WO1999056167A1 - Production de lentille oculaire - Google Patents

Production de lentille oculaire Download PDF

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Publication number
WO1999056167A1
WO1999056167A1 PCT/JP1999/002216 JP9902216W WO9956167A1 WO 1999056167 A1 WO1999056167 A1 WO 1999056167A1 JP 9902216 W JP9902216 W JP 9902216W WO 9956167 A1 WO9956167 A1 WO 9956167A1
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WIPO (PCT)
Prior art keywords
group
ophthalmic lens
producing
lens according
acid
Prior art date
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PCT/JP1999/002216
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English (en)
Japanese (ja)
Inventor
Naoki Shimoyama
Masataka Nakamura
Yoshihiro Kawabe
Nobuo Saito
Mitsuru Yokota
Original Assignee
Toray Industries, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Priority claimed from JP11861198A external-priority patent/JP3937576B2/ja
Priority claimed from JP11861098A external-priority patent/JP3941217B2/ja
Application filed by Toray Industries, Inc. filed Critical Toray Industries, Inc.
Publication of WO1999056167A1 publication Critical patent/WO1999056167A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041—Lenses
    • G02B1/043—Contact lenses

Definitions

  • the present invention relates to a method for producing a polymer for an ophthalmic lens suitably used for an ophthalmic lens such as a contact lens, an intraocular lens, and an artificial cornea.
  • an ophthalmic lens such as a contact lens, an intraocular lens, and an artificial cornea.
  • polymers for ophthalmic lenses having high oxygen permeability such as tris (trimethylsiloxy) silylpropyl methacrylate, and a polymer containing siloxanyl group-containing methacrylate and modified polysiloxane as one component have been developed. (USP 4, 594, 401 and USP 4, 260, 725).
  • polymers composed of these monomers or macromers have poor water wettability on the surface due to the effects of siloxanyl 'groups or polysiloxane components introduced for the purpose of improving oxygen permeability, and polymers for ophthalmic lenses. was not a good thing.
  • An object of the present invention is to solve the above-mentioned drawbacks of the prior art, and it is an object of the present invention to provide a method for producing an ophthalmic lens polymer having high oxygen permeability and excellent surface wettability. Aim. The purpose is to provide.
  • the method for producing an ophthalmic lens according to the present invention comprises an ophthalmic lens comprising a polymer represented by the following general formula (1) and comprising a compound having an amino group and an organosiloxane group as an essential component:
  • An ophthalmic lens characterized by being subjected to an acid treatment, a plasma treatment in an atmosphere of one or more types of gas containing hydrogen, or a treatment for generating a hydrophilic group by deprotecting a protected hydrophilic group in a polymer. It is a manufacturing method of.
  • X is a group having a polymerizable double bond
  • R 1 is each independently a hydrogen atom, an alkyl group, an aryl group, an alkyl group having a substituent, an aryl group having a substituent, or a substituent.
  • m, ⁇ , and ⁇ are independently selected from 0 or 1
  • 'q is an integer from 0 to 10
  • 2 is a substituent containing an organosiloxane.
  • the general formula (1) satisfies one of the following conditions.
  • R ′ is other than a hydrogen atom or a methyl group.
  • the acid treatment in the present invention is a method characterized by contacting an ophthalmic lens with a 5% to 100% by weight of an inorganic acid solution, an organic acid solution or an organic acid solution. It is preferable that the ophthalmic lens manufactured as described above is treated under basic conditions, and is further preferably heated and hydrolyzed.
  • the acid treatment in the present invention includes the following preferred embodiments.
  • the concentration of the inorganic acid solution is from 30% by weight to 100% by weight.
  • the inorganic acid is an oxygen acid containing a sulfur atom, an oxygen acid containing a nitrogen atom, and a phosphorus source; Must be at least one selected from oxyacids containing offspring.
  • the inorganic acid is at least one selected from oxygen acids containing a sulfur atom.
  • the inorganic acid is sulfuric acid.
  • the contact time between the polymer and the inorganic acid is within 10 minutes.
  • the monomer having a siloxanyl group is a monomer represented by the following formula (a) or (b).
  • the organic acid solution is preferably an organic acid aqueous solution or an organic acid alcohol solution, and the organic acid is an organic carboxylic acid having 1 to 20 carbon atoms and a carbon number. It is preferable that at least one selected from 1 to 20 organic sulfonic acids is used.
  • the present invention further provides a method comprising performing a plasma treatment under one or more gaseous atmospheres containing hydrogen, and a treatment for deprotecting a protected hydrophilic group in a polymer to generate a hydrophilic group.
  • the method also includes a method characterized by: BEST MODE FOR CARRYING OUT THE INVENTION
  • BEST MODE FOR CARRYING OUT THE INVENTION BEST MODE FOR CARRYING OUT THE INVENTION
  • R is a hydrogen atom or a methyl group
  • R is preferably used because its double bond has high polymerizability or its copolymerization with other monomers is weak (Ph is phenyl).
  • R 1 is independently selected from a hydrogen atom, an alkyl group, an aryl group, an alkyl group having a substituent, an aryl group having a substituent, an ester group having a substituent, and an amide group having a substituent. Represents a substituent.
  • the alkyl group which may be substituted is not particularly limited, whether it is linear or branched, but preferably has 1 to 20 carbon atoms.
  • R 3 to R 5 are each independently selected from the group consisting of a hydrogen atom, an optionally substituted alkyl group and an optionally substituted aryl group. Represents a substituent. R 4 and R 5 may combine with each other to form a ring containing an N atom. ]
  • v represents an integer of 3 to 8.
  • the aryl group which may be substituted is not particularly limited, but preferably has 6 to 20 carbon atoms.
  • a 4-hydroxyphenyl group , 2-Hydroxyphenyl group and the like have a hydroxyl group and thus have high hydrophilicity, and have a phenyl group and may have a high elastic modulus.
  • R ′ may be a group containing a protected hydrophilic group.
  • the protected hydrophilic group refers to a hydrophilic group protected by a protecting group.
  • hydrophilic group examples include a carboxyl group, a sulfo group, a sulfino group, a sulfeno group, Examples thereof include a wood suphono group, a phosphinico group, a hydroxyl group, an amino group, a carbamoyl group, a sulfamoyl group, a sulfinamoyl group, a sulfenamoyl group, and a mercapto group.
  • more preferred hydrophilic groups for improving the water wettability of the surface are a carboxyl group, a sulfo group, a phosphono group, a hydroxyl group and an amino group.
  • Such a hydrophilic group need not be directly bonded to a carbon atom, but is bonded to a carbon atom through one or more hetero atoms such as an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom. May be.
  • the protective group for the hydrophilic group is not particularly limited as long as it can protect the hydrophilic group and can be deprotected under specific conditions.
  • R ′ is a group containing a protected hydrophilic group
  • specific examples of R ′ include groups represented by the following formulas (yz-1) to (yz—l9), but are not limited thereto. It is not something.
  • Z represents a protecting group.
  • V represents an integer of 3 to 8.
  • Numerous such protecting groups are known, for example, Protective Groups in Organic Synthes is ", Theodora W. Greene, Many examples are shown in A Wiley-liters Science Publication, and these protecting groups can be used in the present invention.
  • Z represents a protecting group, and preferable examples thereof include a protected state such as a tetrahydrobiranil group, a methoxymethyl group, a methoxyAethoxymethyl group, a benzyloxymethyl group, and a methylthiomethyl group.
  • alkyl groups such as methyl group, ethyl group, t-butyl group and adamantyl group; t-butoxycarbonyl group, adamantyloxycarbonyl group, benzyloxycarbonyl
  • An alkoxycarbonyl group such as a P-methoxybenzyloxycarbonyl group, a p-methoxybenzyloxycarbonyl group, a 9-fluorophenylenylcarbonyl group, or a 2- (phenylsulfonyl) ethoxycarbonyl group; Trimethylsilyl; formyl, acetyl, propionyl, benzoyl, bivaloyl, and other acyl groups; trimethylsilyl Group, triethylsilyl group, isopropyldimethylsilyl group, methyldiisopropylsilyl group, triiso
  • R 2 a substituent represented by the following general formula (4) is preferably used.
  • a and B independently represent a C 1, a C 5 -C 5 alkyl group which may be substituted, an aryl group which may be substituted, or a fluorinated alkyl group which may be substituted.
  • a and B include a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isopropyl group, a sec-butyl group, a t-butyl group, a hexyl group and a cycloalkyl group.
  • alkyl groups such as hexyl group, 2-ethylhexyl group and octyl group, and aryl groups such as phenyl group and naphthyl group.
  • i is an integer of 0 to 200, preferably 0 to 50, and more preferably 0 to 10.
  • the polymer for an ophthalmic lens applicable to the present invention can further contain another monomer as a copolymer component.
  • the copolymerization component in that case is not particularly limited as long as it is copolymerizable, and may be a (meth) acryloyl group, a styryl group, an aryl group, a vinyl group, and other copolymerizable carbon-carbon unsaturated bonds. It is possible to use a monomer having the following. Hereinafter, some examples will be given, but the present invention is not limited to these.
  • Alkyl (meth) acrylates such as methyl (meth) acrylate and ethyl (meth) acrylate, polyalkylene glycol mono (meth) acrylate, polyalkylene glycol mono Alkyl ether (meth) acrylate, polyalkylene glycol bis (meth) acrylate, trimethylolpropane tris (meth) acrylate, pentaerythritol tetrakis (meta) acrylate Polyfunctional (meth) acrylates such as siloxane macromers having a carbon-carbon unsaturated bond at both terminals, trifluroyl (meth) acrylate, hexafluoroisopropyl (meth) acrylate Alkyl (meth) acrylates, such as salts, tris (trimethylsiloxy) silyl Siloxanyl (meth) acrylates, such as ropyl (meth) acrylate and bis (trimethylethyl) methylsilyl
  • the polymer for an ophthalmic lens applicable to the present invention can also be obtained by copolymerizing a monomer having a protected hydrophilic group.
  • Suitable examples of such a monomer having a protected hydrophilic group include compounds represented by the following formulas (si) to (s31), but are not limited thereto.
  • the copolymerization ratio of the monomer having a protected hydrophilic group is preferably 1% by weight to 7% by weight. 0% by weight, more preferably 3% to 50% by weight, water; 'The higher the content, the better from the viewpoint of demand, but the lower the better, the better from the viewpoint of oxygen permeability.
  • the copolymerization ratio of the monomer having a siloxanyl group is preferably 30% by weight to 99% by weight, and more preferably 50% by weight to 9% by weight. 7% by weight.
  • the balance with water wettability is also important, so that it is most preferably 60% by weight to 95% by weight.
  • the polymer for an ophthalmic lens applicable to the present invention preferably contains as a copolymer component a monomer having two or more copolymerizable carbon-carbon unsaturated bonds in one molecule.
  • the surface of the polymer for an ophthalmic lens may be roughened and its transparency may be impaired, or the mechanical properties of the polymer for an ophthalmic lens may be degraded.
  • a copolymerization component a monomer having two or more copolymerizable carbon-carbon unsaturated bonds in the molecule, it is possible to reduce or prevent surface roughness and deterioration of mechanical properties.
  • a monomer having at least two copolymerizable carbon-carbon unsaturated bonds in one molecule should contain 0.5% by weight or more as a copolymer component.
  • the polymer for an ophthalmic lens applicable to the present invention may contain an ultraviolet absorbent, a dye, a coloring agent, and the like. Further, an ultraviolet absorber, a dye, and a colorant having a polymerizable group may be contained in a copolymerized form.
  • a polymerization method and a molding method of the polymer for ophthalmic lenses applicable to the present invention known methods can be used.
  • the polymer for an ophthalmic lens is once polymerized and molded into a round bar or a plate shape, and then processed into a desired shape by cutting or the like, a mold polymerization method, a spin cast polymerization method, or the like.
  • the acid treatment in the present invention is characterized in that an ophthalmic lens made of the above polymer is brought into contact with an inorganic acid solution, an organic acid or an organic acid solution of 5 to 100% by weight.
  • the inorganic acid that can be used in the present invention is not particularly limited, but oxygen acids containing a sulfur atom (for example, sulfuric acid, sulfurous acid, nitrous acid, etc.), oxygen containing a nitrogen atom, and the like in terms of obtaining a large reforming effect.
  • Acids eg, nitric acid, nitrous acid, hyponitrite, etc.
  • oxygen acids containing phosphorus atoms eg, phosphoric acid, diphosphoric acid, triphosphoric acid, polyphosphoric acid, metallic acid, diphosphorous acid
  • Acid, phosphorous acid, hypophosphorous acid, etc. among which oxyacids containing sulfur atoms are preferred, and sulfuric acid is most preferred.
  • organic acid that can be used in the present invention is not particularly limited. However, the organic acid having 1 to 20 carbon atoms and the organic acid having 1 to 2 carbon atoms are easily available and easily obtain a large modifying effect. Organic sulfonic acids of 0 are preferred.
  • Preferred examples of the organic carboxylic acid having 1 to 20 carbon atoms include various amino acids, formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid,
  • organic sulfonic acids having 20 to 20 carbon atoms include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and dodesulfonic acid. And silbenzene sulfonic acid.
  • Organic acids can be used as a mixture of two or more.
  • various organic solvents can be used as a solvent for the inorganic acid solution and as a solvent for the organic acid solution.
  • various alcohols such as water, methanol, ethanol, propanol, 2-propanol, butanol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, and glycerin , Benzene, toluene, xylene, etc., various aromatic hydrocarbons, hexane, heptane, octane, decane, petroleum ether, kerosene, lignin, paraffin, etc., aliphatic hydrocarbons, acetone, methyl Various ketones such as ethyl ketone and methyl isobutyl ketone; various esters such as ethyl acetate, butyl acetate, methyl benzoate and di-octyl phthalate; getyl ether; tetrahydrofuran; di-xan; ethylene glycol Recall dialkyl ether Various ethers such as di
  • Halogen solvents and chlorofluorocarbon solvents are most preferred as the solvent for the inorganic acid solution from the viewpoints of economy, simplicity of handling, and chemical stability.
  • water and various alcohols are preferred in that they do not reduce the mechanical properties of the polymer for ophthalmic lenses.
  • a mixture of two or more substances can be used as a solvent.
  • the concentration of the inorganic acid solution is from 5% by weight to 100% by weight, preferably from 30% by weight to 100% by weight, more preferably from 50% by weight to 100% by weight, in view of the magnitude of the modifying effect. 0% by weight is most preferred.
  • the concentration of the inorganic acid solution is 50% by weight to 100% by weight, a large modifying effect can be obtained even if the treatment time is as short as 10 minutes or less.
  • the concentration of the organic acid solution is preferably 0.1% by weight or more, more preferably 1% by weight or more, and most preferably 5% by weight or more from the viewpoint of the effect of the modification. If the concentration of the organic acid solution is less than 0.1% by weight, the resulting modifying effect is not sufficient, which is not preferable.
  • the inorganic acid solution used in the present invention may contain components other than the inorganic acid and the solvent. Particularly preferred as components other than the inorganic acid and the solvent are oxidizing agents such as hydrogen peroxide and reducing agents.
  • the organic acid or the organic acid solution used in the present invention may contain components other than the organic acid and the solvent. Particularly when a basic compound is contained, a large reforming effect may be obtained. In this case, it is preferable to use water or alcohols as a solvent from the viewpoint of solubility.
  • the basic compound include alkali metal hydroxides, alkaline earth metal hydroxides, various carbonates, various borates, various phosphates, ammonia, various ammonium salts, and various types of basic compounds. Examples include amines.
  • the method of bringing the ophthalmic lens into contact with an inorganic acid solution, an organic acid or an organic acid solution is not particularly limited.
  • the temperature at which the ophthalmic lens is brought into contact with an organic acid or an organic acid solution is not particularly limited, but is usually performed within a temperature range of about 150 ° C. to 300 ° C. Considering this, the temperature range is preferably from 10 ° C. to 150 ° C., and more preferably from 150 ° C. to 60 ° C.
  • the optimal time for contacting the ophthalmic lens with the inorganic acid solution varies depending on the concentration and temperature of the inorganic acid solution, but is generally preferably within 10 minutes, more preferably within 1 minute. If the contact time is too long, not only the workability and productivity may deteriorate, but also the surface of the ophthalmic lens may be roughened and the transparency may be impaired.
  • the optimal time for contacting the ophthalmic lens with an organic acid or an organic acid solution varies depending on the concentration and temperature of the organic acid or organic acid solution, but is generally within 100 hours. Is preferred, within 24 hours is more preferred, and within 12 hours is most preferred.
  • the ophthalmic lens is preferably brought into contact with an inorganic acid solution, an organic acid or an organic acid solution, and then the organic acid is removed by washing.
  • washing solvent Various inorganic and organic solvents can be used as the washing solvent.
  • various alcohols such as water, methanol, ethanol, propanol, 2-propanol, butanol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, glycerin, etc.
  • Aromatic hydrocarbons such as benzene, toluene, xylene, etc., hexane, heptane, octane, decane, petroleum ether, kerosene, lignin, paraffin, etc., acetone, methyle
  • ketones such as methyl ketone and methyl isobutyl ketone
  • esters such as ethyl acetate, butyl acetate, methyl benzoate, di-octyl phthalate, getyl ether, tetrahydrofuran, di-xane, ethylene glycol dialkyl
  • Various ethers such as ether, diethylene glycol dialkyl ether, triethylene glycol dialkyl ether, tetraethylene glycol dialkyl ether, polyethylene glycol dialkyl ether, dimethylformamide, dimethylacetamide N-methyl-2-pyrrolidone, dimethylimidazolidinone, hex
  • a mixture of two or more solvents can be used as the washing solvent.
  • the washing solvent may contain components other than the solvent, for example, inorganic salts, surfactants, and detergents.
  • the acid treatment of the present invention after the ophthalmic lens is brought into contact with an inorganic acid solution, an organic acid or an organic acid solution, it can be further treated under basic conditions. Further water wettability can be imparted by treating under basic conditions. Examples of the treatment under the basic conditions include a method of contacting an ophthalmic lens treated with an inorganic acid solution, an organic acid or an organic acid solution with a basic solution, and a method of contacting with a basic gas.
  • Can be The simplest method of obtaining a large modifying effect is to immerse the ophthalmic lens in a basic compound solution.
  • the basic compound include alkali metal hydroxides, alkaline earth metal hydroxides, various carbonates, various borates, various phosphates, ammonia, various ammonium salts, and various types of basic compounds. Amines and the like can be mentioned. Water and alcohol may be used as the solvent for the basic compound solution. Are preferred.
  • a pH buffer having a pH of more than 7 can also be preferably used.
  • the temperature at the time of the treatment under the basic condition is not particularly limited, but it is usually carried out within a temperature range of about ⁇ 50 ° C. to about 300 ° C. A temperature range of 150 ° C is more preferred, with a temperature of 150 ° C to 60 ° C being most preferred.
  • the treatment under such basic conditions may also serve as the treatment for removing the organic acid by the above-mentioned washing.
  • a pH buffer having a pH of 7 to 8 may be used as a preservation solution for the ophthalmic lens.
  • preservation in this preservation solution requires treatment under the above basic conditions. It can serve as both.
  • the treatment time under basic conditions is not particularly limited, but is generally preferably within 100 hours, more preferably within 50 hours. If the processing time is too long, the workability and the productivity are unfavorably deteriorated. However, as described above, this is not applied when the storage of the ophthalmic lens in the storage solution also serves as the treatment under the basic condition.
  • a further greater reforming effect can be obtained by further performing a heating water treatment.
  • the term “heated water treatment” means a treatment in which heated water molecules are brought into contact. Specifically, a method of immersing the ophthalmic lens in water to heat it, or a method of exposing the ophthalmic lens to heated steam can be applied.
  • the heating temperature in this case is selected from the range of 50 ° C to 300 ° C. If the heating temperature exceeds 100 ° C, the heating water treatment should be performed in a pressure vessel. In the case of the heating water treatment, about 1 minute to 24 hours is preferable, and about 10 minutes to 12 hours is more preferable.
  • the hydrophilicity (water wettability) of the ophthalmic lens can be effectively improved and maintained.
  • a low-temperature plasma treatment method is preferably used from the viewpoint of preventing deterioration of the ophthalmic lens due to heat.
  • the treatment is preferably performed at room temperature to about 50 ° C.
  • the gas may contain hydrogen, but its content is preferably not less than 1% by volume and not more than 80% by volume in the gas.
  • it is necessary to mix hydrogen with at least one selected from helium, neon and argon. It is preferable to perform plasma treatment with a gas.
  • the content of hydrogen in the mixed gas is preferably 1% by volume or more and 80% by volume or less.
  • the atmospheric pressure after the introduction of the gas is usually in the range of 0.01 to 5.0 torr. Further, in order to effectively improve hydrophilicity (water wettability) and further maintain the effect for a long time, it is more preferable that the content is in the range of 0.1 to 1.0 torr.
  • a vacuum chamber provided with a high-frequency or low-frequency oscillator. Among them, plasma treatment with high frequency has a remarkable effect of improving the hydrophilicity, and usually 13.56 MHz is preferably used.
  • the discharge output is appropriately selected depending on the size of the apparatus and the ophthalmic lens to be processed, but is usually from 10 to 500 W.
  • a sufficient processing effect is usually obtained at about 0.5 to 30 min.
  • the present invention is not limited by these conditions. More specifically, for example, using a vacuum chamber having a gas inlet and an exhaust means for exhausting to a predetermined reduced pressure state, an ophthalmic lens to be treated is arranged between the negative and positive electrodes, and maintained at a predetermined reduced pressure state. After that, one or more types of mixed gas containing hydrogen at a predetermined flow rate are introduced and discharged. It is preferably performed by creating a plasma state by plasma treatment. The method for deprotecting a protected hydrophilic group in a polymer according to the present invention thereby generates a hydrophilic group to improve hydrophilicity.
  • Deprotection methods can include irradiation with electromagnetic waves (including light), heating, hydrolysis, solvolysis, the use of specific deprotection reagents, and combinations thereof. Of these reforming means, simple and preferred are hydrolysis and solvolysis, with hydrolysis being most preferred. Examples of the organic solvent used for the solvolysis for deprotection include alcohols, amines, and thiols, but alcohols are the easiest to handle and are preferred.
  • alcohols include methanol, ethanol, propanol, 2-propanol, butanol, cyclohexanol, propanediol, short diol, hexanediol, ethylene glycol, ethylene glycol, triethylene glycol, Tetraethylene render alcohol, polyethylene glycol, ethylene glycol monoalkyl ether, diethylene diol glycol monoalkyl ether, triethylene glycol monoalkyl ether, tetraethylene glycol monoalkyl ether, polyethylene glycol monoalkyl ether, glycerin, etc. is there.
  • the treatment by deprotection of the ophthalmic lens by hydrolysis or solvolysis can be performed by bringing the ophthalmic lens into contact with water or an organic solvent.
  • the specific method is not particularly limited, for example, a method of dipping the ophthalmic lens in water or an organic solvent, a method of spraying the ophthalmic lens with water or an organic solvent, a method of Examples thereof include a method of applying water or an organic solvent with a spatula or a brush, and a method of applying water or an organic solvent to an ophthalmic lens by a spin coat method or a dip coat method.
  • the temperature at which the ophthalmic lens is brought into contact with water or an organic solvent is not particularly limited, but is usually within a temperature range of about 50 ° C to 300 ° C. Will be Considering workability, the temperature range of 10 ° C to 150 ° C is more preferable, and —5 ° C to 60 ° C is most preferable.
  • the optimal time for contacting the ophthalmic lens with water or an organic solvent for treatment by deprotection varies depending on the temperature, but is generally preferably within 100 hours, more preferably within 24 hours. Preferably, within 12 hours is most preferred.
  • the deprotection reaction can be promoted by using water or an organic solvent in which a base and an acid are dissolved.
  • a base alkali metal hydroxides, alkaline earth metal hydroxides, various carbonates, various borates, various phosphates, ammonia, various ammonium salts, various amines, and the like can be used.
  • the acid examples include inorganic acids such as hydrochloric acid, hydrobromic acid, hydrofluoric acid, sulfuric acid, sulfurous acid, nitric acid, nitrous acid, phosphoric acid, polyphosphoric acid, phosphorous acid, hypophosphorous acid, and the like. And various organic carboxylic acids and various organic sulfonic acids can be used.
  • the c deprotection process can also promote the deprotection reaction by further combination with heating may be performed on the entire polymer, for example be carried out only on a part of the polymer, such as performing only the surface Good.
  • the hydrophilic group formed after the deprotection treatment of the ophthalmic lens of the present invention can be used in the form of a salt thereof.
  • the hydrophilic group is a carboxyl group or a sulfo group
  • the hydrophilic group is preferably used in the form of a salt in order to give higher water wettability.
  • Specific methods for converting the hydrophilic group into a salt form include a method of immersing the ophthalmic lens in a basic aqueous solution after deprotection treatment, and a method of immersing the ophthalmic lens polymer in a basic aqueous solution.
  • the water wettability is preferably 90 ° or less, more preferably 70 ° or less, and more preferably 70 ° or less, with a dynamic contact angle with pure water (at the time of advancement, immersion speed of 0.1 mmZsec).
  • the oxygen permeability, the oxygen permeability coefficient [m I (STP) cm ' cm- 2' sec- '' mm H g- '] is 5 5 X 1 0 - 1 1 or more on are preferable, 7 5 X 1 0 It is more preferable that the value is “” or more, and most preferable is “85 ⁇ 10” or more.
  • the tensile modulus of the polymer for the ophthalmic lens obtained by the present invention is preferably 0.1 to 30 MP, and 0.1 to 30 MP. 7 MPa is more preferred, and 0.4 to 1.5 MPa is most preferred.
  • the method for producing an ophthalmic lens of the present invention is suitable for producing ophthalmic lenses such as contact lenses, intraocular lenses, and artificial corneas.
  • the measurement was carried out using an EX270 model manufactured by JEOL Ltd. Cloth form-d was used as the solvent.
  • the measurement was performed using an FTS-7 model manufactured by BIORAD. It was measured by the liquid film method using a rock salt plate.
  • the oxygen permeability coefficient of the film-like sample was measured in water at 35 ° C using a Kakenhi-type film oxygen permeability system manufactured by Rika Seiki Kogyo.
  • a film having a size of about 2 mm ⁇ 15 mm ⁇ 0.2 mm was used, and the measurement was carried out using Tensilon RTM-100 manufactured by Saito Rientech. The tensile speed was 100 mm Zmin and the distance between grips was 5 mm.
  • the water on the surface was blown off with nitrogen blow, and the static contact angle of water was measured under the following conditions using CA-D type manufactured by Kyowa Interface Science Co., Ltd.
  • the water content (%) of the polymer was measured by the following equation.
  • W represents the weight (g) of the ophthalmic lens after the hydration treatment
  • W ⁇ represents the weight (g) of the ophthalmic lens in a dry state.
  • the appearance of the surface of the ophthalmic lens after the hydration treatment was visually observed, and evaluated according to the following criteria.
  • A The surface of the ophthalmic lens is uniformly wet.
  • ⁇ Wetting of more than half of the surface area of the ophthalmic lens is non-uniform.
  • X The surface of the ophthalmic lens is hardly wet.
  • Synthesis Example 5 Synthesis of Monomer Having Compound Represented by Formula (M 5) as a Main Component
  • a compound of the formula (M 4) (96.4 g, 0.2 0 m 0 I) and glycidyl methacrylate (29.9 g, 0.21 moi) were added, and the mixture was stirred at 60 at ⁇ 8 hours. After the completion of the reaction, volatile components were removed under reduced pressure at 60 ° C. for 5 hours. Proton nuclear magnetic resonance spectrum of the obtained liquid was measured, and as a result of the measurement, it was confirmed that the liquid was a monomer containing the compound represented by the formula (M 5) as a main component.
  • Monomer 100 parts by weight, based on the compound represented by the formula (M 1), Synthesis Example 1) and triethylene glycol dimethacrylate (5 parts by weight) are uniformly mixed, and 2,2′-azobis-mono (2,4-dimethylvaleronitrile) (0.1 part by weight) is used as a polymerization initiator. After the addition, the monomer mixture was degassed under an argon atmosphere, poured between glass plates, and sealed. First, polymerize at 100 ° C for 4 hours, then cool from 100 ° C to 40 ° C over 3.5 hours, hold at 40 ° C for 2 hours or more, Was obtained.
  • a film sample of an ophthalmic lens was obtained in the same manner as in Polymerization Example 2 except that Synthesis Example 5) was used.
  • a monomer having a compound represented by the formula (M 3) as a main component 46 parts by weight, Synthesis Example 1), tris (trimethylcyclohexyl) silylpropyl acrylate (24 parts by weight), N, Dimethyl acrylamide (30 parts by weight), acrylic acid (1 part by weight) and triethylene glycol dimethacrylate (0.5 part by weight) are uniformly mixed, and 2,2'-azobis is used as a polymerization initiator.
  • 2- (2,4-dimethylvaleronitrile) 0.1 part by weight
  • the monomer mixture was degassed under an argon atmosphere, injected between glass plates, and sealed. First, polymerize at 40 ° C for 10 hours, then start at 40 ° C
  • the temperature was raised to 110 ° C over 24 hours, the temperature was kept at 110 ° C for 4 hours to obtain a film sample of an ophthalmic lens.
  • the monomer mixture was degassed under an argon atmosphere, poured between glass plates and sealed. First, polymerize at 100 ° C for 4 hours, then cool from 100 ° C to 40 ° C over 3.5 hours, hold at 40 ° C for at least 2 hours, A film sample was obtained.
  • a monomer (100 parts by weight) containing a compound of the formula (M 3) as a main component and triethylene glycol dimethacrylate (1 part by weight) are uniformly mixed, and 2,2′-azobis is used as a polymerization initiator. (2,4-dimethylvaleronitrile) (0.1 parts by weight)
  • the monomer mixture was degassed under an argon atmosphere, poured between glass plates and sealed. First, polymerize at 100 ° C for 4 hours, then cool from 100 ° C to 40 over 3.5 hours, hold at 40 ° C for at least 2 hours, A film sample was obtained.
  • a monomer (85 parts by weight) containing the compound of the formula (M7) as a main component, trimethylsilyl acrylate (15 parts by weight) and triethylene glycol dimethacrylate (1 part by weight) are uniformly mixed, After adding 2,2'-azobis- (2,4-dimethylvaleronitrile) (0.1 parts by weight) as a polymerization initiator, the monomer mixture was degassed under an argon atmosphere, and injected between glass plates. , Sealed. First, polymerize at 100 ° C for 4 hours, then cool from 100 ° C to 40 over 3.5 hours, hold at 40 ° C for at least 2 hours, and fill the ophthalmic lens. Sample was obtained.
  • a monomer (100 parts by weight) containing the compound of the formula (M5) as a main component and triethylene glycol dimethacrylate (1 part by weight) are uniformly mixed, and 2,2′-azobis-one is used as a polymerization initiator. After adding (2,4-dimethylvaleronitrile) (0.1 part by weight), the monomer mixture was degassed under an argon atmosphere, injected between glass plates, and sealed. First, polymerize at 100 ° C for 4 hours, then cool from 100 ° C to 40 ° C over 3.5 hours, hold at 40 ° C for at least 2 hours, and polymerize for ophthalmic lenses. Was obtained.
  • Monomer (85 parts by weight) containing the compound of formula (M 1) as a main component, acrylic acid (75 parts by weight) and triethylene glycol dimethacrylate (1 part by weight) are uniformly mixed to initiate polymerization. After adding 2,2'-azobis (2,4-dimethylvaleronitrile) (0.1 parts by weight) as an agent, the monomer mixture was degassed under an argon atmosphere and injected between glass plates. , Sealed. First, polymerize at 100 ° C for 4 hours, Subsequently, the temperature was lowered from 100 ° C. to 40 over 3.5 hours, and then kept at 40 ° C. for 2 hours or more to obtain a film sample of the polymer for ophthalmic lenses.
  • 2,2'-azobis (2,4-dimethylvaleronitrile) 0.1 parts by weight
  • the film sample of the ophthalmic lens obtained in Polymerization Example 1 was immersed in concentrated sulfuric acid (96% by weight) for 3 seconds, immediately immersed in pure water, and rinsed with pure water. This was immersed in a 1 M aqueous sodium hydroxide solution at 40 ° C. for 60 minutes. Next, it was immersed in pure water and washed twice (5 minutes) with an ultrasonic cleaner. Pure water was replaced each time washing was completed.
  • the obtained sample was immersed in a sodium phosphate noborate-based PH 7.2 buffer solution (hereinafter, abbreviated as "buffer solution A”) and allowed to stand at room temperature for 24 hours. The dynamic contact angle and oxygen permeability coefficient of this sample with pure water were measured. It was found that it had high oxygen permeability and excellent surface wettability. The results are shown in Table 1.
  • Example 1 The procedure was performed in the same manner as in Example 1 except that the film sample obtained in Polymerization Example 2 was used instead of the film sample of the ophthalmic lens obtained in Polymerization Example 1. It was found to have high oxygen permeability and excellent surface wettability. The results are shown in Table 1.
  • Example 1 The procedure was performed in the same manner as in Example 1 except that the film sample obtained in Polymerization Example 3 was used instead of the film sample of the ophthalmic lens obtained in Polymerization Example 1. It was found to have high oxygen permeability and excellent surface wettability. The results are shown in Table 1.
  • a film-shaped sample of the ophthalmic lens obtained in Polymerization Example 2 was mixed with a 50% by weight aqueous sulfuric acid solution. After immersion in pure water for 15 seconds, it was immediately immersed in pure water and rinsed with pure water. It was immersed in a 1 M aqueous solution of sodium hydroxide at 40 ° C for 60 minutes. Next, it was immersed in pure water and washed twice with an ultrasonic cleaner (5 minutes). Pure water was replaced each time washing was completed. The obtained sample was immersed in buffer A and left at room temperature for 24 hours. Then, the dynamic contact angle and oxygen permeability coefficient of this sample with respect to pure water were measured. It was found to have high oxygen permeability and excellent surface water wettability. The results are shown in Table 1.
  • the film-shaped sample of the ophthalmic lens obtained in Polymerization Examples 1 to 3 was immersed in Buffer A without any special treatment, and allowed to stand at room temperature for 24 hours.
  • the film sample of the ophthalmic lens obtained in Polymerization Example 4 was immersed in a 50% by weight aqueous solution of acrylic acid at room temperature for 24 hours. After that, it was immersed in pure water and rinsed with pure water. It was immersed in a 1 M aqueous sodium hydroxide solution at 40 ° C for 15 minutes. Next, it was immersed in pure water and washed twice with an ultrasonic cleaner (5 minutes). Pure water was replaced each time washing was completed. The obtained sample was immersed in buffer A and left at room temperature for 24 hours. The dynamic contact angle of the obtained sample with pure water and the oxygen permeability coefficient were measured. It was found that it had high oxygen permeability and excellent surface wettability. The results are shown in Table 1.
  • Example 6 The procedure was performed in the same manner as in Example 5 except that a 50% by weight aqueous solution of propionic acid was used instead of the 50% by weight aqueous solution of acrylic acid. It was found to have high oxygen permeability and excellent surface wettability. The results are shown in Table 1.
  • the film sample of the ophthalmic lens obtained in Polymerization Example 5 was immersed in a mixture of acrylic acid and an aqueous 0.1 M sodium hydroxide solution (weight ratio: 1 Z 1) at room temperature for 24 hours. After that, it was immersed in pure water and rinsed with pure water. It was immersed in pure water and subjected to a heating water treatment at 120 ° C for 30 minutes in a storage tank. The obtained sample was immersed in buffer A and left at room temperature for 24 hours. The dynamic contact angle of the obtained sample with pure water and the oxygen permeability coefficient were measured. It was found that it had high oxygen permeability and excellent surface wettability. The results are shown in Table 1.
  • Example 7 was carried out in the same manner as in Example 7, except that the film sample obtained in Polymerization Example 6 was used instead of the film sample of the ophthalmic lens obtained in Polymerization Example 5. It was found that it had high oxygen permeability and excellent surface wettability. The results are shown in Table 1.
  • the film sample of the ophthalmic lens obtained in Polymerization Examples 4 to 6 was immersed in Buffer A without any special treatment, and allowed to stand at room temperature for 24 hours.
  • the film-like sample of the ophthalmic lens obtained in Polymerization Example 7 was used.
  • the water content of this ophthalmic lens is 40%, and the static contact angle of water is
  • the obtained sample was immersed in buffer A and left at room temperature for 24 hours.
  • the dynamic contact angle, oxygen permeability coefficient and elastic modulus of the obtained sample with respect to pure water were measured. It was found that it had high oxygen permeability and excellent surface water wettability. The results are shown in the table.
  • the film samples of the ophthalmic lenses obtained in Polymerization Examples 7 and 8 were immersed in Buffer A without any special treatment, and allowed to stand at room temperature for 24 hours.
  • the film sample obtained in Polymerization Example 9 was immersed in a 0.1 M sodium hydroxide aqueous solution, and subjected to a deprotection treatment at 40 ° C. for 30 hours. After deprotection treatment, immerse in pure water / 5 Washing with an ultrasonic cleaner (5 minutes) was performed twice. Pure water was replaced each time washing was completed.
  • the film sample obtained in Polymerization Example 10 was immersed in a 1 M aqueous sodium hydroxide solution, and subjected to a deprotection treatment at 40 ° C. for 20 hours. After the deprotection treatment, it was immersed in pure water and washed twice with an ultrasonic cleaner (for 5 minutes). Pure water was replaced each time washing was completed.
  • the film-like sample obtained in Polymerization Example 11 was immersed in a 0.1 M aqueous sodium hydroxide solution, and subjected to a deprotection treatment at 40 ° C. for 30 hours. After the deprotection treatment, it was immersed in pure water and washed twice with an ultrasonic cleaner (for 5 minutes). Pure water was replaced each time washing was completed.
  • the film-like sample obtained in Polymerization Example 12 was immersed in 1 M hydrochloric acid and subjected to a deprotection treatment at 40 ° C. for 18 hours. After washing with pure water, further Hitatsubushi a hydrophilic group to 0. 1 M aqueous sodium hydroxide to the salt form, 4 0 ° 1 6 h the £ After completion of the treatment was carried out in C, and pure water It was immersed and washed twice with an ultrasonic cleaner (5 minutes). Pure water was replaced every time washing was completed.
  • the film-like sample obtained in Polymerization Example 1 was immersed in a 0.1 M aqueous sodium hydroxide solution and treated at 40 ° C. for 30 hours. After the treatment, it was immersed in pure water and washed twice with an ultrasonic cleaner (for 5 minutes). Pure water was replaced every time washing was completed. The dynamic contact angle, oxygen permeability coefficient and tensile modulus of the treated film sample were measured. The results are shown in Table 1. Since the film did not have a protected hydrophilic group, it was inferior in water wettability even after the treatment (dynamic contact angle exceeded 90 °).
  • the film-like sample obtained in Polymerization Example 13 was immersed in a 0.1 M aqueous sodium hydroxide solution and treated at 40 ° C. for 30 hours. After the treatment, it was immersed in pure water and washed twice (5 minutes) with an ultrasonic cleaner. Pure water was replaced every time washing was completed. The dynamic contact angle and oxygen permeability coefficient of the treated film sample were measured. It was too brittle to measure the tensile modulus. The results are shown in Table 1. Since the film does not have a protected hydrophilic group, and water swelling, it was inferior to the oxygen permeability (oxygen permeability coefficient 5 5 X 1 0- '' ml (STP) cm ⁇ cm "2 ⁇ sec " 1 ⁇ mmHg, less). According to the present invention, an ophthalmic lens having high oxygen permeability and good surface wettability can be obtained.
  • Trimethylsilyl acrylate 1 Measurement results of dynamic contact angle, oxygen permeation and elastic modulus (continued)
  • Ar / hydrogen 95/5 volume 3 ⁇ 4; 50W 20min plasma treatment with gas

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
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Abstract

La présente invention concerne un procédé permettant la production d'une lentille oculaire. Ce procédé consiste à prendre un polymère, en l'occurrence, un copolymère comprenant des monomères essentiels portant un groupe aminé et un groupe siloxanyl, et à le soumettre à un traitement. Ce traitement peut être un traitement à l'acide ou un traitement au plasma sous une atmosphère constituée d'au moins un gaz dont l'hydrogène. Ce traitement peut également être d'un type privant de leurs groupes de protection les groupes hydrophiles protégés du polymère de façon à laisser des groupes hydrophiles libres. L'invention concerne également un procédé permettant de produire le polymère convenant à la production d'une lentille oculaire hautement perméable à l'oxygène et suffisamment mouillable en surface par l'eau.
PCT/JP1999/002216 1998-04-28 1999-04-26 Production de lentille oculaire WO1999056167A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP11861198A JP3937576B2 (ja) 1998-04-28 1998-04-28 眼用レンズ用ポリマーおよびその改質方法
JP11861098A JP3941217B2 (ja) 1998-04-28 1998-04-28 コンタクトレンズの製造方法およびそれを用いたコンタクトレンズ
JP10/118611 1998-04-28
JP10/118610 1998-04-28

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WO1999056167A1 true WO1999056167A1 (fr) 1999-11-04

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003042265A1 (fr) * 2001-11-13 2003-05-22 Toray Industries, Inc. Polymere et lentilles ophthalmologiques realisees a l'aide de ce polymere
US8883928B2 (en) 2008-07-21 2014-11-11 Novartis Ag Silicone-containing polymeric materials with hydrolyzable groups
CN109475660A (zh) * 2016-05-16 2019-03-15 宾视研发公司 疏水性人工晶状体

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57181524A (en) * 1981-05-01 1982-11-09 Toyo Contact Lens Co Ltd Contact lens and its manufacture
JPH05257093A (ja) * 1990-02-23 1993-10-08 Ciba Geigy Ag アモルファスフッ素ポリマーをベースとする眼用レンズ
JPH05297330A (ja) * 1992-04-16 1993-11-12 Menicon Co Ltd 非含水性眼用レンズの表面処理法およびその表面処理法によって処理が施された非含水性眼用レンズ
JPH0667122A (ja) * 1992-08-18 1994-03-11 Nippon Oil & Fats Co Ltd ソフトコンタクトレンズ
JPH06510811A (ja) * 1991-09-12 1994-12-01 ボシュ　アンド　ロム　インコーポレイテッド ぬれ性のシリコーンヒドロゲル組成物および方法
JPH07266443A (ja) * 1994-03-30 1995-10-17 Hoya Corp ソフトコンタクトレンズの製造方法
JPH10170874A (ja) * 1996-12-06 1998-06-26 Toray Ind Inc プラスチック成形品
JPH10212355A (ja) * 1997-01-31 1998-08-11 Toray Ind Inc プラスチック成形品

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57181524A (en) * 1981-05-01 1982-11-09 Toyo Contact Lens Co Ltd Contact lens and its manufacture
JPH05257093A (ja) * 1990-02-23 1993-10-08 Ciba Geigy Ag アモルファスフッ素ポリマーをベースとする眼用レンズ
JPH06510811A (ja) * 1991-09-12 1994-12-01 ボシュ　アンド　ロム　インコーポレイテッド ぬれ性のシリコーンヒドロゲル組成物および方法
JPH05297330A (ja) * 1992-04-16 1993-11-12 Menicon Co Ltd 非含水性眼用レンズの表面処理法およびその表面処理法によって処理が施された非含水性眼用レンズ
JPH0667122A (ja) * 1992-08-18 1994-03-11 Nippon Oil & Fats Co Ltd ソフトコンタクトレンズ
JPH07266443A (ja) * 1994-03-30 1995-10-17 Hoya Corp ソフトコンタクトレンズの製造方法
JPH10170874A (ja) * 1996-12-06 1998-06-26 Toray Ind Inc プラスチック成形品
JPH10212355A (ja) * 1997-01-31 1998-08-11 Toray Ind Inc プラスチック成形品

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003042265A1 (fr) * 2001-11-13 2003-05-22 Toray Industries, Inc. Polymere et lentilles ophthalmologiques realisees a l'aide de ce polymere
US8883928B2 (en) 2008-07-21 2014-11-11 Novartis Ag Silicone-containing polymeric materials with hydrolyzable groups
CN109475660A (zh) * 2016-05-16 2019-03-15 宾视研发公司 疏水性人工晶状体

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