WO2018042803A1 - コーティング組成物および被覆物品 - Google Patents
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- WO2018042803A1 WO2018042803A1 PCT/JP2017/020992 JP2017020992W WO2018042803A1 WO 2018042803 A1 WO2018042803 A1 WO 2018042803A1 JP 2017020992 W JP2017020992 W JP 2017020992W WO 2018042803 A1 WO2018042803 A1 WO 2018042803A1
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- oxide
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
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Definitions
- the present invention relates to a coating composition and a coated article. More specifically, the present invention relates to a room temperature curable coating composition containing ultraviolet light absorbing inorganic fine particles, and an article coated with a cured film of the composition.
- Patent Document 1 and Patent Document 2 the deterioration of building materials is suppressed by using an organic phenyltriazine compound as an ultraviolet absorber.
- the phenyl triazine type ultraviolet absorber is an organic compound, there is a problem that the phenyl triazine itself is deteriorated by being exposed to ultraviolet rays for a long period of time, so that the ultraviolet absorbing ability is greatly lowered and discolored.
- Patent Literature 3 and Patent Literature 4 report a method using zinc oxide.
- titanium oxide has a larger extinction coefficient than zinc oxide, it may be able to solve the problem that occurs with zinc oxide, but it is difficult to disperse titanium oxide stably and transparently in the coating composition. It was.
- titanium oxide has a strong photocatalytic activity, it has not been considered to exhibit weathering resistance when it is blended in a coating composition, exhibiting a cracking action and a choking action.
- Patent Document 5 reports that the photocatalytic activity is suppressed in core-shell particles having a manganese dioxide layer on the surface of titanium oxide particles.
- manganese dioxide is known to act as an oxidizing agent, and in a coating composition containing the above particles, organic compounds such as synthetic resins contained in the composition may be oxidized to deteriorate the coating film. There is sex.
- Patent Document 6 and Patent Document 7 a silicone coating composition containing tetragonal titanium oxide solid solution fine particles in which tin and manganese are solid-solved does not cause cracking, Although it has been found that it exhibits high weather resistance, the silicone coating agent of each of the above-mentioned patent documents requires heat curing, so that it is difficult to apply it to coating applications such as building exterior materials and interior materials.
- the silicone coating agent of each of the above-mentioned patent documents requires heat curing, so that it is difficult to apply it to coating applications such as building exterior materials and interior materials.
- titanium oxide fine particles are introduced into a room temperature curable coating, there is a problem that the particles cause aggregation / white turbidity and the transparency and ultraviolet light absorption ability are greatly reduced.
- there is no room temperature curable coating composition that has a property that the cured coating film exhibits ultraviolet shielding properties while maintaining transparency and also has a property of protecting the substrate from long-term outdoor exposure.
- Japanese Patent No. 4669992 Japanese Patent No. 5361513 JP 2010-261012 A JP2011-225660A Japanese Patent No. 5404421 Japanese Patent No. 5704133 JP 2016-14132 A
- the present invention has been made in view of the above circumstances, exhibits room temperature curability when curing a coating film, exhibits ultraviolet shielding properties while maintaining transparency of visible light, and does not impair the appearance of the substrate. It is an object of the present invention to provide a coating composition capable of providing a cured film capable of suppressing fading and deterioration of a material, and a coated article using the composition.
- a composition obtained by blending core-shell fine particles having a predetermined titanium oxide nucleus in a predetermined ratio with respect to a room-temperature curable resin at room temperature when the coating film is cured In order to give a cured film that exhibits UV shielding properties while maintaining the transparency of visible light while exhibiting curability, it has been found to be a composition suitable for coating applications such as exterior materials and interior materials such as buildings, The present invention has been completed.
- the present invention 1.
- the room temperature curable resin is an acrylic resin, a polyester resin, a silicone-modified polyester resin, a silicone-modified acrylic resin, an epoxy resin, a polycarbonate resin, a silicone resin, a fluororesin, a chlorine resin, a polyolefin resin, a urethane resin, and an acrylic urethane resin.
- 1 or 2 coating compositions comprising one or more resins selected from the group consisting of: 4). And 1 selected from the group consisting of aluminum oxide, cerium oxide, zinc oxide, indium tin oxide, zirconium oxide, tin oxide, iron oxide, silicon oxide, and titanium oxide (excluding the core-shell fine particles of (B) above). Any of 1-3 coating compositions comprising seeds or two or more, 5).
- the coating composition of the present invention can be cured at room temperature, and the cured film exhibits ultraviolet shielding properties while maintaining the transparency of visible light, so that the substrate fading or deterioration without impairing the appearance of the substrate. Can be suppressed.
- the coating composition of the present invention having such characteristics is suitable as a room temperature curing type UV shielding clear coating agent that can be applied to various materials such as exterior materials and interior materials such as buildings. By using the composition, the appearance and characteristics of the substrate can be maintained over a long period of time.
- FIG. 6 is an ultraviolet-visible transmitted light spectrum diagram of the cured coating produced in Example 4.
- 6 is an ultraviolet-visible transmitted light spectrum diagram of a cured coating produced in Example 5.
- FIG. It is an ultraviolet-visible transmitted light spectrum figure of the cured film produced in Example 6.
- 6 is an ultraviolet-visible transmitted light spectrum diagram of a cured coating produced in Comparative Example 2.
- the coating composition according to the present invention has (A) room temperature curable resin: 100 parts by mass, and (B) tetragonal titanium oxide solid solution fine particles in which tin and manganese are solid-solved as nuclei, and silicon oxide on the outside of the nuclei.
- Core-shell fine particles having a shell characterized by containing 0.1 to 50 parts by mass.
- “room temperature” when curing a coated film usually means 0 to 40 ° C., preferably 5 to 35 ° C.
- Room temperature curable resin Specific examples of the room temperature curable resin used in the coating composition of the present invention include acrylic resin, polyester resin, silicone modified polyester resin, silicone modified acrylic resin, epoxy resin, polycarbonate resin, and silicone resin. , Transparent coating compositions containing one or more resin components selected from the group consisting of fluororesins, chlorinated resins, polyolefin resins, urethane resins, and acrylic urethane resins. By appropriately selecting a resin having a high affinity with the target base material, it is possible to impart high adhesion to the base material to the coating film.
- paints for these resin components, commercially available room temperature curable paints may be used. Specific examples thereof include a solventless silicone coating composition (KR-400, manufactured by Shin-Etsu Chemical Co., Ltd.), an oil-based epoxy. Paint (clear epoxy anticorrosion paint, manufactured by Niphome Products), water-based acrylic silicone paint (transparent water-based versatile color, manufactured by Asahi Pen Co., Ltd.), oil-based silicone paint (waterproof most clear, Nippon Special Paint Co., Ltd.) )), Water-based acrylic varnish (transparent water-based varnish, manufactured by Asahi Pen Co., Ltd.), oil-based urethane paint (oil-based varnish, manufactured by Washin Paint Co., Ltd.), water-based urethane paint (water-based urethane varnish, manufactured by Washin Paint Co., Ltd.) ) And the like. These paints may contain water or an organic solvent as a solvent, and even if the resin component as an active ingredient exists as an emulsion with the solvent, it is
- the core-shell fine particles used in the coating composition of the present invention have tetragonal titanium oxide solid solution fine particles in which tin and manganese are solid-solved as nuclei and have a silicon oxide shell outside the nuclei.
- titanium oxide There are generally three types of titanium oxide: rutile type, anatase type, and brookite type.
- rutile type titanium oxide having low photocatalytic activity and excellent ultraviolet absorption ability is used as a solid solution of tin and manganese. Used as a solvent.
- the tin component as a solid solute should just be derived from a tin salt, and specific examples thereof include tin chalcogenides such as tin oxide and tin sulfide, and tin oxide is preferred.
- Tin salts include tin halides such as tin fluoride, tin chloride, tin bromide and tin iodide; tin pseudohalides such as tin cyanide and tin isothiocyanide; tin such as tin nitrate, tin sulfate and tin phosphate Examples thereof include mineral acid salts, but tin chloride is preferable because of its stability and availability.
- the tin valence in the tin salt can be selected from divalent to tetravalent, but tetravalent is preferred.
- the manganese component as a solid solute may be one derived from a manganese salt, and specific examples thereof include manganese chalcogenides such as manganese oxide and manganese sulfide. Among these, manganese oxide is preferable.
- Manganese salts include manganese halides such as manganese fluoride, manganese chloride, manganese bromide and manganese iodide; manganese pseudohalides such as manganese cyanide and manganese isothiocyanide; manganese such as manganese nitrate, manganese sulfate and manganese phosphate Examples thereof include mineral acid salts, and manganese chloride is preferred from the viewpoint of stability and availability.
- the manganese valence in the manganese salt can be any of bivalent to heptavalent, but divalent is preferred.
- the solid solution amount of the tin component is preferably 10 to 1,000, more preferably 20 to 200, in terms of a molar ratio with titanium (Ti / Sn).
- the solid solution amount of the manganese component is preferably 10 to 1,000, more preferably 20 to 200, in terms of a molar ratio with titanium (Ti / Mn).
- the solid solution amount of the tin component and the manganese component is less than 10 in terms of molar ratio (Ti / Sn) and (Ti / Mn) with titanium, light absorption in the visible region derived from tin and manganese becomes remarkable.
- the photocatalytic activity may not be sufficiently deactivated, and the crystal system may be an anatase type having a small ultraviolet absorbing ability.
- the solid solution mode of the tin component and the manganese component may be a substitution type or an interstitial type.
- the substitution type is a solid solution mode formed by substituting tin and manganese at the site of titanium (IV) ions of titanium oxide
- the interstitial type is tin between crystal lattices of titanium oxide. It is a solid solution mode formed by the presence of manganese.
- the F center that causes coloring is easily formed, and since the symmetry around the metal ion is poor, the Frank-Condon factor of the vibronic transition in the metal ion also increases, and it becomes easy to absorb visible light.
- the substitution type is preferred.
- the shell of silicon oxide formed outside the nucleus of tetragonal titanium oxide fine particles in which tin and manganese are dissolved may contain silicon oxide as a main component and may contain other components such as tin and aluminum.
- Such a method of forming the silicon oxide shell is arbitrary, and for example, it can be formed by reacting an organic silicon compound or an inorganic silicon compound on the surface of the titanium oxide fine particles.
- organosilicon compound that can be used include tetraalkoxysilane, and a silicon oxide shell can be formed outside the core of the titanium oxide fine particles by hydrolysis and condensation.
- tetraalkoxysilane include those usually available such as tetramethoxysilane, tetraethoxysilane, tetra (n-propoxy) silane, tetra (i-propoxy) silane, and tetra (n-butoxy) silane.
- tetraethoxysilane is preferred from the viewpoints of reactivity and safety.
- tetraalkoxysilane Commercially available tetraalkoxysilane may be used, and specific examples thereof include tetraethoxysilane KBE-04 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.
- the hydrolytic condensation of tetraalkoxysilane can be carried out in water using a condensation catalyst such as ammonia, aluminum salt, organoaluminum, tin salt, organotin as appropriate.
- ammonia can be preferably used because it also serves as a dispersant for the nuclear fine particles.
- inorganic silicon compounds include alkali silicates and activated silicic acid obtained by cation exchange of alkali silicates. By mixing these with titanium oxide fine particles, the outer side of the core of the titanium oxide fine particles can be used. A silicon oxide shell can be formed.
- alkali silicate include those usually available such as sodium silicate and potassium silicate.
- a commercially available product may be used as the alkali silicate, and specific examples thereof include “sodium silicate” (manufactured by Fuji Chemical Co., Ltd.).
- the activated silicic acid is obtained, for example, by cation exchange by bringing an alkali silicate aqueous solution into contact with a cation exchange resin.
- the raw material of the alkali silicate aqueous solution include the above-mentioned various alkali silicates.
- commercially available “sodium silicate” (manufactured by Fuji Chemical Co., Ltd.) can be used.
- the cation exchange resin may be appropriately selected from those usually available, and specific examples thereof include “Amberjet 1024H” (manufactured by Organo Corporation).
- Examples of the contact method between the alkali silicate aqueous solution and the cation exchange resin include a method of adding a strongly acidic cation exchange resin (H + type) to an alkali silicate aqueous solution diluted with water, and a strongly acidic cation exchange resin ( And a method of flowing an alkali silicate aqueous solution diluted with water through an ion exchange resin tower packed with H + type.
- the concentration of the aqueous alkali silicate solution is not particularly limited, but is preferably 1 to 10% by mass in terms of silica in terms of production efficiency and prevention of gelation of the obtained active silicic acid. 1 to 5% by mass is more preferable, and 2 to 4% by mass is even more preferable.
- the cation exchange treatment is preferably performed so that the pH of the resulting active silicic acid solution is 1 to 5, and more preferably 2 to 4.
- the mixing method of the alkali silicate or active silicic acid and the titanium oxide fine particles is not particularly limited, and examples thereof include a method of gradually adding an aqueous solution of alkali silicate or active silicic acid to the dispersion of the titanium oxide fine particles.
- the ratio of silicon oxide in the shell to the entire core-shell type tetragonal titanium oxide solid solution is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, and even more preferably 15 to 40% by mass. If the ratio of silicon oxide is less than 5% by mass, the shell may not be formed sufficiently. On the other hand, if it exceeds 50% by mass, the core-shell fine particles are likely to aggregate and the dispersion may become opaque.
- titanium oxide used in the present invention may be further doped with a metal other than tin or manganese.
- the dope described here has a broad meaning, and includes both simple dope and dope via a chemical bond.
- the particle diameter (average cumulative particle diameter) of the core-shell fine particles can be measured by various methods.
- the 50% cumulative diameter (D 50 ) in the volume-based particle size distribution measured by a dynamic light scattering method using laser light is used, but it is also possible to observe using electron microscopy as evidence.
- the values obtained by these measurement methods do not depend on the measurement device, but for example, a device such as Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) can be used as the dynamic light scattering method.
- An example of the electron microscope method is a transmission electron microscope H-9500 (manufactured by Hitachi High-Technologies Corporation).
- D 50 of the core-shell fine particles is preferably 1 to 200 nm, more preferably 1 to 100 nm, and even more preferably 1 to 80 nm. 1 to 50 nm is more preferable.
- the average cumulative particle diameter of the core-shell fine particles exceeds 200 nm, the particle diameter becomes larger than the light wavelength in the visible region, and the scattering may be remarkable.
- the thickness is less than 1 nm, the total surface area of the core-shell fine particles in the system may become extremely large, which may make it difficult to handle the particles as particles.
- the silicon oxide shell on the surface of the core-shell fine particles may be surface-treated with an organosilyl group via a siloxane bond.
- This organosilyl group can be introduced, for example, by modifying the core-shell particle surface with a silane compound represented by the following general formula (I), a (co) hydrolysis condensate of the silane compound, or a mixture thereof. .
- R 1 m Si (Y) 4-m (I) (Wherein R 1 s may be the same or different and each has 1 to 20 carbon atoms which may be substituted with a (meth) acryl group, an oxiranyl group, an amino group, a mercapto group, an isocyanate group or a fluorine atom).
- Y represents a substituent selected from the group consisting of an alkyl group, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a (poly) dimethylsiloxy group having 50 or less silicon atoms, or Y is And represents a substituent selected from the group consisting of an alkoxy group, an acetoxy group, an enol group, a hydroxyl group, and a chlorine atom, and m is an integer of 1 to 3.
- the alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, or an n-propyl group.
- the alkenyl group is preferably an alkenyl group having 2 to 6 carbon atoms, more preferably a vinyl group or an allyl group.
- As the aryl group an aryl group having 6 to 10 carbon atoms is preferable, and a phenyl group is more preferable.
- the silicon number of the (poly) dimethylsiloxy group is preferably 1 to 50, and more preferably 1 to 30.
- Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, and an n-butoxy group, and a methoxy group is preferable.
- Dimethylmethoxysilane iso-propyldiethylmethoxysilane, propyldimethylethoxysilane, n-butyldimethylmethoxysilane, n-butyldimethylethoxysilane, n-hexyldimethylmethoxysilane, n-hexyldimethylethoxysilane, n-pentyldimethylmethoxysilane , N-pentyldimethylethoxysilane, n-hexyldimethylmethoxysilane, n-hexyldimethylethoxysilane, n-decyldimethylmethoxysilane, n-decyldimethyl Silane and the like.
- n is preferably an integer of 0 to 50, more preferably an integer of 5 to 40, and even more preferably an integer of 10 to 30.
- n is larger than 50, the properties as a silicone oil become strong, and the solubility of the surface-treated organosol in various resins may be limited.
- the silane compounds used for the surface treatment may be used singly or in combination of two or more, or may be used as two or more cohydrolyzate condensates.
- the surface treatment of the core-shell fine particles may be performed stepwise with the same or different silane compounds.
- the amount of the silane compound used is preferably 0.5 to 50 times, more preferably 1 to 25 times, and even more preferably 2 to 10 times the mass of the core-shell fine particles. If the amount used is more than 50 times, gelation may occur. On the other hand, if the amount used is less than 0.5 times, the coating may be insufficient, resulting in aggregation.
- the surface treatment using the silane compound is preferably performed using a colloidal dispersion of core-shell fine particles using water as a dispersion medium.
- the dispersoid concentration of the colloidal dispersion is preferably 1 to 35% by mass, more preferably 5 to 30% by mass, and even more preferably 10 to 25% by mass from the viewpoint of increasing production efficiency and preventing gelation.
- the dispersion medium may contain a monohydric alcohol that is arbitrarily miscible with water in the step of producing the aqueous dispersion colloidal solution.
- the monohydric alcohol that is optionally miscible with water may be derived from a co-solvent in the production of the core-shell microparticles and a hydrolysis by-product of the metal alkoxide in the sol-gel reaction.
- Examples of monohydric alcohols miscible with water include methanol, ethanol, 1-propanol, 2-propanol and the like.
- the solvent for dilution include monohydric alcohols such as methanol, ethanol, 1-propanol, 2-propanol and 1-butanol; polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin; propylene glycol monomethyl ether, Ethers such as ethylene glycol monomethyl ether, glyme and diglyme; Ketones such as acetone and methyl isobutyl ketone; Esters such as ethyl acetate and propylene glycol monomethyl ether acetate; Hexanediol diacrylate, Trimethylolpropane triacrylate, Pentaerythritol tetra And reactive esters such as acrylate and dipentaerythritol hexaacrylate.
- ethanol and 2-propanol are preferred. Arbitrariness.
- the silane compound may be added to the water-dispersed colloidal solution described above by dropping in the liquid, dropping outside the liquid, adding a portion, or the like, but adding by dropping in the liquid is preferable.
- the temperature at the time of adding the silane compound is preferably 0 to 45 ° C, more preferably 5 to 40 ° C, and more preferably 10 to 35 ° C, from the viewpoint of alteration of the colloidal aqueous dispersion and prevention of unexpected hydrolytic condensation of the silane compound. Even more preferred.
- the temperature of a reaction liquid may rise to less than about 70 degreeC by the heat of reaction by hydrolysis condensation.
- an acid or base catalyst can be added for the purpose of promoting the reaction, if necessary.
- the base catalyst include potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate and basic ion exchange resin.
- Specific examples of the acid catalyst include hydrochloric acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, acetic acid, and a cationic ion exchange resin.
- Specific examples of the cationic ion exchange resin include Amberlite (manufactured by Organo), Levatit (manufactured by LANXESS), Purolite (manufactured by Purolite), Muromac (manufactured by Muromachi Chemical Co., Ltd.), and the like.
- the amount of these catalysts used is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, and more preferably 1 to 5% by mass with respect to the core-shell fine particles from the viewpoint of appropriately controlling the reaction rate. % Is even more preferred.
- the organosilyl group introduced on the surface of the core-shell fine particles can be evaluated by confirming a peak characteristic of the organosilyl group by IR spectrum or solid NMR spectrum.
- the introduction amount of the organosilyl group can be estimated from the difference between the mass reduction rate of the core-shell fine particles before the reaction with the organosilyl group and the mass reduction rate of the surface-treated fine particles having the organosilyl group. From the viewpoint of imparting dispersibility to an organic solvent, it is preferably 2% by mass or more of the fine particles.
- the dispersion medium in the reaction liquid may be replaced with a polar organic solvent as necessary.
- the dispersion medium in the dispersion liquid is leached by ultrafiltration, It is preferable to perform substitution and concentration, whereby the solid content concentration of the dispersion in the filtration chamber is preferably 1 to 30% by mass, more preferably 5 to 25% by mass, and even more preferably 10 to 20% by mass. adjust.
- water contained in the aqueous dispersion colloidal solution alcohols derived from silicic acid esters formed by hydrolysis and condensation of the added silicon compound or hydrolysis condensate of the silicon compound, added as necessary 1 Contains monohydric alcohols and other organic solvents.
- a porous ceramic filter can be suitably used for ultrafiltration of a dispersion medium composed of such a complex mixture. More specifically, it is preferable to use a filter plate provided with an inorganic ceramic membrane having an average pore diameter of 5 nm or more and less than 20 nm, more preferably an average pore diameter of 6 to 18 nm, and even more preferably an average pore diameter of 7 nm.
- the shape is preferably a rotatable disk.
- the porous inorganic ceramic membrane can be produced by a known method.
- the material of the porous inorganic ceramic film include spinel-based, alumina-based, titania-based, zirconia-based, and the like. If the spinel-based material is used, a method known in the literature (Ueno, S et al. Journal of Physics: Conference Series 2009, 165, No. 1, Fabrication of Porous Magnesium spinel with Cylindrical Pores by Undirective Solidification, Zhang, Guo-chang, et al., 2000, 03, MgAl 2 Ot. Can be synthesized. It is preferable to control the pore diameter by controlling the synthesis conditions and crystal growth of spinel.
- the filter plate is preferably formed by epitaxially growing a surface layer having a uniform pore diameter on a porous disk-shaped unglazed plate made of alumina or the like by a sol-gel method.
- a porous disc-shaped unglazed plate made of alumina or the like it is preferable to use a porous disc-shaped plate having a pore diameter of 0.05 to 1 ⁇ m.
- the average pore diameter of the surface layer is preferably 5 nm or more and less than 20 nm, more preferably 6 to 18 nm, and even more preferably 7 nm. This pore diameter is preferably determined by electron microscopy. Examples of electron microscopes that can be used for such purposes include scanning electron microscopes, transmission electron microscopes, and atomic force microscopes.
- the size of the disk-shaped filter plate is preferably 100 mm or more and less than 500 mm, more preferably 120 to 300 mm, and still more preferably 140 to 200 mm. If the diameter is less than 100 mm, it may be difficult to secure the area, and it may be difficult to apply shear stress when rotating. If it is 500 mm or more, the torque required for rotation may increase. It may be easier to handle.
- the thickness of the filter plate is preferably 1 mm or more and less than 10 mm, more preferably 3 to 5 mm in consideration of ensuring mechanical strength and securing the volume of the filtration chamber. Such a filter may be manufactured by a known method, or a commercially available filter may be used.
- the static pressure when the dispersion medium is leached is preferably less than 0.5 MPa, preferably 0.4 MPa or less, considering the ease of selecting the interface of the filtration device and efficiently leaching the dispersion medium. 3 MPa or less is more preferable, and 0.03 to 0.2 MPa is particularly preferable.
- the static pressure is preferably applied by a hydraulic head tube whose surface is in contact with the atmosphere, or by a hydraulic pressure and a compressed air pressure in a closed system. In particular, since the apparatus can be made compact, it is preferably applied by a compressed air pressure. Compressed air can be easily created using a known method or a commercially available compressor.
- the shear stress applied to the disc-shaped filter plate when replacing the dispersion medium is preferably 0.1 to 10 Pa, more preferably 0.5 to 5 Pa, and even more preferably 1 to 5 Pa.
- the shear stress may be applied by the flow of the dispersion or by rotating the disk-shaped filter plate. However, since the shear rate of the filter plate surface increases, the shear stress may be applied by rotating the filter plate. preferable.
- the shear stress can be calculated from the distance between the walls in the filter chamber and the rotational speed. For the purpose of reducing the distance between the walls in the filter chamber, an appropriate baffle (baffle plate) can be provided in the filter chamber as necessary. Increasing the shear stress by rotation and baffles is a known means.
- the maximum shear stress ( ⁇ ) acting on the circumference is the diameter of the disk-shaped filter plate ( ⁇ [m]), the rotation speed of the filter plate ( ⁇ [rps]), and the distance between the filter plate and the filtration chamber wall (L [m]), the circumference is ( ⁇ ), and the viscosity of the dispersion is ( ⁇ [Pa ⁇ s]), for example, it can be calculated as in Equation (1).
- ⁇ ( ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ) / L [Pa] (1)
- the diameter ⁇ 0.15 [m]
- the rotational speed of the filter plate ⁇ 16.7 [rps] ( ⁇ 1,000 [rpm])
- the circumference ⁇ 3.14
- 0.001 [Pa ⁇ s] and the inter-wall distance L 0.003 [m]. 6 [Pa].
- the shear stress can be given by changing each parameter of ⁇ , ⁇ , and L so that the preferred range is reached.
- the rotational energy applied to the dispersion is preferably defined by the above-described shear stress, but can also be defined in the state of fluid.
- the fluid state can be defined by the Reynolds number.
- the stirring Reynolds number is preferably 3,000 to 5,000,000 in consideration of increasing the efficiency of dispersion by preventing laminar stirring and increasing the energy required for stirring within an appropriate range. 000 to 1,000,000 is more preferable, and 10,000 to 500,000 is even more preferable.
- This Reynolds number (Re) can be obtained from Equation (2).
- ⁇ represents density (kg / m 3 )
- ⁇ rotational speed (rps)
- ⁇ represents filter plate diameter (m)
- ⁇ viscosity (Pa ⁇ s).
- Re ⁇ ⁇ ⁇ ⁇ 2 / ⁇ ...
- ⁇ is preferably 900 to 2,000 (kg / m 3 ), more preferably 1,000 to 1,500 (kg / m 3 ).
- ⁇ is preferably 0.001 to 0.05 (Pa ⁇ s), and more preferably 0.002 to 0.01 (Pa ⁇ s).
- a 0.15 (m) disk-shaped filter plate is treated with a core-shell fine particle dispersion with 16.7 (rps), ⁇ of 1,000 (kg / m 3 ), and ⁇ of 0.001 (Pa ⁇ s).
- Re is about 3.8 ⁇ 10 5 .
- the temperature at the time of replacing the dispersion medium is preferably 5 to 80 ° C., and more preferably 10 to 60 ° C. from the viewpoint of preventing the dispersion medium from freezing and volatilization, and further gelation when using reactive esters. Preferably, 15 to 50 ° C is even more preferable, and 20 to 40 ° C is optimal. Since the viscosity of the dispersion generally depends on the temperature and the viscosity affects the rotational torque, it is preferable to adjust the temperature so that the electromagnetic rotating machine and the motor are not overloaded. When replacing the dispersion medium, unreacted compounds and by-products can be removed by continuous ultrafiltration as necessary.
- organic solvent used for replacing the dispersion medium examples include 1 such as methanol, ethanol, 1-propanol, 2-propanol, cyclopentanol, ethylene glycol, propylene glycol, ⁇ -thiadiglycol, butylene glycol, glycerin and the like.
- Divalent and polyhydric alcohols diethyl ether, dipropyl ether, cyclopentyl methyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol mono Butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether Ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, butylene glycol monomethyl ether, butylene glycol monoethyl ether, butylene glycol monopropyl ether, butylene glycol monobutyl ether; methyl formate, ethyl formate, propyl formate, butyl formate , Methyl acetate, ethyl acetate, propyl acetate, butyl a
- amides Among these, methanol, ethanol, 1-propanol, 2-propanol, propylene glycol monomethyl ether, and the like are preferable from the viewpoint of dispersibility of the core-shell fine particles and ease of evaporation of the dispersion medium.
- the amount of the organic solvent used for solvent replacement is preferably 1 to 20 times by volume, more preferably 2 to 10 times by volume, more preferably 3 to 8 volumes with respect to the filtration chamber capacity, considering the replacement efficiency and production efficiency of the dispersion medium Double is even more preferred.
- the coating composition of the present invention comprises the room temperature curable resin and the core-shell fine particles described above.
- the amount of the core-shell fine particles blended in the coating composition is 0.1 to 50 parts by mass with respect to 100 parts by mass of the room temperature curable resin in consideration of the ultraviolet absorption ability of the obtained cured film and the fine particle dispersibility. 1 to 20 parts by mass is preferable.
- room temperature curable resin is a composition containing a solvent
- the compounding quantity of core-shell fine particles is determined on the basis of 100 mass parts of resin components in the said composition.
- fine-particles as a dispersion liquid it mix
- the coating composition of the present invention is provided with aluminum oxide, cerium oxide, titanium oxide, zinc oxide, oxidation for the purpose of imparting mechanical properties, imparting ultraviolet shielding properties, imparting electrical conductivity, etc.
- Metal oxide or metal composite oxide particles such as indium tin, zirconium oxide, tin oxide, iron oxide, and silicon oxide may be included.
- composite oxides containing at least one kind of silicon oxide, aluminum oxide, tin oxide, boron oxide and metal elements constituting them can be suitably used.
- Titanium oxide, zinc oxide, cerium oxide, or the like can be suitably used for imparting ultraviolet shielding properties.
- an indium oxide-tin oxide composite or the like can be suitably used.
- any kind of metal oxide or metal composite oxide may be used in combination.
- the compounding amount of these metal oxides is preferably 0.1 to 50 parts by mass, and preferably 1 to 20 parts by mass with respect to 100 parts by mass of the room temperature curable resin.
- a known antioxidant such as 2,6-di-t-butyl-4-methylphenol may be blended in order to suppress the occurrence of coloring, white turbidity, oxidative degradation, etc. of the coating composition of the present invention.
- an inorganic filler such as fumed silica may be blended in order to improve the coating strength within a range that does not affect the transparency of the cured coating obtained from the coating composition of the present invention.
- dyes, pigments, flame retardants, leveling agents and the like may be blended. These components may be used alone or in combination of two or more.
- the coating composition of the present invention can be prepared by mixing room temperature curable resin, core-shell fine particles, and additives used as necessary in any order.
- a coated article can be obtained by applying the coating composition of the present invention to the surface of a substrate and curing to form a coating layer.
- the coating layer may be formed on only one surface of the base material or on all surfaces.
- the coating layer is formed on at least one surface thereof. do it.
- a plastic molding, a wood-type product, ceramics, glass, a metal, those composites, etc. are mentioned.
- those whose surfaces of these base materials are treated, specifically, chemical conversion treatment, corona discharge treatment, plasma treatment, base materials treated with an acid or an alkali solution, and the types in which the surface layer is different from the base material body.
- a decorative plywood or the like covered with a paint can also be used.
- other functional layers include a primer layer, a rust prevention layer, a gas barrier layer, a waterproof layer, a heat ray shielding layer, and the like, and any one or more of these layers may be formed in advance on the substrate.
- the coated article has a hard coat layer, a rust preventive layer, a gas barrier layer, a waterproof layer, a heat ray shielding layer, an antifouling layer, a photocatalyst on the opposite side of the surface on which the coating film made of the coating composition is formed. It may be covered with one layer or a plurality of layers such as a layer and an antistatic layer.
- the coating method may be appropriately selected from known methods. For example, various coating methods such as brush coating, spraying, dipping, flow coating, roll coating, curtain coating, spin coating, and knife coating may be used. Can do.
- the coating composition of the present invention is a composition that can be cured at about 0 to 40 ° C., preferably about 5 to 35 ° C., but it is preferable that a cured film can be formed after 12 hours at 25 ° C. What can form a cured film within 5 hours is more preferable. In addition, you may heat in the temperature range which does not have a bad influence on a base material etc. in order to shorten hardening time.
- the thickness of the coating film (coating layer) is not particularly limited, but is preferably 0.1 to 100 ⁇ m, more preferably 1 to 50 ⁇ m. If it is this range, long-term stable adhesion and suppression of coating film cracks can be achieved.
- the coating film produced from the coating composition of the present invention is characterized by excellent weather resistance.
- the weather resistance can be evaluated by a change in the appearance of the coating film after the weather resistance test of the cured coating film.
- Iwasaki Electric Co., Ltd. Eye UV Ozone Decomposition Device (OCA-150L-D), Iwasaki Electric Co., Ltd. Eye Super UV Tester W-151, etc. are used to change the appearance of the coating film in the weather resistance test. It can be evaluated by measuring the change in the color difference ( ⁇ E * ) of the coating after irradiation with ultraviolet light for a certain period of time.
- the color difference can be measured using, for example, a chromaticity meter Z-300A (manufactured by Nippon Denshoku Industries Co., Ltd.).
- the color difference is preferably 10 or less, more preferably 5 or less, and even more preferably 2 or less. If it exceeds 10, the color change may show a level of color change that can be visually confirmed. Yellowing resistance can be measured by the yellow index of the coated article.
- an integrated ultraviolet energy of 1,500 MJ per 1 m 2 corresponds to about 10 years of outdoor exposure.
- the correlation between the test conditions and outdoor exposure can be easily estimated. For example, when the amount of outdoor ultraviolet rays is measured using an ultraviolet illuminance meter (IUV illuminance meter UVP365-1 manufactured by Iwasaki Electric Co., Ltd.), 1 ⁇ 10 1 It can be seen that it is W / m 2 (when measured at noon on an equinox on a sunny day in Matsuida-machi, Annaka-shi, Gunma Prefecture).
- titanium chloride (IV) aqueous solution product name: TC-36, manufactured by Ishihara Sangyo Co., Ltd., 66.0 g
- 50% stannic chloride (IV) solution product name: TC-36, manufactured by Ishihara Sangyo Co., Ltd., 66.0 g
- stannic chloride (IV) solution 50% stannic chloride (IV) solution
- II manganese monoxide
- 0.1 g was added and mixed well, and then diluted with 1000 g of ion-exchanged water.
- the molar ratio of Sn and Mn to Ti in this metal salt aqueous solution is 20 for [Ti / Sn] and 100 for [Ti / Mn].
- Precipitate of titanium hydroxide containing tin and manganese by gradually adding 300 g of 5% by mass of ammonia water (manufactured by Wako Pure Chemical Industries, Ltd.) to this metal salt aqueous solution mixture to neutralize and hydrolyze. Got. The pH of the titanium hydroxide slurry at this time was 8. The resulting precipitate of titanium hydroxide was deionized by repeatedly adding ion-exchanged water and decanting. 100 g of 30% by mass hydrogen peroxide water (manufactured by Wako Pure Chemical Industries, Ltd.) is gradually added to the titanium hydroxide precipitate containing tin and manganese after the deionization treatment, and then stirred at 60 ° C. for 3 hours. And fully reacted. Thereafter, ion-exchanged water was added to adjust the concentration, thereby obtaining a translucent tin and manganese-containing peroxotitanic acid solution (solid content concentration 1% by mass).
- the diluted colloidal solution was concentrated to 8.8% by mass by ultrafiltration to obtain an aqueous dispersion (TW-1) of core-shell fine particles.
- TW-1 D 50 was determined by a dynamic light scattering method (manufactured by Nikkiso Co., Ltd., apparatus name “Nanotrack”) to be 17.9 nm.
- the ratio of silicon oxide in the shell to the entire core-shell fine particles was 18.0% by mass in terms of SiO 2 .
- TE-1 titanium oxide fine particle ethanol dispersion
- the solid content concentration of TE-1 was 9.2% by mass, and the water concentration was 1.1% by mass.
- D 50 was determined to be 9.9 nm by the dynamic light scattering method (manufactured by Nikkiso Co., Ltd., apparatus name “Nanotrack”).
- 200 g of TE-1 was introduced into a distillation flask, and propylene glycol monomethyl ether (PGM, manufactured by Nippon Emulsifier Co., Ltd., 250 g) was added as an organic solvent while stirring with a magnetic stirrer (700 rpm). After the addition of the organic solvent, the reaction solution was uniform and transparent.
- PGM propylene glycol monomethyl ether
- the content was distilled off by heating under a pressure of 760 mmHg. Distillation occurred when the temperature inside the flask was about 85 ° C. Distillation was continued until the amount of distillation reached 315 g. The internal temperature at the end of the distillation was about 120 ° C.
- the resulting dispersion had a solid content concentration of 14.5% by mass and a water concentration of 0.12% by mass. Furthermore, dehydration was performed with molecular sieve 4A (manufactured by Kanto Chemical Co., Inc.) to obtain a core shell fine particle PGM dispersion (TPG-1).
- Example 1 Aqueous emulsion type coating composition (transparent aqueous versatile color, Co., Ltd.) comprising 1 g of an aqueous dispersion of core-shell fine particles obtained in Synthesis Example 1 (TW-1, solid concentration 8.8% by mass) and a silicone-modified acrylic resin And 10 g of Asahi Pen) were mixed to prepare a coating composition containing core-shell fine particles. It was confirmed that the core-shell fine particles were dispersed in the aqueous emulsion type coating composition without agglomeration.
- Example 2 Solvent-free coating composition (KR-400, Shin-Etsu Chemical Co., Ltd.) comprising 1 g of PGM dispersion of core-shell fine particles obtained in Synthesis Example 2 (TPG-1, solid content concentration 14.5 mass%) and silicone resin 10 g) was mixed to prepare a coating composition containing core-shell fine particles. It was confirmed that the core-shell fine particles were dispersed in KR-400 without aggregation.
- Example 3 10 g of an organic coating composition (oil-based varnish, manufactured by Wasin Paint Co., Ltd.) composed of 1 g of a PGM dispersion of core-shell fine particles obtained in Synthesis Example 2 (TPG-1, solid content concentration 14.5% by mass) and urethane resin And a coating composition containing core-shell fine particles was prepared. It was confirmed that the core-shell fine particles were dispersed in the organic coating composition made of urethane resin without agglomeration.
- an organic coating composition oil-based varnish, manufactured by Wasin Paint Co., Ltd.
- TPG-1 solid content concentration 14.5% by mass
- KR solventless coating composition
- any of the coating materials prepared in Examples 1 to 3 no aggregation or white turbidity of the core-shell fine particles was observed, and it was confirmed that they were uniformly dispersed in the coating material.
- Example 4 The coating composition prepared in Example 1 was applied to a quartz substrate using a bar coater # 8 and placed at 25 ° C. for 3 hours to obtain a cured film.
- the ultraviolet-visible light absorption spectrum of the obtained coating substrate is shown in FIG.
- Example 5 The coating composition prepared in Example 2 was applied to a quartz substrate using a bar coater # 8 and placed at 25 ° C. for 3 hours to obtain a cured film.
- the ultraviolet-visible light transmission spectrum of the obtained coating substrate is shown in FIG.
- Example 6 The coating composition prepared in Example 3 was applied to a quartz substrate using a bar coater # 8 and placed at 25 ° C. for 3 hours to obtain a cured film.
- the ultraviolet-visible light transmission spectrum of the obtained coating substrate is shown in FIG.
- Comparative Example 2 The coating composition prepared in Comparative Example 1 was applied to a quartz substrate using a bar coater # 8 and placed at 25 ° C. for 3 hours to obtain a cured film.
- the ultraviolet-visible light transmission spectrum of the obtained coating substrate is shown in FIG.
- the cured films (Examples 4 to 6) produced from the coating compositions of Examples 1 to 3 have both high visible light transparency and ultraviolet shielding properties.
- the cured film (comparative example 2) produced from the coating composition using the commercially available titanium oxide particle dispersion prepared in the comparative example 1 has a light transmittance in the visible light region. Is 80% or less, and the light transmittance in the ultraviolet region is not significantly changed as compared with the visible light region, indicating that the transparency is poor and that the ultraviolet shielding ability is hardly exhibited.
- the coating composition obtained by the present invention not only impairs the transparency of paints based on various organic resins, but also has a high ultraviolet shielding ability. Therefore, by using the coating composition obtained in the present invention, it is possible to suppress deterioration of the substrate material due to ultraviolet rays while maintaining the characteristics of the paint containing each base resin.
- Example 7 A red water-based acrylic paint made of an acrylic resin (Hapio Color, manufactured by Campehapio Co., Ltd.) was applied to a glass substrate with a brush and placed at 25 ° C. for 3 hours to obtain a cured film.
- the coating composition prepared in Example 2 was applied onto the obtained cured film using a bar coater # 8 and placed at 25 ° C. for 3 hours to obtain a cured film.
- Example 7 and Comparative Example 3 were irradiated with ultraviolet rays for 3 hours using an ozone decomposing apparatus (IUV UV decomposing apparatus OCA-150L-D manufactured by Iwasaki Electric Co., Ltd.), and a color difference meter was used.
- the coating deterioration was evaluated by reflected light measurement. Specifically, the difference in lightness index ( ⁇ L * ), the difference in chromaticness index ( ⁇ a * , ⁇ b * ), and the L * a * b * color difference ( ⁇ E * ) before and after UV irradiation by an ozonolysis apparatus are expressed as color. It was determined by measuring reflected light using a meter. The results are shown in Table 1.
- the cured film produced in Example 7 has a smaller color difference before and after UV irradiation than Comparative Example 3.
- This result shows that the core-shell fine particles having tetragonal titanium oxide solid solution fine particles in which tin and manganese are solid-solved of the present invention as the core and the silicon oxide shells outside the core absorb the ultraviolet rays, and the base coating is irradiated with ultraviolet rays. It shows that the deterioration of the base paint is suppressed by being inhibited.
- Example 8 Solvent-free coating composition (KR-400, Shin-Etsu Chemical Co., Ltd.) comprising 5 g of PGM dispersion (TPG-1, solid content concentration 14.5% by mass) of core-shell fine particles obtained in Synthesis Example 2 and silicone resin (Manufactured) was mixed with 10 g to prepare a coating composition containing titanium oxide.
- the prepared coating composition was applied to a polycarbonate substrate (PC-1600, manufactured by Takiron Co., Ltd.) using a bar coater # 8 and placed at 25 ° C. for 3 hours to obtain a cured film.
- PC-1600 manufactured by Takiron Co., Ltd.
- Example 9 10 g of an organic coating composition (oil-based varnish, manufactured by Wasin Paint Co., Ltd.) comprising 5 g of PGM dispersion (TPG-1, solid content concentration 14.5 mass%) of core-shell fine particles obtained in Synthesis Example 2 and urethane resin And a coating composition containing titanium oxide was prepared.
- the prepared coating composition was applied to a polycarbonate substrate (PC-1600, manufactured by Takiron Co., Ltd.) using a bar coater # 8 and placed at 25 ° C. for 3 hours to obtain a cured film.
- PC-1600 manufactured by Takiron Co., Ltd.
- Solvent-free coating composition comprising 1 g of a 4% by weight PGM solution of 2- (2,4-dihydroxyphenol) 4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and a silicone resin ( KR-400 (manufactured by Shin-Etsu Chemical Co., Ltd.) 10 g was mixed to prepare a coating composition containing phenyltriazine as an organic ultraviolet absorber. The obtained coating composition was applied to a polycarbonate substrate (PC-1600, manufactured by Takiron Co., Ltd.) using a bar coater # 8 and placed at 25 ° C. for 3 hours to obtain a cured film.
- PC-1600 polycarbonate substrate
- bar coater # 8 placed at 25 ° C. for 3 hours to obtain a cured film.
- the substrates of Examples 8 and 9 having a cured film prepared from a coating composition containing core-shell fine particles are comparative examples having a cured film prepared from a coating composition into which core-shell fine particles are not introduced.
- the difference in yellow index before and after UV irradiation is small, indicating that yellowing of the polycarbonate due to UV is suppressed.
- This result shows that the core-shell fine particles having tetragonal titanium oxide solid solution fine particles in which tin and manganese are solid-solved of the present invention as a nucleus and having a silicon oxide shell on the outer side of the nucleus absorb the ultraviolet rays, and the ultraviolet rays to the polycarbonate substrate are obtained.
Abstract
Description
このような問題を解決する手段として、材料表面に紫外線吸収剤を含んだコーティングを施すことによって、紫外線による材料劣化を抑制することが従来広く行われている。
しかし、フェニルトリアジン型紫外線吸収剤は、有機化合物であるため、長期間紫外線に曝されることでフェニルトリアジン自体が劣化して紫外線吸収能が大きく低下し、変色するという問題があった。
しかし、これらの技術では、十分な紫外線遮蔽能を塗膜に付与するためには酸化亜鉛の配合量を多くする必要があり、結果として保存安定性や屋外暴露時の白化といった問題が生じていた。
一方、酸化チタンは、酸化亜鉛よりも大きな吸光係数を有するため、酸化亜鉛で発生する問題を解決できる可能性があるものの、酸化チタンを塗料組成物に安定かつ透明に分散させることは困難であった。
しかも、酸化チタンは、強い光触媒活性を有するため、塗料組成物に配合した場合にクラッキング作用およびチョーキング作用を示し、耐候性を示すとは考えられてこなかった。
しかし、二酸化マンガンは、酸化剤として作用することが知られており、上記粒子を含んだコーティング組成物では、組成物中に含まれる合成樹脂等の有機化合物が酸化され、塗膜を劣化させる可能性がある。
また、一般に市販されている酸化チタン微粒子を室温硬化性塗料に導入した場合、粒子が凝集・白濁を引き起こし、透明性や紫外光吸収能が大きく低下することが問題となっている。
このように、硬化塗膜が透明性を維持しながら紫外線遮蔽性を発現し、かつ、長期の屋外暴露から基材を保護する特性を兼ね備えた室温硬化性のコーティング組成物は存在していない。
1. (A)室温硬化性樹脂:100質量部、ならびに
(B)スズおよびマンガンを固溶した正方晶系酸化チタン固溶体微粒子を核とし、この核の外側に酸化ケイ素の殻を有するコアシェル微粒子:0.1~50質量部
を含むことを特徴とするコーティング組成物、
2. 前記コアシェル微粒子の、動的光散乱法で測定した体積基準の粒度分布における50%累積径が1~50nmである1のコーティング組成物、
3. 前記室温硬化性樹脂が、アクリル樹脂、ポリエステル樹脂、シリコーン変性ポリエステル樹脂、シリコーン変性アクリル樹脂、エポキシ樹脂、ポリカーボネート樹脂、シリコーン樹脂、フッ素樹脂、塩素系樹脂、ポリオレフィン樹脂、ウレタン樹脂、およびアクリルウレタン樹脂からなる群より選ばれる1種または2種以上の樹脂を含む1または2のコーティング組成物、
4. さらに、酸化アルミニウム、酸化セリウム、酸化亜鉛、酸化インジウムスズ、酸化ジルコニウム、酸化スズ、酸化鉄、酸化ケイ素、および酸化チタン(ただし、前記(B)のコアシェル微粒子は除く)からなる群より選ばれる1種または2種以上を含む1~3のいずれかのコーティング組成物、
5. 前記コアシェル微粒子表面の酸化ケイ素の殻が、シロキサン結合を介したオルガノシリル基を有している1~4のいずれかのコーティング組成物、
6. 1~5のいずれかのコーティング組成物が硬化してなる硬化膜、
7. 1~5のいずれかのコーティング組成物が硬化してなる硬化膜を有する被覆物品、
8. 基材と、この基材の少なくとも一方の面に積層された、1~5のいずれかのコーティング組成物が硬化してなる硬化膜とを有する被覆物品
を提供する。
このような特性を有する本発明のコーティング組成物は、建築物等の外装材、内装材等の様々な材料に適応可能な室温硬化型の紫外線遮蔽性クリアコーティング剤として好適であり、本発明の組成物を用いることで、基材の外観や特性を長期に亘って維持することができる。
本発明に係るコーティング組成物は(A)室温硬化性樹脂:100質量部、ならびに(B)スズおよびマンガンを固溶した正方晶系酸化チタン固溶体微粒子を核とし、この核の外側に酸化ケイ素の殻を有するコアシェル微粒子:0.1~50質量部を含むことを特徴とする。
なお、本発明において、塗装した被膜を硬化する際の「室温」とは、通常0~40℃を意味し、好適には5~35℃の温度範囲を意味する。
本発明のコーティング組成物に用いられる室温硬化性樹脂の具体例としては、アクリル樹脂、ポリエステル樹脂、シリコーン変性ポリエステル樹脂、シリコーン変性アクリル樹脂、エポキシ樹脂、ポリカーボネート樹脂、シリコーン樹脂、フッ素樹脂、塩素系樹脂、ポリオレフィン樹脂、ウレタン樹脂、およびアクリルウレタン樹脂からなる群より選ばれる1種または2種以上の樹脂成分を含有する透明塗料組成物が挙げられ、これらの中から、塗布対象である基材との親和性の高い樹脂を適宜選択することで、塗膜に基材との高い密着性を付与することができる。
なお、これらの塗料中には、溶媒として水や有機系溶剤が含まれていてもよく、有効成分である樹脂成分が、溶剤とのエマルジョンとして存在していても、溶剤中に均一に溶解した状態で存在していてもよい。
本発明のコーティング組成物に用いられるコアシェル微粒子は、上述のとおり、スズおよびマンガンを固溶した正方晶系酸化チタン固溶体微粒子を核とし、核の外側に酸化ケイ素の殻を有する。
酸化チタンには、通常、ルチル型、アナターゼ型、ブルッカイト型の3つがあるが、本発明では、光触媒活性が低く、紫外線吸収能力に優れた正方晶系ルチル型の酸化チタンをスズおよびマンガンの固溶媒として用いる。
スズ塩としては、フッ化スズ、塩化スズ、臭化スズ、ヨウ化スズ等のスズハロゲン化物;シアン化スズ、イソチオシアン化スズ等のスズ擬ハロゲン化物;硝酸スズ、硫酸スズ、燐酸スズ等のスズ鉱酸塩などが挙げられるが、安定性と入手の容易さから塩化スズが好適である。
なお、スズ塩におけるスズの原子価は2価から4価のいずれも選択できるが、4価が好ましい。
固溶質としてのマンガン成分は、マンガン塩から誘導されるものであればよく、その具体例としては、酸化マンガン、硫化マンガン等のマンガンカルコゲナイドが挙げられ、これらの中でも酸化マンガンが好ましい。
マンガン塩としては、フッ化マンガン、塩化マンガン、臭化マンガン、ヨウ化マンガン等のマンガンハロゲン化物;シアン化マンガン、イソチオシアン化マンガン等のマンガン擬ハロゲン化物;硝酸マンガン、硫酸マンガン、燐酸マンガン等のマンガン鉱酸塩等が挙げられるが、安定性と入手の容易さから、塩化マンガンが好適である。
なお、マンガン塩におけるマンガンの原子価は2価から7価のいずれも選択できるが、2価が好ましい。
一方、マンガン成分の固溶量は、チタンとのモル比(Ti/Mn)で10~1,000が好ましく、20~200がより好ましい。
スズ成分、マンガン成分の固溶量が、チタンとのモル比(Ti/Sn)、(Ti/Mn)で10未満であると、スズおよびマンガンに由来する可視領域の光吸収が顕著となる場合があり、一方、1,000を超えると、光触媒活性が十分に失活せず、結晶系も紫外線吸収能の小さいアナターゼ型となる場合がある。
ここで、置換型とは、酸化チタンのチタン(IV)イオンのサイトにスズおよびマンガンが置換されて形成される固溶様式のことであり、侵入型とは、酸化チタンの結晶格子間にスズおよびマンガンが存在することにより形成される固溶様式のことである。
侵入型では、着色の原因となるF中心が形成され易く、また金属イオン周囲の対称性が悪いため金属イオンにおける振電遷移のフランク-コンドン因子も増大し、可視光を吸収し易くなることから、置換型が好ましい。
このような酸化ケイ素の殻の形成手法は任意であり、例えば、有機ケイ素化合物または無機ケイ素化合物を酸化チタン微粒子の表面に反応させて形成できる。
テトラアルコキシシランの具体例としては、テトラメトキシシラン、テトラエトキシシラン、テトラ(n-プロポキシ)シラン、テトラ(i-プロポキシ)シラン、テトラ(n-ブトキシ)シラン等の通常入手可能なものが挙げられるが、反応性と安全性の観点からテトラエトキシシランが好ましい。
テトラアルコキシシランは、市販品を用いてもよく、その具体例としては、テトラエトキシシランであるKBE-04(信越化学工業(株)製)等が挙げられる。
テトラアルコキシシランの加水分解縮合は、アンモニア、アルミニウム塩、有機アルミニウム、スズ塩、有機スズ等の縮合触媒を適宜用いて水中で行うことができる。これらの縮合触媒の中でもアンモニアは、核微粒子の分散剤としての作用も兼ね備えていることから、好適に用いることができる。
ケイ酸アルカリの具体例としては、ケイ酸ナトリウム、ケイ酸カリウム等の通常入手可能なものが挙げられる。
ケイ酸アルカリは、市販品を用いてもよく、その具体例としては、「珪酸ソーダ」(富士化学(株)製)等が挙げられる。
ケイ酸アルカリ水溶液の原料としては、上述した各種ケイ酸アルカリが挙げられ、この場合も、市販の「珪酸ソーダ」(富士化学(株)製)を用いることができる。
陽イオン交換樹脂としても、通常入手可能なものから適宜選択して用いればよく、その具体例としては、「アンバージェット1024H」(オルガノ(株)製)等が挙げられる。
ケイ酸アルカリ水溶液とカチオン交換樹脂の接触方法としては、例えば、水で希釈したケイ酸アルカリ水溶液に対し、強酸性陽イオン交換樹脂(H+型)を添加する方法や、強酸性陽イオン交換樹脂(H+型)を詰めたイオン交換樹脂塔に水で希釈したケイ酸アルカリ水溶液を流す方法などが挙げられる。
この際、ケイ酸アルカリ水溶液の濃度は、特に限定されるものではないが、生産効率や、得られた活性ケイ酸のゲル化防止等の観点から、シリカ換算濃度で1~10質量%が好ましく、1~5質量%がより好ましく、2~4質量%がより一層好ましい。
なお、カチオン交換処理は、得られる活性ケイ酸溶液のpHが1~5となるように行うことが好ましく、2~4となるように行うことがより好ましい。
ケイ酸アルカリまたは活性ケイ酸と、酸化チタン微粒子との混合方法は特に限定されないが、例えば、酸化チタン微粒子の分散液にケイ酸アルカリまたは活性ケイ酸の水溶液を徐々に添加する方法が挙げられる。
本発明では、レーザー光による動的光散乱法で測定した体積基準の粒度分布における50%累積径(D50)を用いるが、傍証として電子顕微鏡法を用いて観測することも可能である。これらの測定法によって求められる値は、測定装置に依存したものではないが、例えば、動的光散乱法としては、ナノトラックUPA-EX150(日機装(株)製)等の装置を用いることができる。また、電子顕微鏡法としては透過型電子顕微鏡H-9500(日立ハイテクノロジーズ(株)製)を装置として例示することができる。
本発明のコーティング組成物の硬化膜は、可視領域における透明性が重要であるため、コアシェル微粒子のD50は、1~200nmが好ましく、1~100nmがより好ましく、1~80nmがより一層好ましく、1~50nmがさらに好ましい。コアシェル微粒子の平均累計粒子径が200nmを超えると、可視領域の光波長より大きくなり、散乱が顕著となる場合がある。また、1nm未満になると、コアシェル微粒子の系中での総表面積が極めて大きくなることにより、粒子としての取り扱いが困難になる場合がある。
このオルガノシリル基は、例えば、下記一般式(I)で表されるシラン化合物、同シラン化合物の(共)加水分解縮合物、またはそれらの混合物によりコアシェル粒子表面を修飾することで導入可能である。
R1 mSi(Y)4-m (I)
(式中、R1は、それぞれ同一または異なっていてもよく、(メタ)アクリル基、オキシラニル基、アミノ基、メルカプト基、イソシアネート基もしくはフッ素原子で置換されていてもよい炭素数1~20のアルキル基、炭素数2~20のアルケニル基、炭素数6~20のアリール基、およびケイ素数50以下の(ポリ)ジメチルシロキシ基からなる群から選ばれる置換基、または水素原子を表し、Yは、アルコキシ基、アセトキシ基、エノール基、ヒドロキシル基、および塩素原子からなる群から選ばれる置換基を表し、mは、1~3の整数である。)
アルケニル基としては、炭素数2~6のアルケニル基が好ましく、ビニル基、アリル基がより好ましい。
アリール基としては、炭素数6~10のアリール基が好ましく、フェニル基がより好ましい。
(ポリ)ジメチルシロキシ基のケイ素数は、1~50が好ましく、1~30がより好ましい。
アルコキシ基としては、メトキシ基、エトキシ基、n-プロポキシ基、n-ブトキシ基等が挙げられ、メトキシ基が好ましい。
一般式(II)において、nは0~50の整数が好ましく、5~40の整数がより好ましく、10~30の整数がより一層好ましい。nが50より大きくなると、シリコーンオイルとしての性質が強くなり、表面処理されたオルガノゾルの各種樹脂への溶解性が限定される場合がある。下記一般式(II)中において、平均構造がn=30の化合物は、商品名「X-24-9822」(信越化学工業(株)製)として入手することができる。
シラン化合物の使用量は、コアシェル微粒子の質量に対し、0.5~50倍が好ましく、1~25倍がより好ましく、2~10倍がより一層好ましい。上記使用量が50倍よりも多いと、ゲル化する場合があり、一方、0.5倍よりも少ないと、被覆が不十分となる結果、凝集する場合がある。
コロイド分散液の分散質濃度は、製造効率を高めるとともに、ゲル化を防止するという点から、1~35質量%が好ましく、5~30質量%がより好ましく、10~25質量%がより一層好ましい。
分散媒には、水分散コロイド溶液を製造する工程で水と任意に混和可能な1価のアルコールを含んでいてもよい。水と任意に混和可能な1価のアルコールは、コアシェル微粒子を製造する際の共溶媒およびゾル-ゲル反応における金属アルコキシドの加水分解副生成物由来のものでもよい。
水と任意に混和可能な1価のアルコールとしては、メタノール、エタノール、1-プロパノール、2-プロパノール等が挙げられる。
希釈用溶剤の具体例としては、メタノール、エタノール、1-プロパノール、2-プロパノール、1-ブタノール等の1価アルコール類;エチレングリコール、プロピレングリコール、グリセリン等の多価アルコール類;プロピレングリコールモノメチルエーテル、エチレングリコールモノメチルエーテル、グリム、ジグリム等のエーテル類;アセトン、メチルイソブチルケトン等のケトン類;酢酸エチル、プロピレングリコールモノメチルエーテルアセテート等のエステル類;ヘキサンジオールジアクリレート、トリメチロールプロパントリアクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールヘキサアクリレート等の反応性エステル類などが挙げられ、これらの中でも、エタノール、2-プロパノールが好ましい。
シラン化合物添加時の温度は、コロイド水分散液の変質およびシラン化合物の予期せぬ加水分解縮合を防止する観点から、0~45℃が好ましく、5~40℃がより好ましく、10~35℃がより一層好ましい。なお、加水分解縮合による反応熱によって、反応液の温度が70℃未満程度まで上昇することがある。
塩基触媒の具体例としては、水酸化カリウム、水酸化ナトリウム、炭酸カリウム、炭酸ナトリウムや塩基性イオン交換樹脂等が挙げられる。
酸触媒の具体例としては、塩酸、硫酸、メタンスルホン酸、トリフルオロメタンスルホン酸、酢酸、カチオン性イオン交換樹脂等が挙げられる。
カチオン性イオン交換樹脂の具体例としては、アンバーライト(オルガノ社製)、レバチット(ランクセス社製)、ピューロライト(ピューロライト社製)、ムロマック(室町ケミカル(株)製)等が挙げられる。
これらの触媒の使用量は、反応速度を適切にコントロールするという点から、コアシェル微粒子に対して、0.01~20質量%が好ましく、0.1~10質量%がより好ましく、1~5質量%がより一層好ましい。
オルガノシリル基の導入量は、オルガノシリル基との反応前のコアシェル微粒子の質量減少率とオルガノシリル基を有する表面処理微粒子の質量減少率の差から見積もることができ、その導入量は、表面処理微粒子の2質量%以上であることが、有機溶媒への分散性付与の点から望ましい。
分散媒には、水分散コロイド溶液に含まれる水、添加したケイ素化合物やケイ素化合物の加水分解縮合物が加水分解縮合することで生成した珪酸エステルに由来するアルコール類、必要に応じて添加した1価アルコールやその他の有機溶剤類が含まれる。
より具体的には、好ましくは平均細孔径5nm以上20nm未満、より好ましくは平均細孔径6~18nm、より一層好ましくは平均細孔径7nmの無機セラミック製の膜を備えたろ板を用いることが好ましく、その形状は、回転可能な円盤状であることが好ましい。
合成条件、スピネルの結晶成長を制御することによって細孔径を制御することが好ましい。
アルミナ製等の多孔性円盤状素焼き板としては、細孔径0.05~1μmのものを用いることが好ましい。
表面層の平均細孔径は、5nm以上20nm未満が好ましく、6~18nmがより好ましく、7nmがより一層好ましい。この細孔径は、電子顕微鏡法によって求めることが好ましい。このような目的に利用できる電子顕微鏡としては、走査型電子顕微鏡、透過型電子顕微鏡、原子間力顕微鏡等が挙げられる。
ろ板の厚さは、機械的強度を確保するとともに、ろ過室の容積を確保することを考慮すると、1mm以上10mm未満が好ましく、3~5mmがより好ましい。
このようなフィルターは公知の手法によって製造してもよく、また市販のものを用いてもよい。
静圧力は、表面が大気に接触した形の水頭管、または閉鎖系における油圧および圧縮空気圧によって付与することが好ましく、特に装置をコンパクトにできることから、圧縮空気圧によって付与することが好ましい。圧縮空気は、公知の手法、または市販のコンプレッサーを利用して容易に作り出すことができる。
剪断応力は、ろ室内の壁間距離と回転速度から計算することができる。なお、ろ室内の壁間距離を小さくする目的で、ろ室内には必要に応じて適切なバッフル(邪魔板)を設けることができる。回転およびバッフルによって剪断応力を高めることは公知の手段である。
円周上に働く最大の剪断応力(τ)は、円盤状ろ板の直径を(φ[m])、ろ板の回転速度を(ω[rps])、ろ板とろ過室の壁間距離を(L[m])、円周率を(π)、分散液の粘度を(η[Pa・s])とした場合に、一例として数式(1)のように計算することができる。
τ=(η・π・φ・ω)/L [Pa] …… 数式(1)
例えば、直径φ=0.15[m]、ろ板の回転速度ω=16.7[rps](≒1,000[rpm])、円周率π=3.14、分散液の粘度η=0.001[Pa・s]、壁間距離L=0.003[m]とした場合のτ=(0.001×3.14×0.15×16.7)/0.003≒2.6[Pa]である。剪断応力は、上記好ましい範囲になるように、φ・ω・Lのそれぞれのパラメーターを変化させることで与えることができる。
流体の状態は、レイノルズ数によって規定できる。撹拌レイノルズ数は、層流撹拌を防いで分散効率を高めるとともに、撹拌に要するエネルギーを適切な範囲として生産性を高めることなどを考慮すると、3,000~5,000,000が好ましく、5,000~1,000,000がより好ましく、10,000~500,000がより一層好ましい。
このレイノルズ数(Re)は、数式(2)から求めることができる。数式(2)においてρは密度(kg/m3)、ωは回転数(rps)、φはろ板直径(m)、ηは粘度(Pa・s)をそれぞれ表す。
Re=ρ・ω・φ2/η …… 数式(2)
例えば、0.15(m)の円盤状ろ板を16.7(rps)でρが1,000(kg/m3)、ηが0.001(Pa・s)のコアシェル微粒子分散液を処理した場合のReは約3.8×105である。ωとφを適宜選択することによって上記所望のReの範囲となるように調節することができる。
なお、撹拌効率の向上を図る目的で、バッフルを設置した反応器を用いてもよい。
分散液の粘度は、一般に温度に依存し、粘度は回転トルクに影響を与えるため、電磁回転機や発動機に負荷がかかりすぎないように、温度を調整することが好ましい。
分散媒を置換する際には、連続した限外ろ過によって、必要に応じて未反応化合物や副生成物を除去することもできる。
これらの中でも、コアシェル微粒子の分散性や分散媒留去の容易さから、メタノール、エタノール、1-プロパノール、2-プロパノール、プロピレングリコールモノメチルエーテル等が好適である。
本発明のコーティング組成物は、上述した室温硬化性樹脂およびコアシェル微粒子を含むものである。
コーティング組成物における上記コアシェル微粒子の配合量は、得られる硬化膜の紫外線吸収能および微粒子の分散性等を考慮して室温硬化性樹脂100質量部に対し、0.1~50質量部であるが、1~20質量部が好ましい。
なお、室温硬化性樹脂が溶剤を含む組成物である場合、コアシェル微粒子の配合量は、当該組成物中の樹脂成分100質量部を基準として決定する。
また、コアシェル微粒子を分散液として用いる場合は、その固形分量が、室温硬化性樹脂100質量部に対し、上記範囲となるように配合する。
機械的特性の付与のためには、酸化ケイ素、酸化アルミニウム、酸化スズ、酸化ホウ素およびこれらを構成する金属元素を1種類以上含有する複合酸化物が好適に使用できる。
紫外線遮蔽特性の付与のためには、酸化チタン、酸化亜鉛、酸化セリウム等が好適に使用できる。
電気伝導性の付与のためには、酸化インジウム-酸化スズ複合体等が好適に使用できる。
なお、これらの特性の2つ以上を付与するため、任意の種類の金属酸化物または金属複合酸化物を併用してもよい。
これらの金属酸化物の配合量は、室温硬化性樹脂100質量部に対し、0.1~50質量部が好ましく、1~20質量部が好ましい。
さらに、本発明のコーティング組成物から得られる硬化塗膜の透明性に影響を与えない範囲で、塗膜強度を向上させるためにヒュームドシリカ等の無機質充填剤を配合してもよく、必要に応じて、染料、顔料、難燃剤、レべリング剤等を配合してもよい。
これらの成分は、それぞれ単独で用いても2種以上を併用してもよい。
この際、上記被覆層は、基材の1つの面のみに形成しても、全ての面に形成してもよく、例えば、板状基材では、その少なくとも一方の面に、被覆層を形成すればよい。
基材としては、特に限定されることはないが、プラスチック成形体、木材系製品、セラミックス、ガラス、金属、およびそれらの複合物等が挙げられる。
さらに、これらの基材の表面が処理されたもの、具体的には、化成処理、コロナ放電処理、プラズマ処理、酸やアルカリ液で処理されている基材や、基材本体と表層が異なる種類の塗料で被覆されている化粧合板等も用いることもできる。
その他の機能層としては、プライマー層、防錆層、ガスバリア層、防水層、熱線遮蔽層等が挙げられ、これらのいずれか一層または複数層が基材上に予め形成されていてもよい。
なお、被覆物品は、上記コーティング組成物からなる塗膜が形成された面とは反対側の面が、ハードコート層、防錆層、ガスバリア層、防水層、熱線遮蔽層、防汚層、光触媒層、帯電防止層等の1層または複数層によって被覆されていてもよい。
本発明のコーティング組成物は、0~40℃程度、好ましくは5~35℃程度で硬化可能な組成物であるが、25℃で12時間後に硬化被膜を形成し得ることが好ましく、同温度で5時間以内に硬化被膜を形成し得るものがより好ましい。
なお、硬化時間を短縮する目的で、基材等に悪影響を及ぼさない温度範囲で加熱してもよい。
耐候性は、硬化塗膜の耐候性試験後における、塗膜の外観の変化で評価できる。
耐候性試験での塗膜の外観の変化は、例えば、岩崎電気(株)製アイUVオゾン分解装置(OCA-150L-D)や岩崎電気(株)製アイスーパーUVテスターW-151等を使用し、紫外光を一定時間照射した後の、被膜の色差(ΔE*)の変化を測定することで評価できる。
色差は、例えば、色度計Z-300A(日本電色工業(株)製)を用いて測定できる。色差は、10以下が好ましく、5以下がより好ましく、2以下がより一層好ましい。10を超える場合は、色の変化が目視で確認できるレベルの変色を示すことがある。
耐黄変性は、被覆物品のイエローインデックスでその尺度を計ることができる。例えば、色度計Z-300A(日本電色工業(株)製)を用いて測定した、初期のイエローインデックスをYI0、試験後のイエローインデックスをYI1としたときに、耐候イエローインデックスの差(ΔYI’=YI1-YI0)を求め、耐黄変性の指標とすることができる。耐候イエローインデックスの差(ΔYI’=YI1-YI0)は、10以下が好ましく、8以下がより好ましく、5以下がより一層好ましい。10を超える場合は、黄変が進行し、基材の劣化および意匠性の悪化が顕著となることがある。
試験条件と屋外暴露との相関は容易に見積もることができ、例えば、紫外線照度計(岩崎電気(株)製アイ紫外線照度計UVP365-1)を用いて屋外の紫外線量を測定すると1×101W/m2であることわかる(群馬県安中市松井田町において晴天時の春分の日の正午に測定した場合)。年間を通して一日の平均日照時間を12時間であると仮定すれば、12(h/日)×365(日/年)×10(年)×10(W/m2)=438(kWh/m2)≒1,500(MJ/m2)となる。
屋外の環境は、緯度や気候にも依存し、耐候性試験が人工的な環境であることを考慮すると、概算で1,500MJを10年の屋外暴露に相当すると考えるのが妥当である。試験条件は、硬化塗膜の使用環境に応じて適宜変更すればよい。
[合成例1]コアシェル微粒子水分散液(TW-1)の調製
無機酸化物コロイド水分散液として、スズおよびマンガンを固溶した正方晶系酸化チタン微粒子を核とし、酸化ケイ素を殻とするコアシェル微粒子を分散質とし、水を分散媒とするものを調製した。
まず、核微粒子を含有する分散液を製造し、次いで、テトラエトキシシランを加水分解縮合することで、コアシェル微粒子を含有するコロイド溶液とした。
36質量%の塩化チタン(IV)水溶液(石原産業(株)製、製品名:TC-36)66.0gに、50%塩化第二スズ(IV)溶液(日本化学産業(株)製)3.3g、一酸化マンガン(II)((株)高純度化学研究所製)0.1gを添加し、良く混合した後、これをイオン交換水1000gで希釈した。この金属塩水溶液中のTiに対するSnおよびMnのモル比は[Ti/Sn]が20、[Ti/Mn]が100である。
この金属塩水溶液混合物に、5質量%のアンモニア水(和光純薬工業(株)製)300gを徐々に添加して中和、加水分解することによりスズおよびマンガンを含有する水酸化チタンの沈殿物を得た。このときの水酸化チタンスラリーのpHは8であった。
得られた水酸化チタンの沈殿物を、イオン交換水の添加とデカンテーションを繰り返して脱イオン処理した。この脱イオン処理後のスズおよびマンガンを含有する水酸化チタン沈殿物に30質量%過酸化水素水(和光純薬工業(株)製)100gを徐々に添加し、その後60℃で3時間撹拌して十分に反応させた。その後、イオン交換水を添加して濃度調整を行うことにより、半透明のスズおよびマンガン含有ペルオキソチタン酸溶液(固形分濃度1質量%)を得た。
磁気回転子と温度計を備えたセパラブルフラスコに、酸化チタン分散液(i)1,000質量部、エタノール100質量部、アンモニア2.0質量部を室温(25℃)で加えて磁気撹拌した。このセパラブルフラスコを氷浴に浸漬し、内容物温度が5℃になるまで冷却した。ここに、テトラエトキシシラン18質量部(信越化学工業(株)製、商品名「KBE-04」)を加えた後に、セパラブルフラスコをμReactorEx(四国計測工業(株)製)内に設置して、周波数2.45GHz・出力1,000Wのマイクロ波を1分間にわたって照射しながら磁気撹拌した。その間、温度計を観測して内容物温度が85℃に達するのを確認した。得られた混合物を定性ろ紙(Advantec 2B)でろ過して希薄コロイド溶液を得た。この希薄コロイド溶液を限外ろ過によって8.8質量%まで濃縮し、コアシェル微粒子の水分散液(TW-1)を得た。TW-1について、動的光散乱法(日機装(株)製、装置名「ナノトラック」)によってD50を求めたところ、17.9nmであった。また、コアシェル微粒子全体に対する殻の酸化ケイ素の割合はSiO2換算で18.0質量%であった。
ジムロート冷却管、窒素導入管、温度計、および機械撹拌羽を備えた4つ口2Lセパラブルフラスコに、合成例1で得られたコアシェル微粒子の水分散液(TW-1、300g、固形分濃度8.8質量%)および触媒としてスルホン酸系カチオン性イオン交換樹脂3gを入れた。ここにメチルトリメトキシシラン(信越化学工業(株)製、製品名「KBM-13」、225g)を入れて激しく撹拌(250rpm)した。撹拌によって分散液とアルコキシシランが反応し、均一になる様子が観測された。その際、分散液の温度が25℃から52℃まで上昇する様子が観測された。
分散液の温度が50℃になるように2時間加熱撹拌した後、分散液にエタノール(750g)を撹拌(250rpm)しながら添加して希釈した。希釈分散液を限外ろ過機に導入し、滲出液を800g分取した。濃縮された分散液に対して、継続して有機溶剤(エタノール)を加圧供給したところ、分散液が滲出する様子が観測された。フィルター排出口に受器(5,000mL)を設け、滲出液が800gに達するまでエタノールの加圧供給を行った。ろ過室から分散液を取り出し、酸化チタン微粒子エタノール分散液(TE-1)を得た。TE-1の固形分濃度は9.2質量%、水分濃度1.1質量%であった。TE-1について、動的光散乱法(日機装株式会社製、装置名「ナノトラック」)によってD50を求めたところ、9.9nmであった。
TE-1を蒸留用フラスコに200g導入し、磁気撹拌子で撹拌(700rpm)しながら、有機溶媒としてプロピレングリコールモノメチルエーテル(PGM、日本乳化剤(株)製、250g)を添加した。有機溶媒添加後、反応液は均一で透明な状態を呈した。続いて、内容物を760mmHgの圧力下において加熱留去した。フラスコ内温が約85℃の時点で留去が起こった。留出量が315gに達するまで留去を続けた。留去終了時の内温は約120℃であった。得られた分散液の固形分濃度は14.5質量%、水分濃度0.12質量%であった。さらに、モレキュラーシーブ4A(関東化学(株)製)によって脱水を行い、コアシェル微粒子のPGM分散液(TPG-1)を得た。
[実施例1]
合成例1で得られたコアシェル微粒子の水分散液(TW-1、固形分濃度8.8質量%)1gとシリコーン変性アクリル樹脂からなる水性エマルジョン型コーティング組成物(透明水性多用途カラー、(株)アサヒペン製)10gとを混合し、コアシェル微粒子を含むコーティング組成物を調製した。コアシェル微粒子は水性エマルジョン型コーティング組成物中に凝集することなく分散することが確認された。
合成例2で得られたコアシェル微粒子のPGM分散液(TPG-1、固形分濃度14.5質量%)1gとシリコーン樹脂からなる無溶剤型コーティング組成物(KR-400、信越化学工業(株)製)10gとを混合し、コアシェル微粒子を含むコーティング組成物を調製した。コアシェル微粒子はKR-400中に凝集することなく分散することが確認された。
合成例2で得られたコアシェル微粒子のPGM分散液(TPG-1、固形分濃度14.5質量%)1gとウレタン樹脂からなる有機系コーティング組成物(油性ニス、和信ペイント(株)製)10gとを混合し、コアシェル微粒子を含むコーティング組成物を調製した。コアシェル微粒子はウレタン樹脂からなる有機系コーティング組成物中に凝集することなく分散することが確認された。
酸化チタン分散液(Hombitec RM223LP、ザハトレーベン社製、D50=22nm、分散媒:ジプロピレングリコールメチルエーテル、固形分濃度42質量%)0.12gと、シリコーン樹脂からなる無溶剤型コーティング組成物(KR-400、信越化学工業(株)社製)5gとを混合し、酸化チタンを含むコーティング組成物を調製した。酸化チタンのシリコーン樹脂中における凝集に起因した白濁が確認された。
[実施例4]
実施例1で調製したコーティング組成物を石英基板にバーコーター#8を用いて塗布し、25℃で3時間置くことで硬化被膜を得た。得られたコーティング基板の紫外可視光吸収スペクトルを図1に示した。
実施例2で調製したコーティング組成物を石英基板にバーコーター#8を用いて塗布し、25℃で3時間置くことで硬化被膜を得た。得られたコーティング基板の紫外可視光透過スペクトルを図2に示した。
実施例3で調製したコーティング組成物を石英基板にバーコーター#8を用いて塗布し、25℃で3時間置くことで硬化被膜を得た。得られたコーティング基板の紫外可視光透過スペクトルを図3に示した。
比較例1で調製したコーティング組成物を石英基板にバーコーター#8を用いて塗布し、25℃で3時間置くことで硬化被膜を得た。得られたコーティング基板の紫外可視光透過スペクトルを図4に示した。
一方、図4に示されるように、比較例1で調製した、市販の酸化チタン粒子分散液を用いたコーティング組成物から作製された硬化被膜(比較例2)は、可視光領域の光透過率が80%以下であり、さらに紫外領域の光透過率が可視光領域と比較して大きく変化していないことから、透明性が悪く、紫外線遮蔽能をほとんど示していないことがわかる。
以上の結果から、本発明で得られるコーティング組成物は種々の有機樹脂をベースとした塗料の透明性を損なわないのみならず、高い紫外線遮蔽能をも有していることがわかる。
したがって、本発明で得られるコーティング組成物を用いることで、各ベース樹脂が含まれる塗料の特性を維持しながら、基板材料の紫外線による劣化を抑制することができる。
アクリル樹脂からなる赤色水性アクリル塗料(ハピオカラー、(株)カンペハピオ製)をガラス基板に刷毛を用いて塗布し、25℃で3時間置くことで硬化被膜を得た。加えて、得られた硬化被膜上に実施例2で調製したコーティング組成物をバーコーター#8を用いて塗布し、25℃で3時間置くことで硬化被膜を得た。
アクリル樹脂からなる赤色水性アクリル塗料(ハピオカラー、(株)カンペハピオ製)をガラス基板に刷毛を用いて塗布し、25℃で3時間置くことで硬化被膜を得た。加えて、得られた硬化被膜上にシリコーン樹脂からなる無溶剤型コーティング組成物(KR-400、信越化学工業(株)製)をバーコーター#8を用いて塗布し、25℃で3時間置くことで硬化被膜を得た。
具体的には、オゾン分解装置による紫外線照射前後の明度指数の差(ΔL*)、クロマティクネス指数の差(Δa*、Δb*)、およびL*a*b*色差(ΔE*)を、色彩計を用いた反射光測定により求めた。結果を表1に示す。
この結果は、本発明のスズおよびマンガンを固溶した正方晶系酸化チタン固溶体微粒子を核とし、核の外側に酸化ケイ素の殻を有するコアシェル微粒子が紫外線を吸収し、下地塗料への紫外線照射が阻害されることで下地塗料の劣化が抑制されていることを示している。
合成例2で得られたコアシェル微粒子のPGM分散液(TPG-1、固形分濃度14.5質量%)5gとシリコーン樹脂からなる無溶剤型コーティング組成物(KR-400、信越化学工業(株)製)10gとを混合し、酸化チタンを含むコーティング組成物を調製した。
調製したコーティング組成物をポリカーボネート基板(PC-1600、タキロン(株)製)にバーコーター#8を用いて塗布し、25℃で3時間置くことで硬化被膜を得た。
合成例2で得られたコアシェル微粒子のPGM分散液(TPG-1、固形分濃度14.5質量%)5gとウレタン樹脂からなる有機系コーティング組成物(油性ニス、和信ペイント(株)製)10gとを混合し、酸化チタンを含むコーティング組成物を調製した。
調製したコーティング組成物をポリカーボネート基板(PC-1600、タキロン(株)製)にバーコーター#8を用いて塗布し、25℃で3時間置くことで硬化被膜を得た。
シリコーン樹脂からなる無溶剤型コーティング組成物(KR-400、信越化学工業(株)製)をポリカーボネート基板(PC-1600、タキロン(株)製)にバーコーター#8を用いて塗布し、25℃で3時間置くことで硬化被膜を得た。
有機系コーティング組成物(油性ニス、和信ペイント(株)製)をポリカーボネート基板(PC-1600、タキロン(株)製)にバーコーター#8を用いて塗布し、25℃で3時間置くことで硬化被膜を得た。
有機系紫外線吸収剤を含んだシリコーン系無溶剤型コーティング組成物(X-40-9309A、信越化学工業(株)製)をポリカーボネート基板(PC-1600、タキロン(株)製)にバーコーター#8を用いて塗布し、25℃で3時間置くことで硬化被膜を得た。
2-(2,4-ジヒドロキシフェノール)4,6-ビス(2,4-ジメチルフェニル)―1,3,5-トリアジンの4質量%PGM溶液1gとシリコーン樹脂からなる無溶剤型コーティング組成物(KR-400、信越化学工業(株)製)10gとを混合し、有機系紫外線吸収剤としてフェニルトリアジンを含むコーティング組成物を調製した。
得られたコーティング組成物をポリカーボネート基板(PC-1600、タキロン(株)製)にバーコーター#8を用いて塗布し、25℃で3時間置くことで硬化被膜を得た。
この結果は、本発明のスズおよびマンガンを固溶した正方晶系酸化チタン固溶体微粒子を核とし、核の外側に酸化ケイ素の殻を有するコアシェル微粒子が紫外線を吸収し、基板であるポリカーボネートへの紫外線照射が阻害されることで、光劣化が抑制されていることを示している。
また、実施例8,9の基板を、有機系紫外線吸収剤を含む比較例6,7の基板と比較しても、イエローインデックスの差は小さい。これは紫外線によって分解しやすい有機系色素と比較して、高い耐光性と環境安定性を有する無機粒子を用いたことで、紫外線吸収能が光劣化によって低下することなく、下地基板への紫外線照射を効果的に阻害したためであると考えられる。
Claims (8)
- (A)室温硬化性樹脂:100質量部、ならびに
(B)スズおよびマンガンを固溶した正方晶系酸化チタン固溶体微粒子を核とし、この核の外側に酸化ケイ素の殻を有するコアシェル微粒子:0.1~50質量部
を含むことを特徴とするコーティング組成物。 - 前記コアシェル微粒子の、動的光散乱法で測定した体積基準の粒度分布における50%累積径が1~50nmである請求項1記載のコーティング組成物。
- 前記室温硬化性樹脂が、アクリル樹脂、ポリエステル樹脂、シリコーン変性ポリエステル樹脂、シリコーン変性アクリル樹脂、エポキシ樹脂、ポリカーボネート樹脂、シリコーン樹脂、フッ素樹脂、塩素系樹脂、ポリオレフィン樹脂、ウレタン樹脂、およびアクリルウレタン樹脂からなる群より選ばれる1種または2種以上の樹脂を含む請求項1または2記載のコーティング組成物。
- さらに、酸化アルミニウム、酸化セリウム、酸化亜鉛、酸化インジウムスズ、酸化ジルコニウム、酸化スズ、酸化鉄、酸化ケイ素、および酸化チタン(ただし、前記(B)のコアシェル微粒子は除く)からなる群より選ばれる1種または2種以上を含む請求項1~3のいずれか1項記載のコーティング組成物。
- 前記コアシェル微粒子表面の酸化ケイ素の殻が、シロキサン結合を介したオルガノシリル基を有している請求項1~4のいずれか1項記載のコーティング組成物。
- 請求項1~5のいずれか1項記載のコーティング組成物が硬化してなる硬化膜。
- 請求項1~5のいずれか1項記載のコーティング組成物が硬化してなる硬化膜を有する被覆物品。
- 基材と、この基材の少なくとも一方の面に積層された、請求項1~5のいずれか1項記載のコーティング組成物が硬化してなる硬化膜とを有する被覆物品。
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- 2017-06-06 CN CN201780052310.XA patent/CN109661443A/zh active Pending
- 2017-06-06 WO PCT/JP2017/020992 patent/WO2018042803A1/ja active Application Filing
- 2017-06-06 US US16/312,146 patent/US20190225821A1/en not_active Abandoned
- 2017-06-06 KR KR1020197004045A patent/KR20190045165A/ko unknown
- 2017-06-06 JP JP2018536953A patent/JPWO2018042803A1/ja active Pending
- 2017-07-05 TW TW106122563A patent/TW201815683A/zh unknown
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Cited By (3)
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WO2020201883A1 (en) * | 2019-04-01 | 2020-10-08 | 3M Innovative Properties Company | Transparent hydrophilic ultraviolet-absorbing laminate and coating agent |
JP2020168764A (ja) * | 2019-04-01 | 2020-10-15 | スリーエム イノベイティブ プロパティズ カンパニー | 透明親水性紫外線吸収積層体、及び透明親水性紫外線吸収コーティング剤 |
JP7395263B2 (ja) | 2019-04-01 | 2023-12-11 | スリーエム イノベイティブ プロパティズ カンパニー | 透明親水性紫外線吸収積層体、及び透明親水性紫外線吸収コーティング剤 |
Also Published As
Publication number | Publication date |
---|---|
US20190225821A1 (en) | 2019-07-25 |
KR20190045165A (ko) | 2019-05-02 |
TW201815683A (zh) | 2018-05-01 |
EP3505580A4 (en) | 2020-01-29 |
EP3505580A1 (en) | 2019-07-03 |
JPWO2018042803A1 (ja) | 2019-02-14 |
CN109661443A (zh) | 2019-04-19 |
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