JP4854130B2 - Contact lens material comprising hydrophilic polysiloxane monomer and copolymer thereof, and contact lens - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an ophthalmic lens material made of a copolymer containing hydrophilic polysiloxane as a component. More specifically, the present invention relates to a hydrophilic copolymer excellent in water wettability, oxygen permeability, contamination resistance, flexibility, optical transparency, and strength useful as an ophthalmic lens such as a contact lens.
[0002]
[Prior art]
Polysiloxane compounds are singularly modified or modified with other materials by taking advantage of their unique functions such as heat resistance, chemical stability, electrical insulation, flexibility, lubricity, and water repellency, as represented by dimethylsilicone compounds. It is widely used industrially. For example, polydimethylsiloxane having methacrylic groups at both ends, which is a polymerizable polysiloxane compound, is used to modify various polymers such as acrylic polymer and polystyrene by utilizing its polymerizability. In addition, since the polysiloxane polymer exhibits high gas permeability, it is also used for a gas selective permeable membrane. For example, taking advantage of its excellent oxygen permeability, flexibility, and optical transparency, application to contact lenses has been studied, and many patents have been proposed (for example, Japanese Patent No. 1430546, Japanese Patent Laid-Open No. 63). -29741, Japanese Patent No. 2532406, Japanese Patent No. 2716181).
[0003]
Contact lenses can be broadly classified into hard lenses and soft lenses, but hard contact lenses are hard and have poor wearing feeling, but in recent years the improvement in oxygen permeability has been remarkable and most of them are products that can be used continuously. On the other hand, soft contact lenses are soft and wearable, but have various problems. Hydrous soft contact lenses have poor oxygen permeability and durability, are easily damaged, and there is a risk of bacterial growth, so periodic disinfection is necessary and is often inconvenient in handling. Although it is somewhat improved by the high water content soft contact lens, the oxygen permeability is still not sufficient and it is not satisfactory as a long-wearing lens. Non-hydrous soft contact lenses are significantly inferior in lens contamination, particularly lipid contamination, compared to hydrous lenses.
[0004]
In recent years, hydrous soft contact lenses have been developed with hydrophilic siloxane as the main component and have high oxygen permeability, flexibility, and good wearing feeling (Patent No. 2938131). Since hydrophilicity cannot be obtained, wettability of tears is poor, and surface hydrophilization treatment such as plasma treatment or grafting of a hydrophilic monomer is performed. However, sufficient hydrophilicity and durability are not obtained by these treatments. In addition, since the hydrophilic polysiloxane monomer has a large molecular weight, a sufficient crosslinking density cannot be obtained in the polymerization composition, it is inferior in mechanical strength and very easily damaged, and lipid penetration into the lens is easy. The material is easily contaminated.
[0005]
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to eliminate the above-mentioned drawbacks, that is, to provide an ophthalmic lens that has sufficient surface hydrophilicity despite being high oxygen permeability, and further has high strength and excellent stain resistance. It is.
[0006]
[Means for Solving the Problems]
As a result of intensive studies by the present inventors, a monomer having a polymerizable unsaturated group at least at a terminal where a polysiloxane group and a polyoxyalkylene group are linked, and at least two polymerizable unsaturated groups at one terminal It has been found that a hydrophilic polysiloxane monomer characterized by having the above is extremely effective in solving the above-mentioned problems, and has led to the present invention.
Namely, a hydrophilic monomer characterized by having a polymerizable unsaturated group at the terminal where at least a polysiloxane group and a polyoxyalkylene group are linked, and having at least two polymerizable unsaturated groups at one terminal An ophthalmic lens such as a contact lens made of a functional polysiloxane monomer and a (co) polymer thereof is provided.
[0007]
Specific hydrophilic polysiloxane monomers are represented by the formula (I) or (II), (III), (IV).
X1- (Z1-P1-Z2-S1) _p −Z3−P2−Z4−X2 (I)
X3- (Z5-S2-Z6-P3) _q −Z7−S3−Z8−X4 (II)
X5− (Z9 −P4−Z10 −S4) _r −Z11 −P5−Z12 −S5 (III)
X6- (Z13-S6-Z14-P6) _s −Z15 −S7−Z16 −P7 (IV)
[Wherein, p and q are 1 to 10. r and s are 0-10. X1 and X2, X3, and X4 are independently selected from Formula (1) and Formulas (2) and (3). At least one of X1 or X2 is the formula (1) or (2), and at least one of X3 or X4 is the formula (1) or (2). X5 and X6 are represented by the formula (1) or (2).
[0008]
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(Each a and b 1, c 2, d 3 and e are each independently 0 or 1.
Each W is independently -O-or -NR _Five -.
[0009]
R ₁ And R ₂ , R _Three , R _Four Is independently interrupted at any one or more points by an amide group or urethane group, urea group, oxy group, ester group, carbonyl group, aryl group or alicyclic hydrocarbon group having 5 to 7 carbon atoms. It is also a linear hydrocarbon group having 1 to 10 carbon atoms. The chain hydrocarbon group having 1 to 10 carbon atoms is an aryl group, and the alicyclic hydrocarbon group having 5 to 7 carbon atoms is C. _1-4 Any one or more points may be substituted with an alkyl group, a fluoro group, a C1-C10 fluoro-substituted hydrocarbon group, or a hydroxyl group.
[0010]
A ₁ And A ₂ , A _Three Is independently hydrogen, a hydroxyl group, a methyl group, or any one of the formulas (i), (ii), (iii), and A ₁ And A ₂ , A _Three At least two of these are selected from the formula (i) or (ii), (iii) and may be the same or different.
A _Four Is selected from formulas (i) and (ii), (iii).
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Where each R _Five Are each independently hydrogen or a hydrocarbon group having 1-4 carbon atoms. )
S1 and S2, S3, S4, S6, and S7 are independently polysiloxane groups represented by the formula (4).
[0011]
S5 is a polysiloxane group represented by the formula (5).
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(Each R ₆ And R ₇ Are each independently interrupted at any one or more points by an amide group, urethane group, urea group, oxy group, ester group, carbonyl group, aryl group, or alicyclic hydrocarbon group having 5 to 7 carbon atoms. It may be a chain hydrocarbon group having 1 to 30 carbon atoms. The above 1-30 chain hydrocarbon group is an aryl group, and the alicyclic hydrocarbon group having 5-7 carbon atoms is substituted with an alkyl group having 1-4 carbon atoms, a fluoro group, or a fluoro group having 1-10 carbon atoms. It may be substituted at any one point or more by a hydrocarbon group or a hydroxyl group.
[0012]
R ₈ And R ₉ , R _Ten , R ₁₁ , R ₁₂ Are groups selected from a hydrocarbon group having 1 to 12 carbon atoms or a trimethylsiloxy group, which may be the same or different.
Y is a structural unit represented by the following formula (iv), (v), (vi) connected in random or block form, and the number of connections of (iv), (v), (vi) is 1 to 1000. However, (v) and (vi) may be 0.
[0013]
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Where R ₁₃ And R ₁₄ Is independently a hydrocarbon group having 1 to 12 carbon atoms or a trimethylsiloxy group. R ₁₅ And R ₁₆ Is independently a hydrocarbon group having 1 to 12 carbon atoms or a trimethylsiloxy group, a fluoro group-substituted hydrocarbon group having 1 to 12 carbon atoms, and R ₁₅ Or R ₁₆ At least one of these is a fluoro group-substituted hydrocarbon group. R ₁₇ And R ₁₈ Are independently a hydrocarbon group having 1 to 12 carbon atoms, a trimethylsiloxy group, a group consisting of a hydrophilic substituent, and R ₁₇ Or R ₁₈ At least one of these is a hydrophilic substituent. The hydrophilic substituent here is a chain or cyclic hydrocarbon group formed by bonding at least one substituent selected from a hydroxyl group, a carboxylic acid group, an amino group, an imino group, an amide group, and an oxyalkylene group. Say. )
[0014]
P1 and P2, P3, P4, P5, and P6 are independently polyoxyalkylene groups represented by the formula (6).
P7 is a polyoxyalkylene group represented by the formula (7).
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[0015]
(U is formed by connecting structural units (vii) represented by the following formula, and the number of connections is 1 to 200.
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Where each R ₁₉ And R ₂₀ , R _{twenty one} , R _{twenty two} , R _{twenty three} , R _{twenty four} Are independently hydrogen, fluoro group, C _1-10 A hydrocarbon group, a C1-C10 fluoro-substituted hydrocarbon group, and an aryl group.
n is 0-4. )
[0016]
Z1 and Z2-Z16 are each independently a linking group represented by the formula (5a), (5b), or (5c).
LR ₆ L (5a)
LR ₆ (5b)
R ₆ L (5c)
(L is -C (O) NR _Five -, -NR _Five C (O)-, -C (O) O-, -OC (O)-, and -C (O)-. )]
[0017]
The present invention includes the following inventions.
A hydrophilic polysiloxane monomer in which p and q in formula (I) and formula (II) are each 1 and r and s in formula (III) and formula (IV) are each selected from 0.
A hydrophilic polysiloxane monomer in which X1 and X2, X3, and X4 in the formulas (I) and (II) are selected from the following formulas (8), (9), and (10).
However, at least one of X1 and X2 is the formula (8) or (9), and at least one of X3 and X4 is the formula (8) or (9).
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[0018]
A hydrophilic polysiloxane monomer in which X5 and X6 in the formulas (III) and (IV) are selected from the following formulas (11) or (12).
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[0019]
In formulas (I) and (II), (III) and (IV), S1 and S2, S3, S4, S6 and S7 are selected from the following polysiloxane groups of formula (13) and S5: A hydrophilic polysiloxane monomer.
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(Where k is 0 to 4)
[0020]
In formulas (I) and (II), (III), and (IV), S1 and S2, S3, S4, S6, and S7 are selected from the following polysiloxane groups of formula (15) and S5: A hydrophilic polysiloxane monomer.
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[0021]
In the formula (I) and the formulas (II), (III) and (IV), S1 and S2, S3, S4, S6 and S7 are selected from the following polysiloxane groups of the formula (17) and S5: A hydrophilic polysiloxane monomer.
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[0022]
In formulas (I) and (II), (III), and (IV), P1 and P2, P3, P4, P5, and P6 are selected from the following formula (19), and P7 is a polyoxyalkylene group of formula (20) A hydrophilic polysiloxane monomer.
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(M is 1 to 200)
[0023]
In formulas (I) and (II), (III) and (IV), P1 and P2, P3, P4, P5 and P6 are selected from the following formula (21) and P7 is a polyoxyalkylene group of formula (22) A hydrophilic polysiloxane monomer.
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(M is 1 to 200)
[0024]
A hydrophilic polysiloxane monomer in which in formulas (I) and (II), (III) and (IV), Z1 and Z2 to Z16 are selected from the linking group of the following formula (23).
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[0025]
In the hydrophilic polysiloxane monomer of the present invention, the number of linked polysiloxane groups and polyoxyalkylene groups in the molecule is important. When the number of linked polysiloxane groups is relatively large, oxygen permeability is improved, but hydrophilicity is lowered and lipid contamination is increased. If the relative number of polyoxyethylene groups is large, the reverse phenomenon occurs. Therefore, it is preferable that the total number of Y is selected from a combination of a siloxane group having 10 to 200 and a polyoxyalkylene group having a total number of U of 2 to 50.
[0026]
Various methods for synthesizing the hydrophilic polysiloxane monomer disclosed in the present invention are conceivable. For example, there are the following methods. Polyoxyalkylene derivatives having a hydroxyl group at the end, such as polyethylene glycol and polypropylene glycol of various molecular weights, or polyethylene glycol and polypropylene glycol block copolymers, hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, xylylene diisocyanate, naphthalene diisocyanate Etc. are reacted to synthesize an isocyanate-modified polyoxyalkylene derivative. Next, a polysiloxane compound whose end is modified with a functional group reactive with isocyanate such as carbinol, amine, phenol, etc. is reacted with an isocyanate-modified polyoxyalkylene derivative. At this time, when a catalyst such as dibutyltin dilaurate, stannous chloride, triethylamine, or diethylenetriamine is used in combination, the reaction can be efficiently performed.
[0027]
Moreover, it is possible to adjust the amount of repeating units of the polysiloxane and polyoxyalkylene derivative in the molecule by changing the charging ratio of the polysiloxane compound and the isocyanate-modified polyoxyalkylene derivative. Subsequently, a polyfunctional polymerizable compound reactive with an isocyanate such as glycerin dimethacrylate, 3-acryloyloxyglycerin monomethacrylate, or pentaerythritol triacrylate, or in some cases, the above polyfunctional polymerizable compound is added to the diisocyanate compound in advance. Charge the reacted compound. It is also possible to use a mixture of a monofunctional polymerizable compound such as 2-hydroxyethyl methacrylate or isocyanate ethyl methacrylate and the above polyfunctional polymerizable compound.
[0028]
The ophthalmic lens material of the present invention comprises one or more hydrophilic polysiloxane monomers represented by the formulas (I) and (II), (III), and (IV), and the hydrophilic polysiloxane monomer alone. Or a copolymer obtained by copolymerizing with one or more kinds of copolymerizable monomers. In order to constitute a good hydrophilic polysiloxane monomer, depending on the target performance of the ophthalmic lens material, for example, required oxygen permeability, softness, resistance to dirt, strength, moisture content, etc. Selected. That is, the number and type of reactive double bond groups in the monomer, the type and number of units constituting the Y of the polysiloxane group, the type and number of units constituting the polyoxyalkylene group, and the like. The copolymer comprising the hydrophilic polysiloxane monomer disclosed in the present invention is applicable not only to a composition having a water content exceeding 1% but also to a composition containing substantially no water having a water content of 1% or less. . That is, the contact lens material can be used as a hydrous soft lens material or a non-hydrous soft lens material. Furthermore, it is also useful for intraocular lenses that are other ophthalmic lens materials.
[0029]
Here, the copolymerizable monomer will be described below. In the present invention, any monomer can be used as long as it can be copolymerized, but a hydrophilic monomer is particularly useful. This is because it can be used as a monomer for further improving the surface wettability of the polymer or changing the water content. For example, hydroxyl group-containing monomers such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, glycerol methacrylate, 3- (1,1,2,2-tetrafluoroethoxy) -2-hydroxypropyl methacrylate, etc. Hydroxyl group-containing monomers having fluorine-containing substituents, carboxylic acid group-containing monomers such as methacrylic acid, acrylic acid and itaconic acid, alkyl-substituted amino group-containing monomers such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate, methoxypolyethylene glycol monomethacrylate, Examples thereof include oxyalkylene group-containing monomers such as polypropylene glycol monoacrylate, preferably N, N-dimethylacrylamido. , N, N-diethylacrylamide, N-methylacrylamide, methylenebisacrylamide, diacetone acrylamide, N-methyl N-vinylacetamide, N-vinylpyrrolidone and other monomers containing amide groups or imide groups are more effective. The hydrophilicity of can be improved. Particularly preferably, by selecting N, N-dimethylacrylamide, N-methyl N-vinylacetamide, or N-vinylpyrrolidone, the surface wettability is remarkably good and a transparent copolymer can be obtained.
[0030]
Examples of other available monomers include fluorine-containing monomers such as acrylic acid fluoroalkyl esters and methacrylic acid fluoroalkyl esters, such as trifluoroethyl acrylate, tetrafluoroethyl acrylate, tetrafluoropropyl acrylate, and pentafluoropropyl acrylate. , Hexafluorobutyl acrylate, hexafluoroisopropyl acrylate and methacrylates for these acrylates, and the like, which can be selected according to the required compatibility, hydrophilicity, water content, and contamination resistance.
[0031]
In order to adjust oxygen permeability, so-called siloxanyl acrylates are also useful copolymerization monomers. For example, tris (trimethylsiloxy) silylpropyl methacrylate, bis (trimethylsiloxy) methylsilylpropyl methacrylate, pentamethyldisiloxanyl methacrylate, and the like. For the same purpose, polymerizable polydimethylsiloxane substituted with a methacrylate group or the like can also be used.
[0032]
Moreover, an acrylic acid alkyl ester monomer, a methacrylic acid alkyl ester monomer, etc. can be used as needed. Examples include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, tert-butyl acrylate, cyclopentyl acrylate, cyclohexyl acrylate, n-stearyl acrylate, and methacrylates corresponding to these acrylates.
[0033]
Furthermore, in order to improve mechanical properties, dimensional stability, etc., the monomers described below can be copolymerized as desired. Examples of the monomer for improving the mechanical properties include aromatic vinyl compounds such as styrene, tert-butylstyrene, and α-methylstyrene. Examples of monomers for improving dimensional stability include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, bisphenol A dimethacrylate. Vinyl methacrylate, acrylic methacrylate and acrylates corresponding to these methacrylates, divinylbenzene, triallyl isocyanurate, and the like. These monomers may be used alone or in combination of two or more.
[0034]
Good balance of properties such as optical properties, oxygen permeability, mechanical strength, deformation recovery, dirt adhesion when worn on the eye, dimensional stability in tears and changes in diameter of the copolymer Therefore, a mixed monomer in which these copolymerizable monomers are combined can be used, but various additives may be added before or after the polymerization, if necessary. Examples of additives include various colorants, UV absorbers, and antioxidants.
[0035]
The copolymer used as the ophthalmic lens material of the present invention is, for example, a so-called mold forming method in which a mixture of a hydrophilic polysiloxane monomer and a hydrophilic monomer is filled in a mold and radical polymerization is performed by a known method, It can be molded into an ophthalmic lens by a so-called spin casting method in which a monomer mixture is charged and polymerized. In this case, a solution obtained by adding a solvent to the monomer mixture is polymerized in a mold and can be used for adjusting the polymerization rate and the lens swelling rate. As the additive solvent, those having good solubility of the monomer can be used. For example, alcohol, ketone, ether, ester, carboxylic acid, sulfoxide, amine, amide and nitrile compound are selected. Preferably, the solvent that can be used varies depending on the combination of the hydrophilic polysiloxane monomer and the copolymerizable monomer. However, when butanol, hexanol, methyl ethyl ketone, tetrahydrofuran, ethyl acetate, dimethyl sulfoxide, N, N dimethylformamide, acetonitrile is selected, polymerization is performed. Later, peeling from the mold is easy, water wettability is good, and a transparent contact lens can be manufactured. These solvents can be added in a proportion of 1% to 99% of the polymerizable composition. Preferably, when 10% to 90%, more preferably 20% to 80% is added, a contact lens having good dimensional stability and water wettability can be produced.
[0036]
The template material used in the mold polymerization method or cast polymerization method is substantially insoluble in the monomer mixture, and can be used if the lens can be separated after polymerization. For example, polyolefin resins such as polypropylene and polyethylene can be used, but a material having a polar group on the surface and a small contact angle with water is suitable. The polar group is an atomic group having a strong affinity for water, and includes a hydroxyl group, a nitrile group, a carboxyl group, a polyoxyethylene group, an amide group, a urethane group, and the like. A preferred template material is insoluble in the polymerization monomer composition, and the part forming at least one lens surface of the template has a contact angle with water of 90 ° or less by the droplet method.
[0037]
More preferably, the contact angle of the mold material surface is 65 to 80 ° by the droplet method. A lens formed by using a mold having a contact angle of less than 80 ° on the surface of the mold material has particularly good water wettability and exhibits stable performance for lipid adhesion. In addition, a material having a contact angle smaller than 65 ° makes it difficult to separate the lens and the mold material after polymerization, and is liable to cause fine scratches on the surface and chipping on the edge portion, which is not practical.
More preferably, the mold material is a resin selected from polyamide, polyethylene terephthalate, and ethylene vinyl alcohol copolymer. In particular, the ethylene vinyl alcohol copolymer can be molded easily and a mold having a stable dimension can be obtained. Stable water wettability can be imparted to the lens. The ethylene vinyl alcohol copolymer resin used is commercially available as “SOARITE” manufactured by Nippon Synthetic Chemical Industry Co., Ltd. or “EVAL” manufactured by Kuraray Co., Ltd., with various ethylene copolymerization ratios of about 25 to about 50 mol%. Grades can be used in the present invention.
[0038]
The copolymerization method is preferably a method in which a photopolymerization initiator is present in the monomer mixture and polymerized by irradiating with ultraviolet rays, or a radical polymerization method in which polymerization is performed using an azo compound or an organic peroxide. Examples of the photopolymerization initiator used include benzoin ethyl ether, benzyl dimethyl ketal, α, α'-diethoxyacetophenone, and organic peroxides such as benzoyl peroxide and t-butyl peroxide. As azobisisobutyronitrile, azobisdimethylvaleronitrile and the like are used.
[0039]
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described based on examples. The present invention is not limited to these synthesis examples.
[Synthesis Example 1]
1.8 mmol of carbinol-modified silicone (KF6003) manufactured by Shin-Etsu Chemical Co., Ltd., 36 mmol of hexamethylene diisocyanate (HMDI) -modified polyethylene glycol 600 (DPEG600), and 10 mg of dibutyltin dilaurate as a catalyst were dissolved in 200 g of acetone. The mixture was refluxed for 2 hours under a nitrogen stream. After cooling, 80 mmol of glycerin dimethacrylate (G-101P) manufactured by Kyoeisha Chemical Co., Ltd. was added to the reaction solution and heated to 40 ° C. overnight. 150 g of water was poured into the stirring reaction solution to precipitate the target compound. The precipitate was collected by centrifugation and then dried to obtain a viscoelastic solid. It was confirmed by IR and NMR that the compound was the target compound (A-1). The yield was 78%.
[0040]
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(In the formula, the number of linkages between polyoxyalkylene and polysiloxane is an average value, and the actual compound has a range in molecular weight. The number of linkages in the following formulas is also the same.)
[0041]
[Synthesis Example 2]
In the same manner as in Synthesis Example 1, KF6003, HMDI-modified polyethylene glycol 400 (DPEG400), and G-101P were reacted to obtain the target compound (A-2). The yield was 82%.
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[0042]
[Synthesis Example 3]
In the same manner as in Synthesis Example 1, KF6003, HMDI-modified polypropylene glycol 1200 (DPPG1200), and G-101P were further reacted to obtain the target compound (A-3). The yield was 68%.
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[0043]
[Synthesis Example 4]
In the same manner as in Synthesis Example 1, KF6003, DPEG600, and pentaerythritol triacrylate (PE-3A) manufactured by Kyoeisha Chemical Co., Ltd. were reacted, and the target compound (A- Four ) The yield was 74%.
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[0044]
[Synthesis Example 5]
1.8 mmol of double-ended amine-modified silicone (FM3325) manufactured by Chisso Corporation, 36 mmol of DPEG600, and 10 mg of dibutyltin dilaurate were dissolved in 200 g of methyl ethyl ketone and refluxed for 2 hours under a nitrogen stream. After cooling, 80 mmol of G-101P was added to the reaction solution, and the mixture was further heated to 40 ° C. overnight. Purification by the same method as in Synthesis Example 1, and the target compound (A- Five ) The yield was 80%.
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[0045]
[Synthesis Example 6]
In the same manner as in Synthesis Example 1, 1.8 mmol of modified one-end carbinol-modified silicone (X-22-170B) manufactured by Shin-Etsu Chemical Co., Ltd., 18 mmol of DPEG600, and 40 mmol of G-101P were reacted, and the target compound (A- 6) was obtained. The yield was 79%.
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[0046]
[Synthesis Example 7]
In the same manner as in Synthesis Example 1, 1.8 mmol of KF6003 and 36 mmol of DPEG600 were reacted, and then 40 mmol of G101P and 40 mmol of 2-hydroxyethyl methacrylate (HEMA) were reacted to obtain the target compound (A-7). The yield was 85%.
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[0047]
[Synthesis Example 8]
Dissolve 20 mmol of KF6003, 1 mmol of DPEG600 and 20 mg of dibutyltin dilaurate in 500 g of acetone. After refluxing for 2 hours under a nitrogen stream, 40 mmol of hexamethylene diisocyanate was continuously added and refluxed for 2 hours. After cooling, 80 mmol of G-101P was added to the reaction solution, and the mixture was further heated to 40 ° C. overnight. The product was purified by the same method as in Synthesis Example 1 to obtain the target compound (A-8). The yield was 62%.
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[0048]
[Comparative synthesis example]
In the same manner as in Synthesis Example 1, KF6003, DPEG600 and HEMA were reacted to obtain the target compound (B-1). The yield was 88%.
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[0049]
[Example 1]
80 parts by weight of the synthesized hydrophilic polysiloxane monomer (A-1), 20 parts by weight of N, N-dimethylacrylamide and 0.5 parts by weight of 2,4,6-trimethylbenzoyldiphenylphosphine oxide are dissolved in 80 parts by weight of 2-butanol. After stirring and mixing, the monomer mixture was poured into a contact lens molding mold made of ethylene vinyl alcohol resin (Soareite S). Ultraviolet rays were irradiated for 1 hour in a light irradiation apparatus to obtain a lens-like polymer. The lens was immersed in ethanol overnight, and then immersed in water at 90 ° C. for 3 hours to obtain a transparent and flexible lens.
[0050]
The physical properties of the obtained lens were evaluated by the following methods.
(1) Optical transparency
By visual inspection. A sample having good transparency without cloudiness was marked with ◯, a cloudy, semi-transparent sample with Δ, and an opaque product with ×.
(2) Water wettability
The wettability with respect to purified water was visually evaluated. The lens was immersed in purified water for a whole day and night, then pulled up vertically, the water wettability for maintaining the water film for 5 seconds or more was evaluated as “◯”, the one for 1 to 5 seconds as “Δ”, and the case of 1 second or less as “X”.
[0051]
(3) Contact angle
Using a contact angle measuring device (CA-DT type manufactured by Kyowa Interface Science Co., Ltd.), the contact angle between the material surface and water droplets was measured at 25 ° C.
(4) Moisture content
After leaving the lens in physiological saline at 37 ° C. for 72 hours, the lens was taken out and the surface adhering water was wiped off and weighed. Next, the lens was dried at 80 ° C. under vacuum until a constant weight was obtained, and the weight was determined by the following formula.
Moisture content (%) = (weight change / weight before drying) x 100
[0052]
(5) Oxygen permeability coefficient
According to the contact lens society standard Dk value measuring method, it measured by the electrode method using the K-316-IPI type | mold film oxygen permeation measuring apparatus by a Rika Seiki Co., Ltd. product. For the sample piece, a lens having a diameter of about 14 mm and a thickness of about 0.1 to 0.5 mm was prepared with a mold and used for measurement. The measurement was performed in 35 ° C. physiological saline. The oxygen permeation coefficient was determined from the slope of the oxygen permeation amount with respect to the sample thickness. Unit is (ml · cm / cm ² ・ Sec ・ mmHg) × 10 ^-11 Expressed in
(6) Tensile strength
Using a universal testing machine AGS-50B manufactured by Shimadzu Corporation, the measurement was performed in physiological saline at 25 ° C. The lens was cut out with a width of 3 mm at the center, and the strength at break was determined. The unit is (MPa).
[0053]
(7) Lipid adhesion
Place one lens in 10 ml of 0.1% triolein (phosphate buffer) suspension and stir at 40 ° C for 2 hours. Washing was repeated 5 times with 5 ml of purified water for 30 seconds. This lens is vacuum-dried, extracted with acetone, colored with a triglyceride test agent (Triglyceride G-Test Wako, manufactured by Wako Pure Chemical Industries, Ltd.), and an absorbance spectrophotometer (V-550, manufactured by JASCO Corporation). The absorbance at 505 nm was measured. The amount of attached lipid per lens was determined from a separately determined calibration curve. The evaluation results are shown in Table 1.
[0054]
[Examples 2 to 8]
Contact lenses were prepared from the synthesized hydrophilic polysiloxane monomers (A-2 to A-8) with the same composition as in Example 1, and the physical properties were evaluated. The results are shown in Table 1.
[Example 9]
Synthesized hydrophilic polysiloxane monomer (A-1) 60 parts by weight, N-vinylpyrrolidone 30 parts by weight, 3-tris (trimethylsiloxy) silylpropyl methacrylate 10 parts by weight, 2,4,6-trimethylbenzoyldiphenylphosphine oxide 0.5 After dissolving parts by weight in 60 parts by weight of tetrahydrofuran and stirring and mixing, contact lenses were prepared in the same manner as in Example 1, and physical properties were evaluated. The results are shown in Table 1.
[0055]
[Example 10]
50 parts by weight of the synthesized hydrophilic polysiloxane monomer (A-1), 15 parts by weight of N-vinylpyrrolidone, 15 parts by weight of N-vinyl-N-methylacetamide, 20 parts by weight of 3-tris (trimethylsiloxy) silylpropyl methacrylate, After dissolving 1 part by weight of ethylene glycol dimethacrylate and 0.5 part by weight of 2,4,6-trimethylbenzoyldiphenylphosphine oxide in 50 parts by weight of methyl ethyl ketone and stirring and mixing, a contact lens was prepared in the same manner as in Example 1, and the physical properties were Evaluated. The results are shown in Table 1.
[0056]
[Comparative Example 1]
A contact lens having a composition similar to that of Example 1 was prepared using a both-end methacryl-modified silicone (FM7721) manufactured by Chisso Corporation, and the physical properties were evaluated. The results are shown in Table 1.
[Comparative Example 2]
A contact lens was produced from the synthesized hydrophilic polysiloxane monomer (B-1) with the same composition as in Example 1, and the physical properties were evaluated. The results are shown in Table 1.
[0057]
[Table 1]
[0058]
【The invention's effect】
The copolymer comprising the hydrophilic polysiloxane monomer of the present invention as a component has surface hydrophilicity and high oxygen permeability, and is excellent in stain resistance, flexibility, optical transparency, and strength. It is useful as an ophthalmic lens material.
[Brief description of the drawings]
FIG. 1 is an NMR spectrum of Synthesis Example 1 (A-1).
FIG. 2 is an IR spectrum of Synthesis Example 1 (A-1).

Claims (22)

A monomer having a polymerizable unsaturated group at least at a terminal where a polysiloxane group and a polyoxyalkylene group are linked, having at least two polymerizable unsaturated groups at one terminal, and having the formulas (I) and (I) A hydrophilic polysiloxane monomer for an ophthalmic lens, which is selected from II), (III) and (IV).
X1− (Z1 −P1−Z2−S1) _p −Z3−P2−Z4−X2 (I)
X3-(Z5-S2-Z6-P3) _q- Z7-S3-Z8-X4 (II)
X5− (Z9 −P4−Z10 −S4) _r −Z11 −P5−Z12 −S5 (III)
X6− (Z13−S6−Z14 −P6) _s −Z15 −S7−Z16 −P7 (IV)
[Wherein, p and q are 1 to 10. r and s are 0-10. X1 and X2, X3, and X4 are independently selected from the following formulas (1), (2), and (3). At least one of X1 or X2 is the following formula (1) or (2), and at least one of X3 or X4 is the following formula (1) or (2). X5 and X6 are represented by the following formula (1) or (2).
(Each a and b 1, c 2, d 3, e are each independently 0 or 1. Each W is independently -O- or -NR5 -. R1 and R2, R3, and R4 are each independently selected from amide group, urethane group, urea group, oxy group, ester group, carbonyl group, aryl group, or alicyclic hydrocarbon group having 5 to 7 carbon atoms. A chain hydrocarbon group having 1 to 10 carbon atoms which may be interrupted in the above points. The chain hydrocarbon group having 1 to 10 carbon atoms is an aryl group, the alicyclic hydrocarbon group having 5 to 7 carbon atoms is an alkyl group having 1 to 4 carbon atoms, a fluoro group, or a fluoro group having 1 to 10 carbon atoms. Any one point or more points may be substituted with a substituted hydrocarbon group or a hydroxyl group.
A1, A2, and A3 are independently hydrogen, a hydroxyl group, a methyl group, or any one of formulas (i), (ii), and (iii), and at least two of A1, A2, and A3 are represented by formula (i) or It is selected from (ii) and (iii) and may be the same or different.
A4 is selected from formulas (i) and (ii), (iii).
Here, each R5 is independently hydrogen or a hydrocarbon group having 1-4 carbon atoms. )
S1 and S2, S3, S4, S6, and S7 are independently polysiloxane groups represented by the formula (4). S5 is a polysiloxane group represented by the formula (5).
(Each R6 and R7 are each independently one or more points depending on the amide group, urethane group, urea group, oxy group, ester group, carbonyl group, aryl group, alicyclic hydrocarbon group having 5-7 carbon atoms. A chain hydrocarbon group having 1 to 30 carbon atoms which may be interrupted at the above point.The chain hydrocarbon group having 1 to 30 carbon atoms is an aryl group, an alicyclic hydrocarbon having 5 to 7 carbon atoms. The group may be substituted at any one or more points with an alkyl group having 1-4 carbon atoms, a fluoro group, a fluoro group-substituted hydrocarbon group having 1-10 carbon atoms, or a hydroxyl group.
R8 And R9, R10 , R11 , R12 Are groups selected from a hydrocarbon group having 1 to 12 carbon atoms or a trimethylsiloxy group, which may be the same or different.
Y is formed by linking structural units (iv), (v), (vi) represented by the following formula, and (iv), (v), (vi) has 1 to 1000 linkages, v) and (vi) may be 0.
Where R13 And R14 Is independently a hydrocarbon group having 1 to 12 carbon atoms or a trimethylsiloxy group. R15 And R16 Is independently a hydrocarbon group having 1-12 carbon atoms or a trimethylsiloxy group, a substituted hydrocarbon group having 1-12 carbon atoms, and R15 Or R16 At least one of these is a fluoro group-substituted hydrocarbon group. R17 And R18 Is independently a group consisting of a hydrocarbon group having 1-12 carbon atoms or a trimethylsiloxy group, a hydrophilic substituent, R17 Or R18 At least one of these is a hydrophilic substituent. The hydrophilic substituent here is a chain or cyclic hydrocarbon group formed by bonding at least one substituent selected from a hydroxyl group, a carboxylic acid group, an amino group, an imino group, an amide group, and an oxyalkylene group. Say. )
P1 and P2, P3, P4, P5, and P6 are independently polyoxyalkylene groups represented by formula (19) or formula (21), and P7 is a polyoxyalkylene group represented by formula (20) or formula (22). An alkylene group;
(M is 1 to 200.)
Z1 and Z2-Z16 are each independently a linking group represented by the formula (5a), (5b), or (5c).
LR6L (5a)
LR6 (5b)
R6L (5c)
(Where L is −C (O) NR5 -, -NR5C (O)-, -C (O) O-, -OC (O)-, -C (O)-. )] The hydrophilicity for an ophthalmic lens according to claim 1, wherein p and q in formula (I) and formula (II) are each selected from 1, and r and s in formula (III) and formula (IV) are each selected from 0. Polysiloxane monomer. The hydrophilic poly for the ophthalmic lens according to claim 1 or 2, wherein X1 and X2, X3, X4 in the formulas (I) and (II) are selected from the formulas (8), (9), and (10): Siloxane monomer. However, at least one of X1 and X2 is the formula (8) or (9), and at least one of X3 and X4 is the formula (8) or (9).
The hydrophilic polysiloxane monomer for ophthalmic lenses according to claim 1 or 2, wherein X5 and X6 in formula (III) and formula (IV) are selected from formula (11) or (12).
S1 and S2, S3, S4, S6, and S7 are selected from the formula (13) and S5 is selected from the polysiloxane group of the formula (14) in the formula (I) and the formulas (II), (III), and (IV). The hydrophilic polysiloxane monomer for ophthalmic lenses as described in any one of Claims 1-4.
(Where k is 0 to 4) S1 and S2, S3, S4, S6, and S7 in the formula (I) and formulas (II), (III), and (IV) are selected from the polysiloxane group in the formula (15) and S5 in the formula (16) The hydrophilic polysiloxane monomer for ophthalmic lenses as described in any one of Claims 1-4.
S1 and S2, S3, S4, S6, and S7 are selected from the formula (17) and S5 is selected from the polysiloxane group of the formula (18) in the formula (I) and the formulas (II), (III), and (IV). The hydrophilic polysiloxane monomer for ophthalmic lenses as described in any one of Claims 1-4.
In formula (I) and formula (II), (III), (IV), P1 and P2, P3, P4, P5, P6 are selected from the polyoxyalkylene group of formula (19), and P7 is selected from the polyoxyalkylene group of formula (20). The hydrophilic polysiloxane monomer for an ophthalmic lens according to any one of claims 1 to 7.
A (co) polymer obtained by polymerizing a polymerizable composition containing at least one hydrophilic polysiloxane monomer for ophthalmic lenses according to any one of claims 1 to 8. A copolymer obtained by polymerizing a polymerizable composition comprising at least one hydrophilic polysiloxane monomer for ophthalmic lenses according to any one of claims 1 to 8 and one or more copolymerizable monomers. Polymer. It contains at least one kind of hydrophilic polysiloxane monomer for ophthalmic lenses according to any one of claims 1 to 8, one or more types of copolymerizable monomers, and one or more kinds of solvents that do not participate in polymerization. A copolymer obtained by polymerizing a polymerizable composition. The copolymer according to claim 10 or 11, wherein the copolymerizable monomer has an amide group. The copolymer according to claim 12, wherein the copolymerizable monomer is at least one monomer selected from N, N-dimethylacrylamide, N-vinylpyrrolidone, and N-methylN-vinylacetamide. The copolymer according to any one of claims 11 to 13, wherein the solvent not involved in the polymerization is selected from alcohols, ketones, ethers, esters, carboxylic acids, sulfoxides, amines, amides, and nitrile compounds. The copolymer according to claim 14, wherein the solvent not involved in the polymerization is selected from butanol, hexanol, methyl ethyl ketone, tetrahydrofuran, ethyl acetate, dimethyl sulfoxide, N, N dimethylformamide, and acetonitrile. An ophthalmic lens comprising the (co) polymer according to any one of claims 9 to 15. The contact lens which consists of a (co) polymer as described in any one of Claims 9-15. A hydrous contact lens comprising the (co) polymer according to any one of claims 9 to 15. The contact lens according to claim 17 or 18, wherein the (co) polymerized composition is polymerized into a lens shape in a mold. The contact lens according to claim 19, wherein the contact lens is polymerized in a mold selected from resins having a contact angle with water of 90 ° or less in a droplet method. 21. The contact lens according to claim 20, wherein the contact lens is polymerized in a mold selected from resins having a contact angle with water in a droplet method of 65 ° to 80 °. The contact lens according to claim 19, wherein the mold is made of a resin selected from polyamide, polyethylene terephthalate, and ethylene vinyl alcohol copolymer.