WO2018047841A1 - Hydroxyde métallique composite microparticulaire, produit calciné de celui-ci, son procédé de production et composition de résine associée - Google Patents

Hydroxyde métallique composite microparticulaire, produit calciné de celui-ci, son procédé de production et composition de résine associée Download PDF

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WO2018047841A1
WO2018047841A1 PCT/JP2017/032035 JP2017032035W WO2018047841A1 WO 2018047841 A1 WO2018047841 A1 WO 2018047841A1 JP 2017032035 W JP2017032035 W JP 2017032035W WO 2018047841 A1 WO2018047841 A1 WO 2018047841A1
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composite metal
metal hydroxide
primary particles
sample
aqueous solution
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PCT/JP2017/032035
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English (en)
Japanese (ja)
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哲郎 亀田
茂男 宮田
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協和化学工業株式会社
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Priority to KR1020197009352A priority Critical patent/KR102085040B1/ko
Priority to KR1020207005788A priority patent/KR102262069B1/ko
Priority to JP2018538429A priority patent/JP6593942B2/ja
Priority to CN201780067191.5A priority patent/CN109906202B/zh
Publication of WO2018047841A1 publication Critical patent/WO2018047841A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of 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
    • C08K9/00—Use of pretreated ingredients
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2262—Oxides; Hydroxides of metals of manganese
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2293—Oxides; Hydroxides of metals of nickel

Definitions

  • the present invention relates to a composite metal hydroxide having a small average lateral width of primary particles, in which primary particles are dispersed and having high acid resistance, a fired product thereof, a production method thereof, and a resin composition thereof.
  • Patent Document 1 as an inorganic filler, an aspect using a metal hydroxide is preferable from the viewpoints of flame retardant improvement effect, handling property, static elimination effect, battery durability improvement effect, and the like, among which aluminum hydroxide or water It is disclosed that magnesium oxide is preferable, and that the average particle diameter of the inorganic filler is preferably in the range of 0.1 to 2 ⁇ m from the viewpoint of short circuit resistance at high temperature, moldability, and the like.
  • Patent Document 1 further discloses a method for forming a heat-resistant porous layer on at least one surface of a polyolefin porous substrate as a method for producing a separator for a lithium ion battery. More specifically, an inorganic filler is dispersed in an organic solvent to prepare a coating slurry, which is applied to a polyolefin porous substrate. Since a uniform coating film cannot be obtained unless the inorganic filler is dispersed in the coating slurry, the inorganic filler is required to have high dispersibility. When the dispersibility of the inorganic filler is not preferred, a technique is disclosed in which the inorganic filler is surface-treated with a silane coupling agent or the like to improve the dispersibility.
  • the average particle size is 0.8 ⁇ m or less because the average particle size is reflected in the thickness of the separator. It is preferable that the average particle size is 0.7 ⁇ m or less, and a magnesium compound having an average particle size of 0.1 ⁇ m or less can be synthesized. It is disclosed that it is not preferable because it affects the coating process in forming the layer.
  • magnesium hydroxide having an average primary particle width of 1 ⁇ m or less For example, in Patent Document 3, magnesium hydroxide having an average primary particle width of 20 to 50 nm and an average secondary particle width of 1 to 100 nm is synthesized using a microreactor.
  • magnesium hydroxide having an average secondary particle diameter of 25.4 nm is synthesized by reacting magnesium salt and hydroxide salt using a microreactor.
  • Acid resistance is a problem when magnesium hydroxide is used in lithium ion battery separators.
  • hydrogen fluoride (HF) present in a minute amount in a battery reacts with an inorganic filler, and the surface of the inorganic filler is fluorinated, and water is generated at that time, and this water is used as an electrolyte or an electrode.
  • SEI Solid Electrolyte Interface
  • Patent Document 6 as in the present invention, more specifically, by combining a hydroxide of at least one transition metal selected from Mn, Fe, Co, Ni, Cu and Zn with magnesium hydroxide, more specifically, Discloses that the acid resistance of the particles is improved by forming a solid solution of both.
  • the disclosed composite metal hydroxide has a secondary particle diameter of 0.2 to 4 ⁇ m, and it has been necessary to make the particle diameter less than 0.2 ⁇ m in order to use it in a thinner film separator.
  • magnesium hydroxide having fine particles, high dispersibility, high purity and excellent acid resistance has not been provided so far.
  • An object of the present invention is to overcome weak acid resistance and aggregation of primary particles, which are problems of the prior art that occur when the average width of primary particles of magnesium hydroxide is reduced. Solving these problems, more specifically, (1) By improving acid resistance, the reaction with hydrogen fluoride, which occurs when magnesium hydroxide is used for separators of lithium ion batteries, is suppressed. It is possible to maintain the durability of the battery, and (2) to improve the dispersibility to form a heat-resistant porous layer having no irregularities when it is thinned.
  • the present invention provides a composite metal hydroxide represented by the following formula (1) satisfying the following (A) and (B), which has overcome the above problems.
  • Mg 1-X (M 2+ ) X (OH) 2 (1)
  • M 2+ is at least one divalent metal selected from Cr, Mn, Fe, Co, Ni, Cu and Zn, and the range of X is 0 ⁇ X ⁇ 0.5.
  • A) The average lateral width of primary particles by SEM method is 10 nm or more and less than 200 nm;
  • the monodispersity represented by the following formula is 50% or more;
  • Monodispersity (%) (Average width of primary particles by SEM method / Average width of secondary particles by dynamic light scattering method) ⁇ 100
  • the method for producing a composite metal hydroxide of the present invention includes the following steps (1) to (4).
  • Raw material preparation for obtaining a water-soluble composite metal salt aqueous solution by mixing a water-soluble magnesium salt aqueous solution and at least one water-soluble metal salt aqueous solution selected from Cr, Mn, Fe, Co, Ni, Cu, and Zn Process.
  • a wet pulverization step of wet pulverizing the slurry containing the product after aging obtained in (3).
  • anionic surfactant cationic surfactant
  • phosphate ester treatment agent silane coupling agent, titanate coupling agent, aluminum coupling agent, silicone treatment agent, sodium silicate after wet grinding
  • the composite metal hydroxide of the present invention can overcome weakness in acid resistance and aggregation of primary particles, which are problems of the prior art that occur when the average width of primary particles of magnesium hydroxide is reduced. . For this reason, by mix
  • the composite metal hydroxide of the present invention can be suitably used for various applications such as antibacterial agents, bactericides in the oral cavity, heat conductive fillers, fine ceramic raw materials, adsorbents and the like. Further, by firing the composite metal hydroxide of the present invention, a composite metal oxide having fine particles, high dispersion and high acid resistance can be produced.
  • the oxides are fine particles and highly dispersed, so they are used for pharmaceutical gastrointestinal drugs, acid acceptors for synthetic rubbers and adhesives, thickeners for FRP production, additives for producing electrical steel sheets, heat conductive fillers, magnesia grinding stone materials It can be suitably used for various applications such as fine ceramic raw materials, brake materials and adsorbents.
  • FIG. 1 is an SEM photograph of 100000 times the composite metal hydroxide of Sample 1 of Example 1.
  • FIG. 4 is a SEM photograph at 100000 times the composite metal oxide of Sample 23 in Example 33.
  • the metal type, the range of X, the average width of primary particles, and the monodispersity of the composite metal hydroxide of the present invention are as follows.
  • M 2+ is at least one divalent metal selected from Cr, Mn, Fe, Co, Ni, Cu, and Zn.
  • Preferred M 2+ is Ni and / or Zn because of excellent acid resistance and easy availability.
  • the range of X is 0 ⁇ X ⁇ 0.5
  • the preferable range is 0.005 ⁇ X ⁇ 0.4
  • the more preferable range is 0.01 ⁇ X ⁇ 0.2.
  • the value of X is 0.5 or more, molding defects due to foaming occur, which is not preferable. This is because the dehydration temperature of M 2+ metal hydroxide is lower than that of magnesium hydroxide.
  • the average lateral width of the primary particles by the SEM method is 10 nm or more and less than 200 nm, preferably 10 nm or more and less than 100 nm, more preferably 10 nm or more and 50 nm. Is less than.
  • the average lateral width of the primary particles is determined from the arithmetic average of the measured values of the lateral width of any 100 crystals in the SEM photograph by SEM (scanning electron microscope).
  • FIG. 1 is a schematic view of how to measure the width of primary particles when the SEM method is used. As shown by the arrows in FIG.
  • the lateral width of the primary particles is measured by measuring the diameter of the particles when the primary particles have a hexagonal plate shape.
  • the lateral width of primary particles cannot be measured by the dynamic light scattering method in principle. Therefore, an accurate value can be calculated by visually confirming with the SEM method.
  • the monodispersity represented by the following formula (B) is 50% or more, preferably 80% or more.
  • the monodispersity is obtained by the following formula.
  • Monodispersity (%) (Average width of primary particles by SEM method / Average width of secondary particles by dynamic light scattering method) ⁇ 100
  • the average lateral width of the secondary particles is measured by a dynamic light scattering method. Secondary particles are formed by aggregation of a plurality of primary particles.
  • FIG. 2 is a schematic diagram of how to measure the width of secondary particles when the dynamic light scattering method is used.
  • the longest diameter of the secondary particles is the width. That is, as shown by the arrows and dotted lines in FIG. 2, the diameter of the sphere when the secondary particles are considered to be wrapped by the sphere is measured. In the SEM method, it is difficult to accurately measure the lateral width of the secondary particles.
  • surface treatment In the composite metal hydroxide represented by the formula (1), in order to improve acid resistance and dispersibility, it is desirable to perform a surface treatment on the particle surface.
  • surface treatment agents include anionic surfactants, cationic surfactants, phosphate ester treatment agents, silane coupling agents, titanate coupling agents, aluminum coupling agents, silicone treatment agents, sodium silicate, etc.
  • a preferable surface treatment agent from the viewpoint of improving acid resistance includes the combined use of sodium silicate and a cationic surfactant. Since the crystal surface of magnesium hydroxide has a positive charge, high acid resistance can be imparted by first treating the surface with sodium silicate and then treating the surface with a cationic surfactant.
  • the total amount of the surface treatment agent is 0.01 to 20% by weight, preferably 0.5 to 10% by weight, based on the weight of the composite metal hydroxide represented by the formula (1).
  • the composite metal oxide of the present invention is represented by the following formula (2), and the metal type, the range of X, the average lateral width of the primary particles, and the monodispersity are as follows. (Mg) 1-X (M 2+ ) X O (2)
  • M 2+ is at least one divalent metal selected from Cr, Mn, Fe, Co, Ni, Cu, and Zn.
  • Preferred M 2+ is Ni and / or Zn because of excellent acid resistance and easy availability.
  • the range of X is 0 ⁇ X ⁇ 0.5
  • the preferable range is 0.005 ⁇ X ⁇ 0.4
  • the more preferable range is 0.01 ⁇ X. ⁇ 0.2.
  • the average lateral width of the primary particles by the SEM method is 10 nm or more and less than 200 nm, preferably 10 nm or more and less than 100 nm, more preferably 10 nm or more and less than 50 nm. It is.
  • the average lateral width of the primary particles is obtained from the arithmetic average of the measured lateral widths of any 100 crystals in the SEM photograph by the SEM method.
  • the monodispersity represented by the following formula (B) is 50% or more, preferably 80% or more.
  • the average lateral width of the secondary particles is measured by a dynamic light scattering method. This is because it is difficult for the SEM method to accurately measure the lateral width of the secondary particles.
  • Monodispersity (%) (Average width of primary particles by SEM method / Average width of secondary particles by dynamic light scattering method) ⁇ 100
  • surface treatment In the composite metal oxide represented by the formula (2), in order to improve acid resistance and dispersibility, it is desirable to perform surface treatment on the particle surface.
  • surface treatment agents include anionic surfactants, cationic surfactants, phosphate ester treatment agents, silane coupling agents, titanate coupling agents, aluminum coupling agents, silicone treatment agents, sodium silicate, etc.
  • the total amount of the surface treatment agent is 0.01 to 20% by weight, preferably 0.5 to 10% by weight, based on the weight of the composite metal oxide represented by the formula (1).
  • the resin composition of the present invention contains 0.1 to 250 parts by weight of the composite metal hydroxide of the present invention with respect to 100 parts by weight of the resin.
  • the compounding amount of the composite metal hydroxide is preferably 1 to 200 parts by weight.
  • the mixing and kneading method of the resin and the composite metal hydroxide of the present invention there is no particular restriction on the mixing and kneading method of the resin and the composite metal hydroxide of the present invention, and any method can be used as long as both can be mixed uniformly. For example, they are mixed and kneaded by a single or twin screw extruder, a roll, a Banbury mixer or the like.
  • molding method According to the kind of resin and rubber, the kind of desired molded article, etc., a well-known shaping
  • the resin used in the present invention means a resin and / or rubber.
  • a resin and / or rubber for example, polyethylene, a copolymer of ethylene and another ⁇ -olefin, a copolymer of ethylene and vinyl acetate, ethylene and an acrylate ether, Copolymers of ethylene and methyl acrylate, polypropylene, copolymers of propylene and other ⁇ -olefins, polybutene-1, poly-4-methylpentene-1, polystyrene, styrene and acrylonitrile.
  • Copolymer Copolymer, Copolymer of ethylene and propylene diene rubber, Copolymer of ethylene and butadiene, Polyvinyl acetate, Polylactic acid, Polyvinyl alcohol, Polyacrylate, Polymethacrylate, Polyurethane, Polyester, Polyether, Polyamide, ABS , Polycarbonate, polyphenylene sulfide, etc.
  • a plastic resin is mentioned.
  • thermosetting resins such as a phenol resin, a melamine resin, an epoxy resin, an unsaturated polyester resin, an alkyd resin, are mentioned.
  • EPDM EPDM, SBR, NBR, butyl rubber, chloroprene rubber, isoprene rubber, chlorosulfonated polyethylene rubber, silicon rubber, fluorine rubber, chlorinated butyl rubber, brominated butyl rubber, epichlorohydrin rubber, chlorinated polyethylene and the like can be mentioned.
  • the resin composition of the present invention includes other additives such as antioxidants, reinforcing agents such as talc, ultraviolet absorbers, lubricants, matting agents such as fine silica, carbon black and the like.
  • Flame retardants such as pigments, bromine-based flame retardants and phosphate ester-based flame retardants can be appropriately selected and blended.
  • flame retardant aids such as zinc stannate, alkali metal stannate, carbon powder, and fillers such as calcium carbonate can be appropriately selected and blended.
  • the preferred compounding amounts of these additives are 0.01 to 5 parts by weight of antioxidant, 0.1 to 50 parts by weight of reinforcing agent, and 0.01 to 5 parts by weight of UV absorber with respect to 100 parts by weight of the resin.
  • the method for producing a composite metal hydroxide of the present invention includes the following steps (1) to (4).
  • a water-soluble magnesium salt aqueous solution and at least one water-soluble metal salt aqueous solution selected from Cr, Mn, Fe, Co, Ni, Cu, and Zn are mixed to prepare a water-soluble composite metal salt aqueous solution.
  • the water-soluble magnesium salt include, but are not limited to, magnesium chloride, magnesium nitrate, magnesium acetate, magnesium sulfate and the like. In order to prevent aggregation of primary particles, it is preferable to use magnesium chloride, magnesium nitrate, or magnesium acetate.
  • Examples of the aqueous solution of at least one water-soluble composite metal salt selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, and Zn include chloride salts, nitrates, acetates, sulfates, etc. is not. From the viewpoint of increasing acid resistance and preventing agglomeration of primary particles, hydrochloride, nitrate, and acetate are preferred.
  • the concentration of the composite metal salt aqueous solution is (Mg + M 2+ ) of 0.1 to 5.0 mol / L, preferably 0.4 to 4.0 mol / L.
  • the ratio of Mg to M 2+ is 0 ⁇ M 2+ / Mg ⁇ 1, preferably 0.005 ⁇ M 2+ /Mg ⁇ 0.667, more preferably 0.010 ⁇ M 2+ /Mg ⁇ 0.250. is there.
  • a slurry containing a composite metal hydroxide can be produced by reacting an aqueous solution of a composite metal salt with an aqueous alkali metal hydroxide solution.
  • the alkali metal hydroxide include sodium hydroxide and potassium hydroxide, but are not limited thereto.
  • the reaction method include batch reaction and continuous reaction, but are not limited thereto. In consideration of productivity and reaction uniformity, a continuous reaction is preferably used.
  • the pH during the reaction is adjusted to 9.0 to 12.0, preferably 9.5 to 11.5, more preferably 10.0 to 11.0. When the reaction pH is lower than 9.0, the primary particles grow when the slurry is aged, which is not preferable.
  • the concentration of the alkali metal hydroxide is 0.1 to 20.0 mol / L, preferably 0.4 to 15.0 mol / L.
  • the concentration during the reaction is 0.1 to 5.0 mol / L, preferably 0.4 to 4.0 mol / L, in terms of composite metal hydroxide.
  • the reaction temperature is 0 to 100 ° C., preferably 10 to 60 ° C., more preferably 20 to 40 ° C. When the reaction temperature is higher than 100 ° C., the primary particles grow to 200 nm or more, which is not preferable.
  • the reaction temperature is less than 0 ° C., the slurry freezes, which is not preferable.
  • the slurry after the reaction is stirred and held at 0 to 100 ° C. for 1 to 24 hours. By passing through this step, it is possible to relax the aggregation of primary particles that are strong immediately after the reaction. If the aging time is less than 1 hour, it is not sufficient as a time for loosening the aggregation of the primary particles. Aging for longer than 24 hours does not make sense because there is no change in the aggregated state. A preferred aging time is 2 to 18 hours, and more preferably 4 to 15 hours. If the aging temperature is higher than 100 ° C., the primary particles grow to 200 nm or more, which is not preferable. An aging temperature of less than 0 ° C. is not preferable because the slurry freezes.
  • a more preferable aging temperature is 10 to 60 ° C., and most preferably 20 to 40 ° C.
  • the concentration at the time of aging is 0.1 to 5.0 mol / L, preferably 0.4 to 4.0 mol / L in terms of composite metal hydroxide.
  • the productivity is low, and when it is higher than 5.0 mol / L, the primary particles are aggregated, which is not preferable.
  • the slurry after the aging treatment is dehydrated, washed with deionized water having a weight 20 times the solid content, and then re-emulsified with deionized water.
  • the slurry after re-emulsification is wet pulverized.
  • a bead mill or a high-pressure homogenizer is preferably used.
  • the temperature during wet pulverization is 0 to 100 ° C., more preferably 10 to 60 ° C., and most preferably 20 to 40 ° C. If the temperature during wet pulverization is 100 ° C. or higher, the primary particles grow to 200 nm or more, which is not preferable.
  • the concentration at the time of wet pulverization is 0.1 to 5.0 mol / L, preferably 0.4 to 4.0 mol / L, in terms of composite metal hydroxide.
  • concentration during wet pulverization is lower than 0.1 mol / L, productivity is low, and when it is higher than 5.0 mol / L, aggregation of primary particles cannot be solved, which is not preferable.
  • the preferred bead diameter is 0.001 mm to 0.1 mm, more preferably 0.01 mm to 0.05 mm.
  • the preferred pressure is from 100 bar to 1000 bar, more preferably from 400 bar to 700 bar.
  • the dispersibility in the resin when added, kneaded, and dispersed in the resin can be improved.
  • a wet method or a dry method can be used. In consideration of processing uniformity, a wet method is preferably used.
  • the slurry after the wet pulverization is dehydrated, washed with deionized water having a weight 20 times the solid content, and then suspended in deionized water.
  • the temperature of the slurry after suspension is controlled, and a surface treatment agent dissolved under stirring is added. The temperature during the surface treatment is appropriately adjusted to a temperature at which the surface treatment agent is dissolved.
  • the surface treatment agent examples include an anionic surfactant, a cationic surfactant, a phosphate ester treatment agent, a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, a silicone treatment agent, and sodium silicate. At least one selected from can be used. From the viewpoint of improving acid resistance, a preferred surface treatment agent is a combination of sodium silicate and a cationic surfactant.
  • the total amount of the surface treatment agent is preferably 0.01 to 20% by weight, more preferably 0.5 to 10% by weight, based on the weight of the composite metal hydroxide.
  • the slurry after the surface treatment is dehydrated, washed with deionized water having a weight 20 times the solid content, and then dried to obtain the composite metal hydroxide of the present invention.
  • the drying method can be hot air drying, vacuum drying, or the like, but is not particularly limited.
  • the composite metal oxide of the present invention can be obtained by firing the composite metal hydroxide of the present invention. After firing, a surface treatment is performed by a dry method or a wet method, whereby aggregation of primary particles can be prevented and a composite metal oxide having a high monodispersity can be obtained.
  • the composite metal oxide of the present invention can be obtained by firing the composite metal hydroxide of the present invention at 400 to 1000 ° C. for 1 to 10 hours.
  • a more preferable firing temperature is 450 to 900 ° C., and further preferably 500 to 800 ° C.
  • the firing temperature is 400 ° C. or lower, magnesium oxide is not generated, and when the firing temperature is 1000 ° C. or higher, the primary particles are coarsened by sintering.
  • a more preferable firing time is 1 to 8 hours, and further preferably 1 to 6 hours. If the firing time is less than 1 hour, it is not sufficient to produce magnesium oxide, and if it is 10 hours or more, the primary particles are coarsened by sintering, which is not preferable.
  • the dispersibility in the resin when added, kneaded, and dispersed in the resin can be improved.
  • a wet method or a dry method can be used. In consideration of processing uniformity, a wet method is preferably used.
  • the surface treatment agent in which the powder after firing is dispersed in an alcohol solvent and dissolved under stirring is added. The temperature during the surface treatment is appropriately adjusted to a temperature at which the surface treatment agent is dissolved.
  • the surface treatment agent examples include an anionic surfactant, a cationic surfactant, a phosphate ester treatment agent, a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, a silicone treatment agent, and sodium silicate. At least one selected from can be used.
  • the addition amount of the surface treatment agent is preferably 0.01 to 20% by weight, more preferably 0.5 to 10% by weight, based on the weight of the composite metal hydroxide.
  • a sample was added to ethanol, subjected to ultrasonic treatment for 5 minutes, and then subjected to arbitrary 100 crystals using a scanning electron microscope (SEM) (manufactured by JEOL, JSM-7600F). The horizontal width of the primary particles was measured, and the arithmetic average was taken as the average primary particle width. The horizontal width of the primary particles is measured by measuring the diameter of the particles when the primary particles are hexagonal plate-like plate surfaces as indicated by arrows in FIG.
  • SEM scanning electron microscope
  • ELSZ-2000S dynamic scattering particle size analyzer
  • the titration is completed when 5.15 mL of 0.1N hydrochloric acid is added. Acid resistance was evaluated by the time from the start to the end of 5.15 mL of 0.1N hydrochloric acid. The longer the time, the better the acid resistance.
  • (H) Acid resistance test method of resin composition (carbon dioxide gas blowing test)
  • the test piece prepared in (g) was impregnated with 500 mL of deionized water, the temperature was maintained at 20 ° C., and carbon dioxide gas was blown in at a rate of 500 mL / min, and maintained for 24 hours.
  • the acid resistance was evaluated by the Mg concentration in the solution after holding. The lower the Mg concentration in the solution, the better the acid resistance.
  • reaction process Each solution was continuously supplied to the reaction vessel at 20 mL / min using a metering pump to cause a coprecipitation reaction.
  • the reaction tank is made of stainless steel and overflows with a capacity of 500 mL, and 300 mL of deionized water is put in advance in this reaction tank, the temperature is adjusted to 30 ° C., and the mixture is stirred at 500 rpm using a stirrer.
  • the raw material whose temperature was adjusted to 30 ° C. was supplied to the reaction vessel, and the flow rate was adjusted so that the reaction pH was 10.3.
  • the obtained slurry was temperature-controlled at 30 ° C. and aged for 10 hours while stirring at 300 rpm.
  • the reaction product was filtered and washed with deionized water, and then the cake was dispersed in deionized water to obtain a slurry.
  • the slurry was wet pulverized using a bead mill (Hiroshima Metal & Machinery, Ultra Apex Mill). 400 mL of a slurry with a concentration of 0.5 mol / L was circulated at 200 mL / min, and pulverized for 20 minutes at a diameter of 0.03 mm beads and a rotation speed of 400 Hz. The ground slurry was filtered with suction and deionized. The cake was put into a hot air dryer, dried at 110 ° C. for 12 hours, and then pulverized to obtain a composite metal hydroxide sample 1 of the present invention.
  • a bead mill Hiroshima Metal & Machinery, Ultra Apex Mill
  • FIG. 3 shows an SEM photograph of Sample 1 at a magnification of 100,000.
  • Example 1 In the raw material preparation step of Example 1, a sample was prepared in the same manner except that reagent grade zinc chloride was used instead of reagent grade nickel chloride to obtain the composite metal hydroxide sample 2 of the present invention. It was.
  • the composite metal hydroxide sample of the present invention was prepared in the same manner as in the raw material preparation step of Example 1, except that reagent grade manganese chloride (2) was used instead of reagent grade nickel chloride. 3 was obtained.
  • Example 1 In the reaction step of Example 1, a sample was prepared in the same manner except that the pH during the reaction was set to 9.3 to obtain a composite metal hydroxide sample 5 of the present invention.
  • Example 1 In the reaction step of Example 1, a sample was prepared in the same manner except that the pH during the reaction was set to 11.6 to obtain a composite metal hydroxide sample 6 of the present invention.
  • Example 1 In the aging step of Example 1, a sample was prepared in the same manner except that the aging temperature was set to 60 ° C. to obtain a composite metal hydroxide sample 7 of the present invention.
  • Example 1 In the aging step of Example 1, a sample was prepared in the same manner except that the aging temperature was 10 ° C., and a composite metal hydroxide sample 8 of the present invention was obtained.
  • Example 1 In the aging step of Example 1, a sample was prepared in the same manner except that the aging time was 3 hours, and a composite metal hydroxide sample 9 of the present invention was obtained.
  • Example 1 In the aging process of Example 1, a sample was prepared in the same manner except that the aging time was set to 20 hours to obtain a composite metal hydroxide sample 10 of the present invention.
  • Example 1 instead of the bead mill, a sample was prepared in the same manner except that wet pulverization was performed using a high-pressure homogenizer (manufactured by SMT, LAB1000) to obtain the composite metal hydroxide sample 11 of the present invention. It was. 400 mL of slurry having a concentration of 0.5 mol / L was circulated at 200 mL / min, and wet pulverization was performed at 500 bar for 20 minutes.
  • a high-pressure homogenizer manufactured by SMT, LAB1000
  • Example 1 the sodium silicate-containing treatment liquid heated to 80 ° C. was added to the slurry after wet pulverization, and the mixture was stirred and held at 80 ° C. for 20 minutes. Subsequently, a dioleyldimethylammonium chloride treatment solution heated to 80 ° C. was added, and the mixture was stirred and held at 80 ° C. for 20 minutes. After cooling the surface-treated slurry to 30 ° C., suction filtration and deionization washing were performed. Thereafter, the cake was put into a hot air dryer, dried at 110 ° C. for 12 hours, and then pulverized to obtain a composite metal hydroxide sample 12 of the present invention.
  • Example 12 In the surface treatment step of Example 12, a sample was prepared in the same manner except that No. 3 sodium silicate was used alone to obtain a composite metal hydroxide sample 13 of the present invention.
  • Example 12 In the surface treatment step of Example 12, a sample was prepared in the same manner except that dioleyldimethylammonium chloride was used alone to obtain a composite metal hydroxide sample 14 of the present invention.
  • Example 12 In the surface treatment step of Example 12, a sample was prepared in the same manner except that 1% by weight of sodium stearate was used instead of sodium silicate, and the composite metal water of the present invention was used. An oxide sample 15 was obtained.
  • Example 12 In the surface treatment step of Example 12, a sample was prepared in the same manner except that 1% by weight of sodium stearate was used alone with respect to the composite metal hydroxide, and the composite metal hydroxide sample of the present invention was used. 16 was obtained.
  • Example 1 In the raw material preparation step of Example 1, a sample was prepared in the same manner except that reagent grade magnesium chloride was used alone, and Sample 17 was obtained.
  • Example 2 A sample was prepared in the same manner as in Example 1 except that the pH during the reaction was set to 8.5.
  • Example 4 In the aging step of Example 1, a sample was prepared in the same manner except that the aging temperature was 120 ° C., and Sample 20 was obtained.
  • Example 5 A sample was prepared in the same manner as in Example 1 except that the aging step was omitted, and a sample 21 was obtained.
  • Example 6 A sample was prepared in the same manner as in Example 1 except that the wet pulverization step was omitted, and a sample 22 was obtained.
  • the composite metal hydroxide of the present application has an average primary particle width of 200 nm or less and a monodispersity of 50% or more.
  • the composite metal hydroxide of Example 1 has a significantly improved powder acid resistance while maintaining a high degree of monodispersity.
  • the samples of Examples 12 to 16 subjected to surface treatment show higher monodispersity and powder acid resistance than the samples without surface treatment.
  • Example 12 using sodium silicate and dioleyldimethylammonium chloride shows a significant improvement in monodispersity and acid resistance.
  • Example 1 110 parts by weight of the powder sample 1 prepared in Example 1 was added to 100 parts by weight of polyethylene to produce a resin composition.
  • Polyethylene manufactured by Nippon Polyethylene, Novatec LL UF-240
  • a powder sample are melt-kneaded at 150 ° C. using a plast mill (manufactured by BRABENDER), and the resulting resin composition is press molded (manufactured by Shindo Metal Co., Ltd.
  • a test piece was prepared by performing a formula SF type hydraulic press. Table 3 shows the results of the flame retardancy test and the acid resistance test.
  • Test pieces were prepared in the same manner as in Example 17 using the powder sample 2 prepared in Example 2.
  • Example 3 Using the powder sample 3 prepared in Example 3, a test piece was prepared in the same manner as in Example 17.
  • Test pieces were prepared in the same manner as in Example 17 using the powder sample 4 prepared in Example 4.
  • Test pieces were prepared in the same manner as in Example 17 using the powder sample 5 prepared in Example 5.
  • Test pieces were prepared in the same manner as in Example 17 using the powder sample 6 prepared in Example 6.
  • Test pieces were prepared in the same manner as in Example 17 using the powder sample 7 prepared in Example 7.
  • Test pieces were prepared in the same manner as in Example 17 using the powder sample 8 prepared in Example 8.
  • Test pieces were prepared in the same manner as in Example 17 using the powder sample 9 prepared in Example 9.
  • Test pieces were prepared in the same manner as in Example 17 using the powder sample 10 prepared in Example 10.
  • Test pieces were prepared in the same manner as in Example 17 using the powder sample 11 prepared in Example 11.
  • Test pieces were prepared in the same manner as in Example 17 using the powder sample 12 prepared in Example 12.
  • Test pieces were prepared in the same manner as in Example 17 using the powder sample 13 prepared in Example 13.
  • Test pieces were prepared in the same manner as in Example 17 using the powder sample 14 prepared in Example 14.
  • Test pieces were prepared in the same manner as in Example 17, using the powder sample 15 prepared in Example 15.
  • Example 16 Using the powder sample 16 produced in Example 16, a test piece was produced in the same manner as in Example 17.
  • Comparative Example 7 Using the powder sample 17 produced in Comparative Example 1, a test piece was produced in the same manner as in Example 17.
  • the resin composition containing the composite metal hydroxide of the present invention satisfied the V-0 or V-1 standard in the UL94 vertical test (1/8 inch), and in the carbon dioxide blowing test, Mg resin It can be seen that there is little elution of.
  • Example 1 The powder sample 1 produced in Example 1 was fired at 500 ° C. for 1 hour in a siliconite electric furnace in an air atmosphere. After cooling, the mixture was pulverized using a mortar to obtain a composite metal oxide sample 23 of the present invention.
  • the experimental conditions of Sample 23 are shown in Table 4, and the chemical composition, average primary particle width, secondary particle average width, monodispersity, and acid resistance test results are shown in Table 5.
  • FIG. 4 shows an SEM photograph of sample 23 at a magnification of 100,000.
  • Example 33 A composite metal oxide sample 24 of the present invention was obtained in the same manner except that the firing temperature was set to 800 ° C.
  • Example 33 A composite metal oxide sample 25 of the present invention was obtained in the same manner except that the firing time was 8 hours.
  • Example 33 the fired composite metal oxide was dispersed in an ethanol solvent under stirring, and the temperature was adjusted to 60 ° C. Similarly, a stearic acid-containing treatment solution heated to 60 ° C. was added, and the mixture was stirred and held at 60 ° C. for 20 minutes. After the surface-treated slurry was cooled to 30 ° C., suction filtration was performed. The cake was naturally dried and then pulverized to obtain a composite metal oxide sample 26 of the present invention.
  • Example 33 in place of the powder sample 1 produced in Example 1, Sample 29 produced in Comparative Example 1 was prepared in the same manner except that it was baked at 500 ° C. for 1 hour in an air atmosphere in a siliconite electric furnace. Got.
  • Table 4 and Table 5 show that the composite metal oxide of the present application has a primary particle size of less than 200 nm, a monodispersity of 50% or more, and high acid resistance.
  • sample 26 Example 36
  • Sample 28 Comparative Example 14
  • Sample 29 Comparative Example 15
  • Sample 29 has poor acid resistance of the powder.
  • the composite metal hydroxide of the present invention can be added to the separator of a lithium ion battery, thereby suppressing the reaction with hydrogen fluoride while suppressing the thickness of the separator and improving the safety of the battery. Further, the composite metal hydroxide of the present invention can be suitably used as a flame retardant. Since the fine particles are highly dispersed, the amount of the resin can be reduced, and the acid resistance of the resin can be improved.
  • the composite metal hydroxide of the present invention can be suitably used for various applications such as antibacterial agents, bactericides in the oral cavity, heat conductive fillers, fine ceramic raw materials, adsorbents and the like. Further, by firing the composite metal hydroxide of the present invention, a composite metal oxide having fine particles, high dispersion and high acid resistance can be produced.
  • the oxides are fine particles and highly dispersed, so they are used for pharmaceutical gastrointestinal drugs, acid acceptors for synthetic rubbers and adhesives, thickeners for FRP production, additives for producing electrical steel sheets, heat conductive fillers, magnesia grinding stone materials It can be suitably used for various applications such as fine ceramic raw materials, brake materials and adsorbents.

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  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
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  • Inorganic Compounds Of Heavy Metals (AREA)
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Abstract

Le problème décrit par la présente invention est de surmonter la faiblesse de la résistance aux acides et l'agrégation de particules primaires qui se produisent lorsque la largeur moyenne de particules primaires d'hydroxyde de magnésium est réduite. La solution selon l'invention porte sur un hydroxyde métallique composite représenté par la formule (1) qui satisfait (A) et (B) ci-dessous. (Mg)1-X(M2+)X(OH)2 (1) (où, dans la formule, M2+ est au moins un métal divalent choisi parmi Cr, Mn, Fe, Co, Ni, Cu et Zn, et la plage de X est 0 0 < X < 0.5.) (A) La largeur moyenne des particules primaires telle que mesurée par MEB est d'au moins 10 nm et inférieure à 200 nm; (B) la monodispersivité représentée par la formule suivante est de 50 % ou plus : monodispersivité (%) = (largeur moyenne des particules primaires telle que mesurée par MEB/largeur moyenne de particules secondaires telle que mesurée par diffusion dynamique de la lumière) x 100.
PCT/JP2017/032035 2016-09-07 2017-09-06 Hydroxyde métallique composite microparticulaire, produit calciné de celui-ci, son procédé de production et composition de résine associée WO2018047841A1 (fr)

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KR1020207005788A KR102262069B1 (ko) 2016-09-07 2017-09-06 미립자 복합 금속 수산화물, 그 소성물, 그 제조 방법 및 그 수지 조성물
JP2018538429A JP6593942B2 (ja) 2016-09-07 2017-09-06 微粒子複合金属水酸化物、その焼成物、その製造方法及びその樹脂組成物
CN201780067191.5A CN109906202B (zh) 2016-09-07 2017-09-06 微粒复合金属氢氧化物、其烧制物、其制造方法及其树脂组合物

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KR20200023553A (ko) 2020-03-04
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