WO2018185865A1 - Agent conférant un caractère hydrophile, procédé de formation de film de revêtement hydrophile, film de revêtement hydrophile et panneau solaire - Google Patents

Agent conférant un caractère hydrophile, procédé de formation de film de revêtement hydrophile, film de revêtement hydrophile et panneau solaire Download PDF

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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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fine particles
hydrophilicity
diameter group
silicate
imparting agent
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PCT/JP2017/014156
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English (en)
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/fr
Publication of WO2018185865A1 publication Critical patent/WO2018185865A1/fr

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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.

Abstract

Le problème à la base de la présente invention concerne : un nouvel agent conférant un caractère hydrophile qui peut conférer un caractère hydrophile élevé à un objet à traiter et qui permet une transparence améliorée dans la région infrarouge pour des matériaux transparents tels qu'un couvercle de protection pour un panneau solaire ; et un procédé de formation de film de revêtement hydrophile. Un autre but de la présente invention concerne : un film de revêtement hydrophile formé par ledit procédé de formation de film de revêtement hydrophile ; et un panneau solaire dans lequel ledit film de revêtement hydrophile est formé sur une surface d'un couvercle de protection. Selon la solution de l'invention, le caractère hydrophile est conféré à un objet à traiter par un agent conférant un caractère hydrophile qui contient un solvant et des microparticules de type acide silicique comprenant un silicate ou de la silice, les microparticules de type acide silicique comprenant au moins un groupe de petit diamètre présentant un mode qui n'est pas supérieur à 10 nm et un groupe de grand diamètre présentant un mode de 15 à 30 nm, le rapport pondéral des solides dans le solvant entre le groupe de petit diamètre et le groupe de grand diamètre étant de 3:1 à 1:5 et la teneur en microparticules de type acide silicique dans l'agent conférant un caractère hydrophile étant de 0,3 % en poids à 3,0 % en poids.
PCT/JP2017/014156 2017-04-04 2017-04-04 Agent conférant un caractère hydrophile, procédé de formation de film de revêtement hydrophile, film de revêtement hydrophile et panneau solaire WO2018185865A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002088269A1 (fr) * 2001-04-27 2002-11-07 Clariant International Ltd. Solution d'enduction anti-salissures contenant du polysilazane anorganique
JP2009108187A (ja) * 2007-10-30 2009-05-21 Mitsubishi Rayon Co Ltd 塗膜、および水性被覆材とその製造方法
JP2011521776A (ja) * 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 親水性／透過率を高めるためのシリカコーティング
JP2012246440A (ja) * 2011-05-30 2012-12-13 Nippon Paint Co Ltd 無機コーティング組成物
JP2015078315A (ja) * 2013-10-17 2015-04-23 パンサーフェス株式会社 親水性向上剤、被膜の親水性向上方法、親水処理被膜
JP2016087561A (ja) * 2014-11-06 2016-05-23 富士フイルム株式会社 水性塗布液、膜及びその製造方法、積層体、並びに太陽電池モジュール

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002088269A1 (fr) * 2001-04-27 2002-11-07 Clariant International Ltd. Solution d'enduction anti-salissures contenant du polysilazane anorganique
JP2009108187A (ja) * 2007-10-30 2009-05-21 Mitsubishi Rayon Co Ltd 塗膜、および水性被覆材とその製造方法
JP2011521776A (ja) * 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 親水性／透過率を高めるためのシリカコーティング
JP2012246440A (ja) * 2011-05-30 2012-12-13 Nippon Paint Co Ltd 無機コーティング組成物
JP2015078315A (ja) * 2013-10-17 2015-04-23 パンサーフェス株式会社 親水性向上剤、被膜の親水性向上方法、親水処理被膜
JP2016087561A (ja) * 2014-11-06 2016-05-23 富士フイルム株式会社 水性塗布液、膜及びその製造方法、積層体、並びに太陽電池モジュール

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