WO2019039495A1 - Matériau de revêtement composite et verre - Google Patents

Matériau de revêtement composite et verre Download PDF

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Publication number
WO2019039495A1
WO2019039495A1 PCT/JP2018/030921 JP2018030921W WO2019039495A1 WO 2019039495 A1 WO2019039495 A1 WO 2019039495A1 JP 2018030921 W JP2018030921 W JP 2018030921W WO 2019039495 A1 WO2019039495 A1 WO 2019039495A1
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Prior art keywords
glass
composite paint
coating
composite
coating film
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PCT/JP2018/030921
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English (en)
Japanese (ja)
Inventor
真治 西堀
真 東條
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日本電気硝子株式会社
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Priority to JP2019537647A priority Critical patent/JPWO2019039495A1/ja
Publication of WO2019039495A1 publication Critical patent/WO2019039495A1/fr

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    • 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
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
    • C04B41/61—Coating or impregnation
    • C04B41/65—Coating or impregnation with inorganic materials
    • C04B41/68—Silicic acid; Silicates
    • 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
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds

Definitions

  • the present invention relates to a composite paint and glass used for coating a hardened cement.
  • the paint used to coat the hardened cement makes direct contact with the hardened cement produced by the chemical reaction of water and cement. However, since the alkali component is eluted from the cement-hardened product, a paint having excellent alkali resistance is used as the coating material to be coated.
  • glass flakes are used in order to improve the barrier performance and transparency of a coating film regarding the transparent coating film which coat
  • the coating material used for coating a cement-hardened body is often used outdoors and is exposed to severe conditions.
  • ultraviolet rays deteriorate the resin contained in the paint, and therefore there is a risk of causing peeling of the coating from the frame, discoloration, cracks and the like.
  • inorganic nanoparticles are stable with little influence on other components in the coating, but they are expensive and may contain coating properties if they are contained in a certain amount or more.
  • organic UV absorbers lack stability and have a large influence on other components in the paint to cause a reaction, so it is also difficult to introduce a certain amount or more.
  • the pigment is inexpensive and has a large effect and stability, it is preferable not to contain a certain amount or more because the transparency of the coating is lost and the state of the base material becomes difficult to confirm.
  • a paint that can not contain a large amount of the ultraviolet light absorbing compound or the pigment it is difficult to suppress the deterioration of the coating film due to the ultraviolet light.
  • An object of the present invention is to provide a composite paint for use in a cement cured product, which is excellent in alkali resistance, and can form a coating film that is not easily deteriorated by ultraviolet light, and a glass used in the composite paint.
  • the inventors of the present invention conducted intensive experiments on the composite paint used for the cement hardened body, and as a result, deterioration due to alkaline elution of the coating film or deterioration due to ultraviolet light was caused by glass containing ZrO 2 and TiO 2 as essential components. It has been found that it can be solved by using it.
  • the composite paint of the present invention contains at least a film-forming resin and glass, and is a composite paint used for a film of a cement-hardened body, wherein the glass contains, as a glass composition, ZrO 2 12 to 24 by mass%. % And TiO 2 2 to 20%.
  • the glass further contains 50 to 65% of SiO 2 , 10 to 30% of Li 2 O + Na 2 O + K 2 O, and 0 to 10% of MgO + CaO + SrO + BaO as a glass composition by mass. .
  • the chemical durability (acid resistance, water resistance, alkali resistance) of the glass is further improved, and in turn the chemical durability of the coating is improved.
  • the composite paint of the present invention preferably has a light path length of 3 ⁇ m of glass and a transmittance of 75% or more at a wavelength of 555 nm.
  • the transmittance in the visible region (especially 555 nm) of the coating film is high, so the transparency of the coating film is high, and as a result, it becomes easy to obtain a coating film transparent to visible light.
  • transparent means "a state in which the other side of the coating can be visually recognized visually”.
  • the transmittance of glass is a value obtained by measuring a glass having a thickness of 3 ⁇ m with a spectrophotometer (V-670, manufactured by JASCO Corporation).
  • the light path length of glass is preferably 3 ⁇ m, and the transmittance at a wavelength of 275 nm is preferably 70% or less.
  • the wavelength of the ultraviolet region (200 to 380 nm) is easily absorbed by the glass, the deterioration of the coating film due to ultraviolet light can be further suppressed.
  • the glass surface is preferably coated with a silane coupling agent.
  • the wettability and adhesion of the glass-resin interface can be secured, and therefore the transmittance and strength of the coating film can be improved.
  • the composite paint of the present invention preferably has a glass content of 0.1 to 30% by mass.
  • the glass contains scaly glass.
  • the glass can be efficiently disposed in the coating film or on the cement-hardened body, so that the barrier performance against ultraviolet light etc. is excellent and the cement-hardened body can be hardly deteriorated.
  • "scale-like” means that the glass film is crushed to be scale-like.
  • the average thickness of the scaly glass is 0.1 to 20 ⁇ m, and the average particle diameter of the scaly glass is 20 to 1000 ⁇ m.
  • average thickness is an average value which extract
  • an average particle diameter is a light scattering equivalent diameter measured by the laser diffraction method.
  • the particle size distribution (D50) corresponds to the particle size distribution from the smallest particle size to the 50% cumulative volume.
  • the glass preferably contains milled fibers.
  • milled fibers refer to those obtained by crushing long glass fibers into a powder.
  • the composite paint of the present invention preferably has a milled fiber aspect ratio (average single fiber length / average single fiber diameter) of 1 to 100.
  • average single fiber diameter is a value measured by A method (contour method) of JIS R 3420: 2013, average single fiber length is a value measured by a method according to A method (contour method) of JIS R 3420: 2013. It is.
  • the composite paint of the present invention preferably has an average single fiber diameter of 3 to 30 ⁇ m of milled fibers and an average single fiber length of 20 to 400 ⁇ m of milled fibers.
  • the coating film-forming resin is preferably one or more selected from a thermoplastic resin, a thermosetting resin, and a UV curable resin.
  • the resin to be selected is preferably one having alkali resistance, and may be emulsified.
  • the composite paint of the present invention preferably further contains one or more selected from silicone compounds, siloxane compounds, silane coupling agents, and fluorine compounds.
  • the composite paint of the present invention preferably further comprises 0 to 5% by mass of an ultraviolet absorbing compound.
  • the cost of the composite coating can be reduced.
  • the ultraviolet ray absorbing performance can be improved while securing the stability and the coating film properties of the composite paint.
  • the glass of the present invention as a glass composition, in mass%, ZrO 2 12 ⁇ 24% , contains TiO 2 2 ⁇ 20%, and is characterized by using a coating of cured cement.
  • the glass of the present invention When the glass of the present invention is used, it is possible to form a coating film which is excellent in alkali resistance and which is not easily deteriorated by ultraviolet light.
  • the glass of the present invention preferably further comprises, as a glass composition, 50 to 65% of SiO 2 , 10 to 30% of Li 2 O + Na 2 O + K 2 O, and 0 to 10% of MgO + CaO + SrO + BaO as% by mass.
  • the glass of the present invention is preferably a scaly glass.
  • the glass can be efficiently disposed in the coating film or on the cement-hardened body, so that the barrier performance against ultraviolet light etc. is excellent, and the cement-hardened body can be hardly deteriorated.
  • the glass of the present invention is preferably a milled fiber.
  • the dispersibility in the coating becomes good, and a uniform coating film can be formed in the coating film or on the cement-hardened body, so the barrier property of the coating to ultraviolet light etc. is excellent, and the cemented-hardened steel It can be difficult to deteriorate.
  • the glass of the present invention may take the form of scaly glass or milled fiber. That is, the glass of the present invention may contain only scaly glass among scaly glass and milled fiber, or may contain only milled fiber. The following description applies to both the case where the glass is a scaly glass and the case where it is a milled fiber, unless otherwise noted.
  • the glass of the present invention as a glass composition, in mass%, ZrO 2 12 ⁇ 24% , containing TiO 2 2 ⁇ 20%.
  • "%" indication indicates “mass%”.
  • the glass of the present invention contains ZrO 2 as an essential component as a glass composition.
  • ZrO 2 is a component that improves the alkali resistance, acid resistance and water resistance of glass. Therefore, when the composite paint contains glass with a high content of ZrO 2 as the glass composition, the coating film is less likely to be corroded by the alkali component derived from cement.
  • the content of ZrO 2 is 12 to 24%, preferably 13 to 20%, 14 to 19.5%, particularly 16 to 19%. If the content of ZrO 2 is too small, the alkali resistance, the acid resistance and the water resistance will be reduced, and the alkali resistance, the acid resistance and the water resistance of the coating film will be reduced. On the other hand, when the content of ZrO 2 is too large, the liquidus temperature of the glass is increased, the productivity is lowered, and the cost of the raw material is also increased.
  • the glass of the present invention contains 2% by mass or more of TiO 2 as an essential component as a glass composition.
  • TiO 2 is a component that improves the water resistance and the alkali resistance of the glass and significantly reduces the liquidus temperature.
  • by containing TiO 2 as the glass composition it is possible to reduce the transmittance in the ultraviolet region (200 to 380 nm) and to remarkably improve the ultraviolet light absorbing performance.
  • TiO 2 since TiO 2 has high ultraviolet absorption performance, deterioration of the coating film due to ultraviolet light can be suppressed by containing glass containing TiO 2 in a certain amount or more in the composite paint.
  • TiO 2 can be contained in the glass at a high density, and does not significantly reduce the transmittance of the glass in the visible light region. Therefore, it is possible to effectively suppress the deterioration due to ultraviolet rays while maintaining the transparency of the coating film, particularly in a transparent composite paint.
  • the content of TiO 2 is 2 to 20%, preferably 5 to 19%, more preferably 5.6 to 18%, 6 to 17%, 6.5 to 16%, 6.8 to 15%, particularly 7 to 13% is preferred.
  • the content of TiO 2 is too small, the water resistance and the alkali resistance of the glass are reduced, and the ultraviolet absorbing performance of the glass is also reduced.
  • the molding temperature is increased and the production cost is increased.
  • the content of TiO 2 is too large, crystals containing TiO 2 are easily precipitated in the glass, the productivity is lowered, and the raw material cost is increased.
  • the glass of the present invention further comprises, as a glass composition, 50 to 65% of SiO 2 , 10 to 30% of Li 2 O + Na 2 O + K 2 O, and 0 to 10% of MgO + CaO + SrO + BaO in mass%.
  • SiO 2 is a main component that forms the skeletal structure of glass. Moreover, it is a component which improves the acid resistance of glass.
  • the content of SiO 2 is preferably 50 to 65%, more preferably 55 to 60%, particularly preferably 57 to 60%. When the content of SiO 2 is too small, the mechanical strength and the acid resistance of the glass are likely to be reduced, which in turn reduces the strength and the acid resistance of the coating. On the other hand, when the content of SiO 2 is too large, the alkali resistance of the glass is lowered and the alkali resistance of the coating film is lowered. In addition, the viscosity of the glass is increased, the energy required for melting the glass is increased, and the manufacturing cost is increased.
  • the alkali metal oxide is a component that reduces the viscosity of the glass and enhances the meltability and the formability.
  • an alkali metal oxide is a component that reduces the water resistance of the glass if it is contained in a large amount.
  • the total content of the alkali metal oxides (Li 2 O + Na 2 O + K 2 O) is preferably 10 to 30%, 12 to 25%, 14 to 22%, and particularly preferably 15 to 18%. If the total content of the alkali metal oxides is too small, the viscosity of the glass will be increased, the energy required for melting the glass will be increased, and the production cost will be high. On the other hand, when the total amount of alkali metal oxides is too large, the water resistance of the glass tends to be reduced, and the water resistance of the coating film is consequently reduced.
  • Li 2 O is a component that significantly lowers the liquidus temperature and improves productivity by the addition of a small amount.
  • the content of Li 2 O is preferably 0 to 5%, more preferably 0 to 1%, particularly preferably 0 to 0.6%.
  • the content of Li 2 O is too large, the manufacturing cost will increase and there is concern about the raw material supply instability, so it may not be contained excluding unavoidable impurities.
  • Na 2 O is a component that improves the meltability and formability of glass by reducing the viscosity of the glass.
  • the content of Na 2 O is preferably 10 to 20%, more preferably 10 to 18%, particularly preferably 12 to 18%.
  • the viscosity of the glass is increased, the energy required for melting the glass is increased, and the production cost is increased.
  • the content of Na 2 O is too large, the liquidus temperature of the glass becomes high, and the productivity is lowered.
  • the water resistance of the glass tends to decrease, which in turn reduces the water resistance of the coating.
  • K 2 O is a component that improves the meltability and formability of glass by reducing the viscosity of the glass. Further, it has a function to lower the liquidus temperature, and the effect of reducing the fluctuation of the devitrification due to the composition change is large.
  • the content of K 2 O is preferably 0 to 5%, more preferably 0 to 3%, 0 to 2.5%, particularly preferably 0.1 to 2%.
  • the content of K 2 O is too small, the devitrification property is rapidly changed due to the composition change, which is not preferable.
  • the content of K 2 O is too large, the water resistance of the glass tends to be reduced, and the water resistance of the coating film is consequently reduced.
  • An alkaline earth metal oxide is a component that reduces the viscosity of glass.
  • the total content of the alkaline earth metal oxides (MgO + CaO + SrO + BaO) is preferably 0 to 10%, and 0.1 to 5%, 0.3 to 3%, particularly preferably 0.4 to 2%.
  • the total amount of the alkaline earth metal oxides is too small, it is difficult to obtain the above effect.
  • the total amount of alkaline earth metal oxides is too large, crystals composed of Zr, Si, Na, alkaline earth metal oxides etc. are easily precipitated in the glass, and the liquidus temperature of the glass becomes high, and the productivity Decreases.
  • CaO is a component that reduces the viscosity of glass.
  • the content of CaO is preferably 0 to 10%, 0.1 to 5%, 0.3 to 3%, and particularly 0.4 to 2%.
  • the content of CaO is too small, it is difficult to obtain the above effect.
  • the content of CaO is too large, crystals composed of Zr, Si, Na, Ca, etc. are easily precipitated in the glass, the liquidus temperature of the glass becomes high, and the productivity is lowered.
  • Al 2 O 3 is a component that enhances the chemical durability and mechanical strength of the glass.
  • Al 2 O 3 is also a component to increase the viscosity of glass.
  • the content of Al 2 O 3 is preferably 0 to 5%, more preferably 0 to 3%, particularly preferably 0 to 1%. If the content of Al 2 O 3 is too low, the chemical durability of the glass tends to be reduced, which in turn reduces the chemical durability of the coating. On the other hand, when the content of Al 2 O 3 is too large, the viscosity of the glass is increased, and the energy required for melting the glass is increased.
  • the glass of the present invention contains components other than the above-mentioned components (ZrO 2 and TiO 2 , SiO 2 , Li 2 O, Na 2 O, K 2 O, MgO, CaO, SrO, BaO, Al 2 O 3 ) sell.
  • components other than the above-mentioned components ZrO 2 and TiO 2 , SiO 2 , Li 2 O, Na 2 O, K 2 O, MgO, CaO, SrO, BaO, Al 2 O 3 .
  • the reason is that when the total amount of these components is less than 98%, inconveniences such as decrease in alkali resistance, acid resistance, water resistance or decrease in productivity due to unintended mixing of different components easily occur. It is from.
  • minor components such as H 2 , CO 2 , CO, H 2 O, He, Ne, Ar, N 2 and the like may be contained up to 0.1%.
  • noble metal elements such as Pt, Rh and Au may be added to the glass to 500 ppm.
  • B 2 O 3 , ZnO, Fe 2 O 3 , P 2 O 5 , Cr 2 O 3 , Sb 2 O 3 , SO 3 , MnO , SnO 2 , CeO 2 , Cl 2 , La 2 O 3 , WO 3 , Nb 2 O 5 , Y 2 O 3 and the like may be contained in a total amount of up to 2%.
  • the glass of the present invention preferably has a transmittance of 75% or more at an optical path length of 3 ⁇ m and a wavelength of 555 nm, and preferably 78% or more and 80% or more, particularly 85% or more. Furthermore, the average transmittance in the visible range (380 to 780 nm) is also more preferably 75% or more, 78% or more, 80% or more, 85% or more. In this way, the transmittance of the glass can be improved, and the transmittance of the coating can be improved. As a result, it becomes possible to obtain a coating film excellent in transparency.
  • the coating film of the composite paint can improve the transparency of
  • the glass of the present invention preferably has a transmittance of 70% or less at an optical path length of 3 ⁇ m and a wavelength of 275 nm, and preferably 65% or less, 60% or less, 50% or less, particularly 30% or less. Furthermore, the average transmittance in the ultraviolet region (200 to 380 nm) is also more preferably 60% or less, 55% or less, 50% or less, or 45% or less. In this case, the glass absorbs ultraviolet light, so the coating film is less likely to be deteriorated by the ultraviolet light.
  • the glass of the present invention is preferably coated with various silane coupling agents.
  • silane coupling agent various coupling agents such as aminosilane, vinylsilane, epoxysilane and ureidosilane can be used. In this case, since the compatibility with the silanol bonding portion of the glass surface is good, the adhesion between the glass and the film-forming resin and the coating can be improved.
  • the scale-like glass preferably has an average thickness of 0.1 to 20 ⁇ m and an average particle size of 20 to 1000 ⁇ m.
  • the scaly glass more preferably has an average particle diameter of 50 to 1000 ⁇ m. Further, it is preferable that the glass flakes have a longest particle diameter / thickness ratio of 10 or more.
  • the average thickness of the scaly glass is preferably 0.1 to 20 ⁇ m, more preferably 1 to 15 ⁇ m, 2 to 14 ⁇ m, and particularly preferably 2 to 10 ⁇ m.
  • the above range is preferable also from the viewpoint of efficiently arranging the scaly glass in parallel in the coating.
  • the composite paint may be applied two or more times as needed.
  • the average thickness of the scale-like glass is preferably 0.1 to 20 ⁇ m, more preferably 2 to 18 ⁇ m, and particularly preferably 3 to 15 ⁇ m. preferable. In this way, the heat resistance of the coating can be effectively improved.
  • the scaly glass in order to disperse scaly glass uniformly in the coating film or on the coated surface, preferably has an average particle diameter of 20 to 1000 ⁇ m, 30 to 1000 ⁇ m, 40 to 1000 ⁇ m, 50 to 1000 ⁇ m, The thickness is preferably 100 to 900 ⁇ m, 200 to 850 ⁇ m, and particularly 300 to 800 ⁇ m. It becomes difficult to apply
  • the milled fiber When the glass of the present invention is in the form of a milled fiber, the milled fiber preferably has an aspect ratio (average single fiber length / average single fiber diameter) of 1 to 100, and 1.5 to 50, 2.0 to It is preferably 20, particularly 2.5 to 10.
  • the application process for attaching a sheet-like reinforcing material for the purpose of repair or reinforcement to a painted or concrete structure is carried out under various natural conditions such as outdoors, so it is applied when drying and shrinking after application.
  • cracks may occur in the film, since the milled fibers contained in the composite paint of the present invention are in the form of fibers, they have the effect of suppressing the cracks.
  • the aspect ratio is too small, it is difficult to disperse the stress, so it is difficult to obtain the effect.
  • the aspect ratio is too large, it becomes difficult to disperse the milled fiber in the paint and the surface condition of the coating film is deteriorated. If the surface condition of the coating film is deteriorated, it may not only impair the appearance but also cause cracking of the coating film and cracking of the cement-hardened body.
  • the milled fibers preferably have an average single fiber diameter of 3 to 30 ⁇ m, 8 to 20 ⁇ m, 9 to 17 ⁇ m, and particularly 10 to 14 ⁇ m.
  • the average single fiber diameter is too small, it is difficult to form long fibers, and the productivity is deteriorated.
  • the average single fiber diameter is too large, when forming a coating, milled fibers are easily protruded to the surface of the coating, and the surface condition is deteriorated. If the surface condition of the coating film is deteriorated, it may not only impair the appearance but also cause cracking of the coating film and cracking of the cement-hardened body.
  • the milled fibers preferably have an average single fiber length of 20 to 400 ⁇ m, 30 to 300 ⁇ m, 40 to 250 ⁇ m, 50 to 200 ⁇ m, and particularly 60 to 150 ⁇ m. Since milled fibers are produced by grinding long fibers, if the average single fiber length is too short, not only grinding becomes difficult, but also the production cost increases. On the other hand, if the average single fiber length is too long, the milled fibers are entangled with each other, making it difficult to disperse in the paint, and the surface condition of the coating film is deteriorated. If the surface condition of the coating film is deteriorated, it may not only impair the appearance but also cause cracking of the coating film and cracking of the cement-hardened body.
  • the composite paint of the present invention comprises glass.
  • the details of the glass are as described above, and the description is omitted here.
  • the content of glass is preferably 0.1 to 30%, more preferably 1 to 20%, and particularly preferably 3 to 10%. If the content of glass is too small, the ultraviolet light absorbing performance can not be exhibited and the barrier performance of the coating film is lowered, so it is difficult to inhibit the entry of water or carbon dioxide in the atmosphere into the coating or the cured concrete. Become. Furthermore, the mechanical strength is also reduced. On the other hand, when the content of glass is too large, the dispersibility of the glass in the composite paint tends to deteriorate, and it is difficult to obtain a uniform coating film. Moreover, it becomes difficult to apply
  • the composite paint may be applied two or more times as needed.
  • the composite paint of the present invention contains at least a film-forming resin.
  • thermoplastic resin As a film formation resin, a thermoplastic resin, a thermosetting resin, and a UV curable resin are preferable. Specifically, acrylic resin, urethane resin, acrylic urethane resin, polyester resin, polyamide resin, melamine resin, phenol resin, alkyd resin, epoxy resin, vinyl chloride resin, fluorine resin, silane resin, acrylic silicone resin, etc. are listed. Be Among these, those having excellent alkali resistance are particularly preferable.
  • 1 type, or 2 or more types of resin selected from other than that resin can be selected arbitrarily according to a desired characteristic and a use.
  • an acrylic resin, an acrylic urethane resin or a urethane resin is preferably used as a coating application that requires an aesthetic appearance
  • an epoxy resin or an acrylic resin is preferably used as an anti-peeling application that requires a strength.
  • a fluorine resin can be used for applications where weather resistance and chemical resistance are required.
  • the composite paint of the present invention is excellent in alkali resistance and is suppressed from being deteriorated by ultraviolet rays, and therefore, it can be applied without any top coating (protective coating) in any use.
  • the composite paint of the present invention can further contain any of a silicone compound, a siloxane compound, a silane coupling agent, and a fluorine compound.
  • a silane compound in particular, the compatibility with the silanol bond portion of the glass surface is good, and the adhesion between the glass and the film-forming resin, and further, the coating can be improved.
  • the composite paint of the present invention contains glass having high alkali resistance and ultraviolet absorption performance, it is possible to suppress ultraviolet ray deterioration of the coating film.
  • a coating having transparency after coating and drying that is, a coating having a transmittance of 75% or more in the visible light region, the effect is remarkable.
  • the composite paint of the present invention may further contain 0 to 5%, preferably 0 to 3%, particularly 0 to 1% of an ultraviolet absorbing compound.
  • inorganic nanoparticles such as titanium and zinc as the ultraviolet absorbing compound
  • benzotriazole ultraviolet absorber and hydroxyphenyl triazine (HPT) ultraviolet absorber as the organic ultraviolet absorber
  • one or more of these may be contained to the above amount.
  • the ultraviolet absorbing compound is not contained in a certain amount or more. Since the composite paint of the present invention contains glass having high UV absorption performance, the content of the UV absorbing compound can be reduced.
  • the composite paint of the present invention may impart a water repellent function to a coating film by containing, for example, a silicone resin, a fluorine resin, or the like.
  • the composite paint of the present invention may be colored by adding a coloring component such as a pigment, if necessary.
  • the composite paint of the present invention may optionally contain both scaly glass and milled fiber.
  • both the scaly glass and the milled fiber may be the glass of the present invention, or either one may be a glass different from the present invention.
  • glass different from this invention A glass, E glass, EC glass etc. which are different in composition from glass of this invention are mentioned. By doing so, the barrier performance of the coating film to ultraviolet light, water and gas can be further improved.
  • the mixing ratio of the scaly glass and the milled fiber in the composite paint can be arbitrarily adjusted in accordance with the required characteristics.
  • milled fibers may be blended at a high ratio.
  • scaly glass may be blended at a high ratio.
  • the composite paint of the present invention can not only be applied directly to a cement-cured product but also be used as an intermediate coat or a top coat (protective coat). Specifically, it may be used as a protective paint for a surface after repairing a cement-hardened body or a reinforcing fiber (such as an anti-slip net).
  • the composite paint of the present invention is excellent in alkali resistance and is suppressed from being deteriorated by ultraviolet rays, so that the durability is improved.
  • the glass of the present invention is excellent in alkali resistance as well as high in ultraviolet absorption performance and high in barrier performance, so it can be developed into composite materials for various uses besides composite paints.
  • the glass of the present invention can be used as a water repellent by mixing with an organic solvent.
  • a silane type compound As an organic solvent, a silane type compound, a silicone type compound, a siloxane compound, a silane coupling agent, a fluorine type compound etc. are mentioned, for example.
  • a silane compound in particular, the compatibility with the silanol bonding portion of the glass surface is good, and the adhesion between the glass and the coating can be improved. Therefore, it can also be suitably used for a cement-hardened material permeable water repellent.
  • a film-forming resin such as a fluorocarbon resin
  • a water-repellent agent containing the above-mentioned organic solvent as a main agent
  • a water-repellent agent having permeability and forming a coating film may also be used. Good.
  • the glass of the present invention is scale-like glass, it is easy to be oriented parallel to the surface of the coated surface or the coated surface in the coating because it is scaly.
  • the entry of carbon dioxide in the medium can be significantly inhibited. Thereby, the swelling of the coating film itself, the shrinkage deformation of the hardened concrete body, and the neutralization can be suppressed.
  • the glass of the present invention when the glass of the present invention is milled fiber, the glass can be dispersed uniformly in the coating, and since it is fibrous, cracking of the coating can be suppressed, and water to the coating and the cured concrete can be obtained. Alternatively, the entry of carbon dioxide in the atmosphere can be significantly inhibited. Thereby, the swelling of the coating film itself, the shrinkage deformation of the hardened concrete body, and the neutralization can be suppressed. Furthermore, since the dispersibility in the paint is good, a large amount of glass can be contained in the composite paint, and the above-described effects can be effectively obtained.
  • the glass of the present invention has a high ultraviolet absorbing ability, so that the ultraviolet ray deterioration of the water repellent can be suppressed even when it is used as a water repellent, so the film performance is improved and the water repellent effect is long lasting. Moreover, since it is easy to orientate in parallel in the coating surface surface and the coating surface direction in a coating film, barrier performance is high and deterioration of a concrete hardening body can be suppressed. In particular, in the case of a water repellent having transparency after coating and drying, that is, a water repellent having a transmittance of 75% or more in the visible light region, a remarkable effect can be expected.
  • the glass of the present invention may be used as a repair material to be used for repairing cracks in concrete or as an anti-slip material for preventing the peeling of concrete pieces.
  • the repair material is, for example, a filler of epoxy resin or acrylic resin injected into a crack of concrete for filling or coating, thereby reinforcing and improving waterproof performance and suppressing the development of the crack.
  • the material for preventing peeling is coated with an epoxy resin or an acrylic resin at a location where it is structurally necessary to prevent peeling, thereby preventing peeling of concrete pieces.
  • the barrier performance of the material for preventing or repairing the material is improved, the deterioration is suppressed, and the durability is improved.
  • the effect of inhibiting the entry of water or atmospheric carbon dioxide into the material for preventing or repairing the material itself or the concrete can be enhanced over a long period of time.
  • the said material may add coloring components, such as a pigment, as needed for the purpose of not only what has transparency but an aesthetics and a concrete and a color tone are adjusted.
  • a reinforcing fiber such as an anti-falling net.
  • Example Nos. 1 and 2 show Examples (Sample Nos. 1 and 2) and Comparative Examples (Sample Nos. 3 and 4) of the present invention.
  • Example No. No. 1, 2 and Comparative Example No. 1 No. 3 is an example containing scale-like glass
  • Comparative Example No. 3 is an example.
  • 4 is an example which does not contain scaly glass.
  • Example No. 1 and 2 contain scaly glass satisfying the glass composition of the present invention.
  • various glass raw materials such as natural raw materials and chemical conversion raw materials were weighed and mixed so as to have the glass compositions shown in the table, to produce glass batches.
  • this glass batch was put into a platinum-rhodium alloy crucible, and heated at 1550 ° C. for 5 hours in an indirect heating electric furnace to obtain a molten glass.
  • the molten glass was stirred several times using a heat resistant stirring rod at the time of heating. Thereafter, molten glass is wound around a heat resistant steel tube, air is poured from the opposite side, the glass is expanded, cooled, and then crushed to obtain flake glass having an average thickness of 3 ⁇ m and an average particle diameter of 600 ⁇ m.
  • the transmittance of the scaly glass having a thickness of 3 ⁇ m was measured under the following conditions. The results are shown in FIG. Instrument: JASCO Spectrophotometer V-670 Sampling pitch: 1 nm Scanning speed: 200 nm / min
  • the glasses of No. 1 and No. 2 are comparative examples no. Although the wavelength of the ultraviolet region (200 to 380 nm) is easily absorbed as compared with the glass of No. 3, the transmittance in the visible region (particularly, 555 nm) is equal. Therefore, the composite paint using the glass of the present invention can suppress the deterioration of the coating film due to ultraviolet light, and can easily ensure the transparency in the visible region when it is formed into a coating film.
  • the alkali resistance of glass was measured as follows. First, the molten glass obtained by the above method was poured out to prepare a plate-like glass sample. The plate glass is crushed, and a glass having a particle size of 300 to 500 ⁇ m in diameter is precisely weighed by a specific gravity ⁇ 2 weight minutes, subsequently immersed in 100 ml of 10% by mass NaOH solution and shaken at 80 ° C. for 90 hours. Thank you. Thereafter, the weight loss rate of the glass sample was measured. The smaller this value, the better the alkali resistance.
  • an acrylic polyol-based urethane resin and hexamethylene diisocyanate were prepared in a ratio of 4: 1, and in the two-component resin kneaded, sample No. 1 was prepared. 15% by mass of 1 to 3 scaly glass was added. Thereafter, a thinner made of ethyl acetate, butyl acetate or the like was added, and the viscosity of the composite paint was adjusted to a coatable viscosity to obtain a composite paint.
  • comparative example No. 4 is a paint prepared without adding scaly glass.
  • a plate-like fiber-reinforced cement is obtained by kneading the obtained composite paint or paint with a mortar having a sand-cement ratio of 1 and a water-cement ratio of 0.42 and a glass fiber having a length of 13 mm. It applied so that the thickness of the coating film after drying on a body might be 100 micrometers.
  • the degree of transmission of the base of the coating-coated cemented body is visually evaluated, and those which the base does not transmit at all are visually observed ⁇ , those which transmit a little ⁇ , transmission Evaluations were made with ⁇ being good and ⁇ being sufficiently transparent.
  • the coated cement hardened body is irradiated with ultraviolet light according to JIS K 5600-7-7 xenon lamp method (irradiance 180 w / m 2 ) for 1000 hours, and the change is remarkable regarding the change such as coloring and peeling visually
  • the evaluation was made as x for those that were ⁇ ⁇ ⁇ , ⁇ for those that were ⁇ ⁇ , ⁇ for those that were hardly present, and ⁇ for those that were not at all.
  • the scaly glass of the present invention has a high transmittance in the visible range and a high ultraviolet light absorbing performance. Therefore, in Example No. As shown in 1 and 2, the composite paint of the present invention had good transparency in the visible region when it was formed into a coating, and further, deterioration of the coating due to ultraviolet light was suppressed.
  • Example Nos. 5 and 6 show Examples (Sample Nos. 5 and 6) and Comparative Examples (Sample Nos. 7 to 9) of the present invention.
  • Example No. 5, 6 and comparative example no. Nos. 7 and 8 are examples including milled fibers. 9 is an example which does not contain a milled fiber.
  • Example No. Nos. 5 and 6 contain milled fibers that satisfy the glass composition of the present invention.
  • Example 1 Each sample of Table was produced by the method demonstrated in Example 1 in order to use for the measurement of the transmittance
  • the transmittance and the alkali resistance largely depend on the glass composition.
  • Sample No. Sample No. 5 of Example 1 was obtained.
  • Sample No. 1 with the same glass composition as No. 1. 6 is the sample No. 6 of Example 1.
  • Sample No. 2 with the same glass composition as No. 2. 7 and No. Sample No. 8 of Example 1 was obtained. It is the same glass composition as 3. Therefore, sample no.
  • the results of the measurement of transmittance and the measurement of alkali resistance of 5 to 8 are the same as the measurement results of the corresponding sample of Example 1. Therefore, sample no.
  • the results of the measurement of the transmittance and the measurement of the alkali resistance of 5 to 8 use the measurement results of the corresponding sample of Example 1 and omit the detailed description.
  • the molten glass obtained by the method described in Example 1 was supplied to a noble metal bushing having hundreds of nozzles, and drawn into a fiber to obtain glass fibers having a predetermined average single fiber diameter.
  • the obtained glass fiber was first cut to 3 mm, and then ground to a predetermined average single fiber length by a Henschel mixer and a ball mill crusher to obtain a milled fiber.
  • an average single fiber diameter is measured by A method (contour method) of JIS R 3420: 2013, and an average single fiber length is measured by a method according to A method (contour method) of JIS R 3420: 2013 did.
  • the aspect ratio is a value obtained by dividing the average single fiber length by the average single fiber diameter.
  • an acrylic polyol-based urethane resin and hexamethylene diisocyanate were prepared in a ratio of 4: 1, and in the two-component resin kneaded, sample No. 1 was prepared. 15% by mass of 5 to 8 milled fibers were added. Thereafter, a thinner made of ethyl acetate, butyl acetate or the like was added, and the viscosity of the composite paint was adjusted to a coatable viscosity to obtain a composite paint.
  • comparative example No. 9 is a paint prepared without adding milled fiber.
  • the composite paint or paint prepared in this manner is transferred to a 500 ml beaker with a scale and set for 30 minutes, and then the precipitated state of the milled fiber is visually confirmed while the fluorescent light is transmitted from the side of the beaker did.
  • dispersibility those in which most of the milled fibers were sedimented below the scale of 200 ml were x, those in which they were sedimented below the scale of 400 ml were ⁇ , and those that were hardly sedimented were o And
  • the see-through condition of the base of the coating-coated cemented body is evaluated visually, and those which can not see through at all are x, those which can see through a little are ⁇ , those which can see through are ⁇ , sufficient see-through
  • the transparency of the coating film was evaluated as ⁇ ⁇ ⁇ which can be made.
  • the coated cement hardened body is irradiated with ultraviolet light according to JIS K 5600-7-7 xenon lamp method (irradiance 180 w / m 2 ) for 1000 hours, and the change is remarkable regarding the change such as coloring and peeling visually
  • the evaluation of the state of the coated film after the ultraviolet irradiation was carried out by setting what was X, what was ⁇ , what was seldom ⁇ , and ⁇ which was not at all.
  • the milled fiber of the present invention has a high transmittance in the visible range and a high ultraviolet absorption performance. Therefore, in Example No. As shown in 5 and 6, the composite paint of the present invention had good transparency in the visible region when it was formed into a coating, and further, deterioration of the coating due to ultraviolet light was suppressed.
  • the composite paint and glass of the present invention are used for coating concrete structures and cements, and in particular, are suitably used for clear coating.
  • the glass of the present invention can also be used as a water repellent by mixing it with an organic solvent. Furthermore, it may be used as an anti-falling material for preventing the fall-off of a repair material or a concrete piece for use in crack repair of concrete.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Structural Engineering (AREA)
  • Glass Compositions (AREA)
  • Paints Or Removers (AREA)
  • Aftertreatments Of Artificial And Natural Stones (AREA)

Abstract

La présente invention concerne un matériau de revêtement composite qui contient au moins une résine filmogène de revêtement et un verre et peut être utilisé pour le revêtement d'un article durci en ciment, le matériau de revêtement composite étant caractérisé en ce que le verre a une composition de verre comprenant, en % en masse, de 12 à 24% de ZrO2 et 2 à 20% de TiO2.
PCT/JP2018/030921 2017-08-24 2018-08-22 Matériau de revêtement composite et verre WO2019039495A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020186283A (ja) * 2019-05-10 2020-11-19 日本電気硝子株式会社 複合塗料

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09110453A (ja) * 1995-10-25 1997-04-28 Nippon Glass Fiber Co Ltd 耐アルカリ性ガラスフレーク並びにこのガラスフレークで補強された熱可塑性樹脂組成物及び熱硬化性樹脂組成物
JP2005097080A (ja) * 2003-08-29 2005-04-14 Nippon Sheet Glass Co Ltd 鱗片状ガラス
JP2009513470A (ja) * 2005-10-28 2009-04-02 サン ゴバン ヴェトロテックス フランス ソシエテ アノニム ガラスストランドの製造のための耐アルカリ及び耐酸性ガラス組成物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09110453A (ja) * 1995-10-25 1997-04-28 Nippon Glass Fiber Co Ltd 耐アルカリ性ガラスフレーク並びにこのガラスフレークで補強された熱可塑性樹脂組成物及び熱硬化性樹脂組成物
JP2005097080A (ja) * 2003-08-29 2005-04-14 Nippon Sheet Glass Co Ltd 鱗片状ガラス
JP2009513470A (ja) * 2005-10-28 2009-04-02 サン ゴバン ヴェトロテックス フランス ソシエテ アノニム ガラスストランドの製造のための耐アルカリ及び耐酸性ガラス組成物

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020186283A (ja) * 2019-05-10 2020-11-19 日本電気硝子株式会社 複合塗料
JP7299561B2 (ja) 2019-05-10 2023-06-28 日本電気硝子株式会社 複合塗料

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