[go: up one dir, main page]

WO2005022208A1 - Plaque coulee en resine methacrylique a microstructure de surface et procede de fabrication de ladite plaque - Google Patents

Plaque coulee en resine methacrylique a microstructure de surface et procede de fabrication de ladite plaque Download PDF

Info

Publication number
WO2005022208A1
WO2005022208A1 PCT/JP2004/011921 JP2004011921W WO2005022208A1 WO 2005022208 A1 WO2005022208 A1 WO 2005022208A1 JP 2004011921 W JP2004011921 W JP 2004011921W WO 2005022208 A1 WO2005022208 A1 WO 2005022208A1
Authority
WO
WIPO (PCT)
Prior art keywords
methacrylic resin
cast plate
surface microstructure
plate
monomer mixture
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2004/011921
Other languages
English (en)
Japanese (ja)
Inventor
Masahiro Higuchi
Takanari Kusafuka
Yoshiaki Maeno
Nissho Iwamoto
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sanyo Electric Co Ltd
Sanyo Mavic Media Co Ltd
MSK Japan Co Ltd
Original Assignee
Sanyo Electric Co Ltd
Sanyo Mavic Media Co Ltd
MSK Japan Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sanyo Electric Co Ltd, Sanyo Mavic Media Co Ltd, MSK Japan Co Ltd filed Critical Sanyo Electric Co Ltd
Priority to JP2005513425A priority Critical patent/JPWO2005022208A1/ja
Publication of WO2005022208A1 publication Critical patent/WO2005022208A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/118—Anti-reflection coatings having sub-optical wavelength surface structures designed to provide an enhanced transmittance, e.g. moth-eye structures
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/12—Reflex reflectors
    • G02B5/122—Reflex reflectors cube corner, trihedral or triple reflector type
    • G02B5/124—Reflex reflectors cube corner, trihedral or triple reflector type plural reflecting elements forming part of a unitary plate or sheet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
    • B29C39/003—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor characterised by the choice of material
    • B29C39/006—Monomers or prepolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
    • B29C39/02—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B29C39/026—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of definite length, i.e. discrete articles characterised by the shape of the surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
    • B29C39/14—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of indefinite length
    • B29C39/148—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of indefinite length characterised by the shape of the surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
    • B29C39/22—Component parts, details or accessories; Auxiliary operations
    • B29C39/26—Moulds or cores
    • B29C39/265—Moulds or cores comprising two large plates positioned at a small distance from each other, e.g. for making panels
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2033/00—Use of polymers of unsaturated acids or derivatives thereof as moulding material
    • B29K2033/04—Polymers of esters
    • B29K2033/12—Polymers of methacrylic acid esters, e.g. PMMA, i.e. polymethylmethacrylate

Definitions

  • the present invention relates to a methacrylic resin cast plate having a surface microstructure and a method for producing the same.
  • the present invention relates to a methacrylic resin cast plate having a surface microstructure for realizing various optical characteristics such as antireflection and polarization separation, and a method for producing the same.
  • an optical element having an anti-reflection (AR) function has been used for a display of an electronic device, and an optical pickup having a polarization separation function has been used for an optical pickup for recording information on or reproducing information from an optical disk. Used.
  • These optical elements have a multilayer structure in which a plurality of layers are laminated on a substrate.
  • multilayer films having a multilayer structure have different refractive indices, and a desired optical function such as an AR function or a polarization separation function can be obtained due to the overall optical characteristics of the multilayer film.
  • the AR function is a function of suppressing the reflection and scattering of incident light and increasing the transmittance of an optical element. For example, when external light (incident light) is reflected or scattered on the surface of a display of a mobile phone or a computer, a so-called reflection that lowers visibility is generated. Therefore, in the case of a display, the reflectance on the display surface is generally reduced to avoid reflection and diffusion of incident light.
  • the polarization separation function is to allow only one of the P-polarized light and the S-polarized light having polarization planes orthogonal to each other to pass through the optical element, and reflect the other to form a P-polarized light. It is a function to separate S-polarized light from S-polarized light.
  • Patent Document 1 JP-A-11-312330
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2000-76685
  • Patent Document 3 JP 2001-201746 A
  • the thickness of each film constituting the multilayer film is The desired optical characteristics can be obtained by adjusting the parameters.
  • the types of film materials that can form a multilayer film are limited, and the degree of freedom in designing optical elements is low.
  • Patent Document 3 proposes a method of transferring a microstructure and a fine pattern to a flat plastic plate by mounting the die having a fine structure on a press machine and pressing the die against a transparent plastic plate. Te, ru.
  • An object of the present invention is to provide a methacrylic resin cast plate excellent in mass productivity and provided with a highly accurate surface microstructure, and a method for producing the same.
  • one embodiment of the present invention provides a methacrylic resin cast plate having a surface microstructure that achieves desired optical characteristics by changing an effective refractive index.
  • the methacrylic resin cast plate is formed by a filling polymerization in which a monomer mixture of a methacrylic resin is injected into a cell having at least one inner surface having a negative pattern corresponding to the surface microstructure. .
  • the monomer mixture is a monomer mixture containing methyl methacrylate as a main component.
  • the monomer mixture is a mixture containing 50% by weight or more of a methyl methacrylate monomer and another monomer copolymerizable with the methyl methacrylate.
  • the other monomeric methatalinoleic acid or its ester copolymerizable with the methyl methacrylate is used.
  • the other monomer copolymerizable with the methyl methacrylate is a polyfunctional unsaturated monomer.
  • the monomer mixture contains a radical polymerization initiator.
  • the monomer mixture contains a photopolymerization initiator.
  • the negative pattern has a surface on which a coating composition for surface treatment of the methacrylic resin cast plate is applied, and the methacrylic resin cast plate has the paint composition at the time of the encapsulation polymerization. It has a surface layer to which an object is transferred.
  • the transfer rate of the surface microstructure of the methacrylic resin cast plate to the negative pattern of the surface microstructure is 94% or more.
  • the surface microstructure is an antireflection structure in which conical protrusions having an aspect ratio of 1 or more and a pitch of 150 to 300 nm are provided in a matrix.
  • Another aspect of the present invention provides a method for producing a methacrylic resin cast plate having a surface microstructure that achieves desired optical characteristics by changing the effective refractive index.
  • the method comprises the steps of: preparing a cell having at least one inner surface having a negative pattern corresponding to the surface microstructure; injecting a monomer mixture of a methacrylic resin into the cell; A step of causing the body mixture to undergo a polymerization reaction in the cell; a step of removing the resin body solidified by the polymerization reaction from the cell; and a step of cutting the resin body into desired dimensions.
  • Still another embodiment of the present invention provides a method for producing a methacrylic resin cast plate having a surface microstructure that achieves desired optical characteristics by changing an effective refractive index.
  • the method includes the steps of providing a filling tank including a continuous cell of a belt conveyor type, wherein each cell has at least one inner surface having a negative pattern corresponding to the surface microstructure.
  • the monomer mixture contains a radical polymerization initiator
  • the step of causing the polymerization reaction includes a heat treatment step for accelerating the polymerization reaction of the monomer mixture.
  • the monomer mixture contains a photopolymerization initiator
  • the step of performing the polymerization reaction includes an ultraviolet irradiation treatment step for accelerating a polymerization reaction of the monomer mixture.
  • a coating composition for surface treatment of the methacrylic resin cast plate is coated on at least one inner surface having the negative pattern.
  • the method further includes a step of applying.
  • a step of manufacturing the mold having the negative pattern by electrical fabrication using the master, wherein the step of preparing the cell comprises: using the mold to form the at least one inner surface of the cell.
  • Irradiating the ultraviolet-curable resin with ultraviolet light to cure the ultraviolet-curable resin to form a resin layer having the negative pattern, wherein the step of preparing the cell comprises: Providing the at least one interior surface of the cell.
  • the step of preparing the cell includes providing the at least one inner surface using the mold or the resin layer having an area corresponding to a plurality of the masters.
  • the step of preparing the cell includes providing at least one inner surface having the negative pattern.
  • the method includes detachably attaching a member to be provided to the cell.
  • the step of manufacturing the master includes forming a surface in which conical protrusions having an aspect ratio of 1 or more and a pitch of 150 to 300 ⁇ m are arranged in a matrix.
  • the resin plate includes a resin substrate having a uniform composition and having at least one surface on which a surface microstructure exhibiting the optical characteristics is formed.
  • the surface microstructure includes a plurality of cone-shaped projections formed with a pitch of 150 to 300 nm, and the aspect ratio of each cone-shaped projection is 1 or more.
  • the optical resin plate includes a coating applied to a surface of the resin molded body so as to cover the plurality of conical protrusions.
  • the coating is a scratch-resistant coating that protects the plurality of conical protrusions. 28.
  • the resin substrate is made of a methacrylic resin.
  • the methacrylic resin is a polymer containing methyl methacrylate.
  • the methacrylic resin includes a copolymer of methyl methacrylate and another monomer.
  • the optical property is an anti-reflection property.
  • a methacrylic resin cast plate having a surface on which a microstructure pattern is transferred with an extremely high transfer rate can be obtained by being solidified through a polymerization reaction. Due to the surface microstructure, the cast plate is useful as an optical element having desired optical properties. Further, in the present invention, by adopting the built-in polymerization, the productivity is naturally improved, and a methacrylic resin cast plate having an extremely accurate surface microstructure can be provided in large quantities at low cost.
  • FIG. 1] (a)-(d) is a schematic cross-sectional view showing a manufacturing process of a master used for manufacturing a cast methacrylic resin plate according to the first embodiment of the present invention.
  • FIG. 2 (a)-(c) is a schematic cross-sectional view showing a manufacturing process of the master.
  • (D) is a schematic perspective view of the master.
  • FIG. 3 is a schematic view showing a mold forming process using a master.
  • FIG. 4 is a perspective view showing a step of forming a cell.
  • FIG. 5 is a perspective view showing a step of forming a cell.
  • FIG. 6 is a perspective view showing a cell forming process.
  • FIG. 7 is a plan view of FIG. 6.
  • FIG. 8 is a perspective view showing a step of forming a cell.
  • FIG. 9 is a cross-sectional view of the cell corresponding to the A-A cross section in FIG. 8;
  • FIG. 10 is a perspective view showing a step of injecting a monomer mixture.
  • FIG. 11 is a perspective view showing a polymerization step of a monomer mixture.
  • FIG. 12 is a perspective view showing a step of taking out a methacrylic resin cast plate.
  • FIG. 13 is a schematic perspective view of a methacrylic resin cast plate according to the first embodiment of the present invention.
  • FIG. 14 is a cross-sectional view of the cast plate of FIG. 13 taken along line BB.
  • FIG. 15 is a graph showing the relationship between reflectance and wavelength for an optical element having a methacrylic resin cast plate of the first embodiment and a conventional multilayer antireflection film.
  • FIG. 16 is a schematic view showing a method for producing a methacrylic resin cast plate that is effective in a second embodiment of the present invention.
  • FIG. 17 is a sectional view of a cell according to a second embodiment.
  • FIG. 18 is a sectional view showing a modification of the cell.
  • FIG. 19 is a perspective view showing a modified example of a large cell.
  • FIG. 20 is a schematic view of an apparatus for performing a continuous casting type bubble polymerization.
  • the methacrylic resin cast plate according to the first embodiment is provided with a surface having an extremely accurate microstructure.
  • the microstructure provides a high AR (anti-reflective or non-reflective) function.
  • the method of manufacturing a cast plate according to the first embodiment mainly includes the following steps A to D, and is repeated by at least one cell defined by two opposing flat plates or a plurality of flat plates.
  • the so-called batch casting method is used.
  • Step A A cell 27 (FIG. 9) in which a negative (reverse) pattern corresponding to a desired surface microstructure is provided on at least one cavity surface.
  • Step B Inject the methacrylic resin monomer mixture into the cell 27 (FIG. 10).
  • Step C The injected monomer mixture undergoes a polymerization reaction in the cell 27 (FIG. 11). The monomer mixture is solidified by the polymerization reaction.
  • Step D The solidified resin body (cast plate 30) is taken out of the cell 27, and the resin cast plate 30 is cut into a desired size (FIGS. 12 and 13).
  • the pretreatment step includes the following steps al and bl.
  • a resist is applied to the surface of the substrate to draw and develop a fine structure pattern, then an appropriate mask is formed, and etching is performed based on the mask to form a master having the fine structure (mother) Mold 13 is manufactured (Fig. 1 and Fig. 2).
  • the metal mold 14 used as a stamper for imparting a fine structure is manufactured by electric structure (Fig. 3).
  • step al first, as shown in FIG. 1A, a resist 11 is applied to a substrate 10 made of, for example, silicon (Si) or quartz. Then, a fine structure pattern is drawn on the resist 11 by electron beam drawing, two-beam interference exposure, or the like, and is developed to form a resist pattern shown in FIG. 1B.
  • a substrate 10 made of, for example, silicon (Si) or quartz.
  • chromium (Cr) is deposited from the surface side of the resist pattern. Only the chromium (Cr) film 12 is left by lift-off. Subsequently, by removing the resist 11, a chromium (Cr) mask 12a is formed on the substrate 10 as shown in FIG. 1 (d).
  • the pattern of the mask 12a is a fine pattern on the order of submicrons that is equal to or less than the wavelength of visible light, specifically a two-dimensional pattern having a repetition pitch P of 250 nm to 300 nm. In the first embodiment, when viewed from above, the mask 12a is a matrix pattern.
  • the surface 10a of the substrate 10 is etched using the chromium (Cr) mask 12a.
  • the substrate 10 is etched by reactive ion etching using a reactive gas. It is toching.
  • a reactive gas a mixed gas obtained by mixing CF and CHF at a predetermined ratio, or CHF can be used.
  • the etching conditions when using a mixed gas of CF and CHF are as follows.
  • Antenna power is high-frequency power applied to an antenna in an etching apparatus for plasma generation.
  • the bias power is a high-frequency power applied to draw plasma onto the substrate 10.
  • the mixing ratio of CHF in the reaction gas can be adjusted between 10-50%. If the proportion of CHF is lower than 10%, the angle of the recess removed by etching becomes too large, and the aspect ratio of the protrusion becomes less than 1.0. Conversely, if the proportion of CHF is higher than 50%, the concave portion removed by etching becomes a rounded u-shaped concave portion.
  • FIGS. 2A to 2C show the etching of the substrate 10 step by step.
  • the chromium (Cr) mask 12a which is not only the surface exposed from the chromium (Cr) mask 12a, is also gradually etched, and its diameter is reduced.
  • the surface of the substrate 10 has a cone-shaped (conical) projection 10b having a predetermined tip angle (taper angle) and has an anti-reflection function.
  • a surface microstructure is formed.
  • the etching conditions (such as the mixing ratio of C HF in the reaction gas) are determined so that the height T1 of the protrusion 10b is 00 to 500 nm.
  • the pitch P1 of the projection 10b corresponds to the pitch P in FIG. 1 (d).
  • a master 13 having a surface fine structure as shown in FIG. 2 (d) is manufactured.
  • a mold 14 is manufactured using the master 13 (step b).
  • the mold 14 is manufactured by, for example, an electric fabrication process using nickel (Ni).
  • a nickel (Ni) thin film is formed on the master 13 by a sputtering method.
  • the conductive film is formed with a thickness of several hundreds of A.
  • a nickel electrical structure is directly applied to the conductive film of the nickel thin film, and a metal layer made of the nickel is laminated.
  • the laminated metal layer is peeled off from the master 13 to obtain the mold 14.
  • the inverted structure (negative pattern) of the fine structure (fine pattern) of the master 13 is almost faithfully transferred to the mold 14 by such an electric structure.
  • the negative pattern may be called an inverted pattern.
  • step A is a step of forming the cell 27 provided with the negative pattern as described above.
  • the cavity 26 is defined by the two flat plates 20 and 22. Therefore, the flat plates 20 and 22 are preferably made of glass or metal which is not affected by a monomer mixture containing methyl methacrylate as a main component described later. In the first embodiment, the thickness of the two flat plates 20 and 22 is about 2.0-5. Ocm according to the thickness of the methacrylic resin cast plate.
  • FIG. 4 is an exploded perspective view showing a step of attaching the mold 14 to one of the two flat plates constituting the cell 27.
  • the mold 14 is attached to the first flat plate 20.
  • the outer dimensions of the first flat plate 20 are substantially the same as the outer dimensions of the mold 14.
  • a screw hole 20a for fixing the mold 14 is formed at each corner of the flat plate 20.
  • An opening (through hole) 14a corresponding to the screw hole 20a is formed at each corner of the mold 14.
  • the die 14 is placed on the upper surface of the flat plate 20 so that the surface on which the negative pattern (recess 14b) is formed is exposed, and the screw 21 is inserted into the opening 14a of the die 14 and the corresponding screw hole 20a of the flat plate 20. Is screwed in to fix the mold 14 to the flat plate 20. Thereby, the flat plate 20 integrally provided with the negative pattern is obtained.
  • the main component (main component) of the coating composition is a curable compound having a function of protecting the surface microstructure.
  • the curable compound is exposed to radiation such as ultraviolet rays or electron beams, or heated by a heat source such as hot air, hot water, or an infrared heater. Cures to form a scratch resistant film.
  • Additives such as conductive fine particles for realizing antistatic properties, a solvent for adjusting the viscosity of the paint, or a curing catalyst can be mixed with the curable compound.
  • curable compound examples include acrylate, urethane acrylate, epoxy acrylate, epoxy acrylate modified with epoxy group, polyester acrylate, copolymer acrylate, alicyclic epoxy resin, and glycidinole ether epoxy. Resins, butyl ether compounds, oxetane compounds and the like can be mentioned. Above all, curable compounds that impart high abrasion resistance to the film include radically polymerizable curable compounds such as polyfunctional acrylates, urethane acrylates, and epoxy acrylates, and alkoxysilanes. And thermosetting compounds such as alkylalkoxysilanes. Each of these curable compounds may be used alone, or a plurality of compounds may be used in combination.
  • curable compounds preferred are compounds having at least three (meth) acryloyloxy groups in the molecule.
  • compounds having at least three (meth) acryloyloxy groups in the molecule are preferred.
  • the exemplified monomer may be used as it is, an oligomer such as a dimer or trimer thereof may be used, or a monomer and an oligomer may be used in combination. Is also good.
  • the compound having at least three (meth) acroyloxy groups is preferably used in a content of 50 parts by weight or more, more preferably 60 parts by weight or more, based on 100 parts by weight of the solid content of the coating composition. If the content of the curable compound having at least three (meth) acryloxy groups is less than 50 parts by weight, the surface hardness may be insufficient.
  • the (meth) atalyloyloxy group refers to an atalyloyloxy group or a methacryloxy group.
  • the conductive inorganic particles that impart antistatic properties to the film include tin oxide doped with antimony, tin oxide doped with phosphorus, antimony oxide, zinc antimonate, titanium oxide, and titanium oxide. (Indium tin oxide) and the like.
  • the particle size of the conductive inorganic particles can be appropriately selected depending on the type of the particles, and is usually 0 or less. From the viewpoint of the antistatic property and transparency of the scratch-resistant film, the average particle diameter is preferably 0.001 ⁇ m or more and 0.1 / im or less. When the average particle size of the conductive inorganic particles exceeds 0.1 ⁇ m, the haze (haze value) of the scratch-resistant coating increases, and there is a concern that transparency may decrease.
  • the amount of the conductive inorganic particles to be used is generally about 2 to 50 parts by weight, preferably about 3 to 20 parts by weight, based on 100 parts by weight of the curable compound. If the amount of the conductive inorganic particles used is less than 2 parts by weight based on 100 parts by weight of the curable compound, the effect of improving the antistatic property will be poor. On the other hand, if the amount exceeds 50 parts by weight, the transparency of the cured film may be reduced.
  • the conductive inorganic particles can be produced by, for example, a gas phase decomposition method, a plasma evaporation method, an alkoxide decomposition method, a coprecipitation method, a hydrothermal method, or the like.
  • the surface of the conductive inorganic particles may be treated with, for example, a nonionic surfactant, a cationic surfactant, an anionic surfactant, a silicone coupling agent, an aluminum coupling agent, or the like. ,.
  • the solvent for adjusting the viscosity of the coating composition a solvent that can dissolve the curable compound and that volatilizes after the coating composition is applied is desirable.
  • the solvent include diacetone alcohol, methanol, ethanol, isopropyl alcohol, 1-methoxy-2-propyl Alcohols such as lopanol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate, 2-ethoxyethanol, 2 — Cellosolves such as butoxyethanol, and water.
  • the amount of the solvent used in the coating composition is not particularly limited, and is adjusted according to the properties of the curable compound.
  • the dispersion of the conductive inorganic particles in the coating composition can be promoted.
  • the conductive inorganic particles may be mixed with a solvent and then mixed with the curable compound, or the mixture of the curable compound and the solvent may be mixed with the conductive inorganic particles. May be.
  • a photopolymerization initiator be added to the coating composition.
  • the photopolymerization initiator include benzyl, benzophenone and derivatives thereof, thioxanthones, benzyldimethylketals, polyhydroxyalkylphenones, hydroxyketones, aminoalkylphenones, and acylphosphine oxides.
  • the amount of the photopolymerization initiator is generally in the range of 0.1 to 5 parts by weight based on 100 parts by weight of the curable compound.
  • the coating composition may be applied, the solvent may be volatilized, and then the curable film may be hardened, or the volatilization of the solvent and the curing of the curable film may be performed simultaneously. That is, they may be performed in parallel.
  • each square bar 23 is substantially equal to the thickness of the cast plate 30.
  • the thickness of the cast plate 30 is in a range of about 0.210 mm.
  • a tube 24 made of an elastic material such as a silicone resin is arranged along the square 23 inside the three squares 23.
  • the tube 24 has an outer diameter slightly larger than the thickness L of the square bar 23, that is, a desired thickness of the cast plate.
  • the first flat plate 20 and the second flat plate 22 face each other so that the square bar 23 and the tube 24 surround the negative pattern of the first flat plate 20.
  • the first flat plate 20 and the second flat plate 22 are fastened by a fastening member 25.
  • FIG. 9 corresponds to a cross-sectional view taken along line AA of FIG. 8 in a state where the cell 27 is completed.
  • a monomer mixture M containing methyl methacrylate as a main component is injected into the completed cell 27 (cavity 26).
  • the fastening member 25 is not shown.
  • the monomer mixture M a mixture containing 50% by weight or more of a methyl methacrylate monomer and another monomer copolymerizable with the methyl methacrylate is used.
  • Examples of the other copolymerizable monomers include (meth) acrylic acid and esters thereof.
  • Examples of (meth) acrylates include:
  • esters of (meth) acrylic acid with an alicyclic alcohol such as tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, and cyclohexyl (meth) acrylate.
  • esters of (meth) acrylic acid and alcohol such as esters of (meth) acrylic acid and aromatic alcohol such as benzyl (meth) acrylate;
  • Examples include hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate.
  • the (meth) acrylic acid-based monomers can be used alone or in combination of two or more, depending on the desired properties.
  • the (meth) acrylic acid monomer is a monofunctional unsaturated monomer having one radically polymerizable double bond in the molecule, and is a compound that can be copolymerized with the methacrylic acid monomer. It is.
  • Step C the monomer mixture M was polymerized in the senor 27 (cavity 26). Let react.
  • the monomer mixture M contains a radical polymerization initiator, and the monomer mixture M is heated to accelerate the polymerization reaction.
  • the timing of adding the radical polymerization initiator to the monomer mixture M is not particularly limited as long as it is before the polymerization reaction.
  • FIG. 11 shows the cell 27 into which the monomer mixture M has been injected.
  • a heat source such as hot air, hot water, or an infrared heater.
  • the heating temperature is 50 130 ° C
  • the heating time is several tens of minutes to several tens of hours.
  • the conditions for the heat treatment can be changed according to the type and amount of the radical polymerization initiator. Through the heat treatment, the polymerization reaction of the monomer mixture M is accelerated, and finally, the monomer mixture M is solidified to obtain a resin molded body (cast plate 30) having a uniform composition.
  • the abrasion-resistant film adhered to the surface of the first flat plate 20 (the negative pattern surface of the mold 14) is adsorbed by the resin molded body during this polymerization (embedding polymerization) process. It becomes the surface layer of the resin molded body.
  • radical polymerization initiator examples include:
  • Dialkyl peroxide initiators such as dicumyl peroxide, t-butyl tamyl peroxide, di-t-butyl peroxide, benzoyl peroxide, and lauroyl peroxide;
  • t_butyl peroxy_3,3,5_trimethylhexanoate t_butyl peroxy laurate
  • t_butynoleoxy isobutyrate
  • t-butynoleoxy acetate di-t_butynole Peroxyhexahydroterephthalate
  • di_t_ptinoleperoxyzelarate t-butinoleperoxy-1--2-ethynolehexanoate
  • 1,1,3,3-tetramethinolebutinoliveroxy_2_ Ethylhexanoate t-amyl peroxy_2_ethylhexanoate Any peroxyester-based initiator;
  • Percarbonate-based initiators such as t-butyl peroxyaryl carbonate and t-butyl peroxyisopropyl carbonate;
  • the above radical polymerization initiators can be used alone or in combination of two or more.
  • the added amount of the radical polymerization initiator is preferably 0.01 to 11 parts by weight per 100 parts by weight of the unsaturated monomer mixture containing methyl methacrylate as a main component. If the amount is less than 0.01 parts by weight, the polymerization reaction takes a long time. On the other hand, if it exceeds 1 part by weight, it may be difficult to control the polymerization reaction.
  • step D as shown in FIG. 12, the fastening of the first and second flat plates 20 and 22 is released to disassemble the cell 27, and the cast plate in which the monomer mixture M is solidified is formed. 30 is removed from the cell 27.
  • protrusions 30a to which a negative pattern has been transferred are formed on the surface of the methacrylic resin cast plate 30.
  • the pitch P2 of the protrusion 30a is 250 to 300 ridges
  • the height T2 is 300 to 500 ridges.
  • the methacrylic resin cast plate 30 integrally has a surface layer composed of the scratch-resistant film 30 b transferred from the surface of the mold 14.
  • FIG. 15 is a graph showing the relationship between the reflectance and the wavelength dependence of the cast plate 30 of the first embodiment and the AR optical element employing the conventional multilayer film.
  • TM indicates the characteristics of an AR optical element (prior art) employing a multilayer film formed by an evaporation method.
  • the MC shows the characteristics of the cast plate (the present invention) having a fine structure pattern in which the pitch and the aspect ratio of the projections 30a are 300 nm and 1, respectively.
  • Fig. 15 shows the measured characteristics of the abrasion-resistant coating 30b formed on the cast plate 30 in order to more accurately examine the relationship between the reflectance and the wavelength of the microstructure pattern. Indicated.
  • the AR optical element (TM) employing the multilayer film has a reflectivity of 1% or less in a wavelength region of about 400 ⁇ m 580 nm and a reflectivity in other wavelength regions. I can't keep it low.
  • the reflectivity is low in almost all wavelength regions of visible light, so that the cast plate 30 of the present invention has a high antireflection function. That is, it is understood that the cast plate 30 having the above-described fine structure pattern can realize a suitable non-reflection function in a wider wavelength range.
  • a monomer mixture M of a methacrylic resin is injected into a cell 27 in which a negative pattern having a surface microstructure for realizing an AR function is arranged, and this is subjected to a polymerization reaction in the cell 27, so-called A methacrylic resin cast plate 30 having a surface microstructure is manufactured by the incorporation polymerization.
  • the methacrylic resin cast plate 30 has a surface microstructure pattern that realizes the AR function with an extremely high transfer rate. Transcribed.
  • the productivity of the methacrylic resin cast plate 30 is improved by employing the built-in polymerization. Therefore, it is possible to provide a large amount of methacrylic resin cast plate 30 having an extremely accurate surface microstructure at a low cost.
  • a monomer mixture M containing 50% by weight or more of a methyl methacrylate monomer and another monomer copolymerizable with the methyl methacrylate is used.
  • a methacrylic resin cast plate 30 having high transparency, weather resistance and hardness can be obtained.
  • the monomer mixture M to which the radical polymerization initiator has been added is heated in the cell 27. This suitably promotes the polymerization reaction of the monomer mixture M.
  • a coating composition containing a curable compound and conductive fine particles was applied to the negative pattern surface of the mold 14.
  • the applied coating composition is adsorbed on the surface layer of a methacrylic resin cast plate having a fine surface structure, and a scratch-resistant film 30b is applied to the cast plate.
  • the scratch-resistant film 30b has a function of protecting the surface microstructure (hard coat) or an antistatic function, and improves the reliability and practicality of the methacrylic resin cast plate having the surface microstructure.
  • a molded article of a methacrylic resin is originally difficult to be surface-treated, but as described above, the coating composition is adhered to the polymerization reaction of the monomer mixture M of the methacrylic resin, so that the methacrylic resin is adhered. It is possible to perform an accurate surface treatment with a coating composition on the surface layer of the base resin.
  • the surface of the cast plate 30 is already covered with the scratch-resistant film 30b. Therefore, even when methyl methacrylate is used as the main agent, problems such as the intrusion of foreign matter between the cast plate 30 and the scratch-resistant film 30b are suppressed.
  • the cast plate 30 in which the surface microstructure is transferred at an extremely high transfer rate specifically, a transfer rate of 94% or more, is obtained.
  • a methacrylic resin cast plate 30 having an aspect ratio of 1 or more and a surface fine structure (antireflection structure) having a pitch of about 250 nm to 300 nm can be manufactured relatively easily. Since the pitch of 250 nm to 300 nm is shorter than all visible light wavelengths, the anti-reflection effect of the cast plate 30 is high. For example, if the methacrylic resin cast plate 30 is used for the display of various electronic devices, the reflection is suppressed and the visibility of the display is greatly improved.
  • the mold 14 serving as a stamper is manufactured by electrical fabrication based on the master 13 having a precise fine structure, so that the negative pattern itself can be formed with high precision. Made Power to make S Therefore, it is possible to reliably manufacture the cast plate 30 having desired optical characteristics.
  • the monomer mixture M of the methacrylic resin is cured with the same molecular weight.
  • thermal, chemical, and mechanical properties such as surface hardness, rigidity, heat resistance, strength, and solvent resistance are maintained higher than those of press molding or injection molding.
  • FIGS. 16 and 17 the same or corresponding elements as those in the first embodiment shown in FIGS. 1 and 15 are denoted by the same or corresponding reference numerals, respectively. A duplicate description of is omitted.
  • the methacrylic resin cast plate having a surface microstructure that is strong in the second embodiment is characterized in that an extremely accurate microstructure pattern transferred to the surface thereof enables highly accurate optically accurate AR ( (Reflection prevention or non-reflection) function is realized.
  • AR Reflection prevention or non-reflection
  • the second embodiment also employs a so-called batch-type casting method in which one or more cells 27a including two flat plates that partition the cavity 26 are repeatedly used, and the process of the first embodiment is performed. After A-D, a methacrylic resin cast plate with a surface microstructure is manufactured.
  • a mask pattern is used instead of a mold. Therefore, in a pre-processing step of manufacturing a negative pattern corresponding to a desired fine structure, a step b2 of forming a translucent mask pattern is performed after the step al of manufacturing a master.
  • Step b2 of forming a mask pattern will be described.
  • a substrate 10 having a surface (fine structure surface) 10a on which a fine structure including a conical protrusion 10b is formed is used as a master.
  • An ultraviolet curable resin is injected between the surface 10a of the substrate 10 and the flat plate 120 made of a highly translucent material such as glass or quartz.
  • the surface 10 a of the substrate 10 is brought into contact with the flat plate 120. Irradiate ultraviolet rays UV from the back surface 120a side of the flat plate 120 to The ultraviolet curable resin is cured on the plate 120 to form the resin layer 114.
  • the fine structure pattern of the substrate 10 is transferred to the resin layer 114 provided integrally with the flat plate 120 while being almost faithfully inverted. That is, a negative pattern including a concave portion 114b corresponding to the protrusion 10b of the substrate 10 is formed in the resin layer 114.
  • the coating composition is applied to the surface of the flat plate 120, or more precisely, the upper surface of the resin layer 114 on which the negative pattern is formed, and cured, whereby the scratch resistance is improved.
  • a film is formed (not shown).
  • the abrasion-resistant film is transferred to the surface of the methacrylic resin cast plate 30. It should be noted that a coating composition similar to that of the first embodiment can be used.
  • the cell 27a is manufactured in the same manner as in the step A of the first embodiment. That is, a flat plate 120 is used in place of the flat plate 20, a second flat plate 22, a square bar 23, and a tube 24 made of an elastic material such as a silicone resin are assembled in the above-described manner, and the two flat plates 120 and 22 are assembled. Fasten with the fastening member 25. Thus, the cavity 26 partitioned between the two flat plates 120 and 22 is sealed by the tube 24 to complete the cell 27a.
  • the cell 27a is basically the same as the cell 27 of the first embodiment, and the flat plates 120 and 22 face each other with a distance corresponding to the thickness of the square bar 23. are doing.
  • a resin layer 114 having a negative pattern is provided on one inner surface of the cell 27a that defines the cavity 26.
  • a monomer mixture M of a methacrylic resin mainly containing methyl methacrylate is injected into the senole 27a (cavity 26).
  • step C the injected monomer mixture M is subjected to a polymerization reaction.
  • ultraviolet irradiation treatment is performed to accelerate the polymerization reaction, and prior to this ultraviolet irradiation treatment, a photopolymerization initiator is added to the monomer mixture M in advance. deep.
  • one or a plurality of snoles 27a are housed in a polymerization tank (not shown), and the ultraviolet irradiation treatment is performed by a light source (not shown).
  • the scratch-resistant film (resin layer 114) formed on the surface of the flat plate 120 is adsorbed to the surface layer of the cast plate 30 in which the monomer mixture M has been solidified during the photopolymerization process.
  • Examples of the photopolymerization initiator that can be used in the second embodiment include benzyl, benzophenone and derivatives thereof, thioxanthones, benzyldimethyl ketals, polyhydroxyalkylphenones, hydroxyketones, and aminoketones. Examples thereof include alkylphenones and acylphosphine oxides.
  • a methacrylic resin cast plate 30 having a surface microstructure substantially similar to that shown in FIG. 14 is completed by Step D as in the first embodiment.
  • the resin layer 114 functioning as a negative pattern can be directly formed on the flat plate 120, the step of separately disposing the negative pattern can be omitted, and the working efficiency is further improved. I do.
  • the methacrylic resin cast plate having a surface microstructure according to the present invention and the method of manufacturing the same are not limited to the embodiments, but may be modified as follows, for example.
  • the mold 14 is fixed to the flat plate 20 by the screws 21, but the manner of fixing the mold 14 can be changed as appropriate.
  • an outer frame that matches the outer shape of the mold 14 may be formed on the flat plate 20 in advance, and the mold may be fitted into the outer frame.
  • the mold 14 and the flat plate 20 may be directly fixed using an appropriate adhesive or the like.
  • an optical element that achieves desired optical characteristics by changing the effective refractive index by the fine structure of the surface there are usually many optical elements such as an optical element having an antireflection function and an optical element having a polarization separation function. There is a device. Accordingly, it is possible to produce a plurality of types of negative patterns corresponding to the surface microstructure of various optical elements.
  • the mold 14 (negative pattern) to the flat plate 20, that is, for exchanging the mold.
  • the exchange of the negative pattern is easy, and it is possible to easily cope with the production of a methacrylic resin cast plate having various kinds of surface microstructures having various different optical characteristics.
  • one of the flat plates defining the cavity 26 is provided with a negative pattern having a surface microstructure. It can be changed appropriately according to the characteristics.
  • a cast plate may be manufactured using a cell 27b in which a mold 14 having a negative pattern is mounted on each of two opposing flat plates 20.
  • a methacrylic resin cast plate having a surface microstructure on both surfaces is generated. This is the same as in the second embodiment using the negative pattern composed of the ultraviolet curable resin layer 114 illustrated in FIGS. 16 and 17.
  • the master 13 provided with the conical (conical) protrusions 10b in a matrix is provided.
  • Arrangement of the projections 10b is arbitrary.
  • a master having a structure in which rows of conical projections 10b are arranged obliquely can be used. Since this arrangement further reduces the exposed area of the surface 10a of the substrate 10, it is expected that a methacrylic resin cast plate having a better antireflection effect can be manufactured.
  • the surface microstructure formed on the methacrylic resin cast plate has a conical projection 30a having a pitch of 250nm 300nm and a depth of 300nm 500nm.
  • the pitch should be in the range of 150 nm to 300 nm.
  • a coating material for realizing abrasion resistance and antistatic properties is applied to the negative pattern surface of the cavity 26 in advance.
  • the composition was to be applied.
  • the material, the amount of addition and the like of such a coating composition can be appropriately changed according to the desired characteristics. For example, when a material having a higher refractive index than the metal-based resin is used as the coating composition, the aspect ratio of the surface microstructure of the metal-based resin cast plate 30 is artificially increased due to the difference in the refractive index. Can be
  • the surface treatment step can be omitted.
  • a pattern having an area corresponding to a plurality of substrates 10 serving as a master may be used.
  • the master itself is poor in mass production, and the area of the master is naturally limited due to the use of silicon, quartz, etc. .
  • the ultraviolet curing resin layer 114 is cured by sequentially changing the positions of the masters on the flat plate 120, or based on one master. It is also possible to produce a large area negative pattern by connecting a plurality of translucent plates (flat plates) of the ultraviolet curable resin layer 114 produced in this way.
  • the ultraviolet curable resin layer 114 as a negative pattern is formed directly on the upper surface of the flat plate 120 that partitions the cavity 26.
  • this ultraviolet curable resin layer 114 is formed of another transparent material. It may be separately formed on a plate material or the like, and this plate material may be mounted on the flat plate 120.
  • a step of attaching a plate material to the flat plate 120 is added, also in this case, a plurality of types of negative patterns realizing different optical characteristics are attached through a detachable and replaceable mechanism.
  • a methacrylic resin cast plate having a plurality of types of surface microstructures corresponding to various optical characteristics.
  • the surface microstructure including the ultraviolet curable resin layer 114 is transferred from the mold 14.
  • a negative pattern may be directly formed on the flat plates 20 and 22 by a semiconductor processing technique or an electron beam processing technique.
  • the methacrylic resin cast plate having a more precise surface microstructure can be produced in combination with the extremely high transfer rate as the embedding polymer.
  • the point of the present invention is that the method of forming the negative pattern itself is arbitrary.
  • the monomer mixture M is not necessarily limited to a complete monomer, but may be a pre-polymerized mixture having a certain viscosity. S can.
  • the heat treatment is performed to accelerate the polymerization reaction of the monomer mixture M filled in the cell 27.
  • the flat plate 22 facing the mold 14 is made of glass.
  • the ultraviolet irradiation treatment employed in the second embodiment can be performed instead of the heat treatment.
  • the polymerization reaction of the monomer mixture M filled in the cell 27a is accelerated by performing the ultraviolet irradiation treatment.
  • the heat treatment adopted in the first embodiment may be applied also in the second embodiment.
  • a heat treatment or an ultraviolet irradiation treatment is employed to accelerate the polymerization reaction.
  • an acceleration is certainly effective, but for the present invention, these acceleration treatment and addition of an initiator are not essential, and may be appropriately changed or omitted.
  • embedded polymerization by a batch casting method was employed.
  • the present invention is not limited to a batch type, but is based on a continuous cell cast type in which a monomer mixture of a metathalyl resin is polymerized and solidified in a continuous (endless) cavity of a belt conveyor type. Bulk polymerization can be employed.
  • a method for producing a methacrylic resin cast plate using this continuous casting type polymerization is described.
  • This continuous casting type polymerization includes the following steps A2 to D2.
  • a belt conveyor type continuous cell having a negative pattern corresponding to a desired surface microstructure is formed on at least one of two opposing surfaces.
  • FIG. 20 schematically shows an example of an apparatus used for continuous casting type bubble polymerization.
  • This apparatus includes a pair of continuously driven endless belts ELB1 and ELB2, and the endless belts ELB1 and ELB2 are arranged at a predetermined distance L2 from each other.
  • the endless belts ELB1 and ELB2 are formed of, for example, a stainless alloy.
  • a monomer mixture M of a methacrylic resin is continuously injected as shown by a white arrow in FIG.
  • the belts ELB1 and ELB2 are driven, the monomer mixture M moves to the polymerization zone, the heat treatment zone, and the cooling zone in this order.
  • a desired surface fine structure is provided on the entire surface of the endless belt ELB2.
  • a thin metal-like foil-like mold 214 having a negative pattern corresponding to the structure is provided continuously (with a resin).
  • the mold 214 is basically formed with a negative pattern including protrusions having a pitch of S250 nm to 300 nm and a height of 300 nm to 500 nm, similarly to the mold 14. Further, both sides of the space between the endless belts ELB1 and ELB2 are lined with partitions (not shown), thereby forming a filling tank.
  • Step B2—D2 is the same as Step BD of the first embodiment.
  • the cast plate 30 of the methacrylic resin solidified by the polymerization reaction is taken out. It becomes possible to manufacture a methacrylic resin cast plate in a larger amount and at a lower cost.
  • a polyfunctional unsaturated monomer using methacrylic acid or an ester thereof may be used as another copolymerizable monomer.
  • a polyfunctional unsaturated monomer is a compound having two or more radically polymerizable double bonds in the molecule.
  • Compounds having two or more radically polymerizable double bonds in the molecule include, for example, allyl methacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, and polypropylene.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

L'invention concerne un procédé de fabrication d'une plaque coulée en résine méthacrylique (30) qui présente une excellente aptitude à la fabrication en série et une microstructure de surface hautement précise. Un moule métallique (14), sur lequel un modèle négatif (14b) correspondant à une microstructure de surface spécifiée est formé, est fixé à une première plaque plane (20). Cette première plaque plane (20) est opposée à une seconde plaque plane (22) pour former une cellule (27). Une surface de la cavité (26) de cette cellule est cloisonnée par le moule métallique. La cavité est remplie d'un mélange de monomères de résine méthacrylique. Ce mélange de monomères est soumis à une réaction de polymérisation dans la cavité de manière à durcir. Un corps moulé en résine durcie est extrait de la cellule et découpé aux dimensions spécifiées pour permettre la fabrication de ladite plaque coulée.
PCT/JP2004/011921 2003-08-28 2004-08-19 Plaque coulee en resine methacrylique a microstructure de surface et procede de fabrication de ladite plaque Ceased WO2005022208A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2005513425A JPWO2005022208A1 (ja) 2003-08-28 2004-08-19 表面微細構造をもつメタクリル系樹脂キャスト板及びその製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2003-305054 2003-08-28
JP2003305054 2003-08-28

Publications (1)

Publication Number Publication Date
WO2005022208A1 true WO2005022208A1 (fr) 2005-03-10

Family

ID=34269290

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2004/011921 Ceased WO2005022208A1 (fr) 2003-08-28 2004-08-19 Plaque coulee en resine methacrylique a microstructure de surface et procede de fabrication de ladite plaque

Country Status (4)

Country Link
JP (1) JPWO2005022208A1 (fr)
KR (1) KR20060058123A (fr)
CN (1) CN1842726A (fr)
WO (1) WO2005022208A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008108441A1 (fr) * 2007-03-08 2008-09-12 Toshiba Kikai Kabushiki Kaisha Procédé de formation d'un motif fin, moule formé par le procédé, procédé de transfert et procédé de formation d'un motif fin à l'aide du moule
JP2008233849A (ja) * 2007-02-23 2008-10-02 Mitsubishi Rayon Co Ltd 光学的ローパスフィルタ及びその製造方法
JP2008247022A (ja) * 2007-03-08 2008-10-16 Toshiba Mach Co Ltd 微細パターン形成方法、この微細パターン形成方法によって形成される型、この型を用いた転写方法および微細パターン形成方法
JP2011070116A (ja) * 2009-09-28 2011-04-07 Dainippon Printing Co Ltd 反射防止フィルム製造用組成物、反射防止フィルム、反射防止フィルムの製造方法、偏光板、および液晶表示装置
JP2012036404A (ja) * 2005-10-04 2012-02-23 Dnp Fine Chemicals Co Ltd 特定の表面形状と物性を有する構造体及びその構造体形成用の（メタ）アクリル系重合性組成物
CN116419836A (zh) * 2020-11-10 2023-07-11 盛禧奥欧洲有限责任公司 用于生产聚甲基丙烯酸甲酯板材的方法及衬垫

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI425643B (zh) * 2009-03-31 2014-02-01 Sony Corp 固態攝像裝置及其製造方法、攝像裝置和抗反射結構之製造方法
KR101597210B1 (ko) * 2015-03-23 2016-02-24 가천대학교 산학협력단 비 포토리소그래피 기반의 랩온어칩용 마이크로채널 형성방법

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5718251A (en) * 1980-07-04 1982-01-30 Mitsubishi Rayon Co Acryl group resin diffusing board and its manufacture
JPS62268615A (ja) * 1986-05-16 1987-11-21 Mitsubishi Rayon Co Ltd 光拡散性メタクリル樹脂板の製造方法
JP2001261924A (ja) * 2000-03-21 2001-09-26 Shin Dick Kako Kk 成形材料及び成形品
JP2002347045A (ja) * 2001-05-24 2002-12-04 Mitsubishi Rayon Co Ltd アクリル樹脂積層体の製法
JP2003080524A (ja) * 2001-09-12 2003-03-19 Nitto Denko Corp 光学フィルムの製造方法及び液晶表示装置
JP2003240903A (ja) * 2002-02-20 2003-08-27 Dainippon Printing Co Ltd 反射防止物品

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5718251A (en) * 1980-07-04 1982-01-30 Mitsubishi Rayon Co Acryl group resin diffusing board and its manufacture
JPS62268615A (ja) * 1986-05-16 1987-11-21 Mitsubishi Rayon Co Ltd 光拡散性メタクリル樹脂板の製造方法
JP2001261924A (ja) * 2000-03-21 2001-09-26 Shin Dick Kako Kk 成形材料及び成形品
JP2002347045A (ja) * 2001-05-24 2002-12-04 Mitsubishi Rayon Co Ltd アクリル樹脂積層体の製法
JP2003080524A (ja) * 2001-09-12 2003-03-19 Nitto Denko Corp 光学フィルムの製造方法及び液晶表示装置
JP2003240903A (ja) * 2002-02-20 2003-08-27 Dainippon Printing Co Ltd 反射防止物品

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012052125A (ja) * 2005-10-04 2012-03-15 Dnp Fine Chemicals Co Ltd 特定の表面形状と物性を有する構造体及びその構造体形成用の（メタ）アクリル系重合性組成物
KR101362637B1 (ko) 2005-10-04 2014-02-12 가부시키가이샤 디엔피 파인 케미칼 특정한 표면 형상과 물성을 갖는 구조체 및 그 구조체형성용의 (메트)아크릴계 중합성 조성물
JP4938675B2 (ja) * 2005-10-04 2012-05-23 株式会社Ｄｎｐファインケミカル 特定の表面形状と物性を有する構造体及びその構造体形成用の（メタ）アクリル系重合性組成物
JP2012036404A (ja) * 2005-10-04 2012-02-23 Dnp Fine Chemicals Co Ltd 特定の表面形状と物性を有する構造体及びその構造体形成用の（メタ）アクリル系重合性組成物
JP2008233849A (ja) * 2007-02-23 2008-10-02 Mitsubishi Rayon Co Ltd 光学的ローパスフィルタ及びその製造方法
US8685862B2 (en) 2007-03-08 2014-04-01 Toshiba Kikai Kabushiki Kaisha Method of forming micropattern, die formed by this method of forming micropattern, transfer method and micropattern forming method using this die
US8247330B2 (en) 2007-03-08 2012-08-21 Toshiba Kikai Kabushiki Kaisha Method of forming micropattern, die formed by this method of forming micropattern, transfer method and micropattern forming method using this die
JP2008247022A (ja) * 2007-03-08 2008-10-16 Toshiba Mach Co Ltd 微細パターン形成方法、この微細パターン形成方法によって形成される型、この型を用いた転写方法および微細パターン形成方法
WO2008108441A1 (fr) * 2007-03-08 2008-09-12 Toshiba Kikai Kabushiki Kaisha Procédé de formation d'un motif fin, moule formé par le procédé, procédé de transfert et procédé de formation d'un motif fin à l'aide du moule
US8703618B2 (en) 2007-03-08 2014-04-22 Toshiba Kikai Kabushiki Kaisha Method of forming micropattern, die formed by this method of forming micropattern, transfer method and micropattern forming method using this die
US8716140B2 (en) 2007-03-08 2014-05-06 Toshiba Kikai Kabushiki Kaisha Method of forming micropattern, die formed by this method of forming micropattern, transfer method and micropattern forming method using this die
JP2011070116A (ja) * 2009-09-28 2011-04-07 Dainippon Printing Co Ltd 反射防止フィルム製造用組成物、反射防止フィルム、反射防止フィルムの製造方法、偏光板、および液晶表示装置
CN116419836A (zh) * 2020-11-10 2023-07-11 盛禧奥欧洲有限责任公司 用于生产聚甲基丙烯酸甲酯板材的方法及衬垫
US20240001594A1 (en) * 2020-11-10 2024-01-04 Trinseo Europe Gmbh Method and Gasket for Producing a Polymethyl Methacrylate Plate
US12447649B2 (en) * 2020-11-10 2025-10-21 Trinseo Europe Gmbh Method and gasket for producing a polymethyl methacrylate plate

Also Published As

Publication number Publication date
CN1842726A (zh) 2006-10-04
JPWO2005022208A1 (ja) 2007-11-22
KR20060058123A (ko) 2006-05-29

Similar Documents

Publication Publication Date Title
US8092723B2 (en) Method of producing a diffraction grating element
EP0226123A2 (fr) Procédé de fabrication d'un article plastique transparent
JP2002286906A (ja) 反射防止方法及び反射防止構造並びに反射防止構造を有する反射防止構造体及びその製造方法
KR101020634B1 (ko) 기능성 나노패턴을 갖는 렌즈의 제조방법
JP2005092099A (ja) 硬化性樹脂組成物、及び光学物品、並びにそれを用いた画像表示装置
KR20190029489A (ko) 회절 도광판 및 회절 도광판의 제조 방법
JP2003222701A (ja) 光学部品及びその製造方法
JP6037627B2 (ja) インプリント成型用光硬化性樹脂組成物、インプリント成型硬化体及びこれらの製造方法
KR101085307B1 (ko) 중합체 물질로 투명 광학 소자를 제조하는 방법 및 몰드
KR20190045865A (ko) 회절 도광판 및 회절 도광판의 제조 방법
JP2003098304A (ja) 反射防止転写フィルム及びそれを用いた反射防止加工方法
WO2005022208A1 (fr) Plaque coulee en resine methacrylique a microstructure de surface et procede de fabrication de ladite plaque
KR20060048107A (ko) 표면 미세 구조를 갖는 메타크릴계 수지 성형체 및 그 제조방법
JP2004287238A (ja) 反射防止部材及びこれを用いた電子機器
JP4827164B2 (ja) 成形体およびその製造方法
JP2004013081A (ja) 複合型光学素子、複合型光学素子の製造方法、及び光学装置
CN101523245B (zh) 成形体及其制造方法
JP2003149405A (ja) 光重合法による反射防止物品の製造方法
JPH0722985B2 (ja) ホログラム化粧樹脂成形品の製造方法
JP2006343758A (ja) 反射防止方法及び反射防止構造並びに反射防止構造を有する反射防止構造体及びその製造方法
CN101490590B (zh) 一种光导波路的制造方法
CN108363272B (zh) 用于压印的下层膜形成用组合物以及图案形成方法
JP2007030373A (ja) 成形体の製造方法
Okabe et al. Fabrication of Moth-eye Antireflective Nanostructures via Oxygen Ion-beam Etching on a UV-curable Polymer
JP2014210361A (ja) 微細構造形成用母型およびその製造方法

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200480024517.9

Country of ref document: CN

AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DPEN Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed from 20040101)
WWE Wipo information: entry into national phase

Ref document number: 2005513425

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 1020067003855

Country of ref document: KR

WWP Wipo information: published in national office

Ref document number: 1020067003855

Country of ref document: KR

122 Ep: pct application non-entry in european phase