JP2010111880A - Method for producing contact lens material - Google Patents

Abstract

The present invention provides a CL material having high oxygen permeability and mechanical strength, a very small amount of unpolymerized monomer remaining, low water absorption, and excellent lens shape stability.
A contact lens material comprising a copolymer obtained by polymerizing a copolymer component containing a specific silicone-containing monomer, wherein the copolymer is an unpolymerized monomer component remaining in the copolymer. The total residual amount of 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 more. A contact lens material having a water absorption of 0.3% by weight or less.
[Selection figure] None

Description

  The present invention relates to a contact lens (hereinafter referred to as “CL”) material. More specifically, the present invention relates to a CL material that has high oxygen permeability and high mechanical strength, and has an extremely small amount of unpolymerized monomer and water absorption in the CL material and excellent shape stability.

  In general, the oxygen-permeable CL material is mainly composed of silicone-based (meth) acrylate or silicone-based styrene, and other components include, for the purpose of imparting stain resistance, strength, water wettability, and the like. Monomers matching the target performance are selected and polymerized as copolymerization components.

  However, in the case of copolymerization in a multi-component system, the structure and characteristics of the polymerization site of each monomer are different, so it is basically difficult to copolymerize these monomers, and it is often left to experience and know-how. . Therefore, it took a very long time and labor to progress further good copolymerization with good reproducibility and to complete as a final product. In particular, when a hydrophilic monomer is selected as a copolymerization component, it has a polarity opposite to that of the main component silicone-based monomer, and it is extremely difficult to proceed with good polymerization. In such systems, it was necessary to polymerize slowly over a very long time.

  In addition, a hydrophilic monomer is added to impart water wettability, but basically, silicone having a low surface free energy appears on the lens surface, so that the effect of water wettability by addition is not so great. In other words, oxygen permeability is impaired by adding a hydrophilic monomer.

  On the other hand, in order to stabilize the shape of CL, it is considered that residual components in the lens, in particular, volatile components and elution components into the aqueous solvent must be suppressed as much as possible, and the water absorption rate of the lens material is also involved. If water absorption is applied more than necessary, the substitution phenomenon between water and residual components in the lens occurs, or if slight distortion remains in the material, the distortion is alleviated by absorbing water, and the lens There is a possibility that the deformation is accelerated.

  Patent Document 1 discloses a polymer comprising at least one styrene having a silane or siloxane bond having 15 or less Si atoms, or at least one styrene having the silane or siloxane bond, a hydrophobic monomer, and / or An oxygen-permeable hard CL made of a copolymer made of a hydrophilic monomer is described.

  However, CL described in Patent Document 1 is not intended for the copolymerization of the monomer component and cannot be favorably copolymerized (the amount of unpolymerized monomers increases) or must be polymerized slowly over a very long time. There were problems such as poor copolymerization. Specifically, when a siloxane-containing styrene monomer and a hydrophilic monomer are copolymerized (even if a hydrophobic monomer other than the siloxane-containing styrene monomer is included), the polarity is opposite, and the structure and polymerization characteristics of the polymerization site are different. Therefore, when the polymerization is carried out in a short time within a few minutes to a few hours, the polymerization reaction becomes incomplete, and a large amount of unpolymerized monomer remains in the copolymer. As a result, not only was there concern about safety to the eye, but there was a possibility that the CL shape would change due to volatilization of the unpolymerized monomer, elution into tear fluid, preservative fluid, and the like. Therefore, in the case of such a combination, it has to be slowly polymerized over a long period of time, which requires labor and is not satisfactory in terms of production cost.

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

  Patent Document 2 describes a CL material with improved dimensional stability and creep resistance, characterized by containing 3.5% by weight or less of a volatile component having a molecular weight of 700 or less.

  However, in order to obtain such CL, a silicon resin or CL material containing 5% by weight or less of a volatile component having a molecular weight of 700 or less is irradiated with high energy radiation to bring the volatile component to 3.5% by weight or less. However, it was very complicated and labor-intensive, and it was not satisfactory in terms of manufacturing cost. In addition, this technology performs post-processing to remove components such as volatile components (unpolymerized monomers) on the CL resin material after the production of the silicon-based resin, resulting in a volatile component of 5% by weight or less. It only gives dimensional stability and creep resistance, and it is not a technique to reduce the volatile component by specifying the monomer component, blending ratio, or polymerization method, and it is intended to copolymerize the monomer component. It was n’t. The use of a hydrophilic monomer is also not preferable because it can be considered to promote deformation of the lens shape as described above.

  Further, in Patent Document 3, 20 to 70 parts by weight of a silicon monomer having a silicon atom content of 10 to 50% and having one radical polymerizable functional group in the molecule as the first component, the second component 1 to 5 parts by weight of a monomer having two or more radically polymerizable functional groups in the molecule, and 30 to 70 parts by weight of alkyl (meth) acrylate, styrene or alkylstyrene copolymerizable with these as the third component CL having a specific gravity of 0.9 to 1.05 at 36 ° C. and an oxygen permeability coefficient of 40 or more is described. However, the oxygen permeability coefficient of this CL is actually 120 or less, and the oxygen permeability is not sufficient.

  In addition, such CL is intended to improve tear fluid exchange at the time of wearing by reducing the specific gravity, to reduce the burden on the cornea, and to make the lens surface hydrophilic by surface graft polymerization. The object is different from the present invention.

  As described above, in the case of an oxygen-permeable CL material mainly composed of silicone-based (meth) acrylate or silicone-based styrene, including a multi-component material, particularly a hydrophilic monomer, it is very complicated, and It took a lot of effort. Further, even after such complicated processes, the lens shape stability, eye safety, oxygen permeability and the like are not satisfactory.

  The present invention is a CL material comprising a copolymer obtained by polymerizing a copolymer component containing a silicone-containing monomer, and the residual amount of the unpolymerized monomer component remaining in the copolymer is low, and the oxygen permeability In addition, since the water absorption is excellent, it is excellent in shape stability, mechanical strength, safety to eyes, and the like, and as a result, a reduction in manufacturing cost can be achieved.

JP 60-142324 A JP-A-6-27424 JP 11-326847 A

  Provided is a CL material that has high oxygen permeability and mechanical strength, has a very small amount of unpolymerized monomer remaining, has a low water absorption, and is excellent in lens shape stability.

That is, the present invention relates to a contact lens material comprising a copolymer obtained by polymerizing a copolymer component containing a silicone-containing monomer represented by the general formula (I), which is not yet remained in the copolymer. The total residual amount of the polymerization monomer components with respect to 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 more, and the water absorption rate of the copolymer relates to a contact lens material of 0.3% by weight or less.

  In the copolymer, the silicone-containing monomer represented by the general formula (I) and the alkyl group have 1 to 6 carbon atoms, and at least one hydrogen atom of the alkyl group is substituted with a fluorine atom. It is preferably obtained by polymerizing a monomer component consisting essentially of an alkyl (meth) acrylate and a crosslinking agent.

  The copolymer includes 45 to 70 parts by weight of the silicone-containing monomer represented by the general formula (I), 20 to 45 parts by weight of the alkyl (meth) acrylate, and 5 to 15 parts by weight of a crosslinking agent. More preferably, it is obtained by polymerizing the components.

  More preferably, the copolymer further contains an ultraviolet absorber and / or a dye.

  It is preferable that the copolymer is obtained by polymerizing the monomer component and the crosslinking agent at 40 to 120 ° C. for 30 minutes to 5 hours.

  The present invention also relates to a contact lens made of the contact lens material.

  The CL material of the present invention has an extremely small amount of unpolymerized monomer remaining, an excellent oxygen permeability, and a low water absorption rate. Therefore, the CL material is superior in safety and shape stability. In addition, since the processability is good and the shape stability is excellent, it becomes possible to reduce the thickness of the CL, leading to an improvement in wearing feeling.

The present invention is a CL material obtained by polymerizing a copolymer component containing a silicone-containing monomer, which can be polymerized to a state where the amount of unpolymerized monomer is extremely small, the material does not absorb water, and has sufficient oxygen permeability. It is related with CL material preferable at the point which can be exhibited. More specifically, it is a CL material comprising a copolymer obtained by polymerizing a copolymer component containing a silicone-containing monomer represented by the general formula (I), and is an unpolymerized monomer remaining in the copolymer. The total amount of the 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 more, and the copolymer has a water absorption of 0.3 wt% or less.

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

  Specific examples of the silicone-containing monomer include various compounds depending on the structure of the silane or siloxane bond portion. Examples of the silicone-containing monomer used in the present invention include compounds represented by the above general formula (I).

  In the compound represented by the general formula (I), when 1 is 0 rather than 1, it is preferable because it is a compound that is easy to synthesize and is stable, and as n and m increase, the compound becomes soft and brittle. Regarding n and m, a CL material having particularly preferable oxygen permeability, excellent hardness and hardness, and a high refractive index can be obtained in the case of about 1 to 5.

  The straight chain and branched siloxane bonds can be used for the siloxane bond portion in the compound represented by the general formula (I), but the branched chain is harder than the straight chain. It is preferable because it becomes a thing.

  Representative examples of the compound represented by the general formula (I) include, for example, trimethylsilyl styrene, pentamethyldisiloxanyl styrene, heptamethyltrisiloxanyl styrene, nonamethyltetrasiloxanyl styrene, pentadecamethylheptasiloxa. Nyl styrene, heneicosamethyl decasiloxanyl styrene, heptacosamethyl tridecacyloxanyl styrene, hentriacontamethylpentadecasiloxanyl styrene, bis (trimethylsiloxy) methylsilylstyrene, tris (trimethylsiloxy) silylstyrene , Trimethylsiloxy / pentamethyldisiloxy / methylsilylstyrene, tris (pentamethyldisiloxy) silylstyrene, (tris / trimethylsiloxy) siloxanyl / bis (trimethylsiloxy) silylstyrene Bis (heptamethyltrisiloxy) methylsilylstyrene, tris (methylbis-trimethylsiloxy-siloxy) silylstyrene, trimethylsiloxy-bis (tris-trimethylsiloxy-siloxy) silylstyrene, heptakis (trimethylsiloxy) trisiloxanylstyrene , Nonamethyltetrasiloxy / undecylpentasiloxy / methylsilylstyrene, tris (tris / trimethylsiloxy / siloxy) silylstyrene, (tristrimethylsiloxy / hexamethyl) tetrasiloxy / (tris / trimethylsiloxy) siloxy / trimethylsiloxysilylstyrene, Nomekis (trimethylsiloxy) tetrasiloxanylstyrene, bis (tridecamethylhexasiloxy) methylsilylstyrene and the like. These may be used alone or in combination of two or more.

  Among the representative examples, for the purpose of improving oxygen permeability, mechanical strength, workability, and refractive index, for example, the formula:

Trimethylsilylstyrene represented by the formula:

Bis (trimethylsiloxy) methylsilylstyrene represented by the formula:

Tris (trimethylsiloxy) silylstyrene represented by

  In the CL material of the present invention, the residual amount of the unpolymerized monomer component remaining in the copolymer with respect to the copolymer is 3.5% by weight or less, preferably 2.5% by weight or less, more preferably Is 2.0% by weight or less. When the residual amount exceeds 3.5% by weight, processability and shape stability are inferior.

The oxygen permeability coefficient (Dk) of the copolymer is 130 × 10 ⁻¹¹ (cm ² / sec) · (mLO ₂ / (mL · mmHg)) or more, preferably 140 × 10 ⁻¹¹ (cm ² / sec). sec) · (mLO ₂ / (mL · mmHg)) or more. When Dk is less than 130 × 10 ⁻¹¹ (cm ² / sec) · (mLO ₂ / (mL · mmHg)), the amount of oxygen supplied to the eye when the lens is worn is not sufficient and the safety tends to be inferior. There is. In addition, when a copolymer having a low oxygen permeability coefficient is used as the CL material, it becomes difficult to sufficiently supply oxygen necessary for the cornea from the corneal surface via the lens, and when continuous wearing for a long time, The physiological burden of the cornea tends to increase.

  The water absorption of the copolymer is 0.3% by weight or less, preferably 0.2% by weight or less, and more preferably 0.1% by weight or less. If the water absorption exceeds 0.3% by weight, the shape stability tends to be lowered.

  The CL material of the present invention has high oxygen permeability and high mechanical strength, and has an extremely small amount of unpolymerized monomer and water absorption in the CL material, and is excellent in shape stability.

  In the present specification, “... (Meth) acrylate” generically refers to two compounds of “... Acrylate” and “.

  In the copolymer of the present invention, the silicone-containing monomer represented by the general formula (I) and the alkyl group preferably have 1 to 6 carbon atoms, and at least one hydrogen atom of the alkyl group is a fluorine atom. It is obtained by polymerizing a monomer component consisting essentially of an alkyl (meth) acrylate substituted with a crosslinking agent.

  Here, the “monomer component” means that the silicone-containing monomer represented by the general formula (I) and the alkyl group have 1 to 6 carbon atoms, and at least one hydrogen atom of the alkyl group is substituted with a fluorine atom. The two components of alkyl (meth) acrylate that are used are components other than these monomer components (polymerizable and non-polymerizable UV absorbers, dyes, polymerization initiators and other polymerizable monomers). It does not correspond to the monomer component.

  In addition, “substantially” means that other polymerizable monomers (excluding polymerizable and non-polymerizable UV absorbers, dyes and polymerization initiators) other than the monomer components are sufficient for the properties of the monomer components. To the extent that it can be exerted, specifically, in the mixture of the monomer component and the crosslinking agent, 10 parts by weight or less, preferably 5 parts by weight or less with respect to 100 parts by weight of the mixture of the monomer component, the crosslinking agent and other polymerizable monomers. It means that it may contain. When the polymerizable monomer other than the monomer component is used in an amount of more than 10 parts by weight, the amount of unpolymerized monomer increases due to the decrease in copolymerizability, thereby deteriorating the shape stability and further safety. Tend to be inferior. Moreover, there exists a tendency for oxygen permeability to fall.

  Specific examples of other polymerizable monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, tert-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-amyl (meta ) Alkyl esters of methacrylic acid or acrylic acid such as acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate; styrene, p-methylstyrene, m-methylstyrene, p-tert-butyl Styryl compounds such as styrene, m-tert-butylstyrene, p-1,1,3,3-tetramethylbutylstyrene; alkyl esters of itaconic acid or crotonic acid; glycidyl (meth) acrylate; Tetrahydrofurfuryl (meth) acrylate; benzyl (meth) acrylate.

  An alkyl (meth) acrylate having an alkyl group with 1 to 6 carbon atoms and at least one hydrogen atom of the alkyl group substituted with a fluorine atom is resistant to contamination and processing while maintaining oxygen permeability. It is a component for improving the property.

  Specific examples of the alkyl (meth) acrylate 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-tetrafluoro-tert-amyl (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-octafluoro Examples thereof include pentyl (meth) acrylate. These may be used alone or in admixture of two or more. Of these, 2,2,2-trifluoroethyl methacrylate, hexafluoroisopropyl methacrylate, 2,2,2 are preferable for improving processability and copolymerization with the silicone-containing monomer represented by the general formula (I). 3,3-tetrafluoropropyl methacrylate and 2,2,3,3,3-pentafluoropropyl methacrylate are preferred.

  In the system containing the silicone-containing monomer represented by the general formula (I) and the alkyl (meth) acrylate with respect to the residual amount of the unpolymerized monomer component remaining in the copolymer with respect to the copolymer, the silicone-containing monomer The residual amount with respect to the copolymer is preferably 3.0% by weight or less, more preferably 2.0% by weight or less, and the residual amount of the alkyl (meth) acrylate with respect to the copolymer is preferably Is 0.5% by weight or less, more preferably 0.3% by weight or less. When the residual amount of the silicone-containing monomer exceeds 3.0% by weight, the processability tends to be deteriorated and the shape stability tends to be inferior. In addition, if the residual amount of alkyl (meth) acrylate exceeds 0.5% by weight, the hardness is remarkably lowered, the workability is deteriorated, and the shape is unstable due to volatilization from the CL material, causing deformation and the like. Tend to be.

  Specific examples of the crosslinking agent include, for example, ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, Dipropylene glycol di (meth) acrylate, diallyl fumarate, allyl (meth) acrylate, vinyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, methacryloyloxyethyl (meth) acrylate, divinylbenzene, diallyl phthalate, adipic acid Diallyl, triallyl diisocyanate, α-methylene-N-vinylpyrrolidone, 4-vinylbenzyl (meth) acrylate, 3-vinylbenzyl (meth) acrylate 2,2-bis ((meth) acryloyloxyphenyl) hexafluoropropane, 2,2-bis ((meth) acryloyloxyphenyl) propane, 1,4-bis (2- (meth) acryloyloxyhexafluoroisopropyl) benzene 1,3-bis (2- (meth) acryloyloxyhexafluoroisopropyl) benzene, 1,2-bis (2- (meth) acryloyloxyhexafluoroisopropyl) benzene, 1,4-bis (2- (meth)) Examples include acryloyloxyisopropyl) benzene, 1,3-bis (2- (meth) acryloyloxyisopropyl) benzene, 1,2-bis (2- (meth) acryloyloxyisopropyl) benzene. These can be used alone or in admixture of two or more. Among them, ethylene glycol dimethacrylate and 4-vinylbenzyl methacrylate are particularly preferable because they give good mechanical strength, and have a large effect of improving workability, hardness, strength, solvent resistance and copolymerization. preferable.

  When the copolymer is obtained by polymerizing the monomer component and the crosslinking agent, the blending amount of the silicone-containing monomer in the mixture of the monomer component and the crosslinking agent is preferably 45 to 70 parts by weight. If the blending amount is less than 45 parts by weight, the oxygen permeability tends to decrease. On the other hand, when the amount exceeds 70 parts by weight, the oxygen permeability is improved, but the obtained copolymer becomes brittle and the workability is lowered, the solvent resistance is lowered, and the material surface is very easily damaged. There is a tendency that the amount of unpolymerized monomer of the silicone-containing monomer is increased and the shape stability of the CL is affected.

  Moreover, the compounding quantity of the alkyl (meth) acrylate in the mixture of the said monomer component and a crosslinking agent becomes like this. Preferably it is 20-45 weight part. When the blending amount is less than 20 parts by weight, the stain resistance and workability tend to be lowered. On the other hand, if the amount exceeds 45 parts by weight, the relative amount of silicon atoms in the resulting copolymer is reduced, so that the oxygen permeability is lowered, and further, the amount of unpolymerized monomer of alkyl (meth) acrylate is increased. However, it tends to affect the shape stability of CL.

  The blending amount of the crosslinking agent in the mixture of the monomer component and the crosslinking agent is preferably 5 to 15 parts by weight. If the blending amount is less than 5 parts by weight, the processability tends to be deteriorated, scratches easily occur, the solvent resistance decreases, and the amount of the unpolymerized monomer of the monomer component increases. On the other hand, if it exceeds 15 parts by weight, the resulting copolymer tends to be brittle.

  According to the present invention, by particularly not using a hydrophilic monomer, the polymerizability between the silicone-containing monomer and the alkyl (meth) acrylate is improved, and as a result, the phenomenon that the amount of unpolymerized monomer is remarkably increased is advantageously avoided. can do. Moreover, since the water absorption rate can be kept low, the shape stability of CL is excellent due to the synergistic effect with the decrease in the amount of the unpolymerized monomer, and in addition, the decrease in the oxygen permeability coefficient can be suppressed.

  In the present invention, if necessary, various additives conventionally used in CL materials, for example, in order to impart UV absorbing ability to CL materials or to color CL materials, it is polymerizable. Alternatively, non-polymerizable ultraviolet absorbers, dyes, ultraviolet absorbing dyes, and the like may be present in the copolymer component to be copolymerized or added after polymerization.

  Examples of the ultraviolet absorber include a benzophenone polymerizable ultraviolet absorber and a benzotriazole polymerizable ultraviolet absorber.

  Examples of the benzophenone polymerizable ultraviolet absorber include 2-hydroxy-4- (meth) acryloyloxybenzophenone, 2-hydroxy-4- (meth) acryloyloxy-5-tert-butylbenzophenone, 2-hydroxy-4- (meta ) Acryloyloxy-2 ′, 4′-dichlorobenzophenone, 2-hydroxy-4- (2′-hydroxy-3 ′-(meth) acryloyloxypropoxy) benzophenone, and the like.

  Examples of the benzotriazole-based polymerizable UV absorber 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 ′-(meth) acryloyloxyethylphenyl) -5-chloro-2H-benzotriazole, 2- (2'-hydroxy-5 '-(meth) acryloyloxypropylphenyl) -2H-benzotriazole, 2- (2'-hydroxy-5'-(meth) acryloyloxypropyl-3'-tert-butylphenyl)- 5-chloro-2H-benzotriazole and the like.

  A polymerizable ultraviolet absorber having the same chemical structure as those of the ultraviolet absorber and having a functional group capable of being polymerized with the polymerization component in the present invention can also be used. These can be used alone or in admixture of two or more.

  The dye is not particularly limited as long as safety to the living body is required, and dyes (non-polymerizable dyes and polymerizable dyes) used in the fields of foods and pharmaceuticals are selected.

  As specific examples of the non-polymerizable dye, for example, 1,4-bis [(4-methylphenyl) amino] -9,10-anthraquinone (D & C Green No. 6), 1-[[4- (phenylazo) phenyl Azo] -2-naphthalenol (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-pyrazole-3- ON (C.I Solvent Yellow 18), 2- (1,3-dioxo-2-indanyl) -3-hydroxyquinoline (MACROL EX (trademark) Yellow-G).

  Specific examples of the polymerizable dye include azo polymerizable dyes, anthraquinone polymerizable dyes, nitro polymerizable dyes, and phthalocyanine polymerizable dyes.

  Examples of the azo polymerizable dye include 1-phenylazo-4- (meth) acryloyloxynaphthalene, 1-phenylazo-2-hydroxy-3- (meth) acryloyloxynaphthalene, 1-naphthylazo-2-hydroxy-3- (meta ) Acryloyloxynaphthalene, 1- (α-anthrylazo) -2-hydroxy-3- (meth) acryloyloxynaphthalene, 1-((4′-phenylazo) phenyl) azo-2-hydroxy-3- (meth) acryloyloxy Naphthalene, 1- (2 ′, 4′-xylylazo) -2- (meth) acryloyloxynaphthalene, 1- (o-tolylazo) -2- (meth) acryloyloxynaphthalene, 2- (m- (meth) acryloylamide -Anilino) -4,6-bis (1 '-(o-tolylazo) -2'-na Tilamino) -1,3,5-triazine, 3- (meth) acryloylamide-4-phenylazophenol, 3- (meth) acryloylamide-4- (8′-hydroxy-3 ′, 6′-disulfo-1) '-Naphthylazo) -phenol, 3- (meth) acryloylamide-4- (1'-phenylazo-2'-naphthylazo) -phenol, 3- (meth) acryloylamide-4- (p-tolylazo) phenol, 4- Phenylazo-7- (meth) acryloylamide-1-naphthol, 2- (m-vinylanilino) -4-((p-nitrophenylazo) -anilino) -6-chloro-1,3,5-triazine, 2- (1- (o-tolylazo) -2′-naphthyloxy) -4- (m-vinylanilino) -6-chloro-1,3,5-triazine, 2- (P-vinylanilino) -4- (1 ′-(o-tolylazo) -2′-naphthylamino) -6-chloro-1,3,5-triazine, N- (1 ′-(o-tolylazo) -2 '-Naphtyl) -3-vinylphthalic acid monoamide, N- (1'-(o-tolylazo) -2'-naphthyl) -6-vinylphthalic acid monoamide, 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'-hydroxy-1'-naphthylazo) anilino) -6 Isoprop 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'-hydroxy-4'-pyrazolylazo) anilino) -6-isopropenyl-1,3,5-triazine, 2-amino-4- (p-phenylazoanilino) -6-isopropenyl -1,3,5-tria Such as emissions, and the like.

  Anthraquinone-based polymerizable dyes include 1,5-bis ((meth) acryloylamino) -9,10-anthraquinone, 1-amino-4- (3 ′-(meth) acryloylaminophenylamino) -9,10- Anthraquinone-2-sulfonic acid, 2- (3 ′-(meth) acryloylamide-anilino) -4- (3 ′-(3 ″ -sulfo-4 ″ -aminoanthraquinone-1 ″ -yl) -amino -Anilino) -6-chloro-1,3,5-triazine, 2- (3 '-(meth) acryloylamide-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′-vinylbenzoylamide) -9,10-anthraquinone, 8-amino-1- (4′-vinylbenzoylamide) -9,10-anthraquinone, 4-nitro-1- (4'-vinylbenzoylamide) -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′-isopropenyl Benzoylamide) -9,10-anthraquinone, 1,4-bis- (4′-vinylbenzoylamide) -9,10-anthraquinone, 1,4-bis- (4′-isopropenylbenzoylamide) -9,10 -Anthraquinone, 1,5-bis- (4'-vinylbenzoylamide) -9,10-anthraquinone, 1,5-bis- (4'-isopropenylbenzoylamide) -9,10-anthraquinone, 1-methylamino -4- (3'-vinylbenzoylamide) -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) C) -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-isopropoxy Carbonylallylamino) -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 ″ -aminoanthraquinone-1 ″-) Le - amino) - anilino) such as 6-chloro-1,3,5-triazine and the like.

  Examples of the nitro polymerizable dye include o-nitroanilinomethyl (meth) acrylate.

  Examples of the phthalocyanine-based polymerizable dye include (meth) acryloylated tetraamino copper phthalocyanine and (meth) acryloylated (dodecanoylated tetraamino copper phthalocyanine).

  Examples of polymerizable ultraviolet absorbing dyes include 2,4-dihydroxy-3- (P- (meth) acryloyloxymethylphenylazo) benzophenone, 2,4-dihydroxy-5- (p- (meth) acryloyloxymethylphenylazo). ) Benzophenone, 2,4-dihydroxy-3- (p- (meth) acryloyloxyethylphenylazo) benzophenone, 2,4-dihydroxy-5- (p- (meth) acryloyloxyethylphenylazo) benzophenone, 2,4 -Dihydroxy-3- (p- (meth) acryloyloxypropylphenylazo) benzophenone, 2,4-dihydroxy-5- (p- (meth) acryloyloxypropylphenylazo) benzophenone, 2,4-dihydroxy-3- ( o- (Meth) acryloyloxymethyl Nylazo) benzophenone, 2,4-dihydroxy-5- (o- (meth) acryloyloxymethylphenylazo) benzophenone, 2,4-dihydroxy-3- (o- (meth) acryloyloxyethylphenylazo) benzophenone, 2, 4-dihydroxy-5- (o- (meth) acryloyloxyethylphenylazo) benzophenone, 2,4-dihydroxy-3- (o- (meth) acryloyloxypropylphenylazo) benzophenone, 2,4-dihydroxy-5 (O- (meth) acryloyloxypropylphenylazo) benzophenone, 2,4-dihydroxy-3- (p- (N, N-di (meth) acryloyloxyethylamino) phenylazo) benzophenone, 2,4-dihydroxy-5 -(P-N, N-di (meta) Acryloyloxyethylamino) phenylazo) benzophenone, 2,4-dihydroxy-3- (o-N, N-di (meth) acryloyloxyethylamino) phenylazo) benzophenone, 2,4-dihydroxy-5- (o- ( N, N-di (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) acryloyloxyethylamino) phenylazo) benzophenone, 2,4-dihydroxy-3- (o- (N-ethyl-N- (meth) acryloyloxy) Ethylamino) phenylazo) benzophenone, 2,4-dihydroxy -5- (o- (N-ethyl-N- (meth) acryloyloxyethylamino) phenylazo) benzophenone, 2,4-dihydroxy-3- (p- (N-ethyl-N- (meth) acryloylamino) phenylazo ) Benzophenone, 2,4-dihydroxy-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-styrenoazo) Benzophenone, 2,4-dihydroxy-5- (p-styrenoazo) benzophenone, 2-hydro Such as Shi-4-(p-Suchirenoazo) polymerizable ultraviolet absorbing dyes such as phenyl benzoate and the like. These may be used alone or in combination of two or more.

  In consideration of the fact that the content of the monomer component and the cross-linking agent in the mixture is greatly affected by the thickness of the material, the content is usually based on 100 parts by weight of the mixture of the monomer component, the cross-linking agent and other polymerizable monomers. In the case of an ultraviolet absorber, 0.01 to 1 part by weight is preferable, and in the case of a dye and an ultraviolet absorbing dye, 0.001 to 0.1 part by weight is desirable. It may be appropriately adjusted according to the application, and is not particularly limited.

  When the contents of the ultraviolet absorber and the dye are excessive, the mechanical strength of the CL material may be lowered, and there is a problem that transparency is lowered. Further, when the CL material is used in contact with a living tissue, the content of the CL material must be adjusted in consideration of the toxicity of the ultraviolet absorber, the dye and the ultraviolet absorbing dye.

  The copolymer used as the CL material of the present invention can be obtained by polymerizing the mixture of the monomer component and the crosslinking agent at 40 to 120 ° C. for 30 minutes to 5 hours. This is because good polymerization was possible in a short time by substantially selecting and using monomer components having excellent copolymerizability.

  About polymerization temperature, it is preferable to adjust suitably in the temperature range of 40-120 degreeC, and to heat up in the middle of superposition | polymerization. In a polymerization reaction at a constant temperature in a low temperature range of about 40 to 50 ° C., the polymerization is not completed, or the polymerization time is long, so that a temperature increase is required. For example, when the initial temperature is 40 to 60 ° C., prepolymerization is performed at this temperature for 1 to 4 hours, and then the temperature is raised to 80 to 120 ° C. and heated for 10 to 60 minutes to complete the polymerization reaction. be able to. In addition, when the polymerization reaction is performed at 70 ° C. or higher from the beginning without performing preliminary polymerization, a polymerization time of 3 hours or less is preferable. In the prepolymerization at an initial temperature of 40 ° C. or lower, the progress of the polymerization is slow, and it tends to take time to complete the polymerization reaction. Further, at a polymerization temperature exceeding 120 ° C., the polymerization reaction tends to run away and unpolymerized monomers tend to increase.

  The polymerization time is preferably 30 minutes to 5 hours. If the polymerization time is less than 30 minutes, the polymerization tends to be incomplete (the number of unpolymerized monomers increases). Moreover, when it becomes longer than 5 hours, manufacturing time will become long and there exists a tendency for cost to become high as a result.

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

  When copolymerizing the monomer components, conventionally known various radical polymerization initiators, photopolymerization initiators and the like can be appropriately selected and used.

  Examples of the radical polymerization initiator include azobisisobutyronitrile, azobisdimethylvaleronitrile, benzoyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, and the like. These can be used alone or in admixture of two or more.

  The addition amount is 0.001 to 2 parts by weight, and more preferably 0.01 to 1 part by weight with respect to 100 parts by weight of the mixture of the monomer component, the crosslinking agent and other polymerizable monomers.

  Examples of the photopolymerization initiator include benzoin photopolymerization initiators such as methyl orthobenzoyl benzoate, methyl benzoyl formate, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzoin-n-butyl ether; 2 -Hydroxy-2-methyl-1-phenylpropan-1-one, p-isopropyl-α-hydroxyisobutylphenone, p-tert-butyltrichloroacetophenone, 2,2-dimethoxy-2-phenylacetophenone, α, α-dichloro Phenone-based photopolymerization initiators such as -4-phenoxyacetophenone and N, N-tetraethyl-4,4-diaminobenzophenone; 1-hydroxycyclohexyl phenyl ketone; 1-phenyl- , 2-propanedione-2- (o-ethoxycarbonyl) oxime; thioxanthone photopolymerization initiators such as 2-chlorothioxanthone and 2-methylthioxanthone; dibenzosbarone; 2-ethylanthraquinone; benzophenone acrylate; benzophenone; Is given. These can be used alone or in admixture of two or more.

  As an addition amount, 0 to 2 parts by weight, more preferably 0.001 to 2 parts by weight, and further preferably 0.01 to 1 part by weight with respect to 100 parts by weight of the mixture of the monomer component, the crosslinking agent and other polymerizable monomers. Parts by weight.

  In photopolymerization, when an electron beam is irradiated, the monomer component can be polymerized without adding such a photopolymerization initiator.

  Since the obtained CL material is substantially composed of a hydrophobic component, the lens surface becomes water repellent. Therefore, in order to give water wettability to the lens surface, some surface treatment such as graft polymerization or coating of hydrophilic monomer on the lens surface, plasma treatment using various gases, combined use of plasma and graft polymerization is required. Become.

  Among these, as a method for easily and uniformly imparting water wettability to the lens surface, plasma treatment with oxygen gas (for example, plasma treatment apparatus: low temperature ashing apparatus PA-102AT manufactured by Kyoto Electronics Measurement Co., Ltd., condition: 40W) -2 minutes, oxygen gas atmosphere, vacuum degree: 0.8 Torr).

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to these Examples.

Example 1
45 parts by weight of tris (trimethylsiloxy) silylstyrene (hereinafter referred to as TMSiSt), 45 parts by weight of trifluoroethyl methacrylate (hereinafter referred to as 3FEMA), and 10 parts by weight of ethylene glycol dimethacrylate (hereinafter referred to as EDMA) were mixed. To the obtained mixture, 2,2′-azobis (2,4-dimethylvaleronitrile) (hereinafter referred to as V-65) as a polymerization initiator was added in an amount of 0.3 part by weight based on 100 parts by weight of this mixture. Stir and mix.

  The mixture was poured into a polypropylene mold (diameter 12 mm, depth 5 mm), covered with a PET (polyethylene terephthalate) film, sealed, and preliminarily polymerized at 50 ° C. for 2 hours in a circulation dryer in a nitrogen atmosphere. Then, the temperature was raised to 90 ° C. and kept heated for 30 minutes to complete the polymerization (polymerization condition A).

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

Examples 2-9
A copolymer was produced and cut in the same manner as in Example 1 except that the formulation was changed as shown in Table 1. The physical properties of the obtained test pieces were measured according to the following methods. The results are shown in Table 1.

Comparative Examples 1-2, 4-5
A copolymer was prepared and cut in the same manner as in Example 1 except that the formulation was changed as shown in Table 1. The physical properties of the obtained test pieces were measured according to the following methods. The results are shown in Table 1.

Comparative Example 3
The copolymer components blended according to Table 1 were poured into a glass test tube, purged with nitrogen, sealed, put in a circulating thermostatic bath, prepolymerized at 35 ° C for 40 hours, and then heated to 50 ° C. And heated for 8 hours. Then, it heated at the temperature increase rate of 10 degree-C / 1.5 hours to 50-120 degreeC in the circulation type thermostat, and superposition | polymerization was completed (polymerization condition B).

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

Physical property measurement <Oxygen transmission coefficient (Dk)>
Using a GTG (GAS to GAS) ANALYZER (manufactured by REMDERDEVELOPENT COMPANY (USA)), the measurement time was 2 minutes and the temperature was measured at 35 ° C., and the obtained measurement value was standardized by ISO 9912-2 Conversion was performed using Menicon EX (Dk value = 64) to obtain a Dk value, and the result is shown in Table 1. The Dk value means the value of oxygen permeability coefficient [(cm ² / sec) · (mLO ₂ / (mL · mmHg))], and in particular, a value obtained by multiplying the value of oxygen permeability coefficient by 10 ^−11. is there.

<Water absorption rate>
The test piece (dried) of 0.5mm thickness was made into a set of 10 pieces, and the weight (A [g]) was measured for each set, and the sample bottle containing distilled water was placed at a temperature of 25 ° C. After dipping for 24 hours, the wet weight (B [g]) of the test piece was measured. The water absorption was calculated by the following formula. The results are shown in Table 1.
Water absorption (%) = {(B−A) / A} × 100

<Residual components>
FDA GUIDANCE DOCUMENT FOR CLASS III CONTACT LENSES APRIL 1989 p. 18 With reference to “Leachable and residual monomers”, one plate having a diameter of 12 mm and a thickness of 0.5 mm was extracted with 5 mL of acetonitrile at 50 ° C. for 72 hours, and subjected to high performance liquid chromatography (HPLC; high performance liquid chromatograph: 2695 manufactured by WATERS). Separation module; Detector: Photodiode array detector 996 manufactured by WATERS, Inc .; Column: Develosil ODS HG-5 Length 250 mm × ID 4.6 mm manufactured by Nomura Chemical Co., Ltd.) From the calibration curve created from the above, the concentration of each unpolymerized monomer component in the acetonitrile extract was quantified, and the residual amount of the unpolymerized monomer component was calculated by the following equation. The HPLC analysis conditions were as follows. The initial setting value of the mobile phase was acetonitrile / distilled water = 30/70, and the composition of the mobile phase was continuously changed (linear gradient) simultaneously with the start of measurement. After 30 minutes, acetonitrile / distilled water = It was set to be 100/0. And it kept at acetonitrile / distilled water = 100/0 until the end of analysis. The detection wavelength was 210 nm, the flow rate was 1.0 mL / min, the oven temperature was 40 ° C., and the implantation amount was 20 μL.

Residual amount of each unpolymerized monomer component (wt%)
= (Concentration of each unpolymerized monomer in acetonitrile extract (10 ^-6 g / mL) x 5 (mL)
/ Plate weight (g)) × 100

<Hardness>
Using a Rockwell superficial hardness meter manufactured by Akashi Seisakusho Co., Ltd., in a constant temperature and humidity chamber at a temperature of 25 ° C. and a relative humidity of 50% with a load of 30 kg and an indenter of 1/4 inch (about 0.64 cm). Measurement was performed on a test piece having a thickness of 0 mm and a thickness of 4.0 mm.

<Processability>
Using a cutting machine using a diamond cutting tool, processing was performed on a CL-shaped test piece. The workability and the surface state of the sample piece after processing were visually observed and evaluated based on the following evaluation criteria.
(Evaluation criteria)
○: Can be easily processed and polished into a lens. Δ: Processing is possible, but slight wrinkles occur. ×: Chipping-like wrinkles are severe and processing is difficult.

<Scratches>
After both surfaces of the obtained test piece were polished and rubbed with a cloth or tissue paper, the surface state of the test piece was visually observed and evaluated based on the following evaluation criteria.
(Evaluation criteria)
○: scars are hardly seen Δ: some scratches are observed ×: many scratches are observed (they are easily scratched even when rubbed with a weak force)

<Shape stability>
The polymerized button-shaped copolymer was cut to produce a lens having a certain standard (base curve: 7.90 mm, power: −10.0 D (diopter), lens diameter: 9.2 mm). The base curve and the lens diameter were measured after 6 months of storage under severe conditions at 40 ° C. in a wet state (surfactant-containing CL care product) and a dry state.

  The lenses obtained from the copolymers of all Examples and Comparative Examples had a variation in base curve and lens diameter within 0.05 mm in both wet and dry conditions.

Claims (7)

A contact lens comprising a copolymer, wherein the silicone-containing monomer represented by the general formula (I) and a crosslinking agent are polymerized under polymerization conditions of a polymerization temperature of 40 to 120 degrees and a polymerization time of 30 minutes to 5 hours. The total amount of unpolymerized monomer components remaining in the copolymer with respect to the copolymer is 3.5% by weight or less, and the oxygen permeability coefficient of the copolymer is a method for producing a material. , 130 × 10 ⁻¹¹ (cm ² / sec) · (mLO ₂ / (mL · mmHg)) or more, and the water absorption of the copolymer is 0.3% by weight or less. Method.

The contact lens material according to claim 1, wherein the polymerization conditions are prepolymerization at a polymerization temperature of 40 to 60 degrees and a polymerization time of 1 to 4 hours, and then polymerization is performed at a polymerization temperature of 80 to 120 degrees and a polymerization time of 10 to 60 minutes. Production method. In the copolymer, the silicone-containing monomer represented by the general formula (I) and the alkyl group have 1 to 6 carbon atoms, and at least one hydrogen atom of the alkyl group is substituted with a fluorine atom. The method for producing a contact lens material according to claim 1 or 2, which is obtained by polymerizing a monomer component consisting only of alkyl (meth) acrylate and a crosslinking agent. The copolymer includes 45 to 70 parts by weight of the silicone-containing monomer represented by the general formula (I), 20 to 45 parts by weight of the alkyl (meth) acrylate, and 5 to 15 parts by weight of a crosslinking agent. The method for producing a contact lens material according to claim 3, which is obtained by polymerizing components. The manufacturing method of the contact lens material of any one of Claims 1-4 in which the said copolymer contains a ultraviolet absorber and / or a pigment | dye further. The method for producing a contact lens material according to claim 1, wherein the copolymer is obtained by polymerizing the monomer component and the crosslinking agent at 40 to 120 ° C. for 30 minutes to 5 hours. The contact lens obtained by the manufacturing method of the contact lens material of any one of Claims 1-6.