CN1894620B - Contact lens material - Google Patents

Abstract

The present invention provides a CL material which has high oxygen permeability and mechanical strength, has a very small amount of residual unpolymerized monomer, has low water absorption and has excellent shape stability of a lens. A contact lens material comprising a copolymer obtained by polymerizing a copolymerized component of a polysiloxane-containing monomer represented by the general formula , wherein the total amount of unpolymerized monomer components remaining in the copolymer is 3.5% by weight or less, and the copolymer has an oxygen permeability of 130X 10^-11(cm²/sec)·(mLO₂/(mL. mmHg)) or higher, and the water absorption of the copolymer is 0.3 wt% or lower.

Description

contact lens material

technical field

The present invention relates to a contact lens (hereinafter referred to as CL) material. More specifically, it relates to a material that has high oxygen permeability and high mechanical strength, and at the same time, the amount of unpolymerized monomers in the CL material, the amount of water absorption is extremely small, and the shape CL material with excellent stability.

Background technique

General oxygen-permeable CL materials contain polysiloxane-based (meth)acrylate or polysiloxane-based styrene as the main component, and as other components in order to impart stain resistance, strength, and water wettability, etc. , Select monomers that match various target properties as copolymerization components and polymerize them.

However, when a multi-component system is used for copolymerization, due to the different structures and characteristics of the polymerization sites of each monomer, it is basically difficult to make them perform good copolymerization, and in most cases, it is determined by experience and expertise. However, it takes a long time and labor to carry out the copolymerization with good reproducibility and to complete the final product. In particular, when a hydrophilic monomer is selected as a copolymerization component, it is extremely difficult to perform good polymerization because it has a polarity opposite to that of the polysiloxane-based monomer as the main component. When such a system is used, it is necessary to carry out polymerization slowly over a very long time.

In addition, a hydrophilic monomer is added to impart water wettability, but basically on the surface of the lens, since polysiloxane and the like with low surface free energy appear, the effect of water wettability is not so effective by addition . In other words, the addition of a hydrophilic monomer impairs oxygen permeability.

On the other hand, in order to stabilize the CL shape, the residual components in the lens, especially the volatile components and the eluted components in aqueous solvents must be suppressed as much as possible. In addition, the water absorption rate of the lens material is also involved. When the water absorption rate exceeds the necessary amount, it is considered that the replacement phenomenon of water and the remaining components in the lens occurs, and if it remains in a slightly deformed material, the deformation is alleviated by water absorption, and the deformation of the lens may be accelerated.

Japanese Patent Application Laid-Open No. 60-142324 proposes a polymer composed of at least one of silane or styrene with a Si atom number of 15 or less, or the above-mentioned silane or styrene with a siloxane bond Oxygen-permeable hard CL made of at least one of copolymers composed of hydrophobic monomers and/or hydrophilic monomers.

However, the CL proposed in JP-A-60-142324 does not take into account the copolymerizability of the monomer components, and cannot perform good copolymerization (increased unpolymerized monomers), or spends a very long time to slowly polymerize but cannot quickly Problems such as good copolymerization exist. Specifically, when a siloxane-containing styrene monomer is copolymerized with a hydrophilic monomer (the same applies to hydrophobic monomers other than a siloxane-containing styrene monomer), since the polarity is reversed, the polymerization site The structure and polymerization characteristics are different, and when the polymerization is performed in a short time from several minutes to several hours, the polymerization reaction becomes incomplete, and many unpolymerized monomers remain in the copolymer. As a result, not only the safety to eyes is concerned, but also the shape of CL may change due to volatilization and elution of unpolymerized monomers into tear fluid, preservation solution, and the like. However, such a combination requires slow polymerization over a long period of time, which is unsatisfactory in terms of labor and production costs.

In addition, as a result of adding a hydrophilic monomer, not only the oxygen permeability is lowered, but also the water absorption of the copolymer is increased, and the deformation of the lens shape is accelerated as described above.

JP-A-6-27424 discloses a CL material having improved dimensional stability and crack resistance, characterized by containing 3.5% by weight or less of a volatile component with a molecular weight of 700 or less.

However, in order to obtain such CL, a silicone resin or CL material containing 5% by weight or less of a volatile component with a molecular weight of 700 or less must be irradiated with high-energy radiation to reduce the volatile component to 3.5% by weight or less, which is very It is cumbersome and labor-intensive, and it is not satisfactory in terms of manufacturing cost. In addition, this technology is to remove components such as volatile components (unpolymerized monomers) by performing post-treatment in CL resin materials whose volatile components are 5% by weight or less after the production of silicone resins, but only impart In order to ensure dimensional stability and crack resistance, it is not a technology to specify monomer components, compounding ratios, polymerization methods, or reduce volatile components. In addition, it does not consider the copolymerizability of monomer components. In addition, the use of a hydrophilic monomer is considered to be undesirable because it promotes deformation of the lens shape as described above.

In addition, Japanese Patent Laid-Open No. 11-326847 discloses that the silicon-based monomer having a radically polymerizable functional group with a silicon atom content of 10 to 50% in the molecule as the first component is 20 to 70 parts by weight, As the second component, there are 1 to 5 parts by weight of monomers having two or more radically polymerizable functional groups in the molecule, and as the third component, alkyl (meth)acrylates, benzene, etc., which can be copolymerized with them Ethylene or alkyl styrene is composed of 30-70 parts by weight of copolymer, CL with a specific gravity of 0.9-1.05 at 36°C and an oxygen transmission coefficient of 40 or higher. However, the CL oxygen permeability coefficient is actually 120 or lower, and it can be said that the oxygen permeability is not sufficient.

In addition, since such CL has a low specific gravity, it exchanges well with tear fluid during installation and use, and reduces the burden on the cornea. The purpose of making the surface of the lens hydrophilic by surface graft polymerization is different from the purpose of the present invention.

As mentioned above, the oxygen-permeable CL material whose main component is polysiloxane-based (meth)acrylate or polysiloxane-based styrene is a multi-component material, especially when it contains a hydrophilic monomer , is very complicated and requires a lot of labor. In addition, even through such a complicated process, it is difficult to satisfy the stability of lens shape, safety to eyes, oxygen permeability, and the like.

The present invention relates to a CL material including a copolymer obtained by polymerizing a copolymerization component of a polysiloxane-containing monomer, which has a low residual amount of unpolymerized monomer components remaining in the copolymer, has excellent oxygen permeability, and is water-absorbent The rate is low, so the shape stability, mechanical strength, eye safety, etc. are excellent, and the manufacturing cost can be reduced.

The present invention also relates to styrene-based monomers and fluoro(meth)acrylate-based monomers, by combining them with a crosslinking agent in a specific type and compounding ratio, and without adding a hydrophilic monomer, even within a few hours Copolymerization within a short period of time can still suppress the low amount of unpolymerized monomers, give full play to the properties of each monomer such as oxygen permeability, mechanical strength, and pollution resistance, and can achieve lens shape stability and eye alignment. The safety and oxygen permeability are very good, thereby reducing the manufacturing cost.

Contents of the invention

The present invention provides a CL material that has high oxygen permeability and mechanical strength, has a very small amount of residual unpolymerized monomer even if it is polymerized within several hours, has a low water absorption rate, and has excellent shape stability of a lens.

That is, the present invention relates to a contact lens material, a copolymer obtained by polymerizing a copolymerization component containing a polysiloxane-containing monomer represented by the general formula (I), and the unpolymerized monomer component remaining in the copolymer is relatively The copolymer has an oxygen transmission coefficient of 130×10 ^-11 (cm ² /sec)·(mLO ₂ /(mL·mmHg)) or higher when the total residual amount of the copolymer is 3.5% by weight or less, and The copolymer has a water absorption of 0.3% by weight or less.

[chemical 1]

(In the formula, 1 is 0 or 1, n and m are integers from 1 to 15)

The above-mentioned copolymer is preferably basically composed of a polysiloxane-containing monomer represented by the above-mentioned general formula (I) and an alkyl group having 1 to 6 carbon atoms, and at least one hydrogen atom of the alkyl group is replaced by a fluorine atom. It is obtained by polymerizing the monomer component composed of alkyl (meth)acrylate and cross-linking agent.

The above-mentioned interpolymer more preferably comprises 45 to 70 parts by weight of the polysiloxane-containing monomer represented by the above general formula (I), 20 to 45 parts by weight of the above-mentioned alkyl (meth)acrylate and 5 to 5 parts by weight of the crosslinking agent. 15 parts by weight of the copolymerization component were polymerized. In addition, these components are blended so that the total may be 100 parts by weight.

The above-mentioned copolymer more preferably further contains an ultraviolet absorber and/or a pigment.

The above-mentioned copolymer is preferably a copolymer obtained by polymerizing the above-mentioned monomer components and a crosslinking agent at 40 to 120° C. for 30 minutes to 5 hours.

In addition, the contact lens material according to the present invention contains a monomer component consisting essentially of tris(trimethylsiloxy)silylstyrene and trifluoroethyl methacrylate and a crosslinking agent. The copolymer obtained by polymerization, wherein three (trimethylsilyloxy) silyl styrene is 45 to 70 parts by weight, trifluoroethyl methacrylate is 20 to 45 parts by weight and crosslinking agent is 5 to 5 parts by weight. 15 parts by weight.

As the above-mentioned crosslinking agent, ethylene glycol dimethacrylate and/or 4-vinylbenzyl methacrylate are preferable.

It is more preferable that the above-mentioned copolymer further contains an ultraviolet absorber and/or a pigment.

The above-mentioned copolymer, the above-mentioned monomer components and crosslinking agent are more preferably obtained by polymerizing at 40 to 120° C. for 30 minutes to 5 hours.

The residual amount of unpolymerized monomer components in the above-mentioned copolymer to the copolymer is 3.0% by weight or less for tris(trimethylsiloxy)silylstyrene, and for trifluoroethyl methacrylic acid The ester is 0.5% by weight or less, the copolymer has an oxygen permeability coefficient of 130×10 ^-11 (cm ² /sec)·(mLO ₂ /(mL·mmHg)) or higher, and the copolymer has a water absorption A ratio of 0.3% by weight or less is preferable.

Moreover, this invention relates to the contact lens which consists of the said contact lens material.

Detailed ways

The present invention relates to a CL material comprising a copolymer obtained by polymerizing a copolymerization component containing a polysiloxane-containing monomer represented by general formula (I).

[Chem 2]

(In the formula, 1 is 0 or 1, and n and m are integers of 1 to 15).

The polysiloxane-containing monomer is a component that improves oxygen permeability.

As specific examples of polysiloxane-containing monomers, there are many kinds depending on the structure of the silane or siloxane-bonding moiety. As the polysiloxane-containing monomers used in the present invention, the above general formula Compound represented by (I).

Among the compounds represented by the general formula (I), 1 is preferably 0 or 1, which is easy to synthesize and produces a stable compound, and the larger n and m are, the more soft and brittle the compound is produced. Regarding n and m, it is particularly preferable to be about 1 to 5, since it has oxygen permeability, excellent hardness and rigidity, and a CL material with a high refractive index can be obtained.

In the compound represented by the above-mentioned general formula (I), the siloxane binding part can also be obtained by combining any siloxane of a straight chain and a branched chain, and the branched chain has better properties than the straight chain. Rigidity, so it is preferred.

As a representative of the compound represented by the general formula (I), for example, trimethylsilyl styrene, pentamethyldisiloxane styrene, heptamethyltrisiloxane styrene, nonamethylsilyl styrene, tetrasiloxane styrene, pentamethylheptasiloxane styrene, twenty-one methyl decasiloxane styrene, twenty seven heptamethyl trisiloxane styrene, thirty Monomethylpentadetasilyloxystyrene, bis(trimethylsiloxy)methylsilylstyrene, tris(trimethylsiloxy)silylstyrene, trimethylsilyl Silyloxy·pentamethyldisiloxy·methylsilylstyrene, tris(pentamethyldisiloxy)silylstyrene, (tris·trimethylsilyloxy)silicon Oxygenyl bis(trimethylsiloxy)silylstyrene, bis(heptamethyltrisiloxy)methylsilylstyrene, tris(methylbistrimethylsilyloxy) silyloxy)silylstyrene, trimethylsiloxybis(tritrimethylsiloxysiloxy)silylstyrene, hepta(trimethylsiloxy) Siloxy)trisiloxylstyrene, nonamethyltetrasiloxy·undecylpentasiloxy·methylsilylstyrene, tris(tritrimethylsilyloxy· Silyloxy) silyl styrene, (three trimethylsilyloxy hexamethyl) tetrasiloxy (three trimethylsiloxy) silyloxy three Methylsiloxysilylstyrene, nonamethyltetrasiloxy·undecylpentasilyloxymethylsilylstyrene, tris(tritrimethylsilyloxy· Silyloxy) silyl styrene, (three trimethylsilyloxy hexamethyl) tetrasiloxy (three trimethylsiloxy) silyloxy three Methylsiloxysilylstyrene, Nine(trimethylsiloxy)tetrasiloxylstyrene, Bis(trimethylhexasiloxy)methylsilylstyrene, etc. . These may be used alone or in admixture of 2 or more.

Among the above representative examples, in order to improve oxygen permeability, mechanical strength, workability and refractive index, compounds represented by the following formulas are preferable, for example: formula

[Formula 3]

Represented trimethylsilyl styrene; formula

[Formula 4]

Represented bis(trimethylsiloxy)methylsilylstyrene; formula

[chemical 5]

Represented tris(trimethylsiloxy)silylstyrene and the like. Among them, tris(trimethylsiloxy)silylstyrene is particularly preferred.

In the copolymer of the present invention, it is preferable that the polysiloxane-containing monomer represented by the above general formula (I) and an alkyl group have 1 to 6 carbon atoms and at least one of the alkyl groups It is obtained by polymerizing a monomer component composed of an alkyl (meth)acrylate in which hydrogen atoms are replaced by fluorine atoms and a crosslinking agent.

Here, the so-called "monomer component" means a monomer containing polysiloxane represented by the above general formula (I) and an alkyl group having 1 to 6 carbon atoms and at least one hydrogen atom of the alkyl group being The two components of fluorine atom-substituted alkyl (meth)acrylates, components other than these monomer components (polymerizable and non-polymerizable ultraviolet absorbers, pigments, polymerization initiators, and other polymerizable monomers) are not It belongs to the monomer component described in the present invention.

In addition, the term "basically" means that other polymerizable components (except polymerizable and non-polymerizable ultraviolet absorbers, pigments, and polymerization initiators) other than these monomer components can be used in a manner that can fully exert the properties of the above-mentioned monomer components. Specifically, in the mixture of the monomer component and the crosslinking agent, 10 parts by weight or less of the mixture of the monomer component, the crosslinking agent and other polymerizable monomers, preferably 5 parts by weight or lower. When other polymerizable monomers other than the above-mentioned monomer components are used in an amount of more than 10 parts by weight, the copolymerizability decreases and the amount of unpolymerized monomers increases, thereby deteriorating shape stability and safety tends to deteriorate. In addition, oxygen permeability tends to decrease.

In addition, in this specification, "... (meth)acrylate" means the generic term of two types of compounds of "... acrylate" and "... methacrylate".

As specific examples of other polymerizable monomers, for example, methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, tert-butyl (meth)acrylate, ( Methacrylic acid or Alkyl esters of acrylic acid; styrene; p-methylstyrene; m-methylstyrene; p-tert-butylstyrene; m-tert-butylstyrene; p-1,1,3,3-tetra Styryl compounds such as methyl butyl styrene; alkyl esters of itaconic acid or crotonic acid; glycidyl (meth)acrylate; tetrahydrofurfuryl (meth)acrylate; benzyl (meth)acrylate, etc. .

The number of carbon atoms in the alkyl group is 1 to 6, and at least one hydrogen atom of the alkyl group is replaced by a fluorine atom. It is an alkyl (meth)acrylate that not only maintains oxygen permeability but also improves pollution resistance and processability. ingredients.

Specific examples of alkyl (meth)acrylates in which the above-mentioned alkyl group has 1 to 6 carbon atoms and at least one hydrogen atom of the alkyl group is replaced by a fluorine atom include, for example, 2,2,2- Trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 2,2,3,3,3-pentafluoropropyl (meth)acrylate , Hexafluoroisopropyl (meth)acrylate, 2,2,3,3-tetrafluoropentyl (meth)acrylate, 2,2,3,4,4,4-hexafluorobutyl ( Meth) acrylate, 2,2,3,4,4,4-hexafluoro-tert-hexyl (meth)acrylate, 2,2,3,3,4,4,5,5-octafluoropentyl ( Meth)acrylate, etc. These may be used alone or in admixture of 2 or more. Among them, 2,2,2-trifluoroethyl methacrylate, hexafluoroisopropylmethyl Acrylates, 2,2,3,3-tetrafluoropropyl methacrylate, 2,2,3,3,3-pentafluoropropyl methacrylate are preferred, while 2,2,2-tri Fluoroethyl methacrylate is particularly preferred.

Specific examples of the crosslinking agent include, for example, ethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, di(meth)acrylate, ) triethylene glycol acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, diallyl fumarate, allyl (meth)acrylate, vinyl (meth)acrylate , trimethylolpropane tri(meth)acrylate, methacryloxyethyl(meth)acrylate, divinylbenzene, diallyl phthalate, diallyl adipate, Triallyl diisocyanate, α-methylene-N-vinylpyrrolidone, 4-vinylbenzyl (meth)acrylate, 3-vinylbenzyl (meth)acrylate, 2,2 -Bis((meth)acryloxyphenyl)hexafluoropropane, 2,2-bis((meth)acryloxyphenyl)propane, 1,4-bis(2-(meth)propene Acyloxyhexafluoroisopropyl)benzene, 1,3-bis(2-(meth)acryloyloxyhexafluoroisopropyl)benzene, 1,2-bis(2-(meth)acryloyloxy Hexafluoroisopropyl)benzene, 1,4-bis(2-(meth)acryloyloxyisopropyl)benzene, 1,3-bis(2-(meth)acryloyloxyisopropyl) ) benzene, 1,2-bis(2-(meth)acryloyloxyisopropyl)benzene, etc. These may be used alone or in admixture of 2 or more. Among them, ethylene glycol dimethacrylate, 4-vinylbenzyl methacrylate, etc. is particularly preferred.

When the above-mentioned copolymer is obtained by polymerizing the monomer component and the cross-linking agent, the compounding amount of the polysiloxane-containing monomer in the mixture of the above-mentioned monomer component and the cross-linking agent is preferably 45 to 70 parts by weight, more preferably 50 parts by weight. ~65 parts by weight, more preferably 50~60 parts by weight. When the compounding amount is less than 45 parts by weight, oxygen permeability tends to decrease. On the other hand, when it is greater than 70 parts by weight, although the oxygen permeability is improved, the resulting copolymer becomes brittle, and the processability is reduced. In addition, the solvent resistance is reduced, and the surface of the material is very easily scratched. , the amount of unpolymerized monomers of polysiloxane-containing monomers increases, which tends to affect the shape stability of CL.

The compounding quantity of the alkyl (meth)acrylate in the mixture of the said monomer component and a crosslinking agent is preferably 20-45 weight part, More preferably, it is 25-40 weight part. When the compounding amount is less than 20 parts by weight, stain resistance and workability tend to decrease. On the other hand, when it is greater than 45 parts by weight, the relative amount of silicon atoms in the resulting copolymer decreases, and the oxygen permeability decreases. Further, the amount of unpolymerized monomers of the alkyl (meth)acrylate increases, and there are Tendency to affect CL shape stability.

The blending amount of the crosslinking agent in the mixture of the monomer components and the crosslinking agent is preferably 5 to 15 parts by weight. When the compounding amount is less than 5 parts by weight, processability tends to be deteriorated, scratches are likely to occur, solvent resistance decreases, and the amount of unpolymerized monomers in monomer components tends to increase. On the other hand, when it exceeds 15 parts by weight, the resulting copolymer tends to become brittle.

Furthermore, the CL material of the present invention has high oxygen permeability and high mechanical strength, and at the same time, the amount of unpolymerized monomers in the CL material, the water absorption rate are extremely small, and the shape stability is excellent.

In the CL material of the present invention, the total amount of unpolymerized monomer components remaining in the copolymer is 3.5% by weight or less, and the oxygen permeability coefficient of the copolymer is 130×10 ^-11 (cm ² /sec)·(mLO ₂ /(mL·mmHg)) or higher, and the water absorption of the copolymer is preferably 0.3% by weight or lower.

In the CL material of the present invention, the amount of unpolymerized monomer components remaining in the copolymer relative to the copolymer is preferably 3.5% by weight or less, more preferably 2.5% by weight or less, and especially preferably 2.0% by weight or less. lower. When the remaining amount exceeds 3.5% by weight, workability and shape stability tend to deteriorate.

The oxygen permeability coefficient (Dk) of the copolymer is preferably 130×10 ^-11 (cm ² /sec)·(mLO ₂ /(mL·mmHg)) or higher, more preferably 140× ^10-11 (cm ² /sec )·(mLO ₂ /(mL·mmHg)) or higher. When the Dk is lower than 130×10- ¹¹ (cm ² /sec)·(mLO ₂ /(mL·mmHg)), the oxygen supply to the eye cannot be said to be sufficient when the lens is installed and used, and the safety tends to deteriorate . In addition, when a copolymer with a low oxygen transmission coefficient is used as a CL material, it is difficult to sufficiently supply the necessary oxygen to the cornea from the surface of the cornea through the lens, and the physiological burden on the cornea tends to increase during long-term continuous use.

The water absorption of the above copolymer is preferably 0.3% by weight or less, more preferably 0.2% by weight or less, further preferably 0.1% by weight or less. When the water absorption exceeds 0.3% by weight, the shape stability tends to decrease.

The residual amount of unpolymerized monomer components remaining in the copolymer to the copolymer, in the system containing the polysiloxane-containing monomer represented by the above general formula (I) and the above-mentioned alkyl (meth)acrylate Among them, the residual amount of polysiloxane-containing monomers to the copolymer is preferably 3.0% by weight or less, more preferably 2.0% by weight or less, and the amount of the above-mentioned alkyl (meth)acrylate to the copolymer The residual amount of the substance is preferably 0.5% by weight or less, more preferably 0.3% by weight or less. When the residual amount of the polysiloxane-containing monomer exceeds 3.0% by weight, processability tends to decrease and shape stability tends to deteriorate. In addition, when the residual amount of alkyl (meth)acrylate exceeds 0.5% by weight, the hardness is significantly lowered, the workability is deteriorated, and the shape tends to become unstable due to volatilization of the CL material, deformation, etc.

The CL material of the present invention, as a copolymer used as a CL material, has a high oxygen transmission coefficient and a high Excellent mechanical strength, at the same time, the amount of unpolymerized monomers and water absorption in CL materials are very small, and the shape stability is excellent.

According to the present invention, especially by not using a hydrophilic monomer, the polymerizability of the polysiloxane-containing monomer and the alkyl (meth)acrylate becomes good, and as a result, it is advantageous to avoid a significant amount of unpolymerized monomer. increased phenomenon. In addition, since the water absorption can be suppressed to a low value, the shape stability of CL is excellent due to the synergistic effect with the above-mentioned reduction in the amount of unpolymerized monomers, and the oxygen transmission coefficient can also be suppressed to a low value.

In the present invention, as needed, various additives generally used in CL materials, such as polymerizable or non-polymerizable ultraviolet absorbers, pigments, ultraviolet absorbing pigments, etc. Copolymerization may be carried out while existing in the copolymerization component, or it may add after polymerization.

In addition, in the present invention, basically, 45 to 70 parts by weight of tris(trimethylsiloxy)silylstyrene not containing a hydrophilic polymer and 20 to 45 parts by weight of trifluoroethyl methacrylate Polymerization is carried out at 5 to 15 parts by weight of the monomer components and the crosslinking agent, and good copolymerization can be performed in a short time. That is, the present invention is preferable in terms of polymerization in a state in which the amount of unpolymerized monomer is extremely small, in terms of not absorbing water in the material, and in terms of fully exerting oxygen permeability.

Examples of the ultraviolet absorber include benzophenone-based polymerizable ultraviolet absorbers, benzotriazole-based polymerizable ultraviolet absorbers, and the like.

Examples of benzophenone-based polymerizable ultraviolet absorbers include 2-hydroxy-4-(meth)acryloyloxybenzophenone, 2-hydroxy-4-(meth)acryloyloxy-5 -tert-butylbenzophenone, 2-hydroxy-4-(meth)acryloyloxy-2',4'-dichlorobenzophenone, 2-hydroxy-4-(2'-hydroxy-3 '-(meth)acryloyloxypropoxy)benzophenone and the like.

Examples of benzotriazole-based polymerizable ultraviolet absorbers include 2-(5-chloro-2H-benzotriazol-2-yl)-6-(1,1-dimethylethyl)-4- Methylphenol, 2-(2′-hydroxy-5′-(meth)acryloyloxyethylphenyl)-2H-benzotriazole, 2-(2′-hydroxy-5′-(methyl ) Acryloyloxyethylphenyl) -5-chloro-2H-benzotriazole, 2-(2'-hydroxyl-5'-(meth)acryloyloxypropylphenyl)-2H-benzene triazole, 2-(2'-hydroxy-5'-(meth)acryloyloxypropyl-3'-tert-butylphenyl)-5-chloro-2H-benzotriazole and the like.

A polymerizable ultraviolet absorber having the same chemical structural moiety as these ultraviolet absorbers and having a functional group capable of polymerizing with the polymerizable component in the present invention can also be used. These may be used either alone or in combination of 2 or more.

The dye is not particularly limited as long as it is safe to the living body, and dyes (non-polymerizable dyes and polymerizable dyes) used in the fields of food and pharmaceuticals can be selected.

As specific examples of non-polymerizable pigments, for example, 1,4-bis[(4-methylphenyl)amino]-9,10-anthraquinone (D&C Green No.6), 1-[[( 4-Phenylazo)phenyl]]azo-2-naphthol (D&C Red No.17), 1-hydroxy-4-[(4-methylphenyl)amino]-9,10-anthraquinone (D&C Violet No.2), 2-(2-quinolyl)-1,3-indandione (D&C Yellow No.11), 4-[(2,4-dimethylphenyl)azo ]-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-one (C.I.Solvent Yellow18), 2-(1,3-dioxo-2-indanyl) -3-Hydroxyquinoline (MACROLEX (trademark Yellow-G), etc.

Specific examples of the polymerizable dye include an azo-based polymerizable dye, an anthraquinone-based polymerizable dye, a nitro-based polymerizable dye, and a phthalocyanine-based polymerizable dye.

Examples of azo polymerizable dyes include 1-phenylazo-4-(meth)acryloyloxynaphthalene, 1-phenylazo-2-hydroxy-3-(meth)acryloyloxy Naphthalene, 1-naphthylazo-2-hydroxy-3-(meth)acryloyloxynaphthalene, 1-(α-anthracenylazo)-2-hydroxy-3-(meth)acryloyloxy Naphthalene, 1-((4′-phenylazo)phenyl)azo-2-hydroxy-3-(meth)acryloyloxynaphthalene, 1-(2′,4′-xylyl azo Nitro)-2-(meth)acryloyloxynaphthalene, 1-(o-tolyl azo)-2-(meth)acryloyloxynaphthalene, 2-(m)(meth)acryloylamide -anilino)-4,6-bis(1′-o-tolyl azo)-2′-naphthylamino)-1,3,5-triazine, 3-(meth)acrylamide-4 -phenylazophenol, 3-(meth)acrylamide-4-(8'-hydroxy-3',6'-disulfo(sulfo))-1'-naphthylazo)-phenol, 3-(meth)acrylamide-4-(1′-phenylazo-2′-naphthylazo)-phenol, 3-(meth)acrylamide-4-(p-tolyl Nitro)phenol, 4-phenylazo-7-(meth)acrylamide-1-naphthol, 2-(m-vinylanilino)-4-((p-nitrophenylazo) -anilino)-6-chloro-1,3,5-triazine, 2-(1-(o-tolyl azo)-2'-naphthyloxy)-4-(m-vinylanilino) -6-Chloro-1,3,5-triazine, 2-(p-vinylanilino)-4-(1'-(o-tolyl azo)-2'-naphthylamino)-6- Chloro-1,3,5-triazine, N-(1′-(o-tolyl azo)-2′-naphthyl)-3-vinylphthalic acid monoamide, N-(1′-(o- -Tolyl azo)-2′-naphthyl)-6-vinylphthalic acid-amide, 3-vinylphthalic acid-(4′-(p-sulfophenylazo))-1′-naphthyl ) monoester, 6-vinylphthalic acid-(4′-(p-sulfophenylazo))-1′-naphthyl) monoester, 2-amino-4-(m-(2′-hydroxy- 1′-Naphthylazo)anilino)-6-isopropenyl-1,3,5-triazine, 2-amino-4-(N-methyl-p-(2′-hydroxyl-1′- Naphthylazo)anilino)-6-isopropenyl-1,3,5-triazine, 2-amino-4-(m-(4′-hydroxy-1′-phenylazo)anilino) -6-isopropenyl-1,3,5-triazine, 2-amino-4-(N-methyl-p-(4'-hydroxyphenylazo)anilino)-6-isopropenyl- 1,3,5-Triazine, 2-amino-4-(m-(3′-methyl-1′-phenyl-5′-hydroxy-4′-pyrazolylazo)anilino)-6 -Isopropenyl-1,3,5-triazine, 2-amino-4-(N-methyl-p-(3′-methyl-1′-phenyl-5′-hydroxyl-4′-pyridine Azolyl azo)anilino)-6- Isopropenyl-1,3,5-triazine, 2-amino-4-(p-phenylazoanilino)-6-isopropenyl-1,3,5-triazine and the like.

Examples of anthraquinone-based polymerizable dyes include 1,5-bis((meth)acryloylamino)-9,10-anthraquinone, 1-amino-4-(3'-(meth)acryloylamino) Phenylamino)-9,10-anthraquinone-2-sulfonic acid, 2-(3′-(meth)acrylamide-anilino)-4-(3′-(3″-sulfo-4″ -Aminoanthraquinone-1″-yl)-amino-anilino)-6-chloro-1,3,5-triazine, 2-(3′-(meth)acrylamide-anilino)-4- (3′-(3″-sulfo-4″-aminoanthraquinone-1″-yl)-amino-anilino)-6-hydrazino-1,3,5-triazine, 1-(4′- Vinylbenzoylamide)-9,10-anthraquinone, 4-amino-1-(4′-vinylbenzoylamide)-9,10-anthraquinone, 5-amino-1-(4′-vinyl Benzoylamide)-9,10-anthraquinone, 8-amino-1-(4′-vinylbenzoylamide)-9,10-anthraquinone, 4-nitro-1-(4′-vinylbenzene Acylamide)-9,10-anthraquinone, 4-hydroxy-1-(4′-vinylbenzoylamide)-9,10-anthraquinone, 1-(3′-vinylbenzoylamide)-9, 10-anthraquinone, 1-(2'-vinylbenzoylamide)-9,10-anthraquinone, 1-(4'-isopropenylbenzoylamide)-9,10-anthraquinone, 1-(3 '-isopropenylbenzoylamide)-9,10-anthraquinone, 1-(2'-isopropenylbenzoylamide)-9,10-anthraquinone, 1,4-bis-(4'-vinyl Benzoylamide)-9,10-anthraquinone, 1,4-bis-(4′-isopropenylbenzoylamide)-9,10-anthraquinone, 1,5-bis-(4′-vinylbenzene Acylamide)-9,10-anthraquinone, 1,5-bis-(4′-isopropenylbenzoylamide)-9,10-anthraquinone, 1-methylamino-4-(3′-vinyl Benzoylamide)-9,10-anthraquinone, 1-methylamino-4-(4'-vinylbenzoyloxyethylamino)-9,10-anthraquinone, 1-amino-4-(3 '-vinylphenylamino)-9,10-anthraquinone-2-sulfonic acid, 1-amino-4-(4'-vinylphenylamino)-9,10-anthraquinone-2-sulfonic acid, 1-Amino-4-(2′-vinylbenzylamino)-9,10-anthraquinone-2-sulfonic acid, 1-(β-ethoxycarbonylallylamino)-9,10-anthraquinone , 1-(β-carboxyallylamino)-9,10-anthraquinone, 1,5-di-(β-carboxyallylamino)-9,10-anthraquinone, 1-(β-isopropyl Oxycarbonylallylamino)-5-benzoylamide-9,10-anthraquinone, 2,4-bis-((4″-methoxyanthraquinone-1″-yl)-amino)-6- (3′-vinylanilino)-1,3,5-triazine, 2-(2′-vinylphenoxy)-4-(4′-(3″-sulfo-4″-aminoanthracene Quinone-1″-yl-amino)-anilino)-6- Chloro-1,3,5-triazine, etc.

Examples of the nitro polymerizable dye include o-nitroanilino methyl (meth)acrylate and the like.

Examples of the phthalocyanine-based polymerizable dye include (meth)acryloylated tetraaminocopper phthalocyanine, (meth)acryloyl (dodecanoylated tetraaminocopper phthalocyanine), and the like.

Examples of polymerizable ultraviolet absorbing dyes include 2,4-dihydroxy-3-(p-(meth)acryloyloxymethylphenylazo)benzophenone, 2,4-dihydroxy-5 -(p-(meth)acryloyloxydimethylphenylazo)benzophenone, 2,4-dihydroxy-3-(p-(meth)acryloyloxyethylphenylazo) Benzophenone, 2,4-dihydroxy-5-(p-(meth)acryloyloxyethylphenylazo)benzophenone, 2,4-dihydroxy-3-(p-(methyl) ) acryloyloxyethylphenylazo)benzophenone, 2,4-dihydroxy-5-(p-(meth)acryloyloxyethylphenylazo)benzophenone, 2, 4-Dihydroxy-3-(o-(meth)acryloyloxypropylphenylazo)benzophenone, 2,4-dihydroxy-5-(o-(meth)acryloyloxypropyl Phenylazo)benzophenone, 2,4-dihydroxy-3-(o-(meth)acryloyloxymethylphenylazo)benzophenone, 2,4-dihydroxy-5- (O-(meth)acryloyloxymethylphenylazo)benzophenone, 2,4-dihydroxy-3-(o-(meth)acryloyloxyethylphenylazo)diphenyl Methanone, 2,4-dihydroxy-5-(o-(meth)acryloyloxyethylphenylazo)benzophenone, 2,4-dihydroxy-3-(p-N,N- Di(meth)acryloyloxyethylamino)phenylazo)benzophenone, 2,4-dihydroxy-5-(p-N,N-bis(meth)acryloyloxyethyl Amino)phenylazo)benzophenone, 2,4-dihydroxy-3-(o-N,N-di(meth)acryloyloxyethylamino)phenylazo)benzophenone , 2,4-dihydroxy-5-(o-N,N-bis(meth)acryloyloxyethylamino)phenylazo)benzophenone, 2,4-dihydroxy-3-( p-N-ethyl-N-(meth)acryloyloxyethylamino)phenylazo)benzophenone, 2,4-dihydroxy-5-(p-N-ethyl-N- (Meth)acryloyloxyethyloxyethylamino)phenylazo)benzophenone, 2,4-dihydroxy-3-(o-N-ethyl-N-(meth)propene Acyloxyethylamino)phenylazo)benzophenone, 2,4-dihydroxy-5-(o-N-ethyl-N-(meth)acryloyloxyethylamino)phenyl Azo)benzophenone, 2,4-dihydroxy-3-(o-N-ethyl-N-(meth)acryloylamino)phenylazo)benzophenone, 2,4-di Hydroxy-5-(p-N-ethyl-N-(meth)acryloylamino)phenylazo)benzophenone, 2,4-dihydroxy-3-(o-N-ethyl-N -(meth)acryloylamino)phenylazo)benzophenone, 2,4-dihydroxy-5-o-(N-ethyl-N-(meth)acryloylamino)phenylazo ) benzophenone, 2,4-dihydroxy-3-(p-styryl azo) benzophenone, 2,4-di-hydroxy-5-(p-styryl azo) diphenyl Methanone, 2-Hydroxy-4-(p-styrylazo)benzoic acid Polymerizable ultraviolet-absorbing dyes such as phenyl esters, etc. These may be used either alone or in combination of 2 or more.

The content of the above-mentioned monomer components and cross-linking agent in the mixture is considered to have a great influence on the thickness of the material, etc., usually for 100 parts by weight of the mixture of monomer components, cross-linking agents and other polymerizable monomers, preferably ultraviolet absorbing 0.01 to 1 part by weight of the agent, and 0.001 to 0.1 parts by weight of the pigment and the ultraviolet absorbing pigment can be appropriately adjusted according to the application of the intended CL material, and are not particularly limited.

When the content of the ultraviolet absorber and the pigment is too large, there is a possibility that the mechanical strength of the CL material will be reduced, and there will also be a problem that the transparency will be reduced. In addition, when CL materials are used in contact with biological tissues, the toxicity of ultraviolet absorbers, pigments, and ultraviolet absorbing pigments must be considered, and their content must be adjusted.

The copolymer constituting the CL material of the present invention can be obtained by polymerizing a mixture of the above-mentioned monomer components and a crosslinking agent at 40-120° C. for 30 minutes to 5 hours. This enables good polymerization to be performed in a short time by substantially selecting and employing monomer components having excellent copolymerizability.

The polymerization temperature can be appropriately adjusted within a temperature range of 40 to 120° C., but it is preferable to raise the temperature in the middle of the polymerization. In the polymerization reaction at a certain temperature in the low temperature range of about 40 to 50° C., the polymerization cannot be completed, or the polymerization takes a long time, so it is necessary to raise the temperature. For example, when the initial temperature is 40-60°C, prepolymerization is carried out at this temperature for 1-4 hours, and then the temperature is raised to 80-120°C and heated for 10-60 minutes to complete the polymerization reaction. In addition, when polymerization is initially performed at 70°C or higher without performing prepolymerization, a polymerization time within 3 hours is preferable. When the prepolymerization is carried out at an initial temperature of 40°C or lower, the polymerization proceeds slowly, and there is a tendency that the time needs to be prolonged in order to complete the polymerization reaction. In addition, at a polymerization temperature exceeding 120° C., the polymerization reaction becomes uncontrolled, and unpolymerized monomers tend to increase.

In addition, the polymerization time is preferably 30 minutes to 5 hours. When the polymerization time is less than 30 minutes, the polymerization tends to be incomplete (there are many unpolymerized monomers). In addition, when it is longer than 5 hours, the manufacturing time becomes longer, and as a result, the cost tends to increase.

In order to remove deformation of the obtained copolymer, heat treatment may be further performed for about 1 hour under the temperature condition of the glass transition temperature or higher of the copolymer.

When the above-mentioned monomer components are copolymerized, various conventionally known radical polymerization initiators, photopolymerization initiators, and the like can be appropriately selected and used.

As a radical polymerization initiator, for example, azobisisobutyronitrile, azodimethylvaleronitrile, benzoyl peroxide, tert-butyl hydroperoxide, cumyl hydroperoxide, etc. can be used, and these can be used alone It can also be used in combination of 2 or more kinds.

The added amount is preferably 0.001 to 2 parts by weight, more preferably 0.01 to 1 part by weight, based on 100 parts by weight of the mixture of monomer components, crosslinking agent and other polymerizable monomers.

As a photopolymerization initiator, for example, methyl o-benzoyl benzoate, methyl benzoyl formate, benzoyl methyl ether, benzoyl ethyl ether, benzoyl isopropyl ether, benzoyl isobutyl ether, Benzoyl photopolymerization initiators such as benzoyl n-butyl ether; 2-hydroxy-2-methyl-1-phenylpropane-1-one, p-isopropyl-α-hydroxy-isobutyl phenone, p- -tert-butyl trichloroacetophenone, 2,2-dimethoxy-2-phenylacetophenone, α,α-dichloro-4-phenoxyacetophenone, N,N-tetraethyl -4,4-diaminobenzophenone and other benzophenone photopolymerization initiators; 1-hydroxycyclohexyl phenyl ketone; 1-phenyl-1,2-propanedione-2-(o-ethoxy Carbonyl) oxime; thioxanthone photopolymerization initiators such as 2-chlorothioxanthone and 2-methylthioxanthone; dibenzocycloheptanone; 2-ethylanthraquinone; benzophenone acrylate; Benzophenone; diphenyl ethanedione (benzil), etc. These may be used alone or in admixture of 2 or more.

The added amount is 0 to 2 parts by weight, more preferably 0.001 to 2 parts by weight, and especially preferably 0.01 to 1 part by weight, based on 100 parts by weight of the mixture of monomer components, crosslinking agent and other polymerizable monomers.

During photopolymerization, monomer components can be polymerized without adding these photopolymerization initiators when irradiating electron beams.

Since the obtained CL material is basically composed of a hydrophobic component, the surface of the lens is hydrophobic. Therefore, in order to impart water wettability to the lens surface, it is necessary to carry out graft polymerization or coating of a hydrophilic monomer on the lens surface, use plasma treatment of various gases, use plasma and graft polymerization in combination, etc. A surface treatment.

Among them, as a simple method of imparting uniform water wettability to the lens surface, oxygen plasma treatment (for example, a plasma treatment device: manufactured by Kyoto Denshi Measurement Co., Ltd., a low-temperature ashing device PA-102AT, conditions: 40W-2 min, oxygen atmosphere, vacuum degree: 0.8 Torr) is preferred.

Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited by these examples.

Example

Example 1

Three (trimethylsiloxy) silyl styrene (hereinafter referred to as TMSiSt) 45 parts by weight, trifluoroethyl methacrylate (hereinafter referred to as 3FEMA) 45 parts by weight, ethylene glycol dimethyl 10 parts by weight of acrylate (hereinafter referred to as EDMA) was mixed. To the obtained mixture, 2,2'-azobis(2,4-dimethylvaleronitrile) (hereinafter referred to as V-65) was added as a polymerization initiator to make 0.3 parts by weight per 100 parts by weight of the mixture, Stir well to combine.

Pour the above mixture into a molding mold made of polypropylene (diameter 12mm, depth 5mm), cover it with a PET (polyethylene terephthalate) film to seal it, and place it in a circulating dryer with a nitrogen atmosphere at 50°C. After 2 hours of prepolymerization, the temperature was raised to 90° C. and kept heating for 30 minutes to complete the polymerization (polymerization condition A).

The obtained button-shaped copolymer was subjected to cutting processing to prepare test pieces for measuring various physical properties. The physical properties of the test pieces were measured by the following methods. The results are shown in Table 1.

Embodiment 2-9

Except changing by the proportioning of Table 1, carry out the same operation with embodiment 1, make copolymer, implement cutting process, the physical property of the test piece that obtains is measured by following method. The results are shown in Table 1.

Comparative Examples 1-2, 4-5

Except changing by the proportioning of Table 1, carry out the same operation with embodiment 1, make copolymer, implement cutting process, the physical property of the test piece that obtains is measured by following method. The results are shown in Table 1.

Comparative example 3

Pour the copolymer components according to Table 1 into a glass test tube, replace with nitrogen, plug it, put it into a circulating constant temperature water tank, prepolymerize at 35°C for 40 hours, then raise the temperature to 50°C, and keep heating for 8 hours. Then, heat to 50-120° C. in a circulating constant temperature dryer at a temperature increase rate of 10° C./1.5 hours to complete polymerization (polymerization condition B).

The obtained copolymer was subjected to cutting processing to prepare test pieces for measuring various physical properties. The physical properties of the test pieces were measured by the following methods. The results are shown in Table 1.

Determination of physical properties

<Oxygen transmission coefficient (Dk)>

Using a GTG (gas to gas) analyzer (manufactured by REHDER DEVELOPMENT COMPANY (U.S.)), the measurement time is 2 minutes, the measurement temperature is 35° C., and the measured value obtained is converted using Menicon EX (Dk value = 64) standardized by ISO9912-2. The Dk value was calculated and the results are shown in Table 1. Also, the Dk value means an oxygen transmission coefficient value [(cm ² /sec)·(mLO ₂ /(mL·mmHg)], specifically a value in which the oxygen transmission coefficient value is multiplied by 10 ⁻¹¹ .

<Water Absorption>

Take 10 test pieces (after drying) with a thickness of 0.5 mm as a group, measure the weight (A [g]) of each group, and dip in a sample bottle filled with distilled water at a temperature of 25°C for 24 hours, then measure the test piece. Wet weight of the tablet (B[g]). The water absorption rate was calculated according to the following formula. The results are shown in Table 1.

Water absorption (%)={(B-A)/A}×100

<Residual ingredients>

Referring to FDA GuIDANCE DOCUMENT FOR CLASS III CONTACT LENSESSAPRIL 1989 p.18 "Leachable and residual monomers", a plate with a diameter of 12mm and a thickness of 0.5mm was extracted with 5mL of acetonitrile at 50°C for 72 hours, and high performance liquid chromatography (HPLC: High performance liquid chromatography, manufactured by WATERS Corporation, 2695 separation module, detector: manufactured by WATERS Corporation, photodiode array detector 996, column: manufactured by Nomura Chemical Co., Ltd., Develosil ODS HG-5, length 250mm×I.D.4.6mm), from The working curve made by the standard solution of each copolymerization component, the concentration of each unpolymerized monomer component in the acetonitrile extract is quantified, and the residual amount of unpolymerized monomer component is calculated according to the following formula. The analytical conditions of HPLC: mobile phase initial set value: acetonitrile/distilled water=30/70, change mobile phase composition (linear gradient) continuously simultaneously with measuring and start, set after 30 minutes and make acetonitrile/distilled water=100/0. Then, until the analysis was terminated, acetonitrile/distilled water = 100/0 was maintained. In addition, the detection wavelength was 210 nm, the flow rate was 1.0 mL/min, the oven temperature was 40° C., and the injection volume was 20 μL.

The residual amount of each unpolymerized monomer component (% by weight) = (the concentration of each unpolymerized monomer in the acetonitrile extract (10 ^-6 g/mL) × 5 (mL) / plate weight (g)) × 100

hardness

Using the Rockwell surface hardness tester manufactured by Akashi Manufacturing Co., Ltd., with a load of 30kg and a pressure of 1/4 inch (about 0.64cm), in a constant temperature and humidity chamber with a temperature of 25°C and a relative humidity of 50%, the diameter of 12.0mm and thickness 4.0mm test piece for measurement.

<Processability>

The CL shape test piece was machined using a cutting machine using a diamond knife. The processability and the surface state of the processed test piece were visually observed, and evaluated using the following evaluation criteria.

(evaluation standard)

○: Easy to process and polish the lens

△: Can be processed, but some burrs are generated

×: Debris-like burrs, especially difficult to process

<injury>

Both sides of the obtained test piece were ground, and after wiping with a cloth or paper towel, the surface state of the test piece was observed with the naked eye, and evaluated according to the following evaluation criteria.

(evaluation standard)

○: Almost no scratches were found

△: A few scratches were found

×: A lot of scratches were found (scratches are easy to occur even if rubbed with a small force)

<Shape Stability>

Cut the button-shaped copolymer obtained by polymerization to make a lens with a certain specification (basic curve: 7.90mm, power: -10.0D) (diopter), lens diameter 9-2mm). The base curve and lens diameter were measured after being stored under severe conditions at 40°C for 6 months in a wet state (CL protection product containing a surfactant) and a dry state.

In the lenses obtained from the copolymers of the examples, the variation of the base curve and lens diameter was within 0.05 mm in all wet and dry states.

<Comprehensive evaluation>

In the polymerization condition A in which the total polymerization time is within 3 hours, the total residual components are 2% by weight or less, the Dk is 150 or more, and the processability and scratch resistance are "○" and the lens evaluation is "○" , especially Dk at 180 or more was evaluated as "⊚", and the others were evaluated as "×".

In "⊚", in order to further improve the workability, the one with high hardness is selected, and in this point, Example 3 is particularly preferable.

TMSiSt: Tris(trimethylsiloxy)silylstyrene

3FEMA: Trifluoroethyl methacrylate

6FIPMA: Hexafluoroisopropyl methacrylate

EDMA: Ethylene glycol dimethacrylate

UV absorber: 2-(5-chloro-2H-benzotriazol-2-yl)-6-(1,1-dimethylethyl)-4-methylphenol

Pigment: D&C Green No.6

N.D. below detection limit

BTMSiSt: Bis(trimethylsiloxy)methylsilylstyrene

5FPMA: 2,2,3,3,3-Pentafluoropropyl methacrylate

MAA: methacrylic acid

VBMA: 4-vinylbenzyl methacrylate

Polymerization initiator: 2,2'-azobis(2,4-dimethylvaleronitrile)

Possibility of industrial use

The CL material of the present invention has excellent oxygen permeability and low water absorption due to the extremely small amount of residual unpolymerized monomers, and therefore has excellent safety and shape stability. In addition, due to good processability and excellent shape stability, the thickness of CL can be reduced, and the performance of installation and use can be improved.

In addition, polymerization can be carried out in a short time by selecting monomer components (tris(trimethylsiloxy)silylstyrene and trifluoroethyl methacrylate) and crosslinking agent with excellent copolymerizability , In addition, the amount of unpolymerized monomer is significantly reduced, and it has an excellent oxygen transmission coefficient (Dk). Therefore, it can be made into a CL that is superior in safety and shape stability than before. In addition, due to good processability and excellent shape stability, the thickness of CL can be reduced, and the performance of installation and use can be improved.

Claims (8)

1. contact lens material; It comprises a copolymerization composition that contains the monomer of representing with general formula (I) that contains polysiloxane and carries out the multipolymer that polymerization obtains; The residual quantity of residual relative this multipolymer of unconverted monomer composition is aggregated in 3.5 weight % or lower in this multipolymer, and the oxygen transmission coefficient of this multipolymer is 130 * 10 ^-11(cm ²/ sec) (mLO ₂/ (mLmmHg)) or higher, and the water-intake rate of this multipolymer is 0.3 weight % or lower:

In the formula, l is 0 or 1, and n and m are 1～15 integer,

Above-mentioned multipolymer is being obtained by monomer component and the crosslinking chemical polymerization that fluorine atom substituted (methyl) alkyl acrylate constitutes by the carbon number 1～6 of monomer of representing with above-mentioned general formula (I) that contains polysiloxane and alkyl and at least one hydrogen atom of this alkyl

And above-mentioned multipolymer is containing that copolymerization composition with the monomer that contains polysiloxane 45～70 weight portions, above-mentioned (methyl) alkyl acrylate 20～45 weight portions and crosslinking chemical 5～15 weight portions of above-mentioned general formula (I) expression carries out polymerization and the multipolymer that obtains.

2. according to the contact lens material of claim 1 record, wherein, above-mentioned multipolymer also contains ultraviolet light absorber and/or pigment.

3. contact lenses, it comprises the contact lens material of claim 1 or 2 records.

4. contact lens material; It comprises the monomer component and the crosslinking chemical that are made up of three (trimethylsiloxy) silicyl styrene and trifluoroethyl methacrylate and carries out the multipolymer that polymerization obtains; Wherein, three (trimethylsiloxy) silicyl styrene is that 45～70 weight portions, trifluoroethyl methacrylate are that 20～45 weight portions and crosslinking chemical are 5～15 weight portions.

5. according to the contact lens material of claim 4 record, wherein, above-mentioned crosslinking chemical is ethylene glycol dimethacrylate and/or 4-vinyl benzyl methacrylate.

6. according to the contact lens material of claim 4 or 5 records, wherein, above-mentioned multipolymer also contains ultraviolet light absorber and/or pigment.

7. the contact lens material of putting down in writing according to claim 4 or 5; Wherein, Unconverted monomer composition in the above-mentioned multipolymer is with respect to the residual quantity of this multipolymer; For three (trimethylsiloxy) silicyl styrene is 3.0 weight % or lower, is 0.5 weight % or lower for the trifluoroethyl methacrylate, and the oxygen transmission coefficient of this multipolymer is 130 * 10 ^-11(cm ²/ sec) (mLO ₂/ (mLmmHg)) or higher, and the water-intake rate of this multipolymer is at 0.3 weight % or lower.

8. contact lenses, it comprises the contact lens material of each record among the claim 4-7.