Eye lenses

Abstract

The present invention provides an ophthalmic lens that has both oxygen permeability and surface hydrophilicity and has lipid adhesion suppressed. The ophthalmic lens of the present invention is an ophthalmic lens comprising a polymer material obtained by polymerizing a polymerizable composition, the polymerizable composition comprising a siloxane monomer having a siloxane bond and a siloxane-free crosslinking monomer having no siloxane bond as monomer components, the siloxane-free crosslinking monomer comprising an alkylene glycol chain-containing crosslinking monomer having a chain portion comprising 6 or more alkylene glycol repeating units and polymerizable groups disposed at both ends of the chain portion.

Description

Technical Field

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

[0002] Contact lenses are roughly divided into hard contact lenses and soft contact lenses. In recent years, most hard contact lenses are formed using siloxane polymers having siloxane bonds (Si-O-Si), thereby having high oxygen permeability, but due to their hardness, there are cases where a foreign body sensation is generated when worn. On the other hand, soft contact lenses are formed by using a water-containing hydrogel using a copolymer having a hydrophilic monomer and a (meth) acrylic monomer as copolymer components, thereby obtaining an excellent wearing feel, but on the other hand, there is a tendency for low oxygen permeability compared to hard contact lenses. In response to this, the following contact lenses have been developed, that is, using a silicone hydrogel containing a siloxane monomer as a further copolymer component, thereby taking into account both high oxygen permeability and excellent wearing feel (Patent Document 1).

[0003] However, contact lenses made of silicone hydrogels are prone to lipid adhesion on the surface. Therefore, there is a demand for a contact lens that has both high oxygen permeability and excellent wearing comfort and in which lipid adhesion is suppressed.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent No. 6433790 Summary of the invention

[0007] A main object of the present invention is to provide an ophthalmic lens that achieves both oxygen permeability and wearing comfort and in which lipid adhesion is suppressed.

[0008] According to one aspect of the present invention, there is provided an ophthalmic lens comprising a polymer material obtained by polymerizing a polymerizable composition comprising, as monomer components, a siloxane monomer having a siloxane bond and a siloxane-free crosslinking monomer having no siloxane bond, wherein the siloxane-free crosslinking monomer comprises an alkylene glycol chain-containing crosslinking monomer having a chain portion comprising 6 or more alkylene glycol repeating units and polymerizable groups disposed at both ends of the chain portion.

[0009] In one embodiment, the chain portion of the crosslinkable monomer containing an alkylene glycol chain contains 6 to 50 alkylene glycol repeating units.

[0010] In one embodiment, the alkylene glycol repeating unit comprises at least one selected from the group consisting of ethylene glycol repeating units, propylene glycol repeating units, and butanediol repeating units.

[0011] In one embodiment, the polymerizable composition further comprises a hydrophilic polymer.

[0012] In one embodiment, the blending ratio of the crosslinking monomer not containing siloxane is 2% by weight or more relative to the total blending ratio of all monomer components in the polymerizable composition and the hydrophilic polymer when the hydrophilic polymer is present, and the blending ratio of the crosslinking monomer containing an alkylene glycol chain is 0.9% by weight or more relative to the total blending ratio of all monomer components in the polymerizable composition and the hydrophilic polymer when the hydrophilic polymer is present.

[0013] In one embodiment, the blending ratio of the alkylene glycol chain-containing crosslinking monomer is 2% by weight or more relative to the total blending amount of all monomer components in the polymerizable composition and the hydrophilic polymer when the hydrophilic polymer is present.

[0014] In one embodiment, the blending ratio of the alkylene glycol chain-containing crosslinking monomer is 3 to 25 wt % relative to the total blending amount of all monomer components in the polymerizable composition and the hydrophilic polymer when the hydrophilic polymer is present.

[0015] In one embodiment, the HLB value of the cross-linking monomer containing an alkylene glycol chain is 5-20.

[0016] In one embodiment, the blending ratio of the siloxane monomer is 10% by weight to 70% by weight relative to the total blending amount of all monomer components in the polymerizable composition and the hydrophilic polymer when the hydrophilic polymer is present.

[0017] In one embodiment, the siloxane monomer has a single polymerizable group.

[0018] In one embodiment, the siloxane monomer has 100 or less repeating siloxane bonds.

[0019] In one embodiment, the siloxane monomer has 20 or less repeating siloxane bonds.

[0020] In one embodiment, the weight average molecular weight of the siloxane monomer is 10,000 or less.

[0021] In one embodiment, the weight average molecular weight of the siloxane monomer is 1000 or less.

[0022] In one embodiment, the siloxane monomer comprises a siloxane monomer A having a weight average molecular weight of 1000 or less and a siloxane monomer B having a weight average molecular weight of more than 1000, wherein the proportion of the siloxane monomer B is 20 wt % or less relative to the total of the siloxane monomer A and the siloxane monomer B.

[0023] In one embodiment, the monomer component further includes a copolymerizable monomer.

[0024] In one embodiment, the copolymerizable monomer comprises at least one hydrophilic monomer selected from the group consisting of hydroxyl-containing alkyl (meth)acrylates, (meth)acrylamide, N-vinyl lactam, N-methyl lactam, methyl (meth)acrylate, and alkoxyalkyl (meth)acrylates.

[0025] In one embodiment, the copolymerizable monomer is contained in an amount of 20% by weight to 70% by weight relative to the total amount of all monomer components in the polymerizable composition and the hydrophilic polymer when the hydrophilic polymer is present.

[0026] In one embodiment, the hydrophilic polymer comprises at least one selected from the group consisting of poly-N-vinyl pyrrolidone, polyalkylene glycol, polysaccharide, poly(meth)acrylic acid and polyvinyl alcohol.

[0027] In one embodiment, the stress relaxation rate of the polymer material is 10% to 40%.

[0028] In one embodiment, the Young's modulus of the polymer material is 0.3 MPa to 2.3 MPa.

[0029] In one embodiment, the ophthalmic lens is a contact lens.

[0030] According to the present invention, by using a polymer material obtained by polymerizing a monomer component including a siloxane monomer and a specific crosslinking monomer, an ophthalmic lens that has both oxygen permeability and a comfortable fit and has lipid adhesion suppressed can be obtained. In addition, the ophthalmic lens obtained by the present invention can have appropriate flexibility and deformation recovery properties in order to ensure good operability. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 It is a graph showing the evaluation results of the ophthalmic lenses obtained in Examples and Comparative Examples.

[0032] Figure 2 It is a figure explaining the jig used for measuring the stress relaxation rate. DETAILED DESCRIPTION

[0033] In this specification, the so-called "monomer" refers to a polymerizable compound having one or more polymerizable groups. As the polymerizable group, an ethylenically unsaturated group can be preferably exemplified, and the polymerizable group can be, for example, a (meth)acryloyl group, a vinyl group or an allyl group. Here, "(meth)" refers to any methyl substitution. Therefore, "(meth)acryloyl" refers to methacryloyl and / or acryloyl. Other records such as "(meth)acrylic group" are also the same.

[0034] The ophthalmic lens according to an embodiment of the present invention comprises a polymer material obtained by polymerizing a polymerizable composition, wherein the polymerizable composition comprises a siloxane monomer having a siloxane bond and a siloxane-free crosslinking monomer having no siloxane bond as monomer components, and as the siloxane-free crosslinking monomer, at least a crosslinking monomer containing an alkylene glycol chain is used, wherein the crosslinking monomer containing an alkylene glycol chain has a chain portion containing 6 or more alkylene glycol repeating units and polymerizable groups arranged at both ends of the chain portion. The ophthalmic lens according to an embodiment of the present invention typically has a hemispherical shape along the curve of the cornea. The ophthalmic lens according to an embodiment of the present invention can be used as, for example, a contact lens, an artificial cornea, a cornea patch (cornea onlay), preferably a silicone hydrogel contact lens.

[0035] 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 combined as appropriate.

[0036] A. Polymerizable Composition

[0037] The polymerizable composition comprises a siloxane monomer having a siloxane bond and a cross-linking monomer not containing siloxane having a siloxane bond as a monomer component, wherein the cross-linking monomer not containing siloxane comprises a cross-linking monomer containing an alkylene glycol chain, wherein the cross-linking monomer containing an alkylene glycol chain has a chain portion containing 6 or more alkylene glycol repeating units and a polymerizable group disposed at both ends of the chain portion. The monomer component preferably further comprises a copolymerizable monomer. In one embodiment, the copolymerizable monomer comprises a hydrophilic monomer. In one embodiment, the copolymerizable monomer comprises a compatibilizing monomer. In addition, the polymerizable composition may further comprise a hydrophilic polymer. By polymerizing the polymerizable composition comprising a monomer component and a hydrophilic polymer, a polymer material in which a polymer comprising a structural unit derived from the monomer component and a hydrophilic polymer component are highly composited can be obtained. In addition, the polymerizable composition may further comprise any appropriate additive as required.

[0038] A-1. Monomer components

[0039] The monomer component contains a siloxane monomer and a crosslinkable monomer containing no siloxane including a crosslinkable monomer containing an alkylene glycol chain, and preferably further contains a copolymerizable monomer.

[0040] A-1-1. Siloxane monomer

[0041] As long as the siloxane monomer has a siloxane bond (Si-O-Si) and a polymerizable group, any appropriate monomer can be used. Since the siloxane monomer has a siloxane bond, it can impart high oxygen permeability to the polymer material. In one embodiment, the siloxane monomer can 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 can be a crosslinked siloxane monomer having two or more polymerizable groups in the molecule. It should be noted that in the embodiment of the present invention, only one siloxane monomer can be used, or two or more can be used in combination.

[0042] Examples of the siloxane monomer include monomers conventionally used as materials for contact lenses, such as the siloxane monomers described in paragraphs 0039 to 0044 of JP-A-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 by formula (A-1), formula (A-2) or (A-3)). In the present specification, these publications are cited in their entirety for reference.

[0043] A 1 -Z 1 -U 1 -Z 2 -Z 3 -(-S 1 -U 2 -) n -S 2 -Z 4 -Z 5 -U 3 -Z 6 -A 2

[0044] ···(A)

[0045] In the general formula (A),

[0046] 1) n is 0 or an integer from 1 to 10.

[0047] 2) A 1 and A 2Each is a group represented by the following general formula (A-II) and general formula (A-III). In the following general formula (A-II) and general formula (A-III), Y 21 and Y 22 are each independently acryloyloxy, methacryloyloxy, vinyl or allyl, and R 21 and R 22 Each independently represents a direct bond or a linear or branched alkylene group having 2 to 6 carbon atoms.

[0048] Y 21 -R 21 -··· (A-II)

[0049] -R 22 -Y 22 (A-III)

[0050] 3) Z 1 , Z 2 , Z 3 , Z 4 , Z 5 and Z 6 Each is independently a polyalkylene glycol chain having a direct bond or an alkylene glycol (oxyalkylene) as a repeating unit. 1 ~Z 6 At least one of the Z is a polyethylene glycol chain having a repeating number of ethylene glycol of 2 or more, preferably 4 to 15, and Z is not a polyethylene glycol chain. 1 ~Z 6 At least one of them 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 structural unit, and as a specific example, a polypropylene glycol chain having 5 to 16 repeating units of propylene glycol).

[0051] 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. 21 is -NHCO- (in this case, E 21 With X 21 A urethane bond is formed), or a divalent group derived from a diisocyanate selected from the group consisting of a saturated or unsaturated aliphatic, alicyclic and aromatic diisocyanate (in this case, E 21 In Z 1 and X 21 A carbamate bond is formed between 21 For oxygen atoms.

[0052] -E 21 -X 21-··· (A-IV)

[0053] 5) U 2 is a group represented by the following general formula (A-VI), and contains a urethane bond in the molecular chain of the siloxane monomer. 41 and R 42 are each independently a linear or branched alkylene group having 2 to 6 carbon atoms, 41 and X 42 Each independently represents an oxygen atom or an alkylene glycol group, E 41 is a divalent group derived from a diisocyanate selected from the group consisting of a saturated or unsaturated aliphatic, alicyclic and aromatic diisocyanate (in this case, E 41 In X 41 and X 42 A urethane bond is formed between them).

[0054] -R 41 -X 41 -E 41 -X 42 -R 42 -··· (A-VI)

[0055] 6) U 3 is a group represented by the following general formula (A-VII), and contains a urethane bond in the molecular chain of the siloxane monomer. 22 is the oxygen atom, E 22 is -NHCO- (in this case, E 22 In with X 22 A urethane bond is formed between the two groups), or a divalent group derived from a diisocyanate selected from the group consisting of a saturated or unsaturated aliphatic, alicyclic and aromatic diisocyanate (in this case, E 22 In Z 5 and X 22 A urethane bond is formed between them).

[0056] -X 22 -E 22 -··· (A-VII)

[0057] 7) S 1 and S 2 Each is independently a group represented by the following general formula (AV). 31 and R 38 Each independently represents a linear or branched alkylene group having 2 to 6 carbon atoms, R 32 , R 33 , R 34 , R35 , R 36 and R 37 Each is independently an alkyl group having 1 to 6 carbon atoms, an alkyl group substituted by fluorine, or a phenyl group. In addition, K is an integer of 1 to 1500, L is 0 or an integer of 1 to 1500, and the sum of K and L: "K+L" is, for example, an integer of 1 to 1500, preferably an integer of 2 to 1000, and more preferably an integer of 3 to 500.

[0058]

[0059] General formula (A-1):

[0060]

[0061] (In the 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. 52 and R 53 is a hydrogen atom or a methyl group, in R5 2 When R is a hydrogen atom, 53 Methyl, in R 52 In the case of methyl group, R 53 is a hydrogen atom.)

[0062] General formula (A-2):

[0063]

[0064] (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. In addition, R 61 and R 62 is a hydrogen atom or a methyl group, in R 61 When R is a hydrogen atom, 62 Methyl, in R 61 In the case of methyl, R 62 is a hydrogen atom.)

[0065] General formula (A-3):

[0066]

[0067] (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. In addition, R 81 and R 82 is a hydrogen atom or a methyl group, in R 81 When R is a hydrogen atom, 82 Methyl, in R 81 In the case of methyl group, R 82 is a hydrogen atom.)

[0068] Other specific examples of the siloxane monomer 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 (meth)acrylate, tris(trimethylsiloxy)silylpropyl glyceryl (meth)acrylate, mono[methylbis(trimethylsiloxy)siloxy]bis(trimethylsiloxy)silylpropyl (meth)acrylate, (meth)acrylate alkyl esters containing silicone, such as trimethylsilylethyltetramethyldisiloxypropyl(meth)acrylate, trimethylsilylmethyl(meth)acrylate, trimethylsilylpropyl(meth)acrylate, trimethylsilylpropyl(meth)acrylate, trimethylsilylpropyl(meth)acrylate, trimethylsilylpropyl(meth)acrylate, trimethylsilylpropyl(meth)acrylate, trimethylsilyloxydimethylsilylpropyl(meth)acrylate, methylbis(trimethylsiloxy)silylethyltetramethyldisiloxymethyl(meth)acrylate, tetramethyltriisopropylcyclotetrasiloxypropyl(meth)acrylate, and tetramethyltriisopropylcyclotetrasiloxybis(trimethylsiloxy)silylpropyl(meth)acrylate;Tris(trimethylsiloxy)silylstyrene, bis(trimethylsiloxy)methylsilylstyrene, (trimethylsiloxy)dimethylsilylstyrene, tris(trimethylsiloxy)siloxydimethylsilylstyrene, [bis(trimethylsiloxy)methylsiloxy]dimethylsilylstyrene, (trimethylsiloxy)dimethylsilylstyrene, heptamethyltrisiloxystyrene, nonamethyltetrasiloxystyrene, pentamethylheptasiloxystyrene, heneicomethyldecasiloxystyrene, heptacosyltridecylstyrene, heptacosyltridecylstyrene, heptacosylpentadecasiloxystyrene, tris(pentamethyldisiloxy)silylstyrene, tris(trimethylsiloxy)siloxybis(trimethylsiloxy)silylstyrene, bis(heptamethyltrisiloxy)methylsilylstyrene, tris[methylbis(trimethylsiloxy)siloxy]silylstyrene, heptacosyltrisiloxy oxy) trisilylstyrene, trimethylsiloxybis[tris(trimethylsiloxy)siloxy]silylstyrene, nonamethyltetrasiloxyundecylmethylpentasiloxymethylsilylstyrene, tris[tris(trimethylsiloxy)siloxy]silylstyrene, (tris-trimethylsiloxyhexamethyl)tetrasiloxy[tris(trimethylsiloxy)siloxy]trimethylsiloxysilylstyrene, nona(trimethylsiloxy)tetrasilylstyrene, bis(tridecamethyl)tetrasilylstyrene Styrene derivatives containing silicone, such as bis(3-(trimethylsilyl)propyl)fumarate, bis(3-(pentamethyldisiloxanyl)propyl)fumarate, bis(tris(trimethylsiloxy)silylpropyl)fumarate, etc.;

[0069] As further specific examples of the siloxane monomer, there can be mentioned: mono(meth)acryloxypropyl terminal mono-n-butyl terminal polydimethylsiloxane, mono(meth)acryloxypropyl terminal mono-n-methyl terminal polydimethylsiloxane, mono(meth)acryloxypropyl terminal mono-n-butyl terminal polydiethylsiloxane, mono(meth)acryloxypropyl terminal mono-n-methyl terminal polydiethylsiloxane, mono(meth)acrylaminopropyl terminal mono-n-butyl terminal polydimethylsiloxane, mono(meth)acrylaminopropyl terminal mono-n-methyl terminal polydimethylsiloxane, mono(meth)acrylaminopropyl terminal mono-n-butyl terminal polydiethylsiloxane, mono(meth)acrylaminopropyl terminal mono-n-methyl terminal polydiethylsiloxane, etc. In these siloxane monomers, the number of repetitions of (Si—O) can be, for example, 4 to 20, preferably 4 to 12, and more preferably 4 to 10.

[0070] 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, and as a result, a silicone hydrogel having excellent transparency can be obtained even when the mixing ratio of the siloxane monomer is increased.

[0071] In one embodiment, a siloxane monomer without a hydrophilic group and a siloxane monomer with a hydrophilic group can be used in combination. By using these two siloxane monomers in combination, the compatibility with the hydrophilic monomer is improved, and as a result, a silicone hydrogel with excellent transparency can be obtained regardless of the presence or absence of a compatible monomer.

[0072] As the hydrophilic group, hydroxyl group, carboxyl group, sulfonic acid group, phosphoric acid group, etc. can be listed. Among them, siloxane monomers having hydroxyl groups are preferred. As siloxane monomers having hydroxyl groups, (3-methacryloyloxy-2-hydroxypropyloxy)propylbis(trimethylsiloxy)methylsilane (SiGMA) and the like can be listed.

[0073] The weight average molecular weight of the siloxane monomer is typically less than 10000 g / mol. In one embodiment, a siloxane monomer having a weight average molecular weight of, for example, less than 1000 g / mol, preferably 200 g / mol to 900 g / mol, and 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 operations such as injection into the mold become easier. In addition, in another embodiment, a siloxane monomer having a weight average molecular weight of, for example, more than 1000 g / mol and less than 10000 g / mol, preferably 2000 g / mol to 9000 g / mol, and more preferably 3000 g / mol to 8000 g / mol can be preferably used. By using such a siloxane monomer, a higher oxygen permeability improvement effect can be obtained. These siloxane monomers can be used alone or in combination. By using such two siloxane monomers in combination, high oxygen permeability can be exhibited while maintaining the appropriate viscosity of the polymerizable composition.

[0074] The number of repetitions of the siloxane bonds possessed by the siloxane monomer is typically less than 1500, preferably less than 100. In one embodiment, a siloxane monomer having a repetition number of, for example, 1 to 20, preferably 2 to 20, more preferably 3 to 12, and further preferably 4 to 10 of the siloxane bonds can be preferably used. By using such a siloxane monomer, the viscosity of the entire polymerizable composition can be reduced, and operations such as injection into the mold become easier. In addition, in another embodiment, a siloxane monomer having a repetition number of, for example, more than 20 and less than 1500, preferably more than 20 and less than 100, more preferably more than 20 and less than 80 of the siloxane bonds can be preferably used. By using such a siloxane monomer, a higher oxygen permeability improvement effect can be obtained. These siloxane monomers can be used alone or in combination. By using two siloxane monomers in combination, high oxygen permeability can be exhibited while maintaining an appropriate viscosity of the polymerizable composition. It should be noted that in these embodiments, the polysiloxane structure contained in the siloxane monomer may be a straight chain or a branched chain. In addition, in this specification, a siloxane monomer having more than 20 siloxane bonds or a siloxane monomer having a weight average molecular weight of more than 1000 g / mol is also referred to as a siloxane macromonomer.

[0075] The blending ratio of the siloxane monomer (the total blending ratio when 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 in the polymerizable composition and the hydrophilic polymer when the hydrophilic polymer is present. If the blending ratio of the siloxane monomer is within this range, a polymer material having high oxygen permeability can be obtained.

[0076] When a siloxane macromonomer (for example, a siloxane monomer represented by formula (A)) is used in combination with other siloxane monomers, the blending ratio of the siloxane macromonomer relative to all siloxane monomers (the total of the siloxane macromonomer and other siloxane monomers) may be preferably 20 wt % or less, more preferably 5 wt % to 15 wt %.

[0077] When a siloxane monomer having a hydrophilic group and a siloxane monomer having no hydrophilic group are used in combination, the blending ratio of the siloxane monomer having a hydrophilic group is preferably 1% by weight to 60% by weight, more preferably 5% by weight to 50% by weight, relative to all siloxane monomers (the total of the siloxane monomer having a hydrophilic group and the siloxane monomer having no hydrophilic group).

[0078] A-1-2. Crosslinking monomers not containing silicone

[0079] The crosslinkable monomer not containing siloxane has no siloxane bond and has two or more polymerizable groups. In the embodiment of the present invention, as the crosslinkable monomer not containing siloxane, one of its characteristics is to use a crosslinkable monomer containing an alkylene glycol chain, wherein the crosslinkable monomer containing an alkylene glycol chain has a chain portion containing 6 or more alkylene glycol repeating units and polymerizable groups arranged at both ends of the chain portion. As required, a crosslinkable monomer other than the crosslinkable monomer containing an alkylene glycol chain (hereinafter also referred to as a second crosslinkable monomer) may be further used as the crosslinkable monomer not containing siloxane.

[0080] The proportion of the crosslinkable monomer not containing siloxane (the total proportion when two or more crosslinkable monomers not containing siloxane are used) relative to the total amount of all monomer components in the polymerizable composition and the hydrophilic polymer when the hydrophilic polymer is present can be, for example, 2% by weight or more, preferably 2.2% by weight or more, more preferably 3% by weight to 25% by weight, and even more preferably 3% by weight to 20% by weight.

[0081] A-1-2-1. Crosslinking monomer containing alkylene glycol chain

[0082] The cross-linking monomer containing an alkylene glycol chain has a chain portion containing 6 or more alkylene glycol repeating units and a polymerizable group disposed at both ends of the chain portion. By using a cross-linking monomer having a structure in which a polymerizable group is disposed at both ends of a relatively long polyether chain, a hydrophilic mesh structure is formed using the polyether chain, thereby forming a polymer network structure that can suppress the invasion of hydrophobic molecules such as lipids while maintaining oxygen permeability. As a result, it is inferred that a polymer material that takes into account both oxygen permeability and surface hydrophilicity and suppresses the attachment of lipids can be obtained. It should be noted that in the embodiment of the present invention, only one cross-linking monomer containing an alkylene glycol chain can be used, or two or more can be used in combination.

[0083] The HLB (Hydrophilic-Lipophilic Balance) of the cross-linking monomer containing an alkylene glycol chain is preferably 5 to 20, more preferably 5.5 to 18, and further preferably 6 to 15. If the HLB is within this range, the compatibility with the siloxane monomer is excellent. It should be noted that in this specification, the HLB of the cross-linking monomer containing an alkylene glycol chain is a value calculated using the Davies method based on the following formula (wherein the number of groups of (EO (i.e., ethylene oxide)) is 0.33, the number of groups of (PO (i.e., propylene oxide)) is -0.15, and the total number of groups of the terminal methacrylic groups is 0.1).

[0084] HLB = 7 + Σ (number of hydrophilic groups) + Σ (number of lipophilic groups)

[0085] In one embodiment, the crosslinkable monomer containing an alkylene glycol chain can be represented by the following formula (1).

[0086] P 1 -X-(A 1 O) m1 -[L 1 -(A 2 O) m2 ] n1 -[L 2 -(A 3 O) m3 ] n2 -ZP 2 (1)

[0087] (Where,

[0088] P 1 and P 2 represents polymerizable groups which may be the same as or different from each other,

[0089] A 1 O.A 2 O and A 3 O represents alkylene glycol repeating units which may be the same as or different from each other,

[0090] X represents a single bond, -O-, -NH-, -O-CH 2 CH 2 -NH-CO-O- or -O-CH 2 CH(OH)CH 2 O-,

[0091] Z represents a single bond, -NH-, -CH 2 CH 2 -NH-CO-O- or -CH 2 CH(OH)CH 2 O-,

[0092] L 1 and L 2 Each is independently a single bond or a divalent linking group,

[0093] n1 and n2 are each independently 0 or 1,

[0094] m1, m2 and m3 are each independently an integer greater than 1,

[0095] Among them, the relationship m1+m2×n1+m3×n2≥6 is satisfied. )

[0096] In formula (1), P 1 and P 2The polymerizable group specified in is preferably a (meth)acryloyl group, a vinyl group or an allyl group, and more preferably a (meth)acryloyl group.

[0097] In formula (1), L 1 and L 2 The linking group specified in is a single bond or a divalent linking group as described above. Examples of the divalent linking group include a linear or branched alkylene group having 1 to 5 carbon atoms. 1 and L 2 The connecting group specified in is preferably a single bond.

[0098] In formula (1), -(A 1 O) m1 -[L 1 -(A 2 O) m2 ] n1 -[L 2 -(A 3 O) m3 ] n2 - The predetermined chain part contains 6 or more alkylene glycol repeating units. The number of alkylene glycol repeating units contained in the chain part (m1+m2×n1+m3×n2) is preferably 6 to 50, more preferably 6 to 40, further preferably 6 to 30, further more preferably 6 to 25, further more preferably 7 to 20. The number of alkylene glycol repeating units contained in the chain part may be, for example, 8 or more or 9 or more. If the number of repeating units is within this range, an excellent effect of preventing lipid adhesion can be obtained.

[0099] The alkylene glycol repeating units may be arranged discontinuously or continuously in the chain part. Preferably, the chain part contains 6 or more alkylene glycol repeating units continuously, more preferably 6 to 50 alkylene glycol repeating units continuously, further preferably 6 to 40 alkylene glycol repeating units continuously, further preferably 6 to 30 alkylene glycol repeating units continuously, further preferably 6 to 25 alkylene glycol repeating units continuously, further preferably 7 to 20 alkylene glycol repeating units continuously. The number of continuous repeating units in the chain part may be, for example, 8 or more or 9 or more.

[0100] As the alkylene glycol repeating unit contained in the chain portion (A in formula (1) 1 O.A 2 O or A 3O), preferably an alkylene glycol repeating unit having 5 or less carbon atoms, more preferably an ethylene glycol repeating unit (EO), a propylene glycol (representatively propane-1,2-diol) repeating unit (PO) and a butanediol (representatively 1,3-butanediol or 1,4-butanediol) repeating unit (BO (i.e., butylene oxide)), and further preferably an ethylene glycol repeating unit and a propylene glycol repeating unit. It should be noted that 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 O's may be different alkylene glycol repeating units or the same alkylene glycol repeating units.

[0101] Specific examples of the crosslinking monomer containing an alkylene glycol chain 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.

[0102] In addition, although the structure in which each alkylene glycol repeating unit forms a block structure is shown in formula (1), when the crosslinkable monomer containing an alkylene glycol chain contains two or more alkylene glycol repeating units, each repeating unit may be randomly arranged.

[0103] The blending ratio of the crosslinking monomer containing an alkylene glycol chain (the total blending ratio when two or more crosslinking monomers containing an alkylene glycol chain are used) relative to the total blending amount of all monomer components in the polymerizable composition and the hydrophilic polymer when the hydrophilic polymer is present is, for example, 0.9 wt % or more, and for example, 1 wt % or more, preferably 2 wt % or more, more preferably 3 wt % to 25 wt %, and further more preferably 3 wt % to 20 wt %. In addition, the blending ratio of the crosslinking monomer containing an alkylene glycol chain relative to the total 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 a crosslinking monomer containing an alkylene glycol chain in such a blending ratio, a polymer material having both oxygen permeability and surface hydrophilicity and in which lipid adhesion is suppressed can be preferably obtained.

[0104] A-1-2-2. Second crosslinking monomer

[0105] As the second crosslinking monomer, any appropriate crosslinking monomer not containing siloxane can be used except the crosslinking monomer containing an alkylene glycol chain. 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-vinyl pyrrolidone, (meth)acrylate 4-vinylbenzyl ester, 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.

[0106] The blending ratio of the second crosslinkable monomer (the total blending ratio when two or more second crosslinkable monomers are used) can be selected so that the total blending ratio with the crosslinkable monomer containing an alkylene glycol chain is, for example, 2% by weight or more, more preferably 2.2% by weight or more, further preferably 3% by weight to 25% by weight, and further preferably 3% by weight to 20% by weight, relative to the total blending ratio of all monomer components in the polymerizable composition and the hydrophilic polymer when the hydrophilic polymer is present. The blending ratio of the second crosslinkable monomer alone in the polymerizable composition can be, for example, 0.1% by weight to 10% by weight, and can also be, for example, 0.5% by weight to 5% by weight, relative to the total blending ratio of all monomer components in the polymerizable composition and the hydrophilic polymer when the hydrophilic polymer is present.

[0107] A-1-3. Copolymerizable monomers

[0108] As the copolymerizable monomer, a monomer having a single polymerizable group and having no siloxane bond can be used. Specific examples of the copolymerizable monomer include hydrophilic monomers, compatibilizing monomers, and functional monomers.

[0109] The proportion of the copolymerizable monomer to the total amount of all monomer components in the polymerizable composition and the hydrophilic polymer when present is 20 to 70% by weight, preferably 25 to 65% by weight, and more preferably 30 to 65% by weight. In addition, the total proportion of the siloxane monomer, the crosslinking monomer containing an alkylene glycol chain, the hydrophilic monomer, and the compatibilizing monomer to the total amount of all monomer components and the hydrophilic polymer when present is 80% by weight or more, preferably 90% by weight or more, and more preferably 94% by weight or more, and the upper limit thereof may be 100% by weight, for example, 99.99% by weight or less, and for example, 99% by weight or less. In addition, the total proportion of the siloxane monomer, the cross-linking monomer containing an alkylene glycol chain, the hydrophilic monomer and the compatibilizing monomer 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, and the upper limit thereof can be 100% by weight, for example, 99.99% by weight or less, and for example, 99% by weight or less.

[0110] A-1-3-1. Hydrophilic monomer

[0111] The hydrophilic monomer can increase the hydrophilicity of the obtained polymer material. As the hydrophilic monomer, 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 (excluding monomers containing silicon atoms and monomers having two or more polymerizable groups) can be used.

[0112] Specific examples of the hydrophilic monomer include: hydroxyl-containing alkyl (meth)acrylates (e.g., hydroxyl-containing alkyl (meth)acrylates having an alkyl group with 1 to 5 carbon atoms), such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, dihydroxypropyl (meth)acrylate, and glycerol mono(meth)acrylate; (meth)acrylamides (e.g., alkyl (meth)acrylamides having an alkyl group with 1 to 5 carbon atoms), such as N,N-dimethyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-2-hydroxyethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, and N-acryloylmorpholine; N-vinyl lactams such as N-vinylpyrrolidone, N-vinylpiperidone, and N-vinylcaprolactam; N-methyllactams such as 1-methyl-3-methylene-2-pyrrolidone, and methyl (meth)acrylate; and alkoxyalkyl (meth)acrylates having an alkoxyalkyl group with 2 to 4 carbon atoms. Among them, preferably used are 2-hydroxyethyl (meth)acrylate, N,N-dimethyl (meth)acrylamide, N-vinyl pyrrolidone, methoxyethyl acrylate, methyl acrylate, glycerol mono(meth)acrylate, etc. The hydrophilic monomer may be used alone or in combination of two or more.

[0113] The mixing ratio of the hydrophilic monomer in the polymerizable composition (the total mixing ratio when 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 mixing amount of all monomer components in the polymerizable composition and the hydrophilic polymer when the hydrophilic polymer is present. If the mixing ratio of the hydrophilic monomer is within this range, a polymer material having a high water content and surface hydrophilicity can be obtained.

[0114] A-1-3-2. Compatibilizing monomer

[0115] The compatibilizing monomer can improve the compatibility of the siloxane monomer with the hydrophilic monomer and / or the hydrophilic polymer. As the compatibilizing monomer, preferably used is a monomer having a group containing a proton having a hydrogen bond and having no silicon atom and having 4 or more carbon atoms in addition to the carbon atoms contained in the polymerizable group.

[0116] The number of carbon atoms in the compatibilizing monomer (excluding carbon atoms in the polymerizable group) is, for example, 6 or more, preferably 6 to 25, more preferably 7 to 15, and further preferably 8 to 13. In the compatibilizing monomer, for example, each hydrogen-bonding proton-containing group has 4 or more carbon atoms, and may have, for example, 5 to 15, and further preferably 8 to 13 carbon atoms.

[0117] Examples of the hydrogen-bonding proton-containing group include a hydroxyl group, a carboxyl group, an amino group, an amide bond, a sulfonic acid group (-SO 3 H), urethane bonds, urea bonds, etc. Among them, hydroxyl groups are preferred. The number of groups containing hydrogen bond protons possessed by the compatibilizing monomer is, for example, 1 to 12, preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 or 2.

[0118] 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 having a proton-containing group such as a hydroxyl group but having a hydrophobic property as a whole can help improve the compatibility of the siloxane monomer with the hydrophilic monomer and / or the hydrophilic polymer.

[0119] In one embodiment, the compatibilizing monomer not only has a polymerizable group and a group containing a hydrogen-bonding proton, but also has a hydrophobic group containing more than 2 carbon atoms, preferably more than 4 carbon atoms. In this embodiment, preferably, the compatibilizing monomer has a polymerizable group, a middle part containing a group containing a hydrogen-bonding proton, and a hydrophobic terminal part containing more than 2 carbon atoms, more specifically, preferably, a polymerizable group is configured at one of the terminal parts of the compatibilizing monomer molecule, a hydrophobic group is configured at another terminal part, and a relatively high group of hydrophilicity of the group containing a hydrogen-bonding proton is configured between these. The compatibilizing monomer having a group containing a hydrogen-bonding proton at a relatively close position to a polymerizable group such as (methyl) acryloyl and a terminal hydrophobic group at a relatively far position can help improve the compatibility of the siloxane monomer with a hydrophilic monomer and / or a hydrophilic polymer.

[0120] The compatibilizing monomer of the embodiment can be represented by the following formula (B).

[0121] P 3 -AB (B)

[0122] (Where,

[0123] P 3 represents a (meth)acryloyl group,

[0124] A contains a group containing a proton containing a hydrogen bond, or represents 3 A divalent group of atoms that together form a group containing hydrogen-bonding protons,

[0125] B represents a hydrocarbon group having 2 to 20 carbon atoms,

[0126] The total number of carbon atoms contained in A and B is 4 or more.)

[0127] In the formula (A), the divalent atomic group specified in A can be represented by the following formula, for example:

[0128] *-XR a1 -(L a1 ) r1 -[(R a2 ) r2 -(L a2 ) r3 ] r4 -

[0129] (i)

[0130] (Here, * indicates the same 3 The bonding site of

[0131] X represents O or NR a3 ,

[0132] R a1 and R a2 each independently represents an alkylene group having 1 to 20 carbon atoms which may have a hydroxyl group,

[0133] R a3 represents hydrogen or an alkyl group having 1 to 4 carbon atoms,

[0134] 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,

[0135] r1 to r3 each independently represent 0 or 1,

[0136] r4 represents an integer from 0 to 10,

[0137] in,

[0138] In R a2 When there is no hydroxyl group, r3 and r4 are not 0,

[0139] (i) The atomic group has at least one group containing a hydrogen-bonding proton.

[0140] R a1 and R a2 Each independently represents an alkylene group having 1 to 6 carbon atoms which may preferably 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 At least one of them has a hydroxyl group, and more preferably R a1 As such an embodiment, R a1 With hydroxyl group and without R a2 Implementations (e.g., implementations in which r1=0 or 1, r2=0, r3=0) or R a1 and R a2 Both of these have an embodiment in which a hydroxyl group is present (for example, an embodiment in which r1=1, r2=1, and r3=0 or 1), and the like.

[0141] In the presence of L a1 and L a2 When L a1 and L a2 Each independently may be preferably an ether bond or an ester bond. a1 and R a2 When neither of them has a hydroxyl group, L a1 and L a2 At least one of them is an amide bond, a urethane bond, or a urea bond.

[0142] The hydrocarbon group specified in B may be straight chain, branched chain, or contain a cyclic structure, or contain a heteroatom at any position. The heteroatom is not limited as long as the effect 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 5 to 12 carbon atoms.

[0143] Specific examples of the compatibilizing monomer according to the above embodiment are shown in the following formula (I), formula (V) or formula (VI).

[0144]

[0145] (Where,

[0146] R 1 represents a hydrogen atom or a methyl group,

[0147] R 2 and R 3 each independently represents an alkylene group having 1 to 6 carbon atoms,

[0148] R 4 represents a hydrocarbon group having 2 to 20 carbon atoms, represented by -(R 5a ) s -OR 5b 、-(R 5a ) s -O(C=O)-R 5b Or -(R 5a ) s -(C=O)OR 5b The structure represented (here, R 5a represents an alkylene group having 1 to 4 carbon atoms, R 5b represents a hydrocarbon group having 2 to 20 carbon atoms, s represents 0 or 1),

[0149] X 1 Indicates O or NR 6 , (here, R 6 represents hydrogen or an alkyl group having 1 to 4 carbon atoms),

[0150] X 2 represents a single bond or an alkylene group having 1 to 3 carbon atoms,

[0151] X 3 represents 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 formula (II) to formula (IV),

[0152]

[0153] (Here, 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, t and u each independently represent 0 or 1),

[0154] n is an integer from 0 to 10,

[0155] q1 and q2 are each independently 0 or 1,

[0156] in,

[0157] Removal of polymerizable groups (CH 2 =CR 1 The total number of carbon atoms contained in the residue after -CO-) is 4 or more,

[0158] R 4 , R 5b , R 6 , R 8a and R 8b The hydrocarbon group or alkyl group specified in each independently may have a heteroatom. )

[0159] Regarding formula (I), R 4 and R 5b The hydrocarbon groups specified in the formula are each preferably an aliphatic hydrocarbon group (e.g., an alkyl group) having 2 to 12 carbon atoms, more preferably 3 to 10 carbon atoms, and 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 these hydrocarbon groups function as terminal hydrophobic groups, and the compatibilizing monomer can exert affinity for the siloxane-containing monomer.

[0160] As R 4 or R 5bSpecific examples of the hydrocarbon groups specified in the above include straight-chain alkyl groups such as ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl; isopropyl, methylpropyl, tert-butyl, dimethylpropyl, ethylpropyl, diethylpropyl, methylbutyl, dimethylbutyl, trimethylbutyl, ethylbutyl, propylbutyl, methylpentyl, dimethylpentyl, ethylpentyl, propylpentyl, butylpentyl, methylhexyl, dimethylhexyl, trimethylhexyl, ethylhexyl, propylhexyl, butylhexyl, methylheptyl, dimethylheptyl, ethylheptyl, propylheptyl, methyloctyl, dimethyloctyl, and ethyloctyl. , methylnonyl and other branched alkyl groups; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and other cycloalkyl groups; cyclooctylethyl, cycloheptylmethyl, cycloheptylethyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, cyclohexylbutyl, cyclopentylethyl, cyclopentylpropyl, cyclopentylbutyl, cyclopentylpentyl, cyclobutylpropyl, cyclobutylbutyl, cyclobutylpentyl, cyclopropylbutyl, cyclopropylpentyl, cyclopropylhexyl and other alkyl groups containing cycloalkyl rings; norbornyl, tricyclodecyl, tetracyclododecyl, adamantyl, methyladamantyl, ethyladamantyl, butyladamantyl and the like.

[0161] R 6 , R 8a and R 8b The groups are each preferably hydrogen or an alkyl group having 1 or 2 carbon atoms.

[0162] X 3 , R 2 , R 3 , R 5a and R 7a The alkylene group specified in each of the above 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.

[0163] R 7b The alkylene group defined in the above is preferably an alkylene group having 1 to 8 carbon atoms, more preferably an alkylene group having 1 to 4 carbon atoms.

[0164] 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 methylene or ethylene, and R is absent 2 Implementation method (i.e., implementation method with q1=0); X 2 and R 2 (The embodiments in which all of them are methylene groups, etc.) It is considered that the compatibilizing monomer can exhibit affinity for the hydrophilic monomer and / or the hydrophilic polymer by arranging the hydroxyl group close to the (meth)acryloyl group.

[0165] X3 The total number of carbon atoms contained in the group is preferably 0-10, more preferably 1-5, and further preferably 1-3.

[0166] As R 4 , R 5b , R 6 , R 8a and R 8b The heteroatoms that the hydrocarbon group or alkyl group specified in the above may have are not limited as long as the effects of the present invention can be obtained, and examples thereof include halogens such as fluorine. 4 , R 5a , R 6 , R 8a or R 8b The hydrocarbon group or alkyl group specified in may be a fluoroalkyl group or a perfluoroalkyl group.

[0167] n is preferably 0-5, more preferably 0, 1 or 2.

[0168] In one embodiment, in formula (I), R 1 is a hydrogen atom or a methyl group, X 1 O, X 2 is methylene or ethylene, preferably methylene, n is 0, R 4 For -(R 5a ) s -OR 5b (Among them, R 5a is methylene, s is 1, R 5b is a hydrocarbon group having 2 to 20 carbon atoms which may be substituted by fluorine), q1 is 0 or 1, and preferably 0.

[0169] In one embodiment, in formula (I), R 1 is a hydrogen atom or a methyl group, X 1 O, X 2 is methylene or ethylene, preferably methylene, n is 0, R 4 For -(R 5a ) s -O(C=O)-R 5b (Among them, R 5a is methylene, s is 1, R 5b is a hydrocarbon group having 2 to 20 carbon atoms which may be substituted by fluorine), q1 is 0 or 1, and preferably 0.

[0170] In one embodiment, in formula (I), R 1 is a hydrogen atom or a methyl group, X 1 O, X 2 is methylene or ethylene, preferably methylene, n is 0, R 4It is a hydrocarbon group having 2 to 20 carbon atoms which may be substituted by fluorine; q1 is 0 or 1, and preferably 0.

[0171]

[0172] (Where,

[0173] R 9 represents a hydrogen atom or a methyl group,

[0174] R 10 represents a hydrocarbon group having 4 to 20 carbon atoms, represented by -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 represents an alkylene group having 1 to 4 carbon atoms, R 10b represents a structure represented by a hydrocarbon group having 2 to 20 carbon atoms,

[0175] in,

[0176] R 10 The total number of carbon atoms contained in the group is 4 or more,

[0177] R 10 or R 10b The hydrocarbon group specified in the formula may have heteroatoms.)

[0178] Regarding formula (V), R 10 or R 10b The hydrocarbon groups specified in the formula are preferably aliphatic hydrocarbon groups (e.g., alkyl groups) having 4 to 12 carbon atoms, and more preferably 4 to 10 carbon atoms. Each of these hydrocarbon groups may be linear, branched, or may include a cyclic structure. It is believed that these hydrocarbon groups function as terminal hydrophobic groups, and the compatibilizing monomer can exert affinity for the siloxane monomer.

[0179] As R 10 or R 10b Specific examples of the hydrocarbon group specified in the formula (a) include the following: 4 or R 5b The specific examples of the hydrocarbon groups specified in hereinafter are the same hydrocarbon groups (including hydrocarbon groups having 4 or more carbon atoms).

[0180] R 10a The alkylene group specified in 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.

[0181] As R 10 or R 10b The heteroatom that the hydrocarbon group specified in the above may have is not limited as long as the effect of the present invention can be obtained, and examples thereof include halogens such as fluorine. In one embodiment, R 10 or R 10b The hydrocarbon group specified in may be a fluoroalkyl group or a perfluoroalkyl group.

[0182]

[0183] (Where,

[0184] R 11 represents a hydrogen atom or a methyl group,

[0185] X 4 Indicates O or NR 14 (Here, R 14 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms),

[0186] R 12 represents an alkylene group having 2 to 14 carbon atoms,

[0187] X 5 is a single bond, O or a structure represented by the following formula (VII) to formula (IX),

[0188]

[0189] (Here, R 15a and R 15b each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms),

[0190] R 13 represents a hydrocarbon group having 2 to 20 carbon atoms,

[0191] in,

[0192] In X 4 When not NH, X 5 is a structure containing a carbamate bond (-NHCOO-) or a urea bond (-NHCONH-),

[0193] R 12 , R 13 , R 14 , R 15a and R 15b Each independently may have a heteroatom. )

[0194] Regarding formula (VI), R 12 The alkylene group defined in R may be linear or branched, or may contain a cyclic structure. 12An alkylene group having 2 to 6 carbon atoms is preferred, and an ethylene group, a propylene group, or a butylene group is more preferred.

[0195] R 13 The hydrocarbon group specified in 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 or branched, or may include a cyclic structure. It is believed that the compatibilizing monomer can exert affinity for the siloxane monomer by functioning as a terminal hydrophobic group.

[0196] As R 13 Specific examples of the hydrocarbon group specified in the formula (a) include the following: 4 or R 5b The specific examples of the hydrocarbon groups specified in .

[0197] As R 14 , R 15a and R 15b Specific examples of the alkyl group defined in the above include a methyl group and an ethyl group.

[0198] As R 12 , R 13 , R 14 , R 15a and R 15b The heteroatom that may be present 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 15b It may be a fluoroalkyl group or a perfluoroalkyl group.

[0199] 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 substituted with a group containing a hydrogen-bonding proton. As the alicyclic ring, preferably alicyclic rings with 5 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and further preferably 8 to 12 carbon atoms can be listed, and alicyclic rings with a bridged structure can also be used. As a specific example of the compatibilizing monomer of this embodiment, (meth)acrylates having a bridged alicyclic group substituted with one or more hydroxyl groups (for example, adamantyl, norbornyl, tricyclodecyl, tetracyclododecyl, etc.) can be preferably exemplified, and more specifically, hydroxy(meth)acryloyloxyadamantane, dihydroxy(meth)acryloyloxyadamantane, etc. can be preferably exemplified.

[0200] The blending ratio of the compatibilizing monomer (the total blending ratio when two or more compatibilizing monomers are used) can be, for example, 1 wt % to 40 wt %, preferably 5 wt % to 35 wt %, and more preferably 10 wt % to 30 wt % relative to the total blending ratio of all monomer components in the polymerizable composition and the hydrophilic polymer when the hydrophilic polymer is present. 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.

[0201] A-1-3-3. Functional monomer

[0202] The functional monomer is added as needed for the purpose of imparting a predetermined function to the polymer material. Examples of the functional monomer include polymerizable dyes, polymerizable ultraviolet absorbers, and polymerizable ultraviolet absorbing dyes.

[0203] Specific examples of the polymerizable dye include azo polymerizable dyes, anthraquinone polymerizable dyes, nitro polymerizable dyes, phthalocyanine polymerizable dyes, etc. These can be used alone or in combination of two or more.

[0204] Specific examples of polymerizable UV absorbers include benzophenone-based polymerizable UV absorbers, benzotriazole-based polymerizable UV absorbers, salicylic acid derivative-based polymerizable UV absorbers, 2-cyano-3-phenyl-3-(3'-(methyl)acryloyloxyphenyl) methyl acrylate, etc. These can be used alone or in combination of two or more.

[0205] 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.

[0206] The blending ratio of the functional monomer is, for example, 0.001 to 5% by weight, and preferably 0.05 to 3% by weight, relative to the total blending amount of all monomer components in the polymerizable composition and the hydrophilic polymer when the hydrophilic polymer is present.

[0207] A-1-3-4. Other copolymerizable monomers

[0208] As other copolymerizable monomers, any appropriate monomer can be used according to the purpose. For example, (meth) alkyl acrylates having an alkyl carbon number of 2 to 5 can be cited. 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 in the polymerizable composition and the hydrophilic polymer when the hydrophilic polymer is present.

[0209] A-2. Hydrophilic polymer

[0210] The hydrophilic polymer is typically a non-polymerizable component having no polymerizable group. By polymerizing the monomer component in the presence of the hydrophilic polymer, a polymer material having a highly complexed polymer containing a structural unit derived from the monomer component and the hydrophilic polymer and having increased surface hydrophilicity can be obtained.

[0211] As a hydrophilic polymer, any appropriate polymer that can impart surface hydrophilicity to a polymer material can be used. For example, polymers such as polyvinylamide (e.g., polyvinyl lactam), polyamide, polylactone, polyimide, polylactam, etc. can be used as hydrophilic polymers. Among them, polymers containing cyclic structures, such as cyclic amide structures or cyclic imide structures, in the main chain or side chains can be preferably used. The hydrophilic polymer can also be a random copolymer, alternating copolymer, block copolymer, or graft copolymer containing two or more monomers. In addition, the hydrophilic polymer can be used only one, or two or more can be used in combination.

[0212] Specific examples of the hydrophilic polymer include poly-N-vinylpyrrolidone, poly-N-vinyl-2-piperidone, poly-N-vinyl-2-caprolactam, poly-N-vinyl-3-methyl-2-caprolactam, 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, polyvinyl imidazole, poly-NN-dimethylacrylamide, polyvinyl alcohol, poly(meth)acrylic acid, poly(2-hydroxyethyl)(meth)acrylate, polyalkylene glycols such as polyethylene glycol, and poly-2-ethyl-2-pyrrolidone. Oxazoline, heparin-polysaccharide, polysaccharide, and copolymers thereof. Among them, poly-N-vinyl pyrrolidone, polyalkylene glycol, polysaccharide, poly(meth)acrylic acid, polyvinyl alcohol, poly(2-hydroxyethyl) (meth)acrylate, etc. can be preferably used.

[0213] The weight average molecular weight of the hydrophilic polymer may be, for example, 100,000 or more, preferably 150,000 to 2,000,000, more preferably 300,000 to 1,800,000, and further preferably 500,000 to 1,500,000.

[0214] 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 by the first method <2.53> of the viscosity measurement method in the 16th revision of the Japanese Pharmacopoeia, and by the method described in the "K value" column of the Pharmacopoeia, using the Fikentscher formula.

[0215] The proportion of the hydrophilic polymer in the polymerizable composition is typically 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 the hydrophilic polymer in the polymerizable composition. If the amount of the hydrophilic polymer is within this range, a polymer material having a high water content and excellent surface hydrophilicity can be obtained.

[0216] A-3. Additives

[0217] As the additive, any appropriate additive may be selected according to the purpose. Examples of the additive include a polymerization initiator and an organic solvent.

[0218] The polymerization initiator can be appropriately selected according to the polymerization method. As the thermal polymerization initiator used in the polymerization performed by heating, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), benzoyl peroxide, tert-butyl hydroperoxide, isopropylbenzene hydroperoxide, lauroyl peroxide, tert-butyl peroxyhexanoate, 3,5,5-trimethylhexanoyl peroxide, etc. can be cited. These thermal polymerization initiators can be used alone or in combination of two or more.

[0219] 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).

[0220] Examples of the photopolymerization initiator used in the polymerization by light irradiation include: phosphine oxide photopolymerization initiators such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO) and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; benzoin photopolymerization initiators such as methyl o-benzoylbenzoate, methyl benzoylformate, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzoin n-butyl ether; 2-hydroxy-2-methyl-1-phenylpropane-1-one (HMPPO), para- Isopropyl-α-hydroxyisobutylbenzophenone, p-tert-butyltrichloroacetophenone, 2,2-dimethoxy-2-phenylacetophenone, α,α-dichloro-4-phenoxyacetophenone, N,N-tetraethyl-4,4-diaminobenzophenone and other benzophenone-based photopolymerization initiators; 1-hydroxycyclohexyl phenyl ketone; 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime; 2-chlorothioxanthone, 2-methylthioxanthone and other thioxanthone-based photopolymerization initiators; dibenzosuberone; 2-ethylanthraquinone; benzophenone acrylate; benzophenone; diphenylethanedione, etc. These photopolymerization initiators may be used alone or in combination of two or more. In addition, a photosensitizer may be used together with the photopolymerization initiator.

[0221] The mixing ratio of the photopolymerization initiator and the photosensitizer in the polymerizable composition is preferably 0.001 to 2 wt %, more preferably 0.01 to 1 wt %, based on all components in the polymerizable composition (excluding the organic solvent).

[0222] The organic solvent may be a water-soluble organic solvent with high polarity or a water-insoluble organic solvent with low polarity. As the water-soluble organic solvent, alcohols having 1 to 4 carbon atoms, acetone, methyl ethyl ketone, dimethylformamide, dimethyl sulfoxide, acetonitrile, N-methyl-2-pyrrolidone, dimethoxyethane, tetrahydrofuran, 1,4-dimethoxyethane, By using a water-soluble organic solvent, the compatibility between monomer components or between a hydrophilic polymer and a monomer component can be improved. In addition, the water-soluble organic solvent can be easily removed from the polymer material by immersing it in water.

[0223] As the water-insoluble organic solvent, hexane, cyclohexane, heptane, octane, dimethyl ether, diethyl ether, benzene, toluene, xylene, ethyl acetate, propyl acetate, butyl acetate, dichloromethane, chloroform, carbon tetrachloride, alcohols with 6 or more carbon atoms, etc. can be used. By using a water-insoluble organic solvent, the compatibility between monomer components or between a hydrophilic polymer and a monomer component can be improved. In addition, when added to a polymerizable composition, the dynamic viscosity of the polymerizable composition is reduced compared to the case of using a water-soluble organic solvent, so that it can be easily handled.

[0224] The amount of the 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 all components (including the organic solvent) in the polymerizable composition.

[0225] As other additives other than the above, additives conventionally used for ophthalmic lenses can be used, for example, coolants, thickeners, surfactants, non-polymerizable pigments, ultraviolet absorbers or ultraviolet absorbing pigments, etc. can be mentioned.

[0226] The blending ratio of the other additives in the polymerizable composition can be, for example, 0.001% by weight to 5% by weight, preferably 0.005% by weight to 3% by weight, relative to all components in the polymerizable composition (excluding the organic solvent).

[0227] B. Aggregation Methods

[0228] The polymer material can be obtained, for example, by heating and / or irradiating a polymerizable composition containing the components described above 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.

[0229] As the polymerization method, bulk polymerization or solution polymerization can be used. In bulk polymerization, there is a situation where a part of the monomer components remain in an unpolymerized state. In addition, in the solution polymerization, the solvent that does not participate in the reaction may remain in the obtained polymer. In the manufacture of contact lenses as medical devices, in order to minimize these residues, the following treatment can be implemented: by immersing the obtained polymer material in water or an organic solvent or a mixed solution of these, preferably repeatedly performing this operation, so that these residues are dissolved and removed from the polymer material.

[0230] When the polymer material is used for contact lenses, the polymerizable composition can be reacted and formed into a desired shape (e.g., a hemispherical shape) by a casting method. When the polymerizable composition is heated and polymerized by the casting method, the polymerizable composition is filled in a casting mold corresponding to the shape of the desired ophthalmic lens material, and the casting mold is gradually heated.

[0231] 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. In addition, 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.

[0232] In the casting method, when the polymerizable composition is polymerized by light irradiation, the polymerizable composition is filled into a casting mold corresponding to the shape of the desired ophthalmic lens, and then the casting mold is irradiated with light. The material of the casting mold used in the polymerization by light irradiation is not particularly limited as long as it is a material that can transmit the light required for polymerization.

[0233] The wavelength of light irradiated to the polymerizable composition in the mold is appropriately set according to the type of photopolymerization initiator used, etc. The light irradiance and irradiation time are appropriately set according to the composition of the polymerizable composition, etc. The light irradiance is preferably 0.1 mW / cm 2 ~100mW / cm 2 The irradiation time is preferably 1 minute or longer. Light of different illuminances may also be irradiated in stages.

[0234] By utilizing the polymerization of the casting method, a polymer material having a desired shape can be obtained. The polymer material obtained as a molded body can also be subjected to mechanical processing such as cutting processing and grinding processing as required. Cutting can be performed over the entire surface of one or both surfaces of the polymer material, or can be performed on a portion of one or both surfaces of the polymer material.

[0235] The polymer material may be subjected to a surface modification treatment such as low-temperature plasma treatment, atmospheric pressure plasma, corona discharge, etc. for the purpose of surface modification.

[0236] C. Properties of polymer materials

[0237] The Young's modulus of the polymer material of 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 feeling and operability when processed into a contact lens can be obtained.

[0238] The stress relaxation rate of the polymer material of 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 wearing feeling and operability when processed into a contact lens can be obtained.

[0239] The oxygen permeability coefficient (Dk value) of the polymer material according to one embodiment of the present invention is preferably 20 Barrers or more, more preferably 30 Barrers or more, and even more preferably 50 to 150 Barrers.

[0240] The water content of the polymer material of one embodiment of the present invention is preferably 11% by weight or more, more preferably 30% by weight or more, and further preferably 30% by weight to 70% by weight. By setting the water content of the polymer material to 11% by weight or more, the obtained polymer material can be made into a hydrogel, which can improve the wearing feeling when processed into a contact lens, and can set the strength, oxygen permeability, and surface hydrophilicity in a balanced manner.

[0241] Example

[0242] The present invention will be specifically described below by way of examples, but the present invention is not limited to these examples. It should be noted that, unless otherwise specified, "parts" and "%" in the examples and comparative examples are based on weight.

[0243] [Ingredients used]

[0244] The meanings of the abbreviations of the components used in the following Examples and Comparative Examples are shown below.

[0245] <Siloxane monomer>

[0246] AA-PDMS: A polymerizable compound having the structure shown below

[0247]

[0248] MAUS: A polymerizable compound having the following structure (where n=about 40)

[0249]

[0250] · SiGMA: (3-methacryloyloxy-2-hydroxypropyloxy)propylbis(trimethylsiloxy)methylsilane (structure shown below)

[0251]

[0252] <Crosslinking monomer>

[0253] ·EDMA: Ethylene glycol dimethacrylate (HLB: 7.43)

[0254] ·TEGMA: Tetraethylene glycol methacrylate (HLB: 8.42)

[0255] PEGDMA (n=6): Hexaethylene glycol dimethacrylate (HLB: 9.08)

[0256] PEGDMA (n=9): polyethylene glycol dimethacrylate (EO repeat number: 9, HLB: 10.07, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., "NK Ester 9G")

[0257] PEGDMA (n=14): polyethylene glycol dimethacrylate (EO repeat number: 14, HLB: 11.72, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., "NK Ester 14G")

[0258] PEGDMA (n=23): polyethylene glycol dimethacrylate (EO repeat number: 23, HLB: 14.69, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., "NK Ester 23G")

[0259] 9PG (n=7): polypropylene glycol dimethacrylate (PO repeating number: 7, HLB: 6.05, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., "NK Ester 9PG")

[0260] 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, manufactured by NOF Corporation, "25PDC-900B")

[0261] 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, manufactured by NOF Corporation, "40PDC-1700B")

[0262] ·AMA: Allyl Methacrylate

[0263] <Compatibilizing Monomer>

[0264] · EH(OH)MA: A polymerizable compound having the structure shown below (solubility in water at 20°C: less than 0.01 g / mL)

[0265]

[0266] <Hydrophilic Monomer>

[0267] DMAA: N,N-dimethylacrylamide

[0268] HEMA: 2-Hydroxyethyl Methacrylate

[0269] ·N-VP: N-vinyl-2-pyrrolidone

[0270] ·2-MTA: Methoxyethyl acrylate

[0271] <Functional monomer>

[0272] ·HMEPBT: Benzotriazole polymeric UV absorber (2-(2'-hydroxy-5'-methacryloyloxyethylphenyl)-2H-benzotriazole)

[0273] RB246: Anthraquinone polymeric pigment

[0274] <Hydrophilic polymer>

[0275] ·PVP K-90: ​​Polyvinylpyrrolidone (Mw = 1000000 ~ 1500000)

[0276] <Additives>

[0277] ·TPO: Initiator (2,4,6-trimethylbenzoyl-diphenylphosphine oxide)

[0278] IPA: Isopropyl alcohol

[0279] [Synthesis Example 1: Preparation of EH(OH)MA]

[0280] 1) Ethylhexyl glycidyl ether, methacrylic acid, tetrabutylammonium bromide and p-methoxyphenol were added and dissolved in a brown eggplant-shaped flask, and a Deed condenser was installed, followed by stirring at 90° C. in an oil bath overnight.

[0281] 2) The reaction solution was returned to room temperature, dissolved in hexane, and transferred to a separatory funnel.

[0282] 3) The hexane layer was washed with a 1 M sodium bicarbonate aqueous solution.

[0283] 4) Wash the hexane layer with distilled water.

[0284] 5) Wash the hexane layer with saturated brine.

[0285] 6) Recover the hexane layer, add an appropriate amount of sodium sulfate, dry it, and leave it for a while.

[0286] 7) Remove the sodium sulfate by filtration.

[0287] 8) The hexane layer was concentrated under reduced pressure to obtain a slightly yellowish transparent liquid. 1 H NMR (CDCl 3 , 400 MHz) and gas chromatogram, confirming that the desired compound was obtained.

[0288] [Synthesis Example 2: Preparation of Hexaethylene Glycol Dimethacrylate]

[0289] 1) Hexaethylene glycol and methacrylic acid were added to a brown eggplant-shaped flask and dissolved. A small amount of sulfuric acid was added and stirred in an oil bath at 100° C. for four hours.

[0290] 2) The reaction solution was returned to room temperature, dissolved in a toluene-hexane mixed solvent, and transferred to a separatory funnel.

[0291] 3) The organic layer was washed with a sodium bicarbonate aqueous solution.

[0292] 4) Wash the organic layer with distilled water.

[0293] 5) The organic layer was washed with saturated brine.

[0294] 6) Recover the organic layer, add an appropriate amount of sodium sulfate, dry it, and leave it for a while.

[0295] 7) Remove the sodium sulfate by filtration.

[0296] 8) The organic layer was concentrated under reduced pressure to obtain a colorless transparent liquid. 1 H NMR (CDCl 3 , 400 MHz) and gas chromatogram, confirming that the desired compound was obtained.

[0297] [Example 1-A]

[0298] 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 pigment, 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 for photopolymerization. After polymerization, the contact lens-shaped polymer material was taken out from the mold. Thus, a silicone hydrogel contact lens was obtained.

[0299] [Example 1-B to Example 4-A, Comparative Example 1-A to Comparative Example 3-B]

[0300] A silicone hydrogel contact lens was obtained in the same manner as in Example 1-A except that the respective components were mixed so as to have the compositions described in Tables 1 to 4 to prepare polymerizable compositions.

[0301]

[0302]

[0303]

[0304] [Table 4]

[0305]

[0306] (parts by weight)

[0307] The contact lenses obtained in the examples and comparative examples were immersed in distilled water, swelled until equilibrium was reached, and replaced with pH 7.5 phosphate buffer, which was then swelled until equilibrium was reached. Thereafter, the phosphate buffer was replaced with the same amount of new water, and sterilized in an autoclave at 121°C for 20 minutes, and then the following property evaluations were performed. However, in the determination of the oxygen permeability coefficient, a plate-type sample was used. The plate-type sample was obtained by using a PP casting mold that can obtain a plate-type sample with an average thickness of about 0.3 mm instead of a casting mold having a contact lens shape. Otherwise, polymerization, hydration treatment and sterilization treatment were performed in the same manner as above, and the sample was processed into a circle with a diameter of 14.0 mm. The evaluation results are shown in Figure 1 middle.

[0308] 《Evaluation of lipid adhesion》

[0309] 1) Solid artificial lipid (product name "Pharmasol") was heated to 60°C at room temperature to be melted, and then placed in the well in an amount of 1.7 mL per lens.

[0310] 2) Wipe off the moisture on the surface of the contact lens, place the contact lens in each well, and place in a desiccator at 60° C. for 1 hour.

[0311] 3) The contact lens was removed from the hole, cleaned in a contact lens cleaning solution (manufactured by Menicon, product name "Epicacold") placed in a beaker, and then both sides were cleaned using contact lens cleaning solution (manufactured by Menicon, product name "Epicacold") or hot water, with each side being cleaned 20 times.

[0312] 4) Contact lens cleaning solution (manufactured by Menicon, product name "Epicacold") and contact lenses were placed in each well of the multi-well plate and left at 10°C for 4 hours. Then, the contact lenses were taken out of the wells and cleaned, and then left overnight.

[0313] 5) After removing the contact lens from the hole and further cleaning the lens, the appearance was confirmed with the naked eye and evaluated based on the following criteria. In addition, a microscope photograph of each lens is shown in Figure 1 middle.

[0314] [Judgment criteria]

[0315] 0: Almost no whitening is observed

[0316] 1: Whitening is observed only partially

[0317] 2: About 50% of the whole body is observed to be white

[0318] 3: The lens is observed to be white as a whole, but there are some areas with light turbidity

[0319] 4: The entire lens is observed to be white

[0320] 《Determination of tensile elastic modulus (Young's modulus)》

[0321] The contact lenses were punched to produce dumbbell-shaped samples with a width of about 1.8 mm and a thickness of about 0.1 mm in the stretched portion as test samples. A tensile test was performed in 20°C saline using a Shimadzu precision universal testing machine Autograph AG-IS MS manufactured by Shimadzu Corporation, and the Young's modulus (MPa) was calculated from the stress-stretch curve as the tensile elastic modulus. The stretching speed was set to 100 mm / min.

[0322] 《Determination of stress relaxation rate》

[0323] The same measuring equipment and method as for the tensile elastic modulus were used. Figure 2 Specifically, the center of the contact lens C was pressed into saline with a test force of 0.1 N using an indenter P having a tip PT of about 1.6 mm in diameter, and the stress relaxation rate (%) was calculated based on the change in stress after the stroke was maintained for 1 minute.

[0324] like Figure 1 As shown, the contact lens of the example suppresses the adhesion of lipids compared with the contact lens of the comparative example. In addition, it is known that the contact lens of the example has a Young's modulus and stress relaxation rate that are preferred as a contact lens, and is excellent in operability and wearing feeling.

[0325] 《Determination of moisture content》

[0326] The water content of the contact lens obtained in Example 1-C was measured.

[0327] Specifically, the water on the surface of the contact lens adjusted in a phosphate buffer solution of pH 7.5 at 20°C was gently wiped off, and the mass (W (g)) in the equilibrium water-containing state was measured. Thereafter, the lens was dried in a dryer set at 105°C, and then the mass (W0 (g)) in the cooling state 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%.

[0328] Water content (mass %) = {(W-W0) / W} × 100

[0329] 《Determination of oxygen permeability coefficient (Dk value)》

[0330] The Dk value was measured using the circular plate-shaped sample having a diameter of 14.0 mm obtained in Example 1-C as a measurement sample.

[0331] Specifically, as a reference standard, a similar plate sample was produced using a raw material of "2WEEK Menicon Premio" (manufactured by Menicon Corporation), and its Dk value was set to 129.

[0332] The test sample is placed on the electrode, and a thin film oxygen permeability meter (manufactured by Rika Seiki Kogyo Co., Ltd.) is used to bubble nitrogen in 35°C physiological saline and set the current value at equilibrium to zero. Then, oxygen is bubbled and the current value at equilibrium is recorded. The same operation is performed on the reference standard. The oxygen permeability coefficient of the lens is calculated according to the following formula. It should be noted that the unit of the oxygen permeability coefficient is (×10 -11 (cm 2 / sec)·(mLO 2 / (mL×mmHg))=Barrer). As a result, the Dk value of the measured sample was 78 Barrer.

[0333] Dk value=R×(IS / IR)×(TS / TR)×(PR / PS)

[0334] Here, the symbols in the above formula have the following meanings.

[0335] R: Dk value of the reference standard (129)

[0336] IS: Current value of the measured sample (μA)

[0337] IR: Reference standard current value (μA)

[0338] TS: average thickness of the test sample (mm)

[0339] TR: Average thickness of reference standard (mm)

[0340] PS: Atmospheric pressure when measuring the sample (mmHg)

[0341] PR: Atmospheric pressure when measuring reference standard (mmHg)

[0342] Industrial Applicability

[0343] The ophthalmic lens of the present invention is preferably used for ophthalmic lenses such as contact lenses, artificial corneas, and corneal patches.

Claims

1. An ophthalmic lens comprising a polymer material obtained by polymerizing a polymerizable composition, wherein the polymerizable composition comprises, as monomer components, a siloxane monomer having a siloxane bond and a siloxane-free crosslinking monomer having no siloxane bond, The crosslinkable monomer not containing siloxane includes a crosslinkable monomer containing an alkylene glycol chain, wherein 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. The polymerizable composition further includes a hydrophilic polymer, and the monomer component is polymerized in the presence of the hydrophilic polymer.

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

3. The ophthalmic lens according to claim 1 or 2, in, The alkylene glycol repeating unit includes at least one selected from the group consisting of an ethylene glycol repeating unit, a propylene glycol repeating unit, and a butanediol repeating unit.

4. The ophthalmic lens according to claim 1, in, The blending ratio of the crosslinkable monomer not containing siloxane is 2% by weight or more relative to the total blending amount of all monomer components and the hydrophilic polymer in the polymerizable composition, The blending ratio of the alkylene glycol chain-containing crosslinking monomer is 0.9% by weight or more relative to the total blending amount of all monomer components and the hydrophilic polymer in the polymerizable composition.

5. The ophthalmic lens according to claim 1, in, The blending ratio of the alkylene glycol chain-containing crosslinking monomer is 2% by weight or more relative to the total blending amount of all monomer components and the hydrophilic polymer in the polymerizable composition.

6. The ophthalmic lens according to claim 1, in, The blending ratio of the alkylene glycol chain-containing crosslinking monomer is 3% to 25% by weight relative to the total blending amount of all monomer components and the hydrophilic polymer in the polymerizable composition.

7. The ophthalmic lens according to claim 1, in, The HLB value of the crosslinking monomer containing an alkylene glycol chain is 5-20.

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

9. The ophthalmic lens according to claim 1, in, The siloxane monomer has a single polymerizable group.

10. The ophthalmic lens according to claim 1, in, The siloxane monomer has 100 or less repeating siloxane bonds.

11. The ophthalmic lens according to claim 1, in, The siloxane monomer has 20 or less repeating siloxane bonds.

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

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

14. The ophthalmic lens according to claim 1, in, The siloxane monomers include a siloxane monomer A having a weight average molecular weight of less than 1000, and a siloxane monomer B having a weight average molecular weight of more than 1000. The 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.

15. The ophthalmic lens according to claim 1, in, The polymerizable composition further includes a copolymerizable monomer as the monomer component.

16. The ophthalmic lens according to claim 15, in, The copolymerizable monomer includes at least one hydrophilic monomer selected from the group consisting of hydroxyl-containing alkyl (meth)acrylates, (meth)acrylamide, N-vinyl lactam, N-methyl lactam, methyl (meth)acrylate, and alkoxyalkyl (meth)acrylates.

17. The ophthalmic lens according to claim 15, in, The copolymerizable monomer is contained in an amount of 20% by weight to 70% by weight relative to the total amount of all monomer components and the hydrophilic polymer contained in the polymerizable composition.

18. The ophthalmic lens according to claim 1, in, The hydrophilic polymer comprises at least one selected from the group consisting of poly-N-vinyl pyrrolidone, polyalkylene glycol, polysaccharide, poly(meth)acrylic acid and polyvinyl alcohol.

19. The ophthalmic lens according to claim 1, in, The stress relaxation rate of the polymer material is 10% to 40%.

20. The ophthalmic lens according to claim 1, in, The Young's modulus of the polymer material is 0.3 MPa to 2.3 MPa.

21. The ophthalmic lens of claim 1 which is a contact lens.

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