WO2019039495A1 - Composite coating material and glass - Google Patents

Composite coating material and glass 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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WO
WIPO (PCT)
Prior art keywords
glass
composite paint
coating
composite
coating film
Prior art date
Application number
PCT/JP2018/030921
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French (fr)
Japanese (ja)
Inventor
真治 西堀
真 東條
Original Assignee
日本電気硝子株式会社
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Application filed by 日本電気硝子株式会社 filed Critical 日本電気硝子株式会社
Priority to JP2019537647A priority Critical patent/JPWO2019039495A1/en
Publication of WO2019039495A1 publication Critical patent/WO2019039495A1/en

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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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Abstract

A composite coating material according to the present invention contains at least a coating film-forming resin and a glass and can be used for the coating of a cement cured article, the composite coating material being characterized in that the glass has a glass composition comprising, in mass%, 12 to 24% of ZrO2 and 2 to 20% of TiO2.

Description

複合塗料及びガラスComposite paint and glass
　本発明は、セメント硬化体の被覆に用いる複合塗料及びガラスに関する。 The present invention relates to a composite paint and glass used for coating a hardened cement.
　従来、コンクリート構造物やセメント製品表面に様々な塗料を被覆し、経年劣化を抑制する方法が知られている。 DESCRIPTION OF RELATED ART Conventionally, the method of coat | covering various paints on a concrete structure or cement product surface, and suppressing aging deterioration is known.
　セメント硬化体の被覆に用いられる塗料は、水とセメントとの化学反応により生成されるセメント硬化体と直接接触する。しかし、セメント硬化体からはアルカリ成分が溶出するため、被覆する塗料は、耐アルカリ性に優れた塗料が使用されている。 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.
特公平４－２１５７９号公報Tokuhei 4-21579 特開２０１６－７９１９３号公報JP, 2016-79193, A
　特許文献１では、コンクリート保護材料の耐アルカリ性の低下を抑制するために、エチレン性不飽和単量体を含む樹脂組成物を用いている。 In patent document 1, in order to suppress the alkali-resistance fall of a concrete protective material, the resin composition containing an ethylenically unsaturated monomer is used.
　さらに近年、コンクリート構造物やセメント製品の下地の色・柄を生かし、表面の透明感や光沢を出すことを目的として、無色塗料によるクリア塗装が行われるようになってきた。このクリア塗装は、コンクリート構造物表面の亀裂等の劣化を早期に発見するためにも有用である。 Furthermore, in recent years, clear coating with a colorless paint has come to be performed for the purpose of giving the surface a sense of transparency and luster by making use of the underlying color and pattern of concrete structures and cement products. This clear coating is also useful for early detection of deterioration such as cracks on the surface of a concrete structure.
　特許文献２では、コンクリート構造物の表面を被覆する透明塗膜に関し、塗膜のバリア性能及び透明性を向上させるためにガラスフレーク（鱗片状ガラス）が用いられている。 In patent document 2, glass flakes (scale-like glass) are used in order to improve the barrier performance and transparency of a coating film regarding the transparent coating film which coat | covers the surface of a concrete structure.
　ところで、セメント硬化体の被覆に用いる塗料は、屋外で使用されることが多く、過酷な状況に晒される。その中でも特に紫外線は、塗料に含有されている樹脂を劣化させるため、塗膜の躯体からの剥がれ、変色、クラック等を惹起する虞がある。 By the way, the coating material used for coating a cement-hardened body is often used outdoors and is exposed to severe conditions. Among them, in particular, 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.
　そのため、紫外線への対応として、チタンや亜鉛などの無機ナノ粒子、また有機系の紫外線吸収剤としてベンゾトリアゾール系紫外線吸収剤やヒドロキシフェニルトリアジン（ＨＰＴ）系紫外線吸収剤、更に、顔料を導入させる場合がある。 Therefore, in the case of introducing inorganic nanoparticles such as titanium and zinc, benzotriazole-based ultraviolet absorbers and hydroxyphenyltriazine (HPT) -based ultraviolet absorbers as organic-based ultraviolet absorbers, and pigments in order to cope with ultraviolet rays. There is.
　これらの紫外線吸収性化合物のうち、無機ナノ粒子は塗料中の他成分への影響が少なく安定であるが、高コストとなると共に、一定量以上含有させると塗膜特性を損なう可能性がある。一方、有機系の紫外線吸収剤は安定性に欠ける上、塗料中の他成分への影響が大きく反応が起こる虞があるため、こちらも一定量以上の導入が難しい。加えて顔料は、安価で効果が大きく安定性も良いが、塗膜の透明性が失われ母材の状態が確認し難くなるため、一定量以上含有させないことが好ましい。このように、紫外線吸収化合物や顔料を多量に含有させることができない塗料では、紫外線による塗膜の劣化を抑制することが困難であった。 Among these UV absorbing compounds, 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. On the other hand, 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. In addition, although 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. As described above, in 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.
　本発明の課題は、セメント硬化体に用いる複合塗料であって、耐アルカリ性に優れ、しかも、紫外線によって劣化し難い塗膜を形成できる複合塗料及び複合塗料に用いるガラスを提供することである。 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.
　本発明者等はセメント硬化体に用いる複合塗料に関して鋭意実験した結果、塗膜のアルカリ溶出による劣化や、紫外線による劣化は、ガラス組成として、ＺｒＯ2及びＴｉＯ2を必須成分として含有させたガラスを用いることにより解決できることを見出した。 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.
　すなわち、本発明の複合塗料は、少なくとも塗膜形成樹脂とガラスとを含み、セメント硬化体の被膜に用いられる複合塗料であって、ガラスが、ガラス組成として、質量％で、ＺｒＯ2　１２～２４％、ＴｉＯ2　２～２０％を含有することを特徴とする。 That is, 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%.
　このようにすることで、耐アルカリ性に優れ、しかも、紫外線によって劣化し難い塗膜を形成することができる複合塗料を得ることができる。 By doing this, it is possible to obtain a composite paint which can form a coating film which is excellent in alkali resistance and which is not easily deteriorated by ultraviolet light.
　本発明の複合塗料は、ガラスが、更に、ガラス組成として、質量％で、ＳｉＯ2　５０～６５％、Ｌｉ2Ｏ＋Ｎａ2Ｏ＋Ｋ2Ｏ　１０～３０％、ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ　０～１０％を含有することが好ましい。 In the composite paint of the present invention, it is preferable that 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. .
　このようにすることで、ガラスの化学耐久性（耐酸性、耐水性、耐アルカリ性）がより向上し、ひいては塗膜の化学耐久性が向上する。 By doing so, 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.
　本発明の複合塗料は、ガラスの光路長３μｍ、波長５５５ｎｍにおける透過率が７５％以上であることが好ましい。 The composite paint of the present invention preferably has a light path length of 3 μm of glass and a transmittance of 75% or more at a wavelength of 555 nm.
　このようにすることで、塗膜の可視域（特に５５５ｎｍ）における透過率が高くなるため、塗膜の透明性が高くなり、その結果、可視光に対して透明な塗膜を得易くなる。なお、本発明において、「透明」とは、「目視で塗膜の向こう側が視認できる状態」を指す。また、「ガラスの透過率」は、厚み３μｍのガラスを分光光度計（日本分光製　Ｖ－６７０）にて測定した値である。 By doing this, 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. In the present invention, "transparent" means "a state in which the other side of the coating can be visually recognized visually". Further, “the transmittance of glass” is a value obtained by measuring a glass having a thickness of 3 μm with a spectrophotometer (V-670, manufactured by JASCO Corporation).
　本発明の複合塗料は、ガラスの光路長３μｍ、波長２７５ｎｍにおける透過率が７０％以下であることが好ましい。 In the composite paint of the present invention, the light path length of glass is preferably 3 μm, and the transmittance at a wavelength of 275 nm is preferably 70% or less.
　このようにすることで、ガラスに紫外域（２００～３８０ｎｍ）の波長が吸収され易いため、塗膜の紫外線による劣化をより抑制できる。 In this way, since 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.
　本発明の複合塗料は、ガラスの表面がシランカップリング剤で被覆されていることが好ましい。 In the composite paint of the present invention, the glass surface is preferably coated with a silane coupling agent.
　このようにすることで、ガラスと樹脂界面の濡れ性や接着性を確保できることから、塗膜の透過率や強度を向上できる。 By so doing, 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.
　本発明の複合塗料は、ガラスの含有量が０．１～３０質量％であることが好ましい。 The composite paint of the present invention preferably has a glass content of 0.1 to 30% by mass.
　このようにすることで、塗膜のバリア性能や強度が向上する。 By doing this, the barrier performance and the strength of the coating film are improved.
　本発明の複合塗料は、ガラスが鱗片状ガラスを含むことが好ましい。 In the composite paint of the present invention, it is preferable that the glass contains scaly glass.
　このようにすることで、塗膜中或いはセメント硬化体上にガラスを効率よく配置できるため、紫外線等に対するバリア性能に優れ、セメント硬化体を劣化し難くできる。なお、本発明では、「鱗片状」とは、ガラス膜を破砕して鱗片状にしたものである。 In this way, 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. In the present invention, "scale-like" means that the glass film is crushed to be scale-like.
　本発明の複合塗料は、鱗片状ガラスの平均厚みが０．１～２０μｍであり、且つ、前記鱗片状ガラスの平均粒径が２０～１０００μｍであることが好ましい。 In the composite paint of the present invention, it is preferable that the average thickness of the scaly glass is 0.1 to 20 μm, and the average particle diameter of the scaly glass is 20 to 1000 μm.
　このようにすることで、塗膜のバリア性能が向上する。なお、平均厚みは、試料１０枚を採取し、ダイヤルゲージを用いて１枚ごとにμｍ単位まで測定し、算出した平均値であり、平均粒径は、レーザ回折法により測定した光散乱相当径の粒度分布において、粒径が小さなものから体積累計５０％に相当する粒径（Ｄ５０）である。 By doing this, the barrier performance of the coating film is improved. In addition, average thickness is an average value which extract | collected 10 samples, measured to the micrometer unit every sheet using a dial gauge, and was calculated, and 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.
　本発明の複合塗料は、ガラスがミルドファイバーを含むことが好ましい。 In the composite paint of the present invention, the glass preferably contains milled fibers.
　このようにすることで、塗料中におけるガラスの分散性が良好になり、塗膜中或いはセメント硬化体上に均一な塗膜を形成できるため、紫外線等に対する塗膜のバリア性に優れ、セメント硬化体を劣化し難くできる。なお、本発明では、「ミルドファイバー」とは、ガラス長繊維を粉砕して粉末状にしたものを指す。 By doing this, the dispersibility of the glass in the paint becomes good, and a uniform paint film can be formed in the paint film or on the cement hardened body, so the barrier property of the paint film against ultraviolet light etc. is excellent, cement hardening It can be difficult to deteriorate the body. In the present invention, "milled fibers" refer to those obtained by crushing long glass fibers into a powder.
　本発明の複合塗料は、ミルドファイバーのアスペクト比（平均単繊維長／平均単繊維直径）が１～１００であることが好ましい。 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.
　このようにすることで、よりガラスの分散性が良い複合塗料を得ることができる。また、その結果、均一な塗膜を得ることが容易になる。なお、平均単繊維直径はＪＩＳ　Ｒ　３４２０：２０１３のＡ法（輪郭法）で測定した値であり、平均単繊維長はＪＩＳ　Ｒ　３４２０：２０１３のＡ法（輪郭法）に準ずる方法で測定した値である。 By doing this, a composite paint with better glass dispersibility can be obtained. In addition, as a result, it becomes easy to obtain a uniform coating film. In addition, 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.
　本発明の複合塗料は、ミルドファイバーの平均単繊維直径が３～３０μｍであり、且つミルドファイバーの平均単繊維長が２０～４００μｍであることが好ましい。 The composite paint of the present invention preferably has an average single fiber diameter of 3 to 30 μm of milled fibers and an average single fiber length of 20 to 400 μm of milled fibers.
　このようにすることで、より分散性が良い複合塗料を得ることができる。また、その結果、より均一な塗膜を得ることが容易になり、紫外線に対する塗膜のバリア性能が向上する。 By doing this, a composite paint with better dispersibility can be obtained. Moreover, as a result, it becomes easy to obtain a more uniform coating film, and the barrier performance of the coating film to ultraviolet light is improved.
　本発明の複合塗料は、塗膜形成樹脂が、熱可塑性樹脂、熱硬化性樹脂、ＵＶ硬化性樹脂の中から選択される１種又は２種以上であることが好ましい。 In the composite paint of the present invention, the coating film-forming resin is preferably one or more selected from a thermoplastic resin, a thermosetting resin, and a UV curable resin.
　このようにすることで、セメント硬化体を被覆する塗膜を形成することができる。なお、選択される樹脂は耐アルカリ性を有するものが好ましく、エマルジョン化されたものでも良い。 By doing this, it is possible to form a coating film that covers the hardened cement body. The resin to be selected is preferably one having alkali resistance, and may be emulsified.
　本発明の複合塗料は、更にシリコーン系化合物、シロキサン化合物、シランカップリング剤、フッ素系化合物の中から選択される１種又は２種以上を含むことが好ましい。 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.
　このようにすることで、塗膜の撥水性が向上する。 By doing this, the water repellency of the coating film is improved.
　本発明の複合塗料は、更に紫外線吸収性化合物を０～５質量％含むことが好ましい。 The composite paint of the present invention preferably further comprises 0 to 5% by mass of an ultraviolet absorbing compound.
　紫外線吸収性化合物の含有量をこのように規制することで、複合塗料を低コストにできる。また、複合塗料の安定性や塗膜特性を確保しつつも紫外線吸収性能を向上させることができる。 By thus regulating the content of the ultraviolet absorbing compound, the cost of the composite coating can be reduced. In addition, the ultraviolet ray absorbing performance can be improved while securing the stability and the coating film properties of the composite paint.
　本発明のガラスは、ガラス組成として、質量％で、ＺｒＯ2　１２～２４％、ＴｉＯ2　２～２０％を含有し、且つセメント硬化体の被覆に用いることを特徴とする。 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.
　本発明のガラスを用いると、耐アルカリ性に優れ、しかも、紫外線によって劣化し難い塗膜を形成することができる。 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.
　本発明のガラスは、更に、ガラス組成として、質量％で、ＳｉＯ2　５０～６５％、Ｌｉ2Ｏ＋Ｎａ2Ｏ＋Ｋ2Ｏ　１０～３０％、ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ　０～１０％を含有することが好ましい。 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.
　このようにすることで、ガラスの化学耐久性がより向上する。 By doing this, the chemical durability of the glass is further improved.
　本発明のガラスは、鱗状片ガラスであることが好ましい。 The glass of the present invention is preferably a scaly glass.
　このようにすることで、ガラスが、塗膜中或いはセメント硬化体上に効率よく配置できるため、紫外線等に対するバリア性能に優れ、セメント硬化体を劣化し難くできる。 In this way, 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.
　本発明のガラスは、ミルドファイバーであることが好ましい。 The glass of the present invention is preferably a milled fiber.
　このようにすることで、塗料中の分散性が良好になり、塗膜中或いはセメント硬化体上に均一な塗膜を形成できるため、紫外線等に対する塗膜のバリア性に優れ、セメント硬化体を劣化し難くできる。 By doing this, 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.
実施例と比較例のガラスの透過率を示す図である。It is a figure which shows the transmittance | permeability of the glass of an Example and a comparative example.
　本発明のガラスは、鱗片状ガラス又はミルドファイバーの形態を取りうる。すなわち、本発明のガラスは、鱗片状ガラス及びミルドファイバーのうち、鱗片状ガラスのみを含んでいてもよいし、ミルドファイバーのみを含んでいてもよい。以下の説明は、特に断りがない限り、ガラスが鱗片状ガラスである場合と、ミルドファイバーである場合との両方に当てはまるものとする。 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.
　本発明のガラスは、ガラス組成として、質量％で、ＺｒＯ2　１２～２４％、ＴｉＯ2　２～２０％を含有する。なお、本発明において「％」表示は「質量％」のことを示す。 The glass of the present invention, as a glass composition, in mass%, ZrO 2 12 ~ 24% , containing TiO 2 2 ~ 20%. In the present invention, "%" indication indicates "mass%".
　本発明のガラスは、ガラス組成として、ＺｒＯ2を必須成分として含有する。ＺｒＯ2は、ガラスの耐アルカリ性、耐酸性及び耐水性を向上させる成分である。そのため、ガラス組成として、ＺｒＯ2の含有量が多いガラスを複合塗料に含有させることで、塗膜がセメント由来のアルカリ成分に浸食され難くなる。 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.
　ＺｒＯ2の含有量は１２～２４％であり、１３～２０％、１４～１９．５％、特に１６～１９％が好ましい。ＺｒＯ2の含有量が少なすぎると、耐アルカリ性、耐酸性及び耐水性が低下し、ひいては塗膜の耐アルカリ性、耐酸性及び耐水性が低下する。一方、ＺｒＯ2の含有量が多すぎるとガラスの液相温度が高くなって生産性が低下する上、原料コストも高くなる。 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.
　本発明のガラスは、ガラス組成として、ＴｉＯ2を必須成分として２質量％以上含有する。ＴｉＯ2は、ガラスの耐水性と耐アルカリ性を向上させると共に、液相温度を大幅に低下させる成分である。本発明では、ガラス組成として、ＴｉＯ2を含有させることで、紫外域（２００～３８０ｎｍ）の透過率を低下させて、紫外線吸収性能を顕著に向上させることが可能である。このように、ＴｉＯ2は高い紫外線吸収性能を有するため、ＴｉＯ2を一定以上含有させたガラスを複合塗料に含有させることで、塗膜の紫外線による劣化を抑制できる。また、紫外線吸収性化合物の添加量に比べると、ＴｉＯ2はガラス中に高密度で含有させることが可能な上、可視光域におけるガラスの透過率をあまり低下させない。そのため、特に透明な複合塗料において、塗膜の透明性を維持したまま紫外線による劣化を効果的に抑制できる。 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. In the present invention, 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. As described above, 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. Moreover, compared with the addition amount of the ultraviolet absorbing compound, 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.
　ＴｉＯ2の含有量は２～２０％であり、５～１９％、より好ましくは５．６～１８％、６～１７％、６．５～１６％、６．８～１５％、特に７～１３％が好ましい。ＴｉＯ2の含有量が少なすぎると、ガラスの耐水性と耐アルカリ性が低下する上、ガラスの紫外線吸収性能が低下する。また、成形温度が上昇して生産コストが高くなる。一方、ＴｉＯ2の含有量が多すぎると、ガラス中にＴｉＯ2を含む結晶が析出し易くなって生産性が低下する上、原料コストが高くなる。 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. When 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. In addition, the molding temperature is increased and the production cost is increased. On the other hand, when 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.
　また、本発明のガラスは、更に、ガラス組成として、質量％で、ＳｉＯ2　５０～６５％、Ｌｉ2Ｏ＋Ｎａ2Ｏ＋Ｋ2Ｏ　１０～３０％、ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ　０～１０％を含有する。 Further, 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%.
　ＳｉＯ2は、ガラスの骨格構造を形成する主要成分である。また、ガラスの耐酸性を向上させる成分である。ＳｉＯ2の含有量は５０～６５％が好ましく、５５～６０％、特に５７～６０％が好ましい。ＳｉＯ2の含有量が少なすぎると、ガラスの機械的強度や耐酸性が低下し易くなり、ひいては塗膜の強度や耐酸性が低下する。一方、ＳｉＯ2の含有量が多すぎると、ガラスの耐アルカリ性が低下し、塗膜の耐アルカリ性が低下してしまう。また、ガラスの粘度が高くなってガラスの溶融に必要なエネルギーが増大し、製造コストが高くなる。 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.
　アルカリ金属酸化物は、ガラスの粘度を低下させ、溶融性や成形性を高める成分である。一方、アルカリ金属酸化物は、多量に含有しすぎるとガラスの耐水性を低下させてしまう成分である。アルカリ金属酸化物の合量（Ｌｉ2Ｏ＋Ｎａ2Ｏ＋Ｋ2Ｏ）は１０～３０％が好ましく、１２～２５％、１４～２２％、特に１５～１８％が好ましい。アルカリ金属酸化物の合量が少なすぎると、ガラスの粘度が高くなってガラスの溶融に必要なエネルギーが増大し、製造コストが高くなる。一方、アルカリ金属酸化物の合量が多すぎると、ガラスの耐水性が低下し易くなり、ひいては塗膜の耐水性が低下する。 The alkali metal oxide is a component that reduces the viscosity of the glass and enhances the meltability and the formability. On the other hand, 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.
　Ｌｉ2Ｏは少量の添加によって液相温度を大幅に下げ生産性を向上させる成分である。Ｌｉ2Ｏの含有量は、０～５％が好ましく、０～１％、特に０～０．６％が好ましい。一方、Ｌｉ2Ｏの含有量が多すぎると製造コストが増加する上、原料供給不安の懸念があるため、不可避不純物を除いて、含有しなくても良い。 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%. On the other hand, if 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.
　Ｎａ2Ｏはガラスの粘度を低下させることによって、ガラスの溶融性や成形性を高める成分である。Ｎａ2Ｏの含有量は１０～２０％が好ましく、１０～１８％、特に１２～１８％が好ましい。Ｎａ2Ｏの含有量が少なすぎると、ガラスの粘度が高くなってガラスの溶融に必要なエネルギーが増大し、製造コストが高くなる。一方、Ｎａ2Ｏの含有量が多すぎるとガラスの液相温度が高くなり、生産性が低下する。また、ガラスの耐水性が低下し易くなり、ひいては塗膜の耐水性が低下する。 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%. When the content of Na 2 O is too low, the viscosity of the glass is increased, the energy required for melting the glass is increased, and the production cost is increased. On the other hand, when the content of Na 2 O is too large, the liquidus temperature of the glass becomes high, and the productivity is lowered. In addition, the water resistance of the glass tends to decrease, which in turn reduces the water resistance of the coating.
　Ｋ2Ｏはガラスの粘度を低下させることによって、ガラスの溶融性や成形性を高める成分である。また、液相温度を下げる働きがあり、組成変化による失透性の変動を小さくする効果が大きい。Ｋ2Ｏの含有量は０～５％が好ましく、０～３％、０～２．５％、特に０．１～２％が好ましい。Ｋ2Ｏの含有量が少なすぎると、組成変化によって失透性が急激に変化するため好ましくない。一方、Ｋ2Ｏの含有量が多すぎるとガラスの耐水性が低下し易くなり、ひいては塗膜の耐水性が低下する。また、Ｋ2Ｏの含有量が多すぎると原料バッチが水分を吸収しやすくなり、原料粉末の凝集体（いわゆる「だま」）が形成されやすくなる。その結果、原料バッチの溶解性が悪化し、ガラス中に未溶解のジルコニアが残留しやすくなって好ましくない。 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%. When the content of K 2 O is too small, the devitrification property is rapidly changed due to the composition change, which is not preferable. On the other hand, when 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. In addition, when the content of K 2 O is too large, the raw material batch is likely to absorb water, and aggregates of the raw material powder (so-called “balls”) are easily formed. As a result, the solubility of the raw material batch is deteriorated, and undissolved zirconia tends to remain in the glass, which is not preferable.
　アルカリ土類金属酸化物は、ガラスの粘度を低下させる成分である。アルカリ土類金属酸化物の合量（ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ）は０～１０％が好ましく、０．１～５％、０．３～３％、特に０．４～２％が好ましい。アルカリ土類金属酸化物の合量が少なすぎると上記効果を得難くなる。一方、アルカリ土類金属酸化物の合量が多すぎるとガラス中にＺｒ、Ｓｉ、Ｎａ、アルカリ土類金属酸化物等からなる結晶が析出し易くなり、ガラスの液相温度が高くなり生産性が低下する。 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%. When the total amount of the alkaline earth metal oxides is too small, it is difficult to obtain the above effect. On the other hand, if 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はガラスの粘度を低下させる成分である。ＣａＯの含有量は０～１０％が好ましく、０．１～５％、０．３～３％、特に０．４～２％が好ましい。ＣａＯの含有量が少なすぎると上記効果を得難くなる。一方、ＣａＯの含有量が多すぎるとガラス中にＺｒ、Ｓｉ、Ｎａ、Ｃａ等からなる結晶が析出し易くなり、ガラスの液相温度が高くなり生産性が低下する。 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%. When the content of CaO is too small, it is difficult to obtain the above effect. On the other hand, when 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.
　Ａｌ2Ｏ3は、ガラスの化学的耐久性や機械的強度を高める成分である。一方、Ａｌ2Ｏ3は、ガラスの粘度を高める成分でもある。Ａｌ2Ｏ3の含有量は０～５％が好ましく、０～３％、特に０～１％が好ましい。Ａｌ2Ｏ3の含有量が少なすぎると、ガラスの化学耐久性が低下し易くなり、ひいては塗膜の化学耐久性が低下する。一方、Ａｌ2Ｏ3の含有量が多すぎるとガラスの粘度が高くなってガラスの溶融に必要なエネルギーが増大する。 Al 2 O 3 is a component that enhances the chemical durability and mechanical strength of the glass. On the other hand, 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.
　また本発明のガラスは、上記した成分（ＺｒＯ2及びＴｉＯ2、ＳｉＯ2、Ｌｉ2Ｏ、Ｎａ2Ｏ、Ｋ2Ｏ、ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ、Ａｌ2Ｏ3）以外の成分を含みうる。ただし上記した成分の含有量が合量で９８％以上、特に９９％以上となるように組成を調節することが望ましい。その理由は、これらの成分の合量が９８％未満の場合、意図しない異種成分の混入によって耐アルカリ性、耐酸性、耐水性が低下したり、生産性が低下したりする等の不都合が生じ易いからである。 Moreover, 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. However, it is desirable to adjust the composition such that the total content of the components described above is 98% or more, particularly 99% or more. 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.
　上記した成分以外の成分として、例えばＨ2、ＣＯ2、ＣＯ、Ｈ2Ｏ、Ｈｅ、Ｎｅ、Ａｒ、Ｎ2等の微量成分をそれぞれ０．１％まで含有してもよい。また、ガラス中にＰｔ、Ｒｈ、Ａｕ等の貴金属元素を５００ｐｐｍまで添加してもよい。 As components other than the above components, for example, 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%. In addition, noble metal elements such as Pt, Rh and Au may be added to the glass to 500 ppm.
　さらに耐アルカリ性、耐酸性、耐水性、液相温度の改善のために、Ｂ2Ｏ3、ＺｎＯ、Ｆｅ2Ｏ3、Ｐ2Ｏ5、Ｃｒ2Ｏ3、Ｓｂ2Ｏ3、ＳＯ3、ＭｎＯ、ＳｎＯ2、ＣｅＯ2、Ｃｌ2、Ｌａ2Ｏ3、ＷＯ3、Ｎｂ2Ｏ5、Ｙ2Ｏ3等を合量で２％まで含有してもよい。 Furthermore, for the improvement of alkali resistance, acid resistance, water resistance and liquid phase temperature, 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%.
　本発明のガラスは、光路長３μｍ、波長５５５ｎｍにおける透過率が７５％以上であることが好ましく、７８％以上、８０％以上、特に８５％以上であることが好ましい。更に、可視域（３８０～７８０ｎｍ）における平均透過率も、７５％以上、７８％以上、８０％以上、８５％以上であれば、より好ましい。このようにすれば、ガラスの透過率が向上するため、塗膜の透過率を向上させることができる。その結果、透明性に優れた塗膜を得ることが可能になる。 The glass of the present invention preferably has a transmittance of 75% or more at an optical path length of 3 μm 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.
　なお、更に塗膜の透明性を向上させるためには、上記のようにガラスの透過率を向上させるだけではなく、ガラスと塗膜形成樹脂塗膜の屈折率を整合させることが好ましい。屈折率差は、０．５％以下であることが好ましく、０．３％以下、０．２％以下、特に０．１％以下であることが好ましい、このようにすると、複合塗料の塗膜の透明性を向上させることができる。 In addition, in order to further improve the transparency of the coating film, it is preferable not only to improve the transmittance of the glass as described above, but to match the refractive indices of the glass and the coating film-forming resin coating film. The refractive index difference is preferably 0.5% or less, preferably 0.3% or less, 0.2% or less, particularly preferably 0.1% or less. In this way, the coating film of the composite paint Can improve the transparency of
　本発明のガラスは、光路長３μｍ、波長２７５ｎｍにおける透過率は７０％以下であることが好ましく、６５％以下、６０％以下、５０％以下、特に３０％以下であることが好ましい。更に、紫外域（２００～３８０ｎｍ）における平均透過率も、６０％以下、５５％以下、５０％以下、４５％以下であれば、より好ましい。このようにすれば、ガラスが紫外線を吸収するため、塗膜が紫外線によって劣化し難くなる。 The glass of the present invention preferably has a transmittance of 70% or less at an optical path length of 3 μm 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.
　本発明のガラスは、各種シランカップリング剤で被覆されていることが好ましい。シランカップリング剤としては、アミノシラン、ビニルシラン、エポキシシラン、ウレイドシラン等、各種カップリング剤を用いることができる。このようにすると、ガラス表面のシラノール結合部分との相溶性が良いため、ガラスと塗膜形成樹脂、更には被覆物との密着性を向上できる。 The glass of the present invention is preferably coated with various silane coupling agents. As the 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.
　本発明のガラスが鱗片状ガラスの形態である場合、鱗片状ガラスは、平均厚みが０．１～２０μｍ、平均粒径が２０～１０００μｍであることが好ましい。また、鱗片状ガラスは、平均粒径が５０～１０００μｍであることがより好ましい。更に、鱗片状ガラスは、最長の粒径／厚みの比率が１０以上になることが好ましい。 When the glass of the present invention is in the form of scale-like glass, the scale-like glass preferably has an average thickness of 0.1 to 20 μm and an average particle size of 20 to 1000 μm. The scaly glass more preferably has an average particle diameter of 50 to 1000 μm. Further, it is preferable that the glass flakes have a longest particle diameter / thickness ratio of 10 or more.
　塗膜にバリア性能を持たせる観点からは、鱗片状ガラスの平均厚みが０．１～２０μｍであることが好ましく、１～１５μｍ、２～１４μｍ、特に２～１０μｍであることが好ましい。また、例えばセメント硬化体塗布後の塗膜の乾燥厚みが２００μｍ以下の場合には、鱗片状ガラスを効率よく塗膜内に並列に配列させる観点からも上記範囲が好ましい。なお、複合塗料は、必要に応じて２回以上重ねて塗布してもよい。 From the viewpoint of imparting barrier properties to the coating film, the average thickness of the scaly glass is preferably 0.1 to 20 μm, more preferably 1 to 15 μm, 2 to 14 μm, and particularly preferably 2 to 10 μm. For example, in the case where the dry thickness of the coating after application of the cured cement is 200 μm or less, 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.
　また、耐火塗膜など塗膜に耐火性、耐熱性が要求される場合は鱗片状ガラスの平均厚みは０．１～２０μｍであることが好ましく、２～１８μｍ、特に３～１５μｍであることが好ましい。このようにすると、塗膜の耐熱性を効果的に高めることができる。 When the coating is required to have fire resistance and heat resistance, such as a fire resistant coating, the average thickness of the scale-like glass is preferably 0.1 to 20 μm, more preferably 2 to 18 μm, and particularly preferably 3 to 15 μm. preferable. In this way, the heat resistance of the coating can be effectively improved.
　また、塗膜内や塗布面に均一に鱗片状ガラスを分散させるためには、鱗片状ガラスの平均粒径が２０～１０００μｍであることが好ましく、３０～１０００μｍ、４０～１０００μｍ、５０～１０００μｍ、１００～９００μｍ、２００～８５０μｍ、特に３００～８００μｍであることが好ましい。上記の範囲外であると塗布し難くなり、鱗片状ガラスを均一に分散し難くなる。また、塗膜のバリア性能及び耐熱性が低下する。 In addition, in order to disperse scaly glass uniformly in the coating film or on the coated surface, the scaly glass preferably has an average particle diameter of 20 to 1000 μm, 30 to 1000 μm, 40 to 1000 μm, 50 to 1000 μm, The thickness is preferably 100 to 900 μm, 200 to 850 μm, and particularly 300 to 800 μm. It becomes difficult to apply | coat outside the said range, and it becomes difficult to disperse | distribute scaly glass uniformly. Moreover, the barrier performance and heat resistance of a coating film fall.
　本発明のガラスがミルドファイバーの形態である場合、ミルドファイバーは、アスペクト比（平均単繊維長／平均単繊維直径）が１～１００であることが好ましく、１．５～５０、２．０～２０、特に２．５～１０であることが好ましい。塗装又はコンクリート構造物への補修・補強などの目的でシート状の補強材を貼り付ける際の塗布工程は屋外等様々な自然条件の中で施工されるため、塗布後に乾燥・収縮する際に塗膜にひび割れが発生する場合があるが、本発明の複合塗料中に含まれるミルドファイバーは繊維状であるため、前記ひび割れを抑制する効果がある。しかし、アスペクト比が小さすぎると、応力を分散し難くなるため、その効果が得難い。一方、アスペクト比が大きすぎると、ミルドファイバーを塗料に分散させ難くなる上、塗膜の表面状態が悪化する。塗膜の表面状態が悪化すると、美観を損なうだけではなく、塗膜のひび割れや、セメント硬化体のひび割れを惹起する虞がある。 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. Although 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. However, if the aspect ratio is too small, it is difficult to disperse the stress, so it is difficult to obtain the effect. On the other hand, when 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.
　また、ミルドファイバーは、平均単繊維直径が、３～３０μｍ、８～２０μｍ、９～１７μｍ、特に１０～１４μｍであることが好ましい。平均単繊維直径が小さすぎると長繊維化が困難になり、生産性が悪化する。一方、平均単繊維直径が大きすぎると、塗膜を形成したときに、塗膜表面にミルドファイバーが突出しやすくなるため、表面状態が悪化する。塗膜の表面状態が悪化すると、美観を損なうだけではなく、塗膜のひび割れや、セメント硬化体のひび割れを惹起する虞がある。 The milled fibers preferably have an average single fiber diameter of 3 to 30 μm, 8 to 20 μm, 9 to 17 μm, and particularly 10 to 14 μm. When the average single fiber diameter is too small, it is difficult to form long fibers, and the productivity is deteriorated. On the other hand, when 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.
　また、ミルドファイバーは、平均単繊維長が、２０～４００μｍ、３０～３００μｍ、４０～２５０μｍ、５０～２００μｍ、特に６０～１５０μｍであることが好ましい。ミルドファイバーは、長繊維を粉砕加工して製造することから、平均単繊維長が短すぎると粉砕が困難になるばかりか、製造コストが上昇する。一方、平均単繊維長が長すぎると、ミルドファイバー同士の絡まりにより、塗料に分散させ難くなる上、塗膜の表面状態が悪化する。塗膜の表面状態が悪化すると、美観を損なうだけではなく、塗膜のひび割れや、セメント硬化体のひび割れを惹起する虞がある。 The milled fibers preferably have an average single fiber length of 20 to 400 μm, 30 to 300 μm, 40 to 250 μm, 50 to 200 μm, and particularly 60 to 150 μm. 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.
　本発明の複合塗料は、ガラスを含む。ガラスの詳細は既述のとおりであり、ここでは説明を省略する。 The composite paint of the present invention comprises glass. The details of the glass are as described above, and the description is omitted here.
　本発明の複合塗料は、ガラスの含有量が０．１～３０％であることが好ましく、１～２０％、特に３～１０％であることが好ましい。ガラスの含有量が少なすぎると、紫外線吸収性能が発揮できず、また、塗膜のバリア性能が低下するため、塗膜やコンクリート硬化体への水或いは大気中の二酸化炭素の進入を阻害し難くなる。更に、機械的強度も低下する。一方、ガラスの含有量が多すぎると、複合塗料中のガラスの分散性が悪化し易くなり、均一な塗膜を得難い。また、塗布し難くなり、所望の塗膜特性を得られなくなる。なお、複合塗料は、必要に応じて２回以上重ねて塗布してもよい。 In the composite paint of the present invention, 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 | coat and it becomes impossible to obtain a desired coating-film characteristic. The composite paint may be applied two or more times as needed.
　本発明の複合塗料は、少なくとも塗膜形成樹脂を含む。 The composite paint of the present invention contains at least a film-forming resin.
　塗膜形成樹脂としては、熱可塑性樹脂、熱硬化性樹脂、ＵＶ硬化性樹脂が好ましい。具体的には、アクリル樹脂、ウレタン樹脂、アクリルウレタン樹脂、ポリエステル樹脂、ポリアミド樹脂、メラミン樹脂、フェノール樹脂、アルキッド樹脂、エポキシ樹脂、塩化ビニル樹脂、フッ素樹脂、シラン樹脂、アクリルシリコン樹脂、などが挙げられる。特にこれらの中でも、耐アルカリ性に優れるものが好ましい。 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.
　また、塗膜形成樹脂は、所望の特性や用途に合わせて、上述した樹脂やそれ以外から選択される１種又は２種以上のものを任意で選択可能である。例えば、主に美観を求められるような塗装用途としてはアクリル樹脂、アクリルウレタン樹脂やウレタン樹脂、強度を求められるような剥落防止用途としてはエポキシ樹脂やアクリル樹脂が好適に用いられる。また、耐候性や耐薬品性を求められる用途には、例えば、フッ素樹脂を用いることができる。本発明の複合塗料は、耐アルカリ性に優れる上、紫外線による劣化が抑制されているため、いずれの用途でも、上塗り（保護塗装）なしで施工することが可能である。 Moreover, according to a desired characteristic and a use, 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. For example, an acrylic resin, an acrylic urethane resin or a urethane resin is preferably used as a coating application that requires an aesthetic appearance, and an epoxy resin or an acrylic resin is preferably used as an anti-peeling application that requires a strength. In addition, for applications where weather resistance and chemical resistance are required, for example, a fluorine resin can be used. 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.
　また、本発明の複合塗料は、更に、シリコーン系化合物、シロキサン化合物、シランカップリング剤、フッ素系化合物のいずれかを含有することができる。特にシラン系化合物の場合、ガラス表面のシラノール結合部分との相溶性が良く、ガラスと塗膜形成樹脂、更には被覆物との密着性を向上できる。 In addition, 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. In the case of 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.
　本発明の複合塗料は、耐アルカリ性及び紫外線吸収性能が高いガラスを含有するため、塗膜の紫外線劣化を抑制できる。特に、塗布乾燥後に透明性を有する塗膜の場合、すなわち可視光線領域で７５％以上の透過率を有する塗膜では、その効果が顕著である。 Since 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. In particular, in the case of 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.
　また、本発明の複合塗料は、更に、紫外線吸収性化合物を０～５％含んでもよく、０～３％、特に０～１％含むことが好ましい。 In addition, 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.
　紫外線吸収性化合物としては、チタンや亜鉛などの無機ナノ粒子、また有機系の紫外線吸収剤としてベンゾトリアゾール系紫外線吸収剤やヒドロキシフェニルトリアジン（ＨＰＴ）系紫外線吸収剤、更に、顔料を導入させる場合があり、このうちの１種又は２種以上をそれぞれ上記の量まで含有させてもよい。しかし、紫外線吸収性化合物は、コストや塗膜特性、安定性、塗料中の他成分への影響を鑑みると、一定量以上含有させないことが好ましい。本発明の複合塗料は、紫外線吸収性能が高いガラスを含有しているため、紫外線吸収性化合物の含有量を低減できる。 In the case of introducing 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, and further a pigment However, one or more of these may be contained to the above amount. However, in view of the cost, the coating film characteristics, the stability, and the influence on other components in the paint, it is preferable that 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.
　また、本発明の複合塗料は、例えば、シリコーン樹脂やフッ素樹脂等を含有させることで、塗膜に撥水機能を付与してもよい。 In addition, 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.
　また、本発明の複合塗料は、必要に応じて、顔料等の着色成分を添加することで着色してもよい。 In addition, the composite paint of the present invention may be colored by adding a coloring component such as a pigment, if necessary.
　更に、本発明の複合塗料は、必要に応じて、鱗片状ガラスとミルドファイバーの両方を含んでいてもよい。 Furthermore, the composite paint of the present invention may optionally contain both scaly glass and milled fiber.
　この場合、鱗片状ガラス及びミルドファイバーの両方が、本発明のガラスであってもよいし、いずれか一方が本発明とは異なるガラスであってもよい。例えば、本発明とは異なるガラスとしては、本発明のガラスとは組成の異なるＡガラス、Ｅガラス、ＥＣガラス等が挙げられる。このようにすることで、紫外線、水、ガスに対する塗膜のバリア性能をより向上させることができる。 In this case, 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. For example, as 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.
　また、複合塗料中における鱗片状ガラスとミルドファイバーの配合割合は、要求される特性に合わせて任意で調整可能である。例えば、複合塗料の分散性や、塗膜の均一性をより高めたい場合は、ミルドファイバーを高割合で配合させればよい。一方、紫外線、水、ガスに対する塗膜のバリア性能をより高めたい場合には、鱗片状ガラスを高割合で配合させればよい。 In addition, 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. For example, in order to further improve the dispersibility of the composite paint and the uniformity of the coating film, milled fibers may be blended at a high ratio. On the other hand, when it is desired to further enhance the barrier performance of the coating film against ultraviolet light, water and gas, scaly glass may be blended at a high ratio.
　更に、本発明の複合塗料は、セメント硬化体へと直接塗布するだけではなく、中塗りや、上塗り（保護塗装）として用いることもできる。具体的には、セメント硬化体補修後の表面や、補強用繊維（剥落防止用ネット等）の保護塗料として用いても良い。本発明の複合塗料は、耐アルカリ性に優れる上、紫外線による劣化が抑制されているため、耐久性が向上する。 Furthermore, 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.
　なお、上述したとおり、本発明のガラスは、紫外線吸収性能が高いことはもちろん、耐アルカリ性に優れ、バリア性能が高いため、複合塗料の他にも、様々な用途の複合材料に展開可能である。例えば、本発明のガラスは、有機溶剤と混合することで、撥水剤として用いることができる。 In addition, as described above, 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. . For example, the glass of the present invention can be used as a water repellent by mixing with an organic solvent.
　有機溶剤としては、例えば、シラン系化合物、シリコーン系化合物、シロキサン化合物、シランカップリング剤、フッ素系化合物等が挙げられる。特にシラン系化合物の場合、ガラス表面のシラノール結合部分との相溶性が良く、ガラスと被覆物との密着性を向上できる。そのため、セメント硬化体浸透性の撥水剤にも好適に使用できる。また、前述の有機溶剤を主剤とする撥水剤に、更にフッ素樹脂等の塗膜形成樹脂を混合させることで、浸透性を有しかつ塗膜も形成するような撥水剤とすることもよい。 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. In the case of 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. In addition, by mixing a film-forming resin such as a fluorocarbon resin with 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.
　本発明のガラスが鱗片状ガラスである場合、鱗片状であることから、塗面表面や、塗膜中の塗面方向と平行に配向し易いため、塗膜やコンクリート硬化体への水或いは大気中の二酸化炭素の進入を顕著に阻害できる。これにより、塗膜自体の膨れや、コンクリート硬化体の収縮変形、中性化を抑制できる。 When 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.
　また、本発明のガラスがミルドファイバーである場合、塗料中にガラスを均一に分散できる上、繊維状であるため、塗膜のひび割れを抑制することができ、塗膜やコンクリート硬化体への水或いは大気中の二酸化炭素の進入を顕著に阻害できる。これにより、塗膜自体の膨れや、コンクリート硬化体の収縮変形、中性化を抑制できる。更に、塗料中での分散性が良いため、複合塗料にガラスを多く含有でき、前述した効果を効果的に享受できる。 In addition, 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.
　本発明のガラスは、紫外線吸収性能が高いため、撥水剤に用いた際にも撥水剤の紫外線劣化を抑制できるため、被膜性能が向上し、撥水効果が長持ちする。また、塗面表面や、塗膜中の塗面方向に並列に配向し易いため、バリア性能が高く、コンクリート硬化体の劣化が抑制できる。特に、塗布乾燥後に透明性を有する撥水剤の場合、すなわち可視光線領域で７５％以上の透過率を有する撥水剤には顕著な効果が期待できる。 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.
　その他に、本発明のガラスは、コンクリートのひび割れ補修に用いるための補修材料或いはコンクリート片の剥落を防止する剥落防止材料として用いてもよい。なお、補修材料とは、例えば、コンクリートのひび割れにエポキシ樹脂やアクリル樹脂を注入し充填或いは塗布することで、補強し、防水性能を向上させ、ひび割れの進展を抑えるものである。また、剥落防止材料は、既設・新設問わず、構造的に剥落防止が必要な箇所にエポキシ樹脂やアクリル樹脂を塗布し、コンクリート片の剥落防止を行うものである。 In addition, 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. Incidentally, 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. In addition, regardless of existing and new materials, 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.
　本発明のガラスを用いると、補修或いは剥落防止材料のバリア性能が向上し、劣化が抑制され耐久性が向上する。その結果、補修或いは剥落防止材料そのものやコンクリート躯体への水或いは大気中の二酸化炭素の進入を阻害する効果を長期にわたって高めることができる。なお、前記材料は、透明性を有するものだけでなく、美観や、コンクリートと色調を合わせる目的のために、必要に応じて顔料等の着色成分を添加してもよい。更に、必要に応じて補強用繊維（剥落防止用ネット等）と複合して使用してもよい。 When the glass of the present invention is used, the barrier performance of the material for preventing or repairing the material is improved, the deterioration is suppressed, and the durability is improved. As a result, 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. In addition, 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. Furthermore, if necessary, it may be used in combination with a reinforcing fiber (such as an anti-falling net).
　表１は本発明の実施例（試料Ｎｏ．１、２）及び比較例（試料Ｎｏ．３、４）を示している。なお、実施例Ｎｏ．１、２及び比較例Ｎｏ．３は鱗片状ガラスを含む例であり、比較例Ｎｏ．４は鱗片状ガラスを含まない例である。実施例Ｎｏ．１、２は、本発明のガラス組成を満たす鱗片状ガラスを含んでいる。 Table 1 shows Examples (Sample Nos. 1 and 2) and Comparative Examples (Sample Nos. 3 and 4) of the present invention. In addition, Example No. No. 1, 2 and Comparative Example No. 1 No. 3 is an example containing scale-like glass, and 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.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表の各試料は、次のようにして作製した。 Each sample in the table was prepared as follows.
　まず、表中のガラス組成になるように、天然原料、化成原料等の各種ガラス原料を秤量、混合して、ガラスバッチを作製した。次に、このガラスバッチを白金ロジウム合金製坩堝に投入した後、間接加熱電気炉内で１５５０℃、５時間加熱して、溶融ガラスを得た。なお、均質な溶融ガラスを得るために、加熱時に、耐熱性撹拌棒を用いて、溶融ガラスを複数回攪拌した。その後、耐熱鋼製チューブに溶融ガラスを巻き付け、反対側から空気を流し込みガラスを膨らませた後、冷却してから破砕して、平均厚み３μｍ、平均粒径６００μｍの鱗片状ガラスを得た。 First, 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. Next, 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. In addition, in order to obtain a homogeneous 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 μm and an average particle diameter of 600 μm.
　厚み３μｍの鱗片状ガラスについて、下記の条件で透過率測定を行った。その結果を図１に示す。
機器：日本分光製　分光光度計　Ｖ－６７０
サンプリングピッチ：１ｎｍ
走査速度：２００ｎｍ／ｍｉｎ The transmittance of the scaly glass having a thickness of 3 μm 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
　図１から分かるように、実施例Ｎｏ．１、２のガラスは、比較例Ｎｏ．３のガラスに比べて紫外域（２００～３８０ｎｍ）の波長が吸収されやすいにも関わらず、可視域（特に５５５ｎｍ）における透過率は同等である。そのため、本発明のガラスを用いた複合塗料は、紫外線による塗膜の劣化を抑制できる上、塗膜にしたときの可視域における透明性を確保し易い。 As can be seen from FIG. 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.
　また、ガラスの耐アルカリ性は次のようにして測定した。まず、上記したような方法で得た溶融ガラスを流し出し板状のガラス試料を作製した。その板状ガラスを粉砕し、直径３００～５００μｍの粒度のガラスを比重×２重量分だけ精秤し、続いて１０質量％ＮａＯＨ溶液１００ｍｌ中に浸漬して、８０℃、９０時間の条件で振とうした。その後、ガラス試料の重量減少率を測定した。この値が小さいほど耐アルカリ性に優れていることになる。 Moreover, 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 μm 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.
　続いて、アクリルポリオール系ウレタン樹脂とヘキサメチレンジイソシアネートを４：１の割合に調合し、混練した２液性樹脂の中に、試料Ｎｏ．１～３の鱗片状ガラスを１５質量％添加した。その後、酢酸エチル、酢酸ブチルなどからなるシンナーを添加し、複合塗料を塗布可能な粘度に調整することで複合塗料を得た。なお、比較例Ｎｏ．４は、鱗片状ガラスを添加せずに作製した塗料である。 Subsequently, 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. In addition, comparative example No. 4 is a paint prepared without adding scaly glass.
　次に、得られた複合塗料又は塗料を、砂セメント比が１かつ水セメント比が０．４２のモルタルと、１３ｍｍの長さのガラス繊維を混練して得た、板状の繊維補強セメント硬化体上に乾燥後の塗膜の厚みが１００μｍになるように塗布した。 Next, 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.
　それぞれの塗膜に関し、塗膜付セメント硬化体の下地の透過具合について、目視にて評価を行い、目視にて下地が全く透過していないものを×、少し透過しているものを△、透過しているものを○、十分透過しているものを◎として評価を行った。 With respect to each coating film, 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 Δ, transmission Evaluations were made with ○ being good and ◎ being sufficiently transparent.
　その後、塗膜付セメント硬化体にＪＩＳ　Ｋ５６００－７－７キセノンランプ法（放射照度１８０ｗ/ｍ2）に準じた紫外線を１０００時間照射し、目視にて着色や剥がれ等の変化に関し、変化が顕著であったものを×、あったものを△、ほとんどなかったものを○、全くなかったものを◎として評価を行った。 After that, 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 で あ っ, △ for those that were も の, ○ for those that were hardly present, and ◎ for those that were not at all.
　本発明の鱗片状ガラスは、可視域における透過率が高く、紫外線吸収性能が高い。そのため、実施例Ｎｏ．１、２で示すように、本発明の複合塗料は、塗膜にしたときの可視域における透明性が良好であり、更に紫外線による塗膜の劣化が抑制されていた。 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.
　表２は本発明の実施例（試料Ｎｏ．５、６）及び比較例（試料Ｎｏ．７～９）を示している。なお、実施例Ｎｏ．５、６及び比較例Ｎｏ．７、８はミルドファイバーを含む例であり、比較例Ｎｏ．９はミルドファイバーを含まない例である。実施例Ｎｏ．５、６は、本発明のガラス組成を満たすミルドファイバーを含んでいる。 Table 2 shows Examples (Sample Nos. 5 and 6) and Comparative Examples (Sample Nos. 7 to 9) of the present invention. In addition, 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.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　透過率及び耐アルカリ性の測定に供するため、実施例１で説明した方法で表の各試料を作製した。なお、透過率及び耐アルカリ性は、ガラス組成に依存するところが大きい。試料Ｎｏ．５は実施例１の試料Ｎｏ．１と同じガラス組成であり、試料Ｎｏ．６は実施例１の試料Ｎｏ．２と同じガラス組成であり、試料Ｎｏ．７及びＮｏ．８は実施例１の試料Ｎｏ．３と同じガラス組成である。そのため、試料Ｎｏ．５～８の透過率測定及び耐アルカリ性の測定の各結果は、実施例１の対応する試料の測定結果と同じになる。したがって、試料Ｎｏ．５～８の透過率測定及び耐アルカリ性の測定の各結果は、実施例１の対応する試料の測定結果を援用し、詳しい説明を割愛する。 Each sample of Table was produced by the method demonstrated in Example 1 in order to use for the measurement of the transmittance | permeability and alkali resistance. 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.
　次に、実施例１で説明した方法で得た溶融ガラスを、数百のノズルを有する貴金属製ブッシングに供給し、繊維状に引き出して所定の平均単繊維直径を有するガラス繊維を得た。得られたガラス繊維をまず３ｍｍにカットし、その後、ヘンシェルミキサーとボールミル式粉砕機によって所定の平均単繊維長になるように粉砕し、ミルドファイバーを得た。 Next, 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.
　得られたミルドファイバーについて、ＪＩＳ　Ｒ　３４２０：２０１３のＡ法（輪郭法）で平均単繊維直径を測定し、ＪＩＳ　Ｒ　３４２０：２０１３のＡ法（輪郭法）に準ずる方法で平均単繊維長を測定した。なお、アスペクト比は、平均単繊維長を平均単繊維直径で割った値である。 About the obtained 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.
　続いて、アクリルポリオール系ウレタン樹脂とヘキサメチレンジイソシアネートを４：１の割合に調合し、混練した２液性樹脂の中に、試料Ｎｏ．５～８のミルドファイバーを１５質量％添加した。その後、酢酸エチル、酢酸ブチルなどからなるシンナーを添加し、複合塗料を塗布可能な粘度に調整することで複合塗料を得た。また、比較例Ｎｏ．９は、ミルドファイバーを添加せずに作製した塗料である。 Subsequently, 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. Moreover, comparative example No. 9 is a paint prepared without adding milled fiber.
　このようにして作製した複合塗料又は塗料を、目盛付きの５００ｍｌのビーカーに移して３０分間整置した後、蛍光灯光をビーカーの横から透過させた状態でミルドファイバーの沈降状態を目視にて確認した。分散性の評価は、殆どのミルドファイバーが２００ｍｌの目盛より下側に沈降していたものを×、４００ｍｌの目盛より下側に沈降していたものを△、殆ど沈降していなかったものを〇とした。 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. In the evaluation of 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 Δ, and those that were hardly sedimented were o And
　次に、得られた複合塗料を、砂セメント比が１かつ水セメント比が０．４２のモルタルと、１３ｍｍの長さのガラス繊維を混練して得た、板状の繊維補強セメント硬化体上に乾燥後の塗膜の厚みが１００μｍになるように塗布した。 Next, on the plate-like fiber-reinforced cement-hardened body obtained by kneading the obtained composite 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. To a thickness of 100 μm after drying.
　それぞれの塗膜に関し、塗膜付セメント硬化体の下地の透視具合について、目視にて評価を行い、下地が全く透視できないものを×、少し透視できるものを△、透視できるものを○、十分透視できるものを◎として塗膜の透明性の評価を行った。 With respect to each coating film, 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 Δ, those which can see through are ○, sufficient see-through The transparency of the coating film was evaluated as で き る which can be made.
　その後、塗膜付セメント硬化体にＪＩＳ　Ｋ５６００－７－７キセノンランプ法（放射照度１８０ｗ/ｍ2）に準じた紫外線を１０００時間照射し、目視にて着色や剥がれ等の
変化に関し、変化が顕著であったものを×、あったものを△、ほとんどなかったものを○、全くなかったものを◎として紫外線照射後の塗膜の状態の評価を行った。 After that, 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.
　本発明のミルドファイバーは、可視域における透過率が高く、紫外線吸収性能が高い。そのため、実施例Ｎｏ．５、６で示すように、本発明の複合塗料は、塗膜にしたときの可視域における透明性が良好であり、更に紫外線による塗膜の劣化が抑制されていた。 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.
　本発明の複合塗料およびガラスは、コンクリート構造物やセメントの塗装用に用いられ、特に、クリア塗装用として好適に用いられる。また、本発明のガラスは、有機溶剤と混合することで、撥水剤として用いることも可能である。更に、コンクリートのひび割れ補修に用いるための補修材料或いはコンクリート片の剥落を防止する剥落防止材料として用いてもよい。 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.

Claims (18)

  1. 　少なくとも塗膜形成樹脂とガラスとを含み、セメント硬化体の被覆に用いられる複合塗料であって、
    　前記ガラスが、ガラス組成として、質量％で、ＺｒＯ2　１２～２４％、ＴｉＯ2　２～２０％を含有することを特徴とする複合塗料。     A composite paint comprising at least a film-forming resin and glass and used for coating a cured cement,
    The glass is a glass composition including, in mass%, ZrO 2 12 ~ 24% , the composite coating, characterized by containing TiO 2 2 ~ 20%.
  2. 　前記ガラスが、更に、ガラス組成として、質量％で、ＳｉＯ2　５０～６５％、Ｌｉ2Ｏ＋Ｎａ2Ｏ＋Ｋ2Ｏ　１０～３０％、ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ　０～１０％を含有することを特徴とする請求項１に記載の複合塗料。 The glass is further a glass composition including, in mass%, SiO 2 50 ~ 65% , Li 2 O + Na 2 O + K 2 O 10 ~ 30%, to claim 1, characterized in that it contains 0 ~ 10% MgO + CaO + SrO + BaO Composite paint described.
  3. 　前記ガラスの光路長３μｍ、波長５５５ｎｍにおける透過率が７５％以上であることを特徴とする請求項１又は２に記載の複合塗料。 The composite paint according to claim 1 or 2, wherein the glass has an optical path length of 3 μm and a transmittance at a wavelength of 555 nm of 75% or more.
  4. 　前記ガラスの光路長３μｍ、波長２７５ｎｍにおける透過率が７０％以下であることを特徴とする請求項１～３の何れか１項に記載の複合塗料。 The composite paint according to any one of claims 1 to 3, wherein the glass has an optical path length of 3 μm and a transmittance at a wavelength of 275 nm of 70% or less.
  5. 　前記ガラスの表面がシランカップリング剤で被覆されていることを特徴とする請求項１～４の何れか１項に記載の複合塗料。 The composite paint according to any one of claims 1 to 4, wherein the surface of the glass is coated with a silane coupling agent.
  6. 　前記ガラスの含有量が０．１～３０質量％であることを特徴とする請求項１～５の何れか１項に記載の複合塗料。 The composite paint according to any one of claims 1 to 5, wherein the content of the glass is 0.1 to 30% by mass.
  7. 　前記ガラスが鱗片状ガラスを含むことを特徴とする請求項１～６の何れか１項に記載の複合塗料。 The composite paint according to any one of claims 1 to 6, wherein the glass comprises scale-like glass.
  8. 　前記鱗片状ガラスの平均厚みが０．１～２０μｍであり、且つ、前記鱗片状ガラスの平均粒径が２０～１０００μｍであることを特徴とする請求項７に記載の複合塗料。 The composite paint according to claim 7, wherein the average thickness of the scaly glass is 0.1 to 20 μm, and the average particle diameter of the scaly glass is 20 to 1000 μm.
  9. 　前記ガラスがミルドファイバーを含むことを特徴とする請求項１～８の何れか１項に記載の複合塗料。 A composite paint as claimed in any one of the preceding claims, characterized in that the glass comprises milled fibres.
  10. 　前記ミルドファイバーのアスペクト比（平均単繊維長／平均単繊維直径）が１～１００であることを特徴とする請求項９に記載の複合塗料。 The composite paint according to claim 9, wherein the aspect ratio (average single fiber length / average single fiber diameter) of the milled fibers is 1 to 100.
  11. 　前記ミルドファイバーの平均単繊維直径が３～３０μｍであり、且つ、前記ミルドファイバーの平均単繊維長が２０～４００μｍであることを特徴とする請求項９又は１０に記載の複合塗料。 11. The composite paint according to claim 9, wherein the average single fiber diameter of the milled fibers is 3 to 30 μm, and the average single fiber length of the milled fibers is 20 to 400 μm.
  12. 　前記塗膜形成樹脂が、熱可塑性樹脂、熱硬化性樹脂、ＵＶ硬化性樹脂の中から選択される１種又は２種以上であることを特徴とする請求項１～１１の何れか１項に記載の複合塗料。 The film-forming resin is one or more selected from a thermoplastic resin, a thermosetting resin, and a UV curable resin, according to any one of claims 1 to 11. Composite paint described.
  13. 　更にシリコーン系化合物、シロキサン化合物、シランカップリング剤、フッ素系化合物の中から選択される１種又は２種以上を含むことを特徴とする請求項１～１２の何れか１項に記載の複合塗料。 The composite paint according to any one of claims 1 to 12, further comprising one or more selected from silicone compounds, siloxane compounds, silane coupling agents, and fluorine compounds. .
  14. 　更に紫外線吸収性化合物を０～５質量％含むことを特徴とする請求項１～１３の何れか１項に記載の複合塗料。 The composite paint according to any one of claims 1 to 13, further comprising 0 to 5% by mass of an ultraviolet absorbing compound.
  15. 　ガラス組成として、質量％で、ＺｒＯ2　１２～２４％、ＴｉＯ2　２～２０％を含有し、且つセメント硬化体の被覆に用いることを特徴とするガラス。 A glass comprising, as a glass composition, 12 to 24% of ZrO 2 and 2 to 20% of TiO 2 by mass%, and used for coating a cement-hardened body.
  16. 　更に、ガラス組成として、質量％で、ＳｉＯ2　５０～６５％、Ｌｉ2Ｏ＋Ｎａ2Ｏ＋Ｋ2Ｏ　１０～３０％、ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ　０～１０％を含有することを特徴とする請求項１５に記載のガラス。 The glass according to claim 15, further comprising 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.
  17. 　鱗状片ガラスを含むことを特徴とする請求項１５又は１６に記載のガラス。 The glass according to claim 15 or 16, characterized in that it comprises a scaly glass.
  18. 　ミルドファイバーを含むことを特徴とする請求項１５～１７の何れか１項に記載のガラス。 A glass according to any of claims 15 to 17, characterized in that it comprises milled fibres.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020186283A (en) * 2019-05-10 2020-11-19 日本電気硝子株式会社 Composite coating

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JPH09110453A (en) * 1995-10-25 1997-04-28 Nippon Glass Fiber Co Ltd Alkali-resistant glass flake and thermoplastic resin composition or thermosetting resin composition reinforced with the flake
JP2005097080A (en) * 2003-08-29 2005-04-14 Nippon Sheet Glass Co Ltd Scaly glass
JP2009513470A (en) * 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 Alkali and acid resistant glass compositions for the production of glass strands

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09110453A (en) * 1995-10-25 1997-04-28 Nippon Glass Fiber Co Ltd Alkali-resistant glass flake and thermoplastic resin composition or thermosetting resin composition reinforced with the flake
JP2005097080A (en) * 2003-08-29 2005-04-14 Nippon Sheet Glass Co Ltd Scaly glass
JP2009513470A (en) * 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 Alkali and acid resistant glass compositions for the production of glass strands

Cited By (2)

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

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