Patent Application
20100200740
The present invention relate to a method of molding a fluorores in and optic devices, and more particularly, to a method of precisely molding an amorphous perfluoro resin with an accuracy of submicron or less and optic devices molded of the resin.
Conventionally, synthetic quartz and acrylic resins have been used as precision optic devices having ultraviolet transparency. Particularly, quartz and magnesium fluoride have been used as a material for a neutron beam focusing device.
However, quartz is expensive, lower in workability than resins, and is not suitable for precision processing. The acrylic resin enables injection molding of complicated shapes by thermoplastic molding, is used generally as an optic material, but contains hydrogen with a large neutron scattering cross-section, and is not suitable for a material for a neutron beam focusing device. Further, magnesium fluoride is also very hard to perform high-precision processing.
Meanwhile, as a material with excellent ultraviolet transparency, attention is directed toward an amorphous perfluoro resin that is one of fluororesins.
Fluororesins typified by polytetrafluoroethylene (PTFE) are excellent in heat resistance, chemical resistance, water repellency, weatherability resistance, electrical insulating properties, etc. and used in various fields such as semiconductors, batteries and excellent weather resistant coatings due to their properties. Among the resins, the amorphous perfluoro resin is provided with aforementioned properties specific to fluororesins, while being amorphous, and therefore, has a feature of being transparent in a wide wavelength range of ultraviolet, visible and near-infrared regions. Further, as compared with the acrylic resin, the amorphous perfluoro resin is excellent in optical transparency in a wide wavelength range of from the ultraviolet region to infrared region, corrosion resistance, water repellency, oil repellency, etc.
From the figure, it can be understood that the ultraviolet transparency of the amorphous perfluoro resin is greatly excellent as compared with the acrylic resin.
However, generally, the fluororesin is hard to mold, and it is not possible to perform precision molding on the fluororesin. Particularly, an amorphous perfluoro resin is originally a fluororesin for thin-film coating for antireflection, water proof, water repellency, etc. and is supplied while being dissolved in a specific fluorine-containing solvent. Usually, the amorphous perfluoro resin solution is applied on a substrate, heated and dried, and the thin film is formed. However, when a mold is used as a substrate, since the formed thin film is not removed from the mold easily, it is not possible to fabricate a molded component as a single item.
When the amorphous perfluoro resin can be molded precisely, it is possible to manufacture high-performance optic devices with ultraviolet transparency, particularly, neutron beam focusing device with high efficiency.
In view of the above-mentioned conventional problem, it is an object of the invention to provide a method of precisely molding an amorphous perfluoro resin with an accuracy of submicron or less and optic devices molded of the resin.
Therefore, the present invention provides a method of molding an amorphous perfluoro resin characterized by having the steps of (a) dissolving an amorphous perfluoro resin in a solvent, (b) pouring a solution of the amorphous perfluoro resin in a first mold, (c) heating a vessel with the solution placed therein, thereby volatilizing the solvent, and forming the amorphous perfluoro resin in the shape of a plate, and (d) pouring the amorphous perfluoro resin formed in the shape of a plate in a second mold, and pressurizing from one surface side to the other surface side of the second mold while heating, where the amorphous perfluoro resin is molded into a desired shape.
Herein, the solvent in the step (a) is an aprotic fluorine-containing, solvent, and the first mold in the step (b) is made of a material where a surface in contact with the solution is excellent in smoothness. Then, the first mold in the step (b) is glass where a surface in contact with the solution is mirror-finished.
Further, the second mold in the step (d) is a mold with a desired shape. The second mold in the step (d) is comprised of mirror-finished glass on one surface side and a mold with a desired shape on the other surface side. Then, a heating temperature of the solution in the step (c) ranges from 50° C. to 300° C. Further, a heating temperature of the mold in the step (d) ranges from 50° C. to 300° C., and an applied pressure is adjusted corresponding to the heating temperature.
Herein, the optic device is a micro lens, Fresnel lens, grating lens, micro prism or grating, and the invention provides a neutron optic device that refracts or reflects a neutron and thereby controls its traveling direction. Then, the invention further provides a neutron lens, neutron focusing apparatus, neutron speed discrimination apparatus, neutron bender or neutron chopper comprised of the neutron optic device.
According to the invention, it is possible to manufacture precision optic devices made of an amorphous perfluoro resin that have not existed previously. Particularly, it is possible to fabricate precision optic devices (such as, for example, a micro lens, Fresnel lens, grating lens, micro prism, grating, etc.) with optical transparency from ultraviolet to infrared region and also excellence in corrosion resistance, water repellency, oil repellency and the like.
These precision optic devices are considered particularly being applied as an optical apparatus lens, prism, etc. in the ultraviolet region. Further, the amorphous perfluoro resin does not change polarization of the transmitted light, and therefore, can be used in a polarization optics system.
Moreover, by fabricating a thin-film Fresnel lens by the method of the invention, it is possible to manufacture a neutron beam focusing device with high efficiency not heretofore attained.
Further, by using the invention, it is possible to mass produce the precision optic devices as described above with ease, and it is thereby possible to provide the devices at low prices. Furthermore, the optic device of the invention is made of a fluororesin, and can be reduced in weight as compared with the conventional product. Still furthermore, according to the invention, since it is possible to perform fine molding, products can be made smaller in size.
1 Amorphous perfluoro solution
2 Vessel
3, 13 Plate-shaped amorphous perfluoro resin
4, 5, 15 Mold
In the invention, an amorphous perfluoro resin is an amorphous perfluoro resin dissolvable in a solvent, and preferable examples thereof are fluorine-containing polymers (hereinafter, referred to as fluorine-containing cyclic polymers) having a fluorine-containing aliphatic cyclic structure in a main chain dissolvable in a fluorine-containing solvent.
In this description, the fluorine-containing polymer having a fluorine-containing aliphatic cyclic structure in a main chain means that one or more carbon atoms constituting the fluorine-containing aliphatic ring are carbon atoms constituting the main chain of the fluorine-containing cyclic polymer. Among carbon atoms constituting the fluorine-containing aliphatic cyclic structure, carbon atoms constituting the main chain are derived from polymerizable double bonds of monomers constituting the fluorine-containing cyclic polymer.
For example, when the fluorine-containing cyclic polymer is a fluorine-containing polymer obtained by polymerizing cyclic monomers described later, two carbon atoms constituting the double bond are carbon atoms constituting the main chain.
Further, in the case of the fluorine-containing cyclic polymer obtained by cyclo-polymerizing monomers having two polymerizable double bonds, among four carbon atoms constituting two polymerizable double bonds, at least two carbon atoms are carbon atoms constituting the main chain.
The fluorine-containing aliphatic cyclic structure may be a cyclic structure that a ring is comprised of only carbon atoms, or may be a heterocyclic structure containing hetero atoms such as oxygen atoms and nitrogen atoms as well as carbon atoms. Preferable as the fluorine-containing aliphatic ring are fluorine-containing aliphatic rings having one or two ethereal oxygen atoms in the ring.
The number of atoms constituting the ring of the fluorine-containing aliphatic cyclic structure preferably ranges from 4 to 7. In other words, the fluorine-containing aliphatic cyclic structure is preferably a four-to-seven membered ring.
Preferable as the fluorine-containing cyclic polymer are fluorine-containing cyclic polymers (I′) and fluorine-containing cyclic polymers (II′) as described below. Fluorine-containing cyclic polymers (I′): Polymers having units based on a cyclic fluorine-containing monomer: Fluorine-containing cyclic polymer (II′): Polymers having unit s formed by cyclopolymerization of diene fluorine-containing monomers.
The “cyclic fluorine-containing monomer” is a monomer having a polymerizable double bond between carbon atoms constituting the fluorine-Containing aliphatic ring or a monomer having a polymerizable double bond between a carbon atom constituting the fluorine-containing aliphatic ring and a carbon atom that is not contained in the fluorine-containing aliphatic ring.
Preferable as the cyclic fluorine-containing monomer is a compound (1) or compound (II).
In the formula, X11, X12, X13, X14, Y11 and Y12 area fluorine atom, perfluoroalkyl group, or perfluoroalkoxy group independently of one another.
As the perfluoroalkyl group in X11, X12, X13, X14, Y11 and Y12, the carbon number preferably ranges from 1 to 7, and more preferably, from 1 to 4. The perfluoroalkyl group is preferably linear or branched, and more preferably, linear. More specifically, examples thereof are a trifluoromethyl group, pentafluoroethyl group and heptafluoropropyl group, and a trifluoromethyl group is particularly preferable.
As the perfluoroalkoxy group in X11, X12, X13, X14, Y11 and Y12, examples thereof are that an oxygen atom (—O—) is bound to the perfluoroalkoxy group.
A fluorine atom is preferable as X11.
X12 is preferably a fluorine atom, trifluoromethyl group, or perfluoroalkoxy group with the carbon number ranging from 1 to 4, and more preferably, a fluorine atom or trifluoromethoxy group.
X13 and X14 are preferably a fluorine atom or perfluoroalkyl group with the carbon number ranging from 1 to 4, and more preferably, a fluorine atom or trifluoromethyl group, independently of each other.
Y11 and Y12 are preferably a fluorine atom, perfluoroalkyl group with the carbon number ranging from 1 to 4, perfluoroalkoxy group with the carbon number ranging from 1 to 4, and more preferably, a fluorine atom or trifluoromethyl group, independently of each other.
In compound (1), X13 and X14 may be bound mutually to form the fluorine-containing aliphatic ring together with carbon atoms of bound X13 and X14.
The fluorine-containing aliphatic ring is preferably a four-to-six membered ring.
The fluorine-containing aliphatic ring is preferably a saturated aliphatic ring.
The fluorine-containing aliphatic ring may have an ethereal oxygen atom (—O—) in the ring. In this case, the number of ethereal oxygen atoms in the fluorine-containing aliphatic ring is preferably 1 or 2.
In compound (2), Y11 and Y12 may be bound mutually to form the fluorine-containing aliphatic ring together with carbon atoms of bound Y11 and Y12.
The fluorine-containing aliphatic ring is preferably a four-to-six membered ring.
The fluorine-containing aliphatic ring is preferably a saturated aliphatic ring.
The fluorine-containing aliphatic ring may have an ethereal oxygen atom (—O—) in the ring. In this case, the number of ethereal oxygen atoms in the fluorine-containing aliphatic ring is preferably 1 or 2.
Preferable specific examples of compound (1) include compounds (1-1) to (1-5).
Preferable specific examples of compound (2) include compounds (2-1) to (2-2).
The fluorine-containing cyclic polymer (I′) may be a homopolymer of the above-mentioned cyclic fluorine-containing monomer, or a copolymer of the cyclic fluorine-containing monomer and another monomer except such a monomer.
In addition, in the fluorine-containing cyclic polymer (I′), a rate of units based on the cyclic fluorine-containing monomer relative to the total of all the repetitive units constituting the fluorine-containing cyclic polymer (I′) is preferably 20 mole % or more, more preferably 40 mole % or more, and can be 100 mole %.
The another monomer is not limited particularly, as long as the monomer can be copolymerized with the cyclic fluorine-containing monomer. More specifically, examples thereof are a diene fluorine-containing monomer, tetrafluoroethylene, chlorotrifluoroethylene, perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), and perfluoro (propyl vinyl ether).
The “diene fluorine-containing monomer” is a monomer having two polymerizable double bonds and fluorine atoms. The polymerizable double bond is not limited particularly, and is preferably a vinyl group, allyl group, acryloyl group and methacryloyl group.
As the diene fluorine-containing monomer, compound (3) is preferable.
CF2═CF-Q-CF═CF2 (3)
In the formula, Q may have an ethereal oxygen atom, and is a perfluoro alkylene group with the carbon number ranging from 1 to 3 such that a part of fluorine atoms can be replaced with halogen atoms except the fluorine atom. Examples of the halogen atom except the fluorine atom are a chlorine atom and bromine atom.
When Q is a perfluoro alkylene group having ethereal oxygen atoms, the ethereal oxygen atoms in the perfluoro alkylene group may exist at one terminal of the group, at both terminals of the group, or between carbon atoms of the group. From the viewpoint of cyclopolymerization, the oxygen atoms preferably exist at one terminal.
As a unit formed by cyclopolymerization of compound (3), examples thereof are repetition units of following formulas (3-1) to (3-4).
Specific examples of compound (3) include following compounds:
CF2═CFOCF2CF═CF2
CF2═CFOCF(CF3)CF═CF2
CF2═CFOCF2CF2CF═CF2
CF2═CFOCF2CF(CF3)CF═CF2
CF2═CFOCF(CF3)CF2CF═CF2
CF2═CFOCFClCF2CF═CF2
CF2═CFOCCl2CF2CF═CF2
CF2═CFOCF2COCF═CF2
CF2═CFOC (CF3)2OCF═CF2
CF2═CFOCF2CF(OCF3)CF═CF2
CF2═CFCF2CF═CF2
CF2═CFCF2CF2CF═CF2
CF2═CFCF2OCF2CF═CF2
The fluorine-containing cyclic polymer (II′) may be comprised of only units formed by cyclopolymerization of the above-mentioned diene fluorine-containing monomer, or may be a copolymer having the units and other units except the units.
In addition, in the fluorine-containing cyclic polymer (II′), a rate of units formed by cyclopolymerization of the diene fluorine-containing monomer relative to the total of all the repetitive units constituting the fluorine-containing cyclic polymer (II′) is preferably 50 mole % or more, more preferably 80 mole % or more, and most preferably 100 mole %.
The other monomer is not limited particularly, as long as the monomer can be copolymerized with the diene fluorine-containing monomer. More specifically, examples thereof are cyclic fluorine-containing monomers such as compound (1) and compound (2) as described previously, tetrafluoroethylene, chlorotrifluoroethylene, perfluoro(methyl vinyl ether), perfluoro(ethyl vinyl ether), and perfluoro(propyl vinyl ether).
The average molecular weight of the fluorine-containing cyclic polymer ranges preferably from 3,000 to 1,000,000, and more preferably, from 10,000 to 300,000.
In addition, as a cyclopolymerization method, homopolymerization method, and copolymerization method of the above-mentioned monomers, for example, it is possible to apply conventional publicly known methods disclosed in Japanese Laid-Open Patent Publication No. H04-189880, etc.
Commercially available products of the fluorine-containing cyclic polymer include CYTOP (produced by ASAHI GLASS Co., Ltd.), etc.
In the invention, a solvent to dissolve the above-mentioned amorphous perfluoro resin is preferably a fluorine-containing solvent, and more preferably, an aprotic fluorine-containing solvent.
The molecular weight of the fluorine-containing solvent being excessively high results in not only increases in the viscosity of the fluorine-containing polymer solution, but also decreases in the solubility of the fluorine-containing polymer, and therefore, the molecular weight of the fluorine-containing solvent is preferably 1000 or less. Further, to increase the solubility of the fluorine-containing polymer, the fluorine content of the fluorine-containing solvent is preferably in the range of 60 percent to 80 percent by weight. Examples of the preferable fluorine-containing solvent include following solvents.
Examples of the aprotic fluorine-containing solvent are polyfluoro aromatic compound, polyfluoro trialkyl amine, polyfluoro alkane, polyfluoro cyclic ether and hydro fluoro ether (HFE). These aprotic fluorine-containing solvents may be used alone, or in combination of two or more kinds.
Examples of the polyfluoro aromatic compound include perfluorobenzene, pentafluorobenzene, 1,3-bis(trifluoromethyl)benzene and 1,4-bis(trifluoromethyl)benzene.
Examples of the polyfluoro trialkyl amine are perfluoro tributyl amine and perfluoro tripropyl amine.
Examples of the polyfluoro cyclic ether include perfluoro(2-butyl tetrahydrofuran).
Examples of the polyfluoro alkane are perfluoro hexane, perfluoro octane, perfluoro decane, perfluoro dodecane, perfluoro(2,7-dimethyloctane), 1,1,2-trichloro-1,2,2-trifluoroethane, 1,1,1-trichloro-2,2,2-trifluoroethane, 1,3-dichloro-1,1,2,2,3-pentafluoropropane, 1,1,1,3-tetrachloro-2,2,3,3-tetrafluoropropane, 1,1,3,4-tetrachloro-1,2,2,3,4,4-hexafluorobutane, perfluoro(1,2-dimethylhexane), perfluoro(1,3-dimethylhexane), perfluoro cyclohexane, perfluoro(1,3,5-trimethylcyclohexane), 2H,3H-perfluoropentane, 1H-perfluorohexane, 1H-perflurooctane, 1H-perfluorodecane, 1H,1H,1H,2H,2H-perfluorohexane, 1H,1H,1H,2H,2H-perfluorooctane, 1H,1H,1H,2H,2H-perfluorodecane 3H,4H-perfluoro-2-methylpentane, 2H,3H-perfluoro-2-methylpentane, 1H-1,1-dichloro perfluoropropane and 1H-1,3-dichloro perfluoropropane.
The hydro fluoro ether (HFE) is preferably an HFE represented by general formula R1—O—R2 (R1 is a linear or branched polyfluoro alkyl group with the carbon number ranging from 5 to 12 that may have an ether bond, and R2 is a linear or branched alkyl group with the carbon number ranging from 1 to 5.)
When the carbon number of R1 is 4 or less, it is hard to dissolve the fluorine-containing polymer, and since the R1 with the carbon number being 13 or more is hard to commercially get, the carbon number of R1 is selected from the range of 5 to 12. The carbon number of R1 preferablyranges from 6 to 10, and more preferably, from 6 to 7 and from 9 to 10.
The polyfluoro alkyl group is a group where two or more hydrogen atoms of the alkyl group are replaced with fluorine atoms, and includes perfluoro alkyl groups where all the hydrogen atoms of the alkyl group are replaced with fluorine atoms, and groups where two or more hydrogen atoms of the alkyl group are replaced with fluorine atoms while one or morehydrogen atoms of the alkyl group are replaced with halogen atoms except the fluorine atom. The halogen atom except the fluorine atom is preferably a chlorine atom.
The polyfluoro alkyl group is preferably a group where 60% or more of the number of hydrogen atoms of a corresponding alkyl group are replaced with fluorine atoms, and more preferably, a group where 80% or more of such a number are replaced with fluorine atoms. The polyfluoro alkyl group is further preferably a perfluoro alkyl group.
In the case of R1 having an ether bond, since the solubility is inhibited when the number of ether bonds is too high, the number of ether bonds in the R1 preferably ranges from 1 to 3, and more preferably, 1 or 2. When the carbon number of R2 is or more, the solubility of the polymer containing the fluorine-containing cyclic structure is extremely inhibited. Preferable examples of R2 are a methyl group or ethyl group.
Examples of the HFE are F(CH2)5OCH3, F(CH2)6OCH3, F(CH2)7OCH3, F(CH2)8OCH3, F(CH2)9OCH3, F(CH2)10OCH3, H(CH2)6OCH3, (CF3)2CF(OCH3)CFCF2CF3, F(CF2)3OCF(CF3)CF2OCH3, F(CF2)3OCF(CF3)CF2OCF(CF3)CF2OCH3, F(CF2)8OCH2CH2CH3, (CF3)2CFCF2CF2OCH3, and F(CF2)2O(CF2)4OCH2CH3.
As the HFE, (CF3)2CF(OCH3)CFCF2CF3 is particularly suitable.
Among the fluorine-containing solvents except the above-mentioned solvents are fluorine-containing polyethers of low molecular weights, etc.
Embodiments of the invention will specifically be described below with reference to drawings.
As Embodiment 1, specific steps will be described below to precisely mold an amorphous perfluoro resin.
First, an amorphous perfluoro resin is dissolved in a perfluoro solvent (step S1).
Next, as shown in
Then, when the perfluoro solvent is volatilized by heating the vessel 2 with the amorphous perfluoro solution 1 placed thereinto 50° to 300° C., a plate-shaped amorphous perfluoro resin 3 is obtained as shown in
Next, as shown in
Thus, by forming an amorphous perfluoro resin in the shape of a thin film or plate and then heating and molding the resin while pressurizing, poor releasability from a mold is overcome which is the conventional problem, and it is possible to easily manufacture precise molded components such as a micro lens, etc. Then, the optic device manufactured by the molding method of the invention is excellent in ultraviolet transparency, corrosion resistance, water repellency, oil repellency and the like, and can be made an inexpensive light-weight small-size optic device.
As Embodiment 2, other specific steps will be described below to precisely mold an amorphous perfluoro resin.
First, an amorphous perfluoro resin is dissolved in a perfluoro solvent (step S11). Next, prepared is a vessel made of a material such as glass with good releasability against the amorphous perfluoro resin, and the amorphous perfluoro solution prepared in step S11 is poured into the vessel (step S12) (see
Then, when the perfluoro solvent is volatilized by heating the vessel with the amorphous perfluoro solution placed therein to 50° to 300° C., a plate-shaped amorphous perfluoro resin is obtained (step S13) (see
Next, as shown in
By the aforementioned method, it is possible to manufacture precision optic devices made of a fluororesin that have not existed previously. Particularly, it is possible to easily fabricate precision optic devices (such as, for example, a micro lens, Fresnel lens, grating lens, micro prism, grating, etc.) with optical transparency from ultraviolet to infrared region and further excellent in corrosion resistance, water repellency, oil repellency and the like.
These precision optic devices are considered particularly being applied as an optical apparatus lens, prism, etc. in the ultraviolet region. Further; the amorphous perfluoro resin used in the invention is amorphous, does not change polarization of the transmitted light, and therefore, can be used in a polarization optics system.
Moreover, by fabricating a thin-film Fresnel lens by the method of the invention, it is possible to manufacture a neutron beam focusing device with high efficiency not heretofore attained.
Optical characteristics and electric characteristics of the amorphous perfluoro resin used in the invention are as described below. In addition, herein, CYTOP (Trademark) is used as an example of the amorphous perfluoro resin.
Further,
In the invention, it is possible to mold optic devices exploiting these characteristics. More specifically, the invention is applicable to optical apparatuses as described below.
(1) Ultraviolet-Ray Disk
Each of optical disks (Blue-ray Disk, HDD and DVD) with high recording densities currently in practical use applies light (blue light) with a wavelength of 405 nm. By using a fine lens for ultraviolet-ray manufactured by the invention, since light (ultraviolet light) with a wavelength of about 200 nm can be used, it is possible to improve the recording density by about four times.
(2) Ultraviolet-Ray Camera
According to the invention, it is possible to take pictures in a wide wavelength range of from the infrared region to ultraviolet region.
(3) Ultraviolet-Ray Telescope
According to the invention, it is possible to observe celestial phenomena, etc. that cannot be observed in the visible region.
(4) Ultraviolet-Ray Microscope
According to the invention, it is possible to observe minute objects, phenomena, etc. that cannot be observed in the visible region.
(5) Broadband Spectrometer
According to the invention, it is possible to conduct spectral observations in a wide wavelength range of from the ultraviolet region to infrared region.
(6) Small-Size Ultraviolet-Ray Projector
By using the invention in a projection optics system of an ultraviolet light source, it is possible to actualize ultraviolet illumination, generation of ultraviolet-ray beams, and the like.
Further, by using the invention, it is possible to mass produce the precision optic devices as described above with ease, and it is thereby possible to provide the devices at low prices. Furthermore, the optic device of the invention is made of a fluororesin, and can be reduced in weight as compared with the conventional product. Still furthermore, according to the invention, since it is possible to perform fine molding, products can be made smaller in size.
In the foregoing, Embodiments of the invention are described, but the invention is not limited to the aforementioned Embodiments, and is capable of being modified in various manners based on the subject matter of the invention, and the modifications is not excluded from the scope of the invention.
The invention relates to a method of molding a fluororesin and optic devices, and more particularly, to a method of precisely molding an amorphous perfluoro resin with an accuracy of submicron or less and optic devices molded of the resin, and has industrial applicability.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2007-233890 | Sep 2007 | JP | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP2008/066189 | 9/8/2008 | WO | 00 | 3/29/2010 |
