Highly oriented metal composite 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

[Technical Field]

[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 in which part of OH groups in Mg(OH)₂ are substituted with organic ligands, and which has large primary particle width, extremely small thickness, and is easily oriented in the width direction. [Background Art]

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

[0003] However, the present inventors developed nearly monodisperse magnesium hydroxide (trade name: Kisuma 5), which has a primary particle (single crystal) width of about 0.8 to 1 µm, a thickness of about 0.2 µm, and almost no secondary aggregation (primary particle size = secondary particle size) (Patent Document 1), which opened up a large market as a non-halogen flame retardant for resins. Prior to that, magnesium hydroxide had a primary particle width of about 0.2 µm or less, strong aggregation, and large secondary particles (particles formed by aggregation of primary particles, measured by particle size distribution) of 5 µm or more.

[0004] In order to further expand the applications of magnesium hydroxide-based compounds, the present inventors provide the following formula (2): Mg 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 high-aspect-ratio hexagonal plate-shaped magnesium hydroxide-based solid solution with an average width of 1 to 10 μm, a thickness of 0.01 to 0.5 μm, and an aspect ratio of 10 or higher, represented by (x) (where x is in the range of 0.01 ≤ x < 0.5), and calcined hydroxide. This solid solution is produced by hydrating the oxide obtained by calcining the hydroxide represented by formula (2) in an aqueous medium in the presence of a monocarboxylic acid and / or an oxymonocarboxylic acid. By increasing the aspect ratio, new applications such as resin reinforcing agents have been opened up (Patent Document 2).

[0005] The present inventors have further advanced their research on high-aspect-ratio magnesium hydroxide and have developed a high-aspect-ratio magnesium hydroxide with a width of 0.5 μm or more, a thickness of 0.2 μm or less, and an aspect ratio of 10 or more by (A) adding alkali to an aqueous mixed solution of a water-soluble magnesium salt and an alkali metal salt and / or ammonium salt of a monovalent organic acid to coprecipitate, or (B) adding alkali to an aqueous solution of a water-soluble magnesium salt to coprecipitate, followed by the addition of 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 higher (Patent Document 3).

[0006] Furthermore, the inventors have developed a method for producing a high aspect ratio magnesium hydroxide-based solid solution represented by formula (2) at a reduced cost. The method involves (A) a water-soluble Mg salt and (B) a water-soluble divalent metal salt (M 2+ (C) A mixed aqueous solution of (D) or a metal complex thereof is reacted with (C) an alkaline aqueous solution such as sodium hydroxide in the presence or absence of (D) monocarboxylate ions, and then 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, with the aim of developing fine-particle magnesium hydroxide, some of the hydroxyl groups (OH) were replaced with monovalent organic acids, as shown in formula (3): Mg(OH) 2-x Rx (3) A magnesium hydroxide-based solid solution represented by (wherein R is a monovalent organic acid, and x represents the range of 0 < x < 1) and having an average secondary particle diameter of 300 nm or less has been developed. This fine-particle solid solution is produced by either: method (A), which comprises adding an alkali substantially equivalent to Mg to a mixed aqueous solution of a water-soluble magnesium salt and a monovalent organic acid or a salt thereof to effect coprecipitation, followed by hydrothermal treatment; or method (B), which comprises adding an aqueous alkali solution to an aqueous solution of a water-soluble magnesium salt to effect coprecipitation, then adding a monovalent organic acid or a salt thereof to the obtained magnesium hydroxide, followed by hydrothermal treatment (Patent Document 5).

Prior Art Document

Patent Documents

[0008]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Summary of the Invention

Problems to be Solved by the Invention

[0009] The higher the aspect ratio, the higher the reinforcing effect on resins, which expands the range of applications. However, the maximum aspect ratio of conventional magnesium hydroxide-based compounds is 50 or less. Therefore, the first object of the present invention is to provide a magnesium hydroxide-based compound having a high aspect ratio with an aspect ratio exceeding 50.

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

[0011] The inventors of the present invention conducted intensive studies to solve the above problems, and as a result, found that the following formula (1): (Mg) 1-x (M 2+ ) x (OH) 2-ny A y (1) (wherein in the formula, M 2+ represents at least one or more divalent metals other than Mg, A represents at least one or more organic ligands, x and y each fall 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, and n represents an integer in the range of 1 to 4, preferably 1, or zero) and succeeded in developing a highly oriented metal composite salt represented by the formula, having an X-ray diffraction intensity ratio (orientation H) of the (101) plane to the (001) plane of 60% or less, and having a hexagonal Cd(OH)2-type crystal structure. The X-ray diffraction intensity ratio (orientation H) described above 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 in the range of 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 is zero.

[0014] Furthermore, the present inventors have succeeded in developing a method for producing the above-mentioned highly oriented metal composite salt, characterized by (A) adding an organic ligand 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 to an aqueous solution of the divalent metal containing at least Mg, (B) coprecipitation with an alkali in an amount of at least 0.95 equivalents or less relative to the total equivalent amount of the divalent metal containing at least Mg, and then hydrothermally treating it at 100°C or higher.

[0015] The production of highly oriented metal complex salts is carried out by (A) adding (B) approximately 0.01 moles of an organic ligand capable of forming a metal complex to an aqueous solution of water-soluble magnesium salt relative to Mg, and (C) supplying alkali in an amount of at least 0.95 equivalents or less, preferably 0.9 equivalents or less, relative to Mg 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 a reduced production cost. The amount of organic ligand required is extremely small, equivalent to about 1 / 100 of the amount of monovalent organic acid or its salt required in conventional technology. If the amount is increased or decreased, the orientation (aspect ratio) decreases rapidly. This is a novel discovery that could not be anticipated at all under the conventional idea that increasing the amount of monovalent organic acid leads to a higher aspect ratio.

[0016] A second important manufacturing condition in this invention is the amount of alkali added to Mg, which is at least 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. By suppressing the amount of alkali added to less than an equivalent, the function of the organic ligand can be exerted. [Effects of the Invention]

[0017] The highly oriented composite metal salt according to the present invention has a thinner primary particle (crystallite) thickness (minimum of approximately 5 nm), a significantly larger width (maximum of approximately 40 μm), and less aggregation compared to conventional techniques using monovalent organic acids or their salts. As a result, the orientation is extremely high, and therefore a higher aspect ratio (maximum of approximately 200 in the present invention compared to a maximum of approximately 40 in conventional techniques). Consequently, the reinforcing effect on resins is higher than that of conventional products, and because reinforcing can be achieved with a smaller amount, it further contributes to the weight reduction of automobiles and expands the range of applications to other automobile parts such as door trims, bumpers, and instrument panels.

[0018] Beyond automotive applications, resins can be used as flame retardants, smoke suppressants, heat conductive agents, gas barrier materials, oxygen absorbers, and biodegradation accelerators. Furthermore, they can be used as rust inhibitors in paints, dyes in textiles, and flame retardants in paper. Additionally, their excellent lubricity and pearlescent gloss make them suitable for use as a cosmetic lubricating powder, replacing mica and talc.

[0019] Because the amount of organic ligand required for the production of highly oriented metal composite salts according to the present invention is extremely small, approximately 0.01 moles per mole of Mg, raw material costs can be significantly reduced compared to conventional technologies. Furthermore, the equipment and processes for recovering organic matter can be omitted, resulting in further cost reductions. [Brief explanation of the drawing]

[0020] [Figure 1] XRD patterns of products from Example 1, Example 4 and Comparative Example 5 [Figure 2] SEM images of Example 1 and Example 4 [Modes for carrying out the invention]

[0021] This invention has discovered a novel synthesis method in which an organic ligand capable of forming a metal complex is used instead of the conventional monovalent carboxylic acid, and an alkali is coprecipitation reaction is carried out with an alkali of 0.95 equivalents or less, preferably 0.9 equivalents or less, 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, particularly preferably 180°C or higher.

[0022] This invention was obtained as a result of diligent research based on the following ideas. By creating conditions that facilitate the formation of complexes between Mg ions and organic ligands, two new functions not found in conventional technologies can be added. First, since the organic ligand binds to the Mg ion 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 technologies that use monovalent organic acids that can only bind at one site. Second, since the complex with Mg has a certain degree of water solubility, which is a characteristic of metal complexes, improved solubility can be expected, and as a result, the growth of primary particles is promoted, aggregation is reduced, and dispersibility is improved.

[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 it has the same hexagonal Cd(OH)2 type crystal structure as magnesium hydroxide. Some of the OH groups of Mg(OH)2 are substituted with organic ligands, but the crystal structure is the same as Mg(OH)2. (2) The ratio of X-ray diffraction intensity 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 of H indicates a higher aspect ratio of primary particles and less aggregation. Further testing of the examples in Patent Document 5, which describes a solid solution similar to the present invention, revealed that the H content of the glycolic acid solid solution (Example 2) and the lactic acid solid solution (Example 3) was 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, 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, particularly preferably 10 nm to 50 nm. (5) The aspect ratio, which is the ratio of the width to the thickness of the primary particle, 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, and therefore, secondary aggregation is minimal. (7) When the primary particles are 2 μm or larger, they exhibit excellent lubricity (low dynamic friction) and gloss (pearlescent color). (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 composite salt according to the present invention preferably has one carboxyl group or sulfone group, is preferably bidentate-coordinated, and is suitably slightly larger than an OH group. Preferred organic ligands include, for example: (1) oxycarboxylic acids (which are 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 benzylic acid, preferably glycolic acid, lactic acid, glyceric acid, hydroxybutyric acid, hydroxybenzoic acid, vanillic acid, gallic acid and mandelic acid; (2) amines such as ethylenediamine, hexamethylenediamine, diethanolamine, triethanolamine, putrescine, cadaverine, ethambutol, phenylenediamine, toluidine, piperazine, imidazole, pyridazine, pyrimidine, pyrazine, oxazole and thiazole, preferably ethylenediamine, hexamethylenediamine, diethanolamine, triethanolamine, cadaverine, 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 anthocyanins and catechins. Particularly preferred organic ligands are those represented by the above formulas (1) and (2). The range of the amount x of the organic ligand is 0≦x<0.2, preferably 0≦x<0.1, and particularly preferably 0.01≦x<0.06. The range of the amount y of the organic ligand is 0<y<0.05, preferably 0.0001<y<0.02, and particularly preferably 0.001<y<0.015. n is an integer in the range of 1 to 4, and preferably represents 1 or zero.

[0025] The highly oriented metal composite salt according to the present invention contains, in addition to pure magnesium hydroxide, a portion of the Mg in Mg(OH)2 is replaced with another divalent metal M. 2+ Preferably Ca 2+ ,Mn 2+ Fe 2+ Co 2+ Ni 2+ ,Cu 2+ and Zn 2+ Ca is particularly preferred. 2+ Fe 2+ Ni 2+ and Zn 2+ It contains a solid solution substituted with at least one of the following: M 2+ The solid solution range x is 0 ≤ x < 0.3, preferably 0 ≤ x ≤ 0.2, and particularly preferably 0 ≤ x ≤ 0.1. Ca 2+ Ni enhances basicity. 2+ and Zn 2+ It improves flame retardancy through dehydrogenation catalytic action, Ni 2+ This improves acid resistance. Furthermore, Mn 2+ Fe 2+ , and Co 2+ It has oxygen-absorbing properties and an oxidative decomposition effect on resins, and can be incorporated into food packaging resin films as an oxygen absorber and / or biodegradation accelerator. Furthermore, Fe 2+ It can be used as a treatment for iron deficiency anemia.

[0026] In addition to the above, the highly oriented metal composite salt according to the present invention is suitable for applications such as mechanical reinforcing agents for resins such as polypropylene, flame retardants, thermal conductivity improvers (heat dissipation materials), gas barrier materials, smoke suppressants, fillers for artificial marble, lubricating powder base materials for cosmetics (substituting for the functions of talc or mica), base materials for pearl pigments (surface coated with fine particles of titanium dioxide, iron oxide, etc.), and iron deficiency anemia treatment agents.

[0027] The highly oriented metal composite salt according to the present invention is obtained by calcining at 400-1000°C, resulting in a thin, highly oriented, and highly dispersible salt, and a portion of magnesium oxide and / or Mg with excellent adhesion and reactivity. 2+A magnesium oxide solid solution substituted with this compound can be produced. Therefore, it can be used as an annealing separator for electrical steel sheets, a heat dissipation material for resins and rubbers, an acid acceptor for halogen-containing rubbers, and a vulcanization accelerator for rubbers, taking advantage of its characteristics.

[0028] <Manufacturing method> Step 1 (coprecipitation reaction) (A) A mixed aqueous solution of a water-soluble magnesium salt and an organic ligand, or a water-soluble magnesium salt and a water-soluble divalent metal (M 2+ To the mixed solution of the salt and the organic ligand, add an alkali in an amount of at least 0.95 equivalents, preferably 0.9 equivalents, and particularly preferably 0.8 equivalents to 0.6 equivalents or more, relative to the total equivalent weight of the divalent metal, and allow to co-precipitate. 2nd process (hydrothermal treatment) The coprecipitation obtained in the first step is subjected to hydrothermal treatment at 100°C or higher, preferably 120°C or higher, and particularly preferably 180°C to 250°C for 1 hour or more, preferably 2 to 10 hours. By changing the hydrothermal treatment temperature, the width of the primary particles can be adjusted to a range of 0.21 to 40 μm.

[0029] <Surface treatment> The highly oriented metal composite salts according to the present invention can be given various functions by surface treatment. For example, to improve compatibility with resins and acid resistance, (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 dialkylsulfosucrate, alkyl ether sulfate, 2-ethylhexylalkyl sulfate sodium salt, sodium acylmethyltaurate, sodium alkylbenzenesulfonate, and oleoylsarcosine, and (d) acidic / alkali metal / amine salts of mono or diesters of orthophosphate and stearyl alcohol. Phosphate esters, (e) silane coupling agents such as vinylethoxysilane and γ-aminopropyltrimethoxysilane, (f) titanate coupling agents such as isopropyltriisostearoyl titanate, (g) aluminum coupling agents such as acetalkoxyaluminum diisopropylate, (h) fatty acid esters of polyhydric alcohols such as sorbitan monostearate, (i) polycarboxylic acids such as sodium polyacrylate and sodium polystyrene sulfonate, and (j) alkali metal salts of polysulfonic acid can be used. To improve acid resistance, silica coating by chemical adsorption of water glass followed by acid addition, silica coating by hydrolysis of methyl silicate, ethyl silicate, etc., or silicone coating with silicone oil can be performed. To enhance ultraviolet absorption and / or scattering, coating with fine particles such as titanium dioxide, zinc oxide, and cerium oxide can be used. Pearl pigments can be manufactured by dispersing highly oriented metal composite salts, with or without acid-resistant surface treatment, in a solvent such as water, and then uniformly coating the surface by adding metal oxide fine particles such as titanium dioxide, iron oxide, and zinc oxide. Examples of surface treatment agents used as flame retardants for paper include carboxymethylcellulose and sodium alginate.

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

[0031] <Resin composition> The resin composition according to the present invention is blended with 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 composite salt per 100 parts by weight of resin. The optimal blending amount varies depending on the purpose. For example, if the purpose is mechanical strengthening of the resin, such as flexural modulus, flexural strength, or Izod strength, the amount is 1 to 40 parts by weight; if it is used as a dispersant for halogen-containing rubber, it is 1 to 20 parts by weight; if it is used as a flame retardant or gas barrier agent for resin, it is 50 to 200 parts by weight; and if it is used as an acid acceptor for resins such as polyamide, it is 0.01 to 5 parts by weight.

[0032] <Processing method> There are no special restrictions on the method of mixing and kneading with the resin; any method that allows for uniform mixing of the two is acceptable. For example, mixing and kneading can be performed using a single-screw or twin-screw extruder, open roll, Banbury mixer, etc. There are also no special restrictions on the molding method; any known molding means can be arbitrarily adopted depending on the type of resin and rubber, the type of molded product desired, etc. Examples of molding means include injection molding, rotational molding, calendering, sheet forming, transfer molding, lamination, and vacuum forming.

[0033] <Types of resin> The resins used in this invention mean resins and / or rubbers, and 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, styrene and acyllonitrile, 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 phenolic resins, melamine resins, epoxy resins, unsaturated polyester resins, and alkyd resins; 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, mixtures of polypropylene and olefin rubber, polyethylene, polyamide, EPDM, butyl rubber, and chloroprene rubber.

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

[0036] In addition to reinforcing agents, other conventional additives such as antioxidants, UV absorbers, lubricants, pigments like carbon black, brominated or phosphate ester-based flame retardants, flame retardant aids such as zinc stannate, alkali metal stannate salts, 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 determined by the methods described below. (A)XRD measurement The powder used is obtained by sieving the dried material through a 30-mesh sieve and then through a 60-mesh sieve. (B) Primary particle size The powder sieved through the 60-mesh sieve mentioned above was dispersed in water using ultrasound for 5 minutes. The maximum width and thickness of five primary particles were then measured using a scanning electron microscope (SEM), and the arithmetic mean was used to determine the result. (C) Average secondary particle diameter The dispersed sample, prepared in the same manner as in (B), was measured using a laser diffraction particle size analyzer (Horiba LA960), and the 50% cumulative secondary particle size was taken as the average secondary particle size.

[0038] The organic ligands were analyzed using spectrophotometric analysis. i) When the organic ligands were lactic acid, glycolic acid, triethanolamine, and p-toluidine-2-sulfonic acid, the measurements were performed according to the method described in the following literature: LNBorshchevskaya et al., J. Analytical Chemistry, 71, No.8, 755-758 (2016). ii) When the organic ligand is ethylenediamine, it was measured according to the method described in the following literature: Goro Hihara et al., Bull. Chem. Soc. Jpn, 54, 268-271 (1981).

[0039] TG-DTA measurements were performed using a Rigaku Corporation TG-8120 under the conditions of air atmosphere and a heating rate of 20°C / min. [Examples]

[0040] A mixed aqueous solution (approximately 20°C) was prepared by adding and dissolving 1 g of sodium lactate (reagent, 70% solution), equivalent to 1 mol% of the organic ligand relative to Mg, to 400 mL of a 2.0 mol / L magnesium chloride (reagent grade 1) aqueous solution. This solution was placed in a 1 L container, and 320 mL of a 4 mol / L sodium hydroxide aqueous solution (approximately 20°C), equivalent to 0.8 equivalents relative to Mg, was added while stirring to induce coprecipitation. The coprecipitation was transferred to a 1 L autoclave and subjected to hydrothermal treatment at 200°C for 4 hours. The hydrothermal treated material was filtered, washed with water, dried, and sieved (30 mesh sieving followed by resieving with a 60 m mesh). XRD (powder X-ray diffraction) (Figure 1) of the sieved sample was measured, and the diffraction intensity ratio H (%) of the (101) plane to the (001) plane was determined. The sieved sample was sonicated in an aqueous medium for 5 minutes, and then measured using SEM (Figure 2). The maximum width and thickness of five primary particles were measured, and their average values ​​were determined. The lactic acid and Mg content was measured by dissolving the sample in hydrochloric acid and then measuring by spectrophotometric method (a sample solution containing 10-200 ppm lactic acid was mixed with an equal volume of 0.2% ferric chloride aqueous solution to adjust the pH to approximately 3.1, causing it to turn yellow, and measuring the intensity at a wavelength of 390 nm; a control was used which was 0.2% ferric chloride aqueous solution diluted with an equal volume of water) and chelation titration. The results of these measurements are shown in Table 1 below. The XRD pattern is the same as that of magnesium hydroxide, indicating that this sample has the same Cd(OH)2 type crystal structure as magnesium hydroxide. The interplanar spacing d=4.67Å of the (001) plane is shorter than that of magnesium hydroxide d=4.77Å (POWDER DIFFRACTION FILE 7-239), which supports the idea that lactate ions are substituting and solid-solving a portion of the OH groups. The orientation H of the sieved sample was 1%, and the orientation of the above FILE was calculated to be 111%, indicating that the product of the present invention has extremely high orientation. The average primary particle diameter was 6.1 μm, while the average secondary particle diameter was 6.2 μm, indicating that there was almost no secondary aggregation. According to TG-DTA data, the endothermic decomposition peak temperature is 419°C. [Examples]

[0041] The procedure was the same as in Example 1, except that the amount of sodium lactate aqueous solution added 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. [Examples]

[0042] The procedure was the same as in Example 1, except that the amount of sodium lactate aqueous solution added 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] In Example 1, the procedure was carried out in the same manner as in Example 1, except that the amount of sodium lactate aqueous solution added to Mg was changed to 10 mol%. The measurement results are shown in Table 1 below.

[0044] [Comparative Example 2] The procedure was carried out in the same manner as in Example 1, except that the amount of 4 mol / L sodium hydroxide aqueous 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] In Example 1, the procedure was carried out in the same manner as in Example 1, except that the addition of sodium lactate was omitted. The measurement results are shown in Table 1 below. According to TG-DTA data, the endothermic decomposition peak temperature is 411°C.

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

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

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

[0049] In Example 1, the procedure was carried out in the same manner as in Example 1, except that ethylenediamine reagent was used at a concentration of 0.5 mol% relative to Mg instead of sodium lactate. The ethylenediamine content was determined by spectrophotometric analysis 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. From the TG-DTA data, the endothermic decomposition peak temperature is 406°C. [Examples]

[0050] In Example 1, the procedure was carried out in the same manner as in Example 1, except that reagent glycolic acid was added at a concentration of 1.5 mol% relative to Mg instead of sodium lactate. The glycolic acid content was determined by the same spectrophotometric 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. According to TG-DTA data, the endothermic decomposition peak temperature is 428°C. [Examples]

[0051] In Example 1, the procedure was carried out in the same manner as in Example 1, except that reagent glycine was added at a concentration of 1 mol% relative to Mg instead of sodium lactate. The glycine content was determined by spectrophotometric analysis 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. [Examples]

[0052] In Example 1, the procedure was carried out in the same manner as in Example 1, except that 4 mol% of the reagent triethanolamine was added relative to Mg instead of sodium lactate. The measurement results are shown in Table 1 below. However, the triethanolamine content was determined using the same spectrophotometric 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. [Examples]

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

[0054] In Example 1, the procedure was carried out in the same manner as in Example 1, except that 2 mol% of the reagent nickel chloride was mixed with Mg in an aqueous magnesium chloride solution, and 2 mol% of glycolic acid was added to Mg instead of sodium lactate. The measurement results are shown in Table 1 below. The XRD pattern is the same as that of magnesium hydroxide. [Examples]

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

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

[0057] In Example 1, the procedure was carried out in the same manner as in Example 1, except that 0.05 moles of industrial ferrous chloride solution (manufactured by Taiki Pharmaceutical Co., Ltd., concentration 32% by weight) was added to 1 mole of magnesium chloride, and lactic acid (reagent grade 1, 90% solution) was used instead of sodium lactate. The measurement results are shown in Table 1 below.

[0058] The obtained product was white. The XRD pattern was the same as that of magnesium hydroxide. It was found that divalent iron was in solid solution. The composition of this solid solution was determined by chelation titration after dissolving the sample in hydrochloric acid, and it was found to be Mg 0.95 Fe 2+ 0.05 It is (OH)2. The resulting product, utilizing the fact that divalent iron is oxidized by oxygen to stable trivalent iron, can be added to plastic films for food packaging and used as an oxygen absorber. Furthermore, since this solid solution readily dissolves in stomach acid and can supply easily absorbed divalent iron, it can be used as a treatment for iron deficiency anemia in humans. Existing iron supplements have a metallic taste and are prone to causing adverse reactions, making it difficult for many people to continue using them for the required month or more. This solid solution, like magnesium hydroxide, has no metallic taste and is easy to swallow, offering the advantage of long-term continuous use.

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

[0060] <Resin composition> 500 g of the highly oriented metal composite salt powder 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 for surface treatment. After this, the mixture was filtered, washed with water, and dried. 12 parts by weight (corresponding to approximately 20% by weight of the total) of the mixture was mixed with 0.2 parts by weight of an antioxidant (IRGANOX1010) per 100 parts by weight of polypropylene. This mixture was kneaded at approximately 190°C using a twin-screw extruder to prepare pellets. After vacuum drying, these pellets were injection molded at approximately 230°C using an injection molding machine to prepare test specimens. Using these test specimens, the flexural modulus (measured according to JIS 7171) and Izod impact strength (measured according to JIS 7110) were measured, and the melt flow index (MFR) (measured according to JIS 7210) was measured using the pellets. The results are shown in Table 2 below.

[0061] [Comparative Example 6] In Example 11, the procedure was the same as in Example 11, except that 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] In Example 11, the procedure was the same as in Example 11, except that talc (primary particle size 5 μm, thickness 0.2 μm, aspect ratio 20), which is commonly used as a reinforcing agent for automotive resins, was used instead of the highly oriented metal composite salt in Example 11. In the control example, the procedure was the same as in Example 11, except that no reinforcing agent was used. The evaluation results are shown in Table 2 below.

[0063] [Table 2] [Examples]

[0064] <Cosmetics with excellent spreadability (smoothness)> Using the 60-mesh sieved powder of the highly oriented metal composite salt of the present invention obtained in Example 11, the static and dynamic friction coefficients corresponding to the spreadability performance as a cosmetic were measured. The results are shown in Table 3 below. It can be seen that the powder of the present invention exhibits spreadability (slipperiness) equal to or better than existing lubricating cosmetics. The filtered cake after hydrothermal treatment in the production of this powder exhibits a high pearlescent luster.

[0065] [Comparative Examples 8-1 and 8-2] The static and dynamic friction coefficients 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 and dynamic friction coefficients were measured using the following equipment and conditions. Equipment: Static friction measuring instrument TL201Tt, manufactured by Trinity Lab Co., Ltd. Test specimen: Test powder (60 mesh sieved) was placed on a 5cm x 10cm sheet at a concentration of 0.5mg / m². 2 Application Load: 25g Sample transfer speed: 1 mm / second Measurement distance range: 20mm

[0067] [Table 3]

[0068] Since it is known that the spreadability (slipperiness) of cosmetics is better when the dynamic friction coefficient is small, it can be seen that Example 15 (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) (However, in the formula, M ２＋ (where represents at least one divalent metal other than Mg, A represents at least one organic ligand, x and y are in the following ranges: 0 ≤ x < 0.2 and 0 < y < 0.05, respectively, and n is an integer in the range of 1 to 4.) A hexagonal Cd(OH) molecule is represented as such, and its organic ligand includes one or more selected from lactic acid, ethylenediamine, glycolic acid, glycine, triethanolamine, and p-toluidine-2-sulfonic acid, and the X-ray diffraction intensity ratio (orientation H) of the (101) plane to the (001) plane is 60% or less. ２ A highly oriented metal composite salt having a specific crystal structure.

2. The highly oriented metal composite salt according to Claim 1, wherein the X-ray diffraction intensity ratio (orientation H) is 30% or less.

3. The highly oriented metal composite salt according to Claim 1, wherein the X-ray diffraction intensity ratio (orientation H) is 60% or less (excluding 30% or less).

4. The average width of the primary particles of the aforementioned highly oriented metal composite salt is 0.4 μm or more and 50 μm or less. The above-mentioned average width is expressed as the arithmetic mean of the maximum widths of five primary particles measured with a scanning electron microscope, according to claim 1.

5. The orientation H is 6% or less, and the average width of the primary particles of the highly oriented metal composite salt is 2 μm or more and 50 μm or less. The above-mentioned average width is expressed as the arithmetic mean of the maximum widths of five primary particles measured with a scanning electron microscope, according to claim 1.

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

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

02.

8. A highly oriented metal composite salt according to claim 1, 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 dioxide, zinc oxide and cerium oxide, metal oxide fine particles, and carboxymethylcellulose and sodium alginate.

9. A resin composition containing 0.01 to 300 parts by weight of a highly oriented metal composite salt according to any one of claims 1 to 8, per 100 parts by weight of resin.

10. A method for producing a highly oriented metal composite salt according to any one of claims 1 to 8, characterized by: (A) adding 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 to an aqueous solution of a water-soluble salt of a divalent metal containing at least Mg; (B) co-precipitation with an alkali in an amount of at least 0.95 equivalents or less relative to the total equivalent amount of the divalent metal containing Mg; and (C) hydrothermal treatment at 100°C or higher.

11. Divalent metals other than Mg, Ca ２＋、 Mn ２＋ , Fe ２＋ Co ２＋ Ni ２＋ Cu ２＋ and Zn ２＋ The manufacturing method according to claim 10, wherein at least one of the following is selected.

Images