Process for producing an ocular lens
Abstract
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Term
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- Priority and filed
- Granted
- Today
8 claims: 3 independent, 5 dependent
- 1A method for manufacturing an ophthalmic lens using a molding die, which is a step of irradiating at least a part of an ocular lens surface forming surface of the molding die with excima light, and an ophthalmic lens material on the excimer light irradiation surface of the molding die. A step of uniformly applying a compound or a solution of the compound that can be fixed to the surface of an ophthalmic lens by interaction with a polymer component inside.The step in which the coating is performed in a state where the molding die is rotated.A step of filling the molding die with an ophthalmic lens material and polymerizing the molding die, and removing the polymer obtained as a result of the polymerization from the molding die to obtain an ophthalmic lens material in which the applied compound is fixed on the surface. A method for producing an ophthalmic lens, which comprises a step and a step of extracting unfixed and unreacted compounds in the obtained ophthalmic lens material. 成形型を用いる眼用レンズの製造方法であって、成形型の眼用レンズ表面形成面の少なくとも一部にエキシマ光を照射する工程と、該成形型のエキシマ光照射面に、眼用レンズ材料中の重合成分との相互作用によって眼用レンズ表面に固定可能な化合物または該化合物の溶液を均一に塗布する工程であり、該塗布が成形型を回転させた状態においておこなわれる工程と、前記成形型に眼用レンズ材料を充填し重合させる工程と、該重合の結果得られた重合物を成形型から脱離し、前記塗布した化合物が表面に固定された眼用レンズ素材を得る工程と、得られた眼用レンズ素材内の未固定、未反応化合物を抽出する工程とからなる眼用レンズの製造方法。
- 6The first, second or third claim, wherein the solution of the compound that can be fixed on the surface of the ophthalmic lens is a solution in which a monomer or a macromonomer is dissolved in a solvent, or a solution in which a mixture of the monomer and the macromonomer is dissolved in the solvent. Manufacturing method. 前記眼用レンズ表面に固定可能な化合物の溶液が、モノマーまたはマクロモノマーを溶剤に溶解させた溶液、あるいはモノマーとマクロモノマーの混合物を溶剤に溶解させた溶液である請求項1、2または3記載の製造方法。
- 8The compound that can be fixed to the surface of the ophthalmic lens is a hydrophilic monomer, a macromonomer containing a hydrophilic monomer as a main component, a polymer containing a hydrophilic monomer as a main component, or a mixture thereof. The manufacturing method described in 6 or 7. 前記眼用レンズ表面に固定可能な化合物が、親水性モノマー、親水性モノマーを主成分として含むマクロモノマー、または親水性モノマーを主成分として含むポリマー、あるいはこれらの混合物である請求項4、5、6または7記載の製造方法。
Independent claims3
1 paragraph, as filed
[0001] [Technical field to which the invention belongs] The present invention relates to an ophthalmic lens and a method for producing the same, and more particularly to an ophthalmic lens having a surface layer composed of a component different from the polymerized component of the main body of the ophthalmic lens and a method for producing the same. [0002] [Conventional technology] Lenses are widely used as a means of correcting vision. Lenses for the eye include those worn on the eyeball such as contact lenses, and so-called intraocular lenses that are inserted into the eyeball after removal of the crystalline lens of a cataract patient. [0003] Traditionally, these ocular lenses have usually been manufactured by cutting. However, due to the problem of mass productivity, the manufacturing method has changed to mold polymerization using a molding mold. In the manufacturing method by mold polymerization, the molding mold is a combination of a male mold and a female mold, and a lens forming material is filled in a space formed between the two and polymerized to obtain an ophthalmic lens material. An ophthalmic lens is manufactured by taking out the obtained ophthalmic lens material from a molding die and performing a treatment such as removal of unreacted residual components. [0004] By the way, in recent years, as causes of eye diseases of eye lens wearers, a decrease in hydrophilicity (tear wettability) on the surface of an eye lens and adhesion of stains such as proteins and fats have been attracting attention. Then, improvement of the ophthalmic lens is being studied in order to prevent eye diseases by improving the hydrophilicity of the surface of the ophthalmic lens and preventing the adhesion of dirt. [0005] For example, Japanese Patent Application Laid-Open No. 57-34518 discloses a method of applying plasma treatment to the surface of an ophthalmic lens material to modify the surface and improve water wettability. Further, Japanese Patent Application Laid-Open No. 6-49251 discloses a method of modifying the surface of an ophthalmic lens by grafting a hydrophilic monomer on the surface of the ophthalmic lens material. [0006] However, in these methods, physical and chemical treatment is applied to the surface of the once molded eye lens material, which causes deformation of the eye lens material and obtains the required shape in the finished eye lens. I can't do it. [0007] On the other hand, a polymer solution having a zwitterionic group having excellent biocompatibility is applied to the surface of a molding die, and a lens polymer is produced using the molding die after the coating to form a polymer coat layer on the surface. A method for obtaining an ophthalmic lens material to have is disclosed in PCT International Publication WO 00/04078. Since this method can form the entire ocular lens material including the surface coat layer by one polymerization, it is possible to avoid deformation of the lens material as compared with the above-mentioned method of applying a treatment to the polymerized lens material. Seems to be excellent. [0008] However, in this method, when the polymer solution is applied to the molding die, a liquid pool is generated along the shape of the molding die, so that there is a problem that the coat layer is formed non-uniformly. Normally, the coat layer is composed of a substance different from the polymerized component of the ophthalmic lens, so that the non-uniform formation of the coat layer tends to cause deformation of the ophthalmic lens material and cloudiness during polymerization, and the optics of the ophthalmic lens. There is a risk of threatening the function. [0009] [Problems to be Solved by the Invention] Therefore, an object of the present invention is to provide an ophthalmic lens which is not deformed at the time of manufacture and has a uniform coat layer on the surface. Another object of the present invention is to produce an ophthalmic lens material having a uniform coat layer on the surface by a single mold polymerization. [0010] [Means for solving problems] The ophthalmic lens according to the present invention has a step of irradiating at least a part of the surface forming surface of the molded ophthalmic lens with excima light, and a compound to be a coat layer or a solution of the compound on the molded surface after the excima light irradiation. A step of uniformly applying the above, a step of filling a mold with an ophthalmic lens material and polymerizing the same, and a step of desorbing the polymer obtained as a result of the polymerization from the mold and fixing the compound to the surface of the ophthalmic lens material. Is produced by a step of obtaining an unfixed and unreacted compound in the obtained lens material for an eye. [0011] The compound to be the coat layer is a compound that can be fixed to the surface of the ophthalmic lens by interacting with the polymerized component in the ophthalmic lens material. [0012] BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a method for manufacturing an ophthalmic lens according to the present invention will be described with reference to FIG. FIG. 1 (a) is a cross-sectional view showing a molding die used for manufacturing an ophthalmic lens and an ophthalmic lens material formed in the molding die, and FIG. 1 (b) is an enlarged view of part B thereof. .. Further, FIG. 1 (c) is a diagram showing an eye lens material detached from the molding die. [0013] <Process 1> In the method for manufacturing an ophthalmic lens according to the present invention, first, the lens surface forming surface of the molded mold to be used, that is, the lower surface (convex surface) of the male mold 2 and / or the upper surface (concave surface) of the female mold 4 is irradiated with excimer light. [0014] The molding mold is generally a resin mold, and is made of, for example, a polyolefin such as polyethylene or polypropylene, polystyrene, polycarbonate, polymethylmethacrylate, an ethylene-vinyl alcohol copolymer, a polyacetal, a polyamide, polyester, or a synthetic resin such as polysulfone. [0015] As the types of excimer light, argon (center wavelength of emission: 126 nm), krypton (same: 146 nm), xenon (same: 172 nm), krypton chloride (same: 222 nm), xenon chloride (same: 308 nm) are used as discharge gas. It is possible that there was something. Preferably, vacuum ultraviolet rays having a emission center wavelength of 172 nm using xenon as the discharge gas can be mentioned. The irradiation time of excimer light is 1 second to 60 minutes, more preferably 1 second to 10 minutes. [0016] Irradiation with excimer light promotes the generation of active species (radicals) and physical erosion on the surface of the mold. [0017] In the process described later, a material to be a coat layer of an ophthalmic lens (hereinafter, also referred to as a coat layer material) is applied to the surface of the molding die, but depending on the combination of the molding die material and the coat layer material to be applied, it may be applied. Since the repulsive force acting between the materials is strong, it becomes difficult to uniformly apply the coat layer material. Further, the molding die is generally manufactured by injection molding, but the surface of the molding die obtained by injection molding is not good in smoothness. For this reason, the surface of the mold has high surface energy, which hinders the affinity at the interface with different materials (that is, the coat layer material), and it is also difficult to uniformly apply the coat layer material. [0018] However, according to the present invention, active species (radicals) are generated on the surface of the mold by irradiation with excimer light, and the surface of the mold is eroded to improve the smoothness. The active species (radicals) serve as a scaffold when applying the coat layer material, and the smooth surface has low physical surface energy and has an excellent affinity with the coat layer material. Therefore, by modifying the surface of the mold by excimer light irradiation, it is possible to form a good coat layer regardless of the type of coat layer material. [0019] A method of irradiating the surface of a mold with plasma in an oxygen gas atmosphere or an inert gas atmosphere to generate active species (radicals) and using it as a scaffold for coating a coat layer material is already known. [0020] However, when the coat layer material is applied after generating a large amount of active species (radicals) on the surface of the mold, a chemically strong interaction occurs at the interface between the mold and the coat layer material depending on the combination of materials. There is something. This interaction makes it difficult to remove (remove) the ophthalmic lens material from the mold, leaving only the coat layer material on the surface of the mold, damaging the coat layer material or the ophthalmic lens material itself. This may cause problems such as the need for special techniques and materials for detachment from the molding die. [0021] [0021] Therefore, it is desirable to appropriately suppress the generation of active species and physically erode the surface of the mold to change the surface energy. [0022] According to the present invention, the generation of active species (radicals) and the smoothing of the surface are simultaneously performed by irradiation with excimer light, and the generation of active species (radicals) is compared with the modification of the mold surface by conventional plasma irradiation. Few. Therefore, the interaction between the molding die and the coat layer material at the interface can be suppressed, and the removal from the molding die is not difficult. [0023] <Process 2> Next, as described above, the coat layer material is uniformly applied to the excimer light irradiation surface of the molding die. [0024] The coat layer material is a compound or a solution thereof that can be fixed to the surface of the ophthalmic lens by interaction during the polymerization of the ophthalmic lens material. Since the coat layer material is fixed on the surface of the ophthalmic lens material, a material capable of copolymerizing with the polymerization component of the ophthalmic lens material is desirable. Further, in order to uniformly apply the coating layer to the surface of the molding mold, the coating layer material is preferably a monomer which is a solid or a highly viscous liquid at room temperature, and the coating layer is formed by dissolving it in a solvent, applying it to the molding mold as a solution, and drying it. It is desirable to form. [0025] Specific examples of such monomers include N-vinylacetamide; N-vinylformamide; N-vinyl-N-methylacetamide; N-isopropylacrylamide; 2-acrylamide-2-methylpropanesulfonic acid; N, N-dimethyl. Alkyl (meth) acrylamides such as (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-dipropyl (meth) acrylamide; N-vinyl-2-pyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, N-vinyllactams such as N-vinylcaprylolactam; hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate; Examples include (meth) acrylic acid. Preferred are N-vinylacetamide; N-vinylformamide; N-vinyl-N-methylacetamide; N-isopropylacrylamide; 2-acrylamide-2-methylpropanesulfonic acid, and more preferably, it is easy to dry with the solvent. N-vinylacetamide is used to stabilize (immobilize) the surface of the mold. [0026] Here, the solvent refers to an organic solvent having a low boiling point, that is, an organic solvent having a boiling point of 15 to 150 ° C, preferably 30 to 120 ° C. If the boiling point is 15 ° C or less, the volatilization in the coating process is too fast to obtain a uniform coating, and if the boiling point is 150 ° C or more, the appropriate volatilization rate of the solvent cannot be obtained in the coating process at room temperature. [0027] Specific examples of the low boiling solvent include alcohols such as methanol, ethanol, propanol, butanol, and pentanol; acetone; tetrahydrofuran; N, N-dimethylformamide; hexane; benzene; toluene; acetonitrile; methylene chloride and the like. These can be used alone or in combination of two or more. In particular, ethanol is conveniently used because it is excellent in safety and volatility and inexpensive. [0028] Further, the coat layer material is not limited to the monomer having a relatively low molecular weight as described above, and a macromonomer or a polymer which is a solid or a highly viscous liquid at room temperature and can be dissolved in a solvent is used. You can also do it. [0029] Specific examples of such macromonomers include alkyl (meth) acrylate-based monomers 65 to 98.8 [mol%] and hydrophilic groups described as component (A) in JP-A-5-29091. Consists of 1 to 30 [mol%] of the monomer and 0.2 to 5 [mol%] of the monomer having two polymerizable groups in the molecule, and has a hydrophilic group and at least one polymerizable group in the molecule (meth). ) Acrylate-based polymer can be mentioned. [0030] Here, in the alkyl (meth) acrylate-based monomer, the alkyl group in the monomer may be linear, branched, or cyclic, and the hydrogen atom in these alkyl groups is a halogen atom such as fluorine. It may be substituted, and specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, and dodecyl (meth). Examples thereof include alkyl (meth) acrylates such as meta) acrylate, cyclohexyl (meth) acrylate, trifluoroethyl (meth) acrylate, and pentafluoroethyl (meth) acrylate. These may be used alone or in combination of two or more. [0031] The hydrophilic group-containing monomer is a monomer containing a hydrophilic group such as a hydroxyl group, a polyalkylene glycol residue, a carboxyl group, an amide group, an N-substituted amide group, an amino group, and an N-substituted amino group. Examples include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, dihydroxypropyl (meth) acrylate, dihydroxybutyl (meth) acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol. Hydroxyl-containing (meth) acrylates such as mono (meth) acrylates and dipropylene glycol mono (meth) acrylates; (meth) acrylic acids; (meth) acrylamides; N-methyl (meth) acrylamides, N-ethyl (meth) acrylamides, N-mono-substituted (meth) acrylamides such as N-hydroxyethyl (meth) acrylamide; N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-ethyl-N-aminoethyl (meth) N, N-di-substituted (meth) acrylamides such as acrylamide; (meth) acryloyloxyalkylamines such as (meth) acryloyloxyethylamine; N-mono-substituted (meth) acryloyloxys such as N-methyl (meth) acryloyloxyethylamine Alkylamine; N, N-di-substituted (meth) acryloyloxyalkylamine such as N, N-dimethyl (meth) acryloyloxyethylamine; N-vinyllactams such as N-vinylpyrrolidone can be mentioned. In addition, 2,3-O-isopropylidene glycerol (meth) acrylate, 2-methyl-2-ethyl-4- (meth) acrylic oxymethyl-1,3-dioxolane, methyl-2, A compound obtained by ketalizing two hydroxyl groups in a dihydroxyalkyl (meth) acrylate such as 3-O-isopropyrideneglycerol (meth) acrylate can also be mentioned as having the same effect as the hydrophilic group-containing monomer. .. These monomers may be used alone or in combination of two or more. Among the above-mentioned monomers, a hydroxyl group-containing (meth) acrylate is preferable. [0032] Specific examples of the monomer having two polymerizable groups in the molecule include ethylene glycol di (meth) acrylate, allyl (meth) acrylate, vinyl (meth) acrylate, diethylene glycol di (meth) acrylate, and triethylene glycol di. Examples thereof include (meth) acrylate, propylene glycol di (meth) acrylate, and dipropylene glycol di (meth) acrylate. These monomers may be used alone or in combination of two or more. [0033] Further, as other specific examples of the macromonomer suitable for the coat layer material, the alkyl (meth) acrylate-based monomer described as the component (A) in JP-A-3-57454 and 2 in the molecule. Examples thereof include (meth) acrylate-based polymers which are composed of monomers having individual polymerizable groups and have at least one polymerizable group in the molecule on average. [0034] Here, in the alkyl (meth) acrylate-based monomer, the alkyl group in the monomer may be linear, branched, or cyclic, and the hydrogen atom in these alkyl groups is a halogen atom such as fluorine. It may be substituted, and specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, and dodecyl (meth). Examples thereof include alkyl (meth) acrylates such as meta) acrylate, cyclohexyl (meth) acrylate, trifluoroethyl (meth) acrylate, and pentafluoropropyl (meth) acrylate. These may be used alone or in combination of two or more. [0035] Specific examples of the monomer having two polymerizable groups in the molecule include allyl (meth) acrylate, vinyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and triethylene glycol. Examples thereof include di (meth) acrylate and dipropylene glycol di (meth) acrylate. These monomers may be used alone or in combination of two or more. [0036] Further, specific examples of polymers suitable for the coat layer material include polyalkylene glycol (mono) acrylates such as polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate; polyvinyl alcohol; polyacrylic acid; polyethylene oxide; poly. Polyethylene oxide-bisacetic acid; examples thereof include polymers that are polymerized by combining one or more of the above monomers. [0037] Examples of the means for applying the solution of the coat layer material to the surface of the mold include a method of directly immersing the surface of the mold in the solution of the coat layer material and a method of applying the solution by a brush or the like. However, in either method, it is difficult to uniformly apply the solution to the entire surface of the mold, and a good coat layer cannot be obtained. In particular, the molding mold for an ophthalmic lens has dents in which the coating solution tends to collect due to its structure, so that uneven thickness of the coat layer cannot be avoided. [0038] Therefore, it is desirable to dissolve the coating material in a low boiling point solvent and then spray it using a spray or the like. In addition to the advantage that the coating material can be applied uniformly to the surface of the mold, spraying adheres to the surface of the mold while volatilizing the solvent, so it is possible to accelerate the stabilization (fixation) of the coating material on the surface of the mold. There is also the advantage of being. [0039] However, it is difficult to apply the coating completely uniformly even by spraying, and it takes a long time to dry in a place where a large amount of coating material is attached. Variations in the drying time on the mold surface cause non-uniformity of the coat layer. This is because, in general, the coating material is stabilized by being dissolved in the solvent, and tends to constantly move in the direction of being dissolved in the solvent (that is, to a place where it has not been dried) during the drying process. .. [0040] Therefore, in order to enable more uniform coating and to form a more uniform coat layer, it is desirable to spray the coat layer material in a state where the molding die is rotated and to continue the rotation even in the drying process. .. The central axis of rotation may be in a direction perpendicular to the central portion of the lens forming surface of the molding die. [0041] By rotating the molding die, it is possible to absorb even a slight unevenness in spraying and average the spray amount with respect to the entire mold, and it is possible to form a uniform coat layer. Further, by continuing the rotation even in the drying process, the drying rate can be increased and the drying rate at each position on the mold surface can be averaged, and a more uniform coat layer can be formed. [0042] Here, the rotation speed of the mold is preferably 100 to 10000 [rpm], more preferably 500 to 5000 [rpm]. If the rotation speed is 100 [rpm] or less, the drying speed cannot be averaged by rotation, and if it is 10000 [rpm] or more, the applied solution is almost scattered and the desired coating is applied. Can no longer be done. [0043] <Process 3> The material for the ophthalmic lens is filled and polymerized in the molding mold coated with the coat layer material. [0044] In the present invention, the polymerization component of the ophthalmic lens material is not particularly limited, and all the polymerization components of the ophthalmic lens material can be applied regardless of water content / non-water content or hard / soft. [0045] For example, the polymerization component is from a hydrophilic monomer (hereinafter, component C) containing polysiloxane macromonomer (hereinafter, component A), silicon-containing alkyl (meth) acrylate (hereinafter, component B) and N-vinylpyrrolidone as main components. The ratio of the total of component A and component B to component C [total of component A and component B / component C (weight ratio)] is 30/70 to 70/30, and the total of component A and component B The ratio [component A / component B (weight ratio)] is 25/75 to 75/25, and the ratio of N-vinylpyrrolidone to other hydrophilic monomers in component C [N-vinylpyrrolidone / component X ( Examples of eye lens materials have a weight ratio of)] of 50/50 or more. [0046] Examples of the polymerization component include an ophthalmic lens material containing a siloxane macromonomer having two or more active unsaturated groups and a number average molecular weight of 2000 to 100,000 and a lower fatty acid vinyl ester. [0047] The polymerization method of the ophthalmic lens material is radical polymerization by heat or light, and it is essential that the lens material contains a polymerization initiator suitable for the polymerization method. This polymerization initiator may be contained in the material (coat layer material) applied in the above <Step 2>, and the type of the polymerization initiator is the same as that contained in the polymerization component of the lens material. It may or may be different. [0048] When polymerizing an ophthalmic lens material by photopolymerization, it is desirable to irradiate ultraviolet rays with a wavelength of 200 to 500 [nm] to carry out the polymerization, and the irradiation intensity is 0.1 [mW / cm].<sup>2</sup>] Above, preferably 0.5 ~ 20 [mW / cm<sup>2</sup>] Irradiance intensity is desirable. The irradiation time of ultraviolet rays is not particularly limited, and is the time required for the polymerized component in the lens material for the eye to be sufficiently cured and the coated layer material applied to be immobilized on the lens surface. However, the irradiation time is preferably 24 hours or less, preferably 60 minutes or less, so that the function as an optical material is not impaired due to deformation of the lens or deterioration of transparency after ultraviolet irradiation. [0049] <Process 4> The obtained polymer is removed from the molding die to obtain an ophthalmic lens material in which the coat layer material is fixed on the surface. [0050] Desorption is performed by separating the male and female 2 and the female type 4. By this forced desorption, either male or female 2 or female type 4 is usually desorbed from the polymerized lens material. The type desorbed at this time may be a male type or a female type, and is not limited to either one. [0051] Next, the lens polymer that remains fixed to the surface of one mold is desorbed, if possible, by deforming the mold in a direction that increases the curvature of the mold surface. As another desorption method, there is a method of immersing the lens polymer and the molding die in water and / or an organic solvent. In this method, the lens polymer is swelled to be detached from the mold. This swelling desorption method is more preferably used because it reduces the load due to strain on the lens polymer and greatly avoids the risk of lens breakage. [0052] <Process 5> Next, the unfixed / unreacted compound in the obtained ophthalmic lens material is extracted. [0053] By the above <steps 1> to <step 4>, an ophthalmic lens material whose surface is coated with a coat layer material can be obtained, but further, the surface of the ophthalmic lens material is further mixed with water and / or an organic solvent. It is desirable to remove unreacted residual components from the layer. [0054] The organic solvent used for the desorption of <Step 4> and / or the removal of unreacted residual components in <Step 5> includes alcohols such as methanol, ethanol, propanol, butanol, and pentanol; acetone; tetrahydrofuran; Examples include N, N-ditimelformamide; hexane; benzene; toluene; acetonitrile; methylene chloride. To remove the unreacted residual component, for example, after extraction by a Soxhlet extraction method or the like, the ophthalmic lens material may be boiled with water or physiological saline if necessary. [0055] Thus, according to the method for manufacturing an ophthalmic lens of the present invention, it is possible to obtain an ophthalmic lens having a shape faithful to a molding mold without deformation of the material and having a uniform coat layer. Moreover, such an ophthalmic lens can be manufactured by a single mold polymerization. [0056] [Example] Example 1 As an example of the present invention, a silicon-containing non-hydrous soft contact lens provided with a coat layer on the surface and a method for producing the same will be described. [0057] Excimer light was irradiated to a polypropylene contact lens manufacturing mold (male type and female type) using an irradiator (UER20-172, manufactured by Ushio Denki Co., Ltd.). Irradiation intensity at the measurement wavelength (172 [nm]) is 13.5 [mW / cm]<sup>2</sup>], And irradiation was carried out for 5 minutes at room temperature, normal pressure, and atmospheric atmosphere. [0058] [0058] Then, as a coat layer material, a 3.0 [w / w%] ethanol solution in which N-vinylacetamide was dissolved in ethanol was prepared, and sprayed on the surface of a mold rotating at 1000 [rpm] using a spray. .. [0059] After spraying, the rotation was maintained for 2 minutes to volatilize ethanol to form a coat layer of N-vinylacetamide on the surface of the mold. It was confirmed by observation with the naked eye and a stereoscope that a uniform and even coat layer was formed. [0060] Next, a compounding solution of an ophthalmic lens material consisting of the following polymerization components (the numbers indicate the composition by weight) was prepared and filled in a female mold of a molding mold; Urethane-containing polysiloxane macromonomer (Chemical formula 1) 40 parts Tris (trimethylsiloxy) propyl acrylate 12 parts 20 parts of 2-hydroxy-3-perfluorohexylpropyl acrylate 28 parts vinyl acetate Ethylene glycol dimethacrylate 0.4 part 0.8 parts of diethylene glycol diallyl ether 2-Hydroxy-2-methyl-1-phenylpropan-1-one 0.2 part [0061] [Chemical 1]<img file="JP4909469B2_D0001.tif" />[0062] After assembling the male mold into the female mold after filling the lens material for the eye, the polymerization was carried out by irradiating with ultraviolet rays using an ultraviolet irradiation device (made by Eye Graphics Co., Ltd., UX0302-03). Irradiance intensity at measurement wavelength (365 [nm]) is 10.0 [mW / cm]<sup>2</sup>], And irradiation was performed for 10 minutes at room temperature. [0063] The molding die after the polymerization was forcibly separated, and one of the molding dies was separated from the lens polymer. At this time, the lens polymer was not damaged. Next, the mold with the lens polymer fixed on the surface was immersed in a 2-propanol / water (50/50) solution for 2 hours. By this immersion, the lens polymer was sufficiently swollen and completely removed from the mold. [0064] The lens polymer was transferred into 2-propanol and immersed for 1 hour in order to facilitate the removal of the polymerized components of the lens material and the unreacted residual components of the coat layer material. Then, in order to replace and remove 2-propanol, the lens polymer was transferred to distilled water and immersed for 2 hours. Further, this lens polymer was transferred to physiological saline and autoclaved at 121 ° C. for 20 minutes. [0065] X-ray photoelectron spectrometer (Japan) to confirm the presence of N-vinylacetamide, which is a coat layer material, on the surface of the lens polymer (hereinafter referred to as sample 1 ) produced as described above. Surface analysis was performed by JPS-9000MX, manufactured by Denshi Co., Ltd. The results are shown in Table 1 as sample 1 . [0066] In addition, sample 2 was prepared for comparison. Sample (2) was produced by the same production method as sample (1), but the molding die was not irradiated with excimer light and the coat layer material was not applied. The surface of sample 2 was also analyzed by an X-ray photoelectron spectrometer (JPS-9000MX manufactured by JEOL Ltd.). The results are shown in Table 1 as sample 2 . [0067] [table 1]<img file="JP4909469B2_D0002.tif" />[0068] From Table 1, it can be seen that the surface of sample 1 has more nitrogen atoms (N) and less silicon atoms (Si) and fluorine atoms (F) than sample 2 . [0069] Nitrogen atom (N) is abundantly contained in N-vinylacetamide, but its proportion in the polymerized component of the lens body is low. Further, the silicon atom (Si) and the fluorine atom (F) are one of the main components in the polymerization component of the lens body, and are not contained in N-vinylacetamide. [0070] Therefore, the surface analysis results in Table 1 suggest that the component of N-vinylacetamide, which is a coat layer material, is present on the surface of the lens polymer. [0071] Comparative example 1 In order to examine the treatment conditions of the mold surface, the state of the coat layer to be formed, the treatment conditions of the mold surface and the ease of desorption of the lens material after polymerization, several types of molding molds having different surface treatments were prepared. [0072] The types of molding dies are: molding dies without surface treatment (mold A), molding dies with oxygen atmosphere reduced pressure plasma treatment (mold B), molding dies with nitrogen atmosphere reduced pressure plasma treatment (mold C), and helium. A molding die (mold D) subjected to atmospheric decompression plasma treatment and a molding die (mold E: same as Example 1) subjected to excimer light irradiation were used, and a lens polymer was produced using these. [0073] The manufacturing method is the same as that of Example 1 except for the surface treatment of the molding die. The conditions for plasma treatment are as follows. Atmospheric gas O<sub>2</sub>, N<sub>2</sub>, He Gas flow rate 10 [ml / sec] Decompression degree 60 [Pa] Output 10 [Watt] Processing time 5 [seconds] [0074] First, the surface condition after applying the coat layer material to the surface of the mold was visually observed and stereomicroscoped, and evaluated based on the following evaluation criteria. The results are shown in the upper part of Table 2. [0075] (Evaluation criteria) : A uniform coat layer is formed throughout the mold. Δ: The entire mold is coated, but the thickness of the coat layer is uneven. X: The coating substance is dispersed and the coat layer is not formed. [0076] Further, after the lens material is polymerized, the molding die is forcibly separated, but in the mold A, the mold B, the mold C, and the mold D, the interaction between the molding die and the coat layer is strong, so that the lens is damaged. Or it was often inseparable. The percentage of the lenses that could be recovered while maintaining their shape was evaluated as a percentage. The results are shown in the lower part of Table 2. [0077] [Table 2]<img file="JP4909469B2_D0003.tif" />[0078] From the results shown in Table 2, when the surface treatment of the molding mold is performed by plasma irradiation, it is possible to provide a scaffold for forming a good coat layer, but it becomes difficult to remove the lens material after polymerization. It turns out that it is not practical. On the other hand, the treatment of the mold surface by excimer light irradiation promoted the formation of a good coat layer, and the desorption work was also good. [0079] Reference example 1 The surface treatment effect of excimer light irradiation was confirmed using an atomic force microscope (AFM). [0080] [0080] Excimer light was irradiated to a polypropylene contact lens manufacturing mold using an irradiator (Ushio, Inc., UER20-172). Irradiation intensity at the measurement wavelength (172 [nm]) is 13.5 [mW / cm]<sup>2</sup>], And irradiation was carried out for 5 minutes at room temperature, normal pressure, and atmospheric atmosphere. [0081] The surface of the molded mold before and after irradiation was observed using a scanning probe microscope (manufactured by Seiko Instruments, SPI3800 / SPA300). The result is shown in figure 2. Fig. 2 (a) shows the mold surface before excimer light irradiation, and Fig. 2 (b) shows the mold surface after excimer light irradiation for 180 seconds. [0082] From FIG. 2, it can be seen that the undulations on the surface of the mold are smoothed by irradiation with excimer light. [0083] In addition, for the surface of the mold that was irradiated with excimer light for 0 seconds (that is, without surface treatment), 60 seconds, and 180 seconds, respectively, "average surface roughness (Ra [nm])" and "maximum height difference (PV)" [nm]) and root mean square roughness (RMS [nm]) were measured. The results are shown in Table 3. [0084] [Table 3]<img file="JP4909469B2_D0004.tif" />[0085] The results in Table 3 suggest that the undulations on the mold surface were smoothed as a result of the excimer irradiation eroding the mold surface. Further, it can be seen that the longer the excimer light irradiation time, the smoother the surface of the mold. Therefore, by controlling the illuminance and time of excimer light irradiation, it is possible to smooth the mold and provide a desired surface roughness. [0086] Comparative example 2 In order to examine the coating method of the coat layer and the state of the coated layer to be formed, the coating method of the coat layer and the ease of desorption of the lens material after polymerization, the coating method of the coat layer was changed to prepare a lens polymer. did. [0087] In Example 1 above, the solution of the coat layer material was sprayed using a spray. In addition, spraying was performed in a state where the molding die was rotated. [0088] On the other hand, here, as a comparative example, the molding die is immersed in the solution of the coat layer material (means A), the solution of the coat layer material is spread on the surface of the molding die with a brush (means B), and the solution of the coat layer material is sprayed. The coat layer material was applied by three methods of spraying using (means C). The molding die was not rotated. A lens polymer was produced by the same production method as in Example 1 described above, except for the coating method of the coat layer and the rotation of the molding die. [0089] First, the surface of the mold after coating the coat layer material was visually observed and observed with a stereomicroscope, and evaluation was performed based on the following evaluation criteria. The results are shown in the upper part of Table 4. [0090] (Evaluation criteria) : A uniform coat layer is formed on the entire molding die. Δ: The entire molding die is coated, but the thickness of the coating layer is uneven. ×: The entire molding die is coated, but the thickness of the coating layer is uneven and a liquid pool is formed in the dent. [0091] In addition, the percentage at which the lens shape was maintained and recovered when the molding die was forcibly separated after the lens polymerization was evaluated. The results are shown in the lower part of Table 4. [0092] [Table 4]<img file="JP4909469B2_D0005.tif" />[0093] From this result, in the method of immersing the molding die in the solution of the coating layer material (means A) and the method of spreading with a brush (means B), a liquid pool is generated in the dent of the molding die, and a good coat layer is obtained. It turns out that it cannot be formed. Further, even the method of spraying using a spray (means C) is not suitable for use as an ophthalmic lens material because the thickness of the coat layer is partially different. In addition, these coating methods did not adversely affect the desorption work. [0094] Comparative example 3 In Example 1, the coat layer material was sprayed while rotating the molding die to form the coat layer. [0095] Therefore, a comparative study was conducted on the rotation of the molding die and the state of the coated layer formed, and the rotation of the molding die and the ease of desorption of the lens material after polymerization. [0096] The coat layer is formed under three conditions: a condition in which the molding die is not rotated when the coat layer material is sprayed (condition A), a condition in which the mold is rotated at 100 rpm (condition B), and a condition in which the mold is rotated at 1000 rpm (condition C). For the others, a lens polymer was produced under the same conditions as in Example 1. [0097] First, the coating layer material was sprayed and applied to the surface of the molding die, and then the surface condition was observed visually and with a stereomicroscope, and evaluated based on the following evaluation criteria. The results are shown in the upper part of Table 5. [0098] (Evaluation criteria) : A uniform coat layer is formed throughout the mold. Δ: The entire mold is coated, but the thickness of the coat layer is slightly uneven. ×: The entire mold is coated, but the thickness of the coat layer is uneven. [0099] In addition, the percentage at which the lens shape was maintained and recovered when the molding die was forcibly separated after the polymerization of the lens material was evaluated. The results are shown in the lower part of Table 5. [0100] [Table 5]<img file="JP4909469B2_D0006.tif" />[0101] From the results shown in Table 5, it is shown that a uniform coat layer can be formed by spraying the coat layer material while rotating the molding die at about 1000 rpm. [0102] Example 2 As another embodiment of the present invention, a silicon-containing non-hydrous soft contact lens provided with a coat layer on the surface and a method for producing the same will be described. [0103] First, under the same conditions as in Example 1, a polypropylene contact lens molding mold was irradiated with excimer light. [0104] Next, a macromonomer (CA registration number 169873-86-3) (Chemical formula 2) consisting of methyl methacrylate, 2-hydroxybutyl methacrylate, allyl methacrylate and ethylene glycol dimethacrylate was dissolved in ethanol 3.0 [w / w%]. The ethanol solution of the above was prepared and sprayed on the surface of the mold rotating at 1000 [rpm] using a spray. [0105] [Chemical 2]<img file="JP4909469B2_D0007.tif" />[0106] After spraying, the rotation was maintained for 2 minutes to volatilize ethanol to form a coat layer of the macromonomer on the surface of the mold. It was confirmed by observation with the naked eye and a stereoscope that a uniform and even coat layer was formed. [0107] Further, the lens polymer was obtained by performing filling and polymerization of the lens material, desorption from the molding mold, solvent treatment and autoclave treatment under the same conditions as in Example 1. [0108] The surface of the obtained lens polymer was clearly eliminated from the stickiness as compared with the uncoated lens polymer having no coated layer. [0109] Example 3 As another embodiment of the present invention, a silicon-containing water-containing soft contact lens provided with a coat layer on the surface and a method for producing the same will be described. [0110] First, an excimer light was irradiated to a polypropylene contact lens manufacturing molding die (male mold and female mold configuration) using an irradiator (Ushio, Inc., UER20-172). Irradiation intensity at the measurement wavelength (172 [nm]) is 13.5 [mW / cm]<sup>2</sup>], And irradiation was carried out for 5 minutes at room temperature, normal pressure, and atmospheric atmosphere. [0111] Next, prepare a 3.0 [w / w%] butanol solution of polyvinyl alcohol (average molecular weight 1,700, saponification degree 88%) dissolved in 1-butanol, and mold the surface rotating at 1000 [rpm]. Was sprayed using a spray. [0112] After spraying, rotation was maintained for 10 minutes to volatilize butanol to form a coat layer of polyvinyl alcohol on the surface of the mold. It was confirmed by observation with the naked eye and a stereoscope that a uniform and even coat layer was formed. [0113] A compounding solution of an ophthalmic lens material consisting of the following polymerization components (the numbers indicate the composition by weight) was prepared and filled in the female mold of the molding mold; Urethane-containing polysiloxane macromonomer (Chemical formula 1) 40 parts 30 parts of 2-hydroxyethyl methacrylate 1-Butanol 30 parts Ethylene glycol dimethacrylate 1.0 part 2-Hydroxy-2-methyl-1-phenylpropan-1-one 0.2 part [0114] After assembling the male mold into this female mold, the polymerization was carried out by irradiating with ultraviolet rays using an ultraviolet irradiation device (manufactured by Eye Graphics Co., Ltd., UX0302-03). Irradiance intensity at measurement wavelength (365 [nm]) is 10.0 [mW / cm]<sup>2</sup>], And irradiation was performed for 10 minutes at room temperature. [0115] The molding die after the polymerization was forcibly separated, and one of the molding dies was separated from the lens polymer. At this time, the lens polymer was not damaged. Next, the mold with the lens polymer fixed on the surface was immersed in a 2-propanol / water (50/50) solution for 2 hours. By this immersion, the lens polymer was sufficiently swollen and completely removed from the mold. [0116] In order to facilitate the removal of the lens polymerization component and the unreacted residual component of the coat layer material, the lens polymer was transferred into 2-propanol and immersed for 1 hour. Then, in order to replace and remove 2-propanol, the lens polymer was transferred to distilled water and immersed for 2 hours. Further, this lens polymer was transferred to physiological saline and autoclaved at 121 ° C. for 20 minutes. [0117] When the cross section of the ophthalmic lens manufactured as described above was analyzed using an energy dispersive X-ray analyzer (JED-2140, manufactured by JEOL Ltd.), no Si component was observed on the surface. From this result, it can be inferred that a coat layer of polyvinyl alcohol is well formed on the surface of the obtained ophthalmic lens. [0118] [Effect of the invention] According to the present invention, it is possible to form a uniform and homogeneous coat layer on the surface of an ophthalmic lens. Further, a uniform and homogeneous coat layer can be obtained regardless of the lens molding type material and the coat layer material, and no special lens material is required. [0119] Further, since both the lens body and the coat layer can be formed by one polymerization reaction, the number of manufacturing steps can be suppressed, and an ophthalmic lens having a coat layer can be easily and inexpensively manufactured. Further, since the ophthalmic lens taken out from the molding die is not processed, the molded lens is not deformed, and an ophthalmic lens having a desired optical shape can be surely obtained. [Simple explanation of drawings] FIG. 1 is a mold used for manufacturing an eye lens and FIG. 1 (a) showing an eye lens material formed in the mold, and FIG. 1 is an enlarged view of part B of FIG. 1 (a). FIG. 1 (b) shows the lens material for the eye after detachment from the mold and FIG. 1 (c). FIG. 2 is FIG. 2 (a) showing the surface of the mold before excimer light irradiation, and FIG. 2 (b) showing the surface of the mold after excimer light irradiation. [Explanation of symbols] 2 male type 4 female type 6 Eye lens (body of eye lens) 8 Coat layer (coat layer for eye lenses)
2 priority claims, no other members on record
Priority claims2
| Document | Office | Kind | Date |
|---|---|---|---|
| 2001191303 | Japan | A | |
| JP20010191303 | – | – | – |
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Numbers
- Publication
- 4909469
- Publication, DOCDB
- 4909469
- Publication, EPODOC
- JP4909469B
- Application
- 191303
- Application, DOCDB
- 2001191303
- Application, EPODOC
- JP20010191303
Titles2
- Japanese
- 眼用レンズおよびその製造方法
- English
- Ocular lens and its manufacturing method
Classification
- CPC, 6
- B29C37/0032
- B29C35/0888
- B29C71/0009
- B29C2035/0827
- B29D11/00125
- B29L2011/0041
- IPC, 13
- B29C39 12
- A61L27 00
- B29C39 22
- B29D11 00
- C08J7 00
- C08J7 04
- G02C7 04
- B29K105 32
- B29L11 00
- C08L101 00
- B29C35 08
- B29C37 00
- B29C71 00