CN110199219B - Monomer composition for contact lens, polymer for contact lens and method for producing same, and contact lens and method for producing same - Google Patents
Monomer composition for contact lens, polymer for contact lens and method for producing same, and contact lens and method for producing same Download PDFInfo
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- CN110199219B CN110199219B CN201880007012.3A CN201880007012A CN110199219B CN 110199219 B CN110199219 B CN 110199219B CN 201880007012 A CN201880007012 A CN 201880007012A CN 110199219 B CN110199219 B CN 110199219B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
- C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
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- G—PHYSICS
- G02—OPTICS
- G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
- G02C7/00—Optical parts
- G02C7/02—Lenses; Lens systems ; Methods of designing lenses
- G02C7/04—Contact lenses for the eyes
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Abstract
The present invention provides a monomer composition for a contact lens, which is useful for producing a contact lens having excellent surface hydrophilicity, oxygen permeability, mechanical strength and wearing feeling. Further provided are a polymer for contact lenses obtained from the composition, and a contact lens. The composition comprises: a specific amount of (A) a phosphorylcholine group-containing methacrylate monomer; (B) one or more hydroxyl-containing monomers selected from the group consisting of hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyethyl acrylamide, ethylene glycol monovinyl ether and diethylene glycol monovinyl ether; (C) a siloxane-containing itaconic acid diester monomer; (D) a siloxane group-containing (meth) acrylate; and (E) a crosslinking agent.
Description
Technical Field
The present invention relates to a monomer composition for a contact lens, a polymer of the composition and a method for producing the same, and a contact lens formed from a hydrate of the polymer and a method for producing the same.
Background
Conventional hydrogel contact lenses have a problem in safety when worn for a long time because oxygen supply to the cornea of the eye is insufficient. As a contact lens which solves this drawback and has improved safety, a silicone hydrogel contact lens has been developed.
However, silicone hydrogel contact lenses have a problem in that it is difficult to make the lens surface hydrophilic. In general, soft contact lenses are manufactured by a cast molding method, and in this method, a polypropylene mold is often used. When silicone hydrogel contact lenses are produced by this method, since polypropylene is hydrophobic, silicone monomers are polymerized in a state of being oriented on the mold surface. Therefore, a silicone part is formed on the lens surface, and the hydrophilicity of the surface is lowered. When the hydrophilicity of the lens surface is insufficient, lipids, proteins, and the like may adhere to the lens, causing cloudiness of the lens and eye diseases.
Therefore, it has been proposed to perform coating with plasma gas or hydrophilic polymer or to form surface graft polymer using hydrophilic monomer on the lens surface after the preparation of silicone hydrogel contact lenses. However, these surface treatments require many apparatuses and are not expected in mass production because the process is complicated.
For the purpose of improving the hydrophobicity of the surface of a soft contact lens using a silicone-containing copolymer, a method of using a hydrophilic monomer having a vinyl group such as N, N-dimethylacrylamide, N-vinyl-2-pyrrolidone, N-methyl-N-vinylacetamide, N-vinylpyrrolidone in a monomer composition has been proposed. However, even when such a hydrophilic monomer is used, the hydrophilicity of the lens surface is not sufficient.
Patent document 1 discloses a method for producing a lens from a composition for silicone hydrogel, the composition for silicone hydrogel containing: a silicone monomer having a (meth) acryloyl group, a hydrophilic monomer having a vinyl group, a crosslinkable monomer, and a polymerization initiator having a 10-hour half-life temperature of 70 to 100 ℃. This method aims to improve the hydrophilicity of the lens surface by utilizing the poor polymerizability of the raw material monomer, but still cannot obtain satisfactory hydrophilicity.
Patent document 2 discloses a monomer composition for a contact lens, which contains a phosphorylcholine group-containing (meth) acrylate monomer, a hydroxyl group-containing (meth) acrylate silicone monomer, and a crosslinking agent. Patent document 3 discloses a silicone hydrogel contact lens obtained from a composition containing 2-Methacryloyloxyethyl Phosphorylcholine (MPC), a dimethacryloyl silicone macromer, and (3-methacryloyloxy-2-hydroxypropoxy) propyl bis (trimethylsiloxy) methylsilane (SiGMA). Patent document 4 discloses a contact lens obtained from a composition containing a (meth) acrylate monomer containing a phosphorylcholine group or a carboxybetaine group, a (meth) acrylate silicone monomer having a secondary hydroxyl group, a (meth) acrylate cyclic silicone monomer having no hydroxyl group, a maleic acid or fumaric acid diester silicone monomer having a fluorinated alkyl group, and the like. However, the contact lenses of patent documents 2 to 4 have a problem that the oxygen permeability is reduced although the hydrophilicity of the lens surface is improved.
Patent document 5 discloses a composition containing a phosphorylcholine group-containing (meth) acrylate monomer, a hydroxyl group-containing (meth) acrylate silicone monomer, and a silicone (meth) acrylate, and describes that the polymer can be used in a contact lens. Patent document 6 discloses a composition containing a siloxane group-containing itaconic acid diester monomer having a primary hydroxyl group and MPC, and describes that the polymer can be used for a contact lens. Patent documents 5 and 6 have obtained good results in terms of hydrophilicity and oxygen permeability of the lens surface.
Documents of the prior art
Patent document
Patent document 1: international publication No. 2015/001811
Patent document 2: japanese patent laid-open publication No. 2007-009060
Patent document 3: japanese patent laid-open No. 2014-089477
Patent document 4: japanese laid-open patent publication No. 2007-056220
Patent document 5: japanese laid-open patent publication No. 2007-197513
Patent document 6: international publication No. 2010/104000
Disclosure of Invention
Technical problem to be solved by the invention
However, the contact lenses of patent documents 5 and 6 are excellent in hydrophilicity and oxygen permeability of the lens surface, but are insufficient in mechanical strength and wearing sensation, and further improvement is considered to be required.
The present invention addresses the problem of providing a contact lens that exhibits excellent surface hydrophilicity, oxygen permeability, mechanical strength, and wearing comfort even when produced using a hydrophobic mold made of polypropylene or the like. The term "excellent surface hydrophilicity" refers to a property of having a water film retention time of 30 seconds or more in the wbut (water film break up time) evaluation described in detail in examples.
Another object of the present invention is to provide a composition and a polymer which can be suitably used for obtaining the above-mentioned contact lens.
It is still another object of the present invention to provide a method for producing the polymer and the contact lens.
Means for solving the problems
The present inventors have conducted extensive studies and, as a result, have found that all of the above objects can be achieved by using a monomer composition containing two hydrophilic monomers and two siloxane-containing silicone monomers as a raw material for a contact lens, and have completed the present invention.
According to one embodiment of the present invention, there is provided a monomer composition for a contact lens, wherein the composition comprises: (A) a phosphorylcholine group-containing methacrylate monomer represented by the following formula (1); (B) one or more hydroxyl-containing monomers selected from the group consisting of hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyethyl acrylamide, ethylene glycol monovinyl ether and diethylene glycol monovinyl ether; (C) a siloxane group-containing itaconic acid diester monomer represented by the following formula (2); (D) a siloxane group-containing (meth) acrylate represented by the following formula (3); and (E) a crosslinking agent. The content of the component (A) is 5-20% by mass, the content of the component (B) is 5-25% by mass, the content of the component (C) is 30-70% by mass, the content of the component (D) is 5-40% by mass, and the content of the component (E) is 0.1-10% by mass, based on 100% by mass of the total of all monomer components in the composition.
[ chemical formula 1]
[ chemical formula 2]
[ chemical formula 3]
In the formula (3), R1Is a hydrogen atom or a methyl group, m is 0 or 1, and n is 10 to 20.
According to another embodiment of the present invention, there are provided a polymer for a contact lens formed from the polymer of the above-mentioned monomer composition for a contact lens, and a method for preparing the same.
According to still another embodiment of the present invention, there are provided a contact lens comprising the hydrate of the above-mentioned contact lens polymer and a method for producing the same.
Effects of the invention
The monomer composition for a contact lens of the present invention contains components (a) to (E) as essential components. Therefore, the contact lens of the present invention obtained using the polymer of the composition can exhibit excellent surface hydrophilicity, oxygen permeability, mechanical strength and wearing sensation. Further, according to the method for producing a polymer for a contact lens and the method for producing a contact lens of the present invention, a silicone hydrogel soft contact lens having the above-described excellent properties can be produced.
Detailed Description
The monomer composition for a contact lens of the present invention is a uniform transparent liquid, and contains components (a) to (E) described later as essential components, and may further contain component (F) as an optional component. The polymer for a contact lens of the present invention is formed from a polymer of the monomer composition for a contact lens, and the contact lens of the present invention is formed from a hydrate of the polymer for a contact lens. Hereinafter, the monomer composition for a contact lens of the present invention is simply referred to as a composition. The polymer for a contact lens of the present invention is simply referred to as a polymer.
(A) The components: methyl acrylate monomer containing phosphorylcholine group
(A) The component (A) is a phosphorylcholine group-containing methacrylate monomer represented by the following formula (1), specifically 2-Methacryloyloxyethyl Phosphorylcholine (MPC). By containing the component (a), the surface of the contact lens produced from the polymer of the composition of the present invention can be made to have good hydrophilicity and lubricity.
[ chemical formula 4]
In the composition of the present invention, the content of the component (A) is 5 to 20% by mass, preferably 8 to 20% by mass, based on 100% by mass of the total of all monomer components. If the content of the component (A) is less than 5% by mass. Sufficient surface hydrophilicity cannot be obtained. On the other hand, if it exceeds 20 mass%, the component (a) is difficult to dissolve in the composition, and the mechanical strength of the contact lens may decrease. In the present invention, the "monomer component" refers to the components (A) to (F).
(B) The components: hydroxyl group-containing monomer
(B) The component (A) is one or more hydroxyl-containing monomers selected from the group consisting of hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyethyl acrylamide, ethylene glycol monovinyl ether and diethylene glycol monovinyl ether. By containing the component (B) in a predetermined amount, the component (a) can be dissolved well in the composition of the present invention. From the viewpoint of the solubility of the component (A), the hydroxyl group of the component (B) is preferably a primary hydroxyl group. In the present invention, "(meth) acrylate" means "acrylate and/or methacrylate", and "(meth) acrylic acid" means "acrylic acid and/or methacrylic acid".
Specific examples of the component (B) include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, polyethylene glycol monomethacrylate, N- (2-hydroxyethyl) acrylamide, N-methyl-N- (2-hydroxyethyl) acrylamide, ethylene glycol monovinyl ether, diethylene glycol monovinyl ether, and 4-hydroxybutyl vinylether. (B) The component (B) may be any one of these monomers, or may be a mixture of two or more of them.
From the viewpoint of better solubility of component (A), 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, N- (2-hydroxyethyl) acrylamide, N-methyl-N- (2-hydroxyethyl) acrylamide, ethylene glycol monovinyl ether and diethylene glycol monovinyl ether are preferable, and 2-hydroxyethyl acrylate, N- (2-hydroxyethyl) acrylamide, N-methyl-N- (2-hydroxyethyl) acrylamide and ethylene glycol monovinyl ether are particularly preferable.
In the composition of the present invention, the content of the component (B) is 5 to 25% by mass, where the total of all monomer components is 100% by mass. If the content of the component (B) is less than 5% by mass, the composition of the present invention may be difficult to be a uniform transparent liquid. On the other hand, if it exceeds 25 mass%, the oxygen permeability of the contact lens may be decreased.
(C) The components: siloxane group-containing itaconic acid diester monomer
(C) The component (A) is a siloxane group-containing itaconic acid diester monomer represented by the following formula (2). (C) The ingredients help to improve oxygen permeability and transparency of the contact lens.
[ chemical formula 5]
The monomer of formula (2) can be obtained by esterification of monoethylene glycol itaconate with 3-iodopropyl [ tris (trimethylsiloxy) ] silane. The monoethylene glycol itaconate can be obtained by reacting itaconic anhydride with ethylene glycol, as described in patent document 6, for example. Further, 3-iodopropyl [ tris (trimethylsiloxy) ] silane is commercially available, but in order to increase the purity of the obtained silicone monomer of the present invention, it is preferable to use a high purity product.
In the esterification reaction, a small amount of a structural isomer represented by the following formula (2') may be produced as a by-product. In the present invention, a mixture of the monomer of formula (2) with a small amount of the monomer of formula (2') may be used as the component (C). That is, in the present invention, the "siloxane group-containing itaconic acid diester monomer represented by the formula (2)" includes not only the monomer of the formula (2) but also a part of the isomer of the formula (2') in addition to the monomer of the formula (2).
[ chemical formula 6]
In the composition of the present invention, the content of the component (C) is 30 to 70% by mass, preferably 30 to 60% by mass, based on 100% by mass of the total of all monomer components. When the content of the component (C) is less than 30% by mass, the component (a) may be difficult to dissolve in the composition of the present invention, or the produced polymer for a contact lens may be clouded. On the other hand, if the amount exceeds 70 mass%, the surface hydrophilicity of the contact lens may be insufficient.
(D) The components: (meth) acrylate containing a siloxane group
(D) The component (A) is a siloxane group-containing (meth) acrylate represented by the following formula (3). (D) The ingredients help to improve oxygen permeability and adjust mechanical strength of the contact lens. (D) The component (c) may be prepared by the method disclosed in Japanese patent application laid-open No. 2014-031338, or may be a commercially available product.
[ chemical formula 7]
In the formula (3), R1Is a hydrogen atom or a methyl group. m represents the number of ethyleneoxy groups and is 0 or 1. n is the number of repetitions of the dimethylsiloxane moiety and is 10 to 20. (D) The component (C) may be a mixture of a plurality of compounds having different repetition numbers nA compound (I) is provided. In this case, n is an average value of number average molecular weights, and is within a range of 10 to 20. n is less than 10, which is not preferable because the oxygen permeability is lowered. In addition, when n is greater than 20, the surface hydrophilicity or mechanical strength of the contact lens decreases.
M in formula (3) is preferably 0. That is, the component (D) is preferably a siloxane group-containing (meth) acrylate represented by the following formula (4). R in the formula (4)1And n and R in the formula (3)1And n are the same.
[ chemical formula 8]
In the composition of the present invention, the content of the component (D) is 5 to 40% by mass, based on 100% by mass of the total of all monomer components. If the content of the component (D) is less than 5 mass%, the mechanical strength of the contact lens may become too high, and the wearing sensation may not be excellent. On the other hand, if the amount exceeds 40 mass%, the hydrophilicity of the surface of the contact lens may decrease.
In the composition of the present invention, the total content ratio of the component (C) and the component (D) is preferably 40 to 75% by mass, more preferably 60 to 65% by mass, based on 100% by mass of the total of all monomer components. By setting the total content to 40% by mass or more, the composition of the present invention which is a uniform transparent liquid can be easily obtained. On the other hand, by setting the content to 75% by mass or less, the contact lens can be prevented from becoming excessively hard.
(E) The components: crosslinking agent
(E) Component (c) functions as a crosslinking agent during polymerization of the monomers of components (a) to (D). (E) The component (B) usually has 2 or more polymerizable unsaturated groups. Since the composition of the present invention contains a predetermined amount of the component (E), the polymer of the present invention has a crosslinked structure, and thus the contact lens of the present invention exhibits excellent solvent resistance.
For example, the component (E) may be a silicone dimethacrylate represented by the following formula (5).
[ chemical formula 9]
In the formula (5), p and r are equal to each other and are 0 or 1. q represents the number of repetitions of a dimethylsiloxane moiety, and is 10 to 70. The silicone dimethacrylate represented by the formula (5) may be a mixture of a plurality of compounds having different repeating numbers q. In this case, q is an average value of the number average molecular weights, and is within a range of 10 to 70 from the viewpoint of availability.
Specific examples of the component (E) include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, methylenebisacrylamide, allyl methacrylate, ethyl (2-allyloxy) methacrylate, ethyl 2- (2-vinyloxyethoxy) acrylate, and ethyl 2- (2-vinyloxyethoxy) methacrylate, in addition to the silicone dimethacrylate of the formula (5). (E) The component (C) may be any one of these crosslinking agents, or may be a mixture of two or more thereof.
In the composition of the present invention, the content of the component (E) is 0.1 to 10% by mass, where the total of all monomer components is 100% by mass. If the content of the component (E) is less than 0.1% by mass, the solvent resistance of the contact lens is lowered. On the other hand, if the content exceeds 10 mass%, the contact lens may be brittle and damaged, and the mechanical strength may be too high, which may deteriorate the wearing feeling of the contact lens.
(F) The components: monomers other than the components (A) to (E)
(F) The component (A) is a monomer other than the components (A) to (E). (F) The component (b) is an arbitrary component and can be used for the purpose of adjusting the water content of the contact lens.
The component (F) may be a monomer having one or more functional groups selected from amide groups, carboxyl groups, and ester groups. Specific examples of the monomer having an amide group include N-vinylpyrrolidone, N-vinylpiperidin-2-one, N-vinyl-caprolactam, N-vinyl-3-methyl-2-caprolactam, N-dimethylacrylamide, N-diethylacrylamide, acrylamide, N-isopropylacrylamide, acryloylmorpholine, N-vinyl-N-methylacetamide, N-vinylacetamide, N-vinylformamide and the like. Specific examples of the monomer having a carboxyl group include (meth) acrylic acid, and mono [2- [ (2-methyl-acryloyl) oxy ] ethyl ] succinate. Specific examples of the monomer having an ester group include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate, methoxypolyethylene glycol methacrylate, and the like. (F) The component (B) may be any one of these monomers, or may be a mixture of two or more of them.
When the composition of the present invention contains the component (F), the content of the component (F) is preferably 25% by mass or less, assuming that the total of all monomer components is 100% by mass. When the content is 25% by mass or less, the solubility of the component (A) in the composition is good, and the surface hydrophilicity of the contact lens is also good.
The composition of the present invention may contain a solvent in addition to the above components (A) to (F). The solvent is not particularly limited as long as it improves the solubility of each component in the composition, and is preferably a solvent having a hydroxyl group. By using a solvent having a hydroxyl group, the dissolution rate of the component (a) in the composition of the present invention becomes high, and the dissolution becomes easy.
The solvent having a hydroxyl group may be an alcohol or a carboxylic acid. Specific examples of the alcohols include ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, 1-pentanol, 2-methyl-2-butanol, 1-hexanol, 1-octanol, 1-decanol, and 1-dodecanol. Specific examples of the carboxylic acids include glycolic acid, lactic acid, and acetic acid. The solvent may be any one of these solvents, or may be a mixture of two or more of these solvents. From the viewpoint of solubility of the component (A) and pH stability of the composition, the solvent is particularly preferably formed of at least one selected from the group consisting of ethanol, 1-propanol and 2-propanol.
When the composition of the present invention contains a solvent, the content of the solvent is preferably 25 parts by mass or less, assuming that the total amount of all monomer components in the composition is 100 parts by mass. When the amount is 25 parts by mass or less, the mechanical strength of the contact lens is good.
The composition of the present invention may contain a polymerization initiator in addition to the above components (A) to (F). The polymerization initiator may be a known polymerization initiator, and is preferably a thermal polymerization initiator. When a thermal polymerization initiator is used, the copolymerizability of each monomer component is likely to change due to a temperature change during the polymerization. Examples of the thermal polymerization initiator include 2,2 '-azobisisobutyronitrile, dimethyl azobisisobutyrate, 2' -azobis [2- (2-imidazolin-2-yl) propane ] hydrochloride, 2 '-azobis (2, 4-dimethylvaleronitrile), 2' -azobis [2- (2-imidazolin-2-yl) propane ] disulfate dihydrate, 2 '-azobis (2-methylpropionamidine) dihydrochloride, 2' -azobis [ N- (2-carboxyethyl) -2-methylpropionamidine ] dihydrate, 2 '-azobis [2- (2-imidazolin-2-yl) propane ], 2' -azobis (1-imino-1-pyrrolidinyl-2-methylpropane) propane ) Azo polymerization initiators such as dihydrochloride, azobismethyl N-bishydroxymethyl hydroxyethyl propionamide, 2 ' -azo [ 2-methyl-N- (2-hydroxyethyl) propionamide ], 2 ' -azobis (2-methylpropionamidine) dihydrochloride, and 2,2 ' -azo [ 2-methyl-N- (2-hydroxyethyl) propionamide ], and peroxide polymerization initiators such as benzoyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, dilauroyl peroxide, t-butyl peroxyhexanoate, and bis (3,5, 5-trimethylhexanoyl) peroxide. These polymerization initiators may be used alone, or two or more of them may be used in combination. Among them, the azo polymerization initiator is preferable from the viewpoint of safety and availability, and 2,2 '-azobisisobutyronitrile, dimethyl azobisisobutyrate and 2, 2' -azobis (2, 4-dimethylvaleronitrile) are particularly preferable from the viewpoint of reactivity.
The amount of the polymerization initiator to be added is preferably 0.1 to 3 parts by mass, more preferably 0.1 to 2 parts by mass, and particularly preferably 0.2 to 1 part by mass, based on 100 parts by mass of the total of all monomer components in the composition. When the amount is less than 0.1 part by mass, the polymerizability of the composition may be insufficient, and the advantage of blending the polymerization initiator may not be obtained. When the amount exceeds 3 parts by mass, the extraction and removal of the decomposition product of the polymerization initiator may be insufficient in the case of cleaning the polymer for contact lenses and producing contact lenses.
The composition of the present invention may contain additives such as a polymerizable ultraviolet absorber and a polymerizable coloring matter (colorant) in addition to the components (a) to (F) as long as the object of the present invention is not impaired. By incorporating an ultraviolet absorber, the burden of ultraviolet rays such as sunlight on eyes can be reduced. Further, by blending a coloring matter, a colored contact lens can be produced.
The method for producing the composition of the present invention is not particularly limited, and for example, the composition can be produced by adding the respective components in an arbitrary order or all at once to a stirring (mixing) apparatus, and stirring (mixing) at a temperature of 10 to 50 ℃ until uniform. Among them, when the composition contains a polymerization initiator, care should be taken not to initiate polymerization reaction at the time of mixing, and mixing at 40 ℃ or lower is preferable. From the viewpoint of improving the solubility of the component (a), it is preferable to mix and dissolve three components (a), (B), and (C) and then add and mix the other components.
The polymer of the present invention is formed from the polymer of the above-described composition of the present invention. The following is a description of the method for producing the polymer of the present invention. The production method shown below is only one embodiment of the method for obtaining the polymer, and the polymer of the present invention is not limited to the one obtained by the production method.
The polymer of the present invention can be prepared by filling the composition of the present invention in a mold and performing polymerization. As the mold, a mold having a hydrophobic surface formed of polypropylene or the like can be used.
The polymerization reaction can be carried out, for example, by a one-stage polymerization method in which the composition is maintained at a temperature of 45 to 140 ℃ for 1 hour or more in accordance with the decomposition temperature of the polymerization initiator used, and is preferably carried out by a two-stage or more polymerization method including a polymerization step 1 and a polymerization step 2 as described below. In this case, the hydrophilicity of the surface of the contact lens can be further improved. After completion of the polymerization, the polymer may be cooled to, for example, 60 ℃ or lower, and then taken out of the mold.
[ polymerization Process 1]
In the polymerization step 1, the polymerization initiator is added to the composition as needed, and polymerization is carried out at a temperature of 45 to 75 ℃ for 1 hour or more.
The polymerization temperature in the polymerization step 1 is preferably 50 to 70 ℃ and more preferably 55 to 70 ℃. When the polymerization temperature in the polymerization step 1 is from 45 ℃ to 75 ℃, a polymer having good physical properties such as surface hydrophilicity can be stably obtained.
The polymerization time in the polymerization step 1 is preferably 2 hours to 12 hours. When the polymerization time in the polymerization step 1 is 1 to 12 hours, a polymer having good physical properties such as surface hydrophilicity can be efficiently obtained.
[ polymerization Process 2]
The polymerization step 2 is carried out after the polymerization step 1, and the polymerization reaction is carried out at 90 to 140 ℃ which is higher than the temperature in the polymerization step 1.
The polymerization temperature in the polymerization step 2 is preferably 100 to 120 ℃. When the polymerization temperature in the polymerization step 2 is 90 to 140 ℃, a polymer having good physical properties such as surface hydrophilicity can be stably obtained, the polymer can be efficiently obtained, and a mold made of polypropylene or the like is not deformed.
The polymerization time in the polymerization step 2 is preferably 1 hour to 10 hours. When the polymerization time in the polymerization step 2 is 1 to 10 hours, a polymer having good physical properties such as surface hydrophilicity can be efficiently obtained.
The atmosphere in which the polymerization steps 1 and 2 are carried out is not particularly limited, but it is preferable that the polymerization steps 1 and 2 are carried out in an inert gas atmosphere such as nitrogen or argon from the viewpoint of increasing the polymerization rate. In this case, an inert gas may be introduced into the composition or the composition-filling portion of the mold may be made to have an inert gas atmosphere.
The pressure in the mold may be from atmospheric to slightly positive. When the polymerization is carried out in an inert gas atmosphere, the pressure is preferably 1kgf/cm in gauge (gauge pressure)2The following.
The contact lenses of the invention are silicone hydrogel contact lenses formed from hydrates of the above-described polymers. That is, the contact lens of the present invention is obtained by hydrating the polymer of the present invention to make it hydrated and form a hydrogel. In the present specification, the term "silicone hydrogel" refers to a hydrogel having a silicone moiety in a polymer. Since the composition of the present invention contains the components (C) and (D) as silicone-containing monomers, the polymer thereof has a silicone moiety, and a silicone hydrogel can be formed by hydrating (containing water).
The water content (ratio of water to the total mass of the contact lens) of the contact lens is preferably 35 mass% to 60 mass%, more preferably 35 mass% to 50 mass%. When the water content is 35 to 60 mass%, the balance with oxygen permeability can be made excellent.
Next, a method for producing a contact lens of the present invention will be described. The production method described below is only one embodiment of the method for producing the contact lens of the present invention, and the contact lens of the present invention is not limited to the production method.
After the polymerization reaction, the polymer may be in a state of a mixture with an unreacted monomer component (unreacted product), a residue of each component, a by-product, a residual solvent, or the like. Although such a mixture can be directly subjected to hydration treatment, it is preferable to purify the polymer using a purification solvent before the hydration treatment.
Examples of the solvent for purification include water, methanol, ethanol, 1-propanol, 2-propanol, and a mixture of these solvents. The purification can be carried out, for example, in the following manner: immersing the polymer in an alcohol solvent at a temperature of 10 to 40 ℃ for 10 minutes to 5 hours, and then immersing in water for 10 minutes to 5 hours, etc. After the immersion in the alcohol solvent, the mixture may be immersed in an aqueous alcohol having an alcohol concentration of 20 to 50 wt% for 10 minutes to 5 hours, and then immersed in water. As the water, pure water, ion-exchanged water, and the like are preferable.
The contact lens of the present invention can be obtained by immersing the polymer in physiological saline and hydrating the polymer so that the polymer has a predetermined water content. The physiological saline may be boric acid-buffered physiological saline, phosphoric acid-buffered physiological saline, or the like. Further, the solution may be immersed in a solution for soft contact lens containing physiological saline. From the point of hydration, the osmotic pressure of the physiological saline is preferably 250-400 mOms/kg.
The contact lens of the present invention has good hydrophilicity on the lens surface, is less likely to adhere dirt such as lipid, is easy to clean and remove even when adhering, and has excellent mechanical strength, and therefore can be used for about one month in a normal use form as required. Of course, it may be replaced in a period shorter than one month.
Examples
The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples and comparative examples. First, the components used in examples and comparative examples are shown below.
(A) Component (methacrylic acid ester monomer containing phosphorylcholine group)
MPC: (2-methacryloyloxyethyl) phosphorylcholine
(B) Component (hydroxyl group-containing monomer)
HEA: 2-Hydroxyethyl acrylate
HEMA: 2-Hydroxyethyl methacrylate
HPMA 2-hydroxypropyl methacrylate (2-hydroxypropyl ester, 2-hydroxy-1-methylethyl ester mixture, NIPPON SHOKUBAI CO., &lTtT transfer = L "&gTt L &lTt/T &gTt TD. manufactured)
HBMA 2-hydroxybutyl methacrylate (2-hydroxybutyl ester, 2-hydroxy-1-ethyl ester mixture, Sigma-Aldrich Co. LL C.)
HPA 2-hydroxypropyl acrylate (2-hydroxypropyl ester, 2-hydroxy-1-methylethyl ester mixture, manufactured by Tokyo chemical Industry Co., L td.)
HBA: acrylic acid 4-hydroxybutyl ester
HEAA: hydroxyethyl acrylamide
EMVE: ethylene glycol monovinyl ether
DEFV: diethylene glycol monovinyl ether
(C) Ingredient (siloxane group-containing itaconic acid diester monomer)
ES: a compound of formula (2) as the esterification reaction product of monoethylene glycol itaconate with 3-iodopropyl [ tris (trimethylsiloxy) ] silane
(D) Component (siloxane group-containing methacrylate)
FM-0711: a compound (R) represented by the formula (3)1Methyl, m 0, n 11, Mn 1000, and the number average molecular weight Mn
(E) Component (crosslinking agent)
TEGDV: triethylene glycol divinyl ether
DEGDV: diethylene glycol divinyl ether
EGDV: ethylene glycol divinyl ether
VEEA: 2- (2-ethyleneoxyethoxy) acrylic acid ethyl ester
FM-7711: a compound represented by formula (5) (p ═ r ═ 0, number average molecular weight Mn ═ 1,000)
FM-7721: a compound represented by formula (5) (p ═ r ═ 0, number average molecular weight Mn ═ 5,000)
TEGDMA: tetraethyleneglycol divinyl ether
(F) Component (monomers other than the components (A) to (E))
NVP: n-vinyl pyrrolidone
DMAA: n, N-dimethylacrylamide
NIPA: n-isopropyl acrylamide
VMA: N-vinyl-N-methylacetamide
VFA: n-vinyl formamide
MA: methacrylic acid
MMA: methacrylic acid methyl ester
Solvent(s)
EtOH: ethanol
NPA: 1-propanol (n-propanol)
IPA: 2-propanol (isopropanol)
Polymerization initiator
AIBN: 2, 2' -azobis (isobutyronitrile) (10 h half-life temperature 65 ℃ C.)
ADVN: 2, 2' -azobis (2, 4-dimethylvaleronitrile) (10 hour half-life temperature 51 ℃ C.)
The compositions, polymers and contact lenses of examples and comparative examples were evaluated for the following items. Hereinafter, the "composition", "polymer" and "contact lens" in each evaluation item and each table include not only the "composition", "polymer" and "contact lens" in each example but also the "composition", "polymer" and "contact lens" in comparative examples.
Homogeneity and transparency of the composition
The composition was placed in a colorless transparent container, and the state of the composition was evaluated visually according to the following criteria.
○ even and transparent
× white turbidity or precipitate
Morphology of the Polymer
The morphology of the polymer was visually evaluated according to the following criteria.
○ solid
× liquid (including viscous liquid)
Transparency of the Polymer
The transparency of the polymer was evaluated visually according to the following criteria.
○ transparent
△ slight turbidity
× white turbidity
Transparency of contact lenses
After purifying the polymer, the polymer was immersed in physiological saline described in ISO-18369-3 to swell the polymer, to obtain a hydrogel (contact lens), and the transparency of the hydrogel (contact lens) was visually evaluated according to the following criteria.
○ transparent
△ slight turbidity
× white turbidity
Surface hydrophilicity of contact lens (WBUT)
The surface hydrophilicity of the contact lenses was evaluated by WBUT (water film break up time). Specifically, the contact lens was immersed in ISO normal saline overnight, and the outer peripheral portion was pulled out from the water surface with tweezers, and the time (water film retention time) from pulling out from the water surface until the water film on the lens surface disappeared was measured. The state of disappearance of the water film was judged by naked eyes. The measurement was performed 3 times, the average value was obtained, and it was judged that the surface hydrophilicity was good when 30 seconds or more.
Water content of contact lens
The water content was measured by the method described in ISO-18369-4.
Mechanical strength of contact lenses
The modulus [ MPa ] of the contact lens was measured in accordance with JIS-K7127 using a breaking strength analysis apparatus BAS-3305(W) manufactured by yamaden co., ltd. Specifically, a sample obtained by cutting a contact lens into pieces having a width of 2mm was used, and the pieces were stretched at a rate of 1 mm/sec with a distance of 6mm between clamps (clamps) using a load cell of 200gf, to measure the modulus. The mechanical strength was judged to be good when the modulus was 0.2MPa or more and less than 0.7 MPa.
Oxygen permeability of contact lenses
The oxygen permeability coefficient of a sample in which 2 to 4 contact lenses were superimposed was measured by a measurement method based on the polarography described in ISO 18369-4. In the assay, O of Createch/Rehder-dev Co2PermeeterModel 201T. The thickness of the lens was plotted on the x-axis and the t/Dk value obtained by the measurement was plotted on the y-axis, and the reciprocal of the gradient of the regression line was taken as the oxygen permeability coefficient. The larger the oxygen permeability coefficient, the better the oxygen permeability.
Surface lubricity of contact lenses
The lubricity was evaluated by sensory evaluation of fingertips. Polymacon and omafilcon a were used as standard contact lenses for evaluation. The lubricity of polymacon was evaluated in 10 stages of 1 to 10, with the lubricity of omafilcon being 2 and the lubricity of omafilcon a being 8. The surface lubricity was judged to be good when the evaluation score was 6 points or more, and poor when the evaluation score was 5 points or less.
Example 1
0.5g (5.0 mass%) of MPC, 1.0g (10.0 mass%) of HEA, 4.0g (40.0 mass%) of ES and 0.5g (5 parts by mass) of EtOH were mixed in a vessel and stirred at room temperature until MPC was dissolved. Further, 1.9g (19.0 mass%) of FM-0711, 0.1g (1.0 mass%) of TEGDV, 2.5g (25.0 mass%) of NVP, and 0.05g (0.5 part by mass) of AIBN were added to a vessel and stirred at room temperature until homogeneous to obtain a composition. The above evaluation was performed on this composition.
0.3g of the composition was poured into a 25mm × 70mm × 0.2.2 mm cell (cell) sandwiched between two polypropylene plates with a polyethylene terephthalate sheet having a thickness of 0.1mm as a spacer (spacer), and the cell was placed in an oven, after which the inside of the oven was replaced with nitrogen, the temperature was raised to 65 ℃ and maintained at the temperature for 3 hours, then further raised to 120 ℃ and maintained for 2 hours to polymerize the composition, thereby obtaining a polymer, and the polymer was taken out of the cell to perform the above evaluation.
The polymer was immersed in 40g of 2-propanol for 4 hours, and then immersed in 50g of ion-exchanged water for 4 hours to remove unreacted substances and the like, thereby purifying the polymer. The polymer was further immersed in physiological saline described in ISO-18369-3 to swell (hydrate) the polymer, thereby producing a contact lens. The contact lenses were processed into samples having a size and a shape suitable for each evaluation test, and each evaluation was performed. The blending ratio of each component in the composition, polymerization conditions, and evaluation results are shown in table 1.
Examples 2 to 27
Compositions, polymers and contact lenses of examples 2 to 27 were prepared and manufactured in the same manner as in example 1 except that the content ratios of the respective components and the polymerization conditions were changed as shown in tables 1 to 4, and evaluation tests were performed. The results are shown in tables 1 to 4.
Comparative example 1
1.98g (19.8 mass%) of HEA, 4.95g (49.5 mass%) of ES, and 0.5g (5 parts by mass) of EtOH were mixed in a vessel and stirred at room temperature. Further, 1.98g (19.8 mass%) of FM-0711, 0.1g (1.0 mass%) of TEGDV, 0.99g (9.9 mass%) of DMAA, and 0.1g (1.0 mass part) of AIBN were added to the vessel and stirred at room temperature until uniform, thereby obtaining the composition of comparative example 1. The above evaluation was performed on this composition.
0.3g of the composition into a 0.1mm polyethylene terephthalate sheet as a gasket and clamped between two polypropylene plates in 25mm × 70mm × 0.2mm pool, and placed in the oven, the oven with nitrogen replacement, heating to 65 degrees and maintained at the temperature for 3 hours, further heating to 120 degrees, maintained for 2 hours, the composition polymerization, to obtain comparative example 1 polymer, the polymer from the pool, the evaluation.
The polymer of comparative example 1 was immersed in 40g of 2-propanol for 4 hours, and then immersed in 50g of ion-exchanged water for 4 hours to remove unreacted substances and the like, thereby purifying the polymer. The polymer was further immersed in physiological saline described in ISO-18369-3 to swell (hydrate) the polymer, thereby producing a contact lens of comparative example 1. The contact lenses were processed into samples having a size and a shape suitable for each evaluation test, and each evaluation was performed. The blending ratio of each component in the composition of comparative example 1, the polymerization conditions, and the evaluation results are shown in table 5. In the evaluation of surface hydrophilicity, WBUT was 0 second, which is a poor result, and therefore, no other evaluation was performed.
Comparative examples 2 to 5
Compositions, polymers and contact lenses of comparative examples 2 to 5 were prepared and manufactured in the same manner as in comparative example 1, except that the content ratios of the respective components and the polymerization conditions were changed as shown in table 5, and evaluation tests were performed. The results are shown in Table 5. In comparative example 5, as in comparative example 1, WBUT was 0 seconds, which is a poor result, and therefore, evaluation was not performed except for this. In comparative examples 2 and 3, polymerization was not carried out because of unevenness in the composition. Therefore, the polymers and contact lenses of comparative examples 2 and 3 could not be produced and evaluated. The contact lens of comparative example 4 had good surface hydrophilicity, but had a mechanical strength of 0.9MPa and an oxygen permeability of 67, which were inferior to those of examples.
[ Table 1]
The additive amount of the components in the corresponding color 1(A) to (F): the content ratio of the total monomer components in the composition is 100% by mass
And 2, mixing amount of other components: the content ratio of the total monomer components in the composition is 100 parts by mass
Folding 3 contact lens
[ Table 2]
The additive amount of the components in the corresponding color 1(A) to (F): the content ratio of the total monomer components in the composition is 100% by mass
And 2, mixing amount of other components: the content ratio of the total monomer components in the composition is 100 parts by mass
Folding 3 contact lens
[ Table 3]
The additive amount of the components in the corresponding color 1(A) to (F): the content ratio of the total monomer components in the composition is 100% by mass
And 2, mixing amount of other components: the content ratio of the total monomer components in the composition is 100 parts by mass
Folding 3 contact lens
[ Table 4]
The additive amount of the components in the corresponding color 1(A) to (F): the content ratio of the total monomer components in the composition is 100% by mass
And 2, mixing amount of other components: the content ratio of the total monomer components in the composition is 100 parts by mass
Folding 3 contact lens
The crude phase is processed at 55 deg.C for 7 hr and at 75 deg.C for 5 hr
[ Table 5]
The additive amount of the components in the corresponding color 1(A) to (F): the content ratio of the total monomer components in the composition is 100% by mass
And 2, mixing amount of other components: the content ratio of the total monomer components in the composition is 100 parts by mass
Folding 3 contact lens
Claims (7)
1. A monomer composition for a contact lens, comprising a component A, a component B, a component C, a component D and a component E:
the component A is a phosphorylcholine group-containing methacrylate monomer represented by the following formula (1);
the component B is more than one hydroxyl-containing monomer selected from the group consisting of hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyethyl acrylamide, ethylene glycol monovinyl ether and diethylene glycol monovinyl ether;
the component C is an itaconic acid diester monomer containing a siloxane group represented by the following formula (2);
the component D is a siloxane group-containing (meth) acrylate represented by the following formula (3); and
the component E is a cross-linking agent,
the content of the component A is 5-20 mass%, the content of the component B is 5-25 mass%, the content of the component C is 30-70 mass%, the content of the component D is 5-40 mass%, and the content of the component E is 0.1-10 mass% based on 100 mass% of the total of all monomer components in the composition,
[ chemical formula 1]
[ chemical formula 2]
[ chemical formula 3]
In the formula (3), R1Is a hydrogen atom or a methyl group, m is 0 or 1, and n is 10 to 20.
2. The monomer composition for a contact lens according to claim 1, wherein,
the composition further comprises a component F: the content of the component F is 25% by mass or less based on 100% by mass of the total of all monomer components in the composition.
3. The monomer composition for a contact lens according to claim 1 or 2, wherein,
the composition further contains a solvent having a hydroxyl group, and the content of the solvent is 25 parts by mass or less based on 100 parts by mass of the total of all monomer components in the composition.
4. A polymer for a contact lens, which is formed from a polymer of the monomer composition for a contact lens according to any one of claims 1 to 3.
5. A method for producing the polymer for a contact lens according to claim 4, comprising:
a polymerization step 1 of adding a polymerization initiator to the monomer composition for a contact lens according to any one of claims 1 to 3, and maintaining the mixture at a temperature of 45 to 75 ℃ for 1 hour or more to carry out polymerization; and
and a polymerization step 2 in which the mixture is maintained at 90 to 140 ℃ for 1 hour or more after the polymerization step 1 to carry out polymerization.
6. A contact lens formed from a hydrate of the polymer for a contact lens of claim 4.
7. A method of manufacturing a contact lens, comprising:
mixing the polymer for a contact lens according to claim 4 with at least one solvent selected from the group consisting of water, methanol, ethanol, 1-propanol and 2-propanol, and immersing the polymer in the solvent at a temperature of 10 to 40 ℃ for 10 minutes to 5 hours to purify the polymer; and
and a step of immersing the purified polymer in physiological saline having an osmotic pressure of 250 to 400mOms/kg, and hydrating the polymer so that the water content of the obtained contact lens is 35 to 60 mass%.
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| EP3855241B1 (en) | 2018-09-18 | 2024-01-24 | NOF Corporation | Contact lens treatment solution |
| US11867875B2 (en) | 2018-09-25 | 2024-01-09 | Nof Corporation | Monomer composition for contact lenses, polymer for contact lenses, contact lens, and method of producing the contact lens |
| TWI690424B (en) * | 2018-10-29 | 2020-04-11 | 優你康光學股份有限公司 | Method for preparing contact lens with polymer multilayer film |
| US20220153884A1 (en) * | 2019-04-15 | 2022-05-19 | Nof Corporation | Phosphoryl-choline-group-containing vinyl monomer |
| JP7551059B2 (en) * | 2019-04-25 | 2024-09-17 | 日油株式会社 | Monomer composition for contact lenses, polymer for contact lenses and method for producing same, and contact lenses and method for producing same |
| US11609438B2 (en) * | 2019-10-31 | 2023-03-21 | Menicon Singapore Pte Ltd. | Ocular lens with friction control structures |
| WO2021187394A1 (en) * | 2020-03-19 | 2021-09-23 | 日油株式会社 | Monomer composition for contact lens and polymer for contact lens |
| KR20220158710A (en) * | 2020-03-26 | 2022-12-01 | 니치유 가부시키가이샤 | Inorganic particulate adsorption inhibitor for soft contact lenses |
| TW202248228A (en) | 2021-04-21 | 2022-12-16 | 日商日油股份有限公司 | Monomer composition for contact lenses, polymer of said monomer composition, contact lens, and method for producing said contact lens |
| WO2024058213A1 (en) * | 2022-09-15 | 2024-03-21 | 日油株式会社 | Monomer composition for contact lens, polymer for contact lens, and contact lens |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007197513A (en) * | 2006-01-24 | 2007-08-09 | Nof Corp | Transparent liquid composition and polymer |
| CN102348726A (en) * | 2009-03-09 | 2012-02-08 | 日油株式会社 | Silicone monomer |
| CN103224597A (en) * | 2013-03-28 | 2013-07-31 | 明基材料有限公司 | Contact lens material, contact lenses and method for manufacturing contact lenses |
| CN103360591A (en) * | 2013-06-25 | 2013-10-23 | 明基材料有限公司 | Fluorine-containing ether monomer, contact lens material and contact lens |
| CN103415802A (en) * | 2011-02-28 | 2013-11-27 | 库柏维景国际控股公司 | Wettable silicone hydrogel contact lenses |
| CN104602886A (en) * | 2013-07-02 | 2015-05-06 | Hoya株式会社 | Method for fabricating silicone-containing copolymer molded article having hydrophilic surface and silicone hydrogel contact lens having hydrophilic surface |
| JP5972090B2 (en) * | 2012-08-03 | 2016-08-17 | 信越化学工業株式会社 | Method for producing high purity (meth) acryl silicone compound |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2522516T3 (en) * | 2008-07-24 | 2014-11-14 | Thomas Dudley Limited | Tank drain device with movable siphon |
| WO2013024799A1 (en) * | 2011-08-17 | 2013-02-21 | 東レ株式会社 | Medical treatment device, composition for coating solution, and method for manufacturing medical treatment device |
| TW201718768A (en) * | 2015-10-30 | 2017-06-01 | 日油股份有限公司 | Medical contact lens for controlled release of drug |
| WO2017072739A1 (en) * | 2015-10-30 | 2017-05-04 | Teclite Industries Limited | A pre-formed insert body |
| US11021558B2 (en) * | 2016-08-05 | 2021-06-01 | Johnson & Johnson Vision Care, Inc. | Polymer compositions containing grafted polymeric networks and processes for their preparation and use |
-
2018
- 2018-01-15 WO PCT/JP2018/000765 patent/WO2018135421A1/en active Application Filing
- 2018-01-15 JP JP2018563306A patent/JP7014185B2/en active Active
- 2018-01-15 CN CN201880007012.3A patent/CN110199219B/en active Active
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007197513A (en) * | 2006-01-24 | 2007-08-09 | Nof Corp | Transparent liquid composition and polymer |
| CN102348726A (en) * | 2009-03-09 | 2012-02-08 | 日油株式会社 | Silicone monomer |
| CN103415802A (en) * | 2011-02-28 | 2013-11-27 | 库柏维景国际控股公司 | Wettable silicone hydrogel contact lenses |
| JP5972090B2 (en) * | 2012-08-03 | 2016-08-17 | 信越化学工業株式会社 | Method for producing high purity (meth) acryl silicone compound |
| CN103224597A (en) * | 2013-03-28 | 2013-07-31 | 明基材料有限公司 | Contact lens material, contact lenses and method for manufacturing contact lenses |
| CN103360591A (en) * | 2013-06-25 | 2013-10-23 | 明基材料有限公司 | Fluorine-containing ether monomer, contact lens material and contact lens |
| CN104602886A (en) * | 2013-07-02 | 2015-05-06 | Hoya株式会社 | Method for fabricating silicone-containing copolymer molded article having hydrophilic surface and silicone hydrogel contact lens having hydrophilic surface |
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