WO2005083476A1 - Microstructure-bearing articles of high refractive index - Google Patents
Microstructure-bearing articles of high refractive index Download PDFInfo
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- WO2005083476A1 WO2005083476A1 PCT/US2004/002049 US2004002049W WO2005083476A1 WO 2005083476 A1 WO2005083476 A1 WO 2005083476A1 US 2004002049 W US2004002049 W US 2004002049W WO 2005083476 A1 WO2005083476 A1 WO 2005083476A1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- 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
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
- C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
-
- 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
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/057—Metal alcoholates
Definitions
- This invention relates to the replication of microstructure-bearing surfaces, and more particularly to a genus of resin-based compositions capable of such replication.
- Mi.crostructure replication in resinous surfaces is of importance in such diverse technical fields as the fabrication of traffic signs, in which reflectivity is provided by cube-corner embossed sheeting; the production of Fresnel ophthalmic lens elements and flexible video disks; and the fabrication of "brightness enhancement” or “light management” films (hereinafter sometimes designated “LMF” for brevity) for liquid crystal displays.
- LMF light management films
- the resin have optimum physical properties, including substantial transparency, a glass transition temperature (Tg) high enough for shape retention during storage and use and viscoelastic properties facilitating shaping, typically by molding, and long-term shape retention which includes the micro structure aspects of the shaped articles.
- Tg glass transition temperature
- Suitable viscoelastic properties include moduli in the glassy and rubbery states within certain ranges, as well as suitable transition temperatures between those states. It is also desirable for the LMF . to be adherent to substrates such as polycarbonate and to have good resistance to abrasion and scratching.
- compositions for the replication of microstructure are disclosed in the patent literature.
- a patent whose disclosure is generic to a large variety of such compositions is US Patent 4,576,850.
- the compositions described therein are characterized by "hard” and “soft” segments or moieties in combination with radiation-polymerizable moieties. Most often, all three of these types of segments are present in the same molecule.
- a key feature of the "hard” segments is the presence therein of cyclic (i.e., carbocyclic or heterocyclic) groups.
- Later-issued patents frequently make reference to 4,576,850 for its disclosure of suitable polymeric compositions and precursors therefor.
- an LMF will have a high refractive index, preferably at least about 1.70. Attainment of a refractive index this high is, for the most part, not possible when using only resinous materials of reasonable cost.
- the refractive indices of polymers of highly brominated monomers such as pentabromophenyl methacrylate are about 1.71, but such polymers sometimes have unfavorable physical properties.
- US Patent 6,291,070 discloses highly transparent nanostructured molded articles having a wide range of refractive indices, prepared from such inorganic materials as titanium dioxide combined with polymerizable or polycondensable surface groups such as those derived from (meth)acrylic and epoxy compounds. There may also be present other monomeric species such as (meth)acrylic acid esters.
- compositions of high refractive index comprising highly crystalline metallic particles such as those of titanium dioxide, combined with an organic solvent and a. dispersing aid to form colloidal particles. Such particles may be combined with organic polymers such as those derived from acrylates and methacrylates to form said compositions.
- the present invention is directed to mixed organic-inorganic compositions which are curable by radiation to optical articles having high refractive indices.
- Said compositions may be employed to form articles with replicated microstructures.
- the proportions of constituents therein may be varied to provide a wide assortment of property profiles.
- the invention includes articles which are radiation curable to optical resinous articles having surfaces with a replicated microstructure comprising a plurality of utilitarian discontinuities having an optical purpose, said article being curable to a cured article having a haze rating corresponding to a value, as determined by ASTM procedure D1003 on a flat film 3.2 mm thick on a bisphenol A polycarbonate substrate, of up to 5% and comprising:
- At least one oligomeric urethane multi(meth)acrylate optionally in combination with at least one other monomer effective to reduce viscosity,' improve thermomechanical properties or increase refractive index;
- Another aspect of the invention is optical resinous articles prepared by radiation curing of the above-described curable articles.
- the drawing is a schematic view of a LMF in a backlit liquid crystal display.
- the optical resinous articles of the present invention are characterized by a surface with replicated microstructure comprising a plurality of utilitarian discontinuities, such as projections and depressions, which surface may be readily released from a mold after radiation curing without loss of the detail of the mold and with retention of the replication of such detail under a wide variety of conditions during use.
- the articles have a wide variety of desired properties, such as toughness, flexibility, optical clarity and homogeneity, and resistance to common solvents.
- the microstructures of such articles have high thermal dimensional stability, resistance to abrasion and impact, and integrity even when the articles are bent to an angle as great as 180°.
- the term "microstructure" is used herein as defined and explained in US Patent 4,576,850, the disclosure of which is incorporated by reference herein.
- Discontinuities such as projections and indentations in the surface of said article will deviate in profile from the average center line drawn through the microstructure such that the sum of the areas embraced by the surface profile above the center line is equal to the sum of the areas below the line, said line being essentially parallel to the nominal surface (bearing the microstructure) of the article.
- the heights of said deviations will typically be about ⁇ 0.005 to ⁇ 750 microns, as measured by an optical or electron microscope, through a representative characteristic length of the surface, e.g., 1-30. cm.
- Said average center line can be piano, concave, convex, aspheric or combinations thereof.
- Articles where said deviations are of low order, e.g., from ⁇ 0.005 to ⁇ 0.1 or, preferably, to ⁇ 0.05 microns, and said deviations are of infrequent or minimal occurrence, i.e., the surface is free of any significant discontinuities are those where the microstructure-bearing surface is an essentially "flat" or " smooth" surface, such articles being useful, for example, as precision optical elements or elements with a precision optical interface, such as ophthalmic lenses.
- Articles where said deviations are of low order and of frequent occurrence include those having anti- reflective microstructure.
- Articles where said deviations are of high order, e.g., from ⁇ 0.1 to ⁇ 750 microns, and attributable to microstructure comprising a plurality of utilitarian discontinuities which are the same or different and spaced apart or contiguous in a random or ordered manner, are articles such as retroreflective cube- corner sheeting, linear Fresnel lenses, video discs and LMF's.
- the microstructure- bearing surface can contain utilitarian discontinuities of both said low and high orders.
- the microstructure-bearing surface may contain extraneous or non-utilitarian discontinuities, so long as the amounts or types thereof do not significantly interfere with or adversely affect the predetermined desired utilities of said articles.
- a backlit liquid crystal display generally indicated at 10 includes a LMF 11 which is typically positioned between a diffuser 12 and a liquid crystal display panel 14.
- the backlit liquid crystal display also includes a light source 16 such as a fluorescent lamp, a light guide 18 for transporting light for reflection toward the liquid crystal display panel 14, and a white reflector 20 for reflecting light also toward the liquid crystal display panel.
- the LMF 11 collimates light emitted from the light guide 18 thereby increasing the brightness of the liquid crystal display panel 14, enabling a sharper image to be produced by the liquid crystal display panel and allowing the power of the light source 16 to be reduced to produce a selected brightness.
- the LMF 11 in the backlit liquid crystal display is useful in equipment such as computers, personal televisions, video recorders, mobile communication devices, and automobile and avionic instrument displays.
- Component A of the articles of this invention is at least one oligomeric urethane multi(meth)acrylate.
- the term "(meth)acrylate” is used to designate esters of acrylic and methacrylic acids, and "multi(meth)acrylate” designates a molecule containing more than one (meth)acrylic group, as opposed to "poly(meth)acrylate” which commonly designates (meth)acrylate polymers.
- the multi(meth)acrylate is a di(meth)acrylate, but it is also contemplated to employ tri(mefh)acrylates, tetra(meth)acrylates and so on.
- Oligomeric urethane multi(meth)acrylates may be obtained commercially; e.g., from Sartomer Co. They may also be prepared by the initial reaction of an alkylene diisocyanate of the formula OCN-R 3 -NCO with a polyol. Most often, the polyol is a diol of the formula HO-R 4 -OH, wherein R 3 is a C 2 - ⁇ o 0 alkylene or an arylene group and R is a C 2 - ⁇ 00 alkylene group. The intermediate product is then a urethane diol diisocyanate, which subsequently can undergo reaction with a hydroxyalkyl (meth)acrylate.
- Suitable diisocyanates include 2,2,4-trimethylhexylene diisocyanate and toluene diisocyanate; alkylene diisocyanates are generally preferred.
- a particularly preferred compound of this type may be prepared from 2,2,4-trimethylhexylene diisocyanate, poly(caprolactone)diol and 2-hydroxyethyl methacrylate.
- the radiation curable compositions forming the articles of the invention may also comprise at least one other monomer effective to reduce viscosity, improve thermomechanical properties or increase refractive index.
- Monomers having these properties include acrylic monomers (i.e., acrylate and methacrylate esters, acrylamides and methacrylamides), styrenic monomers and ethylenically unsaturated nitrogen heterocycles.
- Suitable acrylic monomers include monomeric (meth)acrylate esters. They include alkyl (meth)acrylates such as methyl acrylate, ethyl' acrylate,' 1-propyl acrylate, methyl methacrylate and t-butyl acrylate.
- (meth)acrylate esters having other functionality.
- Compounds of this type are illustrated by the 2-(N-butylcarbamyl)ethyl (meth)acrylates, 2,4- dichlorophenyl acrylate, 2,4,6-tribromophenyl acrylate, t-butylphenyl acrylate, phenyl acrylate, phenyl thioacrylate, phenylthioethyl acrylate, alkoxylated phenyl acrylate, isobornyl acrylate and phenoxyethyl acrylate.
- the other monomer may also be a monomeric N-substituted or N,N-disubstituted (meth)acrylamide, especially an acrylamide.
- acrylamide include N-alkylacrylamides and N,N-dialkylacrylamides, especially those containing C ⁇ - 4 alkyl groups. Examples are N-isopropylacrylamide, N-t-butylacrylamide, N,N-dimethylacrylamide and N,N- diethylacrylamide.
- the other monomer may further be a polyol multi(meth)acrylate.
- Such compounds are typically prepared from aliphatic diols, triols and/or tetraols containing 2-10 carbon atoms.
- suitable poly(meth)acrylates are ethylene glycol diacrylate, 1,6- hexanediol diacrylate, 2-ethyl-2-hydroxymethyl-l,3-propanediol triacrylate (trimethylolpropane triacrylate), di(trimethylol ⁇ ropane) tetraacrylate, pentaerythritol tetraacrylate, the corresponding methacrylates and the (meth)acrylates of alkoxylated (usually ethoxylated) derivatives of said polyols.
- Styrenic compounds suitable for use as the other monomer include styrene, dichlorostyrene, 2,4,6-trichlorostyrene, 2,4,6-tribromostyrene, 4-methylstyrene and 4- phenoxystyrene.
- Ethylenically unsaturated nitrogen heterocycles include N- vinylpyrrolidone and vinylpyridine.
- Component B is at least one ethylenically unsaturated metal compound selected from the group consisting of tetravalent titanium and tetravalent zirconium compounds, with titanium compounds generally being preferred by reason of their reasonable cost and particular suitability. By reason of the unsaturated functionalization therein, it is possible to incorporate the metal compound into the polymer formed upon radiation curing.
- component B is in the form of nanoparticles.
- nanoparticles particles having a mean diameter up to 200 ran.
- the particle diameter is up to 100 ran, more preferably up to 70 ran and most preferably in the range of about 5- 50 ran.
- Particles of this size may be prepared by art-recognized techniques including flame pyrolysis, plasma processes, condensation processes in the gas phase, colloid techniques, precipitation processes, sol-gel processes, controlled nucleation and growth processes, MOCVD processes and (micro)emulsion processes.
- sol-gel processes starting with corresponding alkoxides (i.e., titanium or zirconium tetraalkoxides).
- Functionalization of the metal-containing nanoparticles may be effected simultaneously with or following their fo ⁇ nation, by contact of the alkoxide or the particles produced therefrom with an ethylenically unsaturated compound, typically an unsaturated trialkoxysilane.
- an ethylenically unsaturated compound typically an unsaturated trialkoxysilane.
- said compound is a (meth)acrylic compound which is often preferably a (meth)acryloxyalkyltrialkoxysilane such as 3-methacryloxypropyltrimethoxysilane (hereinafter sometimes "MPTMS").
- MPTMS functionalization it is frequently preferred for MPTMS functionalization to be conducted in the presence of a free radical scavenger, such as a stable free radical as exemplified by 4-hydroxy- 2,2,6,6-tetramethylpiperidinyloxy (hereinafter sometimes "4-OH TEMPO"). It is believed that Such functionalization affects primarily the surfaces of the nanoparticles, although the invention is not dependent on any theory of operation.
- a free radical scavenger such as a stable free radical as exemplified by 4-hydroxy- 2,2,6,6-tetramethylpiperidinyloxy (hereinafter sometimes "4-OH TEMPO"). It is believed that Such functionalization affects primarily the surfaces of the nanoparticles, although the invention is not dependent on any theory of operation.
- a molar ratio of titanium and/or zirconium to (meth)acrylic cpmpound in the range of about 5-10:1 is normally employed.
- the proportion of free radical compound is a catalytic proportion, effective to promote the reaction.
- the reaction temperature is typically in the range of about 30-80°C.
- a solvent such as an alkanol may also be present, provided it is removed by vacuum stripping or the like prior to formation of the curable article. It is often convenient to formulate the nanoparticles as a sol in a suitable suspending agent such as propylerie glycol methyl ether acetate.
- Component C of the radiation curable articles of this invention is at least one photoinitiator effective to promote polymerization of said articles upon exposure to ultraviolet radiation.
- Suitable materials for use as photoinitiators are identified in the aforementioned US Patent 4,576,850 and in such reference works as Encyclopedia of Polymer Technology. Examples are benzoin ethers, hydroxy- and alkoxyalkyl phenyl ketones, thioalkylphenyl morpholinoalkyl ketones and acylphosphine oxides.
- component A can comprise about 30-100%) oligomeric urethane multi(meth)acrylate, with any balance being the other (meth) . acrylate monomer.
- Component B most often comprises about 5-90%> of total components A and B; all percentages are by weight.
- Component C the photoinitiator, is present in a minor amount effective to promote polymerization upon exposure to ultraviolet radiation, generally in the range of about 0.005-3.0%o and preferably about 0.005- 1.0%) based on total polymerizable components.
- An important property of the cured articles of the invention is a haze rating corresponding to a value no greater than 5%>, as determined by ASTM procedure D1003 on a flat film 3.2 mm thick on a bisphenol A polycarbonate substrate.
- Other preferred properties are an abrasion rating no greater than 20, preferably no greater than 10, as determined by the falling sand abrasion test (ASTM procedure D968), and an adhesion rating to bisphenol A polycarbonate of 5B as determined by the Crosshatch adhesion test (ASTM procedure D3359).
- the radiation curable articles of this invention may be prepared by simply blending the components thereof, with efficient mixing to produce a homogeneous mixture, and then removing any solvent employed in preparation of said components. It is often preferred to remove air bubbles by application of vacuum or the like, with gentle heating if the mixture is viscous, and casting or otherwise creating a film of the resulting blend on a desired surface.
- the film can then be charged to a mold bearing the microstructure to be replicated and polymerized by exposure to ultraviolet radiation, producing cured optical resinous articles of the invention having the aforementioned properties. If polymerized on a surface other than the one on which it is to be used, the optical resinous article can be transferred to another surface.
- Such a polymerization process lends itself to rapid, mass production of articles with no adverse environmental impact because no or only a minor amount of solvent or other volatiles are evolved and the polymerization can be carried out at ambient temperatures and pressures.
- the process also lends itself to replication of articles with microstructure comprising utilitarian discontinuities, such as projections and depressions, which are readily released from the mold without loss of the detail of the mold and with retention of the replication of such detail under a wide variety of conditions during use.
- the articles can be formed with a wide variety of desired properties, such as toughness, flexibility, optical clarity and homogeneity, and resistance to common solvents, the microstructure of such articles having high thermal dimensional stability, resistance to abrasion and impact, and integrity even when the articles are bent.
- oligomer dimethacrylate The product was the desired oligomeric urethane dimethacrylate, hereinafter sometimes designated "oligomer dimethacrylate".
- Titanium tetraisopropoxide 105 g was added with stirring to a mixture of 1 ,000 g of 2-propanol, 49.05 g of concentrated hydrochloric acid and 5.25 g. of distilled water. The resulting mixture was stirred at room temperature for 72 hours, after which 0.23 g of a 33%o solution of 4-OH TEMPO in l-methoxy-2-propanol and 13.75 g of 3- methacryloxypropyltrimethoxysilane was added. The solution was heated for 6.5 hours at 50°C, after which 447 g of the solution was transferred to a round-bottomed flask and stripped of a large portion of the volatiles using a rotary evaporator.
- compositions, curable articles and cured articles were prepared in propylene glycol methyl ether acetate from the oligomer dimethacrylate of Example 1, the nanoparticle dispersion of Example 2, "Darocur 4265" (0.5%>) as photoinitiator and, in Examples 5, 6, 8 and 10, hexanediol diacrylate ("HDD A").
- the cured articles of the invention have refractive indices close to the preferred range (particlularly in Example 9), haze ratings no greater than 5 and an abrasion rating within the desired range. With the exception of the article of Example 8, they also have suitable adhesion ratings. As with the article of Example 3, it is expected that the adhesion of the article of Example 8 could be improved by addition of minor proportions of a multifunctional (meth)acrylate monomer, as determined by simple experimentation.
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2004316424A AU2004316424A1 (en) | 2004-01-26 | 2004-01-26 | Microstructure-bearing articles of high refractive index |
CA002554156A CA2554156A1 (en) | 2004-01-26 | 2004-01-26 | Microstructure-bearing articles of high refractive index |
BRPI0418066-6A BRPI0418066A (en) | 2004-01-26 | 2004-01-26 | microstructure-supported articles with high refractive index |
EP04705267A EP1711848A1 (en) | 2004-01-26 | 2004-01-26 | Microstructure-bearing articles of high refractive index |
CNB2004800410227A CN100405088C (en) | 2004-01-26 | 2004-01-26 | Microstructure-bearing articles of high refractive index |
JP2006551021A JP2007522499A (en) | 2004-01-26 | 2004-01-26 | High refractive index product with fine structure |
PCT/US2004/002049 WO2005083476A1 (en) | 2004-01-26 | 2004-01-26 | Microstructure-bearing articles of high refractive index |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/US2004/002049 WO2005083476A1 (en) | 2004-01-26 | 2004-01-26 | Microstructure-bearing articles of high refractive index |
Publications (2)
Publication Number | Publication Date |
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WO2005083476A1 true WO2005083476A1 (en) | 2005-09-09 |
WO2005083476A8 WO2005083476A8 (en) | 2006-01-19 |
Family
ID=34912863
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2004/002049 WO2005083476A1 (en) | 2004-01-26 | 2004-01-26 | Microstructure-bearing articles of high refractive index |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP1711848A1 (en) |
JP (1) | JP2007522499A (en) |
CN (1) | CN100405088C (en) |
AU (1) | AU2004316424A1 (en) |
BR (1) | BRPI0418066A (en) |
CA (1) | CA2554156A1 (en) |
WO (1) | WO2005083476A1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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KR20170076732A (en) * | 2014-10-22 | 2017-07-04 | 미츠비시 가스 가가쿠 가부시키가이샤 | Triacrylate compound, production method therefor, and composition |
CN106350703B (en) * | 2015-07-16 | 2018-07-10 | 东北大学 | A kind of method for preparing kalzium metal with electrolysis raw aluminum liquid fused salt thermal reduction |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03145602A (en) * | 1989-11-01 | 1991-06-20 | Seiko Epson Corp | Laminate and production thereof |
EP0832917A1 (en) * | 1995-06-09 | 1998-04-01 | Mitsubishi Rayon Co., Ltd. | Molded resin articles having marproof organic hard coat layer and nonfogging organic hard coat layer, process for the production of the same, and coating materials therefor |
US6291070B1 (en) * | 1997-05-13 | 2001-09-18 | Institut für Neue Materialien Gemeinnützige GmbH | Nanostructured moulded bodies and layers and method for producing same |
US20020058737A1 (en) * | 1999-02-15 | 2002-05-16 | Isao Nishiwaki | Resin composition and cured product |
US6432526B1 (en) * | 1999-05-27 | 2002-08-13 | 3M Innovative Properties Company | Nanosize metal oxide particles for producing transparent metal oxide colloids and ceramers |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0963329A (en) * | 1995-08-30 | 1997-03-07 | Minnesota Mining & Mfg Co <3M> | Reflection sheet for liquid-crystal backlight |
-
2004
- 2004-01-26 WO PCT/US2004/002049 patent/WO2005083476A1/en active Application Filing
- 2004-01-26 AU AU2004316424A patent/AU2004316424A1/en not_active Abandoned
- 2004-01-26 CN CNB2004800410227A patent/CN100405088C/en not_active Expired - Fee Related
- 2004-01-26 BR BRPI0418066-6A patent/BRPI0418066A/en not_active IP Right Cessation
- 2004-01-26 CA CA002554156A patent/CA2554156A1/en not_active Abandoned
- 2004-01-26 EP EP04705267A patent/EP1711848A1/en not_active Withdrawn
- 2004-01-26 JP JP2006551021A patent/JP2007522499A/en not_active Withdrawn
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03145602A (en) * | 1989-11-01 | 1991-06-20 | Seiko Epson Corp | Laminate and production thereof |
EP0832917A1 (en) * | 1995-06-09 | 1998-04-01 | Mitsubishi Rayon Co., Ltd. | Molded resin articles having marproof organic hard coat layer and nonfogging organic hard coat layer, process for the production of the same, and coating materials therefor |
US6291070B1 (en) * | 1997-05-13 | 2001-09-18 | Institut für Neue Materialien Gemeinnützige GmbH | Nanostructured moulded bodies and layers and method for producing same |
US20020058737A1 (en) * | 1999-02-15 | 2002-05-16 | Isao Nishiwaki | Resin composition and cured product |
US6432526B1 (en) * | 1999-05-27 | 2002-08-13 | 3M Innovative Properties Company | Nanosize metal oxide particles for producing transparent metal oxide colloids and ceramers |
Non-Patent Citations (1)
Title |
---|
PATENT ABSTRACTS OF JAPAN vol. 0153, no. 72 (P - 1254) 19 September 1991 (1991-09-19) * |
Also Published As
Publication number | Publication date |
---|---|
JP2007522499A (en) | 2007-08-09 |
AU2004316424A1 (en) | 2005-09-09 |
CA2554156A1 (en) | 2005-09-09 |
CN1906506A (en) | 2007-01-31 |
BRPI0418066A (en) | 2007-04-17 |
WO2005083476A8 (en) | 2006-01-19 |
CN100405088C (en) | 2008-07-23 |
EP1711848A1 (en) | 2006-10-18 |
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