JP2011219512A - Polymerizable composition, polymer material, ophthalmic lens, and contact lens - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymerizable composition which can reduce a monomer residual ratio of the resulting polymer material because of high compatibility and copolymerizability between monomer components including a silicone compound and N-vinylpyrrolidinone and which can attain high oxygen permeability and high surface wettability, and a polymer material obtained from the polymerizable composition.SOLUTION: The polymerizable composition contains as monomer components [A] a polymerizable compound having an acryloyloxy group, not having a silicon atom, and showing a glass transition temperature of ≤10°C as a homopolymer thereof, [B] a silicone compound having a polymerizable group, and [C] N-vinylpyrrolidinone. It is preferable that the polymerizable compound as [A] component further contains an ether bond and shows water absorption of ≤20% as a homopolymer thereof.

Description

  The present invention relates to a polymerizable composition, a polymer material obtained by curing the polymerizable composition, and an ophthalmic lens and a contact lens made of the polymer material.

  Silicone hydrogel is used as a material for ophthalmic lenses such as contact lenses because of its high oxygen permeability. However, since silicone hydrogels generally have low surface wettability, various efforts have been made to improve surface wettability, such as surface treatment and inclusion of hydrophilic polymers.

  As one of the techniques for improving the water wettability of the surface of such a silicone hydrogel, N-vinylpyrrolidinone (N-VP), which is widely used as a hydrophilic monomer, is incorporated as one of copolymerization components. It has been proposed (see US Pat. No. 5,486,579, etc.). However, since N-VP is poorly compatible with the silicone compound, it is not possible to obtain a uniform transparent lens material by simply mixing them, and in addition, the copolymerizability is low. Therefore, in the technology using such N-VP as a copolymerization component, N, N-dimethylacrylamide (DMAA), which is commonly used as an amphiphilic monomer having both hydrophilic and lipophilic properties, is used in combination. It is necessary to make the system uniform by using a large amount of organic solvent. According to the method using the amphiphilic monomer, the hydrophilicity is increased, but the inclusion of a large amount of DMAA causes a disadvantage that the water content becomes too high and high oxygen permeability cannot be obtained. Also, the heavy use of organic solvents is not a preferable method even if the manufacturing process is complicated or the influence on the environment is taken into consideration.

  Moreover, since this N-VP has a vinyl group as a polymerization group, it has low copolymerizability with (meth) acrylate generally used as a component of ophthalmic lenses, and may remain as an unreacted monomer in the material. High nature. Therefore, in order to manufacture a highly safe medical device without residue, a great deal of labor is required in the construction and operation of the manufacturing process. Therefore, for example, (1) Technology for reducing residual components in the system by unifying the polymerization groups of other monomers into vinyl groups in order to improve copolymerization with N-VP in silicone hydrogel (WO94). (See Japanese Patent No. 03324), and (2) a technique (see Japanese Patent No. 3850729) for reducing residual monomers by strictly controlling the amount of a monomer containing a crosslinking agent. However, it is very difficult to improve the chemical structure of all the monomers having various structures in the technique of unifying the polymerization group of the other monomer (1) into a vinyl group. It is hard to say that it is practical. In addition, the technique for strictly controlling the amount of the monomer containing the crosslinking agent (2) can be achieved only when a limited monomer type is used and a limited mixing ratio is applied.

US Pat. No. 5,486,579 WO94 / 03324 Publication Japanese Patent No. 3850729

  The present invention has been made in view of these disadvantages, and is highly compatible and copolymerizable between monomer components including a silicone compound and N-VP, and has a reduced monomer residual ratio and high oxygen permeation in the resulting polymer material. It is an object of the present invention to provide a polymerizable composition capable of realizing the properties and wettability of the surface and a polymer material obtained from the composition. It is another object of the present invention to provide an ophthalmic lens and a contact lens made of this polymer material.

The invention made to solve the above problems is
[A] a polymerizable compound having an acryloyloxy group, having no silicon atom, and having a glass transition temperature of 10 ° C. or less as a homopolymer thereof,
[B] A polymerizable composition containing a silicone compound having a polymerizable group and [C] N-vinylpyrrolidinone as monomer components.

  The polymerizable compound of the component [A] has an acryloyloxy group, so that it is compatible with the silicone compound of the component [B] and the N-vinylpyrrolidinone (hereinafter referred to as “N-VP”) of the component [C]. And the copolymerizability of both the [B] component silicone compound and the [C] component N-VP is enhanced. In addition, the polymerizable compound of the component [A] has a glass transition temperature of 10 ° C. or less as its homopolymer, so that the polymer growth terminal can easily move even in the later stage of polymer formation where the curing has progressed to a certain degree. . Therefore, according to the polymerizable composition, by containing the monomer component, the polymerization can be performed in a state where the monomer components are uniformly mixed, and at the time of curing polymerization, the silicone of [B] component Since N-VP of the compound and the [C] component can be efficiently incorporated into the polymer chain, both the polymerization rates of the [B] component and the [C] component can be increased. As a result, it is possible to reduce both the residual ratio of the silicone compound of the [B] component and the N-VP monomer component of the [C] component in the obtained polymer material.

  Moreover, since the silicone compound of [B] component has a silicone unit in a molecule | numerator, it can provide high oxygen permeability to the polymer material obtained from the said polymeric composition. Furthermore, since N-VP of [C] component has hydrophilicity, the water wettability of the polymer material obtained from the said polymeric composition can be improved.

  That is, the polymerizable composition has a property that each monomer component is uniformly mixed and a property that the polymerization rate is high, and can impart high oxygen permeability and water wettability to the obtained polymer material. . Therefore, according to the polymerizable composition, in the obtained polymer material, it is possible to reduce the amount of the [B] component silicone compound and the [C] component N-VP monomer component remaining unpolymerized. A highly safe polymer material can be provided for various applications. Further, steps such as elution treatment can be omitted or simplified in the production stage of the polymer material.

  The polymerizable compound of component [A] preferably further has an ether bond. Since the polymerizable compound of [A] component further has an ether bond, the compatibility of the polymerizable compound of [A] component with the silicone compound of [B] component and N-VP of [C] component is further improved. To do. Therefore, since the polymerization can be performed in a state where each monomer component is further uniformly mixed, the residual ratio of the silicone component of [B] component and the N-VP monomer component of [C] component in the obtained polymer material is determined. Further reduction can be achieved.

  The water absorption as a homopolymer of the polymerizable compound [A] is preferably 20% or less. The polymerizable composition has a water absorption of 20% or less as a homopolymer of the compound of the component [A], so that the water content of the resulting polymer material is kept below a certain level, resulting in a decrease in oxygen permeability. Can be suppressed.

The polymerizable compound as the component [A] is more preferably a compound represented by the following formula (1).
_{CH 2 = CH-CO- (OCH} 2 CH 2) n -OR 1 (1)
(In formula (1), R ¹ represents a methyl group or an ethyl group. N represents an integer of 1 to 3.)

  When the polymerizable compound of the component [A] is a compound represented by the above formula, the polymerizable compound of the component [A], the silicone compound of the component [B] and the N-VP of the component [C] The compatibility and copolymerization are particularly high. Therefore, it is possible to further reduce the unpolymerized residual ratio of the silicone compound of the [B] component and the N-VP of the [C] component in the obtained polymer material. As a result, the safety of the resulting polymer material can be further enhanced. Thus, the compatibility of the [B] component silicone compound and the [C] component with N-VP is particularly high, and the [B] component silicone compound and the [C] component N-VP are copolymerizable. As the specific polymerizable compound of the component [A], which is particularly high, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-methoxyethoxyethyl acrylate or 2-ethoxyethoxyethyl acrylate is preferable.

The silicone compound of [B] component is
[B1] a compound having an ethylenically unsaturated double bond and a polydimethylsiloxane structure via a urethane bond, and / or [B2] consisting of a silicone-containing alkyl (meth) acrylate, a silicone-containing styrene derivative and a silicone-containing fumaric acid diester It is preferably at least one compound selected from the group.
The silicone compound as the component [B1] can impart high oxygen permeability to the resulting polymer material due to the siloxane moiety. In addition, such a silicone compound of [B1] component has an elastic bond called urethane bond, thereby improving the elasticity of the polymer material obtained from the polymerizable composition, eliminating brittleness, and mechanical strength. Can be improved. By using the silicone compound as the component [B2], not only oxygen permeability but also high flexibility can be imparted to the resulting polymer material. Further, by using the [B1] component and the [B2] component together, a silicone hydrogel having both high oxygen permeability, appropriate flexibility, and good shape retention can be obtained.

（式（５）中、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５及びＲ^１６は、それぞれ独立に炭素数１〜６のアルキル基、フッ素置換されたアルキル基、フェニル基又は水素原子であり、Ｋは１０〜１００の整数、Ｌは０又は１〜９０の整数であり、Ｋ＋Ｌは１０〜１００の整数である。）
−Ｒ^４−Ｘ^３−Ｅ^２−Ｘ^４−Ｒ^５− （６）
（式（６）中、Ｒ^４及びＲ^５はそれぞれ独立に炭素数１〜６の直鎖状又は分岐鎖を有するアルキレン基であり、Ｘ^３及びＸ^４は、それぞれ独立に酸素原子又はアルキレングリコール基であり、Ｅ^２は、飽和もしくは不飽和脂肪族系、脂環式系及び芳香族系の群から選ばれたジイソシアネート由来の２価の基（但し、この場合、Ｅ^２はＸ^３及びＸ^４の間で２つのウレタン結合を形成している。）である。）］ The silicone compound of the component [B1] is represented by the following formula (2), so that the elasticity, flexibility and mechanical strength of the polymer material obtained from the polymerizable composition can be further improved. .
A ¹ -U ^1- (S ¹ -W) _m -S ² -U ² -A ² (2)
[In the formula (2), A ¹ and A ² are each independently the following formula (3), U ¹ and U ² are each independently the following formula (4), and S ¹ and S ² are each independently the following formula (5 ) And W are groups represented by the following formula (6), and m represents an integer of 0 to 10.
Y-Z-R ^2- (3)
(In Formula (3), Y is a (meth) acryloyl group, a vinyl group or an allyl group, Z is an oxygen atom or a direct bond, R ² is a direct bond or a straight chain having 1 to 12 carbon atoms, branched. (It is an alkylene group having a chain or an aromatic ring, provided that Y in A ¹ and A ² may be the same or different.)
^{-X 1 -E 1 -X 2 -R 3} - (4)
(In Formula (4), X ¹ and X ² are each independently selected from a direct bond, an oxygen atom and an alkylene glycol group, E ¹ is an —NHCO— group (where X ¹ is a direct bond, X ² is an oxygen atom or an alkylene glycol group, E ¹ forms a urethane bond with X ² ), —CONH— group (in this case, X ¹ is an oxygen atom or an alkylene glycol group, X ² is a direct bond, and E ¹ forms a urethane bond with X ^1. ) Or 2 derived from a diisocyanate selected from the group of saturated or unsaturated aliphatic, alicyclic and aromatic systems A valent group (provided that, in this case, X ¹ and X ² are each independently selected from an oxygen atom and an alkylene glycol group, and E ¹ forms two urethane bonds between X ¹ and X ² ). at is, R Is an alkylene group having a linear or branched chain having 1 to 6 carbon atoms.)

(In the formula (5), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently an alkyl group having 1 to 6 carbon atoms, a fluorine-substituted alkyl group, a phenyl group or a hydrogen atom. K is an integer of 10 to 100, L is 0 or an integer of 1 to 90, and K + L is an integer of 10 to 100.)
^{-R 4 -X 3 -E 2 -X 4} -R 5 - (6)
(In Formula (6), R ⁴ and R ⁵ are each independently an alkylene group having a linear or branched chain having 1 to 6 carbon atoms, and X ³ and X ⁴ are each independently an oxygen atom or alkylene glycol. E ² represents a divalent group derived from a diisocyanate selected from the group consisting of saturated or unsaturated aliphatic, alicyclic and aromatic groups (where E ² represents X ³ and X Forming two urethane bonds between ⁴ ).)]]

  As a blending ratio of the monomer component, the polymerization of the component [A] is performed with respect to a total amount of 100 parts by mass of the polymerizable compound of the component [A], the silicone compound of the component [B], and the N-vinylpyrrolidinone of the component [C]. 10 parts by mass or more and 45 parts by mass or less of the functional compound, 10 parts by mass or more and 70 parts by mass or less of the silicone compound as the component [B], and 10 parts by mass or more and 50 parts by mass or less of N-VP as the component [C]. When the polymerizable composition has the above blending ratio, it is possible to further reduce the amount of unpolymerized monomer in the obtained polymer material, and to realize higher oxygen permeability and water wettability of the obtained polymer material. .

  In the polymerizable composition, the non-polymerizable additive is further added to 100 parts by mass of the total amount of the polymerizable compound [A], the silicone compound [B], and the N-vinylpyrrolidinone [C]. 5 parts by mass or less, and the additive is preferably at least one selected from the group consisting of a water-soluble organic solvent, a surfactant, a cooling agent, and a thickening agent. Since the polymerizable composition promotes uniform dispersion of N-VP of each monomer component, particularly [C] component, by containing the additive, the amount of unpolymerized monomer in the resulting polymer material is further increased. Can be reduced. For the same reason, the wettability of the resulting polymer material can be improved. Furthermore, according to the said polymerizable composition, the further functionality can be added to the polymer material obtained by containing the said additive.

  The water-soluble organic solvent is at least one selected from the group consisting of alcohols having 1 to 3 carbon atoms, acetone, methyl ethyl ketone, dimethylformamide, dimethyl sulfoxide, acetonitrile, N-methyl-2-pyrrolidone and dimethoxyethane. preferable. According to the water-soluble organic solvent, the compatibility between the monomer components in the polymerizable composition can be further improved, and as a result, the unpolymerization rate of the monomer components in the resulting polymer material can be further reduced. it can.

  The surfactant is preferably nonionic and has a polyoxyethylene group. Since the surfactant to be added has a polyoxyethylene group, the dispersibility of N-VP as the component [C] can be increased, so that the wettability of the polymer material obtained from the polymerizable composition is improved. be able to.

  Further, the nonionic surfactant having a polyoxyethylene group may be polyoxyethylene hydrogenated castor oil, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene polysiloxane ethers and polyoxyethylene polysiloxane ethers. Since the dispersibility of N-VP of [C] component can be further enhanced by being at least one selected from the group consisting of oxyethylene polyoxypropylene copolymers, a polymer obtained from the polymerizable composition The water wettability of the material can be further improved.

  Examples of the refreshing agent include l-menthol, d-menthol, dl-menthol, d-camphor, dl-camphor, d-borneol, dl-borneol, geraniol, eucalyptus oil, bergamot oil, fennel oil, peppermint oil, rose Being at least one selected from the group consisting of oil and cool mint increases the dispersibility of N-VP as the component [C] in the polymerizable composition, and increases the water wettability of the resulting polymer material surface. It is preferable in that it can provide a refreshing feeling suitable for use of the polymer material obtained from the polymerizable composition.

  Further, the thickening agent is sodium hyaluronate, sodium chondroitin sulfate, sodium alginate, sorbitol, dextran 70, sodium carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, carboxyvinyl polymer, polyvinyl alcohol, polyvinylpyrrolidone and macrogol 4000. And at least one selected from the group consisting of [C] can particularly enhance the dispersibility of the N-VP component, and can particularly improve the water wettability of the polymer material obtained from the polymerizable composition. The polymer material obtained from the polymerizable composition is preferable in that a suitable moist feeling can be imparted.

  The polymer material of the present invention can be obtained by curing the polymerizable composition. The polymer material has a low amount of unpolymerized residual monomer and has high oxygen permeability and water wettability.

  The polymer material preferably has a water content of 40% or more. The polymer material can exhibit higher water wettability by setting the moisture content to 40% or more.

  Therefore, an ophthalmic lens made of the polymer material, particularly a contact lens, has low unpolymerized residual monomer components as described above, and has high oxygen permeability and water wettability. In addition, the product value and reliability can be high.

  As described above, in the polymerizable composition of the present invention, the monomer components can be mixed uniformly, and the contained monomer components have high copolymerizability with each other. The component is easily incorporated into the polymer chain. Accordingly, it is possible to reduce unpolymerized residual monomer components, and to provide a polymer material that is highly safe for various uses and has high oxygen permeability and water wettability. Further, steps such as elution treatment can be omitted or simplified in the manufacturing stage. The polymer material having the above characteristics can be used in various applications such as ophthalmic lenses such as contact lenses, catheters, tubes, stents, tubes, blood bags, probes, and thin films.

  Hereinafter, preferred embodiments of the polymerizable composition of the present invention and a polymer material obtained by curing the polymerizable composition will be described in order.

[Polymerizable composition]
The polymerizable composition of the present invention includes a polymerizable compound having [A] an acryloyloxy group, no silicon atom, and a glass transition temperature of 10 ° C. or less as a homopolymer thereof, [B] a polymerizable group And [C] N-vinylpyrrolidinone as monomer components, and suitable optional components include [D] cross-linking agent, [E] additive, [F] UV absorber, dye, and UV absorbing dye [G] A polymerization initiator may be contained, and other optional components may be further contained.

<[A] component: a polymerizable compound having an acryloyloxy group, having no silicon atom, and having a glass transition temperature of 10 ° C. or less as its homopolymer>
The polymerizable compound of component [A] has an acryloyloxy group (CH ₂ ═CH—CO—O—), does not have a silicon atom, and has a glass transition temperature of 10 ° C. or less as a homopolymer thereof. The polymerizable compound of the [A] component has high compatibility with the silicone compound of the [B] component and the N-VP of the [C] component by having the above structure. Moreover, the said polymeric compound has high copolymerizability with both the silicone compound of a [B] component, and N-VP of a [C] component by providing the said structure. Therefore, according to the polymerizable composition, by including the polymerizable compound of the component [A], the polymerization can be performed in a state where the monomer components are uniformly mixed, and the components [B] and [C] Both the polymerization rates of the components can be increased. As a result, the residual ratio of the unreacted [B] component silicone compound and the [C] component N-VP in the polymer material obtained from the polymerizable composition can be reduced.

  In addition, it is important that the polymerizable compound of the component [A] has a homopolymer glass transition temperature of 10 ° C. or lower. The reason for this will be described below. In the polymer material, when the compound of the component [A] is located at the polymer growth end during polymerization, the growth end portion may move easily in the polymer being formed. This is because if the growth terminal moves easily, the polymer growth terminal approaches the silicone compound of [B] component and N-VP of [C] component even in the later stage of polymer formation where the curing has progressed to a certain degree. This is because it becomes easy to react. As a result, according to the polymer material, the polymer growth terminal can be bonded to the silicone compound of the [B] component and the N-VP of the [C] component even in the later stage of polymer formation. The remaining [B] component silicone compound and [C] component N-VP are reduced.

  When the polymerizable compound of component [A] is located at the polymer growth end, the ease of movement of the growth end in the forming polymer is largely related to the low glass transition temperature of the homopolymer of this compound. That is, the lower the glass transition temperature in the homopolymer, the easier the polymer growth ends in the polymer being formed move. The above is the reason why the compound having the [A] component preferably has a glass transition temperature of 10 ° C. or lower. Specifically, as the polymerizable compound of the component [A], it is important that the glass transition temperature of the homopolymer is 10 ° C or lower, preferably 0 ° C or lower, and -20 ° C or lower. Particularly preferred. On the other hand, if the glass transition temperature is too low, the polymer material obtained from the polymerizable composition containing the component [A] is not preferable because the surface is highly sticky or the shape retention is lowered. There is a risk of having characteristics. Specifically, the compound of [A] component preferably has a homopolymer glass transition temperature of −150 ° C. or higher, more preferably −120 ° C. or higher, and −100 ° C. or higher. Particularly preferred.

  As described above, when the polymerizable compound of the component [A] has an acryloyloxy group and the glass transition temperature as a homopolymer thereof is 10 ° C. or less, the polymer material obtained from the polymerizable composition is Since the amount of unreacted monomer contained is reduced, it has high safety. As the polymerizable compound of the component [A], one type or a plurality of types can be used.

The water absorption as a homopolymer of the polymerizable compound [A] is preferably 20% or less, more preferably 10% or less. This is because the polymer material contains N-vinylpyrrolidinone, which is a highly hydrophilic [C] component, so that the oxygen permeability may be lowered. Therefore, by containing a compound having low water absorption as the component [A], the water content of the polymer material can be kept below a certain level, and as a result, a decrease in oxygen permeability of the polymer material can be suppressed. In addition, the water absorption as a homopolymer is the mass W1 of the homopolymer immersed in distilled water at 25 ° C. for 16 hours or more and the mass W2 of the homopolymer after being dried in an oven at 105 ° C. for 16 hours. Measured and calculated from the following formula.
Water absorption (%) = (W1-W2) / W1 × 100

  The polymerizable compound of the component [A] is not particularly limited as long as it has an acryloyloxy group, does not have a silicon atom, and has a glass transition temperature as a homopolymer of 10 ° C. or lower. It is preferable to have. When the polymerizable compound of the component (A) has an ether bond in addition to the acryloyloxy group, the compatibility of each monomer component constituting the polymerizable composition is further improved. As a result, since the polymerization rate is improved, the amount of residual monomer can be further reduced.

Among them, the polymerizable compound of the component [A] is preferably a compound represented by the following formula (1).
_{CH 2 = CH-CO- (OCH} 2 CH 2) n -OR 1 (1)
(In formula (1), R ¹ represents a methyl group or an ethyl group. N represents an integer of 1 to 3.)

  When the compound of the component [A] is a compound represented by the above formula (1), the compatibility with the silicone compound of the component [B] and the N-VP of the component [C] is particularly high, and at the terminal of the growing polymer It can have suitable easiness of movement, and the copolymerizability with both the silicone compound of the [B] component and the N-VP of the [C] component is further improved. As a result, it is possible to further reduce the unpolymerized residual ratio of the silicone compound of the [B] component and the N-VP of the [C] component.

  Specific [A] component compounds include 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-methoxyethoxyethyl acrylate, 2-ethoxyethoxyethyl acrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, Examples include hexyl acrylate, cyclohexyl acrylate, phenyl acrylate, and benzyl acrylate. Among them, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-methoxyethoxyethyl acrylate, or 2-ethoxyethoxyethyl acrylate is [B]. It is preferable in terms of particularly high compatibility and copolymerizability with the component silicone compound and the component [C] N-VP.

  The proportion of the polymerizable compound used as the component [A] is not particularly limited, but includes all monomer components (the polymerizable compound as the component [A], the silicone compound as the component [B], and the N-VP as the component [C]. 10 parts by mass or more and 45 parts by mass or less are preferable, and 15 parts by mass or more and 35 parts by mass or less are more preferable. By making the use ratio of the component [A] 10 parts by mass or more, the compatibility and copolymerization of each monomer component can be improved, and the use ratio of the component [A] is 45 parts by mass or less. Thus, the oxygen permeability and water content of the resulting polymer material can be increased. Moreover, it is preferable that the usage-amount of the polymeric compound of [A] component is 0.3 to 2 times the usage-amount of [C] component, and it is further more preferable that it is 0.5 to 1.8 times. By setting the ratio of the usage ratio of the [A] component and the usage ratio of the [C] component within the above range, the copolymerization of the [A] component and the [C] component proceeds efficiently, and the unpolymerized residue Monomers can be further reduced.

<[B] component: silicone compound having a polymerizable group>
[B] The silicone compound having a polymerizable group is a compound having a polymerizable group and a siloxanyl group. By including the silicone compound of the component [B] having the structure in the polymerizable composition, high oxygen permeability and flexibility are imparted to a polymer material obtained by polymerizing and curing the polymerizable composition. be able to. The silicone compound having such a polymerizable group is not particularly limited as long as it has a polymerizable group and a siloxanyl group. The polymerizable functional group is not particularly limited as long as it is a polymerizable group, but a typical example is an ethylenically unsaturated group. Specific examples of the ethylenically unsaturated group include a terminal vinyl group, an internal vinyl group, an allyl group, a (meth) acryloyl group, an α-substituted acryloyl group, and a styryl group. As the silicone compound of the component [B], one type or a plurality of types can be used.

  As a preferable example of the silicone compound of [B] component, the compound ([B1] component) which has an ethylenically unsaturated group and a polydimethylsiloxane structure through a urethane bond is mentioned. By providing such a silicone compound with a urethane bond and a siloxane moiety, the resulting polymer material has a function of imparting flexibility, elastic resilience, and oxygen permeability, and at the same time improving mechanical strength. That is, such a silicone compound has an ethylenically unsaturated group that is a polymerizable group at both ends of the molecule, and is copolymerized with other monomer components via this polymerizable group. In addition to physical reinforcement by cross-linking, the reinforcement effect by chemical bonding is imparted.

（式（５）中、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５及びＲ^１６は、それぞれ独立に炭素数１〜６のアルキル基、フッ素置換されたアルキル基、フェニル基又は水素原子であり、Ｋは１０〜１００の整数、Ｌは０又は１〜９０の整数であり、Ｋ＋Ｌは１０〜１００の整数である。）
−Ｒ^４−Ｘ^３−Ｅ^２−Ｘ^４−Ｒ^５− （６）
（式（６）中、Ｒ^４及びＲ^５はそれぞれ独立に炭素数１〜６の直鎖状又は分岐鎖を有するアルキレン基であり、Ｘ^３及びＸ^４は、それぞれ独立に酸素原子又はアルキレングリコール基であり、Ｅ^２は、飽和もしくは不飽和脂肪族系、脂環式系及び芳香族系の群から選ばれたジイソシアネート由来の２価の基（但し、この場合、Ｅ^２はＸ^３及びＸ^４の間で２つのウレタン結合を形成している。）である。）］で表わされるポリシロキサンマクロモノマーが挙げられる。 As a typical example of a compound having an ethylenically unsaturated group and a polydimethylsiloxane structure through the urethane bond of the component [B1],
A ¹ -U ^1- (S ¹ -W) _m -S ² -U ² -A ² (2)
[In the formula (2), A ¹ and A ² are each independently the following formula (3), U ¹ and U ² are each independently the following formula (4), and S ¹ and S ² are each independently the following formula (5 ) And W are groups represented by the following formula (6), and m represents an integer of 0 to 10.
Y-Z-R ^2- (3)
(In Formula (3), Y is a (meth) acryloyl group, a vinyl group or an allyl group, Z is an oxygen atom or a direct bond, R ² is a direct bond or a straight chain having 1 to 12 carbon atoms, branched. (It is an alkylene group having a chain or an aromatic ring, provided that Y in A ¹ and A ² may be the same or different.)
^{-X 1 -E 1 -X 2 -R 3} - (4)
(In Formula (4), X ¹ and X ² are each independently selected from a direct bond, an oxygen atom and an alkylene glycol group, E ¹ is an —NHCO— group (where X ¹ is a direct bond, X ² is an oxygen atom or an alkylene glycol group, E ¹ forms a urethane bond with X ² ), —CONH— group (in this case, X ¹ is an oxygen atom or an alkylene glycol group, X ² is a direct bond, and E ¹ forms a urethane bond with X ^1. ) Or 2 derived from a diisocyanate selected from the group of saturated or unsaturated aliphatic, alicyclic and aromatic systems A valent group (provided that, in this case, X ¹ and X ² are each independently selected from an oxygen atom and an alkylene glycol group, and E ¹ forms two urethane bonds between X ¹ and X ² ). at is, R Is an alkylene group having a linear or branched chain having 1 to 6 carbon atoms.)

(In the formula (5), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently an alkyl group having 1 to 6 carbon atoms, a fluorine-substituted alkyl group, a phenyl group or a hydrogen atom. K is an integer of 10 to 100, L is 0 or an integer of 1 to 90, and K + L is an integer of 10 to 100.)
^{-R 4 -X 3 -E 2 -X 4} -R 5 - (6)
(In Formula (6), R ⁴ and R ⁵ are each independently an alkylene group having a linear or branched chain having 1 to 6 carbon atoms, and X ³ and X ⁴ are each independently an oxygen atom or alkylene glycol. E ² represents a divalent group derived from a diisocyanate selected from the group consisting of saturated or unsaturated aliphatic, alicyclic and aromatic groups (where E ² represents X ³ and X ^And 2 urethane bonds are formed between ^{4 and 4} ).

In the above formula (2), Y in A ¹ and A ² is a polymerizable group, but can be easily copolymerized with the compound of [A] component and N-VP of [C] component. And an acryloyl group is particularly preferred.

In the above formula (2), each of Z in A ¹ and A ² is an oxygen atom or a direct bond, preferably an oxygen atom. Further, A ¹ and A ² in R ² is a direct either bond or C 1 -C 12 straight, a branched chain or alkylene group having an aromatic ring, preferably an alkylene group having 2 to 4 carbon atoms is there. U ¹ , U ² and W represent a group containing a urethane bond in the molecular chain.

In U ¹ and U ² in the above formula (2), E ¹ is, as described above, -CONH- group, -NHCO- group, or saturated or unsaturated aliphatic system, alicyclic system and aromatic system, respectively. Represents a divalent group derived from diisocyanate selected from the group consisting of Here, examples of the divalent group derived from diisocyanate selected from the group of saturated or unsaturated aliphatic, alicyclic and aromatic groups include ethylene diisocyanate, 1,3-diisocyanate propane, hexamethylene diisocyanate. Divalent groups derived from saturated aliphatic diisocyanates such as: divalent groups derived from alicyclic diisocyanates such as 1,2-diisocyanatecyclohexane, bis (4-isocyanatocyclohexyl) methane, isophorone diisocyanate; Examples thereof include divalent groups derived from aromatic diisocyanates such as 1,5-diisocyanate naphthalene; and divalent groups derived from unsaturated aliphatic diisocyanates such as 2,2′-diisocyanate diethyl fumarate. Among these examples, from the viewpoint of availability and imparting strength to the resulting polymer material, a divalent group derived from hexamethylene diisocyanate, a divalent group derived from tolylene diisocyanate, and a divalent group derived from isophorone diisocyanate. Groups are preferred.

In U ¹ and U ² in the above formula (2), when E ¹ is a —NHCO— group, X ¹ is a direct bond, X ² is an oxygen atom or an alkylene glycol group, and E ¹ is A urethane bond represented by X ² and the formula: —NHCOO— is formed. When E ¹ is a —CONH— group, X ¹ is an oxygen atom or an alkylene glycol group, X ² is a direct bond, and E ¹ is a urethane represented by X ¹ and the formula: —OCONH—. Form a bond. Further, when E ¹ is a divalent group derived from the above diisocyanate, X ¹ and X ² are preferably each independently selected from an oxygen atom and an alkylene glycol group having 1 to 6 carbon atoms, and E ¹ is X two forms a urethane bond between the ¹ and X ^2. R ³ is an alkylene group having a linear or branched chain having 1 to 6 carbon atoms.

In W in the above formula (2), E ² represents a divalent group derived from a diisocyanate selected from the group consisting of saturated or unsaturated aliphatic, alicyclic and aromatic groups, as described above. Here, as an example of the divalent group derived from diisocyanate selected from the group of saturated or unsaturated aliphatic, alicyclic and aromatic, the same divalent group as in U ¹ and U ² can be used. Groups. Among these examples, from the viewpoint of easy availability and imparting strength to the resulting polymer material, a divalent group derived from hexamethylene diisocyanate, a divalent group derived from tolylene diisocyanate, and a divalent group derived from isophorone diisocyanate. Groups are preferred. E ² forms two urethane bonds between X ³ and X ⁴ . X ³ and X ⁴ are preferably each independently an oxygen atom or an alkylene glycol group having 1 to 6 carbon atoms, and R ⁴ and R ⁵ are each independently a straight chain having 1 to 6 carbon atoms or It is an alkylene group having a branched chain.

The ^{X 1, X 2, X 3} , X 4 in the formula (4) and (6), preferably an alkylene glycol group having 1 to 20 carbon atoms. Such an alkylene glycol group having 1 to 20 carbon atoms is represented by the following formula (7).
_{-O- (C x H 2x -O)} y - (7)
(In formula (7), x represents an integer of 1 to 4, and y represents an integer of 1 to 5.)

In the above formula (5), as an example in which R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are fluorine-substituted alkyl groups, — (CH ₂ ) _g —C _p F _{2p + 1} And groups represented by (g = 1 to 10, p = 1 to 10). Specific examples of such a fluorine-substituted alkyl group include 3,3,3-trifluoro-n-propyl group, 2- (perfluorobutyl) ethyl group, 2- (perfluorooctyl) ethyl group, and the like. Examples include a side-chain fluorine-substituted alkyl group and a branched-chain fluorine-substituted alkyl group such as 2- (perfluoro-5-methylhexyl) ethyl group. When the compounding amount of the compound having such a fluorine-substituted alkyl group is increased, the antilipid contamination of the resulting polymer material is improved.

In the above formula (5) representing S ¹ and S ² , K is an integer of 10 to 100, L is an integer of 0 or 1 to 90, and K + L is an integer of 10 to 100, preferably 10 to 80 is there. When K + L is greater than 100, the molecular weight of the silicone compound increases, so the compatibility between this and the [C] component N-VP deteriorates, and phase separation occurs during polymerization, resulting in white turbidity. New polymer materials may not be obtained. Moreover, when K + L is less than 10, the oxygen permeability of the obtained polymer material is lowered, and the flexibility tends to be lowered.

  In said formula (2), m is an integer of 0-10, Preferably it is an integer of 0-5. When m is larger than 10, since the molecular weight of the silicone compound is increased as described above, the compatibility between this and the [C] component N-VP deteriorates, and phase separation occurs during polymerization, resulting in white turbidity. A uniform and transparent polymer material may not be obtained.

  Typical examples of the silicone compound of the [B1] component represented by the above formula (2) include compounds represented by the following formula (8) and the following formula (9).

  In the polymerizable composition, in order to improve the oxygen permeability of the obtained polymer material and to impart high flexibility, the polymerizable composition is used as a silicone compound of [B] as a silicone-containing alkyl. It is preferable to contain at least one compound ([B2] component) selected from the group consisting of (meth) acrylates, silicone-containing styrene derivatives, and silicone-containing fumaric acid diesters.

  Examples of silicone-containing alkyl (meth) acrylates include trimethylsiloxydimethylsilylmethyl (meth) acrylate, trimethylsiloxydimethylsilylpropyl (meth) acrylate, methylbis (trimethylsiloxy) silylpropyl (meth) acrylate, tris (trimethylsiloxy) silyl Propyl (meth) acrylate, mono [methylbis (trimethylsiloxy) siloxy] bis (trimethylsiloxy) silylpropyl (meth) acrylate, tris [methylbis (trimethylsiloxy) siloxy] silylpropyl (meth) acrylate, methylbis (trimethylsiloxy) silylpropyl Glyceryl (meth) acrylate, tris (trimethylsiloxy) silylpropyl glyceryl (meth) acrylate, mono [ Rubis (trimethylsiloxy) siloxy] bis (trimethylsiloxy) silylpropyl glyceryl (meth) acrylate, trimethylsilylethyltetramethyldisiloxypropyl glyceryl (meth) acrylate, trimethylsilylmethyl (meth) acrylate, trimethylsilylpropyl (meth) acrylate, trimethylsilylpropyl glyceryl (Meth) acrylate, trimethylsiloxydimethylsilylpropyl glyceryl (meth) acrylate, methylbis (trimethylsiloxy) silylethyltetramethyldisiloxymethyl (meth) acrylate, tetramethyltriisopropylcyclotetrasiloxanylpropyl (meth) acrylate, tetramethyl Triisopropylcyclotetrasiloxybis (trimethylsiloxy) Such Rupuropiru (meth) acrylate. Among these, tris (trimethylsiloxy) silylpropyl methacrylate is particularly preferable from the viewpoint of easy availability and the particularly high flexibility of the resulting polymer material.

（式（１０）中、ｑは１〜１５の整数、ｒは０又は１、ｓは１〜１５の整数を示す。） Examples of the silicone-containing styrene derivative include compounds represented by the following formula (10).

(In formula (10), q represents an integer of 1 to 15, r represents 0 or 1, and s represents an integer of 1 to 15.)

  Specific examples of the silicone-containing styrene derivative represented by the above formula (10) include tris (trimethylsiloxy) silylstyrene, bis (trimethylsiloxy) methylsilylstyrene, (trimethylsiloxy) dimethylsilylstyrene, and tris (trimethylsiloxy) siloxy. Dimethylsilylstyrene, [bis (trimethylsiloxy) methylsiloxy] dimethylsilylstyrene, (trimethylsiloxy) dimethylsilylstyrene, heptamethyltrisiloxanylstyrene, nonamethyltetrasiloxanylstyrene, pentadecamethylheptacyloxanylstyrene, Henicosamethyl decasiloxanyl styrene, heptacosa methyl tridecacyloxanyl styrene, Hentria Contamethyl pentadecacyloxanyl styrene, Trimethylsiloxype Tamethyldisiloxymethylsilylstyrene, tris (pentamethyldisiloxy) silylstyrene, tris (trimethylsiloxy) siloxybis (trimethylsiloxy) silylstyrene, bis (heptamethyltrisiloxy) methylsilylstyrene, tris [methylbis (trimethylsiloxy) siloxy ] Silylstyrene, trimethylsiloxybis [tris (trimethylsiloxy) siloxy] silylstyrene, heptakis (trimethylsiloxy) trisilylstyrene, nonamethyltetrasiloxyundecylmethylpentasiloxymethylsilylstyrene, tris [tris (trimethylsiloxy) siloxy] silyl Styrene, (Tristrimethylsiloxyhexamethyl) tetrasiloxy [Tris (trimethylsiloxy) siloxy] trimethylsiloxy Silylstyrene, Nonakis (trimethylsiloxy) tetrasilylstyrene, bis (tridecamethylhexasiloxy) methylsilylstyrene, heptamethylcyclotetrasiloxynylstyrene, heptamethylcyclotetrasiloxybis (trimethylsiloxy) silylstyrene, tripropyltetramethyl Examples include cyclotetrasiloxanyl styrene and trimethylsilyl styrene.

（式（１１）中、Ｒ^２１、Ｒ^２２、Ｒ^２３、Ｒ^２４、Ｒ^２５及びＲ^２６は、それぞれ独立にメチル基又はトリメチルシロキシ基を示し、ｔ及びｕはそれぞれ独立に１〜３の整数を示す。） Examples of the silicone-containing fumaric acid diester include compounds represented by the following formula (11).

(In Formula (11), R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ and R ²⁶ each independently represent a methyl group or a trimethylsiloxy group, and t and u are each independently an integer of 1 to 3) Is shown.)

  Specific examples of the silicone-containing fumaric acid diester represented by the above formula (11) include bis (3- (trimethylsilyl) propyl) fumarate, bis (3- (pentamethyldisiloxanyl) propyl) fumarate, bis (tris And (trimethylsiloxy) silylpropyl) fumarate.

  Although the component [B1] and the component [B2] may be used alone, it is preferable to use both in combination in order to form a flexible silicone hydrogel. Although the usage-amount of the silicone compound of the [B] component containing a [B1] component and a [B2] component is not specifically limited, 10 mass parts or more and 70 mass parts or less are preferable with respect to 100 mass parts of all monomer components, 15 masses More preferred is at least 65 parts by weight. By setting the use ratio of the component [B] to 10 parts by mass or more, a polymer material having sufficient oxygen permeability and high flexibility can be obtained. Moreover, reduction of hydrophilicity, transparency, etc. of the polymer material obtained can be prevented by making the usage-amount of a [B] component 70 mass parts or less.

<[C] component: N-vinylpyrrolidinone>
The N-vinylpyrrolidinone [C] component can be copolymerized with the polymerizable compound [A] component and the silicone compound [B] component. Moreover, since N-vinylpyrrolidinone of [C] component has hydrophilicity, it can improve the water wettability of the obtained polymer material surface.

  Although it does not specifically limit as a usage rate of N-vinyl pyrrolidinone of a [C] component, 10 mass parts or more and 50 mass parts or less are preferable with respect to 100 mass parts of all the monomer components, and 15 mass parts or more and 45 mass parts or less are further. preferable. By making the usage ratio of the component [C] 10 parts by mass or more, the surface water wettability of the polymer material can be improved. Moreover, reduction of the hydrophilicity, transparency, etc. of the lens obtained can be prevented by making the usage-amount of a [C] component or less into 50 mass parts.

<[D] component: cross-linking agent>
In order to adjust the crosslinking density, flexibility, and hardness of the resulting polymer material, a crosslinking agent can be added as a [D] component to the polymerizable composition. Examples of such crosslinking agents include allyl (meth) acrylate, vinyl (meth) acrylate, 4-vinylbenzyl (meth) acrylate, 3-vinylbenzyl (meth) acrylate, (meth) acryloyloxyethyl (meth) acrylate, Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, diethylene glycol diallyl ether, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di ( (Meth) acrylate, butanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 2,2-bis [p- (meth) acryloyloxyphenyl] Xafluoropropane, 2,2-bis [m- (meth) acryloyloxyphenyl] hexafluoropropane, 2,2-bis [o- (meth) acryloyloxyphenyl] hexafluoropropane, 2,2-bis [p- (Meth) acryloyloxyphenyl] propane, 2,2-bis [m- (meth) acryloyloxyphenyl] propane, 2,2-bis [o- (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) acryloyloxyiso Propyl] benzene, 1,3-bis [2- (meth) acryloyloxy isopropyl] benzene, 1,2-bis [2- (meth) acryloyloxy isopropyl] benzene. These crosslinking agents can be used alone or in combination.

  The proportion of the crosslinking agent used in the polymerizable composition is preferably 0.05% by mass or more and 1% by mass or less, more preferably 0.1% by mass or more and 0.8% by mass with respect to 100 parts by mass of the total monomer components. It is as follows. By setting the use ratio of the crosslinking agent to 0.05% by mass or more, flexibility and the like can be reliably adjusted. On the other hand, by setting the use ratio of the crosslinking agent to 1% by mass or less, it is possible to suppress a decrease in mechanical strength and durability of the polymer material.

<[E] component: additive>
When further reducing the residual unreacted monomer component of the resulting polymer material or when further desired properties are to be imparted, it is a non-polymerizable water-soluble organic solvent, surfactant, cooling agent, viscosity. A thickener or the like can be used as an additive for the component [E].

  As an upper limit of the usage rate of these additives, 5 mass parts is preferable with respect to 100 mass parts of all monomer components, and 3 mass parts is particularly preferable. Moreover, as a minimum of the usage-amount of these additives, 0.1 mass part is preferable with respect to 100 mass parts of all the monomer components, and 0.3 mass part is especially preferable. If the use ratio of the additive exceeds the above upper limit, these non-polymerizable components increase, so that it takes time to elute in the elution process after curing, and it is difficult to sufficiently dissolve these non-polymerizable components. There is a risk of remaining in the polymer material. On the contrary, if the use ratio of the additive is smaller than the above lower limit, the effect of using the additive may not be sufficiently exhibited.

  As the water-soluble organic solvent, alcohol having 1 to 3 carbon atoms, acetone, methyl ethyl ketone, dimethylformamide, dimethyl sulfoxide, acetonitrile, N-methyl-2-pyrrolidone, dimethoxyethane and the like can be used. According to the water-soluble organic solvent, compatibility between monomer components such as N-vinylpyrrolidinone [C] component can be improved, so that uniform dispersion in the polymerizable composition can be further promoted, and as a result, the monomer It is possible to reduce the unpolymerized rate.

  The surfactant is a compound having a hydrophilic group and a hydrophobic group, and each monomer component can be uniformly dispersed in the polymerizable composition. As a result, the unpolymerization rate can be reduced. The surfactant is not particularly limited, and known surfactants such as cationic surfactants, anionic surfactants, ionic surfactants such as amphoteric surfactants, and nonionic surfactants may be used. However, a surfactant having a polyoxyethylene group is preferable from the viewpoint of excellent compatibility with each monomer component.

  Examples of the surfactant having a polyoxyethylene group include polyoxyethylene hydrogenated castor oil, polyoxyethylene castor oil, polyoxyethylene glycerin fatty acid ester, polyoxyethylene alkyl ether such as polyoxyethylene lauryl ether, polyoxyethylene poly Polyoxyethylene such as oxypropylene copolymer, polyoxyethylene polysiloxane ether block copolymer, polyoxyethylene polyoxypropylene ethylenediamine, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene sorbitan monooleate (eg polysorbate 80) Sorbitan fatty acid esters (polysorbate), polyoxyethylene sorbite fatty acid ester, polyoxyethylene alkylphenyl ether , Polyoxyethylene alkyl phenyl ether formaldehyde condensates such as tyloxapol, polyoxyethylene sterol, polyoxyethylene hydrogenated sterol, polyoxyethylene fatty acid esters such as polyethylene glycol monostearate, polyoxyethylene lanolin alcohol, polyoxyethylene alkylamine , Polyoxyethylene alkylamide, polyoxyethylene alkyl ether phosphoric acid and the like.

  Among the surfactants having a polyoxyethylene group described above, they are nonionic and have a polyoxyethylene group from the viewpoint of improving water wettability due to compatibility with each monomer component and ease of remaining in a polymer material. A surfactant is preferred. Among these, polyoxyethylene hydrogenated castor oils, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene polysiloxane ethers and polyoxyethylene polyoxypropylene copolymers are particularly preferable.

  The refreshing agent can increase the compatibility of each monomer component and reduce unreacted residual components in the resulting polymer material. For example, when a contact lens is produced from the polymer material, it is refreshing to the eyes. It is possible to give a feeling and to eliminate the feeling of foreign matter and itchiness when wearing contact lenses.

  Although it does not specifically limit as said refreshing agent, 1-menthol, d-menthol, dl-menthol, d-camphor, dl-camphor, d-borneol, dl-borneol, geraniol, eucalyptus oil, bergamot oil, fennel oil, Mentha oil, rose oil, cool mint and the like can be mentioned.

  The thickening agent can increase the compatibility of each monomer component, reduce unreacted residual components in the resulting polymer material, and adjust the viscosity of the polymerizable composition. Moreover, according to the said thickening agent, when manufacturing a contact lens etc. from a polymer material, for example, a moist feeling can be given with respect to eyes and the foreign material feeling at the time of wearing and a dry feeling can be reduced.

  The thickening agent is not particularly limited, but sodium hyaluronate, sodium chondroitin sulfate, sodium alginate, sorbitol, dextran 70, sodium carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, carboxyvinyl polymer, polyvinyl alcohol, polyvinylpyrrolidone, Examples include Macrogol 4000.

<[F] component: UV absorber, dye, UV absorber>
When the polymer material obtained by polymerizing the polymerizable composition is used as an ophthalmic lens such as a contact lens, a polymerizable or non-polymerizable ultraviolet absorber, dye or ultraviolet absorbing dye is further added to the polymerizable composition. It is preferable to make it contain. Thereby, ultraviolet absorptivity can be imparted or the material can be colored. These may be used alone or in combination of two or more.

  Specific examples of the polymerizable ultraviolet absorber include, for example, 2-hydroxy-4- (meth) acryloyloxybenzophenone, 2-hydroxy-4- (meth) acryloyloxy-5-t-butylbenzophenone, 2-hydroxy- Benzophenone-based polymerizable ultraviolet absorbers such as 4- (meth) acryloyloxy-2 ′, 4′-dichlorobenzophenone and 2-hydroxy-4- (2′-hydroxy-3 ′-(meth) acryloyloxypropoxy) benzophenone; 2- (2′-hydroxy-5 ′-(meth) acryloyloxyethylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-5 ′-(meth) acryloyloxyethylphenyl) -5-chloro-2H -Benzotriazole, 2- (2'-hydroxy-5 '-(meth) a Liloyloxypropylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-5 ′-(meth) acryloyloxypropyl-3′-t-butylphenyl) -5-chloro-2H-benzotriazole, 2- Benzotriazole-based polymerizable ultraviolet absorbers such as (2′-hydroxy-5 ′-(2 ″ -methacryloyloxyethoxy) -3′-t-butylphenyl) -5-methyl-2H-benzotriazole; 2-hydroxy- Salicylic acid derivative-based polymerizable ultraviolet absorbers such as phenyl 4-methacryloyloxymethylbenzoate; 2-cyano-3-phenyl-3- (3 ′-(meth) acryloyloxyphenyl) propenyl acid methyl ester, etc. Can be used alone or in admixture of two or more.

  Specific examples of the polymerizable dye include 1-phenylazo-4- (meth) acryloyloxynaphthalene, 1-phenylazo-2-hydroxy-3- (meth) acryloyloxynaphthalene, 1-naphthylazo-2-hydroxy- 3- (meth) acryloyloxynaphthalene, 1- (α-anthrylazo) -2-hydroxy-3- (meth) acryloyloxynaphthalene, 1-((4 ′-(phenylazo) -phenyl) azo) -2-hydroxy- 3- (meth) acryloyloxynaphthalene, 1- (2 ′, 4′-xylylazo) -2- (meth) acryloyloxynaphthalene, 1- (o-tolylazo) -2- (meth) acryloyloxynaphthalene, 2- ( m- (meth) acryloylamide-anilino) -4,6-bis (1 ′-(o- Rilazo) -2'-naphthylamino) -1,3,5-triazine, 2- (m-vinylanilino) -4- (4'-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'-naphthyl) -3-vinylphthal Acid monoamide, N- (1 ′-(o-tolylazo) -2′-naphthyl) -6-vinylphthalic acid monoamide, 3-vinylphthalic acid- (4 ′-(p-sulfophenylazo) -1′-naphthyl) mono Esters, 6-vinyl vinyl Talic acid- (4 ′-(p-sulfophenylazo) -1′-naphthyl) monoester, 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, 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-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'-hydroxy-4'-pyrazolylazo) anilino ) -6-isopropenyl-1,3,5-triazine, 2-amino-4- (p-phenylazoanilino) -6-isopropenyl-1,3,5-triazine, 4-phenylazo-7- ( Meta) Acryl Ruamido-1-azo polymerizable dye such as naphthol;

  1,5-bis ((meth) acryloylamino) -9,10-anthraquinone, 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′-isopropyl) Nylbenzoylamide) -9,10-anthraquinone, 1- (3′-isopropenylbenzoylamide) -9,10-anthraquinone, 1- (2′-isopropenylbenzoylamide) -9,10-anthraquinone, 1,4 -Bis (4'-vinylbenzoylamide) -9,10-anthraquinone, 1,4-bis (4'-isopropenylbenzoylamide) -9,10-anthraquinone, 1,5'-bis (4'-vinylbenzoyl) Amido) -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-an Laquinone, 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-amino-4- (3 '-(meth) acryloylaminophenylamino) -9 , 10-anthraquinone-2-sulfonic acid, 1-amino-4- (3 ′-(meth) acryloylaminobenzylamino) -9,10-anthraquinone-2-sulfonic acid, 1- (β-ethoxycarbonylallylamino) -9,10-anthraquinone, 1- (β-carboxyallylamino) -9,10-anthraquinone, 1,5-di- (β-carboxyallylamine Mino) -9,10-anthraquinone, 1- (β-isopropoxycarbonylallylamino) -5-benzoylamide-9,10-anthraquinone, 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, 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" -yl-amino) -anilino) -6-chloro-1,3,5-triazine and other anthraquinone polymerizable dyes; o-nitroanilinomethyl (meth) acrylate and the like And (meth) acryloylated tetraamino copper phthalocyanine, (meth) acryloylated (dodecanoylated tetraamino copper phthalocyanine), and the like. These can be used alone or in admixture of two or more.

  Specific examples of the polymerizable ultraviolet-absorbing dye include 2,4-dihydroxy-3 (p-styrenoazo) benzophenone, 2,4-dihydroxy-5- (p-styrenoazo) benzophenone, and 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) acryloyloxypropylphenyl) Azo) benzophenone, 2,4-dihydroxy -5- (p- (meth) acryloyloxypropylphenylazo) benzophenone, 2,4-dihydroxy-3- (o- (meth) acryloyloxymethylphenylazo) benzophenone, 2,4-dihydroxy-5- (o- (Meth) acryloyloxymethylphenylazo) benzophenone, 2,4-dihydroxy-3- (o- (meth) acryloyloxyethylphenylazo) benzophenone, 2,4-dihydroxy-5- (o- (meth) acryloyloxyethyl) Phenylazo) 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 (meth) acryloyloxyethylamino) phenylazo) Benzophenone, 2,4-dihydroxy-3- (o- (N, N-di (meth) acryloyloxyethylamino) phenylazo) benzophenone, 2,4-dihydroxy-5- (o- (N, N-di (meta ) Acryloylethylamino) 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) acryloyloxyethylamino) 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) benzofu And benzophenone type polymerizable ultraviolet absorbing dyes such as non, such as 2-hydroxy-4-(p-Suchirenoazo) benzoic acid such as benzoic acid phenyl polymerizable ultraviolet absorbing dye and the like. These can be used alone or in admixture of two or more.

Further, the polymerizable ultraviolet absorber, dye or ultraviolet absorbing dye is copolymerized in advance with a comonomer (for example, a component typified by the component [A], [B] or [C]) to obtain a polymer. It can also be added to the polymerizable composition.
Furthermore, for example, a polyamide synthesized using amino group-containing copper phthalocyanine as a component, or a monomer (for example, a component represented by [A] component, [B] component or [C] component) using azo group-containing copper phthalocyanine as an initiator in advance. It is also possible to add a dye or the like that has been polymerized to the polymerizable composition.

  The total content of the [F] component UV absorber, dye and UV-absorbing dye is 3 parts by mass or less, preferably 0.01 parts by mass or more and 2 parts by mass with respect to 100 parts by mass of all monomer components. Or less. When these amounts exceed 3 parts by mass, the mechanical strength of the ophthalmic lens material tends to decrease. Furthermore, in consideration of the toxicity of ultraviolet absorbers and pigments, they tend to be unsuitable as materials for ophthalmic lenses such as contact lenses that come into direct contact with living tissue and intraocular lenses that are embedded in living bodies. In particular, in the case of a pigment, if the amount is too large, the lens color becomes dark and the transparency is lowered, and the lens tends to be difficult to transmit visible light.

<[G] component: polymerization initiator>
When the polymer material of the present invention is used as an ophthalmic lens material, the polymerizable composition can be cured by a mold method or the like. In order to perform such curing, it is preferable to further include [G] a polymerization initiator in the polymerizable composition. By adding a polymerization initiator of the component [G] to the polymerizable composition, heating and / or simple operation by irradiating ultraviolet rays and / or visible light (hereinafter simply referred to as “light”). The polymerizable composition can be cured.

  Examples of thermal polymerization initiators used for polymerization by heating include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), benzoyl peroxide, and t-butyl hydro gen. Examples include peroxide, cumene hydroperoxide, lauroyl peroxide, t-butylperoxyhexanoate, 3,5,5-trimethylhexanoyl peroxide, and the like. These radical polymerization initiators can be used alone or in admixture of two or more. These radical polymerization initiators are preferably used in an amount of 0.001 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of all monomer components.

  Examples of photopolymerization initiators used for polymerization by light irradiation include phosphines such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO) and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide. Oxide photopolymerization initiators; benzoin photopolymerization initiators such as methyl orthobenzoyl benzoate, methyl benzoyl formate, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin-n-butyl ether; 2-hydroxy 2-methyl-1-phenylpropan-1-one (HMPPO), p-isopropyl-α-hydroxyisobutylphenone, pt-butyltrichloroacetophenone, 2,2-dimethoxy Phenone photopolymerization initiators such as 2-phenylacetophenone, α, α-dichloro-4-phenoxyacetophenone, N, N-tetraethyl-4,4-diaminobenzophenone; 1-hydroxycyclohexyl phenyl ketone; 1-phenyl-1 , 2-propanedione-2- (o-ethoxycarbonyl) oxime; thioxanthone photopolymerization initiators such as 2-chlorothioxanthone and 2-methylthioxanthone; dibenzosvalon; 2-ethylanthraquinone; benzophenone acrylate; Benzophenone; benzyl and the like can be mentioned. These photopolymerization initiators can be used alone or in admixture of two or more. Moreover, you may use a photosensitizer with a photoinitiator. The ratio of use of these photopolymerization initiator and photosensitizer is preferably 0.001 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of all monomer components. It is as follows.

  In either case, if the amount of the polymerization initiator is too large, the material itself may become too soft or brittle. Moreover, when there is too little quantity of an initiator, the monomer and oligomer which remain in the polymer material obtained may increase, and as a result, the material surface may become sticky.

[Polymer material]
The polymer material of the present invention can be obtained by heating and / or irradiating the polymerizable composition with ultraviolet rays and / or visible light to copolymerize and cure the monomer components in the polymerizable composition. It can also be obtained by copolymerization by electron beam irradiation instead of ultraviolet irradiation.

The water content of the polymer material is preferably 40% or more, and more preferably 50% or more. When the water content of the polymer material is 40% or more, water wettability on the surface of the polymer material can be improved. The water content of the polymer material was immersed in distilled water until equilibrium was reached, then the mass W3 of the polymer material adjusted at 20 ° C. for 1 hour or more, and then in a dryer set at 105 ° C. for 16 hours. The mass W4 of the polymer material after drying is measured, and is a value calculated from the following equation.
Moisture content (%) = (W3-W4) / W3 × 100

  In the polymer material, additives such as the above-described surfactant, cooling agent, thickening agent and the like can be held inside. When the polymer material is used as an ophthalmic lens, these additives can be kept inside the ophthalmic lens even after the hydration, elution, and sterilization steps in the production stage. Therefore, the polymer material obtained by the additive retained inside can be provided with various characteristics and functionality. That is, the surfactant can improve the water wettability of the polymer material surface, and the refreshing agent can add functionality that gives a refreshing sensation to the eye of the ophthalmic lens wearer. The agent can add functionality that moisturizes the eyes of the ophthalmic lens wearer.

  The polymer material has good flexibility. The lower limit of the tensile modulus representing the flexibility of the polymer material is preferably 0.1 MPa, more preferably 0.15 MPa. On the other hand, the upper limit of the tensile modulus is preferably 0.8 MPa, and more preferably 0.7 MPa. If the tensile modulus of the polymer material is smaller than the above lower limit, the polymer material is not stiff, and when used as an ophthalmic lens, the shape retention on a finger is poor and handling may be difficult. Conversely, when the tensile modulus of the polymer material exceeds the above upper limit, the polymer material becomes hard and the wearing feeling of the ophthalmic lens may be deteriorated.

  In the production of the polymer material, a bulk polymerization method or a solution polymerization method is used. In the bulk polymerization method, the viscosity of the system extremely increases with the progress of polymerization, the monomer component cannot diffuse in the high viscosity system, and the monomer that can no longer participate in the polymerization reaction often remains unpolymerized. . In the solution polymerization method, the solvent often does not participate in the reaction and therefore remains in the polymer. In the production of contact lenses that are medical devices, in order to reduce these residues as much as possible, the polymer material obtained by curing is immersed in water or an organic solvent or a mixed solution thereof, and this is preferably repeated. Thus, the residue is eluted and removed from the polymer material. As a solvent for such treatment, an aqueous solution in which an inorganic compound such as physiological saline is dissolved, or a mixed solution of these with an organic solvent may be used.

  On the other hand, the polymer material obtained from the polymerizable composition of the present invention has a reduced amount of monomer which is cured and remains unpolymerized in the polymer material. Therefore, the polymer material is highly safe when used in various applications. In particular, the polymer material is particularly suitable for use as an ophthalmic lens such as a contact lens because it is used in contact with or close to the eye. Moreover, since the residual monomer is reduced in the polymer material, for example, in the manufacturing process of the ophthalmic lens, an extraction step for removing the residual monomer from the polymer material can be omitted or simplified. As a result, the manufacturing process can be simplified and the manufacturing cost can be reduced. By using the polymer material as a material for contact lenses that are widely used for daily life, there are few residual monomer components, high safety, and excellent oxygen permeability and water wettability. A highly reliable contact lens can be provided at low cost.

  When the polymer material of the present invention is used as an ophthalmic lens material, the polymerizable composition can be cured by a mold method. When the polymerizable composition is heated and polymerized by the mold method, the polymerizable composition containing the thermal polymerization initiator is filled in a mold corresponding to the shape of the desired ophthalmic lens material, and the mold is used. The ophthalmic lens material can be produced by heating and polymerizing gradually, and subjecting the obtained polymer material to mechanical processing such as cutting and polishing as necessary. This cutting may be performed on the entire surface of one or both surfaces of the polymer material, or may be performed on a part of one surface or both surfaces of the polymer material.

  The heating temperature when heating the polymerizable composition in the mold is preferably 50 ° C. or higher and 150 ° C. or lower, more preferably 60 ° C. or higher and 140 ° C. or lower. In addition, the heating time for heating the polymerizable composition in the mold is preferably 10 minutes to 120 minutes, more preferably 20 minutes to 60 minutes. By setting the heating temperature in the mold to 50 ° C. or more, the polymerization time can be shortened, and by setting the heating time to 10 minutes or more, the residual monomer component can be reduced. On the other hand, by setting the heating temperature in the mold to 150 ° C. or less or the heating time to 120 minutes or less, volatilization of each monomer component can be suppressed and deformation of the mold can be prevented.

  In the mold method, when the polymerizable composition is polymerized by irradiating light, after filling the polymerizable composition containing the photopolymerization initiator into the mold corresponding to the shape of the desired ophthalmic lens material. The ophthalmic lens material can be produced by irradiating the mold with light and performing polymerization, and subjecting the obtained molded body to mechanical processing such as cutting and polishing as necessary. In such polymerization by light irradiation, as in the case of polymerization by heating, cutting may be performed over the entire surface of one or both surfaces of the polymer material, or one surface of one or both surfaces of the polymer material may be cut. You may carry out with respect to a part.

  The material of the mold used for polymerization by light irradiation is not particularly limited as long as it is a material that can transmit light necessary for polymerization and curing, and general-purpose resins such as polypropylene, polystyrene, nylon, and polyester are preferable. It may be. By molding and processing these materials, a mold having a desired shape can be obtained.

After the polymerizable composition containing each polymerization component is filled in such a mold, polymerization is performed by irradiating light. The wavelength range of the irradiated light can be selected according to the function of the ophthalmic lens material. However, it is necessary to select the type of photopolymerization initiator to be used depending on the wavelength range of light to be irradiated. The illuminance of light is preferably 0.1 mW / cm ² or more and 100 mW / cm ² or less. You may irradiate light of different illumination intensity in steps. The light irradiation time is preferably 1 minute or longer. By setting such a predetermined illuminance and irradiation time, the polymerizable composition can be sufficiently cured while preventing deterioration of the mold material. Furthermore, the polymerizable composition may be heated simultaneously with the light irradiation, whereby the polymerization reaction is promoted and a copolymer can be easily formed.

  The amount of residual monomer in the polymer material obtained under the above polymerization conditions is preferably 1% by mass or less, more preferably 0.5% by mass or less for N-VP having a mass ratio of [C] to the polymer material. 0.2 mass% or less is more preferable. In addition, among the silicone compounds of the [B] component, for the [B2] component that has a relatively low molecular weight and is likely to remain or dissolve, a residual amount of 1% by mass or less is preferable, and 0.1% by mass or less is more preferable. Preferably, 0.02 mass% or less is more preferable. By making the residual amount of N-VP as the component [C] 1% by mass or less with respect to the amount used, the safety of the obtained polymer material in various applications, particularly in ophthalmic lens applications, can be improved. Further, in the production stage, steps such as elution treatment of residual monomers in the polymer material can be omitted or simplified. Furthermore, the silicone compound of component [B2] is insoluble in water, and unlike N-VP, it is difficult to elute and remove from a polymer material with an aqueous processing solution such as water or physiological saline. By setting the residual amount of the silicone compound of the [B2] component having such characteristics to 1% by mass or less based on the amount used, it is possible to ensure the safety of the polymer material and to omit or simplify the manufacturing process as described above. In addition, the stability of physical properties and shape of the polymer material can be suppressed.

  In order to improve the surface characteristics of the polymer material such as an ophthalmic lens material, low-temperature plasma treatment, atmospheric pressure plasma, corona discharge and the like can be performed. By performing the low temperature plasma treatment, it is possible to obtain an ophthalmic lens having more excellent water wettability and / or contamination resistance. The low-temperature plasma treatment can be performed in a rare gas atmosphere such as an alkane having 1 to 6 carbon atoms and a fluorine-substituted alkane, nitrogen, oxygen, carbon dioxide, argon, hydrogen, air, water, silane, or a mixture thereof. . In particular, because physical surface modification effect by ion etching and chemical surface modification effect by radical implantation are expected, oxygen alone, carbon dioxide alone, or oxygen and water, tetrafluoromethane, It is preferable to perform the low temperature plasma treatment in a rare gas atmosphere with a mixture of organosilane, methane, nitrogen, or the like. The low temperature plasma treatment may be performed under reduced pressure or under atmospheric pressure. In low-temperature plasma processing, output, processing time, and gas concentration are adjusted as appropriate using high-frequency RF (for example, 13.56 MHz), low-frequency AF (for example, 15.0 to 40.0 KHz), and microwaves (for example, 2.45 GHz). By doing so, the surface modification effect can be controlled.

  As described above, the polymer material obtained from the polymerizable composition has a low residual monomer amount and high oxygen permeability and surface wettability. Therefore, this polymer material is highly safe and suitable for use as an intraocular lens, artificial cornea, corneal onlay, corneal inlay, etc., including ophthalmic lenses, that is, contact lenses.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

[Use ingredients]
Meanings of abbreviations used in the following examples are shown.
N-VP: N-vinyl-2-pyrrolidinone TRIS: Tris (trimethylsiloxy) silylpropyl methacrylate EDMA: Ethylene glycol dimethacrylate
HMPPO: 2-hydroxy-2-methyl-1-phenylpropan-1-one 2-MTA: 2-methoxyethyl acrylate 2-ETA: 2-ethoxyethyl acrylate EEA: ethoxyethoxyethyl acrylate EA: ethyl acrylate EMA: ethyl methacrylate BuA: n-butyl acrylate BuMA: n-butyl methacrylate HEMA: 2-hydroxyethyl methacrylate MMP: 1-methyl-3-methylene-2-pyrrolidinone DMAA: N, N-dimethylacrylamide AMA: allyl methacrylate TPO: 2, 4, 6-Trimethylbenzoyl-diphenylphosphine oxide HMEPBT: 2- (2′-hydroxy-5′-methacryloyloxyethylphenyl) -2H-benzotriazole PCPM A: Polymethacrylic acid ester containing phthalocyanine HCO-60: Polyoxyethylene (60) hydrogenated castor oil Macromonomer (8): Silicone compound represented by the above formula (8)

[Synthesis example]
Synthesis of Macromonomer (8) In a 1 L three-necked flask equipped with a Dimroth condenser, a mechanical stirrer, and a thermometer in a side tube previously substituted with nitrogen, 75.48 g (0.34) of isophorone diisocyanate (IPDI) Mol) and 0.12 g of iron acetylacetonate (FeAA). Next, 529.90 g of both-end hydroxyl group dimethylsiloxane (“KF-6002” manufactured by Shin-Etsu Chemical Co., Ltd., polymerization degree 40, hydroxyl group equivalent 1560 g / mol) was added and heated in an oil bath heated to 80 ° C. for about 4 hours. , Stirred.

Next, 39.47 g (0.34 mol) of 2-hydroxyethyl acrylate (HEA) and 0.20 g of p-methoxyphenol (MEHQ) as a polymerization inhibitor were added to the three-necked flask, and an oil at 80 ° C. was added. Stir in the bath. After about 3 hours, the reaction solution was collected and analyzed using ¹ H-NMR and FT-IR to confirm that the predetermined compound was obtained. Further, the crude product was extracted and washed with n-hexane and acetonitrile, the n-hexane layer was recovered, and the organic solvent and the low molecular compound were distilled off under reduced pressure. In this way, 522.33 g (yield 81%) of a purified compound of the macromonomer (8) was obtained.

The measured values of the macromonomer (8) obtained in the synthesis example are as follows.
(1) ¹ H-NMR (δ value, solvent: chloroform-d)
0.06 ppm (Si—CH ₃ , m), 0.52 ppm (Si—CH ₂ , 2H, m), 2.91 ppm (NH—CH ₂ , 2H, d), 3.02 ppm (CH ₂ —N═C) _{= O, 2H, s),} 3.42ppm (-O-CH 2, 2H, t), 3.61ppm (-O-CH 2, 2H, m), 4.18-4.34ppm (- (O) CO—CH ₂ —, 6H, m), 4.54 ppm (NH, 1H, s), 4.85 ppm (NH, 1H, s), 5.84 ppm (CH = 1H, dd), 6.14 ppm (CH = 1H, dd), 6.43 ppm (CH = 1H, dd)
(2) Infrared absorption spectrum (FT-IR)
1262 cm ⁻¹ and 802 cm ⁻¹ (Si—CH ₃ ), 1094 cm ⁻¹ and 1023 cm ⁻¹ (Si—O—Si), 1632 cm ⁻¹ (C═C), around 1728 cm ⁻¹ (C═O, ester and urethane) ).

[Example 1]
20 parts by mass of 2-MTA as component [A], 30 parts by mass of macromonomer (8) and 30 parts by mass of TRIS as silicone compounds of component [B], 20 parts by mass of N-VP of component [C], A polymerizable composition was prepared containing 0.4 part by mass of EDMA as a crosslinking agent for the component [D] and 0.4 part by mass of HMPPO as a polymerization initiator for the component [G] (composition α in Table 1). The polymerizable composition was injected into a mold having a contact lens shape (made of polypropylene, corresponding to a contact lens having a diameter of 14.2 mm and a center thickness of 0.08 mm), and then a high-pressure mercury lamp (2 kW) was applied to the mold. Used for photopolymerization by irradiation with UV light for 20 minutes. Irradiation was performed only from the side corresponding to the FC surface of the lens. After polymerization, the polymer was removed from the mold to obtain a contact lens-shaped polymer material.

[Example 2]
As a component [A], a contact lens-shaped polymer material was obtained in the same manner as in Example 1 except that 20 parts by mass of 2-ETA was used.

[Example 3]
As a component [A], a contact lens-shaped polymer material was obtained in the same manner as in Example 1 except that 20 parts by mass of EEA was used.

[Example 4]
As a component [A], a contact lens-shaped polymer material was obtained in the same manner as in Example 1 except that 20 parts by mass of EA was used.

[Example 5]
As a component [A], a contact lens-shaped polymer material was obtained in the same manner as in Example 1 except that 20 parts by mass of BuA was used.

[Example 6]
25 parts by mass of 2-MTA as [A] component, 10 parts by mass of macromonomer (8) and 25 parts by mass of TRIS as silicone compound of [B] component, 40 parts by mass of N-VP of [C] component, A polymerizable composition containing 0.4 parts by mass of EDMA as a crosslinking agent of [D] component and 0.4 parts by mass of HMPPO as a polymerization initiator of [G] component (composition β in Table 1) was prepared, and A contact lens-shaped polymer material was obtained in the same manner as in Example 1.

[Example 7]
As a component [A], a contact lens-shaped polymer material was obtained in the same manner as in Example 6 except that 25 parts by mass of 2-ETA was used.

[Example 8]
As a component [A], a contact lens-shaped polymer material was obtained in the same manner as in Example 6 except that 25 parts by mass of EEA was used.

[Example 9]
As a component [A], a contact lens-shaped polymer material was obtained in the same manner as in Example 6 except that 25 parts by mass of EA was used.

[Example 10]
As a component [A], a contact lens-shaped polymer material was obtained in the same manner as in Example 6 except that 25 parts by mass of BuA was used.

[Comparative Example 1]
A contact lens-shaped polymer material was obtained in the same manner as in Example 1 except that 20 parts by mass of HEMA was used instead of the component [A].

[Comparative Example 2]
A contact lens-shaped polymer material was obtained in the same manner as in Example 1 except that 20 parts by mass of DMAA was used instead of the component [A].

[Comparative Example 3]
A contact lens-shaped polymer material was obtained in the same manner as in Example 1 except that 20 parts by mass of MMP was used instead of the component [A].

[Comparative Example 4]
A contact lens-shaped polymer material was obtained in the same manner as in Example 1 except that 20 parts by mass of EMA was used instead of the component [A].

[Comparative Example 5]
A contact lens-shaped polymer material was obtained in the same manner as in Example 1 except that 20 parts by mass of BuMA was used instead of the component [A].

[Comparative Example 6]
A contact lens-shaped polymer material was obtained in the same manner as in Example 6 except that 25 parts by mass of HEMA was used instead of the component [A].

[Comparative Example 7]
A contact lens-shaped polymer material was obtained in the same manner as in Example 6 except that 25 parts by mass of DMAA was used instead of the component [A].

[Comparative Example 8]
A contact lens-shaped polymer material was obtained in the same manner as in Example 6 except that 25 parts by mass of MMP was used instead of the component [A].

[Comparative Example 9]
A contact lens-shaped polymer material was obtained in the same manner as in Example 6 except that 25 parts by mass of EMA was used instead of the component [A].

[Comparative Example 10]
A contact lens-shaped polymer material was obtained in the same manner as in Example 6 except that 25 parts by mass of BuMA was used instead of the component [A].

For the homopolymer obtained by polymerizing the monomer used as the [A] component in Examples 1 to 10 and the monomer used in place of the [A] component in Comparative Examples 1 to 10, the glass transition temperature (Tg) and Table 2 shows the water absorption values. The glass transition temperature of each homopolymer is a value measured by differential scanning calorimetry (DSC) at a scanning speed of 20 ° C./min, or a value cited from literature (Polymer Handbook 3rd Ed.). Moreover, the water absorption of each homopolymer is the mass W1 (g) of the homopolymer immersed in distilled water at 25 ° C. for 16 hours or more, and the mass of the homopolymer after being dried in an oven at 105 ° C. for 16 hours. Each of W2 (g) was measured and calculated from the following formula. Each homopolymer was cured by the method described in Example 1 by adding 0.4 parts by mass of EDMA as a crosslinking agent and 0.4 parts by mass of HMPPO as a polymerization initiator to 100 parts by mass of each monomer. I got it.
Water absorption (%) = (W1-W2) / W1 × 100

  About the polymer material of the contact lens shape obtained in Examples 1-10 and Comparative Examples 1-10, the monomer residual ratio was measured in accordance with the following method. The obtained results are shown in Table 3.

[Quantification of residual monomer components]
<Quantification of residual N-VP>
The contact lens-shaped polymer materials obtained in Examples 1 to 10 and Comparative Examples 1 to 10 were immersed in acetonitrile to extract residual components. This extract was analyzed by HPLC, and the residual ratio (%) of the monomer was calculated for the remaining [C] component N-VP. When quantifying the residual ratio, an acetonitrile solution of N-VP having a known concentration is prepared and subjected to HPLC analysis. From this analysis result, the N-VP concentration (ppm) is plotted on the x-axis, and the HPLC analysis peak area is plotted on the y-axis. A calibration curve was created. The residual ratio S1 (%) with respect to the blending amount in the polymerizable composition of N-VP and the mass ratio S2 (%) of the residual monomer with respect to the contact lens-shaped polymer material are calculated by the following, both up to the order of 0.1% Asked. In addition, V: amount of extraction solvent (mL), A: peak area of N-VP, a: calibration curve slope, b: calibration curve intercept, W: mass (g) of polymer material, w: N in the polymerizable composition -VP blending mass fraction (%).
S1 (%) = {V × (A−b)} / (a × W × w × 100)
S2 (%) = {V × (A−b)} / (a × W × 10000)

<Quantification of residual TRIS>
For the contact lens-shaped polymer materials obtained in Examples 1 to 10 and Comparative Examples 1 to 10, the residual ratio of the monomer with respect to the blending amount of TRIS which is the [B2] component was measured. The measurement is carried out in the same manner as in the case of N-VP. Similar to S1 (%) and S2 (%) in the case of N-VP, the residual ratio S3 to the blending amount in the polymerizable composition of TRIS ( %) And the mass ratio S4 (%) of the residual monomer to the contact lens-shaped polymer material, both were calculated to the order of 0.01%.

  As is clear from the results in Table 3, in Examples 1 to 10, the residual ratio of N-VP is clear regardless of the amount of N-VP in the polymerizable composition compared to Comparative Examples 1 to 10. It was shown to be reduced. Moreover, in Examples 1-10, it was also shown that the residual rate of TRIS insoluble in water is suppressed to be extremely low as compared with Comparative Examples 1-10.

[Example 11]
24 parts by mass of 2-MTA as the [A] component, 5 parts by mass of the macromonomer (8) and 30 parts by mass of TRIS as the [B] component, 41 parts by mass of N-VP of the [C] component, [D] Polymerization of 0.3 part by mass of AMA as a cross-linking agent of the component, 1.0 part by mass of HMEPBT as an ultraviolet absorber, 0.02 part by mass of PCPMA as a dye, and [G] component A polymerizable composition containing 0.6 parts by mass of TPO as an initiator was prepared. This polymerizable composition was injected into a mold having a contact lens shape (made of polypropylene, corresponding to a contact lens having a diameter of 14.2 mm and a center thickness of 0.08 mm), and then a blue lamp (TL20W03 manufactured by PHILIPS) was applied to the mold. ) For 20 minutes to carry out photopolymerization. Irradiation was performed only from the side corresponding to the FC surface of the lens. After the polymerization, the polymer material having the contact lens shape obtained by taking out from the mold is subjected to plasma treatment (RF output 50 W, 100 Pa) in a carbon dioxide atmosphere, and then immersed in distilled water to perform hydration treatment and equilibrate. Swelled until Then, the polymer material was subjected to an elution treatment by rinsing in distilled water, and then a sterilization (high pressure steam sterilization) treatment (121 ° C., 20 minutes) in a phosphate buffer according to Example 11. Contact lenses were obtained.

[Example 12]
25 parts by mass of 2-MTA as component [A], 10 parts by mass of macromonomer (8) and 25 parts by mass of TRIS as component [B], 40 parts by mass of N-VP of component [C], [D] Polymerizable composition using 0.3 part by weight of AMA as a cross-linking agent of the component, 0.02 part by weight of PCPMA as the dye of the [F] component, and 0.4 part by weight of HMPPO as the polymerization initiator of the [G] component A contact lens according to Example 12 was obtained in the same manner as in Example 11 except that a high pressure mercury lamp (2 kW) was used as the irradiator.

  The contact lenses obtained in Examples 11 and 12 were subjected to evaluation of water wettability and surface lubricity, measurement of moisture content and tensile elastic modulus, and cytotoxicity test according to the following methods. Table 4 shows the obtained results.

[Evaluation of water wettability]
For the contact lenses obtained in Examples 11 and 12, after sterilization, the lens was taken out with tweezers and shaken lightly twice, and the water wettability of the lens surface after removing water adhering to the lens was confirmed visually. The determination was made according to the following evaluation criteria.
-Evaluation criteria-
A: The whole lens is uniformly wet.
B: Although the entire lens is uniformly wet, it is partially repelled after being left for a certain period of time.
C: Slightly lacking in water wettability, and water repellency is seen around the lens.
D: Strong water repelling is observed.

[Surface lubricity]
For the contact lenses obtained in Examples 11 and 12, after sterilization, the contact lens was folded in half on the fingers and lubricated when the lenses were rubbed together (the adhesion between the lenses, the lens and fingers) ) Was evaluated. The water wettability of the lens surface was also confirmed visually. The determination was made according to the following evaluation criteria.
-Evaluation criteria-
A: Good sliding between lenses, which is suitable as a contact lens.
B: A slight squeak is felt when the lenses are rubbed together.
C: Although there is no adhesion between the lens and fingers, there are times when the lens slips poorly and stops moving.
D: The lens surface is sticky and the adhesion between the lens and fingers is strong.

[Measurement of moisture content]
The contact lenses obtained in Examples 11 and 12 were adjusted at 20 ° C. for 1 hour or longer to measure mass W3 (g), then dried in a dryer set at 105 ° C. for 16 hours, and again mass W4 (g ) Was measured. The moisture content was calculated from these measured values according to the following formula.
Moisture content (%) = (W3-W4) / W3 × 100

[Measurement of tensile modulus]
From the contact lenses obtained in Examples 11 and 12, a measurement piece was produced by punching into a dumbbell shape having a tensile portion width of 1.8 mm. Using the measurement piece thus obtained, the tensile modulus was measured with a universal tester “AG-IS MS type” manufactured by Shimadzu Corporation. The measurement was performed in a physiological saline solution at 20 ° C. at a tensile rate of 100 mm / min, and the tensile elastic modulus (Young's modulus) was calculated from the obtained stress-elongation curve.

[Cytotoxicity test]
The contact lenses obtained in Examples 11 and 12 were subjected to a cytotoxicity test using V79 cells (Chinese hamster lung fibroblasts). The determination was made according to the following evaluation criteria.
○: It can be judged that there is no problem in biological safety.
X: It cannot be judged that there is no problem in biological safety.

  As is apparent from the results in Table 4, the contact lenses of Examples 11 and 12 were both flexible and excellent in water wettability and surface lubricity. It was also shown that there are no biological safety issues.

[Example 13]
Polymerizable composition prepared in Example 12 (25 parts by mass of 2-MTA as component [A], 10 parts by mass of macromonomer (8) as component [B], 25 parts by mass of TRIS, and component [C] 40 parts by mass of N-VP, 0.3 part by mass of AMA as a crosslinking agent for the component [D], 0.02 parts by mass of PCPMA as a pigment for the component [F], and a polymerization initiator for the component [G] A polymerizable composition containing 0.4 parts by mass of HMPPO and 1.0 part by mass of ethanol as a water-soluble organic solvent as an additive of the component [E] was prepared, and contact was made in the same manner as in Example 12. A lens-shaped polymer material was obtained. Further, the obtained polymer material was subjected to plasma treatment, hydration treatment, elution treatment, and sterilization treatment in the same manner as in Example 12 to obtain a contact lens according to Example 13.

[Example 14]
A contact lens according to Example 14 was obtained in the same manner as in Example 13 except that 3.0 parts by mass of ethanol, which is a water-soluble organic solvent, was used as an additive for the component [E].

[Example 15]
The contact lens according to Example 15 was obtained in the same manner as in Example 13 except that 1.0 part by mass of N-methyl-2-pyrrolidone, which is a water-soluble organic solvent, was used as an additive of [E] component. Obtained.

[Example 16]
A contact lens according to Example 16 was obtained in the same manner as in Example 13 except that 0.5 part by mass of 1-menthol as a refreshing agent was used as an additive for the component [E].

[Example 17]
A contact lens according to Example 17 was obtained in the same manner as in Example 13 except that 1.0 part by mass of 1-menthol as a cooling agent was used as an additive for the component [E].

[Example 18]
A contact lens according to Example 18 was obtained in the same manner as in Example 13 except that 0.5 part by mass of HCO-60 as a surfactant was used as an additive for the component [E].

[Example 19]
A contact lens according to Example 19 was obtained in the same manner as in Example 13 except that 1.0 part by mass of HCO-60 as a surfactant was used as an additive for the component [E].

  The contact lens-shaped polymer material obtained by taking out from the mold after curing in Examples 13 to 19 was immersed in acetonitrile in the same manner as described above to perform extraction treatment, and the residual ratio of residual N-VP monomer (S1, S2) Was measured. In addition, according to the description of Example 11, contact lenses obtained by sequentially subjecting the polymer material to surface treatment, hydration, elution, and sterilization treatment have water wettability and surface lubricity in the same manner as described above. Evaluation was performed. The results obtained are shown in Table 5. In addition, cytotoxicity tests were performed on the contact lenses in the same manner as the above method, and it was confirmed that there was no problem from the viewpoint of biological safety.

  As is clear from the results in Table 5, it was shown that the residual N-VP of the resulting polymer material was further reduced by using the additive of the [E] component. It was also shown that even when the additive of the component [E] is used, it has good surface lubricity and water wettability and has a surface suitable as an ophthalmic lens material.

[Example 20]
18 parts by mass of 2-MTA as component [A], 15 parts by mass of macromonomer (8) and 37 parts by mass of TRIS as component [B], 30 parts by mass of N-VP of component [C], [D] A polymerizable composition comprising 0.1 part by weight of AMA as a cross-linking agent of the component, 0.01 part by weight of PCPMA as a dye of the [F] component, and 0.4 part by weight of HMPPO as a polymerization initiator of the [G] component The polymer was prepared and photopolymerized in the same manner as in Example 12 to obtain a contact lens-shaped polymer material. Then, it is immersed in distilled water to swell until equilibrium is reached, and then the polymer material is immersed in physiological saline and sterilized (high-pressure steam sterilization) in the liquid to obtain a contact lens according to Example 20. It was.

[Example 21]
24 parts by mass of 2-MTA as component [A], 10 parts by mass of macromonomer (8) and 25 parts by mass of TRIS as component [B], 41 parts by mass of N-VP of component [C], [D] A polymerizable composition comprising 0.1 part by weight of AMA as a cross-linking agent of the component, 0.02 part by weight of PCPMA as a pigment of the [F] component, and 0.4 part by weight of HMPPO as a polymerization initiator of the [G] component A contact lens according to Example 21 was obtained in the same manner as Example 20 except that the lens was prepared.

[Comparative Example 11]
35 parts by mass of MMP and 10 parts by mass of DMAA instead of [A] component, 10 parts by mass of macromonomer (8) as component [B] and 22 parts by mass of TRIS, and EDMA as a crosslinking agent for [D] component 0.4 parts by weight, except that 0.01 parts by weight of PCPMA as a pigment for the [F] component and 0.4 parts by weight of HMPPO as a polymerization initiator for the [G] component were used to prepare a polymerizable composition. A contact lens according to Comparative Example 11 was obtained in the same manner as Example 20.

[Comparative Example 12]
In place of [A] component, 47 parts by mass of MMP and 15.5 parts by mass of DMAA, 22.5 parts by mass of macromonomer (8) and 15 parts by mass of TRIS as [B] component, and crosslinking of [D] component A polymerizable composition was prepared using 0.4 parts by mass of EDMA as an agent, 0.02 parts by mass of PCPMA as a pigment of the [F] component, and 0.4 parts by mass of HMPPO as a polymerization initiator of the [G] component. A contact lens according to Comparative Example 12 was obtained in the same manner as Example 20 except for the above.

  The water content was measured using the contact lenses prepared in Examples 20 and 21 and Comparative Examples 11 and 12. The contact lenses obtained were evaluated for surface lubricity and water wettability by the above methods. The results obtained are shown in Table 6.

  As is clear from the results in Table 6, Example 20 and Comparative Example 11, and Example 21 and Comparative Example 12 are polymer materials having the same water content, but the surface water wettability is: It is shown that the polymer materials of Example 20 and Example 21 obtained from the polymerizable composition containing all the monomer components [A], [B] and [C] are superior. It was.

  The polymerizable composition of the present invention can be used as a highly safe polymer material with a reduced amount of residual monomers in addition to the obtained polymer material having high oxygen permeability and surface wettability. It is preferably used for intraocular lenses, artificial corneas, corneal onlays, corneal inlays, and the like, for use in lenses, ie, contact lenses. In addition to the ophthalmic lens, it can be used for various applications such as a catheter, a tube, a stent, a tube, a blood bag, a probe, and a thin film.

Claims (18)

[A] a polymerizable compound having an acryloyloxy group, having no silicon atom, and having a glass transition temperature of 10 ° C. or less as a homopolymer thereof,
[B] A silicone composition having a polymerizable group, and [C] a polymerizable composition containing N-vinylpyrrolidinone as a monomer component.   The polymerizable composition according to claim 1, wherein the polymerizable compound of the component (A) further has an ether bond.   The polymerizable composition according to claim 1 or 2, wherein the water absorption as a homopolymer of the polymerizable compound of component [A] is 20% or less. The polymerizable composition according to claim 1, 2 or 3, wherein the polymerizable compound of the component (A) is a compound represented by the following formula (1).
_{CH 2 = CH-CO- (OCH} 2 CH 2) n -OR 1 (1)
(In formula (1), R ¹ represents a methyl group or an ethyl group. N represents an integer of 1 to 3.)   The polymerizable compound of the component [A] is at least one selected from the group consisting of 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-methoxyethoxyethyl acrylate and 2-ethoxyethoxyethyl acrylate. Polymerizable composition. The silicone compound of [B] component is
[B1] a compound having an ethylenically unsaturated double bond and a polydimethylsiloxane structure via a urethane bond, and / or [B2] consisting of a silicone-containing alkyl (meth) acrylate, a silicone-containing styrene derivative, and a silicone-containing fumaric acid diester The polymerizable composition according to claim 1, which is at least one compound selected from the group. The polymerizable compound according to claim 6, wherein the silicone compound of the component [B1] is represented by the following formula (2):
A ¹ -U ^1- (S ¹ -W) _m -S ² -U ² -A ² (2)
[In the formula (2), A ¹ and A ² are each independently the following formula (3), U ¹ and U ² are each independently the following formula (4), and S ¹ and S ² are each independently the following formula (5 ) And W are groups represented by the following formula (6), and m represents an integer of 0 to 10.
Y-Z-R ^2- (3)
(In Formula (3), Y is a (meth) acryloyl group, a vinyl group or an allyl group, Z is an oxygen atom or a direct bond, R ² is a direct bond or a straight chain having 1 to 12 carbon atoms, branched. (It is an alkylene group having a chain or an aromatic ring, provided that Y in A ¹ and A ² may be the same or different.)
^{-X 1 -E 1 -X 2 -R 3} - (4)
(In Formula (4), X ¹ and X ² are each independently selected from a direct bond, an oxygen atom and an alkylene glycol group, E ¹ is an —NHCO— group (where X ¹ is a direct bond, X ² is an oxygen atom or an alkylene glycol group, E ¹ forms a urethane bond with X ² ), —CONH— group (in this case, X ¹ is an oxygen atom or an alkylene glycol group, X ² is a direct bond, and E ¹ forms a urethane bond with X ^1. ) Or 2 derived from a diisocyanate selected from the group of saturated or unsaturated aliphatic, alicyclic and aromatic systems A valent group (provided that, in this case, X ¹ and X ² are each independently selected from an oxygen atom and an alkylene glycol group, and E ¹ forms two urethane bonds between X ¹ and X ² ). at is, R Is an alkylene group having a linear or branched chain having 1 to 6 carbon atoms.)

(In the formula (5), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently an alkyl group having 1 to 6 carbon atoms, a fluorine-substituted alkyl group, a phenyl group or a hydrogen atom. K is an integer of 10 to 100, L is 0 or an integer of 1 to 90, and K + L is an integer of 10 to 100.)
^{-R 4 -X 3 -E 2 -X 4} -R 5 - (6)
(In Formula (6), R ⁴ and R ⁵ are each independently an alkylene group having a linear or branched chain having 1 to 6 carbon atoms, and X ³ and X ⁴ are each independently an oxygen atom or alkylene glycol. E ² represents a divalent group derived from a diisocyanate selected from the group consisting of saturated or unsaturated aliphatic, alicyclic and aromatic groups (where E ² represents X ³ and X Forming two urethane bonds between ⁴ ).)]]   10 parts by mass or more of the polymerizable compound of [A] component is 45 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable compound of [A] component, the silicone compound of [B] component and N-vinylpyrrolidinone of [C] component. 8 parts by weight or less, 10 parts by weight or more and 70 parts by weight or less of [B] component silicone compound, and 10 parts by weight or more and 50 parts by weight or less of [C] component N-vinylpyrrolidinone. 2. The polymerizable composition according to item 1. Containing 5 parts by mass or less of the non-polymerizable additive with respect to 100 parts by mass of the total amount of the polymerizable compound of [A] component, the silicone compound of [B] component and the N-vinylpyrrolidinone of [C] component;
The polymerizable composition according to any one of claims 1 to 8, wherein the additive is at least one selected from the group consisting of a water-soluble organic solvent, a surfactant, a cooling agent, and a thickening agent. object.   The water-soluble organic solvent is at least one selected from the group consisting of alcohols having 1 to 3 carbon atoms, acetone, methyl ethyl ketone, dimethylformamide, dimethyl sulfoxide, acetonitrile, N-methyl-2-pyrrolidone and dimethoxyethane. 10. The polymerizable composition according to 9.   The polymerizable composition according to claim 9 or 10, wherein the surfactant is nonionic and has a polyoxyethylene group.   The nonionic surfactants having polyoxyethylene groups are polyoxyethylene hydrogenated castor oils, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene polysiloxane ethers and polyoxyethylene poly The polymerizable composition according to claim 11, which is at least one selected from the group consisting of oxypropylene copolymers.   The refreshing agent is 1-menthol, d-menthol, dl-menthol, d-camphor, dl-camphor, d-borneol, dl-borneol, geraniol, eucalyptus oil, bergamot oil, fennel oil, peppermint oil, rose oil and The polymerizable composition according to claim 9, wherein the polymerizable composition is at least one selected from the group consisting of cool mint.   The thickening agent is a group consisting of sodium hyaluronate, sodium chondroitin sulfate, sodium alginate, sorbitol, dextran 70, sodium carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, carboxyvinyl polymer, polyvinyl alcohol, polyvinylpyrrolidone and macrogol 4000. The polymerizable composition according to claim 9, which is at least one selected from the group consisting of:   A polymer material obtained by curing the polymerizable composition according to any one of claims 1 to 14.   The polymer material according to claim 15, wherein the water content is 40% or more.   An ophthalmic lens comprising the polymer material according to claim 15 or 16.   A contact lens made of the polymer material according to claim 15 or 16.