WO2022168451A1 - Liquide de dispersion de particules métalliques planes et procédé de production de film intermédiaire pour verre feuilleté - Google Patents

Liquide de dispersion de particules métalliques planes et procédé de production de film intermédiaire pour verre feuilleté Download PDF

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WO2022168451A1
WO2022168451A1 PCT/JP2021/045908 JP2021045908W WO2022168451A1 WO 2022168451 A1 WO2022168451 A1 WO 2022168451A1 JP 2021045908 W JP2021045908 W JP 2021045908W WO 2022168451 A1 WO2022168451 A1 WO 2022168451A1
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laminated glass
metal
metal tabular
particle dispersion
particles
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English (en)
Japanese (ja)
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尚治 清都
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富士フイルム株式会社
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    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • C08L101/14—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity the macromolecular compounds being water soluble or water swellable, e.g. aqueous gels

Definitions

  • the present disclosure relates to a method for producing a metal tabular particle dispersion and an interlayer film for laminated glass.
  • a metal particle dispersion containing metal particles as a dispersoid is used for various purposes depending on the properties of the metal particles.
  • the following metal particle dispersion is known.
  • Patent Document 1 discloses an infrared shielding material fine particle dispersion.
  • the dispersion disclosed in Patent Document 1 below uses metal oxide particles such as tungsten oxide fine particles and composite tungsten oxide fine particles.
  • Patent Document 2 discloses a heat shielding particle dispersion.
  • the dispersion disclosed in Patent Document 2 below uses metal oxide particles such as tin-doped indium oxide particles and antimony-doped tin oxide particles.
  • Patent Document 3 discloses a silver tabular particle-containing dispersion used for forming a heat ray reflective layer.
  • dispersion disclosed in Patent Document 3 below tabular silver particles are used.
  • Patent Document 1 and Patent Document 2 are used as raw materials for interlayer films for laminated glass.
  • the metal oxide particles used in the dispersion liquid as described above absorb heat rays and cannot sufficiently reflect the heat rays. Therefore, the interlayer film for laminated glass obtained using the dispersion liquid as described above cannot exhibit high heat ray shielding properties.
  • the flat silver particles used in the dispersion disclosed in Patent Document 3 can exhibit high heat ray reflectivity.
  • the dispersion as described above is an aqueous dispersion, it is difficult to mix with a polymer such as polyvinyl butyral (PVB), which is generally used as a raw material for interlayer films for laminated glass. As a result, the haze of the laminated glass may increase.
  • PVB polyvinyl butyral
  • the flat silver particles tend to agglomerate, and further improvement in dispersibility is desired. When the dispersibility is lowered, not only does the storage period become shorter, but also the properties of the tabular silver particles may not be exhibited sufficiently.
  • An object of the present disclosure is to provide a metal tabular particle dispersion having excellent dispersibility and a method for producing an interlayer film for laminated glass using the metal tabular particle dispersion.
  • the present disclosure includes the following aspects.
  • ⁇ 1> A metal tabular particle dispersion containing 50% by mass or more of silver and a liquid plasticizer.
  • the liquid plasticizer is dihexyl adipate, triethylene glycol di(2-ethylhexanoate), tetraethylene glycol di(2-ethylhexanoate), triethylene glycol di(2-ethylbutyrate), Any one of ⁇ 1> to ⁇ 4>, which is at least one selected from the group consisting of tetraethylene glycol di(2-ethylbutyrate), tetraethylene glycol diheptanoate and triethylene glycol diheptanoate One is a metal tabular particle dispersion.
  • ⁇ 7> The metal tabular particle dispersion according to any one of ⁇ 1> to ⁇ 6>, further comprising an organic solvent having a boiling point of 100° C. or higher at 1013.25 hPa.
  • ⁇ 8> The metal tabular particle dispersion according to any one of ⁇ 1> to ⁇ 7>, further comprising a dispersant that dissolves in the liquid plasticizer.
  • a method for producing an interlayer film for laminated glass comprising obtaining an interlayer film for laminated glass using the metal tabular particle dispersion liquid according to any one of ⁇ 1> to ⁇ 8>.
  • a metal tabular particle dispersion having excellent dispersibility and a method for producing an interlayer film for laminated glass using the metal tabular particle dispersion are provided.
  • FIG. 1 is a schematic diagram showing an example of a method for producing an intermediate film for laminated glass and a laminated glass.
  • a numerical range indicated using "-" indicates a range that includes the numerical values described before and after "-" as lower and upper limits, respectively.
  • upper or lower limits described in a certain numerical range may be replaced with upper or lower limits of other numerical ranges described step by step.
  • upper or lower limits described in a certain numerical range may be replaced with values shown in Examples.
  • the amount of each component in the composition means the total amount of the multiple substances present in the composition unless otherwise specified when there are multiple substances corresponding to each component in the composition. .
  • step includes not only independent steps, but also if the intended purpose of the step is achieved even if it cannot be clearly distinguished from other steps. .
  • ordinal numbers are terms used to distinguish constituent elements, and do not limit the number of constituent elements or their superiority or inferiority.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) are TSKgel GMHxL (trade name manufactured by Tosoh Corporation), TSKgel G4000HxL (trade name manufactured by Tosoh Corporation) and TSKgel It is a molecular weight converted using polystyrene as a standard substance using a gel permeation chromatography (GPC) analyzer using a column of G2000HxL (manufactured by Tosoh Corporation) and a differential refractometer. Tetrahydrofuran (THF) is used as solvent.
  • GPC gel permeation chromatography
  • a metal tabular particle dispersion according to an embodiment of the present disclosure includes metal tabular particles containing 50% by mass or more of silver, and a liquid plasticizer. According to the embodiment described above, a metal tabular particle dispersion having excellent dispersibility is provided. Although the detailed mechanism is not clear, it is presumed that the liquid plasticizer functioned as a dispersion medium for the metal tabular particles, improving the dispersibility of the metal tabular particles.
  • a metal tabular grain dispersion liquid according to an embodiment of the present disclosure includes metal tabular grains containing 50% by mass or more of silver (hereinafter sometimes simply referred to as “metal tabular grains” or “silver tabular grains”).
  • metal tabular grains means a grain containing two principal planes facing in opposite directions.
  • Metal tabular grains containing 50% by mass or more of silver can exhibit high heat ray reflectivity. Therefore, for example, when an intermediate film for laminated glass and laminated glass are produced using the metal tabular particle dispersion according to an embodiment of the present disclosure, the heat ray shielding properties of the intermediate film for laminated glass and laminated glass are improved.
  • the tabular metal particles contain 50% by mass or more of silver.
  • the proportion of silver in the tabular metal grains is 50% by mass or more.
  • the metal tabular grains may contain metals other than silver, if necessary. From the viewpoint of improving heat ray shielding properties, the proportion of silver in the tabular metal grains is preferably 50% by mass to 100% by mass, more preferably 80% by mass to 100% by mass, and more preferably 95% by mass to 100% by mass is particularly preferred.
  • the proportion of silver in the metal tabular grains is calculated by the ICP (Inductively Coupled Plasma) measurement method. Specific procedures are shown below. Proportion of silver in the tabular metal particles based on the amount of metal contained in the tabular metal particles (for example, the amount of silver, the amount of gold, and the amount of platinum) measured using an ICP measurement device (Optima 7300DV, manufactured by PerkinElmer) is calculated.
  • ICP Inductively Coupled Plasma
  • the metal tabular particles include triangular metal tabular particles, hexagonal metal tabular particles, and circular metal tabular particles.
  • the metal tabular grains are preferably at least one selected from the group consisting of hexagonal or more polygonal metal tabular grains and circular metal tabular grains. and circular metal tabular grains. Further, the metal tabular grains are preferably hexagonal or polygonal tabular grains or circular tabular metal grains, more preferably hexagonal tabular metal grains or circular tabular metal grains.
  • circular in the circular metal tabular grain means a shape in which the number of sides having a length of 50% or more of the average circle equivalent diameter of the metal tabular grain is 0 per one metal tabular grain. do. For example, when the main planes of circular metal tabular grains are observed using a transmission electron microscope, a round shape with no corners is observed.
  • hexagonal in the hexagonal metal tabular grain means a shape in which one metal tabular grain has 6 sides having a length of 20% or more of the average circle equivalent diameter of the metal tabular grain. do.
  • the applicability of a polygonal shape other than a hexagon is determined according to the number of sides having a length of 20% or more of the average equivalent circular diameter of the metal tabular grain. For example, when the main planes of hexagonal tabular metal grains are observed using a transmission electron microscope, a hexagonal shape is observed.
  • the hexagonal corners may be sharp or rounded. From the viewpoint of reducing absorption in the visible light region, the hexagonal corners are preferably rounded. The degree of roundness of the hexagonal corners may be determined depending on the purpose.
  • the content of the hexagonal tabular metal particles and the circular tabular metal particles is preferably 60% or more, more preferably 65% or more, of the total number of metal particles. It is more preferably 70% or more, particularly preferably 70% or more.
  • Metal particles in this paragraph means particles containing metal.
  • the average equivalent circle diameter of the metal tabular grains is preferably 10 nm to 500 nm, more preferably 10 nm to 300 nm, and particularly preferably 50 nm to 300 nm. Furthermore, the average equivalent circle diameter of the metal tabular grains is preferably 70 nm to 300 nm, more preferably 80 nm to 250 nm. When the average equivalent circle diameter of the metal tabular grains is increased, the heat ray shielding property is improved. When the average equivalent circle diameter of the metal tabular grains is reduced, the visible light transmittance is improved.
  • the average circle-equivalent diameter of the metal tabular grains is calculated by the following method.
  • the metal tabular grains are observed using a transmission electron microscope (TEM), and the obtained image is imported into image processing software "ImageJ" and subjected to image processing.
  • Image analysis is performed on 1,000 metal tabular grains arbitrarily extracted from TEM images of a plurality of fields of view, and the average circle equivalent diameter of the 1,000 metal tabular grains is calculated. The obtained value is employed as the average circle equivalent diameter of the tabular metal grains.
  • the coefficient of variation of the equivalent circle diameter of the metal tabular grains is preferably 35% or less, more preferably 30% or less, and particularly preferably 20% or less. When the coefficient of variation becomes small, the reflection wavelength range of heat rays in the interlayer film for laminated glass becomes sharp.
  • the variation coefficient of the equivalent circle diameter of the metal tabular grains is calculated by dividing the standard deviation of the equivalent circle diameters of 1,000 metal tabular grains by the average equivalent circle diameter of the metal tabular grains.
  • the circle-equivalent diameter of the metal tabular grains is calculated using the image processing software "ImageJ" described above.
  • the average thickness of the metal tabular grains is preferably 14 nm or less, more preferably 5 nm to 14 nm, and particularly preferably 5 nm to 12 nm.
  • the average thickness of the metal tabular grains is calculated by arithmetically averaging the thicknesses of 100 metal tabular grains by the FIB-TEM method.
  • the thickness of a metal tabular grain corresponds to the distance between two main planes of the metal tabular grain.
  • the average aspect ratio of the metal tabular grains is preferably 6 or more, more preferably 10 or more.
  • the average aspect ratio of the tabular metal grains is preferably 6-40, more preferably 10-35.
  • the average aspect ratio of the metal tabular grains is calculated by dividing the average circle equivalent diameter of the metal tabular grains by the average thickness of the metal tabular grains.
  • a preferred relationship between the average equivalent circle diameter of the metal tabular grains and the average aspect ratio of the metal tabular grains is as follows. In one embodiment, it is preferable that the average equivalent circle diameter of the metal tabular grains is 10 nm to 300 nm and the average aspect ratio of the metal tabular grains is 6 or more. In one embodiment, it is more preferable that the average equivalent circle diameter of the metal tabular grains is 10 nm to 300 nm and the average aspect ratio of the metal tabular grains is 10 or more. In one embodiment, it is particularly preferred that the average equivalent circle diameter of the metal tabular grains is 70 nm to 300 nm and the average aspect ratio of the metal tabular grains is 10 to 35. In the relationship between the average equivalent circle diameter and the average aspect ratio described above, the upper and lower limits of the average equivalent circle diameter may be replaced by the preferred numerical values described above, and the upper and lower limits of the average aspect ratio are already may be replaced with the preferred numerical values described above.
  • Metal tabular grains are manufactured, for example, by a publicly known synthetic method.
  • methods for synthesizing tabular metal grains include a liquid phase method.
  • Liquid phase methods include, for example, chemical reduction methods, photochemical reduction methods, and electrochemical reduction methods. From the viewpoint of the controllability of the shape and size of the metal tabular grains, the chemical reduction method and the photochemical reduction method are preferred.
  • As a method for synthesizing tabular metal grains for example, there is a method in which seed crystals are fixed on the surface of a transparent base material, and then the grains are crystal-grown in a tabular shape.
  • a method for synthesizing tabular metal grains is described, for example, in JP-A-2014-194446. The contents of the above documents are incorporated herein by reference.
  • a metal tabular particle dispersion according to an embodiment of the present disclosure may contain one or more types of metal tabular particles.
  • the proportion of the metal tabular grains in the metal tabular grain dispersion is preferably 0.3% by mass to 30% by mass, more preferably 0.5% by mass to 25% by mass, and 1% by mass to 20% by mass. % by weight is particularly preferred.
  • the proportion of the metal tabular particles in the metal tabular particle dispersion increases, the heat ray shielding property is improved.
  • the proportion of the metal tabular particles in the metal tabular particle dispersion becomes small the dispersibility is improved.
  • a metal tabular particle dispersion according to an embodiment of the present disclosure contains a liquid plasticizer.
  • liquid as used with respect to “liquid plasticizer” means that the substance is in a liquid state under normal atmospheric pressure (ie 1013.25 hPa) and 25°C.
  • the liquid plasticizer contributes to improving the dispersibility of the metal tabular particles.
  • the liquid plasticizer contributes to softening the interlayer film for laminated glass.
  • liquid plasticizer is not limited.
  • Liquid plasticizers include known liquid plasticizers.
  • Liquid plasticizers include, for example, fatty acid esters and phosphoric acid compounds.
  • fatty acid esters include dihexyl adipate, tetraethylene glycol di(2-ethylhexanoate), triethylene glycol di(2-ethylbutyrate), triethylene glycol di(2-ethylhexanoate), triethylene Glycol dicaprylate, triethylene glycol di(n-octanoate), triethylene glycol diheptanoate, tetraethylene glycol diheptanoate, dibutyl sebacate, dioctyl azelate, dibutyl carbitol adipate, ethylene glycol di(2- ethyl butyrate), 1,3-propylene glycol di(2-ethylbutyrate), 1,4-propylene glycol di(2-ethylbutyrate), 1,4-butylene glycol di(2-ethylbutyrate), 1,2-butylene glycol di(2-ethylene butyrate), diethylene glycol di(2-ethylbutyrate), di
  • Examples of phosphoric acid compounds include tributoxyethyl phosphate, isodecylphenyl phosphate and triisopropyl phosphite.
  • the liquid plasticizer is preferably a fatty acid ester, such as dihexyl adipate, triethylene glycol di(2-ethylhexanoate), tetraethylene glycol di(2-ethylhexanoate), At least one selected from the group consisting of triethylene glycol di(2-ethylbutyrate), tetraethylene glycol di(2-ethylbutyrate), tetraethylene glycol diheptanoate and triethylene glycol diheptanoate is more preferred, and triethylene glycol di(2-ethylhexanoate) is particularly preferred.
  • a fatty acid ester such as dihexyl adipate, triethylene glycol di(2-ethylhexanoate), tetraethylene glycol di(2-ethylhexanoate), At least one selected from the group consisting of triethylene glycol di(2-ethylbutyrate), tetraethylene glycol di(2-ethyl
  • the combined metal tabular particle dispersion according to one embodiment of the present disclosure may contain one or more liquid plasticizers.
  • the proportion of the liquid plasticizer in the metal tabular particle dispersion is preferably 50% by mass to 99.7% by mass, more preferably 60% by mass to 99.5% by mass. is more preferable, and 70% by mass to 99% by mass is particularly preferable.
  • the ratio of the content of the liquid plasticizer to the content of the tabular metal particles is preferably 1 to 1,000, more preferably 2 to 500, in terms of mass. 3 to 200 is particularly preferred.
  • the metal tabular particle dispersion according to an embodiment of the present disclosure may further contain a solvent.
  • solvents include water and organic solvents.
  • Preferred organic solvents include, for example, organic solvents having a boiling point of 100° C. or higher at 1013.25 hPa.
  • the metal tabular particle dispersion liquid according to an embodiment of the present disclosure further contains an organic solvent having a boiling point of 100°C or higher at 1013.25 hPa (hereinafter sometimes referred to as "specific organic solvent").
  • the specific organic solvent contributes to improving the dispersibility of the tabular metal particles.
  • organic solvents examples include toluene, xylene, 1,2-dibromoethane, tetrachloroethylene, chlorobenzene, bromobenzene, o-dichlorobenzene, 1-butanol, isobutyl alcohol, isopentyl alcohol, cyclohexanol, ethylene glycol, propylene glycol.
  • a metal tabular particle dispersion according to an embodiment of the present disclosure may contain one or more solvents.
  • the ratio of the solvent (preferably the specific organic solvent) in the metal tabular particle dispersion is preferably 0.1% by mass or more and less than 100% by mass, and is 1% by mass to 50% by mass. is more preferable, and 2% by mass to 20% by mass is particularly preferable.
  • the metal tabular particle dispersion according to an embodiment of the present disclosure may further contain a dispersant.
  • the type of dispersant is not limited. Dispersants include known dispersants. Preferred dispersants include, for example, dispersants that are soluble in liquid plasticizers.
  • the metal tabular particle dispersion liquid according to an embodiment of the present disclosure further includes a dispersant that dissolves in the liquid plasticizer (hereinafter sometimes referred to as "specific dispersant”).
  • soluble in the liquid plasticizer used in relation to the "dispersant soluble in the liquid plasticizer” means the property of dissolving 0.1 g or more per 100 g of the liquid plasticizer at 25°C.
  • the specific dispersant contributes to improving the dispersibility of the tabular metal grains.
  • Specific dispersants include, for example, acrylic resins, phosphate esters, polyurethanes, epoxy resins, and polyglycerin fatty acid esters. From the viewpoint of improving dispersibility, the specific dispersant is preferably a polyglycerin fatty acid ester.
  • Polyglycerin fatty acid esters include, for example, polyglycerin condensed ricinoleic acid esters and polyglycerin-bound ricinoleic acid esters.
  • Polyglycerin fatty acid esters include, for example, polyglycerin fatty acid esters described in JP-A-2013-112791. Examples of commercially available polyglycerin fatty acid esters include "SY Glister” (Sakamoto Yakuhin Kogyo Co., Ltd.).
  • Commercially available products of polyglycerin-bound ricinoleate include, for example, "SY Glister CRED" (Sakamoto Yakuhin Kogyo Co., Ltd.).
  • a metal tabular particle dispersion according to an embodiment of the present disclosure may contain one or more dispersants.
  • the proportion of the dispersant (preferably the specific dispersant) in the metal tabular particle dispersion is preferably 0.1% by mass to 50% by mass, more preferably 0.2% by mass to 20% by mass. is more preferable, and 0.5% by mass to 10% by mass is particularly preferable.
  • the ratio of the content of the dispersant (preferably the specific dispersant) to the content of the metal tabular grains is preferably 0.01 to 100, more preferably 0.05 to 50 in terms of mass. It is more preferably 0.1 to 10, particularly preferably 0.1 to 10.
  • the metal tabular particle dispersion according to an embodiment of the present disclosure may further contain a water-soluble resin, if necessary. However, as will be described later, it is preferable that the content of the water-soluble resin is small in the metal tabular particle dispersion according to an embodiment of the present disclosure.
  • the term "water-soluble” used in relation to the "water-soluble resin” means a property of dissolving 5 g or more in 100 g of water at 25°C.
  • water-soluble resins examples include polyvinyl acetal, polyvinyl alcohol, acrylic resin, polycarbonate, polyvinyl chloride, polyester, polyurethane, gelatin and cellulose. However, as will be described later, from the viewpoint of improving dispersibility, it is preferable to limit the amount of the water-soluble resin used.
  • a metal tabular particle dispersion according to an embodiment of the present disclosure may contain one or more water-soluble resins.
  • the content of the water-soluble resin is small.
  • the ratio of the content of the water-soluble resin to the content of the tabular metal particles is preferably 1% or less, more preferably 0.5% or less, and 0.2% or less in terms of mass. is particularly preferred.
  • the ratio of the content of the water-soluble resin to the content of the tabular metal particles may be 0% in terms of mass.
  • the content of water-soluble resin is measured by the BCA method (viciconinic acid method). Specific procedures (1) to (3) are shown below.
  • a mixture of water-soluble resin (10 g) and ion-exchanged water (115 g) (hereinafter referred to as "mother liquor 1" in this paragraph), a mixture of water-soluble resin (5 g) and ion-exchanged water (120 g) (hereinafter referred to as “mother liquor 2" in this paragraph), a mixture of water-soluble resin (5 g) and ion-exchanged water (245 g) (hereinafter referred to as “mother liquor 3” in this paragraph), and water-soluble resin ( 5 g) and deionized water (495 g) (hereinafter referred to as "mother liquor 4" in this paragraph) is prepared.
  • the water-soluble resin in the mother liquor is dissolved in deionized water while stirring at 40° C. for 30 minutes to obtain a calibration curve solution.
  • the calibration curve solution (2.5 mL) obtained using the mother liquor 1 into the first test tube and the calibration curve solution (2.5 mL) obtained using the mother liquor 2 into the second test tube.
  • a calibration solution (2.5 mL) obtained using mother liquor 3 was added to a third test tube, and a calibration solution (2.5 mL) obtained using mother liquor 4 was added to a fourth test tube. into a test tube.
  • a method for producing a metal tabular particle dispersion liquid according to an embodiment of the present disclosure is not limited.
  • the metal tabular particle dispersion is produced, for example, by mixing the metal tabular particles and a liquid plasticizer. Mixing of the metal tabular particles and the liquid plasticizer may be carried out under heating conditions. The heating temperature is preferably 20°C to 150°C.
  • a composition containing metal tabular particles, a dispersant, and a solvent may be used as the supply source of the metal tabular particles.
  • the composition as described above is obtained, for example, in the process of manufacturing tabular metal grains by a liquid phase method.
  • Liquid-phase methods often use a water-soluble resin (eg, gelatin) as a dispersant and water as a solvent.
  • the water-soluble resin is preferably replaced with a dispersant that has a high affinity for the liquid plasticizer.
  • the dispersant having a high affinity for the liquid plasticizer include the specific dispersant described above.
  • the replacement of the water-soluble resin with a dispersant that has a high affinity for the liquid plasticizer is preferably carried out, for example, in the presence of a substance that decomposes the water-soluble resin.
  • a substance that decomposes the water-soluble resin When the water-soluble resin is degraded, dispersant replacement readily occurs.
  • Substances that decompose gelatin, which is a type of water-soluble resin include, for example, proteolytic enzymes. Examples of commercially available proteolytic enzymes include Bioplase AL-15FG (Nagase ChemteX Corporation).
  • the metal tabular particles are usually dispersed in the oil phase containing the liquid plasticizer.
  • a metal tabular particle dispersion is obtained by taking out the oil phase containing the metal tabular particles.
  • a metal tabular particle dispersion liquid according to an embodiment of the present disclosure is used, for example, as a raw material for an intermediate film for laminated glass and laminated glass.
  • the interlayer film for laminated glass is used as a raw material for laminated glass.
  • Applications of laminated glass include, for example, vehicle (eg, automobile, railcar and airplane) glazing and building glazing.
  • the use of the metal tabular particle dispersion liquid is not limited to the specific examples described above.
  • a method for producing an interlayer film for laminated glass according to an embodiment of the present disclosure is to obtain an interlayer film for laminated glass using a metal tabular particle dispersion liquid according to an embodiment of the present disclosure (hereinafter, “formation of interlayer film (sometimes referred to as "process").
  • the metal tabular particle dispersion is used as the raw material for the interlayer film for laminated glass, the heat ray shielding property of the interlayer film for laminated glass is improved.
  • the metal tabular particle dispersion is easily mixed with a polymer such as polyvinyl butyral (PVB), which is commonly used as a raw material for interlayer films for laminated glass. As a result, the haze of the interlayer film for laminated glass is reduced.
  • PVB polyvinyl butyral
  • metal tabular particle dispersion liquid used as the raw material is described in the above section "Metal tabular particle dispersion liquid”.
  • Preferred aspects of the metal tabular particle dispersion liquid used as the raw material are the same as the preferred aspects of the metal tabular particle dispersion liquid described in the above section "Metal tabular particle dispersion liquid”.
  • a method for producing an interlayer film for laminated glass according to an embodiment of the present disclosure includes mixing a metal tabular particle dispersion and a polymer (hereinafter, “mixing step” ), and extruding the composition obtained by mixing the metal tabular particle dispersion and the polymer using an extruder (hereinafter sometimes referred to as the “first extrusion step”). and preferably include The mixing step and the first extrusion step contribute to improving the heat ray shielding property of the interlayer film for laminated glass and reducing the haze of the interlayer film for laminated glass.
  • polymers examples include polyvinyl acetal, polyvinyl alcohol, acrylic resin, polycarbonate, polyvinyl chloride, polyester, polyurethane, gelatin and cellulose.
  • the polymer comprises polyvinyl acetal.
  • the polyvinyl acetal preferably contains a cyclic structure containing —O—CHR 1 —O— bonds.
  • R 1 represents a hydrogen atom or a monovalent organic group.
  • the cyclic structure is preferably a 6-membered ring structure.
  • R 1 is preferably a monovalent organic group. Examples of monovalent organic groups include alkyl groups. Alkyl groups may be linear, branched or cyclic alkyl groups. The number of carbon atoms in the alkyl group is preferably 1-10, more preferably 2-8, and particularly preferably 2-4.
  • Polyvinyl acetals include, for example, polyvinyl formal and polyvinyl butyral (PVB). The polyvinyl acetal is preferably polyvinyl butyral (PVB).
  • the degree of acetalization of the polyvinyl acetal is preferably 55 mol% or more, more preferably 67 mol% or more. From the viewpoint of shortening the production time of polyvinyl acetal, the degree of acetalization of polyvinyl acetal is preferably 75 mol % or less, more preferably 71 mol % or less. The degree of acetalization is calculated, for example, by a method based on "ASTM D1396-92".
  • the polyvinyl acetal may be a synthetic product or a commercial product.
  • Polyvinyl acetal is produced, for example, by a known method.
  • Polyvinyl acetal is produced, for example, by acetalizing polyvinyl alcohol with an aldehyde.
  • the polyvinyl alcohol may be a synthetic product or a commercial product.
  • Polyvinyl alcohol is produced, for example, by saponifying polyvinyl acetate.
  • the degree of saponification of polyvinyl alcohol is preferably 70 mol % to 99.9 mol %.
  • the average degree of polymerization of polyvinyl alcohol is preferably 200 or more, more preferably 500 or more, and particularly preferably 1,500 or more.
  • the average degree of polymerization of polyvinyl alcohol is preferably 1,600 or more, more preferably 2,600 or more, and particularly preferably 2,700 or more.
  • the average degree of polymerization of polyvinyl alcohol is preferably 5,000 or less, more preferably 4,000 or less, and 3,500 or less. is particularly preferred.
  • the average degree of polymerization of polyvinyl alcohol is determined, for example, by a method conforming to "JIS K 6726:1994" (polyvinyl alcohol test method).
  • aldehydes include, for example, aldehydes having 1 to 10 carbon atoms.
  • aldehydes having 1 to 10 carbon atoms include formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, 2-ethylbutyraldehyde, n-hexylaldehyde, n-octylaldehyde, n -nonylaldehyde, n-decylaldehyde and benzaldehyde.
  • Propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde or n-hexylaldehyde are preferred, propionaldehyde, n-butyraldehyde or isobutyraldehyde are more preferred, and n-butyraldehyde is particularly preferred.
  • the mixing step is performed, for example, by a known method.
  • the mixing step may be performed in an extruder and a kneading device associated with the extruder. Other ingredients may be added during the mixing step. Other ingredients may be added to the composition obtained by the mixing step.
  • Other components include, for example, additives described in paragraphs 0066 to 0067 of JP-A-2014-194446.
  • Other ingredients also include, for example, antioxidants.
  • antioxidants examples include phenol antioxidants, sulfur antioxidants and phosphorus antioxidants.
  • a phenolic antioxidant is an antioxidant containing a phenol skeleton.
  • a sulfur antioxidant is an antioxidant containing a sulfur atom.
  • a phosphorus antioxidant is an antioxidant containing a phosphorus atom. The antioxidant is preferably a phenolic antioxidant or a phosphorus antioxidant.
  • Phenolic antioxidants include, for example, 2,6-di-t-butyl-p-cresol (BHT), butylated hydroxyanisole (BHA), 2,6-di-t-butyl-4-ethylphenol, Stearyl- ⁇ -(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,2′-methylenebis(4-methyl-6-butylphenol), 2,2′-methylenebis(4-ethyl-6 -t-butylphenol), 4,4′-butylidene-bis(3-methyl-6-t-butylphenol), 1,1,3-tris-(2-methyl-hydroxy-5-t-butylphenyl)butane, tetrakis[methylene-3-(3′,5′-butyl-4-hydroxyphenyl)propionate]methane, 1,3,3-tris-(2-methyl-4-hydroxy-5-t-butylphenol)butane, 1 , 3,5-trimethyl-2
  • Phosphorus-based antioxidants include, for example, tridecyl phosphite, tris(tridecyl) phosphite, triphenyl phosphite, trinonylphenyl phosphite, bis(tridecyl) pentaerythritol diphosphite, bis(decyl) pentaerythritol diphosphite, Phosphite, tris(2,4-di-t-butylphenyl)phosphite, bis(2,4-di-t-butyl-6-methylphenyl)ethyl ester phosphorous acid, tris(2,4-di- t-butylphenyl)phosphite and 2,2'-methylenebis(4,6-di-t-butyl-1-phenyloxy)(2-ethylhexyloxy)phosphorus.
  • the composition obtained by the mixing step is extruded using an extruder.
  • the shape of the composition extruded from the extruder usually corresponds to the shape of the exit (ie, discharge port) of the extruder.
  • a first extrusion step results in a film-like composition.
  • the composition extruded from the extruder can form regions containing metal tabular particles in the interlayer film for laminated glass.
  • the extruder may be any known extruder.
  • the extruder conditions are determined, for example, according to the thickness of the interlayer film for laminated glass. In order to reduce the thickness of the interlayer film for laminated glass, it is effective to increase the pressure and temperature.
  • a method for manufacturing an interlayer film for laminated glass according to an embodiment of the present disclosure comprises a metal flat particle dispersion and a polymer under conditions of a pressure of 10 kgf/cm 2 to 150 kgf/cm 2 and a temperature of 140°C to 250°C. It preferably comprises extruding the composition obtained by mixing with an extruder.
  • first intermediate film The composition extruded from the extruder in the first extrusion step (hereinafter referred to as "first intermediate film”) is used as an intermediate film for laminated glass or a raw material for an intermediate film for laminated glass.
  • first intermediate film a first interlayer film is used as a raw material for an interlayer film for laminated glass
  • the interlayer film for laminated glass may be manufactured through a process of stacking the first interlayer film and another interlayer film.
  • a method for manufacturing an interlayer film for laminated glass includes forming a first interlayer film into two interlayer films containing a polymer (hereinafter referred to as “second intermediate film” and “third intermediate film”) and extruding using an extruder (hereinafter sometimes referred to as "second extrusion step").
  • the second intermediate film, the first intermediate film, and the third intermediate film are stacked in this order and extruded to reduce the existence range of the metal tabular particles in the thickness direction of the interlayer film for laminated glass,
  • the heat ray shielding property of the interlayer film for glass can be improved.
  • the first intermediate film is produced by extruding, using an extruder, a composition obtained by mixing a dispersion of metal tabular particles and a polymer.
  • Each of the second intermediate film and the third intermediate film is produced, for example, by extruding a composition containing a polymer or a polymer using an extruder.
  • Polymers used as raw materials include, for example, the polymers described above.
  • Each of the second intermediate film and the third intermediate film preferably contains a plasticizer (preferably a liquid plasticizer).
  • Each of the second intermediate film and the third intermediate film may contain other components as described above, if necessary.
  • the extruder used in the second extrusion step may be the same as or different from the extruder used in the first extrusion step.
  • Preferred conditions for the second extrusion step are the same as preferred conditions for the first extrusion step.
  • composition extruded from the extruder in the second extrusion step is used as a raw material for an intermediate film for laminated glass or an intermediate film for laminated glass, similar to the first intermediate film.
  • the composition extruded from the extruder in the second extrusion step may be used over other interlayers, as described below.
  • a method for producing an interlayer film for laminated glass according to an embodiment of the present disclosure includes a composition extruded from an extruder in a second extrusion step, containing a polymer It may further include sandwiching between two intermediate films (hereinafter, the two intermediate films are referred to as "fourth intermediate film” and "fifth intermediate film", respectively) and extruding using an extruder.
  • the fourth intermediate film, the second intermediate film, the first intermediate film, the third intermediate film and the fifth intermediate film may be stacked in this order, or the fifth intermediate film and the second intermediate film may be stacked in this order.
  • the first intermediate film, the third intermediate film and the fourth intermediate film may be stacked in this order.
  • Each of the fourth intermediate film and the fifth intermediate film is manufactured by, for example, the same method as the manufacturing method of the second intermediate film or the third intermediate film described above.
  • Each of the fourth intermediate film and the fifth intermediate film preferably contains a plasticizer (preferably a liquid plasticizer).
  • a plasticizer preferably a liquid plasticizer.
  • Each of the fourth intermediate film and the fifth intermediate film may contain other components as described above, if necessary.
  • FIG. 1 is a schematic diagram showing an example of a method for producing an intermediate film for laminated glass and a laminated glass.
  • FIG. 1 the boundaries between the intermediate films used as raw materials are shown for the explanation of the intermediate film for laminated glass and the method of manufacturing the laminated glass.
  • some or all of the boundary between interlayer films as shown in FIG. 1 may not be clearly observed.
  • an intermediate film 10 As shown in FIG. 1(a), an intermediate film 10, an intermediate film 11 containing metal tabular particles P, and an intermediate film 12 are stacked in this order and extruded using an extruder to obtain an intermediate film laminate 100. can get.
  • interlayer films 13, 10, 11, 12 and 14 are laminated in this order as shown in FIG.
  • the intermediate film for laminated glass 200 is obtained by extrusion using a machine.
  • the intermediate film 10 corresponds to the second intermediate film
  • the intermediate film 11 corresponds to the first intermediate film
  • the intermediate film 12 corresponds to the third intermediate film.
  • Reference numeral 13 corresponds to the already-described fourth intermediate film
  • intermediate film 14 corresponds to the already-described fifth intermediate film.
  • the interlayer film for laminated glass obtained by the method for producing an interlayer film for laminated glass according to an embodiment of the present disclosure contains at least metal tabular particles.
  • the interlayer film for laminated glass formed using the metal tabular particle dispersion may contain a part or all of the components of the metal tabular particle dispersion.
  • highly volatile components e.g., solvent
  • highly volatile components among the components of the metal tabular particle dispersion liquid may be intentionally or accidentally removed during the manufacturing process of the interlayer film for laminated glass. may not be included in
  • the interlayer film for laminated glass may apparently have a single-layer structure or a multi-layer structure.
  • the interlayer for laminated glass may contain other layers.
  • Other layers include, for example, a heat ray absorbing layer, an ultraviolet absorbing layer, an adhesive layer, a hard coat layer and an overcoat layer.
  • other layers include, for example, a support described in paragraphs 0068 to 0072 of JP-A-2014-194446, an undercoat layer described in paragraph 0085 of JP-A-2014-194446, and a JP-A-2014-194446.
  • Also included are the back coat layers described in paragraph 0086 of JP-A-2014-194446.
  • the interlayer film for laminated glass may include a heat-absorbing layer containing metal oxide particles.
  • Metal oxides in the metal oxide particles include tin-doped indium oxide (ITO), cesium-doped tungsten oxide (CWO), antimony-doped tin oxide (ATO), zinc oxide, zinc antimonate, titanium oxide, indium oxide, and tin oxide. , antimony oxide, glass ceramics and lanthanum hexaboride (LaB 6 ).
  • a composition of cesium-doped tungsten oxide includes, for example, Cs 0.33 WO 3 .
  • the metal oxide in the metal oxide particles is preferably at least one selected from the group consisting of tin-doped indium oxide (ITO) and cesium-doped tungsten oxide (CWO).
  • the volume average particle size of the primary particles of the metal oxide particles is preferably 100 nm or less, more preferably 80 nm or less, and 60 nm or less. It is particularly preferred to have
  • the shape of the metal oxide particles includes, for example, a spherical shape, a needle shape, and a plate shape.
  • the heat-absorbing layer may contain one or more metal oxide particles.
  • the content of metal oxide particles in the heat ray absorbing layer is preferably 0.5 g/m 2 to 5.0 g/m 2 , more preferably 0.5 g/m 2 to 4 g/m 2 with respect to the total mass of the heat ray absorbing layer. 0 g/m 2 is more preferred, and 1.0 g/m 2 to 3.0 g/m 2 is particularly preferred.
  • the content of the metal oxide particles is 0.5 g/m 2 or more, the heat ray shielding properties are improved.
  • the content of the metal oxide particles is 5 g/m 2 or less, the visible light transmittance is improved.
  • the content of cesium-doped tungsten oxide (CWO) in the heat-absorbing layer is preferably 0.3 g/m 2 to 1.3 g/m 2 , more preferably 0.6 g/m 2 with respect to the total mass of the heat-absorbing layer. More preferably 2 to 1.3 g/m 2 .
  • the mass ratio of ITO and CWO is preferably 5-95:95-5, more preferably 10-90:90-10. , 20-80:80-20.
  • the thickness of the heat ray absorbing layer is preferably within the range of 0.5 ⁇ m to 10 ⁇ m, more preferably within the range of 1.0 ⁇ m to 3.0 ⁇ m.
  • the interlayer film for laminated glass according to one embodiment of the present disclosure may include an ultraviolet absorbing layer.
  • the ultraviolet absorption layer may be a layer having other functions in addition to the function of absorbing ultraviolet rays.
  • the number of ultraviolet absorbing layers may be one or two or more. From the viewpoint of reducing the thickness of the interlayer film for laminated glass, the interlayer film for laminated glass according to one embodiment of the present disclosure preferably includes one ultraviolet absorbing layer.
  • the transmittance of the ultraviolet absorption layer at a wavelength of 390 nm is preferably 50% or less, more preferably 40% or less, and particularly preferably 30% or less.
  • the transmittance of the ultraviolet absorbing layer at a wavelength of 390 nm is adjusted, for example, by the content and type of the ultraviolet absorbing agent in the ultraviolet absorbing layer.
  • the ultraviolet absorbing layer preferably contains an ultraviolet absorber.
  • UV absorbers include triazine-based compounds, benzotriazole-based compounds, cyclic iminoester-based compounds, benzophenone-based compounds, merocyanine-based compounds, cyanine-based compounds, dibenzoylmethane-based compounds, cinnamic acid-based compounds, and cyanoacrylate-based compounds. and benzoic acid ester compounds.
  • UV absorbers also include compounds described in paragraphs 0040 to 0088 of JP-A-2012-136019. The contents of the above documents are incorporated herein by reference.
  • the ultraviolet absorbing layer may contain one or more ultraviolet absorbers.
  • the content of UV absorbers is not limited.
  • the content of the ultraviolet absorbent is determined, for example, according to the function of the ultraviolet absorbing layer, that is, the required ultraviolet transmittance.
  • the ultraviolet absorbing layer may contain a polymer as a binder.
  • Polymers include, for example, acrylic resins, polyvinyl butyral, polyvinyl alcohol, and polyesters. From the viewpoint of improving heat reflection by the metal tabular particles, the polymer is preferably selected from polymers that do not absorb light in the wavelength range of 450 nm to 1,500 nm.
  • the ultraviolet absorbing layer may contain at least one selected from the group consisting of fine particles having a low refractive index and fine particles having a high refractive index. Fine particles with a low refractive index can reduce the refractive index of the UV absorbing layer. Fine particles with a high refractive index can increase the refractive index of the UV absorbing layer. Fine particles having a low refractive index include, for example, magnesium fluoride fine particles and silica fine particles. Silica fine particles are preferred from the viewpoint of refractive index, dispersion stability and cost. From the viewpoint of reducing the refractive index, hollow silica fine particles are preferred.
  • the refractive index of the hollow silica fine particles is preferably 1.17 to 1.40, more preferably 1.17 to 1.35, particularly preferably 1.17 to 1.30.
  • the refractive index of the hollow silica fine particles represents the refractive index of the entire particle, and does not represent the refractive index of only the outer shell silica forming the hollow silica fine particles.
  • the average particle size of the fine particles having a low refractive index is preferably 30 nm to 100 nm, more preferably 35 nm to 80 nm, and particularly preferably 40 nm to 60 nm.
  • Fine particles having a high refractive index include, for example, metal oxide fine particles containing at least one selected from the group consisting of titanium, zirconium, aluminum, indium, zinc, tin and antimony.
  • the average particle size of the fine particles having a high refractive index is preferably 0.2 ⁇ m or less, more preferably 0.1 ⁇ m or less, and particularly preferably 0.06 ⁇ m or less.
  • the thickness of the ultraviolet absorbing layer is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more. From the viewpoint of visible light transmission, the thickness of the ultraviolet absorbing layer is preferably 200 ⁇ m or less, more preferably 100 ⁇ m or less.
  • the interlayer film for laminated glass according to one embodiment of the present disclosure may include an adhesive layer.
  • Components of the adhesive layer include, for example, polyvinyl butyral, acrylic resin, styrene/acrylic resin, polyurethane, polyester and silicone. Components of the adhesive layer also include, for example, antistatic agents, lubricants and antiblocking agents.
  • the thickness of the adhesive layer is preferably within the range of 0.1 ⁇ m to 30 ⁇ m, more preferably within the range of 5 ⁇ m to 20 ⁇ m.
  • the interlayer film for laminated glass may include a hard coat layer.
  • the hard coat layer can impart scratch resistance to the interlayer film for laminated glass.
  • Components of the hard coat layer include, for example, acrylic resins, silicone resins, melamine resins, urethane resins, alkyd resins, and fluorine resins.
  • the hard coat layer may contain metal oxide particles.
  • the thickness of the hard coat layer is preferably within the range of 1 ⁇ m to 50 ⁇ m.
  • the interlayer film for laminated glass according to one embodiment of the present disclosure may include an overcoat layer.
  • Components of the overcoat layer include, for example, binders, matting agents and surfactants.
  • binders include acrylic resins, silicone resins, melamine resins, urethane resins, alkyd resins, and fluorine resins.
  • the thickness of the overcoat layer is preferably within the range of 0.01 ⁇ m to 5 ⁇ m, more preferably within the range of 0.05 ⁇ m to 1 ⁇ m.
  • the thickness of the interlayer film for laminated glass according to an embodiment of the present disclosure is preferably in the range of 10 ⁇ m to 2,000 ⁇ m, preferably 20 ⁇ m to 1,000 ⁇ m. It is more preferably within the range of 500 ⁇ m, and particularly preferably within the range of 30 ⁇ m to 1,000 ⁇ m.
  • the interlayer film for laminated glass obtained by the method for producing an interlayer film for laminated glass according to an embodiment of the present disclosure is used as an interlayer film for various laminated glasses.
  • Applications of laminated glass include, for example, vehicle (eg, automobile, railcar and airplane) glazing and building glazing.
  • an interlayer film for laminated glass is divided into two glass plates (hereinafter, the two glass plates may be referred to as "first glass plate” and “second glass plate”, respectively). .).
  • a method for manufacturing laminated glass according to an embodiment of the present disclosure preferably includes sandwiching an interlayer film for laminated glass between two glass plates and pressing them while heating.
  • the interlayer film for laminated glass is manufactured, for example, by the method described in the section "Method for producing interlayer film for laminated glass” above.
  • the interlayer film for laminated glass is preferably an interlayer film for laminated glass produced by the method described in the section "Method for producing interlayer film for laminated glass” above.
  • the type of glass plate is not limited.
  • the glass plate may be a known glass plate.
  • Glass plates include soda plate glass and green glass.
  • the glass plate may be a glass substitute resin molding.
  • Glass substitute resins include, for example, polycarbonate and acrylic resins.
  • the glass substitute resin molded article may be produced by forming a hard coat layer on the glass substitute resin.
  • the hard coat layer include a layer in which inorganic fine particles are dispersed in an acrylic hard coat material, a silicone hard coat material, or a melamine hard coat material.
  • examples of inorganic fine particles include silica, titania, alumina and zirconia.
  • the type of the first glass plate may be the same as or different from the type of the second glass plate.
  • the interlayer film for laminated glass and the two glass plates may be pre-press-bonded and then pressure-bonded while being heated in a device such as an autoclave.
  • Preliminary pressure bonding is performed, for example, under a reduced pressure environment at a temperature of 80° C. to 120° C. for a treatment time of 30 minutes to 60 minutes.
  • Thermocompression bonding by an autoclave is performed, for example, at a pressure of 1.0 MPa to 1.5 MPa and a temperature of 120°C to 150°C.
  • the time for thermocompression bonding is preferably 20 to 90 minutes.
  • the range in which the interlayer film for laminated glass and the glass plate are heat-pressed may be a range over the entire area of the glass plate, or may be only the peripheral edge of the glass plate.
  • the thermocompression bonding of the peripheral portion of the glass plate can further suppress the occurrence of wrinkles.
  • the laminated glass body may be produced by allowing it to cool while appropriately releasing the pressure after the thermocompression bonding. From the viewpoint of improving wrinkles and cracks in the laminated glass body, it is preferable to lower the temperature while the pressure is maintained after the thermocompression bonding.
  • the expression "lowering the temperature while maintaining the pressure” means that the pressure inside the device at 40°C is lowered to 75% to 100% of the pressure during thermocompression bonding.
  • a method of lowering the temperature while maintaining the pressure there is a method of lowering the temperature without leaking the pressure from the inside of the device so that the pressure inside the device naturally decreases as the temperature decreases, or a method in which the pressure inside the device decreases as the temperature decreases.
  • a method of lowering the temperature while further pressurizing it from the outside is preferable so as not to reduce the temperature.
  • the pressure it is preferable to release the pressure after the temperature is lowered while the pressure is maintained. After the temperature is lowered while the pressure is maintained, it is preferable to release the pressure and lower the temperature after the temperature inside the apparatus reaches 40° C. or less.
  • a method for manufacturing laminated glass according to an embodiment of the present disclosure includes (1) sandwiching an interlayer film for laminated glass between two glass plates; (3) lowering the temperature while maintaining the pressure; and (4) releasing the pressure. preferable.
  • the method for producing laminated glass is not limited to the following method.
  • the laminated glass 300 is obtained by sandwiching the interlayer film 200 for laminated glass between the first glass plate 20 and the second glass plate 21 and pressing them while heating.
  • a laminated glass obtained by a method for manufacturing laminated glass according to an embodiment of the present disclosure includes an intermediate film for laminated glass and two glass plates sandwiching the intermediate film for laminated glass. That is, the laminated glass includes a first glass plate, an intermediate film for laminated glass, and a second glass plate in this order.
  • the interlayer for laminated glass may contact at least one of the two glass sheets. Another layer may be arranged between the glass plate and the interlayer film for laminated glass.
  • a laminated glass according to an embodiment of the present disclosure may include other layers.
  • Other layers include the other layers described in the above section "Interlayer film for laminated glass".
  • a laminated glass according to an embodiment of the present disclosure includes, for example, window glass for vehicles (for example, automobiles, railroad vehicles, and airplanes) and window glass for buildings.
  • a laminated glass according to an embodiment of the present disclosure is preferably used as a window glass for automobiles.
  • Dispersion B1 was prepared by the following procedure.
  • Dispersion B1 is a metal tabular particle dispersion in the present disclosure.
  • the aqueous gelatin solution was prepared by dissolving inert gelatin (33.5 g) with a weight average molecular weight of 200,000 and oxidized gelatin (22.3 g) with a weight average molecular weight of 20,000 in pure water (409 mL).
  • a silver sulfite white precipitate mixture prepared by mixing 13.5% by mass sodium sulfite aqueous solution (67 mL), 10% by mass aqueous silver nitrate solution (228 mL) and pure water (369 mL) was added to the reactor. added.
  • Dispersion B1 Dispersion A1 (200 mL), proteolytic enzyme (Bioplase AL-15FG, 1 g, manufactured by Nagase Chemtex Co., Ltd.), and polyglycerin fatty acid ester (manufactured by Sakamoto Pharmaceutical Co., Ltd., polyglycerin-bound ricinoleic acid ester "SY Glyster CRED , 0.5 g) and a plasticizer (triethylene glycol di(2-ethylhexanoate), 10 g) were mixed and stirred well at 40°C.
  • proteolytic enzyme Bioplase AL-15FG, 1 g, manufactured by Nagase Chemtex Co., Ltd.
  • polyglycerin fatty acid ester manufactured by Sakamoto Pharmaceutical Co., Ltd., polyglycerin-bound ricinoleic acid ester "SY Glyster CRED , 0.5 g) and a plasticizer (triethylene glycol di(2-ethylhexanoate
  • gelatin which is a dispersant for silver tabular particles
  • a proteolytic enzyme the dispersant is replaced with polyglycerin fatty acid ester, and silver tabular particles are dispersed in an oil phase containing a liquid plasticizer.
  • the aqueous phase liquid was discarded to obtain dispersion liquid B1.
  • the proportion of silver tabular grains in Dispersion B1 was 10% by mass.
  • the median diameter of the silver tabular grains in Dispersion B1 was measured using a Microtrac particle size distribution meter manufactured by Nikkiso Co., Ltd.
  • the median diameter of the silver tabular grains on a volume basis was 80 nm.
  • Dispersion B1 was dropped onto the mesh to evaporate the solvent, and then the silver tabular grains were observed using a transmission electron microscope (TEM) at an observation magnification ranging from 5,000 times to 20,000 times. .
  • TEM transmission electron microscope
  • the obtained image was loaded into image processing software "ImageJ" and subjected to image processing. Image analysis was performed on 1,000 silver tabular grains arbitrarily extracted from TEM images of a plurality of fields of view, and the average circle equivalent diameter of the 1,000 silver tabular grains was calculated. The average equivalent circle diameter of the silver tabular grains was 120 nm.
  • (Thickness of silver tabular grain) Dispersion B1 was dropped onto a silicon substrate and dried, and the thickness of silver tabular grains was measured by the FIB-TEM method. Specifically, 100 silver tabular grains were observed at a magnification in the range of 5,000 to 20,000 times, and the thickness of 100 metal tabular grains was arithmetically averaged to obtain an average of the silver tabular grains. Thickness was calculated. The average thickness of the silver tabular grains was 8 nm. Since the average equivalent circle diameter of the silver tabular grains is 120 nm and the average thickness of the silver tabular grains is 8 nm, the volume of the silver tabular grains can be determined, and the diameter of the sphere at this volume is determined to be 56 nm.
  • the median diameter of tabular silver grains measured using the aforementioned Microtrac grain size distribution analyzer is larger than the primary grain diameter, reflecting the aggregation state of the grains. Therefore, the closer the median diameter of the silver tabular grains to the primary particle diameter of the silver tabular grains, the better the dispersion state.
  • a centrifuge manufactured by Kokusan Co., Ltd., H200-N
  • the proportion of silver tabular grains in Dispersion B2 was 5% by mass.
  • the grain size and average thickness of the silver tabular grains were measured according to the method described above.
  • the median diameter (specifically, the median diameter based on volume) of the silver tabular grains in dispersion B2 was 150 nm.
  • the average equivalent circle diameter of the silver tabular grains was 120 nm.
  • the average thickness of the silver tabular grains was 8 nm. Therefore, the primary particle diameter of the silver tabular grains was 56 nm.
  • Dispersion B3 was prepared by the following procedure.
  • Dispersion B3 is a metal tabular particle dispersion in the present disclosure.
  • a 2.5 mmol/L sodium citrate aqueous solution (132.7 mL) and ion-exchanged water (87.1 mL) were added to the reactor and heated to 35°C.
  • 10 mmol/L ascorbic acid aqueous solution (2 mL) was added, seed solution (42.4 mL) was added, and 0.5 mmol/L silver nitrate aqueous solution (79.6 mL) was added at 10 mL/min. Add with stirring.
  • a 0.35 mol/L potassium hydroquinone sulfonate aqueous solution (71.1 mL) was added to the reaction kettle, and a 7 mass % gelatin aqueous solution (200 g) was added to the reaction kettle.
  • a silver sulfite white precipitate mixture prepared by mixing 0.25 mol/L sodium sulfite aqueous solution (107 mL) and 0.47 mol/L silver nitrate aqueous solution (107 mL) was added to the solution in the reaction kettle. .
  • 0.17 mol/L NaOH aqueous solution 72 mL was added to the reactor.
  • Dispersion B3 Dispersion A3 (200 mL), proteolytic enzyme (Bioplase AL-15FG, 1 g, manufactured by Nagase Chemtex Co., Ltd.), and polyglycerin fatty acid ester (manufactured by Sakamoto Pharmaceutical Co., Ltd., polyglycerin-bound ricinoleic acid ester "SY Glyster CRED , 0.5 g) and a plasticizer (triethylene glycol di(2-ethylhexanoate), 10 g) were mixed and stirred well at 40°C.
  • proteolytic enzyme Bioplase AL-15FG, 1 g, manufactured by Nagase Chemtex Co., Ltd.
  • polyglycerin fatty acid ester manufactured by Sakamoto Pharmaceutical Co., Ltd., polyglycerin-bound ricinoleic acid ester "SY Glyster CRED , 0.5 g) and a plasticizer (triethylene glycol di(2-ethylhexanoate
  • gelatin which is a dispersant for silver tabular particles
  • gelatin which is a dispersant for silver tabular particles
  • the dispersant is replaced with polyglycerin fatty acid ester
  • silver tabular particles are dispersed in an oil phase containing a liquid plasticizer.
  • the aqueous phase liquid was discarded to obtain a dispersion liquid B3.
  • the proportion of silver tabular grains in Dispersion B3 was 10% by mass.
  • the grain size and average thickness of the silver tabular grains were measured according to the method described above.
  • the median diameter (specifically, the median diameter based on the volume) of the silver tabular grains in Dispersion B3 was 120 nm.
  • the average circle equivalent diameter of the silver tabular grains was 200 nm.
  • the average thickness of the silver tabular grains was 10 nm. Therefore, the primary particle diameter of the silver tabular grains was 84 nm.
  • ⁇ Dispersion C1> Cs 0.33 WO 3 particles (CWO particles, 50% diameter in particle size distribution: 1.2 ⁇ m, 95% diameter in particle size distribution: 4.8 ⁇ m, 100 parts by mass) as heat shielding particles, and polyglycerol fatty acid ester as a dispersant “SY Glister CRED” (5 parts by mass) and triethylene glycol di(2-ethylhexanoate) (3,500 parts by mass) as a plasticizer were mixed to prepare 3 kg of slurry.
  • the medium stirring mill is a horizontal cylindrical annular type (manufactured by Ashizawa Finetech Co., Ltd.), and the inner wall of the vessel and the rotor (rotary stirring part) are made of ZrO2.
  • YSZ Yttria-Stabilized Zirconia beads with a diameter of 0.1 mm were used as the beads.
  • the rotational speed of the rotor was set to 13 m/sec, and the powder was pulverized for 12 hours at a slurry flow rate of 1 kg/min to prepare dispersion C1.
  • the proportion of Cs 0.33 WO 3 in dispersion C1 was 24.7% by mass.
  • the particle size of Cs 0.33 WO 3 in dispersion liquid C1 was measured according to the method described above.
  • the median diameter of Cs 0.33 WO 3 (specifically, median diameter based on volume) was 18 nm.
  • Cs 0.33 WO 3 was observed using a transmission electron microscope (TEM) at an observation magnification ranging from 5,000 times to 20,000 times. Particles were observed.
  • TEM transmission electron microscope
  • Image analysis was performed on 1,000 silver tabular grains arbitrarily extracted from TEM images of multiple fields of view, and the average circle equivalent diameter of 1,000 Cs 0.33 WO 3 grains was calculated. Since the Cs 0.33 WO 3 particles are almost spherical, this average circular equivalent diameter was taken as the primary particle diameter of the Cs 0.33 WO 3 particles and was 14 nm.
  • nitric acid 144 g was added, heated to 65° C., and aged at 67.5° C. for 2 hours. Next, after the solution was cooled and neutralized, the polyvinyl butyral was washed with water and dried to obtain polyvinyl acetal Q.
  • An intermediate film A (thickness: 1,000 ⁇ m) was produced by extruding the resulting composition using an extruder.
  • An intermediate film X (thickness: 20 ⁇ m) was produced by stacking the intermediate film A, the intermediate film B, and the intermediate film A in this order and extruding them using an extruder.
  • An intermediate film C (thickness: 760 ⁇ m) was produced by stacking the intermediate film A, the intermediate film X and the intermediate film A in this order and extruding them using an extruder.
  • An intermediate film Y (thickness: 20 ⁇ m) was produced by stacking the intermediate film A, the intermediate film D, and the intermediate film A in this order and extruding them using an extruder.
  • An intermediate film E (thickness: 760 ⁇ m) was produced by stacking the intermediate film A, the intermediate film Y, and the intermediate film A in this order and extruding them using an extruder.
  • ⁇ Glass plate> Two glass plates, washed and dried, were prepared. Specifically, the two glass plates include soda plate glass (length 25 cm ⁇ width 10 cm ⁇ thickness 2 mm) and green glass (length 25 cm ⁇ width 10 cm ⁇ thickness 2 mm).
  • Example 1 A laminate was produced by stacking the three members in the following order.
  • First glass plate Soda plate glass
  • Interlayer film for laminated glass Interlayer film
  • Second glass plate soda plate glass
  • the obtained laminate was placed in a rubber bag and deaerated for 20 minutes at a degree of vacuum of 2,660 Pa (20 torr).
  • the laminate was vacuum pressed while being held at 90° C. for 30 minutes in an autoclave while being degassed.
  • the preliminarily pressure-bonded laminate was pressure-bonded in an autoclave at 135° C. and 1.2 MPa (12 kg/cm 2 ) for 20 minutes to obtain a laminated glass.
  • Example 2 Using dihexyl adipate (DHA) instead of triethylene glycol di(2-ethylhexanoate) used as a plasticizer in the preparation of dispersion B1 and triethylene used as a plasticizer in the preparation of the interlayer A laminated glass was obtained in the same manner as in Example 1, except that dihexyl adipate (DHA) was used instead of glycol di(2-ethylhexanoate).
  • DHA dihexyl adipate
  • Example 3 Laminated glass was prepared in the same manner as in Example 1, except that the amount of triethylene glycol di(2-ethylhexanoate) used as a plasticizer in the preparation of dispersion B1 was changed from 10 g to 330 g. Obtained.
  • Example 4 Laminated glass was prepared in the same manner as in Example 1, except that the amount of triethylene glycol di(2-ethylhexanoate) used as a plasticizer in the preparation of dispersion B1 was changed from 10 g to 100 g. Obtained.
  • Example 5 Laminated glass was prepared in the same manner as in Example 1, except that the amount of triethylene glycol di(2-ethylhexanoate) used as a plasticizer in the preparation of dispersion B1 was changed from 10 g to 20 g. Obtained.
  • Example 6 Laminated glass was prepared in the same manner as in Example 1, except that the amount of triethylene glycol di(2-ethylhexanoate) used as a plasticizer in the preparation of dispersion B1 was changed from 10 g to 5 g. Obtained.
  • Example 7 Laminated glass was prepared in the same manner as in Example 1, except that the amount of triethylene glycol di(2-ethylhexanoate) used as a plasticizer in the preparation of dispersion B1 was changed from 10 g to 3 g. Obtained.
  • Example 8 Laminated glass was prepared in the same manner as in Example 1, except that in the preparation of dispersion B1, the amount of proteolytic enzyme (Bioplase AL-15FG manufactured by Nagase ChemteX Co., Ltd.) was changed from 1 g to 0.2 g. got
  • Example 9 In the preparation of dispersion B1, the method of Example 8 was repeated except that the temperature in the mixing after adding the proteolytic enzyme (Bioplase AL-15FG manufactured by Nagase ChemteX Corporation) was changed from 40°C to 30°C. A laminated glass was obtained by the same method.
  • the proteolytic enzyme Bioplase AL-15FG manufactured by Nagase ChemteX Corporation
  • Example 10 In the preparation of dispersion B1, the method of Example 9 except that 0.5 mol / L sulfuric acid (1 g) was further added after adding the protease (Bioplase AL-15FG manufactured by Nagase ChemteX Co., Ltd.) Laminated glass was obtained by the same method as above.
  • Example 11 In the preparation of dispersion B1, the method of Example 9 except that 0.5 mol / L sulfuric acid (2 g) was further added after adding the protease (Bioplase AL-15FG manufactured by Nagase ChemteX Co., Ltd.) Laminated glass was obtained by the same method as above.
  • Example 12 A laminated glass was obtained in the same manner as in Example 1, except that Dispersion B1 was changed to Dispersion B3.
  • the water-soluble resin in the mother liquor was dissolved in deionized water while stirring at 40° C. for 30 minutes to obtain a gelatin solution for calibration curve.
  • the standard curve gelatin solution (2.5 mL) obtained using mother liquor 1 was placed in the first test tube, and the standard curve gelatin solution (2.5 mL) obtained using mother liquor 2 was added to the second test tube.
  • a standard gelatin solution (2.5 mL) obtained using mother liquor 3 was added to a third test tube, and a standard gelatin solution (2.5 mL) obtained using mother liquor 4 was added to a third test tube. ) was placed in a fourth test tube.
  • a subject dispersion (1 mL) and deionized water (1.5 mL) were placed in a test tube to prepare a sample for gelatin determination.
  • a quantitative reagent was prepared by mixing reagent A, reagent B, and reagent C of Micro BCA Protein Assay Kit solution manufactured by Thermo Fisher Scientific at a volume ratio of 25:24:1, respectively. Put the quantitative reagent (2.5 mL) into each test tube containing the gelatin solution for the standard curve, and after putting the quantitative reagent (2.5 mL) into the test tube containing the sample for gelatin determination, cap each test tube. and stirred well.
  • the sample in each test tube is colored at 60 ° C., 1 hour and 160 reciprocating / min shaking speed, cooled to room temperature 10 minutes later, U- A 3300 was used to immediately measure absorbance at 562 nm. Based on the absorbance of the gelatin solution for the calibration curve, the amount of gelatin contained in the sample for gelatin quantification was calculated.
  • Table 1 shows that the dispersibility of the metal tabular particle dispersions in Examples 1 to 12 is superior to that of the metal tabular particle dispersion in Comparative Example 1.
  • Table 1 shows that the use of the metal tabular particle dispersions in Examples 1 to 12 improves the heat ray shielding properties of the laminated glass and reduces the haze of the laminated glass.
  • the laminated glass obtained using the dispersion in Comparative Example 2 did not contain silver tabular particles, the heat ray shielding properties of Comparative Example 2 were inferior to those of Examples 1 to 12.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Joining Of Glass To Other Materials (AREA)

Abstract

La présente invention concerne : un liquide de dispersion de particules métalliques planes qui contient un plastifiant liquide et des particules métalliques planes qui contiennent 50 % en masse ou plus d'argent; et des applications de ce liquide de dispersion de particules métalliques planes.
PCT/JP2021/045908 2021-02-05 2021-12-13 Liquide de dispersion de particules métalliques planes et procédé de production de film intermédiaire pour verre feuilleté WO2022168451A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001014943A (ja) * 1999-06-30 2001-01-19 Harima Chem Inc 回路描画用導電性ペーストおよび回路印刷方法
JP2013506295A (ja) * 2009-09-24 2013-02-21 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー メッキリンクとしての使用のためのポリマー厚膜銀電極組成物
WO2019003783A1 (fr) * 2017-06-30 2019-01-03 富士フイルム株式会社 Matériau de protection contre les rayons thermiques, film intermédiaire pour verre feuilleté et verre feuilleté

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001014943A (ja) * 1999-06-30 2001-01-19 Harima Chem Inc 回路描画用導電性ペーストおよび回路印刷方法
JP2013506295A (ja) * 2009-09-24 2013-02-21 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー メッキリンクとしての使用のためのポリマー厚膜銀電極組成物
WO2019003783A1 (fr) * 2017-06-30 2019-01-03 富士フイルム株式会社 Matériau de protection contre les rayons thermiques, film intermédiaire pour verre feuilleté et verre feuilleté

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