Eye lenses

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 Art

[0002] Contact lenses are roughly classified into hard contact lenses and soft contact lenses. In recent years, many hard contact lenses are formed using a siloxane polymer having a siloxane bond (Si—O—Si), and thus have high oxygen permeability. However, due to their hardness, they may cause a foreign body sensation during wearing. On the other hand, soft contact lenses are formed from a water-containing hydrogel using a copolymer polymer having a hydrophilic monomer and a (meth)acrylic monomer as copolymerization components, and thus an excellent wearing feeling can be obtained. However, they tend to have lower oxygen permeability than hard contact lenses. In contrast, contact lenses that achieve both high oxygen permeability and excellent wearing feeling have been developed using a silicone hydrogel containing a siloxane monomer as a further copolymerization component (Patent Document 1).

[0003] However, contact lenses formed from silicone hydrogel tend to have lipids adhering to their surfaces. Therefore, there is a demand for the realization of contact lenses that achieve both high oxygen permeability and excellent wearing feeling and suppress the adhesion of lipids.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] A main object of the present invention is to provide an ophthalmic lens that achieves both oxygen permeability and wearing feeling and suppresses the adhesion of lipids.

Means for Solving the Problems

[0006] According to one aspect of the present invention, an ophthalmic lens is provided, comprising a polymer material obtained by polymerizing a polymerizable composition comprising, as a monomer component, a siloxane monomer having a siloxane bond and a siloxane-free crosslinkable monomer not having a 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 disposed 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 repeating alkylene glycol units. In one embodiment, the alkylene glycol repeating unit includes 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 proportion of the siloxane-free crosslinkable monomer relative to the total amount of all monomer components and the hydrophilic polymer (if present) in the polymerizable composition is 2% by weight or more, and the proportion of the alkylene glycol chain-containing crosslinkable monomer relative to the total amount of all monomer components and the hydrophilic polymer (if present) in the polymerizable composition is 0.9% by weight or more. In one embodiment, the proportion of the alkylene glycol chain-containing crosslinkable monomer to the total 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 proportion of the alkylene glycol chain-containing crosslinkable monomer to the total amount of all monomer components and the hydrophilic polymer (if present) in the polymerizable composition is 3% to 25% by weight. In one embodiment, the HLB value of the alkylene glycol chain-containing crosslinkable monomer is 5 to 20. In one embodiment, the proportion of the siloxane monomer to the total amount of all monomer components and the hydrophilic polymer (if present) in the polymerizable composition is 10% to 70% by weight. In one embodiment, the siloxane monomer has a single polymerizable group. In one embodiment, the number of repeating siloxane bonds in the siloxane monomer is 100 or less. In one embodiment, the number of repeating siloxane bonds in the siloxane monomer is 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 comprises siloxane monomer A having a weight-average molecular weight of 1,000 or less and siloxane monomer B having a weight-average molecular weight of more than 1,000, wherein the ratio of siloxane monomer B to the total of siloxane monomer A and 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 is a hydroxyl group-containing alkyl (meth)acrylate or (meth)acrylamide. kind It comprises at least one hydrophilic monomer selected from N-vinyl lactam, N-methyl lactam, methyl (meth)acrylate, and alkoxyalkyl (meth)acrylate. In one embodiment, the proportion of the copolymerizable monomer to the total amount of all monomer components and the hydrophilic polymer (if present) in the polymerizable composition is 20% 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 stress relaxation rate of the polymer material is 10% to 40%. In one embodiment, the Young's modulus of the polymer material is 0.3 MPa to 2.3 MPa. In one embodiment, the ophthalmic lens is a contact lens. [Effects 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 crosslinkable monomer, it is possible to obtain an ophthalmic lens that balances oxygen permeability and wearing comfort while suppressing lipid adhesion. Furthermore, the ophthalmic lens obtained according to the present invention may have appropriate flexibility and deformation recovery properties to ensure good handling. [Brief explanation of the drawing]

[0008] [Figure 1] This figure shows the evaluation results of ophthalmic lenses obtained in the examples and comparative examples. [Figure 2] This diagram illustrates the jig used in measuring the stress relaxation rate. [Modes for carrying out the invention]

[0009] In this specification, “monomer” means a polymerizable compound having one or more polymerizable groups. Preferably, the polymerizable group is 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. Therefore, “(meth)acryloyl” means methacryloyl and / or acryloyl. The same applies to other descriptions such as “(meth)acrylic.”

[0010] An ophthalmic lens according to an embodiment of the present invention comprises a polymer material obtained by polymerizing a polymerizable composition containing a siloxane monomer having siloxane bonds and a siloxane-free crosslinkable monomer that does not have siloxane bonds, wherein at least an alkylene glycol chain-containing crosslinkable monomer having a chain portion containing 6 or more alkylene glycol repeating units and polymerizable groups disposed at both ends of the chain portion is used as the siloxane-free crosslinkable monomer. An ophthalmic lens according to an embodiment of the present invention typically has a hemispherical shape that follows the curvature of the cornea. An ophthalmic lens according to an embodiment of the present invention can be used, for example, as a contact lens, an artificial cornea, or a corneal onlay, and is preferably a silicone hydrogel contact lens.

[0011] The following describes specific embodiments of the present invention, but the present invention is not limited to these embodiments. Furthermore, each embodiment can be combined as appropriate.

[0012] A. Polymerizable composition The polymerizable composition comprises, as monomer components, a siloxane monomer having siloxane bonds and a siloxane-free crosslinkable monomer not having siloxane bonds, wherein 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 positioned at both ends of the chain portion. The monomer components preferably further include copolymerizable monomers. In one embodiment, the copolymerizable monomer includes a hydrophilic monomer. In one embodiment, the copolymerizable monomer includes a compatibilizer monomer. The polymerizable composition may further include a hydrophilic polymer. By polymerizing the polymerizable composition containing monomer components and a hydrophilic polymer, a polymer material can be obtained in which a polymer containing structural units derived from the monomer components and a hydrophilic polymer component are highly composited. The polymerizable composition may also further include any suitable additives as needed.

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

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

[0015] Examples of siloxane monomers include monomers conventionally used as materials for contact lenses, such as the siloxane monomers described in paragraphs 0039 to 0044 of Japanese Patent Publication No. 2015-503631, the siloxane monomers described in paragraphs 0060 to 0065 of Japanese Patent Application Publication No. 2014-40598, and the siloxane monomers described in paragraphs 0024 to 0037 of Japanese Patent Application Publication No. WO2015 / 92858 (specifically, siloxane monomers represented by the following formula (A), preferably formula (A-1), (A-2), or (A-3)). These publications are incorporated herein by reference in their entirety.

[0016] [ka] In the above general formula (A), 1) n is 0 or an integer between 1 and 10. 2) A 1 and A 2are each a group represented by the following general formula (A-II) and (A-III). In the following general formula (A-II) and general formula (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 an alkylene group having a linear or branched chain with 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. However, at least one of Z 1 to Z 6 is a polyethylene glycol chain having a repeating number of ethylene glycol of 2 or more, preferably 4 to 15, and at least one of Z 1 to Z 6 is a polyalkylene glycol chain having an alkylene glycol different from ethylene glycol as a repeating unit (for example, a polypropylene glycol chain having propylene glycol as a constituent unit, and as a specific example, a polypropylene glycol chain having a repeating number of propylene glycol of 5 to 16). 4) U 1 is a group represented by the following general formula (A-IV) and contains a urethane bond in the molecular chain of the siloxane monomer. In the following general formula (A-IV), E 21 is a -NHCO- group (in this case, E 21 is X 21(forming a urethane bond with) or a divalent group derived from a diisocyanate selected from the group of saturated or unsaturated aliphatic, alicyclic and aromatic (in this case, E 21 is Z 1 and X 21 (A urethane bond is formed between them) and X 21 It is an oxygen atom. -E 21 -X 21 - ···(A-IV) 5)U 2 R is a group represented by the following general formula (A-VI) and contains a urethane bond in the molecular chain of the siloxane monomer. In the following general formula (A-VI), R 41 and R 42 Each of these is an alkylene group having a linear or branched chain with 2 to 6 carbon atoms, and X 41 and X 42 Each is independently an oxygen atom or an alkylene glycol group, and E 41 This is a divalent group (in this case, E) derived from diisocyanates selected from the group of saturated or unsaturated aliphatic, alicyclic, and aromatic. 41 is X 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 X is a group represented by the following general formula (A-VII) and 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, E 22 is an -NHCO- group (in this case, E 22 is X 22 (forming a urethane bond with) or a divalent group derived from a diisocyanate selected from the group of saturated or unsaturated aliphatic, alicyclic and aromatic (in this case, E 22 is Z 5 and X 22(A urethane bond is formed between them.) -X 22 -E 22 - ···(A-VII) 7)S 1 and S 2 These are groups that are independently represented by the following general formula (AV). In the following general formula (AV), R 31 and R 38 Each of these is an alkylene group having a linear or branched chain with 2 to 6 carbon atoms, and R 32 , R 33 , R 34 , R 35 , R 36 and R 37 Each of these is independently an alkyl group having 1 to 6 carbon atoms, a fluorine-substituted alkyl group, or a phenyl group. K is an integer from 1 to 1500, L is 0 or an integer from 1 to 1500, and the sum of K and L, "K + L", is, for example, an integer from 1 to 1500, preferably an integer from 2 to 1000, and more preferably an integer from 3 to 500. [ka]

[0017] [ka] (In the above formula, R 51 represents a hydrogen atom or a methyl group, a is an integer greater than or equal to 2, b is an integer greater than or equal to 2, and n is an integer from 1 to 1500. Also, R 52 and R 53 R is a hydrogen atom or a methyl group, 52 If R is a hydrogen atom, 53 R is a methyl group, 52 If it is a methyl group, R 53 (This is a hydrogen atom.)

[0018] [ka] (In the above formula, a' is an integer greater than or equal to 2, b' is an integer greater than or equal to 2, and n' is an integer from 1 to 1500. Also, R 61 and R 62 R is a hydrogen atom or a methyl group, 61 If R is a hydrogen atom, 62 R is a methyl group, 61 If it is a methyl group, R 62 (This is a hydrogen atom.)

[0019] [ka] (In the above formula, a'' is an integer greater than or equal to 2, b'' is an integer greater than or equal to 2, and n'' is an integer from 1 to 1500. Also, R 81 and R 82 R is a hydrogen atom or a methyl group, 81 If R is a hydrogen atom, 82 R is a methyl group, 81 If it is a methyl group, R 82 (This 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)silylpropylglyceryl(meth)acrylate, tris(trimethylsiloxy)silylpropylglyceryl(meth)acrylate, mono[methylbis(trimethylsiloxy)siloxy]bis( Silicone-containing alkyl (meth)acrylates such as dimethylsiloxy)silylpropylglyceryl (meth)acrylate, trimethylsilylethyltetramethyldisiloxypropylglyceryl (meth)acrylate, trimethylsilylmethyl (meth)acrylate, trimethylsilylpropylglyceryl (meth)acrylate, trimethylsilylpropyl (meth)acrylate, trimethylsiloxydimethylsilylpropylglyceryl (meth)acrylate, methylbis(trimethylsiloxy)silylethyltetramethyldisiloxymethyl (meth)acrylate, tetramethyltriisopropylcyclotetrasiloxanylpropyl (meth)acrylate, tetramethyltriisopropylcyclotetrasiloxybis(trimethylsiloxy)silylpropyl (meth)acrylate;Tris(trimethylsiloxy)silylstyrene, bis(trimethylsiloxy)methylsilylstyrene, (trimethylsiloxy)dimethylsilylstyrene, Tris(trimethylsiloxy)siloxydimethylsilylstyrene, [bis(trimethylsiloxy)methylsiloxy]dimethylsilylstyrene, (trimethylsiloxy)dimethylsilylstyrene, heptamethyltrisiloxanylstyrene, nonamethyltetrasiloxanylstyrene, pentadecamethylheptasiloxanylstyrene, heneicosamethyldecasiloxane Nylstyrene, heptacosamethyltridecasiloxanylstyrene, hentricontamethylpentadecasiloxanylstyrene, trimethylsiloxypentamethyldisyloxymethylsilylstyrene, tris(pentamethyldisyloxy)silylstyrene, tris(trimethylsiloxy)siloxybis(trimethylsiloxy)silylstyrene, bis(heptamethyltrisiloxy)methylsilylstyrene, tris[methylbis(trimethylsiloxy)siloxy]silylstyrene, heptakis(trimethylsiloxy)trisilyl Lustyrene, trimethylsiloxybis[tris(trimethylsiloxy)siloxy]silylstyrene, nonamethyltetrasiloxyundecylmethylpentasiloxymethylsilylstyrene, tris[tris(trimethylsiloxy)siloxy]silylstyrene, (tristrimethylsiloxyhexamethyl)tetrasiloxy[tris(trimethylsiloxy)siloxy]trimethylsiloxysilylstyrene, nonakis(trimethylsiloxy)tetrasilylstyrene, bis(tridecamethylhexasiloxy)methylsilylstyrene Examples include silicone-containing styrene derivatives such as heptamethylcyclotetrasiloxanylstyrene, heptamethylcyclotetrasiloxybis(trimethylsiloxy)silylstyrene, tripropyltetramethylcyclotetrasiloxanylstyrene, and trimethylsilylstyrene; and silicone-containing fumarate diesters such as bis(3-(trimethylsilyl)propyl) fumarate, bis(3-(pentamethyldisiloxanyl)propyl) fumarate, and bis(tris(trimethylsiloxy)silylpropyl) fumarate.

[0021] Further specific examples of siloxane monomers 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 (Si-O) repeats may be, for example, 4 to 20, preferably 4 to 12, and more preferably 4 to 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 its compatibility with hydrophilic monomers, resulting in a silicone hydrogel with excellent transparency even when the proportion of siloxane monomer is increased.

[0023] In one embodiment, a siloxane monomer without hydrophilic groups and a siloxane monomer having hydrophilic groups can be used in combination. By using these two types of siloxane monomers in combination, the compatibility with the hydrophilic monomer is improved, resulting in a silicone hydrogel with excellent transparency, regardless of the presence or absence of the compatible monomer.

[0024] Examples of the hydrophilic groups mentioned above include hydroxyl groups, carboxyl groups, sulfonic acid groups, and phosphate groups. Among these, siloxane monomers having a hydroxyl group are preferred. Examples of siloxane monomers having a hydroxyl group include (3-methacryloxy-2-hydroxypropyloxy)propylbis(trimethylsiloxy)methylsilane (SiGMA).

[0025] The weight-average molecular weight of the above 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, and more preferably 300 g / mol to 800 g / mol, may be preferably used. By using such a siloxane monomer, the viscosity of the entire polymerizable composition can be reduced, making it easier to handle when dispensing into molds, etc. 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, and more preferably 3,000 g / mol to 8,000 g / mol, may be preferably used. By using such a siloxane monomer, a higher oxygen permeability improvement effect can be obtained. These siloxane monomers may be used individually or in combination. By using these two types of siloxane monomers in combination, it is possible to achieve high oxygen permeability while maintaining the appropriate viscosity of the polymerizable composition.

[0026] The number of repeating siloxane bonds in the above-mentioned siloxane monomer is typically 1500 or less, preferably 100 or less. In one embodiment, a siloxane monomer having, for example, 1 to 20 repeating siloxane bonds, preferably 2 to 20, more preferably 3 to 12, and even more preferably 4 to 10 repeating siloxane bonds may be preferably used. By using such a siloxane monomer, the viscosity of the entire polymerizable composition can be reduced, making it easier to handle when dispensing into a mold, etc. In another embodiment, a siloxane monomer having, for example, more than 20 and 1500 or less repeating siloxane bonds, preferably more than 20 and 100 or less, and more preferably more than 20 and 80 or less repeating siloxane bonds may be preferably used. By using such a siloxane monomer, a higher oxygen permeability improvement effect can be obtained. Either 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, high oxygen permeability can be achieved 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. Furthermore, in this specification, siloxane monomers containing more than 20 siloxane bonds or siloxane monomers with a weight-average molecular weight exceeding 1,000 g / mol are also referred to as siloxane macromonomers.

[0027] The blending ratio of siloxane monomers (or the total blending ratio if two or more siloxane monomers are used) can be, for example, 10% to 70% by weight, preferably 15% to 65% by weight, and more preferably 20% to 60% by weight, relative to the total blending amount of all monomer components and any hydrophilic polymers present in the polymerizable composition. If the blending ratio of siloxane monomers is within this range, a polymer material with 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 proportion of the siloxane macromonomer can be preferably 20% by weight or less, and more preferably 5% to 15% by weight, relative to the total amount of siloxane monomers (the sum of the siloxane macromonomer and other siloxane monomers).

[0029] When using a siloxane monomer having a hydrophilic group and a siloxane monomer not having a hydrophilic group in combination, the proportion of the siloxane monomer having a hydrophilic group can preferably be 1% to 60% by weight, more preferably 5% to 50% by weight, relative to the total siloxane monomer (the sum of the siloxane monomer having a hydrophilic group and the siloxane monomer not having a hydrophilic group).

[0030] A-1-2. Siloxane-free crosslinkable monomers Siloxane-free crosslinkable monomers do not have siloxane bonds and have two or more polymerizable groups. One feature of the present invention is that an alkylene glycol chain-containing crosslinkable monomer is used as the siloxane-free crosslinkable monomer, which has a chain portion containing six or more alkylene glycol repeating units and polymerizable groups positioned at both ends of the chain portion. If necessary, a crosslinkable monomer other than the alkylene glycol chain-containing crosslinkable monomer (hereinafter also referred to as a second crosslinkable monomer) may be used as the siloxane-free crosslinkable monomer.

[0031] The proportion of siloxane-free crosslinkable monomers (or the total proportion if two or more siloxane-free crosslinkable monomers are used) can be, for example, 2% by weight or more, preferably 2.2% by weight or more, more preferably 3% to 25% by weight, and even more preferably 3% to 20% by weight, relative to the total amount of all monomer components and hydrophilic polymers present in the polymerizable composition.

[0032] A-1-2-1. Alkylene glycol chain-containing crosslinkable monomer The crosslinkable monomer containing an alkylene glycol chain has a chain portion containing 6 or more alkylene glycol repeating units and polymerizable groups disposed at both ends of the chain portion. By using a crosslinkable monomer having a structure in which polymerizable groups are disposed at both ends of a relatively long polyether chain, a polymer network structure can be formed that suppresses the intrusion of hydrophobic molecules such as lipids while maintaining oxygen permeability by forming a hydrophilic network structure with the polyether chain. As a result, it is presumed that a polymer material having both oxygen permeability and surface hydrophilicity and suppressing lipid adhesion can be obtained. In the embodiments of the present invention, only one kind of the crosslinkable monomer containing an alkylene glycol chain may be used, or two or more kinds may be used in combination.

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

[0034] In one embodiment, the crosslinkable monomer containing an alkylene glycol chain can 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 -Z-P 2 (1) (In the formula, P 1 and P2 represents a polymerizable group which may be the same as or different from each other, A 1 O, A 2 O and A 3 O represents an alkylene glycol repeating unit which may be the same as 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 represent 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, provided that the relationship of m1 + m2×n1 + m3×n2 ≧ 6 is satisfied.)

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

[0036] In formula (1), L 1 and L 2 The linking groups defined by are as described above, a single bond or a divalent linking group. Examples of the divalent linking group include a linear or branched alkylene group having 1 to 5 carbon atoms and the like. L 1 and L 2 The linking groups defined by are 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 (m1+m2×n1+m3×n2) contained in the chain portion 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. If 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 within the chain-like structure. Preferably, the chain-like structure contains 6 or more consecutive alkylene glycol repeating units, more preferably 6 to 50 consecutively, 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-like structure may be, for example, 8 or more or 9 or more.

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

[0040] Specific examples of the alkylene glycol chain-containing crosslinkable monomers mentioned above 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 formula (1), the configuration shown is one in which each alkylene glycol repeating unit forms a block structure. However, if the alkylene glycol chain-containing crosslinkable monomer contains two or more alkylene glycol repeating units, the repeating units may be arranged randomly.

[0042] The blending ratio of the alkylene glycol chain-containing crosslinkable monomer (or the total blending ratio if two or more alkylene glycol chain-containing crosslinkable monomers are used) is, for example, 0.9% by weight or more, preferably 1% by weight or more, more preferably 2% by weight or more, more preferably 3% to 25% by weight, and even more preferably 3% to 20% by weight, relative to the total blending amount of all monomer components and hydrophilic polymers present in the polymerizable composition. The blending ratio of the alkylene glycol chain-containing crosslinkable monomer relative 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 alkylene glycol chain-containing crosslinkable monomers in such blending ratios, a polymer material that achieves both oxygen permeability and surface hydrophilicity, while suppressing lipid adhesion, can be suitably obtained.

[0043] A-1-2-2. Second crosslinkable monomer As the second crosslinkable monomer, any suitable siloxane-free crosslinkable monomer other than the alkylene glycol chain-containing crosslinkable monomers mentioned above can be used. Specific examples of the second crosslinkable monomer include butanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 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 Examples include vinyl benzyl (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, and 1,2-bis(2-(meth)acryloyloxyisopropyl)benzene. The second crosslinkable monomer may be used alone or in combination of two or more.

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

[0045] A-1-3. Copolymerizable monomers Copolymerizable monomers are those that have a single polymerizable group and do not contain siloxane bonds. Specific examples of copolymerizable monomers include hydrophilic monomers, compatibilizer monomers, and functional monomers.

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

[0047] A-1-3-1. Hydrophilic Precursors Hydrophilic monomers can increase the hydrophilicity of the resulting polymer material. Examples of hydrophilic monomers used include those with a solubility in water at 20°C of 0.03 g / mL or higher, preferably 0.1 g / mL or higher (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 with 1 to 5 carbon atoms in the alkyl group); and (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. kind Examples include alkyl(meth)acrylamides in which the alkyl group has 1 to 5 carbon atoms; N-vinyl lactams such as N-vinylpyrrolidone, N-vinylpiperidone, and N-vinylcaprolactam; N-methyl lactams such as 1-methyl-3-methylene-2-pyrrolidinone and methyl(meth)acrylates; and alkoxyalkyl(meth)acrylates in which the alkoxyalkyl group has 2 to 4 carbon atoms. Among these, 2-hydroxyethyl(meth)acrylate, N,N-dimethyl(meth)acrylamide, N-vinylpyrrolidone, methoxyethyl acrylate, ethyl acrylate, and glycerol mono(meth)acrylate are preferably used. Hydrophilic monomers can be used alone or in combination of two or more types.

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

[0050] A-1-3-2. Compatibilized monomers Compatibilizing monomers can improve the compatibility between siloxane monomers and hydrophilic monomers and / or hydrophilic polymers. Preferably, compatibilizing monomers are monomers that have hydrogen-bonding proton-containing groups and do not contain silicon atoms, and that have four or more carbon atoms in addition to the carbon atoms contained in the polymerizable groups.

[0051] The number of carbon atoms in the compatibilizing monomer (excluding carbon atoms contained in polymerizable groups) 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 per hydrogen-bonding proton-containing group, more preferably 5 to 15, and even more preferably 8 to 13 carbon atoms.

[0052] Examples of the above-mentioned hydrogen-bonding proton-containing groups include hydroxyl groups, carboxyl groups, amino groups, amide bonds, sulfonic acid groups (-SO3H), urethane bonds, and urea bonds. Among these, hydroxyl groups are preferred. The number of hydrogen-bonding proton-containing groups in the compatibilized monomer is, for example, 1 to 12, preferably 1 to 5, more preferably 1 to 3, and even more 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. By using monomers that have hydrogen-bonding proton-containing groups such as hydroxyl groups, while being hydrophobic overall, it is possible to improve the compatibility between siloxane monomers and hydrophilic monomers and / or hydrophilic polymers.

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

[0055] The compatibilized monomer in the above embodiment may be represented by the following formula (B). P 3 -AB (B) (In the formula, P 3 This represents a (meth)acryloyl group, A contains a hydrogen-bonding proton-containing group, or P 3 It represents a divalent group of atoms that forms a hydrogen-bonding proton-containing group, B represents a hydrocarbon group with 2 to 20 carbon atoms. However, the total number of carbon atoms in A and B must be 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 represented as follows. (Here, * is P) 3 This represents a bonding relationship with, X is O or NR a3 This represents, R a1 and R a2 Each of these independently represents an alkylene group having 1 to 20 carbon atoms, which may have a hydroxyl group. R a3 This represents hydrogen or an alkyl group having 1 to 4 carbon atoms. L a1 and L a2 Each of these independently represents an ether bond, ester bond, carbonyl group, amide bond, urethane bond, or urea bond. r1 to r3 each independently represent either 0 or 1. r4 represents an integer between 0 and 10. however, R a2 If it does not have a hydroxyl group, then r3 and r4 are not 0, (i) The atomic group has at least one hydrogen-bonding proton-containing group.

[0057] R a1 and R a2 Each of these independently represents an alkylene group having 1 to 6 carbon atoms, preferably having a hydroxyl group, and more preferably an alkylene group having 1 to 4 carbon atoms, preferably having a hydroxyl group. Specifically, R a1 and R a2 Preferably, at least one of them has a hydroxyl group, R a1 It is more preferable that it has a hydroxyl group. Such embodiments include R a1 It has a hydroxyl group, R a2 Embodiments in which R does not exist (for example, embodiments where r1=0 or 1, r2=0, r3=0) or Ra1 and R a2 Examples include embodiments in which both have hydroxyl groups (for example, embodiments in which r1=1, r2=1, r3=0 or 1).

[0058] If L exists a1 and L a2 Each of these can be independently preferably an ether bond or an ester bond. However, R a1 and R a2 If neither of them has a hydroxyl group, L a1 and L a2 Preferably, at least one of them is an amide bond, a urethane bond, or a urea bond.

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

[0060] Specific examples of the compatibilized monomers in the above embodiment are shown in the following formulas (I), (V), or (VI). [ka] (In the formula, R 1 This represents a hydrogen atom or a methyl group. R 2 and R 3 Each of these independently represents an alkylene group with 1 to 6 carbon atoms. R 4 These are hydrocarbon groups with 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 This represents the structure shown by (where R 5a R represents an alkylene group with 1 to 4 carbon atoms. 5b (where represents a hydrocarbon group with 2 to 20 carbon atoms, and s represents 0 or 1), X 1 is O or NR 6 This represents (where R 6 (represents hydrogen or an alkyl group having 1 to 4 carbon atoms), X 2 This represents a single bond or an alkylene group with 1 to 3 carbon atoms. X 3 This refers to 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 represent the structure shown by the following equations (II) to (IV) [ka] (Here, R 7a R represents an alkylene group with 1 to 4 carbon atoms. 7b R represents an alkylene group with 1 to 20 carbon atoms. 8a and R 8b (Each of these independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and t and u independently represent 0 or 1.) n is an integer between 0 and 10. q1 and q2 are independently either 0 or 1. however, Polymerizable group (CH2=CR 1 The total number of carbon atoms in the residues excluding -CO- is 3 or more. R4 , R 5b , R 6 , R 8a and R 8b The hydrocarbon groups or alkyl groups defined in the formula may each independently contain heteroatoms.

[0061] Regarding equation (I), R 4 and R 5b The hydrocarbon groups defined are preferably aliphatic hydrocarbon groups (e.g., alkyl groups) having 2 to 12 carbon atoms, more preferably 3 to 10 carbon atoms, and even more preferably 4 to 10 carbon atoms. These hydrocarbon groups may be linear, branched, or include a cyclic structure. It is believed that these hydrocarbon groups function as terminal hydrophobic groups, allowing the compatible monomer to exhibit affinity for the siloxane monomer.

[0062] R 4 or R 5bSpecific examples of hydrocarbon groups defined by include linear alkyl groups such as ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, and n-decyl group; branched alkyl groups such as isopropyl group, methylpropyl group, t-butyl group, dimethylpropyl group, ethylpropyl group, diethylpropyl group, methylbutyl group, dimethylbutyl group, trimethylbutyl group, ethylbutyl group, propylbutyl group, methylpentyl group, dimethylpentyl group, ethylpentyl group, propylpentyl group, butylpentyl group, methylhexyl group, dimethylhexyl group, trimethylhexyl group, ethylhexyl group, propylhexyl group, methylheptyl group, dimethylheptyl group, ethylheptyl group, propylheptyl group, methyloctyl group, dimethyloctyl group, ethyloctyl group, and methylnonyl group; and methyl Examples include cycloalkyl groups such as hydroxypropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and cyclononyl group; cyclooctylethyl group, cycloheptylmethyl group, cycloheptylethyl group, cyclohexylmethyl group, cyclohexylethyl group, cyclohexylpropyl group, cyclohexylbutyl group, cyclopentylethyl group, cyclopentylpropyl group, cyclopentylbutyl group, cyclopentylpentyl group, cyclobutylpropyl 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 The alkylene groups defined are preferably a methylene group, an ethylene group, or a propylene group, or a butylene group, and more preferably a methylene group or an ethylene group.

[0065] R 7b The alkylene group defined 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 in the group is preferably 3 or less, more preferably 0 to 2, and even more preferably 1 or 2 (for example, X 2 is a methylene group or an ethylene group, R 2 Embodiments in which X does not exist (i.e., embodiments where q1=0), 2 and R 2 This includes embodiments in which both are methylene groups. It is believed that the compatibility monomer can exhibit affinity for hydrophilic monomers and / or hydrophilic polymers by having the hydroxyl group positioned in close proximity to the (meth)acryloyl group.

[0067] X 3 The total number of carbon atoms 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 heteroatoms that the hydrocarbon group or alkyl group defined by are may have are not limited as long as the effects of the present invention are obtained, and examples include halogens such as fluorine. In one embodiment, R 4 , R 5b , R 6 , R 8a or R 8b The hydrocarbon group or alkyl group specified may be a fluoroalkyl group or a 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 X is a hydrogen atom or a methyl group, 1 O is X 2 is a methylene group or an ethylene group, preferably a methylene group, n is 0, R 4 ga-(R 5a ) s -OR 5b (However, R 5a is a methylene group, s is 1, R 5b (where is 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 X is a hydrogen atom or a methyl group, 1 O is X 2 is a methylene group or an ethylene group, preferably a methylene group, n is 0, R 4 ga-(R 5a ) s -O(C=O)-R 5b (However, R 5a is a methylene group, s is 1, R 5b (where is 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 X is a hydrogen atom or a methyl group, 1 O is X 2 is a methylene group or an ethylene group, preferably a methylene group, n is 0, R 4 is a hydrocarbon group having 2 to 20 carbon atoms, which may be substituted with fluorine, and q1 is 0 or 1, preferably 0.

[0073] [ka] (In the formula, R 9 This represents a hydrogen atom or a methyl group. R 10 These are hydrocarbon groups with 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 (Here, R 10a R represents an alkylene group with 1 to 4 carbon atoms. 10b The structure is represented by (where represents a hydrocarbon group with 2 to 20 carbon atoms), however, R 10 The total number of carbon atoms in the group is 4 or more. R 10 or R 10b The hydrocarbon group defined may have a heteroatom.

[0074] Regarding equation (V), R 10 or R 10b Each of the hydrocarbon groups defined is preferably an aliphatic hydrocarbon group (e.g., alkyl group) having 4 to 12 carbon atoms, more preferably 4 to 10 carbon atoms. These hydrocarbon groups may be linear, branched, or include a cyclic structure. It is believed that these hydrocarbon groups function as terminal hydrophobic groups, allowing the compatible monomer to exhibit affinity for the siloxane monomer.

[0075] R 10 or R 10b Specific examples of hydrocarbon groups defined by include R 4 or R 5b Examples of specific hydrocarbon groups defined in [the relevant text] (provided they have four or more carbon atoms) can be given.

[0076] R 10aThe alkylene group specified is preferably a methylene group, an ethylene group, or a propylene group, butylene group, and more preferably a methylene group or an ethylene group.

[0077] R 10 or R 10b The heteroatoms that the hydrocarbon group defined by can have are not limited as long as the effects of the present invention are obtained, and examples include halogens such as fluorine. In one embodiment, R 10 or R 10b The hydrocarbon group specified may be a fluoroalkyl group or a perfluoroalkyl group.

[0078] [ka] (In the formula, R 11 This represents a hydrogen atom or a methyl group. X 4 is O or NR 14 This represents (where R 14 (represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), R 12 This represents an alkylene group with 2 to 14 carbon atoms. X 5 This is a structure consisting of a single bond, O, or the following formulas (VII) to (IX). [ka] (Here, R 15a and R 15b Each of these independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R 13 This represents a hydrocarbon group with 2 to 20 carbon atoms. however, X 4 When X is not NH, 5 It has a structure containing a urethane bond (-NHCOO-) or a urea bond (-NHCONH-), R 12 , R 13 , R 14 , R15a and R 15b Each of these elements may independently contain a heteroatom.

[0079] Regarding equation (VI), R 12 The alkylene group defined by may be linear, branched, or include a cyclic structure. 12 Preferably, it is 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 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 even more preferably 4 to 10 carbon atoms. The hydrocarbon group may be linear, branched, or include a cyclic structure. It is believed that the hydrocarbon group functions as a terminal hydrophobic group, allowing the compatible monomer to exhibit affinity for the siloxane monomer.

[0081] R 13 Specific examples of hydrocarbon groups defined by include R 4 or R 5b The same specific examples of hydrocarbon groups defined in [the relevant text] can be used as examples.

[0082] R 14 , R 15a and R 15b Specific examples of alkyl groups defined in the formula include methyl groups and ethyl groups.

[0083] R 12 , R 13 , R 14 , R 15a and R 15b The heteroatoms that may be present are not limited as long as the effects of the present invention are obtained, and examples include halogens such as fluorine. In one embodiment, R 12 , R 13 , R 14 , R 15a or R 15bThis can 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 four or more carbon atoms, with at least one hydrogen atom substituted with a hydrogen-bonding proton-containing group. The alicyclic ring preferably has 5 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and even more preferably 8 to 12 carbon atoms, and may have a crosslinking structure. Specific examples of the compatibilizing monomer in this embodiment include (meth)acrylates having a crosslinked alicyclic group substituted with one or more hydroxyl groups (e.g., adamantyl group, norbornyl group, tricyclodecanyl group, tetracyclododecyl group, etc.), more specifically, hydroxy(meth)acryloyloxyadamantane, dihydroxy(meth)acryloyloxyadamantane, and the like.

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

[0086] A-1-3-3. Functional Monomers Functional monomers are added as needed to impart a specific function to polymer materials. Examples of functional monomers include polymerizable dyes, polymerizable ultraviolet absorbers, and polymerizable ultraviolet absorbing dyes.

[0087] Specific examples of polymerizable dyes include azo polymerizable dyes, anthraquinone polymerizable dyes, nitro polymerizable dyes, and phthalocyanine polymerizable dyes. These can be used individually or in combination of two or more.

[0088] Specific examples of polymerizable ultraviolet absorbers include, for example, benzophenone-based polymerizable ultraviolet absorbers, benzotriazole-based polymerizable ultraviolet absorbers, salicylic acid derivative-based polymerizable ultraviolet absorbers, and 2-cyano-3-phenyl-3-(3'-(meth)acryloyloxyphenyl)propenyl methyl ester. These can be used individually or in combination of two or more.

[0089] Specific examples of polymerizable UV-absorbing dyes include, for example, benzophenone-based polymerizable UV-absorbing dyes and benzoic acid-based polymerizable UV-absorbing dyes. These can be used individually or in combination of two or more types.

[0090] The proportion of functional monomers is, for example, 0.001% to 5% by weight, preferably 0.05% to 3% by weight, relative to the total amount of all monomer components and hydrophilic polymers present in the polymerizable composition.

[0091] A-1-3-4. Other copolymerizable monomers Other copolymerizable monomers may be any suitable monomer depending on the purpose. For example, alkyl (meth)acrylates with 2 to 5 carbon atoms in the alkyl group are used. The proportion of other copolymerizable monomers is, for example, 0.001% to 5% by weight, preferably 0.05% to 3% by weight, relative to the total amount of all monomer components and hydrophilic polymers present in the polymerizable composition.

[0092] A-2. Hydrophilic polymers Hydrophilic polymers are typically non-polymerizable components that do not possess polymerizable groups. By polymerizing the above monomer components in the presence of a hydrophilic polymer, a polymer containing structural units derived from the above monomer components and the hydrophilic polymer become highly composited, and a polymer material with increased surface hydrophilicity can be obtained.

[0093] Any suitable polymer capable of imparting surface hydrophilicity to the polymer material can be used as the hydrophilic polymer. For example, polymers such as polyvinylamide (e.g., polyvinyl lactam), polyamide, polylactone, polyimide, and polylactam can be used as hydrophilic polymers. Among these, polymers containing a cyclic structure in the main chain or side chain, such as a cyclic amide structure or a cyclic imide structure, can be preferably used. The hydrophilic polymer may be a random copolymer, alternating copolymer, block copolymer, or graft copolymer composed of two or more monomers. Furthermore, the hydrophilic polymer may be used alone or in combination of two or more types.

[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 and poly-N-vinyl-4,5-dimethyl-2-pyrrolidone, polyvinylimidazole, 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, polysaccharide, and copolymers thereof. Among these, poly-N-vinylpyrrolidone, polyalkylene glycol, polysaccharide, poly(meth)acrylic acid, polyvinyl alcohol, and poly(2-hydroxyethyl)(meth)acrylate 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. Here, the K value can be determined by measuring the viscosity according to the viscosity measurement method 1 <2.53> in the 16th edition of the Japanese Pharmacopoeia, and then using Fikentscher's formula according to the method described in the "K value" column of the Pharmacopoeia.

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

[0098] A-3. Coatings As additives, any suitable additive can be selected depending on the purpose. Examples of additives include polymerization initiators and organic solvents.

[0099] The polymerization initiator is appropriately selected depending on the polymerization method. Examples of thermal polymerization initiators used for 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 individually or in combination of two or more.

[0100] The proportion 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, relative to the total components (excluding organic solvents) in the polymerizable composition.

[0101] Examples of photopolymerization initiators used in polymerization by light irradiation include phosphine oxide-based photopolymerization initiators such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO) and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; benzoin-based photopolymerization initiators such as methyl orthobenzoyl benzoate, methyl benzoyl formate, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzoin-n-butyl ether; and 2-hydroxy-2-methyl-1-phenylpropan-1-one (HMPPO) and p-isopropyl Examples of photopolymerization initiators include phenone-based photopolymerization initiators such as pyr-α-hydroxyisobutylphenone, pt-butyltrichloroacetophenone, 2,2-dimethoxy-2-phenylacetophenone, α,α-dichloro-4-phenoxyacetophenone, and N,N-tetraethyl-4,4-diaminobenzophenone; 1-hydroxycyclohexylphenyl ketone; 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime; thioxanthone-based photopolymerization initiators such as 2-chlorothioxanthone and 2-methylthioxanthone; dibenzosvalone; 2-ethylanthraquinone; benzophenone acrylate; benzophenone; and benzyl. These photopolymerization initiators can be used individually or in combination of two or more. Photosensitizers may also be used together with the photopolymerization initiators.

[0102] The proportion of photopolymerization initiators and photosensitizers in the polymerizable composition is preferably 0.001% to 2% by weight, more preferably 0.01% to 1% by weight, relative to the total components (excluding organic solvents) in the polymerizable composition.

[0103] The above-mentioned organic solvent may be a highly polar, water-soluble organic solvent, or a less polar, water-insoluble organic solvent. Examples of water-soluble organic solvents include C1-C4 alcohols, acetone, methyl ethyl ketone, dimethylformamide, dimethyl sulfoxide, acetonitrile, N-methyl-2-pyrrolidone, dimethoxyethane, tetrahydrofuran, and 1,4-dioxane. Using a water-soluble organic solvent can improve the compatibility between monomer components or between hydrophilic polymers and monomer components. Furthermore, the water-soluble organic solvent can be easily removed from the polymer material by immersion in water.

[0104] Examples of non-water-soluble organic solvents 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 with 6 or more carbon atoms. Using a non-water-soluble organic solvent can improve the compatibility between monomer components or between hydrophilic polymers and monomer components. Furthermore, when added to a polymerizable composition, the kinematic viscosity of the polymerizable composition decreases compared to when a water-soluble organic solvent is used, making it easier to handle.

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

[0106] Other additives not mentioned above include those conventionally used in ophthalmic lenses. Examples include cooling agents, viscosity modifiers, surfactants, non-polymerizable dyes, UV absorbers, or UV-absorbing dyes.

[0107] The proportion of the above-mentioned other additives in the polymerizable composition can be, for example, 0.001% to 5% by weight, preferably 0.005% to 3% by weight, relative to the total components (excluding organic solvents) in the polymerizable composition.

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

[0109] Polymerization methods that can be used include bulk polymerization and solution polymerization. In bulk polymerization, some monomer components may remain unpolymerized. In solution polymerization, solvents that do not participate in the reaction may remain in the resulting polymer. In the manufacture of medical devices such as contact lenses, in order to reduce these residues as much as possible, the resulting polymer material may be immersed in water, an organic solvent, or a mixture thereof, and preferably this process may be repeated to dissolve and remove these residues from the polymer material.

[0110] When the polymer material is used for contact lenses or the like, the polymerizable composition can be molded into a desired shape (e.g., a hemispherical shape) by reacting it using a mold method. When polymerizing the polymerizable composition by heating it using a mold method, the polymerizable composition is filled into a mold corresponding to the desired shape of the ophthalmic lens material, and this mold is gradually heated.

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

[0112] In the molding method, when polymerizing a polymerizable composition by light irradiation, the polymerizable composition is first filled into a mold corresponding to the desired shape of an ophthalmic lens, and then light is irradiated onto the mold. 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 light irradiated onto the polymerizable composition in the mold is appropriately set according to the type of photopolymerization initiator used. The light intensity and irradiation time are appropriately set according to the composition of the polymerizable composition. The light intensity is preferably 0.1 mW / cm². 2 ~100mW / cm 2 The following applies: The irradiation time is preferably 1 minute or more. Light of different illuminances may be irradiated in stages.

[0114] Polymerization using the above molding method yields a polymer material having the desired shape. The resulting polymer material as a molded body may be subjected to mechanical processing such as cutting and polishing as needed. Cutting may be performed over the entire surface of one or both surfaces of the polymer material, or on a portion of one or both surfaces of the polymer material.

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

[0116] C. Properties of Polymer Materials In one embodiment of the present invention, the Young's modulus of the polymer material 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, it is possible to obtain ophthalmic lenses with excellent wearing comfort and handling when processed into contact lenses.

[0117] In one embodiment of the present invention, the stress relaxation rate of the polymer material is preferably 10% to 40%, more preferably 10% to 30%. By using a polymer material having such a stress relaxation rate, it is possible to obtain an ophthalmic lens with excellent wearing comfort and handling when processed into a contact lens.

[0118] In one embodiment of the present invention, the oxygen permeability coefficient (Dk value) of the polymer material is preferably 20 Barrer or more, more preferably 30 Barrer or more, and even more preferably 50 Barrer 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% to 70% by weight. By setting the water content of the polymer material to 11% by weight or more, the resulting polymer material can be made into a hydrogel, improving the wearing comfort when processed into contact lenses, and allowing for a good balance of strength, oxygen permeability, and surface hydrophilicity. [Examples]

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

[0121] [Ingredients used] The meanings of the abbreviations for the components used in the following examples and comparative examples are shown below. <Siloxane monomer> • AA-PDMS: A polymerizable compound having 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] <Cross-linkable monomers> • 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 count: 9, HLB: 10.07, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., "NK Ester 9G") • PEGDMA (n=14): Polyethylene glycol dimethacrylate (EO repeat count: 14, HLB: 11.72, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., "NK Ester 14G") • PEGDMA (n=23): Polyethylene glycol dimethacrylate (EO repeat count: 23, HLB: 14.69, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., "NK Ester 23G") • 9PG (n=7): Polypropylene glycol dimethacrylate (PO repeat count: 7, HLB: 6.05, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., "NK Ester 9PG") • 25PDC: Polyethylene glycol, polypropylene glycol, dimethacrylate (EO repeat count: 8, PO repeat count: 9, AO repeat structure: EO-PO-EO block type, HLB: 8.39, manufactured by NOF Corporation, "25PDC-900B") • 40PDC: Polyethylene glycol, polypropylene glycol, dimethacrylate (EO repeat count: 15, PO repeat count: 18, AO repeat structure: EO-PO-EO block type, HLB: 9.35, manufactured by NOF Corporation, "40PDC-1700B") • AMA: Allyl methacrylate <Compatibilized monomers> ·EH(OH)MA: A polymerizable compound having the structure shown below (solubility in water at 20°C: less than 0.01 g / mL) [Chemical formula] <Hydrophilic monomer> ·DMAA: N,N-Dimethylacrylamide ·HEMA: 2-Hydroxyethyl methacrylate ·N-VP: N-Vinyl-2-pyrrolidone ·2-MTA: Methoxyethyl acrylate <Functional monomer> ·HMEPBT: A benzotriazole-based polymerizable ultraviolet absorber (2-(2’-Hydroxy-5’-methacryloyloxyethylphenyl)-2H-benzotriazole) ·RB246: An anthraquinone-based polymerizable dye <Hydrophilic polymer> ·PVP K-90: Polyvinylpyrrolidone (Mw = 1,000,000 - 1,500,000) <Additive> ·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 eggplant flask and dissolved. A Dimroth condenser was 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 a 1M aqueous sodium hydrogen carbonate solution. 4) The hexane layer was washed with distilled water. 5) The hexane layer was washed with saturated brine. 6) The hexane layer was recovered, an appropriate amount of sodium sulfate was added for drying, and it was left standing for a while. 7) Sodium sulfate was removed by filtration. 8) The hexane layer was concentrated under reduced pressure to obtain a slightly yellowish, transparent liquid. 1 ¹H NMR (CDCl3, 400 MHz) and gas chromatography were performed to confirm that the desired compound was obtained.

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

[0124] [Example 1-A] 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 crosslinkable 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 were mixed to prepare a polymerizable composition. The obtained polymerizable composition was injected into a mold having a contact lens shape (made of polypropylene, corresponding to a contact lens with a diameter of 14.2 mm and a thickness of 0.08 mm). Then, at room temperature, the mold was irradiated with LED light to perform photopolymerization. After polymerization, the contact lens-shaped polymer material was taken out of the mold. Thereby, a silicone hydrogel contact lens was obtained.

[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 each component was mixed to prepare a polymerizable composition so as to have the composition described in Tables 1 to 4.

[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 swelled until equilibrium was reached. Then, the solution was replaced with pH 7.5 phosphate buffer and swelled until equilibrium was reached. After that, the solution was replaced with the same amount of fresh phosphate buffer, autoclaved at 121°C for 20 minutes, and then the following characteristics were evaluated. However, for the measurement of the oxygen permeability coefficient, a PP mold was used to obtain a plate-shaped sample with an average thickness of approximately 0.3 mm instead of a mold with a contact lens shape. Otherwise, polymerization, hydration, and sterilization treatments were performed in the same manner as above, 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) A solid artificial lipid (product name "Pharmazol") at room temperature was heated to 60°C to melt it, and 1.7 mL was added to each well of the lens. 2) After wiping off any moisture from the surface of the contact lenses, they were placed in each well and left in a 60°C dryer for 1 hour. 3) Remove the contact lenses from the wells, rinse them in contact lens cleaning solution (Menicon Co., Ltd., product name "Epica Cold") in a beaker, and then rub each side 20 times with contact lens cleaning solution (Menicon Co., Ltd., product name "Epica Cold") or hot water. 4) Contact lens cleaning solution (Menicon, product name "Epica Cold") and contact lenses were placed in each well of a multi-well plate and left at 10°C for 4 hours. After that, the contact lenses were removed from the wells, rubbed and rinsed, and then left to stand overnight. 5) After removing the contact lenses from the well and rubbing them clean, their appearance was examined with the naked eye and evaluated based on the following criteria. Microscopic images of each lens are shown in Figure 1. [Judgment criteria] 0: Almost no whiteness observed 1: A small portion is observed to be white. 2: Approximately 50% of the whole is observed to be white. 3: The lens appears almost entirely white, but there are areas with less turbidity. 4: The lens appears white all over.

[0132] Measurement of Tensile Modulus (Young's Modulus) A dumbbell-shaped sample with a stretched portion width of approximately 1.8 mm and a thickness of approximately 0.1 mm was created by punching out the fabricated contact lens and used as the test sample. Tensile tests were performed in physiological saline solution at 20°C using a Shimadzu Autograph AG-IS MS type universal testing machine manufactured by Shimadzu Corporation, and Young's modulus (MPa) was calculated as the tensile modulus 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 and fixture as shown in Figure 2 as used for tensile modulus measurement. Specifically, the center of the fabricated contact lens C was pressed into physiological saline solution with an indenter P equipped with a tip PT of approximately 1.6 mm in diameter, using a test force of 0.1 N. The stress relaxation rate (%) was calculated from the change in stress after holding the stroke for 1 minute.

[0134] As shown in Figure 1, the contact lenses of the example exhibit suppressed lipid adhesion compared to the contact lenses of the comparative example. Furthermore, the contact lenses of the example possess desirable Young's modulus and stress relaxation rate for contact lenses, and can be found to offer superior handling and wearing comfort.

[0135] ≪Moisture content measurement≫ The water content of the contact lenses obtained in Example 1-C was measured. Specifically, the surface moisture of a contact lens adjusted in pH 7.5 phosphate buffer at 20°C was lightly wiped off, and the mass (W(g)) at equilibrium water content was measured. Then, the lens was dried in a dryer set to 105°C, and its mass (W0(g)) after cooling 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] ≪Measurement of oxygen permeability coefficient (Dk value)≫ The Dk value was measured using a circular plate-type sample with a diameter of 14.0 mm obtained in Example 1-C as the measurement sample. Specifically, a similar plate-type sample was prepared using the material of "2WEEK Menicon Premio" (manufactured by Menicon Corporation) as a reference standard, and its Dk value was set to 129. The sample was placed on the electrode, and using a Seikaken-type film oxygen permeability meter (manufactured by Rika Seiki Kogyo Co., Ltd.), nitrogen bubbling was performed in physiological saline at 35°C. The current value at equilibrium was set to zero. Next, oxygen bubbling was performed, and the current value at equilibrium was recorded. This was also performed for the reference standard. The oxygen permeability coefficient of the lens was calculated according to the following formula. The unit of the oxygen permeability coefficient is (×10⁻⁶). -11 (cm 2 The formula is ( / 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: Reference standard Dk value (129) IS: Current value of the sample being measured (μA) IR: Current value of the reference standard (μA) TS: Average thickness of the sample being measured (mm) TR: Average thickness of the reference standard (mm) PS: Atmospheric pressure (mmHg) at the time of sample measurement. PR: Atmospheric pressure (mmHg) during reference standard measurement [Industrial applicability]

[0137] The ophthalmic lens of the present invention is suitably used in 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 that includes, as monomer components, a siloxane monomer having a siloxane bond, a copolymerizable monomer containing a compatible monomer and a hydrophilic monomer, and a siloxane-free crosslinkable monomer that does not have a siloxane bond, and further comprising a hydrophilic polymer, or not comprising a hydrophilic polymer, The compatibilizing monomer has a hydrogen-bonding proton-containing group, does not contain a silicon atom, and has six or more carbon atoms in addition to the carbon atoms contained in the polymerizable group. An ophthalmic lens comprising an alkylene glycol chain-containing crosslinkable monomer, wherein the siloxane-free crosslinkable monomer has a chain portion containing six or more alkylene glycol repeating units and polymerizable groups positioned at both ends of the chain portion.

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

3. The ophthalmic lens according to claim 1 or 2, wherein the alkylene glycol repeating unit comprises at least one selected from the group consisting of ethylene glycol repeating units, propylene glycol repeating units, and butylene glycol repeating units.

4. The ophthalmic lens according to any one of claims 1 to 3, wherein the hydrophilic monomer comprises at least one selected from hydroxyl group-containing alkyl (meth)acrylate, (meth)acrylamides, N-vinyl lactam, N-methyl lactam, methyl (meth)acrylate, and alkoxyalkyl (meth)acrylate.

5. The ophthalmic lens according to any one of claims 1 to 4, wherein the polymerizable composition comprises the hydrophilic polymer.

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

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

8. The ophthalmic lens according to any one of claims 5 to 7, wherein the proportion of the copolymerizable monomer to the total amount of all monomer components and the hydrophilic polymer in the polymerizable composition is 20% to 70% by weight.

9. The ophthalmic lens according to any one of claims 5 to 8, wherein the hydrophilic polymer comprises at least one selected from poly-N-vinylpyrrolidone, polyalkylene glycol, polysaccharide, poly(meth)acrylic acid, and polyvinyl alcohol.

10. The ophthalmic lens according to any one of claims 1 to 9, wherein the HLB value of the alkylene glycol chain-containing crosslinkable monomer is 5 to 20.

11. The ophthalmic lens according to any one of claims 1 to 10, wherein the proportion of the siloxane monomer to the total amount of all monomer components and the hydrophilic polymer (if present) in the polymerizable composition is 10% by weight to 70% by weight.

12. The ophthalmic lens according to any one of claims 1 to 11, wherein the number of repeating siloxane bonds in the siloxane monomer is 100 or less.

13. The ophthalmic lens according to any one of claims 1 to 12, wherein the number of repeating siloxane bonds in the siloxane monomer is 20 or less.

14. The ophthalmic lens according to any one of claims 1 to 13, wherein the weight-average molecular weight of the siloxane monomer is 10,000 or less.

15. The ophthalmic lens according to any one of claims 1 to 14, wherein the weight-average molecular weight of the siloxane monomer is 1,000 or less.

16. The siloxane monomer comprises siloxane monomer A having a weight-average molecular weight of 1,000 or less, and siloxane monomer B having a weight-average molecular weight of more than 1,000. The ophthalmic lens according to any one of claims 1 to 15, wherein the ratio of siloxane monomer B to the total of siloxane monomer A and siloxane monomer B is 20% by weight or less.

17. The ophthalmic lens according to any one of claims 1 to 16, wherein the stress relaxation rate of the polymer material is 10% to 40%.

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

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

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

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