact lenses, eye applications, glass, windows, windshields, transparent coatings, hair care products In applications where light refraction and optical appearance are important, such as cosmetics, the materials of the present invention can be beneficially utilized. In one most preferred embodiment, the high refractive index siloxane (co) polymer of the present invention is used in the manufacture of ocular lenses.

  Forming an ocular lens or optical device with the high refractive index siloxane (co) polymer of the present invention may be performed by liquid injection molding or by casting or compression molding or other molding. These processes are well known in the art. The vulcanization temperature suitable for these steps is 20 to 200 ° C. In one more preferred embodiment, injection molding is a cheap and rapid molding process that forms high quality lenses, so that the polymer of the present invention is preferably highly refractive by a process known as injection molding. It is used when manufacturing an ocular lens having a certain degree of flexibility.

The following examples show some specific examples of the present invention and do not limit the present invention.
Example 1
Method by monomer: addition to monomer Tetravinyltetramethylcyclotetrasiloxane and triphenylsilane were mixed in a molar ratio of 1: 4. 11 ppm of platinum divinyltetramethyldisiloxane was added as a 2.5 wt% xylene solution. Air was removed by replacing the air with an argon atmosphere and the mixture was heated to 90 ° C. The mixture was stirred for 96 hours at the reaction temperature. After 96 hours, a small amount of vinyldiethylmethylsilane or other vinyl-containing silane was added and the mixture was stirred at 90 ° C. for 24 hours in an argon atmosphere.

Monomer method: modified monomer purification After the addition reaction, the mixture was cooled to room temperature and 2 parts by volume of methanol were added. After stirring for 4 hours in boiling methanol, stirring was stopped and the mixture was allowed to precipitate for 2 hours. Boiling methanol was removed, 2 parts by volume of fresh methanol was added, and the mixture was stirred in boiling methanol overnight. Stirring was stopped again and the mixture was allowed to settle and the boiling methanol was removed. The material thus obtained was dried in a vacuum oven at 70 ° C. to remove methanol and then cooled to room temperature.

  A transparent vitreous solid having a refractive index of 1.6 to 1.66 as measured with a refractometer was obtained. Nuclear magnetic resonance analysis confirmed that unreacted triphenylsilane had been removed and the vinyl group was almost completely eliminated (greater than 92%). Instead, protons from bridging alkyl groups and protons from phenyl groups formed by addition reaction were present.

Monomer Method: Polymerization Forming a (co) polymer from a tetravinyltetramethylcyclotetrasiloxane monomer modified with triphenylsilane may be done in any of several ways.

  Modified tetratriphenylsilyl ethane tetramethylcyclotetrasiloxane monomers (over 92% of converted vinyl groups) include, for example, octamethylcyclotetrasiloxane and tetravinyltetramethylcyclotetrasiloxane (or equivalent cyclosiloxane) It may be reacted with other cyclic monomers such as

  Alternatively, a modified tetratriphenylsilylethane tetramethylcyclotetrasiloxane monomer (over 92% of the converted vinyl groups) may be a (co) polymer such as polydimethylsiloxane or polydimethylvinylmethylsiloxane, or for example polydimethyl It may be copolymerized with a combination of siloxane monomer and tetravinyltetramethylcyclotetrasiloxane monomer.

The following experiments illustrate the present invention.
1.2 g of modified monomer (converted vinyl groups> 92%) was mixed with 1.0 g of octamethylcyclotetrasiloxane. In tests conducted in parallel, a small amount of T resin or Q resin was added to improve the properties of the polymer. In other parallel tests, small amounts of other monomers containing functional groups such as hydride groups or vinyl groups were added. A small amount of potassium trimethylsilanolate was added as a catalyst to these mixtures. The mixture was stirred in a nitrogen atmosphere at 100 ° C. for 24 hours and at 150-200 ° C. for 120 hours. As a result, a transparent polymer was obtained. After cooling to 100 ° C., 0.059 g of tetravinyltetramethylcyclotetrasiloxane was added and the reaction was carried out for 4 hours in a nitrogen atmosphere. After cooling to 50 ° C., dichlorodimethylsilane was added as a chain extender, or chlorodimethylvinylsilane was added as an end group former. In the method as described in this specification, for example, trichlorosilane or dichlorodiphenylsilane may be added as a chain extender.
The polymer is dried, heated and stirred in air at 90 ° C. for 2 hours, or in the presence of divinyltetramethyldisiloxane and in parallel tests 1, The mixture was stirred for 2 hours in an argon atmosphere in the presence of other vinyl group-containing compounds such as 4-divinyltetramethyldisilylethane and butadiene.

Example 2
Polymer method: (Pre) polymer formation 0.025 g of potassium silanolate, 6.7 g of tetravinyltetramethylcyclotetrasiloxane, 13.3 g of octamethylcyclotetrasiloxane, 40 μl of divinyltetramethyl Disiloxane was mixed and allowed to react for 96 hours at 100 ° C. in an argon atmosphere. After the formed copolymer was cooled to 50 ° C., 0.025 g of dimethylvinylchlorosilane was added to the copolymer and allowed to react for 24 hours while stirring in an argon atmosphere. .

Polymer Method: Addition to (Co) polymer The copolymer contains 10 ppm of platinum catalyst and an amount (a sufficient amount to be 1 mole per mole of vinyl groups in the copolymer). Added. The mixture was stirred at 50 ° C. in an argon atmosphere until 1 to 5 mol% (measured by nuclear magnetic resonance analysis) vinyl groups remained in the copolymer.

Polymer method: purification After the addition reaction, the mixture was cooled to room temperature and 2 parts by volume of methanol were added. After stirring for 4 hours in boiling methanol, stirring was stopped and the mixture was allowed to precipitate for 2 hours. Boiling methanol was removed, 2 parts by volume of fresh methanol was added, and the mixture was stirred in boiling methanol overnight. Stirring was stopped again and the mixture was allowed to settle and the boiling methanol was removed. The material thus obtained was dried at 70 ° C. in a vacuum furnace and then cooled.

  The polymer is dried, heated and stirred in air at 90 ° C. for 2 hours, or in the presence of divinyltetramethyldisiloxane and in parallel tests 1, The mixture was stirred for 2 hours in an argon atmosphere in the presence of other vinyl group-containing compounds such as 4-divinyltetramethyldisilylethane and butadiene.

Example 3
Ocular Lens (IOL) Preparation The (co) polymer of Example 1 was divided into two parts. A hydride functional crosslinker (tetrakisdimethylsiloxysilane) was added to one part so that the ratio of hydride groups to vinyl groups in the material after mixing the two parts was 1: 1. In addition, 10 ppm of platinum divinyltetramethyldisiloxane was added to the other portions. In this part, 0.1 wt% of 1,2,3,4-tetramethyl-1,2,3,4-tetravinyl-cyclotetrasiloxane crosslinking inhibitor, based on the weight of the polymer, is a hydride functional crosslinking agent. A benzophenone UV blocker (0.1 wt% based on the weight of the polymer) was added to both parts, which was added together with and was capable of reacting with the (co) polymer during the hydrosilylation cure.

  These two parts were mixed in an extrusion molding machine, and liquid was injected into the mold at a vulcanization temperature of 110 ° C. to form an eyeball lens body. Post-curing was performed at 120 ° C. for 2 hours in an oven. A foldable silicone eyeball lens body having a high refractive index of 1.50 and high transparency was obtained.

2 illustrates cyclic siloxanes that may be used as monomer precursors to form high refractive index siloxane (co) polymers according to the present invention. The refractive index modifying group shows a cluster incorporated in the high refractive index siloxane (co) polymer according to the present invention, and also the polysiloxane backbone, alkanedyl crosslinks, carrier component (X), refractive index modifying group (Y ). It is. A is an explanatory view of one embodiment of the present invention showing an addition reaction between triphenylsilane and trivinylpentamethylcyclotetrasiloxane and a high refractive index siloxane (co) polymer obtained thereby, B These are explanatory drawings of one Example of this invention which shows the addition reaction between triphenylsilane and divinylhexamethyltetrasiloxane and the high refractive index siloxane (co) polymer obtained by this.

Claims (40)

  An ophthalmic lens comprising a cross-linked high refractive index polysiloxane, wherein the polysiloxane is a polysiloxane via an alkane di-crosslink such that one alkane di cross-link connects at least two refractive index modifying groups to the polysiloxane backbone. An ocular lens comprising a clustered refractive index modifying group chemically bonded to a siloxane backbone.   The eyeball according to claim 1, wherein the refractive index correcting group is individually selected from the group consisting of a cyclic hydrocarbon portion, a straight chain hydrocarbon portion, and a side chain hydrocarbon portion. lens.   The ocular lens according to claim 1, wherein the refractive index correcting group is individually selected from the group consisting of an aromatic group, an aryl group, an arylalkyl group, a cycloalkyl group, and a side chain alkyl group. .   The eyeball lens according to claim 3, wherein the refractive index correcting group is a phenyl group.   The ocular lens according to any one of claims 1 to 4, wherein the alkanediyl cross-linking is an ethanediyl cross-linking.   The eyeball lens according to claim 1, wherein the cluster-like refractive index correction group includes a silicon atom in the center.   The polysiloxane is tetravinyltetramethylcyclotetrasiloxane, trivinyltrimethylcyclotrisiloxane, octamethylcyclotetrasiloxane, hexamethylcyclotrisiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, trifluoropropylmethyl. A cyclic comonomer selected from the group consisting of cyclotrisiloxane, hexaphenylcyclotrisiloxane, octaphenylcyclotetrasiloxane, or a (co) polymer derived from these cyclic (co) monomers, or 7. A (co) polymer derived from a (co) polymerization reaction between a comonomer and a high refractive index siloxane monomer, according to any one of claims 1 to 6 Eye lens. An ocular lens comprising a copolymer according to the following chemical formula I:

Wherein R is individually selected from the group consisting of alkyl radicals, substituted alkyl radicals, aryl radicals, substituted aryl radicals, aromatic radicals, cycloalkyl radicals, arylalkyl radicals, allyl radicals, vinyls, hydrides,
R1 is an alkyl radical, substituted alkyl radical, aryl radical, substituted aryl radical, aromatic radical, cycloalkyl radical, arylalkyl radical, allyl radical, vinyl, hydride, an optionally substituted one having multiple bonds Individually selected from the group consisting of an optionally substituted monovalent hydrocarbon radical having a valent hydrocarbon radical, a silicon hydride group and a triphenylsiloxane group;
R2 is a group consisting of triarylsilylalkyl radical, diarylalkylsilylalkyl radical, aryldialkylsilylalkyl radical, trialkylalkylsilyl radical, tricycloalkylsilylalkyl radical, dicycloalkylalkylsilylalkyl radical, cycloalkyldialkylsilylalkyl radical More selected,
R3 is individually selected from the group consisting of alkyl radicals, substituted alkyl radicals, aryl radicals, substituted aryl radicals, aromatic radicals, cycloalkyl radicals, arylalkyl radicals, allyl radicals, vinyl, hydrides,
m is 10 to about 2,000,000;
n is from 10 to about 2,000,000.   9. The ocular lens according to claim 8, wherein R2 is a triphenylsilylethyl radical.   10. The ocular lens according to claim 8, wherein R1 is vinyl or hydride and R3 is a methyl radical.   One alkanediyl crosslink includes clustered refractive index modifying groups that are chemically bonded to the siloxane backbone via alkanediyl crosslinks to bond at least two refractive index modifying groups to the siloxane backbone. High refractive index siloxane (co) polymer.   The refractive index correction group is individually selected from the group consisting of a cyclic hydrocarbon portion, a linear hydrocarbon portion, and a side chain hydrocarbon portion. Co) polymer.   12. The (refractive index modifying group) is individually selected from the group consisting of an aromatic group, an aryl group, an arylalkyl group, a cycloalkyl group, and a side chain alkyl group. ) Polymer.   14. The (co) polymer according to claim 13, wherein the refractive index correcting group is a phenyl group.   15. The (co) polymer according to any one of claims 11 to 14, wherein the alkanediyl cross-link is an ethanediyl cross-link.   The (co) polymer according to any one of claims 11 to 15, wherein the cluster-like refractive index correcting group contains a silicon atom in the center. Copolymer according to the following chemical formula I:

Wherein R is individually selected from the group consisting of alkyl radicals, substituted alkyl radicals, aryl radicals, substituted aryl radicals, aromatic radicals, cycloalkyl radicals, arylalkyl radicals, allyl radicals, vinyls, hydrides,
R1 is an alkyl radical, substituted alkyl radical, aryl radical, substituted aryl radical, aromatic radical, cycloalkyl radical, arylalkyl radical, allyl radical, vinyl, hydride, an optionally substituted one having multiple bonds Individually selected from the group consisting of an optionally substituted monovalent hydrocarbon radical having a valent hydrocarbon radical, a silicon hydride group and a triphenylsiloxane group;
R2 is a group consisting of triarylsilylalkyl radical, diarylalkylsilylalkyl radical, aryldialkylsilylalkyl radical, trialkylalkylsilyl radical, tricycloalkylsilylalkyl radical, dicycloalkylalkylsilylalkyl radical, cycloalkyldialkylsilylalkyl radical More selected,
R3 is individually selected from the group consisting of alkyl radicals, substituted alkyl radicals, aryl radicals, substituted aryl radicals, aromatic radicals, cycloalkyl radicals, arylalkyl radicals, allyl radicals, vinyl, hydrides,
m is 10 to about 2,000,000;
n is from 10 to about 2,000,000.   The copolymer according to claim 17, wherein R2 is a triphenylsilylethyl radical.   The copolymer according to claim 17 or 18, wherein R1 is vinyl or hydride, and R3 is a methyl radical.   Poly produced by chemically bonding a clustered refractive index modifying group to the siloxane backbone via an alkanedyl crosslinking bond so that one alkanedyl crosslinking bond binds at least two refractive index modifying groups to the siloxane backbone. Siloxane (co) polymer.   The polysiloxanes thus formed are chemically bonded to the siloxane backbone via alkanediyl crosslinks so that one alkanediyl crosslinkage binds at least two refractive index modification groups to the siloxane backbone. A polysiloxane (co) polymer produced by copolymerizing a siloxane (co) polymer with one of another polysiloxane and cyclosiloxane.   The polysiloxane (co) polymer according to claim 20 or 21, wherein the refractive index correcting group is derived from triphenylsilane.   The polysiloxane (co) polymer according to any one of claims 20 to 22, which is substantially not crosslinked.   The polysiloxane (co) polymer according to any one of claims 11 to 23, further comprising an additive of at least one of an ultraviolet blocker, a dye, a pigment, and a crosslinking inhibitor.   Monomer cyclohexane containing a clustered refractive index modifying group chemically bonded to the siloxane backbone via an alkanedyl crosslinking bond so that one alkanedyl crosslinking bond binds at least two refractive index modifying groups to the siloxane backbone. Siloxane.   A method for producing an ocular lens using any of the polysiloxane (co) polymer according to any one of claims 11 to 24 and the monomeric cyclosiloxane according to claim 25. a) a step of chemically modifying a cyclic siloxane by causing an addition reaction in the presence of an addition reaction catalyst, wherein at least two cluster-like refractive index modifying groups are bonded via one alkanedyl bridge. Attaching an index modifying group to the backbone via an alkanedyl crosslink by an addition reaction so that it is attached to the backbone of the cyclic siloxane;
b) accelerating subsequent polymerization of the resulting reaction product, thereby forming a high refractive index polysiloxane (co) polymer;
A method for producing a polysiloxane (co) polymer having a high refractive index containing a) reacting a cyclic siloxane of formula II below with any of triphenylsilane, diphenylsilane, triphenyldimethyldisiloxane, diphenylalkyldimethyldisiloxane in the presence of an addition reaction catalyst;
b) promoting the subsequent (co) polymerization of the resulting reaction product, thereby forming a high refractive index polysiloxane (co) polymer;
28. The method for producing a high refractive index polysiloxane (co) polymer according to claim 27, comprising chemically modifying a cyclic siloxane of the following chemical formula II by performing:

Where R is individually alkyl, vinyl or hydride,
R1 is vinyl,
n is 0, 1, 2, or 3. a) In the presence of an addition reaction catalyst, a cyclic siloxane having the following chemical formula II is converted into triphenylvinylsilane, diphenylalkylvinylsilane, phenyldialkylvinylsilane, triphenyldimethylvinyldisiloxane, diphenylethene, 3,3,3-triphenyl- Reacting with any of 1-propene, 3,3-diphenyl-1-propene, any other hydride reactive polyphenyl;
b) promoting the subsequent (co) polymerization of the resulting reaction product, thereby forming a high refractive index polysiloxane (co) polymer;
28. The method for producing a high refractive index polysiloxane (co) polymer according to claim 27, comprising chemically modifying a cyclic siloxane of the following chemical formula II by performing:

Where R is individually alkyl, vinyl or hydride,
R1 is a hydride,
n is 0, 1, 2, or 3.   30. A method according to any one of claims 27 to 29, wherein the cyclic siloxane is a cyclic tetrasiloxane.   31. The method of claim 30, wherein the cyclic tetrasiloxane is reacted with either triphenylsilane or triphenylvinylsilane.   A high refractive index comprising reacting the (co) polymer according to any one of claims 11 to 24 with either a cyclic siloxane comonomer or a polysiloxane in the presence of a (co) polymerization catalyst. A method for producing a polysiloxane (co) polymer.   A high refractive index polysiloxane (co) polymer produced by the method according to any one of claims 27 to 31 is copolymerized with either a cyclic siloxane comonomer or a polysiloxane. A method for producing a polysiloxane (co) polymer having a high refractive index.   The cyclic siloxane is tetravinyltetramethylcyclotetrasiloxane, trivinyltrimethylcyclotrisiloxane, octamethylcyclotetrasiloxane, hexamethylcyclotrisiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, trifluoropropyl. It is selected from the group consisting of methylcyclotrisiloxane, hexaphenylcyclotrisiloxane, octaphenylcyclotetrasiloxane, or (co) polymers derived from these cyclic (co) monomers. The method according to claim 32 or 33.   A process of chemically modifying a polysiloxane (co) polymer by performing an addition reaction in the presence of an addition reaction catalyst, wherein at least two cluster-like refractive index modifying groups form one alkanedyl crosslink. A high refractive index polysiloxane comprising a step of attaching a cluster-like refractive index modifying group to the siloxane backbone of the (co) polymer via an alkanedyl crosslink by an addition reaction so as to be bonded to the siloxane backbone via (Co) polymer production method.   A process of chemically modifying a polysiloxane (co) polymer by performing an addition reaction in the presence of an addition reaction catalyst, wherein at least two cluster-like refractive index modifying groups form one alkanedyl crosslink. Attaching a cluster-like refractive index modifying group to the siloxane backbone of the (co) polymer via an alkanedyl bridge through an addition reaction so that it is bonded to the siloxane backbone via the addition reaction, and thus the modified polysiloxane A process for producing a polysiloxane (co) polymer having a high refractive index, comprising a step of (co) polymerizing a (co) polymer with any of other polysiloxanes and cyclosiloxanes.   37. A method according to claim 35 or 36, wherein the clustered refractive index modifying group is triphenylsilane.   38. A method according to any one of claims 35 to 37, wherein the high refractive index polysiloxane (co) polymer is substantially uncrosslinked.   25. A method comprising the step of forming the (co) polymer according to any one of claims 11 to 24 into an eyeball lens, wherein the step of treating includes a step of crosslinking the (co) polymer. 40. The method of claim 39, wherein the processing step comprises injection molding prior to completing the crosslinking of the (co) polymer.

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