Ophthalmic lens

Abstract

To provide an ophthalmic lens that has both oxygen permeability and surface hydrophilicity and suppresses adhesion of lipids.SOLUTION: An ophthalmic lens of the present invention includes a polymer material obtained by polymerizing a polymerizable composition containing, as monomer components, a siloxane monomer having a siloxane bond and a siloxane-free crosslinkable monomer having no siloxane bond. The siloxane-free crosslinkable monomer includes an alkylene glycol chain-containing crosslinkable monomer having a chain portion containing 6 or more alkylene glycol repeating units and polymerizable groups placed at both ends of the chain portion.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an ophthalmic lens. [Background technology]

[0002] Contact lenses are broadly classified into hard contact lenses and soft contact lenses. In recent years, many hard contact lenses have high oxygen permeability due to being formed using siloxane polymers having siloxane bonds (Si-O-Si), but may cause a foreign body sensation when worn due to their hardness. On the other hand, soft contact lenses are formed from a hydrous hydrogel using a copolymer polymer having a hydrophilic monomer and a (meth)acrylic monomer as copolymerization components, and while they provide excellent wearing comfort, they tend to have lower oxygen permeability than hard contact lenses. In response to this, contact lenses that combine high oxygen permeability and excellent wearing comfort have been developed using a silicone hydrogel containing a siloxane monomer as an additional copolymerization component (Patent Document 1).

[0003] However, contact lenses made of silicone hydrogels are prone to adhesion of lipids to their surfaces, and therefore there is a need for contact lenses that combine high oxygen permeability with excellent wearing comfort and that suppress the adhesion of lipids. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 6433790 Summary of the Invention [Problem to be solved by the invention]

[0005] A primary object of the present invention is to provide an ophthalmic lens which achieves both oxygen permeability and wearing comfort and in which adhesion of lipids is suppressed. [Means for solving the problem]

[0006] According to one aspect of the present invention, there is provided an ophthalmic lens comprising a polymer material obtained by polymerizing a polymerizable composition containing, as monomer components, a siloxane monomer having a siloxane bond and a siloxane-free crosslinkable monomer having no siloxane bond, wherein the siloxane-free crosslinkable monomer comprises an alkylene glycol chain-containing crosslinkable monomer having a chain portion containing 6 or more alkylene glycol repeating units and polymerizable groups located at both ends of the chain portion. In one embodiment, the chain portion of the alkylene glycol chain-containing crosslinkable monomer contains 6 to 50 alkylene glycol repeating units. In one embodiment, the alkylene glycol repeating units include at least one selected from the group consisting of ethylene glycol repeating units, propylene glycol repeating units, and butylene glycol repeating units. In one embodiment, the polymerizable composition further comprises a hydrophilic polymer. In one embodiment, the blending ratio of the non-siloxane-containing crosslinkable monomer to the total blending amount of all monomer components and, if present, the hydrophilic polymer in the polymerizable composition is 2% by weight or more, and the blending ratio of the alkylene glycol chain-containing crosslinkable monomer to the total blending amount of all monomer components and, if present, the hydrophilic polymer in the polymerizable composition is 0.9% by weight or more. In one embodiment, the blending ratio of the alkylene glycol chain-containing crosslinkable monomer to the total blending amount of all monomer components and the hydrophilic polymer, if present, in the polymerizable composition is 2% by weight or more. In one embodiment, the blending ratio of the alkylene glycol chain-containing crosslinkable monomer to the total blending amount of all monomer components and the hydrophilic polymer, if present, in the polymerizable composition is 3% by weight to 25% by weight. In one embodiment, the alkylene glycol chain-containing crosslinkable monomer has an HLB value of 5-20. In one embodiment, the blending ratio of the siloxane monomer to the total blending amount of all monomer components in the polymerizable composition and the hydrophilic polymer, if present, is 10% by weight to 70% by weight. In one embodiment, the siloxane monomer has a single polymerizable group. In one embodiment, the siloxane monomer has a repeating number of siloxane bonds of 100 or less. In one embodiment, the siloxane monomer has a repeating number of siloxane bonds of 20 or less. In one embodiment, the weight average molecular weight of the siloxane monomer is 10,000 or less. In one embodiment, the weight average molecular weight of the siloxane monomer is 1,000 or less. In one embodiment, the siloxane monomer includes a siloxane monomer A having a weight average molecular weight of 1,000 or less and a siloxane monomer B having a weight average molecular weight of more than 1,000, and the proportion of the siloxane monomer B to the total of the siloxane monomer A and the siloxane monomer B is 20% by weight or less. In one embodiment, the monomer component further comprises a copolymerizable monomer. In one embodiment, the copolymerizable monomer comprises at least one hydrophilic monomer selected from hydroxyl group-containing alkyl (meth)acrylates, (meth)acrylamides, N-vinyl lactams, N-methyl lactams, methyl (meth)acrylates, and alkoxyalkyl (meth)acrylates. In one embodiment, the blending ratio of the copolymerizable monomer to the total blending amount of all monomer components and the hydrophilic polymer, if present, in the polymerizable composition is 20% by weight to 70% by weight. In one embodiment, the hydrophilic polymer comprises at least one selected from poly-N-vinylpyrrolidone, polyalkylene glycol, polysaccharide, poly(meth)acrylic acid, and polyvinyl alcohol. In one embodiment, the polymer material has a stress relaxation rate of 10% to 40%. In one embodiment, the polymer material has a Young's modulus of 0.3 MPa to 2.3 MPa. In one embodiment, the ophthalmic lens is a contact lens. Effect of the Invention

[0007] According to the present invention, by using a polymer material obtained by polymerizing a monomer component containing a siloxane monomer and a specific crosslinking monomer, it is possible to obtain an ophthalmic lens that has both oxygen permeability and wearing comfort and is suppressed in adhesion of lipids. In addition, the ophthalmic lens obtained by the present invention can have appropriate flexibility and deformation recovery to ensure good handling properties. [Brief description of the drawings]

[0008] [Figure 1] FIG. 2 is a diagram showing evaluation results of ophthalmic lenses obtained in Examples and Comparative Examples. [Diagram 2] FIG. 2 is a diagram illustrating a jig used in measuring a stress relaxation rate. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] In this specification, "monomer" means a polymerizable compound having one or more polymerizable groups. The polymerizable group is preferably an ethylenically unsaturated group, and the polymerizable group may be, for example, a (meth)acryloyl group, a vinyl group, or an allyl group. Here, "(meth)" means any methyl substitution. Thus, "(meth)acryloyl" means methacryloyl and / or acryloyl. The same applies to other descriptions such as "(meth)acrylic".

[0010] The ophthalmic lens according to the embodiment of the present invention comprises a polymer material obtained by polymerizing a polymerizable composition containing a siloxane monomer having a siloxane bond and a siloxane-free crosslinkable monomer having no siloxane bond as a monomer component, and at least an alkylene glycol chain-containing crosslinkable monomer having a chain portion containing 6 or more alkylene glycol repeating units and a polymerizable group disposed at both ends of the chain portion is used as the siloxane-free crosslinkable monomer. The ophthalmic lens according to the embodiment of the present invention typically has a hemispherical shape following the curve of the cornea. The ophthalmic lens according to the embodiment of the present invention can be used as, for example, a contact lens, an artificial cornea, or a corneal onlay, and is preferably a silicone hydrogel contact lens.

[0011] Hereinafter, the embodiments of the present invention will be described in detail, but the present invention is not limited to these embodiments. In addition, each embodiment can be appropriately combined.

[0012] A. Polymerizable composition The polymerizable composition includes, as monomer components, a siloxane monomer having a siloxane bond and a siloxane-free crosslinkable monomer having no siloxane bond, and the siloxane-free crosslinkable monomer includes an alkylene glycol chain-containing crosslinkable monomer having a chain portion containing 6 or more alkylene glycol repeat units and a polymerizable group disposed at both ends of the chain portion. The monomer component preferably further includes a copolymerizable monomer. In one embodiment, the copolymerizable monomer includes a hydrophilic monomer. In one embodiment, the copolymerizable monomer includes a compatibilizing monomer. The polymerizable composition may further include a hydrophilic polymer. By polymerizing a polymerizable composition including a monomer component and a hydrophilic polymer, a polymer material in which a polymer containing a structural unit derived from the monomer component and a hydrophilic polymer component are highly composited can be obtained. The polymerizable composition may further include any appropriate additive as necessary.

[0013] A-1. Monomer components The monomer component includes a siloxane monomer and a non-siloxane-containing crosslinkable monomer including an alkylene glycol chain-containing crosslinkable monomer, and preferably further includes a copolymerizable monomer.

[0014] A-1-1.Siloxane monomer Any suitable monomer may be used as the siloxane monomer as long as it has a siloxane bond (Si-O-Si) and a polymerizable group. The siloxane monomer may impart high oxygen permeability to the polymer material due to the presence of the siloxane bond. In one embodiment, the siloxane monomer may be a non-crosslinkable siloxane monomer having a single polymerizable group (in other words, having only one polymerizable group in the molecule). In another embodiment, the siloxane monomer may be a crosslinkable siloxane monomer having two or more polymerizable groups in the molecule. In the embodiment of the present invention, only one type of siloxane monomer may be used, or two or more types may be used in combination.

[0015] Examples of the siloxane monomer include monomers conventionally used as contact lens materials, such as the siloxane monomers described in paragraphs 0039 to 0044 of JP-T-2015-503631, the siloxane monomers described in paragraphs 0060 to 0065 of JP-A-2014-40598, and the siloxane monomers described in paragraphs 0024 to 0037 of WO2015 / 92858 (specifically, siloxane monomers represented by the following formula (A), preferably the formula (A-1), (A-2) or (A-3)). These publications are incorporated herein in their entirety by reference.

[0016] [ka] In the above general formula (A), 1) n is 0 or an integer from 1 to 10. 2) A 1 and A 2are groups represented by the following general formulae (A-II) and (A-III), respectively. In the following general formulae (A-II) and (A-III), Y 21 and Y 22 are each independently an acryloyloxy group, a methacryloyloxy group, a vinyl group, or an allyl group, and R 21 and R 22 are each independently a direct bond or a linear or branched alkylene group having 2 to 6 carbon atoms. Y 21 -R 21 - (A-II) -R 22 -Y 22 (A-III) 3) Z 1 , Z 2 , Z 3 , Z 4 , Z 5 and Z 6 are each independently a direct bond or a polyalkylene glycol chain having an alkylene glycol (oxyalkylene group) as a repeating unit. 1 ~Z 6 At least one of the Z is a polyethylene glycol chain having a repeat number of ethylene glycol of 2 or more, preferably 4 to 15, and 1 ~Z 6 At least one of these is a polyalkylene glycol chain having an alkylene glycol other than ethylene glycol as a repeating unit (for example, a polypropylene glycol chain having propylene glycol as a constituent unit, a specific example of which is a polypropylene glycol chain having 5 to 16 repeating units of propylene glycol). 4) U 1 is a group represented by the following general formula (A-IV), which contains a urethane bond in the molecular chain of the siloxane monomer. 21 is the -NHCO- group (in this case, E 21 isX 21and forms a urethane bond), or a divalent group derived from a diisocyanate selected from the group consisting of saturated or unsaturated aliphatic, alicyclic and aromatic diisocyanates (in this case, E 21 Z 1 and X 21 A urethane bond is formed between X 21 is an oxygen atom. -E 21 -X 21 - (A-IV) 5) U 2 is a group represented by the following general formula (A-VI), which contains a urethane bond in the molecular chain of the siloxane monomer. In the following general formula (A-VI), R 41 and R 42 are each independently a linear or branched alkylene group having 2 to 6 carbon atoms; X 41 and X 42 are each independently an oxygen atom or an alkylene glycol group; E 41 is a divalent group derived from a diisocyanate selected from the group consisting of saturated or unsaturated aliphatic, alicyclic and aromatic diisocyanates (in this case, E 41 isX 41 and X 42 (a urethane bond is formed between them). -R 41 -X 41 -E 41 -X 42 -R 42 - (A-VI) 6) U 3 is a group represented by the following general formula (A-VII), which contains a urethane bond in the molecular chain of the siloxane monomer. In the following general formula (A-VII), X 22 is an oxygen atom, and E 22 is the -NHCO- group (in this case, E 22 isX 22 or a divalent group derived from a diisocyanate selected from the group consisting of saturated or unsaturated aliphatic, alicyclic and aromatic diisocyanates (in this case, E 22 Z 5 and X 22(a urethane bond is formed between them). -X 22 -E 22 - (A-VII) 7) S 1 and S 2 are each independently a group represented by the following general formula (AV). In the following general formula (AV), R 31 and R 38 are each independently a linear or branched alkylene group having 2 to 6 carbon atoms; R 32 , R 33 , R 34 , R 35 , R 36 and R 37 are each independently an alkyl group having 1 to 6 carbon atoms, a fluorine-substituted alkyl group, or a phenyl group. 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, for example, an integer of 1 to 1500, preferably an integer of 2 to 1000, and more preferably an integer of 3 to 500. [ka]

[0017] [ka] (In the above formula, R 51 represents 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. 52 and R 53 is a hydrogen atom or a methyl group, and R 52 When is a hydrogen atom, R 53 is a methyl group, and R 52 When is a methyl group, R 53 is a hydrogen atom.)

[0018] [ka] (In the above 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. 61 and R 62 is a hydrogen atom or a methyl group, and R 61 When is a hydrogen atom, R 62 is a methyl group, and R 61 When is a methyl group, R 62 is a hydrogen atom.)

[0019] [ka] (In the above 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. 81 and R 82 is a hydrogen atom or a methyl group, and R 81 When is a hydrogen atom, R 82 is a methyl group, and R 81 When is a methyl group, R 82 is a hydrogen atom.)

[0020] Other specific examples of siloxane monomers include trimethylsiloxydimethylsilylmethyl (meth)acrylate, trimethylsiloxydimethylsilylpropyl (meth)acrylate, methylbis(trimethylsiloxy)silylpropyl (meth)acrylate, tris(trimethylsiloxy)silylpropyl (meth)acrylate, mono[methylbis(trimethylsiloxy)siloxy]bis(trimethylsiloxy)silylpropyl (meth)acrylate, tris[methylbis(trimethylsiloxy)siloxy]silylpropyl (meth)acrylate, methylbis(trimethylsiloxy)silylpropyl glyceryl (meth)acrylate, tris(trimethylsiloxy)silylpropyl glyceryl (meth)acrylate, mono[methylbis(trimethylsiloxy)siloxy]bis(trimethylsiloxy)silylpropyl Silicone-containing alkyl (meth)acrylates such as trimethylsiloxy)silylpropyl glyceryl (meth)acrylate, trimethylsilylethyl tetramethyldisiloxypropyl glyceryl (meth)acrylate, trimethylsilylmethyl (meth)acrylate, trimethylsilylpropyl glyceryl (meth)acrylate, trimethylsilylpropyl (meth)acrylate, trimethylsiloxydimethylsilylpropyl glyceryl (meth)acrylate, methylbis(trimethylsiloxy)silylethyl tetramethyldisiloxymethyl (meth)acrylate, tetramethyltriisopropyl cyclotetrasiloxanylpropyl (meth)acrylate, and tetramethyltriisopropyl cyclotetrasiloxybis(trimethylsiloxy)silylpropyl (meth)acrylate;Tris(trimethylsiloxy)silylstyrene, bis(trimethylsiloxy)methylsilylstyrene, (trimethylsiloxy)dimethylsilylstyrene, tris(trimethylsiloxy)siloxydimethylsilylstyrene, [bis(trimethylsiloxy)methylsiloxy]dimethylsilylstyrene, (trimethylsiloxy)dimethylsilylstyrene, heptamethyltrisiloxanylstyrene, nonamethyltetrasiloxanylstyrene, pentadecamethylheptasiloxanylstyrene, heptamethyldecasiloxanylstyrene, nylstyrene, heptacosamethyltridecasiloxanylstyrene, hentriacontamethylpentadecasiloxanylstyrene, trimethylsiloxypentamethyldisiloxymethylsilylstyrene, tris(pentamethyldisiloxy)silylstyrene, tris(trimethylsiloxy)siloxybis(trimethylsiloxy)silylstyrene, bis(heptamethyltrisiloxy)methylsilylstyrene, tris[methylbis(trimethylsiloxy)siloxy]silylstyrene, heptakis(trimethylsiloxy)trisilyl silylstyrene, trimethylsiloxybis[tris(trimethylsiloxy)siloxy]silylstyrene, nonamethyltetrasiloxyundecylmethylpentasiloxymethylsilylstyrene, tris[tris(trimethylsiloxy)siloxy]silylstyrene, (tristrimethylsiloxyhexamethyl)tetrasiloxy[tris(trimethylsiloxy)siloxy]trimethylsiloxysilylstyrene, nonakis(trimethylsiloxy)tetrasilylstyrene, bis(tridecamethylhexasiloxy)methylsilylstyrene Silicone-containing styrene derivatives such as styrene, heptamethylcyclotetrasiloxanylstyrene, heptamethylcyclotetrasiloxybis(trimethylsiloxy)silylstyrene, tripropyltetramethylcyclotetrasiloxanylstyrene, and trimethylsilylstyrene; silicone-containing fumaric acid diesters such as bis(3-(trimethylsilyl)propyl)fumarate, bis(3-(pentamethyldisiloxanyl)propyl)fumarate, and bis(tris(trimethylsiloxy)silylpropyl)fumarate;

[0021] Further specific examples of the siloxane monomer include mono(meth)acryloyloxypropyl-terminated mono-n-butyl-terminated polydimethylsiloxane, mono(meth)acryloyloxypropyl-terminated mono-n-methyl-terminated polydimethylsiloxane, mono(meth)acryloyloxypropyl-terminated mono-n-butyl-terminated polydiethylsiloxane, mono(meth)acryloyloxypropyl-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, and mono(meth)acryloylaminopropyl-terminated mono-n-methyl-terminated polydiethylsiloxane. In these siloxane monomers, the number of repetitions of (Si-O) may be, for example, 4-20, preferably 4-12, and more preferably 4-10.

[0022] In one embodiment, a siloxane monomer containing a nitrogen atom is used. The inclusion of a nitrogen atom in the siloxane monomer improves compatibility with the hydrophilic monomer, so that even if the blending ratio of the siloxane monomer is increased, a silicone hydrogel having excellent transparency can be obtained.

[0023] In one embodiment, a siloxane monomer that does not have a hydrophilic group and a siloxane monomer that has a hydrophilic group can be used in combination.By using these two kinds of siloxane monomers in combination, compatibility with the hydrophilic monomer is improved, so that a silicone hydrogel with excellent transparency can be obtained regardless of the presence or absence of a compatible monomer.

[0024] The hydrophilic group may be a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, or the like. Among them, a siloxane monomer having a hydroxyl group is preferable. An example of a siloxane monomer having a hydroxyl group is (3-methacryloxy-2-hydroxypropyloxy)propylbis(trimethylsiloxy)methylsilane (SiGMA).

[0025] The weight average molecular weight of the siloxane monomer is typically 10,000 g / mol or less. In one embodiment, a siloxane monomer having a weight average molecular weight of, for example, 1,000 g / mol or less, preferably 200 g / mol to 900 g / mol, more preferably 300 g / mol to 800 g / mol can be preferably used. By using such a siloxane monomer, the viscosity of the entire polymerizable composition can be reduced, and handling during dispensing into a mold, etc. can be facilitated. In another embodiment, a siloxane monomer having a weight average molecular weight of, for example, more than 1,000 g / mol and 10,000 g / mol or less, preferably 2,000 g / mol to 9,000 g / mol, more preferably 3,000 g / mol to 8,000 g / mol can be preferably used. By using such a siloxane monomer, a higher oxygen permeability improvement effect can be obtained. Only one of these siloxane monomers may be used, or both may be used in combination. By using these two types of siloxane monomers in combination, it is possible to achieve high oxygen permeability while maintaining an appropriate viscosity of the polymerizable composition.

[0026] The number of repetitions of the siloxane bond in the siloxane monomer is typically 1500 or less, preferably 100 or less. In one embodiment, a siloxane monomer having a repetition number of the siloxane bond of, for example, 1 to 20, preferably 2 to 20, more preferably 3 to 12, and even more preferably 4 to 10, can be preferably used. By using such a siloxane monomer, the viscosity of the entire polymerizable composition can be reduced, and handling during dispensing into a mold, etc. can be facilitated. In another embodiment, a siloxane monomer having a repetition number of the siloxane bond of, for example, more than 20 and 1500 or less, preferably more than 20 and 100 or less, more preferably more than 20 and 80 or less can be preferably used. By using such a siloxane monomer, a higher oxygen permeability improvement effect can be obtained. These siloxane monomers may be used alone or in combination. By using two kinds of such siloxane monomers in combination, high oxygen permeability can be expressed while maintaining an appropriate viscosity of the polymerizable composition. In these embodiments, the polysiloxane structure contained in the siloxane monomer may be linear or branched. In addition, in this specification, a siloxane monomer containing more than 20 siloxane bonds or a siloxane monomer having a weight average molecular weight of more than 1,000 g / mol is also referred to as a siloxane macromonomer.

[0027] The blending ratio of the siloxane monomer (the total blending ratio when two or more kinds of siloxane monomers are used) can be, for example, 10% by weight to 70% by weight, preferably 15% by weight to 65% by weight, more preferably 20% by weight to 60% by weight, based on the total blending amount of all monomer components and hydrophilic polymers, if any, in the polymerizable composition. If the blending ratio of the siloxane monomer is within this range, a polymer material having high oxygen permeability can be obtained.

[0028] When a siloxane macromonomer (for example, a siloxane monomer represented by formula (A)) is used in combination with other siloxane monomers, the mixing ratio of the siloxane macromonomer can be preferably 20% by weight or less, more preferably 5% by weight to 15% by weight, based on the total siloxane monomers (the total of the siloxane macromonomer and other siloxane monomers).

[0029] When a siloxane monomer having a hydrophilic group and a siloxane monomer not having a hydrophilic group are used in combination, the mixing ratio of the siloxane monomer having a hydrophilic group can be preferably 1 wt % to 60 wt %, more preferably 5 wt % to 50 wt %, based on the total siloxane monomers (the total of the siloxane monomers having a hydrophilic group and the siloxane monomers not having a hydrophilic group).

[0030] A-1-2. Non-siloxane-containing crosslinkable monomer The siloxane-free crosslinking monomer does not have a siloxane bond and has two or more polymerizable groups. In the embodiment of the present invention, one feature is that an alkylene glycol chain-containing crosslinking monomer having a chain portion containing six or more alkylene glycol repeating units and polymerizable groups arranged at both ends of the chain portion is used as the siloxane-free crosslinking monomer. If necessary, a crosslinking monomer other than the alkylene glycol chain-containing crosslinking monomer (hereinafter also referred to as a second crosslinking monomer) may be further used as the siloxane-free crosslinking monomer.

[0031] The blending ratio of the non-siloxane-containing crosslinkable monomer (the total blending ratio when two or more types of non-siloxane-containing crosslinkable monomers are used) can be, for example, 2 wt % or more, preferably 2.2 wt % or more, more preferably 3 wt % to 25 wt %, and even more preferably 3 wt % to 20 wt %, based on the total blending amount of all monomer components and hydrophilic polymers, if present, in the polymerizable composition.

[0032] A-1-2-1. Alkylene glycol chain-containing crosslinking monomer The alkylene glycol chain-containing crosslinkable monomer has a chain portion containing 6 or more alkylene glycol repeating units and a polymerizable group arranged at both ends of the chain portion. By using a crosslinkable monomer having a structure in which a polymerizable group is arranged at both ends of a relatively long polyether chain, a hydrophilic network structure is formed by the polyether chain, and a polymer network structure that can suppress the intrusion of hydrophobic molecules such as lipids while maintaining oxygen permeability is formed. As a result, it is presumed that a polymer material that achieves both oxygen permeability and surface hydrophilicity and suppresses the adhesion of lipids can be obtained. In addition, in the embodiment of the present invention, only one type of alkylene glycol chain-containing crosslinkable monomer may be used, or two or more types may be used in combination.

[0033] The alkylene glycol chain-containing crosslinkable monomer preferably has an HLB (Hydrophilic-Lipophilic Balance) of 5 to 20, more preferably 5.5 to 18, and even more preferably 6 to 15. If the HLB is within this range, the compatibility with the siloxane monomer can be excellent. In this specification, the HLB of the alkylene glycol chain-containing crosslinkable monomer is a value calculated based on the following formula using the Davis method (wherein the number of (EO) groups is 0.33, the number of (PO) groups is -0.15, and the total number of terminal methacryl groups is 0.1). HLB = 7 + Σ (number of hydrophilic groups) + Σ (number of lipophilic groups)

[0034] In one embodiment, the alkylene glycol chain-containing crosslinking monomer may be represented by the following formula (1): P 1 -X-(A 1 O) m1 -[L 1 -(A 2 O) m2 ] n1 -[L 2 -(A 3 O) m3 ] n2 -ZP 2 (1) (In the formula, P 1 and P2 represent polymerizable groups which may be the same or different, A 1 O, A 2 O and A 3 O represents alkylene glycol repeating units which may be the same or different from each other, X represents a single bond, -O-, -NH-, -O-CH2CH2-NH-CO-O- or -O-CH2CH(OH)CH2O-; Z represents a single bond, -NH-, -CH2CH2-NH-CO-O- or -CH2CH(OH)CH2O-; L 1 and L 2 each independently represents a single bond or a divalent linking group, n1 and n2 each independently represent 0 or 1; m1, m2, and m3 each independently represent an integer of 1 or more; However, the relationship m1+m2×n1+m3×n2≧6 is satisfied.)

[0035] In formula (1), P 1 and P 2 The polymerizable group defined as: is preferably a (meth)acryloyl group, a vinyl group or an allyl group, and more preferably a (meth)acryloyl group.

[0036] In formula (1), L 1 and L 2 The linking group defined by is a single bond or a divalent linking group as described above. Examples of the divalent linking group include linear or branched alkylene groups having 1 to 5 carbon atoms. 1 and L 2 The linking group defined as: is preferably a single bond.

[0037] In formula (1), -(A 1 O) m1 -[L 1 -(A 2 O) m2 ] n1 -[L 2 -(A 3 O) m3 ]n2 The chain portion defined by - contains 6 or more alkylene glycol repeating units. The number of alkylene glycol repeating units contained in the chain portion (m1+m2×n1+m3×n2) is preferably 6 to 50, more preferably 6 to 40, even more preferably 6 to 30, even more preferably 6 to 25, and even more preferably 7 to 20. The number of alkylene glycol repeating units contained in the chain portion may be, for example, 8 or more or 9 or more. When the number of repeating units is within this range, an excellent lipid adhesion prevention effect can be obtained.

[0038] The alkylene glycol repeating units may be arranged intermittently or continuously in the chain portion. Preferably, the chain portion contains 6 or more consecutive alkylene glycol repeating units, more preferably 6 to 50 consecutive alkylene glycol repeating units, even more preferably 6 to 40, even more preferably 6 to 30, even more preferably 6 to 25, and even more preferably 7 to 20. The number of consecutive repeating units in the chain portion may be, for example, 8 or more, or 9 or more.

[0039] The alkylene glycol repeating unit contained in the chain portion (in formula (1), A 1 O, A 2 O or A 3 O) is preferably an alkylene glycol repeating unit having 5 or less carbon atoms, more preferably an ethylene glycol repeating unit (EO), a propylene glycol (typically, propane-1,2-diol) repeating unit (PO) and a butylene glycol (typically, 1,3-butanediol or 1,4-butanediol) repeating unit (BO), and further preferably an ethylene glycol repeating unit and a propylene glycol repeating unit. The chain portion may contain only one type of alkylene glycol repeating unit or may contain two or more types. That is, in formula (1), A 1 O, A 2 O or A 3 Each O may be a different alkylene glycol repeating unit or the same alkylene glycol repeating unit.

[0040] Specific examples of the alkylene glycol chain-containing crosslinkable monomer include polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polybutylene glycol di(meth)acrylate, polyethylene glycol-polypropylene glycol di(meth)acrylate, polyethylene glycol-polybutylene glycol di(meth)acrylate, polypropylene glycol-polybutylene glycol di(meth)acrylate, polyethylene glycol-polypropylene glycol-polyethylene glycol-di(meth)acrylate, and the like.

[0041] In addition, in the formula (1), a configuration in which each alkylene glycol repeating unit forms a block structure is shown, but when the alkylene glycol chain-containing crosslinkable monomer contains two or more types of alkylene glycol repeating units, each repeating unit may be arranged randomly.

[0042] The blending ratio of the alkylene glycol chain-containing crosslinkable monomer (the total blending ratio when two or more alkylene glycol chain-containing crosslinkable monomers are used) is, for example, 0.9% by weight or more, or, for example, 1% by weight or more, preferably 2% by weight or more, more preferably 3% by weight to 25% by weight, and even more preferably 3% by weight to 20% by weight, based on the total blending amount of all monomer components and hydrophilic polymers in the polymerizable composition. The blending ratio of the alkylene glycol chain-containing crosslinkable monomer to all monomer components is, for example, 2 mol% to 15 mol%, preferably 4 mol% to 12 mol%, and more preferably 7 mol% to 10 mol%. By using a polymerizable composition containing an alkylene glycol chain-containing crosslinkable monomer at such a blending ratio, a polymer material that has both oxygen permeability and surface hydrophilicity and is suppressed from adhering to lipids can be suitably obtained.

[0043] A-1-2-2. Second crosslinking monomer As the second crosslinking monomer, any suitable siloxane-free crosslinking monomer other than the alkylene glycol chain-containing crosslinking monomer may be used. Specific examples of the second crosslinking monomer include butanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 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, 2,2-bis((meth)acryloyloxyphenyl)hexafluoropropane, 2,2-bis((meth)acryloyloxyphenyl)propane, 1,4-bis(2-(meth)acryloyloxyhexafluoroisopropyl)benzene, 1,3-bis(2-(meth)acryloyloxyhexafluoroisopropyl)benzene, 1,2-bis(2-(meth)acryloyloxyhexafluoroisopropyl)benzene, 1,4-bis(2-(meth)acryloyloxyisopropyl)benzene, 1,3-bis(2-(meth)acryloyloxyisopropyl)benzene, 1,2-bis(2-(meth)acryloyloxyisopropyl)benzene, etc. The second crosslinkable monomer may be used alone or in combination of two or more.

[0044] The mixing ratio of the second crosslinking monomer (when two or more kinds of second crosslinking monomers are used, the total mixing ratio) can be selected so that the total mixing ratio with the alkylene glycol chain-containing crosslinking monomer is, for example, 2% by weight or more, more preferably 2.2% by weight or more, even more preferably 3% by weight to 25% by weight, and even more preferably 3% by weight to 20% by weight, based on the total mixing amount of all monomer components and hydrophilic polymers in the polymerizable composition, if any. The mixing ratio of the second crosslinking monomer alone in the polymerizable composition can be, for example, 0.1% by weight to 10% by weight, or, for example, 0.5% by weight to 5% by weight, based on the total mixing amount of all monomer components and hydrophilic polymers in the polymerizable composition, if any.

[0045] A-1-3. Copolymerizable monomers The copolymerizable monomer is a monomer having a single polymerizable group and no siloxane bond. Specific examples of the copolymerizable monomer include hydrophilic monomers, compatibilizing monomers, and functional monomers.

[0046] The blending ratio of the copolymerizable monomer is, for example, 20% by weight to 70% by weight, preferably 25% by weight to 65% by weight, more preferably 30% by weight to 65% by weight, based on the total blending amount of all monomer components and hydrophilic polymers in the polymerizable composition. The total blending ratio of the siloxane monomer, alkylene glycol chain-containing crosslinkable monomer, hydrophilic monomer, and compatibilizing monomer to the total blending amount of all monomer components and hydrophilic polymers in the polymerizable composition is, for example, 80% by weight or more, preferably 90% by weight or more, more preferably 94% by weight or more, and the upper limit may be 100% by weight, for example, 99.99% by weight or less, or, for example, 99% by weight or less. The total blending ratio of the siloxane monomer, alkylene glycol chain-containing crosslinkable monomer, hydrophilic monomer, and compatibilizing monomer to the total monomer components is, for example, 90% by weight or more, preferably 95% by weight, more preferably 97% by weight or more, and the upper limit may be 100% by weight, for example, 99.99% by weight or less, or, for example, 99% by weight or less.

[0047] A-1-3-1.Hydrophilic monomer The hydrophilic monomer can increase the hydrophilicity of the resulting polymer material. For example, a monomer having a solubility in water at 20° C. of 0.03 g / mL or more, preferably 0.1 g / mL or more, is used as the hydrophilic monomer (excluding those containing silicon atoms and those having two or more polymerizable groups).

[0048] Specific examples of hydrophilic monomers include hydroxyl group-containing alkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, dihydroxypropyl (meth)acrylate, and glycerol mono(meth)acrylate (for example, hydroxyl group-containing alkyl (meth)acrylates in which the alkyl group has 1 to 5 carbon atoms); (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 (for example, alkyl (meth)acrylamides in which the alkyl group has 1 to 5 carbon atoms); N-vinyl lactams such as N-vinyl pyrrolidone, N-vinyl piperidone, and N-vinyl caprolactam; N-methyl lactams such as 1-methyl-3-methylene-2-pyrrolidinone, methyl (meth)acrylate; and alkoxyalkyl (meth)acrylates in which the alkoxyalkyl group has 2 to 4 carbon atoms. Of these, 2-hydroxyethyl (meth)acrylate, N,N-dimethyl (meth)acrylamide, N-vinylpyrrolidone, methoxyethyl acrylate, ethyl acrylate, glycerol mono(meth)acrylate, etc. are preferably used. The hydrophilic monomers can be used alone or in combination of two or more kinds.

[0049] The blending ratio of the hydrophilic monomer in the polymerizable composition (the total blending ratio when two or more hydrophilic monomers are used) is, for example, 10% by weight to 70% by weight, preferably 22% by weight to 65% by weight, more preferably 25% by weight to 60% by weight, based on the total blending amount of all monomer components and hydrophilic polymers, if any, in the polymerizable composition. If the blending ratio of the hydrophilic monomer is within this range, a polymer material having high water content and surface hydrophilicity can be obtained.

[0050] A-1-3-2. Compatibilizing monomer The compatibilizing monomer can improve the compatibility of the siloxane monomer with the hydrophilic monomer and / or hydrophilic polymer. As the compatibilizing monomer, a monomer having a hydrogen-bonding proton-containing group, not having a silicon atom, and having four or more carbon atoms other than the carbon atom contained in the polymerizable group is preferably used.

[0051] The number of carbon atoms contained in the compatibilizing monomer (excluding carbon atoms contained in the polymerizable group) is, for example, 6 or more, preferably 6 to 25, more preferably 7 to 15, and even more preferably 8 to 13. The compatibilizing monomer may have, for example, 4 or more carbon atoms, more preferably 5 to 15, and even more preferably 8 to 13 carbon atoms per hydrogen-bonding proton-containing group.

[0052] The hydrogen-bonding proton-containing group includes a hydroxyl group, a carboxyl group, an amino group, an amide bond, a sulfonic acid group (-SO3H), a urethane bond, a urea bond, and the like. Among them, a hydroxyl group is preferable. The number of hydrogen-bonding proton-containing groups possessed by the compatibilizing monomer is, for example, 1 to 12, preferably 1 to 5, more preferably 1 to 3, and further preferably 1 or 2.

[0053] The solubility of the compatibilizing monomer in water at 20° C. is typically less than 0.03 g / mL, preferably 0.02 g / mL or less, and more preferably 0 g / mL to 0.01 g / mL. The use of a monomer that has a hydrogen-bonding proton-containing group such as a hydroxyl group but is hydrophobic overall can contribute to improving the compatibility of the siloxane monomer with the hydrophilic monomer and / or hydrophilic polymer.

[0054] In one embodiment, the compatibilizing monomer has a hydrophobic group containing two or more carbon atoms, preferably four or more carbon atoms, in addition to the polymerizable group and the hydrogen-bonding proton-containing group. In this embodiment, it is preferable that the compatibilizing monomer has a polymerizable group, an intermediate portion containing a hydrogen-bonding proton-containing group, and a hydrophobic end portion containing two or more carbon atoms, more specifically, that the polymerizable group is disposed at one end portion of the compatibilizing monomer molecule, the hydrophobic group is disposed at the other end portion, and a relatively hydrophilic group containing a hydrogen-bonding proton-containing group is disposed between them. A compatibilizing monomer having a hydrogen-bonding proton-containing group at a position relatively close to a polymerizable group such as a (meth)acryloyl group and a terminal hydrophobic group at a position farther away can contribute to improving the compatibility of the siloxane monomer with a hydrophilic monomer and / or a hydrophilic polymer.

[0055] The compatibilizing monomer in the above embodiment may be represented by formula (B): P 3 -AB (B) (In the formula, P 3 represents a (meth)acryloyl group, A contains a hydrogen-bonding proton-containing group or P 3 represents a divalent atomic group which, together with B represents a hydrocarbon group having 2 to 20 carbon atoms; However, the total number of carbon atoms in A and B is 4 or more.)

[0056] In the above formula (A), the divalent atomic group defined by A is, for example, *-XRa1 -(L a1 ) r1 -[(R a2 ) r2 -(L a2 ) r3 ] r4 - (i) It can be expressed as: (Here, * is P 3 represents a bond with X is O or NR a3 represents R a1 and R a2 each independently represents an alkylene group having 1 to 20 carbon atoms which may have a hydroxyl group, R a3 represents hydrogen or an alkyl group having 1 to 4 carbon atoms, L a1 and L a2 each 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 from 0 to 10; however, R a2 does not have a hydroxyl group, r3 and r4 are not 0, The atomic group (i) has at least one hydrogen-bonding proton-containing group.

[0057] R a1 and R a2 Each 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. a1 and R a2 It is preferable that at least one of R has a hydroxyl group. a1 More preferably, R a1 has a hydroxyl group, and R a2 In an embodiment where r1 is not present (e.g., an embodiment where r1=0 or 1, r2=0, and r3=0), ora1 and R a2 have a hydroxyl group (eg, an embodiment in which r1=1, r2=1, and r3=0 or 1).

[0058] L if present a1 and L a2 may each independently be preferably an ether bond or an ester bond. a1 and R a2 If neither of L a1 and L a2 At least one of these is preferably an amide bond, a urethane bond, or a urea bond.

[0059] The hydrocarbon group defined by B above may be linear, branched, or contain a cyclic structure, and may contain a heteroatom at any position. The heteroatom is not limited as long as the effects of the present invention can be obtained, and examples thereof include halogens such as fluorine. B may be an unsubstituted or fluorine-substituted hydrocarbon group (e.g., an alkyl group) preferably having 4 to 20 carbon atoms, more preferably having 5 to 12 carbon atoms.

[0060] Specific examples of the compatibilizing monomer in the above embodiment are shown in the following formula (I), (V) or (VI). [ka] (In the formula, R 1 represents a hydrogen atom or a methyl group, R 2 and R 3 each independently represents an alkylene group having 1 to 6 carbon atoms, R 4 is a hydrocarbon group having 2 to 20 carbon atoms, -(R 5a ) s -OR 5b , -(R 5a ) s -O(C=O)-R 5b Or -(R 5a ) s-(C=O)OR 5b (wherein R 5a represents an alkylene group having 1 to 4 carbon atoms, R 5b represents a hydrocarbon group having 2 to 20 carbon atoms, and s represents 0 or 1); X 1 is O or NR 6 (where R 6 represents hydrogen or an alkyl group having 1 to 4 carbon atoms), X 2 represents a single bond or an alkylene group having 1 to 3 carbon atoms, X 3 is a single bond, an alkylene group having 1 to 6 carbon atoms, or -(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 a structure represented by the following formulas (II) to (IV): [ka] (where R 7a represents an alkylene group having 1 to 4 carbon atoms, R 7b represents an alkylene group having 1 to 20 carbon atoms, R 8a and R 8b each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and t and u each independently represent 0 or 1; n is an integer from 0 to 10, q1 and q2 are each independently 0 or 1; however, Polymerizable group (CH2=CR 1 The total number of carbon atoms in the residue excluding -CO- is 3 or more, R4 , R 5b , R 6 , R 8a and R 8b Each of the hydrocarbon groups or alkyl groups defined above may independently have a heteroatom.

[0061] With respect to formula (I), R 4 and R 5b Each of the hydrocarbon groups defined by the formula (I) is preferably an aliphatic hydrocarbon group (e.g., an alkyl group) having 2 to 12 carbon atoms, more preferably 3 to 10 carbon atoms, and further preferably 4 to 10 carbon atoms. Each of these hydrocarbon groups may be linear, branched, or may contain a cyclic structure. It is believed that the compatibilizing monomer can exhibit affinity for the siloxane monomer by functioning as a terminal hydrophobic group.

[0062] R 4 or R 5bSpecific examples of the hydrocarbon group defined by the formula (I) include linear alkyl groups 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; branched alkyl groups such as an isopropyl group, a methylpropyl group, a t-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, a dimethyloctyl group, an ethyloctyl group, and a methylnonyl group; cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and cyclononyl group; cycloalkyl ring-containing alkyl groups such as cyclooctylethyl group, cycloheptylmethyl group, cycloheptylethyl group, cyclohexylmethyl group, cyclohexylethyl group, cyclohexylpropyl group, cyclohexylbutyl group, cyclopentylethyl group, cyclopentylpropyl group, cyclopentylbutyl group, cyclopentylpentyl group, cyclobutylpropyl group, cyclobutylbutyl group, cyclobutylpentyl group, cyclopropylbutyl group, cyclopropylpentyl group, and cyclopropylhexyl group; and bridged alicyclic hydrocarbon groups such as norbornyl group, tricyclodecanyl group, tetracyclododecyl group, adamantyl group, methyladamantyl group, ethyladamantyl group, and butyladamantyl group.

[0063] R 6 , R 8a and R 8b Each of the groups is preferably hydrogen or an alkyl group having 1 or 2 carbon atoms.

[0064] X 3 , R 2 , R 3 , R 5a and R7a Each of the alkylene groups defined as: 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.

[0065] R 7b The alkylene group defined by the formula (I) is preferably an alkylene group having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms.

[0066] X 2 and R 2 The total number of carbon atoms contained in the group is preferably 3 or less, more preferably 0 to 2, and further preferably 1 or 2 (for example, X 2 is a methylene group or an ethylene group, and R 2 In an embodiment where q1 is not present (i.e., an embodiment where q1=0), X 2 and R 2 and (b) are both methylene groups. It is believed that the hydroxyl group being located adjacent to the (meth)acryloyl group allows the compatibilizing monomer to exhibit affinity for the hydrophilic monomer and / or hydrophilic polymer.

[0067] X 3 The total number of carbon atoms contained in the group is preferably 0 to 10, more preferably 1 to 5, and even more preferably 1 to 3.

[0068] R 4 , R 5b , R 6 , R 8a and R 8b The heteroatom that may be contained in the hydrocarbon group or alkyl group defined by the formula (I) is not limited as long as the effects of the present invention can be obtained, and examples thereof include halogens such as fluorine. 4 , R 5b , R 6 , R 8a or R 8b The hydrocarbon or alkyl group defined as may be a fluoroalkyl or perfluoroalkyl group.

[0069] n is preferably 0 to 5, and more preferably 0, 1 or 2.

[0070] In one embodiment, in formula (I), R 1 is a hydrogen atom or a methyl group, and X 1 is O and X 2 is a methylene or ethylene group, preferably a methylene group, n is 0, R 4 -(R 5a ) s -OR 5b (where R 5a is a methylene group, s is 1, and R 5b represents a hydrocarbon group having 2 to 20 carbon atoms which may be substituted with fluorine; and q1 is 0 or 1, preferably 0.

[0071] In one embodiment, in formula (I), R 1 is a hydrogen atom or a methyl group, and X 1 is O and X 2 is a methylene or ethylene group, preferably a methylene group, n is 0, R 4 -(R 5a ) s -O(C=O)-R 5b (where R 5a is a methylene group, s is 1, and R 5b represents a hydrocarbon group having 2 to 20 carbon atoms which may be substituted with fluorine; and q1 is 0 or 1, preferably 0.

[0072] In one embodiment, in formula (I), R 1 is a hydrogen atom or a methyl group, and X 1 is O and X 2 is a methylene or ethylene group, preferably a methylene group, n is 0, R 4 represents a hydrocarbon group having 2 to 20 carbon atoms which may be substituted with fluorine, and q1 is 0 or 1, and preferably 0.

[0073] [ka] (In the formula, R 9 represents a hydrogen atom or a methyl group, R 10 is a hydrocarbon group having 4 to 20 carbon atoms, -OR 10b or -R 10a -OR 10b , -R 10a -O(C=O)-R 10b , -R 10a -(C=O)OR 10b Or -R 10a -(C=O)-R 10b (where R 10a represents an alkylene group having 1 to 4 carbon atoms, R 10b represents a hydrocarbon group having 2 to 20 carbon atoms), however, R 10 The total number of carbon atoms contained in the group is 4 or more, R 10 or R 10b The hydrocarbon group defined by may have a heteroatom.

[0074] With respect to formula (V), R 10 or R 10b Each of the hydrocarbon groups defined by is 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, branched, or may contain a cyclic structure. It is believed that the compatibilizing monomer can exhibit affinity for the siloxane monomer by functioning as a terminal hydrophobic group.

[0075] R 10 or R 10b Specific examples of the hydrocarbon group defined by R 4 or R 5b Specific examples of the hydrocarbon group are the same as those defined in the above (provided that they have 4 or more carbon atoms).

[0076] R 10aThe alkylene group defined by the formula (I) 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.

[0077] R 10 or R 10b The heteroatom that may be contained in the hydrocarbon group defined by the formula (I) is not limited as long as the effects of the present invention can be obtained, and examples thereof include halogens such as fluorine. 10 or R 10b The hydrocarbon group defined as can be a fluoroalkyl group or a perfluoroalkyl group.

[0078] [ka] (In the formula, R 11 represents a hydrogen atom or a methyl group, X 4 is O or NR 14 (where R 14 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), R 12 represents an alkylene group having 2 to 14 carbon atoms, X 5 is a single bond, O, or a structure represented by the following formulae (VII) to (IX): [ka] (where R 15a and R 15b each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), R 13 represents a hydrocarbon group having 2 to 20 carbon atoms, however, X 4 When is not NH, X 5 is a structure containing a urethane bond (-NHCOO-) or a urea bond (-NHCONH-), R 12 , R 13 , R 14 , R15a and R 15b may each independently have a heteroatom.

[0079] With respect to formula (VI), R 12 The alkylene group defined by may be linear, branched, or may contain a cyclic structure. 12 is preferably an alkylene group having 2 to 6 carbon atoms, and more preferably an ethylene group, a propylene group, or a butylene group.

[0080] R 13 The hydrocarbon group defined by 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 further preferably 4 to 10 carbon atoms. The hydrocarbon group may be linear, branched, or may contain a cyclic structure. It is believed that the compatibilizing monomer can exhibit affinity for the siloxane monomer by the hydrocarbon group functioning as a terminal hydrophobic group.

[0081] R 13 Specific examples of the hydrocarbon group defined by R 4 or R 5b Specific examples of the hydrocarbon group defined above include those listed above.

[0082] R 14 , R 15a and R 15b Specific examples of the alkyl group defined as above include a methyl group and an ethyl group.

[0083] R 12 , R 13 , R 14 , R 15a and R 15b The heteroatom that may be contained in R is not limited as long as the effects of the present invention can be obtained, and examples thereof include halogens such as fluorine. 12 , R 13 , R 14 , R 15a or R 15bcan be a fluoroalkyl group or a perfluoroalkyl group.

[0084] In another embodiment, the compatibilizing monomer has a (meth)acryloyl group and an alicyclic ring containing 4 or more carbon atoms and at least one hydrogen atom of which is substituted with a hydrogen-bonding proton-containing group. The alicyclic ring may have a carbon number of preferably 5 to 20, more preferably 6 to 15, and even more preferably 8 to 12, and may have a bridged structure. Specific examples of the compatibilizing monomer in this embodiment include (meth)acrylates having a bridged alicyclic group (e.g., an adamantyl group, a norbornyl group, a tricyclodecanyl group, a tetracyclododecyl group, etc.) substituted with one or more hydroxyl groups, more specifically, hydroxy(meth)acryloyloxyadamantane, dihydroxy(meth)acryloyloxyadamantane, etc.

[0085] The blending ratio of the compatibilizing monomer (the total blending ratio when two or more kinds of compatibilizing monomers are used) can be, for example, 1% by weight to 40% by weight, preferably 5% by weight to 35% by weight, more preferably 10% by weight to 30% by weight, based on the total blending amount of all monomer components and hydrophilic polymers, if present, in the polymerizable composition. If the blending ratio of the compatibilizing monomer is within this range, a polymer material having excellent transparency and antifouling properties while maintaining high oxygen permeability can be obtained.

[0086] A-1-3-3.Functional Monomers The functional monomer is added as necessary for the purpose of imparting a predetermined function to the polymer material. Examples of the functional monomer include a polymerizable dye, a polymerizable ultraviolet absorber, and a polymerizable ultraviolet absorbing dye.

[0087] Specific examples of the polymerizable dye include azo-based polymerizable dyes, anthraquinone-based polymerizable dyes, nitro-based polymerizable dyes, phthalocyanine-based polymerizable dyes, etc. These may be used alone or in combination of two or more.

[0088] Specific examples of the polymerizable ultraviolet absorber include benzophenone-based polymerizable ultraviolet absorbers, benzotriazole-based polymerizable ultraviolet absorbers, salicylic acid derivative-based polymerizable ultraviolet absorbers, 2-cyano-3-phenyl-3-(3'-(meth)acryloyloxyphenyl)propenylic acid methyl ester, etc. These can be used alone or in combination of two or more.

[0089] Specific examples of the polymerizable ultraviolet absorbing dye include benzophenone-based polymerizable ultraviolet absorbing dyes, benzoic acid-based polymerizable ultraviolet absorbing dyes, etc. These can be used alone or in combination of two or more kinds.

[0090] The mixing ratio of the functional monomer is, for example, 0.001 to 5% by weight, and preferably 0.05 to 3% by weight, based on the total mixing amount of all monomer components and the hydrophilic polymer, if present, in the polymerizable composition.

[0091] A-1-3-4. Other copolymerizable monomers As the other copolymerizable monomer, any appropriate monomer can be used depending on the purpose. For example, an alkyl (meth)acrylate having an alkyl group with 2 to 5 carbon atoms can be mentioned. The blending ratio of the other copolymerizable monomer is, for example, 0.001% by weight to 5% by weight, preferably 0.05% by weight to 3% by weight, based on the total blending amount of all monomer components and hydrophilic polymers, if present, in the polymerizable composition.

[0092] A-2. Hydrophilic polymer The hydrophilic polymer is typically a non-polymerizable component that does not have a polymerizable group. By polymerizing the monomer component in the presence of the hydrophilic polymer, the polymer containing the structural unit derived from the monomer component and the hydrophilic polymer are highly complexed, and a polymer material having increased surface hydrophilicity can be obtained.

[0093] As the hydrophilic polymer, any suitable polymer capable of imparting surface hydrophilicity to the polymer material can be used. For example, polymers such as polyvinylamide (e.g., polyvinyllactam), polyamide, polylactone, polyimide, and polylactam can be used as the hydrophilic polymer. Among them, polymers containing a cyclic structure, such as a cyclic amide structure or a cyclic imide structure, in the main chain or side chain can be preferably used. The hydrophilic polymer may be a random copolymer, an alternating copolymer, a block copolymer, or a graft copolymer made of two or more monomers. In addition, only one type of hydrophilic polymer may be used, or two or more types may be used in combination.

[0094] Specific examples of hydrophilic polymers include poly-N-vinylpyrrolidone, poly-N-vinyl-2-piperidone, poly-N-vinyl-2-caprolactam, poly-N-vinyl-3-methyl-2-caprolactam, poly-N-vinyl-3-methyl-2-piperidone, poly-N-vinyl-4-methyl-2-piperidone, poly-N-vinyl-4-methyl-2-caprolactam, poly-N-vinyl-3-ethyl-2-pyrrolidone, poly-N-vinyl-4,5-dimethyl-2-pyrrolidone, polyvinyl imidazole, poly-NN-dimethylacrylamide, polyvinyl alcohol, poly(meth)acrylic acid, poly(2-hydroxyethyl)(meth)acrylate, polyalkylene glycols such as polyethylene glycol, poly-2-ethyl oxazoline, heparin polysaccharide, polysaccharides, and copolymers thereof. Among these, poly-N-vinylpyrrolidone, polyalkylene glycol, polysaccharide, poly(meth)acrylic acid, polyvinyl alcohol, poly(2-hydroxyethyl)(meth)acrylate, and the like can be preferably used.

[0095] The weight average molecular weight of the hydrophilic polymer is, for example, 100,000 or more, preferably 150,000 to 2,000,000, more preferably 300,000 to 1,800,000, and even more preferably 500,000 to 1,500,000.

[0096] The K value of the hydrophilic polymer may be, 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 Viscosity Measurement Method 1 <2.53> in the Japanese Pharmacopoeia, 16th Edition, and calculating it using the Fikentscher formula according to the method described in the "K value" column in the Pharmacopoeia.

[0097] The blending ratio of the hydrophilic polymer in the polymerizable composition can be typically 1% by weight to 30% by weight, preferably 3% by weight to 25% by weight, more preferably 4% by weight to 20% by weight, based on the total blending amount of all monomer components and hydrophilic polymer in the polymerizable composition. If the blending amount of the hydrophilic polymer is within this range, a polymer material having a high water content and excellent surface hydrophilicity can be obtained.

[0098] A-3. Additives Any appropriate additive may be selected depending on the purpose. Examples of the additive include a polymerization initiator and an organic solvent.

[0099] The polymerization initiator is appropriately selected depending on the polymerization method. Examples of the thermal polymerization initiator used in polymerization by heating include 2,2'-azobisisobutyronitrile, 2,2'-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 can be used alone or in combination of two or more.

[0100] The blending ratio of the thermal polymerization initiator in the polymerizable composition is preferably 0.001 to 3% by weight, more preferably 0.01 to 2% by weight, based on all components in the polymerizable composition (excluding the organic solvent).

[0101] Examples of photopolymerization initiators used in polymerization by irradiation with light 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 orthobenzoyl benzoate, methyl benzoyl formate, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzoin-n-butyl ether; 2-hydroxy-2-methyl-1-phenylpropan-1-one (HMPPO), p-isopropyl ether, and the like. Examples of the photopolymerization initiator include phenone-based photopolymerization initiators such as p-α-hydroxyisobutylphenone, pt-butyltrichloroacetophenone, 2,2-dimethoxy-2-phenylacetophenone, α,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; dibenzosubalone; 2-ethylanthraquinone; benzophenone acrylate; benzophenone; and benzyl. These photopolymerization initiators can be used alone or in combination of two or more. A photosensitizer may also be used together with the photopolymerization initiator.

[0102] The blending ratio of the photopolymerization initiator and photosensitizer in the polymerizable composition is preferably 0.001 to 2% by weight, more preferably 0.01 to 1% by weight, based on all components in the polymerizable composition (excluding the organic solvent).

[0103] The organic solvent may be a water-soluble organic solvent having high polarity, or a water-insoluble organic solvent having low polarity. Examples of the water-soluble organic solvent include alcohols having 1 to 4 carbon atoms, acetone, methyl ethyl ketone, dimethylformamide, dimethyl sulfoxide, acetonitrile, N-methyl-2-pyrrolidone, dimethoxyethane, tetrahydrofuran, and 1,4-dioxane. By using a water-soluble organic solvent, the compatibility between the monomer components or between the hydrophilic polymer and 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.

[0104] Examples of the non-water-soluble organic solvent that can be used include hexane, cyclohexane, heptane, octane, dimethyl ether, diethyl ether, benzene, toluene, xylene, ethyl acetate, propyl acetate, butyl acetate, dichloromethane, chloroform, carbon tetrachloride, and alcohols having 6 or more carbon atoms. By using a non-water-soluble organic solvent, the compatibility between the monomer components or between the hydrophilic polymer and the monomer components can be improved. In addition, when added to the polymerizable composition, the kinetic viscosity of the polymerizable composition is lower than that when a water-soluble organic solvent is used, making it easier to handle.

[0105] The amount of the organic solvent in the polymerizable composition can be, for example, 50% by weight or less, preferably 40 parts by weight or less, and more preferably 30 parts by weight or less, based on all components (including the organic solvent) in the polymerizable composition.

[0106] As additives other than those mentioned above, additives conventionally used in ophthalmic lenses can be used, such as cooling agents, thickening agents, surfactants, non-polymerizable dyes, ultraviolet absorbers or ultraviolet absorbing dyes.

[0107] The blending ratio of the other additives in the polymerizable composition can be, for example, 0.001% by weight to 5% by weight, and preferably 0.005% by weight to 3% by weight, based on all components in the polymerizable composition (excluding the organic solvent).

[0108] B. Polymerization method The polymer material can be obtained, for example, by heating and / or irradiating a polymerizable composition containing the above components with light (ultraviolet light and / or visible light) to polymerize the monomer components in the polymerizable composition. Alternatively, the polymer material can be obtained by polymerization using electron beam irradiation instead of light irradiation.

[0109] As the polymerization method, bulk polymerization or solution polymerization can be used. In bulk polymerization, a part of the monomer components may remain unpolymerized. In solution polymerization, a solvent that is not involved in the reaction may remain in the obtained polymer. In the manufacture of medical devices such as contact lenses, in order to reduce these residues as much as possible, the obtained polymer material may be immersed in water, an organic solvent, or a mixture thereof, preferably repeatedly, to dissolve and remove these residues from the polymer material.

[0110] When the polymer material is used for contact lenses, etc., the polymerizable composition can be reacted by a casting method to form a desired shape (e.g., a hemispherical shape). When the polymerizable composition is heated and polymerized by the casting method, the polymerizable composition is filled into a mold corresponding to the shape of the desired ophthalmic lens material, and the mold is gradually heated.

[0111] The heating temperature and heating time when the polymerizable composition in the mold is heated are appropriately set according to the composition of the polymerizable composition, etc. The heating temperature is preferably 50° C. or more and 150° C. or less, more preferably 60° C. or more and 140° C. or less. The heating time when the polymerizable composition in the mold is heated is preferably 10 minutes or more and 120 minutes or less, more preferably 20 minutes or more and 60 minutes or less.

[0112] In the case of polymerizing the polymerizable composition by light irradiation in the mold method, the polymerizable composition is filled into a mold corresponding to the shape of the desired 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 the light necessary for polymerization.

[0113] The wavelength of the light irradiated to the polymerizable composition in the mold is appropriately set depending on the type of photopolymerization initiator used, etc. The light illuminance and irradiation time are appropriately set depending on the composition of the polymerizable composition, etc. The light illuminance is preferably 0.1 mW / cm 2 ~100mW / cm 2 The irradiation time is preferably 1 minute or more. Light with different illuminance may be irradiated in stages.

[0114] Polymerization by the above-mentioned mold method can obtain a polymer material having a desired shape. The obtained polymer material as a molded body may be subjected to mechanical processing such as cutting and polishing, if necessary. Cutting may be performed over the entire surface of one or both sides of the polymer material, or may be performed on a part of one or both sides of the polymer material.

[0115] The above polymer materials can be subjected to surface modification treatments such as low-temperature plasma treatment, atmospheric pressure plasma, and corona discharge for the purpose of surface modification.

[0116] C. Polymer Material Properties The Young's modulus of the polymer material in one embodiment of the present invention is preferably 0.3 MPa to 2.3 MPa, more preferably 0.3 MPa to 1.2 MPa. By using a polymer material having such a Young's modulus, an ophthalmic lens having excellent wearing comfort and handling properties when processed into a contact lens can be obtained.

[0117] The stress relaxation rate of the polymer material in one embodiment of the present invention is preferably 10% to 40%, more preferably 10% to 30%. By using a polymer material having such a stress relaxation rate, an ophthalmic lens having excellent comfort when worn and ease of handling when processed into a contact lens can be obtained.

[0118] The oxygen permeability coefficient (Dk value) of the polymer material in one embodiment of the present invention is preferably 20 Barrer or more, more preferably 30 Barrer or more, and further preferably 50 to 150 Barrer.

[0119] In one embodiment of the present invention, the water content of the polymer material is preferably 11% by weight or more, more preferably 30% by weight or more, and even more preferably 30% by weight to 70% by weight. By making the water content of the polymer material 11% by weight or more, the obtained polymer material can be made into a hydrogel, and the wearing comfort when processed into a contact lens can be improved, and the strength, oxygen permeability, and surface hydrophilicity can be set in a well-balanced manner. EXAMPLES

[0120] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In the examples and comparative examples, "parts" and "%" are by weight unless otherwise specified.

[0121] [Ingredients used] The meanings of the abbreviations of the components used in the following Examples and Comparative Examples are shown below. <Siloxane monomer> AA-PDMS: A polymerizable compound with the structure shown below. [ka] MAUS: a polymerizable compound having the structure shown below (wherein n=approximately 40) [ka] SiGMA: (3-methacryloxy-2-hydroxypropyloxy)propylbis(trimethylsiloxy)methylsilane (structure shown below) [ka] <Crosslinking monomer> EDMA: Ethylene glycol dimethacrylate (HLB: 7.43) TEGMA: Tetraethylene glycol methacrylate (HLB: 8.42) PEGDMA (n=6): Hexaethylene glycol dimethacrylate (HLB: 9.08) PEGDMA (n = 9): polyethylene glycol dimethacrylate (EO repeat number: 9, HLB: 10.07, manufactured by Shin-Nakamura Chemical Co., Ltd., "NK Ester 9G") PEGDMA (n = 14): polyethylene glycol dimethacrylate (EO repeat number: 14, HLB: 11.72, Shin-Nakamura Chemical Co., Ltd., "NK Ester 14G") PEGDMA (n = 23): polyethylene glycol dimethacrylate (EO repeat number: 23, HLB: 14.69, Shin-Nakamura Chemical Co., Ltd., "NK Ester 23G") 9PG (n = 7): Polypropylene glycol dimethacrylate (PO repeat number: 7, HLB: 6.05, Shin-Nakamura Chemical Co., Ltd., "NK Ester 9PG") 25PDC: Polyethylene glycol polypropylene glycol dimethacrylate (EO repeat number: 8, PO repeat number: 9, AO repeat structure: EO-PO-EO block type, HLB: 8.39, NOF Corp., "25PDC-900B") 40PDC: Polyethylene glycol polypropylene glycol dimethacrylate (EO repeat number: 15, PO repeat number: 18, AO repeat structure: EO-PO-EO block type, HLB: 9.35, NOF Corp., "40PDC-1700B") ·AMA: Allyl methacrylate <Compatibilizing monomer> EH(OH)MA: A polymerizable compound having the structure shown below (solubility in water at 20°C: less than 0.01 g / mL) [ka] <Hydrophilic Monomer> ·DMAA: N,N-Dimethylacrylamide HEMA: 2-hydroxyethyl methacrylate ·N-VP: N-vinyl-2-pyrrolidone · 2-MTA: Methoxyethyl acrylate <Functional Monomer> HMEPBT: Benzotriazole-based polymerizable UV absorber (2-(2'-hydroxy-5'-methacryloyloxyethylphenyl)-2H-benzotriazole) RB246: Anthraquinone-based polymerizable dye <Hydrophilic polymer> PVP K-90: ​​Polyvinylpyrrolidone (Mw=1,000,000~1,500,000) <Additives> ·TPO: Initiator (2,4,6-trimethylbenzoyl-diphenylphosphine oxide) IPA: Isopropyl alcohol

[0122] [Synthesis Example 1: Preparation of EH(OH)MA] 1) Ethylhexyl glycidyl ether, methacrylic acid, tetrabutylammonium bromide, and p-methoxyphenol were added to a brown recovery flask and dissolved. A Dimroth condenser was then attached and the mixture was stirred overnight at 90°C 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 solution. 4) The hexane layer was washed with distilled water. 5) The hexane layer was washed with saturated saline. 6) The hexane layer was collected, dried by adding an appropriate amount of sodium sulfate, and left to stand for a while. 7) The sodium sulfate was removed by filtration. 8) The hexane layer was concentrated under reduced pressure to give a slightly yellowish transparent liquid. 1 1 H NMR (CDCl3, 400 MHz) and gas chromatography were measured, and it was confirmed that the desired compound was obtained.

[0123] [Synthesis Example 2: Preparation of hexaethylene glycol dimethacrylate] 1) Hexaethylene glycol and methacrylic acid were added to a brown recovery flask and dissolved, and a small amount of sulfuric acid was added, followed by stirring for 4 hours in an oil bath at 100°C. 2) The reaction solution was returned to room temperature, dissolved in a toluene-hexane mixed solvent, and transferred to a separatory funnel. 3) The organic layer was washed with an aqueous solution of sodium bicarbonate. 4) The organic layer was washed with distilled water. 5) The organic layer was washed with saturated saline. 6) The organic layer was collected, dried over an appropriate amount of sodium sulfate, and left to stand for a while. 7) The sodium sulfate was removed by filtration. 8) The organic layer was concentrated under reduced pressure to give a colorless, transparent liquid. 1 1 H NMR (CDCl3, 400 MHz) and gas chromatography were measured, and it was confirmed that the desired compound was obtained.

[0124] [Example 1-A] A polymerizable composition was prepared by mixing 30 parts by weight of AA-PDMS as a siloxane monomer, 25.5 parts by weight of EH(OH)MA as a compatibilizing monomer, 26 parts by weight of DMAA and 5 parts by weight of HEMA as hydrophilic monomers, 3.6 parts by weight of PEGDMA (E=6) as a crosslinking monomer, 1.8 parts by weight of HMEPBT as a polymerizable ultraviolet absorber, 0.01 parts by weight of RB246 as a polymerizable dye, 7 parts by weight of PVP K-90 (manufactured by BASF) as a hydrophilic polymer, 0.4 parts by weight of TPO as a polymerization initiator, and 20 parts by weight of IPA as a solvent. The obtained polymerizable composition was poured into a mold (made of polypropylene, corresponding to a contact lens with a diameter of 14.2 mm and a thickness of 0.08 mm) having a contact lens shape. Next, the mold was irradiated with LED light at room temperature to perform photopolymerization. After polymerization, the polymer material in the shape of a contact lens was taken out of the mold. This resulted in a silicone hydrogel contact lens.

[0125] [Examples 1-B to 4-A, Comparative Examples 1-A to 3-B] A silicone hydrogel contact lens was obtained in the same manner as in Example 1-A, except that the components were mixed to obtain the compositions shown in Tables 1 to 4 to prepare polymerizable compositions.

[0126] [Table 1]

[0127] [Table 2]

[0128] [Table 3]

[0129] [Table 4]

[0130] The contact lenses obtained in the above examples and comparative examples were immersed in distilled water and swollen to equilibrium, then replaced with pH 7.5 phosphate buffer and swollen to equilibrium.Then, the same amount of the phosphate buffer was replaced, autoclave sterilized at 121°C for 20 minutes, and the following characteristic evaluation was performed.However, in the measurement of oxygen permeability coefficient, polymerization, hydration and sterilization were performed in the same manner as above, except that a PP mold that can obtain a plate-shaped sample with an average thickness of about 0.3 mm was used instead of a mold having a contact lens shape, and a plate-shaped sample processed into a circle with a diameter of 14.0 mm was used.The evaluation results are shown in Figure 1.

[0131] <Evaluation of lipid adhesion> 1) Artificial lipid (product name: Pharmasol), which is solid at room temperature, was heated to 60°C to melt it, and 1.7 mL was placed in each well per lens. 2) The moisture on the surface of the contact lenses was wiped off, and they were then placed in each well and left in a dryer at 60°C for 1 hour. 3) The contact lens was removed from the well and rinsed in a beaker containing contact lens cleaning solution (Menicon Co., Ltd., product name "Epica Cold"), and then both sides were scrubbed with contact lens cleaning solution (Menicon Co., Ltd., product name "Epica Cold") or with hot water 20 times per side. 4) Contact lens cleaning solution (Menicon Co., Ltd., product name "Epica Cold") and contact lenses were placed in each well of a multi-well plate and left to stand at 10°C for 4 hours. The contact lenses were then removed from the wells and scrubbed, and then left to stand overnight. 5) The contact lenses were removed from the wells and further scrubbed, after which the appearance was checked with the naked eye and evaluated based on the following criteria. Microscopic photographs of each lens are shown in Figure 1. [Judgment criteria] 0: Almost no white observed 1: A small part is observed as white. 2: Approximately 50% of the total area is observed as white. 3: The lens is observed to be white over almost the entire surface, with some areas of light turbidity. 4: The entire lens is white.

[0132] <Measurement of tensile modulus (Young's modulus)> The contact lenses thus produced were punched out to produce dumbbell-shaped samples with an extension width of approximately 1.8 mm and a thickness of approximately 0.1 mm, which were used as test samples. A tensile test was carried out in physiological saline at 20°C using a Shimadzu precision universal testing machine, Autograph AG-IS MS type, manufactured by Shimadzu Corporation, and the Young's modulus (MPa) was calculated as the tensile modulus of elasticity from the stress-elongation curve. The tensile speed was 100 mm / min.

[0133] <Measurement of stress relaxation rate> The stress relaxation rate was measured using the same measuring equipment as used for measuring the tensile modulus and a jig as shown in Fig. 2. Specifically, the center of the prepared contact lens C was pressed into physiological saline with a test force of 0.1 N using an indenter P with a tip PT having a diameter of about 1.6 mm, and the stress relaxation rate (%) was calculated from the change in stress after maintaining the stroke for 1 minute.

[0134] 1, the contact lenses of the Examples have less adhesion of lipids than the contact lenses of the Comparative Examples. It is also clear that the contact lenses of the Examples have preferable Young's modulus and stress relaxation rate for contact lenses, and are excellent in handleability and wearing comfort.

[0135] ≪Moisture content measurement≫ The water content of the contact lens obtained in Example 1-C was measured. Specifically, the moisture on the surface of a contact lens adjusted in a pH 7.5 phosphate buffer solution at 20°C was gently wiped off, and the mass (W(g)) in an equilibrium water content state was measured. The lens was then dried in a dryer set at 105°C, and the mass (W0(g)) after being allowed to cool was measured. Using these measured values ​​W0 and W, the water content (mass%) was calculated according to the following formula. As a result, the water content of the contact lens obtained in Example 1-C was 37%. Moisture content (mass%)={(W-W0) / W}×100

[0136] <Oxygen permeability coefficient (Dk value) measurement> The Dk value was measured using the circular plate-shaped sample having a diameter of 14.0 mm obtained in Example 1-C as the measurement sample. Specifically, a similar plate-type sample was prepared as a reference standard using the material "2WEEK Menicon Premio" (manufactured by Menicon Co., Ltd.), and its Dk value was set to 129. The measurement sample was set on the electrodes, and a Seikaken film oxygen permeability meter (manufactured by Rika Seiki Kogyo Co., Ltd.) was used to bubble nitrogen into physiological saline at 35°C, and the current value was set to zero when equilibrium was reached. Next, the current value was recorded when equilibrium was reached by bubbling oxygen. This was also performed on the reference standard. The oxygen permeability coefficient of the lens was calculated according to the following formula. The unit of oxygen permeability coefficient is (×10 -11 (cm 2 / sec)·(mLO2 / (mL×mmHg)))=Barrer). As a result, the Dk value of the measured sample was 78 Barrer. Dk value=R×(IS / IR)×(TS / TR)×(PR / PS) Here, the meanings of the symbols in the above formula are as follows: R: Dk value of the reference standard (129) IS: Current value of the measurement sample (μA) IR: Reference standard current value (μA) TS: Average thickness of the measured sample (mm) TR: average thickness of the reference standard (mm) PS: Atmospheric pressure (mmHg) when measuring the sample PR: Atmospheric pressure at the time of reference standard measurement (mmHg) [Industrial Applicability]

[0137] The ophthalmic lens of the present invention is suitably used for ophthalmic lenses such as contact lenses, artificial corneas, and corneal onlays.

Claims

1. An ophthalmic lens comprising a polymer material obtained by polymerizing a polymerizable composition containing, as monomer components, a siloxane monomer having a siloxane bond, a copolymerizable monomer including a compatibilizing monomer and a hydrophilic monomer, and a siloxane-free crosslinkable monomer having no siloxane bond, the compatibilizing monomer has a hydrogen-bonding proton-containing group, has no silicon atom, and has four or more carbon atoms other than the carbon atom contained in the polymerizable group; The ophthalmic lens, wherein the siloxane-free crosslinkable monomer comprises an alkylene glycol chain-containing crosslinkable monomer having a chain portion containing 6 or more alkylene glycol repeating units and polymerizable groups located at both ends of the chain portion.

2. 2. The ophthalmic lens according to claim 1, wherein the chain portion of the alkylene glycol chain-containing crosslinkable monomer contains 6 to 50 alkylene glycol repeating units.

3. 3. The ophthalmic lens according to claim 1, wherein the alkylene glycol repeating unit comprises at least one selected from the group consisting of an ethylene glycol repeating unit, a propylene glycol repeating unit, and a butylene glycol repeating unit.

4. 4. The ophthalmic lens according to claim 1, wherein the hydrophilic monomer comprises at least one selected from the group consisting of hydroxyl group-containing alkyl (meth)acrylates, (meth)acrylamides, N-vinyl lactams, N-methyl lactams, methyl (meth)acrylates, and alkoxyalkyl (meth)acrylates.

5. The ophthalmic lens of claim 1 , wherein the polymerizable composition further comprises a hydrophilic polymer.

6. a mixing ratio of the non-siloxane-containing crosslinkable monomer to a total amount of all monomer components and the hydrophilic polymer in the polymerizable composition is 2% by weight or more; 6. The ophthalmic lens according to claim 5, wherein a mixing ratio of the alkylene glycol chain-containing crosslinkable monomer to a total mixing amount of all monomer components and the hydrophilic polymer in the polymerizable composition is 0.9% by weight or more.

7. 7. The ophthalmic lens according to claim 5, wherein a mixing ratio of the alkylene glycol chain-containing crosslinkable monomer to a total mixing amount of all monomer components and the hydrophilic polymer in the polymerizable composition is 2% by weight or more.

8. 8. The ophthalmic lens according to claim 5, wherein a mixing ratio of the copolymerizable monomer to a total mixing amount of all monomer components and the hydrophilic polymer in the polymerizable composition is 20% by weight to 70% by weight.

9. 9. The ophthalmic lens according to claim 5, wherein the hydrophilic polymer comprises at least one selected from poly-N-vinylpyrrolidone, polyalkylene glycol, polysaccharide, poly(meth)acrylic acid, and polyvinyl alcohol.

10. 10. The ophthalmic lens according to claim 1, wherein the alkylene glycol chain-containing crosslinkable monomer has an HLB value of 5 to 20.

11. 11. The ophthalmic lens according to claim 1, wherein a mixing ratio of the siloxane monomer to a total mixing amount of all monomer components and the hydrophilic polymer in the polymerizable composition is 10% by weight to 70% by weight.

12. 12. The ophthalmic lens according to claim 1, wherein the siloxane monomer has a repeating number of siloxane bonds of 100 or less.

13. 13. The ophthalmic lens according to claim 1, wherein the siloxane monomer has a repeating number of siloxane bonds of 20 or less.

14. 14. The ophthalmic lens according to claim 1, wherein the weight average molecular weight of the siloxane monomer is 10,000 or less.

15. 15. The ophthalmic lens according to claim 1, wherein the weight average molecular weight of the siloxane monomer is 1,000 or less.

16. The siloxane monomer includes a siloxane monomer A having a weight average molecular weight of 1,000 or less and a siloxane monomer B having a weight average molecular weight of more than 1,000, 16. The ophthalmic lens according to claim 1, wherein a ratio of the siloxane monomer B to the total of the siloxane monomer A and the siloxane monomer B is 20% by weight or less.

17. 17. The ophthalmic lens according to claim 1, wherein the polymer material has a stress relaxation rate of 10% to 40%.

18. 18. An ophthalmic lens according to any one of claims 1 to 17, wherein the polymer material has a Young's modulus of 0.3 MPa to 2.3 MPa.

19. 19. An ophthalmic lens according to any one of claims 1 to 18, wherein the water content of the polymeric material is 11% by weight or more.

20. 20. An ophthalmic lens according to any one of claims 1 to 19 which is a contact lens.

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