阅读说明：本技术 聚合物材料 (Polymer material ) 是由 佐竹康介 浅井健吾 砂原一润 佐竹有里香 于 2020-02-21 设计创作，主要内容包括：本发明提供一种含硅酮聚合物材料,是包含内部湿润剂且透明性优异的含硅酮聚合物材料,含硅酮聚合物材料对脂质的防污性得到提高。本发明的聚合物材料是使包含(a)单体成分和(b)亲水性聚合物成分的聚合性混合物聚合而得到的聚合物材料,(a)单体成分包含(a-1)具有硅氧烷键且不具有羟基的含硅酮单体和(a-2)具有含氢键性质子的基团且不具有硅原子的相容单体,该相容单体具有4个以上的碳原子(其中,不包括聚合性官能团中所含的碳原子),且在25℃的水中的溶解度小于0.03g/mL。(The present invention provides a silicone-containing polymer material which contains an internal wetting agent and has excellent transparency, and which has improved stain resistance to lipids. The polymer material of the present invention is a polymer material obtained by polymerizing a polymerizable mixture containing (a) a monomer component containing (a-1) a silicone-containing monomer having a siloxane bond and no hydroxyl group and (a-2) a compatible monomer having a hydrogen-bonding proton-containing group and no silicon atom, the compatible monomer having 4 or more carbon atoms (excluding carbon atoms contained in a polymerizable functional group), and having a solubility in water at 25 ℃ of less than 0.03g/mL, and (b) a hydrophilic polymer component.)

1. 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 a siloxane bond and no hydroxyl group and (a-2) a compatible monomer having a hydrogen bond proton-containing group and no silicon atom,

the compatible monomer has 4 or more carbon atoms excluding the carbon atoms contained in the polymerizable functional group, and has a solubility in water at 25 ℃ of less than 0.03 g/mL.

2. The polymeric material of claim 1, wherein the (a-2) compatible monomer has 6 or more carbon atoms excluding carbon atoms contained in the polymerizable functional group.

3. The polymeric material of claim 1 or 2, wherein the (a) monomeric component further comprises (a-3) a hydrophilic monomer.

4. The polymer material according to claim 3, wherein the blending ratio of the hydrophilic polymer component (b) in the polymerizable mixture is 1 to 30% by mass relative to the total blending amount of the monomer component (a) and the hydrophilic polymer component (b).

5. The polymer material according to any one of claims 1 to 4, wherein the (a-2) compatible monomer has a polymerizable functional group, an intermediate portion containing a hydrogen-bonding proton-containing group, and a hydrophobic terminal portion containing 2 or more carbon atoms.

6. The polymeric material of claim 5, wherein the hydrophobic terminal portion comprises a branched hydrocarbon group and/or a hydrocarbon group comprising a cyclic structure.

7. The polymeric material of any one of claims 1 to 6, wherein the (a-2) compatible monomer is represented by the following formula (A),

Z-A-B(A)

in the formula (I), the compound is shown in the specification,

z represents a (meth) acryloyl group,

a comprises a hydrogen-bonded proton-containing group, or represents a divalent atomic group which forms a hydrogen-bonded proton-containing group together with Z,

b represents a hydrocarbon group having 2 to 20 carbon atoms,

wherein the total number of carbon atoms contained in A and B is 4 or more.

8. The polymer material according to claim 7, wherein the divalent radical represented by A is represented by the following formula (i),

*-X-R^a1-(L^a1)_r1-[(R^a2)_r2-(L^a2)_r3]_r4- (i)

wherein X represents a bonding site to Z,

x represents O or NR^a3，

R^a1And R^a2Each independently represents an alkylene group having 1 to 20 carbon atoms which may have a hydroxyl group,

R^a3represents hydrogen or an alkyl group having 1 to 4 carbon atoms,

L^a1and L^a2Each independently represents an ether bond, an ester bond, a carbonyl group, an amide bond, a urethane bond or a urea bond,

r1 to r3 each independently represent 0 or 1,

r4 represents an integer of 0 to 10,

wherein the content of the first and second substances,

at R^a2In the case of no hydroxyl group, r3 and r4 are not 0,

(i) has at least 1 hydrogen-bonded proton-containing group.

9. The polymeric material of claim 8, wherein R^a1Represents an alkylene group having 1 to 6 carbon atoms and having a hydroxyl group, r1 is 0 or 1, and r2 and r3 are 0.

10. The polymeric material of any of claims 1-9, wherein the hydrogen-bonded proton-containing group comprises a hydroxyl group.

11. The polymeric material of any one of claims 1-10, wherein the (a-1) silicone-containing monomer comprises a nitrogen atom.

12. The polymer material according to any one of claims 1 to 11, wherein the (b) hydrophilic polymer component has a weight average molecular weight of 100000 or more.

13. The polymeric material of any one of claims 1-12, wherein the (b) hydrophilic polymer component is a polyvinyl amide.

14. The polymeric material of any one of claims 1-12, wherein the (b) hydrophilic polymer component comprises at least 1 selected from the group consisting of poly-N-vinylpyrrolidone, polyalkylene glycol, polysaccharide, poly (meth) acrylic acid, and polyvinyl alcohol.

15. The polymeric material of any one of claims 1-12, wherein the (b) hydrophilic polymer component is poly-N-vinylpyrrolidone.

16. The polymeric material of any one of claims 1-15, wherein the young's modulus is 0.05MPa to 2.0 MPa.

17. An ophthalmic medical device comprising the polymeric material of any one of claims 1 to 16.

18. The ophthalmic medical device of claim 17, which is a contact lens.

Technical Field

The present invention relates to a polymeric material, and more particularly to a polymeric material suitable for ophthalmic lens applications.

Background

Contact lenses (contact lenses) are roughly classified into hard contact lenses and soft contact lenses. In recent years, most of hard contact lenses have high oxygen permeability due to the use of a silicone-containing polymer having a siloxane structure (Si-O-Si), but sometimes have a foreign body sensation during wearing due to the hardness thereof. On the other hand, soft contact lenses are formed from aqueous hydrogels using a copolymer polymer containing a hydrophilic monomer and a (meth) acrylic monomer as copolymerization components, and thus provide excellent wearing comfort, while they tend to have lower oxygen permeability than hard contact lenses. In contrast, soft contact lenses have been developed which have both high oxygen permeability and excellent wearing feel using silicone hydrogels containing a silicone-based monomer as a further copolymerization component.

However, soft contact lenses formed from silicone hydrogels tend to have lipids attached to the 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, since the internal wetting agent having a high degree of hydrophilicity has low compatibility with a silicone-based monomer having a high degree of hydrophobicity, a silicone-containing monomer having a hydroxyl group such as methyldi (trimethylsiloxy) silylpropylglycerol methacrylate (also referred to as "SiGMA") is generally used to compatibilize both (for example, patent document 1). Thus, a transparent polymer material can be obtained with adhesion of lipids suppressed, but further improvement in the antifouling property of lipids is required.

Documents of the prior art

Patent document

Patent document 1: japanese Kohyo publication No. 2005-518826

Disclosure of Invention

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

According to one aspect of the present invention, there is provided a polymer material obtained by polymerizing a polymerizable mixture containing (a) a monomer component containing (a-1) a silicone-containing monomer having a siloxane bond and no hydroxyl group and (a-2) a compatible monomer having a hydrogen bond proton-containing group and no silicon atom, the compatible monomer having 4 or more carbon atoms (excluding carbon atoms contained in a polymerizable functional group), and having a solubility in water at 25 ℃ of less than 0.03g/mL, and (b) a hydrophilic polymer component.

In 1 embodiment, the compatible monomer (a-2) has 6 or more carbon atoms (excluding the carbon atoms contained in the polymerizable functional group).

In 1 embodiment, the monomer component (a) further comprises a hydrophilic monomer (a-3).

In 1 embodiment, the blending ratio of the hydrophilic polymer component (b) in the polymerizable mixture is 1 to 30% by mass relative to the total blending amount of the monomer component (a) and the hydrophilic polymer component (b).

In 1 embodiment, the (a-2) compatible monomer has a polymerizable functional group, an intermediate portion containing a hydrogen-bonding proton-containing group, and a hydrophobic terminal portion containing 2 or more carbon atoms.

In 1 embodiment, the hydrophobic terminal portion includes a branched hydrocarbon group and/or a hydrocarbon group having a cyclic structure.

In 1 embodiment, the above-mentioned (a-2) compatible monomer is represented by the following formula (A).

Z-A-B (A)

(in the formula, wherein,

z represents a (meth) acryloyl group,

a comprises a hydrogen-bonded proton-containing group, or represents a divalent atomic group which forms a hydrogen-bonded proton-containing group together with Z,

b represents a hydrocarbon group having 2 to 20 carbon atoms,

wherein the total number of carbon atoms contained in A and B is 4 or more)

In 1 embodiment, the divalent group represented by a is represented by the following formula (i).

*-X-R^a1-(L^a1)_r1-[(R^a2)_r2-(L^a2)_r3]_r4- (i)

(wherein X represents a bonding site to Z,

x represents O or NR^a3，

R^a1And R^a2Each independently represents an alkylene group having 1 to 20 carbon atoms which may have a hydroxyl group,

R^a3represents hydrogen or an alkyl group having 1 to 4 carbon atoms,

L^a1and L^a2Each independently represents an ether bond, an ester bond, a carbonyl group, an amide bond, a urethane bond or a urea bond,

r1 to r3 each independently represent 0 or 1,

r4 represents an integer of 0 to 10,

wherein the content of the first and second substances,

at R^a2In the case of no hydroxyl group, r3 and r4 are not 0,

(i) having at least 1 radical containing hydrogen-bonded protons)

In 1 embodiment, R is^a1Represents an alkylene group having 1 to 6 carbon atoms and having a hydroxyl group, r1 is 0 or 1, and r2 and r3 are 0.

In 1 embodiment, the hydrogen bonding proton-containing group includes a hydroxyl group.

In 1 embodiment, the above-mentioned (a-1) silicone-containing monomer contains a nitrogen atom.

In 1 embodiment, the hydrophilic polymer component (b) has a weight average molecular weight of 100000 or more.

In 1 embodiment, the hydrophilic polymer component (b) is a polyvinyl amide.

In 1 embodiment, the (b) hydrophilic polymer component comprises at least 1 selected from the group consisting of poly-N-vinylpyrrolidone, polyalkylene glycol, polysaccharide, poly (meth) acrylic acid, and polyvinyl alcohol.

In 1 embodiment, the hydrophilic polymer component (b) is poly-N-vinylpyrrolidone.

In 1 embodiment, the young's modulus of the polymer material is 0.05MPa to 2.0 MPa.

According to another aspect of the present invention, there is provided an ophthalmic medical device comprising the above polymeric material.

In 1 embodiment, the ophthalmic medical device is a contact lens.

According to the present invention, a silicone-containing polymer material which is transparent and contains an internal wetting agent and has improved stain resistance against lipids can be obtained.

Detailed Description

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

The polymer material according to 1 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 monomer component (a) is polymerized in a state where the monomer component (a) and the hydrophilic polymer component (b) are mixed, preferably in a compatible state. The hydrophilic polymer component (b) used in the present invention is typically a non-polymerizable component having no polymerizable functional group, and by polymerizing the monomer component (a) in such a state, a polymer material in which a polymer containing a structural unit derived from the monomer component (a) and the hydrophilic polymer component (b) are highly complexed can be obtained.

In the present specification, the "monomer" refers to a polymerizable compound having 1 or more polymerizable functional groups. Therefore, a polymerizable compound (also referred to as an oligomer) composed of 2 or more monomer units and a polymerizable compound having a large molecular weight (also referred to as a macromonomer or macromonomer) are also included in the monomers.

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

In the present specification, "(methyl)" means any methyl substitution. Thus, "(meth) acryloyl" refers to methacryloyl and/or acryloyl. The same applies to other descriptions such as "(meth) acrylic group".

A. Polymerizable mixture

The polymerizable mixture contains (a) a monomer component containing (a-1) a silicone-containing monomer having a siloxane bond and no hydroxyl group and (a-2) a compatible monomer having a hydrogen bond proton-containing group and no silicon atom, and (b) a hydrophilic polymer component. The compatible monomer (a-2) compatibilizes the silicone-containing monomer (a-1) and the hydrophilic polymer component (b), and contributes to the improvement of the antifouling property against lipids, so that a polymer material having excellent transparency and antifouling property can be obtained. The polymerizable mixture may further contain any appropriate additive (c) as needed.

In one embodiment 1, the polymerizable mixture is substantially free of a silicone-containing monomer having a hydroxyl group, and more specifically, substantially free of a silicone-containing monomer having a hydroxyl group such as SiGMA. Here, "silicone-containing monomer having substantially no hydroxyl group" means that the blending ratio of the monomer in the polymerizable mixture is 0.1 mass% or less with respect to the total blending amount of the (a) monomer component and the (b) hydrophilic polymer component.

(a) Monomer component

The monomer component contains (a-1) a silicone-containing monomer having a siloxane bond and no hydroxyl group and (a-2) a compatible monomer having a hydrogen bond proton-containing group and no silicon atom, and preferably further contains (a-3) a hydrophilic monomer. The monomer component may further contain 1 or more selected from (a-4) a crosslinkable monomer, (a-5) a functional monomer and (a-6) another comonomer, as required. The total content of the silicone-containing monomer (a-1), the compatible monomer (a-2) and the hydrophilic monomer (a-3) in the entire monomer component may be, for example, 30 to 99% by mass, preferably 70 to 95% by mass.

(a-1) Silicone-containing monomer

The silicone-containing monomer is capable of imparting high oxygen permeability to the polymeric material due to its siloxane structure (Si-O-Si). As the silicone-containing monomer, any suitable monomer may be used as long as it has a siloxane bond and does not have a hydroxyl group. In 1 embodiment, a silicone-containing monomer having not only no hydroxyl group but also no plasma group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group can be used.

Examples of the silicone-containing monomer include those conventionally used as a material for a contact lens, for example, silicone-containing monomers described in paragraphs 0039 to 0044 of Japanese patent application laid-open No. 2015-503631 (excluding a monomer having a hydroxyl group), silicone-containing monomers described in paragraphs 0060 to 0065 of Japanese patent application laid-open No. 2014-40598, and silicone-containing monomers described in paragraphs 0024 to 0037 of WO2015/92858 (specifically, silicone-based macromonomers represented by the following formula (A), preferably formula (A-1), formula (A-2), or (A-3)). In the present specification, these publications are incorporated by reference in their entirety. The silicone-containing monomers may be used alone or in combination of 2 or more.

A¹-Z¹-U¹-Z²-Z³-(-S¹-U²-)_n-S²-Z⁴-Z⁵-U³-Z⁶-A²

…(A)

In the above-mentioned general formula (A),

1) n is 0 or an integer of 1 to 10.

2)A¹And A²Groups represented by the following general formulae (A-II) and (A-III), respectively. In the following general formulae (A-II) and (A-III), Y²¹And Y²²Each independently is acryloxy, methacryloxy, vinyl or allyl, and R²¹And R²²Each independently is a direct bond or a linear chain of 2 to 6 carbon atomsAlkylene groups having a branched or cyclic structure.

Y²¹-R²¹-…(A-II)

-R²²-Y²²…(A-III)

3)Z¹、Z²、Z³、Z⁴、Z⁵And Z⁶Each independently is a direct bond or a polyoxyalkylene chain having an oxyalkylene group as a repeating unit. Wherein Z is¹～Z⁶At least 1 or more of them are polyoxyethylene chains having a repetition number of oxyethylene groups of 2 or more, preferably 4 to 15, and Z which is not a polyoxyethylene chain¹～Z⁶At least 1 or more of them are polyoxyalkylene chains having an oxyalkylene group different from the oxyethylene group as a repeating unit (for example, a polyoxypropylene chain having an oxypropylene group as a constituent unit, and a polyoxypropylene chain having a repeating number of an oxypropylene group of 5 to 16 as a specific example).

4)U¹The group represented by the following general formula (A-IV) contains a urethane bond in the molecular chain of the polysiloxane macromonomer. In the following general formula (A-IV), E²¹is-NHCO-yl (in this case, E²¹And X²¹Forming a urethane bond), or a 2-valent group derived from a diisocyanate selected from the group consisting of saturated or unsaturated aliphatic, alicyclic and aromatic (in this case, E²¹At Z¹And X²¹Urethane bond formed therebetween), X²¹Is an oxygen atom.

-E²¹-X²¹-…(A-IV)

5)U²The group represented by the following general formula (A-VI) contains a urethane bond in the molecular chain of the polysiloxane macromonomer. In the following general formulae (A-VI), R⁴¹And R⁴²Each independently a linear or branched alkylene group having 2 to 6 carbon atoms, X⁴¹And X⁴²Each independently an oxygen atom or an alkylene glycol group, E⁴¹Is a 2-valent group derived from a diisocyanate selected from the group consisting of saturated or unsaturated aliphatic, alicyclic and aromatic (in this case, E⁴¹At X⁴¹And X⁴²Forming urethane bonds therebetween).

-R⁴¹-X⁴¹-E⁴¹-X⁴²-R⁴²-…(A-VI)

6)U³The group represented by the following general formula (A-VII) contains a urethane bond in the molecular chain of the polysiloxane macromonomer. In the following general formula (A-VII), X²²Is an oxygen atom, E²²is-NHCO-yl (in this case, E²²In the reaction with X²²Forming a urethane bond therebetween), or a 2-valent group derived from a diisocyanate selected from the group consisting of saturated or unsaturated aliphatic, alicyclic and aromatic diisocyanates (in this case, E²²At Z⁵And X²²Forming urethane bonds therebetween).

-X²²-E²²-…(A-VII)

7)S¹And S²Each independently is a group represented by the following general formula (A-V). In the following general formula (A-V), R³¹And R³⁸Each independently a linear or branched alkylene group having 2 to 6 carbon atoms, R³²、R³³、R³⁴、R³⁵、R³⁶And R³⁷Each independently is an alkyl group having 1 to 6 carbon atoms, a fluorine-substituted alkyl group, or a phenyl group. In addition, K is an integer of 1 to 1500, L is 0 or an integer of 1 to 1500, and the sum of K and L: "K + L" is an integer of 1 to 1500.

General formula (A-1)

(in the above formula, R⁵¹Represents a hydrogen atom or a methyl group, a is an integer of 2 or more, b is an integer of 2 or more, and n is an integer of 1 to 1500. In addition, R⁵²And R⁵³Is a hydrogen atom or a methyl group, in R⁵²In the case of a hydrogen atom, R⁵³Is methyl at R⁵²In the case of methyl, R⁵³Is a hydrogen atom)

General formula (A-2)

(in the formula, a ' is an integer of 2 or more, b ' is an integer of 2 or more, and n ' is an integer of 1 to 1500.)⁶¹And R⁶²Is a hydrogen atom or a methyl group, in R⁶¹In the case of a hydrogen atom, R⁶²Is methyl at R⁶¹In the case of methyl, R⁶²Is a hydrogen atom)

General formula (A-3)

(in the formula, a ' is an integer of 2 or more, b ' is an integer of 2 or more, and n ' is an integer of 1 to 1500.)⁸¹And R⁸²Is a hydrogen atom or a methyl group, in R⁸¹In the case of a hydrogen atom, R⁸²Is methyl at R⁸¹In the case of methyl, R⁸²Is a hydrogen atom)

Other specific examples of the silicone-containing monomer include trimethylsiloxydimethylsilylmethyl (meth) acrylate, trimethylsiloxydimethylsilylpropyl (meth) acrylate, methyldi (trimethylsiloxy) silylpropyl (meth) acrylate, tris (trimethylsiloxy) silylpropyl (meth) acrylate, mono [ methyldi (trimethylsiloxy) silyloxy ] bis (trimethylsiloxy) silylpropyl (meth) acrylate, tris [ methyldi (trimethylsiloxy) silyloxy ] silylpropyl (meth) acrylate, methyldi (trimethylsiloxy) silylpropyl (meth) acrylate, tris (trimethylsiloxy) silylpropyl (meth) acrylate, mono [ methyl bis (trimethylsiloxy) siloxy ] bis (trimethylsiloxy) silylpropyl glycerol (meth) acrylate, trimethylsilylethyltrimethylsiloxypropyl glycerol (meth) acrylate, trimethylsilylmethyl (meth) acrylate, trimethylsilylpropyl glycerol (meth) acrylate, trimethylsilylpropyl propyl (meth) acrylate, silicone-containing alkyl (meth) acrylates such as trimethylsiloxy dimethylsilyl propyl glycerol (meth) acrylate, methyl bis (trimethylsiloxy) silylethyl tetramethyldisiloxymethyl (meth) acrylate, tetramethyltriisopropylcyclotetrasiloxane propyl (meth) acrylate, and tetramethyltriisopropylcyclotetrasiloxane bis (trimethylsiloxy) silylpropyl (meth) acrylate; tris (trimethylsiloxy) silylstyrene, bis (trimethylsiloxy) methylsilylstyrene, (trimethylsiloxy) dimethylsilylstyrene, tris (trimethylsiloxy) silyldimethylsilylstyrene, [ bis (trimethylsiloxy) methylsiloxy ] dimethylsilylstyrene, (trimethylsiloxy) dimethylsilylstyrene, heptamethyltrisiloxane-alkylstyrene, nonamethyltetrasiloxane-styrene, pentadecmethylheptasiloxane-styrene, heneicosyl-tridecylsiloxane-styrene, heptamethyltridenesiloxane-styrene, trimethylsiloxypentamethylsiloxy-methylsilylstyrene, tris (pentamethyldisiloxy) silylstyrene, tris (trimethylsiloxy) methylsilylstyrene, tris (trimethylsiloxy) methylsilyl-styrene, tris (trimethylsiloxy) silylstyrene, tris (trimethylsiloxy) dimethylsilylene, and the like, Tris (trimethylsiloxy) siloxy bis (trimethylsiloxy) silylstyrene, bis (heptamethyltrimethoxysiloxy) methylsilylstyrene, tris [ methyl bis (trimethylsiloxy) siloxy ] silylstyrene, hepta (trimethylsiloxy) trimethylsilylstyrene, trimethylsiloxybis [ tris (trimethylsiloxy) siloxy ] silylstyrene, nonamethyltrimethylsiloxyundecylmethylpentasiloxymethylsilylmethylsilyl styrene, tris [ tris (trimethylsiloxy) siloxy ] silylstyrene, (trimethylsiloxyhexamethyl) tetramethoxysilyloxy [ tris (trimethylsiloxy) siloxy ] trimethylsiloxysilylstyrene, nona (trimethylsiloxy) tetramethylsilylstyrenes, Silicone-containing styrene derivatives such as bis (tridecylmethylhexasiloxy) methylsilylstyrene, heptamethylcyclotetrasiloxane-styrene, heptamethylcyclotetrasiloxy bis (trimethylsiloxy) silylstyrene, tripropyltetramethylcyclotetrasiloxane-styrene, and trimethylsilylstyrene; silicone-containing fumaric diesters such as bis (3- (trimethylsilyl) propyl) fumarate, bis (3- (pentamethyldisiloxanyl) propyl) fumarate, and bis (tris (trimethylsiloxy) silylpropyl) fumarate.

Still another specific example of the silicone-containing monomer includes mono (meth) acryloxypropyl-terminated mono-n-butyl-terminated polydimethylsiloxane, mono (meth) acryloxypropyl-terminated mono-n-methyl-terminated polydimethylsiloxane, mono (meth) acryloxypropyl-terminated mono-n-butyl-terminated polydiethylsiloxane, mono (meth) acryloxypropyl-terminated mono-n-methyl-terminated polydiethylsiloxane, mono (meth) acryloylaminopropyl terminated mono-n-butyl terminated polydimethylsiloxane, mono (meth) acryloylaminopropyl terminated mono-n-methyl terminated polydimethylsiloxane, mono (meth) acryloylaminopropyl terminated mono-n-butyl terminated polydiethylsiloxane, mono (meth) acryloylaminopropyl terminated mono-n-methyl terminated polydiethylsiloxane and the like. In these silicone-containing monomers, the number of repetitions of (Si-O) may be, for example, 4 to 20, preferably 4 to 12, and more preferably 4 to 10.

In 1 embodiment, a silicone-containing monomer containing a nitrogen atom is used. By including a nitrogen atom in the silicone-containing monomer, the compatibility with the hydrophilic monomer becomes higher, and by the synergistic effect with the compatible monomer, the transparency of the lens can be maintained even if the content of the silicone-containing monomer becomes higher.

The compounding ratio of the silicone-containing monomer in the polymerizable mixture may be, for example, 1 to 70% by mass, preferably 5 to 60% by mass, and more preferably 10 to 50% by mass, based on the total compounding amount of the (a) monomer component and the (b) hydrophilic polymer component. If the compounding ratio of the silicone-containing monomer is within this range, a polymer material having high oxygen permeability can be obtained.

(a-2) compatible monomers

The compatible monomer can help to improve the compatibility of the hydrophilic polymer component with the silicone-containing monomer and the stain resistance to lipids. As compatible monomers, the following monomers can be used: has a hydrogen bond proton-containing group, does not have a silicon atom, and has 4 or more carbon atoms in addition to the carbon atoms contained in the polymerizable functional group. In a conventional silicone hydrogel containing a hydrophilic polymer (internal wetting agent), compatibility between a silicone component and the hydrophilic polymer is ensured by using a silicone-containing monomer (typically SiGMA) having a hydroxyl group having a high affinity for the hydrophilic polymer and a siloxane (-Si-O-Si-) moiety having a high affinity for the silicone component. On the other hand, in the present invention, although a monomer having no silicon atom is used, better compatibility can be ensured than in the case of using SiGMA, and further, an effect of improving the antifouling property against lipid can be obtained.

Examples of the hydrogen bond proton-containing group include a hydroxyl group, a carboxyl group, an amino group, an amide bond, and a sulfonic acid group (-SO)₃H) Urethane bond, urea bond, and the like. Among them, hydroxyl group is preferable. The number of the hydrogen-bonded proton-containing groups of the compatible monomer is, for example, 1 to 12, preferably 1 to 5, more preferably 1 to 3, and further preferably 1 or 2.

The compatible monomer has, for example, 6 or more carbon atoms (excluding carbon atoms contained in the polymerizable functional group), preferably 6 to 25 carbon atoms, more preferably 7 to 15 carbon atoms, and still more preferably 8 to 13 carbon atoms. In the compatible monomer, for example, the number of carbon atoms per 1 hydrogen-bonded proton-containing group is 4 or more, more preferably 5 to 15, and still more preferably 8 to 13.

The solubility of the compatible monomer in water at 25 ℃ is typically less than 0.03g/mL, preferably 0.02g/mL or less, and more preferably 0g/mL to 0.01 g/mL. The use of a monomer having a hydrogen-bonding proton-containing group such as a hydroxyl group but having a hydrophobic property as a whole can contribute to improvement in compatibility of the silicone-containing monomer with the hydrophilic polymer or the hydrophilic monomer.

In 1 embodiment, the compatible monomer has a hydrophobic group containing 2 or more carbon atoms, preferably 4 or more carbon atoms, in addition to the polymerizable functional group and the hydrogen-bonding proton-containing group. In this embodiment, the compatible monomer preferably has a polymerizable functional group, an intermediate portion containing a hydrogen-bonding proton-containing group, and a hydrophobic terminal portion containing 2 or more carbon atoms, and more specifically, it is preferable that the polymerizable functional group is disposed at one terminal portion of the molecule of the compatible monomer, the hydrophobic group is disposed at the other terminal portion, and a group having high hydrophilicity containing a hydrogen-bonding proton-containing group is disposed between them. A compatible monomer having a hydrogen-bonding proton-containing group at a position closer to a polymerizable functional group such as a (meth) acryloyl group and a terminal hydrophobic group at a position farther away therefrom can exhibit excellent affinity for both a hydrophilic polymer and a silicone-containing monomer.

The compatible monomer of the above embodiment may be represented by the following formula (a).

Z-A-B (A)

(in the formula, wherein,

z represents a (meth) acryloyl group,

a comprises a hydrogen-bonded proton-containing group, or represents a divalent atomic group which forms a hydrogen-bonded proton-containing group together with Z,

b represents a hydrocarbon group having 2 to 20 carbon atoms,

wherein the total number of carbon atoms contained in A and B is 4 or more)

In the above formula (a), the divalent group defined by a can be represented by, for example, the following formula:

*-X-R^a1-(L^a1)_r1-[(R^a2)_r2-(L^a2)_r3]_r4- (i)

(here, denotes a bonding site to Z,

x represents O or NR^a3，

R^a1And R^a2Each independently represents an alkylene group having 1 to 20 carbon atoms which may have a hydroxyl group,

R^a3represents hydrogen or an alkyl group having 1 to 4 carbon atoms,

L^a1and L^a2Each independently represents an ether bond, an ester bond, a carbonyl group, an amide bond, a urethane bond or a urea bond,

r1 to r3 each independently represent 0 or 1,

r4 represents an integer of 0 to 10,

wherein the content of the first and second substances,

at R^a2In the case of no hydroxyl group, r3 and r4 are not 0,

(i) having at least 1 radical containing hydrogen-bonded protons)

R^a1And R^a2Each independently preferably represents an alkylene group having 1 to 6 carbon atoms which may have a hydroxyl group, and more preferably represents an alkylene group having 1 to 4 carbon atoms which may have a hydroxyl group. Specifically, R is preferred^a1And R^a2Has a hydroxyl group, more preferably R^a1Having a hydroxyl group. Such an embodiment includes R^a1Having hydroxy groups and being free of R^a2Embodiments of (e.g., embodiments in which R1 is 0 or 1, R2 is 0, and R3 is 0), or R^a1And R^a2Examples of such embodiments include those in which both have a hydroxyl group (for example, embodiments in which r1 is 1, r2 is 1, and r3 is 0 or 1).

L when present^a1And L^a2Each independently preferably may be an ether linkage or an ester linkage. Wherein, in R^a1And R^a2When both of them do not have a hydroxyl group, L is preferably L^a1And L^a2At least one of them is an amide bond, a urethane bond or a urea bond.

The hydrocarbon group defined by B may be linear or branched, may have a cyclic structure, or may have a hetero atom at any position. The hetero atom is not limited as long as the effect of the present invention can be obtained, and examples thereof include halogen such as fluorine. B may be an unsubstituted or fluorine-substituted hydrocarbon group (e.g., an alkyl group) having preferably 4 to 20 carbon atoms, more preferably 5 to 12 carbon atoms.

Specific examples of the compatible monomer of the above embodiment are shown in the following formula (I), formula (V) or formula (VI).

(in the formula, wherein,

R¹represents a hydrogen atom or a methyl group,

R²and R³Each independently represents an alkylene group having 1 to 6 carbon atoms,

R⁴a hydrocarbon group having 2 to 20 carbon atoms, - (R)^5a)_s-O-R^5b、-(R^5a)_s-O(C＝O)-R^5bOr- (R)^5a)_s-(C＝O)O-R^5bShown structure (here, R^5aRepresents an alkylene group having 1 to 4 carbon atoms, R^5bRepresents a hydrocarbon group having 2 to 20 carbon atoms, s represents 0 or 1),

X¹represents O or NR⁶(Here, R is⁶Represents hydrogen or an alkyl group having 1 to 4 carbon atoms),

X²represents a single bond or an alkylene group having 1 to 3 carbon atoms,

X³represents a single bond, an alkylene group having 1 to 6 carbon atoms or a group represented by- (R)^7a)_t-O-(R^7b)_u-、-(R^7a)_t-O(C＝O)-(R^7b)_u-、-(R^7a)_t-(C＝O)O-(R^7b)_u-、-(R^7a)_t-(C＝O)-(R^7b)_u-or structures represented by the following formulae (II) to (IV),

(Here, R is^7aRepresents an alkylene group having 1 to 4 carbon atoms, R^7bRepresents an alkylene group having 1 to 20 carbon atoms, R^8aAnd R^8bEach independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, t and u each independently represents 0 or 1),

n is an integer of 0 to 10,

q1 and q2 are each independently 0 or 1,

wherein the content of the first and second substances,

removal of polymerizable functional group (CH)₂＝CR¹A total of 3 or more carbon atoms contained in the residue after-CO-,

R⁴、R^5b、R⁶、R^8aand R^8bThe hydrocarbon group or the alkyl group as defined may each independently have a hetero atom)

With respect to formula (I), R⁴And R^5bThe predetermined hydrocarbon groups are each preferably an aliphatic hydrocarbon group (e.g., an alkyl group) having 2 to 12 carbon atoms, more preferably 3 to 10 carbon atoms, and still more preferably 4 to 10 carbon atoms. Each of these hydrocarbon groups may be linear or branched, and may have a cyclic structure. It is thought that the compatible monomer can exert affinity for the silicone-containing monomer by functioning as a terminal hydrophobic group.

As R⁴Or R^5bSpecific examples of the hydrocarbon group include a linear alkyl group such as an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, and an n-decyl group; a branched alkyl group such as an isopropyl group, a methylpropyl group, a tert-butyl group, a dimethylpropyl group, an ethylpropyl group, a diethylpropyl group, a methylbutyl group, a dimethylbutyl group, a trimethylbutyl group, an ethylbutyl group, a propylbutyl group, a methylpentyl group, a dimethylpentyl group, an ethylpentyl group, a propylpentyl group, a butylpentyl group, a methylhexyl group, a dimethylhexyl group, a trimethylhexyl group, an ethylhexyl group, a propylhexyl group, a butylhexyl group, a methylheptyl group, a dimethylheptyl group, an ethylheptyl group, a propylheptyl group, a methyloctyl group; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and cyclononyl; cycloalkyl ring-containing alkyl groups such as cyclooctylethyl, cycloheptylmethyl, cycloheptylethyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, cyclohexylbutyl, cyclopentylethyl, cyclopentylbutyl, cyclopentylpentyl, cyclobutylpropyl, cyclobutylbutyl, cyclobutylpentyl, cyclopropylbutyl, cyclopropylpentyl, and cyclopropylhexyl; norbornyl, tricyclodecanyl, tetracyclododecyl, adamantyl, methyladamantyl, ethyladamantyl, butyladamantylAnd iso-bridged alicyclic hydrocarbon groups.

R⁶、R^8aAnd R^8bThe groups (C) are each preferably hydrogen or an alkyl group having 1 or 2 carbon atoms.

X³、R²、R³、R^5aAnd R^7aThe alkylene group is preferably a methylene group, an ethylene group, a propylene group or a butylene group, and more preferably a methylene group or an ethylene group.

R^7bThe alkylene group is preferably an alkylene group having 1 to 8 carbon atoms, and more preferably an alkylene group having 1 to 4 carbon atoms.

X²And R²The total number of carbon atoms contained in the group (a) is preferably 3 or less, more preferably 0 to 2, and still more preferably 1 or 2 (for example, X)²Is methylene or ethylene and no R is present²Embodiments of (e) (i.e., embodiments in which q1 is 0); x²And R²Embodiments in which all are methylene, etc.). It is considered that the compatible monomer can exert affinity for the hydrophilic polymer by disposing the hydroxyl group close to the (meth) acryloyl group.

X³The total number of carbon atoms contained in the group (1) is preferably 0 to 10, more preferably 1 to 5, and further preferably 1 to 3.

As R⁴、R^5b、R⁶、R^8aAnd R^8bThe predetermined hydrocarbon group or alkyl group may have a hetero atom, and is not limited as long as the effect of the present invention can be obtained, and examples thereof include halogen such as fluorine. In 1 embodiment, R⁴、R^5a、R⁶、R^8aOr R^8bThe specified hydrocarbyl or alkyl groups can be fluoroalkyl or perfluoroalkyl groups.

n is preferably 0 to 5, more preferably 0, 1 or 2.

In 1 embodiment, of formula (I), R¹Is a hydrogen atom or a methyl group, X¹Is O, X²Is methylene or ethylene, preferably methylene, n is 0, R⁴Is- (R)^5a)_s-O-R^5b(wherein, R^5aIs methylene, s is 1, R^5bCan be fluorinated and substituted with 2-20 carbon atomsSubstituted hydrocarbyl) q1 is 0 or 1, preferably 0.

In 1 embodiment, of formula (I), R¹Is a hydrogen atom or a methyl group, X¹Is O, X²Is methylene or ethylene, preferably methylene, n is 0, R⁴Is- (R)^5a)_s-O(C＝O)-R^5b(wherein, R^5aIs methylene, s is 1, R^5bA hydrocarbon group which may be substituted with fluorine and has 2 to 20 carbon atoms), q1 is 0 or 1, preferably 0.

In 1 embodiment, of formula (I), R¹Is a hydrogen atom or a methyl group, X¹Is O, X²Is methylene or ethylene, preferably methylene, n is 0, R⁴Is a C2-20 hydrocarbon group which may be substituted by fluorine, and q1 is 0 or 1, preferably 0.

(in the formula, wherein,

R⁹represents a hydrogen atom or a methyl group,

R¹⁰a hydrocarbon group having 4 to 20 carbon atoms, -O-R^10bor-R^10a-O-R^10b、-R^10a-O(C＝O)-R^10b、-R^10a-(C＝O)O-R^10bor-R^10a-(C＝O)-R^10b(Here, R is^10aRepresents an alkylene group having 1 to 4 carbon atoms, R^10bA hydrocarbon group having 2 to 20 carbon atoms),

wherein the content of the first and second substances,

R¹⁰the total number of carbon atoms contained in the group (2) is 4 or more,

R¹⁰or R^10bThe hydrocarbon group as defined may have a hetero atom)

With respect to formula (V), R¹⁰Or R^10bThe predetermined hydrocarbon groups are each preferably an aliphatic hydrocarbon group (e.g., an alkyl group) having 4 to 12 carbon atoms, more preferably 4 to 10 carbon atoms. Each of these hydrocarbon groups may be linear or branched, and may have a cyclic structure. It is considered that these hydrocarbon groups are terminated byThe hydrophobic groups function and the compatible monomer is capable of exerting an affinity for the silicone-containing monomer.

As R¹⁰Or R^10bSpecific examples of the specified hydrocarbon groups include R⁴Or R^5bSpecific examples of the hydrocarbon group to be specified are the same hydrocarbon groups (among them, hydrocarbon groups having 4 or more carbon atoms).

R^10aThe alkylene group is preferably a methylene group, an ethylene group, a propylene group, or a butylene group, and more preferably a methylene group or an ethylene group.

As R¹⁰Or R^10bThe hetero atom that the predetermined hydrocarbon group may have is not limited as long as the effect of the present invention can be obtained, and examples thereof include halogen such as fluorine. In 1 embodiment, R¹⁰Or R^10bThe specified hydrocarbon group may be a fluoroalkyl group or a perfluoroalkyl group.

(in the formula, wherein,

R¹¹represents a hydrogen atom or a methyl group,

X⁴represents O or NR¹⁴(Here, R is¹⁴Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms),

R¹²an alkylene group having 2 to 14 carbon atoms,

X⁵is a single bond, O or a structure represented by the following formulae (VII) to (IX),

(Here, R is^15aAnd R^15bEach independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms),

R¹³represents a hydrocarbon group having 2 to 20 carbon atoms,

wherein the content of the first and second substances,

X⁴when not NH, X⁵Is a compound containing a urethane bond (-NHCOO-) or a urea bond (-NHCONH-)In the structure of (a) to (b),

R¹²、R¹³、R¹⁴、R^15aand R^15bEach independently may have a hetero atom)

With respect to formula (VI), R¹²The alkylene group may be linear or branched, and may have a cyclic structure. R¹²Preferably an alkylene group having 2 to 6 carbon atoms, and more preferably an ethylene group, a propylene group, or a butylene group.

R¹³The hydrocarbon group is preferably an aliphatic hydrocarbon group (e.g., an alkyl group) having 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and still more preferably 4 to 10 carbon atoms. The hydrocarbon group may be linear or branched, and may have a cyclic structure. It is thought that the compatible monomer can exert affinity for the silicone-containing monomer by the hydrocarbon group functioning as a terminal hydrophobic group.

As R¹³Specific examples of the specified hydrocarbon groups include R⁴Or R^5bSpecific examples of the hydrocarbon group are the same as those of the above-mentioned hydrocarbon group.

As R¹⁴、R^15aAnd R^15bSpecific examples of the alkyl group include a methyl group and an ethyl group.

As R¹²、R¹³、R¹⁴、R^15aAnd R^15bThe heteroatom which may be contained is not limited as long as the effect of the present invention can be obtained, and examples thereof include halogen such as fluorine. In 1 embodiment, R¹²、R¹³、R¹⁴、R^15aOr R^15bMay be a fluoroalkyl group or a perfluoroalkyl group.

In another embodiment, the compatible monomer comprises a (meth) acryloyl group and 4 or more carbon atoms, and has an alicyclic ring in which at least 1 hydrogen atom is substituted with a hydrogen-bonded proton-containing group. The alicyclic ring is preferably an alicyclic ring having 5 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and still more preferably 8 to 12 carbon atoms, and may be an alicyclic ring having a bridging structure. Specific examples of the compatible monomer of this embodiment include (meth) acrylates having an alicyclic bridging group (e.g., adamantyl, norbornyl, tricyclodecanyl, tetracyclododecyl, etc.) substituted with 1 or more hydroxyl groups, more specifically, hydroxy (meth) acryloyloxyadamantane, dihydroxy (meth) acryloyloxyadamantane, etc.

The blending ratio of the compatible monomer in the polymerizable mixture may be, for example, 1 to 60% by mass, preferably 5 to 50% by mass, and more preferably 10 to 40% by mass, based on the total blending amount of the (a) monomer component and the (b) hydrophilic polymer component. When the blending ratio of the compatible monomers is within this range, a polymer material having excellent transparency and antifouling property while maintaining high oxygen permeability can be obtained.

(a-3) hydrophilic monomer

The hydrophilic monomer imparts hydrophilicity to the silicone-containing polymer produced by polymerization of the (a) monomer component, and the polymer material as a composite with the (b) hydrophilic polymer component can be made into a hydrogel. As the hydrophilic monomer, for example, a monomer having a solubility in water at 25 ℃ of 0.03g/mL or more (excluding a silicon atom-containing monomer and a monomer having 2 or more polymerizable functional groups) can be used.

Specific examples of the hydrophilic monomer include hydroxyl group-containing alkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and dihydroxypropyl (meth) acrylate; (meth) acrylamides such as N, N-dimethyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-2-hydroxyethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and N-acryloylmorpholine; n-vinyl lactams such as N-vinylpyrrolidone, N-vinylpiperidone and N-vinylcaprolactam; n-methyllactams such as 1-methyl-3-methylene-2-pyrrolidone. Among them, 2-hydroxyethyl (meth) acrylate, N-dimethyl (meth) acrylamide, N-acryloylmorpholine and 1-methyl-3-methylene-2-pyrrolidone can be preferably used. The hydrophilic monomers may be used alone or in combination of 2 or more.

The blending ratio of the hydrophilic monomer in the polymerizable mixture may be, for example, 0.1 to 90% by mass, preferably 20 to 80% by mass, more preferably 25 to 70% by mass, and still more preferably 25 to 50% by mass, based on the total blending amount of the (a) monomer component and the (b) hydrophilic polymer component. If the blending ratio of the hydrophilic monomer is within this range, a polymer material having a high water content and surface hydrophilicity can be obtained.

(a-4) crosslinkable monomer

The crosslinkable monomer is added as necessary for the purpose of improving the mechanical strength, shape stability and the like of the polymer material. As the crosslinkable monomer, a monomer having 2 or more polymerizable functional groups can be used.

Specific examples of the crosslinkable monomer include butylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, diallyl fumarate, allyl (meth) acrylate, vinyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, methacryloyloxyethyl (meth) acrylate, divinylbenzene, diallyl phthalate, diallyl adipate, triallyl diisocyanate, α -methylene-N-vinylpyrrolidone, 4-vinylbenzyl (meth) acrylate, 3-vinylbenzyl (meth) acrylate, 2-bis ((meth) acryloyloxyphenyl) hexafluoropropane, allyl (meth) acrylate, vinyl acetate, vinyl, 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) acryloyloxyisopropyl) benzene, 1, 2-bis (2- (meth) acryloyloxyisopropyl) benzene and the like. Among them, butylene glycol di (meth) acrylate and/or ethylene glycol di (meth) acrylate can be preferably used. The crosslinkable monomer may be used alone or in combination of 2 or more.

The blending ratio of the crosslinkable monomer in the polymerizable mixture may be, for example, 0 to 3% by mass, preferably 0.1 to 2.5% by mass, more preferably 0.3 to 2% by mass, and still more preferably 1.0 to 1.8% by mass, based on the total blending amount of the (a) monomer component and the (b) hydrophilic polymer component. When the blending ratio of the crosslinkable monomer is within this range, a polymer material having good mechanical strength can be obtained.

(a-5) functional monomer

The functional monomer is added as needed 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, a polymerizable ultraviolet absorbing dye, and the like.

Specific examples of the polymerizable dye include 1-phenylazo-4- (meth) acryloyloxynaphthalene, 1-phenylazo-2-hydroxy-3- (meth) acryloyloxynaphthalene, 1-naphthylazo-2-hydroxy-3- (meth) acryloyloxynaphthalene, 1- (. alpha. -anthrazo) -2-hydroxy-3- (meth) acryloyloxynaphthalene, 1- ((4 ' - (phenylazo) -phenyl) azo) -2-hydroxy-3- (meth) acryloyloxynaphthalene, 1- (2 ', 4 ' -xylylazo) -2- (meth) acryloyloxynaphthalene, 1- (o-tolylazo) -2- (meth) acryloyloxynaphthalene, and the like, 2- (m- (meth) 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-tolylazo) -2' -naphthyl) -3-vinylphthalic acid monoamide, N- (1 '- (o-tolylazo) -2' -naphthyl) -6-vinylphthalic acid monoamide, 3-vinylphthalic acid- (4 '- (p-sulfophenylazo) -1' -naphthyl) monoester, 6-vinylphthalic acid- (4 '- (p-sulfophenylazo) -1' -naphthyl) monoester, 3- (meth) acryloylamide-4-phenylazophenol, 3- (meth) acryloylamide-4- (8 '-hydroxy-3', 6 '-disulfo-1' -naphthylazo) -phenol, a salt thereof, a hydrate thereof, 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, and mixtures thereof, Azo-based polymerizable pigments such as 2-amino-4- (p-phenylazoanilino) -6-isopropenyl-1, 3, 5-triazine and 4-phenylazo-7- (meth) 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 '-vinylbenzoyloxyethylamino) -9, 10-anthraquinone, 1-amino-4- (3' -vinylphenylamino) -9, 10-anthraquinone-2-sulfonic acid, 1-amino-4- (4 '-vinylphenylamino) -9, 10-anthraquinone-2-sulfonic acid, 1-amino-4- (2' -vinylbenzylamino) -9, 10-anthraquinone-2-sulfonic acid, 1-amino-4- (3 '- (meth) acryloylaminophenylamino) -9, 10-anthraquinone-2-sulfonic acid, 1-amino-4- (3' - (meth) acryloylaminobenzylamino) -9, 10-anthraquinone-2-sulfonic acid, 1- (. beta. -ethoxycarbonylallylamino) -9, 10-anthraquinone, 1- (. beta. -carboxyallylamino) -9, 10-anthraquinone, 1, 5-di- (. beta. -carboxyallylamino) -9, 10-anthraquinone, 1- (. beta. -isopropoxycarbonylallylamino) -5-benzoylamide-9, 10-anthraquinone, 2- (3 ' - (meth) acryloylamide-anilino) -4- (3 ' - (3 "-sulfo-4" -aminoanthraquinone-1 "-yl) -amino-anilino) -6-chloro-1, 3, 5-triazine, 2- (3 ' - (meth) acryloylamide-anilino) -4- (3 ' - (3" -sulfo-4 "-aminoanthraquinone-1" -yl) -amino-anilino) -6-hydrazino-1, 3, 5-triazine, 2, 4-bis- ((4 "-methoxyanthraquinone-1" -yl) -amino) -6- (3 ' -vinylanilino) -1, anthraquinone-based polymerizable pigments such as 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-methacryloyloxyethyl) phenylamino) 9, 10-anthraquinone, and 1, 4-bis ((2-methacryloyloxyethyl) amino) 9, 10-anthraquinone; nitro-based polymerizable dyes such as o-nitroanilinomethyl (meth) acrylate; phthalocyanine-based polymerizable dyes such as (meth) acrylated tetraaminocopper phthalocyanine and (meth) acrylated (dodecylated tetraaminocopper phthalocyanine). They may be used alone or in combination of 2 or more.

Specific examples of the polymerizable ultraviolet absorber include benzophenone-based polymerizable ultraviolet absorbers such as 2-hydroxy-4- (meth) acryloyloxybenzophenone, 2-hydroxy-4- (meth) acryloyloxy-5-tert-butylbenzophenone, 2-hydroxy-4- (meth) acryloyloxy-2 ', 4' -dichlorobenzophenone, and 2-hydroxy-4- (2 '-hydroxy-3' - (meth) acryloyloxypropyl) benzophenone; benzene such as 2- (2 ' -hydroxy-5 ' - (meth) acryloyloxyethylphenyl) -2H-benzotriazole, 2- (2 ' -hydroxy-5 ' - (meth) acryloyloxyethylphenyl) -5-chloro-2H-benzotriazole, 2- (2 ' -hydroxy-5 ' - (meth) acryloyloxypropylphenyl) -2H-benzotriazole, 2- (2 ' -hydroxy-5 ' - (meth) acryloyloxypropyl-3 ' -tert-butylphenyl) -5-chloro-2H-benzotriazole, and 2- (2 ' -hydroxy-5 ' - (2 ' -methacryloyloxyethoxy) -3 ' -tert-butylphenyl) -5-methyl-2H-benzotriazole A benzotriazole-based polymerizable ultraviolet absorber; salicylic acid derivative-based polymerizable ultraviolet absorbers such as 2-hydroxy-4-methacryloyloxymethylbenzoate; methyl 2-cyano-3-phenyl-3- (3' - (meth) acryloyloxyphenyl) acrylate, and the like. They may be used alone or in combination of 2 or more.

Specific examples of the polymerizable ultraviolet-absorbing coloring matter include 2, 4-dihydroxy-3- (p-styrylazo) benzophenone, 2, 4-dihydroxy-5- (p-styrylazo) benzophenone, 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, and, 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) acryloyloxypropylphenylazo) benzophenone, mixtures thereof, and mixtures thereof, 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) acryloyloxyethylamino) phenylazo) benzophenone, 2, 4-dihydroxy-3- (p- (N-ethyl-N- (meth) acryloyloxyethylamino) phenylazo) benzophenone, 2, 4-dihydroxy-5- (p- (N-ethyl-N- (meth) acryloyloxyethylamino) phenylazo) benzophenone, 2, 4-dihydroxy-3- (o- (N-ethyl-N- (meth) acryloyloxyethylamino) phenylazo) benzophenone, 2, 4-dihydroxy-5- (o- (N-ethyl-N- (meth) acryloyloxyethylamino) phenylazo) benzophenone, 2, 4-dihydroxy-3- (p- (N-ethyl-N- (meth) acryloylamino) phenylazo) benzophenone, 2, 4-dihydroxy-5- (p- (N-ethyl-N- (meth) acryloylamino) phenylazo) benzophenone, a salt thereof, a hydrate thereof, a pharmaceutical composition comprising the compound, Benzophenone-based polymerizable ultraviolet absorbing coloring matters such as 2, 4-dihydroxy-3- (o- (N-ethyl-N- (meth) acryloylamino) phenylazo) benzophenone and 2, 4-dihydroxy-5- (o- (N-ethyl-N- (meth) acryloylamino) phenylazo) benzophenone; benzoic acid-based polymerizable ultraviolet absorbing pigments such as phenyl 2-hydroxy-4- (p-styrylazo) benzoate and the like. They may be used alone or in combination of 2 or more.

The total amount of the functional monomers may be, for example, 0.001 to 5% by mass, preferably 0.05 to 3% by mass, based on the total amount of the monomer component (a) and the hydrophilic polymer component (b).

(a-6) other comonomers

As the other comonomers (a-1) to (a-5) mentioned above, any suitable comonomers can be selected according to the purpose. For example, alkyl (meth) acrylates having an alkyl group having 1 to 20 carbon atoms, preferably 1 to 5 carbon atoms; alkoxyalkyl (meth) acrylates having an alkoxyalkyl group having 1 to 20 carbon atoms, preferably 1 to 5 carbon atoms.

The blending ratio of the other comonomer in the polymerizable mixture may be, for example, 0 to 40% by mass, preferably 0 to 30% by mass, and more preferably 0 to 20% by mass, based on the total blending amount of the (a) monomer component and the (b) hydrophilic polymer component.

(b) Hydrophilic polymer component

As the hydrophilic polymer component, any suitable polymer capable of imparting surface hydrophilicity to the polymer material can be used. For example, polymers such as polyvinyl amides (e.g., polyvinyl lactams), polyamides, polylactones, polyimides, and polylactams can be used as the hydrophilic polymer. Among them, a polymer containing a cyclic structure, for example, a cyclic amide structure or a cyclic imide structure, in a main chain or a side chain can be preferably used. The hydrophilic polymer may be a random copolymer, an alternating copolymer, a block copolymer or a graft copolymer composed of 2 or more kinds of monomers. In addition, as the hydrophilic polymer component, only 1 kind of hydrophilic polymer may be used, or 2 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-piperidone, poly-N-vinyl-4-methyl-2-caprolactam, poly-N-vinyl-3-ethyl-2-pyrrolidone and poly-N-vinyl-4, 5-dimethyl-2-pyrrolidone, Polyalkylene glycols such as polyvinyl imidazole, poly-N-N-dimethylacrylamide, polyvinyl alcohol, poly (meth) acrylic acid, poly (2-hydroxyethyl) (meth) acrylate, and polyethylene glycol, and poly-2-ethyl-Oxazolines, 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 may be, for example, 100000 or more, preferably 150000 to 2000000, more preferably 300000 to 1800000, and still more preferably 500000 to 1,500000.

The hydrophilic polymer may have a K value of, for example, 30 to 150, preferably 60 to 120, and more preferably 90 to 120. The K value can be determined by measuring the viscosity according to the 16 th modification of the 1 st method < 2.53 > viscometry in the Japanese pharmacopoeia and by the formula of Fikentscher (Fikentscher) according to the method described in the section "K value" in the pharmacopoeia.

The amount of the hydrophilic polymer component (b) in the polymerizable mixture may be typically 1 to 30% by mass, preferably 3 to 25% by mass, and more preferably 5 to 20% by mass, based on 100 parts by mass of the total amount of the monomer component (a) and the hydrophilic polymer component (b). When the amount of the hydrophilic polymer component is within this range, a polymer material having high water content and excellent surface hydrophilicity can be obtained.

(c) Additive agent

The additive may be selected from any suitable additives according to the purpose. Examples of the additive include a polymerization initiator and an organic solvent.

The polymerization initiator may be appropriately selected depending on the polymerization method. Examples of the thermal polymerization initiator used for the polymerization by heating include 2,2 '-azobisisobutyronitrile, 2' -azobis (2, 4-dimethylvaleronitrile), benzoyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, lauroyl peroxide, t-butyl peroxyhexanoate, and 3,5, 5-trimethylhexanoyl peroxide. These thermal polymerization initiators may be used alone or in combination of 2 or more.

The amount of the thermal polymerization initiator to be blended in the polymerizable mixture is preferably 0.001 to 2 parts by mass, and more preferably 0.01 to 1 part by mass, based on 100 parts by mass of the total amount of the monomer component (a) and the hydrophilic polymer component (b).

Examples of the photopolymerization initiator used for polymerization by light irradiation include phosphine oxide-based photopolymerization initiators such as 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO) and bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide; benzoin-based photopolymerization initiators such as methyl benzoylbenzoate, methyl benzoylformate, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzoin n-butyl ether; benzophenone-based photopolymerization initiators such as 2-hydroxy-2-methyl-1-phenylpropan-1-one (HMPPO), p-isopropyl- α -hydroxyisobutyl benzophenone, p-tert-butyltrichloroacetophenone, 2-dimethoxy-2-phenylacetophenone, α -dichloro-4-phenoxyacetophenone, and N, N-tetraethyl-4, 4-diaminobenzophenone; 1-hydroxycyclohexyl phenyl ketone; 1-phenyl-1, 2-propanedione-2- (o-ethoxycarbonyl) oxime; thioxanthone-based photopolymerization initiators such as 2-chlorothioxanthone and 2-methylthioxanthone; dibenzosuberone; 2-ethyl anthraquinone; benzophenone acrylate; benzophenone; benzil, and the like. These photopolymerization initiators may be used alone or in combination of 2 or more. In addition, a photosensitizer may be used together with the photopolymerization initiator.

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

The organic solvent may be a water-soluble organic solvent having a high polarity, or may be a water-insoluble organic solvent having a low polarity. 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, tetrahydrofuran, 1, 4-bis (tetrahydrofuran) can be usedAlkanes, and the like. By using a water-soluble organic solvent, the compatibility of the monomer components with each other or the hydrophilic polymer component with the monomer components can be improved. In addition, the water-soluble organic solvent can be easily removed from the polymer material by immersion in water.

As the water-insoluble organic solvent, hexane, cyclohexane, heptane, octane, dimethyl ether, diethyl ether, benzene, toluene, xylene, ethyl acetate, propyl acetate, butyl acetate, methylene chloride, chloroform, carbon tetrachloride, an alcohol having 6 or more carbon atoms, or the like can be used. By using the water-insoluble organic solvent, the compatibility of the monomer components with each other or the hydrophilic polymer component with the monomer components can be improved. In addition, when added to the polymerizable mixture, the kinematic viscosity of the polymerizable mixture is reduced as compared with the case of using a water-soluble organic solvent, and therefore, the handling can be easily performed.

The amount of the organic solvent to be blended in the polymerizable mixture may be, for example, 50 parts by mass or less, preferably 40 parts by mass or less, and more preferably 30 parts by mass or less, based on 100 parts by mass of the total amount of the monomer component (a) and the hydrophilic polymer component (b). In the present invention, since the compatibility of each component in the polymerizable mixture is good, it is not necessary to add an organic solvent, or the amount of the organic solvent to be added can be reduced.

As other additives than the above, additives conventionally used for ophthalmic lenses can be used. Examples thereof include a cooling agent, a thickener, a surfactant, a non-polymerizable dye, an ultraviolet absorber, an ultraviolet absorbing dye, and the like.

The amount of the other additive to be blended in the polymerizable mixture may be, for example, 0.01 to 5 parts by mass, preferably 0.01 to 3 parts by mass, based on 100 parts by mass of the total amount of the monomer component (a) and the hydrophilic polymer component (b).

B. Polymerization process

The polymer material of the present invention can be obtained, for example, by: the polymerizable mixture containing the above-mentioned components is heated and/or irradiated with light (ultraviolet rays and/or visible light) to copolymerize the monomer components in the polymerizable mixture. Alternatively, instead of light irradiation, copolymerization by electron beam irradiation may be used.

As the polymerization method, a bulk polymerization method or a solution polymerization method may be used. In the bulk polymerization method, a part of the monomer component may remain in an unpolymerized state. In the solution polymerization method, a solvent which does not participate in the reaction may remain in the obtained polymer. In order to minimize these residues in the production of contact lenses and the like as medical instruments, the following treatments are performed: the polymer material obtained is immersed in water, an organic solvent, or a mixed solution thereof, and this operation is preferably repeated to dissolve and remove these residues from the polymer material.

When the polymer material of the present invention is used as a material for an ophthalmic lens such as a contact lens, the polymerizable mixture can be reacted by a casting method. When the polymerizable mixture is heated and polymerized by a mold casting method, the mold corresponding to the shape of the desired material for the ophthalmic lens is filled with the polymerizable mixture, and the mold is slowly heated.

The heating temperature and the heating time when the polymerizable mixture in the mold is heated can be appropriately set depending on the composition of the polymerizable mixture and the like. The heating temperature is preferably 50 ℃ or more and 150 ℃ or less, and more preferably 60 ℃ or more and 140 ℃ or less. The heating time when the polymerizable mixture in the mold is heated is preferably 10 minutes to 120 minutes, more preferably 20 minutes to 60 minutes.

In the case of the mold casting method, in which the polymerizable mixture is polymerized by light irradiation, the polymerizable mixture is filled in a mold corresponding to the shape of a desired material for an ophthalmic lens, and then the mold is irradiated with light. The material of the mold used for polymerization by light irradiation is not particularly limited as long as it is a material that can transmit light necessary for polymerization.

The wavelength of light to be irradiated to the polymerizable mixture in the mold is appropriately set according to the kind of the photopolymerization initiator used, and the like. The illuminance and the irradiation time can be appropriately set according to the composition of the polymerizable mixture and the like. The illuminance is preferably 0.1mW/cm²～100mW/cm²The following. The irradiation time is preferably 1 minute or more. It is also possible to irradiate light of different illuminance in stages.

By polymerization using the above-described molding method, a polymer material having a desired shape can be obtained. The polymer material obtained as a molded article may be subjected to machining such as cutting or polishing as needed. The cutting may be performed over the entirety of one or both faces of the polymer material, or may be performed on one or both faces of the polymer material, or on a portion of both faces.

The polymer material of the present invention has excellent surface hydrophilicity because it contains a hydrophilic polymer component as an internal wetting agent, but may be subjected to surface modification treatment such as low-temperature plasma treatment, atmospheric pressure plasma, corona discharge, and the like for the purpose of further surface modification.

C. Characteristics of the Polymer Material

The oxygen permeability coefficient (Dk value) of the polymer material according to 1 embodiment of the present invention is preferably 20Barrer or more, more preferably 30Barrer or more, and still more preferably 50 to 150 Barrer.

The polymer material according to 1 embodiment of the present invention has a water content of preferably 11% by mass or more, more preferably 30% by mass or more, and further preferably 30% by mass to 70% by mass. By setting the water content of the polymer material to 11 mass% or more, the obtained polymer material can be made into hydrogel, so that the wearing feeling when the polymer material is processed into a contact lens can be improved, and the strength, the oxygen permeability, and the surface wettability can be set in a well-balanced manner.

The Young's modulus of the polymer material of 1 embodiment of the present invention is preferably 0.05MPa to 2.0MPa, more preferably 0.1MPa to 1.5MPa, and still more preferably 0.3MPa to 1.5 MPa. By setting the Young's modulus of the polymer material to 0.05MPa to 2.0MPa, the wearing feeling and handling properties when processed into a contact lens can be achieved at the same time.

Examples

The present invention will be specifically described below 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.

[ ingredients used ]

The meanings of the components used in the following examples and comparative examples are simply given below.

(1) Hydrophilic polymers

PVP (K-90, K-120): polyvinyl pyrrolidone

(2) Silicone-containing monomers

AA-PDMS: polymerizable silicone compound having the structure shown below

Silicone macromer a: a silicone macromer of the general formula (a-2) wherein a '═ 6, b' ═ 10 and n ═ 39

TRIS: tris (trimethylsiloxy) silylpropyl methacrylate (structure shown below)

(3) Compatible monomers

EH (OH) MA: a polymerizable compound having the structure shown below (solubility in water at 25 ℃: less than 0.01g/mL)

tBu (OH) MA: a polymerizable compound having the structure shown below (solubility in water at 25 ℃: less than 0.01g/mL)

HADA: a polymerizable compound (manufactured by Mitsubishi gas chemical corporation) having a structure shown below (solubility in water at 25 ℃ C.: less than 0.01g/mL)

DHADM: a polymerizable compound (manufactured by Mitsubishi gas chemical corporation) having a structure shown below (solubility in water at 25 ℃ C.: less than 0.01g/mL)

MA (OH) OCO (OH) Hp: a polymerizable compound having the structure shown below (solubility in water at 25 ℃: less than 0.01g/mL)

C4F9CH2CH (OH) CHMA: a polymerizable compound having the structure shown below (solubility in water at 25 ℃: less than 0.01g/mL)

tBuCO (OH) MA: a polymerizable compound having the structure shown below (solubility in water at 25 ℃: less than 0.01g/mL)

CyCO (OH) MA: a polymerizable compound having the structure shown below (solubility in water at 25 ℃: less than 0.01g/mL)

AdaCO (OH) MA: a polymerizable compound having the structure shown below (solubility in water at 25 ℃: less than 0.01g/mL)

iPr (OH) MA: a polymerizable compound having the structure shown below (solubility in water at 25 ℃: less than 0.01g/mL)

(4) Silicone-containing monomer having hydroxyl group

SiGMA: (3-methacryloxy-2-hydroxypropoxy) propylbis (trimethylsiloxy) methylsilane (structure shown below)

(5) Hydrophilic monomers

DMAA: n, N-dimethylacrylamide

HEMA: 2-Hydroxyethyl methacrylate

(6) Crosslinkable monomer

BDDA: 1, 4-butanediol diacrylate

(7) Functional monomer

HMEPBT: benzotriazole-based polymerizable ultraviolet absorber (2- (2 '-hydroxy-5' -methacryloyloxyethylphenyl) -2H-benzotriazole)

(8) Additive agent

TPO: initiator (2,4, 6-trimethylbenzoyl-diphenylphosphine oxide)

IPA: isopropanol (I-propanol)

Synthetic example 1: preparation of EH (OH) MA

1) Ethylhexyl glycidyl ether, methacrylic acid, tetrabutylammonium bromide, and p-methoxyphenol were added to a brown eggplant-type flask and dissolved, and a diemol condenser was attached thereto, and the mixture was stirred overnight at 90 ℃ in an oil bath.

2) The reaction solution was returned to room temperature, dissolved in hexane, and transferred to a separatory funnel.

3) The hexane layer was washed with 1M aqueous sodium bicarbonate.

4) The hexane layer was washed with distilled water.

5) The hexane layer was washed with saturated brine.

6) The hexane layer was recovered, dried by adding sodium sulfate in an appropriate amount, and left to stand for a while.

7) Sodium sulfate was removed by filtration.

8) The hexane layer was concentrated under reduced pressure to give a slightly yellowish transparent liquid. Measurement of¹H NMR(CDCl₃400MHz) and gas chromatography confirmed that the desired compound was obtained.

[ Synthesis example 2: preparation of tBu (OH) MA

Synthesis and purification were performed in the same manner as in synthesis example 1, except that ethylhexyl glycidyl ether was replaced with tert-butyl glycidyl ether.

[ Synthesis example 3: preparation of MA (OH) OCO (OH) Hp

1) 2-Hydroxyoctanoic acid, glycidyl methacrylate, 4-dimethylaminopyridine and p-methoxyphenol were put into a brown eggplant-shaped flask, and the mixture was stirred overnight at 85 ℃ in an oil bath with a Dimerosal condenser.

2) The reaction solution was returned to room temperature, dissolved in ethyl acetate, and transferred to a separatory funnel.

3) The ethyl acetate layer was washed with a saturated aqueous sodium chloride solution.

4) Using a saturated aqueous sodium bicarbonate solution: distilled water 5: 1 the ethyl acetate layer was washed.

5) The ethyl acetate layer was washed with distilled water.

6) The ethyl acetate layer was washed with saturated saline.

7) Recovering ethyl acetate layer, adding sodium sulfate, drying, and standing for a certain period of time.

8) Sodium sulfate was removed by filtration.

9) The ethyl acetate layer was concentrated under reduced pressure to obtain a transparent liquid. Measurement of¹H NMR(CDCl₃400MHz) and gas chromatography confirmed that the desired compound was obtained.

[ Synthesis example 4: preparation of C4F9CH2CH (OH) CHMA

Synthesis and purification were carried out in the same manner as in Synthesis example 1 except that ethylhexyl glycidyl ether was replaced with 2,2,3,3,4,4,5,5, 5-nonafluoropentyl oxirane and tetrabutylammonium bromide was replaced with triethylamine.

[ Synthesis example 5: preparation of tBuCO (OH) MA

Synthesis and purification were performed in the same manner as in synthesis example 1, except that ethylhexyl glycidyl ether was replaced with glycidyl methacrylate, methacrylic acid was replaced with pivalic acid, and the reaction temperature was set to 60 ℃.

[ Synthesis example 6: preparation of CyCO (OH) MA

Synthesis and purification were performed in the same manner as in synthesis example 1, except that ethylhexyl glycidyl ether was replaced with glycidyl methacrylate, methacrylic acid was replaced with cyclohexanecarboxylic acid, and the reaction temperature was set to 60 ℃.

[ Synthesis example 7: preparation of AdaCO (OH) MA

Synthesis and purification were carried out in the same manner as in Synthesis example 1, except that ethylhexyl glycidyl ether was replaced with glycidyl methacrylate, and methacrylic acid was replaced with 1-adamantanecarboxylic acid.

[ Synthesis example 8: preparation of iPr (OH) MA

Synthesis and purification were carried out in the same manner as in synthesis example 1, except that ethylhexyl glycidyl ether was replaced with glycidyl isopropyl ether.

[ example 1]

PVP (K-90) (manufactured by BASF corporation) 7 parts by mass as a hydrophilic polymer, AA-PDMS 28 parts by mass as a silicone-containing monomer, eh (oh) MA28 parts by mass as a compatible monomer, DMAA30 parts by mass and HEMA7 parts by mass as a hydrophilic monomer, BDDA1.4 parts by mass as a crosslinking monomer, HMEPBT 1.8 parts by mass as a polymerizable ultraviolet absorber, and TPO 0.4 parts by mass as a polymerization initiator were mixed to prepare a polymerizable mixture without using a solvent. The polymerizable mixture was injected into a mold (made of polypropylene, corresponding to a contact lens having a diameter of 14.2mm and a thickness of 0.08 mm) having the shape of a contact lens. Then, the mold is irradiated with LED) light at room temperature to perform photopolymerization. After polymerization, the contact lens-shaped polymeric material is removed from the mold. Thus, a contact lens was obtained.

Examples 2 to 13 and comparative examples 1 to 8

Contact lenses were obtained in the same manner as in example 1, except that the polymerizable mixtures were prepared by mixing the respective components so as to have the compositions shown in table 1 or table 2.

The contact lenses obtained in the above examples and comparative examples were immersed in distilled water to swell until equilibrium was reached, and were replaced with phosphate buffer solution of pH7.5 to swell until equilibrium was reached. Then, the same amount of the phosphate buffer solution was replaced, and the autoclave was sterilized at 121 ℃ for 20 minutes, and then the following characteristic evaluation was performed. However, in the measurement of the oxygen permeability coefficient, a plate-type sample was used, which was obtained by processing a sample into a circular shape having a diameter of 14.0mm by performing polymerization, hydration treatment and sterilization treatment in the same manner as described above, except that a mold having a contact lens shape was replaced with a mold made of PP from which a plate-type sample having an average thickness of about 0.3mm was obtained. The results are shown in tables 1 to 2.

Evaluation of appearance

The appearance of the contact lens was observed with the naked eye.

Evaluation of lipid adhesion

1) 1g of solid artificial lipid (product name "Pharmasol") was put into each well of the multi-well plate at room temperature, and heated to 80 ℃ to be melted.

2) The surface of the contact lens was wiped off, and the contact lens was placed in each well, and then left at room temperature overnight, followed by standing at 60 ℃ for 1 hour.

3) The contact lens was taken out of the hole, washed in a contact lens cleaning solution manufactured by Menion corporation and placed in a beaker under the product name "Epicacid", and then scrubbed 30 times with the contact lens cleaning solution (manufactured by Menion corporation and under the product name "Epicacid").

4) A contact lens cleaning solution (product name "Epicacid" manufactured by Menison) and a contact lens were put into each well of a multi-well plate, and the plate was left at 10 ℃ overnight.

5) The contact lens was taken out from the hole, visually checked for appearance, and evaluated based on the following criteria.

[ judgment standards ]

0: whitening is hardly observed

1: only a partial whitening was observed

2: an overall whitening of about 50% was observed

3: approximately the entire whitening of the lens was observed, but there were portions with low haze

4: whitening of the lens as a whole was observed

Determination of Water content

The surface of the contact lens adjusted in the phosphate buffer solution of pH7.5 at 20 ℃ was gently wiped off to measure the mass (W (g)) in an equilibrium water-containing state. Then, the lens was dried by a drier set at 105 ℃ and the mass (W) in a cooled state was measured₀(g) ). Using these measured values W₀And W, the water content (% by mass) was calculated according to the following equation.

Water content (mass%) { (W-W)₀)/W}×100

Measurement of tensile elastic modulus (Young's modulus)

The contact lens thus produced was punched to produce a dumbbell-shaped sample having a stretched portion of about 1.8mm in width and about 0.1mm in thickness as a test sample. A tensile test was carried out in physiological saline at 20 ℃ using an Shimadzu precision Universal tester Autograph AG-IS MS model manufactured by Shimadzu corporation, and Young's modulus (MPa) was calculated from a stress-elongation curve as a tensile elastic modulus. The drawing speed was 100 mm/min.

Determination of oxygen permeability coefficient (Dk value)

As described above, a circular plate-shaped sample having a diameter of 14.0mm was used as a measurement sample. As a reference standard, the same plate type sample was prepared using the raw material "2 WEEK Menicon Premio" (manufactured by Menicon corporation) so that the Dk value was 129.

The measurement sample was placed on an electrode, and a scientific film oxygen permeability meter (manufactured by seiko chemical industries, Ltd.) was used to conduct nitrogen bubbling in physiological saline at 35 ℃ to set the current value at the equilibrium state to zero. Then, oxygen bubbling was performed, and the current value at the time of equilibrium was recorded. The operation is carried out in the same way as for the reference standard. The oxygen permeability coefficient of the lens was calculated according to the following equation. The unit of the oxygen permeability coefficient is (× 10)^-11(cm²/sec)·(mLO₂/(mL×mmHg))＝Barrer)。

Dk value R (IS/IR) x (TS/TR) x (PR/PS)

Here, the symbols in the above formula have the following meanings.

R: dk value of reference standard (129)

IS: measuring the Current value (. mu.A) of the sample

IR: reference standard Current value (μ A)

TS: the average thickness (mm) of the test specimen was measured

TR: average thickness (mm) of reference standard

PS: measurement of atmospheric pressure (mmHg) of a sample during measurement

PR: atmospheric pressure (mmHg) as determined with reference to a standard

[ Table 1]

[ Table 2]

As shown in table 1, the contact lenses of the examples had high transparency and exhibited superior antifouling property against lipid compared to the contact lenses of the comparative examples. As shown in table 2, the contact lenses of the examples had practically sufficient oxygen permeability and water content, and had mechanical strength suitable for use as contact lenses.

[ examples 14 to 17]

Contact lenses were obtained in the same manner as in example 1, except that the respective components were mixed so as to have the compositions shown in table 3 to prepare polymerizable mixtures.

The contact lenses obtained in examples 14 to 17 were immersed in distilled water to swell the lenses until equilibrium was reached, and then replaced with a phosphate buffer solution having a pH of 7.5 to swell the lenses until equilibrium was reached. Then, the same amount of the fresh phosphate buffer was replaced, and the autoclave was sterilized at 121 ℃ for 20 minutes, and then subjected to the same appearance evaluation and lipid adhesion evaluation as in example 1. The results are shown in table 3.

[ Table 3]

As shown in table 3, the contact lenses of the examples can achieve practically sufficient transparency and have excellent antifouling property against lipids.

[ examples 18 and 19]

Contact lenses were obtained in the same manner as in example 1, except that the polymerizable mixtures were prepared by mixing the respective components so as to have the compositions shown in table 4.

The contact lenses obtained in examples 18 and 19 were immersed in distilled water and allowed to swell until equilibrium was reached, and then replaced with a phosphate buffer solution of pH7.5 and allowed to swell until equilibrium was reached. Then, the same amount of the fresh phosphate buffer was replaced, and the autoclave was sterilized at 121 ℃ for 20 minutes, and then subjected to the same appearance evaluation and lipid adhesion evaluation as in example 1, and the respective properties were measured. The results are shown in table 4.

[ Table 4]

As shown in table 4, the contact lenses of the examples have high transparency and exhibit excellent antifouling property against lipids. Further, the contact lenses of the examples were found to have practically sufficient oxygen permeability and water content and to have mechanical strength suitable for use as contact lenses.

Industrial applicability

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