Modifying agent for ophthalmic devices

Abstract

Provided is an ophthalmic device modifier capable of imparting high wettability and lubricity to a silicone hydrogel, and in detail, an ophthalmic device modifier capable of exhibiting its effects at a small content. Further, provided are a silicone hydrogel obtained by curing a silicone hydrogel composition containing the ophthalmic device modifier, and an ophthalmic device using the silicone hydrogel. It has been found that a water-soluble silicone-containing water-soluble copolymer obtained by copolymerizing a choline phosphate group-containing monomer and a specific silicone monomer is capable of imparting high wettability and lubricity to a silicone hydrogel at a small content.

Description

TECHNICAL FIELD

[0001] The present application relates to a modifier for ophthalmic devices containing a silicone-containing water-soluble copolymer, which is most suitable for use in the manufacture of ophthalmic devices such as contact lenses, intraocular lenses, keratoprosthesis, and the like.

[0002] This application claims priority to Japanese Application No. 2020-199789, which is hereby incorporated by reference. BACKGROUND

[0003] Silicone hydrogel contact lenses have significantly higher oxygen permeability than conventional contact lenses, and thus provide more oxygen to the cornea, which reduces the burden on the ocular tissues. In recent years, silicone hydrogel contact lenses are becoming the mainstream of prescribed contact lenses, and it is expected that they will be further popularized in the future.

[0004] On the other hand, since silicone hydrogel lenses have low water content and high hydrophobicity, they have the disadvantage of easily repelling tears and easily attaching lipid stains. In recent years, it has been reported that the rubbing of the palpebral conjunctival margin against the ocular surface during blinking causes the detachment and degeneration of epithelial cells in the palpebral conjunctival surface (Non-Patent Literature 1, Non-Patent Literature 2). Thus, it is required to impart hydrophilicity to silicone hydrogel lenses while also imparting lubricity. Therefore, various approaches have been studied to improve the surface hydrophilicity and lubricity of silicone hydrogel lenses.

[0005] For example, an approach that includes a plasma treatment step for the lenses in the production process of contact lenses is widely practiced. Although plasma treatment has the advantage of being able to impart high hydrophilicity and durability, it has the disadvantage of being unable to impart lubricity and requiring a large-scale equipment investment.

[0006] As a method that does not require a large-scale equipment investment, a method of manufacturing lenses using a hydrophilic monomer is widely practiced. In particular, it is known that when 2-methacryloyloxyethyl phosphorylcholine having a zwitterionic structure (hereinafter sometimes abbreviated as "MPC") is used, the lenses can obtain high hydrophilicity and high lubricity.

[0007] Patent Literature 1 describes silicone hydrogel lenses obtained from a specific composition that can contain MPC. However, in Patent Literature 1, although the hydrophilicity of the lens surface was shown to be improved by measuring the break up time of water, the lubricity was not studied from the perspective of reducing the friction of the lens surface, and there is room for improvement.

[0008] Patent Literature 2 discloses a silicone hydrogel lens having also good lubricity by using MPC with a specific other monomer in a specific composition ratio. However, in order to obtain good lubricity, it is necessary to add 5% by weight or more of MPC, and in order to obtain the highest lubricity, it is necessary to add about 20% by weight of MPC, and in order to make such a high concentration of MPC compatible with a silicone component having high hydrophobicity, there is a certain restriction on the lens monomer composition.

[0009] In view of the above, a technology capable of being applied to a wider range of lens compositions is required.

[0010] Prior Art Documents

[0011] Patent Literature

[0012] Patent Literature 1: Japanese Patent Application Publication No. 2014-89477

[0013] Patent Literature 2: International Publication No. 2020 / 054711

[0014] Non-Patent Literature

[0015] Non-Patent Literature 1: D. R. Korb et al., 2002, CLAO J., 28, 211-126

[0016] Non-Patent Literature 2: D. R. Korb et al., 2005, Eye & Contact Lens, 31, 2-8 SUMMARY

[0017] Technical Problem to be Solved by the Invention

[0018] The technical problem of the present invention is to provide a modifier for ophthalmic devices capable of imparting high wettability and high lubricity to a silicone hydrogel, and in detail, to provide a modifier for ophthalmic devices which can exhibit its effects with a small amount of content. In addition, to provide a silicone hydrogel obtained by curing a silicone hydrogel composition containing the modifier for ophthalmic devices, and an ophthalmic device using the same.

[0019] Technical Means for Solving the Technical Problem

[0020] The inventors of the present application conducted intensive studies on the above technical problem, and as a result, surprisingly found that a water-soluble silicone-containing water-soluble copolymer obtained by copolymerizing a phosphocholine group-containing monomer and a specific silicone monomer can impart high wettability and high lubricity to a silicone hydrogel with a small amount of content, thereby completing the present invention.

[0021] That is, the present invention is as described below.

[0022] 1. A modifier for ophthalmic devices, comprising a copolymer which is not dissolved in water at 20°C at 1.0% (w / v) but is dissolved in boiling water at 0.1% (w / v) or more, the copolymer containing a structural unit based on a hydrophilic monomer a represented by the following formula (1), and a structural unit based on a silicone monomer b represented by the following formula (2) or formula (3).

[0023] [Chemical Formula 1]

[0024]

[0025] In formula (1), R 1 represents a hydrogen atom or a methyl group, L 1 represents an organic group having 2 to 6 carbon atoms, which can optionally contain an ether bond and / or a hydroxyl group, R 2 ~ R 4 each independently represent a hydrocarbon group having 1 to 3 carbon atoms.

[0026] [Chemical Formula 2]

[0027]

[0028] In formula (2), X 1 represents a (meth)acryloyloxy group, a 3-(2-hydroxyethoxycarbonyl)-2-methylene propanoyloxy group, a 3-(2-hydroxyethoxycarbonyl)-3-butenoxy group or a 3-(2-hydroxyethoxycarbonyl)-2-propenoxy group, L 2 represents an organic group having 2 to 6 carbon atoms, which can optionally contain an ether bond and / or a hydroxyl group, R 5 ~ R 13 each independently represent a methyl group or an ethyl group, and n1 represents 0 or 1.

[0029] [Chemical Formula 3]

[0030]

[0031] In formula (3), R 14 represents a hydrogen atom or a methyl group, L 3 represents an organic group having 2 to 6 carbon atoms, which can optionally contain an ether bond and / or a hydroxyl group, n2 represents an integer of 4 to 20, R 15 ~ R 17 each independently represent an alkyl group having 1 to 8 carbon atoms.

[0032] 2. The modifier for ophthalmic devices according to the preceding item 1, wherein the copolymer further contains a structural unit based on a thermally reactive monomer or a photo-reactive monomer c.

[0033] 3. The modifier for ophthalmic devices according to the preceding 2, wherein the structural unit based on the hydrophilic monomer a represented by the formula (1) is 2-methacryloyloxyethylphosphocholine, the structural unit based on the silicone monomer b represented by the formula (2) or formula (3) is tris(triethylsiloxy)silylpropyl methacrylate, polydimethylsiloxane monomethacrylate, 4-(2-hydroxyethyl)-2-methylene-1-(tris(trimethylsiloxy)silylpropyl)butan-1,4-dioate or 3-(3-(ethylbis(trimethylsiloxy)silyl)propyl)glycerol-1-methacrylate, and the structural unit based on the thermal or photo reactive monomer c is glycidyl methacrylate, methacryloyloxybenzophenone or 4-(4-azidobenzoyloxy methyl)vinylbenzene.

[0034] 4. The modifier for ophthalmic devices according to the preceding 2, wherein the combination of the structural unit based on the hydrophilic monomer a represented by the formula (1), the structural unit based on the silicone monomer b represented by the formula (2) or formula (3), and / or the structural unit based on the thermal or photo reactive monomer c is selected from any one of the following:

[0035] 1) 2-methacryloyloxyethylphosphocholine and tris(triethylsiloxy)silylpropyl methacrylate;

[0036] 2) 2-methacryloyloxyethylphosphocholine and polydimethylsiloxane monomethacrylate;

[0037] 3) 2-methacryloyloxyethylphosphocholine and 4-(2-hydroxyethyl)-2-methylene-1-(tris(trimethylsiloxy)silylpropyl)butan-1,4-dioate;

[0038] 4) 2-methacryloyloxyethylphosphocholine, tris(triethylsiloxy)silylpropyl methacrylate and glycidyl methacrylate;

[0039] 5) 2-methacryloyloxyethylphosphocholine, polydimethylsiloxane monomethacrylate and glycidyl methacrylate;

[0040] 6) 2-methacryloyloxyethylphosphocholine, methacryloylpropyltris(trimethylsiloxy)silane and methacryloyloxybenzophenone;

[0041] 7) 2-methacryloyloxyethylphosphocholine, dimethicone monomethacrylate and methacryloyloxybenzophenone;

[0042] 8) 2-methacryloyloxyethylphosphocholine, 4-(2-hydroxyethyl)-2-methylene-l- (tris(trimethylsiloxy)silylpropyl)-1,4-butanediol and 4-(4-azidobenzoyloxymethyl) vinylbenzene; and

[0043] 9) 2-methacryloyloxyethylphosphocholine, 3-(3-(methylbis(trimethylsiloxy)silyl) propyl)glycerol-1-methacrylate and methacryloyloxybenzophenone.

[0044] 5. A silicone hydrogel composition comprising the copolymer described in the preceding item 1 or 2 and a base composition,

[0045] The silicone hydrogel composition comprises 0.05 to 2 parts by mass of the copolymer with respect to 100 parts by mass of the base composition.

[0046] 6. A silicone hydrogel obtained by curing the silicone hydrogel composition described in the preceding item 5.

[0047] 7. An ophthalmic device using the silicone hydrogel described in the preceding item 6.

[0048] 8. The ophthalmic device described in the preceding item 7, which is a soft contact lens.

[0049] 9. A method for producing a silicone hydrogel, comprising a step of curing a silicone hydrogel composition comprising a copolymer, in which method,

[0050] The copolymer contains structural units based on a hydrophilic monomer a represented by the following formula (1) and structural units based on a silicone monomer b represented by the following formula (2) or formula (3), and the copolymer is not dissolved in water at 20°C at 1.0% (w / v) but is dissolved in boiling water at 0.1% (w / v) or more.

[0051] [Chemical Formula 4]

[0052]

[0053] In formula (1), R 1 represents a hydrogen atom or a methyl group, L 1 represents an organic group having a carbon atom number of 2 to 6, and the organic group can optionally contain one ether bond and / or one hydroxyl group, and R2 ~R 4 each independently represents a hydrocarbon group having 1 to 3 carbon atoms.

[0054] [Chemical Formula 5]

[0055]

[0056] In formula (2), X 1 represents a (meth)acryloyloxy group, a 3-(2-hydroxyethoxycarbonyl)-2-methylene propanoyloxy group, a 3-(2-hydroxyethoxycarbonyl)-3-butenoyloxy group, or a 3-(2-hydroxyethoxycarbonyl)-2-propenoyloxy group, L 2 represents an organic group having 2 to 6 carbon atoms, which can optionally contain an ether bond and / or a hydroxyl group, and R 5 ~R 13 each independently represents a methyl group or an ethyl group, and n1 represents 0 or 1.

[0057] [Chemical Formula 6]

[0058]

[0059] In formula (3), R 14 represents a hydrogen atom or a methyl group, L 3 represents an organic group having 2 to 6 carbon atoms, which can optionally contain an ether bond and / or a hydroxyl group, and n2 represents an integer of 4 to 20, and R 15 ~R 17 each independently represents an alkyl group having 1 to 8 carbon atoms.

[0060] 10. The method of preparing a silicone hydrogel according to the preceding item 9, wherein the amount of the copolymer in the silicone hydrogel composition is 0.1 to 1 parts by mass.

[0061] 11. The method of preparing a silicone hydrogel according to the preceding item 9, wherein the silicone hydrogel composition further comprises a base composition, and the copolymer is 0.05 to 2 parts by mass with respect to 100 parts by mass of the base composition.

[0062] 12. The method for producing a silicone hydrogel according to the preceding item 9, wherein the structural unit based on the hydrophilic monomer a represented by the formula (1) is 2-methacryloyloxyethyl phosphorylcholine, the structural unit based on the silicone monomer b represented by the formula (2) or formula (3) is methacryloyloxypropyl tris(trimethylsiloxy)silane, dimethicone monomethacrylate, 4-(2-hydroxyethyl)-2-methylene-l-(tris(trimethylsiloxy)silylpropyl)-l,4-butanediol diester or 3-(3-(methylbis(trimethylsiloxy)silyl)propyl)glycerol-l-methacrylate, and the structural unit based on the thermal or photo reactive monomer c is glycidyl methacrylate, methacryloyloxybenzophenone or 4-(4-azidobenzoyloxy-methyl)vinylbenzene.

[0063] 13. The method for producing a silicone hydrogel according to the preceding item 9, wherein the combination of the structural unit based on the hydrophilic monomer a represented by the formula (1), the structural unit based on the silicone monomer b represented by the formula (2) or formula (3), and / or the structural unit based on the thermal or photo reactive monomer c is selected from any one of the following:

[0064] 1) 2-methacryloyloxyethyl phosphorylcholine and methacryloyloxypropyl tris(trimethylsiloxy)silane;

[0065] 2) 2-methacryloyloxyethyl phosphorylcholine and dimethicone monomethacrylate;

[0066] 3) 2-methacryloyloxyethyl phosphorylcholine and 4-(2-hydroxyethyl)-2-methylene-l-(tris(trimethylsiloxy)silylpropyl)-l,4-butanediol diester;

[0067] 4) 2-methacryloyloxyethyl phosphorylcholine, methacryloyloxypropyl tris(trimethylsiloxy)silane and glycidyl methacrylate;

[0068] 5) 2-methacryloyloxyethyl phosphorylcholine, dimethicone monomethacrylate and glycidyl methacrylate;

[0069] 6) 2-methacryloyloxyethyl phosphorylcholine, methacryloyloxypropyl tris(trimethylsiloxy)silane and methacryloyloxybenzophenone;

[0070] 7) 2-methacryloyloxyethyl phosphorylcholine, dimethicone monomethacrylate and methacryloyloxybenzophenone;

[0071] 8) 2-methacryloyloxyethylphosphocholine, 4-(2-hydroxyethyl)-2-methylene-l- (tris(trimethylsilyl) silylpropyl)- 1,4-butanediol diester and 4-(4-azidobenzoyloxy- methyl) vinylbenzene; and

[0072] 9) 2-methacryloyloxyethylphosphocholine, 3-(3-(methylbis(tri- methylsilyl) silyl) propyl) glycerol- 1 -methacrylate and methacryloyloxybenzophenone.

[0073] 14. Use of a copolymer in the production of a modifier for ophthalmic devices, wherein the copolymer contains structural units based on a hydrophilic monomer a represented by the following formula (1), and structural units based on a silicone monomer b represented by the following formula (2) or formula (3), the copolymer being incapable of dissolving in water at 20°C at 1.0% (w / v) but capable of dissolving in boiling water at 0.1% (w / v) or more.

[0074] [Chemical Formula 7]

[0075]

[0076] In formula (1), R 1 represents a hydrogen atom or a methyl group, L 1 represents an organic group having 2 to 6 carbon atoms, which can optionally contain an ether bond and / or a hydroxyl group, R 2 ~ R 4 each independently represent a hydrocarbon group having 1 to 3 carbon atoms.

[0077] [Chemical Formula 8]

[0078]

[0079] In formula (2), X 1 represents a (meth)acryloyloxy group, a 3-(2-hydroxyethoxycarbonyl)-2- methylenepropionyloxy group, a 3-(2-hydroxyethoxycarbonyl)-3-butenoyloxy group or a 3-(2-hydroxyethoxycarbonyl)-2-propenoyloxy group, L 2 represents an organic group having 2 to 6 carbon atoms, which can optionally contain an ether bond and / or a hydroxyl group, R 5 ~ R 13 each independently represent a methyl group or an ethyl group, and n1 represents 0 or 1.

[0080] [Chemical Formula 9]

[0081]

[0082] In formula (3), R 14 represents a hydrogen atom or a methyl group, L3 represents an organic group having 2 to 6 carbon atoms, which can optionally contain an ether bond and / or a hydroxyl group, n2 represents an integer of 4 to 20, R 15 ~R 17 each independently represents an alkyl group having 1 to 8 carbon atoms.

[0083] 15. The use in the production of a modifier for ophthalmic devices according to the preceding item 14, wherein the structural unit based on the hydrophilic monomer a represented by the formula (1) is 2-methacryloyloxyethyl phosphorylcholine, the structural unit based on the silicone monomer b represented by the formula (2) or formula (3) is methacryloyloxypropyl tris(trimethylsiloxy)silane, polydimethylsiloxane monomethacrylate, 4-(2-hydroxyethyl)-2-methylene-l-(tris(trimethylsiloxy)silylpropyl)-l,4-butanediol diester or 3-(3-(methylbis(trimethylsiloxy)silyl)propyl)glycerol-l-methacrylate, and the structural unit based on the thermal or photo reactive monomer c is glycidyl methacrylate, methacryloyloxybenzophenone or 4-(4-azidobenzoyloxy methyl)vinylbenzene.

[0084] 16. The use in the production of a modifier for ophthalmic devices according to the preceding item 14, wherein the combination of the structural unit based on the hydrophilic monomer a represented by the formula (1), the structural unit based on the silicone monomer b represented by the formula (2) or formula (3), and / or the structural unit based on the thermal or photo reactive monomer c is selected from any one of the following:

[0085] 1) 2-methacryloyloxyethyl phosphorylcholine and methacryloyloxypropyl tris(trimethylsiloxy)silane;

[0086] 2) 2-methacryloyloxyethyl phosphorylcholine and polydimethylsiloxane monomethacrylate;

[0087] 3) 2-methacryloyloxyethyl phosphorylcholine and 4-(2-hydroxyethyl)-2-methylene-l-(tris(trimethylsiloxy)silylpropyl)-l,4-butanediol diester;

[0088] 4) 2-methacryloyloxyethyl phosphorylcholine, methacryloyloxypropyl tris(trimethylsiloxy)silane and glycidyl methacrylate;

[0089] 5) 2-methacryloyloxyethyl phosphorylcholine, polydimethylsiloxane monomethacrylate and glycidyl methacrylate;

[0090] 6) 2-methacryloyloxyethyl phosphorylcholine, methacryloyloxypropyl tris(trimethylsiloxy)silane and methacryloyloxybenzophenone;

[0091] 7) 2-Methacryloxyethyl phosphate choline, polydimethylsiloxane monomethacrylate and methacryloyloxybenzophenone;

[0092] 8) 2-Methacryloxyethyl phosphate choline, 4-(2-hydroxyethyl)-2-methylene-1-(tris(trimethylsiloxy)silylpropyl)-1,4-succinate and 4-(4-azidobenzoyloxymethyl)vinylbenzene; and

[0093] 9) 2-Methacryloxyethyl phosphate choline, 3-(3-(methylbis(trimethylsiloxy)silyl)propyl)glycerol-1-methacrylate and methacryloyloxybenzophenone.

[0094] Invention Effects

[0095] If the ophthalmic device modifier of the present invention is used, it is possible to impart high wettability and high lubricity to silicone hydrogels. Detailed Implementation

[0096] The present invention will now be described in further detail.

[0097] Additionally, in this specification, "(meth)acrylic acid" means "acrylic acid or methacrylic acid", and the same applies to other similar terms.

[0098] Furthermore, in this specification, when preferred numerical ranges (e.g., ranges of content or weight-average molecular weight) are described as intervals, each lower limit and upper limit can be combined independently. For example, for the description "preferably 10 to 100, more preferably 20 to 90", "preferably lower limit: 10" and "more preferably upper limit: 90" can be combined into "10 to 90".

[0099] One embodiment of the copolymer contained in the ophthalmic device modifier or silicone hydrogel composition of the present invention (hereinafter, sometimes referred to as "the copolymer of the present invention") is a copolymer obtained by copolymerizing a hydrophilic monomer a shown in formula (1) and a silicone monomer b shown in formula (2) or (3) (a copolymer containing structural units based on the hydrophilic monomer a shown in formula (1) and the structural units based on the silicone monomer b shown in formula (2) or (3), said copolymer being insoluble in water at 20°C at 1.0% (w / v) but soluble in boiling water at 0.1% (w / v) or more.

[0100] [Chemical Formula 10]

[0101]

[0102] In equation (1), R1 L represents a hydrogen atom or a methyl group. 1 Represents an organic group having 2 to 6 carbon atoms, wherein the organic group may arbitrarily contain an ether bond and / or a hydroxyl group, R 2 ~R 4 Each of the 1 to 3 carbon atoms can be represented independently as a hydrocarbon group.

[0103] [Chemical Formula 11]

[0104]

[0105] In equation (2), X 1 This indicates (meth)acryloyloxy, 3-(2-hydroxyethoxycarbonyl)-2-methylenepropionyloxy, 3-(2-hydroxyethoxycarbonyl)-3-butenoyloxy, or 3-(2-hydroxyethoxycarbonyl)-2-acryloyloxy. Additionally, L... 2 This indicates an organic group having 2 to 6 carbon atoms, wherein the organic group may optionally contain an ether bond and / or a hydroxyl group. Furthermore, R... 5 ~R 13 Each can be used independently to represent either methyl or ethyl. n1 represents 0 or 1.

[0106] [Chemical Formula 12]

[0107]

[0108] In equation (3), R 14 This indicates a hydrogen atom or a methyl group. Additionally, L... 3 This indicates an organic group having 2 to 6 carbon atoms, wherein the organic group may arbitrarily contain one ether bond and / or one hydroxyl group. n2 represents an integer from 4 to 20. R 15 ~R 17 Each can be used to independently represent an alkyl group having 1 to 8 carbon atoms.

[0109] [Hydrophilic monomer a]

[0110] The R of the hydrophilic monomer a shown in formula (1) 1 It can represent a hydrogen atom or a methyl group, but from the perspective of easy availability of raw materials, a methyl group is preferred.

[0111] In addition, L 1 It refers to an organic group having 2 to 6 carbon atoms, wherein the organic group may arbitrarily contain an ether bond and / or a hydroxyl group, but from the perspective of easy availability of raw materials, -C2H4-, -C2H4-O-C2H4-, and -C2H5- are preferred, and -C2H5- is particularly preferred.

[0112] wherein the organic group is a group composed of C, Si, N, P, O, S, and can also be a polymer having a repeating unit. Furthermore, a ketone group, an ester group, an ether group, a hydroxyl group, an amide group, a sulfide group, an isocyanurate group, or the like can be included in the structure thereof.

[0113] Furthermore, R 2 ~R 4 each independently represent a hydrocarbon group having 1 to 3 carbon atoms, but from the viewpoint of easy availability of raw materials, R 2 ~R 4 are each set to a methyl group.

[0114] Therefore, as specific examples of the hydrophilic monomer a, 2-methacryloyloxyethylphosphocholine and the like can be preferably cited.

[0115] As the monomer a used in the present application, a single monomer can be used, or a plurality of monomers can be used in combination.

[0116] [Silicone monomer b]

[0117] When represented by Formula (2), X 1 represents any one of a (meth)acryloyloxy group, a 3-(2-hydroxyethoxycarbonyl)-2-methylenepropionyloxy group, a 3-(2-hydroxyethoxycarbonyl)-3-butenoyloxy group, or a 3-(2-hydroxyethoxycarbonyl)-2-propenoyloxy group. Among these, from the viewpoint of easy availability of raw materials, a methacryloyloxy group is preferred, and furthermore, from the viewpoint of compatibility with the hydrophilic monomer, a 3-(2-hydroxyethoxycarbonyl)-2-methylenepropionyloxy group is preferred.

[0118] Furthermore, L 2 represents an organic group having 2 to 6 carbon atoms, and the organic group can optionally include an ether bond and / or a hydroxyl group, but from the viewpoint of easy availability of raw materials, -n-C3H6- is preferred.

[0119] Furthermore, R 5 ~R 13 each independently represent a methyl group or an ethyl group, but from the viewpoint of easy availability of raw materials, R 5 ~R 13 are each set to a methyl group.

[0120] Furthermore, n1 represents 0 or 1, but from the viewpoint of improving compatibility with the silicone hydrogel composition, n1 is preferably set to 1.

[0121] Therefore, as specific examples of the monomer b represented by formula (2), methacryloyloxypropyl tris(trimethylsilyl) silane, 4-(2-hydroxyethyl)-2-methylene-l-(tris(trimethylsiloxy)silylpropyl)-l,4-butanediol, and the like can be preferably exemplified.

[0122] R of the silicone monomer b represented by formula (3) 14 represents a hydrogen atom or a methyl group, but from the viewpoint of storage stability of the obtained copolymer, it is preferable to set R 14 to a methyl group.

[0123] Further, L 3 represents an organic group having 2 to 6 carbon atoms, and the organic group can arbitrarily include one ether bond and / or one hydroxyl group.

[0124] Further, n2 represents an integer of 4 to 20. Further, n2 generally has a distribution, and in this case, it is preferable that the number average thereof is in the range of 4 to 20.

[0125] Further, R 15 to R 17 each independently represent an alkyl group having 1 to 8 carbon atoms.

[0126] Therefore, as specific examples of the monomer b represented by formula (3), polydimethylsiloxane monomethyl acrylate, mono-terminal monomethyl acryloyloxypropyl-modified polydimethylsiloxane, and the like can be preferably exemplified.

[0127] As the monomer b used in the present application, a single monomer can be used, or a plurality of monomers can be used in combination. Further, only the monomer represented by formula (2) and any one of the monomers represented by formula (3) can be used, or both of them can be used in combination.

[0128] From the viewpoint of compatibility in the silicone hydrogel monomer blend (silicone hydrogel composition), it is preferable to use the monomer represented by formula (2) alone.

[0129] [Ratio of monomer a to monomer b]

[0130] Regarding the ratio of the monomer a to the monomer b, it is preferable to set monomer a: monomer b = 2: 1 to 300: 1 (mass ratio), more preferable to set 5: 1 to 50: 1, and further more preferable to set 7: 1 to 25: 1. By setting to these ranges, the effect of imparting wettability and lubricity to the silicone hydrogel obtained by curing the silicone hydrogel composition is increased.

[0131] Further, with respect to 100 parts by mass of the monomer a, the monomer b can be set to 0.3 to 50 parts by mass, preferably to 2 to 20 parts by mass, and more preferably to 4 to 14 parts by mass.

[0132] Further, the total proportion of monomer a and monomer b in all monomers used in the production of the copolymer of the present application is preferably set to 50 to 100 mol%, and further preferably to 90 to 100 mol%. This is because the effects of the present application are well exhibited.

[0133] [thermally or photo-reactive monomer c]

[0134] Another aspect of the copolymer of the present application is a copolymer (copolymer containing a structural unit based on the hydrophilic monomer a, a structural unit based on the silicone monomer b, and a structural unit based on the thermally or photo-reactive monomer c) obtained by further copolymerizing a thermally or photo-reactive monomer c in addition to the monomer a and the monomer b, which cannot be dissolved in water at 20°C at 1.0% (w / v) but can be dissolved in boiling water at 0.1% (w / v) or more.

[0135] The thermally or photo-reactive monomer c of the present application refers to a monomer which, by heating or light irradiation, derives a copolymer copolymerized with the monomer c, and has a functional group capable of imparting reactivity which forms a covalent bond between carbon elements between the copolymer and an organic substance coexisting with the copolymer.

[0136] When the production method of the silicone hydrogel using the copolymer of the present application is performed by thermal polymerization, the monomer c is preferably a thermally reactive monomer which derives by heating. Further, when the production method of the silicone hydrogel is performed by photopolymerization, the monomer c is preferably a photo-reactive monomer which derives by light irradiation.

[0137] As a specific example of the monomer c which derives reactivity by heating, (meth)acrylic acid glycidyl ester and the like can be preferably listed.

[0138] As a specific example of the monomer c which derives reactivity by light irradiation, 4-(meth)acryloyloxybenzophenone, (azidobenzoyloxy methyl)vinylbenzene and the like can be preferably listed.

[0139] From the gist of the present application, the reactivity of the above monomer c can also be utilized to introduce a polymerizable functional group such as a (meth)acryloyl group, a vinyl group, and the like by a polymer reaction after the synthesis of the copolymer.

[0140] As the monomer c used in the present application, a single monomer can be used, or a plurality of monomers can be used in combination.

[0141] The proportion of the monomer c in all monomers used in the production of the copolymer of the present application is preferably set to 0 to 50 mol%, and further preferably to 0 to 10 mol%. This is because the effects of the present application are well exhibited.

[0142] [Other monomer d]

[0143] The copolymer of monomers a and b and the copolymer of monomers a, b and c of the present application can be further copolymerized with other monomer d, within a range not impairing the effects of the present application.

[0144] Monomer d can be arbitrarily selected from monomers copolymerizable with monomers a, b and c.

[0145] As such monomers, for example, (meth)acrylic acid and derivatives thereof, (meth)acrylamide and derivatives thereof, and vinyl compounds can be preferably cited.

[0146] As derivatives of (meth)acrylic acid, for example, (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, and the like; (meth)acrylic acid hydroxyalkyl esters such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and the like can be preferably cited.

[0147] As (meth)acrylamide derivatives, for example, dimethyl (meth)acrylamide, hydroxyethyl (meth)acrylamide, and the like can be preferably cited.

[0148] As vinyl compounds, for example, hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, and the like; oligomeric glycol mono vinyl ethers such as diethylene glycol mono vinyl ether; and pyrrolidone derivatives such as N-vinyl pyrrolidone can be preferably cited.

[0149] Monomer d can be used as a single monomer or a plurality of monomers in combination.

[0150] It is preferable to set the proportion of monomer d in all monomers used in the production of the copolymer of the present application to 0 to 10 mol%. This is because the effects of the present application are well exhibited.

[0151] [Production of copolymer]

[0152] As the polymerization method for obtaining the copolymer of the present application, known methods such as solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, and the like can be used, and for example, a method of polymerizing monomers a and monomers b, and further monomers c and d as necessary, in a solvent and in the presence of a polymerization initiator, radical polymerization, and the like can be employed.

[0153] As an initiator for the polymerization, any one can be used as long as it is generally used, for example, an aliphatic azo compound, an organic peroxide, a persulfate salt or the like can be used in the case of radical polymerization. As examples of these polymerization initiators, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, diisopropyl peroxydicarbonate, t-butyl peroxy(2-ethylhexanoate), t-butyl peroxyneopentanoate, t-butyl peroxydiisobutyrate, potassium persulfate, ammonium persulfate or the like can be listed. Two or more of these polymerization initiators can also be used in mixture. In addition, a radical promoter of the redox type can also be used in combination with the polymerization initiator.

[0154] As the polymerization temperature, 30 to 80°C is preferred, and 40 to 70°C is more preferred. In addition, the polymerization time is preferably 2 to 72 hours. This is because the polymerization reaction will proceed well.

[0155] Further, a solvent can also be used in order to smoothly proceed with the polymerization reaction, and as the solvent, water, methanol, ethanol, propanol and the like alcohols, benzene, toluene, dimethylformamide, tetrahydrofuran, dioxane, chloroform or a mixed solvent thereof can be listed.

[0156] [Molecular weight of copolymer]

[0157] The weight average molecular weight of the copolymer of the present application is preferably set to 20,000 to 2,000,000, further preferably to 50,000 to 1,600,000, more further preferably to 100,000 to 1,000,000, and particularly preferably to 200,000 to 500,000. By setting the weight average molecular weight within such a range, it is easy to be compatible with the silicone hydrogel monomer blend (silicone hydrogel composition), and it is possible to impart good wetting property and lubricity to the silicone hydrogel.

[0158] In addition, the weight average molecular weight of the copolymer of the present application can be determined by GPC (gel permeation chromatography) using an EcoSEC system (manufactured by TOSOH CORPORATION) by conversion to polyethylene glycol, for example.

[0159] [Water solubility of copolymer]

[0160] The copolymer of the present application cannot be dissolved in water at 20°C at 1.0% (w / v), but can be dissolved in boiling water at 0.1% (w / v) or more.

[0161] When having a high water solubility of 1.0% (w / v) or more dissolved in water at 20°C, the possibility of impairing the compatibility with a silicone hydrogel monomer blend containing a silicone component having a high hydrophobicity increases. In addition, when being a low water solubility of not being dissolved in boiling water at 0.1% (w / v), the possibility of impairing the effect of imparting a wetting property to a silicone hydrogel is high.

[0162] The water solubility of the copolymer of the present application can be easily evaluated, for example, by the following steps.

[0163] (1) An appropriate amount of the copolymer is weighed in a sealable heat-resistant container. As such a container, for example, a glass vacuum sample bottle can be exemplified.

[0164] (2) Pure water is added to the container to prepare a prescribed concentration.

[0165] For example, when prepared at 5.0% (w / v), 10 mL of pure water is added with respect to 0.5 g of the copolymer.

[0166] (3) The solubility is confirmed by stirring at 20°C and observing with the naked eye.

[0167] (4) After boiling for 30 minutes under normal pressure, the solubility is confirmed by stirring and observing with the naked eye after returning to room temperature (solubility in boiling water).

[0168] Instead of boiling, autoclaving at 121°C for 20 minutes can also be performed.

[0169] In addition, the "dissolution" referred to here means that, under observation with the naked eye, the copolymer put in is uniformly mixed with water, and a state in which insoluble components or turbidity, precipitation are not observed.

[0170] The water solubility of the copolymer of the present application is positively correlated with the ratio of monomer a / monomer b (mass ratio) of the copolymer, and is negatively correlated with the weight average molecular weight of the copolymer.

[0171] Therefore, the water solubility index WSI (Water Solubility Index) can be defined by the following formula (4).

[0172] [Formula 1]

[0173]

[0174] The WSI described above is preferably 5 or more and 1,000 or less, is further preferably set to 9 or more and 700 or less, and is still further preferably set to 20 or more and 300 or less.

[0175] When the WSI is in the range described above, a copolymer having a good water solubility is easily obtained.

[0176] Silicone hydrogel composition

[0177] The present application also targets a silicone hydrogel composition as described below.

[0178] A silicone hydrogel composition containing a copolymer and a base composition, the copolymer containing a structural unit based on a hydrophilic monomer a represented by the following formula (1), and a structural unit based on a silicone monomer b represented by the following formula (2) or formula (3), or

[0179] The copolymer contains a structural unit based on a hydrophilic monomer a represented by the following formula (1), a structural unit based on a silicone monomer b represented by the following formula (2) or formula (3), and a structural unit based on a thermally or photo-reactive monomer c,

[0180] wherein the copolymer is not soluble in water at 20°C at 1.0% (w / v) but is soluble in boiling water at 0.1% (w / v) or more,

[0181] The silicone hydrogel composition contains 0.05 to 2 parts by mass of the copolymer with respect to 100 parts by mass of the base composition.

[0182] [Chemical Formula 13]

[0183]

[0184] In formula (1), R 1 represents a hydrogen atom or a methyl group, L 1 represents an organic group having 2 to 6 carbon atoms, which can optionally contain an ether bond and / or a hydroxyl group, R 2 to R 4 each independently represent a hydrocarbon group having 1 to 3 carbon atoms.

[0185] [Chemical Formula 14]

[0186]

[0187] In formula (2), X 1 represents a (meth)acryloyloxy group, a 3-(2-hydroxyethoxycarbonyl)-2-methylene propanoyloxy group, a 3-(2-hydroxyethoxycarbonyl)-3-butenoxy group, or a 3-(2-hydroxyethoxycarbonyl)-2-propenoxy group, L 2 represents an organic group having 2 to 6 carbon atoms, which can optionally contain an ether bond and / or a hydroxyl group, R 5 to R 13 each independently represent a methyl group or an ethyl group, and n1 represents 0 or 1.

[0188] [Chemical Formula 15]

[0189]

[0190] In formula (3), R 14 represents a hydrogen atom or a methyl group, L 3 represents an organic group having 2 to 6 carbon atoms, which can optionally contain an ether bond and / or a hydroxyl group, n2 represents an integer of 4 to 20, and R 15 ~R 17 each independently represents an alkyl group having 1 to 8 carbon atoms.

[0191] [Silicone hydrogel]

[0192] Another aspect of the present application is a silicone hydrogel obtained by curing a monomer composition (silicone hydrogel composition) containing 0.05 to 2 parts by mass of the copolymer of the present application with respect to 100 parts by mass of a base composition.

[0193] More preferably, the amount of the copolymer of the present application in the silicone hydrogel composition is set to 0.1 to 1 parts by mass. Thereby, the silicone hydrogel composition is well compatible, and the silicone hydrogel can be more favorably endowed with wetting property and lubricating property.

[0194] If the above preferable ranges are integrated, the proportion of the monomer a in 100 parts by weight of the silicone hydrogel composition of the present application is preferably at most 2 parts by mass. That is, by blending a relatively small amount of the MPC type hydrophilic monomer compared to the prior art, the silicone hydrogel can be favorably endowed with wetting property and lubricating property.

[0195] The base composition of the present specification refers to a mixture of monomers, a reaction initiator, and other components added as necessary for preparing a silicone hydrogel.

[0196] The base composition preferably contains 15 parts by weight or more of an alcohol such as propanol, and a hydroxyl-containing monomer such as hydroxyethyl (meth)acrylate in total. This is because the compatibility of the copolymer of the present application is improved.

[0197] As examples of the compounds contained in the base composition, there are propanol, hexanol, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, N-vinylpyrrolidone, methyl (meth)acrylate, tetraethylene glycol di(meth)acrylate, triethylene glycol divinyl ether, (meth)acrylic acid, aminoethyl (meth)acrylate, 4-(2-hydroxyethyl)-2-methylene-1-(tris(trimethylsiloxy)silylpropyl)-1,4-butanediol di(meth)acrylate, polydimethylsiloxane mono(meth)acrylate, and the like, but are not particularly limited.

[0198] The preparation of the silicone hydrogel composition, and the preparation of the silicone hydrogel using the silicone hydrogel composition can be performed using various publicly known methods disclosed in International Publication No. WO2020 / 054711, etc.

[0199] The step of curing the silicone hydrogel composition is preferably performed based on heating (thermal polymerization) or light irradiation (photopolymerization).

[0200] [Method for manufacturing silicone hydrogel including step of curing silicone hydrogel composition containing copolymer of the present invention]

[0201] The present invention also includes the following method for manufacturing a silicone hydrogel.

[0202] A method for manufacturing a silicone hydrogel, including a step of curing a silicone hydrogel composition containing a copolymer of the present invention.

[0203] The copolymer contains structural units based on a hydrophilic monomer a represented by the following formula (1), and structural units based on a silicone monomer b represented by the following formula (2) or formula (3), and the copolymer cannot be dissolved in water at 20°C at 1.0% (w / v), but can be dissolved in boiling water at 0.1% (w / v) or more.

[0204] [Chemical Formula 16]

[0205]

[0206] In formula (1), R 1 represents a hydrogen atom or a methyl group, L 1 represents an organic group having 2 to 6 carbon atoms, which can optionally contain one ether bond and / or one hydroxyl group, R 2 to R 4 each independently represent a hydrocarbon group having 1 to 3 carbon atoms.

[0207] [Chemical Formula 11]

[0208]

[0209] In formula (2), X 1 represents a (meth)acryloyloxy group, a 3-(2-hydroxyethoxycarbonyl)-2-methylene propanoyloxy group, a 3-(2-hydroxyethoxycarbonyl)-3-butenoxy group, or a 3-(2-hydroxyethoxycarbonyl)-2-propenoxy group, L 2 represents an organic group having 2 to 6 carbon atoms, which can optionally contain one ether bond and / or one hydroxyl group, R 5 to R 13 each independently represent a methyl group or an ethyl group, and n1 represents 0 or 1.

[0210] [Chemical Formula 12]

[0211]

[0212] In formula (3), R 14 represents a hydrogen atom or a methyl group, L 3 represents an organic group having 2 to 6 carbon atoms, which can optionally contain an ether bond and / or a hydroxyl group, n2 represents an integer of 4 to 20, and R 15 ~R 17 each independently represents an alkyl group having 1 to 8 carbon atoms.

[0213] In addition, the amount of the copolymer in the silicone hydrogel composition is preferably 0.1 to 1 parts by mass.

[0214] In addition, it is preferable that the silicone hydrogel composition further comprises a base composition, and the copolymer is 0.05 to 2 parts by mass with respect to 100 parts by mass of the base composition.

[0215] [Use of the copolymer of the present invention in the production of a modifier for ophthalmic devices]

[0216] The present invention also encompasses the use of the copolymer of the present invention in the production of a modifier for ophthalmic devices.

[0217] The use of the copolymer in the production of a modifier for ophthalmic devices, wherein the copolymer contains a structural unit based on a hydrophilic monomer a represented by the following formula (1), and a structural unit based on a silicone monomer b represented by the following formula (2) or formula (3), and the copolymer cannot be dissolved in water at 20°C at 1.0% (w / v), but can be dissolved in boiling water at 0.1% (w / v) or more.

[0218] [Chemical Formula 13]

[0219]

[0220] In formula (1), R 1 represents a hydrogen atom or a methyl group, L 1 represents an organic group having 2 to 6 carbon atoms, which can optionally contain an ether bond and / or a hydroxyl group, R 2 ~R 4 each independently represents a hydrocarbon group having 1 to 3 carbon atoms.

[0221] [Chemical Formula 14]

[0222]

[0223] In formula (2), X 1represents a (meth)acryloyloxy group, 3-(2-hydroxyethoxycarbonyl)-2-methylene propanoyloxy group, 3-(2-hydroxyethoxycarbonyl)-3-butenoxy group, or 3-(2-hydroxyethoxycarbonyl)-2-propenoxy group, L 2 represents an organic group having 2 to 6 carbon atoms, wherein the organic group can optionally contain an ether bond and / or a hydroxyl group, R 5 ~R 13 each independently represents a methyl group or an ethyl group, and n1 represents 0 or 1.

[0224] [Chemical Formula 15]

[0225]

[0226] In formula (3), R 14 represents a hydrogen atom or a methyl group, L 3 represents an organic group having 2 to 6 carbon atoms, wherein the organic group can optionally contain an ether bond and / or a hydroxyl group, and n2 represents an integer of 4 to 20, R 15 ~R 17 each independently represents an alkyl group having 1 to 8 carbon atoms.

[0227] As for the combination of the structural unit based on the hydrophilic monomer a represented by formula (1), the structural unit based on the silicone monomer b represented by formula (2) or formula (3), the structural unit based on the thermally reactive monomer or the photo-reactive monomer c, and / or the structural unit based on the other monomer d of the copolymer of the present application, the combinations described in Table 1 below can be exemplified.

[0228] Furthermore, a person skilled in the art can obtain copolymers containing various structural units by appropriately altering the constitution of each structural unit described in Table 1.

[0229] Examples

[0230] Hereinafter, the present application will be further described in detail using examples, but the present application is not limited thereto.

[0231] [Synthesis of Copolymer]

[0232] In order to synthesize the copolymers used in the examples, 14 kinds of copolymers shown in Table 1, i.e., copolymers 1-1 to 3-6 within the scope of the present application were synthesized.

[0233] [Synthesis Example 1-1]

[0234] A glass-made polymerization flask was weighed with 22.5 g of 2-methacryloyloxyethyl phosphorylcholine (hereinafter referred to as MPC) and 1.0 g of methacryloyloxypropyl tris(trimethylsiloxy)silane (hereinafter referred to as TRIS) (molar ratio of monomer composition: MPC / TRIS = 97 / 3), and 35.3 g of ethanol as a polymerization solvent was added to dissolve them. After sufficiently performing nitrogen substitution in the reaction vessel, 12 mg of 2,2'-azobis(2,4-dimethylvaleronitrile) (hereinafter referred to as ADVN) as a polymerization initiator was added, and the temperature was slowly increased to 60°C and directly maintained at 60°C overnight, whereby a polymerization reaction was performed. The obtained reaction solution was added dropwise to an excess of acetone to precipitate the polymer. After filtration and washing with acetone, vacuum drying was performed to obtain a white solid of copolymer 1-1.

[0235] The weight average molecular weight of the obtained copolymer 1-1 was determined to be 356,000 in terms of polyethylene glycol by gel permeation chromatography (hereinafter referred to as GPC).

[0236] [Synthesis Example 1-2]

[0237] A glass-made polymerization flask was weighed with 21.2 g of MPC and 2.3 g of TRIS (molar ratio of monomer composition: MPC / TRIS = 93 / 7), and 35.3 g of n-propanol (hereinafter referred to as NPA) as a polymerization solvent was added to dissolve them. After sufficiently performing nitrogen substitution in the reaction vessel, 12 mg of ADVN as a polymerization initiator was added, and then polymerization and recovery were performed in the same manner as in Synthesis Example 1-1 to obtain a white solid of copolymer 1-2.

[0238] The weight average molecular weight of the obtained copolymer 1-2 was determined to be 288,000 in terms of polyethylene glycol by GPC.

[0239] [Synthesis Example 1-3]

[0240] A glass-made polymerization flask was weighed with 19.5 g of MPC and 4.0 g of TRIS (molar ratio of monomer composition: MPC / TRIS = 87.5 / 12.5), and 35.3 g of NPA as a polymerization solvent was added to dissolve them. After sufficiently performing nitrogen substitution in the reaction vessel, 8 mg of ADVN as a polymerization initiator was added, and then polymerization and recovery were performed in the same manner as in Synthesis Example 1-1 to obtain a white solid of copolymer 1-3.

[0241] The weight average molecular weight of the obtained copolymer 1-3 was determined to be 411,000 in terms of polyethylene glycol by GPC.

[0242] [Synthesis Example 1-4]

[0243] A glass-made polymerization flask was weighed with 23.1 g of MPC, 0.5 g of polydimethylsiloxane monomethacrylate (manufactured by Shin-Etsu Chemical Co., Ltd., hereinafter referred to as PDMSMA) (molar ratio of monomer composition: MPC / PDMSMA = 99.4 / 0.6, calculated by assuming the number average molecular weight of PDMSMA to be 1,000), and 94.1 g of NPA as a polymerization solvent was added to dissolve it. After sufficiently performing nitrogen substitution in the reaction vessel, 6 mg of ADVN as a polymerization initiator was added, and then polymerization and recovery were performed in the same manner as in Synthesis Example 1-1 to obtain a white solid of Copolymer 1-4.

[0244] The weight average molecular weight of the obtained Copolymer 1-4 was determined to be 364,000 by GPC measurement.

[0245] [Synthesis Example 1-5]

[0246] A glass-made polymerization flask was weighed with 23.1 g of MPC, 0.5 g of PDMSMA (molar ratio of monomer composition: MPC / PDMSMA = 99.4 / 0.6), and 35.3 g of NPA as a polymerization solvent was added to dissolve it. After sufficiently performing nitrogen substitution in the reaction vessel, 8 mg of 2,2'-azobisisobutyronitrile (hereinafter referred to as AIBN) as a polymerization initiator was added, and then polymerization and recovery were performed in the same manner as in Synthesis Example 1-1 to obtain a white solid of Copolymer 1-5.

[0247] The weight average molecular weight of the obtained Copolymer 1-5 was determined to be 1,550,000 by GPC measurement.

[0248] [Synthesis Example 1-6]

[0249] A glass-made polymerization flask was weighed with 21.4 g of MPC, 2.6 g of 4-(2-hydroxyethyl)-2-methylene-1-(tris(trimethylsiloxy)silylpropyl)-1,4-butanediol (hereinafter referred to as ETS), and 1.0 g of hydroxyethyl acrylamide (hereinafter referred to as HEAA) (molar ratio of monomer composition: MPC / ETS / HEAA = 84 / 6 / 10), and 100.0 g of NPA as a polymerization solvent was added to dissolve it. After sufficiently performing nitrogen substitution in the reaction vessel, 6 mg of ADVN as a polymerization initiator was added, and then polymerization and recovery were performed in the same manner as in Synthesis Example 1-1 to obtain a white solid of Copolymer 1-6.

[0250] The weight average molecular weight of the obtained Copolymer 1-6 was determined to be 301,000 by GPC measurement.

[0251] [Synthesis Example 2-1]

[0252] A glass reaction vessel was charged with 19.0 g of MPC, 2.1 g of TRIS, 1.1 g of glycidyl methacrylate (hereinafter referred to as GMA) (molar ratio of monomer composition: MPC / TRIS / GMA = 84 / 6 / 10), and 88.9 g of NPA as a polymerization solvent, and the mixture was dissolved. After the reaction vessel was sufficiently replaced with nitrogen, 55 mg of ADVN as a polymerization initiator was added, and the polymerization and recovery were carried out in the same manner as in Synthesis Example 1-1 to obtain a white solid copolymer 2-1.

[0253] The weight average molecular weight of the obtained copolymer 2-1 was determined to be 72,000 by GPC measurement.

[0254] [Synthesis Example 2-2]

[0255] A glass reaction vessel was charged with 20.7 g of MPC, 0.4 g of PDMSMA, 1.1 g of GMA (molar ratio of monomer composition: MPC / PDMSMA / GMA = 89.5 / 0.5 / 10), and 88.9 g of NPA as a polymerization solvent, and the mixture was dissolved. After the reaction vessel was sufficiently replaced with nitrogen, 55 mg of ADVN as a polymerization initiator was added, and the polymerization and recovery were carried out in the same manner as in Synthesis Example 1-1 to obtain a white solid copolymer 2-2.

[0256] The weight average molecular weight of the obtained copolymer 2-2 was determined to be 150,000 by GPC measurement.

[0257] [Synthesis Example 3-1]

[0258] A glass reaction vessel was charged with 18.4 g of MPC, 1.9 g of TRIS, 2.0 g of 4-methacryloyloxybenzophenone (hereinafter referred to as MBP) (molar ratio of monomer composition: MPC / TRIS / MBP = 84 / 6 / 10), and 88.9 g of NPA as a polymerization solvent, and the mixture was dissolved. After the reaction vessel was sufficiently replaced with nitrogen, 55 mg of ADVN as a polymerization initiator was added, and the polymerization and recovery were carried out in the same manner as in Synthesis Example 1-1 to obtain a white solid copolymer 3-1.

[0259] The weight average molecular weight of the obtained copolymer 3-1 was determined to be 72,000 by GPC measurement.

[0260] [Synthesis Example 3-2]

[0261] A glass reaction vessel was charged with 16.0 g of MPC, 3.3 g of TRIS, 1.8 g of MBP (molar ratio of monomer composition: MPC / TRIS / MBP = 79 / 11 / 10), and 84.2 g of NPA as a polymerization solvent to dissolve the same. After sufficiently replacing the inside of the reaction vessel with nitrogen, 52 mg of ADVN as a polymerization initiator was added, and polymerization and recovery were performed in the same manner as in Synthesis Example 1-1 to obtain a white solid of Copolymer 3-2.

[0262] The weight average molecular weight of the obtained Copolymer 3-2 was determined to be 21,000 by GPC measurement.

[0263] [Synthesis Example 3-3]

[0264] A glass reaction vessel was charged with 21.0 g of MPC, 0.4 g of PDMSMA, 2.1 g of MBP (molar ratio of monomer composition: MPC / PDMSMA / MBP = 89.5 / 0.5 / 10), and 94.1 g of NPA as a polymerization solvent to dissolve the same. After sufficiently replacing the inside of the reaction vessel with nitrogen, 59 mg of ADVN as a polymerization initiator was added, and polymerization and recovery were performed in the same manner as in Synthesis Example 1-1 to obtain a white solid of Copolymer 3-3.

[0265] The weight average molecular weight of the obtained Copolymer 3-3 was determined to be 105,000 by GPC measurement.

[0266] [Synthesis Example 3-4]

[0267] A glass reaction vessel was charged with 21.0 g of MPC, 0.4 g of PDMSMA, 2.1 g of MBP (molar ratio of monomer composition: MPC / PDMSMA / MBP = 89.5 / 0.5 / 10), and 35.3 g of NPA as a polymerization solvent to dissolve the same. After sufficiently replacing the inside of the reaction vessel with nitrogen, 6 mg of ADVN as a polymerization initiator was added, and polymerization and recovery were performed in the same manner as in Synthesis Example 1-1 to obtain a white solid of Copolymer 3-4.

[0268] The weight average molecular weight of the obtained Copolymer 3-4 was determined to be 951,000 by GPC measurement.

[0269] [Synthesis Example 3-5]

[0270] A glass-made flask for polymerization was weighed with 18.4 g of MPC, 1.9 g of 3-(3-(methylbis(trimethylsilyl)oxy)silyl)propyl)glycerol-1-methacrylate (hereinafter referred to as SiGMA), and 2.0 g of MBP (molar ratio of monomer composition: MPC / SiGMA / MBP = 84 / 6 / 10), and 88.9 g of NPA as a polymerization solvent was added to dissolve them. After sufficiently performing nitrogen substitution in the reaction vessel, 55 mg of ADVN as a polymerization initiator was added, and then polymerization and recovery were performed in the same manner as in Synthesis Example 1-1 to obtain a copolymer 3-6 as a white solid.

[0271] The weight average molecular weight of the obtained copolymer 3-6 was determined to be 74,000 by GPC measurement in terms of a polyethylene glycol.

[0272] [Synthesis Example 3-6]

[0273] A glass-made flask for polymerization was weighed with 18.4 g of MPC, 1.9 g of 3-(3-(methylbis(trimethylsilyl)oxy)silyl)propyl)glycerol-1-methacrylate (hereinafter referred to as SiGMA), and 2.0 g of MBP (molar ratio of monomer composition: MPC / SiGMA / MBP = 84 / 6 / 10), and 88.9 g of NPA as a polymerization solvent was added to dissolve them. After sufficiently performing nitrogen substitution in the reaction vessel, 55 mg of ADVN as a polymerization initiator was added, and then polymerization and recovery were performed in the same manner as in Synthesis Example 1-1 to obtain a copolymer 3-6 as a white solid.

[0274] The weight average molecular weight of the obtained copolymer 3-6 was determined to be 74,000 by GPC measurement in terms of a polyethylene glycol.

[0275] [GPC measurement]

[0276] The GPC measurement of each of the copolymers of the above Synthesis Examples 1-1 to 3-6 was performed under the following conditions.

[0277] GPC system: EcoSEC system (manufactured by TOSOH CORPORATION)

[0278] Chromatography column: Shodex OHpak SB-802.5HQ (manufactured by SHOWA DENKO K.K.) and SB-806HQ (manufactured by SHOWA DENKO K.K.) were connected in series

[0279] Eluent: 20 mM sodium phosphate buffer (pH 7.4)

[0280] Detector: Differential refractive index detector

[0281] Molecular weight standard: EasiVial PEG / PEO (manufactured by Agilent Technologies, Inc.)

[0282] Flow rate: 0.5 mL / min

[0283] Column temperature: 40°C

[0284] Sample: The resulting copolymer was diluted with a developing solvent to a final concentration of 0.1% by weight

[0285] Injection amount: 100 μL

[0286] [Assessment of water solubility]

[0287] The assessment of water solubility of each copolymer described in Synthesis Examples 1-1 to 3-6 was performed according to the following procedure.

[0288] (1) An appropriate amount of each copolymer was weighed in a 30-cc glass sample bottle to adjust to the prescribed concentration described below.

[0289] (2) 10 mL of ion exchange water was added.

[0290] (3) The stirring was performed at 20°C, and the solubility in water at 20°C was confirmed by visual observation.

[0291] (4) The stirring was performed after autoclaving at 121°C for 20 minutes, and the solubility in boiling water was confirmed by visual observation after returning to room temperature.

[0292] (5) The above (1) to (4) were performed for concentrations of 0.1% (w / v), 0.5% (w / v), 1.0% (w / v), and 5.0% (w / v).

[0293] (6) The maximum concentration in which solubility was confirmed among the above four concentrations was recorded for water at 20°C and boiling water, respectively. In this case, the case in which solubility was not confirmed even at 0.1% (w / v) was recorded as "X".

[0294] The water solubility and weight average molecular weight of each copolymer obtained in Synthesis Examples 1-1 to 3-6 are described in Table 1.

[0295] [Table 1]

[0296]

[0297] *1

[0298] MPC: 2-methacryloyloxyethyl phosphorylcholine

[0299] TRIS: methacryloyloxypropyl tris(trimethylsiloxy)silane

[0300] PDMSMA: polydimethylsiloxane monomethacrylate

[0301] ETS: 4-(2-hydroxyethyl)-2-methylene-l-(tris(trimethylsiloxy)silylpropyl)-l,4-butanediol diester

[0302] HEAA: hydroxyethyl acrylamide

[0303] GMA: glycidyl methacrylate

[0304] MBP: methacryloyloxybenzophenone

[0305] AzSt: 4-(4-azidobenzoyloxymethyl)vinylbenzene

[0306] SiGMA: 3-(3-(methylbis(trimethylsiloxy)silyl)propyl)glycero-l-methacrylate

[0307] -: not containing the corresponding monomer

[0308] ※2

[0309] The maximum concentration at which each copolymer dissolves is described for water at 20°C and boiling water (100°C or higher) (unit: % (w / v)). In the description, a case where the copolymer does not dissolve even at 0.1% (w / v) is described as "X".

[0310] It was confirmed that the copolymers 1-1 to 3-6 did not dissolve in water at 20°C at 1.0% (w / v), but dissolved in boiling water at 0.1% (w / v) or more.

[0311] [Preparation of silicone hydrogel composition]

[0312] The effects of the copolymers of the present application were verified by preparing silicone hydrogels and performing evaluations described later.

[0313] The preparation of silicone hydrogels for the examples and comparative examples was performed according to the following protocol.

[0314] [Preparation of monomer composition]

[0315] Each copolymer prepared in each of the synthesis examples described above was mixed with each lens monomer of the common components Heat 1 to 3 and Light 1 to 2 shown in Table 2 in a prescribed amount to prepare a monomer composition.

[0316] A prescribed amount of each copolymer prepared in each of the synthesis examples (see Table 3), NPA, hydroxyethyl methacrylate (hereinafter referred to as HEMA) was weighed and mixed, and then a prescribed amount of N-vinylpyrrolidone (hereinafter referred to as NVP), light 1, and a prescribed amount of methyl methacrylate (hereinafter referred to as MMA) added to light 2, tetraethylene glycol dimethacrylate (hereinafter referred to as TEGDMA), triethylene glycol divinyl ether (hereinafter referred to as TEGDV), a prescribed amount of methacrylic acid (hereinafter referred to as MA) added to heat 2, and a prescribed amount of aminoethyl methacrylate (hereinafter referred to as AeMA) added to heat 3 were mixed again, ETS was added and mixed again, PDMSMA was added and mixed further again, and finally AIBN as a reaction initiator was added in heat 1 to 3, 2-hydroxy-2-methyl-l-phenylpropanone (hereinafter referred to as O-1173) as a reaction initiator was added in light 1, and phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide (hereinafter referred to as O-819) as a reaction initiator was added in light 2, whereby preparation was performed.

[0317] [Table 2]

[0318]

[0319] NPA: n-propanol

[0320] HEMA: hydroxyethyl methacrylate

[0321] NVP: N-vinylpyrrolidone

[0322] MMA: methyl methacrylate

[0323] TEGDMA: tetraethylene glycol dimethacrylate

[0324] TEGDV: triethylene glycol divinyl ether

[0325] MA: methacrylic acid

[0326] AeMA: aminoethyl methacrylate (11 wt% aqueous solution)

[0327] ETS: 4-(2-hydroxyethyl)-2-methylene-l-(tris(trimethylsiloxy)silylpropyl)-l,4-butanediol

[0328] PDMSMA: polydimethylsiloxane monomethacrylate

[0329] AIBN: 2,2'-azobisisobutyronitrile

[0330] O-1173: 2-hydroxy-2-methyl-l-phenylpropanone

[0331] O-819: phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide

[0332] [Preparation of silicone hydrogel based on thermal curing]

[0333] Thermal 1, Thermal 2 and Thermal 3 (see Table 2) as the monomer composition were injected into a mold made of polypropylene having an inner size of φ 1.1 cm x 0.1 mm, and left in an oven to be shaped into a disc shape as a model of a contact lens. After nitrogen replacement was performed in the oven, the temperature was slowly increased to 80°C, and directly incubated at 80°C for 12 hours, whereby thermal curing was performed to obtain a cured product.

[0334] The cured product was taken out of the mold, and each piece of the cured product was immersed in 40 g of isopropyl alcohol (hereinafter referred to as IPA) for 4 hours, and then immersed in 50 g of ion-exchange water for 4 hours, to perform extraction and purification to remove unreacted substances and the like.

[0335] Next, the cured product was taken out and immersed in physiological saline (hereinafter referred to as PBS) described in ISO-18369-3 for 4 hours, and autoclave sterilization was performed in a state of being immersed in fresh PBS, to obtain a silicone hydrogel.

[0336] [Preparation of silicone hydrogel based on light curing]

[0337] Light 1 and Light 2 (see Table 2) as the monomer composition were injected into a mold made of polypropylene having an inner size of φ 1.1 cm x 0.1 mm, and left in a photoreactor to be shaped into a disc shape as a model of a contact lens. Light having a wavelength of 365 nm or 405 nm and an illuminance of 1.5 mW / cm 2 was irradiated for 20 minutes, whereby light curing was performed to obtain a cured product.

[0338] Thereafter, the cured product was taken out in the same manner as the thermal curing, and purification and sterilization were performed, to obtain a silicone hydrogel.

[0339] [Compatibility of monomer composition]

[0340] The prepared monomer composition was put in a transparent glass container, and the compatibility of the monomer composition was evaluated by visual observation according to the following standards.

[0341] ++: uniform, transparent

[0342] +: slightly turbid, diffused

[0343] x: turbid, precipitated

[0344] [Evaluation of silicone hydrogel]

[0345] The following evaluations were performed on the prepared silicone hydrogel.

[0346] [Transparency]

[0347] The transparency of the prepared silicone hydrogel was determined by visual observation according to the following criteria.

[0348] ++: transparent

[0349] +: slightly turbid

[0350] x: turbid

[0351] [Shape]

[0352] The shape of the prepared silicone hydrogel was determined by visual observation according to the following criteria.

[0353] ++: no deformation observed

[0354] +: slight deformation observed

[0355] x: deformation and poor curing observed

[0356] [Wettability]

[0357] The surface wettability of the prepared silicone hydrogel was evaluated according to the following procedure.

[0358] (1) The prepared silicone hydrogel immersed in PBS was taken out into the air using tweezers.

[0359] (2) The surface of the silicone hydrogel was observed with the naked eye, and the time [seconds] from the start of the rupture of the water film on the surface until the silicone hydrogel was taken out (BUT) was measured. That is, the longer the BUT, the higher the evaluation of the surface wettability.

[0360] (3) The following criteria were used for determination.

[0361] +++ : 30 seconds < BUT

[0362] ++ : 10 seconds < BUT < 30 seconds

[0363] + : 5 seconds < BUT < 10 seconds

[0364] x : BUT < 5 seconds

[0365] [Lubricity]

[0366] The surface lubricity of the prepared silicone hydrogel was evaluated according to the following procedure.

[0367] (1) The silicone hydrogel lens was pinched with the thumb and index finger.

[0368] (2) The lubricity of Polymacon was rated 2 points, and the lubricity of Omafilcon A was rated 8 points, and the scores of 0 to 10 points were given by sensory evaluation. That is, the higher the score, the higher the lubricity.

[0369] (3) The following criteria were used for the determination.

[0370] +++: 8 to 10 points

[0371] ++: 5 to 7 points

[0372] +: 3 to 4 points

[0373] x: 0 to 2 points

[0374] [Examples 1-1 to 1-5]

[0375] The monomers b, copolymers 1-1 to 1-3 shown by the formula (2) were added to the silicone hydrogel composition, respectively, and the silicone hydrogels obtained at this time were evaluated. In addition, the common composition used was Heat 1, and the curing was performed by thermal curing.

[0376] [Examples 1-6 to 1-7]

[0377] The copolymers 1-4 to 1-5 were added to the silicone hydrogel composition, respectively, and the silicone hydrogels obtained at this time were evaluated. In addition, the common composition used was Heat 1, and the curing was performed by thermal curing.

[0378] [Example 1-8]

[0379] The copolymer 1-6 was added to the silicone hydrogel composition, and the silicone hydrogel obtained at this time was evaluated. In addition, the common composition used was Heat 1, and the curing was performed by thermal curing.

[0380] [Examples 2-1 to 2-4]

[0381] The copolymers described in Table 3, the common composition, and the curing method were used, and the silicone hydrogels obtained were evaluated in the same manner as in Example 1.

[0382] [Examples 3-1 to 3-8]

[0383] The copolymers described in Table 3, the common composition were used, and the silicone hydrogels obtained were evaluated in the same manner as in Example 1. In addition, the curing was performed by irradiation of ultraviolet light having a wavelength of 365 nm and an illuminance of 1.5 mW / cm 2 .

[0384] [Example 3-9]

[0385] The silicone hydrogels obtained were evaluated in the same manner as in Example 1 using the copolymers, common compositions set forth in Table 3. In addition, the curing was performed by irradiation of a violet light having a wavelength of 405 nm and an illuminance of 1.5 mW / cm2. 2

[0386] The preparation of the silicone hydrogels performed according to the above procedure and the results of the evaluation thereof are set forth in Table 3.

[0387] [Table 3-1]

[0388]

[0389] [Table 3-2]

[0390]

[0391] [Table 3-3]

[0392]

[0393] *1

[0394] MPC: 2-methacryloyloxyethyl phosphoryl choline

[0395] TRIS: methacryloyloxypropyl tris(trimethylsiloxy)silane

[0396] PDMSMA: polydimethylsiloxane monomethacrylate

[0397] ETS: 4-(2-hydroxyethyl)-2-methylene-l-(tris(trimethylsiloxy)silylpropyl)-l,4-butanediol

[0398] HEAA: hydroxyethyl acrylamide

[0399] GMA: glycidyl methacrylate

[0400] MBP: 4-methacryloyloxybenzophenone

[0401] AzSt: (azidobenzoyloxy methyl)vinylbenzene

[0402] SiGMA: 3-(3-(methylbis(trimethylsiloxy)silyl)propyl)glycero-l-methacrylate

[0403] *2

[0404] The water-soluble case was confirmed under each condition of 20°C 1% (w / v) and boiling water 0.1% (w / v) and is noted as ++, and the water-insoluble case was not confirmed and is noted as —.

[0405] [Comparative Examples 1-1 to 2-3]​

[0406] As a control test in which the copolymer of the present application was not used, seven silicone hydrogels shown in Table 4 were prepared in the same manner as in the examples and evaluated in the same manner as in the examples.

[0407] [Table 4]

[0408]

[0409] MPC: 2-methacryloyloxyethyl phosphorylcholine

[0410] From the results of Table 3 and Table 4, the silicone hydrogels of Examples 1-1 to 3-9 had excellent compatibility, transparency, and shape, and further showed high wettability and high lubricity at the same time, unlike Comparative Examples 1-1 to 2-3, which did not contain the copolymer of the present application, and thus had low wettability and lubricity, either one or both. In Comparative Examples 1-2 and 2-2, even if MPC was blended as a monomer instead of the copolymer of the present application, wettability and lubricity were low.

[0411] From the above examples and comparative examples, it was known that by using the ophthalmic device modifier of the present application, the wettability and lubricity of the silicone hydrogel could be appropriately improved.

[0412] Industrial applicability

[0413] The silicone hydrogel obtained by curing the silicone hydrogel composition containing the ophthalmic device modifier of the present application can provide an ophthalmic device exemplified by a contact lens, an intraocular lens, a keratoprosthesis, and the like.

Claims

1. A modifier for ophthalmic devices, comprising a copolymer which is not soluble in water at 20°C at 1.0% (w / v) but is soluble in boiling water at 0.1% (w / v) or more, the copolymer containing a structural unit based on a hydrophilic monomer a represented by the following formula (1) and a structural unit based on a silicone monomer b represented by the following formula (2) or formula (3), In formula (1), R 1 represents a hydrogen atom or a methyl group, L 1 represents an organic group having 2 to 6 carbon atoms, wherein, The organic group can optionally contain an ether linkage and / or a hydroxyl group, R 2 ~R 4 each independently represents a hydrocarbon group having 1 to 3 carbon atoms, In formula (2), X 1 represents (meth)acryloyloxy group, 3-(2-hydroxyethoxycarbonyl)-2-methylene propanoyloxy group, 3-(2-hydroxyethoxycarbonyl)-3-butenoxy group or 3-(2-hydroxyethoxycarbonyl)-2-propenoxy group, L 2 represents an organic group having 2 to 6 carbon atoms, wherein the organic group can optionally contain an ether bond and / or a hydroxyl group, R 5 ~R 13 each independently represents a methyl group or an ethyl group, and n1 represents 0 or 1, In formula (3), R 14 represents a hydrogen atom or a methyl group, L 3 represents an organic group having 2 to 6 carbon atoms, wherein the organic group can optionally contain an ether bond and / or a hydroxyl group, n2 represents an integer of 4 to 20, R 15 ~R 17 each independently represents an alkyl group having 1 to 8 carbon atoms, wherein the copolymer is contained in a silicone hydrogel composition together with a base composition and cured to obtain a silicone hydrogel, wherein the silicone hydrogel composition contains 0.05 to 2 parts by mass of the copolymer with respect to 100 parts by mass of the base composition.

2. The modifier for ophthalmic devices according to claim 1, wherein, The copolymer further contains a structural unit based on a thermal or photo reactive monomer c.

3. The modifier for ophthalmic devices according to claim 2, wherein, The structural unit based on the hydrophilic monomer a represented by the formula (1) is 2-methacryloyloxyethyl phosphorylcholine, the structural unit based on the silicone monomer b represented by the formula (2) or formula (3) is methacryloylpropyl tris(trimethylsiloxy)silane, polydimethylsiloxane monomethacrylate, 4-(2-hydroxyethyl)-2-methylene-l-(tris(trimethylsiloxy)silylpropyl)-l,4-butanediol diester or 3-(3-(methylbis(trimethylsiloxy)silyl)propyl)glycerol-l-methacrylate, and the structural unit based on the thermal or photo reactive monomer c is glycidyl methacrylate, methacryloyloxybenzophenone or 4-(4-azidobenzoyloxy methyl)vinylbenzene.

4. The modifier for ophthalmic devices according to claim 2, wherein The combination of the structural unit based on the hydrophilic monomer a represented by the formula (1), the structural unit based on the silicone monomer b represented by the formula (2) or formula (3), and / or the structural unit based on the thermal or photo reactive monomer c is selected from any one of the following: 1) 2-methacryloyloxyethyl phosphorylcholine and methacryloylpropyl tris(trimethylsiloxy)silane; 2) 2-methacryloyloxyethyl phosphorylcholine and polydimethylsiloxane monomethacrylate; 3) 2-methacryloyloxyethyl phosphorylcholine and 4-(2-hydroxyethyl)-2-methylene-l-(tris(trimethylsiloxy)silylpropyl)-l,4-butanediol diester; 4) 2-methacryloyloxyethyl phosphorylcholine, methacryloylpropyl tris(trimethylsiloxy)silane and glycidyl methacrylate; 5) 2-methacryloyloxyethyl phosphorylcholine, polydimethylsiloxane monomethacrylate and glycidyl methacrylate; 6) 2-methacryloyloxyethyl phosphorylcholine, methacryloylpropyl tris(trimethylsiloxy)silane and methacryloyloxybenzophenone; 7) 2-methacryloyloxyethyl phosphorylcholine, polydimethylsiloxane monomethacrylate and methacryloyloxybenzophenone; 8) 2-methacryloyloxyethylphosphocholine, 4-(2-hydroxyethyl)-2-methylene-1- (tris(trimethylsiloxy)silylpropyl)-1,4-butanediol diester and 4-(4-azidobenzoyloxy- methyl)vinylbenzene; and 9) 2-methacryloyloxyethylphosphocholine, 3-(3-(methylbis(tri- methylsiloxy)silyl)propyl)glycerol-1-methacrylate and methacryloyloxybenzophenone.

5. A silicone hydrogel composition comprising a copolymer which is insoluble in water at 20°C at 1.0% (w / v) but is soluble in boiling water at 0.1% (w / v) or more and a base composition, the copolymer containing a structural unit of a hydrophilic monomer a represented by the following formula (1) and a structural unit of a silicone monomer b represented by the following formula (2) or formula (3), In formula (1), R 1 represents a hydrogen atom or a methyl group, L 1 represents an organic group having 2 to 6 carbon atoms, wherein, The organic group can optionally contain an ether linkage and / or a hydroxyl group, R 2 ~R 4 each independently represents a hydrocarbon group having 1 to 3 carbon atoms, In formula (2), X 1 represents (meth)acryloxy group, 3-(2-hydroxyethoxycarbonyl)-2-methylene propanoyloxy group, 3-(2-hydroxyethoxycarbonyl)-3-butenoxy group or 3-(2-hydroxyethoxycarbonyl)-2-propenoxy group, L 2 represents an organic group having 2 to 6 carbon atoms, wherein the organic group can optionally contain an ether bond and / or a hydroxyl group, R 5 ~R 13 each independently represents a methyl group or an ethyl group, and n1 represents 0 or 1. In formula (3), R 14 represents a hydrogen atom or a methyl group, L 3 represents an organic group having 2 to 6 carbon atoms, wherein the organic group can optionally contain an ether bond and / or a hydroxyl group, n2 represents an integer of 4 to 20, R 15 ~R 17 each independently represents an alkyl group having 1 to 8 carbon atoms, the silicone hydrogel composition containing 0.05 to 2 parts by mass of the copolymer with respect to 100 parts by mass of the base composition.

6. A silicone hydrogel obtained by curing the silicone hydrogel composition according to claim 5.

7. An ophthalmic device using the silicone hydrogel according to claim 6.

8. The ophthalmic device according to claim 7, which is a soft contact lens.

9. Use of a copolymer in the preparation of a modifier for ophthalmic devices, wherein, the copolymer which is insoluble in water at 20°C at 1.0% (w / v) but is soluble in boiling water at 0.1% (w / v) or more, the copolymer containing a structural unit of a hydrophilic monomer a represented by the following formula (1) and a structural unit of a silicone monomer b represented by the following formula (2) or formula (3), In formula (1), R 1 represents a hydrogen atom or a methyl group, L 1 represents an organic group having 2 to 6 carbon atoms, wherein the organic group can optionally contain an ether bond and / or a hydroxyl group, R 2 ~R 4 each independently represents a hydrocarbon group having 1 to 3 carbon atoms, In formula (2), X 1 represents (meth)acryloxy group, 3-(2-hydroxyethoxycarbonyl)-2-methylene propanoyloxy group, 3-(2-hydroxyethoxycarbonyl)-3-butenoxy group or 3-(2-hydroxyethoxycarbonyl)-2-propenoxy group, L 2 represents an organic group having 2 to 6 carbon atoms, wherein the organic group can optionally contain an ether bond and / or a hydroxyl group, R 5 ~R 13 each independently represents a methyl group or an ethyl group, and n1 represents 0 or 1. In formula (3), R 14 represents a hydrogen atom or a methyl group, L 3 represents an organic group having 2 to 6 carbon atoms, wherein the organic group can optionally contain an ether bond and / or a hydroxyl group, n2 represents an integer of 4 to 20, R 15 ~R 17 each independently represents an alkyl group having 1 to 8 carbon atoms, wherein the copolymer is contained in a silicone hydrogel composition together with a base composition and is cured to obtain a silicone hydrogel, wherein the silicone hydrogel composition contains 0.05 to 2 parts by mass of the copolymer with respect to 100 parts by mass of the base composition.

10. The use of claim 9, wherein the modified agent is prepared by the process of claim 1. the structural unit of the hydrophilic monomer a represented by the formula (1) is 2-methacryloyloxyethylphosphocholine, the structural unit of the silicone monomer b represented by the formula (2) or formula (3) is methacryloylpropyltris(trimethylsiloxy)silane, polydimethylsiloxane monomethacrylate, 4-(2-hydroxyethyl)-2-methylene-1-(tris(trimethylsiloxy)silylpropyl)-1,4-butanediol diester or 3-(3-(methylbis(tri- methylsiloxy)silyl)propyl)glycerol-1-methacrylate, and the structural unit based on a thermal or photo reactive monomer c is glycidyl methacrylate, methacryloyloxybenzophenone or 4-(4-azidobenzoyloxy- methyl)vinylbenzene.

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