JPWO2020174570A1 - Polymer material - Google Patents

Abstract

The present invention provides a silicone-containing polymer material containing an internal wetting agent and having excellent transparency, which has improved antifouling property against lipids. The polymer material of the present invention is a polymer material obtained by polymerizing a polymerizable mixture containing (a) a monomer component and (b) a hydrophilic polymer component, and (a) the monomer component is (a-). 1) A silicone-containing monomer having an anionic group is contained, and the blending amount of (b) hydrophilic polymer component in the polymerizable mixture is 100 mass by total of (a) monomer component and (b) hydrophilic polymer component. It is about 1 part by mass to about 30 parts by mass with respect to the part.

Description

The present invention relates to polymer materials and more specifically to polymer materials suitable for ophthalmic lens applications.

Contact lenses are roughly classified into hard contact lenses and soft contact lenses. In recent years, most hard contact lenses have high oxygen permeability by being formed by using a silicone-containing polymer having a siloxane structure (Si—O—Si), but due to its hardness, foreign substances are foreign substances when worn. May cause a feeling. On the other hand, soft contact lenses are formed from a water-containing hydrogel obtained by copolymerizing a hydrophilic monomer, a (meth) acrylic monomer, and a cross-linking agent, so that an excellent wearing feeling can be obtained, while a hard contact lens can be used. Oxygen permeability tends to be lower than that. On the other hand, soft contact lenses have been developed that have both high oxygen permeability and excellent wearing feeling by using a silicone hydrogel containing a silicone-based monomer as a further copolymerization component.

However, soft contact lenses formed from silicone hydrogels tend to have lipids attached to their surface. Therefore, the adhesion of lipids is suppressed by plasma treatment or mixing a hydrophilic polymer as an internal wetting agent in the hydrogel.

When an internal wetting agent is used, the compatibility between the highly hydrophilic internal wetting agent and the highly hydrophobic silicone-based monomer is low. Therefore, in order to make the two compatible with each other, methyldi (trimethylsiloxy) silylpropyl is usually used. Silicone-containing monomers having a hydroxyl group such as glycerol methacrylate (also referred to as "SiGMA") are used (for example, Patent Document 1). As a result, a polymer material in which the adhesion of lipids is suppressed and has excellent transparency can be obtained, but further improvement in antifouling property against lipids is required.

Special Table 2005-51826A.

A main object of the present invention is to provide a silicone-containing polymer material containing an internal wetting agent and having excellent transparency, which has improved antifouling property against lipids.

［式（Ｉ）中、
Ｒ^ａ１〜Ｒ^ａ８はそれぞれ独立して、水素原子あるいはヘテロ原子を有していてもよい炭素数１〜５０の炭化水素基であり、
Ｚ^１およびＺ^２はそれぞれ独立して、下記式（１）で表される基であり、
−Ｒ^ｂ１−Ｘ−Ｒ^ｂ２ （１）
（式（１）中、
Ｒ^ｂ１は、ヘテロ原子を有していてもよい炭素数１〜２０アルキレン基であり、
Ｒ^ｂ２は、（メタ）アクリロイル基、ビニル基またはアリル基であり、
Ｘは、単結合、−Ｏ−または−ＮＲ^ｂ３−であり（ここで、Ｒ^ｂ３は、水素原子または炭素数１〜３のアルキル基である））、
Ａ^１は、ｋ４個の水素原子がＢ^１の基によって置換された炭素数１〜１２のアルキレン基（ただし、Ｂ^１の基以外のヘテロ原子を有していてもよい）であり、
Ａ^２は、ｋ５個の水素原子がＢ^２の基によって置換された炭素数１〜１２のアルキレン基（ただし、Ｂ^２の基以外のヘテロ原子を有していてもよい）であり、
Ａ^３は、ｋ１１個の水素原子がＢ^３の基によって置換された炭素数１〜１２のアルキレン基（ただし、Ｂ^３の基以外のヘテロ原子を有していてもよい）であり、
Ａ^４は、ｋ１２個の水素原子がＢ^４の基によって置換された炭素数１〜１２のアルキレン基（ただし、Ｂ^４の基以外のヘテロ原子を有していてもよい）であり、
Ｂ^１〜Ｂ^４はそれぞれ独立して、アニオン性基を有する一価の基であり、
Ｅは、−Ｏ−または−ＮＲ^ｃ１−であり（ここで、Ｒ^ｃ１は、水素原子または炭素数１〜４のアルキル基である）、
Ｌ^１は、単結合または（ｋ２＋１）価の連結基であり、
Ｌ^２は、単結合または（ｋ３＋１）価の連結基であり、
ｋ１およびｋ１’はそれぞれ独立して、４以上の整数であり、
ｋ２およびｋ３はそれぞれ独立して、１〜３の整数であり、
ｋ４およびｋ５はそれぞれ独立して、１〜５の整数であり、
ｋ６は、０または１であり、
ｋ７は、０〜１００の整数であり、
ｋ８は、０〜５の整数であり、
ｋ９およびｋ１０はそれぞれ独立して、０または１であり、
ｋ１１およびｋ１２はそれぞれ独立して、０〜５の整数である。］
１つの実施形態において、上記アニオン性基が、カルボキシル基を含む。
１つの実施形態において、上記（ｂ）親水性ポリマー成分の重量平均分子量が、１００，０００以上である。
１つの実施形態において、上記（ｂ）親水性ポリマー成分が、ポリビニルアミドである。
１つの実施形態において、上記（ｂ）親水性ポリマー成分が、ポリ−Ｎ−ビニルピロリドン、ポリアルキレングリコール、ポリサッカライド、ポリ（メタ）アクリル酸およびポリビニルアルコールから選択される少なくとも１種を含む。
１つの実施形態において、上記（ｂ）親水性ポリマー成分が、ポリ−Ｎ−ビニルピロリドンである。
１つの実施形態において、上記ポリマー材料の酸素透過係数が、３０Ｂａｒｒｅｒ〜１２０Ｂａｒｒｅｒである。
本発明の別の局面によれば、上記ポリマー材料を含む、眼科用医療機器が提供される。
１つの実施形態において、上記眼科医療機器は、コンタクトレンズである。According to one aspect of the present invention, a polymer material obtained by polymerizing a polymerizable mixture containing (a) a monomer component and (b) a hydrophilic polymer component, wherein the (a) monomer component is a polymer material. (A-1) Contains a silicone-containing monomer having an anionic group, and the blending amount of (b) hydrophilic polymer component in the polymerizable mixture is the total blending of (a) monomer component and (b) hydrophilic polymer component. A polymeric material is provided that is from about 1 part by mass to about 30 parts by mass with respect to 100 parts by mass.
In one embodiment, the (a) monomer component further comprises (a-2) a hydrophilic monomer.
In one embodiment, the (a) monomer component further comprises (a-3) a silicone-containing monomer having no anionic group.
In one embodiment, the silicone-containing monomer having the (a-1) anionic group has two or more polymerizable functional groups.
In one embodiment, the silicone-containing monomer having the (a-1) anionic group has three or more polymerizable functional groups.
In one embodiment, the silicone-containing monomer having the anionic group (a-1) has a structure represented by the following formula (I).

[In formula (I),
R ^{a1 to} R ^a8 are hydrocarbon groups having 1 to 50 carbon atoms, which may independently have a hydrogen atom or a hetero atom, respectively.
Z ¹ and Z ² are independent groups represented by the following formula (1).
-R ^b1 -X-R ^b2 (1)
(In equation (1),
R ^b1 is an alkylene group having 1 to 20 carbon atoms which may have a hetero atom.
R ^b2 is a (meth) acryloyl group, a vinyl group or an allyl group.
X is a single bond, -O- or -NR ^b3- (where R ^b3 is a hydrogen atom or an alkyl group with 1-3 carbon atoms).
A ¹ is k4 amino alkylene group having 1 to 12 carbon atoms in which hydrogen atom is substituted by a group B ¹ (provided that may have a hetero atom other than groups B ^1),
A ² is a k5 hydrogen atoms B ² alkylene group having 1 to 12 carbon atoms which is substituted by group (which may have a hetero atom other than groups B ^2),
A ³ is a k11 hydrogen atoms B ³ alkylene group having 1 to 12 carbon atoms which is substituted by group (which may have a hetero atom other than group B ^3),
A ⁴ is a k12 amino alkylene groups have been 1 to 12 carbon atoms substituted hydrogen atoms by a group of B ⁴ (provided that it may have a hetero atom other than group B ^4),
B ^{1 to} B ⁴ are monovalent groups having anionic groups independently of each other.
E is -O- or -NR ^c1- (where R ^c1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms).
L ¹ is a single bond or (k2 + 1) valence linking group.
L ² is a single bond or (k3 + 1) valent linking group.
k1 and k1'are independent integers of 4 or more, respectively.
k2 and k3 are independently integers 1 to 3, respectively.
k4 and k5 are independently integers of 1 to 5, respectively.
k6 is 0 or 1 and
k7 is an integer from 0 to 100 and
k8 is an integer from 0 to 5,
k9 and k10 are independently 0 or 1, respectively.
k11 and k12 are independently integers from 0 to 5. ]
In one embodiment, the anionic group comprises a carboxyl group.
In one embodiment, the weight average molecular weight of the hydrophilic polymer component (b) is 100,000 or more.
In one embodiment, the hydrophilic polymer component (b) is polyvinylamide.
In one embodiment, the hydrophilic polymer component (b) comprises at least one selected from poly-N-vinylpyrrolidone, polyalkylene glycol, polysaccharides, poly (meth) acrylic acid and polyvinyl alcohol.
In one embodiment, the hydrophilic polymer component (b) is poly-N-vinylpyrrolidone.
In one embodiment, the polymer material has an oxygen permeability coefficient of 30 Barrer to 120 Barrer.
According to another aspect of the invention, an ophthalmic medical device comprising the above polymeric material is provided.
In one embodiment, the ophthalmic medical device is a contact lens.

According to the present invention, by using a silicone-containing monomer having an anionic group, it is a silicone-containing polymer material containing an internal wetting agent and having excellent transparency, and the silicone-containing polymer having improved antifouling property against lipids. The material can be obtained.

Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to these embodiments.

The polymer material in one embodiment of the present invention is obtained by polymerizing a polymerizable mixture containing (a) a monomer component and (b) a hydrophilic polymer component. More specifically, the (a) monomer component is polymerized in a state where (a) a monomer component and (b) a hydrophilic polymer component are mixed, preferably in a compatible state. The (b) hydrophilic polymer component used in the present invention is typically a non-polymerizable component having no polymerizable functional group, and (a) the monomer component is polymerized in such a state. Therefore, a polymer material in which (a) a polymer containing a structural unit derived from a monomer component and (b) a hydrophilic polymer component are highly complexed can be obtained.

As used herein, the term "monomer" means a polymerizable compound having one or more polymerizable functional groups. Therefore, a polymerizable compound (also referred to as an oligomer) composed of two or more monomer units and a polymerizable compound having a large molecular weight (also referred to as macromer or macromonomer) are also included in the monomer.

Examples of the polymerizable functional group include a (meth) acryloyl group, a vinyl group, an allyl group and the like.

As used herein, "(meth)" means any methyl substitution. Thus, "(meth) acryloyl" means methacryloyl and / or acryloyl. The same applies to other descriptions such as "(meth) acrylic".

As used herein, when a number is accompanied by the term "about", it is intended to include the range ± 10%, ± 5%, ± 1% or ± 0.5% of that value. Further, in the present specification, it should be understood that the numerical values used to indicate the component content, the numerical value range, etc. are modified by the term "about" unless otherwise specified.

In the present specification, the structural notation of a polyvalent group does not specify the bonding direction of the group unless otherwise specified. Specifically, ^{the formula when R 2} is -C (= O) O-: R ^1- R ^2- R ³ is R ^1- C (= O) O-R ³ or R ^1- OC ( = O) -R ³ can be.

A. Polymerizable Mixture The polymerizable mixture contains (a) a monomer component and (b) a hydrophilic polymer component, and the (a) monomer component contains (a-1) a silicone-containing monomer having an anionic group. (A-1) The silicone-containing monomer having an anionic group has excellent compatibility with (b) the hydrophilic polymer component, and can contribute to the improvement of oxygen permeability and the antifouling property against lipids. It is possible to obtain a polymer material having excellent transparency and oxygen permeability, and further suppressing the adhesion of lipids. In addition, the polymerizable mixture may further contain the additive (c), if necessary.

In one embodiment, the polymerizable mixture is substantially free of hydroxyl group-containing silicone-containing monomers such as Sigma. Here, "substantially free of a silicone-containing monomer having a hydroxyl group" means that the content of the monomer in the monomer component is 0.1% by mass or less.

(A) Monomer component The monomer component contains (a-1) a silicone-containing monomer having an anionic group, preferably (a-2) a hydrophilic monomer and / or (a-3) having no anionic group. It further contains a silicone-containing monomer. The monomer component may further contain (a-4) hydrophobic monomer, (a-5) crosslinkable monomer, (a-6) functional monomer and the like, if necessary. The total content ratio of (a-1) a silicone-containing monomer having an anionic group, (a-2) a hydrophilic monomer, and (a-3) a silicone-containing monomer having no anionic group in the monomer component is, for example, 30. It can be from% by mass to 99% by mass, preferably 70% by mass to 95% by mass.

(A-1) Silicone-containing monomer having an anionic group The silicone-containing monomer having an anionic group (hereinafter, may be referred to as a first silicone-containing monomer) has a siloxane structure (Si—O—Si). Therefore, it is possible to impart high oxygen permeability to the polymer material, and it is possible to contribute to the improvement of compatibility with the hydrophilic polymer component and antifouling property against lipids due to having an anionic group. The silicone-containing monomer having an anionic group does not have a hydroxyl group.

The first silicone-containing monomer has one or more polymerizable functional groups, preferably two or more, for example, three or more, four or more, or five or more polymerizable functional groups. Since the first silicone-containing monomer has two or more polymerizable functional groups, a polymer material having good mechanical properties can be obtained even when a crosslinkable monomer is not used. In addition, effects such as reduction of unreacted monomers and easy removal of the polymer material (for example, an ophthalmic lens) obtained by the polymerization from the mold during mold polymerization can be obtained.

The number of anionic groups contained in the first silicone-containing monomer is one or more, preferably 2 to 10. When the number of anionic groups is within the above range, the effect of improving the compatibility with the hydrophilic polymer component and the antifouling property against lipids can be obtained. On the other hand, if there are too many anionic groups, for example, when the polymer material of the present invention is used as a contact lens, a disinfectant during cleaning may adhere to it, causing eye damage, and the water content of the contact lens. May become too high, causing problems such as difficulty in obtaining appropriate oxygen permeability and mechanical properties.

Examples of the anionic group, a carboxyl group, a sulfonic acid group, phosphoric acid group, a sulfuric acid ester group ₍₃ -O-SO ^-), and the like. The anionic group is preferably a carboxyl group.

The first silicone-containing monomer can be, for example, a macromonomer having a weight average molecular weight of 500 or more, preferably 1,000 to 100,000. When the first silicone-containing monomer is a macromonomer, effects such as improvement of mechanical properties and improvement of deformation recovery can be obtained.

［式（Ｉ）中、
Ｒ^ａ１〜Ｒ^ａ８はそれぞれ独立して、水素原子あるいはヘテロ原子を有していてもよい炭素数１〜５０の炭化水素基であり、
Ｚ^１およびＺ^２はそれぞれ独立して、下記式（１）で表される基であり、
−Ｒ^ｂ１−Ｘ−Ｒ^ｂ２ （１）
（式（１）中、
Ｒ^ｂ１は、ヘテロ原子を有していてもよい炭素数１〜２０アルキレン基であり、
Ｒ^ｂ２は、（メタ）アクリロイル基、ビニル基またはアリル基であり、
Ｘは、単結合、−Ｏ−または−ＮＲ^ｂ３−であり（ここで、Ｒ^ｂ３は、水素原子または炭素数１〜３のアルキル基である））、
Ａ^１は、ｋ４個の水素原子がＢ^１の基によって置換された炭素数１〜１２のアルキレン基（ただし、Ｂ^１の基以外のヘテロ原子を有していてもよい）であり、
Ａ^２は、ｋ５個の水素原子がＢ^２の基によって置換された炭素数１〜１２のアルキレン基（ただし、Ｂ^２の基以外のヘテロ原子を有していてもよい）であり、
Ａ^３は、ｋ１１個の水素原子がＢ^３の基によって置換された炭素数１〜１２のアルキレン基（ただし、Ｂ^３の基以外のヘテロ原子を有していてもよい）であり、
Ａ^４は、ｋ１２個の水素原子がＢ^４の基によって置換された炭素数１〜１２のアルキレン基（ただし、Ｂ^４の基以外のヘテロ原子を有していてもよい）であり、
Ｂ^１〜Ｂ^４はそれぞれ独立して、アニオン性基を有する一価の基であり、
Ｅは、−Ｏ−または−ＮＲ^ｃ１−であり（ここで、Ｒ^ｃ１は、水素原子または炭素数１〜４のアルキル基である）、
Ｌ^１は、単結合または（ｋ２＋１）価の連結基であり、
Ｌ^２は、単結合または（ｋ３＋１）価の連結基であり、
ｋ１およびｋ１’はそれぞれ独立して、４以上の整数であり、
ｋ２およびｋ３はそれぞれ独立して、１〜３の整数であり、
ｋ４およびｋ５はそれぞれ独立して、１〜５の整数であり、
ｋ６は、０または１であり、
ｋ７は、０〜１００の整数であり、
ｋ８は、０〜５の整数であり、
ｋ９およびｋ１０はそれぞれ独立して、０または１であり、
ｋ１１およびｋ１２はそれぞれ独立して、０〜５の整数である。］In one embodiment, the first silicone-containing monomer may have, for example, a structure represented by the following general formula (I).

[In formula (I),
R ^{a1 to} R ^a8 are hydrocarbon groups having 1 to 50 carbon atoms, which may independently have a hydrogen atom or a hetero atom, respectively.
Z ¹ and Z ² are independent groups represented by the following formula (1).
-R ^b1 -X-R ^b2 (1)
(In equation (1),
R ^b1 is an alkylene group having 1 to 20 carbon atoms which may have a hetero atom.
R ^b2 is a (meth) acryloyl group, a vinyl group or an allyl group.
X is a single bond, -O- or -NR ^b3- (where R ^b3 is a hydrogen atom or an alkyl group with 1-3 carbon atoms).
A ¹ is k4 amino alkylene group having 1 to 12 carbon atoms in which hydrogen atom is substituted by a group B ¹ (provided that may have a hetero atom other than groups B ^1),
A ² is a k5 hydrogen atoms B ² alkylene group having 1 to 12 carbon atoms which is substituted by group (which may have a hetero atom other than groups B ^2),
A ³ is a k11 hydrogen atoms B ³ alkylene group having 1 to 12 carbon atoms which is substituted by group (which may have a hetero atom other than group B ^3),
A ⁴ is a k12 amino alkylene groups have been 1 to 12 carbon atoms substituted hydrogen atoms by a group of B ⁴ (provided that it may have a hetero atom other than group B ^4),
B ^{1 to} B ⁴ are monovalent groups having anionic groups independently of each other.
E is -O- or -NR ^c1- (where R ^c1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms).
L ¹ is a single bond or (k2 + 1) valent linking group.
L ² is a single bond or (k3 + 1) valent linking group.
k1 and k1'are independent integers of 4 or more, respectively.
k2 and k3 are independently integers 1 to 3, respectively.
k4 and k5 are independently integers of 1 to 5, respectively.
k6 is 0 or 1 and
k7 is an integer from 0 to 100 and
k8 is an integer from 0 to 5,
k9 and k10 are independently 0 or 1, respectively.
k11 and k12 are independently integers from 0 to 5. ]

In the formula ^(I), the hydrocarbon group having 1 to 50 carbon atoms as defined with respect to R a1 ^{to R a8,} an alkyl group, an aryl group or an aralkyl group can be exemplified.

The alkyl group may be linear, branched, or may contain a cyclic structure. The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, still more preferably a methyl group or an ethyl group, and even more preferably a methyl group.

The alkyl group can have a heteroatom. The hetero atom may be contained in a monovalent substituent that replaces a hydrogen atom, or is contained in a divalent substituent that replaces a _{group containing a carbon atom in the main chain or a branched chain (−CH 2−).} You may be.

Examples of the monovalent substituent containing the hetero atom include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group having 1 to 3 carbon atoms, a carboxyl group and an amino group.

Examples of the divalent substituent containing the heteroatom include -O-, -NR ^a9- , -C (= O) O-, -NR ^a9 C (= O)-, and -NR ^a9 C (= O) O. −, −NR ^a9 C (= O) NR ^a10 −, −CH = N−, −C (= O) −NR ^a9 −C (= O) −, etc. (Here, R ^a9 and R ^a10 are Each independently is a hydrogen or an alkyl group having 1-3 carbon atoms).

As the aryl group or the aralkyl group, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms is preferable. Specific examples include a phenyl group, a benzyl group, a tolyl group, a xsilyl group and the like.

The aryl group or aralkyl group can have a hetero atom. Heteroatoms are typically included in monovalent substituents that replace hydrogen atoms. The monovalent substituent containing a heteroatom is as described above.

The ^{alkylene group having 1 to 12 carbon atoms specified for A 1 to} A ⁴ may be linear, branched, or may contain a cyclic structure. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 to 8 carbon atoms.

Each of the alkylene groups defined with respect to A ^{1 to} A ⁴ can have a hetero atom other than a monovalent group having an anionic group (a group of B ¹ , B ² , B ³ or B ^4). The hetero atom may be contained in a monovalent substituent that replaces the hydrogen atom of the alkylene group, and is a divalent substituent that replaces the group containing the carbon atom of the main chain or the branched chain (−CH _2- ). May be included in. The monovalent and divalent substituents containing heteroatoms are as described above.

Each of the above B ^{1 to} B ⁴ can be independently, for example, an organic group having an anionic group and having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms. Specific examples of B ¹ and B ² include a carboxyl group, a carboxymethyl group, a 2-carboxyethyl group, a 3-carboxypropyl group, a 4-carboxybutyl group, a sulfonic acid group, a sulfomethyl group, a 2-sulfoethyl group, and a few. -Disulfopropyl group, 3-sulfopropyl group, 4-sulfobutyl group, phosphoric acid group, phosphomethyl group, phosphoethyl group, 3-phosphopropyl group, 4-phosphobutyl group and the like can be mentioned.

In the above formula (1), the ^{alkylene group having 1 to 20 carbon atoms defined for R b1} may be linear, branched, or may contain a cyclic structure. The alkylene group is preferably an alkylene group having 1 to 18 carbon atoms, more preferably an alkylene group having 1 to 12 carbon atoms, and further preferably an alkylene group having 1 to 8 carbon atoms.

The ^{alkylene group defined for R b1} can have a heteroatom. The hetero atom may be contained in a monovalent substituent that replaces a hydrogen atom, or is contained in a divalent substituent that replaces a _{group containing a carbon atom in the main chain or a branched chain (−CH 2−).} You may be. The monovalent substituent containing a heteroatom is as described above. The above-mentioned divalent substituents containing a heteroatom are also mentioned, and among them, -NH-, -NHC (= O)-or -NHC (= O) O- are preferable. Since these substituents have hydrogen-bonding protons, the number of introduced anionic groups is suppressed, and the affinity with the hydrophilic polymer component and the compatibility between the hydrophilic polymer component with other monomers are improved. be able to. Among them, it is preferable to include a urethane bond (-NHC (= O) O-). By having a polymerizable end and having a urethane bond between the polymerizable functional group and the siloxane segment, the effect of the present invention can be preferably obtained with a small number of anionic groups. Also, the mechanical strength of the resulting polymeric material can be increased.

In one ^{embodiment, R b1} is "- ^{R b3} - urethane bond ^{-R b4} -" having the structure of or ^{"-R b3} - urethane bond ^{-R b4} - - urethane bond ^{-R b5".} In these structures, R ^b3 , R ^b4 and R ^b5 are independently alkylene groups having 1 to 10 carbon atoms which may have a hetero atom (preferably ether oxygen), and preferably carbon. It can be an alkylene group of numbers 1-5.

R ^b2 is preferably a (meth) acryloyl group, in which case X is preferably −O−.

（式（２）中、
Ｒ^ｄ１、Ｒ^ｄ２、Ｒ^ｄ４およびＲ^ｄ５はそれぞれ独立して、炭素数１〜６、好ましくは炭素数１〜３の直鎖または分岐アルキレン基であり、
Ｒ^ｄ３は、炭素数１〜６の直鎖、分岐または環状アルキレン基あるいはその組み合わせからなる基であり、
Ｒ^ｄ６は、水素またはメチル基であり、
ｐ１およびｐ２はそれぞれ独立して、０〜１５の整数であり、
ｐ３は、０または１であり、
ただし、（メタ）アクリロイルオキシ基（ＣＨ_２＝ＣＲ^ｄ６−ＣＯＯ−）を除いた残基に含まれる炭素原子数は、２０以下である。）As a specific example of the group represented by the formula (1), the group represented by the following formula (2) or (3) can be exemplified.

(In equation (2),
R ^d1 , R ^d2 , R ^d4 and R ^d5 are independently linear or branched alkylene groups having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms.
R ^d3 is a group consisting of a linear, branched or cyclic alkylene group having 1 to 6 carbon atoms or a combination thereof.
R ^d6 is a hydrogen or methyl group and
p1 and p2 are independently integers from 0 to 15, respectively.
p3 is 0 or 1 and
However, the number of carbon atoms contained in the residue excluding the (meth) acryloyloxy group (CH ₂ = CR ^{d6-COO-) is 20 or less.} )

（式（３）中、
Ｒ^ｄ７およびＲ^ｄ8はそれぞれ独立して、炭素数１〜６、好ましくは炭素数１〜３の直鎖または分岐アルキレン基であり、
Ｒ^ｄ9は、水素またはメチル基であり、
ｐ４は、０〜１５の整数であり、
ただし、（メタ）アクリロイルオキシ基（ＣＨ_２＝ＣＲ^ｄ９−ＣＯＯ−）を除いた残基に含まれる炭素原子数は、２０以下である。）

(In equation (3),
R ^d7 and R ^d8 are independently linear or branched alkylene groups having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms.
R ^d9 is a hydrogen or methyl group and
p4 is an integer from 0 to 15 and
However, the number of carbon atoms contained in the residue excluding the (meth) acryloyloxy group (CH ₂ = CR ^{d9 −COO−) is 20 or less.} )

（上記式中、
Ｒ^ｅ１、Ｒ^ｅ２およびＲ^ｅ３はそれぞれ独立して、水素または炭素数１〜５のアルキル基である。）Specific examples of the linking group when L ¹ and / or L ² are linking groups include the groups represented by the following formulas (4) to (10) and a group consisting of two or more combinations of these groups. it can. In formulas (4) to (10), * indicates a bond, and any bond may be bonded to ^{A 1} or A ^2.

(In the above formula,
R ^e1 , ^{Re 2} and ^{Re 3} are independently hydrogen or alkyl groups having 1 to 5 carbon atoms. )

k1 and k1'are independent of each other, for example, an integer of 10 to 200, preferably an integer of 15 to 150, and more preferably an integer of 20 to 80.

k2 and k3 are independently integers of 1 to 3, and are preferably selected to satisfy the relationship of k2 + k3 ≧ 3, and more preferably k2 + k3 ≧ 4. In one embodiment, k2 and k3 are both 1, 2 or 3.

k4 and k5 are independent, preferably 1 or 2, respectively. In one embodiment, k4 and k5 are both 1 or 2. Further, k11 and k12 are independently, preferably 0, 1, or 2. The sum of k4, k5, k11 and k12 (k4 + k5 + k11 + k12) is preferably an integer of 2-8, more preferably an integer of 2-6.

k7 is preferably an integer of 50 or less, and more preferably an integer of 30 or less. When k7 is an integer of 1 or more, − {CH _2- CH _2- (E) _k6 } _k7 − is preferably an ethylene (or polyethylene) group or an oxyethylene (or polyoxyethylene) group.

k8 is preferably an integer of 0 to 3, more preferably 0, 1, or 2, and even more preferably 0 or 1.

k9 and k10 are independently 0 or 1, respectively.

（式中、
Ｒ^f１、Ｒ^f２、Ｒ^f３およびＲ^f４はそれぞれ独立して、上記式（２）または（３）で表される基であり、
Ｌ^３およびＬ^４はそれぞれ独立して、二価または三価の連結基であり、
ｍ１、ｍ２、ｍ４およびｍ５はそれぞれ独立して、０〜５の整数であり、
ｍ３は、１０〜２００の整数であり、
ｍ６およびｍ７はそれぞれ独立して、０〜５の整数であり、
ただし、Ｌ^３が二価の連結基であるとき、Ｒ^ｆ２は存在せず、
Ｌ^４が二価の連結基のとき、Ｒ^ｆ４は存在しない。）An example of a more specific structure of the first silicone-containing monomer represented by the general formula (I) is shown in the following formula (II).

(During the ceremony,
R ^f1 , R ^f2 , R ^f3 and R ^f4 are independent groups represented by the above formula (2) or (3), respectively.
L ³ and L ⁴ are independently divalent or trivalent linking groups, respectively.
m1, m2, m4 and m5 are independently integers from 0 to 5, respectively.
m3 is an integer of 10 to 200 and
m6 and m7 are independently integers from 0 to 5, respectively.
However, when L ³ is a divalent linking group, R ^f2 does not exist and
When L ⁴ is a divalent linking group, R ^{f 4} does not exist. )

The blending ratio of the first silicone-containing monomer in the polymerizable mixture is, for example, 1% by mass to 70% by mass, preferably 5% by mass, based on the total blending amount of the (a) monomer component and (b) hydrophilic polymer component. It can be% to 60% by mass, more preferably 10% to 40% by mass. When the blending ratio of the first silicone-containing monomer is within the above range, a polymer material having high oxygen permeability and transparency and excellent antifouling property against lipids can be obtained.

(A-2) Hydrophilic Monomer The hydrophilic monomer can be copolymerized with a first silicone-containing monomer or the like to form a highly hydrophilic silicone-containing polymer, and the obtained polymer material can be a hydrogel. Examples of the hydrophilic monomer include a monomer having a solubility in water at 25 ° C. of 0.03 g / mL or more, preferably a monomer having a solubility of 0.07 g / mL or more (however, those containing a silicon atom and polymerizable functionality). (Except those having two or more groups) can be used.

Specific examples of the hydrophilic monomer include hydroxyl group-containing alkyl (meth) acrylate, (meth) acrylamide and N-vinyllactam having an alkyl group having 1 to 4 carbon atoms. The hydrophilic monomer can be used alone or in combination of two or more.

The alkyl group of the hydroxyl group-containing alkyl (meth) acrylate may be branched, if necessary. Specific examples of the hydroxyl group-containing alkyl (meth) acrylate include hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate, and dihydroxypropyl (meth). Examples thereof include dihydroxyalkyl (meth) acrylates such as acrylates, dihydroxybutyl (meth) acrylates and dihydroxypentyl (meth) acrylates.

Examples of the (meth) acrylamide include N, N-dialkyl (meth) acrylamide such as N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, and N, N-dipropyl (meth) acrylamide. Examples thereof include N, N-dialkylaminoalkyl (meth) acrylamide such as N, N-dimethylaminopropyl (meth) acrylamide and N, N-diethylaminopropyl (meth) acrylamide.

Examples of N-vinyllactam include N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam and the like.

The hydrophilic monomer is not limited to those described above. Other hydrophilic monomers that can be used include, for example, alkoxypolyalkylene glycol mono (meth) acrylate, polyalkylene glycol mono (meth) acrylate, (meth) acrylic acid, 1-methyl-3-methylene-2-pyrrolidinone, and the like. Maleic anhydride, maleic acid, maleic acid derivative, fumaric acid, fumaric acid derivative, aminostyrene, hydroxystyrene, 2-methoxyethyl acrylate and the like can be mentioned.

Among the hydrophilic monomers exemplified above, hydroxyl group-containing alkyl (meth) acrylates having 1 to 4 carbon atoms, N, N-dimethyl (meth) acrylamide, N-vinylpyrrolidone, and alkoxypolyalkylene glycol mono (meth). ) Acrylate can be preferably used.

The blending ratio of the hydrophilic monomer in the polymerizable mixture is, for example, 0.1% by mass to 90% by mass, preferably 20% by mass, based on the total blending amount of the (a) monomer component and (b) hydrophilic polymer component. It can be ~ 80% by mass, more preferably 30% by mass to 70% by mass. When the blending ratio of the hydrophilic monomer is within the above range, a polymer material having a high water content can be obtained.

(A-3) Silicone-containing monomer having no anionic group A silicone-containing monomer having no anionic group (hereinafter, may be referred to as a second silicone-containing monomer) improves the oxygen permeability of the polymer material. It can be further improved. The second silicone-containing monomer has a siloxane structure and is any suitable monomer as long as it does not have an anionic group and a hydroxyl group (for example, a monomer used in conventional ophthalmic lens applications). Can be used. Examples of such a monomer include the silicone-containing monomers described in paragraphs 0039 to 0044 of Japanese Patent Application Laid-Open No. 2015-503631 (excluding those having a hydroxyl group), and paragraph 0060 of Japanese Patent Application Laid-Open No. 2014-40598. Examples thereof include the silicone-containing monomers described in paragraphs ~ 0065. The second silicone-containing monomer can be used alone or in combination of two or more.

Specific examples of the second silicone-containing monomer include trimethylsiloxydimethylsilylmethyl (meth) acrylate, trimethylsiloxydimethylsilylpropyl (meth) acrylate, methylbis (trimethylsiloxy) silylpropyl (meth) acrylate, and tris (trimethylsiloxy) silyl. Propyl (meth) acrylate, mono [methylbis (trimethylsiloxy) syroxy] bis (trimethylsiloxy) silylpropyl (meth) acrylate, tris [methylbis (trimethylsiloxy) syroxy] silylpropyl (meth) acrylate, methylbis (trimethylsiloxy) silylpropyl Glyceryl (meth) acrylate, tris (trimethylsiloxy) silylpropyl glyceryl (meth) acrylate, mono [methylbis (trimethylsiloxy) syroxy] bis (trimethylsiloxy) silylpropylglyceryl (meth) acrylate, trimethylsilylethyltetramethyldisyloxypropylglyceryl ( Meta) acrylate, trimethylsilylmethyl (meth) acrylate, trimethylsilylpropyl glyceryl (meth) acrylate, trimethylsilylpropyl (meth) acrylate, trimethylsiloxydimethylsilylpropylglyceryl (meth) acrylate, methylbis (trimethylsiloxy) silylethyltetramethyldisyloxymethyl (meth) Silicone-containing alkyl (meth) acrylates such as meta) acrylate, tetramethyltriisopropylcyclotetrasiloxanylpropyl (meth) acrylate, tetramethyltriisopropylcyclotetrasiloxybis (trimethylsiloxy) silylpropyl (meth) acrylate; tris (trimethyl) Syroxy) Cyril styrene, bis (trimethylsiloxy) methylsilylstyrene, (trimethylsiloxy) dimethylsilylstyrene, tris (trimethylsiloxy) syroxydimethylsilylstyrene, [bis (trimethylsiloxy) methylsiloxy] dimethylsilylstyrene, (trimethylsiloxy) dimethyl Cyril styrene, heptamethyltrisiloxanyl styrene, nonamethyltetrasiloxanyl styrene, pentadecamethyl heptasiloxanyl styrene, henei kosamethyldecasyloxanyl styrene, heptacosamethyl tridecacyloxanyl styrene, gentria Contamethylpentadecacyloxanylstyrene, trimethylsiloxypen Tamethyldisyloxymethylsilylstyrene, Tris (pentamethyldisiloxy) silylstyrene, Tris (trimethylsiloxy) syroxybis (trimethylsiloxy) silylstyrene, bis (heptamethyltrisiloxy) methylsilylstyrene, Tris [methylbis (trimethylsiloxy) syroxy ] Cyril styrene, heptaxis (trimethylsiloxy) trisilylstyrene, trimethylsiloxybis [tris (trimethylsiloxy) siloxy] silylstyrene, nonamethyltetrasiloxyundecylmethylpentasiloxymethylsilylstyrene, tris [tris (trimethylsiloxy) siloxy] silyl Styrene, (Tristrimethylsiloxyhexamethyl) tetrasiloxy [Tris (trimethylsiloxy) siloxy] trimethylsiloxysilylstyrene, nonakis (trimethylsiloxy) tetrasilylstyrene, bis (tridecamethylhexasiloxy) methylsilylstyrene, heptamethylcyclotetrasiloki Silicone-containing styrene derivatives such as sanylstyrene, heptamethylcyclotetrasiloxybis (trimethylsiloxy) silylstyrene, tripropyltetramethylcyclotetrasiloxanylstyrene, trimethylsilylstyrene; bis (3- (trimethylsilyl) propyl) fumarate, bis ( Silicone-containing fumaric acid diesters such as 3- (pentamethyldisyloxanyl) propyl) fumarate and bis (tris (trimethylsiloxy) silylpropyl) fumarate; and the like.

As another specific example of the second silicone-containing monomer, mono (meth) acryloyloxypropyl-terminated mono-n-butyl-terminated polydimethylsiloxane, mono- (meth) acryloyloxypropyl-terminated mono-n-methyl-terminated polydimethylsiloxane, Mono (meth) acryloyloxypropyl terminal mono-n-butyl terminal polydiethylsiloxane, mono (meth) acryloyloxypropyl terminal mono-n-methyl terminal polydiethylsiloxane, mono (meth) acryloylaminopropyl terminal mono-n-butyl terminal Polydimethylsiloxane, mono (meth) acryloylaminopropyl-terminated mono-n-methyl-terminated polydimethylsiloxane, mono (meth) acryloylaminopropyl-terminated mono-n-butyl-terminated polydiethylsiloxane, mono- (meth) acryloylaminopropyl-terminated mono- Examples thereof include n-methyl-terminated polydiethylsiloxane. In these silicone-containing monomers, the number of repetitions of (Si—O) can be, for example, 4 to 20, preferably 4 to 12, more preferably 4 to 10.

The blending ratio of the second silicone-containing monomer in the polymerizable mixture is, for example, 0% by mass to 70% by mass, preferably 5% by mass, based on the total blending amount of the (a) monomer component and (b) hydrophilic polymer component. It can be% to 60% by mass, more preferably 10% to 40% by mass. When the content ratio of the second silicone-containing monomer is within the above range, a polymer material having high oxygen permeability while maintaining transparency can be obtained.

The total blending ratio of the first silicone-containing monomer and the second silicone-containing monomer in the polymerizable mixture is, for example, 1% by mass or more with respect to the total blending amount of the (a) monomer component and (b) hydrophilic polymer component. It can be 90% by mass, preferably 10% by mass to 80% by mass, and more preferably 20% by mass to 70% by mass. It can be said that one of the features of the present invention is that compatibility with the hydrophilic polymer component can be ensured even when the blending ratio of the silicone-containing monomer is high as described above.

(A-4) Hydrophobic Monomer The hydrophobic monomer is added as necessary for the purpose of improving the copolymerization reactivity, adjusting the hardness or mechanical strength of the polymer material, and the like. As the hydrophobic monomer, for example, a monomer having a solubility in water at 25 ° C. of less than 0.03 g / mL (excluding those containing a silicon atom and those having two or more polymerizable functional groups) is used. Can be

As a specific example of the hydrophobic monomer, a monomer conventionally used for an ophthalmic lens material can be appropriately used. Specific examples include alkyl (meth) acrylates having a solubility in water at 25 ° C. of less than 0.03 g / mL (for example, alkyl (meth) acrylates having an alkyl group having 20 or less carbon atoms) and alkoxyalkyl (meth). Examples thereof include acrylates (for example, alkoxyalkyl (meth) acrylates having an alkoxyalkyl group having 20 or less carbon atoms). The alkyl (meth) acrylate may have a substituent such as a hydroxyl group.

The blending ratio of the hydrophobic monomer in the polymerizable mixture is, for example, 0% by mass to 40% by mass, preferably 0% by mass to 30% with respect to the total blending amount of the (a) monomer component and (b) hydrophilic polymer component. It can be mass%, more preferably 0 mass% to 20 mass%. When the content ratio of the hydrophobic monomer is within the above range, a polymer material having excellent transparency and mechanical strength can be obtained.

(A-5) Crosslinkable Monomer The crosslinkable monomer is added as necessary for the purpose of improving the mechanical strength and shape stability of the polymer material. As the crosslinkable monomer, a monomer having two or more polymerizable functional groups (excluding those containing a silicon atom) is used.

Specific examples of the crosslinkable monomer include butanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and di (di). Propropylene glycol di (meth) acrylate, diallyl fumarate, allyl (meth) acrylate, vinyl (meth) acrylate, trimethylpropantri (meth) acrylate, methacryloyloxyethyl (meth) acrylate, divinylbenzene, diallyl phthalate, diallyl adipate , Triallyl diisocyanate, α-methylene-N-vinylpyrrolidone, 4-vinylbenzyl (meth) acrylate, 3-vinylbenzyl (meth) acrylate, 2,2-bis ((meth) acryloyloxyphenyl) hexafluoropropane, 2, , 2-Bis ((meth) acryloyloxyphenyl) propane, 1,4-bis (2- (meth) acryloyloxyhexafluoroisopropyl) benzene, 1,3-bis (2- (meth) acryloyloxyhexafluoroisopropyl) Benzene, 1,2-bis (2- (meth) acryloyloxyhexafluoroisopropyl) benzene, 1,4-bis (2- (meth) acryloyloxyisopropyl) benzene, 1,3-bis (2- (meth) acryloyl) Examples thereof include oxyisopropyl) benzene and 1,2-bis (2- (meth) acryloyloxyisopropyl) benzene. Of these, butanediol di (meth) acrylate and / or ethylene glycol di (meth) acrylate may be preferably used. The crosslinkable monomer may be used alone or in combination of two or more.

The blending ratio of the crosslinkable monomer in the polymerizable mixture is appropriately set according to the purpose. For example, when the monomer according to (a-1) or (a-3) is polyfunctional, the use of the crosslinkable monomer is not essential, and the blending ratio thereof can be 0%. When a crosslinkable monomer is used, the blending ratio thereof is, for example, 2% by mass or less, 1% by mass or less, or 0.5% by mass with respect to the total blending amount of the (a) monomer component and (b) hydrophilic polymer component. It can be as follows.

(A-6) Functional Monomer The functional monomer is added as necessary for the purpose of imparting a predetermined function to the polymer material. Examples of the functional monomer include a polymerizable dye, a polymerizable ultraviolet absorber, and a polymerizable ultraviolet absorbing dye.

Specific examples of the polymerizable dye include 1-phenylazo-4- (meth) acryloyloxynaphthalene, 1-phenylazo-2-hydroxy-3- (meth) acryloyloxynaphthalene, and 1-naphthylazo-2-hydroxy-3. -(Meta) acryloyloxynaphthalene, 1- (α-anthrylazo) -2-hydroxy-3- (meth) acryloyloxynaphthalene, 1-((4'-(phenylazo) -phenyl) azo) -2-hydroxy-3 -(Meta) acryloyloxynaphthalene, 1- (2', 4'-xylylazo) -2- (meth) acryloyloxynaphthalene, 1- (o-tolylazo) -2- (meth) acryloyloxynaphthalene, 2- (m) -(Meta) acryloylamide-anilino) -4,6-bis (1'-(o-tolylazo) -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-Acryloylazo) -2'-naphthyl) -3-vinylphthalic acid monoamide, N- (1'-(o-cryloylazo) -2'-naphthyl) -6-vinylphthalic acid monoamide, 3 -Vinylphthalic acid- (4'-(p-sulfophenylazo) -1'-naphthyl) monoester, 6-vinylphthalic acid- (4'-(p-sulfophenylazo) -1'-naphthyl) monoester, 3 -(Meta) 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- (meth) Azo-based polymerizable dyes such as acryloylamide-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'-isopropenylbenzoylamide) -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'-vinylbenzoylamide) -9 , 10-Anthraquinone, 1,5-bis (4'-isopropenylbenzoylamide) -9,10-anthraquinone, 1-methylamino-4- (3'-vinylbenzoylamide) -9,10-anthraquinone, 1- Methylamino-4- (4'-vinylbenzo Iloxyethylamino) -9,10-anthraquinone, 1-amino-4- (3'-vinylphenylamino) -9,10-anthraquinone-2-sulfonic acid, 1-amino-4- (4'-vinylphenyl) Amino) -9,10-anthraquinone-2-sulfonic acid, 1-amino-4- (2'-vinylbenzylamino) -9,10-anthraquinone-2-sulfonic acid, 1-amino-4- (3'-) (Meta) 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-carboxyallylamino) -9,10 -Antraquinone, 1- (β-isopropoxycarbonylallylamino) -5-benzoylamide-9,10-anthraquinone, 2- (3'-(meth) acryloylamide-anilino) -4- (3'-(3 " -Sulfon-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" -methoxy) Anthraquinone-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, 1,4-bis (4- (2-methacryloxyethyl) phenylamino) 9,10 -Anthraquinone-based polymerizable dyes such as anthraquinone, 1,4-bis ((2-methacryloxyethyl) amino) 9,10-anthraquinone; Nitro-based polymerizable dyes such as o-nitroanilinomethyl (meth) acrylate; Examples thereof include phthalocyanine-based polymerizable dyes such as (meth) acryloylated tetraamino copper phthalocyanine and (meth) acryloylated (dodecanoylated tetraamino copper phthalocyanine). These can be used alone or in admixture of two or more.

Specific examples of the polymerizable ultraviolet absorber include 2-hydroxy-4- (meth) acryloyloxybenzophenone, 2-hydroxy-4- (meth) acryloyloxy-5-t-butylbenzophenone, and 2-hydroxy-4. -(Meta) acryloyloxy-2', 4'-dichlorobenzophenone, 2-hydroxy-4- (2'-hydroxy-3'-(meth) acryloyloxypropoxy) benzophenone and other benzophenone-based polymerizable ultraviolet absorbers; 2 -(2'-Hydroxy-5'-(meth) acryloyloxyethylphenyl) -2H-benzotriazole, 2- (2'-hydroxy-5'-(meth) acryloyloxyethylphenyl) -5-chloro-2H- Benzotriazole, 2- (2'-hydroxy-5'-(meth) acryloyloxypropylphenyl) -2H-benzotriazole, 2- (2'-hydroxy-5'-(meth) acryloyloxypropyl-3'-t -Butylphenyl) -5-chloro-2H-benzotriazole, 2- (2'-hydroxy-5'-(2 "-methacryloyloxyethoxy) -3'-t-butylphenyl) -5-methyl-2H-benzo Bentotriazole-based polymerizable UV absorbers such as triazole; salicylic acid derivative-based polymerizable UV absorbers such as 2-hydroxy-4-methacryloyloxymethylbenzoate; 2-cyano-3-phenyl-3- (3'-(3'-( Examples thereof include meta) acryloyloxyphenyl) propenylate methyl ester, etc. These can be used alone or in combination 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) acryloyloxypropylphenylazo) ) 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) acryloyloxyethylphenylazo) benzophenone, 2,4-dihydroxy-3- (o- (meth) acryloyloxypropylphenylazo) benzophenone, 2,4-dihydroxy-5-(o- (meth) acryloyl) Oxypropylphenylazo) benzophenone, 2,4-dihydroxy-3-(p-(N, N-di (meth) acryloyloxyethylamino) phenylazo) benzophenone, 2,4-dihydroxy-5-(p- (N,) N-di (meth) acryloyloxyethylamino) phenylazo) benzophenone, 2,4-dihydroxy-3- (o- (N, N-di (meth) acryloyloxyethylamino) phenylazo) benzophenone, 2,4-dihydroxy- 5- (o- (N, N-di (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) phenylazophenone) benzophenone, 2,4-dihydroxy-5-(o- (N-ethyl-N- (meth) acryloyl) Oxyethylamino) phenylazo) benzophenone, 2,4-dihydroxy-3-(p- (N-ethyl-N- (meth) acryloylamino) phenylazo) benzophenone, 2,4-dihydroxy-5-(p- (N-) Ethyl-N- (meth) acryloylamino) phenylazo) benzophenone, 2,4-dihydroxy-3-(o- (N-ethyl-N- (meth) acryloylamino) phenylazo) benzophenone, 2,4-dihydroxy-5 (O- (N-ethyl-N- (meth) acryloylamino) phenylazo) Benzophenone-based polymerizable ultraviolet-absorbing dyes such as benzophenone, and benzoic acid-based polymerization such as 2-hydroxy-4- (p-styrenoazo) phenyl benzoate. Examples include sex-ultraviolet absorbing pigments. These can be used alone or in admixture of two or more.

The total amount of the functional monomer is, for example, 0.001 part by mass to 5 parts by mass, preferably 0.05 part by mass with respect to 100 parts by mass of the total amount of the (a) monomer component and (b) hydrophilic polymer component. It can be 3 parts to 3 parts by mass.

(B) Hydrophilic Polymer Component As the hydrophilic polymer component, any suitable polymer that can impart surface hydrophilicity to the polymer material can be used. For example, polymers such as polyvinylamide (for example, polyvinyllactam), polyamide, polylactone, polyimide, and polylactam can be used as the hydrophilic polymer. The hydrophilic polymer may be a random copolymer composed of two or more kinds of monomers, an alternating copolymer, a block copolymer, or a graft copolymer. Among them, a polymer having a cyclic structure, for example, a cyclic amide structure or a cyclic imide structure in the main chain or the side chain can be preferably used. As the hydrophilic polymer component, only one kind of hydrophilic polymer may be used, or two or more kinds of hydrophilic polymers may be used in combination.

Specific examples of the hydrophilic polymer include poly-N-vinylpyrrolidone, poly-N-vinyl-2-piperidone, poly-N-vinyl-2-caprolactam, poly-N-vinyl-3-methyl-2-caprolactam, and the like. Poly-N-Vinyl-3-methyl-2-piperidone, poly-N-vinyl-4-methyl-2-piperidone, poly-N-vinyl-4-methyl-2-caprolactam, poly-N-vinyl-3- Ethyl-2-pyrrolidone and poly-N-vinyl-4,5-dimethyl-2-pyrrolidone, polyvinylimidazole, poly-N-N-dimethylacrylamide, polyvinyl alcohol, poly (meth) acrylic acid, poly (2-hydroxyethyl) ) (Meta) acrylates, polyalkylene glycols such as polyethylene glycol, poly-2-ethyl oxazoline, heparin polysaccharides, polysaccharides, and copolymers thereof. Among them, poly-N-vinylpyrrolidone, polyalkylene glycol, polysaccharide, poly (meth) acrylic acid, polyvinyl alcohol, poly (2-hydroxyethyl) (meth) acrylate and the like can be preferably used.

The weight average molecular weight of the hydrophilic polymer is, for example, 100,000 or more, preferably 150,000 to 2,000,000, more preferably 300,000 to 1,800,000, still more preferably 500,000 to 1. , 500,000.

The K value of the hydrophilic polymer may be, for example, 30 to 150, preferably 60 to 120, more preferably 90 to 120. Here, the K value is obtained by measuring the viscosity by the first method <2.53> of the viscosity measurement method in the 16th revised Japanese Pharmacopoeia, and by using the Fikenscher formula according to the method described in the "K value" column described in the Pharmacopoeia. be able to.

The blending amount of the hydrophilic polymer component in the polymerizable mixture is typically 1 part by mass to 30 parts by mass with respect to 100 parts by mass of the total amount of the (a) monomer component and (b) hydrophilic polymer component. It can be preferably 3 parts by mass to 20 parts by mass, and more preferably 5 parts by mass to 15 parts by mass. When the blending amount of the hydrophilic polymer is within the above range, a polymer material having excellent surface hydrophilicity can be obtained.

(C) Additive As the additive, any suitable additive can be selected depending on the purpose. Examples of the additive include a polymerization initiator, an organic solvent and the like.

The polymerization initiator is appropriately selected depending on the polymerization method. Examples of the thermal polymerization initiator used for polymerization by heating include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), benzoyl peroxide, and t-butylhydro. Examples thereof include peroxide, cumenehydroperoxide, lauroyl peroxide, t-butylperoxyhexanoate, 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 blended in the polymerizable mixture is preferably 0.001 part by mass to 2 parts by mass with respect to 100 parts by mass of the total amount of the (a) monomer component and (b) hydrophilic polymer component. More preferably, it is 0.01 part by mass to 1 part by mass.

Examples of the photopolymerization initiator used for polymerization by light irradiation include phosphine such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO) and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide. Oxide-based photopolymerization initiators; benzoin-based photopolymerization initiators such as methyl orthobenzoyl benzoate, methyl benzoyl formate, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin-n-butyl ether; 2-hydroxy -2-Methyl-1-phenylpropan-1-one (HMPPO), p-isopropyl-α-hydroxyisobutylphenone, pt-butyltrichloroacetophenone, 2,2-dimethoxy-2-phenylacetophenone, α, α- Phenone-based photopolymerization initiators such as dichloro-4-phenoxyacetophenone, N, N-tetraethyl-4,4-diaminobenzophenone; 1-hydroxycyclohexylphenyl ketone; 1-phenyl-1,2-propanedione-2- (o) −ethoxycarbonyl) oxime; thioxanson-based photopolymerization initiators such as 2-chlorothioxanson and 2-methylthioxanson; 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 together with a photopolymerization initiator.

The blending amount of the photopolymerization initiator and the photosensitizer in the polymerizable mixture is preferably 0.001 part by mass with respect to 100 parts by mass of the total blending amount of the (a) monomer component and (b) hydrophilic polymer component. ~ 2 parts by mass, more preferably 0.01 parts by mass to 1 part by mass.

As the organic solvent, a water-soluble organic solvent is preferable. As the water-soluble organic solvent, alcohol having 1 to 4 carbon atoms, acetone, methyl ethyl ketone, dimethylformamide, dimethyl sulfoxide, acetonitrile, N-methyl-2-pyrrolidone, dimethoxyethane, tetrohydrofuran and the like can be used. By using a water-soluble organic solvent, the compatibility between the monomer components or between the hydrophilic polymer component and the monomer component can be improved. In addition, the water-soluble organic solvent can be easily removed by immersing in water.

The amount of the organic solvent to be blended in the polymerizable mixture is, for example, 40 parts by mass or less, preferably 25 parts by mass or less, more preferably 10 parts by mass with respect to 100 parts by mass of the total of the monomer component and the hydrophilic polymer component in the polymerizable mixture. It can be parts by mass, more preferably 0 parts to 5 parts by mass. In the present invention, since the compatibility of each component in the polymerizable mixture is good, the amount of the water-soluble organic solvent blended can be reduced.

As the additive other than the above, an additive conventionally used for ophthalmic lens applications can be used. For example, a cooling agent, a thickening agent, a surfactant and a non-polymerizable dye, an ultraviolet absorber or an ultraviolet absorbing dye and the like can be mentioned.

The blending amount of the other additives in the polymerizable mixture is, for example, 0.01 parts by mass to 5 parts by mass, preferably 0.01 parts by mass with respect to 100 parts by mass of the total amount of the (a) monomer component and (b) hydrophilic polymer. Can be 0.01 parts by mass to 3 parts by mass.

B. Polymerization method In the polymer material of the present invention, for example, a polymerizable mixture containing each of the above components is heated and / or irradiated with light (ultraviolet rays and / or visible light) to copolymerize each monomer component in the polymerizable mixture. Can be obtained by It can also be obtained by copolymerization by electron beam irradiation instead of light irradiation.

As the polymerization method, a massive polymerization method or a solution polymerization method can be used. In the massive polymerization method, a part of the monomer components may remain unpolymerized. Further, in the solution polymerization method, a solvent that does not participate in the reaction can remain in the obtained polymer. In the manufacture of contact lenses and the like, which are medical devices, the obtained polymer material is immersed in water, an organic solvent, or a mixed solution thereof, and preferably repeated, in order to reduce the amount of these residues as much as possible. A treatment can be performed to elute the residue and remove it from the polymeric material.

When the polymer material of the present invention is used as a material for an ophthalmic lens such as a contact lens, the above-mentioned polymerizable mixture can be reacted by a template method. When the polymerizable mixture is heated and polymerized by the mold method, the above-mentioned polymerizable mixture is filled in a mold corresponding to a desired shape of an ophthalmic lens material, and the mold is gradually heated.

The heating temperature and heating time when heating the polymerizable mixture in the mold are appropriately set according to the composition of the polymerizable mixture and the like. The heating temperature is preferably 50 ° C. or higher and 150 ° C. or lower, and more preferably 60 ° C. or higher and 140 ° C. or lower. The heating time for heating the polymerizable mixture in the mold is preferably 10 minutes or more and 120 minutes or less, and more preferably 20 minutes or more and 60 minutes or less.

In the mold method, when the polymerizable mixture is polymerized by light irradiation, the mold is filled with the above-mentioned polymerizable mixture in a mold corresponding to a desired shape of an ophthalmic lens material, and then the mold is irradiated with light. The material of the mold used for the polymerization by light irradiation is not particularly limited as long as it is a material capable of transmitting the light required for the polymerization.

The wavelength of the light irradiating the polymerizable mixture in the mold is appropriately set according to the type of the photopolymerization initiator used and the like. The light illuminance and the irradiation time are appropriately set according to the composition of the polymerizable mixture and the like. The light illuminance is preferably 0.1 mW / cm ^{2 to} 100 mW / cm ² or less. The irradiation time is preferably 1 minute or more. Light of different illuminance may be irradiated stepwise.

By the polymerization by the above-mentioned mold method, a polymer material having a desired shape can be obtained. The obtained polymer material as a molded product may be subjected to mechanical processing such as cutting or polishing, if necessary. The cutting may be performed over the entire surface of one or both surfaces of the polymer material, or may be performed on a part of one surface or both surfaces of the polymer material.

The polymer material of the present invention has excellent surface hydrophilicity because it contains a hydrophilic polymer component as an internal wetting material, but for the purpose of further surface modification, the surface of low temperature plasma treatment, atmospheric pressure plasma, corona discharge, etc. It can be modified.

C. Characteristics of Polymer Material The oxygen permeability coefficient (Dk value) of the polymer material in one embodiment of the present invention is preferably 30 Barrer to 120 Barrer, more preferably 40 Barrer to 110 Barrer, and further preferably 50 Barrer to 100 Barrer.

The water content of the polymer material in one embodiment of the present invention is preferably 10% by mass or more, more preferably 30% by mass or more, and further preferably 35% by mass to 70% by mass. By setting the water content of the polymer material to 10% by mass, the obtained polymer material can be made into a hydrogel, and the wearing feeling when processed into a contact lens can be improved.

The Young's modulus of the polymer material in one embodiment of the present invention is preferably 0.05 MPa to 1.5 MPa, more preferably 0.1 MPa to 0.8 MPa, still more preferably 0.15 MPa to 0.7 MPa. By setting the Young's modulus of the polymer material to 0.05 MPa to 1.5 MPa, it is possible to achieve both a feeling of wearing and handleability when the contact lens is processed.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. Unless otherwise specified, "parts" and "%" in Examples and Comparative Examples are based on mass.

・シリコーンマクロモノマーＢ： 下記式に示す構造を有する重合性シリコーン化合物（式中、ｎ＝３０〜８０）

・シリコーンマクロモノマーＣ： 下記式に示す構造を有する重合性シリコーン化合物（式中、ｎ＝１５〜５０）

・シリコーンマクロモノマーＤ、Ｅ： 下記式に示す構造を有する重合性シリコーン化合物（式中、ｎ＝１５〜８０）

・シリコーンマクロモノマーＦ： 下記式に示す構造を有する重合性シリコーン化合物（式中、ｎ＝１５〜５０）

（３）第２のシリコーン含有モノマー
・ＡＡ−ＰＤＭＳ： 以下に示す構造を有する重合性シリコーン化合物

・ＴＲIＳ：トリス（トリメチルシロキシ）シリルプロピルメタクリレート（構造を以下に示す）

（４）ヒドロキシル基を有するシリコーン含有モノマー
・ＳｉＧＭＡ： （３−メタクリロキシ−２−ヒドロキシプロピルオキシ）プロピルビス（トリメチルシロキシ）メチルシラン（構造を以下に示す）

（５）親水性モノマー
・ブレンマーＰＭＥ−２００： オキシエチレン鎖の繰り返しユニット数が約４であるメトキシポリエチレングリコールモノメタクリレート
・ＨＥＭＡ： ２−ヒドロキシエチルメタクリレート
・２−ＨＰＭＡ: ２−ヒドロキシプロピルメタクリレート
・ＤＭＡＡ： Ｎ，Ｎ−ジメチルアクリルアミド
・２−ＭＴＡ： ２−メトキシエチルアクリレート
（６）架橋性モノマー
・ＥＤＭＡ： エチレングリコールジメタクリレート
（７）疎水性モノマー
・ＭＭＡ: メチルメタクリレート
・ＨＯＢ： ３−ヒドロキシブチルメタクリレートと２−ヒドロキシブチルメタクリレートとの混合物
（８）機能性モノマー
・ＨＭＥＰＢＴ： ベンゾトリアゾール系重合性紫外線吸収剤（２−（２’−ヒドロキシ−５’−メタクリロイルオキシエチルフェニル）−２Ｈ−ベンゾトリアゾール）
・ＲＢ２４６： アントラキノン系重合性色素（１，４−ビス（４−（２−メタクリルオキシエチル）フェニルアミノ）９，１０−アントラキノン）
（９）添加剤
・ＴＰＯ： 開始剤（２，４，６−トリメチルベンゾイル−ジフェニルホスフィンオキサイド）
・ＥｔＯＨ： エタノール
・ＩＰＡ： イソプロピルアルコール[Ingredients used]
The meanings of the abbreviations of the components used in Examples and Comparative Examples are shown below.
(1) Hydrophilic polymer PVP (K-90): Polyvinylpyrrolidone (K value 90)
-PVP (K-120): Polyvinylpyrrolidone (K value 120)
(2) First Silicone-Containing Monomer / Silicone Macromonomer A: A polymerizable silicone compound having a structure represented by the following formula (in the formula, n = 30 to 80).

-Silicone macromonomer B: A polymerizable silicone compound having a structure represented by the following formula (in the formula, n = 30 to 80).

-Silicone macromonomer C: A polymerizable silicone compound having a structure represented by the following formula (in the formula, n = 15 to 50).

-Silicone macromonomers D and E: Polymerizable silicone compounds having a structure represented by the following formula (in the formula, n = 15 to 80).

-Silicone macromonomer F: A polymerizable silicone compound having a structure represented by the following formula (in the formula, n = 15 to 50).

(3) Second Silicone-Containing Monomer-AA-PDMS: Polymerizable Silicone Compound Having the Structure Shown below

-TRIS: Tris (trimethylsiloxy) silylpropyl methacrylate (structure shown below)

(4) Silicone-containing monomer having a hydroxyl group-SiGMA: (3-methacryloxy-2-hydroxypropyloxy) propylbis (trimethylsiloxy) methylsilane (structure is shown below)

(5) Hydrophilic Monomer Blemmer PME-200: Methoxypolyethylene glycol monomethacrylate / HEMA: 2-hydroxyethyl methacrylate / 2-HPMA: 2-hydroxypropyl methacrylate / DMAA: in which the number of repeating units of the oxyethylene chain is about 4. N, N-Dimethylacrylamide, 2-MTA: 2-Methoxyethyl acrylate (6) Crosslinkable monomer, EDMA: Ethylene glycol dimethacrylate (7) Hydrophilic monomer, MMA: Methyl methacrylate, HOB: 3-Hydroxybutyl methacrylate and 2 -Mixed with hydroxybutyl methacrylate (8) Functional monomer-HMEPBT: Bentriazole-based polymerizable ultraviolet absorber (2- (2'-hydroxy-5'-methacryloyloxyethylphenyl) -2H-benzotriazole)
RB246: Anthraquinone-based polymerizable dye (1,4-bis (4- (2-methacryloxyethyl) phenylamino) 9,10-anthraquinone)
(9) Additives / TPO: Initiator (2,4,6-trimethylbenzoyl-diphenylphosphine oxide)
・ EtOH: Ethanol ・ IPA: Isopropyl alcohol

最初に、上記に示す合成経路にて二級アミンを有するウレタンジメタクリレートを合成した。具体的な合成手順は、以下のとおりである。
１）１Ｌ褐色ナスフラスコにジエタノールアミン（２１．０４ｇ，２００．０ｍｍｏｌ）、ジクロロメタン（２００．３８ｇ）を加えて氷浴で０℃にして撹拌した。１００ｍＬ滴下ロートにて二炭酸ジ−ｔｅｒｔ−ブチル（４８．０２ｇ，２２０．０ｍｍｏｌ）をジクロロメタン（４９．８１ｇ）に溶解させ、３０分かけて滴下した。滴下ロートは少量のジクロロメタンで３回洗い、反応溶液に加えた。滴下終了後、反応溶液を室温に戻し、１時間撹拌した。
２）反応溶液にｐ−メトキシフェノール（０．０４２ｇ，０．３４ｍｍｏｌ）とテトラキス（２，４−ペンタンジオナト）ジルコニウム（ＩＶ）（０．４０２ｇ，０．８２ｍｍｏｌ）を加え、氷浴で０℃にて撹拌した。１００ｍＬ滴下ロートにてカレンズＭＯＩ（６８．２７ｇ，４４０．０ｍｍｏｌ）を４０分かけて滴下した。滴下ロートは少量のジクロロメタンで３回洗い、反応溶液に加えた。滴下終了後、反応溶液を室温に戻し、１時間撹拌した。その後、蒸留水２０．０４ｇを加えてさらに室温で１時間撹拌した。
３）反応溶液にトリフルオロ酢酸（２２８．１１ｇ，２．０ｍｏｌ）を加えて、ジムロート冷却器を装着し、オイルバス中で４０℃として４時間撹拌した。
４）反応溶液を室温に戻した後に氷浴に移し、トリエチルアミン（２０２．９５ｇ，２．１ｍｏｌ）をゆっくり加え、中和した。
５）反応溶液を分液ロートに移し、４００ｍＬのジクロロメタンを加えた。その後、蒸留水４００ｍＬで３回洗浄した。得られたジクロロメタン溶液を、硫酸ナトリウムを用いて脱水乾燥した。
６）硫酸ナトリウムを濾過し、残った溶液を減圧留去した。
７）得られた粗製物をアセトニトリル２００ｍＬに溶解して分液ロートに移し、ヘキサン２００ｍＬで３回洗浄した。得られたアセトニトリル溶液にｐ−メトキシフェノール（０．０４２ｇ，０．３４ｍｍｏｌ）を加えて減圧留去し、オイル状化合物を収率８５％（７０．６５ｇ，１７０．１ｍｍｏｌ）で得た。^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）にて目的の化合物の構造であることを確認した。[Synthesis Example 1: Preparation of Silicone Macromonomer A]

First, urethane dimethacrylate having a secondary amine was synthesized by the synthetic route shown above. The specific synthesis procedure is as follows.
1) Diethanolamine (21.04 g, 200.0 mmol) and dichloromethane (200.38 g) were added to a 1 L brown eggplant flask, and the mixture was stirred at 0 ° C. in an ice bath. Di-tert-butyl dicarbonate (48.02 g, 220.0 mmol) was dissolved in dichloromethane (49.81 g) with a 100 mL dropping funnel, and the mixture was added dropwise over 30 minutes. The dropping funnel was washed 3 times with a small amount of dichloromethane and added to the reaction solution. After completion of the dropping, the reaction solution was returned to room temperature and stirred for 1 hour.
2) Add p-methoxyphenol (0.042 g, 0.34 mmol) and tetrakis (2,4-pentanedionato) zirconium (IV) (0.402 g, 0.82 mmol) to the reaction solution, and place in an ice bath at 0 ° C. Was stirred. Calends MOI (68.27 g, 440.0 mmol) was added dropwise over 40 minutes using a 100 mL dropping funnel. The dropping funnel was washed 3 times with a small amount of dichloromethane and added to the reaction solution. After completion of the dropping, the reaction solution was returned to room temperature and stirred for 1 hour. Then, 20.04 g of distilled water was added, and the mixture was further stirred at room temperature for 1 hour.
3) Trifluoroacetic acid (228.11 g, 2.0 mol) was added to the reaction solution, a Dimroth condenser was attached, and the mixture was stirred at 40 ° C. for 4 hours in an oil bath.
4) After returning the reaction solution to room temperature, the reaction solution was transferred to an ice bath, and triethylamine (202.95 g, 2.1 mol) was slowly added to neutralize the reaction solution.
5) The reaction solution was transferred to a separatory funnel and 400 mL of dichloromethane was added. Then, it was washed three times with 400 mL of distilled water. The obtained dichloromethane solution was dehydrated and dried over sodium sulfate.
6) Sodium sulfate was filtered, and the remaining solution was distilled off under reduced pressure.
7) The obtained crude product was dissolved in 200 mL of acetonitrile, transferred to a separating funnel, and washed 3 times with 200 mL of hexane. P-methoxyphenol (0.042 g, 0.34 mmol) was added to the obtained acetonitrile solution and distilled off under reduced pressure to obtain an oily compound in a yield of 85% (70.65 g, 170.1 mmol). ¹ It was confirmed by 1 H-NMR (CDCl ₃ , 400 MHz) that the structure of the target compound was obtained.

次いで、上記に示す合成経路にてシリコーンマクロモノマーＡを合成した。具体的な合成手順は、以下のとおりである。
１）５００ｍＬ褐色ナスフラスコに両末端無水コハク酸変性シリコーン（５６．６０ｇ、官能基当量１５９０ｇ／ｍｏｌより平均分子量３１８０ｇ／ｍｏｌとして１７．８ｍｍｏｌ）、ヘキサン５５．３４ｇ、二級アミンを有するウレタンジメタクリレート（１８．４８ｇ，４４．５ｍｍｏｌ）を加え、ジムロート冷却器を装着し、オイルバス中で４０℃として２時間撹拌した。
２）反応溶液を室温に戻した後に、２Ｌの分液ロートに移した。ヘキサン６００ｍＬとアセトニトリル３００ｍＬを加えて、分液操作を行った。３層分離した最も下層を廃棄した。残った溶液に、アセトニトリル３００ｍＬ加えて、再度分液操作を行い、３層分離した最も下層を廃棄した。
３）残った溶液にアセトニトリル３００ｍＬを加えて、再度分液操作を行った。３層分離した上層と中層を１Ｌ褐色フラスコに移し、ｐ−メトキシフェノール（０．０２２ｇ，０．０１８ｍｍｏｌ）を加えて、減圧留去することで、高粘度の液体を５６．３３ｇ得た。ＳＥＣ測定によって得られたシリコーンマクロモノマーＡの分子量を求めたところ、数平均分子量（Ｍｎ）が６０００、重量平均分子量（Ｍｗ）が７０００（ポリスチレン換算）であった。

Next, the silicone macromonomer A was synthesized by the synthetic route shown above. The specific synthesis procedure is as follows.
1) Urethane dimethacrylate having succinic anhydride-modified silicone (56.60 g, functional group equivalent 1590 g / mol, 17.8 mmol as average molecular weight 3180 g / mol), hexane 55.34 g, and secondary amine in a 500 mL brown eggplant flask. (18.48 g, 44.5 mmol) was added, a Dimroth condenser was attached, and the mixture was stirred in an oil bath at 40 ° C. for 2 hours.
2) After returning the reaction solution to room temperature, it was transferred to a 2 L separatory funnel. A liquid separation operation was performed by adding 600 mL of hexane and 300 mL of acetonitrile. The lowest layer separated by 3 layers was discarded. 300 mL of acetonitrile was added to the remaining solution, and the liquid separation operation was performed again, and the lowest layer separated into three layers was discarded.
3) 300 mL of acetonitrile was added to the remaining solution, and the liquid separation operation was performed again. The upper layer and the middle layer separated into three layers were transferred to a 1 L brown flask, p-methoxyphenol (0.022 g, 0.018 mmol) was added, and the mixture was distilled off under reduced pressure to obtain 56.33 g of a highly viscous liquid. When the molecular weight of the silicone macromonomer A obtained by the SEC measurement was determined, the number average molecular weight (Mn) was 6000 and the weight average molecular weight (Mw) was 7000 (in terms of polystyrene).

最初に、上記に示す合成経路にて二級アミンを有するジメタクリレートを合成した。具体的な合成手順は、以下のとおりである。
１）５００ｍＬ褐色ナスフラスコにジエタノールアミン（１０．５２ｇ，１００．０ｍｍｏｌ）、ジクロロメタン（１０１．０３ｇ）を加えて氷浴で０℃にして撹拌した。１００ｍＬ滴下ロートにて二炭酸ジ−ｔｅｒｔ−ブチル（２４．０２ｇ，１１０．１ｍｍｏｌ）をジクロロメタン（２５．０９ｇ）に溶解させ、２０分かけて滴下した。滴下ロートは少量のジクロロメタンで３回洗い、反応溶液に加えた。滴下終了後、反応溶液を室温に戻し、２０時間撹拌した。
２）反応溶液にトリエチルアミン（２３．００ｇ，２２７.２ｍｍｏｌ）を加え、氷浴で０℃にして撹拌した。滴下ロートにてメタクリロイルクロリド（２３．２０ｇ，２２１．９ｍｍｏｌ）を２０分かけて滴下した。滴下ロートは少量のジクロロメタンで３回洗い、反応溶液に加えた。滴下終了後、反応溶液を室温に戻し、１.５時間撹拌した。
３）反応溶液にトリフルオロ酢酸（１１４．３０ｇ，１．０ｍｏｌ）を加えて、ジムロート冷却器を装着し、オイルバス中で４０℃として２．５時間撹拌した。
４）反応溶液を室温に戻した後に氷浴に移し、トリエチルアミン（１０４．３０ｇ，１．０ｍｏｌ）をゆっくり加え、中和した。
５）反応溶液を分液ロートに移し、２００ｍＬのジクロロメタンを加えた。その後、蒸留水２００ｍＬで３回洗浄した。得られたジクロロメタン溶液を、硫酸ナトリウムを用いて脱水乾燥した。
６）硫酸ナトリウムを濾過し、残った溶液を減圧留去した。
７）得られた粗製物をアセトニトリル２００ｍＬに溶解して分液ロートに移し、ヘキサン２００ｍＬで３回洗浄した。得られたアセトニトリル溶液にｐ−メトキシフェノール（０．０２４ｇ，０．１９ｍｍｏｌ）を加えて減圧留去し、オイル状化合物を収率６５％（１５．６１ｇ，６４．７ｍｍｏｌ）で得た。^１Ｈ−ＮＭＲ（ＣＤＣｌ_３，４００ＭＨｚ）にて目的の化合物の構造であることを確認した。[Synthesis Example 2: Synthesis of Silicone Macromonomer B]

First, dimethacrylate having a secondary amine was synthesized by the synthetic route shown above. The specific synthesis procedure is as follows.
1) Diethanolamine (10.52 g, 100.0 mmol) and dichloromethane (101.03 g) were added to a 500 mL brown eggplant flask, and the mixture was stirred in an ice bath at 0 ° C. Di-tert-butyl dicarbonate (24.02 g, 110.1 mmol) was dissolved in dichloromethane (25.09 g) with a 100 mL dropping funnel and added dropwise over 20 minutes. The dropping funnel was washed 3 times with a small amount of dichloromethane and added to the reaction solution. After completion of the dropping, the reaction solution was returned to room temperature and stirred for 20 hours.
2) Triethylamine (23.00 g, 227.2 mmol) was added to the reaction solution, and the mixture was stirred at 0 ° C. in an ice bath. Methacryloyl chloride (23.20 g, 221.9 mmol) was added dropwise over 20 minutes using a dropping funnel. The dropping funnel was washed 3 times with a small amount of dichloromethane and added to the reaction solution. After completion of the dropping, the reaction solution was returned to room temperature and stirred for 1.5 hours.
3) Trifluoroacetic acid (114.30 g, 1.0 mol) was added to the reaction solution, a Dimroth condenser was attached, and the mixture was stirred at 40 ° C. for 2.5 hours in an oil bath.
4) After returning the reaction solution to room temperature, the reaction solution was transferred to an ice bath, and triethylamine (104.30 g, 1.0 mol) was slowly added to neutralize the reaction solution.
5) The reaction solution was transferred to a separatory funnel and 200 mL of dichloromethane was added. Then, it was washed three times with 200 mL of distilled water. The obtained dichloromethane solution was dehydrated and dried over sodium sulfate.
6) Sodium sulfate was filtered, and the remaining solution was distilled off under reduced pressure.
7) The obtained crude product was dissolved in 200 mL of acetonitrile, transferred to a separating funnel, and washed 3 times with 200 mL of hexane. P-methoxyphenol (0.024 g, 0.19 mmol) was added to the obtained acetonitrile solution and distilled off under reduced pressure to obtain an oily compound in a yield of 65% (15.61 g, 64.7 mmol). ¹ It was confirmed by 1 H-NMR (CDCl ₃ , 400 MHz) that the structure of the target compound was obtained.

次いで、上記に示す合成経路にてシリコーンマクロモノマーＢを合成した。具体的な合成手順は、以下のとおりである。
１）２００ｍＬ褐色ナスフラスコに（４４．１２ｇ、官能基当量１４７０ｇ／ｍｏｌより平均分子量２９４０ｇ／ｍｏｌとして１５．０ｍｍｏｌ）、ヘキサン４５．２２ｇ、二級アミンを有するジメタクリレート（９．１０ｇ，３７．７ｍｍｏｌ）を加え、ジムロート冷却器を装着し、オイルバス中で４０℃として３時間撹拌した。
２）反応溶液を室温に戻した後に、２Ｌの分液ロートに移した。ヘキサン４００ｍＬとアセトニトリル２００ｍＬを加えて、分液操作を行い、アセトニトリル層を廃棄した。同様な操作を２回繰り返し行った。
３）得られたヘキサン溶液を褐色ナスフラスコに移し、ｐ−メトキシフェノール（０．０２１ｇ，０．０１７ｍｍｏｌ）を加えて、減圧留去することで、高粘度の液体を４１．７７ｇ得た。ＳＥＣ測定によって得られたシリコーンマクロモノマーＢの分子量を求めたところ、数平均分子量（Ｍｎ）が４５００、重量平均分子量（Ｍｗ）が６３００（ポリスチレン換算）であった。

Next, the silicone macromonomer B was synthesized by the synthetic route shown above. The specific synthesis procedure is as follows.
1) In a 200 mL brown eggplant flask (44.12 g, 15.0 mmol as an average molecular weight of 2940 g / mol from a functional group equivalent of 1470 g / mol), 45.22 g of hexane, and dimethacrylate having a secondary amine (9.10 g, 37.7 mmol). ) Was added, a Dimroth condenser was attached, and the mixture was stirred in an oil bath at 40 ° C. for 3 hours.
2) After returning the reaction solution to room temperature, it was transferred to a 2 L separatory funnel. 400 mL of hexane and 200 mL of acetonitrile were added, a liquid separation operation was performed, and the acetonitrile layer was discarded. The same operation was repeated twice.
3) The obtained hexane solution was transferred to a brown eggplant flask, p-methoxyphenol (0.021 g, 0.017 mmol) was added, and the mixture was distilled off under reduced pressure to obtain 41.77 g of a highly viscous liquid. When the molecular weight of the silicone macromonomer B obtained by the SEC measurement was determined, the number average molecular weight (Mn) was 4500 and the weight average molecular weight (Mw) was 6300 (in terms of polystyrene).

上記に示す合成経路にてシリコーンマクロモノマーＣを合成した。具体的な合成手順は以下のとおりである。
１）３００ｍＬナスフラスコに両末端無水コハク酸変性シリコーン（１１４．４５ｇ、官能基当量９５６ｇ／ｍｏｌより平均分子量１９１２ｇ／ｍｏｌとして５９．９ｍｍｏｌ）、エチレングリコール（１．８６ｇ，３０．０ｍｍｏｌ）、を加えトリエチルアミン（１８．２５ｇ，１８０．３ｍｍｏｌ）を室温にて７分間かけて滴下した。
２）オイルバス中４５℃にて３０分間撹拌した。
３）ＨＥＭＡ（１１．７３ｇ，９０．１ｍｍｏｌ）を系中へ加え、ジムロート冷却器を装着し、オイルバス中４５℃にて１時間撹拌した。
４）反応液をヘキサン８００ｍＬに溶解し、２Ｌ分液ロートへ移した。ヘキサン層を、トリフルオロ酢酸（２５．１４ｇ，２２．０ｍｍｏｌ）を溶解させたアセトニトリル４００ｍＬで洗浄した。
５）ヘキサン層をアセトニトリル４００ｍＬにて３回洗浄した。
６）ヘキサン層を回収し、減圧濃縮して無色の透明液体を１０２．９６ｇ得た。ＳＥＣ測定によって得られたシリコーンマクロモノマーＣの分子量を求めたところ、数平均分子量（Ｍｎ）が５０００、重量平均分子量（Ｍｗ）が７４００（ポリスチレン換算）であった。[Synthesis Example 3: Synthesis of Silicone Macromonomer C]

Silicone macromonomer C was synthesized by the synthetic route shown above. The specific synthesis procedure is as follows.
1) Add succinic anhydride-modified silicone (114.45 g, 59.9 mmol as an average molecular weight of 1912 g / mol from a functional group equivalent of 956 g / mol) and ethylene glycol (1.86 g, 30.0 mmol) to a 300 mL eggplant flask. Triethylamine (18.25 g, 180.3 mmol) was added dropwise at room temperature over 7 minutes.
2) The mixture was stirred in an oil bath at 45 ° C. for 30 minutes.
3) HEMA (11.73 g, 90.1 mmol) was added to the system, a Dimroth condenser was attached, and the mixture was stirred in an oil bath at 45 ° C. for 1 hour.
4) The reaction solution was dissolved in 800 mL of hexane and transferred to a 2 L separatory funnel. The hexane layer was washed with 400 mL of acetonitrile in which trifluoroacetic acid (25.14 g, 22.0 mmol) was dissolved.
5) The hexane layer was washed 3 times with 400 mL of acetonitrile.
6) The hexane layer was recovered and concentrated under reduced pressure to obtain 102.96 g of a colorless transparent liquid. When the molecular weight of the silicone macromonomer C obtained by the SEC measurement was determined, the number average molecular weight (Mn) was 5000 and the weight average molecular weight (Mw) was 7400 (in terms of polystyrene).

上記に示す合成経路にてシリコーンマクロモノマーＤを合成した。具体的な合成手順は以下のとおりである。
１）１００ｍＬ褐色ナスフラスコに両末端無水コハク酸変性シリコーン（２８．６０ｇ、官能基当量９５３ｇ／ｍｏｌより平均分子量１９０６ｇ／ｍｏｌとして１５．０ｍｍｏｌ）、グリセロールジメタクリレート（８．５７ｇ，３７．５ｍｍｏｌ）、トリエチルアミン（４．５７ｇ，４５．１ｍｍｏｌ）を加え、室温にて３０分撹拌した後、ジムロート冷却器を装着し、オイルバス中で４０℃として１時間３０分撹拌した。
２）反応溶液を室温に戻した後、分液ロートに移した。ヘキサン２００ｍＬとトリフルオロ酢酸（６．１５ｇ，５３．９ｍｍｏｌ）を溶解させたアセトニトリル１００ｍＬを加えて、分液操作を行い、アセトニトリル層を廃棄した。残った溶液に、アセトニトリル２００ｍＬ加えて、再度分液操作を行い、アセトニトリル層を廃棄した。同様の操作を繰り返した。
３）残ったヘキサン溶液を褐色フラスコに移し、減圧留去することで、高粘度の液体を２３．１５ｇ得た。ＳＥＣ測定によって得られたシリコーンマクロモノマーＤの分子量を求めたところ、数平均分子量（Ｍｎ）が３４００、重量平均分子量（Ｍｗ）が４３００（ポリスチレン換算）であった。[Synthesis Example 4: Synthesis of Silicone Macromonomer D]

Silicone macromonomer D was synthesized by the synthetic route shown above. The specific synthesis procedure is as follows.
1) In a 100 mL brown eggplant flask, succinic anhydride-modified silicone at both ends (28.60 g, 15.0 mmol with an average molecular weight of 1906 g / mol from a functional group equivalent of 953 g / mol), glycerol dimethacrylate (8.57 g, 37.5 mmol), After adding triethylamine (4.57 g, 45.1 mmol) and stirring at room temperature for 30 minutes, a Dimroth condenser was attached and the mixture was stirred at 40 ° C. for 1 hour and 30 minutes in an oil bath.
2) After returning the reaction solution to room temperature, it was transferred to a separating funnel. 200 mL of hexane and 100 mL of acetonitrile in which trifluoroacetic acid (6.15 g, 53.9 mmol) was dissolved were added, a liquid separation operation was performed, and the acetonitrile layer was discarded. 200 mL of acetonitrile was added to the remaining solution, and the liquid separation operation was performed again to discard the acetonitrile layer. The same operation was repeated.
3) The remaining hexane solution was transferred to a brown flask and distilled off under reduced pressure to obtain 23.15 g of a highly viscous liquid. When the molecular weight of the silicone macromonomer D obtained by SEC measurement was determined, the number average molecular weight (Mn) was 3400 and the weight average molecular weight (Mw) was 4300 (in terms of polystyrene).

[Synthesis Example 5: Synthesis of Silicone Macromonomer E]
With reference to Synthesis Example 4, a silicone macromonomer E having a molecular weight different from that of the silicone macromonomer D was synthesized. The specific synthesis procedure is as follows.
1) In a 100 mL brown eggplant flask, succinic anhydride-modified silicone at both ends (31.84 g, 10.0 mmol with an average molecular weight of 3180 g / mol from a functional group equivalent of 1590 g / mol), glycerol dimethacrylate (5.77 g, 25.0 mmol), Triethylamine (3.05 g, 30.0 mmol) was added and a Dimroth condenser was attached, and the mixture was stirred at room temperature for about 40 minutes, then a Dimroth condenser was attached, and the mixture was stirred at 40 ° C. for about 3 hours in an oil bath.
2) The reaction solution was returned to room temperature, dissolved in 200 mL hexane, and transferred to a separating funnel.
3) 100 mL of acetonitrile containing 36 mL of 1M HCl was transferred to a separatory funnel, and the hexane solution was washed once. Then, the hexane solution was washed twice with 100 mL acetonitrile.
4) The obtained hexane solution was distilled off under reduced pressure to obtain 31.87 g of an oily compound. When the molecular weight of the silicone macromonomer E obtained by the SEC measurement was determined, the number average molecular weight (Mn) was 4600 and the weight average molecular weight (Mw) was 6200 (in terms of polystyrene).

上記に示す合成経路にてシリコーンマクロモノマーＦを合成した。具体的な合成手順は以下のとおりである。
１）１００ ｍＬ褐色ナスフラスコに両末端無水コハク酸変性シリコーン（官能基当量９５３ｇ／ｍｏｌより平均分子量１９０６ｇ／ｍｏｌとして２８．８２ｇ，１５．０ｍｍｏｌ）、ＨＯＢ（５．９５ｇ、３７．６ｍｍｏｌ）、トリエチルアミン（４．６１ｇ，４５．６ｍｍｏｌ）を加えてジムロート冷却器を装着し、室温で約４０分間撹拌した後、オイルバス中で４０℃とし約１時間撹拌した。
２）反応溶液を室温に戻し、２００ｍＬヘキサンに溶解させ、分液ロートに移した。
３）分液ロートにトリフルオロ酢酸（６．６４ｇ，５８．２ｍｍｏｌ）を溶解させた１００ｍＬアセトニトリルを加え、ヘキサン溶液を１回洗浄した。その後、１００ｍＬアセトニトリルでヘキサン溶液を２回洗浄した。
４）得られたヘキサン溶液を減圧留去し、オイル状化合物を２６．２２ｇで得た。ＳＥＣ測定によって得られたシリコーンマクロモノマーＦの分子量を求めたところ、数平均分子量（Ｍｎ）が３２００、重量平均分子量（Ｍｗ）が３９００（ポリスチレン換算）であった。[Synthesis Example 6: Synthesis of Silicone Macromonomer F]

Silicone macromonomer F was synthesized by the synthetic route shown above. The specific synthesis procedure is as follows.
1) In a 100 mL brown eggplant flask, succinic anhydride-modified silicone at both ends (28.82 g, 15.0 mmol with an average molecular weight of 1906 g / mol from a functional group equivalent of 953 g / mol), HOB (5.95 g, 37.6 mmol), triethylamine. (4.61 g, 45.6 mmol) was added, a Dimroth condenser was attached, and the mixture was stirred at room temperature for about 40 minutes, and then stirred at 40 ° C. for about 1 hour in an oil bath.
2) The reaction solution was returned to room temperature, dissolved in 200 mL hexane, and transferred to a separating funnel.
3) 100 mL of acetonitrile in which trifluoroacetic acid (6.64 g, 58.2 mmol) was dissolved was added to the separating funnel, and the hexane solution was washed once. Then, the hexane solution was washed twice with 100 mL acetonitrile.
4) The obtained hexane solution was distilled off under reduced pressure to obtain 26.22 g of an oily compound. When the molecular weight of the silicone macromonomer F obtained by the SEC measurement was determined, the number average molecular weight (Mn) was 3200 and the weight average molecular weight (Mw) was 3900 (in terms of polystyrene).

In addition, in the said synthesis example 1-6, the SEC measurement was performed under the conditions described below.
≪SEC measurement≫
Differential refractometer detector Shodex RI-101 (manufactured by Showa Denko), column constant temperature bath Shodex AO-30 (manufactured by Showa Denko), dissolved gas remover ERC3115α (manufactured by ERC INC), liquid feed pump Shodex DS-4 (manufactured by Showa Denko) SEC measurement of the obtained silicone macromonomer was carried out using a SEC column Shodex KF802.5 (manufactured by Showa Denko KK) and a guard column Shodex KF-G (manufactured by Showa Denko KK). The measurement was carried out using a THF solution having a sample concentration of about 0.3 mg / 10 mL under the conditions of a flow velocity: 1.0 mL / min, a mobile phase: THF, and a column temperature: 40 ° C. A calibration curve was prepared from polystyrene standard solutions having different molecular weights, and the number average molecular weight (Mn), the weight average molecular weight (Mw), and the molecular weight distribution (Mw / Mn) were calculated.

[Example 1]
13 parts by mass of PVP (K-90) (manufactured by BASF) as a hydrophilic polymer component, 10 parts by mass of silicone macromonomer A as a first silicone-containing monomer, and 20 parts by mass of AA-PDMS as a second silicone-containing monomer. 31 parts by mass of DMAA (manufactured by KJ Chemical Co., Ltd.), 5 parts by mass of Blemmer PME-200 (manufactured by Nichiyu Co., Ltd.) and 6 parts by mass of 2-MTA (manufactured by Osaka Organic Chemical Co., Ltd.) as hydrophilic monomers, hydrophobic 15 parts by mass of HOB (manufactured by Kyoeisha Chemical Co., Ltd.) as a monomer, 1.8 parts by mass of HMEPBT (manufactured by Daiwa Kasei Co., Ltd., DAISORB-T31) as a polymerizable ultraviolet absorber, and 0 parts of RB246 (manufactured by ARRAN) as a polymerizable dye. A polymerizable mixture was prepared by mixing 0.01 parts by mass, 1.0 part by mass of TPO (Daiwa Kasei, IHI-PI-TPO) as a polymerization initiator, and 4 parts by mass of IPA as a water-soluble organic solvent. .. The polymerizable mixture was injected into a mold having a contact lens shape (corresponding to a polypropylene, 14.2 mm diameter and 0.08 mm thick contact lens). Next, at room temperature, this mold was irradiated with blue LED light having a main wavelength of 405 nm (illuminance of 1.5 mW / cm ^{2 at} 405 nm) for 20 minutes to perform photopolymerization. After the polymerization, a contact lens-shaped polymer material was taken out from the mold.

[Examples 2 to 14]
A contact lens-shaped polymer material was obtained in the same manner as in Example 1 except that each component was mixed to prepare a polymerizable mixture so as to have the composition shown in Table 1.

[Comparative Examples 1 to 13]
A contact lens-shaped polymer material was obtained in the same manner as in Example 1 except that each component was mixed to prepare a polymerizable mixture so as to have the composition shown in Table 1.

The polymer materials obtained in the above Examples and Comparative Examples were immersed in a phosphate buffer solution having a pH of 7.5, swollen to equilibrium, and then autoclaved at 121 ° C. for 20 minutes to obtain the same amount of new phosphate. Those equilibrated by substituting with a buffer solution were subjected to the following characteristic evaluations. However, in the measurement of the oxygen permeation coefficient, the same as above except that a PP mold for obtaining a plate-type sample having an average thickness of about 0.3 mm was used instead of the mold having a contact lens shape. Was polymerized, hydrated, and sterilized, and a plate-type sample processed into a circle with a diameter of 14.0 mm was used. The results are shown in Table 1.

≪Measurement of oxygen permeability coefficient (Dk value)≫
As described above, a circular plate-type sample having a diameter of 14.0 mm was used as the measurement sample. A similar plate-type sample was prepared from the material of "2WEEK Menicon Premio" (manufactured by Menicon) as a reference standard, and this Dk value was set to 129.
Set the measurement sample on the electrode, and set the current value when the equilibrium state is reached by nitrogen bubbling in physiological saline at 35 ° C using a Kaken-type film oxygen transmissometer (manufactured by Rika Seiki Kogyo Co., Ltd.). I set it. Then, the current value at the time of oxygen bubbling and equilibrium was recorded. This was also done for the reference standard. The oxygen permeability coefficient of the lens was calculated according to the following formula. The unit of the oxygen permeability coefficient is (× 10 ^-11 (cm ² / sec) · (mLO ₂ / (mL × mmHg)) = Barrer).
Dk value = R x (IS / IR) x (TS / TR) x (PR / PS)
Here, the meanings of the symbols in the above formula are as follows.
R: Reference standard Dk value (129)
IS: Current value (μA) of the measurement sample
IR: Reference standard current value (μA)
TS: Average thickness of measurement sample (mm)
TR: Average thickness of reference standard (mm)
PS: Atmospheric pressure (mmHg) at the time of measurement of the measurement sample
PR: Atmospheric pressure (mmHg) at the time of reference standard measurement

≪Measurement of tensile elastic modulus (Young's modulus)≫
The prepared contact lens was punched out to prepare a dumbbell-shaped sample having a width of about 1.8 mm and a thickness of about 0.1 mm at the stretched portion, which was used as a test sample. A tensile test was carried out in a physiological saline solution at 20 ° C. using the Shimadzu Precision Universal Testing Machine Autograph AG-IS MS manufactured by Shimadzu Corporation, and Young's modulus (MPa) was calculated as the tensile elastic modulus from the stress-elongation curve. Was calculated. The tensile speed was 100 mm / min.

≪Measurement of water content≫
Moisture on the surface of the contact lens adjusted in a pH 7.5 phosphate buffer solution at 20 ° C. was lightly wiped off, and the mass (W (g)) in an equilibrium water-containing state was measured. Then, the lens was dried in a dryer set at 105 ° C., and then the mass (W ₀ (g)) in a allowed state was measured. Using these measured values W ₀ and W, the water content (mass%) was calculated according to the following formula.
Moisture content (mass%) = {(W-W ₀ ) / W} x 100

≪Appearance evaluation≫
The appearance of contact lenses was observed with the naked eye.

≪Evaluation of lipid adhesion≫
1) 1 g of an artificial lipid (product name "Pharmazole") solid at room temperature was placed in each well of the multi-well plate, and the mixture was heated to 80 ° C. and melted.
2) After wiping off the water on the surface of the contact lens and putting it in each well, it was left at room temperature overnight and then at 80 ° C. for 1 hour.
3) Take the contact lens out of the well, rinse it in a contact lens cleaning solution (Menicon, product name "Epica Cold") in a beaker, and then rinse it in a contact lens cleaning solution (Menicon, product name "Epica Cold"). Scrubbed 30 times.
4) Contact lens cleaning solution (manufactured by Menicon, product name "Epica Cold") and contact lenses were placed in each well of the multi-well plate and left at 10 ° C. overnight.
5) The contact lens was taken out from the well, the appearance was confirmed with the naked eye, and the evaluation was made based on the following criteria.
[Criteria]
0: Almost not observed white 1: Slightly partly observed white 2: Approximately 50% of the whole is observed white 3: The lens is observed almost entirely white, but there are some areas with low turbidity 4: The lens is observed white throughout

As shown in Table 1, the polymer materials of Examples obtained by using the silicone-containing monomer having an anionic group have high transparency and oxygen permeability, and the polymer material of Comparative Example has antifouling property against lipids. Was better than.

The polymer material of the present invention is suitably used for ophthalmic medical devices, for example, eye lenses such as contact lenses, intraocular lenses, artificial corneas, corneal onlays, and corneal inlays.

Claims (14)

A polymer material obtained by polymerizing a polymerizable mixture containing (a) a monomer component and (b) a hydrophilic polymer component.
(A) The monomer component contains (a-1) a silicone-containing monomer having an anionic group.
The amount of the (b) hydrophilic polymer component in the polymerizable mixture is about 1 part by mass to about 30 parts by mass with respect to 100 parts by mass of the total amount of the (a) monomer component and (b) hydrophilic polymer component. Part, polymer material. The polymer material according to claim 1, wherein the (a) monomer component further contains (a-2) a hydrophilic monomer. The polymer material according to claim 1 or 2, wherein the (a) monomer component further contains (a-3) a silicone-containing monomer having no anionic group. The polymer material according to any one of claims 1 to 3, wherein the silicone-containing monomer having the (a-1) anionic group has two or more polymerizable functional groups. The polymer material according to any one of claims 1 to 4, wherein the silicone-containing monomer having the (a-1) anionic group has three or more polymerizable functional groups. The polymer material according to any one of claims 1 to 5, wherein the silicone-containing monomer having an anionic group (a-1) has a structure represented by the following formula (I).

[In formula (I),
R ^{a1 to} R ^a8 are hydrocarbon groups having 1 to 50 carbon atoms, which may independently have a hydrogen atom or a hetero atom, respectively.
Z ¹ and Z ² are independent groups represented by the following formula (1).
-R ^b1 -X-R ^b2 (1)
(In equation (1),
R ^b1 is an alkylene group having 1 to 20 carbon atoms which may have a hetero atom.
R ^b2 is a (meth) acryloyl group, a vinyl group or an allyl group.
X is a single bond, -O- or -NR ^b3- (where R ^b3 is a hydrogen atom or an alkyl group with 1-3 carbon atoms).
A ¹ is k4 amino alkylene group having 1 to 12 carbon atoms in which hydrogen atom is substituted by a group B ¹ (provided that may have a hetero atom other than groups B ^1),
A ² is a k5 hydrogen atoms B ² alkylene group having 1 to 12 carbon atoms which is substituted by group (which may have a hetero atom other than groups B ^2),
A ³ is a k11 hydrogen atoms B ³ alkylene group having 1 to 12 carbon atoms which is substituted by group (which may have a hetero atom other than group B ^3),
A ⁴ is a k12 amino alkylene groups have been 1 to 12 carbon atoms substituted hydrogen atoms by a group of B ⁴ (provided that it may have a hetero atom other than group B ^4),
B ^{1 to} B ⁴ are monovalent groups having anionic groups independently of each other.
E is -O- or -NR ^c1- (where R ^c1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms).
L ¹ is a single bond or (k2 + 1) valent linking group.
L ² is a single bond or (k3 + 1) valent linking group.
k1 and k1'are independent integers of 4 or more, respectively.
k2 and k3 are independently integers 1 to 3, respectively.
k4 and k5 are independently integers of 1 to 5, respectively.
k6 is 0 or 1 and
k7 is an integer from 0 to 100 and
k8 is an integer from 0 to 5,
k9 and k10 are independently 0 or 1, respectively.
k11 and k12 are independently integers from 0 to 5. ] The polymer material according to any one of claims 1 to 6, wherein the anionic group contains a carboxyl group. (B) The polymer material according to any one of claims 1 to 7, wherein the hydrophilic polymer component has a weight average molecular weight of 100,000 or more. The polymer material according to any one of claims 1 to 8, wherein the hydrophilic polymer component (b) is polyvinylamide. Any of claims 1 to 8, wherein the hydrophilic polymer component (b) comprises at least one selected from poly-N-vinylpyrrolidone, polyalkylene glycol, polysaccharide, poly (meth) acrylic acid and polyvinyl alcohol. Polymer material described in. The polymer material according to any one of claims 1 to 8, wherein the hydrophilic polymer component (b) is poly-N-vinylpyrrolidone. The polymer material according to any one of claims 1 to 11, wherein the oxygen permeability coefficient is 30 Barrer to 120 Barrer. An ophthalmic medical device comprising the polymeric material according to any one of claims 1-12. The ophthalmic medical device according to claim 13, which is a contact lens.