WO2005073290A1 - 光学部品用成形体およびその製造方法 - Google Patents
光学部品用成形体およびその製造方法 Download PDFInfo
- Publication number
- WO2005073290A1 WO2005073290A1 PCT/JP2005/001221 JP2005001221W WO2005073290A1 WO 2005073290 A1 WO2005073290 A1 WO 2005073290A1 JP 2005001221 W JP2005001221 W JP 2005001221W WO 2005073290 A1 WO2005073290 A1 WO 2005073290A1
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- WIPO (PCT)
- Prior art keywords
- molded article
- optical component
- matrix
- optical
- refractive index
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B27/00—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
- G02B27/42—Diffraction optics, i.e. systems including a diffractive element being designed for providing a diffractive effect
- G02B27/46—Systems using spatial filters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/18—Diffraction gratings
- G02B5/1847—Manufacturing methods
- G02B5/1857—Manufacturing methods using exposure or etching means, e.g. holography, photolithography, exposure to electron or ion beams
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/18—Diffraction gratings
- G02B5/1866—Transmission gratings characterised by their structure, e.g. step profile, contours of substrate or grooves, pitch variations, materials
- G02B5/1871—Transmissive phase gratings
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
Definitions
- the present invention relates to a molded product for an optical component and a method for producing the same, and more particularly, to diffraction, deflection,
- the present invention relates to a molded article for optical parts such as an optical sheet or an optical film having optical characteristics such as diffusion and a method for producing the same.
- the molded article for an optical component of the present invention for example, there is an optical low-pass filter that suppresses the occurrence of moire in an image sensor using a CCD detector.
- Non-Patent Document 1 a structure in which block polymers are regularly arranged in a plane perpendicular to the film thickness direction has been proposed.
- the film-shaped ultraviolet-curable composition is irradiated with ultraviolet rays from a predetermined angle to cure the ultraviolet-curable composition.
- the second ultraviolet-curable composition is held in a film form on the ultraviolet-curable composition thus obtained, and in this state, the second ultraviolet-curable composition is cured by irradiating ultraviolet rays from another angle in this state.
- Patent Document 1 There has been proposed a structure in which portions having different optical characteristics are laminated in a direction perpendicular to the thickness direction of the substrate.
- Non-Patent Document 1 Maclomoecules 2003, 36, 3272-3288
- Patent Document 1 JP-A-63-309902
- Non-Patent Document 1 has an arrangement period on the order of "nanometers", a general arrangement requiring an arrangement period of about 80 nm to 1000 zm is required. It could not be used for optical applications.
- Patent Document 1 has a regularity on the order of sub-microns, and is not suitable for optical applications that require a high degree of light control due to low precision of the force arrangement. Had.
- the present invention has been made in order to solve such a problem, and a highly regular structure in which the refractive index periodically changes in the order of 80 nm and about 1000 ⁇ m has been developed. It is an object of the present invention to provide a molded article for an optical component which can be used for general optical applications such as an optical sheet and an optical film, and a method for producing the same.
- a molded article for optical parts obtained by photopolymerizing a photopolymerizable composition, comprising: a matrix; and a plurality of columnar structures arranged in one direction in the matrix.
- the columnar structure has a refractive index different from that of the matrix, and is arranged in a lattice in a plane perpendicular to the orientation direction, and the refractive index periodically changes in the order of 80 nm to 1000 ⁇ .
- a molded article for an optical component characterized by having a structure having high regularity, is provided.
- the diameter of the columnar structure is 80 nm or more and 100 Ozm or less.
- the arrangement period of the columnar structures is 80 nm or more and 1000 zm or less.
- a method for producing a molded article for an optical component comprising: forming a photopolymerizable composition containing a bifunctional or higher polyfunctional monomer or oligomer and a photopolymerization initiator. Injecting into a mold, irradiating the photopolymerizable composition with parallel light, polymerizing and curing the photopolymerizable composition, and forming a matrix and a large number of columnar structures arranged in one direction in the matrix. Forming a molded article for an optical component provided with the method for manufacturing a molded article for an optical component.
- the full width at half maximum of the wavelength of the parallel light is 100 nm or less.
- the light intensity distribution of the parallel light is substantially constant.
- a molded article obtained by photopolymerizing the photopolymerizable composition is formed on the molded article when the molded article is irradiated with a laser beam.
- a molded article for an optical component capable of obtaining a diffraction pattern reflecting a change in the periodic refractive index is provided.
- an object of the present invention is to provide a molded article for an optical component and a method for producing the molded article.
- FIG. 1 is a perspective view schematically showing a regular structure of a molded body 1 according to one embodiment of the present invention.
- the molding 1 is a molding for an optical component.
- the molded body 1 includes a matrix 2 in the form of a sheet or a film, and a large number of columnar structures 3 arranged in the matrix 2.
- the columnar structures 3 have a different refractive index from that of the matrix 2, are oriented in one direction (the thickness direction of the matrix 2), and are regularly arranged.
- the arrangement period of the columnar structures 3 is set to 80 nm to 1000 / im, and is preferably 90 nm, 5000 nm, and more preferably 100 nm, 500 nm.
- the diameter of the columnar structure 3 (in the case of a prismatic shape, the diameter of a circumscribed circle) is from 80 nm to 1000 / im, and is approximately 90 nm, is 5000 nm, and is more i.
- the lOOnm level is 500 ⁇ m.
- a columnar structure having an arrangement period or a diameter of the columnar structure 3 of less than 80 nm or greater than 1000 / im has no optical function because of a weak interference effect on light in a wavelength range of 350 nm to 2000 nm. Therefore, in the present embodiment, by setting the diameter of the columnar structure 3 to 80 nm to 1000 zm, it is required for a general optical component. Optical characteristics such as diffraction and deflection.
- the molded article 1 has a highly regular structure in which the refractive index periodically changes in the order of 80 nm to 1000 / im.
- Such a molded article is suitable for general optical applications because of its advanced light control, and can be used as an optical component such as an optical sheet or an optical film.
- the molded article 1 is formed by injecting a photopolymerizable composition into a predetermined mold, irradiating the photopolymerizable composition with light, and polymerizing and curing the composition.
- a photopolymerizable composition a composition containing a bifunctional or higher polyfunctional monomer or oligomer and a photopolymerization initiator can be used.
- the degree of polymerization tends to be increased or decreased in a plane perpendicular to the thickness direction of the photopolymerizable composition during polymerization and curing.
- a portion having a high degree of polymerization has a higher refractive index than a portion having a low degree of polymerization.
- bifunctional or higher functional polyfunctional monomer examples include, but are not particularly limited to, monomers having two or more polymerizable carbon-carbon double bonds in the molecule. Those containing a (meth) atalyloyl group, a vinyl group, an aryl group and the like are particularly preferred.
- (Meth) acrylate polyethylene glycol di (meth) acrylate, neopentyl diol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) ate , Hydrogenated dicyclopentagenenyl di (meth) acrylate, ethylene oxide-modified bisphenol A di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, tetramethylol Methanetetra (meth) acrylate, pentaerythritol hex (meth) acrylate, multifunctional epoxy Si (meth) acrylate, polyfunctional urethane (meth) acrylate, divinylbenzene, triaryl cyanurate, triallyl isocyanurate, triallyl trimellitate, diaryl chloren
- Particularly preferred polyfunctional monomers having three or more polymerizable carbon-carbon double bonds include trimethylolpropane tri (meth) atalylate, pentaerythritol tetra (meth) atalylate, and tetramethylonole methane tetra.
- the refractive index difference be 0.01 or more. It is more preferable that it is not less than 05.
- the difference in refractive index between at least two of the homopolymers must be within the above range.
- the two monomers or oligomers having the largest difference in the refractive index of the homopolymer are used in a weight ratio of 10:90 to 90:90 to obtain functions such as high-efficiency diffraction, deflection and diffusion.
- a monofunctional monomer or oligomer having one polymerizable carbon-carbon double bond in the molecule together with the polyfunctional monomer or oligomer described above is used. You can use it.
- a monofunctional monomer or oligomer those containing a (meth) atalyloyl group, a butyl group, an aryl group and the like are particularly preferable.
- the monofunctional monomer include, for example, methyl (meth) acrylate and tetrahydrofuran.
- Rufuryl (meth) atalylate ethyl carbitol (meth) atalylate, dicyclopentenyl oxochetyl (meth) atalylate, isobonyl (meth) atalylate, fenyl carbitol nore (meth) atalylate, noelfenoxicetyl (meta) )
- Atharylate 2-hydroxy-3-phenoxypropyl (meth) atalylate, (meth) atalyloyloxetyl succinate, (meth) atalyloyloxetyl phthalate, phenyl (meth) atalylate , Cyanoethyl (meth) acrylate, tribromophenyl (meth) acrylate, phenoxethyl (meth) acrylate
- These monofunctional monomers or oligomers are used for imparting flexibility to a molded article.
- the amount of the monofunctional monomer or oligomer is preferably in the range of 10 to 99% by mass, more preferably 10 to 50% by mass, based on the total amount with the polyfunctional monomer or oligomer.
- a homogeneous solution mixture containing the polyfunctional monomer or oligomer and a compound having no polymerizable carbon-carbon double bond can be used.
- the compound having no polymerizable carbon-carbon double bond include, for example, polystyrene, polymethyl methacrylate, polyethylene oxide, polybierpyrrolidone, polybier alcohol, polymers such as nylon, tonolene, n-hexane, Low molecular weight compounds such as cyclohexane, acetone, methinoethyl ketone, methyl alcohol, ethyl alcohol, ethyl acetate, acetonitrile, dimethylacetamide, dimethinolehonolemamide, tetrahydrofuran, organic halogen compounds, organic silicon compounds, plasticizers And additives such as stabilizers.
- the amount of the compound having no polymerizable carbon-carbon double bond is used in order to lower the viscosity of the photopolymerizable composition and to improve the handleability when producing a molded article.
- Government It 1 of the total amount of the capacity monomer or oligomer preferably by order to form a columnar structure having a regular Hai ⁇ 1J with may be the preferred tool handling properties in the range of 99 mass 0/0 Ranges from 1 to 50% by weight.
- the photopolymerization initiator used in the photopolymerizable composition is not particularly limited as long as it is used in ordinary photopolymerization in which polymerization is performed by irradiating active energy rays such as ultraviolet rays. It is not something.
- the amount of the photopolymerization initiator to be used is preferably in the range of 0.001 to 10 parts by weight with respect to 100 parts by weight of the other photopolymerizable composition, so as not to lower the transparency of the molded article. In order to reduce the amount of 0.01, it is more preferable to use 5 parts by weight.
- a large number of columnar structures 3 having a different refractive index from the matrix 2 are arranged in the matrix 2 in the negative direction.
- the columnar structures 3 are arranged with a two-dimensional regularity in a plane perpendicular to the orientation direction. Examples of the columnar structure include a columnar shape, an elliptical columnar shape, and a prismatic shape.
- This regularity is represented by a two-dimensional Bravais lattice composed of basic translation vectors a and b.
- the unit cell is any of the five kinds of cells shown in FIGS. 2 to 6, that is, square, hexagonal, simple rectangular, face-centered rectangular, and oblique. These unit cells are represented by the magnitudes of the vectors a and b shown in Table 1 and the angle ⁇ between them.
- FIG. 7 schematically shows a state in which the columnar structures 3 are arranged in a matrix 2) or in a square lattice
- This is preferable as an optical low-pass filter that generates an axial or biaxial diffraction pattern and allows multiaxial separation in one molded article.
- the hexagonal lattice includes a triangular lattice and a honeycomb lattice.
- the regularity is preferably such that diffraction patterns up to the first order as shown in FIG. Turn 4 is good
- the screen 8 When the molded body 1 of the present embodiment is placed at the position of the sample 7 in FIG. 9, and irradiated with the laser beam 6 from the laser light source 5 in the orientation direction of the cylindrical structure 3, the screen 8 has a cylindrical shape. A diffraction pattern 9 based on the regularity of the structure 3 is observed.
- a polymer solid As a method for evaluating a higher-order structure based on crystallization and phase separation of a polymer solid such as a plastic film, a polymer solid is irradiated with a laser beam, and a scattering pattern generated by reflecting the structure is detected. There is a method called a light scattering method.
- FIG. 10 shows an optical system used for the light diffusion method.
- the sample 7 is irradiated with the laser beam 6 from the laser light source 5 through the polarizer 10, and the scattered light caused by the internal structure of the sample 7 is projected on the screen 8 behind through the analyzer 11 to observe the scattering pattern 12.
- the arrow 13 indicates the polarization direction of the light after passing through the polarizer 10 and the analyzer 11.
- the optical system when the polarization direction is orthogonal is Hv scattering
- Vv scattering Information on the optical anisotropy of the sample can be obtained from the Hv diffuser L, and information on the density fluctuation and optical anisotropy of the sample can be obtained from the Vv scattering.
- the optical system shown in FIG. When the scattering pattern is projected on the screen 8 by the optical system from which the analyzer 11 has been removed, a diffraction pattern is obtained by the light interference effect based on the regular arrangement of the columnar structures. In the present invention, a diffraction pattern is obtained when a diffraction pattern as shown in FIG. 14 is observed.
- the shape of the molded article 1 of the present embodiment is particularly suitable for a sheet or film used as an optical component, but is not limited thereto.
- FIG. 11 shows the molding die 14, in which (a) is a plan view and (b) is a cross-sectional view.
- a light-transmitting member that does not absorb optically with respect to irradiation light is used.
- a transparent plastic material such as Neurex (registered trademark) glass, quartz glass, or fluorinated (meth) acrylic resin can be used.
- the molding die 14 can be of various shapes according to the shape of the molded article to be molded. For example, in the case of obtaining a film-shaped molded article other than a rectangular one as shown in FIG. In this case, a gap may be provided between two glass plates so that the photopolymerizable mixture is held in the gap.
- the photopolymerizable composition when the photopolymerizable composition is photopolymerized, the photopolymerizable composition is sealed in a molding die 14 so as not to be in contact with air so that the polymerization is not inhibited.
- the photopolymerizable composition is sealed in a molding die 14 so as not to be in contact with air so that the polymerization is not inhibited.
- the molding die 14 Preferably.
- the photopolymerizable composition is filled into the voids of the mold (cell) 14.
- the photopolymerizable composition encapsulated in the mold 14 is irradiated with parallel light such as ultraviolet light to polymerize and cure the photopolymerizable composition.
- parallel light such as ultraviolet light to polymerize and cure the photopolymerizable composition.
- the irradiated parallel light has a substantially constant light intensity distribution in a cross section orthogonal to the light traveling direction, in order to form a regular array of columnar structures.
- the light source is not particularly limited, but may be, for example, a point light source or a rod-shaped light source.
- the light is converted into a parallel light having a substantially constant light intensity distribution (hat-shaped distribution) by a mirror or a lens, or a planar light source such as a surface emitting semiconductor laser (VCSEL).
- VCSEL surface emitting semiconductor laser
- the parallelism of the irradiated light is preferably such that the beam spread angle is ⁇ 0.03 rad or less, more preferably ⁇ 0.03 rad, in order to form a regular array of columnar structures.
- the range is below OOlrad.
- the laser beam is a light source that is a preferable light source in terms of parallelism. Since the light intensity distribution has a Gaussian distribution, the light intensity distribution is made approximately constant using an appropriate filter or the like. Is preferred.
- the light intensity at a plurality of points (I to IX) in the irradiation area is measured, and the value of the illuminance distribution given by the following equation (1) is preferably 2.0% or less. % Or less is preferable.
- Illuminance distribution (maximum value-minimum value) / (maximum value + minimum value) X 100
- the full width at half maximum is preferably 100 nm or less, more preferably 20 nm or less.
- a photopolymerizable composition As a photopolymerizable composition, a mixture of 50 parts by mass of methyl methacrylate having a refractive index of a single polymer of 1.489 and 50 parts by mass of trimethylolpropane triatalylate having a refractive index of a single polymer of 1.535 is also used. A photopolymerizable composition in which 1 part by weight of 1-hydroxycyclohexyldifluoroketone was dissolved as a photopolymerization initiator was used.
- the obtained photopolymerizable composition was sealed in a film shape in a glass cell having a size of 50 mm ⁇ 50 mm and a thickness of 0.1 mm as shown in FIG.
- the divergence angle of the beam from the direction perpendicular to the surface of the upper cover 15 is ⁇ 0.001 rad or less
- the illuminance distribution in the light intensity distribution in the section perpendicular to the traveling direction of light is 2.0. % Or less
- the photopolymerizable composition was polymerized and cured to obtain a plastic film.
- the light source used was a collimated UV irradiation device using an ultra-high pressure mercury lamp with an emission spectrum as shown in Fig. 13. did.
- the obtained plastic film was irradiated with a laser beam having a wavelength of 532 nm from the film thickness direction as shown in FIG. 9, and the diffraction pattern was evaluated.
- FIG. A diffraction pattern was observed due to the arrangement of the columnar structures with a diameter of 2 microns in a hexagonal lattice with a period of 5 microns in a plane perpendicular to the film thickness direction inside.
- the obtained plastic film was observed with a polarizing microscope, and the image is shown in FIG. In the Fourier transform image of this polarized light microscope image, as shown in FIG. 16, a pattern due to the arrangement of the columnar structures in a hexagonal lattice pattern 1J was observed.
- the photopolymerizable composition is irradiated with ultraviolet light having a divergence angle of ⁇ 0.0OOlrad or less and an illuminance distribution of 2.0% or less in a light intensity distribution in a cross section perpendicular to the light traveling direction.
- the light source used was a collimated UV irradiation device using an ultra-high pressure mercury lamp having an emission spectrum as shown in Fig. 13, and a UV transmission filter (Suruga Seiki U360) with a wavelength of 250 nm with a full width at half maximum of 100 nm. Or 400 nm ultraviolet light was used.
- Example 2 When the diffraction pattern of the obtained plastic film was evaluated in the same manner as in Example 1, a columnar structure having a diameter of 2 ⁇ m in a plane perpendicular to the film thickness direction inside the polymer was obtained in the same manner as in Example 1. A diffraction pattern was obtained due to the arrangement of the bodies in a hexagonal lattice with a period of 6 microns.
- photopolymerizable composition 100 parts by mass of trimethylolpropane triatalylate having a refractive index of a single polymer of 1.535, and 1 part by mass of a photopolymerization initiator of 2-benzyl-2-methylamino-1_ ( 4_morpholinofinyl) -butanone-1 dissolved in photopolymerizable composition It was used.
- a parallel light ultraviolet irradiation device using an ultra-high pressure mercury lamp having an emission spectrum as shown in Fig. 13 was used, and the divergence angle was ⁇ 0.001 rad or less, and light in a cross section perpendicular to the light traveling direction was obtained.
- Ultraviolet light having an illuminance distribution of 2.0% or less in the intensity distribution was irradiated to a glass cell filled with the photopolymerizable composition without passing through an optical filter or the like to obtain a plastic film.
- the diffraction pattern of the obtained plastic film was evaluated in the same manner as in Example 1. As a result, a light scattering image shown in FIG. 17 was obtained, and no characteristic pattern was observed.
- the obtained plastic film was observed with a polarizing microscope, and the image is shown in FIG. No characteristic pattern was observed in the Fourier transform image of the polarizing microscope image.
- FIG. 1 is a drawing schematically showing a molded article of the present invention.
- FIG. 2 is an explanatory diagram of a square lattice.
- FIG. 3 is an explanatory diagram of a hexagonal lattice.
- FIG. 4 is an explanatory diagram of a simple rectangular lattice.
- FIG. 5 is an explanatory diagram of a face-centered rectangular lattice.
- FIG. 6 is an explanatory diagram of an oblique lattice.
- FIG. 7 is a drawing schematically showing a regular arrangement of columnar structures of a molded article of the present invention.
- FIG. 8 Drawing schematically showing the next diffraction pattern
- FIG. 9 is a schematic configuration diagram for measuring a diffraction pattern of a molded product.
- FIG. 10 is a schematic configuration diagram of an optical system of a light scattering method.
- FIG. 11 shows the structure of a cell which is a molding die for producing the molded article of the present invention, where (a) is a plan view and (b) is a cross-sectional view.
- FIG. 12 is a drawing showing measurement points for measuring the illuminance distribution of irradiation light.
- FIG. 13 is a drawing showing an emission spectrum of the extra-high pressure mercury lamp used in the present invention.
- FIG. 14 is a drawing showing diffraction spots observed on the molded article of the present invention.
- FIG. 15 is a drawing showing a polarizing microscope image of a molded article of the present invention.
- FIG. 16 A drawing showing a Fourier transform image of a polarizing microscope image of the molded article of the present invention.
- Garden 17 is a drawing showing a light scattering image observed in a molded article of a comparative example.
- Garden 18 is a drawing showing a polarizing microscope image of a molded article of a comparative example.
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- Polymers & Plastics (AREA)
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Abstract
Description
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Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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EP20050709447 EP1710273B1 (en) | 2004-01-30 | 2005-01-28 | Optical component-use molding and production method therefor |
KR1020067017446A KR100874558B1 (ko) | 2004-01-30 | 2005-01-28 | 광학 부품용 성형체 및 그의 제조방법 |
US11/494,627 US20060263583A1 (en) | 2004-01-30 | 2006-07-28 | Shaped article for use as an optical component and method of producing the shaped article |
US12/938,243 US8828283B2 (en) | 2004-01-30 | 2010-11-02 | Method of producing a shaped article for use as an optical component |
Applications Claiming Priority (2)
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JP2004-024354 | 2004-01-30 | ||
JP2004024354 | 2004-01-30 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US11/494,627 Continuation US20060263583A1 (en) | 2004-01-30 | 2006-07-28 | Shaped article for use as an optical component and method of producing the shaped article |
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WO2005073290A1 true WO2005073290A1 (ja) | 2005-08-11 |
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Family Applications (1)
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PCT/JP2005/001221 WO2005073290A1 (ja) | 2004-01-30 | 2005-01-28 | 光学部品用成形体およびその製造方法 |
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US (2) | US20060263583A1 (ja) |
EP (1) | EP1710273B1 (ja) |
KR (1) | KR100874558B1 (ja) |
CN (1) | CN100451051C (ja) |
TW (1) | TWI353457B (ja) |
WO (1) | WO2005073290A1 (ja) |
Cited By (1)
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JP2008194863A (ja) * | 2007-02-09 | 2008-08-28 | Mitsubishi Rayon Co Ltd | 成形体およびその製造方法 |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US8173329B2 (en) | 2006-10-31 | 2012-05-08 | Mitsubishi Rayon Co., Ltd. | Molded product and method for manufacturing same |
TWI360669B (en) * | 2006-10-31 | 2012-03-21 | Mitsubishi Rayon Co | Molded body and method for producing molded body |
JP5354771B2 (ja) * | 2008-09-05 | 2013-11-27 | 富士フイルム株式会社 | 樹脂構造体の製造方法 |
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2005
- 2005-01-28 TW TW94102604A patent/TWI353457B/zh not_active IP Right Cessation
- 2005-01-28 EP EP20050709447 patent/EP1710273B1/en not_active Not-in-force
- 2005-01-28 WO PCT/JP2005/001221 patent/WO2005073290A1/ja active Application Filing
- 2005-01-28 CN CNB2005800032779A patent/CN100451051C/zh not_active Expired - Fee Related
- 2005-01-28 KR KR1020067017446A patent/KR100874558B1/ko not_active IP Right Cessation
-
2006
- 2006-07-28 US US11/494,627 patent/US20060263583A1/en not_active Abandoned
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2010
- 2010-11-02 US US12/938,243 patent/US8828283B2/en active Active
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JP2008194863A (ja) * | 2007-02-09 | 2008-08-28 | Mitsubishi Rayon Co Ltd | 成形体およびその製造方法 |
Also Published As
Publication number | Publication date |
---|---|
US20060263583A1 (en) | 2006-11-23 |
KR100874558B1 (ko) | 2008-12-16 |
EP1710273A1 (en) | 2006-10-11 |
TW200532250A (en) | 2005-10-01 |
US20110042838A1 (en) | 2011-02-24 |
CN100451051C (zh) | 2009-01-14 |
KR20060118001A (ko) | 2006-11-17 |
EP1710273B1 (en) | 2014-09-10 |
US8828283B2 (en) | 2014-09-09 |
CN1914259A (zh) | 2007-02-14 |
EP1710273A4 (en) | 2011-10-26 |
TWI353457B (en) | 2011-12-01 |
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