WO2006054888A2 - Composition liquide durcissable, film durci et stratifie antistatique - Google Patents

Composition liquide durcissable, film durci et stratifie antistatique Download PDF

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Publication number
WO2006054888A2
WO2006054888A2 PCT/NL2005/000785 NL2005000785W WO2006054888A2 WO 2006054888 A2 WO2006054888 A2 WO 2006054888A2 NL 2005000785 W NL2005000785 W NL 2005000785W WO 2006054888 A2 WO2006054888 A2 WO 2006054888A2
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Prior art keywords
composition
metal
cured
less
laminate
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PCT/NL2005/000785
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English (en)
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WO2006054888A3 (fr
Inventor
John Edmond Southwell
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Jsr Corporation
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Publication of WO2006054888A3 publication Critical patent/WO2006054888A3/fr

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Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields
    • H05K9/0073—Shielding materials
    • H05K9/0094—Shielding materials being light-transmitting, e.g. transparent, translucent
    • H05K9/0096—Shielding materials being light-transmitting, e.g. transparent, translucent for television displays, e.g. plasma display panel
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2211/00—Plasma display panels with alternate current induction of the discharge, e.g. AC-PDPs
    • H01J2211/20—Constructional details
    • H01J2211/34—Vessels, containers or parts thereof, e.g. substrates
    • H01J2211/44—Optical arrangements or shielding arrangements, e.g. filters or lenses
    • H01J2211/446—Electromagnetic shielding means; Antistatic means

Definitions

  • the present invention relates to antistatic laminates for coating display screens and optical lenses. More particularly, the present invention relates to coatings made of radiation curable liquid compositions for displays and lenses.
  • the coatings have good liquid stability and curability, and are capable of forming a cured film (cured coating) which excels in antistatic properties, hardness, scratch resistance, and transparency when applied to various plastic substrates used to make display panels and lenses , including polycarbonate, polymethylmethacrylate, polystyrene, polyester, polyethyleneterephtalate, polyolefin, epoxy resin, melamine resin, triacetylcellulose resin, ABS resin, AS resin, norbomene resin, and the like.
  • coating materials are to form laminates on substrates, including, for example, display monitors (like flat screen computer and/or television monitors such as those utilizing technology discussed in, for example, U.S. Pat. Nos. 6,091 ,184 and 6,087,730, which are hereby incorporated by reference and made a part hereof), optical discs, touch screens, smart cards, flexible glass and the like.
  • display monitors like flat screen computer and/or television monitors such as those utilizing technology discussed in, for example, U.S. Pat. Nos. 6,091 ,184 and 6,087,730, which are hereby incorporated by reference and made a part hereof
  • optical discs touch screens
  • smart cards flexible glass and the like.
  • flexible glass flexible glass
  • coated plastic substrates for, for instance, LCD (liquid crystal display, CRT displays, plasma display panel (PDP).
  • Suitable substrates to be coated include organic substrates.
  • Organic substrates are preferably polymeric ("plastic") substrates, such as substrates comprising polyester, polynorbornene, polyethyleneterephtalate, polymethylmethacrylate, polycarbonate, polyethersulphone, polyimide, fluorene polyester (e.g. a polymer consisting essentially of repeating interpolymerized units derived from 9,9-bis(4-hydroxyphenyl)fluorene and isophthalic acid, terephthalic acid or mixtures thereof), cellulose (e.g. triacetate cellulose), and/or polyethernaphtalene.
  • Particularly preferred substrates include polynorbornene substrates, fluorene polyester substrates, triacetate cellulose substrates, and polyimide substrates.
  • 60- 60166 describing a composition containing tin oxide particles, a polyfunctional acrylate, and a copolymer of methylmethacrylate and a polyether acrylate as major components; (3) Japanese Patent Application Laid-open No. 2000-143924, describing a curable liquid composition containing a reaction product of an alkoxysilane having a polymerizable unsaturated group in the molecule with metal oxide particles, a trifunctional acrylic compound, and a radiation polymerization promoter.
  • the approaches disclosed in the above documents have not been entirely successful in creating coatings with the desired antistatic properties, hardness and long-term storage stability.
  • Objectives of the present invention include providing curable liquid compositions having good liquid stability and which are capable of forming a cured coating (cured film) with improved antistatic properties, hardness, scratch resistance, transparency on the surface of various substrates, and at the same time having a high refractive index and good curability when applied as thin films.
  • the present invention also relates to a process of making a coated substrate, an antistatic laminate and a display.
  • a radiation curable composition comprising: (A) nanoparticles of a metal oxide, metal nitride, metal sulfide, metal phosphide, metal carbide, metal boride, metal selenide or a mixture thereof; (B) a compound having at least two polymerizable unsaturated groups; (C) one or more solvents, wherein the solubility of said component (B) in said solvents is 60wt% or higher; wherein said composition maintains its liquid stability after aging at 54°C for 72 hours.
  • (A) nanoparticles including as a major component an oxide of at least one element selected from the group consisting of antimony, indium, zinc, and tin;
  • composition one or more solvents wherein the solubility of said component (B) in said solvents is 60wt% or higher;. wherein said composition maintains its liquid stability after aging at 54 0 C for 72 hours.
  • a further embodiment of the present invention is a radiation curable composition
  • a radiation curable composition comprising: (A) 45 wt % to 90wt %, relative to the total weight of the composition, of a colloidal zinc-doped antimony oxide dispersion;
  • compositions of the present invention are used to provide coatings for various applications, for instance in optical media, hardcoat and/or display, and as curable materials for use in stereolithography. Additional objects, advantages and features of the present invention are set forth in this specification, and in part will become apparent to those skilled in the art on examination of the following, or may be learned by practice of the invention.
  • the invention disclosed in this application is not limited to any particular set of or combination of objects, advantages and features but may be adapted within the teachings set forth herein and the general knowledge to optimize and/or comply with particular design criteria.
  • -"Nanoparticles refers to a particle mixture wherein the majority of particles in the mixture have a dimension below 1 ⁇ m.
  • -"(Meth)acrylate refers to "acrylate and/or methacrylate”.
  • -"Liquid stability" of a composition refers to a composition that does not form agglomeration, sediment or phase separation after accelerated aging at 54°C for 72 hours or after aging at 25°C for 6 months
  • Solid content of a composition refers to the total content of metal nanoparticles (A), component (B), photoinitiator (D) and additives, if any, in the radiation curable composition. Solid content of the composition is determined gravimetrically by evaporation of volatiles from sample solutions in an aluminum weigh pan in a 120C oven for a period of one hour. Solid content is determined by measuring the weight difference between un-evaporated and evaporated sample.
  • -"Inorganic content refers to the total amount inorganic nanoparticles (A) in the solids portion of the radiation curable composition. The inorganic content percentage was determined empirically by calculating the ratio of inorganic solids (generally present as solid nanoparticles in a nanoparticle dispersion) to total solids in the composition and multiplying by 100%.
  • the invention relates, inter alia, to a radiation curable composition
  • a radiation curable composition comprising:
  • A nanoparticles of a metal oxide, metal nitride, metal sulfide, metal phosphide, metal carbide, metal boride, metal selenide or a mixture thereof;
  • composition one or more solvents, wherein the solubility of said component (B) in said solvents is 60wt% or higher; wherein said composition maintains its liquid stability after aging at 54 0 C for 72 hours.
  • Component (A) used in the present invention comprises nanoparticles of a metal oxide, metal nitride, metal sulfide, metal phosphide, metal carbide, metal boride, metal selenide or a mixture thereof.
  • Suitable metals that can be used in these compounds include antimony, zinc, tin, zirconium, titanium, indium, aluminum and gallium.
  • These nanoparticles are electro-conductive nanoparticles.
  • these nanoparticles contain, as a major component, an oxide of at least one element selected from the group consisting of indium, antimony, zinc, and tin, in order to achieve the desired conductivity and transparency of the cured film.
  • Major component in this context means either that the component (A) is made entirely of one of these oxides or that component (A) is a metal oxide (A1 ) doped with another metal oxide (A2) (for example, antimony oxide doped with zinc oxide), and the amount of component (A1 ) is at least 90% by weight.
  • A1 metal oxide
  • A2 antimony oxide doped with zinc oxide
  • oxide nanoparticles used as the component (A) include tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), fluorine- doped tin oxide (FTO), phosphorus-doped tin oxide (PTO), zinc antimonate (AZO), indium-doped zinc oxide (IZO), and zinc oxide.
  • ITO tin-doped indium oxide
  • ATO antimony-doped tin oxide
  • ITO tin-doped indium oxide
  • ITO tin-doped indium oxide
  • These particles may be used either individually or in combination of two or more.The same combinations can also be used in the case of nitride particles, sulfide particles, phosphide particles, carbide particles, boride particles, and selenides.
  • component (A) examples of commercially available oxide particles that can be used alone or in combination for component (A) are T- 1 (ITO) (manufactured by Mitsubishi Materials Corporation), Passtran (ITO, ATO) (manufactured by Mitsui Mining & Smelting Co., Ltd.), SN-100P (ATO) (manufactured by lshihara Sangyo Kaisha, Ltd.), NanoTek ITO (manufactured by C.I. Kasei Co., Ltd.), ATO, FTO (manufactured by Nissan Chemical Industries, Ltd.) and the like.
  • the nanoparticles used as component (A) may be used in a powdered state or they may be dispersed in a solvent.
  • the weight percentage of solid nanoparticles, relative to the combined weight of particles and solvent in the dispersion is preferably 30wt% to 70wt%, more preferably from 35wt% to 60wt%
  • colloidal dispersions of metal oxides such as Celnax CX-Z401 M (methanol dispersion of zinc antimonate), Celnax CX-Z641 (Methanol sol of antimony oxide), and the like.
  • the weight percentage of the colloidal dispersion containing metal nanoparticles is from 45wt% to 90wt%, relative to the total weight of the radiation curable composition. In another embodiment, the weight percentage of the colloidal dispersion is from 60wt% to 85wt%, relative to the total weight of the radiation curable composition.
  • Component (B) used in the present invention comprises a compound having at least two polymerizable unsaturated groups.
  • a cured product having improved scratch resistance and organic solvent resistance can be obtained by using compounds of this type for component (B).
  • Component (B) is believed to function as a surface treatment agent for the metal nanoparticles of component (A) and to improve the dispersibility of the metal nanoparticles in the radiation curable composition while at the same time improving film formability and transparency of the cured film of the curable liquid composition.
  • Examples of compounds that can be used for component (B) include (meth)acrylate compounds and vinyl compounds.
  • Examples of (meth)acrylates compounds include trimethylolpropane tri(meth)acrylate, alkoxylated trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, glycerol tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, ethylene glycol di(meth)acrylate, 1 ,3- butanediol di(meth)acrylate, 1 ,4-butanediol di(meth)acrylate,
  • hydroxy-containing multifunctional (meth)acrylates such as pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylatepentaerythritol tetra(meth)acrylate, trimethylolpropane multi (meth)acrylates such as trimethylolpropane tri(meth)acrylate, alkoxylated trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and isocyanurate multi(meth)acrylates such as tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, bis(2-hydroxyethyl)isocyanurate di(meth)acrylate, melamine pentaacrylates, and tricyclodecanedimethanol di(meth)acrylates, and tricyclodecaned
  • component (B) examples include divinylbenzene, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, and the like.
  • Component (B) can also be urethane-containing multi(meth)acrylates, a product of the reaction between polyisocyanates and reactive (meth)acrylate monomers.
  • Suitable polyisocyanates used as reactants in the production of such urethane-containing multi(meth)acrylates include diisocyanates, such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1 ,3-xylylene diisocyanate, 1 ,4-xylylene diisocyanate, 1 ,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethylphenylene diisocyanate, 4,4'-biphenylene diisocyanate, 6- isopropyl-1 ,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, lysine diisocyanate, hydrogenated dipheny
  • diisocyanates 2,4-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, and methylenebis(4-cyclohexylisocyanate) are desired.
  • diisocyanate compounds can be used either individually or as combinations of two or more.
  • Suitable reactive (meth)acrylate monomers used in the production of such urethane-containing multi(meth)acrylates include hydroxy-, mercapto- or amine- functional acrylate monomers.
  • suitable hydroxy, mercapto or amine functional acrylate compounds include 2-hydroxyethyl (meth)acrylate, 2-hydroxy butyl (meth)acrylate), hydroxy propyl (meth)acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth
  • (meth)acrylate 7-amino-3,7-dimethyloctyl (meth)acrylate thioethyl acrylate, aminoethyl acrylate and the like.
  • Examples of urethane-containing multi(meth)acrylates include reaction products of reactive group terminated oligomers or polymers.
  • Examples of reactive group terminated oligomers or polymers include "polyols" that are used as oligomeric/polymeric backbones in the urethane-multiacrylate compound.
  • suitable polyols to be used as backbones in the additional oligomer are polyether polyols, polyester polyols, polycarbonate polyols, polycaprolactone polyols, acrylic polyols, and the like. These polyols may be used either individually or in combinations of two or more. There are no specific limitations to the manner of polymerization of the structural units in these polyols.
  • Component (B) is added to the radiation curable composition of the present invention in an amount of 1 % to 65wt %, relative to the total weight of the composition, preferably 10wt% to 55wt%, relative to the total weight of the composition, more preferably, 15wt% to 45wt%, relative to the total weight of the composition.
  • the component (B) may comprise any one of the compounds listed above or may comprise a combination of two or more such compounds.
  • Component (B) is used in an amount of 25-65 parts by weight for 100 parts by weight of the total amount of the components (A) and (B) in order to maintain antistatic property and high refractive index for the cured coating as well as the liquid stability of the uncured composition.
  • Component (C) used in the present invention is a solvent in which component (B) has a solubility of 50wt% or higher; the solubility of component (B) in the component (C) solvent can also be 60wt% or higher, or 80 % or higher.
  • Solvent (C) can also be a solvent in which the component (B) is infinitely soluble.
  • Solvent (C) can be the same type of solvent used in the dispersion of the component (A) nanoparticles if, as described above, component (A) takes the form of a colloidal dispersion of nanoparticles. "Solubility" is defined as saturation solubility of the component (B) at 25 0 C.
  • the solubility is determined by measuring the solid content of the component (B) in a solution consisting of the component (B) and the solvent.
  • the type of solvent that may be used. In general, however, it is preferable to use a solvent having a boiling point of 200 0 C or less at atmospheric pressure.
  • the solvent may be used either individually or in combination with one or more additional solvents.
  • the amount of one or more solvents (component (C)) in the radiation curable composition of the present invention is 3wt% to 15wt%, relative to the total weight of the composition; more preferably, 4wt% to 10wt%, relative to the total weight of the composition.
  • These weight percentages refer to component (C) alone and are independent of any solvent present in the colloidal dispersion of the component (A) nanoparticles, in the event such a colloidal dispersion is used as described above.
  • suitable solvents that may be used for component (C) are alcohols such as methanol, ethanol, 1-propanol, isopropyl alcohol, isobutanol, n- butanol, tert-butanol, ethoxyethanol, butoxyethanol, diethylene glycol monoethyl ether, and diacetone alcohol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and methyl amyl ketone; ethers such as dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; esters such as ethyl acetate, butyl acetate, ethyl lactate, methyl acetoacetoate, and ethyl acetoacetate; hydrocarbon
  • components (A) through (C) may also be used in the composition of the present invention.
  • examples of other components typically used in the composition include photoinitiators and other additives.
  • the radiation curable liquid composition of the present invention is preferably cured by exposing it to radiation, such as visible rays, ultraviolet rays, deep ultraviolet rays, X-rays, electron beams, ⁇ -rays, ⁇ -rays, ⁇ -rays, and the like.
  • radiation such as visible rays, ultraviolet rays, deep ultraviolet rays, X-rays, electron beams, ⁇ -rays, ⁇ -rays, ⁇ -rays, and the like.
  • a photoinitiator may be added.
  • the photoinitiators are desirably free-radical photoinitiators.
  • Free- radical photoinitiators include benzoin derivatives, methyloylbenzoin and 4-benzoyl-1 ,3- dioxolane derivatives, benzilketals, ⁇ , ⁇ -dialkoxyacetophenones, ⁇ -hydroxy alkylphenones, ⁇ -aminoalkylphenones, acylphosphine oxides, bisacylphosphine oxides, acylphosphine sulphides, halogenated acetophenone derivatives, and the like.
  • lrgacure 651 (benzildimethyl ketal or 2,2-dimethoxy-i ,2- diphenylethanone, Ciba-Geigy), lrgacure 184 (1-hydroxy-cyclohexyl-phenyl ketone as the active component, Ciba-Geigy), Darocur 1173 (2-hydroxy-2-methyl-1- phenylpropan-1-one as the active component, Ciba-Geigy), lrgacure 907 (2-methyl-1- [4-(methylthio)phenyl]-2-morpholino propan-1-one, Ciba-Geigy), lrgacure 369 (2- benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one as the active component, Ciba-Geigy), Esacure KIP 150 (poly ⁇ 2-hydroxy-2-methyl-1-[4-(1
  • photoinitiators are aromatic ketones such as benzophenone, xanthone, derivatives of benzophenone (e.g. chlorobenzophenone), blends of benzophenone and benzophenone derivatives (e.g. Photocure 81 , a 50/50 blend of 4-methyl-benzophenone and benzophenone), Michler's Ketone, Ethyl Michler's Ketone, thioxanthone and other xanthone derivatives like Quantacure ITX (isopropyl thioxanthone), benzil, anthraquinones (e.g. 2-ethyl anthraquinone), coumarin, and the like. Chemical derivatives and combinations of these photoinitiators can also be used.
  • aromatic ketones such as benzophenone, xanthone, derivatives of benzophenone (e.g. chlorobenzophenone), blends of benzophenone and benzophenone derivatives (e.g. Photocure
  • photoinitiators which generally are used together with an amine synergist.
  • the amine synergist is chosen from the group consisting of a monomer tertiary amine compound, an oligomer (polymer) tertiary amine compound, a polymerizable amino acrylate compound, a polymerized amino acrylate compound and mixtures thereof.
  • the amine-synergist may include tertiary amine compounds, such as alkanol-dialkylamines (e.g., ethanol-diethylamine), alkyldialkanolamines (e.g.
  • methyldiethanolamine methyldiethanolamine
  • trialkanolamines e.g. triethanolamine
  • ethylenically unsaturated amine-functional compounds including amine-functional polymer compounds, copolymerizable amine acrylates, and the like.
  • the ethylenically unsaturated amine compounds may also include dialkylamino alkyl(meth)acrylates (e.g., diethylaminoethylacrylate) or N-morpholinoalkyl-(meth)acrylates (e.g., N- morpholinoethyl-acrylate).
  • the photoinitiator may also be an oligomeric photoinitiator.
  • an oligomeric photoinitiators examples include oligomers of 2-hydroxy-2-methyl-1- phenyl(4-(1-methylvinyl)phenyl)-1-propanone as well as 2-hydroxy-2-methyl-1-phenyl- 1-propanone.
  • the oligomeric photoinitiator can include Esacure KIP 100F, available from Lamberti Corporation.
  • the photoinitiator is added in an amount of 0.1wt% to 15wt%, relative to the total weight of the composition, preferably 0.5wt% to 10wt%, relative to the total weight of the composition.
  • the photoinitiator may be used either individually or in combination with other photoinitiators.
  • Antioxidants, antistatic agents, UV absorbers, light stabilizers, heat polymerization inhibitors, leveling agents, surfactants, lubricants, as well as other additives, may be added to the composition of the present invention.
  • antioxidants include Irganox 1010, 1035, 1076, 1222 manufactured by Ciba Specialty Chemicals Co., Ltd.), and the like.
  • UV absorbers include Tinuvin P234, 320, 326, 327, 328, 213, 329 (manufactured by Ciba Specialty Chemicals Co., Ltd.), Seesorb 102, 103, 501 , 202, 712, (manufactured by Shipro Kasei Kaisha, Ltd.), and the like.
  • Examples of light stabilizers include Tinuvin 292, 144, 622LD (manufactured by Ciba Specialty Chemicals Co., Ltd.), Sanol LS770, LS440 (manufactured by Sankyo Co., Ltd.), Sumisorb TM-061 (manufactured by Sumitomo Chemical Co., Ltd.), and the like.
  • Examples of antistatic additives include Larostat additives such as Larostat HTS905 (manufactured by BASF corp.), Crodastat additives such as Crodastat 1450 (manufactured by Croda Inc.), and the like.
  • the amount of the additives used in the radiation curable composition can be in the range, for example, of from 0.01 wt% to about 7.0 wt%; more preferably, the amount of additives can be from 0.1 wt% to 5w%; still more preferably, the amount of additives can be from 0.5wt% to 4 wt%, relative to the total weight of the composition.
  • the cured film of the present invention can be obtained by applying the radiation curable liquid composition onto an uncoated or a previously coated substrate and drying said composition; the dried composition is then cured by applying radiation.
  • the radiation curable composition of the present invention when cured, has a surface resistivity of 1 x 10 12 ⁇ / square or less, preferably 1 x 10 9 ⁇ / square or less, and still more preferably 1 x 10 8 ⁇ / square or less at a film thickness of 4 ⁇ m or less when measured at 25°C and 50% Relative Humidity.
  • 50% Relative Humidity refers to the % of humidity that the air can hold up at a certain temperature.
  • the radiation curable composition of the present invention when cured, has a surface resistivity of 1 x 10 12 ⁇ / square or less, preferably 1 x 10 9 ⁇ / square or less, and still more preferably 1 x 10 8 ⁇ / square or less at a film thickness of 4 ⁇ m or less, when measured at 25°C after exposure to 0% humidity for a period of 21 days.
  • 0% humidity refers to the humidity in a standard laboratory dessicator equipped with self-sealing lid and Drierite® brand anhydrous calcium sulfate with cobalt chloride humidity indicator (available from VWR International). Internal dessicant humidity/temperature was monitored using a BYK Gardner Model 201 humidity/temperature monitor. More detail descriptions are in the test method portion.
  • any suitable method such as a roll coating, spray-coating, flow coating, dipping, screen printing, or ink jet printing may be used.
  • the radiation source that may be used to cure the composition provided that the applied composition can be cured in a relatively short period of time.
  • Examples of potential sources of visible rays include sunlight, lamp, fluorescent lamp, and laser.
  • Potential sources of ultraviolet rays include mercury lamp, halide lamp, laser, and the like.
  • Suitable sources of electron beams include a method of utilizing thermoelectrons produced by a commercially available tungsten filament, a cold cathode method which causes electron beams to be generated by applying a high voltage pulse to a metal, a secondary electron method which utilizes secondary electrons produced by the collision of ionized gaseous molecules and a metal electrode, and the like.
  • Potential sources of ⁇ -rays, ⁇ -rays, and ⁇ -rays include fissionable materials such as 60 Co.
  • the source of ⁇ -rays can include a vacuum tube which causes accelerated electrons to collide against an anode.
  • the radiation may be applied by any one of the methods described above or in combinations of two or more such methods
  • the thickness of the cured film is preferably 0.1 ⁇ m -20 ⁇ m. In applications such as a touch panel or a CRT in which scratch resistance of the outermost surface is important, the thickness of the cured film is preferably 2 ⁇ m -15 ⁇ m. In the case of using the cured film as an antistatic film for an optical film or lens, the thickness of the cured film is preferably 0.1 ⁇ m -10 ⁇ m. Transparency is an important characteristic of the cured film when it is used as an optical film.
  • the average total light transmission percentage at 400nm-700nm of the composition, when cured, is 80% or greater at a cured film thickness of 4 ⁇ m or less. More preferably, the total light transmission percentage at 400nm-700nm of the composition, when cured, is 83% or greater at a cured film thickness of 4 ⁇ m or less.
  • the composition of the present invention when cured, provides a cured film with a high refractive index.
  • the cured film has a refractive index of 1.60 or higher, preferably 1.60 to 2.0, more preferably 1.65 to 1.9.
  • the composition may be used as a high refractive index layer in a multiple layer anti reflective film comprised of high and low refractive index layers.
  • the composition of the present invention when cured, exhibits an average haze percentage (which represents the amount of visible light scattered by the cured film) at 400nm-700nm of 8 % or less at a cured film thickness of 4 ⁇ m or less.
  • the haze percentage at 400nm-700nm is 4 % or less at a cured film thickness of 4 ⁇ m or less.
  • composition of the present invention when cured, provides a cured film with good surface hardness and abrasion resistance. These properties are characterized by the pencil test for film hardness and steel wool resistance test.
  • the composition when cured, has a pencil hardness of F or greater at a cured film thickness of 4 ⁇ m or less; preferably H or greater, more preferably, 2H or greater.
  • the composition of the present invention when cured, has a steel wool resistance of grade 3 to grade 5; preferably grade 4 to grade 5
  • the cured film of the present invention demonstrates a Crosshatch adhesion to hardcoated or uncoated polyester (PET), triacetate cellulose (TAC) or polycarbonate (PC) of 4B to 5B.
  • the viscosity of the composition of the present invention at 25 0 C prior to curing is usually 1-20,000 mPa-s, preferably 1-1 ,000 mPa-s.
  • the radiation curable composition of the present invention maintains its liquid stability after aging at 54 0 C for 72 hours (accelerated aging), or after aging at 25°C for 6 months.
  • the radiation curable composition of the present invention exhibits fast curability.
  • the UV cure dose used to polymerize 95% of the unsaturated acrylate groups in the composition is less than 10J/cm 2 , preferably less than 9J/cm 2 .
  • a substrate made from metal, ceramics, glass, plastic, wood, slate, or the like may be used without specific limitations as a substrate onto which the cured film of the present invention is applied.
  • the cured film it is preferable to apply the cured film to a film-type or fiber-type substrate.
  • a plastic film or a plastic sheet is a particularly preferable material, particularly when the composition is to be used as a coating for display panels and optical lenses.
  • plastic substrates examples include polycarbonate, polymethylmethacrylate, polyethyleneterephtalate, polystyrene/polymethylmethacrylate copolymer, polystyrene, polyester, polyolefin, triacetylcellulose resin, diallylcarbonate of diethylene glycol (CR-39), ABS resin, AS resin, polyamide, epoxy resin, melamine resin, cyclic polyolefin resin (norbornene resin, for example), and the like.
  • the cured film of the present invention is useful as a hardcoat for display panels because of its excellent scratch resistance and adhesion. Since the cured film has excellent antistatic properties, the cured film is suitably applied to various substrates such as film-type, sheet-type, or lens-type substrates as an antistatic film.
  • the cured film of the present invention examples include, but not limited to, application as a hardcoat for preventing scratches on the surface of the product or for preventing adhesion of dust due to static electricity, such as a protective film for touch panels, transfer foil, hard coat for optical disks, film for automotive windows, antistatic protective film for lenses, and surface protective film for cosmetics containers; the cured film of the present invention can also be used as an antistatic/antireflective film for various display panels such as CRTs, liquid crystal display panels, plasma display panels, and electroluminescence display panels; it can also be used as an antistatic/ antireflective film for plastic lenses, polarization film, and solar battery panel.
  • a hardcoat for preventing scratches on the surface of the product or for preventing adhesion of dust due to static electricity such as a protective film for touch panels, transfer foil, hard coat for optical disks, film for automotive windows, antistatic protective film for lenses, and surface protective film for cosmetics containers
  • the cured film of the present invention can also be used as an antistatic/anti
  • One method of providing antireflective properties to an optical article is to form a multi-layer structure consisting of a low refractive index layer and a high refractive index layer on a substrate or a substrate to which a hardcoat treatment has previously been applied.
  • the cured film of the present invention is useful as a layer structure which is antistatic and at the same time has a high refractive index. Consequently, an antistatic laminate having antireflection properties can be produced by using the cured film of the present invention in combination with a film having a refractive index lower than that of the cured film.
  • An antistatic laminate can include a coating layer having a thickness of 0.05 ⁇ m -0.20 ⁇ m and a refractive index of 1.30-1.48 as a low refractive index layer formed on the cured film of the present invention.
  • the cured film of the present invention acts at the same time as an antistatic layer and a high refractive index layer.
  • an antistatic laminate including a laminate having a coating layer with a thickness of 0.05 ⁇ m -0.20 ⁇ m and a refractive index of 1.60-2.20 as a high refractive index layer formed on the cured film of the present invention, and a coat layer having a thickness of 0.05 ⁇ m -0.20 ⁇ m and a refractive index of 1.30-1.48 as a low refractive index layer formed on the high refractive index layer.
  • the antistatic laminate of the present invention is composed of a substrate, a hardcoat layer, an antistatic layer having high refractive index and a low refractive index layer; this antistatic layer was made from the composition of the present invention.
  • This laminate also exhibits antireflective property (antistatic/antireflective laminate).
  • a layer including light scattering particles with a thickness of 1 ⁇ m or more, a layer including dyes, a layer including UV absorbers, an adhesive layer, or an adhesive layer and a delamination layer may be added.
  • the components which provide such functions may be added to the antistatic curable composition of the present invention.
  • the antistatic laminate of the present invention is also suitable for use as a hardcoat material for preventing stains or cracks (scratches) on plastic optical parts, touch panels, film-type liquid crystal elements, and the like. It may also be used to provide such a protective function when applied to plastic casings, plastic containers, or flooring materials, wall materials, and artificial marble used for an architectural interior finish; it can also be used as an adhesive or a sealing material for various substrates; as a vehicle for printing ink; or the like.
  • the present invention relates to an antistatic laminate comprising a layer of a cured film obtained by curing a radiation-curable composition comprising: (A) nanoparticles of a metal oxide, metal nitride, metal sulfide, metal phosphide, metal carbide, metal boride, metal selenide or a mixture thereof; (B) a compound having at least two polymerizable unsaturated groups;
  • the antistatic laminate of the present invention has a surface resistivity of 1 x 10 7 ⁇ / square to 1 x 10 10 ⁇ / square, preferably 2 x 10 7 ⁇ / square to 5 x 10 9 ⁇ / square, and still more preferably 3 ⁇ 10 7 ⁇ / square to 1x 10 9 , when measured at 25°C and 50% Relative Humidity.
  • the antistatic laminate of the present invention has a surface resistivity of 1 x 10 7 ⁇ / square to 1 x 10 10 ⁇ / square, preferably 2 x 10 7 ⁇ / square to 5 x 10 9 ⁇ / square, and still more preferably 3 ⁇ 10 7 ⁇ / square to 1x 10 9 , when measured at 25°C and 0% Relative Humidity.
  • the antistatic laminate of the present invention exhibits an average haze percentage at 400nm-700nm of 8 % or less.
  • the haze percentage at 400nm-700nm is 4 % or less.
  • the antistatic laminate of the present invention has an average total light transmission percentage at 400nm-700nm of 70% to 100%, preferably 75% to 97%, more preferably, 80% to 93%.
  • the antistatic laminate of the present invention without being exposed to a caustic solution, has a reflectance percentage at 340nm- 700nm of 0%-5%, preferably 0.1%-3%, more preferably 0.2%-2%. In another embodiment, the antistatic laminate of the present invention has a reflectance percentage at 340nm-700nm of 0.1%-7%, preferably 0.2%-5%, more preferably 0.3%- 3%, when exposed to a caustic solution for 30 minutes.
  • Caustic solution refers to an aqueous solution of NaOH 5%.
  • the contact angle formed between this surface and the tangent surface of the drop of water is 85 degree to 160 degree, preferably 90 degree to 155 degree, more preferably 95 degree to 150 degree.
  • the antistatic laminate of the present invention has a steel wool resistance of grade 3 to grade 5; preferably grade 4 to grade 5, measured by ASTM D3359.
  • the present invention also relates to a display comprising: a) a substrate; b) a hardcoat layer; c) an antistatic coating on said hardcoat layer, said antistatic coating is obtained by curing a radiation-curable composition comprising: (A) nanoparticles of a metal oxide, metal nitride, metal sulfide, metal phosphide, metal carbide, metal boride, metal selenide or a mixture thereof; (B) a compound having at least two polymerizable unsaturated groups;
  • the present invention also relates to a process for preparing a coated substrate having an antistatic coating comprising:
  • A nanoparticles of a metal oxide, metal nitride, metal sulfide, metal phosphide, metal carbide, metal boride, metal selenide or a mixture thereof;
  • composition one or more solvents, wherein the solubility of said component (B) in said solvents is 60wt% or higher.; wherein said composition maintains its liquid stability after aging at 54°C for 72 hours.
  • part and % respectively refer to “part by weight” and “wt%” unless otherwise indicated.
  • the residual isocyanate content in the reaction product (reactive surface treatment agent) in the reaction solution was measured by FT-IR and found to be 0.1 wt% or less. This indicates that each reaction was completed almost quantitatively. It was confirmed that the reactive surface treatment agent had a thiourethane bond, a urethane bond, an alkoxysilyl group, and a polymerizable unsaturated group.
  • Examples 1-4 and Comparative Examples 5-6 Preparation of Examples and Comparative Examples: Examples 1-4 and Comparative Examples 5-6 were prepared by: a. Admixing components B, C 1 and D b. Filtering the above mixture through 1 ⁇ m-encapsulated depth filter, available from Millipore, Inc. c. Mixing the filtered mixture with component A.
  • A-1 Colloidal Antimony Pentoxide Methanol dispersion (Celnax Z401 M available from
  • B-1 SR 444 Pentaerythritol Triacrylate available from Sartomer Company. «> B-2: SR 399 Dipentaerythritol Pentaacrylate available from Sartomer Company.
  • B-6 Larostat HTS905 organic antistatic agent, available from BASF.
  • D-1 lrgacure 907 available from Ciba Specialty Chemicals.
  • D-2 lrgacure 184 available from Ciba Specialty Chemicals.
  • Solid content (%) weight percentage of solid content relative to total weight of the whole composition (solids + solvent).
  • Inorganic content (%) weight percentage of inorganic solids relative to total weight of solids in the composition (inorganic solids + organic solids).
  • Table 3 Properties of antistatic/ antireflective laminate using the example compositions as high Rl layer.
  • compositions obtained in Examples 1-5 and Comparative Examples 6-7 were applied to a polyester film ("A4300" available from Toyobo Co., Ltd., thickness: 188 Gm) using a wire bar coater #3 or #4 rod for appropriate wet film thickness versus solid contents to obtain same cured film thickness values shown in Table 2.
  • Wet films were then dried in an oven at 8O 0 C for three minutes to form films.
  • the films were cured by exposure to a UV-radiation dose of 1.0 J/cm 2 using a 300W Fusion D-lamp in an air atmosphere.
  • compositions obtained in Examples 1-4 and Comparative Examples 5-6 were applied to a hardcoated polyester film ("A4300" manufactured by Toyobo Co., Ltd., thickness: 188 ⁇ m, with a hardcoat layer Desolite® 4D5-15 manufactured by DSM Desotech Inc. applied and cured to a 3 ⁇ m cured hardcoat thickness using a #3 wire-wound rod applicator, evaporation step of 3 minutes at room temperature, and exposure to a UV-radiation dose of 1.0 J/cm 2 using a 300W Fusion D-lamp in an air atmosphere) using a wire bar coater, and dried in an oven at 8O 0 C for one minute to form films.
  • the films were cured by applying ultraviolet rays in air at a dose of 1 J/cm 2 using a metal halide lamp to obtain cured films (hardcoat layers) having a thickness shown in Table 1.
  • a low refractive index coat material (“Desolite® DZ-0009” manufactured by DSM Desotech Inc., solid content: 5% in MEK) was applied to the above cured film by spin coating at 7500 rpm, 3000rpm/s for 12 seconds. The films were then exposed to a UV-radiation dose of 1.0 J/cm 2 using a 300W Fusion D-lamp in a Nitrogen atmosphere, forming low refractive index film having a thickness of 0.1 ⁇ m to obtain antistatic laminate having antireflection properties.
  • Desolite® DZ-0009 manufactured by DSM Desotech Inc., solid content: 5% in MEK
  • Liquid compositions were tested for liquid stability in the following manner: 15g of each coating example were placed in a 2OmL glass scintillation vial with Teflon® cap and the vials were sealed. The sealed vials were placed in a 54 ° C oven for a period of 72 hours and then removed from the oven and allowed to come to room temperature. The liquid coatings were examined through the glass vial to determine if sedimentation of any coating components had occurred. Sedimentation is an indicator of liquid stability and can indicate nanoparticle flocculation and agglomeration. Coating compositions were also tested for agglomeration by producing 4 micron cured films of the aged compositions and visually examining the cured films for particulates. The presence of particulates having developed after 54 ° C aging is an indicator of poor liquid composition stability. Particulates can be in the form of agglomerations of inorganic nanoparticles showing an improperly dispersed composition. Steel wool scratch resistance:
  • Grade 5 No scratch was observed.
  • Grade 4 1-5 scratches were observed.
  • Grade 3 6-50 scratches were observed.
  • Grade 2 51-100 scratches were observed.
  • Grade 1 Peeling of film was observed.
  • a cured product or laminate with a scratch resistance of grade 3 or more is acceptable in actual application.
  • a cured product or laminate with a scratch resistance of grade 4 or more is preferable since excellent durability is obtained in actual application.
  • a cured product or laminate with a scratch resistance of grade 5 is still more preferable since durability in actual application is significantly improved.
  • the reflectance (minimum reflectance in measurement wavelength region) percentage of the laminate was measured at a wavelength of 340nm-700nm using a spectral reflectance measurement system (Perkin Elmer Lambda 9 UV-VIS spectrophotometer or equivalent equipped with specular reflectance accessory) reflectance of the laminate (antireflection film) at each wavelength was measured while using the reflectance of a deposited aluminum film as a standard (100%). The results are shown in Table 3. Reflectance after caustic exposure:
  • Antistatic/antireflective laminates were tested for change in reflectance after exposure to aqueous caustic solutions to partially quantify chemical resistance.
  • Caustic test solutions were prepared by dissolving NaOH solid pellets (available from Aldrich Co.) into distilled H 2 O to provide aqueous solutions of 5%w/w aqueous NaOH.
  • Laminate samples were tested for %Reflectance (as described previously). The samples were then placed on a flat surface and 2 mL of the caustic test solution was placed on the samples for a period of 30 minutes. At the end of this time period, the caustic solution was removed from each sample and the sample was gently rinsed with distilled water and allowed to dry at ambient laboratory conditions.
  • Total light transmission % and Haze% The total light transmission percentage and haze percentage of the cured film and the laminate were measured according to ASTM D1003 standard method using a Haze-gard plus model (available from BYK-Gardner Corp.). The results are shown in Table 2 and Table 3.
  • the surface resistivity ( ⁇ /square) of the cured film and the laminate was measured according to ASTM D257-99 using a high resistance meter/electrometer (6517A Electrometer manufactured by Keithley Instruments, Inc) and a resistivity cell (model 8009 Resistivity test fixture manufactured by Keithley Instruments, Inc.) The results are shown in Table 2 and Table 3.
  • the pencil hardness was measured according to standard method ASTM D3363: The composition was cured on a glass substrate and the coated substrate was placed on a firm horizontal surface. The pencil is held firmly against the film at a 45° angle (point away from the operator) and pushed away from the operator in a 6.5 mm (1/4 in.) stroke. The process started with the hardest pencil and continued down the scale of hardness to either of two end points: one, the pencil that will not cut into or gouge the film (pencil hardness), or two, the pencil that will not scratch the film (scratch hardness)
  • the pencil hardness of the film is represented by the following letter designations (the film hardness increases from left to right):
  • a glass microscope slide is coated with a test coating and the coating is cured by UV exposure.
  • Standard cure conditions solvent evaporation, cure at 1.0 J/cm 2 , Fusion 300 W D-lamp, air atmosphere.
  • 2mm x 2mm squares are cut into the cured film using a razor blade. Alternating squares are removed from the cured film.
  • the slide is then placed under 10x microscope set up for collimated axial transmitted illumination, and fitted with objectives of up to at least 0.70 numerical aperture.
  • Monochromatic illumination is used, which is generally provided by placing narrow bandwidth interference filters in the path of the microscope's built-in illumination system. If provision is made for external illumination sources, a monochromator may also be used to provide a continuously variable source.
  • the normal wavelength used is 589 nm or the Sodium D-line, from whence the designation of refractive index figures as "n".
  • the cured film is then compared to standard liquids of known refractive index (Cargill Index of Refraction Liquids, Standard Group available from McCrone Microscopy Inc.).
  • standard liquids of known refractive index Cargill Index of Refraction Liquids, Standard Group available from McCrone Microscopy Inc.
  • the Becke' line will move into the outline of the squares as the focus is moved "up". These steps are repeated on fresh coating squares until the outline of the squares disappears or the Becke' line reverses direction from that observed from the previous observation.
  • a higher or lower refractive index liquid is chosen depending on the direction of the refractive index mismatch indicated by the initial observation. If the outline of the coating squares fails to disappear and two liquids adjacent to one another in the set are found which give opposite signs of Becke' line movement, the refractive index of the material then lies between the two values, most likely centered in the range.
  • the viscosity of the radiation curable composition was measured using the viscometer Paar Physica Z2, with a shear speed of 39rpm at 25°C. The results are shown in Table 2.
  • the relative cure rate for the ultraviolet cured coating was determined using an FTIR transmission technique.
  • the instrument used was a Nicolet Nexus 470 FTIR equipped with a DTGS detector.
  • a 100 W mercury lamp was affixed to a shelf in front of the FTIR sample compartment such that the UV light could be focused on a sample placed in the beam path.
  • the lamp was equipped with an electronic shutter capable of controlling exposures of the sample of 0.01 seconds and greater.
  • FTIR sampling parameters were: 4 cm "1 resolution and 10 co-added scans for each spectrum.
  • a drop of the desired liquid coating was spin-coated on a KBr crystal until completely covered with the experimental coating at a thickness not exceeding 1.0 micron.
  • the sample was scanned using 100 co-added scans and the spectrum is converted to absorbance. The net peak area of the acrylate absorbance at 810 cm "1 of the liquid coating was then measured.
  • the net peak area was measured using the "baseline” technique in which a baseline is drawn tangent to absorbance minima on either side of the peak. The area under the peak and above the baseline was then determined.
  • the sample was exposed to a 100W mercury lamp (model 6281 from Oriel Corp.) in an air atmosphere.
  • the FTIR scan of the sample and the measurement of net peak absorbance for the spectrum of the cured coating are repeated.
  • Baseline frequencies are not necessarily the same as those of the liquid coating, but were chosen such that the baseline was still tangent to the absorbance minima on either side of the analytical band.
  • the peak area measurement for a non-acrylate reference peak of both the liquid and cured coating spectrum is repeated. For each subsequent analysis of the same formulation, the same reference peak, with the same baseline points, was utilized.
  • the ratio of the acrylate absorbance to the reference absorbance for the liquid coating was determined using the following equation:
  • a AL area of acrylate absorbance of liquid
  • a RL area of reference absorbance of liquid
  • a A F area of acrylate absorbance of cured coating
  • a RF area of reference absorbance of cured coating
  • R F area ratio of cured coating
  • compositions containing an appreciable level of multifunctional acrylates are known to have relatively low %RAU values, even when fully cured ("% Ultimate RAU"), usually on the order of 55-70% RAU.
  • % Relative RAU represents the degree of curing of a coating composition relative to its % Ultimate RAU, and is defined by the following equation:
  • % Relative RAU ((% RAU of test composition)/(% Ultimate RAU))100
  • the average % Relative RAU was determined for the duplicate analyses for each time exposure for the sample. The time of exposure was then plotted versus %RAU for the sample. Based on the time of exposure and the wattage power of the UV lamp used, the UV exposure experienced by the sample was then calculated in J/cm 2 and recorded. The UV dose required to provide 95% of total final %Relative RAU was also calculated and recorded. These values of UV dose to 95% of final %Relative RAU are used to compare the cure speed of one composition to other compositions and comparative examples.

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Abstract

La présente invention concerne une composition liquide durcissable par rayonnement ayant une bonne stabilité liquide, excellente de par son aptitude au durcissement et susceptible de former un film durci ayant d’excellentes propriétés antistatiques, de dureté, de résistance aux rayures et de transparence sur différents substrats. Cette composition comprend des nanoparticules d’un oxyde métallique, nitrure métallique, sulfure métallique, phosphure métallique, carbure métallique, borure métallique, séléniure métallique ou de leurs mélanges, un composé ayant au moins deux groupes insaturés polymérisables et un ou plusieurs solvants ; la solubilité dudit composant (B) dans lesdits solvants est de 60 % en poids ou plus. Cette composition conserve sa stabilité liquide après vieillissement à 54 °C pendant 72 heures, et a un indice de réfraction de 1,60 ou supérieur après durcissement. La présente invention concerne également un procédé pour la fabrication d’un substrat revêtu, un stratifié antistatique et un afficheur.
PCT/NL2005/000785 2004-11-16 2005-11-09 Composition liquide durcissable, film durci et stratifie antistatique WO2006054888A2 (fr)

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WO2009005975A1 (fr) * 2007-06-29 2009-01-08 3M Innovative Properties Company Compositions flexibles de couche dure, articles et procédés
EP2048116A1 (fr) * 2007-10-09 2009-04-15 ChemIP B.V. Dispersion de nanoparticules dans des solvants organiques
EP2174989A1 (fr) 2008-10-08 2010-04-14 ChemIP B.V. Dispersions aqueuses d'oxydes métalliques et matériaux de revêtement préparés à partir de ces dispersions
US9296622B2 (en) 2012-08-22 2016-03-29 Hy-Power Coatings Limited Method for continuous preparation of indium-tin coprecipitates and indium-tin-oxide nanopowders with substantially homogeneous indium/tin composition, controllable shape and particle size
WO2017098053A1 (fr) * 2015-12-11 2017-06-15 Dsm Ip Assets B.V. Système et procédé destinés à des mesures optiques sur une feuille transparente
US10208190B2 (en) 2009-07-03 2019-02-19 3M Innovative Properties Company Hydrophilic coatings, articles, coating compositions, and methods
US10297698B2 (en) 2010-05-11 2019-05-21 3M Innovative Properties Company Articles, coating compositions, and methods
CN111032235A (zh) * 2017-10-23 2020-04-17 Mec株式会社 膜形成基材的制造方法、膜形成基材及表面处理剂
US11215738B2 (en) 2015-12-04 2022-01-04 Essilor International Antistatic film and lamination thereof
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WO2008061962A1 (fr) 2006-11-21 2008-05-29 Chemip B.V. Composition de revêtement liquide durcissable, film durci et stratifié antistatique
WO2009005975A1 (fr) * 2007-06-29 2009-01-08 3M Innovative Properties Company Compositions flexibles de couche dure, articles et procédés
EP2048116A1 (fr) * 2007-10-09 2009-04-15 ChemIP B.V. Dispersion de nanoparticules dans des solvants organiques
WO2009047302A1 (fr) * 2007-10-09 2009-04-16 Chemip B.V. Dispersion de nanoparticules dans des solvants organiques
US8333831B2 (en) 2007-10-09 2012-12-18 Chemip B.V. Dispersion of nanoparticles in organic solvents
EP2174989A1 (fr) 2008-10-08 2010-04-14 ChemIP B.V. Dispersions aqueuses d'oxydes métalliques et matériaux de revêtement préparés à partir de ces dispersions
US10208190B2 (en) 2009-07-03 2019-02-19 3M Innovative Properties Company Hydrophilic coatings, articles, coating compositions, and methods
US10297698B2 (en) 2010-05-11 2019-05-21 3M Innovative Properties Company Articles, coating compositions, and methods
US9296622B2 (en) 2012-08-22 2016-03-29 Hy-Power Coatings Limited Method for continuous preparation of indium-tin coprecipitates and indium-tin-oxide nanopowders with substantially homogeneous indium/tin composition, controllable shape and particle size
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