WO2004068202A1 - 蓄熱効果を利用する自発的フロンタルポリメリゼーションによる屈折率分布型光伝送体の作製方法 - Google Patents
蓄熱効果を利用する自発的フロンタルポリメリゼーションによる屈折率分布型光伝送体の作製方法 Download PDFInfo
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- WO2004068202A1 WO2004068202A1 PCT/JP2004/000698 JP2004000698W WO2004068202A1 WO 2004068202 A1 WO2004068202 A1 WO 2004068202A1 JP 2004000698 W JP2004000698 W JP 2004000698W WO 2004068202 A1 WO2004068202 A1 WO 2004068202A1
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- refractive index
- index distribution
- monomer
- polymerization
- distribution type
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/02—Optical fibres with cladding with or without a coating
- G02B6/02033—Core or cladding made from organic material, e.g. polymeric material
- G02B6/02038—Core or cladding made from organic material, e.g. polymeric material with core or cladding having graded refractive index
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B3/00—Simple or compound lenses
- G02B3/0087—Simple or compound lenses with index gradient
Definitions
- the present invention relates to a method for producing a graded index (GRIN) optical transmission body in which a refractive index gradually changes from a central axis using spontaneous fluorocarbon polymerization using a heat storage effect. Further, the present invention relates to an optical transmitter such as an optical fiber or a lens manufactured by such a method.
- GRIN graded index
- a refractive index distribution type optical transmission body whose refractive index gradually changes from the central axis is a rod lens (cylindrical lens) having a convex lens action or a concave lens action, or a gradient index optical fiber.
- graded-index optical transmitters made of polymer materials have better impact resistance than graded-index optical transmitters made of quartz-based materials. Because of its light weight and flexibility, it has the advantages of being able to have a large diameter, easy end face treatment, and excellent economic efficiency. With respect to a method of manufacturing a graded-index optical transmission body made of a polymer material having such characteristics, the following methods have been conventionally proposed.
- Japanese Patent No. 1858593 focuses on the difference between the monomer reactivity ratio of two types of monomers and r 2 , and proposes a method for producing an optical transmission body having a refractive index gradient (refractive index distribution).
- the reactivity ratio is a measure of the hardness of the polymerization in the copolymerization.
- the polymerization vessel itself is formed of a polymer, and a monomer that dissolves the polymerization vessel is contained in the polymerization vessel.
- a mixture of a monomer having a larger molecular size or a low-molecular compound that does not participate in polymerization is injected, the inner wall of the polymerization vessel is brought into a gel state, and energy is irradiated from the outside of the polymerization vessel to perform polymerization. It shows a method in which the gel effect is induced on the inner wall of the container, polymerization is started from the inner wall of the polymerization tube, and gradually proceeds in the direction of the central axis. When only a monomer is used, copolymerization occurs.
- a monomer having a small molecular size easily enters the gel layer formed on the inner wall of the polymerization tube, so that a monomer having a large molecular size or a small molecule is placed near a central axis of a polymer finally formed.
- a composition distribution of monomer molecules or a composition of monomers and low molecules is formed from near the central axis to the peripheral direction.
- the finally produced optical transmission body must have a refractive index distribution by using a combination of monomers that will exhibit different refractive indices when the polymer is used as a monomer. become.
- the refractive index of the low molecular weight compound is different from the refractive index when the monomer used is polymerized to form a polymer, so that a refractive index distribution type is obtained. It becomes possible to manufacture an optical transmission body.
- a polymer monomer mixture having a polymerization rate of 50 to 90% is supplied from an outer discharge hole of a spinning spout having a double concentric discharge hole, and a colorless transparent liquid is supplied from an inner discharge hole.
- a monomer mixture containing a high refractive index compound or a polymer monomer mixture with a polymerization rate of 50% or less is supplied from an inner discharge hole.
- the high refractive index compound in the inner layer mixture is diffused into the outer layer mixture.
- a method of obtaining a refractive index distribution type optical transmission body by performing polymerization and further polymerizing is shown.
- Japanese Patent Application Laid-Open No. 6-194530 a method of forming a refractive index distribution at this time is performed by gradually dropping a monomer solution for polymerization in a polymerization vessel.
- Japanese Patent No. 241036 a method for initiating polymerization from the inner wall of a polymerization vessel is shown.
- a part of a core is formed by injecting a solution obtained by dissolving a high-refractive-index compound in a monomer inside a cylindrical polymerization container and polymerizing the solution while rotating.
- 1 shows a method of manufacturing an optical transmission body.
- Japanese Patent Application Laid-Open No. 8-62434 discloses a method of manufacturing a plastic optical fiber preform which is a refractive index distributed optical transmitter, in which a high refractive index polymer rod is formed and a low molecular compound having a high refractive index is formed outside the polymer rod.
- a solution with a reduced refractive index By injecting a solution with a reduced refractive index by changing the compounding ratio of the organic low-molecular-weight material, polymerizing while rotating as necessary, and repeating this operation several times, a refractive index distribution type optical transmitter is obtained. The method is shown.
- a device for applying pressure is used to prevent the formation of a cavity near the center formed when polymerization is performed from the periphery. This is a method for producing an optical transmission body.
- Patent 1858593 discloses a method that utilizes the difference in the reactivity ratio between monomers.
- the difference in the reactivity ratio and the value of r 2 makes it easier to form a refractive index distribution.
- the highly reactive monomer produces a homopolymer, and the macromolecules of the homopolymer are dispersed and present in the finally obtained optical transmitter (phase-separated state).
- the obtained optical transmission body becomes cloudy, and the optical transmission efficiency decreases.
- monomers with low reactivity have low reactivity, so it is difficult to complete the polymerization. Even after the polymerization operation is completed, the monomers remain as residual monomers, and post-treatment to remove these remains. May be necessary.
- the method disclosed in Japanese Patent Application Laid-Open No. 6-186441 requires a polymer solution to be extruded in advance, and further requires an apparatus for continuous extrusion. Equipment is required, which is very time-consuming. In addition, it is difficult to obtain a large-diameter gradient index lens by this method.
- the refractive index distribution is formed from the outside of the optical transmission body.However, since the refractive index distribution is gradually formed several times for each layer, It takes time and effort.
- Japanese Patent Application Laid-Open No. 8-62434 discloses a method of polymerizing from the vicinity of the center axis of the polymer. In this case, too, the polymer is formed one layer at a time, so that the It takes a lot of time, and at the same time, it is necessary to pay attention to the positioning in order to obtain a centrally symmetric optical transmitter.
- Patent Document 1 Patent 9765G7
- Patent Document 2 Patent No. 1858593
- Patent Document 3 JP-A-5-173026
- Patent Document 4 JP-A-5-241036
- Patent Document 5 JP-A-6-186441
- Patent Document 6 JP-A-6-194530
- Patent Document 9 JP-A-9-269424 DISCLOSURE OF THE INVENTION
- the present invention uses a simple apparatus without the need for pre-treatment and complicated equipment, and does not limit the material of the polymerization vessel, and the refractive index gradually changes from the central axis.
- the objective is to produce a graded-index optical transmission body, and to obtain a graded-index optical transmission body that is free of bubbles and cavities and has excellent transparency.
- An object of the present invention is to obtain a refractive index distribution type optical transmission body which has flexibility and can change its shape even at around room temperature.
- an object of the present invention is to fabricate the refractive index distribution type optical transmission body using spontaneous frontal polymerization utilizing a heat storage effect.
- the present inventors aimed to establish a method of easily producing a graded-index optical transmitter having excellent transparency without bubbles and cavities that could not be easily produced by the conventional method. We worked diligently.
- the present inventors have been studying the polymerization reaction from the standpoint of nonlinear kinetic analysis of autocatalytic chemical systems.
- the two types of self-promotion of the Tromsdorf effect and thermal runaway As a result, they found that the reaction progressed in the center of the reaction system and a high-temperature region appeared, forming an interface with the peripheral part called the front, which moved to the peripheral part.
- Such front formation is usually observed by intentionally overheating a part of the reaction system and artificially forming a temperature gradient, but it has been found that a spontaneous front formation by the heat storage effect is possible. .
- a target refractive index distribution type optical transmission body can be manufactured by the following method, and the present invention has been completed.
- a monomer and this monomer are polymerized into a polymer.
- a suitable polymerization initiator and polymerization temperature are set and polymerization is performed, the heat storage effect occurs at the center of the polymerization vessel.
- the spontaneous promotion of polymer formation from the center of the polymerization vessel by raising the temperature at the center of the polymerization vessel more than anywhere in the polymerization vessel.
- the interface between the formed polymer-rich portion and the monomer-rich portion becomes the front, which gradually progresses toward the inner wall of the polymerization vessel to form polymer.
- the polymer in the refractive index distribution type optical transmitter can be formed in which the monomers in the polymerization vessel are gathered at the center of the polymer as compared with the low molecular weight compound and have a distribution of the refractive index.
- frontal polymerization In general, in a polymerization reaction, a polymer form in which a front is formed by a polymer in the early stage of polymerization and the polymerization proceeds while moving is referred to as frontal polymerization.
- the present invention utilizes the heat storage effect to utilize the heat storage effect.
- the method is characterized in that a front is spontaneously formed at the center of the polymerization vessel, and polymerization is gradually progressed in the outer shape direction.
- a monomer having a low glass transition temperature as a monomer for forming the polymer of the present inventors, it is possible to produce a refractive index distribution type optical transmission body which has flexibility and can change its shape even at around room temperature. Was found.
- the present inventors have succeeded in producing a refractive index distribution type optical material by utilizing this spontaneous front formation phenomenon. According to the present invention, it has become possible to significantly reduce the production cost as compared with the conventional interfacial gel copolymerization method and doping method.
- the present invention is as follows.
- a method of manufacturing a refractive index distribution type optical transmission body in which a refractive index gradually changes from a central axis a monomer and a refractive index different from a refractive index when the monomer is polymerized into a polymer.
- the polymerization vessel is filled with a low-molecular compound having a polymerizable compound and a polymerization initiator.
- the polymerization initiator is selected from the group consisting of organic peroxides, persulfates, and azo compounds;
- (1 0) monomer is a Bok methacrylic acid hydroxyethyl E chill or glycerin monomethyl Takurire, production of graded index optical transmission element of the low-molecular compound is H 2 0 or adipic acid ester compounds (9) Method,
- the monomer is selected from the group consisting of octyl methacrylate, dodecyl methyl methacrylate, hexyl methacrylate, methacrylic acid-3,5,5-trimethylhexyl and -3-oxabutyl methacrylate (1 Any one of (1) to (1 3),
- Ethylene glycol dimethacrylate (EGDMA) as a flexibility modifier, Add a polyfunctional monomer selected from the group consisting of poly (ethylene glycol methacrylate) (PEGDMA), divinyl hexane diate (DAP), and divinylbenzene (DBz).
- PEGDMA poly (ethylene glycol methacrylate)
- DAP divinyl hexane diate
- DBz divinylbenzene
- Figure 1 is a photograph showing the progress of frontal polymerization.
- FIG. 2 is a photograph of an optical transmitter manufactured by the method of the present invention using methyl methacrylate as a monomer and methyl isobutyrate as a low molecular compound.
- FIG. 3 is a diagram showing a refractive index distribution of an optical transmission body manufactured by the method of the present invention using methyl methacrylate as a monomer and isobutymethyl as a low molecular compound.
- FIG. 4 is a diagram showing a refractive index distribution of an optical transmission body manufactured by the method of the present invention using methyl methacrylate as a monomer and methyl perryprate as a low molecular compound.
- FIG. 5 is a diagram showing a refractive index distribution of an optical transmission body manufactured by the method of the present invention using methyl methacrylate as a monomer and methyl caprylate as a low molecular compound.
- FIG. 6 is a diagram showing the W-type refractive index distribution of an optical transmission body manufactured by the method of the present invention using methyl methacrylate as a monomer and methyl methacrylate as a low molecular compound.
- FIG. 7 is a diagram showing the refractive index distribution of a flexible optical transmitter manufactured by the method of the present invention using octyl methacrylate as a monomer and benzyl methacrylate as a copolymerization monomer.
- FIG. 8 is a photograph showing the flexibility of the polymer shown in FIG. It is made by processing a polymer to a diameter of 15 mm and a thickness of 1.5 mni and bending it.
- the method of the present invention enables the production of a gradient index optical transmission body having an arbitrary shape and an arbitrary refractive index distribution by using a polymerization vessel having an arbitrary shape.
- the shape of the polymerization vessel used in the present invention may be a hollow spherical shape, a hollow egg-like shape, or a cylindrical shape, such as a cylindrical shape, in which a heat storage effect is induced.
- a container having the shape of a lens may be manufactured and used as a polymerization container.
- the heat storage effect means that when a polymerization vessel containing a raw material for an optical transmitter is heated inside, the reaction heat of the polymerization reaction initiated by the applied heat is more likely to be stored in the central part than in the peripheral part of the polymerization vessel.
- the shape in which the above-mentioned heat storage effect is induced means a shape in which the heat of reaction accompanying the polymerization can be concentrated at the center of the container. Since the central part where heat is stored is determined by the shape of the polymerization container, the polymerization can be started from an arbitrary position by designing the shape of the polymerization container. Further, since the polymerization vessel itself does not require reactivity, any material such as metal, plastic, glass, porcelain, and ceramic can be used. Further, an arbitrary shape can be formed by using a plastic material.
- the material of the light transmitting body of the present invention includes a monomer, a low molecular compound (also referred to as a dopant) having a refractive index different from the refractive index that is shown when this monomer is polymerized into a polymer, and a polymerization initiator. These materials are filled in the polymerization vessel.
- a polymerization initiator acts to accelerate the polymerization of the monomer in the center of the polymerization vessel and form a polymer front. The polymerization proceeds while moving from the center toward the inner wall of the polymerization vessel (frontal polymerization).
- Figure 1 shows a photograph showing the progress of the Freon evening report.
- the refractive index distribution type optical transmission body of the present invention has a feature that, when manufactured, the refractive index is distributed to the periphery of the optical transmission body, and that no air bubbles are observed inside.
- graded-index optical transmitter with a distributed index and no air bubbles inside could not be fabricated by conventional methods.
- the graded index optical transmission body of the present invention also has a feature that the refractive index distribution can be widened. For example, if the refractive index distribution is
- graded index optical transmitters ranging from 1.8 to 1.28.
- the refractive index distribution of the optical transmitter can be measured by a known method, for example, a non-destructive measurement method such as a lateral interference pattern method, a backscattering pattern method, a convergence method, a spatial filtering method, and a near-field pattern method.
- a destructive measurement method such as a longitudinal interference pattern method.
- the present invention also includes such an optical transmitter and a method for manufacturing the optical transmitter.
- Monomers that can be used in the present invention include polyfunctional monomers having one or more double bonds, such as an aryl group, an acryl group, a methyl group, and a vinyl group.
- polyfunctional monomers having one or more double bonds such as an aryl group, an acryl group, a methyl group, and a vinyl group.
- Styrene (1.592, 373), parachlorostyrene (1.610, 383), acrylonitrile (1.520, 370), methacrylonitrile ( 1.520), vinyl phenylacetate (1.567), vinyl benzoate (1.578, 314), vinylnaphthalene (1.682), methyl acrylate (1.480, 283), methyl methacrylate (1.
- Alkyl (meth) acrylate monomers are particularly preferred.
- the monomer may be copolymerized using a plurality of monomers, for example, but not limited to, octyl methacrylate and benzyl methacrylate.
- the refractive index distribution, flexibility, and the like of the optical transmitter can be adjusted depending on the type of the monomer to be copolymerized.
- the vicinity of room temperature, in such q conventional interfacial gel polymerization method refers to a temperature of between 10 ° C of 30 ° C, the glass transition temperature for using the tube made of a polymer of a monomer as a container Since a low transmission could not be used, it was impossible to produce a flexible transmission body.
- the glass transition temperature of the monomer used for producing a flexible optical transmitter is 300K or lower, preferably 250K or lower.
- Examples of such monomers include octyl methacrylate, dodecyl methacrylate, hexyl methacrylate, -3,5,5-trimethylhexyl methacrylate, and 3-oxabutyl methacrylate.
- the type and the concentration of the polyfunctional monomer described below are appropriately selected to give a certain degree of hardness.
- the softness of the refractive index distribution type optical transmission body having flexibility of the present invention is not limited, and can be arbitrarily soft depending on the application.For example, when used as an intraocular lens, the lens is bent. It is hard enough to completely bend a lens with a diameter of 15 and a thickness of 1.5, using tweezers to be worn inside the eye.
- the softness can be evaluated, for example, as follows.
- the lens of the present invention When the lens of the present invention with a diameter of 15 mm and a thickness of 1.5 cm is completely bent at room temperature (18 ⁇ -27 ° C) using tweezers, it can be bent without applying extra force. If it cannot bend without applying force, it is evaluated as B. If it cannot be bent, it is evaluated as C.
- the flexible lens of the present invention preferably has flexibility of A or B evaluation, and more preferably has flexibility of A evaluation. Further, the lens of the present invention has a shape recovering property that when bent in this way, it can easily be restored to its original shape by being left alone. For example, when the flexible lens of the present invention is bent under the above-described conditions and left to stand, it recovers to almost its original shape in a few seconds to over a dozen minutes.
- the low molecular compound (dopant) that can be used in the present invention is not limited, but in consideration of compatibility with the polymer material, propionic acid esters and disobutyric esters, phthalic esters and adipic esters. And the like.
- the molecular weight of the low molecular weight compound is larger than the molecular weight of the monomer used.
- the inside of the box indicates the refractive index.
- the refractive index of a low-molecular compound is different from the refractive index shown when a monomer used is polymerized to form a polymer, but may be larger or smaller than the refractive index of a polymer formed by monomer polymerization. It is good, but for use as an optical fiber or an artificial intraocular lens, the refractive index of a low molecular compound is smaller than that of a polymer made of a monomer. If it is small, a gradient index optical transmission body whose refractive index decreases outward from the central axis is obtained, and if it is large, the refractive index increases from the central axis outward. A distributed optical transmitter is obtained.
- an optical transmitter having a desired refractive index distribution can be manufactured.
- the type and mixing ratio of the monomer and the low-molecular compound to be used should be determined in consideration of the refractive index and solubility of the high-molecular compound and the low-molecular compound formed by polymerization of the monomer, and the ease of polymerization of the monomer. Can be done.
- both the monomer and the low molecular weight compound may include a plurality of types, and the mixing ratio of different types of monomers and the mixing ratio of different types of low molecular weight compounds are not limited.
- a monomer that is more easily polymerized will be polymerized at a more central portion of the optical transmitter.
- An optical transmitter having a desired refractive index distribution can be produced by selecting the type of the monomer and the low-molecular compound in consideration of the refractive index, solubility, polymerization of the monomer, and the like.
- the low molecular weight compound used to form the refractive index distribution is reactive with the monomer or reacts with itself as long as it provides a different refractive index from the monomer used. Such a substance may be used.
- biocompatibility refers to an attribute of a material that can coexist with a living body while performing its original function without giving an adverse effect or strong stimulation to the living body for a long period of time.
- Biocompatible monomers (meth) Akuriru hydroxyalkyl E chill, glycerol monomethacrylate and the like, biocompatible H 2 0 as a low-molecular compound, diisononyl adipate, hexyl adipate Echiru, adipic acid di-n-alkyl ( Adipate-based compounds such as those having 6, 8, 10, and 10 carbon atoms in the alkyl portion) can be exemplified, but are not limited thereto.
- the polymerization initiator is used as a mixture with a monomer and a low molecular compound.
- Known polymerization initiators can be used, but the polymerization reaction of the present invention proceeds at a relatively low temperature, preferably 50 ° C or lower, and therefore the polymerization initiator also operates at a relatively low temperature. It is preferable that the 10-hour half-life temperature is lower than the temperature at the time of polymerization, for example, about 40.
- the polymerization initiator used can be appropriately selected based on the 10-hour half-life temperature depending on the temperature at which the polymerization proceeds.
- polymerization initiator examples include azo-based compounds such as azobisisobutyronitrile and azobisisovaleronitrile, organic peroxides such as peroxycarboxylic acids and carboxylic esters, and persulfates. These can be used alone or in appropriate combination.
- azo-based compounds such as azobisisobutyronitrile and azobisisovaleronitrile
- organic peroxides such as peroxycarboxylic acids and carboxylic esters
- persulfates persulfates.
- 0.1 to 10% by weight may be mixed.
- persulfates are mainly used as aqueous polymerization initiators, and examples of persulfates include ammonium persulfate, sodium persulfate, and potassium persulfate.
- the peroxycapsulants include diisopropyl peroxydicarbonate (10-hour half-life temperature 40.5 ° C), g-n-propyl peroxyponic acid (40.5 ° C), bis (4-t-butylcyclohexyl) peroxydicarbonate (at 40.8), di (2-ethoxyxetyl) peroxydi-carbonate (43.4), di (2-ethylhexyl) peroxydicarbonate (43.5 °) C) and the like, and as peroxyesters, cumyl peroxy neodecanoate (36.5 ° C), 1,1,3,3 tetramethylbutyl peroxy neodecanoate (40 7 ° C), t-hexyl peroxy neo
- a molecular weight modifier can be used alone or in an appropriate combination.
- the molecular weight regulator include alkyl halides such as carbon tetrachloride and carbon tetrabromide, and butyl mercaptan, lauryl mercaptan, octyl mercaptan, dodecyl mercaptan, 2-hydroxyethyl mercaptan, and octyl thiocholate. Mercaps and the like.
- a polyfunctional monomer may be added as a crosslinking agent as long as the transparency of the produced polymer is not hindered. By doing so, the rigidity of the produced polymer is increased, and at the same time, the polymer is also excellent in chemical resistance.
- a multifunctional monomer is used to prevent the flexibility of the transmitter from becoming too large.
- Ethylene glycol dimethacrylate as a polyfunctional monomer Rate, divinylbenzene, ethylene glycol dimethacrylate (EGDMA), ethylene glycol polymethacrylate (PEGDMA), divinyl hexanoate (also known as divinyl adipic acid) (DAP), divinylbenzene (DBz), etc. .
- EGDMA ethylene glycol dimethacrylate
- PEGDMA ethylene glycol polymethacrylate
- DAP divinyl hexanoate
- DAP divinyl adipic acid
- DBz divinylbenzene
- octyl methacrylate, dodecyl methacrylate, hexyl methacrylate, methacrylic acid-3,5,5-trimethylhexyl-3-oxaxabutyl methacrylate were used as monomers to produce a flexible optical transmitter.
- ethylene glycol dimethacrylate ELDMA
- PEGDMA polyethylene glycol methacrylate
- DAP divinyl hexanoate
- the amount of the polyfunctional monomer to be added may be changed according to the rigidity and hardness required for the obtained optical transmitter.
- the polyfunctional monomer may be added in an amount of about 20% by weight based on the monomer, which is a case where a flexible transmitting body is manufactured.
- octyl methacrylate, dodecyl methacrylate, hexyl methacrylate, 3,5,5-trimethylhexyl methacrylate, or 3-oxabutyl methacrylate is used as a monomer, , 5% by weight or less, preferably 2% by weight or less.
- an antioxidant may be added, and examples of the antioxidant include hindered phenol and hindered amine.
- a solvent may be used.However, when a solvent is used, a solvent removal step after the polymerization is required, and since a harmful effect due to the removal of the solvent occurs, the solvent is usually used. It is desirable to carry out the polymerization reaction without using the monomer itself or a low molecular compound instead of the soot.
- a polymerization vessel is filled with a mixture of the above monomer, low molecular weight compound, polymerization initiator and the like at a predetermined mixing ratio, and polymerization is started.
- the mixing may be performed at the same time as the filling, or may be performed after filling in the polymerization vessel.
- the mixture is desirably replaced with nitrogen in order to prevent the polymerization from being inhibited by oxygen in the mixture.
- the polymerization vessel is allowed to stand and heated. The heating may be performed, for example, by placing a polymerization vessel containing the material under a predetermined temperature atmosphere.
- the present invention In the method, since polymerization is started from the center, bubbles are easily generated near the inner wall of the polymerization vessel due to volume shrinkage during polymerization. The reason for this is that the supply of monomers is stopped due to the increase in viscosity due to polymerization of the monomer due to heating of the polymerization vessel.However, polymerization at low temperatures makes it difficult for monomer polymerization to occur, so that viscosity does not increase. Since the supply of the monomer can be maintained, the generation of bubbles is suppressed.
- the heating temperature in the method of the present invention is 60 ° C or lower, preferably 50 ° C or lower, particularly preferably 45 or lower.
- the center of the container means the point where the container is equidistant from all points on the container surface, or the point where the container surface is symmetrical to it.
- heat is not always accurately stored at the center of the container depending on the shape of the container and the manner of heating, and polymerization is promoted near the center of the container.
- the center of the container means a portion near the center of the container as defined above.
- the temperature at which the polymerization is promoted can be appropriately adjusted by selecting a polymerization initiator having a specific 10-hour half-life temperature.
- a polymerization initiator having a 10-hour half-life temperature of 20 ° C. to 50 ° C. may be used.
- the polymerization is started from the center of the polymerization vessel, so the polymerization initiation site is determined by the shape of the vessel, and the polymerization initiation site, that is, the vessel where the maximum or minimum refractive index is the desired part, is appropriately set. Shape can be designed.
- the refractive index distribution type optical transmission in which the refractive index gradually changes from the central axis by the manufacturing method of the present invention.
- the refractive index distribution can be controlled by changing the type of the monomer and the low-molecular compound used as described above, and an optical transmitter having a desired refractive index distribution can be obtained. .
- the refractive index distribution type optical transmitter obtained by the production method of the present invention can be formed in a lump without processing by producing it using a polymerization container having a desired shape, or a polymerization container having an appropriate shape can be obtained.
- An optical transmission body having a desired shape can also be obtained by processing using such a method.
- the optical transmission body obtained by the method of the present invention can be polished and processed into a lens shape as a base material, or can be drawn and used as an optical fiber.
- the graded-index optical transmitter manufactured by the method of the present invention can be used as an optical fiber, a lens for eyeglasses, a contact lens, and the like.
- an optical transmitter having an arbitrary shape and an arbitrary refractive index distribution.
- an intraocular lens imitating an animal particularly a human lens. it can.
- a biocompatible material to produce an intraocular lens, and since the refractive index is as low as 1.3 to 1.4, a monomer with a low refractive index when polymerized and a small molecule with a low refractive index It is necessary to use a compound.
- One such monomer that satisfies these requirements is hydroxyethyl methyl methacrylate, and H 20 is a low molecular compound.
- the shape and refractive index distribution of the crystalline lens are known.
- the shape and refractive index distribution of an intraocular lens can be designed according to the description of Liu Longhui et al., Optics 30, 6 (2001) 407-413.
- the intraocular lens since the intraocular lens is folded and attached to the eye, it has an arbitrary shape and an arbitrary refractive index distribution according to the present invention, and has flexibility.
- the optical transmitter can be freely folded and attached to the eye. It can be used as a simple intraocular lens.
- the flexibility of the intraocular lens of the present invention is as described above.
- the flexible optical transmitter can be used not only for an intraocular lens but also for various uses.
- the intraocular lens of the present invention may contain an ultraviolet ray absorbent such as a bentriazol type ultraviolet ray absorbent, and a yellow pigment (for example, Solvent Yellow), an orange pigment (for example, Solvent Orange) And the like.
- an ultraviolet ray absorbent such as a bentriazol type ultraviolet ray absorbent
- a yellow pigment for example, Solvent Yellow
- an orange pigment for example, Solvent Orange
- MMA methyl methyl methacrylate
- methyl isobutyrate methyl isobutyrate
- azobisisobutyronitrile The solution mixed with 0.1 lg of AIBN was purged with nitrogen, poured into a cylindrical glass polymerization vessel having an inner diameter of 15 mm, and allowed to stand at 45 ° C. for 2 days for polymerization.
- Fig. 2 shows a photograph of the fabricated graded-index optical transmitter
- Fig. 3 shows the radial refractive index distribution of the transmitter.
- the vertical axis of the refractive index distribution indicates the refractive index
- the horizontal axis indicates the normalized radius, where 0 means the central axis of the polymer.
- FIG. 4 shows the refractive index distribution in the radial direction of the manufactured gradient index transmission body.
- the vertical axis is the refractive index
- the horizontal axis is the normalized radius
- 0 means the central axis of the polymer.
- Methyl methacrylate iOg as a monomer polymer refractive index is 1.492
- methyl perrylate as a low molecular weight compound 1.5 g (15 wt% based on monomer) (refractive index is 1.417)
- polymerization initiator A solution prepared by mixing 0.20 g of azobis (isoptyronitrile) (2.0% by weight with respect to the monomer) was replaced with nitrogen, and then poured into a cylindrical glass polymerization vessel having an inner diameter of 12 mDi and allowed to stand. In this state, polymerization was carried out at 50 ° C. for 1 day.
- Fig. 5 shows the refractive index distribution in the radial direction of the manufactured gradient index transmission body.
- the vertical axis represents the refractive index difference ( ⁇ ) when the refractive index at the central axis is 0, and the horizontal axis is This is the normalized radius, and 0 means the central axis of the polymer.
- FIG. 6 shows the refractive index distribution in the radial direction of the manufactured gradient index transmission body. As shown in the figure, a graded index transmitter having a W-shaped refractive index distribution was obtained.
- the vertical axis represents the refractive index difference ( ⁇ ) when the refractive index at the central axis is 0, and the horizontal axis is the normalized radius, where 0 represents the central axis of the polymer.
- EHMA octyl methyl methacrylate
- BzMA benzyl methacrylate
- EDMA Ethylene glycol dimethacrylate
- AIBN AIBN A solution containing 0.25 g (2.5 wt% based on the monomer) was replaced with nitrogen, and then poured into a cylindrical glass polymerization vessel having an inner diameter of 15 mni and allowed to stand at 45 ° C. For one day.
- FIG. 7 shows the refractive index distribution in the radial direction of the manufactured flexible refractive index distribution type transmitter.
- the vertical axis is the refractive index
- the horizontal axis is the normalized radius
- 0 means the central axis of the polymer.
- an optical transmission body having flexibility and capable of changing its shape near room temperature can be manufactured.
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- Optics & Photonics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
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JP2005504709A JP4270571B2 (ja) | 2003-01-31 | 2004-01-27 | 蓄熱効果を利用する自発的フロンタルポリメリゼーションによる屈折率分布型光伝送体の作製方法 |
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007034063A (ja) * | 2005-07-28 | 2007-02-08 | Keio Gijuku | 蓄熱効果を利用する自発的フロンタルポリメリゼーションによる改良された屈折率分布型光伝送体の作製方法 |
JP2012077227A (ja) * | 2010-10-04 | 2012-04-19 | Mitsubishi Rayon Co Ltd | 重合性組成物、アクリルフィルム及び光学部材 |
JP2016144648A (ja) * | 2006-02-08 | 2016-08-12 | キー メディカル テクノロジーズ インコーポレイテッド | 眼科適用のための紫外、紫及び青色光のフィルタリングポリマー |
US11529230B2 (en) | 2019-04-05 | 2022-12-20 | Amo Groningen B.V. | Systems and methods for correcting power of an intraocular lens using refractive index writing |
US11564839B2 (en) | 2019-04-05 | 2023-01-31 | Amo Groningen B.V. | Systems and methods for vergence matching of an intraocular lens with refractive index writing |
US11583389B2 (en) | 2019-04-05 | 2023-02-21 | Amo Groningen B.V. | Systems and methods for correcting photic phenomenon from an intraocular lens and using refractive index writing |
US11583388B2 (en) | 2019-04-05 | 2023-02-21 | Amo Groningen B.V. | Systems and methods for spectacle independence using refractive index writing with an intraocular lens |
US11678975B2 (en) | 2019-04-05 | 2023-06-20 | Amo Groningen B.V. | Systems and methods for treating ocular disease with an intraocular lens and refractive index writing |
US11944574B2 (en) | 2019-04-05 | 2024-04-02 | Amo Groningen B.V. | Systems and methods for multiple layer intraocular lens and using refractive index writing |
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Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007034063A (ja) * | 2005-07-28 | 2007-02-08 | Keio Gijuku | 蓄熱効果を利用する自発的フロンタルポリメリゼーションによる改良された屈折率分布型光伝送体の作製方法 |
JP2016144648A (ja) * | 2006-02-08 | 2016-08-12 | キー メディカル テクノロジーズ インコーポレイテッド | 眼科適用のための紫外、紫及び青色光のフィルタリングポリマー |
JP2018171469A (ja) * | 2006-02-08 | 2018-11-08 | キー メディカル テクノロジーズ インコーポレイテッド | 眼科適用のための紫外、紫及び青色光のフィルタリングポリマー |
JP2012077227A (ja) * | 2010-10-04 | 2012-04-19 | Mitsubishi Rayon Co Ltd | 重合性組成物、アクリルフィルム及び光学部材 |
US11529230B2 (en) | 2019-04-05 | 2022-12-20 | Amo Groningen B.V. | Systems and methods for correcting power of an intraocular lens using refractive index writing |
US11564839B2 (en) | 2019-04-05 | 2023-01-31 | Amo Groningen B.V. | Systems and methods for vergence matching of an intraocular lens with refractive index writing |
US11583389B2 (en) | 2019-04-05 | 2023-02-21 | Amo Groningen B.V. | Systems and methods for correcting photic phenomenon from an intraocular lens and using refractive index writing |
US11583388B2 (en) | 2019-04-05 | 2023-02-21 | Amo Groningen B.V. | Systems and methods for spectacle independence using refractive index writing with an intraocular lens |
US11678975B2 (en) | 2019-04-05 | 2023-06-20 | Amo Groningen B.V. | Systems and methods for treating ocular disease with an intraocular lens and refractive index writing |
US11931296B2 (en) | 2019-04-05 | 2024-03-19 | Amo Groningen B.V. | Systems and methods for vergence matching of an intraocular lens with refractive index writing |
US11944574B2 (en) | 2019-04-05 | 2024-04-02 | Amo Groningen B.V. | Systems and methods for multiple layer intraocular lens and using refractive index writing |
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JP4270571B2 (ja) | 2009-06-03 |
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