CN110199219A - Contact lenses monomer composition, contact lenses polymer and preparation method thereof and contact lenses and its manufacturing method - Google Patents
Contact lenses monomer composition, contact lenses polymer and preparation method thereof and contact lenses and its manufacturing method Download PDFInfo
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- CN110199219A CN110199219A CN201880007012.3A CN201880007012A CN110199219A CN 110199219 A CN110199219 A CN 110199219A CN 201880007012 A CN201880007012 A CN 201880007012A CN 110199219 A CN110199219 A CN 110199219A
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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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- Optics & Photonics (AREA)
- General Health & Medical Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Eyeglasses (AREA)
Abstract
The present invention provides a kind of useful contact lenses monomer composition in the contact lenses that there is excellent surface hydrophilicity, oxygen permeability, mechanical strength and wearing to feel for manufacture.Further provide for a kind of contact lenses polymer and contact lenses obtained by the composition.The composition contains: the methacrylate monomers of (A) base containing Phosphorylcholine of specific quantity；(B) the hydroxyl monomer selected from one or more of the group being made of (methyl) Hydroxyethyl Acrylate, (methyl) hydroxypropyl acrylate, (methyl) hydroxy butyl acrylate, hydroxyethyl acrylamide, ethylene glycol monovinyl ether and diethylene glycol monovinyl base ether；(C) two ester monomer of itaconic acid of silicone-containing base；(D) (methyl) acrylate of silicone-containing base；And (E) crosslinking agent.
Description
Technical field
The present invention relates to contact lenses monomer composition, the polymer of the composition and preparation method and by this
The contact lenses of the gas hydrate synthesis of polymer and its manufacturing method.
Background technique
The hydrogel contact lens of previous type are insufficient to the oxygen-supplying amount of cornea eye, the safety when long-time is worn
There are problems in property.As the contact lenses for solving the defect, improving safety, silicone hydrogel contact eye is had developed
Mirror.
It is difficult to make lens surface in hydrophilic problem however, silicone hydrogel contact lenses exist.In general, soft stealth
Glasses are manufactured by cast molding method, use polypropylene molding jig in the method more.Silicone water-setting is being manufactured using this method
When glue contact lenses, since polypropylene is hydrophobicity, behavior aggregate of the silicone monomer to be orientated in die surface.Cause
This forms silicone portion in lens surface, and the hydrophily on the surface is lower.When the hydrophily of lens surface is insufficient, there are rouge
A possibility that matter or protein etc. are adhered to, and the gonorrhoea or eye disease of eyeglass are caused.
Therefore, it is proposed to after preparing silicone hydrogel contact lenses, in the enterprising enforcement plasma gas of lens surface
Or coating or the use hydrophilic monomer formation surface grafting polymerization object of hydrophilic polymer.However, these surface treatments need
Many devices, process is tedious, therefore is not expected in batch production.
For the purpose of the hydrophobicity on surface for improving Soft contact lens of the use containing silicone copolymer, a kind of incite somebody to action is proposed
N, N- dimethylacrylamide, n-vinyl-2-pyrrolidone, N- methyl-Nvinylacetamide, n-vinyl pyrrolidone
Deng the hydrophilic monomer with vinyl for the method in monomer composition.However, even if using such hydrophilic monomer,
The hydrophily of lens surface also be cannot say for sure sufficiently.
A kind of method for manufacturing eyeglass with composition by silicon hydrogel, the silicon hydrogel are disclosed in patent document 1
Contained with composition: the silicone monomer with (methyl) acryloyl group, the hydrophilic monomer with vinyl, cross-linkable monomer and
The polymerization initiator that 10 hours half life temperatures are 70 DEG C~100 DEG C.This method with the difference using the polymerism of starting monomer come
For the purpose of the hydrophily for improving lens surface, but still it cannot get satisfactory hydrophily.
A kind of contact lenses monomer composition is disclosed in patent document 2, contains (methyl) of the base containing Phosphorylcholine
Acrylate monomer, (methyl) acrylate silicone monomer and crosslinking agent with hydroxyl.A kind of silicon is disclosed in patent document 3
Ketone hydrogel contact lens, by big containing 2- methylacryoyloxyethyl Phosphorylcholine (MPC), Dimethylacryloyl silicone
Molecule monomer and bis- (trimethylsiloxy group) methyl-monosilanes (SiGMA) of (3- methacryloxy -2- hydroxy propyloxy group) propyl
Composition obtain.A kind of contact lenses are disclosed in patent document 4, by containing base containing Phosphorylcholine or carboxybetaine base
(methyl) acrylate monomer, (methyl) the acrylate silicone monomer with secondary hydroxyl, (methyl) without hydroxyl of group
The composition of acrylate cyclic silicone monomer, the maleic acid with fluorinated alkyl or dimethyl ester silicone monomer etc. obtains.
Although there are under oxygen permeability however, the contact lenses of patent document 2~4 are improved in the hydrophily of lens surface
The problem of drop.
A kind of composition is disclosed in patent document 5, contains (methyl) acrylate monomer, tool of the base containing Phosphorylcholine
There are (methyl) the acrylate silicone monomer and silicone (methyl) acrylate of hydroxyl, describing can utilize the polymer hidden
In shape glasses.A kind of composition is disclosed in patent document 6, contains the itaconic acid diester of the silicone-containing base with primary hydroxyl
Monomer and MPC, object can be polymerized by, which describing, utilizes in contact lenses.Patent document 5 and 6 lens surface hydrophily and
Good result has been obtained in terms of oxygen permeability.
Existing technical literature
Patent document
Patent document 1: International Publication No. 2015/001811
Patent document 2: Japanese Unexamined Patent Publication 2007-009060 bulletin
Patent document 3: Japanese Unexamined Patent Publication 2014-089477 bulletin
Patent document 4: Japanese Unexamined Patent Publication 2007-056220 bulletin
Patent document 5: Japanese Unexamined Patent Publication 2007-197513 bulletin
Patent document 6: International Publication No. 2010/104000
Summary of the invention
The technical problem to be solved in the present invention
Although however, the contact lenses of patent document 5 and 6 are good in terms of the hydrophily of lens surface and oxygen permeability,
It is that mechanical strength and wearing sense are insufficient, it is believed that it needs further improvement.
Technical problem of the invention is to provide a kind of contact lenses, even if using by the hydrophobic of the formation such as polypropylene
Property mold when being manufactured, also can express excellent surface hydrophilicity, oxygen permeability, mechanical strength and wear sense.In addition, " excellent
During different surface hydrophilicity " refers to that the WBUT (water film break up time) described in detail in embodiment is evaluated,
The characteristic that the moisture film retention time is 30 seconds or more.
Another technical problem of the invention is, provide a kind of composition that can be suitable for obtaining above-mentioned contact lenses and
Polymer.
Another technical problem of the invention is, provides a kind of for obtaining the manufacturer of above-mentioned polymer and contact lenses
Method.
Solve the technological means of technical problem
Present inventor is conscientiously studied, as a result, it has been found that, by using containing there are two types of hydrophilic monomer and two
The monomer composition of kind silicone-containing base silicone monomer can reach above-mentioned whole purposes as contact lenses raw material, thus
Complete the present invention.
According to embodiment of the present invention, a kind of contact lenses monomer composition is provided, wherein the composition contains
Have: the methacrylate monomers of the base containing Phosphorylcholine represented by (A) following formula (1)；(B) selected from by (methyl) acrylic acid hydroxyl
Base ethyl ester, (methyl) hydroxypropyl acrylate, (methyl) hydroxy butyl acrylate, hydroxyethyl acrylamide, ethylene glycol list ethylene
The hydroxyl monomer of one or more of the group of base ether and diethylene glycol monovinyl base ether composition；(C) represented by following formula (2)
Two ester monomer of itaconic acid of silicone-containing base；(D) (methyl) acrylate of silicone-containing base represented by following formula (3)；And
(E) crosslinking agent.Relative to total 100 mass % of monomer components whole in the composition, the content ratio of (A) ingredient is 5
~20 mass %, the content ratio of (B) ingredient are 5~25 mass %, and the content ratio of (C) ingredient is 30~70 mass %, (D)
The content ratio of ingredient is 5~40 mass %, and the content ratio of (E) ingredient is 0.1~10 mass %.
[chemical formula 1]
[chemical formula 2]
[chemical formula 3]
In formula (3), R1For hydrogen atom or methyl, m is 0 or 1, and n is 10~20.
Another embodiment according to the present invention is provided and is formed by the polymer of above-mentioned contact lenses monomer composition
Contact lenses polymer and preparation method thereof.
Another embodiment according to the present invention provides the stealth of the gas hydrate synthesis by above-mentioned contact lenses polymer
Glasses and its manufacturing method.
Invention effect
Contact lenses monomer composition of the invention contains (A)~(E) ingredient as an essential component.Therefore, this is used
It is strong that contact lenses of the invention obtained from the polymer of composition can express excellent surface hydrophilicity, oxygen permeability, machinery
Degree and wearing sense.In addition, the preparation method of contact lenses polymer according to the present invention and the manufacturing method of contact lenses, energy
Enough manufactures have the silicon hydrogel Soft contact lens of above-mentioned excellent properties.
Specific embodiment
Contact lenses monomer composition of the invention is uniform transparency liquid, contains (A) described hereinafter~(E)
Ingredient as an essential component, can further contain (F) ingredient as any ingredient.Contact lenses polymer of the invention is by this
The polymer of contact lenses monomer composition is formed, contact lenses of the invention by the contact lenses polymer hydrate
It is formed.Hereinafter, contact lenses of the invention are referred to as composition with monomer composition.In addition, by contact lenses of the invention
Polymer is referred to as with polymer.
(A) ingredient: the methacrylate monomers of the base containing Phosphorylcholine
(A) ingredient is the methacrylate monomers of the base containing Phosphorylcholine represented by following formula (1), specifically, being
2- methylacryoyloxyethyl Phosphorylcholine (MPC).By containing (A) ingredient, can make by the polymerization of composition of the invention
The hydrophily and lubricity on the surface of the contact lenses of object manufacture are good.
[chemical formula 4]
In the present compositions, when whole monomer components total is set as 100 mass %, (A) ingredient contains
Proportional is 5~20 mass %, preferably 8~20 mass %.If the content ratio of (A) ingredient is less than 5 mass %.Then it cannot get
Sufficient surface hydrophilicity.On the other hand, if more than 20 mass %, (A) ingredient is difficult to dissolve in the composition, and there are hidden
A possibility that mechanical strength decline of shape glasses.In addition, in the present invention, " monomer component " refers to (A)~(F) ingredient.
(B) ingredient: hydroxyl monomer
(B) ingredient is selected from by (methyl) Hydroxyethyl Acrylate, (methyl) hydroxypropyl acrylate, (methyl) acrylic acid
One of hydroxybutyl, hydroxyethyl acrylamide, ethylene glycol monovinyl ether and group of diethylene glycol monovinyl base ether composition
Above hydroxyl monomer.By containing (B) ingredient with specified amount, the dissolution of (A) ingredient in the present compositions becomes
Well.From the deliquescent point of (A) ingredient, the hydroxyl of (B) ingredient is preferably primary hydroxyl.In addition, in the present invention,
" (methyl) acrylate " refers to " acrylate and/or methacrylate ", " (methyl) acrylic acid " refer to " acrylic acid and/
Or methacrylic acid ".
As the specific example of (B) ingredient, can enumerate acrylic acid 2- hydroxy methacrylate, 2-hydroxyethyl methacrylate,
(methyl) acrylic acid 2- hydroxy propyl ester, (methyl) acrylic acid 4- hydroxybutyl, (methyl) acrylic acid 2- hydroxybutyl, polyethylene glycol
Monomethacrylates, N- (2- ethoxy) acrylamide, N- methyl-N- (2- ethoxy) acrylamide, ethylene glycol list ethylene
Base ether, diethylene glycol monovinyl base ether, 4- hydroxy butyl vinyl ether etc..(B) ingredient can be any one in these monomers,
Or two or more mixture.
From the more good point of the dissolubility of (A) ingredient, preferably 2-hydroxyethyl methacrylate, acrylic acid 2- hydroxyl
Ethyl ester, N- (2- ethoxy) acrylamide, N- methyl-N- (2- ethoxy) acrylamide, ethylene glycol monovinyl ether and diethyl
Monovinyl ether, particularly preferred acrylic acid 2- hydroxy methacrylate, N- (2- ethoxy) acrylamide, N- methyl-N- (2- hydroxyl second
Base) acrylamide and ethylene glycol monovinyl ether.
In the present compositions, when whole monomer components total is set as 100 mass %, (B) ingredient contains
Proportional is 5~25 mass %.If the content ratio of (B) ingredient is less than 5 mass %, there are compositions of the invention to be difficult into
A possibility that for homogeneous transparent liquid.On the other hand, if more than 25 mass %, there are the oxygen permeability of contact lenses decline can
It can property.
(C) ingredient: two ester monomer of itaconic acid of silicone-containing base
(C) ingredient is two ester monomer of itaconic acid of silicone-containing base represented by following formula (2).(C) ingredient helps to mention
The oxygen permeability and the transparency of high contact lenses.
[chemical formula 5]
The monomer of formula (2) can pass through the ester of itaconic acid monoethylene glycol ester and 3- iodine propyl [three (trimethylsiloxy group)] silane
Change reaction to obtain.Itaconic acid monoethylene glycol ester for example can be as recording, by making itaconic anhydride and second in patent document 6
Glycol reaction obtains.In addition, commercially available product can be used in 3- iodine propyl [three (trimethylsiloxy group)] silane, but in order to improve gained
The purity of the silicone monomer of the invention arrived is, it is preferable to use high-purity product.
In above-mentioned esterification, the by-product of constitutional isomer represented by following formula (2 ') is generated on a small quantity sometimes.
In the present invention, the monomer of formula (2) and the mixture of the monomer of a small amount of formula (2 ') can be used to be used as (C) ingredient.That is, in this hair
In bright, " two ester monomer of itaconic acid of silicone-containing base represented by formula (2) " does not only include the monomer of formula (2), and removes formula
It (2) also include the isomers of a part of formula (2 ') other than monomer.
[chemical formula 6]
In the present compositions, when whole monomer components total is set as 100 mass %, (C) ingredient contains
Proportional is 30~70 mass %, preferably 30~60 mass %.If the content ratio of (C) ingredient is deposited less than 30 mass %
A possibility that the dissolution of (A) ingredient in the present compositions becomes difficult, or there is the contact lenses polymer of manufacture
There is a possibility that gonorrhoea.On the other hand, if more than 70 mass %, there are the surface hydrophilicity of contact lenses it is insufficient can
It can property.
(D) ingredient: (methyl) acrylate of silicone-containing base
(D) ingredient is (methyl) acrylate of silicone-containing base represented by following formula (3).(D) ingredient helps to mention
The oxygen permeability and adjusting mechanical strength of high contact lenses.(D) ingredient can pass through side disclosed in Japanese Unexamined Patent Publication 2014-031338
Prepared by method etc., or commercially available product.
[chemical formula 7]
In formula (3), R1For hydrogen atom or methyl.M indicates the quantity of ethyleneoxy, is 0 or 1.N is dimethyl siloxane portion
The repeat number divided is 10~20.(D) ingredient can be the mixture of the different multiple compounds of repeat number n.At this point, n is that number is equal
Average value in molecular weight, in the range of 10~20.Less than 10 oxygen permeabilities of n decline, so not preferably.In addition, when n is greater than
When 20, the surface hydrophilicity or mechanical strength of contact lenses decline.
M in formula (3) is preferably 0.That is, (D) ingredient is preferably (methyl) of silicone-containing base represented by following formula (4)
Acrylate.In addition, the R in formula (4)1And the R in n and formula (3)1And n is identical.
[chemical formula 8]
In the present compositions, when whole monomer components total is set as 100 mass %, (D) ingredient contains
Proportional is 5~40 mass %.If the content ratio of (D) ingredient became less than 5 mass %, the mechanical strength of contact lenses
Greatly, there is a possibility that wearing sense is not excellent.On the other hand, if there are the surface hydrophilics of contact lenses more than 40 mass %
Property decline a possibility that.
In addition, in the present compositions, when whole monomer components total is set as 100 mass %, (C) ingredient
Total content ratio with (D) ingredient is preferably 40~75 mass %, more preferably 60~65 mass %.Contained by adding up to this
It is proportional to be set as 40 mass % or more, it is easy to get the composition of the invention for homogeneous transparent liquid.On the other hand, by setting
It is 75 mass % hereinafter, can prevent contact lenses from becoming really up to the mark.
(E) ingredient: crosslinking agent
(E) ingredient plays a role in the polymerization reaction of the monomer of (A)~(D) ingredient as crosslinking agent.(E) ingredient is logical
Often with there is 2 or more polymerism unsaturated groups.Since composition of the invention contains (E) ingredient of specified amount, this hair
Bright polymer has cross-linked structure, so contact lenses of the invention show excellent solvent resistance.
For example, (E) ingredient can be silicone dimethylacrylate represented by following formula (5).
[chemical formula 9]
In formula (5), p and r are mutually equal, are 0 or 1.Q indicates the repeat number of dimethylsiloxane portion, is 10~70.Formula
(5) the silicone dimethylacrylate represented by can be the mixture of the different multiple compounds of repeat number q.At this point, q is number
Average value in average molecular weight, from acquired angle, in the range of 10~70.
It can be enumerated other than the silicone dimethylacrylate of above-mentioned formula (5) as the specific example of (E) ingredient
Ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethyleneglycol divinylether, methylene-bisacrylamide, methyl-prop
Olefin(e) acid allyl ester, (2- allyloxy) ethyl methacrylate, 2- (2- vinyloxyethoxy) ethyl acrylate and 2- (2- second
Alkenyloxy group ethyoxyl) ethyl methacrylate etc..(E) ingredient can be any one in these crosslinking agents, or two
Kind or more mixture.
In the present compositions, when whole monomer components total is set as 100 mass %, (E) ingredient contains
Proportional is 0.1~10 mass %.If the content ratio of (E) ingredient is less than 0.1 mass %, under the solvent resistance of contact lenses
Drop.On the other hand, if more than 10 mass %, that there are contact lenses is crisp, generates a possibility that damaged, and there is also mechanical strong
Degree becomes a possibility that excessively high, contact lenses wearing senses are deteriorated.
(F) ingredient: the monomer in addition to (A)~(E) ingredient
(F) ingredient is the monomer in addition to (A)~(E) ingredient.(F) ingredient is any ingredient, can be to adjust stealthy eye
Carried out for the purpose of moisture content of mirror etc. using.
As (F) ingredient, the monomer that the functional group of amide groups, carboxyl and ester group is selected from more than one can be exemplified.
As the specific example of the monomer with amide groups, n-vinyl pyrrolidone, N- vinylpiperidine -2- ketone, N- can be enumerated
Vinyl-Epsilon-caprolactam, N- vinyl -3- methyl -2- caprolactam, N, N- dimethylacrylamide, N, N- diethyl third
Acrylamide, acrylamide, n-isopropyl acrylamide, acryloyl morpholine, N- vinyl-N-methylacetaniide, N- vinyl second
Amide, N- vinyl formamide etc..As the specific example of the monomer with carboxyl, (methyl) acrylic acid, amber can be enumerated
Sour single [2- [(2- methyl-acryloyl) oxygen] ethyl] ester etc..As the specific example of the monomer with ester group, can enumerate
(methyl) alkyl acrylate or the methoxies such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate
Base polyethylene glycol methacrylate-styrene polymer etc..(F) ingredient can be any one in these monomers, or two or more
Mixture.
In the case where composition of the invention contains (F) ingredient, the total of whole monomer components is being set as 100 matter
When measuring %, the content ratio of (F) ingredient is preferably 25 mass % or less.If 25 mass % hereinafter, then (A) ingredient is in composition
In favorable solubility, and the surface hydrophilicity of contact lenses is also good.
Other than above-mentioned (A)~(F) ingredient, composition of the invention can also contain solvent.As long as solvent can improve respectively
The dissolubility of ingredient in the composition is not particularly limited, it is however preferred to have the solvent of hydroxyl.By using with hydroxyl
Solvent, the solution rate of (A) ingredient in the present compositions are got higher, and dissolution becomes easy.
Solvent with hydroxyl can be alcohols or carboxylic acids.As the specific example of alcohols, ethyl alcohol, 1- third can be enumerated
Alcohol, 2- propyl alcohol, n-butyl alcohol, 2- butanol, the tert-butyl alcohol, 1- amylalcohol, 2- amylalcohol, 2- methyl -2- butanol, 1- hexanol, 1- octanol, the 1- last of the ten Heavenly stems
Alcohol, DODECANOL, 1- etc..As the specific example of carboxylic acids, glycolic, lactic acid, acetic acid etc. can be enumerated.The solvent can be
Any one in these solvents, or two or more mixtures.It is steady from the dissolubility of (A) ingredient and the pH of composition
Qualitatively point sets out, and the solvent selected from more than one of ethyl alcohol, 1- propyl alcohol and 2- propyl alcohol particularly preferably by forming.
In the case where composition of the invention contains solvent, it is set as by the total of monomer component whole in composition
When 100 mass parts, the content ratio of solvent is preferably 25 below the mass.Below the mass if 25, then the machine of contact lenses
Tool intensity is good.
Other than above-mentioned (A)~(F) ingredient, composition of the invention can also contain polymerization initiator.Polymerization initiator
It can be well known polymerization initiator, preferably thermal polymerization.If using thermal polymerization, based in polymerization process
Temperature change, the copolymerizable of each monomer component is easily varied.As the example of thermal polymerization, it is even that 2,2 '-can be enumerated
Nitrogen bis-isobutyronitrile, azo-bis-iso-dimethyl, 2,2 '-azos bis- [2- (2- imidazoline -2- base) propane] hydrochlorides, 2,2 ' -
Azo two (2,4- methyl pentane nitrile), 2,2 '-azo two [2- (2- imidazoline -2- base) propane] dithionate dihydrates, 2,
2 '-azo two (2- methyl-prop amidine) dihydrochlorides, 2,2 '-azo two [N- (2- carboxyethyl) -2- methyl-prop amidine] dihydrates, 2,
2 '-azos two [2- (2- imidazoline -2- base) propane], 2,2 '-azos two (1- imino group -1- pyrrolidinyl -2- methylpropane)
The bis- hydroxymethylhydroxyethyl propionamides of dihydrochloride, azo dimethyl N-, 2,2 '-azos [2- methyl-N- (2- hydroxyethyl) propionyl
Amine], 2,2 '-azo two (2- methyl-prop amidine) dihydrochlorides, 2,2 '-azos [2- methyl-N- (2- hydroxyethyl) propionamide] etc.
Azo type polymerization initiator or benzoyl peroxide, tert-butyl hydroperoxide, isopropyl benzene hydroperoxide, the double lauroyl of peroxidating,
T-butyl peroxy capronate (tert-butyl peroxy hexanoate), bis- (3,5,5- trimethyl acetyl) peroxide etc.
Peroxide type polymerization initiator etc..These polymerization initiators can be used alone, and also can be used in combination two or more.Wherein, from
Safety is set out with acquired point, preferably azo type polymerization initiator, even from reactive point, particularly preferred 2,2 '-
Nitrogen bis-isobutyronitrile, azo-bis-iso-dimethyl and 2,2 '-azos two (2,4- methyl pentane nitrile).
When monomer components whole in composition total is set as 100 mass parts, the amount of the polymerization initiator of addition is excellent
It is selected as 0.1~3 mass parts, more preferably 0.1~2 mass parts, particularly preferably 0.2~1 mass parts.Less than 0.1 mass parts
When, the polymerism of composition is insufficient, there is a possibility that the advantages of cannot blending polymerization initiator.More than 3 mass parts
When, in cleaning contact lenses polymer, manufacture contact lenses, there are the extraction of polymerization initiator decomposition product removals to become
A possibility that insufficient.
Other than above-mentioned (A)~(F) ingredient, in the range of not hindering the purpose of the present invention, composition of the invention
The additives such as polymerism ultraviolet absorbing agent, polymerism pigment (colorant) can also be contained.By blending ultraviolet absorbing agent, energy
The ultraviolet lights such as daylight are enough reduced to the burden of eyes.In addition, colorful contact lens can be made by blending pigment.
The preparation method of composition of the invention is not particularly limited, for example, can by by each ingredient with random order or one
And be added into stirring (mixing) device, with 10 DEG C~50 DEG C of temperature stirring (mixing) to uniform and prepare.Wherein, work as combination
When object contains polymerization initiator, needs to pay attention to the not initiated polymerization in mixing, preferably mixed at 40 DEG C or less.From making
(A) dissolubility of ingredient becomes good point and sets out, and preferably adds after these three ingredients of mixed dissolution (A), (B) and (C) ingredient
Adduction mixes other compositions.
Polymer of the invention is formed by the polymer of the composition of aforementioned present invention.Hereinafter, to polymer of the invention
Preparation method be illustrated.Preparation method as shown below is only to obtain an embodiment of the method for the polymer, this
The polymer of invention is not limited by preparation method acquisition.
By filling composition of the invention in a mold and carrying out polymerization reaction, polymerization of the invention can be prepared
Object.As the mold, the mold with hydrophobic surface by formation such as polypropylene can be used.
Polymerization reaction for example can by cooperate used in polymerization initiator decomposition temperature, with 45 DEG C~140 DEG C of temperature
Composition is maintained 1 hour or more a stage polymerization to carry out by degree, preferably by it is as shown below include polymerization process 1 and
The polymerization more than two stages of polymerization process 2 is implemented.At this point, the hydrophilic of the surface of contact lenses can be further increased
Property.After polymerization, such as 60 DEG C can be cooled to hereinafter, being removed from the molds polymer.
[polymerization process 1]
In polymerization process 1, above-mentioned polymerization initiator is added into composition as needed, with 45 DEG C~75 DEG C of temperature
Polymerization in progress 1 hour or more.
The polymerization temperature of polymerization process 1 is preferably 50 DEG C~70 DEG C, more preferably 55 DEG C~70 DEG C.If polymerization process 1
Polymerization temperature is 45 DEG C~75 DEG C, then can stably obtain the good polymer of the physical property such as surface hydrophilicity.
The polymerization time of polymerization process 1 is preferably 2 hours or more, 12 hours or less.If the polymerization time of polymerization process 1 is
1~12 hour, then it can effectively obtain the good polymer of the physical property such as surface hydrophilicity.
[polymerization process 2]
Polymerization process 2 is implemented after polymerization process 1, is polymerize with being higher than 90 DEG C~140 DEG C of temperature of polymerization process 1
Reaction.
The polymerization temperature of polymerization process 2 is preferably 100 DEG C~120 DEG C.If the polymerization temperature of polymerization process 2 be 90 DEG C~
140 DEG C, then the good polymer of the physical property such as surface hydrophilicity can be stably obtained, can effectively obtain polymer, and by
The mold of the formation such as polypropylene does not deform.
The polymerization time of polymerization process 2 is preferably 1 hour or more, 10 hours or less.If the polymerization time of polymerization process 2 is
1~10 hour, then it can effectively obtain the good polymer of the physical property such as surface hydrophilicity.
The atmosphere for carrying out polymerization process 1 and 2 is not particularly limited, from the point for improving aggregate rate, preferred polymeric process 1
And 2 carry out in the atmosphere of inert gases such as nitrogen or argon gas.At this point, can be passed through inert gas or this to composition makes mold
Composition, which fills place, becomes atmosphere of inert gases.
Pressure in mold can be atmospheric pressure~micro-positive pressure.When being polymerize in atmosphere of inert gases, with gauge pressure
(gauge pressure) meter, is preferably set to 1kgf/cm2Below.
Contact lenses of the invention are by the silicone hydrogel contact lenses of the gas hydrate synthesis of above-mentioned polymer.That is, logical
It crosses and polymer of the invention is hydrated, keep its aqueous and water-setting glue is made, to obtain contact lenses of the invention.Separately
Outside, in the present specification, " silicon hydrogel " refers to hydrogel in the polymer with silicone portion.Composition of the invention contains
Have as (C) and (D) ingredient containing silicone monomer, therefore its polymer has silicone portion, it, can by making it be hydrated (aqueous)
Form silicon hydrogel.
The moisture content (ratio of the water phase for contact lenses gross mass) of contact lenses is preferably 35 mass % or more, 60 matter
% is measured hereinafter, more preferably 35 mass % or more, 50 mass % or less.If moisture content be 35~60 mass %, can make with thoroughly
The balancing good of oxygen.
Then, the manufacturing method of contact lenses of the invention is illustrated.Manufacturing method as shown below is only to obtain
One embodiment of the method for contact lenses of the invention, contact lenses of the invention are not limited to obtain by the manufacturing method
It arrives.
After above-mentioned polymerization reaction, polymer be in sometimes for unreacted monomer ingredient (unreacted reactant), each ingredient
The state of the mixture of residue, by-product, residual solvent etc..Although can by such mixture directly for hydration-treated,
But it is preferred that before hydration-treated using purification with solvent come purifying polymer.
As purification solvent, water outlet, methanol, ethyl alcohol, 1- propyl alcohol, 2- propyl alcohol, mixture of these solvents etc. can be enumerated.
Purification can for example implement in the following manner: 10 DEG C~40 DEG C at a temperature of, polymer is impregnated 10 minutes in alcoholic solvent
It~5 hours, then impregnates 10 minutes~5 hours etc. in water.In addition, can be 20 in determining alcohol after being impregnated in alcoholic solvent
It impregnates 10 minutes~5 hours in the aqueous alcohol of~50 weight %, further impregnates in water.As water, preferably pure water, ion is handed over
Change water etc..
It is hydrated in physiological saline, in a manner of becoming defined moisture content by polymer impregnated, it can
Obtain contact lenses of the invention.Physiological saline can be borate buffer physiological saline, phosphate buffer normal saline etc..In addition,
It can also be immersed in the Soft contact lens conditioning liquid containing physiological saline.From the point of hydration, the infiltration of physiological saline
Pressure is preferably 250~400mOms/kg.
The hydrophily of the lens surface of contact lenses of the invention is good, is not easy to adhere to the dirts such as lipid, and even if
Also removal easy to clean, and mechanical strength when attachment, therefore one can be used under common use form according to demand
Month or so.Certainly it can also be replaced in a period of shorter than one month.
Embodiment
Hereinafter, by Examples and Comparative Examples, the present invention will be described in more detail, but the present invention is not by these realities
It applies example and comparative example limits.Firstly, ingredient used in Examples and Comparative Examples described below.
(A) ingredient (methacrylate monomers of the base containing Phosphorylcholine)
MPC:(2- methylacryoyloxyethyl) Phosphorylcholine
(B) ingredient (hydroxyl monomer)
HEA: acrylic acid 2- hydroxy methacrylate
HEMA: 2-hydroxyethyl methacrylate
HPMA: methacrylic acid 2- hydroxy propyl ester (2- hydroxy-propyl ester, 2- hydroxyl -1- Methylethyl ester admixture,
NIPPON SHOKUBAI CO., LTD. manufacture)
HBMA: methacrylic acid 2- hydroxybutyl (2- hydroxybutyl ester, 2- hydroxyl -1- ethyl diethyldithiocarbamate ester admixture,
Sigma-Aldrich Co.LLC. manufacture)
HPA: acrylic acid 2- hydroxy propyl ester (2- hydroxy-propyl ester, 2- hydroxyl -1- Methylethyl ester admixture, Tokyo
Chemical Industry Co., Ltd. manufacture)
HBA: acrylic acid 4- hydroxybutyl
HEAA: hydroxyethyl acrylamide
EMVE: ethylene glycol monovinyl ether
DEMVE: diethylene glycol monovinyl base ether
(C) ingredient (two ester monomer of itaconic acid of silicone-containing base)
ES: the esterification reaction product as itaconic acid monoethylene glycol ester and 3- iodine propyl [three (trimethylsiloxy group)] silane
Formula (2) compound
(D) ingredient (methacrylate of silicone-containing base)
FM-0711: compound (R represented by formula (3)1=methyl, m=0, n=11, number-average molecular weight Mn=is about 1000)
(E) ingredient (crosslinking agent)
TEGDV: triethyleneglycol divinylether
DEGDV: diethylene glycol divinyl ether
EGDV: ethylene glycol divinyl ether
VEEA:2- (2- vinyloxyethoxy) ethyl acrylate
FM-7711: compound represented by formula (5) (p=r=0, number-average molecular weight Mn=about 1,000)
FM-7721: compound represented by formula (5) (p=r=0, number-average molecular weight Mn=about 5,000)
TEGDMA: tetraethylene glycol divinyl ether
(F) ingredient (monomer in addition to (A)~(E) ingredient)
NVP:N- vinyl pyrrolidone
DMAA:N, N- dimethylacrylamide
NIPA:N- N-isopropylacrylamide
VMA:N- vinyl-N-methylacetaniide
VFA:N- vinyl formamide
MA: methacrylic acid
MMA: methyl methacrylate
Solvent
EtOH: ethyl alcohol
NPA:1- propyl alcohol (normal propyl alcohol)
IPA:2- propyl alcohol (isopropanol)
Polymerization initiator
AIBN:2,2 '-azo two (isobutyronitrile) (10 hours 65 DEG C of half life temperatures)
ADVN:2,2 '-azo two (2,4- methyl pentane nitrile) (10 hours 51 DEG C of half life temperatures)
For the composition, polymer and contact lenses of Examples and Comparative Examples, project below is evaluated.Hereinafter, respectively
" composition ", " polymer " and " contact lenses " in assessment item and each table not only include " composition " of each embodiment, " gather
Close object " and " contact lenses ", it also include " composition ", " polymer " and " contact lenses " of comparative example.
The uniformity and the transparency of composition
Composition is put into colorless and transparent container, according to standard below, by the state for being visually evaluated composition.
Zero: homogeneous transparent
×: there are gonorrhoea or precipitating
The form of polymer
According to standard below, by the form for being visually evaluated polymer.
Zero: solid
×: liquid (including thick liquid)
The transparency of polymer
According to standard below, by the transparency for being visually evaluated polymer.
Zero: transparent
△: micro- turbid
×: gonorrhoea
The transparency of contact lenses
After purifying to polymer, being immersed in the physiological saline recorded in ISO-18369-3 makes its swelling,
Hydrogel (contact lenses) are obtained, according to standard below, by the transparency for being visually evaluated hydrogel (contact lenses).
Zero: transparent
△: micro- turbid
×: gonorrhoea
The surface hydrophilicity (WBUT) of contact lenses
The surface hydrophilicity of contact lenses is evaluated by WBUT (water film break up time).Specifically,
Contact lenses are immersed in ISO physiological saline overnight, peripheral part is clamped with tweezers and is pulled out from the water surface, measurement from the water surface pull out to
Time (moisture film retention time) until the moisture film disappearance of lens surface.The state that moisture film disappears is determined by naked eyes.It carries out 3 times
The measurement finds out its average value, and 30 seconds or more situations are determined as that surface hydrophilicity is good.
The moisture content of contact lenses
Moisture content is measured by the method recorded in ISO-18369-4.
The mechanical strength of contact lenses
Using yamaden co., BAS-3305 (W) breaking strength resolver of ltd. manufacture is surveyed according to JIS-K7127
Determine the modulus [MPa] of contact lenses, evaluates mechanical strength.Specifically, using the sample that contact lenses are cut into wide 2mm,
Using the load sensor of 200gf, the interval fixture (clamps) is set as 6mm and with 1mm/ seconds speed tensiles, measurement modulus.
Modulus is determined as that mechanical strength is good more than and less than the case where 0.7MPa for 0.2MPa.
The oxygen permeability of contact lenses
According to the measuring method based on the polarography recorded in ISO 18369-4,2~4 contact lenses are overlapped by measurement
Made of sample oxygen permeability coefficient.In the assay, using the O of Createch/Rehder-dev Co.2Permeometer
Model 201T.Using drawing with a thickness of x-axis, using the t/Dk value found out by measurement as y-axis for eyeglass, by the oblique of the tropic
The inverse of rate is as oxygen permeability coefficient.Oxygen permeability coefficient is bigger, then oxygen permeability is the better.
The surface lubrication of contact lenses
By the sensory evaluation of finger tip, lubricity is evaluated.Use polymacon and omafilcon A as evaluation
Standard contact lens.The lubricity of polymacon is set as 2, the lubricity of omafilcon A is set as 8, with the 10 of 1~10
A stage is evaluated.The situation that evaluation is scored at 6 points or more is determined as that surface lubrication is good, 5 points or less of situation is sentenced
It is bad to be set to surface lubrication.
Embodiment 1
By the ES of HEA, 4.0g (40.0 mass %) of MPC, 1.0g (10.0 mass %) of 0.5g (5.0 mass %) and
The EtOH of 0.5g (5 mass parts) is mixed in a reservoir, is stirred at room temperature to MPC and is dissolved.Further, 1.9g is added into container
The NVP and 0.05g (0.5 of TEGDV, 2.5g (25.0 mass %) of FM-0711, the 0.1g (1.0 mass %) of (19.0 mass %)
Mass parts) AIBN, be stirred at room temperature to uniform, obtain composition.Above-mentioned evaluation is carried out to the composition.
The above-mentioned composition of 0.3g is injected into using the polyethylene terephthalate piece with a thickness of 0.1mm as gasket
(spacer) it is clamped in the pond 25mm × 70mm × 0.2mm (cell) between two panels polypropylene board Nei, and is placed on baking oven
It is interior.After carrying out nitrogen displacement in baking oven, after being warming up to 65 DEG C and maintaining 3 hours at such a temperature, further heat up to 120
DEG C, it maintains 2 hours, polymerize composition, obtain polymer.Polymer is taken out from pond, carries out above-mentioned evaluation.
After above-mentioned polymer is impregnated 4 hours in the 2- propyl alcohol of 40g, impregnated 4 hours in the ion exchange water of 50g,
Unreacted reactant etc. is removed, is purified.Further by the polymer impregnated physiological saline recorded in ISO-18369-3, make
It is swollen (hydration), and contact lenses are made.The contact lenses are processed into the sample for being suitble to the size and shape of each evaluation test,
Carry out each evaluation.By the mix proportions of each ingredient in composition, polymerizing condition and respectively evaluation result is shown in table 1.
Embodiment 2~27
Other than being changed to shown in table 1~4 by the content ratio of each ingredient and polymerizing condition, with same as Example 1
Mode prepare/manufacture the composition, polymer and contact lenses of embodiment 2~27, carry out evaluation test.Show the result in table
1~4.
Comparative example 1
The EtOH of the ES and 0.5g (5 mass parts) of HEA, 4.95g (49.5 mass %) of 1.98g (19.8 mass %) are existed
It mixes, is stirred at room temperature in container.Further, FM-0711, the 0.1g of 1.98g (19.8 mass %) are added into container
The AIBN of the DMAA and 0.1g (1.0 mass parts) of TEGDV, the 0.99g (9.9 mass %) of (1.0 mass %), are stirred at room temperature
To uniform, the composition of comparative example 1 is obtained.Above-mentioned evaluation is carried out to the composition.
The above-mentioned composition of 0.3g is injected into using the polyethylene terephthalate piece with a thickness of 0.1mm as gasket and
It is clamped in the pond 25mm × 70mm between two panels polypropylene board × 0.2mm, and is placed in baking oven.To carrying out nitrogen in baking oven
After gas displacement, after being warming up to 65 DEG C and maintaining 3 hours at such a temperature, further heats up to 120 DEG C, maintain 2 hours, make to combine
Object polymerization, obtains the polymer of comparative example 1.Polymer is taken out from pond, carries out above-mentioned evaluation.
After the polymer of comparative example 1 is impregnated 4 hours in the 2- propyl alcohol of 40g, 4 are impregnated in the ion exchange water of 50g
Hour, removal unreacted reactant etc. is purified.Further by the polymer impregnated physiological saline recorded in ISO-18369-3
In, so that it is swollen (hydration), the contact lenses of comparative example 1 are made.The contact lenses are processed into the ruler for being suitble to each evaluation test
Very little and shape sample, carries out each evaluation.By the mix proportions of each ingredient in the composition of comparative example 1, polymerizing condition and each
Evaluation result is shown in table 5.In the evaluation of surface hydrophilicity, since WBUT is 0 second, is poor outcome, it is not carried out except this
Except evaluation.
Comparative example 2~5
Other than being changed to the content ratio of each ingredient and polymerizing condition as shown in table 5, with identical with comparative example 1
Mode prepares/manufactures the composition, polymer and contact lenses of comparative example 2~5, carries out evaluation test.Show the result in table 5.
Comparative example 5 is identical as comparative example 1, and since WBUT is 0 second, is poor outcome, evaluation in addition to this is not carried out.Comparing
In example 2 and 3, due to composition unevenness, polymerization is not carried out.Therefore, it is impossible to prepare/manufacture comparative example 2 and 3 polymer and
Contact lenses, evaluation can not also be implemented.Although the surface hydrophilicity of the contact lenses of comparative example 4 is good, mechanical strength is
0.9MPa, oxygen permeability 67 are poor compared with embodiment.
[table 1]
※ 1 (A)~(F) ingredient blended amount: add up to containing for 100 mass % relative to monomer components whole in composition
Ratio
2 other compositions blended amount of ※: the content ratio of total 100 mass parts relative to monomer components whole in composition
3 contact lenses of ※
[table 2]
※ 1 (A)~(F) ingredient blended amount: add up to containing for 100 mass % relative to monomer components whole in composition
Ratio
2 other compositions blended amount of ※: the content ratio of total 100 mass parts relative to monomer components whole in composition
3 contact lenses of ※
[table 3]
※ 1 (A)~(F) ingredient blended amount: add up to containing for 100 mass % relative to monomer components whole in composition
Ratio
2 other compositions blended amount of ※: the content ratio of total 100 mass parts relative to monomer components whole in composition
3 contact lenses of ※
[table 4]
※ 1 (A)~(F) ingredient blended amount: add up to containing for 100 mass % relative to monomer components whole in composition
Ratio
2 other compositions blended amount of ※: the content ratio of total 100 mass parts relative to monomer components whole in composition
3 contact lenses of ※
After ※ 4 is carried out 7 hours with 55 DEG C, carried out 5 hours with 75 DEG C
[table 5]
※ 1 (A)~(F) ingredient blended amount: add up to containing for 100 mass % relative to monomer components whole in composition
Ratio
2 other compositions blended amount of ※: the content ratio of total 100 mass parts relative to monomer components whole in composition
3 contact lenses of ※
Claims (7)
1. a kind of contact lenses monomer composition, wherein the composition contains:
(A) methacrylate monomers of the base containing Phosphorylcholine represented by following formula (1)；
(B) selected from by (methyl) Hydroxyethyl Acrylate, (methyl) hydroxypropyl acrylate, (methyl) hydroxy butyl acrylate,
One or more of the group of hydroxyethyl acrylamide, ethylene glycol monovinyl ether and diethylene glycol monovinyl base ether composition contains hydroxyl
Base monomer；
(C) two ester monomer of itaconic acid of silicone-containing base represented by following formula (2)；
(D) (methyl) acrylate of silicone-containing base represented by following formula (3)；And
(E) crosslinking agent,
Relative to total 100 mass % of monomer components whole in the composition, the content ratio of (A) ingredient is 5~20 matter
% is measured, the content ratio of (B) ingredient is 5~25 mass %, and the content ratio of (C) ingredient is 30~70 mass %, (D) ingredient
Content ratio is 5~40 mass %, and the content ratio of (E) ingredient is 0.1~10 mass %,
[chemical formula 1]
[chemical formula 2]
[chemical formula 3]
In formula (3), R1For hydrogen atom or methyl, m is 0 or 1, and n is 10~20.
2. contact lenses monomer composition according to claim 1, wherein
The composition further contains the monomer of (F) in addition to (A)~(E) ingredient, relative to complete in the composition
Total 100 mass % of portion's monomer component, the content ratio of (F) ingredient are 25 mass % or less.
3. contact lenses monomer composition according to claim 1 or 2, wherein
The composition further contains the solvent with hydroxyl, relative to the total of monomer components whole in the composition
100 mass parts, the content ratio of the solvent are 25 below the mass.
4. a kind of contact lenses polymer, by contact lenses monomer composition according to any one of claims 1 to 3
Polymer formed.
5. a kind of preparation method of contact lenses polymer is the system of contact lenses polymer as claimed in claim 4
Preparation Method comprising:
It is with 45 DEG C~75 DEG C of temperature that contact lenses according to any one of claims 1 to 3 are small with monomer composition maintenance 1
When more than, the polymerization process 1 that is polymerize；And
After the polymerization process 1, maintained 1 hour with 90 DEG C~140 DEG C of temperature or more, the polymerization process 2 being polymerize.
6. a kind of contact lenses, by the gas hydrate synthesis of contact lenses polymer as claimed in claim 4.
7. a kind of manufacturing method of contact lenses, includes
Hybrid right contact lenses polymer and selects Free water, methanol, ethyl alcohol, 1- propyl alcohol and 2- propyl alcohol group described in requiring 4
At one or more of group solvent, the process that the polymer is purified；And
Will be described polymer impregnated in physiological saline, the process for being hydrated it.
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| JP2017005765 | 2017-01-17 | ||
| PCT/JP2018/000765 WO2018135421A1 (en) | 2017-01-17 | 2018-01-15 | Contact lens monomer composition, contact lens polymer and method for manufacturing same, and contact lens and method for manufacturing same |
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| CN115315657A (en) * | 2020-03-26 | 2022-11-08 | 日油株式会社 | Inorganic microparticle adsorption inhibitor for soft contact lens |
| 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 |
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| SG11202102294TA (en) * | 2018-09-14 | 2021-04-29 | Nof Corp | Monomer composition for contact lens, polymer thereof, contact lens, and production method thereof |
| EP3855241B1 (en) * | 2018-09-18 | 2024-01-24 | NOF Corporation | Contact lens treatment solution |
| 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 |
| WO2020213524A1 (en) * | 2019-04-15 | 2020-10-22 | 日油株式会社 | Phosphoryl-choline-group-containing vinyl monomer |
| SG11202111751QA (en) * | 2019-04-25 | 2021-11-29 | Nof Corp | Monomer composition for contact lenses, polymer for contact lenses and method for producing same, and contact lens and method for producing same |
| US11609438B2 (en) * | 2019-10-31 | 2023-03-21 | Menicon Singapore Pte Ltd. | Ocular lens with friction control structures |
| TW202140584A (en) * | 2020-03-19 | 2021-11-01 | 日商日油股份有限公司 | Monomer composition for contact lens and polymer for contact lens |
| JPWO2022224790A1 (en) | 2021-04-21 | 2022-10-27 | ||
| 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 |
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| TW201827892A (en) | 2018-08-01 |
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| WO2018135421A1 (en) | 2018-07-26 |
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