WO2007018270A1 - Article antibuée et procédé servant à produire celui-ci - Google Patents

Article antibuée et procédé servant à produire celui-ci Download PDF

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Publication number
WO2007018270A1
WO2007018270A1 PCT/JP2006/315871 JP2006315871W WO2007018270A1 WO 2007018270 A1 WO2007018270 A1 WO 2007018270A1 JP 2006315871 W JP2006315871 W JP 2006315871W WO 2007018270 A1 WO2007018270 A1 WO 2007018270A1
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WIPO (PCT)
Prior art keywords
hydrophilic
antifogging
group
crosslinking agent
inorganic
Prior art date
Application number
PCT/JP2006/315871
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English (en)
Japanese (ja)
Inventor
Takeshi Yabuta
Takeshi Sunaga
Mizuho Matsuda
Kazutaka Kamitani
Original Assignee
Nippon Sheet Glass Company, Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2005231588A external-priority patent/JP2008272935A/ja
Priority claimed from JP2005231605A external-priority patent/JP2008273746A/ja
Application filed by Nippon Sheet Glass Company, Limited filed Critical Nippon Sheet Glass Company, Limited
Publication of WO2007018270A1 publication Critical patent/WO2007018270A1/fr

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
    • C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
    • C03C2217/47—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase consisting of a specific material
    • C03C2217/475—Inorganic materials
    • C03C2217/478—Silica
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/75—Hydrophilic and oleophilic coatings
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/77—Coatings having a rough surface

Definitions

  • the present invention relates to an antifogging article and a method for producing the same.
  • an antifogging agent containing an organic polymer having a carboxylate group may be used.
  • an organic polymer having a carboxylate group may be used.
  • at least one functional metal chelate compound is 5 parts by weight or less, and at least one organic polymer containing a carboxyl group and / or a hydroxyl group is 2 to 20 weights.
  • An antifogging coating composition characterized by being contained in a water-containing organic solvent is disclosed.
  • an organic material antifogging agent having water absorption is used.
  • the film in Japanese Patent Application Laid-Open No. 2005-110918, in an antifogging mirror comprising a mirror main body and a film in close contact with the mirror main body, the film is a film exhibiting water absorption and hydrophilicity, Discloses an anti-fog mirror having a diameter of 5 ⁇ m or more and 30 ⁇ m or less. In this antifogging mirror, the film has sufficient water absorption due to the oxyethylene chains present in the film.
  • the antifogging coatings of Examples described in JP-A-10-195423 require a relatively thick film thickness of 2 to 5 zm.
  • the present invention has been made paying attention to such conventional problems, and its purpose is to An object of the present invention is to provide an antifogging article having a good antifogging property even with a relatively thin film thickness, as an antifogging article using a hydrophilic coating containing an aqueous organic polymer.
  • the inventors of the present invention have studied a hydrophilic film containing a hydrophilic organic polymer formed on the surface of an inorganic article that achieves the above object, focusing on the hydrophilic functional group of the hydrophilic organic polymer. Went.
  • an antifogging film containing a hydrophilic organic polymer having a carboxynole group and a crosslinking agent is formed on the surface of the inorganic article, and only a part of the carboxynore group is crosslinked by the crosslinking agent.
  • a hydrophilic organic polymer having a carboxynole group and a crosslinking agent is formed on the surface of the inorganic article, and only a part of the carboxynore group is crosslinked by the crosslinking agent.
  • a hydrophilic film comprising a hydrophilic organic polymer having a carboxylate group and a crosslinking agent as main components is formed on the surface of an inorganic article. It is an antifogging article in which only a part of the group is crosslinked by the crosslinking agent.
  • This antifogging article exhibits good antifogging properties even when the hydrophilic coating film is thin. Moreover, in the hydrophilic film, since the carboxyl group is partially crosslinked, the water resistance is also excellent. In addition, when a thin hydrophilic coating is formed, the abrasion resistance and scratch resistance of the hydrophilic coating are improved. In addition, when a base having a convex group composed of inorganic fine particles is formed, the hydrophilic film is further excellent in wear resistance and scratch resistance.
  • FIG. 1 is a FE-SEM photograph showing the observation results of the base formed in Example 2-1.
  • FIG. 2 is a FE-SEM photograph showing the observation results of the antifogging article produced in Example 2_1.
  • examples of the inorganic article include articles such as glass, ceramics, and metals, preferably glass articles, and specifically, glass plates and glass mirrors.
  • a hydrophilic organic polymer having a carboxyl group (a hydrophilic organic polymer containing a carboxyl group in the molecule) is used.
  • the carboxyl group serves as a cross-linking point in the cross-linking reaction with the cross-linking agent, and thus strengthens the bond between the hydrophilic organic polymers and strengthens the hydrophilic film.
  • the carboxynole group has hydrophilicity, Contributes to improved fogging performance.
  • the hydrophilic organic polymer having a carboxynole group is preferably at least one selected from an acrylic acid polymer and a maleic acid polymer.
  • acrylic acid polymers include polyacrylic acid and acrylic acid copolymers.
  • acrylic acid copolymers include acrylic acid-maleic acid copolymer, ethylene-acrylic acid copolymer, styrene-acrylic acid copolymer, isobutylene-acrylic acid copolymer, and acrylamide-acrylic acid.
  • Copolymers, diallyldimethylammonium chloride acrylic acid copolymer, starch-acrylic acid copolymer, N-Buracetamide-acrylic acid copolymer, acrylicamine-acrylic acid copolymer, and their sodium Examples include salt.
  • maleic acid polymers include polymaleic acid and maleic acid copolymers.
  • maleic acid-based copolymers include acrylic acid-maleic acid copolymer, attalinoleamide monomaleic acid copolymer, acrylic acid ester-maleic anhydride copolymer, ethylene ethyl acrylate, maleic anhydride copolymer.
  • Polymer ethylene maleic anhydride copolymer, styrene maleic anhydride copolymer, isobutylene maleic anhydride copolymer, butadiene maleic anhydride copolymer, diisobutene maleic anhydride copolymer, butyl methyl ether maleic anhydride copolymer Polymer, vinyl acetate-maleic anhydride copolymer, sulfonated styrene, isobutylene, maleic anhydride copolymer, divinyl ether, maleic anhydride copolymer, methoxyethylene, maleic anhydride copolymer, alkylstyrene, maleic anhydride copolymer , Polyethylene oxide anhydrous male Examples thereof include an in acid copolymer, a norbornene-maleic anhydride copolymer, a dimethyl diallyl ammonium chloride monomaleic acid copolymer, and a sodium salt thereof.
  • hydrophilic organic polymer having a carboxynole group may be used alone or in combination of two or more.
  • the crosslinking agent is not particularly limited as long as it can react with two or more force lpoxyl groups of the hydrophilic organic polymer per molecule of the crosslinking agent, and is not limited.
  • Epoxy compound, carbodiimide compound, amine compound , Ethyleneimine compounds, oxazoline compounds One selected from the group consisting of polyvinyl alcohols, glycerin, glycols, and organometallic compounds is preferred.
  • a surfactant having a function as a cross-linking agent described later can also be used. These may be used alone or in combination of two or more.
  • the hydrophilic coating contains a hydrophilic organic polymer having a carboxyl group and a crosslinking agent as main components.
  • the hydrophilic coating contains a hydrophilic organic polymer having a carboxyl group and a crosslinking agent. It means to contain at least 70% by mass, preferably at least 70% by mass.
  • the hydrophilic organic polymer and the crosslinking agent may be bonded to each other by a reaction.
  • the hydrophilic film may further contain a surfactant.
  • the surfactant has the effect of further improving the antifogging property of the coating.
  • any of anionic, nonionic, cationic and zwitterionic types can be used.
  • a surfactant having a polyalkylene oxide group and an alkyl group can be suitably used.
  • the hydrophilic organic polymer having a carboxyl group is a maleic acid polymer
  • the carboxylate group adjacent to the maleic acid unit exhibits high water absorption.
  • adjacent carboxyl groups are bonded to each other by a hydrogen bond, resulting in a decrease in water absorption, resulting in a decrease in antifogging property.
  • hydrogen bonding between the carboxynole groups can be suppressed due to steric hindrance.
  • the hydrophilic film further contains a surfactant and the hydrophilic organic polymer is a maleic acid polymer.
  • a method for immobilizing the surfactant on the carboxyl group of the maleic acid unit is, for example, immobilization by a covalent bond.
  • the surfactant having a polyalkylene oxide group and an alkyl group usually has a ⁇ H group at the end of the polyalkylene oxide group, and therefore, an ester bond is formed between the OH group and the carboxyl group of the maleic acid unit. It can be fixed more.
  • a surfactant power that can be immobilized on a carboxyl group of a maleic acid unit and has a polyalkylene oxide group and an alkyl group.
  • a more preferred example is polyoxyethylene lauryl.
  • a surfactant having two or more polyoxyalkylene oxide groups can react with the base force S of the polyalkylene oxide group terminal and two or more carboxy groups of the hydrophilic organic polymer. Therefore, in the present invention, a surfactant having two or more polyoxyalkylene oxide groups and an alkyl group can also be used as the above-mentioned crosslinking agent. Even by crosslinking only with the surfactant, a strong film that does not dissolve in water can be obtained, and many carboxynole groups of the hydrophilic organic polymer can be left, so that it is possible to obtain a small amount having good antifogging properties. it can.
  • the above surfactants may be used alone or in combination of two or more.
  • content of surfactant 1-30 mass% is preferable with respect to the mass of a hydrophilic organic polymer. It should be noted that the presence of a surfactant in the hydrophilic film can be confirmed by infrared spectroscopy.
  • the hydrophilic film is formed on the surface of the inorganic article, but may be formed only in a region where the antifogging property of the surface of the inorganic article is required.
  • the hydrophilic film only a part of the carboxyl group of the hydrophilic organic polymer is crosslinked by the crosslinking agent.
  • the hydrophilic organic polymer has a carboxyl group in the molecule, and the functional group itself has a high hydrogen bondability and can form a relatively strong film. Remaining.
  • by crosslinking a part of the carboxyl groups in the hydrophilic organic polymer it is possible to form a hydrophilic film having water resistance without losing the antifogging property.
  • the ratio of carboxyl groups to be crosslinked may be at least 0.1% or more, preferably 1% or more of the total number of carboxyl groups (before crosslinking). However, if all the carboxyl groups are cross-linked, the anti-fogging property will not be exerted. Therefore, in the present invention, a part of the carboxyl groups cross-linked by the cross-linking agent is used.
  • the ratio of the crosslinking agent to be used is determined in consideration of the type of the crosslinking agent, that is, the hydrophilicity of the crosslinking agent itself, the equivalent of the functional group of the crosslinking agent that can react with the carboxyl group, the reactivity of the functional group, and the like. What is necessary is just to determine suitably.
  • the lower limit of the proportion of the cross-linking agent is preferably 0.1% by mass with respect to the hydrophilic organic polymer, more preferably 1.0% by mass.
  • the upper limit of the ratio of the crosslinking agent can be up to about 2.5 to 3 times the mass of the hydrophilic organic polymer.
  • the hydrophilic film it can be confirmed by infrared spectroscopy that the carboxyl group is crosslinked by a crosslinking agent and that the carboxyl group is in a free state without being crosslinked. it can.
  • the hydrophilic coating can be blended with any component within a range not contrary to the object of the present invention.
  • Optional ingredients include additives such as antistatic agents, antioxidants, UV absorbers, infrared absorbers, light stabilizers, heat stabilizers, lubricants, nucleating agents, antiblocking agents, heat retention agents, and various stabilizers.
  • Inorganic fillers such as calcium carbonate, silica, titanium oxide and talc; pigments and the like.
  • the thickness of the hydrophilic coating is defined as the distance between the surface of the inorganic article and the outermost surface (exposed surface) of the hydrophilic coating.
  • the thickness of this hydrophilic coating can be made thinner than the conventional thickness (micron order), and a thickness in the range of 20 to 800 nm is preferred. If the thickness is less than 20 nm, the antifogging property may be insufficient. If the thickness exceeds 800 nm, the wear resistance may be poor.
  • the thickness of the hydrophilic coating is more preferably 150 nm or less, more preferably 100 ⁇ m or less, and even 50 nm or less.
  • a base having a convex group composed of inorganic fine particles is formed on the surface of an inorganic article on which a hydrophilic film is formed.
  • This base is very strong against the compressive force in the direction perpendicular to the surface due to the inherent hardness of the inorganic fine particles.
  • a hydrophilic film is formed on the convex group, at least a part of the hydrophilic film enters the gaps between the inorganic fine particles and is fixed (preferably, the hydrophilic film is the It is filled and fixed in the gaps of the convex group of the base).
  • the area of the joint surface with the hydrophilic film is enlarged and the surface shape is complicated, so that the adhesion is drastically improved. Further, since there is a base having a convex group, when a force parallel to the film surface such as surface wear is applied, the hydrophilic film has an effect that it is difficult to peel off the article easily. As a result, the wear resistance of the antifogging coating is improved. Since the hydrophilic film is formed on the hard substrate with an appropriate thickness, the anti-fogging film has excellent scratch resistance.
  • the antifogging article of the present invention further includes a base having a convex group composed of organic fine particles between the inorganic article and the hydrophilic coating, It is preferable that a hydrophilic film is formed. That is, in the antifogging article, specifically, a base having a convex group composed of inorganic fine particles is formed on the surface of the inorganic article, and a hydrophilic organic polymer having a carboxyl group is formed on the base. A hydrophilic film comprising a crosslinking agent as a main component is formed, and the hydrophilic film is an antifogging article in which only a part of the carboxyl group is crosslinked by the crosslinking agent.
  • the average height of the convex group is 20 to 300 nm.
  • the average height of the convex portion group is an average of the height from the surface of the inorganic article to the apex of each convex portion of the convex portion group, and can be measured by a scanning electron microscope.
  • the height of each convex portion of the convex portion group is preferably within a predetermined range.
  • This predetermined range is within ⁇ 30%, preferably within ⁇ 20%, more preferably within ⁇ 10%, based on the average height of the convex group.
  • the convex portion of the convex portion group may be composed of a single particle or an aggregate of a plurality of particles.
  • the base having a convex group is formed by bonding inorganic fine particles to the surface of the inorganic article.
  • the bonding method is not particularly limited, and inorganic fine particles that are not particularly limited may be directly bonded to the surface of the inorganic article, or a binder or the like may be used. May be combined.
  • inorganic fine particles constituting the convex group fine particles such as tin oxide and silica are preferable.
  • Tin oxide fine particles are preferably formed by chemical vapor deposition (CVD). According to the CVD method, tin oxide fine particles strongly bonded to an inorganic article can be formed.
  • CVD chemical vapor deposition
  • silica fine particles having a uniform particle diameter are readily available, it is easy to control the average height of the convex group. Since the silica fine particles may not have sufficient binding force with the inorganic article, the silica fine particles are preferably bonded to the surface of the inorganic article via a binder.
  • the particle size of the silica fine particles is preferably 20 to 300 nm force S. When silica fine particles having this particle diameter are used, a convex group having a preferable average height can be easily formed.
  • the particle size of the silica fine particles is an average of the primary particle sizes, and can be measured using a scanning electron microscope.
  • silica fine particles having different particle diameters can be used in combination.
  • the height of the convex portion group is determined by the silica fine particles having a large particle diameter.
  • the fine silica particle having a small particle size contributes to an increase in the surface area of the substrate, and supplements the bonding force between the fine silica particle having a large particle size and the surface of the inorganic article as a binder.
  • the antifogging article of the present invention is not particularly limited in its production method.
  • a coating liquid containing a hydrophilic organic polymer having a carboxyl group and a crosslinking agent is applied to the surface of the machine article, and a hydrophilic film is formed by crosslinking only a part of the carboxyl group with the crosslinking agent.
  • a base having a convex group composed of inorganic fine particles is formed on the surface of the inorganic article, and a hydrophilic group having a carboxyl group is formed on the surface of the base. It can be produced by applying a coating liquid containing an organic polymer and a crosslinking agent, and forming a hydrophilic film by crosslinking only a part of the carboxyl group with a crosslinking agent.
  • the base is formed by applying a dispersion liquid in which inorganic fine particles and, if necessary, an inorganic binder, a catalyst, and the like are mixed in a solvent, to the inorganic article and drying.
  • the solvent and the catalyst may be appropriately determined according to the type of the inorganic binder.
  • what is necessary is just to determine the addition amount of each component suitably.
  • the hydrophilic film is formed by mixing a hydrophilic organic polymer having a carboxyl group, a crosslinking agent, and, if necessary, a surfactant in a solvent to form a coating liquid, which is used as an inorganic article. It can be applied by applying to the surface (surface of the underlayer) and drying, followed by heating to a temperature higher than the initiation temperature of the crosslinking reaction, or by heating to a temperature higher than the initiation temperature of the crosslinking reaction and drying while crosslinking. In order to crosslink only a part of the carboxyl group with the crosslinking agent, it is convenient to adjust the amount of the reactive functional group of the crosslinking agent relative to the carboxyl group.
  • the conventional hydrophilic coating required a thickness on the order of micron, but the thickness of the hydrophilic coating was on the order of several hundred nm. Therefore, it has the required anti-fogging property. Furthermore, it is excellent also in water resistance. Further, when the inorganic article has a base, the antifogging article is excellent in wear resistance and scratch resistance.
  • the antifogging article can be suitably used as a glass plate, an optical lens, a mirror or the like for automobiles and building materials.
  • a hydrophilic film (antifogging film) is formed on a glass plate as an antifogging article. Obtained protection Various characteristics shown below were evaluated for the cloudy glass plate.
  • Example 2 The lack of uneven coating and streaks of the hydrophilic coating (antifogging coating) generated by flow coating was judged visually. In Example 2 and Comparative Example 2, the determination was made according to the following criteria.
  • A The surface is uniform with no unevenness or streaks.
  • the antifogging property was evaluated by the following method called an exhalation method. That is, a certain amount of exhaled air was sprayed on a glass with a hydrophilic film (antifogging film) kept at room temperature, and the degree of cloudiness was judged visually.
  • the hydrophilic coating (antifogging coating) before and after the wear of the compress was evaluated. In Example 2 and Comparative Example 2, the determination was made according to the following criteria.
  • Example 2 the surface of the film was rubbed back and forth using a poultice, and the degree of scratches was visually determined. Judgment criteria are as follows.
  • Table 1 shows purified water as a solvent, butyl methyl ether-maleic anhydride copolymer (Gantrez AN-119) as a hydrophilic organic polymer, and glycerin as a crosslinking agent. The resulting mixture was mixed to give a coating solution for forming a hydrophilic film.
  • the numbers in parentheses are the proportions (mass percent) of each component in the coating solution.
  • the flow coating was performed in a room adjusted to a temperature of 20 ° C and a humidity of 30%. After coating, it was naturally dried and heated in an oven heated to 120 ° C. for 30 minutes to obtain a glass plate with a hydrophilic film.
  • the film thickness of the hydrophilic film was about lOOnm.
  • a glass plate with a hydrophilic coating was obtained in the same manner as in Example 1-1 except that heating was omitted and crosslinking was not performed.
  • this glass plate was evaluated as above, it showed antifogging properties.
  • the surface was wiped with a cloth soaked in water, the hydrophilic film peeled off and no longer showed anti-fogging lifetime.
  • each component was mixed so as to have the composition shown in Table 1 to obtain a coating solution for forming a hydrophilic film.
  • a hydrophilic coating was formed on the cleaned substrate in the same manner as in Example 1 to obtain a glass plate with a hydrophilic coating.
  • the film thickness of the antifogging film in Examples 1-2 and 1-3 was about 10 nm, in Examples 14 and 15 it was about 40 nm, and in Example 6 it was about 6 Onm.
  • AN— 119 Bier methyl ether-maleic anhydride copolymer, Gantrez AN— 1 19
  • PAS-84 Maleic acid-dimethyl diallyl ammonium chloride copolymer, PAS-8
  • Glycerin Glycerin
  • EX-830 Epoxy crosslinking agent, Denacol EX—830
  • PVA—117 water-soluble polymer, polybulal alcohol, PVA—117
  • Ethanol solvent manufactured by Nippon Alcohol Sales Co., AP-7
  • concentrated hydrochloric acid cHCl
  • colloidal silica dispersion as inorganic fine particles manufactured by Nissan Chemical Industries, Snowtex C
  • tetraethoxy as a binder Silane
  • TEOS tetraethoxy
  • ureidosilane 3-ureidopropyltrimethoxysilane
  • the coating solution obtained above was flow-coated on a soda lime glass plate (150 ⁇ 60 ⁇ 3.4 mm) washed as a substrate. Flow coating was performed in a room adjusted to a temperature of 20 ° C and a humidity of 30%. After the flow coating, the film was cured by natural drying. In this way, a base having a convex group composed of silica fine particles as inorganic fine particles was formed on the surface of the glass plate, which was an inorganic article.
  • the cross section of the base thus obtained was observed obliquely from above with a field emission scanning electron microscope (FE-SEM, manufactured by Hitachi, Ltd., S-4500). The results are shown in Fig. 1.
  • the shooting conditions were an applied voltage of 10 kV and a shooting magnification of 100,000. From Fig. 1, it can be seen that the silica particles with uniform particle size are bonded to the surface of the glass plate to form a base having convex groups.
  • the film thickness of the underlayer was about 30 nm.
  • a coating solution A1 for forming a hydrophilic film was flow-coated on a substrate with a base.
  • the flow coating was performed in a room adjusted to a temperature of 20 ° C and a humidity of 30%. After coating, it was naturally dried and heated in an oven heated to 120 ° C. for 30 minutes to form a hydrophilic film, thereby obtaining a glass plate with an antifogging film.
  • FIG. 2 shows a result of observing a cross section of the antifogging article according to the present invention obtained from the above obliquely from above with an FE-SEM.
  • the shooting conditions are the same as the above conditions.
  • FIG. 2 shows that a hydrophilic film is formed so as to cover the surface of the base described above.
  • the film thickness of the hydrophilic film was about 30 nm.
  • A-103 Burmethyl ether-maleic anhydride copolymer
  • VEMA A-103 A-106 Vinyl methyl ether maleic anhydride copolymer
  • VEMA A—106 TL-400 Acrylic acid maleic acid copolymer salt
  • PAS-84 Maleic acid-dimethyl diallyl ammonium chloride copolymer, PAS-8
  • EX-830 Epoxy crosslinking agent, Denacol EX—830
  • EX-614B Epoxy crosslinking agent, Denacol EX-614B
  • WS-700 Oxazoline compound
  • PVA 217 water-soluble polymer, polyvinyl alcohol, PVA 217
  • TPG glycol-based solution, tripropylene glycol
  • TC 400 Water-soluble titanium compound, ORGATICS TC 400
  • PVP Water-soluble polymer, polybulurpyrrolidone
  • Example 2-1 Except for changing the composition of the coating solution for forming a hydrophilic film, a substrate with a base was prepared in the same manner as in Example 2-1, and a hydrophilic film was formed on the substrate. A lath plate was obtained.
  • the film thicknesses of the hydrophilic coatings in each Example and Comparative Example were both about 30 nm.
  • the method for preparing the coating liquid for forming a hydrophilic film used in each example and comparative example is shown below.
  • composition in Table 3 While referring to the composition in Table 3, purified water as a solvent, concentrated hydrochloric acid as a catalyst, butyl methyl ether-maleic anhydride copolymer (VEMA A-103) and acrylic acid-maleic acid copolymer as hydrophilic organic polymers.
  • Combined salt (Aquaric TL-400) and carboji Carpolite V-02 was mixed as an imide-based cross-linking agent and subjected to a hydrolysis reaction in a thermostatic bath at 50 ° C for about 3 hours. Thereafter, each component was diluted with purified water so that the ratios shown in Table 3 were obtained, and at that time, Lapisol A-30 was added as a surfactant to obtain a coating solution A4.
  • VEMA A_103 butyl methyl ether-hydrous maleic acid copolymer
  • the hydrolyzed solution was added to a solution in which purified water was adjusted to be alkaline.
  • the ethyleneimine compound epomin SP-012 was added thereto and stirred. Thereafter, each component was diluted with purified water so that the proportions shown in Table 3 were obtained, and used as coating solution A5.
  • VEMA A-106 butyl methyl ether-hydrous maleic acid copolymer
  • this hydrolysis solution was mixed with a diluted solution of Epoxol WS-700, which is an oxazoline-based compound, and the surfactant lapizol A-30. After that, each component was diluted with purified water so that the ratio shown in Table 3 was obtained, and it was used as coating solution A6.
  • Purified water was used as a solvent to hydrolyze vinyl methyl ether water-free maleic acid copolymer (VEMA A-106) as a hydrophilic organic polymer.
  • VEMA A-106 vinyl methyl ether water-free maleic acid copolymer
  • PVA 217 polyvinyl alcohol
  • VEMA A-106 butyl methyl ether-hydrous maleic acid copolymer
  • this hydrolysis solution and a solution obtained by diluting glycerin with purified water were mixed. Thereafter, each component was diluted with purified water so that the proportions shown in Table 3 were obtained, and used as coating solution A8.
  • VEMA®-103 butyl methyl ether-hydrous maleic acid copolymer
  • this hydrolyzed solution was mixed with a solution in which ORGATICS TC-400, which is a water-soluble titanium compound, was dissolved in purified water, and RAPISOL ⁇ _30 as a surfactant. Thereafter, each component was diluted with purified water so that the proportions shown in Table 3 were obtained, and used as coating solution A10.
  • Coating liquid composition B3 for forming a hydrophilic film in Comparative Example 2-3 (Coating liquid composition B3 for forming a hydrophilic film in Comparative Example 2-3)
  • Polyvinylpyrrolidone which is a water-soluble polymer, and calpolite V-02 as a carpositimide-based crosslinking agent were dissolved in purified water with the composition shown in Table 3 to obtain coating liquid B3.
  • Example 2-1 is an example using an epoxy-based crosslinking agent.
  • Example 2-1 both excellent antifogging properties and scratch resistance could be achieved. This is considered to be because the hydrophilic film was crosslinked by the crosslinking agent.
  • Example 2-2 is an example using an epoxy-based crosslinking agent having a structure different from that of the crosslinking agent used in Example 2-1.
  • the anti-fogging property was a practical level, although it was slightly inferior before and after the wear of the compresses compared with Example 2-1.
  • the gender is also considered different.
  • Examples 2-3 are examples in which an acrylic monomaleic acid copolymer was added as the second component of the hydrophilic organic polymer.
  • examples 2-3 both excellent anti-fogging properties and scratch resistance are achieved. I was able to do S. In particular, it was excellent in antifogging property after wear of a compress. This is because by adding an acrylic acid maleic acid copolymer, the carboxyl group contained in the acrylic acid contributes to the antifogging property, and further has a cross-linked structure due to the addition of a cross-linking agent. It is thought that anti-fogging properties could be maintained afterwards.
  • Example 2_4 is an example in which the crosslinking agent in Example 2_3 was changed to a carpositimide system. As a result, although the antifogging property and scratch resistance were slightly deteriorated from those of Example 2-3, good results were shown. Carpositimide cross-linking agents are highly reactive, so it is considered that the cross-linking structure was efficiently formed with a small amount of addition.
  • Examples 2_5 to 2_9 were examined by adding various compounds as crosslinking agents to the same hydrophilic organic polymer. All the examples showed practically sufficient antifogging properties and scratch resistance. The amount of the base polymer is adjusted as appropriate.
  • Example 2-10 was an example using a water-soluble titanium compound as a crosslinking agent, and exhibited antifogging properties and scratch resistance corresponding to those of Example 2-1. This is thought to be because the scratch resistance was improved because the carboxyl groups were crosslinked by coordinating the metal titanium to the carboxyl group.
  • Examples 2-11 and 2-12 are examples in which a maleic acid-dimethyldiammyl ammonium chloride copolymer was used as the hydrophilic organic polymer. In all examples, the appearance after film formation was slightly white, but showed practical antifogging properties. In Examples 2 to 11, the antifogging property before and after the compress was apt to be slightly inferior.
  • Comparative Example 2-1 is an example using a hydrophilic organic polymer (PVP) having no carboxyl group. Although antifogging property was good, it was inferior to scratch resistance. In particular, the film surface was scratched, and the antifogging deterioration immediately after wear of the compress was noticeable. This is probably because uncrosslinked PVP is very soluble in water, so the hydrophilic coating was dissolved when the compress was worn.
  • PVP hydrophilic organic polymer
  • Comparative Example 2_2 is an example in which a crosslinking agent is added to the same hydrophilic organic polymer as Comparative Example 2-1. Although the antifogging property was good, the scratch resistance was poor. This is probably because the PVP used did not have a carboxyl group, so even if a cross-linking agent was added, it did not form a cross-linked structure, so the wear resistance was poor.
  • Comparative Examples 2-3 are also examples in which a crosslinking agent was added to PVP. This is the same as Comparative Example 2-2. Thus, although the antifogging property showed a good result, it was inferior in scratch resistance. This is probably because the PVP used did not have a carboxynole group, so even if a cross-linking agent was added, a cross-linked structure was not formed, and thus the wear resistance was poor.
  • the antifogging article of the present invention can be suitably used as an article requiring antifogging properties, such as a window glass plate (for automobiles, building materials, etc.), optical lenses, mirrors, and the like.

Abstract

Article antibuée ayant un revêtement hydrophile contenant un polymère organique hydrophile. Il possède des propriétés antibuée satisfaisantes même lorsque le revêtement est relativement mince. L'article antibuée est caractérisé en ce qu'il comprend un article inorganique et, formé sur la surface de celui-ci, un revêtement hydrophile comprenant un polymère organique hydrophile carboxylé et un agent de réticulation comme ingrédients principaux et en ce que le revêtement hydrophile a été réticulé au niveau de seulement une partie des groupes carboxyles avec l'agent de réticulation. Former une couche primaire ayant des protubérances constituées de fines particules inorganiques sur la surface de l'article inorganique entraîne une meilleure résistance à l'usure et une meilleure résistance aux rayures.
PCT/JP2006/315871 2005-08-10 2006-08-10 Article antibuée et procédé servant à produire celui-ci WO2007018270A1 (fr)

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JP2005231588A JP2008272935A (ja) 2005-08-10 2005-08-10 防曇性物品およびその製造方法
JP2005231605A JP2008273746A (ja) 2005-08-10 2005-08-10 防曇性物品およびその製造方法
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2080740A1 (fr) * 2007-12-17 2009-07-22 Guardian Industries Corp. Revêtement hydrophile et son procédé de fabrication
JPWO2013145595A1 (ja) * 2012-03-27 2015-12-10 日本板硝子株式会社 やけの防止に適した被膜が形成されたガラス板およびその製造方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62129367A (ja) * 1985-12-02 1987-06-11 Dainippon Ink & Chem Inc 防曇性被覆用硬化性樹脂組成物
JPH07164971A (ja) * 1993-12-15 1995-06-27 Nissan Motor Co Ltd 親水性ミラーおよびその製造方法
JPH1025468A (ja) * 1996-07-11 1998-01-27 Mitsui Petrochem Ind Ltd 防曇剤組成物
JP2000192021A (ja) * 1998-12-25 2000-07-11 Central Glass Co Ltd 親水性・防曇防汚基材およびその製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62129367A (ja) * 1985-12-02 1987-06-11 Dainippon Ink & Chem Inc 防曇性被覆用硬化性樹脂組成物
JPH07164971A (ja) * 1993-12-15 1995-06-27 Nissan Motor Co Ltd 親水性ミラーおよびその製造方法
JPH1025468A (ja) * 1996-07-11 1998-01-27 Mitsui Petrochem Ind Ltd 防曇剤組成物
JP2000192021A (ja) * 1998-12-25 2000-07-11 Central Glass Co Ltd 親水性・防曇防汚基材およびその製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2080740A1 (fr) * 2007-12-17 2009-07-22 Guardian Industries Corp. Revêtement hydrophile et son procédé de fabrication
JPWO2013145595A1 (ja) * 2012-03-27 2015-12-10 日本板硝子株式会社 やけの防止に適した被膜が形成されたガラス板およびその製造方法

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