WO2011090156A1 - Article anti-buée - Google Patents

Article anti-buée Download PDF

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Publication number
WO2011090156A1
WO2011090156A1 PCT/JP2011/051070 JP2011051070W WO2011090156A1 WO 2011090156 A1 WO2011090156 A1 WO 2011090156A1 JP 2011051070 W JP2011051070 W JP 2011051070W WO 2011090156 A1 WO2011090156 A1 WO 2011090156A1
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WIPO (PCT)
Prior art keywords
antifogging
film
group
polyacrylic acid
coating
Prior art date
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PCT/JP2011/051070
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English (en)
Japanese (ja)
Inventor
敏裕 平野
芳彦 小原
伸行 板倉
Original Assignee
セントラル硝子株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Priority claimed from JP2010013621A external-priority patent/JP2011153164A/ja
Priority claimed from JP2010155164A external-priority patent/JP2012017394A/ja
Priority claimed from JP2010155231A external-priority patent/JP2012017220A/ja
Application filed by セントラル硝子株式会社 filed Critical セントラル硝子株式会社
Publication of WO2011090156A1 publication Critical patent/WO2011090156A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • 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
    • C09D7/65—Additives macromolecular
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B27/00—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
    • G02B27/0006—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00 with means to keep optical surfaces clean, e.g. by preventing or removing dirt, stains, contamination, condensation

Definitions

  • the present invention relates to an antifogging article that can be used for various applications such as antifogging window glass or antifogging mirrors, lenses, and displays for vehicles and buildings, and is excellent in antifogging properties and heat resistance.
  • Transparent substrates such as glass and plastic have a sudden temperature change with respect to the substrate when one surface falls below the dew point due to the difference in temperature and humidity between the inner and outer surfaces of the substrate.
  • moisture in the atmosphere adheres as water droplets, and the substrate surface is condensed.
  • ⁇ cloudy '' occurs, and the visibility is hindered, and in general window glass, automobile and aircraft windshields, reflectors, glasses, sunglasses, etc. Safety is significantly impaired.
  • Patent Document 1 includes an antifogging coating material comprising an inorganic alkoxide, an inorganic alkoxide hydrolyzate and an inorganic alkoxide hydrolysis polycondensate, polyacrylic acid and polyvinyl alcohol, and Disclosed is an antifogging coating film mainly composed of a composition obtained by causing at least a polycondensation reaction of a hydrolyzate of an inorganic alkoxide in the presence of polyacrylic acid and polyvinyl alcohol.
  • Patent Document 2 discloses an antifogging layer made of a polyvinyl acetal resin having a degree of acetalization of 2 to 40 mol% (polyvinylphenylacetoacetal, polyvinylbenzacetal, polyvinyl butyral, etc.).
  • Patent Document 3 discloses the use of an antifogging film and a primer containing an ultraviolet curable resin, a metal oxide, and a hydrophilic resin.
  • Antifogging articles are desired to be able to maintain antifogging properties and visibility over a long period of time.
  • water absorption In the coating film having swells, peeling from the substrate is likely to occur due to swelling during water absorption, and the anti-fogging property cannot be maintained after peeling, and thus the visibility tends to decrease.
  • Antifogging articles are required to have heat resistance in applications where they are exposed to heat such as solar radiation for a long period of time.
  • any of the antifogging articles obtained in the inventions described in the above Patent Documents 1 to 3 tends to yellow when heated for a long period of time, and tends to cause problems in appearance and visibility. Then, this invention makes it a subject to obtain the anti-fogging article excellent in anti-fogging property and heat resistance.
  • an antifogging article having a base material and a heat-resistant antifogging film (hereinafter sometimes simply referred to as “coating”) formed on the base material.
  • the antifogging film is a composite film containing a binder substrate component derived from a binder component and a component derived from polyacrylic acid, and the antifogging property is expressed when the component derived from polyacrylic acid absorbs water.
  • An antifogging article (first antifogging article) is provided.
  • the first antifogging article is a film in which the antifogging film contains a copolymer of the binder component and the polyacrylic acid, It may be an antifogging article (second antifogging article) characterized by having a primer layer between the coating.
  • the first antifogging article comprises a copolymer of the binder component and the polyacrylic acid, wherein the antifogging film is in close contact with the substrate.
  • a composite film containing the antifogging film having a water absorption per unit volume of 0.05 to 3 mg / mm 3 when the water absorption is saturated, and the antifogging film being heat resistant to heat of 100 ° C. or less. May be an antifogging article (third antifogging article).
  • the second antifogging article may have the characteristics of the third antifogging article
  • the third antifogging article may have the characteristics of the second antifogging article
  • a heat-resistant antifogging film-forming coating agent containing a binder component and polyacrylic acids, which absorbs water when the heat-resistant antifogging film is formed.
  • the present invention is a composite film containing a binder substrate component derived from a binder component and a component derived from polyacrylic acid, and the antifogging property is expressed by water absorption of the component derived from polyacrylic acid.
  • a heat-resistant antifogging film for producing the first to third antifogging articles is provided.
  • a method for forming first to third antifogging articles characterized by including at least the following steps.
  • a method for forming a second antifogging article comprising at least the following steps. (1) A step of forming a primer layer comprising a hydrolysis product of the silicon compound A on the surface of the substrate (2) A step of preparing a coating agent for forming an antifogging film containing a binder component and polyacrylic acids (3) A step of applying the antifogging film-forming coating agent to the primer layer to obtain a coating film, and (4) a step of curing the coating film.
  • the antifogging article of the present invention preferably has heat resistance against heat of 100 ° C. or less. 100 degreeC assumes the thermal load of the glass for motor vehicles described in JISR3212 "Safety glass test method for motor vehicles".
  • “having heat resistance to heat of 100 ° C. or less” means that the anti-fogging article is not exposed to heat of 100 ° C. or less and the visibility and antifogging of the article are It means that there is no problem in sex.
  • an anti-fogging test assuming an actual vehicle environment in a vehicle window glass (hereinafter referred to as an actual vehicle anti-fogging test). It is preferable that condensation does not occur for 10 minutes or more.
  • the actual vehicle assumed anti-fogging property test is a test in which a sample is installed between two chambers in which the temperature and humidity can be controlled as shown in FIG.
  • the film side is assumed to be the inside of the vehicle and the substrate side is assumed to be the outside of the vehicle.
  • the assumed outside temperature is assumed to be 20 ° C
  • the assumed inside temperature is 25 ° C
  • the assumed inside humidity is 95%.
  • the assumed outside temperature is 0 ° C.
  • the assumed inside temperature is 25 ° C.
  • the assumed inside humidity is 60%.
  • the antifogging article of the present invention preferably has excellent adhesion between the substrate and the coating.
  • Excellent adhesion means that the substrate and the coating do not physically peel easily due to interactions such as bond formation and hydrogen bonding.
  • the film in close contact with the substrate refers to a film that is not peeled off by an artificial operation such as scratching, and a film in which the film itself or a component in the film does not elute over time.
  • the water absorption amount in the present invention indicates the mass of water present in the coating film based on the mass of the coating film in a state where no water is absorbed.
  • the antifogging article comprises an antifogging material having a base material, a film containing a binder component and a copolymer of polyacrylic acids, and a primer layer between the base material and the film. It is a sex product.
  • the substrate surface before forming the primer layer is subjected to treatment such as plasma irradiation, corona discharge, high-pressure mercury lamp irradiation, and the like.
  • An active group for example, a ketone group, an ether group, or an OH group may be generated on the surface.
  • the formation of the primer layer and the coating on the substrate may be performed on only one side of the substrate or on both sides.
  • the primer layer and the film may be formed on the entire surface of the substrate or a part thereof.
  • the primer layer is preferably made of a hydrolysis product of silicon compound A represented by the following general formula [1].
  • R 1 m SiX 4-m [1]
  • R 1 is an organic group containing at least one group selected from the group consisting of an amino group, a glycidoxy group, and a mercapto group
  • X is an alkoxy group having 1 to 18 carbon atoms
  • the silanol group of the hydrolysis product of the silicon compound A and the active group for example, ketone group, ether group, OH group, etc.
  • the active group for example, ketone group, ether group, OH group, etc.
  • excellent adhesion between the primer layer and the coating film is expressed by the interaction such as bond formation by reaction of OH group, glycidoxy group, etc. and hydrogen bond.
  • silicon compound A examples include trimethoxy [3- (phenylamino) propyl] silane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyldimethylmethoxysilane, 3-aminopropyltri Ethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyldimethylethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-aminoethylamino) propyltriethoxysilane, 3- Mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyldimethylmethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldiethoxy Run, 3-mercaptopropyl di
  • the primer layer is obtained by hydrolyzing the silicon compound A, and a liquid obtained by mixing the silicon compound A with water, an acidic aqueous solution, or a basic aqueous solution and hydrolyzing the mixture is used. It can form by apply
  • the solvent used for dissolving the silicon compound A is not particularly limited as long as it dissolves the silicon compound A.
  • Isopropyl alcohol is preferred from the viewpoint of price and safety.
  • a coating method of the hydrolysis product of the silicon compound A for example, known coating means such as dip coating, flow coating, spin coating, roll coating, spray coating, screen printing, flexographic printing, hand coating method, and ink jet method are used. Can be used.
  • the hydrolysis product of the silicon compound A As a method for drying the hydrolysis product of the silicon compound A, wiping at room temperature is sufficient, but the solution is applied to the substrate in order to quickly develop the adhesion between the substrate and the primer layer. Later, it may be fired at 50 to 100 ° C.
  • the coating preferably contains a component having a metalloxane bond derived from a binder component, and the component is preferably a component obtained by condensing an organometallic compound.
  • the composite film in which the binder component and the polyacrylic acid are combined can prevent the elution of the component derived from the polyacrylic acid from the film, and can exhibit antifogging properties over a long period of time. Since it becomes difficult to deteriorate, it is more preferable that the organometallic compound is copolymerized with polyacrylic acids.
  • an organometallic compound (A) represented by the following general formula [1], a compound (B) in which the organometallic compound (A) is partially condensed, or the (A) and (B ) can be used.
  • R is a hydrocarbon group having 1 to 18 carbon atoms, and at least one selected from the group consisting of an epoxy group, a glycidoxy group, an amino group, a fluorine atom, and a chlorine atom as a partial hydrogen atom of the hydrocarbon group.
  • M is at least one element selected from the group consisting of Si, Ti, Al, Zr, Sn, and Zn
  • X is at least one group selected from an alkoxy group, a chloro group, an isocyanate group, and a hydroxy group
  • n is an integer of 0 to 3.
  • organometallic compound (A) examples include methoxytrimethylsilane, ethoxytriethylsilane, (chloromethyl) dimethylisopropoxysilane, and [bicyclo [2.2.1] hept-5-en-2-yl] triethoxy.
  • Silane trimethyl [3- (triethoxysilyl) propyl] ammonium chloride, trimethoxy [3- (phenylamino) propyl] silane, trimethoxysilane, trimethoxyphenylsilane, trimethoxy (propyl) silane, trimethoxy (p-tolyl) silane , Trimethoxy (methyl) silane, triethoxysilane, triethoxyphenylsilane, triethoxymethylsilane, triethoxyfluorosilane, triethoxyethylsilane, triethoxy-1H, 1H, 2H, 2H-tridecafluoro-n- Octylsilane, pentyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, N- [2- (N-vinylbenzylamino) ethyl]
  • the organometallic compound is selected so that the refractive index difference between the substrate and the coating is within 10% in consideration of matching of the refractive index between the substrate and the coating. This is very important.
  • the organometallic compound is preferably an organosilicon compound from the viewpoint of refractive index matching and adhesion to the substrate. Moreover, you may use in combination of multiple types of said organometallic compound.
  • At least one of the organometallic compounds (A) is a compound in which M in the general formula [1] is Si because a film having excellent antifogging properties and heat resistance can be obtained.
  • the binder component is one or more alkoxysilanes (for example, methyltriethoxysilane) modified with a hydrocarbon group having 1 to 18 carbon atoms, and a part of hydrogen atoms of the hydrocarbon group is an epoxy group, Those containing one or more alkoxysilanes modified with an organic group substituted with a glycidoxy group, amino group, etc. (for example, 3-glycidoxypropyltrimethoxysilane), hydrolyzed thereof, or hydrolyzed It is particularly preferred that it is decomposed and partially condensed, or a mixture of two or more of the above, because a heat-resistant antifogging film excellent in antifogging properties and heat resistance can be obtained.
  • alkoxysilanes for example, methyltriethoxysilane
  • the molecular weight of the polyacrylic acid is preferably 1,000 to 250,000. When the molecular weight is less than 1,000, there is a tendency that antifogging properties are not exhibited or sufficient antifogging properties cannot be obtained. When the molecular weight is more than 250,000, the viscosity of the coating agent increases greatly, and the film formability tends to decrease. In the present invention, the molecular weight is a weight average molecular weight.
  • Polyacrylic acids include polyacrylic acid, polymethacrylic acid, polyacrylic acid ester, or polymethacrylic acid ester, and hydrogen in the methylene chain of polyacrylic acid, polymethacrylic acid, polyacrylic acid ester, or polymethacrylic acid ester At least one selected from the group consisting of compounds in which some of the atoms are substituted with an epoxy group, a glycidoxy group, or a substituent having reactivity with an amino group can be used.
  • the reactive substituent examples include amino group, hydroxyl group, epoxy group, mercapto group, isocyanate group, alkoxy group, vinyl group, acrylic group, and methacryl group.
  • part which has polyacrylic acid and the reactive group Y as shown by the following general formula [2] copolymerized may be sufficient.
  • the reactive group Y is an amino group, a hydroxyl group, an epoxy group, a mercapto group, an isocyanate group, an alkoxy group, a vinyl group, an acrylic group, or a methacryl group, s is 10 to 350, t is It is preferably 5 to 200.
  • the compound of the general formula [2] may be a block copolymer, an alternating copolymer, or a random copolymer.
  • s and t represent the number of each repeating unit in the case of a block copolymer, and represent the total number of each structural unit in the case of an alternating copolymer and a random copolymer.
  • polyacrylic acids examples include polyacrylic acid, polymethacrylic acid, polymethyl acrylate, polymethyl methacrylate, sodium polyacrylate, acrylic acid-maleic acid copolymer salt, acrylic acid-sulfonic acid copolymer salt And a cross-linked product of neutralized polyacrylic acid, a self-crosslinked polyacrylic acid neutralized product, and the like.
  • the acrylic acid is particularly preferably polyacrylic acid.
  • the heat-resistant antifogging film of the present invention is a composite film containing a binder substrate component derived from a binder component and a component derived from polyacrylic acid, and has antifogging properties due to water absorption of the component derived from polyacrylic acid. It is preferable to express. This is because by using the composite film having such a configuration, excellent heat resistance and antifogging properties can be realized over a long period of time.
  • the coating agent it is preferable to copolymerize the binder component and polyacrylic acid by heating because the curing reaction can proceed efficiently.
  • water absorption of the coating is performed by a component derived from polyacrylic acid present in the coating, and the water absorption of the unit volume at the time of water absorption saturation of the coating is 0.05 to 3 mg / mm 3 .
  • the water absorption amount in the present invention indicates the mass of water present in the coating film based on the mass of the coating film in a state where no water is absorbed.
  • the amount of water absorption of the unit volume to the film at the time of water absorption saturation is set in the above range. If it is less than 0.05 mg / mm 3, it is necessary to increase the film thickness in order to lengthen the time until water absorption is saturated. As a result, optical distortion is likely to occur, and productivity may be lowered. This is because if it exceeds 3 mg / mm 3 , the sticky feeling of the coating becomes large, the strength is lowered, and the water resistance is deteriorated.
  • a more preferable water absorption per unit volume is 0.1 to 2 mg / mm 3 .
  • the water absorbing function can be efficiently performed by a component derived from polyacrylic acids present in the coating.
  • the carboxyl group contained in the polyacrylic acid-derived component has a function of absorbing water as bound water, and can exhibit antifogging properties due to water absorption. If the component that contributes to water absorption in the coating is a component derived from polyacrylic acid, the coating itself has excellent heat resistance, so both antifogging properties and heat resistance are excellent in the resulting antifogging article. Can be made.
  • a film that exhibits anti-fogging properties due to conventional water absorption may contain a component derived from polyvinyl alcohols or polyvinyl acetals as a water-absorbing component, but the polyvinyl alcohols or polyvinyl acetals in the coating obtained in the present invention. It is preferable that the component derived from a class is 5 mass% or less. If it exceeds 5% by mass, the film tends to be colored by heat of 100 ° C. or less, which is not preferable. A more preferable concentration of the component derived from polyvinyl alcohols or polyvinyl acetals in the coating is 1% by mass or less, more preferably 0.01% by mass or less. Further, in the obtained coating, the polyvinyl alcohols or It is particularly preferable that components derived from polyvinyl acetals are not substantially contained.
  • a difference in refractive index between the substrate and the coating is within 10%. If the refractive index difference is more than 10%, the interference action is increased, and the visibility is lowered, and interference fringes and coloring are observed visually, which is not preferable. More preferably, the refractive index difference is within 5%.
  • the refractive index difference (%) is obtained by measuring the refractive index of the base material and the coating film at a wavelength of 633 nm with an ellipsometer, and (absolute refractive index of the coating film ⁇ refractive index of the base material / refractive index of the base material) ⁇ 100. Calculate as a value.
  • the heat-resistant anti-fogging film formed from the heat-resistant anti-fogging film-forming coating agent of the present invention is excellent in heat resistance and anti-fogging property, so that it can be used in members and applications that are exposed to heat over a long period of time. I can do it. Moreover, since it is difficult for a film to peel from a base material by swelling at the time of water absorption, anti-fogging property can be maintained over a long period of time. The effect is particularly remarkable when used for a window material for a vehicle, and a safe and comfortable interior environment can be provided.
  • the heat-resistant antifogging film-forming coating agent of the present invention is a coating agent for forming a heat-resistant antifogging film on a substrate, and the heat-resistant antifogging film-forming coating agent comprises a binder component and a poly A coating agent containing acrylic acid.
  • the coating film is preferably a composite film containing a binder component and a copolymer of polyacrylic acids.
  • the coating film has excellent heat resistance and antifogging properties due to the heat resistance of the component derived from the binder component and the water absorption and heat resistance of the component derived from the polyacrylic acid.
  • antifogging properties of the antifogging article of the present invention contributes to water absorption by components derived from polyacrylic acids. Further, in addition to the water absorption effect by the component derived from the polyacrylic acid, when the component derived from the binder component contains a hydroxyl group, a carbonyl group, an amino group, a carboxyl group, a sulfo group, etc., the water absorption effect is due to their hydrophilicity. It may be promoted.
  • the water absorption effect is obtained due to the hydrophilicity of the component. It may be promoted.
  • the polyacrylic acid is copolymerized with a binder component to form a composite film containing a component derived from the polyacrylic acid and a component derived from the binder component. Elution of components derived from acids can be prevented, and antifogging properties can be expressed over a long period of time.
  • the polyacrylic acid is preferably 5 to 60% by mass based on the total amount of the binder component and the polyacrylic acid. If it is less than 5% by mass, the resulting coating film tends not to exhibit antifogging properties, or sufficient antifogging properties tend not to be obtained. If it exceeds 60% by mass, polyacrylic acids cannot be immobilized in the resulting coating, and the polyacrylic acids tend to elute upon water absorption. From the viewpoint of antifogging properties and immobilization of polyacrylic acids, the amount is more preferably 10 to 50% by mass, and still more preferably 20 to 40% by mass.
  • the coating agent may contain a solvent.
  • the solvent is not particularly limited as long as it dissolves the coating agent, and examples thereof include water, methyl alcohol, ethyl alcohol, propyl alcohol, butanol, ethylene glycol, 1,2-propanediol, and cyclohexanol. From the viewpoints of compatibility and safety, ethyl alcohol is preferred. Moreover, it is good also as a mixed solvent using a some solvent.
  • a catalyst may be added to the coating agent for forming a film for the purpose of promoting the curing reaction of the coating agent.
  • an acidic aqueous solution used as the catalyst, an aqueous solution having an acid catalyst such as an inorganic acid such as hydrochloric acid, sulfuric acid or nitric acid, or an organic acid such as acetic acid, phthalic acid or succinic acid may be selected according to the hydrolysis rate. preferable.
  • the acid catalyst is preferably added so that the pH value in the coating agent is 1 to 5.
  • a metal complex such as tin, aluminum, titanium, or zirconium can be used as the catalyst.
  • the metal complex is preferably a fluoride, chloride, bromide, iodide, acetate, nitrate, sulfate, acetylacetonate salt or the like.
  • the catalyst may be added in an amount up to 0.05 times by mass with respect to the amount of silicon compound B in the coating solution. Even if it exceeds 0.05 times the amount, there is a tendency that the catalytic effect with respect to the amount added does not further improve, so that it is not necessary to add a large amount of catalyst.
  • the curing catalyst is preferably added in an amount of 0.0001 times or more by mass ratio to the amount of silicon compound B in the treating agent.
  • the coating agent for forming a film includes a photopolymerization initiator, a thermal polymerization initiator, a surfactant, and a crosslinking agent as components other than the polyacrylic acids and the binder component as long as the object of the present invention is not impaired.
  • Other components such as an antioxidant, an ultraviolet absorber, an infrared absorber, a flame retardant, a hydrolysis inhibitor, and an antifungal agent may be added.
  • the water absorption effect is promoted by the hydrophilicity of the component in addition to the water absorption effect by the component derived from the polyacrylic acid. Therefore, it is preferable.
  • the coating agent for film formation for example, with a known application means such as dip coating, flow coating, spin coating, roll coating, spray coating, screen printing, flexographic printing, hand coating method, inkjet method, etc.
  • the coating agent for forming a film can be applied on the surface of the substrate or the primer layer formed on the surface of the substrate.
  • the step of obtaining the heat-resistant antifogging film-forming coating agent and the step of applying the coating agent on the substrate surface are preferably performed at 10 to 50 ° C.
  • the coating film of the coating agent for forming a film it can be cured by heat curing, photo curing or the like.
  • the heating temperature is preferably 50 to 200 ° C, more preferably 80 to 150 ° C. If it is less than 50 degreeC, since a cure rate is slow and hardening takes time, it is unpreferable. On the other hand, if it exceeds 200 ° C., polyacrylic acids are liable to deteriorate.
  • photocuring a general radical polymerization initiator or cationic polymerization initiator is used, and the light irradiation method is not particularly limited, and a high-pressure mercury lamp, a xenon lamp, or the like can be used.
  • the thickness of the coating is 5 ⁇ m or more. As the film thickness is increased, the water absorption capacity of the film is increased. However, if the film is too thick, optical distortion is likely to occur and productivity is reduced.
  • a treatment for improving the adhesive strength between the base material and the film can be performed on the base material surface in advance.
  • the treatment include primer treatment (second feature of the present invention), plasma irradiation, corona discharge, and high-pressure mercury lamp irradiation.
  • primer treatment it is preferable to apply a liquid having a silane coupling agent as a primer on the surface of the base material before application of the coating liquid.
  • silane coupling agent for example, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like can be used.
  • the base material a material having light transmittance, light reflectivity, or glossiness and whose safety, appearance, and design properties are significantly impaired by fogging is used.
  • Glass is used as a typical base material having optical transparency.
  • the glass is a plate glass usually used for automobiles, architectural and industrial glasses, and is a plate glass by a float method, a duplex method, a roll-out method, etc., and the manufacturing method is not particularly limited.
  • As glass types it can be used for various colored glasses such as clear, green and bronze, various functional glasses such as UV, IR cut glass and electromagnetic shielding glass, netted glass, low expansion glass, zero expansion glass and fireproof glass.
  • tempered glass, similar glass, laminated glass, multilayer glass and the like can be used.
  • a resin film such as polyethylene terephthalate, a resin plate such as polycarbonate and acrylic, and the like can also be used.
  • a typical base material having light reflectivity a mirror, a metal, a metal-plated article or the like produced by a silvering method or a vacuum film forming method can be used.
  • the plate thickness is not particularly limited, but is preferably 1.0 mm or more and 10 mm or less.
  • the window material for a vehicle is preferably 1.0 mm or more and 5.0 mm or less.
  • the formation of the coating on the substrate may be performed on only one side of the substrate or on both sides. In addition, the coating may be formed on the entire surface of the base material or a part thereof.
  • the application of the heat-resistant antifogging film-forming coating agent of the present invention includes indoor mirrors for buildings, mirrors for bathrooms, toilets, etc., windows, vehicles, ships, aircraft, etc. Glass or mirrors, specifically room mirrors, door mirrors, etc. Other lenses such as glasses and cameras, goggles, helmet shields, refrigerated showcases, refrigerated showcases, testing machines, precision instrument cases, etc. Examples include viewing windows, road reflectors, and mobile communication displays such as mobile phones.
  • the heat-resistant anti-fogging film formed from the heat-resistant anti-fogging film-forming coating agent of the present invention is excellent in heat resistance and anti-fogging property, so that it can be exposed to heat over a long period of time, such as vehicles, ships, and aircraft. It is particularly effective when used for external use such as a window glass, a mirror, a road reflector, and a display of a mobile communication body.
  • Example 1 The first feature of the present invention will be specifically described by the following Examples 1 to 5.
  • the following Comparative Examples 1 and 2 are in contrast to Examples 1-5.
  • quality evaluation was performed by the method shown below for the anti-fogging articles obtained in the present examples and comparative examples.
  • the results are shown in Table 1.
  • the amount of polyacrylic acid added refers to the mass% of the polyacrylic acid relative to the total mass of the binder component and the polyacrylic acid.
  • Pencil hardness was measured according to JISK5600.
  • Example 1 [Preparation of substrate]
  • a float glass having a thickness of 3 mm and 100 mm square was used as the substrate.
  • the surface of the substrate glass was polished with ceria fine particles, washed by brushing and dried.
  • the coating agent was applied to the base glass by a spin coating method.
  • the base glass coated with the coating agent was placed in an electric furnace maintained at 100 ° C. for 2 hours and cured to form a heat-resistant antifogging film.
  • Table 1 shows the quality evaluation results.
  • the film thickness is 35 ⁇ m
  • the transparency haze is 0.5%
  • ⁇ the antifogging property
  • the pencil hardness is HB
  • the heat resistance is unchanged in appearance and antifogging property. It was ⁇ .
  • Example 2 In Example 1, a heat-resistant antifogging film was formed in the same manner as in Example 1 except that MTES was changed to 20.78 g of tetraethoxysilane (hereinafter TEOS).
  • TEOS tetraethoxysilane
  • the film thickness is 35 ⁇ m
  • the transparent haze is 0.3%
  • ⁇ the antifogging property
  • the pencil hardness is 2H
  • the heat resistance is unchanged in appearance and antifogging property. It was ⁇ .
  • Example 3 In Example 1, a heat-resistant antifogging film was formed in the same manner as in Example 1 except that MTES was changed to 9.73 g of dimethyldiethoxysilane (hereinafter DMDES).
  • DMDES dimethyldiethoxysilane
  • the film thickness is 35 ⁇ m
  • the transparency haze is 0.5%
  • ⁇ the antifogging property
  • ⁇ the antifogging property
  • ⁇ the heat resistance is unchanged in appearance and antifogging property. It was ⁇ .
  • Example 4 In Example 1, a heat-resistant antifogging film was formed in the same manner as in Example 1 except that the molecular weight of polyacrylic acid was 5,000.
  • the film thickness is 35 ⁇ m
  • the transparency haze is 0.3%
  • ⁇ the antifogging property
  • the pencil hardness is F
  • the heat resistance is unchanged in appearance and antifogging property. It was ⁇ .
  • Example 5 a heat-resistant antifogging film was formed in the same manner as in Example 1 except that GPTMS was 8.34 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (hereinafter referred to as EETMS). .
  • the film thickness is 35 ⁇ m
  • the transparency haze is 0.5%
  • ⁇ the antifogging property
  • the pencil hardness is F
  • the heat resistance is unchanged in appearance and antifogging property. It was ⁇ .
  • Comparative Example 1 The same operation as in Example 1 was performed except that 5 g of 10 g of polyacrylic acid in Example 1 was changed to polyvinyl alcohol (hereinafter, PVA) (made by Kishida Chemical Co., Ltd.) having a molecular weight of 2,000 as a water-absorbing component other than polyacrylic acids. A heat resistant antifogging film was formed. In this heat-resistant antifogging film, the film turned yellow after the heat resistance test, and the result was x.
  • PVA polyvinyl alcohol
  • Example 2 a heat-resistant antifogging film was formed by the same operation as in Example 1 except that GPTMS was 4.24 g, MTES was 5.16 g, and polyacrylic acid was 20 g. In this heat-resistant antifogging film, the film was eluted during the antifogging test, which was a problem in appearance, and was x.
  • Example 2 The second feature of the present invention will be specifically described by the following Examples 1 to 3.
  • the following Comparative Examples 1 to 3 are in contrast to Examples 1 to 3.
  • quality evaluation was performed by the method shown below for the anti-fogging articles obtained in the present examples and comparative examples. The results are shown in Table 2.
  • the method of film thickness measurement and the 35 ° C. water vapor anti-fogging test and the evaluation criteria are the same as those described above (see the examples relating to the first feature of the present invention).
  • the test method is the same as described above, but in the evaluation criteria, it passed the test with no defects in appearance and anti-fogging property (35 ° C water vapor anti-fogging property, anti-fogging property of actual vehicle). Those with ( ⁇ ) and those with defects in appearance and those with unacceptable anti-fogging properties were taken as ( ⁇ ).
  • Condition 1 Assumed rainy season Assumed temperature outside the vehicle 20 ° C, assumed temperature inside the vehicle 25 ° C, assumed humidity inside the vehicle 95%
  • Condition 2 Assuming winter season The assumed constant temperature outside the vehicle is 0 ° C, the assumed constant temperature inside the vehicle is 25 ° C, and the assumed constant temperature inside the vehicle is 60%
  • Example 1 [Preparation of substrate]
  • a float glass having a thickness of 3 mm and 100 mm square was used as the substrate.
  • the surface of the substrate glass was polished with ceria fine particles, washed by brushing and dried.
  • Primer layer 1N nitric acid (reagent, manufactured by Kishida Chemical Co., Ltd.) mixed with 1 g of 3-aminopropyltriethoxysilane (KBM-903, manufactured by Shin-Etsu Silicone) as a silicon compound A and 98 g of denatured alcohol (Echinen F-1, manufactured by Kishida Chemical Co., Ltd.) was added to prepare a primer coating solution.
  • This primer coating solution is moistened with a wiper made of cellulose fiber (trade name “Bencot”, model M-1, 50 mm ⁇ 50 mm, manufactured by Ozu Sangyo), applied to the surface of the float glass substrate, dried and then wiped dry to apply the primer.
  • a prepared substrate was prepared.
  • GPTMS 3-glycidoxypropyltrimethoxysilane
  • MTES methyltriethoxysilane
  • KBE-13 methyltriethoxysilane
  • the coating agent was applied on the primer layer of the base glass by a spin coating method.
  • the base glass on which the coating agent was applied was placed in an electric furnace maintained at 100 ° C. for 16 hours and cured to form an antifogging film to obtain an antifogging article.
  • Table 2 shows the quality evaluation results.
  • the film thickness is 35 ⁇ m
  • the water absorption per unit volume of the film is ⁇ at 0.7 mg / mm 3
  • the 35 ° C. water vapor antifogging property is ⁇ at 120 seconds, assuming anti-fogging on the actual vehicle.
  • the property test was ⁇ for 60 minutes or more under condition 1, ⁇ in condition 2 and ⁇ at 21 minutes, adhesion did not peel, and the appearance and antifogging property did not change even after the heat test.
  • Example 2 An antifogging article is obtained by the same operation as in Example 1 except that the silicon compound A of Example 1 is changed from 3-aminopropyltriethoxysilane to 3-mercaptopropyltrimethoxysilane (KBM-803, manufactured by Shin-Etsu Silicone). It was.
  • the film thickness is 35 ⁇ m
  • the water absorption per unit volume of the film is ⁇ at 0.7 mg / mm 3
  • the 35 ° C. water vapor antifogging property is ⁇ at 120 seconds, assuming anti-fogging on the actual vehicle.
  • the property test was ⁇ for 60 minutes or more under condition 1, ⁇ in condition 2 and ⁇ at 21 minutes, adhesion did not peel, and the appearance and antifogging property did not change even after the heat test.
  • Example 3 In Example 1 [Preparation of coating agent for forming anti-fogging film], except that MTES of 15.48 g was changed to 20.78 g of tetraethoxysilane (hereinafter referred to as TEOS), it was the same as Example 1.
  • An antifogging article was obtained by the operation. In the coating of this antifogging article, the film thickness is 35 ⁇ m, the water absorption of the unit volume of the coating is ⁇ at 0.2 mg / mm 3 , and the 35 ° C. water vapor antifogging property is ⁇ at 40 seconds.
  • the property test was 45 minutes under condition 1, ⁇ under condition 2, ⁇ after 15 minutes, adhesion did not peel, and the appearance and antifogging property did not change even after the heat test.
  • Example 1 an antifogging article was obtained by the same operation as in Example 1 except that the primer layer was not formed.
  • the film thickness is 35 ⁇ m
  • the water absorption per unit volume of the film is ⁇ at 0.7 mg / mm 3
  • the 35 ° C. water vapor antifogging property is ⁇ at 120 seconds, assuming anti-fogging on the actual vehicle.
  • the condition 1 was 60 minutes or more
  • ⁇ in the condition 2
  • ⁇ in 21 minutes the adhesion was peeled
  • the appearance and antifogging property were unchanged after the heat test.
  • Comparative Example 2 Similar to Example 1 except that 10 g of polyvinyl alcohol (made by Kishida Chemical Co., Ltd.) having a molecular weight of 2,000 was used in place of 10 g of polyacrylic acid in “Preparation of antifogging film-forming coating agent” in Example 1.
  • the anti-fogging article was obtained by the operation.
  • the film thickness is 35 ⁇ m
  • the water absorption of the unit volume of the film is ⁇ at 1.0 mg / mm 3
  • the 35 ° C. water vapor antifogging property is ⁇ at 150 seconds.
  • the condition 1 was 60 minutes or more
  • ⁇ in the condition 2 ⁇ in 30 minutes
  • the adhesion was not peeled
  • ⁇ and the film was yellowed after the heat test.
  • Example 3 An antifogging article was obtained in the same manner as in Example 1 except that polyvinyl acetal having a degree of acetalization of 9% (KX-1, solid content 9%, manufactured by Sekisui Chemical Co., Ltd.) was used as the coating agent for forming an antifogging film.
  • the film thickness is 10 ⁇ m
  • the water absorption of the unit volume of the coating is ⁇ at 1.5 mg / mm 3
  • the 35 ° C. water vapor antifogging property is ⁇ at 60 seconds, assuming anti-fogging on an actual vehicle.
  • the condition 1 was 50 minutes, and in the condition 2, it was ⁇ in 18 minutes, the adhesion was not peeled, and the film was yellowed after the heat test.
  • Example 3 The third feature of the present invention will be specifically described by the following Examples 1 and 2.
  • the following Comparative Examples 1 to 5 are in contrast to Examples 1 and 2.
  • quality evaluation was performed by the method shown below for the anti-fogging articles obtained in the present examples and comparative examples.
  • the results are shown in Table 3.
  • the methods and evaluation criteria of “measurement of water absorption per unit volume of coating”, “35 ° C. water vapor antifogging test” and “heat resistance test” are the same as those described above.
  • the “actual vehicle anti-fogging property test” is the same as that described above, except that a test with less than 10 minutes or a problem with appearance was determined as (x).
  • the refractive index difference between the substrate and the coating is within 10% when the refractive index of the substrate and the coating at a wavelength of 633 nm is measured with an ellipsometer (DVA-FL3G type manufactured by Mizoji Optical Co., Ltd.) using a He-Ne laser as the light source. Was acceptable (O), and those exceeding 10% were regarded as unacceptable (X).
  • Example 1 [Preparation of substrate]
  • a float glass having a thickness of 3 mm and 100 mm square was used as the substrate.
  • the surface of the substrate glass was polished with ceria fine particles, washed by brushing and dried.
  • GPTMS 3-glycidoxypropyltrimethoxysilane
  • MTES methyltriethoxysilane
  • the coating agent was applied to the base glass by a spin coating method.
  • the base glass coated with the coating agent was placed in an electric furnace maintained at 100 ° C. for 16 hours and cured to form a coating.
  • Table 3 shows the quality evaluation results. This film had no defects in appearance, the film thickness was 35 ⁇ m, and the water absorption amount per unit volume of the film was 0.7 mg / mm 3 , which was good.
  • the refractive indexes of the float glass of a base material and the obtained coating film were 1.52 and 1.48, respectively, and the refractive index difference was 3%, and was (circle). The 35 ° C.
  • water vapor anti-fogging property of the anti-fogging article was ⁇ at 120 seconds
  • the actual anti-fogging anti-fogging test was ⁇ for 60 minutes or more under Condition 1, and ⁇ at 21 minutes under Condition 2.
  • the antifogging property 35 ° C. water vapor antifogging property, anti-fogging property of actual vehicle
  • Example 2 In Example 1 [Preparation of coating agent for forming anti-fogging film], in addition to GPTMS and MTES as binder components, titanium tetraisopropoxide (manufactured by Wako Pure Chemical Industries, Ltd.) (hereinafter referred to as TiTIP) is used. 15 g was added, and an antifogging article was obtained by the same operation as in Example 1 except that lead-based glass having a refractive index of 1.80 was used as a base material. This coating film had no defects in appearance, the film thickness was 35 ⁇ m, and the water absorption amount per unit volume of the coating film was ⁇ at 0.2 mg / mm 3 .
  • TiTIP titanium tetraisopropoxide
  • the refractive index of the obtained film was 1.68, the refractive index difference was 7%, and it was good.
  • the 35 ° C. water vapor anti-fogging property of the anti-fogging article was ⁇ in 35 seconds, the actual vehicle anti-fogging test was 30 minutes in Condition 1, and ⁇ in Condition 2 was ⁇ in 12 minutes.
  • the antifogging article even after holding the antifogging article at 100 ° C. for 200 hours as a heat resistance test, there is no defect in appearance, and it passes the antifogging property (35 ° C. water vapor antifogging property, antifogging property assumed in actual vehicles) test, It was ⁇ .
  • Comparative Example 1 Similar to Example 1 except that 10 g of polyvinyl alcohol (made by Kishida Chemical Co., Ltd.) having a molecular weight of 2,000 was used in place of 10 g of polyacrylic acid in “Preparation of antifogging film-forming coating agent” in Example 1.
  • the anti-fogging article was obtained by the operation. In the film of this antifogging article, no defects in appearance were observed, the film thickness was 35 ⁇ m, the water absorption per unit volume of the film was 1.0 mg / mm 3 , and the obtained film was refracted. The rate is 1.49, the refractive index difference is 2%, and the 35 ° C.
  • water vapor anti-fogging property is ⁇ in 150 seconds
  • the actual vehicle anti-fogging property test is 60 minutes or more in Condition 1 and in Condition 2 Although it was (circle) in 30 minutes, the film
  • Example 2 An antifogging article was obtained in the same manner as in Example 1 except that polyvinyl acetal having a degree of acetalization of 9% (KX-1, solid content 9%, manufactured by Sekisui Chemical Co., Ltd.) was used as the coating agent for forming an antifogging film.
  • KX-1 solid content 9%, manufactured by Sekisui Chemical Co., Ltd.
  • the film thickness was 10 ⁇ m
  • the water absorption per unit volume of the film was 1.5 mg / mm 3
  • the resulting film was refracted.
  • the rate is 1.46
  • the refractive index difference is 4%, ⁇ , the 35 ° C.
  • water vapor anti-fogging property is ⁇ in 60 seconds
  • the actual vehicle anti-fogging property test is 60 minutes in condition 1, and 15 in condition 2.
  • membrane turned yellow and was x by hold
  • Example 3 An antifogging article was obtained in the same manner as in Example 1 except that the amount of polyacrylic acid added was changed to 1 g in [Preparation of antifogging film-forming coating agent] in Example 1.
  • the film thickness was 35 ⁇ m
  • the water absorption of the unit volume of the film was 0.01 mg / mm 3
  • the refraction of the obtained film The rate is 1.48
  • the refractive index difference is 3%
  • the 35 ° C. water vapor anti-fogging property is x in 5 seconds
  • the actual vehicle anti-fogging property test is 3 minutes in condition 1
  • x in condition 2 is 1 X in minutes.
  • the appearance of the antifogging article was not defective even when it was held at 100 ° C. for 200 hours, but the antifogging property (35 ° C. water vapor antifogging property, anti-fogging property of actual vehicle) was rejected. And x.
  • Example 4 An antifogging article was obtained in the same manner as in Example 1 except that the amount of polyacrylic acid added was changed to 50 g in [Preparation of antifogging film-forming coating agent] in Example 1.
  • This film had stickiness and had a perspective distortion in appearance x, the film thickness was 35 ⁇ m, and the water absorption amount per unit volume of the film was 3.2 mg / mm 3 .
  • the refractive indexes of the float glass of a base material and the obtained coating film were 1.52 and 1.48, respectively, and the refractive index difference was 3%, and was (circle).
  • the anti-fogging article had a 35 ° C.
  • Comparative Example 5 An antifogging article was obtained in the same manner as in Comparative Example 1 except that lead-based glass having a refractive index of 1.80 was used as the substrate. This coating had a perspective distortion X in appearance, a film thickness of 35 ⁇ m, and a water absorption amount per unit volume of the coating of 1.0 mg / mm 3 was ⁇ . Moreover, the refractive index of the float glass of a base material and the obtained coating film was 1.80 and 1.49, respectively, and the refractive index difference was 17% and was x. The 35 ° C.
  • water vapor anti-fogging property of the anti-fogging article was ⁇ in 150 seconds
  • the actual vehicle anti-fogging test was ⁇ for 60 minutes or more in Condition 1, and ⁇ in 30 minutes in Condition 2.
  • the film was yellowed by holding the antifogging article at 100 ° C. for 200 hours, and the result was x.

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  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

L'invention porte sur un article anti-buée qui comprend une base et un film anti-buée résistant à la chaleur qui est formé sur la base. L'article antibuée est caractérisé en ce que le film anti-buée est un film composite qui contient un composant substrat liant issu d'un composant liant et un composant issu de poly(acides acryliques) et les propriétés anti-buée se manifestent lorsque le composant issu de poly(acides acryliques) absorbe de l'eau. L'article antibuée possède des propriétés anti-buée et une résistance à la chaleur excellentes et peut être utilisé dans diverses applications telles que des vitres anti-buée pour des véhicules ou des bâtiments, des miroirs anti-buée, des lentilles et des dispositifs d'affichage.
PCT/JP2011/051070 2010-01-25 2011-01-21 Article anti-buée WO2011090156A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP2010013621A JP2011153164A (ja) 2010-01-25 2010-01-25 耐熱性防曇膜及びその形成方法並びに耐熱性防曇膜形成用塗布剤
JP2010-013621 2010-06-02
JP2010155164A JP2012017394A (ja) 2010-07-07 2010-07-07 防曇性物品
JP2010-155164 2010-07-07
JP2010155231A JP2012017220A (ja) 2010-07-07 2010-07-07 防曇性物品
JP2010-155231 2010-07-07

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014025654A1 (fr) * 2012-08-09 2014-02-13 Illinois Tool Works Inc. Composition antibuée absorbant l'humidité et un procédé pour l'utilisation de celle-ci
US20150111043A1 (en) * 2012-03-13 2015-04-23 Central Glass Company, Limited Anti-Fogging Film-Forming Material, Coating Liquid for Forming Anti-Fogging Film, Anti-Fogging Article, and Methods for Producing These
JP2016058025A (ja) * 2014-09-12 2016-04-21 株式会社小糸製作所 車両用記録装置
WO2023166761A1 (fr) * 2022-03-02 2023-09-07 株式会社レゾナック Agent antibuée, procédé antibuée pour structure de lampe de véhicule, et structure de lampe de véhicule
EP4317098A1 (fr) * 2022-08-01 2024-02-07 Papadopoulos Nikolaos-Xafakis Sotirios G.P. Systèmes de nano-revêtement durables faciles à nettoyer

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Publication number Priority date Publication date Assignee Title
JPH05271549A (ja) * 1992-03-30 1993-10-19 Arakawa Chem Ind Co Ltd ポリシロキサン複合重合体の製造法およびコーティング組成物
JPH09113704A (ja) * 1995-10-20 1997-05-02 Nakato Kenkyusho:Kk 防曇性反射防止膜、光学部品、及び防曇性反射防止膜の製造方法
JPH1121512A (ja) * 1997-07-01 1999-01-26 Asahi Denka Kogyo Kk 親水性コーティング用樹脂組成物
JP2000109631A (ja) * 1998-10-06 2000-04-18 Toto Ltd 防曇性複合材料

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05271549A (ja) * 1992-03-30 1993-10-19 Arakawa Chem Ind Co Ltd ポリシロキサン複合重合体の製造法およびコーティング組成物
JPH09113704A (ja) * 1995-10-20 1997-05-02 Nakato Kenkyusho:Kk 防曇性反射防止膜、光学部品、及び防曇性反射防止膜の製造方法
JPH1121512A (ja) * 1997-07-01 1999-01-26 Asahi Denka Kogyo Kk 親水性コーティング用樹脂組成物
JP2000109631A (ja) * 1998-10-06 2000-04-18 Toto Ltd 防曇性複合材料

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150111043A1 (en) * 2012-03-13 2015-04-23 Central Glass Company, Limited Anti-Fogging Film-Forming Material, Coating Liquid for Forming Anti-Fogging Film, Anti-Fogging Article, and Methods for Producing These
US9765224B2 (en) * 2012-03-13 2017-09-19 Central Glass Company, Limited Anti-fogging film-forming material, coating liquid for forming anti-fogging film, anti-fogging article, and methods for producing these
WO2014025654A1 (fr) * 2012-08-09 2014-02-13 Illinois Tool Works Inc. Composition antibuée absorbant l'humidité et un procédé pour l'utilisation de celle-ci
US9150766B2 (en) 2012-08-09 2015-10-06 Illinois Tool Works, Inc. Moisture absorbing anti-fog composition and process for the use thereof
JP2016058025A (ja) * 2014-09-12 2016-04-21 株式会社小糸製作所 車両用記録装置
WO2023166761A1 (fr) * 2022-03-02 2023-09-07 株式会社レゾナック Agent antibuée, procédé antibuée pour structure de lampe de véhicule, et structure de lampe de véhicule
EP4317098A1 (fr) * 2022-08-01 2024-02-07 Papadopoulos Nikolaos-Xafakis Sotirios G.P. Systèmes de nano-revêtement durables faciles à nettoyer

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