WO2018185865A1 - Hydrophilicity-imparting agent, hydrophilic coating film forming method, hydrophilic coating film, and solar panel - Google Patents

Hydrophilicity-imparting agent, hydrophilic coating film forming method, hydrophilic coating film, and solar panel Download PDF

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Publication number
WO2018185865A1
WO2018185865A1 PCT/JP2017/014156 JP2017014156W WO2018185865A1 WO 2018185865 A1 WO2018185865 A1 WO 2018185865A1 JP 2017014156 W JP2017014156 W JP 2017014156W WO 2018185865 A1 WO2018185865 A1 WO 2018185865A1
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Prior art keywords
fine particles
hydrophilicity
diameter group
silicate
imparting agent
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PCT/JP2017/014156
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French (fr)
Japanese (ja)
Inventor
藤原正典
鹿取茂雄
天倉弘行
時吉猛
山縣宏之
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パンサーフェス株式会社
京浜化成株式会社
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Priority to PCT/JP2017/014156 priority Critical patent/WO2018185865A1/en
Publication of WO2018185865A1 publication Critical patent/WO2018185865A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/16—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer formed of particles, e.g. chips, powder or granules
    • 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
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to a hydrophilicity imparting agent for forming a hydrophilic film on an object to be treated, and a hydrophilic film forming method, and further, the hydrophilic film and the hydrophilic film on the surface of a protective cover. It is related with the solar panel formed.
  • a solar panel (solar panel) is a power generation means that mainly receives light energy from the sun and generates electricity by the photovoltaic effect. Since the solar panels are often installed outdoors such as the roof of a house, they are exposed to wind and rain. Therefore, a protective cover is usually provided on the surface of the solar panel.
  • the protective cover is required to have high translucency and performance that is difficult to get dirty.
  • the coating liquid disclosed in Patent Document 1 includes an antistatic material (tin oxide having an average particle diameter of 2 nm or less), a low refractive material (silica having an average particle diameter of 10 nm or less), and a hydrophilic material (average particle diameter of 2 nm).
  • an antistatic material titanium oxide having an average particle diameter of 2 nm or less
  • a low refractive material silicon having an average particle diameter of 10 nm or less
  • a hydrophilic material average particle diameter of 2 nm.
  • the protective cover that can improve the transmittance by such means is limited to a cover that is not provided with a so-called AR (Anti Reflection) coat.
  • the light transmittance of the protective cover not coated with AR coating is about 85% from the visible light region to the infrared region.
  • the protective cover without AR coating was applied to a chemical solution prepared by the present inventor and having a mode value of 10 nm or less dispersed in a solvent. It was confirmed that the light transmittance was improved by about 1%.
  • the light transmittance of the protective cover with AR coating is generally around 88% from the visible light region to the infrared region.
  • medical solution with respect to this protective cover it was confirmed that light transmittance falls.
  • a protective cover of a solar panel an AR-coated one is mainly used. Therefore, means for improving the light transmittance of the protective cover with the AR-coated is required.
  • the hot spot phenomenon is a phenomenon in which a shadowed solar battery cell becomes a resistor when current flows and generates heat.
  • the solar battery cell is damaged, and the power generation amount and long-term durability of the solar battery module are reduced.
  • the present invention has been completed in view of the technical problem described above, and can impart high hydrophilicity to an object to be processed. Further, for translucent materials such as a protective cover for a solar panel, It is an object of the present invention to provide a novel hydrophilicity imparting agent and a hydrophilic film forming method capable of improving the translucency in the infrared region. Another object of the present invention is to provide a hydrophilic film formed by the hydrophilic film forming method and a solar panel in which the hydrophilic film is formed on the surface of a protective cover.
  • the present invention provides a hydrophilic property-imparting agent having high self-cleaning property (self-cleaning property) that suppresses hot spot phenomenon, a hydrophilic film, a method for forming a hydrophilic film, and a solar panel. Let it be an issue.
  • the hydrophilicity-imparting agent of the present invention for solving the technical problem is a hydrophilicity-imparting agent for forming a hydrophilic film on an object to be treated, which is a silicate-based fine particle composed of silicate or silica, and a solvent.
  • the silicate-based fine particles include a small diameter group having a mode value of 10 nm or less and a large diameter group having a mode value of 15 to 30 nm, and the solid particles of the small diameter group and the large diameter group in the solvent
  • the weight ratio is 3: 1 to 1: 5
  • the blending ratio of the silicic acid-based fine particles in the hydrophilicity-imparting agent is 0.3 wt% to 3.0 wt% ( Hereinafter, referred to as “the agent of the present invention”).
  • the hydrophilic film forming method of the present invention is a hydrophilic film forming method for forming a hydrophilic film on an object to be treated, and comprises a small diameter group having a mode value of 10 nm or less and a large diameter group having a mode value of 15 to 30 nm.
  • Silicate-based fine particles comprising at least silicate or silica contained in the solvent are blended in a solvent such that the weight ratio of the solid content between the small diameter group and the large diameter group is 3: 1 to 1: 5.
  • An application step of applying a hydrophilicity-imparting agent having a blending ratio of 0.3 wt% to 3.0 wt% to the object to be processed one or more times is performed.
  • the hydrophilic coating of the present invention is a hydrophilic coating containing silicate fine particles made of silicate or silica, wherein the silicate fine particles have a small diameter group with a mode value of 10 nm or less and a large size with a mode value of 15 to 30 nm.
  • the solid content weight ratio of the small diameter group and the large diameter group is 3: 1 to 1: 5.
  • the present invention includes a solar panel characterized in that the hydrophilic film of the present invention is formed on the surface of a protective cover.
  • the present invention it is possible to impart high hydrophilicity and self-cleaning properties to an object to be processed, and particularly for translucent materials such as a protective cover for a solar panel, translucency for light in the infrared region. It becomes possible to further improve the sex.
  • FIG. 1 is a chart showing the light transmittance of a protective panel not coated with AR.
  • FIG. 2 is a chart showing the light transmittance of a protective panel coated with an AR coating.
  • FIG. 3 is a graph in which the transmittance integrated value of the protective panel coated with the hydrophilicity imparting agent is plotted against the blending ratio of the silicate fine particles in the hydrophilicity imparting agent.
  • the hydrophilicity-imparting agent of the present invention is a hydrophilicity-imparting agent for forming a hydrophilic film on an object to be treated, which contains silicate-based fine particles composed of silicate or silica, and a solvent,
  • the fine particles include a small diameter group having a mode value of 10 nm or less and a large diameter group having a mode value of 15 to 30 nm, and the solid content weight ratio of the small diameter group to the large diameter group in the solvent is 3: 1 to 1: 5, and the mixing ratio of the silicic acid-based fine particles in the hydrophilicity-imparting agent is 0.3 wt% to 3.0 wt%.
  • the agent of the present invention is used for forming the hydrophilic film on the object to be treated.
  • the “object to be treated” is not particularly limited, and examples thereof include a building outer wall, an automobile exterior, a window, and a solar panel protective cover.
  • the “silicic acid-based fine particles” mean “at least one selected from silicate fine particles or silica fine particles”.
  • the silicate is an anion having a structure in which an electronegative ligand such as oxygen surrounds one or a plurality of silicon atoms, a cation such as sodium ion or ammonium ion, It is a compound which comprises.
  • the silica SiO 2
  • the silica does not have a negative charge around the silicon atom and thus does not have a cation, but is a kind of silicate.
  • the binding of the formed hydrophilic coating to the object to be processed is mainly due to intermolecular force.
  • silicate fine particles when silicate fine particles are used as the silicic acid-based fine particles, the formed hydrophilic film is bonded to the object by the silanol reaction in addition to the intermolecular force. This is due to chemical bonding by siloxane.
  • the silicic acid-based fine particles as the silicic acid-based fine particles, a small diameter group having a mode value of 10 nm or less (preferably 1 to 7 nm) and a large diameter having a mode value of 15 to 30 nm (preferably 20 to 30 nm). And at least a group is used.
  • An object to be processed on which a hydrophilic film containing the silicate fine particles is formed has a surface having a textured structure with fine irregularities due to the silicate fine particles having different particle diameters. As a result, when it rains, water enters between the dirt adhering to the hydrophilic film and the hydrophilic film, and the dirt floats and is washed away, so that the object to be treated has a high self-cleaning property.
  • the particle size distribution of the small-diameter group having a mode value of 10 nm or less among the silicate-based fine particles before blending is preferably 15% or less, more preferably 10% or less, and even more preferably, the weight ratio of particles of 7 nm or more. Is 5% or less. This is because if the weight ratio of particles of 7 nm or more is 15% or less, the durability of the formed hydrophilic coating is further improved.
  • the particle size distribution of the large-diameter group having a mode value of 15 to 30 nm is preferably such that the weight ratio of particles of 12 nm or less is 15% or less, more preferably 10% or less. More preferably, it is 5% or less. This is because if the weight ratio of particles of 12 nm or less is 15% or less, the durability of the formed hydrophilic coating is further improved.
  • the “mode” means the most appearance ratio when the particle size distribution is measured by a laser analysis / scattering method, with a group of the silicate-based fine particles (the large diameter group or the small diameter group) as a population. Means a high particle size.
  • the mode is a normal distribution that matches the average particle diameter with a difference within ⁇ 10% (more preferably within ⁇ 5%). It is preferable to use one having a close particle size distribution.
  • silica fine particles produced according to a known method such as a sol-gel method, a production method using water glass as a raw material, a gas phase method, and the silica fine particles are stabilized with sodium by a known method, or Ammonium-stabilized silicate microparticles or ammonium silicate prepared according to known methods can be used.
  • the silicic acid-based fine particles for example, ion-exchange of sodium silicate by a water glass method to prepare active silicic acid, and then heating this, the seed particle-containing aqueous solution whose pH is adjusted with NaOH
  • the method include manufacturing by adding particles and growing the particles.
  • a method of producing silica particles while performing condensation and particle growth simultaneously with hydrolysis of alkyl silicate (tetraalkoxysilane) in the presence of a basic catalyst by an alkoxide method can also be mentioned.
  • the small diameter group and the large diameter group are blended in the solvent at a solid content weight ratio of 3: 1 to 1: 5.
  • the hydrophilic coating formed by the agent of the present invention has a structure in which the surface causes capillary action.
  • the hydrophilicity of the surface of the hydrophilic coating is improved.
  • the solid content weight ratio between the small diameter group and the large diameter group is more preferably 2: 1 to 1: 5, further preferably 1: 1 to 1: 5, and particularly preferably 1: 2 to 1. : 4.
  • the mode value of the silicate-based fine particles after blending the small diameter group and the large diameter group is preferably 5 nm or more, more preferably 10 nm or more, still more preferably 15 nm or more, preferably 28 nm or less, more preferably 26 nm or less, More preferably, it is 24 nm or less.
  • the mode value of the silicate fine particles is a particle size having the highest appearance ratio obtained when the particle size distribution of the silicate fine particles is measured by a laser analysis / scattering method.
  • the average particle diameter of the silicic acid fine particles is 5 nm or more. More preferably, it is 10 nm or more, More preferably, it is 20 nm or more, 50 nm or less is preferable, More preferably, it is 40 nm or less, More preferably, it is 30 nm or less.
  • the weight ratio of particles having a particle diameter of 15 nm to 28 nm is: It is preferably 30% or more, more preferably 40% or more, and further preferably 50% or more.
  • the “solvent” is not particularly limited as long as it can disperse the silicate-based fine particles.
  • a liquid medium selected from water and an organic solvent such as alcohol is used alone or in combination. Can be used.
  • a lower alcohol such as isopropyl alcohol
  • the blending ratio of the silicic acid-based fine particles in the hydrophilicity imparting agent of the present invention agent is preferably 0.3% by weight to 3.0% by weight. If the mixing ratio of the silicic acid fine particles is too low or too high, the light transmittance of the object to be processed may decrease when a predetermined amount is applied to the object to be processed. On the other hand, if the mixing ratio of the silicic acid-based fine particles is too low, the number of times of applying the hydrophilicity-imparting agent is increased in order to form a film, which is not preferable.
  • the blending ratio is preferably 0.4% by weight or more, more preferably 0.5% by weight or more, further preferably 1.0% by weight or more, preferably 2.5% by weight or less, more Preferably it is 2.0 weight% or less.
  • the blending ratio of the silicate-based fine particles is 0.5 ⁇ 0.2% by weight. It is preferable to do.
  • the mixing ratio of the silicate-based fine particles is 1.5 ⁇ 0.5 wt% is preferable.
  • agent it does not deny containing components other than the said silicic acid type microparticles
  • desired components such as an antistatic agent, may be mix
  • the hydrophilic film forming method of the present invention is a hydrophilic film forming method for forming a hydrophilic film on an object to be treated, and comprises a small diameter group having a mode value of 10 nm or less and a large diameter group having a mode value of 15 to 30 nm.
  • Silicate-based fine particles composed of at least silicate or silica are mixed in a solvent so that the small diameter group and the large diameter group have a solid content weight ratio of 3: 1 to 1: 5.
  • An application step of applying a hydrophilicity-imparting agent having a blending ratio of 0.3 wt% to 3.0 wt% to the object to be processed one or more times is performed (hereinafter referred to as “the present invention”). Referred to as “method").
  • the agent of the present invention is a one-component type in which the small-diameter group and the large-diameter group coexist in the solvent.
  • a hydrophilicity-imparting agent a first chemical solution in which the small-diameter group is dispersed and a second chemical solution in which the large-diameter group is dispersed in the solvent are prepared and mixed at the time of performing the coating process. It may be used. Alternatively, a stock solution containing an excessive amount of the silicic acid-based fine particles may be prepared, and the hydrophilicity-imparting agent having a desired concentration may be adjusted by diluting with the solvent during execution of the coating process.
  • the same one-component type as the agent of the present invention may be used.
  • a one-component type hydrophilicity imparting agent similar to the agent of the present invention for example, a first stock solution in which silicate-based fine particles of a small diameter group having a mode value of 10 nm or less are dispersed in a dispersion medium. And a second stock solution in which a silicate-based fine particle of a large diameter group having a mode value of 15 nm to 30 nm is dispersed in a dispersion medium, and a diluent, thereby mixing a one-component type hydrophilicity imparting agent having a desired concentration. May be prepared.
  • the “solvent” is composed of a dispersion medium of the first stock solution, a dispersion medium of the second stock solution, and a diluent.
  • the concentration of the silicate particles as a solid content is preferably 5% by weight to 30% by weight, and preferably 7% by weight to 25% by weight. % Is more preferable, and 10% by weight to 20% by weight is more preferable.
  • the concentration of the silicate fine particles as a solid content is preferably 10 wt% to 60 wt%, preferably 15 wt% to 50% by weight is more preferable, and 25% by weight to 40% by weight is further preferable.
  • the coating amount of the hydrophilic agent in the coating step it is preferable to 30mg / m 2 ⁇ 300mg / m 2 by dry weight.
  • the coating amount it is preferable to 30mg / m 2 ⁇ 300mg / m 2 by dry weight.
  • the coating amount of the hydrophilicity-imparting agent on the object to be treated is more preferably 45 mg / m 2 or more, more preferably 50 mg / m 2 or more, particularly preferably 75 mg / m 2 or more, and most preferably 100 mg / m, in terms of dry weight. 2 or more, more preferably 250 mg / m 2 or less, further preferably 200 mg / m 2 or less, and particularly preferably 150 mg / m 2 or less.
  • the polysilazane is an inorganic polymer having “— (SiH 2 NH) —” as a basic unit.
  • a pretreatment agent in which this polysilazane is dissolved in an organic solvent or the like is applied to the object to be treated, a deammonia reaction occurs due to a reaction with moisture in the atmosphere, and a dense material having excellent adhesion to the object to be treated.
  • a silica coating is formed. Since the deammonification reaction proceeds relatively slowly, if the pretreatment step is performed before the coating step, the hydrophilic film is more strongly bonded to the object to be processed, and the hydrophilic property is increased. The durability of the coating is improved.
  • the blending ratio of the polysilazane contained in the pretreatment agent is determined according to the coating amount and the number of coatings, and is not particularly limited, but is within the range of 0.1 to 1% by weight ( More preferably, it is within the range of 0.3 to 0.7% by weight.
  • the hydrophilic coating of the present invention is a hydrophilic coating containing silicate fine particles made of silicate or silica, and the silicate fine particles have a small diameter group with a mode value of 10 nm or less and a large size with a mode value of 15 to 30 nm.
  • the solid content weight ratio of the small diameter group and the large diameter group is a weight ratio of 3: 1 to 1: 5 (hereinafter referred to as “the coating film of the present invention”). ).
  • the coating of the present invention is preferably provided on the object to be treated so that the dry weight is 30 mg / m 2 or more, more preferably 45 mg / m 2 or more, still more preferably 75 mg / m 2 or more, It is particularly preferably 100 mg / m 2 or more, preferably 300 mg / m 2 or less, more preferably 250 mg / m 2 or less, further preferably 200 mg / m 2 or less, particularly preferably 150 mg. / M 2 or less.
  • the coating amount is within the above range in terms of dry weight, a film having high light transmittance and excellent hydrophilicity can be obtained.
  • those having a contact angle of 10 degrees or less are preferred, those having a hydrophilicity of 7 degrees or less are more preferred, and those having a hydrophilicity of 5 degrees or less are a more preferred embodiment.
  • the solar panel of the present invention is characterized in that the film of the present invention is formed on the surface of a protective cover (hereinafter referred to as “the present invention panel”).
  • the solar panel of the present invention includes at least one solar cell module.
  • the solar cell module preferably includes a solar cell layer, a protective cover provided on the upper surface of the solar cell layer, and a back sheet provided on the lower surface of the solar cell layer.
  • the protective cover is generally tempered glass.
  • An AR coat antireflection coating
  • Tables 1 to 3 below show prescriptions of the present invention according to Examples 1 to 24 and prescriptions of chemical solutions according to Comparative Examples 1 to 18.
  • the inventive agent according to each example and the chemical solution according to each comparative example are prepared in such a manner that the weight ratio of the solid content of the large diameter group and the small diameter group becomes a value described in each table.
  • a first stock solution in which water is dispersed in water and / or a second stock solution in which silicate-based fine particles of a large diameter group having a mode value of 15 to 30 nm are dispersed in water, water, or a mixture of water and IPA It was prepared by diluting with.
  • the ratio of the total weight of water in the first stock solution, the water in the second stock solution, and the water in the mixed solution to the weight of IPA in the mixed solution is as follows. It was prepared to be 1: 1.
  • Example 1 the silicic acid-based fine particles in which the solid content weight ratio of the small diameter group and the large diameter group was blended at 3: 1 had an average particle diameter in terms of weight of 25.9 nm.
  • Example 2 the silicic acid-based fine particles in which the solid content weight ratio of the small diameter group and the large diameter group was blended at 1: 5 had an average particle diameter in terms of weight of 23.7 nm.
  • Example 3 the silicic acid-based fine particles in which the solid content weight ratio of the small diameter group and the large diameter group was blended at 1: 3 had an average particle diameter in terms of weight of 21.7 nm.
  • the average particle diameter in terms of weight of the silicic acid-based fine particles of Comparative Example 2 was 3.5 nm.
  • the average particle diameter in terms of weight of the silicic acid-based fine particles of Comparative Example 5 was 26.8 nm.
  • the silicic acid-based fine particles in which the solid weight ratio between the small diameter group and the large diameter group was blended at a ratio of 1: 5 had a mode value of 18.7 nm, a weight-converted average particle diameter of 23.7 nm, and distribution. As a result, the weight ratio of 18 nm to 23 nm was 50% or more.
  • the silicic acid-based fine particles in which the solid weight ratio of the small diameter group and the large diameter group was blended at 1: 3 had a mode value of 17.3 nm, a weight-converted average particle diameter of 21.7 nm, and distribution. As a result, the weight ratio of 15 nm to 18 nm was 50% or more.
  • Mode value 1 nm Mode value 1 nm
  • Silica-based fine particles (ammonia-stabilized amorphous silica) having a solid content concentration of 10% by weight
  • Aqueous dispersion mode value 5 nm Mode value 5 nm
  • solid content Silica-based fine particles having a concentration of 15% by weight (ammonia-stabilized amorphous silica) mode of aqueous dispersion
  • 10 nm Silicate-based fine particles having a mode value of 10 nm and a solid concentration of 20% by weight (ammonia stable)
  • Mode value 15 nm Mode value 15 nm
  • Silica-based fine particles (ammonia-stabilized amorphous silica) having a solid content concentration of 20% by weight
  • Aqueous dispersion mode value 25 nm Mode value 25 nm
  • solid content Silica-based fine particles (ammonia-based fine particles (ammonia-)
  • Mode value 1 nm Mode dispersion value 1 nm
  • Silica-based fine particles sidium-stabilized amorphous silica having a solid content concentration of 10% by weight
  • Aqueous dispersion mode value 5 nm Mode value 5 nm
  • solid content Silica-based fine particles having a concentration of 15% by weight (sodium-stabilized amorphous silica) in an aqueous dispersion mode of 10 nm: Silica-based fine particles having a mode value of 10 nm and a solid content concentration of 20% by weight (sodium-stable Type amorphous silica) aqueous dispersion
  • Mode value 15 nm Mode dispersion value 15 nm
  • Silica-based fine particles siodium-stabilized amorphous silica
  • Aqueous dispersion mode value 25 nm Mode value 25 solid content Silica-based fine
  • Mode value 1 nm: Mode dispersion value of 1 nm, solid dispersion concentration of 10 wt% silicate fine particles (ammonium silicate) in aqueous dispersion mode: 5 nm: Mode value of 5 nm, solid content concentration of 15 wt% Silica fine particles (ammonium silicate) aqueous dispersion mode value 10 nm: Mode dispersion value 10 nm, solid content concentration 20 wt% silicate fine particles (ammonium silicate) aqueous dispersion [second stock solution ] Mode 15 nm: Mode dispersion value 15 nm, solid dispersion concentration 20 wt% silicate fine particles (ammonium silicate) aqueous dispersion mode 25 nm: Mode value 25 nm, solid content concentration 40 wt% Silica fine particles (ammonium silicate) aqueous dispersion mode value 30 nm: Mode dispersion value 30 nm,
  • the silicic acid type fine particles to be used were set in a wet measuring cell of a laser diffraction particle size measuring device (manufactured by Otsuka Electronics Co., Ltd., model number: FPAR-1000), and the particle size was measured with a sample refractive index of 1.3313. From the obtained weight-based frequency distribution graph (frequency distribution obtained by dividing the logarithmic plot particle diameter of 1 nm to 10000 nm into 45), the average particle diameter, the mode value, and the weight ratio of the particles were obtained.
  • ⁇ Test 1> Workpiece- Protective cover for solar panels with AR coating -
  • the present invention Hydrophilicity in which the mixing ratio of the silicic acid-based fine particles in which the small diameter group and the large diameter group are mixed in the solid content weight ratio shown in Examples 1 to 24 in Tables 1 to 3 is 0.5 ⁇ 0.2 wt%.
  • Giving agent-method of the present invention- The coating film of the present invention is formed by executing a coating step of coating the agent of the present invention on the surface of the protective cover.
  • execution of the method of the present invention was performed in two ways: when the pretreatment process was not executed and when the pretreatment process was executed.
  • a pretreatment step is performed in which a pretreatment agent (0.5 wt% polysilazane aqueous solution) is uniformly applied (10 ml / m 2 (25 ° C.)). To do. After natural drying for 15 minutes, an application step of uniformly applying the agent of the present invention (10 g / m 2 (25 ° C.) by wet) is performed, thereby forming the coating of the present invention on one side of the protective cover. .
  • a pretreatment agent 0.5 wt% polysilazane aqueous solution
  • ⁇ Evaluation test> Evaluation of wettability-
  • the wettability (ease of application) of the agent of the present invention with respect to the protective cover is evaluated.
  • the symbol for evaluating the wettability means that ⁇ ⁇ ⁇ is the best, and hereinafter, the wettability is inferior in the order of ⁇ ⁇ ⁇ ⁇ ⁇ x.
  • this invention film is formed in the one side of the said protective cover by air-drying for 12 hours, and a contact angle is measured.
  • the contact angle was determined by dropping 1 ⁇ l of distilled water onto the surface of the coating of the present invention, and measuring the contact angle of the water drop after 1 second with a contact angle measuring device (CAX-150 (manufactured by Kyowa Interface Chemical Co., Ltd.)). It is the value obtained by measuring.
  • the wear process in which the coating of the present invention formed on one side surface of the protective cover is rubbed once and vertically with a car wash sponge, rinsed with tap water, and then wiped up with a waste cloth is repeated a plurality of times.
  • the contact angle was measured every time the wear process was performed five times, and it was evaluated how many times the wear process was performed to lose hydrophilicity.
  • the symbol which evaluates abrasion resistance shall mean the following.
  • ⁇ The contact angle is maintained until after 40 times.
  • ⁇ The contact angle is maintained until 30 times.
  • X The contact angle increases by 30 times.
  • ⁇ Test 2> Workpiece- Protective cover for solar panels without AR coating -Invention agent- Hydrophilicity in which the mixing ratio of the silicic acid-based fine particles in which the small diameter group and the large diameter group are mixed in the solid content weight ratio shown in Examples 1 to 24 in Tables 1 to 3 is 1.5 ⁇ 0.2 wt%.
  • Giving agent-method of the present invention- The coating of the present invention is formed by executing the coating step of coating the agent of the present invention on the surface of the protective cover (the rest is the same as in Test 1).
  • the hydrophilic coating of the present invention is formed on the protective cover and the contact angle of water is reduced, so that the dust, bird droppings, etc. It was confirmed that water wets and spreads between dirt such as organic matter and volcanic ash and the protective cover, and the dirt floats up, and the dirt flows down with the water according to the inclination of the protective cover. That is, it was found that the protective cover on which the coating film of the present invention was formed exhibited self-cleaning properties.
  • FIG. 1 and 2 show charts for verifying light transmittance in the wavelength range of 300 nm to 1500 nm.
  • the chart shown in FIG. 1 is obtained by measuring the light transmittance of a protective cover without AR coating
  • the chart shown in FIG. 2 is measured by the light transmittance of a protective cover with AR coating.
  • the solid line in the chart shown in FIG. 1 indicates the translucency of the untreated protective cover before the execution of the method of the present invention
  • the dotted line indicates the coating of the present invention by the agent of the present invention according to Example 4. It shows the translucency about the protective cover (NPC) in which is formed.
  • the dotted line in the chart shown in FIG. 2 indicates the translucency of the untreated protective cover before execution of the method of the present invention, and the solid line indicates that the coating of the present invention is formed by the agent of the present invention according to Example 4. It shows the translucency about the made protective cover (NPC).
  • the light transmittance at a wavelength of less than 450 nm is lower than the light transmittance of the untreated protective cover. That is, it can be said that the coating of the present invention formed on the surface of the protective cover on which the AR coating has been made inhibits transmission of light having a wavelength of 450 nm or less.
  • the transmittance of a light beam having a wavelength of 450 nm or more is improved over a wide range, and therefore the total amount of light beam that can be transmitted through the protective cover is larger than that of the untreated protective cover.
  • light having a wavelength of 450 nm or more contains a large amount of light in the infrared region (infrared rays). Therefore, if the coating of the present invention is formed on the protective cover of the solar panel, the light in the infrared region is improved. Properties that can be incorporated can be imparted.
  • the panel of the present invention having a characteristic capable of capturing light in the infrared region satisfactorily enables efficient power generation particularly in the dim time zone during morning and evening or cloudy weather.
  • ⁇ Test 4> Evaluation of transmittance with respect to mixing ratio of silicate fine particles-
  • the light transmittance (%) at a wavelength of 300 to 1500 nm was measured for the protective cover of the solar panel coated with AR before the hydrophilicity imparting agent was applied. Then, the total S 0 of the light transmittance (%) values of each wavelength for each 1 nm from 300 nm to 886 nm corresponding to the band gap energy of silicon was calculated.
  • the light transmittance (%) at a wavelength of 300 to 1500 nm is measured, and the total sum S x of the light transmittance (%) at each wavelength from 300 nm to 886 nm for each wavelength.
  • FIG. 3 shows the result of plotting the obtained transmittance integral value against the mixing ratio of the silicate fine particles.
  • the protective cover having the hydrophilic film has an integral value of transmittance. Became a positive value, and it was confirmed that the light transmittance was improved by the hydrophilic coating. Further, when the blending ratio is 1.0 wt% or more and 2.5 wt% or less, the transmittance integrated value becomes a larger value, and it was confirmed that the light transmittance is further improved by the hydrophilic coating.
  • the panel of the present invention has a characteristic that it is difficult to get dirty because the protective panel is formed with the coating film of the present invention that is highly hydrophilic and self-cleaning.
  • the panel of the present invention has a high light transmittance and two characteristics that are difficult to get dirty, and can maintain a stable power generation capacity.
  • the amount of power generation per day was actually measured, it was confirmed that the amount of power generation increased by 3% or more (about 3-5%) compared to the case of the untreated protective cover.
  • FIG. 1 and FIG. 2 verify the translucency of the protective cover on which the coating film of the present invention is formed by the agent of the present invention according to the fourth embodiment. It has been confirmed that the protective cover in which the coating of the present invention is formed by the agent of the present invention exhibits the same behavior.
  • the present invention has good antifouling properties for various products such as automobile bodies, interior and exterior of buildings, toilets, kitchens, toilets, bathtubs, and other water-based products, signs, signs, plastic products, glass products, etc. It can be suitably used as a means for imparting. Moreover, it can also be suitably used as means for constructing a solar panel that realizes highly efficient photovoltaic power generation.

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Abstract

[Problem] A purpose of the present invention is to provide: a novel hydrophilicity-imparting agent that can impart high hydrophilicity to an object to be treated and that enables improved transparency in the infrared region for transparent materials such as a protective cover for a solar panel; and a hydrophilic coating film forming method. Another purpose of the present invention is to provide: a hydrophilic coating film formed by said hydrophilic coating film forming method; and a solar panel in which said hydrophilic coating film is formed on a surface of a protective cover. [Solution] Hydrophilicity is imparted to an object to be treated by a hydrophilicity-imparting agent that contains a solvent and silicic acid-type microparticles comprising a silicate or silica, wherein the silicic acid-type microparticles include at least a minor diameter group having a mode of not more than 10 nm and a major diameter group having a mode of 15 to 30 nm, the solids weight ratio in the solvent between the minor diameter group and the major diameter group is 3:1 to 1:5, and the content of the silicic acid-type microparticles in the hydrophilicity-imparting agent is 0.3 wt% to 3.0 wt%.

Description

親水性付与剤、親水性被膜形成方法、親水性被膜、及び太陽光パネルHydrophilic imparting agent, hydrophilic film forming method, hydrophilic film, and solar panel
　本発明は、被処理物に親水性被膜を形成するための親水性付与剤、及び親水性被膜形成方法に関するものであり、更に、親水性被膜、並びに、保護カバーの表面に前記親水性被膜が形成されてなる太陽光パネルに関する。 The present invention relates to a hydrophilicity imparting agent for forming a hydrophilic film on an object to be treated, and a hydrophilic film forming method, and further, the hydrophilic film and the hydrophilic film on the surface of a protective cover. It is related with the solar panel formed.
　太陽光パネル（ソーラーパネル）は、主として太陽からの光エネルギーを受け、光起電力効果によって電気を発生させる発電手段である。前記太陽光パネルは、家屋の屋根等の屋外に設置されるものが多いため、風雨に晒されることになる。そのため、通常、前記太陽光パネルの表面には保護カバーが設けられる。 A solar panel (solar panel) is a power generation means that mainly receives light energy from the sun and generates electricity by the photovoltaic effect. Since the solar panels are often installed outdoors such as the roof of a house, they are exposed to wind and rain. Therefore, a protective cover is usually provided on the surface of the solar panel.
　前記太陽光パネルによって効率の高い光発電を実現するにあたっては、前記太陽光パネルに存するセルにできるだけ多くの光エネルギーを取り込む必要がある。そのため、前記保護カバーには、高い透光性と、汚れ難い性能とが要求される。 In order to realize highly efficient photovoltaic power generation using the solar panel, it is necessary to capture as much light energy as possible into the cells existing in the solar panel. Therefore, the protective cover is required to have high translucency and performance that is difficult to get dirty.
　最近では、前記保護カバーに親水性を付与し、もって、降雨時に、前記保護カバーの表面に付着した汚れが除去されるようにする手段が開発されている（例えば、下記特許文献１参照。）。 Recently, a means has been developed to impart hydrophilicity to the protective cover so that dirt attached to the surface of the protective cover is removed during rain (see, for example, Patent Document 1 below). .
特開２０１３‐８００６７号公報JP 2013-80067 A
　特許文献１に開示された塗布液は、帯電防止材料（平均粒径が２ｎｍ以下の酸化スズ）と、低屈折材料（平均粒径が１０ｎｍ以下のシリカ）と、親水性材料（平均粒径２ｎｍ以下のアモルファスシリカ）と、を溶媒中に分散させたものである。この塗布液を太陽光パネルの保護カバーに塗布すれば、前記帯電防止材料が前記保護カバーの帯電を抑制することによって汚れが付着し難くなり、又、前記低屈折材料が前記保護カバーの表面反射を抑制することによって光線透過率が向上し、更に、前記親水性材料が前記保護カバーの接触角を下げることによって親水性が付与されると記載されている。 The coating liquid disclosed in Patent Document 1 includes an antistatic material (tin oxide having an average particle diameter of 2 nm or less), a low refractive material (silica having an average particle diameter of 10 nm or less), and a hydrophilic material (average particle diameter of 2 nm). The following amorphous silica) is dispersed in a solvent. If this coating solution is applied to the protective cover of the solar panel, the antistatic material is less likely to be contaminated by suppressing the charging of the protective cover, and the low refractive material is not reflected on the surface of the protective cover. It is described that the light transmittance is improved by suppressing, and that the hydrophilic material is imparted with hydrophilicity by lowering the contact angle of the protective cover.
　但し、係る手段によって透過率を向上させ得る保護カバーは、いわゆるＡＲ（Anti Reflection）コートがなされていないものに限られる。 However, the protective cover that can improve the transmittance by such means is limited to a cover that is not provided with a so-called AR (Anti Reflection) coat.
　通常、ＡＲコートがなされていない保護カバーの光線透過率は、可視光領域から赤外領域にかけて８５％前後となる。このＡＲコートがなされていない保護カバーに対し、本発明者が作製した、最頻値１０ｎｍ以下のシリカを溶媒に分散させた薬液に塗布したところ、可視光領域から赤外領域にかけて０．５～１％程度、光線透過率が改善されることが確認された。 Usually, the light transmittance of the protective cover not coated with AR coating is about 85% from the visible light region to the infrared region. The protective cover without AR coating was applied to a chemical solution prepared by the present inventor and having a mode value of 10 nm or less dispersed in a solvent. It was confirmed that the light transmittance was improved by about 1%.
　一方、ＡＲコートがなされた保護カバーの光線透過率は、可視光領域から赤外領域にかけて８８％前後のものが一般的である。本発明者が、この保護カバーに対し、前記薬液を塗布したところ、光線透過率が下がることが確認された。現在、太陽光パネルの保護カバーとしてはＡＲコートがなされたものが主流であり、従って、係るＡＲコートがなされた保護カバーの光線透過率を向上させる手段が求められている。 On the other hand, the light transmittance of the protective cover with AR coating is generally around 88% from the visible light region to the infrared region. When this inventor applied the said chemical | medical solution with respect to this protective cover, it was confirmed that light transmittance falls. At present, as a protective cover of a solar panel, an AR-coated one is mainly used. Therefore, means for improving the light transmittance of the protective cover with the AR-coated is required.
　また、太陽光パネルの保護カバーに汚れが付着すると、付着したところが影になり、ホットスポット現象が起こる。ホットスポット現象とは、影になった太陽電池セルが、電流が流れる際に抵抗体となり、熱を発生させる現象である。ホットスポット現象が起こると、太陽電池セルが破損し、太陽電池モジュールの発電量の低下や長期耐久性が低下する。 Also, if dirt adheres to the protective cover of the solar panel, the place where it adheres becomes a shadow and a hot spot phenomenon occurs. The hot spot phenomenon is a phenomenon in which a shadowed solar battery cell becomes a resistor when current flows and generates heat. When the hot spot phenomenon occurs, the solar battery cell is damaged, and the power generation amount and long-term durability of the solar battery module are reduced.
　本発明は、前記技術的課題に鑑みて完成されたものであり、被処理物に対し、高い親水性を付与できるうえ、太陽光パネルの保護カバーなどの透光性材料に対しては、更に赤外領域の透光性の向上を可能にする新規な親水性付与剤、及び親水性被膜形成方法を提供することを目的とする。又、本発明は、前記親水性被膜形成方法によって形成された親水性被膜、並びに、保護カバーの表面に前記親水性被膜が形成されてなる太陽光パネルを提供することも目的とする。さらに、本発明は、ホットスポット現象を抑制するセルフクリーニング性（自己洗浄性）の高い親水性付与剤、親水性被膜、および、親水性被膜の形成方法、ならびに、太陽光パネルを提供することを課題とする。 The present invention has been completed in view of the technical problem described above, and can impart high hydrophilicity to an object to be processed. Further, for translucent materials such as a protective cover for a solar panel, It is an object of the present invention to provide a novel hydrophilicity imparting agent and a hydrophilic film forming method capable of improving the translucency in the infrared region. Another object of the present invention is to provide a hydrophilic film formed by the hydrophilic film forming method and a solar panel in which the hydrophilic film is formed on the surface of a protective cover. Furthermore, the present invention provides a hydrophilic property-imparting agent having high self-cleaning property (self-cleaning property) that suppresses hot spot phenomenon, a hydrophilic film, a method for forming a hydrophilic film, and a solar panel. Let it be an issue.
　前記技術的課題を解決するための本発明の親水性付与剤は、被処理物に親水性被膜を形成するための親水性付与剤であって、シリケート又はシリカからなるケイ酸系微粒子と、溶媒とを含有し、前記ケイ酸系微粒子が、最頻値１０ｎｍ以下の小径群と最頻値１５～３０ｎｍの大径群とを含み、前記溶媒中の前記小径群と前記大径群との固形分重量比率が、３：１～１：５であり、前記親水性付与剤における前記ケイ酸系微粒子の配合割合が、０．３重量％～３．０重量％であることを特徴とする（以下、「本発明剤」と称する。）。 The hydrophilicity-imparting agent of the present invention for solving the technical problem is a hydrophilicity-imparting agent for forming a hydrophilic film on an object to be treated, which is a silicate-based fine particle composed of silicate or silica, and a solvent. The silicate-based fine particles include a small diameter group having a mode value of 10 nm or less and a large diameter group having a mode value of 15 to 30 nm, and the solid particles of the small diameter group and the large diameter group in the solvent The weight ratio is 3: 1 to 1: 5, and the blending ratio of the silicic acid-based fine particles in the hydrophilicity-imparting agent is 0.3 wt% to 3.0 wt% ( Hereinafter, referred to as “the agent of the present invention”).
　本発明の親水性被膜形成方法は、被処理物に親水性被膜を形成する親水性被膜形成方法であって、最頻値１０ｎｍ以下の小径群と最頻値１５～３０ｎｍの大径群とを少なくとも含むシリケート又はシリカからなるケイ酸系微粒子が、前記小径群と前記大径群との固形分重量比率が３：１～１：５となるように溶媒に配合され、前記ケイ酸系微粒子の配合割合が、０．３重量％～３．０重量％である親水性付与剤を、前記被処理物に、一ないし複数回塗布する塗布工程を実行することを特徴とする。 The hydrophilic film forming method of the present invention is a hydrophilic film forming method for forming a hydrophilic film on an object to be treated, and comprises a small diameter group having a mode value of 10 nm or less and a large diameter group having a mode value of 15 to 30 nm. Silicate-based fine particles comprising at least silicate or silica contained in the solvent are blended in a solvent such that the weight ratio of the solid content between the small diameter group and the large diameter group is 3: 1 to 1: 5. An application step of applying a hydrophilicity-imparting agent having a blending ratio of 0.3 wt% to 3.0 wt% to the object to be processed one or more times is performed.
　本発明の親水性被膜は、シリケート又はシリカからなるケイ酸系微粒子を含む親水性被膜であって、前記ケイ酸系微粒子が、最頻値１０ｎｍ以下の小径群と最頻値１５～３０ｎｍの大径群とを含み、前記小径群と前記大径群との固形分重量比率が、３：１～１：５であることを特徴とする。 The hydrophilic coating of the present invention is a hydrophilic coating containing silicate fine particles made of silicate or silica, wherein the silicate fine particles have a small diameter group with a mode value of 10 nm or less and a large size with a mode value of 15 to 30 nm. The solid content weight ratio of the small diameter group and the large diameter group is 3: 1 to 1: 5.
　本発明には、保護カバーの表面に、本発明の親水性被膜が形成されていることを特徴とする太陽光パネルが含まれる。 The present invention includes a solar panel characterized in that the hydrophilic film of the present invention is formed on the surface of a protective cover.
　本発明によれば、被処理物に対し、高い親水性および自己洗浄性を付与できるうえ、太陽光パネルの保護カバーなどの透光性材料に対しては、特に赤外領域の光線に対する透光性の更なる向上が可能となる。 According to the present invention, it is possible to impart high hydrophilicity and self-cleaning properties to an object to be processed, and particularly for translucent materials such as a protective cover for a solar panel, translucency for light in the infrared region. It becomes possible to further improve the sex.
図1は、ＡＲコートがなされていない保護パネルの光線透過率を示すチャートである。FIG. 1 is a chart showing the light transmittance of a protective panel not coated with AR. 図２は、ＡＲコートがなされた保護パネルの光線透過率を示すチャートである。FIG. 2 is a chart showing the light transmittance of a protective panel coated with an AR coating. 図３は、親水性付与剤におけるケイ酸系微粒子の配合割合に対して、親水性付与剤を塗布した保護パネルの透過率積分値をプロットしたグラフである。FIG. 3 is a graph in which the transmittance integrated value of the protective panel coated with the hydrophilicity imparting agent is plotted against the blending ratio of the silicate fine particles in the hydrophilicity imparting agent.
　本発明の親水性付与剤は、被処理物に親水性被膜を形成するための親水性付与剤であって、シリケート又はシリカからなるケイ酸系微粒子と、溶媒とを含有し、前記ケイ酸系微粒子が、最頻値１０ｎｍ以下の小径群と最頻値１５～３０ｎｍの大径群とを含み、前記溶媒中の前記小径群と前記大径群との固形分重量比率が、３：１～１：５であり、前記親水性付与剤における前記ケイ酸系微粒子の配合割合が、０．３重量％～３．０重量％であることを特徴とする。 The hydrophilicity-imparting agent of the present invention is a hydrophilicity-imparting agent for forming a hydrophilic film on an object to be treated, which contains silicate-based fine particles composed of silicate or silica, and a solvent, The fine particles include a small diameter group having a mode value of 10 nm or less and a large diameter group having a mode value of 15 to 30 nm, and the solid content weight ratio of the small diameter group to the large diameter group in the solvent is 3: 1 to 1: 5, and the mixing ratio of the silicic acid-based fine particles in the hydrophilicity-imparting agent is 0.3 wt% to 3.0 wt%.
　前記本発明剤は、前記被処理物に前記親水性被膜を形成するために用いられるものである。前記「被処理物」としては、特に限定されるものではなく、例えば、建物外壁、自動車外装、窓、太陽光パネルの保護カバー等を挙げることができる。 The agent of the present invention is used for forming the hydrophilic film on the object to be treated. The “object to be treated” is not particularly limited, and examples thereof include a building outer wall, an automobile exterior, a window, and a solar panel protective cover.
　本発明において、前記「ケイ酸系微粒子」は、「シリケートの微粒子又はシリカの微粒子、から選ばれた少なくとも一種以上」を意味する。前記シリケート（ケイ酸塩）は、一個又は複数個のケイ素原子を中心として、酸素等の電気陰性な配位子がこれを取り囲んだ構造を持つアニオンと、ナトリウムイオンやアンモニウムイオンなどのカチオンと、を具備する化合物である。一方、前記シリカ（ＳｉＯ２）は、ケイ素原子周りが負電荷を帯びないため、カチオンを具備しないが、ケイ酸塩の一種とされている。 In the present invention, the “silicic acid-based fine particles” mean “at least one selected from silicate fine particles or silica fine particles”. The silicate (silicate) is an anion having a structure in which an electronegative ligand such as oxygen surrounds one or a plurality of silicon atoms, a cation such as sodium ion or ammonium ion, It is a compound which comprises. On the other hand, the silica (SiO 2 ) does not have a negative charge around the silicon atom and thus does not have a cation, but is a kind of silicate.
　ここで、前記本発明剤において、前記ケイ酸系微粒子としてシリカの微粒子を用いた場合、形成された前記親水性被膜の前記被処理物に対する結びつきは、主として分子間力によるものとなる。一方、前記本発明剤において、前記ケイ酸系微粒子としてシリケートの微粒子を用いた場合、形成された前記親水性被膜の前記被処理物に対する結びつきは、前記分子間力に加えて、シラノール反応によって生じたシロキサンによる化学的な結合によるものとなる。 Here, in the agent of the present invention, when silica fine particles are used as the silicic acid-based fine particles, the binding of the formed hydrophilic coating to the object to be processed is mainly due to intermolecular force. On the other hand, in the agent of the present invention, when silicate fine particles are used as the silicic acid-based fine particles, the formed hydrophilic film is bonded to the object by the silanol reaction in addition to the intermolecular force. This is due to chemical bonding by siloxane.
　そして、前記本発明剤では、前記ケイ酸系微粒子として、最頻値１０ｎｍ以下（好ましくは、１～７ｎｍ）の小径群と、最頻値１５～３０ｎｍ（好ましくは、２０～３０ｎｍ）の大径群と、を少なくとも含むものが用いられる。当該ケイ酸系微粒子を含む親水性被膜が形成された被処理物は、粒径の異なるケイ酸系微粒子により表面が親水性となり、かつ、その表面が微細な凹凸のテクスチャー構造となる。その結果、雨が降ると、親水性被膜に付着した汚れと親水性被膜との間に水が入り込み、汚れが浮いて洗い流されるため、当該被処理物は高い自己洗浄性を有するものとなる。 In the agent of the present invention, as the silicic acid-based fine particles, a small diameter group having a mode value of 10 nm or less (preferably 1 to 7 nm) and a large diameter having a mode value of 15 to 30 nm (preferably 20 to 30 nm). And at least a group is used. An object to be processed on which a hydrophilic film containing the silicate fine particles is formed has a surface having a textured structure with fine irregularities due to the silicate fine particles having different particle diameters. As a result, when it rains, water enters between the dirt adhering to the hydrophilic film and the hydrophilic film, and the dirt floats and is washed away, so that the object to be treated has a high self-cleaning property.
　配合前の前記ケイ酸系微粒子のうち最頻値１０ｎｍ以下の小径群の粒子径分布は、７ｎｍ以上の粒子の重量比率が１５％以下であることが好ましく、より好ましくは１０％以下、さらに好ましくは５％以下である。７ｎｍ以上の粒子の重量比率が１５％以下であれば、形成された親水性被膜の耐久性が、より向上するからである。 The particle size distribution of the small-diameter group having a mode value of 10 nm or less among the silicate-based fine particles before blending is preferably 15% or less, more preferably 10% or less, and even more preferably, the weight ratio of particles of 7 nm or more. Is 5% or less. This is because if the weight ratio of particles of 7 nm or more is 15% or less, the durability of the formed hydrophilic coating is further improved.
　配合前の前記ケイ酸系微粒子のうち、最頻値１５～３０ｎｍの大径群の粒子径分布は、１２ｎｍ以下の粒子の重量比率が１５％以下であることが好ましく、より好ましくは１０％以下、さらに好ましくは５％以下である。１２ｎｍ以下の粒子の重量比率が１５％以下であれば、形成された親水性被膜の耐久性が、より向上するからである。 Among the silicate-based fine particles before blending, the particle size distribution of the large-diameter group having a mode value of 15 to 30 nm is preferably such that the weight ratio of particles of 12 nm or less is 15% or less, more preferably 10% or less. More preferably, it is 5% or less. This is because if the weight ratio of particles of 12 nm or less is 15% or less, the durability of the formed hydrophilic coating is further improved.
　本発明において「最頻値」とは、前記ケイ酸系微粒子からなる一群（前記大径群若しくは前記小径群）を母集団とし、レーザー解析・散乱法によって粒度分布測定した場合の、最も出現比率の高い粒径を意味する。本発明においては、前記母集団となる前記ケイ酸系微粒子の一群につき、前記最頻値が、±１０％以内（より好ましくは±５％以内）の相違で平均粒径と一致する正規分布に近い粒度分布を有するものを用いることが好ましい。 In the present invention, the “mode” means the most appearance ratio when the particle size distribution is measured by a laser analysis / scattering method, with a group of the silicate-based fine particles (the large diameter group or the small diameter group) as a population. Means a high particle size. In the present invention, for each group of the silicate-based fine particles as the population, the mode is a normal distribution that matches the average particle diameter with a difference within ± 10% (more preferably within ± 5%). It is preferable to use one having a close particle size distribution.
　なお、前記ケイ酸系微粒子には、アンモニア安定化タイプや、ナトリウム安定化タイプなど、表面処理の違いによる各種タイプが存在するが、本発明においてはいずれのタイプを用いても良い。前記ケイ酸系微粒子としては、ゾルゲル法、水ガラスを原料とした製造法、気相法などの公知の方法に従って製造したシリカの微粒子や、このシリカの微粒子を公知の方法でナトリウム安定化、またはアンモニウム安定化したシリケートの微粒子、または、公知の方法に従って製造したケイ酸アンモニウムを使用することができる。 There are various types of silicic acid-based fine particles depending on the surface treatment, such as an ammonia stabilizing type and a sodium stabilizing type, and any type may be used in the present invention. As the silicate-based fine particles, silica fine particles produced according to a known method such as a sol-gel method, a production method using water glass as a raw material, a gas phase method, and the silica fine particles are stabilized with sodium by a known method, or Ammonium-stabilized silicate microparticles or ammonium silicate prepared according to known methods can be used.
　前記ケイ酸系微粒子の具体的な製造方法としては、例えば、水ガラス法でケイ酸ソーダをイオン交換し、活性ケイ酸を調製後、これを加熱下において、ＮａＯＨでｐＨ調整した種粒子含有水溶液中に添加し、粒子成長させて製造する方法を挙げることができる。また、例えば、アルコキシド法で、ケイ酸アルキル（テトラアルコキシシラン）を塩基性触媒の存在下で加水分解すると同時に縮合・粒子成長を行いながらシリカ粒子を製造する方法も挙げることができる。 As a specific method for producing the silicic acid-based fine particles, for example, ion-exchange of sodium silicate by a water glass method to prepare active silicic acid, and then heating this, the seed particle-containing aqueous solution whose pH is adjusted with NaOH Examples of the method include manufacturing by adding particles and growing the particles. In addition, for example, a method of producing silica particles while performing condensation and particle growth simultaneously with hydrolysis of alkyl silicate (tetraalkoxysilane) in the presence of a basic catalyst by an alkoxide method can also be mentioned.
　又、前記本発明剤では、前記溶媒中に、前記小径群と前記大径群とが、３：１～１：５の固形分重量比率にて配合される。小径群と大径群との固形分重量比率を前記範囲内とすることで、本発明剤によって形成された親水性被膜は、その表面が毛細管現象を引き起こす構造となる。その結果、親水性被膜の表面の親水性が向上する。また、前記小径群と大径群との固形分重量比率は、２：１～１：５であることがより好ましく、さらに好ましくは１：１～１：５、特に好ましくは１：２～１：４である。 In the agent of the present invention, the small diameter group and the large diameter group are blended in the solvent at a solid content weight ratio of 3: 1 to 1: 5. By setting the solid content weight ratio of the small diameter group and the large diameter group within the above range, the hydrophilic coating formed by the agent of the present invention has a structure in which the surface causes capillary action. As a result, the hydrophilicity of the surface of the hydrophilic coating is improved. Further, the solid content weight ratio between the small diameter group and the large diameter group is more preferably 2: 1 to 1: 5, further preferably 1: 1 to 1: 5, and particularly preferably 1: 2 to 1. : 4.
　小径群と大径群の配合後のケイ酸系微粒子の最頻値は、５ｎｍ以上が好ましく、より好ましくは１０ｎｍ以上、さらに好ましくは１５ｎｍ以上であり、２８ｎｍ以下が好ましく、より好ましくは２６ｎｍ以下、さらに好ましくは２４ｎｍ以下である。なお、前記ケイ酸系微粒子の最頻値とは、前記ケイ酸系微粒子を、レーザー解析・散乱法によって粒度分布測定したときに得られる最も出現比率の高い粒径である。 The mode value of the silicate-based fine particles after blending the small diameter group and the large diameter group is preferably 5 nm or more, more preferably 10 nm or more, still more preferably 15 nm or more, preferably 28 nm or less, more preferably 26 nm or less, More preferably, it is 24 nm or less. The mode value of the silicate fine particles is a particle size having the highest appearance ratio obtained when the particle size distribution of the silicate fine particles is measured by a laser analysis / scattering method.
　小径群と大径群の配合後のケイ酸系微粒子を、レーザー解析・散乱法によって粒度分布測定したときに得られる重量基準頻度分布グラフにおいて、前記ケイ酸系微粒子の平均粒子径は、５ｎｍ以上が好ましく、より好ましくは１０ｎｍ以上、さらに好ましくは２０ｎｍ以上であり、５０ｎｍ以下が好ましく、より好ましくは４０ｎｍ以下、さらに好ましくは３０ｎｍ以下である。 In the weight-based frequency distribution graph obtained by measuring the particle size distribution of the silicic acid fine particles after blending the small diameter group and the large diameter group by laser analysis / scattering method, the average particle diameter of the silicic acid fine particles is 5 nm or more. More preferably, it is 10 nm or more, More preferably, it is 20 nm or more, 50 nm or less is preferable, More preferably, it is 40 nm or less, More preferably, it is 30 nm or less.
　小径群と大径群の配合後のケイ酸系微粒子を、レーザー解析・散乱法によって粒度分布測定したときに得られる重量基準頻度分布グラフにおいて、粒子径が１５ｎｍ～２８ｎｍの粒子の重量比率は、３０％以上であることが好ましく、より好ましくは４０％以上、さらに好ましくは５０％以上である。 In the weight-based frequency distribution graph obtained by measuring the particle size distribution of the silicic acid-based fine particles after blending the small diameter group and the large diameter group by laser analysis / scattering method, the weight ratio of particles having a particle diameter of 15 nm to 28 nm is: It is preferably 30% or more, more preferably 40% or more, and further preferably 50% or more.
　前記「溶媒」としては、前記ケイ酸系微粒子を分散し得るものであれば、特に限定されるものではなく、例えば、水や、アルコール等の有機溶媒から選択された液状媒体を単独、又は混合して用いることができる。前記被処理物に対する本発明剤の濡れ性を向上させる観点からは、イソプロピルアルコール等の低級アルコールを前記溶媒として用いることが好ましい。但し、溶媒として前記低級アルコールを用いる場合にあっては、消泡性及び引火性を鑑みて、水を４０重量％以上（好ましくは、５０重量％以上）配合することが好ましい。 The “solvent” is not particularly limited as long as it can disperse the silicate-based fine particles. For example, a liquid medium selected from water and an organic solvent such as alcohol is used alone or in combination. Can be used. From the viewpoint of improving the wettability of the agent of the present invention to the object to be treated, it is preferable to use a lower alcohol such as isopropyl alcohol as the solvent. However, when the lower alcohol is used as a solvent, it is preferable to add water in an amount of 40% by weight or more (preferably 50% by weight or more) in view of defoaming properties and flammability.
　本発明剤の親水性付与剤における前記ケイ酸系微粒子の配合割合は、０．３重量％～３．０重量％であることが好ましい。ケイ酸系微粒子の配合割合が低すぎる、あるいは、高すぎると、被処理物に所定量塗布した場合に、被処理物の光線透過率が低下する場合がある。また、ケイ酸系微粒子の配合割合が低すぎると、被膜を形成するために、親水性付与剤を塗布する回数が増加するので好ましくない。前記配合割合は、好ましくは０．４重量％以上であり、より好ましくは０．５重量％以上であり、さらに好ましくは１．０重量％以上であり、好ましくは２．５重量％以下、より好ましくは２．０重量％以下である。 The blending ratio of the silicic acid-based fine particles in the hydrophilicity imparting agent of the present invention agent is preferably 0.3% by weight to 3.0% by weight. If the mixing ratio of the silicic acid fine particles is too low or too high, the light transmittance of the object to be processed may decrease when a predetermined amount is applied to the object to be processed. On the other hand, if the mixing ratio of the silicic acid-based fine particles is too low, the number of times of applying the hydrophilicity-imparting agent is increased in order to form a film, which is not preferable. The blending ratio is preferably 0.4% by weight or more, more preferably 0.5% by weight or more, further preferably 1.0% by weight or more, preferably 2.5% by weight or less, more Preferably it is 2.0 weight% or less.
　より具体的な例を挙げると、被処理物がＡＲコートされた保護カバーを有する太陽光パネルの場合にあっては、前記ケイ酸系微粒子の配合割合を０．５±０．２重量％とすることが好ましい。 To give a more specific example, in the case of a solar panel having an AR-coated protective cover as an object to be processed, the blending ratio of the silicate-based fine particles is 0.5 ± 0.2% by weight. It is preferable to do.
　一方、被処理物がＡＲコートされた保護カバーを有する太陽光パネル以外の場合（ＡＲコートされていない保護カバーを有する太陽光パネルを含む）にあっては、前記ケイ酸系微粒子の配合割合を、１．５±０．５重量％とすることが好ましい。 On the other hand, when the object to be processed is other than a solar panel having an AR-coated protective cover (including a solar panel having an AR-coated protective cover), the mixing ratio of the silicate-based fine particles is 1.5 ± 0.5 wt% is preferable.
　なお、本発明剤においては、前記溶媒中に前記ケイ酸系微粒子以外の成分を含むことを否定するものではなく、例えば、帯電防止剤等の所望の成分が配合されていても良い。 In addition, in this invention agent, it does not deny containing components other than the said silicic acid type microparticles | fine-particles in the said solvent, For example, desired components, such as an antistatic agent, may be mix | blended.
　本発明の親水性被膜形成方法は、被処理物に親水性被膜を形成する親水性被膜形成方法であって、最頻値１０ｎｍ以下の小径群と最頻値１５～３０ｎｍの大径群とを少なくとも含むシリケート又はシリカからなるケイ酸系微粒子が、前記小径群と前記大径群とが３：１～１：５の固形分重量比となるように溶媒に配合され、前記ケイ酸系微粒子の配合割合が０．３重量％～３．０重量％である親水性付与剤を、前記被処理物に、一ないし複数回塗布する塗布工程を実行することを特徴とする（以下、「本発明方法」と称する。）。 The hydrophilic film forming method of the present invention is a hydrophilic film forming method for forming a hydrophilic film on an object to be treated, and comprises a small diameter group having a mode value of 10 nm or less and a large diameter group having a mode value of 15 to 30 nm. Silicate-based fine particles composed of at least silicate or silica are mixed in a solvent so that the small diameter group and the large diameter group have a solid content weight ratio of 3: 1 to 1: 5. An application step of applying a hydrophilicity-imparting agent having a blending ratio of 0.3 wt% to 3.0 wt% to the object to be processed one or more times is performed (hereinafter referred to as “the present invention”). Referred to as "method").
　前記本発明剤は、前記溶媒中に前記小径群と前記大径群とを共存させた一液タイプのものとなされているが、前記本発明方法を実行するにあたっては、例えば、前記溶媒中に前記小径群を分散させた第一薬液と、前記溶媒中に前記大径群を分散させた第二薬液とを、準備し、前記塗布工程実行時に混合する二液混合タイプを親水性付与剤として用いても良い。又、前記ケイ酸系微粒子を過剰に含んでなる原液を準備し、前記塗布工程実行時に前記溶媒にて希釈することによって所望の濃度の親水性付与剤を調整しても良い。勿論、前記本発明方法を実行するにあたり、前記本発明剤と同様の一液タイプを用いても良い。 The agent of the present invention is a one-component type in which the small-diameter group and the large-diameter group coexist in the solvent. In carrying out the method of the present invention, for example, in the solvent As a hydrophilicity-imparting agent, a first chemical solution in which the small-diameter group is dispersed and a second chemical solution in which the large-diameter group is dispersed in the solvent are prepared and mixed at the time of performing the coating process. It may be used. Alternatively, a stock solution containing an excessive amount of the silicic acid-based fine particles may be prepared, and the hydrophilicity-imparting agent having a desired concentration may be adjusted by diluting with the solvent during execution of the coating process. Of course, in executing the method of the present invention, the same one-component type as the agent of the present invention may be used.
　前記本発明方法において、前記本発明剤と同様の一液タイプの親水性付与剤を用いる場合、例えば、最頻値１０ｎｍ以下の小径群のケイ酸系微粒子を分散媒に分散させた第一原液と、最頻値１５ｎｍ～３０ｎｍの大径群のケイ酸系微粒子を分散媒に分散させた第二原液と、希釈剤とを混合することで、所望の濃度の一液タイプの親水性付与剤を調製してもよい。これらの分散媒、希釈剤としては、前記溶媒として使用できるものと同じものが使用できる。なお、この方法で調製された親水性付与剤において、「溶媒」は、第一原液の分散媒と、第二原液の分散媒と、希釈剤とで構成される。 In the method of the present invention, when a one-component type hydrophilicity imparting agent similar to the agent of the present invention is used, for example, a first stock solution in which silicate-based fine particles of a small diameter group having a mode value of 10 nm or less are dispersed in a dispersion medium. And a second stock solution in which a silicate-based fine particle of a large diameter group having a mode value of 15 nm to 30 nm is dispersed in a dispersion medium, and a diluent, thereby mixing a one-component type hydrophilicity imparting agent having a desired concentration. May be prepared. As these dispersion media and diluents, the same ones that can be used as the solvent can be used. In the hydrophilicity imparting agent prepared by this method, the “solvent” is composed of a dispersion medium of the first stock solution, a dispersion medium of the second stock solution, and a diluent.
　最頻値１０ｎｍ以下の小径群のケイ酸系微粒子を分散させた第一原液中、固形分であるケイ酸系微粒子の濃度は、５重量％～３０重量％が好ましく、７重量％～２５重量％がより好ましく、１０重量％～２０重量％がさらに好ましい。 In the first stock solution in which small-diameter silicate particles having a mode value of 10 nm or less are dispersed, the concentration of the silicate particles as a solid content is preferably 5% by weight to 30% by weight, and preferably 7% by weight to 25% by weight. % Is more preferable, and 10% by weight to 20% by weight is more preferable.
　最頻値１５ｎｍ～３０ｎｍの大径群のケイ酸系微粒子を分散させた第二原液中、固形分であるケイ酸系微粒子の濃度は、１０重量％～６０重量％が好ましく、１５重量％～５０重量％がより好ましく、２５重量％～４０重量％がさらに好ましい。 In the second stock solution in which the large-diameter silicate fine particles having a mode value of 15 nm to 30 nm are dispersed, the concentration of the silicate fine particles as a solid content is preferably 10 wt% to 60 wt%, preferably 15 wt% to 50% by weight is more preferable, and 25% by weight to 40% by weight is further preferable.
　本発明方法においては、前記塗布工程における親水性付与剤の塗布量を、乾燥重量で３０ｍｇ／ｍ２～３００ｍｇ／ｍ２とすることが好ましい。塗布量をこの範囲内とすることで、被処理物の光線透過率を向上させることができる。塗布量が３０ｍｇ／ｍ２未満である場合、親水性の付与効果が小さくなる。また、光線透過率向上効果も小さくなる。一方、塗布量が、３００ｍｇ／ｍ２超である場合、光線透過率向上効果が低下する。被処理物に対する親水性付与剤の塗布量は、乾燥重量で、より好ましくは４５ｍｇ／ｍ２以上、さらに好ましくは５０ｍｇ／ｍ２以上、特に好ましくは７５ｍｇ／ｍ２以上、最も好ましくは１００ｍｇ／ｍ２以上であり、より好ましくは２５０ｍｇ／ｍ２以下、さらに好ましくは２００ｍｇ／ｍ２以下、特に好ましくは１５０ｍｇ／ｍ２以下である。 In the method of the present invention, the coating amount of the hydrophilic agent in the coating step, it is preferable to 30mg / m 2 ~ 300mg / m 2 by dry weight. By setting the coating amount within this range, the light transmittance of the object to be processed can be improved. When the coating amount is less than 30 mg / m 2 , the hydrophilic effect is reduced. Moreover, the light transmittance improvement effect is also reduced. On the other hand, when the coating amount is more than 300 mg / m 2 , the light transmittance improving effect is lowered. The coating amount of the hydrophilicity-imparting agent on the object to be treated is more preferably 45 mg / m 2 or more, more preferably 50 mg / m 2 or more, particularly preferably 75 mg / m 2 or more, and most preferably 100 mg / m, in terms of dry weight. 2 or more, more preferably 250 mg / m 2 or less, further preferably 200 mg / m 2 or less, and particularly preferably 150 mg / m 2 or less.
　前記本発明方法においては、前記塗布工程の実行前に、ポリシラザンを少なくとも含む下処理剤を、前記被処理物に塗布する下処理工程を実行することが好ましい態様となる。 In the method of the present invention, it is preferable to perform a pretreatment step of applying a pretreatment agent containing at least polysilazane to the object to be treated before the execution of the coating step.
　前記ポリシラザンは、「‐（ＳｉＨ２ＮＨ）‐」を基本ユニットとする無機ポリマーである。このポリシラザンが有機溶媒等に溶解された下処理剤を前記被処理物に塗布すれば、大気中の水分と反応して脱アンモニア反応が起こり、前記被処理物との密着性に優れた緻密なシリカ被膜が形成される。前記脱アンモニア反応は、比較的ゆっくりと進むため、前記塗布工程の実行前に、前記下処理工程を実行すれば、前記被処理物に対する前記親水性被膜の結びつきがより強固になり、前記親水性被膜の耐久性が向上する。 The polysilazane is an inorganic polymer having “— (SiH 2 NH) —” as a basic unit. When a pretreatment agent in which this polysilazane is dissolved in an organic solvent or the like is applied to the object to be treated, a deammonia reaction occurs due to a reaction with moisture in the atmosphere, and a dense material having excellent adhesion to the object to be treated. A silica coating is formed. Since the deammonification reaction proceeds relatively slowly, if the pretreatment step is performed before the coating step, the hydrophilic film is more strongly bonded to the object to be processed, and the hydrophilic property is increased. The durability of the coating is improved.
　前記下処理剤中に含まれる前記ポリシラザンの配合割合は、塗布量や塗布回数に応じて決定されるものであり、特に限定されるものではないが、０．１～１重量％の範囲内（より好ましくは、０．３～０．７重量％の範囲内）とすることが好ましい。 The blending ratio of the polysilazane contained in the pretreatment agent is determined according to the coating amount and the number of coatings, and is not particularly limited, but is within the range of 0.1 to 1% by weight ( More preferably, it is within the range of 0.3 to 0.7% by weight.
　本発明の親水性被膜は、シリケート又はシリカからなるケイ酸系微粒子を含む親水性皮膜であって、前記ケイ酸系微粒子が、最頻値１０ｎｍ以下の小径群と最頻値１５～３０ｎｍの大径群とを含み、前記小径群と前記大径群との固形分重量比率が、３：１～１：５の重量比率であることを特徴とする（以下、「本発明被膜」と称する。）。 The hydrophilic coating of the present invention is a hydrophilic coating containing silicate fine particles made of silicate or silica, and the silicate fine particles have a small diameter group with a mode value of 10 nm or less and a large size with a mode value of 15 to 30 nm. The solid content weight ratio of the small diameter group and the large diameter group is a weight ratio of 3: 1 to 1: 5 (hereinafter referred to as “the coating film of the present invention”). ).
　本発明被膜は、被処理物上に、乾燥重量で、３０ｍｇ／ｍ２以上となるように設けられていることが好ましく、より好ましくは４５ｍｇ／ｍ２以上、さらに好ましくは７５ｍｇ／ｍ２以上、特に好ましくは１００ｍｇ／ｍ２以上であり、３００ｍｇ／ｍ２以下となるように設けられていることが好ましく、より好ましくは２５０ｍｇ／ｍ２以下、さらに好ましくは２００ｍｇ／ｍ２以下、特に好ましくは１５０ｍｇ／ｍ２以下である。塗布量が、乾燥重量で前記範囲内であれば、光線透過率が高く、親水性に優れる被膜が得られる。 The coating of the present invention is preferably provided on the object to be treated so that the dry weight is 30 mg / m 2 or more, more preferably 45 mg / m 2 or more, still more preferably 75 mg / m 2 or more, It is particularly preferably 100 mg / m 2 or more, preferably 300 mg / m 2 or less, more preferably 250 mg / m 2 or less, further preferably 200 mg / m 2 or less, particularly preferably 150 mg. / M 2 or less. When the coating amount is within the above range in terms of dry weight, a film having high light transmittance and excellent hydrophilicity can be obtained.
　前記本発明被膜においては、接触角１０度以下の親水性を有するものが好ましく、７度以下の親水性を有するものがより好ましく、５度以下の親水性を有するものがさらに好ましい態様となる。 In the coating of the present invention, those having a contact angle of 10 degrees or less are preferred, those having a hydrophilicity of 7 degrees or less are more preferred, and those having a hydrophilicity of 5 degrees or less are a more preferred embodiment.
　本発明の太陽光パネルは、保護カバーの表面に、前記本発明被膜が形成されてなることを特徴とする（以下、「本発明パネル」と称する。）。本発明の太陽光パネルは、太陽電池モジュールが少なくとも１枚配置されてなる。前記太陽電池モジュールは、太陽電池セル層と、前記太陽電池セル層の上面に設けられた保護カバーと、前記太陽電池セル層の下面に設けられたバックシートとを有することが好ましい。保護カバーは、一般に強化ガラスである。また、ＡＲコート（反射防止被膜）は、保護カバーの表面に設けられる。 The solar panel of the present invention is characterized in that the film of the present invention is formed on the surface of a protective cover (hereinafter referred to as “the present invention panel”). The solar panel of the present invention includes at least one solar cell module. The solar cell module preferably includes a solar cell layer, a protective cover provided on the upper surface of the solar cell layer, and a back sheet provided on the lower surface of the solar cell layer. The protective cover is generally tempered glass. An AR coat (antireflection coating) is provided on the surface of the protective cover.
　以下、本発明を実施するための形態を説明するが、本発明はこの実施形態に限定されるものではない。 Hereinafter, although the form for implementing this invention is demonstrated, this invention is not limited to this embodiment.
　下記表１～３に実施例１～２４に係る本発明剤の処方、及び比較例１～１８に係る薬液の処方を示す。各実施例に係る本発明剤、及び各比較例に係る薬液は、大径群と小径群の固形分の重量比が各表中に記載の値となるように、小径群のケイ酸系微粒子を水に分散させた第一原液、および／または、最頻値１５ｎｍ～３０ｎｍの大径群のケイ酸系微粒子を水に分散させた第二原液を、水、または、水とＩＰＡの混合液で希釈することによって調製したものである。なお、実施例４、１２および２０は、第一原液中の水、第二原液中の水、および、前記混合液中の水の合計重量と、前記混合液中のＩＰＡの重量との比率が、１：１となるように調製した。 Tables 1 to 3 below show prescriptions of the present invention according to Examples 1 to 24 and prescriptions of chemical solutions according to Comparative Examples 1 to 18. The inventive agent according to each example and the chemical solution according to each comparative example are prepared in such a manner that the weight ratio of the solid content of the large diameter group and the small diameter group becomes a value described in each table. A first stock solution in which water is dispersed in water and / or a second stock solution in which silicate-based fine particles of a large diameter group having a mode value of 15 to 30 nm are dispersed in water, water, or a mixture of water and IPA It was prepared by diluting with. In Examples 4, 12 and 20, the ratio of the total weight of water in the first stock solution, the water in the second stock solution, and the water in the mixed solution to the weight of IPA in the mixed solution is as follows. It was prepared to be 1: 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　実施例１において、小径群と大径群との固形分重量比率を３：１で配合したケイ酸系微粒子は、重量換算の平均粒子径が２５．９ｎｍであった。
　実施例２において、小径群と大径群との固形分重量比率を１：５で配合したケイ酸系微粒子は、重量換算の平均粒子径が２３．７ｎｍであった。
　実施例３において、小径群と大径群との固形分重量比率を１：３で配合したケイ酸系微粒子は、重量換算の平均粒子径が２１．７ｎｍであった。
　比較例２のケイ酸系微粒子は、重量換算の平均粒子径が３．５ｎｍであった。
　比較例５のケイ酸系微粒子は、重量換算の平均粒子径が２６．８ｎｍであった。
　実施例１８において、小径群と大径群との固形分重量比率を１：５で配合したケイ酸系微粒子は、最頻値が１８．７ｎｍ、重量換算の平均粒子径が２３．７ｎｍ、分布として１８ｎｍ～２３ｎｍの重量比率が５０％以上であった。
　実施例１９において、小径群と大径群との固形分重量比率を１：３で配合したケイ酸系微粒子は、最頻値が１７．３ｎｍ、重量換算の平均粒子径が２１．７ｎｍ、分布として１５ｎｍ～１８ｎｍの重量比率が５０％以上であった。 In Example 1, the silicic acid-based fine particles in which the solid content weight ratio of the small diameter group and the large diameter group was blended at 3: 1 had an average particle diameter in terms of weight of 25.9 nm.
In Example 2, the silicic acid-based fine particles in which the solid content weight ratio of the small diameter group and the large diameter group was blended at 1: 5 had an average particle diameter in terms of weight of 23.7 nm.
In Example 3, the silicic acid-based fine particles in which the solid content weight ratio of the small diameter group and the large diameter group was blended at 1: 3 had an average particle diameter in terms of weight of 21.7 nm.
The average particle diameter in terms of weight of the silicic acid-based fine particles of Comparative Example 2 was 3.5 nm.
The average particle diameter in terms of weight of the silicic acid-based fine particles of Comparative Example 5 was 26.8 nm.
In Example 18, the silicic acid-based fine particles in which the solid weight ratio between the small diameter group and the large diameter group was blended at a ratio of 1: 5 had a mode value of 18.7 nm, a weight-converted average particle diameter of 23.7 nm, and distribution. As a result, the weight ratio of 18 nm to 23 nm was 50% or more.
In Example 19, the silicic acid-based fine particles in which the solid weight ratio of the small diameter group and the large diameter group was blended at 1: 3 had a mode value of 17.3 nm, a weight-converted average particle diameter of 21.7 nm, and distribution. As a result, the weight ratio of 15 nm to 18 nm was 50% or more.
　表１では、以下の原料を用いた。
［第一原液］
最頻値１ｎｍ：最頻値が１ｎｍ、固形分濃度が１０重量％のケイ酸系微粒子（アンモニア安定化タイプ非晶質シリカ）の水分散液
最頻値５ｎｍ：最頻値が５ｎｍ、固形分濃度が１５重量％のケイ酸系微粒子（アンモニア安定化タイプ非晶質シリカ）の水分散液
最頻値１０ｎｍ：最頻値が１０ｎｍ、固形分濃度が２０重量％のケイ酸系微粒子（アンモニア安定化タイプ非晶質シリカ）の水分散液
［第二原液］
最頻値１５ｎｍ：最頻値が１５ｎｍ、固形分濃度が２０重量％のケイ酸系微粒子（アンモニア安定化タイプ非晶質シリカ）の水分散液
最頻値２５ｎｍ：最頻値が２５ｎｍ、固形分濃度が４０重量％のケイ酸系微粒子（アンモニア安定化タイプ非晶質シリカ）の水分散液
最頻値３０ｎｍ：最頻値が３０ｎｍ、固形分濃度が４０重量％のケイ酸系微粒子（アンモニア安定化タイプ非晶質シリカ）の水分散液 In Table 1, the following raw materials were used.
[First stock solution]
Mode value 1 nm: Mode value 1 nm, Silica-based fine particles (ammonia-stabilized amorphous silica) having a solid content concentration of 10% by weight Aqueous dispersion mode value 5 nm: Mode value 5 nm, solid content Silica-based fine particles having a concentration of 15% by weight (ammonia-stabilized amorphous silica) mode of aqueous dispersion 10 nm: Silicate-based fine particles having a mode value of 10 nm and a solid concentration of 20% by weight (ammonia stable) Type amorphous silica) aqueous dispersion [second stock solution]
Mode value 15 nm: Mode value 15 nm, Silica-based fine particles (ammonia-stabilized amorphous silica) having a solid content concentration of 20% by weight Aqueous dispersion mode value 25 nm: Mode value 25 nm, solid content Silica-based fine particles (ammonia-stabilized amorphous silica) with a concentration of 40% by weight in aqueous dispersion mode 30 nm: mode value 30 nm, solid content concentration 40% by weight of silicate-based fine particles (ammonia stable Amorphous silica) aqueous dispersion
　表２では、以下の原料を用いた。
［第一原液］
最頻値１ｎｍ：最頻値が１ｎｍ、固形分濃度が１０重量％のケイ酸系微粒子（ナトリウム安定化タイプ非晶質シリカ）の水分散液
最頻値５ｎｍ：最頻値が５ｎｍ、固形分濃度が１５重量％のケイ酸系微粒子（ナトリウム安定化タイプ非晶質シリカ）の水分散液
最頻値１０ｎｍ：最頻値が１０ｎｍ、固形分濃度が２０重量％のケイ酸系微粒子（ナトリウム安定化タイプ非晶質シリカ）の水分散液
［第二原液］
最頻値１５ｎｍ：最頻値が１５ｎｍ、固形分濃度が２０重量％のケイ酸系微粒子（ナトリウム安定化タイプ非晶質シリカ）の水分散液
最頻値２５ｎｍ：最頻値が２５、固形分濃度が４０重量％のケイ酸系微粒子（ナトリウム安定化タイプ非晶質シリカ）の水分散液
最頻値３０ｎｍ：最頻値が３０ｎｍ、固形分濃度が４０重量％のケイ酸系微粒子（ナトリウム安定化タイプ非晶質シリカ）の水分散液 In Table 2, the following raw materials were used.
[First stock solution]
Mode value 1 nm: Mode dispersion value 1 nm, Silica-based fine particles (sodium-stabilized amorphous silica) having a solid content concentration of 10% by weight Aqueous dispersion mode value 5 nm: Mode value 5 nm, solid content Silica-based fine particles having a concentration of 15% by weight (sodium-stabilized amorphous silica) in an aqueous dispersion mode of 10 nm: Silica-based fine particles having a mode value of 10 nm and a solid content concentration of 20% by weight (sodium-stable Type amorphous silica) aqueous dispersion [second stock solution]
Mode value 15 nm: Mode dispersion value 15 nm, Silica-based fine particles (sodium-stabilized amorphous silica) having a solid content concentration of 20% by weight Aqueous dispersion mode value 25 nm: Mode value 25, solid content Silica-based fine particles (sodium-stabilized amorphous silica) with a concentration of 40% by weight in aqueous dispersion mode value 30 nm: Silicate-based fine particles with a mode value of 30 nm and a solid content concentration of 40% by weight (sodium stable) Amorphous silica) aqueous dispersion
　表３では、以下の原料を用いた。
［第一原液］
最頻値１ｎｍ：最頻値が１ｎｍ、固形分濃度が１０重量％のケイ酸系微粒子（ケイ酸アンモニウム）の水分散液
最頻値５ｎｍ：最頻値が５ｎｍ、固形分濃度が１５重量％のケイ酸系微粒子（ケイ酸アンモニウム）の水分散液
最頻値１０ｎｍ：最頻値が１０ｎｍ、固形分濃度が２０重量％のケイ酸系微粒子（ケイ酸アンモニウム）の水分散液
［第二原液］
最頻値１５ｎｍ：最頻値が１５ｎｍ、固形分濃度が２０重量％のケイ酸系微粒子（ケイ酸アンモニウム）の水分散液
最頻値２５ｎｍ：最頻値が２５ｎｍ、固形分濃度が４０重量％のケイ酸系微粒子（ケイ酸アンモニウム）の水分散液
最頻値３０ｎｍ：最頻値が３０ｎｍ、固形分濃度４０重量％のケイ酸系微粒子（ケイ酸アンモニウム）の水分散液 In Table 3, the following raw materials were used.
[First stock solution]
Mode value: 1 nm: Mode dispersion value of 1 nm, solid dispersion concentration of 10 wt% silicate fine particles (ammonium silicate) in aqueous dispersion mode: 5 nm: Mode value of 5 nm, solid content concentration of 15 wt% Silica fine particles (ammonium silicate) aqueous dispersion mode value 10 nm: Mode dispersion value 10 nm, solid content concentration 20 wt% silicate fine particles (ammonium silicate) aqueous dispersion [second stock solution ]
Mode 15 nm: Mode dispersion value 15 nm, solid dispersion concentration 20 wt% silicate fine particles (ammonium silicate) aqueous dispersion mode 25 nm: Mode value 25 nm, solid content concentration 40 wt% Silica fine particles (ammonium silicate) aqueous dispersion mode value 30 nm: Mode dispersion value 30 nm, solid content concentration 40 wt% of silicate fine particles (ammonium silicate) aqueous dispersion
－粒子径の測定－
　使用するケイ酸系微粒子をレーザー回折粒子径測定装置（大塚電子社製、型番：ＦＰＡＲ―１０００）の湿式の測定セルにセットし、試料屈折率を１．３３１３として粒子径を測定した。得られた重量基準頻度分布グラフ（対数プロットの粒子径１ｎｍ～１００００ｎｍを４５分割して得られる頻度分布）から、平均粒径、最頻値および、粒子の重量比率を求めた。 -Measurement of particle size-
The silicic acid type fine particles to be used were set in a wet measuring cell of a laser diffraction particle size measuring device (manufactured by Otsuka Electronics Co., Ltd., model number: FPAR-1000), and the particle size was measured with a sample refractive index of 1.3313. From the obtained weight-based frequency distribution graph (frequency distribution obtained by dividing the logarithmic plot particle diameter of 1 nm to 10000 nm into 45), the average particle diameter, the mode value, and the weight ratio of the particles were obtained.
＜試験１＞
‐被処理物‐
　ＡＲコートがなされた太陽光パネル用の保護カバー
‐本発明剤‐
　表1～３の実施例１～２４に示した固形分重量比率で、小径群と大径群とを配合したケイ酸系微粒子の配合割合を０．５±０．２重量％とした親水性付与剤
‐本発明方法‐
　前記保護カバーの表面に本発明剤を塗布する塗布工程を実行することによって、本発明被膜を形成する。なお、本発明方法の実行は、下処理工程を実行しない場合と、下処理工程を実行する場合と、の二通りを行った。 <Test 1>
-Workpiece-
Protective cover for solar panels with AR coating -The present invention-
Hydrophilicity in which the mixing ratio of the silicic acid-based fine particles in which the small diameter group and the large diameter group are mixed in the solid content weight ratio shown in Examples 1 to 24 in Tables 1 to 3 is 0.5 ± 0.2 wt%. Giving agent-method of the present invention-
The coating film of the present invention is formed by executing a coating step of coating the agent of the present invention on the surface of the protective cover. In addition, execution of the method of the present invention was performed in two ways: when the pretreatment process was not executed and when the pretreatment process was executed.
‐下処理工程を実行しない場合（ＮＰＣ）‐
　前記保護カバーの片側面を水溶性シリコンオフにて脱脂洗浄した後、前記本発明剤を均一に塗布（ウエットで１０ｇ／ｍ２）する塗布工程を実行し、もって、前記保護カバーの片側面に本発明被膜を形成する。 -When the pretreatment process is not executed (NPC)-
After degreasing and cleaning one side of the protective cover with water-soluble silicon off, an application step of uniformly applying the agent of the present invention (10 g / m 2 by wet) is performed, and thus, on one side of the protective cover The coating film of the present invention is formed.
‐下処理工程を実行する場合（ＰＣ）‐
　前記保護カバーの片側面を水溶性シリコンオフにて脱脂洗浄した後、下処理剤（０．５重量％ポリシラザン水溶液）を均一に塗布（１０ｍｌ／ｍ２（２５℃））する下処理工程を実行する。１５分の自然乾燥の後、前記本発明剤を均一に塗布（ウエットで１０ｇ／ｍ２（２５℃））する塗布工程を実行し、もって、前記保護カバーの片側面に本発明被膜を形成する。 -When executing the pretreatment process (PC)-
After degreasing and cleaning one side of the protective cover with water-soluble silicon off, a pretreatment step is performed in which a pretreatment agent (0.5 wt% polysilazane aqueous solution) is uniformly applied (10 ml / m 2 (25 ° C.)). To do. After natural drying for 15 minutes, an application step of uniformly applying the agent of the present invention (10 g / m 2 (25 ° C.) by wet) is performed, thereby forming the coating of the present invention on one side of the protective cover. .
＜評価試験＞
‐濡れ性の評価‐
　前記塗布工程の実行の際に、前記保護カバーに対する前記本発明剤の濡れ性（塗り易さ）を評価する。なお、濡れ性を評価する記号は、◎◎を最良とし、以下、◎→○→△→×の順に濡れ性が劣っていることを意味する。 <Evaluation test>
-Evaluation of wettability-
During the execution of the coating step, the wettability (ease of application) of the agent of the present invention with respect to the protective cover is evaluated. The symbol for evaluating the wettability means that ◎ 最 良 is the best, and hereinafter, the wettability is inferior in the order of →→ ○ → Δ → x.
‐接触角の測定‐
　又、前記塗布工程を実行した後、１２時間自然乾燥させることによって、前記保護カバーの片側面に本発明被膜を形成させ、接触角を測定する。なお、前記接触角は、前記本発明被膜の表面に蒸留水１μｌを滴下し、１秒経過時の水滴の接触角を、接触角測定装置（ＣＡＸ‐１５０（協和界面化学株式会社製））にて測定することによって得られた値である。 -Measurement of contact angle-
Moreover, after performing the said application | coating process, this invention film is formed in the one side of the said protective cover by air-drying for 12 hours, and a contact angle is measured. The contact angle was determined by dropping 1 μl of distilled water onto the surface of the coating of the present invention, and measuring the contact angle of the water drop after 1 second with a contact angle measuring device (CAX-150 (manufactured by Kyowa Interface Chemical Co., Ltd.)). It is the value obtained by measuring.
‐耐摩耗性の評価‐
　更に、前記保護カバーの片側面に形成された前記本発明被膜を、洗車用スポンジで縦横一回ずつ擦り、水道水で洗い流した後、ウェスにて拭き上げるといった摩耗工程を複数回繰り返す。そして、前記摩耗工程を五回施行する度に前記接触角を測定し、前記摩耗工程を何回施行すれば親水性が喪失されるかを評価した。なお、耐摩耗性を評価する記号は、下記を意味するものとする。
　◎：５０回施行後も接触角を維持する。
　○：４０回施行後まで接触角を維持する。
　△：３０回施行後まで接触角を維持する。
　×：３０回施行までに接触角が大きくなる。 -Evaluation of wear resistance-
Further, the wear process in which the coating of the present invention formed on one side surface of the protective cover is rubbed once and vertically with a car wash sponge, rinsed with tap water, and then wiped up with a waste cloth is repeated a plurality of times. The contact angle was measured every time the wear process was performed five times, and it was evaluated how many times the wear process was performed to lose hydrophilicity. In addition, the symbol which evaluates abrasion resistance shall mean the following.
A: The contact angle is maintained even after 50 times.
○: The contact angle is maintained until after 40 times.
Δ: The contact angle is maintained until 30 times.
X: The contact angle increases by 30 times.
‐自己洗浄性の評価‐
　前記保護カバーの片側面に形成された前記本発明被膜に、試験用粉体１の８種（ＪＩＳ　Ｚ　８９０１：２００６）を５ｇ／ｍ２散布した。散布後の本発明被膜を、３０秒間、水で洗浄した後、残留汚染を目視にて評価することにより、自己洗浄性を評価した。自己洗浄性を評価した結果を表す記号を、下記に示す。
　◎：まったく残留しない。
　○：わずかに残留する
　△：少し残留する。
　×：ほとんど残留する。 -Evaluation of self-cleaning properties-
Eight kinds (JIS Z 8901: 2006) of the test powder 1 were sprayed at 5 g / m 2 on the coating of the present invention formed on one side of the protective cover. After the sprayed coating of the present invention was washed with water for 30 seconds, the residual contamination was visually evaluated to evaluate self-cleaning properties. Symbols representing the results of evaluating self-cleaning properties are shown below.
A: No residue at all.
○: Slightly remains Δ: Slightly remains
X: Almost remains.
　前記評価試験の結果を下記表４に示す。 The results of the evaluation test are shown in Table 4 below.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
＜比較試験１＞
　比較試験として、前記比較例１～１８に係る薬液（ケイ酸系微粒子の配合割合を０．５±０．２重量％）を用い、前記試験１に準じて、前記保護カバーの片側面に形成した被膜についても同様の条件下で評価した。結果を下記表５に示す。 <Comparison test 1>
As a comparative test, the chemical solutions according to Comparative Examples 1 to 18 (the blending ratio of silicate-based fine particles was 0.5 ± 0.2 wt%) were used and formed on one side of the protective cover according to Test 1. The coated film was also evaluated under the same conditions. The results are shown in Table 5 below.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
＜試験２＞
‐被処理物‐
　ＡＲコートがなされていない太陽光パネル用の保護カバー
‐本発明剤‐
　表1～３の実施例１～２４に示した固形分重量比率で、小径群と大径群とを配合したケイ酸系微粒子の配合割合を１．５±０．２重量％とした親水性付与剤
‐本発明方法‐
　前記保護カバーの表面に本発明剤を塗布する塗布工程を実行することによって、本発明被膜を形成する（その余は、試験１と同様）。 <Test 2>
-Workpiece-
Protective cover for solar panels without AR coating -Invention agent-
Hydrophilicity in which the mixing ratio of the silicic acid-based fine particles in which the small diameter group and the large diameter group are mixed in the solid content weight ratio shown in Examples 1 to 24 in Tables 1 to 3 is 1.5 ± 0.2 wt%. Giving agent-method of the present invention-
The coating of the present invention is formed by executing the coating step of coating the agent of the present invention on the surface of the protective cover (the rest is the same as in Test 1).
＜評価試験＞
　試験１と同様にして、濡れ性、接触角、耐摩耗性を評価する。前記評価試験の結果を下記表６に示す。 <Evaluation test>
In the same manner as in Test 1, wettability, contact angle, and wear resistance are evaluated. The results of the evaluation test are shown in Table 6 below.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
＜比較試験２＞
　比較試験として、前記比較例１～１８に係る薬液（ケイ酸系微粒子の配合割合を１．５±０．２重量％）を用い、前記試験２に準じて、前記保護カバーの片側面に形成した被膜についても同様の条件下で評価した。結果を下記表７に示す。 <Comparison test 2>
As a comparative test, the chemical solution according to Comparative Examples 1 to 18 (the blending ratio of silicate-based fine particles is 1.5 ± 0.2% by weight) is formed on one side surface of the protective cover according to Test 2. The coated film was also evaluated under the same conditions. The results are shown in Table 7 below.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
＜考察＞
‐濡れ性‐
　濡れ性については、前記ケイ酸系微粒子の最頻値が大きくなるにつれて悪くなる傾向が確認された（表５、表７参照）。但し、前記ケイ酸系微粒子中に前記大径群と前記小径群とを共存させてなる本発明剤については、いずれも十分に良好な濡れ性を示すことが確認された（表４、表６参照）。又、溶媒として水のみを用いた場合よりも、溶媒として低級アルコールを含む液状媒体を用いた場合の方が、良好な濡れ性を示すことが確認された。 <Discussion>
-Wettability-
About the wettability, the tendency which became worse as the mode value of the said silicic acid type fine particle became large was confirmed (refer Table 5 and Table 7). However, it was confirmed that all of the agents of the present invention in which the large-diameter group and the small-diameter group coexist in the silicic acid-based fine particles exhibit sufficiently good wettability (Tables 4 and 6). reference). Further, it was confirmed that the wettability was better when the liquid medium containing the lower alcohol was used as the solvent than when only water was used as the solvent.
‐接触角‐
　接触角については、前記ケイ酸系微粒子の最頻値が小さくなるにつれて大きくなり、親水性が低くなる傾向が確認された（表５、表７参照）。但し、前記ケイ酸系微粒子中に前記大径群と前記小径群とを共存させてなる本発明剤によって形成された本発明被膜については、いずれも十分に小さな接触角を示しており、高い親水性を有することが確認された（表４、表６参照）。 -Contact angle-
The contact angle increased as the mode value of the silicate-based fine particles decreased, and it was confirmed that the hydrophilicity tends to decrease (see Tables 5 and 7). However, the coating film of the present invention formed by the agent of the present invention in which the large-diameter group and the small-diameter group coexist in the silicic acid-based fine particles all show a sufficiently small contact angle and has a high hydrophilicity. (See Tables 4 and 6).
‐耐摩耗性‐
　耐摩耗性については、前記ケイ酸系微粒子の最頻値が大きくなるにつれて、悪くなることが確認された（表５、表７参照）。但し、前記ケイ酸系微粒子中に前記大径群と前記小径群とを共存させてなる本発明剤によって形成された本発明被膜については、十分な耐摩耗性を有することが確認された（表４、表６参照）。又、前記ケイ酸系微粒子としてシリケートを用いた場合、シラノール反応によって生じたシロキサンによる化学的な結合が、耐摩耗性をより向上させることが確認された。更に、ポリシラザンを含む下処理剤にて下処理工程を実行することによって、より一層耐摩耗性が向上することが確認された。 -Abrasion resistance-
About abrasion resistance, it was confirmed that it gets worse as the mode value of the silicic acid-based fine particles increases (see Tables 5 and 7). However, it was confirmed that the coating film of the present invention formed by the agent of the present invention in which the large-diameter group and the small-diameter group coexist in the silicic acid-based fine particles have sufficient wear resistance (Table 4, see Table 6). In addition, when silicate was used as the silicic acid-based fine particles, it was confirmed that chemical bonding by siloxane generated by silanol reaction further improved the wear resistance. Furthermore, it was confirmed that the wear resistance was further improved by performing the pretreatment step with a pretreatment agent containing polysilazane.
‐自己洗浄性‐
　本発明剤に含まれるケイ酸系微粒子により、親水性を持つ本発明被膜が保護カバーに形成されて水の接触角が低下することで、保護カバーの上に乗った砂塵、鳥の糞などの有機物、火山灰などの汚れと保護カバーとの間に水が濡れ広がり、汚れを浮かびあがらせて、保護カバーの傾斜に従って汚れが水とともに流れ落ちることが確認された。すなわち、本発明被膜が形成された保護カバーは自己洗浄性が発揮されていることが分かった。 -Self-cleaning-
By the silicic acid-based fine particles contained in the agent of the present invention, the hydrophilic coating of the present invention is formed on the protective cover and the contact angle of water is reduced, so that the dust, bird droppings, etc. It was confirmed that water wets and spreads between dirt such as organic matter and volcanic ash and the protective cover, and the dirt floats up, and the dirt flows down with the water according to the inclination of the protective cover. That is, it was found that the protective cover on which the coating film of the present invention was formed exhibited self-cleaning properties.
＜試験３＞
‐透光性の評価‐
　本発明皮膜が形成された太陽光パネル用の保護カバー（試験１及び試験２によって得られたもの）について、波長３００ｎｍ～１５００ｎｍの範囲の光線透過率を測定することによって、各保護カバーの透光性を評価した。なお、光線透過率の測定は、株式会社島津製作所製、SolidSpec-3700を用いて行った。 <Test 3>
-Evaluation of translucency-
For the protective cover for solar panels (obtained by Test 1 and Test 2) on which the coating of the present invention was formed, the light transmittance of each protective cover was measured by measuring the light transmittance in the wavelength range of 300 nm to 1500 nm. Sex was evaluated. The light transmittance was measured using SolidSpec-3700 manufactured by Shimadzu Corporation.
　図１、及び図２に、波長３００ｎｍ～１５００ｎｍの範囲の光線透過率を検証したチャートを示す。なお、図１に示すチャートは、ＡＲコートがなされていない保護カバーについての光線透過率を測定したものであり、図２に示すチャートはＡＲコートがなされた保護カバーについての光線透過率を測定したものである。又、図１に示すチャート中の実線は、本発明方法実行前の未処理の保護カバーについての透光性を示すものであり、点線は、前記実施例４に係る本発明剤によって本発明被膜が形成された保護カバー（ＮＰＣ）についての透光性を示すものである。図２に示すチャート中の点線は、本発明方法実行前の未処理の保護カバーについての透光性を示すものであり、実線は、前記実施例４に係る本発明剤によって本発明被膜が形成された保護カバー（ＮＰＣ）についての透光性を示すものである。 1 and 2 show charts for verifying light transmittance in the wavelength range of 300 nm to 1500 nm. The chart shown in FIG. 1 is obtained by measuring the light transmittance of a protective cover without AR coating, and the chart shown in FIG. 2 is measured by the light transmittance of a protective cover with AR coating. Is. Further, the solid line in the chart shown in FIG. 1 indicates the translucency of the untreated protective cover before the execution of the method of the present invention, and the dotted line indicates the coating of the present invention by the agent of the present invention according to Example 4. It shows the translucency about the protective cover (NPC) in which is formed. The dotted line in the chart shown in FIG. 2 indicates the translucency of the untreated protective cover before execution of the method of the present invention, and the solid line indicates that the coating of the present invention is formed by the agent of the present invention according to Example 4. It shows the translucency about the made protective cover (NPC).
　図１のチャートに示すように、ＡＲコートがなされてない保護カバーについては、波長３００ｎｍ～１５００ｎｍの全領域にわたって、光線透過率が向上していることが確認された。 As shown in the chart of FIG. 1, it was confirmed that the light transmittance of the protective cover without AR coating was improved over the entire wavelength range of 300 nm to 1500 nm.
　一方、図２のチャートに示すように、ＡＲコートがなされた保護カバーついては、波長４５０ｎｍ未満の光線透過率が、未処理の保護カバーの光線透過率より低くなっている。即ち、ＡＲコートがなされた保護カバーの表面に形成されている本発明被膜は、波長４５０ｎｍ以下の光線の透過を阻害するものと言える。 On the other hand, as shown in the chart of FIG. 2, for the protective cover with AR coating, the light transmittance at a wavelength of less than 450 nm is lower than the light transmittance of the untreated protective cover. That is, it can be said that the coating of the present invention formed on the surface of the protective cover on which the AR coating has been made inhibits transmission of light having a wavelength of 450 nm or less.
　しかしながら、波長４５０ｎｍ以上の光線については、広範囲にわたって透過率が向上しているため、係る保護カバーを透過し得る光線の総量は、未処理の保護カバーより多くなる。 However, the transmittance of a light beam having a wavelength of 450 nm or more is improved over a wide range, and therefore the total amount of light beam that can be transmitted through the protective cover is larger than that of the untreated protective cover.
　ここで、波長４５０ｎｍ以上の光線は、赤外領域の光線（赤外線）を多く含むものであり、従って、太陽光パネルの保護カバーに本発明被膜を形成すれば、赤外領域の光線を良好に取り込み得る特性を付与することができる。 Here, light having a wavelength of 450 nm or more contains a large amount of light in the infrared region (infrared rays). Therefore, if the coating of the present invention is formed on the protective cover of the solar panel, the light in the infrared region is improved. Properties that can be incorporated can be imparted.
　そして、赤外領域の光線を良好に取り込み得る特性を有する本発明パネルは、特に、朝夕や曇曇天時の薄暗い時間帯において、効率の良い発電を可能にする。 The panel of the present invention having a characteristic capable of capturing light in the infrared region satisfactorily enables efficient power generation particularly in the dim time zone during morning and evening or cloudy weather.
＜試験４＞
－ケイ酸系微粒子の配合割合に対する透過率の評価－
　親水性付与剤が塗布される前の、ＡＲコートがなされた太陽光パネルの保護カバーについて、波長３００～１５００ｎｍの光線透過率（％）を測定した。そして、３００ｎｍから、シリコンのバンドギャップエネルギーに相当する８８６ｎｍまでの、１ｎｍごとの各波長の光線透過率（％）の値の総和Ｓ０を算出した。次に、実施例４に示した固形分重量比率で、小径群と大径群とを配合したケイ酸系微粒子の配合割合をｘ重量％（ｘ＝０．５、０．７５、１．０、１．４、２．０、２．５、３．０）とした親水性付与剤を、ＡＲコートがなされた太陽光パネルの保護カバーに、ウエットで１０ｇ／ｍ２の塗布量になるように塗布し、乾燥させて、親水性被膜を形成した。親水性被膜が形成された保護カバーについて、波長３００～１５００ｎｍの光線透過率（％）を測定し、３００ｎｍから８８６ｎｍまでの、１ｎｍごとの各波長の光線透過率（％）の値の総和Ｓｘを算出した。そして、ＳｘからＳ０を引いた値を、ケイ酸系微粒子がｘ重量％配合されたときの透過率積分値として得た。得られた透過率積分値を、ケイ酸系微粒子の配合割合に対してプロットした結果を図３に示した。 <Test 4>
-Evaluation of transmittance with respect to mixing ratio of silicate fine particles-
The light transmittance (%) at a wavelength of 300 to 1500 nm was measured for the protective cover of the solar panel coated with AR before the hydrophilicity imparting agent was applied. Then, the total S 0 of the light transmittance (%) values of each wavelength for each 1 nm from 300 nm to 886 nm corresponding to the band gap energy of silicon was calculated. Next, in the solid content weight ratio shown in Example 4, the mixing ratio of the silicic acid-based fine particles in which the small diameter group and the large diameter group were mixed was x wt% (x = 0.5, 0.75, 1.0). , 1.4, 2.0, 2.5, 3.0) with a wet coating amount of 10 g / m 2 on the protective cover of the solar panel with AR coating. And dried to form a hydrophilic film. For the protective cover on which the hydrophilic coating is formed, the light transmittance (%) at a wavelength of 300 to 1500 nm is measured, and the total sum S x of the light transmittance (%) at each wavelength from 300 nm to 886 nm for each wavelength. Was calculated. Then, a value obtained by subtracting the S 0 from S x, silicate-based particles as a transmittance integrated value of when x wt% blend. FIG. 3 shows the result of plotting the obtained transmittance integral value against the mixing ratio of the silicate fine particles.
　図３に示されるように、親水性付与剤におけるケイ酸系微粒子の配合割合が、０．３重量％～３．０重量％である場合、親水性被膜を有する保護カバーは、透過率積分値が正の値となり、親水性被膜により光線透過率が向上することが確認された。また、配合割合が１．０重量％以上、２．５重量％以下である場合、透過率積分値はより大きい値となり、親水性被膜により光線透過率が一層向上することが確認された。 As shown in FIG. 3, when the blending ratio of the silicic acid-based fine particles in the hydrophilicity imparting agent is 0.3% by weight to 3.0% by weight, the protective cover having the hydrophilic film has an integral value of transmittance. Became a positive value, and it was confirmed that the light transmittance was improved by the hydrophilic coating. Further, when the blending ratio is 1.0 wt% or more and 2.5 wt% or less, the transmittance integrated value becomes a larger value, and it was confirmed that the light transmittance is further improved by the hydrophilic coating.
　又、本発明パネルは、保護パネルに、親水性が高く、自己洗浄性のある本発明被膜が形成されているため、汚れ難い特性を有する。 In addition, the panel of the present invention has a characteristic that it is difficult to get dirty because the protective panel is formed with the coating film of the present invention that is highly hydrophilic and self-cleaning.
　即ち、本発明パネルは、高い光線透過率と、汚れ難い二つの特性を有するものとなり、安定した発電能力を維持し得るものとなる。実際に１日当たりの発電量を測定すると、未処理の保護カバーの場合と比較して３％以上（３～５％程度）の発電量の増加が確認された。 That is, the panel of the present invention has a high light transmittance and two characteristics that are difficult to get dirty, and can maintain a stable power generation capacity. When the amount of power generation per day was actually measured, it was confirmed that the amount of power generation increased by 3% or more (about 3-5%) compared to the case of the untreated protective cover.
　なお、図１及び図２に示すチャートは、前記実施例４に係る本発明剤によって本発明被膜が形成された保護カバーについての透光性を検証したものであるが、その他の実施例に係る本発明剤によって本発明被膜が形成された保護カバーについても同様の挙動を示すことが確認されている。 The charts shown in FIG. 1 and FIG. 2 verify the translucency of the protective cover on which the coating film of the present invention is formed by the agent of the present invention according to the fourth embodiment. It has been confirmed that the protective cover in which the coating of the present invention is formed by the agent of the present invention exhibits the same behavior.
　本発明は、その精神又は主要な特徴から逸脱することなく、他のいろいろな形態で実施することができる。そのため、上述の実施形態（実施例）はあらゆる点で単なる例示に過ぎず、限定的に解釈してはならない。本発明の範囲は特許請求の範囲によって示すものであって、明細書本文には何ら拘束されない。更に、特許請求の範囲の均等範囲に属する変形や変更は、すべて本発明の範囲内のものである。 The present invention can be implemented in various other forms without departing from the spirit or main features thereof. Therefore, the above-described embodiments (examples) are merely examples in all respects and should not be interpreted in a limited manner. The scope of the present invention is indicated by the claims, and is not restricted by the text of the specification. Further, all modifications and changes belonging to the equivalent scope of the claims are within the scope of the present invention.
　本発明は、自動車の車体や、建築物の内外装、トイレ、台所、洗面所、浴槽などの水回り製品、看板、標識、プラスチック製品、ガラス製品等の各種製品に対して良好な防汚特性を付与する手段として好適に利用することができる。又、効率の高い光発電を実現する太陽光パネルを構築する手段として好適に利用することもできる。 The present invention has good antifouling properties for various products such as automobile bodies, interior and exterior of buildings, toilets, kitchens, toilets, bathtubs, and other water-based products, signs, signs, plastic products, glass products, etc. It can be suitably used as a means for imparting. Moreover, it can also be suitably used as means for constructing a solar panel that realizes highly efficient photovoltaic power generation.

Claims (9)

  1. 　被処理物に親水性被膜を形成するための親水性付与剤であって、
    　シリケート又はシリカからなるケイ酸系微粒子と、
    　溶媒とを含有し、
    　前記ケイ酸系微粒子が、最頻値１０ｎｍ以下の小径群と最頻値１５～３０ｎｍの大径群とを含み、
    　前記溶媒中の前記小径群と前記大径群との固形分重量比率が、３：１～１：５であり、
    　前記親水性付与剤における前記ケイ酸系微粒子の配合割合が、０．３重量％～３．０重量％であることを特徴とする親水性付与剤。     A hydrophilicity-imparting agent for forming a hydrophilic film on a workpiece,
    Silicate-based fine particles composed of silicate or silica;
    Containing a solvent,
    The silicate-based fine particles include a small diameter group having a mode value of 10 nm or less and a large diameter group having a mode value of 15 to 30 nm,
    The solid content weight ratio of the small diameter group and the large diameter group in the solvent is 3: 1 to 1: 5,
    The hydrophilicity-imparting agent, wherein a blending ratio of the silicic acid-based fine particles in the hydrophilicity-imparting agent is 0.3% by weight to 3.0% by weight.
  2. 　請求項１に記載の親水性付与剤において、
    　前記ケイ酸系微粒子の配合割合が、０．５±０．２重量％となされた親水性付与剤。     In the hydrophilicity imparting agent according to claim 1,
    A hydrophilicity imparting agent in which the blending ratio of the silicic acid-based fine particles is 0.5 ± 0.2% by weight.
  3. 　請求項１に記載の親水性付与剤において、
    　前記ケイ酸系微粒子の配合割合が、１．５±０．５重量％となされた親水性付与剤。     In the hydrophilicity imparting agent according to claim 1,
    A hydrophilicity imparting agent in which the blending ratio of the silicic acid fine particles is 1.5 ± 0.5% by weight.
  4. 　被処理物に親水性被膜を形成する親水性被膜形成方法であって、
    　最頻値１０ｎｍ以下の小径群と最頻値１５～３０ｎｍの大径群とを少なくとも含むシリケート又はシリカからなるケイ酸系微粒子が、前記小径群と前記大径群との固形分重量比率が３：１～１：５となるように溶媒に配合され、前記ケイ酸系微粒子の配合割合が、０．３重量％～３．０重量％である親水性付与剤を、
    　前記被処理物に、一ないし複数回塗布する塗布工程を実行することを特徴とする親水性被膜形成方法。     A hydrophilic film forming method for forming a hydrophilic film on a workpiece,
    Silicate-based fine particles composed of silicate or silica including at least a small diameter group having a mode value of 10 nm or less and a large diameter group having a mode value of 15 to 30 nm have a solid content weight ratio of 3 to the small diameter group and the large diameter group. A hydrophilicity-imparting agent that is blended in a solvent so that the ratio is 1 to 1: 5, and the blending ratio of the silicic acid-based fine particles is 0.3 wt% to 3.0 wt%.
    A hydrophilic film forming method, wherein an application step of applying the object to be processed one or more times is executed.
  5. 　乾燥重量で、３０ｍｇ／ｍ２～３００ｍｇ／ｍ２となるように、前記親水性付与剤を被処理物に塗布する請求項４に記載の親水性被膜形成方法。 The hydrophilic film forming method according to claim 4, wherein the hydrophilicity-imparting agent is applied to an object to be treated so that the dry weight is 30 mg / m 2 to 300 mg / m 2 .
  6. 　請求項４または５に記載された親水性被膜形成方法において、
    　前記塗布工程の実行前に、ポリシラザンを少なくとも含む下処理剤を、前記被処理物に塗布する下処理工程を実行する親水性被膜形成方法。     In the hydrophilic film forming method according to claim 4 or 5,
    The hydrophilic film formation method which performs the pretreatment process of apply | coating the pretreatment agent which contains polysilazane at least to the said to-be-processed object before execution of the said application | coating process.
  7. 　シリケート又はシリカからなるケイ酸系微粒子を含む親水性被膜であって、
    　前記ケイ酸系微粒子が、最頻値１０ｎｍ以下の小径群と最頻値１５～３０ｎｍの大径群とを含み、
    　前記小径群と前記大径群との固形分重量比率が、３：１～１：５であることを特徴とする親水性被膜。     A hydrophilic film containing silicate-based fine particles made of silicate or silica,
    The silicate-based fine particles include a small diameter group having a mode value of 10 nm or less and a large diameter group having a mode value of 15 to 30 nm,
    The hydrophilic coating film, wherein the solid content weight ratio of the small diameter group and the large diameter group is 3: 1 to 1: 5.
  8. 　被処理物上に乾燥重量で、３０ｍｇ／ｍ２～３００ｍｇ／ｍ２となるように設けられている請求項７に記載の親水性被膜。 The hydrophilic coating according to claim 7, wherein the hydrophilic coating is provided on the workpiece to have a dry weight of 30 mg / m 2 to 300 mg / m 2 .
  9. 　保護カバーの表面に、請求項７または８に記載の親水性被膜が形成されていることを特徴とする太陽光パネル。 A solar panel, wherein the hydrophilic film according to claim 7 or 8 is formed on a surface of the protective cover.
PCT/JP2017/014156 2017-04-04 2017-04-04 Hydrophilicity-imparting agent, hydrophilic coating film forming method, hydrophilic coating film, and solar panel WO2018185865A1 (en)

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WO2002088269A1 (en) * 2001-04-27 2002-11-07 Clariant International Ltd. Anti-staining coating solution comprising inorganic polysilazane
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JP2012246440A (en) * 2011-05-30 2012-12-13 Nippon Paint Co Ltd Inorganic coating composition
JP2015078315A (en) * 2013-10-17 2015-04-23 パンサーフェス株式会社 Hydrophilicity improver, method for improving film hydrophilicity, and hydrophilic treated film
JP2016087561A (en) * 2014-11-06 2016-05-23 富士フイルム株式会社 Aqueous coating liquid, film, production method of the same, laminate and solar cell module

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002088269A1 (en) * 2001-04-27 2002-11-07 Clariant International Ltd. Anti-staining coating solution comprising inorganic polysilazane
JP2009108187A (en) * 2007-10-30 2009-05-21 Mitsubishi Rayon Co Ltd Coating film, aqueous coating material, and its manufacturing method
JP2011521776A (en) * 2008-05-16 2011-07-28 スリーエム イノベイティブ プロパティズ カンパニー Silica coating to increase hydrophilicity / permeability
JP2012246440A (en) * 2011-05-30 2012-12-13 Nippon Paint Co Ltd Inorganic coating composition
JP2015078315A (en) * 2013-10-17 2015-04-23 パンサーフェス株式会社 Hydrophilicity improver, method for improving film hydrophilicity, and hydrophilic treated film
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