KR102085040B1 - Fine particle composite metal hydroxide, its baked material, its manufacturing method, and its resin composition - Google Patents

Abstract

(Problem) The subject of this invention is the weakness of the acid resistance and the aggregation of a primary particle which generate | occur | produce when the average width of the primary particle of magnesium hydroxide is made small.
(Solution means) The present invention provides a composite metal hydroxide represented by the following formula (1) that satisfies the following (A) and (B).
(Mg) _1-X (M ²⁺ ) _X (OH) ₂ (1)
( ^Wherein M ²⁺ is at least one or more divalent metals selected from Cr, Mn, Fe, Co, Ni, Cu, Zn, and the range of X is 0 <X <0.5)
(A) the average width of the primary particles by the SEM method is 10 nm or more and less than 200 nm; (B) 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

Description

Fine particle composite metal hydroxide, its baked material, its manufacturing method, and its resin composition

The present invention relates to a composite metal hydroxide having a small average width of primary particles, dispersing primary particles, and having high acid resistance, a fired product thereof, a production method thereof, and a resin composition thereof.

In recent years, the technique which uses magnesium hydroxide for the separator of a lithium ion battery is popular. In nonaqueous electrolyte batteries, especially nonaqueous electrolyte secondary batteries, heat generation due to the decomposition of the positive electrode is considered to be the most dangerous, and this decomposition takes place around 300 ° C. For this reason, when the magnesium hydroxide whose endothermic reaction generate | occur | produces the temperature of the range of 300 degreeC-400 degreeC is mix | blended with a separator, it is effective in preventing the heat generation of a battery. In Patent Literature 1, an aspect using a metal hydroxide is preferable from the viewpoints of improving the flame retardancy, handling property, antistatic effect, and durability improvement of the battery as the inorganic filler, and among them, aluminum hydroxide or magnesium hydroxide is preferred, and inorganic filler It is disclosed that the average particle diameter is preferably in the range of 0.1 to 2 µm from the viewpoints of short circuit resistance and moldability at high temperatures.

Patent Document 1 also discloses a method of forming a heat resistant porous layer on at least one side of a polyolefin porous substrate as a method for producing a separator of a lithium ion battery. More specifically, the inorganic filler is dispersed in an organic solvent to form a slurry for coating, and applied to a polyolefin porous substrate. If an inorganic filler is not disperse | distributed in a coating slurry, a uniform coating film will not be obtained and high dispersibility is calculated | required by an inorganic filler. When the dispersibility of an inorganic filler is not preferable, the method of surface-treating an inorganic filler with a silane coupling agent etc. and improving dispersibility is disclosed.

With the miniaturization of lithium ion batteries, thinning of the separator is required, and the inorganic filler to be blended is also required to have fine particles. In patent document 2, when using magnesium hydroxide as an ultra-thin battery separator use, when an average particle diameter becomes large, it will be reflected also in the thickness of a separator, It is preferable that an average particle diameter is 0.8 micrometer or less, It is more preferable that it is 0.7 micrometer or less, The average particle diameter is Although the compound of magnesium which is 0.1 micrometer or less can also be synthesize | combined, it is disclosed that it cannot say that it is preferable at this size because strong interparticle interaction is expressed and affects the coating process at the time of forming a porous ceramic layer.

Attempts have been made to synthesize particulate magnesium hydroxide having an average width of primary particles of 1 µm or less. For example, in patent document 3, the magnesium hydroxide whose average width of a primary particle is 20-50 nm, and the average width of a secondary particle is 1-100 nm is synthesize | combined using a microreactor.

Similarly, in Patent Document 4, magnesium hydroxide having an average secondary particle size of 25.4 nm is synthesized by reacting a magnesium salt with a hydroxide salt using a microreactor.

When magnesium hydroxide is used in the separator of a lithium ion battery, it is acid resistance. In Patent Literature 5, hydrogen fluoride (HF) present in a small amount in the battery reacts with the inorganic filler to fluorine the surface of the inorganic filler, and water is generated at this time, so that moisture is formed on the surface of the electrolyte or the electrode (Solid Electrolyte Interface). It is disclosed that when the film is decomposed, when the electrolyte solution or the SEI film is decomposed, the internal resistance of the battery increases and lithium required for charging and discharging is deactivated, which may lower the durability of the battery.

In Patent Document 6, as in the present invention, at least one hydroxide of a transition metal selected from Mn, Fe, Co, Ni, Cu, and Zn is combined with magnesium hydroxide to more specifically form a solid solution of both to improve acid resistance of the particles. Is disclosed. However, the secondary particle diameter of the composite metal hydroxide disclosed is 0.2-4 micrometers, and in order to use it for thin film separators, it was necessary to make particle diameter less than 0.2 micrometer. However, magnesium hydroxide has not been provided so far with fine particles, high dispersibility, high purity and excellent acid resistance.

WO 2012-081556 A1 Japanese Patent Publication 2016-62689 WO 2013-122239 A1 Japanese Patent Publication 2011-195384 Japanese Patent Publication 2010-278018 Japanese Patent Laid-Open No. 6-41441

An object of the present invention is to overcome the weakness of acid resistance and aggregation of primary particles, which is a problem of the prior art that occurs when the average width of the primary particles of magnesium hydroxide is reduced. To solve these problems, more specifically (1) to maintain the durability of the battery by suppressing the reaction with hydrogen fluoride generated when magnesium hydroxide is used in separator applications of lithium ion batteries by improving acid resistance, (2 By improving the dispersibility, it becomes possible to form a heat resistant porous layer having no unevenness when thinned.

The present invention provides a composite metal hydroxide represented by the following formula (1) that satisfies the following problems (A) and (B).

(Mg) _1-X (M ²⁺ ) _X (OH) ₂ (1)

( ^Wherein M ²⁺ is at least one or more divalent metals selected from Cr, Mn, Fe, Co, Ni, Cu, Zn, and the range of X is 0 <X <0.5)

(A) the average width of the primary particles by the SEM method is 10 nm or more and less than 200 nm;

(B) 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 manufacturing method of the composite metal hydroxide of this invention includes the process of the following (1)-(4).

(1) A raw material adjusting step of mixing a water-soluble aqueous magnesium salt solution with at least one water-soluble metal salt aqueous solution selected from Cr, Mn, Fe, Co, Ni, Cu, and Zn to obtain a water-soluble aqueous composite metal salt solution.

(2) A reaction step of obtaining a slurry containing a product by reacting an aqueous aqueous solution of a composite metal salt obtained in (1) with an aqueous alkali metal hydroxide solution.

(3) A aging step of stirring and maintaining the slurry containing the product obtained in (2) at 0 to 100 ° C for 1 to 24 hours.

(4) A wet grinding step of wet grinding a slurry containing a product after aging obtained in (3).

After wet grinding, surface treatment is carried out with at least one member selected from the group consisting of anionic surfactants, cationic surfactants, phosphate ester treatment agents, silane coupling agents, titanate coupling agents, aluminum coupling agents, silicone treatment agents and sodium silicate. Acid resistance can be further improved, and aggregation of the primary particle at the time of drying can be prevented.

(Effects of the Invention)

The composite metal hydroxide of the present invention can overcome the weakness of acid resistance and aggregation of primary particles, which is a problem of the prior art, which occurs when the average width of the primary particles of magnesium hydroxide is reduced.

For this reason, by mix | blending with the separator of a lithium ion battery, reaction with hydrogen fluoride can be suppressed, suppressing the film thickness of a separator, and battery safety can be improved. The composite metal hydroxide of the present invention can also be suitably used as a flame retardant. The amount of the fine particles dispersed in the resin can be reduced, and the acid resistance of the resin can be improved.

The composite metal hydroxide of this invention can be used suitably also for various uses, such as an antibacterial agent, an oral fungicide, a heat conductive filler, a fine ceramic raw material, and an adsorbent. Further, by firing the composite metal hydroxide of the present invention, it is possible to produce a composite metal oxide having fine particles and high dispersion and high acid resistance. The oxides are fine particles, highly dispersed, such as medicinal gastrointestinal, acid acceptor of synthetic rubber or adhesive, thickener for manufacturing FRP, additive for manufacturing steel sheet, heat conducting filler, magnesia whetstone material, fine ceramic raw material, brake material, adsorbent, etc. It can be used suitably for various uses.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram of the method of measuring the width of a primary particle when the SEM method is used.
2 is a schematic diagram of a method for measuring the width of secondary particles when the dynamic light scattering method is used.
3 is an SEM photograph of 100,000 times the composite metal hydroxide of Sample 1 of Example 1. FIG.
4 is a SEM photograph of 100,000 times the composite metal oxide of Sample 23 of Example 33.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated concretely.

<Composite metal hydroxide>

The metal, the range of X, the average width of a primary particle, and monodispersity of the metal of the composite metal hydroxide of this invention are as follows.

(Type of metal)

In the composite metal hydroxide represented by the formula (1), M ²⁺ is at least one or more divalent metals selected from Cr, Mn, Fe, Co, Ni, Cu, and Zn. M ²⁺ is preferably Ni and / or Zn in view of excellent acid resistance and easy availability. As a flame retardant, the formation of the carbonized layer on the surface of a plastic can be promoted by the dehydrogenation catalyst effect of a M2 ⁺ metal element, and a flame retardance can be improved.

(Range of X)

In the composite metal hydroxide represented by the formula (1), the range of X is 0 <X <0.5, the preferred range is 0.005≤X≤0.4, and the more preferable range is 0.01≤X≤0.2. When the value of X is 0.5 or more, since the molding defect by foaming arises, it is unpreferable. This is because the dehydration temperature of M ²⁺ metal hydroxide is lower than that of magnesium hydroxide.

(Average width of primary particles)

In the composite metal hydroxide represented by the formula (1), the average width of the primary particles by the (A) 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 width of a primary particle is calculated | required from the arithmetic mean of the measured value of the width of any 100 crystal | crystallization in a SEM photograph by SEM (scanning electron microscope). BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram of the method of measuring the width of a primary particle when the SEM method is used. As shown by the arrow shown in FIG. 1, the width | variety of a primary particle measures the diameter of the particle | grains when the primary particle is a hexagonal plate shape. The width of the primary particles cannot in principle be measured by the dynamic light scattering method. Therefore, an accurate value can be calculated by visually confirming by SEM method.

Monodispersity

In the composite metal hydroxide represented by the formula (1), the monodispersity represented by the following formula (B) is 50% or more, preferably 80% or more. Monodispersity is calculated | required by the following formula | equation.

Monodispersity (%) = (Average Width of Primary Particles by SEM Method / Average Width of Secondary Particles by Dynamic Light Scattering Method) × 100

By increasing monodispersity, when used for the separator of a lithium ion battery, the heat resistant porous layer without an unevenness | corrugation can be formed. The average width of the secondary particles is measured by the dynamic light scattering method. Secondary particles are formed by aggregation of a plurality of primary particles. 2 is a schematic diagram of a method for measuring the width of secondary particles when the dynamic light scattering method is used. The longest diameter of the secondary particles becomes the width. That is, as shown by the arrow and the dotted line of FIG. 2, the diameter of the sphere when the secondary particle is considered to be enclosed by the sphere is measured. In addition, it is difficult to accurately measure the width of the secondary particles by the SEM method.

(Surface treatment)

In the composite metal hydroxide represented by Formula (1), in order to improve acid resistance and dispersibility, it is preferable to surface-treat a particle surface. Examples of the surface treatment agent include anionic surfactants, cationic surfactants, phosphate ester treatment agents, silane coupling agents, titanate coupling agents, aluminum coupling agents, silicon treatment agents, sodium silicate, and the like, but are not limited thereto. The combination of sodium silicate and cationic surfactant is mentioned as a preferable surface treating agent from a viewpoint of acid resistance improvement. Since the crystal surface of magnesium hydroxide has a positive charge, high acid resistance can be imparted by first surface-treating with sodium silicate and then surface-treating with a cationic surfactant. The total amount of the surface treating 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).

<Composite metal oxide>

The composite metal oxide of this invention is represented by Formula (2) shown below, and the kind of metal, the range of X, the average width of a primary particle, and monodispersity are as follows.

(Mg) _1-X (M ²⁺ ) _X O (2)

(Type of metal)

In the composite metal oxide represented by the formula (2), M ²⁺ is at least one or more divalent metals selected from Cr, Mn, Fe, Co, Ni, Cu, and Zn. M ²⁺ is preferably Ni and / or Zn in view of excellent acid resistance and easy availability.

(Range of X)

In the composite metal oxide represented by the formula (1), the range of X is 0 <X <0.5, the preferred range is 0.005≤X≤0.4, and the more preferable range is 0.01≤X≤0.2.

(Average width of primary particles)

In the composite metal oxide represented by the formula (2), the average width of the primary particles by the (A) 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 width of the primary particles is determined from the arithmetic mean of the measured values of the widths of any 100 crystals in the SEM photograph by the SEM method.

Monodispersity

In the composite metal oxide represented by the formula (2), the monodispersity represented by the following formula (B) is 50% or more, preferably 80% or more. The average width of the secondary particles is measured by the dynamic light scattering method. This is because it is difficult to accurately measure the width of the secondary particles by the SEM method.

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 Formula (2), in order to improve acid resistance and dispersibility, it is preferable to surface-treat the particle surface. Examples of the surface treatment agent include anionic surfactants, cationic surfactants, phosphate ester treatment agents, silane coupling agents, titanate coupling agents, aluminum coupling agents, silicon treatment agents, sodium silicate, and the like, but are not limited thereto. The total amount of the surface treating 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 (2).

<Resin composition>

The resin composition of this invention contains 0.1-250 weight part of composite metal hydroxide of this invention with respect to 100 weight part of resin. The compounding quantity of a composite metal hydroxide becomes like this. Preferably it is 1-200 weight part.

There is no restriction | limiting in particular in the mixing and kneading | mixing method of resin and the composite metal hydroxide of this invention, What is necessary is just a method which can mix both uniformly. For example, they are mixed and kneaded by a single screw or twin screw extruder, a roll, a Banbury mixer, or the like. There is no restriction | limiting in particular also in the shaping | molding method, A well-known shaping | molding means can be employ | adopted arbitrarily according to the kind of resin and rubber, the kind of desired molded article, etc. For example, injection molding, extrusion molding, blow molding, press molding, rotary molding calendar molding, sheet forming molding, transfer molding, lamination molding, vacuum molding and the like.

The resin used in the present invention means resins and / or rubbers, for example, copolymers of polyethylene, ethylene and other α-olefins, copolymers of ethylene and vinyl acetate, copolymers of ethylene and acrylic acid ethers, ethylene and acrylic acid Copolymers of methyl, polypropylene, copolymers of propylene and other α-olefins, polybutene-1, poly 4-methylpentene-1, polystyrene, copolymers of styrene and acrylonitrile, copolymers of ethylene and propylene diene rubber , Copolymers of ethylene and butadiene, polyvinyl acetate, polylactic acid, polyvinyl alcohol, polyacrylates, polymethacrylates, polyurethanes, polyesters, polyethers, polyamides, ABS, polycarbonates, polyphenylene sulfides, etc. Thermoplastic resins may be mentioned. Moreover, thermosetting resins, such as a phenol resin, a melamine resin, an epoxy resin, unsaturated polyester resin, an alkyd resin, are mentioned. In addition, EPDM, SBR, NBR, butyl rubber, chloroprene rubber, isoprene rubber, chlorosulfonated polyethylene rubber, silicone rubber, fluororubber, chlorinated butyl rubber, butyl bromide rubber, epichlorohydrin rubber, chlorinated polyethylene, etc. may be mentioned. .

In addition to the composite metal hydroxide, the resin composition of the present invention may contain other additives such as antioxidants, reinforcing agents such as talc, ultraviolet absorbers, lubricants, gloss removers such as fine silica, pigments such as carbon black, bromine flame retardants and phosphate ester flame retardants Flame retardants, such as these, can be suitably selected and mix | blended. Moreover, fillers, such as a flame retardant adjuvant, such as zinc stannate, an alkali metal stannate salt, and carbon powder, and a calcium carbonate, can be suitably selected and mix | blended. Preferred blending amounts of these additives are 0.01 to 5 parts by weight of antioxidant, 0.1 to 50 parts by weight of reinforcing agent, 0.01 to 5 parts by weight of UV absorber, 0.1 to 5 parts by weight of lubricant, 0.01 to 5 parts by weight of gloss remover, 0.01 to 5 parts by weight of pigment, 0.1 to 50 parts by weight of flame retardant, 0.01 to 10 parts by weight of flame retardant aid, and 1 to 50 parts by weight of filler.

<Method of producing a composite metal hydroxide>

The manufacturing method of the composite metal hydroxide of this invention includes the process of the following (1)-(4).

(1) A raw material adjusting step of mixing a water-soluble aqueous magnesium salt solution with at least one water-soluble metal salt aqueous solution selected from Cr, Mn, Fe, Co, Ni, Cu, and Zn to obtain a water-soluble aqueous composite metal salt solution.

(2) A reaction step of obtaining a slurry containing a product by reacting an aqueous aqueous solution of a composite metal salt obtained in (1) with an aqueous alkali metal hydroxide solution.

(3) A aging step of stirring and maintaining the slurry containing the product obtained in (2) at 0 to 100 ° C for 1 to 24 hours.

(4) A wet grinding step of wet grinding a slurry containing a product after aging obtained in (3).

(Raw material adjustment process)

A water-soluble magnesium salt aqueous solution and at least 1 type or more of water-soluble metal salt aqueous solution chosen from Cr, Mn, Fe, Co, Ni, Cu, Zn are mixed, and aqueous water-soluble composite metal salt aqueous solution is produced. Examples of the water-soluble magnesium salt include magnesium chloride, magnesium nitrate, magnesium acetate, magnesium sulfate, and the like, but are not limited thereto. In order to prevent aggregation of a primary particle, it is preferable to use magnesium chloride, magnesium nitrate, and magnesium acetate. 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 includes, but is not limited to, chloride salts, nitrates, acetates, sulfates, and the like. Hydrochloride, nitrate, and acetate are preferable from the viewpoint of improving acid resistance and preventing aggregation of primary particles. The concentration of the aqueous composite metal salt solution is 0.1 to 5.0 mol / L, preferably 0.4 to 4.0 mol / L, as (Mg + M ²⁺ ). The ratio of Mg and 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.

(Reaction step)

The slurry containing a composite metal hydroxide can be produced by making water-soluble composite metal salt aqueous solution and alkali metal hydroxide aqueous solution react. Examples of the alkali metal hydroxides include sodium hydroxide and potassium hydroxide, but are not limited thereto. As a reaction method, although batch reaction and continuous reaction are mentioned, it is not limited to this, for example. In consideration of productivity and uniformity of the reaction, preferably, a continuous reaction is suitably used. The pH at the time of reaction is adjusted to 9.0-12.0, Preferably it is 9.5-11.5, More preferably, it is 10.0-11.0. When the reaction pH is lower than 9.0, since the primary particles grow at the time of aging of the slurry, it is not preferable. When the reaction pH is higher than 12.0, impurities derived from the raw material tend to precipitate, but it is not preferable for economic reasons. The concentration of the alkali metal hydroxide is 0.1 to 20.0 mol / L, and preferably 0.4 to 15.0 mol / L. The concentration at the time of reaction is 0.1-5.0 mol / L in conversion of a composite metal hydroxide, Preferably it is 0.4-4.0 mol / L. When the concentration at the time of reaction is lower than 0.1 mol / L, productivity is low, and when it is higher than 5.0 mol / L, since primary particle | grains aggregate, it is not preferable. Reaction temperature is 0-100 degreeC, Preferably it is 10-60 degreeC, More preferably, it is 20-40 degreeC. When reaction temperature is higher than 100 degreeC, since primary particle will grow to 200 nm or more, it is unpreferable. If the reaction temperature is lower than 0 ° C, the slurry is frozen, which is not preferable.

(Aging process)

After the reaction, the slurry is stirred and maintained at 0 to 100 ° C. for 1 to 24 hours. By passing through this step, aggregation of strong primary particles can be alleviated immediately after the reaction. If the aging time is less than 1 hour, it is not enough time to alleviate aggregation of the primary particles. Aging longer than 24 hours does not form a meaning because there is no change in the aggregation state. Preferable aging time is 2 to 18 hours, More preferably, it is 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. It is not preferable because the slurry freezes when the aging temperature is lower than 0 ° C. Moreover, preferable aging temperature is 10-60 degreeC, Most preferably, it is 20-40 degreeC. The concentration at the time of aging is 0.1 to 5.0 mol / L in terms of composite metal hydroxide, preferably 0.4 to 4.0 mol / L. When the concentration at the time of aging is lower than 0.1 mol / L, productivity is low, and when it is higher than 5.0 mol / L, since primary particle | grains aggregate, it is not preferable.

(Wet grinding process)

The slurry after the aging treatment is dewatered, washed with 20 times the weight of deionized water relative to the solid content, and then the cake is reemulsified with deionized water. The slurry after reemulsification is wet milled. As wet grinding, a bead mill, a high pressure homogenizer, etc. are used suitably, for example. The temperature at the time of wet grinding is 0-100 degreeC, More preferably, it is 10-60 degreeC, Most preferably, it is 20-40 degreeC. When the temperature at the time of wet grinding is 100 ° C or higher, the primary particles grow to 200 nm or more, which is not preferable. It is not preferable because the slurry freezes when the temperature at the time of wet grinding is less than 0 ° C. The concentration at the time of wet grinding is 0.1-5.0 mol / L in conversion of a composite metal hydroxide, Preferably it is 0.4-4.0 mol / L. If the concentration at the time of wet grinding is lower than 0.1 mol / L, productivity is low, and if it is higher than 5.0 mol / L, it is not preferable because the aggregation of a primary particle cannot be solved. In the case of a bead mill, the preferable beads diameter is 0.001 mm-0.1 mm, More preferably, it is 0.01 mm-0.05 mm. In the case of a high pressure homogenizer, the preferred pressure is 100 bar to 1000 bar, more preferably 400 bar to 700 bar.

(Surface Treatment Process)

After wet grinding, the surface treatment of the composite metal hydroxide can improve the dispersibility in the resin when added, kneaded, or dispersed in the resin. Surface treatment can use a wet method or a dry method. In consideration of the uniformity of the treatment, the wet method is suitably used. The slurry after wet grinding is dewatered, washed with 20 times the weight of deionized water relative to the solid content, and then suspended in deionized water. The slurry after suspension is temperature-controlled, and the surface treating agent melt | dissolved under stirring is added. The temperature at the time of surface treatment is suitably adjusted to the temperature at which a surface treating agent melt | dissolves.

As the surface treatment agent, for example, at least one selected from anionic surfactants, cationic surfactants, phosphate ester treatment agents, silane coupling agents, titanate coupling agents, aluminum coupling agents, silicone treatment agents, sodium silicate and the like can be used. have. 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 treating 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.

(Drying process)

The slurry after the surface treatment is dewatered, washed with 20 times the weight of deionized water with respect to the solid content, and then dried to obtain the composite metal hydroxide of the present invention. The drying method may be hot air drying, vacuum drying, or the like, but is not particularly limited.

<Method of producing a composite metal oxide>

The composite metal oxide of the present invention is obtained by firing the composite metal hydroxide of the present invention. After firing, surface treatment may be performed by a dry or wet method to prevent aggregation of primary particles, thereby obtaining a composite metal oxide having a high monodispersity.

(Firing process)

The composite metal oxide of this invention can be obtained by baking the composite metal hydroxide of this invention for 400 to 1000 degreeC for 1 to 10 hours. More preferable baking temperature is 450-900 degreeC, More preferably, it is 500-800 degreeC. Magnesium oxide is not produced at a calcination temperature of 400 ° C. or lower, and is preferable because primary particles are coarsened by sintering at 1000 ° C. or higher. More preferable baking time is 1-8 hours, More preferably, it is 1-6 hours. If the firing time is less than 1 hour, magnesium oxide is not enough to be produced. If the firing time is 10 hours or more, the primary particles are coarsened by sintering, which is not preferable.

(Surface Treatment Process)

After firing, the surface treatment of the composite metal oxide can improve the dispersibility in the resin when added, kneaded, or dispersed in the resin. Surface treatment can use a wet method or a dry method. In consideration of the uniformity of the treatment, the wet method is suitably used. The powder after baking is disperse | distributed to alcohol solvent, and the surface treating agent melt | dissolved under stirring is added. The temperature at the time of surface treatment is suitably adjusted to the temperature at which a surface treating agent melt | dissolves.

As the surface treatment agent, for example, at least one selected from anionic surfactants, cationic surfactants, phosphate ester treatment agents, silane coupling agents, titanate coupling agents, aluminum coupling agents, silicon treatment agents, sodium silicate, and the like can be used. . The addition amount of the surface treating 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.

EXAMPLES Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited to these examples. In the Example, each physical property was measured by the following method.

(a) Average width of primary particles

After the sample was added to ethanol and sonicated for 5 minutes, the width of the primary particles of any 100 crystals was measured using a scanning electron microscope (SEM) (manufactured by JEOL Ltd., JSM-7600F). The arithmetic mean was taken as the average width of the primary particles. In addition, the width | variety of the primary particle measures the diameter of the particle | grains when the primary particle is set as a hexagonal plate shape like the arrow shown in FIG.

(b) average width of secondary particles

After the sample was added to ethanol and sonicated for 5 minutes, the particle size distribution was measured using a dynamic scattering particle size analyzer (ELSZ-2000S, manufactured by Otsuka Electronics Co., Ltd.), and the number average diameter was 2 It was set as the average width of a tea particle. That is, the diameter of the sphere when the secondary particle was enclosed by the sphere was measured as the width of a secondary particle, and the number average was made into the average width of a secondary particle.

(c) monodispersity

It calculated from the values of (a) and (b) based on the following formula | equation. Monodispersity (%) = (average width of primary particles / average width of secondary particles) x 100

(d) Quantification of chemical composition

After the sample was heated and dissolved in nitric acid, Mg, Mn, Ni, and Zn were quantified by chelate titration.

(e) Quantification of Surface Throughput

(Silicic acid) and then the sample was heated and dissolved using sulfuric acid and nitric acid, and calculating the covering amount of silica (as SiO ₂₎ relative to the weight of the sample by a gravimetric method.

(Stearic acid) The coating amount of stearic acid with respect to the weight of a sample was computed by the ether extraction method.

(Cation-Based Surfactant) After extracting the nitrogen content of the sample by the Kjeldahl method, the nitrogen content was measured from the absorbance using a spectrophotometer. From the nitrogen content in the sample, the coating amount of the cationic surfactant to the weight of the sample was calculated. .

(f) Acid resistance test method of powder

2 mL of ethanol at 32 ° C and a rotor are placed in a beaker kept at 32 ° C, and the beaker is immersed in a thermostat (32 ° C) to start stirring. After 1 minute, 0.1 g of sample is added. After 1 minute from the sample addition, 40 mL of water at 32 ° C. is added and the pH meter electrode and the set of burettes are soaked in the beaker. After 1 minute from adding water, 0.1 N hydrochloric acid is added to the test slurry so that the pH of the test slurry is always 4.0 and the temperature is 32 ° C. using an automatic titrator (manufactured by DKK-TOA Corporation). The titration is terminated when 5.15 mL of 0.1 N hydrochloric acid is added. Acid resistance was evaluated by the time from the start of stock price to 5.15 mL of 0.1 N hydrochloric acid. The longer the time, the better acid resistance.

(g) Flame Retardancy Test Method of Resin Composition (UL 94 Vertical Test (1/8 inch))

110 weight part of each sample was added with respect to 100 weight part of polyethylene, and the resin composition was created. The test piece was created by melt-kneading polyethylene and each sample at 150 degreeC using the platomil (made by BRABENDER), and press-molding the obtained resin composition (made by Shinto Metal Industries Corportation, the Shindo type SF hydraulic press). The flame retardancy of the resin composition was measured according to the UL 94 vertical test method (1/8 inch). In order of high flame retardancy, the specifications of V-0, V-1, and V-2 are given. Failure to meet the flame retardant specification is out of specification.

(h) Acid resistance test method (carbonic acid gas blowing test) of resin composition

The test piece prepared in (g) was impregnated with 500 mL of deionized water, the temperature was maintained at 20 ° C., and the carbon dioxide gas was blown at a rate of 500 mL / min and maintained for 24 hours. Acid resistance was evaluated by the Mg concentration in the solution after fat and oil. The lower the Mg concentration in the solution, the better the acid resistance.

Example 1

(Raw material adjustment process)

Reagent primary magnesium chloride and reagent primary nickel chloride were dissolved in deionized water to prepare an aqueous solution of a composite metal salt of Mg = 0.9 mol / L and Ni = 0.1 mol / L. On the other hand, sodium hydroxide of reagent 1 was dissolved in deionized water to prepare an aqueous solution of an alkali metal hydroxide of Na = 2 mol / L.

(Reaction step)

Each solution was continuously supplied to the reactor at 20 mL / min using a metering pump, and coprecipitation reaction was carried out. The reactor is made of stainless steel and has a capacity of 500 mL and overflows. 300 mL of deionized water is added to the reactor in advance, and the temperature is adjusted to 30 ° C., followed by stirring at 500 rpm using a stirrer. Similarly, the raw material adjusted to 30 degreeC was supplied to the reaction tank, and the flow volume was adjusted so that reaction pH might be 10.3.

(Aging process)

The obtained slurry was temperature-controlled at 30 degreeC, and it aged for 10 hours, stirring at 300 rpm. After the reaction product was filtered and washed with deionized water, the cake was dispersed in deionized water to obtain a slurry.

(Wet grinding process)

The slurry was wet milled using a bead mill (Ultra Apex Mill, manufactured by Hiroshima Metal & Machinery Co., Ltd.). 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 slurry after grinding | pulverization was suction filtered and deionized water wash | cleaned. The cake was placed in a hot air dryer, dried at 110 ° C. for 12 hours, and then ground to obtain a composite metal hydroxide sample 1 of the present invention. Table 1 shows the chemical composition, the average width of the primary particles, the average width of the secondary particles, the monodispersity, and the acid resistance test results in Table 1. In FIG. 3, the SEM photograph of 100,000 times of the sample 1 is shown.

Example 2

In the raw material adjustment process of Example 1, the sample was produced similarly except having used the reagent primary zinc chloride instead of the reagent primary nickel chloride, and the composite metal hydroxide sample 2 of this invention was obtained.

Example 3

In the raw material adjustment process of Example 1, the sample was produced similarly except having used the reagent primary manganese chloride instead of the reagent primary nickel chloride, and the composite metal hydroxide sample 3 of this invention was obtained.

Example 4

In the raw material adjustment process of Example 1, the sample was produced similarly except having made the concentration of the composite metal salt aqueous solution into Mg = 0.7mol / L, Ni = 0.3mol / L, and obtained the composite metal hydroxide sample 4 of this invention. .

Example 5

In the reaction process of Example 1, the sample was produced similarly except having made the pH at the time of reaction into 9.3, and obtained the composite metal hydroxide sample 5 of this invention.

Example 6

In the reaction process of Example 1, the sample was produced similarly except having made the pH at the time of reaction into 11.6, and obtained the composite metal hydroxide sample 6 of this invention.

Example 7

In the aging step of Example 1, a sample was produced in the same manner as in the aging temperature except that the aging temperature was 60 ° C., thereby obtaining the composite metal hydroxide sample 7 of the present invention.

Example 8

In the aging step of Example 1, a sample was produced in the same manner except that the aging temperature was 10 ° C., thereby obtaining the composite metal hydroxide sample 8 of the present invention.

Example 9

In the aging step of Example 1, except that the aging time was 3 hours, a sample was produced in the same manner to obtain a composite metal hydroxide sample 9 of the present invention.

Example 10

In the aging step of Example 1, except that the aging time was 20 hours, a sample was produced in the same manner to obtain a composite metal hydroxide sample 10 of the present invention.

Example 11

In Example 1, the sample was produced similarly except having carried out wet grinding using the high pressure homogenizer (made by SMT Corporation, LAB1000) instead of the bead mill, and obtained the composite metal hydroxide sample 11 of this invention. 400 mL of a slurry having a concentration of 0.5 mol / L was circulated at 200 mL / min, and wet grinding was performed at 500 bar for 20 minutes.

Example 12

(Surface Treatment Process)

Sodium silicate was used with 4% by weight of reagent No. 3 sodium silicate solution based on the composite metal hydroxide, and the volume thereof was made up to 50 mL with deionized water, i. It was set as the treatment liquid. Using 1% by weight of reagent-grade dioleyldimethylammonium chloride solution relative to the composite metal hydroxide, the volume was made up to 50 mL with deionized water to obtain a dioleyldimethylammonium chloride treatment solution.

In Example 1, the sodium silicate containing process liquid heated up at 80 degreeC was added to the slurry after wet grinding, and it stirred and maintained at 80 degreeC for 20 minutes. Then, the dioleyl dimethylammonium chloride treatment liquid heated up at 80 degreeC was added, and it stirred and maintained at 80 degreeC for 20 minutes. After cooling the slurry after surface treatment to 30 degreeC, suction filtration and deionized water washing | cleaning were performed. Thereafter, the cake was placed in a hot air dryer, dried at 110 ° C. for 12 hours, and then ground to obtain a composite metal hydroxide sample 12 of the present invention.

Example 13

In the surface treatment process of Example 12, the sample was produced likewise except having used No. 3 sodium silicate independently, and the composite metal hydroxide sample 13 of this invention was obtained.

Example 14

In the surface treatment process of Example 12, the sample was produced similarly except having used dioleyl dimethylammonium chloride independently, and the composite metal hydroxide sample 14 of this invention was obtained.

Example 15

In the surface treatment process of Example 12, the sample was produced similarly except having used 1 weight% of sodium stearate with respect to the composite metal hydroxide instead of sodium silicate, and obtained the composite metal hydroxide sample 15 of this invention.

Example 16

In the surface treatment process of Example 12, the sample was produced likewise except having used 1 weight% of sodium stearate alone with respect to the composite metal hydroxide, and the composite metal hydroxide sample 16 of this invention was obtained.

(Comparative Example 1)

In the raw material adjustment process of Example 1, the sample was produced similarly except having used reagent grade magnesium chloride independently, and the sample 17 was obtained.

(Comparative Example 2)

In the reaction process of Example 1, the sample was produced similarly except having set the pH at the time of reaction to 8.5, and sample 18 was obtained.

(Comparative Example 3)

In the aging step of Example 1, a sample was produced in the same manner except that the aging time was 30 minutes, to obtain sample 19.

(Comparative Example 4)

In the aging step of Example 1, a sample was produced in the same manner except that the aging temperature was 120 ° C., and sample 20 was obtained.

(Comparative Example 5)

In Example 1, the sample was produced similarly except having omitted the aging process, and the sample 21 was obtained.

(Comparative Example 6)

In Example 1, the sample was produced similarly except except the wet grinding process, and the sample 22 was obtained.

Table 1-1

TABLE 1-2

Table 1-3

TABLE 2-1

Table 2-2

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TABLE 2-3

Table 1 and Table 2 show that the composite metal hydroxide of the present application has an average width of the primary particles of 200 nm or less and a monodispersity of 50% or more. Compared to the magnesium hydroxide of Comparative Example 1, the composite metal hydroxide of Example 1 has significantly improved powder acid resistance while maintaining high monodispersity. The samples of Examples 12 to 16 subjected to the surface treatment showed higher monodispersity and powder acid resistance than the samples without the surface treatment. In particular, Example 12 using sodium silicate and dioleyldimethylammonium showed significant monodispersity and improved acid resistance.

Example 17

110 parts by weight of powder sample 1 prepared in Example 1 was added to 100 parts by weight of polyethylene to prepare a resin composition. Polyethylene (manufactured by Japan Polyethylene Corporation, Novatec LL UF-240) and powder samples were melt kneaded at 150 ° C using a platomill (manufactured by BRABENDER), and the resulting resin composition was press-molded (manufactured by Shinto Metal Industries Corporation, Shindo-type SF). Type hydraulic press) to create a test piece. The flame retardancy test results and the acid resistance test results are shown in Table 3.

Example 18

The test piece was created by the method similar to Example 17 using the powder sample 2 produced in Example 2.

Example 19

The test piece was created by the method similar to Example 17 using the powder sample 3 produced in Example 3.

Example 20

The test piece was created by the method similar to Example 17 using the powder sample 4 produced in Example 4.

Example 21

The test piece was created by the method similar to Example 17 using the powder sample 5 produced in Example 5.

Example 22

The test piece was created by the method similar to Example 17 using the powder sample 6 produced in Example 6.

Example 23

The test piece was created by the method similar to Example 17 using the powder sample 7 produced in Example 7.

Example 24

The test piece was created by the method similar to Example 17 using the powder sample 8 produced in Example 8.

Example 25

The test piece was created by the method similar to Example 17 using the powder sample 9 produced in Example 9.

Example 26

The test piece was created by the method similar to Example 17 using the powder sample 10 produced in Example 10.

Example 27

The test piece was created by the method similar to Example 17 using the powder sample 11 produced in Example 11.

Example 28

The test piece was created by the method similar to Example 17 using the powder sample 12 produced in Example 12.

Example 29

The test piece was created by the method similar to Example 17 using the powder sample 13 produced in Example 13.

Example 30

The test piece was created by the method similar to Example 17 using the powder sample 14 produced in Example 14.

Example 31

The test piece was created by the method similar to Example 17 using the powder sample 15 produced in Example 15.

Example 32

The test piece was created by the method similar to Example 17 using the powder sample 16 produced in Example 16.

(Comparative Example 7)

The test piece was created by the method similar to Example 17 using the powder sample 17 produced by the comparative example 1.

(Comparative Example 8)

The test piece was created by the method similar to Example 17 using the powder sample 18 produced by the comparative example 2.

(Comparative Example 9)

The test piece was created by the method similar to Example 17 using the powder sample 19 produced by the comparative example 3.

(Comparative Example 10)

The test piece was created by the method similar to Example 17 using the powder sample 20 produced by the comparative example 4.

(Comparative Example 11)

The test piece was created by the method similar to Example 17 using the powder sample 21 produced by the comparative example 5.

(Comparative Example 12)

The test piece was created by the method similar to Example 17 using the powder sample 22 produced in the comparative example 6.

Table 3-1

Table 3-2

Table 3-3

From Table 3, the resin composition incorporating the composite metal hydroxide of the present invention satisfies the V-0 or V-1 standard in the UL 94 vertical test (1/8 inch), and the elution of Mg in the carbon dioxide blowing test is You can see little.

Example 33

(Firing process)

The powder sample 1 produced in Example 1 was calcined at 500 ° C. for 1 hour in an atmosphere of silicon in an electric furnace. After cooling, the mortar was ground to obtain a composite metal oxide sample 23 of the present invention. The experimental conditions of the sample 23 are shown in Table 4, and the chemical composition, average width of primary particles, average width of secondary particles, monodispersity, and acid resistance test results are shown in Table 5. In FIG. 4, the SEM photograph of 100,000 times of the sample 23 is shown.

Example 34

In Example 33, the composite metal oxide sample 24 of the present invention was obtained in the same manner except that the firing temperature was 800 ° C.

Example 35

In Example 33, the composite metal oxide sample 25 of the present invention was obtained in a similar manner except that the firing time was 8 hours.

Example 36

(Surface Treatment Process)

It was made to dissolve in 50 mL of ethanol using 1 weight% of reagent primary stearic acid with respect to a composite metal oxide, and it was set as the stearic acid containing process liquid.

In Example 33, the composite metal oxide after calcining was dispersed in an ethanol solvent under stirring, and the temperature was adjusted to 60 ° C. Similarly, the stearic acid containing process liquid heated up at 60 degreeC was added, and it stirred and maintained at 60 degreeC for 20 minutes. After cooling the slurry after surface treatment to 30 degreeC, suction filtration was performed. The cake was naturally dried and then ground to obtain a composite metal oxide sample 26 of the present invention.

(Comparative Example 13)

In Example 33, the sample 27 was obtained similarly except having set baking temperature to 1200 degreeC.

(Comparative Example 14)

In Example 33, the sample 28 was obtained similarly except having set baking time to 12 hours.

(Comparative Example 15)

In Example 33, Sample 29 was obtained in the same manner as in Example 1 except that Sample 17 produced in Comparative Example 1 was calcined at 500 ° C in an air atmosphere for 1 hour in place of Powder Sample 1 prepared in Example 1.

TABLE 4

TABLE 5

delete

It can be seen from Table 4 and Table 5 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. In particular, sample 26 (Example 36) surface-treated with stearic acid showed high acid resistance. It can be seen that in Sample 27 (Comparative Example 13) and Sample 28 (Comparative Example 14), primary particles were greatly grown by sintering, and Sample 29 (Comparative Example 15) had poor acid resistance of the powder.

(Industrial availability)

The composite metal hydroxide of the present invention can be blended with a separator of a lithium ion battery to suppress the reaction with hydrogen fluoride while suppressing the film thickness of the separator, thereby improving safety of the battery. The composite metal hydroxide of the present invention can also be suitably used as a flame retardant. The amount of the fine particles dispersed in the resin can be reduced, and the acid resistance of the resin can be improved.

The composite metal hydroxide of this invention can be used suitably also for various uses, such as an antibacterial agent, an oral fungicide, a heat conductive filler, a fine ceramic raw material, and an adsorbent. Further, by firing the composite metal hydroxide of the present invention, it is possible to produce a composite metal oxide having fine particles and high dispersion and high acid resistance. The oxides are fine particles, highly dispersed, such as medicinal gastrointestinal, acid acceptor of synthetic rubber or adhesive, thickener for manufacturing FRP, additive for manufacturing steel sheet, heat conducting filler, magnesia whetstone material, fine ceramic raw material, brake material, adsorbent, etc. It can be used suitably for various uses.

Claims (13)

The composite metal hydroxide represented by following formula (1) which satisfy | fills the following (A) and (B).
(Mg) _1-X (M ²⁺ ) _X (OH) ₂ (1)
( ^Wherein M ²⁺ is at least one or more divalent metals selected from Cr, Mn, Fe, Co, Ni, Cu, Zn, and the range of X is 0 <X <0.5)
(A) The average width of the primary particles by the SEM method is 10 nm or more and less than 100 nm;
(B) 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 delete The method of claim 1,
(A) Composite metal hydroxide whose average width of a primary particle by SEM method is 10 nm or more and less than 50 nm. The method of claim 1,
(B) A composite metal hydroxide having a monodispersity of 80% or more. The method of claim 1,
The composite metal hydroxide whose range of X of Formula (1) is 0.005 <= X <0.4. The method of claim 1,
The composite metal hydroxide whose range of X of Formula (1) is 0.01 <= <= 0.2. The method of claim 1,
A composite metal hydroxide wherein M ²⁺ in formula (1) is Ni and / or Zn. The method of claim 1,
A composite metal hydroxide surface-treated with at least one selected from the group consisting of anionic surfactants, cationic surfactants, phosphate ester treatment agents, silane coupling agents, titanate coupling agents, aluminum coupling agents, silicon treatment agents and silicic acids. The method of claim 1,
Composite metal hydroxides surface-treated with silicic acid and cationic surfactants. The composite metal oxide represented by following formula (2) which satisfy | fills the following (A) and (B).
(Mg) _1-X (M ²⁺ ) _X O (2)
( ^Wherein M ²⁺ is at least one or more divalent metals selected from Cr, Mn, Fe, Co, Ni, Cu, Zn, and the range of X is 0 <X <0.5)
(A) the average width of the primary particles by the SEM method is 10 nm or more and less than 200 nm;
(B) 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 resin composition containing 0.1-250 weight part of composite metal hydroxides of Claim 1 with respect to 100 weight part of resin. As a manufacturing method of the composite metal hydroxide of Claim 1,
The manufacturing method of the composite metal hydroxide containing the following process.
(1) a raw material adjusting step of mixing a water-soluble aqueous magnesium salt solution with at least one water-soluble metal salt aqueous solution selected from Cr, Mn, Fe, Co, Ni, Cu, and Zn to obtain an aqueous water-soluble composite metal salt solution;
(2) A reaction step of obtaining a slurry containing a product by reacting the aqueous aqueous solution of the aqueous composite metal salt obtained in (1) with an alkali metal hydroxide aqueous solution adjusted to a range of pH 9.0 to 12.0,
(3) a aging step of stirring and maintaining the slurry containing the product obtained in (2) at 0 to 100 ° C. for 1 to 24 hours,
(4) Wet grinding step of wet grinding the slurry containing the product after aging obtained in (3). As a manufacturing method of the composite metal oxide of Claim 10,
The manufacturing method of the composite metal oxide containing the following process.
(1) a raw material adjusting step of mixing a water-soluble aqueous magnesium salt solution with at least one water-soluble metal salt aqueous solution selected from Cr, Mn, Fe, Co, Ni, Cu, and Zn to obtain an aqueous water-soluble composite metal salt solution;
(2) A reaction step of obtaining a slurry containing a product by reacting the aqueous aqueous solution of the aqueous composite metal salt obtained in (1) with an alkali metal hydroxide aqueous solution adjusted to a range of pH 9.0 to 12.0,
(3) a aging step of stirring and maintaining the slurry containing the product obtained in (2) at 0 to 100 ° C. for 1 to 24 hours,
(4) a wet grinding step of wet grinding a slurry containing a product after aging obtained in (3),
(5) a drying step of dehydrating the slurry after wet grinding obtained in (4) and drying the cake obtained to obtain a composite metal hydroxide;
(6) A firing step of firing the composite metal hydroxide obtained in (5) at 400 to 1000 ° C for 1 to 10 hours.

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