JP2014040598A - Polymer material, ocular lens, and contact lens - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer material capable, by retaining a surfactant within the polymer material so as to preclude a gradual release thereof, of providing a polymer material having an advanced polymer material water wettability and surface lubricity and capable of sustaining these characteristics.SOLUTION: The polymer material of the present invention includes [I] a cross-linked and hydrogelled polymer containing (A) structural units derived from a polymerizable compound having acryloyloxy groups and having no silicon atoms and (B) structural units derived from a silicone compound having polymerizable groups and [II] a surfactant; the glass transition point, as homopolymer, of the polymerizable compound (A) is -70°C or above and 10°C or below. It is desirable for the content of the surfactant [II] to be 0.05 mass% or above and 1 mass% or below. It is desirable for the surfactant to be a nonionic surfactant having polyoxyethylene groups.

Description

  The present invention relates to a polymer material and an ophthalmic lens and a contact lens comprising the polymer material. Specifically, in addition to high oxygen permeability, the surface is excellent in water wettability, lubricity and flexibility, and is suitable for an ophthalmic lens and a contact lens. Relating to various polymer materials.

  Silicone hydrogels are used as materials for ophthalmic lenses such as contact lenses because of their high oxygen permeability. However, since the silicone hydrogel generally has low water wettability and lubricity on the surface, various efforts such as surface treatment and inclusion of a hydrophilic polymer have been made to improve these points.

  As a technique for improving the surface lubricity and water wettability of a contact lens using such a silicone hydrogel, (1) a technique for incorporating polyvinylpyrrolidone as a hydrophilic polymer in a mixture of monomer components (International Publication No. 01) (2) Technology in which a contact lens is impregnated with a storage solution containing a surfactant or a hydrophilic polymer, and the surfactant is adhered to the surface of the contact lens (Japanese Patent Laid-Open No. 61-69023) ), (3) Technology for covalently bonding a surfactant molecule directly to the surface of a silicone hydrogel lens (see US Pat. No. 4,546,123), (4) A monomer component comprising a silicone-containing monomer and a hydrophilic monomer By using a surfactant or an organic solvent as an additive during the production of contact lenses (5) A mixture of a polymer substrate, a carrier liquid, and an impregnating agent containing a surfactant in a supercritical fluid such as carbon dioxide gas. A technique for encapsulating a surfactant in a polymer by bringing the polymer into contact with each other (JP-A-8-506612) has been developed.

  However, in the conventional technique (1), it is difficult to uniformly dissolve the hydrophobic silicone-containing monomer and the hydrophilic polymer in the monomer mixture. Lubricity is not easily obtained. Moreover, in the said prior art (2), the wettability and surface lubricity of a contact lens cannot be maintained for a long time. In the above prior arts (3) and (4), since the amount of the surfactant used is relatively large, the surfactant aggregated on the contact lens surface and the surfactant contained in the contact lens are gradually released. In addition, water wettability and surface lubricity do not last long, and eye irritation may occur when using contact lenses.

  In addition, in the above conventional technique (5), since the surfactant having a substantially small interaction with the polymer is used, the surfactant is easily eluted from the polymer in a solvent such as water or a buffer solution. In addition, water wettability and surface lubricity cannot be maintained for a long time. In addition, when a surfactant is contained in a polymer material such as a contact lens, the polymer material itself tends to be deformed due to the behavior at the time of incorporation or sustained release, resulting in inconvenience that the stability is impaired.

International Publication No. 01/70837 JP-A-61-69023 U.S. Pat. No. 4,546,123 US Pat. No. 4,534,916 JP-A-8-506612

  The present invention has been made in view of these problems. That is, the main object of the present invention is to impart high water wettability and surface lubricity in the polymer material by maintaining the polymer material so that the surfactant is not gradually released, and to maintain these. It is to provide a polymer material that can be used. Another object of the present invention is to provide a polymer material having excellent shape stability.

The invention made to solve the above problems is
[I] (A) A polymer containing a structural unit derived from a polymerizable compound having an acryloyloxy group and not having a silicon atom, and [II] a polymer material containing a surfactant.

  Since the [I] polymer includes a structural unit derived from the component (A), the polymer material can be contained in the polymer material without releasing the [II] surfactant. In addition, the polymer material can be retained inside the surfactant without eluting the surfactant to the outside due to the interaction between the structural unit derived from the component (A) and the surfactant. As a result, the wettability and surface lubricity of the polymer material can be improved, and the effect can be maintained.

  The polymerizable compound (A) is highly compatible and copolymerizable with other monomer components (for example, a silicone compound as the component (B) described later and a compound having an amide group as the component (C)). Accordingly, the polymerizable composition forming the polymer [I] contains the polymerizable compound (A), so that the polymerization can be performed in a state where the monomer components are uniformly mixed, and the polymerization rate is increased. Can be high. As a result, the polymer material has improved stability and can be prevented from being deformed due to this, and in addition, the residual ratio of the monomer component can be reduced.

  As content of said [II] surfactant, 0.05 mass% or more and 1 mass% or less are preferable. By making content of the said surfactant more than the said minimum, the water wettability and lubricity of the said polymer material surface improve more. Moreover, by making the content of the surfactant not more than the above upper limit, the deformation of the polymer material itself and the elution amount of the surfactant from the polymer material are suppressed.

  As said [II] surfactant, the nonionic surfactant which has a polyoxyethylene group is preferable. Such a surfactant having a polyoxyethylene group is effectively taken in and held in the polymer material by the interaction with the polymerizable compound (A), so that the wettability and lubricity of the surface of the polymer material are increased. Can be improved. In addition, when (A) a polymerizable composition containing a polymerizable compound is mixed with [II] surfactant and cured, the polymerizable composition is caused by the action of a nonionic surfactant having a polyoxyethylene group. The dispersibility of the polymerizable compound (A) and the uniformity of the polymerizable composition therein can be improved, and a polymer material suitable for an ophthalmic lens or the like can be provided.

  Examples of the nonionic surfactant having a polyoxyethylene group include polyoxyethylene hydrogenated castor oil, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene polysiloxane ethers and polyoxyethylene. Particularly preferred is at least one selected from the group consisting of polyoxypropylene copolymers. Such a surfactant having a polyoxyethylene group and a hydrophobic part has a particularly high interaction with the [I] polymer, interacts with the polymer material and is taken into the polymer material, and further strongly into the polymer material. Since it is held, the water wettability and surface lubricity of the polymer material can be further improved.

  (A) As for the glass transition temperature as a homopolymer of a polymeric compound, 10 degrees C or less is preferable. [I] When the polymer contains a structural unit derived from the polymerizable compound (A) having such a glass transition temperature, the polymer growth terminal can easily move even at a later stage of the polymer formation where the curing has progressed to a certain degree, Since other monomer components can be efficiently incorporated into the polymer chain during the curing polymerization, the amount of monomer remaining unpolymerized can be further reduced.

  (A) The water absorption as a homopolymer of the polymerizable compound is preferably 20% or less. [I] The polymer contains a structural unit derived from the polymerizable compound (A) having a water absorption of 20% or less of such a homopolymer, so that the water content of the polymer material is kept below a certain level. The decrease in oxygen permeability can be suppressed.

(A) The polymerizable compound may be 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.)

  Such a compound represented by the above formula (1) can be contained in the polymer material without slow release of the surfactant, and is particularly highly compatible and copolymerizable with other monomer components. . Therefore, by using the compound represented by the above formula (1) as the polymerizable compound (A), the unpolymerized residual ratio of other monomer components in the polymer material can be further reduced, and the polymer material The safety of can be further increased. As described above, specific examples of the polymerizable compound (A) having a particularly high compatibility with other monomer components and a particularly high copolymerization property include 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2 -Methoxyethoxyethyl acrylate or 2-ethoxyethoxyethyl acrylate is preferred.

The above [I] polymer is:
(B) It is good to further contain the structural unit derived from the silicone compound which has a polymeric group. The polymer material can improve elasticity, flexibility, and mechanical strength by using a silicone compound having a polymerizable group as one of the monomer components.

(B) As a silicone compound,
(B1) A compound having an ethylenically unsaturated double bond and a polydimethylsiloxane structure via a urethane bond, and / or (B2) comprising a silicone-containing alkyl (meth) acrylate, a silicone-containing styrene derivative and a silicone-containing fumaric acid diester. At least one compound selected from the group is preferred.

  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 as the component (B1) has an elastic bond called a urethane bond, thereby increasing the elasticity of the polymer material, eliminating brittleness, and improving mechanical strength. . On the other hand, by using the silicone compound of component (B2), not only oxygen permeability but also high flexibility can be imparted to the resulting polymer material. Further, by using the component (B1) and the component (B2) in combination, it is possible to impart higher oxygen permeability to the silicone hydrogel and to achieve both appropriate flexibility and good shape retention.

（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、飽和若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。）］ As the silicone compound of component (B1), those represented by the following formula (2) are preferable. Thus, by using what is represented by following formula (2) as a silicone compound of (B1) component, the oxygen permeability of the said polymer material, elasticity, and mechanical strength can further be 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 is a divalent group derived from a diisocyanate selected from the group of saturated or unsaturated aliphatic, alicyclic and aromatic groups (where E ² is X ³ and X Forming two urethane bonds between ⁴ ).)]]

The above [I] polymer is:
(C) A structural unit derived from a compound having an amide group may be further included. When the [I] polymer further includes a structural unit derived from a compound having an amide group, the wettability of the polymer material can be further improved.

  As the compound having an amide group as the component (C), N-vinylpyrrolidinone is preferable. Since such N-vinylpyrrolidinone has high hydrophilicity, the water wettability of the polymer material can be further enhanced.

  The above [I] polymer is formed from a polymerizable composition containing (A) a polymerizable compound, (B) a silicone compound and (C) N-vinylpyrrolidinone, and the above (A), (B) and (C) As a compounding ratio of the components, the content of the polymerizable compound (A) is 10 parts by mass or more and 45 parts by mass with respect to 100 parts by mass of the total amount of (A) polymerizable compound, (B) silicone compound and (C) N-vinylpyrrolidinone. It is preferable that the content of the (B) silicone compound is 10 parts by mass or more and 70 parts by mass or less and the content of the (C) N-vinylpyrrolidinone is 10 parts by mass or more and 50 parts by mass or less. When the polymerizable composition has the above blending ratio, excellent surface lubricity and water wettability can be realized in the polymer material, and the characteristics of each component described above can be expressed in a balanced manner.

  The polymerizable composition further contains a non-polymerizable additive, and the additive is at least one selected from the group consisting of a water-soluble organic solvent, a refreshing agent, and a thickening agent. The amount is preferably 5 parts by mass or less based on 100 parts by mass of the total amount of (A) the polymerizable compound, (B) the silicone compound and (C) N-vinylpyrrolidinone. By containing the additive in the polymerizable composition, uniform dispersion of each monomer component is promoted, and the uniformity and transparency of the polymer material can be improved. Moreover, the amount of unpolymerized monomers in the polymer material can be further reduced by containing these additives. Furthermore, according to the said polymeric composition, the further functionality can be added to the said polymer material by containing the said additive.

  The water-soluble organic solvent is preferably 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. 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 uniformity and copolymerizability of the polymer 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 At least one selected from the group consisting of oil and cool mint is preferred. By containing such a refreshing agent, the dispersibility of the compound having an amide group as the component (C) in the polymerizable composition can be increased, and the water wettability of the surface of the polymer material can be increased. A refreshing feeling suitable for use of the polymer material obtained from the adhesive composition can be imparted.

  The thickening agent comprises sodium hyaluronate, sodium chondroitin sulfate, sodium alginate, sorbitol, dextran 70, sodium carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, carboxyvinyl polymer, polyvinyl alcohol, polyvinylpyrrolidone and macrogol 4000. At least one selected from the group is preferred. By containing such a thickening agent, the dispersibility of the compound having an amide group as the component (C) can be particularly improved, and the water wettability of the polymer material obtained from the polymerizable composition can be particularly improved. At the same time, it is possible to impart a moist feeling suitable for use of the polymer material.

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

  Therefore, an ophthalmic lens made of the polymer material, particularly a contact lens, has high oxygen permeability and water wettability as described above, and thus can have high commercial value and reliability.

  As described above, the polymer material of the present invention contains a polymer containing a structural unit derived from a polymerizable compound having an acryloyloxy group and not having a silicon atom. It can be well contained inside and can be retained without eluting outside. Therefore, the polymer material has excellent surface lubricity, water wettability, and shape stability. 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 polymer material of the present invention will be described in order.

The polymer material of the present invention comprises:
[I] a polymer containing a predetermined structural unit, and [II] a surfactant.

[I] Polymer [I] The polymer is
(A) including a structural unit derived from a polymerizable compound having an acryloyloxy group and not having a silicon atom,
A structural unit derived from (B) a silicone compound having a polymerizable group and / or (C) a compound having an amide group may be included.
Such a polymer [I] can be formed by curing a polymerizable composition containing a polymerizable compound having an acryloyloxy group as component (A) and not having a silicon atom. The polymerizable composition may preferably contain (B) a silicone compound having a polymerizable group and / or (C) a compound having an amide group, in addition to (D) a crosslinking agent and (E) an additive. , A dye, an ultraviolet absorber, an ultraviolet absorbing dye, a polymerization initiator, and the like.

((A) component: a polymerizable compound having an acryloyloxy group and no silicon atom)
The polymerizable compound (A) has an acryloyloxy group (CH ₂ ═CH—CO—O—) and does not have a silicon atom. The polymerizable compound of the component (A) can efficiently contain a surfactant inside the polymer material by having the above structure. Further, the surfactant can be held inside the polymer material without being eluted out of the polymer material due to the interaction between the component (A) and the surfactant. As a result, the wettability and surface lubricity of the polymer material can be improved, and the effect can be maintained.

  Moreover, the polymerizable compound of the component (A) has high compatibility with the silicone compound of the component (B) and the compound having an amide group of the component (C) which are preferable components described later. Moreover, the polymerizable compound of component (A) has high copolymerizability with both the silicone compound of component (B) and the compound having an amide group of component (C) by having the above structure. Therefore, when the polymerizable composition contains the polymerizable compound of the component (A), the polymerization can be performed in a state where the monomer components are uniformly mixed, and the polymerization rate can be increased. it can. As a result, the residual ratio of the unreacted (B) component silicone compound and the (C) component amide group-containing compound in the polymer material obtained from the polymerizable composition can be reduced. Thus, the polymer material has high safety since the amount of the unreacted monomer contained is reduced. As the polymerizable compound of component (A), one or more kinds of compounds can be used.

  (A) As a compound of a component, the thing whose glass transition temperature of a homopolymer is 10 degrees C or less is preferable. [I] In the polymerization for obtaining the polymer, when the compound of the component (A) is located at the polymer growth terminal during polymerization, it is preferable that the growth terminal part easily moves in the polymer being formed. This is because if the growth terminal is easy to move, the polymer growth terminal can be added to the (B) component silicone compound and the (C) compound having an amide group even in the later stage of polymer formation where the curing has progressed to a certain degree. This is because they approach and react easily. As a result, even at the later stage of polymer formation, the polymer growth terminal and the (B) component silicone compound and the (C) component amide group-containing compound can be bonded, and the polymer material is not polymerized. The amount of the (B) component silicone compound and the (C) component amide group-containing compound remaining as they are is reduced.

  When the 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 of the component (A) is preferably a homopolymer having a glass transition temperature of 10 ° C. or lower. Specifically, as the compound of the component (A), a homopolymer having a glass transition temperature of 10 ° C. or less is preferable, one having 0 ° C. or less is more preferable, and one having −20 ° C. or less is particularly preferable. . On the other hand, if the glass transition temperature is too low, the polymer material containing the component (A) may have undesirable properties such as excessive surface tackiness or reduced shape retention. There is. Specifically, as the compound of component (A), the homopolymer has a glass transition temperature of −150 ° C. or higher, more preferably −120 ° C. or higher, and −100 ° C. or higher. Particularly preferred.

The water absorption as a homopolymer of the component (A) is preferably 20% or less, more preferably 10% or less. This is because when the polymer material contains a compound having an amide group as the component (C) having high hydrophilicity, oxygen permeability may be lowered. Therefore, by using a compound having low water absorption as the component (A), the water content of the polymer material can be kept at a certain level or less, and as a result, a decrease in oxygen permeability of the polymer material can be suppressed. The water absorption rate 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 set at 105 ° C. for 16 hours. Each value is measured and calculated from the following formula.
Water absorption (%) = (W1-W2) / W1 × 100

  The polymerizable compound of component (A) is not particularly limited as long as it has an acryloyloxy group and does not have a silicon atom, but preferably has an ether bond. When the polymerizable compound of the component (A) has an ether bond in addition to the acryloyloxy group, the surfactant can be effectively contained inside the polymer material more efficiently. As a result, the water wettability and surface lubricity of the polymer material can be further improved.

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 water wettability and surface lubricity of the polymer material can be further improved. In addition, the above compound has particularly high compatibility and copolymerization with other monomer components, and can have suitable mobility at the terminal of the growing polymer. As a result, the unpolymerized residual ratio of other monomer components in the polymer material can be further reduced.

  Specific examples of the component (A) compound include 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-methoxyethoxyethyl acrylate, 2-ethoxyethoxyethyl acrylate, methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate. Hexyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, etc., among which 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-methoxyethoxyethyl acrylate or 2-ethoxyethoxyethyl acrylate This is preferable in that the water wettability and surface lubricity of the polymer material are particularly excellent.

  Although it does not specifically limit as a usage-amount of the polymeric compound of (A) component, All the monomer components ((A) component, (B) component, and (C) component in said polymeric composition are said. ) 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) more than the above lower limit, the compatibility and copolymerization of each monomer component can be increased, and by making the use ratio of the component (A) less than the above upper limit, Since the content of the silicone component and the hydrophilic component constituting the polymer material can be relatively increased, high oxygen permeability or water content can be imparted to the polymer material in accordance with the purpose.

((B) component: silicone compound)
The silicone compound having a polymerizable group (B) is a compound having a polymerizable group and a siloxanyl group. [I] The polymer preferably contains a structural unit derived from the silicone compound as the component (B) having the structure. When the polymer [I] has such a structural unit, high oxygen permeability and flexibility can be imparted to the polymer material containing the polymer [I]. 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 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. (B) As a silicone compound of a component, 1 type or multiple types of things can be used.

  Preferable examples of the component (B) silicone compound include (B1) a compound having an ethylenically unsaturated group and a polydimethylsiloxane structure via a urethane bond. 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 the physical strengthening effect due to crosslinking, the reinforcing effect due to 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、飽和若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 is a divalent group derived from a diisocyanate selected from the group of saturated or unsaturated aliphatic, alicyclic and aromatic groups (where E ² is 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 having the component (A) and the compound having the amide group as the component (C). In this respect, an acryloyl group is particularly preferable.

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 an 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), as described above, E ¹ represents —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 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 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} and ^{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 the compound and the compound having an amide group as the component (C) deteriorates, phase separation occurs during polymerization, and white turbidity occurs. In some cases, a transparent polymer material cannot 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-vinylpyrrolidinone deteriorates, causing phase separation during polymerization and causing cloudiness. A uniform and transparent polymer material may not be obtained.

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

  In addition, as the silicone compound of component (B), in order to improve the oxygen permeability of the resulting polymer material and to impart high flexibility, (B2) silicone-containing alkyl (meth) acrylate, silicone-containing styrene derivative and It is preferable to use at least one compound selected from the group consisting of silicone-containing fumaric acid diesters.

  Examples of silicone-containing alkyl (meth) acrylates include, for example, trimethylsiloxydimethylsilylmethyl (meth) acrylate, trimethylsiloxydimethylsilylpropyl (meth) acrylate, methylbis (trimethylsiloxy) silylpropyl (meth) acrylate, tris (trimethylsiloxy) ) Silylpropyl (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, No [methylbis (trimethylsiloxy) siloxy] bis (trimethylsiloxy) silylpropyl glyceryl (meth) acrylate, trimethylsilylethyltetramethyldisiloxypropyl glyceryl (meth) acrylate, trimethylsilylmethyl (meth) acrylate, trimethylsilylpropyl glyceryl (meth) acrylate, Trimethylsilylpropyl (meth) acrylate, trimethylsiloxydimethylsilylpropylglyceryl (meth) acrylate, methylbis (trimethylsiloxy) silylethyltetramethyldisiloxymethyl (meth) acrylate, tetramethyltriisopropylcyclotetrasiloxanylpropyl (meth) acrylate, Tetramethyltriisopropylcyclotetrasiloxybis (trimethylsilo Shi) silyl propyl (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, for example, tris (trimethylsiloxy) silylstyrene, bis (trimethylsiloxy) methylsilylstyrene, (trimethylsiloxy) dimethylsilylstyrene, and tris (trimethylsiloxy). ) Siloxydimethylsilylstyrene, [bis (trimethylsiloxy) methylsiloxy] dimethylsilylstyrene, (trimethylsiloxy) dimethylsilylstyrene, heptamethyltrisiloxanylstyrene, nonamethyltetrasiloxanylstyrene, pentadecamethylheptacyloxanyl Styrene, heneicosamethyldecacyloxanyl styrene, heptacosamethyltridecacyloxanyl styrene, hentriacontamethylpentadecyloxanyl styrene, trimethylcyl Xypentamethyldisiloxymethylsilylstyrene, tris (pentamethyldisiloxy) silylstyrene, tris (trimethylsiloxy) siloxybis (trimethylsiloxy) silylstyrene, bis (heptamethyltrisiloxy) methylsilylstyrene, tris [methylbis (trimethylsiloxy) Siloxy] silylstyrene, heptakis (trimethylsiloxy) trisilylstyrene, trimethylsiloxybis [tris (trimethylsiloxy) siloxy] silylstyrene, nonamethyltetrasiloxyundecylmethylpentasiloxymethylsilylstyrene, tris [tris (trimethylsiloxy) siloxy] Silylstyrene, (tristrimethylsiloxyhexamethyl) tetrasiloxy [tris (trimethylsiloxy) siloxy] trimethyl Siloxysilylstyrene, Nonakis (trimethylsiloxy) tetrasilylstyrene, bis (tridecamethylhexasiloxy) methylsilylstyrene, heptamethylcyclotetrasiloxanylstyrene, heptamethylcyclotetrasiloxybis (trimethylsiloxy) silylstyrene, tripropyltetra Examples include methylcyclotetrasiloxanyl 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 (Trimethylsiloxy) silylpropyl) fumarate and the like.

  The component (B1) and the component (B2) may be used alone, but in order to impart higher oxygen permeability to the silicone hydrogel and achieve both good shape retention and excellent flexibility, It is preferable to use both in combination. The ratio of the silicone compound of the component (B) including the component (B1) and the component (B2) is not particularly limited, but is preferably 10 parts by mass or more and 70 parts by mass or less with respect to 100 parts by mass of all monomer components, and 15 masses. More preferred is at least 65 parts by weight. By setting the use ratio of the component (B) to the above lower limit or more, a polymer material having sufficient oxygen permeability and high flexibility can be obtained. Moreover, reduction of the hydrophilic property, transparency, etc. of the polymer material obtained can be prevented by making the usage-amount of (B) component below the said upper limit.

  The silicone compound as the component (B) may have a hydrophilic partial structure in the molecule. Thus, when the silicone compound has a hydrophilic partial structure, the compatibility between the silicone compound of the component (B) and the compound having an amide group of the component (C) is improved, and the water wettability of the resulting polymer material Can be improved. Examples of hydrophilic partial structures of silicone compounds include polyethylene glycol, polypropylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone, poly (meth) acrylic acid, poly (meth) acrylate, poly (2-hydroxyethyl (meth) acrylate), Examples thereof include polytetrahydrofuran, polyoxetane, polyoxazoline, polyacrylamide, polydimethylacrylamide, polydiethylacrylamide, poly (2-methacryloyloxyethyl phosphorylcholine), and block polymers thereof. This hydrophilic partial structure may be bonded to the silicone compound in a comb shape, or may be bonded to one end or both ends. The molecular weight of this hydrophilic partial structure is preferably 100 to 1,000,000, and more preferably 1,000 to 500,000. When the molecular weight is less than the above lower limit, there is a possibility that sufficient hydrophilicity that is compatible with the compound having an amide group as the component (C) cannot be imparted. On the other hand, when the molecular weight exceeds the above upper limit, each of the hydrophilic and hydrophobic domains tends to be large, and a transparent polymer material tends not to be obtained.

((C) component: a compound having an amide group)
The compound having an amide group as the component (C) can be copolymerized with the polymerizable compound as the component (A) and the silicone compound as the component (B). The above [I] polymer preferably includes a structural unit derived from the compound (C) having an amide group. When the [I] polymer contains a structural unit derived from the component (C), the hydrophilicity of the polymer material can be improved, and the water wettability and lubricity of the surface can be improved. (C) As a compound having an amide group as component, N such as acrylamide or N, N-dimethylacrylamide, N, N-diethylacrylamide, N- (2-hydroxyethyl) acrylamide, N-isopropylacrylamide, acryloylmorpholine, etc. -Substituted acrylamide, N-vinylpyrrolidinone, N-vinylacetamide and the like. Among them, N-vinylpyrrolidinone is preferable in that it has high hydrophilicity and can further improve water wettability and lubricity on the surface of the polymer material.

  Although it does not specifically limit as the usage-amount of the said N-vinyl pyrrolidinone, 10 to 50 mass parts is preferable with respect to 100 mass parts of all the monomer components, and 15 to 45 mass parts is further more preferable. By setting the use ratio of N-vinylpyrrolidinone to the above lower limit or more, the water wettability of the polymer material can be enhanced. Moreover, reduction of the oxygen permeability of the said polymer material, transparency, etc. can be prevented by making the usage-amount of N-vinyl pyrrolidinone below the said upper limit.

((D) Crosslinking agent)
In order to adjust the crosslinking density, flexibility, and hardness of the polymer material, a crosslinking agent can be added as the component (D) 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 parts by mass or more and 1 part by mass or less, particularly 0.1 parts by mass or more and 0.8 parts by mass or less, with respect to 100 parts by mass of all monomer components. preferable. By setting the use ratio of the crosslinking agent to the above lower limit or more, shape stability, strength, durability and the like can be imparted to the polymer material, and flexibility and the like can be adjusted reliably. On the other hand, it can suppress that a polymer material becomes too hard by making the usage-amount of a crosslinking agent below into the said upper limit.

((E) component: additive)
In order to impart desired characteristics to the polymer material, non-polymerizable water-soluble organic solvents, cooling agents, thickening agents, and the like can be used as additives for the component (E). . In addition, surfactant is not contained in the additive of the said (E) component.

  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. Among these additives, if the proportion of water-soluble organic solvent exceeds the upper limit, these non-polymerizable components increase, so it takes time to elute in the elution step after curing, and these non-polymerizable components Sufficient elution of the components becomes difficult and may remain in the polymer material. On the other hand, when the use ratio of the refreshing agent or the thickening agent exceeds the above upper limit, the polymerizable composition or the resulting polymer material may be non-uniform / opaque. On the contrary, if the use ratio of the additive is smaller than the lower limit, the effect of using the additive may not be sufficiently exhibited regardless of the type of the additive.

  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, the compatibility between the monomer components such as the component (C) N-vinylpyrrolidinone is improved, so that uniform dispersion in the polymerizable composition can be further promoted. As a result, the monomer It is possible to reduce the unpolymerized rate.

  The refreshing agent can increase the compatibility of each monomer component and reduce unreacted residual components in the polymer material. For example, when a contact lens or the like is produced from the polymer material, a refreshing feeling to the eyes. Or eliminating the feeling of foreign objects and itchiness when wearing contact lenses.

  The refreshing agent is not particularly limited, but 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 polymer material, and adjust the viscosity of the polymerizable composition. Moreover, according to the said thickener, when a contact lens etc. are manufactured from a polymer material, a moist feeling can be given with respect to eyes.

  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.

  When the polymer material obtained by polymerizing the polymerizable composition is used as an ophthalmic lens such as a contact lens, the composition further contains a polymerizable or non-polymerizable ultraviolet absorber, dye or ultraviolet absorbing dye. It is possible to impart UV absorption or to color the material. 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) acrylic Yloxypropylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-5 ′-(meth) acryloyloxypropyl-3′-t-butylphenyl) -5-chloro-2H-benzotriazole, 2- ( 2′-hydroxy-5 ′-(2 ″ -methacryloyloxyethoxy) -3′-tert-butylphenyl) -5-methyl-2H-benzotriazole and other benzotriazole-based polymerizable ultraviolet absorbers; 2-hydroxy-4 -Salicylic acid derivative-based polymerizable UV absorbers such as phenyl methacryloyloxymethylbenzoate; 2-cyano-3-phenyl-3- (3 '-(meth) acryloyloxyphenyl) propenyl acid methyl ester, etc. It can use individually or in mixture of 2 or more types.

  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-to) Ruazo) -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 Ester, 6-vinyl lid Luric 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 ) Acrylloy Azo polymerization dye amide-1-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) phthalocyanine polymerizable dye, 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) acryloyloxyethylphenyl) Azo) benzophenone, 2,4-dihydroxy-3- (o- (meth) acryloyloxypropylphenylazo) benzophenone, 2,4-dihydroxy-5- (o- (meth) acryloyloxypropylphenylazo) benzophenone, 2, 4-dihydroxy- -(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 (meth)) 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- (meta ) 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) benzofe And benzophenone type polymerizable ultraviolet absorbing dyes such as emission, 2-hydroxy-4-(p-Suchirenoazo) benzoic acid type polymerizable ultraviolet absorbing dyes phenyl benzoate and the like. These can be used alone or in admixture of two or more.

  In addition, the polymerizable dye, the ultraviolet absorber, and the ultraviolet absorbing dye are copolymerized in advance with a comonomer (for example, a component represented by (A), (B), or (C)) to obtain a polymer. It can also be added to the composition. Further, for example, a polyamide synthesized with amino group-containing metal phthalocyanine as a component, or a monomer (for example, a component represented by (A), (B), (C)) using azo group-containing metal phthalocyanine as an initiator is polymerized in advance. A dye or the like as a polymer can also be added to the polymerizable composition.

  The content of the polymerizable dye, the ultraviolet absorbent and the ultraviolet absorbent dye is preferably 3 parts by mass or less, more preferably 0.01 parts by mass or more and 2 parts by mass or less with respect to 100 parts by mass of all monomer components. When the total amount of these dyes, ultraviolet absorbers and ultraviolet absorbing dyes exceeds 3 parts by mass, the mechanical strength and the like of the ophthalmic lens material tend to decrease. Furthermore, in consideration of the toxicity of ultraviolet absorbers and pigments, there is a tendency that the composition is not suitable as an ophthalmic lens composition such as a contact lens that is in direct contact with a living tissue or an intraocular lens that is embedded in a living body. In particular, in the case of a pigment, if the amount is too large, the color of the lens becomes dark and the transparency is lowered, and the lens tends to be difficult to transmit visible light.

[II] Surfactant A surfactant is contained in the polymer material. Examples of the method of inclusion include (1) a method of hydrating the above-mentioned [I] polymer after production in an aqueous surfactant solution, and (2) an aqueous surfactant solution of [I] polymer after hydration. And (3) a method in which the surfactant is contained in a polymerizable composition at the time of production of the polymer [I] and polymerized. Since the surfactant contained in the polymer material has a strong interaction with the [I] polymer and is difficult to release slowly, the surfactant is held inside the polymer material. Therefore, the surfactant can improve water wettability and surface lubricity of the polymer material. Further, when the surfactant is contained by the method (3), each monomer component can be uniformly dispersed in the polymerizable composition, so that it can be efficiently present inside the polymer and is not polymerized. The monomer ratio can be reduced.

  The content of the surfactant in the polymer material is preferably 0.05% by mass or more and 1% by mass or less. By making the content of the surfactant 0.05% by mass or more, water wettability and lubricity of the polymer material surface are further improved. Moreover, the deformation | transformation of polymer material itself and the elution amount of surfactant from a polymer material are suppressed because content of surfactant shall be 1 mass% or less.

  As this surfactant, known ones such as cationic surfactants, anionic surfactants, ionic surfactants such as amphoteric surfactants, and nonionic surfactants can be used, but there is a particular limitation. Not done. Among the above surfactants, 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 the wettability due to the compatibility with each monomer component and the ease of being retained in the 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.

[Polymer material]
The polymer material of the present invention is, for example, heated and / or irradiated with light (ultraviolet rays and / or visible light) the polymerizable composition containing each of the above components and [II] surfactant. Each monomer component can be copolymerized and cured. It can also be obtained by copolymerization by electron beam irradiation instead of light irradiation. The polymer material can also be obtained by adding [II] surfactant to a polymer obtained by polymerizing the polymerizable composition containing or not containing [II] surfactant.

The water content of the polymer material is preferably 40% or more, and more preferably 50% or more. By setting the water content of the polymer material to 40% or more, water wettability of the polymer material surface 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-mentioned refreshing agent and thickening agent can be held inside. In the case where 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 can be provided with various characteristics and functions by the additive retained inside. In other words, it is possible to add functionality that gives a refreshing feeling to the eye of the ophthalmic lens wearer by the cooling agent, and adds functionality that gives a moist feeling to the eye of the ophthalmic lens wearer by the thickening agent. can do.

  The polymer material has good flexibility. The lower limit of the tensile modulus that is an index of the hardness and flexibility of the polymer material is preferably 0.1 MPa, and 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 elastic 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 the finger is deteriorated, and the 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.

  Compared to the general polymer material obtained by the polymerization method as described above, the polymer material of the present invention has a reduced amount of monomer remaining unpolymerized. 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. Further, since the amount of residual monomer in the polymer material is reduced, for example, an extraction step for removing the residual monomer from the polymer material can be unnecessary or simplified in the manufacturing process of the ophthalmic lens. As a result, the manufacturing process can be simplified and the manufacturing cost can be reduced.

  When the polymer material of the present invention is used as a material for an ophthalmic lens such as a contact lens, 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 and the radical polymerization initiator are blended in a mold corresponding to the shape of the desired ophthalmic lens material, and the mold is prepared. The ophthalmic lens material can be produced by subjecting the obtained polymer material to polymerization by gradually heating 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.

  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-butyl peroxyhexanoate, 3,5,5-trimethylhexanoyl peroxide, and the like. These thermal polymerization initiators can be used alone or in admixture of two or more. The amount of the thermal polymerization initiator used is preferably 0.001 part by mass or more and 2 parts by mass or less, more preferably 0.01 part by mass or more and 1 part by mass with respect to 100 parts by mass of all monomer components of the polymerizable composition. It is as follows.

  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.

  When the polymerizable composition is polymerized by irradiating the polymerizable composition with ultraviolet rays and / or visible light (hereinafter simply referred to as “light”), the polymerization is carried out in the mold corresponding to the shape of the desired ophthalmic lens material. The composition is blended with a photopolymerization initiator, polymerized by irradiating the mold with light, and the molded product obtained is subjected to mechanical processing such as cutting and polishing as necessary. Lens material can be manufactured. 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 template used for polymerization by light irradiation is not particularly limited as long as it is a material that can transmit light necessary for polymerization / curing, but general-purpose resins such as polypropylene, polystyrene, nylon, and polyester are preferable, Glass may also be used. By molding and processing these materials, a mold having a desired shape can be obtained.

After the polymerizable composition containing each monomer component is blended in such a mold, polymerization is carried out 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 light illuminance 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 light 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.

  Examples of photopolymerization initiators used for polymerization by light irradiation include, for example, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like. Phosphine oxide photopolymerization initiators; benzoin photopolymerization initiators such as methyl orthobenzoylbenzoate, methylbenzoylformate, 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-dimethyl Phenone photopolymerization initiators such as xyl-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. 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 part by mass or more and 2 parts by mass or less, more preferably 0.01 parts by mass with respect to 100 parts by mass of all monomer components of the polymerizable composition. It is not less than 1 part by mass.

  The amount of residual monomer in the polymer material under the above polymerization conditions is preferably 1% by mass or less, and more preferably 0.5% by mass or less for the compound having an amide group as the component (C) in the mass ratio to the polymer material. 0.2 mass% or less is more preferable. In addition, among the silicone compounds of component (B), for component (B2) 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 the compound having an amide group of component (C) 1% by mass or less, it is possible to improve safety in various uses of the polymer material, in particular, ophthalmic lens use. 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 water-insoluble and, unlike the compound having an amide group of component (C), can be eluted and removed from the polymer material by an aqueous treatment solution such as water or physiological saline. Have difficulty. By setting the residual amount of the silicone compound of the component (B2) having such characteristics to 1% by mass or less, it is possible to ensure the safety of the polymer material and to omit or simplify the manufacturing process as described above. The deterioration of the physical properties and the stability of the shape 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, an ophthalmic lens having more excellent wettability and / or contamination resistance can be obtained. 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 with organosilane, methane, nitrogen, or the like. The low temperature plasma treatment may be performed under reduced pressure or under atmospheric pressure. In the low-temperature plasma processing, the output, processing time, and gas concentration are appropriately adjusted with high-frequency RF (for example, 13.56 MHz), low-frequency AF (for example, 15.0 to 40.0 KHz), and microwave (for example, 2.45 GHz). As a result, the surface modification effect can be controlled.

  As described above, the 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. A component that is similar to the component (A) but different from the component (A) is defined as “component other than (A)”, and the components other than (A) and (A) are combined. It is defined as “Monomer A component”.
(A) Component 2-ETA: 2-ethoxyethyl acrylate 2-MTA: 2-methoxyethyl acrylate BuA: n-butyl acrylate BuMA: Components other than n-butyl methacrylate (A) 2-HEMA: 2-hydroxyethyl methacrylate DMAA : N, N-dimethylacrylamide EA: Ethyl acrylate EEA: Ethoxyethoxyethyl acrylate EMA: Ethyl methacrylate MMP: 1-methyl-3-methylene-2-pyrrolidinone (B) component Macromonomer (8): In the above formula (8) Compound shown TRIS: Tris (trimethylsiloxy) silylpropyl methacrylate (C) component N-VP: N-vinyl-2-pyrrolidinone (D) cross-linking agent EDMA: ethylene glycol dimethacrylate AMA: allyl methacrylate Rate UV absorber HMEPBT: 2- (2′-hydroxy-5′-methacryloyloxyethylphenyl) -2H-benzotriazole dye PCPMA: Phthalocyanine-containing polymethacrylate polymerization initiator TPO: 2,4,6-trimethylbenzoyl- Diphenylphosphine oxide HMPPO: 2-hydroxy-2-methyl-1-phenylpropan-1-one

[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]
30 parts by mass of component (A) 2-MTA as monomer A component in Table 1, 70 parts by mass of component 2-HEMA other than (A), and 0.4 parts by mass of EDMA as a crosslinking agent for component (D) A polymerizable composition containing 0.5 parts by mass of HMPPO as a polymerization initiator was prepared. 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 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. After polymerization, the polymer was removed from the mold to obtain a contact lens-shaped polymer. After the polymer is immersed in distilled water and swollen until equilibrium is reached, the polymer material is rinsed in distilled water, and polyoxyethylene (60) hydrogenated castor oil (hereinafter referred to as HCO-60) as a surfactant. The sample was immersed in the polymer material using a phosphate buffer containing (0.05% by mass) and autoclaved in the solution (121 ° C., 20 minutes).

[Example 2]
The above examples except that 20 parts by mass of 2-MTA as component (A), 50 parts by mass of DMAA as components other than (A), and 30 parts by mass of macromonomer (8) as the silicone compound of component (B) were used. In the same manner as in Example 1, a contact lens was obtained.

[Comparative Example 1]
A contact lens was obtained in the same manner as in Example 1 except that 100 parts by mass of 2-HEMA as a monomer A component other than (A) was used.

[Comparative Example 2]
A contact lens was prepared in the same manner as in Example 1 except that 50 parts by mass of DMAA other than (A) was used as the monomer A component, and 50 parts by mass of macromonomer (8) was used as the silicone compound of component (B). Obtained.

[Comparative Example 3]
A contact lens was obtained in the same manner as in Example 1 except that sterilization (high-pressure steam sterilization) was performed in a phosphate buffer solution containing no surfactant during sterilization.

[Comparative Example 4]
A contact lens was obtained in the same manner as in Example 2 except that sterilization (high-pressure steam sterilization) was performed in a phosphate buffer solution containing no surfactant during sterilization.

[Comparative Example 5]
A contact lens was obtained in the same manner as in Comparative Example 1 except that sterilization (high-pressure steam sterilization) was performed in a phosphate buffer solution containing no surfactant during sterilization.

[Comparative Example 6]
A contact lens was obtained in the same manner as in Comparative Example 2 except that sterilization (high-pressure steam sterilization) was performed in a phosphate buffer solution containing no surfactant during sterilization.

  About the contact lens of Examples 1-2 and Comparative Examples 1-6, surface lubricity and water wettability were evaluated. The obtained results are shown in Table 1.

[Evaluation of surface lubricity]
The contact lens was folded in half on the fingers and pinched, and the lubricity (rubbing feeling between the lenses and the feeling between the lenses and fingers) when rubbing the lens with the fingers was evaluated. The determination was made according to the following 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: The lens and fingers are not easily mounted, but there is a case where the lenses are not slippery and the movement is lost.
D: The lens surface is sticky and the adhesion between the lens and fingers is strong.

[Evaluation of water wettability]
After sterilization, the lens was taken out with tweezers and shaken lightly twice to visually confirm the water wettability of the lens surface after removing the water adhering to the lens, and judged according to the following 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.

  As is clear from the results in Table 1, the contact lenses of Examples 1 and 2 in which 2-MTA, which is the component (A), was used as the monomer A component, and a surfactant was contained in the liquid used during the sterilization treatment. Gave good results in terms of surface lubricity and water wettability. On the other hand, Comparative Example 1 and Comparative Example 2 using only 2-HEMA or DMAA, which is a component other than (A), as the monomer A component, do not use 2-ATA as the component (A), Although the surfactant was contained in the liquid, the results were inferior to those of Examples 1 and 2. Moreover, although Comparative Example 3 and Comparative Example 4 using a phosphate buffer solution containing no surfactant during sterilization treatment had the same formulation as Example 1 and Example 2, surface lubricity and water wetting Both sexes were inferior in evaluation. As the monomer A component, 2-ATA which is the component (A) is not used, and only 2-HEMA or DMAA which is a component other than the component (A) is used. About the comparative example 5 and the comparative example 6 using this, the water wettability was inferior.

  Based on the above results, surface lubricity and water wettability can be improved by using (A) a polymerizable compound having an acryloyloxy group as the monomer component of the polymerizable composition and adding a surfactant to the liquid during sterilization. Was shown to do.

[Example 3]
As monomer A component in Table 2, (A) component 2-MTA is 24 parts by mass, (B) component is a silicone compound, 10 parts by mass of macromonomer (8) and TRIS is 25 parts by mass, and (C) component 41 parts by mass of N-VP as a compound having an amide group, 0.1 parts by mass of AMA as a crosslinking agent of component (D), 0.4 parts by mass of HMPPO as a polymerization initiator, and 0.02 of PCPMA as a dye A polymerizable composition containing parts by mass was prepared. This polymerizable composition was poured 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 thickness of 0.08 mm). Next, this mold was irradiated with UV light for 20 minutes using a high-pressure mercury lamp (2 kW) to carry out photopolymerization. After polymerization, the polymer was removed from the mold to obtain a contact lens-shaped polymer. The polymer is subjected to plasma treatment (RF output 50 W, 100 Pa) in a carbon dioxide atmosphere, and then immersed in distilled water containing HCO-60 (0.5% by mass) as a surfactant to achieve equilibrium. Hydrated by swelling. Thereafter, it was rinsed in distilled water and sterilized in a phosphate buffer (high pressure steam sterilization) to obtain a contact lens.

[Example 4]
As monomer A component, 18 parts by mass of component (A) 2-MTA, 15 parts by mass of macromonomer (8) as silicone compound of component (B), 37 parts by mass of TRIS, and amide group of component (C) A contact lens was obtained in the same manner as in Example 3 except that 30 parts by mass of N-VP was used as the compound having N.

[Comparative Example 7]
As monomer A component, 35 parts by mass of MMP of components other than (A), 10 parts by mass of DMAA, 33 parts by mass of macromonomer (8) as a silicone compound of component (B), and 22 parts by mass of TRIS (D ) A contact lens was obtained in the same manner as in Example 3 except that 0.4 parts by mass of EDMA was used as a crosslinking agent.

[Comparative Example 8]
As monomer A component, 47 parts by mass of MMP other than (A), 15.5 parts by mass of DMAA, 22.5 parts by mass of macromonomer (8) as a silicone compound of component (B), and 15 parts by mass of TRIS A contact lens was obtained in the same manner as in Example 3 except that 0.4 parts by mass of EDMA was used as a crosslinking agent for component (D).

[Comparative Example 9]
A contact lens was obtained in the same manner as in Example 3 except that distilled water containing no surfactant was used as the liquid to be immersed during hydration.

[Comparative Example 10]
A contact lens was obtained in the same manner as in Example 4 except that distilled water containing no surfactant was used as the liquid to be immersed during hydration.

[Comparative Example 11]
A contact lens was obtained in the same manner as in Comparative Example 7 except that distilled water containing no surfactant was used as the liquid to be immersed during hydration.

[Comparative Example 12]
A contact lens was obtained in the same manner as in Comparative Example 8 except that distilled water containing no surfactant was used as the liquid to be immersed during hydration.

  The contact lenses of Examples 3 to 4 and Comparative Examples 7 to 12 were evaluated for surface lubricity and water wettability. The obtained results are shown in Table 2. The water content was determined according to the following method.

[Moisture content]
The obtained contact lens was adjusted at 20 ° C. for 1 hour or longer to measure the weight (W1), then dried in a dryer set at 105 ° C. for 16 hours, and the weight (W2) was measured again. The water content was determined according to the following formula.
Moisture content (%) = (W1-W2) / W1 × 100

  As is apparent from the results of Table 2, Examples 3 and 4 using 2-MTA as the component (A) as the monomer A component and distilled water containing a surfactant during the hydration treatment were used. The contact lens gave good results in surface lubricity and water wettability. On the other hand, Comparative Examples 7 and 8 using MMP and DMAA which are components other than (A) as the monomer A component were carried out despite using distilled water containing a surfactant during hydration treatment. The results were inferior to those of Example 3 and Example 4. Further, Comparative Example 9 and Comparative Example 10 using distilled water containing no surfactant at the time of hydration treatment had the same formulation and the same water content as those of Example 3 and Example 4, but surface lubrication. Both the property and water wettability were inferior to the evaluation. For Comparative Example 11 and Comparative Example 12, a component other than (A) was used as the monomer A component, and distilled water not containing a surfactant was used during the hydration treatment. Both material properties and surface lubricity were the poorest materials.

[Repeated cleaning test]
The contact lens of Example 4 was repeatedly cleaned with a contact lens cleaning stock solution according to a care regimen. Table 3 shows the results of evaluating the lens diameter, lens surface lubricity, and water wettability measured at 20 ° C. in physiological saline before and after 15 cycles of washing and storage.

  As is clear from the results in Table 3, no changes in lens diameter, surface lubricity, and water wettability were observed before and after washing and storage. Therefore, it was shown that the ophthalmic lens material using the polymer material of the present invention is excellent in shape stability because the surfactant is hardly eluted from the polymer material in a solvent such as washing.

[Example 5]
24 parts by mass of 2-MTA as the component (A) in Table 4, 5 parts by mass of the macromonomer (8) and 30 parts by mass of TRIS as the silicone compound of the component (B), and a compound having an amide group as the component (C) 41 parts by mass of N-VP, 0.3 parts by mass of AMA as a crosslinking agent for component (D), 0.6 parts by mass of TPO as a polymerization initiator, 1.0 part by mass of HMEPBT as an ultraviolet absorber, and A polymerizable composition containing 0.02 parts by mass of PCPMA as a dye was prepared. This polymerizable composition was poured 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 thickness of 0.08 mm). Subsequently, this mold was irradiated with a blue lamp (TL20W03 manufactured by PHILIPS) for 20 minutes for photopolymerization. After polymerization, the polymer was removed from the mold to obtain a contact lens-shaped polymer. The polymer was hydrated by plasma treatment (RF output 50 W, 100 Pa) in a carbon dioxide atmosphere, then immersed in distilled water and swollen until equilibrium was reached. Thereafter, it was rinsed in distilled water and sterilized (phosphate steam sterilization) in a phosphate buffer containing HCO-60 (0.05% by mass) as a surfactant to obtain a contact lens.

[Example 6]
As the component (A) in Table 4, 25 parts by mass of 2-MTA, as the silicone compound of component (B), 10 parts by mass of macromonomer (8) and 25 parts by mass of TRIS, and the compound having an amide group as component (C) Polymerization containing 40 parts by mass of N-VP, 0.3 parts by mass of AMA as a crosslinking agent for component (D), 0.4 parts by mass of HMPPO as a polymerization initiator, and 0.02 parts by mass of PCPMA as a dye A composition was prepared. This polymerizable composition was poured 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 thickness of 0.08 mm). Next, this mold was irradiated with UV light for 20 minutes using a high-pressure mercury lamp (2 kW) to carry out photopolymerization. Thereafter, contact lenses were obtained in the same manner as in Example 5.

  For the contact lenses of Examples 5 and 6, the surface lubricity and water wettability were evaluated and the water content was measured according to the method described above. Further, the tensile modulus was measured according to the following method. Table 4 shows the obtained results.

[Tensile modulus]
The contact lens was punched out so as to have a dumbbell shape with a tensile portion width of 1.8 mm, and a tensile test was performed using a universal testing machine AG-IS MS type manufactured by Shimadzu Corporation. The measurement was performed in 20 ° C. physiological saline, and the tensile elastic modulus (Young's modulus) was calculated from the stress-elongation curve.

  As is clear from the results in Table 4, the contact lenses of Example 5 and Example 6 were both excellent in flexibility and excellent in surface lubricity and water wettability.

[Example 7]
A contact lens was obtained in the same manner as in Example 6 except that a physiological saline solution (0.9% NaCl aqueous solution) containing HCO-60 (0.05% by mass) as a surfactant was used during sterilization. It was.

[Example 8]
A contact lens was prepared in the same manner as in Example 6 except that a physiological saline (0.9% NaCl aqueous solution) containing polyoxyethylene (100) hydrogenated castor oil (0.05% by mass) was used during sterilization. Obtained.

[Example 9]
A contact lens was obtained in the same manner as in Example 6 except that a physiological saline solution (0.9% NaCl aqueous solution) containing polyoxyethylene (9) lauryl ether (0.05% by mass) was used during sterilization. .

[Example 10]
The same as in Example 6 except that a physiological saline (0.9% NaCl aqueous solution) containing polyoxyethylene sorbitan laurate (polysorbate 20) (0.05 mass%) was used during sterilization. Contact lenses were obtained.

[Comparative Example 13]
A contact lens was obtained in the same manner as in Example 6 except that a physiological saline solution (0.9% NaCl aqueous solution) containing polyethylene glycol (molecular weight 1,000) (0.05% by mass) was used during sterilization. .

[Comparative Example 14]
A contact lens was obtained in the same manner as in Example 6 except that a physiological saline (0.9% NaCl aqueous solution) containing polyethylene glycol (molecular weight 35,000) (0.05% by mass) was used during sterilization. .

[Comparative Example 15]
A contact lens was obtained in the same manner as in Example 6 except that a physiological saline solution (0.9% NaCl aqueous solution) containing polyvinylpyrrolidone (molecular weight 10,000) (0.05% by mass) was used during sterilization. .

[Comparative Example 16]
A contact lens was obtained in the same manner as in Example 6 except that a physiological saline (0.9% NaCl aqueous solution) containing polyvinylpyrrolidone (molecular weight 40,000) (0.05% by mass) was used during sterilization. .

[Comparative Example 17]
A contact lens was obtained in the same manner as in Example 6 except that a physiological saline solution (0.9% NaCl aqueous solution) containing polyvinyl alcohol (0.05% by mass) was used during sterilization.

[Comparative Example 18]
A contact lens was obtained in the same manner as in Example 6 except that a physiological saline (0.9% NaCl aqueous solution) containing methoxy-terminated polyoxyethylene (molecular weight 350) (0.05% by mass) was used during sterilization. It was.

[Comparative Example 19]
A contact lens was obtained in the same manner as in Example 6 except that nothing was added to the physiological saline solution (0.9% NaCl aqueous solution) used during sterilization.

  As is apparent from the results in Table 5, Examples 7 to 10 using a physiological saline containing a surfactant during sterilization were excellent in surface lubricity and water wettability. On the other hand, it was shown that Comparative Examples 13-18 which used the physiological saline containing components other than surfactant at the time of sterilization were inferior to evaluation of surface lubricity and water wettability compared with the said Example. Moreover, the excellent effect was not acquired also about the comparative example 19 which used the physiological saline which has not added the additive at the time of sterilization.

[Example 11]
In the purified water (10 mL) containing the polyoxyethylene (20) hydrogenated castor oil (0.5 mass%) which is surfactant, using the lens before hydration produced in Example 5, at 50 degreeC. Hydration was performed for 10 minutes, and elution was performed by immersing in fresh purified water for 10 minutes at room temperature. Thereafter, sterilization (high-pressure steam sterilization) was performed in about 2 mL of phosphate buffer to obtain a contact lens.

[Example 12]
Contact as in Example 11 except that purified water (10 mL) containing polyoxyethylene (40) hydrogenated castor oil (0.5% by mass) as a surfactant was applied as the liquid used during hydration. I got a lens.

[Example 13]
A contact lens was obtained in the same manner as in Example 11 except that purified water (10 mL) containing HCO-60 (0.5% by mass), which is a surfactant, was applied as the liquid used during hydration.

[Example 14]
Contact as in Example 11 except that purified water (10 mL) containing polyoxyethylene (100) hydrogenated castor oil (0.5% by mass) as a surfactant was applied as the liquid used during hydration. I got a lens.

[Example 15]
A contact lens was obtained in the same manner as in Example 11 except that purified water (10 mL) containing polysorbate 80 (0.5% by mass), which is a surfactant, was applied as the liquid used during hydration.

[Example 16]
A contact lens was obtained in the same manner as in Example 11 except that purified water (10 mL) containing Poloxamer 407 (0.5% by mass), which is a surfactant, was applied as the liquid used during hydration.

[Comparative Example 20]
A contact lens was obtained in the same manner as in Example 11 except that purified water (10 mL) containing no surfactant was applied as the liquid used during hydration.

  As water wettability evaluation of the lenses obtained in Examples 11 to 16 and Comparative Example 20, contact angle (droplet method and bubble method) measurement was performed by the following method. The results are shown in Table 6.

[Contact angle]
Using a Drop Master 500 manufactured by Kyowa Interface Chemical Co., Ltd., a contact angle (droplet method) using 2 μL of physiological saline or a contact angle (bubble method) using 2 μL of bubbles is measured in an environment at a temperature of 25 ° C. It was. In the case of the bubble method, physiological saline was used as the surrounding liquid.

  From the results of Table 6, Examples 11 to 16 in which aqueous solutions containing various surfactants were used during hydration had a lower contact angle than Comparative Example 20 in which purified water containing nothing was used during hydration. It was shown that. This result showed that the wettability of the polymer material of the present invention can be improved by using an aqueous solution containing a surfactant during hydration.

[Example 17]
The contact lens of Example 13 was stored at 45 ° C. for 1 month. When the diameter of the contact lens after storage was measured, it was 0.04 mm smaller than that before storage, but it was found that there was no particular problem in use, and the polymer material of the present invention was excellent in shape stability.

[Example 18]
Polymerizable composition prepared in Example 5 (24 parts by mass of 2-MTA as component (A), 5 parts by mass of macromonomer (8) and 30 parts by mass of TRIS as silicone compound of component (B), (C ) 41 parts by mass of N-VP as a compound having an amide group, 0.3 parts by mass of AMA as a crosslinking agent of (D) component, 0.6 parts by mass of TPO as a polymerization initiator, and HMEPBT as an ultraviolet absorber 1.0 parts by weight, and 0.02 parts by weight of PCPMA as a pigment) is 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 thickness of 0.08 mm). did. Subsequently, this mold was irradiated with a blue lamp (TL20W03 manufactured by PHILIPS) for 20 minutes for photopolymerization. After polymerization, the polymer was removed from the mold to obtain a contact lens-shaped polymer. The polymer was subjected to plasma treatment (RF output 25 W, 100 Pa) in a carbon dioxide atmosphere, and then the dry lens was immersed in 0.05 mass% surfactant polysorbate 80 aqueous solution (2 mL) at 50 ° C. After hydrating for 5 minutes, it was immersed in 2 mL of purified water and subjected to an elution treatment at room temperature for 60 minutes. Thereafter, sterilization treatment (high-pressure steam sterilization) was performed in about 2 mL of a phosphate buffer solution, and visual appearance observation was performed as an evaluation of water wettability of the lens after sterilization. Further, the amount of surfactant incorporated into the lens was determined based on the amount of polysorbate 80 in the external solution before and after hydration from the above treatment. The results are shown in Table 7.

[Example 19]
A contact lens was obtained in the same manner as in Example 18 except that the concentration of the surfactant polysorbate 80 aqueous solution to be immersed during hydration was 0.02% by mass.

[Comparative Example 20]
A contact lens was obtained in the same manner as in Example 18 except that the concentration of the surfactant polysorbate 80 aqueous solution immersed in hydration was 0.01% by mass.

[Comparative Example 21]
A contact lens was obtained in the same manner as in Example 18 except that purified water was used as the liquid to be immersed during hydration.

[Quantification of surfactant polysorbate 80]
1) Ammonium tetrathiocyanocobalt (II) acid solution (hereinafter referred to as a cobalt solution): In a 100 mL volumetric flask, 31.0 g of ammonium thiocyanate and 14.0 g of cobalt (II) nitrate hexahydrate were weighed, It was made up with purified water.
2) Preparation of measurement solution and absorbance measurement: In a 10 mL sample bottle, take 1 mL of test solution (hydration solution before and after lens immersion), 6 mL of saturated saline solution and 200 μL of cobalt solution, and after shaking well for 1 hour, Absorbance at 622 nm was measured.
3) Lens incorporation amount of surfactant: Polysorbate 80 concentration (W0, W1, unit%) in the solution before and after lens immersion was determined from a calibration curve prepared using a polysorbate 80 solution with a known concentration. In consideration of the immersion liquid amount of 2 mL, the amount of surfactant incorporated into the lens was determined as shown in the following formula (a).
Furthermore, since the weight of the lens used in the test (at 20 ° C. under equilibrium swelling) was 30 mg, the content of the surfactant relative to the total weight of the contact lens was calculated according to the following formula (b).

Incorporated surfactant (μg) = (W0−W1) / 100 × 2 × 10 ⁶
W0: Polysorbate 80 concentration (%) in the solution before lens immersion
W1: Polysorbate 80 concentration (%) in the liquid after lens immersion (a)

Surfactant content in contact lenses (%)
= Incorporated surfactant (μg) / contact lens weight (mg) / 10 (b)

  From the results of Table 7, Example 18 and Example 19 in which the amount of the surfactant incorporated into the contact lens is 0.07 to 0.17% with respect to the total weight of the contact lens are excellent in water wettability. It was shown that. On the other hand, in Comparative Example 20 in which the amount of surfactant to be incorporated is 0.03% with respect to the total weight of the contact lens and Comparative Example 21 not containing the surfactant, the surface becomes wet as compared with Examples 18 and 19 above. It was shown to be inferior.

[Production Example 1]
As monomer A component in Table 8, 20 parts by mass of 2-ATA as component (A), 30 parts by mass of macromonomer (8) as silicone compound of component (B), and 30 parts by mass of TRIS, component (C) A polymerizable composition containing 20 parts by mass of N-VP, 0.4 parts by mass of EDMA as a crosslinking agent of component (D), and 0.4 parts by mass of HMPPO as a polymerization initiator (composition α in Table 8) Prepared. This polymerizable composition is 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 thickness of 0.08 mm), and then a high-pressure mercury lamp (2 kW) is used for the mold. Then, UV polymerization was performed for 20 minutes for photopolymerization. After the polymerization, the product was taken out from the mold to obtain a polymer.

[Production Example 2]
A contact lens-shaped polymer was obtained in the same manner as in Production Example 1 except that 20 parts by mass of 2-ETA as the component (A) was used as the monomer A component.

[Production Example 3]
A contact lens-shaped polymer was obtained in the same manner as in Production Example 1 except that 20 parts by mass of EEA as component (A) was used as the monomer A component.

[Production Example 4]
A contact lens-shaped polymer was obtained in the same manner as in Production Example 1 except that 20 parts by mass of EA as the component (A) was used as the monomer A component.

[Production Example 5]
A contact lens-shaped polymer was obtained in the same manner as in Production Example 1 except that 20 parts by mass of BuA as the component (A) was used as the monomer A component.

[Production Example 6]
As monomer A component, 25 parts by mass of 2-ATA as component (A), 10 parts by mass of macromonomer (8) and 25 parts by mass of TRIS as silicone compounds of component (B), N- Except for using 40 parts by mass of VP, 0.4 parts by mass of EDMA as a crosslinking agent for component (D), and 0.4 parts by mass of HMPPO (composition β in Table 8) as a polymerization initiator, Similarly, a contact lens-shaped polymer was obtained.

[Production Example 7]
A contact lens-shaped polymer was obtained in the same manner as in Production Example 6 except that 25 parts by mass of 2-ETA as the component (A) was used as the monomer A component.

[Production Example 8]
A contact lens-shaped polymer was obtained in the same manner as in Production Example 6 except that 25 parts by mass of EEA as the component (A) was used as the monomer A component.

[Production Example 9]
A contact lens-shaped polymer was obtained in the same manner as in Production Example 6 except that 25 parts by mass of EA as the component (A) was used as the monomer A component.

[Production Example 10]
A contact lens-shaped polymer was obtained in the same manner as in Production Example 6 except that 25 parts by mass of BuA as the component (A) was used as the monomer A component.

[Comparative Production Example 1]
A contact lens-shaped polymer was obtained in the same manner as in Production Example 1 except that 20 parts by mass of 2-HEMA, which is a component other than (A), was used as the monomer A component.

[Comparative Production Example 2]
A contact lens-shaped polymer was obtained in the same manner as in Production Example 1 except that 20 parts by mass of DMAA, which is a component other than (A), was used as the monomer A component.

[Comparative Production Example 3]
A contact lens-shaped polymer was obtained in the same manner as in Production Example 1 except that 20 parts by mass of MMP, which was a component other than (A), was used as the monomer A component.

[Comparative Production Example 4]
A contact lens-shaped polymer was obtained in the same manner as in Production Example 1 except that 20 parts by mass of EMA, which was a component other than (A), was used as the monomer A component.

[Comparative Production Example 5]
A contact lens-shaped polymer was obtained in the same manner as in Production Example 1 except that 20 parts by mass of BuMA, which is a component other than (A), was used as the monomer A component.

[Comparative Production Example 6]
A contact lens-shaped polymer was obtained in the same manner as in Production Example 6 except that 25 parts by mass of 2-HEMA, which is a component other than (A), was used as the monomer A component.

[Comparative Production Example 7]
A contact lens-shaped polymer was obtained in the same manner as in Production Example 6 except that 25 parts by mass of DMAA, which was a component other than (A), was used as the monomer A component.

[Comparative Production Example 8]
A contact lens-shaped polymer was obtained in the same manner as in Production Example 6 except that 25 parts by mass of MMP, which is a component other than (A), was used as the monomer A component.

[Comparative Production Example 9]
A contact lens-shaped polymer was obtained in the same manner as in Production Example 6 except that 25 parts by mass of EMA, which is a component other than (A), was used as the monomer A component.

[Comparative Production Example 10]
A contact lens-shaped polymer was obtained in the same manner as in Production Example 6 except that 25 parts by mass of BuMA, which is a component other than (A), was used as the monomer A component.

  Table 9 shows the glass transition temperature (Tg) and water absorption values of the monomer A homopolymer used. The glass transition temperature of the homopolymer of the monomer A component is a value measured by differential scanning calorimetry (DSC) at a scanning speed of 20 ° C./min, or a value quoted from literature (Polymer Handbook 3rd Ed.). The water absorption of the homopolymer of the monomer A component is the mass W1 (g) of the homopolymer immersed in distilled water for 16 hours or more at 25 ° C., and then dried for 16 hours in an oven set at 105 ° C. The mass W2 (g) of the homopolymer was measured and calculated from the following formula. The homopolymer of the monomer A component is obtained by curing a mixture obtained by adding 0.4 part by mass of EDMA as a crosslinking agent and 0.4 part by mass of HMPPO as a polymerization initiator to 100 parts by mass of the monomer A component. I got it.

    Water absorption (%) = (W1-W2) / W1 × 100

  The monomer residual ratio of the contact lens-shaped polymers obtained in Production Examples 1 to 10 and Comparative Production Examples 1 to 10 was measured according to the following method. Table 10 shows the obtained results.

[Quantification of residual monomer components]
<Quantification of residual N-VP>
The contact lens-shaped polymers obtained in Production Examples 1 to 10 and Comparative Production 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 N-VP component (C). 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 are calculated as follows, and are calculated to the order of 0.1%. It was. 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 -The blending mass fraction (%) of VP.

S1 (%) = {V × (A−b)} / (a × W × w × 100)
S2 (%) = {V × (A−b)} / (a × W × 10000)

<Quantification of residual TRIS>
About the manufacture examples 1-10 and the comparative manufacture examples 1-10, about the obtained contact lens-shaped polymer material, the residual ratio of the monomer with respect to the compounding quantity of TRIS which is (B) 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 residual monomer mass ratio S4 (%) to the contact lens-shaped polymer material was calculated to the order of 0.01%.

  As is clear from the results of Table 10, Production Examples 1 to 10 were compared with Comparative Production Examples 1 to 10, regardless of the amount of N-VP remaining in the N-VP polymerizable composition. It was clearly reduced. In addition, in Production Examples 1 to 10, compared to Comparative Production Examples 1, 4, 5, 9, and 10, it was also shown that the residual ratio of TRIS insoluble in water was extremely low.

[Example 20]
A contact lens was prepared in the same manner as in Example 6 except that 0.5 parts by mass of 1-menthol as a cooling agent was added as an additive of the component (E) to the polymerizable composition prepared in Example 6. Obtained. However, a phosphate buffer solution containing no surfactant was used during sterilization.

[Example 21]
A contact lens was obtained in the same manner as in Example 20 except that 1.0 part by mass of l-menthol, which is a water-soluble organic solvent, was added to the polymerizable composition as an additive of the component (E).

[Example 22]
A contact lens was obtained in the same manner as in Example 20 except that 0.5 parts by mass of HCO-60 as a surfactant was added to the polymerizable composition.

[Example 23]
A contact lens was obtained in the same manner as in Example 20 except that 1.0 part by mass of HCO-60 as a surfactant was added to the polymerizable composition.

  In Example 6, 20 to 23, the contact lens-shaped polymer material obtained by taking out from the mold after curing 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, The measurement of S2) was performed. Further, contact lubrication obtained by sequentially subjecting the polymer material to surface treatment, hydration, elution, and sterilization treatment was evaluated for surface lubricity and water wettability in the same manner as described above. The obtained results are shown in Table 11.

  As apparent from the results of Table 11, it was shown that the residual N-VP of the polymer material was further reduced by using the additive of the component (E). Moreover, it was shown that the residual N-VP of the polymer material was further reduced even when a surfactant was used instead of the additive of component (E). Even when the additive of component (E) is used or when a surfactant is used instead of (E), the surface lubricity and water wettability are the same as when the surfactant is applied during sterilization. It has also been shown to have a suitable surface as an ophthalmic lens material.

[Example 24]
The l-menthol content in the contact lens produced in Example 20 was confirmed by performing GC analysis of the methanol extract. The 1-menthol content after sterilization in physiological saline was equivalent to 11% of the theoretical amount. From this, it is considered that a large amount was eluted in the lens manufacturing process. However, after that, even when stored in the same solution at room temperature for 6 months, the l-menthol content in the lens was 8% of the theoretical amount, indicating that there was no significant change.

[Example 25]
In Example 20, a contact lens was produced in the same manner as in Example 20, except that sterilization was performed in a physiological saline solution containing 0.05% of the surfactant HCO-60. Similarly, when the l-menthol content was quantified, it was 14% of the theoretical amount immediately after sterilization, and 8% of the theoretical amount after storage at room temperature for 6 months. It is considered that the surfactant in the preservation solution has no influence on the dissolution property of 1-menthol.

  The polymer material of the present invention has excellent water wettability and surface wettability, and can be highly stable despite containing a surfactant. It is suitably used for ophthalmic lenses, intraocular lenses, artificial corneas, corneal onlays, corneal inlays and the like. 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 (19)

[I] (A) a structural unit derived from a polymerizable compound having an acryloyloxy group and not having a silicon atom, and (B) a structural unit derived from a silicone compound having a polymerizable group, and a crosslinked and hydrogel A polymer, and [II] a surfactant,
(A) A polymer material having a glass transition temperature of −70 ° C. or more and 10 ° C. or less as a homopolymer of a polymerizable compound.   [II] The polymer material according to claim 1, wherein the content of the surfactant is 0.05% by mass or more and 1% by mass or less.   [II] The polymer material according to claim 1 or 2, wherein the surfactant is a nonionic surfactant having a polyoxyethylene group.   The nonionic surfactant having a polyoxyethylene group is a polyoxyethylene hydrogenated castor oil, a polyoxyethylene sorbitan fatty acid ester, a polyoxyethylene polyoxypropylene copolymer and a polyoxyethylene polysiloxane ether block copolymer. The polymer material according to claim 3, wherein the polymer material is at least one selected from the group consisting of coalesces.   The polymer material according to any one of claims 1 to 4, wherein (A) the water absorption as a homopolymer of the polymerizable compound is 20% or less. The polymer material according to any one of claims 1 to 5, wherein the polymerizable compound (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 (A) is at least one selected from the group consisting of 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-methoxyethoxyethyl acrylate, and 2-ethoxyethoxyethyl acrylate. Polymer material. (B) the silicone compound is
(B1) A compound having an ethylenically unsaturated double bond and a polydimethylsiloxane structure via a urethane bond, and / or (B2) comprising a silicone-containing alkyl (meth) acrylate, a silicone-containing styrene derivative and a silicone-containing fumaric acid diester. The polymer material according to any one of claims 1 to 7, which is at least one compound selected from the group. The polymer material according to claim 8, wherein the silicone compound of 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 is a divalent group derived from a diisocyanate selected from the group of saturated or unsaturated aliphatic, alicyclic and aromatic groups (where E ² is X ³ and X Forming two urethane bonds between ⁴ ).)]] The above [I] polymer is
The polymer material according to claim 1, further comprising (C) a structural unit derived from a compound having an amide group.   The polymer material according to claim 10, wherein the compound (C) having an amide group is N-vinylpyrrolidinone. The above [I] polymer is formed from a polymerizable composition containing (A) a polymerizable compound, (B) a silicone compound and (C) N-vinylpyrrolidinone,
With respect to 100 parts by mass of the total amount of (A) polymerizable compound, (B) silicone compound and (C) N-vinylpyrrolidinone,
(A) The content of the polymerizable compound is 10 parts by mass or more and 45 parts by mass or less,
(B) The content of the silicone compound is 10 parts by mass or more and 70 parts by mass or less,
The polymer material according to claim 11, wherein the content of (C) N-vinylpyrrolidinone is 10 parts by mass or more and 50 parts by mass or less. The polymerizable composition further contains a non-polymerizable additive,
This additive is at least one selected from the group consisting of a water-soluble organic solvent, a cooling agent and a thickening agent,
The polymer material according to claim 12, wherein the content of the additive is 5 parts by mass or less with respect to 100 parts by mass of the total amount of (A) the polymerizable compound, (B) the silicone compound, and (C) N-vinylpyrrolidinone. .   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. 14. The polymer material according to 13.   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 polymer material according to claim 13 or 14, which 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 polymer material according to claim 13, claim 14, or claim 15, which is at least one selected from the group consisting of:   The polymer material according to any one of claims 1 to 16, which has a water content of 40% or more.   An ophthalmic lens made of the polymer material according to any one of claims 1 to 17.   A contact lens made of the polymer material according to claim 1.