Highly oriented metal complex salt

Abstract

[Problem] The purpose of the present invention is to develop a low-cost and higher aspect ratio material that is available as a substitute for conventional high aspect ratio magnesium hydroxide which requires a large amount of a monocarboxylic acid. [Solution] The present invention relates to a highly oriented metal complex salt which is represented by formula (1): (Mg1-x(M2+)x(OH)2-nyAy [wherein: M2+ represents one or more divalent metals other than Mg; A represents one or more organic ligands; x and y are each in the following range, 0≤x<0.2, preferably 0≤x<0.1, and particularly preferably 0.01≤x<0.06, and 0<y<0.05, preferably 0.0001<y<0.02, and particularly preferably 0.001<y<0.015; and n is an integer in the range of 1 to 4, preferably 1 or zero], which has an X-ray diffraction intensity ratio (orientation H) of the (101) plane to the (001) plane of 60% or less, and which has a hexagonal Cd(OH)2-type crystal structure.

Description

Highly oriented metal composite salt

[0001] The present invention relates to a novel highly oriented metal composite salt containing Mg as a main component. More specifically, the present invention relates to a novel highly oriented metal composite salt containing Mg(OH) ２ The present invention relates to a novel highly oriented metal composite salt in which some of the OH groups are substituted with organic ligands, and the primary particles have a large width and an extremely thin thickness, and are easily oriented in the width direction.

[0002] Magnesium hydroxide is a hexagonal Cd(OH) ２ It belongs to the α-type structure, and because crystal growth in the c-axis direction (thickness) is poorer than in the a-axis direction (width), it often exhibits a plate-like crystal shape. Its characteristics include a low specific gravity of 2.37, non-toxicity, and basicity. It has a long history of use as a gastric acid neutralizer and laxative, but its industrial uses are limited other than flue gas desulfurization, and demand has been low.

[0003] However, the present inventors developed a magnesium hydroxide (product name: Kisuma 5) that is close to monodisperse, with primary particles (single crystals) having a width of approximately 0.8 to 1 μm and a thickness of approximately 0.2 μm, with almost no secondary aggregation (primary particle size = secondary particle size) (Patent Document 1), which opened up a large market as a halogen-free flame retardant for resins.Previous magnesium hydroxides had primary particles with a width of approximately 0.2 μm or less, and were highly aggregated, with secondary particles (particles formed by aggregation of primary particles, measured by particle size distribution) being large, at 5 μm or more.

[0004] In order to further expand the applications of magnesium hydroxide-based compounds, the present inventors have developed a magnesium hydroxide-based compound represented by the following formula (2): １－ｘ M ２＋ ｘ (OH) ２ (2) (wherein, M ２＋ is Mn ２＋ , Fe ２＋ , Co ２＋ , Ni ２＋ , Cu ２＋ and Zn ２＋We have developed a hexagonal plate-shaped magnesium hydroxide solid solution with a high aspect ratio of 10 or more, represented by the formula (2): (x represents at least one divalent metal selected from the group consisting of 1 and 2, where x is in the range of 0.01≦x<0.5), an average width of 1 to 10 μm, a thickness of 0.01 to 0.5 μm, and an average aspect ratio of 10 or more. This solid solution is produced by calcining a hydroxide represented by formula (2) and hydrating the resulting oxide in an aqueous medium in the presence of a monocarboxylic acid and / or an oxymonocarboxylic acid. The high aspect ratio has opened up new applications, such as a reinforcing agent for resins (Patent Document 2).

[0005] As a result of further research into high aspect ratio magnesium hydroxide, the present inventors have developed a high aspect ratio magnesium hydroxide having a width of 0.5 μm or more and a thickness of 0.2 μm or less, and an aspect ratio of 10 or more, by (A) adding an alkali to a mixed aqueous solution of a water-soluble magnesium salt and an alkali metal salt and / or ammonium salt of a monovalent organic acid to cause coprecipitation, or (B) adding an alkali to an aqueous solution of a water-soluble magnesium salt to cause coprecipitate, and then adding an alkali metal salt and / or ammonium salt of a monovalent organic acid, and (C) hydrothermally treating the resulting coprecipitate slurry at 100° C. or more (Patent Document 3).

[0006] Furthermore, the present inventors have developed a method for producing a magnesium hydroxide-based solid solution having a high aspect ratio represented by formula (2) at reduced cost. The method comprises the steps of: (A) a water-soluble Mg salt; and (B) a water-soluble divalent metal salt (M ２＋ (C) A mixed aqueous solution of (C) a monocarboxylic acid ion or a metal complex thereof and (D) an aqueous alkali solution such as sodium hydroxide are subjected to a coprecipitation reaction in the presence or absence of a monocarboxylic acid ion, and then the mixture is heated and aged at 60 to 300°C in the presence of (D) and (E) one or more chlorides selected from sodium chloride, potassium chloride, ammonium chloride, magnesium chloride, and calcium chloride (Patent Document 4).

[0007] On the other hand, for the purpose of developing fine particle magnesium hydroxide, a part of the hydroxyl group OH was substituted with a monovalent organic acid, and the following formula (3): Mg(OH) ２－ｘA magnesium hydroxide-based solid solution has been developed, having an average secondary particle size of 300 nm or less, represented by Rx (3) (wherein R represents a monovalent organic acid and x represents a range of 0 < x < 1). This solid solution of fine particles can be produced by (A) adding an alkali in an amount roughly equivalent to Mg to an aqueous mixture of a water-soluble magnesium salt and a monovalent organic acid or a salt thereof to cause coprecipitation, followed by hydrothermal treatment, or (B) adding an aqueous alkali solution to an aqueous solution of a water-soluble magnesium salt to cause coprecipitation, adding a monovalent organic acid or a salt thereof to the resulting magnesium hydroxide, followed by hydrothermal treatment (Patent Document 5).

[0008] JP 52-11579 A JP 8-259235 A International Publication No. 2012 / 050222 JP 2020-152626 A International Publication No. 2016 / 031803

[0009] The higher the aspect ratio, the greater the reinforcing effect on resins and the wider the range of applications, but the maximum aspect ratio of conventional magnesium hydroxide compounds is 50 or less. Therefore, the first object of the present invention is to provide a magnesium hydroxide compound with a high aspect ratio, that is, an aspect ratio of more than 50.

[0010] In conventional methods for producing magnesium hydroxide with a high aspect ratio, the more monovalent organic acid or its salt is used relative to Mg, the higher the aspect ratio tends to be, so it is necessary to use a large amount of the monovalent organic acid, 1 to 1.5 moles per mole of Mg. Conventional production methods require a large amount of monovalent organic acid, which is more expensive than the Mg raw material, and this, coupled with the difficulty of separating the monovalent organic acid from water, results in high raw material costs. At the same time, because the wastewater contains a large amount of monovalent organic acid, expensive wastewater treatment equipment is required, and the running costs are also required, resulting in high production costs. Therefore, a second object of the present invention is to provide an inexpensive production method.

[0011] As a result of intensive research to solve the above problems, the present inventors have found that a compound represented by the following formula (1): (Mg) １－ｘ (M ２＋ ) ｘ (OH) ２－ｎｙ A ｙ　 (1) (wherein, M ２＋represents at least one divalent metal other than Mg; A represents at least one organic ligand; x and y are within the following ranges: 0≦x<0.2, preferably 0≦x<0.1, particularly preferably 0.01≦x<0.06, and 0<y<0.05, preferably 0.0001<y<0.02, particularly preferably 0.001<y<0.015; n represents an integer ranging from 1 to 4, preferably 1 or zero); and the X-ray diffraction intensity ratio (orientation H) of the (101) plane to the (001) plane is 60% or less, and the Cd(OH) ２ The present inventors have succeeded in developing a highly oriented metal complex salt having a crystalline structure of the present invention. The X-ray diffraction intensity ratio (orientation H) is, for example, 60% or less, preferably 30% or less, more preferably 3% or less, and particularly preferably 1% or less.

[0012] In one embodiment, n represents an integer ranging from 1 to 4, and the X-ray diffraction intensity ratio (orientation H) is 60% or less, preferably 30% or less, more preferably 3% or less, and particularly preferably 1% or less.

[0013] In one embodiment, n represents zero.

[0014] Furthermore, the present inventors have succeeded in developing a method for producing the above-mentioned highly oriented metal composite salt, which is characterized by adding (B) an organic ligand to an aqueous solution of (A) a water-soluble salt of a divalent metal containing at least Mg in an amount of less than 10 mol %, preferably 5% or less, relative to the total number of moles of the divalent metal containing at least Mg, and (C) causing a coprecipitation reaction with an alkali in an amount of at least 0.95 equivalents relative to the total equivalents of the divalent metal containing at least Mg, followed by hydrothermal treatment at 100°C or higher.

[0015] Highly oriented metal composite salts are produced by (A) adding approximately 0.01 moles of an organic ligand capable of forming a metal complex relative to the Mg to an aqueous magnesium salt solution, and (C) supplying at least 0.95 equivalents, preferably 0.9 equivalents, relative to the Mg, of alkali to cause a coprecipitation reaction, followed by (D) hydrothermal treatment at 100°C or higher. This allows for the production of highly oriented (high aspect ratio) magnesium hydroxide at reduced production costs. The required amount of organic ligand is an extremely small amount, approximately 1 / 100 of the amount of monovalent organic acid or its salt required in conventional technology. Adding more or less than this amount results in a rapid decrease in the orientation (aspect ratio). This is a new discovery that could not have been predicted based on the conventional thinking that increasing the amount of monovalent organic acid results in a higher aspect ratio.

[0016] The second important production condition in the present invention is the alkali equivalent relative to Mg, which should be at least 0.95 equivalents or less, preferably 0.9 equivalents or less, and particularly preferably 0.85 to 0.6 equivalents or more. By controlling the alkali addition amount to less than the equivalent, the function of the organic ligand can be fully exerted.

[0017] The highly oriented composite metal salt according to the present invention has primary particles (crystallites) that are thinner (minimum about 5 nm) and conversely significantly wider (maximum about 40 μm) with less aggregation than conventional techniques that use monovalent organic acids or salts thereof, resulting in extremely high orientation and therefore a higher aspect ratio (maximum about 200 in the present invention compared to a maximum of about 40 in the conventional technique). Therefore, the reinforcing effect on resins is higher than in conventional products, and reinforcement can be achieved with a smaller amount, further contributing to weight reduction in automobiles and expanding the range of applications for other automobile parts such as door trims, bumpers, and instrument panels.

[0018] In addition to automobiles, it can be used in resins as a flame retardant, smoke suppressant, thermal conductive agent, gas barrier material, oxygen absorber, biodegradation accelerator, etc. It can also be used as a rust inhibitor in paints, a dyeing agent for textiles, and a flame retardant for paper. Taking advantage of its excellent lubricity and pearlescent luster, it can also be used as a lubricating powder in cosmetics to replace mica or talc.

[0019] The amount of organic ligand required for the production of the highly oriented metal composite salt according to the present invention is extremely small, about 0.01 mole per mole of Mg, so raw material costs can be significantly reduced compared to conventional techniques. Furthermore, the equipment and process for recovering organic substances can be omitted, resulting in further cost reductions.

[0020] XRD patterns of the products of Examples 1, 4, and Comparative Example 5. SEM photographs of Examples 1 and 4.

[0021] The present invention has discovered a novel synthesis method in which an organic ligand capable of forming a metal complex is used instead of the monocarboxylic acid used in conventional techniques, and an alkali is co-precipitated in an amount of 0.95 equivalents or less, preferably 0.9 equivalents or less, and particularly preferably 0.85 equivalents or less to 0.6 equivalents or more relative to Mg, followed by hydrothermal treatment at 100°C or higher, preferably 120°C or higher, and particularly preferably 180°C or higher.

[0022] The present invention was achieved through extensive research based on the following concept. By creating conditions that facilitate the formation of complexes between Mg ions and organic ligands, two new functions not found in conventional technology can be added. First, because the organic ligands bond with Mg ions at two or more sites, it should be possible to effectively suppress the growth of primary particles in the thickness direction with a small amount, compared to conventional technology that uses monovalent organic acids that can only bond at one site. Second, because the complex with Mg has a certain degree of water solubility, which is a characteristic of metal complexes, improved solubility can be expected, which in turn promotes the growth of primary particles and reduces aggregation, improving dispersibility.

[0023] The highly oriented metal composite salt represented by formula (1) of the present invention has the following characteristics: (1) The powder X-ray diffraction pattern shows that the salt has the same hexagonal crystal structure as magnesium hydroxide, Cd(OH) ２ It has a Mg(OH) type crystal structure. ２ Some of the OH groups are replaced with organic ligands, but the crystal structure is Mg(OH) ２(2) The X-ray diffraction intensity ratio H (orientation) of the (101) plane to the (001) plane is at least 60% or less, preferably 30% or less, and particularly preferably 3% or less. A higher orientation H means a higher aspect ratio of the primary particles and less aggregation. Re-examination of the examples of Patent Document 5, which uses the same solid solution as the present invention, revealed that the H values ​​of the glycolic acid solid solution (Example 2) and the lactic acid solid solution (Example 3) were 143% and 147%, respectively, clearly demonstrating the difference from the highly oriented metal composite salt according to the present invention. (3) The average width of the primary particles is 0.21 μm or more, more preferably 2 μm or more, more preferably 3 μm to 50 μm, even more preferably 3 μm to 20 μm, or more preferably 4 μm to 50 μm, even more preferably 4 μm to 20 μm, and particularly preferably 4 μm to 10 μm. (4) The average thickness of the primary particles is in the range of 1 nm to 100 nm, preferably 5 nm to 100 nm, more preferably 5 nm to 70 nm, even more preferably 5 nm to 60 nm, and particularly preferably 5 nm to 50 nm, or preferably 10 nm to 100 nm, more preferably 10 nm to 70 nm, even more preferably 10 nm to 60 nm, and particularly preferably 10 nm to 50 nm. (5) The aspect ratio, which is the ratio of the width to the thickness of the primary particles, is 20 or more, preferably 50 or more, and particularly preferably 100 or more. (6) The average secondary particle size is approximately the same as or slightly larger than the primary particle size, thereby reducing secondary aggregation. (7) Primary particles of 2 μm or larger provide excellent lubricity (low dynamic friction) and gloss (pearl color tone). (8) The endothermic decomposition peak temperature differs from that of magnesium hydroxide, changing by up to approximately 20°C.

[0024] The organic ligand constituting the highly oriented metal complex salt according to the present invention preferably has one carboxyl group or sulfonic group, preferably bidentate, and is slightly larger than an OH group.Preferred organic ligands include, for example, (1) oxycarboxylic acids (also hydroxycarboxylic acids) such as glycolic acid, lactic acid, glyceric acid, hydroxybutyric acid, pantoic acid, quinic acid, salicylic acid, vanillic acid, syringic acid, orsellinic acid, hydroxybenzoic acid, vanillic acid, gallic acid, mandelic acid, and benzilic acid, preferably glycolic acid, lactic acid, glyceric acid, hydroxybutyric acid, hydroxybenzoic acid, vanillic acid, gallic acid, and mandelic acid; (2) ethylenediamine, hexamethylenediamine, diethanolamine, triethanolamine, putrescine, cataverine, ethambutol, phenylenediamine, toluidine, piperazine, imidazole, pyridazine, pyrimidine, pyrazine, oxazole, and thiazole; Preferred examples include amines such as ethylenediamine, hexamethylenediamine, diethanolamine, triethanolamine, kataverin, toluidine, piperazine, imidazole, pyridazine, pyrimidine, pyrazine, oxazole, and thiazole; (3) aminocarboxylic acids such as glycine, tryptophan, histidine, glutamic acid, aspartic acid, proline, 2-aminobenzenecarboxylic acid, and 4-aminobenzenecarboxylic acid; (4) sulfonic acids such as aminoethanesulfonic acid, 2-aminobenzenesulfonic acid, and 4-aminobenzenesulfonic acid; (5) polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin; and (6) polyphenols such as anthocyanin and catechin. Particularly preferred organic ligands are those represented by the above formulas (1) and (2). The amount x of the organic ligand is within the range of 0≦x<0.2, preferably 0≦x<0.1, and particularly preferably 0.01≦x<0.06. The amount y of the organic ligand is in the range of 0<y<0.05, preferably 0.0001<y<0.02, and particularly preferably 0.001<y<0.015. n represents an integer ranging from 1 to 4, preferably 1 or zero.

[0025] The highly oriented metal complex salt according to the present invention may contain, in addition to pure magnesium hydroxide, Mg(OH)２ A part of Mg in the above is replaced with another divalent metal M ２＋ , preferably Ca ２＋ , Mn ２＋ , Fe ２＋ , Co ２＋ , Ni ２＋ , Cu ２＋ and Zn ２＋ , particularly preferably Ca ２＋ , Fe ２＋ , Ni ２＋ and Zn ２＋ It includes a solid solution substituted with at least one of the following. ２＋ The solid solution range x of Ca is 0≦x<0.3, preferably 0≦x≦0.2, and particularly preferably 0≦x≦0.1. ２＋ strengthens the basicity, and Ni ２＋ and Zn ２＋ improves flame retardancy through dehydrogenation catalytic action, and Ni ２＋ improves acid resistance. ２＋ , Fe ２＋ , and Co ２＋ has oxygen absorbing properties and oxidative decomposition properties for resins, and can be used as an oxygen absorber and / or biodegradation accelerator by being blended into food packaging resin films. ２＋ can be used as a therapeutic agent for iron deficiency anemia.

[0026] In addition to the above, the highly oriented metal complex salt according to the present invention is suitable for applications such as a mechanical reinforcement agent for resins such as polypropylene, a flame retardant, a thermal conductivity improver (heat dissipation material), a gas barrier material, a smoke suppressant, a filler for artificial marble, a base material for lubricating powders in cosmetics (a functional substitute for talc or mica), a base material for pearl pigments (surface coated with fine particles of titanium oxide, iron oxide, etc.), and a therapeutic agent for iron deficiency anemia.

[0027] The highly oriented metal composite salt according to the present invention is fired at 400 to 1000°C, whereby it has a thin thickness, high orientation, and excellent dispersibility, and therefore, magnesium oxide and / or magnesium oxide having excellent adhesiveness and reactivity is partly converted into magnesium. ２＋ Therefore, by taking advantage of this characteristic, it is possible to use it as an annealing separator for electrical steel sheets, a heat dissipating material for resins and rubbers, an acid acceptor for halogen-containing rubbers, a vulcanization accelerator for rubbers, etc.

[0028] <Production Method> Step 1 (Coprecipitation Reaction) (A) A mixed aqueous solution of a water-soluble magnesium salt and an organic ligand, or a mixed aqueous solution of a water-soluble magnesium salt and a water-soluble divalent metal (M ２＋ To a mixed solution of the divalent metal salt and the organic ligand, at least 0.95 equivalents, preferably 0.9 equivalents or less, and particularly preferably 0.8 to 0.6 equivalents or more of alkali are added relative to the total equivalents of the divalent metal, resulting in coprecipitating. Second Step (Hydrothermal Treatment): The coprecipitate obtained in Step 1 is hydrothermally treated at 100°C or higher, preferably 120°C or higher, particularly preferably 180°C to 250°C, for 1 hour or more, preferably 2 to 10 hours. By changing the hydrothermal treatment temperature, the lateral width of the primary particles can be adjusted to a range of 0.21 to 40 μm.

[0029] <Surface Treatment> Various functions can be imparted to the highly oriented metal composite salt according to the present invention by surface treatment. For example, in order to improve compatibility with resins and acid resistance, the highly oriented metal composite salt may be treated with a surface treatment such as (a) higher fatty acids such as stearic acid and lauric acid, (b) alkali metal salts of the above higher fatty acids, (c) anionic surfactants such as sodium dialkylsulfosuccinate, alkyl ether sulfate, 2-ethylhexyl alkyl sulfate sodium salt, sodium acylmethyl taurate, sodium alkylbenzenesulfonate, and oleoyl sarcosine, and (d) acid type / or alkali metal salt / or amine salt of a mono- or diester of orthophosphoric acid and stearyl alcohol. Examples of suitable coupling agents include phosphate esters, (e) silane coupling agents such as vinylethoxysilane and γ-aminopropyltrimethoxysilane, (f) titanate coupling agents such as isopropyltriisostearoyltitanate, (g) aluminum coupling agents such as acetoalkoxyaluminum diisopropylate, (h) fatty acid esters of polyhydric alcohols such as sorbitan monostearate, (i) polycarboxylic acids such as sodium polyacrylate and sodium polystyrenesulfonate, and (j) alkali metal salts of polysulfonic acid. To enhance acid resistance, silica coating can be achieved by chemical adsorption of water glass followed by the addition of acid, silica coating by hydrolysis of methyl silicate, ethyl silicate, or the like, or silicone coating with silicone oil. To enhance ultraviolet absorption and / or scattering, coating with fine particles such as titanium oxide, zinc oxide, or cerium oxide can be used. The pearl pigment can be produced by a method in which a highly oriented metal composite salt with or without surface treatment for improving acid resistance is dispersed in a solvent such as water, and then fine particles of a metal oxide such as titanium oxide, iron oxide, or zinc oxide are added to uniformly coat the surface. Examples of surface treatment agents used as flame retardants for paper include carboxymethyl cellulose and sodium alginate.

[0030] The surface treatment is preferably carried out by a wet or dry method. The wet method is a method in which a metal composite salt is dispersed in a solvent such as water or alcohol, and a surface treatment agent is added while stirring. The dry method is a method in which a surface treatment agent is added to a powdered highly oriented metal composite salt while stirring using a high-speed stirrer such as a Henschel mixer. The amount of the surface treatment agent is appropriately selected and determined depending on the purpose, but the preferred range is generally 0.5 to 20 wt % relative to the weight of the highly oriented metal composite salt.

[0031] <Resin Composition> The resin composition according to the present invention contains 0.01 to 300 parts by weight, preferably 0.5 to 200 parts by weight, and particularly preferably 1 to 100 parts by weight, of a highly oriented metal complex salt per 100 parts by weight of resin. The optimal amount varies depending on the purpose. For example, when the purpose is to mechanically strengthen the resin, such as the flexural modulus, flexural strength, and Izod strength, the amount is 1 to 40 parts by weight; when used as a diffuser for halogen-containing rubber, the amount is 1 to 20 parts by weight; when used as a flame retardant or gas barrier agent for resin, the amount is 50 to 200 parts by weight; and when used as an acid acceptor for resins such as polyamide, the amount is 0.01 to 5 parts by weight.

[0032] <Processing Method> There are no particular limitations on the method of mixing and kneading with the resin, as long as the two can be mixed uniformly. For example, mixing and kneading can be performed using a single-screw or twin-screw extruder, an open roll, a Banbury mixer, etc. There are also no particular limitations on the molding method, and any known molding means can be used depending on the types of resin and rubber, the type of desired molded product, etc. Examples of molding means include injection molding, rotational molding, calendar molding, sheet forming, transfer molding, lamination molding, and vacuum molding.

[0033] <Types of Resin> The resin used in the present invention means resin and / or rubber, and examples thereof include (A) thermoplastic resins such as polyethylene, copolymers of ethylene and other α-olefins, copolymers of ethylene and vinyl acetate, ethyl acrylate or methyl acrylate, polybutene-1, poly-4-methylpentene-1, polystyrene, copolymers of styrene and acrylonitrile, copolymers of ethylene and propylene diene rubber or butadiene, polyvinyl acetate, polyvinyl alcohol, polyacrylate, polymethacrylate, polyurethane, polyester, polyether, polyamide, ABS, polycarbonate and polyphenylene sulfide; (B) thermosetting resins such as phenol resin, melamine resin, epoxy resin, unsaturated polyester resin and alkyd resin; and (C) rubbers such as EPDM, SBR, NBR, butyl rubber, chloroprene rubber, isoprene rubber, chlorosulfonated polyethylene rubber, silicone rubber, fluororubber, chlorinated butyl rubber, epichlorohydrin rubber and chlorinated polyethylene rubber.

[0034] Examples of preferred resins include polypropylene, a mixture of polypropylene and olefinic rubber, polyethylene, polyamide, EPDM, butyl rubber, and chloroprene rubber.

[0035] The resin composition according to the present invention may contain, in addition to the highly oriented metal composite salt, a conventionally known reinforcing agent such as talc, mica, glass fiber, basic magnesium sulfate fiber, etc. The amount of these reinforcing agents to be blended is 1 to 50 parts by weight, preferably 1 to 20 parts by weight, per 100 parts by weight of the resin.

[0036] In addition to the reinforcing agent, other commonly used additives, for example, antioxidants, ultraviolet absorbers, lubricants, pigments such as carbon black, bromine-based or phosphate-based flame retardants, flame retardant assistants such as zinc stannate, alkali metal stannate and carbon powder, and fillers such as calcium carbonate, zeolite and kaolin, can be appropriately selected and blended.

[0037] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the examples, (A) pretreatment for XRD measurement, (B) primary particle size, and (C) average secondary particle size of the highly oriented metal composite salt were measured by the methods described below. (A) XRD measurement: The dried product was sieved through a 30 mesh sieve and then sieved through a 60 mesh sieve to prepare a powder. (B) Primary particle size: The powder sieved through the 60 mesh sieve was dispersed in water for 5 minutes using ultrasonic waves, and the maximum width and thickness of five primary particles were measured using a scanning electron microscope (SEM), and the arithmetic mean value was used. (C) Average secondary particle size: A sample dispersed in the same manner as in (B) was measured using a laser diffraction particle size distribution analyzer (HORIBA LA960), and the 50% cumulative secondary particle size was taken as the average secondary particle size.

[0038] The organic ligands were analyzed by spectrophotometry. i) When the organic ligands were lactic acid, glycolic acid, triethanolamine, and p-toluidine-2-sulfonic acid, they were analyzed by the method described in the following literature: L. N. Borshchevskaya et al., J. Analytical Chemistry, 71, No. 8, 755-758 (2016). ii) When the organic ligand was ethylenediamine, they were analyzed by the method described in the following literature: Goro Hihara et al., Bull. Chem. Soc. Jpn., 54, 268-271 (1981).

[0039] The TG-DTA measurement was carried out using a TG-8120 manufactured by Rigaku Corporation under the conditions of an atmosphere of air and a temperature rise rate of 20° C. / min.

[0040] A 400 mL solution of 2.0 mol / L magnesium chloride (reagent grade) was mixed with 1 g of sodium lactate (70% solution, reagent), equivalent to 1 mol% of the organic ligand relative to the Mg, at approximately 20°C. The resulting solution was placed in a 1 L container and, with stirring, 320 mL of a 4 mol / L sodium hydroxide solution (approximately 20°C), equivalent to 0.8 equivalents relative to the Mg, was added to cause coprecipitation. The coprecipitation was transferred to a 1 L autoclave and hydrothermally treated at 200°C for 4 hours. The hydrothermally treated product was filtered, washed with water, dried, and sieved (through a 30-mesh sieve and then re-sieved through a 60-m mesh sieve). XRD (powder X-ray diffraction) (Figure 1) of the sieved sample was performed, and the diffraction intensity ratio H (%) of the (101) plane to the (001) plane was measured. The sieved sample was ultrasonically treated in an aqueous medium for 5 minutes, followed by SEM analysis (Figure 2). The maximum width and thickness of the primary particles were measured for five primary particles, and the average values ​​were calculated. The lactic acid and Mg contents were measured by dissolving the sample in hydrochloric acid and then using absorptiometry (a sample solution containing 10 to 200 ppm of lactic acid was added with an equal volume of 0.2% aqueous ferric chloride solution to adjust the pH to approximately 3.1, causing a yellow color, and the intensity at a wavelength of 390 nm was measured; a control was used in which 0.2% aqueous ferric chloride solution was diluted with an equal volume of water) and chelate titration. The results are shown in Table 1 below. The XRD pattern was identical to that of magnesium hydroxide, indicating that this sample contained the same Cd(OH) as magnesium hydroxide. ２ It has a crystalline structure. The interplanar spacing of the (001) plane, d = 4.67 Å, ​​is shorter than that of magnesium hydroxide, d = 4.77 Å (POWDER DIFFRACTION FILE 7-239), which supports the fact that lactate ions replace some of the OH groups in the solid solution. The orientation H of the sieved sample was 1%, and the orientation of the above FILE was calculated to be 111%, indicating that the orientation of the product of the present invention is extremely high. The average primary particle size was 6.1 μm, while the average secondary particle size was 6.2 μm, indicating almost no secondary aggregation. TG-DTA data indicates that the endothermic decomposition peak temperature is 419°C.

[0041] The same procedure as in Example 1 was repeated except that the amount of sodium lactate added to the aqueous sodium lactate solution relative to Mg was changed to 2.5 mol %. The measurement results are shown in Table 1 below. The XRD pattern is the same as that of magnesium hydroxide.

[0042] The same procedure as in Example 1 was repeated except that the amount of sodium lactate added to the aqueous sodium lactate solution relative to Mg was changed to 0.5 mol %. The measurement results are shown in Table 1 below. The XRD pattern is the same as that of magnesium hydroxide.

[0043] Comparative Example 1 The same procedure as in Example 1 was repeated except that the amount of sodium lactate added to the aqueous sodium lactate solution relative to Mg was changed to 10 mol %. The measurement results are shown in Table 1 below.

[0044] Comparative Example 2 The same procedure as in Example 1 was repeated, except that the amount of 4 mol / L aqueous sodium hydroxide solution added was changed to 400 mL, which corresponds to 1.0 equivalent relative to Mg. The measurement results are shown in Table 1 below.

[0045] Comparative Example 3 The same procedure as in Example 1 was repeated except that the addition of sodium lactate was omitted. The measurement results are shown in Table 1 below. From the TG-DTA data, the endothermic decomposition peak temperature was 411°C.

[0046] Comparative Example 4 The same procedure as in Example 1 was repeated, except that instead of sodium lactate as the organic ligand, sodium acetate was added in an amount of 150 mol % relative to Mg according to a conventional method for producing high aspect ratio magnesium hydroxide (Patent Document 3, Example 1). The measurement results are shown in Table 1 below.

[0047] The same procedure as in Example 1 was carried out except that the hydrothermal treatment temperature was changed from 200°C to 120°C. The measurement results are shown in Table 1 below. The XRD pattern is shown in Figure 1 and the SEM photograph is shown in Figure 2. The XRD pattern is the same as that of magnesium hydroxide.

[0048] Comparative Example 5 The same procedure as in Example 4 was repeated except that the amount of sodium hydroxide added was changed to 400 mL, which corresponds to 1.0 equivalent relative to Mg (corresponding to Example 3 of Patent Document 4). The measurement results are shown in Table 1 below. The XRD is shown in Figure 1.

[0049] The same procedure as in Example 1 was repeated, except that 0.5 mol % of ethylenediamine, a reagent, relative to Mg, was used instead of sodium lactate. The ethylenediamine content was measured by absorptiometry after dissolving the sample in hydrochloric acid. The measurement results are shown in Table 1 below. The XRD pattern is the same as that of magnesium hydroxide. TG-DTA data indicates that the endothermic decomposition peak temperature is 406°C.

[0050] The same procedure as in Example 1 was repeated, except that glycolic acid was added as a reagent in an amount of 1.5 mol % relative to Mg instead of sodium lactate. The glycolic acid content was measured using the same absorptiometry method as in Example 1. The measurement results are shown in Table 1 below. The XRD pattern is the same as that of magnesium hydroxide. The TG-DTA data indicates that the endothermic decomposition peak temperature is 428°C.

[0051] The same procedure as in Example 1 was repeated, except that 1 mol % of glycine was added as a reagent to magnesium instead of sodium lactate. The glycine content was measured by absorptiometry after dissolving the sample in hydrochloric acid. The measurement results are shown in Table 1 below. The XRD pattern is the same as that of magnesium hydroxide.

[0052] The same procedure as in Example 1 was repeated, except that the reagent triethanolamine was added in an amount of 4 mol % relative to Mg instead of sodium lactate. The measurement results are shown in Table 1 below. However, the triethanolamine content was measured using the same absorptiometry method as in Example 5. The XRD pattern is the same as that of magnesium hydroxide. From the TG-DTA data, the endothermic decomposition peak temperature is 416°C.

[0053] The same procedure as in Example 1 was repeated, except that the magnesium chloride aqueous solution was mixed with 2 mol % of zinc chloride as a reagent relative to Mg, and the hydrothermal treatment temperature was changed to 250° C. The measurement results are shown in Table 1 below. The XRD pattern was the same as that of magnesium hydroxide.

[0054] The same procedure as in Example 1 was repeated, except that nickel chloride (reagent) was mixed into the magnesium chloride aqueous solution at 2 mol % relative to Mg, and glycolic acid (representing 2 mol % relative to Mg) was added instead of sodium lactate. The measurement results are shown in Table 1 below. The XRD pattern was the same as that of magnesium hydroxide.

[0055] The same procedure as in Example 1 was carried out, except that industrial grade magnesium chloride (manufactured by Naikai Salt Industry, special grade) was used instead of first-grade reagent magnesium chloride, and the hydrothermal treatment temperature was changed to 250°C. The measurement results are shown in Table 1 below. The XRD pattern was the same as that of magnesium hydroxide.

[0056] The same procedure as in Example 11 was repeated, except that p-toluidine-2-sulfonic acid was used as a reagent instead of sodium lactate. Analysis of p-toluidine-2-sulfonic acid was carried out by HPLC. The measurement results are shown in Table 1 below. The XRD pattern is the same as that of magnesium hydroxide. TG-DTA data indicates that the endothermic decomposition peak temperature is 405°C.

[0057] The same procedures as in Example 1 were repeated except that 0.05 mol of industrial ferrous chloride solution (manufactured by Taiki Pharmaceutical Co., Ltd., concentration 32% by weight) was added per mol of magnesium chloride, and lactic acid (first-grade reagent, 90% solution) was used instead of sodium lactate. The measurement results are shown in Table 1 below.

[0058] The resulting product was white. The XRD pattern was the same as that of magnesium hydroxide. It was found that divalent iron was dissolved in the solid solution. The composition of this solid solution was measured by chelate titration after dissolving the sample in hydrochloric acid. 0.95 Fe ２＋ 0.05(OH)2. The resulting product can be used as an oxygen absorber by adding it to plastic film for food packaging, taking advantage of the fact that divalent iron is oxidized by oxygen to stable trivalent iron. Furthermore, this solid solution is easily dissolved in gastric acid and can provide easily absorbed divalent iron, making it suitable for use in treating iron deficiency anemia in humans. Existing iron supplements have a metallic taste and are prone to rejection, making it difficult for many people to take them for more than the one month required for iron supplements. This solid solution, similar to magnesium hydroxide, has no metallic taste and is easy to swallow, which also allows for long-term continuous use.

[0059] 1) Molar percentage of added organic substance relative to 1 mole of Mg 2) Molar percentage of added organic ligand relative to 1 mole of Mg 3) Ratio (%) of X-ray diffraction intensity of (101) plane to X-ray diffraction intensity of (001) plane

[0060] <Resin Composition> 500 g of the powder of the highly oriented metal composite salt prepared by the method of Example 1 was added to 5 L of water and dispersed using a chemical stirrer. The mixture was then heated to 80°C, and 10 g of sodium stearate was added under stirring to perform a surface treatment. The mixture was then filtered, washed with water, and dried. 12 parts by weight (equivalent to approximately 20% by weight of the total) of the powder was mixed with 100 parts by weight of polypropylene together with 0.2 parts by weight of an antioxidant (IRGANOX 1010). This mixture was kneaded at approximately 190°C using a twin-screw extruder to produce pellets. The pellets were vacuum dried and then injection molded at approximately 230°C using an injection molding machine to produce test specimens. The test specimens were used to measure the flexural modulus (measured in accordance with JIS 7171) and Izod impact strength (measured in accordance with JIS 7110), and the pellets were used to measure the melt flow index (MFR) (measured in accordance with JIS 7210). The results are shown in Table 2 below.

[0061] Comparative Example 6 The same procedure as in Example 11 was repeated, except that the high aspect ratio magnesium hydroxide prepared by the method of Comparative Example 4 (Patent Document 3) was used instead of the highly oriented metal composite salt prepared by the method of Example 1. The evaluation results are shown in Table 2 below.

[0062] Comparative Example 7 The same procedure as in Example 11 was carried out except that talc (primary particle size: 5 μm, thickness: 0.2 μm, aspect ratio: 20), which is often used as a reinforcing agent for automotive resins, was used instead of the highly oriented metal composite salt of Example 11. In a control example, the same procedure as in Example 11 was carried out except that no reinforcing agent was used. The evaluation results are shown in Table 2 below.

[0063]

[0064] <Cosmetic with excellent spreadability (smoothness)> The highly oriented metal complex salt of the present invention obtained in Example 11 was sieved through a 60 mesh sieve to measure the static and dynamic friction coefficients, which correspond to the spreadability of the cosmetic. The results are shown in Table 3 below. It can be seen that the powder of the present invention exhibits spreadability (smoothness) equal to or greater than that of existing smooth cosmetics. The filter cake after hydrothermal treatment in the production of this powder exhibits a pearly color tone and a high luster.

[0065] [Comparative Examples 8-1 and 8-2] The static and dynamic coefficients of friction were measured using commercially available mica (SERICITE JS-1) (Comparative Example 8-1) and talc (JA-467 talc) (Comparative Example 8-2), which are representative lubricating powders for cosmetics. The results are shown in Table 3 below.

[0066] The static friction coefficient and dynamic friction coefficient were measured using the following device and conditions. Device: Static and dynamic friction measuring device TL201Tt manufactured by Trinity Lab Co., Ltd. Test piece: Test powder (passed through a 60 mesh sieve) was placed on a 5 cm x 10 cm sheet at a concentration of 0.5 mg / m ２ Application load: 25 g Sample movement speed: 1 mm / sec Measurement distance range: 20 mm

[0067]

[0068] It is known that the spreadability (smoothness) of cosmetics is better when the dynamic friction coefficient is smaller, so it can be seen that Example 15 (the product of the present invention) has the same or better spreadability than Comparative Examples 8-1 and 8-2 (existing products).

Claims

1. The following formula (1): (Mg) １－ｘ (M ２＋ ) ｘ (OH) ２－ｎｙ A ｙ (1) (wherein, M ２＋ represents at least one divalent metal other than Mg, A represents at least one organic ligand, x and y are within the following ranges: 0≦x<0.2 and 0<y<0.05, and n represents an integer ranging from 1 to 4 or zero. and the X-ray diffraction intensity ratio (orientation H) of the (101) plane to the (001) plane is 60% or less. ２ Highly oriented metal complex salt with a crystalline structure.

2. n is an integer ranging from 1 to 4; 2. The highly oriented metal complex salt according to claim 1, wherein the X-ray diffraction intensity ratio (orientation H) is 60% or less.

3. n is an integer ranging from 1 to 4; 2. The highly oriented metal complex salt according to claim 1, having an X-ray diffraction intensity ratio (orientation H) of 30% or less.

4. n is an integer ranging from 1 to 4; 2. The highly oriented metal complex salt according to claim 1, wherein the X-ray diffraction intensity ratio (orientation H) is 60% or less (excluding 30% or less).

5. The highly oriented metal complex salt according to claim 1 , wherein n is zero.

6. 2. The highly oriented metal composite salt according to claim 1, wherein the average lateral width of the primary particles of the highly oriented metal composite salt is 0.4 μm or more and 50 μm or less.

7. 2. The highly oriented metal composite salt according to claim 1, wherein the orientation H is 6% or less, and the average lateral width of the primary particles of the highly oriented metal composite salt is 2 μm or more and 50 μm or less.

8. 2. The highly oriented metal complex salt according to claim 1, wherein in formula (1), the organic ligand A is at least one selected from the group consisting of hydroxycarboxylic acids, amines, amino acids, polyhydric alcohols, and polyphenols.

9. In formula (1), M ２＋ is Ca ２＋ , Mn ２＋ , Fe ２＋ , Co ２＋ , Ni ２＋ , Cu ２＋ and Zn ２＋ 2. The highly oriented metal complex salt according to claim 1, which is at least one selected from the group consisting of:

10. 2. The highly oriented metal complex salt according to claim 1, wherein in formula (1), x is in the range of 0.001<x<0.

02.

11. 2. The highly oriented metal composite salt according to claim 1, which is surface-treated with at least one selected from higher fatty acids, alkali metal salts, anionic surfactants, phosphate esters, silane coupling agents, titanium coupling agents, and aluminum coupling agents, fatty acid esters, polycarboxylic acids, alkali metal salts, water glass, methyl silicate, ethyl silicate, silicone oil, titanium oxide, zinc oxide, and cerium oxide, metal oxide fine particles, and carboxymethyl cellulose and sodium alginate.

12. A resin composition comprising 0.01 to 300 parts by weight of the highly oriented metal complex salt according to any one of claims 1 to 11 per 100 parts by weight of resin.

13. 12. A method for producing a highly oriented metal composite salt according to claim 1, characterized in that (A) an aqueous solution of a water-soluble salt of a divalent metal containing at least Mg is added with (B) an organic ligand in an amount of less than 10 mol % relative to the total number of moles of the divalent metal containing at least Mg, and (C) the resulting solution is co-precipitated with at least 0.95 equivalents of an alkali relative to the total equivalents of the divalent metal containing Mg, followed by hydrothermal treatment at 100°C or higher.

14. The divalent metal other than Mg is Ca ２＋、 Mn ２＋ , Fe ２＋ , Co ２＋ , Ni ２＋ , Cu ２＋ and Zn ２＋ The method according to claim 13, wherein the at least one selected from the group consisting of: