WO2004076566A1 - Composite hybride organique-inorganqiue, sa preparation, et composition de revetement anti-buee renfermant ce composite - Google Patents

Composite hybride organique-inorganqiue, sa preparation, et composition de revetement anti-buee renfermant ce composite Download PDF

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Publication number
WO2004076566A1
WO2004076566A1 PCT/KR2003/001481 KR0301481W WO2004076566A1 WO 2004076566 A1 WO2004076566 A1 WO 2004076566A1 KR 0301481 W KR0301481 W KR 0301481W WO 2004076566 A1 WO2004076566 A1 WO 2004076566A1
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Prior art keywords
poly
methacrylate
acrylate
alkoxysilane
hydrophilic
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PCT/KR2003/001481
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English (en)
Inventor
Yun Ho Han
Sang Soo Oh
Jun Beom Kim
Dae Sung Lee
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Luvantix Co., Ltd.
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Priority to AU2003303974A priority Critical patent/AU2003303974A1/en
Publication of WO2004076566A1 publication Critical patent/WO2004076566A1/fr

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    • 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
    • C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/062—Polyethers
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/42—Introducing metal atoms or metal-containing groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites

Definitions

  • the present invention relates to an organic-inorganic hybrid composite and a coating composition comprising same which, by photo-curing, provides a transparent anti-fogging coating layer having high surface hardness and improved anti-fogging ability.
  • Patent Publication No. 2002/0061950A1 Korean Patent Publication No. 2000-8569 and Korean Patent No. 302,326 are based on water-soluble organic polymers, e.g., polyvinylalcohol. Coating layers formed therefrom, however, show poor durability and surface hardness under a humid condition.
  • water-soluble organic polymers e.g., polyvinylalcohol.
  • European Patent No. 0,716,051 teaches a thermal-curable coating composition comprising a metal oxide together with an organic polymer
  • the present inventors have endeavored to develop an improved anti-fogging composition capable of providing a coating, layer having high surface hardness as well as improved anti-fogging property.
  • an organic-inorganic hybrid composite which comprises the steps of:
  • the organic-inorganic hybrid composite of the present invention is a complex containing hydrophilic, UV-curable and nano-sized metal oxide moieties intimately bonded to each other.
  • the hydrophilic polymer that is prepared in step (a) may be an acryl polymer or a urethane polymer depending on whether the polymerizable alkoxysilane is an unsaturated alkoxysilane to be reacted with an unsaturated hydrophilic compound or an alkoxysilane isocyanate to be reacted with one of the functional groups of the hydrophilic organic compound.
  • a hydrophilic acryl polymer may be prepared by polymerizing an organic compound containing terminal hydrophilic groups such as amine, hydroxy and thol groups, photo-curable unsaturated hydrocarbon groups and ester groups with an alkoxysilane containing one or more terminal unsaturated groups of the structure R x Si(OR') 4-x (R is C 1-10 alkenyl, R' is C 1-10 alkyl, and x is an integer in the range of 1 to 3) in the presence of a thermal-polymerization initiator at a temperature ranging from 40 to 80 ° C .
  • hydrophilic polymer examples include poly(ethyleneglycol) phenyl ether methacrylate, poly(ethyleneglycol) diacrylate (PEGDA), poly(propyleneglycol) dimethacrylate, poly(propyleneglycol) diacrylate (PPGDA), poly(ethyleneglycol) dimethacrylate, poly(ethyleneglycol) acrylate, poly(ethyleneglycol) methyl ether acrylate, poly(propyleneglycol) acrylate, ⁇ oly(ethyleneglycol) phenyl ether methacrylate, poly(ethyleneglycol) 2,4,6-tris(l-phenylethyl) phenyl ether methacrylate and the like.
  • polymerizable hydrophilic organic compound examples include 2-hydroxyethylmethacrylate (2-HEMA), 2-hydroxypropylacrylate (2-HPA), dipentaerythritol caprolacton hexa acrylate, ethoxylated (9) trimethylol propane triacrylate, ethoxylated (4) pentaerythritol tetraacrylate, ethoxylated (6) trimethylol propane triacrylate, 4-tert-butyl cyclohexyl acrylate, glycidyl vinyl benzyl ether, N,N-diglycidyl aniline, bis(4-glycidyloxyphenyl)methane, 2-(sulfoxy)ethyl methacrylate ammonium salt and the like.
  • 2-HEMA 2-hydroxyethylmethacrylate
  • 2-HPA 2-hydroxypropylacrylate
  • Examples of the unsaturated alkoxysilane suitable for use in this reaction are (3-acryloxypropyl)methyldimethoxysilane, methacryloxypropyltrimethoxysilane (MAPTMOS), acryloxypropyltrimethoxysilane (APTMOS),
  • MAPTMOS methacryloxypropyltrimethoxysilane
  • APTMOS acryloxypropyltrimethoxysilane
  • the unsaturated alkoxysilane may be employed so that the amount of the unsaturated group thereof is in the range of 1 to 1.5 equivalents based on the amount of the unsaturated groups of the hydrophilic organic compound.
  • the amount of unsaturated alkoxysilane is more than the upper limit defined above, unreacted unsaturated groups bring about undesirable gelation and lower the stability of the composition.
  • the acryl polymerization may be conducted by dissolving an unsaturated alkoxysilane in a suitable solvent, adding thereto a mixture of a polymerizable hydrophilic organic compound and a thermal-polymerization initiator dissolved in the same solvent at a temperature ranging from 40 to 80 C over a period ranging from 10 to 120 min with stirring, and stirring further for a period ranging from 4 to 10 hrs.
  • a temperature ranging from 40 to 80 C over a period ranging from 10 to 120 min with stirring, and stirring further for a period ranging from 4 to 10 hrs.
  • the reaction temperature is less than 40 ° C 5 the reaction is too slow, and when more than 80 ° C , undesired gelation occurs.
  • thermal-polymerization initiator any one of those known in the art may be used. Representative examples thereof include commercially available TRIAM-605 (diallyl chlorendate), TRIAM-606 (diallyl hexahydrophthalate), TRIAM-705 (triallyl trimellitate or triallyl 1,2,4-benzenetricarboxylate), V-30 (2-cyano-2-propylazoformamide), V-40 (l,l '-azobis(cyclohexane-l-carbonitrile)), V-50 (2,2'-azobis(2-amidinopropane)dihydrochloride), V-59 (2,2'-azobis(2-methylbutyronitrile)), V-60 (2,2'-azobisisobutyiOnitrile)), V-65 (2,2'-azobis(2,4-dimethylvaleronitrile)) 5 N-70
  • thermal-polymerization initiator may be used in an amount ranging from 0.01 to 1% by weight based on the total amount of the reactants. When the amount is less than 0.01% by weight, the reaction proceeds too slowly, and when more than 1% by weight, undesired gelation occurs.
  • the solvent which is used in the present invention may be any one of those known in the art, and representative examples thereof include isopropyl alcohol, diacetone alcohol, n-butanol, toluene, xylene, ethyl cellusolve, butyl cellusolve, methyl isobutyl ketone, methyl ethyl ketone, ethyl acetate and normal butyl acetate, among which preferred are isopropyl alcohol, n-butanol, toluene, ethyl cellusolve, methyl isobutyl ketone, methyl ethyl ketone and ethyl acetate.
  • the solvent may be used in an amount ranging from 40 to 90% by weight based on a total amount of the reactants.
  • a hydrophilic urethane polymer may be prepared by polymerizing an organic compound containing terminal hydrophilic groups such as -NH 2 , -OH and -SH with an alkoxysilane containing at least one isocyanate group in the presence of a urethane polymerization catalyst.
  • the isocyanate group (-NCO) of the alkoxysilane reacts with the hydrophilic groups, e.g., hydroxy (-OH), amine (-NH 2 ) and thiol (-SH), of the hydrophilic organic compound.
  • the hydrophilic groups e.g., hydroxy (-OH), amine (-NH 2 ) and thiol (-SH)
  • the organic compound may be a glycol containing two or more hydroxy groups at its ends, ether-, polyester-based polyol, polyether-based caprolactone polyol, polycarbonate-based polyol or polyamine, and representative examples thereof include polyoxyethylene glycol, polyoxypropylene glycol, polyoxypropylene triol, polyoxytetramethylene glycol, polyethylene adiphate, polypropylene adiphate, polybutylene adiphate, polyethylene glycol (PEG), polypropylene glycol (PPG), polytetramethylene glycol (PTMG), ethylene diamine (EDA) and diethylene triamine (DETA).
  • PEG polyoxypropylene glycol
  • PPG polypropylene glycol
  • PTMG polytetramethylene glycol
  • EDA ethylene diamine
  • DETA diethylene triamine
  • Suitable for use in this reaction is an alkoxysilane such as y -isocyanatopropyltrimethoxysilane.
  • the isocyanate groups of the alkoxysilane may be employed in an amount ranging from 1 to 1.5 equivalents based on the amount of hydrophilic groups of the hydrophilic organic compound.
  • amount of the isocyanate group of the alkoxysilane is less than 1 equivalent, unreacted hydrophilic groups lead to phase separation of the composition and poor abrasion resistance.
  • Suitable urethane polymerization catalysts include dibutyltindiraurate, dibutyltindibromide, dibutyltindichloride and l,4-diazabicyclo(2,2,2)octane, wherein dibutyltindichloride and l,4-diazabicyclo(2,2,2)octane are preferred. It may be used in an amount ranging from 0.001 to 1% by weight based on the total solid amount of reactants. When the amount is less than 0.001% by weight, the reaction proceeds too slowly, and when more than 1% by weight, undesired gelation occurs.
  • the solvent may be used in an amount ranging from 5 to 95% by weight based on a total amount of the reactants.
  • Step (h) Preparation of Nano-sized Organic-T organic Hybrid
  • the hydrophilic nano-sized organic-inorganic hybrid may be prepared by hydrolyzing the hydrophilic polymer formed in step (a) and condensing with a nano-sized silica sol in the presence of a hydrolysis catalyst at a temperature ranging from 5 to 80 C 5 preferably for 2 to 30 hrs.
  • the silica sol may be prepared by a sol-gel reaction, or commercially available nano-sized colloidal SiO 2 particles may be used, examples of which are SNOWTEX 40 (40% SiO 2 , diameter: 10-20nm, Nissan Chemical), SNOWTEX C (20% SiO 2 , diameter: 10-20nm, Nissan Chemical), SNOWTEX O (20% SiO 2 , diameter: 10-20nm, Nissan Chemical), MA-ST (30% SiO 2 , diameter: 10-20nm, Nissan Chemical), IPA-ST (30% SiO 2 , diameter: 10-20nm, Nissan Chemical), s LUDOX HS-40 (40% SiO 2 , diameter: 12nm, Dupont), LUDOX HS-30 (30% SiO 2 , diameter: 12nm, Dupont), LUDOX SM (50% SiO 2 , diameter: 7nm, Dupont), LUDOX AM (30% SiO 2 , diameter: 12nm, Dupont), NYACOL DP5820 (30% SiO 2 , diameter
  • Such a silica sol may be used in an amount ranging from 15 to 95% by weight based on the total amount of the reactants. When the amount is less than 15%) by weight, a coating layer with low hardness is formed, and when more than o 95% by weight, shrinkage of the coating layer occurs.
  • hydrolysis catalysts such as 0.001 to 1.2N HC1 and an acetic acid solution.
  • a hydrophilic organic-inorganic hybrid composite may be prepared by hydrolyzing and condensing the hydrophilic nano-sized organic-inorganic hybrid formed in step (b) together with an alkoxysilane containing one or more photo-curable unsaturated hydrocarbon groups in the presence of a hydrolysis catalyst at a temperature ranging from 5 to 80 C 5 preferably for 2 to 30 hrs. 0 In this reaction, photo-curable alkoxysilane chemically bonds to the surface of silica sol of the hybrid through a sol-gel reaction.
  • alkoxysilane having photo-curable unsaturated hydrocarbon groups such as acryl, vinyl and methacryl groups
  • the inventive hybrid may be employed in an amount ranging from 25 to 75% by weight based on the total amount of the reactants.
  • the amount is less than 25%o by weight, the coating layer shows low hardness and poor anti-fogging property, and when more than 75% by weight, the curing rate becomes slow.
  • Suitable for use in this reaction as a hydrolysis catalyst are 0.001 to 1.2N HC1 and an acetic acid solution.
  • the present invention also includes within its scope an anti-fogging coating composition comprising the organic-inorganic hybrid composite, an organic compound having unsaturated hydrocarbon groups and one or more hydrophilic groups, a photo-curing initiator and an organic solvent.
  • the anti-fogging coating composition of the present invention comprises the organic-inorganic hybrid composite in an amount ranging from 2 to 20% by weight, preferably from 5 to 15% by weight based on the total weight of the composition.
  • amount is less than 2% by weight, it is difficult to obtain the expected effects of the inventive hybrid composite, and when more than 20% by weight, the viscosity of the coating composition becomes excessively high.
  • the inventive coating composition further comprises a photo-curable unsaturated organic compound having one or more hydrophilic groups such as ether and hydroxy moieties in the form of a monomer, oligomer or polymer, which serves to increase the compatibility and anti-fogging property of the hybrid composite, in an amount ranging from 10 to 70% by weight, preferably from 20 to 40% by weight based on the total weight of the composition.
  • a photo-curable unsaturated organic compound having one or more hydrophilic groups such as ether and hydroxy moieties in the form of a monomer, oligomer or polymer, which serves to increase the compatibility and anti-fogging property of the hybrid composite, in an amount ranging from 10 to 70% by weight, preferably from 20 to 40% by weight based on the total weight of the composition.
  • the amount is less than 10% by weight, the viscosity of the coating composition becomes excessively high, and when more than 70% by weight, the surface hardness as well as the durability of the anti-fogging property of the coating
  • organic compound examples include 2-hydroxyethyl methacrylate (HEMA), 2-hydroxypropyl methacrylate (HPMA), 2-hydroxyethyl acrylate (HEA), 2-hydroxypropyl acrylate (HP A), polypropyleneglycol 5 methacrylate, polyethyleneglycol 6 methacrylate, polypropyleneglycol 6 acrylate, polyethyleneglycol 6 acrylate, polyalkyleneglycol methacrylate, ammonium sulphatoethyl methacrylate, 2-(2-ethoxyethoxy)ethyl acrylate, polyethyleneglycol 200 diacrylate, triethyleneglycol diacrylate, tripropyleneglycol diacrylate, polyethyleneglycol 400 diacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, pentaerythritol triacrylate, 3mole added ethoxylated trimethylolpropane triacrylate
  • HEMA polyethyleneglycol 6 methacrylate, polyethyleneglycol 6 acrylate, polyethyleneglycol 200 diacrylate, triethyleneglycol diacrylate, polyethyleneglycol 400 diacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, pentaerythritol triacrylate, 3mole added propoxylated trimethylolpropane triacrylate, 6mole added ethoxylated trimethylolpropane triacrylate, 6mole added propoxylated trimethylolpropane triacrylate, 9mole added ethoxylated trimethylolpropane triacrylate and 15mole added ethoxylated trimethylolpropane triacrylate.
  • the inventive coating composition comprises a photo-curing initiator, which acts to cross-link unsaturated hydrocarbon groups, in an amount ranging from 1 to 10% by weight based on the total weight of the composition.
  • Photo-curing initiators are Irgacure 184 (1-hydroxy cyclohexyl phenyl ketone), Irgacure 819
  • Irganox 1010 penentaerythritol bis(3-(3,5-di-tert-butyl l)propionate
  • Irganox 1035 triodiethylene bis(3-(3,5-di-tert-butyl l)propionate
  • Irganox 1076 octadecyl(3-(3,5-di-tert-butyl l)propionate
  • Irgacure 184, Irgacure 819, Irganox 1076 and TPO are preferably used in the present invention.
  • the inventive coating composition also comprises an organic solvent in an amount ranging from 0 to 90% by weight, preferably from 30 to 70% by weight based on the total weight of the composition.
  • an organic solvent in an amount ranging from 0 to 90% by weight, preferably from 30 to 70% by weight based on the total weight of the composition.
  • the organic solvents suitable for use in the present invention include isopropyl alcohol, diacetone alcohol, n-butanol, toluene, xylene, ethyl cellusolve, butyl cellusolve, methylisobutyl ketone, methylethyl ketone, ethyl acetate and normal butyl acetate, preferably including isopropyl alcohol, n-butanol, toluene, ethyl cellusolve, methylisobutyl ketone, methylethyl ketone and ethyl acetate.
  • the inventive coating composition comprises the organic-inorganic hybrid composite containing hydrophilic organic functional groups, photo-curable unsaturated hydrocarbon groups and nano-sized metal oxides for increasing surface hardness, when photo-cured, it provides a transparent anti-fogging coating layer having high adhesion to transparent plastic substrates made of, e.g., polycarbonate, polyacrylate, polyethylene terephthalate and polymethyl methacrylate, high surface hardness and improved, durable anti-fogging property.
  • Example 1 The procedure of Example 1 was repeated using the hybrid composites obtained in Preparation Examples 2 to 9, to obtain respective coating compositions
  • Example 1 The procedure of Example 1 was repeated except that 50 g of poly(ethyleneglycol) 2,4,6-tris(l- ⁇ henylethyl) ⁇ henylether methacrylate was employed instead of 9-ethyleneglycol diacrylate oligomer, to obtain a coating composition.
  • Example 1 The procedure of Example 1 was repeated except that 100 g of methacryloxypropyltrimethoxysilane was employed instead of acryloxypropyltrimethoxysilane, to obtain a coating composition.
  • a coating composition comprising a mixture of hydrophilic organic materials, silica sols and photo-curable silane was prepared as follows; 248 g of methacryloxypropyltrimethoxysilane was dissolved in 200 g of isopropylalcohol at 50 C 5 and a mixture of 156 g of 2-hydroxyethylmethacrylate and 2 g of V-60 dissolved in 150 g of isopropylalcohol was added thereto at room temperature over a period of 90 min with stirring, and stirred further for 8 hrs to form an acryl polymer.
  • IPA-ST (30% SiO 2 , diameter: 10-20nm, Nissan Chemical) was added thereto over a period of 10 min with stirring, and stirred further for 3 hrs.
  • 184 g of methacryloxypropyltrimethoxy silane was added to the resulting mixture over a period of 30 min to obtain a mixed composite.
  • An anti-fogging coating composition was prepared as described in U.S. Patent Publication No. 2002/0061950A1.
  • Example 1 The procedure of Example 1 was repeated except that the organic-inorganic hybrid composite was not used, to obtain a coating composition.
  • the coating compositions obtained in Examples 1 to 11, and Comparative Examples 1, 3 and 4 were each coated on a transparent polycarbonate plate by a flow method, which was subject to drying at 65 ° C for 5 min to remove the solvent and photo-curing at a rate of lOmpm in UV lamp curing apparatus ('D' type bulb commercially available by Fusion Company) to prepare a respective coating layer.
  • UV lamp curing apparatus 'D' type bulb commercially available by Fusion Company
  • the coating composition obtained in Comparative Example 2 was coated on a transparent polycarbonate plate by a flow method, which was subject to curing at 100 C for 10 min to prepare a coating layer.
  • a coating layer was cut in a checkered pattern at 1mm intervals to form
  • IB large ribbon type of peeling - the area peeled is in a range from 35 to
  • a coated sample was dipped in distilled water of 100 C for 15 min., pulled out and dried. The state of the coating layer was examined with the naked eye.
  • OWarm breath test a person blew on the surface of a coating layer for 3 seconds, and observed the clearance of the fogged area.
  • "Rating 5" corresponds to the case of no fogging, and "Rating 1", the case that fogging disappears after 10 seconds or more.
  • #Freezer test a coated sample was kept in a freezer of -20 C for 10 minutes, and exposed to ambient condition to observe fogging.
  • "Rating 5" corresponds to the case that fogging disappears within 30 seconds, and "Rating 1", the case that fogging disappears after 6 minutes or more.
  • Steam test a coated sample was brought into contact with water vapor for 2 seconds, and fogging was observed.
  • “Rating 5" corresponds to the case that fogging disappears within 60 seconds, and “Rating 1", the case that fogging disappears after 6 minutes or more.
  • Cold water test a coated sample was dipped in cold water of 5 ° C for 10 seconds, and observed.
  • “Rating 5" corresponds to the case of no fogging, and "Rating 1", the case that fogging disappears after 1 minute or more.
  • a coating layer was scratched with a pencil under a constant pressure at an angle of 45 degrees, which was repeated five times.
  • the hardness value of the pencil produced only one scratch or breakage of the coating layer is referred as to pencil hardness.
  • a coating layer placed at a distance of 15cm from a spray nozzle was sprayed with 50 5 80 psi water for 30 min.
  • the state of the sprayed coating was examined with the naked eye to see whether or not peeling occurred, and then the sprayed coating was evaluated as in the warm breath test.
  • the coating composition comprising the hydrophilic organic-inorganic hybrid composite of the present invention can be advantageously used in the preparation of a transparent anti-fogging coating layer having high adhesion to a substrate, high surface hardness and improved, durable anti-fogging property.

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Abstract

L'invention concerne une composition de revêtement anti-buée comprenant un nouveau composé hybride organique-inorganique, utilisée pour préparer une couche de revêtement anti-buée transparente ayant une haute dureté superficielle et présentant des propriétés durables améliorées anti-buée.
PCT/KR2003/001481 2003-02-27 2003-07-24 Composite hybride organique-inorganqiue, sa preparation, et composition de revetement anti-buee renfermant ce composite WO2004076566A1 (fr)

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AU2003303974A AU2003303974A1 (en) 2003-02-27 2003-07-24 Organic-inorganic hybrid composite, preparation thereof and anti-fogging coating composition comprising same

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KR10-2003-0012206A KR100533905B1 (ko) 2003-02-27 2003-02-27 자외선 경화형 친수성 유-무기 하이브리드 물질을포함하는 김서림 방지 코팅 조성물
KR10-2003-0012206 2003-02-27

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Cited By (6)

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US7153584B2 (en) * 2001-12-28 2006-12-26 Hoya Corporation Hybrid film, antireflection film comprising it, optical product, and method for restoring the defogging property of hybrid film
WO2007131474A1 (fr) * 2006-05-17 2007-11-22 Nano-X Gmbh Matériau de revêtement
WO2008034409A3 (fr) * 2006-09-18 2008-12-04 Nano X Gmbh Matériau de revêtement de silane et procédé pour la fabrication d'un revêtement de silane
WO2009118415A1 (fr) * 2008-03-28 2009-10-01 Dsm Ip Assets B.V. Composition de revêtement, revêtement et objet revêtu de la composition de revêtement
US9834699B2 (en) 2012-06-19 2017-12-05 Watever Inc. Coating composition
CN113637345A (zh) * 2021-07-19 2021-11-12 武汉中科先进技术研究院有限公司 一种水性环保耐磨型有机无机杂化防雾涂料及其制备

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KR101419876B1 (ko) * 2008-12-31 2014-07-16 코오롱인더스트리 주식회사 고성능 유기-무기 하이브리드 입자의 단일공정 제조 방법
KR101137515B1 (ko) * 2009-09-29 2012-04-20 대흥화학공업주식회사 유-무기 하이브리드 화합물
KR101652057B1 (ko) 2014-11-21 2016-08-29 주식회사 대신테크젠 개질그라파이트가 함유된 카본계 무기필러 융합을 통한 김서림방지용 발열소재의 제조방법
KR101963981B1 (ko) * 2016-12-05 2019-04-01 세종대학교산학협력단 카테콜 유도체를 함유하는 코팅제 및 상기 코팅제를 이용한 가죽 상에 코팅막 또는 패턴 형성방법
KR102030133B1 (ko) * 2018-04-10 2019-10-08 (주)제이엔티아이엔씨 도로용 투수 콘크리트 조성물 및 그것으로 제조한 투수 콘크리트
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