WO2017022433A1 - Liquide de revêtement aqueux, film et procédé de production associé, stratifié et module photovoltaïque - Google Patents

Liquide de revêtement aqueux, film et procédé de production associé, stratifié et module photovoltaïque Download PDF

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Publication number
WO2017022433A1
WO2017022433A1 PCT/JP2016/070586 JP2016070586W WO2017022433A1 WO 2017022433 A1 WO2017022433 A1 WO 2017022433A1 JP 2016070586 W JP2016070586 W JP 2016070586W WO 2017022433 A1 WO2017022433 A1 WO 2017022433A1
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film
aqueous coating
silica particles
coating solution
coating film
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PCT/JP2016/070586
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English (en)
Japanese (ja)
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優介 畠中
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富士フイルム株式会社
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Publication of WO2017022433A1 publication Critical patent/WO2017022433A1/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
    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • 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
    • C09D5/02—Emulsion paints including aerosols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • 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 an aqueous coating solution, a film and a manufacturing method thereof, a laminate, and a solar cell module.
  • the aqueous coating liquid containing silica fine particles uses a solvent containing water, and since the surface energy of the film formed from the coating liquid is low and the transparency is excellent, it is used for various applications.
  • Examples of the application include an antireflection film, an optical lens, an optical filter, a flattening film for a thin film transistor (TFT) of various displays, a dew condensation prevention film, an antifouling film, and a surface protective film.
  • TFT thin film transistor
  • the antireflection film and the antifouling film are useful because they can be used for protective films for solar cell modules, surveillance cameras, lighting equipment, signs, and the like.
  • aqueous coating liquids containing silica fine particles used for applications such as antifouling films.
  • silica fine particles used for applications such as antifouling films.
  • an antifouling coating liquid that can be uniformly applied to the surface of a coating film having a water repellent property, it contains silica fine particles, water, a surfactant as essential components, and alcohol.
  • An antifouling coating solution that does not substantially contain has been proposed (see, for example, Japanese Patent Application Publication No. 2010-138358).
  • antifouling agents for hard surfaces containing positively charged silica compounds with an average particle diameter of 1 to 100 nm and water are proposed as antifouling agents that have excellent antifouling effects on hard surfaces and also have easy washing effects. (See, for example, JP-A-2002-3820).
  • the present invention has been made in view of the above circumstances, and a problem in one embodiment of the present invention is to provide an aqueous coating liquid that can form a film excellent in antireflection properties, scratch resistance, and antifouling properties. There is to do. Moreover, the subject of another embodiment of this invention is providing the film
  • Means for solving the problems include the following embodiments.
  • aqueous coating according to [1], wherein at least one of a trivalent element and a pentavalent element that dissociates in a solution containing water is at least one selected from aluminum, phosphorus, chromium, and iron. liquid.
  • the aqueous coating solution according to [1] or [2], wherein the content ratio of the binder precursor to the silica particles in the aqueous coating solution is 0.0050 or more and 0.0525 or less by mass ratio.
  • At least the coating film that has undergone the coating film drying step has an average reflectance at 5 ° incidence with light having a wavelength of 400 nm to 1100 nm that is lower than the average reflectance of the substrate, and is defined by the following formula (1)
  • a laminate having the film according to [13] or [14] on a substrate [16] The laminate according to [15], wherein the substrate is a glass substrate. [17] A solar cell module comprising the laminate according to [15] or [16].
  • an aqueous coating solution that can form a film excellent in antireflection properties, scratch resistance, and antifouling properties.
  • membrane excellent in antireflective property, scratch resistance, and antifouling property, its manufacturing method, a laminated body, and a solar cell module can be provided.
  • a numerical range indicated by using “to” means a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • the amount of each component in the composition is the total amount of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. Means.
  • process is not limited to an independent process, and is included in this term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes. It is.
  • the aqueous coating liquid of the present embodiment includes water, silica particles having an average primary particle size of 100 nm or less, A binder precursor having a molecular weight of 600 or less, which is a salt of a compound containing at least one of a trivalent element and a pentavalent element that dissociates in a solution containing water. According to the aqueous coating liquid, it is possible to form a film having good antireflection properties, scratch resistance, and antifouling properties.
  • the aqueous coating solution contains silica particles having an average primary particle size of 100 nm or less, a film having excellent hydrophilicity and antireflection properties can be formed.
  • the binder precursor is a salt of a compound containing at least one of a trivalent element and a pentavalent element that dissociates in a solution containing water, and includes a binder precursor having a molecular weight of 600 or less.
  • Silica particles play a role as fillers, and the hydroxyl groups on the surface of the particles act to contribute to hydrophilicity. Therefore, the film formed of the aqueous coating solution containing silica particles has good surface hydrophilicity and excellent antifouling properties.
  • the binder precursor used in the aqueous coating solution of the present embodiment is a salt of a compound having a relatively low molecular weight, strong inorganicity, and high ionicity. For this reason, the salt of the compound is dissociated in the aqueous coating solution, and the ions of the trivalent element and pentavalent element are adsorbed on the surface of the silica particles in the dissociated state, so that undesired silica particles in the aqueous coating solution Aggregation can be suppressed.
  • the binder derived from the binder precursor has a dense bond network derived from trivalent elements and pentavalent elements, and can firmly bond silica particles even in a small area. Is done.
  • the silica particles are strongly bonded to each other by a binder having a high inorganicity and a dense bonding network derived from the binder precursor.
  • the binder existing between the formed silica particles is a very thin layer, and the silica particles are fixed in a small area close to the point adhesion with the adjacent particles, and fixed between the silica particles with a conventional organic binder.
  • a film having a larger void is formed than in the case of the above. It is considered that the antireflection property of the film is superior to the conventional product due to the silica particles having high antireflection properties and the wide gaps between the silica particles in the film. Further, even when the amount of the binder is small, adjacent silica particles are firmly bonded to each other, and as a result, the formed film is considered to have good scratch resistance. Note that the present embodiment is not limited to the above-described estimation mechanism.
  • high ionicity of a salt of a compound means both low ionization energy, ie, high cationicity, and high electronegativity, ie, high anionicity. It is used in the meaning including.
  • a salt of a compound containing a tetravalent element for example, a salt of a compound containing a trivalent element is lower in ionization energy than a salt of sodium silicate, and a salt of a compound containing a pentavalent element has an electronegativity. From a higher point, it is considered that since the ionicity is high, the ease of adsorption onto silica particles is further improved.
  • the aqueous coating liquid of this embodiment contains silica particles having an average primary particle diameter of 100 nm or less.
  • Silica particles have a function of further exerting hydrophilicity while enhancing the physical resistance of a film formed by an aqueous coating solution. That is, the silica particles contribute to the hydrophilic expression of the film formed by the action of hydroxy groups on the particle surface.
  • the silica particles contained in the aqueous coating solution can be used without particular limitation as long as the average primary particle diameter is 100 nm or less. Examples of silica particles that can be used in the aqueous coating solution of the present embodiment include hollow silica particles, porous silica particles, and nonporous silica particles.
  • the shape of the silica particles examples include a spherical shape, a plate shape, a needle shape, and a bead shape.
  • the silica particles may be surface-treated silica particles whose surface is treated with an aluminum compound or the like. From the viewpoint of the antifouling property of the formed film, it is preferable to select an agent that does not inhibit the surface hydrophilicity of the silica particles.
  • the average primary particles Silica particles having a diameter of 100 nm or less are used.
  • the average primary particle size of the silica particles is preferably 50 nm or less, and more preferably 30 nm or less.
  • an average primary particle diameter is 1 nm or more from a viewpoint that aggregation of silica particles is suppressed more effectively. That is, the average primary particle diameter of the silica particles is preferably 1 nm or more and 50 nm or less.
  • the film formed using the aqueous coating liquid of the present embodiment is used for, for example, an antireflection layer of a security camera cover, a cover for various sensors installed outdoors, the antireflection property is better.
  • the average primary particle diameter of the silica particles is preferably 1 nm or more and 50 nm or less.
  • the film formed using the aqueous coating liquid of the present embodiment is used for, for example, a protective layer of a solar cell module, a protective layer of an automobile exterior member, etc., it has better scratch resistance and durability.
  • the average primary particle diameter of the silica particles is preferably 8 nm or less, more preferably 6 nm or less, and further preferably 2 nm or more and 4 nm or less. Since the average primary particle diameter of the silica particles contained in the aqueous coating liquid is finer, in the film formed using the aqueous coating liquid, the silica particles are densely arranged to form a dense film with high hardness. It is considered that the scratch resistance of the film is improved. In addition, a dense film in which silica particles are densely arranged has a smooth film surface, so that the antifouling property of the formed film is considered to be more excellent.
  • the average primary particle diameter of the silica particles can be determined from an image of a photograph taken by observing the silica particles dispersed in 1-methoxy-2-propanol with a transmission electron microscope. Specifically, it was obtained by measuring the projected area of the silica particles from the image of the transmission electron micrograph, obtaining the equivalent circle diameter from the measured projected area, and arithmetically averaging the obtained equivalent circle diameter value. The value is the average primary particle diameter of the silica particles. In the present specification, the average primary particle diameter of the silica particles is obtained by measuring the projected areas of 300 silica particles, obtaining the equivalent circle diameters from the measured projected areas, and arithmetically averaging the obtained equivalent circle diameter values. The value obtained by is adopted.
  • the silica particles contained in the aqueous coating solution are preferably nonporous silica particles from the viewpoint of improving the scratch resistance of the formed film.
  • “Nonporous silica particles” mean silica particles having no voids inside the particles, and are distinguished from silica particles having voids inside the particles such as hollow silica particles and porous silica particles.
  • the “nonporous silica particles” have a core such as a polymer inside the particles, and the outer shell (shell) of the core is silica or a silica precursor (for example, silica by firing). It does not include core-shell structured silica particles composed of changing materials.
  • the nonporous silica particles are a state where each nonporous silica particle is aggregated into a single particle (aggregated by van der Waals force). After the coating film is dried, at least some of the non-porous silica particles adjacent to each other are connected to each other via a binder and fixed. Exists. Since the silica particles contained in the aqueous coating liquid are nonporous silica particles, the hardness of the film is increased and the scratch resistance is further improved.
  • silica particles commercially available products may be used as long as the average primary particle diameter is 100 nm or less.
  • examples of commercially available products include NALCO (registered trademark) 8699 (aqueous dispersion of nonporous silica particles, average primary particle size: 3 nm, solid content: 15% by mass, manufactured by NALCO), NALCO (registered trademark) 1130 ( Aqueous dispersion of nonporous silica particles, average primary particle size: 8 nm, solid content: 30% by mass, manufactured by NALCO, Snowtex (registered trademark) XS (aqueous dispersion of nonporous silica particles, average primary particles) Diameter: 5 nm, solid content: 20% by mass, manufactured by Nissan Chemical Co., Ltd.). These commercially available products can be selected and used according to the purpose.
  • the aqueous coating solution may contain only one type of silica particles or two or more types of silica particles.
  • the silica particles can be arbitrarily selected according to the purpose, such as particles having different sizes or particles having different shapes.
  • the content of silica particles is preferably 64% by mass to 95% by mass, and more preferably 70% by mass to 95% by mass with respect to the total solid content of the aqueous coating liquid. Moreover, 30 mass% or less is preferable with respect to the aqueous coating liquid whole quantity, 20 mass% or less is more preferable, and 10 mass% or less is further more preferable.
  • the content of silica particles indicates the total amount when the aqueous coating solution contains two or more types of silica particles. When the content of the silica particles is within the above range, the dispersibility of the silica particles in the aqueous coating solution is enhanced, which is advantageous in preventing aggregation and the like. Further, the scratch resistance of the film formed using the aqueous coating solution becomes better, and a more excellent planar film can be formed.
  • the silica particles contained in the aqueous coating solution are preferably negatively charged on the surface.
  • Silica particles whose surface is negatively charged have better dispersion stability in an aqueous coating solution, and as a result, coating accuracy is further improved and the coated surface is improved. For this reason, the film formed of the aqueous coating solution has better antireflection properties and further improves the surface appearance.
  • the surface of the silica particles is negatively charged, the surface of the film formed by the aqueous coating solution is also negatively charged, dirt is less likely to adhere, and the antifouling property of the film becomes better.
  • the charged state of the silica particles contained in the aqueous coating solution can be confirmed by measuring the Zeda potential.
  • the aqueous coating solution is appropriately diluted with deionized water while maintaining the pH, and the Zeda potential is measured for the obtained diluted aqueous coating solution, and the measurement result is negative. Is assumed that the silica particles are charged “negative”, and if the measurement result is positive, the silica particles are charged “positive”.
  • a Zeda potential measuring device for example, a Zeda potential measuring system (model number: ELSZ-1, manufactured by Otsuka Electronics Co., Ltd.) can be used.
  • the aqueous coating liquid of this embodiment is a salt of a compound containing at least one of a trivalent element and a pentavalent element that dissociates in a solution containing water, and has a molecular weight of 600 or less.
  • binder precursor When the binder precursor contains a salt of a compound containing at least one of a trivalent element and a pentavalent element, the salt dissociates in the aqueous coating solution, and ions containing a trivalent or pentavalent element are produced.
  • the silica particles When the generated ions are adsorbed and coated on the surface of the silica particles, undesired aggregation of the silica particles in the aqueous coating liquid can be suppressed.
  • the solvent containing water By drying the coating film formed by applying the aqueous coating solution, the solvent containing water is removed from the binder precursor, and at least one of a trivalent element and a pentavalent element is applied by applying thermal energy.
  • a multimer such as a dimer or a trimer, whereby a bonded network of inorganic compounds is formed between the silica particles.
  • the formed dense bonded network is formed into a binder. It is considered that the silica particles can be firmly bonded to each other.
  • the binder precursor has a molecular weight of 600 or less. In a relatively high molecular weight compound having a molecular weight of over 600, even if it contains a trivalent element and a pentavalent element, it is difficult to form a multimer by the reaction as described above depending on the application of thermal energy, and it is strong. Binder formation cannot be expected.
  • the molecular weight of the binder precursor is preferably 450 or less, and preferably 300 or less because the formation reaction of multimers caused by the trivalent element and the pentavalent element more easily proceeds. Since formation can be expected, it is preferable.
  • At least one of the trivalent element and pentavalent element at least one selected from aluminum, phosphorus, chromium, and iron can be given. Any of the elements described above is preferably used in the aqueous coating solution of the present embodiment.
  • the bond network formed by at least one element selected from trivalent or pentavalent elements such as aluminum, phosphorus, chromium, and iron is compared with the case where a tetravalent element such as silicon is used. It becomes denser and silica particles can be bonded more firmly.
  • Examples of the salt of the compound containing at least one of trivalent element and pentavalent element include aluminum metaphosphate, aluminum phosphate, sodium tripolyphosphate, lithium phosphate, magnesium phosphate, aluminum sulfate, aluminum silicate, and silicic acid.
  • Examples include sodium aluminum (zeolite A), potassium chromate, potassium dichromate, and iron (III) phosphate. From the viewpoint of the effect, there are a plurality of reaction sites that contribute to the formation of the multimer, as the element, aluminum metaphosphate with phosphorus and aluminum with a plurality of trivalent and pentavalent elements. This is preferable because a stronger bond network is formed.
  • the aqueous coating solution of the present embodiment may contain only one kind of the salt of the compound described above, or may contain two or more kinds.
  • a salt of a compound containing at least one of a trivalent element and a pentavalent element that dissociates in a solution containing water is a strong bond network when a compound having a molecular weight of 600 or less, such as aluminum metaphosphate, is used. According to the study of the present inventors, the aluminum phosphate having a molecular weight exceeding 600 does not form a bond network even by the same operation, and the silica particles by the binder are formed. The strong bond was not formed.
  • the salt content of the compound containing at least one of trivalent and pentavalent elements as a binder precursor in the aqueous coating solution is connected to a capillary column having an inner diameter of 1 mm or less using a microflow pump. It can be measured by a measuring method using high performance liquid chromatography after feeding.
  • the content of the binder precursor is preferably 0.0050 or more and 0.0525 or less, and 0.0100 or more and 0.0350 or less in terms of mass ratio with respect to the content of silica particles contained in the aqueous coating solution. It is more preferable. That is, by using the aqueous coating liquid of this embodiment, strong bonding can be achieved even in a ratio where the content of the binder precursor is extremely small with respect to the content of silica particles.
  • an organic binder such as tetraethoxysilane has a mass ratio of about 0.0530 or more with respect to the content of silica particles in order to bond silica particles firmly.
  • the aqueous coating liquid of this embodiment contains water.
  • the water used for the aqueous coating solution is preferably deionized water or ion-exchanged water that does not contain impurities or has the content of impurities reduced as much as possible.
  • the content of water contained in the aqueous coating solution is preferably 50% by mass or more, more preferably 65% by mass or more, and more preferably 80% by mass or more with respect to the total amount of liquid components in the aqueous coating solution. More preferably it is.
  • the aqueous coating liquid of the present embodiment may contain components other than silica particles having an average primary particle size of 100 nm or less, a binder precursor, and water depending on the purpose within a range that does not impair the effects of the present embodiment.
  • Other components that can be optionally contained in the aqueous coating solution may be hereinafter referred to as “other components”. Examples of other components that can be used in this embodiment include a surfactant, a hydrophilic organic solvent, a water-soluble polymer, and a water-dispersed latex.
  • the aqueous coating solution of the present embodiment can contain a surfactant for the purpose of improving the coating property of the aqueous coating solution and improving the effect of suppressing the aggregation of silica particles.
  • the surfactant can be selected and used according to the purpose of use of the aqueous coating solution.
  • a nonionic surfactant is preferably used from the viewpoint of not impairing the dispersibility of the hydrophilic silica particles in the aqueous coating solution.
  • the aqueous coating liquid of this embodiment may contain a polyol type nonionic surfactant.
  • a polyol-type nonionic surfactant having a property that it is difficult to adsorb on the surface of silica particles can reduce the surface tension of an aqueous coating solution in a small amount without reducing the dispersibility of silica particles.
  • a polyol type nonionic surfactant for the coating solution it is considered that the wettability of the aqueous coating solution to the substrate becomes better.
  • the uniformity of the formed coating film is increased, and the surface shape of the film after heating is improved, and the formed film has better antireflection properties. It is thought that it will become a thing.
  • Polyol type nonionic surfactant is a surfactant having a plurality of hydroxyl groups, which does not contain an ion-dissociating moiety such as an anionic surfactant, a cationic surfactant, and an amphoteric surfactant. is there.
  • examples of the polyol type nonionic surfactant include sorbitan fatty acid ester, sucrose fatty acid ester, alkyl polyglucoside having a cyclic polyether structure as a hydrophilic group.
  • the glycerin fatty acid ester which does not have a cyclic polyether structure the alkyl fatty acid ester of polyglycerol, the alkyl glyceryl ether, sorbitol, etc. are mentioned.
  • the polyol type nonionic surfactant a nonionic surfactant having a cyclic polyether as a hydrophilic group is preferable from the viewpoint that a better planar film can be formed.
  • alkylpolyglucoside is more preferable from the viewpoint that a film having better antireflection properties and antifouling properties can be formed.
  • the number of carbon atoms in the alkyl chain of the alkylpolyglucoside is preferably 5 to 20, more preferably 6 to 14, and still more preferably 8 to 14.
  • the alkyl chain of the alkylpolyglucoside may be linear or branched.
  • the average degree of polymerization of glucoside is preferably from 1 to 10, and more preferably from 1 to 5.
  • Specific examples of the alkyl polyglucoside include decyl glucoside and octyl glucoside.
  • the weight average molecular weight of the alkyl polyglucoside is preferably 100 to 2000, and more preferably 100 to 1000.
  • a commercially available product may be used as the polyol type nonionic surfactant.
  • commercially available products include TRITON (registered trademark) BG-10 (alkyl polyglucoside surfactant, manufactured by Dow Chemical), Mydol (registered trademark) 10, 12 (alkyl polyglucoside surfactant, Kao ( ), Rheodor (registered trademark) SP-P10 (Sorbitan fatty acid ester surfactant, manufactured by Kao Corporation), Riquemar (registered trademark) L-71-D (diglycerin fatty acid ester surfactant, RIKEN vitamin ( ), Exel (registered trademark) 95N (glycerin fatty acid ester, manufactured by Kao Corporation), Poem (registered trademark) PR-100 (alkyl glyceryl ether, manufactured by Riken Vitamin Co., Ltd.), DK Ester (registered trademark) (Sucrose fatty acid ester, manufactured by Daiichi Kogyo Seiyaku Co
  • the content when the aqueous coating solution contains a polyol-type nonionic surfactant is preferably 0.07% by mass to 1.0% by mass with respect to the total mass of the aqueous coating solution, More preferably, the content is from 0.8% to 0.8% by mass, and even more preferably from 0.07% to 0.5% by mass.
  • the content of the polyol type nonionic surfactant in the aqueous coating liquid is within the above range, the effect of addition, that is, the surface tension of the aqueous coating liquid is lowered, the wettability is improved, and the aqueous coating liquid is used.
  • the micelle formation inside is suppressed, and the denseness of the silica particles in the formed film can be further increased.
  • the aqueous coating solution may contain at least one hydrophilic organic solvent having excellent affinity with water in addition to water.
  • the aqueous coating solution contains a hydrophilic organic solvent, the surface tension of the aqueous coating solution becomes lower, and a more uniform coating film can be formed.
  • the hydrophilic organic solvent is a low boiling point organic solvent, there are advantages such as easy drying of the aqueous coating solution.
  • the hydrophilic organic solvent is not particularly limited, and examples thereof include methanol, ethanol, isopropanol, butanol, acetone, ethylene glycol, and ethyl cellosolve. From the viewpoint of easy availability and reduction of environmental burden, the hydrophilic organic solvent is preferably alcohol, and ethanol, isopropanol and the like are more preferable.
  • the aqueous coating solution contains a hydrophilic organic solvent in addition to water as an aqueous medium
  • the content of water used in the aqueous coating solution is preferably 30% by mass or more based on the total mass of the aqueous medium. More preferably, it is at least mass%.
  • the solid content in the aqueous coating solution is preferably 0.1% by mass to 30% by mass, more preferably 0.2% by mass to 20% by mass, with respect to the total mass of the aqueous coating solution. More preferably, it is 0.5 mass% to 10 mass%.
  • the solid content in the aqueous coating solution can be adjusted by the content of the solvent, particularly water.
  • the pH of the aqueous coating solution is preferably from 8 to 12, and more preferably from 9 to 11.
  • the pH of the aqueous coating solution is preferably from 8 to 12, and more preferably from 9 to 11.
  • the uniformity and surface shape of the film formed by the aqueous coating solution are improved, and in particular, it is easy to form a film with better antireflection properties.
  • the pH of the aqueous coating solution is 8 to 12
  • aggregation of silica particles in the aqueous coating solution is suppressed, and when a film is formed using the aqueous coating solution, a good planar film is formed. . Therefore, a film excellent in antireflection property, scratch resistance, and antifouling property is formed by the aqueous coating solution.
  • the isoelectric point of the silica particles varies slightly depending on the production method of the silica particles, the primary particle diameter, the surface state of the silica particles, etc., but in this case, the pH of the aqueous coating solution is adjusted to the pH of the isoelectric point of the silica particles. May be adjusted.
  • the pH of the aqueous coating solution in this specification is a value measured at 25 ° C. using a pH meter (model number: HM-31, manufactured by Toa DKK Co., Ltd.).
  • the film manufacturing method of the present embodiment includes a coating film forming step of forming a coating film by applying the above-described aqueous coating liquid on a substrate, a coating film drying step of drying the formed coating film, including.
  • the aforementioned aqueous coating liquid is a salt of a compound containing water, silica particles having an average primary particle size of 100 nm or less, and at least one trivalent or pentavalent element that dissociates in a solution containing water, And the aqueous coating liquid containing the binder precursor whose molecular weight is 600 or less.
  • the film production method of the present embodiment preferably includes a coating film baking step of baking the dried coating film at a temperature of 150 ° C. or higher and 400 ° C. or lower after the coating film drying step.
  • the film manufacturing method of the present embodiment may include other steps as necessary within a range not impairing the effects of the present embodiment.
  • a coating film is formed by applying an aqueous coating solution containing a binder precursor having a molecular weight of 600 or less, which is a salt of a compound containing one kind, and then drying the formed coating film, A film having excellent antireflection properties, scratch resistance and antifouling properties can be obtained.
  • the binder precursor used in the aqueous coating liquid of the present embodiment contains a salt of a compound containing a trivalent element and a pentavalent element having strong inorganicity and high ionicity.
  • the salt of the compound is dissociated in the aqueous coating solution and adsorbed on the surface of the silica particles.
  • the ions adsorbed on the silica particles are multivalent ions derived from at least one of a trivalent element and a pentavalent element.
  • the binder precursor has more reaction sites and an odd number of reaction sites than when monovalent, divalent, or tetravalent ions are adsorbed.
  • the binder obtained from the binder precursor has a dense bond network and can firmly bond the silica particles even in a small area.
  • the formed binder is a very thin layer, so silica particles are fixed in a small area close to point adhesion with adjacent particles, and than when fixed by a conventional organic binder between silica particles. However, a film having a larger void is formed.
  • the antireflection property of the film becomes better.
  • the silica particles are coated with the polyvalent ions derived from the binder precursor in the aqueous coating solution, so that the aggregation of the silica particles is suppressed, the dispersibility of the silica particles is improved, and the coating accuracy of the aqueous coating solution is improved. Therefore, the formed film is considered to have excellent antireflection properties.
  • a coating film forming process In the coating film forming step, a compound containing at least one of water, silica particles having an average primary particle diameter of 100 nm or less, a trivalent element and a pentavalent element dissociating in a solution containing water is formed on the substrate.
  • a coating film is formed by applying an aqueous coating solution containing a salt and a binder precursor having a molecular weight of 600 or less.
  • the dispersion and dispersion stability of the silica particles in the aqueous coating liquid are good, so the coating film is formed with good coating accuracy. I think it can be done.
  • the coating amount of the aqueous coating solution is not particularly limited, and can be appropriately set in consideration of operability and the like according to the solid content concentration in the aqueous coating solution, the desired film thickness, and the like.
  • the coating amount of the base material in the aqueous coating solution is generally is preferably 0.1mL / m 2 ⁇ 1000mL / m 2, more preferably 1mL / m 2 ⁇ 100mL / m 2, More preferably, it is 1 mL / m 2 to 50 mL / m 2 .
  • the method for applying the aqueous coating solution on the substrate is not particularly limited.
  • any known coating method such as spray coating, brush coating, roller coating, bar coating, dip coating, or the like can be applied.
  • the substrate on which the aqueous coating solution is applied is not particularly limited.
  • the substrate include substrates such as glass, resin, metal, ceramic, and composite materials thereof, and any of these substrates can be suitably used.
  • a glass substrate is preferable as the substrate.
  • the condensation through the binder of hydroxy groups in the glass substrate is not only between the hydroxy groups of the silica particles but also between the hydroxy groups of the silica particles and the hydroxy groups of the glass surface.
  • produces, the coating film excellent in adhesiveness with a base material can be formed.
  • the coating film drying step is a step of drying the coating film formed in the previous step.
  • the coating film drying step by drying the coating film formed by applying an aqueous coating solution, the silica particles are partially immobilized on the substrate via the binder formed by the binder precursor. A film is formed. Silica particles are fixed to each other via an inorganic binder, so that voids are generated between the silica particles, and the dried coating film is a film with excellent antireflection properties combined with the characteristics of the silica particles. It is considered to be.
  • the coating film formed in the coating film forming process is accurately applied and the coating film formed more uniformly is dried.
  • the coating film after drying has a uniform thickness and excellent antireflection. It becomes a film with excellent properties.
  • moisture in the aqueous coating solution is removed, so that a dense multimer of elements formed by a binder precursor containing a trivalent element and a pentavalent element is present between the silica particles.
  • a binder in the binding network silica particles are firmly bonded to each other through the binder, a dense film containing voids is formed between the silica particles, and a dry film with higher antireflection properties and hardness is formed, reflecting It is considered that a film having excellent scratch resistance as well as prevention can be obtained.
  • the film becomes dense and the film surface becomes smooth it is considered that dirt is difficult to adhere and excellent antifouling properties can be obtained.
  • the coating film can be dried using a heating device.
  • the heating device is not particularly limited as long as it can be heated to a target temperature, and any known heating device can be used.
  • the heating device an oven, an electric furnace, or the like, or a heating device uniquely manufactured according to the production line can be used.
  • the coating film may be dried by, for example, heating the coating film at an ambient temperature of 40 ° C. to 400 ° C. using the above heating device.
  • the heating time can be about 1 to 30 minutes.
  • the drying conditions for the coating film are preferably drying conditions in which the coating film is heated at an atmospheric temperature of 40 ° C. to 200 ° C. for 1 minute to 10 minutes, and drying is performed at an atmospheric temperature of 100 ° C. to 180 ° C. for 1 minute to 5 minutes. Conditions are more preferred.
  • the coating film thickness after drying can be appropriately selected according to the purpose of use of the film. Especially, it is preferable that the film thickness after drying is 50 nm or more. When the film thickness is 50 nm or more, the coating film after drying is more excellent in antireflection properties.
  • the coating film after drying preferably has a thickness of 50 nm to 350 nm, more preferably 100 nm to 300 nm, and particularly preferably 100 nm to 250 nm.
  • the content of the silica particles in the coating film after the coating film drying step and before the coating film baking step is 64% by mass to 95% by mass with respect to the total solid content of the coating film. It is preferably 70% by mass to 95% by mass.
  • the content of the silica particles in the coating film after drying subjected to the coating film baking step is within the above range, a film excellent in antireflection properties, scratch resistance and antifouling properties can be formed.
  • the film manufacturing method of the present embodiment preferably includes a coating film baking step of baking the dried coating film at an ambient temperature of 150 ° C. or more and 400 ° C. or less after the above-described coating film drying step. .
  • the baking temperature in the coating film baking step may be a temperature exceeding 400 ° C., for example, exceeding 400 ° C. and not more than 800 ° C.
  • baking at an atmospheric temperature of 400 ° C. or lower further increases the hardness of the dense film formed in the coating film drying step, resulting in more scratch resistance.
  • the anti-reflection property is remarkably improved by the formation of voids resulting from the improvement and the solid bonding of the silica particles through the binder.
  • the coating film can be baked using a heating device.
  • the heating device is not particularly limited as long as it can be heated to a target temperature, and any known heating device can be used.
  • As the heating device in addition to an electric furnace or the like, it is possible to use a firing device uniquely produced in accordance with a production line.
  • the firing temperature (atmosphere temperature) of the coating film is preferably 150 ° C. or higher and 400 ° C. or lower, more preferably 150 ° C. or higher and 350 ° C. or lower, and further preferably 200 ° C. or higher and 300 ° C. or lower.
  • the firing time is preferably 1 minute to 20 minutes, more preferably 1 minute to 10 minutes.
  • the coating film thickness after firing can be appropriately selected according to the intended use of the film. Especially, it is preferable that the film thickness after baking is 50 nm or more. When the film thickness is 50 nm or more, the coating film after baking is more excellent in antireflection properties.
  • the coating film after baking preferably has a film thickness of 50 nm to 350 nm, more preferably 100 nm to 300 nm, and particularly preferably 100 nm to 250 nm.
  • the baking temperature is preferably 150 ° C. or higher and 400 ° C. or lower, and the baking temperature range includes the drying temperature range.
  • membrane of this embodiment can perform the coating film drying process and the coating film baking process performed after the coating film drying process if needed in one process.
  • the heating condition is preferably 150 ° C. or more and 400 ° C. or less, more preferably 180 ° C. or more and 350 ° C. or less, and 200 ° C. More preferably, it is 300 degrees C or less.
  • the firing time is preferably 1 minute to 30 minutes, more preferably 1 minute to 150 minutes.
  • the film manufacturing method of the present embodiment may include other steps as necessary within a range not impairing the effects of the present embodiment.
  • Examples of other processes include a cleaning process, a surface treatment process, and a cooling process.
  • At least the coating film after passing through the coating film drying step has an average reflectivity at 5 ° incidence with light having a wavelength of 400 nm to 1100 nm that is lower than the average reflectivity of the substrate, and is defined by the following formula (1).
  • the antireflection performance can be expressed by the absolute value of the average reflectance change ⁇ R.
  • the “coating film after having undergone at least the coating film drying process” may be a coating film that has undergone the above-described coating film drying process, and a film or coating that has undergone only the coating film drying process after the coating film forming process.
  • the average reflectance change ⁇ R in the formula (1) is the average reflectance of the base material on which the coating film is not formed (average reflectance of the R base material ) and the average reflection of the base material having the coating film formed with the aqueous coating liquid.
  • the rate average reflectance of the base material after the R film is formed ) can be determined by measuring a white barium sulfate plate as a reference.
  • the reflectance can be measured by using a spectrophotometer with an integrating sphere.
  • an ultraviolet-visible infrared spectrophotometer (model number: UV3100PC, manufactured by Shimadzu Corporation) is used as a measuring device, and the reflectance in light having a wavelength of 400 nm to 1100 nm is measured using an integrating sphere.
  • a value obtained by arithmetically averaging the reflectance values at the respective wavelengths is adopted as the average reflectance.
  • At least the absolute value of the coating film average reflectance change ⁇ R after drying is preferably 2.0% or more, and more preferably 2.5% or more, from the viewpoint of antireflection properties.
  • the film of the present embodiment includes silica particles having an average primary particle size of 100 nm or less and at least one of a trivalent element and a pentavalent element. Adjacent silica particles are composed of a trivalent element and a pentavalent element. It is a film
  • silica particles when spherical silica particles are used, there is no deformation due to heating, and the silica particles Since the amount of the binder containing at least one of a trivalent element and a pentavalent element existing between them is extremely small, it is possible to confirm an appearance such that spherical silica particles are point-bonded to each other.
  • the presence of at least one of trivalent and pentavalent elements between the silica particles can be confirmed by X-ray photoelectric spectroscopy analysis from the cross-sectional direction of the film.
  • a film formed by bonding between silica particles via a silicon compound such as alkoxysilane contains a silicon compound between the silica particles when the film is observed by electron microscopic analysis from the cross-sectional direction of the film described above.
  • the presence of the binder layer can be confirmed, and voids having a smaller volume than the voids between the silica particles of this embodiment are observed.
  • the presence of silicon as an element can be confirmed by X-ray photoelectric spectroscopy analysis from the cross-sectional direction of the film, the presence of a trivalent element and a pentavalent element cannot be confirmed.
  • SEM-EDX manufactured by JEOL Ltd. is preferably used because the surface shape and elemental analysis can be performed simultaneously.
  • a method of measuring the cross section of the membrane at a magnification of 10,000 times or more with a fracture surface generated by breaking a membrane frozen in liquid nitrogen as a measurement target is preferable.
  • the silica particles are strongly bonded via a binder, and the amount of the binder is extremely small. As a result, it has excellent antireflection properties. Furthermore, since it is a dense film with a smooth surface, it is excellent in scratch resistance and antifouling properties.
  • the film of the present embodiment is preferably a film produced by the film production method of the present embodiment using the aqueous coating liquid of the present embodiment described above.
  • the aqueous coating solution preferably used for forming the film is synonymous with the aqueous coating solution of the present embodiment described above and the aqueous coating solution in the method of manufacturing a film of the present embodiment, and the preferred embodiments are also the same.
  • the film of this embodiment preferably has a thickness of 50 nm to 350 nm, more preferably 100 nm to 300 nm, and still more preferably 100 nm to 250 nm from the viewpoint of antireflection properties.
  • the laminated body of this embodiment has the film
  • the laminate having the film of this embodiment is excellent in antireflection properties, scratch resistance, and antifouling properties due to the characteristics of the film of this embodiment.
  • the base material in the laminated body of this embodiment is not specifically limited.
  • the substrate the substrate used in the film forming method of the present embodiment described above can be similarly applied.
  • the substrate that can be used for the laminate include substrates such as glass, resin, metal, ceramic, and composite materials thereof, and any of these substrates can be suitably used in this embodiment.
  • a base material a glass base material is preferable from an adhesive viewpoint with the film
  • the laminate having the film of the present embodiment on the substrate is excellent in antireflection, scratch resistance, and antifouling properties, for example, it is used for solar cell modules, surveillance cameras, lighting equipment, protective films for signs, etc. Can be suitably used.
  • the solar cell module of the present embodiment includes the laminate of the present embodiment described above.
  • the solar cell module of the present embodiment is excellent in antireflection, scratch resistance, and antifouling properties provided on the solar light incident side of the solar cell element that converts the light energy of sunlight into electrical energy. It may be arranged between a laminate having the above film and a solar cell backsheet represented by a polyester film.
  • the laminate of the present embodiment and the back sheet for solar cells such as a polyester film are sealed with a sealing material typified by a resin such as an ethylene-vinyl acetate copolymer.
  • the solar cell module of the present embodiment preferably includes the laminated body of the present embodiment on the side on which sunlight is incident, and other configurations other than having the laminated body of the present embodiment are arbitrary.
  • Examples of the substrate provided on the side on which sunlight is incident include a glass substrate and a transparent resin substrate such as an acrylic resin, and a glass substrate is preferable.
  • the solar cell module of this embodiment includes silicon-based solar cell elements such as single crystal silicon, polycrystalline silicon, and amorphous silicon, copper-indium-gallium-selenium, copper-indium-selenium, cadmium-tellurium, gallium-arsenide, etc. Any of various known solar cell elements such as III-V group II-VI compound semiconductor solar cell elements can be applied. Since the solar cell module of the present embodiment includes a laminate having a film having good antireflection properties, scratch resistance, and antifouling properties, preferably on a glass substrate, undesired reflection of sunlight is suppressed, Sunlight can be efficiently supplied to the solar cell element.
  • Example 1 [Preparation of aqueous coating solution 1] Aqueous dispersion of silica particles (nonporous silica particles, NALCO (registered trademark) 8699: trade name, average primary particle diameter of silica particles: 3 nm, solid content: 15% by mass, surface potential: minus (negative), NALCO (Manufactured) 0.300 parts by mass of aluminum metaphosphate (manufactured by Taihei Chemical Industrial Co., Ltd., molecular weight 263.9) was added as a binder precursor to 89.40 parts by mass.
  • NALCO registered trademark
  • Al metaphosphate manufactured by Taihei Chemical Industrial Co., Ltd., molecular weight 263.9
  • a polyol type nonionic surfactant (trade name: TRITON (registered trademark) BG-10, alkylpolyglucoside surfactant, solid content: 70% by mass, manufactured by Dow Chemical Company) was added. Thereafter, deionized water was added in an amount such that the total amount became 1000 parts by mass, and the aqueous coating solution 1 was prepared by stirring.
  • the content ratio of the binder precursor with respect to the silica particle in the aqueous coating liquid 1 is 0.0224 in mass ratio.
  • the aqueous coating solution 1 was coated on a glass substrate using a bar coater (coating amount: 10 mL / m 2 to 20 mL / m 2 ) to form a coating film (coating film forming step).
  • the coating film was heated using an oven at an ambient temperature of 100 ° C. for 2 minutes and dried (coating film drying step).
  • the dried coating film is baked at an atmospheric temperature of 280 ° C. for 3 minutes using an electric furnace (coating film baking step), and a film sample 1 including a film formed using an aqueous coating solution on a glass substrate is obtained.
  • the film sample 1 was produced on the application
  • aqueous coating solution 2 Preparation of aqueous coating solution 2
  • an aqueous dispersion of silica particles was prepared from Snowtex (registered trademark) 50 (trade name, average primary particle diameter of silica particles: 25 nm, solid content: 48% by mass, surface potential: minus, Nissan.
  • Aqueous coating solution 2 was prepared in the same manner as aqueous coating solution 1 except that the amount added was changed to 27.9 parts by mass.
  • the content ratio of the binder precursor with respect to the silica particle in the aqueous coating liquid 2 is 0.0224 in mass ratio.
  • a membrane sample 2 was produced in the same manner as the membrane sample 1 except that the aqueous coating solution 1 used in the production of the membrane sample 1 was changed to the aqueous coating solution 2.
  • aqueous coating solution 3 Preparation of aqueous coating solution 3
  • an aqueous dispersion of silica particles was prepared by using a trade name: Snowtex (registered trademark) ZL, average primary particle diameter of silica particles: 100 nm, solid content: 40% by mass, surface potential: minus, Nissan Aqueous coating solution 3 was prepared in the same manner as aqueous coating solution 1 except that the amount was changed to 33.5 parts by mass from Chemical Industries.
  • the content ratio of the binder precursor with respect to the silica particles in the aqueous coating liquid 3 is 0.0224 in mass ratio.
  • a membrane sample 3 was produced in the same manner as the membrane sample 1 except that the aqueous coating solution 1 used in the production of the membrane sample 1 was changed to the aqueous coating solution 3.
  • aqueous coating solution 4 Preparation of aqueous coating solution 4
  • the aqueous coating solution was the same as the aqueous coating solution 1 except that the addition amount of aluminum metaphosphate as a binder precursor was changed from 0.300 parts by mass to 0.120 parts by mass. 4 was prepared. In addition, the content ratio of the binder precursor with respect to the silica particles in the aqueous coating liquid 4 is 0.0089 in mass ratio.
  • a membrane sample 4 was produced in the same manner as the membrane sample 1 except that the aqueous coating solution 1 used in the production of the membrane sample 1 was changed to the aqueous coating solution 4.
  • aqueous coating solution 5 Preparation of aqueous coating solution 5
  • the aqueous coating solution was the same as the aqueous coating solution 1 except that the addition amount of aluminum metaphosphate as a binder precursor was changed from 0.300 parts by mass to 0.500 parts by mass. 5 was prepared.
  • the content ratio of the binder precursor with respect to the silica particle in the aqueous coating liquid 5 is 0.0373 by mass ratio.
  • a membrane sample 5 was produced in the same manner as the membrane sample 1 except that the aqueous coating solution 1 used in the production of the membrane sample 1 was changed to the aqueous coating solution 5.
  • Example 6 [Production of membrane sample 6] The film was formed except that the film formed on the glass substrate was changed to a film thickness of 130 nm after drying and baking using the aqueous coating solution 1 used in the preparation of the film sample 1 and changed to a film thickness of 40 nm. In the same manner as Sample 1, a membrane sample 6 was produced.
  • Example 7 [Production of membrane sample 7] Using the aqueous coating solution 1 used in the production of the film sample 1, the film formed on the glass substrate was changed from a film thickness of 130 nm after drying and baking to a film thickness of 360 nm. Similarly, a membrane sample 7 was produced.
  • aqueous coating solution 8 Preparation of aqueous coating solution 8
  • the aqueous coating solution was the same as the aqueous coating solution 3 except that the addition amount of aluminum metaphosphate as a binder precursor was changed from 0.300 parts by mass to 0.704 parts by mass. 8 was prepared.
  • the content ratio of the binder precursor with respect to the silica particles in the aqueous coating liquid 8 is 0.0525 in mass ratio.
  • a membrane sample 8 was produced in the same manner as the membrane sample 1 except that the aqueous coating solution 1 used in the production of the membrane sample 1 was changed to the aqueous coating solution 8.
  • aqueous coating solution 9 Preparation of aqueous coating solution 9
  • the aqueous coating solution was the same as the aqueous coating solution 3 except that the addition amount of aluminum metaphosphate as a binder precursor was changed from 0.300 parts by mass to 0.067 parts by mass. 8 was prepared.
  • the content ratio of the binder precursor with respect to the silica particle in the aqueous coating liquid 8 is 0.0050 by mass ratio.
  • a membrane sample 9 was produced in the same manner as the membrane sample 1 except that the aqueous coating solution 1 used in the production of the membrane sample 1 was changed to the aqueous coating solution 9.
  • aqueous coating solution 10 Preparation of aqueous coating solution 10
  • an aqueous dispersion of silica particles was prepared using a trade name: Snowtex (registered trademark) XL, an average primary particle diameter of silica particles: 50 nm, a solid content: 40% by mass, a surface potential: minus, Nissan. Made by Chemical Industry Co., Ltd., except that the addition amount was changed to 33.5 parts by mass, and the addition amount of aluminum metaphosphate as a binder precursor was changed from 0.300 parts by mass to 0.704 parts by mass.
  • An aqueous coating solution 10 was prepared in the same manner as Solution 3.
  • the content ratio of the binder precursor with respect to the silica particles in the aqueous coating liquid 10 is 0.0525 by mass ratio.
  • a membrane sample 10 was produced in the same manner as the membrane sample 1 except that the aqueous coating solution 1 used in the production of the membrane sample 1 was changed to the aqueous coating solution 10.
  • aqueous coating solution 11 Preparation of aqueous coating solution 11
  • an aqueous dispersion of silica particles was made from Snowtex (registered trademark) XL (trade name, average primary particle diameter of silica particles: 50 nm, solid content: 40 mass%, surface potential: minus, Nissan Chemical Co., Ltd. Manufactured by Kogyo Co., Ltd.), the addition amount was changed to 33.5 parts by mass, and the addition amount of aluminum metaphosphate as a binder precursor was changed from 0.300 parts by mass to 0.067 parts by mass.
  • An aqueous coating solution 11 was prepared in the same manner as the coating solution 3.
  • the content ratio of the binder precursor with respect to the silica particle in the aqueous coating liquid 11 is 0.0050 by mass ratio.
  • aqueous coating solution 12 Preparation of aqueous coating solution 12
  • an aqueous dispersion of silica particles was prepared by using a trade name: NALCO (registered trademark) 1130, nonporous silica particles, average primary particle diameter of silica particles: 8 nm, solid content: 30% by mass, surface Potential: minus, made by NALCO, the addition amount was changed to 44.70 parts by mass, and the addition amount of aluminum metaphosphate as a binder precursor was changed from 0.300 parts by mass to 0.134 parts by mass
  • NALCO registered trademark
  • the content ratio of the binder precursor with respect to the silica particle in the aqueous coating liquid 12 is 0.0100 by mass ratio.
  • aqueous coating solution 13 Preparation of aqueous coating solution 13
  • an aqueous dispersion of silica particles was prepared by using a trade name: NALCO (registered trademark) 1130, nonporous silica particles, average primary particle diameter of silica particles: 8 nm, solid content: 30 mass%, surface Potential: minus, made by NALCO, the addition amount was changed to 44.70 parts by mass, and the addition amount of aluminum metaphosphate as a binder precursor was changed from 0.300 parts by mass to 0.469 parts by mass
  • NALCO registered trademark
  • the content ratio of the binder precursor with respect to the silica particle in the aqueous coating liquid 13 is 0.0350 by mass ratio.
  • aqueous coating solution 14 In the preparation of the aqueous coating liquid 1, an aqueous dispersion of silica particles was prepared using a trade name: Snowtex (registered trademark) AK, average primary particle diameter of silica particles: 10 nm, solid content: 18% by mass, surface potential: plus, Nissan An aqueous coating solution 14 was prepared in the same manner as the aqueous coating solution 1 except that the amount was changed to 74.4 parts by mass from Chemical Industries. In addition, the content ratio of the binder precursor with respect to the silica particle in the aqueous coating liquid 14 is 0.0224 in mass ratio. [Production of membrane sample 14] A membrane sample 14 was produced in the same manner as the membrane sample 1 except that the aqueous coating solution 1 used in the production of the membrane sample 1 was changed to the aqueous coating solution 14.
  • aqueous coating solution 15 An aqueous coating solution 15 was prepared in the same manner as the aqueous coating solution 1 except that no polyol type nonionic surfactant was added in the preparation of the aqueous coating solution 1. In addition, the content ratio of the binder precursor with respect to the silica particles in the aqueous coating liquid 15 is 0.0224 in mass ratio. [Preparation of membrane sample 15] A membrane sample 15 was produced in the same manner as the membrane sample 1 except that the aqueous coating solution 1 used in the production of the membrane sample 1 was changed to the aqueous coating solution 15.
  • aqueous coating solution 16 was prepared in the same manner as the aqueous coating solution 1 except that 0.1 mol / L hydrochloric acid was further added to adjust the pH to 8.0 in the preparation of the aqueous coating solution 1. In addition, the content ratio of the binder precursor with respect to the silica particles in the aqueous coating liquid 16 is 0.0224 in mass ratio. [Production of membrane sample 16] A membrane sample 16 was produced in the same manner as the membrane sample 1 except that the aqueous coating solution 1 used in the production of the membrane sample 1 was changed to the aqueous coating solution 16.
  • Example 17 [Preparation of aqueous coating solution 17]
  • an aqueous dispersion of silica particles was prepared using a trade name: Snowtex (registered trademark) O, an average primary particle diameter of silica particles: 10 nm, a solid content: 20% by mass, a surface potential: plus, Nissan.
  • Aqueous coating solution 17 was prepared in the same manner as aqueous coating solution 1 except that the amount was 66.9 parts by mass and the polyol type nonionic surfactant was not added.
  • the content ratio of the binder precursor with respect to the silica particle in the aqueous coating liquid 17 is 0.0224 in mass ratio.
  • a membrane sample 17 was produced in the same manner as the membrane sample 1 except that the aqueous coating solution 1 used in the production of the membrane sample 1 was changed to the aqueous coating solution 17.
  • Example 18 [Production of membrane sample 18] A membrane sample 18 was produced in the same manner as the membrane sample 1 except that the firing condition was changed to 150 ° C. in the production of the membrane sample 1.
  • Example 19 [Preparation of membrane sample 19] A membrane sample 19 was produced in the same manner as the membrane sample 1 except that the firing condition was changed to 400 ° C. in the production of the membrane sample 1.
  • Example 20 [Production of membrane sample 20] A membrane sample 20 was produced in the same manner as the membrane sample 1 except that the firing condition was changed to 500 ° C. in the production of the membrane sample 1.
  • Example 21 [Production of membrane sample 21] A membrane sample 21 was produced in the same manner as the membrane sample 1 except that the firing condition was changed to 130 ° C. in the production of the membrane sample 1.
  • membrane sample 22 production A membrane sample 22 was produced in the same manner as the membrane sample 1 except that the coating film drying step performed in the production of the membrane sample 1 and the optional coating film baking step were performed in one step.
  • Example 23 [Preparation of aqueous coating solution 23]
  • an aqueous coating liquid 23 was prepared in the same manner as the aqueous coating liquid 1 except that the amount of the binder precursor added was changed to 0.80 parts by mass.
  • the content ratio of the binder precursor with respect to the silica particles in the aqueous coating liquid 23 is 0.0600 in mass ratio.
  • a membrane sample 23 was produced in the same manner as the membrane sample 1 except that the aqueous coating solution 1 used in the production of the membrane sample 1 was changed to the aqueous coating solution 23.
  • Example 24 [Preparation of aqueous coating solution 24]
  • the aqueous coating solution 24 was prepared in the same manner as the aqueous coating solution 1 except that the amount of addition of aluminum metaphosphate as a binder precursor was changed from 0.300 parts by mass to 0.05 parts by mass. Was prepared.
  • the content ratio of the binder precursor with respect to the silica particles in the aqueous coating liquid 24 is 0.0040 in mass ratio.
  • a membrane sample 24 was produced in the same manner as the membrane sample 1 except that the aqueous coating solution 1 used in the production of the membrane sample 1 was changed to the aqueous coating solution 24.
  • aqueous coating solution 25 In the preparation of the aqueous coating liquid 1, an aqueous dispersion of silica particles was prepared by using a trade name: Snowtex (registered trademark) ST-30, an average primary particle diameter of silica particles: 10 nm, a solid content: 30% by mass, and a surface potential: minus. An aqueous coating solution 25 was prepared in the same manner as the aqueous coating solution 1 except that the amount was changed to 44.6 parts by mass from Nissan Chemical Industries. In addition, the content ratio of the binder precursor with respect to the silica particles in the aqueous coating liquid 25 is 0.0224 in mass ratio. [Preparation of membrane sample 25] A membrane sample 25 was produced in the same manner as the membrane sample 1 except that the aqueous coating solution 1 used in the production of the membrane sample 1 was changed to the aqueous coating solution 25.
  • Comparative Example 1 [Preparation of comparative aqueous coating solution 1] 89.4 parts by mass of an aqueous dispersion of silica particles (trade name: NALCO (registered trademark) 8699, nonporous silica particles, average primary particle diameter of silica particles: 450 nm, solid content: 15% by mass, manufactured by NALCO)
  • a binder precursor 0.300 parts by mass of aluminum metaphosphate (manufactured by Taihei Chemical Industry, molecular weight 263.9) was added.
  • the comparative aqueous coating liquid 1 was prepared by adding the amount of deionized water used as a total amount to 1000 mass parts, and stirring.
  • the content ratio of the binder precursor with respect to the silica particle in the comparative aqueous coating liquid 1 is 0.0220 by mass ratio.
  • the pH of the comparative aqueous coating solution 1 (25 ° C.) was measured by the same method as that of the aqueous coating solution 1 and found to be 10.5.
  • a comparative membrane sample 1 was produced in the same manner as the membrane sample 1 except that the aqueous coating solution 1 used in the production of the membrane sample 1 was changed to the comparative aqueous coating solution 1.
  • Comparative Example 2 [Preparation of comparative aqueous coating solution 2]
  • a comparative aqueous coating solution 2 was prepared in the same manner as in the aqueous coating solution 1 except that the binder precursor aluminum metaphosphate was not added.
  • the content ratio of the binder precursor to the silica particles in the comparative aqueous coating solution 2 is 0.000 in terms of mass ratio.
  • a comparative membrane sample 2 was produced in the same manner as the membrane sample 1 except that the aqueous coating solution 1 used in the production of the membrane sample 1 was changed to the comparative aqueous coating solution 2.
  • Comparative Example 3 [Preparation of comparative aqueous coating solution 3]
  • the product name tetraethoxysilane (98% solution, molecular weight 208.3), solid content: 98% by mass, manufactured by Wako Pure Chemical Industries
  • a comparative aqueous coating solution 3 was prepared in the same manner as the aqueous coating solution 1 except that the amount added was changed to 0.450 parts by mass.
  • the content ratio of the binder precursor with respect to the silica particle in the comparative aqueous coating liquid 3 is 0.0329 by mass ratio.
  • a comparative membrane sample 3 was produced in the same manner as the membrane sample 1 except that the aqueous coating solution 1 used in the production of the membrane sample 1 was changed to the comparative aqueous coating solution 3.
  • Comparative Example 4 [Preparation of comparative aqueous coating solution 4]
  • the trade name sodium sulfite (molecular weight: 126.0), solid content: 100% by mass, manufactured by Wako Pure Chemical Industries, Ltd.
  • a comparative aqueous coating solution 4 was prepared in the same manner as the aqueous coating solution 1 except that was changed to 0.450 parts by mass.
  • the content ratio of the binder precursor to the silica particles in the comparative aqueous coating solution 4 is 0.0347 in mass ratio.
  • a comparative membrane sample 4 was produced in the same manner as the membrane sample 1 except that the aqueous coating solution 1 used in the production of the membrane sample 1 was changed to the comparative aqueous coating solution 4.
  • Comparative Example 5 [Preparation of comparative aqueous coating solution 5]
  • aqueous coating solution 1 instead of aluminum metaphosphate as a binder precursor, sodium silicate (molecular weight 122.1), solid content: 38% by mass aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) was added.
  • a comparative aqueous coating solution 5 was prepared in the same manner as the aqueous coating solution 1 except that the amount was changed to 0.750 parts by mass.
  • the content ratio of the binder precursor to the silica particles in the comparative aqueous coating solution 5 is 0.0213 in terms of mass ratio.
  • a comparative membrane sample 5 was produced in the same manner as the membrane sample 1 except that the aqueous coating solution 1 used in the production of the membrane sample 1 was changed to the comparative aqueous coating solution 5.
  • a comparative membrane sample 6 was produced in the same manner as the membrane sample 1 except that the aqueous coating solution 1 used in the production of the membrane sample 1 was changed to the comparative aqueous coating solution 6.
  • ⁇ Film thickness> Each film sample was cut with a microtome and observed with a field emission scanning electron microscope (FE-SEM) from the cross-sectional direction to measure the film thickness. Each film sample was measured at 10 locations, and the average value was calculated to obtain the film thickness.
  • FE-SEM field emission scanning electron microscope
  • ⁇ Antireflection (AR)> The reflectivity of each film sample with light having a wavelength of 400 nm to 1100 nm was measured using an integrating sphere with an ultraviolet-visible infrared spectrophotometer (model number: UV3100PC, manufactured by Shimadzu Corporation). At the time of reflectance measurement, a black tape was attached to the glass substrate surface on the back surface in order to suppress reflection on the back surface of the glass substrate having the film sample (the surface on which the glass substrate film was not formed). .
  • the average reflectance is calculated from the reflectance of each wavelength at wavelengths of 400 nm to 1100 nm obtained by measurement, and the absolute value (
  • ⁇ R is negative, and
  • ⁇ Scratch resistance> Using a rubbing tester under environmental conditions of a temperature of 25 ° C. and a relative humidity of 55%, the membrane surface of the membrane sample was subjected to a load of 50 g on steel wool (# 0000, manufactured by Nippon Steel Wool Co., Ltd.) at a speed of 1000 mm / min. After reciprocating 10 times in a fixed direction, the film surface was observed visually and with an optical microscope (magnification: 100 times), and scratch resistance was evaluated according to the following evaluation criteria. Visual observation was performed under a fluorescent lamp and a tungsten light source. As for scratch resistance, [A], [B] and [C] are acceptable.
  • a natural ocher pigment (manufactured by Holbein Co., Ltd.) was uniformly dispersed on the membrane of the membrane sample and adhered, and then the back surface of the membrane sample was struck to remove the attached natural ocher pigment. This operation was repeated 10 times. Thereafter, the adhesion state of the natural ocher pigment was visually confirmed, and the antifouling property was evaluated according to the following evaluation criteria. As for the antifouling property, [A] and [B] are acceptable.
  • ⁇ Surface shape The surface of the film sample after drying and before baking and the surface of the film sample after baking were observed visually and with an optical microscope (magnification: 100 times), and the surface condition was evaluated according to the following evaluation criteria.
  • Table 1 “after baking and before baking” is expressed as “unfired”, and “after baking” is expressed as “baking”.
  • “A], [B] and [C] are allowable ranges.
  • each film sample of the example formed using the aqueous coating liquid of the example was excellent in antireflection property, scratch resistance, and antifouling property. From the comparison between Example 1 and Example 22, even when the coating film drying step and the coating film baking step are performed in one step, the resulting film is antireflective, as in the case where it is performed in two steps. It can be seen that both scratch resistance and antifouling properties are good. On the other hand, even if the binder precursor was contained, Comparative Example 1 in which the particle diameter of the silica particles was large was inferior in all of antireflection properties, scratch resistance, and antifouling properties.

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Abstract

La présente invention concerne un liquide de revêtement aqueux qui contient de l'eau, des particules de silice ayant un diamètre de particule primaire moyen de 100 nm ou moins, et un précurseur de liant qui a un poids moléculaire de 600 ou moins et qui est composé d'un sel d'un composé contenant au moins un élément choisi parmi des éléments trivalents et des éléments pentavalents qui sont dissociés dans une solution contenant de l'eau ; un film utilisant ce liquide de revêtement aqueux ; un procédé de production de ce film ; et des applications de ce film.
PCT/JP2016/070586 2015-07-31 2016-07-12 Liquide de revêtement aqueux, film et procédé de production associé, stratifié et module photovoltaïque WO2017022433A1 (fr)

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JP2015152648A JP2017031325A (ja) 2015-07-31 2015-07-31 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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JP6848906B2 (ja) * 2018-03-12 2021-03-24 株式会社豊田中央研究所 コーティング液及び熱電部材の製造方法

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JPS4834938A (fr) * 1971-09-09 1973-05-23
JPS4994716A (fr) * 1972-11-30 1974-09-09
JPS50156519A (fr) * 1974-06-08 1975-12-17
JPS50157423A (fr) * 1974-06-12 1975-12-19
JPS53149225A (en) * 1977-06-01 1978-12-26 Nisshin Eng Inorganic coating composition
JPH03103379A (ja) * 1989-09-14 1991-04-30 Shinagawa Refract Co Ltd 基板表面処理剤
JPH0762268A (ja) * 1993-08-20 1995-03-07 Kansai Paint Co Ltd プライマー塗装鋼板およびこのものに用いられるプライマー組成物
JP2000034579A (ja) * 1998-04-22 2000-02-02 Toyobo Co Ltd 表面処理金属材料
JP2003231827A (ja) * 2002-02-12 2003-08-19 Canon Inc 防曇性コーティング材料、防曇性コーティング膜および防曇性光学部材
JP2006272767A (ja) * 2005-03-29 2006-10-12 Kobe Steel Ltd 樹脂塗装金属板
JP2006336106A (ja) * 2005-05-04 2006-12-14 Furakuto:Kk 金属用クロムフリー表面処理剤及び表面処理金属材料
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JP2008137876A (ja) * 2006-12-05 2008-06-19 Catalysts & Chem Ind Co Ltd シリカゾルおよびこれを含む塗料組成物
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JP2015085561A (ja) * 2013-10-29 2015-05-07 株式会社神戸製鋼所 黒色塗装金属板

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